Fluorine-containing compound having unsaturated bond, and surface modifier using the same
11352457 · 2022-06-07
Assignee
Inventors
- Shinichiro Nakamura (Shunan, JP)
- Norihisa Kondo (Shunan, JP)
- Takayuki Yamasaki (Shunan, JP)
- Tomohiro Shirai (Shunan, JP)
Cpc classification
C07C69/653
CHEMISTRY; METALLURGY
C07F9/091
CHEMISTRY; METALLURGY
C07C21/215
CHEMISTRY; METALLURGY
C09K3/18
CHEMISTRY; METALLURGY
C08F220/14
CHEMISTRY; METALLURGY
C09D133/16
CHEMISTRY; METALLURGY
C07C33/423
CHEMISTRY; METALLURGY
B29C33/60
PERFORMING OPERATIONS; TRANSPORTING
C07C69/54
CHEMISTRY; METALLURGY
International classification
C08F220/14
CHEMISTRY; METALLURGY
B29C33/60
PERFORMING OPERATIONS; TRANSPORTING
C09K3/18
CHEMISTRY; METALLURGY
C07C21/215
CHEMISTRY; METALLURGY
C07C69/54
CHEMISTRY; METALLURGY
C07C69/653
CHEMISTRY; METALLURGY
C07F7/18
CHEMISTRY; METALLURGY
Abstract
To provide a novel fluorine-containing compound that does not include any long chain perfluoroalkyl unit having 8 or more carbon atoms, which is problematic in terms of the environment, and that is excellent in water repellency/oil repellency, and a surface modifier using the compound. [Solution] There are used a fluorine-containing compound represented by the following general formula (1), the following general formula (2) or the following general formula (5): Rf.sup.1—(CR.sup.1═CR.sup.2—X—Rf.sup.2).sub.n—Y—Z (1), Rf.sup.1—(X—CR.sup.1═CR.sup.2—Rf.sup.2).sub.n—Y—Z (2) or Rf.sup.3—(CF═CR.sup.3—CR.sup.4═CF—Rf.sup.4).sub.n—Y—Z (5); and a surface modifier using the compound.
Claims
1. A fluorine-containing compound represented by the following general formula (1) or the following general formula (2):
Rf.sup.1—(CR.sup.1═CR.sup.2—X—Rf.sup.2).sub.n—Y—Z (1)
Rf.sup.1—(X—CR.sup.1═CR.sup.2—Rf.sup.2).sub.n—Y—Z (2) wherein in the formula (1) or in the formula (2), Rf.sup.1 represents a perfluoroalkyl group having 1 to 6 carbon atoms, with a CF.sub.3 terminal, Rf.sup.2 represents a perfluoroalkylene group having 1 to 6 carbon atoms, in the formula (1) R.sup.1 and R.sup.2 represent a hydrogen atom and X is absent, in the formula (1) R.sup.1 represents a fluorine atom, R.sup.2 represents a hydrogen atom and X represents CH.sub.2, or in the formula (2) R.sup.1 represents a hydrogen atom, R.sup.2 represents a fluorine atom and X represents CH.sub.2, n represents an integer of 1 to 5, Y is represented by the following general formula (8):
(CH.sub.2).sub.l—Q—(CH.sub.2).sub.m (8) wherein in the formula (8), the sum of l and m is an integer of 2 to 6, when l and/or m represents 2 or more, a —CH═CH— structure is optionally included instead of —CH2CH2—; and Q is absent in the formula (8), or represents —OCONH—, —CONH—, —O—, —NH—, —CO—O—, —O—CO—, —NHCONH— or —C.sub.6H.sub.4—, and Z represents any structure of the following (i) to (iii): (i) a structure represented by the following general formula (3) or the following general formula (4):
—P(═O)(OM.sup.1)(OM.sup.2) (3)
—O—P(═O)(OM.sup.1)(OM.sup.2) (4) wherein in the formula (3) or in the formula (4), M.sup.1 and M.sup.2 each independently represent a hydrogen atom, an ammonium salt, an organic amine salt, or an alkyl group having 1 to 4 carbon atoms; (ii) a vinyl group, an allyl group, a styryl group, a methacryloyl group, or an acryloyl group; or (iii) SiL.sub.kL′.sub.(3-k) wherein L represents a hydrolyzable group or a hydroxyl group, L′ represents a hydrocarbon group having 1 to 6 carbon atoms, k represents an integer of 1 to 3, and, the L and L′ groups may be different from or the same as each other.
2. The fluorine-containing compound according to claim 1, wherein Rf.sup.2 represents a linear perfluoroalkylene group having 1 to 6 carbon atoms.
3. The fluorine-containing compound according to claim 1, wherein R.sup.1 and/or R.sup.2 represent(s) a hydrogen atom.
4. The fluorine-containing compound according to claim 1, wherein the hydrolyzable group L represents Cl or OR.sup.5 wherein R.sup.5 represents an alkyl group having 1 to 4 carbon atoms.
5. A surface modifier comprising the fluorine-containing compound according to claim 1.
6. A fluorine-containing compound represented by the following general formula (5):
Rf.sup.3—(CF═CR.sup.3—CR.sup.4═CF—Rf.sup.4).sub.n—Y—Z (5) wherein in the formula (5), Rf.sup.3 represents a perfluoroalkyl group having 1 to 5 carbon atoms, with a CF.sub.3 terminal, Rf.sup.4 represents a perfluoroalkylene group having 1 to 5 carbon atoms, R.sup.3 and R.sup.4 each independently represent a hydrogen atom or a fluorine atom, n represents an integer of 1 to 5, Y is represented by the following general formula (8):
(CH.sub.2).sub.l—Q—(CH.sub.2).sub.m (8) wherein in the formula (8), the sum of l and m is an integer of 2 to 6, when l and/or m represents 2 or more, a —CH═CH— structure is optionally included instead of —CH.sub.2CH.sub.2—; and Q is absent in the formula (8), or represents —OCONH—, —CONH—, —O—, —NH—, —CO—O—O—CO—, —NHCONH— or —C.sub.6H.sub.4—, and Z represents any structure of the following (i) to (iii): (i) a structure represented by the following general formula (6) or the following general formula (7):
—P(═O)(OM.sup.3)(OM.sup.4) (6)
—O—P(═O)(OM.sup.3)(OM.sup.4) (7) wherein in the formula (6) or in the formula (7), M.sup.3 and M.sup.4 each independently represent a hydrogen atom, an ammonium salt, an organic amine salt, or an alkyl group having 1 to 4 carbon atoms; (ii) a vinyl group, an allyl group, a styryl group, a methacryloyl group, or an acryloyl group; or (iii) SiL.sub.kL′.sub.(3-k) wherein L represents a hydrolyzable group or a hydroxyl group, L′ represents a hydrocarbon group having 1 to 6 carbon atoms, k represents an integer of 1 to 3, and, the L and L′ groups may be different from or the same as each other.
7. The fluorine-containing compound according to claim 6, wherein Rf.sup.4 represents a linear perfluoroalkylene group having 1 to 5 carbon atoms.
8. The fluorine-containing compound according to claim 6, wherein R.sup.3 and/or R.sup.4 represent(s) a hydrogen atom.
9. The fluorine-containing compound according to claim 6, wherein the hydrolyzable group L represents Cl or OR.sup.5 wherein R.sup.5 represents an alkyl group having 1 to 4 carbon atoms.
10. A surface modifier comprising the fluorine-containing polymer according to claim 6.
11. A fluorine-containing polymer represented by the following general formula (1) or the following general formula (2):
Rf.sup.1—(CR.sup.1═CR.sup.2—X—Rf.sup.2).sub.n—Y—Z (1)
Rf.sup.1—(X—CR.sup.1═CR.sup.2—Rf.sup.2).sub.n—Y—Z (2) wherein Z in general formula (1) or (2) comprises a repeating unit that is a vinyl group, an allyl group, a styryl group, a methacryloyl group, or an acryloyl group and that is derived from a monomer A, wherein the monomer A is the fluorine-containing compound according to claim 1, wherein in the formula (1) or in the formula (2), Rf.sup.1 represents a perfluoroalkyl group having 1 to 6 carbon atoms, with a CF.sub.3 terminal, Rf.sup.2 represents a perfluoroalkylene group having 1 to 6 carbon atoms, R.sup.1 and R.sup.2 each independently represent a hydrogen atom or a fluorine atom, n represents an integer of 1 to 5, X is absent in the formula (1) or in the formula (2), or represents CH.sub.2, O or S, Y is represented by the following general formula (8):
(CH.sub.2).sub.l—Q—(CH.sub.2).sub.m (8) wherein in the formula (8), the sum of l and m is an integer of 2 to 6, when l and/or m represents 2 or more, a —CH═CH— structure is optionally included instead of —CH.sub.2CH.sub.2—; and Q is absent in the formula (8), or represents —OCONH—, —CONH—, —O—, —NH—, —CO—O—, —O—CO—, —NHCONH— or —C.sub.6H.sub.4—.
12. The fluorine-containing polymer according to claim 11, obtained by copolymerization of the monomer A with a monomer B having at least one polymerizable group in a molecule, wherein the monomer B is the following compounds (X.sub.1) to (X.sub.9): (X.sub.1) acrylic acid and methacrylic acid, and esters thereof: methyl, ethyl, butyl, isobutyl, t-butyl, propyl, 2-ethylhexyl, hexyl, decyl, lauryl, stearyl, isobornyl, behenyl, .beta.-hydroxyethyl, glycidyl, phenyl, benzyl and 4-cyanophenyl esters; (X2) fatty acid vinyl esters: acetic acid, propionic acid, caprylic acid, lauric acid, stearic acid, behenic acid and the like; (X.sub.3) styrene-based compounds: styrene, .alpha.-methylstyrene, and p-methylstyrene; (X4) halogenated vinyl or vinylidene compounds: vinyl fluoride, vinyl chloride, vinyl bromide, vinylidene fluoride, and vinylidene chloride; (X.sub.5) aliphatic allyl esters: allyl heptanoate, allyl caprate, and allyl caproate; (X.sub.6) vinyl alkyl ketones: vinyl methyl ketone, and vinyl ethyl ketone; (X.sub.7) acrvlamides: N-methylacrvlamide, N-methylolacrylamide, and N-methylolmethacrylamide; (X.sub.8) dienes: 2,3-dichloro-1,3-butadiene, and isoprene; and (X.sub.9) ethylene, acrylonitrile, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, methoxy polypropylene glycol (meth)acrylate, vinyl alkyl ether, and isoprene.
13. The fluorine-containing polymer according to claim 12, wherein the monomer B is a (meth)acrylic acid or an ester thereof, fatty acid_vinyl ester, aliphatic allyl ester, vinyl alkyl ketone, acrylamide, diene, ethylene, acrylonitrile, or a halogen monomer.
14. The fluorine-containing polymer according to claim 11, having a weight average molecular weight of 1,000 to 200,000.
15. A surface modifier comprising the fluorine-containing polymer according to claim 11.
16. A fluorine-containing polymer represented by the following general formula (1) or the following general formula (2):
Rf.sup.1—(CR.sup.1═CR.sup.2—X—Rf.sup.2).sub.n—Y—Z (1)
Rf.sup.1—(X—CR.sup.1═CR.sup.2—Rf.sup.2).sub.n—Y—Z (2) wherein Z in general formula (1) or (2) comprises a repeating unit that is a vinyl group, an allyl group, a styryl group, a methacryloyl group, or an acryloyl group and that is derived from a monomer A, wherein the monomer A is the fluorine-containing compound according to claim 8, wherein in the formula (1) or in the formula (2), Rf.sup.1 represents a perfluoroalkyl group having 1 to 6 carbon atoms, with a CF.sub.3 terminal, Rf.sup.2 represents a perfluoroalkylene group having 1 to 6 carbon atoms, R.sup.1 and R.sup.2 each independently represent a hydrogen atom or a fluorine atom, n represents an integer of 1 to 5, X is absent in the formula (1) or in the formula (2), or represents CH.sub.2, O or S, Y is represented by the following general formula (8):
(CH.sub.2).sub.l—Q—(CH.sub.2).sub.m (8) wherein in the formula (8), the sum of l and m is an integer of 2 to 6, when l and/or m represents 2 or more, a —CH═CH— structure is optionally included instead of —CH.sub.2CH.sub.2—; and Q is absent in the formula (8), or represents —OCONH—, —CONH—, —O—, —NH—, —CO—O—, —O—CO—, —NHCONH— or —C.sub.6H.sub.4—.
Description
EXAMPLES
(1) Hereinafter, Examples of the present invention are shown, but the present invention is not intended to be limited by these Examples.
(2) Here, the following instruments were used in analysis.
(3) .sup.1H-NMR, .sup.19F-NMR: AVANCE II 400 manufactured by Bruker Corporation
(4) GC-MS: GCMS-QP2010Plus (Shimadzu Corporation)
(5) Contact angle measurement: VHX-500F (manufactured by Keyence Corporation)
(6) Gel permeation chromatography (GPC):
(7) Apparatus: 8320GPC manufactured by Tosoh Corporation
(8) Column: TSKgel SuperHM-H, SuperHM-M manufactured by Tosoh Corporation
(9) Column temperature: 40° C.
(10) Solvent: tetrahydrofuran
(11) Detector: RI
(12) Spin coater: ACT-300A manufactured by Active Co., Ltd.
Example 1
Synthesis of 3,3,4,4,5,5,6,6,9,9,10,10,11,12,12,13,13,14,14,14-henicosafluorotetradeca-1,7-diene (3)
1-1) 3,3,4,4,5,5,6,6-octafluoro-8-iodo-1-octene (1)
(13) ##STR00001##
(14) A 100-ml eggplant flask was charged with 150 g (294 mol) of 3,3,4,4,5,5,6,6-octafluoro-1,8-diiodooctane (α.sub.1) (reagent of SynQuest Laboratories) and 150 g of THF, and dissolved. After cooling to 5° C. or less, a liquid in which 44.8 g (294 mmol) of diazabicycloundecene was dissolved in 25 g of THF was placed over 1 hour with stirring.
(15) Thereafter, the reaction was conducted at room temperature for 3 hours, thereafter 60 g of water and 120 g of diisopropyl ether were added thereto, and the resultant was separated into two phases. The organic phase was washed with water and saturated saline, and thereafter dried with magnesium sulfate, and the solvent was removed under reduced pressure.
(16) The resulting light yellow slurry was heated and dissolved in hexane and thereafter crystallized by cooling, a crystal precipitated was removed, and the solvent of a filtrate was removed under reduced pressure and thereafter distillated under reduced pressure, to provide 52.9 g of light pink oily compound (1).
(17) The purity and the yield with gas chromatography (GC) were 98.7% and 46.5%, respectively.
(18) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 5.86 (m, 2H, CH.sub.2═CH—), 5.67 (m, 1H, CH.sub.2═CH—), 3.14 (m, 2H, CH.sub.2I), 2.61 (m, 2H, CF.sub.2CH.sub.2CH.sub.2I)
(19) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm) −114.44 (s, 2F, CH.sub.2═CH—CF.sub.2), −115.54 (s, 2F, CF.sub.2CH.sub.2CH.sub.2I), −123.77 (s, 2F, CF.sub.2), −124.06 (s, 4F, CF.sub.2)
1-2)1,1,1,2,2,3,3,4,4,5,5,6,6,9,9,10,10,11,11,12,12-henicosafluoro-8,14-diiodotetradecene (2)
(20) ##STR00002##
(21) A 150-ml SUS autoclave was charged with 61.3 g (137.4 mmol) of 1-iodoperfluorohexane (α.sub.2) (reagent of Tokyo Chemical Industry Co., Ltd.), 50.0 g (130.9 mmol) of 3,3,4,4,5,5,6,6-octafluoro-8-iodo-1-octene (1) and 0.19 g (1.3 mmol) of di-tert-butyl peroxide, the autoclave was sufficiently purged with nitrogen, and thereafter the temperature was raised to conduct the reaction at 120° C. for 2 hours with stirring.
(22) The resulting reaction liquid was subjected to distillation under reduced pressure, to provide 26.7 g of compound (2) being a colorless and transparent liquid as a fraction at 85 to 90° C. (2 kPa).
(23) The purity and the yield with gas chromatography (GC) were 90.5% and 24.7%, respectively.
(24) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 4.56 (m, 1H, CF.sub.2CHI), 3.17 (t, 2H, CH.sub.2I), 3.04 (m, 2H, CH.sub.2CHI), 2.69 (m, 2H, CF.sub.2CH.sub.2CH.sub.2I)
(25) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.34 (s, 3F, CF.sub.3), −109.99 (dd, 2F, CF.sub.2CHI), −115.09 (dd, 2F, CF.sub.2CH.sub.2CHI), −115.43 (s, 2F, CF.sub.2CH.sub.2CH.sub.2I), −117.89 (m, 2F, CH.sub.2CF.sub.2CF.sub.2), −122.27 (s, 2F CF.sub.2), −123.2-124.2 (m, 4F, CF.sub.2), −126.67 (s, 2F, CF.sub.3—CF.sub.2)
(26) GC-MS (m/e): 828 (M+)
1-3)3,3,4,4,5,5,6,6,9,9,10,10,11,12,12,13,13,14,14,14-henicosafluorotetradeca-1,7-diene (3)
(27) ##STR00003##
(28) In a 200-ml three-necked flask, 43.5 g (52.5 mmol) of compound (2) was dissolved in 100 g of dichloromethane and thereafter cooled under a nitrogen atmosphere, and 17.6 g (115.5 mmol) of diazabicycloundecene was dropped thereto at 5 to 10° C. over 1 hour.
(29) The reaction was conducted at room temperature with stirring overnight, and thereafter 100 g of a 1% by weight hydrochloric acid solution was added to separate an aqueous phase. An organic phase was washed with water, 1% by weight potassium hydrogen carbonate, and saturated saline, thereafter the solvent was removed, and the resultant was treated with silica and then subjected to distillation under reduced pressure, to obtain 19.0 g of compound (3) being a colorless and transparent liquid as a fraction at 90 to 94° C. (2 kPa). The yield was 90.1%.
(30) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 6.43 (m, 2H, —CH═CH—), 5.96 (m, 2H, —CH═CH.sub.2), 5.82 (m, 1H, —CH═CH.sub.2)
(31) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.34 (s, 3F, CF.sub.3), −112.34 (m, 2F, CF.sub.2CH═), −114.48 (m, 2F, CF.sub.2CH═), −114.58 (m, 2F, CF.sub.2CH═), −122.07 (s, 2F, CF.sub.2), −123.32 (s, 2F, CF.sub.2), −123.4-123.9 (m, 6F, CF.sub.2), −126.64 (s, 2F, CF.sub.3—CF.sub.2)
(32) MS (m/e): 553 (M−F)
Example 2
Synthesis of 4,4,5,5,6,6,7,7,8,8,9,9,12,12,13,13,14,14,15,15,15-henicosafluoro-10-pentadecen-1-ol (7)
2-1) Synthesis of 1,1,2,2,3,3,4,4,5,5,6,6,9,9,10,10,11,11,12,12,12-henicosafluoro-1,8-diiodododecane (4)
(33) ##STR00004##
(34) A 150-ml SUS autoclave was charged with 88.42 g (0.36 mol) of 3,3,4,4,5,5,6,6,6-nonafluoro-1-octene (α.sub.3) (reagent of Tokyo Chemical Industry Co., Ltd.), 199.00 g (0.36 mol) of 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoro-1,6-diiodohexane (α.sub.4) (produced by Tosoh F-Tech, Inc.) and 0.53 g (0.004 mol) of di-tert-butyl peroxide, and the autoclave was purged with nitrogen.
(35) After sealing, the temperature was raised to conduct the reaction at 120° C. for 3 hours and at 150° C. for 2 hours. After cooling, the resulting reaction liquid was subjected to distillation under reduced pressure, to obtain 85.13 g of compound (4) as a fraction at 111° C. and 0.4 kPa. The yield was 29.2%.
(36) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 4.63 (m, 1H, CF.sub.2CHI), 3.16 (m, 1H, CF.sub.2CH.sub.2)
(37) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −59.38 (m, 2F, CF.sub.2I), −81.31 (t, 3F, CF.sub.3), −105.81 (dd, 2F, CF.sub.2CHI), −113.49 (m, 2F, CF.sub.2CF.sub.2I), −114.95 (m, 2F, CH.sub.2CF.sub.2), −119.27 (m, 2F, CH.sub.2CF.sub.2), −121.46 (m, 2F, CF.sub.2), −122.00 (m, 2F, CF.sub.2), −124.13 (s, 2F, CF.sub.2), −126.31 (m, 2F, CF.sub.2)
2-2) Synthesis of 1,1,2,2,3,3,4,4,5,5,6,6,9,9,10,10,11,11,12,12,12-henicosafluorol-iodo-7-dodecene (5)
(38) ##STR00005##
(39) A 100-ml two-necked flask was charged with 41.45 g of a 10% potassium hydroxide-methanol solution, and 80.00 g (116.63 mmol) of compound (4) was dropped at room temperature over 40 minutes. After the reaction at room temperature for 1.5 hours, the reaction liquid was washed with 35 g of water, and the organic layer was diluted with dichloromethane. Furthermore, the organic layer was washed with 35 g of 1% hydrochloric acid, 40 g of water and 40 g of saturated saline, and thereafter the water content was removed from the organic phase by anhydrous sodium sulfate to obtain 63.94 g of compound (5). The yield was 53.9%.
(40) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 6.48 (m, 2H, C.sub.4F.sub.9CH═CHC.sub.6F.sub.12)
(41) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −59.38 (m, 2F, CF.sub.2I), −81.60 (t, 3F, CF.sub.3), −113.47 (m, 2F, CF.sub.2CF.sub.2I), −114.42 (m, 2F, CF.sub.2CH), −114.67 (m, 2F, CHCF.sub.2), −121.49 (m, 2F, CF.sub.2), −121.86 (m, 2F, CF.sub.2), −123.77 (m, 2F, CF.sub.2), −124.78 (m, 2F, CF.sub.2), −126.31 (m, 2F, CF.sub.2)
2-3) Synthesis of 4,4,5,5,6,6,7,7,8,8,9,9,12,12,13,13,14,14,15,15,15-henicosafluoro-10-pentadecen-1-ol (6)
(42) ##STR00006##
(43) A 100-ml eggplant flask was charged with 10.00 g (14.45 mmol) of compound (5) and 7.7 g of an aqueous 25% by weight sodium disulfite solution, and the flask was sufficiently purged with nitrogen. The inner temperature was raised to 70° C., and a solution in which 0.05 g (0.30 mmol) of azobisisobutyronitrile was dissolved in 1.01 g (17.34 mmol) of allyl alcohol (α.sub.5) was slowly dropped under vigorous stirring over 1 hour with the inner temperature being kept at 75 to 85° C. After the dropping, the reaction was performed at 75° C. for 16 hours, and thereafter the resultant was treated at 100° C. for 10 minutes.
(44) After cooling, the resultant was subjected to extraction with 15 g of dichloromethane and separated into two phases, and thereafter the organic phase was washed with 15 g of water and 20 g of saturated saline, and thereafter dried with magnesium sulfate. The organic phase was condensed under reduced pressure to obtain 9.96 g of compound (6). The yield was 89.4%.
(45) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 6.47 (m, 2H, C.sub.4F.sub.9CH═CHC.sub.6F.sub.12), 4.40 (m, 1H, CHI), 3.77 (m, 2H, CH.sub.2O), 2.88 (m, 2H, CH.sub.2CF.sub.2), 1.99 (s, 1H, OH)
(46) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.58 (t, 3F, CF.sub.3), −113.93 (m, 2F, CF.sub.2CH.sub.2), −114.42 (m, 2F, CF.sub.2CH), −122.00 (m, 4F, CF.sub.2CF.sub.2), −123.98 (m, 4F, CF.sub.2CF.sub.2), −124.82 (m, 2F, CF.sub.2), −126.33 (m, 2F, CF.sub.2)
2-4) Synthesis of 4,4,5,5,6,6,7,7,8,8,9,9,12,12,13,13,14,14,15,15,15-henicosafluoro-10-pentadecen-1-ol (7)
(47) ##STR00007##
(48) A 50-ml two-necked flask was charged with 0.34 g (1.95 mmol) of azobisisobutyronitrile, 9.50 g (13.01 mmol) of compound (6) and 5.98 g (19.52 mmol) of tributyltin hydride, and the reaction was conducted at 70° C. for 3 hours. The reaction liquid was diluted with 40 g of diisopropyl ether, washed with 50 g of water, 50 g of an aqueous 1 M potassium fluoride solution and 50 g of saturated saline, and thereafter dried with anhydrous magnesium sulfate. The organic layer was condensed under reduced pressure and thereafter recrystallized in hexane to obtain 4.45 g of compound (7). The yield was 54.0%.
(49) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 6.47 (m, 2H, C.sub.4F.sub.9CH═CHC.sub.6F.sub.12), 3.70 (m, 2H, CH.sub.2O), 2.22 (m, 2H, CH.sub.2CF.sub.2), 1.85 (m, 2H, CH.sub.2), 1.49 (s, 1H, OH)
(50) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.59 (t, 3F, CF.sub.3), −114.53 (m, 4F, CF.sub.2CH), −114.85 (m, 2F, CF.sub.2CH.sub.2), −122.17 (m, 4F, CF.sub.2CF.sub.2), −123.97 (m, 4F, CF.sub.2CF.sub.2), −124.78 (m, 2F, CF.sub.2), −126.33 (m, 2F, CF.sub.2)
Example 3
Synthesis of 4,4,5,5,6,6,7,7,8,8,9,9,12,12,13,13,14,14,15,15,16,16,17,17,17-pentacosafluoro-10-heptadecen-1-ol (11)
3-1) Synthesis of 1,1,2,2,3,3,4,4,5,5,6,6,9,9,10,10,11,11,12,12,13,13,14,14,14-pentacosafluoro-1,8-diiodotetradecane (8)
(51) ##STR00008##
(52) A 150-ml SUS autoclave was charged with 31.24 g (0.090 mol) of 3,3,4,4,5,5,6,6,7,7,8,8,8-nonafluoro-1-decene (α.sub.6) (reagent of Tokyo Chemical Industry Co., Ltd.), and 50.00 g (0.090 mol) of 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoro-1,6-diiodohexane (α.sub.4) (produced by Tosoh F-Tech, Inc.) and 0.13 g (0.001 mol) of di-tert-butyl peroxide, and the autoclave was purged with nitrogen.
(53) After sealing, the temperature was raised to conduct the reaction at 120° C. for 3 hours and at 150° C. for 2 hours. After cooling, the resulting reaction liquid was condensed under reduced pressure to provide 65.21 g of a crude product of compound (8). The purity with gas chromatography (GC) was 48.5%.
3-2) Synthesis of 1,1,2,2,3,3,4,4,5,5,6,6,9,9,10,10,11,11,12,12,13,13,14,14,14-pentacosafluoro-1-iodo-7-tetradecene (9)
(54) ##STR00009##
(55) A 100-ml two-necked flask was charged with 65.21 g of a mixture including (8) obtained in the reaction, and 55.71 g of a 10% potassium hydroxide-methanol solution was dropped under room temperature over 15 minutes. After the reaction at room temperature for 1 hour, the reaction liquid was washed with 50 g of water, 50 g of an aqueous 10% ammonium chloride solution and 50 g of saturated saline. The organic layer was diluted with dichloromethane. Furthermore, the organic layer was washed with g of 1% hydrochloric acid, 40 g of water and 40 g of saturated saline. The resulting organic layer was subjected to distillation under reduced pressure, to obtain 21.69 g of compound (9) as a fraction at 108° C. and 0.8 kPa. The yield was 31.1%.
(56) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 6.46 (m, 2H, C.sub.4F.sub.9CH═CHC.sub.6F.sub.12)
(57) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −59.43 (m, 2F, CF.sub.2I), −81.44 (t, 3F, CF.sub.3), −113.49 (m, 2F, CF.sub.2CF.sub.2I), −114.42 (m, 4F, CF.sub.2CH), −121.46 (m, 2F, CF.sub.2), −121.84 (m, 2F, CF.sub.2), −122.09 (m, 2F, CF.sub.2), −123.35 (m, 2F, CF.sub.2), −123.84 (m, 4F, CF.sub.2CF.sub.2), −126.73 (m, 2F, CF.sub.2CF.sub.3)
3-3) Synthesis of 4,4,5,5,6,6,7,7,8,8,9,9,12,12,13,13,14,14,15,15,16,16,17,17,17-pentacosafluoro-2-iodo-10-heptadecen-1-ol (10)
(58) ##STR00010##
(59) A 100-ml eggplant flask was charged with 10.00 g (12.95 mmol) of compound (9) and 6.9 g of an aqueous 25% by weight sodium disulfite solution, and the flask was sufficiently purged with nitrogen. The inner temperature was raised to 70° C., and a solution in which 0.04 g (0.27 mmol) of azobisisobutyronitrile was dissolved in 0.90 g (15.54 mmol) of allyl alcohol (α.sub.5) was slowly dropped under vigorous stirring over 1 hour with the inner temperature being kept at 75 to 85° C. After the dropping, the reaction was performed with stirring at 75° C. for 16 hours, and thereafter the resultant was treated at 100° C. for 10 minutes.
(60) After cooling, the resultant was subjected to extraction with 50 g of dichloromethane and separated into two phases, and thereafter the organic phase was washed with 20 g of water and 20 g of saturated saline, and thereafter dried with magnesium sulfate. The organic phase was condensed under reduced pressure to obtain 9.68 g of compound (10). The yield was 90.0%.
(61) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 6.49 (m, 2H, C.sub.4F.sub.9CH═CHC.sub.6F.sub.12), 4.43 (m, 1H, CHI), 3.79 (m, 2H, CH.sub.2O), 2.92 (m, 2H, CH.sub.2CF.sub.2), 1.99 (s, 1H, OH)
(62) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.32 (t, 3F, CF.sub.3), −113.96 (m, 2F, CF.sub.2CH.sub.2), −114.38 (m, 4F, CF.sub.2CH), −122.17 (m, 6F, CF.sub.2CF.sub.2CF.sub.2), −123.38 (m, 2F, CF.sub.2), −123.89 (m, 4F, CF.sub.2CF.sub.2), −124.09 (m, 2F, CF.sub.2), −126.67 (m, 2F, CF.sub.2)
3-4) Synthesis of 4,4,5,5,6,6,7,7,8,8,9,9,12,12,13,13,14,14,15,15,16,16,17,17,17-pentacosafluoro-10-heptadecen-1-ol (11)
(63) ##STR00011##
(64) A 50-ml two-necked flask was charged with 0.15 g (0.90 mmol) of azobisisobutyronitrile, 5.00 g (6.02 mmol) of compound (10), 2.63 g (9.03 mmol) of tributyltin hydride and 10 g of toluene, and the reaction was conducted at 70° C. for 3 hours. The reaction liquid was diluted with 40 g of diisopropyl ether, washed with 40 g of water, 40 g of an aqueous 1 M potassium fluoride solution and 40 g of saturated saline, and thereafter dried with anhydrous magnesium sulfate. The organic layer was condensed under reduced pressure and thereafter recrystallized in hexane to obtain 3.48 g of compound (11). The yield was 75.2%.
(65) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 6.48 (m, 2H, C.sub.4F.sub.9CH═CHC.sub.6F.sub.12), 3.71 (m, 2H, CH.sub.2O), 2.20 (m, 2H, CH.sub.2CF.sub.2), 1.86 (m, 2H, CH.sub.2), 1.70 (s, 1H, OH)
(66) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.36 (t, 3F, CF.sub.3), −114.39 (m, 4F, CF.sub.2CH), −114.86 (m, 2F, CF.sub.2CH.sub.2), −122.13 (m, 6F, CF.sub.2CF.sub.2CF.sub.2), −123.39 (m, 2F, CF.sub.2), −123.96 (m, 6F, CF.sub.2CF.sub.2CF.sub.2), −126.69 (m, 2F, CF.sub.2)
Example 4
Synthesis of 4,4,5,5,6,6,7,7,10,11,11,12,12,13,13,14,14,15,15,15-eicosafluoro-9-pentadecen-1-ol (16)
4-1) Synthesis of 1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,11,11,12,12,12-henicosafluoro-1,6-diiodododecane (12)
(67) ##STR00012##
(68) A 150-ml SUS autoclave was charged with 76 g (0.22 mol) of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octene (α.sub.6) (reagent of Tokyo Chemical Industry Co., Ltd.), and 200 g (0.44 mol) of 1,1,2,2,3,3,4,4-octafluoro-1,4-diiodobutane (α.sub.7) (produced by Tosoh F-Tech, Inc.) and 0.65 g (0.004 mol) of di-tert-butyl peroxide, and the autoclave was purged with nitrogen.
(69) After sealing, the temperature was raised to conduct the reaction at 120° C. for 3 hours and at 150° C. for 2 hours. After cooling, the resulting reaction liquid was subjected to distillation under reduced pressure, to obtain 94.58 g of compound (12) as a fraction at 130 to 135° C. and 0.4 kPa. The yield was 53.9%.
(70) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 4.55 (m, 1H, CF.sub.2CHI), 2.97 (m, 1H, CF.sub.2CH.sub.2)
(71) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −59.33 (s, 2F, CF.sub.2I), −81.30 (s, 3F, CF.sub.3), −105.54 (dd, 2F, CF.sub.2CHI), −112.98 (m, 2F, CF.sub.2CF.sub.2CHI), −114.99 (m, 2F, CH.sub.2CF.sub.2), −117.92 (m, 2F, CH.sub.2CF.sub.2CF.sub.2), −122.16 (s, 2F, CF.sub.2), −123.23-123.25 (m, 4F, CF.sub.2x2), −126.61 (s, 2F, CF.sub.3—CF.sub.2)
(72) MS (m/e): 800 (M+)
4-2) Synthesis of 4,4,5,5,6,6,7,7,10,10,11,11,12,12,13,13,14,14,15,15,15-henicosafluoro-2,9-diiodo-1-pentadecanol (13)
(73) ##STR00013##
(74) A 100-ml eggplant flask was charged with 27.75 g (34.7 mmol) of compound (12) and 18.5 g of an aqueous 25% by weight sodium disulfite solution, and the flask was sufficiently purged with nitrogen.
(75) The inner temperature was raised to 70° C., and a solution in which 0.12 g (0.73 mmol) of azobisisobutyronitrile was dissolved in 4.03 g (69.4 mmol) of allyl alcohol (α.sub.5) was slowly dropped under vigorous stirring over 2 hours with the inner temperature being kept at 75 to 85° C. After the dropping, the reaction was performed with stirring at 75° C. for 16 hours, and thereafter the resultant was treated at 100° C. for 10 minutes.
(76) After cooling, the resultant was subjected to extraction with 23 g of dichloromethane and separated into two phases, and thereafter the organic phase was washed with 38 g of water and 40 g of saturated saline, and thereafter dried with magnesium sulfate. The organic phase was condensed under reduced pressure to obtain a brown crude product of compound (13).
(77) The purity and the yield with gas chromatography (GC) were 31.9% and 24.7%, respectively.
(78) The crude product included 19.3% of raw material (12), 17.2% of reduced product (14) with one iodine and 10.6% of 2-adduct (15). Each calculation was made depending on the area percentage by GC.
4-3) Synthesis of 4,4,5,5,6,6,7,7,10,11,11,12,12,13,13,14,14,15,15,15-eicosafluoro-9-pentadecen-1-ol (16)
(79) ##STR00014##
(80) To a 100-ml four-necked flask whose content was purged with nitrogen were added 1.27 g (33.51 mmol) of lithium aluminum hydride and 43.68 g of tetrahydrofuran, and cooled to −10° C. or less, and a solution in which 5.66 g of a mixture including (13) obtained in the reaction was dissolved in 21.6 g of tetrahydrofuran was dropped at −10° C. over 1 hour.
(81) After the above reaction, the reaction was conducted with stirring at room temperature overnight. The reaction liquid was slowly added to 300 g of an aqueous saturated ammonium chloride solution with careful attention to foaming. Thereafter, filtration was made, a crystal was rinsed with 300 ml of ethyl acetate, and the resulting filtrate was separated into two phases. The organic phase was washed with 220 g of 2.5% saline and 150 g of saturated saline, thereafter the water content was removed from the organic phase by anhydrous sodium sulfate, and thereafter the solvent was distilled off under reduced pressure.
(82) The resulting orange oily product was purified and separated by a silica column chromatographic method (filler: silica gel 60N produced by Kanto Kagaku, eluent: dichloromethane) to obtain 0.32 g of compound (20). The yield from compound (12) was 1.5%.
(83) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 5.66 (dt, 1H, CF═CH—), 3.66 (t, 2H, CH.sub.2OH), 3.01 (td, 2H, CF.sub.2CH.sub.2CH═), 2.10 (tt, 2H, CF.sub.2CH.sub.2CH.sub.2), 1.78 (m, 2H, CH.sub.2CH.sub.2CH.sub.2), 1.66 (s, 1H, —OH)
(84) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.33 (t, 3F, CF.sub.3), −113.06 (s, 2F, CF.sub.2—CF═), −114.95 (m, 2F, CF.sub.2), −118.49 (m, 2F, CH.sub.2CF.sub.2CF.sub.2), −123.43 (s, 2F, CF.sub.2), −123.7-124.2 (m, 6F, CF.sub.2x3), −125.42 (s, 1F, —CF═CH), −126.62 (s, 2F, CF.sub.3—CF.sub.2)
(85) GC-MS (m/e): 800 (M+)
Example 5
Synthesis of 3,3,4,4,5,5,6,6,7,7,8,11,11,12,12,13,13,14,14,15,15,16,16,16-tetracosafluoro-8-hexadecen-1-ol (18)
5-1) Synthesis of 3,3,4,4,5,5,6,6,7,7,8,11,11,12,12,13,13,14,14,15,15,16,16,16-tetracosafluorohexadecyl-1,8-diene (17)
(86) ##STR00015##
(87) A 500-ml three-necked flask was charged with 6.09 g (225.90 mol) of an aluminum powder (reagent of Wako Pure Chemical Industries, Ltd.), 5.37 g (22.59 mmol) of nickel chloride hexahydrate (reagent of Wako Pure Chemical Industries, Ltd.), 177 g of acetonitrile and 40.00 g (113.0 mmol) of 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluorooctadecyl-1,9-diene (α.sub.8) (produced by Tosoh F-Tech, Inc.), and 50.37 g (446.0 mol) of 1-iodo-1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexane (α.sub.2) was dropped under room temperature over 15 minutes. After the reaction at room temperature for 12 hours, 100 g of 2.5% hydrochloric acid was added to the reaction liquid, and the resultant was subjected to extraction with 100 g of diisopropyl ether three times. The resulting organic layer was washed with 200 g of an aqueous 5% sodium hydrogen carbonate solution and 200 g of saturated saline, and thereafter dried with anhydrous magnesium sulfate. The organic layer was condensed under reduced pressure and thereafter distillated under reduced pressure to obtain 19.21 g of compound (17) as a fraction at 168 to 170° C. and 0.4 kPa. The yield was 25.8%.
(88) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 5.92 (m, 2H, CH═CH.sub.2) 5.73 (m, 1H, CH═CH.sub.2) 5.67 (m, 1H, CH.sub.2CHCF) 3.03 (m, 2H, CH.sub.2CHCF)
(89) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.43 (t, 3F, CF.sub.3), −112.96 (m, 2F, CF.sub.2CH), −114.38 (m, 2F, CF.sub.2CH.sub.2), −118.47 (m, 2F, CF.sub.2), −121.99 (m, 4F, CF.sub.2CF.sub.2), −123.50 (m, 6F, CF.sub.2CF.sub.2CF.sub.2), −124.20 (m, 2F, CF.sub.2), −124.59 (m, 1F, CF), −126.66 (m, 2F, CF.sub.2)
5-2) Synthesis of 3,3,4,4,5,5,6,6,7,7,8,11,11,12,12,13,13,14,14,15,15,16,16,16-tetracosafluoro-8-hexadecen-1-ol (18)
(90) ##STR00016##
(91) A 100-ml three-necked flask was charged with 0.28 g (0.31 mmol) of tris(triphenylphosphine)rhodium (I) chloride (reagent of Tokyo Chemical Industry Co., Ltd.), 20 g of tetrahydrofuran and 2.30 g (16.8 mmol) of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (α.sub.9) (reagent of Tokyo Chemical Industry Co., Ltd.), and the resulting mixture was stirred under room temperature for 5 minutes. 10.00 g (15.3 mmol) of compound (17) was added thereto, and the reaction was conducted at room temperature for 24 hours, and thereafter 30 g of an aqueous 3 M sodium hydroxide solution was added to the reaction liquid, and g of an aqueous 30% hydrogen peroxide solution was dropped over 5 minutes. After 150 g of an aqueous saturated ammonium chloride solution was added, the resultant was subjected to extraction with 150 g of diisopropyl ether twice. The resulting organic layer was washed with 150 g of saturated saline, and thereafter dried with anhydrous magnesium sulfate. The organic layer was condensed under reduced pressure and thereafter the resulting brown oily product was purified and separated by silica gel column chromatography (filler: silica gel C-300 produced by Wako Pure Chemical Industries Co., Ltd., eluent: ethyl acetate/hexane=1:2) to obtain 3.00 g of compound (18).
(92) The yield was 29.2%.
(93) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 5.68 (m, 1H, CH═CH.sub.2), 3.94 (t, 2H, CF.sub.2CH.sub.2CH.sub.2OH), 3.04 (m, 2H, CH.sub.2CHCF), 2.35 (m, 2H, CF.sub.2CH.sub.2CH.sub.2OH) 2.01 (s, 1H, OH)
(94) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.41 (t, 3F, CF.sub.3), −112.91 (m, 2F, CF.sub.2CH), −113.97 (m, 2F, CF.sub.2CH.sub.2), −118.45 (m, 2F, CF.sub.2), −122.30 (m, 4F, CF.sub.2CF.sub.2), −123.47 (m, 6F, CF.sub.2CF.sub.2CF.sub.2), −124.34 (m, 2F, CF.sub.2), −124.34 (m, 1F, CF), −126.66 (m, 2F, CF.sub.2)
Example 6
Synthesis of 3,3,4,4,5,5,6,6,7,7,8,11,12,12,13,13,14,14,15,15,16,16,16-tricosafluoro-1,8,10-hexadecatriene (19)
(95) ##STR00017##
(96) A 10-ml vial was charged with 5.00 g of compound (17), and 4.67 g of a 10% potassium hydroxide-methanol solution was dropped under room temperature over 5 minutes. After the reaction at room temperature for 1 hour, the reaction liquid was washed with 5 g of an aqueous 10% ammonium chloride solution, 5 g of water and 5 g of saturated saline. The resulting organic layer was condensed under reduced pressure to obtain 4.46 g of compound (19). The yield was 93.9%.
(97) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 6.46 (m, 2H, CFCH—CHCF), 5.93 (m, 2H, CH═CH.sub.2), 5.75 (m, 1H, CH═CH.sub.2)
(98) 19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.38 (m, 3F, CF.sub.3), −114.34 (m, 2F, CF.sub.2CH), −118.46 (m, 4F, CF.sub.2CF), −119.67 (m, 1F, CF), −120.56 (m, 1F, CF), −121.92 (m, 2F, CF.sub.2), −123.30 (m, 6F, CF.sub.2CF.sub.2CF.sub.2), −124.17 (m, 2F, CF.sub.2), −126.66 (m, 2F, CF.sub.2)
Example 7
Synthesis of 3,3,4,4,5,5,6,6,7,7,8,11,12,12,13,13,14,14,15,15,16,16,16-tricosafluoro-8,10-hexadecadien-1-ol (20)
(99) ##STR00018##
(100) A 200-ml three-necked flask which was purged with nitrogen was charged with 1.72 g (22.6 mmol) of a borane dimethyl sulfide complex and 47.9 g of tetrahydrofuran, and cooled to −15° C.
(101) Under a nitrogen atmosphere, 3.72 g (45.3 mmol) of cyclohexene (α.sub.10) was dropped at −15° C. or less over 30 minutes with stirring by a magnetic stirrer. After the dropping, the resultant was stirred at 0° C. for 2 hours and thereafter a solution in which 10 g (15.29 mmol) of compound (17) was dissolved in 30 g of tetrahydrofuran was dropped at 5° C. or less over 60 minutes.
(102) Thereafter, the reaction was conducted with stirring at 5° C. for 3 hours and at room temperature for 63 hours. After cooling to 0° C. again, 15.29 g (76.4 mmol) of an aqueous 20% by weight sodium hydroxide solution was dropped over 10 minutes, 17.33 g (152.9 mmol) of a 30% by weight hydrogen peroxide solution was subsequently dropped over 30 minutes, and thereafter the reaction was performed with stirring at room temperature for 2 hours.
(103) After 27.56 g of 10% by weight hydrochloric acid was dropped to the reaction liquid over 30 minutes, 30 g of diisopropyl ether was added to perform extraction, and thereafter the organic phase was washed with 30 g of water once and 30 g of saturated saline twice. The organic phase was dehydrated by anhydrous magnesium sulfate and thereafter the solvent was distilled off under reduced pressure to provide 9.89 g of a light yellow oily product.
(104) The resulting crude product was subjected to removal of cyclohexanol by Kugelrohr distillation and thereafter purified by silica gel column chromatography (eluent: ethyl acetate) to obtain 1.30 g of compound (20).
(105) The resulting compound (20) was analyzed, and the following results were obtained.
(106) The purity with gas chromatography (GC) was 89.3%. The yield was 11.8%.
(107) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 6.63 (dt, 2H, —CF═CHCH═CF—), 3.74 (t, 2H, CH.sub.2O), 3.28 (b, 1H, —OH), 2.28 (tt, CF.sub.2CH.sub.2)
(108) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.69 (t, 3F, CF.sub.3), −114.03 (m, 2F, CF.sub.2CH.sub.2), −118.47 (m, 4F, CF.sub.2), −121.09 (m, 1F, CF═CH), −21.88 (m, 1F, CF═CH), −122.31 (m, 2F CF.sub.2), −123.42 (m, 2F, CF.sub.2), −123.55 (m, 2F CF.sub.2), −124.42 (m, 4F CF.sub.2x2), −126.82 (m, 2F, CF.sub.2)
(109) GC-MS (m/e): 652 (M+)
Example 8
Synthesis of 1-trichlorosilyl-3,3,4,4,5,5,6,6,9,9,10,10,11,11,12,12,13,13,14,14,14-henicosafluoro-7-tetradecene (21)
(110) ##STR00019##
(111) A glass pressure-resistant tube (manufactured by Ace Glass Inc.: 40 ml) was charged with 1.00 g (1.7 mmol) of compound (3), 0.004 g (0.01 mmol) of chloroplatinic acid hexahydrate (reagent of Wako Pure Chemical Industries, Ltd.) and 0.45 g (3.3 mmol) of trichlorosilane (reagent of Tokyo Chemical Industry Co., Ltd.), and the reaction was performed under stirring at 50° C. for 3 days.
(112) After the reaction, excessive trichlorosilane was removed by nitrogen bubbling, and thereafter Kugelrohr distillation was performed to obtain 0.72 g of colorless liquid compound (21). The yield was 42.7%.
(113) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 6.45 (m, 2H, —CH═CH—), 2.29 (m, 2H, CF.sub.2CH.sub.2), 1.65 (m, 2H, CH.sub.2—Si)
(114) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.34 (s, 3F, CF.sub.3), −114.3-−114.6 (m, 4F, CF.sub.2CH═), −116.13 (t, 2F, CF.sub.2CH.sub.2), −122.08 (s, 2F, CF.sub.2), −123.30 (b, 4F, CF.sub.2), −123.6-123.9 (m, 4F, CF.sub.2), −126.64 (s, 2F, CF.sub.3—CF.sub.2)
Example 9
Synthesis of 1-[3-(triethoxysilyl)-propyl]carbamoyloxy-4,4,5,5,6,6,7,7,8,8,9,9,12,12,13,13,14,14,15,15,15-henicosafluoro-10-pentadecene (22)
(115) ##STR00020##
(116) In 4 g of dichloromethane were dissolved 4.00 g (6.62 mmol) of compound (7) and 1.72 g (6.95 mmol) of 3-(triethoxysilyl)propyl isocyanate, and 0.04 g (0.07 mmol) of dibutyltin dilaurate was added thereto. The reaction was conducted with stirring at room temperature for 2 hours, and purification was performed by a silica column chromatographic method (filler: silica gel C-300 produced by Wako Pure Chemical Industries Co., Ltd., eluent: dichloromethane) to provide 5.41 g of the product of interest (22). The yield was 95.4%.
(117) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 6.47 (m, 2H, C.sub.4F.sub.9CH═CHC.sub.6F.sub.12), 5.03 (t, 1H, NH), 4.12 (t, 2H, CH.sub.2O), 3.81 (q, 6H, CH.sub.2CH.sub.3), 3.20 (q, 2H, NHCH.sub.2), 2.22 (m, 2H, CH.sub.2CF.sub.2), 2.15 (m, 2H, CH.sub.2CF.sub.2), 1.91 (m, 2H, NHCH.sub.2CH.sub.2CH.sub.2), 1.65 (m, 2H, CF.sub.2CH.sub.2CH.sub.2CH.sub.2), 1.23 (t, 9H, CH.sub.2CH.sub.3), 0.65 (t, 2H, CH.sub.2Si)
(118) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.58 (t, 3F, CF.sub.3), −114.51 (m, 4F, CF.sub.2CH), −114.92 (m, 2F, CF.sub.2CH.sub.2), −122.15 (m, 4F, CF.sub.2CF.sub.2), −123.95 (m, 4F, CF.sub.2CF.sub.2), −124.78 (m, 2F, CF.sub.2), −126.32 (m, 2F, CF.sub.2)
Example 10
Synthesis of 1-[3-(triethoxysilyl)-propyl]carbamoyloxy-4,4,5,5,6,6,7,7,8,8,9,9,12,12,13,13,14,14,15,15,16,16,17,17,17-pentacosafluoro-10-heptadecene (23)
(119) ##STR00021##
(120) In 4 g of dichloromethane were dissolved 2.26 g (3.21 mmol) of compound (11) and 0.83 g (3.37 mmol) of 3-(triethoxysilyl)propyl isocyanate, and 0.02 g (0.03 mmol) of dibutyltin dilaurate was added thereto. The reaction was conducted with stirring at room temperature for 2 hours, and purification was performed by a silica column chromatographic method (filler: silica gel C-300 produced by Wako Pure Chemical Industries Co., Ltd., eluent: dichloromethane) to provide 2.78 g of the product of interest (23). The yield was 91.3%.
(121) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 6.48 (m, 2H, C.sub.6F.sub.13CH═CHC.sub.6F.sub.12), 5.03 (t, 1H, NH), 4.12 (t, 2H, CH.sub.2O), 3.82 (q, 6H, CH.sub.2CH.sub.3), 3.20 (q, 2H, NHCH.sub.2), 2.22 (m, 2H, CH.sub.2CF.sub.2), 2.15 (m, 2H, CH.sub.2CF.sub.2), 1.91 (m, 2H, NHCH.sub.2CH.sub.2CH.sub.2), 1.65 (m, 2H, CF.sub.2CH.sub.2CH.sub.2CH.sub.2), 1.23 (t, 9H, CH.sub.2CH.sub.3), 0.65 (t, 2H, CH.sub.2Si)
(122) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.35 (t, 3F, CF.sub.3), −114.38 (m, 4F, CF.sub.2CH), −114.94 (m, 2F, CF.sub.2CH.sub.2), −122.09 (m, 6F, CF.sub.2CF.sub.2CF.sub.2), −123.37 (m, 2F, CF.sub.2), −123.95 (m, 6F, CF.sub.2CF.sub.2CF.sub.2), −126.67 (m, 2F, CF.sub.2)
Example 11
Synthesis of 1-[3-(triethoxysilyl)-propyl]carbamoyloxy-4,4,5,5,6,6,7,7,10,11,11,12,12,13,13,14,14,15,15,15-eicosafluoro-9-pentadecene (24)
(123) ##STR00022##
(124) In 1 g of dichloromethane were dissolved 0.2513 g (0.41 mmol) of compound (16) and 0.1077 g (0.44 mmol) of 3-(triethoxysilyl)propyl isocyanate, and 0.0026 g (0.004 mmol) of dibutyltin dilaurate was added thereto.
(125) The reaction was conducted with stirring at room temperature for 2 hours, and purification was performed by a silica column chromatographic method (filler: silica gel 60N produced by Kanto Kagaku, eluent: hexane) to provide 0.33 g of the product of interest (24). The yield was 93.3%.
(126) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 5.67 (dt, 1H, CF═CH—), 4.97 (b, 1H, —CONH—), 4.05 (m, 2H, CH.sub.2O), 3.75 (q, 6H, CH.sub.3CH.sub.2O), 3.11 (m, 2H, N—CH.sub.2), 3.01 (td, 2H, CF.sub.2CH.sub.2CH═) 2.10 (m, 2H, CF.sub.2CH.sub.2CH.sub.2), 1.83 (m, 2H, CH.sub.2CH.sub.2CH.sub.2O), 1.56 (m, 2H, NCH.sub.2CH.sub.2CH.sub.2), 1.15 (9H, CH.sub.3), 0.56 (m, 2H, CH.sub.2—Si)
(127) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.34 (t, 3F, CF.sub.3), −113.07 (s, 2F, CF.sub.2—CF═), −115.11 (m, 2F, CF.sub.2), −118.51 (m, 2F, CH.sub.2CF.sub.2CF.sub.2), −123.48 (s, 2F, CF.sub.2), −123.7-124.2 (m, 6F, CF.sub.2), −125.39 (s, 1F, —CF═CH), −126.73 (s, 2F, CF.sub.3—CF.sub.2)
Example 12
Synthesis of 1-trichlorosilyl-3,3,4,4,5,5,6,6,7,7,8,11,11,12,12,13,13,14,14,15,15,16,16,16-tetracosafluoro-8-hexadecene (25)
(128) ##STR00023##
(129) A glass pressure-resistant tube (manufactured by Ace Glass Inc.: 40 ml) was charged with 1.00 g (1.53 mmol) of compound (17), 0.008 g (0.02 mmol) of chloroplatinic acid hexahydrate (reagent of Wako Pure Chemical Industries, Ltd.) and 0.31 g (2.29 mmol) of trichlorosilane (reagent of Tokyo Chemical Industry Co., Ltd.), and the reaction was performed under stirring at 50° C. for 15 hours.
(130) After the reaction, excessive trichlorosilane was removed by nitrogen bubbling, and thereafter Kugelrohr distillation was performed to obtain 0.54 g of yellow liquid compound (25). The yield was 44.7%.
(131) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 5.71 (m, 1H, CH.sub.2CHCF), 3.10 (m, 2H, CH.sub.2CHCF), 2.31 (m, 2H, CH.sub.2CH.sub.2Si), 1.65 (m, 2H, CH.sub.2CH.sub.2Si)
(132) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.28 (t, 3F, CF.sub.3), −112.84 (m, 2F, CF.sub.2CH.sub.2CF), −116.10 (m, 2F, CF.sub.2CH.sub.2CH.sub.2), −118.48 (m, 2F, CF.sub.2), −122.43 (m, 4F, CF.sub.2CF.sub.2), −123.79 (m, 8F, CF.sub.2CF.sub.2CF.sub.2CF.sub.2), −124.50 (m, 1F, CF), −126.65 (m, 2F, CF.sub.2)
Example 13
Synthesis of 1-triethoxysilyl-3,3,4,4,5,5,6,6,7,7,8,11,11,12,12,13,13,14,14,15,15,16,16,16-tetracosafluoro-8-hexadecene (26)
(133) ##STR00024##
(134) A glass pressure-resistant tube (manufactured by Ace Glass Inc.: 40 ml) was charged with 2.00 g (3.06 mmol) of compound (17), 0.012 g (0.03 mmol) of a Karstedt catalyst (reagent of Tokyo Chemical Industry Co., Ltd.) and 0.60 g (3.67 mmol) of triethoxysilane (reagent of Tokyo Chemical Industry Co., Ltd.), and the reaction was performed under stirring at 80° C. for 15 hours.
(135) The resulting orange oily product was purified and separated by silica gel column chromatography (filler: silica gel C-300 produced by Wako Pure Chemical Industries Co., Ltd., eluent: dichloromethane/hexane=1:3) to obtain 1.19 g of compound (26). The yield was 47.5%.
(136) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 5.71 (m, 1H, CH.sub.2CHCF) 3.84 (q, 6H, CH.sub.2CH.sub.3) 3.10 (m, 2H, CH.sub.2CHCF) 3.06 (m, 2H, CH═CH.sub.2) 2.17 (m, 2H, CH.sub.2CH.sub.2Si) 1.23 (t, 9H, CH.sub.2CH.sub.3) 0.86 (m, 2H, CH.sub.2CH.sub.2Si)
(137) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.36 (t, 3F, CF.sub.3), −112.92 (m, 2F, CF.sub.2CH.sub.2CF), −116.91 (m, 2F, CF.sub.2CH.sub.2CH.sub.2), −118.45 (m, 2F, CF.sub.2), −122.34 (m, 4F, CF.sub.2CF.sub.2), −123.89 (m, 8F, CF.sub.2CF.sub.2CF.sub.2CF.sub.2), −124.49 (m, 1F, CF), −126.62 (m, 2F, CF.sub.2)
Example 14
Synthesis of 1-trichlorosilyl-3,3,4,4,5,5,6,6,7,7,8,11,12,12,13,13,14,14,15,15,16,16,16-tricosafluoro-8,10-hexadecadiene (27)
(138) ##STR00025##
(139) A glass pressure-resistant tube (manufactured by Ace Glass Inc.: 40 ml) was charged with 1.00 g (1.63 mmol) of compound (19), 0.008 g (0.02 mmol) of chloroplatinic acid hexahydrate (reagent of Wako Pure Chemical Industries, Ltd.) and 0.33 g (2.44 mmol) of trichlorosilane (reagent of Tokyo Chemical Industry Co., Ltd.), and the reaction was performed under stirring at 50° C. for 15 hours.
(140) After the reaction, excessive trichlorosilane was removed by nitrogen bubbling, and thereafter Kugelrohr distillation was performed to obtain 0.31 g of yellow liquid compound (27). The yield was 25.0%.
(141) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 6.48 (m, 2H, CFCH—CHCF), 2.30 (m, 2H, CH.sub.2CH.sub.2Si), 1.66 (m, 2H, CH.sub.2CH.sub.2Si)
(142) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.27 (m, 3F, CF.sub.3), −114.39 (m, 2F, CF.sub.2CH), −116.91 (m, 2F, CF.sub.2CF), −118.45 (m, 2F, CF.sub.2CF.sub.2), −119.50 (m, 1F, CF), −120.43 (m, 1F, CF), −121.21 (m, 2F, CF.sub.2), −123.34 (m, 6F, CF.sub.2CF.sub.2CF.sub.2), −124.20 (m, 2F, CF.sub.2), −126.69 (m, 2F, CF.sub.2)
Example 15
Synthesis of 1-[3-(triethoxysilyl)-propyl]carbamoyloxy-3,3,4,4,5,5,6,6,7,7,8,11,12,12,13,13,14,14,15,15,16,16,16-tricosafluoro-8,10-hexadecadiene (28)
(143) ##STR00026##
(144) In a 5-ml eggplant flask purged with nitrogen, 1.00 g (1.53 mmol) of compound (20) and 0.38 g (1.53 mmol) of 3-(triethoxysilyl)propyl isocyanate were dissolved in 1.78 g of tetrahydrofuran, and 0.0097 g (0.02 mmol) of dibutyltin dilaurate was added thereto.
(145) The reaction was conducted under a nitrogen atmosphere with stirring at room temperature for 65 hours, purification was performed by a silica column chromatographic method (filler: silica gel 60N produced by Kanto Kagaku, eluent: hexane-ethyl acetate 95/5 (volume/volume)) to provide 0.75 g of the compound of interest (28). The yield was 55.3%.
(146) The resulting compound (28) was analyzed, and the following results were obtained.
(147) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 6.48 (dt, 2H, CF═CH—CH═CF), 5.06 (b, 1H, —CONH—), 4.36 (t, 2H, CH.sub.2O), 3.81 (q, 6H, CH.sub.3CH.sub.2O), 3.20 (m, 2H, N—CH.sub.2), 2.43 (m, 2H, CF.sub.2CH.sub.2), 1.63 (m, 2H, CH.sub.2CH.sub.2CH.sub.2O), 1.23 (t, 9H, CH.sub.3), 0.64 (m, 2H, CH.sub.2—Si)
(148) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.34 (t, 3F, CF.sub.3), −114.15 (m, 2F, CF.sub.2CH.sub.2), −118.49 (m, 4F, CF.sub.2CF═), −119.8 (m, 1F, CF═CH), −120.44 (m, 1F, CF═CH), −122.24 (m, 2F, CF.sub.2), −123.36 (m, 6F, CF.sub.2), −124.20 (m, 2F, CF.sub.2), −126.72 (m, 2F, CF.sub.3—CF.sub.2)
Example 16
Synthesis of 4,4,5,5,6,6,7,7,8,8,9,9,12,12,13,13,14,14,15,15,16,16,17,17,17-pentacosafluoro-10-heptadecenyl 2-methylpropenate (29)
(149) ##STR00027##
(150) A glass pressure-resistant tube (manufactured by Ace Glass Inc.: 40 ml) was charged with 1.00 g (1.42 mmol) of compound (11), 4.7 g of dichloromethane and 0.22 g (2.13 mmol) of triethylamine (reagent of Wako Pure Chemical Industries, Ltd.), and 0.28 g (2.13 mmol) of methacryloyl chloride (α.sub.12) (reagent of Tokyo Chemical Industry Co., Ltd.) was dropped under stirring at 0° C. over 5 minutes. After the reaction was performed under stirring at room temperature for 1 hour, the solvent was removed by nitrogen bubbling, and the reaction liquid was diluted with 20 g of diisopropyl ether and washed with 20 g of saturated saline three times. The organic layer was dried with anhydrous magnesium sulfate and condensed under reduced pressure, and thereafter the resulting yellow oily product was purified and separated by silica gel column chromatography (filler: silica gel C-300 produced by Wako Pure Chemical Industries Co., Ltd., eluent: ethyl acetate/hexane=1:9) to obtain 0.70 g of compound (29). The yield was 63.8%.
(151) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 6.47 (m, 2H, C.sub.6F.sub.13CH═CHC.sub.6F.sub.12), 6.11 (m, 1H, CH), 5.55 (m, 1H, CH), 4.20 (t, 2H, CH.sub.2O), 2.19 (m, 2H, CH.sub.2CF.sub.2), 1.99 (m, 2H, CH.sub.2CH.sub.2CH.sub.2), 1.93 (m, 3H, CH.sub.3)
(152) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.39 (t, 3F, CF.sub.3), −114.34 (m, 4F, CF.sub.2CH), −114.80 (m, 2F, CF.sub.2CH.sub.2), −122.04 (m, 6F, CF.sub.2CF.sub.2CF.sub.2), −123.31 (m, 2F, CF.sub.2), −123.87 (m, 6F, CF.sub.2CF.sub.2CF.sub.2), −126.64 (m, 2F, CF.sub.2)
Example 17
Synthesis of 4,4,5,5,6,6,7,7,8,8,9,9,12,12,13,13,14,14,15,15,16,16,17,17,17-pentacosafluoro-10-heptadecenyl propenate (30)
(153) ##STR00028##
(154) A glass pressure-resistant tube (manufactured by Ace Glass Inc.: 40 ml) was charged with 0.50 g (0.71 mmol) of compound (11), 2.4 g of dichloromethane and 0.11 g (1.07 mmol) of triethylamine (reagent of Wako Pure Chemical Industries, Ltd.), and 0.12 g (1.07 mmol) of acryloyl chloride (α.sub.13) (reagent of Tokyo Chemical Industry Co., Ltd.) was dropped under stirring at 0° C. over 5 minutes. After the reaction was performed under stirring at room temperature for 1 hour, the solvent was removed by nitrogen bubbling, and the reaction liquid was diluted with 20 g of diisopropyl ether and washed with 20 g of saturated saline three times. The organic layer was dried with anhydrous magnesium sulfate and condensed under reduced pressure, and thereafter the resulting yellow oily product was purified and separated by silica gel column chromatography (filler: silica gel C-300 produced by Wako Pure Chemical Industries Co., Ltd., eluent: ethyl acetate/hexane=1:9) to obtain 0.11 g of compound (30). The yield was 20.4%.
(155) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 6.49 (m, 2H, C.sub.6F.sub.13CH═CHC.sub.6F.sub.12), 6.45 (m, 1H, CH), 6.13 (m, 1H, CH), 5.85 (m, 1H, CH), 4.24 (t, 2H, CH.sub.2O), 2.19 (m, 2H, CH.sub.2CF.sub.2), 2.01 (m, 2H, CH.sub.2CH.sub.2CH.sub.2)
(156) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.31 (t, 3F, CF.sub.3), −114.36 (m, 4F, CF.sub.2CH), −114.91 (m, 2F, CF.sub.2CH.sub.2), −122.12 (m, 6F, CF.sub.2CF.sub.2CF.sub.2), −123.37 (m, 2F, CF.sub.2), −123.95 (m, 6F, CF.sub.2CF.sub.2CF.sub.2), −126.65 (m, 2F, CF.sub.2)
Example 18
Synthesis of 3,3,4,4,5,5,6,6,7,7,8,11,11,12,12,13,13,14,14,15,15,16,16,16-tetracosafluoro-8-hexadecenyl 2-methylpropenate (31)
(157) ##STR00029##
(158) A glass pressure-resistant tube (manufactured by Ace Glass Inc.: 40 ml) was charged with 0.50 g (0.74 mmol) of compound (18), 2.5 g of dichloromethane and 0.11 g (1.12 mmol) of triethylamine (reagent of Wako Pure Chemical Industries, Ltd.), and 0.15 g (1.12 mmol) of methacryloyl chloride (α.sub.12) (reagent of Tokyo Chemical Industry Co., Ltd.) was dropped under stirring at 0° C. over 5 minutes. After the reaction was performed under stirring at room temperature for 1 hour, the solvent was removed by nitrogen bubbling, and the reaction liquid was diluted with 20 g of diisopropyl ether and washed with 20 g of saturated saline three times. The organic layer was dried with anhydrous magnesium sulfate and condensed under reduced pressure, and thereafter the resulting yellow oily product was purified and separated by silica gel column chromatography (filler: silica gel C-300 produced by Wako Pure Chemical Industries Co., Ltd., eluent: ethyl acetate/hexane=1:9) to obtain 0.31 g of compound (31). The yield was 56.6%.
(159) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 6.14 (m, 1H, CH), 5.71 (m, 1H, CH═CH.sub.2), 5.60 (m, 1H, CH), 4.45 (t, 2H, CF.sub.2CH.sub.2CH.sub.2OH), 3.09 (m, 2H, CH.sub.2CHCF), 2.50 (m, 2H, CF.sub.2CH.sub.2CH.sub.2OH), 1.95 (m, 3H, CH.sub.3)
(160) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.37 (t, 3F, CF.sub.3), −112.91 (m, 2F, CF.sub.2CH), −114.13 (m, 2F, CF.sub.2CH.sub.2), −118.45 (m, 2F, CF.sub.2), −122.36 (m, 4F, CF.sub.2CF.sub.2), −123.47 (m, 6F, CF.sub.2CF.sub.2CF.sub.2), −124.18 (m, 2F, CF.sub.2), −124.57 (m, 1F, CF), −126.67 (m, 2F, CF.sub.2)
Example 19
Synthesis of 3,3,4,4,5,5,6,6,7,7,8,11,12,12,13,13,14,14,15,15,16,16,16-tricosafluoro-8,10-hexadecadienyl 2-methylpropenate (32)
(161) ##STR00030##
(162) A glass pressure-resistant tube (manufactured by Ace Glass Inc.: 40 ml) was charged with 0.44 g (0.67 mmol) of compound (20), 2.2 g of dichloromethane and 0.10 g (1.01 mmol) of triethylamine (reagent of Wako Pure Chemical Industries, Ltd.), and 0.13 g (1.01 mmol) of methacryloyl chloride (α.sub.12) (reagent of Tokyo Chemical Industry Co., Ltd.) was dropped under stirring at 0° C. over 5 minutes. After the reaction was performed under stirring at room temperature for 1 hour, the solvent was removed by nitrogen bubbling, and the reaction liquid was diluted with 20 g of diisopropyl ether and washed with 20 g of saturated saline three times. The organic layer was dried with anhydrous magnesium sulfate and condensed under reduced pressure, and thereafter the resulting yellow oily product was purified and separated by silica gel column chromatography (filler: silica gel C-300 produced by Wako Pure Chemical Industries Co., Ltd., eluent: ethyl acetate/hexane=1:9) to obtain 0.24 g of compound (32). The yield was 49.7%.
(163) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 6.48 (m, 2H, CFCH—CHCF), 6.14 (m, 1H, CH═CH.sub.2), 5.61 (m, 1H, CH), 4.45 (t, 2H, CF.sub.2CH.sub.2CH.sub.2OH), 2.51 (m, 2H, CF.sub.2CH.sub.2CH.sub.2OH), 1.95 (m, 3H, CH.sub.3)
(164) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.27 (m, 3F, CF.sub.3), −114.13 (m, 2F, CF.sub.2CH), −118.46 (m, 4F, CF.sub.2CF), −119.59 (m, 1F, CF), −120.32 (m, 1F, CF), −122.23 (m, 2F, CF.sub.2), −123.35 (m, 6F, CF.sub.2CF.sub.2CF.sub.2), −124.17 (m, 2F, CF.sub.2), −126.669 (m, 2F, CF.sub.2)
Example 20
Synthesis of 4,4,5,5,6,6,7,7,8,8,9,9,12,12,13,13,14,14,15,15,16,16,17,17,17-pentacosafluoro-10-heptadecenyl phosphate (33)
(165) ##STR00031##
(166) A 50-ml two-necked flask was charged with 1.96 g (12.78 mmol) of phosphorus oxychloride (reagent of Wako Pure Chemical Industries, Ltd.) and 2.00 g (2.84 mmol) of compound (11), and the reaction was performed under stirring at 80° C. for 3 hours. The reaction liquid was dropped to 20 g of water, and extracted with 30 g of chloroform. The aqueous layer was subjected to decantation, and the organic layer was washed with saturated saline and extracted with 50 g of acetone. The organic layer was condensed under reduced pressure, thereafter the resulting yellow oily product was dissolved in 20 g of acetone, and a precipitate was removed by suction filtration. The filtrate was condensed under reduced pressure to obtain 1.65 g of compound (33). The yield was 74.1%.
(167) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 6.51 (m, 2H, C.sub.6F.sub.13CH═CHC.sub.6F.sub.12), 4.44 (m, 2H, CH.sub.2OP), 2.32 (m, 2H, CH.sub.2CF.sub.2), 2.13 (m, 2H, CH.sub.2CH.sub.2CH.sub.2)
(168) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.73 (t, 3F, CF.sub.3), −114.00 (m, 4F, CF.sub.2CH), −114.86 (m, 2F, CF.sub.2CH.sub.2), −122.21 (m, 6F, CF.sub.2CF.sub.2CF.sub.2), −123.51 (m, 2F, CF.sub.2), −123.94 (m, 6F, CF.sub.2CF.sub.2CF.sub.2), −126.86 (m, 2F, CF.sub.2)
Example 21
Synthesis of diethyl 4,4,5,5,6,6,7,7,8,8,9,9,12,12,13,13,14,14,15,15,16,16,17,17,17-pentacosafluoro-10-heptadecenyl phosphate (34)
(169) ##STR00032##
(170) A glass pressure-resistant tube (manufactured by Ace Glass Inc.: 40 ml) was charged with 1.00 g (1.42 mmol) of compound (11), 4.7 g of dichloromethane and 0.43 g (4.26 mmol) of triethylamine (reagent of Wako Pure Chemical Industries, Ltd.), and 0.74 g (4.26 mmol) of diethyl chlorophosphate (reagent of Tokyo Chemical Industry Co., Ltd.) was dropped under stirring at 0° C. over 5 minutes. After the reaction was performed under stirring at room temperature for 1 hour, the solvent was removed by nitrogen bubbling, and the reaction liquid was diluted with 20 g of diisopropyl ether and washed with 20 g of saturated saline three times. The organic layer was dried with anhydrous magnesium sulfate and condensed under reduced pressure, and thereafter the resulting yellow oily product was purified and separated by silica gel column chromatography (filler: silica gel C-300 produced by Wako Pure Chemical Industries Co., Ltd., eluent: ethyl acetate/hexane=1:1) to obtain 1.02 g of compound (34). The yield was 85.5%.
(171) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 6.48 (m, 2H, C.sub.6F.sub.13CH═CHC.sub.6F.sub.12), 4.14 (m, 2H, CH.sub.2OP), 4.12 (m, 4H, CH.sub.2CH.sub.3), 2.23 (m, 2H, CH.sub.2CF.sub.2), 1.98 (m, 2H, CH.sub.2CH.sub.2CH.sub.2), 1.33 (m, 6H, CH.sub.2CH.sub.3)
(172) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.35 (t, 3F, CF.sub.3), −114.33 (m, 4F, CF.sub.2CH), −114.83 (m, 2F, CF.sub.2CH.sub.2), −122.04 (m, 6F, CF.sub.2CF.sub.2CF.sub.2), −123.32 (m, 2F, CF.sub.2), −123.85 (m, 6F, CF.sub.2CF.sub.2CF.sub.2), −126.68 (m, 2F, CF.sub.2)
Example 22
Synthesis of diethyl 3,3,4,4,5,5,6,6,7,7,8,11,11,12,12,13,13,14,14,15,15,16,16,16-tetracosafluoro-8-hexadecenyl phosphate (35)
(173) ##STR00033##
(174) A glass pressure-resistant tube (manufactured by Ace Glass Inc.: 40 ml) was charged with 0.50 g (0.74 mmol) of compound (18), 2.5 g of dichloromethane and 0.23 g (2.23 mmol) of triethylamine (reagent of Wako Pure Chemical Industries, Ltd.), and 0.39 g (2.23 mmol) of diethyl chlorophosphate (reagent of Tokyo Chemical Industry Co., Ltd.) was dropped under stirring at 0° C. over 5 minutes. After the reaction was performed under stirring at room temperature for 1 hour, the solvent was removed by nitrogen bubbling, and the reaction liquid was diluted with 20 g of diisopropyl ether and washed with 20 g of saturated saline three times. The organic layer was dried with anhydrous magnesium sulfate and condensed under reduced pressure, and thereafter the resulting yellow oily product was purified and separated by silica gel column chromatography (filler: silica gel C-300 produced by Wako Pure Chemical Industries Co., Ltd., eluent: ethyl acetate/hexane=1:1) to obtain 0.51 g of compound (35). The yield was 85.3%.
(175) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 5.71 (m, 1H, CH═CH.sub.2), 4.33 (q, 2H, CF.sub.2CH.sub.2CH.sub.2OH), 4.13 (m, 4H, CH.sub.2OP), 3.09 (m, 2H, CH.sub.2CHCF), 2.53 (m, 2H, CF.sub.2CH.sub.2CH.sub.2OH), 1.35 (m, 6H, CH.sub.2CH.sub.3)
(176) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.28 (t, 3F, CF.sub.3), −112.91 (m, 2F, CF.sub.2CH), −114.17 (m, 2F, CF.sub.2CH.sub.2), −118.47 (m, 2F, CF.sub.2), −122.41 (m, 4F, CF.sub.2CF.sub.2), −123.47 (m, 6F, CF.sub.2CF.sub.2CF.sub.2), −124.28 (m, 2F, CF.sub.2), −124.57 (m, 1F, CF), −126.66 (m, 2F, CF.sub.2)
Example 23
Synthesis of diethyl 3,3,4,4,5,5,6,6,7,7,8,11,12,12,13,13,14,14,15,15,16,16,16-tricosafluoro-8,10-hexadecadienyl phosphate (36)
(177) ##STR00034##
(178) A glass pressure-resistant tube (manufactured by Ace Glass Inc.: 40 ml) was charged with 0.25 g (0.39 mmol) of compound (20), 1.3 g of dichloromethane and 0.12 g (1.18 mmol) of triethylamine (reagent of Wako Pure Chemical Industries, Ltd.), and 0.39 g (2.23 mmol) of diethyl chlorophosphate (reagent of Tokyo Chemical Industry Co., Ltd.) was dropped under stirring at 0° C. over 5 minutes. After the reaction was performed under stirring at room temperature for 1 hour, the solvent was removed by nitrogen bubbling, and the reaction liquid was diluted with 20 g of diisopropyl ether and washed with 20 g of saturated saline three times. The organic layer was dried with anhydrous magnesium sulfate and condensed under reduced pressure, and thereafter the resulting yellow oily product was purified and separated by silica gel column chromatography (filler: silica gel C-300 produced by Wako Pure Chemical Industries Co., Ltd., eluent: ethyl acetate/hexane=1:1) to obtain 0.26 g of compound (36). The yield was 86.5%.
(179) .sup.1H-NMR (solvent: deuterochloroform, internal standard: tetramethylsilane) δ (ppm): 6.49 (m, 2H, CFCH—CHCF), 4.33 (t, 2H, CF.sub.2CH.sub.2CH.sub.2OH), 4.14 (m, 4H, CH.sub.2OP), 2.54 (m, 2H, CF.sub.2CH.sub.2CH.sub.2OH), 1.35 (m, 6H, CH.sub.2CH.sub.3)
(180) .sup.19F-NMR (solvent: deuterochloroform, internal standard: trifluoromethylbenzene) δ (ppm): −81.28 (m, 3F, CF.sub.3), −114.15 (m, 2F, CF.sub.2CH), −118.46 (m, 4F, CF.sub.2CF), −119.63 (m, 1F, CF), −120.29 (m, 1F, CF), −122.24 (m, 2F, CF.sub.2), −123.35 (m, 6F, CF.sub.2CF.sub.2CF.sub.2), −124.23 (m, 2F, CF.sub.2), −126.69 (m, 2F, CF.sub.2)
Comparative Example 1
Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl phosphate (37)
(181) ##STR00035##
(182) Synthesis was made based on the method described in Patent Document 4 (Japanese Patent Laid-Open No. 2015-71552). After 32.7 g (225.7 mmol) of phosphorus pentoxide, 118.7 g of 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane and 23.2 g of 85% by mass phosphoric acid (100.5 mmol of phosphorus pentoxide and 495.1 mmol of water) were added to a 500-ml three-necked flask at room temperature (25° C.), stirring was performed for 10 minutes and thereafter 118.7 g (326.2 mmol) of perfluorohexylethyl alcohol (α.sub.14) was added thereto. An oil bath was heated to 50° C. and the reaction was conducted under stirring at the same temperature for 24 hours. Next, the oil bath was heated to 60° C., the reaction was conducted under stirring at the same temperature for 24 hours, thereafter the solvent was removed, and 150 g of ethyl acetate was newly added for dissolution. The same amount of water was added thereto, the resultant was washed with water under stirring, and an operation for removal of water used was performed three times in total. Thereafter, the solvent was removed, and the resultant was dried to provide 145 g of white powdery compound (37). The yield was 93.5 mol %.
Example 24
(183) Glass Modification Conditions
(184) A glass slide (manufactured by Matsunami Glass Ind., Ltd., size: 76 mm×26 mm×1.2 mm)) was immersed in a saturated potassium hydroxide-isopropyl alcohol solution at room temperature for 17 hours, washed with water and dried at 60° C. for 2 hours before use, and the resultant was immediately used as a pre-treated glass.
(185) This pre-treated glass was treated with being stirred and immersed in a surface modifier solution, in which compound (21) synthesized in Example 8 was dissolved in a chloroform solvent so as to be in an amount of 0.3% by weight, at 50° C. for 2 hours. The glass was taken out from the modification solution, an excessive surface modifier attached to the glass surface was wiped off by Novec (registered trademark) 7100 (produced by 3M) and water, and thereafter the resultant was treated at 150° C. for 2 hours to provide a surface-modified glass substrate.
(186) Contact Angle Measurement
(187) Contact angle measurement was performed using the following instrument and method.
(188) Instrument: VHX-500F (manufactured by Keyence Corporation)
(189) Method: the contact angle was determined by dropping 1 μL of a droplet onto the surface of the surface-modified glass substrate, imaging the resultant as viewed edge-on, and subjecting the resulting projected image to a θ/2 method.
Example 25
(190) The contact angle was measured by using compound (22) synthesized in Example 9 instead of compound (21) to modify the surface of the glass slide in the same manner as in Example 24.
Example 26
(191) The contact angle was measured by using compound (23) synthesized in Example 10 instead of compound (21) to modify the surface of the glass slide in the same manner as in Example 24.
Example 27
(192) The contact angle was measured by using compound (24) synthesized in Example 11 instead of compound (21) to modify the surface of the glass slide in the same manner as in Example 24.
Example 28
(193) The contact angle was measured by using compound (25) synthesized in Example 12 instead of compound (21) to modify the surface of the glass slide in the same manner as in Example 24.
Example 29
(194) The contact angle was measured by using compound (26) synthesized in Example 13 instead of compound (21) to modify the surface of the glass slide in the same manner as in Example 24.
Example 30
(195) The contact angle was measured by using compound (27) synthesized in Example 14 instead of compound (21) to modify the surface of the glass slide in the same manner as in Example 24.
Example 31
(196) The contact angle was measured by using compound (28) synthesized in Example 15 instead of compound (21) to modify the surface of the glass slide in the same manner as in Example 24.
Comparative Example 2
(197) The contact angle was measured by using CF.sub.3(CF.sub.2).sub.5CH.sub.2CH.sub.2Si (OMe).sub.3 (produced by Sigma-Aldrich) as a comparative agent instead of compound (21) to modify the surface of the glass slide in the same manner as in Example 24.
(198) The results obtained were shown in Table 1.
(199) TABLE-US-00001 TABLE 1 Fluorine- Contact angle [°] containing compound Water Hexadecane Example 24 Compound (21) 109.5 76.0 Example 25 Compound (22) 97.3 60.4 Example 26 Compound (23) 105.7 63.5 Example 27 Compound (24) 100.1 49.8 Example 28 Compound (25) 110.6 75.7 Example 29 Compound (26) 104.5 66.7 Example 30 Compound (27) 103.3 67.1 Example 31 Compound (28) 109.4 64.4 Comparative Comparative agent 55.1 33.9 Example 2
Example 32
(200) Synthesis of Polymer 1
(201) A 50-ml three-necked flask was charged with 0.52 g (5.18 mmol) of methyl methacrylate (reagent of Tokyo Chemical Industry Co., Ltd.), 1.00 g (1.29 mmol) of compound (29), 0.016 g (0.06 mmol) of 2,2′-azobis(2,4-dimethylvaleronitrile) (reagent of Wako Pure Chemical Industries, Ltd.) and 2.9 g of 2-butanone, purged with nitrogen by allowing nitrogen to flow into for 5 minutes with stirring, and thereafter stirred at 80° C. for 7 hours. The reaction liquid was dropped to 42.4 g of hexane to precipitate a polymer, and the supernatant solution was subjected to decantation. The remaining precipitate was again dissolved in 3.5 g of tetrahydrofuran, and the solution was added to 42.4 g of hexane to reprecipitate a polymer. The precipitate was subjected to suction filtration, and dried in vacuum to provide 0.92 g of the product of interest (polymer 1) as a white powder. The yield was 60.5%. The weight average molecular weight Mw and the dispersibility Mw/Mn of the resulting product of interest, in terms of polystyrene measured by GPC, were 17,000 and 1.5, respectively.
Example 33
(202) Synthesis of Polymer 2
(203) A 50-ml three-necked flask was charged with 0.53 g (5.28 mmol) of methyl methacrylate (reagent of Tokyo Chemical Industry Co., Ltd.), 1.00 g (1.32 mmol) of compound (30), 0.017 g (0.07 mmol) of 2,2′-azobis(2,4-dimethylvaleronitrile) (reagent of Wako Pure Chemical Industries, Ltd.) and 2.9 g of 2-butanone, purged with nitrogen by allowing nitrogen to flow into for 5 minutes with stirring, and thereafter stirred at 80° C. for 7 hours. The reaction liquid was dropped to 42.4 g of hexane to precipitate a polymer, and the supernatant solution was subjected to decantation. The remaining precipitate was again dissolved in 3.5 g of tetrahydrofuran, and the solution was added to 42.4 g of hexane to reprecipitate a polymer. The precipitate was subjected to suction filtration, and dried in vacuum to provide 0.95 g of the product of interest (polymer 2) as a white powder. The yield was 61.7%. The weight average molecular weight Mw and the dispersibility Mw/Mn of the resulting product of interest, in terms of polystyrene measured by GPC, were 32,000 and 2.0, respectively.
Example 34
(204) Synthesis of Polymer 3
(205) A 50-ml three-necked flask was charged with 0.54 g (5.40 mmol) of methyl methacrylate (reagent of Tokyo Chemical Industry Co., Ltd.), 1.00 g (1.35 mmol) of compound (31), 0.017 g (0.07 mmol) of 2,2′-azobis(2,4-dimethylvaleronitrile) (reagent of Wako Pure Chemical Industries, Ltd.) and 2.9 g of 2-butanone, purged with nitrogen by allowing nitrogen to flow into for 5 minutes with stirring, and thereafter stirred at 80° C. for 7 hours. The reaction liquid was dropped to 42.4 g of hexane to precipitate a polymer, and the supernatant solution was subjected to decantation. The remaining precipitate was again dissolved in 3.5 g of tetrahydrofuran, and the solution was added to 42.4 g of hexane to reprecipitate a polymer. The precipitate was subjected to suction filtration, and dried in vacuum to provide 0.85 g of the product of interest (polymer 3) as a white powder. The yield was 55.2%. The weight average molecular weight Mw and the dispersibility Mw/Mn of the resulting product of interest, in terms of polystyrene measured by GPC, were 18,000 and 1.7, respectively.
Example 35
(206) Synthesis of Polymer 4
(207) A 50-ml three-necked flask was charged with 0.53 g (5.25 mmol) of methyl methacrylate (reagent of Tokyo Chemical Industry Co., Ltd.), 1.00 g (1.28 mmol) of compound (32), 0.017 g (0.07 mmol) of 2,2′-azobis(2,4-dimethylvaleronitrile) (reagent of Wako Pure Chemical Industries, Ltd.) and 2.9 g of 2-butanone, purged with nitrogen by allowing nitrogen to flow into for 5 minutes with stirring, and thereafter stirred at 80° C. for 7 hours. The reaction liquid was dropped to 42.4 g of hexane to precipitate a polymer, and the supernatant solution was subjected to decantation. The remaining precipitate was again dissolved in 3.5 g of tetrahydrofuran, and the solution was added to 42.4 g of hexane to reprecipitate a polymer. The precipitate was subjected to suction filtration, and dried in vacuum to provide 0.81 g of the product of interest (polymer 4) as a white powder. The yield was 52.6%. The weight average molecular weight Mw and the dispersibility Mw/Mn of the resulting product of interest, in terms of polystyrene measured by GPC, were 19,000 and 1.6, respectively.
Comparative Example 3
(208) Synthesis of Polymer 5
(209) A 50-ml three-necked flask was charged with 1.85 g (18.51 mmol) of methyl methacrylate (reagent of Tokyo Chemical Industry Co., Ltd.), 2.00 g (4.63 mmol) of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-n-octyl 2-methylpropenate (reagent of Tokyo Chemical Industry Co., Ltd.), 0.057 g (0.23 mmol) of 2,2′-azobis(2,4-dimethylvaleronitrile) (reagent of Wako Pure Chemical Industries, Ltd.) and 6.17 g of 2-butanone, purged with nitrogen by allowing nitrogen to flow into for 5 minutes with stirring, and thereafter stirred at 80° C. for 7 hours. The reaction liquid was dropped to 151.5 g of hexane to precipitate a polymer, and the supernatant solution was subjected to decantation. The remaining precipitate was again dissolved in 12.5 g of tetrahydrofuran, and the solution was added to 151.5 g of hexane to reprecipitate a polymer. The precipitate was subjected to suction filtration, and dried in vacuum to provide 2.01 g of the product of interest (polymer 5) as a white powder. The yield was 52.2%. The weight average molecular weight Mw and the dispersibility Mw/Mn of the resulting product of interest, in terms of polystyrene measured by GPC, were 21,000 and 2.0, respectively.
Example 36
(210) Evaluation of Physical Properties of Polymer
(211) In 4.75 g of 2-butanone was dissolved 0.25 g of polymer 1 obtained in Example 32, and subjected to filtration by a filter, to prepare a polymer solution. A glass substrate (50 mm×50 mm×1.0 mm) was spin-coated with the polymer solution (slope for 5 seconds, then at 1,500 rpm for 10 seconds, and slope for additional 5 seconds), and a heat treatment at 120° C. for 1 hour was performed to thereby evaporate the solvent, to form a film. The contact angle of the resulting thin film to each of water and hexadecane was measured.
Example 37
(212) A thin film was formed in the same manner as in Example 36 by use of polymer 2 synthesized in Example 33 instead of polymer 1, and the contact angle thereof was measured.
Example 38
(213) A thin film was formed in the same manner as in Example 36 by use of polymer 3 synthesized in Example 34 instead of polymer 1, and the contact angle thereof was measured.
Example 39
(214) A thin film was formed in the same manner as in Example 36 by use of polymer 4 synthesized in Example 35 instead of polymer 1, and the contact angle thereof was measured.
Comparative Example 4
(215) A thin film was formed in the same manner as in Example 36 by use of polymer 5 synthesized in Comparative Example 3 instead of polymer 1, and the contact angle thereof was measured.
(216) The results obtained were shown in Table 2.
(217) TABLE-US-00002 TABLE 2 Fluorine- Contact angle [°] containing polymer Water Hexadecane Example 36 Polymer 1 112.1 65.9 Example 37 Polymer 2 115.6 68.3 Example 38 Polymer 3 111.0 64.3 Example 39 Polymer 4 110.4 63.6 Comparative Polymer 5 106.9 61.0 Example 4
Example 40
(218) Preparation of Release Agent Solution
(219) An aqueous release agent solution including 0.5% by weight of compound (33) obtained in Example 20, 49.8% by weight of pure water and 49.7% by weight of isopropanol was prepared. The release agent solution was used to perform evaluation of releasability according to the following measurement method.
(220) Evaluation of Releasability
(221) A polyurethane prepolymer and a curing agent were poured into a mold (made of aluminum, 60 mm in diameter and 50 mm in depth) coated with the release agent, and cured under a heated and pressurized condition, and thereafter the load at which a molded product was released from the mold was measured by a push-pull scale. The releasability in a case where the load required was less than 10 N was rated as “Excellent”, that in a case where the load was 10 N or more and less than 20 N was rated as “Good”, that in a case where the load was 20 N or more and less than 50 N rated as “Fair”, and that in a case where the load was 50 N or more was rated as “Poor”. In addition, the number of times where releasing was possible under a load of less than 50 N under the same condition was measured and defined as the repeatability.
Examples 41 to 44
(222) Each aqueous release agent solution in which the release agent compound, the amount of the additive and the amount of the solvent in Example 40 were variously changed was used to measure the same measurement.
Comparative Examples 5 to 6
(223) Each aqueous release agent solution in which the release agent compound, the amount of the additive and the amount of the solvent in Example 40 were variously changed was used to measure the same measurement.
(224) The results obtained were shown, together with the amount of each release agent solution component (unit: % by weight), in Table 3.
(225) TABLE-US-00003 TABLE 3 Release agent Release agent Pure Repeatability compound concentration water Isopropanol Triethylamine Releasability (times) Example 40 Compound (33) 0.5 49.8 49.7 0 Excellent 20 Example 41 Compound (33) 0.5 99.45 0 0.05 Excellent 10 Example 42 Compound (34) 0.5 49.8 49.7 0 Good 6 Example 43 Compound (35) 0.5 49.8 49.7 0 Good 4 Example 44 Compound (36) 0.5 49.8 49.7 0 Good 5 Comparative Compound (37) 0.5 49.8 49.7 0 Fair 1 Example 5 Comparative Compound (37) 0.5 99.45 0 0.05 Poor 0 Example 6
INDUSTRIAL APPLICABILITY
(226) The novel fluorine-containing compound and the surface modifier using the compound, of the present invention, exhibit high water repellency and oil repellency, and can be utilized in surface modifiers such as a release agent and a antifouling agent.