CN103351315A - General preparation method of sulfonyl chloride - Google Patents
General preparation method of sulfonyl chloride Download PDFInfo
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Abstract
The invention provides a general preparation method of sulfonyl chloride. The preparation method is characterized in that S-alkyl isothiourea salt, mercaptan, thiophenol, disulfide, thiol acetate, ethanethioate, xanthogenate and other sulfur-containing compounds are used as raw materials to prepare the sulfonyl chloride through the oxidation and chlorination of chlorous acid or its salt under acidic conditions. In the preparation method, the raw materials come from wide sources and are easily available, the operation is convenient, no toxic or polluting raw materials are needed, and no poisonous and harmful byproducts and organic byproducts are generated. Therefore, the preparation method is suitable for industrial production and can be applied to the preparation of optically active sulfonyl chloride and compounds containing a plurality of chlorosulfonyl. The obtained compounds may be used as the raw materials of organic, drugs, dyes, antibacterial agents, surfactants and plant-growth regulators.
Description
Technical field
The invention belongs to technical field of organic synthesis, be specifically related to the preparation method of SULPHURYL CHLORIDE.
Background technology
SULPHURYL CHLORIDE is the very important compound of a class, is widely used as intermediate and raw material (Hoyle, J. organic and that medicine is synthetic
In the Chemistry of Sulfonic Acids, Esters and Their Derivatives (The Chemistry of Functional Groups); Kociensky, P. J.
Protecting Groups; Thieme:New York, 1994.), be the important sources of alkylsulfonyl.
Owing to vital role and the extensive use of SULPHURYL CHLORIDE, now developed the preparation method of multiple SULPHURYL CHLORIDE.Generally speaking, alkyl sulfonyl chloride can prepare by following two kinds of methods: (1) utilizes chlorination reagent that alkylsulphonic acid or its salt are carried out direct chlorination (Bossard, H. H. Mory, R. Schmid M.; Zollinger, H.
Helv. Chim. Acta 1959,
42, 1653; Albright, J. D. Benz, E. Lanzilotti A. E.; Goldman, L.
Chem. Commun. 1965,
413JoharyN. S.; Owen. L. N.
J. Chem. Soc. 1955, 1307; Fujita, S.
Synthesis 1982, 423; Barco, A. Benetti, S. Pollini P.; Tadia, R.
Synthesis 1974, 877; Brouwer, A. J. Monnee M. C. F.; Liskamp, R. M. J.
Synthesis 2000, 1579.); (2) to mercaptan and precursor thereof or derivative (mercaptan,
S-alkyl isothiourea salt, disulfide, acetic acid mercaptan ester, carboxylamine mercaptan ester etc.) carry out oxidation chlorination (Monnee, M. C. F. Marijne, M. F. Brouwer A. J.; Liskamp, R. M. J.
Tetrahedron Lett. 2000,
41, 7991; Piatek, A. Chapuis C.; Jurczak, J.
Helv. Chim. Acta 2002,
85, 1973; Humljan J.; Gobec, S.
Tetrahedron Lett. 2005,
46, 4069; Bahrami, K. Khodaei M. M.; Soheilizad. M.
J. Org. Chem. 2009,
74, 9287; Kv rn, L. Werder, M. Hauser H.; Carreira, E. M.
Org. Lett. 2005,
7, 1145; Park, Y. J. Shin H. H.; Kim, Y. H.
Chem. Lett. 1992, 1483; Meinzer, A. Breckel, A. Thaher, B. A. Manicone N.; Otto, H.-H.
Helv. Chim. Acta 2004,
87, 90; Kim, D. W. Ko Y. K.; Kim, S. H.
Synthesis 1992, 1203; Nishiguchi, A. Maeda K. and Miki, S.
Synthesis 2006, 4131; Surya Prakash, G. K. Mathew, T. Panja C.; Olah. G. A.
J. Org. Chem. 2007,
72, 5847; ).First method have severe reaction conditions, reaction times long, functional group's tolerance is lower, use excess chlorination reagent, generate the shortcomings such as acidity or toxic by-products; Although second method has obtained significant progress in the century in the past, but still is faced with deficiency.For example, the oxidation chlorination reagent that has is not easy to obtain (O
3-SOCl
2, Kv rn, L. Werder, M. Hauser, H. Carreira, E. M.
Org. Lett. 2005,
7, 1145.), what have exists operational hazards (SO
2Cl
2-KNO
3: Park, Y. J. Shin H. H. Kim, Y. H.
Chem. Lett. 1992, 1483. Br
2-POCl
3: Meinzer, A. Breckel, A. Thaher, B. A. Manicone N. Otto, H.-H.
Helv. Chim. Acta 2004,
87, 90. H
2O
2-SOCl
2: Monnee, M. C. F. Marijne, M. F. Brouwer A. J. Liskamp, R. M. J.
Tetrahedron Lett. 2000,
41, 7991; Piatek, A. Chapuis, C. Jurczak, J.
Helv. Chim. Acta 2002,
85, 1973; Humljan, J. Gobec, S.
Tetrahedron Lett. 2005,
46, 4069; Bahrami, K. Khodaei M. M. Soheilizad. M.
J. Org. Chem. 2009,
74, 9287.), also have some can cause heavy metal contamination (H
2O
2-ZrCl
4: Bahrami, K. Khodaei, M. M. Soheilizad, M.
Synlett 2009, 2773. KMnO
4-HCl: Zhen Xiaoli, Kang Ruhong, Han Jianrong, the chemistry circular,
1996, 37.), some then can produce organic by-products, the purification of interference product (HCl-silica gel PhIO:Sohmiya, H. Kimura, T. Fujita, M. Ando, T.
Chem. Lett. 1992, 891; Sohmiya, H. Kimura, T. Fujita, M. T. Ando,
Tetrahedron 1998,
54 ,13737. N-chlorosuccinimide-hydrochloric acid: Kim, D. W. Ko, Y. K. Kim, S. H.
Synthesis 1992, 1203; Nishiguchi, A. Maeda, K. Miki, S.
Synthesis 2006, 4131; Veisi, H. Ghorbani-Vagheit, R. Hemmatia S. Mahmoodic, J.
Synlett 2011, 2315; Liu, J. Hou, S. L. Xu, J. X.
Phosphous, Sulfur Sillicon Relat. Elem. 2011,
186, 2377; Meng, F. H. Chen, N. Xu, J. X.
Sci. China:Chem. 2012,
55, 2548. Yang, Z. H. Xu, J. X.
Synthesis 2013,
45, 1675. trimethylchlorosilanes-saltpetre: Surya Prakash, G. K. Mathew, T. Panja, C. Olah, G. A.
J. Org. Chem. 2007,
72, 5847. trichlorine isonitrile uric acid: Massah, A. R. Sayadi, S. Ebrahimi, S.
RSC Adv. 2012,
2, 6606. 2,4-, two chloro-5,5-T10: Pu, Y.-M. Christesen A. Ku, Y.-Y.
Tetrahedron Lett. 2010,
51, 418. t-butyl hypochlorates: Joyard, Y. Papamicael, C. Bohn, P. Bischoff, L.
Org. Lett. 2013,
15, 2294.).Therefore, how preparing easily SULPHURYL CHLORIDE just seems and becomes more and more important.
The present invention is right under acidic conditions by chlorous acid and salt thereof
SThe oxidation chlorination reaction of-alkyl isothiuronium salts, mercaptan and thiophenol, disulfide, acetic acid mercaptan ester and the sulfocompounds such as acetic acid thiophenol ester, xanthate has prepared SULPHURYL CHLORIDE.This process operation is easy, and the reaction times, short productive rate was high, and product is easy to separate.The sulfur-bearing raw material sources that adopt extensively and be simple and easy to.
Summary of the invention
The method that the purpose of this invention is to provide a kind of general simple preparation SULPHURYL CHLORIDE.This preparation method's raw material is simple and easy to, and is easy and simple to handle, and productive rate is high, and product is easy to separate, and is a kind of short-cut method that is suitable for effective preparation SULPHURYL CHLORIDE of large-scale commercial production.
Technical scheme of the present invention is as follows:
A kind of general SULPHURYL CHLORIDE preparation method,
SCorresponding SULPHURYL CHLORIDE is prepared in the oxidation chlorination reaction under acidic conditions of the sulfocompounds such as-alkyl isothiuronium salts [1a], mercaptan and thiophenol [1b], disulfide [1c], acetic acid mercaptan ester and acetic acid thiophenol ester [1d] and xanthate [1e] process chlorous acid or its salt.
In the above-mentioned reaction formula:
R represents alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, alkoxyalkyl, aryloxy alkyl, alkoxycarbonyl alkyl etc., wherein the alkyl in alkyl, aralkyl, aryloxyalkyl group, alkoxyalkyl and the alkoxycarbonyl alkyl all can be straight chain and side chain, cycloalkyl and aryl can be fused rings, and aryl wherein can contain the substituting groups such as alkyl, alkoxyl group, acyl group, ester group, halogens chlorine, bromine and iodine, amino, nitro and cyano group; For the raw material that contains two sulfur derivatives, R can also be alkylidene group;
X represents chlorion, bromide anion, iodide ion, methanesulfonate, tosic acid root, bisulfate ion, sulfate radical;
R ' expression alkyl, cycloalkyl;
Wherein said alkyl refers to have the straight or branched alkyl of 1～20 carbon atom, such as: 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 1～10 carbon atom, most preferably has the straight or branched alkyl of 1～8 carbon atom.
Described cycloalkyl refers to the cycloalkyl of 3～20 carbon atoms, comprises the upper substituted cycloalkyl of ring.Most preferably be 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, for example cyclopropyl methyl, cyclobutylmethyl, cyclopentyl-methyl, cyclohexyl methyl, suberyl methyl, ring octyl group methyl, cyclopropyl ethyl, cyclobutyl ethyl, cyclopentyl ethyl, cyclohexyl ethyl, suberyl ethyl, ring octyl group ethyl, cyclopropyl propyl group, cyclobutyl propyl group, cyclopentyl propyl group, cyclohexyl propyl group, suberyl propyl group, ring octyl group propyl group, encircle the third butyl, ring the third amyl group, ring the third hexyl, ring the third heptyl, etc.Preferred cyclopropyl methyl, cyclopentyl-methyl, cyclohexyl methyl, suberyl methyl, cyclopropyl ethyl, cyclopentyl ethyl, cyclohexyl ethyl, suberyl ethyl, cyclopropyl propyl group, cyclopentyl propyl group, cyclohexyl propyl group, suberyl propyl group.Most preferably be cyclopropyl methyl, cyclobutylmethyl, cyclopentyl-methyl, cyclohexyl methyl, cyclopropyl ethyl, cyclobutyl ethyl, cyclopentyl ethyl, cyclohexyl ethyl.
Described alkylidene group refers to have 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-.Most preferably be trimethylene, tetramethylene, pentamethylene, hexamethylene, 1, the inferior heptyl of 7-, octamethylene.
Described aryl refers to have the aryl of 6～20 atoms.Be preferably phenyl; the 2-furyl; the 3-furyl; the 2-pyridyl; the 3-pyridyl; the 4-pyridyl; the 1-naphthyl; the 2-naphthyl; replace menaphthyl; the 1-anthryl; the 2-anthryl; replace anthryl; xenyl; p-methoxyphenyl; p-methylphenyl; o-methyl-phenyl-; between aminomethyl phenyl; 2; the 3-3,5-dimethylphenyl; 2; the 4-3,5-dimethylphenyl; 2; the 5-3,5-dimethylphenyl; 2; the 6-3,5-dimethylphenyl; 3; the 4-3,5-dimethylphenyl; 2; 4; the 6-trimethylphenyl; to fluorophenyl; to the chloro phenyl; Chloro-O-Phenyl; between chloro-phenyl-; to bromophenyl; to iodophenyl; to cyano-phenyl; p-nitrophenyl; to acetylphenyl; to carbethoxy phenyl; p-trifluoromethyl phenyl; 2; 6-two (trifluoromethyl) phenyl; 2; 4,6-three (trifluoromethyl) phenyl.Most preferably be phenyl, 2-pyridyl, p-methylphenyl, to fluorophenyl, to the chloro phenyl, to bromophenyl, to iodophenyl, to cyano-phenyl, p-nitrophenyl.
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; 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.Most preferably be phenmethyl, to mehtoxybenzyl, to the methylbenzene methyl, to the fluorobenzene methyl, to chloro phenmethyl, adjacent chlorophenylmethyl, a chlorophenylmethyl, to Brombenzyl, to the iodobenzene methyl, to the cyano group phenmethyl, to the acetylbenzene methyl, to the ethoxycarbonyl phenmethyl, to trifluoromethyl phenmethyl, styroyl, hydrocinnamyl.
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.Most preferably be methoxyethyl, methoxycarbonyl propyl, methoxy butyl, methoxy amyl group.
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; 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.Most preferably be Phenoxymethyl, benzene oxygen ethyl, benzene oxygen propyl group.
Described alkoxycarbonyl alkyl refers to have the alkoxycarbonylalkyl group of 3～20 carbon atoms.Be preferably methoxycarbonyl methyl, methoxycarbonyl ethyl, methoxycarbonyl propyl group, ethoxycarbonylmethyl group, ethoxycarbonyl-ethyl, ethoxycarbonyl propyl group, tertiary butyloxycarbonyl ylmethyl, tertbutyloxycarbonyl ethyl, tertbutyloxycarbonyl propyl group, benzene methoxycarbonyl methyl, benzene methoxycarbonyl ethyl, benzene methoxycarbonyl propyl group
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; octyl group; nonyl; decyl; undecyl; dodecyl; tridecyl; tetradecyl; pentadecyl; cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; suberyl; the ring octyl group; the ring nonyl; the ring decyl; the cyclopropyl methyl; cyclobutylmethyl; cyclopentyl-methyl; cyclohexyl methyl; the cyclopropyl ethyl; the cyclobutyl ethyl; the cyclopentyl ethyl; the cyclohexyl ethyl; phenyl; the 2-pyridyl; p-methylphenyl; to fluorophenyl; to the chloro phenyl; to bromophenyl; to iodophenyl; to cyano-phenyl; p-nitrophenyl; 1; the 4-butylidene; 1; the 5-pentylidene; 1; the 6-hexylidene; 1; the inferior heptyl of 7-; octamethylene; phenmethyl; to mehtoxybenzyl; to the methylbenzene 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; styroyl; hydrocinnamyl; methoxyethyl; methoxycarbonyl propyl; the methoxy butyl; the methoxy amyl group; the methoxycarbonyl methyl; the methoxycarbonyl ethyl; the methoxycarbonyl propyl group; ethoxycarbonylmethyl group; ethoxycarbonyl-ethyl; the ethoxycarbonyl propyl group; the tertiary butyloxycarbonyl ylmethyl; the tertbutyloxycarbonyl ethyl; the tertbutyloxycarbonyl propyl group; benzene methoxycarbonyl methyl; benzene methoxycarbonyl ethyl; benzene methoxycarbonyl propyl group.
Prepared SULPHURYL CHLORIDE is for example following
2a～
2r18 kinds of compounds:
2a：R?=?PhCH
2;
2b：R?=?
p-MeC
6H
4CH
2;
2c-----：R?=?
p-ClC
6H
4CH
2;
2d：R?=?
o-ClC
6H
4CH
2;
2e：R?=?
m-ClC
6H
4CH
2;
2f：R?=?
p-FC
6H
4CH
2;
2g：R?=?
p-BrC
6H
4CH
2;
2h：R?=?
p-NCC
6H
4CH
2;
2i：R?=?
p-O
2NC
6H
4CH
2;
2j?：R?=?Et；
2k?：R?=?
n-Hexyl；
2l?：R?=?
n-Cetyl；
2m?：R?=?3-Methylbutyl；
2n：R?=?
n-Bu；
2o:R=(CH
2)
4(product in this example is Isosorbide-5-Nitrae-butyl disulfonic acid chloride);
2p?：R?=?PhCH
2CH
2；
2q?：R?=?Ph；
2r?：R?=?MeOCH
2CH
2；
Above-mentioned preparation method normally will
S-alkyl isothiuronium salts, acetic acid mercaptan ester, acetic acid thiophenol ester,
OCorresponding sulfonic acid chloride is directly prepared in the oxidation chlorination reaction under acidic conditions of-xanthogenic acid ester, mercaptan, thiophenol, disulfide, carboxylamine mercaptan ester process chlorous acid or its salt.
Above-mentioned preparation method, described raw material can be formula [1a] to a plurality of sulphur structural units that contain shown in the formula [1e], can be used for preparing molecule and contain two to the compound of four chlorosulfonyls.
Above-mentioned preparation method, described raw material can be to have optically actively, can be used for preparation and have optically active SULPHURYL CHLORIDE.
Above-mentioned preparation method, described raw material (
S-alkyl isothiuronium salts, acetic acid mercaptan ester, acetic acid thiophenol ester,
O-xanthogenic acid ester, mercaptan, thiophenol, disulfide, carboxylamine mercaptan ester) can buy by disclosed commercial market channel with reagent (chlorous acid acid or its salt) and acid (hydrochloric acid, sulfuric acid, phosphoric acid, formic acid and acetic acid), or prepare by the synthetic method of bibliographical information.
Above-mentioned preparation method, described oxygenant is chlorous acid or its salt sodium normally, comprises lithium salts, sodium salt, sylvite, cesium salt, magnesium salts, calcium salt etc.; Required acid is hydrochloric acid, sulfuric acid, phosphoric acid, formic acid and the acetic acid of 0.01～12 mol/L normally.
Above-mentioned preparation method, described solvent is generally methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, water, tetrahydrofuran (THF), dioxane, acetonitrile or their miscellany.
Above-mentioned preparation method normally will
S-alkyl isothiuronium salts, acetic acid mercaptan ester, acetic acid thiophenol ester,
O-xanthogenic acid ester, mercaptan, thiophenol, disulfide, carboxylamine mercaptan ester directly join in the miscellany of chlorous acid or its salt and acid, and the control temperature of reaction is at ﹣ 30～150
oThe C reaction.
Advantage of the present invention and positively effect:
The SULPHURYL CHLORIDE of the present invention's preparation is widely used in medicine as important organic and medicinal intermediates, and dyestuff is in the production of tensio-active agent, ion exchange resin, synthetic chloroprene rubber, weedicide etc.
Preparation method's raw material sources provided by the invention extensively and be simple and easy to, easy to operate, the reaction times is short, productive rate is high, to purify convenient, by product is NaCl, not to environment.Therefore, the method is suitable for large-scale industrial 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 dissolved in 5 mL ethanol, and behind back flow reaction 30 min, decompression is removed solvent and is obtained white solid.This white solid slowly is added drop-wise to NaClO
2(1.61 g, 15 mmol, 85% purity), dense HCl(3 mL) and MeCN(10 mL) mixed system in.In the reinforced process with temperature in the water-bath control reaction system 10～20
OCBetween.After reinforced complete, continue stirring reaction 30 min, acetonitrile is removed in decompression under the cold condition, adds 25 mL water, and with the solid filtering in the system, drying obtains product clear crystal benzyl SULPHURYL CHLORIDE
3a, 90～91 ℃ of fusing points, 0.781 g, productive rate 82%.
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 among the embodiment one method of describing, take to methyl benzyl chlorine and thiocarbamide as raw material, obtain to methyl benzyl SULPHURYL CHLORIDE clear crystal, 86～88 ℃ of fusing points, 0.665 g, productive rate 65%.
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 among the embodiment one method of describing, take to benzyl chloride chlorine and thiocarbamide as raw material, obtain to the benzyl chloride SULPHURYL CHLORIDE clear crystal, 90～92 ℃ of fusing points, 1.080 g, productive rate 96%.
1H?NMR?(400?MHz,?CDCl
3)?δ:?7.46～7.42?(m,?4H),?4.83?(s,?2H).
Embodiment four
Adjacent benzyl chloride SULPHURYL CHLORIDE
2dPreparation
Press among the embodiment one method of describing, take o-chloro benzyl chloride and thiocarbamide as raw material, obtain adjacent benzyl chloride SULPHURYL CHLORIDE, clear crystal, 64～65 ℃ of fusing points, 1.024 g, productive rate 91%.
1H?NMR?(400?MHz,?CDCl
3)?δ:?7.61～7.35?(m,?4H),?5.12?(s,?2H).
Embodiment five
Between the benzyl chloride SULPHURYL CHLORIDE
2ePreparation
Press among the embodiment one method of describing, obtain a benzyl chloride SULPHURYL CHLORIDE, clear crystal, 76～78 ℃ of fusing points, 1.035 g, productive rate 92% take a benzyl chloride chlorine and thiocarbamide as raw material.
1H?NMR?(400?MHz,?CDCl
3)?δ:?7.48～7.37?(m,?4H),?4.83?(s,?2H).
Embodiment six
To fluorine benzyl SULPHURYL CHLORIDE
2fPreparation
Press among the embodiment one method of describing, take to fluorine benzyl chlorine and thiocarbamide as raw material, obtain to fluorine benzyl SULPHURYL CHLORIDE clear crystal, 66～67 ℃ of fusing points, 0.776 g, productive rate 75%.
1H?NMR?(400?MHz,?CDCl
3)?δ:?7.49～7.13?(m,?4H),?4.84?(s,?2H).
Embodiment seven
To the bromobenzyl SULPHURYL CHLORIDE
2gPreparation
Press among the embodiment one method of describing, take to bromobenzyl chlorine and thiocarbamide as raw material, obtain to the bromobenzyl SULPHURYL CHLORIDE clear crystal, 125～127 ℃ of fusing points, 1.212 g, productive rate 90%.
1H?NMR?(400?MHz,?CDCl
3)?δ:?7.61～7.35?(m,?4H),?4.81?(s,?2H).
Embodiment eight
To cyano group benzyl SULPHURYL CHLORIDE
2hPreparation
Press among the embodiment one method of describing, take to cyano group benzyl chlorine and thiocarbamide as raw material, obtain to cyano group benzyl SULPHURYL CHLORIDE clear crystal, 109～111 ℃ of fusing points, 0.766 g, productive rate 71%.
1H?NMR?(400?MHz,?CDCl
3)?δ:?7.78～7.62?(m,?4H),?4.91?(s,?2H).
Embodiment nine
To the nitrobenzyl SULPHURYL CHLORIDE
2iPreparation
Press among the embodiment one method of describing, take to nitrobenzyl chlorine and thiocarbamide as raw material, obtain to the nitrobenzyl SULPHURYL CHLORIDE clear crystal, 92～93 ℃ of fusing points, 0.636 g, productive rate 54%.
1H?NMR?(400?MHz,?CDCl
3)?δ:?8.33?(dd,?
J?=?2.0,?9.1?Hz),?7.71?(dd,?
J?=?2.0,?9.1Hz),?4.97?(s,?2H).
Embodiment ten
Ethyl chloride
2jPreparation
The 3mL acetonitrile solution of ethyl disulfide (0.611 g, 5 mmol) slowly is added drop-wise to NaClO
2(3.22 g, 30 mmol, 85% purity), dense HCl(6 mL) and MeCN(20 mL) mixed system in.In the reinforced process with temperature in the water-bath control reaction system 10～20
OCBetween.After reinforced complete, continue stirring reaction 30 min, acetonitrile is removed in decompression under the cold condition, adds 25 mL water, with 25 mL ethyl acetate extractions, anhydrous Na
2SO
4Drying, desolventizing obtains ethyl chloride, light yellow oily liquid, 0.591 g, productive rate 46%.
1H?NMR?(400?MHz,?CDCl
3)?δ:?3.74?(q,?
J?=?7.3?Hz,?2?H),?1.57?(t,?
J?=?7.3?Hz,?3?H).
Embodiment 11
The n-hexyl SULPHURYL CHLORIDE
2kPreparation
Pressing the method for describing among the embodiment one, is raw material with bromo normal hexane and thiocarbamide.In the last handling process, after acetonitrile is removed in decompression, add 25 mL water, with 25 mL ethyl acetate extractions, anhydrous Na
2SO
4Drying, desolventizing obtains the n-hexyl SULPHURYL CHLORIDE, light yellow oily liquid, 0.886 g, productive rate 96%.
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 12
N-Hexadecylsulfuryl Chloride
2lPreparation
Pressing the method for describing among the embodiment 11, is raw material with bromo n-hexadecane and thiocarbamide, obtains n-Hexadecylsulfuryl Chloride, clear crystal, 51～52 ℃ of fusing points, 1.540 g, productive rate 95%.
1H?NMR?(400?MHz,?CDCl
3)?δ:?3.73～3.51?(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 13
3-methyl butyl SULPHURYL CHLORIDE
2mPreparation
Pressing the method for describing among the embodiment 11, is raw material with 1-bromo-3-methylbutane and thiocarbamide, obtains 3-methyl butyl SULPHURYL CHLORIDE, light yellow oily liquid, 0.632 g, productive rate 74%.
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 14
The normal-butyl SULPHURYL CHLORIDE
2nPreparation
The 3mL acetonitrile solution of n-butyl mercaptan (0.451 g, 5 mmol) slowly is added drop-wise to NaClO
2(1.61 g, 15 mmol, 85% content), dense HCl(3 mL) and MeCN(10 mL) mixed system in.In the reinforced process with temperature in the water-bath control reaction system 10～20
OCBetween.After reinforced complete, continue stirring reaction 30 min, acetonitrile is removed in decompression under the cold condition, adds 25 mL water, with 25 mL ethyl acetate extractions, anhydrous Na
2SO
4Drying, desolventizing obtains light yellow oily liquid normal-butyl SULPHURYL CHLORIDE, 0.642 g, productive rate 82%.
1H?NMR?(200?MHz,?CDCl
3)?
δ:?1.00?(t,?
J?=?7.3?Hz,?3?H,?CH
3),?1.45～1.63?(m,?2?H,?CH
2),?1.95～2.10?(m,?2?H,?CH
2),?3.63～3.73?(m,?2?H,?CH
2).
Embodiment 15
The tetramethylene disulfonic acid chloride
2oPreparation
Thiocarbamide (774 mg, 10 mmol) and Isosorbide-5-Nitrae-dibromobutane (1.08 g, 5 mmol) are dissolved in 5 mL ethanol, and behind back flow reaction 30 min, decompression is removed solvent and is obtained white solid.This white solid slowly is added drop-wise to NaClO
2(3.22 g, 30 mmol, 85% purity), dense HCl(6 mL) and MeCN(20 mL) mixed system in.In the reinforced process with temperature in the water-bath control reaction system 10～20
oBetween the C.After reinforced complete, continue stirring reaction 30 min, acetonitrile is removed in decompression under the cold condition, adds 50 mL water, and with the solid filtering in the system, drying obtains clear crystal product tetramethylene disulfonic acid chloride, 89～90 ℃ of fusing points, 1.206 g, productive rate 94%.
1H?NMR?(400?MHz,?CDCl
3)?δ:?3.85～3.75?(m,?4H),?2.32～2.27?(m,?4H).
Embodiment 16
2-phenyl ethyl sulfonyl chloride
2pPreparation
Pressing the method for describing among the embodiment 11, is raw material with 2-phenyl-bromide ethane and thiocarbamide, obtains 2-phenyl ethyl sulfonyl chloride, light yellow oily liquid, 0.627 g, productive rate 62%.
1H?NMR?(400?MHz,?CDCl
3)?δ:?7.38～7.20?(m,?5H),?3.99～3.88?(m,?2H),?3.36～3.30?(m,?2H).
Embodiment 17
The phenyl SULPHURYL CHLORIDE
2nPreparation
The 3mL acetonitrile solution of thiophenol (0.551 g, 5 mmol) slowly is added drop-wise to NaClO
2(1.61 g, 15 mmol, 85% content), dense HCl(3 mL) and MeCN(10 mL) mixed system in.In the reinforced process with temperature in the water-bath control reaction system 10～20
OCBetween.After reinforced complete, continue stirring reaction 30 min, acetonitrile is removed in decompression under the cold condition, adds 25 mL water, with 25 mL ethyl acetate extractions, anhydrous Na
2SO
4Drying, desolventizing obtains light yellow oily liquid benzene base SULPHURYL CHLORIDE, 0.724 g, productive rate 82%.
1H?NMR?(400?MHz,?CDCl
3)?δ:?8.05～7.63?(m,?5?H).
Embodiment 18
2-methoxyl group ethyl sulfonyl chloride
2rPreparation
Pressing the method for describing among the embodiment 11, is raw material with methylsulfonic acid 2-methoxyl group ethyl ester and thiocarbamide, obtains 2-methoxyl group ethyl sulfonyl chloride, light yellow oily liquid, 0.690 g, productive rate 87%.
1H?NMR?(400?MHz,?CDCl
3)?δ:?3.97～3.94?(m,?4H),?3.43?(s,?3H).
Embodiment 19
The benzyl SULPHURYL CHLORIDE
2aPreparation
3 mL acetonitrile solutions of benzyl sulfhydrate (0.621 g, 5 mmol) slowly are added drop-wise to NaClO
2(1.61 g, 15 mmol, 85% content), dense HCl(3 mL) and MeCN(10 mL) mixed system in.In the reinforced process with temperature in the water-bath control reaction system 10～20
OCBetween.After reinforced complete, continue stirring reaction 30 min, acetonitrile is removed in decompression under the cold condition, adds 25 mL water, and with the solid filtering in the system, drying obtains clear crystal benzyl SULPHURYL CHLORIDE, 90～91 ℃ of fusing points, 0.781 g, productive rate 82%.
1H?NMR?(400?MHz,?CDCl
3)?δ:?7.61～7.35?(m,?4H),?5.12?(s,?2H)。
Claims (7)
1. general SULPHURYL CHLORIDE preparation method, with formula [1a] to shown in the formula [1e]
S-alkyl isothiuronium salts [1a], mercaptan and thiophenol [1b], disulfide [1c], acetic acid mercaptan ester and acetic acid thiophenol ester [1d], xanthate [1e], the oxidation chlorination under acidic conditions through chlorous acid or its salt obtains the SULPHURYL CHLORIDE shown in the formula [2];
Wherein: R represent to have 1～20 carbon atom alkyl, have 3～20 carbon atoms cycloalkyl, have 4～20 carbon atoms cycloalkylalkyl, have 6～20 carbon atoms aryl, have 7～20 carbon atoms aralkyl, have 2～20 carbon atoms alkoxyalkyl, have 7～20 carbon atoms aryloxyalkyl group, have 3～20 carbon atoms alkoxycarbonyl alkyl, have the alkylidene group of 2～20 carbon atoms; X represents chlorion, bromide anion, iodide ion, methanesulfonate, tosic acid root, bisulfate ion, sulfate radical; R ' expression has alkyl, cycloalkyl and the cycloalkylalkyl of 1～10 carbon atom; Alkyl wherein can be straight chain and side chain, and cycloalkyl and aryl can be and ring that aryl wherein can contain alkyl, alkoxyl group, acyl group, ester group, halogens chlorine, bromine and iodine, amino, nitro and cyano group substituting group.
2. general SULPHURYL CHLORIDE preparation method as claimed in claim 1, it is characterized in that described raw material can be formula [1a] to a plurality of sulphur structural units that contain shown in the formula [1e], can be used for preparing molecule and contain two to the compound of four chlorosulfonyls.
3. such as general SULPHURYL CHLORIDE preparation method as described in claim 1 and 2, it is characterized in that described raw material can be to have optically actively, can be used for preparation and have optically active SULPHURYL CHLORIDE.
4. such as general SULPHURYL CHLORIDE preparation method as described in the claim 1,2 and 3, it is characterized in that described chlorite can be sodium salt, lithium salts, sylvite, cesium salt, calcium salt, magnesium salts.
5. such as general SULPHURYL CHLORIDE preparation method as described in the claim 1,2 and 3, it is characterized in that described acid is hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, the acetic acid of 0.01～12 mol/L.
6. such as general SULPHURYL CHLORIDE preparation method as described in the claim 1,2 and 3, it is characterized in that described solvent is selected from water, tetrahydrofuran (THF), dioxane, acetonitrile or their mixture.
7. such as general SULPHURYL CHLORIDE preparation method as described in the claim 1,2 and 3, it is characterized in that described oxidation chlorination reaction is-30～150
oCarry out under the C condition.
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| CN109721530A (en) * | 2017-10-31 | 2019-05-07 | 成都博腾药业有限公司 | A method of preparing the fluoro- 2- pyridine sulfonyl chloride of 6- |
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| 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 |
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