CN1156433C - 8-烷基-8-三环癸基(甲基)丙烯酸酯及其制备方法 - Google Patents
8-烷基-8-三环癸基(甲基)丙烯酸酯及其制备方法 Download PDFInfo
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- CN1156433C CN1156433C CNB011038896A CN01103889A CN1156433C CN 1156433 C CN1156433 C CN 1156433C CN B011038896 A CNB011038896 A CN B011038896A CN 01103889 A CN01103889 A CN 01103889A CN 1156433 C CN1156433 C CN 1156433C
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/40—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing carbon-to-metal bonds
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- C07C67/00—Preparation of carboxylic acid esters
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- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
- C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
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Abstract
本发明提供了一种新型的三环癸基(甲基)丙烯酸酯化合物及其制备方法。该化合物为分子式(1)的8-烷基-8-三环癸基(甲基)丙烯酸酯,其中R1为甲基或乙基,R2为氢或甲基。
Description
本发明涉及一种新型三环癸基(甲基)丙烯酸酯化合物及其制备方法,尤其是8-烷基-8-三环癸基(甲基)丙烯酸酯化合物及其制备方法。
丙烯酸酯或甲基丙烯酸酯是非常有用的单体,它们可以单独聚合或与其它单体共聚制得各种性能极好的聚合物。由此制得的聚合物具有极好的耐候性和透明性。且根据酯基的类型不同,可以制备各种性能等级的聚合物。特别地,当酯基为低化学反应活性的大脂肪族化合物时,所制备的聚合物可以工业化用作各种阻燃剂,其制备方法也受到广泛关注。
但是,普通带有大的脂肪族取代基的(甲基)丙烯酸酯化合物反应条件很难控制,导致产率低且不易提纯。因此,大批量制备普通(甲基)丙烯酸酯化合物是很困难的。
为了解决上述问题,本发明的一个目的是提供一种带有大取代基的丙烯酸酯化合物,其能够通过简单的适于工业化制备的方法制备和提纯。
本发明的另一个目的是提供一种制备丙烯酸酯化合物的方法。
此外,为了达到第一个目的,本发明提供分子式(1)所示的8-烷基-8-三环癸基(甲基)丙烯酸酯:
其中R1为甲基或乙基,R2为氢或甲基。
为了达到第二个目的,本发明提供制备所述化合物的方法,其包括以下步骤:a)由三环癸-8-酮与烷基格利雅试剂或烷基锂试剂反应合成8-烷基-8-三环癸醇;b)由步骤a)中合成的8-烷基-8-三环癸醇与(甲基)丙烯酰氯反应合成8-烷基-8-三环癸基(甲基)丙烯酸酯。
优选地,格利雅试剂选用烷基溴化镁或烷基氯化镁。
更优选地,如果烷基选用乙基,则选用乙基溴化镁或乙基氯化镁作为格利雅试剂。
根据本发明,在丙烯酸酯化合物的制备方法中,可以在每个步骤结束以后进行分离。但是,也可以在所有步骤都进行完之后,再就地进行分离。
参考下列附图,通过本发明的优选实施例的详细描述,可以更加清楚地了解本发明的上述目的和优点:
图1是本发明实施例1中所制备的8-乙基-8-三环癸基丙烯酸酯的NMR(核磁)谱图;
图2是本发明实施例1中所制备的8-乙基-8-三环癸基丙烯酸酯的FT-IR(傅立叶-红外光)谱图。
优选实施例的描述
现在详细描述本发明所述的8-烷基-8-三环癸基(甲基)丙烯酸酯的制备方法。
如下面的反应流程(1)所示,由三环癸基-8-酮与烷基格利雅试剂或烷基锂试剂反应合成8-烷基-8-三环癸基醇。[反应流程(1)]
其中R1为甲基或乙基,X为Cl或Br。
考虑到对副反应的抑制作用和对反应产率的影响,如果想要得到8-乙基-8-三环癸基(甲基)丙烯酸酯化合物,则优选地用乙基溴化镁或乙基氯化镁作为格利雅试剂。
由于上述反应是通过普通的格利雅反应机理进行的,所以在本发明中,反应温度和压力是没有意义的。
接着,如反应流程(2)所示,由8-烷基-8-三环癸醇与(甲基)丙烯酰氯反应合成8-烷基-8-三环癸基(甲基)丙烯酸酯。[反应流程(2)]
其中R1与上面所述相同,R2为氢或甲基。
下面参考下列实施例详细描述本发明,实施例是为了举例说明而不是为了限制本发明。
实施例18-乙基-8-三环癸基丙烯酸酯a.8-乙基-8-三环癸醇的合成
将440ml乙基溴化镁的四氢呋喃溶液(1.0M)用100ml四氢呋喃(THF)稀释。然后,将上述溶液倒入1升的烧瓶中,再保持在0℃下。用滴液漏斗缓慢滴入三环癸基-8-酮(60g,0.4mol),然后在搅拌下于室温反应大约12小时。反应结束后,用旋转蒸发仪除去过量THF,然后将终产物倒入水中。然后,用稀硫酸中和终产物,并用二乙基醚萃取,再然后在硫酸镁上干燥。所获得的产物通过柱状色谱法(乙烷∶乙酸乙酯=8∶1)过滤,以制备出所需产物8-乙基-8-三环癸醇(产率:70%)。b.8-乙基-8-三环癸基丙烯酸酯的合成
将8-乙基-8-三环癸醇(36g,0.2mol)和三乙基胺(0.22mol)溶解在250mlTHF中,然后用滴液漏斗缓慢滴入丙烯酰氯(19g,0.21mol)。然后,在搅拌下室温反应大约12小时。反应结束后,用旋转蒸发仪除去过量THF,然后将终产物倒入水中。然后,用稀盐酸中和终产物,并用二乙基醚萃取,再然后在硫酸镁上干燥。所获得的产物通过柱状色谱法(己烷∶乙酸乙酯=4∶1)过滤,以制备出所需产物8-乙基-8-三环癸基丙烯酸酯(产率:80%)。图1和图2分别是该化合物的NMR和FT-IR谱图。
1H-NMR(CDCl3;ppm):6.3(1H,d),6.1(1H,dd),5.7(1H,d),2.5(1H,s),
2.2(2H,m),1.4(2H,d),0.8(3H,t)
FT-IR(NaCl;cm-1): 2947,2863,1722,1638,1621,1402,1205
实施例2 8-甲基-8-三环癸基丙烯酸酯
目标化合物的制备方法同实施例1,只是用甲基溴化镁代替乙基溴化镁(产率:60%)。
实施例3 8-乙基-8-三环癸基甲基丙烯酸酯
目标化合物的制备方法同实施例1,只是用甲基丙烯酰氯代替丙烯酰氯(产率:65%)。
实施例4 8-甲基-8-三环癸基甲基丙烯酸酯
目标化合物的制备方法同实施例2,只是用甲基丙烯酰氯代替丙烯酰氯(产率:68%)。
本发明所述的8-烷基-8-三环癸基(甲基)丙烯酸酯能够通过现场制备法以很高的产率制备,有利于工业化大批量生产,且由于大环癸基取代基的引入导致该化合物的化学反应性低,因此适于大量用作各种类型的阻燃剂。
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020000008035A KR20010081854A (ko) | 2000-02-19 | 2000-02-19 | 8-알킬-8-트리싸이클로데카닐 (메타)아크릴레이트 및 그제조방법 |
KR8035/2000 | 2000-02-19 |
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Publication Number | Publication Date |
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CN1310165A CN1310165A (zh) | 2001-08-29 |
CN1156433C true CN1156433C (zh) | 2004-07-07 |
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CNB011038896A Expired - Fee Related CN1156433C (zh) | 2000-02-19 | 2001-02-19 | 8-烷基-8-三环癸基(甲基)丙烯酸酯及其制备方法 |
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US (1) | US6433215B1 (zh) |
JP (1) | JP2001233832A (zh) |
KR (1) | KR20010081854A (zh) |
CN (1) | CN1156433C (zh) |
TW (1) | TWI278449B (zh) |
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KR20030055875A (ko) * | 2001-12-27 | 2003-07-04 | 주식회사 켐써치 | 선형 또는 고리형 알콜을 갖는 비닐 에테르 유도체, 이를이용한 감광성 고분자 및 이 감광성 고분자를 이용한포토레지스트 조성물 |
KR100865864B1 (ko) * | 2002-11-04 | 2008-10-29 | 주식회사 동진쎄미켐 | 사이클로도데실이 결합된 펜던트 기를 가지는 화학적으로증폭된 고분자와 그 제조방법, 및 이를 포함하는 레지스트조성물 |
US20090214644A1 (en) * | 2003-07-31 | 2009-08-27 | Xanodyne Pharmaceuticals, Inc. | Tranexamic acid formulations with reduced adverse effects |
US20050025825A1 (en) * | 2003-07-31 | 2005-02-03 | Xanodyne Pharmacal, Inc. | Tranexamic acid formulations with reduced adverse effects |
US7947739B2 (en) | 2004-03-04 | 2011-05-24 | Ferring B.V. | Tranexamic acid formulations |
US20090215898A1 (en) * | 2004-03-04 | 2009-08-27 | Xanodyne Pharmaceuticals, Inc. | Tranexamic acid formulations |
US8022106B2 (en) * | 2004-03-04 | 2011-09-20 | Ferring B.V. | Tranexamic acid formulations |
US20050244495A1 (en) | 2004-03-04 | 2005-11-03 | Xanodyne Pharmaceuticals, Inc. | Tranexamic acid formulations |
US20050245614A1 (en) * | 2004-03-04 | 2005-11-03 | Xanodyne Pharmaceuticals, Inc. | Tranexamic acid formulations |
JP2006104172A (ja) * | 2004-10-08 | 2006-04-20 | Honshu Chem Ind Co Ltd | 新規な1−アルキルシクロヘキシル(メタ)アクリレート類 |
US20100280117A1 (en) * | 2009-04-30 | 2010-11-04 | Xanodyne Pharmaceuticals, Inc. | Menorrhagia Instrument and Method for the Treatment of Menstrual Bleeding Disorders |
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JPH08240881A (ja) * | 1995-03-02 | 1996-09-17 | New Oji Paper Co Ltd | 写真印画紙用支持体 |
KR20010081852A (ko) * | 2000-02-19 | 2001-08-29 | 김동석 | 8-알킬-8-트리싸이클로데카닐5-노르보르넨-2-카르복실레이트 및 그 제조방법 |
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- 2000-02-19 KR KR1020000008035A patent/KR20010081854A/ko not_active Application Discontinuation
- 2000-03-01 US US09/516,611 patent/US6433215B1/en not_active Expired - Fee Related
- 2000-10-13 JP JP2000313915A patent/JP2001233832A/ja active Pending
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- 2001-02-07 TW TW090102590A patent/TWI278449B/zh not_active IP Right Cessation
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US6433215B1 (en) | 2002-08-13 |
KR20010081854A (ko) | 2001-08-29 |
CN1310165A (zh) | 2001-08-29 |
TWI278449B (en) | 2007-04-11 |
JP2001233832A (ja) | 2001-08-28 |
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