CN102603582A - Method for synthesizing o-methyl formate benzene sulfonamide - Google Patents

Method for synthesizing o-methyl formate benzene sulfonamide Download PDF

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CN102603582A
CN102603582A CN2012100476061A CN201210047606A CN102603582A CN 102603582 A CN102603582 A CN 102603582A CN 2012100476061 A CN2012100476061 A CN 2012100476061A CN 201210047606 A CN201210047606 A CN 201210047606A CN 102603582 A CN102603582 A CN 102603582A
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acid
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toluene
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王继龙
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Abstract

The invention relates to a method for synthesizing o-methyl formate benzene sulfonamide which is capable of effectively solving the problems that a conventional o-methyl formate benzene sulfonamide synthesizing method is complex in process, high in cost, low in efficiency and pollutes environment and comprises the steps of: heating water, adding sodium nitrite, dissolving, and adding methyl o-aminobenzoate to obtain a methyl ester mixture; putting the water in a diazo pot, adding sulfuric acid and hydrochloric acid to obtained mixed acid; reducing the temperature of the mixed acid, adding the methyl ester mixture, reacting to obtain a diazonium salt solution, adding copper sulfate, introducing sulfur dioxide, determining by utilizing an H acid reagent solution and fading by utilizing the H acid; adding toluene, introducing liquid chlorine, determining to be darkgreen by utilizing a benzidine reagent solution, standing and layering to obtain an o-methyl formate benzene sulfonamide solution at the upper layer; and adding anhydrous toluene and carbinol, introducing liquid ammonia, adjusting pH (potential Of Hydrogen) value to be neutral by using acetic acid, removing the acetic acid, washing till being colourless by using the toluene, removing the toluene, beating by using the water, washing to be neutral, removing the water and drying. The method disclosed by the invention has the advantages of easiness in operation, high efficiency, low cost and good quality, and saves energy and raw material, and is environment-friendly.

Description

A kind of method of synthetic adjacent methyl-formiate benzsulfamide
Technical field
The present invention relates to chemical industry, the method for particularly a kind of synthetic adjacent methyl-formiate benzsulfamide (claiming first sulfanilamide (SN) again).
Background technology
Adjacent methyl-formiate benzsulfamide (first sulfanilamide (SN)) is a kind of important agricultural chemicals, medicine intermediate, is mainly used in the synthetic of sulfonylurea herbicide.Wherein have the sulfonylurea herbicide of kinds such as a series products such as chlorimuronethyl, amine sulfometuron-methyl, primisulfuronmethyl, procarbazone, sulfometuronmethyl, tribenuronmethyl, metsulfuronmethyl relevant with adjacent methyl-formiate benzsulfamide (first sulfanilamide (SN)), it is one of main raw material of synthetic above-mentioned several herbicides.Its traditional compound method is to be got with methanol esterification by o-benzoic sulfimide (asccharin), and method is to obtain forming amination liquid with the ammoniacal liquor amination behind the adjacent methyl-formiate benzene sulfonyl chloride; Add activated carbon decolorizing, generate o-benzoic sulfimide (asccharin), through dehydration, oven dry with 30% sulfuric acid acid out; O-benzoic sulfimide (asccharin) and methyl alcohol carry out esterification under sulphuric acid catalysis, generate adjacent methyl-formiate benzsulfamide, complex process; Cost is high; Unstable product quality, production efficiency is low, contaminate environment; Therefore, how to develop a kind of more energy-conservation, more optimize, more efficiently, more environmental protection, the more economical synthetic adjacent methyl-formiate benzsulfamide of the method problem that always is in the industry to be paid close attention to.
Summary of the invention
To above-mentioned situation, for overcoming the defective of prior art, the object of the invention just provides a kind of method of synthetic adjacent methyl-formiate benzsulfamide, can effectively solve adjacent methyl-formiate benzsulfamide complex manufacturing, and cost is high, the low and problem of environment pollution caused of efficient.
The technical scheme that the present invention solves is to be starting raw material with the methyl o-aminobenzoate, after diazotization reaction, replacement(metathesis)reaction, chlorination reaction obtain adjacent methyl-formiate benzene sulfonyl chloride; Add methyl alcohol; Use the liquefied ammonia amination reaction, get adjacent methyl-formiate benzsulfamide, step is following:
1. preparation mixtures of methyl esters:
Water is put into dissolving pan, and the adding Sodium Nitrite is stirred in heating, and dissolving adds methyl o-aminobenzoate again, gets mixtures of methyl esters;
2. doazo reaction:
(1) preparation nitration mixture: water is put into the diazonium pot, add sulfuric acid (H 2SO 4), add hydrochloric acid (HCl) again, get nitration mixture;
(2) doazo reaction: when the nitration mixture temperature reduce to≤0 ℃ the time, under agitation evenly drip the mixtures of methyl esters that step 1 makes, reaction becomes transparent faint yellow diazonium salt solution;
3. replacement(metathesis)reaction:
In the diazonium salt solution that step 2 makes, add copper sulfate (CuSO 4), feed liquid sulfur dioxide (SO 2), to measure with H acid test solution, H acid is faded;
4. chlorination reaction:
After the replacement(metathesis)reaction, under agitation add toluene, feed liquid chlorine, stir, be determined as blackish greenly with the p-diaminodiphenyl test solution, leave standstill, layering, adjacent methyl-formiate benzene sulfonyl chloride (claiming SULPHURYL CHLORIDE toluene again) solution that must the upper strata;
5. aminating reaction gets adjacent methyl-formiate benzsulfamide:
In the adjacent methyl-formiate benzene sulfonyl chloride solution that step 4 obtains, add dry toluene and methyl alcohol, feed liquefied ammonia, making the pH value is 9; (HAc) is adjusted to neutrality with acetate, and suction filtration is removed acetate (HAc), and be extremely colourless with toluene wash; The centrifugal toluene of removing, water making beating again, washing are to neutral, and centrifugal removing anhydrated; The dry adjacent methyl-formiate benzsulfamide (first sulfanilamide (SN)) that gets, packing.
The inventive method is simple, and is reliable and stable, easy to operate, and production efficiency is high, save energy and starting material, and environmental protection, cost is low, and good product quality is the innovation on adjacent methyl-formiate benzsulfamide is produced.
Description of drawings
Fig. 1 is a reaction formula sign picture of the present invention.
Fig. 2 is a process flow sheet of the present invention.
Embodiment
Elaborate below in conjunction with the accompanying drawing specific embodiments of the invention.
The present invention is realized by following steps in practical implementation:
1. preparation mixtures of methyl esters:
480 kg water are put into dissolving pan, be heated to 25-30 ℃, under agitation add the 150kg Sodium Nitrite, dissolving adds the 320kg methyl o-aminobenzoate again, stirs 15min down at 30 ℃, gets mixtures of methyl esters;
2. doazo reaction:
(1) preparation nitration mixture: 320kg water is put into the diazonium pot, add 167kg sulfuric acid (H 2SO 4); ℃ following 605kg hydrochloric acid (HCl) that adds in temperature≤35; Get nitration mixture; Acidity is 39.5～47 g/100ml (because the quality of height, sulfuric acid and the hydrochloric acid quality of temperature can cause the instability of nitration mixture concentration, if the concentration of nitration mixture does not reach 39.5～47 g/100ml, then add hydrochloric acid and transfer to 39.5～47 g/100ml);
(2) doazo reaction: when the nitration mixture temperature reduce to≤0 ℃ the time; Under agitation evenly drip the mixtures of methyl esters that step 1 makes, temperature in the dropping process≤20 ℃ dropwise; Reaction becomes transparent faint yellow diazonium salt solution; Acidity is that (owing to receive the influence of nitration mixture acidity, rate of addition, speed of response, in order to guarantee the quality of doazo reaction, acidity is necessary for 10.5～12.5g/100ml to 10.5～12.5g/100ml; As do not reach the acidity requirement, can add hydrochloric acid and transfer to 10.5～12.5g/100ml);
3. replacement(metathesis)reaction:
The diazonium salt solution that step 2 is made adds 74kg copper sulfate (CuSO down at 12-16 ℃ 4) postcooling is to 7-9 ℃, feeds 245kg liquid sulfur dioxide (SO 2), the time is 60 minutes, in the feeding process, temperature is controlled at≤and 35 ℃, keep 45min down at≤35 ℃ then, to measure with H acid test solution, H acid is faded, and does not fade as if H acid, should add liquid sulfur dioxide (SO in addition 2), fade until H acid, feed liquid sulfur dioxide (SO 2) in the process, pressure remains on 0.08～0.1Mpa;
4. chlorination reaction:
After the replacement(metathesis)reaction, under agitation add 700 kg toluene, be cooled to 24-26 ℃, under≤35 ℃; Evenly feed liquid chlorine 80kg in the 45min, stir 30min after, be determined as with the p-diaminodiphenyl test solution blackish green, if not blackish green; Then the logical liquid chlorine of benefit is blackish green to being determined as with the p-diaminodiphenyl test solution again, and logical chlorine finishes, and behind the stirring 20min, leaves standstill>=30min; Layering, lower floor is a copper water, and the middle level is an emulsion layer, and the upper strata is adjacent methyl-formiate benzene sulfonyl chloride (claiming a SULPHURYL CHLORIDE toluene again) solution;
5. aminating reaction gets adjacent methyl-formiate benzsulfamide:
The adjacent methyl-formiate benzene sulfonyl chloride solution that step 4 obtains from the upper strata is put into pot, add 830 kg dry toluenes and 154kg methyl alcohol, under agitation be cooled to 0～5 ℃, feed liquefied ammonia 85-95min; Making the pH value is 9, feeds that temperature is controlled in the liquefied ammonia process≤30 ℃, closes freezingly, continues to stir 0.5 hour; Repetition measurement pH=9 is if repetition measurement pH＜9 then replenish liquefied ammonia pH value=9 (were stirred 0.5 hour because continue; Sometimes the adjacent completely methyl-formiate benzene sulfonyl chloride of unreacted continues reaction and makes the pH value less than 9, at this moment should replenish liquefied ammonia and make the pH value equal 9), reaction finishes; Be cooled to room temperature (18-25 ℃), (HAc) is adjusted to neutrality with acetate, and suction filtration is removed acetate (HAc); Extremely colourless with toluene wash, the centrifugal toluene of removing, water making beating again, washing are to neutral; Centrifugal removing anhydrated, the dry adjacent methyl-formiate benzsulfamide (first sulfanilamide (SN)) that gets, packing.
Described methyl o-aminobenzoate mass concentration is>=97%; The Sodium Nitrite mass concentration is>=96%; Mass concentration>=31% of hydrochloric acid (HCl); Sulfuric acid (H 2SO 4) mass concentration be>=92.5%; Copper sulfate (CuSO 4) mass concentration be>=95%; Sulfurous gas (SO 2) mass concentration be>=95%; Liquid chlorine (Cl 2) mass concentration be>=99%; Toluene is industrial goods.
Proportioning with the material proportion amount increases or reduces the adjacent methyl-formiate benzsulfamide that can prepare any amount as stated above.
Products obtained therefrom of the present invention confirms that through chemical examination adjacent methyl-formiate benzsulfamide (first sulfanilamide (SN)) content is more than 98.5%; And be used to produce agricultural chemicals and as medicine intermediate by producer; As being delivered to Jiangsu China auspicious chemical industry ltd, adjacent methyl-formiate benzsulfamide (the first sulfanilamide (SN)) 500 kilograms of gained is used to produce metsulfuronmethyl; The metsulfuronmethyl that produces qualified fully, adjacent methyl-formiate benzsulfamide (first sulfanilamide (SN)) consumes and other producer's product indifferences.
The present invention compares with the traditional technology that with o-benzoic sulfimide (asccharin) is raw material; Reduced multiple middle-chain; Shorten operational path, practiced thrift raw material consumption, improved yield; Avoid the waste discharge pollution, be the synthetic raw material that super quality and competitive price are provided of sulfonylurea herbicide.One ton of adjacent methyl-formiate benzsulfamide of every production is practiced thrift 300 kilograms in sulfuric acid, 500 kilograms of ammoniacal liquor, 50 kilograms of gacs; 200 kilograms of methyl alcohol, product yield improves 5%, and 8 tons of ammonia nitrogen waste waters are analysed in few acid discharge; 100 kilograms of waste active carbons, and, all obtained identical and akin result through (12 times) TE repeatedly; Show that method is stable, reliable, have practicality.
It is simple, reliable and stable that the synthetic adjacent methyl-formiate benzsulfamide of the inventive method has method, and production efficiency is high, save energy and starting material, and environmental protection, product cost is low, advantages such as good product quality.The present invention is that prior art is incomparable for synthetic adjacent methyl-formiate benzsulfamide provides optimized new way, is the innovation in adjacent methyl-formiate benzsulfamide (first sulfanilamide (SN)) production, and economic and social benefit is huge.

Claims (2)

1. the method for a synthetic adjacent methyl-formiate benzsulfamide is characterized in that, is realized by following steps:
(1) preparation mixtures of methyl esters:
480 kg water are put into dissolving pan, be heated to 25-30 ℃, under agitation add the 150kg Sodium Nitrite, dissolving adds the 320kg methyl o-aminobenzoate again, stirs 15min down at 30 ℃, gets mixtures of methyl esters;
(2) doazo reaction:
1. prepare nitration mixture: 320kg water is put into the diazonium pot, add 167kg sulfuric acid (H 2SO 4), ℃ following 605kg hydrochloric acid that adds gets nitration mixture in temperature≤35, and acidity is 39.5～47 g/100ml;
2. doazo reaction: when the nitration mixture temperature reduce to≤0 ℃ the time; Under agitation evenly drip the mixtures of methyl esters that step (1) makes, temperature in the dropping process≤20 ℃ dropwise; Reaction becomes transparent faint yellow diazonium salt solution, and acidity is 10.5～12.5g/100ml;
(3) replacement(metathesis)reaction:
The diazonium salt solution that step (2) is made adds 74kg copper sulfate postcooling down to 7-9 ℃ at 12-16 ℃, feeds the 245kg liquid sulfur dioxide, and the time is 60 minutes, in the feeding process; Temperature is controlled at≤and 35 ℃, keep 45min down at≤35 ℃ then, with H acid test solution mensuration; H acid is faded, if H acid is not faded, should add liquid sulfur dioxide in addition; Fade until H acid, feed in the liquid sulfur dioxide process, pressure remains on 0.08～0.1Mpa;
(4) chlorination reaction:
After the replacement(metathesis)reaction, under agitation add 700 kg toluene, be cooled to 24-26 ℃, under≤35 ℃; Evenly feed liquid chlorine 80kg in the 45min, stir 30min after, be determined as with the p-diaminodiphenyl test solution blackish green, if not blackish green; Then the logical liquid chlorine of benefit is blackish green to being determined as with the p-diaminodiphenyl test solution again, and logical chlorine finishes, and behind the stirring 20min, leaves standstill>=30min; Layering, lower floor is a copper water, and the middle level is an emulsion layer, and the upper strata is adjacent methyl-formiate benzene sulfonyl chloride solution;
(5) aminating reaction gets adjacent methyl-formiate benzsulfamide:
The adjacent methyl-formiate benzene sulfonyl chloride solution that step (4) obtains from the upper strata is put into pot, add 830 kg dry toluenes and 154kg methyl alcohol, under agitation be cooled to 0～5 ℃, feed liquefied ammonia 85-95min, making the pH value is 9; Feed that temperature is controlled in the liquefied ammonia process≤30 ℃, close freezingly, continue to stir repetition measurement pH=9 0.5 hour; If repetition measurement pH＜9 then replenish liquefied ammonia and make pH value=9, reaction finishes, and is cooled to room temperature; Be adjusted to neutrality with acetate, suction filtration is removed acetate, and is extremely colourless with toluene wash, the centrifugal toluene of removing; Water making beating again, washing are to neutral, and centrifugal removing anhydrated, dry adjacent methyl-formiate benzsulfamide, packing.
2. the method for synthetic adjacent methyl-formiate benzsulfamide according to claim 1 is characterized in that, described methyl o-aminobenzoate mass concentration is>=97%; The Sodium Nitrite mass concentration is>=96%; Mass concentration>=31% of hydrochloric acid (HCl); Sulfuric acid (H 2SO 4) mass concentration be>=92.5%; Copper sulfate (CuSO 4) mass concentration be>=95%; Sulfurous gas (SO 2) mass concentration be>=95%; Liquid chlorine (Cl 2) mass concentration be>=99%.
CN2012100476061A 2012-02-28 2012-02-28 Method for synthesizing o-methyl formate benzene sulfonamide Pending CN102603582A (en)

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CN103724224A (en) * 2013-12-19 2014-04-16 中国平煤神马集团开封兴化精细化工有限公司 Diazo reaction technology in saccharin production
CN103739525A (en) * 2013-12-30 2014-04-23 黄河三角洲京博化工研究院有限公司 Preparation method of substituted benzene sulfonyl chloride
CN104402760A (en) * 2014-09-28 2015-03-11 中国平煤神马集团开封兴化精细化工有限公司 Diazotization reaction continuous production method in saccharin production process
CN105085333A (en) * 2015-08-07 2015-11-25 新乡市辉普化工科技有限公司 Preparation method of methyl o-sulphamoylbenzoate
CN105294602A (en) * 2015-12-01 2016-02-03 珠海格力电器股份有限公司 Method for synthesizing amide compounds from sulfur dioxide and amide compounds
CN105732441A (en) * 2016-02-25 2016-07-06 浙江工业大学 Method for continuously preparing 2-(chlorosulfonyl) methyl benzoate and device adopted for method
CN105949091A (en) * 2016-03-17 2016-09-21 田子馨 Method of preparing 2-chlorosulfonylmethyl benzoate from phthalic anhydride and urea
CN106946749A (en) * 2017-01-10 2017-07-14 田振民 A kind of production method of first sulfanilamide (SN)
CN111606829A (en) * 2020-07-07 2020-09-01 淄博腾煜化工工程有限公司 Production method of o-methyl formate benzyl sulfonamide
CN112457226A (en) * 2020-12-17 2021-03-09 安达市海纳贝尔化工有限公司 Synthesis process of high-purity o-methyl formate benzenesulfonamide
CN113842862A (en) * 2021-12-02 2021-12-28 东营市金凤凰化工股份有限公司 Ammoniation reactant optimization device for producing anthranilic acid

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103724224A (en) * 2013-12-19 2014-04-16 中国平煤神马集团开封兴化精细化工有限公司 Diazo reaction technology in saccharin production
CN103739525A (en) * 2013-12-30 2014-04-23 黄河三角洲京博化工研究院有限公司 Preparation method of substituted benzene sulfonyl chloride
CN104402760B (en) * 2014-09-28 2018-05-25 中国平煤神马集团开封兴化精细化工有限公司 Diazo-reaction continuous production method in a kind of saccharin production process
CN104402760A (en) * 2014-09-28 2015-03-11 中国平煤神马集团开封兴化精细化工有限公司 Diazotization reaction continuous production method in saccharin production process
CN105085333A (en) * 2015-08-07 2015-11-25 新乡市辉普化工科技有限公司 Preparation method of methyl o-sulphamoylbenzoate
CN105294602A (en) * 2015-12-01 2016-02-03 珠海格力电器股份有限公司 Method for synthesizing amide compounds from sulfur dioxide and amide compounds
CN105732441A (en) * 2016-02-25 2016-07-06 浙江工业大学 Method for continuously preparing 2-(chlorosulfonyl) methyl benzoate and device adopted for method
CN105732441B (en) * 2016-02-25 2017-12-15 浙江工业大学 Serialization prepares the method and its device of 2 (chlorosulfonyl) methyl benzoates
CN105949091A (en) * 2016-03-17 2016-09-21 田子馨 Method of preparing 2-chlorosulfonylmethyl benzoate from phthalic anhydride and urea
CN106946749A (en) * 2017-01-10 2017-07-14 田振民 A kind of production method of first sulfanilamide (SN)
CN111606829A (en) * 2020-07-07 2020-09-01 淄博腾煜化工工程有限公司 Production method of o-methyl formate benzyl sulfonamide
CN112457226A (en) * 2020-12-17 2021-03-09 安达市海纳贝尔化工有限公司 Synthesis process of high-purity o-methyl formate benzenesulfonamide
CN113842862A (en) * 2021-12-02 2021-12-28 东营市金凤凰化工股份有限公司 Ammoniation reactant optimization device for producing anthranilic acid

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Application publication date: 20120725