CN111548258A - Use of sulfonyl type compounds as chlorination reagents - Google Patents
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- 238000005660 chlorination reaction Methods 0.000 title description 22
- 239000003153 chemical reaction reagent Substances 0.000 title description 14
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000012320 chlorinating reagent Substances 0.000 claims abstract description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 12
- 125000003545 alkoxy group Chemical class 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- 125000005843 halogen group Chemical class 0.000 claims abstract 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- -1 sulfonyl compound Chemical class 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical class [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 3
- KADOHHPNWMXGNG-UHFFFAOYSA-N 1-(1-chlorocyclopropyl)ethanone Chemical compound CC(=O)C1(Cl)CC1 KADOHHPNWMXGNG-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- XQRGPXLSPCQVBC-UHFFFAOYSA-N 2-chloro-1-cyclohexylethanone Chemical compound ClCC(=O)C1CCCCC1 XQRGPXLSPCQVBC-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- ZALMZWWJQXBYQA-UHFFFAOYSA-N [N].[Cl] Chemical compound [N].[Cl] ZALMZWWJQXBYQA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- SMEDVXJKKOXLCP-UHFFFAOYSA-N cyamelide Chemical compound N=C1OC(=N)OC(=N)O1 SMEDVXJKKOXLCP-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229950009390 symclosene Drugs 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the use of a sulfonyl-type compound as a chlorinating agent, wherein the structural formula of the sulfonyl-type compound is shown in the following formula (I), in the formula (I), R is a substituted or unsubstituted straight-chain or branched-chain alkyl group with 1 to 30 carbon atoms, the substitution refers to the substitution of halogen, alkoxy with 1 to 20 carbon atoms and 6 to 14-membered aryl, the 6 to 14-membered aryl can be further substituted by alkyl with 1 to 20 carbon atoms, alkoxy with 1 to 20 carbon atoms and halogen.
Description
Technical Field
The invention relates to the field of fine organic synthesis, in particular to application of a sulfonyl compound as a chlorination reagent.
Background
The alpha-chloro carbonyl compound can be used for obtaining intermediates and products with different structures and functions through reactions such as substitution, coupling, elimination and the like, and has wide application in the fields of organic synthesis, research and development of medicines and agricultural chemicals and production (edited by schofulyu, handbook of medical intermediates, publishers of chemical industry, 2000; edited by schuman, handbook of agricultural chemicals intermediates, publishers of chemical industry, 2004). At present, the common chlorination method still has the defects of poor stability, inconvenient operation, more byproducts, high equipment requirement, difficult treatment of reactants and the like. Therefore, improvements in chlorinating agents and chlorination processes are needed both economically and practically.
In 1948, Takara and others chlorinated alpha-position of a sulfonyl-substituted ketone using sulfonyl chloride as a chlorinating agent (Yakugakuzu Zasshi,1948, vol.68, p.165, chem.Abstr.,1954, p.3965). In 1990, the process was adopted by Bayer for the chlorination of chloroacetylcyclohexane. The chlorination time was 14 hours, the reaction solvent was dichloromethane, and the yield was 74% as reported in U.S. Pat. No. 4,493,8791, which does not further illustrate the treatment of the off-gas sulfur dioxide and hydrogen chloride generated during the reaction.
In 2012, Zhou and Swamy et al reported a mild and highly efficient chlorinating reagent, ammonium chloride and the commercial reagent Oxone (2 KHSO)5·KHSO4·K2SO4) For a series of substituted benzophenones, estersThe α -position chlorination of aliphatic ketones with a reaction yield of 30-90% (chem.lett.,2012,41,432), however, this process has the disadvantages that the amount of Oxone used is large and that the large amount of waste potassium salts produced after the reaction needs to be recovered, which is not suitable for industrialization3)3SiCl-KNO3DCDMH (1, 3-dichloro-5, 5-dimethylhydantoin), NCS (N-chlorosuccinimide), NCS-DMSO, NCS-UHP (urea-hydrogen peroxide), and the like (china. chem. lett.,2012,23, 1213; Tetrahedron lett.2011,52,1217; synth. commu.2006, 36,255; Tetrahedron,2008,64, 5191). These systems suffer to varying degrees from the disadvantages of expensive reagents, large amounts of reagents, potential explosion risks, etc.
In 2015, the chinese patent CN104610100A discloses a nitrogen-chlorine type chlorinating reagent, which partially overcomes the above disadvantages, but the operation is inconvenient because fluorine gas and chlorine gas are continuously used in the preparation process of the chlorinating reagent, and industrial application is not utilized.
In 2017, Chinese invention patent CN107118090A discloses a chlorination process of a carbonyl alpha-site, which uses stable solid trichloroisocyanuric acid as a chlorination reagent and Lewis acid as a catalyst, and avoids the problems of toxicity, irritation and stability caused by using chlorination reagents such as chlorine, sulfonyl chloride and the like. However, after the reaction is completed, insoluble cyanuric acid is produced and mixed with a lewis acid catalyst, and thus, there is a demand for product purification and cyanuric acid recovery.
For example, chinese patent CN105384617A discloses a process for chlorination using a microreactor, and the chlorination reagent is chlorine gas, which increases the yield by about 20-30% compared with the conventional method.
In summary, the chlorination reagent for carbonyl alpha-site has the problems of inconvenient operation, toxicity, explosive risk and the like, and has the problems of high raw material cost and high equipment corrosion resistance requirement, which is not favorable for the requirement of industrial production.
Disclosure of Invention
The invention aims to provide a sulfonyl-type chlorinating reagent, so that the three-waste emission and safety risk of the conventional chlorinating reagent in the reaction process are reduced, and meanwhile, the chlorination reaction condition is mild, the selectivity is high, the post-treatment is simple, and the method is suitable for industrial production.
The invention therefore discloses the use of a class of sulfonyl-type compounds as chlorinating agents, the structural formula of said sulfonyl-type compounds being represented by the following formula (I):
in formula (I), R is a substituted or unsubstituted, straight or branched alkyl group having 1 to 30 carbon atoms, which means that it may be substituted with halogen, alkoxy group having 1 to 20 carbon atoms, 6 to 14-membered aryl group, which may be further substituted with alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, halogen. Specifically, R may be selected from one of methyl, ethyl, propyl, n-butyl, benzyl or substituted benzyl, which may be ortho-, meta-or para-substituted.
In one embodiment, the sulfonyl-type compound is the following compound (a):
in one embodiment, the sulfonyl-type compound is the following compound (b):
in one embodiment, the sulfonyl-type compound is prepared by the following method:
at low temperature, sulfuryl chloride is added dropwise to an alcohol compound R-OH, wherein R is as defined above, and the produced hydrogen chloride and the excess alcohol are removed by distillation, wherein the molar ratio of sulfuryl chloride to alcohol compound is 0.8 to 1.5, preferably 1.0 to 1.05.
In one embodiment, the reaction of the sulfonyl chloride with the alcohol is carried out at a temperature of from 0 to-5 ℃.
Advantageous effects
Due to the steric hindrance effect, the chlorination reagent disclosed by the invention can be used for carrying out single chlorination on the carbonyl alpha-position of organic molecules such as aldehyde, ketone, ester and the like in a high-selectivity manner under a mild condition, so that the generation of polychlorinated byproducts is reduced, the chlorination reagent disclosed by the invention can be used for solving the safety problem existing in the use process of the existing chlorination reagents such as chlorine, sulfonyl chloride and the like, the post-treatment and three-waste treatment steps are reduced, and the chlorination reagent is suitable for industrial-scale production.
Drawings
FIG. 1 is a gas chromatogram of the chlorinated product obtained in example 1.
FIG. 2 is a gas chromatogram of the chlorinated product obtained in example 2.
FIG. 3 is a gas chromatogram of the chlorinated product obtained in comparative example 1.
Detailed Description
The chlorinating agents disclosed herein are described below in conjunction with specific embodiments. These descriptions are not intended to limit the scope of the present invention.
Preparation example 1: preparation of Compound (a)
The method comprises the following steps: adding 20g (0.435mol) of ethanol into a 250mL round-bottom flask, reducing the temperature of a system to 0-5 ℃, then slowly dropwise adding 58.7g (0.435mol) of sulfonyl chloride into the ethanol, and controlling the dropwise adding speed with vigorous stirring to ensure that the temperature of the system is maintained at 0-5 ℃ in the whole dropwise adding process, reacting to release hydrogen chloride gas, and absorbing tail gas through water to obtain hydrochloric acid with the mass concentration of 10-15%;
step two: after the dropwise addition, a small amount of hydrogen chloride and unreacted ethanol dissolved in the reaction system are removed by reduced pressure distillation, and 58.7g of light yellow liquid, namely the compound (a), is obtained, and the content of the effective chlorinating agent is about 90% by chlorination measurement with a substrate.
1H-NMR(400MH，CDCl3)：＝3.57(m，2H)；＝1.38(m，3H)。MS(EI)：m/z found，143.96(100％)；m/z found，145.96(36.5％)。
Preparation example 2: preparation of Compound (b)
The method comprises the following steps: adding 47g (0.435mol) of benzyl alcohol and 50mL of dichloromethane into a 250mL round-bottom flask, reducing the temperature of the system to 0-5 ℃, then slowly dropwise adding 58.7g (0.435mol) of sulfonyl chloride into the system, and controlling the dropwise adding speed with vigorous stirring to ensure that the temperature of the system is maintained at 0-5 ℃ in the whole dropwise adding process, reacting to release hydrogen chloride gas, and performing tail gas absorption through water to obtain hydrochloric acid with the mass concentration of 10-15%;
step two: after the dropwise addition, a small amount of hydrogen chloride and a solvent dichloromethane which are dissolved in the reaction system are removed by reduced pressure distillation, and 84.5g of yellow oily liquid, namely the compound (b), is obtained, and the content of the effective chlorinating agent is about 90% by chlorination measurement with a substrate.
1H-NMR(400MH，CDCl3)：＝7.47(m，2H)；＝7.38(m，3H)；＝4.79(s，2H)。MS(EI)：m/z found，205.98(100％)；m/z found，207.98(37.2％)。
Example 1
1-chloro-1' -acetylcyclopropane was chlorinated using the compound (a) prepared in preparation example 1 as a chlorinating agent, and the reaction formula was:
adding 50g of 1-chloro-1' -acetyl cyclopropane and 50ml of dichloromethane into a 250ml three-neck round-bottom flask, placing the flask in a 0 ℃ cold bath for cooling, dropwise adding 67g (containing 90% effective chlorinating agent) of the compound (a) while stirring, controlling the temperature in the dropwise adding process between 0 and-5 ℃, controlling the dropwise adding time to be 3 hours, continuing to react for 1 hour after the addition is finished, reducing the pressure at room temperature to remove the organic solvent, raising the temperature to 60 ℃, continuing to distill under reduced pressure to remove the residual sulfur dioxide in the reaction system to obtain 64g of light yellow transparent oily liquid, and confirming that the product is 1-chloro-1-chloroacetyl cyclopropane with the purity of 96.5 percent through GC-MS and H-NMR. The product can be used directly in the reaction without further purification operations. Higher content products can be obtained by rectification.
1H-NMR(400MH，CDCl3)：＝4.54(s，2H)；＝0.82(m，2H)；＝0.57(m，2H)。
The waste gas produced in the reaction process is mainly sulfur dioxide, the mixed tail gas is led into an industrial liquid alkali tank after passing through a saturated sodium sulfite solution, high-purity sodium sulfite can be obtained, and no other VOC is discharged in the reaction process.
Example 2
1-chloro-1' -acetylcyclopropane was chlorinated using compound (b) prepared in preparation example 2, according to the reaction formula:
adding 50g of 1-chloro-1-acetyl cyclopropane and 50ml of dichloromethane into a 250ml three-neck round-bottom flask, cooling the flask in a cooling bath at 0 ℃, dropwise adding 97g of the compound (b) (containing 94% of effective chlorinating agent) while stirring, controlling the temperature in the dropwise adding process between 0 and-5 ℃, keeping the dropwise adding time for 3 hours, continuing to react for 1 hour after the dropwise adding is finished, carrying out reduced pressure distillation at room temperature, removing the organic solvent, heating the temperature to 60 ℃, keeping on the reduced pressure distillation to remove residual sulfur dioxide, transferring the crude product to a rectifying tower, rectifying to obtain a target product, and directly recycling benzyl alcohol at the bottom of the kettle for preparing the compound (b). 55g of colorless transparent liquid can be obtained, and the product 1-chloro-1-chloroacetylcyclopropane is confirmed to have purity of more than 99.0% by GC and H-NMR.
The reaction off-gas was treated in the same manner as in example 1.
Comparative example 1
Adding 50g of 1-chloro-1-acetyl cyclopropane and 50mL of dichloromethane into a 250mL three-neck round-bottom flask, cooling the flask in a 0 ℃ cold bath, dropwise adding 85g (1.5eq.) of sulfonyl chloride while stirring, controlling the temperature in the dropwise adding process to be between 0 and 5 ℃ below zero, controlling the dropwise adding time to be 3 hours, continuing to react for 6 hours at room temperature after the dropwise adding is finished, carrying out center-control sampling analysis until the reaction is complete, dropwise adding 100mL of distilled water to quench the reaction, controlling the temperature of the system to be not more than 40 ℃ during the quenching process, continuing to stir for 30 minutes after the quenching process, carrying out phase separation, washing an organic phase with saturated sodium bicarbonate and water, drying, carrying out reduced pressure distillation to remove a solvent, continuing to carry out reduced pressure distillation on a crude product, and obtaining 45g of a mixture of the 1-chloro-1-chloroacetyl cyclopropane.
As can be seen from the above examples 1-2 and comparative example 1, the chlorinating agent of the present invention can be used to prepare a high purity monochlorinated product, greatly improves the selectivity to the monochlorinated product compared with the existing chlorinating agent, and simplifies the post-treatment and three-waste treatment steps, thus being suitable for industrial scale production.
The above description is only two specific examples of the present invention, but the types and application ranges of the chlorinating agents described in the present invention are not limited thereto, and any person skilled in the art who applies the chlorinating agents and the application methods disclosed in the present invention is within the protection scope of the present patent.
Claims (4)
1. Use of a sulfonyl-type compound as a chlorinating agent, the sulfonyl-type compound having the formula (I):
in formula (I), R is a substituted or unsubstituted, linear or branched alkyl group having 1 to 30 carbon atoms, which means that it may be substituted with halogen, alkoxy group having 1 to 20 carbon atoms, 6 to 14-membered aryl group, which may be further substituted with alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms or halogen.
2. Use according to claim 1, wherein R of formula (I) is selected from one of methyl, ethyl, propyl, n-butyl, benzyl or substituted benzyl, and
the substituted benzyl group may be ortho, meta or para substituted.
3. Use according to claim 1, wherein the sulfonyl-type compound is the following compound (a):
4. use according to claim 1, wherein the sulfonyl-type compound is the following compound (b):
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8308615D0 (en) * | 1983-03-29 | 1983-05-05 | Leo Pharm Prod Ltd | Chemical compounds |
| CN101395167A (en) * | 2006-02-28 | 2009-03-25 | V.B.医疗保险私人有限公司 | A novel chlorination reagent and a novel process for chlorination of sugars using thionyl chloride |
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