JPS5931497B2 - 2-Hydroxy-3-methyl-3-(6-methoxy-2-naphthyl)acrylonitrile compound and method for producing the same - Google Patents
2-Hydroxy-3-methyl-3-(6-methoxy-2-naphthyl)acrylonitrile compound and method for producing the sameInfo
- Publication number
- JPS5931497B2 JPS5931497B2 JP4854576A JP4854576A JPS5931497B2 JP S5931497 B2 JPS5931497 B2 JP S5931497B2 JP 4854576 A JP4854576 A JP 4854576A JP 4854576 A JP4854576 A JP 4854576A JP S5931497 B2 JPS5931497 B2 JP S5931497B2
- Authority
- JP
- Japan
- Prior art keywords
- methoxy
- naphthyl
- methyl
- hydroxy
- producing
- 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.)
- Expired
Links
Landscapes
- Epoxy Compounds (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は式（Ｉ）
□Ｃ−７−ＣＮ（Ｉ）
ＣＨ３０ＯＨ
で不される２−ヒドロキシー３一メチルー３一（６−メ
トキシー ２−ナフチル）アクリロニトリル化合物およ
びその製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a 2-hydroxy-3-methyl-3-(6-methoxy-2-naphthyl)acrylonitrile compound having the formula (I) □C-7-CN(I) CH30OH and a method for producing the same. It is related to.
式（Ｉ）で示される化合物は消炎鎮痛作用を有する式（
）で示される２−（６−メトキシ−２一ナフチル）プロ
ピオン酸を製造する土に有用な中間体である。今回、本
発明者らは公知方法とは異なる下式に示すような方法で
、しかも公知方法よりも収率よく式（）で示される化合
物が得られることが判明し、本発明を完成したのである
。The compound represented by formula (I) has an anti-inflammatory and analgesic effect.
) is a useful intermediate for producing 2-(6-methoxy-2-naphthyl)propionic acid. This time, the present inventors have found that the compound represented by the formula () can be obtained by the method shown in the following formula, which is different from the known method, and in a higher yield than the known method, and have completed the present invention. be.
本発明で得られる新規中間体（１）の合成は２ーシアノ
−３−メチル−３−（６−メトキシ−２一ナフチル）グ
リシド酸エステルを加水分解してグリシド酸あるいはそ
の塩にした後、遊離グリシド酸を加熱等により脱炭酸さ
せて式（１）で示される２−ヒドロキシ−３−メチル−
３−（６−メトキシ−２−ナフチル）アクリロニトリル
を製造することができる。The novel intermediate (1) obtained in the present invention is synthesized by hydrolyzing 2-cyano-3-methyl-3-(6-methoxy-2-naphthyl)glycidic acid ester to glycidic acid or its salt, and then releasing the free 2-hydroxy-3-methyl- represented by formula (1) is obtained by decarboxylating glycidic acid by heating etc.
3-(6-methoxy-2-naphthyl)acrylonitrile can be produced.
エステルの加水分解反応はアルカリ、例えば水酸化カリ
ウム、炭酸カリウム、重炭酸カリウム、水酸化ナトリウ
ム、炭酸ナトリウム、重炭酸ナトリウムを用いて加水分
解を行ない、溶媒としてはメタノール、エタノール、プ
ロパノール等のアルコール系溶媒、水等適当な溶媒中反
応を行なう。Hydrolysis of esters is carried out using an alkali such as potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium hydroxide, sodium carbonate, or sodium bicarbonate, and an alcohol-based solvent such as methanol, ethanol, or propanol is used as the solvent. The reaction is carried out in an appropriate solvent such as solvent or water.
反応温度としてはＯ〜１００℃程度で、好ましくは１０
〜４０℃程度である。反応時間は１〜４０時間程度であ
る。得られたカルボン酸の金属アルカリ塩を遊離にした
後、加熱等により脱炭酸させて、式（１）で示される２
−ヒドロキシ−３−メチル−３−（６一メトキシ一２−
ナフチル）アクリロニトリルを製造することができる。The reaction temperature is approximately 0 to 100°C, preferably 10°C.
~40°C. The reaction time is about 1 to 40 hours. After liberating the obtained metal alkali salt of carboxylic acid, it is decarboxylated by heating etc. to obtain 2 shown by formula (1).
-Hydroxy-3-methyl-3-(6-methoxy-2-
naphthyl)acrylonitrile can be produced.
脱炭酸の方法としては溶媒中または無溶媒で加熱するこ
とにより脱炭酸することができる。Decarboxylation can be carried out by heating in a solvent or without a solvent.
用いる溶媒としては水、あるいはメタノール、エタノー
ル、プロパノール等のアルコール類、あるいはベンゼン
、トルエン、キシレン等の炭化水素系溶媒、酢酸メチル
エステル、酢酸エチルエステル等の溶媒中で加熱し脱炭
酸することができる。加熱の温度としては５０〜１５０
℃程度である。反応処理としては自体公知の手段（例え
ば再結晶、カラムクロマトグラフイ一等）により精製す
るのがよい。本発明で得られた中間体（１）は新規物質
のため各種機器分析の測定によりその構造を確認した。
なお、（１）および（）は幾何異性体の混合物である。
次に実施例にて本発明を具体的に説明するが、これに限
定されるものではない。The solvent to be used is water, alcohols such as methanol, ethanol, and propanol, hydrocarbon solvents such as benzene, toluene, and xylene, and decarboxylation by heating in a solvent such as methyl acetate and ethyl acetate. . The heating temperature is 50 to 150
It is about ℃. As the reaction treatment, it is preferable to purify by means known per se (for example, recrystallization, column chromatography, etc.). Since the intermediate (1) obtained in the present invention is a new substance, its structure was confirmed by various instrumental analyses.
Note that (1) and () are mixtures of geometric isomers.
Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.
実施例 １
２−シアノ−３−メチル−３−（６−メトキシ−２−ナ
フチル）アクリル酸エチルの製造法６−メトキシ−２−
アセチルナフタレン１０．０７、シアノ酢酸エチル７．
４７、酢酸アンモニウム３．８７、氷酢酸９．２ｍ１１
ベンゼン５０ｍ１の混合物を水分定量装置を用いて４３
時間加熱還流する。Example 1 Method for producing ethyl 2-cyano-3-methyl-3-(6-methoxy-2-naphthyl)acrylate 6-methoxy-2-
Acetylnaphthalene 10.07, Ethyl cyanoacetate 7.
47, ammonium acetate 3.87, glacial acetic acid 9.2ml11
A mixture of 50 ml of benzene was measured using a moisture meter.
Heat to reflux for an hour.
放冷後ベンゼン層を水、飽和重曹水および飽和食塩水で
洗浄後、硫酸マグネシウムで乾燥。溶媒留去して得られ
る油状物をシリカゲルカラムクロマトグラフイ一に付し
、クロロホルム流出分画より黄色油状物１２．９７を得
。本物質は幾何異性体の混合物である。赤外線吸収スペ
クトル（ＫＢｒ）ＣＴｒＬ−１：１７２０（Ｃ−０）・
２２１５（ＣＮ）核磁気共鳴スペクトルδ（ＣＤＣｌ３
）：０．９５、１．２９（３Ｈ、各三重線、ＣＨ２Ｃ塩
、二異性体）２．４２、２。After cooling, the benzene layer was washed with water, saturated sodium bicarbonate solution, and saturated saline, and then dried over magnesium sulfate. The oily substance obtained by distilling off the solvent was subjected to silica gel column chromatography, and 12.9% of a yellow oily substance was obtained from the chloroform effluent fraction. This substance is a mixture of geometric isomers. Infrared absorption spectrum (KBr) CTrL-1:1720(C-0)・
2215 (CN) nuclear magnetic resonance spectrum δ (CDCl3
): 0.95, 1.29 (3H, each triplet, CH2C salt, diisomer) 2.42, 2.
６１（３Ｈ１各一重線、ＣＨ３、二異性体）３．７１（
３Ｈ１一重線、０ＣＨ３）
３．９３、４．２０（２Ｈ１各四重線、Ｃ川ＣＨ３、二
異性体）６．８０〜７．８０（６Ｈ１多重線、芳香環プ
ロトン）異性体の一方が結晶化しエタノ゛−ルより再結
晶してＭｐ９２〜９３℃の結晶４７を得。61 (3H1 each singlet, CH3, diisomer) 3.71 (
3H1 singlet, 0CH3) 3.93, 4.20 (2H1 each quartet, C river CH3, diisomer) 6.80-7.80 (6H1 multiplet, aromatic ring proton) One of the isomers is crystal The crystals were recrystallized from ethanol to obtain crystal 47 with an Mp of 92-93°C.
元素分析 Ｃｌ８Ｈｌ７Ｏ３Ｎ
計算値：Ｃｌ７３．２２；Ｈｌ５．７６；Ｎｌ４．７５
実験値：Ｃｌ７３．ｌＯ；Ｈｌ５．４５；Ｎｌ４．８２
実施例 ２２−シアノ−３−メチル−３−（６−メトキ
シ−２−ナフチル）グリシド酸エチルの製造法アクリル
酸エチル誘導体２．９５７およびタングステン酸ナトリ
ウム０．９ｆのエタノール溶液１０ｍ１に室温にて攪拌
下３０％過酸化水素水１．８ｍｊを滴下する。Elemental analysis Cl8Hl7O3N Calculated value: Cl73.22; Hl5.76; Nl4.75
Experimental value: Cl73. lO; Hl5.45; Nl4.82
Example 2 Production method of ethyl 2-cyano-3-methyl-3-(6-methoxy-2-naphthyl)glycidate Add 2.957 ethyl acrylate derivative and 0.9 f of sodium tungstate to 10 ml of ethanol solution and stir at room temperature. Add 1.8 mj of 30% hydrogen peroxide solution dropwise.
室温で４８時間撹拌したのちエタノールを留去し、残渣
をクロロホルムに溶かす。クロロホルム層を水洗後硫酸
マグネシウムで乾燥し、溶媒留去して得られる残渣をシ
リカゲルカラムクロマトグラフィ一に付し、クロロホル
ム流出分画より無色油状物２．５ｙを得。本物質は幾何
異性体の混合物である。赤外線吸収スペクトル（ＫＢｒ
）ＣＴｒＬ−１：１７５０（Ｃ−０）、２２４０（Ｃ王
Ｎ）核磁気共鳴スペクトルδ（ＣＤＣｌ３）：０．７３
、１．３１（３Ｈ１各三重線、ＣＨ２ＣＨ３、二異性体
）１．８１、１。After stirring at room temperature for 48 hours, ethanol was distilled off and the residue was dissolved in chloroform. The chloroform layer was washed with water, dried over magnesium sulfate, the solvent was distilled off, and the resulting residue was subjected to silica gel column chromatography to obtain 2.5y of a colorless oil from the chloroform effluent fraction. This substance is a mixture of geometric isomers. Infrared absorption spectrum (KBr
) CTrL-1: 1750 (C-0), 2240 (CN) nuclear magnetic resonance spectrum δ (CDCl3): 0.73
, 1.31 (3H1 each triplet, CH2CH3, diisomer) 1.81, 1.
９８（３Ｈ，各一重線、ＣＨ３、 二異性体）３．７７
（３Ｈ１一重線、０ＣＨ３）
３．７９、４．２９（２Ｈ１各四重線、ＣＨ２ＣＨ３、
二異性体）６．８０〜７．８０（６Ｈ、多重線、芳香環
プロトン）異性体の一力が結晶化しメタノールより再結
晶してＭｐｌｌ４〜１１５℃の結晶０．９７を得。98 (3H, each singlet, CH3, diisomer) 3.77
(3H1 singlet, 0CH3) 3.79, 4.29 (2H1 each quartet, CH2CH3,
Diisomer) 6.80-7.80 (6H, multiplet, aromatic ring proton) One of the isomers was crystallized and recrystallized from methanol to obtain Mpll of 0.97 with a temperature of 4-115°C.
元素分析 Ｃｌ８Ｈｌ７Ｏ４Ｎ計算値：Ｃｌ６９．４５
；Ｈ、５．４７；Ｎｌ４．５Ｏ実験値：Ｃｌ６９．６２
；Ｈｌ５．５ｌ；Ｎｌ４．３２実施例 ３２−ヒドロキ
シ−３−メチル−３−（６−メトキシ−２−ナフチル）
アクリロニトリルの製造法エステル体５５０即をエタノ
ール３０ｍ１に溶解したものに、水酸化カリウム１１８
ηのエタノール溶解を室温にて撹拌下加える。Elemental analysis Cl8Hl7O4N calculated value: Cl69.45
; H, 5.47; Nl4.5O Experimental value: Cl69.62
; Hl 5.5l; Nl 4.32 Example 32-hydroxy-3-methyl-3-(6-methoxy-2-naphthyl)
Production method of acrylonitrile To a solution of 550 esters in 30 ml of ethanol, add 118 ml of potassium hydroxide.
A solution of η in ethanol is added under stirring at room temperature.
１時間攪拌し室温で一夜放置後エタノールを留去するこ
とによりカルボン酸のナトリウム塩が得られる。After stirring for 1 hour and standing overnight at room temperature, the ethanol is distilled off to obtain the sodium salt of the carboxylic acid.
赤外吸収スペクトル（ＫＢｒ）ＣＴＬ−１：１６２０（
ＣＯＯ−）、２２４０（ＣＮ）得られたナトリウム塩を
少量の水に溶解し、永冷下１０％塩酸水溶液を加えて酸
性とし酢酸エチルで抽出する。Infrared absorption spectrum (KBr) CTL-1:1620 (
COO-), 2240 (CN) The obtained sodium salt was dissolved in a small amount of water, acidified by adding 10% aqueous hydrochloric acid solution under constant cooling, and extracted with ethyl acetate.
Claims (1)
２−ヒドロキシ−３−メチル−３−（６−メトキシ−２
−ナフチル）アクリロニトリル化合物。 ２ 一般式（II） ▲数式、化学式、表等があります▼（II）（式中、Ｒは
低級アルキル基を示す）で示される２−シアノ−３−メ
チル−３−（６−メトキシ−２−ナフチル）グリシド酸
エステル類を加水分解後脱炭酸させることを特徴とする
式（ I ）▲数式、化学式、表等があります▼（ I ）で
示される２−ヒドロキシ−３−メチル−３−（６−メト
キシ−２−ナフチル）アクリロニトリルの製造法。[Claims] 1 Formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ 2-hydroxy-3-methyl-3-(6-methoxy-2) represented by (I)
-naphthyl)acrylonitrile compound. 2 General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ 2-cyano-3-methyl-3-(6-methoxy-2) represented by (II) (in the formula, R represents a lower alkyl group) - Naphthyl) glycidic acid esters are hydrolyzed and then decarboxylated (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ 2-Hydroxy-3-methyl-3-( A method for producing 6-methoxy-2-naphthyl)acrylonitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4854576A JPS5931497B2 (en) | 1976-04-30 | 1976-04-30 | 2-Hydroxy-3-methyl-3-(6-methoxy-2-naphthyl)acrylonitrile compound and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4854576A JPS5931497B2 (en) | 1976-04-30 | 1976-04-30 | 2-Hydroxy-3-methyl-3-(6-methoxy-2-naphthyl)acrylonitrile compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS52133961A JPS52133961A (en) | 1977-11-09 |
| JPS5931497B2 true JPS5931497B2 (en) | 1984-08-02 |
Family
ID=12806330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4854576A Expired JPS5931497B2 (en) | 1976-04-30 | 1976-04-30 | 2-Hydroxy-3-methyl-3-(6-methoxy-2-naphthyl)acrylonitrile compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5931497B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6125611A (en) * | 1984-07-16 | 1986-02-04 | Yoshinobu Eguchi | Method for discharging settled material |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7544350B2 (en) | 2002-11-22 | 2009-06-09 | Hallstar Innovations Corp. | Method of decreasing the UV light degradation of polymers |
| US8158678B2 (en) | 2005-04-07 | 2012-04-17 | Cph Innovations Corp. | Photoabsorbing, highly conjugated compounds of cyanoacrylic esters, sunscreen compositions and methods of use |
-
1976
- 1976-04-30 JP JP4854576A patent/JPS5931497B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6125611A (en) * | 1984-07-16 | 1986-02-04 | Yoshinobu Eguchi | Method for discharging settled material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS52133961A (en) | 1977-11-09 |
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