GB2054587A - Esters of 2,2-dimethyl-3-acetoxymethyl- cyclopropane-carboxylic acid and their preparation - Google Patents
Esters of 2,2-dimethyl-3-acetoxymethyl- cyclopropane-carboxylic acid and their preparation Download PDFInfo
- Publication number
- GB2054587A GB2054587A GB8022436A GB8022436A GB2054587A GB 2054587 A GB2054587 A GB 2054587A GB 8022436 A GB8022436 A GB 8022436A GB 8022436 A GB8022436 A GB 8022436A GB 2054587 A GB2054587 A GB 2054587A
- Authority
- GB
- United Kingdom
- Prior art keywords
- dimethyl
- diazoacetate
- preparation
- acetoxymethyl
- acetate
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 150000002148 esters Chemical class 0.000 title claims abstract description 6
- DRBHABDFIYSLEV-UHFFFAOYSA-N 3-(acetyloxymethyl)-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC(=O)OCC1C(C(O)=O)C1(C)C DRBHABDFIYSLEV-UHFFFAOYSA-N 0.000 title claims description 5
- XXIKYCPRDXIMQM-UHFFFAOYSA-N Isopentenyl acetate Chemical compound CC(C)=CCOC(C)=O XXIKYCPRDXIMQM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 11
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 9
- BXEFQPCKQSTMKA-UHFFFAOYSA-N OC(=O)C=[N+]=[N-] Chemical compound OC(=O)C=[N+]=[N-] BXEFQPCKQSTMKA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 239000012442 inert solvent Substances 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 3
- 125000004494 ethyl ester group Chemical group 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 0.000 abstract 1
- 238000010992 reflux Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- XLOPRKKSAJMMEW-UHFFFAOYSA-N chrysanthemic acid Chemical compound CC(C)=CC1C(C(O)=O)C1(C)C XLOPRKKSAJMMEW-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- OALLZRITWFSDNC-UHFFFAOYSA-O propan-2-ylidenephosphanium Chemical compound CC(C)=[PH2+] OALLZRITWFSDNC-UHFFFAOYSA-O 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GZVJRUASQZSDKH-UHFFFAOYSA-N 3-(hydroxymethyl)-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)C(CO)C1C(O)=O GZVJRUASQZSDKH-UHFFFAOYSA-N 0.000 description 1
- PTQGFDXPHNRDCV-UHFFFAOYSA-N 3-formyl-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C=O)C1C(O)=O PTQGFDXPHNRDCV-UHFFFAOYSA-N 0.000 description 1
- XLOPRKKSAJMMEW-SFYZADRCSA-N Chrysanthemic acid Natural products CC(C)=C[C@@H]1[C@@H](C(O)=O)C1(C)C XLOPRKKSAJMMEW-SFYZADRCSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- FSSGNHHCDSKKJH-UHFFFAOYSA-N ethyl 3-(hydroxymethyl)-2,2-dimethylcyclopropane-1-carboxylate Chemical compound CCOC(=O)C1C(CO)C1(C)C FSSGNHHCDSKKJH-UHFFFAOYSA-N 0.000 description 1
- LDDOSDVZPSGLFZ-UHFFFAOYSA-N ethyl cyclopropanecarboxylate Chemical compound CCOC(=O)C1CC1 LDDOSDVZPSGLFZ-UHFFFAOYSA-N 0.000 description 1
- YVPJCJLMRRTDMQ-UHFFFAOYSA-N ethyl diazoacetate Chemical compound CCOC(=O)C=[N+]=[N-] YVPJCJLMRRTDMQ-UHFFFAOYSA-N 0.000 description 1
- 229940035423 ethyl ether Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- KNWIYLJZVYHGDV-UHFFFAOYSA-N triphenyl(propan-2-ylidene)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=C(C)C)C1=CC=CC=C1 KNWIYLJZVYHGDV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
Landscapes
- 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)
Abstract
A process for the preparation of compounds of formula; <IMAGE> in which R represents a lower alkyl group in which 3,3-dimethyl-allyl- acetate is reacted with a diazoacetate of formula N2CH-COOR (VI> in an inert solvent and in the presence of anhydrous copper sulphate and metal copper in the form of powder. The esters are useful intermediates in the synthesis of pyrethroids.
Description
SPECIFICATION
Esters of 2,2-dimethyl-3-acetoxymethyl-cyclopropane-carboxylic acid and their preparation
This invention relates to esters with lower alcohols of 2,2-dimethyl-3-acetoxymethyl-cyclopropanecarboxylic acid and to their preparation.
The above esters having general formula
in which R represents a lower alkyl group, are useful intermediates for the synthesis of pyrethroid insecticides.
The compound of formula (I) may be converted, by simple hydrolysis, into 2,2-dimethyl-3hydroxymethyl-cyclopropanecarboxylic acid (II), which, by oxidation, provides caronaldehyde (2,2-dimethyl-3-formyl-cyclopropanecarboxylic acid) (III), from which it is possible to obtain chrysanthemic acid (IV) by reaction with isopropylidene-triphenylphosphorane, see, for example,
Tetrahedron Letters 43, 3915 (1976).
The reaction scheme may be represented as follows:
H3C\c/CH3 (I) hydrolysis / \ HOOCH2 - CH CH - COOH (II) \ / C (II) oxidation / (11) oxidation H - C - CM CM - COOH (III) II o H3C\ c/CII3 H H3C\y CH3 (III) iSopropylidene phosphorane 3 \ > isopropylidene phosphorane C=CH-CH CH-COOH CIV) H3C It is an object of the present invention to provide a method for the preparation of compounds of general formula (I).
Therefore according to the invention there is provided a process for preparation of compounds of formula:
in which R represents a lower alkyl group,
in which 3,3-dimethyl-allyl acetate is reacted with a diazoacetate of formula:
N2CH-COOR (VI)
in which R represents a lower alkyl group,
in an inert solvent and in the presence of anhydrous copper sulphate and metal copper in the form of powder.
The reaction is conducted in an inert solvent such as cyclohexane and in the presence of anhydrous copper sulphate and metal copper in the form of powder as catalysts.
The amount of anhydrous copper sulphate employed is about one tenth of mole per mole of prenyl acetate (3,3-dimethyl-allyl acetate). Metal copper is employed approximately in the same amount as copper sulphate.
According to a practical embodiment, the reaction is conducted by gradually adding a slight excess of diazoacetate dissolved in cyclohexane to a suspension of copper sulphate and metal copper in cyclohexane containing the desired amount of prenyl acetate under stirring. The reaction mass is maintained under a slight nitrogen stream and heated at slight reflux (about 80 C).
After addition of the diazoacetate, the reaction mixture is left a few minutes at reflux, whereupon it is treated according to conventional laboratory techniques to separate the product.
After removal of the solvent, a crude product is obtained which is subjected to distillation to collect the pure product.
The invention will now be illustrated by the following Examples
Example 1
Preparation of the ethyl ester of Z2-dimethyl-3-aceto;'ymethyl-cydoprnpanecarooxyllc acid.
0.6 moles of prenyl acetate, 0.07 moles of anhydrous copper sulphate, 0.05 moles of powdered copper and 340 cc of cyclohexane were introduced into a flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel. The suspension was heated at slight reflux (about 80"C). Under a slight nitrogen flow, 0.72 moles of ethyl diazoacetate mixed with 300 cc of cyclohexane were added dropwise over a period of 2 hours. During the addition the external heating was reduced so as to keep the reaction at gentle reflux.On conclusion of the addition, the reaction mass was maintained under reflux for a further 10 minutes whereupon the mixture was filtered, the salt was washed with 2 portions of 30 cc each of cyclohexane, the united organic phases were washed with water (3 X 100 cc), dried over sodium sulphate and the solvent was removed by evaporation at 1 5 mm Hg and at 40"C.
The reaction crude product (weight = 140 to 150 g) was distilled at 0.1 mm Hg/75-80 C, to obtain compound (3) with yields ranging from 55 to 60%.
The nuclear magnetic resonance (NMR) analysis revealed a ratio between cis and trans isomers of about 1 :1.
The infrared analysis revealed meaningful bands at 1 720, 1 380, 1240, 1 175 and 1025 cm-'.
Example 2
This Example illustrates the preparation of 2, 2-dimethyl-3-hydroxymethyl.cyclopropanecar- boxylic acid ethyl ester starting from the compounds prepared by the process of the invention.
A solution of 10.7 g (0.05 mols) of 2,2-dimethyi-3-acetoxymethyl-cyclopropane carboxylic acid ethyl ester (prepared as described in Example 1) in 20 ml of ethanol, was slowly added to a solution of 0.2 g of sodium (0.01 mols) in 100 ml of absolute ethanol stirred at room temperature. The resulting mixture was stirred at room temperature over night, then the solvent was removed by dilstillation at reduced pressure.
The residue was treated with 200 ml of ethylether andl 20 ml of water. The organic phase was separated dried over anhydrous Na2SO4 and the solvent was evaporated. The residue was distilled at reduced pressure gathering the fraction boiling at 100 to 108"C at the pressure of 1.6 mm Hg, consisting of 2,2-dimethyl-3-hydroxymethyl-cyclopropanecarboxylic acid ethyl ester. (IR spectroscopic data consistent with the assigned structure).
The oxidation of the alcohol to caronaldehyde can be performed according to known methods e.g. Journal Organic Chem. page 885 (1976).
Claims (8)
1. A process for the preparation of compounds of formula:
in which R represents a lower alkyl group
in which 3,3-dimethyl-allyl acetate is reacted with a diazoacetate of formula:
N2CH-COOR (VI)
in which R represents a lower alkyl group,
in an inert solvent and in the presence of anhydrous copper sulphate and metal copper in the form of powder.
2. A process as claimed in Claim 1 in which cyclohexane is used as a solvent.
3. A process as claimed in Claim 1 or Claim 2 in which copper sulphate is employed in a molar ratio of about 1 :10 with respect to 3,3-dimethyl-allyl acetate.
4. A process as claimed in any preceding claim in which metal copper is employed in a molar ratio of about 1 :10 with respect to 3,3-methyl-allyl acetate.
5. A process as claimed in any preceding claim in which the reaction between 3,3-dimethylallyl acetate and diazoacetate is conducted at about 80"C.
6. A process as claimed in any preceding claim in which the reaction between 3,3-dimethylallyl acetate and diazoacetate is conducted by adding a solution of the diazoacetate in cyclohexane to a suspension of copper sulphate, metal copper and 3,3-dimethyl-allyl acetate in cyclohexane maintained under stirring in a nitrogen atmosphere at 80"C.
7. A process for preparing an ester of 2,2-dimethyl-3-acetoxymethyl-cyclopropanecarboxylic acid as claimed in Claim 1 substantially as herein described with reference to Example 1.
8. The ethyl ester of 2,2-dimethyl-3-acetoxymethyl-cyclopropanecarboxylic acid.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT24225/79A IT1122093B (en) | 1979-07-10 | 1979-07-10 | ESTERS OF THE 2,2-DIMETHYL-3-ACETOXY-METHYL-CYCLOPROPANCARBOXYLIC ACID AND THEIR PREPARATION |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2054587A true GB2054587A (en) | 1981-02-18 |
| GB2054587B GB2054587B (en) | 1983-07-13 |
Family
ID=11212646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8022436A Expired GB2054587B (en) | 1979-07-10 | 1980-07-09 | Esters of 2,2-dimethyl-3-acetoxymethylcyclopropane carboxylic acid and their preparation |
Country Status (8)
| Country | Link |
|---|---|
| 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) |
Family Cites Families (1)
| 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 |
-
1979
- 1979-07-10 IT IT24225/79A patent/IT1122093B/en active
-
1980
- 1980-07-07 NL NL8003910A patent/NL8003910A/en not_active Application Discontinuation
- 1980-07-08 JP JP9232280A patent/JPS5625137A/en active Pending
- 1980-07-08 FR FR8015128A patent/FR2460918A1/en active Granted
- 1980-07-09 GB GB8022436A patent/GB2054587B/en not_active Expired
- 1980-07-09 DE DE19803026011 patent/DE3026011A1/en not_active Withdrawn
- 1980-07-10 BE BE0/201361A patent/BE884260A/en not_active IP Right Cessation
- 1980-07-10 CH CH527980A patent/CH645338A5/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| FR2460918A1 (en) | 1981-01-30 |
| NL8003910A (en) | 1981-01-13 |
| CH645338A5 (en) | 1984-09-28 |
| FR2460918B1 (en) | 1984-03-30 |
| JPS5625137A (en) | 1981-03-10 |
| BE884260A (en) | 1981-01-12 |
| DE3026011A1 (en) | 1981-02-05 |
| IT7924225A0 (en) | 1979-07-10 |
| IT1122093B (en) | 1986-04-23 |
| GB2054587B (en) | 1983-07-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |