Method for preparation of halogenated organic compounds

专利摘要:
The invention relates to halogenated organic substances, in particular the preparation of compounds of the total f-ly 1: X-CRiR2-CH2-CXiX2-Y, where is either CH3. , 2-propyl, C (0) -OR or C (CH3B-CH2-C (with R CH3 or C2Hs; X - CI or Br; Xi and X2 F, Cl, Br, Y - F. Cl, C (X - intermediates for the synthesis of insecticides. The goal is to increase the yield of the target product. Synthesis is carried out by reacting the compounds of f-II and the compounds of f-III: II) RiR2C CH2. Ill) X-CXiX2-Y, in the presence of a catalytic system containing copper - copper chloride and amine f-IV: R3-NH-R4, where either the group R4, a - or branched C1-C4-alkyl or cyclohexyl, and the ratio is 1: (1-20) :( 0.01- 0.1) :( 0.2-1.) The process is carried out at 50-120 ° C and stirring. These conditions increase the yield of the target product. CTA from 40 to 86.7%. Table 1. i
公开号:SU1703636A1
申请号:SU877774468
申请日:1987-03-24
公开日:1992-01-07
发明作者:Милан Гайек；Ян Чермак；Пржемысл Шилгавы；Мирослав НОВАК
申请人:Ческословенска Академие Вед. (Инопредприятие)；
IPC主号:

专利说明:

This invention relates to a process for the production of halogenated organic compounds of the formula used to manufacture pyrethroids.
RI nx,
htn
R2 H X2
0)
where RI is hydrogen or methyl;
R2 is methyl or 2-propyl, or the COOR group. or C (CHa) 2CH2COOR. where R-Ci-C2 alkyl
X is chlorine or bromine, Xi and X2 is chlorine or bromine;
Y is fluorine, chlorine or C (X |) h, where X | has the indicated meanings.
Some types of halogenated compounds are very significant intermediates in the production of insecticidally active substances called synthetic pyrethroids. These halogenated compounds in most cases are obtained by radical addition reactions of halogen alkanes to the corresponding unsaturated compounds. The known initiators and catalysts used in the addition reactions are little active and selective, require either elevated reaction temperatures and pressures, or are difficult to access and expensive. . For example, for the addition reaction of haloalkanes, such as carbon tetrachloride, 1,1.1-trichlorotrifluoroethane, freons, etc. to unsaturated compounds, such as Z-methyl-1-butene, alkyl acrylates, zlkyl-Z.Z-dimethyl-4-pentenoates, etc., organic peroxides, ruthenium complexes, iron and copper chlorides are used as catalysts. in combination with etav | ABOUT
GJ O CO O

nolamine or diethyl hydrochloride chloride, copper chloride in ethyl acetate and iron pentacarbonyl. The maximum product yields reached signs of 60-85%. In the case of a little reactive 1,1,1-trichlorotrifluoroethane in the reaction with ethyl acrylate, the product yield at 140 ° C is only 40%. The latest catalysts based on a combination of metal oxides with organic bases also require high (120-140 ° C) reaction temperatures.
The purpose of the invention is to increase the yield of the target product.
EXAMPLE 1 A mixture of 14.1 g of Z-methyl-1-butene, 307.6 g of carbon tetrachloride, 0.398 g of copper chloride and 4.14 g of 2-propylamine is heated to boiling point at 63-75.5 ° C for 6 h when the conversion of 3-methyl-1-butene reaches 89%. The reaction mixture is cooled, washed with dilute 7% hydrochloric acid and water, freed from excess carbon tetrachloride and unreacted 3-methyl-1-butene by stripping and subsequent distillation under reduced pressure to obtain 36.3 g 1.1.1.3 - tetrachloro-4-methylpentane with T.kip. 90-91 ° C / 1.6 kPa with a yield of 81.1%, i.e. 91.1% for reacted 3-methyl-1-butene. Distillation residue 1.0 g.
PRI mme R 2. A mixture of 3.5 g of 3-methyl methyl 1-butene, 38.5 g of carbon tetrachloride, 0.1 g of copper chloride and 1.7 g of cyclohexylamine is heated in a sealed ampoule with vibration stirring in a nitrogen atmosphere at 80 ° C for 5 hours. The method described in Example 1. 9.6 g of 1,1,1,3-tetrachloro-4-methyl-pentane are obtained with a yield of 85.7%, which corresponds to a yield of 92.3% by reacted 3-methyl-1-butene. Distillation residue 0.10 g.
Examples 3-19. Carried out as in Example 2, the possibility of varying the reaction conditions and different types of catalysts systems by reacting 3-methyl-1-butane (A) with carbon tetrachloride (B) is determined. The indicated yields of 1,1,1,3-tetrachloro-4-methylpentane are determined chromatographically in terms of the initial 3-methyl-1-butene.
EXAMPLE 20 A mixture of 40.0 g of ethyl acrylate, 184.6 g of carbon tetrachloride, 1.1 g of chloride and 5.9 g of 2-propylamine is heated to a boil at 78-88 ° C for 5 hours. described in example 1, receive 90.1 g of ethyl-2,4,4,4-tetrachlorobutyrate with T.Kig, 109-110 ° C / 2 kPa with a yield of 88.7%. Distillation residue 2.56 g.
EXAMPLE 21 A mixture of 0.3229 g of ethyl acrylate, 9.92 g of carbon tetrachloride, 0.0095 g of copper chloride, and 0.0685 g of 2-propylamine is heated in a sealed ampoule with vibration stirring under nitrogen at 80 ° C. for 6.5 hours. The chromatographically determined yield of ethyl 2,4,4,4-tetrachlorobutyrate is
97%.
Example 22. A mixture of 0.4578 g of ethyl acrylate, 8.65 g of carbon tetrachloride, 0.055 g of copper chloride and 0.189 g of 2-propylamine is heated in a sealed ampoule with vibration stirring under nitrogen at 80 ° C for 3 hours. The chromatographic yield of ethyl -2,4,4,4-tetrachlorobutyrate was 94.3%.
EXAMPLE 23 A mixture of 34.4 g of methyl acrylate, 123.0 g of carbon tetrachloride, 0.4 g of copper chloride and 4.73 g of 2-propylamine is heated to boiling for 7 hours. The method described in Example 1, 87.3 g of methyl 2.4,4,4-tetrachlorobutyrate are obtained from a b.pip of 101-102 ° C./2.1.
kPa with a yield of 91%. The distillation residue is 3.2 g.
PRI me R 24. A mixture of 1.756 g of 2-methylpropene, 19.26 g of carbon tetrachloride, 0.063 g of copper chloride and 0.83 g of 2-propylamine is heated in a sealed ampoule with vibration stirring under nitrogen at 80 ° C within 8 hours. By the method described in example 1, 5.92 g of 1,1.1,3-tetrachloro-3-methylbutanasT.kip 70-71 ° C / 1.6 kPas are obtained.
yield 90.1%. Distillation residue
is 0.042 g.
PRI mme R 25. A mixture of 1.42 g of Z-methyl-1-bu:
tena, 9.45 g of 1,1.1-trichlorotrifluoroethane, 0.06
g of copper chloride, 0.30 g of 2-propylamine and 6 ml
dichloromethane is heated in a sealed ampoule with vibration stirring in a nitrogen atmosphere at 80 ° C for 6 hours. The method described in Example 1 gives 3.92 g of 1,1,1-trifluoro-2,2,4-trichloro-5 -methylhexane with Ti.kip 65 ° C / 1, b kPa with a yield of 75%. The distillation residue is 0.32 g.
PRI me R 26. A mixture of 2.02 g of ethyl acrylate, 9.5 g of 1,1,1-trichlorotrifluoroethane, 0.06 g of copper chloride, 0.66 g of cyclohexylamine and 6 ml of dichloromethane are heated in a sealed ampoule while vibrating in nitrogen atmosphere at 90 ° C for 5 hours. By the method described in Example 1, 4.15 g of ethyl 2, 4,4-trichloro-5,5,5-trifluoropentanoate are obtained with the so-called p 58-60 ° C / 133 Pa with a yield of 71.5%.
PRI me R 27. A mixture of 15.6 g of ethyl-Z.-3-dimethyl-pentanoate, 37.5 g of 1,1,1-trichlorotrifluoromethane, 0.1 g of copper chloride and 0.24 g
2-Propylamine is heated in a sealed ampoule with vibration mixing in a nitrogen atmosphere at 80 ° C for 4 hours. The method described in Example 1 gives 31.3 g of Ethyl-3,3-dimethyl-4,6,6-trichloro- 7,7,7-trifluorohep
tanoate with Tipp 86 87 ° C / 20 Pa with a yield of 91%.
For example, a mixture of 1.29 g of 3-methyl-1-butene, 18.66 g of 1,2-difluorotetrachlorochloroethane, 0.073 g of copper chloride and 0.163 g of 2-propylamine is heated in a sealed ampoule at vibrating at 80 ° C for 7 hours. The method described in example 1 gives 1.54 g of 1,2-difluoro-1,1-2,4-tetrachloro-5-methylhexane with Ti.p. 84-86 ° C / 1.6 kPa with a yield of 30.7%, corresponding to a yield of 867% of the reacted 3-methyl-1-butene. The distillation residue is g.
PRI me R 29. A mixture of 1.22 g of 3-methyl-1-butene, 23.95 g of 1.1.2-trifluoro-2-chloro-1,2-dibromethane, 0.068 g of copper chloride and 0.82 g of 2-propylamine is heated in a sealed ampoule with vibration mixing in a nitrogen atmosphere at 80 ° C for 6.5 hours. The method described in Example 1 gives 2.13 g of 1,1,2-trifluoro-2- chloro-1,4-dibromo-5-methylg exan with bp. 88-92 ° C / 1.6 kPa with a yield of 35.4%, corresponding to a yield of 85.6% for the reacted Z-methyl-1-butene. The distillation residue is 0.094 g.
13c NMR (CDCl3, TMS) analysis of a mixture of diastereoisomers:
 - 16.26, 17.69. 20.58, 21.85; 43.08 (CF) 19.2 Hz. 42.7 (CF 19.5 CH 6 - 32.96, 35.36; Snoot 53.92, 56.20; CF b 110.6, 110.8 (CF) 244 Hz CF2 d 120.1, 120.3 (CF) - 353 Hz
For example. A mixture of 1.29 g3-methyl-1-butene, 12.2 gtetrabromomethane, 0.037 g of copper chloride and 0.81 g of 2-propylamine is heated in a sealed ampoule with vibration mixing in a nitrogen atmosphere at 80 ° C for 7 hours. 4.45 g of 1,1,1,3-tetrabromo-4-methylpentane with T. Kip 99 ° C / 160 Pa with a yield of 60.2%, corresponding to a yield of 85.2% unreacted, are obtained by the method described in Example 1 -methyl-1-butene. The distillation residue is 0.32 g. Analysis of 13C NMR (CDCl3. TMS): CH3 (5 17.46, 21.22; CHD 34.99; SNVns3 - 60.10; 64.90; CBhz 5 36.93.
The results are tabulated.
This method allows to significantly increase the yield of the target product in comparison with the known method.

权利要求:
Claims (1)
[1]
The invention The method of obtaining halogenated organic compounds of general formula
tv
X-C-C-C-Y (,,
III
R2 H X2
where RI is hydrogen or methyl; R2 is methyl or 2-propyl, or the COOR group. or C (CH3) 2CH2COOR, where R is Ci-C2-alkyl;
X is chlorine or bromine; Xi and X2 - fluorine, chlorine or bromine; Y is fluorine, chlorine or C (X |) h, where X | has the indicated values
by reacting unsaturated compounds of the general formula
Sc CH2 (IO
K2
where RI and R2 are as defined, with a halogenated compound of the general formula v
Y-r- Y Ayr (|)
X2
where X-X2 and Y have the indicated values in the presence of a catalytic system containing copper compounds and an amine, characterized in that, in order to increase the yield of the target product, copper chloride is taken as the copper compound, and amine is used as the amine formulas
R3-NH-R4IV
where Cs is hydrogen or R-j group; PA - normal or branched C1 C4-alkyl, cyclohexyl,
and the process is carried out at a molar ratio of unsaturated compound of formula (II), halogenated compound of formula (III), copper chloride and amine, equal to 1: (120): (0.01-0.1) :( 0.2-1.0) respectively, with stirring at 50-120 ° C.

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同族专利:

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公开号 | 公开日

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GB8707110D0|1987-04-29|

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CS257965B1|1988-07-15|

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FR2597093B1|1990-02-23|

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DD271818A3|1989-09-20|

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BG48383A1|1991-02-15|

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JPS62242635A|1987-10-23|

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DE3712304A1|1987-10-15|

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CH671220A5|1989-08-15|

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GB2188929A|1987-10-14|

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GB2188929B|1990-06-13|

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NL8700852A|1987-11-02|

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CS260886A1|1987-11-12|

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FR2597093A1|1987-10-16|

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US6040487A|1996-07-31|2000-03-21|E. I. Du Pont De Nemours And Company|Process for the manufacture of halocarbons|

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FR2744442B1|1996-02-01|1998-02-27|Atochem Elf Sa|PREPARATION OF 1,1,1,3,3-PENTACHLOROBUTANE AND 1,1,1,3,3, -PENTAFLUOROBUTANE|

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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CS862608A|CS257965B1|1986-04-10|1986-04-10|Method of halogenated organic compounds production|

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