CN1660800A - 2(2-chlorine-4-phenyl fluoride) bisulfide, preparation and aplication - Google Patents
2(2-chlorine-4-phenyl fluoride) bisulfide, preparation and aplication Download PDFInfo
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Abstract
A novel bis (2-chloro-4-fluorophenyl) bisulfide is prepared from 3,4-dichloronitrobenzene, sodium sulfide, sulfur, H2O2, sodium nitrite, fluoroboric acid, hydrochloric acid, nitric acid and smoke sulfuric acid. Its application is also disclosed. Its advantages are high purity and selectivity.
Description
(1) technical field
The present invention relates to a kind of novel substance two (2-chloro-4-fluorophenyl) disulphide, and the preparation method and the application of this novel substance.
(2) background technology
2-chloro-4-fluoro-5-nitrobenzene sulfonyl chloride is a kind of important organic synthesis intermediate, can be used for the synthetic of agricultural chemicals such as ultra-high efficiency weedicide fluthiacetmethyl.
The open JP1-168622 of Japanese Patent handles 4-chloro-2-fluoronitrobenzene with chlorsulfonic acid and has synthesized 2-chloro-4-fluoro-5-nitrobenzene sulfonyl chloride (seeing formula A).
Yet the starting raw material 4-chloro-2-fluoronitrobenzene of this method is difficult preparation (Chinese patent CN1162393C), and not commercialization production as yet at present makes this method be difficult to realize suitability for industrialized production.
(3) summary of the invention
The present invention can be used for preparing 2-chloro-4-fluoro-5-nitrobenzene sulfonyl chloride in order to provide a kind of, is easy to suitability for industrialized production and the simple novel substance of route reasonable process---two (2-chloro-4-fluorophenyl) disulphide, and the preparation of this novel substance and application.
For reaching goal of the invention the technical solution used in the present invention be:
A kind of two (2-chloro-4-fluorophenyl) disulphide, structural formula is shown in (I):
The method for preparing described two (2-chloro-4-fluorophenyl) disulphide, described method is as follows: it is in 20～40% the sulfuric acid that two (4-amino-2-chloro-phenyl-) disulphide is suspended in concentration, dropping concentration is 20～40% sodium nitrite in aqueous solution under 5～10 ℃, continuing at 5～10 ℃ after adding reacted 1～2 hour down, remove by filter insolubles, filtrate adding concentration under the ice bath cooling is 20～40% fluoborate aqueous solution, control reaction temperature stirred 0.5～1 hour for 5～10 ℃, suction filtration, washing, dry, get pale yellow powder shape NITRODIAZONIUM FLUOROBORATE, NITRODIAZONIUM FLUOROBORATE promptly gets described two (2-chloro-4-fluorophenyl) disulphide 130～140 ℃ of following thermolysiss; The mol ratio of two (4-amino-2-chloro-phenyl-) disulphide, sulfuric acid, Sodium Nitrite and fluoroboric acid is 1.0: 8～16: 2.0～2.1: 2.2～2.4.
Described two (4-amino-2-chloro-phenyl-) disulphide is obtained by following method:
With 3, the suspension of 4-dichloronitrobenzene and water is heated to 50～60 ℃, stir, the solution that then keeps this temperature dropping sodium sulphite and sulphur to be made into, add back temperature rising reflux 8～12h, reaction solution is cooled to 40～50 ℃ then, drips concentration and be 20～40% hydrogen peroxide solution, after suction filtration, washing, ethyl alcohol recrystallization, oven dry promptly get described two (4-amino-2-chloro-phenyl-) disulphide; 3, the mol ratio of 4-dichloronitrobenzene, sodium sulphite, sulphur and hydrogen peroxide is 1.0: 2.0～3.0: 1.0～1.5: 0.9～1.2.
Concrete, preparation method's following steps of described two (2-chloro-4-fluorophenyl) disulphide are carried out:
(1) 3, the suspension of 4-dichloronitrobenzene and water is heated to 50～55 ℃, stir, the solution (water content 60%-80%) that then keeps this temperature dropping sodium sulphite and sulphur to be made into, add back temperature rising reflux 10～12h, reaction solution is cooled to 40～50 ℃ then, dropping concentration is 30% hydrogen peroxide solution, add postcooling to room temperature, promptly get described two (4-amino-2-chloro-phenyl-) disulphide through suction filtration, washing, ethyl alcohol recrystallization, oven dry; 3, the mol ratio of 4-dichloronitrobenzene, sodium sulphite, sulphur and hydrogen peroxide is 1.0: 3.0: 1.5: 1.0;
(2) two (4-amino-2-chloro-phenyl-) disulphide being suspended in concentration is in 20～40% the sulfuric acid, stir, dropping concentration is 30% sodium nitrite in aqueous solution under 5～10 ℃, period is in 30min, continuing at 5～10 ℃ after adding reacted 1.5 hours down, suction filtration is removed insolubles, filtrate adding concentration under the ice bath cooling is 40% fluoborate aqueous solution, control reaction temperature stirred 0.5 hour for 5～10 ℃, suction filtration, washing, drying, get pale yellow powder shape NITRODIAZONIUM FLUOROBORATE, NITRODIAZONIUM FLUOROBORATE promptly gets described two (2-chloro-4-fluorophenyl) disulphide 130 ℃ of following thermolysiss; The mol ratio of two (4-amino-2-chloro-phenyl-) disulphide, sulfuric acid, Sodium Nitrite and fluoroboric acid is 1.0: 16: 2.0: 2.4.
Described two (2-chloro-4-fluorophenyl) disulphide can be applicable to prepare 2-chloro-4-fluorobenzene SULPHURYL CHLORIDE.Described application is that to be scattered in concentration with two (2-chloro-4-fluorophenyl) disulphide be in 35～40% the concentrated hydrochloric acid, add nitrosonitric acid, feed chlorine reaction 1～2h down at 70～90 ℃, obtain described 2-chloro-4-fluorobenzene SULPHURYL CHLORIDE through cooling, layering, washing, drying again; The mol ratio of two (2-chloro-4-fluorophenyl) disulphide, concentrated hydrochloric acid and nitric acid is 1: 10～15: 2～3.
Described two (2-chloro-4-fluorophenyl) disulphide also can be applicable to prepare 2-chloro-4-fluoro-5-nitrobenzene sulfonyl chloride.Described application is that to be scattered in concentration with two (2-chloro-4-fluorophenyl) disulphide be 35～40% concentrated hydrochloric acid, add nitrosonitric acid, feed chlorine reaction 1～2h down at 70～90 ℃, again through cooling, layering, washing, after drying obtains 2-chloro-4-fluorobenzene SULPHURYL CHLORIDE, again 2-chloro-4-fluorobenzene SULPHURYL CHLORIDE is added in the nitration mixture by 20% oleum and the preparation of 95% nitrosonitric acid, stirring is warming up to 60～90 ℃ of reaction 2～8h, react completely postcooling to room temperature, standing demix, acid layer chloroform extraction, merge organic layer, washing, be drying to obtain described 2-chloro-4-fluoro-5-nitrobenzene sulfonyl chloride; The mol ratio of two (2-chloro-4-fluorophenyl) disulphide, concentrated hydrochloric acid and nitric acid is 1: 10～15: 2～3; The mol ratio of 2-chloro-4-fluorobenzene SULPHURYL CHLORIDE, oleum and nitric acid is 1: 2.0～3.0: 1.1～1.5.
Concrete, described application is that to be scattered in concentration with two (2-chloro-4-fluorophenyl) disulphide be 35～40% concentrated hydrochloric acid, add nitrosonitric acid, feed chlorine reaction 2h down at 70 ℃, again through cooling, layering, organic layer is water, 10% sodium hydrogen carbonate solution and water washing, anhydrous magnesium sulfate drying successively, obtains weak yellow liquid, is 2-chloro-4-fluorobenzene SULPHURYL CHLORIDE; The mol ratio of two (2-chloro-4-fluorophenyl) disulphide, concentrated hydrochloric acid and nitric acid is 1: 15: 3; 2-chloro-4-fluorobenzene SULPHURYL CHLORIDE with gained adds in the nitration mixture of being prepared by 20% oleum and 95% nitrosonitric acid again, stirring is warming up to 80 ℃ of reaction 2h, react completely postcooling to room temperature, standing demix, acid layer chloroform extraction merges organic layer, water, 10% sodium bicarbonate aqueous solution and a water washing, anhydrous magnesium sulfate drying, the decompression precipitation gets faint yellow solid, is described 2-chloro-4-fluoro-5-nitrobenzene sulfonyl chloride; The mol ratio of 2-chloro-4-fluorobenzene SULPHURYL CHLORIDE, oleum and nitric acid is 1: 1.3: 2.5.
2-chloro-4-fluoro-5-nitrobenzene sulfonyl chloride of the present invention and preparation thereof and the beneficial effect of using are mainly reflected in: the preparation raw material of (1) two (2-chloro-4-fluorophenyl) disulphide is easy to get, the main raw material that is adopted has 3,4-dichloronitrobenzene, sodium sulphite, sulphur, hydrogen peroxide, Sodium Nitrite, fluoroboric acid, hydrochloric acid, nitric acid, oleum etc., be common Chemicals, price is also cheaper; (2) route is reasonable, and reaction involved in the present invention is common chemical reaction, and selectivity is better, is easy to realize industrialization; (3) technology is simple, raw materials used easy storing of the inventive method and use, and reaction conditions is relatively gentleer, simple to operate, and reaction preference is all better, and the purity of intermediate and product is higher.
(4) embodiment
The present invention is described further below in conjunction with specific embodiment:
The preparation of 1: two (4-amino-2-chloro-phenyl-) disulphide of embodiment
In the 1000mL four-hole boiling flask, add 3,4-dichloronitrobenzene (96.0g, 0.5mol) and water (150mL), be warming up to 50～55 ℃, stir fast add down by nine water cure sodium (360.0g, 1.5mol), sulphur (24.0g, 0.75mol) and the solution that is made into of water (210mL), 10min adds, reflux 10～12h then, and HPLC analyzes and reacts completely; Component distillation is told minor by-products 3, and 4-dichlorphenamide bulk powder (2.5g, yield 3.1%) steams 150mL water this moment approximately; In reaction solution, add 150mL water and adjust the temperature to 45 ℃, the water-bath cooling, drip 30% hydrogen peroxide (56.7g down in 40～50 ℃, 0.5mol), add postcooling to room temperature, suction filtration, washing, ethyl alcohol recrystallization, get orange-yellow crystal 76.5g, yield 95.0%, content 98.3%, 190.5～192.0 ℃ of fusing points.
Embodiment 2～5: the preparation of two (4-amino-2-chloro-phenyl-) disulphide
With reference to the method for embodiment 1, change proportioning raw materials, the result is as follows.
| Embodiment | 3,4-dichloronitrobenzene g (mol) | Nine water cure sodium g (mol) | Sulphur g (mol) | 30% hydrogen peroxide g (mol) | Two (2-chloro-4-aminophenyl) disulphide | ||
| Output g | Yield % | Content % | |||||
| ????2 | ????96.0(0.5) | ????360.0(1.5) | ????24.0(0.75) | ????51.0(0.45) | ????74.8 | ????92.9 | ????98.1 |
| ????3 | ????96.0(0.5) | ????360.0(1.5) | ????24.0(0.75) | ????68.0(0.6) | ????72.1 | ????89.5 | ????97.2 |
| ????4 | ????96.0(0.5) | ????300.0(1.25) | ????20.0(0.63) | ????56.7(0.5) | ????73.4 | ????91.2 | ????97.8 |
| ????5 | ????96.0(0.5) | ????240.0(1.0) | ????16.0(0.5) | ????56.7(0.5) | ????68.7 | ????85.3 | ????98.1 |
The preparation of 6: two (2-chloro-4-fluorophenyl) disulphide of embodiment
In the 500ml there-necked flask, add two (2-chloro-4-aminophenyl) disulphide (20.0g, 62mmol) with 30% dilute sulphuric acid (250g), stirring at room 1h, ice-water bath is cooled to 5～10 ℃, (29.7g 129mmol), continues at 5～10 ℃ of stirring reaction 1.5h after adding to drip 30% sodium nitrite in aqueous solution then under this temperature in 30min.Suction filtration is removed a small amount of insolubles, filtrate slowly adds 40% fluoborate aqueous solution (33g under the ice-water bath cooling, 150mmol), control reaction temperature stirs 30min for 5～10 ℃, suction filtration then, use a little cold water, methanol (1: 10) solution and ether washing successively, vacuum-drying gets pale yellow powder shape NITRODIAZONIUM FLUOROBORATE (30.5g); The gained diazonium salt is placed exsiccant 250mL there-necked flask, carefully be warming up to 130 ℃, diazonium salt begins to decompose, by regulating thermal source height control reaction temperature at 130～140 ℃, about 1h decomposes fully, is cooled to room temperature, with sherwood oil (60～90 ℃) recrystallization, get light yellow crystal 14.6g, yield 71.9%.82～84 ℃ of fusing points.
Embodiment 7～10: the preparation of two (2-chloro-4-fluorophenyl) disulphide
With reference to the method for embodiment 6, change proportioning raw materials, the result is as follows.
| Embodiment | Two (2-chloro-4-aminophenyl) disulphide g (mmol) | Dilute sulphuric acid | 30% Sodium Nitrite g (mmol) | 40% fluoroboric acid g (mmol) | Two (2-chloro-4-fluorophenyl) disulphide | |||
| Concentration % | Weight g | Output g | Yield % | Content % | ||||
| ???7 | ??20.0(62) | ????30 | ????250 | ?29.7(129) | 33(150) | 14.6 | ?71.9 | ?96.5 |
| ???8 | ??20.0(62) | ????40 | ????250 | ?29.7(129) | 33(150) | 14.3 | ?70.4 | ?97.1 |
| ???9 | ??20.0(62) | ????30 | ????250 | ?28.5(124) | 33(150) | 13.9 | ?68.5 | ?96.6 |
| ???10 | ??20.0(62) | ????30 | ????250 | ?29.7(129) | 30(136) | 14.2 | ?70.0 | ?95.9 |
The preparation of embodiment 11:2-chloro-4-fluorobenzene SULPHURYL CHLORIDE
In the 250mL four-hole boiling flask, add two (2-chloro-4-fluorophenyl) disulphide (16.4g, 50mmol), 36% concentrated hydrochloric acid (76g, 750mmol) and 95% nitrosonitric acid (10.9g, 150mmol), stir and be warming up to 70 ℃, slowly feed chlorine, 2.0h back gas spectrum detection reaction is complete, is cooled to room temperature, standing demix, organic layer is water, 10% sodium hydrogen carbonate solution and water washing successively, anhydrous magnesium sulfate drying filters, and gets weak yellow liquid 21.3g, yield 93.0%, content 98.5%.
The preparation of embodiment 12～16:2-chloro-4-fluorobenzene SULPHURYL CHLORIDE
With reference to the method for embodiment 11, change proportioning raw materials and temperature of reaction, the result is as follows.
| Embodiment | Two (2-chloro-4-fluorophenyl) disulphide g (mmol) | 36% concentrated hydrochloric acid g (mmol) | 95% nitrosonitric acid g (mmol) | Temperature ℃ | Time h | 2-chloro-4-fluorobenzene sulfonic acid fluoride | ||
| Output g | Yield % | Content % | ||||||
| ??12 | ?16.4(50) | ????76.0(750) | ????10.9(150) | ????80 | ????2.0 | ????21.8 | ????95.2 | ????98.3 |
| ??13 | ?16.4(50) | ????76.0(750) | ????10.9(150) | ????90 | ????1.0 | ????20.8 | ????90.8 | ????97.1 |
| ??14 | ?16.4(50) | ????50.7(500) | ????10.9(150) | ????80 | ????1.5 | ????20.5 | ????89.5 | ????98.2 |
| ??15 | ?16.4(50) | ????76.0(750) | ????7.3(100) | ????80 | ????1.5 | ????18.9 | ????82.5 | ????96.8 |
| ??16 | ?16.4(50) | ????50.7(500) | ????7.3(100) | ????80 | ????2.0 | ????17.1 | ????74.7 | ????95.1 |
The preparation of embodiment 17:2-chloro-4-fluoro-5-nitrobenzene sulfonyl chloride
In the 50mL there-necked flask, add 20% oleum (20.0g, 50mmol SO
3) and 95% nitrosonitric acid (1.9g, 26mmol), drip 2-chloro-4-fluorobenzene SULPHURYL CHLORIDE (4.6g under the stirring at room, 20mmol), about 10min adds, and continues stirring at room 30min, be warming up to 80 ℃ of stirring reaction 3h then, gas spectrum detection reaction is complete, is cooled to room temperature, standing demix, the acid layer extracts with chloroform (15mL * 2), merge organic layer, water, 10% sodium hydrogen carbonate solution and water washing successively, anhydrous magnesium sulfate drying, the decompression precipitation, get faint yellow solid 4.9g, yield 89.4%, content 97.4%.60～62 ℃ of fusing points (literature value: 63～64 ℃).
The preparation of embodiment 18～22:2-chloro-4-fluoro-5-nitrobenzene sulfonyl chloride
With reference to the method for embodiment 17, change proportioning raw materials, temperature of reaction and time, the result is as follows.
| Example | 2-chloro-4-fluorobenzene SULPHURYL CHLORIDE g (mmol) | 20% oleum g (mmol) | 95% nitrosonitric acid g (mmol) | Temperature ℃ | Time h | 2-chloro-4-fluoro-5-nitrobenzene sulfonyl chloride | ||
| Output g | Yield % | Content % | ||||||
| ??18 | ???4.6(20) | ????20.0(50) | ????1.9(26) | ????60 | ????8 | ????3.9 | ????71.1 | ????94.3 |
| ??19 | ???4.6(20) | ????20.0(50) | ????1.9(26) | ????70 | ????6 | ????4.2 | ????76.6 | ????95.1 |
| ??20 | ???4.6(20) | ????20.0(50) | ????1.9(26) | ????90 | ????2 | ????4.6 | ????83.9 | ????92.8 |
| ??21 | ???4.6(20) | ????16.0(40) | ????1.6(22) | ????80 | ????5 | ????3.1 | ????56.6 | ????90.7 |
| ??22 | ???4.6(20) | ????24.0(60) | ????2.2(30) | ????80 | ????3 | ????4.9 | ????89.4 | ????93.3 |
Claims (9)
1. one kind two (2-chloro-4-fluorophenyl) disulphide, structural formula is shown in (I):
2. the method for preparing two (2-chloro-4-fluorophenyl) as claimed in claim 1 disulphide, it is characterized in that described method is as follows: it is in 20～40% the sulfuric acid that two (4-amino-2-chloro-phenyl-) disulphide is suspended in concentration, dropping concentration is 20～40% sodium nitrite in aqueous solution under 5～10 ℃, continuing at 5～10 ℃ after adding reacted 1～2 hour down, remove by filter insolubles, filtrate adding concentration under the ice bath cooling is 20～40% fluoborate aqueous solution, control reaction temperature stirred 0.5～1 hour for 5～10 ℃, suction filtration, washing, dry, get pale yellow powder shape NITRODIAZONIUM FLUOROBORATE, NITRODIAZONIUM FLUOROBORATE promptly gets described two (2-chloro-4-fluorophenyl) disulphide 130～140 ℃ of following thermolysiss; The mol ratio of two (4-amino-2-chloro-phenyl-) disulphide, sulfuric acid, Sodium Nitrite and fluoroboric acid is 1.0: 8～16: 2.0～2.1: 2.2～2.4.
3. the preparation method of two (2-chloro-4-fluorophenyl) as claimed in claim 2 disulphide, it is characterized in that described two (4-amino-2-chloro-phenyl-) disulphide is obtained by following method: with 3, the suspension of 4-dichloronitrobenzene and water is heated to 50～60 ℃, stir, the solution that then keeps this temperature dropping sodium sulphite and sulphur to be made into, add back temperature rising reflux 8～12h, reaction solution is cooled to 40～50 ℃ then, dropping concentration is 20～40% hydrogen peroxide solution, after suction filtration, washing, ethyl alcohol recrystallization, oven dry promptly gets described two (4-amino-2-chloro-phenyl-) disulphide; 3, the mol ratio of 4-dichloronitrobenzene, sodium sulphite, sulphur and hydrogen peroxide is 1.0: 2.0～3.0: 1.0～1.5: 0.9～1.2.
4. as the preparation method of claim 2 or 3 described two (2-chloro-4-fluorophenyl) disulphide, it is characterized in that described method carries out as follows:
(1) 3, the suspension of 4-dichloronitrobenzene and water is heated to 50～55 ℃, stir, the solution (water content 60-80%) that then keeps this temperature dropping sodium sulphite and sulphur to be made into, add back temperature rising reflux 10～12h, reaction solution is cooled to 40～50 ℃ then, dropping concentration is 30% hydrogen peroxide solution, add postcooling to room temperature, promptly get described two (4-amino-2-chloro-phenyl-) disulphide through suction filtration, washing, ethyl alcohol recrystallization, oven dry; 3, the mol ratio of 4-dichloronitrobenzene, sodium sulphite, sulphur and hydrogen peroxide is 1.0: 3.0: 1.5: 1.0;
(2) two (4-amino-2-chloro-phenyl-) disulphide being suspended in concentration is in 20～40% the sulfuric acid, stir, dropping concentration is 30% sodium nitrite in aqueous solution under 5～10 ℃, period is in 30min, continuing at 5～10 ℃ after adding reacted 1.5 hours down, suction filtration is removed insolubles, filtrate adding concentration under the ice bath cooling is 40% fluoborate aqueous solution, control reaction temperature stirred 0.5 hour for 5～10 ℃, suction filtration, washing, drying, get pale yellow powder shape NITRODIAZONIUM FLUOROBORATE, NITRODIAZONIUM FLUOROBORATE promptly gets described two (2-chloro-4-fluorophenyl) disulphide 130 ℃ of following thermolysiss; The mol ratio of two (4-amino-2-chloro-phenyl-) disulphide, sulfuric acid, Sodium Nitrite and fluoroboric acid is 1.0: 16: 2.0: 2.4;
5. the application of two (2-chloro-4-fluorophenyl) disulphide in preparation 2-chloro-4-fluorobenzene SULPHURYL CHLORIDE.
6. the application of two (2-chloro-4-fluorophenyl) as claimed in claim 5 disulphide in preparation 2-chloro-4-fluorobenzene SULPHURYL CHLORIDE, it is characterized in that described application is that to be scattered in concentration with two (2-chloro-4-fluorophenyl) disulphide be in 35～40% the concentrated hydrochloric acid, add nitrosonitric acid, feed chlorine reaction 1～2h down at 70～90 ℃, obtain described 2-chloro-4-fluorobenzene SULPHURYL CHLORIDE through cooling, layering, washing, drying again; The mol ratio of two (2-chloro-4-fluorophenyl) disulphide, concentrated hydrochloric acid and nitric acid is 1: 10～15: 2～3.
7. the application of two (2-chloro-4-fluorophenyl) disulphide in preparation 2-chloro-4-fluoro-5-nitrobenzene sulfonyl chloride.
8. the application of two (2-chloro-4-fluorophenyl) as claimed in claim 7 disulphide in preparation 2-chloro-4-fluoro-5-nitrobenzene sulfonyl chloride, it is characterized in that: described application is that to be scattered in concentration with two (2-chloro-4-fluorophenyl) disulphide be 35～40% concentrated hydrochloric acid, add nitrosonitric acid, feed chlorine reaction 1～2h down at 70～90 ℃, again through cooling, layering, washing, after drying obtains 2-chloro-4-fluorobenzene SULPHURYL CHLORIDE, again 2-chloro-4-fluorobenzene SULPHURYL CHLORIDE is added in the nitration mixture by 20% oleum and the preparation of 95% nitrosonitric acid, stirring is warming up to 60～90 ℃ of reaction 2～8h, react completely postcooling to room temperature, standing demix, acid layer chloroform extraction, merge organic layer, washing, be drying to obtain described 2-chloro-4-fluoro-5-nitrobenzene sulfonyl chloride; The mol ratio of two (2-chloro-4-fluorophenyl) disulphide, concentrated hydrochloric acid and nitric acid is 1: 10～15: 2～3; The mol ratio of 2-chloro-4-fluorobenzene SULPHURYL CHLORIDE, oleum and nitric acid is 1: 2.0～3.0: 1.1～1.5.
9. the application of two (2-chloro-4-fluorophenyl) as claimed in claim 8 disulphide in preparation 2-chloro-4-fluoro-5-nitrobenzene sulfonyl chloride, it is characterized in that: described application is that to be scattered in concentration with two (2-chloro-4-fluorophenyl) disulphide be 35～40% concentrated hydrochloric acid, add nitrosonitric acid, feed chlorine reaction 2h down at 70 ℃, again through cooling, layering, organic layer is water, 10% sodium hydrogen carbonate solution and water washing, anhydrous magnesium sulfate drying successively, obtain weak yellow liquid, be 2-chloro-4-fluorobenzene SULPHURYL CHLORIDE; The mol ratio of two (2-chloro-4-fluorophenyl) disulphide, concentrated hydrochloric acid and nitric acid is 1: 15: 3; 2-chloro-4-fluorobenzene SULPHURYL CHLORIDE with gained adds in the nitration mixture of being prepared by 20% oleum and 95% nitrosonitric acid again, stirring is warming up to 80 ℃ of reaction 2h, react completely postcooling to room temperature, standing demix, acid layer chloroform extraction merges organic layer, water, 10% sodium bicarbonate aqueous solution and a water washing, anhydrous magnesium sulfate drying, the decompression precipitation gets faint yellow solid, is described 2-chloro-4-fluoro-5-nitrobenzene sulfonyl chloride; The mol ratio of 2-chloro-4-fluorobenzene SULPHURYL CHLORIDE, oleum and nitric acid is 1: 1.3: 2.5.
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| CN106699614A (en) * | 2015-07-20 | 2017-05-24 | 韶远科技（上海)有限公司 | Amplified synthesis method of 3-nitro-4-halogeno-benzenesulfonamide |
| CN107698467A (en) * | 2017-08-21 | 2018-02-16 | 湖北江田精密化学有限公司 | A kind of synthetic method of the carboxyl benzene sulfonic acid of 2 chlorine, 4 nitro 5 |
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| CN106699614A (en) * | 2015-07-20 | 2017-05-24 | 韶远科技（上海)有限公司 | Amplified synthesis method of 3-nitro-4-halogeno-benzenesulfonamide |
| CN106699614B (en) * | 2015-07-20 | 2018-11-02 | 韶远科技（上海)有限公司 | The halogenated benzsulfamide scalable synthesis methods of 3- nitros -4- |
| CN107698467A (en) * | 2017-08-21 | 2018-02-16 | 湖北江田精密化学有限公司 | A kind of synthetic method of the carboxyl benzene sulfonic acid of 2 chlorine, 4 nitro 5 |
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