GB2204313A - Bisbenzotrifluoride derivatives and method of preparing same - Google Patents
Bisbenzotrifluoride derivatives and method of preparing same Download PDFInfo
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- GB2204313A GB2204313A GB08809137A GB8809137A GB2204313A GB 2204313 A GB2204313 A GB 2204313A GB 08809137 A GB08809137 A GB 08809137A GB 8809137 A GB8809137 A GB 8809137A GB 2204313 A GB2204313 A GB 2204313A
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- 238000000034 method Methods 0.000 title claims description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 17
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical group CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005859 coupling reaction Methods 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- NTFZDVDWIVFEEI-UHFFFAOYSA-N 1-(trichloromethyl)-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(C(Cl)(Cl)Cl)C=C1 NTFZDVDWIVFEEI-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- VDEUYVGUNSJXAE-UHFFFAOYSA-N 1-(trichloromethyl)-2-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC=CC=C1C(Cl)(Cl)Cl VDEUYVGUNSJXAE-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- DVFVNJHIVAPTMS-UHFFFAOYSA-N 1-methyl-2-(trifluoromethyl)benzene Chemical compound CC1=CC=CC=C1C(F)(F)F DVFVNJHIVAPTMS-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000013256 coordination polymer Substances 0.000 claims 1
- -1 trihalomethyl benzotrifluoride Chemical compound 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- OVUAUGZRYXICFV-UHFFFAOYSA-N 1-(trifluoromethyl)-2-[2-[2-(trifluoromethyl)phenyl]ethynyl]benzene Chemical group FC(F)(F)C1=CC=CC=C1C#CC1=CC=CC=C1C(F)(F)F OVUAUGZRYXICFV-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical class FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 3
- QEQNRERDWZEPBB-UHFFFAOYSA-N 1-[1,2,2,2-tetrachloro-1-[2-(trifluoromethyl)phenyl]ethyl]-2-(trifluoromethyl)benzene Chemical compound FC(C1=C(C=CC=C1)C(C(Cl)(Cl)Cl)(Cl)C1=C(C=CC=C1)C(F)(F)F)(F)F QEQNRERDWZEPBB-UHFFFAOYSA-N 0.000 description 3
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- SKWWCKGHUDPXOZ-UHFFFAOYSA-N 1-(trichloromethyl)-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(Cl)(Cl)Cl)=C1 SKWWCKGHUDPXOZ-UHFFFAOYSA-N 0.000 description 2
- QCNIMLJOVLXUSO-UHFFFAOYSA-N 1-(trifluoromethyl)-2-[1-[2-(trifluoromethyl)phenyl]ethyl]benzene Chemical compound FC(F)(F)C1=C(C=CC=C1)C(C)C1=C(C=CC=C1)C(F)(F)F QCNIMLJOVLXUSO-UHFFFAOYSA-N 0.000 description 2
- LZRAUNCUFOGKDN-UHFFFAOYSA-N 1-(trifluoromethyl)-2-[2-[2-(trifluoromethyl)phenyl]ethenyl]benzene Chemical group FC(F)(F)C1=CC=CC=C1C=CC1=CC=CC=C1C(F)(F)F LZRAUNCUFOGKDN-UHFFFAOYSA-N 0.000 description 2
- JVPNVOZUSGFXEC-UHFFFAOYSA-N 1-[1,1,2,2-tetrachloro-2-[3-(trifluoromethyl)phenyl]ethyl]-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(Cl)(Cl)C(Cl)(Cl)C=2C=C(C=CC=2)C(F)(F)F)=C1 JVPNVOZUSGFXEC-UHFFFAOYSA-N 0.000 description 2
- IQHBDRUNRCUWNS-UHFFFAOYSA-N 1-[1,2-dichloro-2-[2-(trifluoromethyl)phenyl]ethenyl]-2-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=C(C=CC=C1)C(=C(Cl)C1=C(C=CC=C1)C(F)(F)F)Cl IQHBDRUNRCUWNS-UHFFFAOYSA-N 0.000 description 2
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical class [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 description 2
- ZDVRPKUWYQVVDX-UHFFFAOYSA-N 2-(trifluoromethyl)benzaldehyde Chemical compound FC(F)(F)C1=CC=CC=C1C=O ZDVRPKUWYQVVDX-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 230000000382 dechlorinating effect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 description 1
- XGIRWNFILAXTJE-UHFFFAOYSA-N 1,2-dichloro-3-(fluoromethyl)-4-(trifluoromethyl)benzene Chemical compound ClC1=C(C(=C(C=C1)C(F)(F)F)CF)Cl XGIRWNFILAXTJE-UHFFFAOYSA-N 0.000 description 1
- BBXDMCQDLOCXRA-UHFFFAOYSA-N 1-(chloromethyl)-2-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1CCl BBXDMCQDLOCXRA-UHFFFAOYSA-N 0.000 description 1
- ZMOUIPJONKNSLM-UHFFFAOYSA-N 1-[1,1,2,2-tetrachloro-2-[4-(trifluoromethyl)phenyl]ethyl]-4-(trifluoromethyl)benzene Chemical compound C1=CC(C(F)(F)F)=CC=C1C(Cl)(Cl)C(Cl)(Cl)C1=CC=C(C(F)(F)F)C=C1 ZMOUIPJONKNSLM-UHFFFAOYSA-N 0.000 description 1
- AJRORQBMERVXTE-UHFFFAOYSA-N 1-[1,2-dichloro-2-[4-(trifluoromethyl)phenyl]ethenyl]-4-(trifluoromethyl)benzene Chemical group C1=CC(C(F)(F)F)=CC=C1C(Cl)=C(Cl)C1=CC=C(C(F)(F)F)C=C1 AJRORQBMERVXTE-UHFFFAOYSA-N 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical group C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C22/00—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom
- C07C22/02—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings
- C07C22/04—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings
- C07C22/08—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/269—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of only halogenated hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
2201313 -l NOVEL BISBENZOTRIFLUORIDE DERIVATIVES AND METHOD OF PREPARING
SAME This invention relates to a group of novel bis benzotrifluoride derivatives which will be useful as materials of medicines, agricultural chemicals and novel polymers and methods of preparing same.
So far as we know, no literature shows preparation of bisbenzotrifluoride derivatives.
We gave consideration to a possibility of synthe sizing bis(trifluoromethylphenyl)acetylene by the steps of making condensation of trifluoromethylbenzaldehyde into a benzoin form, converting it into a stilbene derivative, adding bromine thereto and then making an elimination reaction. However, this process includes many reactions each of which is not very simple in industrial practice, and trifluoromethylbenzaldehyde is a costly material.
The present invention provides novel bisbenzo trifluoride derivatives represented by the general formula (l):
CF A: R Ct3 wherein R represents -CC1 2 CC1 2_ ' -Ccl=ccl- or -C=-C-.
That is, the novel compounds of the invention are bis(trifluoromethylphenyl)tetrachloroethane, bis(tri fluoromethylphenyl)dichloroethylene and bis(trifluoro methylphenyl)acetylene. These compounds will be useful as intermediate materials for synthesizing medicines and agricultural chemicals and also for producing novel polymers.
We have made the present invention by finding firstly that either bis(trifluoromethylphenyl)tetra- chloroethane or bis(trifluoromethylphenyl)dichloro- ethylene, i.e. a bisbenzotrifluoride derivative repre sented by the general formula (1A), can be prepared by subjecting a trihalomethylbenzotrifluoride represented by the general formula (2) to a dehalogenating coupling reaction in a hydrogen gas atmosphere, CF 3--[: R'-& CF3 (1A) wherein R' represents -CC1 2 CC1 2_ or -CC1=CC1-, CF 3 (2) 1 0 -cci 2X wherein X is Cl or F, and further that bis(trifluoromethylphenyl)acetylene, i.e. a bisbenzotrifluoride derivative represented by the general formula (1B) can be prepared by heating a compound represented by the general formula (1A) at a temperature not lower than 50 0 C in the presence of a metal which acts as a dehalogenating agent:
W 3 ---Q C = C-C CF3 (1B) The dehalogenating coupling reaction to form a compound of the formula (1A) is carried out, by using palladium as a catalyst, at an elevated temperature preferably under some pressure and, also preferably, in the presence of a base. The type of the coupling radical R' of the reaction product depends on the temperature and pressure conditions.
The reaction to convert a compound of the formula (1A) into an acetylenic compound of the formula (1B) is carried out in an organic solvent preferably by using zinc as the dehalogenating metal.
As the starting trihalomethylbenzotrifluoride in preparing a compound of the formula (1A) either tri chloromethylbenzotrifluoride or dichlorofluoromethyl benzotrifluoride is useful, though the former is preferable. The position of the -CC1 3 or -CC1 2 F group with respect to the -W 3 group may be any of o-, m- and p-positions.
For the coupling reaction of the selected trihalc- methylbenzotrifluoride it is suitable to use a palladium catalyst such as a palladium-on-carbon catalyst. The quantity of the palladium catalyst is variable over a wide range such as from 0.01 to 50 wt% (as palladium) of the trihalomethylbenzotrifluoride. Usually a suitable quantity of palladium is from 1 to 10 wt% of the starting compound. The reaction is carried out in an autoclave filled with hydrogen gas by maintaining a temperature not lower than 50 0 C for several hours. The hydrogen gas pressure should not be subatmospheric, and it is preferable to carry out the reaction under moderately elevated pressure. The hydrogen gas pressure and the reaction temperature are selectively varied depending on whether the aimed compound of the formula (1A) is bis(trifluoromethylphenyl)ethane or bis(trifluoromethylphenyl)ethylene. Besides, the position of the -CC1 3 or -CC1 2 F group with respect to the -CF 3 group has to be taken into consideration. That is, in the case of m-position it is necessary to employ severer conditions of reaction than in the case of p-position, and still severer conditions are needed in the case of o-position. It is favorable for the intended coupling reaction to add a base such as potassium hydroxide or sodium hy droxide to the reaction system. In general it is preferable to use potassium hydroxide in a quantity 2 to 4 times the equivalent to the trihalomethylbenzo trifluoride.
In the case of synthesizing 1,2-bis(4'-trifluoromethylphenyl)-1,1,2,2-tetrachloroethane, it is suitable to carry out the coupling reaction under hydrogen gas pressure of 2-4 kg/cm 2 at 50-100 0 C. In the case of synthesizing 1,2-bis(41-trifluoromethylphenyl)-1,2dichloroethylene, it is suitable to carry out the reaction under pressure of 3-4 kg/cm 2 at 100-120 0 C.
When preparing 1,2-bis(31-trifluoromethylphenyl)1,1,2,2-tetrachloroethane, bis(31-trifluoromethyl phenyl)dichloroethylene, bis(2'-trifluoromethylphenyl) tetrachloroethane or bis(21-trifluoromethylphenyl) dichloroethylene, it is favorable for promotion of the coupling reaction to further raise the hydrogen gas pressure by about 1-2 kg/cm 2 and the reaction temperature by about 10-30 0 C.
An acetylenic compound of the formula (1B), viz.
bis(trifluoromethylphenyl)acetylene, can easily be obtained by dechlorinating a compound of the formula (1A), either bis(trifluoromethylphenyl)ethane or bis (trifluoromethylphenyl)ethylene, by using a metal such as zinc or magnesium which acts as a dehalogenating agent. It is preferred to use zinc. The quantity of.
the metal must be at least stoichiometrical, and the presence of an excess of the metal raises little problem. The dechlorinating reaction is carried out in a suitable organic solvent, preferably in acetic anhydride, by continuing heating at a temperature not lower than 50 0 C.
The invention is further illustrated by the following nonlimitative examples. Examples 1 to 5 relate to synthesis of compounds of the general formula (1A) and Examples 6 to 8 acetylenic compounds of the formula (1B).
EXAMPLE 1
A 100-ml stainless steel autoclave was charged with g of p-trichloromethylbenzotrifluoride, 300 mg of palladium-on-carbon catalyst (Pd 5 wt%), 8 g of potassium hydroxide and 10 ml of water. The atmosphere in the autoclave was replaced by hydrogen gas, and the 2 gas pressure was regulated to 3 kg/cm Then the mixture in the autoclave was kept heated at 110 0 C for 4 hr. The reaction product was dissolved in dichloro methane and washed with water. After recovering the palladium catalyst, the solution was concentrated to thereby obtain 17.3 g of 1,2-bis(41-trifluoromethyl phenyl)-1,1,2,2-tetrachloroethane.
EXAMPLE 2
The reaction in Example 1 was modified only in that g of m-trichloromethylbenzotrifluoride was used as the starting compound. The reaction product was treated in the same manner as in Example 1. As the result, 12.1 g of 1,2-bis(3'-trifluoromethylphenyl)-1,1,2,2tetrachloroethane was obtained.
EXAMPLE 3
Among the materials used in Example 1, the benzo- trifluoride was replaced by 20 g of o-trichloromethyl benzotrifluoride. In this case the hydrogen gas 2 pressure in the autoclave was regulated to 4 kg/cm ' and the reaction was carried out at 1200C for 6 hr. The reaction product was treated in the same manner as in Example 1. As the result, 8.8 g of 1,2-bis(21 trifluoromethylphenyl)-1,2-dichloroethylene (mixture of cis-form and trans-form) was obtained.
EXAMPLE 4
A 30-m1 stainless autoclave was charged with 4 g of m-trichloromethylbenzotrifluoride, 100 mg of palladium on-carbon catalyst (Pd 5 wt%), 1 g of potassium hydroxide and 2 ml of water. The atmosphere in the autoclave was replaced by hydrogen gas, and the gas 2 pressure in the autoclave was regulated to 5 kg/cm.
Then the mixture in the autoclave was kept heated at 0 C for 4 hr. The reaction product was dissolved in dichloromethane and washed with water. After recovering the catalyst the solution was concentrated to thereby obtain 2.24 g of 1,2-bis(31-trifluoromethylphenyl)-1,2- dichloroethylene. Stereoisomerism of this compound was examined by gas chromatography. The ratio of cis-form to trans-form was 7:3.
EXAMPLE 5
Among the materials used in Example 4, the benzo- trifluoride was replaced by 4 g of p-trichloromethyl benzotrifluoride. In this case the hydrogen gas pressure was regulated to 3 kg/cm 2, and the reaction was carried out at 120 0 C for 4 hr. The reaction product was treated in the same manner as in Example 4. As the result, 2.8 g of 1,2-bis(4'-trifluoromethylphenyl)-1,2- dichloroethylene was obtained. In this compound, the ratio of cis-form to trans-form was found to be 2:1 by gas chromatography.
EXAMPLE 6
In a glass reactor 41.2 g of 1,2-bis(41-trifluoromethylphenyl)-1,1,2,2-tetrachloroethane was dissolved in 316 ml of acetic anhydride, and the solution was kept heated at reflux temperature for 24 hr while inter mittently (ten times) adding zinc dust to the solution.
In total, 60 g of zinc dust was introduced into the reaction system. After that ether was added to the reaction liquid, and insoluble matter was filtered out.
The filtrate was concentrated to recover organic matter, a 1 -g- which was refined by silica gel column chromatography using hexane as developing solvent. As the result, 23.0 g of 1,2-bis(41-trifluoromethylphenyl)acetylene was obtained.
EXAMPLE 7
A solution of 3.7 g of 1,2-bis(3'-trifluoromethylphenyl)-1,1,2,2-tetrachloroethane in 50 ml of acetic anhydride was kept heated at reflux temperature for 41 hr while intermittently (ten times) adding zinc dust (12 g in total) to the solution. The reaction product was dissolved in ether and refined by silica gel column chromatography in the same manner as in Example 6. As the result, 1.9 g of 1,2-bis(31-trifluoromethylphenyl)- acetylene was obtained.
EXAMPLE 8
A solution of 1.2 g of 1,2-bis(21-trifluoromethylphenyl)-1,2-dichloroethylene in 20 ml of acetic anhydride was kept heated at reflux temperature for hr while intermittently (ten times) adding zinc dust (3.5 g in total) to the solution. The reaction product was dissolved in hexane and refined by silica gel column chromatography in the same manner as in Example 6. As the result, 0.8 g of 1,2-bis(21-trifluoromethylphenyl)- acetylene was obtained.
Tables 1 and 2 show results of analysis of the compounds obtained in the above examples.
TABLE 1
Compound 19F-NMR Mass M.P.
(in CDC1 31 Spectro- standard metry was WC1 3) 0 ( C) (Ppm) (m/e) cr 3 cl cl W 3 Ex. 1 63.43 421 (-Cl) 108-109 cl cl " Ex. 2 63.43 c 168 3 227( (b:CC12 cl cl Ex. 3 cl 60.92 384 (M+) 162-163 W 3 cl er 3 Ex. 3 58.85 384 (M+) oil CF3 cl cl er 3 W 3 CF3 Ex. 4 cl 63.23 + 54-55 t CL 384 (M 0 cl Ex. 4 3 63.68 384 (M+) 48-49 cl cl Ex. 5 W 1 CF3 63.38 384 (M+) 138-139 cl er 3'[==A)'CF3 ' Ex. 5 63.48 384 (M+) 38-39 cl c - 1 11 - TABLE 2
Compound 19 F-NMR Mass M.P.
(in CDC1 31 Spectro- standard metry was WC1 3) 0 ( C) (Ppm) (m/e) Ex. 6 W -(- 314 (M+) 107-108 _1 0 -=-CO--cF 3 63.43 CF3 CF3 63.48 314 (M+) 88 Ex. 7 =_4 6- Ex. 8 62.79 314 (M+) 68-69 -12
Claims (15)
- A compound represented by the general. formula (l):CF 3 -00 - R c 3 (1) wherein R represents -CC1 2 CC1 2- ' -Ccl=ccl- or -C=-C-.
- 2. A method of preparing a compound represented by the general formula (1A), ICF 3 -00 -RI -@- CF 3 (1A) wherein R' represents -CC1 2 CC1 2- or -==CC1-, the method comprising subjecting a trihalomethyl benzotrifluoride represented by the general formulA(2) to dehalogenating coupling reaction in a hydrogen gas atmosphere:CF 3 (2) 0 7CC12x wherein X is Cl or F.
- 3. A method according to Claim 2, wherein said reaction is carried out in the presence of a palladium catalyst.
- 4. A method according to Claim 3, wherein said palladium catalyst comprises carbon as a carrier.1
- 5. A method according to Claim 2, 3 or 4, wherein said reaction is carried out at a temperature not lower than 50 0 C.
- 6. A method according to any of Claims 2 to 5, wherein said hydrogen gas atmosphere has a pressure above the atmospheric pressure.
- 7. A method according to any of Claims 2 to 6, wherein said reaction is carried out in the presence of a base.
- 8. A method according to Claim 7, wherein said base is selected from potassium hydroxide and sodium hydroxide.
- 9. A method according to any of Claims 2 to 8, wherein said trihalomethylbenzotrifluoride is selected from o-trichloromethylbenzotrifluoride, m-trichloro methylbenzotrifluoride and p-trichloromethyl benzotrifluoride.
- 10. A method of preparing a compound represented by the general formula (1A) defined in Claim 2, substantially as hereinbefore described in any of Examples 1 to 5.
- 11. A method of preparing a compound represented by the general formula (1B), CP -CF 3 -( -CC 3 (,B) e; 25 11 the method comprising heating a compound represented by the general formula (1A) at a temperature not lower than 0 C in the presence of a metal which acts as a dehalogenating agent:CF R I --@- CF3 (1A) 3 -00-, wherein RI represents -CC1 2CC12- or -CC'=CC'-'
- 12. A method according to Claim 11, wherein said metal is selected from zinc and magnesium.
- 13. A method according to Claim 11 or 12, wherein the compound represented by the general formula (1A) is heated in an organic solvent.
- 14. A method according to Claim 13, wherein said solvent is acetic anhydride.
- 15. A method of preparing a compound represented by the general formula (1B) defined in Claim 11, substantially as hereinbefore described in any of Examples 6 to S.Published 1988 at The Patent OMce, State House, 6671 High Holborn, London WC1R 4TP. Further copies may be obtained from The Patent Office, Sales Branch, St Mary Cray. Orpington, Kent BR5 3RD. Printed by Multiplex techniques ltd, St Mary Cray, Kent. Con. 1/87.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62100024A JPH0672112B2 (en) | 1987-04-24 | 1987-04-24 | Novel bisbenzotrifluoride derivative and process for producing the same |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8809137D0 GB8809137D0 (en) | 1988-05-18 |
| GB2204313A true GB2204313A (en) | 1988-11-09 |
| GB2204313B GB2204313B (en) | 1990-10-31 |
Family
ID=14262971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8809137A Expired - Fee Related GB2204313B (en) | 1987-04-24 | 1988-04-18 | Novel bisbenzotrifluoride derivatives and method of preparing same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPH0672112B2 (en) |
| DE (1) | DE3813453A1 (en) |
| FR (1) | FR2614296B1 (en) |
| GB (1) | GB2204313B (en) |
| IT (1) | IT1218225B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4918251A (en) * | 1989-04-04 | 1990-04-17 | Mallinckrodt, Inc. | Preparation of 2-halofluorobenzene |
| EP0499984A1 (en) * | 1991-02-16 | 1992-08-26 | Daikin Industries, Limited | Preparation of dimer of fluorine-containing halo-ethane |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2644835A (en) * | 1947-06-05 | 1953-07-07 | Us Rubber Co | Coupled products |
| GB1265051A (en) * | 1968-03-13 | 1972-03-01 | ||
| IT1125157B (en) * | 1976-11-19 | 1986-05-14 | Sarda Off Mec | PROCEDURE FOR THE PREPARATION OF COMPOUNDS, '- ETHYLAROMATIC DIALOGEN |
| US4634797A (en) * | 1985-02-07 | 1987-01-06 | Halocarbon Products Corporation | Coupling of chloroperfluoroalkanes |
-
1987
- 1987-04-24 JP JP62100024A patent/JPH0672112B2/en not_active Expired - Lifetime
-
1988
- 1988-04-18 GB GB8809137A patent/GB2204313B/en not_active Expired - Fee Related
- 1988-04-21 IT IT20278/88A patent/IT1218225B/en active
- 1988-04-21 DE DE3813453A patent/DE3813453A1/en active Granted
- 1988-04-22 FR FR8805400A patent/FR2614296B1/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4918251A (en) * | 1989-04-04 | 1990-04-17 | Mallinckrodt, Inc. | Preparation of 2-halofluorobenzene |
| EP0499984A1 (en) * | 1991-02-16 | 1992-08-26 | Daikin Industries, Limited | Preparation of dimer of fluorine-containing halo-ethane |
| US5382720A (en) * | 1991-02-16 | 1995-01-17 | Daikin Industries, Ltd. | Preparation of dimer of fluorine-containing ethane |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2614296B1 (en) | 1990-06-15 |
| JPS63267737A (en) | 1988-11-04 |
| GB2204313B (en) | 1990-10-31 |
| FR2614296A1 (en) | 1988-10-28 |
| JPH0672112B2 (en) | 1994-09-14 |
| IT1218225B (en) | 1990-04-12 |
| DE3813453A1 (en) | 1988-11-03 |
| DE3813453C2 (en) | 1993-06-09 |
| GB8809137D0 (en) | 1988-05-18 |
| IT8820278A0 (en) | 1988-04-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19980418 |