CN106316808A - Preparation method of 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone - Google Patents
Preparation method of 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone Download PDFInfo
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- CN106316808A CN106316808A CN201610671264.9A CN201610671264A CN106316808A CN 106316808 A CN106316808 A CN 106316808A CN 201610671264 A CN201610671264 A CN 201610671264A CN 106316808 A CN106316808 A CN 106316808A
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- cyclopropyl
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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
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/30—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reactions not involving the formation of esterified sulfo groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
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Abstract
The invention relates to a preparation method of 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone. A compound I and cyclopropyl methyl ketone react at 0-30 DEG C to obtain a compound II under the existence of alkali and organic solvent; the compound II is hydrolyzed under the existence of acid to obtain a compound III, namely 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone. The structural formulas of the compound I, the compound II and the compound III are shown in the description, R1 is any one of trimethylsilyl, acetyl and methyl sulphonyl, and R2 is methyl or ethyl. The method is simple in process, low in cost, little in three wastes, high in target product content and yield and suitable for industrial production.
Description
Technical field
The invention belongs to chemical field, relate to the preparation side of a kind of 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone
Method.
Background technology
SAN-619F is the triazole bactericidal agent of mountain pass scholar company of Switzerland exploitation, is ergosterol demethylation inhibitors,
There is prevention and the effect for the treatment of, to the Erysiphe on cereal crop, coffee, Radix Betae, fruit tree and Fructus Vitis viniferae, Uredinales, spore
Mould Pseudomonas, beak genus, Septoria, Venturia pathogenic bacteria are all effective, can prevent and treat frumentum and coffee rust, frumentum, fruit tree and Portugal
Grape powdery mildew, Semen arachidis hypogaeae, beet tops pinta, scab of apple and Semen arachidis hypogaeae white rot, it is also possible to mixed with other antibacterial.
1-(4-chlorphenyl)-2-cyclopropyl-1-acetone is the key intermediate of SAN-619F, its synthetic method mainly have with
Under several: with Cyclopropylacetic acid and chlorobenzene as raw material, generating through Fu Ke acylation reaction, but Cyclopropylacetic acid is expensive, chloride tries
Agent is easily generated environmental pollution；With allyl chloride, 4-chloro-benzaldehyde as raw material, synthesize through the step such as grignard reaction, oxalyl chloride,
But severe reaction conditions；Being that raw material reaction obtains to 6-chlorophenyl nitrile, allyl bromide, bromoallylene and zinc powder, but the response time is longer, and product is multiple
Miscellaneous, it is not readily separated purification.
For the deficiency of existing technique, need to develop a simple process, operation safety, good economy performance, be suitable for scale
1-(4-the chlorphenyl)-2-cyclopropyl-1-acetone synthetic route of exploitation.
Summary of the invention
The technical problem to be solved is to provide a kind of productivity height, 1-(4-the chlorphenyl)-2-ring of safety and environmental protection
The preparation method of propyl group-1-acetone.
In order to solve above-mentioned technical problem, the present invention adopts the following technical scheme that
It is an object of the invention to provide the preparation method of a kind of 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone, described system
Preparation Method includes the following steps carried out successively:
Step (1), by compounds I and cyclopropyl methyl ketone, in the presence of alkali and organic solvent, anti-at 0～30 DEG C
Compound ii should be obtained；
Step (2), make compound ii hydrolyze in the presence of acid, obtain compound III, i.e. 1-(4-chlorphenyl)-2-ring third
Base-1-acetone；
Wherein: the structural formula of described compounds I is:The structural formula of described compound ii is:The structural formula of described compound III is:R1, acetyl silica-based for trimethyl
Any one in base, methyl sulphonyl；R2It is methyl or ethyl.
Preferably, in step (1), the molar ratio 1.0:0.8 of described compounds I, cyclopropyl methyl ketone and alkali～
2.0:1.0～3.0, more preferably 1.0:1.0～2.0:2～3.0, most preferably 1.0:1.0～2.0:2.0～2.5.
Preferably, in step (1), described alkali is in sodium hydroxide, potassium hydroxide, Feldalat NM, Sodamide.
Plant or several.
Preferably, in step (1), described organic solvent be selected from DMF, N-Methyl pyrrolidone,
One or more in dimethyl sulfoxide, benzene, toluene, oxolane, dioxane.
Preferably, in step (1), the Molar ratio that feeds intake of described organic solvent and described compounds I is 1100
～1300mL/mol.
Preferably, in step (1), described reaction temperature is 20～30 DEG C.
Preferably, step (1) method particularly includes: be dissolved in described organic solvent by described compounds I, adds institute
The alkali stated, is uniformly mixed, and is slowly added dropwise described cyclopropyl methyl ketone, controls the reaction temperature of reaction system, stirs continuously
Mix 2～6 hours, reactant liquor through extraction, be dried, obtain described compound ii after precipitation.
Preferably, in step (2), the molar ratio of described compound ii and described acid is 1.0:1.0～3.0.
Preferably, in step (2), described acid one in hydrochloric acid, sulphuric acid, phosphoric acid, p-methyl benzenesulfonic acid, phosphotungstic acid
Or it is several.
Preferably, in step (2), described compound ii is hydrolyzed the most in presence of organic solvent, and described has
Machine solvent is toluene.
Preferably, step (2) method particularly includes: by described compound ii, organic solvent and acid at 0～40 DEG C anti-
Answer 3～8 hours, then through extracting, wash, being dried, precipitation, after rectification, obtain described 1-(4-chlorphenyl)-2-cyclopropyl-
1-acetone
The reaction equation of the present invention is as follows:
Due to the enforcement of above technical scheme, the present invention compared with prior art has the advantage that
The technique that the present invention uses is relatively easy, and raw material is easy to get, and operating process agents useful for same and cost of drugs are relatively low,
And reaction condition is gentle, the time is short, and yield is high, and cost is relatively low simultaneously, and the three wastes are less, and the content of target product is high, is well suited for
Industrialized production.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further details.Should be understood that these embodiments are for saying
The ultimate principle of the bright present invention, principal character and advantage, and the present invention is not limited by the following examples.Embodiment uses
Implementation condition can do adjustment further according to specific requirement, and not marked implementation condition is usually the condition in normal experiment.
Embodiment 1
(1) 35.05g (0.1mol) α-trimethylsiloxy group p-chlorobenzyl diethyl phosphonate is dissolved in 120mL N, N diformazan
In base Methanamide, add 8.0g (0.2mol) sodium hydroxide, be uniformly mixed, be slowly added dropwise 8.4g (0.1mol) cyclopropyl first
Base ketone, controlling temperature of reaction system is 25 DEG C, continuous stirring 6 hours, and reactant liquor toluene extracts, and obtains after drying, precipitation
26.46g pale yellow oily liquid body, i.e. the chloro-4-of 1-(2-cyclopropyl-1-trimethylsiloxy group propylene-1-base) benzene, purity
93.8%, yield 88.5%.
(2) finished product that will obtain in 23.92g (0.08mol) step (1), 50mL toluene and the hydrochloric acid of 50mL15%, in room
The lower stirring of temperature 5 hours, extracts with toluene, organic layer through washing, be dried, precipitation, after rectification, obtain 15.78g pale yellow oily liquid
Body, i.e. 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone, purity 97.8%, yield 92.5%.
1H NMR(400MHZ, CDCl3, TMS) and δ=7.45-7.6 (d, 2H), 7.80-7.95 (d, 2H), 2.80-3.00 (m,
1H), 1.25-1.27 (d, 3H), 0.93-1.01 (m, 1H), 0.20-0.55 (m, 4H).
Embodiment 2
(1) 29.25g (0.1mol) α-acetate p-chlorobenzyl dimethyl phosphonate is dissolved in 120mL N-Methyl pyrrolidone
In, add 10.8g (0.2mol) Feldalat NM, be uniformly mixed, be slowly added dropwise 16.8g (0.2mol) cyclopropyl methyl ketone, control
Temperature of reaction system processed is 20 DEG C, continuous stirring 5 hours, and reactant liquor toluene extracts, and obtains 24.16g light after drying, precipitation
The chloro-4-of yellow oily liquid, i.e. 1-(2-cyclopropyl-1-acetate propylene-1-base) benzene, purity 92.6%, yield 89.3%.
(2) finished product that will obtain in 21.64g (0.08mol) step (1), 50mL toluene and 100mL15% to toluene sulphur
Acid solution, is stirred at room temperature 8 hours, extracts with toluene, organic layer through washing, be dried, precipitation, after rectification, obtain 15.80g
Pale yellow oily liquid body, i.e. 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone, purity 98.2%, yield 93.0%.
Embodiment 3
(1) 32.85g (0.1mol) Alpha-Methyl sulfonyl p-chlorobenzyl dimethyl phosphonate is dissolved in 120mL toluene solution,
Add 11.2g (0.2mol) potassium hydroxide, be uniformly mixed, be slowly added dropwise 12.6g (0.15mol) cyclopropyl methyl ketone, control
Temperature of reaction system processed is 20 DEG C, continuous stirring 6 hours, and reactant liquor toluene extracts, and obtains 27.85g yellowish after drying, precipitation
The chloro-4-of color oily liquids, i.e. 1-(2-cyclopropyl-1-methyl sulphonyl propylene-1-base) benzene, purity 93.1%, yield 90.5%.
(2) finished product that will obtain in 24.62g (0.08mol) step (1), 50mL toluene and the phosphoric acid of 50mL15%, in room
The lower stirring of temperature 7 hours, extracts with toluene, organic layer through washing, be dried, precipitation, after rectification, obtain 15.89g pale yellow oily liquid
Body, i.e. 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone, purity 96.9%, yield 92.3%.
Embodiment 4
(1) 35.05g (0.1mol) α-trimethylsiloxy group p-chlorobenzyl diethyl phosphonate is dissolved in 120mL dimethyl sub-
In sulfolane solution, add 10.0g (0.25mol) Sodamide., be uniformly mixed, be slowly added dropwise 12.6g (0.15mol) cyclopropyl first
Base ketone, controlling temperature of reaction system is 30 DEG C, continuous stirring 3 hours, and reactant liquor toluene extracts, and obtains after drying, precipitation
27.04g pale yellow oily liquid body, i.e. the chloro-4-of 1-(2-cyclopropyl-1-trimethylsiloxy group propylene-1-base) benzene, purity
94.1%, yield 90.7%.
(2) finished product that will obtain in 23.92g (0.08mol) step (1), 50mL dimethyl sulfoxide and the sulfur of 80mL15%
Acid, is stirred at room temperature 6 hours, extracts with toluene, organic layer through washing, be dried, precipitation, after rectification, obtain 15.64g yellowish
Color oily liquids, i.e. 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone, purity 98.0%, yield 91.9%.
Above-described embodiment simply for technology design and the feature of the present invention are described, its object is to allow and is familiar with technique
People will appreciate that present disclosure and implements according to this, can not limit the scope of the invention with this, all according to the present invention
The equivalence that spirit is made changes or modifies, and all should contain within protection scope of the present invention.
Claims (10)
1. the preparation method of 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone, it is characterised in that: described preparation method bag
Include the following steps carried out successively:
Step (1), by compounds I and cyclopropyl methyl ketone, in the presence of alkali and organic solvent, react at 0～30 DEG C
To compound ii；
Step (2), make compound ii hydrolyze in the presence of acid, obtain compound III, i.e. 1-(4-chlorphenyl)-2-cyclopropyl-
1-acetone；
Wherein: the structural formula of described compounds I is:The structural formula of described compound ii is:The structural formula of described compound III is:R1, acetyl silica-based for trimethyl
Any one in base, methyl sulphonyl；R2It is methyl or ethyl.
The preparation method of 1-the most according to claim 1 (4-chlorphenyl)-2-cyclopropyl-1-acetone, it is characterised in that: step
Suddenly in (1), molar ratio 1.0:0.8～2.0:1.0～3.0 of described compounds I, cyclopropyl methyl ketone and alkali.
The preparation method of 1-the most according to claim 1 (4-chlorphenyl)-2-cyclopropyl-1-acetone, it is characterised in that: step
Suddenly, in (1), described alkali is one or more in sodium hydroxide, potassium hydroxide, Feldalat NM, Sodamide..
The preparation method of 1-the most according to claim 1 (4-chlorphenyl)-2-cyclopropyl-1-acetone, it is characterised in that: step
Suddenly, in (1), described organic solvent is selected from DMF, N-Methyl pyrrolidone, dimethyl sulfoxide, benzene, first
One or more in benzene, oxolane, dioxane.
The preparation method of 1-the most according to claim 1 (4-chlorphenyl)-2-cyclopropyl-1-acetone, it is characterised in that: step
Suddenly, in (1), described reaction temperature is 20～30 DEG C.
The preparation method of 1-the most according to any one of claim 1 to 5 (4-chlorphenyl)-2-cyclopropyl-1-acetone, its
It is characterised by: step (1) method particularly includes: described compounds I is dissolved in described organic solvent, described in addition
Alkali, is uniformly mixed, and is slowly added dropwise described cyclopropyl methyl ketone, controls the reaction temperature of reaction system, continuous stirring 2～
6 hours, reactant liquor through extraction, be dried, obtain described compound ii after precipitation.
The preparation method of 1-the most according to claim 1 (4-chlorphenyl)-2-cyclopropyl-1-acetone, it is characterised in that: step
Suddenly, in (2), the molar ratio of described compound ii and described acid is 1.0:1.0～3.0.
The preparation method of 1-the most according to claim 1 (4-chlorphenyl)-2-cyclopropyl-1-acetone, it is characterised in that: step
Suddenly in (2), one or more in hydrochloric acid, sulphuric acid, phosphoric acid, p-methyl benzenesulfonic acid, phosphotungstic acid of described acid.
The preparation method of 1-the most according to claim 1 (4-chlorphenyl)-2-cyclopropyl-1-acetone, it is characterised in that: step
Suddenly in (2), described compound ii is hydrolyzed the most in presence of organic solvent, and described organic solvent is toluene.
10. according to the preparation side of 1-(4-the chlorphenyl)-2-cyclopropyl-1-acetone according to any one of claim 1,7 to 9
Method, it is characterised in that: step (2) method particularly includes: by described compound ii, organic solvent and acid at 0～40 DEG C anti-
Answer 3～8 hours, then through extracting, wash, being dried, precipitation, after rectification, obtain described 1-(4-chlorphenyl)-2-cyclopropyl-
1-acetone.
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| CN201610671264.9A CN106316808A (en) | 2016-08-16 | 2016-08-16 | Preparation method of 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883266A (en) * | 2017-01-23 | 2017-06-23 | 江苏七洲绿色化工股份有限公司 | A kind of 1（4 chlorphenyls）The Preparation Method And Their Intermediate of the acetone of 2 cyclopropyl 1 |
| CN108530283A (en) * | 2018-06-01 | 2018-09-14 | 山东潍坊润丰化工股份有限公司 | A kind of 1-（4- chlorphenyls）The synthetic method of -2- cyclopropyl -1- acetone |
| CN108610246A (en) * | 2018-06-01 | 2018-10-02 | 山东潍坊润丰化工股份有限公司 | A kind of Cyproconazole intermediate 1-（4- chlorphenyls）The preparation method of -2- cyclopropyl -1- acetone |
| CN113121322A (en) * | 2019-12-30 | 2021-07-16 | 辽宁众辉生物科技有限公司 | Synthesis method of 1- (4-chlorphenyl) -2-cyclopropyl-1-acetone |
| CN114195625A (en) * | 2021-11-30 | 2022-03-18 | 江苏剑牌农化股份有限公司 | Preparation method of 1- (4-chlorphenyl) -2-cyclopropyl-1-acetone |
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| CN102249882A (en) * | 2011-06-02 | 2011-11-23 | 永农生物科学有限公司 | Method for preparing 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone |
| CN102942465A (en) * | 2012-11-22 | 2013-02-27 | 江苏澄扬作物科技有限公司 | Preparation method and intermediate of 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone |
| JP2015030699A (en) * | 2013-08-02 | 2015-02-16 | マナック株式会社 | Oxidative debenzylation reaction of benzyl amine and benzyl ether using alkali metal halide |
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| CN102249882A (en) * | 2011-06-02 | 2011-11-23 | 永农生物科学有限公司 | Method for preparing 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone |
| CN102942465A (en) * | 2012-11-22 | 2013-02-27 | 江苏澄扬作物科技有限公司 | Preparation method and intermediate of 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883266A (en) * | 2017-01-23 | 2017-06-23 | 江苏七洲绿色化工股份有限公司 | A kind of 1（4 chlorphenyls）The Preparation Method And Their Intermediate of the acetone of 2 cyclopropyl 1 |
| CN106883266B (en) * | 2017-01-23 | 2020-03-17 | 江苏七洲绿色化工股份有限公司 | Preparation method of 1- (4-chlorphenyl) -2-cyclopropyl-1-acetone and intermediate thereof |
| CN108530283A (en) * | 2018-06-01 | 2018-09-14 | 山东潍坊润丰化工股份有限公司 | A kind of 1-（4- chlorphenyls）The synthetic method of -2- cyclopropyl -1- acetone |
| CN108610246A (en) * | 2018-06-01 | 2018-10-02 | 山东潍坊润丰化工股份有限公司 | A kind of Cyproconazole intermediate 1-（4- chlorphenyls）The preparation method of -2- cyclopropyl -1- acetone |
| CN113121322A (en) * | 2019-12-30 | 2021-07-16 | 辽宁众辉生物科技有限公司 | Synthesis method of 1- (4-chlorphenyl) -2-cyclopropyl-1-acetone |
| CN114195625A (en) * | 2021-11-30 | 2022-03-18 | 江苏剑牌农化股份有限公司 | Preparation method of 1- (4-chlorphenyl) -2-cyclopropyl-1-acetone |
| CN114195625B (en) * | 2021-11-30 | 2023-12-01 | 江苏剑牌农化股份有限公司 | Preparation method of 1- (4-chlorophenyl) -2-cyclopropyl-1-acetone |
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