CN103910654B - The synthetic method of 1-methyl isophthalic acid-methoxyl group-3-phenylurea - Google Patents
The synthetic method of 1-methyl isophthalic acid-methoxyl group-3-phenylurea Download PDFInfo
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- CN103910654B CN103910654B CN201410163923.9A CN201410163923A CN103910654B CN 103910654 B CN103910654 B CN 103910654B CN 201410163923 A CN201410163923 A CN 201410163923A CN 103910654 B CN103910654 B CN 103910654B
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Abstract
The invention discloses the synthetic method of a kind of 1-methyl isophthalic acid-methoxyl group-3-phenylurea, comprise aniline and obtain phenyl isocyanate with phosgenation reaction in organic solvent; The organic solvent solution of phenyl isocyanate, reacts obtained 1-hydroxyl-3-phenylurea under the effect of catalyst A, in alkaline aqueous solution with oxammonium sulfate; 1-hydroxyl-3-phenylurea reacts obtained 1-methyl isophthalic acid-methoxyl group-3-phenylurea in the basic conditions under the effect of catalyst B with methyl-sulfate.The present invention has that technique is simple and direct, product purity is high, production process is easy to the advantages such as control.
Description
Technical field
The present invention relates to the synthetic method of a kind of 1-methyl isophthalic acid-methoxyl group-3-phenylurea.
Background technology
1-methyl isophthalic acid-methoxyl group-3-phenylurea is the important source material of the fine chemical products such as a kind of agricultural chemicals, medicine, also can be used for polymeric hardener catalyzer.
According to data consultation, also there is no its relevant synthesis patent and relevant synthetic technology report at present.For this reason, those skilled in the art is studying its synthetic technology and utility value always, to realize suitability for industrialized production.
Summary of the invention
The object of the present invention is to provide the synthetic method of a kind of simple and direct 1-methyl isophthalic acid-methoxyl group-3-phenylurea.
Technical solution of the present invention is:
A synthetic method for 1-methyl isophthalic acid-methoxyl group-3-phenylurea, is characterized in that: comprise the following steps:
(1) aniline obtains phenyl isocyanate with phosgenation reaction in organic solvent;
(2) organic solvent solution of phenyl isocyanate, reacts obtained 1-hydroxyl-3-phenylurea under the effect of catalyst A, in alkaline aqueous solution with oxammonium sulfate;
(3) 1-hydroxyl-3-phenylurea reacts obtained 1-methyl isophthalic acid-methoxyl group-3-phenylurea in the basic conditions under the effect of catalyst B with methyl-sulfate.
Reaction equation:
A. the synthesis of phenyl isocyanate
B.1-the synthesis of hydroxyl-3-phenylurea
The synthesis of c.N-phenyl-N '-methoxyl group-N '-MU
The aromatics organic solvents such as organic solvent nail benzene used, dimethylbenzene;
Catalyst A: can have again the character preventing azanol from decomposing in the basic conditions by phase transfer catalysis.As guan ether material.
Catalyst B referred to the material of phase transfer catalysis as: quaternary ammonium salts or other.
The mol ratio of aniline and phosgene: 1:1 ~ 3, optimum proportioning is 1:1.15; The toluene solution concentration of aniline at 7-40%, optimum concn 20-25%,
The mol ratio of phenyl isocyanate and oxammonium sulfate: 1:0.5 ~ 1, optimum proportioning is 1:0.55;
The mol ratio of 1-hydroxyl-3-phenylurea and methyl-sulfate: 1:1 ~ 3, optimum proportioning is 1:2.1;
Between luminescence temperature of reaction-10 DEG C ~ 10 DEG C of phenyl isocyanate synthesis, thermo-optical temperature of reaction 20 DEG C ~ 100 DEG C, preferably between 70 DEG C ~ 75 DEG C; The drip reacting temperature 10 DEG C ~ 40 DEG C of 1-hydroxyl-3-phenylurea synthesis, PH=5 ~ 10, optimal reaction temperature 25 DEG C ~ 40 DEG C, PH=6 ~ 9; The synthesis drip reacting temperature 10 DEG C ~ 50 DEG C of 1-methoxyl group-1-methyl-3-phenylurea, the best answers temperature 35 DEG C ~ 40 DEG C.
The present invention has that technique is simple and direct, product purity is high, production process is easy to the advantages such as control.
Below in conjunction with embodiment, the invention will be further described.
Embodiment
Embodiment 1:
(1) synthesis of phenyl isocyanate
In 500ml flask, add dry toluene 300ml, aniline 80g, stir be made into about 23% aniline toluene solution for subsequent use.
Toluene 250ml is dropped in another 1000ml flask, cooling limit, limit leads to light pre-logical light half an hour between-5 ~ 0 DEG C, start the aniline toluene liquid dripping above-mentioned preparation, dropping limit, limit leads to light, controls rate of addition and makes temperature of reaction control between-5 DEG C ~ 5 DEG C, time for adding is 3 ~ 4 hours, drip off rear continuation and lead to light half an hour, heat up logical light, rises to 70 DEG C ~ 75 DEG C, continue insulation after 0.5 hour, reaction terminates.Start to catch up with light, catch up with light to terminate after 1 ~ 2 hour, it is stand-by to be down to room temperature.Product yield 98%.
(2) preparation of 1-hydroxyl-3-phenylurea
In 1000ml flask, add oxammonium sulfate 76g, water 300ml, catalyzer Shi Ba guan ether 0.5g and 30%NaOH is about the 140ml aqueous solution, PH=8 ~ 9, and start to drip above-mentioned phenyl isocyanate reserve liquid, time for adding is 1 ~ 3 hour, and the best is 2 hours.Dropping temperature is at 35 DEG C ~ 40 DEG C, and to drip after terminating insulation reaction 1 hour at 40 ± 2 DEG C of temperature, suction filtration, dries; Obtain 1-hydroxyl-3-phenylurea 115.5 grams, content 98%.Yield 92%.
(3) synthesis of 1-methoxyl group-1-methyl-3-phenylurea
In 1000ml flask, add step preparation 115.5g1-hydroxyl-3-phenylurea, add toluene 180ml, methyl-sulfate 252g and catalyzer four butyl bromation amine 0.5g.30%NaOH aqueous solution 180g is dripped between 15 ~ 30 DEG C, time for adding is 0.5 ~ 1 hour, be warming up to 60 DEG C ~ 65 DEG C, stratification, branch vibration layer, organic layer adds the washing of 200ml clear water again, stratification, organic layer is cooled to 0 DEG C ~ 10 DEG C crystallizations, suction filtration, filter cake about 52 DEG C vacuum dryings.Obtain product 1-methyl isophthalic acid-methoxyl group-phenylurea 127.3 grams.Product fusing point 58.6 DEG C, content 99%.Product yield 95% (in 1-hydroxyl-3-phenylurea).
Embodiment 2:
(1) synthesis of phenyl isocyanate
In 500ml flask, add anhydrous dimethyl benzene 350ml, aniline 80g, stir be made into about 21% aniline xylene solution for subsequent use.
Dimethylbenzene 250ml is dropped in another 1000ml flask, cooling limit, limit leads to light pre-logical light half an hour between-5 ~ 0 DEG C, start the aniline dimethylbenzene liquid dripping above-mentioned preparation, dropping limit, limit leads to light, controls rate of addition and makes temperature of reaction control between-5 DEG C ~ 5 DEG C, time for adding is 3 ~ 4 hours, drip off rear continuation and lead to light half an hour, heat up logical light, rises to 70 DEG C ~ 75 DEG C, continue insulation after 0.5 hour, reaction terminates.Start to catch up with light, catch up with light to terminate after 1 ~ 2 hour, it is stand-by to be down to room temperature.Product yield 97%.
(2) preparation of 1-hydroxyl-3-phenylurea
In 2000ml flask, add oxammonium sulfate 150g, water 700ml, catalyzer Shi Ba guan ether 0.5g and 30%NaOH is about the 280ml aqueous solution, PH=8 ~ 9, starts to drip above-mentioned phenyl isocyanate 1200ml.Time for adding is 1 ~ 3 hour, and the best is 2 hours.Dropping temperature is at 38 DEG C ~ 40 DEG C, and to drip after terminating insulation reaction 1 hour at 40 ± 2 DEG C of temperature, suction filtration, dries.Obtain 1-hydroxyl-3-phenylurea, 230 grams, content 98%.Yield 91.8%.
(3) synthesis of 1-methoxyl group-1-methyl-3-phenylurea
In 1000ml flask, add step preparation 230g1-hydroxyl-3-phenylurea, add dimethylbenzene 400ml, methyl-sulfate 500g and catalyzer Shi Ba guan ether 0.5g.Between 20 DEG C ~ 40 DEG C, drip 30%NaOH aqueous solution 360g, time for adding is 0.5 ~ 1 hour, is warming up to 65 DEG C ~ 75 DEG C, stratification, branch vibration layer, and organic layer adds the washing of 400ml clear water again, stratification.Organic layer is cooled to 0 DEG C ~ 10 DEG C crystallizations, suction filtration.Filter cake about 52 DEG C vacuum dryings.Obtain product 1-methyl isophthalic acid-methoxyl group-phenylurea 255 grams.Product fusing point 58.7 DEG C, content 99.1%.Product yield 95.1% (in 1-hydroxyl-3-phenylurea).
Claims (1)
1. a synthetic method for 1-methyl isophthalic acid-methoxyl group-3-phenylurea, is characterized in that: comprise the following steps:
(1) synthesis of phenyl isocyanate
In 500ml flask, add anhydrous dimethyl benzene 350ml, aniline 80g, stir be made into about 21% aniline xylene solution for subsequent use;
Dimethylbenzene 250ml is dropped in another 1000ml flask, cooling limit, limit passes into phosgene between-5 ~ 0 DEG C, passes into phosgene half an hour in advance, start the aniline dimethylbenzene liquid dripping above-mentioned preparation, dropping limit, limit passes into phosgene, controls rate of addition and makes temperature of reaction control between-5 DEG C ~ 5 DEG C, time for adding is 3 ~ 4 hours, continue to pass into phosgene half an hour after dripping off, heat up and pass into phosgene, rise to 70 DEG C ~ 75 DEG C, continue insulation after 0.5 hour, reaction terminates; Start to catch up with light, catch up with light to terminate after 1 ~ 2 hour, it is stand-by to be down to room temperature; Product yield 97%;
(2) preparation of 1-hydroxyl-3-phenylurea
In 2000ml flask, add oxammonium sulfate 150g, water 700ml, catalyzer 18 crown ether 0.5g and the 30%NaOH280ml aqueous solution, PH=8 ~ 9, start to drip above-mentioned phenyl isocyanate 1200ml; Time for adding is 1 ~ 3 hour; Dropping temperature is at 38 DEG C ~ 40 DEG C, and to drip after terminating insulation reaction 1 hour at 40 ± 2 DEG C of temperature, suction filtration, dries; Obtain 1-hydroxyl-3-phenylurea, 230 grams, content 98%; Yield 91.8%;
(3) synthesis of 1-methoxyl group-1-methyl-3-phenylurea
In 1000ml flask, add step preparation 230g1-hydroxyl-3-phenylurea, add dimethylbenzene 400ml, methyl-sulfate 500g and catalyzer Shi Ba guan ether 0.5g; Between 20 DEG C ~ 40 DEG C, drip 30%NaOH aqueous solution 360g, time for adding is 0.5 ~ 1 hour, is warming up to 65 DEG C ~ 75 DEG C, stratification, branch vibration layer, and organic layer adds the washing of 400ml clear water again, stratification; Organic layer is cooled to 0 DEG C ~ 10 DEG C crystallizations, suction filtration; Filter cake 52 DEG C of vacuum dryings, obtain product 1-methyl isophthalic acid-methoxyl group-phenylurea 255 grams; Product fusing point 58.7 DEG C, content 99.1%; Product yield counts 95.1% with 1-hydroxyl-3-phenylurea.
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| CN101781236A (en) * | 2010-02-11 | 2010-07-21 | 江苏快达农化股份有限公司 | Method for preparing 3-(3,4-dichlorophenyl)-1-methoxy-1-methyl urea |
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| CN101781236A (en) * | 2010-02-11 | 2010-07-21 | 江苏快达农化股份有限公司 | Method for preparing 3-(3,4-dichlorophenyl)-1-methoxy-1-methyl urea |
Non-Patent Citations (3)
| Title |
|---|
| Possibilities of using 4-chloro-2-methylphenoxyacetohydroxamic acid for synthesis of O-mono- and O,N-dimethylhydroxylamines;Eckstein, Zygmunt et al;《Przem. Chem》;19781231;第57卷(第5期);241-244 * |
| 利谷隆合成研究;沈阳化工研究院农药一室除草剂二组;《农药》;19741231(第3期);13-22 * |
| 碳酸二甲酯做甲基化试剂的研究进展;舒婷等;《化工中间体》;20081231(第1期);20-23 * |
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