CN1156441C - A kind of preparation method of sulfonyl chloride aromatic hydrocarbon - Google Patents
A kind of preparation method of sulfonyl chloride aromatic hydrocarbon Download PDFInfo
- Publication number
- CN1156441C CN1156441C CNB021392390A CN02139239A CN1156441C CN 1156441 C CN1156441 C CN 1156441C CN B021392390 A CNB021392390 A CN B021392390A CN 02139239 A CN02139239 A CN 02139239A CN 1156441 C CN1156441 C CN 1156441C
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- CN
- China
- Prior art keywords
- group
- so2cl
- sulfuryl chloride
- present
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- -1 sulfonyl chloride aromatic hydrocarbon Chemical class 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 5
- OHBQPCCCRFSCAX-UHFFFAOYSA-N 1,4-Dimethoxybenzene Chemical compound COC1=CC=C(OC)C=C1 OHBQPCCCRFSCAX-UHFFFAOYSA-N 0.000 claims description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 238000005957 chlorosulfonylation reaction Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- YZUMYXYLMWRUEW-UHFFFAOYSA-N 2-acetamidonaphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(NC(=O)C)=CC=C21 YZUMYXYLMWRUEW-UHFFFAOYSA-N 0.000 claims 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 229910005948 SO2Cl Inorganic materials 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 229910006069 SO3H Inorganic materials 0.000 abstract 1
- 150000004951 benzene Chemical class 0.000 abstract 1
- 239000005416 organic matter Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- SHELADVIRCCTFN-UHFFFAOYSA-N 2,5-dimethoxybenzenesulfonyl chloride Chemical compound COC1=CC=C(OC)C(S(Cl)(=O)=O)=C1 SHELADVIRCCTFN-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for preparing sulfonyl chloro aromatics. Substituted benzene series or naphthalene series aromatic hydrocarbon is used as a raw material, ClSO3 H/SO2Cl is used as a mixing chlorosulfonation agent, and reaction is carried out at 0 to 45 DEG C; a sulfuryl chloride (-SO2Cl) group can be conveniently added on a ring, or an existing sulfonic group (-SO3H) can be conveniently converted into the sulfuryl chloride (-SO2Cl) group so as to obtain the required sulfonyl chloro aromatics. The present invention takes the ClSO3 H/SO2Cl as the mixing chlorosulfonation agent so as to conveniently add the sulfuryl chloride (-SO2Cl) group on the ring or convert the existing sulfonic group into the sulfuryl chloride group, and yield is respectively more than 90% and more than 95%. The present invention has the advantages of high product purity and simple operation, reduces organic matter content in waste water, greatly improves environment and reduces production cost.
Description
Technical field
The present invention relates to a kind of preparation method of sulphonyl chlorinated aromatic hydrocarbons, it is synthetic to belong to fine chemicals.
Background technology
SULPHURYL CHLORIDE (SO on the aromatic ring
2Cl) group maybe will encircle existing sulfonic group (SO
3H) be transformed into SULPHURYL CHLORIDE, in fine chemicals synthetic, have very important significance.Because-SO
2The Cl base is very active, can be converted into sulphonamide (SO easily
2NH
2) or substituted sulfonamides-SO
2NHR (Ar), or through being reduced to thiophenol (SH), sulphonamide or thiophenol are the intermediate of synthetic drugs or dyestuff, and be of many uses, is subjected to organic synthesis person's attention.
One-SO on the aromatic ring
2Cl has following traditional method: use PCl
5With aryl sulfonic acid through grinding, can be with-SO
3H is transformed into-SO
2Cl, as
PCl
5Smolder in a large number, environment is abominable, and productive rate has only about 50%; Use ClSO
3Direct and the substituted arene reaction of H, as
Though this reaction is easy and simple to handle, shortcoming is ClSO
3The H consumption is big, and therefore productive rate only 65～70%, simplifies reaction, and improving productive rate is to carry out the very actual problem that the chlorosulfonylation reaction is faced.
Summary of the invention
The present invention is exactly the preparation method that a kind of sulphonyl chlorinated aromatic hydrocarbons is provided at the problems referred to above, and this method is not only simple, and productive rate and product purity are higher.
Technical scheme provided by the invention is: with 1,4-dimethoxy benzene (terephthaldehyde's ether) or 2-kharophen naphthene sulfonic acid (acetyl TOBIAS ACID 97MIN.﹠ 98MIN.) are raw material, with ClSO
3H/SO
2Cl is for mixing chlorosulfonylation reagent, and 0～45 ℃ of reaction down, promptly a SULPHURYL CHLORIDE group maybe will encircle existing sulfonic group and be transformed into sulfuryl chlorio and obtain 2,5-dimethoxy benzene sulfonyl chloride or 2-kharophen naphthalic sulfonic chloride on the ring.
Above-mentioned raw materials 1, the amount ratio of 4-dimethoxy benzene or 2-kharophen naphthene sulfonic acid and reagent be, 1, and 4-dimethoxy benzene or 2-kharophen naphthene sulfonic acid: ClSO
3H: SO
2Cl is 10: 20～30: 6～10 (weight ratios).
The present invention ClSO
3H/SO
2Cl for mix chlorosulfonylation reagent can be easily on the ring SULPHURYL CHLORIDE group maybe will encircle existing sulfonic group and be transformed into sulfuryl chlorio.Productive rate reaches respectively more than 90% and 95%.Product purity height of the present invention, easy and simple to handle; Reduce organic content in the waste water, improved environment greatly, and reduced production cost.
Embodiment
The present invention is as the criterion with the amount of substituted arene, adds the ClSO of 2～3 times of amounts
3H, the SO of 0.6～1 times of amount
2Cl, 0～45 ℃ of reaction 3～4 hours needs solubilizing agent as reaction process, then boils off solvent and is product, as not needing solvent, then analyses, washes through ice and be product only.
Embodiment 1: reaction equation is
(cooling of external application ice bath) adding 13.5 gram terephthaldehyde ethers in the 250mL there-necked flask, 80mL methylene dichloride, 28 gram ClSO
3H, 9 gram SO
2Cl, 0～10 ℃ of reaction 3 hours, under agitation pour reaction product in the 240 gram frozen water (ice, each 120 gram of water), be divided into two-layer, lower floor is the dichloromethane solution that contains product, tell lower floor, to its distillation, 40 ℃ steam methylene chloride, product is a light yellow solid, oven-dried weight 21 grams, productive rate 90%, 115～117 ℃ of fusing points.
Embodiment 2: reaction equation
(cooling of external application ice bath) adding 25 gram ClSO in the 100mL there-necked flask
3H under agitation slowly adds acetyl TOBIAS ACID 97MIN.﹠ 98MIN. 11 grams, adds 8 gram SO then
2Cl after 1 hour, removes ice bath, and heating in water bath to 45 ℃ kept 2 hours, stir down, 250 gram frozen water (ice 100 grams, water 150 grams) are separated out light yellow product, and filtration is washed to pH=6～7, oven-dried weight 11.2 grams, productive rate 95% is analyzed content 〉=98% through HPLC.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021392390A CN1156441C (en) | 2002-11-04 | 2002-11-04 | A kind of preparation method of sulfonyl chloride aromatic hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021392390A CN1156441C (en) | 2002-11-04 | 2002-11-04 | A kind of preparation method of sulfonyl chloride aromatic hydrocarbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1405151A CN1405151A (en) | 2003-03-26 |
| CN1156441C true CN1156441C (en) | 2004-07-07 |
Family
ID=4749975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021392390A Expired - Fee Related CN1156441C (en) | 2002-11-04 | 2002-11-04 | A kind of preparation method of sulfonyl chloride aromatic hydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1156441C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633687B (en) * | 2012-04-05 | 2016-06-08 | 天津瑞岭化工有限公司 | The preparation method of a kind of para-orientation alkylbenzene sulfonyl chloride and technique |
-
2002
- 2002-11-04 CN CNB021392390A patent/CN1156441C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1405151A (en) | 2003-03-26 |
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