CN107827734A - A kind of synthesis technique of 2 phenoxy group propionyl chloride - Google Patents
A kind of synthesis technique of 2 phenoxy group propionyl chloride Download PDFInfo
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- CN107827734A CN107827734A CN201711179903.0A CN201711179903A CN107827734A CN 107827734 A CN107827734 A CN 107827734A CN 201711179903 A CN201711179903 A CN 201711179903A CN 107827734 A CN107827734 A CN 107827734A
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- Prior art keywords
- synthesis technique
- propionyl chloride
- phenoxy
- phenoxy groups
- chloride according
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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
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
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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
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
Abstract
The invention discloses a kind of synthesis technique of 2 phenoxy group propionyl chloride, comprise the following steps：(1) under conditions of water and alkali, using phenol and 2 chloropropionic acids as raw material, reacted, after completion of the reaction, it is faintly acid to add acid and adjust pH, filters to obtain 2 phenoxy propionic acids；(2) 2 phenoxy propionic acids are dissolved in organic solvent, add acyl chlorinating agent, reacted, after completion of the reaction, removed organic solvent, regather 80 DEG C of cuts, that is, obtain 2 phenoxy group propionyl chlorides；Wherein, the mol ratio of the phenol and 2 chloropropionic acids is 1：(1.2‑1.5)；The mol ratio of the phenol and alkali is 1：(1.2‑5.0)；The mol ratio of the solid powder a and acyl chlorinating agent are 1：(1.2‑2.0)；The method of the present invention is simple to operate, and selected reaction condition is gentle (0 80 DEG C), and selected reagent is easy to get, and the three wastes are few, environmentally friendly, small to human injury.
Description
Technical field
The invention belongs to pharmaceutical-chemical intermediate to synthesize field, relates generally to a kind of synthesis work of 2- phenoxy groups propionyl chloride
Skill.
Background technology
Zarilamid is a novel systemic fungicide for being used to prevent and treat rice blast, belongs to melanin biosynthesis
Inhibitor (MBI), there is the characteristics such as outstanding treatment, infiltration and printing sporogenesis, can be alone, can also be with protective fungicide
Agent is used with, and the resistant strain and sensitivity to benzamides bactericide are active.Field test shows, is mixed with protective fungicide
With especially good to the epidemic disease preventive effect such as downy mildew of garpe, potato, tomato.2- phenoxy group propionyl chlorides are among the key of zarilamid
Body, at present principal synthetic routes have following several：
Method one：Using phenol as raw material, reacted in the basic conditions using 2 bromopropionic acid, so as to obtain 2- phenoxy groups
Propionic acid (product a), and then product a carries out substitution reaction with oxalyl chloride, obtains 2- phenoxy groups propionyl chloride (target product b), total receipts
Rate is 60%.
Method two：Using 2- phenoxy propionic acids ethyl ester as raw material, low temperature hydrolysis, obtains product a in the basic conditions, and yield is
46%, and then product a carries out substitution reaction with thionyl chloride, obtains target product b, yield 97%.
There is shortcoming in above two synthetic method, DMF is used as solvent in method one, two so that no matter product distill,
The operations such as extraction are inconvenient.Toluene is control class low toxicity material in method one, all produces high risks to human body or environment, no
It is adapted to industrialized production.The low temperature hydrolysis reaction time is long in method two and yield is low, is not suitable for industrialized production.
The content of the invention
The problem of existing for prior art, it is an object of the invention to provide a kind of synthesis work of 2- phenoxy groups propionyl chloride
Skill.
To achieve these goals, the present invention uses following technical scheme：
A kind of synthesis technique of 2- phenoxy groups propionyl chloride, comprises the following steps：
(1) under conditions of water and alkali, using phenol and 2- chloropropionic acids as raw material, reacted, after completion of the reaction, add acid
Tune pH is faintly acid, filters to obtain white solid powder a (2- phenoxy propionic acids)；
(2) solid powder a is dissolved in organic solvent, adds acyl chlorinating agent, reacted, after completion of the reaction, removed
Organic solvent, 80 DEG C of cuts are regathered, that is, obtain pale yellow oily liquid b (2- phenoxy groups propionyl chloride)；
Wherein, the mol ratio of the phenol and 2- chloropropionic acids is 1：(1.2-1.5)；The mol ratio of the phenol and alkali is 1：
(1.2-5.0)；The mol ratio of the 2- phenoxy groups propionyl chloride and acyl chlorinating agent is 1：(1.2-2.0).
Preferably, the alkali is at least one of cesium carbonate, sodium hydroxide, potassium carbonate, sodium carbonate, triethylamine.
It is further preferred that the alkali is potassium carbonate.
Preferably, the acid is at least one of acetic acid, hydrochloric acid, sulfuric acid.
It is further preferred that the acid is hydrochloric acid.
Preferably, the organic solvent is selected from least one of dichloromethane, toluene and DMF.
It is further preferred that the organic solvent is dichloromethane.
Preferably, the acyl chlorinating agent is in thionyl chloride POCl3, phosphorus trichloride, phosphorus pentachloride, oxalyl chloride etc.
At least one.
Preferably, reaction temperature is 60-70 DEG C, preferably 65 DEG C in step (1)；Reaction time is 5-6h.
Preferably, reaction temperature is 15-40 DEG C, preferably 30 DEG C in step (2)；Reaction time 5-7h.
Preferably, step (2) uses and organic solvent is removed under reduced pressure at 70-150 DEG C.
Beneficial effects of the present invention：
(1) method operation handy and safe of the invention, intermediate product and final product are easily separated, three-protection design letter
It is single easy, it is environmentally friendly, it is small to human injury；
(2) equipment that method of the invention uses is simple, and without using special installation, reaction condition is gentle (0-80 DEG C),
It is low without using the specific conditions such as high pressure, high vacuum, cost；
(3) method yield of the invention is higher and stably, and production cost is low, is suitable for industrialized production.
Embodiment
In order to preferably explain the present invention, it is described further in conjunction with specific examples below, but the present invention is unlimited
In specific embodiment.
Embodiment 1
In 2L reaction bulbs, 214g sodium hydroxides 530ml water dissolves, and 200g phenol, 280g2- chloropropionic acids is added, 65
It is complete that 6h reactions are stirred at DEG C, acid adding adjusts pH=4, filtering, obtains white solid powder a, purity 99.8%, yield
80.3%.By 205g white solid powders a in 2L reaction bulbs, add at 400ml dichloromethane, 30 DEG C of 240g thionyl chlorides and stir
It is complete to mix 6h reactions, organic solvent is removed under reduced pressure under lower temperature, regathers 80 DEG C of cuts, that is, obtains pale yellow oily liquid b,
Purity 98.24%, yield 94.5%.
Embodiment 2
In 2L reaction bulbs, 214g sodium hydroxides 530ml water dissolves, and 200g phenol, 345g2- chloropropionic acids is added, 65
It is complete that 6h reactions are stirred at DEG C, acid adding adjusts pH=4, filtering, obtains white solid powder a, purity 99.6%, yield 85%.
By 205g white solid powders a in 2L reaction bulbs, it is anti-to add stirring 6h at 400ml dichloromethane, 30 DEG C of 325g thionyl chlorides
Should be complete, organic solvent is removed under reduced pressure under lower temperature, regathers 80 DEG C of cuts, that is, obtains pale yellow oily liquid b, purity
99.1%, yield 92.6%.
Embodiment 3
In 2L reaction bulbs, 739g potassium carbonate 530ml water dissolves, and 200g phenol, 280g2- chloropropionic acids is added, at 65 DEG C
Lower stirring 6h reactions are complete, and acid adding adjusts pH=4, filtering, obtains white solid powder a, purity 99.8%, yield 82.1%.
By 205g white solid powders a in 2L reaction bulbs, it is anti-to add stirring 6h at 400ml dichloromethane, 30 DEG C of 240g thionyl chlorides
Should be complete, organic solvent is removed under reduced pressure under lower temperature, regathers 80 DEG C of cuts, that is, obtains pale yellow oily liquid b, purity
98.6%, yield 93.6%.
The specific embodiment of the present invention is the foregoing is only, is not intended to limit the scope of the invention, every utilization
The equivalent transformation that the present invention makees, or other related technical fields are directly or indirectly used in, similarly it is included in the present invention's
Among scope of patent protection.
Claims (10)
1. a kind of synthesis technique of 2- phenoxy groups propionyl chloride, it is characterised in that comprise the following steps：
(1) under conditions of water and alkali, using phenol and 2- chloropropionic acids as raw material, reacted, after completion of the reaction, add acid and adjust pH
For faintly acid, 2- phenoxy propionic acids are filtered to obtain；
(2) 2- phenoxy propionic acids are dissolved in organic solvent, add acyl chlorinating agent, reacted, after completion of the reaction, removing has
Solvent, 80 DEG C of cuts are regathered, that is, obtain 2- phenoxy group propionyl chlorides；
Wherein, the mol ratio of the phenol and 2- chloropropionic acids is 1：(1.2-1.5)；The mol ratio of the phenol and alkali is 1：
(1.2-5.0)；The mol ratio of the 2- phenoxy propionic acids and acyl chlorinating agent is 1：(1.2-2.0).
2. the synthesis technique of 2- phenoxy groups propionyl chloride according to claim 1, it is characterised in that the alkali be cesium carbonate,
At least one of sodium hydroxide, potassium carbonate, sodium carbonate, triethylamine.
3. the synthesis technique of 2- phenoxy groups propionyl chloride according to claim 2, it is characterised in that the alkali is potassium carbonate.
4. the synthesis technique of 2- phenoxy groups propionyl chloride according to claim 1, it is characterised in that the acid is acetic acid, salt
At least one of acid, sulfuric acid.
5. the synthesis technique of 2- phenoxy groups propionyl chloride according to claim 1, it is characterised in that the acyl chlorinating agent is selected from
At least one of thionyl chloride, POCl3, phosphorus trichloride, phosphorus pentachloride, oxalyl chloride.
6. the synthesis technique of 2- phenoxy groups propionyl chloride according to claim 1, it is characterised in that the organic solvent is selected from
At least one of dichloromethane, toluene and DMF.
7. the synthesis technique of 2- phenoxy groups propionyl chloride according to claim 1, it is characterised in that the organic solvent is two
Chloromethanes.
8. the synthesis technique of 2- phenoxy groups propionyl chloride according to claim 1, it is characterised in that reaction temperature in step (1)
Spend for 60-70 DEG C, reaction time 5-6h.
9. the synthesis technique of 2- phenoxy groups propionyl chloride according to claim 1, it is characterised in that reaction temperature in step (2)
Spend for 15-40 DEG C, reaction time 5-7h.
10. the synthesis technique of 2- phenoxy groups propionyl chloride according to claim 1, it is characterised in that step (2) uses
Organic solvent is removed under reduced pressure at 70-150 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111355A (en) * | 2018-08-31 | 2019-01-01 | 浙江工业大学 | A kind of chemical synthesis process of (R) -2- phenoxy propionic acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060211717A1 (en) * | 1999-12-24 | 2006-09-21 | Kirin Beer Kabushiki Kaisha | Quinoline and quinazoline derivatives and drugs containing the same |
| CN101307014A (en) * | 2007-05-17 | 2008-11-19 | 鲍菊篱 | Method for synthesizing N-(1-nitrile-1,2-dimethyl propyl)-2-(2,4-dichloro phenoxyl)propionamide |
| CN101492359A (en) * | 2009-02-27 | 2009-07-29 | 黄贤明 | Process for producing phenoxy alkane acid derivative |
-
2017
- 2017-11-23 CN CN201711179903.0A patent/CN107827734A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060211717A1 (en) * | 1999-12-24 | 2006-09-21 | Kirin Beer Kabushiki Kaisha | Quinoline and quinazoline derivatives and drugs containing the same |
| CN101307014A (en) * | 2007-05-17 | 2008-11-19 | 鲍菊篱 | Method for synthesizing N-(1-nitrile-1,2-dimethyl propyl)-2-(2,4-dichloro phenoxyl)propionamide |
| CN101492359A (en) * | 2009-02-27 | 2009-07-29 | 黄贤明 | Process for producing phenoxy alkane acid derivative |
Non-Patent Citations (3)
| Title |
|---|
| HEATHCOCK, CLAYTON H.等: "《Acyclic stereoselection. 23. Lactaldehyde enolate equivalents》", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| VAKAROV, SERGEY A.等: "《Diastereoselective acylation of 3,4-dihydro-3-methyl-2H-[1,4]benzoxazines with 2-phenoxy carbonyl chlorides》", 《TETRAHEDRON: ASYMMETRY》 * |
| 倪沛洲等: "《α1受体拮抗剂DDPH类似物的合成及其降压活性》", 《中国药科大学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111355A (en) * | 2018-08-31 | 2019-01-01 | 浙江工业大学 | A kind of chemical synthesis process of (R) -2- phenoxy propionic acid |
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