CH645338A5 - ESTERS OF THE 2,2-DIMETHYL-3-ACETOXY-METHYL-CYCLOPROPANCARBOXYLIC ACID AND THEIR PREPARATION. - Google Patents

ESTERS OF THE 2,2-DIMETHYL-3-ACETOXY-METHYL-CYCLOPROPANCARBOXYLIC ACID AND THEIR PREPARATION. Download PDF

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Publication number
CH645338A5
CH645338A5 CH527980A CH527980A CH645338A5 CH 645338 A5 CH645338 A5 CH 645338A5 CH 527980 A CH527980 A CH 527980A CH 527980 A CH527980 A CH 527980A CH 645338 A5 CH645338 A5 CH 645338A5
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CH
Switzerland
Prior art keywords
methyl
diazoacetate
dimethyl
process according
cyclohexane
Prior art date
Application number
CH527980A
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Italian (it)
Inventor
Ottorino Palla
Franco Gozzo
Original Assignee
Montedison Spa
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Filing date
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Publication of CH645338A5 publication Critical patent/CH645338A5/en

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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Description

La presente invenzione riguarda esteri con alcoli inferiori dell'acido 2,2-dimetil-3-acetossimetil-ciclopropancarbossilico ed il loro metodo di preparazione. The present invention relates to esters with lower alcohols of 2,2-dimethyl-3-acetoxymethyl-cyclopropancarboxylic acid and their preparation method.

20 I suddetti composti, aventi formula generale 20 The above compounds, having general formula

H3C H3C

H C-C-O-CH - CH H C-C-O-CH - CH

a fl a a fl a

X X

CH - COOR CD CH - COOR CD

30 30

(in cui R = alchile inferiore) (where R = lower alkyl)

sono utili intermedi per la sintesi di insetticidi piretroidi. they are useful intermediates for the synthesis of pyrethroid insecticides.

Infatti per semplice idrolisi i composti di formula (I) vengono trasformati nell'acido 2,2-dimetil-3-idrossimetil-ciclo-35 propancarbossilico (II) e questo per ossidazione fornisce la caronaldeide (acido 2,2-dimetil-3-formil-ciclopropancarbos-silico) (III) dalla quale è possibile ottenere l'acido crisan-temico (TV) mediante reazione con isopropiliden-trifenilfosfo-rano [vedi ad esempio Tetrahedron Letters 43, 3915 (1976)] In fact, by simple hydrolysis the compounds of formula (I) are transformed into 2,2-dimethyl-3-hydroxymethyl-cyclo-35 propancarboxylic acid (II) and this by oxidation provides the caronaldehyde (2,2-dimethyl-3- acid formyl-cyclopropancarbos-silico) (III) from which it is possible to obtain chrysanemic acid (TV) by reaction with isopropyliden-triphenylphospho-rano [see for example Tetrahedron Letters 43, 3915 (1976)]

H3C H3C

(I> (I>

idrolisi hydrolysis

-*HOCH - CH - * HOCH - CH

Ck ck

V V

/\ / \

CH, CH,

- CH - COOH - CH - COOH

(II) (II)

(II) (II)

ossidazione oxidation

H3C H3C

/\ / \

C - CH - CH - COOH C - CH - CH - COOH

II II

(III) (III)

HC CH. HC CH.

3\ / 3 3 \ / 3

,Tm isopropiliden-fosforano H3C\ , » , Tm isopropyliden-phosphorane H3C \, "

(III) 1 ^C=CH-CH - CH-COOH (IV) (III) 1 ^ C = CH-CH - CH-COOH (IV)

HC/ HC /

3 3

3 3

645338 645338

Formano oggetto della presente invenzione i composti di formula generale: The compounds of the general formula form the subject of the present invention:

H.C ,CH, H.C, CH,

o v or v

/\ / \

H C-C-O-CH - CH - H C-C-O-CH - CH -

O fi C» O fi C »

0 0

CH - COOR (I) CH - COOR (I)

in cui R = alchile inferiore. wherein R = lower alkyl.

La preparazione dei composti di formula (I), che costituisce un secondo oggetto della presente invenzione, si attua facendo reagire l'acetato di prenile (acetato di 3,3-di- 15 metil-allile) (V) con diazoacetato (VI). The preparation of the compounds of formula (I), which constitutes a second object of the present invention, is carried out by reacting the prenyl acetate (3,3-di-15 methyl-allyl acetate) (V) with diazoacetate (VI) .

"3C "3C

\ \

H3C H3C

/ /

C=CH-CH -O-C-CH (V) + N CH-COOR (VI) C = CH-CH -O-C-CH (V) + N CH-COOR (VI)

M || O (Z M || O (Z

-> ->

(I) (THE)

0 0

(in cui R = alchile inferiore). (wherein R = lower alkyl).

La suddetta reazione viene eseguita in und solvente inerte quale cicloesano ed in presenza di solfato di rame anidro e rame metallico in polvere come catalizzatori. The above reaction is carried out in an inert solvent such as cyclohexane and in the presence of anhydrous copper sulphate and powdered metallic copper as catalysts.

La quantità di solfato di rame anidro impiegata è di circa un decimo di mole per mole di acetato di prenile. The amount of anhydrous copper sulphate used is about a tenth of a mole per mole of prenyl acetate.

Il rame metallico viene impiegato circa nella stessa quantità del solfato di rame. Metallic copper is used in approximately the same amount as copper sulphate.

In una sua pratica forma di attuazione la reazione viene condotta aggiungendo lentamente un leggero eccesso di diazoacetato sciolto in cicloesano ad una sospensione di solfato di rame e rame metallico in cicloesano contenente già la quantità prestabilita di acetato di prenile. In a practical embodiment, the reaction is carried out by slowly adding a slight excess of diazoacetate dissolved in cyclohexane to a suspension of copper and metallic copper sulphate in cyclohexane already containing the predetermined amount of prenyl acetate.

Il tutto viene mantenuto sotto leggera corrente di azoto e scaldato a leggero riflusso' (circa 80°C). The whole is kept under a light stream of nitrogen and heated to a slight reflux (about 80 ° C).

Terminata l'aggiunta del diazoacetato la miscela di reazione viene lasciata alcuni minuti a riflusso e viene quindi elaborata secondo le normali tecniche di laboratorio. Once the addition of the diazoacetate has been completed, the reaction mixture is left for a few minutes under reflux and is then processed according to normal laboratory techniques.

Dopo eliminazione del solvente si ottiene un grezzo che si sottopone a distillazione per raccogliere il prodotto. After elimination of the solvent, a crude is obtained which is subjected to distillation to collect the product.

Con lo scopo di meglio illustrare l'invenzione vengono ora forniti i seguenti esempi. With the aim of better illustrating the invention, the following examples are now provided.

35 35

Esempio 1 Example 1

Preparazione dell'estere etilico dell'acido 2,2-dimetil-3--acetossimetil-ciclopropancarbossilico. 50 Preparation of the ethyl ester of 2,2-dimethyl-3 -acetoxymethyl-cyclopropanecarboxylic acid. 50

H3C H3C

h3c h3c

\ / \ /

C=CH-CH -O-C-CH„ + N OH-COOC H 2 11 3 2 2 5 C = CH-CH -O-C-CH "+ N OH-COOC H 2 11 3 2 2 5

(1) (1)

0 0

(2) (2)

HC CH 3\/ 3 HC CH 3 \ / 3

•> H C-C-O-CH -CH •> H C-C-O-CH -CH

3 u 2 3 u 2

A TO

- CH - COOC H 2 5 - CH - COOC H 2 5

(3) (3)

645338 645338

4 4

In un pallone munito di agitatore, ricadere, termometro e imbuto gocciolatore, si pongono 0,6 moli di acetato di prenile, 0,07 moli di solfato di rame anidro, 0,05 moli di rame in polvere e cc 340 di cicloesano. La sospensione viene scaldata a leggero riflusso (circa 80°C). Sotto leggera corrente di azoto si aggiungono, per gocciolamento in circa 2 ore, 0,72 moli di diazoacetato di etile miscelato con 300 cc di cicloesano. Durante il gocciolamento si diminuisce il riscaldamento esterno in modo da mantenere la reazione a gentile riflusso. Terminato il gocciolamento si tiene ancora 10 minuti a ricadere e poi si filtra, si lava il sale con 2 porzioni di 30 cc di cicloesano, si lavano le fasi organiche riunite con acqua (3 X 100 cc), si anidrifica su solfato di sodio e si elimina il solvente per evaporazione a 15 mmHg e 40°C. Si distilla il grezzo di reazione (peso 140-150 g) a 0,1 mmHg/ 75°-80°C, ottenendo il composto 3 con rese tra 55 e 60%. In a flask equipped with a stirrer, drop, thermometer and drip funnel, 0.6 moles of prenyl acetate, 0.07 moles of anhydrous copper sulphate, 0.05 moles of copper powder and 340 cc of cyclohexane are placed. The suspension is heated to a slight reflux (about 80 ° C). 0.72 moles of ethyl diazoacetate mixed with 300 cc of cyclohexane are added under a light stream of nitrogen, by dripping in about 2 hours. During the dripping, the external heating is decreased in order to maintain the reaction at gentle reflux. Once the drip is finished, the mixture is kept for 10 minutes and then filtered, the salt is washed with 2 portions of 30 cc of cyclohexane, the organic phases are washed together with water (3 X 100 cc), anhydrified on sodium sulphate and the solvent is eliminated by evaporation at 15 mmHg and 40 ° C. The reaction raw product (weight 140-150 g) is distilled at 0.1 mmHg / 75 ° -80 ° C, obtaining compound 3 with yields between 55 and 60%.

L'analisi NMR (Risonanza Magnetica Nucleare) ha evidenziato che il rapporto tra gli isomeri eis e trans è di circa 1 : 1. The NMR (Nuclear Magnetic Resonance) analysis showed that the ratio between the eis and trans isomers is about 1: 1.

L'analisi all'infrarosso evidenzia bande significative a 1720, 1380, 1240, 1175 e 1025 cm"1. Infrared analysis highlights significant bands at 1720, 1380, 1240, 1175 and 1025 cm "1.

Esempio 2 Example 2

Scopo del presente esempio è quello di mostrare la preparazione di esteri alchilici inferiori dell'acido 2,2-dimetil-3--idrossimetil-ciclopropancarbossilico partendo dai composti preparati per mezzo, del processo oggetto dell'invenzione. The purpose of the present example is to show the preparation of lower alkyl esters of 2,2-dimethyl-3-hydroxymethyl-cyclopropanecarboxylic acid starting from the compounds prepared by means of the process object of the invention.

Ad una soluzione di 0,2 g di sodio (0,01 moli) in 100 mi 5 di alcool etilico assoluto mantenuta in agitazione a temperatura ambiente, viene aggiunta lentamente una soluzione di 10,7 g (0,05 moli) di 2,2-dimetil-3-acetossimetil-ciclopropan-carbossilato di etile (preparato come descritto nell'esempio 1) in 20 mi di alcool etilico. To a solution of 0.2 g of sodium (0.01 moles) in 100 ml 5 of absolute ethyl alcohol kept under stirring at room temperature, a solution of 10.7 g (0.05 moles) of 2 is slowly added, Ethyl 2-dimethyl-3-acetoxymethyl-cyclopropan carboxylate (prepared as described in Example 1) in 20 ml of ethyl alcohol.

io La miscela di reazione viene quindi lasciata in agitazione per una notte a temperatura ambiente quindi il solvente viene allontanato per distillazione a pressione ridotta. The reaction mixture is then left under stirring overnight at room temperature then the solvent is removed by distillation under reduced pressure.

Il residuo viene ripreso con 200 mi di etere etilico e 20 mi di acqua. The residue is taken up in 200 ml of ethyl ether and 20 ml of water.

i5 La fase organica viene separata, anidrificata con Na2S04 anidro ed il solvente viene allontanato per distillazione. i5 The organic phase is separated, anhydrified with anhydrous Na2SO4 and the solvent is removed by distillation.

Il residuo viene distillato a pressione ridotta raccogliendo la frazione che bolle a 100-108°C alla pressione di 1,6 mmHg. Detta frazione è costituita dal composto 2,2-dimetil-20 -3-idrossimetil-ciclopropancarbossilato di etile (Analisi all'infrarosso consistente con la struttura assegnata). The residue is distilled under reduced pressure collecting the fraction boiling at 100-108 ° C at a pressure of 1.6 mmHg. Said fraction consists of the compound 2,2-dimethyl-20 -3-hydroxymethyl-cyclopropanecarboxylate of ethyl (Infrared analysis consistent with the assigned structure).

L'ossidazione del suddetto composto a caronaldeide può essere effettuata secondo tecniche note [Journal of Organic Chemistry, pag. 885 (1976)]. The oxidation of the above compound to caronaldehyde can be carried out according to known techniques [Journal of Organic Chemistry, pag. 885 (1976)].

v v

Claims (9)

645338 645338 2. Composto secondo la rivendicazione 1, in cui il composto di formula (I) è l'estere etilico dell'acido 2,2-dimetil--3-acetossimetil-ciclo-propancarbossilico. 2. A compound according to claim 1, wherein the compound of formula (I) is the ethyl ester of 2,2-dimethyl-3-acetoxymethyl-cyclo-propancarboxylic acid. 2 2 RIVENDICAZIONI 1. Composti di formula generale: CLAIMS 1. Compounds of general formula: ,CH , CH H3C H3C X X H C-C-O-CH - CH - H C-C-O-CH - CH - U fi W U fi W Ö OR in cui R = alchile inferiore. wherein R = lower alkyl. 3. Processo per la preparazione dei composti della rivendicazione 1, caratterizzato dal fatto che l'acetato di 3,3-di-metil-allile viene fatto reagire con un diazoacetato di formula: 3. Process for the preparation of the compounds of claim 1, characterized in that the 3,3-di-methyl-allyl acetate is reacted with a diazoacetate of formula: N2CH - COOR (VI) N2CH - COOR (VI) (in cui R = alchile inferiore) (where R = lower alkyl) in un solvente inerte ed in presenza di solfato di rame anidro e rame metallico in polvere. in an inert solvent and in the presence of anhydrous copper sulphate and metallic copper powder. 4. Processo secondo la rivendicazione 3, caratterizzato dal fatto che come solvente si usa cicloesano. 4. Process according to claim 3, characterized in that cyclohexane is used as the solvent. 5 caratterizzato dal fatto che la reazione fra l'acetato di 3,3-di-metil-allile ed il diazoacetato viene condotta aggiungendo una soluzione di quest'ultimo in cicloesano ad una sospensione di solfato di rame, rame metallico e acetato di 3,3-di-CH - COOR (I) metil-allile in cicloesano mantenuta in agitazione in atmosfe-io ra di azoto a 80°C. 5 characterized in that the reaction between the 3,3-di-methyl-allyl acetate and the diazoacetate is carried out by adding a solution of the latter in cyclohexane to a suspension of copper sulphate, metallic copper and acetate of 3, 3-di-CH - COOR (I) methyl allyl in cyclohexane kept under stirring in a nitrogen atmosphere at 80 ° C. 5. Processo secondo le rivendicazioni 3 o 4, caratterizzato dal fatto che il solfato di rame viene impiegato in rapporto molare circa 1 a 10 rispetto all'acetato di 3,3-dimetil--allile. 5. Process according to claims 3 or 4, characterized in that the copper sulphate is used in a molar ratio of about 1 to 10 with respect to the 3,3-dimethyl-allyl acetate. 6. Processo secondo una delle rivendicazioni 3, 4 o 5, caratterizzato dal fatto che il rame metallico viene impiegato in rapporto molare circa 1 a 10 rispetto all'acetato di 3,3-di-metil-allile. Process according to one of claims 3, 4 or 5, characterized in that the metallic copper is used in a molar ratio of about 1 to 10 with respect to the 3,3-di-methyl-allyl acetate. 7. Processo secondo una delle rivendicazioni da 3 a 6, caratterizzato dal fatto che la reazione tra l'acetato di 3,3-di-metil-allile e il diazoacetato viene condotta a circa 80°C. Process according to one of claims 3 to 6, characterized in that the reaction between the 3,3-di-methyl-allyl acetate and the diazoacetate is carried out at about 80 ° C. 8. Prooesso secondo una delle rivendicazioni da 3 a 7, 8. According to one of claims 3 to 7, 9. Processo secondo una delle rivendicazioni da 3 a 8, caratterizzato dal fatto che il diazoacetato di formula (VI) è diazoacetato di etile. Process according to one of claims 3 to 8, characterized in that the diazoacetate of formula (VI) is ethyl diazoacetate.
CH527980A 1979-07-10 1980-07-10 ESTERS OF THE 2,2-DIMETHYL-3-ACETOXY-METHYL-CYCLOPROPANCARBOXYLIC ACID AND THEIR PREPARATION. CH645338A5 (en)

Applications Claiming Priority (1)

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IT24225/79A IT1122093B (en) 1979-07-10 1979-07-10 ESTERS OF THE 2,2-DIMETHYL-3-ACETOXY-METHYL-CYCLOPROPANCARBOXYLIC ACID AND THEIR PREPARATION

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JP (1) JPS5625137A (en)
BE (1) BE884260A (en)
CH (1) CH645338A5 (en)
DE (1) DE3026011A1 (en)
FR (1) FR2460918A1 (en)
GB (1) GB2054587B (en)
IT (1) IT1122093B (en)
NL (1) NL8003910A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5119747A (en) * 1974-08-09 1976-02-17 Sumitomo Chemical Co 2*22 jimechiru 33 * 2**2** jikurorubiniru * shikuropuropankarubonsanesuteruno seizohoho

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DE3026011A1 (en) 1981-02-05
GB2054587B (en) 1983-07-13
IT7924225A0 (en) 1979-07-10
NL8003910A (en) 1981-01-13
JPS5625137A (en) 1981-03-10
IT1122093B (en) 1986-04-23
FR2460918A1 (en) 1981-01-30
FR2460918B1 (en) 1984-03-30
GB2054587A (en) 1981-02-18
BE884260A (en) 1981-01-12

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