JPS59137424A - Production of polyfluoroalkyl halide - Google Patents

Abstract

PURPOSE:To prepare the titled compound useful as an intermediate of surface agent, etc., economically, by reacting a 1-20C halopolyfluorocarbon with substituted or unsubstituted ethylene or acetylene in the presence of a VIII-group metal carbonyl complex. CONSTITUTION:The objective compound of formula IV or formula V useful as an intermediate of a water-repellent, oil-repellent, textile sizing agent, etc. as well as the above-mentioned use, is prepared in a short time under mild reaction condition, by reacting (A) a 1-20C compound of formula I (X is Cl, Br, or I; R<1> and R<2> are H, halogen or poly-perfluorocarbon residue) with (B) the compound of formula II or III (R<3>-R<8> are group of R<1> or R<2>, or substituted or unsubstituted alkyl, vinyl, aromatic group, alkyloxy, acyloxy, NH2, amido, silyl, etc.) in the presence of (C) a carbonyl complex of the VIII-group metal of the periodic table (preferably Fe or Ru) preferably at room temperature -120 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyfluoroalkyl halides. More specifically, a halopolyfluorocarbon having 1 to 20 carbon atoms is reacted with ethylene or acetylene of a group VIIL of the periodic table in the presence of a metal or a carbonyl substance of group VIIL of the periodic table to form a polyfluoroalkyl halide (however, Here, halogen refers to chlorine, bromine, and iodine).

+47 Polyfluoroalkyl halides are used as world [[IJ activators, water repellents, oil repellents,
It is useful as an intermediate for fiber treatment agents, etc. (see, for example, Japanese Patent Publications No. 50-37644, Japanese Patent Publication No. 49-88811, and Japanese Patent Publication No. 53-8683).

Conventionally, methods for producing the polyfluoroalkyl halide obtained according to the present invention include (a) a method in which a mixture of iodoperfluoroalkanes and olefins/or acetylenes is irradiated with light (for example, LeN, T4ASZELD);
ine, J, Chem, Soc, 2856(1
949); 3037 (1950), ) (b) Iodoperfluoroalkane and olefin or acetylene knowledge 2
A method of obtaining L N
, Haszeldine, J., Chern, S.
oc, + 2789 (1950); L N, Has
zeldine and B, )(.

5teele, J, Chem, 5oc-+ 11
99 (1953)-), (c) A method of reacting a Rancal opener such as di-t-butyl perfluoroalkane and an olefin or acetylene under heating (for example, , Baum, C.
D, Bedford and R, J', ) luna
di + J-Org, Chem, + 4L 225
A method of reacting with an olefin in the presence of a metal salt or an amine-metal salt complex (Japanese Unexamined Patent Publication No. 47-53
No. 68, Time No. 11850-37644 and Special Publication No. 1973
-8683 silkworm j1Q) is known.

However, method 0) requires 1 ij of light irradiation for a long period of time, and has the disadvantage that the yield is generally mediocre. (The direction of ri will also be solved if Tsutsukinoshita does not construct Keiji ftj, but I love it, Yu/j +'tb Toh I'1. Method (c) also generally requires a long-term reaction of lLi4 at a certain reaction temperature, and the Rancal initiation rule used is generally unstable and dangerous, so care must be taken when handling it. In addition, the disadvantage that the radical initiator used cannot be recovered is overcome.The method in (2) requires a long reaction time and the sieve temperature to achieve the desired yield. It has the disadvantage of not being able to obtain I//I [see Comparative Example].

The present inventors have investigated the drawbacks of the rice cleaning method for JV.1 By using a metal carbonyl lead body as a catalyst, polyfluoroalkyl halides can be produced in a short time under mild reaction conditions. They found that it can be manufactured and completed the present invention.

The present invention can be implemented using the following reaction formula.

P゛ Formula 3 ratio 5 1 1 1 (wherein, X is a carrier atom, a paternal atom, or an iodine atom, gl
and 1mo2 is a hydrogen atom, a halogen atom, a poly or perfluorocarbon group. kL3, R4,145,
l(+6, It7 and 几8 are each a hydrogen atom, a halogen atom, a poly or perfluorocarbon group, 1h
Oral or unsubstituted alkyl group, vinyl group, aromatic group,
These include an alkyloxy group, an acyloxy group, an amino group, an amide group, a silyl group, a silyloxy group, an alkylthio group, an alkoxycarbonyl group, an acyl group, a polmyl group, and an /ano group. ) This nine-metal material is made from haloborifurune 1-locarbon having 1 to 20 carbon atoms. 1
~20 (17j (1) Jj/7f, μ, ・ Examples of halopolyfluorocarbons having all children include iodotrifluoromethane, 1-iotohentafluoroethane, 1-
Iodohebutafluoropropane, 1-iodononafluorobutane, 1-iodoperfluorohebutane, 1-iodoherfluorooctane, ■-iodober 7/thiolodecane, 2-iodobutafluoropropane, 2-bromo-1-iodo Tetrafluoroethane, 1,2-dichloro-1-iodotrifluoroethane, 1,2-short tetrafluoroethane, 1-chloro-2-iodo-1,1
, 2-trifluoroethane, 1,4-shorterfluorobutane, 1,6-shorterfluorohexane,
1.8-iodoperfluorooctane, 2-nonafluorobutyl-1゜1-difluoro-1-iodoethane,
1,3,3.3-tetrafluoro-1-iodopropane, iodoperfluorotoluene, difluorodibromomethane, trifluorobromomethane, bromochlorofluoromethane, 1,2-dibromotetrafluoroethane,
1-10 rho 12-cyfuromotrifluoroethane, 1.
2-dibromohexafluoropropane, 1-bromopentafluoroethane, 1-bromohebtafluorofuban, 1-bromoperfluorohexane, etc. can be used.

Substituted or unsubstituted ethylene or acetylene, which is one of the raw materials for Kinoeyu J, includes ethylene, propylene, 1
-butene, 1-pentene, 1-hexene, vinyl chloride,
Beautified vinyl, vinyl acetate, vinyl ethyl ether, vinyloxytrimethylsilane, vinyl ethyl sulfide, N
-Vinyl-2-pyrrolidinone, vinyltrimethylsilane, styrene, hinylpyridine, butadiene, imprene, piperylene, allyl alcohol, allylamine, allylmercaptan, allyl acetate, allyloxytrimethyl 7rane, ・Vinyl acetate methyl, ethyl acrylate, acrolein, Acrylonitrile, 1-penten-3-ol, 3-buten-1-ol, acrolein diethyl acetal, 2-allyloxyethanol, allylbenzene, trifluoropropene, hephtafluoroglopylethylene, 2-butene, cyclohexene, 3- Hexene, croton-branched methyl, 2-butene-1,4-diol, isobutylene, 2-methyl-
2-butene, vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, hexafluorocropene, etc. +7) tft-substituted H or unsubstituted ethylene, acetylene, propyne, butyne, heptyne, phenylacetylene, trimethylsilylacetylene , phlopargyl alcohol, 3-phytin-1-ol, methyl acetylene monocarbon, trifluoropropyne, bis(trimethylsilyl)acetylene, 2-butyne, hexafluoro-2-butyne, 3-hexyne, 2-butyne-1
, 4-diol, acetylenecarboxylated methyl, etc. or unsubstituted acetylene can be used.

The present invention must be carried out in the presence of a metal carbonyl complex of Group V of the periodic table. ■ Examples of group carbonyl complexes include Fe (Co) 5, Fe2 (CO) 9,
Fe5(CO)1□, C4H6Fe, (CO)3, C4
H4Fe(CO)5, [C3H3Fe(CO)2]2,
[Et3NH] [HFO2(CO)+□:), i'yF
e (CO) 4 iron carbonyl complex, B, u3 (Co
)□2, [1 also uC12(Co) a )2 Temple's ruthenium carbonyl complex, C03(CO)8, Co4(C
O) □2, C3) 15Co (CO)2, CPh 3P
Co(CO)3)]2 etc.: 7 bartocarbonyl complex, Rh6(Co)16, Rh4(Co)1°HRb
(CO) (PPh3) 3, (Rh C1(CO)
2] 2.1(h(7(CO) (PPh 3) 2
Rhodium carbonyl complexes such as ■East (CO) 4.1\
i (PPh3)2(CO)2 etc./l/
Hole & j 5 bodies, 1r (CO) 1□, lr ■ (CO)
(PPh3)2, Li1r (CO) (PPha)a
etc. (D iridium carbonyl complex, (J S 3 (
Although (-0)s 2 and the like can be used, it is preferable to use iron or ruthenium metal carbonyl lead to carry out the reaction with good yield. The amount of metal carbonyl complex used is 1/10,000 to 1/10,000 of halopolyfluorocarbore VC.
It can be used in an amount of 1 equivalent. In order for the reaction to proceed smoothly and to be carried out economically, it is preferable to use the amount in the range of 1/1000 to 1/10.

In order to carry out the present invention more efficiently, it is preferable to carry out the process in the presence of an amine. Amines that can be used include methylamine, ethylamine, filobilamine, isopropylamine, butylamine, amylamine, hexylamine,
Heptylamine, octylamine, nonylamine/, decylamine, lanticylamine, dodecylamine, tridecylamine, tetratecylamine, pentadecylamine, senalamine, allylamine, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, aniline, benzyl Primary amines such as amines, toluidine, and naphthylamine; secondary amines such as dimethylamine, dimethylamine, cyclobruamine, diisophyllamine, cyamylamine, cyamylamine, diallylamine, methylaniline, etheraniline, nbenenylamine, diphenylamine, piperazine, and piperidinone; Amine, trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, dimethylethylamine, triallylamine,
Tertiary amines such as N-methylaniline, diethylaniline, tribenylamine, aromatic amines such as pyridine, collidine, lutidine, pyrrole, indole, N-methylethanolamine, aminoethylisopropanolamine, diethylethanolamine , isopropanolamine, triisopropanazine, jetanolamine, l-liethanolamine, morpholine, N-hydroxyethylmorpholine, and other functional amines. The amount of amine used can be in the range of 1/10,000 to 10 parts per halopolyfluorocarbon, but in order to make the reaction proceed smoothly and economically, it should be in the range of 171,000 to 1 part part. I like it.

In carrying out the present invention, the solvent is not necessarily limited, and if desired, methanol, ethanol, glopanol, etc.
Alcohols such as t-butanol, tetrahydrofuran,
Ethers such as ethyl ether, hydrocarbons such as hexane, cyclohexane, benzene, etc. can be conveniently used.

That's preferable. The reaction proceeds smoothly in a very short time.

The present invention will be explained in detail below with reference to Examples.

Example 1 Chloride m@A (4,9Hi, 0.05mmol)
, 1-iodoheptafluoropropane (296Ff, 1
．． Omm o 13 ), vinyltrimethylsilane (
100niζ1. Qmmo)) and ethanolamine (
A mixture of 30.5r'f, Q, 5 mmol) was heated at 60C for 30 minutes in a glass sealed tube. After opening the package, constant voltage was applied using Cass chromatography (1-iodo-3,
3,4,4,5,5,5-hebutafluoropentyl)trimethyl7sine (1) was produced in a yield of 2%.

12 Ferric chloride (8,11W, 0.05mmo 73)'
, 1-iodohebutafluoroglopa 7 (296In
f, 1.0mm0A)% vinyltrimethylsilane (1
A mixture of 00#I7,l,Q mmol) and ethanolamine (30.5m9% 0.5mmOl) was heated at 60U in a glass@blind for 30 minutes. After opening, the production of trimethylsilane (1) was 1% or less.

1) 9 Raheshi A) (11 Dodecacarbonyl Saniron (6,5!, 0.013mmo
l), 1-iodobutafluoropropane (296F
4.1.0 mmol), vinyltrimethylsilane (10
Mixture of 0IW, 1.0 mm o 11) and ethanolamine (7,3#, 0.12 mmol)? J was heated for 30 minutes at 60C in a glass sealant. After the - period, gas chromatography was carried out to determine the presence of (1-iodo-3,3,4-
, 4,5,5,5-hegtafluorobentyl)trimethylsilane (1) was produced in a yield of 85%.

Examples 2 to 43 The same operations as in Example 1 were carried out to react various polyfluorocarbons and olefins. The used lc halophorifluorocarbon, olefin, catalyst, amine, reaction temperature, and reaction time were listed in Table 1 as well as the yield. Although addition products are generally treated as isomer mixtures, only the main products are shown here.

Example 44 ■ Dotecacarbonyl triiron (8.5 mg, 0.017 mmo
l), 1-iodohefurifluoropropa7 (296
/W, 1. Orlmol) and cyclohexene (82”
P, 1.0mm07) in a glass sealed tube.
The mixture was heated for 5 hours.

After opening the package, quantitative analysis using gas chromatography revealed that 1-hebutafluoroprobyl-2-iodocyclohexane (2
0-a and 20-11 were produced in a yield of 36 inches.

Example 45 C81 (1,7■ +CH2:CH2->08F17~
1 Ruthenium sulfonyl (5,1~, 0.008mmo
l) and 1-iodoperfluorooctane (546#,
1, Onun o /3) f: Place the glass container in an autoclave and heat under 20 atmospheres of ethylene pressure for 60 minutes.
The mixture was heated at c for 20 hours. Quantification of the reaction mixture by gas chromatography revealed 1.1.1.2.2.3.3.
4.4.5.5.6.6°7,7.8.8-Hebutadecafluoro-10-iotothicane (21) was produced in a yield of 75%.

Example C8F'17I +CH2=CH2-mi〉ruthenium carbonyl (17.9 mg, 0.028 mmoA) and U'
1-iodoperfluorooctane (546Ing, 1
, □mmo7) 'r: The glass container containing the mixture was placed in an autoclave and reacted at 60C under 20 atmospheres of ethylene pressure for 20 hours to produce Compound 21 in a yield of 88%.

Example 47 C81I゛171+CH2-C■1□ -RA〉dotecacarbonyl Saniron (33.7mg, 0.067mmol)
&H]-iodoperfluorooctane (546Iig,
1. Put a glass container containing Q man o l) into an autoclave and heat it with 60U of ethylene at 20 atm.
When heated for 0 hours, compound 21 was produced in a yield of 87%.

Example 48 C3F7■+Me-SIMe3-→■ Dotecalysulfonyl Santetsu (6,5#V, 0.013
mm all )■-iodobutafluoropropane (
A mixture of 296 ri, 1, QmmoA), 1.limethylnitrylacetylene (98my, 1.Ol-11mOz) and pyridine (3,2 kite 0.04mm0A) was heated at 60C for 30 minutes in a glass sealed tube. A small amount of 1-iodo-2 was determined by gas chromatography after opening.
-Trimethylsilyl-3,3,4,4,5,5,5-heptafluoro-1-pentene together with 1-iodo-1-trimethylsilyl-3,3°4,4.5.5.5-pebutafluoro-1-pentene (22) was produced with a yield of 78%.

Examples 49 to 76 The same operations as in Example Y7 were performed to react the polyfluorocarbons and acetylenes.

Halophoryfluorocarbon, olefin, catalyst,
Amine and reaction temperature, reaction time with yield x2vci
I stopped it. Although addition products are generally obtained as mixtures of positional and stereoisomers, only the mainly obtained positional isomers are shown here.

Example 77 c3F71 + tv1e3SiC'ECSiMe3-
〉Me3Si I dodecacarbonyl triiron (10.7 mfl, 0.2 mm
of3), 1-iotohebutafluoropropane (2,96g, 10mm0l), bis(trimethylsilyl)acetylene (1,70g, 10rmnol)
) and ethanolamine (110t!/, 1.8mm
The mixture of C1) was heated at 60C for 14 hours in a glass container. The reaction mixture was expressed as "half-white" by glue-based gel column chromatography, and 1°2-bis(trimethylsilyl)-1-iodo-3,3,4,4,5,5,5-
Heptafluoro-1-pentene (34) 2.66g
(yield 57%) and 1-trimethylsilylpv-2-(iodomethyl)methylsilyl-3,3,4,4,5,5
,5-hebutafluoro-1-pentene (L5) Loss Example j
Spectral data of the main product served by ~77 i
The tile shown in 3.4. Stereoisomers of 1 and 2f= were obtained, and those with a and b were circled by adding a and b.

Procedure Correction Illness (spontaneous) December 21, 1981 Bq,'ri'r Kazuo Wakasugi! , $ display Shofo 58en Patent Application No. 994.0 2゜Name of invention Process for producing polyfluoroalkyl halide 3o Supplementary j
Column f', -,, r) <λ 5, "Detailed Description of the Invention" in the specification of the person making E Insert "a-" after.

3) “Dodeka” in line 3 of member 20 and line 6 of page 22 of the same is changed to “
Corrected to "Dodeka".

4) On page 23, line 4, "dodeka" is corrected to "dodeka", and line 13, "pepta" is corrected to "hepta".

5) “Olefin” and “acetylene” on page 24, line 4
Correct.

6) Insert the following after Table 4 on page 37.

[Example 78 ■ Dodecacarbonyl triiron (6,5~, 0.013 mrn
ol), 1-iodohebutafluoropropane (296 da, 1.0 mmol), vinyltrimethylsilane (100 m
A mixture of 9,1.0 mmol, triethylamine (6oIng, Ommθl) and ethanol (0-3 ml) was stirred at room temperature for 30 minutes in a glass-sealed tube. After opening, it was quantified by gas chromatography. 3
,4.

4.5,5.5-hebutafluoropentyl)trimethylsilane was produced in a yield of 70%.

Example 79 C3F7I+Me C3H11→c3F70H=c(■)
c5H11 dodecacarbonyl triiron (6,5~, 0.01
3 mmos, 1-iodobutafluoropropane (29
6 mg, 1.0 mmosu, 1-hepty (96 mg
, 1.0 mmo 1 ), ethano-rumy
(12.2m9.0.2mmol) and ethanol (
The 0.3 mQ mixture was stirred at room temperature for 5 minutes. The reaction mixture was quantified by gas chromatography and found to be 1.1.
1.2,2,3,3. -hebutafluoro-5-iodo-
4-decene 2 was produced with a yield of 62%.

Example 80 C6F7I +=-8iMe3→C3F7CH=C(I
) SiMe3 cobalt octacarbonyl (8,5~,0
．． 025 mmol), 1-yo) hebutafluoropropane (296In9.1.0 mmol), trimethylsilylacetylene (98In9.1.0 tnmol)
) and ethanol (0,3d) were heated at 60° C. for 3 hours in a glass sealed tube. After opening the package, it was determined by gas chromatography to find l-iodo-1-trimethylsilyl-3,3,4°4.5,5.5-heptafluoro-1-
Pentene Ωmets was produced with a yield of 77%.

Example 81 Dodecacarbo=/L+Saniron (lo~, 0.02 mmol
), l-iodohebutafluoropropane (296m9,
A mixture of 1.0 mmol I), propargyl trimethyl 7-sine (112 m9゜1.0 mmol) and ethanolamine (14.6 m9.0.24 mmol) was heated at 60°C for 16 hours in a glass sealed tube. After opening the gas As determined by chromatography, 4, 4, 5, 5, 6
, 6.6-hebutafluoro-2-iodo-2-hexenyltrimethelsilane (36) was produced in a yield of 58%.

Example 82 B rCF2CFCIB r + Ribe〉COOMe
-1 → r Dodecacarbonyl saniron (6,5 吃0,013mm0su,
1.2-dibromo-1-chlorotrifluoroethane (2
76,5m9, 1.0 mmos, methyl 3,3-
Dimethyl-4-pentenoate (142~, 1.0mm
and ethanolamine (7,3η, 0.12mm
The mixture was heated at 60° C. for 4 hours in a glass sealed tube.

After opening, it was determined by gas chromatography that methyl 3゜3-dimethyl-4,7-dibromo-6-chloro-
67, foot trifluorohebutanoate (37) is 7
Produced 1-titer in 8% yield. "that's all

Claims (3)

[Claims] (1) Halopolyfluorocarbons having 1 to 20 carbon atoms are converted or converted into ethylene or acetin/in the presence of a periodic carbonyl starting material.
How to make polyfluoroalkyl halides, which is similar to reacting with chlorine (in this case, halogen refers to chlorine, patrilineal, and iodine). (2) The method according to claim (1), which is carried out in the presence of an amine. (3) The method according to item (1) or (2), wherein the Vl group carbonyl is an iron carbonyl complex or a ruthenium carbonyl complex. (4) Range No. 18 (2) or (3) of q9 ¥' + lees, which consists of carrying out the reaction at a reaction temperature of room temperature to 120C.
Seven methods are listed in the section.