GB2025965A - Cyclopropane Derivative - Google Patents
Cyclopropane Derivative Download PDFInfo
- Publication number
- GB2025965A GB2025965A GB7924885A GB7924885A GB2025965A GB 2025965 A GB2025965 A GB 2025965A GB 7924885 A GB7924885 A GB 7924885A GB 7924885 A GB7924885 A GB 7924885A GB 2025965 A GB2025965 A GB 2025965A
- Authority
- GB
- United Kingdom
- Prior art keywords
- compound
- formula
- carene
- cyclopropane
- dimethoxyethyl
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/30—Compounds having groups
- C07C43/315—Compounds having groups containing oxygen atoms singly bound to carbon atoms not being acetal carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Novel intermediate in the manufacture of pyrethroid insecticides has the following formula <IMAGE> The compound preferably has the same stereochemical form as the cyclopropane ring in (+)-3-carene. The novel intermediate can be prepared by a process which comprises hydrolysing under alkaline conditions 1-(2,2-dimethoxyethyl)-3,3- dimethylcyclopropylmethyl acetate, the latter compound being preferably derived from (+)3-carene.
Description
SPECIFICATION
Novel Intermediate in the Preparation of
Cyclopropanecarboxylate Esters and Process for its Manufacture
The invention relates to a compound which is a useful intermediate in the preparation of cyclopropanecarboxylate esters. The invention also relates to a process for the preparation of this intermediate.
The cyclopropanecarboxylate esters are insecticidally-active compounds known as "pyrethroids" and as they combine exceptionally good insecticidal properties with a very low mammalian toxicity, they are of considerable interest to the agrochemical industry and much effort has been expended in finding economic routes to them and to their principal intermediates.
The general formula of one class of these pyrethroid compounds may be represented as follows:
where each asterisk denotes an asymmetric carbon atom; each X is a halogen atom; and R is a member of a group of radicals known to impart insecticidal activity to the molecule, e.g. 3phenoxybenzyl or alphacyano-3-phenoxybenzyl. It is known that the stereoisomeric form of the acid portion of the ester of formula I should be in the (1 R,cis) form for maximum insecticidal activity, i.e. the absolute configuration at carbon atom 1 is
R and the two hydrogen atoms on carbon atoms 1 and 2 are in a cis relationship. This nomenclature is known as the Elliott nomenclature and is defined in M. Elliot, A. W. Farnham, N. F.
James, P. H. Needham and D. A. Pullman,
Nature, 1974, 248, 710.
It follows, therefore, that if these stereoisomeric esters of formula I are to be prepared, either a stereospecific chemical route is required or the desired stereoisomer must be obtained from a racemic form by physical separation techniques. The latter are expensive and laborious and not readily employed on an industrial scale. The Applicant has found a stereospecific route which uses as starting material the naturally-occurring substance (+)-3-carene whose formula is as follows
This compound is an inexpensive readily-available natural terpene and the present application relates to an intermediate which can be used in a route to the (1 R,cis)-acid portion of the pyrethroid ester of formula I starting from (+)3-carene.
The present invention provides a cyclopropane compound of the general formula.
The compound may be named 2-(2hydroxymethyl-3,3-dimethylcyclopropyl)ethanal dimethyl acetal. Preferably the compound of formula Ill is in the same stereoisomeric form as that of the cyclopropane ring present in naturallyoccurring (+)-3-carene.
The present invention also provides a process for the preparation of 2-(2-hydroxymethyl-3,3dimethylcyclopropyl)ethanal dimethyl acetal of formula Ill which comprises hydrolysing under alkaline conditions 1 -(2,2-dimethoxyethyl)-3,3 dimethylcyclopropyl methyl acetate of formula
It wili be seen that the hydrolysis must be carried out in such a manner that the two methoxy groups remain unchanged; generally speaking, the use of an alkaline-reacting medium enables this to be achieved. Other hydrolysis conditions are described in "Methoden der organischen
Chemie" (Houben-Weyl), Volume VIII (1952) 418-423 and 638-639.
The starting material compound IV may be prepared by (a) the ozonolysis of (+)3-carene followed by reduction in the presence of methanol and an acetalising agent of the ozonolysis product; and (b) oxidation of the resulting product with a peracid, e.g. perbenzoic acid, Such a reaction is disclosed in our copending Europeanpatent application 78200351 (K 332 EPC).
The starting material is preferably derived from naturally-occurring (+)-3-carene as this enables the process according to the invention to yield a novel intermediate of formula Ill in a stereoisomeric form which, after conversion to a pyrethroid insecticide produces the highest level of pyrethroid insecticide activity.
The compound and process according to the invention are of interest as part of a multi-step process to pyrethroid insecticides, e.g. esters based on (1 R,cis)-2-(2,2-dichlorovinyl)3,3dimethylcyclopropane carboxylic acid, and their dibromo analogues.
The following Example further illustrates the invention.
Example
Preparation of 2-(2-Hydroxymethyl-3,3dimethylcyclopropyl)ethanal Dimethyl Acetal (Compound lil) A 250 ml flask was charged with water (75 ml), methanol (30 ml), sodium hydroxide (152.2 mmol) and 1 R,cis- 1 -(2,2-dimethoxyethyl)-3,3- dimethylcyclopropylmethyl acetate (145 mmol).
After stirring for three hours at 20 C methanol was evaporated from the contents of the flask at 400C/2 kPa. The aqueous phase left was saturated with sodium chloride and then extracted with three 70 ml portions of diethyl ether. The combined extract phases were washed with two 10 ml portions of water, the washed etherial solution was dried over anhydrous magnesium sulphate and the solvent was evaporated from the dried solution to give 120.7 mmol of compound Ill in 100% 1 R,cis configuration (purity 98%, yield 83%, determined by gas liquid chromatography and nuclear magnetic resonance (NMR) spectroscopy). The
NMR spectrum of compound Ill showed the following absorptions (at 90 MHz, using a solution of compound Ill in deuterochloroform and relative to a tetramethylsilane standard): S=0.97 ppm singlet H3C-C-CH S=3.00 ppm singlet H3C-O-C-O-CH3 S=4.40 ppm double doublet (H3CO)2-CH- S=1.06 ppm singlet H3C-C-CH3 S=3.06 ppm singletHC-O-C-O-CH3 multiplets for the two H atoms bound to the ring and for CK2OH and (H3CO)2CHCH2.
Claims (6)
1. A cyclopropane compound of the formula:
2. A compound according to Claim 1 in the same stereisomeric form as that of the
cyclopropane ring present in naturally
occuring (+)-3-carene.
3. A process for the preparation of a
cyclopropane compound of formula Ill which
comprises hydrolysing under alkaline conditions 1 -(2,2-dimethoxyethyl)-3,3- dimethylcyclopropylmethyl acetate of formula
4. process according to Claim 3 wherein the starting material of formula IV is derived from naturally-occurring (±3-carene.
5. A process according to Claim 3 substantially as hereinbefore described with reference to the
Examples.
6. A compound of formula III prepared by a process claimed in Claim 4 or 5.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB7924885A GB2025965B (en) | 1978-07-19 | 1979-07-17 | Cyclopropane derivative |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB7830371 | 1978-07-19 | ||
GB7924885A GB2025965B (en) | 1978-07-19 | 1979-07-17 | Cyclopropane derivative |
Publications (2)
Publication Number | Publication Date |
---|---|
GB2025965A true GB2025965A (en) | 1980-01-30 |
GB2025965B GB2025965B (en) | 1982-10-13 |
Family
ID=26268274
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB7924885A Expired GB2025965B (en) | 1978-07-19 | 1979-07-17 | Cyclopropane derivative |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB2025965B (en) |
-
1979
- 1979-07-17 GB GB7924885A patent/GB2025965B/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
GB2025965B (en) | 1982-10-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CH636073A5 (en) | Process for the preparation of substituted cyclopropanecarboxylates | |
GB2025965A (en) | Cyclopropane Derivative | |
US4298757A (en) | 2-[2-(2,2-Dihalovinyl)-3,3-dimethylcyclopropyl ]vinyl alkanoates | |
US4281203A (en) | (Cyclopropyl)vinyl alkyl ether derivatives | |
US4258205A (en) | 2,2-Dimethylcyclopropanecarbaldehyde dimethyl acetal derivatives | |
US4257956A (en) | Oxabicycloalkane pyrethroid intermediates | |
EP0002850B1 (en) | Novel intermediates in the preparation of cyclopropylcarboxylate esters and process for their manufacture | |
CA1123016A (en) | Intermediate in the preparation of cyclopropanecarboxylate esters and process for its manufacture | |
EP0002556B1 (en) | Novel intermediate in the preparation of cyclopropylcarboxylate esters and process for its manufacture | |
US5382732A (en) | 2,5-bis(1,1-dialkoxy-2-propyl)-2,5-dihydrofurans, the preparation thereof and the use thereof for the preparation of carotenoids | |
EP0002851B1 (en) | Novel intermediate in the preparation of cyclopropylcarboxylate esters and process for its manufacture | |
EP0002852B1 (en) | Novel intermediate in the preparation of cyclopropylcarboxylate esters and process for its manufacture | |
GB2025964A (en) | Cyclopropane Derivative | |
CA1123857A (en) | Intermediate in the preparation of cyclopropanecarboxylate esters and process for its manufacture | |
CA1126759A (en) | Intermediate in the preparation of cyclopropanecarboxylate esters and process for its manufacture | |
JP3583130B2 (en) | Production of halogenated alcohol | |
US4284820A (en) | 3,6,6-Trimethylbicyclo[3.1.0]hexane derivatives as pyrethrod intermediates | |
CA1147347A (en) | Intermediate in the preparation of cyclopropanecarboxylate esters and process for its manufacture | |
US4247711A (en) | Preparation of 2-formyl-3,3-dimethylcyclopropaneacetic acid | |
GB2025963A (en) | Cyclopropane Derivative | |
CA1119617A (en) | Intermediates in the preparation of cyclopropanecarboxylate esters and process for their manufacture | |
EP0007142B1 (en) | Novel intermediates in the preparation of cyclopropanecarboxylate esters and process for their manufacture | |
GB2052479A (en) | Novel bicyclohexane compound useful as an intermediate in the preparation of pyrethroid insecticides | |
GB2025962A (en) | Cyclopropane Derivatives | |
GB2053901A (en) | Cyclopropane Compounds and Their Manufacture |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19940717 |