PRODUCTION METHOD FOR FLUORINE-CONTAINING OLEFIN COMPOUND

Abstract

A method for producing at least one compound of a fluorine-containing olefin compound (51) or a fluorine-containing olefin compound (52) includes performing a reaction of a fluorine-containing olefin compound (21) with an olefin compound (31) in the presence of a metal-carbene complex compound having an olefin metathesis reaction activity and an olefin compound (41) or (42).

##STR00001##

Claims

1. A method for producing at least one compound of a fluorine-containing olefin compound of formula (51) or a fluorine-containing olefin compound of formula (52), the method comprising: reacting a fluorine containing olefin compound of formula (21) with an olefin compound of formula (31) to form the fluorine-containing olefin compound of formula (51) or the fluorine-containing olefin compound of formula (52); wherein the reacting is carried out in the presence of a metal-carbene complex compound (10) having an olefin metathesis reaction activity and a compound of formula (41), or in the presence of the metal-carbene complex compound (10) and an olefin compound of formula (42): ##STR00052## wherein A.sup.11 and A.sup.12 are each independently a group selected from the group consisting of group (i), group (iia), group (iii), and group (iv), and A.sup.11 and A.sup.12 may bond to each other to form a ring; with the proviso that in the case where one of A.sup.11 or A.sup.12 is a halogen atom, the other is a group selected from the group consisting of group (i), group (iii), and group (iv); A.sup.13 is a group selected from the group consisting of the following group (i), group (iii), and group (iv); E is a group selected from the group consisting of —OR′, —OSiR′.sub.3, —NR′.sub.2, —SR′, and group (iia), and each R′ is independently a group selected from the group consisting of group (i), group (v), and group (vi); A.sup.13 and E may bond to each other to form a ring; X.sup.11 and X.sup.12 are each independently a group selected from the group consisting of group (i), group (ii), group (v), and group (vi), X.sup.11 and X.sup.12 may bond to each other to form a ring; X.sup.13 is a group selected from the group consisting of group (ii), group (v), and group (vi); R.sup.11 to R.sup.14 are each independently a group selected from the group consisting of —H, —CH.sub.2R, —CH(CR.sub.3).sub.2, —C(CR.sub.3).sub.3, and —Ar, wherein each R is independently a group selected from the group consisting of a hydrogen atom, an alkyl group having a carbon number of from 1 to 12, and an alkyl group having a carbon number of from 1 to 12 and having an etheric oxygen atom between carbon atoms, and Ar is an aryl group having a carbon number of from 5 to 12; R.sup.11 and R.sup.12 may bond to each other to form a ring; R.sup.13 and R.sup.14 may bond to each other to form a ring; group (i): a hydrogen atom; group (ii): a halogen atom; group (iia): a chlorine atom, a bromine atom, or an iodine atom; group (iii): a monovalent hydrocarbon group having a carbon number of from 1 to 20; 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; group (v): a 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; group (vi): the group (v) further 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 olefin compound of formula (41) or formula (42) is at least one compound selected from the group consisting of ##STR00053## wherein each R′ is independently a group selected from the group consisting of group (i), group (v), and group (vi).

3. The production method according to claim 1, wherein X.sup.13 is the fluorine-containing olefin compound of formula (21) is a halogen atom or a perhalogenated alkyl group having a carbon number of from 1 to 8.

4. The production method according to claim 1, wherein a metal in the metal-carbene complex compound (10) is ruthenium, molybdenum, or tungsten.

5. The production method according to claim 1, wherein a metal in the metal-carbene complex compound (10) is ruthenium.

6. The production method according to claim 1, wherein a metal in the metal-carbene complex compound (10) is molybdenum or tungsten and the metal-carbene complex compound (10) has an imide ligand and a ligand including two coordinating oxygen atoms as a ligand [L].

7. The production method according to claim 1, wherein in the olefin compound represented by the formula (21), X.sup.11 is group (i), group (ii) group (v), or group (vi), X.sup.12 is group (i), group (ii), group (v), or group (vi), and X.sup.13 is group (ii), group (v) or group (vi).

8. The production method according to claim 1, wherein the olefin compound of formula (21) is a 1,1-difluoroolefin.

9. The production method according to claim 1, wherein the olefin compound of formula (21) is at least one olefin compound selected from the group consisting of ##STR00054## wherein Rf is a (per)fluorinated alkyl group having a carbon number of from 1 to 20, a (per)fluorinated alkyl group having a carbon number of from 1 to 20 and having an etheric oxygen atom between a carbon atom and a carbon atom, or a (per)fluorinated aryl group having a carbon number of from 5 to 20.

10. The production method according to claim 1, wherein the reacting is carried out at a temperature of from 0 to 150° C.

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

Description

EXAMPLES

[0159] The present invention is explained below in detail by reference to Examples, but the invention should not be construed as being limited thereto.

<Commercial Reagents>

[0160] In the Examples, as for the catalyst, commercial products were used in the reaction directly as they are, unless otherwise specifically indicated. As for solvents (benzene-d.sub.6 and o-dichlorobenzene-d.sub.4), commercial products were previously degassed by freeze-pump-thaw cycles and subsequently dried with Molecular Sieve 4A and were then used in the reaction.

<Evaluation Methods>

[0161] The structure of the compound synthesized in the Examples was identified through measurement of .sup.1H-NMR and .sup.19F-NMR spectroscopy with a nuclear magnetic resonance spectroscope (JNM-AL300) manufactured by JEOL Ltd. The molecular weight was measured according to an electron ionization (EI) using a gas chromatography mass s spectrometer (GCMS-QP2010Ultra) manufactured by Shimadzu.

Example 1

[0162] Metathesis of propylene and tetrafluoroethylene with Grubbs' second-generation catalyst in the presence of ethyl vinyl ether.

[0163] In a nitrogen atmosphere, Grubbs' second-generation catalyst shown below (Grubbs 2.sup.nd, 20 mol %, 0.024 mmol), ethyl vinyl ether (20 mol %, 0.024 mmol), and benzene-d.sub.6 (0.6 mL) were weighed and put into a pressure proof NMR tube. Thereafter, the gas-phase part in the NMR tube was replaced with a propylene/tetrafluoroethylene=1/1 mixed gas (v/v, 1.0 atm, 2.7 mL, 0.12 mmol).

[0164] 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 of the liquid content was measured to confirm the formation of 1,1-difluoro-1-propene.

[0165] The series of reactions is shown below.

##STR00024##

Example 2

[0166] Metathesis of styrene and tetrafluoroethylene with Grubbs' second-generation catalyst in the presence of ethyl vinyl ether.

[0167] In a nitrogen atmosphere, styrene (0.12 mmol), Grubbs' second-generation catalyst shown below (Grubbs 2.sup.nd, 20 mol %, 0.024 mmol), ethyl vinyl ether (20 mol %, 0.024 mmol), and o-dichlorobenzene-d.sub.4 (0.6 mL) are weighed and put into a pressure-proof NMR tube. Thereafter, the gas-phase part in the NMR tube is replaced with tetrafluoroethylene (1.0 atm, 2.7 mL, 0.12 mmol),

[0168] The NMR tube is heated at 180° C., and the reaction is conducted at that temperature for 1 hour. After completion of the reaction, NMR of the liquid content is measured to confirm the formation of β, β-difluorostyrene.

[0169] The series of reactions is shown below.

##STR00025##

Example 3

[0170] Metathesis of propylene and tetrafluoroethylene with Grubbs' second-generation catalyst in the presence of ethyl vinyl ether

[0171] In a nitrogen atmosphere, Grubbs' second-generation catalyst shown below (Grubbs 2.sup.nd, 20 mol %, 0.024 mmol), ethyl vinyl ether (20 mol %; 0.024 mmol), and benzene-d.sub.6 (0.6 mL) are weighed and put into a pressure-proof NMR tube. Thereafter, propylene (1.0 atm; 1.35 mL; 0.06 mmol) is put into the gas-phase part in the NMR tube. The NMR tube is heated at 60° C., and the reaction is conducted at that temperature for 1 hour. Thereafter, tetrafluoroethylene (1.0 atm, 1.35 mL, 0.06 mmol) is put into the gas-phase part in the NMR tube, and further the NMR tube is heated at 60° C. to conduct the reaction at that temperature for 1 hour. After completion of the reaction, NMR of the liquid content is measured to confirm the formation of 1,1-difluoro-1-propene.

[0172] The series of reactions is shown below.

##STR00026##

Examples 4 and 5

[0173] Metathesis of propylene and tetrafluoroethylene with ruthenium catalyst in the presence of ethyl vinyl ether

[0174] The Grubbs' second-generation catalyst in Example 1 is replaced with the known ruthenium catalysts B and C represented by the following known formulae, and reaction is conducted in the same manner to obtain the same product as in Example 1.

TABLE-US-00001 TABLE 1 Ex. Catalyst Structure 4 B [00027] 5 C [00028]

Examples 6 to 9

[0175] Metathesis of propylene and tetrafluoroethylene with ruthenium catalyst in the presence of ethyl vinyl ether

[0176] The Grubbs' second-generation catalyst in Example 1 is replaced with the known molybdenum catalysts D to G represented by the following formulae, and reaction is conducted in the same manner to obtain the same product as in Example 1.

TABLE-US-00002 TABLE 2 Ex. Catalyst Structure 6 D [00029] 7 E [00030] 8 F [00031] 9 G [00032]

Example 10

[0177] Metathesis of propylene and tetrafluoroethylene with tungsten catalyst in the presence of ethyl vinyl ether

[0178] The Grubbs' second-generation catalyst in Example 1 is replaced with the known tungsten catalyst H represented by the following formula, and reaction is conducted in the same manner to obtain the same product as in Example 1.

TABLE-US-00003 TABLE 3 Ex. Catalyst Structure 10 H [00033]

Examples 11 and 12

[0179] Metathesis of styrene and tetrafluoroethylene with ruthenium catalyst in the presence of ethyl vinyl ether

[0180] The Grubbs' second-generation catalyst in Example 2 is replaced with the known ruthenium catalysts B and C described above, and reaction is conducted in the same manner to obtain the same product as in Example 2.

Examples 13 to 16

[0181] Metathesis of styrene and tetrafluoroethylene with molybdenum catalyst in the presence of ethyl vinyl ether

[0182] The Grubbs' second-generation catalyst in Example 2 is replaced with the known molybdenum catalysts D to G described above, and reaction is conducted in the same manner to obtain the same product as in Example 2.

Examples 17 to 24

[0183] Metathesis of propylene and tetrafluoroethylene with ruthenium catalyst in the presence of compound (41)

[0184] The ethyl vinyl ether in Example 1 is replaced with the commercial compound (41) represented by the following formulae, and reaction is conducted in the same manner to obtain the same product as in Example 1.

TABLE-US-00004 TABLE 4 Ex. Compound (41) 17 [00034] 18 [00035] 19 [00036] 20 [00037] 21 [00038] 22 [00039] 23 [00040] 24 [00041]

Examples 25 to 28

[0185] Metathesis of propylene and compound (21) with Grubbs' second-generation catalyst in the presence of ethyl vinyl ether

[0186] The tetrafluoroethylene in Example 1 is replaced with the compound (21) represented by the following formulae, and reaction is conducted in the same manner. The fluorine-containing olefin compounds shown in Table 5 are obtained as products.

TABLE-US-00005 TABLE 5 Ex. Compound (21) Fluorine-containing olefin compound (21) 25 [00042] [00043] 26 [00044] [00045] 27 [00046] [00047] 28 [00048] [00049]

Example 29

[0187] Metathesis of propylene and tetrafluoroethylene with Grubbs' second-generation catalyst in the presence of ethyl vinyl ether using no solvent

[0188] In Example 1, the solvent (benzene-d.sub.6) is not put, and reaction is conducted in the same manner. Thus, the same product as in Example 1 is obtained.

Example 30

[0189] Metathesis of styrene and tetrafluoroethylene with Grubbs' second-generation catalyst in the presence of ethyl vinyl ether using no solvent

[0190] In Example 2, the solvent (benzene-d.sub.6) is not put, and reaction is conducted in the same manner. Thus, the same product as in Example 2 is obtained.

Comparative Example 1

[0191] Metathesis of propylene and tetrafluoroethylene with Grubbs' second-generation catalyst in the absence of ethyl vinyl ether

[0192] In a nitrogen atmosphere, Grubbs' second-generation catalyst shown below (Grubbs 2nd; 20 mol %, 0.024 mmol) and benzene-d.sub.6 (0.6 mL) were weighed and put into a pressure-proof NMR tube. Thereafter, the gas-phase part in the NMR tube was replaced with a propylene/tetrafluoroethylene=1/1 mixed gas (v/v, 1.0 atm, 2.7 mL, 0.12 mmol).

[0193] 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 of the liquid content is measured. However, 1,1-difluoro-1-propene was formed only in a trace amount.

[0194] The series of reactions is shown below.

##STR00050##

Comparative Example 2

[0195] Metathesis of styrene and tetrafluoroethylene.with Grubbs' second-generation catalyst in the absence of ethyl vinyl ether

[0196] In a nitrogen atmosphere, styrene (0.12 mmol), Grubbs' second-generation catalyst shown below (Grubbs 2.sup.nd, 20 mol %, 0.024 mmol), and o-dichlorobenzene-d.sub.4 (0.6 mL) are weighed and put into a pressure-proof NMR tube. Thereafter, the gas-phase part in the NMR tube is replaced with tetrafluoroethylene (1.0 atm, 2.7 mL, 0.12 mmol).

[0197] The NMR tube is heated at 180° C., and the reaction is conducted at that temperature for 1 hour. After completion of the reaction, NMR of the liquid content is measured to confirm that β,β-difluorostyrene is generated only in a trace amount or is not formed at all.

[0198] The series of reactions is shown below.

##STR00051##

[0199] While the 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 Mar. 3, 2015 (Application No. 2015-041644), the contents thereof being incorporated herein by reference.

INDUSTRIAL APPLICABILITY

[0200] According to the present invention, a fluorine-containing olefin compound can be easily and highly efficiently produced by carrying out a metathesis reaction of a fluorine-containing olefin and another olefin in the presence of a metal-carbene complex compound and a third olefin compound.