WO2020041927A2 - 一种环状酯类化合物的合成方法 - Google Patents

一种环状酯类化合物的合成方法 Download PDF

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WO2020041927A2
WO2020041927A2 PCT/CN2018/102486 CN2018102486W WO2020041927A2 WO 2020041927 A2 WO2020041927 A2 WO 2020041927A2 CN 2018102486 W CN2018102486 W CN 2018102486W WO 2020041927 A2 WO2020041927 A2 WO 2020041927A2
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cyclic
compound
reaction
synthesis method
anhydride
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PCT/CN2018/102486
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French (fr)
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李志勇
易宗明
赵峰
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湖南阿斯达新材料有限公司
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Priority to PCT/CN2018/102486 priority Critical patent/WO2020041927A2/zh
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
    • C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
    • C07D319/12—1,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms

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  • the invention relates to a method for synthesizing a cyclic ester compound.
  • cyclic ester compounds such as methylene malonate, ethylene glycol diacetate, methylene ethanedisulfonate, methylene methanedisulfonate and the like has become more and more widely used.
  • the above-mentioned monomeric cyclic esters are most commonly prepared by the esterification reaction of a diacid and a diol.
  • this esterification reaction has a narrow preparation path and post-treatment. It is complicated and has a lot of process waste, which affects the yield of the target product.
  • cyclic esters can also be prepared by condensing a hydroxyl group into an oligomeric prepolymer, and then depolymerizing the prepolymer into a cyclic ester.
  • the cyclic ester preparation method of this reaction mechanism also has the defect of incomplete reaction and a lot of process wastes, which is not suitable for industrial large-scale production.
  • the object of the present invention is to provide a new method for preparing cyclic ester compounds with more reasonable process design, complete reaction and high yield.
  • the technical solution of the present invention is to provide a method for synthesizing a cyclic ester compound, which is directly synthesized from a cyclic acid anhydride compound and a cyclic ether compound as reactants.
  • the cyclic ester compound is a cyclic sulfonic acid ester compound or a cyclic carboxylic acid ester compound.
  • the cyclic sulfonic acid ester compound is obtained by reacting a cyclic sulfonic acid anhydride compound with a cyclic ether compound.
  • the sulfur-oxygen single bond in the sulfonic acid group in the cyclic sulfonic anhydride compound is cleaved, which causes the cyclic sulfonic anhydride compound to open the ring, and the carbon-oxygen single bond in the ether group in the cyclic ether compound is cleaved.
  • the cyclic ether compounds are ring-opened; after the ring-opening, a ring-closing reaction is performed to obtain cyclic sulfonate compounds.
  • the cyclic carboxylic acid ester compound is obtained by reacting a cyclic carboxylic acid anhydride compound with a cyclic ether compound.
  • the carbon-oxygen single bond in the carboxylic acid group in the cyclic carboxylic acid anhydride compound is cleaved, and the cyclic carboxylic acid anhydride compound is ring-opened, and the carbon-oxygen single bond in the ether group in the cyclic ether compound is cleaved.
  • the cyclic ether compound is ring-opened; after the ring-opening, the ring-closure reaction is performed to obtain a cyclic carboxylic acid ester compound.
  • the structural formula of the cyclic sulfonate compound is:
  • the structural formula of the cyclic carboxylic acid ester compound is:
  • n is an integer of 0-4, and x is an integer of 1-4;
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from a hydrogen atom, a halogen atom, a C1-C4 alkyl group, or a C1-C4 haloalkyl group.
  • the structural formula of the cyclic sulfonic anhydride compound is The structural formula of cyclic carboxylic anhydride compounds is
  • m C atoms are directly ringed with two sulfonic acid group S and one O atom, R 1 and R 2 are substituents on C.
  • m is an integer greater than 1, That is, there are multiple carbon atoms participating in the ring formation, and R 1 on each carbon atom may be the same or different; similarly, R 2 on each carbon atom may be the same or different.
  • n C atoms are directly cyclized with two carboxyl C atoms and one O atom.
  • R 3 and R 4 are substituents on C.
  • n is an integer greater than 1
  • m is an integer of 1-4
  • n is an integer of 0-4
  • R 1 , R 2 , R 3 , and R 4 are each independently selected from a hydrogen atom, a halogen atom, a C1-C4 alkyl group, or a C1- C4 haloalkyl.
  • C1-C4 represents 1-4 carbon atoms.
  • n 0 or 1.
  • R 1 , R 2 , R 3 , and R 4 are each independently selected from a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, or an n-propyl group.
  • the molecular formula of the cyclic ether compound is [(CR 5 R 6 ) x O] y ; in the formula, x ⁇ y C atoms and y O atoms form a ring, R 5 and R 6 Is a substituent on C.
  • x or y is greater than 1, there are multiple carbon atoms participating in the ring formation, and R 5 on each carbon atom may be the same or different; similarly, the R 6 may be the same or different. Since at least 3 atoms are required to form a ring, x and y cannot be 1 at the same time.
  • x is an integer of 1-4
  • y is an integer of 1-4
  • R 5 and R 6 are each independently selected from a hydrogen atom, a halogen atom, a C1-C4 alkyl group, or a C1-C4 haloalkyl group.
  • the steric hindrance of the reaction will increase, which will affect the reaction, effectively improve the yield, and the reaction conditions are mild.
  • the cyclic acid anhydride compound is oxalic anhydride, 1,3-malonic anhydride, methyldisulfonic anhydride or 1,2-ethanedisulfonic anhydride.
  • the cyclic ether compound is ethylene oxide or trioxane.
  • the cyclic ester compound is:
  • the molar ratio of the cyclic acid anhydride compound and the cyclic ether compound is 2: 1 to 1: 2.
  • the molar ratio of the cyclic acid anhydride compound and the cyclic ether compound is 1: 1 to 1: 2.
  • the molar ratio of the cyclic acid anhydride compound and the cyclic ether compound is 1: 1.1 to 1: 1.2.
  • the reaction temperature is from 0 to 200 ° C, and the reaction time is from 0.5 to 24 hours.
  • the reaction temperature is 50 to 150 ° C. and the reaction time is 1 to 10 h.
  • the reaction temperature is 50 to 100 ° C, and the reaction time is 3 to 8 hours.
  • the reaction is performed without adding a reaction solvent.
  • a reaction solvent is added to carry out the reaction.
  • the reaction solvent is not limited, and the solvent inert to the reaction may be selected from benzenes, halogenated hydrocarbons, sulfones, and the like, such as dichloromethane, 1,2-dichloroethane, One or more of 1,3-dichloropropane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, hexane, heptane, hexane, dimethylsulfoxide and sulfolane.
  • pure product is obtained after recrystallization after the reaction.
  • the solubility of the reaction product is significantly different from the solubility of the reactants, and effective separation can be achieved by recrystallization.
  • Benzene, halogenated hydrocarbon, sulfone, ether, ketone solvents can be selected to dissolve the target compound. Specifically, such as methylene chloride, 1,2-dichloroethane, 1,3-dichloropropane can be selected. , Benzyl toluene, chloroform, ether, tetrahydrofuran, dimethyl sulfoxide, acetone and methyl ethyl ketone.
  • the present invention uses a cyclic acid anhydride and a cyclic ether to perform a direct ring-opening reaction, which widens the preparation route of a cyclic ester and has great significance in the field of cyclic ester preparation.
  • the present invention selects raw materials more directly, and only requires two kinds of raw materials to react, which effectively reduces the introduction of raw material impurities and the production of intermediate impurity products, greatly improves the yield of the target product, and has simple post-processing and three wastes. less.
  • reaction conditions are milder and the environment is friendlier, and large-scale industrial large-scale production can be achieved.
  • the present invention finds the most direct and appropriate preparation method for the preparation of cyclic esters, reduces the production cost of the enterprise and increases the profit of the enterprise.
  • the present invention overcomes technical prejudice, that is, those skilled in the art generally believe that the preparation of cyclic esters requires a solvent, and the present invention can be implemented with or without a solvent.
  • the oxalic anhydride of this embodiment may be purchased, or it may be directly used without isolation after in-situ synthesis (in-situ synthesis).
  • the 1,3-malonic anhydride in this embodiment may be purchased, or it may be directly used after being synthesized without isolation (in-situ synthesis).
  • the methyl disulfonic anhydride of this embodiment may be purchased, or it may be directly used after being synthesized without isolation (in-situ synthesis).
  • the 1,2-ethanedisulfonic anhydride of this embodiment may be purchased, or it may be used directly after being synthesized without isolation (in-situ synthesis).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Description

一种环状酯类化合物的合成方法 技术领域
本发明涉及一种环状酯类化合物的合成方法。
背景技术
近年来，环状酯类化合物，如丙二酸亚甲酯、乙二酸乙二酯、乙烷二磺酸亚甲酯、甲烷二磺酸亚甲酯等的用途越来越广泛。上述这类单体环状酯，不管是从学术上还是实际生产中，最常用的是采用二酸和二醇酯化反应而制得，然而这种酯化反应，制备途径较为狭窄，后处理复杂，工艺废物多，影响目标产物的收率。
现有技术中，环状酯还可以通过如下途径制备：将羟基缩合为低聚的预聚物，然后将预聚物解聚合成环状酯。这种反应机理的环状酯制备方法，也存在反应不完全而导致工艺废物很多的缺陷，不适用于工业化大生产。
为此，开发出一种新的合成前述环状酯类化合物的方法，以扩宽环状酯的制备途径，并提高其得率，非常有必要，这将会在环状酯的制备途径领域中有着重大意义。
发明内容
针对上述现有技术存在的不足，本发明的目的是提供一种工艺设计更为合理且反应完全、收率高的制备环状酯类化合物的新方法。
本发明的技术方案是，提供一种环状酯类化合物的合成方法，所述环状酯类化合物是由环状酸酐类化合物和环状醚类化合物作为反应物直接合成。
优选地，所述环状酯类化合物为环状磺酸酯类化合物或环状羧酸酯类化合物。
优选地，环状磺酸酯类化合物由环状磺酸酐类化合物与环状醚类化合物反应得到。反应过程中，环状磺酸酐类化合物中的磺酸基中的硫氧单键断裂，使环状磺酸酐类化合物开环，环状醚类化合物中的醚基中的碳氧单键断裂使环状醚类化合物开环；开环后再进行闭环反应，得到环状磺酸酯类化合物。
优选地，环状羧酸酯类化合物由环状羧酸酐类化合物与环状醚类化合物反应得到。反应过程中，环状羧酸酐类化合物中的羧酸基中的碳氧单键断裂，使环状羧酸酐类化合物开环，环状醚类化合物中的醚基中的碳氧单键断裂使环状醚类化合物开环；开环后再进行闭环反应，得到环状羧酸酯类化合物。
优选地，所述环状磺酸酯类化合物的结构通式为：
Figure PCTCN2018102486-appb-000001
优选地，所述环状羧酸酯类化合物的结构通式为：
Figure PCTCN2018102486-appb-000002
其中，m为1-4的整数，n为0-4的整数，x为1-4的整数；
R 1、R 2、R 3、R 4、R 5、R 6分别独立地选自氢原子、卤素原子、C1-C4的烷基或C1-C4的卤代烷基。
优选地，所述环状磺酸酐类化合物的结构通式为
Figure PCTCN2018102486-appb-000003
环状羧酸酐类化合物的结构通式为
Figure PCTCN2018102486-appb-000004
(CR 1R 2)m中，m个C原子与两个磺酸基的S和一个O原子直接成环，R 1和R 2为C上的取代基，当m为大于1的整数时，即存在多个参与成环的碳原子，每个碳原子上的R 1可以相同，也可以不同；同样地，每个碳原子上的R 2可以相同，也可以不同。
类似地，(CR 3R 4)n中，n个C原子与两个羧基的C原子和一个O原子直接成环，R 3和R 4为C上的取代基，当n为大于1的整数时，即存在多个参与成环的碳原子，每个碳原子上的R 3可以相同，也可以不同；同样地，每个碳原子上的R 4可以相同，也可以不同。
优选地，m为1-4的整数，n为0-4的整数；R 1、R 2、R 3、R 4分别独立地选自氢原子、卤素原子、C1-C4的烷基或C1-C4的卤代烷基。以防止基团过大而致使反应空间位阻增大影响反应进行，有效提高收率，反应条件温和。C1-C4表示碳原子数为1-4个。
更优选地，m＝1或2；n＝0或1。
更优选地，R 1、R 2、R 3、R 4分别独立地选自氢原子、氟原子、甲基、乙基或正丙基。
优选地，所述环状醚类化合物的分子通式为[(CR 5R 6) xO] y；该通式中x×y个C原子与y个O原子成环，R 5和R 6为C上的取代基，当x或y大于1时，即存在多个参与成环的碳原子，每个碳原子上的R 5可以相同，也可以不同；同样地，每个碳原子上的R 6可以相同，也可以不同。由于成环至少需要3个原子，所以x和y不能同时为1。
优选地，x为1-4的整数，y为1-4的整数；R 5、R 6分别独立地选自氢原子、卤素原子、C1-C4的烷基或C1-C4的卤代烷基。以防止基团过大而致使反应空间位阻增大影响反应进行，有效提高收率，反应条件温和。
更优选地，x＝1或2，y＝1或2。
优选地，所述环状酸酐类化合物为草酸酐、1,3-丙二酸酐、甲基二磺酸酐或1,2-乙烷二磺酸酐。
优选地，所述环状醚类化合物为环氧乙烷或三氧杂环己烷。
优选地，根据具体实施例，所述环状酯类化合物为：
Figure PCTCN2018102486-appb-000005
优选地，环状酸酐类化合物和环状醚类化合物的摩尔比为2:1～1:2。
优选地，环状酸酐类化合物和环状醚类化合物的摩尔比为1:1～1:2。
优选地，环状酸酐类化合物和环状醚类化合物的摩尔比为1:1.1～1:1.2。
优选地，反应温度为0～200℃，反应时间为0.5～24h。
优选地，反应温度50～150℃、反应时间为1～10h。
更优选地，反应温度50～100℃、反应时间为3～8h。
优选地，不添加反应溶剂进行反应。
优选地，添加反应溶剂进行反应，反应溶剂不限，对反应惰性的溶剂均可，可选择苯类、卤代烃类、砜类等，如二氯甲烷、1,2-二氯乙烷、1,3-二氯丙烷、苯、甲苯、二甲苯、氯苯、二氯苯、三氯苯、己烷、庚烷、葵烷、二甲亚砜和环丁砜中的一种或多种。
优选地，反应结束后经过重结晶得到纯品。该反应产物的溶解性与反应物的溶解性存在较大差异，可以利用重结晶即可实现有效分离。可选择苯类、卤代烃类、砜类、醚类、酮类溶剂等将目标化合物溶出，具体可以选择如：二氯甲烷、1,2-二氯乙烷、1,3-二氯丙烷、苯甲苯、三氯甲烷、乙醚、四氢呋喃、二甲亚砜、丙酮和丁酮中的一种或多种。
与现有技术相比，本发明的有益效果是：
(1)本发明采用环状酸酐和环状醚类进行直接开环反应，扩宽了环状酯的制备途径，在环状酯的制备领域中有着重大意义。
(2)本发明对原料的选取更为直接，且只需两种原料进行反应，有效降低原料杂质的引入及中间杂质产物的产生，大大提高了目标产物的收率，而且后处理简单，三废少。
(3)本发明因反应物的有效选取，使得反应条件更温和，环境更友好，可规模化工业大生产。
(4)本发明为环状酯的制备寻找到了最为直接、最为合适的制备途径，降低企业的生产成本，增加企业效益。
(5)本发明克服了技术偏见，即现有技术中的技术人员普遍认为环状酯的制备需要溶剂，而本发明有没有溶剂都能实现。
具体实施方式
现结合具体实施例，来对本发明作进一步阐述。在描述本发明的方法时，以下实施例仅为代表性的，而非限制性的。任何在不脱离本发明构思的同等或相似替换应落入本发明的保护范围。
实施例一
将72g草酸酐
Figure PCTCN2018102486-appb-000006
和48.5g环氧乙烷加入200ml压力反应釜，搅拌，升温至100℃，保温反应2小时；冷却至室温，加入100ml×3次二氯甲烷萃取，合并萃取液，滤液蒸干得到产品111.5g，纯度99％，收率95.1％，经结构鉴定产品结构式为
Figure PCTCN2018102486-appb-000007
本实施例的草酸酐可以是购买的，也可以是自己合成后不经分离直接使用(原位合成)。
实施例二
将86g 1,3-丙二酸酐
Figure PCTCN2018102486-appb-000008
和三氧杂环己烷33g加入250ml三口烧瓶，装上搅拌，冷凝回流管和干燥管，升温至60℃，保温反应4小时，冷却至室温，加入150ml×3次二氯甲烷萃取，合并萃取液，过滤，蒸干滤液，得到产品115.2g，纯度99.1％，收率96.8％，经结构鉴定产品结构式为
Figure PCTCN2018102486-appb-000009
本实施例的1,3-丙二酸酐可以是购买的，也可以是自己合成后不经分离直接使用(原位合成)。
实施例三
将158g甲基二磺酸酐
Figure PCTCN2018102486-appb-000010
和三氧杂环己烷33g加入500ml三口烧瓶，装上搅拌，冷凝回流管和干燥管，升温至70℃，保温反应4小时，冷却至室温，加入300ml×3次二氯甲烷提取，合并提取液，过滤，蒸干滤液，得到产品185.1g，纯度98.9％，收率97.4％，经结构鉴定产品结构式为
Figure PCTCN2018102486-appb-000011
本实施例的甲基二磺酸酐可以是购买的，也可以是自己合成后不经分离直接使用(原位合成)。
实施例四
将172g 1,2-乙烷二磺酸酐
Figure PCTCN2018102486-appb-000012
和48.5g环氧乙烷投入500ml压力反应釜，搅拌，升温至120℃，保温反应1小时；降温至80℃，加入200ml×3次1,2-二氯乙烷提取，合并提取液，过滤除去不溶物，滤液蒸干得到产品213g，纯度99.1％，收率96.8％，经结构鉴定产品结构式为
Figure PCTCN2018102486-appb-000013
本实施例的1,2-乙烷二磺酸酐可以是购买的，也可以是自己合成后不经分离直接使用(原位合成)。

Claims (18)

  1. 一种环状酯类化合物的合成方法，其特征在于，所述环状酯类化合物是由环状酸酐类化合物和环状醚类化合物作为反应物直接合成。
  2. 如权利要求1所述的合成方法，其特征在于，所述环状酯类化合物为环状磺酸酯类化合物或环状羧酸酯类化合物。
  3. 如权利要求2所述的合成方法，其特征在于，环状磺酸酯类化合物由环状磺酸酐类化合物与环状醚类化合物反应得到；环状羧酸酯类化合物由环状羧酸酐类化合物与环状醚类化合物反应得到。
  4. 如权利要求3所述的合成方法，其特征在于，所述环状磺酸酯类化合物的结构通式为：
    Figure PCTCN2018102486-appb-100001
    所述环状羧酸酯类化合物的结构通式为：
    Figure PCTCN2018102486-appb-100002
    其中，m为1-4的整数，n为0-4的整数，x为1-4的整数；
    R 1、R 2、R 3、R 4、R 5、R 6分别独立地选自氢原子、卤素原子、C1-C4的烷基或C1-C4的卤代烷基。
  5. 如权利要求4所述的合成方法，其特征在于，环状磺酸酐类化合物的结构通式为
    Figure PCTCN2018102486-appb-100003
    环状羧酸酐类化合物的结构通式为
    Figure PCTCN2018102486-appb-100004
  6. 如权利要求4或5所述的合成方法，其特征在于，R 1、R 2、R 3、R 4、R 5、R 6分别独立地选 自氢原子、氟原子、甲基、乙基或正丙基。
  7. 如权利要求6所述的合成方法，其特征在于，所述环状酸酐类化合物为草酸酐、1,3-丙二酸酐、甲基二磺酸酐或1,2-乙烷二磺酸酐。
  8. 如权利要求4所述的合成方法，其特征在于，所述环状醚类化合物的分子通式为[(CR 5R 6) xO] y；；其中，y为1-4的整数，且x与y不能同时为1。
  9. 如权利要求8所述的合成方法，其特征在于，所述环状醚类化合物为环氧乙烷或三氧杂环己烷。
  10. 如权利要求1所述的合成方法，其特征在于，所述环状酯类化合物为：
    Figure PCTCN2018102486-appb-100005
  11. 如权利要求1所述的合成方法，其特征在于，环状酸酐类化合物和环状醚类化合物的摩尔比为2:1～1:2。
  12. 如权利要求11所述的合成方法，其特征在于，环状酸酐类化合物和环状醚类化合物的摩尔比为1:1～1:2。
  13. 如权利要求12所述的合成方法，其特征在于，环状酸酐类化合物和环状醚类化合物的摩尔比为1:1.1～1:1.2。
  14. 如权利要求1所述的合成方法，其特征在于，反应温度为0～200℃，反应时间为0.5～24h。
  15. 如权利要求14所述的合成方法，其特征在于，反应温度50～150℃、反应时间为1～10h。
  16. 如权利要求1所述的合成方法，其特征在于，不添加反应溶剂进行反应。
  17. 如权利要求1所述的合成方法，其特征在于，添加反应溶剂进行反应，反应溶剂为：二氯甲烷、1,2-二氯乙烷、1,3-二氯丙烷、苯、甲苯、二甲苯、氯苯、二氯苯、三氯苯、己烷、庚烷、葵烷、二甲亚砜和环丁砜中的一种或多种。
  18. 如权利要求1所述的合成方法，其特征在于，反应结束后经过重结晶得到纯品。
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