JPH03240739A - Production of fluoroalkyl group-containing aromatic derivative - Google Patents

Abstract

PURPOSE:To safely obtain the subject substance in high yield by reacting an aromatic compound with a fluoroalkanesulfonyl chloride in the presence of a metal catalyst. CONSTITUTION:An aromatic compound (e.g. 1,4-dimethoxybenzene) is reacted with a compound expressed by the formula (n is an integer of 1-20) in the presence of a metal catalyst at 20-200 deg.C for 1-24hr to afford the subject substance (e.g. 1,4-dimethoxy-2perfluorohexylbenzene). Cuprous oxide, copper sulfate, ferrous chloride, molybdenum hexacarbonyl, chromium chloride, dichlorotristriphenylphosphine-ruthenium, etc., are cited as the metal catalyst. The charging molar ratio of the metal catalyst to the compound expressed by the formula can be 1:(0.001-0.50) to efficiently introduce fluoroalkyl groups into the aromatic ring. The subject substance is useful as a raw material for medicines, agricultural chemicals, water and oil repellents, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing a fluoroalkyl group-containing aromatic derivative, and particularly to an industrially effective method for producing a fluoroalkyl group-containing aromatic derivative.

<Prior Art> Compounds in which a fluoroalkyl group is introduced into an organic compound have attracted attention in recent years because they exhibit useful properties such as physiological activity, water and oil repellency, and furthermore, chemical resistance. Regarding the method for producing a compound into which a fluoroalkyl group has been introduced, particularly a compound in which a fluoroalkyl group has been introduced into an aromatic compound, for example, 1, for example, by reacting fluoroalkanoyl peroxide with an aromatic compound, a peroxide can be produced. A method has been proposed for introducing fluoroalkyl groups derived from
Publication No.).

However, since the above method uses peroxide as a fluoroalkylating agent, there are problems in its handling method.

<Problems to be Solved by the Invention> An object of the present invention is to be able to obtain a fluoroalkyl group-containing aromatic derivative safely and in high yield. An object of the present invention is to provide an industrially excellent method for producing a fluoroalkyl group-containing aromatic derivative. <Means for Solving the Problems> According to the present invention, fluorocarbon 1M for introducing an alkyl group
Reacting an aromatic compound and a fluoroalkanesulfonyl chloride represented by the following general formula (I)% (I) (wherein n represents an integer of 1 to 20) in the presence of a metal catalyst. A method for producing a characteristic fluoroalkyl group-containing aromatic derivative is provided.

The present invention will be explained in more detail below.

The method for producing a fluoroalkyl group-containing aromatic derivative of the present invention is characterized in that an aromatic compound and a specific fluoroalkanesulfonyl chloride are reacted in the presence of a metal catalyst.

In the present invention, examples of the aromatic compound into which a fluoroalkyl group is introduced include benzene, 1-substituted benzene, and 2-substituted benzene.
substituted benzene, 3-substituted benzene, 4-substituted benzene,
Naphthalene, 1-substituted naphthalene, 2-I! Substituted Naphthalene 3-Substituted Naphthalene.

Examples include 4-substituted naphthalene. The 1-substituted benzene, 2-substituted benzene, 3-substituted benzene, 4
-! Examples of the substituted benzene include chlorobenzene, fluorobenzene, bromobenzene, toluene, ethylbenzene, butylbenzene, anisole, ethoxybenzene, ethoxycarbonylbenzene, methoxycarbonylbenzene, nitrobenzene, benzoic acid, phenol, acetanilide, benzaldehyde, xylene, dimethoxybenzene, Preferred examples include jetoxycarbonylbenzene, diacetylaminobenzene, phthalic acid, trimethylbenzene, and tetramethylbenzene. Also, the l-substituted naphthalene, 2-1 substituted naphthalene, 3-N
Examples of substituted naphthalenes and 4-substituted naphthalenes include chloronaphthalene, bromonaphthalene, fluoronaphthalene, naphthalenecarboxylic acid, and naphthalene dicarboxylic acid.

Preferred examples include naphthalenetetracarboxylic acid, methylnaphthalene, dimethylnaphthalene, trimethylnaphthalene, and tetramethylnaphthalene.

In the present invention, the fluoroalkanesulfonyl chloride reacted with the aromatic compound can be represented by the following general formula (I), where n is an integer of 1 to 20. shows. If n exceeds 20, the compound of the general formula (
The fluoroalkyl group in the fluoroalkanesulfonyl chloride represented by I) is CF3,F (CF,)
! ,F(cpz)3,F(CF2) ,,F(CF
,),,F (CF,),,F(CF2)7,F(C
F,),,F (CF,)! , F (CF2)□. ,
F (CF,) 1□, F (c F 2 ), -1
F (CF2)□3+ F (CF2) 14, F(c
F2) ,s,F (CF,)□5,F (c F2
) 1v,F (CF,) ,1,F (CF,) x
s, F (CF,) is 2°.

Examples of the metal catalyst used in the production method of the present invention include cuprous oxide, cupric cyanide, copper sulfate, cupric acetate, copper sulfide, cupric chloride, cuprous chloride, and cuprous bromide. , cupric bromide, copper iodide, ferrous chloride, ferric chloride, iron pentacarbonyl, iron sulfate, molybdenum hexacarbonyl, chromium hexacarbonyl, chromium chloride, dichlorotristriphenylphosphine ruthenium, dichlorotetrakistriphenyl Phosphine ruthenium, chlorotristriphenylphosphine rhodium, pentacarbonyl ruthenium,
Dodecacarbonyl triruthenium, tricarbonyl (η4
-cyclooctatetraene)ruthenium, dicarbonylbis(η-allyl)ruthenium, bromocarbonyl(η
-allyl)ruthenium, tetrachlorohexacarbonylruthenium, dichlorotricarbonylruthenium, tetracarbonylbis(η-cyclopentadienyl)ruthenium, short dicarbonylruthenium, bis(η-cyclopentadienyl)ruthenium, (η-cyclopentagenyl)ruthenium ruthenium)(η-acetylcyclopentagenyl)ruthenium, (η-cyclopentagenyl)(η-methylcyclopentagenyl)ruthenium, chlorohydridotris(triphenylphosphine)ruthenium, dihydrido(dinitrogen)tris( triphenylphosphine)ruthenium (■), tetrahydridotris(triphenylphosphine)ruthenium, hydridotetrakis(triphenylphosphine)ruthenium.

Tetracarbonylbis(cyclopentagenyl)ruthenium, iododicarbonyl(η-cyclopentagenyl)ruthenium, dicarbonyl(methyl)(η-cyclopentagenyl)ruthenium, chlorodicarbonyl(η-
cyclopentagenyl)ruthenium, tetracarbonylbis(cyclopentagenyl)ruthenium, ruthenium chloride, trans-[chlorohydridobis(I,2-bisdiethylphosphinoethane)ruthenium(If)]
, dichloro(I,5-cyclooctadiene)ruthenium, etc. can be preferably mentioned.

In the production method of the present invention, the aromatic compound can be used not only as a reaction substrate but also as a reaction solvent. In order to efficiently introduce a fluoroalkyl group into the benzene ring or naphthalene ring of an aromatic compound, the molar ratio of the metal catalyst to the fluoroalkanesulfonyl chloride may be adjusted. :
O,OO1-0.50 is preferable. The molar ratio is 0.0
If it is less than 0.01, the yield of the fluoroalkyl group-containing aromatic derivative to be produced will decrease, which is undesirable. In the production method, the aromatic compound and fluoroalkanesulfonyl chloride are
React in the presence of a metal catalyst. The reaction temperature at this time is preferably in the range of 0 to 250°C, preferably 20 to 200°C. If the reaction temperature is less than 0°C, the reaction time will be long, and if it exceeds 250°C, the pressure during the reaction will be high and one reaction operation will be difficult, which is not preferable.
Further, the reaction time can be generally carried out in the range of 30 minutes to 50 hours, but it is practically preferable to set the conditions so that it is in the range of 1 hour to 24 hours.

The reaction product obtained by the production method of the present invention can be purified by a known method such as column chromatography.

The fluoroalkyl group-containing aromatic derivative obtained by the production method of the present invention is not particularly limited as long as a fluoroalkyl group is introduced into the benzene ring or naphthalene ring. -2-perfluorohexylbenzene, 2-perfluorohexyl-1,4-dimethylbenzene, perfluorohexylanisole, perfluorohexyltoluene, perfluorohexylbenzene, perfluorohexyltetramethylbenzene, α-perfluorohexylnaphthalene,
Examples include 1,4-dimethoxy-2-trifluoromethylbenzene and 1,4-dimethoxy-2-perfluorononylbenzene.

<Effects of the Invention> In the production method of the present invention, a specific fluoroalkanesulfonyl chloride is subjected to one reaction in the presence of a metal catalyst.
A fluoroalkyl group-containing aromatic compound can be produced easily and industrially in high yield and without using special equipment. Further, the fluoroalkyl group-containing aromatic compound obtained by the production method of the present invention can be used as a raw material for medicines, agricultural chemicals, etc., and furthermore, for water and oil repellents and the like.

<Examples> Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

4 mQ of 1,4-dimethoxybenzene, 2 mmall of perfluorohexanesulfonyl chloride (0,837 g)
and 0.02 mmoQ (0,019 g) of dichlorotristriphenylphosphine ruthenium were added, and the tube was degassed and sealed.

Next, the reaction was carried out at 120°C for 24 hours, the metal catalyst was removed by column chromatography, and the mixture was purified by gel permeation chromatography. As a result, 1
, 4-dimethoxy-2-perfluorohexylbenzene was obtained in a yield of 81%. The spectral data shown below was measured for the obtained product. The results are shown below.

IR (neat) (ell-1) 1510, 1470
,1430,1280,1240゜1200.1140
, 1050; ” H-NMR (CDCQ 3 ) δ3.76 (3H,
s), 3.79 (3H, s).

6.87-7.27 (3H, m); “C-NMR (CDC flood 3) δ56.0, 56.8.1
14.5(t, J=8.6)1z), 118.9,1
52.9, 153.5; MS, m/e 456 (M”)
, 441,187,139,123,109°HRMS
, M” Actual value 456.0454. Theoretical value C14C1
4H,02456,0395 1044 When the reaction was carried out according to Example 1 except that 1,4-dimethylbenzene was replaced with 1,4-dimethoxybenzene, 2-perfluorohexyl-1,4-dimethylbenzene was 72 % yield. The spectral data shown below was measured for the obtained product. The results are shown below.

IR(neat) (ai-')2930,1500,
1360, 1300, 1240° 1200.1140; ” H-NMR (CDCQ 3) 64.25-4.60
(6H, m), 7.00-7.42 (3H, m); "C-NMR (CDCm,) 619.9 (t, J = 2
．． 4Hz), 20.8°129.1(t, 8.6Hz
), 132.7°135.2(t,,C2,4Hz),
135.8; MS, ra/e 424 (M”), 405
, 186, 155, 105°) IRMs, M+actual value 424.0531. Theoretical value C14H, F□3424.
[0496] When the reaction was carried out according to Example 1 except that 4-dimethoxybenzene was replaced with anisole, perfluorohexylanisole was obtained in a yield of 66%. The spectral data shown below was measured for the obtained product. The results are shown below.

(0-perfluorohexylanisole)IR(nea
t) (as-”)1600.1500.1470.
1240.1200°1140; "H-NMR (CDCJ23) δ3.82 (3B, s)
, 6.80-7.20 (2H, m).

7.27-7.67 (2H, m); "' C-NMR (CDCQ 3) δ56.0,11
2.7, 120.4, 129.3 (t, J=8.5Hz
), 133.6, 158.8; MS, m/e 424 (
M+), 426 (M"), 157, 127, 109.6
9; 14 RMS, M” Actual value 426.0285. Theoretical value C13H, F engineering 30426.0289 (m- and p-perfluorohexylanisole) IR
(neat) (cm-1) 1620, 1520, 130
0,1240,1200°1150; ” H-NMR (CDCQ 1 ) δ3.80 (3H,
s), 6.80-7.60 (4H, ra) -13C-
NMR (CDCQ a) δ55.5, 112.6 (t,
J Near, 3Hz) 114.1, 117.8, 119.2
(t, J=7.3Hz), 128.5(t, J=7.3
Hz).

129.9, 159.9, 162.5; MS, ta/e
424 (M"), 426 (N"), 157, 127,
109,69; HRMS, M” actual value 426.0318
．． Theoretical value C,,H,F engineering, 0426.0289 Preparation 104 (The reaction was carried out according to Example 1 except that 1,4-dimethoxybenzene was replaced with toluene, and perfluorohexyltoluene was obtained in a yield of 63%. The following spectral data were measured for the obtained product.The results are shown below.

(0-perfluorohexyltoluene)IR(neat
)(am-')1295,1230,1190,114
0; 1H-NMR (CDCQ 3) δ2.48 (3H,
t, J=3.0)lz), 7.03-7.70(4H,
m); '3C-NMRCCDCQ, )δ20.4,12
6.0, 128.5 (t, J=8.5Hz), 131.
8,132.6;MStva/e 424 (M”)-
410(M”) -141,91:HRMS, M+
Actual value 410.0323. Theoretical value C□, H, F engineering.

410.0340 (m- and p-perfluorohexyltoluene) IR (
neat) (cn-') 1360, 1290, 1240
, 1200, 1150; 1H-NMR (CDCQ,
) δ2.30 (3H, s), 7.10-7.60 (4H
, m);” 3C-NNR (CDCR3) δ21.4,
124.1 (t, J=7.4Hz).

126.8 (t, J: 6.1Hz), 127.4 (t,
J=6.1Hz); 12g, 6,129.4°132.
7,138.7; MS, m/e 424 (M”) 410 (M+), 14
1.91; HRMS, M+actual value 410.0272. Theoretical values C□, H, F, .

410.0340 114i When the reaction was carried out according to Example 1 except that 1,4-dimethoxybenzene was replaced with benzene, perfluorohexylbenzene was obtained in a yield of 60%.

When the reaction was carried out according to Example 1 except that 1,4-dimethoxybenzene (4 mQ) was replaced with tetramethylbenzene (4 g), perfluorohexyltetramethylbenzene was obtained in a yield of 78%. Ta.

104L 1,4-dimethoxybenzene (4d) was converted into naphthalene (
When the reaction was carried out according to Example 1 except that 4g) was replaced, α-perfluorohexylnaphthalene was obtained in a yield of 5
It was obtained at 9%.

Instead of disappointed and roasted perfluorohexanesulfonyl chloride,
The reaction was carried out according to Example 1 except that trifluoromethanesulfonyl chloride was used, and 1,4-dimethoxy-2-trifluoromethylbenzene was obtained in a yield of 75%.
Obtained with.

Except that perfluorononane sulfonyl chloride was used instead of perfluorohexane sulfonyl chloride.
When the reaction was carried out according to Example 1, the yield of 1,4-dimethoxy-2-perfluorononylbenzene was 60%.
Obtained with.

Dichlorotristriphenylphosphine ruthenium,
When the reaction was carried out according to Example 1 except that benzoyl peroxide was used and the reaction temperature was changed to 100° C., the desired fluoroalkyl group-containing aromatic compound of the present invention was not obtained.

From the above results, it was found that in the production method of the present invention, it is more effective to use a metal catalyst as a reaction catalyst than to use an organic peroxide.

Claims (1)

[Claims] When introducing a fluoroalkyl group into the benzene ring or naphthalene ring of an aromatic compound, the aromatic compound and
It is possible to react a fluoroalkanesulfonyl chloride represented by the following general formula (I) F(CF_2)_nSO_2Cl...(I) (in the formula, n is an integer of 1 to 20) in the presence of a metal catalyst. A method for producing a characteristic fluoroalkyl group-containing aromatic derivative.