CN102351800A - Method for preparing 5-methylbenzimidazole-2-methyl carbamate - Google Patents
Method for preparing 5-methylbenzimidazole-2-methyl carbamate Download PDFInfo
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- CN102351800A CN102351800A CN2011102673464A CN201110267346A CN102351800A CN 102351800 A CN102351800 A CN 102351800A CN 2011102673464 A CN2011102673464 A CN 2011102673464A CN 201110267346 A CN201110267346 A CN 201110267346A CN 102351800 A CN102351800 A CN 102351800A
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- ZSYJMXLJNPEAGP-UHFFFAOYSA-N COC(NC#N)=O Chemical compound COC(NC#N)=O ZSYJMXLJNPEAGP-UHFFFAOYSA-N 0.000 description 1
- DGRGLKZMKWPMOH-UHFFFAOYSA-N Cc(cc1N)ccc1N Chemical compound Cc(cc1N)ccc1N DGRGLKZMKWPMOH-UHFFFAOYSA-N 0.000 description 1
- BCHKNFQUOAQOET-UHFFFAOYSA-N Cc1ccc2[nH]c(NC(OC)=O)nc2c1 Chemical compound Cc1ccc2[nH]c(NC(OC)=O)nc2c1 BCHKNFQUOAQOET-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for preparing 5-methylbenzimidazole-2-methyl carbamate. Three reaction steps, namely cyanamide formation, acidification and ring closing are performed, operating procedures are simplified, strong base such as sodium hydroxide is adopted for cyanamide formation, hydrochloric acid is adopted for acidification, sodium thiosulfate is adopted for catalyzing ring closing, waste acid is reduced, and pollutants are reduced on the premise of ensuring product quality and yield. The method comprises the following step of: performing cyanamide formation reaction, acidification reaction and ring closing reaction on methylclhlorofonmate serving as a raw material to obtain the product, wherein in the cyanamide formation reaction, the methylclhlorofonmate is reacted with cyanamide under the alkaline condition to form methylcyanocarbamate salt; in the acidification reaction, the methylcyanocarbamate salt is reacted with the hydrochloric acid to form methylcyanocarbamate; and in the ring closing reaction, the methylcyanocarbamate and 4-methoxy-o-phenylenediamine are subjected to condensation reaction to form the 5-methylbenzimidazole-2-methyl carbamate.
Description
Technical field
The present invention relates to a kind of preparation method of sterilant, is the preparation method of 5-methyl derosal more specifically to a kind of 5-tolimidazole-2-Urethylane.
Background technology
5-tolimidazole-2-Urethylane is a 5-methyl derosal; The systemic fungicide that belongs to efficient, wide spectrum, low toxicity; Chemical property is stable; Toxicity is low; The acute toxicity mld is the LD50 value: to the big white mouse per os greater than 20g/kg (be better than the LD50 value of derosal, be 15g/kg).Belong to the high-efficiency broad spectrum series bactericidal agent, can transfer to other position, disturb the mitotic division of germ cell, suppress its growth by plant absorbing and through conduction.Various crop there is prevention effect by the disease that fungi (like imperfect fungi, many ascomycetess etc.) causes, can be used for foliar spray, seed treatment and soil treatment etc.Also can be widely used in the antimycotic antiseptic field of industry such as timber, papermaking, weaving, leather, rubber.Present domestic relevant its synthesis method of bibliographical information that do not have.
(Biochemical Pharmacology such as Ernest Lacey only at present; Vol.34; No.7; Pp.1073-1077; 1985) reported to be raw material to monomethylaniline and prepared 5-tolimidazole-2-Urethylane through steps such as acetylize, nitrated, hydrolysis, reduction, Cheng Huan, rearrangements; Wherein reactions step is long, and toxicity such as used reagent such as tin protochloride, cyanogen bromide, isothiourea are bigger, and are difficult for suitability for industrialized production.
Summary of the invention
The objective of the invention is to solve the problems and shortcomings that exist in the present technology; The preparation method of a kind of 5-tolimidazole-2-Urethylane is provided; Method of the present invention is controlled to be cyanamideization, acidifying, three steps of cyclization with reactions step; Simplify schedule of operation, adopted highly basic such as sodium hydroxide cyanamideization, hcl acidifying; Sulfothiorine catalysis cyclization; Reduce the generation of spent acid, under the prerequisite that guarantees quality product and yield, reduced the growing amount of pollutent.
Technical scheme of the present invention is following:
The preparation method of 5-tolimidazole of the present invention-2-Urethylane, step is following: be raw material with the methyl-chloroformate, through obtaining 5-tolimidazole-2-Urethylane after cyanamide reaction, acidification reaction and the cyclization reaction; Wherein,
Described cyanamide reaction is following and cyanamide reaction generation Methyl cyanocarbamate salt for the methyl-chloroformate alkaline condition;
Described acidification reaction is that Methyl cyanocarbamate salt and hydrochloric acid reaction generate Methyl cyanocarbamate;
Condensation reaction takes place for Methyl cyanocarbamate and 4-methyl-o-phenylenediamine in described cyclization reaction under the acid catalysis condition, obtain 5-tolimidazole-2-Urethylane.
The preparation method of 5-tolimidazole of the present invention-2-Urethylane; Its further technical scheme is that described cyanamide reactions step is following: prepare the cyanamide aqueous solution earlier; And adding solvent; Regulate the pH value greater than 9 with the 5mol/L-10mol/L strong alkali aqueous solution again; Add phase-transfer catalyst again; Heat up and stir; Drip the reaction of methyl-chloroformate generation cyanamide; After reaction finishes; Product is poured in the mixture of ice and water, separated out solid, vacuum filtration; Filter cake is washed and is washed with methyl alcohol successively to neutrality, and drying can get the salt crystal of Methyl cyanocarbamate.Further technical scheme is that described cyanamide reactions step is following again: under-10 ℃ of-70 ℃ of agitation conditions; Priority is with the cyanamide aqueous solution of 10%-80% mass concentration; Solvent; The 5mol/L-10mol/L strong alkali aqueous solution; Phase-transfer catalyst drops in the reaction kettle; Control pH value of solution value is greater than 9; Speed with 10g/h-100g/h evenly drips methyl-chloroformate again; Behind the reaction 1h-8h; Obtain the Methyl cyanocarbamate salts solution; Pour in the mixture of ice and water; Separate out crystal; Suction filtration under the 760mmHg vacuum condition; Filter cake is washed and is washed with methyl alcohol successively to neutrality, and drying can get the salt crystal of Methyl cyanocarbamate; Wherein, cyanamide, the alkaline mol ratio in methyl-chloroformate, the cyanamide solution is 1.0: 1.0-2.0: 2.0-5.0.
The preparation method of 5-tolimidazole of the present invention-2-Urethylane, its further again technical scheme can also be that described highly basic is preferably sodium hydroxide or potassium hydroxide; Described solvent is preferably a kind of in water, methyl alcohol, ethanol, the acetone or their mixture, the consumption of solvent be methyl-chloroformate quality consumption 1-10 doubly; Described phase-transfer catalyst is preferably a kind of in benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, polyoxyethylene glycol, the X 2073 or their mixture, and the phase-transfer catalyst consumption is the 0.1%-10% of methyl-chloroformate quality consumption.
The preparation method of 5-tolimidazole of the present invention-2-Urethylane; Its further technical scheme can also be that described acidification reaction step is following: the salt crystal of the Methyl cyanocarbamate that the cyanamide reaction is obtained; With the acidifying of 4mol/L-5mol/L hydrochloric acid hydrolysis; Extract with hexanol; Collect organic phase; Underpressure distillation, fractionation obtains Methyl cyanocarbamate.Technical scheme further is that described acidification reaction step is following: under 20 ℃ of-70 ℃ of agitation conditions; With Methyl cyanocarbamate salt and the reaction of 4mol/L-5mol/L hydrochloric acid thorough mixing; Wherein the mol ratio of the hydrogenchloride in methyl-chloroformate salt and the hydrochloric acid soln is 1.0: 1.0-2.0; The pH value of control solution is between 6-7; Behind the reaction 1h-3h,, collect organic phase with the hexanol extraction; Underpressure distillation, fractionation obtains Methyl cyanocarbamate.
The preparation method of 5-tolimidazole of the present invention-2-Urethylane; Its further technical scheme can also be that described cyclization reactions step is following: getting the 4-methyl-o-phenylenediamine is raw material; Be dissolved in an amount of solvent; Add Methyl cyanocarbamate and catalyzer that acidification reaction obtains; Even Dropwise 35 % concentrated hydrochloric acid solution; Dripping terminal point is that the pH value is at 3-4; Reaction finishes the after heat suction filtration; Stir 0.5h-1h with 35% formaldehyde down at 70 ℃-80 ℃ again; Suction filtration; Drying promptly gets 5-tolimidazole-2-Urethylane.Further technical scheme is that described cyclization reactions step is following again: under 20 ℃ of-100 ℃ of agitation conditions; Successively be that 99% 4-methyl-o-phenylenediamine, Methyl cyanocarbamate, solvent, catalyzer drop in the reaction kettle with purity; Again with the even Dropwise 35 % of the speed concentrated hydrochloric acid of 10g/h-100g/h; 30 ℃-100 ℃ of dropping temperatures; The pH value of control solution is at 3-4; Reaction 2h-3h after heat suction filtration; Stir 0.5h-1h with 35% formaldehyde solution down at 70 ℃-80 ℃ again; Centrifugal; Suction filtration; Drying can get 5-tolimidazole-2-Urethylane; Wherein the mol ratio of 4-methyl-o-phenylenediamine and Methyl cyanocarbamate is 1.0: 1.0-2.0.
The preparation method of 5-tolimidazole of the present invention-2-Urethylane; Its technical scheme further can also be that described solvent is preferably a kind of in water, chloroform, hexanol, methyl alcohol, the ethanol or their mixture, solvent load be methyl-chloroformate quality consumption 1-10 doubly.Described catalyzer is preferably Sulfothiorine, and its consumption is the 0.1%-10% of 4-methyl-o-phenylenediamine.
The reaction equation that said process of the present invention relates to is following:
1. cyanamide chemical industry preface: methyl-chloroformate and cyanamide, sodium hydroxide reaction generate the Methyl cyanocarbamate sodium salt.
2. acidizing process: Methyl cyanocarbamate sodium salt and hydrochloric acid reaction generate Methyl cyanocarbamate.
3. cyclization operation: condensation reaction takes place in Methyl cyanocarbamate and 4-methyl-o-phenylenediamine under the acid catalysis condition, generates 5-tolimidazole-2-Urethylane.
Compared with prior art, beneficial effect of the present invention is mainly reflected in following several respects:
1, this process using methyl-chloroformate and 4-methyl-o-phenylenediamine cheap and easy to get is raw material, and reaction process is controlled to be cyanamideization, acidifying, three steps of cyclization, simplified schedule of operation, reduced production cost.
2, this process using benzyl trimethyl ammonium chloride is as the phase-transfer catalyst of cyanamide reaction, and reaction conditions is gentle, and catalytic effect is good, reduces the consumption of sodium hydroxide then, and the salkali waste liquid measure is reduced.
3, the inexpensive Sulfothiorine of this process using is as the cyclization catalyst for reaction; Reaction conditions is gentle; Catalyst levels is low; And characteristics with high conversion, green cleaning; And then can reduce the consumption of concentrated hydrochloric acid, and the spent acid amount is reduced, reduce the quantity discharged of pollutent greatly; Environmentally friendly, have good economic benefit and social benefit.
4, the sterilization effect of product 5-tolimidazole-2-Urethylane and derosal is suitable; Belong to efficient, low toxicity, wide spectrum, systemic fungicide; Lasting period is long; Toxicity is lower than derosal, can be widely used in the antimycotic antiseptic field of industry such as farm crop, timber, papermaking, weaving, leather, rubber.
The present invention compares with existing synthetic route, has that reaction scheme is easy, reaction conditions is gentle, catalytic activity is high, low in raw material cost is easy to get, the advantage of technology easy clean.
Description of drawings
The MS figure of 5-tolimidazole-2-Urethylane that Fig. 1 makes for embodiment 1
5-tolimidazole-2-Urethylane that Fig. 2 makes for embodiment 1
1H-NMR figure.
Embodiment
Below the present invention is described, but the present invention not merely is defined in these embodiment through specific embodiment.
Having temperature at 250mL takes into account in the four-hole boiling flask of whipping appts; Add 16.8g 50% cyanamide solution (containing cyanamide 0.2mol); The 60ml methanol solvate; NaOH solution of 64g concentration 25% (containing NaOH 0.4mol) and 0.5g benzyl trimethyl ammonium chloride are made phase-transfer catalyst; Speed with 30g/h evenly drips methyl-chloroformate 18.9g (0.2mol); Keep behind 45 ℃ of about 3h of reaction reaction solution being cooled off; Be poured into then in a large amount of mixture of ice and water; The adularescent crystal is separated out; Suction filtration under the 760mmHg vacuum condition; Filter cake is washed and is washed with methyl alcohol successively to neutrality; Drying can get Methyl cyanocarbamate sodium salt 18.7g, and yield is 76.8%.
Having temperature at 250mL takes into account in the four-hole boiling flask of whipping appts; With 18.3g (0.15mol) the Methyl cyanocarbamate sodium salt that makes and 5mol/L hydrochloric acid 30ml (containing hydrogenchloride 0.15mol) behind 40 ℃ of hybrid reaction 2.5h; Extract with hexanol; Collect organic phase; Underpressure distillation; Fractionation obtains Methyl cyanocarbamate 13.5g, and yield is 90.3%.
Having temperature at 250mL takes into account in the four-hole boiling flask of whipping appts; Adding 12.3g (0.2mol) purity is 99% 4-methyl-o-phenylenediamine; The 40ml methanol solvate; 10g (0.1mol) Methyl cyanocarbamate and 0.8g thiosulfuric acid sodium catalyst; The even Dropwise 35 % of speed concentrated hydrochloric acid solution with 30g/h; 50 ℃ of dropping temperatures; Dripping terminal point is that the pH value is about 3-4; Under 90 ℃, carry out insulation reaction 2h; Need cool to 80 ℃ after the insulation reaction; Add complexing agent 35% formaldehyde solution 100ml; Insulation 1h; Centrifugal more at last; Washing is extremely neutral, suction filtration, and drying can get 5-tolimidazole-2-Urethylane 15.0g; Yield is 73.2%, fusing point: 330 ℃-335 ℃.MS(m/z)：206[M+1]
+。
1H-NMR (300Hz, DMSO-d6), δ: 2.36 (s, 3H, 5-CH
3), 3.74 (s, 3H, CH
3), 6.89 (m, 1H, 6-H), 7.19 (d, J=0.63,1H, 4-H), 7.26 (d, J=8.04,1H, 7-H), 11.56 (NH uses D for s, 2H
20 is replaceable).
Having temperature at 250mL takes into account in the four-hole boiling flask of whipping appts; Add 33.6g 50% cyanamide solution (containing cyanamide 0.4mol); The 60ml methanol solvate; NaOH solution of 64g concentration 25% (containing NaOH 0.4mol) and 0.5g benzyl trimethyl ammonium chloride are made phase-transfer catalyst; Speed with 30g/h evenly drips methyl-chloroformate 18.9g (0.2mol); Keep behind 45 ℃ of about 3h of reaction reaction solution being cooled off; Be poured into then in a large amount of mixture of ice and water; The adularescent crystal is separated out; Suction filtration under the 760mmHg vacuum condition; Filter cake is washed and is washed with methyl alcohol successively to neutrality; Drying can get Methyl cyanocarbamate sodium salt 21.0g, and yield is 86.0%.
Having temperature at 250mL takes into account in the four-hole boiling flask of whipping appts; With 18.8g (0.15mol) the Methyl cyanocarbamate sodium salt that makes and 5mol/L hydrochloric acid 60ml (containing hydrogenchloride 0.3mol) behind 40 ℃ of hybrid reaction 2.5h; Extract with hexanol; Collect organic phase; Underpressure distillation; Fractionation obtains Methyl cyanocarbamate 13.8g, and yield is 92.3%.
Having temperature at 250mL takes into account in the four-hole boiling flask of whipping appts; Adding 12.3g (0.1mol) purity is 99% 4-methyl-o-phenylenediamine; The 40ml methanol solvate; 15g (0.15mol) Methyl cyanocarbamate and 0.8g thiosulfuric acid sodium catalyst; The even Dropwise 35 % of speed concentrated hydrochloric acid solution with 30g/h; 50 ℃ of dropping temperatures; Dripping terminal point is that the pH value is about 3-4; Under 90 ℃, carry out insulation reaction 2h; Need cool to 80 ℃ after the insulation reaction; Add complexing agent 35% formaldehyde solution 100ml; Insulation 1h; Centrifugal more at last; Washing is extremely neutral, suction filtration, and drying can get 5-tolimidazole-2-Urethylane 16.3g; Yield is 79.5%, fusing point: 330 ℃-335 ℃.
Embodiment 3
Having temperature at 250mL takes into account in the four-hole boiling flask of whipping appts; Add 33.6g 50% cyanamide solution (containing cyanamide 0.4mol); The 60ml methanol solvate; NaOH solution of 96g concentration 25% (containing NaOH 0.6mol) and 0.5g benzyl trimethyl ammonium chloride are made phase-transfer catalyst; Speed with 30g/h evenly drips methyl-chloroformate 18.9g (0.2mol); Keep behind 45 ℃ of about 3h of reaction reaction solution being cooled off; Be poured into then in a large amount of mixture of ice and water; The adularescent crystal is separated out; Suction filtration under the 760mmHg vacuum condition; Filter cake is washed and is washed with methyl alcohol successively to neutrality; Drying can get Methyl cyanocarbamate sodium salt 20.1g, and yield is 82.2%.
Having temperature at 250mL takes into account in the four-hole boiling flask of whipping appts; With 18.3g (0.15mol) the Methyl cyanocarbamate sodium salt that makes and 5mol/L hydrochloric acid 50ml (containing hydrogenchloride 0.25mol) behind 40 ℃ of hybrid reaction 2.5h; Extract with hexanol; Collect organic phase; Underpressure distillation; Fractionation obtains Methyl cyanocarbamate 13.6g, and yield is 90.3%.
Having temperature at 250mL takes into account in the four-hole boiling flask of whipping appts; Adding 12.3g (0.1mol) purity is 99% 4-methyl-o-phenylenediamine; The 40ml methanol solvate; 20g (0.2mol) Methyl cyanocarbamate and 0.8g thiosulfuric acid sodium catalyst; The even Dropwise 35 % of speed concentrated hydrochloric acid solution with 30g/h; 50 ℃ of dropping temperatures; Dripping terminal point is that the pH value is about 3-4; Under 90 ℃, carry out insulation reaction 2h; Need cool to 80 ℃ after the insulation reaction; Add complexing agent 35% formaldehyde solution 100ml; Insulation 1h; Centrifugal more at last; Washing is extremely neutral, suction filtration, and drying can get 5-tolimidazole-2-Urethylane 15.8g; Yield is 76.8%, fusing point: 330 ℃-335 ℃.
Claims (10)
1. the preparation method of 5-tolimidazole-2-Urethylane is characterized in that: be raw material with the methyl-chloroformate, through obtaining 5-tolimidazole-2-Urethylane after cyanamide reaction, acidification reaction and the cyclization reaction; Wherein,
Described cyanamide reaction is following and cyanamide reaction generation Methyl cyanocarbamate salt for the methyl-chloroformate alkaline condition;
Described acidification reaction is that Methyl cyanocarbamate salt and hydrochloric acid reaction generate Methyl cyanocarbamate;
Condensation reaction takes place for Methyl cyanocarbamate and 4-methyl-o-phenylenediamine in described cyclization reaction under the acid catalysis condition, obtain 5-tolimidazole-2-Urethylane.
2. the preparation method of 5-tolimidazole according to claim 1-2-Urethylane; It is characterized in that described cyanamide reactions step is following: prepare the cyanamide aqueous solution earlier; And adding solvent; Regulate the pH value greater than 9 with the 5mol/L-10mol/L strong alkali aqueous solution again; Add phase-transfer catalyst again; Heat up and stir; Drip the reaction of methyl-chloroformate generation cyanamide; After reaction finishes; Product is poured in the mixture of ice and water, separated out solid, vacuum filtration; Filter cake is washed and is washed with methyl alcohol successively to neutrality, and drying can get the salt crystal of Methyl cyanocarbamate.
3. the preparation method of 5-tolimidazole according to claim 2-2-Urethylane; It is characterized in that described cyanamide reactions step is following: under-10 ℃ of-70 ℃ of agitation conditions; Priority is with the cyanamide aqueous solution of 10%-80% mass concentration; Solvent; The 5mol/L-10mol/L strong alkali aqueous solution; Phase-transfer catalyst drops in the reaction kettle; Control pH value of solution value is greater than 9; Speed with 10g/h-100g/h evenly drips methyl-chloroformate again; Behind the reaction 1h-8h; Obtain the Methyl cyanocarbamate salts solution; Pour in the mixture of ice and water; Separate out crystal; Suction filtration under the 760mmHg vacuum condition; Filter cake is washed and is washed with methyl alcohol successively to neutrality, and drying can get the salt crystal of Methyl cyanocarbamate; Wherein, cyanamide, the alkaline mol ratio in methyl-chloroformate, the cyanamide solution is 1.0: 1.0-2.0: 2.0-5.0.
4. according to the preparation method of claim 2 or 3 described 5-tolimidazole-2-Urethylanes, it is characterized in that described highly basic is sodium hydroxide or potassium hydroxide; Described solvent is a kind of in water, methyl alcohol, ethanol, the acetone or their mixture, the consumption of solvent be methyl-chloroformate quality consumption 1-10 doubly; Described phase-transfer catalyst is a kind of in benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, polyoxyethylene glycol, the X 2073 or their mixture, and the phase-transfer catalyst consumption is the 0.1%-10% of methyl-chloroformate quality consumption.
5. the preparation method of 5-tolimidazole according to claim 1-2-Urethylane; It is characterized in that described acidification reaction step is following: the salt crystal of the Methyl cyanocarbamate that the cyanamide reaction is obtained; With the acidifying of 4mol/L-5mol/L hydrochloric acid hydrolysis; Extract with hexanol; Collect organic phase; Underpressure distillation, fractionation obtains Methyl cyanocarbamate.
6. the preparation method of 5-tolimidazole according to claim 5-2-Urethylane; It is characterized in that described acidification reaction step is following: under 20 ℃ of-70 ℃ of agitation conditions; With Methyl cyanocarbamate salt and the reaction of 4mol/L-5mol/L hydrochloric acid thorough mixing; Wherein the mol ratio of the hydrogenchloride in methyl-chloroformate salt and the hydrochloric acid soln is 1.0: 1.0-2.0; The pH value of control solution is between 6-7; Behind the reaction 1h-3h; Extract with hexanol; Collect organic phase; Underpressure distillation, fractionation obtains Methyl cyanocarbamate.
7. the preparation method of 5-tolimidazole according to claim 1-2-Urethylane; It is characterized in that described cyclization reactions step is following: getting the 4-methyl-o-phenylenediamine is raw material; Be dissolved in an amount of solvent; Add Methyl cyanocarbamate and catalyzer that acidification reaction obtains; Even Dropwise 35 % concentrated hydrochloric acid solution; Dripping terminal point is that the pH value is at 3-4; Reaction finishes the after heat suction filtration; Again with 35% formaldehyde at 70 ℃-80 ℃ following stirring 0.5h-1h; Suction filtration; Drying promptly gets 5-tolimidazole-2-Urethylane.
8. the method for preparing 5-tolimidazole-2-Urethylane according to claim 7; It is characterized in that described cyclization reactions step is following: under 20 ℃ of-100 ℃ of agitation conditions; Priority is 99% 4-methyl-o-phenylenediamine with purity; Methyl cyanocarbamate; Solvent; Catalyzer drops in the reaction kettle; Again with the even Dropwise 35 % of the speed concentrated hydrochloric acid of 10g/h-100g/h; 30 ℃-100 ℃ of dropping temperatures; The pH value of control solution is at 3-4; Reaction 2h-3h after heat suction filtration; Stir 0.5h-1h with 35% formaldehyde solution down at 70 ℃-80 ℃ again; Centrifugal; Suction filtration, drying can get 5-tolimidazole-2-Urethylane; Wherein the mol ratio of 4-methyl-o-phenylenediamine and Methyl cyanocarbamate is 1.0: 1.0-2.0.
9. the method for preparing 5-tolimidazole-2-Urethylane according to claim 8; It is characterized in that described solvent is a kind of in water, chloroform, hexanol, methyl alcohol, the ethanol or their mixture, solvent load be methyl-chloroformate quality consumption 1-10 doubly.
10. the method for preparing 5-tolimidazole-2-Urethylane according to claim 8 is characterized in that described catalyzer is a Sulfothiorine, and its consumption is the 0.1%-10% of 4-methyl-o-phenylenediamine.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103058932A (en) * | 2013-02-01 | 2013-04-24 | 黄河三角洲京博化工研究院有限公司 | Synthetic method of N-(2-benzimidazolyl)-methyl carbamate |
| CN104961685A (en) * | 2015-06-11 | 2015-10-07 | 安徽东至广信农化有限公司 | Method for reducing carbendazim impurity DAP in production process of carbendazim |
| CN104961655A (en) * | 2015-06-11 | 2015-10-07 | 安徽东至广信农化有限公司 | Process for hydrolyzing lime nitrogen at one step |
| CN111423442A (en) * | 2020-04-03 | 2020-07-17 | 重庆美莱德生物医药有限公司 | Epinastine hydrochloride intermediate and synthesis method thereof |
| CN111574460A (en) * | 2020-07-06 | 2020-08-25 | 山东国邦药业有限公司 | Preparation method of albendazole |
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2011
- 2011-09-09 CN CN2011102673464A patent/CN102351800A/en active Pending
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| CN103058932A (en) * | 2013-02-01 | 2013-04-24 | 黄河三角洲京博化工研究院有限公司 | Synthetic method of N-(2-benzimidazolyl)-methyl carbamate |
| CN103058932B (en) * | 2013-02-01 | 2015-10-07 | 京博农化科技股份有限公司 | The synthetic method of N-(2-benzimidazolyl-)-Urethylane |
| CN104961685A (en) * | 2015-06-11 | 2015-10-07 | 安徽东至广信农化有限公司 | Method for reducing carbendazim impurity DAP in production process of carbendazim |
| CN104961655A (en) * | 2015-06-11 | 2015-10-07 | 安徽东至广信农化有限公司 | Process for hydrolyzing lime nitrogen at one step |
| CN104961655B (en) * | 2015-06-11 | 2017-01-18 | 安徽东至广信农化有限公司 | Process for hydrolyzing lime nitrogen at one step |
| CN111423442A (en) * | 2020-04-03 | 2020-07-17 | 重庆美莱德生物医药有限公司 | Epinastine hydrochloride intermediate and synthesis method thereof |
| CN111423442B (en) * | 2020-04-03 | 2022-09-27 | 重庆美莱德生物医药有限公司 | Epinastine hydrochloride intermediate and synthesis method thereof |
| CN115504985A (en) * | 2020-04-03 | 2022-12-23 | 重庆美莱德生物医药有限公司 | Synthesis method of epinastine hydrochloride |
| CN115504985B (en) * | 2020-04-03 | 2024-01-19 | 重庆美莱德生物医药有限公司 | Synthesis method of epinastine hydrochloride |
| CN111574460A (en) * | 2020-07-06 | 2020-08-25 | 山东国邦药业有限公司 | Preparation method of albendazole |
| CN111574460B (en) * | 2020-07-06 | 2021-11-05 | 山东国邦药业有限公司 | Preparation method of albendazole |
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Application publication date: 20120215 |