Nitrileoxide compound

Abstract

The present invention provides a compound of the formula (I): ##STR00001##
wherein, A is R.sup.6(R.sup.7).sub.s, N, O, S, or NR.sup.5; R.sup.6 is an s-valent organic group; R.sup.7 is each independently, O, S, NR.sup.5 or OP(O)OR.sup.4; R.sup.2 and R.sup.3 are each independently a hydrogen atom or a hydrocarbon group; R.sup.4 is each independently, a hydrocarbon group; R.sup.5 is each independently, a hydrogen atom or a hydrocarbon group; and s is an integer of 1-10.

Claims

1. A compound of the formula (I): ##STR00032## wherein: A is R.sup.4O, R.sup.4NR.sup.5, (R.sup.4O).sub.2P(O), R.sup.4S, R.sup.6(R.sup.7).sub.s, N, O, S, or NR.sup.5; R.sup.2 and R.sup.3 are each independently a hydrogen atom, an aryl group, a tert-alkyl group, or a sec-alkyl group, which may have one or more substituents, and at least one of R.sup.2 and R.sup.3 is an aryl group, a tert-alkyl group, or a sec-alkyl group, which may have one or more substituents; s is an integer of 1-10, when A is R.sup.4O, R.sup.4NR.sup.5, or (R.sup.4O).sub.2P(O), then s is 1, R.sup.4 is R.sup.13(R.sup.14).sub.iR.sup.15 R.sup.13 is a hydrogen atom, a halogen atom, or a methyl group which may be substituted by a halogen atom, R.sup.14 is each independently at each occurrence an oxygen atom, an alkylene group, a cycloalkylene group, a heterocycloalkylene group, an arylene group, a heteroarylene group, a divalent polyalkylether group or a divalent siloxane group, when A is R.sup.4O, R.sup.15 is an alkylene group having 2-3 carbon atoms optionally substituted by one or more substituents, wherein the substituent of alkylene is selected from the group consisting of an oxygen atom; a halogen atom; a hydroxyl group; an unsubstituted, mono-substituted or di-substituted amino group; a nitro group; an azide group; a C.sub.1-16 alkyl group, a C.sub.3-16 cycloalkyl group, a C.sub.3-16 cycloalkenyl group, a C.sub.6-16 heterocycloalkyl group, a C.sub.6-16 heterocycloalkenyl group, a C.sub.6-16 aryl group, a C.sub.6-16 heteroaryl group, a C.sub.1-16 alkoxy group, a C.sub.6-16 aryloxy, a C.sub.1-16 alkylthio or a C.sub.1-20 (poly)alkyl ether group which may be substituted by one or more halogen atoms; OC(O)OR.sup.a, OC(O)NR.sup.a.sub.2, C(O)R.sup.a, C(O)OR.sup.a, NR.sup.aC(O)R.sup.a, NR.sup.aC(NR.sup.a)R.sup.a, C(NR.sup.a)R.sup.a or C(NR.sup.a)NR.sup.a.sub.2, wherein R.sup.a represents each independently a hydrogen atom, a C.sub.1-16 alkyl group, a C.sub.2-16 alkenyl group, a C.sub.2-16 alkynyl group, a C.sub.3-16 cycloalkyl group, a C.sub.3-16 cycloalkenyl group, a C.sub.6-16 heterocycloalkyl group, a C.sub.6-16 heterocycloalkenyl group, a C.sub.6-16 aryl group or a C.sub.6-16 heteroaryl group, when A is R.sup.4NR.sup.5 or (R.sup.4O).sub.2P(O), R.sup.15 is an alkylene group optionally substituted by one or more substituents, wherein the substituent of alkylene is selected from the group consisting of an oxygen atom; a halogen atom; a hydroxyl group; an unsubstituted, mono-substituted or di-substituted amino group; a nitro group; an azide group; a C.sub.1-16 alkyl group, a C.sub.2-16 alkynyl group, a C.sub.3-16 cycloalkyl group, a C.sub.3-16 cycloalkenyl group, a C.sub.6-16 heterocycloalkyl group, a C.sub.6-16 heterocycloalkenyl group, a C.sub.6-16 aryl group, a C.sub.6-16 heteroaryl group, a C.sub.1-16 alkoxy group, a C.sub.6-16 aryloxy, a C.sub.1-16 alkylthio or a C.sub.1-20 (poly)alkyl ether group which may be substituted by one or more halogen atoms; OC(O)OR.sup.a, OC(O)NR.sup.a.sub.2, C(O)R.sup.a, C(O)OR.sup.a, NR.sup.aC(O)R.sup.a, NR.sup.aC(NR.sup.a)R.sup.a, C(NR.sup.a)R.sup.a or C(NR.sup.a)NR.sup.a.sub.2, wherein R.sup.a represents each independently a hydrogen atom, a C.sub.1-16 alkyl group, a C.sub.2-16 alkenyl group, a C.sub.2-16 alkynyl group, a C.sub.3-16 cycloalkyl group, a C.sub.3-16 cycloalkenyl group, a C.sub.6-16 heterocycloalkyl group, a C.sub.6-16 heterocycloalkenyl group, a C.sub.6-16 aryl group or a C.sub.6-16 heteroaryl group, l is an integer of 0-5, R.sup.5 is each independently a hydrogen atom or a hydrocarbon group; when A is R.sup.4S, then s is 1, R.sup.4 is R.sup.13(R.sup.14).sub.lR.sup.15, R.sup.13 is a hydrogen atom, a halogen atom, or a methyl group which may be substituted by a halogen atom, R.sup.14 is each independently at each occurrence an oxygen atom, an alkylene group having 1-20 carbon atoms, a cycloalkylene group, a heterocycloalkylene group, an arylene group, a heteroarylene group, a divalent polyalkylether group or a divalent siloxane group, R.sup.15 is an alkylene group having 3 carbon atoms, l is an integer of 0-5; when A is R.sup.6(R.sup.7).sub.s, then s is an integer of 2-10, R.sup.6 is an s-valent organic group, R.sup.7 is each independently O, S, NR.sup.5 or OP(O)OR.sup.4, R.sup.4 is each independently a hydrocarbon group, R.sup.5 is each independently a hydrogen atom or a hydrocarbon group; when A is N, then s is 3, and when A is O, S or NR.sup.5, then s is 2, and R.sup.5 is a hydrogen atom or a hydrocarbon group.

2. The compound according to claim 1, which is a compound of the formula (II): ##STR00033## wherein: R.sup.2 and R.sup.3 are each independently a hydrogen atom, an aryl group, a tert-alkyl group, or a sec-alkyl group, which may have one or more substituents, and at least one of R.sup.2 and R.sup.3 is an aryl group, a tert-alkyl group, or a sec-alkyl group, which may have one or more substituents; when R.sup.1 is R.sup.4O, R.sup.4NR.sup.5, or (R.sup.4O).sub.2P(O), R.sup.4 is R.sup.13(R.sup.14).sub.lR.sup.15, R.sup.13 is a hydrogen atom, halogen atom, or a methyl group which may be substituted by a halogen atom, R.sup.14 is each independently at each occurrence an oxygen atom, an alkylene group, a cycloalkylene group, a heterocycloalkylene group, an arylene group, a heteroarylene group, a divalent polyalkylether group or a divalent siloxane group, when R.sup.1 is R.sup.4O, R.sup.15 is an alkylene group having 2-3 carbon atoms optionally substituted by one or more substituents, wherein the substituent of alkylene is selected from the group consisting of an oxygen atom; a halogen atom; a hydroxyl group; an unsubstituted, mono-substituted or di-substituted amino group; a nitro group; an azide group; a C.sub.1-16 alkyl group, a C.sub.3-16 cycloalkyl group, a C.sub.3-16 cycloalkenyl group, a C.sub.6-16 heterocycloalkyl group, a C.sub.6-16 heterocycloalkenyl group, a C.sub.6-16 aryl group, a C.sub.6-16 heteroaryl group, a C.sub.1-16 alkoxy group, a C.sub.6-16 aryloxy, a C.sub.1-16 alkylthio or a C.sub.1-20 (poly)alkyl ether group which may be substituted by one or more halogen atoms; OC(O)OR.sup.a, OC(O)NR.sup.a.sub.2, C(O)R.sup.a, C(O)OR.sup.a, NR.sup.aC(O)R.sup.a, NR.sup.aC(NR.sup.a)R.sup.a, C(NR.sup.a)R.sup.a or C(NR.sup.a)NR.sup.a.sub.2, wherein R.sup.a represents each independently a hydrogen atom, a C.sub.1-16 alkyl group, a C.sub.2-16 alkenyl group, a C.sub.2-16 alkynyl group, a C.sub.3-16 cycloalkyl group, a C.sub.3-16 cycloalkenyl group, a C.sub.6-16 heterocycloalkyl group, a C.sub.6-16 heterocycloalkenyl group, a C.sub.6-16 aryl group or a C.sub.6-16 heteroaryl group, When R.sup.1 is R.sup.4NR.sup.5 or (R.sup.4O).sub.2P(O), R.sup.15 is an alkylene group optionally substituted by one or more substituents, wherein the substituent of alkylene is selected from the group consisting of an oxygen atom; a halogen atom; a hydroxyl group; an unsubstituted, mono-substituted or di-substituted amino group; a nitro group; an azide group; a C.sub.1-16 alkyl group, a C.sub.2-16 alkynyl group, a C.sub.3-16 cycloalkyl group, a C.sub.3-16 cycloalkenyl group, a C.sub.6-16 heterocycloalkyl group, a C.sub.6-16 heterocycloalkenyl group, a C.sub.6-16 aryl group, a C.sub.6-16 heteroaryl group, a C.sub.1-16 alkoxy group, a C.sub.6-16 aryloxy, a C.sub.1-16 alkylthio or a C.sub.1-20 (poly)alkyl ether group which may be substituted by one or more halogen atoms; OC(O)OR.sup.a, OC(O)NR.sup.a.sub.2, C(O)R.sup.a, C(O)OR.sup.a, NR.sup.aC(O)R.sup.a, NR.sup.aC(NR.sup.a)R.sup.a, C(NR.sup.a)R.sup.a or C(NR.sup.a)NR.sup.a.sub.2, wherein R.sup.a represents each independently a hydrogen atom, a C.sub.1-16 alkyl group, a C.sub.2-16 alkenyl group, a C.sub.2-16 alkynyl group, a C.sub.3-16 cycloalkyl group, a C.sub.3-16 cycloalkenyl group, a C.sub.6-16 heterocycloalkyl group, a C.sub.6-16 heterocycloalkenyl group, a C.sub.6-16 aryl group or a C.sub.6-16 heteroaryl group, l is an integer of 0-5, R.sup.5 is a hydrogen atom or a hydrocarbon group; and when R.sup.1 is R.sup.4S, R.sup.4 is R.sup.13(R.sup.14).sub.lR.sup.15, R.sup.13 is a hydrogen atom, halogen atom, or a methyl group which may be substituted by a halogen atom, R.sup.14 is each independently at each occurrence an oxygen atom, an alkylene group having 1-20 carbon atoms, a cycloalkylene group, a heterocycloalkylene group, an arylene group, a heteroarylene group, a divalent polyalkylether group or a divalent siloxane group, R.sup.15 is an alkylene group having 3 carbon atoms, and l is an integer of 0-5.

3. A compound of the formula (III): ##STR00034## wherein: R.sup.9 is O, S, NR.sup.5 or R.sup.7R.sup.6R.sup.7; R.sup.6 is a divalent organic group; R.sup.7 is each independently O, S, NR.sup.5 or OP(O)OR.sup.4, when R.sup.7 is OP(O)OR.sup.4, oxygen is connected to R.sup.6; R.sup.5 is each independently a hydrogen atom or a hydrocarbon group; R.sup.4 is each independently a hydrocarbon group; and R.sup.2 and R.sup.3 are each independently a hydrogen atom or a hydrocarbon group.

4. The compound according to claim 1 wherein A is R.sup.6(R.sup.7).sub.s, and s is 3.

5. A composition comprising one or more compounds according to claim 1.

6. A composition applied to a material containing a group reactive with a nitrileoxide group, comprising one or more compounds according to claim 1.

7. The composition according to claim 5 which is a hydrophilizing agent.

8. The composition according to claim 6 which is a hydrophilizing agent.

9. A composition comprising one or more compounds according to claim 3.

10. A composition applied to a material containing a group reactive with a nitrileoxide group, comprising one or more compounds according to claim 3.

Description

EXAMPLES

Example 1

(1) ##STR00019##

Preparation of Nitroalkane 1-1

(2) Sodium hydride (0.21 g, 8.6 mmol) was washed with hexane. After adding argon, dry tetrahydrofuran (10 mL) was added. Triethyleneglycol monomethyl ether (0.59 g, 3.6 mmol) was added at 0 C. under ice-cold, and stirred for 1 hour. Diphenylnitroethene (0.68 g, 3.0 mmol) dissolved in dry tetrahydrofuran (5 mL) was added, and stirred for 1 hour at a room temperature. A small amount of acetic acid at 0 C. was added. After dissolving the mixture in diethylether, and was washed with water, saturated brine. The organic layer was dried, and the solvent was distilled off. The product was purified by a silica gel column chromatography (ethyl acetate/hexane=1/1) to obtain Nitroalkane 1-1 (1.1 g) as a yellow viscous material.

(3) Amount (Yield): 1.1 g (93%);

(4) Thin-layer chromatography (Eluent: EtOAc/hexane=1/1): Rf=0.45

(5) .sup.1H NMR (400 MHz, CDCl.sub.3, ppm): 7.35 (m, 10H, Ph-), 5.36 (s, 2H, CH.sub.2NO.sub.2O), 4.78 (t, 2H, J=5.5 Hz, CH.sub.3OC.sub.H2), 3.36 (m, 6H, OCH.sub.2CH.sub.2), 3.55 (m, 4H, OCH.sub.2CH.sub.2), 3.38 (s, 3H, CH.sub.3O)

Preparation of Nitrileoxide 1-2

(6) Nitroalkane 1-1 (1.1 g), dry tetrahydrofuran (20 mL), phenyl isocyanate (0.64 g, 5.4 mmol), and triethylamine (0.82 g, 8.1 mmol) were added under an argon atmosphere, stirred for 4 hours at a room temperature. The reaction mixture was filtered, and the solvent was distilled off. The product was dissolved in chloroform, and the insoluble portion was filtered off. The residue was purified by a silica gel column chromatography (ethyl acetate/hexane=1/4), and a HPLC(chloroform) to obtain Nitroalkane 1-2 (0.48 g) as a colorless viscous body.

(7) Amount (Yield): 0.48 g (48%);

(8) Thin-layer chromatography (Eluent: EtOAc/hexane=1/4): Rf=0.12

(9) IR: 2276 cm.sup.1 (CN.sup.+O.sup.)

(10) .sup.1H NMR (400 MHz, CDCl.sub.3, ppm): 7.42 (m, 4H, Ph-), 7.34 (m, 6H, Ph-), 3.67 (t, 2H, J=5.5 Hz, CH.sub.3OCH.sub.2), 3.67 (m, 8H, OCH.sub.2CH.sub.2), 3.54 (t, 2H, J=5.5 Hz, CH.sub.3OCH.sub.2), 3.37 (s, 3H, CH3O)

Model Click Reaction of Nitrileoxide 1-2

(11) Nitrileoxide 1-2 (0.14 g, 0.38 mmol) and allyl trimethylsilane (0.43 g, 3.8 mmol) were added, dissolved in chloroform, and then heat-stirred for 24 hours at 60 C. A solvent was distilled off, and dried under a reduced pressure to White solid 1-3 (0.14 g).

(12) Amount (Yield): 0.14 g (quantitative)

(13) .sup.1H NMR (400 MHz, CDCl.sub.3, ppm): 7.59 (m, 4H, Ph-), 7.32 (m, 6H, Ph-), 4.66 (m, 1H, OCH), 3.66 (m, 8H, OCH.sub.2CH.sub.2), 3.52 (t, 2H, J=5.5 Hz, CH.sub.3OCH.sub.2), 3.39 (t, 2H, J=5.5 Hz, CH.sub.3OCH.sub.2), 3.35 (s, 3H, CH.sub.3O), 2.98 (m, 1H, OCHCH.sub.2), 2.42 (m, 1H, OCHCH.sub.2), 1.12 (m, 1H, SiCH.sub.2), 0.89 (m, 1H, SiCH.sub.2), 0.02 (s, 9H, SiCH.sub.3)

Example 2

(14) ##STR00020##

Preparation of Nitroalkane 2-1

(15) Sodium hydride (0.42 g, 17 mmol) was washed with hexane. After adding argon, dry tetrahydrofuran (30 mL) was added. Diethyl phosphite (0.99 g, 7.2 mmol) was added at 0 C. under ice-cold and stirred for 1 hour. Diphenylnitroethene (1.40 g, 6.0 mmol) dissolved in dry tetrahydrofuran (10 mL) was added, and stirred for 1 hour at a room temperature. A small amount of acetic acid was added at 0 C., dissolved in dichloromethane, and then washed with water and saturated brine. The organic layer was dried, and the solvent was distilled off, and purified by a silica gel column chromatography (ethyl acetate/hexane=1/1) to obtain Nitroalkane 2-1 (0.94 g) as a white solid.

(16) Amount (Yield): 0.48 g (43%)

(17) Thin-layer chromatography (Eluent: EtOAc/hexane=1/1): Rf=0.45

(18) .sup.1H NMR (400 MHz, CDCl.sub.3, ppm): 7.53 (m, 4H, Ph-), 7.35 (m, 6H, Ph-), 5.45 (d, 2H, J=9.0 Hz, CH.sub.2NO.sub.2O), 3.90-3.74 (m, 4H, CH.sub.3CH.sub.2), 1.16 (t, 6H, J=7.0 Hz, CH.sub.3CH.sub.2)

Preparation of Nitrileoxide 2-2

(19) Nitroalkane 2-1 (0.9 g, 2.5 mmol), dry tetrahydrofuran (20 mL), phenyl isocyanate (0.60 g, 5.0 mmol), and triethylamine (0.76 g, 8.0 mmol) was added under an argon atmosphere, and stirred for 5 hours at a room temperature. The reaction mixture was filtered, and the solvent was distilled off. The product was dissolved in chloroform, and the insoluble portion was filtered off. The residue was purified by a silica gel column chromatography (dichloromethane) to obtain Nitroalkane 2-2 (1.1 g) as a white solid.

(20) Amount (Yield): 0.58 g (67%)

(21) Thin-layer chromatography (Eluent: CH.sub.2Cl.sub.2: Rf=0.45

(22) IR: 2309 cm.sup.1 (CN.sup.+O.sup.)

(23) .sup.1H NMR (400 MHz, CDCl.sub.3, ppm): 7.53 (m, 4H, Ph-), 7.35 (m, 6H, Ph-), 4.05-3.88 (m, 4H, CH.sub.3CH.sub.2), 1.20 (t, 6H, J=7.0 Hz, CH.sub.3CH.sub.2)

Example 3

(24) ##STR00021##

Preparation of Nitroalkane 3-1

(25) Sodium hydride (0.21 g, 8.6 mmol) was washed with hexane. After adding argon, dry tetrahydrofuran (15 mL) was added. Dodecanethiol (0.84 g, 4.2 mmol) was added at 0 C. under ice-cold, and stirred for 1 hour. Diphenylnitroethene (1.4 g, 7.2 mmol) dissolved in dry tetrahydrofuran (10 mL) was added, and stirred for 5 hours at a room temperature. A small amount of acetic acid was added at 0 C., dissolved in dichloromethane, and then washed with water and saturated brine. The organic layer was dried, and the solvent was distilled off. The product was purified by a silica gel column chromatography (dichloromethane/hexane=1/2) to obtain Nitroalkane 3-1 (1.66 g) as a colorless transparent liquid.

(26) Amount (Yield): 1.7 g (92%)

(27) Thin-layer chromatography (Eluent: CH.sub.2Cl.sub.2/hexane=1/1): Rf=0.30

(28) .sup.1H NMR (400 MHz, CDCl.sub.3, ppm): 7.34 (m, 10H, Ph-), 5.32 (s, 2H, CH.sub.2NO.sub.2O), 2.14 (t, 2H, SCH.sub.2CH.sub.2), 1.36 (m, 2H, SCH.sub.2CH.sub.2), 1.24 (m, 18H, CH.sub.2CH.sub.2), 0.87 (t, 3H, J=7.0 Hz, CH.sub.3)

Preparation of Nitrileoxide 3-2

(29) Nitroalkane 3-2 (1.2 g, 2.5 mmol), dry tetrahydrofuran (20 mL), phenyl isocyanate (0.64 g, 5.4 mmol), and triethylamine (0.82 g, 8.1 mmol) were added under an argon atmosphere, and stirred for 4 hours at a room temperature. The reaction mixture was filtered, and the solvent was distilled off. The produce was dissolved in chloroform, and the insoluble portion was filtered off. The residue was purified by a silica gel column chromatography (ethyl acetate/hexane=1/4), and a HPLC(chloroform) to obtain Nitroalkane 3-2 (1.1 g) as a yellow viscous material.

(30) Amount (Yield): 1.07 g (95%)

(31) Thin-layer chromatography (Eluent: CH.sub.2Cl.sub.2/hexane=1/3): Rf=0.30

(32) IR: 2286 cm.sup.1 (CN.sup.+O.sup.)

(33) .sup.1H NMR (400 MHz, CDCl.sub.3, ppm): 7.52 (m, 4H, Ph-), 7.35 (m, 6H, Ph-), 2.56 (t, 2H, SCH.sub.2CH.sub.2), 1.56 (m, 2H, SCH.sub.2CH.sub.2), 1.23 (m, 18H, CH.sub.2CH.sub.2), 0.87 (t, 3H, J=7.0 Hz, CH.sub.3)

Example 4

(34) ##STR00022##

Preparation of Nitroalkane mPEG 4-1 Having High Molecular Weight

(35) Sodium hydride (0.10 g, 4.5 mmol) was washed with hexane. After adding argon, dry tetrahydrofuran (15 mL) was added. Polyethyleneglycol monomethyl ether (Mn=2000, 13.0 g, 1.5 mmol) dissolved in dry tetrahydrofuran (5 mL) and a small amount of dry dimethylformamide (DMF) was added at 0 C. under ice-cold, and stirred for 2 hours at a room temperature. Diphenylnitroethene (0.33 g, 4.5 mmol) dissolved in dry tetrahydrofuran (10 mL) was added, and stirred for 5 hours at a room temperature. A small amount of acetic acid was added at 0 C., dissolved in diethylether, and then washed with water and saturated brine. The organic layer was dried, and the solvent was distilled off. The product was dissolved in a small amount of chloroform and an excessive amount of ether was added. The precipitated solid was filtered, dried under reduced pressure to obtain mPEG 4-1 (2.4 g).

(36) .sup.1H NMR (400 MHz, CDCl.sub.3, ppm): 7.30 (m, 10H, Ph-), 5.34 (s, 2H, CH.sub.2NO.sub.2), 3.64 (br, 4H, OCH.sub.2CH.sub.2O), 3.38 (s, 3H, CH.sub.3 0-)

Preparation of Nitronitrileoxide mPEG 4-2 Having High Molecular Weight

(37) mPEG 4-1 (1.1 g, 0.5 mmol), dry tetrahydrofuran (20 mL), phenyl isocyanate (0.60 g, 5.0 mmol), and triethylamine (0.75 g, 7.5 mmol) were added under an argon atmosphere, and stirred for 4 hours at a room temperature. The reaction mixture was filtered, and the solvent was distilled off. The product was dissolved in chloroform, and the insoluble portion was filtered off. The residue was purified by a silica gel column chromatography (ethyl acetate/hexane=1/4) and a HPLC(chloroform) to obtain Nitrileoxide mPEG 4-2 (0.93 g) having high molecular weight as a white solid.

(38) IR: 2276 cm.sup.1 (CN.sup.+O.sup.)

(39) .sup.1H NMR (400 MHz, CDCl.sub.3, ppm): 7.43 (m, 4H, Ph-), 7.35 (m, 6H, Ph-), 3.64 (br, 4H, OCH.sub.2CH.sub.2O), 3.38 (s, 3H, CH.sub.3O)

Model Click Reaction of Nitronitrileoxide mPEG 4-2 Having High Molecular Weight

(40) mPEG 4-2 (0.1 g, 0.05 mmol) and allyl trimethylsilane (57 mg, 0.5 mmol) was added, dissolved in chloroform, and then heat-stirred at 60 C. A solvent was distilled off, and the product was dissolved in a small amount of chloroform, and precipitated in hexane. The precipitate was filtered, and dried under a reduced pressure to obtain mPEG 4-3 as a white solid.

(41) .sup.1H NMR (400 MHz, CDCl.sub.3, ppm): 7.55 (m, 4H, Ph-), 7.26 (m, 6H, Ph-), 4.63 (m, 1H, OCH), 3.63 (br, 4H, OCH.sub.2CH.sub.2O), 2.95 (m, 1H, OCHCH.sub.2), 2.38 (m, 1H, OCHCH.sub.2), 1.10 (m, 2H, CH.sub.2Si), 0.84 (m, 2H, CH.sub.2Si), 0.00 (s, 9H, Si(CH.sub.3).sub.3)

Example 5

(42) ##STR00023##

(43) Sodium hydride (0.43 g, 16 mmol) was washed with hexane three times. After adding argon, dry DMF (10 mL) was added. Tetraethylene glycol (0.58 g, 3.0 mmol) was added at 0 C. under ice-cold, and stirred for 1 hour. Diphenylnitroethene (2.7 g, 12 mmol) dissolved in Dry DMF (10 mL) was added, and stirred for 1 hour at a room temperature. A small amount of acetic acid was added at 0 C., dissolved in dichloromethane, and then washed with water and saturated brine. The organic layer was dried, and the solvent was distilled off. The product was purified by a silica gel column chromatography (ethyl acetate/hexane=1/2) to obtain Nitroalkane 5-1 (1.9 g) as a yellow viscous material.

(44) Amount (Yield): 1.9 g (98%)

(45) .sup.1H NMR (400 MHz, CDCl.sub.3, ppm): 7.32 (m, 20H, Ph-), 5.33 (s, 4H, CH.sub.2NO.sub.2O), 3.72 (t, 4H, J=5.5 Hz, OCH.sub.2), 3.35 (s, 8H, OCH.sub.2CH.sub.2), 3.51 (t, 4H, J=5.5 Hz, OCH.sub.2)

Preparation of Nitrileoxide 5-2

(46) Dry tetrahydrofuran (30 mL), phenyl isocyanate (1.4 g, 12 mmol) and triethylamine (1.8 g, 18 mmol) were added under an argon atmosphere, and stirred for 8 hours at a room temperature. Because the insoluble portion is precipitated, further dry tetrahydrofuran (10 mL) was added. The reaction mixture was filtered, and the solvent was distilled off. The product was dissolved in chloroform, the insoluble portion was filtered off. The residue was purified by a silica gel column chromatography (chloroform/methanol=97/3) to obtain Nitrileoxide 5-2 (0.66 g) as a colorless viscous body.

(47) Amount (Yield): 0.66 g (37%)

(48) .sup.1H NMR (400 MHz, CDCl.sub.3, ppm): 7.36 (m, 20H, Ph-), 3.70 (m, 16H, OCH.sub.2CH.sub.2)

Example 6: Preparation of Tri-Functional Nitrileoxide

(49) ##STR00024## ##STR00025##

Preparation of Tri-Functional Alcohol Compound

(50) 1,1,1-Tris(4-hydroxyphenyl)ethane (4.2 g, 30 mmol), potassium carbonate (13 g, 90 mmol), and chloroethoxy(ethoxy ethanol (24 g, 66 mmol) were dissolved in dimethylformamide (170 mL), and then stirred for 12 hours at 90 C. in an oil-bath. The progress of the reaction was confirmed by thin-layer chromatography. The residue was filtered and the solvent was distilled off at 90 C. (oil bath) under a reduced pressure. The residue was dissolved in ethyl acetate, and washed with 1M of aqueous hydrochloric acid and saturated brine. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off. The product was purified by a silica gel column chromatography (chloroform/methanol=95/1) to obtain a tri-functional alcohol compound (13 g, yield 89%) as a yellow liquid.

(51) Rf: 0.33 (Eluent; CHCl.sub.3/MeOH=95/5)

(52) .sup.1H NMR (400 MHz, CDCl.sub.3, ppm): 9.84 (s, 1H, CHO), 7.43 (s, 1H, Ph-H), 7.00 (d, J=8.8 Hz, 1H, Ph-H), 6.94 (d, J=8.8 Hz, 1H, Ph-H), 4.23 (t, J=6.8 Hz, 4H, Ph-OCH2-O), 3.92 (m, 4H, Ph-OCH2-O), 3.74 (m, 4H, Ph-OCH2-O), 3.66 (m, 20H, OCH2-), 2.50 (s, 3H, CH.sub.3)

Preparation of Tri-Functional Nitroalkane Compound

(53) Sodium hydride (1.1 g, 45 mmol) was washed with hexane three times. After adding argon, dry DMF (50 mL) was added. Tri-functional alcohol compound (3.5 g, 5.0 mmol) was added under ice-cold (0 C.), and stirred for 2 hours. Diphenylnitroethene (10 g, 23 mmol) dissolved in dry DMF (10 mL) was added, and stirred for 2 hours at a room temperature. A small amount of acetic acid was added at 0 C., dissolved in dichloromethane, and then washed with deionized water and saturated brine. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off. The product was purified by a silica gel column chromatography (ethyl acetate/liquid oxygen=1/1) to obtain tri-functional nitroalkane compound (1.5 g, yield 65%) as a yellow viscous material.

Preparation of Tri-Functional Nitrileoxide

(54) To tri-functional nitroalkane compound (4.4 g, 3.2 mmol) prepared above, dichloromethane (100 mL), p-chlorophenyl isocyanate (4.4 g, 29 mmol), and triethylamine (5.5 g, 54 mmol) were added under an argon atmosphere, and stirred for 2 hours at a room temperature. The insoluble portion was filtered off, and the solvent was distilled off. The product was dissolved in chloroform, and the insoluble portion was filtered off. The residue was purified by a silica gel column chromatography to obtain a desired product.

Example 7: Crosslinking of General Purpose Rubber (PAN)

(55) ##STR00026##

Crosslinking of Polyacrylonitrile (PAN)

(56) While PAN (54 mg, 1.0 mmol) was heated and stirred in DMF (1.0 mL), TEG(CNO).sub.2 7-1 (30 mg, 0.05 mmol) was added, and reacted for 12 hours at 90 C. The mixture was washed with DMF repeatedly, and dried to obtain a pale yellow network polymer 7-2 (73 mg, 87%).

Example 8: Preparation of Block Polymer

(57) ##STR00027##

(58) mPEGCNO (330 mg, 0.15 mmol) and PVLCC (360 mg, 0.05 mmol) were dissolved in dry toluene (2.0 mL), and heat-stirred in oil bath (100 C.) for 24 hours. A solvent was distilled off. The product was dissolved in a small amount of chloroform, and reprecipitated in diethylether to obtain mPEG-b-PVL (417 mg).

(59) Appearance: white solid, yield: 417 mg (89%)

(60) .sup.1H NMR (300 MHz, 298 K, CDCl.sub.3): 7.55-7.30 (m, 10H, Ph(mPEG)), 7.44-7.03 (m, 6H, Ph(PVL)), 6.82 (m, NH), 4.62 (m, 1H, OCH), 4.33 (m, OCH.sub.2), 4.10 (m, OCH.sub.2 (PVL)), 3.56 (m, CH.sub.2CH.sub.2O(mPEG)), 3.39 (s, 3H, CH.sub.3O (mPEG)), 3.08-2.98 (m, 1H, OCHCH.sub.2), 2.62-2.54 (m, 1H, OCHCH.sub.2), 2.54 (m, CH.sub.2CO(PVL)), 1.73-1.68 (m, CH.sub.2CH.sub.2 (PVL))

(61) M.sub.n=9500, M.sub.w/M.sub.n=1.10 (eluent: CHCl.sub.3, PSt standard)

Example 9: Preparation of Block Polymer

(62) ##STR00028##

Preparation of mPEG-b-F Polymer

(63) To mPEGCNO (330 mg, 0.15 mmol) and perfluoropolymer 9-1 (160 mg, 0.05 mmol), 1,3-bis(trifluoromethyl)benzene (2.0 mL) was added, and heat-stirred in oil bath (100 C.) for 24 hours. The product was dissolved in a small amount of chloroform, and reprecipitated in diethylether to obtain mPEG-b-F polymer 9-2.

(64) Appearance: white viscous liquid

(65) .sup.1H NMR (300 MHz, 298 K, CDCl.sub.3): 7.55-7.30 (m, 10H, Ph (mPEG)), 4.66 (m, 1H, OCH), 4.33 (m, OCH.sub.2), 4.10 (m, OCH.sub.2 (PVL)), 3.56 (m, CH.sub.2CH.sub.2O (mPEG)), 3.38 (s, 3H, CH.sub.3O (mPEG))

Example 10: Preparation of Star Polymer (3-Stranded)

(66) ##STR00029##

(67) mPEGCNO (330 mg, 0.15 mmol) and core 3-1 (9.9 mg, 0.03 mmol) was dissolved in toluene (6.0 mL), and heat-stirred in oil bath (100 C.) for 24 hours. A solvent was distilled off. The product was dissolved in a small amount of chloroform, and reprecipitated in diethylether to obtain mPEG-3-star (92 mg).

(68) Appearance: white solid, yield: 92 mg (44%)

(69) .sup.1H NMR (300 MHz, 298 K, CDCl.sub.3): 7.55-7.30 (m, 30H, Ph(mPEG)), 6.93 (d, 6H, J=8.8 Hz, PhH), 6.71 (d, 6H, J=8.8 Hz, PhH), 4.48 (m, 3H, OCH), 3.56 (m, CH.sub.2CH.sub.2O(mPEG)), 3.39 (s, 3H, CH.sub.3O(mPEG)), 3.00 (m, 3H, OCHCH.sub.2), 2.54 (m, 3H, OCHCH.sub.2), 2.07 (s, 3H, CCH.sub.3)

(70) M.sub.n=11000, M.sub.w/M.sub.n=1.06 (eluent: CHCl.sub.3, PSt standard).

Example 11: Preparation of Star Polymer (6-Stranded)

(71) ##STR00030##

Preparation of Star Polymer Having 6-Strand mPEGCNO

(72) mPEGCNO (450 mg, 0.20 mmol) and core 6-1 (12 mg, 0.02 mmol) were dissolved in toluene (10 mL), and then heat-stirred in oil bath (100 C.) for 24 hours. A solvent was distilled off. The product was dissolved in a small amount of chloroform, and reprecipitated in diethylether five times to obtain mPEG-6-star (238 mg).

(73) Appearance: white solid, yield: 238 mg (86%)

(74) .sup.1H NMR (300 MHz, 298 K, CDCl.sub.3): 7.55-7.30 (m, 60H, Ph(mPEG)), 4.47 (m, 6H, OCH), 3.56 (m, CH.sub.2CH.sub.2O(mPEG)), 3.39 (s, 18H, CH.sub.3O(mPEG)), 2.90 (m, 6H, OCHCH.sub.2), 2.44 (m, 6H, OCHCH.sub.2), 1.53 (m, 18H, CCH.sub.3)

(75) M.sub.n=13000, M.sub.w/M.sub.n=1.10 (eluent: CHCl.sub.3, PSt standard)

Example 12: Preparation of Block Polymer (Part 3: Block with Silicone)

(76) ##STR00031##

Preparation of PEG-PDMS-PEG Tri-Block Copolymer

(77) Both-terminals-PDMS 12-1 (90 mg, 0.015 mmol) and mPEGCNO12-2 (130 mg, 0.06 mmol) were stirred in toluene for 12 hours. The process of the reaction was monitored by .sup.1H NMR, and the reaction was stopped at the peak of the olefin was lost. The product was dissolved in a small amount of chloroform and washed with water to obtain PEG-PDMS-PEG tri-block copolymer 12-3.

(78) Appearance: white viscous liquid

(79) .sup.1H NMR (300 MHz, 298 K, CDCl.sub.3): 7.55-7.30 (m, 10H, Ph (mPEG)), 4.32 (m, 1H, OCH), 4.33 (m, OCH.sub.2), 4.10 (m, OCH.sub.2 (PVL)), 3.56 (m, CH.sub.2CH.sub.2O(mPEG)), 3.38 (s, 3H, CH.sub.3O(mPEG)), 3.08-2.98 (m, 1H, OCHCH.sub.2), 2.62-2.54 (m, 1H, OCHCH.sub.2), 0.02 (m, PDMS)

INDUSTRIAL APPLICABILITY

(80) The compound of the present invention can be suitably used in various applications, for example, as a hydrophilizing agent or a surface treating agent.