CN113372208A - 一种反-4-(反-4-烷环己基)环己烷甲醛的制备方法 - Google Patents
一种反-4-(反-4-烷环己基)环己烷甲醛的制备方法 Download PDFInfo
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Abstract
本发明公开了一种反‑4‑(反‑4‑烷基环己基)环己烷甲醛的制备方法,属于液晶中间体合成方法技术领域,包括以下步骤:以(4‑烷基环己基)苯为起始原料,经羰基化反应、醛基保护加氢、脱保护制得反‑4‑(反‑4‑烷基环己基)环己烷甲醛;本发明化合物制备方法简单,达到缩短路线、简化后处理、节约工时成本的目的。
Description
技术领域
本发明属于液晶中间体合成方法技术领域,具体涉及一种反-4-(反-4-烷基环己基)环己烷甲醛的制备方法。
背景技术
近年来能满足液晶显示器宽温度范围、高响应速度的要求的液晶材料成为国内外企业关注的重点,而具有低粘度高热、光、电、化学稳定性的双环类液晶材料成为研究重点,大量应用于TFT-LCD中。液晶中间体反式-4-(反式-4-烷基环己基)环己烷甲醛作为重要的液晶中间体材料,其品质的高低不仅影响单体液晶材料成本问题,最根本的会影响到显示器件的显示效果(响应速度、刷新频率及色彩饱和度等问题)。
目前主要采用以下合称线路,该合成路线反应步骤多,合成路线长、总工艺耗时长,导致时间成本过高;合成工艺中用到氯甲醚三苯基膦盐,原子利用率低;反应中产生很难除去的关键性杂质,不易纯化,直接影响到产品的生产成本及应用前景。
发明内容
本发明的目的在于改进已有技术的不足而提供一种合成路线简单、反应易于控制、反应副产物少、收率高、合成过程中原子利用率高、原料成本减少、产品易于纯化、综合成本低的反-4-(反-4-烷基环己基)环己烷甲醛的制备方法。
本发明的目的是这样实现的,一种反-4-(反-4-烷基环己基)环己烷甲醛的制备方法,包括以下步骤:
S1:(4-烷基-环己基)-苯与一氧化碳在催化剂无水三氯化铝作用反应,生成4-(4-烷基-环己基)-苯甲醛;
S2:4-(4-烷基-环己基)-苯甲醛与乙二醇在甲苯、对甲苯磺酸反应体系中反应,生成2-[4-(4-烷基-环己基)-苯基]-[1,3]二氧戊环;
S3:1-二乙氧基甲基-4-(4-烷基-环己基)-苯加氢生成2-(4'-烷基-双环己基-4-基)-[1,3]二氧戊环;
S4:2-(4'-烷基-双环己基-4-基)-[1,3]二氧戊环经脱保护生成4-(反-4-烷基环己基)环己烷甲醛;
S5:4-(反-4-烷基环己基)环己烷甲醛经过转型生成反-4-(反-4-烷基环己基)环己烷甲醛。
式中n=2~5。
为了进一步实现本发明的目的,可以是所述S1含有式(Ⅱ)化合物具体是通过以下步骤制得:将(4-烷基-环己基)-苯溶于邻二甲苯,加入5~6滴浓盐酸、催化剂无水三氯化铝降温至0℃,在1MPa压力下通入一氧化碳气体后反应,反应结束后,经分液、水洗、干燥、蒸馏得到化合物4-(4-烷基-环己基)-苯甲醛。
为了进一步实现本发明的目的,可以是所述S2含有式(Ⅲ)化合物具体是通过以下步骤制得:4-(4-烷基-环己基)-苯甲醛溶于甲苯溶液中,加入乙二醇、对甲苯磺酸,加热回流分水反应,反应结束后经水洗、浓缩、结晶得到化合物2-[4-(4-烷基-环己基)-苯基]-[1,3]二氧戊环。
为了进一步实现本发明的目的,可以是所述S3含有式(Ⅳ)化合物具体是通过以下步骤制得:2-[4-(4-烷基-环己基)-苯基]-[1,3]二氧戊环溶于乙醇溶液中,加入钯催化剂,通入氢气反应,反应结束后过滤、浓缩得到化合物2-(4'-烷基-双环己基-4-基)-[1,3]二氧戊环。
为了进一步实现本发明的目的,可以是所述S4含有式(Ⅴ)化合物具体是通过以下步骤制得:2-(4'-烷基-双环己基-4-基)-[1,3]二氧戊环溶于甲苯溶液中,滴加无水甲酸反应,反应结束后经中和、水洗、浓缩得到化合物4-(反-4-烷基环己基)环己烷甲醛。
为了进一步实现本发明的目的,可以是所述S5含有式(Ⅵ)化合物具体是通过以下步骤制得:4-(反-4-烷基环己基)环己烷甲醛,溶于甲醇溶液,滴加到氢氧化钾溶液中反应,反应结束后经水洗、干燥、浓缩得到化合物反-4-(反-4-烷基环己基)环己烷甲醛。
本发明与已有技术相比具有以下显著特点和积极效果:合成路线简单,反应副产物少,收率高;合成过程中不使用氯甲醚三苯基膦盐,原子利用率提高;合成路线变短,原料成本减少、产品纯化工序减少、综合成本降低。
具体实施方式
以下结合实施例对本发明进一步说明,需要说明的是以下的实施例仅为了清楚的理解本发明,本发明不限于该实施例。下述实施例中所用的材料、试剂等,如无特殊说明,均可从商业途径得到。
实施例1,一种反-4-(反-4-丙基环己基)环己烷甲醛的制备方法,包括以下步骤:
S1:(4-丙基-环己基)-苯与一氧化碳在催化剂无水三氯化铝作用反应,生成4-(4-丙基-环己基)-苯甲醛;
往1L反应容器中,加入(4-丙基-环己基)-苯50g,邻二甲苯中250ml,加入5~6滴浓盐酸、催化剂无水三氯化铝33g,降温至0℃,在1MPa压力下通入一氧化碳气体后反应。通气反应到设定的时间后,放空尾气至常压,取出反应液倾入盛有300mL碎冰水的烧杯中,搅拌,使之水解。经分液、水洗、干燥、蒸馏得到化合物4-(4-丙基-环己基)-苯甲醛54g;
S2:4-(4-丙基-环己基)-苯甲醛与乙二醇在甲苯、对甲苯磺酸反应体系中反应,生成2-[4-(4-丙基-环己基)-苯基]-[1,3]二氧戊环;
在氮气保护下,往1L反应容器中,加入2-[4-(4-丙基-环己基)-苯基]-[1,3]二氧戊环54g,甲苯300ml,对甲苯磺酸20g,乙二醇17.5g,升温160℃~170℃,回流分水,反应3h,反应结束后经水洗、浓缩、结晶得到化合物1-二乙氧基甲基-4-(4-丙基-环己基)-苯43.8g;
S3:1-二乙氧基甲基-4-(4-丙基-环己基)-苯加氢生成2-(4'-丙基-双环己基-4-基)-[1,3]二氧戊环;
往高压反应容器中加入1-二乙氧基甲基-4-(4-丙基-环己基)-苯43.8g,乙醇300ml,钯催化剂0.2g,氢气置换三次后,通入氢气,在40℃~50℃、0.03MPa下反应5h,反应结束后经过滤,浓缩得到2-(4'-丙基-双环己基-4-基)-[1,3]二氧戊环44g。
S4:2-(4'-丙基-双环己基-4-基)-[1,3]二氧戊环经脱保护生成4-(反-4-丙基环己基)环己烷甲醛;
在氮气保护下,往1L反应容器中,加入2-(4'-丙基-双环己基-4-基)-[1,3]二氧戊环44g,甲苯200ml,无水甲酸15g,加热回流反应,反应结束后,经中和、水洗、浓缩,得到4-(反式-4-丙基环己基)环己烷甲醛30.1g;
S5:4-(反-4-丙基环己基)环己烷甲醛经过转型生成反-4-(反-4-丙基环己基)环己烷甲醛;
在氮气保护下,往1L反应容器中,加入甲醇150g,氢氧化钾20g,搅拌均匀后滴加4-(反-4-丙基环己基)环己烷甲醛30.1,在0℃~10℃保温反应,反应结束后,经水洗、浓缩、结晶,得到反-4-(反-4-丙基环己基)环己烷甲醛29.5g。
实施例2,一种反-4-(反-4-丁基环己基)环己烷甲醛的制备方法,包括以下步骤:
S1:(4-丁基-环己基)-苯与一氧化碳在催化剂无水三氯化铝作用反应,生成4-(4-丁基-环己基)-苯甲醛;
往1L反应容器中,加入(4-丁基-环己基)-苯53.5g,邻二甲苯中250ml,加入5~6滴浓盐酸、催化剂无水三氯化铝33g,降温至0℃,在1MPa压力下通入一氧化碳气体后反应。通气反应到设定的时间后,放空尾气至常压,取出反应液倾入盛有300mL碎冰水的烧杯中,搅拌,使之水解。经分液、水洗、干燥、蒸馏得到化合物4-(4-丁基-环己基)-苯甲醛57.3g;
S2:4-(4-丁基-环己基)-苯甲醛与乙二醇在甲苯、对甲苯磺酸反应体系中反应,生成2-[4-(4-丁基-环己基)-苯基]-[1,3]二氧戊环;
在氮气保护下,往1L反应容器中,加入2-[4-(4-丁基-环己基)-苯基]-[1,3]二氧戊环57.3g,甲苯300ml,对甲苯磺酸20g,乙二醇17.5g,升温160℃~170℃,回流分水,反应3h,反应结束后经水洗、浓缩、结晶得到化合物1-二乙氧基甲基-4-(4-丁基-环己基)-苯46g;
S3:1-二乙氧基甲基-4-(4-丁基-环己基)-苯加氢生成2-(4'-丁基-双环己基-4-基)-[1,3]二氧戊环;
往高压反应容器中加入1-二乙氧基甲基-4-(4-丁基-环己基)-苯46g,乙醇300ml,钯催化剂0.2g,氢气置换三次后,通入氢气,在40℃~50℃、0.03MPa下反应5h,反应结束后经过滤,浓缩得到2-(4'-丁基-双环己基-4-基)-[1,3]二氧戊环46.2g;
S4:2-(4'-丁基-双环己基-4-基)-[1,3]二氧戊环经脱保护生成4-(反-4-丁基环己基)环己烷甲醛;
在氮气保护下,往1L反应容器中,加入2-(4'-丁基-双环己基-4-基)-[1,3]二氧戊环46.2g,甲苯200ml,无水甲酸15g,加热回流反应,反应结束后,经中和、水洗、浓缩,得到4-(反式-4-丁基环己基)环己烷甲醛31.9g;
S5:4-(反-4-丁基环己基)环己烷甲醛经过转型生成反-4-(反-4-丁基环己基)环己烷甲醛;
在氮气保护下,往1L反应容器中,加入甲醇150g,氢氧化钾20g,搅拌均匀后滴加4-(反-4-丁基环己基)环己烷甲醛31.9g,在0℃~10℃保温反应,反应结束后,经水洗、浓缩、结晶,得到反-4-(反-4-丁基环己基)环己烷甲醛31.2g。
Claims (6)
1.一种反-4-(反-4-烷基环己基)环己烷甲醛的制备方法,其特征在于,包括以下步骤:
S1:(4-烷基-环己基)-苯与一氧化碳在催化剂无水三氯化铝作用反应,生成4-(4-烷基-环己基)-苯甲醛;
S2:4-(4-烷基-环己基)-苯甲醛与乙二醇在甲苯、对甲苯磺酸反应体系中反应,生成2-[4-(4-烷基-环己基)-苯基]-[1,3]二氧戊环;
S3:1-二乙氧基甲基-4-(4-烷基-环己基)-苯加氢生成2-(4'-烷基-双环己基-4-基)-[1,3]二氧戊环;
S4:2-(4'-烷基-双环己基-4-基)-[1,3]二氧戊环经脱保护生成4-(反-4-烷基环己基)环己烷甲醛;
S5:4-(反-4-烷基环己基)环己烷甲醛经过转型生成反-4-(反-4-烷基环己基)环己烷甲醛。
式中n=2~5。
2.根据权利要求1所述的一种反-4-(反-4-烷基环己基)环己烷甲醛的合成方法,其特征在于,所述步骤S1中含有式(Ⅱ)化合物具体是通过以下步骤制得:
将(4-烷基-环己基)-苯溶于邻二甲苯,加入5~6滴浓盐酸、催化剂无水三氯化铝,降温到0℃,在1MPa压力下下通入一氧化碳气体后反应,反应结束后,经分液、水洗、干燥、蒸馏得到化合物4-(4-烷基-环己基)-苯甲醛。
3.根据权利要求1所述的一种反-4-(反-4-烷基环己基)环己烷甲醛的合成方法,其特征在于,所述步骤S2中含有式(Ⅲ)化合物具体是通过以下步骤制得:
4-(4-烷基-环己基)-苯甲醛溶于甲苯溶液中,加入乙二醇、对甲苯磺酸,加热回流分水反应,反应结束后经水洗、浓缩、结晶得到化合物2-[4-(4-烷基-环己基)-苯基]-[1,3]二氧戊环。
4.根据权利要求1所述的一种反-4-(反-4-烷基环己基)环己烷甲醛的合成方法,其特征在于,所述步骤S3中含有式(Ⅳ)化合物具体是通过以下步骤制得:
2-[4-(4-烷基-环己基)-苯基]-[1,3]二氧戊环溶于乙醇溶液中,加入钯催化剂,通入氢气反应,反应结束后过滤、浓缩得到化合物2-(4'-烷基-双环己基-4-基)-[1,3]二氧戊环。
5.根据权利要求1所述的一种反4-(反-4-烷基环己基)环己烷甲醛的合成方法,其特征在于,所述步骤S4中含有式(Ⅴ)化合物具体是通过以下步骤制得:
2-(4'-烷基-双环己基-4-基)-[1,3]二氧戊环溶于甲苯溶液中,滴加无水甲酸反应,反应结束后经中和、水洗、浓缩得到化合物4-(反-4-烷基环己基)环己烷甲醛。
6.根据权利要求1所述的一种反-4-(反-4-烷基环己基)环己烷甲醛的合成方法,其特征在于,所述步骤S5中含有式(Ⅵ)化合物具体是通过以下步骤制得:
4-(反-4-烷基环己基)环己烷甲醛,溶于甲醇溶液,滴加到氢氧化钾溶液中反应,反应结束后经水洗、干燥、浓缩得到化合物反-4-(反-4-烷基环己基)环己烷甲醛。
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