JPH055819B2 - - Google Patents
Info
- Publication number
- JPH055819B2 JPH055819B2 JP18325184A JP18325184A JPH055819B2 JP H055819 B2 JPH055819 B2 JP H055819B2 JP 18325184 A JP18325184 A JP 18325184A JP 18325184 A JP18325184 A JP 18325184A JP H055819 B2 JPH055819 B2 JP H055819B2
- Authority
- JP
- Japan
- Prior art keywords
- ethyl
- compound
- sulfolene
- formula
- group
- 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 - Lifetime
Links
- -1 tetrahydropyranyloxydecyl group Chemical group 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- ZTJGMVSDMQAJPE-UHFFFAOYSA-N (11E,13E)-11,13-hexadecadienal Natural products CCC=CC=CCCCCCCCCCC=O ZTJGMVSDMQAJPE-UHFFFAOYSA-N 0.000 claims description 4
- ZTJGMVSDMQAJPE-VNKDHWASSA-N (11e,13e)-hexadeca-11,13-dienal Chemical compound CC\C=C\C=C\CCCCCCCCCC=O ZTJGMVSDMQAJPE-VNKDHWASSA-N 0.000 claims description 4
- GKFQVSXEEVMHMA-VNKDHWASSA-N 11E,13E-Hexadecadien-1-ol Chemical compound CC\C=C\C=C\CCCCCCCCCCO GKFQVSXEEVMHMA-VNKDHWASSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- MBDNRNMVTZADMQ-UHFFFAOYSA-N sulfolene Chemical compound O=S1(=O)CC=CC1 MBDNRNMVTZADMQ-UHFFFAOYSA-N 0.000 claims description 4
- BDQIEHWUIWHSES-UHFFFAOYSA-N 10-(5-ethyl-1,1-dioxo-2,5-dihydrothiophen-2-yl)decan-1-ol Chemical compound CCC1C=CC(CCCCCCCCCCO)S1(=O)=O BDQIEHWUIWHSES-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000000877 Sex Attractant Substances 0.000 description 4
- QQIRAVWVGBTHMJ-UHFFFAOYSA-N [dimethyl-(trimethylsilylamino)silyl]methane;lithium Chemical compound [Li].C[Si](C)(C)N[Si](C)(C)C QQIRAVWVGBTHMJ-UHFFFAOYSA-N 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- ZTPLOZBDGWXJKK-UHFFFAOYSA-N 2-(10-iododecoxy)oxane Chemical compound ICCCCCCCCCCOC1CCCCO1 ZTPLOZBDGWXJKK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 241000607479 Yersinia pestis Species 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- LWGUKTSVKFADQN-UHFFFAOYSA-N 10-iododecan-1-ol Chemical compound OCCCCCCCCCCI LWGUKTSVKFADQN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- HUHXLHLWASNVDB-UHFFFAOYSA-N 2-(oxan-2-yloxy)oxane Chemical compound O1CCCCC1OC1OCCCC1 HUHXLHLWASNVDB-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- 238000006166 Brown acetylene zipper reaction Methods 0.000 description 1
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 244000088415 Raphanus sativus Species 0.000 description 1
- 235000006140 Raphanus sativus var sativus Nutrition 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000005667 attractant Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000031902 chemoattractant activity Effects 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- GKFQVSXEEVMHMA-UHFFFAOYSA-N hexadeca-11,13-dien-1-ol Chemical compound CCC=CC=CCCCCCCCCCCO GKFQVSXEEVMHMA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 238000007242 hydrozirconation reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- ZDYVRSLAEXCVBX-UHFFFAOYSA-N pyridinium p-toluenesulfonate Chemical compound C1=CC=[NH+]C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 ZDYVRSLAEXCVBX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明はアルデヒド誘導体の製造法に関し、さ
らに詳しくはハンマダラノメイガの性フエロモン
である下記式（）で示される（11E，13E）−
11，13−ヘキサデカジエナール（以下、アルデヒ
ド化合物と呼ぶ）の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing aldehyde derivatives, and more specifically, the present invention relates to a method for producing an aldehyde derivative, and more specifically, the present invention relates to a method for producing an aldehyde derivative, which is a sex pheromone of the common leaf borer moth, and is represented by the following formula (11E, 13E)-
The present invention relates to a method for producing 11,13-hexadecadienal (hereinafter referred to as an aldehyde compound).
ハイマダラノメイガは、その幼虫が大根、キヤ
ベツ等のアブラナ科の野菜に重大な食害を与える
ことから、その効率的な防除が望まれている。 Since the larvae of the brown borer moth cause serious feeding damage to cruciferous vegetables such as radish and cabbage, effective control is desired.
本発明の対象である上記のアルデヒド化合物
は、ハイマダラノメイガの雌成虫が分泌し雄成虫
を誘引する性フエロモンとして知られている
（Agr.Bicl.Chem.、46、2395〜2397（1982））。 The above-mentioned aldehyde compound, which is the subject of the present invention, is known as a sex pheromone that is secreted by female adult moths and attracts male adults (Agr. Bicl. Chem., 46 , 2395-2397 (1982)). .
該性フエロモンは、これを誘引物質とする誘蛾
装置に用いることにより、ハイマダラノメイガの
発生密度を予察することが可能となる。 By using the sex pheromone in a moth-attracting device that uses it as an attractant, it becomes possible to predict the density of the occurrence of the common moth.
ところで、害虫の発生密度を予察することがで
きれば、適切な時期に有効な殺虫剤を散布するこ
とが可能となり、よつて効率よく対象害虫を撲滅
することができることから、殊に現代の総合害虫
防除体系において害虫の発生密度の予察は極めて
重要な技術である。 By the way, if it is possible to predict the density of insect pests, it becomes possible to spray effective insecticides at the appropriate time, thereby efficiently eradicating the target pests. Prediction of pest density is an extremely important technique in the system.
本発明者らは、かかるハイマダラノメイガの性
フエロモンを工業的にも有利に製造する方法につ
き鋭意検討した結果、式（）
で示される10−（５−エチル−３−スルホレン−
２−イル）デカン−１−オールをアルカリの存在
下に加熱することにより立体選択的に、しかも高
収率で式（）
で示される（11E，13E）−11，13−ヘキサデカジ
エン−１−オールが得られ、次いで該化合物の水
酸基を酸化することにより目的のアルデヒド化合
物が容易にかつ収率よく得られることを見出し本
発明に至つた。 The present inventors have conducted intensive studies on a method for industrially advantageous production of the sex pheromone of the porphyry moth, and found that the formula () 10-(5-ethyl-3-sulfolene-
By heating 2-yl)decane-1-ol in the presence of an alkali, the formula () can be stereoselectively and in high yield obtained. It was discovered that (11E, 13E)-11,13-hexadecadien-1-ol represented by the formula was obtained, and then by oxidizing the hydroxyl group of the compound, the desired aldehyde compound could be obtained easily and in good yield. This led to the present invention.
上記の本発明方法において、原料となる式
（）で示されるアルコール化合物は新規化合物
であり、式（）
で示される３−スルホレンに、塩基の存在下10−
テトラヒドロピラニロキシデシル基およびエチル
基を導入して得られる式（）
〔式中、THPはテトラヒドロピラニル基を表わ
す。〕
で示される２−（10−テトラヒドロピラニロキシ
デシル）−５−エチル−３−スルホレンを酸で処
理することにより得られる。 In the above-mentioned method of the present invention, the alcohol compound represented by the formula () serving as a raw material is a new compound, and the alcohol compound represented by the formula () In the presence of a base, 10-
Formula () obtained by introducing a tetrahydropyranyloxydecyl group and an ethyl group [In the formula, THP represents a tetrahydropyranyl group. ] It can be obtained by treating 2-(10-tetrahydropyranyloxydecyl)-5-ethyl-3-sulfolene shown by with an acid.
これまでに、上記式（）で示されるアルデヒ
ド化合物の製造法としては、前掲報文に記載のハ
ンドロジルコニル化（hydrozirconation）反応お
よびアセチレンジツパー反応（acetylene zipper
reaction）を用いる方法が知られているが、該方
法は、工業的に取扱い難いアセチレン系合成中間
体を経由すること、高価な貴金属触媒または貴金
属試薬を使用することなどの点で必ずしも有利で
はなく、またその収率も満足し得るものではな
い。 Up to now, methods for producing the aldehyde compound represented by the above formula () include the hydrozirconation reaction and the acetylene zipper reaction described in the previous report.
However, this method is not necessarily advantageous in that it involves the use of acetylenic synthetic intermediates that are difficult to handle industrially, and the use of expensive noble metal catalysts or noble metal reagents. , and the yield is also not satisfactory.
一方、本発明方法によれば、入手容易な３−ス
ルホレンを出発原料として、極めて短かい工程で
しかも収率よく目的のアルデヒド化合物を製造す
ることができ、工業的にも極めて有利である。特
に、本発明方法によれば、誘引活性を有する異性
体成分、即ち（Ｅ，Ｅ）−ジエン体が高い立体選
択性で得られる点で、極めて有利と言える。 On the other hand, according to the method of the present invention, the desired aldehyde compound can be produced in a very short process and with good yield using easily available 3-sulfolene as a starting material, which is extremely advantageous from an industrial standpoint. In particular, the method of the present invention is extremely advantageous in that an isomer component having attracting activity, that is, an (E,E)-diene compound, can be obtained with high stereoselectivity.
以下に本発明方法につき説明する。式（）で
示される３−スルホレンから式（）で示される
テトラヒドロピラニルエーテル化合物を得るに際
し、10−テトラヒドロピラニロキシデシル基およ
びエチル基の導入試薬としては、夫々、10−テト
ラヒドロピラニロキシデシルアイオダイドのよう
な10−テトラヒドロピラニロキシデシルハライド
およびヨウ化エチルなどのエチルハライドが挙げ
られ、これらは、何れを先に反応させてもよい。
また該反応時に存在させる塩基としてはリチウム
ヘキサメチルジシラザン（LiHMDS）、リチウム
ジイソプロピルアミドなどの有機塩基を挙げるこ
とができ、このような塩基は通常ヘキサメチルホ
スホールアマイド（HMPA）のようなカチオン
捕捉剤の共存下に反応に供される。また、該反応
は、通常テトラヒドロフラン（THF）などの有
機溶媒中で冷却下に行なわれる。 The method of the present invention will be explained below. When obtaining the tetrahydropyranyl ether compound represented by formula () from 3-sulfolene represented by formula (), 10-tetrahydropyranyloxydecyl iodide is used as the reagent for introducing 10-tetrahydropyranyloxidecyl group and ethyl group, respectively. Examples include 10-tetrahydropyraniloxydecyl halides such as 10-tetrahydropyraniloxydecyl halides and ethyl halides such as ethyl iodide, and any of these may be reacted first.
In addition, examples of the base present during the reaction include organic bases such as lithium hexamethyldisilazane (LiHMDS) and lithium diisopropylamide. The reaction is carried out in the presence of an agent. Further, the reaction is usually carried out in an organic solvent such as tetrahydrofuran (THF) under cooling.
このようにして得られるテトラヒドロピラニル
エーテル化合物は、常法により塩酸などの鉱酸、
ｐ−トルエンスルホン酸などの有機酸を作用させ
ることにより容易にテトラヒドロピラニル基が離
脱し、式（）で示されるアルコール化合物に導
かれる。 The tetrahydropyranyl ether compound thus obtained can be prepared using a mineral acid such as hydrochloric acid,
The tetrahydropyranyl group is easily separated by the action of an organic acid such as p-toluenesulfonic acid, leading to an alcohol compound represented by the formula ().
次に該アルコールは、化合物は、エタノール、
メタノールなどのプロトン性溶媒中で、例えばカ
性カリ、炭酸カリなどのアルカリの存在下に加熱
することにより、円滑に亜硫酸ガスを放ちながら
熱開裂し、立体選択的に目的の式（）で示され
る（Ｅ，Ｅ）−ジエンアルコールがほぼ定量的に
得られる。 Next, the alcohol, the compound, ethanol,
By heating in a protic solvent such as methanol in the presence of an alkali such as caustic potash or potassium carbonate, the compound is thermally cleaved while smoothly releasing sulfur dioxide gas, and stereoselectively shows the desired formula (). (E,E)-diene alcohol is obtained almost quantitatively.
次いで、該（Ｅ，Ｅ）−ジエンアルコールに、
例えばピリジニウムクロミルクロメート（PCC）
などの、水酸基をホルミル基に変換させるのに使
用される通常の酸化剤を作用させることにより、
容易に目的のアルデヒド化合物を得ることができ
る。 Then, to the (E,E)-diene alcohol,
For example pyridinium chromyl chromate (PCC)
By the action of common oxidizing agents used to convert hydroxyl groups to formyl groups, such as
The desired aldehyde compound can be easily obtained.
以下に本発明を実施例で詳しく説明するが、本
発明は何らこれらに限定されるものではない。 EXAMPLES The present invention will be explained in detail below using Examples, but the present invention is not limited thereto.
実施例
10−（５−エチル−３−スルホレン−２−イ
ル）デカン−１−オールの合成
３−スルホレン26.6ｇ、10−テトラヒドロピ
ラニロキシデシルアイオダイド41.4ｇおよび
HMPA70mlを乾燥THF600mlに溶解し、−78℃
に冷却しておく。次いでLiHMDS20.7ｇを乾
燥THF80mlに溶解し、−78℃に冷却した後、こ
れを先に調製しておいたTHF溶液中に、減圧
下撹拌しながら一気に加え、−78℃で１時間撹
拌する。次に該反応液を徐々に昇温しながら−
20℃で飽和食塩水100mlを加えた後、液温を室
温まで上昇させる。反応液を減圧下に濃縮し、
大部分のTHFを留去した後、水100mlを加え塩
化メチレンで抽出する。塩化メチレン層を無水
硫酸ナトリウムで乾燥後濃縮し、残渣をシリカ
ゲル（Wako Ｃ−200）250ｇを充填したカラ
ムクロマトグラフイー（溶出液：酢酸エチル：
ｎ−ヘキサン＝１：９）に付し、２−（10−テ
トラヒドロピラニロキシデシル）−３−スルホ
レン22.69ｇ（収率：55％）を得た。1
H NMR（CDCl3）
δ（ppm）1.20〜2.20（24H、ｍ）
3.65（2H、ｓ、５−Ｈ）
3.20〜4.00（5H、ｍ）
4.60（1H、ｍ）
6.05（2H、ａ、３−Ｈ、４−Ｈ）
IR（CHCl3） 1310、1140cm-1
MSm／ｚ 357（M+−１）
上記で得られた２−（10−テトラヒドロピラ
ニロキシデシル）−３−スルホレン7.35ｇ、ヨ
ウ化エチル1.83mlおよびHMPA7.2mlを乾燥
THF100mlに溶解し、次いでこれに上記と同様
にして、LiHMDS3.8ｇの乾燥THF溶液を加え
た後、同様に処理し、２−（10−テトラヒドロ
ピラニロキシデシル）−５−エチル−３−スル
ホレン5.06ｇを得た（収率：67％）。1
H NMR（CDCl3）
δ（ppm）1.01（3H、ｔ、Ｊ＝7.0Hz）
1.15〜2.20（26H、ｍ）
3.20〜4.05（6H、ｍ）
4.62（1H、ｍ）
5.98（2H、ｓ、３、４−Ｈ）
IR（CHCl3） 1300、1100cm-1
MSm／ｚ 387（M+＋１）
次に上記で得られた２−（10−テトラヒドロ
ピラニロキシデシル）−５−エチル−３−スル
ホレンを、常法により95％エタノール中ｐ−ト
ルエンスルホン酸−ピリジン塩で処理した後、
通常の後処理を行ない、92％の収率で目的の10
−（５−エチル−３−スルホレン−２−イル）
デカン−１−オールを得た。1
H NMR（CDC3）
δ（ppm）1.00（3H、ｔ、Ｊ＝7.0Hz）
3.20（2H、ｔ、Ｊ＝6.5Hz）
（11E，13E）−11，13−ヘキサデカジエノー
ルの合成
前記で得た10−（５−エチル−３−スルホレ
ン−２−イル）デカン−１−オール300mgを、
95％エタノール５mgに溶解し、これに炭酸カリ
280mgを加え、アルゴン雰囲気下封管中で、1.5
時間130℃に加熱した。次いで反応液を室温ま
で冷却し、これに酢酸エチル20mlを加えた後、
無機塩を去し、さらに溶媒を留去した。得ら
れた残渣をシリカゲル10ｇを用いたカラムクロ
マトグラフイー（溶出液；酢酸エチル：ｎ−ヘ
キサン＝１：９）に付し、目的の（11E，13E）
−11，13−ヘキサデカジエノール230mgを得た
（収率：95％）。1
H NMR（CDCl3）
δ（ppm）1.05（3H、ｔ、Ｊ＝7.0Hz）
1.20〜1.80（16H、ｍ）
2.05（4H、ｍ）
2.68（1H、br、ｓ）
3.60（2H、ｔ、Ｊ＝6.0Hz）
5.60（2H、ｍ）
6.00（2H、ｍ）
13C NMR（CDCl3）
δ（ppm）133.73 32.67
、132.36 29.56
、130.44 29.28
129.55 25.86
62.71 25.61
32.78、13.68
UV λ95%C2H5OH
max230nｍ（ε＝23090）
MSm／ｚ 238（M+）
（11E，13E）−11，13−ヘキサデカジエナー
ルの合成
上記のようにして得られる（11E，13E）−
11，13−ヘキサデカジエノール344mgを塩化メ
チレン10mlおよびｎ−ヘキサン10mlの混合溶媒
に溶かし、これに、D.Michelotらの方法
（Synthesis、1983、130）に準じて調製した
PCC−アルミナ3.56mgを加え、アルゴン雰囲気
下室温で10時間撹拌した。反応液を常法により
処理した後、得られた粗生成物を、シリカゲル
15ｇを用いたカラムクロマトグラフイー（溶出
液；酢酸エチル：ｎ−ヘキサン＝１：９）に付
し、目的の（11E，13E）−11，13−ヘキサデカ
ジエナール260mgを得た（収率：67.2％）。1
H NMR（CDCl3）
δ（ppm）1.00（3H、ｔ、Ｊ＝7.0Hz）
1.20〜1.50（12H、ｍ）
1.60（2H、ｍ）
2.06（4H、ｍ）
2.44（2H、dt、Ｊ＝2.0Hz、Ｊ＝8.0Hz）
5.60（2H、ｍ）
6.03（2H、ｍ）
9.82（1H、ｔ、Ｊ＝2.0Hz）
13C NMR
δ（ppm）202.15 32.59
133.48 29.41
132.01 25.55
129.45 22.18
128.98 13.50
43.88
IR（CHCl3）
MSm／ｚ 236（M+）
参考例
10−テトラヒドロピラニロキシデシルアイオダ
イドの合成
１ 10−デカンジオール20ｇと57％ヨウ化水素
酸100mlを混合し、これにトルエン500mlを加え６
時間加熱還流しながら、生じる10−ヒドロキシデ
シルアイオダイドを連続的に抽出する。次いで室
温に冷却し、沈澱する１ 10−デカンジオールを
去し、トルエン層を1N−炭酸カリ水溶液、ハ
イポおよび飽和食塩水で順次洗浄後、トルエンを
減圧下に留去する。残渣を炭酸カリの存在下に蒸
留し、85〜87℃／0.1Torrの留分として無色油状
の10−ヒドロキシデシルアイオダイド25.08ｇを
得た。Example 1 Synthesis of 0-(5-ethyl-3-sulfolen-2-yl)decane-1-ol 26.6 g of 3-sulfolene, 41.4 g of 10-tetrahydropyranyloxydecyl iodide and
Dissolve 70ml of HMPA in 600ml of dry THF and heat to -78℃
Leave to cool. Next, 20.7 g of LiHMDS was dissolved in 80 ml of dry THF, and after cooling to -78°C, this was added all at once to the previously prepared THF solution with stirring under reduced pressure, and stirred at -78°C for 1 hour. Next, while gradually increasing the temperature of the reaction solution, -
After adding 100 ml of saturated saline at 20°C, raise the temperature of the solution to room temperature. Concentrate the reaction solution under reduced pressure,
After most of the THF is distilled off, 100 ml of water is added and extracted with methylene chloride. The methylene chloride layer was dried over anhydrous sodium sulfate, concentrated, and the residue was subjected to column chromatography packed with 250 g of silica gel (Wako C-200) (eluent: ethyl acetate:
22.69 g (yield: 55%) of 2-(10-tetrahydropyraniloxydecyl)-3-sulfolene was obtained. 1 H NMR (CDCl 3 ) δ (ppm) 1.20-2.20 (24H, m) 3.65 (2H, s, 5-H) 3.20-4.00 (5H, m) 4.60 (1H, m) 6.05 (2H, a, 3 -H, 4-H) IR (CHCl 3 ) 1310, 1140 cm -1 MSm/z 357 (M + -1) 7.35 g of 2-(10-tetrahydropyranyloxydecyl)-3-sulfolene obtained above, iodine Dry 1.83ml of ethyl chloride and 7.2ml of HMPA
2-(10-tetrahydropyranyloxydecyl)-5-ethyl-3-sulfolene 5.06 g of LiHMDS was dissolved in 100 ml of THF, and then 3.8 g of dry THF solution was added thereto in the same manner as above, followed by the same treatment. g (yield: 67%). 1 H NMR (CDCl 3 ) δ (ppm) 1.01 (3H, t, J=7.0Hz) 1.15-2.20 (26H, m) 3.20-4.05 (6H, m) 4.62 (1H, m) 5.98 (2H, s, 3, 4-H) IR (CHCl 3 ) 1300, 1100 cm -1 MSm/z 387 (M + +1) Next, 2-(10-tetrahydropyranyloxydecyl)-5-ethyl-3-sulfolene obtained above was treated with p-toluenesulfonic acid-pyridine salt in 95% ethanol by a conventional method,
After normal post-treatment, the desired 10% yield was 92%.
-(5-ethyl-3-sulfolen-2-yl)
Decan-1-ol was obtained. 1 H NMR (CDC 3 ) δ (ppm) 1.00 (3H, t, J = 7.0Hz) 3.20 (2H, t, J = 6.5Hz) Synthesis of (11E, 13E)-11,13-hexadecadienol Above 300 mg of 10-(5-ethyl-3-sulfolen-2-yl)decane-1-ol obtained in
Dissolve in 5 mg of 95% ethanol and add potassium carbonate to this.
Add 280 mg, and in a sealed tube under argon atmosphere, 1.5
Heated to 130°C for an hour. Next, the reaction solution was cooled to room temperature, and 20 ml of ethyl acetate was added thereto.
The inorganic salts were removed and the solvent was distilled off. The obtained residue was subjected to column chromatography using 10 g of silica gel (eluent: ethyl acetate: n-hexane = 1:9) to obtain the desired (11E, 13E).
230 mg of -11,13-hexadecadienol was obtained (yield: 95%). 1 H NMR (CDCl 3 ) δ (ppm) 1.05 (3H, t, J=7.0Hz) 1.20-1.80 (16H, m) 2.05 (4H, m) 2.68 (1H, br, s) 3.60 (2H, t, J=6.0Hz) 5.60 (2H, m) 6.00 (2H, m) 13 C NMR (CDCl 3 ) δ (ppm) 133.73 32.67 , 132.36 29.56 , 130.44 29.28 129.55 25.86 62.71 25.61 32.78, 13. 68 UV λ95%C 2 H 5 OH max230nm (ε=23090) MSm/z 238(M + ) (11E, 13E)-Synthesis of 11,13-hexadecadienal (11E, 13E)- obtained as above
344 mg of 11,13-hexadecadienol was dissolved in a mixed solvent of 10 ml of methylene chloride and 10 ml of n-hexane, and a mixture was prepared according to the method of D. Michelot et al. (Synthesis, 1983 , 130).
3.56 mg of PCC-alumina was added, and the mixture was stirred at room temperature under an argon atmosphere for 10 hours. After treating the reaction solution in a conventional manner, the obtained crude product was treated with silica gel.
The target (11E, 13E)-11,13-hexadecadienal 260 mg was obtained by column chromatography (eluent; ethyl acetate: n-hexane = 1:9) using 15 g of :67.2%). 1 H NMR (CDCl 3 ) δ (ppm) 1.00 (3H, t, J = 7.0Hz) 1.20 - 1.50 (12H, m) 1.60 (2H, m) 2.06 (4H, m) 2.44 (2H, dt, J = 2.0Hz, J=8.0Hz) 5.60 (2H, m) 6.03 (2H, m) 9.82 (1H, t, J=2.0Hz) 13 C NMR δ (ppm) 202.15 32.59 133.48 29.41 132.01 25.55 129.45 22.18 128.98 13.50 43.88 IR (CHCl 3 ) MSm/z 236 (M + ) Reference Example 10-Synthesis of tetrahydropyranyloxydecyl iodide 1 Mix 20 g of 10-decanediol and 100 ml of 57% hydroiodic acid, add 500 ml of toluene, and add 6
The resulting 10-hydroxydecyl iodide is continuously extracted while heating under reflux for a period of time. The mixture is then cooled to room temperature to remove precipitated 110-decanediol, and the toluene layer is washed successively with a 1N aqueous potassium carbonate solution, hypo and saturated saline, and the toluene is distilled off under reduced pressure. The residue was distilled in the presence of potassium carbonate to obtain 25.08 g of 10-hydroxydecyl iodide as a colorless oil as a fraction at 85-87°C/0.1 Torr.
次いで該アイオダイド11.6ｇを乾燥塩化メチレ
ンに溶解し、これにジヒドロピラン４mlおよびｐ
−トルエンスルホン酸−ピリジン塩１ｇを加え、
常法により対応するテトラハイドロピラニルエー
テルに導びき、得られる粗生成物をシリカゲルカ
ラムクロマトグラフイー（溶出液：ｎ−ヘキサ
ン：酢酸エチル＝９：１）に付し、目的の10−テ
トラハイドロピラニロキシデシルアイオダイド
14.8ｇを得た（収率：98％）。1
H NMR（CDCl3）
δ（ppm）1.34（22H、ｍ）
3.20（2H、ｔ、Ｊ＝6.5Hz）
3.60（4H、ｍ）
4.60（1H、ｍ）。 Then, 11.6 g of the iodide was dissolved in dry methylene chloride, and 4 ml of dihydropyran and p
- Add 1 g of toluenesulfonic acid-pyridine salt,
The corresponding tetrahydropyranyl ether was derived by a conventional method, and the resulting crude product was subjected to silica gel column chromatography (eluent: n-hexane: ethyl acetate = 9:1) to obtain the desired 10-tetrahydropyranyl ether. roxidecyl iodide
14.8g was obtained (yield: 98%). 1H NMR ( CDCl3 ) δ (ppm) 1.34 (22H, m) 3.20 (2H, t, J = 6.5Hz) 3.60 (4H, m) 4.60 (1H, m).
Claims (1)
ル）デカン−１−オールをアルカリの存在下に加
熱することにより、（11E，13E）−11，13−ヘキ
サデカジエン−１−オールに導き、次いで該化合
物の水酸基を酸化することを特徴とする（11E，
13E）−11，13−ヘキサデカジエナールの製造法。 ２ ２−（10−テトラヒドロピラニロキシデシル）
−５−エチル−３−スルホレンを酸で処理するこ
とにより10−（５−エチル−３−スルホレン−２
−イル）デカン−１−オールに導いた後、該化合
物をアルカリの存在下に加熱することにより、
（11E，13E）−11，13−ヘキサデカジエン−１−
オールに導き、次いで該化合物の水酸基を酸化す
ることを特徴とする（11E，13E）−11，13−ヘキ
サデカジエナールの製造法。 ３ ３−スルホレンに、塩基の存在下、10−テト
ラヒドロピラニロキシデシルハライドによる10−
テトラヒドロピラニロキシデシル基の導入および
エチルハライドによるエチル基の導入を行ない、
得られる２−（10−テトラヒドロピラニロキシデ
シル）−５−エチル−３−スルホレンを酸で処理
することにより10−（５−エチル−３−スルホレ
ン−２−イル）デカン−１−オールに導いた後、
該化合物をアルカリの存在下に加熱することによ
り（11E，13E）−11，13−ヘキサデカジエン−１
−オールに導き、次いで該化合物の水酸基を酸化
することを特徴とする（11E，13E）−11，13−ヘ
キサデカジエナールの製造法。[Claims] 1 By heating 10-(5-ethyl-3-sulfolen-2-yl)decane-1-ol in the presence of an alkali, (11E,13E)-11,13-hexadeca dien-1-ol, and then oxidizes the hydroxyl group of the compound (11E,
13E) Method for producing -11,13-hexadecadienal. 2 2-(10-tetrahydropyraniloxydecyl)
10-(5-ethyl-3-sulfolene-2) is obtained by treating -5-ethyl-3-sulfolene with acid.
-yl)decane-1-ol by heating the compound in the presence of an alkali,
(11E, 13E)-11,13-hexadecadiene-1-
1. A method for producing (11E, 13E)-11,13-hexadecadienal, which comprises converting the compound into ol and then oxidizing the hydroxyl group of the compound. 3 3-Sulfolene is treated with 10-tetrahydropyraniloxydecyl halide in the presence of a base.
Introducing a tetrahydropyranyloxydecyl group and an ethyl group using ethyl halide,
The resulting 2-(10-tetrahydropyraniloxydecyl)-5-ethyl-3-sulfolene was treated with acid to yield 10-(5-ethyl-3-sulfolen-2-yl)decane-1-ol. rear,
By heating the compound in the presence of an alkali, (11E, 13E)-11,13-hexadecadiene-1
-ol, and then oxidizing the hydroxyl group of the compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18325184A JPS6160630A (en) | 1984-08-31 | 1984-08-31 | Preparation of aldehyde derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18325184A JPS6160630A (en) | 1984-08-31 | 1984-08-31 | Preparation of aldehyde derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6160630A JPS6160630A (en) | 1986-03-28 |
| JPH055819B2 true JPH055819B2 (en) | 1993-01-25 |
Family
ID=16132407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18325184A Granted JPS6160630A (en) | 1984-08-31 | 1984-08-31 | Preparation of aldehyde derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6160630A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210108939A (en) * | 2018-12-27 | 2021-09-03 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Compounds, (co)polymers, compositions, methods for forming patterns, and methods for preparing compounds |
-
1984
- 1984-08-31 JP JP18325184A patent/JPS6160630A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6160630A (en) | 1986-03-28 |
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