JPS6330291B2 - - Google Patents
Info
- Publication number
- JPS6330291B2 JPS6330291B2 JP60153533A JP15353385A JPS6330291B2 JP S6330291 B2 JPS6330291 B2 JP S6330291B2 JP 60153533 A JP60153533 A JP 60153533A JP 15353385 A JP15353385 A JP 15353385A JP S6330291 B2 JPS6330291 B2 JP S6330291B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- present
- haloketones
- halogen
- rxalh
- 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
- 238000000034 method Methods 0.000 claims description 11
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 230000008707 rearrangement Effects 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 230000000707 stereoselective effect Effects 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000007858 starting material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- NYLOEXLAXYHOHH-UHFFFAOYSA-N 2,2-diphenylethanol Chemical compound C=1C=CC=CC=1C(CO)C1=CC=CC=C1 NYLOEXLAXYHOHH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- AXCPQHPNAZONTH-SSDOTTSWSA-N (2r)-2-chloro-1-phenylpropan-1-one Chemical compound C[C@@H](Cl)C(=O)C1=CC=CC=C1 AXCPQHPNAZONTH-SSDOTTSWSA-N 0.000 description 1
- ZTEHOZMYMCEYRM-UHFFFAOYSA-N 1-chlorodecane Chemical compound CCCCCCCCCCCl ZTEHOZMYMCEYRM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical group 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
Description
〔産業上の利用分野〕
本発明は、α―ハロケトン類を50℃以下で
RxAlH3―ｘ（但しＲはアルキル基、ｘは３又は
２）とAlX3（但しＸはハロゲン）を組合せ作用さ
せることを特徴とする立体選択的に転位と還元を
同時に行わせる方法に関する。
〔従来の技術〕
従来ケトン類に対し立体選択的に転位と還元を
同時に行わせる方法として下式に示す反応［土橋
ら（1984）］が知られているに過ぎない。
（但しＲ、R1、R2は夫々アルキル基もしくはア
リール基を、又ｉ―Buはイソブチル基を、Etは
エチル基を示す）
しかもこの反応は−78℃のような低温で行う必
要があつた。
〔発明が解決しようとする問題点〕
そこで本発明者らは、α―ハロケトン類の立体
選択的転位還元反応を０℃以上でも立体選択性を
失うことなく反応を進行させる方法を種々研究の
結果、発見した。０℃以上の反応温度で反応を行
うことができ、しかも立体選択性が100％ないし
それに近い選択率であることは工業的に大変価値
のある反応であることは言うまでもない。
〔問題点を解決するための手段〕
本発明は、下記一般式［］で表わされるα―
ハロケトン類（但しR′、R″、Ｒはアルキル、
アリール、アリル基でＸはハロゲンを示す）を50
℃以下の温度でRxAlH3―ｘ（但しＲはアルキル
基、ｘは３又は２）とAlX3（但しＸはハロゲン）
を組合せ作用せしめて、α―ハロケトン類に立体
選択的に転位と還元を同時に行わせて下記一般式
［］で表わされるアルコール類（但しR′、R″、
Ｒ、Ｘは前記に同じ）とすることを要旨として
いる。
本発明の基本化学反応式は下記に示す通りで
カルボニル基に結合したR′基の転位及びカル
ボニル基の還元が同時に起る反応である。
〔作 用〕
本発明では出発物質としてα―ハロケトン類
［］を使用するが、その代表例としてのα―ク
ロルケトンは次式に示すように、α―ヒドロキシ
ケトンにチオニルクロリド又は塩化水素―金属ハ
ロゲン化物を作用させて高収率で容易に得られ
る。
この反応の原料であるα―ヒドロキシケトンは
アルデヒドの２量化反応により高収率で得られる
ことも既知である。＊
＊オルガニツクシンセシス（Organic
Syntheses）62、170〜178（1984）
α―ハロケトンの合成法は他にも多数あり省略
するが有機化学的に容易に得られる化合物であ
る。
次に本発明の転位・還元法は溶媒にトルエン、
ベンゼン、ヘキサン、エーテル、メチレンクロリ
ド等の溶媒を使用して、α―ハロケトン類の約15
％〜20％溶液を好ましくは、０℃〜50℃の温度で
代表例としてｉ―Bu2AlHとAlCl3の等モル混合
物を加えて１〜２時間程反応させた後、希塩酸で
加水分解し、溶媒を溜出して生成物を得る。
出発原料が光学活性化合物である例を下記に示
す。例えば天然産の乳酸を原料として下記の反応
式で容易にα―クロルケトンを合成できる。
（Ｒはメチル以外のアルキル基、アリール基又は
アリル基）
この反応で得たα―クロルケトンは出発原料の
乳酸とは反対の不斉炭素を有するが、本発明によ
る転位還元反応が立体的に100％反転の反応であ
るので
再び元の乳酸と同一絶対配置の化合物が得られ
る。
以上の例ではα―クロルケトンを使用し還元剤
としてｉ―Bu2AlH―AlCl3系試薬を用いて説明
したが他のハロゲン化物例えばAlBr3でも同様な
反応が起る。
実施例
以下に実施例を例示して更に本発明を説明する
が本発明はこれによつて何等制限を受けるもので
はない。
実施例 １
デシルクロリド
[Industrial Application Field] The present invention is directed to the treatment of α-haloketones at 50°C or lower.
The present invention relates to a method for simultaneous stereoselective rearrangement and reduction, characterized by the combination of RxAlH 3 --x (wherein R is an alkyl group and x is 3 or 2) and AlX 3 (where X is a halogen). [Prior Art] Conventionally, the only known method for stereoselectively rearranging and reducing ketones at the same time is the reaction shown in the following formula [Tsuchibashi et al. (1984)]. (However, R, R 1 and R 2 each represent an alkyl group or an aryl group, i-Bu represents an isobutyl group, and Et represents an ethyl group.) Moreover, this reaction needs to be carried out at a low temperature such as -78°C. Ta. [Problems to be Solved by the Invention] Therefore, the present inventors have conducted various studies on a method for proceeding the stereoselective rearrangement reduction reaction of α-haloketones without losing stereoselectivity even at temperatures above 0°C. ,discovered. Needless to say, this reaction is industrially very valuable because it can be carried out at a reaction temperature of 0° C. or higher and the stereoselectivity is 100% or close to it. [Means for solving the problems] The present invention provides α-
Haloketones (where R′, R″, R are alkyl,
Aryl, allyl group where X represents halogen) 50
At a temperature below ℃, RxAlH 3 -x (where R is an alkyl group, x is 3 or 2) and AlX 3 (however, X is a halogen)
are reacted in combination to stereoselectively rearrange and reduce α-haloketones at the same time.
R and X are the same as above). The basic chemical reaction formula of the present invention is as shown below. This is a reaction in which rearrangement of the R' group bonded to the carbonyl group and reduction of the carbonyl group occur simultaneously. [Function] In the present invention, α-haloketones [] are used as starting materials, and α-chloroketone as a representative example is a mixture of α-hydroxyketone with thionyl chloride or hydrogen chloride-metal halogen, as shown in the following formula. It can be easily obtained in high yield by reacting with compounds. It is also known that α-hydroxyketone, which is a raw material for this reaction, can be obtained in high yield by a dimerization reaction of aldehydes. * *Organic synthesis
Syntheses) 62 , 170-178 (1984) There are many other methods for synthesizing α-haloketones, and although they are omitted here, they are compounds that can be easily obtained using organic chemistry. Next, the rearrangement/reduction method of the present invention uses toluene as a solvent,
Approximately 15% of α-haloketones can be prepared using solvents such as benzene, hexane, ether, and methylene chloride.
% to 20% solution is preferably reacted at a temperature of 0°C to 50°C with an equimolar mixture of i-Bu 2 AlH and AlCl 3 for about 1 to 2 hours, and then hydrolyzed with dilute hydrochloric acid. , the solvent is distilled off to obtain the product. Examples in which the starting material is an optically active compound are shown below. For example, α-chloroketone can be easily synthesized using the following reaction formula using naturally produced lactic acid as a raw material. (R is an alkyl group other than methyl, an aryl group, or an allyl group) The α-chloroketone obtained by this reaction has an asymmetric carbon opposite to that of the starting material lactic acid, but the rearrangement reduction reaction according to the present invention Since it is a % reversal reaction, A compound having the same absolute configuration as the original lactic acid is obtained again. In the above example, α-chloroketone was used and an i-Bu 2 AlH-AlCl 3 reagent was used as the reducing agent, but a similar reaction occurs with other halides such as AlBr 3 . EXAMPLES The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto in any way. Example 1 Decyl chloride
【式】4.1ｇ（1.78
×10-2mol）をトルエン60mlに溶解し、窒素気流
下ｉ―Bu2AlH2.5ｇ（1.78×10-2mol）と
AlCl32.4ｇ（1.78×10-2mol）の混合物を加えて
30℃で２時間撹拌し希塩酸20mlで加水分解後トル
エン層を分離し、減圧下トルエンを留去すると
２，２―ジフエニルエタノール3.6ｇ（収率100
％）が得られた。mp.55〜56℃
実施例 ２
実施例１のｉ―Bu2AlHにかえて、ｉ―Bu3Al
を使用し、あとは実施例１と同様な反応を行つ
た。その結果、２，２―ジフエニルエタノールを
収率95％で得られた。
実施例 ３
光学活性（Ｓ）―乳酸より有機合成反応により
得た光学活性（Ｒ）―２―クロルプロピオフエノ
ン[Formula] 4.1g (1.78 × 10 -2 mol) was dissolved in 60ml of toluene, and 2.5g (1.78 × 10 -2 mol) of i-Bu 2 AlH was dissolved under a nitrogen stream.
Add a mixture of 2.4 g (1.78 x 10 -2 mol) of AlCl 3
Stir at 30°C for 2 hours, hydrolyze with 20ml of diluted hydrochloric acid, separate the toluene layer, and distill off the toluene under reduced pressure to obtain 3.6g of 2,2-diphenylethanol (yield 100%).
%)was gotten. mp.55-56℃ Example 2 Instead of i-Bu 2 AlH in Example 1, i-Bu 3 Al
The rest of the reaction was carried out in the same manner as in Example 1. As a result, 2,2-diphenylethanol was obtained with a yield of 95%. Example 3 Optically active (R)-2-chloropropiophenone obtained from optically active (S)-lactic acid by organic synthesis reaction
本発明方法によれば反応温度を０℃以上とする
ことができ、しかも出発原料であるα―ハロケト
ン類に光学活性な化合物を用いると他の合成法で
は大変合成が困難なアルコールが光学純度100％
で生成することを特徴にしている。また本発明方
法により合成できるアルコール誘導体は医薬品、
農薬その他の所謂フアインケミストリー分野に於
いて有用な有機化合物である。
According to the method of the present invention, the reaction temperature can be set to 0°C or higher, and when an optically active compound is used as the starting material α-haloketone, an alcohol that is very difficult to synthesize using other synthesis methods can be produced with an optical purity of 100°C. %
It is characterized by being generated by. In addition, the alcohol derivatives that can be synthesized by the method of the present invention are pharmaceuticals,
It is an organic compound useful in agricultural chemicals and other so-called fine chemistry fields.
Claims (1)
アリル基で、夫々同一でも異つてもよい。Ｘは
ハロゲンを示す） で表わされるα―ハロケトン類を50℃以下で
RxAlH3―ｘ（但しＲはアルキル基、ｘは３又は
２）とAlX3（但しＸはハロゲン）を組合せ作用さ
せることにより下記一般式［］ （但しR′、R″、Ｒは前記に同じ） で表わされるアルコール類を製することを特徴と
する立体選択的に転位と還元を同時に行わせる方
法。 ２ α―ハロケトン類が光学活性化合物である特
許請求の範囲第１項記載の方法。 ３ RxAlH3―ｘがｉ―Bu3Al又はｉ―Bu2AlH
である特許請求の範囲第１項又は第２項記載の方
法。 ４ AlX3がAlCl3又はAlBr3である特許請求の範
囲第１項から第３項までのいずれか１項記載の方
法。[Claims] 1. The following general formula [] (However, R′, R″, R are alkyl, aryl,
Allyl groups may be the same or different. (X indicates halogen) α-haloketones represented by
By combining RxAlH 3 -x (where R is an alkyl group and x is 3 or 2) and AlX 3 (where X is a halogen), the following general formula [] (However, R′, R″, and R are the same as above.) A stereoselective method of simultaneously performing rearrangement and reduction, characterized by producing an alcohol represented by A method according to claim 1. 3 RxAlH 3 -x is i-Bu 3 Al or i-Bu 2 AlH
The method according to claim 1 or 2, wherein: 4. The method according to any one of claims 1 to 3, wherein AlX 3 is AlCl 3 or AlBr 3 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60153533A JPS6216435A (en) | 1985-07-12 | 1985-07-12 | Steroselective rearrangement and reduction of alpha-haloketone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60153533A JPS6216435A (en) | 1985-07-12 | 1985-07-12 | Steroselective rearrangement and reduction of alpha-haloketone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6216435A JPS6216435A (en) | 1987-01-24 |
| JPS6330291B2 true JPS6330291B2 (en) | 1988-06-17 |
Family
ID=15564598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60153533A Granted JPS6216435A (en) | 1985-07-12 | 1985-07-12 | Steroselective rearrangement and reduction of alpha-haloketone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6216435A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4576984A (en) * | 1982-02-04 | 1986-03-18 | Morton Thiokol, Inc. | Stabilizer compositions for PVC resins |
| JP4774802B2 (en) * | 2005-05-16 | 2011-09-14 | セントラル硝子株式会社 | Reduction method using lithium aluminum hydride |
| WO2009042864A2 (en) | 2007-09-27 | 2009-04-02 | Graphic Packaging International, Inc. | Carton feeder having friction reducing support shaft |
-
1985
- 1985-07-12 JP JP60153533A patent/JPS6216435A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6216435A (en) | 1987-01-24 |
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