CN1468838A - Prepn process of 2,6-dichloro-4-trifluoro methylaniline - Google Patents
Prepn process of 2,6-dichloro-4-trifluoro methylaniline Download PDFInfo
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- CN1468838A CN1468838A CNA02132607XA CN02132607A CN1468838A CN 1468838 A CN1468838 A CN 1468838A CN A02132607X A CNA02132607X A CN A02132607XA CN 02132607 A CN02132607 A CN 02132607A CN 1468838 A CN1468838 A CN 1468838A
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- 238000000034 method Methods 0.000 title claims abstract description 14
- ITNMAZSPBLRJLU-UHFFFAOYSA-N 2,6-dichloro-4-(trifluoromethyl)aniline Chemical compound NC1=C(Cl)C=C(C(F)(F)F)C=C1Cl ITNMAZSPBLRJLU-UHFFFAOYSA-N 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 238000002360 preparation method Methods 0.000 claims abstract description 25
- 230000026030 halogenation Effects 0.000 claims abstract description 19
- 238000005658 halogenation reaction Methods 0.000 claims abstract description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 15
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 19
- 230000002140 halogenating effect Effects 0.000 claims description 15
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 10
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 8
- DGRVQOKCSKDWIH-UHFFFAOYSA-N 1-chloro-2-(trifluoromethyl)benzene Chemical class FC(F)(F)C1=CC=CC=C1Cl DGRVQOKCSKDWIH-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 238000005576 amination reaction Methods 0.000 claims description 5
- 229960004839 potassium iodide Drugs 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 235000007715 potassium iodide Nutrition 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003983 crown ethers Chemical class 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 239000003444 phase transfer catalyst Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 2
- 235000009518 sodium iodide Nutrition 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- XILPLWOGHPSJBK-UHFFFAOYSA-N 1,2-dichloro-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(Cl)C(Cl)=C1 XILPLWOGHPSJBK-UHFFFAOYSA-N 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000000460 chlorine Substances 0.000 description 13
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 238000010792 warming Methods 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 229940083608 sodium hydroxide Drugs 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- -1 halogen aromatic amines Chemical class 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000001256 steam distillation Methods 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 238000005660 chlorination reaction Methods 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 229960004756 ethanol Drugs 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 150000003457 sulfones Chemical class 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- 229940117389 dichlorobenzene Drugs 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- 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 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QULYNCCPRWKEMF-UHFFFAOYSA-N parachlorobenzotrifluoride Chemical compound FC(F)(F)C1=CC=C(Cl)C=C1 QULYNCCPRWKEMF-UHFFFAOYSA-N 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- 150000003254 radicals Chemical group 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Substances BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 1
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical class ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- KSESZRGARIEOFC-UHFFFAOYSA-N [2-chloro-4-(trifluoromethyl)phenyl]hydrazine Chemical compound NNC1=CC=C(C(F)(F)F)C=C1Cl KSESZRGARIEOFC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The preparation process of 2, 6-dichloro-4-trifluoro methylaniline with 3, 4-dichloro trifluoro toluene as initial material and dimethylamine as methylaminating agent includes four reaction steps of dimethylamination, halogenation, catalytic side chain methyl halogenation and hydrolysis. The said process is easy to realize in industrial production and has easy-to-obtain material, high yield and high product purity.
Description
Technical field: the present invention relates to the new preparation method of a kind of many halogen aromatic amines, specifically, the invention provides a kind of novel process that is suitable for industrial preparation multi-halogenated aniline.
Background technology: 2, the 6-dichlor-4-trifluoromethyl aniline is a kind of important pesticide intermediate, is used to prepare pyrazole compound 5-amino-1-aryl-3-cyano pyrazole for example that insecticidal activity is arranged.In the prior art 2, the 6-dichlor-4-trifluoromethyl aniline has multiple preparation method: as US4, and 096,185; US4 has explained making 4-5-trifluoromethylaniline post chlorization by 4-chloro-phenylfluoroform and ammonia gas react and obtain in 388,472.This method needs high temperature, reaction under high pressure, is catalyzer with similar cuprous chloride and Potassium monofluoride mixture, and yield and transformation efficiency are all undesirable.2, the 6-dichlor-4-trifluoromethyl aniline also can be as EP0, and 384,392; US5 makes the 4-4-trifluoromethylbenzonitrile by 4-chloro-phenylfluoroform and sodium cyanide reaction described in 410,082, makes the 4-5-trifluoromethylaniline through hydrolysis and hoffman degradation reaction, and chlorination makes again.This method step long and the prussiate of use severe toxicity and the Ni (PPh that is difficult to prepare
3)
2Cl
2, technology is comparatively complicated, and yield is lower.Explained by 3 among the WO 00/59862, hydrogenation made 2-chloro-4-5-trifluoromethylaniline after 4-two chlorobenzotrifluorides and hydrazine hydrate reaction made 2-chloro-4-trifluoromethyl phenyl hydrazine, and chlorination makes 2 again, the method for 6-dichlor-4-trifluoromethyl aniline.The employed hydrazine hydrate explosive of this method, pyridine are made the solvent costliness and are had strong stink; Make in addition that pressure is difficult to control in the reaction process of 2-chloro-4-5-trifluoromethylaniline.US5 has explained with N in 401,882, and dinethylformamide is done the methylamine agent and obtained 2, and 6-two chloro-4-methyl fluoride-N, make 2 with sodium-hydroxide treatment, the method for 6-dichlor-4-trifluoromethyl aniline at accelerine after the ultraviolet lighting chlorination; Though halogenation and pendant methyl halogenation can be carried out under UV-irradiation, and light intensity and wavelength are had particular requirement, its suitability for industrialized production is had difficulties; The insolubles that produces influences illumination in the reaction process in addition, causes reaction later stage speed slow, is unfavorable for industrialization.While N, the dinethylformamide price is also more expensive.In sum, there are 3 deficiencies in prior art in preparation 2 in the method for 6-dichlor-4-trifluoromethyl aniline: 1, technology is complicated, and the industrialization difficulty is bigger; 2, raw material ratio is than costliness or poor stability; 3, reaction conversion ratio and product yield are lower.
Summary of the invention: in order to overcome deficiency of the prior art, inventors of the present invention develop one be easy to that industrialization, raw material are cheap and easy to get, reaction yield and product content are more high-new 2, the preparation method of 6-dichlor-4-trifluoromethyl aniline.
Provided by the invention 2, the preparation method of 6-dichlor-4-trifluoromethyl aniline (Compound I) comprises four-step reaction:
(1) diformazan amination reaction:
Compound (VII) compound (VI) (2) halogenating reaction:
Compound (V) compound (IV) (3) pendant methyl halogenating reaction:
Compound (III) (4) hydrolysis reaction
Compound (II)
Compound (I)
Inventors of the present invention select suitable catalyzer for use, replace N with low-cost dimethylamine in the diformazan amination reaction, the N dimethyl formamide is in order to preparation N, accelerine compounds.Reaction pressure is stable, helps suitability for industrialized production.
In the diformazan amination reaction, in 1 mole compound (VII): add 1-20 mole dimethylamine, suitable be the 4-8 mole, preferably the 4-5 mole.
This is reflected under two kinds of catalyzer existence and carries out: catalyst A is selected from alkali-metal halogenide, as iodine, bromine or the villiaumite of potassium, sodium or caesium, and preferred potassiumiodide or sodium iodide; Catalyst B is selected from phase-transfer catalyst such as quaternary amine, quaternary alkylphosphonium salt, crown ether, open chain glymes, preferred benzyltriethylammoinium chloride.The catalyst A add-on is the 0.1-10% of starting compound (VII) weight, preferred 0.5-1.5%; The catalyst B add-on is the 0.1-10% of starting compound (VII) weight, preferred 2-4%.
Reaction is carried out in the presence of solvent usually, can select water, alcohol, acetonitrile, N usually, dinethylformamide or dioxane isopolarity solvent; Preferred inexpensive and easily and the isolating C of product
1-C
6Alcohols is made solvent; Further preferred dehydrated alcohol.Reaction also can be carried out under solvent-free situation.
The reaction pair temperature range requires not strict, and be reflected between the 100-250 ℃ of temperature and all can carry out, be 150-220 ℃ than optimal temperature, preferred 190-195 ℃.
Reaction pressure is decided with temperature of reaction is different with coefficient.Usually reaction pressure is 0.8-8Mpa, and that suitable is 2-5Mpa, preferred 3.5-4Mpa.
Reaction times was generally 3-24 hour, preferred 6-15 hour, most preferably was 8-12 hour.
Another notable feature of the present invention is to use initiator to replace ultraviolet lighting to carry out the pendant methyl halogenation, and in same reactor, under than the demulcent condition, carry out halogenation and pendant methyl halogenation, improved reaction yield, thereby make preparation 2, the method for 6-dichlor-4-trifluoromethyl aniline is realized industrially scalable smoothly.
The available halogenating agent scope of halogenation and pendant methyl halogenation is very wide: can use halogen, as Cl
2, Br
2Deng, preferred Cl
2Also can use the halogenation sulfone, as the chlorination sulfone, bromination sulfone, preferred chlorination sulfone; Can also use Phosphorates phosphorus Halides reagent such as phosphorus pentachloride, phosphorus trichloride; Perhaps use as the N-bromo-succinimide free radical reaction reagent of N-chlorosuccinimide class; And the mix reagent of above any halogenating agent.
In same reactor, carry out halogenation and pendant methyl halogenating reaction, in 1 mole compound (VI): add 3-10 mole halogenating agent; When using the halogenation sulfone, preferably add 4 moles as halogenating agent; When using halogen, preferably add the 4-5 mole as halogenating agent.
The pendant methyl halogenation need be carried out under the initiator catalytic condition, and its initiator can be radical initiators such as peroxide, percarboxylate class, azo-compound class as Diisopropyl azodicarboxylate, benzoyl peroxide; Preferred Diisopropyl azodicarboxylate.The initiator add-on is the 0.1-10% of raw material weight, preferred 2-4%.
Halogenation and pendant methyl halogenating reaction are carried out in the presence of the solvent of free radical reaction can be used for usually.As acetonitrile, methylene dichloride, ethylene dichloride, 1,1,2,2, inertia halohydrocarbon and aromatic hydrocarbons such as-tetrachloroethane, chlorobenzene, dichlorobenzene, trichlorobenzene; Suitable is the lower halogenated hydrocarbon, as tetracol phenixin, methylene dichloride, ethylene dichloride, 1,1,2,2 ,-tetrachloroethane; Preferred tetracol phenixin.The consumption of solvent is generally: every kilomol raw material adds 0.1-2 kilolitre solvent; Preferred 0.5-1.5; Most preferably be 1-1.2.Reaction also can be carried out under solvent-free.
The halogenated temperature of reaction of halogenation and pendant methyl is 0-100 ℃, preferred 40-80 ℃; Reaction times is 1-10 hour, preferred 3-8 hour.
Hydrolysis reaction can carry out according to a conventional method.Usually with alcohol or water as medium, preferably under water medium, carry out.Reaction system can be acid, neutral or alkaline, preferred alkalescence.Usually used alkali is: alkali metal hydroxide, and alkaline carbonate, alkali metal acetate, ammoniacal liquor, or phosphoric acid hydrogen disalt etc., preferred sodium hydroxide or potassium hydroxide.
The pendant methyl halogenation preferentially generates the product that each halogen atom of N-methyl replaces, and also produces the many halogenated product of a certain amount of N-methyl in the reaction process, the more single halo difficulty of its hydrolysis reaction.Compound described in the present invention (VI) is easy to Quantitative yield and becomes compound (I) 2,6-dichlor-4-trifluoromethyl aniline.Hydrolysis reaction can produce formaldehyde, or produces by products such as formic acid and methyl alcohol by formaldehyde disproportionation under alkaline condition, all can wash and remove.
The purpose product can separate with ordinary method and obtain, and for example can obtain 2 by wet distillation, 6-dichlor-4-trifluoromethyl aniline crude product, and rectifying afterwards can obtain content greater than 98% product.
Adopt present method preparation 2, the most significant advantage of 6-dichlor-4-trifluoromethyl aniline is: technology is simple, reaction conditions relaxes and is easy to industrialization.Select for use raw material cheap and easy to get.The reaction yield height.
Embodiment: following embodiment is used to illustrate the present invention, but the present invention is not limited only to following embodiment.Embodiment 1:
2-chloro-4-trifluoromethyl-N, the preparation of accelerine:
Drop into 200g 98%3,4-two chloro-4-phenylfluoroforms, anhydrous potassiumiodide 2g to the 1000ml autoclave, anhydrous benzyltriethylammoinium chloride 6g, the 200g dimethylamine is dissolved in 500ml solution that dehydrated alcohol is joined, and is warming up to 195-200 ℃ of reaction, and reaction is 8-9 hour under this temperature, chromatogram tracking to raw material is finishing reaction below 1%, cooling discharge gets 204g 2-chloro-4-trifluoromethyl-N, accelerine, content 90%, yield 90%.
Embodiment 2-example 8
Device and operation steps change partial reaction conditioned disjunction material proportion with embodiment 1, the results are shown in Table-1:
Table-1:
In the table: a-3,4-two chloro-4-phenylfluoroform b-dimethylamine c-potassiumiodide d-benzyltriethylammoinium chloride e-Tetrabutyl amonium bromide f-Polyethylene Glycol-600s
| ??a | ??b | Solvent | Catalyst A | Catalyst B | Temperature (℃) | Content (%) | Yield (%) |
| ??200g | ??200g | Ethanol | ?c(2g) | ?------ | ?195-200 | ??90 | ??85 |
| ??200g | ??200g | Ethanol | ?------ | ?d(6g) | ?195-200 | ??88 | ??70 |
| ??200g | ??200g | Ethanol | ?c(2g) | ?e(6g) | ?190-195 | ??91 | ??86 |
| ??200g | ??200g | Ethanol | ?c(2g) | ?f(6g) | ?190-195 | ??89 | ??84 |
| ??200g | ??400g | Ethanol | ?c(2g) | ?d(6g) | ?170-175 | ??91 | ??86 |
| ??200g | ??200g | Acetonitrile | ?c(2g) | ?d(6g) | ?190-195 | ??89 | ??87 |
| ??200g | ??200g | ??DMF | ?c(2g) | ?d(6g) | ?190-195 | ??88 | ??83 |
Embodiment 9:
2, the preparation of 6-dichlor-4-trifluoromethyl aniline:
In the 200ml reaction flask, drop into 25g 2-chloro-4-trifluoromethyl-N, accelerine (99%), the 200g tetracol phenixin is warming up to 60-65 ℃, drips 20g SO in 1-2 hour
2Cl
2(85%), dropwise and stir half an hour, cooling adds 0.75g Diisopropyl azodicarboxylate (98%), is warming up to 55-60 ℃, Dropwise 5 0g SO in 4-5 hour
2Cl
2(85%), chromatogram tracking detection reaction terminal point, reaction finishes and boils off tetracol phenixin, the aqueous sodium hydroxide solution of Dropwise 5 0g 30% in residuum, back flow reaction 2-3 hour, reactants water was washed till PH=9, steam distillation gets 23g 2, the 6-dichlor-4-trifluoromethyl aniline, content 94%, yield 85%.
Embodiment 10:
Use benzoyl peroxide 0.75g to replace Diisopropyl azodicarboxylate to make initiator, repeat embodiment 9, obtain similar results, content 94%, yield: 84%
Embodiment 11:
Use chlorobenzene to make solvent and repeat embodiment 9 experiments, content 92%, yield: 73%.
Embodiment 12:
Use dichlorobenzene to make solvent and repeat embodiment 9 experiments, content 93%, yield 64%.
Embodiment 13:
2, the preparation of 6-dichlor-4-trifluoromethyl aniline:
In the 200ml reaction flask, drop into 25g 2-chloro-4-trifluoromethyl-N, accelerine (99%), the 200g tetracol phenixin, be warming up to 55-60 ℃, feed the about 9.5g of chlorine, reacted 3-4 hour, cooling adds 0.75g Diisopropyl azodicarboxylate (98%), be warming up to 50-55 ℃, feed the about 23.5g of chlorine again, chromatogram tracking detection reaction terminal point, reaction finishes and boils off tetracol phenixin, Dropwise 5 0g 30% aqueous sodium hydroxide solution in residuum, back flow reaction 2-3 hour, reactants water was washed till PH=9, steam distillation gets 2,6-dichlor-4-trifluoromethyl aniline 23g, content 89%, yield 80%.
Embodiment 14:
Use the 0.75g benzoyl peroxide to make initiator, repeat embodiment 13 experiments and obtain similar results, content 89%, yield: 79%
Embodiment 15:
Use chlorobenzene to make solvent and repeat embodiment 13 experiments, content 85%, yield: 68%.Embodiment 16:
Use dichlorobenzene to make solvent and repeat embodiment 13 experiments, content 86%, yield 56%.
Embodiment 17:
2-chloro-4-trifluoromethyl-N, the preparation of accelerine:
Drop into 200Kg 98%3,4-two chloro-4-phenylfluoroforms, anhydrous potassiumiodide 2Kg to the 1000L autoclave, anhydrous benzyltriethylammoinium chloride 6Kg, the 200Kg dimethylamine is dissolved in 500L solution that dehydrated alcohol is joined, and is warming up to 190-195 ℃ of reaction, reaction is 10 hours under this temperature, chromatogram tracking is finishing reaction to raw material below 1%, cooling discharge, and rectifying gets 175Kg2-chloro-4-trifluoromethyl-N, accelerine, content 99%, yield 85%, 134-136 ℃/50mmHg.
Embodiment 18:
2, the preparation of 6-dichlor-4-trifluoromethyl aniline:
In the 200L reactor, drop into 25Kg 2-chloro-4-trifluoromethyl-N, accelerine (99%), the 200Kg tetracol phenixin is warming up to 60-65 ℃, drips 20Kg SO in 1-2 hour
2Cl
2(85%), dropwise and stir half an hour, cooling adds 750g Diisopropyl azodicarboxylate (98%), is warming up to 55-60 ℃, Dropwise 5 0Kg SO in 4-5 hour
2Cl
2(85%), chromatogram tracking detection reaction terminal point, reaction finishes and boils off tetracol phenixin, the aqueous sodium hydroxide solution of Dropwise 5 0Kg 30% in residuum, back flow reaction 2-3 hour, reactants water was washed till PH=9, steam distillation gets 22.8Kg 2, the 6-dichlor-4-trifluoromethyl aniline, content 95%, yield 85%.
Embodiment 19:
2, the preparation of 6-dichlor-4-trifluoromethyl aniline:
In the 200L reactor, drop into 25Kg 2-chloro-4-trifluoromethyl-N, accelerine (99%), the 200Kg tetracol phenixin, be warming up to 55-60 ℃, feed the about 9.5Kg of chlorine, reacted 3-4 hour, cooling adds 750g Diisopropyl azodicarboxylate (98%), be warming up to 50-55 ℃, feed the about 23.5Kg of chlorine again, chromatogram tracking detection reaction terminal point, reaction finishes and boils off tetracol phenixin, Dropwise 5 0Kg 30% aqueous sodium hydroxide solution in residuum, back flow reaction 2-3 hour, reactants water was washed till PH=9, steam distillation gets 2,6-dichlor-4-trifluoromethyl aniline 23Kg, content 90%, yield 81%.
More than two examples resulting 2,6-dichlor-4-trifluoromethyl aniline crude product can obtain content greater than 98% product, rectifying yield 90% by rectifying.
According to U.S. Pat 5,401,882 use the comparative examples of UV-light: reference examples 1:
2, the preparation of 6-dichlor-4-trifluoromethyl aniline:
In the 250ml there-necked flask, drop into 25g 2,6-chloro-4-trifluoromethyl-N, accelerine (99%), the 200g tetracol phenixin, under 10-20 ℃, UV-irradiation adds 75g SO
2Cl
2(85%), chromatogram tracking detection reaction terminal point, reaction finishes and boils off tetracol phenixin, Dropwise 5 0g50% sodium hydroxide solution in the residuum, back flow reaction 2-3 hour, reactants water was washed till PH=9, and steam distillation gets 2,6-dichlor-4-trifluoromethyl aniline 17.5g, content is about 90%, yield 71%.Reference examples 2:
2, the preparation of 6-dichlor-4-trifluoromethyl aniline:
In the 250ml there-necked flask, drop into 25g 2,6-chloro-4-trifluoromethyl-N, accelerine (99%), the 200g tetracol phenixin, under 10-20 ℃, UV-irradiation, feed the about 30g of chlorine, chromatogram tracking detection reaction terminal point, reaction finishes and boils off tetracol phenixin, Dropwise 5 0g50% sodium hydroxide solution in the residuum, back flow reaction 2-3 hour, reactants water was washed till PH=9, steam distillation gets 2,6-dichlor-4-trifluoromethyl aniline 17.2g, content is about 85%, yield 66%.
Claims (6)
1, a kind of preparation 2, the novel method of 6-dichlor-4-trifluoromethyl aniline comprises following four-step reaction:
(1) diformazan amination reaction:
Compound (VII) compound (VI)
(2) halogenating reaction:
Compound (V) compound (IV)
(3) pendant methyl halogenating reaction:
Compound (III)
(4) hydrolysis reaction
Compound (II)
Compound (I)
2, according to the described preparation method of claim 1, it is characterized in that: in the diformazan amination reaction, dimethylamine with, the mol ratio of 4-two chlorobenzotrifluorides is 1-20: 1; Catalyst A is selected from iodine, bromine or the villiaumite of potassium, sodium or caesium; Catalyst B is selected from quaternary amine, quaternary alkylphosphonium salt, crown ether, open chain glymes phase-transfer catalyst; The consumption of catalyst A and B is respectively 3, the 0.1-10% of 4-two chlorobenzotrifluoride weight; Temperature of reaction is 100-250 ℃, and the reaction times is 1-30 hour, and reaction pressure is 0.5-5Mp.
3, according to the described preparation method of claim 2, it is characterized in that: dimethylamine and 3, the mol ratio of 4-two chlorobenzotrifluorides is 4-8; The consumption of catalyst A is 3, and the 0.5-1% of 4-two chlorobenzotrifluoride weight, the consumption of catalyst B are 3, the 2-4% of 4-two chlorobenzotrifluoride weight; Temperature of reaction is 150-220 ℃, and the reaction times is 5-15 hour, and reaction pressure is 1.5-4Mp.
4, according to the described preparation method of claim 3, it is characterized in that: catalyst A is selected from potassiumiodide or sodium iodide; Catalyst B is selected from benzyltriethylammoinium chloride.
5, according to the described preparation method of claim 1, it is characterized in that: in halogenation and the pendant methyl halogenating reaction halogenating agent be 3-10 by halid mol ratio: 1, temperature of reaction is 0-100 ℃, the reaction times is 1-10 hour; The pendant methyl halogenation is carried out in the presence of radical initiator, and initiator is selected from Diisopropyl azodicarboxylate or benzoyl peroxide, and consumption is by the 0.1-10% of halide weight.
6, according to the described preparation method of claim 5, it is characterized in that: in halogenation and the pendant methyl halogenating reaction halogenating agent be 4-5 by the halogenide mol ratio: 1, temperature of reaction is 40-80 ℃, and the reaction times is 3-8 hour, and initiator amount is by the 2-4% of halide weight.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011058577A1 (en) * | 2009-11-12 | 2011-05-19 | Keki Hormusji Gharda | Process for synthesizing polyhalogenated perhaloalkylaniline compounds |
| CN101289401B (en) * | 2008-03-24 | 2011-07-20 | 浙江巍华化工有限公司 | Process for preparing 2,6- dichlor-4-trifluoromethyl aniline |
| CN101289400B (en) * | 2008-03-24 | 2011-07-20 | 浙江巍华化工有限公司 | Process for synthesizing 2,6- dichlor-4-trifluoromethyl aniline |
| CN103408437A (en) * | 2013-08-30 | 2013-11-27 | 江苏丰华化学工业有限公司 | Method for preparing 2,6-dichloro-4-trifluoromethyl phenylamine |
| CN106117145A (en) * | 2016-07-12 | 2016-11-16 | 潍坊鑫诺化工有限公司 | The preparation method of 5 amino 1 (2,6 dichloro-4,4 trifluoromethyl) 3 cyano pyrazoles |
| CN111039792A (en) * | 2019-12-11 | 2020-04-21 | 苏州开元民生科技股份有限公司 | Preparation method of aniline compound |
-
2002
- 2002-07-16 CN CN 02132607 patent/CN1209341C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289401B (en) * | 2008-03-24 | 2011-07-20 | 浙江巍华化工有限公司 | Process for preparing 2,6- dichlor-4-trifluoromethyl aniline |
| CN101289400B (en) * | 2008-03-24 | 2011-07-20 | 浙江巍华化工有限公司 | Process for synthesizing 2,6- dichlor-4-trifluoromethyl aniline |
| WO2011058577A1 (en) * | 2009-11-12 | 2011-05-19 | Keki Hormusji Gharda | Process for synthesizing polyhalogenated perhaloalkylaniline compounds |
| CN103408437A (en) * | 2013-08-30 | 2013-11-27 | 江苏丰华化学工业有限公司 | Method for preparing 2,6-dichloro-4-trifluoromethyl phenylamine |
| CN106117145A (en) * | 2016-07-12 | 2016-11-16 | 潍坊鑫诺化工有限公司 | The preparation method of 5 amino 1 (2,6 dichloro-4,4 trifluoromethyl) 3 cyano pyrazoles |
| CN111039792A (en) * | 2019-12-11 | 2020-04-21 | 苏州开元民生科技股份有限公司 | Preparation method of aniline compound |
| CN111039792B (en) * | 2019-12-11 | 2022-10-14 | 苏州开元民生科技股份有限公司 | Preparation method of aniline compound |
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