JPH02101037A - Production of 3-hydroxy-4-phenyl-2-butanone - Google Patents
Production of 3-hydroxy-4-phenyl-2-butanoneInfo
- Publication number
- JPH02101037A JPH02101037A JP63250776A JP25077688A JPH02101037A JP H02101037 A JPH02101037 A JP H02101037A JP 63250776 A JP63250776 A JP 63250776A JP 25077688 A JP25077688 A JP 25077688A JP H02101037 A JPH02101037 A JP H02101037A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- hours
- reaction
- mol
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- QBCUUJGHWFKMDC-UHFFFAOYSA-N 3-Hydroxy-4-phenylbutan-2-one Chemical compound CC(=O)C(O)CC1=CC=CC=C1 QBCUUJGHWFKMDC-UHFFFAOYSA-N 0.000 title claims 4
- -1 2-substituted-3- phenylpropionitrile Chemical class 0.000 claims abstract description 22
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract 2
- 230000007062 hydrolysis Effects 0.000 claims abstract 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 24
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 8
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 abstract description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 239000011593 sulfur Substances 0.000 abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 229940100595 phenylacetaldehyde Drugs 0.000 abstract description 4
- 235000010265 sodium sulphite Nutrition 0.000 abstract description 4
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000796 flavoring agent Substances 0.000 abstract 1
- 235000019634 flavors Nutrition 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 125000005843 halogen group Chemical group 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000005457 ice water Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000003205 fragrance Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- GOOUUOYVIYFDBL-UHFFFAOYSA-N 2-hydroxy-3-phenylpropanenitrile Chemical compound N#CC(O)CC1=CC=CC=C1 GOOUUOYVIYFDBL-UHFFFAOYSA-N 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- KXROTPXCYDXGSC-UHFFFAOYSA-N 2-methyl-1,3-dithiane Chemical compound CC1SCCCS1 KXROTPXCYDXGSC-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 2
- 229940102396 methyl bromide Drugs 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- KRXAVBPUAIKSFF-UHFFFAOYSA-N 3,4-dihydrodithiine Chemical compound C1CC=CSS1 KRXAVBPUAIKSFF-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/004—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with organometalhalides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Seasonings (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は既知の化合物である３−ヒドロキシ４−７エニ
ルー２−ブタノンの製法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a process for the preparation of the known compound 3-hydroxy-4-7enyl-2-butanone.
更に詳しくは、本発明は、香料物質として有用な下記式
（１）
キル基を示す）を示す
で表される２−置換−３−フェニルプロピオニトリルを
メチルマグネシウムハライドまたはメグールリチウムと
反応させ、次いで酸の存在下に加水分解することを特徴
とする下記式（１）で表される３−ヒドロキシ−４−７
エニルー２ブタノンの新規な製法に関する。More specifically, the present invention involves reacting 2-substituted-3-phenylpropionitrile represented by the following formula (1) (indicating a kill group), which is useful as a fragrance substance, with methylmagnesium halide or megurlithium, 3-hydroxy-4-7 represented by the following formula (1), which is then hydrolyzed in the presence of an acid.
This invention relates to a new method for producing enyl-2-butanone.
（従来の技術）
本出願人は、２−メチル−１，３−ジチアンをアルカリ
触媒の存在下にフェニルアセトアルデヒドと縮合反応さ
せて、２−メチル−２−（１’ヒドロキシー２′−フェ
ニルエチル）−１，３ジチアンを形成せしめ、次いで、
該化合物を加水分解して、前記式（１）の化合物を合成
する方法を開発し先に提案している（特開昭６３−８３
０１８号公報参照）。(Prior Art) The present applicant conducted a condensation reaction of 2-methyl-1,3-dithiane with phenylacetaldehyde in the presence of an alkali catalyst to produce 2-methyl-2-(1'hydroxy-2'-phenylethyl). -1,3 dithiane is formed, and then
developed and previously proposed a method for synthesizing the compound of formula (1) by hydrolyzing the compound (Japanese Unexamined Patent Publication No. 63-83
(See Publication No. 018).
（発明が解決しようとする課題）
上述の先に提案した合成方法は、出発原料に硫黄原子を
含む２−メチル−１，３−ジチアンを使用しているため
、いかなる精製手段を用いても生成物である式（１）の
化合物の中にごく微量の原料が残り、これに由来するか
すかな硫黄臭が存在する。従って、先に提案した方法に
より合成された式（１）の化合物を調合香料成分として
使用した場合、調合香料にかすかな硫黄臭がつき、この
硫黄臭のために、式（１）の化合物を調合香料として使
用することが制限され、香気的に解決すべき課題があっ
た。(Problems to be Solved by the Invention) The previously proposed synthesis method uses 2-methyl-1,3-dithiane containing a sulfur atom as a starting material, so no matter what purification method is used, it will not be possible to produce the product. A very small amount of raw material remains in the compound of formula (1), and a faint sulfur odor originating from this remains. Therefore, when the compound of formula (1) synthesized by the method proposed above is used as a blended fragrance ingredient, the blended fragrance will have a faint sulfur odor, and this sulfur odor may cause the compound of formula (1) to be used as a blended fragrance ingredient. There were restrictions on its use as a blended fragrance, and there were problems that needed to be solved in terms of aroma.
本発明者らは、出発原料に硫黄原子を含む２メチル−１
，３−ジチアンを使用しない方法で上記式（１）の化合
物を合成する方法について鋭意研究した結果、後記式（
２）の２−置換−３−フェニルプロピオニトリルを出発
原料に選ぶことにより好収率でしかも硫黄臭のない式（
１）の化合物を合成できることを発見して本発明を完成
した。The present inventors discovered that 2-methyl-1 containing a sulfur atom in the starting material
As a result of intensive research into a method for synthesizing the compound of the above formula (1) without using ,3-dithiane, the following formula (
By selecting 2-substituted-3-phenylpropionitrile (2) as the starting material, the formula (
The present invention was completed by discovering that the compound 1) can be synthesized.
従って、本発明の目的は、好収率でしかも硫黄臭のしな
い式（１）の化合物の製造方法を提供するにある。Therefore, an object of the present invention is to provide a method for producing the compound of formula (1) with good yield and no sulfur odor.
（課題を解決するための手段）
本発明によれば、式（１）の化合物は、下記式（２）
式中、Ｒは水素原子、２−テトラヒドロピラニル基また
は１−アルコキシエチル基
キル基を示す）示す
＝３
で表される２−Ｒ換−３−フェニルプロピオニトリルを
メチルマグネシウムハライドまたはメチルリチウムと反
応させ、次いで酸の存在下に加水分解することにより容
易に合成することができる。(Means for Solving the Problems) According to the present invention, the compound of formula (1) has the following formula (2) where R is a hydrogen atom, a 2-tetrahydropyranyl group, or a 1-alkoxyethyl group. It can be easily synthesized by reacting 2-R-substituted-3-phenylpropionitrile represented by =3 with methylmagnesium halide or methyllithium, and then hydrolyzing it in the presence of an acid.
本発明に従う式（１）の化合物の合成法を反応工程図で
示すと、例えば、以下のように表すことができる。When the method for synthesizing the compound of formula (1) according to the present invention is shown in a reaction process diagram, it can be represented, for example, as follows.
本発明の出発原料である式（２）の化合物は既知の化合
物である。該式（２）に包含される２−ヒドロキシ−３
〜７エニルプロピオニトリル［Ｒが水素原子である式（
２）の化合物］の合成は、例えば、フェニルアセトアル
デヒドを亜硫酸ナトリウムと反応させて得た亜硫酸ナト
リウムの付加物をシアン化ナトリウムなどのシアン化物
と反応させることにより行うことができる。また、式（
２）に包含される２−（１−アルコキシエトキシ）＝３
−フェニルプロピルニトリル［Ｒが１−アルコキシエチ
ル基である式（２）の化合物］および２−（２−テトラ
ヒドロピラノキシ）−３−７エニルプロビオニトリル［
Ｒが２−テトラヒドロピラニル基である式（２）の化合
物Ｊは、例えば、２−ヒドロキシ−３−フェニルプロピ
オニトリルをリン酸、塩酸などの酸の存在下にそれぞれ
アルキルビニルエーテルおよびジヒドロピランと反応さ
せることにより容易に合成することができる。The compound of formula (2) which is the starting material of the present invention is a known compound. 2-hydroxy-3 included in the formula (2)
~7enylpropionitrile [formula in which R is a hydrogen atom (
Compound 2) can be synthesized, for example, by reacting an adduct of sodium sulfite obtained by reacting phenylacetaldehyde with sodium sulfite with a cyanide such as sodium cyanide. Also, the expression (
2-(1-alkoxyethoxy) included in 2) = 3
-Phenylpropylnitrile [compound of formula (2) in which R is a 1-alkoxyethyl group] and 2-(2-tetrahydropyranoxy)-3-7enylprobionitrile [
Compound J of formula (2) in which R is a 2-tetrahydropyranyl group can be obtained by, for example, reacting 2-hydroxy-3-phenylpropionitrile with an alkyl vinyl ether and dihydropyran in the presence of an acid such as phosphoric acid or hydrochloric acid, respectively. It can be easily synthesized by
上記工程図において、上述のようにして得ることのでき
る式（２）の化合物からの式（１）の化合物の合成は、
式（２）の化合物を有機溶媒中、メチルマグネシウムハ
ライドまたはメチルリチウムと反応させ、次いで酸の存
在下に加水分解することにより容易に行うことができる
。In the above process diagram, the synthesis of the compound of formula (1) from the compound of formula (2) that can be obtained as described above is as follows:
This can be easily carried out by reacting the compound of formula (2) with methylmagnesium halide or methyllithium in an organic solvent, and then hydrolyzing it in the presence of an acid.
反応は、例えば、約−５０℃〜約８０℃、より好ましく
は約−２０°Ｃ〜約５０℃程度の範囲内の温度で、通常
約１時間〜約１０時間、より好ましくは約３時間〜約５
時間程度で行うことができる。The reaction is carried out, for example, at a temperature in the range of about -50°C to about 80°C, more preferably about -20°C to about 50°C, and usually for about 1 hour to about 10 hours, more preferably about 3 hours to Approximately 5
It can be done in about an hour.
この反応に使用しうるメチルマグネシウムハライドの具
体例としては、例えば、メチルマグネシウムクロライド
、メチルマグネシウムブロマイド、メチルマグネシウム
クロライドなどを好ましく例示できる。メチルマグネシ
ウムハライドまたはメチルリチウムの使用量は、式（２
）の化合物１モルに対して、約０．５モル〜約５モル、
より好ましくは約１モル〜約３モル程度の範囲内を例示
することができる。また、上記反応に使用する有機溶媒
としては、例えば、エーテル、テトラヒドロフラン、ベ
シセン、トルエンなどを挙げることができる。これら有
機溶媒の使用量は、臨界的ではないが、式（２）の化合
物に対して、約１〜約５０重量倍程度の範囲をより好ま
しく例示することができる。Preferred examples of methylmagnesium halide that can be used in this reaction include methylmagnesium chloride, methylmagnesium bromide, and methylmagnesium chloride. The amount of methylmagnesium halide or methyllithium to be used is determined by the formula (2
) about 0.5 mol to about 5 mol per mol of the compound,
A more preferable range is about 1 mol to about 3 mol. Further, examples of the organic solvent used in the above reaction include ether, tetrahydrofuran, bethicene, and toluene. Although the amount of these organic solvents to be used is not critical, a more preferable range is about 1 to about 50 times the weight of the compound of formula (2).
上述の加水分解反応は、例えば、約１０’Ｏ〜約１００
℃程度、より好ましくは約り０℃〜約５０℃程度の範囲
内の温度で、例えば、約０．５時間〜約１０時間、より
好ましくは約２時間〜約５時間程度で行うことができる
。The above hydrolysis reaction may be performed, for example, from about 10'O to about 100
It can be carried out at a temperature of about 0.degree. C., more preferably about 0.degree. C. to about 50.degree. C., for example, about 0.5 hours to about 10 hours, more preferably about 2 hours to about 5 hours. .
この反応に使用しうる酸としては、例えば、塩酸、硫酸
、リン酸などを挙げることができる。これらの酸の使用
量には、特別な制約はなく適宜選択することができ、例
えば、式（２）の化合物１モルに対して、約１モル〜約
ｌＯモル程度の範囲内、より好ましくは約２モル〜約５
モル程度の範囲内を挙げることができる。Examples of acids that can be used in this reaction include hydrochloric acid, sulfuric acid, and phosphoric acid. The amount of these acids to be used is not particularly restricted and can be selected as appropriate, for example, within the range of about 1 mol to about 10 mol, more preferably about 1 mol to about 10 mol, per 1 mol of the compound of formula (2). Approximately 2 moles to approximately 5
The amount can be within a molar range.
反応終了後は常法に従って水洗浄、乾燥、濃縮後、必要
により、例えば、蒸留のごとき手段で精製して式（１）
の化合物を好収率、好純度で得ることができる。After the reaction is completed, it is washed with water, dried, and concentrated according to a conventional method, and if necessary, purified by means such as distillation to obtain the formula (1).
The compound can be obtained in good yield and purity.
以下に、本発明を参考例および実施例を挙げてさらに詳
細に説明する
（実施例）
参考例１
成
フラスコに亜硫酸ナトリウム５７ｇ （０，５５モル）
および水２００ｍ１を仕込み、氷水冷却下（１０〜１５
℃）に３０分間でフェニルアセトアルデヒド６０ｇ （
０，５モル）を滴下する。滴下後、シアン化ナトリウム
２８ｇ （０，５５モル）と水１２５ｍ１の水溶液を氷
冷却下（１０〜１５℃）に３０分で滴下し反応させる。The present invention will be explained in more detail below by referring to Reference Examples and Examples (Examples) Reference Example 1 57 g (0.55 mol) of sodium sulfite in a synthetic flask
Add 200ml of water and cool with ice water (10~15ml).
60 g of phenylacetaldehyde (
0.5 mol) was added dropwise. After the dropwise addition, an aqueous solution of 28 g (0.55 mol) of sodium cyanide and 125 ml of water was added dropwise over 30 minutes under ice cooling (10-15 DEG C.) to react.
滴下後、更に、室温（２０〜２５℃）で３時間撹拌して
反応を終了させる。反応終了後、反応生成物をトルエン
で抽出し、抽出物を水洗浄、濃縮、乾燥などの処理を行
うことにより、純粋な白色結晶物の２−ヒドロキシル３
−フニニルプロピオニトリル６９ｇ（収率：９４％）を
得た。After the dropwise addition, the mixture is further stirred at room temperature (20 to 25°C) for 3 hours to complete the reaction. After the reaction is completed, the reaction product is extracted with toluene, and the extract is washed with water, concentrated, and dried to obtain a pure white crystalline product of 2-hydroxyl 3
-Funinylpropionitrile 69g (yield: 94%) was obtained.
参考例２
フラスコに２−ヒドロキシ−３−フェニルプロピオニト
リル７３．５ｇ （０，５モル）、８５％リンｒｊ１１
．０ｇ８よびトルエン１００ ｍ ｌを仕込む。この中
に、水冷却下、約０．５時間を要してエチルビニルエー
テル４３ｇ（０，６モル）を滴下する。滴下終了後、さ
らに室温で３時間撹拌して反応を終了させる。反応終了
後、反応生成物を炭酸ナトリウム水溶液に注入し、トル
エン層を分離する。このトルエン層を水洗浄、乾燥、濃
縮して２−（１−エトキシエトキシ）−３−７エニルク
ａビオニトリルをＩ ｌＯｇ （収率：１００％）を得
る。Reference Example 2 73.5 g (0.5 mol) of 2-hydroxy-3-phenylpropionitrile in a flask, 85% phosphorus rj11
．． Charge 0g8 and 100ml of toluene. 43 g (0.6 mol) of ethyl vinyl ether was added dropwise to this solution over a period of about 0.5 hours while cooling with water. After completion of the dropwise addition, the mixture was further stirred at room temperature for 3 hours to complete the reaction. After the reaction is completed, the reaction product is poured into an aqueous sodium carbonate solution and the toluene layer is separated. The toluene layer is washed with water, dried, and concentrated to obtain IIOg of 2-(1-ethoxyethoxy)-3-7enylquabionitrile (yield: 100%).
実施例１
マグネシウム２３．３ｇ （０，９６モル）およびエー
テル１００ｍ１を仕込んだフラスコに、メチルブロマイ
ド９０．８ｇ （０，９６モル）とエーテル９０．８ｇ
の溶液を氷水冷却下（１５〜２０℃）に撹拌しながら滴
下し、メチルマグネシウムブロマイドを調製する。次に
、この中へ２−ヒドロキシ−３−フェニルプロピオニト
リル５５゜９ｇ （０，３８モル）のエーテル１００ｍ
１溶液を氷水冷却下（１５〜２０℃）に１．５時間を要
して滴下し反応させる。滴下後、更に、室温で２時間撹
拌して反応を終了する。反応終了後、２規定の塩酸水溶
液１．２リツトルを仕込んだフラスコの中に反応生成物
を注入し、室温で２時間撹拌した後エーテル層を分離す
る。エーテル層を水洗浄、乾燥、濃縮した後、蒸留して
純粋な式（１）め化合物３６ｇ（収率：５８％）を得た
。Example 1 A flask containing 23.3 g (0.96 mol) of magnesium and 100 ml of ether was charged with 90.8 g (0.96 mol) of methyl bromide and 90.8 g of ether.
The solution was added dropwise while stirring under ice water cooling (15 to 20°C) to prepare methylmagnesium bromide. Next, 55°9 g (0.38 mol) of 2-hydroxy-3-phenylpropionitrile and 100 ml of ether were added to the solution.
1 solution was added dropwise under ice water cooling (15 to 20°C) over a period of 1.5 hours to react. After the dropwise addition, the mixture was further stirred at room temperature for 2 hours to complete the reaction. After the reaction is completed, the reaction product is poured into a flask containing 1.2 liters of a 2N aqueous hydrochloric acid solution, and after stirring at room temperature for 2 hours, the ether layer is separated. The ether layer was washed with water, dried, concentrated, and then distilled to obtain 36 g (yield: 58%) of the pure compound of formula (1).
那点：１０５−１０６°Ｏ／２ｍｍＨｇ実施例２
ルマグネシウムブロマイドと反応させる。滴下後、さら
に２時間撹拌して反応を終了させる。反応終了後、反応
生成物を氷水で冷却した塩酸水溶液の中に注入し、２時
間撹拌する。撹拌終了後、生成物をエーテル抽出し、エ
ーテル層を水洗浄、乾燥、濃縮、蒸留することにより純
粋な式（１）の化合物５９ｇ（収率ニア２％）を得た。Point: 105-106°O/2mmHg Example 2 React with magnesium bromide. After the dropwise addition, the mixture is further stirred for 2 hours to complete the reaction. After the reaction is complete, the reaction product is poured into an aqueous hydrochloric acid solution cooled with ice water and stirred for 2 hours. After stirring, the product was extracted with ether, and the ether layer was washed with water, dried, concentrated, and distilled to obtain 59 g of pure compound of formula (1) (yield: 2%).
実施例３
フラスコにマグネシウム１５．０ｇ （０，６モル）、
テトラヒドロフラン１００ｍ１を仕込む。Example 3 Magnesium 15.0g (0.6 mol) in a flask,
Charge 100ml of tetrahydrofuran.
この中にメチルブロマイド６０ｇ （０，６２５モル）
のテトラヒドロフラン１７０ｍ１の溶液を氷冷却下に１
．５時間で滴下する。滴下終了後、更に０．５時間撹拌
してメチルマグネシウムブロマイドを調製する。次に、
水冷却下でこのフラスコｊ、：２−（１−エトキシエト
キシ）−３−７工ニルプロビオニトリルｌｌＯｇ（０，
５モル）のテトラヒドロフラン２００ ｍ ｌの溶液を
滴下し、メチフラスコに２−（２−テトラヒドロピラノ
キシ）−３−７エニルプロピオニトリル２３．１ｇ （
０゜１モル）および乾燥エーテル２００ｍ１を仕込む。In this, 60g (0,625 mol) of methyl bromide
A solution of 170 ml of tetrahydrofuran was added under ice cooling.
．． Drop in 5 hours. After the addition is complete, the mixture is stirred for an additional 0.5 hour to prepare methylmagnesium bromide. next,
This flask under water cooling: 2-(1-ethoxyethoxy)-3-7-ethylprobionitrile
A solution of 200 ml of tetrahydrofuran (200 ml) of 2-(2-tetrahydropyranoxy)-3-7enylpropionitrile (23.1 g
0°1 mol) and 200 ml of dry ether.
アルゴン雰囲気下に氷水で冷却しながら、メチルリチウ
ムのエーテル溶液（１モル溶液）１２０ｍｌを２時間で
滴下する。滴下後、更に、同じ温度で２時間撹拌し反応
させる。反応終了後、反応生成物を氷水で冷却した２規
定の硫酸水溶液１２０ｍ１中に注入し、室温で５時間撹
拌する。撹拌終了後、エーテル層を分離し、中和、洗浄
、乾燥、濃縮、蒸留などの処理をおこなうことにより純
粋な式（１）の化合物１２．３ｇ （収率ニア５％）を
得た。While cooling with ice water under an argon atmosphere, 120 ml of an ether solution (1 molar solution) of methyllithium was added dropwise over 2 hours. After the dropwise addition, the mixture was further stirred and reacted at the same temperature for 2 hours. After the reaction is completed, the reaction product is poured into 120 ml of a 2N sulfuric acid aqueous solution cooled with ice water and stirred at room temperature for 5 hours. After stirring, the ether layer was separated and subjected to treatments such as neutralization, washing, drying, concentration, and distillation to obtain 12.3 g (yield near 5%) of the pure compound of formula (1).
Claims (1)
は１−アルコキシエチル基 （▲数式、化学式、表等があります▼、ここでＲ＿１は
Ｃ＿１〜Ｃ＿３のアルキル基を示す）を示す で表される２−置換−３−フェニルプロピオニトリルを
メチルマグネシウムハライドまたはメチルリチウムと反
応させ、次いで酸の存在下に加水分解することを特徴と
する下記式（１）▲数式、化学式、表等があります▼（
１） で表される３−ヒドロキシ−４−フェニル−２−ブタノ
ンの製法。[Claims] 1. The following formula (2) ▲ Numerical formula, chemical formula, table, etc. ▼ (2) In the formula, R is a hydrogen atom, a 2-tetrahydropyranyl group, or a 1-alkoxyethyl group (▲ Numerical formula, There are chemical formulas, tables, etc. ▼, where R_1 represents an alkyl group of C_1 to C_3) 2-substituted-3-phenylpropionitrile is reacted with methylmagnesium halide or methyllithium, and then an acidic The following formula (1) is characterized by hydrolysis in the presence of ▲ There are mathematical formulas, chemical formulas, tables, etc.▼ (
1) A method for producing 3-hydroxy-4-phenyl-2-butanone represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63250776A JPH0753679B2 (en) | 1988-10-06 | 1988-10-06 | Process for producing 3-hydroxy-4-phenyl-2-butanone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63250776A JPH0753679B2 (en) | 1988-10-06 | 1988-10-06 | Process for producing 3-hydroxy-4-phenyl-2-butanone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02101037A true JPH02101037A (en) | 1990-04-12 |
| JPH0753679B2 JPH0753679B2 (en) | 1995-06-07 |
Family
ID=17212875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63250776A Expired - Fee Related JPH0753679B2 (en) | 1988-10-06 | 1988-10-06 | Process for producing 3-hydroxy-4-phenyl-2-butanone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0753679B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007254399A (en) * | 2006-03-24 | 2007-10-04 | Mitsui Norin Co Ltd | New substance tmr |
-
1988
- 1988-10-06 JP JP63250776A patent/JPH0753679B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007254399A (en) * | 2006-03-24 | 2007-10-04 | Mitsui Norin Co Ltd | New substance tmr |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0753679B2 (en) | 1995-06-07 |
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