CN100339365C - 3-amido-4-alkylamino lauseto neu preparation method - Google Patents
3-amido-4-alkylamino lauseto neu preparation method Download PDFInfo
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- CN100339365C CN100339365C CNB2005100609913A CN200510060991A CN100339365C CN 100339365 C CN100339365 C CN 100339365C CN B2005100609913 A CNB2005100609913 A CN B2005100609913A CN 200510060991 A CN200510060991 A CN 200510060991A CN 100339365 C CN100339365 C CN 100339365C
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Abstract
The present invention discloses a method for preparing 3-amido-4-alkylamino benzyl sulfone, which comprises the following materials: firstly, p-chlorobenzenesulfonyl chloride is firstly used as raw materials; the p-chlorobenzenesulfonyl chloride is reduced to p-chlorobenzene sulfonate by sulfite under the existence of hydrocarbonate; p-chlorobenzene benzyl sulfone is generated by a condensed decarboxylic reaction of halogenated acetic acid and alkyl sulfonic acid as a catalyst; 4-chloro-3-nitryl benzyl sulfone is obtained by nitration in the mixed acid; amine substituted by alkyl is used for nucleophilic substitution reaction so as to obtain 4-chloro-3-nitryl benzyl sulfone; finally, nitryl is reduced by a reducing agent to obtain the 3-amido-4-alkylamino benzyl sulfone. The method for preparing the 3-amido-4-alkylamino benzyl sulfone has the advantages of mild reaction condition, high product purity and high product yield, and can greatly reduce the production cost.
Description
Technical field
The present invention relates to the preparation method of synthetic white dyes class midbody compound 3-amino-4-alkylamino lauseto neu.
Background technology
It is existing that 3-amino-main preparation methods of 4-alkylamino lauseto neu is with V-Brite B 4-methylamino--3-nitrobenzoyl sulfone to be reduced into 3-amino-4-alkylamino lauseto neu (Dyes andPigments (1989), 11 (2), 147-161), the shortcoming of this method is that the reduction yield is low, have only 52%, by product is more, and environment is had pollution, and the raw material sources difficulty.
Summary of the invention
The method for preparing 3-amino-4-alkylamino lauseto neu that the purpose of this invention is to provide few, the high yield of a kind of three wastes, low cost and constant product quality.
The preparation method of 3-amino of the present invention-4-alkylamino lauseto neu in turn includes the following steps:
The first step is raw material with the parachloroben-zenesulfonyl chloride, in the presence of supercarbonate, with water is solvent, reduce with sulphite, the mol ratio of supercarbonate and parachloroben-zenesulfonyl chloride is 2～4: 1, the mol ratio of sulphite and parachloroben-zenesulfonyl chloride is 1～1.5: 1, and reaction 2～3h makes the chlorobenzene-sulfinate under 60～90 ℃;
Second step was a catalyzer with alkylsulphonic acid, Phenylsulfonic acid or tosic acid, to chlorobenzene-sulfinate and halogenated acetic acids through the condensation decarboxylic reaction, generate down the chlorine lauseto neu in 90 ℃～reflux temperature, the mol ratio of halogenated acetic acids and parachloroben-zenesulfonyl chloride is 1～1.5: 1, and alkylsulphonic acid, Phenylsulfonic acid or tosic acid consumption are 5～50% of halogenated acetic acids weight;
The 3rd step was a nitration mixture with the vitriol oil and nitrosonitric acid, under 20～60 ℃, will be to the nitrated 4-chloro-3-nitrobenzoyl sulfone that makes of chlorine lauseto neu, vitriol oil consumption is to 50～200% of chlorine lauseto neu weight, the nitrosonitric acid consumption is to 70～200% of chlorine lauseto neu weight;
The 4th step was a solvent with alcohol, the amine that replaces with alkyl carries out nucleophilic substitution reaction to 4-chloro-3-nitrobenzoyl sulfone and makes 4-alkylamino-3-nitrobenzoyl sulfone under 60～80 ℃, the amine that alkyl replaces is 1.1～3.2: 1 with mol ratio to 4-chloro-3-nitrobenzoyl sulfone;
The 5th step made 3-amino-4-alkylamino lauseto neu with reduced iron powder or sulfocompound with the nitroreduction in 4-alkylamino-3-nitrobenzoyl sulfone, wherein the mol ratio of reduced iron powder and 4-alkylamino-3-nitrobenzoyl sulfone is 2.3～4.5: 1, and the mol ratio of sulfocompound and 4-alkylamino-3-nitrobenzoyl sulfone is 1.0～3.2: 1; Perhaps the nitroreduction in 4-alkylamino-3-nitrobenzoyl sulfone is made 3-amino-4-alkylamino lauseto neu with catalyzer and liquid hydrogen donor, catalyst levels is 2～15% of 4-alkylamino-3-nitrobenzoyl sulfone weight, and the consumption of liquid hydrogen donor is 20～100% of 4-alkylamino-3-nitrobenzoyl sulfone weight; Perhaps catalytic hydrogenation makes 3-amino-4-alkylamino lauseto neu with the nitroreduction in 4-alkylamino-3-nitrobenzoyl sulfone in alcohols, halohydrocarbon or aromatic solvent, and catalyst levels is 2～15% of 4-alkylamino-3-nitrobenzoyl sulfone weight.
Concrete synthetic route is as follows:
In the formula, R
1And R
2Structure specifically sees the following form
| R 1 | R 2 |
| H | CH 3 |
| CH 3 | CH 3 |
| H | CH 3CH 2 |
| CH 3CH 2 | CH 3CH 2 |
| H | CH 3CH 2CH 2 |
| H | (CH 3) 2CH |
| H | CH 3CH 2CH 2CH 2 |
The used supercarbonate of the first step is sodium bicarbonate or saleratus among the preparation method of the present invention; Used sulphite is S-WAT or potassium sulfite.The used alkylsulphonic acid catalyzer of the second step condensation reaction is methylsulfonic acid, ethyl sulfonic acid, Phenylsulfonic acid or tosic acid; Used halogenated acetic acids is chloracetic acid or monobromo-acetic acid.The 3rd step nitration reaction preferable reaction temperature is 30～45 ℃.The amine that used alkyl replaces in the four-step reaction is methylamine, dimethylamine, ethamine, diethylamine, Tri N-Propyl Amine Isopropylamine or n-Butyl Amine 99; Used solvent alcohol is methyl alcohol or ethanol.Used sulfocompound is sodium sulphite, Sodium sulfhydrate or sodium disulfide in the 5th step reduction reaction; Catalyzer is Raney nickel or 5～10% palladium charcoals in catalyzer and the reduction of liquid hydrogen donor, and liquid hydrogen donor is hydrazine hydrate or anhydrous formic acid ammonium.The catalyzer of catalytic hydrogenation is Raney nickel or 5～10% palladium charcoals in alcohols, halohydrocarbon or aromatic solvent; The solvent alcohols is methyl alcohol, ethanol, n-propyl alcohol, Virahol or the trimethyl carbinol, and halohydrocarbon is methylene dichloride, chloroform, tetracol phenixin or 1, and 2-ethylene dichloride, aromatic hydrocarbons are benzene, toluene or chlorobenzene.
Adopt preparation method of the present invention, synthetic is catalyzer with the alkylsulphonic acid during to the chlorine lauseto neu, carries out condensation decarboxylic reaction yield height with halogenated acetic acids, and the three wastes are few, and condition is relatively gentleer; Reduction reaction all can make 3-amino-4-alkylamino lauseto neu by high yield reduction nitro with different catalyzer, the purity height of product, and the reaction conditions gentleness, and production cost can descend significantly.
Embodiment
Embodiment 1
The first step is synthetic to chlorobenzene-sulfinic acid sodium
In the 2000ml four-hole boiling flask, add sodium sulphite anhydrous 99.3 144g (1.14mol), water 820ml, anhydrous sodium bicarbonate 240g (2.86mol), oil bath is warming up to 70 ℃, add parachloroben-zenesulfonyl chloride 233.6g (1.11mol), be incubated at 70～80 ℃ stirring reaction 2.5 hours, reduce to room temperature, be directly used in next step reaction.
Second step is synthetic to the chlorine lauseto neu
Upwards in the single step reaction liquid, add Mono Chloro Acetic Acid 127.5g (1.3mol), tosic acid 18g, oil bath is warming up to 105 ℃, and back flow reaction 8 hours no longer includes bubble to the reaction solution and bloats, reaction finishes, with the ice-water bath cooling, suction filtration is washed three times, dry, the white granular solid to chlorine lauseto neu 193.2g, mp:95～96 ℃, yield 91.6%.
Synthesizing of the 3rd step 4-chloro-3-nitrobenzoyl sulfone
With vitriol oil 60ml (110.4g, 1.13mol) slowly be added to nitrosonitric acid 100ml (154g, 2.44mol) in, be mixed with nitration mixture, be cooled to 20 ℃, slowly add chlorine lauseto neu 148g (0.777mol), mechanical stirring, temperature control continues reaction 40min for 30 ℃, reaction product is poured in the beaker that frozen water is housed, use 30% sodium hydroxide solution neutralization reaction liquid to alkalescence, suction filtration, drying then, use ethyl alcohol recrystallization, obtain light yellow solid 4-chloro-3-nitrobenzoyl sulfone 160.5g, mp:121.5～122.5 ℃, yield 87.7%.
Synthesizing of the 4th step 4-methylamino--3-nitrobenzoyl sulfone
In the 1000ml four-hole boiling flask, add 4-chloro-3-nitrobenzoyl sulfone 91.4g (0.388mol), ethanol 160ml, mechanical stirring, oil bath is warming up to 50 ℃, drips aqueous methylamine solution 70ml (40%), and about 0.5h drips complete, control reaction temperature 50-60 ℃, continue to stir 2～3h, it is yellow that reaction solution gradually becomes, reaction finishes, and is cooled to room temperature, suction filtration, oven dry, glassy yellow solid 4-methylamino--3-nitrobenzoyl sulfone 86.7g, mp:190～192 ℃, yield 96.9%.
Synthesizing of the 5th step 3-amino-4-methylamino-lauseto neu
With 4-methylamino--3-nitrobenzoyl sulfone 23g (0.1mol), reduced iron powder 19.6g (0.35mol) is added in 100ml 95% ethanol, adds the 5ml concentrated hydrochloric acid, be heated to backflow, reacted 8 hours, reaction finishes, while hot suction filtration, twice of 50ml 95% ethanol rinsing of filter cake, merging filtrate concentrates, and gets purple tabular crystal 3-amino-4-methylamino-lauseto neu 14g, yield: 70%, mp:98～99 ℃.
Embodiment 2
The first step is synthetic to chlorobenzene-sulfinic acid sodium
In the 2000ml four-hole boiling flask, add anhydrous potassium sulfite 181.7g (1.15mol), water 820ml, Carbon Dioxide hydrogen potassium 300g (3.0mol), oil bath is warming up to 70 ℃, add parachloroben-zenesulfonyl chloride 233.6g (1.11mol), be incubated at 70～80 ℃ stirring reaction 2 hours, reduce to room temperature, be directly used in next step reaction.
Second step is synthetic to the chlorine lauseto neu
Upwards in the single step reaction liquid, add bromoacetic acid 154.3g (1.11mol), tosic acid 18g, oil bath is warming up to 90 ℃, and all the other get the white granular solid to the chlorine lauseto neu with 1 second step of embodiment.
Synthesizing of the 3rd step 4-chloro-3-nitrobenzoyl sulfone
Vitriol oil 40.5ml (74.5g) slowly is added among the nitrosonitric acid 192.2ml (296g), is mixed with nitration mixture, be cooled to 20 ℃, slowly add chlorine lauseto neu 148g (0.777mol), mechanical stirring, all the other obtain light yellow solid 4-chloro-3-nitrobenzoyl sulfone with the 3rd step of embodiment 1.
Synthesizing of the 4th step 4-methylamino--3-nitrobenzoyl sulfone
In the 1000ml four-hole boiling flask, add 4-chloro-3-nitrobenzoyl sulfone 91.4g (0.388mol), ethanol 150ml, mechanical stirring, oil bath is warming up to 50 ℃, drip first ammonia soln 90.2ml (40%), all the other get glassy yellow solid 4-methylamino--3-nitrobenzoyl sulfone with the 4th step of embodiment 1.
Synthesizing of the 5th step 3-amino-4-methylamino-lauseto neu
With 4-methylamino--3-nitrobenzoyl sulfone 23g (0.1mol), sodium sulphite 14g (0.18mol) is added in the 100ml water, is heated to backflow, reacts 8 hours, reaction finishes, suction filtration while hot, and filter cake is with twice of 50ml water rinse, merging filtrate concentrates, and gets 3-amino-4-methylamino-lauseto neu.
Embodiment 3
The first step is synthetic to chlorobenzene-sulfinic acid sodium
In the 2000ml four-hole boiling flask, add sodium sulphite anhydrous 99.3 153.8g (1.22mol), water 850ml, anhydrous sodium bicarbonate 186.5g (2.22mol), oil bath is warming up to 70 ℃, add parachloroben-zenesulfonyl chloride 233.6g (1.11mol), be incubated at 85～90 ℃ stirring reaction 3 hours, reduce to room temperature, be directly used in next step reaction.
Second step is synthetic to the chlorine lauseto neu
Upwards in the single step reaction liquid, add Mono Chloro Acetic Acid 131.1g (1.39mol), methylsulfonic acid 20g, oil bath is warming up to backflow, and all the other get the white granular solid to the chlorine lauseto neu with 1 second step of embodiment.
Synthesizing of the 3rd step 4-chloro-3-nitrobenzoyl sulfone
Vitriol oil 64.5ml (118.7g) slowly is added among the nitrosonitric acid 163.4ml (251.6g), is mixed with nitration mixture, be cooled to 20 ℃, slowly add chlorine lauseto neu 148g (0.777mol), mechanical stirring, all the other obtain light yellow solid 4-chloro-3-nitrobenzoyl sulfone with the 3rd step of embodiment 1.
Synthesizing of the 4th step 4-diethylin-3-nitrobenzoyl sulfone
In the 1000ml four-hole boiling flask, add 4-chloro-3-nitrobenzoyl sulfone 91.4g (0.388mol), ethanol 160ml, mechanical stirring, oil bath is warming up to 50 ℃, drip diethylamine 56.6g (0.62mol), all the other get 4-diethylin-3-nitrobenzoyl sulfone with the 4th step of embodiment 1.
Synthesizing of the 5th step 3-amino-4-diethylin lauseto neu
With 4-diethylin-3-nitrobenzoyl sulfone 27.2g (0.1mol), 1.0g 10%Pd/C, hydrazine hydrate 18g (85%) is added in the 100ml ethanol, is heated to backflow, reacts 8 hours, reaction finishes, suction filtration while hot, filter cake is with 50ml water rinse twice, merging filtrate, concentrate, get 3-amino-4-diethylin lauseto neu.
Embodiment 4
The first step is synthetic to chlorobenzene-sulfinic acid sodium
In the 2000ml four-hole boiling flask, add sodium sulphite anhydrous 99.3 167.6g (1.33mol), water 900ml, anhydrous sodium bicarbonate 279.7g (3.33mol), oil bath is warming up to 70 ℃, add parachloroben-zenesulfonyl chloride 233.6g (1.11mol), be incubated at 70～75 ℃ stirring reaction 2.5 hours, reduce to room temperature, be directly used in next step reaction.
Second step is synthetic to the chlorine lauseto neu
Upwards in the single step reaction liquid, add Mono Chloro Acetic Acid 139.9g (1.48mol), methylsulfonic acid 10g, oil bath is warming up to backflow, and all the other get the white granular solid to the chlorine lauseto neu with 1 second step of embodiment.
Synthesizing of the 3rd step 4-chloro-3-nitrobenzoyl sulfone
Vitriol oil 96.5ml (177.6g) slowly is added among the nitrosonitric acid 125ml (192.5g), is mixed with nitration mixture, all the other obtain light yellow solid 4-chloro-3-nitrobenzoyl sulfone with the 3rd step of embodiment 1.
Synthesizing of the 4th step 4-n-propylamine base-3-nitrobenzoyl sulfone
In the 1000ml four-hole boiling flask, add 4-chloro-3-nitrobenzoyl sulfone 91.4g (0.388mol), ethanol 160ml, mechanical stirring, oil bath is warming up to 50 ℃, drips Tri N-Propyl Amine 36.6g (0.62), and about 0.5h drips complete, all the other get 4-n-propylamine base-3-nitrobenzoyl sulfone with the 4th step of embodiment 1.
Synthesizing of the 5th step 3-amino-4-n-propylamine base lauseto neu
With 4-n-propylamine base-3-nitrobenzoyl sulfone 25.8g (0.1mol), the 100ml dehydrated alcohol is put in the autoclave, add 2.3g Raney nickel, fill hydrogen to pressure and reach 10Mpa, reacted 10 hours, no longer reduce to pressure, reaction finishes, the 50ml dehydrated alcohol rinsing twice of suction filtration, filter cake, merging filtrate, concentrate, get 3-amino-4-n-propylamine base lauseto neu.
Embodiment 5
The first step is synthetic to chlorobenzene-sulfinic acid sodium
In the 2000ml four-hole boiling flask, add sodium sulphite anhydrous 99.3 181.4g (1.44mol), water 1000ml, anhydrous sodium bicarbonate 325.9g (3.88mol), oil bath is warming up to 70 ℃, add parachloroben-zenesulfonyl chloride 233.6g (1.11mol), be incubated at 65～70 ℃ stirring reaction 3 hours, reduce to room temperature, be directly used in next step reaction.
Second step is synthetic to the chlorine lauseto neu
Upwards in the single step reaction liquid, add Mono Chloro Acetic Acid 146.5g (1.55mol), Phenylsulfonic acid 30g, oil bath is warming up to backflow, and all the other get the white granular solid to the chlorine lauseto neu with 1 second step of embodiment.
Synthesizing of the 3rd step 4-chloro-3-nitrobenzoyl sulfone
Vitriol oil 144.8ml (266.4g) slowly is added among the nitrosonitric acid 76.7ml (118.1g), is mixed with nitration mixture, all the other obtain light yellow solid 4-chloro-3-nitrobenzoyl sulfone with the 3rd step of embodiment 1.
Synthesizing of the 4th step 4-n-butyl amine base-3-nitrobenzoyl sulfone
In the 1000ml four-hole boiling flask, add 4-chloro-3-nitrobenzoyl sulfone 91.4g (0.388mol), ethanol 160ml, mechanical stirring, oil bath is warming up to 50 ℃, drip n-Butyl Amine 99 34.3ml (0.47mol), all the other get 4-n-butyl amine base-3-nitrobenzoyl sulfone with the 4th step of embodiment 1.
Synthesizing of the 5th step 3-amino-4-n-butyl amine base lauseto neu
With 4-n-butyl amine base-3-nitrobenzoyl sulfone 27.2g (0.1mol), the 100ml dehydrated alcohol is put in the autoclave, add 2.2g 5%Pd/C, fill hydrogen to pressure and reach 8Mpa, reacted 10 hours, no longer reduce to pressure, reaction finishes, the 50ml dehydrated alcohol rinsing twice of suction filtration, filter cake, merging filtrate, concentrate, get 3-amino-4-n-butyl amine base lauseto neu.
Claims (8)
1.3-the preparation method of amino-4-alkylamino lauseto neu in turn includes the following steps:
The first step is raw material with the parachloroben-zenesulfonyl chloride, in the presence of supercarbonate, with water is solvent, reduce with sulphite, the mol ratio of supercarbonate and parachloroben-zenesulfonyl chloride is 2～4: 1, the mol ratio of sulphite and parachloroben-zenesulfonyl chloride is 1～1.5: 1, and reaction 2～3h makes the chlorobenzene-sulfinate under 60～90 ℃;
Second step was a catalyzer with alkylsulphonic acid, Phenylsulfonic acid or tosic acid, to chlorobenzene-sulfinate and halogenated acetic acids through the condensation decarboxylic reaction, generate down the chlorine lauseto neu in 90 ℃～reflux temperature, the mol ratio of halogenated acetic acids and parachloroben-zenesulfonyl chloride is 1～1.5: 1, and alkylsulphonic acid, Phenylsulfonic acid or tosic acid consumption are 5～50% of halogenated acetic acids weight;
The 3rd step was a nitration mixture with the vitriol oil and nitrosonitric acid, under 20～60 ℃, will be to the nitrated 4-chloro-3-nitrobenzoyl sulfone that makes of chlorine lauseto neu, vitriol oil consumption is to 50～200% of chlorine lauseto neu weight, the nitrosonitric acid consumption is to 70～200% of chlorine lauseto neu weight;
The 4th step was a solvent with alcohol, the amine that replaces with alkyl carries out nucleophilic substitution reaction to 4-chloro-3-nitrobenzoyl sulfone and makes 4-alkylamino-3-nitrobenzoyl sulfone under 60～80 ℃, the amine that alkyl replaces is 1.1～3.2: 1 with mol ratio to 4-chloro-3-nitrobenzoyl sulfone;
The 5th step made 3-amino-4-alkylamino lauseto neu with reduced iron powder or sulfocompound with the nitroreduction in 4-alkylamino-3-nitrobenzoyl sulfone, wherein the mol ratio of reduced iron powder and 4-alkylamino-3-nitrobenzoyl sulfone is 2.3～4.5: 1, and the mol ratio of sulfocompound and 4-alkylamino-3-nitrobenzoyl sulfone is 1.0～3.2: 1; Perhaps the nitroreduction in 4-alkylamino-3-nitrobenzoyl sulfone is made 3-amino-4-alkylamino lauseto neu with catalyzer and liquid hydrogen donor, catalyst levels is 2～15% of 4-alkylamino-3-nitrobenzoyl sulfone weight, and the consumption of liquid hydrogen donor is 20～100% of 4-alkylamino-3-nitrobenzoyl sulfone weight; Perhaps catalytic hydrogenation makes 3-amino-4-alkylamino lauseto neu with the nitroreduction in 4-alkylamino-3-nitrobenzoyl sulfone in alcohols, halohydrocarbon or aromatic solvent, and catalyst levels is 2～15% of 4-alkylamino-3-nitrobenzoyl sulfone weight.
2. by the preparation method of the described 3-amino of claim 1-4-alkylamino lauseto neu, it is characterized in that the used supercarbonate of the first step is sodium bicarbonate or saleratus, used sulphite is S-WAT or potassium sulfite.
3. by the preparation method of the described 3-amino of claim 1-4-alkylamino lauseto neu, it is characterized in that the used alkylsulphonic acid catalyzer of the second step condensation reaction is methylsulfonic acid or ethyl sulfonic acid, used halogenated acetic acids is chloracetic acid or monobromo-acetic acid.
4. by the preparation method of the described 3-amino of claim 1-4-alkylamino lauseto neu, it is characterized in that the 3rd step nitration reaction temperature is 30～45 ℃.
5. by the preparation method of the described 3-amino of claim 1-4-alkylamino lauseto neu, it is characterized in that the amine that alkyl used in the four-step reaction replaces is methylamine, dimethylamine, ethamine, diethylamine, Tri N-Propyl Amine, Isopropylamine or n-Butyl Amine 99.
6. by the preparation method of the described 3-amino of claim 1-4-alkylamino lauseto neu, it is characterized in that solvent alcohol used in the four-step reaction is methyl alcohol or ethanol.
7. press the preparation method of the described 3-amino of claim 1-4-alkylamino lauseto neu, it is characterized in that used sulfocompound is sodium sulphite, Sodium sulfhydrate or sodium disulfide in the 5th step reduction reaction, catalyzer is Raney nickel or 5～10% palladium charcoals in catalyzer and the liquid hydrogen donor, and liquid hydrogen donor is hydrazine hydrate or anhydrous formic acid ammonium.
8. press the preparation method of the described 3-amino of claim 1-4-alkylamino lauseto neu, it is characterized in that the 5th step catalyzer of catalytic hydrogenation in alcohols, halohydrocarbon or aromatic solvent is Raney nickel or 5～10% palladium charcoals, the solvent alcohols is methyl alcohol, ethanol, n-propyl alcohol, Virahol or the trimethyl carbinol, halohydrocarbon is methylene dichloride, chloroform, tetracol phenixin or 1,2-ethylene dichloride, aromatic hydrocarbons are benzene, toluene or chlorobenzene.
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| CN103224438B (en) * | 2013-04-07 | 2015-02-25 | 辽宁大学 | Method for synthesizing N, N-dimethyl amine compound by nucleophilic substitution of DMF |
| CN103709095B (en) * | 2014-01-14 | 2016-06-22 | 浙江永宁药业股份有限公司 | The preparation method of 4-cyclic lactam base aniline |
| CN105837528B (en) * | 2016-05-30 | 2018-04-27 | 大连理工大学 | A kind of preparation method of 2- (methyl sulphonyl) -10H- phenthazine |
| CN109134321A (en) * | 2018-10-22 | 2019-01-04 | 江苏长青农化股份有限公司 | A kind of preparation method of mesotrione intermediate |
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| CN86101618A (en) * | 1985-03-14 | 1986-12-17 | 三菱化成工业株式会社 | The preparation method of aromatic sulphones compounds |
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| CN86101618A (en) * | 1985-03-14 | 1986-12-17 | 三菱化成工业株式会社 | The preparation method of aromatic sulphones compounds |
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