CN1075105C - 可聚合的手性化合物和它们的用途 - Google Patents

可聚合的手性化合物和它们的用途 Download PDF

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CN1075105C
CN1075105C CN94194817A CN94194817A CN1075105C CN 1075105 C CN1075105 C CN 1075105C CN 94194817 A CN94194817 A CN 94194817A CN 94194817 A CN94194817 A CN 94194817A CN 1075105 C CN1075105 C CN 1075105C
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K-H·埃茨巴赫
P·德拉维尔
K·西门斯梅耶
G·韦根布拉斯特
L·劳皮彻勒
V·维尔
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Abstract

本发明涉及可聚合的、手性的化合物，它含有至少一个二价或多价手性基团、至少一个可聚合基团、至少一个间隔基团和至少一个介晶基团，和涉及它们在制备胆甾型网络时作为可聚合的、手性的掺杂剂的用途。
该新型化合物适合用于电光显示器或作为向列型或胆甾型液晶的手性掺杂剂、来生产能反射颜色的层。

Description

可聚合的手性化合物和它们的用途
已知在形状上各向异性的分子在受热时会形成液晶相(称为介晶相)。各相的区别一方面在于分子的主要部分的空间排列和另一方面在于就长轴而言的分子排列(G.W.Gray,P.A.Winsor,Liquid crystals和Plasticcrystals,Ellis Horwood Limited,Chichester,1974)。向列型液晶相突出表现在：因各长分子轴平行排齐而使得仅仅单线远程有序。在组成向列相的分子是手性的前提条件下，形成胆甾相，其中分子的长轴形成与它垂直的螺旋式超结构(H.Baessler,Festkperprobleme XI,1971)。手性结构部分可以存在于液晶分子本身或作为掺杂剂加入到向列相中。通过掺杂产生的相称为诱导胆甾相。这一现象首先在胆甾醇衍生物上研究发现(H.Baessler,M.M.Labes,J.Chem.Phys.52(1970)631；H.Baessler,T.M.Laronge,M.M.Labes.J.Chem.Phys.51(1969)3213；H.Finkelmann,H.Stegemeyer,Z.Naturforschg.28a(1973)799)。胆甾相的诱导也可通过添加其它本身不是液晶的手性物质来实现(H.Stegemeyer,K.J.Mainusch,Naturwiss.58(1971)599；H.Finkelmann,H.Stegemeyer,Ber.Bunsenges.Phys.Chem.78(1974)869)。
胆甾相具有突出的光学性能：由胆甾层内的圆偏振光的选择性反射引起的大的旋光性和显著的圆振二向色性。根据视角所观察到的不同颜色取决于螺旋式超结构的螺距，它本身取决于手性组分的扭转能。螺距和胆甾层的选择性反射光的波长范围能够改变，尤其通过改变手性掺杂剂的浓度(J.E.Adams,W.E.L.Haas,Mol.Cryst.Liq.Cryst.16(1972)33)。此类胆甾体系为实际应用提供了有益的机会。因此，在胆甾相中排序(alignment)后向内消旋的丙烯酸酯中引入手性结构部分以及光致交联反应能够得到稳定的、着色的网络，但其中的手性组分的浓度不能被改变(G.Galli,M.Laus,A.Angeloni,Makromol.Chem.187(1986)289)。另外，不能交联的手性化合物与光致交联后的胆甾型丙烯酸酯混合能够得到着色的聚合物(I.Heynderickx,D.J.Broer,Mol.Cryst.Liq.Cryst.203(1991)113)，但仍然含有妨碍应用的挥发性成分。
本发明的目的是提供新型的手性化合物，它首先具有高的扭转能，其次能够按任何所需浓度以稳定方式引入胆甾相中，而不会从胆甾相中扩散出去或结晶出来。
我们发现由可聚合的手性化合物可以实现这一目的。
所以，本发明涉及可聚合的、手性的化合物，它含有至少一个二价或多价手性基团、至少一个可聚合基团、至少一个间隔基团和至少一个介晶基团，和涉及它们在制备胆甾型网络时作为可聚合的、手性的掺杂剂用途。
可聚合基团尤其是乙烯基，它们例如存在于丙烯酸化合物、乙烯基醚或苯乙烯衍生物中。环氧化合物也是合适的。
适合于本新型化合物的手性基团尤其是从糖类，来自联苯或联萘系的双官能或多官能化合物，旋光性乙二醇类、二醇或氨基酸。
间隔基和介晶基是通常为此目的使用的基团。
新型化合物所必需的这些基团是通过桥连基相互连接的，如O、COO、OCO、CONH、NHCO、CON(R)、N(R)CO或直接的键。
特别地，本发明提供结构式Ⅰ的化合物
        (Z-Y-A-Y-M-Y-)nX             Ⅰ,其中，在每一种情况下相互独立地，A    是间隔基，M    是介晶基，Y    是直接的键，O,S,COO,OCO,CON(R)或N(R)CO,Z    是可聚合基团，n    是2-6中的数，X    是手性基团和R    是C1-C4烷基或氢。
间隔基A可以是为此目的所已知的任何基团；间隔基通常通过酯基或醚基或直接的键连接于X。间隔基一般含有2-30个、优选2-12个碳原子，而且在链上可以插入例如O、S、NH或NCH3。间隔基链的可能的取代基是氟、氯、溴、氰基、甲基或乙基。
代表性的间隔基的例子是：(CH2)p,(CH2CH2O)mCH2CH2,CH2CH2SCH2CH2,CH2CH2NHCH2CH2,
Figure C9419481700061
其中m是1-3和p是1-12。
基团M同样可以是已知的介晶基。特别合适的是含有环脂族、芳族或杂芳族基团的基团。介晶基团尤其满足结构式Ⅱ
              (-T-Y1)r-T           Ⅱ其中，每一个T独立地是亚环烷基，芳族基或杂芳族基，每一个Y1独立地是O,COO,OCO,CH2O,OCH2,CH=N,N=CH或直接的键，和r    是0-3。r    优选是0或1。T    一般是非芳族或芳族、碳环族或杂环族环体系，它是未被取代的或被氟、氯、溴、氰基、羟基或硝基取代，并且例如符合以下基本结构：
Figure C9419481700072
或 特别优选的介晶基团例如是：
Figure C9419481700081
或
Figure C9419481700082
结构式Ⅰ中的n优选是2或3，尤其是2。
在手性基团X当中，特别优选的是从糖类，联苯或联萘衍生物或旋光性乙二醇类或二醇衍生而来的基团。在糖类的情况下，可特别提及戊糖和己糖及它们的衍生物。
各X基团的例子是：
Figure C9419481700101
Figure C9419481700111
其中L是C1-C4烷基，C1-C4烷氧基，卤素，COOR,OCOR,CONHR或NHCOR，这里R如上所定义。
特别优选的，例如是：
Figure C9419481700112
Figure C9419481700113
或 旋光性乙二醇类或其衍生物例如对应于以下结构式：
Figure C9419481700121
其中B1和B2相互独立地是C1-C4烷基，它可以被羟基取代和插入-O-，或者是苯基或取代的或未取代的羧基，和这些基团中的一个可以是氢，在相同基团B1和B2的情况下，排除R,S构型。
此类基团B1和B2例如分别是：CO2CH3,CO2CH2CH3,CO2(CH2)2CH3,CO2(CH2)3CH3,CO2CH(CH3)2,CO2C(CH3)3或-CH(OH)CH2(OH)。*合适的还有具有以下结构的特定的双官能手性基团：
Figure C9419481700122
优选的基团Z的例子是：
Figure C9419481700124
或 其中R如上所定义。
根据本发明的单元Z-Y-A-Y-M-Y(其中Z、Y、A和M如上所定义)能够由一般来说已知的合成方法获得，例如按照DE-A 3917196中描述的方法。
手性结构部分能够通过商业途径获得，因而是易得的。
本新型化合物特别适合用于光电显示元件或作为向列型或胆甾型液晶的手性掺杂剂，来生产能反射颜色的层。
实施例1
2,5-双[4’-(2-丙烯酰氧基乙氧基)联苯基-4-羰氧基]-1,4；3,6-二脱水-D-山梨糖醇a    4’-羟乙氧基联苯基-4-羧酸乙酯
Figure C9419481700132
将72.6g(0.3mol)4’-羟基联苯基-4-羧酸乙酯溶于225ml绝对二甲基甲酰胺中，添加45.5g(0.33mol)碳酸钾和3.0g碘化钾。然后添加26.57g(0.33mol)2-氯乙醇，混合物在100℃下加热5小时。在混合物于室温下搅拌过夜后，添加另外的22.77g(0.17mol)碳酸钾和13.3g(0.17mol)2-氯乙醇。混合物在100℃下加热15小时，冷却并在水中沉淀。固体残余物用水洗涤至中性并干燥。湿的产物能够立即进一步反应。
产率：123g湿产物，m.p.(纯物质)128-129℃。b    4’-羟乙氧基联苯基-4-羧酸
将123g(约0.3mol)湿的4’-羟乙氧基联苯基-4-羧酸乙酯溶于258ml乙醇中，添加67.22g(0.6mol)50％浓度的KOH溶液。混合物回流1小时，冷却，过滤出残余物，用乙醇洗涤并抽干。粗产物在水中搅拌，用稀盐酸酸化。抽滤产物，用水洗涤至中性并干燥。
产率：68.0g(约等于88％),m.p.155℃。c    4’-(2-丙烯酰氧基乙氧基)联苯基-4-羧酸
将38.7g(0.15mol)4’-羟乙氧基联苯基-4-羧酸溶于220ml的1,1,1-三氯乙烷中，添加54.0g(0.75mol)新近蒸馏过的丙烯酸和0.5g氢醌。加入10.0g对甲苯磺酸，混合物在水分离器上回流4小时。然后再添加54.0g(0.75mol)新蒸馏过的丙烯酸，混合物被加热3.5小时一直到全部溶解。冷却混合物，抽滤残余物，用1,1,1-三氯乙烷洗涤，随后与叔丁基甲基醚和水搅拌在一起。抽滤固体残余物，用叔丁基甲基醚洗涤，干燥并从1.4l乙酸乙酯重结晶。
产率：19.0g(约等于41％)。d    丙烯酸2-(4’-氯羰基联苯基-4-基氧基)乙基酯
Figure C9419481700142
将9.36g(0.03mol)4’-(2-丙烯酰氧基乙氧基)联苯基-4-羧酸引入25ml草酰氯中，添加一滴二甲基甲酰胺。滴一小滴2,6-二叔丁基甲基酚作为自由基抑制剂，然后反应混合物在40-50℃下加热35分钟。过量的草酰氯随后通过在水泵真空中蒸馏被除去，剩下的油状残余物在油泵真空中干燥过夜。产物可以直接作进一步处理。
产率：10.1g(约等于99％)。e    2,5-双[4’-(2-丙烯酰氧基乙氧基)联苯基-4-羰氧基]-1,4；3,6-二脱水-D-山梨糖醇
将1.99g(0.014mol)1,4；3,6-二脱水-D-山梨糖醇溶于50ml绝对二氯甲烷中，然后添加2.37g(0.03mol)绝对吡啶和一小滴2,6-二叔丁基甲基酚，随后在0-5℃下将9.93g(0.03mol)丙烯酸2-(4’-氯羰基联苯基-4-基氧基)乙基酯溶于20ml绝对二氯乙烷中的溶液滴加进去。混合物在温热下搅拌过夜，然后添加水和小量稀盐酸，混合物用乙醚萃取几次。合并的有机相用水洗涤，用硫酸钠干燥，以及除去溶剂。产物通过柱色谱(硅胶，洗脱液∶甲苯/乙酸乙酯8∶2)提纯。
产率：0.91g(约等于9％),m.p.＞175℃。
1H-NMR(200MHz,CDCl3):δ=4.11(d,J=6.3Hz,2H,-CH2-,环H),4.15(m,2H,-CH2-，
环H),4.25(t,J=6Hz,4H,-CH2-OAr),4.55(t,J=6Hz,4H,
-CH2-OCOR),4.75(d,J=6Hz,1H桥H).5.13(t,J=Hz
1H,桥H),5.45(q,J=6Hz,1H，环H),5.55(m,1H,
环H),5.88(d,J=10.6Hz.2H.烯H),6.20(dd,J=17Hz,
J′=10.6Hz,2H，烯H),7.0(d,J=8.6Hz,4H，芳香H),
7.5-7.7(m,8H，芳香H),8.06(d,J=8.6Hz,2H，芳香H),8.13
(d,J=8.6Hz,2H，芳香H).
实施例2
2,5-双[4’-(2-丙烯酰氧基乙氧基)苯基-4-羰氧基]-1,4；3,6-二脱水-D-山梨糖醇
Figure C9419481700151
使用4-羟基苯甲酸乙酯，按类似于实施例1中的方法制备该化合物。产率：1.24g(约等于16％),m.p.＞156℃。1H-NMR(200MHz,CDCl3):δ=4.05(d,J=5.7Hz,2H,-CH2-，环H),4.12(m,2H,-CH2-，环H),4.24(t,J=6Hz,4H,-CH2-OAr),4.56(t,J=6Hz,4H,-CH2-OCOR),4.70(d,J=6Hz,1H.桥H),5.08(t,J=6Hz,1H，桥H),5.40(q,J=6Hz,1H，环H),5.46(m,1H，环H),5.82(d,J=10.7Hz,2H，烯H),6.18(dd,J=17Hz,J′=10.7Hz,2H，烯H),6.48(d,J=17Hz,2H，烯H),6.95(d,J=8.3Hz,2H，芳香H),7.0(d,J=8.3Hz,2H，芳香H),7.95(d,J=8.3Hz,2H，芳香H),8.05(d,J=8.3Hz,2H，芳香H).
实施例3
2,5-双[4’-(2-丙烯酰氧基乙氧基)联苯基-4-羰氧基]-1,4；3,6-二脱水-D-甘露糖醇
Figure C9419481700161
使用1,4；3,6-二脱水-D-甘露糖醇，按类似于实施例1中的方法制备该化合物。
产率：1.18g(约等于12％)，m.p.＞195℃。1H-NMR(200MHz,CDCl3):δ=3.82(dd,J=6.3Hz,J′=3Hz,2H,-CH2-，环H),3.88(dd,J=6.3Hz,J′=3Hz,2H,-CH2-，环H),4.15(t,J=6Hz,4H,-CH2-OAr),4.4(t,J=6Hz,4H,-CH2-OCOR),4.8(m,2H，桥H),.5.25(m,1H，桥H),5.35(m,1H，环H),5.85(d,J=10.4Hz,2H,烯，H),6.15(dd,J=16Hz,J′=10.4Hz,2H,烯，H),6.4(d,J=16Hz,2H,烯，H),7.1(d,J=8.5Hz,4H，芳香H),7.55(d,J=8.5Hz,4H，芳香H),8.0(d,J=8.5Hz,4H，芳香H),8.1(d,J=8.5Hz,4H，芳香H).
实施例4
2,5-双[4’-(2-丙烯酰氧基乙氧基)联苯基-4-羰氧基]-1,4；3,6-二脱水-L-艾杜糖醇
Figure C9419481700171
使用1,4；3,6-二脱水-L-艾杜糖醇，按类似于实施例1中的方法制备该化合物。
产率：1.89g(约等于19％),m.p.＞195℃。1H-NMR(200MHz,CDCl3):δ=3.93(dd,J=11.0Hz,J′=3.0Hz,2H,-CH2-,环H),3.98(dd,J=11.0Hz,J′=3Hz,2H,-CH2-，环H),4.30(t,J=6Hz,4H,-CH2-OAr),4.50(t,J=6Hz,4H,-CH2-OCOR),5.35(s,2H，桥H),5.65(dd,J=11.0Hz,J′=3Hz,2H，桥H),5.90(d,J=10.7Hz,2H，烯H),6.20(dd,J=16.0Hz,J′=10.7Hz,2H，烯H),6.55(d,J=16Hz,2H,烯H),7.1(d,J=8.7Hz,4H，芳香H),7.50(d,J=8.7Hz,4H，芳香H),8.12(d,J=8.7Hz,4H，芳香H),8.13(d,J=8.7Hz,4H，芳香H)。
实施例5
2,5-双[4’-(2-丙烯酰氧基乙氧基)联苯基-4-羰氧基]-1,4；3,6-二脱水-L-艾杜糖醇
Figure C9419481700172
使用(R,R)一酒石酸二乙酯，按类似于实施例1中的方法制备该化合物。
产率：2.22g(约等于20％),m.p.146℃。1H-NMR(200MHz,CDCl3):δ=1.28(t,J=6.9Hz,6H，酯CH3),4.15(q,J=6.9Hz,4H,酯CH2),4.3(t,J=6.0Hz,4H,-CH2-O-arom.),4.55(t,J=6.0Hz,4H,-CH2-O-COR),5.88(d,J=11.3Hz,2H，烯H),6.04(s,2H,-CH(OR)(CO2R)),6.16(dd,J=17.3,J′=11.3Hz,2H，烯H),6.48(d,J=17.3Hz,1H，烯H),7.05(d,J=8.6Hz,4H,芳香H),7.57(d,J=8.6Hz,4H，芳香H),7.68(d,J=7.6Hz,4H，芳香H),8.16(d,J=7.6Hz,4H，芳香H).
在下表中给出的化合物(它们具有类似的物理性能)也能够通过与前面描述的方法类似的方法制备。表1手性基团：
Figure C9419481700191
Figure C9419481700201
表2手性基团：
Figure C9419481700202
Figure C9419481700211
表3手性基团：
Figure C9419481700212
表4手性基团：
Figure C9419481700221
表5手性基团：
Figure C9419481700232
表6手性基团：
Figure C9419481700234
表7
该化合物能够由类似于实施例2的方法合成。
手性基团：
Figure C9419481700241
实施例35    n=4    HTP:41.5μm-1
实施例36    n=6    HTP:44.7μm-1
实施例37    n=8    HTP:47.7μm-1
实施例38    n=11   HTP:52.3μm-1
HTP=螺旋扭转能
实施例39-42的化合物是由与实施例2的操作程序类似的操作程序，通过与甲基4,6-亚苄基-α-D-吡喃葡糖苷反应而获得的。
表8手性基团：
Figure C9419481700243
Figure C9419481700251
实施例43-47的化合物是由类似于实施例2的方法，通过手性基团与4’-(ω-乙烯氧基)亚烷基氧基苯基-4-羧酸反应而获得的。手性基团：
Figure C9419481700252

Claims (5)

1、下式所示化合物
           (Z-Y-A-Y-M-Y-)nX          Ⅰ,其中，在每一种情况下相互独立地，A    是间隔基，M    是式(T-Y1)r-T所示的介晶基团，Y    是直接的键，O,S,COO,OCO,CON(R)或N(R)CO,Z    是可聚合基团，n    是2-6的数，X    是手性基团，R    是C1-C4烷基或氢，T是亚环烷基，芳族基或杂芳族基，Y1是O,COO,OCO,CH2O,OCH2,CH=N,N=CH或直接的键，和r是0-3。
2、根据权利要求1的化合物，其中r是0或1。
3、根据权利要求1的化合物，其中n是2。
4、根据权利要求1的化合物，其中X是
Figure C9419481700021
或
Figure C9419481700023
其中L是C1-C4烷基，C1-C4烷氧基，卤素，COOR,OCOR,CONHR或NHCOR，这里R如上所定义。
5、权利要求1的化合物用于光电显示器或作为向列型或胆甾型液晶的手性掺杂剂、来产生能反射颜色的层的用途。
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