JP2011162509A - New fluorine-containing acrylic acid ester derivative and method for producing the same - Google Patents
New fluorine-containing acrylic acid ester derivative and method for producing the same Download PDFInfo
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- JP2011162509A JP2011162509A JP2010029042A JP2010029042A JP2011162509A JP 2011162509 A JP2011162509 A JP 2011162509A JP 2010029042 A JP2010029042 A JP 2010029042A JP 2010029042 A JP2010029042 A JP 2010029042A JP 2011162509 A JP2011162509 A JP 2011162509A
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- Prior art keywords
- difluoroacrylate
- group
- trifluoromethyl
- butyl
- iso
- Prior art date
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000011737 fluorine Substances 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 125000005396 acrylic acid ester group Chemical group 0.000 title abstract description 4
- -1 α-trifluoromethylacrylic acid ester Chemical class 0.000 claims abstract description 16
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 11
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- BULLJMKUVKYZDJ-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-6-iodohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I BULLJMKUVKYZDJ-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- KUZGDUCOFKDBCR-UHFFFAOYSA-N CC(C)(C)OC(=O)C(=C(F)F)CC(F)(F)C(F)(F)C(F)(F)F Chemical compound CC(C)(C)OC(=O)C(=C(F)F)CC(F)(F)C(F)(F)C(F)(F)F KUZGDUCOFKDBCR-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 3
- AFYPFACVUDMOHA-UHFFFAOYSA-N chlorotrifluoromethane Chemical compound FC(F)(F)Cl AFYPFACVUDMOHA-UHFFFAOYSA-N 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 description 3
- XTGYEAXBNRVNQU-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-iodopropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)I XTGYEAXBNRVNQU-UHFFFAOYSA-N 0.000 description 2
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- UABUKBOUWSZQOJ-UHFFFAOYSA-N CC(C)(C)OC(=O)C(=C(F)F)CC(F)(C(F)(F)F)C(F)(F)F Chemical compound CC(C)(C)OC(=O)C(=C(F)F)CC(F)(C(F)(F)F)C(F)(F)F UABUKBOUWSZQOJ-UHFFFAOYSA-N 0.000 description 2
- OZDIXBHJUSOWQC-UHFFFAOYSA-N CC(C)(C)OC(=O)C(=C(F)F)CC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F Chemical compound CC(C)(C)OC(=O)C(=C(F)F)CC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F OZDIXBHJUSOWQC-UHFFFAOYSA-N 0.000 description 2
- WUJHIANNOWZPJE-UHFFFAOYSA-N CC(C)(C)OC(=O)C(=C(F)F)CC(F)(F)F Chemical compound CC(C)(C)OC(=O)C(=C(F)F)CC(F)(F)F WUJHIANNOWZPJE-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RCSSZBOUAGQERK-UHFFFAOYSA-N tert-butyl 2-(trifluoromethyl)prop-2-enoate Chemical compound CC(C)(C)OC(=O)C(=C)C(F)(F)F RCSSZBOUAGQERK-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- VPAYJEUHKVESSD-UHFFFAOYSA-N trifluoroiodomethane Chemical compound FC(F)(F)I VPAYJEUHKVESSD-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 0 *CC(C(O*)=O)=C(F)F Chemical compound *CC(C(O*)=O)=C(F)F 0.000 description 1
- YYCFEDCTRHSPLB-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-nonadecafluoro-9-iodononane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I YYCFEDCTRHSPLB-UHFFFAOYSA-N 0.000 description 1
- PGRFXXCKHGIFSV-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-iodobutane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)I PGRFXXCKHGIFSV-UHFFFAOYSA-N 0.000 description 1
- BBZVTTKMXRPMHZ-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoro-2-iodopropane Chemical compound FC(F)(F)C(F)(I)C(F)(F)F BBZVTTKMXRPMHZ-UHFFFAOYSA-N 0.000 description 1
- KQSPFAXUTMJXCT-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoro-2-iodopropane Chemical compound FC(F)(F)C(I)C(F)(F)F KQSPFAXUTMJXCT-UHFFFAOYSA-N 0.000 description 1
- RFCAUADVODFSLZ-UHFFFAOYSA-N 1-Chloro-1,1,2,2,2-pentafluoroethane Chemical compound FC(F)(F)C(F)(F)Cl RFCAUADVODFSLZ-UHFFFAOYSA-N 0.000 description 1
- USYVEDJTMCGMKN-UHFFFAOYSA-N 1-bromo-1,1,2,2,2-pentafluoroethane Chemical compound FC(F)(F)C(F)(F)Br USYVEDJTMCGMKN-UHFFFAOYSA-N 0.000 description 1
- LANNRYWUUQMNPF-UHFFFAOYSA-N 1-bromo-1,1,2,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)Br LANNRYWUUQMNPF-UHFFFAOYSA-N 0.000 description 1
- OWIAIPIQXHPUHV-UHFFFAOYSA-N 1-bromo-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-nonadecafluorononane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)Br OWIAIPIQXHPUHV-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- UENYCJXJJRUIIY-UHFFFAOYSA-N 2-(difluoromethylidene)-4,4,5,5,5-pentafluoropentanoic acid Chemical compound OC(=O)C(=C(F)F)CC(F)(F)C(F)(F)F UENYCJXJJRUIIY-UHFFFAOYSA-N 0.000 description 1
- VLSRKCIBHNJFHA-UHFFFAOYSA-N 2-(trifluoromethyl)prop-2-enoic acid Chemical compound OC(=O)C(=C)C(F)(F)F VLSRKCIBHNJFHA-UHFFFAOYSA-N 0.000 description 1
- SULCAUVYSILBCB-UHFFFAOYSA-N 2-bromo-1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)(Br)C(F)(F)F SULCAUVYSILBCB-UHFFFAOYSA-N 0.000 description 1
- JNUYTCRSXFUQHQ-UHFFFAOYSA-N 2-bromo-1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)C(Br)C(F)(F)F JNUYTCRSXFUQHQ-UHFFFAOYSA-N 0.000 description 1
- KJGXPVLCSICDQG-UHFFFAOYSA-N 2-chloro-1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)(Cl)C(F)(F)F KJGXPVLCSICDQG-UHFFFAOYSA-N 0.000 description 1
- BKWAVXQSZLEURV-UHFFFAOYSA-N 2-chloro-1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)C(Cl)C(F)(F)F BKWAVXQSZLEURV-UHFFFAOYSA-N 0.000 description 1
- FOVGANUDVFJLLX-UHFFFAOYSA-N 2-methylpropyl 2-(trifluoromethyl)prop-2-enoate Chemical compound CC(C)COC(=O)C(=C)C(F)(F)F FOVGANUDVFJLLX-UHFFFAOYSA-N 0.000 description 1
- INNCGMGSHXCCNM-UHFFFAOYSA-N CC(C)(C)OC(=O)C(=C(F)F)CC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F Chemical compound CC(C)(C)OC(=O)C(=C(F)F)CC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F INNCGMGSHXCCNM-UHFFFAOYSA-N 0.000 description 1
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- OPROINNVKKGLNI-UHFFFAOYSA-N CCCCOC(=O)C(=C(F)F)CC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F Chemical compound CCCCOC(=O)C(=C(F)F)CC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F OPROINNVKKGLNI-UHFFFAOYSA-N 0.000 description 1
- OKXPNBLKPIKIOQ-UHFFFAOYSA-N CCCCOC(=O)C(=C(F)F)CC(F)(F)C(F)(F)C(F)(F)F Chemical compound CCCCOC(=O)C(=C(F)F)CC(F)(F)C(F)(F)C(F)(F)F OKXPNBLKPIKIOQ-UHFFFAOYSA-N 0.000 description 1
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- RJCQBQGAPKAMLL-UHFFFAOYSA-N bromotrifluoromethane Chemical compound FC(F)(F)Br RJCQBQGAPKAMLL-UHFFFAOYSA-N 0.000 description 1
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- 238000012824 chemical production Methods 0.000 description 1
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- 238000000605 extraction Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- FWYUJGXEYOXHRJ-UHFFFAOYSA-N fluoromethyl prop-2-enoate Chemical class FCOC(=O)C=C FWYUJGXEYOXHRJ-UHFFFAOYSA-N 0.000 description 1
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- GTRBXMICTQNNIN-UHFFFAOYSA-N methyl 2-(trifluoromethyl)prop-2-enoate Chemical compound COC(=O)C(=C)C(F)(F)F GTRBXMICTQNNIN-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- UXPOJVLZTPGWFX-UHFFFAOYSA-N pentafluoroethyl iodide Chemical compound FC(F)(F)C(F)(F)I UXPOJVLZTPGWFX-UHFFFAOYSA-N 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- XPPLDNPZALIXHM-UHFFFAOYSA-N propan-2-yl 2-(trifluoromethyl)prop-2-enoate Chemical compound CC(C)OC(=O)C(=C)C(F)(F)F XPPLDNPZALIXHM-UHFFFAOYSA-N 0.000 description 1
- OTPPJRROTZEJEB-UHFFFAOYSA-N propyl 2-(trifluoromethyl)prop-2-enoate Chemical compound CCCOC(=O)C(=C)C(F)(F)F OTPPJRROTZEJEB-UHFFFAOYSA-N 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
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- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、新規含フッ素アクリル酸エステル誘導体及びその製造方法に関する。含フッ素アクリル酸エステル誘導体は、医農薬の製造中間体、光学材料及び電子材料の合成原料として有用な化合物である。 The present invention relates to a novel fluorine-containing acrylate derivative and a method for producing the same. The fluorine-containing acrylic acid ester derivative is a useful compound as a synthetic raw material for pharmaceutical and agricultural chemical production intermediates, optical materials and electronic materials.
従来技術として、本発明の含フッ素アクリル酸エステル誘導体及びその製造方法は知られていない。 As the prior art, the fluorine-containing acrylate derivative of the present invention and the production method thereof are not known.
一方、従来の技術として、アクリル酸エステル誘導体にパーフルオロアルキルアイオダイドを付加させ、β−パーフルオロアルキル化カルボン酸誘導体を得る方法や、α−アイオド−β−パーフルオロアルキル化カルボン酸誘導体を得る方法が知られている(非特許文献1、非特許文献2、非特許文献3、非特許文献4) On the other hand, as a conventional technique, a perfluoroalkyl iodide is added to an acrylate derivative to obtain a β-perfluoroalkylated carboxylic acid derivative, or an α-iodo-β-perfluoroalkylated carboxylic acid derivative is obtained. Methods are known (Non-patent document 1, Non-patent document 2, Non-patent document 3, Non-patent document 4)
従来の非特許文献1〜4はα,β−不飽和カルボン酸エステル誘導体へのパーフルオロアルキル基の付加反応に関するもので、本発明の新規パーフルオロアルキル化カルボン酸誘導体が得られることは記載されていない。 Conventional Non-Patent Documents 1 to 4 relate to addition reactions of perfluoroalkyl groups to α, β-unsaturated carboxylic acid ester derivatives, and it is described that the novel perfluoroalkylated carboxylic acid derivatives of the present invention can be obtained. Not.
そこで本発明はパーフルオロアルキル基の付加反応を用いた、新規な含フッ素アクリル酸エステル誘導体の製造方法を提供するものである。 Therefore, the present invention provides a novel method for producing a fluorine-containing acrylate derivative using an addition reaction of a perfluoroalkyl group.
本発明者らは、上記課題を解決する方法について鋭意検討した結果、2−位にトリフルオロメチル基を有するアクリル酸エステル誘導体を原料とし、光をラジカル発生源に用い、パーフルオロアルキル基のラジカル付加反応をすることにより、トリフルオロメチル基の1個フッ素原子が脱離し、新規な含フッ素アクリル酸エステル誘導体が得られることを見出し、本発明を完成させるに至った。 As a result of intensive studies on a method for solving the above problems, the present inventors have used a acrylate derivative having a trifluoromethyl group at the 2-position as a raw material, used light as a radical generation source, and a radical of a perfluoroalkyl group. By carrying out the addition reaction, it was found that one fluorine atom of the trifluoromethyl group was eliminated and a novel fluorine-containing acrylate derivative was obtained, and the present invention was completed.
すなわち本発明は、
[1] 下記一般式(1)
That is, the present invention
[1] The following general formula (1)
(式中Rは水素原子、メチル基、エチル基、n−プロピル基、iso−プロピル基、n−ブチル基、iso−ブチル基又はtert−ブチル基を示し、Rfはトリフルオロメチル基、ペンタフルオロエチル基又は炭素数3〜10の直鎖、分岐若しくは環式のパーフルオロアルキル基を示す)
で表される含フッ素アクリル酸エステル誘導体。
(In the formula, R represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group or a tert-butyl group, and Rf represents a trifluoromethyl group or a pentafluoro group. Represents an ethyl group or a linear, branched or cyclic perfluoroalkyl group having 3 to 10 carbon atoms)
A fluorine-containing acrylic ester derivative represented by:
[2] 下記一般式(2) [2] The following general formula (2)
(式中Rは前記に同じ)
で表されるα−トリフルオロメチルアクリル酸エステル誘導体を光照射下、下記一般式(3)
Rf−X (3)
(式中Rfはトリフルオロメチル基、ペンタフルオロエチル基又は炭素数3〜10の直鎖、分岐若しくは環式のパーフルオロアルキル基を示し、Xはハロゲン原子を示す)
で表されるパーフルオロアルキルハライドと、反応させることを特徴とする項1に記載の一般式(1)で表される含フッ素アクリル酸エステル誘導体の製造方法。
を提供するものである。
(Wherein R is the same as above)
The α-trifluoromethyl acrylate derivative represented by the following general formula (3) under light irradiation:
Rf-X (3)
(Wherein Rf represents a trifluoromethyl group, a pentafluoroethyl group, or a linear, branched or cyclic perfluoroalkyl group having 3 to 10 carbon atoms, and X represents a halogen atom)
The manufacturing method of the fluorine-containing acrylate derivative represented by General formula (1) of Claim 1 characterized by making it react with the perfluoroalkyl halide represented by these.
Is to provide.
本発明により各種医農薬の合成中間体として有用なβ−パーフルオロアルキル化カルボン酸誘導体の工業的が可能となった。 The present invention has made it possible to industrially produce β-perfluoroalkylated carboxylic acid derivatives useful as intermediates for the synthesis of various medical and agricultural chemicals.
以下、本発明の実施形態について説明する。 Hereinafter, embodiments of the present invention will be described.
本発明において、炭素数3〜10の直鎖、分岐若しくは環式のパールルオロアルキル基とは、トリフルオロメチル基、ペンタフルオロエチル基、n−ヘプタフルオロプロピル基、1−(トリフルオロメチル)テトラフルオロエチル基、n−ノナフルオロブチル基、1,1,−ビス(トリフルロメチル)トリフルオロエチル基、n−ウンデカフルオロペンチル基、n−トリデカフルオロヘキシル基又はウンデカフルオロシクロヘキシル基を表す。 In the present invention, a linear, branched or cyclic pearl fluoroalkyl group having 3 to 10 carbon atoms is a trifluoromethyl group, a pentafluoroethyl group, an n-heptafluoropropyl group, or 1- (trifluoromethyl) tetra. Fluoroethyl group, n-nonafluorobutyl group, 1,1, -bis (trifluoromethyl) trifluoroethyl group, n-undecafluoropentyl group, n-tridecafluorohexyl group or undecafluorocyclohexyl group .
本発明の一般式(1)で表される含フッ素アクリル酸エステル誘導体としては、具体的には例えば、2−(2,2,2−トリフルオロエチル)−3,3−ジフルオロアクリル酸、メチル[2−(2,2,2−トリフルオロエチル)−3,3−ジフルオロアクリレート]、エチル[2−(2,2,2−トリフルオロエチル)−3,3−ジフルオロアクリレート]、n−プロピル[2−(2,2,2−トリフルオロエチル)−3,3−ジフルオロアクリレート]、iso−プロピル[2−(2,2,2−トリフルオロエチル)−3,3−ジフルオロアクリレート]、n−ブチル[2−(2,2,2−トリフルオロエチル)−3,3−ジフルオロアクリレート]、iso−ブチル[2−(2,2,2−トリフルオロエチル)−3,3−ジフルオロアクリレート]、tert−ブチル[2−(2,2,2−トリフルオロエチル)−3,3−ジフルオロアクリレート]、2−(2,2,3,3,3−ペンタフルオロプロピル)−3,3−ジフルオロアクリル酸、メチル[2−(2,2,3,3,3−ペンタフルオロプロピル)−3,3−ジフルオロアクリレート]、エチル[2−(2,2,3,3,3−ペンタフルオロプロピル)−3,3−ジフルオロアクリレート]、n−プロピル[2−(2,2,3,3,3−ペンタフルオロプロピル)−3,3−ジフルオロアクリレート]、iso−プロピル[2−(2,2,3,3,3−ペンタフルオロプロピル)−3,3−ジフルオロアクリレート]、n−ブチル[2−(2,2,3,3,3−ペンタフルオロプロピル)−3,3−ジフルオロアクリレート]、iso−ブチル[2−(2,2,3,3,3−ペンタフルオロプロピル)−3,3−ジフルオロアクリレート]、tert−ブチル[2−(2,2,3,3,3−ペンタフルオロプロピル)−3,3−ジフルオロアクリレート]、2−(2,2,3,3,4,4,4−ヘキサフルオロブチル)−3,3−ジフルオロアクリル酸、メチル[2−(2,2,3,3,4,4,4−ヘプタフルオロブチル)−3,3−ジフルオロアクリレート]、エチル[2−(2,2,3,3,4,4,4−ヘプタフルオロブチル)−3,3−ジフルオロアクリレート]、n−プロピル[2−(2,2,3,3,4,4,4−ヘプタフルオロブチル)−3,3−ジフルオロアクリレート]、iso−プロピル[2−(2,2,3,3,4,4,4−ヘプタフルオロブチル)−3,3−ジフルオロアクリレート]、n−ブチル[2−(2,2,3,3,4,4,4−ヘプタフルオロブチル)−3,3−ジフルオロアクリレート]、iso−ブチル[2−(2,2,3,3,4,4,4−ヘプタフルオロブチル)−3,3−ジフルオロアクリレート]、tert−ブチル[2−(2,2,3,3,4,4,4−ヘプタフルオロブチル)−3,3−ジフルオロアクリレート]、2−(2−トリフルオロメチル−2,3,3,3−ヘプタフルオロプロピル)−3,3−ジフルオロアクリル酸、メチル[2−(2−トリフルオロメチル−2,3,3,3−ヘプタフルオロプロピル)−3,3−ジフルオロアクリレート]、エチル[2−(2−トリフルオロメチル−2,3,3,3−ヘプタフルオロプロピル)−3,3−ジフルオロアクリレート]、n−プロピル[2−(2−トリフルオロメチル−2,3,3,3−ヘプタフルオロプロピル)−3,3−ジフルオロアクリレート]、iso−プロピル[2−(2−トリフルオロメチル−2,3,3,3−ヘプタフルオロプロピル)−3,3−ジフルオロアクリレート]、n−ブチル[2−(2−トリフルオロメチル−2,3,3,3−ヘプタフルオロプロピル)−3,3−ジフルオロアクリレート]、iso−ブチル[2−(2−トリフルオロメチル−2,3,3,3−ヘプタフルオロプロピル)−3,3−ジフルオロアクリレート]、tert−ブチル[2−(2−トリフルオロメチル−2,3,3,3−ヘプタフルオロプロピル)−3,3−ジフルオロアクリレート]、2−(2,2,3,3,4,4,5,5,5ノナフルオロペンチル)−3,3−ジフルオロアクリル酸、メチル[2−(2,2,3,3,4,4,5,5,5−ノナフルオロペンチル)−3,3−ジフルオロアクリレート]、エチル[2−(2,2,3,3,4,4,5,5,5−ノナフルオロペンチル)−3,3−ジフルオロアクリレート]、n−プロピル[2−(2,2,3,3,4,4,5,5,5−ノナフルオロペンチル)−3,3−ジフルオロアクリレート]、iso−プロピル[2−(2,2,3,3,4,4,5,5,5−ノナフルオロペンチル)−3,3−ジフルオロアクリレート]、n−ブチル[2−(2,2,3,3,4,4,5,5,5−ノナフルオロペンチル)−3,3−ジフルオロアクリレート]、iso−ブチル[2−(2,2,3,3,4,4,5,5,5−ノナフルオロペンチル)−3,3−ジフルオロアクリレート]、tert−ブチル[2−(2,2,3,3,4,4,5,5,5−ノナフルオロペンチル)−3,3−ジフルオロアクリレート]、2−[2,2−ビス(トリフルオロメチル)−3,3,3−トリフルオロプロピル]−3,3−ジフルオロアクリル酸、メチル{2−[2,2−ビス(トリフルオロメチル)−3,3,3−トリフルオロプロピル]−3,3−ジフルオロアクリレート}、エチル{2−[2,2−ビス(トリフルオロメチル)−3,3,3−トリフルオロプロピル]−3,3−ジフルオロアクリレート}、n−プロピル{2−[2,2−ビス(トリフルオロメチル)−3,3,3−トリフルオロプロピル]−3,3−ジフルオロアクリレート}、iso−プロピル{2−[2,2−ビス(トリフルオロメチル)−3,3,3−トリフルオロプロピル]−3,3−ジフルオロアクリレート}、n−ブチル{2−[2,2−ビス(トリフルオロメチル)−3,3,3−トリフルオロプロピル]−3,3−ジフルオロアクリレート}、iso−ブチル{2−[2,2−ビス(トリフルオロメチル)−3,3,3−トリフルオロプロピル]−3,3−ジフルオロアクリレート}、tert−ブチル{2−[2,2−ビス(トリフルオロメチル)−3,3,3−トリフルオロプロピル]−3,3−ジフルオロアクリレート}、2−(2,2,3,3,4,4,5,5,6,6,6−ウンデカフルオロヘキシル)−3,3−ジフルオロアクリル酸、メチル[2−(2,2,3,3,4,4,5,5,6,6,6−ウンデカフルオロヘキシル)−3,3−ジフルオロアクリレート]、エチル[2−(2,2,3,3,4,4,5,5,6,6,6−ウンデカフルオロヘキシル)−3,3−ジフルオロアクリレート]、n−プロピル[2−(2,2,3,3,4,4,5,5,6,6,6−ウンデカフルオロヘキシル)−3,3−ジフルオロアクリレート]、iso−プロピル[2−(2,2,3,3,4,4,5,5,6,6,6−ウンデカフルオロヘキシル)−3,3−ジフルオロアクリレート]、n−ブチル[2−(2,2,3,3,4,4,5,5,6,6,6−ウンデカフルオロヘキシル)−3,3−ジフルオロアクリレート]、iso−ブチル[2−(2,2,3,3,4,4,5,5,6,6,6−ウンデカフルオロヘキシル)−3,3−ジフルオロアクリレート]、tert−ブチル[2−(2,2,3,3,4,4,5,5,6,6,6−ウンデカフルオロヘキシル)−3,3−ジフルオロアクリレート]、2−(2,2,3,3,4,4,5,5,6,6,7,7,7−トリデカフルオロヘプチル)−3,3−ジフルオロアクリル酸、メチル[2−(2,2,3,3,4,4,5,5,6,6,7,7,7−トリデカフルオロヘプチル)−3,3−ジフルオロアクリレート]、エチル[2−(2,2,3,3,4,4,5,5,6,6,7,7,7−トリデカフルオロヘプチル)−3,3−ジフルオロアクリレート]、n−プロピル[2−(2,2,3,3,4,4,5,5,6,6,7,7,7−トリデカフルオロヘプチル)−3,3−ジフルオロアクリレート]、iso−プロピル[2−(2,2,3,3,4,4,5,5,6,6,7,7,7−トリデカフルオロヘプチル)−3,3−ジフルオロアクリレート]、n−ブチル[2−(2,2,3,3,4,4,5,5,6,6,7,7,7−トリデカフルオロヘプチル)−3,3−ジフルオロアクリレート]、iso−ブチル[2−(2,2,3,3,4,4,5,5,6,6,7,7,7−トリデカフルオロヘプチル)−3,3−ジフルオロアクリレート]、tert−ブチル[2−(2,2,3,3,4,4,5,5,6,6,7,7,7−トリデカフルオロヘプチル)−3,3−ジフルオロアクリレート]、2−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8−ペンタデカフルオロオクチル)−3,3−ジフルオロアクリル酸、メチル[2−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8−ペンタデカフルオロオクチル)−3,3−ジフルオロアクリレート]、エチル[2−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8−ペンタデカフルオロオクチル)−3,3−ジフルオロアクリレート]、n−プロピル[2−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8−ペンタデカフルオロオクチル)−3,3−ジフルオロアクリレート]、iso−プロピル[2−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8−ペンタデカフルオロオクチル)−3,3−ジフルオロアクリレート]、n−ブチル[2−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8−ペンタデカフルオロオクチル)−3,3−ジフルオロアクリレート]、iso−ブチル[2−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8−ペンタデカフルオロオクチル)−3,3−ジフルオロアクリレート]、tert−ブチル[2−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8−ペンタデカフルオロオクチル)−3,3−ジフルオロアクリレート]、2−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9−ヘプタデカフルオロノニル)−3,3−ジフルオロアクリル酸、メチル[2−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9−ヘプタデカフルオロノニル)−3,3−ジフルオロアクリレート]、エチル[2−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9−ヘプタデカフルオロノニル)−3,3−ジフルオロアクリレート]、n−プロピル[2−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9−ヘプタデカフルオロノニル)−3,3−ジフルオロアクリレート]、iso−プロピル[2−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9−ヘプタデカフルオロノニル)−3,3−ジフルオロアクリレート]、n−ブチル[2−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9−ヘプタデカフルオロノニル)−3,3−ジフルオロアクリレート]、iso−ブチル[2−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9−ヘプタデカフルオロノニル)−3,3−ジフルオロアクリレート]、tert−ブチル[2−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9−ヘプタデカフルオロノニル)−3,3−ジフルオロアクリレート]、2−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10−ノナデカフルオロデシル)−3,3−ジフルオロアクリル酸、メチル[2−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10−ノナデカフルオロデシル)−3,3−ジフルオロアクリレート]、エチル[2−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10−ノナデカフルオロデシル)−3,3−ジフルオロアクリレート]、n−プロピル[2−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10−ノナデカフルオロデシル)−3,3−ジフルオロアクリレート]、iso−プロピル[2−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10−ノナデカフルオ
ロデシル)−3,3−ジフルオロアクリレート]、n−ブチル[2−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10−ノナデカフルオロデシル)−3,3−ジフルオロアクリレート]、iso−ブチル[2−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10−ノナデカフルオロデシル)−3,3−ジフルオロアクリレート]又はtert−ブチル[2−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10−ノナデカフルオロデシル)−3,3−ジフルオロアクリレート]等が挙げられる。
Specific examples of the fluorine-containing acrylic ester derivative represented by the general formula (1) of the present invention include 2- (2,2,2-trifluoroethyl) -3,3-difluoroacrylic acid, methyl [2- (2,2,2-trifluoroethyl) -3,3-difluoroacrylate], ethyl [2- (2,2,2-trifluoroethyl) -3,3-difluoroacrylate], n-propyl [2- (2,2,2-trifluoroethyl) -3,3-difluoroacrylate], iso-propyl [2- (2,2,2-trifluoroethyl) -3,3-difluoroacrylate], n -Butyl [2- (2,2,2-trifluoroethyl) -3,3-difluoroacrylate], iso-butyl [2- (2,2,2-trifluoroethyl) -3,3-difluoroa Relate], tert-butyl [2- (2,2,2-trifluoroethyl) -3,3-difluoroacrylate], 2- (2,2,3,3,3-pentafluoropropyl) -3,3 -Difluoroacrylic acid, methyl [2- (2,2,3,3,3-pentafluoropropyl) -3,3-difluoroacrylate], ethyl [2- (2,2,3,3,3-pentafluoro Propyl) -3,3-difluoroacrylate], n-propyl [2- (2,2,3,3,3-pentafluoropropyl) -3,3-difluoroacrylate], iso-propyl [2- (2, 2,3,3,3-pentafluoropropyl) -3,3-difluoroacrylate], n-butyl [2- (2,2,3,3,3-pentafluoropropyl) -3,3-difluoroacrylate Rate], iso-butyl [2- (2,2,3,3,3-pentafluoropropyl) -3,3-difluoroacrylate], tert-butyl [2- (2,2,3,3,3- Pentafluoropropyl) -3,3-difluoroacrylate], 2- (2,2,3,3,4,4,4-hexafluorobutyl) -3,3-difluoroacrylic acid, methyl [2- (2, 2,3,3,4,4,4-heptafluorobutyl) -3,3-difluoroacrylate], ethyl [2- (2,2,3,3,4,4,4-heptafluorobutyl) -3 , 3-difluoroacrylate], n-propyl [2- (2,2,3,3,4,4,4-heptafluorobutyl) -3,3-difluoroacrylate], iso-propyl [2- (2, 2,3,3,4,4,4-hep Tafluorobutyl) -3,3-difluoroacrylate], n-butyl [2- (2,2,3,3,4,4,4-heptafluorobutyl) -3,3-difluoroacrylate], iso-butyl [2- (2,2,3,3,4,4,4-heptafluorobutyl) -3,3-difluoroacrylate], tert-butyl [2- (2,2,3,3,4,4, 4-heptafluorobutyl) -3,3-difluoroacrylate], 2- (2-trifluoromethyl-2,3,3,3-heptafluoropropyl) -3,3-difluoroacrylic acid, methyl [2- ( 2-trifluoromethyl-2,3,3,3-heptafluoropropyl) -3,3-difluoroacrylate], ethyl [2- (2-trifluoromethyl-2,3,3,3-heptafluoropropyl) ) -3,3-difluoroacrylate], n-propyl [2- (2-trifluoromethyl-2,3,3,3-heptafluoropropyl) -3,3-difluoroacrylate], iso-propyl [2- (2-trifluoromethyl-2,3,3,3-heptafluoropropyl) -3,3-difluoroacrylate], n-butyl [2- (2-trifluoromethyl-2,3,3,3-hepta Fluoropropyl) -3,3-difluoroacrylate], iso-butyl [2- (2-trifluoromethyl-2,3,3,3-heptafluoropropyl) -3,3-difluoroacrylate], tert-butyl [ 2- (2-trifluoromethyl-2,3,3,3-heptafluoropropyl) -3,3-difluoroacrylate], 2- (2,2,3 , 4,4,5,5,5 nonafluoropentyl) -3,3-difluoroacrylic acid, methyl [2- (2,2,3,3,4,4,5,5,5-nonafluoropentyl) −3,3-difluoroacrylate], ethyl [2- (2,2,3,3,4,4,5,5,5-nonafluoropentyl) -3,3-difluoroacrylate], n-propyl [2 -(2,2,3,3,4,4,5,5,5-nonafluoropentyl) -3,3-difluoroacrylate], iso-propyl [2- (2,2,3,3,4, 4,5,5,5-nonafluoropentyl) -3,3-difluoroacrylate], n-butyl [2- (2,2,3,3,4,4,5,5,5-nonafluoropentyl) -3,3-difluoroacrylate], iso-butyl [2- (2,2,3 , 3,4,4,5,5,5-nonafluoropentyl) -3,3-difluoroacrylate], tert-butyl [2- (2,2,3,3,4,4,5,5,5) -Nonafluoropentyl) -3,3-difluoroacrylate], 2- [2,2-bis (trifluoromethyl) -3,3,3-trifluoropropyl] -3,3-difluoroacrylic acid, methyl {2 -[2,2-bis (trifluoromethyl) -3,3,3-trifluoropropyl] -3,3-difluoroacrylate}, ethyl {2- [2,2-bis (trifluoromethyl) -3, 3,3-trifluoropropyl] -3,3-difluoroacrylate}, n-propyl {2- [2,2-bis (trifluoromethyl) -3,3,3-trifluoropropyl] -3,3- Difluoroacrylate} iso-propyl {2- [2,2-bis (trifluoromethyl) -3,3,3-trifluoropropyl] -3,3-difluoroacrylate}, n-butyl {2- [2,2-bis ( Trifluoromethyl) -3,3,3-trifluoropropyl] -3,3-difluoroacrylate}, iso-butyl {2- [2,2-bis (trifluoromethyl) -3,3,3-trifluoro Propyl] -3,3-difluoroacrylate}, tert-butyl {2- [2,2-bis (trifluoromethyl) -3,3,3-trifluoropropyl] -3,3-difluoroacrylate}, 2- (2,2,3,3,4,5,5,6,6,6-undecafluorohexyl) -3,3-difluoroacrylic acid, methyl [2- (2,2,3,3 4, 4, 5, 5, 6, 6, 6 -Undecafluorohexyl) -3,3-difluoroacrylate], ethyl [2- (2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl) -3, 3-difluoroacrylate], n-propyl [2- (2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl) -3,3-difluoroacrylate], iso -Propyl [2- (2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl) -3,3-difluoroacrylate], n-butyl [2- (2 , 2,3,3,4,4,5,5,6,6,6-undecafluorohexyl) -3,3-difluoroacrylate], iso-butyl [2- (2,2,3,3, 4,4,5,5,6,6,6-undecafluorohexyl) -3,3- Fluoroacrylate], tert-butyl [2- (2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl) -3,3-difluoroacrylate], 2- ( 2,2,3,3,4,5,5,6,6,7,7,7-tridecafluoroheptyl) -3,3-difluoroacrylic acid, methyl [2- (2,2,3 , 3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl) -3,3-difluoroacrylate], ethyl [2- (2,2,3,3,4, 4,5,5,6,6,7,7,7-tridecafluoroheptyl) -3,3-difluoroacrylate], n-propyl [2- (2,2,3,3,4,4,5 , 5,6,6,7,7,7-tridecafluoroheptyl) -3,3-difluoroacrylate], iso-propyl Pill [2- (2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl) -3,3-difluoroacrylate], n-butyl [2 -(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl) -3,3-difluoroacrylate], iso-butyl [2- (2 , 2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl) -3,3-difluoroacrylate], tert-butyl [2- (2,2,2, 3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl) -3,3-difluoroacrylate], 2- (2,2,3,3,4,4 , 5,5,6,6,7,7,8,8,8-pentadecafluorooctyl) -3,3-difluoroacrylic acid, methyl [2- ( 2,2,3,3,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl) -3,3-difluoroacrylate], ethyl [2- (2 , 2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl) -3,3-difluoroacrylate], n-propyl [2- ( 2,2,3,3,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl) -3,3-difluoroacrylate], iso-propyl [2- (2,2,3,3,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl) -3,3-difluoroacrylate], n-butyl [2 -(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl) -3,3-di Fluoroacrylate], iso-butyl [2- (2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl) -3, 3-difluoroacrylate], tert-butyl [2- (2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl) -3 , 3-difluoroacrylate], 2- (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononyl)- 3,3-difluoroacrylic acid, methyl [2- (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoro Nonyl) -3,3-difluoroacrylate], ethyl [2- (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9) 9-heptadecafluorononyl) -3,3-difluoroacrylate], n-propyl [2- (2,2,3,3,4,4,5,5,6,6,7,7,8,8) , 9,9,9-heptadecafluorononyl) -3,3-difluoroacrylate], iso-propyl [2- (2,2,3,3,4,4,5,5,6,6,7, 7,8,8,9,9,9-heptadecafluorononyl) -3,3-difluoroacrylate], n-butyl [2- (2,2,3,3,4,4,5,5,6) , 6,7,7,8,8,9,9,9-heptadecafluorononyl) -3,3-difluoroacrylate], iso-butyl [2- (2,2,3,3,4,4, 5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononyl) -3,3-difluoroacrylate ], Tert-butyl [2- (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononyl) -3 , 3-difluoroacrylate], 2- (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadeca Fluorodecyl) -3,3-difluoroacrylic acid, methyl [2- (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10) , 10,10-nonadecafluorodecyl) -3,3-difluoroacrylate], ethyl [2- (2,2,3,3,4,4,5,5,6,6,7,7,8, 8,9,9,10,10,10-nonadecafluorodecyl) -3,3-difluoroacrylate], n-propyl [2- (2,2,3,3,4,4,5,5,5) 6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodecyl) -3,3-difluoroacrylate], iso-propyl [2- (2,2,3,3) 4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodecyl) -3,3-difluoroacrylate], n-butyl [2 -(2,2,3,3,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodecyl) -3,3- Difluoroacrylate], iso-butyl [2- (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nona Decafluorodecyl) -3,3-difluoroacrylate] or tert-butyl [2- (2,2,3,3,4,4,5,5,6,6, , 7,8,8,9,9,10,10,10- nona heptadecafluorodecyl) -3,3-difluoro acrylate], and the like.
本発明の一般式(2)で表されるα−トリフルオロメチルアクリル酸エステル誘導体としては、具体的には例えば、2−トリフルオロメチルアクリル酸、メチル(2−トリフルオロメチルアクリレート)、エチル(2−トリフルオロメチルアクリレート)、n−プロピル(2−トリフルオロメチルアクリレート)、iso−プロピル(2−トリフルオロメチルアクリレート)、n−ブチル(2−トリフルオロメチルアクリレート)、iso−ブチル(2−トリフルオロメチルアクリレート)又はtert−ブチル(2−トリフルオロメチルアクリレート)が挙げられる。 Specific examples of the α-trifluoromethyl acrylate derivative represented by the general formula (2) of the present invention include 2-trifluoromethyl acrylic acid, methyl (2-trifluoromethyl acrylate), ethyl ( 2-trifluoromethyl acrylate), n-propyl (2-trifluoromethyl acrylate), iso-propyl (2-trifluoromethyl acrylate), n-butyl (2-trifluoromethyl acrylate), iso-butyl (2- Trifluoromethyl acrylate) or tert-butyl (2-trifluoromethyl acrylate).
本発明の一般式(3)で表されるパーフルオロアルキルハライドとしては、具体的に例えば、トリフルオロメチルクロライド、トリフルオロメチルブロマイド、トリフルオロメチルアイオダイド、ペンタフルオロエチルクロライド、ペンタフルオロエチルブロマイド、ペンタフルオロエチルアイオダイド、n−ヘプタフルオロプロピルクロライド、n−ヘプタフルオロプロピルブロマイド、n−ヘプタフルオロプロピルアイオダイド、1−(トリフルオロメチル)テトラフルオロエチルクロライド、1−(トリフルオロメチル)テトラフルオロエチルブロマイド、1−(トリフルオロメチル)テトラフルオロエチルアイオダイド、n−ノナフルオロブチルクロライド、n−ノナフルオロブチルブロマイド、n−ノナフルオロブチルアイオダイド、1,1,−ビス(トリフルロメチル)トリフルオロエチルクロライド、1,1,−ビス(トリフルロメチル)トリフルオロエチルブロマイド、1,1,−ビス(トリフルロメチル)トリフルオロエチルアイオダイド、n−ウンデカフルオロペンチルクロライド、n−ウンデカフルオロペンチルブロマイド、n−ウンデカフルオロペンチルアイオダイド、n−トリデカフルオロヘキシルクロライド、n−トリデカフルオロヘキシルブロマイド、n−トリデカフルオロヘキシルアイオダイド、ウンデカフルオロシクロヘキシルクロライド、ウンデカフルオロシクロヘキシルブロマイド、ウンデカフルオロシクロヘキシルアイオダイド、n−ペンタデカフルオロヘプチルクロライド、n−ペンタデカフルオロヘプチルブロマイド、n−ペンタデカフルオロヘプチルアイオダイド、n−ヘプタデカフルオロオクチルクロライド、n−ヘプタデカフルオロオクチルブロマイド、n−ヘプタデカフルオロオクチルアイオダイド、n−ノナデカフルオロノニルクロライド、ノナデカフルオロノニルブロマイド又はノナデカフルオロノニルアイオダイド等を挙げることができる。 Specific examples of the perfluoroalkyl halide represented by the general formula (3) of the present invention include trifluoromethyl chloride, trifluoromethyl bromide, trifluoromethyl iodide, pentafluoroethyl chloride, pentafluoroethyl bromide, Pentafluoroethyl iodide, n-heptafluoropropyl chloride, n-heptafluoropropyl bromide, n-heptafluoropropyl iodide, 1- (trifluoromethyl) tetrafluoroethyl chloride, 1- (trifluoromethyl) tetrafluoroethyl Bromide, 1- (trifluoromethyl) tetrafluoroethyl iodide, n-nonafluorobutyl chloride, n-nonafluorobutyl bromide, n-nonafluorobutyl iodide 1,1, -bis (trifluoromethyl) trifluoroethyl chloride, 1,1, -bis (trifluoromethyl) trifluoroethyl bromide, 1,1, -bis (trifluoromethyl) trifluoroethyl iodide, n-undecafluoropentyl chloride, n-undecafluoropentyl bromide, n-undecafluoropentyl iodide, n-tridecafluorohexyl chloride, n-tridecafluorohexyl bromide, n-tridecafluorohexyl iodide, Undecafluorocyclohexyl chloride, undecafluorocyclohexyl bromide, undecafluorocyclohexyl iodide, n-pentadecafluoroheptyl chloride, n-pentadecafluoroheptyl bromide, n-pentade Fluoroheptyl iodide, n-heptadecafluorooctyl chloride, n-heptadecafluorooctyl bromide, n-heptadecafluorooctyl iodide, n-nonadecafluorononyl chloride, nonadecafluorononyl bromide or nonadecafluorononyl iodide Etc.
本発明の反応の実施に当っては、パイレックス製のガラス容器に前記一般式(2)で表されるα−トリフルオロメチルアクリル酸エステル誘導体、パーフルオロアルキルハライド、溶剤及び還元剤水溶液を仕込み光照射下、反応を行う。 In carrying out the reaction of the present invention, an α-trifluoromethyl acrylate derivative represented by the general formula (2), a perfluoroalkyl halide, a solvent and an aqueous reducing agent solution are charged into a Pyrex glass container. The reaction is performed under irradiation.
本発明の反応で使用可能な光発生装置は市販の高圧水銀灯が適用可能で、通常100W〜1000Wのランプを用い光照射を行う。 A commercially available high-pressure mercury lamp can be used as the light generator usable in the reaction of the present invention, and light irradiation is usually performed using a 100 W to 1000 W lamp.
本発明に適用可能な溶剤は、反応に不活性でかつ光の吸収がないものであれば特に規定はないが、具体的には例えば、ジクロロメタン、四塩化炭素等のハロゲン化炭化水素等が挙げられ、反応に具するα−トリフルオロメチルアクリル酸エステル誘導体に対して、10〜1000重量倍量の範囲である。 Solvents applicable to the present invention are not particularly limited as long as they are inert to the reaction and do not absorb light. Specific examples thereof include halogenated hydrocarbons such as dichloromethane and carbon tetrachloride. The amount is in the range of 10 to 1000 times by weight with respect to the α-trifluoromethyl acrylate derivative included in the reaction.
本発明の反応で使用するパーフルオロアルキルハライドの使用量は、反応に具するα−トリフルオロメチルアクリル酸エステル誘導体に対して等モル量の使用で実施可能であるが、反応を完結させるために、通常1.05〜1.50モル量を使用する。 The perfluoroalkyl halide used in the reaction of the present invention can be used in an equimolar amount with respect to the α-trifluoromethyl acrylate derivative included in the reaction, but in order to complete the reaction. Usually, 1.05-1.50 molar amount is used.
本発明の反応に使用する還元剤水溶液は、特に規定はないが、亜硫酸ナトリウム水溶液、亜硫酸水素ナトリウム水溶液、チオ硫酸ナトリウム水溶液等が使用可能で、通常1mmolの水溶液とし、反応に具するα−トリフルオロメチルアクリル酸エステル誘導体に対して、3〜10モル量を使用する。 The reducing agent aqueous solution used in the reaction of the present invention is not particularly limited, but sodium sulfite aqueous solution, sodium hydrogen sulfite aqueous solution, sodium thiosulfate aqueous solution and the like can be used. A 3 to 10 molar amount is used with respect to the fluoromethyl acrylate derivative.
本発明の反応温度及び時間は、基質の種類、高圧水銀灯の能力によりことなるが、通常0〜30℃の温度範囲で2〜20時間の範囲で反応は完結する。 The reaction temperature and time of the present invention vary depending on the type of substrate and the ability of the high-pressure mercury lamp, but the reaction is usually completed in the temperature range of 0 to 30 ° C. and in the range of 2 to 20 hours.
以下実施例により本発明を具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited only to these examples.
実施例1 tert−ブチル[2-(2,2,3,3,4,4,5,5,6,6,7,7,7−トリデカフルオロヘプチル)−3,3−ジフルオロアクリレート]の調製 Example 1 of tert-butyl [2- (2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl) -3,3-difluoroacrylate] Preparation
パイレックスの容器にtert−ブチル(2−トリフルオロメチルアクリレート)(39.0mg,0.2mmol,1当量)、塩化メチレン(5ml)、トリデカフルオロヘキシルアイオダイド(90μL,0.4mmol,2当量)、チオ硫酸ナトリウム水溶液(チオ硫酸ナトリウム:158mg,水:1mL)を順に加えて蓋をし、よく攪拌した後、高圧水銀灯(460W)による光照射下反応を5時間行った。反応終了後、水を加え、酢酸エチルで抽出を行い、有機層を無水硫酸ナトリウムで乾燥後、ろ過、濃縮を行い粗製物を得た。得られた粗生成物をシリカゲルカラムクロマトグラフィーで精製を行うことにより、目的物のtert−ブチル[2-(2,2,3,3,4,4,5,5,6,6,7,7,7−トリデカフルオロヘプチル)−3,3−ジフルオロアクリレート]を収率73%で得た。
1H−NMR(400MHz,CDCl3)δ3.50(1H,m,C6F13CHH),3.18(1H,m,C6F13CHH),1.52(9H,s,tBu)。
In a Pyrex container, tert-butyl (2-trifluoromethyl acrylate) (39.0 mg, 0.2 mmol, 1 equivalent), methylene chloride (5 ml), tridecafluorohexyl iodide (90 μL, 0.4 mmol, 2 equivalents) Then, an aqueous solution of sodium thiosulfate (sodium thiosulfate: 158 mg, water: 1 mL) was added in order and the mixture was capped and stirred well, and then the reaction was carried out for 5 hours under light irradiation with a high-pressure mercury lamp (460 W). After completion of the reaction, water was added, extraction was performed with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, filtered and concentrated to obtain a crude product. The obtained crude product was purified by silica gel column chromatography to obtain the target tert-butyl [2- (2,2,3,3,4,4,5,5,6,6,7, 7,7-tridecafluoroheptyl) -3,3-difluoroacrylate] was obtained in a yield of 73%.
1 H-NMR (400 MHz, CDCl 3 ) δ 3.50 (1H, m, C 6 F 13 CH H ), 3.18 (1H, m, C 6 F 13 CH H ), 1.52 (9H, s, tBu).
実施例2 tetr−ブチル[2-(2,2,3,3,4,4,4−ヘプタフルオロブチル)−3,3−ジフルオロアクリレート]の調製 Example 2 Preparation of tert-butyl [2- (2,2,3,3,4,4,4-heptafluorobutyl) -3,3-difluoroacrylate]
実施例1と同じ反応装置を用い、トリデカフルオロヘキシルアイオダイドに替えて、n−ヘプタフルオロプロピルアイオダイドを用いた以外、実施例1と同じ反応操作を行い、目的物のtetr−ブチル[2-(2,2,3,3,4,4,4−ヘプタフルオロブチル)−3,3−ジフルオロアクリレート]を収率56%で得た。
1H−NMR(400MHz,CDCl3)δ3.46(1H,m,C3F7CHH),3.18(1H,m,C3F7CHH),1.52(9H,s,tBu)。
13C−NMR(150MHz,CDCl3)δ163.8,124.5,122.7,85.5,40.5(t,JC-F=19.1Hz,C3F7C),27.1。
Using the same reaction apparatus as in Example 1, except that n-heptafluoropropyl iodide was used instead of tridecafluorohexyl iodide, the same reaction operation as in Example 1 was carried out, and the target product tert-butyl [2 -(2,2,3,3,4,4,4-heptafluorobutyl) -3,3-difluoroacrylate] was obtained in a yield of 56%.
1 H-NMR (400 MHz, CDCl 3 ) δ 3.46 (1H, m, C 3 F 7 CH H ), 3.18 (1 H, m, C 3 F 7 CH H ), 1.52 (9 H, s, tBu).
13 C-NMR (150 MHz, CDCl 3 ) δ 163.8, 124.5, 122.7, 85.5, 40.5 (t, J C−F = 19.1 Hz, C 3 F 7 C ), 27.1.
実施例3 tetr−ブチル[2-(2−トリフルオロメチル−2,3,3,3−テトラフルオロプロピル)−3,3−ジフルオロアクリレート]の調製 Example 3 Preparation of tert-butyl [2- (2-trifluoromethyl-2,3,3,3-tetrafluoropropyl) -3,3-difluoroacrylate]
実施例1と同じ反応装置を用い、トリデカフルオロヘキシルアイオダイドに替えて、iso−ヘプタフルオロアイオダイドを用いた以外、実施例と同じ反応操作を行い、目的物のtetr−ブチル[2-(2−トリフルオロメチル−2,3,3,3−テトラフルオロプロピル)−3,3−ジフルオロアクリレート]を収率29%で得た。
1H−NMR(400MHz,CDCl3)δ3.24(1H,m,C3F7CHH),2.994 (1H,m,C3F7CHH),1.52(9H,s,tBu)。
Using the same reaction apparatus as in Example 1, except that iso-heptafluoroiodide was used instead of tridecafluorohexyl iodide, the same reaction operation as in Example was performed, and the target product, tert-butyl [2- ( 2-trifluoromethyl-2,3,3,3-tetrafluoropropyl) -3,3-difluoroacrylate] was obtained in a yield of 29%.
1 H-NMR (400 MHz, CDCl 3 ) δ 3.24 (1 H, m, C 3 F 7 CH H ), 2.994 (1 H, m, C 3 F 7 CH H ), 1.52 (9 H, s, tBu).
実施例4 tetr−ブチル[2-(2,2,2−トリフルオロエチル)−3,3−ジフルオロアクリレート]の調製 Example 4 Preparation of tetr-butyl [2- (2,2,2-trifluoroethyl) -3,3-difluoroacrylate]
実施例1と同じ反応装置を用い、トリデカフルオロヘキシルアイオダイドに替えて、トリフルオロメチルアイオダイドを用いた以外、実施例と同じ反応操作を行い、目的物のtetr−ブチル[2-(2,2,2−トリフルオロエチル)−3,3−ジフルオロアクリレート]を収率57%で得た。
1H−NMR(400MHz,CDCl3)δ3.43(1H,m,CF3CHH),3.27(1H,m,CF3CHH),1.511.52(9H,s,tBu)。
Using the same reaction apparatus as in Example 1, except that trifluoromethyl iodide was used instead of tridecafluorohexyl iodide, the same reaction operation as in Example was performed, and the target product tert-butyl [2- (2 , 2,2-trifluoroethyl) -3,3-difluoroacrylate] was obtained in a yield of 57%.
1 H-NMR (400 MHz, CDCl 3 ) δ 3.43 (1H, m, CF 3 CH H ), 3.27 (1 H, m, CF 3 CH H ), 1.511.52 (9H, s, tBu) .
本発明により、医農薬の製造中間体、光学材料及び電子材料の合成原料として期待される新規な含フッ素アクリル酸エステル誘導体及びその工業的な製法を提案できた。 According to the present invention, it has been possible to propose a novel fluorine-containing acrylate derivative that is expected as a synthetic intermediate for producing pharmaceuticals and agricultural chemicals, optical materials and electronic materials, and an industrial production method thereof.
Claims (2)
で表される含フッ素アクリル酸エステル誘導体。 The following general formula (1)
A fluorine-containing acrylic ester derivative represented by:
で表される、α−トリフルオロメチルアクリル酸エステル誘導体を光照射下、下記一般式(3)
Rf−X (3)
(式中Rfはトリフルオロメチル基、ペンタフルオロエチル基又は炭素数3〜10の直鎖、分岐若しくは環式のパーフルオロアルキル基を示し、Xはハロゲン原子を示す)
で表されるパーフルオロアルキルハライドと、反応させることを特徴とする請求項1に記載の一般式(1)で表される含フッ素アクリル酸エステル誘導体の製造方法。 The following general formula (2)
An α-trifluoromethyl acrylate derivative represented by the following general formula (3) under light irradiation:
Rf-X (3)
(Wherein Rf represents a trifluoromethyl group, a pentafluoroethyl group, or a linear, branched or cyclic perfluoroalkyl group having 3 to 10 carbon atoms, and X represents a halogen atom)
A process for producing a fluorine-containing acrylic ester derivative represented by the general formula (1) according to claim 1, wherein the reaction is performed with a perfluoroalkyl halide represented by the formula:
Priority Applications (1)
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JPWO2013122173A1 (en) * | 2012-02-17 | 2015-05-18 | 旭硝子株式会社 | Fluorine-containing aromatic compound and method for producing the same |
WO2017050609A1 (en) * | 2015-09-23 | 2017-03-30 | Basf Se | FLUORINATED ACRYLATES AS ADDITIVES FOR Li-ION BATTERY ELECTROLYTES |
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JP2008195679A (en) * | 2007-02-15 | 2008-08-28 | Sagami Chem Res Center | 2-substituted benzyl-3,3-difluoroacrylate derivative and method for producing the same |
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JPS60161947A (en) * | 1984-01-31 | 1985-08-23 | Sagami Chem Res Center | Preparation of beta,beta-difluoroacrylic acid derivative |
JP2008195679A (en) * | 2007-02-15 | 2008-08-28 | Sagami Chem Res Center | 2-substituted benzyl-3,3-difluoroacrylate derivative and method for producing the same |
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Cited By (4)
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JPWO2013122173A1 (en) * | 2012-02-17 | 2015-05-18 | 旭硝子株式会社 | Fluorine-containing aromatic compound and method for producing the same |
WO2017050609A1 (en) * | 2015-09-23 | 2017-03-30 | Basf Se | FLUORINATED ACRYLATES AS ADDITIVES FOR Li-ION BATTERY ELECTROLYTES |
CN108475820A (en) * | 2015-09-23 | 2018-08-31 | 国轩高科美国研究院 | Fluorinated acrylic ester as lithium ion battery electrolyte additive |
US11133529B2 (en) | 2015-09-23 | 2021-09-28 | Gotion, Inc. | Fluorinated acrylates as additives for Li-ion battery electrolytes |
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