CN101781199B - 一种o-酰基杯[4]芳烃的化学合成方法 - Google Patents
一种o-酰基杯[4]芳烃的化学合成方法 Download PDFInfo
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种式(I)所示的O-酰基杯[4]芳烃的化学合成方法,所述合成方法包括如下步骤:将如式(II)所示的杯芳烃溶解于有机溶剂中,在如式[III]所示的三氟甲磺酸盐催化下,和如式(IV)所示的酰化试剂于0℃~150℃反应0.1~10小时,反应液经后处理得到如式(I)所示的O-酰基杯[4]芳烃;式(I)、式(II)中,R1为C1~C6的烷基或氢;式(I)式(IV)中的R2为C1~C6的烷基、苯基或苄基;式(IV)中的X为Cl或R2COO。本发明的有益成果为:反应所用催化剂可回收套用;反应收率高达(一般在80%以上);工艺路线先进,反应条件温和;催化剂用量少,环境友好。
Description
(一)技术领域
本发明涉及一种O-酰基杯[4]芳烃的绿色合成方法,尤其是使用Lewis酸催化剂三氟甲磺酸盐来制备O-酰基杯[4]芳烃。
(二)背景技术
目前,O-酰基杯[4]芳烃的合成使用浓硫酸、对甲苯磺酸、三氟甲磺酸、三氯化铝、吡啶等传统的酸或碱作催化剂。如Tetrahedron 1982,38,373,提出用催化量的对甲苯磺酸催化,醋酸酐作为溶剂,回流20h得到目标产物,收率54%,Tetrahedron 1987,43,4917,提出用7当量的强碱NaH作为催化剂来完成酚羟基的苯甲酰化,收率80%。
传统的质子酸和有机碱能在高温条件下催化反应,得到相应的O-酰化产物,收率在50-80%之间。但是传统工艺的缺点是,往往要使用大大过量的催化剂和酰化试剂,反应温度高。而且使用的催化剂和试剂都不能回收再利用,在反应过程中和后处理中往往会产生大量HCl等气体,有一定的危险性。综上所述,传统工艺存在着催化剂和试剂的浪费以及能源浪费的问题。因此,寻找一种新型催化剂来替代传统催化剂是十分必要的。
(三)发明内容
为解决现有技术中O-酰基杯[4]芳烃的制备催化剂用量大、溶剂用量大,以及难以回收的缺点,本发明提供了一种工艺合理、反应收率高、催化剂用量少又可方便回收套用、生产成本低、环保的O-酰基杯[4]芳 烃的绿色化学合成方法。
为了达到以上目的,本发明的技术方案为:
一种式(I)所示的O-酰基杯[4]芳烃的化学合成方法,所述合成方法包括如下步骤:将如式(II)所示的杯芳烃溶解于有机溶剂中,在如式[III]所示的三氟甲磺酸盐催化下,和如式(IV)所示的酰化试剂于0℃~150℃反应0.1~10小时,反应液经后处理得到如式(I)所示的O-酰基杯[4]芳烃;
M(SO3CF3)x (III) R2COX (IV)
式(I)、式(II)中,R1为C1~C6的烷基或氢;式(I)式(IV)中的R2为C1~C6的烷基、苯基或苄基,;式(III)中所示的M为下列之一:Bi、Yb、Zn、Cu、Hf、Ga、In、La、Sc或Sm,x为1~4的自然数,x与M的价数相同;式(IV)中的X为Cl或R2COO。
本发明所述的杯芳烃、酰化试剂、三氟甲磺酸盐的物质的量比为1∶1~20∶0.001~1,优选为1∶4~10∶0.01~0.05。
本发明所述酰化试剂优选为乙酸酐、乙酰氯或苯甲酰氯。
优选的,本发明所述的反应温度为40~80℃,所述的反应时间为1~5小时。
本发明所述有机溶剂为下列一种或任意几种任意比例的混合物:二 氯甲烷、三氯甲烷、四氯化碳、1,1-二氯乙烷、1,2-二氯乙烷、1,1,1-三氯乙烷、1,1,2-三氯乙烷、1,1,2,2-四氯乙烷、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酸异丙酯、丙酮、丁酮、乙醚、丙醚、异丙醚、丁醚、四氢呋喃、2-甲基四氢呋喃、硝基甲烷、甲苯、苯、硝基苯、氯苯或乙腈,优选为二氯甲烷、三氯甲烷、乙酸乙酯、硝基甲烷、甲苯、氯苯或乙腈。所述的有机溶剂的用量与如式(II)所示的杯芳烃的质量比为1~100∶1,优选为10~30∶1。
本发明所述后处理方法为:反应完毕,反应液加水继续搅拌30分钟,使未反应的酰化试剂水解掉,静置分层,将有机层蒸除溶剂得到粗产品,粗产品经重结晶溶剂重结晶得到所述的O-酰基杯[4]芳烃。
本发明所述重结晶溶剂为下列一种或任意两种任意比例的混合物:甲醇、乙醇、异丙醇、醋酸、甲酸、二氯甲烷或三氯甲烷。
本发明所述的O-酰基杯[4]芳烃的化学合成方法,推荐按如下步骤进行:将如式(II)所示的杯芳烃溶解于有机溶剂中,在如式[III]所示的三氟甲磺酸盐催化下,和如式(IV)所示的酰化试剂于40℃~80℃反应1~5小时,反应完毕,反应液加水继续搅拌30分钟,这里加水的量足以使未反应的酰化试剂水解掉即可,再静置分层,将有机层蒸除溶剂得到粗产品;粗产品经重结晶溶剂重结晶得到所述的O-酰基杯[4]芳烃;式(I)、式(II)中,R1为C1~C6的烷基或氢;R2为C1~C6的烷基、苯基或苄基;式(III)中所示的M为Bi、Yb或Sc,所述酰化试剂为乙酸酐、乙酰氯或苯甲酰氯;所述的杯芳烃、酰化试剂、三氟甲磺酸盐的物质的量比为1∶4~10∶0.01~0.05;所述的有机溶剂的用量与如式(II) 所示的杯芳烃的质量比为1∶10~30。
本发明的有益成果体现在:1.反应所用催化剂可回收套用;2.反应收率高(一般在80%以上);3.工艺路线先进,反应条件温和;4.催化剂用量少,环境友好。
(四)具体实施方式
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此:
实施例1:
在两口瓶中,装入四叔丁基杯[4]芳烃1.0g(1.54mmol),加入20mL三氯甲烷搅拌溶解,加入0.0154mmol三氟甲磺酸锌,加入乙酸酐1.2g(0.012mol),于50℃反应2小时,反应完毕加15ml水搅拌30min,分去水层,将有机层蒸除溶剂,得黄色粗品,粗品用20ml二氯甲烷/甲醇(按体积比1∶1混合)重结晶,得白色纯品1.1g,收率87%,熔点320℃。
实施例2:
在两口瓶中,装入四叔丁基杯[4]芳烃1.0g(1.54mmol),加入25mL三氯甲烷搅拌溶解,加入0.0231mmol三氟甲磺酸铋,加入乙酸酐1.2g(0.012mol),于20℃反应2小时,反应完毕加15ml水搅拌30min,分去水层,将有机层蒸除溶剂,得黄色粗品,粗品用20ml二氯甲烷/甲醇(按体积比1∶1混合)重结晶,得白色纯品0.9g,收率72%,熔点320℃。
实施例3:
在两口瓶中,装入四叔丁基杯[4]芳烃1.0g(1.54mmol),加入25mL三氯甲烷搅拌溶解,加入0.0308mmol三氟甲磺酸镱,加入乙酸酐1.2g(0.012mol),于20℃反应10小时,反应完毕加10ml水搅拌30min,分去水层,将有机层蒸除溶剂,得黄色粗品,粗品用20ml二氯甲烷/甲醇(按体积比1∶1混合)重结晶,得白色纯品0.85g,收率67%,熔点320℃。
实施例4:
在两口瓶中,装入四叔丁基杯[4]芳烃1.0g(1.54mmol),加入25mL二氯甲烷搅拌溶解,加入0.0308mmol三氟甲磺酸铋,加入乙酸酐1.2g(0.012mol),40℃回流反应1小时,反应完毕加10ml水搅拌30min,分去水层,将有机层蒸除溶剂,得黄色粗品,粗品用20ml二氯甲烷/甲醇(按体积比1∶1混合)重结晶,得白色纯品0.87g,收率68%,熔点320℃。
实施例5:
反应溶剂换为甲苯25mL,110℃回流反应2小时,其他操作同例1,收率70%,熔点321℃。
实施例6:
反应溶剂换为硝基苯20mL,60℃反应3小时,其他操作同例1,收 率75%,熔点320℃。
实施例7:
催化剂三氟甲磺酸镱用量为1.54mmol,乙酸酐3g(0.03mol),其他操作同例1,收率88%,熔点321℃。
实施例8:
催化剂三氟甲磺酸镱用量0.77mmol,乙酸酐3g(0.03mol),其他操作同例1,收率80%,熔点322℃。
实施例9:
重结晶溶剂换为醋酸,其他操作同例1,收率70%,熔点322℃。
实施例10:
重结晶溶剂换为三氯甲烷/乙醇(体积比为1∶1),其他操作同例1,收率80%,熔点320℃。
实施例11:
在两口瓶中,装入去叔丁基杯[4]芳烃1.0g(2.4mmol),加入25mL三氯甲烷搅拌溶解,加入0.0154mmol三氟甲磺酸铋,加入乙酰氯1.0g(12.7mmol),于20℃反应2小时,反应完毕加20ml水搅拌30min,分去水层,将有机层蒸除溶剂,得黄色粗品,粗品用20ml二氯甲烷/甲醇(体 积比为1∶1)重结晶,得白色纯品1.2g,收率86%,熔点402℃。
实施例12:
在二口瓶中,装入去叔丁基杯[4]芳烃1.0g(2.4mmol),加入25mL三氯甲烷搅拌溶解,加入0.0154mmol三氟甲磺酸铋,加入苯甲酰氯2.6g(18.5mmol),于20℃反应2小时,反应完毕加20ml水搅拌30min,分去水层,将有机层蒸除溶剂,得粗品,用20ml二氯甲烷/甲醇(体积比为1∶1)重结晶,得白色纯品1.5g,收率83%,熔点358℃。
实施例13:
催化剂为三氟甲磺酸钪,用量为0.0154mmol,乙酸酐1.3g(13mmol),其他操作同例1,收率89%,熔点321℃。
实施例14
催化剂为三氟甲磺酸镓,用量为0.0154mmol,乙酸酐3g(0.03mol),其他操作同例1,收率71%,熔点321℃。
Claims (8)
1.一种式(I)所示的O-酰基杯[4]芳烃的化学合成方法,其特征在于所述合成方法包括如下步骤:将式(II)所示的杯芳烃溶解于有机溶剂中,在式(III)所示的三氟甲磺酸盐催化下,和式(Ⅳ)所示的酰化试剂于0℃~150℃反应0.1~10小时,反应液经后处理得到式(I)所示的O-酰基杯[4]芳烃;
M(SO3CF3)x (III) R2COX (Ⅳ)
式(I)、式(II)中,R1为C1~C6的烷基或氢;式(I)式(Ⅳ)中的R2为C1~C6的烷基、苯基或苄基,;式(III)中所示的M为下列之一:Bi、Yb、Zn、Ga、或Sc,x为1~4的自然数,x与M的价数相同;式(Ⅳ)中的X为Cl或R2COO;
所述的杯芳烃、酰化试剂、三氟甲磺酸盐的物质的量比为1:4~10:0.01~0.05。
2.如权利要求1所述的O-酰基杯[4]芳烃的化学合成方法,其特征在于所述酰化试剂为乙酸酐、乙酰氯或苯甲酰氯。
3.如权利要求1所述的O-酰基杯[4]芳烃的化学合成方法,其特征在于所述的反应温度为40~80℃,所述的反应时间为1~5小时。
4.如权利要求1所述的O-酰基杯[4]芳烃的化学合成方法,其特征在于所述有机溶剂为下列一种或几种任意比例的混合物:二氯甲烷、三氯甲烷、四氯化碳、1,1-二氯乙烷、1,2-二氯乙烷、1,1,1-三氯乙烷、1,1,2-三氯乙烷、1,1,2,2-四氯乙烷、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酸异丙酯、丙酮、丁酮、乙醚、丙醚、异丙醚、丁醚、四氢呋喃、2-甲基四氢呋喃、硝基甲烷、甲苯、苯、硝基苯、氯苯或乙腈。
5.如权利要求1所述的O-酰基杯[4]芳烃的化学合成方法,其特征在于所述的有机溶剂的用量与式(II)所示的杯芳烃的质量比为1~100:1。
6.如权利要求1所述的O-酰基杯[4]芳烃的化学合成方法,其特征在于所述后处理方法为:反应完毕,反应液加水继续搅拌30分钟使未反应的酰化试剂水解,静置分层,将有机层蒸除溶剂得到粗产品,粗产品经重结晶溶剂重结晶得到所述的O-酰基杯[4]芳烃。
7.如权利要求6所述的O-酰基杯[4]芳烃的化学合成方法,其特征在于所述重结晶溶剂为下列一种或任意两种任意比例的混合物:甲醇、乙醇、异丙醇、醋酸、甲酸、二氯甲烷或三氯甲烷。
8.如权利要求1所述的O-酰基杯[4]芳烃的化学合成方法,其特征在于所述合成方法按如下步骤进行:将式(II)所示的杯芳烃溶解于有机溶剂中,在式(III)所示的三氟甲磺酸盐催化下,和式(Ⅳ)所示的酰化试剂于40℃~80℃反应1~5小时,反应完毕,反应液加水继续搅拌30分钟,静置分层,将有机层蒸除溶剂得到粗产品;粗产品 经重结晶溶剂重结晶得到所述的O-酰基杯[4]芳烃;式(I)、式(II)中,R1为C1~C6的烷基或氢;R2为C1~C6的烷基、苯基或苄基;式(III)中所示的M为Bi、Yb或Sc;所述酰化试剂为乙酸酐、乙酰氯或苯甲酰氯;所述的杯芳烃、酰化试剂、三氟甲磺酸盐的物质的量比为1:4~10:0.01~0.05;所述的有机溶剂的用量与式(II)所示的杯芳烃的质量比为10~30:1。
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