CA2026566A1 - Process for producing a chlorine-containing 2-2-difluoropropane - Google Patents
Process for producing a chlorine-containing 2-2-difluoropropaneInfo
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- CA2026566A1 CA2026566A1 CA 2026566 CA2026566A CA2026566A1 CA 2026566 A1 CA2026566 A1 CA 2026566A1 CA 2026566 CA2026566 CA 2026566 CA 2026566 A CA2026566 A CA 2026566A CA 2026566 A1 CA2026566 A1 CA 2026566A1
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- 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
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT
A process for producing a chlorine-containing 2,2-difluoropropane of the following formula (2), which comprises chlorinating a 2,2-difluoropropane of the following formula (1):
C3HaClbFc (1) C3Ha-xClb+xFc (2) wherein a, b, c and x are integers satisfying the following conditions:
a ? 1, b ? O, c ? 2, x ? 1 and a + b + c = 8.
A process for producing a chlorine-containing 2,2-difluoropropane of the following formula (2), which comprises chlorinating a 2,2-difluoropropane of the following formula (1):
C3HaClbFc (1) C3Ha-xClb+xFc (2) wherein a, b, c and x are integers satisfying the following conditions:
a ? 1, b ? O, c ? 2, x ? 1 and a + b + c = 8.
Description
2~2~6~ :
Our Ref.: AA-562 (F~9-49) DESCRIPTION
TITLE OF THE INVENTION
PROCESS FOR PRODUCING A CHLORINE-CONTAINING
2, 2-DIFLUOROPROPANE
TECHNICAL FIELD
The present invention relates to a process for producing a chlorine-containing 2,2-difluoropropane.
BACKGROVND TECHNIQ~E
As a synthetic route for a chlorine-containing 2,2-difluoropropane, a method has been known in which dichloroEluoromethane or chloromethane i5 added to an .
ethylene having a difluoromethylene unit, such as 1,1-dichloro~2,2-di~luoroethylene or l-chloro-1,2,2-trifluoroethylene in the presence of aluminum chloride.
However, by such a method, not only the desired product, but also a by-product will be formed which has a : ~;
methylene group other than 2,2-difluoromethylene and which has a boiling point close to that of the desired product. There~ore, in order to obtain a product having a high purity, a multi-stage purification process is required.
DISCLOSURE OF THE INVENTION
It is an object of the present invention to overcome :25 such a dra~back of the conventional method and to provide : .
a process for efficiently producing~ a chlorine-containing ~.
2,2-difluoropropane.
, .
.
- 2~2~6i~
The present inventors have conducted an extenslve research for a process for efficiently producing a chlorine-containing 2,2-difluoropropane and, as a result, have found that a chlorine-containing 2,2-difluoropropane of the following formula (2) can be obtained in good yield by substltuting the hydrogen atoms of a 2,2~
difluoropropane of the formula (1) by chlorine atoms by chlorination. The present invention is based on this discovery.
The present invention provldes a process for ;:.
producing a chlorine-containing 2,2-difluoropropane of the following formula (2)/ which comprises chlorinating a 2,2-difluoropropane oE the Eollowing ~ormula tl):
C3HaclbFc C3Ha_xclb+xF~ ~2) : -wherein a, b, c and x are integer~ satisfying the `
following conditions:
a 2 1, b 2 o, c 2 2, x 2 1 and a ~ b ~ c = 8.
The chlorine-containing 2,2-difluoropropane of the formula (2) is expected to be useful as a foaming agent, a cooling agent, a propellant or a solvent like conventional chloro~luorocarbons. Particularly, it includes a promising sùbstitute for 1,1,2-trichlorotrifluoroethane as a solvent. -BEST MODE OF CARRYING OVT THE INVENTION ; :
Reactions of the following formulas (3) to ~6) may be ~mentioned as specific embodiments for the preparation of . . .
'. :.
' -: :. ' ' . ', , ' : ~ ';
2~2~6i~
Our Ref.: AA-562 (F~9-49) DESCRIPTION
TITLE OF THE INVENTION
PROCESS FOR PRODUCING A CHLORINE-CONTAINING
2, 2-DIFLUOROPROPANE
TECHNICAL FIELD
The present invention relates to a process for producing a chlorine-containing 2,2-difluoropropane.
BACKGROVND TECHNIQ~E
As a synthetic route for a chlorine-containing 2,2-difluoropropane, a method has been known in which dichloroEluoromethane or chloromethane i5 added to an .
ethylene having a difluoromethylene unit, such as 1,1-dichloro~2,2-di~luoroethylene or l-chloro-1,2,2-trifluoroethylene in the presence of aluminum chloride.
However, by such a method, not only the desired product, but also a by-product will be formed which has a : ~;
methylene group other than 2,2-difluoromethylene and which has a boiling point close to that of the desired product. There~ore, in order to obtain a product having a high purity, a multi-stage purification process is required.
DISCLOSURE OF THE INVENTION
It is an object of the present invention to overcome :25 such a dra~back of the conventional method and to provide : .
a process for efficiently producing~ a chlorine-containing ~.
2,2-difluoropropane.
, .
.
- 2~2~6i~
The present inventors have conducted an extenslve research for a process for efficiently producing a chlorine-containing 2,2-difluoropropane and, as a result, have found that a chlorine-containing 2,2-difluoropropane of the following formula (2) can be obtained in good yield by substltuting the hydrogen atoms of a 2,2~
difluoropropane of the formula (1) by chlorine atoms by chlorination. The present invention is based on this discovery.
The present invention provldes a process for ;:.
producing a chlorine-containing 2,2-difluoropropane of the following formula (2)/ which comprises chlorinating a 2,2-difluoropropane oE the Eollowing ~ormula tl):
C3HaclbFc C3Ha_xclb+xF~ ~2) : -wherein a, b, c and x are integer~ satisfying the `
following conditions:
a 2 1, b 2 o, c 2 2, x 2 1 and a ~ b ~ c = 8.
The chlorine-containing 2,2-difluoropropane of the formula (2) is expected to be useful as a foaming agent, a cooling agent, a propellant or a solvent like conventional chloro~luorocarbons. Particularly, it includes a promising sùbstitute for 1,1,2-trichlorotrifluoroethane as a solvent. -BEST MODE OF CARRYING OVT THE INVENTION ; :
Reactions of the following formulas (3) to ~6) may be ~mentioned as specific embodiments for the preparation of . . .
'. :.
' -: :. ' ' . ', , ' : ~ ';
2~2~6i~
a chlorine-containing 2,2-difluoropropane of the Eormula (2) from a 2,2-difluoropropane of the formula (1).
C3HmlC15_mlF3 ' C3HnlC15-nlF3 ( ) 1 _ ml c 5 o ~ nl ~ 4I ml > nl The 2,2-difluoropropane (C3HmlCl5_mlF-~ wherein 1 ~ ml ~ 5) to be used as the starting material includes, for example, 1,2,2-trifluoropropane (R-263c), 1-chloro-2,2,3- .
trifluoropropane (R-253ca), 1-chloro-1,2,2-trifluoropropane (R-253cb), 1,3-dichloro-1,2,2-trifluoropropane (R-243ca), 1,1-dichloro-2,2,3~
trifluoropropane (R-243cb), 1,1-dichloro-1,2,2- : `.
trifluoropropane ~R-243cc), 1,1,3-trichloro-1,2,2~ :
tri~luoropropane (R-233cb), 1,1,3,3-tetrachloro-1,2,2-trifluoropropane ~R-223ca) and 1,1,1,3-tetrachloro-2,2,3-trifluoropropane (R-223cb).
The chlorine-containing 2,2-difluoropropane -:
( C3HnlCls_nlF3 wherein O ~ nl 5 4) to be formed by the reaction includes l-chloro-2,2,3-trifluoropropane (R-253ca), 1-chloro-1,2,2-trifluoropropane (R-253cb), 1,3-dichloro-1,2,2-trifluoropropane (R-243ca~, l,l-dichloro- :
2,2,3-trifluoropropane (R-243cb) r 1,1-dichloro-1~2,2-trifluoropropane ~R-243cc), 1,1,3-trichloro-2,2,3-tri~luoropropane (R-233ca), 1,1,3-trichloro-1,2,2-trifluoropropane (R-233cb), 1,1,1-trichloro-2,2,3- `
triEluoropropane (R-233cc), 1,1,3,3-tetrachloro-1,2,2- ~:
trifluoropropane (R-2-3ca), 1,1,1,3-tetrachloro-2,2,3-2~2$~S~
trifluoropropane (R-223cb) and 1,1,1,3,3-pentachloro-2,2,3-trifluoropropane (R-213c).
C3Hm2Cl~_m2F4 C3Hn2Cl4_n2F4 (4) 1 _ m2 ~ 4 0 < n2 ~ 3, m2 > n2 The 2,2-difluoropropane (C3Hm2Cl4_m2Fq wherein 1 ~ m2 ~ 4) to be used as the starting materia:L includes :~
1,2,2,3-tetrafluoropropane (R-254ca), 1,1,2,2-tetrafluoropropane ~R-254cb), 1-chloro-2,2,3,3-tetrafluoropropane ~R-244ca), 1-chloro-1,2,2l3-tetrafluoropropane (R-244cb), 1-chloro-1,1,2,2-tetrafluoropropane (R-244cc), 1,3-dichloro-lr2,2,3- :i :
tetra1uoropropane (R-234ca), 1,1-dichloro-2,2,3,3-tetraEluoropropane ~R-234cb), 1,3-dichloro-1,1,2,2-tetrafluoropropane ~R-234cc), 1,1-dichloro-1,2,2,3-tetrafluoropropane (R-234cd), 1,1,3-trichloro-2,2,3,3- ~ ;
tetrafluoropropane (R-224ca), 1,1,3-trichloro-1,2,2,3-tetrafluoropropane (R-224cb) and 1,1-trichloro-2,2,3,3- ...
tetraEluoropropane (R-224cc).
The chlorine-containing 2,2-difluoropropane ~C3Hn2C14_n2F~ wherein O ~ n2 ~ 3) to be formed by the reaction includes l~chloro-2,2,3,3-tetra~luoropropane ~R-244ca) r 1-chloro-1,2,2,3-tetra~luoropropane tR-244cb), 1-chloro-1,1,2,2-tetrafluoropropane ~R-244cc), 1,3- - : :
dîchloro-1,2,2,3-tetrafluoropropane (R-234ca), 1,1- -dichloro-2,2,3,3-tetrafluoropropane (R-234cb), 1,3 dichloro-1,1,2/2-tetrafluoropropane (R-234cc), 1,1- :
'''"'`'-'' ,"'"' 2 ~ 6 ~
dichloro-1,2,2,3-tetrafluoropropane (R-234cd), 1,lr3-trichloro-2,2,3,3-tetrafluoropropane (R-224ca), 1,1,3- :
trichloro-1,2,2,3-tetrafluoropropane ~R-224cb), 1,1,1-trichloro-2,2,3,3-tetrafluoropropane (R-224cc), 1,1,3,3-tetrachloro-1,2,2,3-tetrafluoropropane (R-214ca) and 1,1,1,3-tetrachloro-2,2,3,3-tetrafluoropropane (R-214cb).
These products can be separated by a usual method such as distillation~
C3Hm3Cl3_m3Fs ' C3Hn3Cl3-n3F5 (5) 1 ~ m3 ~ 3 ~ n3 ~ 2, m3 > n3 The 2r2-difluoropropane (C3Hm3Cl3_m3F5 wherein 1 ~ m ~ 3 to be used as the starting material includes 1,1,2,2,3-pentafluoropropane (R-245ca), 1,1,1,2,2-pentaEluoropropane (R-245cb), 1-chloro-1,2,2,3,3- ;
pentafluoropropane (R-235ca), 1-chloro-2,2,3,3,3-pentafluoropropane (R-235cb), 1-chloro-1,1,2,2,3-penta~luoropropane (R-235cc), 1,1-dichloro-2,2,3,3,3-penta1uoropropane (R-225ca), 1,3-dichloro-1,1,2,2,3-pentafluoropropane (R-225cb) and 1,1-dichloro-1,2,2,3,3-pentafluoropropane (R-225cc).
The chlorine-containing 2,2-difluoropropane (C3Hn3C13_n3F5 wherein 0 ~ n3 ~ 2) to be formed by the reaction includes l-chloro-l,ll2,2,3,3-pentafluoropropane (R-235ca), 1-chloro-2,2,3,3,3-pentafluoropropane (R-235cb~, 1-chloro-1,1,2,2,3-pentafluoropropane (R-235cc), lJl-dichloro-2,2,3,3,3-pentafluoropropane (R-225ça), 1,3- `
,':
- 2 ~ 2 ~
dichloro-1,1,2,2,3-pentafluoropropane (R-225cb), 1,1-dichloro-1,2,2,3,3-pentafluoropropane (R-225cc), 1,1,3-trichloro-1,2,2,3,3-pentafluoropropane (R-215ca) and 1,1,1-trichloro-2,2,3,3,3-pentafluoropropane (R-215cb).
Cl~
C3Hm4cl2-m4F6 -~ C3Hn2C12-n4F5 (6) 1 S m4 5 2 _ n4 ~ 1, m4 > n4 The 2,2-difluoropropane (C3Hm~Cl2_m~F~ wherein 1 ~ m4 ~ 2) to be used as the starting material includes 1,1,2,2,3,3-hexafluoropropane (R-236ca), 1,1,1,2,2,3-hexafluoropropane (R-236cb), 1-chloro-1,2,2,3f3,3-hexafluoropropane (R-226ca) and 1-chloro-1,1,2,2,3,3-hexafluoropropane (R-226cb).
The chlorine-containing 2,2-diEluoropropane (C3HnCl2_nF6 wherein 0 ~ n 5 1) to be Eormed by the reaction includes l-chloro-1,2,2,3,3,3-hexa~luoropropane ~R-226ca), 1-chloro-1,1,2,2,3,3-hexfluoropropane ~R-226cb), 1,3-dichloro-1,1,2,2,3,3-hexafluoropropane (R-216ca) and 1,1-dichloro-1,2,2,3,3,3-hexafluoropropane (R-216cb). The~e products can be separated by a usual 20method such as distillation.
For the reaction, a radical-generating source such as light, heat or a radical initiator, or a combination thereof, may be used. The radical initiator to be used is not particularly limited so long as it is oil-soluble and may be an azo compound or an organic peroxide as shown in the following example. The azo compound may, ~, ' ;~ ,.
2~2~
for example, be a,a'-azobisisobutylonitrile (hereinafter referred to simply as AIBN) or 2,2-azobis-2,4-dimethylvaleronitrile (hereinafter referred to simply as ACVN). The organic peroxide may, for example, be di~t-butyl peroxide.
The reaction ratio between chlorine and the starting material may be varied in a wide range. In order to control the chlorination selectively at a stage where only single chlorine is introduced, chlorine is used in a `
low stoichiometrical amount relative to the 2,2-difluoropropane (C3HaClbFC). Whereas, to let all the hydrogen atoms o~ the 2,2-difluoropropane react substantially completely, chlorine is used in an amount larger than stoichiometry relative to total molar amount of the starting material, for exampler in an amount of 2 or more molar times.
The reaction temperature may suitably be chosen depending upon the radical-generating source and is usually from -78 to 450C.
In the present invention, when the reaction is conducted in a liquid phase, a solvent may be employed.
The solvent to be used is not particularly limited so long as it is capable of dissolving the propane as the starting material and the radical initiator if used, and will hardly be chlorinated itself. For example, a halogenated hydrocarbon such as carbon tetrachloride may suitably be used.
` .. ', :
2 ~ 6 ~
There is no specific limitation to the reaction pressure, when the reaction is conducted in a gas phase.
The pressure for the reaction is not particularly limited and may range from reduced pressure to above atmospheric.
5 ~hen the reaction is conducted in a liquid phase, the -pressure is chosen so that the starting material 2,2-difluoropropane can adequately be present in the liquid phase and may vary depending upon the type of the solvent.
In the case o~ a gas phase reaction, chlorine may be introduced into a reactor together with the starting material as in a flow system, or may be charged initially. In the case of a liquid phase reaction, it may also be charged initially, but it is preEerable to ;~
bubble into the liquid phase.
Now, the present invention will be described in further detail with reference to Examples~ However, it should be understood that the present invention is by no means restricted by such speciic Examples.
A 1,000 cc glass reactor equipped with a condenser of -78C, was cooled to -20C, and 300 g o~ 1,2,2-triEluoropropane was charged. Then, 107 g of chlorine gas was gradually introduced while stirring under 25 irradiation by a high pressure mercury lamp of 500 W. ;~ -After the reaction for 6 hours, the product after removal of acid components, was analyzed by gas chromatography '. ' ..
~2~6~
g : :
and by l9F-NMR and lH-NMR. The results are shown in Table 1-1.
The reaction was conducted for 6 hours in the same 5 manner as in Example 1-1 except that 300 g of 1,1,2-trifluoropropane and 214 g of chlorine gas were used.
The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 1~
EXAMPLE 1-3 .
The reaction was conducted for 6 hours in the same manner as in Example 1-1 except that 300 g of 1,2,2-trifluoropropane and 430 g of chlorine gas were used.
The product was analyzed by gas chromatography and by l9F-NMR and lEI-NMR. The results are shown in Table 1-1.
The reaction was conducted for 6 hours in the same manner as in Example 1-1 except that 300 g of 1,2,2- ~
trifluoropropane and 214 g of chlorine gas were used, and 200 g of CC14 was used as the solvent for the reaction.
The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 1-1.
'' . . .
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Table 1-1 _ _ _ _ _ Example No. 1-1 1-2 1-3 1-4 _ . _ _ _ _ Conversion for CH2FCF2CH3 (~) 40 65 85 57 _ _ _ . _~ _. _ ,, .
Selectivity for CHClFCF2CH3 (~) 76 56 20 60 _ _ __ _ Selectivity for CCl2FCF2CH3 ~%) 8 18 29 20 _ _ _ _ . . .. _ . ..... . _ , .
Selectivity for CH2FCF2CH2Cl (%) 8 5 1 5 _ _ _ _ _ _ . . . . . ,.
Selectivity for CHClFCF2CH2C1 (%) _ _ 1 _ ~
. _ _ _ . ,._ _ _ _ Selectivity for CCl2FCP2CH2Cl (%) _ 2 5 1 ... ~ .
__ _ _ _ _ . __ _ ~ . _ .
Selectivity for CH2FCF2CHCl2 ~j%) 3 10 13 10 :
. _ _ _ _ _ _ _ _, _ . . _-- -- .
Selectivity for CHClFCF2CHCl2 (%) 1 _ 3 _ :
. ~ . . _ ~ _ _ ..
Selectivity for CCl2FCF2CHCl2 (%) 1 2 8 1 _ _ __~ _ .
Selectivity for CH2FCF2CC13 (~) 2 3 10 1 _ _ - _ _ _ ~, Selectivi.ty ~or CHClFCF2CC13 ~) _ 1 4 _ __ . __ _ __ _ _ : ,, Selectivity for CC12FCF2CCl3 ~) 1 2 6 2 _ _ ._ _ _ _ _ Other products (%) _ _ _ _ . _ _ Into a 1,000 cc Hastelloy C autoclave, 300 g of 1,2,2-trifluorolpropane and 20 g of di-~-butyl peroxide were charged. Then, thei temperature was raised to 120C, .
and while stirring, 214 g of chlorine gas was supplied at .: .
a rate of 50 g/hr over a period of 4 hours. Then, the reaction was continued for further 12 hours. The product 25 after removal of acid components, was analyzed by gas :
chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 1-2.
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2~2~
The reaction was conducted in the same manner as in Example 1-5 except that 20 g of AIBN was used as a radical initiator. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 1-2.
~n Inconel 600 reactor having a~ inner diameter of 1.27 cm and a length of 20 cm, ~as maintained at 430C, and gasified 1,2,2-trifluoropropane and chlorine gas were supplied at a rate of 300 ml/min, respectively. The reaction was conducted continuously for 4 hours. The product ~fter removal of acid components was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 1-2.
Table 1-2 _ . _ _ _ . . _ _ _ Example NQ. 1-5 1-6 1-7 _ _ _ _ _ :. . ,.
Conversion for CH2FCF2CH3 (%) 56 45 50 _ _ . __ ~r_: ~
Selectivity for CHClFCF2CH3 (%) 47 60 42 . _ ~ _ _ _ _ _ _ Selectivity for CC12FCF2CH3 (~) 21 23 17 ~ . . . :
Selectivity for CH2FCF2CH2C1 (%) 5 7 2 . _ _ .
Selectivity for CHClFCE'2OEI2Cl (%) _ _ _ ._ _ . __ _ Seleativity for CC12FCF2CH2Cl (%) 1 1 _ _ _ __ _ _ Selectivity for CH2FCF2CHC12 (~) 12 6 5 . _ ~ _ _ .
Selectivity for CHClFCF2CHCl2 (%) _ _ 3 ~ . _ . ,_ .:
Selectivity for CC12FCF2CHC12 (%) 4 _ 4 -~ _ ~
Selectivity for CH2FCF2CCl3 (%~ 4 2 10 ~ __ _ ....
Selectivity for CHClFCF2CC13 (%) 2 _ 4 ~ _ _ . . , Selectivity for CC12FCF2CC13 (%) 4 1 6 ~
. . ~ . _ Other products (%) _ _ _ 7 _ _. __ . _ ' ,i, 2~2~
EX~MPLE 1-8 The reaction was conducted for 6 hours in the same manner as in Example 1-1 except that 300 g l-chloro- . :~
2,~,3-trifluoropropane and 160 g of chlorine gas were :
used. The product was analyzed by gas chromatography and ~i by l9F-NMR and lH-NMR. The results are shown in Table 1-3 :.:
. .
Table 1-3 -. , ~ _ Conversion for CH2ClCF2CH2F (%) 67 . , _ . , . .
Selectivity Eor CHCl2CF2CH2F ~) 52 Selectivity for CC13CF2CH2F ~%) 14 . . , Selectivity for CH2ClCF2CHClF t~) 18 .~
Selectivity Eor CHC12CF2CHClF (%) 7 ~ _ __ I ...
. . Selectivity for CC13CF2CHClF ~%) 4 , _ _ _ Selectivity for CH2ClCF2CCl2F ~%) 3 ~ .
Selectivity for CHC12CF2CC12F (%) 2 -:
_ _ _ , ~
Selectivity for CC13CF2CC12F (%) _ :. .
":' '.: ' The reaction was conducted for 6 hours in the same manner as in Example 1-1 except that 300 g oE l-chloro-1,2,2-trifluoropropane and 160 g of chlorine gas were used. The product was analyzed by gas chromatography and .
by l9F-NMR and lH-NMR. The results are shown in Table 1- :
2S 4~
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Table 1-4 _ __ _ .
Conversion for CHClFCF2CH3 ~%) 77 Selectivity for CCl2FCF2CH3 (%) 77 . . _ _., _ _ ...
Selectivity for CHClFCF2CH2Cl (%) 4 , . , _ _ Selectivity for CCl2FCF2CH2Cl (%) 4 ~ _ ..
Selectivity for CHClFCF2CHCl2 (%) _ _ Selectivity for CCl2FCF2CHCl2 (%) 5 Selectivity for CHClFCF2CCl3 (%) 3 _ _ _ .
Selectivity for CCl2FCF2CCl3 (%3 1 EXAMPLE 1-10 .
The reaction was conducted for 6 hours in the same rnanner as in Example 1-1 except that 300 g of 1,3- :
dichloro-1,2,2-trifluoropropane and 130 9 of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 1-5.
Table 1-5 _ _ _ Conversion for CHClFCF2CH2Cl (~) 74 . .
20. _ _ _ Selectivity for CC12FCF2CH2C1 (~) 26 i Selectivity for CHClFCF2CHCl2 (%) 44 . .
_ _ _ . _ . _.
Selectivity for CCl2FCF2CHCl2 (~) 13 .
~ _ . ., Selectivit~ for CHClFCF2CCl3 (%) 12 _ _ , .
Selectivity for CCl2FCF2CCl3 (%) 5 ~2~6 i;~3 -EXAMPLE 1-11 ;
The reaction was conducted for 6 hours in the same manner as in Example 1-1 except that 300 g of 1,1-dichloro-2,2,3-trifluoropropane and 130 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 1-6.
'.... "
Table 1-6 ~ . _ . : .
Conversion for CHC12CF2CH2F (%) 73 _ _ . . .
10Selectivity for CCl3CF2CH2F (%) 57 :~
, _ _ _ _ _ : i .
Selectivity for CHC12CF2CHClF (%) 11 _ _ _ Selectivity for CC13CF2CHClF (%) 25 .. :
_ : ':
Selectivity ~or CHC12CF2CC12F (~i) 3 . _ Selectivity for CC13CF2CC12F ~i) 4 :
The reaction was conducted for 6 hours in the same .
manner as in Example 1-1 except that 300 g of 1,1- .
dichloro-1,2,2-trifluoropropane and 130 g of chlorine gas 20 were used, The product was analyzed by gas ~.
chromatography and by 19F-NMR and l~-NMR. The results are shown in Table 1-7. ~.
- 2~2~6~3 Table 1-7 _ . _ _ _ _ _ ..
Conversion for CC12FCF2OEI3 ~ 40 Selectivity for CCl2FCF2CH2Cl (%) _ _ Selectivity for CCl2FCF2CHCl2 (%) 67 Selectivity for CCl2FCF2CCl3 (%) 29 The reaction was conducted for 6 hours in the same ~.
manner as in Example 1-1 except that 300 g of 1,1,3-trichloro-2,2,3-trifluoropropane and 105 g of chlorine ga~ were used. The product was analyzed by gas chromatography and by l9F-NMR and l~I~NMR. The results are shown in Table 1-8.
Table 1-8 . _ Conversion for CHCl2CF2CHClF (%) 85 .. ._ _ _ _ . _ . ~ .
Selectivity for CCl3CF2CHClF (%) 70 Selectivity for CHC12CF2CC12F ~) 20 ISelectivity for CCl3CF2CCl2F (%) 10 `.
The reaction was conducted for 6 hours in the same manner as in Example 1-1 except that 300 g of 1,1,3-trichloro-1,2,2-trifluoropropane and 53 g of chlorine gas .:
were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 1-9.
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2 ~
Table 1-9 Conversion for CC12FCF2CH2Cl t~) 38 :.
_ . . T . _ _ .
Selectivity for CC12FCF2CHCl2 (%) 78 _~
~ ~ ~ _ 22 ~, S
The reaction was conducted for 6 hours in the same .~.
manner as in Example 1-1 except that 300 g of 1,1,1- :
trichloro-2,2,3-trifluoropropane and 53 g oE chlorine gas were used. The product was analyzed by gaæ
chromatography and by l9F-NMR and lH-NMR. q'he results are shown in Table 1-10.
Table 1-10 _ _ .
Conversion for CCl3CF2CH2F (%) 38 _ . ~
Selectivity for CCl3CFzCHClF (%) 78 ..
. _ _ _ _ _ _ .
Selectivity for CCl3CF2CCl2F (%) 22 EXAMP~E 1-16 The reaction was conducted for 6 hours in the same manner as in Example 1-1 except that 300 g of 1,1,3,3-tetrachloro-1,2,2~trifluoropropane and 90 g of chlorine ga9 were u5ed. The product was analy2ed by gas chromatography and by 19F-NMR and lH-NMR The results are shown in Table 1-11. 7 " ' '"
2~2~6~ ~:
--Table 1-11 . _ Conversion for CC12FCF2CHC12 (%) 98 ISelectivity for CCl2FCF~CCl3 (%) 100 EXAMPLE 1-17 ~ .
~ he reaction was conducted for 6 hours in the same manner as in Example 1-1 except that 300 9 of 1,1,1,3-tetrachloro-2,2,3-trifluoropropane and 90 9 of chlorine gas were used. The product was analyzed by gas chromatography and by l9F-NMR and lH-NMR. The results are shown in Table 1-12.
Table 1-12 .. _ _ _ . . .
. Conversion or CC13CF2CHClF t%) 97 . I . ~
Selectivity for CCl3CF2CCl2~ (%) 100 :~
~.
A 1,000 cc glass reactor e~uipped with a condenser o~
-78C, was cooled to -20C, and 300 g of 1,2,2,3-tetrafluoropropane was charged. Then, 95 9 of chlorine gas was gradually introduced while stirring under irradiation by a high pressure mercury lamp of 500 W.
After the reaction for 6 hours, the product after removal :
25 o~ acid components, was analyzed by gas chromatography :.
and by 19F-NMR and IH-NMR. The results are shown in ~ :
- .:
Table 2-1. ~
. . .
. :
~. .
~ ~ 2 ~
- lB -The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g o~ 1,2,2,3-tetrafluoropropane and 185 g of chlorine gas were used.
The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 2 - The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g of 1,2,2,3-tetrafluoropropane and 370 g of chlorine gas were used.
The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 2-1.
The reaction was conducted Eor 6 hours in the same lS manner as in Example 2-1 except that 300 g of 1,2,2l3-tetxafluoropropane, 185 g oE chlorine gas and 200 9 of CC14 as a solvent were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 2~1.
6 ~
Table 2-1 . . _ __ .
Example N~. 2-1 2-2 2-3 2-4 _ _ , _ .
Conversion for CH2FCF2CH2F (%) 40 66 92 65 Selectivity for CHClFCF2CH2F (%) 90 61 30 70 _ . _~ ,, ,_ Selectivity for CCl2FCF2CH2F (%) 5 18 25 15 ~ _, . _ ~ ~
Selectivity for CHClFCF2CHClF (~ 3 11 15 g _ . _ . _ _ _ Selectivity for CCl2FCF2CHClF (%) 2 8 19 5 . _ _ _ _ _ _ _ . ., .__ . , Selectivity for CCl2FCF2CClF2 (~) _ 2 11 1 . . ~ . , _. _ . . ,' Into a 1,000 cc Hastelloy C autoclave, 300 g of 1,2 r 2,3-tetrafluorolpropane and 20 g of di t-butyl peroxide were charged. Then, the temperature was raised to 120C, and while stirring, 185 g of chlorine gas was supplied at a rate of 50 g/hr over a period of 4 hours.
Then, the reaction was continued for further 12 hours.
The product ater removal of acid components, was analyzed by gas chromatography and by l9F-NMR and l~-NMR.
~he results are shown in Table 2-2.
EXAMP~E 2-6 The reaction was conducted in the same manner as in Example 2-5 except that 300 g of 1,2,2,3-tetrafluoropropane and 20 g of AIBN as a radical initiator were used. The product was analy~ed by gas , ~ ., , .
2 0 2 6 ~ 6 ~
ch~omatography and by l9F-NMR and lH-NMR. The results are shown in Table 2-2.
An Inconel 600 reactor having an inner diameter of 1.27 cm and a length of 20 cm, was maintained at 430C, and gasified 1,2,2,3-tetra~luoropropane and chlorine gas were supplied at a rate of 150 ml/min, xespectively. The reaction was conducted continuously for 4 hours. The product after removal of acid components was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 2-2.
Table 2-2 Example No. 2-5 Z-6 2-7 ,- _ Conversion Eor CH2FCF2CH2F ~%) 50 35 54 15Selectivity for CHClFCF2CH2F ~) 60 66 53 _ _ _ , Selectivity ~or CC12FCF2CH2F (~) 15 12 16 . ~ ~ . . . . ..
Selectivity for CHClFCF2CHClF (%) 11 7 12 ~ -, ~ _ _ _ _ _ . , .
Selectivity for CC12FCF2CHClF (%) 10 5 7 ,. _ _ .
Selectivity for CC12FC~2CC12F (%) 4 3 5 _ _ . _ . -- . .
. .
EX~MPLE 2-8 The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 9 of 1,1,2,2-tetrafluoropropane and 185 g of chlorine gas were usedand the reaction was carried out at -30C. The product was analyzed by gas chromatography and by l9F-NMR and lH-. .
, , . . . . . .... .. : .. ; .. .. . ,.. ., ,;, ,. . . ~ . .,., ", ~, : .. .,:. . . . .
2~2~6`~
,. .. :
NMR. The results are shown in Table 2-3.
Table 2-3 _ , _ ~
Conversion for CHF2CF2CH3 (%? 54 Selectivity for CClF2CF2CH3 (~) 45 _ _ _ _ _ . __ _ _ Selectivity for CHF2CF2CH2C1 (%) 2 . . . _ .
Selectivity for CClF2CF2CH2Cl (%) 4 ~ . .
Selectivity for CHF2CF2CHCl2 (%) 20 .~ .
_ . .
Selectivity for CClF2CF2CHCl2 (%) 13 Selectivity for CHF2CF2CC13 (%) 15 . . -Selectivity for CClF2CF2CCl3 (%) l :
. _ "... ..
. . . .
The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g oE l-chloro-2,2,3,3-tetrafluoropropane and 140 g of chlorine gas were .
used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 2-4. ;!
Table 2-4 ___ ~ . -Conversion ~or CH2ClCF2CHF2 (%) 57 :~
. __ . .
Selectivity ~ 4 : Selectivity for CHCl2CF2CHF2 (%) 12 , _ . _ _ _ . _ _ ~ __. . ..
Selectivity for CHCl2CF2CCl~2 ~) _ Selectivity for CC13CF2CHF2 (~) 21 . .. _ _ ___,_ . , :
Selectivity ~or CC13CF2CClF2 (%) l . :
, _ _ _ _ _ . ~ .-- ' , .
, ~2~ ~3~ ~
The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g of l-chloro-1,2,2,3-tetrafluoropropane and 140 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 2-5.
Table 2-5 , , , , _ . , ..
Conversion for C~ClFCF2CH2F ~%) 80 , ,, ............. _ . . .
10Selectivity for CCl2FCF2CH2F ~%) 54 _ . .... . . _ ..
Selectivity ~or CHClFCF2CHClF (%) 28 .. ... . ............. . _ .
Selectivity for CC12FCF2C~ClF ~%) 16 , ...... . __ _ :..
The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g of l-chloro- -1,1,2,2-tetrafluoropropane and 140 g of chlorine gas were usedO The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 2-6.
Table 2-6 . ..
l Conversion for CClF2CF2CH3 (%) . .
~ _ ~) S
Selectivity for CClF2CF2CHC12 (%) 65 .. . - . . . . . ~
SPlectivity for CClF2CF2CC13 (%) 30 : .
2 ~
The reaction was conducted for 6 hours in the same manner as in Example 2-l except that 300 g oE 1,3-dichloro-1,2,2,3-tetrafluoropropane and 115 9 of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-~MR and lH-NMR. The results are shown in Table 2-7.
Table 2-7 _ _ . _ , .
Conversion for CHClFCF2CHClF (%) 88 , _ . __ __ _ 10Selectivity for CCl~FCF2CHClF (%) ~9 : :
. _ . _ ~
5electivity for CCl2FCF2CCl2F (%) 11 :
~ _ ,:
The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 9 of l,l- ~:
dichloro-2,2,3,3-tetrafluoropropane and 115 9 of chlorine gas were used. The product was analyzed by gas :.
chromatography and by 19F-NMR and lH-NMR. The results ~ .
20 are shown in Table 2-8.
q'able 2-8 Conversion for C~IC12CF2CHF2 ~) 95 _ _ , ,.
Selectivity for CC13CF2CHF2 (%) 97 ..
. _ __ _ Selectivity for CHC12CF2CC1~2 (~) 3 : ~ :
. . _, _ ~ ___ . .
Selectivity for CCl3CF2CClF2 (%) _ : -_ __ __ . :.. :" .
, .....
2 ~ 2 ~ ~ 6 b The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g of 1,3-dichloro-1,1,2,2-tetrafluoropropane and 58 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 2-9.
~ ;~
Table 2-9 . _ . .
Conversion for CClF2CF2CH2Cl (%) 35 , .
Selectivity for CClE'2CF2CHC12 (%) 80 ~ . ~
Selectivity for CClE`2CF2CCl3 (~) 20 . _ _ EXAMPhE 2-15 The reaction was conducted for 6 hours in the same manner as in Example 2-1 except ~hat 300 9 of 1,1-dichloro-1,2,2,3-tetrafluoropropane and 58 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 2-10.
~able 2-10 _ Conversion ~or CC12FCE'2CH2F (%) 38 -:
_ _ Selectivity for CC12FCF2CHClF ~%) 78 ~ ~
, _ _ . . . .
Selectivity ~or CCI~/Cr~CCI~ 22 ;
2~26~
The reaction was conducted for 6 hours in the same manner as in Example 2-l except that 300 9 o~ l,1,3-trichloro-2,2,3,3-tetrafluoropropane and lO0 g of chlorine gas were used. The product was analy~ed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 2-ll.
Table 2-11 _ _ _ _ Conversion for CHC12CF2CClF2 (%) 98 . ,~_ _ _ _ . .
lUSelectivity ~or CC13CF2CClF3 (%) 100 ._ _ __._ .. :'' ':
. . ,:
The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g of 1,1,3-trichloro-1,2,2,3-tetrafluoropropane and 100 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results 20 are shown in Table 2-12.
:. ::..
Table 2-12 __ __ _ .
Conversion for CCl2FCF2C~IClF ~%~ 97 ~.
. . .
Selectivity for CC12FCF2CCl2F (%) 100 - 26- 2~2~ 3 The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g of 1,1,1-trichloro-2,2,3,3-tetrafluoropropane and 100 9 of chlorine gas were used. The product was analyzed by gas chromatography and by l9F-NMR and lH-NMR. The results are shown in Table 2-13.
Table 2-13 ~ r - ~
Conversion for CCl3CF2CEF2 (%) ¦ 91 ..
_ . _ _ I _ _ . .
Selectivity Eor CC13CF2CClF2 (% ~ 100 EXAMPLE 3-1 .
A 1,000 cc glass reactor equipped with a condenser of -78C, was cooled to -20C, and 300 g of 1,1,2,2,3-pentafluoropropane was charged. Then, 80 g oE chlorine gas was gradually introduced while stirring under irradiation by a high pressure mercury lamp of 500 W.
A~ter the reaction for 6 hours, the product after removal oE acid components, was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 3-1.
The reaction was conducted for 6 hours in the same manner as in Example 3-1 except that 300 g of 1,1,2,2,3- .
pentafluoropropane and 160 g of chlorine gas were used.
' ', '' ', '.
2 ~
The product was analy~ed by gas chromatography and by l9F-NMR and lH-NMR. The results are shown in Table 3-1.
EX~MPLE 3-3 The reaction was conducted for 6 hours in the same manner as in Example 3-1 except that 300 g of 1,1,2,2,3-pentafluoropropane and 320 9 of chlorine gas were used.
The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Ta~le 3-1. ~:~
The reaction was conducted for 6 hours in the same manner as in Example 3~1 except that 300 g Of 1 r 1 r 2,2,3-pentafluoropropane, 160 g o~ chlorine gas and 200 g oE
CC14 as a solvent were used. q'he product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 3-1.
.:~
....... ..
.,:. ~, Table 3-1 .~
_ _ _ _ ~
Example No. 3-1 3-2 3-3 3-4 __ _ _ _ __ Conversion for CHF2CF2CH2F ~i)32 60 97 55 ..
_ _ _ Selectivity for CClF2CF2C~2F (%) 12 12 4 12 ~ . . _ . _ ...
Selectivity for CHF2CF2CHClF (~i) 78 71 20 75 . ..
_ _ _ _ . . _ _ _ . .... ..
Selectivity for CClF2CF2CHClF (%): . 2 5 12 4 . : ~ _ . . _ _ Selectivity for CHF2CF2CC12F (%) 8 11 47 8 .
~_ _ -- . ! - ' Selectivity for CC}F2CF2CC12F (%) . ~ 1 17 1 _ . - . _ _ _ .
. .. . .... .... ..
2632~6i~
Into a l,000 cc Hastelloy C autoclave, 300 g of 1 j1,2,2, 3-pentafluorolpropane and 20 g oE di-t-butyl peroxide were charged. Then, the temperature was raised to 120C, and while stirring, 200 g of chlorine gas was supplied at a rate of 50 g/hr over a period of 4 hours.
Then, the reaction was continued for further 12 hours.
The product after removal of acid components, was analyzed by gas chromatography and by 19F-NMR and lH-NMR.
The results are shown in Table 3-2.
EXAMPLE 3-6 ;
The reaction was conducted while 200 g of chlorine gas was supplied at a rate of 50 g/hr for 4 hours in the same manner as in Example 3-5 except that 300 g of 15 1,1,2,2,3-pentafluoropropane and 20 g of AIBN as a radical initiator were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 3-2.
EXAMPLE 3-7 ~ -An Inconel 600 reactor having an inner diameter of 1,27 cm and a leng~h of 20 cm, was maintained at 430C, and gasified 1,1,2,2,3-pentafluoropropane and chlorine gas were supplied at a rate of 150 ml/min, respectively.
The reaction was conducted continuously for 4 hours. The product after removal of acid components was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 3-2.
, . , ,', . '. . ' ~' ' .; " ' ' " " " ~ .' ' ' " ' ' " ' ', '' " ' '' , ', ' ~ ' ', ' ' , ' ' ' ,., ' " ' ' ' 2 ~
Table 3-2 . _. _ ~ . .
Example No. 3-5 3-6 3-7 _ __ .
Conversion for CHF2CF2CH2F (%) 60 45 50 _ . ,_ Selectivity for CClF2CF2CH2F (%)15 12 20 S - . . ............................. _ .
Selectivity for CHF2CF2CHClF (~) 58 62 58 . . . . , , . ._ ~ ~ _ . . _ Selectivity for CClF2CF2CHClF (%) 5 6 ~ :
Selectivity for CHF2CF2CC12F ~%) 17 15 9 ..
. . ~ _ . . .
Selectivity for CClF2CF2CCl2F (%) ~ ~ 5 6 - . :' EXAMPLE 3-8 ::
The reaction was conducted for 6 hours in the same manner as in Example 3-1 except that 300 g of 1,1,1,2,2-pentafluoropropane and 160 g of chlorine gas were used and the reaction was carried out at -30C. The product was analyzed by gas chromatography and by 19F-NMR and lH- `
NMR. The results are shown in Table 3-3.
Table 3-3 ~ __ Conversion for CF3CF2CH3 (%) 40 Selectivity for CF3CF2CH2Cl (~) 6 . :.:
_ .................. ,.. _ ... . i ' Selectivity for CF3CF2CHC12 (~) 64 . ., .
Selectivity for CF3CP2CC13 (%) 30 ~ ' '',' ' ,~
'.
.':' , 2 ~ 6 ~ :
The reaction was conducted for 6 hours in the same manner as in Example 3-1 except that 300 g of l-chloro-1,2,2,3,3-pentafluoropropane and 130 9 of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 3-4.
Table 3-4 . _ _ _ . _ ~ 9~ . ~"
Selectivity for CC12FCF2CHF2 (%) 90 _ ..
Selectivity for CHClFCF2CClF2 (%) 8 _ _ _ _ __ Selectivity for CC12FCF2CClF2 (%) 2 The reaction ~as conducted for 6 hours in the same manner as in Example 3-1 except that 300 g of l-chloro-2,2,3,3,3-pentafluoropropane and 65 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 3-5.
¦convers~ ~ F 3 1 : Selectivit ~ 9 2:5 ~ ~ 19 i ~ .
2 a~
The reaction was conducted for 6 hours in the same mianner as in Example 3-1 except that 300 g of l-chloro-1,1,2,2,3-pentafluoropropane and 65 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results ;~ .
are shown in Table 3-6.
Table 3-6 _ _ _ _ _ Conversion for CClF2CF2CH2F (~i) 36 __ ..
10Selectivity for CClF2CF2CHClF (%) 76 .
_ . . . ~ _ Selectivity for CClF2CF2CC12F ~%) 24 The reaction was conducted for 6 hours in the same `:
manner as in Example 3-1 except that 300 g of 1,1- :.
dichloro-2,2,3,3,3-pentafluoropropane and 105 g of chlorine gas were used. The product was analyzed by gas , chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 3-7. :':
Table 3-7 _ , .
IConversion for CF3CF2CHC12 (~) _ _ 25j5electivity for cr~Cr~cc~ ) 100 ::
; ~
'.
. i ~2~6~
The reaction was conducted for 6 hours in the same manner as in Example 3-l except that 300 y of 1,3-dichloro-1,1,2,2,3-pentafluoropropane and 105 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 3-8.
Table 3-8 . _ _ _ _ _ _ _ Conversion for CClF2CF2CHClF (%) 97 , ~ . .
Selectlvity for CClF2CF2CCl2F ~%) lO0 r . . _ ____ . - _ _ . .
The reaction was conducted for 6 hours in the same manner as in Example 3-1 except that 300 g of l,l-dichloro-1,2,2,3,3-pentafluoropropane and 105 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 3 9.
Table 3-9 . . _ ..
Conversion for CCl2FCF2CHF2 t%) 91 _ _ Selectivity for CCl2FCF2CClF2 (%) lO0 _ _ , __ _ ~5 .
2~26~
- 33 - :
A 1,000 cc glass reactor equipped with a condenser of -78C, was cooled to -20C, and 300 g of 1,1,2,2,3,3- -hexafluoropropane was charged. Then, 70 g of chlorine gas was gradually introduced while stirring under irradiation by a high pressure mercury lamp of 500 W.
After the reaction for 6 hours, the product after removal of acld components, was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in ;~
Table 4-1.
The reaction was conducted for 6 hours in the same manner as in Example 4-1 except that 300 g of ;~
1,1,2,2,3,3-hexafluoropropane and 140 g of chlorine gas lS were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 4-1.
EXAMP~E 4-3 The reaction was conducted for 6 hours in the same manner as in Example 4-1 except that 300 g of 1,1,2,2,3,3-hexafluoropropane and 280 g of chlorine gas were used. The product was analyzed by gas chromatography and by l9F-NMR and lH-NMR. The results are shown in Table 4-1.
ExAMpLE 4-4 The reaction was conducted for 6 hours in the same manner as in Example 4-1 except that 300 g of ~2~6~
~ 34 -1,1,2,2,3,3-hexafluoropropane, 140 g of chlorine gas and 200 g of CC14 as a solvent ~ere used~ The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR.
The results are shown in Table 4-1.
Table 4-1 . . . ._ . , _ . , .. . _ ..
Example No. 4-1 4-2 4-3 4-4 . . . . . . . . . ~ _ Conversion for CHF2CF2CHF2 (%) 32 64 92 52 . . _ Selectivity for CClF2C~2CHF2 t%) 98 81 32 89 .~ . . . _ ~ . . . ,._ Selectivity for CClF~CF2CClF2 (%) 2 19 68 11 . _ . . . . . ., Other products (~) _ _ _ . _ . _ _ . _ .
, Into a 1,000 cc ~astelloy C autoclave, 300 9 of 1,1,2,2,3,3-hexafluorolpropane and 20 g of di-t~butyl peroxide were charged. Then, the temperature was raised to 120C, and while stirring, 160 g of chlorine gas was supplied at a rate o~ 40 g/hr over a period of 4 hours.
Then, the reaction was continued for further 12 hours.
The product a~ter removal o~ acid components, was -- analyzed by gas chromatography and by l9F-NMR and l~-NMR.
The results are shown in Table 4-2.
EXAMP~E 4-6 The reaction was conducted in the same manner as in :~ "
` ;;
.
, , .
2 a 2 ~
Example 4-5 except that 300 9 of 1,1,2,2,3,3-hexafluoropropane and 20 g of AIBN as a radical initiator were used. 160 of chlorine gas was supplied at a rate of 40 g/hr over a period of 4 hours, and then the reaction :
was continued for further 12 hours. The product was analyzed by gas chromato~raphy and by 19F-NMR and lH-NMR.
The results are shown in Table 4-2. ~.
An Inconel 600 reactor having an inner diameter of ~' 1.27 cm and a length of 20 cm, was maintained at 430~C, and gasified 1,1,2,2,3,3-hexafluoropropane and chlorine gas were supplied at a rate of 150 ml/min, respectively. ;
The reaction was conducted continuously for 4 hours. The product after removal o acid components was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 4-2.
Table 4-2 _ . _ __ .................... .. _ ,.:'.
Example No. 4-5 4-6 4-7 -~ _ . _ _ _ __ _ _ __ Conversion for CHF2CF2CHF2 (%) 50 25 66 - _ _ ~ _ __ Selectivity for CClF2CF2CHF2 (%) 80 95 72 . _ __ .
Selectivity Eor CClF2CF2CClF2 ~%) 20 __ 20 Other products ~) _ _ 8 .. ~ ,. _ _ ,."~
, :' 2 ~ 6 ~
The reaction was conducted for 6 hours in the same manner as in Example 4-1 except that 300 9 of 1,1,1,2,2,3-hexafluoropropane and 70 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMRo The results are shown in Table 4-3.
Table 4-3 ~ ..
Conversion for CF3CF2CH2F (%) 38 1 0 , . ~
Selectivity for CF3CF2CHClF (%) 74 _ _ _ _ .
Selectivity for CF3CF2CC12F (%) 26 ~:
. "
The reaction was conducted for 6 hours in the same manner as in Example 4-1 except that 300 g of l-chloro-1,2,2,3,3,3-hexafluoropropane and 120 9 of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 4-4.
Table 4-4 :
. _ _ _ _.
Conversion for CF3CF2CHClF (~i) 97 . ~ . ' ~:
Selectivity for CF3CF2C.Cl2F (%) 100 . .
_ _ . .
',:
., .:
,', ' ~'':
:, :.
~ ~ 2 ~
The reaction was conducted for 6 hours in the same manner as in Example 4-1 except that 300 g of l-chloro-1,1,2,2,3,3-hexafluoropropane and 120 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 4-S.
Table 4-5 :
. , , , Conversion for CClF2CF2CHF2 (%) 95 :.
. . _ ., Selectivity for CClF2CF2CClF2 (%) 100 ;.
The present invention is effective for producing a chlorine-containing 2,2~difluoropropane sele~tively by chlorinating a 2,2-difluoropropane.
~, . ,, , . , . ,, . . . - . .. ..
. . : . ........ . . ............. . ....... .
.. . . . . ..
C3HmlC15_mlF3 ' C3HnlC15-nlF3 ( ) 1 _ ml c 5 o ~ nl ~ 4I ml > nl The 2,2-difluoropropane (C3HmlCl5_mlF-~ wherein 1 ~ ml ~ 5) to be used as the starting material includes, for example, 1,2,2-trifluoropropane (R-263c), 1-chloro-2,2,3- .
trifluoropropane (R-253ca), 1-chloro-1,2,2-trifluoropropane (R-253cb), 1,3-dichloro-1,2,2-trifluoropropane (R-243ca), 1,1-dichloro-2,2,3~
trifluoropropane (R-243cb), 1,1-dichloro-1,2,2- : `.
trifluoropropane ~R-243cc), 1,1,3-trichloro-1,2,2~ :
tri~luoropropane (R-233cb), 1,1,3,3-tetrachloro-1,2,2-trifluoropropane ~R-223ca) and 1,1,1,3-tetrachloro-2,2,3-trifluoropropane (R-223cb).
The chlorine-containing 2,2-difluoropropane -:
( C3HnlCls_nlF3 wherein O ~ nl 5 4) to be formed by the reaction includes l-chloro-2,2,3-trifluoropropane (R-253ca), 1-chloro-1,2,2-trifluoropropane (R-253cb), 1,3-dichloro-1,2,2-trifluoropropane (R-243ca~, l,l-dichloro- :
2,2,3-trifluoropropane (R-243cb) r 1,1-dichloro-1~2,2-trifluoropropane ~R-243cc), 1,1,3-trichloro-2,2,3-tri~luoropropane (R-233ca), 1,1,3-trichloro-1,2,2-trifluoropropane (R-233cb), 1,1,1-trichloro-2,2,3- `
triEluoropropane (R-233cc), 1,1,3,3-tetrachloro-1,2,2- ~:
trifluoropropane (R-2-3ca), 1,1,1,3-tetrachloro-2,2,3-2~2$~S~
trifluoropropane (R-223cb) and 1,1,1,3,3-pentachloro-2,2,3-trifluoropropane (R-213c).
C3Hm2Cl~_m2F4 C3Hn2Cl4_n2F4 (4) 1 _ m2 ~ 4 0 < n2 ~ 3, m2 > n2 The 2,2-difluoropropane (C3Hm2Cl4_m2Fq wherein 1 ~ m2 ~ 4) to be used as the starting materia:L includes :~
1,2,2,3-tetrafluoropropane (R-254ca), 1,1,2,2-tetrafluoropropane ~R-254cb), 1-chloro-2,2,3,3-tetrafluoropropane ~R-244ca), 1-chloro-1,2,2l3-tetrafluoropropane (R-244cb), 1-chloro-1,1,2,2-tetrafluoropropane (R-244cc), 1,3-dichloro-lr2,2,3- :i :
tetra1uoropropane (R-234ca), 1,1-dichloro-2,2,3,3-tetraEluoropropane ~R-234cb), 1,3-dichloro-1,1,2,2-tetrafluoropropane ~R-234cc), 1,1-dichloro-1,2,2,3-tetrafluoropropane (R-234cd), 1,1,3-trichloro-2,2,3,3- ~ ;
tetrafluoropropane (R-224ca), 1,1,3-trichloro-1,2,2,3-tetrafluoropropane (R-224cb) and 1,1-trichloro-2,2,3,3- ...
tetraEluoropropane (R-224cc).
The chlorine-containing 2,2-difluoropropane ~C3Hn2C14_n2F~ wherein O ~ n2 ~ 3) to be formed by the reaction includes l~chloro-2,2,3,3-tetra~luoropropane ~R-244ca) r 1-chloro-1,2,2,3-tetra~luoropropane tR-244cb), 1-chloro-1,1,2,2-tetrafluoropropane ~R-244cc), 1,3- - : :
dîchloro-1,2,2,3-tetrafluoropropane (R-234ca), 1,1- -dichloro-2,2,3,3-tetrafluoropropane (R-234cb), 1,3 dichloro-1,1,2/2-tetrafluoropropane (R-234cc), 1,1- :
'''"'`'-'' ,"'"' 2 ~ 6 ~
dichloro-1,2,2,3-tetrafluoropropane (R-234cd), 1,lr3-trichloro-2,2,3,3-tetrafluoropropane (R-224ca), 1,1,3- :
trichloro-1,2,2,3-tetrafluoropropane ~R-224cb), 1,1,1-trichloro-2,2,3,3-tetrafluoropropane (R-224cc), 1,1,3,3-tetrachloro-1,2,2,3-tetrafluoropropane (R-214ca) and 1,1,1,3-tetrachloro-2,2,3,3-tetrafluoropropane (R-214cb).
These products can be separated by a usual method such as distillation~
C3Hm3Cl3_m3Fs ' C3Hn3Cl3-n3F5 (5) 1 ~ m3 ~ 3 ~ n3 ~ 2, m3 > n3 The 2r2-difluoropropane (C3Hm3Cl3_m3F5 wherein 1 ~ m ~ 3 to be used as the starting material includes 1,1,2,2,3-pentafluoropropane (R-245ca), 1,1,1,2,2-pentaEluoropropane (R-245cb), 1-chloro-1,2,2,3,3- ;
pentafluoropropane (R-235ca), 1-chloro-2,2,3,3,3-pentafluoropropane (R-235cb), 1-chloro-1,1,2,2,3-penta~luoropropane (R-235cc), 1,1-dichloro-2,2,3,3,3-penta1uoropropane (R-225ca), 1,3-dichloro-1,1,2,2,3-pentafluoropropane (R-225cb) and 1,1-dichloro-1,2,2,3,3-pentafluoropropane (R-225cc).
The chlorine-containing 2,2-difluoropropane (C3Hn3C13_n3F5 wherein 0 ~ n3 ~ 2) to be formed by the reaction includes l-chloro-l,ll2,2,3,3-pentafluoropropane (R-235ca), 1-chloro-2,2,3,3,3-pentafluoropropane (R-235cb~, 1-chloro-1,1,2,2,3-pentafluoropropane (R-235cc), lJl-dichloro-2,2,3,3,3-pentafluoropropane (R-225ça), 1,3- `
,':
- 2 ~ 2 ~
dichloro-1,1,2,2,3-pentafluoropropane (R-225cb), 1,1-dichloro-1,2,2,3,3-pentafluoropropane (R-225cc), 1,1,3-trichloro-1,2,2,3,3-pentafluoropropane (R-215ca) and 1,1,1-trichloro-2,2,3,3,3-pentafluoropropane (R-215cb).
Cl~
C3Hm4cl2-m4F6 -~ C3Hn2C12-n4F5 (6) 1 S m4 5 2 _ n4 ~ 1, m4 > n4 The 2,2-difluoropropane (C3Hm~Cl2_m~F~ wherein 1 ~ m4 ~ 2) to be used as the starting material includes 1,1,2,2,3,3-hexafluoropropane (R-236ca), 1,1,1,2,2,3-hexafluoropropane (R-236cb), 1-chloro-1,2,2,3f3,3-hexafluoropropane (R-226ca) and 1-chloro-1,1,2,2,3,3-hexafluoropropane (R-226cb).
The chlorine-containing 2,2-diEluoropropane (C3HnCl2_nF6 wherein 0 ~ n 5 1) to be Eormed by the reaction includes l-chloro-1,2,2,3,3,3-hexa~luoropropane ~R-226ca), 1-chloro-1,1,2,2,3,3-hexfluoropropane ~R-226cb), 1,3-dichloro-1,1,2,2,3,3-hexafluoropropane (R-216ca) and 1,1-dichloro-1,2,2,3,3,3-hexafluoropropane (R-216cb). The~e products can be separated by a usual 20method such as distillation.
For the reaction, a radical-generating source such as light, heat or a radical initiator, or a combination thereof, may be used. The radical initiator to be used is not particularly limited so long as it is oil-soluble and may be an azo compound or an organic peroxide as shown in the following example. The azo compound may, ~, ' ;~ ,.
2~2~
for example, be a,a'-azobisisobutylonitrile (hereinafter referred to simply as AIBN) or 2,2-azobis-2,4-dimethylvaleronitrile (hereinafter referred to simply as ACVN). The organic peroxide may, for example, be di~t-butyl peroxide.
The reaction ratio between chlorine and the starting material may be varied in a wide range. In order to control the chlorination selectively at a stage where only single chlorine is introduced, chlorine is used in a `
low stoichiometrical amount relative to the 2,2-difluoropropane (C3HaClbFC). Whereas, to let all the hydrogen atoms o~ the 2,2-difluoropropane react substantially completely, chlorine is used in an amount larger than stoichiometry relative to total molar amount of the starting material, for exampler in an amount of 2 or more molar times.
The reaction temperature may suitably be chosen depending upon the radical-generating source and is usually from -78 to 450C.
In the present invention, when the reaction is conducted in a liquid phase, a solvent may be employed.
The solvent to be used is not particularly limited so long as it is capable of dissolving the propane as the starting material and the radical initiator if used, and will hardly be chlorinated itself. For example, a halogenated hydrocarbon such as carbon tetrachloride may suitably be used.
` .. ', :
2 ~ 6 ~
There is no specific limitation to the reaction pressure, when the reaction is conducted in a gas phase.
The pressure for the reaction is not particularly limited and may range from reduced pressure to above atmospheric.
5 ~hen the reaction is conducted in a liquid phase, the -pressure is chosen so that the starting material 2,2-difluoropropane can adequately be present in the liquid phase and may vary depending upon the type of the solvent.
In the case o~ a gas phase reaction, chlorine may be introduced into a reactor together with the starting material as in a flow system, or may be charged initially. In the case of a liquid phase reaction, it may also be charged initially, but it is preEerable to ;~
bubble into the liquid phase.
Now, the present invention will be described in further detail with reference to Examples~ However, it should be understood that the present invention is by no means restricted by such speciic Examples.
A 1,000 cc glass reactor equipped with a condenser of -78C, was cooled to -20C, and 300 g o~ 1,2,2-triEluoropropane was charged. Then, 107 g of chlorine gas was gradually introduced while stirring under 25 irradiation by a high pressure mercury lamp of 500 W. ;~ -After the reaction for 6 hours, the product after removal of acid components, was analyzed by gas chromatography '. ' ..
~2~6~
g : :
and by l9F-NMR and lH-NMR. The results are shown in Table 1-1.
The reaction was conducted for 6 hours in the same 5 manner as in Example 1-1 except that 300 g of 1,1,2-trifluoropropane and 214 g of chlorine gas were used.
The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 1~
EXAMPLE 1-3 .
The reaction was conducted for 6 hours in the same manner as in Example 1-1 except that 300 g of 1,2,2-trifluoropropane and 430 g of chlorine gas were used.
The product was analyzed by gas chromatography and by l9F-NMR and lEI-NMR. The results are shown in Table 1-1.
The reaction was conducted for 6 hours in the same manner as in Example 1-1 except that 300 g of 1,2,2- ~
trifluoropropane and 214 g of chlorine gas were used, and 200 g of CC14 was used as the solvent for the reaction.
The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 1-1.
'' . . .
.:
2 ~
Table 1-1 _ _ _ _ _ Example No. 1-1 1-2 1-3 1-4 _ . _ _ _ _ Conversion for CH2FCF2CH3 (~) 40 65 85 57 _ _ _ . _~ _. _ ,, .
Selectivity for CHClFCF2CH3 (~) 76 56 20 60 _ _ __ _ Selectivity for CCl2FCF2CH3 ~%) 8 18 29 20 _ _ _ _ . . .. _ . ..... . _ , .
Selectivity for CH2FCF2CH2Cl (%) 8 5 1 5 _ _ _ _ _ _ . . . . . ,.
Selectivity for CHClFCF2CH2C1 (%) _ _ 1 _ ~
. _ _ _ . ,._ _ _ _ Selectivity for CCl2FCP2CH2Cl (%) _ 2 5 1 ... ~ .
__ _ _ _ _ . __ _ ~ . _ .
Selectivity for CH2FCF2CHCl2 ~j%) 3 10 13 10 :
. _ _ _ _ _ _ _ _, _ . . _-- -- .
Selectivity for CHClFCF2CHCl2 (%) 1 _ 3 _ :
. ~ . . _ ~ _ _ ..
Selectivity for CCl2FCF2CHCl2 (%) 1 2 8 1 _ _ __~ _ .
Selectivity for CH2FCF2CC13 (~) 2 3 10 1 _ _ - _ _ _ ~, Selectivi.ty ~or CHClFCF2CC13 ~) _ 1 4 _ __ . __ _ __ _ _ : ,, Selectivity for CC12FCF2CCl3 ~) 1 2 6 2 _ _ ._ _ _ _ _ Other products (%) _ _ _ _ . _ _ Into a 1,000 cc Hastelloy C autoclave, 300 g of 1,2,2-trifluorolpropane and 20 g of di-~-butyl peroxide were charged. Then, thei temperature was raised to 120C, .
and while stirring, 214 g of chlorine gas was supplied at .: .
a rate of 50 g/hr over a period of 4 hours. Then, the reaction was continued for further 12 hours. The product 25 after removal of acid components, was analyzed by gas :
chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 1-2.
':' .
2~2~
The reaction was conducted in the same manner as in Example 1-5 except that 20 g of AIBN was used as a radical initiator. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 1-2.
~n Inconel 600 reactor having a~ inner diameter of 1.27 cm and a length of 20 cm, ~as maintained at 430C, and gasified 1,2,2-trifluoropropane and chlorine gas were supplied at a rate of 300 ml/min, respectively. The reaction was conducted continuously for 4 hours. The product ~fter removal of acid components was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 1-2.
Table 1-2 _ . _ _ _ . . _ _ _ Example NQ. 1-5 1-6 1-7 _ _ _ _ _ :. . ,.
Conversion for CH2FCF2CH3 (%) 56 45 50 _ _ . __ ~r_: ~
Selectivity for CHClFCF2CH3 (%) 47 60 42 . _ ~ _ _ _ _ _ _ Selectivity for CC12FCF2CH3 (~) 21 23 17 ~ . . . :
Selectivity for CH2FCF2CH2C1 (%) 5 7 2 . _ _ .
Selectivity for CHClFCE'2OEI2Cl (%) _ _ _ ._ _ . __ _ Seleativity for CC12FCF2CH2Cl (%) 1 1 _ _ _ __ _ _ Selectivity for CH2FCF2CHC12 (~) 12 6 5 . _ ~ _ _ .
Selectivity for CHClFCF2CHCl2 (%) _ _ 3 ~ . _ . ,_ .:
Selectivity for CC12FCF2CHC12 (%) 4 _ 4 -~ _ ~
Selectivity for CH2FCF2CCl3 (%~ 4 2 10 ~ __ _ ....
Selectivity for CHClFCF2CC13 (%) 2 _ 4 ~ _ _ . . , Selectivity for CC12FCF2CC13 (%) 4 1 6 ~
. . ~ . _ Other products (%) _ _ _ 7 _ _. __ . _ ' ,i, 2~2~
EX~MPLE 1-8 The reaction was conducted for 6 hours in the same manner as in Example 1-1 except that 300 g l-chloro- . :~
2,~,3-trifluoropropane and 160 g of chlorine gas were :
used. The product was analyzed by gas chromatography and ~i by l9F-NMR and lH-NMR. The results are shown in Table 1-3 :.:
. .
Table 1-3 -. , ~ _ Conversion for CH2ClCF2CH2F (%) 67 . , _ . , . .
Selectivity Eor CHCl2CF2CH2F ~) 52 Selectivity for CC13CF2CH2F ~%) 14 . . , Selectivity for CH2ClCF2CHClF t~) 18 .~
Selectivity Eor CHC12CF2CHClF (%) 7 ~ _ __ I ...
. . Selectivity for CC13CF2CHClF ~%) 4 , _ _ _ Selectivity for CH2ClCF2CCl2F ~%) 3 ~ .
Selectivity for CHC12CF2CC12F (%) 2 -:
_ _ _ , ~
Selectivity for CC13CF2CC12F (%) _ :. .
":' '.: ' The reaction was conducted for 6 hours in the same manner as in Example 1-1 except that 300 g oE l-chloro-1,2,2-trifluoropropane and 160 g of chlorine gas were used. The product was analyzed by gas chromatography and .
by l9F-NMR and lH-NMR. The results are shown in Table 1- :
2S 4~
':
"."' . .
',,' . -2 ~
Table 1-4 _ __ _ .
Conversion for CHClFCF2CH3 ~%) 77 Selectivity for CCl2FCF2CH3 (%) 77 . . _ _., _ _ ...
Selectivity for CHClFCF2CH2Cl (%) 4 , . , _ _ Selectivity for CCl2FCF2CH2Cl (%) 4 ~ _ ..
Selectivity for CHClFCF2CHCl2 (%) _ _ Selectivity for CCl2FCF2CHCl2 (%) 5 Selectivity for CHClFCF2CCl3 (%) 3 _ _ _ .
Selectivity for CCl2FCF2CCl3 (%3 1 EXAMPLE 1-10 .
The reaction was conducted for 6 hours in the same rnanner as in Example 1-1 except that 300 g of 1,3- :
dichloro-1,2,2-trifluoropropane and 130 9 of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 1-5.
Table 1-5 _ _ _ Conversion for CHClFCF2CH2Cl (~) 74 . .
20. _ _ _ Selectivity for CC12FCF2CH2C1 (~) 26 i Selectivity for CHClFCF2CHCl2 (%) 44 . .
_ _ _ . _ . _.
Selectivity for CCl2FCF2CHCl2 (~) 13 .
~ _ . ., Selectivit~ for CHClFCF2CCl3 (%) 12 _ _ , .
Selectivity for CCl2FCF2CCl3 (%) 5 ~2~6 i;~3 -EXAMPLE 1-11 ;
The reaction was conducted for 6 hours in the same manner as in Example 1-1 except that 300 g of 1,1-dichloro-2,2,3-trifluoropropane and 130 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 1-6.
'.... "
Table 1-6 ~ . _ . : .
Conversion for CHC12CF2CH2F (%) 73 _ _ . . .
10Selectivity for CCl3CF2CH2F (%) 57 :~
, _ _ _ _ _ : i .
Selectivity for CHC12CF2CHClF (%) 11 _ _ _ Selectivity for CC13CF2CHClF (%) 25 .. :
_ : ':
Selectivity ~or CHC12CF2CC12F (~i) 3 . _ Selectivity for CC13CF2CC12F ~i) 4 :
The reaction was conducted for 6 hours in the same .
manner as in Example 1-1 except that 300 g of 1,1- .
dichloro-1,2,2-trifluoropropane and 130 g of chlorine gas 20 were used, The product was analyzed by gas ~.
chromatography and by 19F-NMR and l~-NMR. The results are shown in Table 1-7. ~.
- 2~2~6~3 Table 1-7 _ . _ _ _ _ _ ..
Conversion for CC12FCF2OEI3 ~ 40 Selectivity for CCl2FCF2CH2Cl (%) _ _ Selectivity for CCl2FCF2CHCl2 (%) 67 Selectivity for CCl2FCF2CCl3 (%) 29 The reaction was conducted for 6 hours in the same ~.
manner as in Example 1-1 except that 300 g of 1,1,3-trichloro-2,2,3-trifluoropropane and 105 g of chlorine ga~ were used. The product was analyzed by gas chromatography and by l9F-NMR and l~I~NMR. The results are shown in Table 1-8.
Table 1-8 . _ Conversion for CHCl2CF2CHClF (%) 85 .. ._ _ _ _ . _ . ~ .
Selectivity for CCl3CF2CHClF (%) 70 Selectivity for CHC12CF2CC12F ~) 20 ISelectivity for CCl3CF2CCl2F (%) 10 `.
The reaction was conducted for 6 hours in the same manner as in Example 1-1 except that 300 g of 1,1,3-trichloro-1,2,2-trifluoropropane and 53 g of chlorine gas .:
were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 1-9.
:'.
2 ~
Table 1-9 Conversion for CC12FCF2CH2Cl t~) 38 :.
_ . . T . _ _ .
Selectivity for CC12FCF2CHCl2 (%) 78 _~
~ ~ ~ _ 22 ~, S
The reaction was conducted for 6 hours in the same .~.
manner as in Example 1-1 except that 300 g of 1,1,1- :
trichloro-2,2,3-trifluoropropane and 53 g oE chlorine gas were used. The product was analyzed by gaæ
chromatography and by l9F-NMR and lH-NMR. q'he results are shown in Table 1-10.
Table 1-10 _ _ .
Conversion for CCl3CF2CH2F (%) 38 _ . ~
Selectivity for CCl3CFzCHClF (%) 78 ..
. _ _ _ _ _ _ .
Selectivity for CCl3CF2CCl2F (%) 22 EXAMP~E 1-16 The reaction was conducted for 6 hours in the same manner as in Example 1-1 except that 300 g of 1,1,3,3-tetrachloro-1,2,2~trifluoropropane and 90 g of chlorine ga9 were u5ed. The product was analy2ed by gas chromatography and by 19F-NMR and lH-NMR The results are shown in Table 1-11. 7 " ' '"
2~2~6~ ~:
--Table 1-11 . _ Conversion for CC12FCF2CHC12 (%) 98 ISelectivity for CCl2FCF~CCl3 (%) 100 EXAMPLE 1-17 ~ .
~ he reaction was conducted for 6 hours in the same manner as in Example 1-1 except that 300 9 of 1,1,1,3-tetrachloro-2,2,3-trifluoropropane and 90 9 of chlorine gas were used. The product was analyzed by gas chromatography and by l9F-NMR and lH-NMR. The results are shown in Table 1-12.
Table 1-12 .. _ _ _ . . .
. Conversion or CC13CF2CHClF t%) 97 . I . ~
Selectivity for CCl3CF2CCl2~ (%) 100 :~
~.
A 1,000 cc glass reactor e~uipped with a condenser o~
-78C, was cooled to -20C, and 300 g of 1,2,2,3-tetrafluoropropane was charged. Then, 95 9 of chlorine gas was gradually introduced while stirring under irradiation by a high pressure mercury lamp of 500 W.
After the reaction for 6 hours, the product after removal :
25 o~ acid components, was analyzed by gas chromatography :.
and by 19F-NMR and IH-NMR. The results are shown in ~ :
- .:
Table 2-1. ~
. . .
. :
~. .
~ ~ 2 ~
- lB -The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g o~ 1,2,2,3-tetrafluoropropane and 185 g of chlorine gas were used.
The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 2 - The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g of 1,2,2,3-tetrafluoropropane and 370 g of chlorine gas were used.
The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 2-1.
The reaction was conducted Eor 6 hours in the same lS manner as in Example 2-1 except that 300 g of 1,2,2l3-tetxafluoropropane, 185 g oE chlorine gas and 200 9 of CC14 as a solvent were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 2~1.
6 ~
Table 2-1 . . _ __ .
Example N~. 2-1 2-2 2-3 2-4 _ _ , _ .
Conversion for CH2FCF2CH2F (%) 40 66 92 65 Selectivity for CHClFCF2CH2F (%) 90 61 30 70 _ . _~ ,, ,_ Selectivity for CCl2FCF2CH2F (%) 5 18 25 15 ~ _, . _ ~ ~
Selectivity for CHClFCF2CHClF (~ 3 11 15 g _ . _ . _ _ _ Selectivity for CCl2FCF2CHClF (%) 2 8 19 5 . _ _ _ _ _ _ _ . ., .__ . , Selectivity for CCl2FCF2CClF2 (~) _ 2 11 1 . . ~ . , _. _ . . ,' Into a 1,000 cc Hastelloy C autoclave, 300 g of 1,2 r 2,3-tetrafluorolpropane and 20 g of di t-butyl peroxide were charged. Then, the temperature was raised to 120C, and while stirring, 185 g of chlorine gas was supplied at a rate of 50 g/hr over a period of 4 hours.
Then, the reaction was continued for further 12 hours.
The product ater removal of acid components, was analyzed by gas chromatography and by l9F-NMR and l~-NMR.
~he results are shown in Table 2-2.
EXAMP~E 2-6 The reaction was conducted in the same manner as in Example 2-5 except that 300 g of 1,2,2,3-tetrafluoropropane and 20 g of AIBN as a radical initiator were used. The product was analy~ed by gas , ~ ., , .
2 0 2 6 ~ 6 ~
ch~omatography and by l9F-NMR and lH-NMR. The results are shown in Table 2-2.
An Inconel 600 reactor having an inner diameter of 1.27 cm and a length of 20 cm, was maintained at 430C, and gasified 1,2,2,3-tetra~luoropropane and chlorine gas were supplied at a rate of 150 ml/min, xespectively. The reaction was conducted continuously for 4 hours. The product after removal of acid components was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 2-2.
Table 2-2 Example No. 2-5 Z-6 2-7 ,- _ Conversion Eor CH2FCF2CH2F ~%) 50 35 54 15Selectivity for CHClFCF2CH2F ~) 60 66 53 _ _ _ , Selectivity ~or CC12FCF2CH2F (~) 15 12 16 . ~ ~ . . . . ..
Selectivity for CHClFCF2CHClF (%) 11 7 12 ~ -, ~ _ _ _ _ _ . , .
Selectivity for CC12FCF2CHClF (%) 10 5 7 ,. _ _ .
Selectivity for CC12FC~2CC12F (%) 4 3 5 _ _ . _ . -- . .
. .
EX~MPLE 2-8 The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 9 of 1,1,2,2-tetrafluoropropane and 185 g of chlorine gas were usedand the reaction was carried out at -30C. The product was analyzed by gas chromatography and by l9F-NMR and lH-. .
, , . . . . . .... .. : .. ; .. .. . ,.. ., ,;, ,. . . ~ . .,., ", ~, : .. .,:. . . . .
2~2~6`~
,. .. :
NMR. The results are shown in Table 2-3.
Table 2-3 _ , _ ~
Conversion for CHF2CF2CH3 (%? 54 Selectivity for CClF2CF2CH3 (~) 45 _ _ _ _ _ . __ _ _ Selectivity for CHF2CF2CH2C1 (%) 2 . . . _ .
Selectivity for CClF2CF2CH2Cl (%) 4 ~ . .
Selectivity for CHF2CF2CHCl2 (%) 20 .~ .
_ . .
Selectivity for CClF2CF2CHCl2 (%) 13 Selectivity for CHF2CF2CC13 (%) 15 . . -Selectivity for CClF2CF2CCl3 (%) l :
. _ "... ..
. . . .
The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g oE l-chloro-2,2,3,3-tetrafluoropropane and 140 g of chlorine gas were .
used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 2-4. ;!
Table 2-4 ___ ~ . -Conversion ~or CH2ClCF2CHF2 (%) 57 :~
. __ . .
Selectivity ~ 4 : Selectivity for CHCl2CF2CHF2 (%) 12 , _ . _ _ _ . _ _ ~ __. . ..
Selectivity for CHCl2CF2CCl~2 ~) _ Selectivity for CC13CF2CHF2 (~) 21 . .. _ _ ___,_ . , :
Selectivity ~or CC13CF2CClF2 (%) l . :
, _ _ _ _ _ . ~ .-- ' , .
, ~2~ ~3~ ~
The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g of l-chloro-1,2,2,3-tetrafluoropropane and 140 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 2-5.
Table 2-5 , , , , _ . , ..
Conversion for C~ClFCF2CH2F ~%) 80 , ,, ............. _ . . .
10Selectivity for CCl2FCF2CH2F ~%) 54 _ . .... . . _ ..
Selectivity ~or CHClFCF2CHClF (%) 28 .. ... . ............. . _ .
Selectivity for CC12FCF2C~ClF ~%) 16 , ...... . __ _ :..
The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g of l-chloro- -1,1,2,2-tetrafluoropropane and 140 g of chlorine gas were usedO The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 2-6.
Table 2-6 . ..
l Conversion for CClF2CF2CH3 (%) . .
~ _ ~) S
Selectivity for CClF2CF2CHC12 (%) 65 .. . - . . . . . ~
SPlectivity for CClF2CF2CC13 (%) 30 : .
2 ~
The reaction was conducted for 6 hours in the same manner as in Example 2-l except that 300 g oE 1,3-dichloro-1,2,2,3-tetrafluoropropane and 115 9 of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-~MR and lH-NMR. The results are shown in Table 2-7.
Table 2-7 _ _ . _ , .
Conversion for CHClFCF2CHClF (%) 88 , _ . __ __ _ 10Selectivity for CCl~FCF2CHClF (%) ~9 : :
. _ . _ ~
5electivity for CCl2FCF2CCl2F (%) 11 :
~ _ ,:
The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 9 of l,l- ~:
dichloro-2,2,3,3-tetrafluoropropane and 115 9 of chlorine gas were used. The product was analyzed by gas :.
chromatography and by 19F-NMR and lH-NMR. The results ~ .
20 are shown in Table 2-8.
q'able 2-8 Conversion for C~IC12CF2CHF2 ~) 95 _ _ , ,.
Selectivity for CC13CF2CHF2 (%) 97 ..
. _ __ _ Selectivity for CHC12CF2CC1~2 (~) 3 : ~ :
. . _, _ ~ ___ . .
Selectivity for CCl3CF2CClF2 (%) _ : -_ __ __ . :.. :" .
, .....
2 ~ 2 ~ ~ 6 b The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g of 1,3-dichloro-1,1,2,2-tetrafluoropropane and 58 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 2-9.
~ ;~
Table 2-9 . _ . .
Conversion for CClF2CF2CH2Cl (%) 35 , .
Selectivity for CClE'2CF2CHC12 (%) 80 ~ . ~
Selectivity for CClE`2CF2CCl3 (~) 20 . _ _ EXAMPhE 2-15 The reaction was conducted for 6 hours in the same manner as in Example 2-1 except ~hat 300 9 of 1,1-dichloro-1,2,2,3-tetrafluoropropane and 58 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 2-10.
~able 2-10 _ Conversion ~or CC12FCE'2CH2F (%) 38 -:
_ _ Selectivity for CC12FCF2CHClF ~%) 78 ~ ~
, _ _ . . . .
Selectivity ~or CCI~/Cr~CCI~ 22 ;
2~26~
The reaction was conducted for 6 hours in the same manner as in Example 2-l except that 300 9 o~ l,1,3-trichloro-2,2,3,3-tetrafluoropropane and lO0 g of chlorine gas were used. The product was analy~ed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 2-ll.
Table 2-11 _ _ _ _ Conversion for CHC12CF2CClF2 (%) 98 . ,~_ _ _ _ . .
lUSelectivity ~or CC13CF2CClF3 (%) 100 ._ _ __._ .. :'' ':
. . ,:
The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g of 1,1,3-trichloro-1,2,2,3-tetrafluoropropane and 100 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results 20 are shown in Table 2-12.
:. ::..
Table 2-12 __ __ _ .
Conversion for CCl2FCF2C~IClF ~%~ 97 ~.
. . .
Selectivity for CC12FCF2CCl2F (%) 100 - 26- 2~2~ 3 The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g of 1,1,1-trichloro-2,2,3,3-tetrafluoropropane and 100 9 of chlorine gas were used. The product was analyzed by gas chromatography and by l9F-NMR and lH-NMR. The results are shown in Table 2-13.
Table 2-13 ~ r - ~
Conversion for CCl3CF2CEF2 (%) ¦ 91 ..
_ . _ _ I _ _ . .
Selectivity Eor CC13CF2CClF2 (% ~ 100 EXAMPLE 3-1 .
A 1,000 cc glass reactor equipped with a condenser of -78C, was cooled to -20C, and 300 g of 1,1,2,2,3-pentafluoropropane was charged. Then, 80 g oE chlorine gas was gradually introduced while stirring under irradiation by a high pressure mercury lamp of 500 W.
A~ter the reaction for 6 hours, the product after removal oE acid components, was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 3-1.
The reaction was conducted for 6 hours in the same manner as in Example 3-1 except that 300 g of 1,1,2,2,3- .
pentafluoropropane and 160 g of chlorine gas were used.
' ', '' ', '.
2 ~
The product was analy~ed by gas chromatography and by l9F-NMR and lH-NMR. The results are shown in Table 3-1.
EX~MPLE 3-3 The reaction was conducted for 6 hours in the same manner as in Example 3-1 except that 300 g of 1,1,2,2,3-pentafluoropropane and 320 9 of chlorine gas were used.
The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Ta~le 3-1. ~:~
The reaction was conducted for 6 hours in the same manner as in Example 3~1 except that 300 g Of 1 r 1 r 2,2,3-pentafluoropropane, 160 g o~ chlorine gas and 200 g oE
CC14 as a solvent were used. q'he product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 3-1.
.:~
....... ..
.,:. ~, Table 3-1 .~
_ _ _ _ ~
Example No. 3-1 3-2 3-3 3-4 __ _ _ _ __ Conversion for CHF2CF2CH2F ~i)32 60 97 55 ..
_ _ _ Selectivity for CClF2CF2C~2F (%) 12 12 4 12 ~ . . _ . _ ...
Selectivity for CHF2CF2CHClF (~i) 78 71 20 75 . ..
_ _ _ _ . . _ _ _ . .... ..
Selectivity for CClF2CF2CHClF (%): . 2 5 12 4 . : ~ _ . . _ _ Selectivity for CHF2CF2CC12F (%) 8 11 47 8 .
~_ _ -- . ! - ' Selectivity for CC}F2CF2CC12F (%) . ~ 1 17 1 _ . - . _ _ _ .
. .. . .... .... ..
2632~6i~
Into a l,000 cc Hastelloy C autoclave, 300 g of 1 j1,2,2, 3-pentafluorolpropane and 20 g oE di-t-butyl peroxide were charged. Then, the temperature was raised to 120C, and while stirring, 200 g of chlorine gas was supplied at a rate of 50 g/hr over a period of 4 hours.
Then, the reaction was continued for further 12 hours.
The product after removal of acid components, was analyzed by gas chromatography and by 19F-NMR and lH-NMR.
The results are shown in Table 3-2.
EXAMPLE 3-6 ;
The reaction was conducted while 200 g of chlorine gas was supplied at a rate of 50 g/hr for 4 hours in the same manner as in Example 3-5 except that 300 g of 15 1,1,2,2,3-pentafluoropropane and 20 g of AIBN as a radical initiator were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 3-2.
EXAMPLE 3-7 ~ -An Inconel 600 reactor having an inner diameter of 1,27 cm and a leng~h of 20 cm, was maintained at 430C, and gasified 1,1,2,2,3-pentafluoropropane and chlorine gas were supplied at a rate of 150 ml/min, respectively.
The reaction was conducted continuously for 4 hours. The product after removal of acid components was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 3-2.
, . , ,', . '. . ' ~' ' .; " ' ' " " " ~ .' ' ' " ' ' " ' ', '' " ' '' , ', ' ~ ' ', ' ' , ' ' ' ,., ' " ' ' ' 2 ~
Table 3-2 . _. _ ~ . .
Example No. 3-5 3-6 3-7 _ __ .
Conversion for CHF2CF2CH2F (%) 60 45 50 _ . ,_ Selectivity for CClF2CF2CH2F (%)15 12 20 S - . . ............................. _ .
Selectivity for CHF2CF2CHClF (~) 58 62 58 . . . . , , . ._ ~ ~ _ . . _ Selectivity for CClF2CF2CHClF (%) 5 6 ~ :
Selectivity for CHF2CF2CC12F ~%) 17 15 9 ..
. . ~ _ . . .
Selectivity for CClF2CF2CCl2F (%) ~ ~ 5 6 - . :' EXAMPLE 3-8 ::
The reaction was conducted for 6 hours in the same manner as in Example 3-1 except that 300 g of 1,1,1,2,2-pentafluoropropane and 160 g of chlorine gas were used and the reaction was carried out at -30C. The product was analyzed by gas chromatography and by 19F-NMR and lH- `
NMR. The results are shown in Table 3-3.
Table 3-3 ~ __ Conversion for CF3CF2CH3 (%) 40 Selectivity for CF3CF2CH2Cl (~) 6 . :.:
_ .................. ,.. _ ... . i ' Selectivity for CF3CF2CHC12 (~) 64 . ., .
Selectivity for CF3CP2CC13 (%) 30 ~ ' '',' ' ,~
'.
.':' , 2 ~ 6 ~ :
The reaction was conducted for 6 hours in the same manner as in Example 3-1 except that 300 g of l-chloro-1,2,2,3,3-pentafluoropropane and 130 9 of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 3-4.
Table 3-4 . _ _ _ . _ ~ 9~ . ~"
Selectivity for CC12FCF2CHF2 (%) 90 _ ..
Selectivity for CHClFCF2CClF2 (%) 8 _ _ _ _ __ Selectivity for CC12FCF2CClF2 (%) 2 The reaction ~as conducted for 6 hours in the same manner as in Example 3-1 except that 300 g of l-chloro-2,2,3,3,3-pentafluoropropane and 65 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 3-5.
¦convers~ ~ F 3 1 : Selectivit ~ 9 2:5 ~ ~ 19 i ~ .
2 a~
The reaction was conducted for 6 hours in the same mianner as in Example 3-1 except that 300 g of l-chloro-1,1,2,2,3-pentafluoropropane and 65 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results ;~ .
are shown in Table 3-6.
Table 3-6 _ _ _ _ _ Conversion for CClF2CF2CH2F (~i) 36 __ ..
10Selectivity for CClF2CF2CHClF (%) 76 .
_ . . . ~ _ Selectivity for CClF2CF2CC12F ~%) 24 The reaction was conducted for 6 hours in the same `:
manner as in Example 3-1 except that 300 g of 1,1- :.
dichloro-2,2,3,3,3-pentafluoropropane and 105 g of chlorine gas were used. The product was analyzed by gas , chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 3-7. :':
Table 3-7 _ , .
IConversion for CF3CF2CHC12 (~) _ _ 25j5electivity for cr~Cr~cc~ ) 100 ::
; ~
'.
. i ~2~6~
The reaction was conducted for 6 hours in the same manner as in Example 3-l except that 300 y of 1,3-dichloro-1,1,2,2,3-pentafluoropropane and 105 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 3-8.
Table 3-8 . _ _ _ _ _ _ _ Conversion for CClF2CF2CHClF (%) 97 , ~ . .
Selectlvity for CClF2CF2CCl2F ~%) lO0 r . . _ ____ . - _ _ . .
The reaction was conducted for 6 hours in the same manner as in Example 3-1 except that 300 g of l,l-dichloro-1,2,2,3,3-pentafluoropropane and 105 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 3 9.
Table 3-9 . . _ ..
Conversion for CCl2FCF2CHF2 t%) 91 _ _ Selectivity for CCl2FCF2CClF2 (%) lO0 _ _ , __ _ ~5 .
2~26~
- 33 - :
A 1,000 cc glass reactor equipped with a condenser of -78C, was cooled to -20C, and 300 g of 1,1,2,2,3,3- -hexafluoropropane was charged. Then, 70 g of chlorine gas was gradually introduced while stirring under irradiation by a high pressure mercury lamp of 500 W.
After the reaction for 6 hours, the product after removal of acld components, was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in ;~
Table 4-1.
The reaction was conducted for 6 hours in the same manner as in Example 4-1 except that 300 g of ;~
1,1,2,2,3,3-hexafluoropropane and 140 g of chlorine gas lS were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 4-1.
EXAMP~E 4-3 The reaction was conducted for 6 hours in the same manner as in Example 4-1 except that 300 g of 1,1,2,2,3,3-hexafluoropropane and 280 g of chlorine gas were used. The product was analyzed by gas chromatography and by l9F-NMR and lH-NMR. The results are shown in Table 4-1.
ExAMpLE 4-4 The reaction was conducted for 6 hours in the same manner as in Example 4-1 except that 300 g of ~2~6~
~ 34 -1,1,2,2,3,3-hexafluoropropane, 140 g of chlorine gas and 200 g of CC14 as a solvent ~ere used~ The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR.
The results are shown in Table 4-1.
Table 4-1 . . . ._ . , _ . , .. . _ ..
Example No. 4-1 4-2 4-3 4-4 . . . . . . . . . ~ _ Conversion for CHF2CF2CHF2 (%) 32 64 92 52 . . _ Selectivity for CClF2C~2CHF2 t%) 98 81 32 89 .~ . . . _ ~ . . . ,._ Selectivity for CClF~CF2CClF2 (%) 2 19 68 11 . _ . . . . . ., Other products (~) _ _ _ . _ . _ _ . _ .
, Into a 1,000 cc ~astelloy C autoclave, 300 9 of 1,1,2,2,3,3-hexafluorolpropane and 20 g of di-t~butyl peroxide were charged. Then, the temperature was raised to 120C, and while stirring, 160 g of chlorine gas was supplied at a rate o~ 40 g/hr over a period of 4 hours.
Then, the reaction was continued for further 12 hours.
The product a~ter removal o~ acid components, was -- analyzed by gas chromatography and by l9F-NMR and l~-NMR.
The results are shown in Table 4-2.
EXAMP~E 4-6 The reaction was conducted in the same manner as in :~ "
` ;;
.
, , .
2 a 2 ~
Example 4-5 except that 300 9 of 1,1,2,2,3,3-hexafluoropropane and 20 g of AIBN as a radical initiator were used. 160 of chlorine gas was supplied at a rate of 40 g/hr over a period of 4 hours, and then the reaction :
was continued for further 12 hours. The product was analyzed by gas chromato~raphy and by 19F-NMR and lH-NMR.
The results are shown in Table 4-2. ~.
An Inconel 600 reactor having an inner diameter of ~' 1.27 cm and a length of 20 cm, was maintained at 430~C, and gasified 1,1,2,2,3,3-hexafluoropropane and chlorine gas were supplied at a rate of 150 ml/min, respectively. ;
The reaction was conducted continuously for 4 hours. The product after removal o acid components was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 4-2.
Table 4-2 _ . _ __ .................... .. _ ,.:'.
Example No. 4-5 4-6 4-7 -~ _ . _ _ _ __ _ _ __ Conversion for CHF2CF2CHF2 (%) 50 25 66 - _ _ ~ _ __ Selectivity for CClF2CF2CHF2 (%) 80 95 72 . _ __ .
Selectivity Eor CClF2CF2CClF2 ~%) 20 __ 20 Other products ~) _ _ 8 .. ~ ,. _ _ ,."~
, :' 2 ~ 6 ~
The reaction was conducted for 6 hours in the same manner as in Example 4-1 except that 300 9 of 1,1,1,2,2,3-hexafluoropropane and 70 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMRo The results are shown in Table 4-3.
Table 4-3 ~ ..
Conversion for CF3CF2CH2F (%) 38 1 0 , . ~
Selectivity for CF3CF2CHClF (%) 74 _ _ _ _ .
Selectivity for CF3CF2CC12F (%) 26 ~:
. "
The reaction was conducted for 6 hours in the same manner as in Example 4-1 except that 300 g of l-chloro-1,2,2,3,3,3-hexafluoropropane and 120 9 of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 4-4.
Table 4-4 :
. _ _ _ _.
Conversion for CF3CF2CHClF (~i) 97 . ~ . ' ~:
Selectivity for CF3CF2C.Cl2F (%) 100 . .
_ _ . .
',:
., .:
,', ' ~'':
:, :.
~ ~ 2 ~
The reaction was conducted for 6 hours in the same manner as in Example 4-1 except that 300 g of l-chloro-1,1,2,2,3,3-hexafluoropropane and 120 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and lH-NMR. The results are shown in Table 4-S.
Table 4-5 :
. , , , Conversion for CClF2CF2CHF2 (%) 95 :.
. . _ ., Selectivity for CClF2CF2CClF2 (%) 100 ;.
The present invention is effective for producing a chlorine-containing 2,2~difluoropropane sele~tively by chlorinating a 2,2-difluoropropane.
~, . ,, , . , . ,, . . . - . .. ..
. . : . ........ . . ............. . ....... .
.. . . . . ..
Claims (7)
1. A process for producing a chlorine-containing 2,2-difluoropropane of the following formula (2), which comprises chlorinating a 2,2-difluoropropane of the following formula (1):
C3HaClbFc (1) C3Ha-xClb+xFc (2) wherein a, b, c and x are integers satisfying the following conditions:
a ? 1, b ? 0, c ? 2, x ? 1 and a + b + c = 8.
C3HaClbFc (1) C3Ha-xClb+xFc (2) wherein a, b, c and x are integers satisfying the following conditions:
a ? 1, b ? 0, c ? 2, x ? 1 and a + b + c = 8.
2. The process according to Claim 1, wherein the chlorination is conducted in the presence of a radical-generating source.
3. The process according to Claim 2, wherein the radical-generating source is light, heat or a radical initiator.
4. The process according to Claim 1, wherein the 2,2-difluoropropane of the formula (1) is C3Hm1Cl5-mF3 (1 ?
m1 ? 5), and the chlorine-containing 2,2-difluoropropane of the formula (2) is C3Hn1Cl5-n1F3 (0 ? n1 ? 4, m1 >
n1).
m1 ? 5), and the chlorine-containing 2,2-difluoropropane of the formula (2) is C3Hn1Cl5-n1F3 (0 ? n1 ? 4, m1 >
n1).
5. The process according to Claim 1, wherein the 2,2-difluoropropane of the formula (1) is C3Hm2Cl4-m2F4 (1 ?
m2 ? 4), and the chlorine-containing 2,2-difluoropropane of the formula (2) is C3Hn2Cl4-n2F4 (0 ? n2 ? 3, m2 >
n2).
m2 ? 4), and the chlorine-containing 2,2-difluoropropane of the formula (2) is C3Hn2Cl4-n2F4 (0 ? n2 ? 3, m2 >
n2).
6. The process according to Claim 1, wherein the 2,2-difluoropropane of the formula (1) is C3Hm3Cl3-m3F5 (1 ?
m3 ? 3), and the chlorine-containing 2,2-difluoropropane of the formula (2) is C3Hn3Cl3-n3F5 (0 ? n3 ? 2, m3 >
n3).
m3 ? 3), and the chlorine-containing 2,2-difluoropropane of the formula (2) is C3Hn3Cl3-n3F5 (0 ? n3 ? 2, m3 >
n3).
7. The process according to Claim 1, wherein the 2,2-difluoropropane of the formula (1) is C3Hm4Cl2-m4F6 (1 ?
m4 ? 2), and the chlorine-containing 2,2-difluoropropane of the formula (2) is C3Hn4Cl2-nF6 (0 ? n4 ? 1, m4 >
n4).
m4 ? 2), and the chlorine-containing 2,2-difluoropropane of the formula (2) is C3Hn4Cl2-nF6 (0 ? n4 ? 1, m4 >
n4).
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1-22543 | 1989-02-02 | ||
| JP2254389A JPH02300142A (en) | 1989-02-02 | 1989-02-02 | Production of chlorinated tetrafluoropropanes |
| JP1-22551 | 1989-02-02 | ||
| JP2254489A JPH02204423A (en) | 1989-02-02 | 1989-02-02 | Production of chlorinated pentafluoropropanes |
| JP2255289A JPH02204430A (en) | 1989-02-02 | 1989-02-02 | Production of chlorinated trifluoropropanes |
| JP2255189A JPH02204429A (en) | 1989-02-02 | 1989-02-02 | Production of chlorinated hexafluoropropanes |
| JP1-22552 | 1989-02-02 | ||
| JP1-22544 | 1989-02-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2026566A1 true CA2026566A1 (en) | 1990-08-03 |
Family
ID=27457790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2026566 Abandoned CA2026566A1 (en) | 1989-02-02 | 1990-02-01 | Process for producing a chlorine-containing 2-2-difluoropropane |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0407619A1 (en) |
| CA (1) | CA2026566A1 (en) |
| WO (1) | WO1990008752A1 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9315450D0 (en) * | 1993-07-26 | 1993-09-08 | Zeneca Ltd | Chlorination process |
| US7880040B2 (en) | 2004-04-29 | 2011-02-01 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
| US9308199B2 (en) | 2004-04-29 | 2016-04-12 | Honeywell International Inc. | Medicament formulations |
| US20080275284A1 (en) | 2004-04-16 | 2008-11-06 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
| US7674939B2 (en) | 2004-04-29 | 2010-03-09 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
| US7951982B2 (en) | 2004-04-29 | 2011-05-31 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
| MXPA06012468A (en) | 2004-04-29 | 2007-01-29 | Honeywell Int Inc | Processes for synthesis of 1,3,3,3-tetrafluoropropene. |
| US7659434B2 (en) | 2004-04-29 | 2010-02-09 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
| US8383867B2 (en) | 2004-04-29 | 2013-02-26 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
| WO2007056148A1 (en) * | 2005-11-03 | 2007-05-18 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
| KR101740419B1 (en) | 2008-07-18 | 2017-05-26 | 지알티, 인코포레이티드 | Continuous process for converting natural gas to liquid hydrocarbons |
| US8367884B2 (en) | 2010-03-02 | 2013-02-05 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
| US9193641B2 (en) | 2011-12-16 | 2015-11-24 | Gtc Technology Us, Llc | Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems |
| WO2023164093A2 (en) * | 2022-02-25 | 2023-08-31 | The Chemours Company Fc, Llc | Synthesis of hfo-153-10mczz including catalytic coupling of hcfc-225ca or cfc-215cb |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1004606A (en) * | 1962-05-15 | 1965-09-15 | Ici Ltd | 3:3-dichloro-1:1:2improvements2-tetrafluoropropane |
| GB1171202A (en) * | 1966-02-18 | 1969-11-19 | Squibb & Sons Inc | Preparation of Pentafluorochloropropane |
| DE3017154A1 (en) * | 1980-05-05 | 1981-11-12 | Hoechst Ag, 6000 Frankfurt | METHOD FOR PRODUCING 2-CHLORINE-1,1,1,2,3,3,3, -HEPTAFLUOR-PROPANE |
-
1990
- 1990-02-01 CA CA 2026566 patent/CA2026566A1/en not_active Abandoned
- 1990-02-01 WO PCT/JP1990/000121 patent/WO1990008752A1/en not_active Application Discontinuation
- 1990-02-01 EP EP19900902676 patent/EP0407619A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| EP0407619A1 (en) | 1991-01-16 |
| WO1990008752A1 (en) | 1990-08-09 |
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