CN105820054A - Preparation method of 3-methoxy-2-nitrobenzoate - Google Patents
Preparation method of 3-methoxy-2-nitrobenzoate Download PDFInfo
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- CN105820054A CN105820054A CN201610262994.3A CN201610262994A CN105820054A CN 105820054 A CN105820054 A CN 105820054A CN 201610262994 A CN201610262994 A CN 201610262994A CN 105820054 A CN105820054 A CN 105820054A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/16—Separation; Purification; Stabilisation; Use of additives
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Abstract
The invention discloses a preparation method of 3-methyl-2-nitrobenzoate. The preparation method has the advantages that firstly 3-methyl benzoate is taken as a starting material, nitrification, reduced-pressure concentration, washing with ice water, filtering and recrystallization are carried out for preparing the 3-methyl-2-nitrobenzoate, a new method takes acetic anhydride, instead of sulphuric acid, as a catalyst, so that the reaction selectivity and the yield are improved, the cleanliness of industrial synthesis reaction is improved, and environmental pollution is reduced; secondly, production of a large amount of waste acid and waste water in a production process is avoided; and thirdly, the production cost is reduced. The method disclosed by the invention is relatively mild in reaction conditions, good in selectivity, high in yield and applicable to industrial production.
Description
Technical field
The invention belongs to organic synthesis field, specifically, relate to prepared by a kind of 3-methyl-2-nitrobenzene methyl
Method.
Background technology
3-methyl-2-nitrobenzene methyl is the synthesis 2-chloro-N of amino-5-, the raw material of 3-dimethyl benzamide,
Pesticide, medical market are widely used.
At present it is known that the preparation method about 3-methyl-2-nitrobenzoic acid mainly has following several:
In the Qin Tao Master's thesis " meta replaces the research of methylbenzene nitration selectivity " of document Institutes Of Technology Of Nanjing, with 3-methylbenzene
Methyl formate is raw material, and nitric acid-sulfuric acid nitration mixture, as nitrating agent, has synthesized 3-methyl-2-nitrobenzene methyl, reacted
Journey produces substantial amounts of spent acid, it is difficult to process.
Document Tetrahedron Letters, 47(49): 8,651 8652；2006；With 3-ar-Toluic acid as raw material, urine
Element single nitric acid salt or nitrourea are that nitrating agent synthesis is rough containing 3-methyl-2-nitrobenzoic acid, 3-methyl-4-Nitrobenzol
Formic acid, the mixture of 3-methyl-6-nitrobenzoic acid, in based on 3-methyl-6-nitrobenzoic acid, and 3-methyl-2-nitro
Benzoic acid only accounts for the 23.4% ~ 24.5% of gross product, and reaction selectivity is poor.
Japan Patent JP 05132450A, with 1,3-dimethyl nitrobenzene is raw material, oxidation preparation in Neutral potassium chromate, sulphuric acid
3-methyl-2-nitrobenzoic acid, but productivity only 40%, and have solid waste to produce.
Document Bulletin of the Chemical Society of Japan；60(10)；3659-3662；1987；
With 3-ar-Toluic acid as raw material, nitrogen dioxide and nitric acid, as nitrating agent, obtain 3-methyl-2-nitrobenzoic acid, yield
49%, nitrogen dioxide limits it as nitrating agent because of transport and vent gas treatment difficulty and applies.
Producing to meet 3-methyl-2-nitrobenzene methyl industrialization cleaning, the present invention proposes a kind of 3-methyl-2-
The preparation method of nitrobenzene methyl.
Summary of the invention
The object of the invention is just to provide a kind of method preparing 3-methyl-2-nitrobenzene methyl.
The present invention is achieved by the following technical solutions:
A kind of preparation method of 3-methyl-2-nitrobenzene methyl, the present invention with 3-methyl toluate as initiation material,
3-methyl-2-nitrobenzene methyl is prepared through nitrification, concentrating under reduced pressure, frozen water washing, filtration and recrystallization.
A kind of preparation method of 3-methyl-2-nitrobenzene methyl, nitre used in denitrification step of the present invention
Agent is acetic anhydride and nitric acid, and described 3-methyl toluate with the ratio of nitric acid, the amount of acetic anhydride material is: 1:0.9 ~ 4:
1.7~15。
The preparation method of a kind of 3-methyl-2-nitrobenzene methyl, the preparation method of nitrating agent of the present invention is as follows: take second
The 40-100% of anhydride volume, mixes with described nitric acid, stirs at 0 DEG C ~ 20 DEG C, standby.
The preparation method of a kind of 3-methyl-2-nitrobenzene methyl, by 3-methyl toluate or it is with remaining
The mixed liquor of acetic anhydride is added drop-wise in above-mentioned nitrating agent, carries out reacting 0.25h ~ 3h at 0 DEG C ~ 50 DEG C.
The preparation method of a kind of 3-methyl-2-nitrobenzene methyl, the organic solvent for recrystallization is: methanol, second
Alcohol, isopropanol, acetone, or its aqueous solution.
The invention have the advantage that
The method of the present invention is compared with traditional handicraft, and remarkable advantage is: (1) new method replaces sulphuric acid as catalysis using acetic anhydride
Agent, not only increases reaction selectivity and yield, and improves the spatter property of commercial synthesis reaction, reduce environmental pollution.
(2) this method is avoided producing substantial amounts of spent acid waste water in process of production.(3) reduce consumption, reduce production cost.The present invention
Method reaction condition relatively mild, selectivity is good, and yield is high, is suitable to industrialized production.
Detailed description of the invention
In order to make those skilled in the art be better understood from the technical scheme of invention, disclose some non-limits further below
The present invention is described in detail for embodiment processed.
Embodiment 1
In 100mL round-bottomed flask, add 4.8mL 65% nitric acid (0.07moL), drip 7.6mL(0.08 moL) acetic anhydride, drips
Complete, after reaction 0.5h, after 7.6mL acetic anhydride and 3.0g 3-methyl toluate (0.02moL) are mixed, it is slowly dropped to
In reaction system, above operation is all carried out under condition of ice bath.After dripping off, it is warming up to 30 DEG C of reaction 3h, after stopped reaction, steams
The glacial acetic acid of acetic anhydride, nitric acid and generation, pours into concentrated solution in frozen water, stirring, has yellow solid to separate out, and adds 20mL acetic acid
Ethyl ester will be attached to the product on bottle wall and dissolves, and separatory concentrates, obtains light yellow liquid 3.83g, yield 98.21%.Divide through HPLC
Analysis, the content of 3-methyl-2-nitrobenzene methyl and 3-methyl-4-nitrobenzene methyl ratio is for 72:28.By light yellow liquid
Body mixture dehydrated alcohol carries out recrystallization, obtains 3-methyl-2-nitrobenzene methyl.
Embodiment 2
In 100mL round-bottomed flask, add 2.7mL 65% nitric acid (0.04moL), drip 3.8mL(0.04 moL) acetic anhydride, drips
Complete, after reaction 0.5h, after 3.8mL acetic anhydride and 3.0 g 3-methyl toluate (0.02moL) are mixed, it is slowly dropped to
In reaction system, above operation is all carried out under condition of ice bath.After dripping off, it is warming up to 40 DEG C ~ 50 DEG C reaction 15min, stops anti-
Ying Hou, steams acetic anhydride and glacial acetic acid, is poured into by concentrated solution in frozen water, stirring, has yellow solid to separate out, and adds 20mL acetic acid second
Ester will be attached to the product on bottle wall and dissolves, and separatory concentrates, obtains light yellow liquid 3.66g, yield 93.85%.Analyze through HPLC,
The content of 3-methyl-2-nitrobenzene methyl and 3-methyl-4-nitrobenzene methyl is than about 66:34.This is light yellow
Liquid mixture dehydrated alcohol carries out recrystallization, obtains 3-methyl-2-nitrobenzene methyl.
Embodiment 3
In 100mL round-bottomed flask, add 4.8mL 95% nitric acid (0.11moL), drip 1.0mL(0.011 moL) acetic anhydride, drips
Complete, after reaction 0.5h, after 1.2mL acetic anhydride and 4.7g 3-methyl toluate (0.032moL) are mixed, it is slowly dropped to
In reaction system, above operation is all carried out under condition of ice bath.After dripping off, it is warming up to 15 DEG C ~ 20 DEG C reactions, after stopped reaction,
Steam the glacial acetic acid of acetic anhydride, nitric acid and generation, concentrated solution is poured in frozen water, stirring, there is yellow solid to separate out, add 20mL
Ethyl acetate will be attached to the product on bottle wall and dissolves, and separatory concentrates, obtains light yellow liquid 3.72g, yield 95.38%.Warp
HPLC analyzes, and the content of 3-methyl-2-nitrobenzene methyl and 3-methyl-4-nitrobenzene methyl ratio is for 75:25.Should
Light yellow liquid mixture dehydrated alcohol carries out recrystallization, obtains 3-methyl-2-nitrobenzene methyl.
Claims (5)
1. the preparation method of a 3-methyl-2-nitrobenzene methyl, it is characterised in that the present invention is with 3-ar-Toluic acid first
Ester is initiation material, prepares 3-methyl-2-nitrobenzoic acid first through nitrification, concentrating under reduced pressure, frozen water washing, filtration and recrystallization
Ester.
The preparation method of a kind of 3-methyl-2-nitrobenzene methyl the most according to claim 1, it is characterised in that this
Nitrating agent used in denitrification step described in invention is acetic anhydride and nitric acid, described 3-methyl toluate and nitric acid,
The ratio of the amount of acetic anhydride material is: 1:0.9 ~ 4:1.7 ~ 15.
The preparation method of a kind of 3-methyl-2-nitrobenzene methyl the most according to claim 1, it is characterised in that this
The preparation method of invention nitrating agent is as follows: take the 40-100% of acetic anhydride volume, mixes with described nitric acid, at 0 DEG C ~ 20 DEG C
Stir, standby.
The preparation method of a kind of 3-methyl-2-nitrobenzene methyl the most according to claim 1, it is characterised in that will
3-methyl toluate or its mixed liquor with remaining acetic anhydride are added drop-wise in above-mentioned nitrating agent, carry out at 0 DEG C ~ 50 DEG C
Reaction 0.25h ~ 3h.
The preparation method of a kind of 3-methyl-2-nitrobenzene methyl the most according to claim 1, it is characterised in that use
Organic solvent in recrystallization is: methanol, ethanol, isopropanol, acetone, or its aqueous solution.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496038A (en) * | 2016-11-01 | 2017-03-15 | 安徽安生生物化工科技有限责任公司 | A kind of preparation method of 3 methyl, 2 nitrobenzoic acid of high selectivity |
| CN114560772A (en) * | 2022-02-14 | 2022-05-31 | 南昌大学 | Synthetic method of 3-methyl-2-nitrobenzoic acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196045A (en) * | 1995-09-13 | 1998-10-14 | 曾尼卡有限公司 | Process for nitrating diphenyl ether compounds |
| CN104326918A (en) * | 2014-10-10 | 2015-02-04 | 青岛农业大学 | Compound 3-fluoro-4-hydroxy-5-nitro-1-phenyl butanone and preparation method and agricultural biological activity thereof |
-
2016
- 2016-04-26 CN CN201610262994.3A patent/CN105820054A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196045A (en) * | 1995-09-13 | 1998-10-14 | 曾尼卡有限公司 | Process for nitrating diphenyl ether compounds |
| CN104326918A (en) * | 2014-10-10 | 2015-02-04 | 青岛农业大学 | Compound 3-fluoro-4-hydroxy-5-nitro-1-phenyl butanone and preparation method and agricultural biological activity thereof |
Non-Patent Citations (2)
| Title |
|---|
| H. D. HOLLIS SHOWALTER等: "Concise Syntheses of the Novel 1H-Pyrrolo[3,2-g]quinazoline Ring System and its [2,3-f] Angular Isomer", 《J.ORG.CHEM.》 * |
| 秦涛: "间位取代甲苯硝化选择性的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496038A (en) * | 2016-11-01 | 2017-03-15 | 安徽安生生物化工科技有限责任公司 | A kind of preparation method of 3 methyl, 2 nitrobenzoic acid of high selectivity |
| CN114560772A (en) * | 2022-02-14 | 2022-05-31 | 南昌大学 | Synthetic method of 3-methyl-2-nitrobenzoic acid |
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Application publication date: 20160803 |