CN102584551A - 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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- CN102584551A CN102584551A CN2012100236706A CN201210023670A CN102584551A CN 102584551 A CN102584551 A CN 102584551A CN 2012100236706 A CN2012100236706 A CN 2012100236706A CN 201210023670 A CN201210023670 A CN 201210023670A CN 102584551 A CN102584551 A CN 102584551A
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- pinacolone
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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 the compound method of a kind of triazolone midbody 1-(4-chloro phenoxy)-1-chloro Pinacolone.
Background technology
Triazolone is the systemic fungicide of a kind of efficient, low toxicity, low residue, wide spectrum, and rust, the Powdery Mildew of crops such as wheat class, vegetables, fruit tree had special control effect.
At present, the production process route of triazolone is: make 1-(4-chloro phenoxy) Pinacolone with a chlorine Pinacolone and para-chlorophenol condensation earlier; Make 1-(4-chloro phenoxy)-1-chloro Pinacolone with the sulfuryl chloride chlorination then; With 1,2, the 4-triazole is synthesized triazolone again.
Existing 1-(4-chloro phenoxy) Pinacolone chlorination method adopts sulfuryl chloride as chlorizating agent, and its reaction principle is:
Produce a large amount of sulfurous gas and hydrogen chloride emission in its reaction process, environment is caused certain pollution.At present, to treatment of waste gas, general first water absorbs by-product hydrochloric acid (wherein contain the sulfurous acid about 10%, selling price is lower), absorbs with alkali then and removes sulfurous gas, and the off gas treatment cost is higher.And manufacturing condition is had relatively high expectations, and the product yield also awaits further raising.
Summary of the invention
For overcoming the weak point of prior art; The present invention provides a kind of and replaces the compound method of sulfuryl chloride as triazolone midbody 1-(4-chloro the phenoxy)-1-chloro Pinacolone of chlorizating agent with chlorine, to reduce environmental pollution, improve the product yield, to reduce production costs.
The technical solution adopted for the present invention to solve the technical problems is: 1-(4-chloro phenoxy) Pinacolone is dissolved in the inert solvent, feeds chlorizating agent chlorine then, make 1-(4-chloro phenoxy)-1-chloro Pinacolone; Produce hydrogen chloride emission in the reaction process, absorb by-product hydrochloric acid through water.
The chlorination chemical principle of 1-(4-chloro phenoxy) Pinacolone and chlorine is:
Further, the mol ratio of 1-(4-chloro phenoxy) Pinacolone and chlorine is 1:1～1.3.
Further, said chlorine at the uniform velocity feeds, and the feeding time is 3～9h.
Further, being reflected under-10 ℃～95 ℃ the temperature of 1-(4-chloro phenoxy) Pinacolone and chlorine carried out; Further, be under 0 ℃～60 ℃ temperature, to carry out.
Beneficial effect of the present invention is, because employing chlorine replaces sulfuryl chloride operation chlorizating agent of the prior art, thereby does not produce sulfurous gas in process of production; Reduced pollution to environment; Waste gas absorbs byproduct hydrochloric acid and has improved selling price because of not containing sulfurous acid, has optimized manufacturing condition simultaneously, has improved the product yield; Reduce production cost effectively, had favorable economic benefit, social benefit and environmental benefit.
Embodiment
Below in conjunction with embodiment the present invention is specified further.
Embodiment 1:
680g toluene and 582g (folding hundred) 1-(4-chloro phenoxy) Pinacolone are added in the chlorination tank, stir, 1-(4-chloro phenoxy) Pinacolone is dissolved in the toluene; Feed 185g chlorine then evenly, the time of leading to of chlorine is 3 hours, and temperature of reaction is controlled at 30～40 ℃; After logical chlorine finishes, continue to stir, be incubated, measure some reaction of 1-(4-chloro phenoxy) Pinacolone content≤0.5% and finish; The chlorinated exhaust that reaction produces-hydrogenchloride water absorbs by-product hydrochloric acid; Add 800g water again, stir, leave standstill, isolated liquid spent acid is used for 1-(4-chloro phenoxy) Pinacolone secondary stratification, again to the material dehydration that heats up; Material after the dehydration changes crystallization kettle over to, and cooling is crossed and to be filtered that purity is 97%, 1-(4-chloro phenoxy)-1-chloro Pinacolone finished product of 686g; The product yield is 97%.
Embodiment 2:
720g chlorobenzene and 582g (folding hundred) 1-(4-chloro phenoxy) Pinacolone are added in the chlorination tank, stir, 1-(4-chloro phenoxy) Pinacolone is dissolved in the toluene; Feed 200g chlorine then evenly, the time of leading to of chlorine is 6 hours, and temperature of reaction is controlled at 30～40 ℃; After logical chlorine finishes, continue to stir, be incubated, measure some reaction of 1-(4-chloro phenoxy) Pinacolone content≤0.5% and finish; The chlorinated exhaust that reaction produces-hydrogenchloride water absorbs by-product hydrochloric acid; Add 800g water again, stir, leave standstill, isolated liquid spent acid is used for 1-(4-chloro phenoxy) Pinacolone secondary stratification, again to the material dehydration that heats up; Material after the dehydration changes crystallization kettle over to, and cooling is crossed and to be filtered that purity is 98%, 1-(4-chloro phenoxy)-1-chloro Pinacolone finished product of 679g; The product yield is 97%.
Embodiment 3:
700g propyl ether and 582g (folding hundred) 1-(4-chloro phenoxy) Pinacolone are added in the chlorination tank, stir, 1-(4-chloro phenoxy) Pinacolone is dissolved in the toluene; Feed 220g chlorine then evenly, the time of leading to of chlorine is 4 hours, and temperature of reaction is controlled at 30～40 ℃; After logical chlorine finishes, continue to stir, be incubated, measure some reaction of 1-(4-chloro phenoxy) Pinacolone content≤0.5% and finish; The chlorinated exhaust that reaction produces-hydrogenchloride water absorbs by-product hydrochloric acid; Add 800g water again, stir, leave standstill, isolated liquid spent acid is used for 1-(4-chloro phenoxy) Pinacolone secondary stratification, again to the material dehydration that heats up; Material after the dehydration changes crystallization kettle over to, and cooling is crossed and to be filtered that purity is 97%, 1-(4-chloro phenoxy)-1-chloro Pinacolone finished product of 690g; The product yield is 97.5%.
Embodiment 4:
700g cyclohexane and 582g (folding hundred) 1-(4-chloro phenoxy) Pinacolone are added in the chlorination tank, stir, 1-(4-chloro phenoxy) Pinacolone is dissolved in the toluene; Feed 235g chlorine then evenly, the time of leading to of chlorine is 9 hours, and temperature of reaction is controlled at 50～60 ℃; After logical chlorine finishes, continue to stir, be incubated, measure some reaction of 1-(4-chloro phenoxy) Pinacolone content≤0.5% and finish; The chlorinated exhaust that reaction produces-hydrogenchloride water absorbs by-product hydrochloric acid; Add 800g water again, stir, leave standstill, isolated liquid spent acid is used for 1-(4-chloro phenoxy) Pinacolone secondary stratification, again to the material dehydration that heats up; Material after the dehydration changes crystallization kettle over to, and cooling is crossed and to be filtered that purity is 97.5%, 1-(4-chloro phenoxy)-1-chloro Pinacolone finished product of 683g; The product yield is 97%.
Embodiment 5:
690g YLENE and 582g (folding hundred) 1-(4-chloro phenoxy) Pinacolone are added in the chlorination tank, stir, 1-(4-chloro phenoxy) Pinacolone is dissolved in the toluene; Feed 215g chlorine then evenly, the time of leading to of chlorine is 3 hours, and temperature of reaction is controlled at 85～95 ℃; After logical chlorine finishes, continue to stir, be incubated, measure some reaction of 1-(4-chloro phenoxy) Pinacolone content≤0.5% and finish; The chlorinated exhaust that reaction produces-hydrogenchloride water absorbs by-product hydrochloric acid; Add 800g water again, stir, leave standstill, isolated liquid spent acid is used for 1-(4-chloro phenoxy) Pinacolone secondary stratification, again to the material dehydration that heats up; Material after the dehydration changes crystallization kettle over to, and cooling is crossed and to be filtered that purity is 98%, 1-(4-chloro phenoxy)-1-chloro Pinacolone finished product of 680g; The product yield is 97%.
Claims (5)
1. the compound method of a triazolone midbody 1-(4-chloro phenoxy)-1-chloro Pinacolone; 1-(4-chloro phenoxy) Pinacolone is dissolved in the inert solvent; It is characterized in that: as chlorizating agent, make 1-(4-chloro phenoxy)-1-chloro Pinacolone with chlorine; Produce hydrogen chloride emission in the reaction process, absorb by-product hydrochloric acid through water.
2. the compound method of 1 described a kind of triazolone midbody 1-(4-chloro phenoxy)-1-chloro Pinacolone as requested, it is characterized in that: the mol ratio of 1-(4-chloro phenoxy) Pinacolone and chlorine is 1:1～1.3.
3. the compound method of 1 described a kind of triazolone midbody 1-(4-chloro phenoxy)-1-chloro Pinacolone as requested, it is characterized in that: said chlorine at the uniform velocity feeds, and the feeding time is 3～9h.
4. the compound method of 1 described a kind of triazolone midbody 1-(4-chloro phenoxy)-1-chloro Pinacolone as requested, it is characterized in that: the chlorination reaction of 1-(4-chloro phenoxy) Pinacolone and chlorine is carried out under-10 ℃～95 ℃ temperature.
5. the compound method of 1 described a kind of triazolone midbody 1-(4-chloro phenoxy)-1-chloro Pinacolone as requested, it is characterized in that: the chlorination reaction of 1-(4-chloro phenoxy) Pinacolone and chlorine is carried out under 0 ℃～60 ℃ temperature.
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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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| CN102584551B CN102584551B (en) | 2014-12-17 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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2012
- 2012-02-03 CN CN201210023670.6A patent/CN102584551B/en active Active
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 |
|---|
| 陈宗化 等: "粉锈宁合成工艺综述", 《广东科技》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| CN102584551B (en) | 2014-12-17 |
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