WO1990008752A1 - Process for producing a chlorine-containing 2,2-difluoropropane - Google Patents

Process for producing a chlorine-containing 2,2-difluoropropane Download PDF

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WO1990008752A1
WO1990008752A1 PCT/JP1990/000121 JP9000121W WO9008752A1 WO 1990008752 A1 WO1990008752 A1 WO 1990008752A1 JP 9000121 W JP9000121 W JP 9000121W WO 9008752 A1 WO9008752 A1 WO 9008752A1
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nmr
reaction
hours
chlorine
product
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PCT/JP1990/000121
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French (fr)
Inventor
Shinsuke Morikawa
Shunichi Samejima
Hidekazu Okamoto
Keiichi Ohnishi
Shin Tatematsu
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Asahi Glass Company Ltd.
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Priority claimed from JP2254389A external-priority patent/JPH02300142A/en
Priority claimed from JP2254489A external-priority patent/JPH02204423A/en
Priority claimed from JP2255289A external-priority patent/JPH02204430A/en
Priority claimed from JP2255189A external-priority patent/JPH02204429A/en
Application filed by Asahi Glass Company Ltd. filed Critical Asahi Glass Company Ltd.
Publication of WO1990008752A1 publication Critical patent/WO1990008752A1/en

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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

Definitions

  • the present invention relates to a process for producing a chlorine-containing 2,2-difluoropropane.
  • the present inventors have conducted an extensive 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 substituting 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 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 chlorofluorocarbons. Particularly, it includes a promising substitute for 1,1,2- trichlorotrifluoroethane as a solvent.
  • the 2,2-difluoropropane (C 3 H in iCl 5 _ m i 3 wherein 1 ⁇ ⁇ p 2 ⁇ 5) to be used as the starting material includes, for example, 1,2,2-trifluoropropane (R-263c), l-chloro-2,2,3- trifluoropropane (R-253ca), l-chloro-1,2,2- trifluoropropane (R-253cb), l,3-dichloro-l,2,2- trifluoropropane (R-243ca), l,l-dichloro-2,2,3- trifluoropropane (R-243cb), l,l-dichloro-l,2,2- trifluoropropane (R-243cc), l,l-dichloro-l,2,2- trifluoropropane (R-243cc), l,l,3-trichloro-l,2,2- trifluoropropane (R-233
  • the chlorine-containing 2,2-difluoropropane (C 3 H n ⁇ Cl 5 _ n ⁇ F 3 wherein 0 ⁇ n 1 ⁇ 4) to be formed by the reaction includes l-chloro-2,2,3-trifluoropropane (R- 253ca), 1-chloro-l,2,2-trifluoropropane (R-253cb), 1,3- dichloro-1,2,2-trifluoropropane (R-243ca), 1,1-dichloro- 2,2,3-trifluoropropane (R-243cb), l,l-dichloro-l,2,2- trifluoropropane (R-243cc), l,l,3-trichloro-2,2,3- trifluoropropane (R-233ca), l,l,3-trichloro-l,2,2- trifluoropropane (R-233cb), l,l,l-trichloro-2,2,3- tri
  • 1,2,2,3-tetrafluoropropane R-254ca 1,1,2,2- tetrafluoropropane (R-254cb , l-chloro-2,2,3,3- tetrafluoropropane (R-244ca r l-chloro-1,2,2,3- tetrafluoropropane (R-244cb , 1-chloro-l,1,2,2- tetrafluoropropane (R-244cc , 1,3-dichloro-l,2,2,3- tetrafluoropropane (R-234ca , l,l-dichloro-2,2,3,3- tetrafluoropropane (R-234cb , l,3-dichloro-l,l,2,2- tetrafluoropropane (R-234cc , l,l-dichloro-l,2,2,3- tetrafluoropropane (R-2
  • the chlorine-containing 2,2-difluoropropane (C 3 H n Cl 4 . n 2F 4 wherein 0 ⁇ n 2 ⁇ 3) to be formed by the reaction includes l-chloro-2,2,3,3-tetrafluoropropane (R- 244ca), 1-chloro-l,2,2,3-tetrafluoropropane (R-244cb), 1- chloro-1,1,2,2-tetrafluoropropane (R-244cc), 1,3- dichloro-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- dichloro-1,2,2,3-tetrafluoropropane (R-234cd) , 1,1,3- trichloro-2,2,
  • 3 to be used as the starting material includes 1,1,2,2,3-pentafluoropropane (R-245ca), 1,1,1,2,2- pentafluoropropane (R-245cb), 1-chloro-l,2,2,3,3- pentafluoropropane (R-235ca), l-chloro-2,2,3,3,3- pentafluoropropane (R-235cb), 1-chloro-l,1,2,2,3- pentafluoropropane (R-235cc), l,l-dichloro-2,2,3,3,3- pentafluoropropane (R-225ca), l,3-dichloro-l,l,2,2,3- pentafluoropropane (R-225cb) and l,l-dichloro-l,2,2,3,3- pentafluoropropane (R-225cc).
  • the chlorine-containing 2,2-difluoropropane (C 3 H n3 Cl 3 _ n3 F 5 wherein 0 ⁇ n 3 ⁇ 2) to be formed by the reaction includes l-chloro-l,l,2,2,3,3-pentafluoropropane (R-235ca), l-chloro-2,2,3,3,3-pentafluoropropane (R- 235cb), l-chloro-l,l,2,2,3-pentafluoropropane (R-235cc), l,l-dichloro-2,2,3,3,3-pentafluoropropane (R-225ca), 1,3- dichloro-1,1,2,2,3-pentafluoropropane (R-225cb) , 1,1- dichloro-l,2,2,3,3-pentafluoropropane (R-225cc), 1,1,3- trichloro-1,2,2,3,3-pentafluor
  • the 2,2-difluoropropane (C 3 H r ⁇ 4 Cl 2 _ ⁇ n4 F 6 wherein 1 ⁇ m 4 ⁇ 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) , l-chloro-1,2,2,3,3,3- hexafluoropropane (R-226ca) and l-chloro-1,1,2,2,3,3- hexafluoropropane (R-226cb).
  • the chlorine-containing 2,2-difluoropropane (C 3 H n Cl 2 _ n F 6 wherein 0 ⁇ n ⁇ 1) " to be formed by the reaction includes 1-chloro—1,2,2,3,3,3-hexafluoropropane (R-226ca), 1-chloro-l,1,2,2,3,3-hexfluoropropane (R- 226cb), 1,3-dichloro-l,1,2,2,3,3-hexafluoropropane (R- 216ca) and 1,1-dichloro-l,2,2,3,3,3-hexafluoropropane (R- 216cb) .
  • These products can be separated by a usual method such as distillation.
  • a radical-generating source such as light, heat or a radical initiator, or a combination thereof
  • 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. for example, be ⁇ , ⁇ '-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.
  • chlorine is used in a low stoichiometrical amount relative to the 2,2- difluoropropane (C 3 H a Cl b F c ).
  • chlorine is used in an amount larger than stoichiometry relative to total molar amount of the starting material, for example, 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 450°C.
  • 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.
  • a halogenated hydrocarbon such as carbon tetrachloride may suitably be used.
  • 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.
  • 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.
  • chlorine may be introduced into a reactor together with the starting material as in a flow system, or may be charged initially.
  • a liquid phase reaction it may also be charged initially, but it is preferable to bubble into the liquid phase.
  • Example 1-1 The reaction was conducted for 6 hours in the same 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 19 F-NMR and ⁇ -NMR. The results are shown in Table 1-1.
  • 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 19 F-NMR and ⁇ -H-NMR. The results are shown in Table 1-1.
  • EXAMPLE 1-4 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 19 F-NMR and ⁇ -H-NMR. The results are shown in Table 1-1.
  • Example 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 CC1 4 was used as the solvent for the reaction.
  • the product was analyzed by gas chromatography and by 19 F-NMR and ⁇ -H-NMR. The results are shown in Table 1-1. Table 1-1
  • Example 1-1 The reaction was conducted for 6 hours in the same manner as in Example 1-1 except that 300 g 1-chloro- 2,2,3-trifluoropropane and 160 g of chlorine gas were used.
  • the product was analyzed by gas chromatography and by 19 F-NMR and -NMR. The results are shown in Table 1- 3.
  • EXAMPLE 1-9 The reaction was conducted for 6 hours in the same manner as in Example 1-1 except that 300 g of 1-chloro- 1,2,2-trifluoropropane and 160 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19 F-NMR and X H-NMR. The results are shown in Table 1- 4. Table 1-4
  • Example 1-5 The reaction was conducted for 6 hours in the same manner as in Example 1-1 except that 300 g of 1,3- dichloro-1,2,2-trifluoropropane and 130 g of chlorine gas were used.
  • the product was analyzed by gas chromatography and by 19 F-NMR and 1 H-NMR. The results are shown in Table 1-5.
  • Example 1-1 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 19 F-NMR and ⁇ -H-NMR. The results are shown in Table 1-6.
  • Example 1-1 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 gas were used.
  • the product was analyzed by gas chromatography and by 19 F-NMR and ⁇ -H-NMR. The results are shown in Table 1-8. -
  • Example 1-1 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 19 F-NMR and ⁇ - MR. The results are shown in Table 1-9.
  • Example 1-1 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 of chlorine gas were used.
  • the product was analyzed by gas chromatography and by 19 F-NMR and ⁇ - M . The results are shown in Table 1-10.
  • Example 1-1 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 gas were used.
  • the product was analyzed by gas chromatography and by 19 F-NMR and ⁇ -NMR. The results are shown in Table 1-11.
  • Example 1-1 The reaction was conducted for 6 hours in the same manner as in Example 1-1 except that 300 g of 1,1,1,3- tetrachloro-2,2,3-trifluoropropane and 90 g of chlorine gas were used.
  • the product was analyzed by gas chromatography and by 19 F-NMR and ⁇ -NMR. The results are shown in Table 1-12.
  • Example 2-1 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, 185 g of chlorine gas and 200 g of CC1 4 as a solvent were used.
  • the product was analyzed by gas chromatography and by 19 F-NMR and 1 H-NMR. The results are shown in Table 2-1.
  • Example 2-3 The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g of 1,1,2,2- tetrafluoropropane and 185 g of chlorine gas were used and the reaction was carried out at -30°C.
  • the product was analyzed by gas chromatography and by 19 F-NMR and ⁇ -H- NMR. The results are shown in Table 2-3,
  • Example 2-1 The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g of 1-chloro- 2,2,3,3-tetrafluoropropane and 140 g of chlorine gas were used.
  • the product was analyzed by gas chromatography and by 19 F-NMR and X H-NMR. The results are shown in Table 2- 4.
  • Example 2-1 The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g of 1-chloro- 1,2,2,3-tetrafluoropropane and 140 g of chlorine gas were used.
  • the product was analyzed by gas chromatography and by 19 F _ NMR an d l -H-NMR. Tne results are shown in Table 2- 5.
  • Example 2-1 The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g of 1-chloro- 1,1,2,2-tetrafluoropropane and 140 g of chlorine gas were used.
  • the product was analyzed by gas chromatography and
  • Example 2-7 The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g of 1,3- dichloro-1,2,2,3-tetrafluoropropane and 115 g of chlorine gas were used.
  • the product was analyzed by gas chromatography and by 19 F-NMR and X H-NMR. The results are shown in Table 2-7.
  • Example 2-8 The reaction was conducted for 6 hours in the same manner as in Example 2-1 except "that 300 g of 1,1- dichloro-2,2,3,3-tetrafluoropropane and 115 g of chlorine gas were used.
  • the product was analyzed by gas chromatography and by 19 F-NMR and 1 H-NMR. The results are shown in Table 2-8.
  • Example 2-1 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 19 F-NMR and ⁇ -NMR. The results are shown in Table 2-9.
  • Example 2-1 The reaction was conducted for 6 hours in the same manner as in Example 2-1 except "that 300 g of 1,1- dichloro-l,2,2,3-tetrafluoropropane and 58 g of chlorine gas were used.
  • the product was analyzed by gas chromatography and by 19 F-NMR and ⁇ -H-NMR. The results are shown in Table 2-10.
  • Example 2-1 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-2,2,3,3-tetrafluoropropane and 100 g of chlorine gas were used.
  • the product was analyzed by gas chromatography and by 19 F-NMR and 1 H-NMR. The results are shown in Table 2-11.
  • EXAMPLE 2-17 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 19 F-NMR and 1 H-NMR. The results are shown in Table 2-12.
  • Example 2-1 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 g of chlorine gas were used.
  • the product was analyzed by gas chromatography and by 19 F-NMR and 1 H-NMR. The results are shown in Table 2-13.
  • EXAMPLE 3-1 A 1,000 cc glass reactor equipped with a condenser of -78°C, was cooled to -20°C, and " 30Q g of 1,1,2,2,3- pentafluoropropane was charged. Then, 80 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 acid components, was analyzed by gas chromatography and by 19 F-NMR and X H-NMR. The results are shown in Table 3-1.
  • EXAMPLE 3-2 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. The product was analyzed by gas chromatography and by 19 F-NMR and X H-NMR. The results are shown in Table 3-1.
  • EXAMPLE 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 160 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19 F-NMR and X H-NMR. The results are shown in Table 3-1. EXAMPLE 3-3
  • 1,1,2,2,3-pentafluorolpropane and 20 g of di-t-butyl peroxide were charged. Then, the temperature was raised to 120°C, and while stirring, 200 g of chlorine gas was supplied at a rate of 50 g/hr over a period of 4 hours.
  • 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 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 19 F-NMR and ⁇ -H-NMR. The results are shown in Table 3-2.
  • Example 3-1 The reaction was conducted for 6 hours in the same manner as in Example 3-1 except that 300 g of 1,1,1,2,2- pentafluoropropane and 160 g of chlorine gas were used and the reaction was carried out " at -30°C.
  • the product was analyzed by gas chromatography and by 19 F-NMR and X H- NMR. The results are shown in Table 3-3.
  • Example 3-4 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 g of chlorine gas were used.
  • the product was analyzed by gas chromatography and by 19 F-NMR and ⁇ -H-NMR. The results are shown in Table 3-4.
  • Example 3-1 The reaction was conducted for 6 hours in the same manner as in Example 3-1 except that 300 g of 1-chloro- 2,2,3,3,3-pentafluoropropane and 65 g of chlorine gas were used.
  • the product was analyzed by gas chromatography and by 19 F-NMR and ⁇ - MR. The results are shown in Table 3-5.
  • Example 3-1 The reaction was conducted for 6 hours in the same manner as in Example 3-1 except that 300 g of 1-chloro- 1,1,2,2,3-pentafluoropropane and 65 g of chlorine gas were used.
  • the product was analyzed by gas chromatography and by 19 F-NMR and X H-NMR. The results are shown in Table 3-6.
  • Example 3-7 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 19 F-NMR and ⁇ - R. The results are shown in Table 3-7.
  • Example 3-1 The reaction was conducted for 6 hours in the same manner as in Example 3-1 except that 300 g 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 19 F-NMR and 1 H-NMR. The results are shown in Table 3-8.
  • Example 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- dichloro-l,2,2,3,3-pentafluoropropane and 105 g of chlorine gas were used.
  • the product was analyzed by gas chromatography and by 19 F-NMR and L H-NMR. The results are shown in Table 3-9.
  • Example 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, 140 g of chlorine gas and 200 g of CC1 4 as a solvent were used.
  • the product was analyzed by gas chromatography and by 19 F-NMR and ⁇ -N R. The results are shown in Table 4-1.
  • Example 4-1 The reaction was conducted for 6 hours in the same manner as in Example 4-1 except that 300 g of 1,1,1,2,2,3-hexafluoropropane and 70 g of chlorine gas were used.
  • the product was analyzed by gas chromatography and by 19 F-NMR and ⁇ -NMR. The results are shown in Table 4-3.
  • Example 4-1 The reaction was conducted for 6 hours in the same manner as in Example 4-1 except that 300 g of 1-chloro- 1,2,2,3,3,3-hexafluoropropane and 120 g of chlorine gas were used.
  • the product was analyzed by gas chromatography and by 19 F-NMR and ⁇ -NMR. The results are shown in Table 4-4.
  • Example 4-1 The reaction was conducted for 6 hours in the same manner as in Example 4-1 except that 300 g of 1-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 19 F-NMR and 1 H-NMR. The results are shown in Table 4-5.
  • the present invention is effective for producing a chlorine-containing 2,2-difluoropropane selectively by chlorinating a 2,2-difluoropropane ,

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Abstract

A process for producing a chlorine-containing 2,2-difluoropropane of the formula (2): C3Ha-xClb+xFc, which comprises chlorinating a 2,2-difluoropropane of the formula (1): C3HaClbFc, 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.

Description

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.
BACKGROUND TECHNIQUE As a synthetic route for a chlorine-containing 2,2- difluoropropane, a method has been known in which . dichlorofluoromethane or chloromethane is added to an ethylene having a difluoromethylene unit, such as 1,1- dichloro-2,2-difluoroethylene 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. Therefore, 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 such a drawback of the conventional method and to provide a process for efficiently producing a chlorine-containing 2,2-difluoropropane. The present inventors have conducted an extensive 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 substituting 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 provides 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_χClb+χFc (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. 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 chlorofluorocarbons. Particularly, it includes a promising substitute for 1,1,2- trichlorotrifluoroethane as a solvent. BEST MODE OF CARRYING OUT THE INVENTION
Reactions of the following formulas (3) to (6) may be mentioned as specific embodiments for the preparation of a chlorine-containing 2,2-difluoropropane of the formula (2) from a 2,2-difluoropropane of the formula (1).
Cl2 C3HmlC15-π_lF3 → 3HnlC15-nlF3 (3) 1 ≤ m1 ≤ 5 0 ≤ n1 ≤ 4, m1 > n1
The 2,2-difluoropropane (C3HiniCl5_mi 3 wherein 1 ≤ πp 2≥ 5) to be used as the starting material includes, for example, 1,2,2-trifluoropropane (R-263c), l-chloro-2,2,3- trifluoropropane (R-253ca), l-chloro-1,2,2- trifluoropropane (R-253cb), l,3-dichloro-l,2,2- trifluoropropane (R-243ca), l,l-dichloro-2,2,3- trifluoropropane (R-243cb), l,l-dichloro-l,2,2- trifluoropropane (R-243cc), l,l,3-trichloro-l,2,2- trifluoropropane (R-233cb), l,l,3,3-tetrachloro-l,2,2- trifluoropropane (R-223ca) and l,l,l,3-tetrachloro-2,2,3- trifluoropropane (R-223cb) .-
The chlorine-containing 2,2-difluoropropane (C3HnιCl5_nιF3 wherein 0 ≤ n1 ≤ 4) to be formed by the reaction includes l-chloro-2,2,3-trifluoropropane (R- 253ca), 1-chloro-l,2,2-trifluoropropane (R-253cb), 1,3- dichloro-1,2,2-trifluoropropane (R-243ca), 1,1-dichloro- 2,2,3-trifluoropropane (R-243cb), l,l-dichloro-l,2,2- trifluoropropane (R-243cc), l,l,3-trichloro-2,2,3- trifluoropropane (R-233ca), l,l,3-trichloro-l,2,2- trifluoropropane (R-233cb), l,l,l-trichloro-2,2,3- trifluoropropane (R-233cc), l,l,3,3-tetrachloro-l,2,2- trifluoropropane (R-223ca), l,l,l,3-tetrachloro-2,2,3- trifluoropropane (R-223cb) and 1,1,1,3,3-pentachloro- 2,2,3-trifluoropropane (R-213c) .
Cl,
C3Hrr.2Cl4_-r.2 4 C3 Hπ2Cl4_n2 4 (4) 1 ≤ m2 ≤ 4 0 ≤ n2 ≤ 3, 2 > n2
The 2,2-difluoropropane (C3Hm2Cl4_m2F4 wherein 1 ≤ m2
≤ 4) to be used as the starting material includes
1,2,2,3-tetrafluoropropane R-254ca), 1,1,2,2- tetrafluoropropane (R-254cb , l-chloro-2,2,3,3- tetrafluoropropane (R-244ca r l-chloro-1,2,2,3- tetrafluoropropane (R-244cb , 1-chloro-l,1,2,2- tetrafluoropropane (R-244cc , 1,3-dichloro-l,2,2,3- tetrafluoropropane (R-234ca , l,l-dichloro-2,2,3,3- tetrafluoropropane (R-234cb , l,3-dichloro-l,l,2,2- tetrafluoropropane (R-234cc , l,l-dichloro-l,2,2,3- tetrafluoropropane (R-234cd , l,l,3-trichloro-2,2,3,3- tetrafluoropropane (R-224ca , l,l,3-trichloro-l,2,2,3- tetrafluoropropane (R-224cb and 1,l-trichloro-2,2,3,3- tetrafluoropropane (R-224cc
The chlorine-containing 2,2-difluoropropane (C3Hn Cl4.n2F4 wherein 0 ≤ n2 ≤ 3) to be formed by the reaction includes l-chloro-2,2,3,3-tetrafluoropropane (R- 244ca), 1-chloro-l,2,2,3-tetrafluoropropane (R-244cb), 1- chloro-1,1,2,2-tetrafluoropropane (R-244cc), 1,3- dichloro-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- dichloro-1,2,2,3-tetrafluoropropane (R-234cd) , 1,1,3- trichloro-2,2,3,3-tetrafluoropropane (R-224ca), 1,1,3- trichloro-l,2,2,3-tetrafluoropropane (R-224cb), 1,1,1- trichloro-2,2,3,3-tetrafluoropropane (R-224cc), 1,1,3,3- tetrachloro-l,2,2,3-tetrafluoropropane (R-214ca) and l,l,l,3-tetrachloro-2,2,3,3-tetrafluoropropane (R-214cb) . These products can be separated by a usual method such as distillation.
Cl2 C3Hrn3Cl3_m3 5 → 3Hn3Cl3_n3F5 (5)
1 ≤ m3 ≤ 3 0 ≤ n3 ≤ 2, m3 > n3 The 2,2-difluoropropane (C3Hm3Cl3_m3F5 wherein 1 ≤ m3 ≤. 3 to be used as the starting material includes 1,1,2,2,3-pentafluoropropane (R-245ca), 1,1,1,2,2- pentafluoropropane (R-245cb), 1-chloro-l,2,2,3,3- pentafluoropropane (R-235ca), l-chloro-2,2,3,3,3- pentafluoropropane (R-235cb), 1-chloro-l,1,2,2,3- pentafluoropropane (R-235cc), l,l-dichloro-2,2,3,3,3- pentafluoropropane (R-225ca), l,3-dichloro-l,l,2,2,3- pentafluoropropane (R-225cb) and l,l-dichloro-l,2,2,3,3- pentafluoropropane (R-225cc).
The chlorine-containing 2,2-difluoropropane (C3Hn3Cl3_n3F5 wherein 0 ≤ n3 ≤ 2) to be formed by the reaction includes l-chloro-l,l,2,2,3,3-pentafluoropropane (R-235ca), l-chloro-2,2,3,3,3-pentafluoropropane (R- 235cb), l-chloro-l,l,2,2,3-pentafluoropropane (R-235cc), l,l-dichloro-2,2,3,3,3-pentafluoropropane (R-225ca), 1,3- dichloro-1,1,2,2,3-pentafluoropropane (R-225cb) , 1,1- dichloro-l,2,2,3,3-pentafluoropropane (R-225cc), 1,1,3- trichloro-1,2,2,3,3-pentafluoropropane (R-215ca) and 1,1,l-trichloro-2,2,3,3,3-pentafluoropropane (R-215cb) . Cl2
C3Hm4Cl2_m4F6 -→ C3Hn2Cl2.n4 5 (6)
1 ≤ m4 ≤ 2 0 ≤ n4 ≤ 1, m4 > n4 The 2,2-difluoropropane (C3Hrπ4Cl2_ιn4F6 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) , l-chloro-1,2,2,3,3,3- hexafluoropropane (R-226ca) and l-chloro-1,1,2,2,3,3- hexafluoropropane (R-226cb).
The chlorine-containing 2,2-difluoropropane (C3HnCl2_nF6 wherein 0 ≤ n ≤ 1) "to be formed by the reaction includes 1-chloro—1,2,2,3,3,3-hexafluoropropane (R-226ca), 1-chloro-l,1,2,2,3,3-hexfluoropropane (R- 226cb), 1,3-dichloro-l,1,2,2,3,3-hexafluoropropane (R- 216ca) and 1,1-dichloro-l,2,2,3,3,3-hexafluoropropane (R- 216cb) . These products can be separated by a usual method 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. for example, be α,α'-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 of 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 example, 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 450°C. 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. 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. When 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 of 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 preferable 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 specific Examples. EXAMPLE 1-1
A 1,000 cc glass reactor equipped with a condenser of -78°C, was cooled to -20°C, and 300 g of 1,2,2- trifluoropropane was charged. Then, 107 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 acid components, was analyzed by gas chromatography and by 19F-NMR and XH-NMR. The results are shown in Table 1-1. EXAMPLE 1-2
The reaction was conducted for 6 hours in the same 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 ^-NMR. The results are shown in Table 1-1. 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 19F-NMR and ^-H-NMR. The results are shown in Table 1-1. EXAMPLE 1-4
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 ^-H-NMR. The results are shown in Table 1-1. Table 1-1
Figure imgf000012_0001
EXAMPLE 1-5
Into a 1,000 cc Hastelloy C autoclave, 300 g of
20 1,2,2-trifluorolpropane and 20 g of di-t-butyl peroxide were charged. Then, the temperature was raised to 120°C, 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 ^-NMR. The results are shown in Table 1-2. EXAMPLE 1-6
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 1H-NMR. The results are shown in Table 1-2. EXAMPLE 1-7
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 1,2,2-trifluoropropane and chlorine gas were supplied at a rate of 300 ml/min, respectively. The reaction was conducted continuously for 4 hours. The product after removal of acid components was analyzed by gas chromatography and by 19F-NMR and 1H-NMR. The results are shown iri Table 1-2.
Table 1-2 "
Figure imgf000013_0001
EXAMPLE 1-8
The reaction was conducted for 6 hours in the same manner as in Example 1-1 except that 300 g 1-chloro- 2,2,3-trifluoropropane and 160 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and -NMR. The results are shown in Table 1- 3.
Table 1-3
Figure imgf000014_0001
EXAMPLE 1-9 The reaction was conducted for 6 hours in the same manner as in Example 1-1 except that 300 g of 1-chloro- 1,2,2-trifluoropropane and 160 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and XH-NMR. The results are shown in Table 1- 4. Table 1-4
Figure imgf000015_0001
EXAMPLE 1-10
The reaction was conducted for 6 hours in the same manner as in Example 1-1 except that 300 g of 1,3- dichloro-1,2,2-trifluoropropane and 130 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and 1H-NMR. The results are shown in Table 1-5.
Figure imgf000015_0002
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 ^-H-NMR. The results are shown in Table 1-6.
Table 1-6
Figure imgf000016_0001
EXAMPLE 1-12
The reaction was conducted for 6 hours in the same manner as in Example 1-1 except that 300 g of 1,1- dichloro-l,2,2-trifluoropropane and 130 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and ^-NMR. The results are shown in Table 1-7. Table 1-7
Figure imgf000017_0001
EXAMPLE 1-13
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 gas were used. The product was analyzed by gas chromatography and by 19F-NMR and ^-H-NMR. The results are shown in Table 1-8. -
Table 1-8
Figure imgf000017_0002
EXAMPLE 1-14
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 ^- MR. The results are shown in Table 1-9.
Figure imgf000018_0001
EXAMPLE 1-15
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 of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and ^- M . The results are shown in Table 1-10.-
Table 1-10
Figure imgf000018_0002
EXAMPLE 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 gas were used. The product was analyzed by gas chromatography and by 19F-NMR and ^-NMR. The results are shown in Table 1-11.
Figure imgf000019_0001
EXAMPLE 1-17
The reaction was conducted for 6 hours in the same manner as in Example 1-1 except that 300 g of 1,1,1,3- tetrachloro-2,2,3-trifluoropropane and 90 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and ^-NMR. The results are shown in Table 1-12.
Table 1-12
Conversion for CC13CF2CHC1F (%) 97
Selectivity for CC13CF2CC12F (%) 100
EXAMPLE 2-1
A 1,000 cc glass reactor equipped with a condenser of -78°C, was cooled to -20°C, and 300 g of 1,2,2,3- tetrafluoropropane was charged. Then, 95 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 acid components, was analyzed by gas chromatography and by 19F-NMR and XH-NMR. The results are shown in Table '2-1. EXAMPLE 2-2
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 185 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and ^-H-NMR. The results are shown in Table 2-1. EXAMPLE 2-3
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 XH-NMR. The results are shown in Table 2-1. EXAMPLE 2-4
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, 185 g of chlorine gas and 200 g of CC14 as a solvent were used. The product was analyzed by gas chromatography and by 19F-NMR and 1H-NMR. The results are shown in Table 2-1.
Table 2-1
Figure imgf000021_0001
10
EXAMPLE 2-5
Into a 1,000 cc Hastelloy C autoclave, 300 g of 15 1,2,2,3-tetrafluorolpropane and 20 g of di-t-butyl peroxide were charged. Then, the temperature was raised to 120°C, 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. 20 The product after removal of acid components, was analyzed by gas chromatography and by 19F-NMR and ^Η-NMR.
The results are shown in Table 2-2.
EXAMPLE 2-6"
The reaction was conducted in the same manner as in 25 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 analyzed by gas chromatography and by 19F-NMR and ^-NMR. The results are shown in Table 2-2. EXAMPLE 2-7
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 1,2,2,3-tetrafluoropropane 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 1H-NMR. The results are shown in Table 2-2.
Table 2-2
Figure imgf000022_0001
EXAMPLE 2-8
The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g of 1,1,2,2- tetrafluoropropane and 185 g of chlorine gas were used and the reaction was carried out at -30°C. The product was analyzed by gas chromatography and by 19F-NMR and ^-H- NMR. The results are shown in Table 2-3,
Table 2-3
Figure imgf000023_0001
EXAMPLE 2-9
The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g of 1-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 XH-NMR. The results are shown in Table 2- 4.
Table 2-4
Figure imgf000023_0002
- 22 -
EXAMPLE 2-10
The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g of 1-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 l-H-NMR. Tne results are shown in Table 2- 5.
Table 2-5
10
Figure imgf000024_0001
15 EXAMPLE 2-11
The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g of 1-chloro- 1,1,2,2-tetrafluoropropane and 140 g of chlorine gas were used. The product was analyzed by gas chromatography and
20 by 19F-NMR and ^-H-NMR. The results are shown in Table 2- 6.
Table 2-6
25
Figure imgf000024_0002
EXAMPLE 2-12
The reaction was conducted for 6 hours in the same manner as in Example 2-1 except that 300 g of 1,3- dichloro-1,2,2,3-tetrafluoropropane and 115 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and XH-NMR. The results are shown in Table 2-7.
Table 2-7
Figure imgf000025_0001
EXAMPLE 2-13
The reaction was conducted for 6 hours in the same manner as in Example 2-1 except"that 300 g of 1,1- dichloro-2,2,3,3-tetrafluoropropane and 115 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and 1H-NMR. The results are shown in Table 2-8.
Table 2-8
Figure imgf000025_0002
EXAMPLE 2-14
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 ^-NMR. The results are shown in Table 2-9.
Table 2-9
Figure imgf000026_0001
EXAMPLE 2-15
The reaction was conducted for 6 hours in the same manner as in Example 2-1 except"that 300 g of 1,1- dichloro-l,2,2,3-tetrafluoropropane and 58 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and ^-H-NMR. The results are shown in Table 2-10.
Table 2-10
Figure imgf000026_0002
EXAMPLE 2-16
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-2,2,3,3-tetrafluoropropane and 100 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and 1H-NMR. The results are shown in Table 2-11.
Figure imgf000027_0001
EXAMPLE 2-17 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 1H-NMR. The results are shown in Table 2-12.
Figure imgf000027_0002
EXAMPLE 2-18
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 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and 1H-NMR. The results are shown in Table 2-13.
Table 2-13
Conversion for CC13CF2CHF2 (%) 91
Selectivity for CC13CF2CC1F2 (%) 100
EXAMPLE 3-1 A 1,000 cc glass reactor equipped with a condenser of -78°C, was cooled to -20°C, and"30Q g of 1,1,2,2,3- pentafluoropropane was charged. Then, 80 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 acid components, was analyzed by gas chromatography and by 19F-NMR and XH-NMR. The results are shown in Table 3-1. EXAMPLE 3-2 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. The product was analyzed by gas chromatography and by 19F-NMR and XH-NMR. The results are shown in Table 3-1. EXAMPLE 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 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and XH-NMR. The results are shown in Table 3-1. EXAMPLE 3-4
10 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, 160 g.of chlorine gas and 200 g of CC14 as a solvent were used. The product was analyzed by gas chromatography and by 19F-NMR and ^-NMR. The
15 results are shown in Table 3-1.
Table 3-1
Figure imgf000029_0001
EXAMPLE 3-5
Into a 1,000 cc Hastelloy C autoclave, 300 g of
1,1,2,2,3-pentafluorolpropane and 20 g of di-t-butyl peroxide were charged. Then, the temperature was raised to 120°C, 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 XH-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 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 ^-H-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 length of 20 cm, was maintained at 430°C, 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 ^- MR. The results are shown in Table 3-2. - 29 -
Table 3-2
Figure imgf000031_0001
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 -30°C. The product was analyzed by gas chromatography and by 19F-NMR and XH- NMR. The results are shown in Table 3-3.
Table 3-3
Figure imgf000031_0002
EXAMPLE 3-9
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 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and ^-H-NMR. The results are shown in Table 3-4.
Table 3-4
Figure imgf000032_0001
EXAMPLE 3-10
The reaction was conducted for 6 hours in the same manner as in Example 3-1 except that 300 g of 1-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 ^- MR. The results are shown in Table 3-5.
Table 3-5
Conversion for CF3CF2CH2C1 ( % ) 37
Selectivity for CF3CF2CHC12 ( % ) 81
Selectivity for CF3CF2CC13 ( % ) 19 EXAMPLE 3-11
The reaction was conducted for 6 hours in the same manner as in Example 3-1 except that 300 g of 1-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 XH-NMR. The results are shown in Table 3-6.
Table 3-6
Figure imgf000033_0001
EXAMPLE 3-12
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 ^- R. The results are shown in Table 3-7.
Table 3-7-
Conversion for CF3CF2CHC12 ( % ) 99
Selectivity for CF3CF2CC13 ( % ) 100 EXAMPLE 3-13
The reaction was conducted for 6 hours in the same manner as in Example 3-1 except that 300 g 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 1H-NMR. The results are shown in Table 3-8.
Figure imgf000034_0001
EXAMPLE 3-14
The reaction was conducted "for 6 hours in the same manner as in Example 3-1 except that 300 g of 1,1- dichloro-l,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 CC12FCF2CHF2 (%) 91
Selectivity for CC12FCF2CC1F2 (%) 100 EXAMPLE* 4-1
A 1,000 cc glass reactor equipped with a condenser of -78°C, was cooled to -20°C, 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 acid components, was analyzed by gas chromatography and by 19F-NMR and ^-NMR. The results are shown in Table 4-1. EXAMPLE 4-2
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 were used. The product was analyzed by gas chromatography and by 19F-NMR and 1H-NMR. The results are shown in Table 4-1. EXAMPLE 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 19F-NMR and ^-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 1,1,2,2,3,3-hexafluoropropane, 140 g of chlorine gas and 200 g of CC14 as a solvent were used. The product was analyzed by gas chromatography and by 19F-NMR and ^-N R. The results are shown in Table 4-1.
Figure imgf000036_0001
15
EXAMPLE 4-5
Into a 1,000 cc Hastelloy C autoclave, 300 g of 1,1,2,2,3,3-hexafluorolpropane and 20 g of di-t-butyl peroxide were charged. Then, the temperature was raised
20 to 120°C, and while stirring, 160 g of chlorine gas was supplied at a rate of 40 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 ^-H-NMR.
25 The results are shown in Table 4-2. EXAMPLE 4-6
The reaction was conducted in the same manner as in Example 4-5 except that 300 g 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 chromatography and by 19F-NMR and XH-NMR. The results are shown in Table 4-2. EXAMPLE 4-7
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 of acid components was analyzed by gas chromatography and by 19F-NMR and -"-H-NMR. The results are shown in Table 4-2.
Table 4-2
Figure imgf000037_0001
EXAMPLE 4-8
The reaction was conducted for 6 hours in the same manner as in Example 4-1 except that 300 g 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 ^-NMR. The results are shown in Table 4-3.
Table 4-3
Figure imgf000038_0001
EXAMPLE 4-9
The reaction was conducted for 6 hours in the same manner as in Example 4-1 except that 300 g of 1-chloro- 1,2,2,3,3,3-hexafluoropropane and 120 g of chlorine gas were used. The product was analyzed by gas chromatography and by 19F-NMR and ^-NMR. The results are shown in Table 4-4.
Table 4-4
Conversion for CF3CF2CHC1F (%) 97
Selectivity for CF3CF2CC12F (%) 100 8752
- 37 -
EXAMPLE 4-10
The reaction was conducted for 6 hours in the same manner as in Example 4-1 except that 300 g of 1-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 1H-NMR. The results are shown in Table 4-5.
Table 4-5
Conversion for CC1F2CF2CHF2 (%) 95
Selectivity for CC1F2CF2CC1F2 (%) 100
The present invention is effective for producing a chlorine-containing 2,2-difluoropropane selectively by chlorinating a 2,2-difluoropropane,

Claims

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):
CsW c D
C3Ha_χClb+χFc (2) wherein a, b, c and x are integers satisfying the following conditions: a ≥ l, b ≥ 0, c .≥ 2, x ≥ l 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 C3HmιCl5_mιF3 (1 ≤ m1 -≥ 5), and the chlorine-containing 2,2-difluoropropane of the formula (2) is C3HnιCl5_n_F3 (0 ≤ n1 ≤ 4, m1 > n1).
5. The process according to Claim 1, wherein the 2,2- difluoropropane of the formula (1) is C3Hrn2Cl4_ιπ2F4 (1 ≤ 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 C3Hrn3Cl3_m3F5 (1 ≤ 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_m F6 (1 ≤≥ m4 -S- 2), and the chlorine-containing 2,2-difluoropropane of the formula (2) is C3Hn4Cl2__ F6 (0 ≤ n4 ≤ 1, m4 > n4).
PCT/JP1990/000121 1989-02-02 1990-02-01 Process for producing a chlorine-containing 2,2-difluoropropane WO1990008752A1 (en)

Applications Claiming Priority (8)

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JP1/22551 1989-02-02
JP1/22552 1989-02-02
JP1/22544 1989-02-02
JP2254389A JPH02300142A (en) 1989-02-02 1989-02-02 Production of chlorinated tetrafluoropropanes
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
JP1/22543 1989-02-02

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US6229057B1 (en) * 1993-07-26 2001-05-08 Zeneca Limited Chlorination process
WO2007056148A1 (en) * 2005-11-03 2007-05-18 Honeywell International Inc. Method for producing fluorinated organic compounds
US7345209B2 (en) 2004-04-29 2008-03-18 Honeywell International 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
US7674939B2 (en) 2004-04-29 2010-03-09 Honeywell International Inc. Method for producing fluorinated organic compounds
US7880040B2 (en) 2004-04-29 2011-02-01 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
US8383867B2 (en) 2004-04-29 2013-02-26 Honeywell International Inc. Method for producing fluorinated organic compounds
US8921625B2 (en) 2007-02-05 2014-12-30 Reaction35, LLC Continuous process for converting natural gas to liquid hydrocarbons
US9133078B2 (en) 2010-03-02 2015-09-15 Gtc Technology Us, Llc 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
US9206093B2 (en) 2004-04-16 2015-12-08 Gtc Technology Us, Llc Process for converting gaseous alkanes to liquid hydrocarbons
US9308199B2 (en) 2004-04-29 2016-04-12 Honeywell International Inc. Medicament formulations
WO2023164093A3 (en) * 2022-02-25 2023-10-12 The Chemours Company Fc, Llc Synthesis of hfo-153-10mczz including catalytic coupling of hcfc-225ca or cfc-215cb

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FR1511915A (en) * 1966-02-18 1968-02-02 Squibb & Sons Inc Process for preparing pentafluoro-1, 1, 1, 2-2-chloro-3-propane
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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6229057B1 (en) * 1993-07-26 2001-05-08 Zeneca Limited Chlorination process
US9206093B2 (en) 2004-04-16 2015-12-08 Gtc Technology Us, Llc Process for converting gaseous alkanes to liquid hydrocarbons
US8383867B2 (en) 2004-04-29 2013-02-26 Honeywell International Inc. Method for producing fluorinated organic compounds
US8395000B2 (en) 2004-04-29 2013-03-12 Honeywell International Inc. Method for producing fluorinated organic compounds
US7674939B2 (en) 2004-04-29 2010-03-09 Honeywell International Inc. Method for producing fluorinated organic compounds
US7880040B2 (en) 2004-04-29 2011-02-01 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
US9308199B2 (en) 2004-04-29 2016-04-12 Honeywell International Inc. Medicament formulations
US7345209B2 (en) 2004-04-29 2008-03-18 Honeywell International 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
US9061957B2 (en) 2004-04-29 2015-06-23 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
EP2336102A1 (en) * 2005-11-03 2011-06-22 Honeywell International Inc. Method for producing fluorinated organic compounds
US8921625B2 (en) 2007-02-05 2014-12-30 Reaction35, LLC Continuous process for converting natural gas to liquid hydrocarbons
US9133078B2 (en) 2010-03-02 2015-09-15 Gtc Technology Us, Llc 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
WO2023164093A3 (en) * 2022-02-25 2023-10-12 The Chemours Company Fc, Llc Synthesis of hfo-153-10mczz including catalytic coupling of hcfc-225ca or cfc-215cb

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