METHOD FOR PRODUCING OLEFIN CONTAINING CHLORINE AND FLUORINE

Abstract

A method for producing at least one olefin compound selected from the group consisting of a compound of formula (51) and a compound of formula (52), the method including reacting an olefin compound of formula (21) with a olefin compound of formula (31) in the presence of at least one metal catalyst selected from the group consisting of a compound of formula (11), a compound of formula (12), a compound of formula (13), a compound of formula (14), and a compound of formula (15).

##STR00001##

Claims

1: A method for producing at least one olefin compound selected from the group consisting of a compound of formula (51) and a compound of formula (52), the method comprising: reacting an olefin compound of formula (21) with a olefin compound of formula (31) in the presence of at least one metal catalyst selected from the group consisting of a compound of formula (11), a compound of formula (12), a compound of formula (13), a compound of formula (14), and a compound of formula (15): ##STR00039## wherein [L] is a ligand; M is ruthenium, molybdenum or tungsten; A.sup.1 to A.sup.6 are each independently a functional group selected from the group consisting of functional group (i), functional group (ii), functional group (iii), and functional group (iv); A.sup.1 and A.sup.2 may bond to each other to form a ring; A.sup.3 and A.sup.4 may bond to each other to form a ring; A.sup.5 and A.sup.6 may bond to each other to form a ring; provided that in the case where one of A.sup.1 or A.sup.2 is a halogen atom, the other is a functional group selected from the group consisting of the functional group (i), the functional group (iii) and the functional group (iv); in the case where one of A.sup.3 or A.sup.4 is a halogen atom, the other is a functional group selected from the group consisting of the functional group (i), the functional group (iii) and the functional group (iv); and in the case where one of the A.sup.5 or A.sup.6 is a halogen atom, the other is a functional group selected from the group consisting of the functional group (i), the functional group (iii) and the functional group (iv); and X.sup.1 and X.sup.2 are each independently a functional group selected from the group consisting of the functional group (i), the functional group (ii), the functional group (v), and the functional group (vi), and X.sup.1 and X.sup.2 they may bond to each other to form a ring; provided that in the case where one of X.sup.1 or X.sup.2 is a fluorine atom, the other is a functional group selected from the group consisting of the functional group (i), a halogen atom except for a fluorine atom, the functional group (v) and the functional group (vi): functional group (i): a hydrogen atom; functional group (ii): a halogen atom; functional group (iii): a monovalent hydrocarbon group having a carbon number of from 1 to 20; functional group (iv): a monovalent hydrocarbon group having a carbon number of from 1 to 20 and containing one or more atoms selected from the group consisting of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom; functional group (v): a functional group selected from the group consisting of an alkyl group having a carbon number of from 1 to 12, an alkoxy group having a carbon number of from 1 to 12, an aryl group having a carbon number of from 5 to 20, an aryloxy group having a carbon number of from 5 to 20, a (per)halogenated alkyl group having a carbon number of from 1 to 12, a (per)halogenated alkoxy group having a carbon number of from 1 to 12, a (per)halogenated aryl group having a carbon number of from 5 to 20, and a (per)halogenated aryloxy group having a carbon number of from 5 to 20; and functional group (vi): the functional group (v) containing one or more atoms selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom.

2: The production method according to claim 1, wherein the reacting is carried out with the olefin compound of formula (21), X.sup.1 is the functional group (i), the functional group (ii), the functional group (v), or the functional group (vii) and X.sup.2 is the functional group (ii), the functional group (v), or a functional group (vii): and wherein the functional group (vii) is the functional group (v) having an etheric oxygen atom between a carbon atom and a carbon atom.

3: The production method according to claim 1, comprising reacting at least one compound selected from the group consisting of 1-chloro-1-fluoroethylene, 1,2-dichloro-1,2-difluoroethylene, and 1,3,3-trichloro-1,2,3-trifluoropropene with the olefin compound of formula (31).

4: The production method according to claim 1, wherein M is ruthenium.

5: The production method according to claim 1, wherein M is molybdenum or tungsten, and the metal catalyst has an imide ligand and a ligand including two coordinating oxygen atoms as the ligand [L].

6: The production method according to claim 1, wherein the olefin compound of formula (31) is ethylene, a monosubstituted olefin, or a 1,2-disubstituted olefin.

7: The production method according to claim 1, wherein in the olefin compound of formula (31), A.sup.3 is a hydrogen atom and A.sup.4 is a hydrogen atom, a monovalent hydrocarbon group having a carbon number of from 1 to 20, or a monovalent hydrocarbon group having a carbon number of from 1 to 20 and containing one or more atoms selected from the group consisting of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom.

8: The production method according to claim 1, wherein the olefin compound of formula (31) is at least one olefin compound selected from olefin compounds represented by the following formulae: wherein R is an alkyl group having a carbon number of from 1 to 12 or an alkyl group having a carbon number of from 1 to 12 and having an etheric oxygen atom between a carbon atom and a carbon atom, and Ar is an aryl group having a carbon number of from 5 to 12 ##STR00040##

9: The production method according to claim 1, wherein the olefin compound of formula (31) is an olefin compound having a heteroatom existing adjacent to a carbon atom of the olefin.

10: The production method according to claim 9, wherein the heteroatom is an oxygen atom or a nitrogen atom.

11: The production method according to claim 1, wherein the reacting forms at least one olefin compound selected from olefin compounds represented by the following formulae as the compound of formula (51) and the compound of formula (52): wherein R is an alkyl group having a carbon number of from 1 to 12 or an alkyl group having a carbon number of from 1 to 12 and having an etheric oxygen atom between a carbon atom and a carbon atom, and Ar is an aryl group having a carbon number of from 5 to 12 ##STR00041##

12: The production method according to claim 1, wherein a temperature during the reacting is from 0 to 150° C.

13: The production method according to claim 1, wherein the reacting is carried out in the absence of a solvent.

Description

EXAMPLE 1

[0154] Metathesis of Dodecyl Vinyl Ether and 1,2-dichloro-1,2-difluoroethylene (R-1112) with Umicore M73SIPr Catalyst

[0155] In a nitrogen atmosphere, dodecyl vinyl ether (0.06 mmol), Umicore M73SIPr catalyst (10 mol %; 0.006 mmol), 1,2-dichloro-1,2-difluoroethylene (R-1112) (0.06 mmol), and m-xylene-d.sub.10 (0.6 mL) containing p-bis(trifluoromethyl)benzene (internal standard; 0.02 mmol) dissolved therein were weighed and put into an NMR tube.

[0156] The NMR tube was heated at 60° C., and the reaction was conducted at that temperature for 1 hour. After completion of the reaction, NMR and GC-MS of the liquid content were measured to confirm the formation of (2-chloro-2-fluorovinyl) dodecyl ether.

[0157] The series of the reaction is shown below. The catalyst turnover number (catalyst turnover frequency per hour) calculated from the .sup.19F-NMR spectrum [internal standard, p-bis(trifluoromethyl)benzene] was 0.5.

##STR00022##

REFERENCE EXAMPLE 1

[0158] Metathesis of Dodecyl Vinyl Ether and 1,2-dichloro-1,2-difluoroethylene (R-1112) with Commercial Molybdenum Catalyst B

[0159] In a nitrogen atmosphere, a commercial molybdenum catalyst B (2 mol %; 0.0012 mmol), dodecyl vinyl ether (0.06 mmol), 1,2-dichloro-1,2-difluoroethylene (R-1112) (0.12 mmol), and benzene-d.sub.6 (0.6 mL) containing p-bis(trifluoromethyl)benzene (internal standard; 0.01 mmol) dissolved therein were weighed and put into a pressure-proof NMR tube.

[0160] The NMR tube was heated at 60° C. and held at that temperature for 1 hour. After the 1-hour holding, the starting materials only were recovered and the desired product was not obtained.

##STR00023##

REFERENCE EXAMPLE 2

[0161] Metathesis of Dodecyl Vinyl Ether and 1,2-dichloro-1,2-difluoroethylene (R-1112) with Commercial Molybdenum Catalyst C

[0162] In a nitrogen atmosphere, a commercial molybdenum catalyst C (2 mol %; 0.0012 mmol), dodecyl vinyl ether (0.06 mmol), 1,2-dichloro-1,2-difluoroethylene (R-1112) (0.12 mmol), and benzene-d.sub.6 (0.6 mL) containing p-bis(trifluoromethyl)benzene (internal standard; 0.01 mmol) dissolved therein were weighed and put into a pressure-proof NMR tube.

[0163] The NMR tube was heated at 60° C. and held at that temperature for 1 hour. After the 1-hour holding, the starting materials only were recovered and the desired product was not obtained.

##STR00024##

EXAMPLE 2

[0164] Metathesis of Butyl Vinyl Ether and 1,2-dichloro-1,2-difluoroethylene (R-1112) with Commercial Molybdenum Catalyst D

[0165] In a nitrogen atmosphere, a commercial molybdenum catalyst D (2 mol %; 0.0012 mmol), butyl vinyl ether (0.06 mmol; previously degassed by freeze-pump-thaw cycles and dried over potassium hydroxide), 1,2-dichloro-1,2-difluoroethylene (R-1112) (0.12 mmol), and benzene-d.sub.6 (0.6 mL) containing p-bis(trifluoromethyl)benzene (internal standard; 0.02 mmol) dissolved therein are weighed and put into a pressure-proof NMR tube.

[0166] The NMR tube is heated at 60° C. and the reaction is conducted at that temperature for 1 hour. After completion of the reaction, NMR and GC-MS of the liquid content are measured to confirm the formation of butyl (2-chloro-2-fluorovinyl) ether.

##STR00025##

EXAMPLES 3 AND 4

[0167] The 1,2-dichloro-1,2-difluoroethylene in Example 1 is replaced with each of the compounds shown in Table 1, and the reaction is conducted. The compounds shown in Table 1 are produced as products.

TABLE-US-00001 TABLE 1 Product Example Compound (21) Compound (51) and Compound (52) 3 [00026] [00027] 4 [00028] [00029]

EXAMPLES 5 AND 6

[0168] The 1,2-dichloro-1,2-difluoroethylene in Example 2 is replaced with each of the compounds shown in Table 2, and the reaction is conducted. The compounds shown in Table 2 are produced as products.

TABLE-US-00002 TABLE 2 Product Example Compound (21) Compound (51) and Compound (52) 5 [00030] [00031] 6 [00032] [00033]

EXAMPLES 7 AND 8

[0169] The butyl vinyl ether in Example 1 is replaced with each of the compounds shown in Table 3, and the reaction is conducted. The compounds shown in Table 3 are produced as products.

TABLE-US-00003 TABLE 3 Product Example Compound (31) Compound (51) and Compound (52) 7 [00034] [00035] 8 [00036] [00037]

EXAMPLE 9

[0170] Metathesis of Butyl Vinyl Ether and Tetrafluoroethylene with Commercial Molybdenum Catalyst D

[0171] In a nitrogen atmosphere, the commercial molybdenum catalyst D (1 mol %), 1,2-dichloro-1,2-difluoroethylene (R-1112) (0.12 mmol), and butyl vinyl ether (0.12 mmol; previously degassed by freeze-pump-thaw cycles and dried over potassium hydroxide) are weighed and put into a pressure-proof reactor.

[0172] The NMR tube is heated at 60° C., and the reaction is conducted at that temperature for 1 hour. After completion of the reaction, NMR and GC-MS of the liquid content are measured to confirm the formation of butyl (2-chloro-2-fluorovinyl) ether.

[0173] The series of the reaction is shown below.

##STR00038##

INDUSTRIAL APPLICABILITY

[0174] According to the present invention, other olefins containing chlorine and fluorine can be simply and efficiently produced from industrially-easily-available olefins containing chlorine and fluorine such as R-1112, i.e., 1,2-dichloro-1,2-difluoroethylene, or R-1131a, i.e., 1-chloro-1-fluoroethylene through olefin metathesis.

[0175] While the present invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof. This application is based on a Japanese patent application filed on Dec. 26, 2014 (Application No. 2014-266097), the contents thereof being incorporated herein by reference.