CN103360286A - Simple preparation method for sulfonyl chloride - Google Patents
Simple preparation method for sulfonyl chloride Download PDFInfo
- Publication number
- CN103360286A CN103360286A CN2013103052944A CN201310305294A CN103360286A CN 103360286 A CN103360286 A CN 103360286A CN 2013103052944 A CN2013103052944 A CN 2013103052944A CN 201310305294 A CN201310305294 A CN 201310305294A CN 103360286 A CN103360286 A CN 103360286A
- Authority
- CN
- China
- Prior art keywords
- salt
- methyl
- alkyl
- group
- sulphuryl chloride
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a simple preparation method for sulfonyl chloride. The preparation method comprises the steps: with an S-alkyl isothiourea salt as raw material and under an acidic condition, carrying out oxidation and chlorination of the S-alkyl isothiourea salt by hypochlorous acid and a salt of hypochlorous acid to obtain alkyl sulfonyl chloride. The preparation method has the raw materials which are simple and easy to get, is easy to operate, does not require and also does not produce other toxic harmful organic matters, is suitable for industrialized production, and can be used for preparation of optical activity sulfonyl chloride and a compound containing a plurality of sulfonyl chloride groups. The obtained compound can be used as raw material of organic matters, drugs, pesticides, surfactants and the like.
Description
Technical field
The invention belongs to technical field of organic synthesis, be specifically related to the preparation method of alkyl sulfonyl chloride.
Background technology
SULPHURYL CHLORIDE is the important organic and medicinal intermediates of a class and raw material (Hoyle, J.
In the Chemistry of Sulfonic Acids, Esters and Their Derivatives (The Chemistry of Functional Groups); Kociensky, P. J.
Protecting Groups; Thieme:New York, 1994.), can be used for synthesizing the drug molecule with alkylsulfonyl.SULPHURYL CHLORIDE and amine reaction can obtain sulphonamide (Opitz, G.
Angew. Chem. Int. Ed. 1967,
6, 107; King, J. F.
Acc. Chem. Res. 1975,
8, 10.), and sulphonamide is active structure unit (the McKew J. C. of many medicines
J. Med. Chem. 2008,
51, 3388; Blake, J. F.; Fell, J. B.; Fischer, J. P.; Hendricks, R. T.; Spencer S. R.; Stengel, P. J. PCT Int. Appl. WO 2006117306,
2006; Luzzio, M. J.; Autry, C. L.; Bhattacharya, S. K.; Freeman-Cook, K. D.; Hayward, M. M.; Hulford, C. A.; Nelson, K. L.; Xiao J.; Zhao, X. PCT Int. Appl. WO 2008129380,
2008; Li, H.; Argade, A.; Thota, S.; Carroll, D.; Sran, A.; Cooper, R.; Singh, R.; Tso, K.; Bhamidipati. S. PCT Int. Appl. WO 2008049123,
2008.).
In the synthetic method of existing multiple SULPHURYL CHLORIDE, with
S-alkyl isothiourea salt is relatively economy and the environmental protection of synthetic method of raw material, because
S-alkyl isothiourea salt is nonpoisonous and tasteless, can not produce environment and pollute, and can not damage human body.
S-alkyl isothiourea salt can be easily nucleophilic substitution by thiocarbamide and haloalkane, sulfuric ester or sulphonate prepare.By
S-alkyl isothiourea salt prepares alkyl sulfonyl chloride can be realized by oxidation chlorination.The oxidation chlorination reagent of having reported mainly contains chlorine (Sprague, J. M.; Johnson, T. B.
J. Am. Chem. Soc. 1937,
59, 1837; Griffin, J. W.; Hey, D. H.
J. Chem. Soc. 1952, 3334; Block, E.; Aslam, M.
Tetrahedron Lett 1982,
23, 4203; King, J. F.; Loosmore, S. M.; Aslam, M.; Lock, J. D.; McGarrity, M. J.
J. Am. Chem. Soc.,
1982,
104, 7108), hydrogen peroxide-hydrochloric acid (Dang Zhanqing, Kang Ruhong, applied chemistry, 1995,
12, 103; Dang Zhanqing, Kang Ruhong, Wu Ruitao, Zhang Lanping, chemical reagent,
1995,
17, 165.), potassium permanganate-hydrochloric acid (Zhen Xiaoli, Kang Ruhong, Han Jianrong, chemistry circular,
1996, 37.), Iodosobenzene-HCl-silica gel (Sohmiya, H.; Kimura, T.; Fujita, M.; Ando, T.
Chemistry Lett. 1992, 891; Sohmiya, H.; Kimura, T.; Fujita, M.; Ando, T.
Tetrahedron 1998,
54, 13737.), N-chlorosuccinimide-hydrochloric acid (Yang, Z. H.; Xu, J. X. Synthesis, 2013,
45, 1675.; Xu Jiaxi, Yang Zhanhui. Chinese invention patent prospectus, 201310133787.4) etc.Yet it is large that chlorine has toxicity, poor stability and use in the laboratory and to be inconvenient to measure and the shortcoming such as operation; Potassium permanganate is then seriously polluted, and large usage quantity (4.5 times), and productive rate is undesirable; When hydrogen peroxide-hydrochloric acid was made oxidation chlorination reagent, the consumption of hydrogen peroxide and hydrochloric acid was also larger; Iodosobenzene then price is higher, and inconvenient operation, also is not suitable for a large amount of preparations; N-chlorosuccinimide-salt acid system also can produce organic by-products.
The present invention is right under acidic conditions by hypochlorous acid and salt thereof
SThe oxidation chlorination reaction of-alkyl isothiourea salt has prepared alkyl sulfonyl chloride.This preparation method is easy and simple to handle, and the reaction times is short, and product is easy to separate, and reaction yield is better.
Summary of the invention
The method that the purpose of this invention is to provide a kind of simple preparation SULPHURYL CHLORIDE.This preparation method's raw material is simple and easy to, and is easy and simple to handle, and product is easy to separate, and is a kind of short-cut method of suitable industrial production SULPHURYL CHLORIDE.
Technical scheme of the present invention is as follows:
The present invention is right under acidic conditions by hypochlorous acid and salt thereof
SCorresponding alkyl sulfonyl chloride is prepared in the oxidation chlorination reaction of-alkyl isothiourea salt.
In the above-mentioned reaction formula:
X represents leavings group, comprising: Cl, Br, I, TsO, MsO, SO
4Deng.
R represents alkyl, cycloalkyl, cycloalkylalkyl, aralkyl, alkoxyalkyl, aryloxy alkyl, and wherein the alkyl in alkyl, aralkyl, aryloxyalkyl group and the alkoxyalkyl can be straight chain and side chain, and cycloalkyl and aryl can be fused rings; Alkyl isothiourea salt wherein can be the two isothiuronium saltss of alkyl, and R at this moment is alkylidene group, and aryl wherein can contain alkyl, alkoxyl group, acyl group, ester group, halogens chlorine, bromine and iodine, amino, nitro and cyano group etc.
Wherein said alkyl refers to have the straight or branched alkyl of 1～20 carbon atom, for example: methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, sec-butyl, amyl group, isopentyl, sec.-amyl sec-pentyl secondary amyl, neo-pentyl, hexyl, isohexyl, Sec-Hexyl, heptyl, different heptyl, Zhong Gengji, etc.The straight or branched alkyl that preferably has 1～18 carbon atom particularly preferably has the straight or branched alkyl of 3～10 carbon atoms, most preferably has the straight or branched alkyl of 3～8 carbon atoms.
Described alkylidene group refers to the straight or branched alkylidene group of 2～20 carbon atoms, is preferably ethylene, 1,3-propylidene, 1,4-butylidene, pentamethylene, hexamethylene, 1, the inferior heptyl, 1 of 7-, 8-is octylene, nonamethylene, 1, the inferior decyl, 1 of 10-, the inferior undecyl, 1 of 11-, the inferior dodecyl, 1 of 12-, the inferior tridecyl, 1 of 13-, the inferior tetradecyl, 1 of 14-, the inferior pentadecyl, 1 of 15-, the inferior hexadecyl, 1 of 16-, the inferior heptadecyl, 1 of 17-, the inferior octadecyl, 1 of 18-, the inferior nonadecyl, 1 of 19-, the inferior eicosyl of 20-.
Described cycloalkyl refers to the cycloalkyl of 3～20 carbon atoms, comprises the upper substituted cycloalkyl of ring.Be preferably cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl, ring decyl etc.
Described cycloalkylalkyl refers to have the cyclic alkyl of 4～20 carbon atoms, cyclopropyl methyl for example, cyclobutylmethyl, cyclopentyl-methyl, cyclohexyl methyl, the suberyl methyl, ring octyl group methyl, the cyclopropyl ethyl, the cyclobutyl ethyl, the cyclopentyl ethyl, the cyclohexyl ethyl, the suberyl ethyl, ring octyl group ethyl, the cyclopropyl propyl group, the cyclobutyl propyl group, the cyclopentyl propyl group, the cyclohexyl propyl group, the suberyl propyl group, ring octyl group propyl group, encircle the third butyl, encircle the third amyl group, encircle the third hexyl, encircle the third heptyl, etc., preferred cyclopropyl methyl, cyclopentyl-methyl, cyclohexyl methyl, the suberyl methyl, the cyclopropyl ethyl, the cyclopentyl ethyl, the cyclohexyl ethyl, the suberyl ethyl, the cyclopropyl propyl group, the cyclopentyl propyl group, the cyclohexyl propyl group, the suberyl propyl group.
Described aralkyl refers to have the aralkyl of 7～20 carbon atoms, and the aryl of aralkyl can coverlet replaces also can be by polysubstituted.Be preferably phenmethyl; to mehtoxybenzyl; to the methylbenzene methyl; the o-methyl-benzene methyl; between the methylbenzene methyl; 2; 3-dimethyl benzene methyl; 2; 4-dimethyl benzene methyl; 2; 5-dimethyl benzene methyl; 2; 6-dimethyl benzene methyl; 3; 4-dimethyl benzene methyl; 2; 4; 6-Three methyl Benzene methyl; to the fluorobenzene methyl; to the chloro phenmethyl; adjacent chlorophenylmethyl; between chlorophenylmethyl; to Brombenzyl; to the iodobenzene methyl; to the cyano group phenmethyl; to the acetylbenzene methyl; to the ethoxycarbonyl phenmethyl; to the trifluoromethyl phenmethyl; 2; 6-two (trifluoromethyl) phenmethyl; 2; 4,6-three (trifluoromethyl) phenmethyl; the p-nitrophenyl methyl; the 1-menaphthyl; the 2-menaphthyl; replace menaphthyl; Biphenylmethyl; 1-anthracene methyl; 2-anthracene methyl; 9-anthracene methyl; replace the anthracene methyl; styroyl; hydrocinnamyl; the benzene butyl; the benzene amyl group; the benzene hexyl; the benzene heptyl; the benzene octyl group; the benzene nonyl; the benzene decyl; the naphthalene ethyl; the naphthalene propyl group; the naphthalene butyl; the naphthalene amyl group; the naphthalene hexyl; the naphthalene heptyl; the anthracene ethyl; the anthracene propyl group; the anthracene butyl; the anthracene amyl group; the anthracene hexyl.
Described alkoxyalkyl refers to have the alkoxyalkyl of 2～20 carbon atoms.Be preferably methoxyl methyl, methoxyethyl, methoxycarbonyl propyl, methoxy butyl, methoxy amyl group, methoxy hexyl, 1-methoxy ethyl, 1-methoxy-propyl, 2-methoxy-propyl, ethoxymethyl, ethoxyethyl, ethoxy propyl group, ethoxy butyl, ethoxy amyl group, ethoxy hexyl, the third oxygen methyl, the third oxygen ethyl, the third oxygen propyl group, the third oxygen-butyl, the third oxygen amyl group, the third oxygen hexyl etc.
Described aryloxyalkyl group refers to have the aryloxyalkyl group of 7～20 carbon atoms.Be preferably Phenoxymethyl; to the methoxyl group Phenoxymethyl; to the methylenedioxy phenoxy methyl; o-methyl-benzene oxygen methyl; between the methylenedioxy phenoxy methyl; 2; 3-dimethyl Phenoxymethyl; 2; 4-dimethyl Phenoxymethyl; 2; 5-dimethyl benzene methyl; 2; 6-dimethyl Phenoxymethyl; 3; 4-dimethyl Phenoxymethyl; to fluorobenzene oxygen methyl; to the chloro Phenoxymethyl; adjacent chlorobenzene oxygen methyl; the m-chloro Phenoxymethyl; to bromobenzene oxygen methyl; to iodobenzene oxygen methyl; to the cyano group Phenoxymethyl; to the ethanoyl Phenoxymethyl; to the ethoxycarbonyl Phenoxymethyl; to the trifluoromethyl Phenoxymethyl; 2; 6-two (trifluoromethyl) Phenoxymethyl; 2; 4,6-three (trifluoromethyl) Phenoxymethyl; p-nitrophenyl oxygen methyl; 1-naphthalene oxygen methyl; 2-naphthalene oxygen methyl; biphenyl oxygen methyl; 1-anthracene oxygen methyl; 2-anthracene oxygen methyl; 9-anthracene oxygen methyl; replace anthracene oxygen methyl; benzene oxygen ethyl; benzene oxygen propyl group; the benzene oxygen-butyl; benzene oxygen amyl group; benzene oxygen hexyl; benzene oxygen heptyl; benzene oxygen octyl group; benzene oxygen nonyl; benzene oxygen decyl; naphthalene oxygen ethyl; naphthalene oxygen propyl group; the naphthalene oxygen-butyl; naphthalene oxygen amyl group; naphthalene oxygen hexyl; naphthalene oxygen heptyl; anthracene oxygen ethyl; anthracene oxygen propyl group; the anthracene oxygen-butyl; anthracene oxygen amyl group etc.
Preferred R represent methylidene; ethyl; propyl group; sec.-propyl; butyl; isobutyl-; the tertiary butyl; sec-butyl; amyl group; isopentyl; sec.-amyl sec-pentyl secondary amyl; neo-pentyl; hexyl; isohexyl; Sec-Hexyl; heptyl; different heptyl; Zhong Gengji; cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; suberyl; the ring octyl group; 1; the 2-ethylidene; 1; the inferior third class of 3-; 1; the 4-butylidene; 1; the 5-pentylidene; 1; the 6-hexylidene; 1; the inferior heptyl of 7-; 1; 8-is octylene; 1; 9-is nonamethylene; 1; the inferior decyl of 10-; 1; the inferior undecyl of 11-; 1; the inferior dodecyl of 12-; 1; the inferior tridecyl of 13-; 1; the inferior tetradecyl of 14-; 1; the inferior pentadecyl of 15-; 1; the inferior hexadecyl of 16-; 1; the inferior heptadecyl of 17-; 1; the inferior octadecyl of 18-; 1; the inferior nonadecyl of 19-; 1; the inferior eicosyl of 20-; phenmethyl; to mehtoxybenzyl; to the methylbenzene methyl; 2; 6-dimethyl benzene methyl; 2; 4; 6-Three methyl Benzene methyl; to the fluorobenzene methyl; to the chloro phenmethyl; adjacent chlorophenylmethyl; between chlorophenylmethyl; to Brombenzyl; to the iodobenzene methyl; to the cyano group phenmethyl; to the acetylbenzene methyl; to the ethoxycarbonyl phenmethyl; to the trifluoromethyl phenmethyl; 2; 6-two (trifluoromethyl) phenmethyl; 2; 4; 6-three (trifluoromethyl) phenmethyl; the p-nitrophenyl methyl; the 1-menaphthyl; the 2-menaphthyl; styroyl; hydrocinnamyl; the benzene butyl; the benzene amyl group; methoxyl methyl; methoxyethyl; methoxycarbonyl propyl; the methoxy butyl; the methoxy amyl group; the methoxy hexyl; the 1-methoxy ethyl; the 1-methoxy-propyl; ethoxymethyl; ethoxyethyl; the ethoxy propyl group; the ethoxy butyl; the ethoxy amyl group; the ethoxy hexyl; the third oxygen methyl; the third oxygen ethyl; the third oxygen propyl group; the third oxygen-butyl; the third oxygen amyl group; the third oxygen hexyl; Phenoxymethyl; to the methylenedioxy phenoxy methyl; o-methyl-benzene oxygen methyl; between the methylenedioxy phenoxy methyl; to fluorobenzene oxygen methyl; to the chloro Phenoxymethyl; adjacent chlorobenzene oxygen methyl; the m-chloro Phenoxymethyl; to bromobenzene oxygen methyl; to iodobenzene oxygen methyl; to the cyano group Phenoxymethyl; to the ethanoyl Phenoxymethyl; to the ethoxycarbonyl Phenoxymethyl; to the trifluoromethyl Phenoxymethyl; 2; 6-two (trifluoromethyl) Phenoxymethyl; 2; 4,6-three (trifluoromethyl) Phenoxymethyl; p-nitrophenyl oxygen methyl; 1-naphthalene oxygen methyl; 2-naphthalene oxygen methyl; biphenyl oxygen methyl; 1-anthracene oxygen methyl; 2-anthracene oxygen methyl; 9-anthracene oxygen methyl; benzene oxygen ethyl; benzene oxygen propyl group; the benzene oxygen-butyl; benzene oxygen amyl group; benzene oxygen hexyl; naphthalene oxygen ethyl; naphthalene oxygen propyl group; the naphthalene oxygen-butyl; naphthalene oxygen amyl group; naphthalene oxygen hexyl; naphthalene oxygen heptyl; anthracene oxygen ethyl; anthracene oxygen propyl group; the anthracene oxygen-butyl; anthracene oxygen amyl group etc.
Prepared SULPHURYL CHLORIDE is for example following
2a～
2p16 kinds of compounds:
2a：R?=?PhCH
2;
2b：R?=?
p-MeC
6H
4CH
2;
2c-----：R?=?
p-ClC
6H
4CH
2;
2d：R?=?
p-FC
6H
4CH
2;
2e：R?=?
p-O
2NC
6H
4CH
2;
2f：R?=?
p-NCC
6H
4CH
2;
2g?：R?=?
n-Bu；
2h?：R?=?
n-Hexyl；
2i:?R?=?
n-Octyl;
2j:?R?=?
n-Dodecyl;
2k?：R?=?
n-Cetyl；
2l?：R?=?3-Methylbutyl；
2m:R=(CH
2)
4(the alkyl isothiourea salt in this example is the two isothiuronium saltss of alkylidene group);
2n:R=(CH
2)
3(the alkyl isothiourea salt in this example is the two isothiuronium saltss of alkylidene group);
2o?：R?=?MeOCH
2CH
2；
2p?：R?=?Me.
Above-mentioned preparation method is right under acidic conditions by hypochlorous acid and salt thereof
S-alkyl isothiourea salt oxidation chlorination is prepared corresponding alkyl sulfonyl chloride.
Above-mentioned preparation method, described raw material
S-alkyl isothiourea salt can be
SThe two isothiuronium saltss of-alkylidene group can be used for preparing the compound that molecule contains two chlorosulfonyls.
Above-mentioned preparation method, described raw material
S-alkyl isothiourea salt and
SThe two isothiuronium saltss of-alkylidene group can be have optically active.
Above-mentioned preparation method, described raw material
S-alkyl isothiourea salt and reagent hypochlorous acid and salt thereof and acid can buy by disclosed commercial market channel, or prepare by the method for bibliographical information.
Above-mentioned preparation method, described oxygenant is hypochlorous acid and salt thereof normally, and hypochlorite wherein can be lithium salts, sodium salt, sylvite, cesium salt, magnesium salts, calcium salt.
Above-mentioned preparation method, described acid normally 0.01～12 mol/L hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid or their mixture.
Above-mentioned preparation method, used solvent is generally water, ether, propyl ether, methyl tertiary butyl ether, tetrahydrofuran (THF), dioxane, acetonitrile or their miscellany.
Above-mentioned preparation method, the control temperature of reaction is at ﹣ 30-100
oThe C reaction.
Advantage of the present invention and positively effect:
The alkyl sulfonyl chloride of the present invention's preparation is widely used in the production of medicine, dyestuff, tensio-active agent, ion exchange resin, synthetic chloroprene rubber, weedicide etc. as important organic and medicinal intermediates.
Preparation method's environmental protection provided by the invention, raw material are simple and easy to, and be easy to operate, and the reaction times is short, and it is convenient to purify, without organic by-products.Therefore, the method is suitable for suitability for industrialized production.
Embodiment
Mode below by embodiment further specifies the present invention, does not therefore limit the present invention among the scope of described embodiment.
Embodiment one
The benzyl SULPHURYL CHLORIDE
2aPreparation
Thiocarbamide (0.387 g, 5 mmol) and benzyl chlorine (0.633 g, 5 mmol) are joined in the 5 mL ethanol, and behind back flow reaction 30 min, decompression is removed solvent and is got white solid
S-benzylisothiourea salt.This white solid is directly slowly joined 6 M H
2SO
4In (2 mL, 12 mmol), then add ether (30 mL), 5% NaClO solution, 30 mL that slow adding is newly dispatched from the factory under the ice-water bath condition, temperature is at 10-20 in the control reaction system
OCBetween.After reinforced complete, continue reaction 15 min.Separatory after reaction finishes, gained organic phase anhydrous Na
2SO
4Drying, steaming desolventizes and obtains product
2a, clear crystal, fusing point 92-94 ℃, 0.886 g, productive rate 93%.
1H?NMR?(400?MHz,?CDCl
3)?δ?7.61-7.35?(m,?4H),?5.12?(s,?2H).
Embodiment two
To methyl benzyl SULPHURYL CHLORIDE
2bPreparation
Press the method for describing among the embodiment one, using methyl benzyl chlorine and thiocarbamide is raw material, obtains to methyl benzyl SULPHURYL CHLORIDE clear crystal, fusing point 80-81 ℃, 0.899 g, productive rate 87%.
1H?NMR?(400?MHz,?CDCl
3)?δ?7.38-7.26?(m,?4H),?4.83?(s,?2H),?2.39?(s,?3H).
Embodiment three
To the benzyl chloride SULPHURYL CHLORIDE
2cPreparation
Press the method for describing among the embodiment one, using benzyl chloride chlorine and thiocarbamide is raw material, obtains to the benzyl chloride SULPHURYL CHLORIDE clear crystal, fusing point 96-97 ℃, 1.114 g, productive rate 99%.
1H?NMR?(400?MHz,?CDCl
3)?δ?7.46-7.42?(m,?4H),?4.83?(s,?2H).
Embodiment four
To fluorine benzyl SULPHURYL CHLORIDE
2dPreparation
Press the method for describing among the embodiment one, using fluorine benzyl chlorine and thiocarbamide is raw material, obtains to fluorine benzyl SULPHURYL CHLORIDE clear crystal, fusing point 68-69 ℃, 1.066 g, productive rate 99%.
1H?NMR?(400?MHz,?CDCl
3)?δ?7.49-7.13?(m,?4H),?4.84?(s,?2H).
Embodiment five
To the nitrobenzyl SULPHURYL CHLORIDE
2ePreparation
Press the method for describing among the embodiment one, using nitrobenzyl chlorine and thiocarbamide is raw material, obtains to the nitrobenzyl SULPHURYL CHLORIDE clear crystal, fusing point 88-89 ℃, 1.001 g, productive rate 85%.
1H?NMR?(400?MHz,?CDCl
3)?δ?8.33?(d,?
J?=?8.7?Hz,?2H),?7.70?(d,?
J?=?8.7?Hz,?2H),?4.96?(s,?2H).
Embodiment six
To cyano group benzyl SULPHURYL CHLORIDE
2fPreparation
Press the method for describing among the embodiment one, using cyano group benzyl chlorine and thiocarbamide is raw material, obtains to cyano group benzyl SULPHURYL CHLORIDE clear crystal, fusing point 102-103 ℃, 1.090 g, productive rate 99%.
1H?NMR?(400?MHz,?CDCl
3)?δ?7.78-7.62?(m,?4H),?4.91?(s,?2H).
Embodiment seven
The normal-butyl SULPHURYL CHLORIDE
2gPreparation
Thiocarbamide (387 mg, 5 mmol) and n-butyl bromide (55 mg, 5 mmol) are dissolved in the 5 mL ethanol, and behind back flow reaction 1 h, decompression is removed solvent and is obtained white solid
S-normal-butyl isothiuronium salts.Without further purification, this white solid is slowly joined 6 M H
2SO
4In (2 mL, 12 mmol), add ether (30 mL), 5% NaClO solution, 37.5 mL that then slow adding is newly dispatched from the factory under the ice-water bath condition, temperature is at 10-20 in the control reaction system
OCBetween.After reinforced complete, continue reaction 15 min.Separatory after reaction finishes, gained organic phase anhydrous Na
2SO
4Drying, steaming desolventizes and obtains product, light yellow oily liquid, 0.768 g, productive rate 98%.
1H?NMR?(400?MHz,?CDCl
3)?δ?3.89-3.65?(m,?2H),?2.10-1.97?(m,?2H),?1.61-1.50?(m,?2H),?1.01?(t,?
J?=?7.4?Hz,?3H)..
Embodiment eight
The n-hexyl SULPHURYL CHLORIDE
2hPreparation
Pressing the method for describing among the embodiment seven, is raw material with bromo normal hexane and thiocarbamide, obtains the n-hexyl SULPHURYL CHLORIDE, light yellow oily liquid, 0.90 g, productive rate 75%.
1H?NMR?(400?MHz,?CDCl
3)?δ?3.76-3.65?(m,?2H),?2.08-1.98?(m,?2H),?1.50-1.35?(m,?6H),?0.91?(t,?
J?=?6.2?Hz,?3H).
Embodiment nine
The n-octyl SULPHURYL CHLORIDE
2iPreparation
Pressing the method for describing among the embodiment seven, is raw material with n-octane bromide and thiocarbamide, obtains the n-octyl SULPHURYL CHLORIDE, light yellow oily liquid, 0.958 g, productive rate 96%.
1H?NMR?(400?MHz,?CDCl
3):?δ?=?3.76-3.64?(m,?2H),?2.08-1.98?(m,?2H),?1.53-1.46?(m,?2H),?1.33-1.29?(m,?8H),?0.85?(t,?
J?=?6.8?Hz,?3H).
Embodiment ten
The dodecyl SULPHURYL CHLORIDE
2jPreparation
Pressing the method for describing among the embodiment seven, is raw material with N-dodeeyl bromide and thiocarbamide, obtains the dodecyl SULPHURYL CHLORIDE, white oily solid, 1.304 g, productive rate 97%, m.p. 40-41 ° C.
1H?NMR?(400?MHz,?CDCl
3):?δ?=?3.88-3.72?(m,?2H),?2.14-1.98?(m,?2H),?1.56-1.46?(m,?2H),?1.37-1.27?(m,?16H),?0.88?(t,?
J?=?6.7?Hz,?3H)。
Embodiment 11
N-Hexadecylsulfuryl Chloride
2kPreparation
Pressing the method for describing among the embodiment seven, is raw material with bromo n-hexadecane and thiocarbamide, obtains n-Hexadecylsulfuryl Chloride, clear crystal, fusing point 50-52 ℃, 1.628 g, productive rate 98%.
1H?NMR?(400?MHz,?CDCl
3)?δ?3.75-3.51?(m,?2H),?2.06-2.02?(m,?2H),?1.49-1.26?(m,?26H),?0.88?(t,?
J?=?6.2?Hz,?3H?in?CH
3).
Embodiment 12
3-methyl butyl SULPHURYL CHLORIDE
2lPreparation
Pressing the method for describing among the embodiment seven, is raw material with 1-bromo-3-methylbutane and thiocarbamide, obtains 3-methyl butyl SULPHURYL CHLORIDE, light yellow oily liquid, 0.680 g, productive rate 80%.
1H?NMR?(400?MHz,?CDCl
3)?δ?3.76-3.65?(m,?2H),?1.96-1.88?(m,?2H),?1.84-1.74?(m,?1H),?0.99?(d,?
J?=?6.4?Hz,?6H).
Embodiment 13
Isosorbide-5-Nitrae-butyl disulfonic acid chloride
2mPreparation
Thiocarbamide (774 mg, 10 mmol) and Isosorbide-5-Nitrae-dibromobutane (1.08 g, 5 mmol) are dissolved in the 5 mL ethanol, and behind back flow reaction 30 min, decompression is removed solvent and is obtained the two isothiuronium saltss of white solid.This white solid is slowly joined 6 M H
2SO
4In (4 mL, 24 mmol), add ether (60 mL), 5% NaClO solution, 75 mL that then slow adding is newly dispatched from the factory under the ice-water bath condition, temperature is at 10-20 in the control reaction system
OCBetween.After reinforced complete, continue reaction 15 min.Separatory after reaction finishes, gained organic phase anhydrous Na
2SO
4Drying, steaming desolventizes
,Obtain product
3o, clear crystal, fusing point 90-91 ℃, 1.000 g, productive rate 83%.
1H?NMR?(400?MHz,?CDCl
3)?δ?3.85-3.75?(m,?4H),?2.32-2.27?(m,?4H).
Embodiment 14
1,3-propyl group disulfonic acid chloride
2nPreparation
Pressing the method for describing among the embodiment 13, is raw material with 1,3-dibromopropane and thiocarbamide, obtains 1,3-propyl group disulfonic acid chloride, white solid, fusing point 46-48 ° C, 0.718 g, productive rate 60%.
1H?NMR?(400?MHz,?CDCl
3)?δ?
1H?NMR?(400?MHz,?CDCl
3):?δ?=?4.04-3.94?(m,?4H),?2.80-2.67?(m,?2H).
Embodiment 15
2-methoxyl group ethyl sulfonyl chloride
2oPreparation
Pressing the method for describing among the embodiment seven, is raw material with methylsulfonic acid 2-methoxyl group ethyl ester and thiocarbamide, obtains 2-methoxyl group ethyl sulfonyl chloride, light yellow oily liquid, 0.746 g, productive rate 94%.
1H?NMR?(400?MHz,?CDCl
3)?δ?3.97-3.94?(m,?4H),?3.43?(s,?3H).
Embodiment 16
Methylsulfonyl chloride
2pPreparation
Pressing the method for describing among the embodiment seven, is raw material with methyl-sulfate and thiocarbamide, obtains colourless oil liquid, 0.813 g, productive rate 71%.
1H?NMR?(400?MHz,?CDCl
3)?δ?3.68?(s,?3H)。
Claims (7)
1. the simple and convenient process for preparing of a SULPHURYL CHLORIDE is with shown in the formula [1]
S-alkyl isothiourea salt through hypochlorous acid and the oxidation chlorination of salt under acidic conditions thereof, obtains the alkyl sulfonyl chloride shown in the formula [2];
Wherein: X represents chlorion, bromide anion, iodide ion, methanesulfonate, tosic acid root, bisulfate ion, sulfate radical; R represent to have 1～20 carbon atom alkyl, have 2～20 carbon atoms alkylidene group, have 3～15 carbon atoms cycloalkyl, have 4～20 carbon atoms cycloalkylalkyl, have 7～20 carbon atoms aralkyl, have 2～20 carbon atoms alkoxyalkyl, have the aryloxyalkyl group of 7～20 carbon atoms; Alkyl wherein can be straight chain and side chain; Aryl wherein can contain alkyl, alkoxyl group, acyl group, ester group, chlorine, bromine, iodine, amino, nitro and cyano group.
2. the simple and convenient process for preparing of SULPHURYL CHLORIDE as claimed in claim 1 is characterized in that described raw material
S-alkyl isothiourea salt can be
SThe two isothiuronium saltss of-alkylidene group can be used for preparing the compound that molecule contains two chlorosulfonyls.
3. such as the simple and convenient process for preparing of SULPHURYL CHLORIDE as described in claim 1 and 2, it is characterized in that described raw material
S-alkyl isothiourea salt and
SThe two isothiuronium saltss of-alkylidene group can be have optically active.
4. such as the simple and convenient process for preparing of SULPHURYL CHLORIDE as described in the claim 1,2 and 3, it is characterized in that described solvent is selected from water, ether, propyl ether, methyl tertiary butyl ether, tetrahydrofuran (THF), dioxane, acetonitrile or their mixture.
5. such as the simple and convenient process for preparing of SULPHURYL CHLORIDE as described in the claim 1,2 and 3, it is characterized in that described oxidation chlorination reagent is hypochlorous acid and salt thereof, hypochlorite wherein can be lithium salts, sodium salt, sylvite, cesium salt, magnesium salts, calcium salt.
6. such as the simple and convenient process for preparing of SULPHURYL CHLORIDE as described in the claim 1,2 and 3, it is characterized in that described acid can be formic acid, acetic acid, hydrochloric acid, phosphoric acid, sulfuric acid or their mixture for 0.01～12 mol/L.
7. such as the simple and convenient process for preparing of SULPHURYL CHLORIDE as described in the claim 1,2 and 3, it is characterized in that described oxidation chlorination reaction carries out under-30～100 ° of C conditions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103052944A CN103360286A (en) | 2013-07-21 | 2013-07-21 | Simple preparation method for sulfonyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103052944A CN103360286A (en) | 2013-07-21 | 2013-07-21 | Simple preparation method for sulfonyl chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103360286A true CN103360286A (en) | 2013-10-23 |
Family
ID=49362641
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013103052944A Pending CN103360286A (en) | 2013-07-21 | 2013-07-21 | Simple preparation method for sulfonyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103360286A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104370784A (en) * | 2014-12-11 | 2015-02-25 | 北京彤程创展科技有限公司 | Naphthenic-base zinc sulfide compound and preparation method thereof |
| CN108752274A (en) * | 2018-07-25 | 2018-11-06 | 遂成药业股份有限公司 | A kind of preparation method of 5- isoquinoline sulfonyl chlorides |
| CN109467523A (en) * | 2018-12-17 | 2019-03-15 | 苏州华道生物药业股份有限公司 | A kind of green synthesis method of the third sulfonic acid chloride of 3- chlorine |
| CN113429320A (en) * | 2021-07-15 | 2021-09-24 | 老河口市天和科技有限公司 | Preparation method of pentadecyl sulfonyl chloride and oil tanning agent containing pentadecyl sulfonyl chloride |
| CN116063208A (en) * | 2023-02-13 | 2023-05-05 | 安徽省化工研究院 | Synthesis method of difluoromethane sulfonyl chloride |
-
2013
- 2013-07-21 CN CN2013103052944A patent/CN103360286A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| ATSUK NISHIGUCHI等: "Sulfonyl Chloride Formation from Thiol Derivatives by N-Chlorosuccinimide Mediated Oxidation", 《SYNTHESIS》 * |
| 康汝洪等: "氧化法合成烃基磺酰氯", 《有机化学》 * |
| 李保祥等: "《高中化学学考必备用书》", 30 June 2009 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104370784A (en) * | 2014-12-11 | 2015-02-25 | 北京彤程创展科技有限公司 | Naphthenic-base zinc sulfide compound and preparation method thereof |
| CN108752274A (en) * | 2018-07-25 | 2018-11-06 | 遂成药业股份有限公司 | A kind of preparation method of 5- isoquinoline sulfonyl chlorides |
| CN108752274B (en) * | 2018-07-25 | 2022-03-29 | 遂成药业股份有限公司 | Preparation method of 5-isoquinoline sulfonyl chloride |
| CN109467523A (en) * | 2018-12-17 | 2019-03-15 | 苏州华道生物药业股份有限公司 | A kind of green synthesis method of the third sulfonic acid chloride of 3- chlorine |
| CN113429320A (en) * | 2021-07-15 | 2021-09-24 | 老河口市天和科技有限公司 | Preparation method of pentadecyl sulfonyl chloride and oil tanning agent containing pentadecyl sulfonyl chloride |
| CN116063208A (en) * | 2023-02-13 | 2023-05-05 | 安徽省化工研究院 | Synthesis method of difluoromethane sulfonyl chloride |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103360286A (en) | Simple preparation method for sulfonyl chloride | |
| ES2526140T3 (en) | Procedure for the synthesis of fipronil | |
| CN105418460B (en) | Intermediate of pimavanserin and similar compound thereof, and preparation method thereof, and method for preparing pimavanserin and similar compound thereof | |
| CN103304437B (en) | Method for synthesizing oseltamivir phosphate without using nitrine | |
| CN107573267A (en) | Alkyl sulfonyl fluorine compounds, its preparation method and application containing trifluoromethyl | |
| ITMI20101239A1 (en) | PROCESS AND INTERMEDIATE FOR THE PREPARATION OF AN ACTIVE PRINCIPLE | |
| CN104941508B (en) | Fluorocarbon surfactant containing branch fluorocarbon chain and preparation method thereof | |
| Gordon et al. | Synthesis and purification | |
| CN102229529B (en) | Preparation method of (methyl) crylic acid phenylethanol ester compounds | |
| EP2810931A1 (en) | Process for the preparation of halogenated carboxylic anhydrides | |
| KR20170020350A (en) | Method for producing 2-halogen-acrylic acid esters | |
| CN101983201A (en) | Optically active dibenzazepine derivatives | |
| AR085171A1 (en) | PROCEDURE FOR THE PRODUCTION OF RALFINAMIDE SALTS SUBSTANTIALLY FREE OF IMPURITIES THAT HAVE GENOTOXIC EFFECTS, PSEUDOPOLIMORPHIC FORM OF THE SAME AND PHARMACEUTICAL FORMULATION CONTAINING IT | |
| CN110483274A (en) | A kind of preparation method of cyclopentolate hydrochloride intermediate | |
| CN106565531A (en) | Synthesis method for pharmaceutically acceptable salt of alkylhydrazine | |
| CN103351315A (en) | General preparation method of sulfonyl chloride | |
| CN107074757A (en) | The manufacture method of trifluoromethyl alkylthio compound | |
| JPS5540613A (en) | Preparation of 2, 6-dichloro-4-alkylphenol | |
| CN106045906B (en) | A kind of preparation method of the dihydro quinoline ketone compound of trifluoromethyl substitution | |
| EP3154933B1 (en) | Process for the preparation of 2-(trihalomethyl) benzamide | |
| CN108409557A (en) | Bu Waxitan new intermediates and its synthetic method and application | |
| CN110028434A (en) | A kind of Levetiracetam impurity and preparation method thereof | |
| ES2238029T3 (en) | PROCEDURE FOR THE PREPARATION OF DERIVATIVES OF TIAZOL. | |
| JP7134592B2 (en) | Method for preparing halogenated carboxylic acid anhydride | |
| CN106083668A (en) | A kind of preparation method of 3 bromomethyl 2 halo 4 alkyl sulphonyl benzoate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20131023 |