CN107698467A - A kind of synthetic method of the carboxyl benzene sulfonic acid of 2 chlorine, 4 nitro 5 - Google Patents
A kind of synthetic method of the carboxyl benzene sulfonic acid of 2 chlorine, 4 nitro 5 Download PDFInfo
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- CN107698467A CN107698467A CN201710718514.4A CN201710718514A CN107698467A CN 107698467 A CN107698467 A CN 107698467A CN 201710718514 A CN201710718514 A CN 201710718514A CN 107698467 A CN107698467 A CN 107698467A
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- chloro
- benzene sulfonic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/16—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by oxidation of thiols, sulfides, hydropolysulfides, or polysulfides with formation of sulfo or halosulfonyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
- C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of synthetic method of the carboxyl benzene sulfonic acid of 2 chlorine, 4 nitro 5, belong to chemical technology field, specially with the dichlorotoleune of 2 nitro 3,4 for raw material, the carboxyl benzoic acid of 2 chlorine, 4 nitro 5 is synthesized by curing, oxidation two-step reaction.Raw material of the present invention is easy to get, and cost is cheap, and reaction condition is gentle, and discarded object is few, technique clean environment firendly, and the carboxyl benzene sulfonic acid total recovery of 2 chlorine, 4 nitro 5 of synthesis is 82.7%~87.5%, HPLC high purities 97.5%~98.5%, stay in grade.
Description
Technical field
The invention belongs to chemical technology field, the synthetic method of more particularly to a kind of chloro- 4- nitros -5- carboxyl benzene sulfonic acids of 2-
Technical field.
Background technology
The chloro- 4- nitros -5- carboxyl benzene sulfonic acids of 2- are a kind of intermediates, the conjunction available for fine chemical product and medical product
Into.
The synthetic method for recording the chloro- 4- nitros -5- carboxyl benzene sulfonic acids of 2- is had no in prior art literature.People in the art
Member can carry out sulfonation to synthesize the chloro- 4- nitros -5- carboxyl benzene sulfonic acids of 2- by the chloro- 2- nitrobenzoic acids of 4- by oleum,
Or chlorosulfonation is carried out by chlorosulfonic acid by 4- chloro- 2- nitrobenzoic acids, hydrolyzed to synthesize the chloro- 4- nitros -5- carboxyls benzene sulphurs of 2-
Acid.But be the phenyl ring of a passivation due to containing nitro and carboxyl on the ring of the chloro- 2- nitrobenzoic acids of 4-, reaction condition is severe
Carve, product yield is low, in addition either oleum sulfonation or chlorosulphonic acid, can all produce a large amount of spent acid, administers pressure
It is very big.Therefore extremely it is necessary to develop a kind of chloro- 4- nitros -5- carboxyls benzene sulfonic acid synthetic methods of 2- of cleaning.
The content of the invention
The present invention is to overcome problems of the prior art, there is provided a kind of chloro- 4- nitros -5- carboxyls benzene sulphurs of the 2- of cleaning
Sour synthetic method, the synthetic method raw material are easy to get, and cost is cheap, and reaction condition is gentle, and discarded object is few, technique clean environment firendly, close
Into the chloro- 4- nitros -5- carboxyls benzene sulfonic acid purity of 2- it is high.
The present invention adopts the following technical scheme that to solve above-mentioned problems of the prior art.
The present invention, for raw material, reacts two (the chloro- 5- methyl -4- of 2- of synthesis with 2- nitros -3,4- dichlorotoleune by curing
Nitrobenzophenone) two sulphur, then the oxidized reaction synthesis chloro- 4- nitros -5- carboxyl benzene sulfonic acids of 2-, synthetic reaction formula is as follows：
Further, in curing reaction, vulcanizing agent be anhydrous sodium disulfide, 2- nitros -3,4- dichlorotoleune and
Anhydrous sodium disulfide mol ratio is 1:1.1~1.2, reaction temperature is 100~150 DEG C, 5~10 hours reaction time.
Further, in the curing reaction, solvent is sulfolane, weight of solvent and 2- nitro -3,4- dichlorotoleune
And the weight ratio of anhydrous sodium disulfide gross weight is 5~10：1.
Further, in the oxidation reaction, catalyst is dust technology, and oxidant is oxygen, the dust technology concentration
Mass concentration is 5~10%, and two (the chloro- 5- methyl -4- nitrobenzophenones of 2-) two sulphur are 1 with dust technology weight ratio：5~10, reaction
150~180 DEG C, 3~5MPa of oxygen pressure of temperature, 5~10 hours reaction time.
Relative to prior art, the present invention achieves following beneficial effect：
1st, for the present invention with 2- nitros -3,4- dichlorotoleune for raw material, the more conventional technology of its phenyl ring activity uses raw material
Phenyl ring activity is high, and reaction condition is gentle, and accessory substance is few, and synthesis total recovery is 82.7%~87.5%, product HPLC high purities
97.5%~98.5%, stay in grade.
2nd, the present invention is vulcanized, nitric acid catalytic air with 2- nitros -3,4- dichlorotoleune for raw material by anhydrous sodium disulfide
The two-step reaction synthesis chloro- 4- nitros -5- carboxyl benzene sulfonic acids of 2- are aoxidized, are avoided a large amount of caused by conventional sulphonation or chlorosulfonation technology
Spent acid, technique clean environment firendly.
3rd, the present invention is with 2- nitros -3,4- dichlorotoleune for raw material, and raw material is easy to get, and cost is cheap.
Embodiment
The present invention, for raw material, reacts two (the chloro- 5- methyl -4- of 2- of synthesis with 2- nitros -3,4- dichlorotoleune by curing
Nitrobenzophenone) two sulphur, then the oxidized reaction synthesis chloro- 4- nitros -5- carboxyl benzene sulfonic acids of 2-, enter one with specific embodiment below
Step illustrates the present invention.
Embodiment 1
Step 1: curing is reacted
By 0.1 mole of Chloro-2-Nitrobenzene of (13.4 grams) 4,5- bis-, 0.11 mole of (12.1 grams) anhydrous sodium disulfide and
163.5 grams of sulfolane put into reaction bulb, and stirring under nitrogen protection is warming up to 100~105 DEG C, reacts 10 hours.Then add
1000mL water dilutes, and cools to less than 50 DEG C, filtering, 100ml water washing filter cakes, the vacuum drying 8 hours of 60 DEG C of filter cake, obtains
12.3 gram of two (the chloro- 5- methyl -4- nitrobenzophenones of 2-) two sulphur, HPLC purity 98%, yield 94%.
Step 2: oxidation reaction
Two (the chloro- 5- methyl -4- of 2- that 0.05 mole of (13.05 grams) step 1 obtains are added in 500mL stainless steel pressure kettles
Nitrobenzophenone) two sulphur, and the dust technology of 101.5 gram mass fractions 10%, it is passed through oxygen to pressure 3MPa (gauge pressure), stirring and rises
Temperature to 150~155 DEG C, reacted 10 hours, and kettle is driven after cooling to less than 80 DEG C and pours out reactant, 60 DEG C are concentrated under reduced pressure, and slip by pressurize
Go out 50 grams of dust technologies and water, residue is chilled to -10 DEG C, filtering, collects filter cake, and 80 DEG C are dried in vacuo 10 hours, obtain 12.5
Gram chloro- 4- nitros -5- carboxyls benzene sulfonic acid products of 2-, HPLC purity 98.5%, yield 88.8%.
Embodiment 2
Step 1: curing is reacted
By 0.1 mole of Chloro-2-Nitrobenzene of (13.4 grams) 4,5- bis-, 0.12 mole of (13.2 grams) anhydrous sodium disulfide and
338 grams of sulfolane put into reaction bulb, and stirring under nitrogen protection is warming up to 148~150 DEG C, reacts 5 hours.Then cool to
Less than 100 DEG C, the dilution of 1500mL water is added, then cools to less than 50 DEG C, is filtered, 100ml water washing filter cakes, 60 DEG C of vacuum of filter cake
Dry 10 hours, obtain 12.1 gram of two (the chloro- 5- methyl -4- nitrobenzophenones of 2-) two sulphur, HPLC purity 98.2%, yield
92.4%.
Step 2: oxidation reaction
Two (the chloro- 5- methyl -4- of 2- that 0.05 mole of (13.05 grams) step 1 obtains are added in 500mL stainless steel pressure kettles
Nitrobenzophenone) two sulphur, and the dust technology of 203 gram mass fractions 5%, oxygen is passed through to pressure 5MPa (gauge pressure), stirring heating
To 175~180 DEG C, pressurize is reacted 5 hours, and kettle is driven after cooling to less than 80 DEG C and pours out reactant, 70 DEG C are concentrated under reduced pressure, and slip out
150 grams of dust technologies and water, residue are chilled to -10 DEG C, and filtering, 90 DEG C of filter cake is dried in vacuo 10 hours, and it is chloro- to obtain 12.7 grams of 2-
4- nitro -5- carboxyl benzene sulfonic acid products, HPLC purity 97.5%, yield 90.2%.
Embodiment 3
Step 1: curing is reacted
By 0.1 mole of Chloro-2-Nitrobenzene of (13.4 grams) 4,5- bis-, 0.115 mole of (12.65 grams) anhydrous sodium disulfide and
200 grams of sulfolane put into reaction bulb, and stirring under nitrogen protection is warming up to 135~140 DEG C, reacts 8 hours.Then cool to
Less than 100 DEG C, the dilution of 1500mL water is added, filtering, 100ml water washing filter cakes, the vacuum drying 10 hours of 60 DEG C of filter cake, is obtained
12.6 gram of two (the chloro- 5- methyl -4- nitrobenzophenones of 2-) two sulphur, HPLC purity 96.3%, yield 96.3%.
Step 2: oxidation reaction
In 500mmL stainless steel pressure kettles add 0.05 mole of (13.05 grams) step 1 obtain two (the chloro- 5- methyl of 2--
4- nitrobenzophenones) two sulphur, and the dust technology of 150 gram mass fractions 7%, it is passed through oxygen to pressure 4MPa (gauge pressure), stirring and rises
Temperature to 165~170 DEG C, reacted 8 hours, and kettle is driven after cooling to less than 70 DEG C and pours out reactant, 65 DEG C are concentrated under reduced pressure, and slip out by pressurize
120 grams of dust technologies and water, residue are chilled to -10 DEG C, and filtering, 90 DEG C of filter cake is dried in vacuo 10 hours, and it is chloro- to obtain 12.8 grams of 2-
4- nitro -5- carboxyl benzene sulfonic acid products, HPLC purity 98.5%, yield 90.9%.
2nd, test example part
The embodiment of the present invention 1~3 prepare product quality and yield respectively by weighing and being calculated, its purity analysis
Using liquid chromatography.The testing result that embodiment 1~3 prepares product is shown in Table 1.
The embodiment 1~3 of table 1 prepares product detection result
The chloro- 4- nitros -5- carboxyl benzene sulfonic acids of product 2- prepared by embodiments of the invention 1~3, synthesis total recovery exist
Between 82.7%~87.5%, product HPLC purity is between 97.5~98.5%.
The present invention, for raw material, is vulcanized, nitric acid catalytic air oxidation two with 2- nitros -3,4- dichlorotoleune by sodium disulfide
The step reaction synthesis chloro- 4- nitros -5- carboxyl benzene sulfonic acids of 2-, avoid a large amount of spent acid caused by conventional sulphonation or chlorosulfonation technology,
Technique clean environment firendly.
Claims (4)
- A kind of 1. synthetic method of the chloro- 4- nitros -5- carboxyl benzene sulfonic acids of 2-, it is characterised in that：With 2- nitro -3,4- dichlorotoleune For raw material, reacted by curing and synthesize two (the chloro- 5- methyl -4- nitrobenzophenones of 2-) two sulphur, then oxidized reaction synthesis 2- chloro- 4- nitro -5- carboxyl benzene sulfonic acids, synthetic reaction formula are as follows：
- A kind of 2. synthetic method of the chloro- 4- nitros -5- carboxyl benzene sulfonic acids of 2- according to claim 1, it is characterised in that：Institute State in curing reaction, vulcanizing agent is anhydrous sodium disulfide, and 2- nitros -3,4- dichlorotoleune is with anhydrous sodium disulfide mol ratio 1:1.1~1.2, reaction temperature is 100~150 DEG C, 5~10 hours reaction time.
- A kind of 3. synthetic method of the chloro- 4- nitros -5- carboxyl benzene sulfonic acids of 2- according to claim 2, it is characterised in that：Institute State in curing reaction, solvent is the weight of sulfolane, weight of solvent and 2- nitros -3,4- dichlorotoleune and anhydrous sodium disulfide With the ratio between be 5~10：1.
- A kind of 4. synthetic method of the chloro- 4- nitros -5- carboxyl benzene sulfonic acids of 2- according to claim 1, it is characterised in that：Institute State in oxidation reaction, catalyst is dust technology, and oxidant is oxygen, and the mass concentration of the dust technology concentration is 5~10%, two (the chloro- 5- methyl -4- nitrobenzophenones of 2-) two sulphur are 1 with dust technology weight ratio：5~10,150~180 DEG C of reaction temperature, oxygen pressure 3~5MPa of power, 5~10 hours reaction time.
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| CN201710718514.4A CN107698467A (en) | 2017-08-21 | 2017-08-21 | A kind of synthetic method of the carboxyl benzene sulfonic acid of 2 chlorine, 4 nitro 5 |
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| CN201710718514.4A CN107698467A (en) | 2017-08-21 | 2017-08-21 | A kind of synthetic method of the carboxyl benzene sulfonic acid of 2 chlorine, 4 nitro 5 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2965655A (en) * | 1957-11-07 | 1960-12-20 | Merck & Co Inc | Process for preparing substituted 1-amino 2, 4-benzene-disulfonamides |
| CN1660800A (en) * | 2004-12-04 | 2005-08-31 | 浙江工业大学 | 2(2-chlorine-4-phenyl fluoride) bisulfide, preparation and aplication |
| CN101570501A (en) * | 2009-06-10 | 2009-11-04 | 江苏联化科技有限公司 | Method for synthesizing p-nitrobenzenesulfonyl chloride |
| CN102558000A (en) * | 2011-12-25 | 2012-07-11 | 聊城大学 | Rubber peptizer intermediate 2,2'-dinitro-diphenyl disulfide and preparation method thereof |
-
2017
- 2017-08-21 CN CN201710718514.4A patent/CN107698467A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2965655A (en) * | 1957-11-07 | 1960-12-20 | Merck & Co Inc | Process for preparing substituted 1-amino 2, 4-benzene-disulfonamides |
| CN1660800A (en) * | 2004-12-04 | 2005-08-31 | 浙江工业大学 | 2(2-chlorine-4-phenyl fluoride) bisulfide, preparation and aplication |
| CN101570501A (en) * | 2009-06-10 | 2009-11-04 | 江苏联化科技有限公司 | Method for synthesizing p-nitrobenzenesulfonyl chloride |
| CN102558000A (en) * | 2011-12-25 | 2012-07-11 | 聊城大学 | Rubber peptizer intermediate 2,2'-dinitro-diphenyl disulfide and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| UETHER, R.等: "Triorganoantimony and triorganobismuth disulfonates. Crystal and molecular structure of (C6H5)3M(O3SC6H5)2 (M = Sb, Bi)", 《ZEITSCHRIFT FUER ANORGANISCHE UND ALLGEMEINE CHEMIE 》 * |
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