JP3115410B2 - Method for producing allyl-type carboxylic acid - Google Patents
Method for producing allyl-type carboxylic acidInfo
- Publication number
- JP3115410B2 JP3115410B2 JP04153161A JP15316192A JP3115410B2 JP 3115410 B2 JP3115410 B2 JP 3115410B2 JP 04153161 A JP04153161 A JP 04153161A JP 15316192 A JP15316192 A JP 15316192A JP 3115410 B2 JP3115410 B2 JP 3115410B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- barium
- carboxylic acid
- allyl
- compound
- 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 - Fee Related
Links
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
【0001】[0001]
【産業上の利用分野】本発明は、位置選択性及び立体選
択性の高いアリル型カルボン酸の製造方法に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an allylic carboxylic acid having high regioselectivity and stereoselectivity.
【0002】[0002]
【従来の技術及び発明が解決しようとする課題】従来、
多くのマグネシウムや亜鉛反応剤が有機合成化学の分野
に応用されてきた。例えば、グリニヤール試薬として知
られる有機マグネシウムハライドは、種々の化学反応に
有用な試薬として広く用いられている。例えば、特開平
3−271236号公報には、アリルマグネシウム反応剤に、
シアン化銅と塩化リチウムを加えて調製したアリル化反
応剤がハロゲン化アリル型化合物とヘッド−トゥーテイ
ル型カップリング反応を起こし、位置選択性の高いテル
ペン誘導体が得られることが開示されている。2. Description of the Related Art
Many magnesium and zinc reagents have been applied in the field of synthetic organic chemistry. For example, organomagnesium halides known as Grignard reagents are widely used as reagents useful for various chemical reactions. For example, JP-A-3-271236 discloses that an allyl magnesium reactant
It is disclosed that an allylation reagent prepared by adding copper cyanide and lithium chloride causes a head-to-tail type coupling reaction with an allylic halide compound to obtain a terpene derivative having high regioselectivity.
【0003】しかし、従来知られているアリル金属反応
剤とカルボニル化合物との反応、例えば、アリル型マグ
ネシウムハライドとカルボニル化合物との反応は主とし
てγ置換化合物が生成し、またアリル型マグネシウム反
応剤の出発物質の立体構造も変化することがあり、親電
子剤との反応で生じる位置・立体制御の問題は未だ解決
されいない。However, the conventionally known reaction between an allyl metal reactant and a carbonyl compound, for example, the reaction between an allyl-type magnesium halide and a carbonyl compound mainly produces a γ-substituted compound, and the starting of the allyl-type magnesium reactant. The tertiary structure of the substance may also change, and the problem of position and steric control resulting from the reaction with the electrophile has not been solved yet.
【0004】そこで本発明者らはアリル型バリウム反応
剤を用いてカルボニル化合物との反応を行い、その位置
及び立体選択性について鋭意検討した結果、様々なアル
デヒド及びケトンとの反応において、高収率かつ高選択
的にα付加体が得られ、さらにその二重結合の立体化学
が保持されることを見出し既に特許出願した(特願平3
−317297号)。さらに、本発明者らは、様々なハロゲン
化アリル型化合物から調製したアリル型バリウム反応剤
を用いて、二酸化炭素との反応により、出発物質の立体
構造を保持し、α位に選択的に付加したアリル型不飽和
カルボン酸が得られることを見出し本発明を完成するに
至った。[0004] The present inventors have conducted a reaction with a carbonyl compound using an allyl-type barium reactant, and have conducted intensive studies on the position and stereoselectivity. As a result, in the reaction with various aldehydes and ketones, a high yield was obtained. It has been found that an α-adduct can be obtained with high selectivity and that the stereochemistry of the double bond is retained, and a patent application has already been filed (Japanese Patent Application No. Hei.
No. 317297). Furthermore, the present inventors have maintained the steric structure of the starting material by reaction with carbon dioxide using an allyl-type barium reactant prepared from various allyl halide-type compounds, and selectively added the α-position. The inventors have found that an allyl-type unsaturated carboxylic acid can be obtained, and have completed the present invention.
【0005】[0005]
【課題を解決するための手段】即ち、本発明は、一般式
(I)That is, the present invention provides a compound represented by the general formula (I):
【0006】[0006]
【化5】 Embedded image
【0007】(式中、R1は水素原子、アルキル基又はア
ルケニル基、R2は水素原子、アルキル基又はアルケニル
基、R3は水素原子、アルキル基又はアルケニル基を示
し、R1とR3は一緒になって環を形成していてもよい。X
はハロゲン原子を示す。)で表されるハロゲン化アリル
型化合物とCO2 とを反応させ、一般式(II)(Wherein, R 1 represents a hydrogen atom, an alkyl group or an alkenyl group, R 2 represents a hydrogen atom, an alkyl group or an alkenyl group, R 3 represents a hydrogen atom, an alkyl group or an alkenyl group, and R 1 and R 3 May together form a ring, X
Represents a halogen atom. ) Is reacted with CO 2 to give a compound of the general formula (II)
【0008】[0008]
【化6】 Embedded image
【0009】(式中、R1、R2、R3は前記と同様の意味を
有する。)で表されるアリル型カルボン酸を得る反応に
おいて、活性金属バリウムを用いることを特徴とする、
一般式(II)で表されるアリル型カルボン酸の製造方法
を提供するものである。Wherein R 1 , R 2 , and R 3 have the same meanings as described above, wherein an active metal barium is used in the reaction for obtaining the allylic carboxylic acid.
It is intended to provide a method for producing an allyl-type carboxylic acid represented by the general formula (II).
【0010】本発明の製造方法を更に詳細に説明する。
一般式(I)で表されるハロゲン化アリル型化合物を、
不活性有機溶媒中で活性金属バリウムと反応させ、引続
きCO2 ガスと反応させて、一般式(II)で表されるア
リル型カルボン酸を得ることができる。ここで用いられ
る活性金属バリウムは、ハロゲン化バリウムと、リチウ
ム、ナトリウム又はカリウムのアリール化合物とのアニ
オンラジカル種によって、還元的に調製することができ
る。以下に具体的な調製法を示す。The production method of the present invention will be described in more detail.
An allylic halide compound represented by the general formula (I)
The allyl-type carboxylic acid represented by the general formula (II) can be obtained by reacting with an active metal barium in an inert organic solvent and subsequently reacting with a CO 2 gas. The active metal barium used herein can be prepared reductively by an anionic radical species of a barium halide and an aryl compound of lithium, sodium or potassium. The specific preparation method is shown below.
【0011】即ち、ヨウ化バリウム等のハロゲン化バリ
ウム1当量に対し、2当量のビフェニルリチウム等のリ
チウム、ナトリウム又はカリウムのアリール化合物を加
え、乾燥THF等の不活性有機溶媒中において室温で反
応させることにより得ることができる。ここで用いられ
る不活性有機溶媒としては、THFの他に、例えばジエ
チルエーテルなどのエーテル系の溶媒を使用することが
できる。本発明において必要な活性金属バリウムを生成
するハロゲン化バリウムの量は特に限定されないが、通
常は一般式(I)で表されるハロゲン化アリル型化合物
1当量に対し1〜3当量、好ましくは2当量である。こ
のようにして得られた活性金属バリウムが懸濁した溶媒
を、−78〜0℃に冷却し、一般式(I)で表されるハロ
ゲン化アリル型化合物を加えると、以下の反応式に示す
ように直ちに一般式(III) で表されるアリルバリウム反
応剤の赤色がかった懸濁液が得られる。That is, 2 equivalents of an aryl compound of lithium, sodium or potassium such as biphenyllithium is added to 1 equivalent of barium halide such as barium iodide, and reacted at room temperature in an inert organic solvent such as dry THF. Can be obtained. As the inert organic solvent used here, besides THF, for example, an ether-based solvent such as diethyl ether can be used. The amount of barium halide for forming the active metal barium required in the present invention is not particularly limited, but is usually 1 to 3 equivalents, preferably 2 to 1 equivalent of the allyl halide compound represented by the general formula (I). Is equivalent. The thus-obtained solvent in which the active metal barium is suspended is cooled to −78 ° C. to 0 ° C., and the allyl halide type compound represented by the general formula (I) is added. A reddish suspension of the allyl barium reactant of the general formula (III) is thus obtained immediately.
【0012】[0012]
【化7】 Embedded image
【0013】(式中、R1、R2、R3、X は前記と同様の意
味を有する。)この懸濁液を−78〜0℃に保ったまま、
CO2 ガスと反応させると、一般式(II)で表されるア
リル型カルボン酸が得られる。(Wherein R 1 , R 2 , R 3 , and X have the same meaning as described above.) While maintaining the suspension at −78 to 0 ° C.,
When reacted with CO 2 gas, an allyl-type carboxylic acid represented by the general formula (II) is obtained.
【0014】本発明の原料となる一般式(I)で表され
るハロゲン化アリル型化合物の具体例としては、(E)-n-
C7H15CH=CHCH2Cl, (Z)-n-C7H15CH=CHCH2Cl,(Z)-CH3CH
=CHCH2Cl,Specific examples of the allyl halide type compound represented by the general formula (I) as a raw material of the present invention include (E) -n-
C 7 H 15 CH = CHCH 2 Cl, (Z) -n C 7 H 15 CH = CHCH 2 Cl, (Z) -CH 3 CH
= CHCH 2 Cl,
【0015】[0015]
【化8】 Embedded image
【0016】[0016]
【発明の効果】本発明の方法によると、一般式(II)で
表されるようなα付加体が高選択性で得られ、しかもそ
のβ位の二重結合は出発物質の一般式(I)で表される
ハロゲン化アリル型化合物の立体化学を完全に保持し、
高い立体選択性が得られた。According to the method of the present invention, an α-adduct represented by the general formula (II) can be obtained with high selectivity, and the double bond at the β-position is represented by the general formula (I) ) Completely retains the stereochemistry of the allyl halide compound represented by
High stereoselectivity was obtained.
【0017】[0017]
【実施例】以下、実施例により本発明を更に詳細に説明
するが、本発明はこれらの実施例に限定されるものでは
ない。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
【0018】実施例1Embodiment 1
【0019】[0019]
【化9】 Embedded image
【0020】ヨウ化バリウム470mg(1.2mmol)を50mlのシ
ュレンク管に秤取し、減圧下(5mmHg) 、ヒートガンで
十分加熱乾燥した。冷却後、この反応容器にアルゴンガ
スを満たし、乾燥THF5mlを加えた。一方、別の30ml
のシュレンク管を用意し、リチウム片(16mg, 2.3mmol)
とビフェニル(370mg, 2.4mmol) を秤取した。このもの
を減圧下(5mmHg) で脱気し、アルゴンガスで満たした
後、乾燥THF(5ml)を加えて室温(20℃)で2時間
攪拌したところ、濃青色のリチウムビフェニリドのTH
F溶液が得られた。先に調製したヨウ化バリウムのTH
F懸濁液に室温でリチウムビフェニリドのTHF溶液を
ステンレスチューブを通して滴下し、30分間攪拌するこ
とにより、褐色の活性バリウムの懸濁液が得られた。こ
れを−78℃に冷やした後、式(2)で表される塩化ゲラ
ニル 190μl (0.97mmol)のTHF(2ml)溶液をシリン
ジを用いてゆっくりと加えた。同温度で30分間攪拌した
後、過剰量のドライアイスから発生した炭酸ガスを、ニ
ードルを通じて直接反応液中に30分間導入した。ここに
冷却した1N塩酸(8ml)を加え、反応を終結させた。
反応混合物を室温まで昇温した後、飽和食塩水(20ml)
と酢酸エチル(20ml)を加え、よく振盪した後、有機層
と水層に分けた。水層をさらに濃塩酸でpH値を2以上に
した後、再びクロロホルム(10ml×2)と酢酸エチルで
抽出した。有機層を合わせ、チオ硫酸ナトリウムの希薄
溶液で洗浄した後、無水硫酸マグネシウム上で乾燥し
た。乾燥剤を濾過し、濾液を減圧濃縮して得た粗生成物
をシリカゲルカラムクロマトグラフィー(50g、酢酸エ
チル)に供したところ、上記式(1α)及び(1γ)で
表されるアリル型カルボン酸が無色油状物質として得ら
れた(154mg,87 %収率)。さらに、このカルボン酸をエ
ーテルで薄めた後、ジアゾメタンのエーテル溶液を加え
ることにより、メチルエステル体を得た。この生成物の
GLC分析(25m×0.25mm i.d. 、PEG-HT Bonded 、ガ
スクロ工業、カラム温度 130℃、インジェクター温度 1
50℃、窒素圧0.8kg/cm2)によりα体とγ体の比が>99:
1、α体のE/Z比が98:2であることが確認された。 ・保持時間;γ体 4.23分、α−E体 7.57分、α−Z
体 6.89分470 mg (1.2 mmol) of barium iodide was weighed into a 50-ml Schlenk tube, and sufficiently dried by heating with a heat gun under reduced pressure (5 mmHg). After cooling, the reaction vessel was filled with argon gas and 5 ml of dry THF was added. Meanwhile, another 30ml
Prepare a Schlenk tube with lithium pieces (16 mg, 2.3 mmol)
And biphenyl (370 mg, 2.4 mmol) were weighed. This was degassed under reduced pressure (5 mmHg), filled with argon gas, added with dry THF (5 ml) and stirred at room temperature (20 ° C.) for 2 hours to obtain dark blue lithium biphenylide TH.
An F solution was obtained. TH of previously prepared barium iodide
A THF solution of lithium biphenylide was dropped into the F suspension at room temperature through a stainless steel tube, and stirred for 30 minutes to obtain a brown active barium suspension. After cooling to −78 ° C., a solution of 190 μl (0.97 mmol) of geranyl chloride represented by the formula (2) in THF (2 ml) was slowly added using a syringe. After stirring at the same temperature for 30 minutes, carbon dioxide gas generated from an excessive amount of dry ice was directly introduced into the reaction solution through a needle for 30 minutes. To this was added cooled 1N hydrochloric acid (8 ml) to terminate the reaction.
After warming the reaction mixture to room temperature, saturated saline (20 ml)
And ethyl acetate (20 ml), and the mixture was shaken well, and then separated into an organic layer and an aqueous layer. The aqueous layer was further adjusted to pH 2 or more with concentrated hydrochloric acid, and then extracted again with chloroform (10 ml × 2) and ethyl acetate. The organic layers were combined, washed with a dilute solution of sodium thiosulfate, and then dried over anhydrous magnesium sulfate. The drying agent was filtered, the filtrate was concentrated under reduced pressure, and the crude product obtained was subjected to silica gel column chromatography (50 g, ethyl acetate). Was obtained as a colorless oil (154 mg, 87% yield). Further, the carboxylic acid was diluted with ether, and an ether solution of diazomethane was added to obtain a methyl ester. GLC analysis of this product (25 mx 0.25 mm id, PEG-HT Bonded, Gas Chromatography, column temperature 130 ° C, injector temperature 1
The ratio of α-form to γ-form is> 99 at 50 ° C. and nitrogen pressure 0.8 kg / cm 2 ).
1. It was confirmed that the E / Z ratio of the α-form was 98: 2.・ Retention time: γ-isomer 4.23 minutes, α-E-isomer 7.57 minutes, α-Z
Body 6.89 minutes
【0021】[0021]
【化10】 Embedded image
【0022】・TLC:Rf 0.45 (酢酸エチル) ・1H−NMR (CDCl3, 200MHz) δ:1.60(s,3H,CH3), 1.65
(s,3H,CH3), 1.68(s,3H,CH3), 2.02-2.15(m,4H,2CH2),
3.10(d,2H,J=7Hz,CH2), 5.10(m,1H,ビニル基), 5.31(d
t,1H,J=1.4,8.4Hz,ビニル基), 10.8(br,1H,CO2H)TLC: Rf 0.45 (ethyl acetate) 1 H-NMR (CDCl 3 , 200 MHz) δ: 1.60 (s, 3H, CH 3 ) , 1.65
(s, 3H, CH 3 ), 1.68 (s, 3H, CH 3 ), 2.02-2.15 (m, 4H, 2CH 2 ),
3.10 (d, 2H, J = 7Hz, CH 2), 5.10 (m, 1H, vinyl group), 5.31 (d
t, 1H, J = 1.4,8.4Hz, vinyl group), 10.8 (br, 1H, CO 2 H)
【0023】[0023]
【化11】 Embedded image
【0024】・TLC:Rf 0.70 (1:2 酢酸エチル
/ヘキサン) ・1H−NMR (CDCl3, 200MHz) δ:1.60(s,3H,CH3), 1.64
(s,3H,CH3), 1.68(s,3H,CH3), 1.85-2.23(m,4H,2CH2),
3.06(d,2H,J=7.2Hz,CH2), 3.69(s,3H,OCH3), 5.10(m,1
H, ビニル基), 5.33(t,1H,J=8.4Hz, ビニル基) 実施例2TLC: Rf 0.70 (1: 2 ethyl acetate / hexane) 1 H-NMR (CDCl 3 , 200 MHz) δ: 1.60 (s, 3H, CH 3 ) , 1.64
(s, 3H, CH 3 ), 1.68 (s, 3H, CH 3 ), 1.85-2.23 (m, 4H, 2CH 2 ),
3.06 (d, 2H, J = 7.2Hz, CH 2), 3.69 (s, 3H, OCH 3), 5.10 (m, 1
Example 2 (H, vinyl group), 5.33 (t, 1H, J = 8.4 Hz, vinyl group)
【0025】[0025]
【化12】 Embedded image
【0026】実施例1と同様にして、式(4)で表され
る化合物から式(3α)及び(3γ)で表されるアリル
型カルボン酸及びそのメチルエステル体を得た。この生
成物のGLC分析(25m×0.25mm i.d. 、PEG-HT Bonde
d 、ガスクロ工業、カラム温度 130℃、インジェクター
温度 150℃、窒素圧0.8kg/cm2)によりα体とγ体の比が
98:2、α体のE/Z比が99:1であることが確認され
た。 ・保持時間;γ体 5.97分、α−E体 10.31分、α−Z
体 9.92分In the same manner as in Example 1, allylic carboxylic acids represented by the formulas (3α) and (3γ) and methyl ester thereof were obtained from the compound represented by the formula (4). GLC analysis of this product (25 mx 0.25 mm id, PEG-HT Bonde
d, gas chromatography, column temperature 130 ° C, injector temperature 150 ° C, nitrogen pressure 0.8kg / cm 2 )
It was confirmed that the E / Z ratio of 98: 2 and α-form was 99: 1.・ Retention time: γ-isomer 5.97 minutes, α-E-isomer 10.31 minutes, α-Z
Body 9.92 minutes
【0027】[0027]
【化13】 Embedded image
【0028】・TLC:Rf 0.54 (酢酸エチル) ・1H−NMR (CDCl3, 200MHz) δ:0.88(t,3H,CH3), 1.18
-1.46(m,10H,5CH2), 2.03(m,2H,CH2), 3.07(d,2H,J=6.7
Hz,CH2), 5.56(m,2H,2×ビニル基), 10.1(br,1H,CO2H)TLC: Rf 0.54 (ethyl acetate) 1 H-NMR (CDCl 3 , 200 MHz) δ: 0.88 (t, 3H, CH 3 ) , 1.18
-1.46 (m, 10H, 5CH 2 ), 2.03 (m, 2H, CH 2), 3.07 (d, 2H, J = 6.7
Hz, CH 2 ), 5.56 (m, 2H, 2 x vinyl group), 10.1 (br, 1H, CO 2 H)
【0029】[0029]
【化14】 Embedded image
【0030】・TLC:Rf 0.65 (1:2 酢酸エチル
/ヘキサン) ・1H−NMR (CDCl3, 200MHz) δ:0.88(t,3H,CH3), 1.20
-1.48(m,10H,5CH2), 2.02(m,2H,CH2), 3.04(d,2H,J=4.6
Hz,CH2), 3.69(s,3H,OCH3), 5.53(m,2H,2×ビニル基) 実施例3〜6 実施例1における塩化ゲラニルの替わりに、表1に示す
種々のハロゲン化アリル型化合物を用いる他は、実施例
1と同様にしてアリル型カルボン酸を得た。その結果を
表1に示した。TLC: Rf 0.65 (1: 2 ethyl acetate / hexane) 1 H-NMR (CDCl 3 , 200 MHz) δ: 0.88 (t, 3H, CH 3 ) , 1.20
-1.48 (m, 10H, 5CH 2 ), 2.02 (m, 2H, CH 2), 3.04 (d, 2H, J = 4.6
Hz, CH 2 ), 3.69 (s, 3H, OCH 3 ), 5.53 (m, 2H, 2 × vinyl group) Examples 3 to 6 Instead of geranyl chloride in Example 1, various halogenated compounds shown in Table 1 were used. An allylic carboxylic acid was obtained in the same manner as in Example 1 except that an allylic compound was used. The results are shown in Table 1.
【0031】[0031]
【表1】 [Table 1]
【0032】以上の実施例から明らかなように、本発明
の方法によると、高位置選択性及び高立体選択性で、ア
リル型カルボン酸を得ることができる。As is clear from the above examples, according to the method of the present invention, an allyl-type carboxylic acid can be obtained with high regioselectivity and high stereoselectivity.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7,DB名) C07C 51/15 B01J 23/02 C07C 57/03 C07C 57/26 C07B 61/00 300 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 7 , DB name) C07C 51/15 B01J 23/02 C07C 57/03 C07C 57/26 C07B 61/00 300
Claims (2)
R2は水素原子、アルキル基又はアルケニル基、R3は水素
原子、アルキル基又はアルケニル基を示し、R1とR3は一
緒になって式 【化2】 で表される環を形成していてもよい。X はハロゲン原子
を示す。)で表されるハロゲン化アリル型化合物とCO
2 とを反応させ、一般式(II) 【化3】 (式中、R1、R2、R3は前記と同様の意味を有する。)で
表されるアリル型カルボン酸を得る反応において、ハロ
ゲン化バリウムと、リチウム、ナトリウム又はカリウム
のアリール化合物とのアニオンラジカル種によって、還
元的に調製した活性金属バリウムを用いることを特徴と
する、一般式(II)で表されるアリル型カルボン酸の製
造方法。1. A compound of the general formula (I) (Wherein R 1 is a hydrogen atom, an alkyl group or an alkenyl group,
R 2 represents a hydrogen atom, an alkyl group or an alkenyl group, R 3 represents a hydrogen atom, an alkyl group or an alkenyl group, and R 1 and R 3 together represent a group represented by the formula : May form a ring represented by X represents a halogen atom. ) And CO
2 and reacting with the general formula (II) (Wherein, R 1, R 2, R 3 is. Having the same meanings as defined above) in the reaction for obtaining the allylic carboxylic acid represented by halo
Barium genoide and lithium, sodium or potassium
Depending on the anion radical species with the aryl compound
A method for producing an allyl-type carboxylic acid represented by the general formula (II), wherein an originally prepared active metal barium is used.
る。)で表されるハロゲン化アリル型化合物を、不活性
有機溶媒中で、ハロゲン化バリウムと、リチウム、ナト
リウム又はカリウムのアリール化合物とのアニオンラジ
カル種によって、還元的に調製した活性金属バリウムと
反応させ、引続きCO2ガスと反応させることを特徴と
する、一般式(II) 【化5】 (式中、R1、R2、R3は前記と同様の意味を有する。)で
表されるアリル型カルボン酸の製造方法。2. A compound of the general formula (I) (Wherein R 1 , R 2 , R 3 and X have the same meanings as described above) in an inert organic solvent in a barium halide, lithium and sodium
Anion radicals with aryl compounds of lithium or potassium
General formula (II) characterized by reacting with an active metal barium prepared reductively and subsequently with CO 2 gas, depending on the kind of calcium. (Wherein R 1 , R 2 and R 3 have the same meanings as described above).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP04153161A JP3115410B2 (en) | 1992-06-12 | 1992-06-12 | Method for producing allyl-type carboxylic acid |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP04153161A JP3115410B2 (en) | 1992-06-12 | 1992-06-12 | Method for producing allyl-type carboxylic acid |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05339198A JPH05339198A (en) | 1993-12-21 |
JP3115410B2 true JP3115410B2 (en) | 2000-12-04 |
Family
ID=15556379
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP04153161A Expired - Fee Related JP3115410B2 (en) | 1992-06-12 | 1992-06-12 | Method for producing allyl-type carboxylic acid |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3115410B2 (en) |
-
1992
- 1992-06-12 JP JP04153161A patent/JP3115410B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPH05339198A (en) | 1993-12-21 |
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