JPS6222982B2 - - Google Patents

Description

[Detailed Description of the Invention] The present invention relates to the general formula (wherein, Rf is a perfluoroalkyl group having 1 to 10 carbon atoms).

Among the 3-perfluoroalkylsulfonyl-1,2-propanediol represented by the general formula () of the present invention, for example, 3-n-heptadecafluorooctylsulfonyl-1,2-propanediol is prepared by adding chlorosulfonic acid to 3-n-heptadecafluorooctylsulfonyl-1,2-propanediol in pyridine. A 0.01% by weight aqueous solution of the pyridium salt of 3-n-heptadecafluorooctylsulfonyl-1,2-propadiol disulfate obtained by treatment lowers its surface tension to 32 dynes/cm at 19°C. Therefore, it is useful as an intermediate for surfactants and water and oil repellents for paper, leather, fibers, etc.

The 3-perfluoroalkylsulfonyl-1,2-propanediol represented by the general formula () of the present invention has the general formula (In the formula, Rf is a perfluoroalkyl group having 1 to 10 carbon atoms, and n is 0 or 1.) Produced by oxidizing a perfluoroalkylpropanediol derivative represented by using an oxidizing agent. I can do it.

The perfluoroalkylpropanediol derivatives represented by the above general formula () in which n is 0, which are raw materials for producing the compound of the present invention, are industrially available 3-mercapto-1,2-propanediol and perfluoroalkyl It can be easily produced by reacting with an aryliodonium compound (see Reference Examples below). Alternatively, N-perfluoroalkyl-N-nitrosobenzenesulfonamide is reacted with bis(2,3-dihydroxypropyl) disulfide or a derivative thereof, followed by treatment such as hydrolysis if necessary. It can be manufactured by The perfluoroalkylpropanediol derivative in which n is 1 is obtained by the above method.
It can be easily produced by oxidizing a perfluoroalkylpropanediol derivative having 0 with an oxidizing agent.

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As the oxidizing agent used in the present invention, substances commonly used as oxides of organic compounds in the organic chemical industry can be used, such as hydrogen peroxide, peracetic acid,
Examples include organic or inorganic peracids such as performic acid, perbenzoic acid, m-chloroperbenzoic acid, trifluoroperacetic acid, sodium periodate, and potassium permanganate, ozone, and nitric acid. Organic peracids can be prepared from the reaction of hydrogen peroxide or the like with the corresponding acid or its acid anhydride, or from air oxidation of the corresponding aldehyde, and can be used as such without isolation. The amount of the oxidizing agent used depends on the reaction temperature, reaction time, and solvent, but it is sufficient to allow the reaction to proceed sufficiently and economically when the perfluoroalkylpropanediol derivative represented by the above general formula () where n is 0 is used as the raw material. About 3.5 to 10 oxidation equivalents are preferred to perform. In addition, when a perfluoroalkylpropanediol derivative in which n is 1 is used as a raw material, an oxidation equivalent of about 1.5 to 8 is preferable in order to allow the reaction to proceed sufficiently and to perform it economically. Note that the oxidation equivalent is the amount of oxidizing agent required to supply 1/2 gram atom of oxygen to 1 mole of reactant.

In carrying out the reaction, it is preferable to use a solvent, such as halides such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, and tetrachloroethane, ethers such as diethyl ether, tetrahydrofuran, and dioxane, formic acid, acetic acid, and trichloromethane. Examples include caraboxylic acids such as fluoroacetic acid, water, methanol, ethanol, acetone, and polar solvents such as acetic anhydride. The reaction is from 0℃
The process proceeds smoothly at 150°C, preferably between room temperature and 150°C.

Hereinafter, it will be explained in more detail using reference examples and examples.

Reference example 1 4 ml of methylene chloride and 70μ of 3-mercapto-1,2-propanediol in a 20 ml eggplant flask.
(0.81 mmol) and 65 μ (0.84 mmol) of pyridine were added, the atmosphere was replaced with argon, and while stirring at room temperature, 603 mg (0.78 mmol) of n-heptadecafluorooctyl phenyl iodonium trifluoromethanesulfonate was added.
mol) was added little by little and stirred at room temperature for 60 minutes.
A small amount of silica gel column chromatography was applied to separate iodobenzene, yielding 339 mg (82.5%) of 3-n-heptadecafluorooctylthio-1,2-propanediol as white crystals. This was recrystallized from chloroform.

Melting point: 103-105℃. ^19F -NMR ( _CCl3F internal standard in deuterated acetone): -92.38ppm (t, J = 10Hz, _CF3 ), -86.74
(t, J=13Hz, α−CF ₂ ), −119.3(bs,
CF ₂ ), −120.6 (bs, CF ₂ ), −121.4 (bs, CF _{2 )}
×2), −122.2 (bs, CF ₂ ), −125.7 (bs,
_CF2 ). ¹ H-NMR (measured by exchanging heavy water in heavy acetone): 3.07ppm (dd, _JHA , _HB = 13.0Hz, _JHA , _HX
=7.5Hz, A part of AB type; H _A ), 3.25 (dd, J
_HA , _HB = 13.0Hz, J _HA , _HX = 4.5Hz, B of AB type
Part; H _B ), 3.46-3.56 (m, CH ₂ OH), 3.81
(m, H _x ). IR(nujol): 3400(OH), 1200, 1150cm ^-1
(CF ₂ ). Mass spectrum: (M ⁺ not observed), 509 (M ⁺
-OH). Elemental analysis: Actual value: C, 25.10; H, 1.42%. Calculated value: C, 25.11; H, 1.34%. To reconfirm the structure, acetylation was performed as follows.

3-n-heptadecafluorooctylthio-1,2-propanediol 91.9 in a 10ml eggplant flask
mg (0.17 mmol), pyridine 0.5 ml, acetic anhydride 0.5 ml
and stirred at room temperature for 16 hours. The reaction solution was poured into water, extracted with ether, dried over magnesium sulfate, and the solvent was distilled off to give 97.8 mg of 3-n-heptadecafluorooctylthio-1,2-bis(acetoxy)propane as an oil ( 91.8%)
Obtained.

¹⁹ F-NMR (CCl ₃ F internal standard in deuterated chloroform): -81.32 ppm (tt, J = 10 Hz, J = 2 Hz,
CF ₃ ), −87.38 (t, J=14Hz, α−CF ₂ ), −
120.1 (bs, CF ₂ ), −121.6 (bs, CF ₂ ), −
122.3 (bs, CF ₂ ×2), −123.1 (bs, CF ₂ ), −
126.5 (bs, CF ₂ ). ¹ H−NMR (in deuterated chloroform): 〓〓〓〓〓
2.06ppm (s, CH ₃ CO × 2), 3.16 (d, J _H
X , _HY = 6.0Hz, _HY ), 4.16 (dd, _JHA , _HB =
12.0Hz, J _HA , _HX = 5.0Hz, _HA ), 4.30 (dd,
_JHA , _HB = 12.0Hz, _JHB , _HX = 4.0Hz, _HB ),
5.19 (t, dd, J _HX , _HY = 6.0Hz, J _HA , _HX =
5.0Hz, J _HX , _HB = 4.0Hz, H _X ). IR (neat): 2970 ( _CH2 ), 1750 (C=O), 1200
~1250, 1150cm ^-1 (CF ₂ ). Mass spectrum: 611 (M ⁺ +1), 551 (M ⁺ -
CH ₃ CO ₂ ). Elemental analysis: Actual value: C, 29.60; H, 1.99%. Calculated value: C, 29.52; H, 1.82%. Reference example 2 4 ml of methylene chloride and 76μ of 3-mercapto-1,2-propanediol in a 25 ml eggplant flask.
(0.88 mmol) and 140 μ (1.74 mmol) of pyridine were added thereto, and while stirring at room temperature, 598 mg (0.83 mmol) of mono(n-heptadecafluorooctyl phenyl modenium) sulfate was added, followed by refluxing for 30 minutes. After treatment in the same manner as in Reference Example 1, 236 mg (55.6%) of 3-n-heptadecafluorooctyl-1,2-propanediol was obtained as white crystals.

Reference example 3 4 ml of methylene chloride and 82μ of 3-mercapto-1,2-propanediol in a 20 ml eggplant flask.
(0.95 mmol), 76μ (0.94 mmol) of pyridine was added thereto, and while stirring at room temperature, 764 mg (0.88 mmol) of n-heneicosalfluorodecylphenyl iodonium trifluoromethanesulfonate was added and the mixture was heated at room temperature.
Stirred for 40 minutes. After post-processing in the same way as Reference Example 1,
-n-heneicosalfluorodecylthio-1.
315 mg (57.4%) of 2-propanediol was obtained as white crystals.

Melting point: 138-139℃. ^19F -NMR ( _CCl3F internal standard in deuterated acetone): -80.63ppm (t, J = 10Hz, _CF3 ), -86.70
(t, J=13Hz, α−CF ₂ ), −119.2(bs,
CF ₂ ), −121.2 (bs, CF ₂ ×5), −122.2 (bs,
CF ₂ ), −125.7 (bs, CF ₂ ). ^1H -NMR (in heavy acetone): 3.07ppm (dd, _JHA , _HB = 13.0Hz, _JHA , _HX
=7.5Hz, A part of AB type; H _A ), 3.25 (dd, J
_HA , _HB = 13.0Hz, J _HB , _HX = 4.5Hz, B of AB type
Part; H _B ), 3.56 (m, C H ₂ O), 3.86 (m,
_HX ). IR(nujol): 3370(OH), 1200, 1150cm ^-1
(CF ₂ ). Mass spectrum: 607 (M ⁺ -19). Elemental analysis: Actual value: C, 24.76; H, 1.15%. Calculated value: C, 24.93; H, 1.13%. Reference example 4 8.5 ml of methylene chloride in a 25 ml eggplant flask, 3-
Mercapto-1,2-propanediol 190μ
(2.2 mmol) and 176 μ (2.2 mmol) of pyridine were added thereto, and while stirring at room temperature, 1.0 g (2.1 mmol) of pentafluoroethyl phenyl iodonium trifluoromethanesulfonate was added, and the mixture was stirred at room temperature for 2 hours. After applying silica gel column chromatography and eluting iodobenzene with n-hexane, a mixed solvent of ether-hexane (1:1) was passed to obtain the desired product, 3-pentafluoroethylthio-
435 mg (90.8%) of 1,2-propanediol was obtained as an oil.

^19F -NMR ( _CCl3F internal standard in deuterated chloroform): -83.95 (t, J = 3.5Hz, _CF3 ), -92.17 (q,
J=3.5Hz, _CF2 ). ^1H -NMR (in heavy acetone): 3.08ppm (dd, _JHA , _HB = 12.8Hz, _JHA , _HX
=7.5Hz, A part of AB type; H _A ), 3.26 (dd, J
_HA , _HB = 12.8Hz, J _HB , _HX = 4.5Hz, AB type B
Part; H _B ), 3.17-4.03 (m, CH ₂ OH, H
_X ). IR (neat): 3370 (OH), 2940, 2880, 1440,
〓〓〓〓〓
1330, 1320 ( _CH2 ), 1200, 1090 ( _CF2 ,
CF ₃ ), 750cm ^-1 (CF ₃ ). Mass spectrum: 209 (M ⁺ −OH). Elemental analysis: Actual value: C, 26.29; H, 3.10%. Calculated value: C, 26.55; H, 3.12%. Reference example 5 3-n-heptadecafluorooctylthio-1,2-propanediol 197 in a 25ml eggplant flask
mg (0.37 mmol), 4 ml of 1,2-dichloroethane were added, and while stirring at room temperature, 84 mg of m-chloroperbenzoic acid was added.
(0.41 mmol) and refluxed for 2 hours. The target product, 3-n-heptadecafluorooctylsulfinyl-1,2-propanediol, was separated from m-chlorobenzoic acid by silica gel column chromatography (developed with a mixed solvent of n-hexane and ether) in white. 167 mg (82%) was obtained as crystals.

Melting point: 162-163℃. ^19F -NMR ( _CCl3F internal standard in heavy acetone): -80.68ppm (t, J = 10Hz, _CF3 ), -113.5~
−124.3 (m, CF ₂ ×6), −125.7 (bs,
_CF2 ). ^1H -NMR (in heavy acetone): 2.25-4.40ppm
(m). IR (KBr): 3400 (OH), 1230~1200, 1150
(CF ₂ ), 1080 cm ^-1 . Mass spectrum: 511 (M ⁺ −CH ₂ OH). Elemental analysis: Actual value: C, 24.21; H, 1.09%. Calculated value: C, 24.37; H, 1.30%. Reference example 6 3-pentafluoroethylthio-
Dissolve 140 mg (0.62 mmol) of 1,2-propanediol in ml of ether and m-chloroperbenzoic acid (purity
85%) was added thereto, and the mixture was stirred at room temperature for 30 minutes. Using reactive silica gel column chromatography, the target product 3-
125 mg (83%) of pentafluoroethylsulfinyl-1,2-propanediol as white crystals
Obtained.

Melting point: 66-68℃. ^19F -NMR ( _CCl3F internal standard in deuterated chloroform): -80.24ppm (t, J = 3.5Hz, _CF3 ), -118.8
(d, J _FA , _FB = 245Hz, A part of AB type, F
_A ), −126.2 (d, J _FA , _FB = 245Hz, B of type AB
Part, F _B ). ^1H -NMR (in deuterated chloroform): 2.8-3.9ppm
(m). IR (nujol): 3300 (OH), 1340 ( _CH2 ), 1200
(CF ₂ , CF ₃ ), 1080 (SO), 750 cm ^-1 (CF ₃ ). Mass spectrum: 243 (M ⁺ +1), 211 (M ⁺ -
_C2OH ). Elemental analysis: Actual value: C, 24.93; H, 2.82%. Calculated value: C, 24.80; H, 2.91%. Example 1 3-n-heptadecafluorooctylthio-1,2-propanediol 170 in a 25ml eggplant flask
mg (0.32 mmol) and 5 ml of 1,2-dichloroethane were added, and while stirring at room temperature, 164 mg (0.81 mmol) of m-chloroperbenzoic acid (purity 85%) was added, and after stirring at room temperature for 1 hour, the mixture was stirred for 1 day. It refluxed. When separated from m-chlorobenzoic acid by silica gel column chromatography, 3-n-heptadecafluorooctylsulfonyl-1,2-propanediol was obtained.
Obtained 135 mg (75%) as white crystals. It was purified by recrystallization from methanol.

Melting point: 170-172℃. ¹⁹ F-NMR (CCl ₃ R internal standard in deuterated acetone): -80.61 ppm (t, J = 10 Hz, CF ₃ ), -113.4
(bs, α−CF ₂ ), −119.7 (bs, CF ₂ ), −121.1
(bs, CF ₂ ×3), −122.1 (bs, CF ₂ ), −125.7
(bs, CF ₂ ). ^1H -NMR (in heavy acetone): 3.4-4.7ppm
(m). Mass spectrum: 527 (M ⁺ -CH ₂ OH). IR (nujol): 3400 (OH), 1350 ( _SO2 ), 1240,
1210, 1150cm ^-1 (CF ₂ ). Elemental analysis: Actual value: C, 23.57; H, 1.26%. Calculated value: C, 23.67; H, 1.26%. Example 2 3-n-heneicosafluorodecylthio-1,2-propanediol 180 in a 25ml eggplant flask
mg (0.29 mmol), 1,2-dichloroethane 6.5 ml
and m-chloroperbenzoic acid under stirring at 60℃.
150 mg (purity 85%, 0.74 mmol) was added and refluxed for one day. After distilling off the solvent, add ether and
When the precipitate is filtered, 3-n-heneicosalfluorodecylsulfonyl-1,2-propanediol
134 mg (71%) was obtained as white crystals.

Melting point: 132-134℃. ^19F -NMR ( _CCl3F internal standard in deuterated acetone): -80.53ppm (bs, _CF3 ), -112.8 (bs, α-
CF ₂ ), −119.5 (bs, CF ₂ ), −121.0 (bs, CF _{2 )}
×5), −122.0 (bs, CF ₂ ), −125.5 (bs,
_CF2 ). IR (KBr): 3450 (OH), 2950 ( _CH2 ), 1370
( _CH2 ), 1360 ( _SO2 ), 1340 ( _CH2 ), 1200
(CF ₂ ), 1150cm ^-1 (CF ₂ ). Mass spectrum: M ⁺ is not observed.

Elemental analysis: Actual value: C, 24.01; H, 1.01%. Calculated value: C, 23.72; H, 1.07%. Example 3 3-pentafluoroethylthio-
1,2-propanediol 110 mg (0.49 mmol),
Add 6 ml of 1,2-dichloroethane and 278 mg (1.37 mmol) of m-chloroperbenzoic acid (purity 85%).
Refluxed overnight. After the reaction, silica gel column chromatography was performed to separate m-chlorobenzoic acid and the desired product, 3-pentafluoroethylsulfonyl-
96mg of 1,2-propanediol as white crystals
(76%) obtained.

Melting point: 84-85℃. ^19F -NMR ( _CCl3F internal standard in deuterated acetone): -78.25ppm (bs, _CF3 ), -117.9 (bs,
_CF2 ). ^1H -NMR (in heavy acetone): 3.4-4.7ppm
(m). IR (nujol): 3300 (OH), 1360 ( _SO2 ), 1220,
1180 (CF ₂ , CF ₃ ), 1120 cm ^-1 (SO ₂ ). Mass spectrum: 227 (M ⁺ −CH ₂ OH). Elemental analysis: Actual value: C, 23.21; H, 2.54%. Calculated value: C, 23.26; H, 2.73%. Example 4 100% of 3-n-heptadecafluorooctylsulfinyl-1,2-propanediol was added to the reaction vessel.
mg (0.18 mmol) and 3 ml of 1,2-dichloroethane
and m-chloroperbenzoic acid (purity 85%)
56 mg (0.28 mmol) was added and refluxed overnight. By performing the same post-treatment as in Example 1, 3-n-
heptadecafluorooctylsulfonyl-1,2
−85 mg (83 mg) of propanediol as white crystals
%) obtained.

Example 5 95 mg (0.39 m
mol), 1,2-dichloroethane 5 ml and m-chloroperbenzoic acid (purity 85%) 120 mg (0.59 mmol)
was added and refluxed overnight. After the reaction, m-chlorobenzoic acid was separated by silica gel column chromatography to obtain the target product, 3-pentafluoroethylsulfonyl-1,2-propanediol, as white crystals.
Obtained 82 mg (81%).

Reference Example 7 3-n-heptadecafluorooctylsulfonyl-1,2-propanediol disulfate ester synthesized by treating 3-n-heptadecafluorooctylsulfonyl-1,2-propanediol with chlorosulfonic acid in pyridine of pyridinium salt
A 0.01% by weight aqueous solution was prepared and the surface tension of the solution was measured at 19°C using a Kyowa CBVP type surface tension meter. As a result, a value of 32 dynes/cm was obtained.

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Claims (1)

[Claims] 1. General formula 3-perfluoroalkylsulfonyl-1,2-propanediol represented by (wherein Rf is a perfluoroalkyl group having 1 to 10 carbon atoms).