JPS588365B2 - Fuhouwa 14 Inkanka Gobutsuno Seihou - Google Patents
Fuhouwa 14 Inkanka Gobutsuno SeihouInfo
- Publication number
- JPS588365B2 JPS588365B2 JP11451675A JP11451675A JPS588365B2 JP S588365 B2 JPS588365 B2 JP S588365B2 JP 11451675 A JP11451675 A JP 11451675A JP 11451675 A JP11451675 A JP 11451675A JP S588365 B2 JPS588365 B2 JP S588365B2
- Authority
- JP
- Japan
- Prior art keywords
- trans
- trimethyl
- formula
- compound
- cyclotetrade
- 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
- 150000004678 hydrides Chemical class 0.000 claims description 4
- -1 lithium aluminum hydride Chemical compound 0.000 claims description 4
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 235000014443 Pyrus communis Nutrition 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 241000256602 Isoptera Species 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 description 2
- HVZNIISBCURSMR-ALFIBICVSA-N (1s,2e,6e,10e,14s)-3,7,11-trimethyl-14-propan-2-ylcyclotetradeca-2,6,10-trien-1-ol Chemical compound CC(C)[C@@H]1CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\[C@H]1O HVZNIISBCURSMR-ALFIBICVSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- HVZNIISBCURSMR-UHFFFAOYSA-N Allylcembrol Natural products CC(C)C1CCC(C)=CCCC(C)=CCCC(C)=CC1O HVZNIISBCURSMR-UHFFFAOYSA-N 0.000 description 1
- 241000159174 Commiphora Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- VXMXVCBDKLZKAE-YLFQGFBMSA-N cembrene A Chemical group C1C\C(C)=C\CC\C(C)=C/[C@@H]2[C@@H](C(C)C)CC[C@@](C)(O)[C@@H]21 VXMXVCBDKLZKAE-YLFQGFBMSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229930004069 diterpene Natural products 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZHYZQXUYZJNEHD-VQHVLOKHSA-N geranic acid Chemical compound CC(C)=CCC\C(C)=C\C(O)=O ZHYZQXUYZJNEHD-VQHVLOKHSA-N 0.000 description 1
- 229930008392 geranic acid Natural products 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003016 pheromone Substances 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- ZHYZQXUYZJNEHD-UHFFFAOYSA-N trans-geranic acid Natural products CC(C)=CCCC(C)=CC(O)=O ZHYZQXUYZJNEHD-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
【発明の詳細な説明】
本発明は不飽和１４員環化合物、更に詳細には次の式
および
で表わされるオールトランス−２−イングロビル−５・
９−１３−｝リメチル−シクロテトラデ力＝５・９−ジ
エン（■）およびオールトランスー２−イソプロビル−
５・９・１３−トリメチル−シクロテトラデ力− ５−
９・１３−トリエノール（ＩＶ）の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an unsaturated 14-membered ring compound, more specifically, all-trans-2-ingrovir-5.
9-13-}limethyl-cyclotetrade force = 5,9-diene (■) and all-trans-2-isoprobyl-
5,9,13-trimethyl-cyclotetrade force-5-
The present invention relates to a method for producing 9,13-trienol (IV).
本発明で得られる式（ｆＶ）の化合物は、ｖ．Ｄ．Ｐａ
ｔｉｌらによってＣ ｏｍｍ ｉｐｈｏｒａ ｍｕｋｕ
ｌ （ Ｈｏｏ’ｋ １ｅｘ Ｓ ｔｏｃｋｓ ） Ｅ
ｎｇｌ ，の樹脂成分として発見されたムクロール（
ｍｕｋｕｌｏｌ ）と指称される化合物Ｃ Ｔｅｔｒａ
ｈｅｄｒｏｎ， Ｖｏｌ ２ ９、３４１〜３４８頁（
１９７３年）〕であり、式（■）の化合物と共にセンブ
レン−Ａの骨格を有する１４員環ジテルペン化合物であ
る。The compound of formula (fV) obtained in the present invention has v. D. Pa
Comm iphora muku by til et al.
l (Hoo'k 1ex Stocks) E
Muchlor, which was discovered as a resin component of ngl,
Compound C Tetra, designated as mukulol)
hedron, Vol 2 9, pp. 341-348 (
(1973)], which together with the compound of formula (■) are 14-membered diterpene compounds having a Cembrene-A skeleton.
センブレンーＡはＢ−Ｐ，Ｍｏｏｒｅ（ Ｊ．Ｃｈｅｍ
．Ｓｏｃ．、Ｐｅｒｋｉｎ １、２６５３頁（ １
’Ｊ７ ２ ） ）によって白蟻の道しるべフェロモン
として報告された白蟻１駆除物質として注目されている
が、本発明の式（ｍ）および式（ ｉｖ ）の化合物も
それ自体白蟻に対する生埋活性を有すると共に、この種
の化合物の各種誘導体を製造するための合成原料となり
得る有用な化合物である。Sembran-A is B-P, Moore (J.Chem
．． Soc. , Perkin 1, p. 2653 (1
'J7 2)) has attracted attention as a termite exterminating substance reported as a signpost pheromone for termites, but the compounds of formula (m) and formula (iv) of the present invention also have live burial activity against termites as well as , is a useful compound that can be used as a synthetic raw material for producing various derivatives of this type of compound.
本発明は次の反応式で示される。The present invention is shown by the following reaction formula.
（式中、Ｒは低級アルキル基を示す）
すなわち、本発明はオールトランス−２−（１一メチル
−１−クロロエチル）−５・９・１３−トリメチル−シ
クロテトラデ力−５・９・１３一トリエノン（Ｉ）をト
リアルキルスズハイドライドで還元してオールトランス
−２−インプロビル−５・９・１３−トリメチル−シク
ロテトラデ力−５・９・１３−トリエノン（ｎ）となし
、次いでこれを水素化アルミニウムリチウムで還元して
オールトランス−２−イソプロビル−５・９・１３−ト
リノチルーシクロテトラデ力−５・９ージエノン（■）
およびオールトランス−２−イソプロビル−５・９・１
３−トリメチル−シクロテトラデ力−５・９・１３−ト
リエノール（ＩＶ）を製造する方法である。(In the formula, R represents a lower alkyl group) That is, the present invention relates to all-trans-2-(1-methyl-1-chloroethyl)-5,9,13-trimethyl-cyclotetrade-5,9,13-trienone (I) was reduced with trialkyltin hydride to give all-trans-2-improvyl-5,9,13-trimethyl-cyclotetrade-5,9,13-trienone (n), which was then converted to aluminum hydride. Reduction with lithium yields all-trans-2-isopropyl-5,9,13-trinotyl-cyclotetrade-5,9-dienone (■)
and all-trans-2-isopropyl-5,9,1
This is a method for producing 3-trimethyl-cyclotetrade-5,9,13-trienol (IV).
本発明で原料として使用される式（Ｉ）の化合物は、例
えば今回本発明者によって見出された方法、すなわち、
トランスーゲラニル・ゲラニウム酸クロライドを四塩化
スズまたは塩化アルミニウムと反応せしめて分子内閉環
することにより容易に製せられる。The compound of formula (I) used as a raw material in the present invention can be prepared, for example, by the method discovered by the present inventor, that is, by
It is easily produced by reacting transgeranyl geranic acid chloride with tin tetrachloride or aluminum chloride to undergo intramolecular ring closure.
本発明を実施するには、先ず、式（Ｉ）の化合物をトリ
アルキルスズハイドライドで還元して式（■）の化合物
とする。To carry out the present invention, first, the compound of formula (I) is reduced with trialkyltin hydride to form the compound of formula (■).
トリアルキルスズハイドライドとしてはトリ−ｎ−プチ
ルスズハイドライドがよい結果を与える。As the trialkyltin hydride, tri-n-butyltin hydride gives good results.
本反応はアゾピスイソブチルニトリルの少量を併用する
ことによって促進される。This reaction is accelerated by the concomitant use of a small amount of azopisisobutylnitrile.
通常反応はシクロヘキサン等の溶媒中加熱還流すること
によって行われる。The reaction is usually carried out in a solvent such as cyclohexane by heating to reflux.
式（■）の化合物の還元は、エーテル等の溶媒中、水冷
下水素化アルミニウムリチウムで還元することによって
有利に行われる。The reduction of the compound of formula (■) is advantageously carried out by reduction with lithium aluminum hydride in a solvent such as ether under cooling with water.
斯くするとき式（■）の化合物と式（ＩＶ）の化合物が
略１対の割合で得られるが、これらはシリカゲル力ラム
クロマトグラフイーによって容易に分離できる。In this process, the compound of formula (■) and the compound of formula (IV) are obtained in a ratio of approximately one pair, and these can be easily separated by silica gel column chromatography.
次に実施例を挙げて説明する。Next, an example will be given and explained.
実施例 １
オールトランス−２−（１−メチル−１−クロロエチル
）−５・９・１３−トリメチル−シクロテトラデ力−５
・９・１３−トリエノン２．４１をシクロヘキサン１５
０ｍｌに溶かし、アゾビスイソブチルニトリル０． ２
ｇを加え、窒素気流中加熱還流下、これにトリ−ｎ−プ
チルスズハイドライド２ｇ（１．１当量）のシクロヘキ
サン５０ｍｌ溶液を滴下し、４時間反応させる。Example 1 All-trans-2-(1-methyl-1-chloroethyl)-5,9,13-trimethyl-cyclotetrade-5
・9,13-trienone 2.41 to cyclohexane 15
Dissolve in 0 ml of azobisisobutylnitrile. 2
A solution of 2 g (1.1 equivalents) of tri-n-butyltin hydride in 50 ml of cyclohexane was added dropwise thereto under heating and reflux in a nitrogen stream, and the mixture was allowed to react for 4 hours.
反応液は１ｌの水に注入後エーテルで抽出し、抽出液か
ら溶媒を留去すれば、オールトランス−２−イソプロビ
ル−５・９・１３−トリメチルーシクロテトラデカー５
・９・１３−トリエノン２，１ｇ得る。The reaction solution was poured into 1 liter of water, extracted with ether, and the solvent was distilled off from the extract to obtain all-trans-2-isopropyl-5,9,13-trimethyl-cyclotetradecar 5.
- Obtain 2,1 g of 9,13-trienone.
Ｕｖ：λｍａｘ２４２ｎｍ（ε ４５００）。Uv: λmax 242 nm (ε 4500).
実施例 ２
オールトランス−２−イソゾロビル−５・９・１３−ト
リメチルーシクロテトラデカ−５・９・１３−トリエノ
ン２ｇを無水エーテル４００ｍｌに溶解し、水冷下これ
に水素化アルミニウムリチウム０．４１を少しずつ加え
、添加終了後、再に２時？反応させる。Example 2 2 g of all-trans-2-isozorobyl-5,9,13-trimethyl-cyclotetradeca-5,9,13-trienone was dissolved in 400 ml of anhydrous ether, and 0.41 g of lithium aluminum hydride was added to the solution under water cooling. Add it little by little, and after the addition is complete, add it again at 2 o'clock? Make it react.
反応液に水５００ｍｌを添加して、エーテル層を分取し
、エーテルを留去すれば残留物２１を得る。Add 500 ml of water to the reaction solution, separate the ether layer, and distill off the ether to obtain residue 21.
これをｎ−ヘキサン：酢酸エチル（２０ ： １）を展
開剤としシリカゲルクロマトグラフイーにより分離すれ
ば、オールトランス−２一イソプロビル−５・９・１３
−ｔ−ＩＪメチル−シクロテトラデ力−５・９−ジエノ
ンｏ．ｓｙおよびオールｌ ランスー２−イソプロビル
−５・９・１：３−｝リメチル−シクロテトラデ力−５
・９・１３−トリエノール０．８２？を得る。If this is separated by silica gel chromatography using n-hexane:ethyl acetate (20:1) as a developing agent, all-trans-2-isoprobyl-5,9,13
-t-IJ methyl-cyclotetrade-5,9-dienone o. sy and alll lance-2-isopropyl-5.9.1:3-}limethyl-cyclotetrade-5
・9.13-trienol 0.82? get.
オールトランス−２−イソプロビル−５・９・１３−ト
リメチルーシクロテトラデ力−５・９一ジエノン：
ＩＲ：１７００鍜７１
ＮＭＲ：δ（ｐｐｍ）０．９、５．９５値のプロトンは
認められない。All-trans-2-isopropyl-5,9,13-trimethyl-cyclotetrade-5,9-dienone: IR: 1700 ~ 71 NMR: δ (ppm) 0.9, protons with a value of 5.95 were observed I can't.
オールトランス−２−イソプロビル−５・９・１３−ト
リメチルーシク口テトラデ力−５・９・１３−トリエノ
ール：
融点：３７゜Ｃ
ＩＲ：３３５０、１０２０ｃｒＩＬ−１（ＯＨ）。All-trans-2-isopropyl-5,9,13-trimethyl-5,9,13-trienol: Melting point: 37°C IR: 3350, 1020crIL-1 (OH).
ＭＳ：ｍ／ｅ ２９０（Ｍモ）、 ２ ７ ２ （ Ｍ＋−Ｈ２０ ）。MS: m/e 290 (M mo), 2 7 2 (M+-H20).
Claims (1)
クロロエチル）−５・９・１３− トリメチルーシクロ
テトラデカー５−９・１３−トリエノンをトリアルキル
スズハイドライドで還元して式で表わされるオールトラ
ンス−２−イソプロビル−５・９・１３−トリメチルー
シクロテトラデカ−５・９・１３−トリエノンとなし、
次いでこれを水素化アルミニウムリチウムで還元するこ
とを特徴とする式 で表わされるオールトランス−２−イソプロビル−５・
９・１３−トリメチルーシクロテトラデカ−５・９−ジ
エノンおよびオールトランス−２−イソプロビル−５・
９・１３−トリメチルーシクロテトラデカ−５・９・１
３−トリエノールの製法。[Claims] All-trans-2-(1-methyl-1-
chloroethyl)-5,9,13-trimethyl-cyclotetradecar 5-9,13-trienone is reduced with trialkyltin hydride to produce all-trans-2-isopropyl-5,9,13-trimethyl- cyclotetradeca-5,9,13-trienone and pear,
This is then reduced with lithium aluminum hydride to obtain all-trans-2-isopropyl-5.
9,13-trimethyl-cyclotetradeca-5,9-dienone and all-trans-2-isoprobyl-5.
9,13-trimethyl-cyclotetradeca-5,9,1
Method for producing 3-trienol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11451675A JPS588365B2 (en) | 1975-09-22 | 1975-09-22 | Fuhouwa 14 Inkanka Gobutsuno Seihou |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11451675A JPS588365B2 (en) | 1975-09-22 | 1975-09-22 | Fuhouwa 14 Inkanka Gobutsuno Seihou |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5239651A JPS5239651A (en) | 1977-03-28 |
| JPS588365B2 true JPS588365B2 (en) | 1983-02-15 |
Family
ID=14639698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11451675A Expired JPS588365B2 (en) | 1975-09-22 | 1975-09-22 | Fuhouwa 14 Inkanka Gobutsuno Seihou |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS588365B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0798746B2 (en) * | 1986-12-09 | 1995-10-25 | 三菱化学株式会社 | Lysosome release inhibitor |
-
1975
- 1975-09-22 JP JP11451675A patent/JPS588365B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5239651A (en) | 1977-03-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Corey et al. | A new and general synthesis of polycyclic. gamma.-lactones by double annulation | |
| Corey et al. | Total synthesis of the racemate of the sesquiterpenoid marine allomone 9-isocyanopupukeanane | |
| Zweifel et al. | Thexylchloroborane. A versatile reagent for the preparation of mixed thexyldiorganoboranes | |
| Boekelheide et al. | A Synthesis of Quinolizinium and Dehydroquinolizinium Derivatives1 | |
| Kraus et al. | Timed Diels-Alder reactions | |
| Paquette et al. | Molecular recognition during 1, 2-addition of chiral vinyl organometallics to chiral. beta.,. gamma.-unsaturated ketones. Case studies of three 7, 7-disubstituted 2-norbornenones. Part 5 | |
| Fowler et al. | Synthesis of model compounds for maleylacetoacetic acid. Maleylacetone | |
| Sweat et al. | Dimethyl sulfoxide oxidations | |
| House et al. | Reduction as a side reaction arising from the thermal decomposition of lithium organocuprates to form copper hydride derivatives | |
| Hooz et al. | A new regiospecific synthesis of enol boranes of methyl ketones | |
| JPS588365B2 (en) | Fuhouwa 14 Inkanka Gobutsuno Seihou | |
| DE69329281T2 (en) | Pyridine derivatives as hydroxylase and lyase inhibitors | |
| Paquette et al. | Topologically spherical molecules. An efficient synthesis of C16-hexaquinacene and its lack of neutral homoaromatic character | |
| Dauben et al. | Thermal valence isomerization of cis-fused bicyclic cyclobutenes. A study of orbital symmetry control | |
| Hori et al. | Stable 2-thianaphthalenes: synthesis and reactions with electrophiles | |
| White et al. | Bis homologation of a naphthalene to a dihydroheptalene via carbenoid addition | |
| Ortiz de Montellano et al. | Base-Catalyzed Isomerization of cis-and trans-2, 2-Dimethyl-3-formylcyclopropanecarboxylates. Nature of the Base-Stable cis Intermediate | |
| Thies et al. | Ring expansion of 3-methoxy-6-vinyl-7, 8, 9, 10-tetrahydro-6 (5H)-benzocyclooctenol | |
| CN105143162B (en) | resolve resolution | |
| Mukaiyama et al. | A convenient method for the synthesis of α, β-unsaturated carbonyl compounds | |
| Oliva et al. | AN IMPROVED SYNTHESIS OF ALKYL 1-ALKYL-3-METHYL-2-PYRAZOLINE-5-ONE-4-DITHIOCARBOXYLATES | |
| JPS5857419B2 (en) | Method for producing 1-cyclopropyl-1-phenyl-ω-amino-1-lower alkanoyloxyalkanes | |
| US3845088A (en) | Cyclopentane or cyclohexane substituted unsaturated hydrocarbon esters having juvenile hormone activity | |
| Vinick et al. | Stereospecific cyclopentane synthesis via intramolecular nitrone cycloaddition | |
| Augustine et al. | Assisted thermal decomposition of mixed carbonic anhydrides |