双环氨基衍生物及含有此类化合物的前列腺素d2拮抗剂的制作方法

文档序号:3522599阅读:533来源:国知局
专利名称:双环氨基衍生物及含有此类化合物的前列腺素d2拮抗剂的制作方法
技术领域
本发明涉及双环氨基衍生物和含有此类化合物的前列腺素D2(以下简称PGD2)拮抗剂。
背景技术
本发明地双环氨基衍生物中有一些已知可用作血栓素A2(TXA2)拮抗剂(日本专利公报(KOKOKU)No.79060/1993)。然而,日本专利公报(KOKOKU)No.79060/1993)只描述这些化合物可用作TXA2拮抗剂,而没有提出其作为本发明所公开的PGD2拮抗剂的有用性。
即,TXA2已知具有抗血小板凝集反应、血栓形成等的作用这样的活性。因此,TXA2拮抗剂已被认为可用作抗血栓形成剂,而且也可用于通过拮抗TXA2来治疗心肌梗塞或哮喘。
另一方面,本发明的PGD2拮抗剂可用于改善由于PGD2过量产生而引起的病症。具体地说,它可作为一种药物用于治疗涉及肥大细胞机能障碍的疾病,例如,全身性肥大细胞沉积病和全身性肥大细胞活化失调,而且也可用于治疗气管挛缩、哮喘、变应性鼻炎、变应性结膜炎、荨麻疹、由于局部缺血性重复输注而引起的伤害以及炎症。
从以上所述显而易见,TXA2拮抗剂和PGD2拮抗剂就活性部位、作用机理和应用而言是彼此完全不同的,有十分不同的特征。因此,从来就没有人期待任何一种化合物能同时具有这些活性。
PGD2是借助于由免疫刺激或非免疫刺激活化的环氧酶的作用,从花生四烯酸通过PGG2和PGH2产生的,而且是肥大细胞产生和释放的主要类前列腺素化合物(Prostanoid)。PGD2有各种强效生理活性和病理活性。例如,PGD2会引起强烈气管挛缩从而导致支气管哮喘,而在全身性过敏状态下它会使末梢血管扩张从而导致过敏性休克。特别是,已经有很多人注意到如下想法PGD2是过敏性鼻炎中对鼻塞发生负有责任的病因物质之一。因此,已经有人提出要开发一种能对抗PGD2生物合成的抑制剂或PGD2受体拮抗剂,作为一种减轻鼻塞的药物。然而,PGD2生物合成的抑制剂可能对其它生物体中前列腺素的合成产生很大影响,因此,理想的是开发一种对PGD2受体专一的拮抗剂(阻滞剂)。
发明公开
本发明者等人已经进行锐意研究以期开发对PGD2受体专一的PGD2受体拮抗剂(阻滞剂),发现以下式(I)化合物或其盐具有作为PGD2受体拮抗剂的强活性,而且是化学上和生物上稳定的。
因此,本发明提供一种PGD2拮抗剂,该拮抗剂含有下面通式(I)所示的化合物或其盐或其水合物作为一种活性成分
其中


A是亚烷基,任选地插入杂原子或亚苯基,含有氧代基,和/或有不饱和键;
B是氢、烷基、芳烷基或酰基;
R是COOR1,CH2OR2或CON(R3)R4;
R1是氢或烷基;
R2是氢或烷基;
R3和R4各自独立地是氢、烷基、羟基或烷基磺酰基;
X1是单键、亚苯基、亚萘基、噻吩二基、吲哚二基,或噁唑二基;
X2是单键、-N=N-,-N=CH-,-CH=N-,-CH=N-N-,-CH=N-O-,-C=NNHCSNH-,-C=NNHCONH-,-CH=CH-,-CH(OH)-,-C(C1)=C(C1)-,-(CH2)n-,亚乙炔基,-N(R5)-,-N(R51)CO-,-N(R52)SO2-,-N(R53)CON(R54)-,-CON(R55)-,-SO2N(R56)-,-O-,-S-,-SO-,-SO2-,-CO-、噁二唑二基、噻二唑二基或四唑二基;
X3是烷基、链烯基、炔基、芳基、芳烷基、杂环基、环烷基、环烯基、亚噻唑啉基甲基(thiazolinylidenemethyl)、亚噻唑烷基甲基(thiazolidinylidenemethyl)、-CH=NR6或-N=C(R7)R8;
R5、R51、R52、R53、R54、R55和R56各是氢或烷基;
R6是氢、烷基、羟基、烷氧基、氨基甲酰氧基、硫代氨基甲酰氧基、脲基或硫代脲基;
R7和R8各自独立地是烷基、烷氧基或芳基;
n是1或2;
Z是-SO2-或-CO-;以及
m是0或1;
其中环状取代基可以有1-3个选自下述的取代基硝基、烷氧基、氨磺酰、取代或未取代的氨基、酰基、酰氧基、羟基、卤素、烷基、炔基、羧基、烷氧羰基、芳烷氧羰基、芳氧羰基、甲磺酰氧基、氰基、链烯氧基、羟烷基、三氟甲基、烷硫基、-N=PPh3、氧代、硫代、肟基、烷氧亚氨基、苯基和亚烷二氧基。
实施本发明的最佳方案
可用作上述PGD2拮抗剂的化合物的具体例子包括式(I)的化合物或其盐或其水合物,其中

m是0;且当Z是SO2时,X1和X2两者都是单键;X3是烷基、苯基、萘基、Stylyl(苯乙烯基)、喹啉基或噻吩基;以及这些取代基中环状取代基可任选地带有选自下述的1-3个取代基硝基、烷氧基、取代或未取代的氨基、卤素、烷基和羟烷基。
类似地,具体例子包括式(I)的化合物或其盐或其水合物,其中

当m是1时, X1和X2两者都是单键;而X3是任选地被卤素取代的苯基。
类似地,具体例子包括式(I)的化合物或其盐或其水合物,其中

当m为1时,X1是苯基,X2是-CH2-或-N=N-,而X3是苯基。
类似地,式(I)化合物的例子包括式(1a)的化合物或其盐或其水合物
其中A、B、R、X1、X2和X3的定义同上,其条件是其中(1)X1和X2是单键,而X3是取代或未取代的苯基,或萘基;以及(2)A是5-亚庚烯基,R是COOR1(R1是氢或甲基),X1是1,4-亚苯基,X2是单键,而X3是苯基的那些化合物除外。
类似地,式(I)化合物的例子包括式(Ib)的化合物或其盐或其水合物
其中

A、B、R、X1、X2和X3的定义同上,其条件是其中X1和X2是单键,而X3是苯基,以及其中X1是单键,X2是-O-,而X3是苄基的那些化合物除外。
更具体说,式(I)化合物的例子包括式(Ia)的那些化合物或其盐或其水合物,其中X1和X2都是单键,X3是异噁唑基、噻二唑基、异噻唑基、吗啉基、吲哚基、苯并呋喃基、二苯并呋喃基、二苯并二喔星基、苯并噻吩基、二苯并噻吩基、咔唑基、呫吨基、菲啶基、二苯并噁庚因基、二苯并硫杂七环基(thiepinyl)、肉啉基(cinnolyl)、苯并吡喃基(chromenyl)、苯并咪唑基或二氢苯并硫杂七环基(thiepinyl)。
类似地,式(I)化合物的例子包括式(Ia)的那些化合物或其盐或其水合物,其中X1是单键,X2是亚苯基,X3是链烯基、炔基、-CH=NR6或-N=C(R7)R8。
类似地,式(I)化合物的例子包括式(Ia)的那些化合物或其盐或其水合物,其中R是COOR1,X1是亚苯基或噻吩二基,X2是单键、-N=N-、-CH=CH-、-CONH-、-NHCO-或亚乙炔基,而X3是苯基、亚噻唑啉基甲基、亚噻唑烷基甲基或噻吩基。
更具体说,本发明的化合物(I)的例子包括其中

的式(Ib)化合物或其盐或其水合物更优选的化合物的例子包括其中R是COOR1(R1的定义同上)的式(Ib)化合物或其盐或其水合物。
类似地,化合物(I)的例子包括式(Ib)的那些化合物或其盐或其水合物,其中X1是亚苯基或噻吩二基,X2是单键、-N=N-、-CH=CH-、亚乙炔基、-O-、-S-、-CO-、-CON(R55)-(R55的定义同上)、-N(R51)CO-(R51的定义同上),而X3是苯基。
更具体说,化合物(I)的例子包括式(Ib)的那些化合物或其盐或其水合物,其中

更优选的化合物的例子包括如下定义的那些化合物或其盐或其水合物,其中B是氢,X1和X2两者都是单键,X3是噻吩基、噻唑基、噻二唑基、异噻唑基、吡咯基、吡啶基、苯并呋喃基、苯并咪唑基、苯并噻吩基、二苯并呋喃基、二苯并噻吩基、喹啉基或吲哚基。类似地,例子包括如下定义的那些化合物或其盐或其水合物,其中X1是亚苯基、噻吩二基、吲哚二基或噁唑二基,X2是单键、-N=N-、-CH=CH-、
亚乙炔基、-S-或-O-,而X3是芳基或杂环基。
通式(Ia)和(Ib)的化合物是本发明的发明人合成的新化合物。
本说明书中所用术语定义如下。
术语“亚烷基”是指C1-C9直链或支链亚烷基,例如亚甲基、甲基亚甲基、二甲基亚甲基、甲基乙基亚甲基、亚乙基、三亚甲基、四亚甲基、五亚甲基、六亚甲基、七亚甲基、1,8-亚辛基、1,9-亚壬基,或类似的基团。上述亚烷基中可以插入杂原子(氧、硫、氮等原子)或亚苯基(如1,4-亚苯基、1,3-亚苯基、1,2-亚苯基等),在其链的任何位置可含有一个氧代基,和/或有1个或多双键或三键。其例子包括-(CH2)2-O-CH2-,-(CH2)2-O-(CH2)2-,-(CH2)2-O-(CH2)3-,-(CH2)2-O-(CH2)4-,-(CH2)2-O-(CH2)5-,-(CH2)2-O-(CH2)6-,-(CH2)2-S-(CH2)2-,-(CH2)3-S-(CH2)2-,-CH2-S-CH2-,-CH2-S-(CH2)4-,-CH2-N(CH3)-CH2,-CH2-NH-(CH2)2-,-(CH2)2-N(CH2CH3)-(CH2)3-,-(CH2)2-1,4-亚苯基-CH2-、-(CH2)2-O-1,3-亚苯基-CH2-、-(CH2)2-O-1,2-亚苯基-CH2-、-(CH2)2-O-1,4-亚苯基-CH2-、-CH=CH-S-CH2-1,4-亚苯基-CH2-、-CH=CH-S-1,3-亚苯基-(CH2)2-、2-氧代亚丙基、3-氧代亚戊基、5-氧代亚己基、亚乙烯基、1-亚丙烯基、2-亚丙烯基、1-亚丁烯基、2-亚丁烯基、3-亚丁烯基、1,2-亚丁二烯基、1,3-亚丁二烯基、1-亚戊烯基、2-亚戊烯基、3-亚戊烯基、4-亚戊烯基、1,2-亚戊二烯基、1,3-亚戊二烯基、1,4-亚戊二烯基、2,3-亚戊二烯基、2,4-亚戊二烯基、1-亚己烯基、2-亚己烯基、3-亚己烯基、4-亚己烯基、5-亚己烯基、1,2-亚己二烯基、1,3-亚己二烯基、1,4-亚己二烯基、1,5-亚己二烯基、2,3-亚己二烯基、2,4-亚己二烯基、2,5-亚己二烯基、3,4-亚己二烯基、3,5-亚己二烯基、4,5-亚己二烯基、1,1-二甲基-4-亚己烯基、1-亚庚烯基、2-亚庚烯基、3-亚庚烯基、4-亚庚烯基、5-亚庚烯基、2,2-二甲基-5-亚庚烯基、6-亚庚烯基、1,2-亚庚二烯基、1,3-亚庚二烯基、1,4-亚庚二烯基、1,5-亚庚二烯基、1,6-亚庚二烯基、2,3-亚庚二烯基、2,4-亚庚二烯基、2,5-亚庚二烯基、2,6-亚庚二烯基、3,4-亚庚二烯基、3,5-亚庚二烯基、3,6-亚庚二烯基、4,5-亚庚二烯基、4,6-亚庚二烯基或5,6-亚庚二烯基、1-亚丙炔基、3-亚丁炔基、2-亚戊炔基、5-亚己炔基、6-亚庚炔基、-(CH2)-CH=CH-O-(CH2)2-,-CH2-S-(CH2)3-,-CH2-顺-CH=CH-1,2-亚苯基-CH2-, -CH=CH-1,4-亚苯基-(CH2)2-,-4-OXO-4,5-亚己烯基-,以及类似的基团。
术语“烷基”是指C1-C20直链或支链烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、新戊基、叔戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十九烷基、二十烷基等。
术语“芳基”是指C6-C14单环或稠环,例如苯基、萘基(如1-萘基、2-萘基)、蒽基(如1-蒽基、2-蒽基、9-蒽基)、菲基(如2-菲基、3-菲基、9-菲基)、芴基(如2-芴基)等。苯基是特别优选的。
术语“芳烷基”是指在上述烷基的任何可取代的位置上用上述芳基取代该烷基后所形成的基团。其例子包括苄基、苯乙基、苯丙基(如3-苯基丙基)、萘甲基(如α-萘基甲基)、蒽甲基(如9-蒽基甲基)、菲甲基(如3-菲基甲基)等。
术语“酰基”是指从脂族羧酸衍生来的C1-C9酰基,例如甲酰、乙酰、丙酰、丁酰、戊酰等。
术语“烷基磺酰基”是指用上述烷基取代磺酰基后所形成的基团,例如甲磺酰基、乙磺酰基、丙磺酰基等。
术语“链烯基”是指C2-C20直链或支链的烯,相当于含有1个或多个双键的上述烷基。其例子包括乙烯基、1-丙烯基、2-丙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1,2-丁二烯基、1-戊烯基、1,2-戊二烯基、2-己烯基、1,2-己二烯基、3-庚烯基、1,5-庚二烯基等。
术语“炔基”是指C2-C20直链或支链的炔基,相当于含有1个或多个三键的上述烷基。其例子包括乙炔基、1-丙炔基、2-丙炔基、1-丁炔基、2-丁炔基、3-丁炔基等。
术语“杂环基”是指环上含有1个或多个独立地选自氧、硫和/或氮原子的5-7元环状基团,在任何可取代的位置上可任选地与碳环或其它杂环基稠合。其例子包括吡咯基(如1-吡咯基、3-吡咯基)、吲哚基(如2-吲哚基、3-吲哚基、6-吲哚基)、咔唑基(如2咔唑基、3-咔唑基)、咪唑基(如1-咪唑基、4-咪唑基)、吡唑基(如1-吡唑基、3-吡唑基)、苯并咪唑基(如2-苯并咪唑基、5-苯并咪唑基)、吲唑基(如3-吲唑基)、中氮茚基(如6-中氮茚基)、吡啶基(如2-吡啶基、3-吡啶基、4-吡啶基)、喹啉基(如8-喹啉基)、异喹啉基(如3-异喹啉基)、吖啶基(如1-吖啶基)、菲啶基(如2-菲啶基、3-菲啶基)、哒嗪基(2-哒嗪基)、肉啉基(如3-肉啉基)、2,3-二氮杂萘基(phthaladinyl)(如5-2,3-二氮杂萘基)、喹唑啉基(如2-喹唑啉基)、异噁唑基(如3-异噁唑基、4-异噁唑基)、苯并异噁唑基(如1,2-苯并异噁唑-4-基、2,1-苯并异噁唑-3-基)、噁唑基(如2-噁唑基、4-噁唑基、5-噁唑基)、苯并噁唑基(如2-苯并噁唑基)、苯并噁二唑基(如4-苯并噁二唑基)、异噻唑基(如3-异噻唑基、4-异噻唑基)、苯并异噻唑基(如1,2-苯并异噻唑-3-基、2,1-苯并异噻唑-5-基)、噻唑基(如2-噻唑基)、苯并噻唑基(如2-苯并噻唑基)、噻二唑基(如1,2,3-噻二唑-4-基)、噁二唑基(如1,3,4-噁二唑-2-基)、二氢噁二唑基(如4,5-二氢-1,2,4-噁二唑-3-基)、呋喃基(如2-呋喃基、3-呋喃基)、苯并呋喃基(如3-苯并呋喃基)、异苯并呋喃基(如1-异苯并呋喃基)、噻吩基(如2-噻吩基、3-噻吩基)、苯并噻吩基(1-苯并噻吩-2-基、2-苯并噻吩-1-基)、四唑基(如5-四唑基)、苯并间二氧杂环戊烯基(如1,3-苯并间二氧杂环戊烯-5-基)、二苯并呋喃基(如2-二苯并呋喃基、3-二苯并呋喃基)、二苯并噁庚因基(如二苯并[b,f]噁庚因-2-基)、苯并吡喃基(如2H-苯并吡喃-3-基、4H-苯并吡喃-2-基)、二苯并硫杂七环基(thiepinyl)(如二苯并[b,f]硫杂七环-3-基、二氢二苯并[b,f]硫杂七环-3-基)、吗啉基(如1,4-吗啉-4-基)、吩噻嗪基(phenothiadinyl)(2-吩噻嗪基)、环戊二烯并噻吩基(如环戊二烯并[b]噻吩-3-基)、环己二烯并噻吩(cyclohexathienyl)(如环己二烯并[b]噻吩-3-基)等。
术语“环烷基”是指C3-C8环烷基,例如环丙基、环丁基、环戊基、环己基等。
术语“环烯基”是指C3-C8环烯基,例如环丙烯基(如1-环丙烯基)、环丁烯基(如2-环丁烯-1-基)、环戊烯基(1-环戊烯-1-基)、环己烯基(1-环己烯-1-基)等。
术语“烷氧基”是指C1-C6烷氧基,例如甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基等。
在“取代或未取代的氨基”的定义中,取代的氨基的例子包括一取代或二取代氨基,如甲基氨基、乙基氨基、二甲基氨基、环己基氨基、苯基氨基、二苯基氨基、或环状氨基,如哌啶子基、哌嗪子基(piperadino)或吗啉代基。
术语“酰氧基”是指从上述“酰基”衍生的酰氧基,例如乙酰氧基、丙酰氧基、丁酰氧基、戊酰氧基等。
术语“卤素”是指氟、氯、溴和碘。
术语“烷氧羰基”是指从上述“烷氧基”衍生的烷氧羰基基团,例如甲氧羰基、乙氧羰基、苯氧羰基等。
术语“芳烷氧羰基”是指从上述“芳烷基”衍生的芳烷氧羰基基团,例如苄氧羰基、苯乙氧羰基等。
术语“芳氧羰基”是指从上述“芳基”衍生的芳氧羰基基团,例如苯氧羰基、萘氧羰基等。
术语“链烯氧基”是指从上述“链烯基”衍生的链烯氧基基团,例如乙烯氧基、1-丙烯氧基、2-丁烯氧基等。
术语“羟烷基”是指从上述“烷基”衍生的羟烷基基团,例如羟甲基、羟乙基、羟丙基等。
术语“烷硫基”是指从上述“烷基”衍生的烷硫基基团,例如甲硫基、乙硫基、丙硫基等。
术语“亚烷二氧基”是指从C1-C3亚烷二氧基,例如亚甲二氧基、亚乙二氧基、亚丙二氧基等。
在“亚苯基”、“亚萘基”、“噻吩二基”、“吲哚二基”、“噁唑二基”、“噁二唑二基”和“四唑二基”的情况下,所述基团可以结合到任何两个可取代部位上的相邻基团上。
在上述定义中,当取代基为环状基团时,该取代基可被1-3个选自下述的取代基取代硝基、烷氧基、氨磺酰、取代或未取代的氨基、酰基、酰氧基、羟基、卤素、烷基、炔基、羧基、烷氧羰基、芳烷氧羰基、芳氧羰基、甲磺酰氧基、氰基、链烯氧基、羟烷基、三氟甲基、烷硫基、-N=PPh3、氧代、硫代、肟基、烷氧亚氨基、苯基和亚烷二氧基。这些取代基可以结合到环上任何可取代的位置上。
化合物(I)的盐的例子包括与碱金属(如锂、钠或钾)、碱土金属(如钙)、有机碱(如tromethamine、三甲胺、三乙胺、2-氨基丁烷、叔丁胺、二异丙基乙胺、正丁基甲胺、环己胺、二环己胺、N-异丙基环己胺、糠胺、苄胺、甲苄胺、二苄胺、N,N-二甲基苄胺、2-氯苄胺、4-甲氧基苄胺、1-亚萘基甲胺、二苯基苄胺、三苯胺、1-萘胺、1-氨基蒽(anthoracene)、2-氨基蒽、脱氨枞胺、N-甲基吗啉或吡啶)、氨基酸(如赖氨酸、或精氨酸)等形成的盐。
术语“水合物”是指式(I)化合物或其盐的水合物。其例子包括一水合物和二水合物。
本发明化合物由通式(I)表示,并包括任何类型的立体异构体(如非对映体、差向异构体、对映体)的外消旋化合物形式。
在通式(I)化合物中,其中m=1的那些化合物,尤其下面表3b和3c所列的那些化合物是日本专利公开No 180862/1990中所述的已知化合物。
在通式(I)化合物中,其中m=0的那些化合物〔即通式(I′)所示的那些化合物〕可通过使通式(II)的氨基化合物与相当于部分结构Z-X1-X2-X3的磺酸或羧酸的活性衍生物反应来制备,如下所示
其中A、B、R、X1、X2、X3、Y和Z的定义同上。
相当于部分结构Z-X1-X2-X3的磺酸是通式X3-X2-X1-SO2H所示的化合物,而相当于所述部分结构的羧酸是通式X3-X2-X1-COOH所示的化合物。这类磺酸或羧酸的活性衍生物是指相应的卤化物(如氯化物、溴化物、碘化物)、酸酐(如与甲酸或乙酸形成的混合酸酐)、活性酯(如琥珀酰亚胺酯),其例子通常包括用于氨基基团酰化的酰化剂。在用于胺和羧酸之间的缩合反应的缩合剂(如二环己基碳化二亚胺(DCC)、1-乙基-3-(3-二甲基氨基丙基)碳化二亚胺、N,N′-碳酰二咪唑)的存在下,羧酸X3-X2-X1-COOH不转化成活性衍生物就可用在该反应中。
该反应可在通常用于氨基基团酰化的条件下进行。例如,在使用酰卤进行缩合的情况下,该反应要在溶剂,例如醚类溶剂(如二乙醚、四氢呋喃、二噁烷)、苯类溶剂(如苯、甲苯、二甲苯)、卤代烃类溶剂(如二氯甲烷、二氯乙烷、氯仿)、乙酸乙酯、二甲基甲酰胺、二甲基亚砜、乙腈或类似的溶剂存在下进行,如有必要,可在碱(例如,有机碱如三乙胺、吡啶、N,N-二甲基氨基吡啶、N-甲基吗啉;无机碱如氢氧化钠、氢氧化钾、碳酸钾,或类似的碱)存在下进行,反应可在冷却下、在室温或加热的条件下进行,优选在-20℃至冷却的温度下,或从室温至反应体系的回流温度下进行,反应时间为几分钟至若干小时,优选0.5-24小时,更优选为1-12小时。
其它活性衍生物或游离酸和胺(II)之间的反应的反应条件可按一般方法根据各个活性衍生物或游离酸的特性来决定。
反应产物可用传统的纯化方法,例如溶剂萃取、色谱、重结晶,或类似的方法进行提纯。
作为本发明方法的原料化合物(II)的具体例子列举如下。3-氨基[2.2.1]二环化合物的例子包括7-(3-氨基二环[2.2.1]庚-2-基)-5-庚烯酸、7-(3-氨基二环[2.2.1]庚-2-基)-2,2-二甲基-5-庚烯酸、7-(N-甲基-3-氨基二环[2.2.1]庚-2-基)-5-庚烯酸、6-(3-氨基二环[2.2.1]庚-2-基)-5-己烯酸。2-氨基-6,6-二甲基[3.1.1]二环化合物的具体例子包括7-(2-氨基-6,6-二甲基二环[3.1.1]庚-3-基)-5-庚烯酸。在这些起始化合物中,庚烯酸链可以是饱和的,形成庚酸链,可以插入杂原子或杂基团如-O-、-S-、-NH-,或亚苯基,或被氧代基取代。这类化合物的例子包括7-(3-氨基二环[2.2.1]庚-2-基)庚酸、4-〔2-(2-氨基二环[3.1.1]庚-3-基)乙氧基苯基乙酸、7-(3-氨基二环[2.2.1]庚-2-基)-6-氧代-庚酸。这些起始化合物或者在日本专利公告No.79060/1993或23170/1991中有记载,或者可按其中所述方法制备。
相当于部分结构Z-X1-X2-X3的磺酸X3-X2-X1-SO2H和羧酸X3-X2-X1-COOH是指带有对应于上述Xs的取代基的磺酸或羧酸。就是说,其例子包括链烷-磺酸或链烷-羧酸,链烯-磺酸或-羧酸,链炔-磺酸或-羧酸,环烷-磺酸或-羧酸,芳基-磺酸或-羧酸,芳烷基-磺酸或-羧酸,杂环取代-磺酸或-羧酸,杂芳基烷基-磺酸或-羧酸,以及取代的氨基-磺酸或-羧酸。磺酸和羧酸各自都可以有上述取代基。这些磺酸和羧酸可从市场上购得,或可容易地从已知化合物按已知方法合成。如有必要,反应后可将磺酸和羧酸转化成相应的上述活性衍生物。例如,当需要酰卤时,可按已知方法,例如文献(如Shin-Jikken-Kagaku-Koza,第14卷,1787页(1978);Synthesis(合成),852-854页(1986);Shin-Jikken-Kagaku-Koza,第22卷,115页(1992))中所述的方法让该化合物与亚硫酰卤(如亚硫酰氯)、卤化磷(如三氯化磷、五氯化磷)或草酰卤(如草酰氯)反应。其它活性衍生物也可按已知方法制备。
在目的化合物(I)中,其中侧链A含有不饱和键,尤其双键的那些化合物也可通过使下面通式(III)的醛衍生物与相当于该侧链A-R的其余部分的内鎓盐化合物在用于Wittig反应的条件下进行反应来制备。
其中A、B、R、X1、X2、X3、Y和Z的定义同上。
起始化合物(III)可按照例如日本专利公开No.256650/1990中所述方法制备。此外,相当于侧链A-R的其余部分的内鎓盐化合物可按已知方法让三苯膦与相应的卤代链烷酸或其酯衍生物、醚衍生物或酰胺衍生物在碱存在下进行反应来合成。
在目的化合物(I)中,其中R为COOH的那些化合物,如果希望的话,可转化成相应的酯衍生物、醇衍生物、醚衍生物、酰胺衍生物。例如,酯衍生物可按传统方法通过使羧酸酯化来制备。酯衍生物还原时就得到醇衍生物,而当进行酰胺化时就得到酰胺衍生物。醚衍生物可通过醇衍生物的O-烷基化制得。
本发明的化合物(I)显示通过与PGD2受体结合产生的离体抗PGD2的拮抗效果,而且可作为一种药物用于治疗那些涉及因PGD2过量产生而引起的肥大细胞机能障碍的疾病。例如,化合物(I)可作为一种药物用于治疗多种疾病,例如全身性肥大细胞沉积病和全身性肥大细胞活化失调,也可用于治疗气管挛缩、哮喘、变应性鼻炎、变应性结膜炎、荨麻疹、因局部缺血性重复输注而引起的损伤和发炎。化合物(I)显示出对活体鼻塞的预防效果,因此,尤其可作为一种药物用于治疗它们。
当使用本发明的化合物(I)进行治疗时,可以把它配制成经口给药和非经肠给药用的常用配方。含有本发明化合物(I)的医药组合物可以呈经口和非经肠给药用剂型。具体地说,可以把它配制成经口给药用配方,例如片剂、胶囊剂、颗粒剂、散剂、糖浆剂等;非经肠给药用配方,例如经静脉内、经肌内或经皮下注射用的可注射溶液或悬浮液,吸入剂,眼滴剂,鼻滴剂,栓剂,或经皮配方如软膏剂。
在制备这些配方时,可以使用本门技术上一般熟练人员已知的载体、赋形剂、溶剂和基剂。在片剂的情况下,它们是通过使有效成分(活性组分)连同辅助成分一起压缩或配制来制备的。可用辅助成分的实例包括药物上可接受的赋形剂,例如粘结剂(如玉米淀粉)、填料(如乳糖、微晶纤维素)、崩解剂(如淀粉甘醇酸钠)或润滑剂(如硬脂酸镁)。片剂可以进行适当包衣。在液体配方如糖浆剂、溶液剂或悬浮剂的情况下,它们可以含有悬浮剂(如甲基纤维素),乳化剂(如卵磷脂)、防腐剂等。在可注射配方的情况下,它可以呈溶液或悬浮液或者油基或水基乳液的形式,这些剂型可以含有悬浮稳定剂或分散剂等。在吸入剂的情况下,把它配制成一种适用于吸入器的液体配方。在眼滴剂的情况下,把它配制成一种溶液剂或一种悬浮液剂。特别是,在用于治疗鼻塞的鼻药的情况下,可以把它作为一种用常规配制方法制备的溶液或悬浮液或作为一种用粉末化剂(如羟丙基纤维素、carbopole)配制的粉末剂使用,对鼻腔给药。此外,它也可以在与一种低沸点溶剂一起灌装到一种专用容器中之后作为一种气雾剂使用。
尽管化合物(I)的适用剂量因给药途径、患者的年龄、体重、性别或病情以及一起使用的药物种类(如果有的话)而异,而且最终应当由医生确定,但在经口给药的情况下,日剂量一般可以是每kg体重约0.01~100mg、较好约0.01~10mg、更好的是约0.1~10mg。在非经肠给药的情况下,日剂量一般可以是每kg体重约0.001~100mg、较好约0.001~1mg、更好的是约0.01~1mg。这种日剂量可以分成1~4次给药。
以下实例是为了进一步说明本发明而提供的,不要理解为对其范围的限定。实例1
(Z)-7-〔(1S,2R,3R,4R)-3-氨基二环[2.2.1]庚-2-基〕-5-庚烯酸甲酯(II-1)(251mg,1.0mmol)溶于二氯甲烷(8ml)中,然后在氮气氛围下向其中加入三乙胺(0.238ml,2.00mmol)。在冰冷却下往该混合物中加入2-氯磺酰基二苯并呋喃(350mg,1.31mmol),然后将该混合物搅拌30分钟,并让其温热至室温。反应混合物经硅胶柱色谱提纯(正己烷/乙酸乙酯(1∶4))及正己烷(10ml)重结晶后得到(Z)-7-〔(1S,2R,3R,4R)-3-(2-二苯并呋喃基)磺酰氨基二环[2.2.1]庚-2-基〕-5-庚烯酸甲酯(1a-1)(342mg,0.710mmol)。产率71%,熔点115-116℃。元素分析(C27H31NO5S)
计算值(%)C,67.34;H,6.49;N,2.91;S,6.66
实测值(%)C,67.16;H,6.47;N,2.99;S,6.66 IR(CHCl3)3382,3024,2952,2874,1726,1583,1465,1442,1319,1245,1154,1121,1104,1071,1019,890,840,817/cm.1H NMR(CDCl3)δ0.94-1.92(14H,m),2.15-2.24(3H,m),2.99-3.07(1H,m),3.66(3H,s),4.98(1H,d,J=6.6Hz),5.10-5.22(2H,m),7.39-7.46(1H,m),7.51-7.70(3H,m),7.87-8.13(2H,m),8.5 3(1H,d,J=2.1Hz)[α]D=-0.6°(CHCl3,c=1.01%,23℃).([α]365=+37.0°(CHCl3,c=1.01%,23℃).
(Z)-7-〔(1S,2R,3R,4R)-3-(2-二苯并呋喃基)磺酰氨基二环[2.2.1]庚-2-基〕-5-庚烯酸甲酯(1a-1)(234mg,0.50mmol)溶解在甲醇(6ml)/四氢呋喃(4ml)中。在冰冷却下往该溶液中加入1N氢氧化钾(1.50ml,1.50mmol)。待反应混合物温热至室温后,让其反应16小时,然后浓缩脱除溶剂。往残留物中加入乙酸乙酯(50ml)和水(10ml),然后再加入1NHCl(2.00ml,2.00mmol),并分离出有机层。该有机层用饱和盐水洗涤,用无水硫酸钠干燥,然后浓缩。残留物经硅胶柱色谱提纯(含0.2%乙酸的正己烷/乙酸乙酯(1∶1))后得到(Z)-7-〔(1S,2R,3R,4R)-3-(2-二苯并呋喃基)磺酰氨基二环[2.2.1]庚-2-基〕-5-庚烯酸(1a-2)(203mg,0.434mmo1)。产率87%,油状物。IR(CHCl3)3266,3026,2952,2874,1708,1465,1443,1423,1319,1267,1245,1153,1121,1104,1072,906/cm.1H NMR(CDCl3)δ0.93-1.94(14H,m),2.12-2.19(1H,m),2.26(2H,t,J=7.2Hz),3.00-3.08(1H,m),5.12-5.25(2H,m),5.26(1H,d,J=6.6Hz),7.3 8-7.45(1H,m),7.51-7.70(3H,m),7.87-8.13(2H,m),8.54(1H,d,J=2.1Hz).[α]D=+6.8°(CHCl3,c=1.08%,23℃).
(Z)-7-〔(1S,2R,3R,4R)-3-(2-二苯并呋喃基)磺酰氨基二环[2.2.1]庚-2-基〕-5-庚烯酸(1 a-2)(453mg,0.97mmol)溶解在甲醇(5ml)中。加入1N甲醇钠/甲醇(1.034N,0.937ml,0.97mmol)后让混合物温热至室温,进行反应1小时。用蒸馏法脱除溶剂后得到该酸的钠盐(1a-3)(457mg,0.933mmol)。产率96%。无定形粉末。元素分析(C26H28NO5SNa 0.6H20)
计算值C,62.41;H,5.88;N,2.80;S,6.41;Na,4.59
实测值C,62.45;H,5.92;N,2.99;S,6.49;Na,4.46IR(KBr)434,3280,3074,3007,2952,2873,1566,1467,1444,1417,1344,1315,1270,1248,1200,1189,1154,1124,1107,1075,1058,895,842,818/cm.1H NMR(CD3OD)δ1.02-2.05(16H,m),2.1 6-2.23(1H,m),2.94-3.00(1H,m),4.98-5.05(2H,m),7.41-7.48(1H,m),7.53-7.62(1H,m),7.66(1H,d,J=8.4Hz),7.77(1H,d,J=8.4Hz),8.57(1H,d,J=2.1Hz).[α]D=-15.2°(CH3OH,c=1.07%,22℃).
实例2
将按照日本专利公告No.79060/1993参考例4所述方法制得的(Z)-7-〔(1S,2R,3R,4R)-3-氨基二环[2.2.1]庚-2-基〕-5-庚烯酸甲酯三氟乙酸盐(II-2)(232mg,0.636mmol)溶解在二氯甲烷(5ml)中。在冰冷却下往该溶液中加入三乙胺(0.279ml,2.00mmol)和4-联苯基碳酰氯,然后在同一温度下搅拌7小时。反应混合物经硅胶柱色谱提纯(乙酸乙酯/正己烷(1∶4))后得到(Z)-7-〔(1S,2R,3R,4R)-3-(4-联苯基)碳酰氨基二环[2.2.1]庚-2-基〕-5-庚烯酸甲酯(1K-11)(221mg,0.512mmol)。将该化合物(1K-11)(190mg,0.440mmol)溶解在甲醇(6ml)中。在冰冷却下往该溶液中加入1N KOH(1.10ml,1.10mmol),然后在室温下搅拌15小时。将反应混合物真空浓缩。往残留物中加入水(20ml)和1N HCl(2ml),然后用乙酸乙酯萃取。有机层用饱和盐水洗涤,用无水硫酸钠干燥,然后浓缩。残留物经硅胶柱色谱提纯(含0.3%乙酸的乙酸乙酯/己烷(1∶1))后得到(Z)-7-〔(1S,2R,3R,4R)-3-(4-联苯基)碳酰氨基二环[2.2.1]庚-2-基〕-5-庚烯酸(1K-12)(172mg,0.412mmol)。产率94%。
按照下面的方式也可制备如下化合物。实例3
在室温下在氮气氛围下往由溴化4-羧基丁基三苯基磷鎓(14.8g,33.3mmol)和四氢呋喃(80ml)组成的悬浮液中加入叔丁酸钾(7.55g,67.3mmol)。在室温下搅拌1小时后混合物冷却到-20℃,慢慢加入N-〔(1S,2S,3S,4R)-3-甲酰甲基二环[2.2.1]庚-2-基〕苯磺酰胺(III-1)(日本专利公开No.256650/1990,参考例2)(3.25g,11.1mmol)的四氢呋喃(20ml)溶液。在-20℃搅拌约1小时后,撤除冰浴,混合物再搅拌1小时。往该反应溶液中加入2N HCl,混合物用乙酸乙酯萃取,用水和盐水洗涤,浓缩。往所得粗产物中添加甲苯和1N氢氧化钠,然后分离出水层。有机层用水洗涤,洗涤液与前面得到的水层合并。加入2N HCl后,该水溶液用乙酸乙酯萃取。萃取物用水和盐水洗涤,用硫酸钠干燥,浓缩。残留物用硅胶柱色谱提纯,得到(Z)-7-〔(1R,2S,3S,4S)-3-苯磺酰氨基二环[2.2.1]庚-2-基〕-5-庚烯酸钙(1d-1)(3.29g,产率79%,熔点62℃)。元素分析(C20H27N04S)
计算值C,63.63;H,7.21;N,3.71;S,8.49
实测值C,63.56;H,7.21;N,3.83;S,8.43[α]D=+5.3±0.5°(CHCl3,C=1.003%,22℃)[α]D=+27.1±0.7°(MeOH,c=1.015%,24℃)IR(液体石蜡)3282,3260,3300,2400,1708,1268,1248,1202,1162,1153,1095,1076/cm.1H NMRδ0.88-2.10(m,14H),2.14(brS,1H),2.34(t,J=7.2Hz,2H),2.95-3.07(m,1H),5.13-5.35(m,3H),7.45-7.64(m,3H),7.85-7.94(m,2H),9.52(brS,1H)。
按照上述实例所述方法制备的化合物列于下面各表中。表1a
No.R1 X1-X2-X3
1a-22 H
1a-23 H
No. R1 X1-X2-X3
1a-34 CH3
1a-41 H
No.R1X1-X2-X3
No. R1 X1-X2-X3
1a-84 H
1a-85 H
1a-86 H
1a-87 H
No.R1 X1-X2-X3
1a-94 H
1a-95 H
1a-96 H
1a-97 H
No R1 X1-X2-X3
1a-102 CH3
No. R1 X1-X2-X3
1a-124 CH3
1a-129 CH3
1a-134 H
No. R1X1-X2-X3
No. R1X1-X2-X31a-152 H
1a-155 H
1a-156 H
1a-157 H
1a-158 H
1a-159 H
1a-160 H
No. R1 X1-X2-X31a-161 H
1a-162 H
1a-163 H
1a-164 H
1a-165 H
1a-166 H
1a-167 H
1a-168 H
1a-169 H
1a-170 H
No. R1 X1-X2-X31a-173 H
1a-174 H
1a-181 H
No. R1X1-X2-X31a-184 H
1a-185 H
No.X1-X2-X31a-194
1a-195
1a-198
1a-199
1a-200
1a-0201
1a-202
1a-203
No.X1-X2-X31a-204
1a-205
1a-206
1a-207
1a-208
1a-209
1a-210
1a-211
1a-212
1a-213
No. X1-X2-X31a-214
1a-215
1a-216
1a-217
1a-218
1a-219
1a-220
1a-221
1a-222
1a-223
No. X1-X2-X31a-224
1a-225
1a-226
1a-227
1a-228
1a-229
1a-230
1a-231
1a-232
1a-233
1a-234
1a-235
No. X1-X2-X31a-236
1a-237
1a-238
1a-239
1a-240
1a-241
1a-242
1a-243
1a-244
1a-245
1a-246
No. X1-X2-X31a-247
1a-248
1a-249
1a-250
1a-251
1a-252
1a-253
1a-254
1a-255
1a-256
1a-257
No. X1-X2-X31a-258
1a-259
1a-260
1a-261
1a-262
1a-263
1a-264
1a-265
1a-266
1a-267
1a-268
1a-269
1a-270
1a-271
No. X1-X2-X31a-272
1a-273
1a-274
1a-277
1a-280
1a-281
1a-282
1a-283
No. X1-X2-X3
1a-293
1a-294
No. X1-X2-X3
表1b
No. R1 X1-X2-X31b-1 CH3
1b-2 CH3
1b-3 H
1b-6 H
1b-7 H
1b-8 H
1b-9 H
1b-10H
No. R1 X1-X2-X31b-11H
1b-12H N
1b-13H
1b-14H
1b-15H
表1c
No. R1 X1-X2-X31c-1 CH3
1c-2 CH3
1c-3 K
1c-4 H
1c-5 H
1c-6 H
1c-7 H
1c-8 H
1c-9 H
1c-10 H
表1d
No. R3 R4 X1-X2-X31d-1 H SO2CH3
1d-5 H SO2CH3
1d-6 H SO2CH3
1d-7 H SO2CH3
1d-8 H SO2CH3
1d-9 H SO2CH3
1d-10 H SO2CH3
No. R3 R4 X1-X2-X31d-11HSO2CH3
1d-12HSO2CH3
1d-13HSO2CH3
1d-14HSO2CH3
1d-15HSO2CH3
表1e
No.R1X1-X2-X3
1e-3 H
1e-4 H
1e-5 H
1e-6 H
1e-7 H
1e-8 H
1e-9 H
1e-10 H
表1f
No.R2 X1-X2-X31f-1 H
1f-2 H
1f-3 H
1f-4 H
1f-5 H
1f-6 H
1f-7 H
1f-8 H
1f-9 H
1f-10 H
表1g
No. R1 X1-X2-X31g-1H
1g-2H
1g-3H
1g-4H
1g-5H
1g-6H
1g-7H
1g-8H
1g-9H
1g-10 H
1g-11 H
表1h
No. R1 X1-X2-X31h-1H
1h-2H
1h-3H
1b-4H
1h-5H
1h-6H
1h-7H
1h-8H
1h-9H
1h-10 H
表Ii
No. R2X1-X2-X31i-1H
1i-2H
1i-3H
1i-6H
1i-7H
1i-12 H
表1j
No. R1 X1-X2-X3
1j-8CH3
No. R1 X1-X2-X31j-17H
1j-22H
1j-27H
No R1X1-X2-X31j-30H
1j-31H
1j-32H
1j-33H
1j-34H
1j-35H
1j-36H
1j-37H
1j-38H
表1k
No.R1 X1-X2-X31k-1 H
1k-4 H
1k-5 H
1k-6 H
1k-7 H
1k-8 H
1k-9 H
1k-10 H
1k-11 CH3
1k-12 H
No. R1 X1-X2-X31k-13H
11-14H
1k-15H
1k-16H
1k-17H
1k-18H
11-19H
1k-20H
表1m
No. R1X1-X2-X3
No. R1X1-X2-X3
1m-21H
1m-22H
1m-31H
1m-32H
1m-33H
No. R1 X1-X2-X31m-34H
1m-35H
1m-36H
1m-37H
1m-38H
1m-39H
1m-40H
表2a
No. R1 X1-X2-X3
No. R1 X1-X2-X3
2a-31CH3
No. R1 X1-X2-X3
No. R1 X1-X2-X3
No.R1 X1-X2-X3
No.R1X1-X2-X3
2a-119 H
2a-120 H
2a-121 H
2a-122 H
2a-123 H
2a-124 H
2a-125 H
No. R1 X1-X2-X32a-126H
2a-127H
2a-128H
2a-129H
2a-130H
2a-131H
2a-132H
2a-133H
2a-134H
2a-135H
2a-136H
No. R1 X1-X2-X32a-137H
2a-138H
2a-139H
2a-140H
2a-141H
2a-142H
2a-143H
2a-144H
2a-145H
2a-146H
2a-147H
No. R1 X1-X2-X32a-148H
2a-149H
2a-150H
2a-151H
2a-152H
2a-153H
2a-154H
2a-155H
2a-156H
2a-157H
2a-158H
2a-159H
No. R1 X1-X2-X32a-160H
2a-161H
2a-162H
2a-163H
2a-164H
2a-165H
2a-166H
2a-167H
2a-168H
2a-169H
2a-170H
No. R1X1-X2-X32a-171H
2a-172H
2a-173H
2a-174H
2a-175H
2a-176H
2a-177H
2a-178H
2a-179H
2a-180H
2a-181H
2a-182H
No. R1 X1-X2-X32a-183H
2a-184H
2a-185H
2a-186H
2a-187H
2a-188H
2a-189H
2a-190H
2a-191H
2a-192H
2a-193H
No. R1 X1-X2-X32a-194H
2a-195H
2a-196H
2a-197H
2a-200H
2a-201H
2a-202H
2a-203H
No. X1-X2-X32a-204
2a-205
2a-206
2a-207
2a-208
2a-209
2a-210
2a-211
2a-212
2a-213
No. X1-X2-X32a-214
2a-215
2a-216
2a-217
2a-218
2a-219
2a-220
2a-221
2a-222
2a-223
No. X1-X2-X32a-224
2a-225
2a-226
2a-227
2a-228
2a-229
2a-230
2a-231
2a-232
2a-233
No.X1-X2-X32a-234
2a-235
2a-236
2a-237
2a-238
2a-239
2a-240
2a-241
2a-242
2a-243
No. X1-X2-X32a-244
2a-245
2a-246
2a-247
2a-248
2a-249
2a-250
2a-251
No. X1-X2-X32a-252
2a-253
2a-254
2a-255
2a-256
2a-257
No. X1-X2-X32a-258
2a-259
2a-260
2a-261
2a-262
2a-263
2a-264
2a-265
2a-266
2a-267
No. X1-X2-X32a-268
2a-269
2a-270
2a-271
2a-272
2a-273
2a-274
2a-275
2a-276
2a-277
No. X1-X2-X32a-278
2a-279
2a-280
2a-281
2a-282
2a-283
2a-284
2a-285
2a-286
2a-287
No. X1-X2-X32a-288
2a-289
2a-290
2a-291
2a-292
2a-293
2a-294
2a-295
2a-296
No. X1-X2-X32a-297
2a-298
2a-299
2a-300
2a-301
2a-302
2a-303
2a-304
2a-305
2a-306
No. X1-X2-X32a-307
2a-308
2a-309
2a-310
2a-311
2a-312
2a-313
2a-314
2a-315
表2b
No. R1X1-X2-X32b-1H
2b-2H
表2C
No. R1X1-X2-X32c-1H
2c-2H
2c-3H
表2d
No. R1X1-X2-X32d-1H
2d-2H
2d-3H
表2e
No. R1 X1-X2-X32e-1H
2e-2H
2e-3H
表2f
No. R1 X1-X2-X32f.1H
2f-2H
2f-3H
表2g
No. R3 R4 X1-X2-X32g-1H SO2CH3
表2h
No. X1-X2-X32h-1
2b-2
2h-3
2h-4
2h-5
2b-6
表2i
No. X1-X2-X3
2i-3
2i-4
2i-5
2i-6
表2j
No. X1-X2-X3
2j-4
2j-5
2j-6
表2k
No. X1-X2-X3
2k-3
2k-4
2k-5
2k-6
表3a
No.R1 X1-X2-X3
3a-8 H
3a-9 H
3a-14 CH3
No. R1 X1-X2-X3
3a-25 H-(CH2)3CH33a-26CH33a-27 H-(CH2)7CH33a-28CH3
3a-29H
3a-30CH3
表3b
No.R1 X1-X2-X3
3b-3 H
3b-4 H
表3c
No.R1X 1-X2-X33c-1 H
表3d
No. R1 X1-X2-X3
3d-3 Na
3d-4 Na
No. R1X1-X2-X33d-16 H
3d-17 H
3d-18 H-(CH3)3CH33d-19 CH33d-20 H-NHCH6
3d-23 H
3d-24 H
外消旋化合物
外消旋化合物
外消旋化合物表3e
No. R1 X1-X2-X33e-11/2Ca
下面列出上述化合物的物理化学性质。下面的化合物编号对应于上面表中所列的化合物编号。No.1a-4[α]D=-11.5°(CHCl3,C=1.01,23.5℃)。No.1a-5[α]D=-10.0°(CHCl3,C=1.01,25.0℃)。No.1a-6 CDCl3300MHz 0.93-1.96(14H,m),2.20-2.26(3H,m),3.03(1H,m),3.67(3H,s),4.99(1H,d,J=6.6H z),5.10-5.24(2H,m),7.37-7.51(3H,m),7.54-7.64(3H,m),7.76-7.88(2H,m),8.11(1 H,m).IR(CHCl3)3384,3278,3026,2952,2874,1727,1436,1411,1324,1155,1097/cm.[α]D=-9.0°(CHCl3,C=1.04,22.0℃).No.1a-7 CDCl3300MHz 0.93-2.00(14H,m),2.18(1H,m),2.28(2H,t,J=7.2Hz),3.04(1H,m),5.15-5.25(2H,m),5.28(1H,d,J=6.9Hz),7.36-7.50(3H,m),7.54-7.63(3H,m),7.76-7.89(2H,m),8.12(1H,m).IR(CHCl3)3268,3028,2952,2872,1708,1452,1410,1324,1155,1097/cm.[α]D=-9.1°(CHCl3,C=1.01,24.0℃).No.1a-8CDCl3300MHz 0.94-1.99(14H,m),2.21-2.29(3H,m),3.05(1H,m),3.67(3H,s),4.92(1H,d,J=6.3Hz),5.14-5.30(2H,m),7.70-7.78(6H,m),7.96-8.01(2H,m).IR(CHCl3)3376,3272,3018,2946,2868,1727,1616,1435,1388,1324,1162,1130,1069/cm.[α]D=+1.6°(CHCl3,C=l.01,24.0℃)、mp.117-119℃.No.1a-9CDCl3 300MHz0.95-2.08(14H,m),2.19(1H,m),2.32(2H,t,J=7.2Hz),3.06(1H,m),5.20-5.30(2H,m),5.34(1H,d,J=6.6Hz),7.69-7.78(6H,m),7.96-8.03(2H,m).IR(CHCl3)3260,3020,2950,2868,1708,1389,1324,1162,1130,1069/cm.[α]D=+13.3°(CHCl3,C=1.05,24.0℃).mp. 118-120℃No.1a-10CDCl3 300MHz0.96-1.98(14H,m),2.15-2.32(3H,m),3.04(1H,m),3.66(3H,s),5.12-5.26(5H,m), 7.67-7.78(4H,m),7.93-8.07(4H,m).IR(CHCl3)3276,3018,2946,2868,1726,1595,1435,1341,1162,1095/cm.[α]D=-1.5 °(CHCl3,C=1.01,25.0℃).mp.133-139℃.No.1a-11CD3OD 300MHz1.05-1.98(14H,m),2.13-2.22(3H,m),2.97(1H,m),5.09-5.22(2H,m),7.85-7.92(4H,m),7.95-8.05(4H,m).IR(KBr)3385,3261,3069,3003,2954,2872,1708,1596,1428,1413,1378,1343,1326,1236,1186,1160,1096/cm.mp.144-146℃.No.1a-12CDCl3 300MHz0.96-1.96(14H,m),2.22-2.27(3H,m),3.03(1H,m),3.66(3H,s),3.87(3H,s),4.86(1H,d,J=6.9Hz),5.18-5.24(2H,m),6.99-7.02(2H,m),7.55-7.66(2H,m),7.66-7.69(2H,m),7.89-7.92(2H,m).IR(CHCl3)3374,3270,3016,2948,2870,1726,1608,1518,1487,1458,1437,1248,1157,1037.[α]D=+4.2°(CHCl3,C=1.01,24℃).mp.85-87℃.No.1a-13CDCl3 300MHz0.97-1.99(14H,m),2.18(1H,m),2.30(2H,t,J=7.2Hz), 3.04(1 H,m),3.86(3H,s),5.18(1H,d,J=5.7Hz),5.23-5.26(2H,m),6.99-7.02(2H,m),7.55-7.58(2H,m),7.66-7.68(2H,m),7.89-7.92(2H,m).IR(CHCl3)3380,3260,3020,2948,2868,1708,1608,1519,1487,1458,1306,1293,1248,1156/cm.[α]D=+18.3°(CHCl3,C=1.00,25.5℃).No.1a-14CDCl3 300MHz0.98-2.00(14H,m),2.20(1H,m),2.25(2H,t,J=7.2Hz),3.02(1H,m),3.67(3H,s),4.85(1H,d,J=6.3Hz),5.19-5.25(2H,m),7.13(1H,dd,J=4.8,3.6Hz),7.39(1H,d,J=4.8Hz),7.40(1H,d,J=3.6Hz),7.71-7.74(2H,m),7.86-7.89(2H,m).IR(CHCl3)3374,3270,3018,2946,2868,1727,1593,1434,1322/cm.[α]D= +5.6°(CHCl3,C=1.01,24℃).mp.69-71℃.No.1a-15CDCl3 300MHz0.95-2.00(14H,m),2.17(1H,m),2.32(2H,t,J=7.2Hz),3.03(1H,m),5.20(1H,d,J=6.9Hz),5.24 -5.28(2H,m),7.13(1H,dd,J=4.8,3.3Hz),7.38(1H,d,J=4.8Hz),7.43(1H,d,J=3.3Hz),7.73(2H,d,J=8.4Hz),7.87(2H,d,J=8.4Hz).IR(CHCl3)3260,3022,2948,2868,1709,1593,1404,1321,1154/cm.[α]D=+20.8°(CHCl3,C=1.07,23℃).mp.71-73℃.No.1a-16CDCl3 300MHz0.98-2.00(14H,m),2.27(2H,t,J=7.5Hz),2.28(1H,m),3.13(1H,m),3.66(3H,s),4.90(1H,d,J=6.9Hz),5.25-5.29(2H,m),7.40-7.65(6H,m),7.76(1H,d,J=8.4Hz),7.90-8.02(4H,m).IR(CHCl3)3376,3276,3018,2946,2868,1726,1593,1435,1394,1322,1159/cm.[α]D= +7.0°(CHCl3,C=1.07,24℃).No.1a-17CDCl3 300MHz1.02-2.07(14H,m),2.25(1H,m),2.34(2H,t,J=6.6Hz),3.14(1H,m),5.28-5.33(3H,m),7.39-7.57(4H,m),7.62-7.65(2H,m),7.76(1H,d,J=8.1Hz),7.89-8.02(4H,m).IR(CHCl3)3260,2948,2868,1709,1593,1394,1324,1157/cm.[α]D=+20.2 °(CHCl3,C=1.02,24℃).No.1a-18CDCl3 300MHz1.05-1.97(14H,m),2.25(2H,t,J=7.2Hz),2.33(1H,m),3.12(1H,m),3.67(3H,s),4.91(1H,d,J=6.6Hz),5.24-5.29(2H,m),7.24(1H,d,J=3.9Hz),7.39-7.45(3H,m),7.56(1H,d,J=3.9Hz),7.59-7.62(2H,m).IR(CHCl3)3372,3272,3018,2946,2868,1727,1433,1331,1152/cm.[α]D=-5.7°(CHCl3,C=1.01,23℃).No.1a-19CDCl3 300MHz1.05-2.05(14H,m),2.28-2.33(3H,m),3.13(1H,m),5.18(1H,d,J=6.3Hz),5.27-5.31(2H,m),7.24(1H,d,J=4.2Hz),7.39-7.42(3H,m),7.56(1H,d,J=4.2Hz),7.58- 7.62(2H,m).IR(CHCl3)3372,3254,3018,2948,2868,1707,1431,1328,1151/cm.[α]D=+4.5°(CHCl3,C=1.01,21.5℃).No.1a-20CDCl3 300MHz1.05-2.00(14H,m),2.26(2H,t,J=7.5Hz),2.33(1H,m),3.11(1H,m),3.68(3H,s),4.92(1H,d,J=6.0Hz),5.27(2H,m),7.05(1H,m),7.10(1H,d,J=3.6Hz),7.25(1H,m),7.32(1H,m),7.49(1H,d,J=3.6Hz).IR(CHCl3)3372,3272,3018,2946,2686,1727,1438,1417,1333,1151/cm.[α]D=-9.2°(CHCl3,C=1.01,25℃).No.1a-21CDCl3 300MHz1.02-2.01(14H,m),2.28-2.34(3H,m),3.13(1H,m),5.12(1H,d,J=6.9Hz),5.28-5.32(2H,m),7.06(1H,m),7.10(1H,d,J=3.9Hz),7.25(1H,m),7.32(1H,m),7.50(1H,d,J=3.9Hz).IR(CHCl3)3350,3250,2948,1709,1440,1420,1330,1151.[α]D=+2.5°(CHCl3,C=1.00,25℃).No.1a-22CDCl3 300MHz0.96-2.05(14H,m),2.25(1H,m),2.35(2H,t,J=7.0Hz),3.11(1H,m);5.20-5.34(2H,m),5.41(1H,d,J=6.6Hz),7.31-7.49(5H,m),7.62(1H,d,J=7.8Hz),8.11(1H,d.d,J=1.8and7.8Hz),8.35(1H,d,J=1.8Hz).IR(CHCl3)3384, 3271,3025,2958,1708,1608,1559,1537,1357,1168/cm.[α]D=+18.3°(CHCl3,C=0.31,22℃).No.1a-23CDCl3 300MHz0.97-2.07(14H,m),2.24(1H,m),2.35(2H,t,J=6.9Hz),3.09(1H,m),3.86(3H,s),5.24-5.35(2H,m),5.44(1H,d,J=6.3Hz),6.97-7.00(2H,m),7.26-7.28(2H,m),7.59(1H,d,J=8.1Hz),8.06(1H,d.d,J=2.1and8.1Hz),8.29(1H,d,J=2.1Hz).IR(CHCl3)3384,3270,2959,1709,1609,1535,1519,1357,1302,1255,1226,1169/cm.[α]D=+17.0 °(CHCl3,C=1.00,21℃).No.1No. 1a-24CDCl3 300MHz0.95-2.00(14H,m),2.20-2.25(1H,m),2.26(2H,t,J=7.2Hz),3.02-3.10(1H,m),3.66(3H,s),4.92(1H,d,J=6.6Hz),5.16-5.31(2H,m),7.52-7.60(3H,m),7.94-8.06(6H,m).IR(CHCl3)3376,3020,2946,2868,1726,1436,1366,1298,1164,1090,890/cm.[α]D=+11.2±0.5°(CHCl3,C=1.04,23.5℃)mp.101-103℃No.1a-25CDCl3 300MHz0.95-2.08(14H,m),2.15-2.22(1H,m),2.33(2H,t,J=6.9Hz),3.02-3.10(1H,m),5.21-5.31(2H,m),5.34(1H,d,J=6.3Hz),7.51-7.59(3H,m),7.92-8.07(6H,m).IR(CHCl3)3258,3022,2948,2868,1707,1399,1328,1298,1163,1089,1051,892/cm.[α]D=+29.8±0.7°(CHCl3,C=1.05,25℃)mp.158-160℃No.1a-26Anal.Calcd for C26H30N3O4SNa0.8H2OC,60.29;H,6.15;N,8.11;S,6.19;Na,4.44;FoundC,60.15;H,6.19;N,8.15;S,6.03;Na,4.98.[α]D=-16.6°(CHCl3,C=1.04,25.0℃).No.1a-27CDCl3 300MHz0.92-1.98(14H,m),2.20(1H,m),2.26(2H,t,J=7.5Hz),3.03(1H,m),3.12(6H,s),3.66(3H,s),4.87(1H,d,J=6.6Hz),5.16-5.32(2H,m),6.73-6.80(2H,m),7.88-8.00(6H,m).IR(CHCl3)3376,3020,2946,1726,1601,1518,1442,1419,1362,1312,1163,1133,1088/cm.[α]D=+55.3°(CHCl3,C=0.53,24.0℃).mp.158-168℃No.1a-28CDCl3+CD3OD 300MHz0.99-2.14(14H,m),2.21(1H,m),2.31(2H,t,J=7.2Hz),2.94(1H,m),3.12(6H,s),5.22-5.38(2H,m),6.73-6.81(2H,m),7.87-8.00(6H,m).IR(KBr)3434,3309,2946,1708,1604,1520,1442,1416,1366,1312,1252,1164,1155,1134,1091/cm.[α]D=不可测定(有颜色,能量不足)mp.193-196℃No.1a-29CD3OD 300MHz1.02-1.96(14H,m),2.10(2H,t,J=7.8Hz),2.16(1H,m),2.98(1H,m),3.11(6H,s),5.07-5.27(2H,m),6.80-6.87(2H,m),7.84-8.00(6H,m).IR(KBr)3433,308 7,3004,2949,2871,1604,1565,1520,1444,1420,1364,1312,1253,11638,1136,1090/cm.[α]D=不可测定No.1a-30CDCl3 300MHz0.95-1.99(14H,m),2.22(1H,m),2.26(2H,t,J=7.2Hz),2.35(3H,s),3.06(1H,m),3.66(3H,s),4.95(1H,d,J=6.9Hz),5.15-5.30(2H,m),7.26-7.32(2H,m),7.97-8.06(6H,m).IR(CHCl3)3374,2996,2946,2868,1763,1728,1591,1495,1435,1368,1299,1228,1192,1163,1139/cm.[α]D=+12.9°(CHCl3,C=1.04,26.0℃).No.1a-31CDCl3 300MHz0.93-2.01(14H,m),2.19(1H,m),2.31(2H,t,J=7.2Hz),2.35(3H,s),3.06(1H,m),5.17-5.32(2H,m),7.25-7.32(2H,m),7.96-8.07(6H,m).IR(CHCl3)3267,3028,2952,2874,1759,1708,1592,1495,1368,1328,1299,1163,1138,1088,1050,1008/cm.[α]D=+21.7°(CHCl3,C=0.51,22℃).No.1a-32CDCl3 300MHz0.93-1.99(14H,m),2.21(1H,m),2.27(2H,t,J=7.2Hz),3.05(1H,m),3.67(3H,s),4.92(1H,d,J=6.6Hz),5.15-5.30(2H,m),6.72(1 H,s),6.96-7.00(2H,m),7.86-8.04(6H,m).IR(CHCl3)3374,3276,3018,2946,2686,1725,1605,1589,1502,1433,1396,1330,1271,1164,1135,1089/cm. [α]D=+18.6°(CHCl3,c=1.00,26.0℃).No.1a-33CDCl3+CD3OD 300MHz0.98-2.08(14H,m),2.20(1H,m),2.28(2H,t,J=7.2Hz),2.98(1H,m),5.18-5.32(2H,m),6.92-6.99(2H,m), 7.85-8.02(6H,m).IR(KBr)3385,3248,2948,2876,1717,1601,1505,1430,1399,1296,1280,1219,1165,1136,1092/cm.[α]D=-16.0°(CH3OH,C=1.08,26.0℃).mp.208-210℃No.1a-34mp.82-83℃[α]D=+10.6°(CHCl3,C=1.01,23.5℃).No.1a-35mp.80-82℃[α]D=-1.8°(CHCl3,C=1.07,22.0℃).No.1a-36TLC Rf=0.25(ethyl acetate/n-hexane=1∶1(0.3%乙酸))No.1a-37CDCl3 300MHz0.92-1.96(14H,m),2.21(1H,m),2.27(2H,t,J=7.4Hz),3.01(1H,m),3.66(3H,s),4.71(1H,d,J=6.6Hz),5.14-5.29(2H,m),7.12(1H,d,J=16.2Hz),7.24(1H,d,J=16.2Hz),7.28-7.42(3H,m),7.52-7.56(2H,m),7.62(2H,d,J=8. 7Hz),7.85(2H,d,J=8.7Hz).IR(CHCl3)3384,3283,3023,2954,2876,1730,1595,1494,1317,1163,1147/cm.[α]D=+10.5°(CHCl3,C=1.01,24℃).mp 116-117℃.No.1a-38CDCl3 300MHz0.92-1.99(14H,m),2.17(1H,m),2.32(2H,t,J=7.2Hz),3.02(1H,m),5.23-5.29(3H,m),7.11(1H,d,J=16.2Hz),7.23(1H,d,J=16.2Hz),7.28-7.41(3H,m),7.52-7.55(2H,m),7.61(2H,d,J=8.7Hz),7.86 (2H,d,J=8.7Hz).IR(CHCl3)3515,3384,3270,3022,3015,2957,2876,2669,1708,1595,1496,1320,1157/cm.[α]D=+27.1°(CHCl3,C=1.02,24℃).No.1a-39CDCl3 300MHz0.92-1.99(14H,m),2.15(1H,m),2.28(2H,t,J=7.4Hz),3.0 1(1H,m),3.68(3H,s),4.96(1H,d,J=6.6Hz),5.16-5.32(2H,m),6.60(1H,d,J=12.0Hz),6.74(1H,d,J=12.0Hz),7.16-7.23(5H,m),7.35(2H,d,J=8.4Hz),7.72(2H,d,J=8.4Hz).IR(CHCl3)3384,3283,3023,3015,2954,2876,1730,1595,1493,1324,1163,1147/cm.[α]D=+13.7°(CHCl3,C=1.00,24℃).No.1a-40CDCl3 300MHz0.90-2.16(14H,m),2.12(1H,m),2.34 (2H,t,J=7.2Hz),3.02(1H,m),5.16(1H,d,J=6.9Hz),5.23-5.34(2H,m),6.60(1H,d,J=12.3Hz),6.74(1H,d,J=12.3Hz),7.14-7.24(5H,m),7.35(2H,d,J=8.1Hz),7.72(2H,d,J=8.1Hz).IR(CHCl3)3515,3384,3269,3025,3021,3014,2957,2876,2668,1709,1595,1322,1162,1147/cm.[α]D=+26.4°(CHCl3,C=1.00,24℃).No.1a-41CDCl3 300MHz0.98-1.99(14H,m),2.17(1H,m),2.32(2H,t,J=7.2Hz),3.00(1H,m),3.84(3H,s),5.20-5.26(3H,m),6.90-6.95(2H,m),6.98(1H,d,J=16.2Hz),7.17(1H,d,J=16.2Hz),7.46-7.49(2H,m),7.58(2H,d,J=8.4Hz),7.83(2H,d,J=8.4Hz).IR(CHCl3)3258,3018,3002,2950,1709,1590,1509,1457,1404,1302,1250,1153/cm.[α]D=+30.2°(CHCl3,C=1.00,23℃).mp.99-100℃No.1a-42CDCl3 300MHz1.01-1.99(14H,m),2.28(2H,t,J=7.2Hz),2.30(1H,m),3.10(1H,m),3.66(3H,s),5.07(1H,br),5.25-5.30(2H,m),6.98-7.04(2H,m),7.16(1H,d,J=16.2Hz),7.28-7.37(3H,m),7.47-7.50(3H,m).IR(CHCl3)3372,3276,3020,2946,2870,1727,1491,1433,1331,1152/cm.[α]D=-11.5°(CHCl3,C=1.07,21.5℃).No.1a-43CDCl3 300MHz0.98-2.00(14H,m),2.11-2.36(3H,m),3.12(1H,m),5.10(1H,d,J=6.6Hz),5.29-5.32(2H,m),6.99-7.04(2H,m),7.23(1H,d,J=21.6Hz),7.32-7.49(6H,m).IR(CHCl3)3380,3248,3020,2948,2868,1709,1491,1430,1329,1151/cm.[α]D=+3.4°(CHCl3,C=1.03,25℃).No.1a-44CDCl3 300MHz1.00-2.00(14H,m),2.13(1H,m),2.29(2H,t,J=7.4Hz),2.90-3.13(5H,m),3.68(3H,s),4.74(1H,d,J=6.6Hz),5.15-5.30(2H,m),7.18-7.29(7H,m),7.76(2H,d,J=8.1Hz).IR(CHCl3)3384,3282,3063,3028,3023,3016,2953,2876,1730,1599,1496,1319,1157/cm.[α]D=+2.3°(CHCl3,C=1.00,25℃).mp.85.0-86.0℃No.1a-45CDCl3 300MHz0.90-2.05(14H,m),2.09(1H,m),2.35(2H,t,J=6.9Hz),2.90-3.13(5H,m),5.18(1H,d,J=6.6Hz),5.24-5.34(2H,m),7.10-7.27(7H,m),7.76(2H,d,J=8.4Hz).IR(CHCl3)3510,3384,3270,3087,3063,3026,3018,3014,2955,2876,2670,1708,1599,1496,1318,1157/cm.[α]D=+8.5°(CHCl3,C=1.01,25℃).No.1a-46[α]D=+6.8°(CHCl3,C=1.05,25℃),mp.99-100℃.No.1a-47CDCl3 300MHz0.97-2.01(14H,m),2.14(1H,m),2.36(2H,t,J=7.2Hz),3.02(1H,m),5.23(1H,d,J=5.4Hz),5.26-5.30(2H,m),7.37-7.39(3H,m),7.54-7.58(2H,m),7.63-7.66(2H,m),7.85-7.88(2H,m).IR(CHCl3)3375,3260,3022,2948,2212,1707,1596,1497,1396,1322,1160/cm.[α]D=+25.0°(CHCl3,C=1.02,24℃). mp.117-118℃.No.1a-48CD3OD 30MHz1.05-1.93(14H,m),2.10-2.15(3H,m),2.96(1H,m),5.08-5.28(2H,m),7.38-7.40(3H,m),7.554-7.56(2H,m),7.69(1H,d,J=8.4Hz),7.87(1H,d,J=8.4Hz).No.1a-49CDCl3 300MHz0.96-1.97(14H,m),2.24(1H,m),2.31(2H,t,J=6.9Hz),3.05(1H,m),3.69(3H,s),5.15(1H,d,J=6.6Hz),5.25-5.27(2H,m),7.40-7.43(3H,m),7.61-7.64(2H,m),7.85(1H,d,J=8.1Hz),8.07(1H,dd,J=8.1,1.8Hz),8.58(1H,d,J=1.8Hz).IR(CHCl3)3374,3020,2948,2870,2212,1726,1606,1530,1493,1437,1345,11671cm.[α]D=+2.4°(CHCl3,C=1.03,25℃). mp.77-79℃.No.1a-50CDCl3 300MHz1.00-2.02(14H,m),2.20(1H,m),2.34(2H,t,J=6.6Hz),3.08(1H,m),5.26-5.29(2H,m),5.41(1H,d,J=6.9Hz),7.40-7.43(3H,m),7.61-7.64(2H,m),7.84(1H,d,J=8.1Hz),8.07(1H,dd,J=8.4,1.8Hz),8.57(1H,dd,J=1.8Hz).IR(CHCl3)3380,3254,2952,2880,2212,1707,1606,1531,1493,1409,1344,1166.[α]D=+23.4°(CHCl3,C=1.00,25℃).No.1a-51CDCl3 300MHz0.95-1.98(14H,m),2.23(1H,m),2.30(2H,t,J=7.2Hz),3.00(1H,m),3.66(3H,s),4.56(2H,br),4.70(1H,d,J=6.9Hz),5.20-5.29(2H,m),7.15(1H,dd,J=7.8,1.8Hz),7.23(1H,d,J=1.8Hz),7.36-7.39(3H,m),7.46(1H,d,J=7.8Hz),7.53-7.56(2H,m).IR(CHCl3)3494,3386,3028,2952,2874,1725,1611,1559,1497,1422,1317,1162/cm.No.1a-52CDCl3 300MHz0.96-2.04(16H,m),2.20(1H,m),2.36(2H,t,J=6.9Hz),2.99(1H,m),5.17(1H,d,J=6.3Hz),5.28-5.31(2H,m),7.18(1H,dd,J=9.6,1.8Hz),7.25(1H,m),7.36- 7.39(3H,m),7.46(1H,d,J=7.8Hz),7.52-7.56(2H,m).IR(CHCl3)3482,3378,3260,3022,2948,2868,1708,1612,1495,1422,1317/cm.[α]D=+15.0°(CHCl3,C=1.00,24℃).No.1a-53CDCl3 300MHz1.01-2.05(15H,m),2.31(2H,t,J=7.2Hz),3.10(1H,m),3.67(3H,s),5.02(1H,br),5.26-5.33(2H,m),7.18(1H,d,J=4.2Hz),7.36-7.39(3H,m),7.48(1H,d,J=4.2Hz),7.51-7.55(2H,m). IR(CHCl3)3372,3270,3018,3004,2946,2868,2202,1726,1486,1433,1336,1154/cm.[α]D=+0.6°(CHCl3,C=1.11,25℃),[α]436+17.8°(CHCl3,C=1.11,25℃).No.1a-54CDCl3 300MHz0.99-2.11(14H,m),2.27(1H,m),2.37(2H,t,J=7.5Hz),3.13(1H,m),5.16(1H,d,J=6.6Hz),5.31-5.35(2H,m),7.18(1H,d,J=3.6Hz),7.37-7.39(3H,m),7.50(1H,d,J=3.6Hz),7.52-7.55(2H,m).IR(CHCl3)3484,3370,3246,2948,2868,2202,1708,1486,1429,1335,1153/cm.[α]D=+17.8°(CHCl3,C=1.00,24℃). mp.95-96℃No.1a-55CDCl3 300MHz0.95-1.92(14H,m),2.15(1H,m),2.24(2H,t,J=7.5Hz),3.00(1H,m),3.66(3H,s),5.10-5.30(3H,m),7.40-7.60(7H,m),7.70(1H,d,J=7.8Hz),8.08(1H,d,J=8.1Hz). IR(CHCl3)3356,3020,2948,2868,2210,1727,1490,1458,1437,1341,1165/cm.[α]D=-58.4°(CHCl3,C=1.00,26℃). mp.84-85℃.No.1a-56CDCl3 300MHz0.95-1.95(14H,m),2.10(1H,m),2.27(2H,t,J=6.9Hz),3.00(1H,m),5.17-5.21(2H,m),5.38(1H,d,J=6.9Hz),7.39-7.60(7H,m),7.70(1H,dd,J=7.8,1.5Hz),8.07(1H,J=6.6,1.5Hz).IR(CHCl3)3364,3026,2952,2874,2212,1707,1597,1491,1458,1411,1341,1164/cm.[α]D=-43.1°(CHCl3,C=1.00,25℃).No.1a-57CDCl3 300MHz0.99-1.97(14H,m),2.23-2.30(3H,m),3.01 (1H,m),3.67(3H,s),5.17-5.26(3H,m),7.36-7.38(3H,m),7.50- 7.56(3H,m),7.60(1H,m),7.83(1H,m),8.05(1H,m).IR(CHCl3)3376,3020,2946,2870,1727,1598,1491,1437,1412,1330,1245,1163/cm.[α]D=-12.7°(CHCl3,C=1.00,24℃).No.1a-58CDCl3 300MHz0.97-1.98(14H,m),2.20(1H,m),2.33(2H,t,J=6.9Hz),3.02(1H,m),5.19-5.28(3H,m),7.36-7.38(3H,m),7.47-7.55(3H,m),7.69(1H,m),7.83(1H,m),8.04(1H,m).IR(CHCl3)3376,3260,3022,3002,2948,2868,2220,1708,1598,1490,1455,1412,1327,1162/cm.[α]D=-8.6°(CHCl3,C=1.01,24℃).No.1a-59CDCl3 300MHz0.95-1.99(24H,m),2.20(1H,m),2.28(2H,t,J=7.8Hz),2.53(1H,s),2.96(1H,m),3.69(3H,s),4.99(1H,d,J=6.6Hz),5.18-5.20(2H,m),7.53(2H,d,J=8.4Hz),7.82(2H,d,J=8.4Hz). IR(CHCl3)3583,3376,3002,2936,2852,1725,1591,1490,1437,1393,1325,1160/cm.[α]D=-8.8°(CHCl3,C=1.00,24℃).No.1a-60CDCl3 300MHz0.96-2.05(24H,m),2.22(1H,m),2.33(2H,m),2.88(1H,m),5.22-5.26(2H,m),5.30(1H,d,J=5.7Hz),7.50(2H,d,J=8.7Hz),7.80(2H,d,J=8.7Hz).IR(CHCl3)3376,3260,3022,2936,2852,1710,1592,1491,1452,1395,1325,1159/cm.[α]D=-8.9°(CHCl3,C=1.06,24℃),mp.88-91℃No.1a-61CDCl3 300MHz0.95-2.24(23H,m),2.29(2H,m),2.99(1H,m),3.69(3H,s),4.76(1H,d,J=6.3Hz),5.21-5.24(2H,m),6.28(1H,m),7.50-7.53(2H,m),7.77- 7.80(2H,m).IR(CHCl3)3374,3270,3018,2942,2868,2196,1726,1589,1490,1435,1324,1158/cm.[α]D=+7.7°(CHCl3,C=1.02,24℃), mp.93-95℃No.1a-62CDCl3 300MHz0.96-2.45(23H,m),2.36(2H,d,J=6.9Hz),2.99(1H,m),5.24(1H,d,J=6.3Hz),5.24-5.32(2H,m),6.28(1H,m),7.50-7.53(2H,m),7.78-7.8 1(2H,m).IR(CHCl3)3468,3374,3260,3020,2942,2868,2196,1598,1490,1455,1398,1322,1157/cm.[α]D=+19.4°(CHCl3,C=1.03,24℃).No.1a-63CDCl3 300MHz0.93-1.95(25H,m),2.16(1H,m),2.29(2H,t,J=7.2Hz),2.43(2H,t,J=6.9Hz),2.94(1H,m),3.69 (3H,s),4.95(1H,d,J=6.9Hz),5.21-5.24(2H,m),7.49(2H,d,J=8.7Hz),7.79(2H,J=8.7Hz). IR(CHCl3)3376,3018,2946,2866,2222,1727,1592,1456,1435,1325,1158/cm.[α]D=+3.7°(CHCl3,C=1.00,25℃).No.1a-64CDCl3 300MHz0.93-1.97(26H,m),2.35(2H,t,J=7.2Hz),2.43(2H,t,J=7.2Hz),3.00(1H,m),5.08(1H,d,J=6.6Hz),5.26-5.27(2H,m),7.49(2H,d,J=8.7Hz),7.78(2H,d,J=8.7Hz).IR(CHCl3)3260,3020,2948,2864,2222,1708,1592,1489,1456,1397,1324,1156/cm.[α]D=+14.4°(CHCl3,C=1.00,25℃) mp.70-71℃.No.1a-65CDCl3 300MHz0.95-1.98(14H,m),2.18(1H,m),2.30(2H,t,J=7.2Hz),3.00(1H,m),3.67(3H,s),4.83(1H,d,J=6.9Hz),5.22-5.25(2H,m),5.54(1H,br),6.82-6.85(2H,m),7.42-7.45(2H,m),7.59-7.62(2H,m),7.82-7.85(2H,m).IR(CHCl3)3576,3374,3018,2946,2868,2208,1725,1607,1587,1514,1435,1325,1270,1162,1133/cm.[α]D=+9.1°(CHCl3,C=1.03,24℃),mp.111-112℃No.1a-66CDCl3 300MHz0.97-2.03(14H,m),2.15(1H,m),2.35(2H,t,J=7.5Hz),3.00(1H,m),5.17(1H,d,J=6.6Hz),5.26-5.30(2H,m),6.82-6.85(2H,m),7.42-7.45(2H,m),7.59-7.62(2H,m),7.82-7.85(2H,m).IR(CHCl3)3260,2948,2870,2208,1709,1607,1587,1514,1396,1325,1270,1162,1133/cm.[α]D=-21.0°(CHCl3,C=1.00,23℃),mp.161-162℃No. 1a-67CDCl3 300MHz0.95-1.98(14H,m),2.20(1H,m),2.29(2H,t,J=7.2Hz),3.01(1H,m),3.67(3H,s),4.82(1H,d,J=6.6Hz),5.19-5.27(2H,m),7.05-7.10(2H,m),7.51-7.56(2H,m),7.61-7.64(2H,m),7.84-7.87(2H,m).IR(CHCl3)3374,3280,3020,2946,2868,2214,1727,1589,1509,1435,1327,1233,1161,1134/cm.[α]D=+6.7°(CHCl3,C=1.01,24℃), mp.84-85℃No.1a-68CDCl3 300MHz0.96-2.01(14H,m),2.15(1H,m),2.34(2H,t,J=6.9Hz),3.02(1H,m),5.23-5.27(3H,m),7.04-7.10(2H,m),7.51- 7.56(2H,m),7.61-7.64(2H,m),7.85- 7.88(2H,m).IR(CHCl3)3374,3258,3020,2948,2868,2214,1708,1589,1509,1455,1398,1322,1156/cm.[α]D=+22.6°(CHCl3,C=1.02,24℃),mp.135-136℃No.1a-69CDCl3 300MHz0.95-1.98(14H,m),2.19(1H,m),2.29(2H,t,J=7.2Hz),2.39(3H,s),3.01(1H,m),3.69(3H,s),4.80(1H,d,J=6.6Hz),5.20-5.29(2H,m),7.18(2H,d,J=8.1Hz),7.44(2H,d,J=8.1Hz),7.62(2H,d,J=8.4Hz),7.84(2H,d,J=8.4Hz).IR(CHCl3)3374,3022,2946,2868,2210,1727,1589,1511,1436,1323,1161,1133/cm.[α]D=+9.2°(CHCl3,C=1.02,24℃).mp.116-118℃No.1a-70CDCl3 300MHz1.15-2.00(14H,m),2.13(1H,m),2.33-2.38(5H,m),3.04(1H,m),5.14(1H,d,J=6.6Hz),5.25-5.30(2H,m),7.17(2H,d,J=7.8Hz),7.44(2H,d,J=7.8Hz),7.62(2H,d,J=8.4Hz),7.85(2H,d,J=8.4Hz).IR(CHCl3)3380,3260,3020,2948,2868,2210,1708,1590,1511,1396,1324,1160,1133/cm.[α]D=+24.6°(CHCl3,C=1.00,24℃).No.1a-71CDCl3 300MHz0.95-1.96(14H,m),2.19(1H,m),2.29(2H,t,J=7.2Hz),3.00(1H,m),3.20(1H,s),3.65(3H,s),4.81 (1H,d,J=6.6Hz),5.20-5.27(2H,m),7.46-7.54(4H,m),7.62-7.65(2H,m),7.85-7.88(2H,m).IR(CHCl3)3374,3290,3018,3002,2946,2868,2212,2110,1726,1591,1507,1435,1401,1324,1161/cm.[α]D=+9.6°(CHCl3,C=1.01,24℃),mp.136-138℃,No.1a-72CDCl3 300MHz0.96-2.01(14H,m),2.14(1H,m),2.35(2H,t,J=7.2Hz),3.05 (1H,m),3.20(1H,s),5.16(1H,d,J=7.2Hz),5.26-5.29(2H,m),7.45-7.53(4H,m),7.63(2H, d,J=8.4Hz),7.87(2H,d,J=8.4Hz).IR(CHCl3)3462,3374,3290,3024,2948,2868,2212,2110,1708,1591,1508,1455,1401,1321,1274,1160,1132/cm.[α]D=+24.3°(CHCl3,C=1.03,24℃),mp.96-99℃No.1a-73CDCl3 300MHz0.95-1.98(14H,m),2.19(1H,m),2.27-2.32(5H,m),3.01 (1H,m),3.67(3H,s),4.80(1H,d,J=6.6Hz),5.20-5.27(2H,m),7.12(2H,m),7.56(2H,m),7.63(2H,m),7.84(2H,m).IR(CHCl3)3374,3276,3018,2946,2868,2214,1762,1730,1589,1506,1435,1368,1161/cm.[α]D=+7.8°(CHCl3,C=1.02,24℃),mp.102-104℃No.1a-74CDCl3 300MHz0.95-2.05(14H,m),2.15 (1H,m),2.32-2.37(5H,m),3.02(1H,m),5.14(1H,d,J=6.6Hz),5.26-5.30(2H,m),7.10-7.13(2H,m),7.54-7.57(2H,m),7.62-7.64(2H,m),7.84-7.87(2H,m).IR(CHCl3)3482,3250,3022,2946,2868,2214,1716,1709,1589,1507,1454,1396,1368,1322,1195,1161/cm.[α]D=+15.0°(CHCl3,C=1.00,24℃),mp.129-131℃No.1a-75CDCl3 300MHz0.95-1.99(14H,m),2.20(1H,m),2.30(2H,t,J=7.2Hz),3.02(1H,m),3.67(3H,s),3.94(3H,s),4.79(1H,d,J=6.6Hz),5.19-5.29(2H,m),7.60-7.63(2H,m),7.65-7.67(2H,m),7.86-7.89(2H,m),8.04-8.06(2H,m).IR(CHCl3)3378,3018,2946,2880,1720,1604,1435,1307,1276,1161,1106/cm.[α]D=+7.3°(CHCl3,C=1.01,25℃),mp.132-133℃No.1a-76CDCl3+CD3OD 300MHz1.04-2.05(14H,m),2.19(1H,m),2.32(2H,t,J=6.9Hz),2.93(1H,m),5.27-5.31(2H,m),7.60-7.63(2H,m),7.65-7.68(2H,m),7.86-7.89(2H,m),8.05-8.07(2H,m).IR(CHCl3)3402,3299,2955,2876,2665,2549,1455,1422,1313,1281,1164/cm.[α]D=-21.1°(CH3OH,C=1.03,23℃),mp.227-229(dec.)No.1a-77CDCl3 300MHz0.96-1.99(14H,m),2.20(1H,m),2.30(2H,t,J=7.2Hz),3.02(1H,m),3.68(3H,s),4.88(1H,d,J=6.3Hz),5.19-5.29 (2H,m),7.67-7.72(4H,m),7.89-7.91(2H,m),8.24-8.27(2H,m). IR(CHCl3)3376,3276,3020,2946,2870,2214,1726,1594,1519,1455,1435,1389,1344,1161/cm.[α]D=+7.7°(CHCl3,C=1.02),mp.87-89℃No.1a-78CDCl3 300MHz 0.98-2.00(14H,m),2.18(1H,m),2.34(2H,t,J=7.2Hz),3.02(1H,m),5.24-5.28(2H,m),5.32(1H,d,J=5.7Hz),7.67-7.72(4H,m),7.89-7.92(2H,m),8.23-8.26(2H,m).IR(CHCl3)3374,3260,2948,2214,1708,1595,1344,1160/cm.[α]D=+23.3°(CHCl3,C=1.00),mp.102-103℃.No.1a-79CDCl3 300MHz0.93-2.02(14H,m),2.13(1H,m),2.36(2H,t,J=7.1Hz),3.05(1H,m),3.84(3H,s),5.18(1H,br),5.27-5.31(2H,m),6.88-6.91(2H,m),7.48-7.50(2H,m),7.60-7.63(2H,m),7.83-7.85(2H,m).IR(CHCl3)3380,3252,3020, 2950,2868,2208,1708,1589,1511,1457,1396,1321,1286,1160/cm.[α]D=+26.7°(CHCl3,C=1.00). mp.75-77℃No.1a-80CDCl3 300MHz0.96-1.99(14H,m),2.21(1H,m),2.30(2H,t,J=7.8Hz),3.02(1H,m),3.68(3H,s), 4.80(1H,d,J=6.6Hz),5.19-5.28(2H,m),7.51-7.77(5H,m), 7.87-7.90(2H,m),8.13(1H,m).IR(CHCl3)3374,3270,3018,2946,2868,2216,1726,1607,1567,1527,1495,1456,1436,1344,1296,1161/cm.[α]D=+7.4°(CHCl3,C=1.00,22℃),mp.68-70℃No.1a-81CDCl3 300MHz0.97-2.01(14H,m),2.16(1H,m),2.34(2H,t,J=7.2Hz),3.01(1H,m),5.22-5.28(3H,m),7.51(1H,m),7.65(1H,m)7.70-7.76(3H,m),7.88-7.91(2H,m),8.12(1H,dd,J=6.9Hz,1.5Hz).IR(CHCl3)3480,3382,3262,3026,2952,2872, 2218,1708,1607,1567,1526,1396,1343,1225,1160/cm.[α]D=+22.0°(CHCl3,C=1.00),mp.92-94℃No.1a-82CDCl3 300MHz0.95-1.98(14H,m),2.20(1H,m),2.29(2H,t,J=7.2Hz),3.01(1H,m ),3.67(3 H,s),4.30(2H,br),4.79(1H,d,J=6.9Hz),5.20-5.29(2H,m),6.71-6. 76(2H,m),7.18(1H,m),7.37(1H,dd,J=7.8,1.2Hz),7.61-7.65(2H,m),7.83-7.87(2H,m).IR(CHCl3)3376,3020,2946,2868,2202,1725,1613,1589,1484,1454,1315,1253,1161/cm.[α]D=+8.9°(CHCl3,C=1.00,22℃). mp.68-70℃No.1a-83CDCl3 300MHz0.97-1.99(14H,m),2.17(1H,m),2.33(2H,t,J=6.9Hz),2.99(1H,m),5.20-5.28(2H,m),5.37(1H,d,J=6.9Hz),6.45(2H,br),6.71-6.76(2H,m),7.19(1H,dd,J=7.8,6.6Hz),7.37(1H,m),7.62(2H,d,J=8. 4Hz),7.85(2H,d,J=8.4Hz).IR(CHCl3)3478,3378,3260,3022,2950,2868,2204,1708,1613,1589,1484,1454,1396,1316,1160/cm.[α]D=+17.1°(CHCl3,C=1.01).No.1a-84CDCl3 300MHz1.00-2.08(14H,m),2.21 (1H,m),2.37(2H,t,J=6.9Hz),3.06(1H,m),3.86 (3H,s),5.29-5.33(2H,m),5.45(1H,d,J=6.6Hz),6.91-6.94(2H,m),7.56- 7.59(2H,m),7.81(1H,d.t,J=8.1Hz),8.04(1H,d.d,J=8. 1&1.8Hz),8.57(1H,d,J=2.1Hz).IR(CHCl3)3492,3254,3028,2954,2202,1708,1597,1512,1344,1291,1250/cm.[α]D=+27.4°(CHCl3,C=0.53,23℃).No.1a-85CDCl3 300MHz0.96-2.05(14H,m),2.20(1H,m),2.35(2H,t,J=6.9Hz),2.99(1H,m),3.84(3H,s),5.22-5.31(3H,m),6.89(2H,d,J=8.7Hz),7.19(1H,brs),7.29(1H,brs),7.45-7.50(3H,m).IR(CHCl3)3478,3378,3020,2950,2868,2202,1708,1606,1511,1421,1311,1287,1248,1155/cm.[α]D=+17.1°(CHCl3,C=1.00,23℃).No.1a-86CDCl3 300MHz1.03-2.05(14H,m),2.21(1H,m),2.37(2H,t,J=6.9Hz),3.04(1H,m),5.29-5.33(2H,m),5.57(1H,d,J=6.3Hz),6.84-6.87(2H,m),7.50-7.53(2H,m),7.79(1H,d,J=8.1Hz),8.03(1H,d,d,J=1.5and8.1Hz),8.57(1H,d,J=1.5Hz).IR(CHCl3)3250,3024,2950,2868,2200,1707,1515,1344,1271,1166,1143/cm.[α]D=+21.2°(CHCl3,C=0.26,22℃).No.1a-87CD3OD 300MHz1.04-2.00(14H,m),2.18 (1H,m),2.26(2H,t,J=5.4Hz),2.93(1H,m),5.19-5.24(2H,m),6.77-6.80(2H,m),7.05(1H,d.d,J=2.1and8.1Hz),7.22(1H,d,J=2.1Hz),7.38-7.42(3H,m).IR(CHCl3)3377,2952,2873,2204,1705,1607,1515,1425,1312,1267,1222,1153/cm.[α]D=-15.6°(CH3OH,C=1.02,22℃).No.1a-88CDCl3 300MHz0.90-1.96(14H,m),2.22-2.31(3H,m),2.95(1H,m),3.65(3H,s),4.87(1H,d,J=6.6Hz),5.13-5.28(2H,m),7.46-7.62(3H,m),7.82-7.89(4H,m),7.90-7.96(2H,m),8.42(1H,brs).IR(CHCl3)3376,3016,2946,2868,1720,1677,1592,1514,1498,1429,1376,1314,1241,1156,1094 /cm.[α]D=-10.7°(CHCl3,C=1.04,22.0℃) mp.134-136℃No.1a-89CDCl3+CD3OD 300MHz0.96-2.08(14H,m),2.23(1H,m),2.28(2H,t,J=7.2Hz),2.89(1H,m),5.20-5.32(2H,m),7.46-7.62(3H,m),7.82-7.97 (6H,m).IR(KBr)3272,3007,2952,2874,1708,1660,1592,1527,1498,1433,1400,1317,1260,1152,1094/cm.[α]D=-24.4°(CH3OH,C=1.02,25.0℃).No.1a-90CDCl3 300MHz0.89-1.96(14H,m),2.23-2.33(3H,m),2.92(1H,m),3.67(3H,s),4.85(1H,d,J=6.3Hz),5.10-5.25(2H,m),7.81-7.90(4H,m),8.10-8.18(2H,m),8.31-8.40(2H,m),8.77(1H,s).IR(CHCl3)3372,3018,2946,2868,1718,1685,1592,1527,1436,1397,1346,1318,1256,1154,1099/cm.[α]D=-16.1°(CHCl3,C=1.00,23.0℃).No.1a-91CDCl3+CD3OD 300MHz0.94-2.02(14H,m),2.18-2.36(3H,m),2.87(1H,m),5.15-5.30(2H,m),7.82-7.92(4H,m),8.09-8.16(2H,m),8.30-8.37(2H,m).IR(KBr)3284,3112,3006,2952,2874,1707,1593,1528,1498,1399,1348,1320,1259,1153,1093/cm.[α]D=-26.3°(CH3OH,C=1.01,22℃).No.1a-92CDCl3 300MHz0.93-1.95(14H,m),2.22-2.31(3H,m),2.98(1H,m),3.68(3H,s),5.07(1H,d,J=6.9Hz),5.10-5.24(2H,m),7.18(1H,m),7.35-7.43(2H,m),7.70(2H,d,J=7.8Hz),7.88-8.05(4H,m),8.50(1H,brs).IR(CHCl3)3382,3008,2952,1720,1675,1599,1525,1499,1438,1321,1253,1161,1087/cm.[α]D=-16.6°(CHCl3,C=1.03,24.0℃) mp.100-101℃No.1a-93CDCl3+CD3OD 300MHz0.96-2.00(14H,m),2.18-2.35(3H,m),2.90(1H,m),5.15-5.30(2H,m),7.18(1H,m),7.33-7.42(2H,m),7.65-7.74(2H,m),7.90-8.08(4H,m).IR(KBr)3347,3194,3011,2955,2875,1706,1650,1602,1544, 1499,1443,1325,1265,1165,1091/cm.[α]D=-19.4°(CH3OH,C=1.00,24.0℃) mp.158-159℃No.1a-94CD3OD300MHz1.05-2.00(14H,m),2.14 (1H,m),2.23(2H,t,J=7.2Hz),2.98(1H,m),3.80(3H,s),5.13-5.27(2H,m),6.88-6.98(2H,m),7.54-7.64(2H,m),7.94-8.12(4H,m).IR(KBr)3370,3006,2953,1708,1649,1604,1541,1512,1460,1441,1414,1328,1302,1248,1162,1107,1090,1032/cm.[α]D=-19.1°(CH3OH,C=1.01,24℃).No.1a-95CD3OD300MHz1.04-2.02(14H,m),2.14(1H,m),2.23(2H,t,J=7.2Hz),2.93-3.02(7H,m),5.13-5.27(2H,m),6.82-6.92 (2H,m),7.51-7.59(2H,m),7.95-8.02(2H,m),8.04-8.11(2H,m).IR(KBr)3370,3006,2953,1708,1649,1604,1541,1512,1460,1441,1414,1328,1302,1248,1162,1107,1090,1032/cm.[α]D=-17.6°(CH3OH,C=1.01,24℃).No.1a-96CD3OD300MHz1.05-2.02(14H,m),2.14(1H,m),2.23(2H,t,J=7.2Hz),2.98(1H,m),5.13-5.27(2H,m),6.75-6.84(2H,m),7.43-7.52(2H,m),7.94-8.12(4H,m).IR(KBr)3339,3197,2953,2875,1707,1644,1606,1541,1514,1446,1325,1293,1259,1240,1225,1161,1091/cm.[α]D=-18.7°(CH3OH,C=1.00,24℃). mp.193-196℃No.1a-97d6-DMSO 300MHz1.05-2.08(15H,m),2.15(2H,t,J=7.5Hz),2.89(1H,m),5.18-5.28(2H,m),6.78-7.12(3H,m),7.73(1H,d.d,J=1.4and7.8Hz),7.91-7.95(3H,m),8.14(2H,d,J=8.4Hz),9.71(1H,s).IR(KBr)3407,3191,2953,1711,1646,1614,1603,1537,1457,1326,1162,1151/cm.[α]D=-20.7°(CH3OH,C=1.01,21℃).No.1a-98CDCl3 300MHz0.93-2.00(14H,m),2.21(1H,m),2.31(2H,t,J=7.2Hz),2.93(1H,m),3.84(3H,s),3.85(6H,s),5.15-5.30(2H,m),5.45(1H,d,J=6.3Hz),7.04 (2H,s),7.78-7.86(2H,m),7.90-7.98(2H,m),8.58(1H,s).IR(CHCl3)3264,3008,2954,2874,1707,1670,1607,1537,1506,1451,1421,1308,1158,1129,1088/cm.[α]D=-7.2°(CHCl3,C=1.01,23.5℃).mp.147-149℃.No.1a-99CD3OD 300MHz1.04-1.98(14H,m),2.21(1H,m),2.10(2H,t,J=7.2Hz),2.95(1H,m), 3.76(3H,s),3.86(6H,s),5.07-5.24 (2H,m),7.19(2H,s),7.99(2H,d,J=8.7Hz),8.13(1H,d,J=8.7Hz).IR(KBr)3354,3002,2950,2874,1656,1607,1570,1508,1452, 1413,1314,1233,1185,1157,1127,1092/cm.[α]D=-20.3°(CH3OH,C=1.00,23.5℃).No.1a-100CDCl3 300MHz1.14-1.97(14H,m),2.19(1H,m),2.28(2H,t,J=7.4Hz),3.04(1H,m),3.69(3H,s),5.03(1H,d,J=6.9Hz),5.15-5.29(2H,m),7.65(2H,d,J=8.4Hz), 7.87 (1H,s),7.98(2H,d,J=8.4Hz).IR(CHCl3)3386,3271,3025,3015,2955,2877,1755,1712,1608,1331,1162/cm.[α]D=-29.4°(CH3OH,C=1.01,25℃).No.1a-101d6-DMSO1.00-2.20(17H,m),2.84(1H,m),5.00-5.20(2H,m),7.78(2H,d,J=8.2Hz),7.84(1H,s),7.89-7.95(3H,m).IR(KBr)3269,3065,3008,2952,2874,2763,1746,1707,1607,1322,1157/cm.[α]D=-26.2°(CH3OH,C=1.01,25℃).No.1a-102CD3OD1.00-2.25(17H,m),2.92(1H,s),3.64(3H,s),5.07-5.21(2H,m),7.53(1H,s),7.77(2H,d,J=8.6Hz),7.90(2H,d,J=8.6).IR(KBr)3430,3277,3006,2952,2873,1720,1687,1620,1571,1438,1312,1156 /cm.[α]D=-27.3°(CH3OH,C=0.51,26℃),mp 230-232℃.No.1a-103CDCl3 300MHz0.94-1.96(14H,m),2.19(1H,m),2.28(2H,t,J=7.2Hz),3.04 (1H,m),3.69(3H,s),5.11(1H,d,J=6.6Hz),5.15-5.28(2H,m),7.60(2H,d,J=8.4Hz),7.67(1H,s),7.98(2H,d,J=8.4Hz).IR(CHCl3)3381,3021,2955,2876,1735,1605,1437,1411,1325,1231,1177/cm.[α]D=+8.6°(CHCl3,C=1.00,23℃).No.1a-104CDCl3 300MHz0.94-1.96(14H,m),2.21(1H,m),2.31(2H,t,J=6.8Hz),2.99(1H,m),5.18-5.28(2H,m),5.45(1H,d,J=6.6Hz),7.61(2H,d,J=8.7Hz),7.67(1H,s),7.99 (2H,d,J=8.7Hz).IR(CHCl3)3382,3222,3028,3019,2957,2876,1736,1709,1604,1412,1322,1301,1286,1179,1162/cm.[α]D=+10.4°(CHCl3,C=1.00,23℃).No.1a-105CDCl3 300MHz0.92-1.98(14H,m),2.17(1H,m),2.26(2H.d,J=7.5Hz),3.01(1H,m),3.69(3H,s),4.01(3H,s),4.84(1H,d,J=6.3Hz),5.14-5.30(2H,m),7.71(2H,d,J=8.7Hz),7.87(2H,d,J=8.7Hz),8.09(1H,s).IR(CHCl3)3385,3284,3025,3015,2954,2877,2821,1730,1598, 1459,1438,1403,1341,1160,1052/cm.[α]D=+3.6°(CHCl3,C=1.00,26℃).No.1a-106CDCl3 300MHz0.92-2.08(14H,m),2.14(1H,m),2.34(2H,d,J=7.2Hz),3.02(1H,m),4.01(3H,s),5.19(1H,d,J=6.9Hz),5.23-5.32(2H,m),7.71(2H,d,J=8.4Hz),7.88(2H,d,J=8.4Hz),8.09(1H,s).IR(CHCl3)3510,3384,3268,3028,3021,3014,2957,2877,2821,2667,2821,2666,1707,1598,1459,1404,1341,1324,1160,1052/cm.[α]D=+11.8°(CHCl3,C=1.01,25℃)、mp 955-96℃No.1a-107CDCl3 300MHz0.92-1.97(14H,m),1.34(3H,t,J=7.2Hz),2.18(1H,m),2.28(2H.d,J=7.4Hz),3.01 (1H,m),3.68(3H,s),4.26(2H,q,J=7.2Hz),4.86(1H,d,J-6.6Hz),5.15-5.29(2H,m),7.71(2H,d,J=8.7Hz),7.87(2H,d,J=8.7Hz),8.09(1H,s).IR(CHCl3)3385,3282,3025,3026,3015,2954,2877,1729,1599,1480,1458,1438,1403,1338,1161/cm.[α]D=+4.4°(CHCl3,C=1.00,25℃).No.1a-108CDCl3 300MHz0.90-2.04(14H,m),1.34(3H,t,J=7.2Hz),2.14(1H,m),2.34 (2H, d,J=7.1Hz),3.01(1H,m),4.27 (2H,q,J=7.2Hz),5.20(1H,d,J=6.6Hz),5.21-5.35(2H,m),7.71(2H,d,J=8.4 Hz),7.88(2H,d,J=8.4Hz),8.10(1H,s).IR(CHCl3)3514,3384,3270,3025,3015,3015,2957,2877,1708.1599,1458,1403,1324,1324,1160,1050/cm.[α]D=+12.7°(CHCl3,C=1.00,25℃).No.1a-109[α]D=+8.5°(CHCl3,C=1.00,25℃).mp109.0-111.0℃No.1a-110CDCl3∶CD3OD(95∶5)0.92-2.06(14H,m),2.20(1H,m),2.30(2H,d,J=7.2Hz),2.99(1H,m),5.22-5.33(2H,m),7.54-7.66 (3H,m),8.07(2H,d,J=9.0Hz),8.12-8.20(2H,m),8.29 (2H,d,J=9.0Hz).IR(Nujol)3270,2956,2924,2854,1716,1548,1485,1319,1167/cm.[α]D=+17.0°(CHCl3,C=1.00,25℃). mp.166.5-168℃No.1a-111[α]D=+2.6°(CHCl3,C=1.00,24℃).mp120.0-121.0℃No.1a-112CDCl3 300MHz0.96-2.04(14H,m),2.19(1H,m),2.33(2H,d,J=7.1Hz),3.07(1H,m),5.28-5.31(2H,m),5.33(1H,d,J=6.6Hz),7.54-7.63(3H,m),8.05(2H,d,J=8.4Hz),8.18-8.23(2H,n),8.41 (2H,d,J=8.4Hz).IR(CHCl3)3384,3269,3025,3015,2957,2877,1708,1598,1496,1457,1417,13261164 /cm.[α]D=+12.2°(CHCl3,C=1.00,24℃). mp.163-164℃No.1a-113[α]D=+22.1°(CHCl3,C=1.05,25℃). mp.90-92℃No.1a-114[α]D=+2.2°(CHCl3,C=1.02,25℃).No.1a-115CDCl3 300MHz0.90-1.98(14H,m),2.15-2.22(1H,m),2.27(2H,t,J=7.2Hz),2.95-3.04(1H,m),3.68(3H,s),4.04(2H,s),4.85(1H,d,J=6.6Hz),5.10-5.27(2H,m),7.12-7.34(7H,m),7.76-7.82(2H,m).IR(CHCl3)3384,3026,2952,1727,1595,1493,1436,1318,1155,1091,890/cm.[α]D=0 °[α]436=+4.9±0.4°(CHCl3,C=1.05,23℃)No.1a-116CDCl3 300MHz0.90-2.10(14H,m),2.10-2.18(1H,m),2.32(2H,t,J=7.2Hz),2.96-3.04(1H,m),4.04(2H,s),5.14(1H,d,J=6.6Hz),5.16-5.28(2H,m),7.12-7.34(7H,m),7.76-7.82(2H,m).IR(CHCl3)3260,3020,2950,1709,1407,1318,1154,1091,892/cm.[α]D=+9.1±0.5°(CHCl3,C=1.04,23℃)No.1a-117CD9OD 300MHz0.96-2.18(17H,m),2.89-2.92(1H,m),4.05 (2H,s),4.95-5.22(2H,m),7.15-7.42 (7H,m),7.75-7.81(2H,m).IR(KBr)3429,3279,2951,2872,1563,1494,1453,1408,1313,1155,1093,1057/cm.[α]D=-16.3±0.5°(CH3OH,C=1.06,25℃)No.1a-118CDCl3 300MHz0.98-1.70(15H,m),1.80-2.00(5H,m),2.20-2.40(3H,m),2.98(1H,m),4.06(2H,s),4.72(1H,d,J=6.3Hz),5.00-5.23(3H,m),7.16(2H,d,J=8.4Hz),7.26-7.33(5H,m),7.79(2H,d,J=8.1Hz).IR(CHCl3)3376,3020,2948,2868,1716,1596,1492,1453,1407,1318,1155,1105/cm.[α]D=+2.4°(CHCl3,C=1.08,24℃).No.1a-119CDCl3 300MHz0.90-2.02(14H,m),2.20(1H,m),2.29(2H,t,J=7.2Hz),3.00(1H,m),3.68(3H,s),4.86 (1H,d,J=6.9Hz),5.13-5.34(2H,m),7.00-7.09(4H,m),7.22(1H,m),7.37,7.45(2H,m),7.79-7.86(2H,m).IR(CHCl3)3376,3018,2946,2868,1727,1582,1486,1321,1243,1151,1093/cm.[α]D=+4.5°(CHCl3,C=1.05,23.5℃).No.1a-120CD3OD 300MHz1.00-2.00(14H,m),2.13(2H,t,J=7.5Hz),2.16(1H,m),2.91(1H,m),5.05-5.33(2H,m),7.04-7.11(4H,m),7.18-7.25 (1H,m),7.38-7.48(2H,m),7.80-7.87(2H,m).IR(KBr)3430,3278,3006,2952,2873,1583,1487,1410,1322,1298,1245,1152,1095/cm.[α]D=-8.8°(CH3OH,C=1.05,25.0℃).No.1a-121CDCl3 300MHz0.90-2.10(14H,m),2.15(1H,m),2.35(2H,t,J=7.2Hz),3.01(1H,m),5.20(1H,d,J=6.9Hz),5.22-5.35(2H,m),7.00-7.09(4H,m),7.18-7.25(1H,m),7.37-7.45(2H,m),7.79-7.86(2H,m).IR(CHCl3)3260,3020,2948,2868,1708,1582,1486,1409,1321,1296,1243,1151,1093/cm.[α]D=+13.1°(CHCl3,C=1.04,24.0℃).No.1a-122CDCl3 300MHz0.90-2.00(14H,m),2.23(1H,m),2.28(2H,t,J=7.5Hz),2.96 (1H,m),3.67(3H,s),4.69(1H,d,J=6.6Hz),5.15-5.32(2H,m),6.22(1H,s),6.98- 7.40(5H,m),7.30- 7.38(2H,m),7.68-7.74(2H,m).IR(CHCl3)3416,3370,3018,2946,2868,1725,1587,1508,1437,1400,1320,1149,1094/cm.[α]D=+6.2°(CHCl3,C=1.04,25.0℃).No.1a-123CDCl3 300MHz0.90-2.04(14H,m),2.18(1H,m),2.33(2H,t,J=7.2Hz),2.96(1H,m),5.04-5.35(3H,m),6.98-7.12(3H,m),7.12-7.20(2H,m),7.28-7.38(2H,m),7.66-7.74(2H,m).IR(CHCl3)3424,3270,3028,2952,2872,1708,1587,1508,1445,1399,1320,1148,1092/cm.[α]D=+20.9°(CHCl3,C=1.06,23.0℃).No.1a-124CDCl3 300MHz0.90-2.00(14H,m),2.18(1H,m),2.28(2H,t,J=7.2Hz),3.00(1H,m),3.14(3H,s),3.68(3H,s),4.56(2H,s),4.84(1H,d,J=6.3Hz),5.10-5.29 (2H,m),7.16-7.26(4H,m),7.26-7.34(2H,m),7.78-7.84(2H,m).IR(CHCl3)3384,3028,2952,2874,1727,1598,1501,1435,1410,1370,1329,1172,1148,1091/cm.[α]D=+2.7°(CHCl3,C=1.09,23.0℃).No.1a-125CDCl3 300MHz0.90-2.00(14H,m),2.18(1H,m),2.28(2H,t,J=7.2Hz),2.29(3H,s),3.00(1H,m),3.68(3H,s),4.04(2H,s),4.80(1H,d,J=6.6Hz),5.11-5.29(2H,m),6.99-7.06(2H,m),7.12-7.19(2H,m),7.31(2H,d,J=8.1Hz),7.79(2H,d,J=8.1Hz).IR(CHCl3)3382,3280,3024,2950,2874,1730,1596,1504,1435,1407,1367,1318,1196,1155,1091/cm.[α]D=+2.9°(CHCl3,C=1.06,23.0℃).No.1a-126CDCl3 300MHz0.90-2.02(14H,m),2.14(1H,m),2.29(3H,s),2.32(2H,t,J=7.2Hz),3.01(1H,m),4.03(2H,s),5.10(1H,d,J=6.6Hz),5.15-5.30(2H,m),6.98-7.06(2H,m),7.11-7.18(2H,m),7.30(2H,d,J=8.1Hz),7.79(2H,d,J=8.1Hz).IR(CHCl3)3374,3260,3020,2948,2868,1749,1708,1596,1504,1407,1369,1317,1195,1155,1091 /cm.[α]D=+10.0°(CHCl3,C=1.09,23.0℃).No.1a-127CDCl3 300MHz0.87-1.95(14H,m),2.18-2.32(3H,m),2.95(1H,m),3.69(3H,s),3.96(2H,s),4.79(1H,d,J=6.6Hz),4.97-5.17(2H,m),5.54(1H,s),6.75-6.82(2H,m),6.97-7.05(2H,m),7.25-7.33(2H,m),7.75-7.81(2H,m).IR(CHCl3)3382,3026,2950,2874,1722,1595,1511,1436,1407,1317,1257,1154,1090/cm.[α]D=-2.1°(CHCl3,C=1.00,21.5℃).No.1a-128CDCl3 300MHz0.85-2.02(14H,m),2.18(1H,m),2.31(2H,t,J=7.2Hz),2.96(1H,m),3.95(2H,s),5.05-5.27(3H,m),6.73-6.82(2H,m),6.96-7.04(2H,m),7.25-7.32(2H,m),7.74-7.81(2H,m).IR(CHCl3)3262,3020,2948,2868,1708,1596,1511,1407,1315,1242,1154,1091/cm.[α]D=+4.8°(CHCl3,C=1.04,22℃).No.1a-129CDCl3 300MHz0.89-1.98(14H,m),2.18(1H,m),2.27(2H,t,J=7.2Hz),2.99(1H,m),3.68(3H,s),3.79(3H,s),3.98(2H,s),4.81(1H,d,J=6.6Hz),5.10-5.27(2H,m),6.81-6.87(2H,m),7.03-7.10(2H,m),7.25-7.32(2H,m),7.75-7.82(2H,m).IR(CHCl3)3382,3276,3006,2950,2874,1726,1609,1509,1457,1436,1407,1315,1244,1154,1091,1033/cm.[α]D=+19.3°(CHCl3,C=1.05,23℃).No.1a-130CDCl3 300MHz0.90-2.00(14H,m),2.20(1H,m),2.30(2H,t,J=7.2Hz),2.98(1H,m),3.69(3H,s),4.81(1H,d,J=6.6Hz),5.12-5.32(2H,m),546(1H,brs),6.84- 7.01(6H,m),7.76-7.83(2H,m)IR(CHCl3)3380, 3284,3024,2952,2874,1724,1588,1504,1488,1436,1321,1296,1149,1091/cm.[α]D=+28.9°(CHCl3,C=1.01,23℃).No.1a-131CDCl3 300MHz0.92-2.10(14H,m),2.18(1H,m),2.34(2H,t,J=6.9Hz),2.96(1H,m),5.18-5.35(3H,m),6.84-7.01 (6H,m),7.75-7.83(2H,m).IR(CHCl3)3270,3028, 2952,2874,1708,1589,1505, 1489,1456, 1322,1297,1238,1148,1091/cm.[α]D=+7.7°(CHCl3,C=1.09,24℃).No.1a-132CDCl3 300MHz0.91-2.02(14H,m),2.19(1H,m),2.29(2H,t,J=7.2Hz),2.99(1H,m),3.68(3H,s),3.83(3H,s),4.82(1H,d,J=6.6Hz),5.14-5.33(2H,m),6.90-7.04(6H,m),7.76-7.83(2H,m).IR(CHCl3)3384,3006,2952,2874,1727,1589,1502,1488,1459,1438,1321,1295,1231,1150,1092,1033/cm.[α]D=+3.1°(CHCl3,C=1.01,23℃).No.1a-133TLC Rf=0.21 (乙酸乙酯/正已烷=1∶1(0.3%乙酸))No.1a-134CDCl3 300MHz0.97-2.10(14H,m),2.20(1H,m),2.36(2H,t,J=6.9Hz),3.04(1H,m),5.22-5.33(2H,m),5.41(1H,d,J=6.6Hz),7.02(1H,d,J=9.0Hz),7.09-7.13(2H,m),7.26-7.32(1H,m),7.43-7.49(2H,m),7.93(1H,d.d,J=2.4and9.0Hz),8.46(1H,d,J=2.4Hz).IR(CHCl3)3384,3270,3020,2958,1709,1610,1587,1537,1479,1352,1271,1252,1167/cm.[α]D+20.9°(CHCl3,C=0.51,22℃).No.1a-135CDCl3 300MHz0.96-2.02(14H,m),2.21(1H,m),2.29(2H,t,J=7.2Hz),3.07(1H,m),3.68(3H,s),5.04(1H,d,J=6.9Hz),5.16-5.33(2H,m),7.48-7.55(2H,m),7.64(1H,m),7.76-7.82(2H,m),7.88-7.94(2H,m),7.98-8.04(2H,m).IR(CHCl3)3384,3282,3026,2952,2874,1727,1663,1596,1446,1396,1316,1274,1163,1090/cm.[α]D=+3.1°(CHCl3,C=1.03,22.0℃).No.1a-136CDCl3 300MHz0.95-2.05(14H,m),2.19(1H,m),2.34(2H,t,J=7.2Hz),3.08(1H,m),5.10-5.40(2H,m),5.35(1H,d,J=6.8Hz),7.45-7.58(2H,m),7.64(1H,m),7.74-7.84(2H,m),7.84-7.95(2H,m),7.95-8.06(2H,m).IR(CHCl3)3260,3018,2950,2870,1708,1662,1595,1446,1395,1316,1274,1162,1090/cm.[α]D=+12.9°(CHCl3,C=1.05,21.5℃).No.1a-137CDCl3 300MHz0.97-2.04(14H,m),2.27(1H,m),2.31(2H,t,J=7.2Hz),3.07(1H,m),3.70(3H,s),5.15-5.30(3H,m),7.48- 7.68(5H,m),7.96-8.02(2H,m).IR(CHCl3)3382,3030,2952,2878,1725,1446,1329,1154,1098/cm.[α]D=-12.1°(CHCl3,C=1.03,22.0℃).No.1a-138CDCl3 300MHz0.95-2.04(14H,m),2.25(1H,m),2.35(2H,t,J=7.2Hz),3.08(1H,m),5.15-5.34(2H,m),5.41(1H,d,J=6.6Hz),7.48-7.68(5H,m),7.98-8.03(2H,m).IR(CHCl3)3370,3242,3022,2950,2870,1707,1445,1408,1329,1154,1099/cm.[α]D=-0.6°(CHCl3,C=1.06,21.5℃) [α]365+30.7°(CHCl3,C=1.06,21.5℃).No.1a-139CDCl3 300MHz0.92-2.19(14H,m),2.27-2.34(3H,m),3.26(1H,m),3.65(3H,s),4.28(2H,s),4.37(1H,d,J=7.4Hz),5.34-5.50(2H,m),7.37-7.62(9H,m).IR(CHCl3)3389,3294,3028,3015,2954,2877,1730,1600,1488,1325,1151,1129/cm.[α]D=-24.8°(CHCl3,C=1.01,24℃).No.1a-140CDCl3 300MHz0.92-2.22(15H,m),2.34(2H,t,J=7.1Hz),3.24 (1H,m),4.29(2H, s),4.81(1H,d,J=7.4Hz),5.32-5.52(2H,m),7.36-7.62(9H,m).IR(CHCl3)3510,3388,3251,3031,3015,2956,2877,2668,1708,1601,1488,1318,1151,1129/cm.[α]D=-24.6°(CHCl3,C=1.02,25℃).No.1a-141CDCl3 300MHz0.92-2.19(15H,m),2.32(2H,t,J=7.2Hz),3.26(1H,m),3.65(3H,s),4.31 (2H,s),4.48(1H,d,J=7.4Hz),5.33-5.49(2H,m),7.42-7.80(8H,m).IR(CHCl3)3388,3285,3018,2955,2877,2225,1730,1597,1479,1320,1152,1129/cm.[α]D=-20.1°(CHCl3,C=0.96,25℃).No.1a-142CDCl3 300MHz0.92-2.22(15H,m),2.35(2H,t,J=6.8Hz),3.25(1H,m),4.32(2H,s),4.86(1H,d,J=7.4Hz),5.33-5.53(2H,m),7.43-7.80(8H,m).IR(CHCl3)3512,3388,3258,3031,3023,3014,2956 2877,2225,1708,1597,1479,1319,1151,1128/cm.[α]D=-19.3°(CHCl3,C=1.09,23℃).No.1a-143CDCl3 300MHz1.00-1.93(14H,m),2.17(1H,m),2.27(2H,t,J=7.2Hz),3.07(1H,m),5.17-5.22(2H,m),5.36(1H,d,J=6.9Hz),7.77(1H,d,J=9.0Hz),8.11-8.17(2H,m),8.36(1H,d.d,J=2.1and9.0Hz),8.51(1H,d,J=1.8Hz),8.65(1H,d,J=2.1Hz).IR(CHCl3)3382,3266,3026,2954,2874,1708,1632,1585,1528,1458,1419,1345,1153/cm.[α]D=+7.6°(CHCl3,C=1.04,22℃).No.1a-144CDCl3 300MHz0.95-1.90(14H,m),2.17(1H,m),2.25(2H,t,J=7.5Hz),3.02(1H,m),5.09(1H,d,J=6.6Hz),5.15-5.21(2H,m),6.72(1H,d,J=8.4Hz),6.85(1H,s),7.54 (1H,d,J=8.4Hz),7.72(1H,d,J=9.0Hz),7.83(1H,d.d,J=1.8and9.0Hz),8.32(1H,d,J=1.8Hz).IR(CHCl3)3380,3260,3022,2948,2868,2352,1709,1636,1460,1425,1313,1291,1265,1148,1130/cm.[α]D=+12.9°(CHCl3,C=1.02,22.5℃).No.1a-145CDCl3 300MHz0.97-1.90(14H,m),2.15(1H,m),2.27(2H,t,J=6.9Hz),3.02(1H,m),3.08(6H,s),5.12(1H,d,J=6.3Hz),5.19-5.25(2H,m),6.78-6.84(2H,m),7.53(1H,d,J=8.7Hz),7.76-7.83(2H,m),8.30(1H,d,J=1.8Hz).IR(CHCl3)3272,3030,2950,2874,1708,1635,1601,1511,1457,1425,1357,1328,1151,1124/cm.[α]D=+6.3°(CHCl3,C=1.04,23℃).No.1a-146CDCl3 300MHz0.95-2.00(14H,m),2.16(1H,m),2.29(2H,t,J=7.2Hz),3.05(1H,m),4.10(3H,s),5.13-5.28(2H,m),5.38(1H,d,J=6.9Hz),7.67-7.74(2H,m),8.08(1H,d.d,J=1.8and9.0Hz),8.11(1H,s),8.61(1H,d,J=1.8Hz).IR(CHCl3)3260,3020,2948,2868,1708,1639,1606,1528,1470,1455,1424,1349,1311,1238,1174,1149,1120,1079,1060,1022/cm.[α]D=+7.8°(CHCl3,C=1.00,23℃).No.1a-147CDCl3 300MHz0.92-1.92(14H,m),2.17(1H,m),2.25(2H,t,J=7.2Hz),3.01(1H,m),3.97(3H,s),5.10-5.27(5H,m),6.92(1H,s),7.29(1H,s),7.52(1H,d,J=8.7Hz),7.82(1H,d.d,J=2.1and8.7Hz),8.33(1H,d,J=2.1Hz).IR(CHCl3)3380,3264,3002,2950,2868,1708,1634,1476,1452,1426,1317,1264,1218,1169,1147,1115,1068,1031/cm.[α]D=+5.6°(CHCl3,C=1.02,23℃).No.1a-148CDCl3 300MHz0.90-1.98(14H,m),2.15(1H,m),2.28(2H,t,J=6.9Hz),2.91 (6 H s),3.03(1H,m),4.01(3H,s),5.15-5.26(3H,m),7.18(1H,s),7.38(1H,s),7.59(1H,d,J=8.7Hz),7.87(1H,d.d,J=2.1和8.7Hz),8.40(1H,d,J=2.1Hz).IR(CHCl3)3384,3266,2956,1709,1632,1602,1495,1473,1458,1430,1317,1231,1148,1121/cm.[α]D=+11.2°(CHCl3,C=1.01,23℃).No.1a-149CDCl3 300MHz0.99-1.90(14H,m),2.17(1H,m),2.28(2H,t,J=7.2Hz),3.00(1H,m),5.13-5.19(2H,m),5.43(1H,d,J=6.0Hz),7.02(1H,d.d,J=2.4和9.0Hz),7.38-7.41(2H,m),7.58(1H,d,J=8.7Hz),7.96(1H,d.d,J=1.8和8.7Hz),8.45(1H,d,J=1.8Hz).IR(CHCl3)3270,3020, 2948,2868,1709,1601,1478,1448,1419,1315,1147,1120/cm.[α]D=-11.4°(CHCl3,C=1.01,23℃).No.1a-150CDCl3 300MHz0.97-1.88(14 H,m),2.12-2.31(3H,m),2.38(3H,s),3.01(1H,m),5.14-5.19(2H,m),5.36(1H,d,J=6.6Hz),7.24(1H,d.d,J=2.4和9.0Hz),7.59(1H,d,J=6.3Hz),7.66(1H,d,J=8.7Hz),7.72(1H,d,J=2.4Hz),8.01(1H,d.d,J=1.8和8.7Hz),8.49(1H,d,J= 1.8Hz).IR(CHCl3)3470,3374,3260,3018,2950,2868,1709,1474,1444,1412,1370,1319,1266,1162,1145,1118/cm.[α]D=+4.9°(CHCl3,C=1.00,24℃).No.1a-151CDCl3 300MHz0.97-1.89(14H,m),2.17(1H,m),2.25(2H,t,J=7.2Hz),3.03 (1H,m),3.92(3H,s),5.15-5.20(2H,m),5.32(1H,d,J=6.6Hz),7.11(1H,d.d,J=2.4and9.3Hz),7.45(1H,d,J=2.4Hz),7.50(1H,d,J=9.3Hz),7.62(1H,d,J=8.7H),7.97(1H,d.d,J=2.1and8.7Hz),8.50(1H,d,J=2.1Hz).IR(CHCl3)3260,3018,2948,1708,1483,1454,1432,1314,1287,1268,1188,1169,1147/cm.lα]D=+4.9°(CHCl3,C=1.01,23.5℃).No.1a-152CDCl3 300MHz0.98-2.04(14H,m),2.15(1H,m),2.30(2H,t,J=6.6Hz),3.04 (1H,m),5.17-5.29(3H,m),7.41(1H,d.d,J=1.5and8.1Hz),7.64-7.68(2H,m),7.92(1H,d,J=8.4Hz),8.00(1H,d.d,J=1.8and8.4Hz),8.49(1H,d,J=1.8Hz).IR(CHCl3)3266,3028,2952,2872,1707,1629,1591,1456,1416,1318,1275,1150/cm.[α]D=+3.2°(CHCl3,C=1.04,23℃).No.1a-153CDCl3 300MHz0.97-1.88(14H,m),2.16(1H,m),2.26 (2H,t,J=7.2Hz),3.03 (1H,m),4.64-4.65(2H,m),5.16-5.50(5H,m),6.13(1H,m),7.14(1H,d.d,J=2.7and9.0Hz),7.46-7.52(2H,m),7.63(1H,d,J=8.7Hz),7.97(1H,d.d,J=1.8and8.7Hz),8.49(1H,d,J=1.8Hz).IR(CHCl3)3374,3260,3020,2948,2868,1708,1599,1478,1446,1414,1314,1284,1268,1184,1148,1120/cm.[α]D=+5.3°(CHCl3,C=1.00,23℃).No.1a-154CDCl3 300MHz0.99-2.00(15H,m),2.26(2H,t,J=7.2Hz),3.03(1H,m),4.07(3H,s),5.23-5.27(2H,m),5.36(1H,d,J=7.2Hz),7.20(1H,s),7.36-7.48(2H,m),7.55-7.58(1H,m),7.91-7.93(1H,m),8.52(1H,s).IR(CHCl3)3362,3257,3020,2948,2868,1708,1637,1602,1579,1488,1457,1437,1413,1345,1318,1301,1276,1182,1104/cm.[α]D=+19.4°(CHCl3,C=1.01,25℃).mp.88-90℃No.1a-155CDCl3 300MHz0.92-2.02(14H,m),2.15(1H,m),2.31 (2H,t,J=7.2Hz),3.01(1H,m),4.10(2H,s),5.10(1H,d,J=6.6Hz),5.18-5.35(2H,m),7.04-7.26(5H,m),7.67-7.76(2H,m).IR(CHCl3)3266,3028,2952,2952,2872,1708,1599,1574,1478,1457,1418,1301,1258,1147,1124,1101,1080/cm.[α]365 +33.4°(CHCl3,C=1.00,23℃).No.1a-156CDCl3 300MHz0.91-2.21(15H,m),2.33(2H,t,J=6.9Hz),3.01(1H,m),5.11(1H,d,J=6.6Hz),5.27-5.35(2H,m),6.85-6.96(5H,m),7.35(1H,d,J=2.1Hz),7.42(1H,d.d,J=2.1and8.7Hz).IR(CHCl3)3384,3263,2957,1708,1587,1489,1462,1416,1290,1222,1151,1123/cm.[α]D=+6.4°(CHCl3,C=1.00,23℃).No.1a-157CDCl3 300MHz0.97-1.91(14H,m),2.18(1H,m),2.26(2H,t,J=6.9Hz),3.04(1H,m),5.18-5.26(3H,m),7.52-7.56(2H,m),7.88-8.00(3H,m),8.25(1H,m),8.69(1H,m).IR(CHCl3)3382,3268,2952,2874,1707,1457,1425,1409,1318,1152/cm.[α]D=+4.4°(CHCl3,C=1.02,22℃). No.1a-158 CDCl3 300MHz 1.02-1.97(14H,m),2.20(1H,m),2.29(2H,t,J=7.2Hz),3.06(1H,m),5.19-5.24 (2H, m),5.58(1H,d,J=6.6Hz),7.62(1H,m),7.72(1H,m),7.86- 7.91 (2H,m),7.96(1H,d,J =7.8Hz),8.04(1H,d.d,J=1.5and8.1Hz),8.34(1H,d,J=1.2Hz). IR(CHCl3)3490,3260,3020,2950,2870,1707,1456,1399,1312,1165/cm. [α]D=-8.3°(CHCl3,C=1.00,23℃). No.1a-159 CDCl3 300MHz 0.92-1.88(14H,m),2.13(1H,m),2.24(2H,m),3.02(1H,m),3.90(3H,s),5.12-5.26(3 H,m),7.29-7.58(4H,m),7.97(1H,d.d,J=1.8and7.5Hz),8.13(1H,d,J=7.5Hz),8.64 (1H,d,J=1.8Hz). IR(CHCl3)3382,3266,3018,2956,1708,1629,1594,1476,1467,1325,1245,1227, 1158,1146/cm. [α]D=+14.6°(CHCl3,C=1.00,22℃). No.1a-160 CDCl3 300MHz 0.93-1.88(14H,m),2.18-2.24(3H,m),3.00(1H,m),5.08-5.2 1(3H,m),7.28-7.33(1 H,m),7.47-7.51(3H,m),7.90(1H,d.d,J=1.5and7.8Hz),8.10(1H,d,J=7.8Hz),8.63 -8.64(2H,m). IR(CHCl3)3465,3380,3275,3020,2957,2876,1708,1627,1604,1495,1473,1457,1328,1240,1222,1156,1149/cm.[α]D=+8.2°(CHCl3,C=1.01,22℃).No.1a-161CDCl3 300MHz0.98-1.88(14H,m),2.17(1H,m),2.24(2H,t,J=7.2Hz),3.05(1H,m),5.16-5.20(2H,m),5.35(1H,d,J=6.6Hz),7.40(1H,m),7.55(1H,m),7.63(1H,d,J=8.1Hz),7.89(1H,d. d,J=1.5and8.1Hz),8.01(1H,m),8.06(1H,d,J=8.1Hz),8.12(1H,d,J=1.5Hz).IR(CHCl3)3478,3266,3028,2952,2874,1708,1454,1417,1323,1196,1148/cm.[α]D=+21.9°(CHCl3,C=1.01,23℃).No.1a-162CDCl3 300MHz0.96-1.98(14H,m),2.02(1H,m),2.25(2H,t,J=7.2Hz),3.05(1H,m),4.10(3H,s),5.14-5.25(2H,m),5.41(1H,d,J=7.2Hz),7.35-7.42(1H,m),7.51-7.64(3H,m),7.94-8.00(1H,m),8.16(1H,s).IR(CHCl3)3368,3274,3028,2952,2874,1708,1633,1583,1465,1452,1438,1413,1315,1151,1103,1053,1024/cm.[α]D=+15.1°(CHCl3,C=1.01,23℃). mp.108-110℃No.1a-163d6-DMSO 300MHz0.97-1.84(14H,m),1.92(1H,m),2.04(2H,t,J=7.5Hz),2.90(1H,m),5.08-5.23 (2H,m),7.32(1H,s),7.38-7.61(2H,m),7.62(1H,s)7.68-7.71(1H,m),7.92(1H,s),8.14-8.17(1H,m),10.7(1H,s),11.9(1H,s).IR(KBr)3350,3295,2952,2874,1707,1636,1601,1466,1431,1389,1315,1251,1174,1146,1106/cm.[α]D=-25.3°(CH3OH,C=1.01,25℃). mp.159-162℃No.1a-164CDCl3 300MHz0.98-1.96(17H,m),2.05(1H,m),2.25(2H,t,J=7.2Hz),3.07(1H,m),4.32(2H,q,J=7.2Hz),5.19-5.23(2H,m),5.31(1H,d,J=7.8Hz),7.38(1H,m),7.41-7.62(3H,m),7.95(1H,m),8.15(1H,s).IR(CHCl3)3360,3018,2946,2870,1709,1633,1457,1445,1425,1394,1314,1176,1152,1105/cm.[α]D=+12.7°(CHCl3,C=1.02,25℃). mp.108-109℃No.1a-165CDCl3 300MHz0.95-1.98(15H,m),2.26(2H,t,J=7.5Hz),3.04(1H,m),4.15 (3H,s),5.20-5.26(2H,m),5.34(1H,d,J=6.9Hz),7.41-7.47(1H,m),7.65-7.68(2H,m),7.89-7.92(1H,m),8.32(1H,s).IR(CHCl3)3366,3087,3022,2957,1708,1632,1538,1463,1408,1364,1346,1308,1227,1212,1205,1167/cm.[α]D=+19.6°(CHCl3,C=1.01,25℃).No.1a-166CDCl3 300MHz0.97-2.02(15H,m),2.27(2H,t,J=6.9Hz),3.07(1H,m),4.14(3H,3),5.21-5.27(2H,m),5.47(1H,d,J=6.9Hz),7.64(1H,s),7.72(1H,d.d,J=0.6和9.0Hz),8.25(1H,s),8.47(1H,d.d,J=2.4and9.0Hz),8.94(1H,d.d,J=0.6和2.4Hz).IR(CHCl3)3373,2957,1708,1639,1587,1528,1467,1428,1415,1345,1221,1184,1155/cm.[α]D=+14.4°(CHCl3,C=0.50,25℃)No.1a-167 CDCl3 300MHz0.92-2.00(14H,m),2.15(1H,m),2.27(2H,t,J=7.2Hz),3.04 (1H,m),3.97(2H,s),5.15-5.30(3H,m),7.35-7.47(2H,m),7.55-7.63(1H,m),7.80-7.96(3H,m),8.05(1H,d,J=0,3Hz).IR(CHCl3)3260,3020,2948,2868,1707,1451,1413,1319,1172,1144,1101,1071/cm.[α]D=+18.2°(CHCl3,C=1.04,22℃).No.1a-168CDCl3 300MHz0.90-1.85(14H,m),2.16(1H,m),2.25(2H,t,J=6.9Hz),3.00(1H,m),5.00-5.19(2H,m),5.35(1H,d,J=6.6Hz),7.25-7.30(1H,m),7.48-7.50(2H,m),7.73(1H,d.d,J=1.5and8.1Hz),8.08-8.14(3H,m),8.93(1H,s).IR(CHCl3)3466,3380,3276,3016,2957,1708,1630,1495,1458,1324,1241,1150/cm.[α]D=+18.0°(CHCl3,C=1.00,22℃).No.1a-169CDCl3 300MHz0.87-1.86(14H,m),2.15(1H,m),2.25(2H,t,J=6.9Hz),2.98(1H,m),3.89(3H,s),5.00-5.22(2H,m),5.27(1H,d,J=6.9Hz),6.88(1H,d.d,J=2.1和8.4Hz),6.94(1H,d,J=2.1Hz),7.69(1H,d.d,J=1.5和7.8Hz),7.92-8.01(3H,m),8.83(1H,s).IR(CHCl3)3465,3378,3276,3022,2957,1708,1630,1609,1569,1459,1433,1314,1281,1229,1151/cm.[α]D=+19.3°(CHCl3,C=1.01,21℃).No.1a-170CDCl3 300MHz0.88-2.25(17H,m),3.04(1H,m),3.84(3H,s),3.95(3H,s),5.06-5.26(3H,m),6.87-6.93(2H,m),7.69(1H,d.d,J=1.6和8.2Hz),7.93-9.05(3H,m).IR(CHCl3)3026,2957,1708,1630,1601,1460,1331,1243,1224,1152/cm.[α]D=+17.2°(CHCl3,C=1.00,22℃).No.1a-171CDCl3 300MHz0.95-2.00(14H,m),2.16-2.32(3H,m),2.66(3H,s),3.14(1H,m),3.68(3H,s),5.09(1H,d,J=6.8Hz),5.10-5.28(2H,m),7.45(1H,d.d.,J=1.8&8.6Hz),7.75-7.84(2H,m).IR(CHCl3)3374,3018,2946,2868,1725,1585,1513,1436,1340,1278,1153,1112/cm.[α]D=-14.7°(CHCl3,C=1.07,25.0℃).No.1a-172CDCl3 300MHz0.97-2.02(14H,m),2.23(1H,m),2.28(2H,t,J=7.2Hz),2.66(3H,s),3.14(1H,m),5.12-5.22(2H,m),5.41(1H,d,J=7.2Hz),7.45(1H,d.d.,J=2.1&8.7Hz),7.76(1H,d,J=8.7Hz),7.78(1H,d,J=2.1Hz).IR(CHCl3)3372,3250,3022,2950,2868,1707,1514,1419,1336,1279,1154,1112/cm.[α]D=-4.1°(CHCl3,C=1.08,26.0℃) m.p.141-143℃No.1a-173CDCl3 300MHz1.15-2.42(17H,m),2.91(1H,m),5.15(1H,d,J=4.2Hz),5.25-5.40(2H,m),7.85(1H,t,J=7.2Hz),8.00(1H,t,J=8.1Hz),8.15-8.20(2H,m),8.67(1H,d,J=8.1Hz),8.73(1H,d,J=8.1Hz),8.83(1H,s),9.43(1H,s).IR(KBr)3422,3269,3046,2952,2871,1711,1617,1447,1333,1243,1161,1146/cm.[α]D=-41.0°(CH3OH,C=1.01,23℃).No.1a-174CDCl3+d6-DMSO 300MHz1.00-1.92(14H,m),2.20(2H,t,J=6.6Hz),2.35(1H,m),2.92(1H,m),5.05-5.22(2H,m),6.63(1H,d,J=5.4Hz),7.77-7.92(3H,m),8.31(1H,d.d,J=1.8和8.7Hz),8.59(1H,d,J=8.7Hz),8.73(1H,d,J=8.7Hz),9.01(1H,s),9.55(1H,d,J=1.8Hz).IR(KBr)3433,3252,2952,2871,1696,1578,1423,1335,1308,1219,1185,1160,1106/cm.[α]D=-19.3°(DMSO,C=0.50,23℃).No.1a-175CDCl3 300MHz0.96-1.87(14H,m),2.20-2.25 (3H,m),2.95(1H,m),3.66 (3H,s),4.74(1H,d,J=6.6Hz),5.10-5.12(2H,m),6.88(1H,d,J=1.2Hz),7.37-7.50(3H,m),7.56(1H,dd,J=8.7,1.5Hz),7.68-7.77(3H,m),8.06(1H,s),9.44(1H,dd,J=1.2Hz).IR(CHCl3)3462,3374,3026,3006,2952,2872,1724,1610,1580,1484,1452,1358,1309,1147.[α]D=+16.4°(CHCl3,C=1.05,26℃). mp.130-132℃.No.1a-176CDCl3+CD3OD 300MHz 1.00-2.02(14H,m),2.22(1H,m),2.29(2H,t,J=6.9Hz),2.88 (1H,m),5.16-5.26(2H,m),6.87(1H,s),7.28-7.57(4H,m),7.69(1H,d,J=8.4Hz),7.75-7.78(2H,m),7.99(1H,s).IR(KBr)3254,2944,1704,1484,1453,1358,1305,1147.[α]D=+13.0°(CH3OH,C=1.02,24℃),mp.160-161℃No.1a-177CDCl3 300MHz0.96-1.88(14H,m),1.88-2.26(3H,m),2.94(1H,m),3.67(3H,s),3.87(3H,s),4.67(1H,brs),5.08-5.14(2H,m),6.77(1H,d,J=1.5Hz),6.99-7.02(2H,m),7.53-7.57(1H,m),7.65-7.70(3H,m),8.00(1H,s),9.27(1H,brs).IR(CHCl3)3426,3376,3006,2952,1724,1610,1495,1438,1357,1308,1282,1249,1177,1147/cm.[α]D=+18.1°(CHCl3,C=1.02,22℃).No.1a-178CDCl3+CD3OD 300MHz0.96-1.91(14H,m),2.19(1H,m),2.27(2H,t,J=6.0Hz),2.85(1H,m),3.87(3H,s),5.16-5.23(2H,m),6.99-7.02(2H,m),7.41(1H,m),7.64-7.73(3H,m),7.92(1H,m).IR(CHCl3)3366,3261,3004,2954,2873,1705,1611,1496,1458,1438,1304,1286,1253,1180,1149,1128/cm.[α]D=+14.6°(CHCl3,C=1.02,22℃).No.1a-179CDCl3+CD3OD300MHz0.96-1.87(14H,m),2.15-2.23(3H,m),2.93(1H,m),3.85(3H,s),5.10-5.16(2H,m),6.90-6.93(2H,m),7.50(1H,m),7.60-7.65(3H,m),7.91(1H,d,J=0.9Hz).IR(CHCl3)3369,3270,2950,2873,1719,1612,1498,1456,1440,1359,1306,1269,1219,1146,1127/cm.[α]D=+18.1°(CH3OH,C=1.00,22℃).No.1a-180CDCl3+CD3OD300MHz1.03-1.86(14H,m),2.08-2.17(3H,m),2.91(1H,m),5.06-5.10(2H,m),6.76(1H,m),6.86-6.90(2H,m),7.48(1H,m),7.61-7.69(3H,m),7.89(1H,m).IR(CHCl3)3360,3259,2954,2873,1706,1612,1497,1457,1360,1306,1272,1230,1176,1148,1126/cm.[α]D=+20.3°(CH3OH,C=1.00,22℃).No.1a-181CDCl3 300MHz0.97-1.96(14H,m),2.15(1H,m),2.29(2H,t,J=6.9Hz),3.05(1H,m),3.81(3H,s),5.08(1H,d,J=6.9Hz),5.23-5.25(2H,m),6.62(1H,s),7.47-7.54(5H,m),7.59(1H,m),7.70(1H,m),7.97(1H,m).IR(CHCl3)3380,3260,3020,2946,2868,1708,1466,1388,1328,1149/cm.[α]D=+32.9°(CHCl3,C=1.07,22℃).No.1a-182CDCl3 300MHz0.94-1.90(14H,m),2.25(2H,t,J=7.5Hz),2.30(1H,m),2.98(1H,m),3.70(3H,s),4.83(1H,d,J=6.6Hz),5.13-5.16(2H,m),6.95(1H,d,J=1.5Hz),7.11-7.23(2H,m),7.43(1H,d,J=8.1Hz),7.65(1H,d,J=8.1Hz),7.79-7.93(4H,m),9.08(1H,br).IR(CHCl3)3458,3372,3020,3002,2946,2868,1719,1598,1452,1422,1321,1300,1157/cm.[α]D=-6.6°(CHCl3,C=1.00),mp150-151℃No.1a-183CDCl3 300MHz0.95-1.94(14H,m),2.26(1H,m),2.28(2H,t,J=7.5Hz),3.00(1H,m),5.16-5.19(2H,m),5.32(1H,d,J=7.2Hz),6.93(1H,d,J=1.2Hz),7.13(1H,m),7.22(1H,dd,J=7.8,6.6Hz),7.42(1H,d,J=7.8Hz),7.63(1H,d,J=7.8Hz),7.76 (2H,d,J=8.4Hz),7.90(2H,d,J=8.4Hz),8.95(1H,br).IR(CHCl3)3458,3374,3260,3020,3002,2948,2868,1708,1598,1452,1422,1301,1156/cm.[α]D=+17.9°(CHCl3,C=1.01,22℃).No.1a-184CDCl3 200MHz0.92-2.00(14H,m),2.20(1H,m),2.34(2H,t,J=6.8Hz),3.05(1H,m),5.20-5.36(3H,m),7.39 -7.44(2H,m),7.61-7.66(1H,m),7.80-7.84(1H,m),8.05(2H,d,J=8.6Hz),8.40(2H,d,J=8.6Hz).IR(CHCl3)3384,3271,3019,2958,1709,1615,1599,1551,1453,1405,1344,1326,1243,1163/cm.[α]D=+18.5°(CHCl3,C=1.00,21℃).No.1a-185CDCl3 300MHz0.89-2.20(15H,m ),2.26(2H,d.t,J=2.1and7.2Hz),2.99(1H,m),5.08(1H,d,J=6.3Hz),5.09-5.24(2H,m),6.90(1H,d,J=1.2Hz),7.32-7.48(4H,m),7.64-7.72(3H,m),8.20(1H,d,J=1.2Hz),9.00(1H,s).IR(CHCl3)3464,3375,3275,3022,2956,1707,1605,1490,1449, 1356,1322,1219,1147,1131/cm.[α]D=+21.6°(CHCl3,C=1.01,23℃).No.1a-186CDCl3300MHz1.36-2.24(14H,m),2.31(2H,t,J=7.4Hz),2.49(1H,brs),3.37(1H,m),3.67(3H,s),5.38-5.50(2H,m),7.40-7.68(9H,m).IR(CHCl3)3375,1727,1602,1435,1362,1221,1207,1168,1045/cm.No.1a-187CDCl3300MHz1.10-2.25(14H,m),2.36(2H,t,J=7.2Hz),2.47(1H,m),3.37(1H,m),5.35-5.54(2H,m),5.62(1H,d,J=7.2Hz),7.39-7.70(9H,m).IR(CHCl3)3674,3496,3376,3234,3012,2952,2880,2650,1725(sh),1709,1602,1485,1420,1360,1167/cm.[α]D=+32°(CHCl3,C=1.69).No.1a-188CDCl3 200MHz0.86-1.92(14H,m),2.22(3H,m),2.36(3H,s),2.95(1H,m),3.67(3H,s),3.93(3H,s),4.81(1H,d,J=6.2Hz),5.04-5.20(2H,m),7.02-7.05(2H,m),7.31(1H,d,J=8.6Hz),7.39(1H,d,J=7.8Hz),7.79-7.89(3H,m).IR(CHCl3)3385,3286,3029,3019,3015,2954,2877,1718,1617,1598,1567,1507,1311,1269,1153/cm.[α]D=-29.4°(CHCl3,C=1.01,25℃).No.1a-189[α]D=-7.7°(CHCl3,C=1.00,24℃).No.1a-190[α]D=-17.3°(CHCl3,C=1.00,24℃).No.1a-191CDCl3 300MHz0.95-2.20(14H,m),2.30(1H,m),2.36(2H,d,J=6.9Hz),3.21(1H,m),4.25(2H,s),5.07(1H,d,J=7.8Hz),5.35-5.48(2H,m),7.25(1H,dd,J=1.8和8.1Hz),7.32-7.35(2H,m),7.59(1H,d,J=8.1Hz),7.94(1H,s),8.14(1H,d,J=2.7Hz),8.23(1H,d.d,J=2.7and8.7Hz).IR(CHCl3)3386,3026,3015,2957,2877,2633,1702,1617,1573,1530,1348,1123/cm.[α]D=-6.1°(CHCl3,C=1.01,25℃).No.1a-192CDCl3 300MHz0.92-2.20(14H,m),2.13(3H,m),3.23(1H,m),3.64(3H,s),3.94(3H,s),4.22(2H,s),4.36(1H,d,J=7.8Hz),5.37-5.42(2H,m),7.16-7.42(6H,m),7.53(1H,d,J=8.4Hz),7.94(1H,s).IR(CHCl3)3389,3022,3013,2953,2877,1716,1616,1560,1485,1340,1326,1124/cm.[α]D=-15.2°(CHCl3,C=1.01,25℃).No.1a-193CDCl3 300MHz0.92-2.20(14H,m),2.25(1H,m),2.35(2H,t,J=7.2Hz),3.17(1H,m),4.22(2H,s),4.91(1H,d,J=7.5Hz),5.37-5.42(2H,m),7.13-7.43(6H,m),7.60(1H,d,J=8.1Hz),8.05(1H,s).IR(CHCl3)3511,3387,3029,3020,3011,2957,2877,2651,1698,1614,1560,1505,1320,1280,1252,1126/cm.[α]D=-0.9°(CHCl3,C=1.00,25℃).No.1b-1CDCl3 300MHz0.98-1.56(15H,m),1.85-1.90(5H,m),2.23(1H,m),3.05 (1H,m),3.66(3H,s),4.77(1H,d,J=6.0Hz),5.08-5.28(2H,m),7.46(3H,m),7.38-7.54(2H,d,J=7.5Hz),7.72(2H,d,J=8.4Hz),7.93(2H,d,J=8.4Hz).IR(CHCl3)3384,3028,2952,2876,1719,1595,1391,1322,1155/cm.[α]436 +4.0~+6.0(CHCl3,C=1.00,23℃).mp.96-98℃No.1b-2CDCl3 300MHz0.98-1.52(15H,m),1.85-1.90(5H,m),2.17(1H,m),3.00(1H,m),3.67(3H,s),4.05(2H,s),4.83(1H,d,J=6.0Hz),5.05-5.23(2H,m),7.14(2H,d,J=7.2Hz),7.17-7.32(5H,m),7.78(2H,d,J=8.4Hz).IR(CHCl3)3384,3026,2952,2874,1719,1595,1453,1407,1320,1180/cm.[α]D=+2.5°(CHCl3,C=1.02,24℃).No.1b-3CDCl3 300MHz0.96-2.05(20H,m),2.07(1H,m),3.07(1H,m),4.04(2H,s),5.21-5.35(2H,m),5.55(1H,d,J=6.9Hz),7.14(2H,d,J=6.6Hz),7.20-7.32(5H,m),7.78(2H,d,J=8.1H).IR(CHCl3)3250,3022,2950,1699,1596,1495,1453,1405,1318,1153/cm.[α]D=+17.1°(CHCl3,C=1.01,25℃).mp.129-131℃.No.1b-4CDCl3 200MHz0.90-2.10(15H,m),1.19(3H,s),1.20(3H,s),3.11(1H,m),5.24-5.32(2H,m),5.70(1H,d,J=6.6Hz),7.38-7.68(4H,m),7.96-8.04(2H,m),8.53(1H,d,J= 1.4Hz).IR(CHCl3)3384,3246,2958,1701,1632,1595,1468,1445,1322,1216,1202,1190,1155,1122/cm.[α]D=+10.8°(CHCl3,C=0.51,23℃).No.1b-51.02-2.10(15H,m),1.16(6H,s),3.02(1H,m),4.09(3H,s),5.23-5.28(2H,m),5.76(1H,d,J=7.2Hz),7.36-7.63(4H,m),7.97(1H,d,J=7.8Hz),8.16(1H,s).IR(CHCl3)3369,2959,1702,1635,1585,1468,1454,1441,1415,1318,1222,1189,1170,1154/cm.[α]D=+9.9°(CHCl3,C=1.00,23℃).No.1c-1CDCl3 300MHz1.10-2.02(14H,m),2.27(2H,t,J=7.5Hz),2.50(1H,m),2.89(3H,s),3.31(1H,m),3.64(3H,s),5.16-5.30(2H,m),7.34-7.42(3H,m),7.50-7.59(2H,m),7.62-7.68(2H,m),7.76-7.82(2H,m).IR(CHCl3)3020,2946,2868,2212,1727,1596,1495,1437,1339,1156,1135,1084/cm.[α]D=-16.1°(CHCl3,C=1.05,25.0℃).m.p. 100-102℃No.1c-2CDCl3 300MHz1.10-2.05(14H,m),2.23(2H,t,J=7.5Hz),2.53(1H,m),2.91(3H,s),3.35(1H,m),3.62(3H,s),5.02-5.30(2H,m),7.50-7.60(3H,m),7.90-8.08(6H,m).IR(CHCl3)3016,2946,2868,1728,1437,1398,1340,1160,1086/cm.[α]D=-32.5°(CHCl3,C=1.00,25.0℃).No.1c-3CD3OD 300MHz1.15-2.05(14H,m),2.13(2H,t,J=7.2Hz),2.47(1H,m),2.91(3H,s),3.27(1H,m),4.90-5.30(2H,m),7.37-7.44(3H,m),7.53-7.61(2H,m),7.71-7.77(2H,m),7.81-7.87(2H,m).IR(KBr)3412,2999,2951,2871,2217,1560,1399,1243,1159,1137,1103,1084.[α]D=-8.6°(CH3OH,C=1.03,23℃).No.1d-1CDCl3 300MHz1.00-2.16(15H,m),2.36(2H,t,J=7.2Hz),3.17(1H,m),3.33(3H,s),5.23-5.43(3H,m),7.51-7.59(3H,m),7.91-8.10(6H,m),9.02(1H,brs).IR(CHCl3)3382,3268,3028,2954,2874,1715,1442,1400,1337,1162,1120,1089/cm.[α]D=+40.0°(CHCl3,C=0.53,22℃).No.1d-2CDCl3 300MHz1.03-2.30(17H,m),3.03(1H,m),4.03(2H,s),5.26(2H,m),5.84(1H,br),5.25-5.29(1H,d,J=6.6Hz),6.03(1H,br),7.14(2H,d,J=8.1Hz),7.26-7.31(5H,m),7.80(2H,d,J=8.1Hz).IR(CHCl3)3376,3002,2946,1669,1595,1492,1454,1406,1318,1154/cm.[α]D=+4.3°(CHCl3,C=1.00,23℃).No.1d-3CDCl3 300MHz0.96-2.17(17H,m),2.33(2H,t,J=6.9Hz),3.01(1H,m),4.04(2H,s),5.10(1H,d,J=6.6Hz),5.21-5.26(2H,m),7.14(2H,d,J=8.7Hz),7.16-7.32(5H,m),7.78(2H,d,J=8.4Hz).IR(CHCl3)3260,3020,2946,1711,1596,1492,1457,1407,1318,1154/cm.[α]D=+9.3°(CHCl3,C=1.09,25℃).No.1d-4CDCl3 300MHz0.95-2.14(15H,m),2.34(2H,t,J=7.2Hz),3.09(1H,m),3.30(3H,s),4.04(2H,s),5.19(1H,d,J=7.2Hz),5.22-5.39(2H,m),7.10-7.35(7H,m),7.8 1(2H,d,J=8.1Hz),9.10(1H,brs).IR(CHCl3)3382,3260,3028,2952,2874,2670,1713,1595,1492,1450,1405,1338,1160,1120,1092/cm.[α]D=+22.2°(CHCl3,C=1.07,22℃).No.1d-5CDCl3 300MHz1.00-2.10(14H,m),2.30-2.39(3H,m),3.15(1H,m),3.35(3H,s),5.18-5.40(3H,m),7.41(1H,d.t.,J=0.9and7.8Hz),7.50-7.69(3H,m),7.88-8.15(2H,m),8.60(1H,d,J=1.5Hz),9.06(1H,s).IR(CHCl3)3382,3268,3028,2954,2874,1714,1442,1402,1338,1188,1155,1121,1072/cm.[α]D=+15.3°(CHCl3,C=1.00,22℃).No.1e-1CDCl3 300MHz1.19-2.45(19H,m),2.58(1H,m),5.63(1H,d,J=3.0Hz),7.42- 7.65(4H,m),7.94-8.03(2H,m),8.49-8.50(1H,m).IR(CHCl3)3293,3024,1710,1595,1584,1467,1445,1410,1324,1222,1213,1206,1190,1160/cm.[α]D=-41.1°(CHCl3,C=1.01,23℃).No.1e-2CDCl3 300MHz1.10-2.25(19H,m),2.94(1H,m),4.12(3H,s),5.53(1H,d,J=7.2Hz),7.39(1H,m),7.50-7.62(3H,m),7.96(1H,d,J=7.5Hz),8.13(1H,s).IR(CHCl3)3367,3025,2955,1711,1634,1600,1584,1468,1454,1440,1415,1342,1317,1222,1189,1157/cm.[α]D=+1.2°(CHCl3,C=1.00,25℃).No.1f-1CDCl3 300MHz1.08-2.47(19H,m),2.56(1H,m),3.52(2H,t,J=6.6Hz),5.59(1H,d,J=2.4Hz),7.40-7.66(4H,m),7.95-8.04(2H,m),8.50(1H,d,J=1.8Hz).IR(CHCl3)3624,3383,3295,2950,2877,1705,1595,1584,1468,1445,1405,1347,1337,1324,1224,1190,1160/cm.[α]D=-54.1°(CHCl3,C=1.01,23℃).No.1f-2CDCl3 300MHz1.08-2.24(19H,m),2.94(1H,m),3.53(2H,t,J=6.3Hz),4.13(3H,s),5.47(1H,d,J=6.6Hz),7.36-7.63(4H,m),7.96(1H,d,J=6.3Hz),8.14(1H,s).IR(CHCl3)3625,3368,3025,3013,2949,2877,1710,1634,1600,1584,1468,1454,1440,1415,1342,1317,1232,1220,1189,1157/cm.[α]D=-5.6°(CHCl3,C=1.00,25℃).No.1g-1CDCl3 200MHz1.17-2.34(15H,m),3.22(1H,m),5.10-5.16(2H,m),5.45(1H,d,J=7.0Hz),7.35-7.66(4H,m),7.95-8.01(2H,m),8.51(1H,d,J=2.0Hz).IR(CHCl3)3383,3275,2959,1707,1595,1584,1468,1445,1425,1319,1269,1248,1190,1149,1123/cm.[α]D=+64.3°(CHCl3,C=1.01,23℃).No.1g-2CDCl3 300MHz1.10-2.15(13H,m),2.36(2H,t,J=7.2Hz),3.21(1H,m),4.09(3H,s),5.10-5.22(2H,m),5.43(1H,d,J=7.8Hz),7.36-7.62(4H,m),7.96(1H,d,J=7.8Hz),8.12(1H,s).IR(CHCl3)3366,2959,1708,1635,1600,1585,1467,1454,1440,1415,1345,1318,1233,1189,1152/cm. [α]D=+103.1°(CHCl3,C=1.01,23℃).No.1h-1CDCl3 300MHz0.90-1.60(17H,m),1.83(1H,m),2.11(1H,m),2.22(2H,t,J=7.2Hz),3.07(1H,m),5.11(1H,d,J=7.2Hz),7.38-7.47(1H,m),7.50-7.60(1H,m),7.60-7.72(2H,m),7.88-8.12(2H,m),8.54 (1H,d,J=0.9Hz).IR(CHCl3)3382,3274,2926,1707,1464,1442,1318,1266,1188,1153,1121,1105,1071,1019/cm.[α]D=-2.8°(CHCl3,C=1.01,23℃).No.1i-1[α]365+50.9°(CHCl3,C=1.01,24℃).No.1i-2CDCl3 300MHz0.98-1.70(11H,m),1.80-2.00(5H,m),2.19(1H,m),3.03(1H,m),3.64(2H,t,J=6.6Hz),4.05(2H,s),4.69(1H,d,J=6.6Hz),5.15(1H,m),5.25(1H,m),7.16(2H,d,J=7.2Hz),7.27-7.32(5H,m),7.77(2H,d,J=8.4Hz).IR(CHCl3)3376,3004,2946,2316,1596,1492,1453,1407,1318,1154/cm.[α]D=+3.5°(CHCl3,C=1.00,22℃).mp.80.5-82.0℃No.1j-1[α]436=-7.5±0.5°(CHCl3,C=1.05,22℃).No.1j-2[α]D=-9.7±0.5°(CHCl3,C=1.06,22℃).No.1j-3[α]D=+15.0±0.5°(CH3OH,C=1.06,24.5℃).mp.101-108℃No.1j-4[α]D=-28.0±0.6°(CHCl3,C=1.06,24℃).mp.159-161℃1j-5[α]D=-12.5±0.5°(CHCl3,C=1.04,23℃).mp.99-101℃No.1j-6CDCl3 300MHz0.90-2.03(14H,m),2.20(1H,m),2.30(2H,t,J=7.3Hz),3.00(1H,m)3.68(3H,s),4.76(1H,d,J=6.8Hz),5.13-5.35(2H,m),7.01-7.08(4H,m),7.19-7.26(1H,m),7.37-7.46(2H,m),7.80-7.84(2H,m).IR(CHCl3)3382,3280,3080,3016,2952,2900,1727,1582,1486,1432,1322,1150/cm.[α]D=-31.0°(CHCl3,C=1.05,26℃).No.1j-7CDCl3 300MHz0.91-2.09(14H,m),2.15(1H,m),2.35(2H,t,J=7.5Hz),3.01(1H,m),5.17(1H,d,J=6.8Hz),5.21-5.34(2H,m),7.01-7.08(4H,m),7.15-7.27(1H,m),7.37-7.43(2H,m),7.80-7.85(2H,m).IR(CHCl3)3474,3386,3270,3024,2958,2900,2675,1711,1584,1488,1420,1323,1298,1150/cm.[α]D=-13.4°(CHCl3,C=1.01,26℃).No.1j-8CDCl3 300MHz0.95-2.14(13H,m),2.30(2H,t,J=7.5Hz),2.36(1H,m),2.84(1H,m),2.91(1J=4.8Hz),3.66 (3H,s),5.33-5.52(2H,m),6.82-6.87(1H,m),6.93-7.00(2H,m),7.09-7.15(4H,m),7.28-7.36 (2H,m),7.54-7.59(1H,m).IR(CHCl3)3350,3010,2950,2880,1728,1603,1582,1489 1461,1438,1360,1160/cm.[α]D=+75.1°(CHCl3,C=1.13,26℃).No.1j-9CDCl3 300MHz0.95-2.03(14H,m),2.20(1H,m),2.29(2H,t,J=7.5Hz),3.06(1H,m),3.68(3H,s),4.98(1H,d,J=7.4Hz),5.14-5.34(2H,m),7.46-7.54(2H,m),7.60-7.68(1H,m),7.75-7.80(2H,m),7.88-7.92(2H,m),7.99-8.03(2H,m).IR(CHCl3)3384,3280,3020,2960,2888,1727,1662,1600,1316,1273,1163/cm.[α]D=-41.0°(CHCl3,C=1.17,26℃).No.1j-10CDCl3+CD3OD 300MHz0.94-2.08(14H,m),2.21(1H,m),2.34(2H,t,J=6.2Hz),3.04(1H,m),5.21-5.35(2H,m),5.40(1H,m),7.49-7.58(2H,m),7.64-7.68(1H,m),7.79-8.06(6H,m).IR(CHCl3)3475,3370,3250,3018,2956,2976,2650,1709,1662,1595,1445,1420,1395,1317,1274,1163/cm.[α]D=-17.1°(CHCl3,C=1.13,25℃).No.1j-11CDCl3 300MHz1.06-1.98(14H,m),2.24-2.29(3H,m),3.13(1H,m),3.66(3H,s),5.10-5.24(2H,m),5.40(1H,d,J=6.3Hz),7.39-7.49(3H,m),7.59-7.64(3H,m),7.80-7.83(2H,m),8.08-8.11(1H,m).IR(CHCl3)3302,3012,2948,2905,1727,1661,1593,1435,1332,1312,1287,1271,1165/cm.[α]D=+15.6°(CHCl3,C=1.03,26℃).No.1j-12 CDCl3 300MHz 1.08-1.98(14H,m),2.23(1H,m),2.33(2H,t,J=7.5Hz),3.16(1H,m),5.18-5.26(2H,m),5.39-5.45(1H,m),7.39-7.49(3H,m),7.60-7.64(3H,m),7.80-7.83(2H,m),8.09-8.12(1H,m).IR(CHCl3)3325,3022,2956,2872,2680,1708,1662,1603,1598,1425,1340,1316,1288,1271,1165/cm.[α]D=+9.7°(CHCl3,C=0.52,25℃).No.1j-13CDCl3 300MHz0.95-2.00(14H,m),2.20(1H,m),2.27(2H,t,J=6.3Hz),3.03(1H,m),3.67(3H,s),4.99(1H,d,J=6.6Hz),5.12-5.31(2H,m),7.47-7.55(2H,m),7.60-7.69(2H,m),7.76-7.81(2H,m),7.96-8.05(1H,m),8.08-8.14(1H,m),8.27-8.28(1H,m).IR(CHCl3)3674,3538,3376,3276,3012,2948,2860, 1726,1662,1595,1440,1335,1317,1297,1274,1166,1150/cm.[α]D=+10.2°(CHCl3,C=1.00,25℃).No.1j-14CDCl3 300MHz0.93-2.08(14H,m),2.21(1H,m),2.32(2H,t,J=6.3Hz),3.00(1H,m),5.20-5.36(2H,m),5.38(1H,d,J=6.2Hz),7.50-7.55(2H,m),7.63-7.71(2H,m),7.77-7.81(2H,m),7.99-8.04(1H,m),8.10-8.18(1H,m),8.32-8.36(1H,m).IR(CHCl3)3674,3480,3374,3258,3012,2950,2875,2650,1709,1662,1598,1418,1335,1317,1274,1143/cm.[α]D=+61.0°(CHCl3,C=1.19,25℃).No.1j-15CDCl3 300MHz0.90-2.00(14H,m),2.19(1H,m),2.30(2H,t,J=7.3Hz),3.01(1H,m),3.67(3H,s),4.82(1H,d,J=6.6Hz),5.14-5.34(2H,m),7.36-7.39(3H,m), 7.53-7.57(2H,m),7.62-7.66(2H,m),7.83-7.88(2H,m).IR(CHCl3)3376,3276,3010,2948,2868,2212,1727,1597,1500,1437,1325,1161/cm.[α]D=-7.2°(CHCl3,C=1.00,26℃).No.1j-16CDCl3 300MHz0.93-2.03(14H,m),2.15(1H,m),2.36(2H,t,J=7.5Hz),3.05(1H,m),5.20-5.40(3H,m),7.36-7.39(3H,m),7.55-7.66(4H,m),7.84-7.88(2H,m).IR(CHCl3)3470,3376,3260,3012,2950,2868,2675,2212,1708,1596,1503,1416,1396,1322,1160.[α]D=-22.4°(CHCl3,C=1.00,26℃).No.1j-17CDCl3 300MHz1.00-1.60(9H,m),1.79-1.89(5H,m),2.17(1H,brs),2.23(2H,t,J=7.2Hz),3.03(1H,m),5.10-5.23(2H,m),5.49(1H,d,J=6.6Hz),7.40(1H,t,J=7.4Hz),7.53(1H,t,J=7.2Hz),7.60-7.68(2H,m),7.98-8.03(2H,m),8.55(1H,d,J=1.5Hz).IR(CHCl3)3516,3384,3270,2666,1708,1632,1595,1584,1467,1445,1425,1374,1345,1321,1269,1248,1218/cm.[α]D=-7.8°(CHCl3,C=1.01,22℃).No.1j-18CDCl3 300MHz0.90-2.03(14H,m),2.19(1H,m),2.30(2H,t,J=7.5Hz),3.00(1H,m),3.67(3H,s),4.80(1H,d,J=6.4Hz),5.14-5.35(2H,m),6.99-7.04(2H,m),7.16-7.22(2H,m),7.34-7.49(4H,m),7.57-7.61(1H,m).IR(CHCl3)3376,3276,3012,2948,2875,1727,1583,1488,1471,1432,1330,1311,1150/cm.[α]D=+54.0°(CHCl3,C=0.99,25℃).No.1j-19CDCl3 300MHz0.91-2.09(14H,m),2.15(1H,m),2.34(2H,t,J=7.5Hz),3.01(1H,m),5.16(1H,d,J=6.6Hz),5.24-5.40(2H,m),7.01-7.08(2H,m),7.15-7.25(2H,m),7.35- 7.53(4H,m),7.59-7.65(1H,m).IR(CHCl3)3470,3376,3260,3012,2950,2875,2640,1708,1583,1488,1471,1430,1335,1305,1149/cm.[α]D=-21.0°(CHCl3,C=1.30,25℃).No.1j-20CDCl3 300MHz1.17(1H,m),1.26-1.34(2H,m),1.54-2.24(11H,m),2.31(2H,t,J=7.4Hz),2.48(1H,brs),3.37(1H,m),3.67(3H,s),5.35-5.50(2H,m),7.39-7.68(9H,m).IR(CHCl3)3377,1727,1601,1435,1362,1168/cm.No.1j-21CDCl3 300MHz1,10-2.25(14H,m),2.36(2H,t,J=7.2Hz),2.47(1H,m),2.89(1H,m),5.35-5.53(2H,m),5.63(1H,d,J=7.2Hz),7.40-7.71(9H,m).IR(CHCl3)3674,3496,3374,3234,3010,2952,2870,2640,1730(sh),1710,1605,1485,1425,1360,1167/cm.[α]D=-43.0°(CHCl3,C=1.01,25℃).No.1j-22CDCl3 300MHz0.98-1.95(14H,m),2.25-2.31(3H,m),2.95(1H,m),5.19-5.30(2H,m),5.33(1H,d,J=3.9Hz),6.58(1H,d,J=7.5Hz),6.80(1H,t,J=7.5Hz),6.99-7.05(1H,m),7.44-7.53(6H,m),7.60-7.73(9H,m),7.94-7.73(3H,m),8.23-8.26(2H,m),10.66(1H,s).IR(CHCl3)3475,3372,3260,3008,2952,2868,2722,1725,1710(sh),1663,1590,1571,1525,1448,1437,1345,1314,1161,1112/cm.[α]D=+12.9°(CHCl3,C=0.12,23℃).No.1j-23CDCl3 300MHz0.94~1.94(14H,m),2.23-2.30(3H,m),2.98(1H,m),3.68(3H,s),5.09 (1H,d,J=6.2Hz),5.15-5.28(2H,m),7.14-7.22(1H,m),7.34-7.42(2H,m),7.68-7.73(2H,m),7.89-8.03(4H,m),8.51(1H,s).IR(CHCl3)3372,3275,1724,1673,1599,1438,1320,1161/cm.[α]D=+17.0°(CHCl3,C=1.38,25℃).No.1j-24CDCl3+CD3OD 300MHz0.96-2.05(14H,m),2,25-2.34(3H,m),2.92(1H,m),5.16- 5.34(2H,m),7.14-7.22(1H,m),7.29-7.42(2H,m),7.70(2H,d,J=7.6Hz),7.92-8.05(4H,m).IR(CHCl3)3616,3426,3375,3010,2950,2828,2645,1708,1672,1599,1439,1323,1161/cm.[α]D=+21.0°(CH3OH,C=1.00,22℃).No.1j-25CDCl3 300MHz1.03(1H,m),1.18-2.01(13H,m),2.20(1H,brs),2.27(2H,t,J=7.4Hz),3.08(1H,m),3.66(3H,s),5.11(1H,d,J=6.6Hz),5.14-5.34(2H,m),7.54- 7.62(3H,m),8.04-8.32(6H,m). IR(CHCl3)3384,3278,1726,1605,1484,1448,1331,1161/cm. No.1j-26 CDCl3+CD3OD 300MHz 1,03-2.10(14H,m),2.22(1H,m).2.31(2H,t,J=7.5Hz),2.98(1H,m),5.23-5.38(2H, m),7.55-7.66(3H,m),8.05-8.08(2H,m),8.14-8.18(2H,m),8.28-8.31(2H,m). IR(Nujol)3260,2720,2660,1711,1545,1460,1317,1163/cm. [α]D=+15.8°(CH3OH,C=1.01,22℃).No.1j-27[α]D=+16.7°(CHCl3,C=1.00,23℃).No.1j-28CDCl3 300MHz1.01(1H,m),1.14-1.29(2H,m),1.46-2.19(11H,m),2.33(2H,t,J=7.2Hz),2.41(1H,brs),3.18-3.21(5H,m),3.68(3H,s),3.73-3.76(4H,m),4.37(1H,d,J=7.2Hz),5.35- 5.45(2H,m).IR(CHCl3)3392,1727,1435,1335,1148/cm.[α]D=+10.7°(CHCl3,C=1.39,26℃).No.1j-29CDCl3 300MHz1.00(1H,m),1.20-1.29(2H,m),1.48-2.25(12H,m),2.37(2H,t,J=7.2Hz),3.17-3.22(5H,m),3.74-3.79(4H,m),4.79(1H,d,J=7.8Hz),5.34-5.54(2H,m).IR(CHCl3)3470,3390,3270,2675,1709,1455,1420,1315,1147/cm.[α]D=+16.8°(CHCl3,C=1.42,26℃).No.1k-1[α]D=-25.4°(CHCl3,C=1.08,23℃).No.1k-2CDCl3 200MHz1.07-2.28(14H,m),2.32(2H,t,J=7.4Hz),2.63(1H,m),3.63(3H,s),3.93(1H,m),5.30-5.52(2H,m),6.35(1H,d,J=7.0Hz),7.48-7.60(3H,m),7.88-8.02(6H,m) .IR(CHCl3)3438,3002,2946,2868,1727,1652,1514,1485,1363,1310,1245,1154/cm.[α]D=-80.4°(CHCl3,C=1.01,24.0℃).No.1k-3CDCl3 200MHz1.10-2.26(14H,m),2.37(2H,t,J=7.2Hz),2.60(1H,m),3.93 (1H,m),5.30-5.50(2H,m),6.33(1H,d,J=7.5Hz),7.48-7.58(3H,m),7.88-7.99(6H,m).IR(CHCl3)3446,3004,2952,2874,1709,1652,1515,1485,1305,1153/cm.[α]D=-96.4°(CHCl3,C=1.05,23.0℃).No.1k-4CDCl3 300MHz1.05-2.17(14H,m),2.38(2H,t,J=7.2Hz),2.52(1H,m),3.8 1(1H,m),5.33-5.50(2H,m),6.08(1H,d,J=7.6Hz),7.39-7.53(3H,m),7.57-7.62(6H,m).IR(CHCl3)3420,3250,3008,2948,2870,2660,2208,1735(sh),1705,1640,1500/cm.[α]D=-21.9±0.6°(CHCl3,C=1.02,22℃).No.1k-5CDCl3 300MHz1.05-2.14(14H,m),2.38(2H,t,J=7.2Hz),2.51(1H,m),3.81(1H,m),5.34-5.46(2H,m),6.07(1H,d,J=7.6Hz),7.33-7.56(5H,m).IR(CHCl3)3422,3250,3010,2950,2876,2664,2558,2210,1735(3h),1705,1645,1502,1441,1410,1307,1276/cm.[α]D=-63.6±1.9°(CHCl3,C=0.56,22℃).No.1k-6CDCl3 300MHz1.04-2.24(14H,m),2.36(2H,t,J=7.5Hz),2.58(1H,m),3.88(1H,m),5.30-5.43(2H,m),6.21(1H,d,J=7.2Hz),7.41-7.49(3H,m),7.73-7.77(2H,m).IR(CHCl3)3447,3011,2955,1708,1653,1603,1578,1515,1486,1457,1312,1211,1164/cm.[α]D=-60.3°(CHCl3,C=1.00,23℃).No.1k-7CDCl3 300MHz1.04-2.22(14H,m),2.36(2H,t,J=7.2Hz),2.57(1H,m),3.87(1H,m),5.30-5.44(2H,m),6.17(1H,d,J=8.7Hz),6.99-7.40(7H,m),7.73(2H,d,J=7.5Hz).IR(CHCl3)3449,3013,2955,1739,1708,1651,1609,1588,1522,1487,1243,1227,1169/cm.[α]D=-60.2°(CHCl3,C=0.92,23℃).No.1k-8CDCl3 300MHz1.04-2.25(14H,m),2.34(2H,t,J=7.5Hz),2.56(1H,m),3.87(1H,m),5.30-5.44(2H,m),6.19(1H,d,J=7.5Hz),6.83-6.94(6H,m),7.69(2H,d,J=8.7Hz).IR(CHCl3)3599,3455,3012,2955,1711,1644,1604,1577,1524,1507,1492,1290,1236,1197,1170/cm.[α]D=-47.7°(CHCl3,C=1.01,22℃).No.1k-9CDCl3 300MHz1.04-2.20(14H,m),2.31(3H,s),2.36(2H,t,J=7.2Hz),2.56(1H,m),3.86(1H,m),5.30-5.43(2H,m),6.16(1H,d,J=7.2Hz),7.00-7.11(6H,m),7.74(2H,d,J=8.7Hz).1R(CHCl3)3450,3010,2955,1750,1709,1651,1609,1596,1523,1489,1370,1247,1227,1183/cm.[α]D=-54.7°(CHCl3,C=1.01,22℃).No.1k-10CDCl3 300MHz1.04-2.22(14H,m),2.35(2H,t,J=7.2Hz),2.56(1H,m),3.82(3H,s),3.86(1H,m),5.30-5.43(2H,m),6.17(1H,d,J=6.9Hz),6.89-7.01(6H,m),7.70(2H,d,J=8.7Hz).IR(CHCl3) 3023,2955,1742,1708,1649,1613,1602,1577,1522,1507,1490,1227,1210,1170/cm.[α]D=-58.1°(CHCl3,C=1.01,22℃).No.1m-1CDCl3 300MHz1.06-2.25(14H,m),2.32(2H,t,J=7.4Hz),2.61(1H,m),3.63 (3H,s),3.91 (1H,m),5.33-5.47(2H,m),6.24(1H,d,J=6.9Hz),7.35-7.38(3H,m),7.53-7.60(4H,m),7.75-7.78(2H,m).IR(CHCl3)3438,3008,2946,2875,2212,1732,1650,1605,1519,1496/cm.[α]D=+76°(CHCl3,C=1.39,24℃)No.1m-2CDCl3 300MHz1.05-2.20(14H,m),2.36(2H,t,J=6.2Hz),2.59(1H,m),3.89(1H,m),5.29-5.48(2H,m),6.26(1H,d,J=7.0Hz),7.26-7.38(3H,m),7.52- 7.60(4H,m),7.73-7.77(2H,m).IR(CHCl3)3444,3012,2952,2874,2664,2214,1718(sh),1708,1649,1605,1520,1498/cm.[α]D=+81.4°(CHCl3,C=1.01,23℃)No.1m-3CDCl3 300MHz1.06-2.23(14H,m),2.32(2H,t,J=7.0Hz),2.62(1H,m),3.63(3H,s),3.93(1H,m),5.30-5.50(2H,m),6.28(1H,d,J=7.0Hz),7.38-7.51(3H,m),7.58-7.67(4H,m),7.83-7.88(2H,m).IR(CHCl3)3438,3008,2948,2875,1783(w),1727,1650,1608,1580(w),1523,1501,1482/cm.[α]D= +59°(CHCl3,C=1.49,25℃)No.1m-4CDCl3 300MHz1.08-2.25(14H,m),2.36(2H,t,J=7.4Hz),2.59(1H,m),3.91(1H,m),5.28-5.48(3H,m),6.29(1H,d,J=7.4Hz),7.38-7.50(3H,m),7.61-7.67(4H,m),7.81-7.86(2H,m).IR(CHCl3)3436,3010,2948,2868,1727,1715(sh),1649,1615(w),1524,1502,1482,1372/cm.[α]D=+72°(CHCl3,C=0.98,25℃)No.1m-5CDCl3 300MHz1.09-2.20(14H,m),2.32(2H,t,J=7.2Hz),2.63(1H,m),3.63(3H,s),3.92(1H,m),5.31-5.51(2H,m),6.35(1H,d,J=7.0Hz),7.51-7.60(3H,m),7.92-7.97(6H,m).IR(CHCl3)3436,3008,2946,2875,1727,1652,1608(w),1515,1484/cm.[α]D=+82°(CHCl3,C=0.99,25℃)No.1m-6CDCl3 300MHz1.09-2.23(14H,m),2.37(2H,t,J=7.2Hz),2.60(1H,m),3.92(1H,m),5.30-5.49(2H,m),6.32(1H,d,J=7.4Hz),7.51-7.55(3H,m),7.85-7.98(6H,m).IR(CHCl3)3436,3010,2950,2875,2670,1727,1715(sh),1650,1605(w),1515,1484/cm.[α]D=+84°(CHCl3,C=1.54,25℃)No.1m-7CDCl3 300MHz1.03-2.18(14H,m),2.32(2H,t,J=7.4Hz),2.59(1H,m),3.64(3H,s),3.89(1H,m),5.29-5.49(2H,m),6.16(1H,d,J=7.8Hz),6.98-7.06(4H,m),7.14-7.20(1H,m),7.34-7.41(2H,m),7.73-7.78(2H,m).IR(CHCl3)3438,3008,2946,2868,1727,1648,1610,1586,1519,1485/cm.[α]D=+54°(CHCl3,C=1.29,25℃).No.1m-8CDCl3 300MHz1.06-2.21(14H,m),2.36(2H,t,J=7.5Hz),2.58(1H,m),3.88(1H,m),5.31- 5.46(2H,m),6.17(1H,d,J=6.9Hz),6.99-7.05(4H,m),7.15-7.21(1H,m),7.36-7.41(2H,m),7.72-7.75(2H,m).IR(CHCl3)3436,3010,2948,2868,2675,1730(sh),1709,1647,1608,1586,1520,1485/cm.[α]D=+56°(CHCl3,C=0.97,25℃)No.1m-9CDCl3 300MHz1.05-2.18(14H,m),2.29-2.34(5H,m),2.59(1H,m),3.64(3H,s),3.89(1H,m),5.32-5.46(2H,m),6.16(1H,d,J=7.5Hz),7.00-7.11(6H,m),7.74-7.77(2H,m).IR(CHCl3)3440,3010,2946,2868,1729,1649,1595,1519,1488/cm.[α]D=+47°(CHCl3,C=0.82,25℃).No.1m-10CDCl3 300MHz 1.04-2.20(14H,m),2.31-2.39(5H,m),2.57(1H,m),3.87(1H,m),5.28-5.47(2H,m),6.17(1H,d,J=7.0Hz),6.99-7.12(6H,m),7.72-7.76(2H,m).IR(CHCl3)3674,3572,3438,3010,2948,2868,2626,1748,1710,1648,1615,1595,1520,1489/cm.[α]D=+51°(CHCl3,C=0.91,25℃)No.1m-11CDCl3 300MHz1.04-2.16(14H,m),2.31(2H,t,J=7.2Hz),2.59(1H,m),3.63(3H,s),3.89(1H,m),5.29-5.49(2H,m),6.24(1H,d,J=7.4Hz),6.54(1H,s),6.83-6.93(6H,m),7.69-7.73(2H,m).IR(CHCl3)3674,3588,3438,3296,3010,2946,2868,1725,1646,1603,1520,1504,1489/cm.[α]D=+51°(CHCl3,C=0.91,25℃)No.1m-12CDCl3 300MHz1.04-2.21(14H,m),2.33(2H,t,J=8.0Hz),2.56(1H,m),3.87(1H,m),5.28- 5.48(2H,m),6.23(1H,d,J=8.0Hz),6.75(1H,m),6.87-6.94(6H,m),7.66-7.71(2H,m),9.63(1H,brs).IR(CHCl3)3674,3582,3436,3275,3010,2950,2868,2675,1727,1710(sh),1643,1603,1522,1504,1490/cm.[α]D=+30°(CHCl3,C=0.97,25℃)No.1m-13CDCl3 300MHz1.01-2.18(14H,m),2.31(2H,t,J=7.4Hz),2.58(1H,m),3.63(3H,s),3.82(3H,s),3.89(1H,m),5.29-5.48(2H,m),6.14(1H,d,J=7.0Hz),6.88- 7.02(6H,m),7.70-7.74(2H,m).IR(CHCl3)3442,3402,3004,2946,2868,1727,1648,1600,1518,1499/cm.[α]D=+42°(CHCl3,C=1.82,26℃)No.1m-14CDCl3 300MHz1.05-2.21(14H,m),2.35(2H,t,J=7.2Hz),2.55(1H,m),3.82(3H,s),3.88(1H,m),5.27-5.46(2H,m),6.16(1H,d,J=7.2Hz),6.88-7.02(6H,m),7.68-7.73(2H,m).IR(CHCl3)3438,3012,2948,2870,2650,1730(sh),1709,1647,1615(sh),1601,1519,1492/cm.[α]D=+64°(CHCl3,C=0.70,25℃)No.1m-15CDCl3 300MHz1.05-2.20(14H,m),2.29-2.36(5H,m),2.62(1H,m),3.63(3H,s),3.92(1H,m),5.30-5.50(2H,m),6.25(1H,d,J=7.2Hz),7.16-7.21(2H,m),7.59-7.64(4H,m),7.83-7.87(2H,m).IR(CHCl3)3446,3010,2946,2868,1745(sh),1728,1650,1615,1525,1507,1486/cm.[α]D=+65.0°(CHCl3,C=1.02,23℃)No.1m-16CDCl3 300MHz1.08-2.21(14H,m),2.34-2.40(5H,m),2.59(1H,m),3.90(1H,m),5.29-5.48(2H,m),6.29(1H,d,J=7.0Hz),7.18(2H,d,J=8.6Hz),7.58-7.64(4H,m),7.83(2H,d,J=8.2Hz).IR(CHCl3)3438,3012,2948,2870,2622,1749,1710,1649,1610,1526,1508,1487/cm.[α]D=+66°(CHCl3,C=1.21,24℃)No.1m-17CDCl3 300MHz1.06-2.19(14H,m),2.32(2H,t,J=7.2Hz),2.62(1H,m),3.63(3H,s), 3.93(1H,m),5.30-5.50(2H,m),6.32(1H,d,J=7.6Hz),6.41(1H,s),6.94 (2H,d,J=9.0Hz),7.47(2H,d,J=9.0Hz),7.58(2H,d,J=8.6Hz),7.81(2H,d,J=8.6Hz).IR(CHCl3)3580,3434,3284,3010,2946,2868,1726,1646,1606,1528,1490/cm. [α]D=+62.4°(CHCl3,C=1.01,23℃)No.1m-18CDCl3+CD3OD 300MHz1.11-2.18(14H,m),2.32(2H,t,J=7.4Hz),2.59(1H,m),3.88(1H m),5.30-5.49(2H,m),6.55(1H,d,J=7.0Hz),6.92(2H,d,J=8.6Hz),7.47(2H,d,J=8.6Hz),7.59(2H,d,J=8.6Hz),7.79(2H,d,J=8.2Hz).IR(Nujol)3398,3175,2725,1696,1635,1601,1531,1510/cm.[α]D=+99.5°(CH3OH,C=1.011,25℃)No.1m-19CDCl3 300MHz1.05-2.20(14H,m),2.32(2H,t,J=7.4Hz),2.61(1H,m),3.63(3H,s),3.86(3H,s),3.94(1H,m),5.30-5.50(2H,m),6.24(1H,d,J=7.0Hz),6.99(2H,d,J=8.6Hz),7.53-7.63(4H,m),7.82(2H,d,J=8.6Hz).IR(CHCl3)3440,3006,2946,2875,1726,1649,1606,1527,1510,1489/cm.[α]D=+68°(CHCl3,C=0.88,26℃)No.1m-20CDCl3 300MHz1.09-2.20(14H,m),2.35(2H,t,J=7.3Hz),2.58(1H,m),3.85(3H,s),3.89(1H,m),5.28-5.48(2H,m),6.35(1H,d,J=7.2Hz),6.98(2H,d,J=8.8Hz),7.51-7.61(4H,m),7.81(2H,d,J=8.4Hz),8.34(1H,brs).IR(CHCl3)3446,3012,2952,2881,2640,1730(sh),1707,1647,1606,1527,1510,1489/cm.[α]D=+83°(CHCl3,C=1.00,25℃).No.1m-21CDCl3 300MHz1.05-2.14(14H,m),2.37(2H,t,J=7.2Hz),2.51(1H,m),3.81(1H,m),5.34-5.46(2H,m),6.11(1H,d,J=7.5Hz),7.33-7.48(3H,m),7.53-7.55(2H,m).IR(CHCl3)3420,3250,3008,2948,2870,2660,2210,1735(sh),1705,1645,1503,1441,1409/cm.[α]D=+59.2±1.0°(CHCl3,C=1.023,22℃).No.1m-22CDCl3 300MHz1.05-2.17(14H,m),2.37(2H,t,J=7.2Hz),2.52(1H,m),3.82(1H,m),5.32-5.47(2H,m),6.20(1H,d,J=7.6Hz),7.38-7.53 (3H,m),7.58-7.61(6H,m),9.11(1H,brs).IR(CHCl3)3420,3250,3010,2984,2870,2675,2208,1730(sh),1705,1640,1500,1406/cm.[α]D=+57.4°(CHCl3,C=1.83,23℃).No.1m-23CDCl3 300MHz1.05-2.18(14H,m),2.31(2H,t,J=7.5Hz),2.60(1H,m),3.63(3H,s),3.90(1H,m),5.32-5.47(2H,m),6.22(1H,d,J=6.9Hz),7.40-7.49(3H,m),7.76-7.79(2H,m).IR(CHCl3)3438,3008,2946,2868,1727,1651,1603,1585,1512,1484/cm.[α]D=+52°(CHCl3,C=1.49,25℃).No.1m-24 CDCl3 300MHz 1.05-2.21(14H,m),2.36(2H,t,J=7.2Hz),2.57(1H,m),3.89(1H,m),5.28-5.47(2H, m),6.22(1H,d,J=7.0Hz),7.39-7.55(3H,m),7.73-7.79(2H,m). IR(CHCl3)3676,3572,3436,3010,2948,2875,1730(sh),1709,1650,1600,1580,1 514,1484/cm. [α]D=+57°(CHCl3,C=0.97,26℃). No.1m-25 CDCl3 300MHz 1.04-2.18(14H,m),2.28-2.35(5H,m),2.59(1H,m),3.62(3H,s),3.88(1H,m),5.29-5. 49(2H,m),6.20(1H,d,J=7.2Hz),7.15(2H,d,J=9.0Hz),7.80(2H,d,J=8.8Hz).IR(CHCl3)3436,3010,2946,2868,1752,1727,1653,1602,1519,1491/cm. [α]D=+53°(CHCl3,C=1.63,25℃).No.1m-26CDCl3 300MHz1.05-2.19(14H,m),2.32-2.38(5H,m),2.56(1H,m),3.88(1H,m),5.29-5.47(2H,m),6.25(1H,d,J=7.4Hz),7.15(2H,d,J=9.0Hz),7.78(2H,d,J=8.6Hz).IR(CHCl3)3434,3016,3006,2948,2880,2622,1752,1730(sh),1710,1651,1605,1520,1492/cm.[α]D=+58°(CHCl3,C=3.68,24℃)No.1m-27CDCl3 300MHz1.05-2.16(14H,m),2.30(2H,t,J=7.5Hz),2.57(1H,m),3.62(3H,s),3.87(1H,m),5.27-5.47(2H,m),6.32(1H,d,J=7.4Hz),6.85(2H,d,J=8.6Hz),7.62(2H,d,J=8.6Hz),8.35(1H,s).IR(CHCl3)3580,3450,3216,3010,2946,2868,1726,1640,1608,1584,1528,1496/cm.[α]D=+56.2°(CHCl3,C=0.713,23℃)No.1m-28CDCl3 200MHz1.10-2.25(14H,m),2.32(2H,t,J=7.2Hz),2.55(1H,brs),3.82-3.93(1H,m),5.27-5.47(2H,m),6.25 (1H,d,J=7.4Hz),6.86(2H,d,J=8.6Hz),7.62(2H,d,J=8.6Hz).IR(CHCl3)3438,3242,2675,1730(sh),1708,1639,1607,1585/cm.No.1m-29CDCl3 300MHz1.05-2.18(14H,m),2.31(2H,t,J=7.4Hz),2.58(1H,m),3.64(3H,s),3.85(3H,s),3.89(1H,m),5.29-5.48(2H,m),6.14(1H,d,J=6.6Hz),6.92(2H,d,J=9.0Hz),7.74(2H,d,J=9.0Hz).IR(CHCl3)3445,3008,2946,2858,1727,1646,1606,1578,1523,1493/cm.[α]D=+53°(CHCl3,C=2.03,24℃)No.1m-30CDCl3 300MHz1.04-2.21(14H,m),2.36(2H,t,J=7.3Hz),2.56(1H,m),3.85(3H,s),3.88(1H,m),5.27-5.46(2H,m),6.15(1H,d,J=7.2Hz),6.92(2H,d,J=8.6Hz),7.73(2H,d,J=8.6Hz)IR(CHCl3)3440,3010,2950,2870,2645,1727,1710(sh),1646,1606,1575,1524,1494/cm.[α]D=+62°(CHCl3,C=1.10,24℃).No.1m-31CDCl3+CD3OD 300MHz1.16-2.20(14H,m),2.31(2H,t,J=7.2Hz),2.59(1H,m),3.85(1H,m),5.31-5.51(2H,m),7.13-7.21(1H,m),7.31-7.42(2H,m),7.68-7.93(6H,m).IR(液蜡)3344,3175,2715,2675,1699,1631,1566/cm. [α]D=+67°(CH3OH,C=1.01,24℃). No.1m-32 CDCl3 200MHz 1.09-2.23(14H,m),2.33(2H,t,J=7.1Hz),2.57(1H,brs),3.40-3.93(9H,m),4.41(1H, brs),5.29-5.48(2H,m),6.44(1H,d,J=7.4Hz),7.43(2H,d,J=8.2Hz),7.80(2H,d,J=7. 8Hz). IR(CHCl3)3434,3354,1726,1720(sh),1660(sh),1626/cm. No.1m-33 CDCl3 200MHz 1.14-2.25(14H,m),2.37(2H,t,J=7.3Hz),2.64(1H,brs),3.93-4.01(1H,m),5.30-5.5 1(2H,m),6.47(1H,d,J=7.4Hz),7.63-7.74(2H,m),7.79(2H,s),7.89-7.93(1H,m),8.00(1H,dd,J=2.3,1.0Hz),8.30(1H,d,J=1.0Hz),8.65-8.73(2H,m).IR(CHCl3)3450,2675,1728,1707,1649,1528,1509/cm.[α]D=+82.8±1.2°(CHCl3,C=1.01,23℃).No.2a-1[α]D=+69.0°(MeOH,C=1.01,25℃)No.2a-2CDCl3 300MHz0.99(1H,d,J=10.2Hz),1.15和1.24(每个3H,每个s),1.50-2.50(14H,m),4.30(1H,m).5.35-5.52(2H,m),6.32(1H,d,J=8.7Hz),7.36-7.49(3H,m),7.58-7.62(2H,m),7.66和 7.80(每个2H,每个d,J=8.7Hz).IR(CHCl3)3116,3014,2925,2870,2663,1708,1651,1610,1524,1504,1484,1472/cm.[α]D=+64.1°(MeOH,C=1.02,25℃).No.2a-3[α]D=+76.6°(MeOH,C=1.18,26℃).No.2a-4CDCl3 300MHz0.99(1H,d,J=10.2Hz),1.15和 1.25(每个3H,每个s),1.64-2.51(14H,m),4.31(1H,m),5.36-5.53(2H,m),6.33(1H,d,J=8.4z),7.50-7.56(3H,m),7.85-7.98(6H,m).IR(CHCl3)3515,3452,3014,2925,2870,1740,1708,1654,1517,1486,1470/cm.[α]D=+79.5°(MeOH,c=1.18,22℃).No.2a-5 CD3OD 300MHz 0.98(1H,d,J=9.9Hz),1.18和 1.25(每个3H,每个s),1.56-1.71(3H,m),1.98-2.40(11H,m),4.17(1H,m),5.41-5.52(2H,m),7.52-7.61(3H,m),7.91-8.01(6H,m). IR(KBr)3416,3063,2983,2921,2869,1704,1643,1566,1518,1488,1408/cm.[α]D=+62.0°(MeOH,C=1.00,25℃).No.2a-6[α]D=+64.1°(MeOH,C=1.01,25℃).No.2a-7[α]D=+65.3°(MeOH,C=0.99,25℃).No.2a-8[α]D=+74.0°(MeOH,C=1.01,25℃).No.2a-9[α]D=+71.0°(MeOH,C=1.10,25℃).No.2a-10[α]D=+74.7°(MeOH,C=1.00,25℃).No.2a-11[α]D=+72.1°(MeOH,C=1.00,25℃).No.2a-12[α]D=+53.1°(CHCl3,C=1.01,26℃).m.p.155.0-156.0℃No.2a-13 CDCl3 300MHz0.98(1H,d,J=10.2Hz),1.18和1.25(每个3H,每个s),1.63-2.40(14H,m),4.30(1H,m),5.46-5.58(2H,m),6.44(1H,d,J=8.4Hz),7.49和7.77(每个2H,每个 d,J=8.7Hz),7.54(1H,s).IR(CHCl3)3689,3378,3028,3014,2924,1713,1652,1602,1522,1496/cm.[α]D=+78.3°(MeOH,C=0.84,25℃).m.p.205.0-206.0℃No.2a-14[α]D=+72.5°(MeOH,C=1.07,25℃).No.2a-15 CDCl3 300MHz0.99(1H,d,J=9.9Hz),1.14和1.24(每个3H,每个s),1.55-2.44(14H,m),4.27(1H,m),5.30-5.50(2H,m),6.29(1H,d,J=9.0Hz),7.11和7.20(每个1H,每个d,J=16.2Hz),7.29-7.55(5H,m),7.57和7.72(每个2H,每个d,J=8.7Hz).IR(CHCl3)3453,3083,3022,3013,2925,2870,1708,1650,1607,1560,1522,1496/cm.[α]D=+72.3°(MeOH,C=1.00,27℃).m.p.115.0-117.0℃No.2a-16 CDCl3 300MHz 0.92(1H,d,J=10.2Hz),1.11和1.23(每个3H,每个s),1.50-2.48(14H,m),3.6 2(3H,s),4.29(1H,m),5.30-5.50(2H,m),6.20(1H,d,J=8.7Hz),6.59和6.68(每个1H,每个d,J=12.3Hz),7.23(5H,s),7.29和7.59(每个2H,每个d,J=8.1Hz).IR(CHCl3)3453,3024,3016,2924,2870,1730,1651,1607,1520,1495/cm.[α]D=+56.8°(MeOH,C=1.04,24℃).No.2a-17CDCl3 300MHz0.97(1H,d,J=10.2Hz),1.11和1.23(每个3H,每个s),1.50-2.38(14H,m),4.26(1H,m),5.30-5.50(2H,m),6.23(1H,d,J=8.4Hz),6.59和6.70(每个1H,每个d,J=12.3Hz),7.23(5H,s),7.30和7.57(每个2H,每个d,J=8.7Hz).IR(CHCl3)3452,3081,3019,3014,2925,2870,2665,1708,1650,1607,1521,1495/cm.[α]D=+61.6°(MeOH,C=1.00,27℃).No.2a-18CDCl3 300MHz0.97(1H,d,J=10.2Hz),1.11和1.23(每个3H,每个s),1.50-2.50(14H,m),3.61(3H,s),4.31(1H,m),5.35-5.51(2H,m),6.33(1H,d,J=8.4Hz),7.48-7.64(4H,m),7.79-7.83(2H,m),7.91(1H,dt,J=1.5和7.8Hz),8.01(1H,dt,J=1.5和7.8Hz),8.13(1H,t,J=1.5Hz).IR(CHCl3)3450,3026,3013,2925,2870,1730,1659,1600,1510/cm.[α]D=+56.0°(MeOH,C=1.01,25℃).No.2a-19CDCl3 300MHz0.95(1H,d,J=9.9Hz),1.14和1.21(每个3H,每个s),1.53-2.60(14H,m),4.25(1H,m),5.35-5.64(2H,m),7.21(1H,d,J=7.8Hz),7.49-7.68(4H,m),7.76-7.84(3H,m),8.25(1H,m),8.43(1H,m).IR(CHCl3)3382,3196,3025,3015,2925,2870,1725,1652,1599,1577,1521/cm.[α]D=+55.9°(MeOH,C=1.00,25℃).No.2a-20CDCl3300MHz0.98(1H,d,J=10.2Hz),1.13和1.24(每个3H,每个s),1.50-2.50(14H,m),3.62(3H,s),4.31(1H,m),5.35-5.51(2H,m),6.24(1H,d,J=8.4Hz),7.40-7.52(3H,m),7.71-7.76(2H,m).IR(CHCl3)3453,3025,3013,2925,2870,1730,1753,1579,1514,1486/cm.[α]D=+61.2°(MeOH,C=1.04,25℃).No.2a-21CDCl3 300MHz0.98(1H,d,J=10.2Hz),1.13和1.23(每个3H,每个s),1.52-2.50(14H,m),4.28(1H,m),5.34-5.51(2H,m),6.27(1H,d,J=8.7Hz),7.41-7.53(3H,m),7.71-7.74(2H,m).IR(CHCl3)3452,3063,3027,3014,2925,2871,1708,1652,1578,1515,1486/cm.[α]D=+62.0°(MeOH,C=1.01,27℃).No.2a-22d6-DMSO 300MHz0.86(1H,d,J=9.9Hz),1.10和1.16(每个3H,每个s),1.42-1.52(3H,m),1.85-2.46(11H,m),3.98(1H,m),5.32-5.43(2H,m),7.41(3H,m),7.88(2H,d,J=6.6Hz),8.19(1H,d,J=6.6Hz).IR(KBr)3367,3060,2984,2922,2868,1634,1563,1529,1487/cm.[α]D=+47.7°(MeOH,C=1.00,25℃).No.2a-23[α]D=+62.7°(MeOH,C=1.01,27℃).No.2a-24CDCl3 300MHz0.99(1H,d,J=10.2Hz),1.14和1.25(每个3H,每个s),1.52-2.50(14H,m),4.31(1H,m),5.36-5.52(2H,m),6.34(1H,d,J=8.4Hz),7.47-7.52(2H,m),7.59-7.64(1H,m),7.78-7.83(6H,m).IR(CHCl3)3449,3027,3013,2925,2869,1708,1656,1599,1518,1493/cm.[α]D=+63.1°(MeOH,C=1.00,25℃).No.2a-25[α]D=+35.1°(MeOH,C=1.00,25℃).No.2a-26[α]D=+35.5°(MeOH,C=1.02,25℃).No.2a-27CDCl3 300MHz0.97(1H,d,J=10.2Hz),1.12和1.23(每个3H,每个s),1.52-2.50(14H,m),3.63(3H,s),4.29(1H,m),5.36-5.51(2H,m),6.18(1H,d,J=8.4Hz),7.01和7.71(每个2H,每个d,J=8.7Hz,),6.98-7.05(2H,m),7.16(1H,t,J=7.5Hz),7.34-7.41(2H,m).IR(CHCl3)3455,3024,3016,2924,2870,1730,1651,1588,1520,1487/cm.[α]D=+56.4°(MeOH,C=1.01,25℃).No.2a-28CDCl3 300MHz0.98(1H,d,J=10.2Hz),1.12和1.23(每个3H,每个s),1.52-2.50(14H,m),4.26(1H,m),5.34-5.51(2H,m),6.20(1H,d,J=9.0Hz),7.01和7.70(每个2H,每个d,J=9.0Hz,),6.98-7.15(2H,m),7.17(1H,t,J=7.5Hz),7.34-7.40(2H,m).IR(CHCl3)3454,3031,3018,2925,2870,1708,1650,1588,1523,1487/cm.[α]D=+56.2°(MeOH,C=1.00,25℃).No.2a-29[α]D=+53.0°(MeOH,C=1.03,25℃).No.2a-30CDCl3 300MHz0.97(1H,d,J=10.2Hz),1.10和1.23(每个3H,每个s),1.52-2.50(14H,m),4.25(1H,m),5.30-5.50(2H,m),6.23(1H,d,J=8.7Hz),6.36(1H,s),7.26-7.39(10H,m),7.60和 7.68(每个2H,每个d,J=8.4Hz,).IR(CHCl3)3451,3088,3064,3029,3014,2925,2869,1707,1652,1522,1495/cm.[α]D=+54.2°(MeOH,C=1.00,25℃).No.2a-31CDCl3 300MHz0.98(1H,d,J=10.2Hz),1.14和1.24(每个3H,每个s),1.50-2.50(14H,m),3.63(3H,s),4.31(1H,m),5.30-5.50(2H,m),6.26(1H,d,J=8.4Hz),6.90(1H,t,J=7.4Hz),7.13(1H,d,J=8.7Hz),7.29(2H,t,J=8.0Hz),7.67-7.75(5H,m),7.82(1H,s).IR(Nujol)3380,3244,1723,1638,1601,1578,1535,1495/cm.[α]D=+73.6°(MeOH,C=0.50,26℃)。m.p.133.0-134.0℃No.2a-32[α]D=+56.1°(MeOH,C=1.02,26℃).No.2a-33CDCl3 300MHz0.95(1H,d,J=10.2Hz),1.10和1.21(每个3H,每个s),1.50-2.50(14H,m),4.25(1H,m),5.13(2H,s),5.30-5.70(3H,m),6.41(1H,d,J=8.2Hz),6.89(1H,s),7.09(1H,s),7.17和7.72(每个2H,每个d,J=8.2Hz),7.62(1H,s).IR(CHCl3)3450,3125,3031,3013,2925,2870,2467,1917,1708,1654,1615,1575,1523,1497/cm.[α]D=+55.2°(MeOH,C=1.01,26℃).No.2a-34[α]D=+72.9°(MeOH,C=1.03,25℃).No.2a-35CDCl3 300MHz0.98(1H,d,J=10.2Hz),1.13和1.24(每个3H,每个s),1.52-2.48(14H,m),4.28(1H,m),5.35-5.51(2H,m),6.28(1H,d,J=8.7Hz),7.34-7.37(3H,m),7.52-7.55(2H,m),7.58和 7.71(每个2H,每个d,J=8.7Hz).IR(CHCl3)3515,3452,3030,3012,2925,2870,1739,1708,1652,1607,1555,1521,1497/cm.[α]D=+74.3°(MeOH,C=1.01,25℃).No.2a-36[α]D=+23.4°(MeOH,C=1.07,25℃).No.2a-37CDCl3 300MHz0.83(1H,d,J=10.5Hz),0.95和1.18(每个3H,每个s),1.44-2.46(14H,m),3.92(1H,m),5.34-5.52(3H,m),7.26-7.54(9H,m),7.62(1H,s).IR(CHCl3)3432,3310,3189,3023,3014,2924,2870,1704,1610,1594,1523,1487/cm.[α]D=+25.3°(MeOH,C=1.00,26℃).No.2a-38[α]D=+70.9°(MeOH,C=1.02,25℃).No.2a-39[α]D=+70.6°(MeOH,C=1.01,25℃).No.2a-40[α]D=+74.7°(MeOH,C=1.00,25℃).No.2a-41[α]D=+72.1°(MeOH,C=1.01,24℃).No.2a-42[α]D=+69.2°(MeOH,C=1.00,25℃).No.2a-43[α]D=+70.8°(MeOH,C=1.00,25℃).No.2a-44[α]D=+60.4°(MeOH,C=1.00,26℃).No 2a-45CDCl3 300MHz0.97(1H,d,J=9.9Hz),1.13和1.23(每个3H,每个s),1.55-2.52(14H,m),4.29(1H,m),5.34-5.54(2H,m),6.33(1H,d,J=9.0Hz),7.10(1H,t,J=7.4Hz),7.34(2H,t,J=7.4Hz),7.52(2H,m),7.68和7.75(每个2H,每个d,J=8.4Hz),7.80(1H,s),8.10(1H,s),10.09(1H,s).IR(CHCl3)3393,3195,3093,3033,3013,2925,2870,1698,1656,1598,1537,1498/cm.[α]D=+59.4°(MeOH,C=1.01,24℃).No.2a-46[α]D=+63.5°(MeOH,C=1.00,25℃).No.2a-47CDCl3 300MHz0.97(1H,d,J=9.9Hz),1.12和1.23(每个3H,每个s),1.54-2.48(14H,m),4.29(1H,m),5.35-5.52(2H,m),6.32(1H,d,J=8.7Hz),7.26(1H,m),7.41(2H,t,J=7.8Hz),7.64(2H,d,J=7.5Hz),7.73和7.77(每个2H,每个d,J=8.4Hz),7.95(1H,s),9.20(1H,s),10.38(1H,s).IR(CHCl3)3450,3339,3003,2992,2925,2870,1706,1653,1596,1523,1495/cm.[α]D=+63.3°(MeOH,C=1.00,25℃).No.2a-48[α]D=+63.8°(MeOH,C=1.00,24℃).No.2a-49CDCl3 300MHz1.00(1H,d,J=10.5Hz),1.17和1.26(每个3H,每个s),1.55-2.52(14H,m),4.34(1H,m),5.36-5.54(2H,m),6.35(1H,d,J=9.0Hz),7.50-7.62(3H,m),7.90和8.33(每个2H,每个d,J=8.4Hz),8.21(2H,m).IR(CHCl3)3451,3029,3022,3016,2925,2870,1708,1655,1542,1508,1498,1471,1459/cm.[α]D=+63.5°(MeOH,C=1.02,25℃).m.p.135.0-137.0℃No.2a-50[α]D=+68.9°(MeOH,C=1.01,24℃).No.2a-51 d6-DMSO 300MHz0.87(1H,d,J=9.9Hz),1.10和1.17(每个3H,每个s),1.40-1.60(3H,m),1.90-2.40(11H,m),3.98(1H,m),5.35-5.46(2H,m),7.64(1H,s),7.65和7.91(每个2H,每个d,J=8.7Hz),8.06(1H,d,J=6.0Hz),9.32(1H,brs).IR(KBr)3385,2962,1734,1707,1632,1529,1498/cm.[α]D=+68.4°(MeOH,C=1.01,24℃).No.2a-52[α]D=+76.2°(MeOH,C=1.01,24℃).No.2a-53[α]D=+73.9°(MeOH,C=1.02,24℃).No.2a-54[α]D=+68.1°(MeOH,C=1.00,24℃).No.2a-55[α]D=+67.8°(MeOH,C=1.00,24℃).No.2a-56[α]D=+65.4°(MeOH,C=1.03,25℃).No.2a-57[α]D=+63.4°(MeOH,C=1.01,24℃).No.2a-58[α]D=+66.6°(MeOH,C=1.01,24℃).No.2a-59[α]D=+65.5°(MeOH,C=1.00,24℃).No.2a-60[α]D=+60.9°(MeOH,C=1.02,25℃).No.2a-61CDCl3 300MHz0.97(1H,d,J=10.0Hz),1.10和1.22(每个3H,每个s),1.50-2.50(14H,m),4.26(1H,m),5.30-5.54(2H,m),6.28(1H,d,J=8.6Hz),6.60和6.82(每个1H,每个d,J=12.4Hz,),7.12(2H,d,J=6.0Hz),7.25和7.62(每个2H,每个d,J=8.6Hz),8.47(2H,d,J=6.0Hz).IR(CHCl3)3452,3027,3019,3013,2925,2870,2480,1708,1651,1606,1520,1494/cm.[α]D=+61.6°(MeOH,C=1.01,25℃).No.2a-62[α]D=+72.0°(MeOH,C=0.93,25℃).No.2a-63CDCl3 300MHz0.99(1H,d,J=10.2Hz),1.14和1.24(每个3H,每个s),1.50-2.50(14H,m),4.29(1H,m),5.36-5.55(2H,m),6.35(1H,d,J=9.1Hz),7.04和7.27(每个1H,每个d,J=16.5Hz),7.37(2H,d,J=6.6Hz),7.56和7.76(每个2H,每个d,J=8.4Hz),8.57(2H,d,J=6.6Hz).IR(CHCl3)3452,3024,3018,3014,2925,2870,2470,1933,1708,1652,1605,1521,1496/cm.[α]D=+69.2°(MeOH,C=1.01,25℃).No.2a-64[α]D=+56.9°(MeOH,C=1.24,25℃).No.2a-65CDCl3 300MHz0.98(1H,d,J=10.5Hz),1.12和1.23(每个3H,每个s),1.54-2.46(14H,m),4.27(1H,m),5.23(2H,s),5.34-5.52(2H,m),6.26(1H,d,J=8.4Hz),7.32-7.45(5H,m),7.64和7.71(每个2H,每个d,J=8.4Hz),8.15(1H,s).IR(CHCl3)3452,3088,3065,3032,3013,2925,2870,1708,1653,1611,1559,1522,1496/cm.[α]D=+61.0°(MeOH,C=0.91,25℃).No.2a-66[α]D=+76.0°(MeOH,C=1.01,25℃).No.2a-67CDCl3 300MHz0.98(1H,d,J=10.4Hz),1.14和1.24(每个3H,每个s),1.54-2.46(14H,m),4.28(1H,m),5.32-5.53(2H,m),6.27(1H,d,J=8.6Hz),6,92-7.31(每个1H,每个d,J=16.4Hz),7.02(1H,dd,J=5.8 和3.6Hz),7.12(1H,d,J=3.6Hz),7.24(1H,d,J=5.8Hz),7.51和7.70(每个2H,每个d,J=8.4Hz).IR(CHCl3)3453,3029,3013,2925,2870,1739,1650,1604,1524,1515,1494/cm.[α]D=+76.2°(MeOH,C=1.00,24℃).m.p.104.0-106.0℃No.2a-68[α]D=+57.7°(MeOH,C=1.01,25℃).No.2a-69CDCl3 300MHzo.99(1H,d,J=10.2Hz),1.14和1.24(每个3H,每个s),1.54-2.48(14H,m),4.28(1H,m),5.34-5.53(2H,m),6.29(1H,d,J=9.0Hz),6,54-6.74(每个1H每个d,J=12.oHz),7.02(1H,dd,J=4.8和 3.3Hz),6.97(1H,dd,J=3.3和1.2Hz),7.13(1H,dd,J=4.8和1.2Hz),7.44和7.70(每个2H,每个d,J=8.7Hz).IR(CHCl3)3453,3025,3010,2925,2870,1708,1650,1607,1559,1523,1493/cm.[α]D=+58.4°(MeOH,C=1.00,25℃).No.2a-70[α]D=+48.6°(MeOH,C=1.00,25℃).No.2a-71CDCl3 300MHz0.98(1H,d,J=10.2Hz)1.12和1.23(每个3H,每个s),1.52-2.46(14H,m),2.31(3H,s),4.26(1H,m),5.33-5.52(2H,m),6.20(1H,d,J=9.3Hz),7.02-7.11(6H,m),7.70(2H,d,J=9.0Hz).IR(CHCl3)3460,3031,3022,3011,2925,2870,1750,1708,1650,1608,1597,1523,1490/cm.[α]D=+48.9°(MeOH,C=1.01,25℃).No.2a-72[α]D=+51.2°(MeOH,C=1.02,25℃).No.2a-73CDCl3 300MHz0.97(1H,d,J=9.9Hz),1.11和1.23(每个3H,每个s),1.54-2.48(14H,m),4.27(1H,m),5.32-5.52(2H,m),6.24(1H,d,J=9.0Hz),6.83-6.94(6H,m),7.65(2H,d,J=9.0Hz).IR(CHCl3)3598,3451,3199,3033,3012,2925,2870,1708,1642,1604,1524,1507,1491/cm.[α]D=+52.2°(MeOH,C=1.01,25℃).No.2a-74[α]D=+51.5°(MeOH,C=0.92,25℃).No.2a-75 CDCl3 300MHz0.97(1H,d,J=10.2Hz),1.11和1.23(每个3H,每个s),1.55-2.46(14H,m),3.82(3H,s),4.25(1H,m),5.32-5.52(2H,m),6.19(1H,d,J=8.7Hz),6.89-7.01(6H,m),7.65-7.68(2H,m).IR(CHCl3)3450,3025,3008,2925,2870,2837,1741,1649,1612,1521,1505,1490/cm.[α]D=+51.1°(MeOH,C=1.00,25℃).No.2a-76[α]D=+60.4°(MeOH,C=0.98,25℃).No.2a-77CDCl3 300MHz0.99(1H,d,J=10.5Hz),1.15和1.24(每个3H,每个s),1.54-2.48(14H,m),2.34(3H,s),4.29(1H,m),5.32-5.54(2H,m),6.32(1H,d,J=8.4Hz),7.19和7.60(每个2H,每个d,J=8.4Hz),7.63和7.79(每个2H,每个d,J=8.4Hz).IR(CHCl3)3452,3027,3012,2925,2870,1751,1709,1651,1611,1560,1527,1509,1489/cm.[α]D=+61.2°(MeOH,C=1.00,25℃).No.2a-78[α]D=+67.4°(MeOH,C=1.01,25℃).No.2a-79 CDCl3 300MHz0.99(1H,d,J=10.2Hz),1.15和1.24(每个3H,每个s),1.54-2.54(14H,m),4.31(1H,m),5.32-5.54(2H,m),6.36(1H,d,J=8.2Hz),6.93和7.48(每个2H,每个d,J=8.6Hz),7.59和7.75(每个2H,每个d,J=8.4Hz).IR(CHCl3)3593,3448,3192,3030,3010,2925,2870,1708,1644,1608,1591,1559,1530,1516,1491/cm.[α]D=+65.8°(MeOH,C=1.01,25℃).No.2a-80[α]D=+66.9°(MeOH,C=1.01,25℃).No.2a-81 CDCl3 300MHz0.99(1H,d,J=10.5Hz),1.15和1.24(每个3H,每个s),1.54-2.48(14H,m),3.86(3H,s),4.29(1H,m),5.34-5.52(2H,m),6.20(1H,d,J=8.7Hz),6.99和7.55(每个2H,每个d,J=9.0Hz),7.61和7.77(每个2H,每个d,J=8.7Hz).IR(CHCl3)3450,3009,2925,2870,2838,1740,1708,1650,1608,1557,1528,1512,1491/cm.[α]D=+66.2°(MeOH,C=1.01,25℃).No.2a-82[α]D=+57.7°(MeOH,C=1.02,24℃).No.2a-83CDCl3 300MHz0.97(1H,d,J=10.2Hz),1.12和1.23(每个3H,每个s),1.54-2.48(14H,m),2.33(3H,s),4.26(1H,m),5.32-5.52(2H,m),6.25(1H,d,J=8.7Hz),7.16和7.75 (每个2H,每个d,J=8.7Hz).IR(CHCl3)3452,3030,3022,3012,2925,2870,1754,1709,1654,1604,1585,1522,1493/cm.[α]D=+57.4°(MeOH,C=1.01,24℃).No.2a-84[α]D=+57.8°(MeOH,C=1.01,24℃).No.2a-85CDCl3 300MHz0.95(1H,d,J=10.2Hz),1.12和1.22(每个3H,每个s),1.54-2.48(14H,m),4.25(1H,m),5.32-5.52(2H,m),6.28(1H,d,J=8.7Hz),6.87和7.57(每个2H,每个d,J=9.0Hz).IR(CHCl3)3590,3450,3166,3019,3012,2925,2871,1708,1637,1608,1583,1531,1498/cm.[α]D=+56.0°(MeOH,C=1.01,24℃).No.2a-86[α]D=+59.3°(MeOH,C=1.01,22℃).No.2a-87CDCl3 300MHz0.98(1H,d,J=10.0Hz),1.13和1.23(每个3H,每个s),1.54-2.48(14H,m),3.85(3H,s),4.25(1H,m),5.32-5.53(2H,m),6.19(1H,d,J=8.8Hz),6.93和7.69(每个2H,每个d,J=9.0Hz).IR(CHCl3)3450,3030,3017,3012,2925,2870,2840,1740,1708,1647,1606,1575,1525,1496/cm.[α]D=+58.2°(MeOH,C=0.99,22℃).No.2a-88[α]D=+50.9°(MeOH,C=1.02,25℃).No.2a-89CDCl3 300MHz0.99(1H,d,J=10.2Hz),1.18和1.26(每个3H,每个s),1.56-2.48(14H,m),4.29(1H,m),5.36-5.54(2H,m),7.03(1H,d,J=8.7Hz),7.21(1H,s),7.43(2H,m),7.74(1H,ddd,J=1.8,6.9和8.7Hz),8.22(1H,dd,J=1.8和8.1Hz).IR(CHCl3)3443,3087,3023,3014,2925,2870,1708,1685,1658,1630,1517,1466/cm.[α]D=+57.1°(MeOH,C=1.01,22℃).m.p.117.0-118.0℃No.2a-90[α]D=+54.1°(MeOH,C=1.01,22℃).No.2a-91CDCl3 300MHz0.97(1H,d,J=10.2Hz),1.13和1.23(每个3H,每个s),1.52-2.46(14H,m),4.24(1H,m),5.34-5.52(2H,m),6.49-6.53(2H,m),7.11(1H,dd,J=0.9和3.6Hz),7.44(1H,dd,J=0.9和1.8Hz).IR(CHCl3)3437,3033,3022,3014,2925,2870,1739,1708,1655,1595,1520,1472/cm.[α]D=+55.0°(MeOH,C=1.00,22℃).No.2a-92[α]D=+50.3°(MeOH,C=1.00,22℃).No.2a-93CDCl3 300MHz0.95(1H,d,J=10.5Hz),1.12和1.23(每个3H,每个s),1.52-2.46(14H,m),4.25(1H,m),5.34-5.52(2H,m),6.12(1H,d,J=8.7Hz),7.07(1H,dd,J=3.9和5.1Hz),7.45-7.48(2H,m).IR(CHCl3)3450,3023,3011,2925,2870,1739,1708,1645,1531,1501,1471/cm.[α]D=+49.1°(MeOH,C=1.02,24℃).No.2a-94[α]D=+51.5°(MeOH,C=1.00,24℃).No.2a-95CDCl3 300MHz0.96(1H,d,J=10.5Hz),1.11和1.23(每个3H,每个s),1.52-2.46(14H,m),4.25(1H,m),5.34-5.56(2H,m),6.14(1H,d,J=8.7Hz),7 34(2H,d,J=2.0Hz),7.85(1H,t,J=2.0Hz).IR(CHCl3)3452,3114,3030,3013 2925,2870,1708,1649,1535,1498,1471/cm.[α]D=+55.5°(MeOH,C=1.00,25℃).m.p.87.0-88.0℃No.2a-96D3OD 300MHz0.94(1H,d,J=10.2Hz),1.13和1.22(每个3H,每个s),1.50-1.76(3H,m),1.94-2.39(11H,m),4.11(1H,m),5.39-5.49(2H,m),7.43-7.51(2H,m),8.05(1H,m).IR(KBr)3369,3084,2985,2921,2868,1630,1566,1538,1503/cm.[α]D=+38.8°(MeOH,C=1.01,22℃).No.2a-97CD3OD 300MHz0.93(1H,d,J=9.9Hz),1.13和1.22(每个3H,每个s),1.48-1.58(3H,m),1.96-2.36(11H,m),4.10(1H,m),5.35-5.50(2H,m),7.42-7.51(2H,m),8.06(1H,m).IR(KBr)3447,3087,2987,2922,2868,1629,1545,1501/cm.[α]D=+52.9°(MeOH,C=1.01,24℃).No.2a-98[α]D=+53.2°(MeOH,C=1.02,23℃).No.2a-99CDCl3 300MHz0.97(1H,d,J=10.2Hz),1.12和1.22(每个3H,每个s),1.26-2.45(24H,m),4.25(2H,m),5.34-5.52(2H,m),6.18(1H,d,J=8.7Hz),6.91和7.66(每个2H,每个d,J=9.0Hz).IR(CHCl3)3455,3029,3019,2939,2862,1738,1709,1645,1605,1523,1494/cm.[α]D=+51.4°(MeOH,C=1.00,23℃).No.2a-100[α]D=+49.3°(MeOH,C=1.00,24℃).No.2a-101[α]D=+51.3°(MeOH,C=1.00,24℃).No.2a-102[α]D=+48.8°(MeOH,C=1.01,23℃).No.2a-103CDCl3 300MHz0.94(1H,d,J=10.2Hz),1.12和1.22(每个3H,每个s),1.52-2.46(14H,m),2.48(3H,d,J=O.3Hz),4.20(1H,m),5.32-5.54(2H,m),6.46(1H,brs),7.12(1H,d,J=9.OHz).IR(CHCl3)3415,3144,3029,3011,2926,2871,1708,1671,1598,1538,14564/cm[α]D=+49.6°(MeOH,C=1.01,23℃).No.2a-104[α]D=+77.0°(MeOH,C=1.02,23℃).No.2a-105CDCl3 300MHz93(1H,d,J=9.9Hz),1.09和1.21(每个3H,每个s),1.51-2.44(14H,m),3.90(6H,s),4.20(1H,m),5.38-5.50(2H,m),5.87(1H,d,J=9.0Hz),6.25和7.54(每个1H,每个d,J=15.6Hz),6.84(1H,d,J=8.1Hz),7.03(1H,d,J=1.8Hz),7.09(1H,dd,J=1.8 and 8.1Hz).IR(CHCl3)3439,3028,3012,2937,2871,2841,1739,1708,1661,1620,1600,1513/cm.[α]D=+77.3°(MeOH,C=1.01,23℃).No.2a-106[α]D=+67.O°(MeOH,C=1.00,25℃).No.2a-107[α]D=+66.6°(MeOH,C=1.01,24℃).m.p.168.0-170.0℃No.2a-108 [α]D=+61.8°(MeOH,C=1.00,22℃).No.2a-109CDCl3 300MHz0.96(1H,d,J=10.2Hz),1.10和1.22(每个3H,每个s),1.51-2.45(14H,m),4.25(1H,m),5.33-5.49(2H,m),6.21(1H,d,J=8.7Hz),7.25和 7.60(每个2H,每个d,J=8.7Hz),7.33-7.41(5H,s).IR(CHCl3)3453,3062,3028,3014,2925,2870,1739,1708,1651,1594,1557,1515,1481/cm.[α]D=+61.0°(MeOH,C=1.01,22℃).No.2a-110CD3OD 300MHz0.94(1H,d,J=9.9Hz),1.13和1.22(每个3H,每个s),1.54-2.37(14H,m),4.12(1H,m),5.38-5.49(2H,m),7.25和7.68(每个2H,每个d,J=8.7Hz),7.41(5H,s)IR(KBr)3435,3058,2986,2920,2866,1635,1595,1562,1521,1482,1439,1411/cm.[α]D=+47.3°(MeOH,C=1.01,23℃).No.2a-111[α]D=+65.6°(MeOH,C=1.01,24℃).No.2a-112CDCl3 300MHz0.97(1H,d,J=10.2Hz),1.12和1.23(每个3H,每个s),1.51-2.46(14H,m),4.27(1H,m),5.35-5.50(2H,m),6.22(1H,d,J=8.4Hz),7.40和7.66(每个2H,每个d,J=9.0Hz).IR(CHCl3)3439,3028,3012,2937,2871,2841,1739,1708,1661,1620,1600,1513/cm.[α]D=+65.6°(MeOH,C=1.01,22℃).No.2a-113[α]D=+59.6°(MeOH,C=1.00,24℃).No.2a-114CDCl3 300MHz0.98(1H,d,J=10.2Hz),1.12和1.24(每个3H,每个s),1.52-2.46(14H,m),4.29(1H,m),5.35-5.51(2H,m),6.28(1H,d,J=8.4Hz),7.70和7.83(每个2H,每个d,J=8.4Hz).IR(CHCl3)3439,3028,3012,2937,2871,2841,1739,1708,1661,1620,1600,1513/cm.[α]D=+60.6°(MeOH,C=1.01,22℃).No.2a-115[α]D=+59.7°(MeOH,C=0.99,24℃).No.2a-116CDCl3 300MHz0.97(1H,d,J=10.2Hz),1.12和1.23(每个3H,每个s),1.52-2.46(14H,m),2.39(3H,s),4.27(1H,m),5.33-5.51(2H,m),6.24(1H,d,J=9.0Hz),7.23和7.62(每个2H,每个d,J=8.4Hz).IR(CHCl3)3439,3028,3012,2937,2871,2841,1739,1708,1661,1620,1600,1513/cm.[α]D=+59.7°(MeOH,c=0.99,24℃).No.2a-117[α]D=+56.7°(MeOH,c=1.00,23℃).No.2a-118CDCl3 300MHz0.96(1H,d,J=10.2Hz),1.11和1.23(每个3H,每个s),1.53-2.44(14H,m),4.23(1H,m),5.34-5.51(2H,m),6.02(2H,s),6.13(1H,d,J=8.7Hz),6.83(1H,dd,J=1.2and 7.8Hz),7.22-7.25(2H,m).IR(CHCl3)3453,3031,3020,3012,2924,2870,1740,1708,1650,1619,1605,1519,1504.1480/cm.[α]D=+57.2°(MeOH,c=1.02,23℃).No.2a-119CDCl3 300MHz0.96(1H,d,J=10.5Hz),1.07和1.23(每个3H,每个s),1.51-2.44(14H,m),2.32(3H,s),4.26(1H,m),5.37-5.52(2H,m),6.40(1H,d,J=9.0Hz),7.09(1H,m),7.30(1H,m),7.46(1H,m),7.66(1H,m).IR(CHCl3)3443,3028,3012,2925,2870,1766,1747,1709,1657,1607,1516,1479/cm.[α]D=+53.2°(MeOH,c=0.99,21℃).No.2a-120CDCl3 300MHz0.98(1H,d,J=10.2Hz),1.14和1.24(每个3H,每个s),1.53-2.44(14H,m),4.30(1H,m),5.35-5.52(2H,m),6.42(1H,d,J=8.7Hz),6.85(1H,m),6.99(1H,dd,J=1.2and 8.4Hz),7.27(1H,m),7.39(1H,m).IR(CHCl3)3463,3033,3021,3014,2992,2924,2870,1708,1643,1597,1523,1488/cm.[α]D=+46.3°(MeOH,c=1.01,21℃).No.2a-121CDCl3 300MHz0.98(1H,d,J=10.2Hz),1.14和1.23(每个3H,每个s),1.47-2.47(14H,m),3.95(3H,s),4.31(1H,m),5.32-5.50(2H,m),6.98(1H,dd,J=0.9和8.4Hz),7.09(1H,ddd,J=0.9,7.7和8.4Hz),7.45(1H,m),8.19(1H,dd,J=2.1和8.1Hz),8.32(1H,d,J=9.0Hz).IR(CHCl3)3400,3078,3028,3020,3007,2924,2870,2842,1736,1708,1640,1600,1536,1483,1470/cm.[α]D=+38.1°(MeOH,c=1.02,23℃).No.2a-122[α]D=+42.3°(MeOH,c=0.99,23℃).No.2a-123[α]D=+38.7°(MeOH,c=1.00,21℃).No.2a-124[α]D=+45.0°(MeOH,c=1.01,21℃).m.p.119.0-120.0℃No.2a-125[α]D=+49.8°(MeOH,c=1.01,22℃).No.2a-126CDCl3 300MHz0.97(1H,d,J=10.2Hz),1.11和1.23(每个3H,每个s),1.52-2.47(14H,m),4.26(1H,m),5.34-5.50(2H,m),6.22(1H,d,J=8.7Hz),7.55-7.61(4H,m).IR(CHCl3)3400,3078,3028,3020,3007,2924,2870,2842,1736,1708,1640,1600,1536,1483,1470/cm.[α]D=+63.0°(MeOH,c=1.01,23℃).No.2a-127CDCl3 300MHz0.91(1H,d,J=10.2Hz),1.10和1.20(每个3H,每个s),1.50-2.42(14H,m),4.23(1H,m),5.31-5.51(2H,m),6.45(1H,d,J=8.4Hz),7.01(1H,t,J=7.4Hz),7.22-7.27(2H,m),7.33-7.40(4H,m),7.53(2H,d,J=9.0Hz),8.30和8.48(每个1H,每个s)IR(CHCl3)3452,3028,3022,3015,2925,2870,1708,1654,1590,1514,1478/cm.[α]D=+59.5°(MeOH,c=1.01,23℃).No.2a-128d6-DMSO 300MHz0.84(1H,d,J=9.9Hz),1.06和1.19(每个3H,每个s),1.37-2.37(14H,m),3.79(1H,m),5.35-5.51(2H,m),6.08(1H,d,J=8.7Hz),6.85-6.90(1H,m),7.18-7.23(2H,m),7.35-7.38(2H,m),8.42(1H,s),12.00(1H,s).IR(Nujol)3395,3345,2925,2866,2623,2506,1697,1658,1638,1597,1557/cm.[α]D=+26.0°(MeOH,c=1.01,23℃).m.p.164.0-166.0℃No.2a-129CDCl3 300MHz1.01(1H,d,J=10.0Hz),1.17和1.25(每个3H,每个s),1.54-2.52(14H,m),4.34(1H,m),5.36-5.57(2H,m),6.42(1H,d,J=8.6Hz),7.51-7.60(2H,m),7.77(1H,dd,J=1.8和8.6Hz),7.85-7.96(3H,m),8.24(1H,brs).IR(CHCl3)3451,3060,3028,3010,2925,2870,1708,1652,1629,1600,1517,1502/cm.[α]D=+68.6°(MeOH,c=1.00,22℃).No,2a-130CDCl3 300MHz1.02(1H,d,J=10.2Hz),1.04和1.26(每个3H,每个s),1.54-2.52(14H,m),4.41(1H,m),5.41-5.58(2H,m),6.14(1H,d,J=9.0Hz),7.43-7.59(4H,m),7.85-7.92(2H,m),8.27(1H,dd,J=1.8和7.2Hz).IR(CHCl3)3436,3032,3010,2924,2870,2664,1708,1652,1512,1498/cm.[α]D=+93.9°(MeOH,c=1.00,22℃)m.p.94.0-96.0℃No.2a-131[α]D=+50.2°(MeOH,c=0.95,21℃).No.2a-132[α]D=+10.9°(MeOH,c=0.92,21℃).No.2a-133[α]D=+60.4°(MeOH,c=1.00,21℃).No.2a-134[α]D=+38.5°(MeOH,c=1.01,23℃).No.2a-135[α]D=+52.5°(MeOH,c=1.01,23℃).m.p.180.0-182.0℃No 2a-136[α]D=+35.3°(MeOH,c=1.02,23℃).m.p.79.0-80.0℃No.2a-137CDCl3 300MHz0.97(1H,d,J=10.2Hz),1.11和1.22(每个3H,每个s),1.43(3H,t,J=6.9Hz),1.52-2.44(14H,m),4.03(2H,q,J=6.9Hz),4.26(1H,m),5.33-5.50(2H,m),6.19(1H,d,J=8.7Hz),6.88-7.00(6H,m),7.65-7.68(2H,m).IR(CHCl3)3455,3031,3024,3014,2988,2925,2870,1741,1708,1649,1602,1521,1504,1490/cm.[α]D=+52.0°(MeOH,c=1.01,23℃).No.2a-138CDCl3 300MHz0.97(1H,d,J=10.2Hz),1.11和1.22(每个3H,每个s),1.35(6H,d,J=6.0Hz),1.53-2.46(14H,m),4.25(1H,m),4.51(1H,m),5.33-5.50(2H,m),6.12(1H,d,J=9.0Hz),6.87-6.99(6H,m),7.65-7.68(2H,m).IR(CHCl3)3454,3031,3014,2980,2925,2870,1741,1708,1649,1602,1522,1490/cm.[α]D=+50.0°(MeOH,c=1.05,22℃).No.2a-139CDCl3 300MHz1.00(1H,d,J=10.2Hz),1.16和1.24(每个3H,每个s),1.59-2.52(14H,m),4.31(1H,m),5.40-5.53(2H,m),6.36(1H,d,J=8.7Hz),6.70(1H,d,J=1.5Hz),7.12(1H,m),7.30(1H,m),7.47(1H,dd,J=0.6和 8.1Hz),7.61(1H,d,J=8.4Hz).IR(CHCl3)3449,3243,3029,3022,3013,2925,2871,1707,1631,1542,1505/cm.[α]D=+63.4°(MeOH,c=1.00,23℃).m.p.178.0-179.0℃No.2a-140CDCl3 300MHz0.97(1H,d,J=10.2Hz),1.18和1.23(每个3H,每个s),1.57-2.50(14H,m),4.35(1H,m),5.32-5.55(2H,m),6.42(1H,d,J=8.7Hz),6.70(1H,d,J=1.5Hz),7.21-7.24(2H m),7.46(1H,m),7.76(1H,m),7.86(1H,d,J=3.0Hz),10.20(1H,s).IR(CHCl3)3465,3010,2924,1739,1604,1546,1504/cm.[α]D=+39.4°(MeOH,c=1.01,22℃).m.p.167.0-168.0℃No.2a-141CDCl3 300MHz0.99(1H,d,J=10.2Hz),1.14和1.24(每个3H,每个s),1.55-2.44(14H,m),3.84(3H,s),4.27(1H,m),5.34-5.52(2H,m),6.28(1H,d,J=9.0Hz),6.91和7.47(每个2H,每个d,J=9.0Hz),6.98和7.14(每个1H,每个d,J=16.5Hz),7.54和7.70(每个2H,每个d,J=8.7Hz).IR(CHCl3)3453,3025,3015,2925,2870,2839,1740,1708,1649,1602,1510,1493,1470/cm.[α]D=+73.4°(MeOH,c=1.02,22℃).m.p.155.0-157.0℃No.2a-142CDCl3 300MHz0.97(1H,d,J=10.2Hz),1.11和1.23(每个3H,每个s),1.52-2.45(14H,m),3.79(3H,s),4.27(1H,m),5.34-5.50(2H,m),6.24(1H,d,J=9.0Hz),6.49和6.62(每个1H每个d,J=12.3Hz),6.77和7.16(每个2H,每个d,J=8.7Hz),7.32和 7.59(每个2H,每个d,J=8.1Hz).IR(CHCl3)3453,3025,3014,2925,2870,2839,1739,1708,1649,1606,1510,1494/cm.[α]D=+60.7°(MeOH,c=0.99,22℃).No.2a-143[α]D=+57.3°(MeOH,c=1.01,23℃).No.2a-144[α]D=+12.2°(MeOH,c=1.00,23℃).m.p.114.0-116.0℃No.2a-145CDCl3 300MHz0.95(1H,d,J=10.2Hz),1.10和1.21(每个3H,每个s),1.52-2.44(14H,m),4.25(1H,m),5.33-5.49(2H,m),6.37(1H,d,J=8.7Hz),7.45-7.47(3H,m),7.62-7.66(2H,m),7.69和7.80(每个2H,每个d,J=7.5Hz,).IR(CHCl3)3449,3058,3027,3012,2925,2870,1708,1655,1513,1481,1043/cm.[α]D=+61.0°(MeOH,c=1.01,23℃).No.2a-146CDCl3 300MHz0.95(1H,d,J=10.5Hz),1.09和1.21(每个3H,每个s),1.50-2.41(14H,m),4.25(1H,m),5.33-5.49(2H,m),6.33(1H,d,J=8.4Hz),7.49-7.61(3H,m),7.91.7.92(2H,m),7.82和7.97(每个2H,每个d,J=8.7Hz,).IR(CHCl3)3447,3029,3023,3015,2925,2870,1708,1660,1514,1484,1321,1161/cm.[α]D=+62.0°(MeOH,c=1.00,22℃).No.2a-147CDCl3 300MHz0.97(1H,d,J=10.2Hz),1.12和1.23(每个3H,每个s),1.52-2.46(14H,m),2.51(3H,s),4.26(1H,m),5.34-5.51(2H,m),6.23(1H,d,J=8.4Hz),7.26和7.64(每个2H,每个d,J=8.4Hz).IR(CHCl3)3453,3027,3015,2925,2870,2665,1708,1648,1596,1516,1484/cm.[α]D=+67.7°(MeOH,c=0.82,22℃).No.2a-148[α]D=+72.5°(MeOH,c=1.01,25℃).No.2a.149[α]D=+67.8°(MeOH,c=0.98,25℃).No.2a-150CDCl3 300MHz0.94(1H,d,J=10.2Hz),1.10和1.23(每个3H,每个s),1.52-2.50(14H,m),4.22(1H,m),5.36-5.55(2H,m),6.48(1H,d,J=8.4Hz),8.35(1H,s),8.90(1H,s).IR(CHCl3)3443,3374,3091,3024,3012,2925,2871,1709,1652,1525,1494/cm.[α]D=+58.1°(MeOH,c=1.01,23℃).m.p.120.0-122.0℃No.2a-151[α]D=+40.6°(MeOH,c=1.01,23℃).No.2a-152CDCl3 300MHz0.96(1H,d,J=10.5Hz),1.10和1.24(每个3H,每个s),1.50-2.50(14H,m),2.71(3H,s),4.26(1H,m),5.37-5.51(2H,m),6.02(1H,d,J=9.0Hz),8.73(1H,s).IR(CHCl3)3463,3435,3087,3025,3014,2925,2870,1708,1649,1523,1503/cm.[α]D=+54.1°(MeOH,c=1.02,22℃).No.2a-153CDCl3 300MHz0.95(1H,d,J=9.9Hz),1.11和1.23(每个3H,每个s),1.50.2.50(14H,m),2.50(3H,s),4.26(1H,m),5.36-5.51(2H,m),6.01(1H,d,J=8.4Hz),6.88(1H,d,J=5.1Hz),7.26(1H,d,J=5.1Hz).IR(CHCl3)3469,3431,3025,3013,2925,2871,2664,1708,1639,1544,1505/cm.[α]D=+35.8°(MeOH,c=1.03,22℃).No.2a-154CDCl3 300MHz0.95(1H,d,J=9.9Hz),1.10和1.22(每个3H,每个s),1.52-2.46(14H,m),2.51(3H,d,J=1.2Hz),4.26(1H,m),5.34-5.50(2H,m),6.00(1H,d,J=8.4Hz),6.73(1H,dd,J=5.1和3.6Hz),7.29(1H,d,J=3.6Hz).IR(CHCl3)3450,3431,3026,3011,2925,2869,1739,1708,1639,1547,1508/cm.[α]D=+50.5°(MeOH,c=1.01,22℃).No.2a-155CDCl3 300MHz0.99(1H,d,J=10.2Hz),1.19和1.25(每个3H,每个s),1.53-2.48(14H,m),4.31(1H,m),5.36-5.51(2H,m),6.79(1H,d,J=9.3Hz),7.29(1H,m),7.41(1H,m),7.48(1H,s),7.51(1H,m),7.66(1H,d,J=8.1Hz).IR(CHCl3)3436,3029,3024,3015,2925,2871,2670,1708,1659,1598,1510/cm.[α]D=+69.1°(MeOH,c=1.01,22℃).No.2a-156CDCl3∶CD3OD=10∶1 300MHz0.99(1H,d,J=9.9Hz),1.11和1.21(每个3H,每个s),1.56-2.58(14H,m),4.22(1H,m),5.35-5.59(2H,m),6.83(1H,d,J=8.4Hz),7.48(1H,d,J=8.4Hz),7.61(1H,dd,J=1.5和8.4Hz),8.09(1H,d,J=1.5Hz),8.12(1H,s).IR(KBr)3422,3 115,2985,2922,2869,2609,1708,1636,1578,1529,1470/cm.[α]D=+62.8°(MeOH,c=1.01,22℃).No.2a-157[α]D=+40.0°(MeOH,c=0.95,22℃).No.2a-158CDCl3 300MHz1.00(1H,d,J=10.5Hz),1.17和1.24(每个3H,每个s),1.54-2.50(14H,m),4.34(1H,m),5.36-5.52(2H,m),7.80(1H,d,J=9.0Hz),9.30(1H,s).IR(CHCl3)3410,3122,3030,3012,2925,2871,2668,1709,1667,1538,1466/cm.[α]D=+44.9°(MeOH,c=0.99,22℃).No.2a-159CDCl3 300MHz0.97(1H,d,J=10.2Hz),1.13和1.22(每个3H,每个s),1.55-2.43(14H,m),3.03(6H,s),4.23(1H,m),5.32-5.51(2H,m),6.16(1H,d,J=8.7Hz),6.87和7.63(每个2H,每个d,J=8.7Hz).IR(CHCl3)3457,3028,3006,2924,2870,2654,1739,1709,1637,1608,1608,1534,1501/cm.[α]D=+64.8°(MeOH,c=1.01,22℃).No.2a-160d6-DMSO 300MHz0.83(1H,d,J=9.9Hz),1.02和1.19(每个3H,每个s),1.38-1.61(3H,m),1.90-2.32(11H,m),3.90(1H,m),5.41-5.44(2H,m),7.32(1H,dd,J=0.9和 7.2Hz),7.45-7.60(2H,m),7.77(1H,dd,J=0.9和7.8Hz),8.03(1H,d,J=6.9Hz),12.40(1H,s).IR(液蜡)3315,2924,2856,2656,2535,1737,1703,1637,1598,1581,1541/cm.[α]D=+78.5°(MeOH,c=1.01,24℃).m.p.161.0-162.0℃No.2a-161[α]D=+65.3°(MeOH,c=1.00,22℃).No.2a-162CDCl3 300MHz0.99(1H,d,J=10.2Hz),1.13和1.25(每个3H,每个s),1.53-2.45(14H,m),4.30(1H,m),5.36-5.51(2H,m),6.32(1H,d,J=8.4Hz),7.88和8.28(每个2H,每个d,J=9.0Hz).IR(CHCl3)3448,3029,3016,2925,2870,1708,1664,1602,1527,1484,1347/cm.[α]D=+72.7°(MeOH,c=1.02,22℃).No.2a-163CDCl3 300MHz0.96(1H,d,J=10.2Hz),1.11和1.23(每个3H,每个s),1.55-2.51(14H,m),4.26(1H,m),5.36-5.57(2H,m),6.68(1H,d,J=7.8Hz),7.41(1H,dd,J=4.8和8.1Hz),8.20(1H,d,J=8.1Hz),8.66(1H,d,J=4.8Hz),9.00(1H,s).IR(CHCl3)3448,3026,3013,2925,2870,2534,1709,1658,1590,1515,1471/cm.[α]D=+71.3°(MeOH,c=1.01,22℃).No.2a-164[α]D=+40.8°(MeOH,c=0.98,22℃).No.2a-165CDCl3 300MHz0.96(1H,d,J=10.5Hz),1.11和1.24(每个3H,每个s),1.55-2.52(14H,m),4.24(1H,m),5.37-5.57(2H,m),6.63(1H,d,J=7.8Hz),7.59和8.63(每个2H每个d,J=6.0Hz).IR(CHCl3)3447,3346,3028,3016,2925,2870,2538,1941,1708,1662,1556,1516/cm.[α]D=+75.4°(MeOH,c=1.01,22℃).No.2a-166CDCl3 300MHz0.97(1H,d,J=10.2Hz),1.11和1.22(每个3H,每个s),1.51-2.44(14H,m),2.95(6H,s),4.25(1H,m),5.33-5.50(2H,m),6.19(1H,d,J=8.7Hz),6.77和6.97(每个2H,每个d,J=8.4Hz),6.94和7.65(每个2H,每个d,J=9.0Hz).IR(CHCl3)3453,3024,3016,2924,2871,2806,1739,1708,1647,1612,1604,1515,1490/cm.[α]D=+53.1°(MeOH,c=1.02,23℃).m.p.104.0-105.5℃No.2a-167CDCl3 300MHz1.01(1H,d,J=9.9Hz),1.19和1.26(每个3H,每个s),1.56-2.53(14H,m),4.37(1H,m),5.35-5.55(2H,m),6.47(1H,d,J=8.4Hz),7.61-7.71(2H,m),7.79(2H,s),7.89-7.97(2H,m),8.27(1H,d,J=2.1Hz),8.66-8.73(2H,m).IR(CHCl3)3450,3024,3014,2925,2870,2667,1707,1650,1531,1509/cm.[α]D=+70.5°(MeOH,c=1.00,22℃).No.2a-168CDCl3 300MHz1.02(1H,d,J=10.2Hz),1.20和1.26(每个3H,每个s),1.56-2.50(14H,m),4.38(1H,m),5.36-5.56(2H,m),6.51(1H,d,J=8.4Hz),7.61-7.93(7H,m),8.74(1H,d,J=8.4Hz),9.15(1H,s).IR(CHCl3)3517,3451,3060,3028,3011,2925,2870,2664,1709,1651,1519,1498/cm.[α]D=+54.4°(MeOH,c=1.00,23℃).No.2a-169CDCl3 300MHz0.96(1H,d,J=10.5Hz),1.09和1.21(每个3H,每个s),1.50-2.44(14H,m),3.85(3H,s),4.24(1H,m),5.32-5.48(2H,m),6.19(1H,d,J=8.4Hz),6.94和7.45(每个2H,每个d,J=9.0Hz),7.11和7.45(每个2H,每个d,J=8.7Hz).IR(CHCl3)3516,3453,3029,3009,2925,2870,2840,2665,1708,1650,1593,1515,1493.1482/cm.[α]D=+57.8°(MeOH,c=1.00,23℃).No.2a-170CDCl3 300MHz0.98(1H,d,J=10.2Hz),1.15和1.24(每个3H,每个s),1.52-2.50(14H,m),4.28(1H,m),5.33-5.54(2H,m),6.25(1H,d,J=8.2Hz),7.38-7.44(2H,m),7.74(1H,s),7.81-7.86(2H,m).IR(CHCl3)3517,3448,3427,3024,3013,2925,2870,2669,1708,1650,1562,1535,1500/cm.[α]D=+61.6°(MeOH,c=1.00,23℃).No.2a-171CDCl3 300MHz0.96(1H,d,J=10.2Hz,1.11和1.22(每个3H,每个s),1.52-2.42(14H,m),2.48(3H,s),4.21(1H,m),5.31.5.52(2H,m),6.06(1H,d,J=8.2Hz),6.97和7.59(每个1H,每个d,J=1.2Hz).IR(CHCl3)3452,3113,3028,3007,2925,2870,2669,1708,1645,1554,1509/cm.[α]D=+52.4°(MeOH,c=1.00,23℃).No.2a-172CDCl3 300MHz0.96(1H,d,J=10.2Hz),1.09和1.28(每个3H,每个s),1.50-2.40(14H,m),2.69(3H,s),4.24(1H,m),5.35-5.51(2H,m),5.96(1H,d,J=8.7Hz),7.03和7.07(每个1H,每个d,J=5.4Hz).IR(CHCl3)3451,3031,3013,2925,2870,2666,1708,1647,1542,1497/cm.[α]D=+51.2°(MeOH,c=1.00,23℃).No.2a-173CDCl3 300MHz0.95(1H,d,J=10.2Hz),1.10和1.23(每个3H,每个s),1.50-2.45(14H,m),4.22(1H,m),5.35-5.49(2H,m),6.05(1H,d,J=8.4Hz),7.26和7.75(每个1H,每个d,J=1.5Hz).IR(CHCl3)3451,3011,3029,3011,2925,2870,1708,1652,1538,1500/cm.[α]D=+50.6°(MeOH,c=1.01,23℃).No.2a-174CDCl3 300MHz0.96(1H,d,J=10.2Hz),1.13和1.23(每个3H,每个s),1.52-2.50(14H,m),4.29(1H,m),5.35-5.51(2H,m),7.02(1H,d,J=8.4Hz),7.32和8.16(每个1H,每个d,J=3.9Hz).IR(CHCl3)3417,3115,3023,3014,2925,2870,1708,1645,1530/cm.[α]D=+48.8°(MeOH,c=1.02,23℃).No.2a-175CDCl3 300MHz0.97(1H,d,J=10.2Hz),1.14和1.23(每个3H,每个s),1.50-2.52(14H,m),2.52(3H,s),4.29(1H,m),5.34-5.51(2H,m),7.78(1H,d,J=9.0Hz),7.24和7.52(每个1H,每个d,J=5.4Hz).IR(CHCl3)3329,3093,3023,3015,2924,2871,1708,1640,1526/cm.[α]D=+45.0°(MeOH,c=1.01,23℃).No.2a-176CDCl3 300MHz0.95(1H,d,J=10.5Hz),1.09和1.23(每个3H,每个s),1.52-2.46(14H,m),2.40(3H,d,J=0.9Hz),4.24(1H,m),5.35-5.51(2H,m),6.05(1H,d,J=8.7Hz),6.95(1H,m),7.57(1H,d,J=3.3Hz).IR(CHCl3)3517,3444,3103,3024,3013,2926,2870,1739,1708,1649,1636,1507/cm.[α]D=+54.8°(MeOH,c=1.01,23℃).m.p.97.0-99.0℃No.2a-177CDCl3 300MHz0.97(1H,d,J=10.2Hz),1.11和1.23(每个3H,每个s),1.52-2.45(14H,m),3.93(3H,s),4.27(1H,m),5.34-5.50(2H,m),6,35(1H,d,J=3.3Hz),7.80(1H,d,J=8.7Hz),8.10(1H,d,J=3.3Hz).IR(CHCl3)3395,3121,3031,3019,3012,2925,2871,1739,1709,1640,1557,1533/cm.[α]D=+22.8°(MeOH,c=1.01,23℃).m.p.109.0-112.0℃No.2a-178CDCl3 300MHz0.96(1H,d,J=10.5Hz),1.10和1.23(每个3H,每个s),1.51-2.45(14H,m),4.24(1H,m),5.35-5.50(2H,m),6.09(1H,d,J=8.4Hz),7.17-7.31(6H,m),7.95(1H,d,J=1.5Hz).IR(CHCl3)3510,3451,3062,3031,3022,3011,2925,2870,2662,1708,1651,1582,1535.1497.1477/cm.[α]D=+47.9°(MeOH,c=1.01,25℃).No.2a-179CDCl3 300MHz0.96(1H,d,J=10.2Hz),1.14和1.24(每个3H,每个s),1.52-2.48(14H,m),4.30(1H,m),5.36-5.52(2H,m),6.73(1H,d,J=9.0Hz),6.26和7.37(每个1H,每个d,J=6.0Hz).IR(CHCl3)3509,3429,3115,3094,3025,3014,2925,2871,2666,1708,1649,1529,1510/cm.[α]D=+51.0°(MeOH,c=1.02,25℃).No.2a-180CDCl3 300MHz0.95(1H,d,J=10.2Hz),1.14和1.24(每个3H,每个s),1.52-2.46(14H,m),3.89(3H,s),4.21(1H,m),5.35-5.50(2H,m),6.05(1H,d,J=8.4Hz),6.46和7.04(每个1H,每个d,J=1.8Hz).IR(CHCl3)3516,3450,3114,3031,3010,2925,2871,1708,1648,1546,1511,1477/cm.[α]D=+49.1°(MeOH,c=1.01,25℃).No.2a-181CDCl3 300MHz0.97(1H,d,J=10.2Hz),1.14和1.23(每个3H,每个s),1.52-2.48(14H,m),2.42(3H,s),4.31(1H,m),5.34-5.52(2H,m),8.07(1H,d,J=9.3Hz),7.27和8.17(每个1H,每个d,J=3.3Hz).IR(CHCl3)3510,3301,3112,3023,3007,2924,2871,2663,1708,1636,1534/cm.[α]D=+41.0°(MeOH,c=0.96,25℃).No.2a-182CDCl3 300MHz0.96(1H,d,J=10.2Hz),1.11和1.23(每个3H,每个s),1.53-2.46(14H,m),2.51(3H,s),4.21(1H,m),5.35-5.51(2H,m),6.05(1H,d,J=8.1Hz),7.26和7.78(每个1H,每个d,J=1.8Hz).IR(CHCl3)3509,3450,3109,3024,3012,2925,2870,2666,1708,1650,1535,1498.1471/cm.[α]D=+52.9°(MeOH,c=0.95,25℃).No.2a-183CDCl3 300MHz0.96(1H,d,J=10.5Hz),1.12和1.22(每个3H,每个s),1.52-2.46(14H,m),4.25(1H,m),5.33-5.51(2H,m),6.17(1H,d,J=8.7Hz),7.01-7.05(3H,m).7.14和7.62(每个2H,每个d,J=8.7Hz),7.27-7.34(2H,m).IR(CHCl3)3428,3026,3015,2925,2870,2666,1739,1708,1643,1613,1594,1526,1499/cm.[α]D=+64.8°(MeOH,c=1.02,23℃).No.2a-184CDCl3 300MHz1.01(1H,d,J=10.2Hz),1.18和1.26(每个3H,每个s),1.55-2.50(14H,m),4.35(1H,m),5.35-5.55(2H,m),6.42(1H,d,J=8.7Hz),7.46-7.52(2H,m).7.73(1H,dd,J=1.8和8.4Hz),7.83-7.89(2H,m),8.21(1H,m),8.59(1H,d,J=1.5Hz).IR(CHCl3)3451,3031,3014,2925,2870,2660,1739,1708,1650,1604,1513,1463/cm.[α]D=+58.3°(MeOH,c=1.00,23℃).No.2a-185CDCl3 300MHz1.00(1H,d,J=10.2Hz),1.18和1.25(每个3H,每个s),1.55-2.50(14H,m),4.34(1H,m),5.35-5.54(2H,m),6.36(1H,d,J=8.7Hz),7.37(1H,t,J=7.4Hz),7.50(1H,m),7.57-7.59(2H,m),7.79(1H,dd,J=1.8和8.1Hz),7.99(1H,d,J=7.8Hz),8.39(1H,d,J=1.8Hz).IR(CHCl3)3451,3030,3020,2870,2665,1708,1652,1632,1603,1586,15 14,1469,1448/cm.[α]D=+59.4°(MeOH,c=1.0l,24℃).No.2a-186CDCl3 300MHz1.00(1H,d,J=10.5Hz),1.17和1.25(每个3H,每个s),1.54-2.50(14H,m),4.33(1H,m),5.35-5.54(2H,m),6.37(1H,d,J=8.7Hz),7.37(1H,t,J=7.4Hz),7.51(1H,t,J=7.8Hz),7.56(1H,m),7.70(1H,dd,J=1.2 and 8.4Hz),7.97(3H,m).IR(CHCl3)3451,3030,3014,2924,2870,2671,1739,1708,1652,1577,1517,1488,1471/cm.[α]D=+72.2°(MeOH,c=1.00,24℃).No.2a-187CDCl3 300MHz1.00(1H,d,J=9.8Hz),1.18和1.25(每个3H,每个s),1.54-2.53(14H,m),4.07(3H,s),4.37(1H,m),5.30-5.54(2H,m),7.34(1H,m),7.47(1H,s),7.47-7.60(2H,m),7.93(1H,d,J=7.8Hz),8.43(1H,s),8.49(1H,d,J=9.0Hz).IR(CHCl3)3397,3074,3027,3020,3009,2924,1738,1708,1647,1633,1534,1465,1453/cm.[α]D=+43.7°(MeOH,c=1.01,25℃).No.2a-188CDCl3 300MHz0.97(1H,d,J=10.2Hz),1.11和1.23(每个3H,每个s),1.53-2.50(14H,m),4.23(1H,m),5.37-5.50(2H,m),6.10(1H,d,J=9.0Hz),6.20(1H,m),6.51(1H,m),6.97(1H,m),10.81(1H,brs).IR(CHCl3)3450,3236,3112,3029,3015,2925,2871,2645,1701,1616,1558,1516/cm.[α]D=+50.6°(MeOH,c=1.01,24℃).No.2a-189CDCl3 300MHz0.94(1H,d,J=9.9Hz),1.11和1.23(每个3H,每个s),1.50-2.46(14H,m),3.93(3H,s),4.18(1H,m),5.35-5.52(2H,m),6.03(1H,d,J=9.3Hz),6.09(1H,m),6.48(1H,m),6.73(1H,m).IR(CHCl3)3452,3102,3028,3007,2925,2871,2666,1739,1708,1650,1536,1499,1471/cm.[α]D=+49.8°(MeOH,c=1.01,23℃).m.p.101.5-103.5℃No.2a-190CDCl3 300MHz0.94(1H,d,J=10.2Hz),1.11和1.21(每个3H,每个s),1.54-2.47(14H,m),4.23(1H,m),5.33-5.52(2H,m),6.06(1H,d,J=9.0Hz),6.34(1H,m),6.75(1H,m),6.36(1H,m),9.71(1H,brs).IR(CHCl3)3470,3215,3030,3020,3010,2925,2871,2664,1709,1613,1564,1510/cm.[α]D=+43.3°(MeOH,c=1.01,24℃).No.2a-191CDCl3 300MHz0.96(1H,d,J=10.2Hz),1.11和1.22(每个3H,每个s),1.55-2.44(14H,m),3.66(3H,s),4.20(1H,m),5.35-5.51(2H,m),5.93(1H,d,J=8.4Hz),6.27(1H,dd,J=1.8and 2.7Hz),6.56(1H,t,J=2.7Hz),7.19(1H,t,J=1.8Hz).IR(CHCl3)3452,3031,3018,3006,2925,2871,2662,1736,1710,1634,1609,1556,1498/cm.[α]D=+43.1°(MeOH,c=1.01,23℃).No.2a-192CDCl3 300MHz0.96(1H,d,J=10.5Hz),1.11和1.21(每个3H,每个s),1.43(3H,t,J=7.5Hz),1.54-2.44(14H,m),3.93(2H,q,J=7.5Hz),4.21(1H,m),5.33-5.51(2H,m),5.94(1H,d,J=8.4Hz),6.27(1H,dd,J=1.8和2.7Hz),6.62(1H,t,J=2.7Hz),7.26(1H,t,J=1.8Hz).IR(CHCl3)3630,3452,3032,3018,3006,2925,2871,2661,1735,1710,1633,1610,1555.1497/cm.[α]D=+40.1°(MeOH,c=1.00,23℃).No.2a-193CDCl3 300MHz0.95(1H,d,J=10.2Hz),1.10和1.22(每个3H,每个s),1.53-2.49(14H,m),2.58(3H,s),4.21(1H,m),5.35-5.54(2H,m),6.15(1H,d,J=8.1Hz),6.52(1H,dd,J=1.8和3.6Hz),7.29(1H,t,J=3.6Hz),7.94(1H,t,J=1.8Hz).IR(CHCl3)3516,3450,3410,3152,3027,3015,2925,2871,2670,1732,1648,1574,1509/cm.[α]D=+45.0°(MeOH,c=1.01,25℃).No.2a-194CDCl3 300MHz0.99(1H,d,J=10.2Hz),1.11和1.24(每个3H,每个s),1.52-2.53(14H,m),4.34(1H,m),5.33-5.57(2H,m),6.21(1H,d,J=8.6Hz),7.35-7.50(2H,m),7.83(1H,s),7.86(1H,m),.8.31(1H,m).IR(CHCl3)3443,3067,3013,2925,2870,2665,1708,1651,1515,1493/cm.[α]D=+55.7°(MeOH,c=1.01,23℃).No.2a-195CDCl3 300MHz1.01(1H,d,J=10.0Hz),1.06和1.26(每个3H,每个s),1.50-2.64(14H,m),2.68(3H,s),4.40(1H,m),5.36-5.61(2H,m),6.02(1H,d,J=9.4Hz),7.30-7.42(2H,m),7.73-7.86(2H,m).IR(CHCl3)3510,3434,3062,3029,3014,2924,2871,2669,1708,1650,1563,1539,1500/cm.[α]D=+72.4°(MeOH,c=1.00,23℃).m.p.111.0-112.0℃No.2a-196CDCl3 300MHz0.42和1.04(每个3H,每个s),0.80(1H,d,J=10.0Hz),1.11-2.48(14H,m),2.24(3H,s),4.02(1H,m),5.23-5.44(2H,m),5.53(1H,d,J=8.8Hz),7.27-7.31(2H,m),7.42-7.48(3H,m),7.93(1H,s).IR(CHCl3)3419,3114,3025,3006,2924,2871,2662,1737,1709,1636,1540,1519/cm.[α]D=+43.7°(MeOH,c=1.01,23℃).No.2a-197CDCl3 300MHz0.95(1H,d,J=10.0Hz),1.09和1.23(每个3H,每个s),1.54-2.46(18H,m),2.77(4H,brs),4.21(1H,m),5.32-5.54(2H,m),6.02(1H,d,J=8.6Hz),7.43(1H,s).IR(CHCl3)3445,3101,3024,3014,2928,2865,2661,1739,1708 1646,1550,1507/cm.[α]D=+51.9°(MeOH,c=1.01,23℃).No.2a-198CDCl3 300MHz0.96(1H,d,J=10.2Hz),1.11和1.22(每个3H,每个s),1.50-2.44(14H,m),4.24(1H,m),4.42(2H,s),5.35-5.49(2H,m),6.25(1H,d,J=8.1Hz),7.33(1H,m),7.43(1H,dd,J=1.5和7.5Hz),7.49(1H,d,J=8.1Hz),7.60-7.63(1H,m),7.68(1H,dd,J=1.8和7.8Hz),8.02(1H,d,J=1.8Hz),8.19(1H,dd,J=1.5和8.1Hz).IR(CHCl3)3448,3030,3012,2925,2870,1739,1708,1671,1588,1559,1514,1472/cm.[α]D=+56.9°(MeOH,c=1.01,24℃).No.2a-199CDCl3 300MHz0.96(1H,d,J=10.2Hz),1.11和1.22(每个3H,每个s),1.51-2.46(14H,m),3.40(1H,m),3.76(1H,m),4.24(1H,m),5.33-5.51(3H,m),6.25(1H,m),7.16(1H,m),7.24-7.33(2H,m),7.46(1H,d,J=7.5Hz),7.52-7.60(2H,m),7.85(1H,dd,J=1.8和4.5Hz).IR(CHCl3)3583,3447,3062,3028,3013,2924,2871,2663,1708,1651,1600,1557,1514.1471/cm.[α]D=+54.8°(MeOH,c=1.00,23℃).No.2a-200CDCl3 300MHz0.96(1H,d,J=10.2Hz),1.12和1.23(每个3H,每个s),1.51-2.46(14H,m),4.25(1H,m),5.34-5.51(2H,m),6.25(1H,d,J=8.4Hz),7.02和7.10(每个,1H,每个d,J=12.3Hz),7.23-7.33(4H,m),7.50(1H,m),7.64(1H,dd,J=1.8和7.8Hz),7.82(1H,d,J=1.8Hz).IR(CHCl3)3450,3060,3025,3014,2925,2871,2662,1708,1653,1596,1542,1513,1473/cm.[α]D=+62.5°(MeOH,c=1.00,24℃).No.2a-201CDCl3 300MHz0.95(1H,d,J=9.9Hz),1.15和1.22(每个3H,每个s),1.55-2.60(14H,m),4.26(1H,m),5.35-5.63(2H,m),7.14(1H,d,J=9.9Hz),7.34和7.40(每个,1H,每个d,J=12.9Hz),7.62-7.73(4H,m),8.25-8.30(2H,m),8.72(1H,d,J=1.5Hz).IR(CHCl3)3443,3389,3297,3061,3030,3016,2925 2870,1726,1708 1652,1603,1521,1483,1472,1309/cm.[α]D=+61.1°(MeOH,c=1.01,23℃).No.2a-202CDCl3 300MHz0.96(1H,d,J=10.2Hz),1.09和1.22(每个3H,每个s),1.52-2.43(14H,m),2.63(3H,s),4.25(1H,m),5.33-5.49(2H,m),6.19(1H,d,J=8.4Hz),7.10和7.58(每个2H,每个d,J=9.0Hz),7.21(1H,m),7.30-7.32(2H,m),7.46(1H,d,J=7.5Hz)IR(CHCl3)3511,3453,3062,3032,3014,2925 2870,1739,1708,1650,1595,1556,1516,1482,1471/cm.[α]D=+60.2°(MeOH,c=1.01,25℃).No.2a-203CDCl3 300MHz0.96(1H,d,J=10.5Hz),1.09和1.23(每个3H,每个s),1.52-2.43(14H,m),4.23(1H,m),5.35-5.51(2H,m),5.93(1H,d,J=8.7Hz),6.56(1H,dd,J=0.9和1.8Hz),7.43(1H,t,J=1.8Hz),7.92(1H,dd,J=0.9和1.8Hz).IR(CHCl3)3517,3450,3134,3031,3008,2925,2870,2667,1708,1656,1588,1570,1514/cm.[α]D=+46.7°(MeOH,c=0.92,25℃).No.2b-1[α]D=+25.6°(MeOH,c=1.01,23℃).No.2b-2[α]D=+38.9°(MeOH,c=1.01,24℃).No.2c-1[α]D=+60.5°(MeOH,c=1.01,22℃).No.2c-2[α]D=+55,8°(MeOH,c=0.92,22℃).No.2c-3[α]D=+54,7°(MeOH,c=1.01,22℃).No.2d-1[α]D=-6.2°(MeOH,c=1.00,21℃).No.2d-2[α]D=+15.8°(MeOH,c=0.34,22℃).No.2d-3[α]D=+31.6°(MeOH,c=1.01,22℃).No.2e-1[α]D=-9.4°(MeOH,c=1.00,22℃).No.2e-2[α]D=-1.8°(MeOH,c=1.02,23℃).No.2e-3[α]D=-6.7°(MeOH,c=1.01,23℃).No.2f-1[α]D=+6.8°(MeOH,c=1.01,23℃).No.2f-2[α]D=-2.6°(MeOH,c=1.00,22℃).No.2f-3[α]D=-3.5°(MeOH,c==1.01,22℃).No.2g-1[α]D=+54,6°(MeOH,c=1.01,24℃).No.3a-2CDCl3 300MHz0.98-2.15(14H,m),2.31(2H,t,J=7.2Hz),2.35-2.40(1H,m),3.10-3.20(1H,m),5.00(1H,d,J=6.9Hz),5.30-5.48(2H,m),6.75(1H,d,J=10.2Hz),7.38-7.52(6H,m).IR(CDCl3)3266,3028,2954,2874,1709,1620,1448,1412,1318,1141,970,892/cm.[α]D=+20.3±0.6°(CHCl3,c=1.05,24℃).No.3a-3CDCl3 300MHz0.95-2.00(14H,m),2.20-2.29(3H,m),3.00-3.08(1H,m),3.66(3H,s),5.00(1H,d,J=6.6Hz),5.13-5.29(2H,m),7.38-7.52(3H,m),7.59-7.65(2H,m),7.69-7.75(2H,m),7.92-7.98(2H,m).IR(CHCl3)3376,3018,2946,2868,1727,1594,1436,1395,1322,1157,1095,890/cm.[α]D=+2.3±0.4°(CHCl3,c=1.03,22℃).mp.65-66.5℃No.3a-4CDCl3 300MHz0.93-2.05(14H,m),2.15-2.22(1H,m),2.31(2H,t,J=7.2Hz),3.01-3.10(1H,m),5.18-5.31(3H,m),7.38-7.52(3H,m),7.58-7.66(2H,m),7.69-7.76(2H,m),7.92-7.98(2H,m)IR(CHCl3)3374,3260,3020,2948,2868,1708,1594,1479,1396,1319,1156,1095,1052.891/cm.[α]D=+13.1±0.5°(CHCl3,c=1.16,24℃).No.3a.6CD3OD 300MHz1.04-1.95(14H,m),2.07(2H,t,J=7.8Hz),2.14-2.22(1H,m),2.94-3.00(1H,m),5.04-5.25(2H,m),7.36-7.52(3H,m),7.66-7.71(2H,m),7.78-7.85(2H,m),7.91-7.97(2H,m).IR(KBr)3421,3278,2951,2872,1562,1481,1409,1317,1156,1097,1057,895/cm[α]D=-15.3±0.5°(CHCl3,c=1.06,23℃).mp.105-112℃No.3a-11CDCl3 300MHz0.90-2.04(14H,m),2.08-2.19(1H,m),2.35(2H,t,J=7.2Hz),2.95-3.04(1H,m),5.17-5.32(3H,m),7.56-7.63(2H,m),7.83-7.95(2H,m).IR(CHCl3)3260,3020,2948,2868,1707,1569,1456,1383,1325,1268,1160,1088,1053.1006,892/cm.[α]D=+8.3±0.5°(CHCl3,c=1.00,22℃).No.3a-16CDCl3 300MHz0.80-1.90(14H,m),1.98-2.04(1H,m),2.27(2H,t,J=7.2Hz),2.88(6H,s),2.90-2.98(1H,m),4.88-5.00(2H,m),5.13(1H,d,J=7.2Hz),7.18(1H,d,J=7.5Hz),7.48-7.60(2H,m),8.25-8.33(2H,m),8.53(1H,d,J=8.7Hz).IR(CHCl3)3272,3020,2946,2866,2782,1708,1573,1455,1407,13 11,1229,1160,1142,1070,942,891/cm.[α]D=-19.7±0.6°(CHCl3,c=1.08,23.5℃).No.3a-31CDCl3 300MHz0.80-1.85(14H,m),2.02-2.08(1H,m),2.20(2H,t,J=7.2Hz),2.85-2.95(1H,m),3.68(3H,s),4.80.4.92(2H,m),4.96(1H,d,J=6.9Hz),7.50-7.70(3H,m),7.92-7.98(1H,m),8.07(1H,d,J=8.4Hz),8.29(1H,dd,J=1.5&7.5Hz),8.65(1H,d,J=8.7Hz).IR(CHCl3)3374,3016,2946,2868,1727,1506,1435,1318,1160,1133,1105,1051,984,890/cm.[α]D=-39.3±0.8°(CHCl3,c=1.07,22℃).No.3a-32CDCl3 300MHz0.80-1.90(14H,m),1.95-2.05(1H,m),2.27(2H,t,J=7.2Hz),2.90-2.96(1H,m),4.85-5.00(2H,m),5.23(1H,d,J=6.6Hz),7.50-7.72(3H,m),7.95(1H,d,J=8.1Hz),8.07(1H,d,J=8.4Hz),8.29(1H,dd,J=1.2&7.5Hz),8.66(1H,d,J=9.0Hz).IR(CHCl3)3270,3020,2948,2868,1708,1455,1412,1317,1159,1132,1104,1079,1051,983,89 1/cm.[α]D=-29.2±0.6°(CHCl3,c=1.08,22℃).No.3a-33CD3OD 300MHz0.94-1.84(14H,m),1.96-2.08(3H,m),2.77-2.84(1H,m),4.67-4.84(2H,m),7.55-7.75(3H,m),8.02(1H,d,J=7.8Hz),8.12-8.26(2H,m),8.74(1H,d,J=8.7Hz).IR(KBr)3432,3298,2951,2872,1564,1412,1315,1159,1134,1107,1082,1058,986/cm.[α]D=-79.9±1.2°(CH3OH,c=1.00,23℃).No.3a-34CDCl3 300MHz0.97-1.91(14H,m),2.13-2.20(1H,m),2.42(2H,t,J=7.2Hz),3.00-3.07(1H,m),5.06-5.24(2H,m),5.33(1H,d,J=6.9Hz),7.57-7.68(2H,m),7.82-8.00(4H,m),8.45(1H,d,J=1.2Hz)IR(CHCl3)3260,3020,2948,1708,1408,1319,1154,1129,1073,953,893/cm.[α]D=+20.7±0.6°(CHCl3,c=1.07,22℃).No.3a-35CD3OD 300MHz1.03-2.20(m,17H),2.97(m,1H),5.02(m,2H),7.64(m,2H),8.00(m,4H),8.43(S,1H).IR(KBr)3360,3285,1562,1407,1316,1153,1130,1075/cm.[α]D0[α]365=+20.9±0.6°(CH3OH,c=1.04,23℃).No.3d-1CDCl3 300MHz0.93-2.55(m,17H),3.02(m,1H),5.24(m,2H),6.48(m,1H),7.35-7.60(m,3H),7.85-8.00(m,2H)IR(液蜡)3275,1548,1160,1094,758,719,689,591,557/cm.[α]D=+19.0±0.6°(CH3OH,c=1.010,26.5℃).元素分析 (C20H26NO4S 1/2ca 1.0H2O)计算值C,57.94;H,6.82;N,3.38;Ca,4.83;H2O,4.35实测值C,57.80;H,6.68;N,3.68;Ca,5.06;H2O,4.50No.3d-6[α]D=-20.7±0.6°(CHCl3,c=1.00,24℃).No.3d-7[α]D=-3.2±0.4°(CHCl3c=1.03,22℃).mp.65-67℃No.3d-8[α]D=-14.5±0.5°(CHCl3,c=1.07,24℃).No.3d-9[α]D=+12.2±0.5°(CH3OH,c=1.00,23℃).mp.119-125℃No.3d-10[α]D=+39.7±0.8°(CHCl3,c=1.07,22℃).No.3d-11[α]D=+29.2±0.7°(CHCl3,c=1.06,22℃).No.3d-12[α]D=+76.4±1.1°(CH3OH,c=1.03,24℃).No.3d-14[α]D=-20.6±0.6°(CHCl3,c=1.07,22℃).No.3d-15[α]365=-28.0±0.7°(CH3OH,c=1.03,24.5℃).No.3d-16[α]D=-8.7±0.5°(CHCl3,c=1.06,22℃).No.3d-17CDCl3 300MHz0.80-2.15(m,24H),2.32(t,J=7Hz,2H),2.68(t,J=7Hz,2H),3.02(m,1H),2.15(m,24H),2.32(t,J=7Hz,2H),2.68(t,J=7Hz,2H),3.02(m,1H),5.22(m,2H),5.38(d,J=7Hz,1H),7.30(A2B2q-Apart,J=8Hz,2H),7.81(A2B2qBpart,J=8Hz,2H),9.86(brs,1H).[α]D0[α]365=-9.7±0.5°(CHCl3,c=1.03,22℃).No.3d-24[α]D=+19.2±0.6°(CHCl3,c=1.05,23℃).No.3d-26CD3OD 300MHz0.90-2.20(20H,m),2.88(1H,m),3.07(2H,q,J=7.0Hz),5.00-5.40(2H,m),7.20-7.60(4H,m),7.95(1H,m).IR(KBr)3415,3254,1698,1564,1314,1154/cm.No.3d-28CD3OD 300MHz0.90-2.20(20H,m),2.73(2H,q,J=7.0Hz),2.93(1H,m),5.00-5.30(2H,m),7.40-7.50(2H,m),7.60-7.77(2H,m).IR(KBr)3435,3280,1562,1323,1304,1151/cm.No.3d-30元素分析 (C20H25BrNO4SNa)计算值C50.21;H5.27;Br16.70;N2.93;S6.70;Na4.81实测值C50.22;H5.40;Br15.57;N2.88;S6.41;Na5.10IR(KBr)3425,3280,3085,1697,1570,1410,1321,1165,1155/cm.No.3e-1CD3OD 300MHz0.71(1H,d,J=10.2Hz),1.04(3H,s),1.12(3H,s),1.35-2.28(14H,m),2.42(3H,s),3.17-3.25(1H,m),5.18-5.39(2H,m),7.37(2H,d,J=8.4Hz),7.75(2H,d,J=8.4Hz).IR(CHCl3)3400,3289,2986,2924,2870,1559,1424,1322,1305,1160,1095,1075,1030/cm.[α]D=+25.9±0.7°(CH3OH,c=1.00,23℃).
以上实例中制备的化合物,按照以下实验例中所示的方法进行活体和离体活性试验。
实验1与PGD2受体结合
材料与方法
(1)人体血小板膜级分的制备
血样是用含有3.8%柠檬酸钠的塑料注射器从健康志愿者(成年男性和女性)的静脉抽取的,放入塑料试管中,用颠倒法缓缓混合。然后,该样品以1800转/分、在室温离心分离10分钟,收集含有PRP(富含血小板的血浆)的上清液。使PRP以2300转/分在室温再离心分离22分钟,以得到血小板。这些血小板用一台匀浆机(Ultra-Turrax)匀化,随后以20,000转/分在4℃离心分离10分钟,得到血小板膜级分。在蛋白质测定后,把这种膜级分调制成2mg/ml,在-80℃的电冰箱中保存直至使用。
(2)与PGD2受体结合
向结合反应溶液(50mM Tris/HCl,pH 7.4,5mM MgCl2)(0.2ml)中添加人体血小板膜级分(0.1mg)和5nM[3H]PGD2(115Ci/mmol),在4℃反应90分钟。反应完成后,反应混合物通过玻璃纤维滤纸过滤,用冷却的食盐水洗涤若干次,测定该滤纸上截留的放射性。从总结合量中扣除非特异性结合(10μM PGD2存在下的结合),计算出特异性结合。每种化合物的结合抑制活性表达为50%抑制所需要的浓度(IC50),它是通过将每种化合物存在下的结合比(%)作图绘制一条代换曲线来确定的,在这种情况下,试验化合物不存在时的结合比是100%。结果列于下表中。
化合物号 活性(μM) 化合物号 活性(μM)
3a-4 0.6 2a-4 0.54
1a-1158.6 2a-17 0.12
1a-28 0.0452a-21 5.2
1a-47 0.0086 2a-28 0.046
1a-1000.56 2a-95 1.6
1a-1760.0472a-1090.003
1a-2 0.13 1a-1620.027
实验2 用人体血小板评估对PGD2受体的拮抗活性
用一支事先添加了1/9体积的柠檬酸/右旋葡萄糖溶液的注射器,从健康的志愿者身上抽取末梢血液。使该注射器以180g离心分离10分钟,以得到上清液(PRP富含血小板的血浆)。所得到的PRP用一种洗涤缓冲液洗涤3次,血小板数目用一台微型细胞计数器计数。调节悬浮液,使之以最终浓度为5×108/ml含有血小板,在37℃温热,然后用3-异丁基-l-甲基黄嘌呤(0.5mM)预处理5分钟。向该悬浮液中添加以各种不同浓度稀释的试验化合物。10分钟后,添加0.1~2.0μM PGD2以诱导反应,15分钟后添加HCl以使反应停止。血小板用一台超声匀浆机破坏。离心分离后,用放射试验法测定上清液中的cAMP。药物的PGD2受体拮抗作用评估如下。在各个浓度测定因添加PGD2而增加的关于cAMP的抑制率,然后,计算50%抑制所需要的药物浓度(IC50)。结果列于下表中。
化合物号 对人体血小板cAMP增加的抑制(IC50)(μM)
3a-16 0.37
1a-12 12.1l
1a-28 0.30
1a-47 2.09
2a-2 0.77
2a-4 0.94
2a-35 1.52
2a-75 0.71
实验3 利用鼻塞模型进行的实验
以下描述利用豚鼠测定鼻腔阻力和评估抗鼻塞所用的方法。
一种l%卵白蛋白(OVA)溶液用超声喷雾器处理,得到一种气雾剂。Hartley雄性豚鼠以一周间隔吸入两次该气雾剂各10分钟,使之敏化。敏化后7天,使该豚鼠暴露于一种抗原,以引发反应。然后,在用戊巴比妥(30mg/kg,腹膜内)麻醉下将气管切开,在肺侧和鼻腔侧各将套管插入气管中。在肺侧插入的管子与一个人工呼吸器连接,提供4ml空气×60次/分钟。在用Garamin(2mg/kg,经静脉内)阻止豚鼠的自发呼吸之后,用人工呼吸器以70次/分钟的频率和4ml空气/次的流量率向口鼻部供给空气,利用一个装在支气管上的传感器测定充气所需的大气压力。用该测定值作为鼻腔阻力的一个参数。抗原暴露是通过在该呼吸器与鼻腔套管之间发生3分钟3%0VA溶液的气雾剂进行的。试验药物是在抗原暴露之前10分钟经静脉内注射的。连续测定0~30分钟之间的鼻腔阻力,其效果表达为在30分钟内利用AUC对载体所得到的值的抑制率(纵轴为鼻腔阻力(cm H2O),横轴为时间(0~30分钟)),作为一种指示。结果列于下表中。化合物号抑制率(%)1mg/kg(经静脉内)备 注1a-28 441a-98 691a-100501a-115661a-116481a-120583mg/kg(经静脉内)1a-2 821a-162801a-176601a-267622a-4 602a-21 522a-28 542a-95 772a-96 7710mg/kg(经口)2a-109732a-1106610mg/kg(经口)22a-194 79
配方1 片剂的制备
以常用方式制备每片含有40mg有效成分的片剂。40mg片剂的组分如下(+)-(Z)-7-[(1R,2S,3S,4S)-3-苯磺酰胺基双环[2.2.1]庚-2-基]-5-庚烯酸钙·二水合物 40.0mg羟丙基纤维素 3.6mg硬脂酸镁 0.4mg玉米淀粉18.0mg乳糖58.0mg
合计120.0mg
配方2颗粒剂的制备组分(+)-(Z)-7-[(1R,2S,3S,4S)-3-苯磺酰胺基双环[2.2.1]庚-2-基]-5-庚烯酸钙·二水合物 100.0mg羟丙基纤维素 30.0mg羧甲基纤维素钙 30.0mg滑石粉 10.0mgPoloxamer 18820.0mg结晶纤维素 70.0mg玉米淀粉300.0mg乳糖440.0mg
合计1000.0mg
权利要求
1.一种PGD2拮抗剂,其中包含下面通式(I)的化合物或其盐或其水合物作为活性成分
其中


A是亚烷基,任选地插入杂原子或亚苯基,含有氧代基,和/或有不饱和键;
B是氢、烷基、芳烷基或酰基;
R是COOR1,CH2OR2或CON(R3)R4;
R1是氢或烷基;
R2是氢或烷基;
R3和R4各自独立地是氢、烷基、羟基或烷基磺酰基;
X1是单键、亚苯基、亚萘基、噻吩二基、吲哚二基,或噁唑二基;
X2是单键、-N=N-,-N=CH-,-CH=N-,-CH=N-N-,-CH=N-O-,-C=NNHCSNH-,-C=NNHCONH-,-CH=CH-,-CH(OH)-,-C(Cl)=C(Cl)-,-(CH2)n-,亚乙炔基,-N(R5)-,-N(R51)CO-,-N(R52)SO2-,-N(R53)CON(R54)-,-CON(R55)-,-SO2N(R56)-,-O-,-S-,SO-,SO2-,-CO-、噁二唑二基、噻二唑二基或四唑二基;
X3是烷基、链烯基、炔基、芳基、芳烷基、杂环基、环烷基、环烯基、亚噻唑啉基甲基(thiazolinylidenemethyl)、亚噻唑烷基甲基(thiazolidinylidenemethyl)、-CH=NR6或-N=C(R7)R8;
R5、R51、R52、R53、R54、R55和R56各是氢或烷基;
R6是氢、烷基、羟基、烷氧基、氨基甲酰氧基、硫代氨基甲酰氧基、脲基或硫代脲基;
R7和R8各自独立地是烷基、烷氧基或芳基;
n是1或2;
Z是-SO2-或-CO-;以及
m是0或1;
其中环状取代基可以有1-3个选自下述的取代基硝基、烷氧基、氨磺酰、取代或未取代的氨基、酰基、酰氧基、羟基、卤素、烷基、炔基、羧基、烷氧羰基、芳烷氧羰基、芳氧羰基、甲磺酰氧基、氰基、链烯氧基、羟烷基、三氟甲基、烷硫基、-N=PPh3、氧代、硫代、肟基、烷氧亚氨基、苯基和亚烷二氧基。
2.权利要求1的PGD2拮抗剂,其中活性成分是通式(I)的化合物,或其盐或其水合物,其中

m是0;且当Z是SO2时,X1和X2两者都是单键;X3是烷基、苯基、萘基、Stylyl(苯乙烯基)、喹啉基或噻吩基;以及这些取代基中环状取代基可任选地带有选自下述的1-3个取代基硝基、烷氧基、取代或未取代的氨基、卤素、烷基和羟烷基。
3.权利要求l的PGD2拮抗剂,其中活性成分是通式(I)的化合物,或其盐或其水合物,其中

当m是1时,X1和X2两者都是单键;而X3是任选地被卤素取代的苯基。
4.权利要求l的PGD2拮抗剂,其中活性成分是通式(I)的化合物,或其盐或其水合物,其中

当m是1时,X1是苯基,X2是-CH2-或-N=N-,而X3是苯基。
5.权利要求1的PGD2的拮抗剂,它是一种用于治疗鼻塞的药物。
6.式(Ia)的化合物或其盐或其水合物
其中A、B、R、X1、X2和X3的定义同上,其条件是其中(1)X1和X2是单键,而X3是取代或未取代的苯基,或萘基;以及(2)A是5-亚庚烯基,R是COOR1(R1是氢或甲基),X1是1,4-亚苯基,X2是单键,而X3是苯基的那些化合物除外。
7.权利要求6的化合物、其盐或其水合物,其中X1和X2都是单键,X3是异噁唑基、噻二唑基、异噻唑基、吗啉基、吲哚基、苯并呋喃基、二苯并呋喃基、二苯并二喔星基、苯并噻吩基、二苯并噻吩基、咔唑基、呫吨基、菲啶基、二苯并噁庚因基、二苯并硫杂七环基(thiepinyl)、肉啉基(cinnolyl)、苯并吡喃基(chromenyl)、苯并咪唑基或二氢苯并硫杂七环基(thiepinyl),A、B和R的定义同上。
8.权利要求6的化合物、其盐或其水合物,其中X1是单键,X2是亚苯基,X3是链烯基、炔基、-CH=NR6或-N=C(R7)R8,而A、B、R、R6、R7和R8的定义同上。
9.权利要求6的化合物、其盐或其水合物,其中R是COOR1,X1是亚苯基或噻吩二基,X2是单键、-N=N-、-CH=CH-、-CONH-、-NHCO-或亚乙炔基,而X3是苯基、亚噻唑啉基甲基、亚噻唑烷基甲基或噻吩基,而A、B、R1、R6、R7和R8的定义同上。
10.式(Ib)的化合物或其盐或其水合物
其中


A、B、R、X1、X2和X3的定义同上,其条件是其中X1和X2是单键,而X3是苯基,以及其中X1是单键,X2是-O-,而X3是苄基的那些化合物除外。
11.权利要求10的化合物、其盐或其水合物,其中

而A、B、R、X1、X2和X3的定义同上。
12.权利要求11的化合物、其盐或其水合物,其中R是COOR1(R1的定义同上)。
13.权利要求11的化合物、其盐或其水合物,其中X1是亚苯基或噻吩二基,X2是单键、-N=N-、-CH=CH-、亚乙炔基、-O-、-S-、-CO-、-CON(R55)-(R55的定义同上)、-N(R51)CO-(R51的定义同上),而X3是苯基或噻吩基。
14.权利要求10的化合物、其盐或其水合物,其中

而A、B、R、X1、X2、X3和Z的定义同上。
15.权利要求14的化合物、其盐或其水合物,其中B是氢,X1和X2两者都是单键,X3是噻吩基、噻唑基、噻二唑基、异噻唑基、吡咯基、吡啶基、苯并呋喃基、苯并咪唑基、苯并噻吩基、二苯并呋喃基、二苯并噻吩基、喹啉基或吲哚基。
16.权利要求15的化合物、其盐或其水合物,其中X1是亚苯基、噻吩二基、吲哚二基或噁唑二基,X2是单键、-N=N-、-CH=CH-、亚乙炔基、-S-或-O-,而X3是芳基或杂环基。
全文摘要
通式(Ⅰ)的化合物、其盐或其水合物,其中(a)代表(b)或(c),例如化合物(d)和(e),这些可用作PGD2拮抗剂,因而可用于(例如)全身性肥大细胞沉积病或全身性肥大细胞活化失调的治疗,支气管收缩药,抗哮喘药,变应性鼻炎剂药物,变应性结膜炎药物,荨麻疹药物,局部缺血性回流失调的治疗,和抗炎剂。它尤其可用于治疗鼻塞。
文档编号C07D313/14GK1193315SQ9619632
公开日1998年9月16日 申请日期1996年6月19日 优先权日1995年6月21日
发明者大谷光昭, 有村昭典, 钓达男, 岸野淳二, 本摩恒利 申请人:盐野义制药株式会社
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