JPS63227542A - Production of 4-hydroxyphenylpropionic acid compound or ester thereof - Google Patents
Production of 4-hydroxyphenylpropionic acid compound or ester thereofInfo
- Publication number
- JPS63227542A JPS63227542A JP62062214A JP6221487A JPS63227542A JP S63227542 A JPS63227542 A JP S63227542A JP 62062214 A JP62062214 A JP 62062214A JP 6221487 A JP6221487 A JP 6221487A JP S63227542 A JPS63227542 A JP S63227542A
- Authority
- JP
- Japan
- Prior art keywords
- ester
- acid
- hydroxyphenyl
- butyl
- tert
- 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
- 150000002148 esters Chemical class 0.000 title claims abstract description 10
- -1 4-hydroxyphenylpropionic acid compound Chemical class 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000000126 substance Substances 0.000 claims abstract description 7
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000006208 butylation Effects 0.000 claims description 2
- 238000007429 general method Methods 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 238000009835 boiling Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 abstract 2
- 235000019260 propionic acid Nutrition 0.000 abstract 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical class OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 2
- NGSWKAQJJWESNS-UHFFFAOYSA-N 4-coumaric acid Chemical compound OC(=O)C=CC1=CC=C(O)C=C1 NGSWKAQJJWESNS-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- PXMJCECEFTYEKE-UHFFFAOYSA-N Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-, methyl ester Chemical compound COC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PXMJCECEFTYEKE-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 208000008469 Peptic Ulcer Diseases 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- FHRSHSOEWXUORL-HDJSIYSDSA-N cetraxate Chemical compound C1C[C@@H](C[NH3+])CC[C@@H]1C(=O)OC1=CC=C(CCC([O-])=O)C=C1 FHRSHSOEWXUORL-HDJSIYSDSA-N 0.000 description 1
- 229950009533 cetraxate Drugs 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- VRWWGVRLFPQBSZ-UHFFFAOYSA-N methyl 2-(3-tert-butyl-4-hydroxyphenyl)propanoate Chemical compound COC(=O)C(C)C1=CC=C(O)C(C(C)(C)C)=C1 VRWWGVRLFPQBSZ-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- XFBPLFFEZVVMDA-UHFFFAOYSA-N octadecyl 3-(3-tert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC=C(O)C(C(C)(C)C)=C1 XFBPLFFEZVVMDA-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は工業上有用な４−ヒドロキシフェニルプロピオ
ン酸化合物またはそのエステルの製法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing an industrially useful 4-hydroxyphenylpropionic acid compound or its ester.
４−ヒドロキシフェニルプロピオン酸化合物またはその
エステルは医薬品および酸化防止剤などの工業薬品の合
成中間体として有用であり、たとえば４−ヒドロキシフ
ェニルプロピオン酸は消化性潰瘍薬剤であるセトラキサ
ートの原料として利用されている。これらの化合物のう
ち、４−ヒドロキシフェニルプロピオン酸は、ケミカル
アブストラクツ第９４巻第２１号１７４７８２ｎによる
と、４−ヒドロキシベンズアルデヒドとマロン酸とを縮
合させて得られた４−ヒドロキシ桂皮酸を還元反応に付
すことにより、また、３−第三級ブチル−４−ヒドロキ
シプロピオン酸メチルの場合には特公昭４６−７９３３
号公報に記載されている方法と同様である、２−第三級
ブチルフェノール、水酸化ナトリウムおよびジメチルス
ルホキシドの混合液中に、窒素置換下アクリル酸メチル
を滴下して反応させることにより製造されることが−２
＝
知られている。4-Hydroxyphenylpropionic acid compounds or their esters are useful as synthetic intermediates for pharmaceuticals and industrial chemicals such as antioxidants. For example, 4-hydroxyphenylpropionic acid is used as a raw material for cetraxate, a drug for peptic ulcers. There is. Among these compounds, 4-hydroxyphenylpropionic acid reduces 4-hydroxycinnamic acid obtained by condensing 4-hydroxybenzaldehyde and malonic acid, according to Chemical Abstracts Vol. 94, No. 21, 174782n. By subjecting it to a reaction, in the case of methyl 3-tertiary butyl-4-hydroxypropionate, Japanese Patent Publication No. 46-7933
It is produced by dropping methyl acrylate into a mixed solution of 2-tertiary butylphenol, sodium hydroxide and dimethyl sulfoxide under nitrogen substitution, which is similar to the method described in the above publication. ga-2
= known.
しかしながら、上記ケミカルアブストラクッに記載の方
法では使用する原料価格が高く、また還元反応などの複
雑な工程を含んでいることから、目的物を高純度、高収
率で得ることは容易なことではない。また、３−第三級
ブチル−４−ヒドロキシフェニルプロピオン酸メチルの
製造に当たっても、原料の２−第三級ブチルフェノール
の価格が高いこととあわせて、水酸基の他方のオルト位
が無置換であるため、反応物の純度が悪く、精製が容易
ではない。However, since the method described in the chemical abstract above requires high raw material prices and involves complicated steps such as reduction reactions, it is not easy to obtain the target product with high purity and high yield. isn't it. In addition, in the production of methyl 3-tert-butyl-4-hydroxyphenylpropionate, in addition to the high price of the raw material 2-tert-butylphenol, the other ortho position of the hydroxyl group is unsubstituted. , the purity of the reactant is poor and purification is not easy.
このように、４−ヒドロキシフェニルプロピオン酸化合
物およびそのエステルの従来の製造方法は満足すべき方
法ではない。Thus, conventional methods for producing 4-hydroxyphenylpropionic acid compounds and their esters are not satisfactory.
そこで、本発明者等は上記従来法の問題点を解決すべく
、鋭意検討を重ねた結果、容易に、かつ経済的に高純度
の４−ヒドロキシフェニルプロピオン酸化合物またはそ
のエステルが得られるという方法を見出し、本発明を完
成するに至った。すなわち、本発明は、３− （３，５
−ジ第三級ブチル−４−ヒドロキシフェニル）プロピオ
ン酸またはそのエステルを酸性物質の存在下に脱第三級
ブチル化を行なうことを特徴とする一般式〔式中、Ｒ１
は水素または第三級ブチルを、Ｒ２は水素またはアルキ
ル（メチル、エチル、プロピル、イソプロピル、ブチル
、イソブチル、第三級ブチル、ペンチル、イソペンチル
、ネオペンチル、ヘキシル、ペプチル、オクチル、２−
エチルヘキシル、１，１，４．４−テトラメチルブチル
、ノニル、デシル、ドデシル、テトラデシル、ヘキサデ
シル、オクタデシル、エイコシル、トコシルなどの炭素
数１〜２２個の直鎖または、分枝鎖状のアルキルが望ま
しい。）を示す。〕
で表わされる４−ヒドロキシフェニルプロピオン酸化合
物またはそのエステルの製法に関する。Therefore, in order to solve the problems of the above-mentioned conventional methods, the present inventors have made extensive studies and have found a method that can easily and economically obtain a highly purified 4-hydroxyphenylpropionic acid compound or its ester. They discovered this and completed the present invention. That is, the present invention provides 3-(3,5
-ditertiary butyl-4-hydroxyphenyl)propionic acid or its ester is subjected to detertiary butylation in the presence of an acidic substance [in the formula, R1
is hydrogen or tertiary butyl, R2 is hydrogen or alkyl (methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, peptyl, octyl, 2-
Straight chain or branched alkyl having 1 to 22 carbon atoms such as ethylhexyl, 1,1,4.4-tetramethylbutyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, and tocosyl are preferable. . ) is shown. ] It is related with the manufacturing method of the 4-hydroxyphenylpropionic acid compound or its ester represented by these.
用いられる酸性物質としては、硫酸、塩酸、過塩素酸の
ような無機酸およびベンゼンスルホン酸、パラトルエン
スルホン酸、トリフルオロ酢酸のような有機酸などがあ
げられる。The acidic substances used include inorganic acids such as sulfuric acid, hydrochloric acid, and perchloric acid, and organic acids such as benzenesulfonic acid, paratoluenesulfonic acid, and trifluoroacetic acid.
反応は、適当な溶媒（ベンゼン、トルエン、クロロホル
ム、ジクロロエタン等）中、冷却下または室温から用い
る溶媒の沸点までの温度で３０分から２４時間で進行す
る。得られた目的物は再結晶法、クロマトグラフィー法
などの通常の手段で精製することができる。The reaction proceeds in a suitable solvent (benzene, toluene, chloroform, dichloroethane, etc.) under cooling or at a temperature from room temperature to the boiling point of the solvent used for 30 minutes to 24 hours. The obtained target product can be purified by conventional means such as recrystallization and chromatography.
本発明方法によると、入手しやすい原料化合物を用いて
おり、反応自体も容易であり、また目的物も高純度に得
られるため、従来法に比ベニ業上極めて経済的な方法で
あり、有利である。According to the method of the present invention, readily available starting compounds are used, the reaction itself is easy, and the target product can be obtained with high purity, so it is extremely economical and advantageous compared to conventional methods. It is.
以下、実施例により本発明を具体的に説明するが、本発
明はこれらに限定されないことは言うまでもない。EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but it goes without saying that the present invention is not limited thereto.
実施例１
冷却器および温度針を付した５００ｍ１四日フラスコに
３− （３，５−ジ第三級ブチル−４−ヒドロキシフェ
ニル）プロピオン酸メチルエステル１００ｇ５？！硫酸
１２ｇ、トルエン２５０ｇおよびメタノール５０ｇを仕
込み、還流条件で１２時間攪拌した。反応終了後、反応
液に２０％水酸化ナトリウム水溶液１００ｇを投入し、
激しく攪拌した後、分液を行なった。この操作を２度行
ない、２回分の水層に３５％塩酸８０ｇを投入した。そ
の後、水層からメチルイソブチルケトン２００ｍ１で２
回抽出を行ない、メチルイソブチルケトン層を１回水洗
後濃縮した。残金をトルエンで洗浄し、濾過後乾燥し、
融点１２９〜１３１℃の白色結晶である、３−（４−ヒ
ドロキシフェニル）プロピオン酸３４ｇ（収率６０％）
を得た。Example 1 100 g of 3-(3,5-ditert-butyl-4-hydroxyphenyl)propionic acid methyl ester was placed in a 500 m1 four-day flask equipped with a condenser and a temperature needle. ! 12 g of sulfuric acid, 250 g of toluene, and 50 g of methanol were charged, and the mixture was stirred under reflux conditions for 12 hours. After the reaction was completed, 100 g of a 20% aqueous sodium hydroxide solution was added to the reaction solution.
After vigorous stirring, liquid separation was performed. This operation was repeated twice, and 80 g of 35% hydrochloric acid was added to the aqueous layer for the second time. Then, from the aqueous layer, 200 ml of methyl isobutyl ketone was added.
Extraction was performed twice, and the methyl isobutyl ketone layer was washed once with water and then concentrated. The remaining residue was washed with toluene, filtered, and dried.
34 g of 3-(4-hydroxyphenyl)propionic acid (yield: 60%), white crystals with a melting point of 129-131°C
I got it.
実施例２
冷却器および温度計を付したＩＩｌ四日フラスコ＝ ６
−
に、３−（３，５−ジ第三級ブチル−４−ヒドロキシフ
ェニル）プロピオン酸メチル５００ ｇ、濃硫酸２５ｇ
およびトルエン３００ｍ１を仕込み、還流条件で２時間
半攪拌した。Example 2 IIl four-day flask with condenser and thermometer = 6
- 500 g of methyl 3-(3,5-ditertiary-butyl-4-hydroxyphenyl)propionate, 25 g of concentrated sulfuric acid
and 300 ml of toluene were charged, and the mixture was stirred for 2.5 hours under reflux conditions.
反応終了後、水洗し、溶媒を留去した後、残金にｎ−ヘ
キサンを加え氷冷し、析出した結晶を濾過した。粗結晶
をｎ−ヘキサンから再結晶すると、融点５９〜６１℃の
白色結晶である、１（３−第三級フチル−４−ヒドロキ
シフェニル）プロピオン酸メチル２９０ｇ （収率７２
％）を得た。After the reaction was completed, the mixture was washed with water, the solvent was distilled off, n-hexane was added to the residue, the mixture was cooled on ice, and the precipitated crystals were filtered. When the crude crystals were recrystallized from n-hexane, 290 g of methyl 1(3-tertiary phthyl-4-hydroxyphenyl)propionate (yield 72
%) was obtained.
同様な方法にて、３〜（３，５−ジ第三級ブチル−４−
ヒドロ゛キシフェニル）プロピオン酸ドデシルから微淡
黄色透明な粘稠液体の３−（３−第三級ブチル−４−ヒ
ドロキスジフェニル）プロピオン酸ドデシルを得た。ま
た３−（３，５−ジ第三級ブチル−４−ヒドロキシフェ
ニル）プロピオン酸オクタデシルから、融点４３〜４５
℃白色結晶の、３−（３−第三級ブチル−４−ヒドロキ
シフェニル）プロピオン酸オクタデシルを得た。In a similar manner, 3-(3,5-di-tert-butyl-4-
From dodecyl hydroxyphenyl) propionate, dodecyl 3-(3-tert-butyl-4-hydroxydiphenyl) propionate was obtained as a pale yellow transparent viscous liquid. Also, from octadecyl 3-(3,5-ditertiary-butyl-4-hydroxyphenyl)propionate, melting point 43-45
℃ white crystals of octadecyl 3-(3-tert-butyl-4-hydroxyphenyl)propionate were obtained.
＝７−=7-
Claims (1)
ル）プロピオン酸またはそのエステルを酸性物質の存在
下に脱第三級ブチル化を行なうことを特徴とする一般式 ▲数式、化学式、表等があります▼ （式中、Ｒ＾１は水素または第三級ブチルを、Ｒ＾２は
水素またはアルキルを示す。） で表わされる４−ヒドロキシフェニルプロピオン酸化合
物またはそのエステルの製法。[Claims] A general method characterized by detertiary butylation of 3-(3,5-ditertiary butyl-4-hydroxyphenyl)propionic acid or its ester in the presence of an acidic substance. 4-Hydroxyphenylpropionic acid compound or its Production method of ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62062214A JPS63227542A (en) | 1987-03-17 | 1987-03-17 | Production of 4-hydroxyphenylpropionic acid compound or ester thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62062214A JPS63227542A (en) | 1987-03-17 | 1987-03-17 | Production of 4-hydroxyphenylpropionic acid compound or ester thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63227542A true JPS63227542A (en) | 1988-09-21 |
Family
ID=13193671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62062214A Pending JPS63227542A (en) | 1987-03-17 | 1987-03-17 | Production of 4-hydroxyphenylpropionic acid compound or ester thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63227542A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008538381A (en) * | 2005-04-19 | 2008-10-23 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | Antioxidant |
| CN107011149A (en) * | 2017-04-26 | 2017-08-04 | 哈尔滨理工大学 | The preparation method of the hydroxy phenylpropionic acid of 3 tert-butyl group 4 |
| CN111072579A (en) * | 2019-12-30 | 2020-04-28 | 利安隆（中卫）新材料有限公司 | Preparation method of 3- [3- (benzotriazole-2-yl) -4-hydroxy-5-tert-butylphenyl ] -propionic acid methyl ester |
| CN114026141A (en) * | 2019-07-03 | 2022-02-08 | Si集团有限公司 | Alkylphenol copolymers |
-
1987
- 1987-03-17 JP JP62062214A patent/JPS63227542A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008538381A (en) * | 2005-04-19 | 2008-10-23 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | Antioxidant |
| CN107011149A (en) * | 2017-04-26 | 2017-08-04 | 哈尔滨理工大学 | The preparation method of the hydroxy phenylpropionic acid of 3 tert-butyl group 4 |
| CN107011149B (en) * | 2017-04-26 | 2019-07-30 | 哈尔滨理工大学 | The preparation method of 3- tertiary butyl-4-hydroxy benzenpropanoic acid |
| CN114026141A (en) * | 2019-07-03 | 2022-02-08 | Si集团有限公司 | Alkylphenol copolymers |
| US11345846B2 (en) | 2019-07-03 | 2022-05-31 | Si Group, Inc. | Alkylphenol copolymer |
| CN111072579A (en) * | 2019-12-30 | 2020-04-28 | 利安隆（中卫）新材料有限公司 | Preparation method of 3- [3- (benzotriazole-2-yl) -4-hydroxy-5-tert-butylphenyl ] -propionic acid methyl ester |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3914286A (en) | Lower alkyl esters of p-benzoylphenoxy isobutyric acid | |
| JP3701974B2 (en) | Method for purifying 2,6-diisopropylphenol | |
| PT2152657E (en) | Process for the preparation oftrans-2,3-disubstituted naphthoquinones | |
| JPS5922711B2 (en) | Method for producing benzoxazolinone derivatives | |
| IL31082A (en) | Derivatives of heptenoic acid | |
| JPS63227542A (en) | Production of 4-hydroxyphenylpropionic acid compound or ester thereof | |
| Fry | SYNTHESES OF CYSTINE | |
| EP0169688B1 (en) | Process for preparing anti-inflammatory cycloalkylidenemethylphenylacetic acid derivatives | |
| JPH0134219B2 (en) | ||
| US3535367A (en) | Process for synthesis of 4-hydroxycyclohexanecarboxylic acid and derivatives thereof | |
| PT768296E (en) | PROCESS FOR THE PREPARATION OF CARBOXYLATES BETA-TRIFLUOROMETHYLATED ALPHA BETA.INSUBSTITUIDOS | |
| JPH01143847A (en) | Separation and purification of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid ester | |
| JP3337326B2 (en) | Process for producing bis (hydroxyaryl) pentanoic acids | |
| US4268685A (en) | Salicylamide esters and related pharmaceutical composition | |
| US3062834A (en) | Process for preparing thiophencarboxylic acids and their esters | |
| US3010992A (en) | Process for preparing serines | |
| Koelsch | An Indone to Naphthol Ring Expansion | |
| US3542849A (en) | Process for the preparation of n-aryl-alpha-amino carboxylic acid esters | |
| US3128273A (en) | 4-amino-pteridine-7-carboxamides and method of preparation | |
| US3828049A (en) | Diastereomers of alpha-hydrazino-beta-(3,4-disubstituted phenyl)alkanoic acid derivatives | |
| JPS61263950A (en) | Manufacture of 2-(4-isobutylphenyl)-propiohydroxamic acid | |
| JPS59101437A (en) | Manufacture of fluorene-9-carboxylic acid | |
| US3833573A (en) | Phenothiazine derivatives | |
| US2813895A (en) | Purification of dehydroabietylamine | |
| US3206473A (en) | Sulfolanylalkanoic acids and esters thereof |