CN102584551B - Synthetic method of triazolone intermediate 1-(4-chlorinated phenoxyl)-1-chlorinated pinacoline - Google Patents
Synthetic method of triazolone intermediate 1-(4-chlorinated phenoxyl)-1-chlorinated pinacoline Download PDFInfo
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- CN102584551B CN102584551B CN201210023670.6A CN201210023670A CN102584551B CN 102584551 B CN102584551 B CN 102584551B CN 201210023670 A CN201210023670 A CN 201210023670A CN 102584551 B CN102584551 B CN 102584551B
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Abstract
The invention provides a synthetic method of triazolone intermediate 1-(4-chlorinated phenoxyl)-1-chlorinated pinacoline. 1-(4-chlorinated phenoxyl) pinacoline is dissolved in an inert solvent, then chlorating agent chlorine gas is led in at a temperature of 10 DEG C below zero to 95 DEG C to obtain 1-(4-chlorinated phenoxyl)-1-chlorinated pinacoline, hydrogen chloride waste gas is produced during the reaction process, and by-product hydrochloric acid is absorbed by water. The molar ratio of 1-(4-chlorinated phenoxyl) pinacoline to chlorine gas is 1 : (1 to 1.3). Chlorine gas is adopted to replace a sulfuryl chloride chlorinating agent in the prior art, no sulfur dioxide is produced in the production process, the pollution to environment is reduced, the sale price is raised since sulfurous acid is not contained in by-product hydrochloric acid absorbed by waste gas, meanwhile the condition of the production process is optimized, the product yield is improved, and the production cost is effectively lowered. Therefore, the invention has good economic benefits, social benefits and environmental benefits.
Description
Technical field
The present invention relates to a kind of preparation method of chemical intermediate, specifically, relate to a kind of triazolone intermediate 1-(4-chloro phenoxy group) synthetic method of-1-chloro Pinacolone.
Background technology
Triazolone is a kind of systemic fungicide of efficient, low toxicity, low residue, wide spectrum, has special prevention effect to the rust of the crops such as wheat class, vegetables, fruit tree, Powdery Mildew.
At present, the production process route of triazolone is: first obtain 1-(4-chloro phenoxy group with a chlorine Pinacolone and para-chlorophenol condensation) Pinacolone; Then 1-(4-chloro phenoxy group is obtained with sulfuryl chloride chlorination)-1-chloro Pinacolone; Triazolone is synthesized again with 1,2,4-triazole.
Existing 1-(4-chloro phenoxy group) Pinacolone chlorination method, adopt sulfuryl chloride as chlorizating agent, its reaction principle is:
Produce a large amount of sulfurous gas and hydrogen chloride emission in its reaction process, certain pollution is caused to environment.At present, to the process of waste gas, generally first absorb by-product hydrochloric acid (wherein contain the sulfurous acid of about 10%, selling price is lower) with water, then remove sulfurous gas with Alkali absorption, off gas treatment cost is higher.Further, manufacturing condition requires higher, and product yield also awaits further raising.
Summary of the invention
For overcoming the deficiencies in the prior art part, the invention provides a kind of chlorine and replace sulfuryl chloride as the triazolone intermediate 1-(4-chloro phenoxy group of chlorizating agent) synthetic method of-1-chloro Pinacolone, to reduce environmental pollution, carry high product yield, to reduce production cost.
The technical solution adopted for the present invention to solve the technical problems is: by 1-(4-chloro phenoxy group) Pinacolone is dissolved in inert solvent, then passes into chlorizating agent chlorine, obtained 1-(4-chloro phenoxy group)-1-chloro Pinacolone; Produce hydrogen chloride emission in reaction process, absorb by-product hydrochloric acid through water.
1-(4-chloro phenoxy group) the chlorination chemical principle of Pinacolone and chlorine is:
Further, 1-(4-chloro phenoxy group) mol ratio of Pinacolone and chlorine is 1:1 ~ 1.3.
Further, described chlorine at the uniform velocity passes into, and the time of passing into is 3 ~ 9h.
Further, 1-(4-chloro phenoxy group) reaction of Pinacolone and chlorine carries out at the temperature of-10 DEG C ~ 95 DEG C; Further, be carry out at the temperature of 0 DEG C ~ 60 DEG C.
Beneficial effect of the present invention is, sulfuryl chloride operation chlorizating agent of the prior art is replaced owing to adopting chlorine, thus sulfurous gas is not produced in process of production, decrease the pollution to environment, the hydrochloric acid of waste gas absorption by-product, because not improve selling price containing sulfurous acid, optimizes manufacturing condition simultaneously, improves product yield, significantly reduce production cost, there is good economic benefit, social benefit and environmental benefit.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail further.
Embodiment 1:
By 680g toluene and 582g(folding hundred) 1-(4-chloro phenoxy group) Pinacolone adds in chlorination tank, stir, make 1-(4-chloro phenoxy group) Pinacolone is dissolved in toluene; Then pass into 185g chlorine evenly, chlorine to lead to the time be 3 hours, and temperature of reaction to be controlled at 30 ~ 40 DEG C; After logical chlorine terminates, continue to stir, insulation, measure 1-(4-chloro phenoxy group) Pinacolone content≤0.5% time reaction terminate; Chlorinated exhaust-hydrogenchloride water that reaction produces absorbs by-product hydrochloric acid; Add 800g water again, stir, leave standstill, isolated liquid spent acid is used for 1-(4-chloro phenoxy group) Pinacolone secondary stratification, then intensification dehydration is carried out to material; Material after dehydration proceeds to crystallization kettle, cooling, filter purity be 97%, the 1-(4-chloro phenoxy group of 686g)-1-chloro Pinacolone finished product; Product yield is 97%.
Embodiment 2:
By 720g chlorobenzene and 582g(folding hundred) 1-(4-chloro phenoxy group) Pinacolone adds in chlorination tank, stir, make 1-(4-chloro phenoxy group) Pinacolone is dissolved in toluene; Then pass into 200g chlorine evenly, chlorine to lead to the time be 6 hours, and temperature of reaction to be controlled at 30 ~ 40 DEG C; After logical chlorine terminates, continue to stir, insulation, measure 1-(4-chloro phenoxy group) Pinacolone content≤0.5% time reaction terminate; Chlorinated exhaust-hydrogenchloride water that reaction produces absorbs by-product hydrochloric acid; Add 800g water again, stir, leave standstill, isolated liquid spent acid is used for 1-(4-chloro phenoxy group) Pinacolone secondary stratification, then intensification dehydration is carried out to material; Material after dehydration proceeds to crystallization kettle, cooling, filter purity be 98%, the 1-(4-chloro phenoxy group of 679g)-1-chloro Pinacolone finished product; Product yield is 97%.
Embodiment 3:
By 700g propyl ether and 582g(folding hundred) 1-(4-chloro phenoxy group) Pinacolone adds in chlorination tank, stir, make 1-(4-chloro phenoxy group) Pinacolone is dissolved in toluene; Then pass into 220g chlorine evenly, chlorine to lead to the time be 4 hours, and temperature of reaction to be controlled at 30 ~ 40 DEG C; After logical chlorine terminates, continue to stir, insulation, measure 1-(4-chloro phenoxy group) Pinacolone content≤0.5% time reaction terminate; Chlorinated exhaust-hydrogenchloride water that reaction produces absorbs by-product hydrochloric acid; Add 800g water again, stir, leave standstill, isolated liquid spent acid is used for 1-(4-chloro phenoxy group) Pinacolone secondary stratification, then intensification dehydration is carried out to material; Material after dehydration proceeds to crystallization kettle, cooling, filter purity be 97%, the 1-(4-chloro phenoxy group of 690g)-1-chloro Pinacolone finished product; Product yield is 97.5%.
Embodiment 4:
By 700g cyclohexane and 582g(folding hundred) 1-(4-chloro phenoxy group) Pinacolone adds in chlorination tank, stir, make 1-(4-chloro phenoxy group) Pinacolone is dissolved in toluene; Then pass into 235g chlorine evenly, chlorine to lead to the time be 9 hours, and temperature of reaction to be controlled at 50 ~ 60 DEG C; After logical chlorine terminates, continue to stir, insulation, measure 1-(4-chloro phenoxy group) Pinacolone content≤0.5% time reaction terminate; Chlorinated exhaust-hydrogenchloride water that reaction produces absorbs by-product hydrochloric acid; Add 800g water again, stir, leave standstill, isolated liquid spent acid is used for 1-(4-chloro phenoxy group) Pinacolone secondary stratification, then intensification dehydration is carried out to material; Material after dehydration proceeds to crystallization kettle, cooling, filter purity be 97.5%, the 1-(4-chloro phenoxy group of 683g)-1-chloro Pinacolone finished product; Product yield is 97%.
Embodiment 5:
By 690g dimethylbenzene and 582g(folding hundred) 1-(4-chloro phenoxy group) Pinacolone adds in chlorination tank, stir, make 1-(4-chloro phenoxy group) Pinacolone is dissolved in toluene; Then pass into 215g chlorine evenly, chlorine to lead to the time be 3 hours, and temperature of reaction to be controlled at 85 ~ 95 DEG C; After logical chlorine terminates, continue to stir, insulation, measure 1-(4-chloro phenoxy group) Pinacolone content≤0.5% time reaction terminate; Chlorinated exhaust-hydrogenchloride water that reaction produces absorbs by-product hydrochloric acid; Add 800g water again, stir, leave standstill, isolated liquid spent acid is used for 1-(4-chloro phenoxy group) Pinacolone secondary stratification, then intensification dehydration is carried out to material; Material after dehydration proceeds to crystallization kettle, cooling, filter purity be 98%, the 1-(4-chloro phenoxy group of 680g)-1-chloro Pinacolone finished product; Product yield is 97%.
Claims (2)
1. a triazolone intermediate 1-(4-chloro phenoxy group) synthetic method of-1-chloro Pinacolone, by 1-(4-chloro phenoxy group) Pinacolone is dissolved in inert solvent, it is characterized in that: using chlorine as chlorizating agent, 1-(4-chloro phenoxy group) mol ratio of Pinacolone and chlorine is 1:1 ~ 1.3, chlorine at the uniform velocity passes into, the time of passing into is 3 ~ 9h, 1-(4-chloro phenoxy group) Pinacolone and chlorine carries out chlorination reaction, obtained 1-(4-chloro phenoxy group at the temperature of-10 DEG C ~ 95 DEG C)-1-chloro Pinacolone; Produce hydrogen chloride emission in reaction process, absorb by-product hydrochloric acid through water.
2. a kind of triazolone intermediate 1-(4-chloro phenoxy group as requested described in 1) synthetic method of-1-chloro Pinacolone, it is characterized in that: 1-(4-chloro phenoxy group) chlorination reaction of Pinacolone and chlorine carries out at the temperature of 0 DEG C ~ 60 DEG C.
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| CN201210023670.6A CN102584551B (en) | 2012-02-03 | 2012-02-03 | Synthetic method of triazolone intermediate 1-(4-chlorinated phenoxyl)-1-chlorinated pinacoline |
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| CN201210023670.6A CN102584551B (en) | 2012-02-03 | 2012-02-03 | Synthetic method of triazolone intermediate 1-(4-chlorinated phenoxyl)-1-chlorinated pinacoline |
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| CN108586220A (en) * | 2018-06-27 | 2018-09-28 | 安徽国星生物化学有限公司 | A kind of synthetic method of the chloro- 1- of 2- (1- chlorine cyclopropyl) ethyl ketone |
| CN112047825A (en) * | 2020-09-16 | 2020-12-08 | 南通鸿富达利化工有限公司 | Production process of dichloro pinacolone |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1447954A (en) * | 1974-01-15 | 1976-09-02 | Bayer Ag | Process for the preparation of 1,2,4-triazole derivative |
| US4339612A (en) * | 1980-03-05 | 1982-07-13 | Bayer Aktiengesellschaft | Preparation of 3,3-dimethyl-1-phenoxy-butan-2-ols as fungicide intermediates |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1447954A (en) * | 1974-01-15 | 1976-09-02 | Bayer Ag | Process for the preparation of 1,2,4-triazole derivative |
| US4339612A (en) * | 1980-03-05 | 1982-07-13 | Bayer Aktiengesellschaft | Preparation of 3,3-dimethyl-1-phenoxy-butan-2-ols as fungicide intermediates |
Non-Patent Citations (1)
| Title |
|---|
| 粉锈宁合成工艺综述;陈宗化 等;《广东科技》;20110430(第8期);第52-53页 * |
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