JPS5929058B2 - Novel production method for chrysanthemum acid ester - Google Patents
Novel production method for chrysanthemum acid esterInfo
- Publication number
- JPS5929058B2 JPS5929058B2 JP3830476A JP3830476A JPS5929058B2 JP S5929058 B2 JPS5929058 B2 JP S5929058B2 JP 3830476 A JP3830476 A JP 3830476A JP 3830476 A JP3830476 A JP 3830476A JP S5929058 B2 JPS5929058 B2 JP S5929058B2
- Authority
- JP
- Japan
- Prior art keywords
- methyl
- triphenylisopropylphosphonium
- butenoate
- oxo
- halide
- 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
- 239000002253 acid Substances 0.000 title claims description 12
- 150000002148 esters Chemical class 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 235000007516 Chrysanthemum Nutrition 0.000 title claims description 7
- 244000189548 Chrysanthemum x morifolium Species 0.000 title claims 2
- -1 alkyl 4-oxo-2E-butenoate Chemical compound 0.000 claims description 19
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- CRBJVPSOOMDSPT-NSCUHMNNSA-N methyl (e)-4-oxobut-2-enoate Chemical group COC(=O)\C=C\C=O CRBJVPSOOMDSPT-NSCUHMNNSA-N 0.000 claims description 4
- HHBXWXJLQYJJBW-UHFFFAOYSA-M triphenyl(propan-2-yl)phosphanium;iodide Chemical group [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C(C)C)C1=CC=CC=C1 HHBXWXJLQYJJBW-UHFFFAOYSA-M 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 241000723353 Chrysanthemum Species 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PBIJFSCPEFQXBB-UHFFFAOYSA-N 1,1-dimethylcyclopropane Chemical class CC1(C)CC1 PBIJFSCPEFQXBB-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- VXJPCEOTZNHHOA-UHFFFAOYSA-N [K].OC Chemical compound [K].OC VXJPCEOTZNHHOA-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012259 ether extract Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- 125000006020 2-methyl-1-propenyl group Chemical group 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical class C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229940035423 ethyl ether Drugs 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000006257 total synthesis reaction Methods 0.000 description 1
- VFXPJEJTBCCTIQ-UHFFFAOYSA-M triphenyl(propan-2-yl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C(C)C)C1=CC=CC=C1 VFXPJEJTBCCTIQ-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/30—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 本発明は、菊酸エステルの製造法に関する。[Detailed description of the invention] The present invention relates to a method for producing chrysanthemum acid ester.
本発明は、次式（ここでＲは１〜６個の炭素原子を含有
するアルキル基を表わす）の２・２−ジメチル−３ＲＳ
−（２／−メチル−Ｖプロペニル）シクロプロパン−１
ＲＳ−カルボン酸アルキルエステル、即ちｄｌ−Ｔｒａ
ｎｓ一菊酸エステルの製造法であつて、強塩基の存在下
に次式の４−オキソ一２Ｅ−ブテン酸アルキルを約２当
量のハロゲン化トリフエニルイソプロピルホスホニウム
と反応させることを特徴とする新規な製造法を目的とす
る。The present invention relates to 2,2-dimethyl-3RS of the following formula (wherein R represents an alkyl group containing 1 to 6 carbon atoms)
-(2/-methyl-Vpropenyl)cyclopropane-1
RS-carboxylic acid alkyl ester, i.e. dl-Tra
A novel method for producing ns monochrylate ester, characterized by reacting an alkyl 4-oxo-2E-butenoate of the following formula with about 2 equivalents of triphenylisopropylphosphonium halide in the presence of a strong base. The aim is to create a manufacturing method that is
試剤は不足量よりもむしろ過剰量を使用するのが先験的
に有利であると思われる。It appears a priori that it is advantageous to use an excess amount of the reagent rather than a deficiency.
本発明の方法を実施するための好ましい条件下において
は、少なくとも２当量のハロゲン化トリフエニルイソプ
ロピルホスホニウムが使用される。Under preferred conditions for carrying out the process of the invention, at least 2 equivalents of triphenylisopropylphosphonium halide are used.
事実、塩基の存在下ではハロゲン化トリフエニルイソプ
ロピルホスホニウムの使用当量の一方はアルデヒド官能
基と反応し、他方は４−オキソ一２Ｅ−ブテン酸アルキ
ルのエチレン性二重結合と反応することが認められる。
経験的には２当量よりも多い量のハロゲン化ホスホニウ
ム、例えば３当量を使用すると満足できる結果が得られ
ることが示された。In fact, it is observed that in the presence of a base, one of the used equivalents of triphenylisopropylphosphonium halide reacts with the aldehyde function and the other with the ethylenic double bond of the alkyl 4-oxo-2E-butenoate. .
Experience has shown that using more than 2 equivalents of phosphonium halide, for example 3 equivalents, gives satisfactory results.
前記の反応をもたらすのに使用される強塩基の中でも特
に水素化アルカリ、アルカリアミド、アルカリアルコラ
ード、アルキルリチウム化合物、特にｎ−ブチルリチウ
ムを列挙することができる。Among the strong bases used to bring about the abovementioned reaction, mention may be made in particular of alkali hydrides, alkali amides, alkali alcoholades, alkyllithium compounds, especially n-butyllithium.
４−オキソ一２Ｅ−ブテン酸アルキルとハロゲン化トリ
フエニルイソプロピルホスホニウムとの縮合は、テトラ
ヒドロフラン、ジメチルスルホキシド、ジメトキシエタ
ン、ジエチレングリコールモノエチルエーテル、ジエチ
レングリコールジエチルエーテル又はエチルエーテルの
ような有機溶媒中で有利に行なわれる。The condensation of the alkyl 4-oxo-2E-butenoate with the triphenylisopropylphosphonium halide is advantageously carried out in an organic solvent such as tetrahydrofuran, dimethyl sulfoxide, dimethoxyethane, diethylene glycol monoethyl ether, diethylene glycol diethyl ether or ethyl ether. It will be done.
この縮合を行なうのに使用されるりん試剤は、よう化、
塩化又は臭化トリフエニルイソプロピルホスホニウムと
することができる。The phosphorus reagents used to carry out this condensation are iodide,
It can be triphenylisopropylphosphonium chloride or bromide.
本発明の方法を実施する好ましい態様は、テトラヒドロ
フラン中でよう化トリフエニルイソプロピルホスホニウ
ムとブチルリチウムとを使用することからなる。A preferred embodiment of carrying out the process of the invention consists of using triphenylisopropylphosphonium iodide and butyllithium in tetrahydrofuran.
本発明の方法における化合物の式において、Ｒは特にメ
チル、エチル、直鎖若しくは分枝鎖プロピル、直鎖若し
くは分枝鎖ブチル、直鎖若しくは分枝鎖ペンチル又は直
鎖若しくは分枝鎖ヘキシル基を表わす。In the formula of the compounds in the process of the invention, R in particular represents a methyl, ethyl, straight-chain or branched propyl, straight-chain or branched butyl, straight-chain or branched pentyl or straight-chain or branched hexyl group. represent.
本発明の方法は、容易に入手できる化合物から出発して
一段階でｄｌ−Ｔｒａｎｓ一菊酸エステルの全合成を可
能ならしめる利点を与える。The process of the invention offers the advantage of allowing the total synthesis of dl-Trans monochrylates in one step starting from readily available compounds.
ｄ１−Ｔｒａｎｓ一菊酸エステルから出発すれば、けん
化のような通常の方法によりｄｌ−Ｔｒａｒｌｓ一菊酸
自体、即ち大きな工業的重要性を有する酸を容易に得る
ことができる。Starting from d1-Trans monochrylate ester, dl-Trarls monochrylate acid itself, an acid of great industrial importance, can be easily obtained by conventional methods such as saponification.
例えば、ある種のアルコールによるそのエステル化は非
常に有用且つ有効な殺虫性化合物の取得を可能ならしめ
るからである。アルキリデントリアリールホスホランと
不飽和エステルを縮合させてＧｅｍ−ジメチルシクロプ
ロパン誘導体を形成させる例は文献から既に知られてい
た（Ｐ．Ａ．ＧｒｉｅｃＯ，．Ｒ．Ｓ．Ｆｉｎｋｅｌｈ
ＯｒｌＴｅｔ．Ｌｅｔｔｅｒｓ３７８ｌ、１９７２及び
Ｗ．Ｇ．Ｄａｕｂｅｎ，．Ａ．Ｐ．ＫＯｚｉｋＯｗｓｋ
ｉ，．Ｔｅｔ．Ｌｅｔｔｅｒｓ３７ｌｌ、１９６６）。
しかしながら、Ｇｅｍ−ジメチルシクロプロパン環が形
成されてしまうと、菊酸の特徴である２メチル−１−プ
ロペニル鎖をシクロプロパン環に簡単な態様で導入する
のは困難であつた。For example, their esterification with certain alcohols makes it possible to obtain very useful and effective insecticidal compounds. Examples of the condensation of alkylidene triarylphosphoranes with unsaturated esters to form Gem-dimethylcyclopropane derivatives were already known from the literature (P.A. GriecO, .R.S. Finkelh
OrlTet. Letters 378l, 1972 and W. G. Dauben,. A. P. KOzikOwsk
i,. Tet. Letters 37ll, 1966).
However, once the Gem-dimethylcyclopropane ring was formed, it was difficult to introduce the 2methyl-1-propenyl chain, which is a characteristic of chrysanthemum acid, into the cyclopropane ring in a simple manner.
かくして、出発物質の４−オキソ一２Ｅ−ブテン酸アル
キルを慎重に選択して菊酸構造の合成を一段階で実現さ
せたことは正に本発明の利点である。Thus, it is truly an advantage of the present invention that the starting material, alkyl 4-oxo-2E-butenoate, was carefully selected to enable the synthesis of the chrysanthemum acid structure in one step.
この選択は全く自明のことではなかつた。これらのブテ
ン酸エステルは、塩基の存在下にブテン酸エステルの二
重結合にハロゲン化トリフエニルイソプロピルホスホニ
ウムが作用することによるシクロプロパンジメチル環の
生成と該ハロゲン化物がアルデヒド性カルボニルに作用
することによる菊酸の特徴であるイソプロピリデン鎖の
生成とを同時に行なわしめるという利点を持つている。
本発明の方法の基礎となる反応は、その機構の面からみ
ても、予期できなかつた特徴を与える。事実、まず塩基
の存在下に１モルのみのハロゲン化トリフエニルイソプ
ロピルホスホニウムを４オキソ一２Ｅ−ブテン酸アルキ
ルと反応させるとこの１モルはアルデヒド性カルボニル
ど反応するが、この生成したジエンを単離した後に続い
てさらに１モルのホスホニウム塩を反応させてももはや
菊酸構造を形成させないことが立証された。まだ完全に
は解明されていないけれども、この現象は本発明の方法
の基礎となる反応の驚くべき特徴を十分に示している。
４−オキソ一２Ｅ−ブテン酸メチル、エチル及びプロピ
ルは、Ｒ．Ｒａｍｂａｕｄ氏他によりＢｕｌｌ．ＳＯｃ
．Ｃｈｉｍ．ｌ５６７（１９６１）に記載の方法により
１−ヒドロキシ−２−ブテン酸メチル、エチル及びプロ
ピルを無水クロム酸でそれぞれ酸化することにより得る
ことができる。This choice was not at all obvious. These butenoic acid esters are produced by the formation of a cyclopropanedimethyl ring by the action of triphenylisopropylphosphonium halide on the double bond of the butenoic acid ester in the presence of a base, and the action of the halide on the aldehydic carbonyl. It has the advantage of simultaneously producing isopropylidene chains, which is a characteristic of chrysanthemum acid.
The reaction underlying the method of the invention also presents unexpected features from its mechanistic point of view. In fact, when only 1 mole of triphenylisopropylphosphonium halide is first reacted with alkyl 4oxo-2E-butenoate in the presence of a base, this 1 mole reacts with aldehydic carbonyl, and the diene formed is isolated. It has been demonstrated that subsequent reaction with an additional 1 mole of phosphonium salt no longer results in the formation of a chrysanthemum acid structure. Although still not completely understood, this phenomenon fully illustrates the surprising features of the reaction underlying the method of the invention.
Methyl, ethyl and propyl 4-oxo-2E-butenoates are available from R. Bull. by Rambaud et al. SOc
．． Chim. 1567 (1961) by oxidizing methyl, ethyl and propyl 1-hydroxy-2-butenoates with chromic anhydride.
その他の４オキソ一２Ｅ−ブテン酸アルキルは類似の態
様で得ることができる。下記の例は本発明を例示するも
のである。Other alkyl 4oxo-2E-butenoates can be obtained in a similar manner. The following examples illustrate the invention.
例１
２・２−ジメチル−３ＲＳ−（２′−メチル−Ｖプロペ
ニル）シクロプロパン−１ＲＳ−カルボン酸メチル１．
９７のよう化トリフエニルイソプロピルホスホニウムを
３０ｅｃのテトラヒドロフランに溶解してなる溶液にＯ
℃で２ＣＣの１．７５Ｎｎ−ブチルリチウムヘキサン溶
液を加え、全体を２５℃で３０分攪拌し、−７８℃に冷
却し、１ｃｅのテトラヒドロフランに溶解した０．２３
０７の４−オキソ２Ｅ−ブテン酸メチルを加え、全体を
−７８℃で５分間攪拌し、温度を２０℃に上昇せしめ、
１５時間撹拌し、若干の水を加え、全体をエーテルで抽
出し、脱水し、エーテル抽出物を濃縮乾固し、その残留
物をシリカゲルでクロマトグラフイ一しフエーテルとペ
ンタンとの１：１混合物で溶離し、０．１９０ｙの２・
２−ジメチル−３ＲＳ−（２′メチル−１′−プロペニ
ル）シクロプロパン１ＲＳ−カルボン酸メチルを得る。Example 1 Methyl 2,2-dimethyl-3RS-(2'-methyl-Vpropenyl)cyclopropane-1RS-carboxylate 1.
O
2CC of 1.75N n-butyllithium hexane solution was added, the whole was stirred at 25°C for 30 minutes, cooled to -78°C and 0.23% dissolved in 1ce of tetrahydrofuran.
07 methyl 4-oxo-2E-butenoate was added, the whole was stirred at -78°C for 5 minutes, and the temperature was raised to 20°C.
Stir for 15 hours, add some water, extract the whole with ether, dry, concentrate the ether extract to dryness, and chromatograph the residue on silica gel, a 1:1 mixture of phether and pentane. eluted with 0.190y of 2.
Methyl 2-dimethyl-3RS-(2'methyl-1'-propenyl)cyclopropane 1RS-carboxylate is obtained.
この粗エステルは下記の方法で対応する酸へ変換するこ
とができる。This crude ester can be converted to the corresponding acid in the following manner.
予め得られたメチルエステルに７．５ＣＣのメタノール
と７．５ＣＣの２０％メタノールカリ溶液を加え、全体
を２０℃で１５時間攪拌し、メタノールを減圧蒸留によ
り除去し、若干の水を加え、全体をエーテルで抽出し、
水性相を濃塩酸を添加して酸性化し、全体をエーテルで
抽出し、脱水し、濃縮乾固し、０．０３０ｙの２・２−
ジメチル−３ＲＳ（２′−メチル−Ｖ−プロペニル）シ
クロプロパン１ＲＳ−カルボン酸を得る。7.5 CC of methanol and 7.5 CC of 20% methanol potassium solution were added to the methyl ester obtained in advance, the whole was stirred at 20°C for 15 hours, methanol was removed by vacuum distillation, some water was added, and the whole extracted with ether,
The aqueous phase was acidified by addition of concentrated hydrochloric acid, the whole was extracted with ether, dried, concentrated to dryness, and 0.030y of 2.2-
Dimethyl-3RS(2'-methyl-V-propenyl)cyclopropane 1RS-carboxylic acid is obtained.
例２
２・２−ジメチル−３ＲＳ−（２′−メチル−１′プロ
ペニル）シクロプロパン−１ＲＳ−カルボン酸メチル１
４．２６ｙのよう化トリフエニルイソプロピルホスホニ
ウムを１００ｅｃのテトラヒドロフランに加え、１４．
１ＣＣの１．７５Ｎｎ−ブチルリチウムヘキサン溶液を
加え、全体を−７８℃に冷却し、１．１４７の４−オキ
ソ一２Ｅ−ブテン酸メチルを加え、全体を５分撹拌し、
温度を２０℃に上昇させ、６０時間攪拌し、若干の水を
加え、全体をエーテルで抽出し、脱水し、エーテル抽出
物を蒸留により濃縮乾固し、その残留物に若干のペンタ
ンを加え、全体を沢過して不溶物（トリフエニルホスフ
イン）を除き、ペンタンを蒸留により除去し、全体を減
圧蒸留により濃縮し、１５ｍｍＨｇで精留し、沸点が９
５〜１１０℃である０．８８７の生成物と沸点が１２０
〜１８０℃である０．２７の生成物を得る。Example 2 Methyl 2,2-dimethyl-3RS-(2'-methyl-1'propenyl)cyclopropane-1RS-carboxylate 1
4. Add triphenylisopropylphosphonium iodide of 26y to 100ec of tetrahydrofuran; 14.
Add 1 CC of 1.75N n-butyllithium hexane solution, cool the whole to -78°C, add 1.147 of methyl 4-oxo-2E-butenoate, stir the whole for 5 minutes,
The temperature was raised to 20° C., stirred for 60 hours, some water was added, the whole was extracted with ether, dried, the ether extract was concentrated to dryness by distillation, some pentane was added to the residue, The whole was filtered to remove insoluble matter (triphenylphosphine), pentane was removed by distillation, the whole was concentrated by vacuum distillation, and rectified at 15 mmHg, and the boiling point was 9.
0.887 product which is 5-110°C and boiling point is 120
A product of 0.27 is obtained which is ~180<0>C.
これらの二つの留分は２・２−ジメチル３ＲＳ−（２７
−メチル−ν−プロペニル）シクロプロパン−１ＲＳ−
カルボン酸メチルからなる。These two fractions are 2,2-dimethyl 3RS-(27
-methyl-v-propenyl)cyclopropane-1RS-
Consists of methyl carboxylate.
この粗エステルは下記の方法で純粋な対応する酸へ変換
することができる。メタノールカリでけん化した後、全
体を酸性化し、エーテルで抽出し、脱水し、濃縮乾固し
、０．８７の生成物を得、これをペンタンで５回再結晶
し、０．２３０ｙの２・２−ジメチル−３ＲＳ（２′−
メチル−１１−プロペニル）シクロプロパン１ＲＳ−カ
ルボン酸を得る。This crude ester can be converted to the pure corresponding acid in the following manner. After saponification with methanol-potassium, the whole was acidified, extracted with ether, dehydrated, and concentrated to dryness to obtain a product of 0.87, which was recrystallized five times from pentane to give 0.230y of 2. 2-dimethyl-3RS(2'-
Methyl-11-propenyl)cyclopropane 1RS-carboxylic acid is obtained.
Claims (1)
を表わす）の２・２−ジメチル−３ＲＳ−（２′−メチ
ル−１′−プロペニル）シクロプロパン−１ＲＳ−カル
ボン酸アルキルエステル、即ちｄｌ−ｔｒａｎｓ−菊酸
エステルを製造するにあたり、強塩基の存在下に次式▲
数式、化学式、表等があります▼ の４−オキソ−２Ｅ−ブテン酸アルキルを約２当量のハ
ロゲン化トリフェニルイソプロピルホスホニウムと反応
させることを特徴とする菊酸エステルの製造法。 ２ 少なくとも２当量のハロゲン化トリフェニルイソプ
ロピルホスホニウムを使用することを特徴とする特許請
求の範囲第１項記載の製造法。 ３ 使用される強塩基がｎ−ブチルリチウムであること
を特徴とする特許請求の範囲第１又は２項記載の製造法
。 ４ ４−オキソ−２Ｅ−ブテン酸アルキルが４−オキソ
−２Ｅ−ブテン酸メチルであることを特徴とする特許請
求の範囲第１又は２項記載の製造法。 ５ ハロゲン化トリフェニルイソプロピルホスホニウム
がよう化トリフェニルイソプロピルホスホニウムである
ことを特徴とする特許請求の範囲第１又は２項記載の製
造法。 ６ ４−オキソ−２Ｅ−ブテン酸メチルをテトラヒドロ
フラン中でｎ−ブチルリチウムの存在下に３当量のよう
化トリフェニルイソプロピルホスホニウムと反応させ、
２・２−ジメチル−３ＲＳ−（２′−メチル−１′−プ
ロペニル）シクロプロパン−１ＲＳ−カルボン酸メチル
を得ることを特徴とする特許請求の範囲第１又は２項記
載の製造法。[Claims] 2,2-dimethyl-3RS-(2 '-Methyl-1'-propenyl) cyclopropane-1RS-carboxylic acid alkyl ester, i.e., dl-trans-chrysanthemum acid ester, was prepared using the following formula ▲ in the presence of a strong base.
There are mathematical formulas, chemical formulas, tables, etc. ▼ A method for producing chrysanthemum acid ester, which is characterized by reacting an alkyl 4-oxo-2E-butenoate with about 2 equivalents of triphenylisopropylphosphonium halide. 2. The method according to claim 1, characterized in that at least 2 equivalents of triphenylisopropylphosphonium halide are used. 3. The manufacturing method according to claim 1 or 2, characterized in that the strong base used is n-butyllithium. 4. The manufacturing method according to claim 1 or 2, wherein the alkyl 4-oxo-2E-butenoate is methyl 4-oxo-2E-butenoate. 5. The manufacturing method according to claim 1 or 2, wherein the triphenylisopropylphosphonium halide is triphenylisopropylphosphonium iodide. 6 Methyl 4-oxo-2E-butenoate is reacted with 3 equivalents of triphenylisopropylphosphonium iodide in the presence of n-butyllithium in tetrahydrofuran,
3. The production method according to claim 1 or 2, characterized in that methyl 2,2-dimethyl-3RS-(2'-methyl-1'-propenyl)cyclopropane-1RS-carboxylate is obtained.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE155169A BE827652A (en) | 1975-04-07 | 1975-04-07 | NEW PROCESS FOR THE PREPARATION OF LOWER ALCOYL ESTERS OF HEMICARONIC ALDEHYDE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS51127049A JPS51127049A (en) | 1976-11-05 |
| JPS5929058B2 true JPS5929058B2 (en) | 1984-07-18 |
Family
ID=3842757
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3830576A Pending JPS51127050A (en) | 1975-04-07 | 1976-04-07 | New process for manufacture of hemicaronic acid aldehyde lower alkyl ester |
| JP3830476A Expired JPS5929058B2 (en) | 1975-04-07 | 1976-04-07 | Novel production method for chrysanthemum acid ester |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3830576A Pending JPS51127050A (en) | 1975-04-07 | 1976-04-07 | New process for manufacture of hemicaronic acid aldehyde lower alkyl ester |
Country Status (11)
| Country | Link |
|---|---|
| JP (2) | JPS51127050A (en) |
| BE (1) | BE827652A (en) |
| CA (1) | CA1091250A (en) |
| CH (1) | CH609027A5 (en) |
| DE (1) | DE2615160A1 (en) |
| DK (1) | DK134176A (en) |
| FR (1) | FR2306970A1 (en) |
| GB (1) | GB1502527A (en) |
| IE (1) | IE43363B1 (en) |
| IT (1) | IT1065993B (en) |
| NL (1) | NL7603678A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE827652A (en) * | 1975-04-07 | 1975-10-07 | NEW PROCESS FOR THE PREPARATION OF LOWER ALCOYL ESTERS OF HEMICARONIC ALDEHYDE | |
| DE2923774A1 (en) * | 1979-06-12 | 1980-12-18 | Bayer Ag | METHOD FOR PRODUCING 3,3-DIMETHYL-CYCLOPROPAN-1,2-DICARBONIC ACID ESTERS |
| DE2927133A1 (en) * | 1979-07-05 | 1981-01-08 | Bayer Ag | METHOD FOR PRODUCING 2-FORMYL-3,3-DIMETHYL-CYCLOPROPAN1-CARBONIC ACID ESTERS |
| FR2490633A1 (en) * | 1980-09-24 | 1982-03-26 | Roussel Uclaf | PROCESS FOR THE PREPARATION OF CYCLOPROPANE CARBOXYLIC ACID DERIVATIVES WITH ALDEHYDE FUNCTION |
| FR2624511B1 (en) * | 1987-12-11 | 1990-09-21 | Roussel Uclaf | ENANTIOSELECTIVE PROCESS FOR PREPARING HEMICARONIC ALDEHYDE DERIVATIVES WITH TRANS OR CIS STRUCTURE |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE827652A (en) * | 1975-04-07 | 1975-10-07 | NEW PROCESS FOR THE PREPARATION OF LOWER ALCOYL ESTERS OF HEMICARONIC ALDEHYDE |
-
1975
- 1975-04-07 BE BE155169A patent/BE827652A/en not_active IP Right Cessation
-
1976
- 1976-03-26 DK DK134176A patent/DK134176A/en not_active IP Right Cessation
- 1976-03-31 FR FR7609336A patent/FR2306970A1/en active Granted
- 1976-04-05 CA CA249,575A patent/CA1091250A/en not_active Expired
- 1976-04-06 GB GB1394176A patent/GB1502527A/en not_active Expired
- 1976-04-06 IT IT4888476A patent/IT1065993B/en active
- 1976-04-06 IE IE71976A patent/IE43363B1/en unknown
- 1976-04-07 JP JP3830576A patent/JPS51127050A/en active Pending
- 1976-04-07 DE DE19762615160 patent/DE2615160A1/en not_active Withdrawn
- 1976-04-07 CH CH438276A patent/CH609027A5/en not_active IP Right Cessation
- 1976-04-07 NL NL7603678A patent/NL7603678A/en not_active Application Discontinuation
- 1976-04-07 JP JP3830476A patent/JPS5929058B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS51127050A (en) | 1976-11-05 |
| IE43363B1 (en) | 1981-02-11 |
| NL7603678A (en) | 1976-10-11 |
| CH609027A5 (en) | 1979-02-15 |
| DK134176A (en) | 1976-10-08 |
| BE827652A (en) | 1975-10-07 |
| IT1065993B (en) | 1985-03-04 |
| FR2306970A1 (en) | 1976-11-05 |
| DE2615160A1 (en) | 1976-10-21 |
| GB1502527A (en) | 1978-03-01 |
| IE43363L (en) | 1976-10-07 |
| FR2306970B1 (en) | 1979-10-05 |
| CA1091250A (en) | 1980-12-09 |
| JPS51127049A (en) | 1976-11-05 |
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