JPS6042774B2 - 5-Alkyl-1,5,5-trialkoxy-1-penten-3-yne and its manufacturing method - Google Patents
5-Alkyl-1,5,5-trialkoxy-1-penten-3-yne and its manufacturing methodInfo
- Publication number
- JPS6042774B2 JPS6042774B2 JP52137136A JP13713677A JPS6042774B2 JP S6042774 B2 JPS6042774 B2 JP S6042774B2 JP 52137136 A JP52137136 A JP 52137136A JP 13713677 A JP13713677 A JP 13713677A JP S6042774 B2 JPS6042774 B2 JP S6042774B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- yne
- trialkoxy
- formula
- alkyl
- 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
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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は一般式（１）
Ｒ＾３０ＣＨ＝ＣＨ−Ｃ王Ｃ−Ｃ（０Ｒ＾２）２、、、
（Ｉ）（式中、Ｒ＾”、２個のＲ＾’およびＲ＾゜は同
一または相異なる低級アルキル基を表わす）で示される
新規な化合物およびその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula (1) R^30CH=CH-C-C(0R^2)2,,
The present invention relates to a novel compound represented by (I) (wherein R^'', two R^' and R^゜ represent the same or different lower alkyl groups) and a method for producing the same.
上記一般式（Ｉ）においてＲ＾゛、Ｒ＾”およびＲ＾゜
はメチル基、エチル基、プロピル基、ブチル基などの低
級アルキル基であり、Ｒ＾゛は好ましくはメチル基であ
る。In the above general formula (I), R^'', R^'' and R^゜ are lower alkyl groups such as methyl group, ethyl group, propyl group, butyl group, and R^゛ is preferably a methyl group.
本発明により提供される一般式（Ｉ）で示される５−ア
ルキルー１・ ５ ・ ５−トリアルコキシ−１−ペン
テンー３−インは、催眠剤、抗バクテリア剤あるいはマ
ルトールのような賦香剤となる有機化合物の合成中間体
である後述の２−アルキル−止−ピランー４−オンの合
成中間体として有用である。The 5-alkyl-1.5.5-trialkoxy-1-penten-3-ynes of the general formula (I) provided by the present invention can be used as hypnotic agents, antibacterial agents or excipients such as maltol. It is useful as an intermediate for the synthesis of 2-alkyl-stop-pyran-4-one, which will be described later, which is an intermediate for the synthesis of organic compounds.
すなわち本発明者らの研究によれば、一般式（Ｉ）で示
される５−アルキルー１・５・５−トリアルコキシー１
−ペンテンー３−インは・水または水を含む有機溶媒中
、室温〜１００℃の温度で触媒量の酸、例えば塩酸、硫
酸、リン酸、Ｐ−トルエンスルホン酸、酢酸、安息香酸
などで処理することにより容易に一般式（■）（式中、
Ｒ１は一般式（１）におけると同じ意味を有する）で示
される２−アルキルー化−ピランー４−オンに誘導され
る（後述の参考例を参照）。That is, according to the research of the present inventors, 5-alkyl-1,5,5-trialkoxy 1 represented by general formula (I)
-Penten-3-yne is treated with a catalytic amount of an acid such as hydrochloric acid, sulfuric acid, phosphoric acid, P-toluenesulfonic acid, acetic acid, benzoic acid, etc. in water or an organic solvent containing water at a temperature between room temperature and 100°C. Therefore, the general formula (■) (in the formula,
R1 has the same meaning as in general formula (1)) (see Reference Examples below).
一般式（１）で示される５−アルキルー１・５●５−ト
リアルコキシー１−ペンテンー３−インの代表的なもの
を挙げると下記のとおりである。Representative examples of 5-alkyl-1.5●5-trialkoxy-1-penten-3-yne represented by general formula (1) are as follows.
１●５●５−トリメトキシー１−ヘキセンー３ーイン１
−メトキシー５・５ージエトキシー１−ヘキセンー３−
イン１・５●５−トリエトキシー１−ヘキセンー３−イ
ン１−エトキシー５・５ージメトキシー１−ヘキセンー
３−イン１●５●５−トリエトキシー１−ヘプテンー３
ーイン本発明によれば一般式（１）で示される５−アル
キルー１・５・５−トリアルコキシー１−ペンテンー３
−インは一般式（■）（式中、Ｒ３は一般式（１）にお
けると同じ意味を有する）で示される１−アルコキシー
１−ブテンー１−ブテンー３−インと一般式（■）（式
中、Ｒ１は一般式（１）におけると同じ意味を有し、３
個のＲ２は同一または相異なる低級アルキル基を表わす
）で示されるオルトカルボン酸エステルをフリーデルク
ラフト型ハロゲン化金属触媒の存在下に反応させること
により得られる。1●5●5-trimethoxy1-hexene-3-in-1
-methoxy5,5-diethoxy1-hexene-3-
yne1,5●5-triethoxy1-hexene-3-yne1-ethoxy5,5-dimethoxy1-hexene-3-yne1●5●5-triethoxy1-heptene-3
-in According to the present invention, 5-alkyl-1,5,5-trialkoxy-1-pentene-3 represented by general formula (1)
-yne is 1-alkoxy-1-butene-1-buten-3-yne represented by the general formula (■) (in the formula, R3 has the same meaning as in the general formula (1)) and the general formula (■) (in the formula, R3 has the same meaning as in the general formula (1)). , R1 has the same meaning as in general formula (1), and 3
R2 represents the same or different lower alkyl groups) in the presence of a Friedel-Crafts type metal halide catalyst.
原料である一般式（■）で示される１−アルコキシー１
−ブテンー３−インとしては、例えば１ーメトキシー１
−ブテンー３−イン、１−エトキシー１−ブテンー３−
インなどがあり、これらの化合物はジアセチレンとアル
コールから容易に得られる（特開昭４８−１００１３号
公報および特開昭４８一１００１４号公報参照）。また
一般式（■）で示され７るオルトカルボン酸エステルの
具体例としては１●１・１−トリメトキシエタン、１・
１・１ートリエトキシエタン、１・１・１−トリーｎ−
ブトキシエタン、１・１・１−トリエトキシプロパン、
１●１・１−トリエトキシブタン、１・１・ノ１−トリ
エトキシペンタン、３−メチルー１・１・１−トリエト
キシブタンなどが挙げられる。用いるフリーデルクラフ
ト型ハロゲン化金属触媒は、例えば塩化アルミニウム、
塩化亜鉛、ヨウ化亜鉛、四塩化スズ、四塩化チタン、塩
化第２鉄などであり、好ましくは塩化亜鉛である。触媒
の量は一般式（■）で示される１−アルコキシー１一ブ
テンー３−インに対して１．０〜５０重量％程度であり
、好ましくは１０〜３鍾量％である。この反応は通常、
窒素雰囲気下４０〜２００゜Ｃが好ましくは８０〜９０
℃の温度で生成するアルコールを留出させながら行なわ
れる。次に本発明を実施例および参考例により具体的に
説明する。1-alkoxy 1 represented by the general formula (■) which is a raw material
-butene-3-yne, for example, 1-methoxy-1
-Buten-3-yne, 1-ethoxy-1-butene-3-
These compounds can be easily obtained from diacetylene and alcohol (see JP-A-48-10013 and JP-A-48-10014). Specific examples of orthocarboxylic acid esters represented by the general formula (■) include 1●1,1-trimethoxyethane, 1.
1,1-triethoxyethane, 1,1,1-tri-n-
Butoxyethane, 1,1,1-triethoxypropane,
1●1,1-triethoxybutane, 1,1,no-1-triethoxypentane, 3-methyl-1,1,1-triethoxybutane, and the like. The Friedel-Crafts type metal halide catalyst used is, for example, aluminum chloride,
These include zinc chloride, zinc iodide, tin tetrachloride, titanium tetrachloride, and ferric chloride, with zinc chloride being preferred. The amount of the catalyst is about 1.0 to 50% by weight, preferably 10 to 3% by weight, based on the 1-alkoxy-1-butene-3-yne represented by the general formula (■). This reaction is usually
40-200°C under nitrogen atmosphere, preferably 80-90°C
It is carried out while distilling off the alcohol produced at a temperature of °C. Next, the present invention will be specifically explained using Examples and Reference Examples.
実施例１
オルト酢酸エチル３２．４ｙ１塩化亜鉛３ｙを窒素雰囲
気下に８０゜Ｃで３紛間攪拌し、その混合液に１−メト
キシー１−ブテンー３−イン１５ｍ１を滴下したのち、
生成するエタノールを留出させながらそのまま４時間攪
拌を続けた。Example 1 Three powders of 32.4y of ethyl orthoacetate and 3y of zinc chloride were stirred at 80°C under a nitrogen atmosphere, and 15ml of 1-methoxy-1-buten-3-yne was added dropwise to the mixture.
Stirring was continued for 4 hours while distilling off the produced ethanol.
得られた反応混合物にベンゼン１００ｍ１を加え、固形
分を口過したのち、母液を減圧蒸留し１２５〜１３０′
Ｃ（２１Ｔｆｒ！ＮＨｇ）の留分として下記のＮＭＲス
ペクトルを有する１−メトキシー５・５ージエトキシー
１−ヘキセンー３−インを１６ｇ得た（収率５４％）。
ＮＭＲスペクトル（１００ＭＨｚ）δ弗Ｓｌ３：１．１
２（Ｔ．．Ｊ＝８．０Ｈｚ）６Ｈ；１．５４（ｓ）３Ｈ
；３．５２（Ｑ．．Ｊ＝８．０Ｈｚ）４Ｈ：３．６４（
ｓ）３Ｈ；４．４３（Ｄ，．Ｊ＝６．０Ｈｚ）１Ｈ；６
．１８（Ｄ，．Ｊ＝６．０Ｈｚ）１Ｈ実施例２〜５
種々の１−アルコキシー１−ブテンー３−イン、オルト
酢酸エステルおよびフリーデルクラフト型ハロゲン化金
属触媒を用いて実施例１と同様の方法により各々対応す
る５−メチルー１・５・５−トリアルコキシー１−ペン
テンー３−インを得た。100 ml of benzene was added to the resulting reaction mixture, the solid content was filtered out, and the mother liquor was distilled under reduced pressure to give a concentration of 125 to 130 ml.
16 g of 1-methoxy-5,5-diethoxy-1-hexen-3-yne having the following NMR spectrum was obtained as a fraction of C(21Tfr!NHg) (yield: 54%).
NMR spectrum (100MHz) δF Sl3: 1.1
2 (T..J=8.0Hz) 6H; 1.54 (s) 3H
;3.52(Q..J=8.0Hz)4H:3.64(
s) 3H; 4.43 (D,.J=6.0Hz) 1H; 6
．． 18 (D,.J = 6.0 Hz) 1H Examples 2 to 5 The same procedure as in Example 1 was carried out using various 1-alkoxy-1-buten-3-ynes, orthoacetic esters, and Friedel-Crafts type metal halide catalysts. The corresponding 5-methyl-1,5,5-trialkoxy-1-penten-3-ynes were obtained by the method.
その結果を第１表に示す。参考例
メタノール１０ｍ１および水２ｍＬの混合液に濃硫酸数
滴を加えて加熱還流し、その溶液中に１−メトキシー５
●５ージエトキシー１−ヘキセンー３ーイン１．９ｑの
メタノール溶液６ｍｔを滴下した。The results are shown in Table 1. Reference Example A few drops of concentrated sulfuric acid was added to a mixture of 10 ml of methanol and 2 ml of water, heated to reflux, and 1-methoxy 5 was added to the solution.
●6 mt of a methanol solution of 1.9 q of 5-diethoxy-1-hexene-3-yne was added dropwise.
Claims (1)
は相異なる低級アルキル基を表わす）で示される５−ア
ルキル−１・５・５−トリアルコキシ−１−ペンテン−
３−イン。 ２ 一般式Ｒ＾３ＯＣＨ＝ＣＨ−Ｃ≡ＣＨ（式中、Ｒ＾
３は低級アルキル基を表わす）で示される１−アルコキ
シ−１−ブテン−３−インと一般式Ｒ＾１Ｃ（ＯＲ＾２
）＿３（式中、Ｒ＾１および３個のＲ＾２は同一または
相異なる低級アルキル基を表わす）で示されるオルトカ
ルボン酸エステルをフリーデルクラフト型ハロゲン化金
属触媒の存在下に反応させる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、Ｒ＾２およびＲ＾３は上記の意味を有
する）で示される５−アルキル−１・５・５−トリアル
コキシ−１−ペンテン−３−インの製造方法。[Claims] 1 Represented by the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1, two R^2 and R^3 represent the same or different lower alkyl groups) 5-alkyl-1,5,5-trialkoxy-1-pentene-
3-in. 2 General formula R^3OCH=CH-C≡CH (in the formula, R^3OCH=CH-C≡CH
3 represents a lower alkyl group) and the general formula R^1C (OR^2
)_3 (wherein R^1 and three R^2 represent the same or different lower alkyl groups) is reacted in the presence of a Friedel-Crafts type metal halide catalyst. A general formula characterized by ▲
There are mathematical formulas, chemical formulas, tables, etc.▼ 5-alkyl-1,5,5-trialkoxy-1-pentene represented by (in the formula, R^1, R^2 and R^3 have the above meanings) -3-yne manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52137136A JPS6042774B2 (en) | 1977-11-14 | 1977-11-14 | 5-Alkyl-1,5,5-trialkoxy-1-penten-3-yne and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52137136A JPS6042774B2 (en) | 1977-11-14 | 1977-11-14 | 5-Alkyl-1,5,5-trialkoxy-1-penten-3-yne and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5473714A JPS5473714A (en) | 1979-06-13 |
| JPS6042774B2 true JPS6042774B2 (en) | 1985-09-25 |
Family
ID=15191654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP52137136A Expired JPS6042774B2 (en) | 1977-11-14 | 1977-11-14 | 5-Alkyl-1,5,5-trialkoxy-1-penten-3-yne and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6042774B2 (en) |
-
1977
- 1977-11-14 JP JP52137136A patent/JPS6042774B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5473714A (en) | 1979-06-13 |
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