JPH04149155A - Hydroxybenzoic acid derivative having polymerizable group and its production - Google Patents
Hydroxybenzoic acid derivative having polymerizable group and its productionInfo
- Publication number
- JPH04149155A JPH04149155A JP27356490A JP27356490A JPH04149155A JP H04149155 A JPH04149155 A JP H04149155A JP 27356490 A JP27356490 A JP 27356490A JP 27356490 A JP27356490 A JP 27356490A JP H04149155 A JPH04149155 A JP H04149155A
- Authority
- JP
- Japan
- Prior art keywords
- hydroxybenzoic acid
- group
- acid derivative
- ester
- chloro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 150000005419 hydroxybenzoic acid derivatives Chemical class 0.000 title claims 2
- -1 methacryloyl halide Chemical class 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 230000002140 halogenating effect Effects 0.000 claims abstract description 9
- 125000005843 halogen group Chemical group 0.000 claims abstract description 7
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 6
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 239000002798 polar solvent Substances 0.000 claims abstract description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 3
- 239000000463 material Substances 0.000 abstract description 5
- 150000005422 4-hydroxybenzoic acid derivatives Chemical class 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 4
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- QGNLHMKIGMZKJX-UHFFFAOYSA-N 3-chloro-4-hydroxybenzoic acid Chemical class OC(=O)C1=CC=C(O)C(Cl)=C1 QGNLHMKIGMZKJX-UHFFFAOYSA-N 0.000 description 13
- 150000002148 esters Chemical class 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- FJMFMJLTGJIZHZ-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propyl 3-chloro-4-hydroxybenzoate Chemical compound CC(=C)C(=O)OCCCOC(=O)C1=CC=C(O)C(Cl)=C1 FJMFMJLTGJIZHZ-UHFFFAOYSA-N 0.000 description 3
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 2
- OYEJIILEIQUHPT-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-chloro-4-hydroxybenzoate Chemical compound CC(=C)C(=O)OCCOC(=O)C1=CC=C(O)C(Cl)=C1 OYEJIILEIQUHPT-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- PQFKJRDTOSTPKW-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 3-chloro-4-hydroxybenzoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C1=CC=C(O)C(Cl)=C1 PQFKJRDTOSTPKW-UHFFFAOYSA-N 0.000 description 2
- HRLYGHMUUKCQEB-UHFFFAOYSA-N 8-prop-2-enoyloxyoctyl 3-chloro-4-hydroxybenzoate Chemical compound OC1=CC=C(C(=O)OCCCCCCCCOC(=O)C=C)C=C1Cl HRLYGHMUUKCQEB-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- 150000003511 tertiary amides Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- UWHSPZZUAYSGTB-UHFFFAOYSA-N 1,1,3,3-tetraethylurea Chemical compound CCN(CC)C(=O)N(CC)CC UWHSPZZUAYSGTB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JYUXDXWXTPSAEL-UHFFFAOYSA-N 1,4-dioxane;oxolane Chemical compound C1CCOC1.C1COCCO1 JYUXDXWXTPSAEL-UHFFFAOYSA-N 0.000 description 1
- YQAQDIDLELFZPE-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)propyl 3-chloro-4-hydroxybenzoate Chemical compound CC(=C)C(=O)OC(C)COC(=O)C1=CC=C(O)C(Cl)=C1 YQAQDIDLELFZPE-UHFFFAOYSA-N 0.000 description 1
- QFMCJTPLTCLMLX-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 3-chloro-4-hydroxybenzoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C1=CC=C(O)C(Cl)=C1 QFMCJTPLTCLMLX-UHFFFAOYSA-N 0.000 description 1
- DWKNOLCXIFYNFV-HSZRJFAPSA-N 2-[[(2r)-1-[1-[(4-chloro-3-methylphenyl)methyl]piperidin-4-yl]-5-oxopyrrolidine-2-carbonyl]amino]-n,n,6-trimethylpyridine-4-carboxamide Chemical compound CN(C)C(=O)C1=CC(C)=NC(NC(=O)[C@@H]2N(C(=O)CC2)C2CCN(CC=3C=C(C)C(Cl)=CC=3)CC2)=C1 DWKNOLCXIFYNFV-HSZRJFAPSA-N 0.000 description 1
- FDMCADKIHAADLZ-UHFFFAOYSA-N 2-hydroxyethyl 3-chloro-4-hydroxybenzoate Chemical compound OCCOC(=O)C1=CC=C(O)C(Cl)=C1 FDMCADKIHAADLZ-UHFFFAOYSA-N 0.000 description 1
- APNGCWVLQPGAPX-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl 3-chloro-4-hydroxybenzoate Chemical compound OC1=CC=C(C(=O)OCCOC(=O)C=C)C=C1Cl APNGCWVLQPGAPX-UHFFFAOYSA-N 0.000 description 1
- SHBSUKPWRIKALM-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl 3-chloro-4-hydroxybenzoate Chemical compound C=CC(=O)OC(C)COC(=O)C1=CC=C(O)C(Cl)=C1 SHBSUKPWRIKALM-UHFFFAOYSA-N 0.000 description 1
- VVQWBKQEWCUQGX-UHFFFAOYSA-N 3-hydroxypropyl 3-chloro-4-hydroxybenzoate Chemical compound OCCCOC(=O)C1=CC=C(O)C(Cl)=C1 VVQWBKQEWCUQGX-UHFFFAOYSA-N 0.000 description 1
- QLGVNUUFSQPTAH-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl 3-chloro-4-hydroxybenzoate Chemical compound OC1=CC=C(C(=O)OCCCOC(=O)C=C)C=C1Cl QLGVNUUFSQPTAH-UHFFFAOYSA-N 0.000 description 1
- QPOCZIATSNMHHH-UHFFFAOYSA-N 3-sulfooxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCOS(O)(=O)=O QPOCZIATSNMHHH-UHFFFAOYSA-N 0.000 description 1
- ZBMVBSJTOSQYQN-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 3-chloro-4-hydroxybenzoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C1=CC=C(O)C(Cl)=C1 ZBMVBSJTOSQYQN-UHFFFAOYSA-N 0.000 description 1
- UXHQLGLGLZKHTC-CUNXSJBXSA-N 4-[(3s,3ar)-3-cyclopentyl-7-(4-hydroxypiperidine-1-carbonyl)-3,3a,4,5-tetrahydropyrazolo[3,4-f]quinolin-2-yl]-2-chlorobenzonitrile Chemical compound C1CC(O)CCN1C(=O)C1=CC=C(C=2[C@@H]([C@H](C3CCCC3)N(N=2)C=2C=C(Cl)C(C#N)=CC=2)CC2)C2=N1 UXHQLGLGLZKHTC-CUNXSJBXSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- ZTKDMNHEQMILPE-UHFFFAOYSA-N 4-methoxy-n,n-dimethylaniline Chemical compound COC1=CC=C(N(C)C)C=C1 ZTKDMNHEQMILPE-UHFFFAOYSA-N 0.000 description 1
- HJFQBJIEQIKWNE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl 3-chloro-4-hydroxybenzoate Chemical compound OC1=CC=C(C(=O)OCCCCCCOC(=O)C=C)C=C1Cl HJFQBJIEQIKWNE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（発明の分野）
本発明は、記録材料用重合性単量体として有用な１重合
性基を有する３−ハロ−４−ヒドロキシ安息香酸誘導体
及びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of the Invention) The present invention relates to a 3-halo-4-hydroxybenzoic acid derivative having a monopolymerizable group useful as a polymerizable monomer for recording materials and a method for producing the same.
（従来技術）
記録材料用重合性単量体として４−ヒドロキシ安息香酸
誘導体は種々知られているが２重合性基を有する３−ハ
ロ−４−ヒドロキシ安息香酸誘導体は新規である。(Prior Art) Various 4-hydroxybenzoic acid derivatives are known as polymerizable monomers for recording materials, but 3-halo-4-hydroxybenzoic acid derivatives having a dipolymerizable group are new.
（発明の目的）
本発明の目的は１記録材料用重合性単量体として有用な
、新規な重合性基を有する３−ハロ−４−ヒドロキシ安
息香酸誘導体及び、簡便でしかも精製の容易な重合性基
を有する３−クロロ−４−ヒドロキシ安息香酸誘導体の
製造方法を提供することである。(Objects of the Invention) The objects of the present invention are to provide a novel 3-halo-4-hydroxybenzoic acid derivative having a polymerizable group useful as a polymerizable monomer for recording materials, and a simple and easily purified polymerizable 3-halo-4-hydroxybenzoic acid derivative. An object of the present invention is to provide a method for producing a 3-chloro-4-hydroxybenzoic acid derivative having a functional group.
（発明の構成）
本発明は、下記−儀式（Ｉ）で表される重合性基を有す
る３−ハロ−４−ヒドロキシ安息香酸誘導体
〔上式中、Ｘはハロゲン原子を、Ｒはアクリロイルオキ
シアルキル基またはメタクリロイルオキシアルキル基を
表す 〕
および、下記−儀式（ＩＩ）で表されるアルコール性水
酸基を育する３−ハロ−４−ヒドロキシ安息香酸誘導体
とアクリル酸またはメタクリル酸ハライドを、極性溶媒
中で反応させることを特徴とする一般式（１＞で表され
る重合性基を有する３−ハロ−４−ヒドロキシ安息香酸
誘導体の製造方法ＨＯ−〈■）＞−ｃ○○Ｚ
（Ｉｆ）Ｘ ／
〔上記−儀式（ＩＩ）中、Ｘはハロゲン原子を、Ｚは、
ヒドロキシアルキル基を表す、〕
および、下記一般式（ＩＩ［）で表される重合性基を有
する４−ヒドロキシ安息香酸誘導体をハロゲン化剤の存
在下にハロゲン化させることを特徴とする一般式（Ｉ）
で表される重合性基を有する３−ハロ−４−ヒドロキシ
安息香酸誘導体の製造方法から構成される。(Structure of the Invention) The present invention provides a 3-halo-4-hydroxybenzoic acid derivative having a polymerizable group represented by the following formula (I) [wherein X is a halogen atom and R is an acryloyloxyalkyl or methacryloyloxyalkyl group] and a 3-halo-4-hydroxybenzoic acid derivative that grows an alcoholic hydroxyl group represented by the following -ritual (II) and acrylic acid or methacrylic acid halide in a polar solvent. A method for producing a 3-halo-4-hydroxybenzoic acid derivative having a polymerizable group represented by the general formula (1>, characterized by reacting HO-<■)>-c○○Z
(If) X / [In the above ritual (II), X is a halogen atom, Z is
represents a hydroxyalkyl group] and a 4-hydroxybenzoic acid derivative having a polymerizable group represented by the following general formula (II [)] is halogenated in the presence of a halogenating agent. I)
It consists of a method for producing a 3-halo-4-hydroxybenzoic acid derivative having a polymerizable group represented by:
一般式（１）中、Ｒて表される基は、炭素原子数５〜２
０のアクリロイルオキシ基又はメタクリロイルオキシ基
を有するアルキル基か好ましくアルキル基はアルコキシ
基、アリールオキン基、ハロゲン原子、アリール基等の
置換基または、酸素原子、硫黄原子、あるいはフェニレ
ン基を含有していても良い
またアルキル基は重合性基を２個以上有していてもよい
。In the general formula (1), the group represented by R has 5 to 2 carbon atoms.
An alkyl group having 0 acryloyloxy or methacryloyloxy groups is preferable, and the alkyl group may contain a substituent such as an alkoxy group, an aryloquine group, a halogen atom, an aryl group, or an oxygen atom, a sulfur atom, or a phenylene group. The alkyl group may also have two or more polymerizable groups.
Ｘて表されるハロゲン原子は、塩素原子または臭素原子
か好ましい。The halogen atom represented by X is preferably a chlorine atom or a bromine atom.
Ｒて表される基の具体的な例としては、アクリロイルオ
キンエチル基、メタクリロイルオキソエチル基、３−ア
クリロイルオキンブロビル基、３メタクリロイルオキン
ブロピル基、２−アクリロイルオキシプロピル基、２−
メタクリロイルオキシブチル基、４−アクリロイルオキ
シブチル基、４−メタクリロイルオキシブチル基、６−
アクリロイルオキシヘキシル基、６−メタクリロイルオ
キシヘキシル基、８−アクリロイルオキシオクチル基、
８−メタクリロイルオキソオクチル基。Specific examples of the group represented by R include an acryloyl oxinethyl group, a methacryloyl oxoethyl group, a 3-acryloyl oxoquinbrobyl group, a 3-methacryloyl oximbropyl group, a 2-acryloyloxypropyl group, −
Methacryloyloxybutyl group, 4-acryloyloxybutyl group, 4-methacryloyloxybutyl group, 6-
Acryloyloxyhexyl group, 6-methacryloyloxyhexyl group, 8-acryloyloxyoctyl group,
8-methacryloyloxooctyl group.
】Ｏ−アクリロイルオキシデシル基、１０−メタクリロ
イルオキンデシル基、４−（アクリロイルオキシメチル
）ベンジル基、４−（メタクリロイルオキシメチル）ベ
ンジル基、３−（アクリロイルオキシメチル）ベンジル
基、３−（メタクリロイルオキシメチル）ベンジル基、
２−（アクリロイルオキシメチル）ベンジル基、２−（
メタクリロイルオキシメチル）ベンジル基、１２−メタ
クリロイルオキシドデシル基、２−（アクリロイルオキ
シエトキシ）エチル基、２−（メタクリロイルオキシエ
トキシ）エチル基、３−（３−アクリロイルオキシプロ
ポキシ）プロピル基、３−（３−メタクリロイルオキシ
プロポキシ）プロピル基。] O-acryloyloxydecyl group, 10-methacryloyloxindecyl group, 4-(acryloyloxymethyl)benzyl group, 4-(methacryloyloxymethyl)benzyl group, 3-(acryloyloxymethyl)benzyl group, 3-(methacryloyl) oxymethyl)benzyl group,
2-(acryloyloxymethyl)benzyl group, 2-(
methacryloyloxymethyl)benzyl group, 12-methacryloyloxydodecyl group, 2-(acryloyloxyethoxy)ethyl group, 2-(methacryloyloxyethoxy)ethyl group, 3-(3-acryloyloxypropoxy)propyl group, 3-(3 -methacryloyloxypropoxy)propyl group.
２．３−ビス（アクリロイルオキシ）プロピル基。2.3-bis(acryloyloxy)propyl group.
２．３−ヒス（メタクリロイルオキシ）プロピル基等が
挙げられる。Examples include 2,3-his(methacryloyloxy)propyl group.
一般式（Ｉ）で表される。３−ハロ−４−ヒドロキシ安
息香酸誘導体の具体例としては、３−クロロ−４−ヒド
ロキシ安息香酸アクリロイルオキンエチルエステル ３
−クロロ−４−ヒドロキシ安息香酸メタクリロイルオキ
ノエチルエステル３−クロロ−４−ヒドロキシ安息香酸
（３−アクリロイルオキシプロピル）エステル、３−ク
ロロ−４−ヒドロキシ安息香酸（３−メタクリロイルオ
キシプロピル）エステル、３−クロロ−４−ヒドロキシ
安息香酸（２−アクリロイルオキシプロピル）エステル
、３−クロロ−４−ヒドロキシ安息香酸（２−メタクリ
ロイルオキシプロピル）エステル、３−クロロ−４−ヒ
ドロキシ安息香酸（４−アクリロイルオキシブチル）エ
ステル、３−クロロ−４−ヒドロキシ安息香酸（４−メ
タクリロイルオキシブチル）エステル、３−クロロ−４
−ヒドロキシ安息香酸（６−アクリロイルオキシヘキシ
ル）エステル、３−クロロ−４−ヒドロキシ安息香酸（
６−メタクリロイルオキシヘキシル）エステル、３−ク
ロロ−４−ヒドロキシ安息香酸（８−アクリロイルオキ
シオクチル）エステル、３−クロロ−４−ヒドロキシ安
息香酸（１０メタクリロイルオキシデシル）エステル、
３−クロロ−４−ヒドロキシ安息香酸〔４−（アクリロ
イルオキシメチル）ベンジルコエステル、３−クロロ−
４−ヒドロキシ安息香酸〔３−（メタクリロイルオキシ
メチル）ベンジル基〕エステル３−クロロ−４−ヒドロ
キシ安息香酸〔２−（メタクリロイルオキシメチル）ヘ
ンシル基〕エステル、３−クロロ−４−ヒドロキシ安息
香酸〔２（アクリロイルオキシエトキシ）エチル〕エス
テル、３−クロロ−４−ヒドロキシ安息香酸〔２−（メ
タクリロイルオキシエトキシ）エチル〕エステル、３−
クロロ−４−ヒドロキシ安息香酸〔３−（３−アクリロ
イルオキシプロポキシ）プロピル〕エステル、３−クロ
ロ−４−ヒドロキソ安息香酸［３−（３−メタクリロイ
ルオキシプロポキシ）プロピル〕エステル、３−り四ロ
ー４−ヒドロキシ安息香酸〔２，３−ヒス（メタクリロ
イルオキシ）プロピル〕ニステルル基、３−ブロモ４−
ヒドロキシ安息香酸（３−メタクリロイルオキシプロピ
ル）エステル、３−フロロ−４−ヒドロキシ安息香酸（
３−メタクリロイルオキシプロピル）エステル、等か挙
げられる
上記一般式（ＩＩ）中、Ｚは、炭素原子数２〜１８のヒ
ドロキシアルキル基か好ましく、具体的には、一般式（
１）においてＲて表される置換基の具体例で挙げたもの
からアクリロイル基又はメタクリロイル基を除いたヒド
ロキシアルキル基が挙げられる。It is represented by general formula (I). Specific examples of 3-halo-4-hydroxybenzoic acid derivatives include 3-chloro-4-hydroxybenzoic acid acryloyl oxine ethyl ester 3
-Chloro-4-hydroxybenzoic acid methacryloyl oxinoethyl ester 3-chloro-4-hydroxybenzoic acid (3-acryloyloxypropyl) ester, 3-chloro-4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, 3- Chloro-4-hydroxybenzoic acid (2-acryloyloxypropyl) ester, 3-chloro-4-hydroxybenzoic acid (2-methacryloyloxypropyl) ester, 3-chloro-4-hydroxybenzoic acid (4-acryloyloxybutyl) ester ester, 3-chloro-4-hydroxybenzoic acid (4-methacryloyloxybutyl) ester, 3-chloro-4
-Hydroxybenzoic acid (6-acryloyloxyhexyl) ester, 3-chloro-4-hydroxybenzoic acid (
6-methacryloyloxyhexyl) ester, 3-chloro-4-hydroxybenzoic acid (8-acryloyloxyoctyl) ester, 3-chloro-4-hydroxybenzoic acid (10 methacryloyloxydecyl) ester,
3-chloro-4-hydroxybenzoic acid [4-(acryloyloxymethyl)benzyl coester, 3-chloro-
4-Hydroxybenzoic acid [3-(methacryloyloxymethyl)benzyl group] ester 3-chloro-4-hydroxybenzoic acid [2-(methacryloyloxymethyl)hensyl group] ester, 3-chloro-4-hydroxybenzoic acid [2 (acryloyloxyethoxy)ethyl] ester, 3-chloro-4-hydroxybenzoic acid [2-(methacryloyloxyethoxy)ethyl]ester, 3-
Chloro-4-hydroxybenzoic acid [3-(3-acryloyloxypropoxy)propyl] ester, 3-chloro-4-hydroxobenzoic acid [3-(3-methacryloyloxypropoxy)propyl] ester, 3-di-4-4 -Hydroxybenzoic acid [2,3-his(methacryloyloxy)propyl] nisteryl group, 3-bromo4-
Hydroxybenzoic acid (3-methacryloyloxypropyl) ester, 3-fluoro-4-hydroxybenzoic acid (
3-methacryloyloxypropyl) ester, Z is preferably a hydroxyalkyl group having 2 to 18 carbon atoms, and specifically, Z is a hydroxyalkyl group having 2 to 18 carbon atoms.
Specific examples of the substituent represented by R in 1) include hydroxyalkyl groups excluding the acryloyl group or methacryloyl group.
本発明に係わる製造方法には、アルコール性水酸基をア
クリロイル化またはメタクリロイル化する第一の方法と
１重合性基を有するヒドロキシ安息香酸をハロゲン化す
る第二の方法かあるか、いずれも高収率で目的物か得ら
れ、簡便て精製も容易なものである
本発明に係わる第一の製造方法では、極性溶媒を使用す
ることか好ましく、溶媒としては、ニトリル系溶媒、ハ
ロゲン化炭化水素、エーテル、アミド系溶媒、ケトン系
溶媒等か好ましい、たとえば、アセトニトリル、塩化メ
チレン、クロロホルム１．テトラヒドロフラン、ジオキ
サン、 Ｎ、 Ｎ−ジメチルアセトアミド、Ｎ−メチル
ピロリドン等か好ましい 又これらの溶媒に非極性溶
媒を併用してもよい。The production method according to the present invention includes a first method of acryloylating or methacryloylating an alcoholic hydroxyl group and a second method of halogenating a hydroxybenzoic acid having a monopolymerizable group, both of which have high yields. In the first production method according to the present invention, which is simple and easy to purify, it is preferable to use a polar solvent, and examples of the solvent include nitrile solvents, halogenated hydrocarbons, and ethers. , amide-based solvents, ketone-based solvents, etc. are preferred; for example, acetonitrile, methylene chloride, chloroform; 1. Tetrahydrofuran, dioxane, N,N-dimethylacetamide, N-methylpyrrolidone and the like are preferred.A nonpolar solvent may also be used in combination with these solvents.
本発明に係わる第一の製造方法においては、脱酸剤を併
用してもよく、脱酸剤としては、アルカリ水酸化物、ア
ルカリ炭酸化物、アルカリ水素炭酸化物等の無機塩基ま
たは、トリアルキルアミン。In the first production method according to the present invention, a deoxidizing agent may be used in combination, and examples of the deoxidizing agent include inorganic bases such as alkali hydroxides, alkali carbonates, and alkali hydrogen carbonates, or trialkylamines. .
Ｎ、Ｎジアルキルアニリン誘導体、ピリジン誘導体、３
級アミド誘導体等の有機塩基があげられるか、３級アミ
ド誘導体の併用が特に好ましい、好ましい脱酸剤の例と
しては、Ｎ、Ｎ−ジメチルアセトアミド、Ｎ−メチルピ
ロリドン、Ｎ−メチルモルホリン、Ｎ、Ｎ−ジエチルア
セトアミド、Ｎ１Ｎ−ジメチルプロピオアミド、テトラ
メチルウレア、テトラエチルウレア、Ｎメチルアセトア
ニリド、Ｎ、Ｎ−ジメチルアニリン、Ｎ、Ｎ−ジメチル
アニシジン、ピリジン、２−メチルビリジン等、か挙げ
られる。これら脱酸剤は、溶媒として使用しても差支え
ない
本発明に係わる第一の製造方法を実施する際には、−儀
式（ｎ）で表される化合物１．０モルに対して、アクリ
ル酸クロリド又はメタクリル酸クロリドを１．０〜１０
．０当量使用することか好ましく、特には１０〜３．０
当量使用することか好ましい、脱酸剤を併用する場合は
、脱酸剤の使用量は、アクリル酸クロリド又はメタクリ
ル酸クロリドの使用量に対して、１０当量以上使用する
事か好ましい。N, N dialkylaniline derivative, pyridine derivative, 3
Examples of preferred deoxidizing agents include organic bases such as tertiary amide derivatives, and combinations of tertiary amide derivatives are particularly preferred. Examples include N-diethylacetamide, N1N-dimethylpropioamide, tetramethylurea, tetraethylurea, Nmethylacetanilide, N,N-dimethylaniline, N,N-dimethylanisidine, pyridine, and 2-methylpyridine. These deoxidizing agents may be used as a solvent when carrying out the first production method according to the present invention. Chloride or methacrylic acid chloride from 1.0 to 10
．． It is preferable to use 0 equivalent, especially 10 to 3.0
It is preferable to use an equivalent amount. When a deoxidizing agent is used in combination, the amount of deoxidizing agent used is preferably 10 equivalents or more relative to the amount of acrylic acid chloride or methacrylic acid chloride used.
本発明に係わる第一の製造方法を実施する際の反応温度
は、−ｉｏ’ｃ〜１００°Ｃか好ましく特に５６Ｃ〜５
０°Ｃか好ましい。The reaction temperature when carrying out the first production method according to the present invention is -io'c to 100°C, preferably 56 to 56°C.
0°C is preferable.
本発明に係わる第一の製造方法において使用する一般式
（Ｕ）で表されるアルコール性水酸基を有する３−ハロ
−４−ヒドロキシ安息香酸誘導体は、３−ハロ−４−ヒ
ドロキシ安息香酸のノへ口アルコールによるエステル化
または ３−／Ｓロー４−ヒドロキシ安息香酸の低級ア
ルキルエステルとアルキレンジオールのエステル交換反
応により得られる
本発明に係わる第二の製造方法は、溶媒を使用して実施
されることか好ましく、溶媒としては。The 3-halo-4-hydroxybenzoic acid derivative having an alcoholic hydroxyl group represented by the general formula (U) used in the first production method according to the present invention is a derivative of 3-halo-4-hydroxybenzoic acid. The second production method according to the present invention, which is obtained by esterification with alcohol or transesterification of lower alkyl ester of 3-/S rho-4-hydroxybenzoic acid and alkylene diol, is carried out using a solvent. is preferred as a solvent.
芳香族炭化水素、ハロゲン化炭化水素、エーテル。Aromatic hydrocarbons, halogenated hydrocarbons, ethers.
脂肪酸等が好ましい たとえは、ベンセン、トルエン、
塩化メチレン、クロロホルム、ジクロロエタン、メチル
クロロホルム、テトラヒドロフランジオキサン、酢酸等
か好ましい。Fatty acids, etc. are preferred; examples include benzene, toluene,
Preferred are methylene chloride, chloroform, dichloroethane, methyl chloroform, tetrahydrofuran dioxane, acetic acid and the like.
本発明に係わる第二の製造方法に使用するハロゲン化剤
は、芳香族化合物のハロゲン化に使用する一般的なハロ
ゲン化剤かあげられ１例えば新実験化学講座（丸善）１
４巻３０７ページ〜４５０ページに記載されている。ハ
ロゲン化剤の好ましい例としては、塩素、臭素、塩化ス
ルフリル、Ｎ−クロロサクシイミド、Ｎ−ブロモサクシ
イミド等が挙げられる。The halogenating agent used in the second production method according to the present invention includes general halogenating agents used for halogenating aromatic compounds.For example, Shin Experimental Chemistry Course (Maruzen) 1
It is described in Volume 4, pages 307 to 450. Preferred examples of the halogenating agent include chlorine, bromine, sulfuryl chloride, N-chlorosuccinimide, N-bromosuccimide, and the like.
本発明に係わる第二の製造方法を実施する際の反応温度
は、−１０°Ｃ〜１００°Ｃが好ましく。The reaction temperature when carrying out the second production method according to the present invention is preferably -10°C to 100°C.
特に５°Ｃ〜５０°Ｃか好ましい
本発明に係わる第二の製造方法において使用する一般式
（Ｉ［［）で表される重合性基を有する４−ヒドロキシ
安息香酸誘導体は、公知の方法により容易に得られる。The 4-hydroxybenzoic acid derivative having a polymerizable group represented by the general formula (I easily obtained.
（実施例−１）
３−クロロ−４−ヒドロキシ安息香酸（３−ヒドロキシ
プロピル）エステル２３ｇのアセトニトリル１００ｍ１
の溶液に、攪拌下、Ｎ−メチルピロリドン２０ｍ１を加
え、更にメタクリル酸クロリド１６ｇを加えた さらに
攪拌しなから３０゜Ｃで８時間反応させた９反応混合物
を水にあけ析出した結晶を濾取し、酢酸エチル／ｎ ／
＼キサンから再結晶し、３−クロロ−４−ヒドロキシ安
息香酸（３−メタクリロイルオキシプロピル）エステル
（融点５１〜５２°Ｃ）を得た。(Example-1) 23 g of 3-chloro-4-hydroxybenzoic acid (3-hydroxypropyl) ester in 100 ml of acetonitrile
To the solution, 20 ml of N-methylpyrrolidone was added under stirring, and then 16 g of methacrylic acid chloride was added.9 The reaction mixture was allowed to react at 30°C for 8 hours without further stirring.9 The reaction mixture was poured into water and the precipitated crystals were collected by filtration. and ethyl acetate/n/
Recrystallization from xane gave 3-chloro-4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester (melting point 51-52°C).
（実施例−２）
３−クロロ−４−ヒドロキシ安息香酸（２−ヒドロキシ
エチル）エステル２１ｇのアセトニトリル１００ｍ１の
溶液に、攪拌下、Ｎ、Ｎジメチルアセトアミド２０ｍ１
を加え、更にメタクリル酸クロリド２０ｇを加えた さ
らに攪拌しなから３０°Ｃて８時間反応させた 反応混
合物を重曹水中にあけ、析出した結晶を濾取し、酢酸エ
チル／ｎ−へキサンから再結晶し、３−クロロ−４−ヒ
ドロキシ安息香酸（２−メタクリロイルオキシエチル）
エステル（融点７６〜７８°Ｃ）を得た。(Example-2) 20 ml of N,N dimethylacetamide was added to a solution of 21 g of 3-chloro-4-hydroxybenzoic acid (2-hydroxyethyl) ester in 100 ml of acetonitrile while stirring.
and 20 g of methacrylic acid chloride were further added. The reaction mixture was further stirred at 30°C for 8 hours. The reaction mixture was poured into aqueous sodium bicarbonate solution, and the precipitated crystals were collected by filtration and reconstituted with ethyl acetate/n-hexane. Crystallizes into 3-chloro-4-hydroxybenzoic acid (2-methacryloyloxyethyl)
An ester (melting point 76-78°C) was obtained.
（実施例−３）
脱酸剤としてテトラメチルウレアを使用した他は、実施
例−２と同様にして反応を行い３−クロロ−４−ヒドロ
キシ安息香酸（２−メタクリロイルオキシエチル）エス
テルを得た
（実施例−４）
３−クロロ−４−ヒドロキソ安息香酸（２−メタクリロ
イルオキシプロピル）エステル２６ｇのＮＮンメチルア
セトアミト１００ｍ］の溶液に、攪拌下、メタクリル酸
クロリド２０ｇを加えた。さらに攪拌しなから３５°Ｃ
て６時間反応させた。(Example 3) The reaction was carried out in the same manner as in Example 2, except that tetramethylurea was used as a deoxidizing agent, and 3-chloro-4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester was obtained. (Example 4) 20 g of methacrylic acid chloride was added to a solution of 26 g of 3-chloro-4-hydroxobenzoic acid (2-methacryloyloxypropyl) ester and 100 m of NN-methylacetamide under stirring. 35°C without stirring further.
The mixture was allowed to react for 6 hours.
反応混合物を水にあけ、ｌ！′￥酸エチルて抽出し、酢
酸エチルを減圧留去し、３−クロロ−４−ヒドロキシ安
、＠、香酸（２−メタクリロイルオキシプロピル）エス
テル（液状、純度９７％）を得た。The reaction mixture was poured into water and l! The extract was extracted with ethyl acetate, and the ethyl acetate was distilled off under reduced pressure to obtain 3-chloro-4-hydroxyammonium, fragrant (2-methacryloyloxypropyl) ester (liquid, purity 97%).
（実施例５〜１０） 同様にして以下の化合物を得た。(Examples 5 to 10) The following compounds were obtained in the same manner.
３−クロロ−４−ヒドロキシ安、＠、香酸（４−メタク
リロイルオキシブチル）エステル（融点６２〜６４°Ｃ
）、３−クロロ−４−ヒドロキシ安息香酸（３−アクリ
ロイルオキシエチル）エステル（液状）、３−クロロ−
４−ヒドロキシ安息香酸（６−メタクリロイルオキシヘ
キシル）エステル（融点５６〜５９°Ｃ）、３−クロロ
−４−ヒドロキシ安息香酸（８−アクリロイルオキシオ
クチル）エステル（液状）、３−クロロ−４−ヒドロキ
ノ安息香酸（２，３−ビスアクリロイルオキシプロピル
）エステル（液状）、３−クロロ−４−ヒドロキシ安息
香酸（２−アクリロイルオキシエチル）エステル（融点
４７〜５０°Ｃ）（実施例−１１）
４−ヒドロキソ安息香酸（２−メタクリロイルオキシエ
チル）エステル２６ｇのテトラヒドロフラン８０ｍ１の
溶液に、攪拌下、塩化スルフリノし１１ｍｌを１反応温
度を２０〜２５°Ｃにコントロールし、なから０．５時
間かけて加えた。さらに攪拌しながら２５０Ｃで２時間
反応させた３反応混合物を水にあけ、析出した結晶をろ
取扱、酢酸エチル／ｎ−へキサンを溶媒として再結晶を
行シ）。3-Chloro-4-hydroxyamne, @, fragrant acid (4-methacryloyloxybutyl) ester (melting point 62-64°C
), 3-chloro-4-hydroxybenzoic acid (3-acryloyloxyethyl) ester (liquid), 3-chloro-
4-Hydroxybenzoic acid (6-methacryloyloxyhexyl) ester (melting point 56-59°C), 3-chloro-4-hydroxybenzoic acid (8-acryloyloxyoctyl) ester (liquid), 3-chloro-4-hydroquino Benzoic acid (2,3-bisacryloyloxypropyl) ester (liquid), 3-chloro-4-hydroxybenzoic acid (2-acryloyloxyethyl) ester (melting point 47-50°C) (Example-11) 4- To a solution of 26 g of hydroxobenzoic acid (2-methacryloyloxyethyl) ester in 80 ml of tetrahydrofuran, 11 ml of sulfurinochloride was added under stirring over 0.5 hour while controlling the reaction temperature at 20 to 25°C. . The reaction mixture was reacted at 250C for 2 hours with further stirring, then poured into water, and the precipitated crystals were collected by filtration and recrystallized using ethyl acetate/n-hexane as a solvent.
３−クロロ−４−ヒドロキシ安息香酸（２−メタクリロ
イルオキシエチル）エステルを得た。3-chloro-4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester was obtained.
（実施例−１２）
４−ヒドロキソ安、け香酸（３−メタクリロイルオキシ
プロピル）エステル２７ｇの塩化メチレン］００ｒｎｌ
の溶液に、攪拌下、塩化スルフリル】１ｍｌを１反応温
度を２０〜２５°Ｃにコントロールしながら０．５時間
かけて加えた６ さらに攪拌しなから２５°Ｃて２時間
反応させた１反応温合物を水にあけ、塩化メチレン層を
分液後塩化メチレンを留去し、３−クロロ−４−ヒドロ
キシ安息香酸（３−メタクリロイルオキシプロピル）エ
ステルを得た。(Example-12) 27 g of 4-hydroxoben, sulfuric acid (3-methacryloyloxypropyl) ester of methylene chloride] 00rnl
1 ml of sulfuryl chloride was added over 0.5 hours while stirring the reaction temperature at 20 to 25°C to a solution of 6. 1 reaction was carried out for 2 hours at 25°C without stirring. The warm mixture was poured into water, the methylene chloride layer was separated, and the methylene chloride was distilled off to obtain 3-chloro-4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester.
Claims (1)
−ハロ−４−ヒドロキシ安息香酸誘導体。 ▲数式、化学式、表等があります▼（ I ） 〔上式中、Ｘはハロゲン原子を、Ｒはアクリロイルオキ
シアルキル基またはメタクリロイルオキシアルキル基を
表す。〕 ２）下記一般式（II）で表されるアルコール性水酸基を
有する３−ハロ−４−ヒドロキシ安息香酸誘導体とアク
リル酸またはメタクリル酸ハライドを、極性溶媒中で反
応させることを特徴とする一般式（ I ）で表される重
合性基を有する３−ハロ−４−ヒドロキシ安息香酸誘導
体の製造方法。 ▲数式、化学式、表等があります▼（II） 〔上記一般式（II）中、Ｘはハロゲン原子を、Ｚは、ヒ
ドロキシアルキル基を表す。〕 ３）下記一般式（III）で表される重合性基を有する４
−ヒドロキシ安息香酸誘導体をハロゲン化剤の存在下に
ハロゲン化させることを特徴とする一般式（ I ）で表
される重合性基を有する３−ハロ−４−ヒドロキシ安息
香酸誘導体の製造方法▲数式、化学式、表等があります
▼（III） 〔上記一般式（III）中、Ｒはアクリロイルオキシアル
キル基またはメタクリロイルオキシアルキル基を表す。 〕[Claims] 1) 3 having a polymerizable group represented by the following general formula (I)
-Halo-4-hydroxybenzoic acid derivatives. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the above formula, X represents a halogen atom, and R represents an acryloyloxyalkyl group or a methacryloyloxyalkyl group. ] 2) A general formula characterized by reacting a 3-halo-4-hydroxybenzoic acid derivative having an alcoholic hydroxyl group represented by the following general formula (II) with acrylic acid or methacrylic acid halide in a polar solvent. A method for producing a 3-halo-4-hydroxybenzoic acid derivative having a polymerizable group represented by (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) [In the above general formula (II), X represents a halogen atom and Z represents a hydroxyalkyl group. ] 3) 4 having a polymerizable group represented by the following general formula (III)
- A method for producing a 3-halo-4-hydroxybenzoic acid derivative having a polymerizable group represented by general formula (I), which comprises halogenating a hydroxybenzoic acid derivative in the presence of a halogenating agent ▲Math. , chemical formulas, tables, etc. ▼ (III) [In the above general formula (III), R represents an acryloyloxyalkyl group or a methacryloyloxyalkyl group. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27356490A JPH0832663B2 (en) | 1990-10-12 | 1990-10-12 | Hydroxybenzoic acid derivative having polymerizable group and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27356490A JPH0832663B2 (en) | 1990-10-12 | 1990-10-12 | Hydroxybenzoic acid derivative having polymerizable group and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04149155A true JPH04149155A (en) | 1992-05-22 |
| JPH0832663B2 JPH0832663B2 (en) | 1996-03-29 |
Family
ID=17529563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27356490A Expired - Lifetime JPH0832663B2 (en) | 1990-10-12 | 1990-10-12 | Hydroxybenzoic acid derivative having polymerizable group and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0832663B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9469941B2 (en) | 2011-07-01 | 2016-10-18 | Empire Technology Development Llc | Paraben derivatives for preserving cellulosic materials |
-
1990
- 1990-10-12 JP JP27356490A patent/JPH0832663B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9469941B2 (en) | 2011-07-01 | 2016-10-18 | Empire Technology Development Llc | Paraben derivatives for preserving cellulosic materials |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0832663B2 (en) | 1996-03-29 |
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