Classifications

• • 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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