CN115160102B - Preparation method of gem dihalide - Google Patents
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- CN115160102B CN115160102B CN202210972148.6A CN202210972148A CN115160102B CN 115160102 B CN115160102 B CN 115160102B CN 202210972148 A CN202210972148 A CN 202210972148A CN 115160102 B CN115160102 B CN 115160102B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 150000002576 ketones Chemical class 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims abstract description 11
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- -1 dichloro compound Chemical group 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 6
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical group O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- GKDLTXYXODKDEA-UHFFFAOYSA-N 1-phenylbutan-2-one Chemical compound CCC(=O)CC1=CC=CC=C1 GKDLTXYXODKDEA-UHFFFAOYSA-N 0.000 claims description 3
- UNNIDDWFDCGQSF-UHFFFAOYSA-N 2,4-dibenzyl-1,5-diphenylpentan-3-one Chemical compound C=1C=CC=CC=1CC(CC=1C=CC=CC=1)C(=O)C(CC=1C=CC=CC=1)CC1=CC=CC=C1 UNNIDDWFDCGQSF-UHFFFAOYSA-N 0.000 claims description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229940125782 compound 2 Drugs 0.000 claims description 2
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 claims description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 abstract description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052794 bromium Inorganic materials 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000012216 screening Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 4
- ZEOVXNVKXIPWMS-UHFFFAOYSA-N 2,2-dichloropropane Chemical compound CC(C)(Cl)Cl ZEOVXNVKXIPWMS-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- PNLQPWWBHXMFCA-UHFFFAOYSA-N 2-chloroprop-1-ene Chemical compound CC(Cl)=C PNLQPWWBHXMFCA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000000950 dibromo group Chemical group Br* 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- XWDSASBQVXXTNE-UHFFFAOYSA-N 2,2-dibromobutane Chemical compound CCC(C)(Br)Br XWDSASBQVXXTNE-UHFFFAOYSA-N 0.000 description 1
- MOUDFOLIRVUWKC-UHFFFAOYSA-N 3,3-dichloropentane Chemical compound CCC(Cl)(Cl)CC MOUDFOLIRVUWKC-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/18—Preparation of halogenated hydrocarbons by replacement by halogens of oxygen atoms of carbonyl groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a gem dihalide, belonging to the technical field of organic synthesis. The ketone 1 is used as a raw material to react with phosphorus pentachloride under the action of a catalyst to obtain a gem-dichloro compound, or the ketone 1 reacts with triphenyl phosphite and bromine together to obtain a gem-dibromo compound. The invention only synthesizes the gem dihalide directly in one step, the reaction condition is relatively mild, the product yield is high, and the reliability of the process is further verified by screening different ketones to synthesize the corresponding gem dihalide.
Description
Technical Field
The invention relates to a preparation method of a gem dihalide, belonging to the technical field of organic synthesis.
Background
The geminal dihalides are widely used as intermediates in organic synthesis in the synthesis of pharmaceuticals, pesticides and other fine chemicals. For example, 2-dichloroaldehyde is a bifunctional substrate in organic synthesis, which can be applied to synthesis of nylon and preparation of ethynyl compounds. The gem dihalide can eliminate and synthesize halogenated olefin in one step, and has high yield and high reaction speed. The development of more efficient, direct synthetic methods for gem dihalides has been the subject of investigation.
When preparing the gem-dichlorides, aldehydes or ketones are reacted with chlorinating reagents such as phosphorus pentachloride, tungsten hexachloride, boron trichloride and the like to prepare the gem-dichlorides, or hydrazones are synthesized with hydrazine hydrate first, and then the corresponding gem-dihalides are obtained by combining chlorine/cuprous bromide and lithium tert-butoxide, wherein when the raw material is aldehydes, the reagents or the methods have good yields, however, when the raw material is ketones, the yields are often low by using the reagents or the methods, and alkenyl chloride byproducts can be eliminated by themselves.
In the preparation of gem-dibromo compounds, the literature [ Synthesis,1986, #1, p.122-125] reports the condensation of ketones with trimethyl orthoformate to ketals, subsequent exchange with catechol and final reaction with boron tribromide to give gem-dibromo compounds. The method has long steps and relatively high cost, and is not suitable for industrial production.
Aiming at the defects of the method, the preparation method which is simple and convenient in flow, short in steps, economical and high in yield is adopted, and the method is suitable for factory production so as to meet the increasing market demands.
Disclosure of Invention
In order to overcome the technical defects, ketone 1 is used as a raw material to react with phosphorus pentachloride under the action of a catalyst to obtain a gem-dichloro compound, or ketone 1 is jointly reacted with triphenyl phosphite and bromine to obtain a gem-dibromo compound. The reaction of the invention only synthesizes the gem dihalide directly by one step, the reaction condition is relatively mild, the product yield is high, and the reliability of the process is further verified by screening different ketones to synthesize the corresponding gem dihalide.
The invention relates to a preparation method of a geminal dihalide compound, which comprises the following reaction equation:
and (3) a gem dichloro: mixing ketone 1, phosphorus pentachloride, a catalyst and an organic solvent for reaction to obtain a geminal dichloro compound 2;
and (3) a gem dibromo compound: mixing triphenyl phosphite with an organic solvent, adding bromine for reaction, and then adding ketone 1 for reaction to obtain a gem dibromo 3;
further, in the above technical scheme, the ketone 1 is selected from 3-pentanone, acetone, 2-butanone, dibenzylmethyl ketone or 1-phenyl-2-butanone.
Further, in the above technical scheme, in the geminal dichlorides, the catalyst is selected from anhydrous ferric trichloride, anhydrous zinc chloride or triphenylboron.
Further, in the above technical scheme, in the gem dichloro, the organic solvent is selected from sulfolane and a mixture of n-hexane, n-heptane or toluene.
Further, in the above technical scheme, in the geminal dichloro compound, the molar ratio of the ketone 1, phosphorus pentachloride to the catalyst is 1:1.05-1.2:0.1-0.15.
Further, in the above technical scheme, in the gem dibromo compound, the organic solvent is selected from dichloromethane or chloroform.
Further, in the above technical scheme, in the geminal dibromo compound, the molar ratio of the ketone 1, triphenyl phosphite and bromine is 1:1.1-1.2:1.1-1.2.
Further, in the above technical scheme, in the geminal dichlorides, the reaction temperature is 0 ℃ to 80 ℃; in the geminal dibromo compound, the reaction temperature is-40 ℃ to 0 ℃.
Advantageous effects of the invention
The carbonyl group is catalyzed by ferric chloride, zinc chloride and the like to react with phosphorus pentachloride, and in the presence of a catalyst (especially BPh 3), the reaction can generate geminal dichloro and alkenyl chloride, and meanwhile, byproduct hydrogen chloride gas is added with the alkenyl chloride again to generate more geminal dichloro products under the one-pot condition. The method for generating the gem-dibromo by reacting triphenyl phosphite with bromine is adopted, and the product mainly containing the gem-dibromo is obtained under the condition of no alkali.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The invention is further illustrated by the following specific examples. These examples should be construed as merely illustrative of the present invention and not limiting the scope of the present invention. Various changes and modifications to the present invention may be made by one skilled in the art after reading the description herein, and such equivalent changes and modifications are intended to fall within the scope of the present invention as defined in the appended claims.
Preparation of geminal dichlorides
Example 1
43.7g (0.21 mol) of phosphorus pentachloride, 3.3g (0.02 mol) of anhydrous ferric trichloride and 40mL of sulfolane are mixed under the protection of nitrogen, the temperature is raised to 40-45 ℃, 17.2g (0.2 mol) of 3-pentanone and 150mL of n-hexane mixed solution are added, and the mixture is stirred for 30 minutes after the dropwise addition. Then heating to 60-65 ℃ for reaction for 8 hours, cooling the reaction liquid to room temperature, filtering the catalyst, then decompressing and distilling until no fluid is produced, and rectifying the obtained fraction to obtain 21.6g of 3, 3-dichloropentane; GC 98.9%, yield 76.7%. GCMS: m+1= 142.1.
Example 2
43.7g (0.21 mol) of phosphorus pentachloride, 3.3g (0.04 mol) of anhydrous ferric trichloride and 40mL of sulfolane are mixed under the protection of nitrogen, the temperature is raised to 30-35 ℃, 11.6g (0.2 mol) of acetone and 150mL of n-heptane mixed solution are added, and after the dropwise addition, stirring reaction is carried out for 30 minutes. Then heating to 40-45 ℃ for reaction for 12 hours (the raw materials are completely converted, the GC ratio of 2, 2-dichloropropane and 2-chloropropene is 92/8), cooling the reaction liquid to room temperature, filtering the catalyst, then decompressing and distilling until no liquid flows, and rectifying the obtained fraction to obtain 15.7g of 2, 2-dichloropropane; GC98.4% yield 69.4%. GCMS: m+1=113.9. BPh was used 3 When the catalyst (0.04 mol) replaces anhydrous ferric trichloride, the yield is 82.2% (GC 98.8%); when anhydrous ferric trichloride was not added, the GC ratio of the 2, 2-dichloropropane and 2-chloropropene was 61/39 (the total area normalization ratio was 82%) and the yield was 33.6% (99.1%).
Example 3
43.7g (0.21 mol) of phosphorus pentachloride, 4.1g (0.03 mol) of zinc dichloride and 60mL of sulfolane are mixed under the protection of nitrogen, the temperature is raised to 40-45 ℃, 42.1g (0.2 mol) of dibenzylmethyl ketone and 300mL of toluene are added for mixing, then the temperature is raised to 60-65 ℃ for reacting for 10 hours, the reaction solution is cooled to room temperature, activated carbon and silica gel are added, filtration and reduced pressure concentration are carried out on the filtrate, n-heptane is replaced, and 2, 2-dichloro dimethylbenzene 43.1g is obtained through recrystallization; HPLC 99.4%, yield 81.3%. 1 HNMR(400MHz,CDCl3):7.31-7.11(m,10H),3.12(s,4H).
With reference to the reaction conditions of example 3, the different ketones were exchanged to give the geminal dichlorides, with the following results:
preparation of gem-dibromo compounds
Example 4
Under the protection of nitrogen, 68.3g (0.22 mol) of triphenylphosphine oxide is dissolved in methylene dichloride, the temperature is reduced to-40 ℃, 35.2g (0.22 mol) of bromine is slowly added at the temperature of-40 to-30 ℃, then 14.4g (0.2 mol) of 2-butanone is slowly added dropwise, the reaction is carried out for 2 hours, the reaction solution is warmed to room temperature, the reaction is carried out for 2 hours, reduced pressure concentration is carried out, most of the triphenylphosphine oxide is filtered, and the rest reduced pressure distillation is carried out to obtain 35g of 2, 2-dibromobutane, GC96.9%, and the yield is 81.1%.
Example 5
Under the protection of nitrogen, 68.3g (0.22 mol) of triphenylphosphine oxide is dissolved in methylene dichloride, the temperature is reduced to minus 25 ℃, 35.2g (0.22 mol) of bromine is slowly added under the control of the temperature of minus 25 ℃ to minus 20 ℃, 26.8g (0.2 mol) of 1-phenyl-2-butanone is slowly added dropwise, the reaction is carried out for 2 hours, the reaction solution is heated to room temperature, the reaction is carried out for 2 hours, the reduced pressure concentration is carried out, most of the triphenylphosphine oxide is filtered, 45.8g of dibromo-2, 2-phenyl-1-propane is obtained by the residual column chromatography, HPLC95.7 percent, and the yield is 82.4 percent 1 HNMR(400MHz,CDCl3):7.41-7.25(m,5H),3.49(s,2H),2.58(s,3H).
The results of the exchange of the different ketones to give the geminal dibromo are shown in Table 2:
TABLE 2
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should be covered by the protection scope of the present invention by making equivalents and modifications to the technical solution and the inventive concept thereof.
Claims (4)
1. A process for the preparation of a geminal dichloro compound, comprising the steps of: and (3) a gem dichloro: mixing ketone 1, phosphorus pentachloride, a catalyst and an organic solvent for reaction to obtain a geminal dichloro compound 2; the ketone 1 is selected from 3-pentanone, acetone, 2-butanone, dibenzylmethyl ketone or 1-phenyl-2-butanone; the catalyst is selected from anhydrous ferric trichloride, anhydrous zinc dichloride or triphenylboron.
2. The process for the preparation of geminal dichlorides according to claim 1, characterized in that: the organic solvent is selected from sulfolane and mixture of n-hexane, n-heptane or toluene.
3. The process for the preparation of geminal dichlorides according to claim 1, characterized in that: the molar ratio of the ketone 1 to the phosphorus pentachloride to the catalyst is 1:1.05-1.2:0.1-0.15.
4. The process for the preparation of geminal dichlorides according to claim 1, characterized in that: the reaction temperature is 0-80 ℃.
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