CN1009058B - 旋光性吸附剂 - Google Patents
旋光性吸附剂Info
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Abstract
本发明涉及以旋光性聚甲基丙烯酰胺为主体的吸附剂,它可用于使外消旋混合物分离为其旋光对映体,其中的酰胺与硅胶相键接。
Description
本发明涉及旋光性聚甲基丙烯酰胺类吸附剂,该吸附剂可用于将外消旋混合物分离为相应的旋光对映体,其中的酰胺类与硅胶键合在一起。
这种酰胺类可由下列式Ⅰ的可聚合化合物获得:
其中R1是H或甲基,
这些与硅胶相键合的聚合物可用作为用于分离外消旋混合物的吸附剂,特别是用于层析分离,而用于高压层析更好。
这种把外消旋混合物分离为旋光对映体的分离方法是制备化学的一个很重要的问题。除先将外消旋混合物转变为非对映异构体混合物再根据不同的物理性质将其分离的常规方法外,近年来,分离外消旋混合物的兴趣主要集中在层析方法上,特别是使用旋光吸附剂作为固定相。
其问题主要在于寻找可使大多数化学性质不同的外消旋体均能进行分离的旋光吸附剂,从而可以普遍使用。
例如,在交联剂存在条件下,悬浮聚合旋光性丙烯酰胺和甲基丙烯酰胺,并在适宜的洗脱剂中使已交联的聚酰胺溶胀后将其用于旋光对映体的分离是众所周知的(公开于西德专利(DEP)2500523)。但极为不利的
是这些材料仅能用于低压液相层析。在压力大于5巴时,这些交联聚酰胺受压而不透过洗脱剂,致使迁移速率显著下降。而且,其膨胀程度取决于洗脱剂的组成。对这些凝胶体而言,不能进行高压液相色谱或梯度洗脱。
本发明的一个目的是要制备和生产合用的吸附剂,这种吸附剂可满足高效分离各种结构的外消旋混合物的分离方法,并可普遍用于用梯度洗脱的高压液相色谱。
令人惊奇的是目前已发现,使旋光性聚酰胺键接于硅胶等载体上可制成特别好的分离外消旋体的旋光吸附剂,该吸附剂特别适用于高压液相色谱和/或梯度洗脱。
从而本发明提供了以旋光性聚甲基丙烯酰胺类为基础的吸附剂,且其中的酰胺是键接于硅胶上的。
本发明提供的吸附剂中的旋光性丙烯酰胺或甲基丙烯酰胺由式Ⅰ的可聚合化合物制成,并且该旋光性聚酰胺直接或通过甲基丙烯酰基与硅胶相接。
本发明还提供一种制备旋光性聚合物的方法,其特征在于在聚合反应条件下至少由甲基丙烯酸部分改性的亲水硅胶与式Ⅰ的旋光性单体进行反应。
本发明也提供了键接于硅胶上的本发明的聚合物用于将外消旋混合物层析分离为旋光对映体的方法。一般可以使用任何所需旋光性丙烯酰胺或甲基丙烯酰胺作为单体。但以式Ⅰ的单体为好。
较好的式Ⅰ的单体是其中R1是氢或甲基的那些化合物。
不仅在胺上,而且在氨基酸衍生物中,R2均以是氢为好。
旋光性化合物的旋光对映体均可使用。
例如,式Ⅰ的单体可由-5℃至60℃的温度下,最好是在阻聚剂如4-叔丁基邻苯二酚存在下(S)-苯丙氨酸乙酯与烯丙酰氯进行反应或(S)-环己基乙胺与2-甲基丙烯酰氯进行反应来制取或一般通过旋光性胺类或氨基酸酯类
与2-甲基丙烯酸或丙烯酸进行反应来制取的。在室温下,在惰性有机溶剂存在下,特别是于二氯甲烷或氯仿等卤代烃溶剂中进行该反应是很有利的。反应时间在约30分钟至4小时范围内,主要取决于反应温度。这些反应条件已在本文中反复作了叙述。
旋光性聚酰胺最好联接在亲水硅胶上。其中,以二醇类、氨基或氰基改性的硅胶为好。含有二醇基团的硅胶特别好。按此方法进行改性的硅胶是已知的,市场上可以买到。但也可使用其它载体物质,如氧化铝或氧化钛。
制备这些键接于硅胶上的聚酰胺有两种较好的途径。第一种途径是:按常规方法用甲基丙烯酸使用二醇基改性的硅胶发生酯化。酯化反应在-20℃至80℃之间于惰性溶剂中进行为好,而以在室温下于二恶烷或四氢呋喃中进行反应更好,反应一般进行15分钟至48小时。最好使用甲基丙烯酸的活性衍生物如甲基丙烯酸酐进行反应。该改性反应至少应有部分得到改性。最终酯化反应程度应超过50%是有利的,超过70%特别好。硅胶上
负荷的甲基丙烯酸酯基团为0.5~4.0微摩尔/平方米,最好为2.0~3.0微摩尔/平方米。
然后在悬浮液中,使键接于硅胶上的甲基丙烯酸酯与式Ⅰ的单体进行共聚合反应。在自由基引发剂如过氧化二苯甲酰、过氧化二月桂酰和过氧化二邻甲苯等过氧化物或偶氮二异丁腈等偶氮化合物等存在下按常规方法进行该聚合反应。使反应物悬浮在惰性有机溶剂中,最好是悬浮在苯或甲苯等芳香烃溶剂或环己烷等烃类溶剂中,或悬浮在二氯甲烷、氯仿或1,2-二氯乙烷等囟代烃中进行反应。在惰性气氛(以氮气为好)中,搅拌该混合物,将其加热至40℃至100℃(以70℃至90℃为好)。聚合反应时间为约10至60分钟,以15至30分钟为好。添加叔丁基邻苯二酚等阻聚剂终止该聚合反应。过滤分离、充分洗涤和真空干燥,由此制成与硅胶共价键连的聚酰胺。
按同样方法,以氨基改性的硅胶代替二醇改性的硅胶,与甲基丙烯酸衍生物进行反应并使所得产物与甲基丙烯酰胺单体进行共聚合反应也是可行的。所得产物同样适用于旋光对映体的分离。
在另一加工途径中,在通常的聚合反应条件下使亲水硅胶直接与式Ⅰ的单体进行反应。结果同样是使聚酰胺与硅胶相连接,所得产物同样适用于高压液相色谱法直接分离旋光对映体。如上所述,进行此加工途径的聚合反应。
硅胶的比例:在所述反应中,单体量(按重量份数计)可在1∶0.05至1∶10范围内变化,在1∶0.1至1∶0.5范围内较好,在1∶0.25范围内最好。
因此,硅胶上聚甲基丙烯酰胺的负荷可以保持在0.5~8.0微摩尔/平方米的范围内,保持在2.0~4.0微摩尔/平方米的范围内更好。
本发明的材料通过进行高压液相色谱法,可以高光学效应分离外消旋混合物成为旋光性物质,而使用未与硅胶相接的聚合物进行分离则是不可
能的。对本专业技术领域的普通技术人员而言,外消旋混合物初步分离为旋光性异构体的高压液相色谱法是一种较为熟悉的方法。通常,吸附剂悬浮在洗脱剂中,在压力下用装填设备装入钢柱中。待分离的外消旋体以溶于适宜洗脱剂中的溶液形式引入钢柱中。最后,再用洗脱剂在一定流速下进行洗提并进行检测,可以进行梯度洗脱。
与使用未与硅胶相连接的聚合物的低压液相色谱法的分离方法相比,使用本发明的吸附剂进行高压液相色谱分离旋光对映体的优点在于分离时间很短和分离效率较高。所用的洗脱剂最好是烃类(尤以芳香烃类为好)和醚类或其混合物。二噁烷与己烷的混合物特别适用。用本发明的聚合物可以进行许多类别的化合物的外消旋体的分离。
在下列制备及分离实施例中将更详尽地说明本发明的聚合物。
实施例1:
a.将1.5克甲基丙烯酸溶于10毫升二噁烷并将0.8克二异丙基乙胺溶于30毫升二噁烷,在氮气流下将所得溶液加至20毫升二噁烷与2.5克二醇相(硅胶LichrosorbRDiol 5微米,E.Merck)形成的悬浮液中,室温下搅拌该混合物30分钟,放置24小时,吸滤后用二恶烷洗涤并干燥。制成白色产物〔C(碳)=8.27%,H(氢)=1.76%〕。
b.将7.5克(S)-N-丙烯酰基苯丙氨酸乙酯溶于20毫升甲苯并将22毫克偶氮二异丁腈溶于10毫升甲苯中,在氮气保护下将所得溶液加入10毫升甲苯与2.5克实施例1a中制备的硅胶甲基丙烯酸酯形成的悬浮液中,在80℃下搅拌该混合物15分钟。将200毫克叔丁基邻苯二酚溶于10毫升甲苯中加至混合物中以终止该聚合反应,再进行过滤、洗涤和干燥。得到3.0克白色吸收剂(C=21.35%,H=3.1%,N=1.16%),该吸收剂带有约20%(重量)的聚丙烯酰胺。
实施例2:
按实施例1b的方法,使硅胶甲基丙烯酸酯(按实施例1a制备)与(S)-苯乙基甲基丙烯酰胺进行反应制备相应的硅胶聚甲基丙烯酰胺,但聚合反应时间为30分钟。
按同样方法使用(S)-环己基乙基甲基丙烯酰胺和硅胶甲基丙烯酸酯制备硅胶(S)-环己基乙基聚甲基丙烯酰胺。
实施例3:
将7.5克(S)-N-丙烯酰苯丙氨酸乙酯和22毫克偶氮二异丁腈溶于40毫升甲苯与2.5克硅胶(LichrosorbRDiol5微米,E.Merck)形成的悬浮液中,在80℃氮气氛下加热搅拌15分钟,终止该反应,并洗涤、干燥所得产物。结果获得2.8克白色吸收剂(C=12.48%,H=2.06%,N=0.65%)。
实施例4:
将1.25克(S)-丙烯酰苯丙氨酸乙酯和44毫克偶氮二异丁腈溶于100毫升环己烷与5.0克硅胶(LichrosorbRDiol5微米,E.Merck)形成的悬浮液中,在80℃氮气氛中加热搅拌15分钟,终止该反应,并洗涤、干燥所得产物。
实施例A:
在450~500巴的压力下,将30毫升异丙醇与吸附剂的悬浮液加入钢柱(250×4毫米)中。
以0.5~2.0毫升的迁移速率、20~100巴的压力层析分离微克级量的3~15微克外消旋体在二噁烷中的溶液,所产生的压力取决于洗脱剂和迁移速率。在流动池中以254毫微米的光波进行检测。
下表列出对于多种外消旋体进行层析分离试验的结果。
吸收 洗脱剂 流速 旋光对映体的
剂外消旋体 正己烷/二噁烷 毫升/分钟 洗出体积(毫升)
A 去甲羟基安定 75∶25 1.0 51.8 55.8
A 甲噁安定 80∶20 0.5 12.3/ 15.9/
13.8 18.3
(diast.)
A Penflutizide 53∶47 1.5 41.4 46.8
B N-去甲基氯苯 65∶35 1.0 35.4 43.8
甲酮
B 环戊氯噻嗪 40∶60 2.0 54.9 86.7
C 酞胺哌啶酮 75∶25 1.0 17.1 23.4
C 新抗凝 75∶25 1.0 34.2 39.0
D Lopirazepam 50∶50 1.0 40.8 49.2
D 氯苯甲酮 75∶25 1.0 19.8 23.4
D 氯噻酮 55∶45 0.7 30.2 36.1
吸收剂A:如实施例16所述方法制备。
吸收剂B:如实施例2所述方法制备。
吸收剂C:硅胶环己基乙基聚甲基丙烯酰胺,如实施例2所述方法制备。
吸收剂D:如实施例3所述方法制备。
这些结果表明,本发明的材料非常适用于用高压液相色谱法进行旋光对映体的分离。旋光对映体的洗出体积得到了足够宽的分离,基本上获得了很好的分离基线(base line separation)。
Claims (4)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DEP3619303,8 | 1986-06-07 | ||
DE19863619303 DE3619303A1 (de) | 1986-06-07 | 1986-06-07 | Optisch aktive adsorbentien |
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CN87104030A CN87104030A (zh) | 1987-12-16 |
CN1009058B true CN1009058B (zh) | 1990-08-08 |
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CN87104030A Expired CN1009058B (zh) | 1986-06-07 | 1987-06-05 | 旋光性吸附剂 |
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US (1) | US4882048A (zh) |
EP (1) | EP0249078B1 (zh) |
JP (1) | JP2665513B2 (zh) |
CN (1) | CN1009058B (zh) |
CA (1) | CA1303594C (zh) |
CS (1) | CS274614B2 (zh) |
DD (1) | DD263711A5 (zh) |
DE (2) | DE3619303A1 (zh) |
Cited By (1)
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CN100369920C (zh) * | 2003-03-31 | 2008-02-20 | 特瓦药厂私人有限公司 | 大环内酯物质的结晶与纯化 |
Families Citing this family (34)
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DE3811042A1 (de) * | 1988-03-31 | 1989-10-19 | Merck Patent Gmbh | Ionenaustauscher |
FR2631849B1 (fr) * | 1988-05-30 | 1992-02-14 | Centre Nat Rech Scient | Support pour la separation des proteines, procede pour sa preparation et application en chromatographie |
US5164427A (en) * | 1989-10-12 | 1992-11-17 | Macherey, Nagel & Co. | Column-packing material for gel-permation chromatography method for preparation, and applications |
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-
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-
1987
- 1987-05-23 EP EP87107532A patent/EP0249078B1/de not_active Expired - Lifetime
- 1987-05-23 DE DE8787107532T patent/DE3768052D1/de not_active Expired - Lifetime
- 1987-06-05 CS CS414387A patent/CS274614B2/cs unknown
- 1987-06-05 CA CA000538905A patent/CA1303594C/en not_active Expired - Fee Related
- 1987-06-05 DD DD87303574A patent/DD263711A5/de not_active IP Right Cessation
- 1987-06-05 CN CN87104030A patent/CN1009058B/zh not_active Expired
- 1987-06-05 JP JP62140159A patent/JP2665513B2/ja not_active Expired - Fee Related
-
1989
- 1989-02-21 US US07/313,319 patent/US4882048A/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN100369920C (zh) * | 2003-03-31 | 2008-02-20 | 特瓦药厂私人有限公司 | 大环内酯物质的结晶与纯化 |
Also Published As
Publication number | Publication date |
---|---|
JP2665513B2 (ja) | 1997-10-22 |
JPS631446A (ja) | 1988-01-06 |
DD263711A5 (de) | 1989-01-11 |
DE3768052D1 (de) | 1991-03-28 |
CS274614B2 (en) | 1991-09-15 |
EP0249078A3 (en) | 1988-08-10 |
US4882048A (en) | 1989-11-21 |
EP0249078A2 (de) | 1987-12-16 |
DE3619303A1 (de) | 1987-12-10 |
CN87104030A (zh) | 1987-12-16 |
CS414387A2 (en) | 1990-11-14 |
EP0249078B1 (de) | 1991-02-20 |
CA1303594C (en) | 1992-06-16 |
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