JP4243397B2 - Novel unsaturated secondary alcohol and process for producing the same - Google Patents

Description

〔式中、Ｒはビニル基-CH=CH₂またはエチニル基-C≡CHであり、また式中に示されたフェニル基上のtert-ブトキシ基は該フェニル基のパラ位またはメタ位にある〕で表される不飽和２級アルコールが提供される。
第１の本発明による一般式（Ｉ）の不飽和２級アルコールの好ましい例には、1-(p-tert-ブトキシフェニル)-2-プロペン-1-オール、1-(m-tert-ブトキシフェニル)-2-プロペン-1-オール、1-(p-tert-ブトキシフェニル)-2-プロピン-1-オールまたは1-(m-tert-ブトキシフェニル)-2-プロピン-1-オールがある。
【０００８】
また、第２の本発明においては、一般式（II）
R-MgX (II)
〔式中、Ｒはビニル基またはエチニル基であり、Ｘはハロゲン原子、好ましくは塩素、臭素またはヨウ素原子である〕で表されるビニルまたはエチニル・マグネシウムハライドと一般式（III)

で表わされるp-またはm-tert-ブトキシベンズアルデヒドとをグリニヤール反応により反応させ、次いで加水分解させることを特徴とする、一般式（Ｉ）

〔式中、Ｒはビニル基-CH=CH₂またはエチニル基-C≡CHであり、また式中に示されたフェニル基上のtert-ブトキシ基は該フェニル基のパラ位またはメタ位にある〕で表される不飽和２級アルコールの製造法が提供される。
【０００９】
さらに、第３の本発明においては、一般式（IV）

（式中、Ｘは、ハロゲン原子を示す）で表わされるp-またはm-tert-ブトキシフェニル・マグネシウムハライドと、一般式(Va）
R^a-CHO （Va）
〔式中、Ｒ^aはビニル基である〕のアクロレインとをグリニヤール反応により反応させ、次いで加水分解させることを特徴とする、一般式（Ia）

〔式中、Ｒ^aはビニル基-CH=CH₂であり、また式中に示されたフェニル基上のtert-ブトキシ基は該フェニル基のパラ位またはメタ位にある〕で表される不飽和２級アルコールの製造法が提供される。
【００１０】
【発明の実施の形態】
以下、本発明をさらに詳細に説明する。
第１の本発明による一般式（Ｉ）の化合物のうち、下記の一般式（Ｉ′）の新規な1-(p-またはm-tert-ブトキシフェニル)-2-プロペン-1-オールは、以下の反応式による第２の本発明方法に準ずるの反応経路(A)あるいは第３の本発明方法に準ずる反応経路(B)で合成するのが都合よい。
【００１１】

（式中、Ｘは、ハロゲン原子を示す）。
【００１２】

（式中、Ｘは、ハロゲン原子を示す）。
【００１３】
まず、第２の本発明方法で用いられる合成原料であるグリニヤール試薬の式(II′)の化合物は、公知の化合物であり、公知の方法により得るか、または市販品を用いればよい。また、式（III）のアルデヒド化合物は、公知の化合物であり、公知の方法により得ることができる。
【００１４】
式（II′)の化合物のＸは、ハロゲン原子であり、好ましくは、塩素、ヨウ素、臭素などが挙げられる。この式（II′)の化合物の溶液中に式（III)のアルデヒド化合物を滴下し、１〜２時間攪拌して合成経路(A)に従って反応を行う。この反応に用いる溶媒としては、テトラヒドロフランの単独、あるいはこれとベンゼン、トルエン、キシレンなどの芳香族炭化水素溶媒との混合溶媒、またジエチルエーテル、ジブチルエーテルなどが挙げられる。反応温度は10〜40℃が好ましい。
【００１５】
また別法として、第３の本発明方法で用いる合成原料であるグリニヤール試薬の式（IV）の化合物は、公知の化合物であり、公知の方法により得ることができる。また、式（V′）のアルデヒド化合物すなわちアクロレインは、公知の化合物であり、公知の方法により得ることができる。
【００１６】
式(IV)の化合物のＸは、ハロゲン原子であり、好ましくは、塩素、ヨウ素、臭素などが挙げられる。この式（IV)の化合物の溶液中に式(V′)のアクロレインを滴下し、１〜２時間攪拌して合成経路(B)に従って反応を行う。この反応に用いる溶媒としては、テトラヒドロフランの単独あるいはこれとベンゼン、トルエン、キシレンなどの芳香族炭化水素溶媒との混合溶媒、またジエチルエーテル、ジブチルエーテルなどが挙げられる。反応温度は10〜40℃が好ましい。
反応終了後は、飽和の塩化アンモニウム水または水を、反応液に加え10〜30℃の温度で加水分解すると、式(I′)の1-(p-又はm-tert-ブトキシフェニル)-2-プロペン-1-オールが生成する。さらに式(I′)の化合物を含む有機層を分取し、溶媒を留去して残留物を減圧蒸留すると、高純度の式(I′)の化合物を得ることができる。
【００１７】
また、第１の本発明による一般式（Ｉ）の化合物のうち、下記の一般式（I″)で表される新規な1-(p-又はm-tert-ブトキシフェニル)-2-プロピン-1-オールを、以下の反応式により第２の本発明方法に準ずる反応経路(C)で合成できる。
【００１８】

（式中、Ｘは、ハロゲン原子を示す）。
【００１９】
第２の本発明方法で用いられる合成原料であるグリニヤール試薬の式(II″)のハライド化合物は、公知の化合物であり、公知の方法により得るか、または、市販品を用いればよい。また、式（III）の化合物は、公知の化合物であり、公知の方法により得ることができる。
【００２０】
式（II′)のハライド化合物のＸは、ハロゲン原子であり、好ましくは、塩素、ヨウ素、臭素などが挙げられる。この式（II″)の化合物の溶液中に式（III)のアルデヒド化合物を滴下し、１〜２時間攪拌して合成経路(C)に従って反応を行う。この反応に用いる溶媒としては、テトラヒドロフランの単独あるいはこれとベンゼン、トルエン、キシレンなどの芳香族炭化水素溶媒との混合溶媒、またジエチルエーテル、ジブチルエーテルなどが挙げられる。反応温度は10〜40℃が好ましい。
反応終了後は、飽和の塩化アンモニウム水または、水を反応液に加え10〜30℃の温度で加水分解すると式(I″)の1-(p-又はm-tert-ブトキシフェニル)-2-プロピン-1-オールが生成する。さらに式(I″)の化合物を含む有機層を分取し、溶媒を留去して残留物を減圧蒸留すると、高純度の式(I″)の化合物を得ることができる。
【００２１】
【実施例】
次に、本発明の実施例を示す。
実施例１ 1-(p-tert-ブトキシフェニル)-2-プロペン-1-オールの合成（第２の本発明方法による）
窒素置換した１ｌ容量の４つ口フラスコに削り状の金属マグネシウム9.7 g(0.4 mol)と無水テトラヒドロフラン30 mlを加え、さらに臭化エチル約２ mlを加えて攪拌し、発泡による反応を確認した。次いで、無水テトラヒドロフランを300 ml加えた後、塩化ビニル8960 ml(0.4 mol)を30〜40℃で５時間を要して吹き込みで（マグネシウムが消失した）、ビニル・マグネシウムクロライドの溶液（0.4 mol)を調製した。
【００２２】
この溶液にp-tert-ブトキシベンズアルデヒド71.3 g(0.4 mol)を30〜40℃で２時間を要して滴下し、さらに同温度で１時間攪拌を続けた。反応終了後、この反応液を室温まで冷却し、水60 mlを、30℃以下で加えて加水分解した。
次いで、通常の後処理を行った後（すなわち、反応混合物を食塩水で洗浄し、水層と有機層とに層分離させ、得られる有機層から溶媒を留去した後）、得られた粗生成物に重合防止剤として第三級ブチルカテコールを添加し、減圧条件下で蒸留を行うことにより、1-(p-tert-ブトキシフェニル)-2-プロペン-1-オールが72.5 g(ガスクロマトグラフィーによる純度99.0％、収率88.0％）得られた。得られた化合物の物性値は以下のとおりであった。
沸点:133℃/８ mmHg
¹H-NMR(CDCl₃)のピーク値
δ：1.35(s、9H)、2.40(s、1H)、5.20-5.75(m、3H)、5.90-6.15(m、1H)、6.93(d、2H)、7.60(d、2H)
【００２３】
実施例２ 1-(m-tert-ブトキシフェニル)-2-プロペン-1-オールの合成
実施例１において、p-tert-ブトキシベンズアルデヒドの代りにm-tert-ブトキシベンズアルデヒドを用いた以外は、実施例１と同様な操作を行い、1-(m-tert-ブトキシフェニル)-2-プロペン-1-オールが70.9 g(ガスクロマトグラフィーによる純度99.0％、収率86.0％得られた。得られた化合物の物性値は以下のとおりであった。
沸点:135℃/９ mmHg
¹H-NMR(CDCl₃)のピーク値
δ：1.34(s、9H)、2.60(s、1H)、5.20-5.75(m、3H)、5.90-6.10(m、1H)、7.05-7.40(m、4H)
【００２４】
実施例３ 1-(p-tert-ブトキシフェニル)-2-プロペン-1-オールの合成（第３の本発明方法による）
窒素置換した１ｌ容量の４つ口フラスコに削り状の金属マグネシウム9.7 g(0.4 mol)と無水テトラヒドロフラン30 mlを加え、さらに臭化エチル約２ mlを加えて攪拌し、発泡による反応を確認した。次いでp-tert-ブトキシクロルベンゼン73.9 g(0.4 mol)を、300 mlの無水テトラヒドロフランに溶解し、これを還流温度(70℃)で５時間を要して滴下した。さらに２時間同温度で攪拌を続けて、p-tert-ブトキシフェニルマグネシウムクロライドの溶液（0.4 mol)を調製した。
【００２５】
この溶液に、純度90％のアクロレイン24.9 g(0.4 mol)を30〜40℃で２時間を要して滴下し、さらに同温度で１時間攪拌を続けた。反応終了後、この反応液を室温まで冷却し、水60 mlを、30℃以下で加えて加水分解した。
次いで、通常の後処理を行った後（すなわち、反応混合物を食塩水で洗浄し、水層と有機層とに層分離させ、得られる有機層から溶媒を留去した後）、得られた粗生成物に重合防止剤として第三級ブチルカテコールを添加し、減圧条件下で蒸留を行うことにより、1-(p-tert-ブトキシフェニル)-2-プロペン-1-オールが70.0 g(ガスクロマトグラフィーによる純度98.9％、収率85.0％）得られた。
【００２６】
実施例４ 1-(p-tert-ブトキシフェニル)-2-プロピン-1-オールの合成（第２の本発明方法による）
窒素置換した１ｌ容量の４つ口フラスコに削り状の金属マグネシウム9.7 g(0.4 mol)と無水テトラヒドロフラン30 mlを加え、さらに臭化エチル約２ mlを加えて攪拌し、発泡による反応を確認した。次いで、無水テトラヒドロフランを300 ml加えた後、塩化メチル8960 ml(0.4 mol)を30〜40℃で５時間を要して吹き込んで（マグネシウムが消失した）、メチルマグネシウムクロライドの溶液（0.4 mol)を調製した。さらにこの溶液を20℃以下に冷却し、アセチレン8960 ml(0.4 mol)を10〜20℃で５時間を要して吹き込んでエチニルマグネシウムクロライドの溶液（0.4 mol)を調製した。
【００２７】
この溶液にp-tert-ブトキシベンズアルデヒド71.3 g(0.4 mol)を30℃〜40℃で２時間を要して滴下し、さらに同温度で１時間攪拌を続けた。反応終了後、この反応液を室温まで冷却し、水60 mlを、30℃以下で加えて加水分解した。
次いで、通常の後処理を行った後（すなわち、反応混合物を食塩水で洗浄し、水層と有機層とに層分離させ、得られる有機層から溶媒を留去した後）、得られた粗生成物に重合防止剤として第三級ブチルカテコールを添加し、減圧条件下で蒸留を行うことにより、1-(p-tert-ブトキシフェニル)-2-プロピン-1-オールが74.2 g(ガスクロマトグラフィーによる純度99.8％、収率91.0％）得られた。得られた化合物の物性値は以下のとおりであった。
沸点:135℃/５ mmHg
¹H-NMR(CDCl₃)のピーク値
δ：1.15(s、9H)、2.55(s、1H)、2.80(d、1H)、5.25(d、1H)、6.85(d、2H)、7.35(d、2H)
【００２８】
【発明の効果】
本発明による一般式（Ｉ）の不飽和２級アルコールは、医薬、農薬、液晶などの原料として有用である。また、本発明方法によると、高収率で、しかも簡単な操作で高純度品が得られるため、工業的に極めて有利である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel unsaturated secondary alcohol and to a process for producing the same.
[0002]
More specifically, the present invention relates to 1- (p- or m-tert-butoxyphenyl) -2-propene as a novel unsaturated secondary alcohol useful as a raw material for the production of pharmaceuticals, agricultural chemicals, liquid crystals and the like. It relates to propyn-1-ol and to a process for producing these unsaturated secondary alcohols.
[0003]
[Prior art]
Conventionally, for example, some of the following unsaturated secondary alcohols having a chemical structure similar to the novel unsaturated secondary alcohol of the present invention are known.
[0004]
(1) 1- (p-methoxyphenyl) -2-propen-1-ol is known and is produced in a 79% yield by the reaction of p-methoxybenzaldehyde and vinylmagnesium chloride (“Journal of American Chemical (Journal of American Chemical Society, Vol. 100, pages 6407 to 6413 (1978)).
(2) 1- (p-methoxyphenyl) -2-propyn-1-ol is known and is produced in a yield of 95% by the reaction of p-methoxybenzaldehyde and ethynylmagnesium bromide (“Journal of Chemical Society”). Perkin Trans I (Journal of Chemical Society., Perkin Trans. I), Vol. 6, pages 1425 to 1430 (1988)).
(3) 1- (p-tert-butoxy) -1-ethanol is produced in a yield of 97.9% by the reaction of p-tert-butoxybenzaldehyde and methylmagnesium chloride (see JP-A-61-115040). ).
[0005]
[Problems to be solved by the invention]
However, it provides new unsaturated secondary alcohols that are useful as raw materials or intermediate raw materials for the production of pharmaceuticals, agricultural chemicals, liquid crystals, etc., and also provides a production method for obtaining them in a high yield by industrially easy operation. It is hoped to do.
[0006]
[Means for Solving the Problems]
The present inventors diligently studied to achieve the above object. As a result, they succeeded in synthesizing 1- (p- or m-tert-butoxyphenyl) -2-propene or propyn-1-ol, and found that these unsaturated secondary alcohols were novel compounds. Further, the present invention has been completed by finding an effective production method for obtaining this novel compound in a high yield by an industrially easy operation.
[0007]
That is, in the first present invention, the general formula (I)

[In the formula, R is a vinyl group —CH═CH ₂ or an ethynyl group —C≡CH, and the tert-butoxy group on the phenyl group shown in the formula is in the para position or the meta position of the phenyl group. An unsaturated secondary alcohol represented by the formula:
Preferred examples of the unsaturated secondary alcohol of the general formula (I) according to the first invention include 1- (p-tert-butoxyphenyl) -2-propen-1-ol, 1- (m-tert-butoxy Phenyl) -2-propen-1-ol, 1- (p-tert-butoxyphenyl) -2-propyn-1-ol or 1- (m-tert-butoxyphenyl) -2-propyn-1-ol .
[0008]
In the second present invention, the general formula (II)
R-MgX (II)
[Wherein R is a vinyl group or an ethynyl group, and X is a halogen atom, preferably a chlorine, bromine or iodine atom] and a vinyl or ethynyl magnesium halide represented by the general formula (III)

P- or m-tert-butoxybenzaldehyde represented by the general formula (I), characterized by reacting by Grignard reaction and then hydrolyzing

[In the formula, R is a vinyl group —CH═CH ₂ or an ethynyl group —C≡CH, and the tert-butoxy group on the phenyl group shown in the formula is in the para position or the meta position of the phenyl group. ] The manufacturing method of unsaturated secondary alcohol represented by these is provided.
[0009]
Furthermore, in the third aspect of the present invention, the general formula (IV)

(Wherein X represents a halogen atom) and m-tert-butoxyphenyl magnesium halide represented by the general formula (Va)
R ^a -CHO (Va)
A compound of the general formula (Ia), characterized in that acrolein of [wherein R ^a is a vinyl group] is reacted by Grignard reaction and then hydrolyzed.

Wherein R ^a is a vinyl group —CH═CH ₂ , and the tert-butoxy group on the phenyl group shown in the formula is in the para or meta position of the phenyl group. A method for producing a saturated secondary alcohol is provided.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
Among the compounds of the general formula (I) according to the first invention, the novel 1- (p- or m-tert-butoxyphenyl) -2-propen-1-ol of the following general formula (I ′) is It is convenient to synthesize by the reaction route (A) according to the second method of the present invention or the reaction route (B) according to the third method of the present invention according to the following reaction formula.
[0011]

(In the formula, X represents a halogen atom).
[0012]

(In the formula, X represents a halogen atom).
[0013]
First, the compound of the formula (II ′) of the Grignard reagent, which is a synthetic raw material used in the second method of the present invention, is a known compound and may be obtained by a known method or a commercially available product may be used. The aldehyde compound of the formula (III) is a known compound and can be obtained by a known method.
[0014]
X in the compound of the formula (II ′) is a halogen atom, and preferable examples include chlorine, iodine, bromine and the like. The aldehyde compound of the formula (III) is dropped into the solution of the compound of the formula (II ′) and stirred for 1 to 2 hours to carry out the reaction according to the synthesis route (A). Examples of the solvent used in this reaction include tetrahydrofuran alone, a mixed solvent of this with an aromatic hydrocarbon solvent such as benzene, toluene, and xylene, diethyl ether, dibutyl ether, and the like. The reaction temperature is preferably 10 to 40 ° C.
[0015]
As another method, the compound of formula (IV) of the Grignard reagent, which is a synthetic raw material used in the third method of the present invention, is a known compound and can be obtained by a known method. The aldehyde compound of formula (V ′), that is, acrolein, is a known compound and can be obtained by a known method.
[0016]
X in the compound of the formula (IV) is a halogen atom, and preferable examples include chlorine, iodine, bromine and the like. The acrolein of the formula (V ′) is dropped into the solution of the compound of the formula (IV) and stirred for 1 to 2 hours to carry out the reaction according to the synthesis route (B). Examples of the solvent used in this reaction include tetrahydrofuran alone or a mixed solvent of this with an aromatic hydrocarbon solvent such as benzene, toluene and xylene, diethyl ether, dibutyl ether and the like. The reaction temperature is preferably 10 to 40 ° C.
After completion of the reaction, saturated aqueous ammonium chloride or water is added to the reaction solution and hydrolyzed at a temperature of 10 to 30 ° C. to give 1- (p- or m-tert-butoxyphenyl) -2 of formula (I ′). -Propen-1-ol is produced. Further, an organic layer containing the compound of the formula (I ′) is separated, the solvent is distilled off, and the residue is distilled under reduced pressure to obtain a highly pure compound of the formula (I ′).
[0017]
Among the compounds of the general formula (I) according to the first invention, novel 1- (p- or m-tert-butoxyphenyl) -2-propyne represented by the following general formula (I ″) 1-ol can be synthesized by the reaction route (C) according to the second method of the present invention by the following reaction formula.
[0018]

(In the formula, X represents a halogen atom).
[0019]
The halide compound of the formula (II ″) of the Grignard reagent, which is a synthetic raw material used in the second method of the present invention, is a known compound, and can be obtained by a known method or a commercially available product can be used. The compound of the formula (III) is a known compound and can be obtained by a known method.
[0020]
X of the halide compound of the formula (II ′) is a halogen atom, and preferable examples include chlorine, iodine, bromine and the like. The aldehyde compound of the formula (III) is dropped into the solution of the compound of the formula (II ″) and stirred for 1 to 2 hours to carry out the reaction according to the synthesis route (C). As a solvent used in this reaction, tetrahydrofuran is used. These may be used alone or in combination with an aromatic hydrocarbon solvent such as benzene, toluene, xylene, diethyl ether, dibutyl ether, etc. The reaction temperature is preferably 10 to 40 ° C.
After completion of the reaction, saturated aqueous ammonium chloride or water is added to the reaction solution and hydrolyzed at a temperature of 10 to 30 ° C. to give 1- (p- or m-tert-butoxyphenyl) -2- Propin-1-ol is produced. Further, the organic layer containing the compound of the formula (I ″) is separated, the solvent is distilled off, and the residue is distilled under reduced pressure to obtain a highly pure compound of the formula (I ″). Obtainable.
[0021]
【Example】
Next, examples of the present invention will be described.
Example 1 Synthesis of 1- (p-tert-butoxyphenyl) -2-propen-1-ol (according to the second method of the present invention)
To a 1 l four-necked flask purged with nitrogen, 9.7 g (0.4 mol) of shaved metal magnesium and 30 ml of anhydrous tetrahydrofuran were added, and about 2 ml of ethyl bromide was further added and stirred to confirm the reaction by foaming. Next, 300 ml of anhydrous tetrahydrofuran was added, and then 8960 ml (0.4 mol) of vinyl chloride was blown in at 30 to 40 ° C. for 5 hours (magnesium disappeared) to give a solution of vinyl / magnesium chloride (0.4 mol). Was prepared.
[0022]
To this solution, 71.3 g (0.4 mol) of p-tert-butoxybenzaldehyde was added dropwise at 30 to 40 ° C. over 2 hours, and stirring was further continued at the same temperature for 1 hour. After completion of the reaction, the reaction solution was cooled to room temperature and hydrolyzed by adding 60 ml of water at 30 ° C. or lower.
Next, after the usual post-treatment (that is, the reaction mixture was washed with brine, separated into an aqueous layer and an organic layer, and the solvent was distilled off from the obtained organic layer), the resulting crude product was obtained. Tertiary butyl catechol was added to the product as a polymerization inhibitor and distilled under reduced pressure to obtain 72.5 g of 1- (p-tert-butoxyphenyl) -2-propen-1-ol (gas chromatography). (Graphic purity 99.0%, yield 88.0%). The physical properties of the obtained compound were as follows.
Boiling point: 133 ° C / 8 mmHg
¹ H-NMR (CDCl ₃ ) peak values δ: 1.35 (s, 9H), 2.40 (s, 1H), 5.20-5.75 (m, 3H), 5.90-6.15 (m, 1H), 6.93 (d, 2H ), 7.60 (d, 2H)
[0023]
Example 2 Synthesis of 1- (m-tert-butoxyphenyl) -2-propen-1-ol The same procedure as in Example 1 was carried out except that m-tert-butoxybenzaldehyde was used instead of p-tert-butoxybenzaldehyde. The same operation as in Example 1 was performed to obtain 70.9 g of 1- (m-tert-butoxyphenyl) -2-propen-1-ol (purity 99.0% by gas chromatography, yield 86.0%). The physical property values of the compounds were as follows.
Boiling point: 135 ° C / 9 mmHg
¹ H-NMR (CDCl ₃ ) peak values δ: 1.34 (s, 9H), 2.60 (s, 1H), 5.20-5.75 (m, 3H), 5.90-6.10 (m, 1H), 7.05-7.40 (m , 4H)
[0024]
Example 3 Synthesis of 1- (p-tert-butoxyphenyl) -2-propen-1-ol (according to the third inventive method)
To a 1 l four-necked flask purged with nitrogen, 9.7 g (0.4 mol) of shaved metal magnesium and 30 ml of anhydrous tetrahydrofuran were added, and about 2 ml of ethyl bromide was further added and stirred to confirm the reaction by foaming. Next, 73.9 g (0.4 mol) of p-tert-butoxycyclobenzene was dissolved in 300 ml of anhydrous tetrahydrofuran, and this was added dropwise at reflux temperature (70 ° C.) over 5 hours. Stirring was further continued at the same temperature for 2 hours to prepare a solution (0.4 mol) of p-tert-butoxyphenylmagnesium chloride.
[0025]
To this solution, 24.9 g (0.4 mol) of 90% pure acrolein was added dropwise at 30 to 40 ° C. over 2 hours, and stirring was further continued at the same temperature for 1 hour. After completion of the reaction, the reaction solution was cooled to room temperature and hydrolyzed by adding 60 ml of water at 30 ° C. or lower.
Next, after the usual post-treatment (that is, the reaction mixture was washed with brine, separated into an aqueous layer and an organic layer, and the solvent was distilled off from the obtained organic layer), the resulting crude product was obtained. Tertiary butyl catechol was added to the product as a polymerization inhibitor, and distilled under reduced pressure conditions to give 70.0 g of 1- (p-tert-butoxyphenyl) -2-propen-1-ol (gas chromatography). (Graphic purity 98.9%, yield 85.0%).
[0026]
Example 4 Synthesis of 1- (p-tert-butoxyphenyl) -2-propyn-1-ol (according to the second inventive method)
To a 1 l four-necked flask purged with nitrogen, 9.7 g (0.4 mol) of shaved metal magnesium and 30 ml of anhydrous tetrahydrofuran were added, and about 2 ml of ethyl bromide was further added and stirred to confirm the reaction by foaming. Next, after adding 300 ml of anhydrous tetrahydrofuran, 8960 ml (0.4 mol) of methyl chloride was blown in at 30-40 ° C. for 5 hours (magnesium disappeared), and a solution of methyl magnesium chloride (0.4 mol) was added. Prepared. Further, this solution was cooled to 20 ° C. or less, and 8960 ml (0.4 mol) of acetylene was blown at 10 to 20 ° C. over 5 hours to prepare a solution (0.4 mol) of ethynylmagnesium chloride.
[0027]
To this solution, 71.3 g (0.4 mol) of p-tert-butoxybenzaldehyde was added dropwise at 30 ° C. to 40 ° C. over 2 hours, and stirring was further continued at the same temperature for 1 hour. After completion of the reaction, the reaction solution was cooled to room temperature and hydrolyzed by adding 60 ml of water at 30 ° C. or lower.
Next, after the usual post-treatment (that is, the reaction mixture was washed with brine, separated into an aqueous layer and an organic layer, and the solvent was distilled off from the obtained organic layer), the resulting crude product was obtained. By adding tertiary butylcatechol as a polymerization inhibitor to the product and performing distillation under reduced pressure conditions, 74.2 g (gas chromatography) of 1- (p-tert-butoxyphenyl) -2-propyn-1-ol was obtained. (99.8% purity and 91.0% yield). The physical properties of the obtained compound were as follows.
Boiling point: 135 ° C / 5 mmHg
Peak value δ of ¹ H-NMR (CDCl ₃ ): 1.15 (s, 9H), 2.55 (s, 1H), 2.80 (d, 1H), 5.25 (d, 1H), 6.85 (d, 2H), 7.35 ( d, 2H)
[0028]
【The invention's effect】
The unsaturated secondary alcohol of the general formula (I) according to the present invention is useful as a raw material for pharmaceuticals, agricultural chemicals, liquid crystals and the like. Further, according to the method of the present invention, a high-purity product can be obtained with a high yield and a simple operation, which is extremely advantageous industrially.

Claims (4)

Formula (I)

[In the formula, R is a vinyl group —CH═CH ₂ or an ethynyl group —C≡CH, and the tert-butoxy group on the phenyl group shown in the formula is in the para position or the meta position of the phenyl group. ] The unsaturated secondary alcohol represented by this. The unsaturated secondary alcohol of the general formula (I) is 1- (p-tert-butoxyphenyl) -2-propen-1-ol, 1- (m-tert-butoxyphenyl) -2-propen-1-ol, The secondary alcohol according to claim 1, which is 1- (p-tert-butoxyphenyl) -2-propyn-1-ol or 1- (m-tert-butoxyphenyl) -2-propyn-1-ol. Formula (II)
R-MgX (II)
[Wherein R is a vinyl group or an ethynyl group, and X is a halogen atom, preferably a chlorine, bromine or iodine atom] and a vinyl or ethynyl magnesium halide represented by the general formula (III)

P- or m-tert-butoxybenzaldehyde represented by the general formula (I), characterized by reacting by Grignard reaction and then hydrolyzing

[In the formula, R is a vinyl group —CH═CH ₂ or an ethynyl group —C≡CH, and the tert-butoxy group on the phenyl group shown in the formula is in the para position or the meta position of the phenyl group. ] The manufacturing method of unsaturated secondary alcohol represented by this. Formula (IV)

(Wherein X represents a halogen atom) and m-tert-butoxyphenyl magnesium halide represented by the general formula (Va)
R ^a -CHO (Va)
A compound of the general formula (Ia), characterized in that acrolein of [wherein R ^a is a vinyl group] is reacted by Grignard reaction and then hydrolyzed.

Wherein R ^a is a vinyl group —CH═CH ₂ , and the tert-butoxy group on the phenyl group shown in the formula is in the para or meta position of the phenyl group. A method for producing saturated secondary alcohols.