JPS6346055B2 - - Google Patents
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- Publication number
- JPS6346055B2 JPS6346055B2 JP7480087A JP7480087A JPS6346055B2 JP S6346055 B2 JPS6346055 B2 JP S6346055B2 JP 7480087 A JP7480087 A JP 7480087A JP 7480087 A JP7480087 A JP 7480087A JP S6346055 B2 JPS6346055 B2 JP S6346055B2
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- JP
- Japan
- Prior art keywords
- general formula
- formula
- group
- represented
- reaction
- Prior art date
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 13
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- -1 3-propyl-2-hexenyl group Chemical group 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- RVAUSKMBHSAUGT-UHFFFAOYSA-N 3,3-dimethyl-2-prop-1-en-2-ylpent-4-en-1-ol Chemical compound CC(=C)C(CO)C(C)(C)C=C RVAUSKMBHSAUGT-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 description 3
- 239000005792 Geraniol Substances 0.000 description 3
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 3
- 239000007818 Grignard reagent Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229940113087 geraniol Drugs 0.000 description 3
- 150000004795 grignard reagents Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- HWUMVJBWKZMIKH-AATRIKPKSA-N (2e)-hepta-2,6-dien-1-ol Chemical compound OC\C=C\CCC=C HWUMVJBWKZMIKH-AATRIKPKSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000004808 allyl alcohols Chemical class 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 description 2
- DQEUYIQDSMINEY-UHFFFAOYSA-M magnesium;prop-1-ene;bromide Chemical compound [Mg+2].[Br-].[CH2-]C=C DQEUYIQDSMINEY-UHFFFAOYSA-M 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 150000003505 terpenes Chemical group 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LAAVYEUJEMRIGF-UHFFFAOYSA-N 2,4,4-trimethylpent-2-ene Chemical compound CC(C)=CC(C)(C)C LAAVYEUJEMRIGF-UHFFFAOYSA-N 0.000 description 1
- FVCDMHWSPLRYAB-UHFFFAOYSA-N 2-ethenyl-2-methyloxirane Chemical compound C=CC1(C)CO1 FVCDMHWSPLRYAB-UHFFFAOYSA-N 0.000 description 1
- XEYSEXKESYFZOD-UHFFFAOYSA-N 2-ethenylpent-4-en-1-ol Chemical compound OCC(C=C)CC=C XEYSEXKESYFZOD-UHFFFAOYSA-N 0.000 description 1
- JZQHTTYHPIAPCZ-UHFFFAOYSA-N 2-prop-1-en-2-yloxirane Chemical compound CC(=C)C1CO1 JZQHTTYHPIAPCZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000005952 Cope rearrangement reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZKQFHRVKCYFVCN-UHFFFAOYSA-N ethoxyethane;hexane Chemical compound CCOCC.CCCCCC ZKQFHRVKCYFVCN-UHFFFAOYSA-N 0.000 description 1
- UCCNWJJCBGANDL-UHFFFAOYSA-N hepta-1,6-dien-3-ol Chemical compound C=CC(O)CCC=C UCCNWJJCBGANDL-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LHTVMBMETNGEAN-UHFFFAOYSA-N pent-1-en-1-ol Chemical compound CCCC=CO LHTVMBMETNGEAN-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はテルペン骨格またはテルペンに類似の
骨格を有するアリル型アルコールの製造方法に関
し、詳しくは一般式
〔式中R1およびR4は独立に水素原子もしくは低
級アルキル基を表わすかまたは一緒になつて低級
アルキレン基を表わし、R2およびR3は独立に水
素原子または低級アルキル基を表わし、R5は水
素原子、アルキル基、アルケニル基または式
【式】で示される
基を表わし、ここでｎは２以上の整数を表わし、
R6およびR7は独立に水素原子、アルキル基また
はアルケニル基を表わす〕
で示されるアリル型アルコールの製造方法に関す
る。
本発明の方法によつて得られるゲラニオールな
どに代表される一般式（）で示されるアリル型
アルコールは、香料の香気成分などとして有用で
ある。
〔従来の技術〕
１，２−エポキシ−３−ブテンまたは１，２−
エポキシ−２−メチル−３−ブテンとアリル基、
２−ブテニル基または３−プロピル−２−ヘキセ
ニル基のような炭化水素基を有するグリニヤール
試薬とをテトラヒドロフラン中、５％の臭化銅
（）の存在下で−25℃の温度で反応させること
によつてそれぞれ対応するアリル型アルコールが
得られることが知られている（C.Cahiez et al.、
Synthesis、1978、528参照）。
（各式中Ｘはハロゲン原子を表わす）
〔発明が解決しようとする問題点〕
本発明者らが１，２−エポキシ−３−ブテンと
臭化アリルマグネシウムとをヨウ化銅（）の存
在下または不存在下に反応させたところ、ヨウ化
銅（）の存在下に反応させた場合には２，６−
ヘプタジエン−１−オールと２−ビニル−４−ペ
ンテン−１−オールとが81.2対18.8の割合で得ら
れ、またヨウ化銅（）の不存在下に反応させた
場合には２，６−ヘプタジエン−１−オールと２
−ビニル−４−ペンテン−１−オールとが70.0対
30.0の割合で得られた。
このように、１，２−エポキシ−３−ブテンな
どの不飽和エポキシ化合物と臭化アリルマグネシ
ウムなどのアリル型の炭化水素基を有するグリニ
ヤール試薬との反応では通常２種類の付加生成物
が得られる。
本発明者らは、１般式
（式中R1、R2、R3およびR4は前記定義のとおり
である）
で示される不飽和エポキシ化合物とアリル型の炭
化水素基を有する有機錫化合物をある種のルイス
酸の存在下に反応させる場合には、一般式（）
で示される不飽和エポキシ化合物の２−位に該ア
リル型の炭化水素基が導入された一般式
（式中R1、R2、R3、R4、R5、R6およびR7は前記
定義のとおりである）
で示されるβ−アリル置換−γ，δ−不飽和アル
コールが高選択率で得られるという知見を得た。
しかして、本発明の目的は、一般式（）で示
されるβ−アリル置換−γ，δ−不飽和アルコー
ルを用いて一般式（）で示されるアリル型アル
コールを容易にかつほぼ定量的に製造することが
できる新しい方法を提供することにある。
〔問題点を解決するための手段〕
本発明によれば、上記の目的は、一般式（）
で示されるβ−アリル置換−γ，δ−不飽和アル
コールを加熱転位させることを特徴とする一般式
（）で示されるアリル型アルコールの製造方法
を提供することによつて達成される。
前記の一般式におけるR1、R2、R3、R4、R5、
R6およびR7を以下に詳しく説明する。R1、R2、
R3およびR4が表わす低級アルキル基はメチル、
エチル、ｎ−プロピル、ｉ−プロピル、ｎ−ブチ
ル、ｉ−ブチル、ｎ−ペンチル、ｎ−ヘキシル等
を包含する。またR1とR4とは相互に一緒になつ
てメチレン、エチレン等の低級アルキレン基を構
成することができる。R1〜R4はこれらの基およ
び水素原子から、生成物の所望の構造が得られる
ように適宜選ばれるべきであるが、生成物の有用
性の点ではR1およびR4はともに水素原子である
かまたは一緒になつてメチレンもしくはエチレン
を構成し、R2が水素原子であり、かつR3がメチ
ルまたはエチルである場合がとくに好ましい。
R5は水素原子；メチル、エチル、ブチル、ペン
チル、オクテル、デシル、エイコシル等のアルキ
ル基；ビニル、アリル、イソプロペニル、３−ブ
テン−１−イル、３−メチル−３−ブテン−１−
イル、３−メチル−２−ブテン−１−イル、４−
ペンテン−１−イル、４−メチル−３−ペンテン
−１−イル、フイチルメチル等のアルケニル基；
または式【式】に
おいてｎが２以上の整数である炭化水素基、例え
ばゲラニルメチル、フアルネシルメチル、ゲラニ
ルゲラニルメチル、ソラネシルメチル、デカプレ
ニルメチル等の基を表わす。上記式においてｎは
12以下の整数である場合が好ましい。R6および
R7はR5に関して言及した如きアルキル基、アル
ケニル基および水素原子から目的に応じて選ばれ
る。
本発明に従う加熱転位（コープ転位）反応は、
一般式（）で表わされるβ−アリル置換−γ，
δ−不飽和アルコールを150〜300℃の範囲内の温
度に加熱することによつて実施される。
本発明で使用する一般式（）で示されるβ−
アリル置換−γ，δ−不飽和アルコールは、一般
式（）で示される不飽和エポキシ化合物と一般
式
（式中R5、R6およびR7は前記定義のとおりであ
り、R8、R9およびR10は独立に低級アルキル基ま
たは置換されていてもよいフエニル基を表わす）
で示される有機錫化合物とを三フツ化ホウ素、三
フツ化ホウ素エーテラートまたは塩化アルミニウ
ムの存在下で反応させることによつて高選択率で
製造される。
上記の不飽和エポキシ化合物と有機錫化合物と
の反応は、触媒としての三フツ化ホウ素、三フツ
化ホウ素エーテラート（例えばジエチルエーテラ
ート）または塩化アルミニウムの存在下で両者を
接触させることにより行われるが、反応の選択性
の点から反応温度は０〜−80℃のような比較的低
温が好ましい。反応溶媒は不可欠ではないが、反
応に関与しないものを使用するのが選択性の面で
好ましく、たとえば塩化メチレン、四塩化炭素、
クロロホルムなどを使用することができる。一般
式（）で示される不飽和エポキシ化合物と一般
式（）で示される有機錫化合物との使用割合は
厳密ではないが、前者１モルあたり後者0.2〜５
モルの範囲が適当である。反応剤および触媒の仕
込み順序は任意に選ぶことができるが、例えば三
フツ化ホウ素エーテラートを触媒として用いる反
応では、一般式（）で示される不飽和エポキシ
化合物と一般式（）で示される有機錫化合物と
の混合溶液に三フツ化ホウ素エーテラートを滴下
する場合が一般的に収率が高い。
一般式（）で示される有機錫化合物は、例え
ば次に示すように一般式（）で示される有機ハ
ロゲン化物と一般式（）で示されるリチウム錫
化合物とを反応させることにより調製することが
できる。
なお、一般式（）で示されるリチウム錫化合
物は例えば下記(i)、(ii)または(iii)の反応により得ら
れる。
(i) HSnR8R9R10＋C4H9Li→LiSnR8R9R10
(ii) （R8R9R10Sn）2＋C4H9Li→LiSnR8R9R10
(iii) R8R9R10SnX＋Li→LiSnR8R9R10
別法として下記のように一般式（）で示され
る有機マグネシウムハライドと一般式（）で示
される有機錫ハライドとを反応させることによつ
ても一般式（）で示される有機錫化合物を調整
することができる。
上記の各式において、R5、R6、R7、R8、R9お
よびR10は前記定義のとおりであり、Ｘはハロゲ
ン原子を表わす。
また、一般式（）で示される不飽和エポキシ
化合物は例えば次の反応により調整される。
(1) ジエンと過酸の反応
（式中Ｒは炭化水素基を表わす）
〔例えばJ.K.Crandall et al.、J.Org.Chem.、
33、423（1968）およびN.Heap et、al.、J.
Chem.Soc.、(B)、164（1966）参照〕
(2) イオウイリドとα，β−不飽和アルデヒドの
反応
〔例えばE.J.Corey et al.、J.Amer.Chem.
Soc.、87、1353（1965）およびA.Merz et al.、
Angew.Chem.Internat.Edit.、12、845（1973）
参照〕
〔実施例〕
次に、実施例により本発明を具体的に説明する
が、特定の反応例を示すにすぎない該実施例によ
つて本発明は限定的に解釈されるものでない。
参考例 １
塩化メチレン15mlに１，２−エポキシ−３−メ
チル−３−ブテン３ミリモルと該１，２−エポキ
シ−３−メチル−３−ブテンに対して1.1当量の
トリメチル（３−メチル−２−ブテニル）錫を加
え、得られた溶液中に−78℃で三フツ化ホウ素ジ
エチルエーテラート３ミリモルを加えて１時間反
応させたのち、反応温度を0.5時間を要してゆつ
くりと−10℃まで上昇させた。反応終了後、反応
溶液に水を加え、有機層と水層とに分離し、水層
をジエチルエーテルで２回抽出した。有機層を合
し、水で２回洗滌したのち、無水硫酸マグネシウ
ム上で乾燥した。ガスクロマトグラフイー（カラ
ム10％−Ucon oil LB550、内部標準ｎ−ヘプタ
ノールにより生成物を標品とし比較した結果、
３，３−ジメチル−２−イソプロペニル−４−ペ
ンテノールへの選択率は95％以上であることが判
明した。有機層をロータリーエバポレーターで濃
縮したのち、その残渣をシリカゲルクロマトグラ
フイー（展開溶媒：ヘキサン−ジエチルエーテル
混合溶媒）に付することにより、３，３−ジメチ
ル−２−イソプロペニル−４−ペンテノールを単
離収率91％で得た。なお、得られた３，３−ジメ
チル−２−イソプロペニル−４−ペンテノールの
構造はNMRおよびIRにより同定された。
実施例 １
３，３−ジメチル−２−イソプロペニル−４−
ペンテノール154mgをアルゴン雰囲気下に190〜
195℃で２時間加熱反応させ、ゲラニオール
（Ｅ／Ｚ＝58／42）を定量的に得た。このものの
ガスクロマトグラフイーでの保持時間および
NMRスペクトルが市販の標品のものと一致した
ことにより、生成したゲラニオールの構造を確認
した。
〔発明の効果〕
本発明によれば、上記の実施例から明らかなと
おり、一般式（）で示されるβ−アリル置換−
γ，δ−不飽和アルコールから一般式（）で示
されるアリル型アルコールを容易にかつほぼ定量
的に製造することができる。 [Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing an allylic alcohol having a terpene skeleton or a skeleton similar to a terpene. [In the formula, R 1 and R 4 independently represent a hydrogen atom or a lower alkyl group, or together represent a lower alkylene group, R 2 and R 3 independently represent a hydrogen atom or a lower alkyl group, and R 5 represents a hydrogen atom, an alkyl group, an alkenyl group, or a group represented by the formula [Formula], where n represents an integer of 2 or more,
R 6 and R 7 independently represent a hydrogen atom, an alkyl group, or an alkenyl group. Allyl alcohols represented by the general formula (), such as geraniol, obtained by the method of the present invention are useful as aroma components of perfumes. [Prior art] 1,2-epoxy-3-butene or 1,2-
Epoxy-2-methyl-3-butene and allyl group,
A Grignard reagent having a hydrocarbon group such as a 2-butenyl group or a 3-propyl-2-hexenyl group is reacted with a Grignard reagent having a hydrocarbon group such as a 2-butenyl group or a 3-propyl-2-hexenyl group in the presence of 5% copper bromide () in tetrahydrofuran at a temperature of -25°C. It is known that corresponding allylic alcohols can be obtained in this way (C. Cahiez et al.,
Synthesis, 1978 , 528). (In each formula, X represents a halogen atom) [Problems to be solved by the invention] The present inventors prepared 1,2-epoxy-3-butene and allylmagnesium bromide in the presence of copper iodide (). Or, when the reaction was carried out in the absence of copper iodide, the reaction was carried out in the presence of 2,6-
Heptadien-1-ol and 2-vinyl-4-penten-1-ol were obtained in a ratio of 81.2 to 18.8, and 2,6-heptadien-1-ol was obtained in the absence of copper iodide. -1-all and 2
-70.0 pairs with vinyl-4-penten-1-ol
Obtained at a rate of 30.0. Thus, the reaction of an unsaturated epoxy compound such as 1,2-epoxy-3-butene with a Grignard reagent having an allylic hydrocarbon group such as allylmagnesium bromide usually yields two types of addition products. . The inventors have determined that the general formula (In the formula, R 1 , R 2 , R 3 and R 4 are as defined above.) An unsaturated epoxy compound represented by the formula and an organotin compound having an allyl hydrocarbon group are mixed in the presence of a certain Lewis acid. When reacting with, the general formula ()
A general formula in which the allyl type hydrocarbon group is introduced at the 2-position of an unsaturated epoxy compound represented by (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined above) I obtained the knowledge that it can be obtained by Therefore, an object of the present invention is to easily and almost quantitatively produce an allylic alcohol represented by the general formula () using a β-allyl substituted-γ,δ-unsaturated alcohol represented by the general formula (). Our goal is to provide new ways to do things. [Means for solving the problem] According to the present invention, the above object is achieved by solving the general formula ()
This is achieved by providing a method for producing an allylic alcohol represented by the general formula (), which is characterized by carrying out thermal rearrangement of a β-allyl substituted -γ,δ-unsaturated alcohol represented by the formula (). R 1 , R 2 , R 3 , R 4 , R 5 in the general formula above,
R 6 and R 7 are explained in detail below. R1 , R2 ,
The lower alkyl group represented by R 3 and R 4 is methyl,
Includes ethyl, n-propyl, i-propyl, n-butyl, i-butyl, n-pentyl, n-hexyl, and the like. Furthermore, R 1 and R 4 can be taken together to form a lower alkylene group such as methylene or ethylene. R 1 to R 4 should be appropriately selected from these groups and hydrogen atoms to obtain the desired structure of the product, but in terms of the usefulness of the product, R 1 and R 4 should both be hydrogen atoms. or together form methylene or ethylene, R 2 is a hydrogen atom and R 3 is methyl or ethyl.
R 5 is a hydrogen atom; an alkyl group such as methyl, ethyl, butyl, pentyl, octyl, decyl, eicosyl; vinyl, allyl, isopropenyl, 3-buten-1-yl, 3-methyl-3-buten-1-
yl, 3-methyl-2-buten-1-yl, 4-
Alkenyl groups such as penten-1-yl, 4-methyl-3-penten-1-yl, phythylmethyl;
Or it represents a hydrocarbon group in which n is an integer of 2 or more, such as geranylmethyl, farnesylmethyl, geranylgeranylmethyl, solanesylmethyl, decaprenylmethyl, and the like. In the above formula, n is
Preferably, it is an integer of 12 or less. R6 and
R 7 is optionally selected from alkyl groups, alkenyl groups, and hydrogen atoms as mentioned for R 5 . The heated rearrangement (Cope rearrangement) reaction according to the present invention is
β-allyl substituted −γ represented by the general formula (),
It is carried out by heating the delta-unsaturated alcohol to a temperature within the range of 150-300<0>C. β- represented by the general formula () used in the present invention
Allyl-substituted-γ,δ-unsaturated alcohol is an unsaturated epoxy compound represented by the general formula () and a general formula (In the formula, R 5 , R 6 and R 7 are as defined above, and R 8 , R 9 and R 10 independently represent a lower alkyl group or an optionally substituted phenyl group) It is produced with high selectivity by reacting the compound with boron trifluoride, boron trifluoride etherate, or aluminum chloride. The reaction between the unsaturated epoxy compound and the organotin compound described above is carried out by bringing the two into contact in the presence of boron trifluoride, boron trifluoride etherate (e.g. diethyl etherate) or aluminum chloride as a catalyst. From the viewpoint of reaction selectivity, the reaction temperature is preferably relatively low, such as 0 to -80°C. Although the reaction solvent is not essential, it is preferable to use one that does not participate in the reaction in terms of selectivity, such as methylene chloride, carbon tetrachloride,
Chloroform etc. can be used. The usage ratio of the unsaturated epoxy compound represented by the general formula () and the organic tin compound represented by the general formula () is not strict, but it is 0.2 to 5 mol of the latter per 1 mole of the former.
A molar range is suitable. The order of charging the reactants and catalysts can be arbitrarily selected, but for example, in a reaction using boron trifluoride etherate as a catalyst, an unsaturated epoxy compound represented by the general formula () and an organic tin represented by the general formula () are used. The yield is generally high when boron trifluoride etherate is added dropwise to a mixed solution with the compound. The organotin compound represented by the general formula () can be prepared, for example, by reacting the organic halide represented by the general formula () with the lithium tin compound represented by the general formula () as shown below. . Note that the lithium tin compound represented by the general formula () can be obtained, for example, by the following reaction (i), (ii), or (iii). (i) HSnR 8 R 9 R 10 +C 4 H 9 Li→LiSnR 8 R 9 R 10 (ii) (R 8 R 9 R 10 Sn) 2 +C 4 H 9 Li→LiSnR 8 R 9 R 10 (iii) R 8 R 9 R 10 SnX + Li → LiSnR 8 R 9 R 10 Alternatively, as shown below, by reacting an organomagnesium halide represented by the general formula () with an organotin halide represented by the general formula (). An organic tin compound represented by the general formula () can be prepared. In each of the above formulas, R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are as defined above, and X represents a halogen atom. Further, the unsaturated epoxy compound represented by the general formula () is prepared, for example, by the following reaction. (1) Reaction of diene and peracid (In the formula, R represents a hydrocarbon group) [For example, JK Crandall et al., J.Org.Chem.,
33, 423 (1968) and N. Heap et, al., J.
See Chem.Soc., (B), 164 (1966)] (2) Reaction of sulfur and α,β-unsaturated aldehydes [For example, EJCorey et al., J.Amer.Chem.
Soc., 87 , 1353 (1965) and A. Merz et al.,
Angew.Chem.Internat.Edit., 12 , 845 (1973)
Reference] [Example] Next, the present invention will be specifically explained with reference to Examples, but the present invention should not be construed as being limited by the Examples, which merely show specific reaction examples. Reference Example 1 In 15 ml of methylene chloride, 3 mmol of 1,2-epoxy-3-methyl-3-butene and 1.1 equivalent of trimethyl (3-methyl-2-butene) were added to 15 ml of methylene chloride. -butenyl)tin was added, and 3 mmol of boron trifluoride diethyl etherate was added to the resulting solution at -78°C and reacted for 1 hour, and then the reaction temperature was slowly increased over a period of 0.5 hour to -10 It was raised to ℃. After the reaction was completed, water was added to the reaction solution to separate it into an organic layer and an aqueous layer, and the aqueous layer was extracted twice with diethyl ether. The organic layers were combined, washed twice with water, and then dried over anhydrous magnesium sulfate. Gas chromatography (column 10% - Ucon oil LB550, internal standard n-heptanol, product was compared as a standard,
The selectivity to 3,3-dimethyl-2-isopropenyl-4-pentenol was found to be greater than 95%. After concentrating the organic layer using a rotary evaporator, the residue was subjected to silica gel chromatography (developing solvent: hexane-diethyl ether mixed solvent) to obtain 3,3-dimethyl-2-isopropenyl-4-pentenol. Obtained with an isolated yield of 91%. The structure of the obtained 3,3-dimethyl-2-isopropenyl-4-pentenol was identified by NMR and IR. Example 1 3,3-dimethyl-2-isopropenyl-4-
154mg of pentenol under argon atmosphere 190~
A heating reaction was carried out at 195° C. for 2 hours to quantitatively obtain geraniol (E/Z=58/42). Retention time of this substance in gas chromatography and
The structure of the produced geraniol was confirmed because the NMR spectrum matched that of a commercially available standard. [Effects of the Invention] According to the present invention, as is clear from the above examples, β-allyl substituted -
The allylic alcohol represented by the general formula () can be easily and almost quantitatively produced from a γ,δ-unsaturated alcohol.
Claims (1)
級アルキル基を表わすかまたは一緒になつて低級
アルキレン基を表わし、R2およびR3は独立に水
素原子または低級アルキル基を表わし、R5は水
素原子、アルキル基、アルケニル基または式
【式】で示される 基を表わし、ここでｎは２以上の整数を表わし、
R6およびR7は独立に水素原子、アルキル基また
はアルケニル基を表わす〕 で示されるβ−アリル置換−γ，δ−不飽和アル
コールを加熱転位させることを特徴とする一般式 （式中R1、R2、R3、R4、R5、R6およびR7は前記
定義のとおりである） で示されるアリル型アルコールの製造方法。[Claims] 1. General formula [In the formula, R 1 and R 4 independently represent a hydrogen atom or a lower alkyl group, or together represent a lower alkylene group, R 2 and R 3 independently represent a hydrogen atom or a lower alkyl group, and R 5 represents a hydrogen atom, an alkyl group, an alkenyl group, or a group represented by the formula [Formula], where n represents an integer of 2 or more,
R 6 and R 7 independently represent a hydrogen atom, an alkyl group, or an alkenyl group] A general formula characterized by thermally rearranging a β-allyl-substituted-γ,δ-unsaturated alcohol represented by (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined above.) A method for producing an allyl alcohol represented by the following formula.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7480087A JPS6322041A (en) | 1987-03-27 | 1987-03-27 | Production of allyl type alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7480087A JPS6322041A (en) | 1987-03-27 | 1987-03-27 | Production of allyl type alcohol |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8619680A Division JPS5711930A (en) | 1980-06-24 | 1980-06-24 | Production of unsaturated alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6322041A JPS6322041A (en) | 1988-01-29 |
| JPS6346055B2 true JPS6346055B2 (en) | 1988-09-13 |
Family
ID=13557742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7480087A Granted JPS6322041A (en) | 1987-03-27 | 1987-03-27 | Production of allyl type alcohol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6322041A (en) |
-
1987
- 1987-03-27 JP JP7480087A patent/JPS6322041A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6322041A (en) | 1988-01-29 |
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