IODINE-CONTAINING COMPOUND

Abstract

An iodine compound represented by formula (3) and a polymerization inhibitor including the iodine compound, wherein R.sup.21 to R.sup.25 are as defined herein, X.sup.1 is an n1-valent group, and n1 is an integer of 1 to 10:

##STR00001##

Claims

1. A compound represented by formula (3): ##STR00047## wherein X.sup.1 is an n1-valent group; R.sup.21 is H, F, Cl, CH.sub.3, CF.sub.3, or O(CF.sub.2).sub.p3F; R.sup.22 is R.sup.26OCO wherein R.sup.26 is bonded to X.sup.1; R.sup.23 is H or F; R.sup.24 is H, F, an aryl group, COOR.sup.30, or an alkyl group optionally substituted with fluorine; R.sup.25 is H, F, an aryl group, COOR.sup.30, or an alkyl group optionally substituted with fluorine; R.sup.26 is a single bond or an alkylene group optionally substituted with fluorine; R.sup.30 is H or an alkyl group; p3 is an integer of 1 to 10; and n1 is an integer of 1 to 10.

2. The compound according to claim 1, which is represented by formula (3), wherein X.sup.1 is an n1-valent siloxane group; and the siloxane group is represented by the following formula:
(SiR.sup.27.sub.2O).sub.qSiR.sup.27.sub.2,
SiR.sup.28.sub.rR.sup.29.sub.3-r, or
(R.sup.aSiO.sub.1.5).sub.t wherein R.sup.27, each independently at each occurrence, is a hydrogen atom or an alkyl group; R.sup.28, each independently at each occurrence, is O(SiR.sup.27.sub.2O).sub.sSiR.sup.27.sub.3; R.sup.29 is a single bond; R.sup.a, each independently at each occurrence, is R.sup.b or R.sup.c, provided that at least one R.sup.a is R.sup.b, R.sup.b is a single bond, and R.sup.c is a hydrogen atom or alkyl; q is an integer of 1 to 20; r is an integer of 1 to 3; s is an integer of 0 to 20; and t is any integer.

3. The compound according to claim 1, which is represented by formula (3), wherein X.sup.1 is a linear or branched n1-valent hydrocarbon group or an n1-valent aromatic group.

4. A polymerization initiator comprising the compound according to claim 1.

5. A polymerization initiator comprising the compound according to claim 2.

6. A polymerization initiator comprising the compound according to claim 3.

Description

EXAMPLES

Example 1

[0575] ##STR00030##

[0576] In a Pyrex tube, Compound 14 (279 mg) was dissolved in CH.sub.2Cl.sub.2 (0.4 ml), C.sub.6F.sub.13I (330 L) and an aqueous sodium thiosulfate solution (474 mg, 2 ml aqueous solution) were added thereto, and the mixture was irradiated with ultraviolet ray for 24 hours using a 400 W high-pressure mercury lamp while keeping the temperature of the reaction system constant. After completion of the reaction, the reaction mixture was purified by column chromatography to give Compound 15 (429 mg).

[0577] .sup.1H NMR (400 MHz, CDCl.sub.3); 4.6 (1H, dd, J=3.6, 10.4 Hz, ICH), 4.2 (2H, t, OCH.sub.2), 3.33 (1H, m, CF.sub.2CHH), 2.71 (1H, m, CF.sub.2CHCH), 1.88 (7H, m, CH(CH.sub.3).sub.2), 1.78 (2H, tt, SiCH.sub.2CH.sub.2), 0.97 (21H, d, CH(CH.sub.3).sub.2), 0.68 (2H, tt, CH.sub.2CH.sub.2CH.sub.2), 0.63 (14H, SiCH.sub.2CH) .sup.19F NMR (376 MHz, CDCl.sub.3); 81.3 (3F, s, CF.sub.3), 114.7 (2F, dd, J=276.0, 670.4 Hz, CH.sub.2CF.sub.2), 122.3 (2F, s, CF.sub.2), 123.4 (2F, s, CF.sub.2), 124.1 (2F, s, CF.sub.2), 126.6 (2F, s, CF.sub.2)

Example 2

[0578] ##STR00031##

a) solution polymerization, 25% toluene and 75% monomer
b) MeOH-insoluble fraction
c) GPC measurement in THF (linear polystyrene as calibration standard)

[0579] In a reaction vessel, Compound 15 (0.1 mmol) was dissolved in toluene (0.57 mL), methyl methacrylate (1.7 mL) and tetrabutylammonium iodide (36.6 mg) were added thereto, and the inside of the reaction vessel was sufficiently substituted with an inert gas, followed by heating at 120 C. for 1 hour. After completion of the reaction, the reaction mixture was purified by re-precipitation to give Compound 16 (811 mg, M.sub.n=1.610.sup.4, M.sub.w/M.sub.n=1.5).

[0580] .sup.1H NMR (400 MHz, CDCl.sub.3); 3.83 (s, C(O)OCH.sub.3), 2.0-1.7 (s, C(CH.sub.3)), 1.86 (7H, m, CH(CH.sub.3).sub.2), 1.1 (CH.sub.2C(CH.sub.3)(COOCH.sub.3)), 0.95 (21H, d, CH(CH.sub.3).sub.2), 0.8 (CH.sub.2C(CH.sub.3)(COOCH.sub.3)), 0.60 (14H, SiCH.sub.2CH)

[0581] .sup.19F NMR (376 MHz, CDCl.sub.3); 81.3 (3F, s, CF.sub.3), 114.7 (2F, dd, J=276.0, 670.4 Hz, CH.sub.2CF.sub.2), 122.3 (2F, s, CF.sub.2), 123.4 (2F, s, CF.sub.2), 124.1 (2F, s, CF.sub.2), 126.6 (2F, s, CF.sub.2)

Example 3

[0582] ##STR00032##

[0583] In a Pyrex tube, Compound 11 (397 mg) was dissolved in a mixed solvent of CH.sub.2Cl.sub.2 (4 ml) and Asahiklin AK-225 (4 mL), C.sub.6F.sub.13I (1.1 mL) and an aqueous sodium thiosulfate solution (475 mg, 2 ml aqueous solution) were added thereto, and the mixture was irradiated with ultraviolet ray for 24 hours using a 450 W high-pressure mercury lamp while keeping the temperature of the reaction system constant. After completion of the reaction, the reaction mixture was purified by re-precipitation to give Compound 12 (1.01 g).

[0584] .sup.1H NMR (400 MHz, CDCl.sub.3); 4.6 (8H, ICH), 4.1 (2H, OCH.sub.2), 2.7 (16H, CF.sub.2CH.sub.2), 1.8 (16H, SiCH.sub.2CH.sub.2), 0.97 (21H, 0.7 (14H, SiCH.sub.2)

[0585] .sup.19F NMR (376 MHz, CDCl.sub.3); 81.4 (24F, s, CF.sub.3), 114.7 (2F, CH.sub.2CF.sub.2), 122.4 (2F, s, CF.sub.2), 123.4 (2F, s, CF.sub.2), 124.2 (2F, s, CF.sub.2), 126.7 (2F, s, CF.sub.2)

Example 4

[0586] ##STR00033##

[0587] In a reaction vessel, Compound 12 (489 mg) was dissolved in toluene (0.57 mL), methyl methacrylate (1.7 mL) and tetrabutylammonium iodide (36.5 mg) were added thereto, and the inside of the reaction vessel was sufficiently substituted with an inert gas, followed by heating at 120 C. for 1 hour. After completion of the reaction, the reaction mixture was purified by re-precipitation to give Compound 13 (1.65 g, M.sub.n=3.510.sup.4, M.sub.w/M.sub.n=1.8).

[0588] .sup.1H NMR (400 MHz, CDCl.sub.3); 4.2 (m, (O)CCH(CH.sub.2C.sub.6F.sub.13)(CH.sub.2)), 3.8 (OCH.sub.2), 3.6 (C(O)OCH.sub.3), 2.6 (CF.sub.2CH.sub.2), 1.8 (CH.sub.2C(CH.sub.3)(C(O)OCH.sub.3), 1.6 (SiCH.sub.2CH.sub.2), 1.1 (C(CH.sub.3)), 0.9 (C(CH.sub.3))

[0589] .sup.19F NMR (376 MHz, CDCl.sub.3); 81.4 (24F, s, CF.sub.3), 114 (2F, br, CH.sub.2CF.sub.2), 122.4 (2F, s, CF.sub.2), 123.5 (2F, s, CF.sub.2), 124.4 (2F, s, CF.sub.2), 126.8 (2F, s, CF.sub.2)

Example 5

[0590] ##STR00034##

[0591] In a Pyrex tube, Compound 1 (20.3 mg) was dissolved in CH.sub.2Cl.sub.2 (4 ml), IC.sub.4F.sub.8I (36 L) and an aqueous sodium thiosulfate solution (158 mg, 1 ml aqueous solution) were added thereto, and the mixture was irradiated with ultraviolet ray for 24 hours using a 400 W high-pressure mercury lamp while keeping the temperature of the reaction system constant. The obtained reaction mixture was analyzed by 1H and .sup.19F NMR to confirm that the desired product was obtained.

[0592] .sup.1H NMR (400 MHz, CDCl.sub.3); 4.6 (1H, dd, 3.8, 10.6 Hz, ICH), 4.2 (2H, OCH.sub.2CH.sub.3), 3.2 (1H, m, CF.sub.2CHH), 2.7 (1H, m, CF.sub.2CHH), 1.2 (3H, CH.sub.2CH.sub.3)

[0593] .sup.19F NMR (376 MHz, CDCl.sub.3); 114.8 (2F, dd, J=265.8, 647.1 Hz, CH.sub.2CF.sub.2), 123.8 (2F, s, CH.sub.2CF.sub.2CF.sub.2), 113.2 (2F, s, CF.sub.2CF.sub.2I), 59.1 (2F, s, CF.sub.2I)

Example 6

[0594] ##STR00035##

[0595] In a Pyrex tube, Compound 1 (60.6 mg) was dissolved in CH.sub.2Cl.sub.2 (4 ml), IC.sub.4F.sub.8I (36 L) and an aqueous sodium thiosulfate solution (316 mg, 1 ml aqueous solution) were added thereto, and the mixture was irradiated with ultraviolet ray for 24 hours using a 400 W high-pressure mercury lamp while keeping the temperature of the reaction system constant. The obtained reaction mixture was analyzed by .sup.1H and .sup.19F NMR to confirm that the desired product was obtained.

[0596] .sup.1H NMR (400 MHz, CDCl.sub.3); 4.6 (2H, dd, 3.8, 10.6 Hz, ICH), 4.2 (4H, OCH.sub.2CH.sub.3), 3.2 (2H, m, CF.sub.2CHH), 2.7 (2H, m, CF.sub.2CHH), 1.2 (6H, CH.sub.2CH.sub.3)

[0597] .sup.19F NMR (376 MHz, CDCl.sub.3); 114.8 (4F, dd, J=277.5, 658.8 Hz, CH.sub.2CF.sub.2), 123.1 (4F, s, CF.sub.2)

Example 7

[0598] ##STR00036##

[0599] In a Pyrex tube, Compound 4 (39.9 mg) was dissolved in CH.sub.2Cl.sub.2 (4 ml), C.sub.6F.sub.13I (44 L) and an aqueous sodium thiosulfate solution (158 mg, 1 ml aqueous solution) were added thereto, and the mixture was irradiated with ultraviolet ray for 1 hour using a 400 W high-pressure mercury lamp while keeping the temperature of the reaction system constant. The obtained reaction mixture was analyzed by .sup.1H and .sup.19F NMR to confirm that the desired product was obtained.

[0600] .sup.1H NMR (400 MHz, CDCl.sub.3); 6.4 (1H, dd, CH.sub.2CHC(O)), 6.1 (1H, dd, CH.sub.2CHC(O)), 5.8 (1H, dd, CH.sub.2CHC(O)), 4.2 (4H, OCH.sub.2), 4.2 (1H, m, ICH), 3.3 (1H, m, CF.sub.2CHH), 2.7 (1H, m, CF.sub.2CHCH), 1.8 (4H, OCH.sub.2CH.sub.2)

[0601] .sup.19F NMR (376 MHz, CDCl.sub.3); 81.3 (3F, s, CF.sub.3), 114.7 (2F, dd, J=276.0, 670.4 Hz, CH.sub.2CF.sub.2), 122.3 (2F, s, CF.sub.2), 123.4 (2F, s, CF.sub.2), 124.1 (2F, s, CF.sub.2), 126.6 (2F, s, CF.sub.2)

Example 8

[0602] ##STR00037##

[0603] In a reaction vessel, Compound 15 (138 mg) was dissolved in toluene (0.79 mL), Compound 6 (2.36 mL) and tetrabutylammonium iodide (36.7 mg) were added thereto, and the inside of the reaction vessel was sufficiently substituted with an inert gas, followed by heating at 120 C. for 5 hours. After completion of the reaction, the reaction mixture was purified by re-precipitation to give Compound 7 (yield: 27%, M.sub.n=3.810.sup.3, M.sub.w/M.sub.n=3.5).

[0604] .sup.1H NMR (400 MHz, C.sub.6D.sub.6) 4.17 (262H, br s), 2.25 (314H, br s), 2.02 (133H, br s), 1.41-1.09 (562H, br m), 1.07 (86H, dt, J=9.2, 3.7 Hz), 0.77 (14H, d, J=6.9 Hz).

[0605] .sup.19F NMR (376 MHz, C.sub.6D.sub.6) 79.38 (3 nF, s), 118.80 (2 nF, dd, J=433.5, 283.2 Hz), 130.20 (2 nF, s), 132.08 (2 nF, s)

Example 9

[0606] ##STR00038##

[0607] In a reaction vessel, Compound 15 (138 mg), butyl acrylate (1.40 mL) and tetrabutylammonium iodide (one equivalent) were added thereto, and the inside of the reaction vessel was sufficiently substituted with an inert gas, followed by heating at 110 C. for 48 hours. After completion of the reaction, the reaction mixture was purified by re-precipitation to give Compound 8 (yield 34%, M, =7.010.sup.3, M.sub.w/M.sub.n=1.24).

[0608] .sup.1H NMR (400 MHz, CDCl.sub.3) 4.09-3.96 (53H, m), 2.36-2.28 (23H, br m), 1.92-1.78 (18H, m), 1.67-1.62 (82H, m), 1.49-1.47 (8H, m), 1.37 (55H, dd, J=14.2, 7.3 Hz), 0.96-0.92 (120H, m), 0.60 (14H, t, J=5.7 Hz).

[0609] .sup.19F NMR (376 MHz, CDCl.sub.3) 81.28 (3F, s), 113.95 (2F, s), 122.34 (2F, s), 123.38 (2F, s), 124.12 (1F, s), 126.64 (2F, s).

Example 10

[0610] ##STR00039##

[0611] In a reaction vessel, Compound 15 (138 mg), Compound 9 (1.25 mL) and tetrabutylammonium iodide (148 mg) were added thereto, and the inside of the reaction vessel was sufficiently substituted with an inert gas, followed by heating at 110 C. for 48 hours. After completion of the reaction, the reaction mixture was purified by re-precipitation to give Compound 10 (yield 7%, M.sub.n=2.3103).

[0612] .sup.1H NMR (400 MHz, CDCl.sub.3) 4.47 (12H, br s), 2.47 (6H, br s), 2.05 (3H, br s), 1.86 (6H, tt, J=9.8, 4.5 Hz), 1.78 (8H, br s), 1.56 (5H, br s), 0.95 (40H, t, J=6.4 Hz), 0.62-0.59 (14H, m).

[0613] .sup.19F NMR (376 MHz, CDCl.sub.3) 74.49 (3 nF, s), 81.28 (3F, s), 113.98 (1F, s), 115.30 (1F, s), 121.97-122.60 (2F, m), 123.14-123.78 (2F, m), 123.94-124.40 (1F, m), 126.67 (2F, s).

Example 11

[0614] ##STR00040##

[0615] In a reaction vessel, Compound 12 (488 mg), butyl acrylate (2.30 mL) and tetrabutylammonium iodide (147 mg) were added thereto, and the inside of the reaction vessel was sufficiently substituted with an inert gas, followed by heating at 120 C. for 1 hour. After completion of the reaction, the reaction mixture was purified by re-precipitation to give Compound 17 (yield: 10%, M.sub.n=3.110.sup.4, M.sub.w/M.sub.n=2.05).

[0616] .sup.19F NMR (376 MHz, CDCl.sub.3) 81.43 (3F, s), 109.98 (2F, s), 122.5 (2F, s), 123.5 (2F, s), 123.8-125.0 (2F, m), 126.9 (2F, s).

Example 12

[0617] ##STR00041##

[0618] In a Pyrex tube, Compound 18 (168 mg) was dissolved in CH.sub.2Cl.sub.2 (5.0 ml), Compound 2 (553 mg) and an aqueous sodium thiosulfate solution (317 mg, 1 ml aqueous solution) were added thereto, and the mixture was irradiated with ultraviolet ray for 24 hours using a 400 W high-pressure mercury lamp while keeping the temperature of the reaction system constant. The obtained reaction mixture was analyzed by 1H and .sup.19F NMR, and it was confirmed that Compound 19 was obtained in 52% yield.

[0619] .sup.1H NMR (400 MHz, CDCl.sub.3); 4.60 (1H, m, CH.sub.2CHICO.sub.2CH.sub.2)), 4.23 (2H, q, CO.sub.2CH.sub.2CH.sub.3), 3.30 (1H, m, CF.sub.2CH.sub.2CHI), 3.12 (1H, dd, SiCHICH.sub.2), 2.88 (1H, m, CF.sub.2CH.sub.2CHI), 2.80-2.45 (2H, m, SiCHICH.sub.2CF.sub.2), 1.86 (7H, tq, CH.sub.2CH(CH.sub.3).sub.2), 1.28 (3H, t, CO.sub.2CH.sub.2CH.sub.3), 0.95 (14H, d, CH.sub.2CH(CH.sub.3).sub.2), 0.64 (42H, m, SiCH.sub.2CH(CH.sub.3).sub.2)

[0620] .sup.19F NMR (376 MHz, CDCl.sub.3); 115.0 (2F, dd, CH.sub.2CF.sub.2), 115.6 (2F, dd, CF.sub.2CH.sub.2) 124.1 (4F, s, CF.sub.2CF.sub.2CF.sub.2CF.sub.2)

Example 13

[0621] ##STR00042##

[0622] In a reaction vessel, Compound 19 (150 mg) was dissolved in toluene (0.37 mL), methyl methacrylate (1.1 mL) and tetrabutylammonium iodide (36.7 mg) were added thereto, and the inside of the reaction vessel was sufficiently substituted with an inert gas, followed by heating at 120 C. for 1 hour. After completion of the reaction, the reaction mixture was purified by re-precipitation to give Compound 20 (yield: 36%, M.sub.n=1.210.sup.4, M.sub.w/M.sub.n=1.15).

[0623] .sup.1H NMR (400 MHz, CDCl.sub.3); 4.14 (2H, q, CO.sub.2CH.sub.2CH.sub.3), 3.60 (3nH, s, CO.sub.2CH.sub.3), 3.12 (1H, dd, SiCHICH.sub.2), 2.65-2.45 (2H, m, SiCHICH.sub.2CF.sub.2), 2.1-1.7 (br, CH.sub.2C(CH.sub.3)(CO.sub.2CH.sub.3)), 1.50-1.35 (br, CH.sub.2C(CH.sub.3)(CO.sub.2CH.sub.3)), 1.30-1.18 (br, CH.sub.2C(CH.sub.3)(CO.sub.2CH.sub.3)), 1.02 (s, CH.sub.2C(CH.sub.3)(CO.sub.2CH.sub.3)), 0.95 (14H, d, SiCH.sub.2CH(CH.sub.3).sub.2), 0.85 (s, CH.sub.2C(CH.sub.3)(CO.sub.2CH.sub.3)), 0.64 (42H, m, SiCH.sub.2CH(CH.sub.3).sub.2)

[0624] .sup.19F NMR (376 MHz, CDCl.sub.3); 114.28 (2F, CH.sub.2CF.sub.2), 115.6 (2F, CF.sub.2CH.sub.2), 124.2 (4F, s, CF.sub.2CF.sub.2CF.sub.2CF.sub.2)

Example 14

[0625] ##STR00043##

[0626] In a Pyrex tube, Compound 21 (210 mg) was dissolved in CH.sub.2Cl.sub.2 (7.5 ml), C.sub.6F.sub.13I (0.26 mL) and an aqueous sodium thiosulfate solution (237 mg, 1.5 ml aqueous solution) were added thereto, and the mixture was irradiated with ultraviolet ray for 4 hours using a 400 W high-pressure mercury lamp while keeping the temperature of the reaction system constant. The obtained reaction mixture was analyzed by .sup.1H and .sup.19F NMR, and it was confirmed that 308 mg of Compound 22 was obtained.

[0627] .sup.1H NMR (400 MHz, CDCl.sub.3); 4.61 (1H, dd, J=12.0, 4.0 Hz), 4.18-4.12 (2H, br m), 3.40-3.22 (1H, m), 2.74-2.63 (1H, m), 1.80-1.62 (2H, br m), 0.70-0.4 (2H, br m), 0.30-0.15 ((6n+9)H, br m)

[0628] .sup.19F NMR (376 MHz, CDCl.sub.3); 81.3 (3F, s), 114.7 (2F, dd, J=646.7, 278.2 Hz), 122.3 (2F, s), 123.4 (2F, s), 124.1 (2F, s), 126.6 (2F, s)

Example 15

[0629] ##STR00044##

[0630] In a Pyrex tube, ethyl acrylate (121 mg) was dissolved in CH.sub.2Cl.sub.2 (25 ml), Compound 24 (0.21 mL) and an aqueous sodium thiosulfate solution (791 mg, 5 ml aqueous solution) were added thereto, and the mixture was irradiated with ultraviolet ray for 4 hours using a 400 W high-pressure mercury lamp while keeping the temperature of the reaction system constant. The obtained reaction mixture was analyzed by .sup.1H and .sup.19F NMR, and it was confirmed that 271 mg of Compound 25 was obtained.

[0631] .sup.1H NMR (400 MHz, CDCl.sub.3); 4.57 (1H, dd, J=10.4, 3.6 Hz), 4.32-4.22

[0632] (2H, m), 3.30-3.18 (1H, m), 2.72-2.59 (1H, m), 1.35-1.25 (3H, t, J=7.2 Hz)

[0633] .sup.19F NMR (376 MHz, CDCl.sub.3); 45.1 (1F, s), 82.6 (2F, s), 88.1 (2F, s), 112.7 (2F, s), 118.43 (2F, dd, J=684.6, 259.6 Hz)

Example 16

[0634] ##STR00045##

[0635] In a reaction vessel, Compound 25 (53 mg), butyl acrylate (1.4 mL) and tetrabutylammonium iodide (148 mg) were added thereto, and the inside of the reaction vessel was sufficiently substituted with an inert gas, followed by heating at 110 C. for 15 hours. After completion of the reaction, the reaction mixture was purified by re-precipitation to give Compound 26 (monomer conversion ratio:33%, M.sub.n=6.110.sup.3, M.sub.w/M.sub.n=1.08).

[0636] .sup.1H-NMR (CDCl.sub.3) : 4.09 ((2n)H, br m), 2.28 ((2n)H, br s), 1.91-1.24 ((5n)H, br m), 1.04-0.92 ((3n)H, br m)

[0637] .sup.19F-NMR (CDCl.sub.3) : 45.08 (1F, s), 82.66 (2F, s), 88.19 (2F, s), 112.66 (2F, s), 117.82-118.71 (2F, m).

Example 17

[0638] ##STR00046##

[0639] In a reaction vessel, Compound 25 (53 mg) was dissolved in toluene (0.35 mL), methyl methacrylate (1.1 mL) and methyl tributylphosphonium iodide (34.4 mg) were added thereto, and the inside of the reaction vessel was sufficiently substituted with an inert gas, followed by heating at 70 C. for 4 hours. After completion of the reaction, the reaction mixture was purified by re-precipitation to give Compound 27 (monomer conversion ratio:64%, M.sub.n=1.210.sup.4, M.sub.w/M.sub.n=1.18).

[0640] .sup.1H-NMR (CDCl.sub.3) : 3.69 ((3n)H, br s), 2.17-1.81 ((2n)H, br m), 1.02, 0.87 ((3n) H, br s).

[0641] .sup.19F-NMR (CDCl.sub.3) : 44.90 (1F, s), 82.60 (2F, s), 88.16 (2F, s), 112.66 (2F, s), 118.13 (2F, d, J=69.6 Hz).

INDUSTRIAL APPLICABILITY

[0642] The compound of the present disclosure is suitably used as a polymerization initiator.