CN113045413A - 一种制备单一构型的c-2位单取代降冰片烯衍生物的方法 - Google Patents
一种制备单一构型的c-2位单取代降冰片烯衍生物的方法 Download PDFInfo
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- CN113045413A CN113045413A CN202110282439.8A CN202110282439A CN113045413A CN 113045413 A CN113045413 A CN 113045413A CN 202110282439 A CN202110282439 A CN 202110282439A CN 113045413 A CN113045413 A CN 113045413A
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- FYGUSUBEMUKACF-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carboxylic acid Chemical compound C1C2C(C(=O)O)CC1C=C2 FYGUSUBEMUKACF-UHFFFAOYSA-N 0.000 claims abstract description 41
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- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
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- LUMNWCHHXDUKFI-XLPZGREQSA-N [(1s,4s,5s)-5-bicyclo[2.2.1]hept-2-enyl]methanol Chemical compound C1[C@@H]2[C@@H](CO)C[C@H]1C=C2 LUMNWCHHXDUKFI-XLPZGREQSA-N 0.000 claims description 6
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- VEIDABLYEFTWOL-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C(C=C2)CC2C1C(=O)OC1C(C=C2)CC2C1 VEIDABLYEFTWOL-UHFFFAOYSA-N 0.000 claims description 4
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- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 3
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
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- 238000005481 NMR spectroscopy Methods 0.000 description 3
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- BZBMBZJUNPMEBD-UHFFFAOYSA-N tert-butyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OC(C)(C)C)CC1C=C2 BZBMBZJUNPMEBD-UHFFFAOYSA-N 0.000 description 3
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- ZOMLSPYVIOEUOQ-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl) bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1OC(=O)C1C(C=C2)CC2C1 ZOMLSPYVIOEUOQ-UHFFFAOYSA-N 0.000 description 2
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- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 description 2
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- BMAXQTDMWYDIJX-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carbonitrile Chemical compound C1C2C(C#N)CC1C=C2 BMAXQTDMWYDIJX-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
- C07C45/292—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with chromium derivatives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
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Abstract
本发明公开了一种制备单一构型的C‑2位单取代降冰片烯衍生物的方法,该方法首先以商品化的外型/内型异构体混合的5‑降冰片烯‑2‑羧酸和大位阻一元醇为原料制备外型异构体富集的外型/内型异构体混合的5‑降冰片烯‑2‑羧酸酯,然后通过常用的柱色谱分离或分馏实现单一构型5‑降冰片烯‑2‑羧酸酯的分离,最后由分离后的单一构型5‑降冰片烯‑2‑羧酸酯制备单一构型的C‑2位单取代降冰片烯衍生物。本发明所用原料易得、制备过程简单,且可得到高纯度(大于98%)单一构型的C‑2位单取代降冰片烯衍生物。
Description
技术领域
本发明涉及的是一种制备单一构型的C-2位单取代降冰片烯衍生物的方法,更具体而言,是一种通过商品化的外型/内型异构体混合的5-降冰片烯-2-羧酸与大位阻一元醇反应制备外型/内型异构体混合的5-降冰片烯-2-羧酸酯,在该步反应中外型异构体得到富集,且外型/内型异构体混合的5-降冰片烯-2-羧酸酯可成功地通过柱色谱或分馏而实现单一构型的分离,再由分离后单一构型的5-降冰片烯-2-羧酸酯制备单一构型的C-2位单取代降冰片烯衍生物。
背景技术
降冰片烯(双环[2,2,1]庚-2-烯,Norbornene,NB)及其衍生物由于具有较高的反应活性,可通过烯烃部分的直接加成聚合或开环易位聚合(ROMP)及其与其它单体的共聚合制备功能聚合物,在工程塑料、生物材料以及光学材料等领域具有广泛的应用。C-2位单取代降冰片烯衍生物一般是由环戊二烯与乙烯基衍生物通过Diels-Alder反应(狄尔斯-阿尔德反应)制备,但是该方法制备的降冰片烯衍生物为内型(endo)和外型(exo)异构体的混合物,且由于过渡态的位阻效应以及次级HOMO-LUMO轨道相互作用的影响,所得产物以内型为主。由C-2位单取代降冰片烯衍生物外型和内型异构体的立体结构差异,使聚合反应活性和得到的聚合物的性质不同。与内型异构体相比,外型异构体一般表现出较快的反应速率,且受极性基团的影响小,所得聚合物分子量高。
但是,到目前为止,在商品化的降冰片烯单取代衍生物中,仅有外-5-降冰片烯羧酸((1R,2S,4R)-二环[2.2.1]庚-5-烯-2-羧酸)是单一外型结构,其余均为内型占优(一般70%以上)的内型和外型异构体的混合物,如5-降冰片烯-2-羧酸、5-降冰片烯-2-甲醇和5-降冰片烯-2-甲胺等。
专利申请CN 101918342 A公开了一种基本上纯的外型5/6-取代的降冰片烯型单体的制备方法,该方法通过环戊二烯与丙烯腈反应生成5-降冰片烯甲腈,然后对其蒸馏以分离出外型和内型异构体,再由分离获得的外型-5-降冰片烯甲腈衍生化的外型-5-降冰片烯甲醛,再进一步反应得到外型-5-降冰片烯甲酸和外型-5-降冰片烯甲醇等。该方法的不足之处在于:步骤繁杂且只能获得基本上纯的外型异构体(纯度≥95%),并未报道获得高纯度的外型异构体。
发明内容
针对现有技术的不足,本发明提供了一种制备高纯度的单一构型(可以为外型或内型)的C-2位单取代降冰片烯衍生物的方法,解决现有的外型异构体制备困难或分离条件困难等技术问题。
本发明为实现发明目的,采用如下技术方案:
一种制备单一构型的C-2位单取代降冰片烯衍生物的方法,其特点在于:以已有商品化的外型/内型异构体混合的5-降冰片烯-2-羧酸和大位阻一元醇为起始原料,通过酯化反应制备外型/内型异构体混合的5-降冰片烯-2-羧酸酯;然后通过柱色谱分离或者分馏的方法,分离得到单一构型的5-降冰片烯-2-羧酸酯,包括高纯度的外型-5-降冰片烯-2-羧酸酯和高纯度的内型-5-降冰片烯-2-羧酸酯;再由单一构型的5-降冰片烯-2-羧酸酯制备单一构型的C-2位单取代降冰片烯衍生物。
进一步地,通过外型/内型异构体混合的5-降冰片烯-2-羧酸和大位阻一元醇发生酯化反应的方程式如式(1)所示,反应是在催化剂和脱水剂的作用下进行,反应温度在0℃~100℃之间;
进一步地:所述大位阻一元醇的结构通式如式(2)所示:
其中,R1、R2、R3分别独立地选自含碳原子数为1~20的烃基,非限制性的实例为烷基、环烷基、芳基、芳烷基、烷芳基和烯基;另外,烃基可包含一个或多个杂原子,如N,O,S和Si。
进一步地,本发明的方法适用于目前各种已有商品化的外型/内型异构体,不局限其中外型与内型异构体的摩尔比例。但是目前已有商品化的外型/内型异构体混合的5-降冰片烯-2-羧酸多为内型异构体占优的混合物,其所含内型异构体的摩尔百分含量大多不低于70%。
进一步地,通过酯化反应制备的外型/内型异构体混合的5-降冰片烯-2-羧酸酯中外型异构体的含量高于起始原料外型/内型异构体混合的5-降冰片烯-2-羧酸中外型异构体的含量,即,外型异构体的含量通过酯化反应得到了富集。
进一步地,所述的脱水剂包括但不限于N,N'-二环己基化碳二亚胺(DCC)、N,N'-二异丙基碳二酰亚胺(DIC)、1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐(EDC)、2-(7-偶氮苯并三氮唑)-N,N,N',N'-四甲基脲六氟磷酸酯(HATU)、1H-苯并三唑-1-基氧三吡咯烷基鏻六氟磷酸盐(Pybop)、偶氮二甲酸二异丙酯(DIAD)和偶氮二甲酸二乙酯(DEAD)中的至少一种;所述的催化剂包括但不限于4-二甲氨基吡啶(DMAP)、N-羟基琥珀酰亚胺(NHS)、三乙基苄基氯化铵(TEBAC)、吡啶(Py)和三苯基膦(TPP)中的至少一种。
进一步地,所述柱色谱分离方法中,柱色谱填料优选自硅胶、氧化铝等,洗脱剂包括但不限于环己烷、环戊烷、正己烷、石油醚、二氯甲烷、三氯甲烷、丙酮、乙酸乙酯、甲苯和二甲苯中的至少一种。
进一步地,所述高纯度是指所得产物中相应单一构型异构体的摩尔百分含量不低于98%。
进一步地,所述单一构型的C-2位单取代降冰片烯衍生物包括但不限于外型或内型-5-降冰片烯-2-羧酸、外型或内型-5-降冰片烯-2-甲醇、外型或内型-5-降冰片烯-2-甲醛、外型或内型-5-降冰片烯-2-甲醇乙酸酯、外型或内型-5-降冰片烯-2-羧酸的甲酯等。
与已有技术相比,本发明的有益效果体现在:
本发明所用原料易得、制备过程简单,实现了降冰片烯衍生物的内型/外型异构化,外型异构体的含量通过酯化反应得到了富集,最终可得到高纯度单一构型的C-2位单取代降冰片烯衍生物(纯度﹥98%)。
附图说明
图1为本发明制备单一构型的C-2位单取代降冰片烯衍生物的工艺示意图;
图2为实施例1所使用的外型/内型异构体混合的5-降冰片烯-2-羧酸的1HNMR谱图(溶剂:氘代氯仿);
图3为实施例1所制备的外型/内型异构体混合的5-降冰片烯-2-羧酸特丁酯的1HNMR谱图(溶剂:氘代氯仿);
图4为实施例4所制备的外型-5-降冰片烯-2-羧酸的1HNMR谱图(溶剂:氘代氯仿);
图5为实施例5所制备的内型-5-降冰片烯-2-羧酸的1HNMR谱图(溶剂:氘代氯仿)。
具体实施方式
下面对本发明的实施例作具体说明,本实施例在以本发明技术方案为前提下进行实施,给出了信息的实施方式和具体的操作过程,但本发明的保护范围不限于下述实施实例。
实施例1、外型/内型-5-降冰片烯-2-羧酸特丁酯的制备与分离
在装有磁子的100mL单口烧瓶中加入外型/内型异构体混合的5-降冰片烯-2-羧酸(5.0g,36.2mmol,其1H NMR谱图表明其外型/内型异构体摩尔比约为19:81)。接着加入5mL叔丁醇(4.0g,54.3mmol)和4-二甲氨基吡啶(0.4g,3.6mmol),用20mL二氯甲烷将上述体系溶解,随后向体系中加入15mL二氯甲烷溶解的1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐(8.4g,54.3mmol),室温下搅拌36h。反应完成后,通过萃取对产物进行处理,获得外型/内型异构体混合的5-降冰片烯-2羧酸特丁酯(NMR结果表明其外型/内型异构体比例提高至44:56)。而后,将外型/内型异构体混合的5-降冰片烯-2-羧酸特丁酯以硅胶粉为填料、乙酸乙酯和石油醚的混合溶液为洗脱剂,进行柱色谱分离,分离得到纯度皆在98%以上的外型-5-降冰片烯-2-羧酸特丁酯及内型-5-降冰片烯-2-羧酸特丁酯。
实施例2、外型/内型-5-降冰片烯-2-羧酸异丙酯的制备与分离
在装有磁子的100mL单口烧瓶中加入外型/内型异构体混合的5-降冰片烯-2-羧酸(5.0g,36.2mmol,其1HNMR谱图表明其外型/内型摩尔比约为20:80)。接着加入4mL异丙醇(3.3g,54.3mmol)和N-羟基琥珀酰亚胺(0.4g,3.6mmol),用18mL二氯甲烷将上述体系溶解,随后向体系中加入15mL二氯甲烷溶解的N,N'-二环己基化碳二亚胺(11.2g,54.3mmol),室温下搅拌36h。反应完成后,通过萃取对产物进行处理,获得外型/内型异构体混合的5-降冰片烯-2-羧酸异丙酯(NMR结果表明其外型/内型异构体比例提高至49:51)。而后,将外型/内型异构体混合的5-降冰片烯-2-羧酸异丙酯以分馏的方式分离提纯,得到纯度皆在98%以上的外型-5-降冰片烯-2-羧酸异丙酯及内型-5-降冰片烯-2-羧酸异丙酯。
实施例3、外型/内型-5-降冰片烯-2-羧酸五氟苯酯的制备
在装有磁子的150mL单口烧瓶中加入外型/内型异构体混合的5-降冰片烯-2-羧酸(5.0g,36.2mmol,其1H NMR谱图表明其外型/内型比例约为23:77)。接着加入五氟苯酚(10.0g,54.3mmol)和4-二甲氨基吡啶(0.4g,3.6mmol),用30mL二氯甲烷将上述体系溶解,随后向体系中加入15mL二氯甲烷溶解的1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐(8.4g,54.3mmol),室温下搅拌48h。反应完成后,通过萃取对产物进行处理,获得外型/内型异构体混合的5-降冰片烯-2-羧酸五氟苯酯(NMR结果表明其外型/内型异构体比例提高至57:43)。而后,将外型/内型异构体混合的5-降冰片烯-2-羧酸五氟苯酯以硅胶粉为填料、二氯甲烷和石油醚的混合溶液为洗脱剂,进行柱色谱分离,分离得到纯度皆在98%以上的外型-5-降冰片烯-2-羧酸五氟苯酯及内型-5-降冰片烯-2-羧酸五氟苯酯。
实施例4、外型-5-降冰片烯-2-羧酸的制备
在装有磁子的100mL单口烧瓶中加入外型-5-降冰片烯-2-羧酸特丁酯(2.0g,10.3mmol),接着加入21mL二氯甲烷,然后在恒压漏斗中加入10mL三氟乙酸(15.3g,133.8mmol)并缓慢滴入体系中,室温下酸解2h。除去体系中的溶剂,用乙醚处理残渣,过滤分离沉淀产物,产物经洗涤、真空干燥,最终得到外型-5-降冰片烯-2-羧酸固体(1.4g,收率:98%),图4显示该物质的1H NMR谱图。
实施例5、内型-5-降冰片烯-2-羧酸的制备
在装有磁子的100mL单口烧瓶中加入内型-5-降冰片烯-2-羧酸特丁酯(2.0g,10.3mmol),接着加入21mL二氯甲烷,然后在恒压漏斗中加入10mL三氟乙酸(15.3g,133.8mmol)并缓慢滴入体系中,室温下酸解2.5h。除去体系中的溶剂,用乙醚处理残渣,过滤分离沉淀产物,产物经洗涤、真空干燥,最终得到内型-5-降冰片烯-2-羧酸固体(1.4g,收率:98%),图5显示该物质的1H NMR谱图。
实施例6、外型-5-降冰片烯-2-羧酸甲酯的制备
在装有磁子的100mL单口烧瓶中加入外型-5-降冰片烯-2-羧酸(5.0g,36.2mmol),接着将15mL甲醇(11.6g,362.0mmol)及6mL二氯甲烷加入至单口烧瓶中,开启搅拌并逐滴滴入0.6mL浓硫酸作为反应的催化剂。投料完成后,在单口烧瓶上装配一球形冷凝管,冷凝管顶部以气球密封,通冷凝水,在70℃油浴下反应回流12h。酯化完成后,加入适量二氯甲烷稀释,依次以去离子水、饱和食盐水进行萃取,以无水硫酸钠干燥,将体系溶剂旋干。而后,以乙酸乙酯和石油醚混合溶剂为洗脱剂,进行柱色谱分离,除去体系中残余的羧酸及其他杂质,最终得到外型-5-降冰片烯-2-羧酸甲酯(5.1g,收率:93%)。
实施例7、内型-5-降冰片烯-2-羧酸乙酯的制备
在装有磁子的100mL单口烧瓶中加入内型-5-降冰片烯-2-羧酸(5.0g,36.2mmol),接着将21mL乙醇(16.7g,362.0mmol)及6mL二氯甲烷加入至单口烧瓶中,开启搅拌并逐滴滴入0.6mL浓硫酸作为反应的催化剂。投料完成后,在单口烧瓶上装配一球形冷凝管,冷凝管顶部以气球密封,通冷凝水,在80℃油浴下反应回流14h。酯化完成后,加入适量二氯甲烷稀释,依次以去离子水、饱和食盐水进行萃取,以无水硫酸钠干燥,将体系溶剂旋干。而后,以乙酸乙酯和石油醚混合溶剂为洗脱剂,进行柱色谱分离,除去体系中残余的羧酸及其他杂质,最终得到内型-5-降冰片烯-2-羧酸乙酯(5.5g,收率:91%)。
实施例8、外型-5-降冰片烯-2-甲醇的制备
在25mL单口烧瓶加入四氢化铝锂(2.5g,65.8mmol)并以橡胶塞封口后置于冰水浴中,用注射器注入20mL干燥的四氢呋喃将其溶解备用。而后,在装有磁子的300mL单口烧瓶中加入外型-5-降冰片烯-2-羧酸甲酯(5.0g,32.9mmol)及70mL四氢呋喃,以橡胶塞封口后,在氮气保护下置于冰水浴中。在冰浴条件下向体系中加入预先准备的四氢化铝锂,加入完毕后撤去冰水浴,室温下反应24h。反应完成后,将烧瓶置于冰水浴中,用饱和氯化铵溶液将残余的四氢化铝锂淬灭,得到粘稠状乳液,以二氯甲烷溶解乳液,搅拌1h后用布氏漏斗抽滤,以二氯甲烷反复清洗滤饼2-3次,将所得滤液浓缩,以乙酸乙酯稀释,用饱和食盐水萃取1-2次,以无水硫酸钠干燥,过滤后将体系溶剂去除。最后,以二氯甲烷和石油醚混合溶剂为洗脱剂,进行柱色谱分离,除去体系中残余的杂质,最终得到外型-5-降冰片烯-2-甲醇(3.7g,收率:91%)。
实施例9、内型-5-降冰片烯-2-甲醇的制备
在25mL单口烧瓶加入四氢化铝锂(2.5g,65.8mmol)并以橡胶塞封口后置于冰水浴中,用注射器注入20mL干燥的四氢呋喃将其溶解备用。而后,在装有磁子的300mL单口烧瓶中加入内型-5-降冰片烯-2-羧酸甲酯(5.0g,32.9mmol)及70mL重蒸四氢呋喃,以橡胶塞封口后,在氮气保护下置于冰水浴中。在冰浴条件下向体系中加入预先准备的四氢化铝锂,加入完毕后撤去冰水浴,室温下反应24h。反应完成后,将烧瓶置于冰水浴中,用饱和氯化铵溶液将残余的四氢化铝锂淬灭,得到粘稠状乳液,以二氯甲烷溶解乳液,搅拌1h后用布氏漏斗抽滤,以二氯甲烷反复清洗滤饼2-3次,将所得滤液浓缩,以乙酸乙酯稀释,用饱和食盐水萃取1-2次,以无水硫酸钠干燥,过滤后将体系溶剂去除。最后,以二氯甲烷和石油醚混合溶剂为洗脱剂,进行柱色谱分离,除去体系中残余的杂质,最终得到内型-5-降冰片烯-2-甲醇(3.5g,收率:86%)。
实施例10、外型-5-降冰片烯-2-甲醛的制备
在装有磁子的150mL单口烧瓶中加入30mL二氯甲烷,在氮气气氛下降温至-78℃备用,依次将外型-5-降冰片烯-2-甲酯(2.0g,13.1mol)溶于20mL干燥的二氯甲烷溶液,将二异丁基氢化铝(3.7g,26.2mmol)溶解于6mL干燥的甲苯中,而后将二者缓慢滴入单口烧瓶中,于-78℃下反应3h。反应完成后,向体系内加入30mL四氢呋喃和水的混合溶液(1:1),升至室温。以70mL二氯甲烷稀释,过滤,以无水硫酸钠干燥,过滤后将体系溶剂旋干。最后,以石油醚和二氯甲烷混合溶剂为洗脱剂,进行柱色谱分离,除去体系中残余的杂质,最终得到外型-5-降冰片烯-2-甲醛(1.4g,收率:87%)。
实施例11、内型-5-降冰片烯-2-甲醛的制备
在装有磁子的100mL单口烧瓶中加入内型-5-降冰片烯-2-甲醇(2.0g,16.1mol)及15mL干燥的二氯甲烷溶液,将氯铬酸吡啶嗡盐(5.2g,24.2mmol)溶解于25mL二氯甲烷中,完全溶解后将其滴入单口烧瓶内,可加入适量醋酸钠以调节体系的酸碱度,室温下反应3h。反应完成后,所得混合物以100mL乙醚稀释,过滤,所得固体用乙醚洗涤2-3次,所得滤液依次以去离子水、饱和食盐水萃取,以无水硫酸钠干燥,过滤后将体系溶剂旋干。最后,以石油醚和乙酸乙酯混合溶剂为洗脱剂,进行柱色谱分离,除去体系中残余的杂质,最终得到内型-5-降冰片烯-2-甲醛(1.6g,收率:81%)。
以上仅为本发明的示例性实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所做的任何修改,等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (7)
1.一种制备单一构型的C-2位单取代降冰片烯衍生物的方法,其特征在于:以已有商品化的外型/内型异构体混合的5-降冰片烯-2-羧酸和大位阻一元醇为起始原料,通过酯化反应制备外型/内型异构体混合的5-降冰片烯-2-羧酸酯;然后通过柱色谱分离或者分馏的方法,分离得到单一构型的5-降冰片烯-2-羧酸酯,包括高纯度的外型-5-降冰片烯-2-羧酸酯和高纯度的内型-5-降冰片烯-2-羧酸酯;再由单一构型的5-降冰片烯-2-羧酸酯制备单一构型的C-2位单取代降冰片烯衍生物。
4.根据权利要求1或2所述的制备单一构型的C-2位单取代降冰片烯衍生物的方法,其特征在于:通过酯化反应制备的外型/内型异构体混合的5-降冰片烯-2-羧酸酯中外型异构体的含量高于起始原料外型/内型异构体混合的5-降冰片烯-2-羧酸中外型异构体的含量,即,外型异构体的含量通过酯化反应得到了富集。
5.根据权利要求2所述的制备单一构型的C-2位单取代降冰片烯衍生物的方法,其特征在于:所述的脱水剂包括N,N'-二环己基化碳二亚胺、N,N'-二异丙基碳二酰亚胺、1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐、2-(7-偶氮苯并三氮唑)-N,N,N',N'-四甲基脲六氟磷酸酯、1H-苯并三唑-1-基氧三吡咯烷基鏻六氟磷酸盐、偶氮二甲酸二异丙酯和偶氮二甲酸二乙酯中的至少一种;所述的催化剂包括4-二甲氨基吡啶、N-羟基琥珀酰亚胺、三乙基苄基氯化铵、吡啶和三苯基膦中的至少一种。
6.根据权利要求1所述的制备单一构型的C-2位单取代降冰片烯衍生物的方法,其特征在于:所述高纯度是指所得产物中相应单一构型异构体的摩尔百分含量不低于98%。
7.根据权利要求1所述的制备单一构型的C-2位单取代降冰片烯衍生物的方法,其特征在于:所述单一构型的C-2位单取代降冰片烯衍生物包括外型或内型-5-降冰片烯-2-羧酸、外型或内型-5-降冰片烯-2-甲醇、外型或内型-5-降冰片烯-2-甲醛、外型或内型-5-降冰片烯-2-甲醇乙酸酯、外型或内型-5-降冰片烯-2-羧酸的甲酯。
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020055649A1 (en) * | 2000-08-22 | 2002-05-09 | Sachiko Miyagi | Method for producing carboxylic acid tertiary alkyl ester |
CN101291961A (zh) * | 2005-10-17 | 2008-10-22 | Lg化学株式会社 | 使用催化剂的聚合方法 |
-
2021
- 2021-03-16 CN CN202110282439.8A patent/CN113045413A/zh active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020055649A1 (en) * | 2000-08-22 | 2002-05-09 | Sachiko Miyagi | Method for producing carboxylic acid tertiary alkyl ester |
CN101291961A (zh) * | 2005-10-17 | 2008-10-22 | Lg化学株式会社 | 使用催化剂的聚合方法 |
Non-Patent Citations (5)
Title |
---|
HAROLD WIENER等: "AN IMPROVED METHOD FOR THE CATALYTIC PREPARATION OF t-BUTYL ESTERS OF CARBOXYLIC AND FATTY ACIDS", 《JOURNAL OF MOLECULAR CATALYSIS》 * |
JEROME A. BERSON等: "Resolution, stereochemical correlation, and maximum rotations of the norbornane- and 5-norbornene-2-carboxylic acids. Isotope dilution as an aid in the determination of optical purity", 《J. AM. CHEM. SOC.》 * |
NICOLAS VOGEL等: "Controlled synthesis of reactive polymeric architectures using 5-norbornene-2-carboxylic acid pentafluorophenyl ester", 《MACROMOLECULAR SYMPOSIA》 * |
NILESH JAIN等: "Roof shape chiral alcohol: auxiliary for asymmetric synthesis of a-halo acid derivatives", 《TETRAHEDRON LETTERS》 * |
PALLAB KUMAR BORAH等: "Effects of folic acid esterification on the hierarchical structure of amylopectin corn starch", 《FOOD HYDROCOLLOIDS》 * |
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