WO2018039845A1 - Method for preparing hydroxybenzoic anhydride - Google Patents
Method for preparing hydroxybenzoic anhydride Download PDFInfo
- Publication number
- WO2018039845A1 WO2018039845A1 PCT/CN2016/097106 CN2016097106W WO2018039845A1 WO 2018039845 A1 WO2018039845 A1 WO 2018039845A1 CN 2016097106 W CN2016097106 W CN 2016097106W WO 2018039845 A1 WO2018039845 A1 WO 2018039845A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- anhydride
- benzoic
- hydroxybenzoic
- preparing
- preparation
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 13
- WLPQCHKXJRHZRI-UHFFFAOYSA-N (2-hydroxybenzoyl) 2-hydroxybenzoate Chemical compound OC1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1O WLPQCHKXJRHZRI-UHFFFAOYSA-N 0.000 title claims abstract description 8
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 24
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 claims abstract description 13
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 6
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 6
- 239000011541 reaction mixture Substances 0.000 claims abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 4
- 230000009965 odorless effect Effects 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000012452 mother liquor Substances 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/54—Preparation of carboxylic acid anhydrides
- C07C51/56—Preparation of carboxylic acid anhydrides from organic acids, their salts, their esters or their halides, e.g. by carboxylation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/04—Monocyclic monocarboxylic acids
- C07C63/06—Benzoic acid
Definitions
- the invention belongs to the technical field of preparation of organic compounds, and in particular relates to a preparation method of hydroxybenzoic anhydride.
- Hydroxybenzoic anhydride is a commonly used organic intermediate and has a wide range of uses in organic synthesis, chemical raw materials, pharmaceutical preparation, etc., especially in the pharmaceutical industry as a basic intermediate to derive a large number of organic compounds and new varieties. Commonly used for the determination of water. Benzoic acid liver is formed by the condensation of benzoic acid with acetic anhydride. Benzoic anhydride, also known as benzoic anhydride, is a colorless orthorhombic prism crystal, insoluble in water, soluble in ether and ethanol, stable to water and cold alkali, and can be hydrolyzed by boiling alkali metal carbonates and caustic. The preparation of common benzoic anhydride is low in purity and cannot be used by people.
- the object of the present invention is to provide a method for preparing benzoic anhydride having high purity and high quality in view of the deficiencies of the prior art.
- the technical solution of the present invention is: a method for preparing benzoic anhydride, which is innovative in that the steps are as follows:
- fractional distillation under reduced pressure, and fractions below 145 ° C, 145-175 ° C, and 175-200 ° C are separately collected at 15-19 mmHg, the latter being a crude benzoic anhydride, a lower temperature fraction and the above
- the fractions of 120-130 °C are combined, and after adding a drop of phosphoric acid, fractional distillation is carried out to obtain some 210-220/20 mmHg fractions, ie crude benzoic anhydride, total crude product 1.0-1.2 Kg, normal pressure 120-130 °C
- the fraction is subjected to re-distillation to obtain crude acetic acid below 120 ° C and crude acetic anhydride at 130-140 ° C;
- the preparation method of the benzoic anhydride of the invention is simple and easy to operate, convenient to operate, easy to obtain raw materials, common in equipment, short in cycle and high in purity.
- a method for preparing hydroxybenzoic anhydride the steps are as follows:
- the preparation method of the invention adopts benzoic anhydride, which is simple and easy to operate, convenient to operate, easy to obtain raw materials, common in equipment, short in cycle and high in purity.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Provided is a method for preparing hydroxybenzoic anhydride. Benzoic acid and acetic anhydride are put in a container, a reaction mixture is slowly distilled to obtain a pure hydroxybenzoic anhydride product, and a mother liquor with a melting point of 50ºC is concentrated in a water bath and recrystallized again, so that a pure product is obtained. The advantages lie in that the preparation method using benzoic anhydride is simple and easy to implement, convenient to operate, the raw materials are readily available, the equipment is common, the cycle is short and the purity is high.
Description
技术领域Technical field
本发明属于有机化合物的制备技术领域，具体涉及一种羟基苯甲酸酐的制备方法。 The invention belongs to the technical field of preparation of organic compounds, and in particular relates to a preparation method of hydroxybenzoic anhydride.
背景技术Background technique
羟基苯甲酸酐是一种常用的有机中间体，在有机合成、化工原料、医药制备等有着广泛的用途，尤其在制药行业作为基础中间体衍生大量有机化合物及新品种。常用于水的测定。苯甲酸肝是用苯甲酸与乙酸酐缩合而成。苯甲酸酐又称安息香酸酐，成品为无色正交棱柱晶体，不溶于水、溶于乙醚和乙醇，对水和冷碱稳定，能被沸腾碱金属的碳酸盐和苛性碱水解。常见的苯甲酸酐的制备纯度较低，无法满足人们的使用。
Hydroxybenzoic anhydride is a commonly used organic intermediate and has a wide range of uses in organic synthesis, chemical raw materials, pharmaceutical preparation, etc., especially in the pharmaceutical industry as a basic intermediate to derive a large number of organic compounds and new varieties. Commonly used for the determination of water. Benzoic acid liver is formed by the condensation of benzoic acid with acetic anhydride. Benzoic anhydride, also known as benzoic anhydride, is a colorless orthorhombic prism crystal, insoluble in water, soluble in ether and ethanol, stable to water and cold alkali, and can be hydrolyzed by boiling alkali metal carbonates and caustic. The preparation of common benzoic anhydride is low in purity and cannot be used by people.
发明内容Summary of the invention
本发明的目的在于针对现有技术的不足，现提供一种纯度高、质量高的苯甲酸酐的制备方法。 The object of the present invention is to provide a method for preparing benzoic anhydride having high purity and high quality in view of the deficiencies of the prior art.
为实现上述目的，本发明的技术方案是：一种苯甲酸酐的制备方法，其创新点在于：步骤如下：In order to achieve the above object, the technical solution of the present invention is: a method for preparing benzoic anhydride, which is innovative in that the steps are as follows:
（1）在容器中放入苯甲酸和乙酸酐，慢慢蒸馏反应的混合物，温度为100-120℃，收集150ml馏分后，向蒸馏瓶中加入150ml乙酸酐，继续蒸馏，此过程再重复，共加入2Kg乙酸酐；(1) Put benzoic acid and acetic anhydride in a container, slowly distill the reaction mixture at a temperature of 100-120 ° C, collect 150 ml of the fraction, then add 150 ml of acetic anhydride to the distillation flask, continue to distill, and the process is repeated. A total of 2Kg acetic anhydride was added;
（2）将残余物减压分馏，在15～19mmHg下，分别收集低于145℃，145～175℃，175～200℃的馏分，后者为苯甲酸酐粗品，较低温度的馏分与上述常压的120～130℃的馏分合并，再加一滴磷酸后，再进行分馏，可获得一些210～220/20mmHg馏分即苯甲酸酐粗品，共计粗品1.0～1.2Kg，对常压120～130℃的馏分进行重新蒸馏，可以得到低于120℃乙酸粗品，和130～140℃的乙酸酐粗品；(2) The residue is subjected to fractional distillation under reduced pressure, and fractions below 145 ° C, 145-175 ° C, and 175-200 ° C are separately collected at 15-19 mmHg, the latter being a crude benzoic anhydride, a lower temperature fraction and the above At normal pressure, the fractions of 120-130 °C are combined, and after adding a drop of phosphoric acid, fractional distillation is carried out to obtain some 210-220/20 mmHg fractions, ie crude benzoic anhydride, total crude product 1.0-1.2 Kg, normal pressure 120-130 °C The fraction is subjected to re-distillation to obtain crude acetic acid below 120 ° C and crude acetic anhydride at 130-140 ° C;
（3）提纯方法：每1Kg加0.4～0.6L苯溶解，使溶解成雾浊，冷却，析出无色无味的结晶体，即苯甲酸酐纯品，熔点50℃母液在水浴上浓缩，再次重结晶，获纯品。(3) Purification method: 0.4-0.6L of benzene is added per 1Kg to dissolve, so that it dissolves into haze, cools, and precipitates colorless and odorless crystals, ie pure benzoic anhydride. The mother liquor at 50 ° C is concentrated on a water bath and recrystallized again. , obtained pure.
本发明的有益效果如下：本发明采用苯甲酸酐的制备方法简单易行、操作方便、原料易得、设备通用、周期短并且纯度高。The beneficial effects of the invention are as follows: the preparation method of the benzoic anhydride of the invention is simple and easy to operate, convenient to operate, easy to obtain raw materials, common in equipment, short in cycle and high in purity.
具体实施方式detailed description
以下由特定的具体实施例说明本发明的实施方式，熟悉此技术的人士可由本说明书所揭露的内容轻易地了解本发明的其他优点及功效。The embodiments of the present invention are described below by way of specific embodiments, and those skilled in the art can readily understand other advantages and functions of the present invention from the disclosure.
实施例1Example 1
一种羟基苯甲酸酐的制备方法，步骤如下：A method for preparing hydroxybenzoic anhydride, the steps are as follows:
（1）在容器中放入苯甲酸和乙酸酐，慢慢蒸馏反应的混合物，温度为100℃，继续蒸馏，此过程再重复；(1) Put benzoic acid and acetic anhydride in a container, slowly distill the reaction mixture at a temperature of 100 ° C, continue to distill, and the process is repeated;
（2）提纯方法：每1Kg加0.4L苯溶解，使溶解成雾浊，冷却，析出无色无味的结晶体，即苯甲酸酐纯品。(2) Purification method: 0.4L of benzene is dissolved per 1Kg to dissolve into haze, and it is cooled to precipitate a colorless and odorless crystal, that is, pure benzoic anhydride.
本发明采用苯甲酸酐的制备方法简单易行、操作方便、原料易得、设备通用、周期短并且纯度高。The preparation method of the invention adopts benzoic anhydride, which is simple and easy to operate, convenient to operate, easy to obtain raw materials, common in equipment, short in cycle and high in purity.
上述实施例只是本发明的较佳实施例，并不是对本发明技术方案的限制，只要是不经过创造性劳动即可在上述实施例的基础上实现的技术方案，均应视为落入本发明专利的权利保护范围内。The above embodiments are only preferred embodiments of the present invention, and are not intended to limit the technical solutions of the present invention. Any technical solutions that can be implemented on the basis of the above embodiments without creative work should be considered as falling into the present invention. The scope of protection of rights.
Claims (1)
- 一种羟基苯甲酸酐的制备方法，其特征在于：步骤如下：A method for preparing hydroxybenzoic anhydride, characterized in that the steps are as follows:（1）在容器中放入苯甲酸和乙酸酐，慢慢蒸馏反应的混合物，温度为100℃，继续蒸馏，此过程再重复；(1) Put benzoic acid and acetic anhydride in a container, slowly distill the reaction mixture at a temperature of 100 ° C, continue to distill, and the process is repeated;（2）提纯方法：每1Kg加0.4L苯溶解，使溶解成雾浊，冷却，析出无色无味的结晶体，即苯甲酸酐纯品。(2) Purification method: 0.4L of benzene is dissolved per 1Kg to dissolve into haze, and it is cooled to precipitate a colorless and odorless crystal, that is, pure benzoic anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2016/097106 WO2018039845A1 (en) | 2016-08-29 | 2016-08-29 | Method for preparing hydroxybenzoic anhydride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2016/097106 WO2018039845A1 (en) | 2016-08-29 | 2016-08-29 | Method for preparing hydroxybenzoic anhydride |
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| Publication Number | Publication Date |
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| WO2018039845A1 true WO2018039845A1 (en) | 2018-03-08 |
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| PCT/CN2016/097106 WO2018039845A1 (en) | 2016-08-29 | 2016-08-29 | Method for preparing hydroxybenzoic anhydride |
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| WO (1) | WO2018039845A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1222131A (en) * | 1996-06-20 | 1999-07-07 | 罗狄亚化学公司 | Acylation method for aromatic compound |
| CN1249737A (en) * | 1997-03-12 | 2000-04-05 | 罗狄亚化学公司 | Method for acylation or sulphonation of aromatic compound |
| CN104130121A (en) * | 2014-07-14 | 2014-11-05 | 天津市化学试剂研究所有限公司 | Benzoic anhydride preparation method |
-
2016
- 2016-08-29 WO PCT/CN2016/097106 patent/WO2018039845A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1222131A (en) * | 1996-06-20 | 1999-07-07 | 罗狄亚化学公司 | Acylation method for aromatic compound |
| CN1249737A (en) * | 1997-03-12 | 2000-04-05 | 罗狄亚化学公司 | Method for acylation or sulphonation of aromatic compound |
| CN104130121A (en) * | 2014-07-14 | 2014-11-05 | 天津市化学试剂研究所有限公司 | Benzoic anhydride preparation method |
Non-Patent Citations (1)
| Title |
|---|
| ZHANG GUANLI ET AL.: "The synthesis of 4-cyan-o-phthalic anhydride", NEW CHEMICAL MATERIALS, vol. 7, no. 30, 31 July 2002 (2002-07-31), pages 34 - 35 * |
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