NITRILE OXIDE COMPOUND

Abstract

The present invention provides a compound represented by formula (I) wherein symbols in the formula are as defined in the specification.

##STR00001##

Claims

1. A compound represented by formula (I): ##STR00025## wherein Rf.sup.1 is a fluoroalkyl group, a fluoroalkylene group, or a monovalent or divalent fluoropolyether group; R.sup.2 and R.sup.3 are each independently at each occurrence a hydrogen atom or a hydrocarbon group; R.sup.4 is each independently at each occurrence O, S, NR.sup.7, or OP(O) (OR.sup.8); R.sup.5 is each independently at each occurrence a divalent hydrocarbon group having two or more carbon atoms in the main chain; R.sup.7 is each independently at each occurrence a hydrogen atom or a hydrocarbon group; R.sup.8 is each independently at each occurrence a hydrocarbon group; and s is 1 or 2.

2. The compound according to claim 1, wherein Rf.sup.1 is a perfluoroalkyl group, a perfluoroalkylene group, or a monovalent or divalent perfluoropolyether group.

3. The compound according to claim 1, wherein R.sup.4 is each independently at each occurrence O or S.

4. The compound according to claim 1, wherein R.sup.5 is each independently at each occurrence: ##STR00026## wherein R.sup.6 is a single bond or a divalent organic group; R.sup.11 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R.sup.12 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R.sup.13 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and R.sup.14 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

5. The compound according to claim 4, wherein R.sup.6 is a single bond, an alkylene group, or an alkyleneoxy group.

6. A compound represented by formula (II): ##STR00027## wherein Rf.sup.1 is a fluoroalkyl group, a fluoroalkylene group, or a monovalent or divalent fluoropolyether group; R.sup.2 and R.sup.3 each independently at each occurrence is a hydrogen atom or a hydrocarbon group; R.sup.4 is each independently at each occurrence O, S, NR.sup.7, or OP(O) (OR.sup.8); R.sup.5 is each independently at each occurrence a divalent hydrocarbon group having two or more carbon atoms in the main chain; R.sup.7 is each independently at each occurrence a hydrogen atom or a hydrocarbon group; R.sup.8 is each independently at each occurrence a hydrocarbon group; and s is 1 or 2.

7. A composition comprising one or more compounds according to claim 1 for being applied to a material comprising a group having reactivity with a nitrile oxide group.

Description

EXAMPLES

Synthesis Example 1

Introduction of Oxyethylene Chain into perfluoropolyether Terminal Alcohol

[0499] ##STR00020##

[0500] Ethylene carbonate (900 mg, 10.2 mmol), tetrabutylammonium iodide (40 mg, 0.11 mmol), and p-xylene were added to 1H,1H-perfluoro(2,5,8,11,14-pentamethyl-3,6,9,12,15-oxaoctadecan-1-ol) (5.0 g, 5.10 mmol), and the mixture was stirred at 140 C. for 95 hours. After the solvent was distilled off, the mixture was purified by silica gel column chromatography, and thus oxyethylene chain-introduced perfluoropolyether terminal alcohol (2.67 g, 2.61 mmol, 51.1%) was obtained as brown oil.

[0501] .sup.1H NMR (500 MHz, 298 K, (CD3)2CO): 4.16 (d, 2H, J=13 Hz, CH.sub.2OCH.sub.2CH.sub.2O), 3.83-3.71 (m, 4H, CH.sub.2OCH.sub.2CH.sub.2O, CH.sub.2OCH.sub.2CH.sub.2O) .

Synthesis Example 2

Synthesis of perfluoropolyether Terminal Nitroalkane

[0502] ##STR00021##

[0503] Sodium hydride (26 mg, 0.60 mmol) was sufficiently washed with hexane and purged with inert gas, and then dry tetrahydrofuran (THF, 1 ml) was added. Perfluoropolyether terminal alcohol (200 mg, 0.20 mmol) that was obtained in Synthesis Example 1 and that was dissolved in dry THF (0.5 mL) at 0 C. under ice cooling was added, the mixture was stirred for 30 minutes, diphenylnitroethene (88 mg, 0.40 mmol) dissolved in dry THF (0.5 ml) was added, and the mixture was stirred at room temperature for 5.5 hours. After quenching by adding a small amount of acetic acid and ion-exchanged water at 0 C., the mixture was sufficiently extracted with diethyl ether, and the resulting organic layer was washed with ion-exchanged water, a saturated aqueous sodium hydrogen carbonate solution, and saturated saline. The organic layer was dried over anhydrous magnesium sulfate and concentrated, then purified by silica gel column chromatography, and thereby perfluoropolyether terminal nitroalkane (128 mg, 0.10 mmol, 52.5%) as pale yellow oil was obtained.

[0504] .sup.1H NMR (500 MHz, 298 K, CDCl.sub.3): 7.36-7.27 (m, 6H, Ar), 7.28 (d, 4H, J=7.5 Hz, Ar), 5.35 (s, 2H, CH.sub.2NO.sub.2), 4.16 (d, 2H, J=13 Hz, CH.sub.2OCH.sub.2CH.sub.2O), 3.84 (t, 2H, J=4.5 Hz, CH.sub.2OCH.sub.2CH.sub.2O), 3.56 (br, 2H, CH.sub.2OCH.sub.2CH.sub.2O).

Example 1

Synthesis of perfluoropolyether Terminal Nitrile Oxide

[0505] ##STR00022##

[0506] Dry dichloromethane (1 ml) and 4-chlorophenyl isocyanate (35 mg, 0.23 mmol) were added to perfluoropolyether terminal nitroalkane (128 mg, 0.10 mmol) obtained in Synthesis Example 2, the mixture was purged with inert gas, triethylamine (31 mg, 0.31 mmol) was added, and the mixture was stirred at room temperature for 1 hour and 30 minutes. After stirring was terminated, the precipitated insoluble matter was filtered off, and the filtrate was concentrated. Silica gel column chromatography was performed for purification, and thus nitrile-N-oxide (PEOE4-CNO, 88 mg, 0.07 mmol, 69.8%) was obtained as transparent oil.

[0507] .sup.1H NMR (500 MHz, 298 K, CDCl.sub.3): 7.45-7.42 (m, 4H, Ar), 7.41-7.35 (m, 6H, Ar), 4.13 (d, 2H, J=12 Hz, CH.sub.2OCH.sub.2CH.sub.2O), 3.86 (t, 2H, J=4.0 Hz, CH.sub.2OCH.sub.2CH.sub.2O), 3.68 (t, 2H, J=4.0 Hz, CH.sub.2OCH.sub.2CH.sub.2O).

Example 2

Synthesis of Nitrile Oxide Derived from C.SUB.6.F.SUB.13 .Alcohol

[0508] ##STR00023##

[0509] Synthesis of C.sub.6F.sub.13ONO.sub.2

[0510] In an Ar atmosphere, a THF solution (30 mL) of 1H,1H,2H,2H-tridecafluoro-1-n-octanol (1.0 g, 2.8 mmol) was added at 0 C. to a THF solution (30 mL) of hexane-washed sodium hydride (140 mg, 3.3 mmol). After the mixture was stirred for 30 minutes, a THF solution (30 mL) of diphenylnitroethene (740 mg, 3.3 mmol) was added, and the mixture was stirred at room temperature for 3 hours. Then, a small amount of acetic acid and ion-exchanged water were added at 0 C., and the mixture was dissolved in ethyl acetate, followed by quenching with 1.0 M hydrochloric acid. The mixture was extracted 3 times with ethyl acetate, and the resulting organic layer was washed with ion-exchanged water, a saturated aqueous sodium hydrogen carbonate solution, and saturated saline. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off, silica gel column chromatography was performed for purification, and thus C.sub.6F.sub.13ONO.sub.2 (1.6 g, 2.8 mmol) was obtained as pale yellow oil.

[0511] .sup.1H NMR (500 MHz, 298 K, CDCl.sub.3): 7.40-7.32 (m, 6H, Ar), 7.28 (d, 4H, J=7.5 Hz, Ar), 5.38 (s, 2H, CH.sub.2NO.sub.2), 3.69 (t, 2H, J=7.0 Hz, CF.sub.2CH.sub.2CH.sub.2O), 2.56-2.46 (m, 2H, CF.sub.2CH.sub.2CH.sub.2O) .

[0512] Synthesis of C.sub.6F.sub.13OCNO

[0513] In an Ar atmosphere, triethylamine (840 mg, 8.4 mmol) was added to a dichloromethane solution (30 mL) of C.sub.6F.sub.13ONO.sub.2 (1.6 g, 2.8 mmol) and 4-chlorophenyl isocyanate (940 mg, 6.1 mmol), and the mixture was stirred at room temperature for 90 minutes. After stirring, the precipitated insoluble matter was filtered off, and the filtrate was concentrated. This was purified by silica gel column chromatography (ethyl acetate/hexane=1/20), and thus C.sub.6F.sub.13OCNO (1.5 g, 2.6 mmol) was obtained as colorless oil in a yield of 94%. .sup.1H NMR (500 MHz, 298 K, CDCl.sub.3): 7.45-7.36 (m, 10H, Ar), 3.78 (t, 2H, J=6.0 Hz, CF.sub.2CH.sub.2CH.sub.2O) 2.58-2.48 (m, 2H, CF.sub.2CH.sub.2CH.sub.2O).

Example 3

Synthesis of Nitrile Oxide Derived from C.SUB.8.F.SUB.17 .thiol

[0514] ##STR00024##

[0515] Synthesis of C.sub.8F.sub.17SNO.sub.2

[0516] In an Ar atmosphere, a THF solution (3 mL) of 1H,1H,2H,2H-perfluorodecanethiol (100 mg, 0.21 mmol) was added at 0 C. to a THF solution (3 mL) of hexane-washed sodium hydride (13 mg, 0.31 mmol). After the mixture was stirred for 30 minutes, a THF solution (3 mL) of diphenylnitroethene (61 mg, 0.27 mmol) was added, and the mixture was stirred at room temperature for 2 hours. Then, a small amount of acetic acid and ion-exchanged water were added at 0 C., and the mixture was dissolved in ethyl acetate, followed by quenching with 1.0 M hydrochloric acid. The mixture was extracted 3 times with ethyl acetate, and the resulting organic layer was washed with ion-exchanged water, a saturated aqueous sodium hydrogen carbonate solution, and saturated saline. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off, silica gel column chromatography was performed for purification, and thus C.sub.8F.sub.17SNO.sub.2 (130 mg, 0.18 mmol) was obtained as pale yellow oil in a yield of 86%.

[0517] .sup.1H NMR (500 MHz, 298 K, CDCl.sub.3): 7.33-7.43 (m, 10H, Ar), 5.36 (s, 2H, CH.sub.2NO.sub.2), 2.48 (t, 2H, J=8.0 Hz, CF.sub.2CH.sub.2CH.sub.2S), 1.97-1.86 (m, 2H, CF.sub.2CH.sub.2CH.sub.2S).

[0518] Synthesis of C.sub.8F.sub.17SCNO

[0519] In an Ar atmosphere, triethylamine (29 mg, 0.29 mmol) was added to a dichloromethane solution (1.0 mL) of C.sub.8F.sub.17SNO.sub.2 (69 mg, 0.10 mmol) and 4-chlorophenyl isocyanate (30 mg, 0.19 mmol), and the mixture was stirred at room temperature for 2 hours. After stirring, the precipitated insoluble matter was filtered off, and the filtrate was concentrated. Dichloromethane was added again to the concentrated filtrate, and the precipitated insoluble matter was filtered off. This step was repeated twice, then the solvent was distilled off, silica gel column chromatography (chloroform/hexane=1/2) was performed for purification, and thus C.sub.8F.sub.17SCNO (50 mg, 0.07 mmol) was obtained in a yield of 75% as colorless oil.

[0520] .sup.1H NMR (500 MHz, 298 K, CDCl.sub.3): 7.56-7.53 (m, 4H, Ar), 7.45-7.32 (m, 6H, Ar), 2.84 (t, 2H, J=8.0 Hz, CF.sub.2CH.sub.2CH.sub.2S), 2.30-2.21 (m, 2H, CF.sub.2CH.sub.2CH.sub.2S).

Example 6

Surface Treatment (Coating)

[0521] Nitrile oxide obtained in Example 1 was applied to an allyl-modified glass plate (length 3 cmwidth 2.6 cm) with a spatula, and heated at 70 C. for 14 hours and 30 minutes using a hot plate. After being cooled to room temperature, the glass plate was ultrasonically cleaned with 70 ml of chloroform 3 times and dried with cool air from a dryer. The contact angle of the surface before and after the treatment was measured, and the results are shown in the table below.

Example 7

Surface Treatment (Coating)

[0522] Nitrile oxide obtained in Example 2 was applied to an allyl-modified glass plate (length 3 cmwidth 2.6 cm) with a spatula, and heated at 70 C. for 14 hours and 30 minutes using a hot plate. After being cooled to room temperature, the glass plate was ultrasonically cleaned with 70 ml of chloroform 3 times and dried with cool air from a dryer. The contact angle of the surface before and after the treatment was measured, and the results are shown in the table below.

Example 8

Surface Treatment (Immersion)

[0523] An allyl-modified glass plate (length 3 cmwidth 2.6 cm) was immersed in a solution in which nitrile oxide (0.15 mmol) obtained in Example 1 was added to toluene (30 ml), and heated at 70 C. for 14 hours and 30 minutes using an oil bath. After being cooled to room temperature, the glass plate was ultrasonically cleaned with chloroform (50 ml) 3 times and dried with cool air from a dryer. The contact angle of the surface before and after the treatment was measured, and the results are shown in the table below.

TABLE-US-00001 TABLE 1 Contact angle Before treatment After treatment Example 6 61 111 Example 7 66 102 Example 8 56 97

INDUSTRIAL APPLICABILITY

[0524] The compound of the present disclosure is suitably used in a variety of applications, for example, as a surface-treating agent.