CN103641692B - 一种含氟双酚化合物的制备 - Google Patents
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/02—Lithium compounds
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种新型含氟双酚化合物的制备2,2-双[4-(2,4-二氨基苯氧基)苯基]六氟丙烷的制备方法,包括步骤:间二溴苯的锂化,制备间苯二锂盐;间苯二锂盐和六氟丙酮的加成反应,制备1,3-二(2-羟基-六氟丙叉基)苯;1,3-二(2-羟基-六氟丙叉基)苯与苯酚的缩合反应,制备1,3-二(1-(4-羟基苯基)-六氟丙叉基)苯。本发明操作简单,成本低廉,所得产品纯度>99%,适用于工业化生产。
Description
技术领域
本发明涉及一种新型含氟双酚化合物1,3-二(2-(4-羟基苯基)-六氟丙叉基)苯的合成方法,属于精细化工技术领域。
技术背景
从20世纪30年代初期氟里昂问世以来,有机氟化学一直表现出蓬勃发展的趋势,含氟化合物几乎深入到我们日常生活的方方面面。1945年之后,随着冷战的开始,各种各样的防务计划为不断地发展氟化学和利用含氟化合物提供了经久不衰的原动力。到20世纪的50~60年代由于更多的民用产品如含氟药物,农药及含氟材料的出现将有机氟化学研究推向了前沿领域,如被称为哈龙(Halon)的物质是一类含溴含氟的烷烃类化合物,它是一类直到现在还被广泛使用的化学灭火剂。
1938年,杜邦公司普兰科特(Plunkett)发明的聚四氟乙烯(PTFE)成为含氟聚合物研究和应用的开端【含氟材料的研究开发,[日]山边正显松尾仁主编,闻建勋译,华东理工大学出版社,2003年6月第一版】。目前,PTFE的应用已从最初的航空、航天和军工等国防领域扩展到石油化工、机械、电子电器、建筑、纺织等国民经济的各个领域。高强度高韧性的氟树脂乙烯-四氟乙烯共聚物(ETFE)是另一重要的含氟聚合物。奥运场馆“水立方”便是ETFE膜结构建筑的典型代表。除了聚合物外,很多小分子的有机氟化物在电子工业中也有多方面的应用。一些含氟的有机化合物气体,如:CClF3,CHF3和C2F6等,在制造微芯片的等离子蚀刻过程中,被用做蚀刻剂。在医药化学领域,向有机分子中引入氟原子是开发新的抗癌药物、抗肿瘤药物、抗病毒药物、消炎药物等的重要方向。在现代农作物保护方面,含氟农用化学品已广泛用作除草剂、杀虫剂以及杀菌剂等。近年来,利用正电子发射断层扫描(PET)技术诊断肿瘤及癌症得到广泛的关注和应用。[18F]-2-氟-脱氧葡萄糖(FDG)是应用最为广泛的癌症诊断PET探针【T.Ritter.AFluoride-Derived Electrophilic Late-Stage Fluorination Reagent for PET Imaging.Science2011,334,639】。
综合国内外文献来看,在高分子材料领域,含多氟化合物的制备集中在聚酰亚胺、环氧丙烷表面活性剂和氟碳塑料用单体。联合合碳化工业气体技术公司报导了应用于聚砜膜的含氟单体六氟代BIS-A【川上·詹姆士·河吉美,等.碳化的六氟代BIS-A聚砜膜及其用于流体分离的方法.CN90109597.4】。美国3M公司公开了一种重要的化工中间体六氟代丙酮的制备方法,是从六氟丙酮肟制备六氟丙酮的方法,包括加热六氟丙酮肟(或其溶剂配合物)和一高浓度无机酸以产生六氟丙酮【Y·切布可夫.六氟丙酮及其肟的制备.CN95191786.2】。上海康鹏化学有限公司和央硝子株式会社则公开了双(2-羟基六氟丙基)苯酚的制备方法,以双(2-羟基六氟丙基)苯为原料在溶剂和硫酸中与二溴海因反应得到溴化中间体,将溴化中间体在碱性金属水溶液及催化剂条件下水解成双(2-羟基六氟丙基)苯酚,这是一类重要的含氟酚类化合物【杨建华,等.双(2-羟基六氟丙基)苯酚的制备方法.CN200510028549_2】。
东华大学公开了一种含氟有机胺类2,2-双[4-(2,4-二氨基苯氧基)苯基]六氟丙烷,应用在制备含氟聚酰胺和含氟聚酰亚胺材料中【虞鑫海.2,2-双[4-(2,4-二氨基苯氧基)苯基]六氟丙烷的制备方法.CN200810034956_8】。含氟有机胺也可以用作环氧树脂的含氟固化剂,东华大学和上海睿兔电子材料有限公司公开了一种2,2-双[4-(2,4-二氨基苯氧基)苯基]六氟丙烷型耐高温环氧胶粘剂及其制备方法,由质量比为1:1-2的A组份和B组份组成,其中,A组份是由2,2-双[4-(2,4-二氨基苯氧基)苯基]六氟丙烷与环氧树脂反应而成的共聚物;B组份是由2,2-双[4-(2,4-二氨基苯氧基)苯基]六氟丙烷与芳香族二元酸酐在强极性非质子有机溶剂和甲苯中反应而成的固含量为15%-30%的均相透明溶液【虞鑫海,等.2,2-双[4-(2,4- 二氨基苯氧基)苯基]六氟丙烷型耐高温环氧胶粘剂及其制备方法.CN201310076575_7】。济南大学则公开了一种2,2-双(4-羧基苯基)六氟丙烷的制备方法,以2,2-双(4-甲基苯基)六氟丙烷为原料,在N-羟基邻苯二甲酰亚胺和过渡金属盐催化剂、氧气氧化剂进行催化氧化反应制备【张书香,等.新催化体系下2,2-双(4-羧基苯基)六氟丙烷的制备方法.CN201110400454_4】。
尽管含多氟化合物的报导很多,但关于含氟酚类化合物的报导较少,还没有发现1,3-二(2-(4-羟基苯基)-六氟丙叉基)苯的专利公开报导。本发明公开一种新型含氟双酚化合物1,3-二(2-(4-羟基苯基)-六氟丙叉基)苯的合成方法,操作简便、成本低、产率高和纯度高。本发明公开一种新型含氟双酚化合物1,3-二(2-(4-羟基苯基)-六氟丙叉基)苯是含氟高分子材料的重要原料。
发明内容
本发明的目的在于提供一种新型含氟双酚化合物1,3-二(2-(4-羟基苯基)-六氟丙叉基)苯的合成方法。
为实现上述目的,本发明提供的合成方法如图1所示,其特点在于包含三个连续步骤:a)间二溴苯的锂化,制备间苯二锂盐;b)间苯二锂盐和六氟丙酮的加成反应,制备1,3-二(2-羟基-六氟丙叉基)苯;c)1,3-二(2-羟基-六氟丙叉基)苯与苯酚的缩合反应,制备1,3-二(2-(4-羟基苯基)-六氟丙叉基)苯。
步骤a)中的间二溴苯的锂化,在四氢呋喃、***和甲苯-三乙胺的一种或混合溶剂中进行;间二溴苯和金属锂的摩尔配比控制在(2~3):1;锂化反应在氮气保护的无水无氧条件下进行;锂化反应的温度40~80℃,反应时间3-12h。通过控制以上锂化参数,可以实现间二溴苯的完全锂化。需要特别强调的是,反应必须在无水无氧条件下进行,否则极大影响转化率。溶剂经过4A分子筛除水处理,如果直接采用市售分析纯溶剂,其中的微量水分对于反应顺利进行有所影响。
步骤b)中的间苯二锂盐和六氟丙酮的加成反应,是将六氟丙酮滴加到a)步骤得到的间苯二锂盐溶液中,滴加速度控制在使反应温度<40℃,反应时间1-10h。间苯二锂盐和六氟丙酮的加成反应在室温下即可顺利进行,温度过高反而会导致副反应。因此保持自然温度下反应即可。溶剂对该步影响很大,当选用甲苯等非极性溶剂时,加入一部分四氢呋喃或三乙胺,有利于反应顺利进行。
步骤c)中的1,3-二(2-羟基-六氟丙叉基)苯与苯酚的缩合反应,溶剂是甲苯、四氢呋喃和***中的一种或混合物;反应在酸性催化剂作用下进行,酸性催化剂是硫酸、盐酸、磷酸、对甲苯磺酸、磷钨酸和酸性蒙脱土的一种或混合物,用量是苯酚质量的0.5~3%;缩合反应温度40-100℃,反应时间3-10h。反应温度和反应时间对于转化率影响很大;考虑到该反应没有副反应,建议采用较高的反应温度,比如70-100℃。采用薄板色谱检测反应的进展,当反应基本完全时,即可冷却提纯。
本发明公开的一种新型含氟双酚化合物1,3-二(2-(4-羟基苯基)-六氟丙叉基)苯的合成方法,具有3个特点:
(1)操作简便,易于实现工业化;
(2)采用常用价廉的原料和溶剂,成本低;
(3)作为含氟材料的单体原料,合成含氟环氧树脂、含氟氰酸酯树脂、含氟不饱和聚酯树脂和其它含氟高分子材料,应用广泛。
附图说明
图11,3-二(2-(4-羟基苯基)-六氟丙叉基)苯的合成路线图
具体实施方式
以下是本发明的实施例,但本发明并不局限于以下实施例,任何基于本发明所述方法进行的制备参数调整,都在本发明范围之内。
实施例1
在装有回流冷凝管(冷凝管上端装有氮气保护气球)、温度计和加料漏斗的500mL玻璃瓶中,加入200ml四氢呋喃和2.8g(0.4mol)锂丝,加热到40℃,在激烈搅拌下滴加11.8g(0.2mol)间二溴苯,锂化反应引发后,反应液温度很快升高到沸腾。控制滴加速率保持微沸状态,全部滴完约需1h。保持微沸状态继续反应2h,锂丝完全消失。
以上反应液冷却至室温,在搅拌下滴加62g(0.4mol)六氟丙酮,控制滴加速度保持反应液温度不高于40℃,六氟丙酮在1h内滴加完毕,继续自然反应3h得到混浊悬浮液。用10%盐酸中和,转变为透明反应液。将反应液真空蒸馏除去挥发份得到白色固体。
用100ml甲苯萃取后,用4*30ml去离子水洗涤甲苯溶液,然后加入15g无水硫酸钠干燥剂,静置过夜;过滤除去干燥剂,得甲苯溶液。将甲苯溶液中再加入38g(0.4mol)苯酚,同时加入0.4g对甲苯磺酸,加热到70℃反应6h。冷却到室温后,用6*30ml去离子水洗涤甲苯反应液。将分液得到的甲苯溶液真空蒸馏除去甲苯得到含氟双酚化合物1,3-二(2-(4-羟基苯基)-六氟丙叉基)苯84g。总收率:78%。
元素分析:C,40.5%;H,3.32%;F,38.1%。IC-MS质谱分析:M+(分子量),538。GC:99%(纯度)。熔点(热台显微镜法):136℃。溶解性(良溶剂):乙醇;丙酮;四氢呋喃。
实施例2
在装有回流冷凝管(冷凝管上端装有氮气保护气球)、温度计和加料漏斗的500mL玻璃瓶中,加入200ml甲苯-四氢呋喃(质量比3:1)和2.8g(0.4mol)锂丝,加热到60℃,在激烈搅拌下滴加11.8g(0.2mol)间二溴苯,锂化反应引发后,反应液温度很快升高到微沸。控制滴加速率保持微沸状态,全部滴完约需0.5h(相比四氢呋喃介质沸点要高,滴加速度就可以快一些)。保持微沸状态继续反应1h,锂丝完全消失。
以上反应液冷却至室温,在搅拌下滴加62g(0.4mol)六氟丙酮,控制滴加速度保持反应液温度不高于40℃,六氟丙酮在1h内滴加完毕,继续自然反应5h得到混浊悬浮液。用10%盐酸中和,转变为透明反应液。将反应液真空蒸馏除去挥发份得到白色固体。
用100ml甲苯萃取后,用4*30ml去离子水洗涤甲苯溶液,然后加入15g无水硫酸钠干燥剂,静置过夜;过滤除去干燥剂,得甲苯溶液。将甲苯溶液中再加入38g(0.4mol)苯酚,同时加入0.5g磷酸,加热到80℃反应4h。冷却到室温后,用6*30ml去离子水洗涤甲苯反应液。将分液得到的甲苯溶液真空蒸馏除去甲苯得到含氟双酚化合物1,3-二(2-(4-羟基苯基)-六氟丙叉基)苯79g。总收率:73%。
元素分析:C,40.3%;H,3.32%;F,37.9%。IC-MS质谱分析:M+(分子量),538。GC:99%(纯度)。熔点(热台显微镜法):135℃。溶解性(良溶剂):乙醇;丙酮;四氢呋喃。
Claims (4)
1.一种含氟双酚化合物1,3-二(2-(4-羟基苯基)-六氟丙叉基)苯的制备方法,其特征在于,包含三个连续步骤:a)间二溴苯的锂化,制备间苯二锂盐;b)间苯二锂盐和六氟丙酮的加成反应,制备1,3-二(2-羟基-六氟丙叉基)苯;c)1,3-二(2-羟基-六氟丙叉基)苯与苯酚的缩合反应,制备1,3-二(2-(4-羟基苯基)-六氟丙叉基)苯。
2.根据权利要求1所述的一种含氟双酚化合物1,3-二(2-(4-羟基苯基)-六氟丙叉基)苯的制备方法,其特征在于,步骤a)中的间二溴苯的锂化,在四氢呋喃、***和甲苯-三乙胺的一种或混合溶剂中进行;间二溴苯和金属锂的摩尔配比控制在(2~3):1;锂化反应在氮气保护的无水无氧条件下进行;锂化反应的温度40~80℃,反应时间3-12h。
3.根据权利要求1所述的一种含氟双酚化合物1,3-二(2-(4-羟基苯基)-六氟丙叉基)苯的制备方法,其特征在于,步骤b)中的间苯二锂盐和六氟丙酮的加成反应,是将六氟丙酮滴加到a)步骤得到的间苯二锂盐溶液中,滴加速度控制在使反应温度<40℃,反应时间1-10h。
4.根据权利要求1所述的一种含氟双酚化合物1,3-二(2-(4-羟基苯基)-六氟丙叉基)苯的制备方法,其特征在于,步骤c)中的1,3-二(2-羟基-六氟丙叉基)苯与苯酚的缩合反应,溶剂是甲苯、四氢呋喃和***中的一种或混合物;反应在酸性催化剂作用下进行,酸性催化剂是硫酸、盐酸、磷酸、对甲苯磺酸、磷钨酸和酸性蒙脱土的一种或混合物,用量是苯酚质量的0.5~3%;缩合反应温度40-100℃,反应时间3-10h。
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