CN106117019B - 一种水溶液中制备联萘酚衍生物的方法 - Google Patents
一种水溶液中制备联萘酚衍生物的方法 Download PDFInfo
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- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims abstract description 16
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims abstract description 16
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 5
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- 229910052794 bromium Inorganic materials 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
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- 238000001514 detection method Methods 0.000 description 3
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- 125000000325 methylidene group Chemical class [H]C([H])=* 0.000 description 3
- LBQAJLBSGOBDQF-UHFFFAOYSA-N nitro azanylidynemethanesulfonate Chemical group [O-][N+](=O)OS(=O)(=O)C#N LBQAJLBSGOBDQF-UHFFFAOYSA-N 0.000 description 3
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- 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
- C07C37/20—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 using aldehydes or ketones
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- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
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Abstract
本发明属于有机合成化学的技术领域,涉及一种水溶液中制备联萘酚衍生物的方法。本发明公开了一种在水溶液中,氢溴酸(溴化氢)催化萘酚和醛类的傅‑克反应,高效合成联萘酚衍生物的方法,该方法使用清洁无污染的水取代了有机溶剂,大大节约了制备工艺成本,且反应条件温和,原子利用率高,生产工艺简单,易于工业化,在有机合成领域有着广泛的应用前景。
Description
技术领域
本发明属于绿色化学合成技术领域,涉及一种水溶液中简单高效制备联萘酚衍生物的方法。
背景技术
1987年联合国率先提出可持续发展概念,而绿色化学是实现可持续发展理论的关键。近年来,绿色化学在学术和工业方面都得到了广泛地关注。
“绿色化学”的概念始于上世纪90年代,由美国化学会ACS提出,又称可持续化学或环境友好化学。其核心是“原子经济性”即反应物的原子全部转化为期望的最终产物,利用化学原理尽量减少和消除工业生产危害。(Can M C.J Chem Educ,1999,76(12),1639-1641)随着绿色化学这一概念深入研究,Paul Anastas和John warner首次提出绿色化学12项原则(Tang S L Y,Smith R L,Poliakoff M.Green Chem,2005,7(11),761-762)。其中安全溶剂和反应条件、催化剂的使用是这12项原则中最为关键的两项。实现绿色合成的关键在于选择可供替代的反应介质和反应条件,进而实现设计新的绿色化学过程。因而,安全环保溶剂或无溶剂体系的设计成为绿色化学活跃的研究领域。尽管有机溶剂在化学工业生产中长期受到青睐,但其易挥发、易燃易爆、有毒,容易致癌。溶剂水具有廉价、安全无毒、经济环保、独特反应特性的优势,近年来,在有机反应中引起了广泛地研究兴趣,从而使其成为一种绿色溶剂。近几十年来,经济环保类型的傅克反应得到了广泛关注,并发展了一系列操作简单、易得的合成方法。尤其是催化剂量的金属盐或温和酸催化芳烃和醛或醇的反应。最近,刘教授课题组提出了一种氢溴酸(溴化氢)在溶剂乙腈中催化芳烃的傅-克反应策略,发现HBr是一种催化C-C键成键的独特新颖催化剂,并且此反应高效温和(a)H.Yuan,M.Wang,et al.Chem.Eur.2010,16,13450-13457;b)C .Xu ,M.Wang ,et al.RSC Adv.2014,4,1559-1562)。然而,溶剂乙腈对环境和人体健康的危害制约了该方法在工业上的应用。迄今为止,还没文献报道水溶液中氢溴酸催化C-C键偶联,制备联萘酚衍生物的方法。本发明公开一种水溶液中氢溴酸催化芳烃与醛的绿色傅克反应,及高效制备联萘酚衍生物的合成策略。该方法特点是反应在绿色溶剂水中进行,无需加入任何有机溶剂;解决了纯水溶剂中非水溶性底物反应困难的问题;并且直接通过过滤实现了产物与溶剂、催化剂的分离回收与重复使用。
发明内容
本发明针对现有技术存在的缺陷,提供了一种水溶液中氢溴酸催化芳烃和醛类的傅克反应,及制备联萘酚衍生物的绿色合成方法。该方法反应条件温和、产率高、操作简单、且经过简单的后处理即可得到产物。
本发明所使用的材料如下:
其中,R1、R3为氢原子;各种C1-C6烃基;连有硝基、氰基、磺酸基、羧基、C1-C4烃基的烷氧基、及C1-C4烃基的烷氧基取代的亚甲基;苄基;可拓展。
其中,R2分别为氢原子;各种C1-C6烃基;连有硝基、氰基、磺酸基、羧基、C1-C4烃基的烷氧基、及C1-C4烃基的烷氧基取代的亚甲基;苄基;苯环上连有氟、氯、溴、碘、硝基、氰基、磺酸基、羧基、C1-C4烃基、及C1-C4烃基的烷氧羰基取代的苄基;苯基;可拓展。
其中,R4为氢原子;各种C1-C6烃基;连有硝基、氰基、磺酸基、羧基、C1-C4烃基的烷氧羰基、及C1-C4烃基的烷氧基取代的亚甲基;苄基;苯环上连有氟、氯、溴、碘、硝基、氰基、磺酸基、羧基、C1-C4烃基、C1-C4烃基的烷氧羰基、及C1-C4烃基的烷氧基取代的苄基;苯基;芳环上连有氟,氯、溴、碘、硝基、氰基、磺酸基、羧基、C1-C4烃基、C1-C4烃基的烷氧羰基取代的乙烯基;乙烯基;可拓展。溶剂为水;催化剂为氢溴酸;
本发明的技术方案如下:
水溶液中氢溴酸催化的傅克反应,制备联萘酚衍生物的方法包括以下条件和步骤:
反应中溶剂为:水;
反应中催化剂为:氢溴酸、溴化氢;
向去离子水(5毫升)中加入以上提到的反应物中的一种萘酚(β-萘酚1或α-萘酚2)(2.0毫摩尔)及醛3(1.0毫摩尔)。在25-80℃的反应温度下强烈搅拌,加入催化剂氢溴酸(0.1-1.0毫摩尔)或通入溴化氢气体(连续通入)(以上数量可按比例放大)。薄层色谱检测下反应进行12-24小时。待反应完成后进行后处理分离,视不同反应得到不同类型的联萘酚衍生物。产率视不同反应在80-95%之间,详见具体实施方案中的实施例。
本发明的积极效果在于:水溶液中氢溴酸催化的傅克反应方法无需使用有毒的有机溶剂,反应介质水环境友好,反应条件温和,产率高,在有机合成化学领域具有有价值的潜在应用前景,且易于工艺化、工业化。
附图说明:
下面结合实施案例与附图对本发明进行进一步的说明:
附图为实施案例1中的反应前,反应过程中,反应结束后实验现象图。
具体实施方式
实施例1:
产物为萘酚与醛的2:1加成产物
在50毫升圆底烧瓶中,加入288毫克(2.0毫摩尔)β-萘酚,1 .0毫升1mol/L的甲醛水溶液和5.0毫升去离子水,40度强烈搅拌下,加入1.0毫升氢溴酸水溶液(浓度:0.1mol/L0.1毫摩尔),继续搅拌12小时至β-萘酚反应完全(薄层色谱TLC检测)。过滤得白色固体,用饱和碳酸水溶液和水依次洗涤,晾干,得白色固体1 ,1亚甲基2-萘酚为286毫克,产率95%;在其他条件完全相同情况下,直接通入气体溴化氢替代氢溴酸做催化剂实施反应,可得相同结果,反应见下式:
实施例2:
产物为芳烃与醛的2:1加成产物。
在50毫升圆底烧瓶中,加入288毫克(2.0毫摩尔)β-萘酚,166毫克对硝基苯甲醛和5 .0毫升去离子水。80℃强烈搅拌下,加入1.0毫升氢溴酸水溶液(浓度:0.1mol/L,0.1毫摩尔),继续搅拌12小时至β-萘酚反应完全(薄层色谱TLC检测)。过滤得白色固体,用饱和碳酸水溶液和水依次洗涤,晾干,得白色固体(4-硝基苯基)-二(2-羟基-1-萘基)甲烷365毫克,产率90%;在其他条件完全相同情况下,直接通入气体溴化氢替代氢溴酸做催化剂实施反应,可得相同结果,反应见下式:
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