Nitrileoxide compound

Abstract

A compound of the formula (III): ##STR00001##
wherein R.sup.21 is a hydrogen atom or an alkyl group; R.sup.22 is a hydrogen atom or an alkyl group; and R.sup.23 is a divalent organic group.

Claims

1. A compound of the formula (III): ##STR00060## wherein: R.sup.21 is a hydrogen atom or an alkyl group; R.sup.22 is a hydrogen atom or an alkyl group; and R.sub.23 is —R.sup.24—R.sup.25—R.sup.26—; R.sup.24 is —CO—O—; R.sup.25 is a linker having 1-20 atoms of the main chain; R.sub.26 is —CR.sup.27R.sup.28—; and R.sup.27 and R.sup.28 are each independently an aryl group having 5-10 carbon atoms.

Description

EXAMPLE

Example 1: Preparation of dihydroxydiphenyl nitrileoxide

(1) ##STR00050##

Preparation of triisopropylsilyl(TIPS) benzophenone 1-2

(2) Dihydroxybenzophenone 1-1 (17 g, 78 mmol), imidazole (20 g, 300 mmol), and N,N-dimethyl-4-aminopyridine (DMAP: 4.1 g, 32 mmol) were dissolved in anhydrous tetrahydrofuran (THF: 400 mL), and triisopropylsilyl chloride (33 g, 170 mmol) was added at 0° C. Then, the reaction mixture was stood for 1 day at a room temperature. The solvent was evaporated under reduced pressure, and dichloromethane was added. The mixture was separated with water, and dried. The solvent was evaporated under reduced pressure, and the residue was purified a silica gel column chromatography (ethyl acetate:hexane=1:50) to obtain a colorless transparent oil (30 g, 60 mmol, 73%).

(3) .sup.1H NMR (400 MHz, 298 K, CDCl.sub.3): δ 7.74-7.71 (d, J=8.0 Hz, 4H), 6.94-6.92 (d, J=8.0 Hz, 4H), 1.32-1.26 (m, 6H), 1.13-1.11 (d, J=8.0 Hz, 36H) ppm

Preparation of TIPS diphenylnitroethene 1-4

(4) TIPS benzophenone 1-2 (21 g, 40 mmol) was added to THF (40 mL), and cooled to 0° C. under Ar atmosphere. Lithium bis(trimethylsilyl)amide (48 mL, 48 mmol) was added, and stirred for one day at a room temperature. The solvent was evaporated under reduced pressure, and ethyl acetate was added. The reaction mixture was separated with water, saturated saline solution. The solvent was evaporated under reduced pressure, and nitromethane (40 mL) was added. The mixture was refluxed at 115° C. for one day. The solvent was distilled off to obtain a brown oil. This compound was purified by a flash column chromatography to an orange oil. This was used in the next reaction.

Preparation of TIPS diphenyl nitrileoxide 1-5

(5) The crude TIPSdiphenylnitroethene 1-4 was added to anhydrous THF (400 mL), and cooled to −78° C. under Ar atmosphere. n-BuLi (38 mL, 60 mmol) was added, and stirred for 30 minutes. A concentrated sulfuric acid (>95%, 20 mL, 400 mmol) was added, and stirred as 0° C. for 30 minutes. The mixture was separated with water, and dried. The solvent was removed under a reduced pressure to obtain an orange oil. This was used in the next reaction.

Preparation of dihydroxydiphenyl nitrileoxide 1-6

(6) The crude TIPS diphenyl nitrileoxide 1-5 was dissolved in THF (480 mL), and tetra-n-butylammonium fluoride (TBAF: 73 mL, mmol) was added and stirred for 10 minutes. Dichloromethane was added at an appropriate amount, separated with water and saturated saline solution, and dried. The solvent was evaporated under reduced pressure, and the residue was purified by a silica gel column chromatography (hexane.fwdarw.hexane:ethyl acetate=8:1.fwdarw.4:1.fwdarw.2:1) to obtain a yellow oil (4.1 g, 14 mmol, 34%).

(7) .sup.1H NMR (400 MHz, 298 K, CDCl.sub.3): δ 7.05-7.03 (d, J=8.0 Hz, 4H), 6.77-6.75 (d, J=8.0 Hz, 4H), 2.28-2.25 (t, J=7.0 Hz, 4H), 1.28 (m, 4H), 0.86-0.83 (t, J=7.0 Hz, 3H) ppm

Example 2: Condensation Polymerizing Reaction Using Dihydroxydiphenyl Nitrileoxide

(8) ##STR00051##

Preparation of PE-CNO-5

(9) Dihydroxydiphenyl nitrileoxide 1-6 (0.15 g, 0.50 mmol) and bisphenol A (0.11 g, 0.50 mmol) was added to dehydrated dichloromethane (1.0 mL), and triethylamine (0.44 mL, 4.0 mmol) was added while stirring at 0° C. Then, a solution which adipoyl chloride (0.18 g, 0.1 mmol) was dissolved in chloroform (1 mL) was added slowly, and then stirred for 2 hours at a room temperature. The product was reprecipitated in methanol, and ether. The resulting pale yellow solid was dissolved in chloroform, separated with water, and dried. The solvent was evaporated under reduced pressure to obtain a pale yellow solid (200 mg, 47%).

(10) Yield, 39%

(11) Number average molecular weight (GPC), 14,000

(12) M.sub.w/M.sub.n (GPC), 2.5

(13) Copolymerization Ratio (.sup.1H NMR), 1:1

(14) .sup.1H NMR (400 MHz, 298 K, CDCl.sub.3): δ 7.29-7.27 (d, J=8.4 Hz, 4H, Ph-), 7.21-7.20 (d, J=8.4 Hz, 4H, Ph-), 7.08-7.06 (d, J=8.4 Hz, 4H, Ph-), 6.98-6.96 (d, J=8.4 Hz, 4H, Ph-), 2.61 (m, 8H, —CH.sub.2CH.sub.2CH.sub.2CH.sub.2—), 2.34 (m, 2H, —CH.sub.2CH.sub.2CH.sub.2CH.sub.3), 1.86 (m, 8H, —CH.sub.2CH.sub.2CH.sub.2CH.sub.2—), 1.65 (m, 6H, C(CH.sub.3).sub.2), 1.34 (m, 4H, —CH.sub.2CH.sub.2CH.sub.2CH.sub.3), 0.88 (m, 3H, —CH.sub.2CH.sub.2CH.sub.2CH.sub.3) ppm

Preparation of PE-CNO-10

(15) Dihydroxydiphenyl nitrileoxide 1-6 (0.30 g, 1.00 mmol) was added to dehydrated dichloromethane (1.0 mL), and triethylamine (0.44 mL, 4.0 mmol) was added while stirring at 0° C. Then, a solution which adipoyl chloride (0.18 g, 0.1 mmol) was dissolved in chloroform (1 mL) was added slowly, and then stirred for 2 hours at a room temperature. The product was reprecipitated in methanol, and ether. The resulting pale yellow solid was dissolved in chloroform, separated with water, and dried. The solvent was evaporated under reduced pressure to obtain a pale yellow solid (200 mg, 47%).

(16) Yield, 47%

(17) Number average molecular weight (GPC), 15000

(18) M.sub.w/M.sub.n, 3.4

(19) .sup.1H NMR (400 MHz, 298 K, CDCl.sub.3): δ 7.30-7.28 (d, J=7.8 Hz, 4H, Ph-), 7.09-7.07 (d, J=7.8 Hz, 4H, Ph-), 2.63 (m, 4H, —CH.sub.2CH.sub.2CH.sub.2CH.sub.2—), 2.34 (m, 2H, —CH.sub.2CH.sub.2CH.sub.2CH.sub.3), 1.77 (m, 4H —CH.sub.2CH.sub.2CH.sub.2CH.sub.2—), 1.34 (m, 4H, —CH.sub.2CH.sub.2CH.sub.2CH.sub.3), 0.89 (m, 3H, —CH.sub.2CH.sub.2CH.sub.2CH.sub.3) ppm

Example 3: Click Reaction of PE-CNO and allyl Trimethylsilane

(20) ##STR00052##

Preparation of PE-isoxazoline-5

(21) PE-CNO-10 (25 mg, 0.057 mmol) and allyl trimethylsilane (65 mg, 0.57 mmol) were dissolved in chloroform (0.5 mL), and stirred for 16 hour at 40° C. The solvent and unreacted allyl trimethylsilane were evaporated to obtain a yellow solid.

(22) .sup.1H NMR (400 MHz, 298 K, CDCl.sub.3): δ 7.28-7.26 (d, J=7.8 Hz, 4H, Ph-), 7.22-7.20 (d, J=7.8 Hz, 4H, Ph-), 7.07-7.05 (d, J=7.8 Hz, 4H, Ph-), 6.98-6.96 (d, J=8.4 Hz, 4H, Ph-), 4.58 (m, 1H, —CNOCHCH.sub.2—), 2.63 (m, 8H, —CH.sub.2CH.sub.2CH.sub.2CH.sub.2—), 2.36 (m, 2H, —CH.sub.2CH.sub.2CH.sub.2CH.sub.3), 2.21 (m, 2H, —CNOCHCH.sub.2—), 1.88 (m, 8H, —CH.sub.2CH.sub.2CH.sub.2CH.sub.2—), 1.65 (m, 6H, C(CH.sub.3).sub.2), 1.43 (m, 2H, —CH.sub.2CH.sub.2CH.sub.2CH.sub.3), 1.08 (m, 4H, —CH.sub.2CH.sub.2CH.sub.2CH.sub.3, —CH.sub.2Si(CH.sub.3).sub.3), 0.81 (m, 3H, —CH.sub.2CH.sub.2CH.sub.2CH.sub.3), 0 (s, 9H, Si(CH.sub.3).sub.3) ppm

Preparation of PE-isoxazoline-10

(23) PE-CNO-10 (25 mg) and allyl trimethylsilane (65 mg, 0.57 mmol) were dissolved in chloroform (0.5 mL), and stirred for hour at 40° C. The solvent and unreacted allyl trimethylsilane were evaporated to obtain a pale yellow solid.

(24) .sup.1H NMR (400 MHz, 298 K, CDCl.sub.3): δ 7.30-7.28 (d, J=7.8 Hz, 4H, Ph-), 7.07-7.05 (d, J=7.8 Hz, 4H, Ph-), 4.59 (m, 1H, —CNOCHCH.sub.2—), 2.65 (m, 4H, —CH.sub.2CH.sub.2CH.sub.2CH.sub.2—), 2.34 (m, 2H, —CH.sub.2CH.sub.2CH.sub.2CH.sub.3), 2.23 (m, 2H, —CNOCHCH.sub.2—), 1.89 (m, 4H, —CH.sub.2CH.sub.2CH.sub.2CH.sub.2—), 1.34 (m, 2H, —CH.sub.2CH.sub.2CH.sub.2CH.sub.3), 1.08 (m, 4H, —CH.sub.2CH.sub.2CH.sub.2CH.sub.3, —CH.sub.2Si(CH.sub.3).sub.3), 0.80 (m, 3H, —CH.sub.2CH.sub.2CH.sub.2CH.sub.3), 0 (s, 9H, SiCH.sub.3) ppm

Example 4: Crosslinking Reaction of Natural Rubber by PE-CNO

(25) ##STR00053##

(26) Crosslinking Reaction by PE-CNO-5

(27) A natural rubber was dissolve in toluene, and PE-CNO-5 was added and reacted at 90° C. The produced polymer was immersed in chloroform for one day, and dried under air at a room temperature and under vacuum at 70° C. to obtain a pale yellow network polymer (53%).

(28) Yield: 53%

(29) Degree of swelling (CHCl.sub.3): 5700

(30) Crosslinking Reaction by PE-CNO-10

(31) A natural rubber (67 mg) was dissolve in toluene (1 mL), PE-CNO-10 (7.0 mg) was added and reacted at 90° C. The produced polymer was immersed in chloroform for one day, and dried under air at a room temperature and under vacuum at 70° C. to obtain a pale yellow network polymer (39 mg, 53%).

(32) Yield: 67%

(33) Degree of swelling (CHCl.sub.3): 3700%

Example 5: Preparation of OH diphenyl nitrileoxide

(34) ##STR00054## ##STR00055##

Preparation of OH benzophenone 2-2

(35) 4-hydroxy benzophenone (9.9 g, 50 mmol), 2-bromoethanol (7.5 g, 60 mmol) and potassium carbonate (10 g, 75 mmol) were added to N,N-dimethylformamide (DMF, 150 mL), and stirred at 90° C. for one day. A solvent was distilled off, and dichloromethane was added. The mixture extracted with water and saturated saline solution, and dried. A solvent was distilled off to obtain a pale yellow powder (crude yield 12 g). This compound was used in the next reaction.

Preparation of TIPS benzophenone 2-3

(36) The crude 2-2 (12 g), imidazole (8.5 g, 130 mmol), and DMAP (1.5 g, 1.3 mmol) were dissolved in anhydrous THF (250 mL), and triisopropylsilyl chloride (19 g, 100 mmol) was added at 0° C. The mixture was returned to a room temperature and reacted for one day. The solvent was evaporated under reduced pressure. The dichloromethane was added and separated with water, and dried. The solvent was evaporated under reduced pressure. The residue was purified by a silica gel column chromatography (ethyl acetate:hexane=1:30) to obtain a pale oil (22 g, 45 mmol, 90%).

Preparation of TIPS diphenylnitroethene 2-5

(37) TIPS benzophenone 2-3 (11 g, 23 mmol) was added to THF (20 mL), and cooled to 0° C. under Ar atmosphere. Lithium bis(trimethylsilyl)amide (19 mL, 25 mmol) was added, and stirred at a room temperature for one day. The solvent was evaporated under reduced pressure, and ethyl acetate was added. The mixture was separated with water and saturated saline solution. The solvent was evaporated under reduced pressure. Nitromethane (25 mL) was added, and refluxed at 115° C. for one day. A solvent was distilled off to obtain a brown oil. This compound was used in the next reaction.

Preparation of TIPS diphenyl nitrileoxide 2-6

(38) The crude 2-5 (14 g) was added to anhydrous THF (350 mL), and cooled at −78° C. under Ar atmosphere. n-BuLi (25 mL, 64 mmol) was added, and stirred for 30 minutes. A concentrated sulfuric acid (>95%, 17 mL, 320 mmol) was added, stirred at 0° C. for 30 minutes. The mixture was separated water, and dried. The solvent was evaporated under reduced pressure. The residue was purified by a silica gel column chromatography (dichloromethane:hexane=1:2) to obtain a yellow oil (5.8 g, 12 mmol, 54%).

Preparation of OH diphenyl nitrileoxide 2-7

(39) TIPS diphenyl nitrileoxide 2-6 (2.0 g, 4.5 mmol) was dissolve in THF (50 mL), and TBAF (1.7 mL, 6.7 mmol) was added and stirred for 20 minutes. Dichloromethane was added, and the mixture was separated with water and saturated saline solution, and dried. The solvent was evaporated under reduced pressure. The residue was purified by a silica gel column chromatography (dichloromethane:hexane=10:1) to obtain a yellow oil (2.6 g, 8.2 mmol, 97%).

(40) .sup.1H NMR (400 MHz, 298 K, CDCl.sub.3): δ 7.37-7.28 (m, J=8.7 Hz, 5H), 7.18-7.16 (d, J=8.7 Hz, 2H), 6.82-6.80 (d, J=8.7 Hz, 2H), 5.16 (s, 1H), 2.38-2.34 (t, J=6.8 Hz, 2H), 1.37 (m, 4H), 0.93-0.89 (t, J=6.8 Hz, 3H) ppm

Example 6: Ring-Opening Polymerization Using OH diphenyl nitrileoxide as an Initiator

(41) ##STR00056##

Preparation of macromolecular nitrileoxide PVL-CNO-2

(42) 5-valerolactone (0.96 g, 9.6 mmol) and OHdiphenyl nitrileoxide 3-6 (0.20 g, 0.64 mmol) were added to dehydrated toluene (5 mL), and diphenyl phosphate (0.16 g, 0.64 mmol) was added while stirring at a room temperature, and stirred for 2 hours. Reprecipitation in hexane:ethanol=(9:1) (100 mL) and filtration were repeated two times to obtain a white solid 0.83 g (72%). As a result of the GPC measurement, unimodal peak (Mn=6100, Mw/Mn=1.21) was observed.

(43) .sup.1H NMR (400 MHz, 298 K, CDCl.sub.3): δ 7.34-7.26 (m, 5H, Ph-) 7.22-7.20 (d, J=8.0 Hz, 2H, Ph-), 6.88-6.86 (d, J=8.0 Hz, 2H, Ph-), 4.44-4.42 (t, J=4.0 Hz, 2H, —OCH.sub.2CH.sub.2O—), 4.17 (m, 2H, —OCH.sub.2CH.sub.2O—), 4.08 (m, 62H, —CH.sub.2CH.sub.2OCO—) 3.67-3.64 (t, J=6.0, 2H, —CH.sub.2CH.sub.2OH), 2.34 (m, 64H, —OCOCH.sub.2CH.sub.2—, —CH.sub.2CH.sub.2CH.sub.2CH.sub.3), 1.68 (m, 124H, —CH.sub.2CH.sub.2CH.sub.2CH.sub.2—), 1.35 (m, 4H, —CH.sub.2CH.sub.2CH.sub.2CH.sub.3), 0.90-0.87 (m, J=6.0, 3H, —CH.sub.2CH.sub.2CH.sub.2CH.sub.3) ppm

Example 7: Click Reaction of PVL-CNO-2 and allyl Trimethylsilane

(44) ##STR00057##

Preparation of PVL-isoxazoline

(45) PVL-CNO-2 (75 mg, 0.022 mmol) and allyl trimethylsilane (25 mg, 0.22 mmol) were dissolved in chloroform (0.5 mL), and stirred at 40° C. for one day. The solution was reprecipitated in hexane (50 mL) to obtain a white solid.

(46) .sup.1H NMR (400 MHz, 298 K, CDCl.sub.3): δ 7.32-7.18 (m, 7H), 6.87-6.85 (d, J=8.0 Hz, 2H), 4.59 (m, 1H), 4.45-4.43 (t, J=4.0 Hz, 2H), 4.26 (m, 2H), 4.09 (m, 60H) 3.67-3.64 (t, J=6.0, 2H), 2.77-2.71 (m, 1H) 2.40-2.32 (m, 61H), 1.69-1.67 (m, 120H), 1.28-1.24 (m, 2H), 1.10-1.08 (m, 3H) 0.85-0.79 (m, 4H), 0.00 (s, 9H) ppm

Example 8

(47) ##STR00058## ##STR00059##

Preparation of nitroalkane18-3

(48) Sodium hydride (1.5 g) was washed with hexane. After adding an inert gas, dry DMF (40 mL) was added. 1,6-hexanediol (7.1 g) was added at 0° C., and stirred for 1 hour. diphenyl nitroethene (4.5 g) 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 deionized water and saturated saline solution. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off. The residue was purified by a silica gel chromatography (ethyl acetate/hexane=1/1) to obtain Nitroalkane 18-3 (5.9 g, yield 86%) as a yellow viscous material.

Preparation of monomer NAMA

(49) Nitroalkane 18-3 (2.1 g) and pyridine (0.48 g) was dissolved in dry dichloromethane (15 mL), and methacylic acid chloride (0.56 g) was added dropwise at 0° C., and stirred for 1 hour at a room temperature. After dissolving in chloroform, the mixture was washed with saturated saline solution. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off. The residue was purified by a silica gel chromatography (chloroform/hexane=3/1) to obtain a colorless clear liquid NAMA (1.0 g, yield 42%).

(50) .sup.1H NMR (300 MHz, CDCl.sub.3, ppm) δ 7.67-7.24 (m, 10H, Ph), 6.09 (s, 1H, H.sub.2C═C), 5.43 (s, 1H, H.sub.2C═C), 5.34 (s, 2H, CH.sub.2NO.sub.2), 4.13 (t, 2H, J=6.7 Hz, OCH.sub.2), 4.13 (t, 2H, J=6.7 Hz, C=OOCH.sub.2), 3.56 (t, 2H, J=6.2 Hz, OCH.sub.2), 1.94 (s, 1H, C═CCH.sub.3), 1.72-1.60 (m, 4H, OCH.sub.2CH.sub.2), 1.50-1.31 (m, CH.sub.2CH.sub.2)

Preparation of PNAMA by Free Radical Polymerization

(51)
[M]/[I]=33,[M]=0.6M
wherein M is NAMA, and I is AIBN.

(52) NAMA (0.5 g), azobisisobutyronitrile (AIBN) (6.0 mg), anisole (2.0 mL) was added to a reactor. After freeze-degassing three times, the mixture was stirred at 90° C. for 4 hours. Reprecipitation in hexane/ethanol=9/1 was performed three times to obtain a white solid (0.29 g).

(53) .sup.1H NMR (400 MHz, CDCl.sub.3, ppm): δ 7.3 (m, 10H, Ph-H), 5.3 (s, 2H, —C(Ph).sub.2-CH.sub.2—NO.sub.2), 3.9 (br, 2H, —C(O)O—CH.sub.2—), 3.4 (br, 2H, —C(Ph).sub.2-O—CH.sub.2—), 2.1-0.8 (m, 13H, —O—C.sub.4H.sub.8—O—, —CH.sub.2—C(CH.sub.3)—C(O)—)

Preparation of PCNOMA

(54) PNAMA (0.18 g), dry dichloromethane 10 mL, p-chlorophenyl isocyanate (0.67 g) and triethylamine (0.68 g) was added under an inert gas, and stirred for 2 hours at a room temperature. The insoluble portion was filtered off, and the solvent was evaporated. Reprecipitation in hexane/ethanol=9/1 was performed three times to obtain a white solid (42 mg, yield 23%).

(55) .sup.1H NMR (400 MHz, CDCl.sub.3, ppm): δ 7.3 (m, 10H, Ph-H), 3.9 (br, 2H, —C(O)O—CH.sub.2—), 3.4 (br, 2H, —C(Ph).sub.2-O—CH.sub.2—), 2.1-0.7 (m, 13H, —O—C.sub.4H.sub.8—O—, —CH.sub.2—C(CH.sub.3)—C(O)—)

INDUSTRIAL APPLICABILITY

(56) The compound of the present invention can be suitably used in various applications, for example, hydrophilizing agent, surface treating agent, polymerization initiator, polymerizable monomer, a crosslinking agent, denaturation treatment agent, thermosetting resin, thermosetting elastomer, liquid rubber, low temperature property rubber, modifier of filler or reactive compatibilizing agent.