JPS6254407B2 - - Google Patents
Info
- Publication number
- JPS6254407B2 JPS6254407B2 JP56096950A JP9695081A JPS6254407B2 JP S6254407 B2 JPS6254407 B2 JP S6254407B2 JP 56096950 A JP56096950 A JP 56096950A JP 9695081 A JP9695081 A JP 9695081A JP S6254407 B2 JPS6254407 B2 JP S6254407B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- alkyl group
- reaction
- propargyl alcohol
- lower 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
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 6
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 claims description 6
- 239000007818 Grignard reagent Substances 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 150000004795 grignard reagents Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- GLZPCOQZEFWAFX-JXMROGBWSA-N Nerol Natural products CC(C)=CCC\C(C)=C\CO GLZPCOQZEFWAFX-JXMROGBWSA-N 0.000 claims description 2
- 150000001351 alkyl iodides Chemical class 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000003747 Grignard reaction Methods 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- -1 alkenyl Grignard reagent Chemical class 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 241000486679 Antitype Species 0.000 description 1
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 1
- 239000005792 Geraniol Substances 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- 229910011687 LiCu Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- YSMZEMQBSONIMJ-UHFFFAOYSA-M magnesium;2-methanidylpropane;chloride Chemical compound [Mg+2].[Cl-].CC(C)[CH2-] YSMZEMQBSONIMJ-UHFFFAOYSA-M 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は、プロパギルアルコールからグリニヤ
ール反応を利用して、三置換オレフインを製造す
る方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing trisubstituted olefins from propargyl alcohol using a Grignard reaction.
本発明者らは、Cp2TiCl2（Cpはシクロベンタ
ジエニル基またはその誘導体をあらわす）を触媒
とするグリニヤール反応に関する一連の研究にお
いて、内部アセチレンに対しては立体選択的なハ
イドロマグネセーシヨン反応が起ることを知つ
て、さきに報告した。 In a series of studies on the Grignard reaction catalyzed by Cp 2 TiCl 2 (Cp represents a cyclobentadienyl group or its derivative), the present inventors found that stereoselective hydromagnesis for internal acetylene I reported it earlier, knowing that a reaction would occur.
続いて、反応の位置選択性が置換基の影響を強
く受けるという事実にかんがみ、内部アセチレン
としてプロパギルアルコールをえらんでハイドロ
マグネセーシヨンを行ない、プロパギル位のヒド
ロキシ基の存在が、反応の立体選択性および位置
選択性のどのような影響を及ぼすかを追究した。 Next, considering the fact that the regioselectivity of the reaction is strongly influenced by substituents, we selected propargyl alcohol as the internal acetylene and performed hydromagnesis. We investigated the effects of sex and regioselectivity.
その結果、下式に示すように、プロパギルアル
コールのハイドロマグネセーシヨンは位置およ
び立体選択性に関して特異に進行し、アルケニル
グリニヤール試薬がほぼ定量的に得られること
を見出して本発明に至つた。 As a result, as shown in the following formula, the hydromagnesis of propargyl alcohol proceeds specifically with respect to regioselectivity and stereoselectivity, and it has been found that an alkenyl Grignard reagent can be obtained almost quantitatively, leading to the present invention.
周知のとおり、このアルケニルグリニヤール試
薬はきわめて反応性高く、種々の三置換オレフ
インを与えることができる。 As is well known, this alkenyl Grignard reagent is extremely reactive and can give a variety of trisubstituted olefins.
本発明の三置換オレフインを製造する方法は、次
式のプロパギルアルコール
〔式中、R1およびR2は同一または異なるもの
であつて、水素原子または低級アルキル基をあら
わす。R3はアルキル基、アリール基、アルケニ
ル基またはアルカジエニル基をあらわし、反応に
対して不活性な限り置換基を有していてもよ
い。〕
に、グリニヤール試薬
RMgX
〔Ｒは低級アルキル基をあらわし、ＸはCl，
BrまたはＩである。〕
を、触媒量の
Cp2TiCl2
〔Cpはシクロベンタジエニル基またはその誘
導体をあらわす。〕
の存在下に反応させた後、ヨウ素またはヨウ化ア
ルキルを反応させ、式
〔式中、R1およびR2は同一または異なるもの
であつて、水素原子または低級アルキル基をあら
わす。R3はアルキル基、アリール基、アルケニ
ル基またはアルカジエニル基をあらわし、反応に
対して不活性な限り置換基を有していてもよい。
R4はヨウ素原子またはアルキル基をあらわす。〕
を得ることからなる。 The method for producing the trisubstituted olefin of the present invention includes propargyl alcohol of the following formula: [In the formula, R 1 and R 2 are the same or different and represent a hydrogen atom or a lower alkyl group. R 3 represents an alkyl group, an aryl group, an alkenyl group, or an alkadienyl group, and may have a substituent as long as it is inert to the reaction. ], Grignard reagent RMgX [R represents a lower alkyl group, X is Cl,
Br or I. ] in a catalytic amount of Cp 2 TiCl 2 [Cp represents a cyclobentadienyl group or a derivative thereof. ] After reacting in the presence of iodine or alkyl iodide, the formula [In the formula, R 1 and R 2 are the same or different and represent a hydrogen atom or a lower alkyl group. R 3 represents an alkyl group, an aryl group, an alkenyl group, or an alkadienyl group, and may have a substituent as long as it is inert to the reaction.
R 4 represents an iodine atom or an alkyl group. ] It consists of obtaining.
さきにコーリーらは、プロパギルアルコールに
LiAlH4を作用させたのちヨウ素で分解して
（Ｚ）３−ヨード−２−アルケン−１−オールを
合成し、さらにこれにLiCu（CH3）2を反応させ
て、(E)−３−メチル−アルケン−１−オールを得
ることに成功し、天然物の合成ルートの一つを開
いた。 Previously, Corey et al.
After reacting with LiAlH 4 , it is decomposed with iodine to synthesize (Z) 3-iodo-2-alken-1-ol, which is further reacted with LiCu(CH 3 ) 2 to form (E)-3- We succeeded in obtaining methyl-alken-1-ol, opening one of the synthetic routes for natural products.
E.J.Corey et al，J.Am.Chem.Soc，89，4245
（1967）
上記の付加反応はアンチ型であり、得られた三
置換オレフインはトランス型である。 EJCorey et al, J.Am.Chem.Soc, 89 , 4245
(1967) The above addition reaction is of the anti-type, and the resulting trisubstituted olefin is of the trans-type.
一方、本発明の方法によるときは、これとは逆
にシン型の付加によりシス型の生成物が得られ
る。従つて本発明は、コーリーらの方法とは別の
三置換オレフインの合成ルートを提供することに
なる。本発明の方法は、後記する例に示すとお
り、収率が高いばかりでなく立体選択率がきわめ
て高いから、天然物中に多く存在する、または天
然物合成中間体として有用なγ，γ′−二置換−
２−アルケン−１−オール類の選択的な合成法と
して有力なものといえよう。 On the other hand, when using the method of the present invention, on the contrary, a cis-type product is obtained by addition of a syn-type. The present invention therefore provides an alternative route to the synthesis of trisubstituted olefins than the method of Corey et al. As shown in the examples below, the method of the present invention not only provides a high yield but also has an extremely high stereoselectivity. Disubstitution −
This method can be said to be a promising method for selectively synthesizing 2-alken-1-ols.
プロパギルアルコールに対するグリニヤール試
薬の量は、ほぼ当量ないし少過剰すなわち（1.2
倍程度）あればよい。触媒として用いる
Cp2TiCl2は、これらに対して５〜10モル％加え
れば足りる。 The amount of Grignard reagent relative to propargyl alcohol is approximately equivalent to a slight excess, i.e. (1.2
(approximately double) is sufficient. used as a catalyst
It is sufficient to add 5 to 10 mol % of Cp 2 TiCl 2 to these.
反応媒体は、ジエチルエーテルのようなエーテ
ルが好適である。テトラヒドロフラン中では、反
応が所期のように進み難いことが経験された。反
応温度は常温で十分である。反応剤の組み合わせ
により多少は異なるが、多くの場合、４時間でほ
ぼ100％反応が進行する。 The reaction medium is preferably an ether such as diethyl ether. It was experienced that the reaction did not proceed as expected in tetrahydrofuran. Room temperature is sufficient for the reaction temperature. Although it varies somewhat depending on the combination of reactants, in most cases, the reaction progresses approximately 100% in 4 hours.
実施例 １
10mlのエーテルに、アルゴンガス雰囲気下でイ
ソブチルマグネシウムクロライド8.4ｍmolおよび
Cp2TiCl247mg（0.19ｍmol）を溶解して、０℃で
５分間反応させた。そこへ、２−ヘプチン−１−
オール430mg（3.8ｍmol）を加え、室温で４時間
撹拌して反応させた。Example 1 In 10 ml of ether, 8.4 mmol of isobutylmagnesium chloride and
47 mg (0.19 mmol) of Cp 2 TiCl 2 was dissolved and reacted at 0° C. for 5 minutes. There, 2-heptine-1-
430 mg (3.8 mmol) of ol was added, and the mixture was stirred at room temperature for 4 hours to react.
エーテルを蒸発させてからテトラヒドロフラン
に再溶解し、溶液を二分して、一方にはヨウ素を
加え、他方にはヨウ化メチルを加えた。 The ether was evaporated and redissolved in tetrahydrofuran, and the solution was divided into two parts, with iodine added to one and methyl iodide added to the other.
NMR分析により生成物の構造をしらべ、それ
ぞれ(E)−３−ヨード−２−アルケン−１−オール
および（Ｚ）−３−メチル−２−アルケン−１−
オールを得た。 The structures of the products were determined by NMR analysis, and they were found to be (E)-3-iodo-2-alken-1-ol and (Z)-3-methyl-2-alken-1-ol, respectively.
Got the oars.
実施例 ２
原料プロパギルアルコールとして
の構造の化合物を使用し、実施例１と同様に、ま
ずイソブチルマグネシウムクロライドと
Cp2TiCl2を加えてグリニヤール付加反応を行な
い、さらにCH3Iでメチル化して、ネロールを95
％〔98％純度、（GLC分析）〕の収率で得た。 Example 2 As raw material propargyl alcohol Using a compound with the structure of
Grignard addition reaction was performed by adding Cp 2 TiCl 2 and further methylation with CH 3 I to convert nerol to 95
% [98% purity, (GLC analysis)].
なお、このようなテルペノイドの合成は前述の
ようにコーリーらの方法によつてもできるが、同
じ原料から出発して、製品はゲラニオールとな
る。 Note that such terpenoids can also be synthesized by the method of Corey et al., as described above, but starting from the same raw materials, the product is geraniol.
実施例 ３
出発原料に
の構造の化合物をえらび、実施例２と同様に処理
して、（Ｅ，Ｚ）−フアルネソールを収率96％〔98
％純度、（GLC分析）〕で得た。Example 3 Starting material A compound with the structure was selected and treated in the same manner as in Example 2 to obtain (E,Z)-furnesol in a yield of 96%
% purity, (GLC analysis)].
Claims (1)
であつて、水素原子または低級アルキル基をあら
わす。R3はアルキル基、アリール基、アルケニ
ル基またはアルカジエニル基をあらわし、反応に
対して不活性な限り置換基を有していてもよ
い。〕 に、グリニヤール試薬 RMgX 〔Ｒは低級アルキル基をあらわし、ＸはCl，
BrまたはＩである。〕 を、触媒量の Cp2TiCl2 〔Cpはシクロペンタジエニル基またはその誘
導体をあらわす。〕 の存在下に反応させた後、ヨウ素またはヨウ化ア
ルキルを反応させて次式の三置換オレフイン 〔R1およびR2は同一または異なるものであつ
て、水素原子または低級アルキル基をあらわす。
R3はアルキル基、アリール基、アルケニル基ま
たはアルカジエニル基をあらわし、反応に対して
不活性な限り置換基を有していてもよい。R4は
ヨウ素原子またはアルキル基をあらわす。〕 を製造する方法。 ２ プロパギルアルコールが であり、三置換オレフインとしてネロールを得る
特許請求の範囲第１項の方法。 ３ プロパギルアルコールが であり、三置換オレフインとして（Ｅ，Ｚ）−フ
アルネソールを得る特許請求の範囲第１項の方
法。[Claims] Propargyl alcohol of the primary formula [In the formula, R 1 and R 2 are the same or different and represent a hydrogen atom or a lower alkyl group. R 3 represents an alkyl group, an aryl group, an alkenyl group, or an alkadienyl group, and may have a substituent as long as it is inert to the reaction. ], Grignard reagent RMgX [R represents a lower alkyl group, X is Cl,
Br or I. ] in a catalytic amount of Cp 2 TiCl 2 [Cp represents a cyclopentadienyl group or a derivative thereof. ] and then reacted with iodine or alkyl iodide to form a trisubstituted olefin of the following formula: [R 1 and R 2 are the same or different and represent a hydrogen atom or a lower alkyl group.
R 3 represents an alkyl group, an aryl group, an alkenyl group, or an alkadienyl group, and may have a substituent as long as it is inert to the reaction. R 4 represents an iodine atom or an alkyl group. ] A method of manufacturing. 2 Propargyl alcohol A process according to claim 1 for obtaining nerol as a trisubstituted olefin. 3 Propargyl alcohol The method according to claim 1, wherein (E,Z)-furnesol is obtained as a trisubstituted olefin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56096950A JPS57212131A (en) | 1981-06-23 | 1981-06-23 | Preparation of tri-substituted olefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56096950A JPS57212131A (en) | 1981-06-23 | 1981-06-23 | Preparation of tri-substituted olefin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57212131A JPS57212131A (en) | 1982-12-27 |
| JPS6254407B2 true JPS6254407B2 (en) | 1987-11-14 |
Family
ID=14178568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56096950A Granted JPS57212131A (en) | 1981-06-23 | 1981-06-23 | Preparation of tri-substituted olefin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57212131A (en) |
-
1981
- 1981-06-23 JP JP56096950A patent/JPS57212131A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57212131A (en) | 1982-12-27 |
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