JPH04257543A - Method for selectively esterifying phenolic derivative having alcoholic hydroxyl group - Google Patents
Method for selectively esterifying phenolic derivative having alcoholic hydroxyl groupInfo
- Publication number
- JPH04257543A JPH04257543A JP2009591A JP2009591A JPH04257543A JP H04257543 A JPH04257543 A JP H04257543A JP 2009591 A JP2009591 A JP 2009591A JP 2009591 A JP2009591 A JP 2009591A JP H04257543 A JPH04257543 A JP H04257543A
- Authority
- JP
- Japan
- Prior art keywords
- group
- alcoholic hydroxyl
- hydroxyl group
- derivative
- phenolic derivative
- 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.)
- Pending
Links
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 23
- 230000001476 alcoholic effect Effects 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title abstract 4
- 150000001408 amides Chemical class 0.000 claims abstract description 8
- 150000003672 ureas Chemical class 0.000 claims abstract description 8
- 125000001424 substituent group Chemical group 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 150000004820 halides Chemical class 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 150000002989 phenols Chemical class 0.000 claims description 10
- 230000032050 esterification Effects 0.000 claims 1
- 238000005886 esterification reaction Methods 0.000 claims 1
- -1 sulfonyloxy group Chemical group 0.000 description 32
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 3
- YCCILVSKPBXVIP-UHFFFAOYSA-N 2-(4-hydroxyphenyl)ethanol Chemical compound OCCC1=CC=C(O)C=C1 YCCILVSKPBXVIP-UHFFFAOYSA-N 0.000 description 2
- MXLVVOUBPBBRDE-UHFFFAOYSA-N 2-(4-hydroxyphenyl)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C=C1 MXLVVOUBPBBRDE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- UWHSPZZUAYSGTB-UHFFFAOYSA-N 1,1,3,3-tetraethylurea Chemical compound CCN(CC)C(=O)N(CC)CC UWHSPZZUAYSGTB-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ABFCOJLLBHXNOU-UHFFFAOYSA-N 2-(2-hydroxyphenyl)ethanol Chemical compound OCCC1=CC=CC=C1O ABFCOJLLBHXNOU-UHFFFAOYSA-N 0.000 description 1
- KPMASMMCUMAMLI-UHFFFAOYSA-N 2-[4-(2-methylprop-2-enoyloxy)phenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(OC(=O)C(C)=C)C=C1 KPMASMMCUMAMLI-UHFFFAOYSA-N 0.000 description 1
- KKOWMCYVIXBCGE-UHFFFAOYSA-N 3-(2-hydroxyethoxy)phenol Chemical compound OCCOC1=CC=CC(O)=C1 KKOWMCYVIXBCGE-UHFFFAOYSA-N 0.000 description 1
- 125000001137 3-hydroxypropoxy group Chemical group [H]OC([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- LMTGCJANOQOGPI-UHFFFAOYSA-N n-methyl-n-phenylacetamide Chemical compound CC(=O)N(C)C1=CC=CC=C1 LMTGCJANOQOGPI-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 150000003511 tertiary amides Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、合成中間体、記録材料
用電子受容性化合物として有用なアルコール性水酸基を
有するフェノール誘導体の選択的アルコール性水酸基の
エステル化方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for selectively esterifying the alcoholic hydroxyl group of a phenol derivative having an alcoholic hydroxyl group useful as a synthetic intermediate or an electron-accepting compound for recording materials.
【０００２】0002
【従来の技術】アルコール性水酸基を有するフェノール
誘導体の選択的アルコール性水酸基のエステル化方法は
種々知られており、その製造方法もいくつか知られてい
るが、収率、ハンドリングの点で満足いくものではなか
った。[Prior Art] Various methods for selectively esterifying the alcoholic hydroxyl group of phenol derivatives having an alcoholic hydroxyl group are known, and some production methods are also known, but none of them are satisfactory in terms of yield and handling. It wasn't something.
【０００３】0003
【発明が解決しようとする課題】本発明の課題は、合成
中間体、記録材料用電子受容性化合物として有用なアル
コール性水酸基を有するフェノール誘導体の選択的アル
コール性水酸基のエステル化方法を提供することである
。An object of the present invention is to provide a method for selectively esterifying the alcoholic hydroxyl group of a phenol derivative having an alcoholic hydroxyl group useful as a synthetic intermediate or an electron-accepting compound for recording materials. It is.
【０００４】0004
【課題を解決する手段】本発明は、アルコール性水酸基
を有する基を置換基として有するフェノール誘導体に酸
ハライドを、有機溶剤中、アミドまたは尿素誘導体を併
用して反応させることを特徴とするアルコール性水酸基
を有するフェノール誘導体の選択的エステル化方法から
構成される。本発明に係わるアルコール性水酸基を有す
る基を置換基として有するフェノール誘導体は、分子内
にアルコール性水酸基を有する基を置換基として有する
フェノール誘導体またはナフトール誘導体をさすが、た
とえば下記一般式（Ｉ）で表されるものが挙げられる。
一般式（Ｉ）[Means for Solving the Problems] The present invention provides an alcoholic hydroxyl group characterized in that a phenol derivative having a group having an alcoholic hydroxyl group as a substituent is reacted with an acid halide in combination with an amide or urea derivative in an organic solvent. It consists of a method for selectively esterifying phenol derivatives having hydroxyl groups. The phenol derivative having a group having an alcoholic hydroxyl group as a substituent according to the present invention refers to a phenol derivative or a naphthol derivative having a group having an alcoholic hydroxyl group as a substituent in the molecule, and for example, it is represented by the following general formula (I). Examples include things that are done. General formula (I)
【０００５】[0005]
【化１】[Chemical formula 1]
【０００６】〔上式中、Ｘはアルコール性水酸基を有す
る１価の基を表し、Ｙ、Ｚは同一でも異なっていてもよ
く、アルコール性水酸基を有する１価の基、水素原子、
ヒドロキシ基、アルキル基、アリール基、アルコキシ基
、ハロゲン原子、ニトロ基、シアノ基、アシル基、スル
ホニル基、置換アミノ基、アシルオキシ基、スルホニル
オキシ基等を表し、ＹとＺが連結して環を形成しても良
い。〕[In the above formula, X represents a monovalent group having an alcoholic hydroxyl group, Y and Z may be the same or different, and represent a monovalent group having an alcoholic hydroxyl group, a hydrogen atom,
Represents a hydroxy group, alkyl group, aryl group, alkoxy group, halogen atom, nitro group, cyano group, acyl group, sulfonyl group, substituted amino group, acyloxy group, sulfonyloxy group, etc., and Y and Z are connected to form a ring. It may be formed. ]
【０００７】上記一般式（Ｉ）中、Ｘで表されるアルコ
ール性水酸基を有する１価の基の具体例としては、ヒド
ロキシエチル基、３−ヒドロキシプロピル基、２−ヒド
ロキシプロピル基、４−ヒドロキシブチル基、６−ヒド
ロキシヘキシル基、８−ヒドロキシヘキシル基、１０−
ヒドロキシデシル基、４−（ヒドロキシメチル）ベンジ
ル基、３−（ヒドロキシメチル）ベンジル基、２−（ヒ
ドロキシメチル）ベンジル基、１２−ヒドロキシドデシ
ル基、２−（ヒドロキシエトキシ）エチル基、ヒドロキ
シエトキシ基、３−ヒドロキシプロポキシ基、４−ヒド
ロキシブトキシ基、ヒドロキシエトキシフェニル基、ヒ
ドロキシエトキシカルボニル基、４−（３−ヒドロキシ
プロポキシ）フェニル基、２−ヒドロキシエチルチオ基
、ヒドロキシエトキシフェノキシ基、４−（３−ヒドロ
キシプロポキシ）フェノキシ基、４−（３−ヒドロキシ
プロポキシ）フェニルスルホニル基、４−（２−ヒドロ
キシエトキシ）フェニルスルホニル基、α，α−ジメチ
ル−４−（２−ヒドロキシエトキシ）ベンジル基、α，
α−ジメチル−４−（３−ヒドロキシプロポキシ）ベン
ジル基、Ｎ，Ｎ−ジヒドロキシエチルアミノ基、Ｎ−メ
チル−Ｎ−ヒドロキシエチルアミノ基、Ｎ−アセチル−
Ｎ−ヒドロキシエチルアミノ基等が挙げられる。In the above general formula (I), specific examples of the monovalent group having an alcoholic hydroxyl group represented by X include hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 4-hydroxy Butyl group, 6-hydroxyhexyl group, 8-hydroxyhexyl group, 10-
Hydroxydecyl group, 4-(hydroxymethyl)benzyl group, 3-(hydroxymethyl)benzyl group, 2-(hydroxymethyl)benzyl group, 12-hydroxydodecyl group, 2-(hydroxyethoxy)ethyl group, hydroxyethoxy group, 3-hydroxypropoxy group, 4-hydroxybutoxy group, hydroxyethoxyphenyl group, hydroxyethoxycarbonyl group, 4-(3-hydroxypropoxy)phenyl group, 2-hydroxyethylthio group, hydroxyethoxyphenoxy group, 4-(3- hydroxypropoxy) phenoxy group, 4-(3-hydroxypropoxy) phenylsulfonyl group, 4-(2-hydroxyethoxy) phenylsulfonyl group, α,α-dimethyl-4-(2-hydroxyethoxy)benzyl group, α,
α-dimethyl-4-(3-hydroxypropoxy)benzyl group, N,N-dihydroxyethylamino group, N-methyl-N-hydroxyethylamino group, N-acetyl-
Examples include N-hydroxyethylamino group.
【０００８】本発明に係わる酸ハライドは、置換基を有
していても良い飽和または不飽和の脂肪酸ハライドある
いは置換基を有していても良い芳香族カルボン酸ハライ
ドであり、二塩基酸ハライドも含まれる。本発明に係わ
る製造方法は、アルコール性水酸基を選択的にアシル化
する、高収率で高純度で、精製も容易な製造方法である
。The acid halide according to the present invention is a saturated or unsaturated fatty acid halide which may have a substituent or an aromatic carboxylic acid halide which may have a substituent. included. The production method according to the present invention selectively acylates alcoholic hydroxyl groups, resulting in high yield, high purity, and easy purification.
【０００９】本発明に係わる製造方法は、有機溶媒を使
用することが好ましく、溶媒としては、ニトリル系溶媒
、ハロゲン化炭化水素系溶媒、エーテル、アミド系溶媒
、ケトン系溶媒、エステル系溶媒、芳香族炭化水素等が
好ましい。例えば、アセトニトリル、塩化メチレン、ア
セトン、クロロホルム、酢酸エチル、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、トルエン等が好ましい。[0009] The production method according to the present invention preferably uses an organic solvent, and examples of the solvent include nitrile solvents, halogenated hydrocarbon solvents, ethers, amide solvents, ketone solvents, ester solvents, and aromatic solvents. Group hydrocarbons and the like are preferred. For example, acetonitrile, methylene chloride, acetone, chloroform, ethyl acetate, tetrahydrofuran, dioxane, N,N-dimethylacetamide, N-
Methylpyrrolidone, toluene, etc. are preferred.
【００１０】本発明に係わる製造方法においては、アミ
ド誘導体または尿素誘導体を脱酸剤として併用する。ア
ミド誘導体または尿素誘導体のうち、３級アミド誘導体
または窒素原子が全て置換を有する尿素誘導体が好まし
い。好ましいアミド誘導体または尿素誘導体の例として
は、Ｎ，Ｎ，−ジメチルアセトアミド、Ｎ，Ｎ，−ジエ
チルアセトアミド、Ｎ，Ｎ，−ジメチルプロピオアミド
、Ｎ−メチルピロリドン、、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、等が挙げ
られる。これら脱酸剤は、溶媒として使用しても差し支
えない。[0010] In the production method according to the present invention, an amide derivative or a urea derivative is used in combination as a deoxidizing agent. Among the amide derivatives or urea derivatives, tertiary amide derivatives or urea derivatives in which all nitrogen atoms are substituted are preferred. Examples of preferred amide derivatives or urea derivatives include N,N,-dimethylacetamide, N,N,-diethylacetamide, N,N,-dimethylpropioamide, N-methylpyrrolidone, tetramethylurea, tetraethylurea, N-methylacetanilide, etc. are mentioned. These deoxidizing agents may be used as solvents.
【００１１】本発明に係わる製造方法を実施する際には
、一般式（Ｉ）で表される化合物１．０モルに対して、
酸ハライドを１．０〜１０．０当量使用することが好ま
しく、特には１．０〜５．０当量使用することが好まし
い。アミド誘導体または尿素誘導体は、酸ハライドの使
用量に対して１．０当量以上使用する事が好ましい。反
応温度は、−１０°Ｃ〜１００°Ｃが好ましく、特に５
°Ｃ〜５０°Ｃが好ましい。[0011] When carrying out the production method according to the present invention, for 1.0 mol of the compound represented by general formula (I),
It is preferable to use the acid halide in an amount of 1.0 to 10.0 equivalents, particularly preferably 1.0 to 5.0 equivalents. The amide derivative or urea derivative is preferably used in an amount of 1.0 equivalent or more relative to the amount of acid halide used. The reaction temperature is preferably -10°C to 100°C, especially 5°C.
°C to 50 °C is preferred.
【００１２】0012
【実施例】以下に実施例を示すが、本発明はこれに限定
されるものではない。実施例において特に指定のない限
り、重量％を表す。
実施例−１
４−（２−ヒドロキシエチル）フェノール６ｇのアセト
ニトリル２０ｍｌ溶液に、攪拌下、Ｎ−メチルピロリド
ン１０ｍｌを加え、更にメタクリル酸クロリド８ｇを加
えた。３５°Ｃで５時間、攪拌しながら反応させた後、
反応混合物を氷水にあけ、析出した結晶を濾取し、酢酸
エチル／ｎ−ヘキサンから再結晶し、４−（２−メタク
リロイルオキシエチル）フェノール（融点８７〜８９°
Ｃ）を得た。[Examples] Examples are shown below, but the present invention is not limited thereto. Unless otherwise specified in the examples, weight % is expressed. Example-1 To a solution of 6 g of 4-(2-hydroxyethyl)phenol in 20 ml of acetonitrile, 10 ml of N-methylpyrrolidone was added under stirring, and further 8 g of methacrylic acid chloride was added. After reacting at 35°C for 5 hours with stirring,
The reaction mixture was poured into ice water, the precipitated crystals were collected by filtration, and recrystallized from ethyl acetate/n-hexane to give 4-(2-methacryloyloxyethyl)phenol (melting point 87-89°).
C) was obtained.
【００１３】実施例−２
３−（２−ヒドロキシエトキシ）フェノール７．５ｇの
アセトニトリル３０ｍｌ溶液に、攪拌下、Ｎ，Ｎ−ジメ
チルアセトアミド１０ｍｌを加え、更にテレフタル酸ク
ロリド５ｇを加えた。３５°Ｃで４時間、攪拌しながら
反応させた後、反応混合物を氷水にあけ、析出した結晶
を濾取し、酢酸エチル／ｎ−ヘキサンから再結晶し、テ
レフタル酸ビス〔２−（３−ヒドロキシフェノキシ）エ
チル〕エステル（融点１３７〜１３８°Ｃ）を得た。Example 2 To a solution of 7.5 g of 3-(2-hydroxyethoxy)phenol in 30 ml of acetonitrile, 10 ml of N,N-dimethylacetamide was added under stirring, and further 5 g of terephthalic acid chloride was added. After reacting at 35°C for 4 hours with stirring, the reaction mixture was poured into ice water, and the precipitated crystals were collected by filtration and recrystallized from ethyl acetate/n-hexane to give bis[2-(3- Hydroxyphenoxy)ethyl]ester (melting point 137-138°C) was obtained.
【００１４】実施例−３
フェノール誘導体として２，２−ビス（４−ヒドロキシ
フェニル）酢酸（３−ヒドロキシプロピル）エステルを
使用した他は、実施例−１と同様にして反応を行った。
反応混合物を氷水にあけ、油状物を酢酸エチルで抽出し
、酢酸エチル層を濃縮した。この濃縮物を、高速液体ク
ロマトグラフィーで解析したところ、２，２−ビス（４
−ヒドロキシフェニル）酢酸（３−メタクリロイルオキ
シプロピル）エステルを９８％以上含有していた。Example 3 A reaction was carried out in the same manner as in Example 1, except that 2,2-bis(4-hydroxyphenyl)acetic acid (3-hydroxypropyl) ester was used as the phenol derivative. The reaction mixture was poured into ice water, the oily substance was extracted with ethyl acetate, and the ethyl acetate layer was concentrated. When this concentrate was analyzed by high performance liquid chromatography, it was found that 2,2-bis(4
-Hydroxyphenyl)acetic acid (3-methacryloyloxypropyl) ester in an amount of 98% or more.
【００１５】実施例−４
４−ヒドロキシフェニル−４’−（３−ヒドロキシプロ
ポキシ）フェニルスルホン７．５ｇのテトラヒドロフラ
ン２０ｍｌ溶液に、Ｎ−メチルピロリドン１０ｍｌを加
え、更にメタクリル酸クロリド８ｇを加えた。３０°Ｃ
で４時間、攪拌しながら反応させた後、反応混合物を重
層水にあけ、析出した結晶を濾取し、酢酸エチル／ｎ−
ヘキサンから再結晶し、４−ヒドロキシフェニル−４’
−（３−メタクリロイルオキシプロポキシ）フェニルス
ルホン（融点７３〜７６°Ｃ）を得た。Example 4 To a solution of 7.5 g of 4-hydroxyphenyl-4'-(3-hydroxypropoxy) phenylsulfone in 20 ml of tetrahydrofuran was added 10 ml of N-methylpyrrolidone, and further 8 g of methacrylic acid chloride. 30°C
After reacting with stirring for 4 hours, the reaction mixture was poured into layered water, the precipitated crystals were collected by filtration, and ethyl acetate/n-
Recrystallized from hexane, 4-hydroxyphenyl-4'
-(3-methacryloyloxypropoxy)phenylsulfone (melting point 73-76°C) was obtained.
【００１６】実施例−５〜８
同様にして以下の化合物を得た。４−ヒドロキシフェニ
ル−４’−（３−ｐ−クロロベンゾイルオキシプロポキ
シ）フェニルスルホン（融点１５２〜１５３°Ｃ）、４
−（２−ｐ−クロロベンゾイルオキシエチル）フェノー
ル（融点１０２〜１０３°Ｃ）、２，６−ビス（ｐ−ク
ロロベンゾイルオキシメチル）−４−メチルフェノール
（融点１６３〜１６６°Ｃ）、４−ビス（２−ｐ−クロ
ロベンゾイルオキシエチル）アミノフェノール（融点１
１０〜１１１°Ｃ）。Examples 5 to 8 The following compounds were obtained in the same manner. 4-hydroxyphenyl-4'-(3-p-chlorobenzoyloxypropoxy) phenyl sulfone (melting point 152-153°C), 4
-(2-p-chlorobenzoyloxyethyl)phenol (melting point 102-103°C), 2,6-bis(p-chlorobenzoyloxymethyl)-4-methylphenol (melting point 163-166°C), 4- Bis(2-p-chlorobenzoyloxyethyl)aminophenol (melting point 1
10-111°C).
【００１７】比較例
４−（２−ヒドロキシエチル）フェノール６ｇのアセト
ニトリル２０ｍｌ溶液に、メタクリル酸クロリド８ｇを
加え攪拌下、トリエチルアミン１０ｍｌをゆっくり滴下
した。滴下後３０°Ｃで５時間、攪拌しながら反応させ
た後、反応混合物を氷水にあけたが結晶は析出しなかっ
た。油状物を酢酸エチルで抽出し、酢酸エチル層を濃縮
した。この濃縮物を、高速液体クロマトグラフィーで解
析したところ、４−（２−メタクリロイルオキシエチル
）フェノールと１−（２−メタクリロイルオキシエチル
）−４−メタクリロイルオキシベンゼンの混合物である
ことが判明した。Comparative Example 4 8 g of methacrylic acid chloride was added to a solution of 6 g of (2-hydroxyethyl)phenol in 20 ml of acetonitrile, and 10 ml of triethylamine was slowly added dropwise while stirring. After the dropwise addition, the reaction mixture was stirred at 30°C for 5 hours, and then the reaction mixture was poured into ice water, but no crystals were precipitated. The oil was extracted with ethyl acetate, and the ethyl acetate layer was concentrated. When this concentrate was analyzed by high performance liquid chromatography, it was found to be a mixture of 4-(2-methacryloyloxyethyl)phenol and 1-(2-methacryloyloxyethyl)-4-methacryloyloxybenzene.
Claims (1)
基として有するフェノール誘導体に酸ハライドを、有機
溶剤中、アミドまたは尿素誘導体を併用して反応させる
ことを特徴とするアルコール性水酸基を有するフェノー
ル誘導体の選択的エステル化方法1. A method of producing a phenol derivative having an alcoholic hydroxyl group, which is characterized by reacting a phenol derivative having an alcoholic hydroxyl group as a substituent with an acid halide in an organic solvent in combination with an amide or a urea derivative. Selective esterification method
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009591A JPH04257543A (en) | 1991-02-13 | 1991-02-13 | Method for selectively esterifying phenolic derivative having alcoholic hydroxyl group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009591A JPH04257543A (en) | 1991-02-13 | 1991-02-13 | Method for selectively esterifying phenolic derivative having alcoholic hydroxyl group |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04257543A true JPH04257543A (en) | 1992-09-11 |
Family
ID=12017557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009591A Pending JPH04257543A (en) | 1991-02-13 | 1991-02-13 | Method for selectively esterifying phenolic derivative having alcoholic hydroxyl group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04257543A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7678876B2 (en) | 2004-12-02 | 2010-03-16 | Dsm Ip Assets B.V. | Hydroxy-aromatic compound, process for the preparation thereof, and use of the compound |
-
1991
- 1991-02-13 JP JP2009591A patent/JPH04257543A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7678876B2 (en) | 2004-12-02 | 2010-03-16 | Dsm Ip Assets B.V. | Hydroxy-aromatic compound, process for the preparation thereof, and use of the compound |
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