JPS5857324A - Production of perfluoroalkyl substituted compound - Google Patents

Abstract

PURPOSE:A nucleophilic reagent and a perfluoroalylaryliodonium compound are used to effect the perfluoroalkylation of a compound such as ethylene, as well as make the product nucleophilic, thus producing the titled compound used as an intermediate of surface active agents without side-reactions with saved energy. CONSTITUTION:A nucleophilic reagent of NuM[Nu is halogen, hydroxyl, nitrile; M is H, alkali metal, alkaline earth metal, ammonium residue]and a perfluoroalkylaryliodonium compound of formulaI[Rf is perfluoroalkyl; Ar is phenyl; X is -OSO2Y (Y is alkyl, aryl), -OCOZ (Z is alkylaryl), halogen]are used to effect the reaction with an ene compound of formula II (R<1>-R<6> are H, halogen, R<1> and R<5> can incorporate to form a ring; n is 0, 1) to give a perfluoroalkyl substituted compound of formula III, which can be led to a compound used as a surface active agent or surface treating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula % (1) (where f is a perfluoroalkyl group having 1 to 20 carbon atoms), m, R", R", Wll and t
is a hydrogen atom, a -rogen atom, a substituted or unsubstituted alkyl group, or an aryl group. R1 and male can be combined to form a cyclic structure. Nu is a hydrogen atom, a hydroxyl group, a quano group, a formyloxy group, a thiocyanato group, an azide group, a substituted or unsubstituted alkoxy group, an acyloxy group, an acylthio group, an arylcarbonyloxy group, or an arylcarboxyloxy group, and m is 0 or 1. ) perfluoroalkyl-substituted compound OI
This article relates to an I-making method. The compound represented by the general formula (1) of the present invention can be obtained as a useful intermediate having both activities. For example, among the R/fluoroalkyl substituted compounds represented by the general formula (1) obtained according to the present invention, 2-(berfluoroalkyl)ethanol F1tlWi activator, aqueous layer oil agent,
It is useful as an intermediate for surface treatment agents for paper, leather, fibers, etc., fire extinguishers, oil collecting agents, lubricating oil additives, etc.
&D Report 0 'Chemistry and Industry of Fluorine Compounds', p. 388 (1977, CMC Publishing)].

Conventionally, the method for producing 2-(perfluoroalkyl)ethanol is to react ethylene with ethylene under radical-generating conditions to produce 2-(perfluoroalkyl)ethyl iodide (ill, CI) dimethylforma f. A method of hydrolysis in a reaction field at 140° C. (J, Ohem, 8oc.).

1.2856 and R&D Report, 'Chemistry and Industry of Fluorine Compounds', p. 388 (1977, CMC Publishing)] or (2) a method obtained by treating with a swindling acid chain and hydrolyzing it (J, Org , Ohem, , 23.11
66 (1958) is known.

However, since the reaction of l-doberfluoroalkane and ethylene in the conventional method is under radical reaction conditions, polymerization reactions occur simultaneously, making it difficult to control the reaction). ) requires high temperatures and is therefore undesirable from the viewpoint of energy conservation. Furthermore, method c2) using vinegar is economically disadvantageous because it uses expensive silver salt. From the above points, 2-(perfluoroalkyl)
The method for producing ethanol (OEL) is unsatisfactory as an industrial production method. In addition, when the 2-(perfluoroalkyl)ethyl ester of pyrocytic acid 2-(perfluoroalkyl)ethyl ester of the fluorotetraalkyl-substituted compound expressed by the above-mentioned general formula (1) obtained by Kinoe 1jiK is hydrolyzed, -(Perfluoroalkyl) ζ-tate easily leading to ethanol. (R&
D Report, “Chemistry and Industry of Fluorine Compounds”, p. 388 (published by CMC, 1977)].

Furthermore, among the compounds represented by the general formula (1) obtained by the present invention, 4-(berfluoroalkyl)-2
-Buten-1-ol is converted into 1-(perfluoroalkyl)-1゜3-butadiene by dehydration, which is useful as a binder for fluoropolymer having both surface and active activities.
When guided, a point is made (Reference example 1, fli111 permission No. 289
No. 2824, No. 2912407, and No. 339812
(See No. 8).

Conventionally, as a method for producing 1-(perfluoroalkyl)-1,3-butadiene, for example, when the perfluoroalkyl group is a trifluoromethyl group, (1)) 9fluoroacetylacetoy is heated at high pressure and high temperature (150 atm). ,100℃
) under the conditions of Raney JL? After reduction with Kel to obtain diol and further diacetate with 6-acid anhydride, the mixture was heated at 470°C.
(J, Amer, Oh
cm, 8oc, , 74.5147 (1954)
5,5.5-) Lyyfluoro-tetra-eproic acid (5,5 ,5-t r i fluorolaevu
IcmcId) was reduced with hydrogen lithium aluminum (=lam) to form a diol, further diacetated, and heated at 520°C.
How to decompose straw (Tetra7phedron, u
5) Mixture K of 5.5.5-trifluoro-1-goupine and ethyl alcohol
A method of obtaining an adduct by long-term irradiation with rIiI of
44) is known.

However, methods a) and 3) have long reaction paths and are carried out at a high temperature of around soo C. for the final thermal decomposition reaction #1, which is not preferable from the viewpoint of energy saving.

Method 6) uses Oo, which is a radioactive substance, and has a low collection rate. From the above points, the conventional method for producing 1-(perfluoroalkyl)-1,3-Poutage/ is unsatisfactory as an industrial production method.

In addition, formic acid and acetic acid 4-(perfluoroalkyl)-2-butenyl ester obtained by the present invention can be easily converted into 4-(pe,A/fluoroalkyl)-2-buten-1-ol by hydrolysis. (See Reference Examples 2 and 5). Furthermore, acrylic acid and 4-(perfluoroalkyl methacrylate) obtained according to the present invention
-2-7'tenyl ester can be used as a coating agent for fluorine-based acrylic acid or methacrylic acid ester polymers, which are useful as water and oil repellents for textiles, etc., and as resists for integrated circuits (R&D Report 1 Fluorine Compounds chemistry and industry”,
391 pages and cutting edge application technology of monofluorine compounds”, L5
(See page 8). Acrylic acid and methacrylic [4-(berfluoro-alkyl)-2-butenyl ester] have an unsaturated bond between the acid moiety and the verfluoro-alkyl group moiety.A completely new mow water repellent oil agent is used to manufacture resists for integrated circuits. Things for use! − is. f9, acrylic acid and methacrylic acid 4-(perfluoroalkyl)-2-butenyl esters are acrylic acid chloride and methacrylic acid 9, respectively, obtained according to the invention ~/-(4'-(perfluoroalkyl)-2- pyridinium salt of sulfuric acid ester obtained by treatment with chlorosulfonic acid in pyridine ♂a - amount 1 and 0.001
The weight-efficient aqueous solution is 17.9 da 4y7a at 27°C, respectively.
m and 42.9 da 47/e MLi can lower the surface tension, so it can be used as surfactants, water and oil repellents, surface treatment agents for paper, leather, textiles, etc., fire extinguishers, lubricating oil additives, etc. It is useful as an intermediate for In general, as a surfactant, adding 0.1 weight percent of K to water is sufficient if it can lower the surface tension of water (72 dynes/1) to 30 dynes/1 or less. Obtained 90,
A value of 17.9 dynes/cIL at a concentration as low as 0.01 wt. is an excellent value.

The present inventors have discovered a method for producing a perfluorotetraalkyl-substituted compound, which has been intensively studied in order to overcome the conventional drawbacks, and have completed the present invention.

The present invention is based on the general formula NuM □ value) (wherein Nu is a halogen atom, a hydroxyl group, a cyano group, a formyloxy group, a pencyanato group, an azide group, a substituted or unsubstituted alkyl; an xy group, an acyloxy group, an acylthio group) , arylcarbonyloxy group or arylcarbonylthio group, M water bulky atom, alkali metal atom,
It is an alkaline earth metal atom, ammonium residue or pyridinium residue. ), and a nucleophile represented by the general formula (wherein, Rf is a perfluoroalkyl group having a number of 1 to 20, Ar is a substituted or unsubstituted 7-fluorinyl group, oso, a group represented by y, a group represented by -oooz, a halogen atom, Bii"4, ClO4,
PF4, PF6, As F 4, As F 4.8
bF6 or 8bF4. However, yFi can be substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, halogen atom, OM'i, alkoxy group, It is an alkyl group, a substituted or unsubstituted aryl group, or a behaloalkyl group. M is a hydrogen atom, an alkali metal atom, an ammonium residue, a pyridinium residue, or a Mr group represented by Rf-■-. ) and the general formula n'R2o oi-o.
Geri in' A pan-cyclic structure can be formed by reacting with an ene compound represented by A-, where n is 0 or 1, to form a pan-cyclic structure of the general formula (1).
The company produces perfluoroalkyl-substituted compounds represented by:

The perfluorinated alkylaryrudonium compound represented by the general formula (0), which is a raw material of the present invention, is obtained by oxidizing or fluoridating an industrially available iodized perfluorinated alkali. (Toxy) w-Doberfluoro-alkane or Hashifluoro-Doberfluoro-tetraalkane (ZkOrg, k 1m, 6.329 (
1970), J, FlorinaOh@m,, Dan, 177 (1976) and J, Mummer, Oh@m.

8oc, 9J, 3054 (1969)] with substituted or unsubstituted benzene in the presence of an acid, or a method of reacting with substituted or unsubstituted benzene and then treating with an alkali metal halide salt. (Zk, Org, KhIm,
7.1475 (1971), Zh.

Or H, Km Im, 16.232 (1980
), 1llll Public Patent No. 121226, French National Patent Publication No. 2458527 and 4$-162765].

9 If X is 0 ammonium residue or pyridinium residue in a perfluoro-alkyl aryl polydonium compound which is generally represented by
Y, Y=OH) as a lupril fluorodonium compound, n-heneiconafluorodecyl 7! 7-)
Refluoromethanesulfonate trifluoromethanesulfonate, n-
Hebutadecafluorooctyl 7g nyl fluoride trifluorometa/sulfo*-), 11-pen! Decafluor is hebutyl 7-fluorinyl-donium trifluoromethanesulfonate, n-tridecafluorohexyl 7JE-nyl-donium trifluoromethanesulfonate, hebutyl-tetrapropyl 7-donium trifluoromethanesulfonate, 9-fluorinated methanesulfonium-4- ), n-hebutafluoroglovir 7
Nirufu-donium triple olomethane sulfonate,
Pentafluoroethyl phenyl sulfate-donium trifluoromethanesulfonate, trifluoromethylphenyl blind-donium trifluoromethanesulfonate, pentafluoroethyl 7-dnyliodonium chloride, n-heptafluorotetrapropyl-p-)lylphenyl chloride Nium chloride, n-hebutadecafluorooctyltolyliodonium chloride, n-heptafluoropropyltolyl hundred-donium trifluoroacetate, n-hebutadecafluorocrocodyl octylph! Nyliodonium methanesulfonate, n
-hebutadecafluorooctyl 7-honyliodonium trictetramethane sulfonate, n-hebutafluoroclovir-p-)! chlorinated tonium methanesulfonate,
n-hebutadecafluoro octyltolyliodonium methanesulfonate, n-hebutadecafluoropropyl-p-
) Donium benzene sulfonate, mono(pentafluoroethyl 7-enyl-donium) sulfate, mono(n-heptafluoro-donium) sulfate! -), mono(1-hebutafluoroptetrabilphenyl)sulfm-), mono(n-)
IJ De*Fluor Hexyl 7 Otori El-Donicum) A
/7-t, mono(n-heptadecafluoro-octyl 7
m el fluorodonium) sulfate, mono(n-henei=nafluorodecyl 7oyl fluorodonium) sulfate, bis(n-hebutafluorofluorophore 7 phoenium A/!
I-)' Ella A) Sulfate, n-heptafluoropropyl 7z engineering) &l! l-beadom fluorosulfonate, n-hebutadecafluorotetratyl 7-fluorinyl H-donicum chlorosulfo$-), fi-hebutadecafluoro-tetrabutyl phenylrhodonium methylsulfonate, n-heptadecafluoroctyl Donium pyridinium sulfate, n-heptafluorodonium pyridinium sulfate, n-heptafluorodonium sodium sulfate, n-heptafluoropropyridinium 22ASW-doium potassium sulfate 7
For example, ethylene, propene, 1-heptene, 2-butene, allyl chloride, allylbenzene, allyl acetate, Nyl ether, allyl ethyl ether, phtadiene, 1,3 on allyl 7
-peftadiene, 2-talolo 1,3-ptadiene, 2
-Methyl-1,3-butadiene, Schiff's hequinadiene,
Schifmiophtadiene, styrene, p-claustyrene,
Cyclohexene, Schiff's Heptene, Kuku's Gastric Pebutene, 5
．． Examples include 6-sihydro-2H-bilane, 1°4-dihydronaphthalene, and 1,4-cyclohexadiene. 9 general formula (1) % formula % Benzyl alcohol, -nia#4-pyl artzole, octyl alcohol, ethylene glycol, gv serine, polyethylene glycol, polypropylene/glycol, ethylene glycol 7-methyl ether, polyethylene glycol monomethyl ether, apple Acid, adamandelmethanol, formic acid, acetic acid, acetic acid, propionic acid,
Stearic acid, actiobenzoic acid, p-chlorobenzoic acid, adamantane acetic acid, adamantane carboxylic acid, hequinane carboxylic acid, sodium chloride, sodium fluoride, potassium heptadide, cesium fluoride, potassium iodocyanide, thiocyanic acid An example of this is Natriu V.

In the practice of the present invention, when M is a hydrogen atom, side reactions tend to occur due to the acid produced, so it is preferable to carry out the process in the presence of a base. Examples of the base include triethyl azino, pyridine, 2,6-dimethylpyridine, 2,
Organic amines such as 6-di-t-butyl-4-methylpyridine, O metal carbonates such as sodium carbonate, potassium carbonate, and sodium bicarbonate, alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide, and water. Sodium oxide, potassium hydroxide%4
Bases such as metal hydroxides such as calcium hydroxide can be used, in which case at least equivalent amounts are used.

Although a tonne solvent is not necessarily required for carrying out the reaction,
For example, methychloride, chloroform, tetrachloroethane, tetrachloroethane, 1,1.2-)
9, trifluoroethane, etc., acetone, acetonitrile, dimethyl sulfoxide (DM8
0), polar solvents such as ethyl 2% nitromethane, ethers such as diethyl ether, tetrahydrofuran, and dioquina, hydrocarbon solvents such as benzene, toluene, hexane, cyclohexane, octane, and decalin, carbon disulfide, and nitrobenzene. etc. can be used as a solvent.

The reaction temperature is -50°C to 150°C, but preferably -30°C to 100°C in order for the reaction to proceed efficiently.

Hereinafter, the present invention will be explained in further detail with reference to Examples. 'Il
I do it.

Example 1 -÷n -06F17G (20H=clHCI(2
01 (n-heptadecafluoroctylfluoroyl tetra-donium trifluoromethanesulfonate 386ml!F
(0.5 mmo 1 ) and 9 um of sodium bicarbonate 849 (
1 mmol 1 ) was placed in a reaction vessel, degassed using a vacuum pump, and suspended by adding 3 y of methylene chloride and 1 liter of water. 1,5-Butadiene was introduced, the mixture was stirred at room temperature for 2 hours, and then extracted with methylene chloride. The extract is sulfuric anhydride)
After drying, the solvent was distilled off under reduced pressure. The residue was applied to a silica gel column (developed from 20-ether/n-baytane to 40-ether/n-pentane), and 4-(n-hebutadecafluorooctyl)-2-buten-1-ol 11
Obtained 4 capes.

The yield was 47-0. The physical properties are shown in Table 2.

Example 2 A reaction was carried out in the same manner as in Example 1 under the conditions shown in Table 1. The results are shown in Table 1. Note that the physical property values of the obtained substance are shown in Table 2.

Reference example 1 n-0BF 170H-CIIDH=au.

4-(n-hebutade or fluorootate)-2-buten-1-ol 490 capes (1 mmol) and phosphorus pentoxide 85
2 Misaki (6 mmol) and heated to 80-100℃ while reducing the pressure with a vacuum pump equipped with a liquid nitrogen door wrap.
heated for an hour. The mixture was extracted with methylene chloride and 1-(
n-hebutadecafluoro-1,3-butadiene (144) was also obtained from a trap under liquid nitrogen cooling.
A product of 11f was obtained, giving a total of 191 sv (yield: 40%). Colorless oil.

'H-NMR (ppm, in weight 4C1hokA); 5.3
6-5.87 (m, 3H), 6.16-6.88
(m.

2H).

"F-NMR (ppm, in weighted tetraform, 001.
F internal standard); (-α-0F2).

IR (csa, neat); 1155.1210
．． 1250 (OF), 115,1665 (OF 0).

wxx”C evening)v(m/e);472(M　).

Elemental analysis; actual value; 0.30.491i; H, 1,0
5th grade.

Calculated value; 0.30.5311; H, 1,071 Reference example 2 a -0,F , , 0H2 (I(=OHOH, (H+
OH2=(M)001--1→a -06F 150H
20H=CHG(2000G(=G(24-(n-1lidecafluorohexyl)-2-buten-1-ol22
2 parts (0,57 mmol) and triethylamine 13
Dissolve 8 ki (1,36 mmo 1 ) in 4- ether, ii! 124"l (1,36mmol) of nine acrylic acid dissolved in 2wt of ether with stirring in a lagoon.
was dripped. After stirring the ramie for an additional hour, the precipitate was filtered off. The solvent of the filtrate was distilled off under reduced pressure and
) K applied acrylic acid 4-(n-)lidecafluorohexyl)-2-7'tenyl ester 138 was obtained. Yield 5
5 Arrogant. The physical property values are shown in Table 2.

Reference example 3 n-05F70H2 (IH point) σr, co Toda, =O(
OH, Coffin χ1→a −0iF yOH21mlB■20
000 (αchi) K-cho 4-(Hepta≠#Fluoropto Building)-2-7'ten-1-all 250q (1,04m
mo 1), metatallylic acid 4-
(n-hebutafluoropropyl)-2-+'-nyl ester 154+vt was obtained. Yield: 48%. Physical properties table 2
Shown below.

Patent applicant continued from page 1 161102 Inventor of 7142-4H Shin Nakayama - 4-4-1 Nishionuma, Sagamihara City Sumo Central Chemical Research Institute Procedures Amendment (Spontaneous) December 27, 1982 Kazuo Wakasugi, Commissioner of the Japan Patent Office 1゜Indication of the case Showa D56IiF-Patent Application No. 153855 2゜Name of the invention Process for producing perfluoroalkyl-substituted compounds 3゜Who makes the amendment 5・Contents of the amendment (υ Specification No. 23 of this M specification The following is inserted after the [Example 20J] section of Table 1 on page 1.

Record

Claims (1)

[Claims] d) Reacting a nucleophile represented by the general formula, a perfluoroalkylary+w-doem compound having the general formula % and an ene compound represented by the general formula %. consisting of
A method for producing a perfluoroalkyl-substituted compound represented by the general formula % (in the formula, Rf is a perfluoroalkyl group having 1 to 20 primes, and Ar is a substituted or unsubstituted axl group). , X is a group represented by -oso, y, -oooz
A group represented by, hegen atom, BF4.0I04, p
r4, PF, , AgF2, Muso P6.8bF6 or 8b
It is F4. Tomodashi Y is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a halogen atom,
Z is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryl group. M is a hydrogen atom, an alkali metal atom, an ammonium residue, a pyridine atom, or a substituted or unsubstituted alkyl group or aryl group. B1 and R may also be integrated to form a cyclic structure. No is a halogen atom, a hydroxyl group, a cyano group, a formyloxy group, a thiocyanato group, an azide group, a substituted or unsubstituted alkoxy group, an acyloxy group, an acylthio group, an arylcarbonyloxy group, or an arylcarbonylthio group, and M is a hydrogen atom , an alkali metal atom, an alkaline earth metal atom, a 77% nium residue or a pyridinium residue, and the base is 0 or 1. (2) The method according to claim a), which comprises carrying out the step in the presence of a Hatosha base in which M is a hydrogen atom.