CN103483274B - A kind of method preparing benbbensulfuronmethyl - Google Patents
A kind of method preparing benbbensulfuronmethyl Download PDFInfo
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- CN103483274B CN103483274B CN201310438518.9A CN201310438518A CN103483274B CN 103483274 B CN103483274 B CN 103483274B CN 201310438518 A CN201310438518 A CN 201310438518A CN 103483274 B CN103483274 B CN 103483274B
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Abstract
The invention discloses a kind of method preparing benbbensulfuronmethyl, the method is: phosgene, benzylsulfamide dimethylbenzene and n-butyl isocyanate are added in proportion in photochemical still I and synthesize O-methoxy carboxyl benzyl sulfo group isocyanic ester; Reaction mixture containing O-methoxy carboxyl benzyl sulfo group isocyanic ester and unreacted phosgene and catalyzer n-butyl isocyanate completely enters in photochemical still II, adds optical self-encoding O-methoxy carboxyl benzyl sulfo group isocyanic ester; Enter de-light tower, deviate from n-butyl isocyanate, dimethylbenzene photoreactive gas; O-methoxy carboxybenzyl sulfo group isocyanic ester after de-phosgene and 2-amino-4,6-dimethoxy pyrimidine add in synthesis reactor in proportion; After material enters automatic centrifuge, centrifugation obtains product benbbensulfuronmethyl.Beneficial effect: catalyzer is recycle in photochemical process, reduces consumption, reduces costs, alleviate processing costs; The de-phosgene tower of employing removes the phosgene in xylene solution, decreases the consumption of dimethylbenzene; Adopt mode of the present invention to synthesize, improve synthesis yield and quality product, its synthesis yield is up to 98%.
Description
Technical field
The present invention relates to a kind of method preparing weedicide, particularly relate to a kind of method preparing benbbensulfuronmethyl.
Background technology
Benbbensulfuronmethyl is selectivity inner-adsorption conduction-type herbicide, is applicable to rice field and prevents and kill off life in 1 year and perennial broadleaf weed and nutgrass flatsedge.The general method for making of benbbensulfuronmethyl is that the xylene solution of 2-amino-4,6-dimethoxy pyrimidine and adjacent methyl-formiate benzyl sulfonyl isocyanate is carried out stirring reaction 8-10h in greenhouse, steams dimethylbenzene, also dry with chlorobutane washing, obtained benbbensulfuronmethyl.Adopt the starting material that obtained benbbensulfuronmethyl in this way consumes many, chlorobutane danger is high simultaneously, operate dangerous, therefore, in order to solve the problem, the invention provides a kind of new technical scheme.
Summary of the invention
In order to solve the problem, the invention provides a kind of new technical scheme.
The technical solution used in the present invention: a kind of method preparing benbbensulfuronmethyl comprises the following steps:
A, dimethylbenzene and benzylsulfamide are added in ball mill the benzylsulfamide dimethylbenzene suspension liquid making 30% through pearl grinding-in.
B, by the benzylsulfamide dimethylbenzene suspension liquid 2-4:1 in molar ratio of phosgene and 30%, catalyzer n-butyl isocyanate and 30% benzylsulfamide dimethylbenzene suspension liquid in molar ratio 1-4:20 add continuously in photochemical still I and carry out photochmeical reaction, temperature in photochemical still I is 100-120 DEG C, reaction time is 2-4h, synthesis O-methoxy carboxyl benzyl sulfo group isocyanic ester;
Reaction mixture containing O-methoxy carboxyl benzyl sulfo group isocyanic ester and unreacted phosgene and catalyzer n-butyl isocyanate completely in c, b step enters in photochemical still II continuously, add phosgene simultaneously, phosgene and benzylsulfamide 1-2:4, temperature in photochemical still II is 120-130 DEG C, material is reaction time 1-3h in photochemical still II, synthesis O-methoxy carboxyl benzyl sulfo group isocyanic ester;
D, O-methoxy carboxyl benzyl sulfo group isocyanic ester enter de-light tower continuously, the n-butyl isocyanate deviate from and dimethylbenzene return recycle in photochemical still I, excessive phosgene is through cooling separator, isolated phosgene returns recycle in photochemical still I continuously, and hydrogenchloride non-condensable gas delivers to tower process in light tail gas place;
O-methoxy carboxyl benzyl sulfo group isocyanic ester after e, de-phosgene and the xylene solution of 2-amino-4,6-dimethoxy pyrimidine add in synthesis reactor continuously by the mol ratio of 1:1.02, and the temperature in synthesis reactor is 50-60 DEG C, and the reaction times is 2-7h;
F, material enter insulation reaction still, and the temperature in insulation reaction still is 60-70 DEG C, and the reaction times is 1-3h;
After g, material enter automatic centrifuge, centrifugation obtains product benbbensulfuronmethyl and mother liquor, and the batching that mother liquor makes 2-amino-4,6-dimethoxy pyrimidine uses.
In step a, phosgene and 30% the mol ratio of benzylsulfamide dimethylbenzene suspension liquid be 3:1, catalyzer n-butyl isocyanate and 30% the mol ratio of benzylsulfamide dimethylbenzene suspension liquid be 1:10.
Photochemical still I used, photochemical still II, de-light tower, synthesis reactor are continuous reaction apparatus.
Beneficial effect of the present invention: adopt continuously feeding photochemical process synthesis O-methoxy carboxyl benzyl sulfo group isocyanic ester, decrease the decomposition under the high temperature conditions of O-methoxy carboxyl benzyl sulphonamide, improve O-methoxy carboxyl benzyl sulfo group isocyanate conversion rate, its O-methoxy carboxyl benzyl sulfo group isocyanic ester productive rate is greater than 98%; Catalyzer is recycle in photochemical process, decreases the consumption of catalyzer, reduces product cost, also mitigates the aftertreatment expense in building-up process simultaneously; In O-methoxy carboxyl benzyl sulfo group isocyanate production processes, adopt O-methoxy carboxyl benzyl sulfo group isocyanic ester to take off phosgene tower and remove phosgene in its xylene solution, and to catch up with nitrogen except compared with phosgene, decrease the consumption of solution dimethylbenzene; In tail gas phosgene through with hydrogenchloride refrigerated separation after capable of circulationly to apply mechanically, reduce phosgene raw material consumption, also reduce the processing cost of light tail gas; O-methoxy carboxyl benzyl sulfo group isocyanic ester is adopted to synthesize with the synchronous feed way of 2-amino-4.6-dimethoxypyridin solution, improve synthesis yield and quality product, its synthesis yield is up to 98%, the content of the finished product benbbensulfuronmethyl reaches 98%, and yield reaches 96%(in O-methoxy carboxyl benzyl sulfo group isocyanic ester).
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
By phosgene 33kg/h, 30% benzylsulfamide dimethylbenzene suspension liquid 127.3kg/h and catalyzer n-butyl isocyanate in molar ratio 40:20:1 add continuously in photochemical still I and carry out photochmeical reaction, temperature in photochemical still I is 105 DEG C, reaction time 2h, synthesis O-methoxy carboxyl benzyl sulfo group isocyanic ester; Reaction mixture containing O-methoxy carboxyl benzyl sulfo group isocyanic ester and unreacted phosgene and catalyzer n-butyl isocyanate completely enters in photochemical still II continuously, add phosgene 8.3kg/h, the mol ratio of phosgene and benzylsulfamide xylene solution is 1:4, temperature in photochemical still II is 120 DEG C, reaction time 1h, synthesis O-methoxy carboxyl benzyl sulfo group isocyanic ester; O-methoxy carboxyl benzyl sulfo group isocyanic ester enters de-light tower continuously, the n-butyl isocyanate deviate from and dimethylbenzene return recycle in photochemical still I, excessive phosgene is through cooling separator, isolated phosgene returns recycle in photochemical still I continuously, and hydrogenchloride non-condensable gas delivers to tower process in light tail gas place; The xylene solution that O-methoxy carboxybenzyl sulfo group isocyanic ester after de-phosgene and the 2-amino-4,6-dimethoxy pyrimidine of 30% are sent out adds in synthesis reactor continuously by the mol ratio of 1:1.02, and the temperature in synthesis reactor is 50 DEG C, and the reaction times is 4h; Material enters insulation reaction still, and the temperature in insulation reaction still is 60 DEG C, and the reaction times is 1h; After material enters automatic centrifuge, centrifugation obtains product benbbensulfuronmethyl and mother liquor, and the batching that mother liquor makes 2-amino-4,6-dimethoxy pyrimidine uses.
Embodiment 2
By phosgene 33kg/h, 30% benzylsulfamide dimethylbenzene suspension liquid 127.3kg/h and catalyzer n-butyl isocyanate in molar ratio 30:10:1 add continuously in photochemical still I and carry out photochmeical reaction, temperature in photochemical still I is 110 DEG C, reaction time 2.5h, synthesis O-methoxy carboxyl benzyl sulfo group isocyanic ester; Reaction mixture containing O-methoxy carboxyl benzyl sulfo group isocyanic ester and unreacted phosgene and catalyzer n-butyl isocyanate completely enters in photochemical still II continuously, add phosgene 8.3kg/h, the mol ratio of phosgene and benzylsulfamide dimethylbenzene suspension liquid is 1.2:4, temperature in photochemical still II is 125 DEG C, reaction time 1.5h, synthesis O-methoxy carboxyl benzyl sulfo group isocyanic ester; O-methoxy carboxyl benzyl sulfo group isocyanic ester enters de-light tower continuously, the n-butyl isocyanate deviate from and dimethylbenzene return recycle in photochemical still I, excessive phosgene is through cooling separator, isolated phosgene returns recycle in photochemical still I continuously, and hydrogenchloride non-condensable gas delivers to tower process in light tail gas place; The xylene solution of the O-methoxy carboxybenzyl sulfo group isocyanic ester after de-phosgene and the 2-amino-4,6-dimethoxy pyrimidine of 30% adds in synthesis reactor continuously by the mol ratio of 1:1.02, and the temperature in synthesis reactor is 55 DEG C, and the reaction times is 5h; Material enters insulation reaction still, and the temperature in insulation reaction still is 65 DEG C, and the reaction times is 1.5h; After material enters automatic centrifuge, centrifugation obtains product benbbensulfuronmethyl and mother liquor, and the batching that mother liquor makes 2-amino-4,6-dimethoxy pyrimidine uses.
Embodiment 3
By phosgene 33kg/h, 30% benzylsulfamide dimethylbenzene suspension liquid 127.3kg/h and catalyzer n-butyl isocyanate in molar ratio 60:20:3 add continuously in photochemical still I and carry out photochmeical reaction, temperature in photochemical still I is 115 DEG C, reaction time 3h, synthesis O-methoxy carboxyl benzyl sulfo group isocyanic ester; Reaction mixture containing O-methoxy carboxyl benzyl sulfo group isocyanic ester and unreacted phosgene and catalyzer n-butyl isocyanate completely enters in photochemical still II continuously, add phosgene 8.3kg/h, phosgene and benzylsulfamide dimethylbenzene suspension liquid 1.5:4, temperature in photochemical still II is 127 DEG C, reaction time 2h, synthesis O-methoxy carboxyl benzyl sulfo group isocyanic ester; O-methoxy carboxyl benzyl sulfo group isocyanic ester enters de-light tower, the n-butyl isocyanate deviate from and dimethylbenzene return recycle in photochemical still I, excessive phosgene is through cooling separator, isolated phosgene returns recycle in photochemical still I continuously, and hydrogenchloride non-condensable gas delivers to tower process in light tail gas place; The xylene solution of the O-methoxy carboxybenzyl sulfo group isocyanic ester after de-phosgene and the 2-amino-4,6-dimethoxy pyrimidine of 30% adds in synthesis reactor continuously by the mol ratio of 1:1.02, and the temperature in synthesis reactor is 57 DEG C, and the reaction times is 6h; Material enters insulation reaction still, and the temperature in insulation reaction still is 67 DEG C, and the reaction times is 2h; After material enters automatic centrifuge, centrifugation obtains product benbbensulfuronmethyl and mother liquor, and the batching that mother liquor makes 2-amino-4,6-dimethoxy pyrimidine uses.
Embodiment 4
By phosgene 33kg/h, 30% benzylsulfamide dimethylbenzene suspension liquid 127.3kg/h and catalyzer n-butyl isocyanate in molar ratio 20:5:1 add continuously in photochemical still I and carry out photochmeical reaction, temperature in photochemical still I is 120 DEG C, reaction time 4h, synthesis O-methoxy carboxyl benzyl sulfo group isocyanic ester; Reaction mixture containing O-methoxy carboxyl benzyl sulfo group isocyanic ester and unreacted phosgene and catalyzer n-butyl isocyanate completely enters in photochemical still II continuously, add phosgene 8.3kg/h, the mol ratio of phosgene and benzylsulfamide xylene solution is 2:4, temperature in photochemical still II is 130 DEG C, reaction time 3h, synthesis O-methoxy carboxyl benzyl sulfo group isocyanic ester; O-methoxy carboxyl benzyl sulfo group isocyanic ester enters de-light tower, the n-butyl isocyanate deviate from and dimethylbenzene return recycle in photochemical still I, excessive phosgene is through cooling separator, isolated phosgene returns recycle in photochemical still I continuously, and hydrogenchloride non-condensable gas delivers to tower process in light tail gas place; The xylene solution of the O-methoxy carboxybenzyl sulfo group isocyanic ester after de-phosgene and the 2-amino-4,6-dimethoxy pyrimidine of 30% adds in synthesis reactor continuously by the mol ratio of 1:1.02, and the temperature in synthesis reactor is 60 DEG C, and the reaction times is 7h; Material enters insulation reaction still, and the temperature in insulation reaction still is 70 DEG C, and the reaction times is 3h; After material enters automatic centrifuge, centrifugation obtains product benbbensulfuronmethyl and mother liquor, and the batching that mother liquor makes 2-amino-4,6-dimethoxy pyrimidine uses.
Beneficial effect of the present invention: adopt continuously feeding photochemical process synthesis O-methoxy carboxyl benzyl sulfo group isocyanic ester, decrease the decomposition under the high temperature conditions of O-methoxy carboxyl benzyl sulphonamide, improve O-methoxy carboxyl benzyl sulfo group isocyanate conversion rate, its O-methoxy carboxyl benzyl sulfo group isocyanic ester productive rate is greater than 98%; Catalyzer is recycle in photochemical process, decreases the consumption of catalyzer, reduces product cost, also mitigates the aftertreatment expense in building-up process simultaneously; In O-methoxy carboxyl benzyl sulfo group isocyanate production processes, adopt O-methoxy carboxyl benzyl sulfo group isocyanic ester to take off phosgene tower and remove phosgene in its xylene solution, and to catch up with nitrogen except compared with phosgene, decrease the consumption of solution dimethylbenzene; In tail gas phosgene through with hydrogenchloride refrigerated separation after capable of circulationly to apply mechanically, reduce phosgene raw material consumption, also reduce the processing cost of light tail gas; O-methoxy carboxyl benzyl sulfo group isocyanic ester is adopted to synthesize with the synchronous feed way of 2-amino-4.6-dimethoxypyridin solution, improve synthesis yield and quality product, its synthesis yield is up to 98%, the content of the finished product benbbensulfuronmethyl reaches 98%, and yield reaches 96%(in O-methoxy carboxyl benzyl sulfo group isocyanic ester).
Claims (3)
1. prepare a method for benbbensulfuronmethyl, it is characterized in that: the method comprises the following steps:
A, dimethylbenzene and 2-methoxyl group formyl-benzyl sulphonamide are added in ball mill the 2-methoxyl group formyl-benzyl sulphonamide dimethylbenzene suspension liquid making 30% through pearl grinding-in;
B, by the 2-methoxyl group formyl-benzyl sulphonamide dimethylbenzene suspension liquid 2-4:1 in molar ratio of phosgene and 30%, catalyzer n-butyl isocyanate and 30% 2-methoxyl group formyl-benzyl sulphonamide dimethylbenzene suspension liquid in molar ratio 1-4:20 add continuously in photochemical still I and carry out photochmeical reaction, temperature in photochemical still I is 100-120 DEG C, reaction time is 2-4h, synthesis O-methoxy carboxyl benzyl sulfo group isocyanic ester;
Reacted mixture in c, b step enters in photochemical still II continuously, add phosgene simultaneously, the mol ratio of phosgene and 2-methoxyl group formyl-benzyl sulphonamide xylene solution is 1-2:4, temperature in photochemical still II is 120-130 DEG C, material is reaction time 1-3h in photochemical still II, synthesis O-methoxy carboxyl benzyl sulfo group isocyanic ester;
D, O-methoxy carboxyl benzyl sulfo group isocyanic ester enter de-light tower continuously, the n-butyl isocyanate deviate from and dimethylbenzene return recycle in photochemical still I continuously, excessive phosgene is through cooling separator, isolated phosgene returns recycle in photochemical still I continuously, and hydrogenchloride non-condensable gas delivers to tower process in light tail gas place;
O-methoxy carboxyl benzyl sulfo group isocyanic ester after e, de-phosgene and the xylene solution of 2-amino-4,6-dimethoxy pyrimidine add in synthesis reactor continuously by the mol ratio of 1:1.02, and the temperature in synthesis reactor is 50-60 DEG C, and the reaction times is 2-7h;
F, material enter insulation reaction still, and the temperature in insulation reaction still is 60-70 DEG C, and the reaction times is 1-3h;
After g, material enter automatic centrifuge, centrifugation obtains product benbbensulfuronmethyl and mother liquor, and the batching that mother liquor makes 2-amino-4,6-dimethoxy pyrimidine uses.
2. a kind of method preparing benbbensulfuronmethyl according to claim 1; it is characterized in that: in step a; phosgene and 30% the mol ratio of 2-methoxyl group formyl-benzyl sulphonamide dimethylbenzene suspension liquid be 3:1, catalyzer n-butyl isocyanate and 30% the mol ratio of 2-methoxyl group formyl-benzyl sulphonamide dimethylbenzene suspension liquid be 1:10.
3. a kind of method preparing benbbensulfuronmethyl according to claim 1, is characterized in that: photochemical still I used, photochemical still II, de-light tower, synthesis reactor are continuous reaction apparatus.
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| 新稻田除草剂苄嘧磺隆的合成;孔繁蕾，等;《化学世界》;19901231(第5期);第211-213页 * |
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