JPS58203995A - Preparation of lineatin - Google Patents
Preparation of lineatinInfo
- Publication number
- JPS58203995A JPS58203995A JP57087032A JP8703282A JPS58203995A JP S58203995 A JPS58203995 A JP S58203995A JP 57087032 A JP57087032 A JP 57087032A JP 8703282 A JP8703282 A JP 8703282A JP S58203995 A JPS58203995 A JP S58203995A
- Authority
- JP
- Japan
- Prior art keywords
- lineatin
- cyclobutanediol
- oxidizing agent
- formula
- reacting
- 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
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、一般式
（式中、Ｒはｔ−ブチルジメチルシリル基、テトラヒド
ロピラニル基または１−エトキシエチル基を示す。）
で表わされるシクロブタンジオール誘導体と酸化剤とを
反応させたのち酸処理して式
で表わされるキクイムシの集合フェロモンである８、８
．７−ドリメチルー２，９−ジオキサトリシクロ［”
３ 、３ 、 ｌ 、 ０’・７〕 ノナン（一般名リ
ニアチン、以下この名称を使用する）の製造法である。Detailed Description of the Invention The present invention provides a cyclobutanediol derivative represented by the general formula (wherein R represents a t-butyldimethylsilyl group, a tetrahydropyranyl group, or a 1-ethoxyethyl group) and an oxidizing agent. 8,8 is a bark beetle aggregation pheromone expressed by the formula:
．． 7-drimethyl-2,9-dioxatricyclo[”
3, 3, l, 0'・7] This is a method for producing nonane (common name: linearatin, hereinafter this name will be used).
昆虫フェロモンは昆虫に対し強力な誘引性を示すことか
ら、近年害虫防除の目的に使用されるようになっている
。しかしながら、フェロモンを自然界から多量に単離す
ることはきわめて困難であるため、フェロモンの経済的
な合成法の開発が強く望まれているところである。Insect pheromones have been used for pest control purposes in recent years because they exhibit strong attraction to insects. However, it is extremely difficult to isolate large quantities of pheromones from the natural world, so there is a strong desire to develop an economical method for synthesizing pheromones.
本発明の目的物質であるリニアチンは、５ｉｌｖｅｒｓ
ｔｅＬｎらにより単離されたものであって、下記■およ
び■の２つの推定構造式が提出されていた（ジャーナル
オブ ケミカル エコロジー、第３巻、５４９頁、１
９７７年）。Lineatin, which is the target substance of the present invention, is 5ilvers
It was isolated by teLn et al., and the following two putative structural formulas, ■ and ■, were submitted (Journal of Chemical Ecology, Vol. 3, p. 549, 1).
977).
その後、森ら（テトラヘドロン、３６巻、２１９７頁、
１９８０年ンおよび５ｌｅｓｓｏｒら（ジャーナル オ
ブ オーガニック ケミストリー、４５巻、２２９０頁
、１９８０年）ニョつて、■の構造式が天然物と一致す
ることが合成的に確認された。After that, Mori et al. (Tetrahedron, vol. 36, p. 2197,
(Journal of Organic Chemistry, vol. 45, p. 2290, 1980), it was synthetically confirmed that the structural formula of ① corresponds to that of a natural product.
本発明者らはリニアチン■の短工鵬でしカモ選択的な製
造法を見出すに到り、本発明を完成した。The inventors of the present invention have discovered a selective method for producing linearin (2) in a short and selective manner, and have completed the present invention.
なうことができる。can become.
■ ■
■ ■
ニ脱クロル化して■を得る。■をリチウムシイブチルボ
ロンハイドライドで還元してＯを得る。■ ■ ■ ■ Dechlorination to obtain ■. (2) is reduced with lithium shibutyl boron hydride to obtain O.
■をジメチルホルムアミド中、イミダゾールの存在下、
ターシャリーブチルジメチルンリルクロライドで２級の
アルコールを保護して■ａを得る。■ａをジボランで還
元してジオール体■ａを得る。■をパラトルエンスルホ
ン酸触媒下、ジヒドロビランと反応させて■ｂを得る。■ in dimethylformamide in the presence of imidazole,
Protect the secondary alcohol with tert-butyldimethylsilyl chloride to obtain ①a. (2) Reduce a with diborane to obtain diol compound (2) a. (2) is reacted with dihydrobilane under a para-toluenesulfonic acid catalyst to obtain (2)b.
■ｂをジボランで還元してジオール体■ｂを得る。(2) Reduce b with diborane to obtain diol compound (2) b.
■をパラトルエンスルホン酸触媒下、エチルビニルエー
テルと反応させて■Ｃを得る。■Ｃをジ゛ボランで還元
してジオール体■Ｃを得る。(2) is reacted with ethyl vinyl ether under a para-toluenesulfonic acid catalyst to obtain (2)C. ■C is reduced with diborane to obtain diol compound ■C.
なお、出発原料であるイソプレンは市販品であり、ジク
ロロケテンは既知化合物である（テトラヘドロン、２７
巻、６１５〜６３８頁、１９７１年）、。The starting material isoprene is a commercially available product, and dichloroketene is a known compound (tetrahedron, 27
Vol. 615-638, 1971).
以下に本発明の詳細な説明する。The present invention will be explained in detail below.
シクロブタンジオール銹導体（■ａ−＠ｌをジクロルメ
タン、クロロホルム等の溶媒にとかしたのち冷却し、酸
化剤を加える。酸化剤としては、たとえばピリジニウム
ｌりロロクロメートやピリジニウムジクロメート等があ
げられる。Cyclobutanediol rust conductor (■a-@l) is dissolved in a solvent such as dichloromethane or chloroform, cooled, and an oxidizing agent is added. Examples of the oxidizing agent include pyridinium dichromate and pyridinium dichromate.
仕込モル比は原料シクロブタンジオール誘導体に対して
等モルであろう反応温度はθ℃〜ｌＯ℃、反応時間は８
０分以内である。さらに１５％〜８０％塩酸を加えて５
時間〜４８時間攪拌する。有機層を分離、中和したのち
、蒸留するかまたはカラ４クロマトグラフイー処理する
ことにより、本発明の目的物であるリニアチンが猾られ
る。The charging molar ratio will be equimolar to the raw material cyclobutanediol derivative.The reaction temperature will be θ°C to 10°C, and the reaction time will be 8°C.
Within 0 minutes. Add 15% to 80% hydrochloric acid and
Stir for 48 hours. After separating and neutralizing the organic layer, linearatin, which is the object of the present invention, is obtained by distillation or color 4 chromatography treatment.
次に実施例をあげて本発明の詳細な説明する。Next, the present invention will be explained in detail with reference to Examples.
実施例１
２−ジメチルヒドロキシメチル−３−メチル−８−（２
−ヒドロキシエチル）−１−ジメチル−ｔ−ブチルシリ
ルオキシブタン（■ａ。Example 1 2-dimethylhydroxymethyl-3-methyl-8-(2
-hydroxyethyl)-1-dimethyl-t-butylsilyloxybutane (■a.
２２６ Ｉｆ 、 ０．７５ Ｅリモル）を塩化メチレ
ン２−にとかした。これにピリジニウムクロロクロメー
ト（１６５ｑ、（１７５ミリモ、ル）を５℃以下で加え
３０分間同温度で攪拌した。226 If, 0.75 E mol) was dissolved in methylene chloride 2-. Pyridinium chlorochromate (165q, (175 mmol)) was added to this at a temperature below 5°C, and the mixture was stirred at the same temperature for 30 minutes.
これに１５％塩酸水６ｄを加え４８時間攪拌した。分岐
したのち、水洗、重曹水洗、水洗し、硫酸マグネシウム
で乾燥した。−過したのち塩化メチレンを常圧で留去し
たのち残分をアルミナカラムクロマトグラフィーにより
精製してリニアチン■（３３キ、収ＥＫ２６．２％）を
得た。To this was added 6 d of 15% hydrochloric acid and stirred for 48 hours. After branching, the mixture was washed with water, sodium bicarbonate, water, and dried over magnesium sulfate. After the methylene chloride was distilled off at normal pressure, the residue was purified by alumina column chromatography to obtain Lineatin (33 kg, yield: EK 26.2%).
実施例２
実施例１の酸化剤をピリジニウムジクロメ−）−（２０
２１１Ｆ、０．７５ミリモル）にかえて同様に操作を行
ない、リニアチン■（２６ｑ。Example 2 The oxidizing agent of Example 1 was replaced with pyridinium dichromene)-(20
211F, 0.75 mmol), and linearatin ■ (26q.
収率１１．６％）を得た。A yield of 11.6%) was obtained.
実施例３
２−ジメチルヒドロキシメチル−８−メチル−８−（２
−ヒドロキシエチル）−１−テトラヒドロピラニルオキ
シブタン（■ｂ。Example 3 2-dimethylhydroxymethyl-8-methyl-8-(2
-hydroxyethyl)-1-tetrahydropyranyloxybutane (■b.
２０４ｑ、０．７５ミリモル）をクロロホルムこ；二〜
２ｆｎｔにとかし、これにピリジニウムクロロメート（
１６５ＭｉＯ，７５ミリモル）を１０℃で加え１０分間
攪拌した。さらに３０％塩酸水３ｗ１１を加え１６時間
攪拌した、分液したのち実施例１と同様に欅、作を行な
い、＋１ ニアチン■（８６■、２８．６％）を得た。Dissolve 204q, 0.75 mmol) in chloroform and add pyridinium chloromate (
165MiO, 75 mmol) was added at 10°C and stirred for 10 minutes. Further, 3w11 of 30% hydrochloric acid solution was added, and the mixture was stirred for 16 hours. After separation, the same method as in Example 1 was carried out to obtain +1 niatin (86) (28.6%).
実施例４
２−ジメチルヒドロキシメチル−３−メチル−３−（２
−ヒドロキシエチル）−１−（１−エトキシエチル）オ
キシブタン（■Ｃ。Example 4 2-dimethylhydroxymethyl-3-methyl-3-(2
-hydroxyethyl)-1-(1-ethoxyethyl)oxybutane (■C.
２５８ＩｌＩＰ、１．０ミリモル）を塩化メチレン２−
にとかし、これにピリジニウムジクロメート（２７０＝
η、１．０ミリモル）を１０℃で加え３０分間攪拌した
。さらに２０％塩酸水３−を加え５時間攪拌した。分液
したのち水洗、重曹水洗、水洗し、硫酸マグネシウムで
乾燥した。沖過したのち塩化メチレノを常圧で留去し、
残分を減圧蒸留し、ｌ ニアチン（２４ダ、収率１４，
２％、沸点１２０〜ｔｇｏ℃（バス温）／６０ＩｍｍＨ
２）を得た。258IlIP, 1.0 mmol) in methylene chloride 2-
To this, add pyridinium dichromate (270=
η, 1.0 mmol) was added at 10° C. and stirred for 30 minutes. Furthermore, 20% hydrochloric acid solution 3- was added and stirred for 5 hours. After separating the layers, the mixture was washed with water, sodium bicarbonate, water, and dried over magnesium sulfate. After passing through the water, methylene chloride is distilled off at normal pressure.
The residue was distilled under reduced pressure to obtain 1 niatin (24 Da, yield 14,
2%, boiling point 120~tgo℃ (bath temperature)/60ImmH
2) was obtained.
実ａ例ｔ〜４で得たリニアチン■の分光学的データは前
記の文献中のものと全く一致した。The spectroscopic data of Lineatin II obtained in Examples t-4 were in complete agreement with those in the above-mentioned literature.
Claims (1)
ロピラニル基またはｌ−エトキシエチル基を示す。） で表わされるシクロブタンジオール誘導体と酸化剤とを
反応させたのち、酸処理することを特徴とする式 で表わされる３、３．７−ドリメチルー２，９−ジオキ
サトリシクロＣａ、８．Ｌ、０’・７〕ノナンの製造法
。[Claims] After reacting a cyclobutanediol derivative represented by the general formula (wherein R represents a t-butyldimethylsilyl group, a tetrahydropyranyl group, or a l-ethoxyethyl group) with an oxidizing agent, , 3,3,7-dolimethyl-2,9-dioxatricycloCa, which is represented by the formula characterized by being treated with an acid; 8. L, 0'・7] Method for producing nonane.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57087032A JPS58203995A (en) | 1982-05-21 | 1982-05-21 | Preparation of lineatin |
| SE8207228A SE8207228L (en) | 1981-12-24 | 1982-12-17 | PROCEDURE FOR PREPARING AN INSECT Pheromone |
| NO82824256A NO824256L (en) | 1981-12-24 | 1982-12-17 | PROCEDURE FOR THE PREPARATION OF AN INSECT PHARMACY |
| FI824425A FI824425L (en) | 1981-12-24 | 1982-12-22 | FRAMSTAELLNINGSFOERFARANDE FOER INSEKTFEROMON |
| DE19823247861 DE3247861A1 (en) | 1981-12-24 | 1982-12-23 | Process for the preparation of 3,3,7-trimethyl-2,9-dioxatricyclo[3.3.1.0<4,7>]nonane, and intermediates used in the process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57087032A JPS58203995A (en) | 1982-05-21 | 1982-05-21 | Preparation of lineatin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS58203995A true JPS58203995A (en) | 1983-11-28 |
Family
ID=13903606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57087032A Pending JPS58203995A (en) | 1981-12-24 | 1982-05-21 | Preparation of lineatin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58203995A (en) |
-
1982
- 1982-05-21 JP JP57087032A patent/JPS58203995A/en active Pending
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