CN101307016B - Method for synthesizing 2,6-diisopropyl-4-phenoxy phenylthiourea - Google Patents
Method for synthesizing 2,6-diisopropyl-4-phenoxy phenylthiourea Download PDFInfo
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- CN101307016B CN101307016B CN200810123555XA CN200810123555A CN101307016B CN 101307016 B CN101307016 B CN 101307016B CN 200810123555X A CN200810123555X A CN 200810123555XA CN 200810123555 A CN200810123555 A CN 200810123555A CN 101307016 B CN101307016 B CN 101307016B
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Abstract
The invention provides a method for synthesizing 2, 6-diisopropyl-4-pheonxy phenylthioureal, relating to a process for synthesizing an intermediate of an agriculture insecticide acaricide diafenthiuron. The 2,6-diisopropylaniline has reactions of bromination, etherification and sulfocarbamide in the action of catalysts of 8-copper quinolinate and Dimethylamino pyridine to generate the 2, 6-diisopropyl-4-pheonxy phenylthioureal. The method adopts the continuous reaction and takes the 8-copper quinolinate and the Dimethylamino pyridine as catalysts; the temperature of the etherification reaction is reduced to about 115 DEG C from 150 DEG C; meanwhile, the method adopts one solvent, integrates the three steps of bromination, etherification and sulfocarbamide into one, generates the product directly without the separation, reduces the generation of waste water, has positive significance on the practical production, reaction yield coefficient more than 83 percent and the content up to97 percent, improves the production efficiency and has practical significance on lowering the production cost effectively.
Description
Technical field
The present invention relates to the synthesis technique of the intermediate of agricultural insecticidal miticide butyl ether urea.
Background technology
2,6-di-isopropyl-4-phenoxy phenylthiourea is the insecticidal/acaricidal agent of Switzerland vapour Ba-Jia Ji company exploitation, be widely used on cotton, fruit, vegetables and the tealeaves, 2 of existing bibliographical information, big, the temperature of reaction of wastewater flow rate long, that the produce synthetic method reaction time of 6-di-isopropyl-4-phenoxy phenylthiourea is high at 150 ℃, power consumption, and yield is only about 77%, and the production cost height is unfavorable for that large-scale popularization uses.
Summary of the invention
The object of the invention is to invent a kind of 2 of reaction yield, reduction temperature of reaction, a kind of method of 6-di-isopropyl-4-phenoxy phenylthiourea of improving.
Under the effect of catalyzer copper 8-quinolinolate and Dimethylamino pyridine, with 2, the 6-diisopropyl aniline generates 2,6-di-isopropyl-4-phenoxy phenylthiourea continuously through bromination, etherificate, thiocarbamide reaction.
Concrete grammar may further comprise the steps:
1) with 2,6-diisopropyl aniline and solvent place reaction vessel, drip bromine, and control reaction temperature is 0～-10 ℃, to the reaction end; Described solvent is toluene or dimethylbenzene;
2) under the effect of catalyzer copper 8-quinolinolate and Dimethylamino pyridine, liquid caustic soda, phenol are added reaction vessel, be warming up to reflux temperature, remove the water that steams, back flow reaction is to finishing under 115 ± 5 ℃ of temperature condition;
3) the reaction vessel temperature is reduced to 80～90 ℃, add Sodium Thiocyanate 99, hydrochloric acid, 100 ± 5 ℃ of reactions are reduced to normal temperature to finishing, and add entry again, and are centrifugal, get filtration cakes torrefaction, make 2,6-di-isopropyl-4-phenoxy phenylthiourea.
Because the present invention adopts continuous reaction, adopt copper 8-quinolinolate and Dimethylamino pyridine to mix as catalyzer, etherification reaction temperature can drop to about 115 ℃ by 150 ℃, adopts single solvent simultaneously, and bromination, etherificate, three steps of thiocarbamideization are merged into one, without separation, directly obtain product, reduce the generation of waste water, actual production is had positive effect, reaction yield reaches more than 83% simultaneously, content reaches 97%, enhances productivity, and production cost is effectively reduced have practical significance.
Step 2 of the present invention) gross weight and 2 of catalyzer copper 8-quinolinolate and Dimethylamino pyridine in, the weight ratio of 6-di-isopropyl propylamine is 1: 50～120.As catalyst excess, strengthen reaction cost, catalytic amount is few, then extends the reaction times.
Wherein, the weight ratio of copper 8-quinolinolate and Dimethylamino pyridine is 3: 1～3.Adopting described ratio is to guarantee anhydrous response, and it is a small amount of further to reduce row.
In order to react thoroughly, no excessive or remain, the present invention 2, and the mol ratio of 6-diisopropyl aniline and bromine is 100: 101.
2, the mol ratio of 6-diisopropyl aniline and phenol is 1: 1.
2, the mol ratio of 6-diisopropyl aniline and Sodium Thiocyanate 99 is 1: 1.
Described liquid caustic soda is that concentration is 30% sodium hydroxide, 2, and the mol ratio of 6-diisopropyl aniline and liquid caustic soda is 1: 2.
The concentration of described hydrochloric acid is 30%, 2, and the mol ratio of 6-diisopropyl aniline and hydrochloric acid is 10: 11.
Embodiment
Embodiment 1:
At 1000ml stirring is housed, thermometer, in the reaction flask of reflux exchanger and dropping funnel, add 88.6g (0.5mol) 2, the 6-diisopropyl aniline, 300ml toluene, be controlled at-5 ℃, drip 81.5g (0.505mol) bromine, after insulation finishes, adding 135g (1mol) concentration is 30% sodium hydroxide, 47.5g (0.5mol) phenol, catalyzer (0.6g copper 8-quinolinolate, 0.2g Dimethylamino pyridine), temperature rising reflux, divide and to get the water that steams, 118 ℃ of back flow reaction are 10 hours then, slightly after 80 ℃, add 40.6g (0.5mol) Sodium Thiocyanate 99,66.8g (0.55mol) concentration is 30% hydrochloric acid, 100 ℃ were reacted 5 hours, cooling, and filtration obtains 141g, and (purity: 97%) product 2,6-di-isopropyl-4-phenoxy phenylthiourea (DIPPT), yield 83.3%.
Embodiment 2:
At 1000ml stirring is housed, thermometer, in the reaction flask of reflux exchanger and dropping funnel, add 88.6g (0.5mol) 2, the 6-diisopropyl aniline, 300ml toluene, be controlled at-10 ℃, drip 81.5g (0.505mol) bromine, after insulation finishes, adding 135g (1mol) concentration is 30% sodium hydroxide, 47.5g (0.5mol) phenol, catalyzer (0.6g copper 8-quinolinolate, 0.6g Dimethylamino pyridine), temperature rising reflux, divide and to get the water that steams, 110 ℃ of back flow reaction are 10 hours then, slightly after 90 ℃, add 40.6g (0.5mol) Sodium Thiocyanate 99,66.8g (0.55mol) concentration is 30% hydrochloric acid, 100 ℃ were reacted 5 hours, cooling, and filtration obtains 140g, and (purity: 98.0%) product 2,6-di-isopropyl-4-phenoxy phenylthiourea (DIPPT), yield 83.5%.
Embodiment 3:
At 1000ml stirring is housed, thermometer, in the reaction flask of reflux exchanger and dropping funnel, add 88.6g (0.5mol) 2, the 6-diisopropyl aniline, 350ml toluene, be controlled at-1 ℃, drip 81.5g (0.505mol) bromine, after insulation finishes, adding 148.5g (1.1mol) concentration is 30% sodium hydroxide, 52.2g (0.55mol) phenol, catalyzer (0.6g copper 8-quinolinolate, 0.4g Dimethylamino pyridine), temperature rising reflux, divide and to get the water that steams, 115 ℃ of back flow reaction are 10 hours then, slightly after 80 ℃, add 40.6g (0.5mol) Sodium Thiocyanate 99,66.8g (0.55mol) concentration is 30% hydrochloric acid, 100 ℃ were reacted 5 hours, cooling, and filtration obtains 143g, and (purity: 97.4%) product 2,6-di-isopropyl-4-phenoxy phenylthiourea (DIPPT), yield 84.8%.
Embodiment 4:
At 1000ml stirring is housed, thermometer, in the reaction flask of reflux exchanger and dropping funnel, add 88.6g (0.5mol) 2, the 6-diisopropyl aniline, 350ml dimethylbenzene, be controlled at-8 ℃, drip 81.5g (0.505mol) bromine, after insulation finishes, adding 148.5g (1.1mol) concentration is 30% sodium hydroxide, 52.2g (0.55mol) phenol, catalyzer (0.6g copper 8-quinolinolate, 0.4g Dimethylamino pyridine), temperature rising reflux, divide and to get the water that steams, 115 ± 5 ℃ of back flow reaction are 10 hours then, slightly after 90 ℃, add 40.6g (0.5mol) Sodium Thiocyanate 99,66.8g (0.55mol) concentration is 30% hydrochloric acid, 100 ℃ were reacted 5 hours, cooling, and filtration obtains 143g, and (purity: 97.4%) product 2,6-di-isopropyl-4-phenoxy phenylthiourea (DIPPT), yield 84.8%.
Claims (3)
1.2 the synthetic method of 6-di-isopropyl-4-phenoxy phenylthiourea is characterized in that may further comprise the steps:
1) with 2,6-diisopropyl aniline and solvent place reaction vessel, drip bromine, and control reaction temperature is 0～-10 ℃, to the reaction end; Described solvent is toluene or dimethylbenzene; Described 2, the mol ratio of 6-diisopropyl aniline and bromine is 100: 101;
2) under the effect of catalyzer copper 8-quinolinolate and Dimethylamino pyridine, liquid caustic soda, phenol are added reaction vessel, be warming up to reflux temperature, remove the water that steams, back flow reaction is to finishing under 115 ± 5 ℃ of temperature condition; The gross weight and 2 of described catalyzer copper 8-quinolinolate and Dimethylamino pyridine, the weight ratio of 6-di-isopropyl propylamine is 1: 50～120, the weight ratio of copper 8-quinolinolate and Dimethylamino pyridine is 3: 1～3; Described 2, the mol ratio of 6-diisopropyl aniline and phenol is 1: 1;
3) the reaction vessel temperature is reduced to 80～90 ℃, add Sodium Thiocyanate 99, hydrochloric acid, 100 ± 5 ℃ of reactions are reduced to normal temperature to finishing, and add entry again, and are centrifugal, get filtration cakes torrefaction, make 2,6-di-isopropyl-4-phenoxy phenylthiourea; Described 2, the mol ratio of 6-diisopropyl aniline and Sodium Thiocyanate 99 is 1: 1.
2. described 2 according to claim 1, the synthetic method of 6-di-isopropyl-4-phenoxy phenylthiourea is characterized in that described liquid caustic soda is that concentration is 30% sodium hydroxide, 2, and the mol ratio of 6-diisopropyl aniline and liquid caustic soda is 1: 2.
3. described 2 according to claim 1, the synthetic method of 6-di-isopropyl-4-phenoxy phenylthiourea, the concentration that it is characterized in that described hydrochloric acid is 30%, 2, the mol ratio of 6-diisopropyl aniline and hydrochloric acid is 10: 11.
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| CN200810123555XA CN101307016B (en) | 2008-07-08 | 2008-07-08 | Method for synthesizing 2,6-diisopropyl-4-phenoxy phenylthiourea |
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| CN200810123555XA CN101307016B (en) | 2008-07-08 | 2008-07-08 | Method for synthesizing 2,6-diisopropyl-4-phenoxy phenylthiourea |
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| CN101307016B true CN101307016B (en) | 2011-05-11 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103724213B (en) * | 2014-01-04 | 2015-08-12 | 新发药业有限公司 | A kind of synthetic method of 2,6-di-isopropyl-4-phenoxybenzamine |
| CN113200866A (en) * | 2021-03-29 | 2021-08-03 | 龙曦宁（上海）医药科技有限公司 | Synthetic method of diafenthiuron impurity D |
| CN113651705A (en) * | 2021-08-26 | 2021-11-16 | 襄阳金达成精细化工有限公司 | 4-phenoxy-2, 6-diisopropylaniline intermediate and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0347380A1 (en) * | 1988-06-14 | 1989-12-20 | Ciba-Geigy Ag | Process for the preparation of 4-Bromoaniline-hydrobromide |
| US4997967A (en) * | 1989-12-28 | 1991-03-05 | Ciba-Geigy Corporation | Process for the preparation of isothiocyanates |
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2008
- 2008-07-08 CN CN200810123555XA patent/CN101307016B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0347380A1 (en) * | 1988-06-14 | 1989-12-20 | Ciba-Geigy Ag | Process for the preparation of 4-Bromoaniline-hydrobromide |
| US4997967A (en) * | 1989-12-28 | 1991-03-05 | Ciba-Geigy Corporation | Process for the preparation of isothiocyanates |
Non-Patent Citations (2)
| Title |
|---|
| JP昭61-72777A 1986.04.14 |
| JP特开2000-239207A 2000.09.05 |
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