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Title:
TRICHLORO-TRIFLUORO-PROPYLENE OXIDE AND METHOD FOR PRODUCING TRICHLORO-TRIFLUORO-PROPYLENE OXIDE
Document Type and Number:
WIPO Patent Application WO/2010/114144
Kind Code:
A1
Abstract:
The present invention provides a novel propylene oxide and a method for producing the same as well as a production method using the novel propylene oxide. The present invention is 1,1,3-trichloro-2,3,3-trifluoropropylene oxide. The present invention is a method for producing 1,1,3-trichloro-2,3,3-trifluoropropylene oxide which comprises the step of oxidizing a vinyl compound of CF2Cl-CF=CCl2.

Inventors:
MANTANI, Toshiya (Yodogawa Plant, 1-1, Nishihitotsuya, Settsu-sh, Osaka 85, 56685, JP)
SHINOKI, Noriyuki (Yodogawa Plant, 1-1, Nishihitotsuya, Settsu-sh, Osaka 85, 56685, JP)
KONDO, Masahiro (Yodogawa Plant, 1-1, Nishihitotsuya, Settsu-sh, Osaka 85, 56685, JP)
SUGIYAMA, Akinari (Yodogawa Plant, 1-1, Nishihitotsuya, Settsu-sh, Osaka 85, 56685, JP)
Application Number:
JP2010/056119
Publication Date:
October 07, 2010
Filing Date:
March 30, 2010
Export Citation:
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Assignee:
DAIKIN INDUSTRIES, LTD. (Umeda Center Building, 4-12 Nakazaki-Nishi 2-Chome, Kita-ku, Osaka-Sh, Osaka 23, 53083, JP)
MANTANI, Toshiya (Yodogawa Plant, 1-1, Nishihitotsuya, Settsu-sh, Osaka 85, 56685, JP)
SHINOKI, Noriyuki (Yodogawa Plant, 1-1, Nishihitotsuya, Settsu-sh, Osaka 85, 56685, JP)
KONDO, Masahiro (Yodogawa Plant, 1-1, Nishihitotsuya, Settsu-sh, Osaka 85, 56685, JP)
SUGIYAMA, Akinari (Yodogawa Plant, 1-1, Nishihitotsuya, Settsu-sh, Osaka 85, 56685, JP)
International Classes:
C07D303/48; C07C303/22; C07C309/82; C07D301/02
Domestic Patent References:
WO2005042451A2
Foreign References:
US2549892A
JPH08169850A
JPH08193039A
JPH0132808B2
Attorney, Agent or Firm:
YASUTOMI & Associates (5-36, Miyahara 3-chome Yodogawa-ku, Osaka-sh, Osaka 03, 53200, JP)
Download PDF:
Claims:
CLAIMS

1. l,l,3-Trichloro-2, 3, 3-trifluoropropylene oxide of formula (1) :

CIF2C CF ACCI2 (D

2. A method for producing

1, 1, 3-trichloro-2, 3, 3-trifluoropropylene oxide of formula (1): which comprises the step of oxidizing a vinyl compound of CF2Cl-CF=CCl2.

3. The production method according to Claim 2, which comprises the step of contacting a fluorocarbon compound of CF2Cl-CF2-CHCl2 with a base to give the vinyl compound of CF2Cl-CF=CCl2.

4. A method for producing an acid halide of formula (3) : FSO2CF2CF2OCF(CF2CI)COX (3) wherein X is Cl or F, which comprises the step of reacting

1, 1, 3-trichloro-2, 3, 3-trifluoropropylene oxide of formula

(D : with an alkoxide of formula (2) : FSO2CF2CF2OM (2) wherein M is Na or K.

5. A method for producing a carboxylic acid salt of formula (4) :

FSO2CF2CF2OCF(CF2CI)COOM (4) wherein M is as defined above, which comprises the step of contacting the acid halide of formula (3) as obtained by the production method according to Claim 4 with a base of MHCO3 or M2CO3, wherein M is Na or K.

6. A method for producing a vinyl ether of FSO2CF2CF2OCF=CF2 which comprises the step of decarboxylating the carboxylic acid salt of formula (4) as obtained by the production method according to Claim 5.

Description:
DESCRIPTION

TRICHLORO-TRIFLUORO-PROPYLENE OXIDE AND METHOD FOR PRODUCING

TRICHLORO-TRIFLUORO-PROPYLENE OXIDE

CROSS-REFERENCE TO RELATED APPLICATION

The present application claims priority under 35 U. S. C. §119 to US Provisional Application No.61/165, 391, filed March 31, 2009, the contents of which are incorporated herein by- reference in their entirety.

TECHNICAL FIELD [0001] The present invention relates to a trichlorotrifluoropropylene oxide and a method for producing the same.

BACKGROUND ART [0002]

Patent Document 1 discloses that oxidation of CF 2 ClCF=CCl 2 gives CF 2 C1CFC1COCC1 and CF 2 ClCCl 2 COF; and it is estimated that the reaction proceeds via a compound represented by the following formula: [0003]

[0004]

Patent Document 2 discloses that a fluorocarbon epoxide represented by the following formula reacts with a nucleophile to give an acid fluoride. [0005] [0006]

(In the above formula, X = Cl, I or Br) . PRIOR ART DOCUMENTS PATENT DOCUMENTS [0007]

[Patent Document 1] United States Patent No. 2,549,892 [Patent Document 2] Japanese Patent Publication (Kokoku) H01-32808

DISCLOSURE OF INVENTION

PROBLEMS WHICH THE INVENTION IS TO SOLVE

[0008]

Patent Document 1, however, does not disclose that the compound mentioned above was obtained; it fails to provide confirmation that the compound mentioned above is an intermediate in the process reported. While Patent Document

2 discloses that the fluorocarbon epoxide mentioned above was used, a synthesis of this fluorocarbon epoxide has problems; a complicated reaction pathway is required, the use of a metal catalyst is inevitable, and waste material production is involved.

[0009]

It is an object of the present invention to provide a novel propylene oxide and a method for producing the same as well as a production method using the novel propylene oxide.

MEANS FOR SOLVING THE PROBLEMS [0010]

The present invention relates to 1, 1, 3-Trichloro-2, 3, 3-trifluoropropylene oxide of formula

(D : [ 0011 ]

CIF 2 C CF A CCI 2 (D [0012]

The present invention relates to a method for producing 1, 1, 3-trichloro-2, 3, 3-trifluoropropylene oxide of formula

( 1 ) : [ 0013 ] which comprises the step of oxidizing a vinyl compound of

CF 2 Cl-CF=CCl 2 .

[0014] Further, the production method preferably comprises the step of contacting a fluorocarbon compound of CF 2 Cl-CF 2 -CHCl 2 with a base to give the vinyl compound of CF 2 Cl-CF=CCl 2 . [0015]

The present invention relates to a method for producing an acid halide of formula (3) :

FSO 2 CF 2 CF 2 OCF(CF 2 CI)COX (3) wherein X is Cl or F, which comprises the step of reacting

1, 1, 3-trichloro-2, 3, 3-trifluoropropylene oxide of formula

(D : [0016]

[0017] with an alkoxide of formula (2) :

FSO 2 CF 2 CF 2 OM (2) wherein M is Na or K.

[0018]

The present invention relates to a method for producing a carboxylic acid salt of formula (4) :

FSO 2 CF 2 CF 2 OCF(CF 2 CI)COOM (4) wherein M is as defined above, which comprises the step of contacting the acid halide of formula (3) as obtained by the production method mentioned above with a base of MHCO 3 or M 2 CO 3 , wherein M is Na or K.

[0019]

The present invention relates to a method for producing a vinyl ether of FSO 2 CF 2 CF 2 OCF=CF 2 which comprises the step of decarboxylating the carboxylic acid salt of formula (4) as obtained by the production method mentioned above. EFFECTS OF THE INVENTION [0020] 1, 1, 3-Trichloro-2, 3, 3-trifluoropropylene oxide of the invention is very useful as an intermediate for the production of a fluorinated organic compound and, owing to its specific and high reactivity, it can be converted to an ether compound or an ester compound having a terminal chlorodifluoromethyl group. Further, 1, 1, 3-trichloro-2, 3, 3-trifluoropropylene oxide is useful as a starting material for the production of a vinyl ether of formula CF 2 =CFOCF 2 CF 2 SO 2 F. The vinyl ether is a compound useful as an industrial raw material for the production of an ion exchange membrane material and so forth.

BEST MODES FOR CARRYING OUT THE INVENTION [0021]

The present invention relates to 1, 1, 3-trichloro-2, 3, 3-trifluoropropylene oxide of formula (1):

[0022]

ClF 2 C CF ACCI 2 (D

[0023]

1, 1, 3-Trichloro-2, 3, 3-trifluoropropylene oxide of the invention can be obtained by a production method which comprises the step of oxidizing a vinyl compound of CF 2 Cl-CF=CCl 2 . [0024]

The above oxidation is preferably carried out by contacting the vinyl compound of CF2C1-CF=CC1 2 with an oxidizing agent. The contacting time is generally 3 to 72 hours. The temperature at which the contacting is caused is generally 40 to 80 0 C, preferably 50 to 7O 0 C from the viewpoint of securing a moderate rate of reaction while inhibiting rearrangement reaction of the product

1,1, 3-trichloro-2, 3, 3-trifluoropropylene oxide. [0025]

As the oxidizing agent, there may be mentioned, for example, chloric acid and salts thereof, perchloric acid and salts thereof, chlorous acid and salts thereof, hypochlorous acid and salts thereof, bromic acid and salts thereof, iodic acid and salts thereof, hydrogen peroxide, and a mixture of hydrogen peroxide and a fluoroalcohol . The salts mentioned above are, for example, the sodium, potassium, magnesium, calcium and ammonium salts. The oxidizing agent preferably comprises, among others, at least one species selected from the group consisting of sodium hypochlorite, an aqueous solution of hydrogen peroxide, and an aqueous hydrogen peroxide solution-fluoroalcohol mixture. The oxidizing agent is preferably added in an amount of 100 to 300 parts by mass per 100 parts by mass of the vinyl compound mentioned above. [0026]

For obtaining 1, 1, 3-trichloro-2, 3, 3-trifluoropropylene oxide in high yields, the above oxidation is preferably caused to proceed by adding the vinyl compound of CF 2 Cl-CF=CCl 2 , the oxidizing agent and water to a reactor to thereby contacting the vinyl compound of CF 2 Cl-CF=CCl 2 with the oxidizing agent. The water may be the water contained in the aqueous oxidizing agent solution or the water contained in the aqueous hydrogen peroxide solution. The reason why high yields are obtained is inferred that the addition of water causes separation of a field of reaction into an organic phase and an aqueous phase, so that the rearrangement reaction of the product 1, 1, 3-trichloro-2, 3, 3-trifluoropropylene oxide is inhibited. The aqueous oxidizing agent solution generally has an oxidizing agent concentration of 10% to 50% by mass.

[0027]

The above oxidation is preferably carried out in the presence of a phase transfer catalyst. The use of the phase transfer catalyst allows the reaction to proceed smoothly even in the case that the reaction field separates into an organic phase and an aqueous phase. As the phase transfer catalyst, there may be mentioned a quaternary ammonium salt such as a tetrabutylammonium salt, a trioctylmethylammonium salt and a benzyldimethyloctadecylammonium salt; a quaternary phosphonium salt such as a tetrabutylphosphonium salt and a benzyltrimethylphosphonium salt; a macrocyclic polyether such as 12-crown-4, 18-crown-β and benzo-18-crown-6, and so forth; preferred is trioctylmethylammonium chloride (TOMAC) . [0028]

The above-mentioned oxidation may also be carried out in the presence of a catalytic amount of a water-soluble organic substance. As the organic substance, there may be mentioned methyl alcohol, ethyl alcohol, acetonitrile, acetone, diglyme, tetraglyme and the like; diglyme is preferred since it facilitates the isolation of the product. [0029]

According to the production method of the invention, it is possible to obtain

1, 1, 3-trichloro-2, 3, 3-trifluoropropylene oxide of formula (1) in a yield not lower than 30 mole percent, preferably not lower than 40 mole percent. Such a yield can be confirmed by gas chromatographic analysis. [0030]

The vinyl compound of CF 2 Cl-CF=CC^ can be prepared, for example, by contacting the fluorocarbon compound of CF 2 CI-CF2-CHCI 2 with a base such as potassium hydroxide or sodium hydroxide. The contacting time is generally 2 to 10 hours, and the contacting temperature is generally 50 to 9O 0 C. [0031]

The production method of the invention preferably comprises the step of contacting the fluorocarbon compound of CF2CI-CF2-CHCI2 with the base to give the vinyl compound of CF 2 Cl-CF=CCl 2 . [0032]

The fluorocarbon compound of CF 2 CI-CF 2 -CHCI2 can be obtained in a conventional manner, for example by allowing chloroform to add to tetrafluoroethylene in the presence of such a catalyst as aluminum chloride. [0033]

1, 1, 3-Trichloro-2, 3, 3-trifluoropropylene oxide of formula (1) of the invention is useful, for example, as a raw material for the production of the fluorinated fluorosulfonylalkyl vinyl ether of FSO 2 CF 2 CF 2 OCF=CF 2 and can be suitably utilized in particular in the following production method according to the invention. [0034]

The invention also relates to a method for producing the acid halide of formula (3) :

FSO 2 CF 2 CF 2 OCF(CF 2 CI)COCI (3), which comprises the step of reacting

1, 1, 3-trichloro-2, 3, 3-trifluoropropylene oxide of formula (1) with the alkoxide of formula (2) : FSO 2 CF 2 CF 2 OM (2) wherein M is Na or K. [0035]

The alkoxide of formula (2) can be prepared with ease, for example, by reacting a corresponding β-sultone with an alkali metal fluoride MF. In the formula, M is Na or K. The alkoxide of formula (2) is a compound unstable in the air at room temperature and, therefore, the alkoxide is preferably prepared in a system in which the reaction mentioned above is carried out and used as it is for the reaction. [0036] The reaction of

1, 1, 3-trichloro-2, 3, 3-trifluoropropylene oxide with the alkoxide proceeds in the same manner as a reaction of a halogen-substituted propylene oxide with a nucleophile as described in Japanese Patent Publication (Kokoku) H01-32808. [0037]

The present invention also relates to the method for producing the carboxylic acid salt of formula (4) : FSO 2 CF 2 CF 2 OCF(CF 2 CI)COOM (4) wherein M is as defined above, which comprises the step of contacting the acid halide of formula (3) with a base of MHCO 3 or M 2 CO 3 (in which M is Na or K) . [0038]

Preferred as the base of MHCO 3 or M 2 CO 3 is Na 2 CO 3 or K 2 CO 3 . [0039]

The present invention also relates to the method for producing the vinyl ether of FSO 2 CF 2 CF 2 OCF=CF 2 , which comprises the step of decarboxylating the carboxylic acid of formula (4) . [0040] The decarboxylation reaction is preferably carried out in a dried organic solvent; the organic solvent is diglyme, glyme or tetraglyme, for instance. [0041]

The decarboxylation reaction can be carried out by heating the carboxylic acid salt of formula (4) . The heating temperature is generally 100 to 200°C.

[0042]

The acid halide of formula (3) can also be applied to the process for a vinyl compound production described in Japanese Patent Publication (Kokoku) H01-32808.

[0043]

The method mentioned above can give the vinyl ether of

FSO 2 CF 2 CF 2 OCF=CF 2 in good yields.

[0044] The vinyl ether obtained may be purified in the conventional manner, for example by distillation and/or column chromatography .

[0045]

The vinyl ether of FSO 2 CF 2 CF 2 OCF=CF 2 as obtained by the above method is a compound useful as a starting monomer for the production of a polymer for constituting an electrolyte membrane or ion exchange membrane. [0046]

The electrolyte membrane or ion exchange membrane is used, for example, as an electrolyte membrane in a solid polymer electrolyte fuel cell, a membrane in a lithium cell, a membrane for brine electrolysis, a membrane for water electrolysis, a membrane for hydrohalic acid electrolysis, a membrane in an oxygen concentrator, a membrane in a humidity sensor, and a membrane in a gas sensor. EXAMPLES [0047]

The following examples illustrate the present invention in further detail. These examples are, however, by no means limitative of the scope of the invention. [0048]

Method of 19 F-NMR analysis

Apparatus: Nuclear magnetic resonance spectrometer (product of Nippon Denshi (JEOL)), model: JEOL JNM-EX270 Measurement conditions (solvent: CDCI 3 , internal standard: trichlorofluoromethane) [0049] Method of GC-Mass analysis

Apparatus: Clarus 500 GC/MS gas chromatograph-mass spectrometer (product of PerkinElmer)

Column used: DB-624 [0050] Example 1

To CF 2 Cl-CF 2 -CHCl 2 (500 g, 2.28 mol) were added a 30% (by mass) aqueous KOH solution (570 g) and trioctylmethylammonium chloride (TOMAC) (0.5 g) as the phase transfer catalyst, and the reaction was allowed to proceed with stirring at 70°C for 4 hours. The reaction mixture obtained was allowed to separate into two phases by 1 hour of standing, and the lower layer was recovered. Gas chromatographic analysis of the lower layer recovered indicated 95% progress of the reaction. The lower layer recovered was purified by distillation to give 420 g of CF 2 Cl-CF=CCl 2 . [0051] To the CF 2 Cl-CF=CCl 2 obtained (5Og, 0.25 mol) were added a 15% (by mass) aqueous NaOCl solution (370 g) and TOMAC (0.5 g) as the phase transfer catalyst, and the reaction was allowed to proceed with stirring at 6O 0 C for 6 hours. The reaction mixture obtained was allowed to separate into two phases by 1 hour of standing, and the lower layer was recovered. Gas chromatographic analysis of the lower layer recovered indicated 42% progress of the reaction. 19 F-NMR analysis and GC-Mass analysis of the lower layer revealed that the layer was composed of 1, 1, 3-trichloro-2, 3, 3-trifluoropropylene oxide of formula: [0052]

[0053]

The results of 19 F-NMR analysis and GC-Mass analysis are shown below. [0054]

Result of 19 F-NMR analysis

19 F-NMR: δ -65.8 (d, J = 13.8 Hz, 2F) , -148.2 (t, J = 13.8 Hz, IF) [0055] Result of GC-Mass analysis

MS (GC-Mass): (m/z (relative intensity) ) 220 (M+6, 1) , 218 (M+4, 10), 216 (M+2, 30), 214 (M + , 30), 198 (31), 163 (77), 144 (10), 116 (25), 85 (35), 82 (100), 50 (50) [0056]

Example 2

(Example of production of FSO 2 CF2CF 2 OCF=CF 2 )

A 100-ml four-necked flask equipped with a thermometer holder, two Dimroth condensers and a dropping funnel was charged with 30 ml of diglyme and 3 g of KF, then the flask was cooled to 0°C and the contents were stirred. The β-sultone (30 g, 167 mmol) was added from the dropping funnel and

1, 1, 3-trichloro-2, 3, 3-trifluoropropylene oxide (35.6 g, 166 mmol) was then added. After the dropwise addition, the resultant mixture was stirred at 0°C for 1 hour and then stirred at 4O 0 C for 2 hours. After stopping the stirring, the mixture was allowed to separate into two layers by 30 minutes of standing, and then the lower layer (58.2 g) was drawn out. 19 F-NMR analysis of the lower layer revealed that it was 88% pure FSO 2 CF 2 CF 2 OCF(CF 2 CI)COCI (yield 78%). [0057]

The FSO 2 CF 2 CF 2 OCF(CF 2 CI)COCI obtained in the above manner was added dropwise at room temperature to an aqueous solution of Na 2 CO 3 prepared by dissolving Na 2 CO 3 (17.9 g, 169 mmol) in 200 ml of water. After 4 hours of stirring, the content fluid was filtered, and then the filtrate was dried under reduced pressure. The solid obtained was washed with 20 ml of chloroform and further dried. The thus-obtained solid was identified as the carboxylic acid salt of FSO 2 CF 2 CF 2 OCF (CF 2 Cl) COONa . [0058]

The solid (52 g) obtained in the above manner and 100 ml of diglyme were placed in a 200-ml flask equipped with a distillation apparatus and heated at 140°C. The distillate fraction showing a boiling point of 75 to 8O 0 C was taken out and subjected to GC-Mass analysis and 19 F-NMR analysis. The fraction was found to consist of 98% of FSO 2 CF 2 CF 2 OCF=CF 2 and 2% of FSO 2 CF 2 CF 2 OCHFCCIF 2 . The overall yield of FSO 2 CF 2 CF 2 OCF=CF 2 was 69%. INDUSTRIAL APPLICABILITY [0059]

1, 1, 3-Trichloro-2, 3, 3-trifluoropropylene oxide of the invention is a novel compound useful, in particular, as a starting monomer for the production of an electrolyte polymer for use in a fuel cell.