IE47130B1 - Preparation of methyl and ethyl esters of cyclopropane carboxylic acids - Google Patents
Preparation of methyl and ethyl esters of cyclopropane carboxylic acidsInfo
- Publication number
- IE47130B1 IE47130B1 IE1441/78A IE144178A IE47130B1 IE 47130 B1 IE47130 B1 IE 47130B1 IE 1441/78 A IE1441/78 A IE 1441/78A IE 144178 A IE144178 A IE 144178A IE 47130 B1 IE47130 B1 IE 47130B1
- Authority
- IE
- Ireland
- Prior art keywords
- group
- reaction
- carbon atoms
- process according
- methyl
- Prior art date
Links
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 6
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical class OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 title description 4
- 125000004494 ethyl ester group Chemical group 0.000 title description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- -1 dimethylvinyl group Chemical group 0.000 claims abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 12
- AUQDITHEDVOTCU-UHFFFAOYSA-N cyclopropyl cyanide Chemical compound N#CC1CC1 AUQDITHEDVOTCU-UHFFFAOYSA-N 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 239000002516 radical scavenger Substances 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000001117 sulphuric acid Substances 0.000 claims description 5
- 235000011149 sulphuric acid Nutrition 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 7
- 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 description 4
- 239000000543 intermediate Substances 0.000 abstract description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract 1
- 239000011707 mineral Substances 0.000 abstract 1
- 150000002825 nitriles Chemical class 0.000 description 11
- 238000006136 alcoholysis reaction Methods 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 150000002596 lactones Chemical class 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000003482 Pinner synthesis reaction Methods 0.000 description 2
- 238000010932 ethanolysis reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- KGANAERDZBAECK-UHFFFAOYSA-N (3-phenoxyphenyl)methanol Chemical compound OCC1=CC=CC(OC=2C=CC=CC=2)=C1 KGANAERDZBAECK-UHFFFAOYSA-N 0.000 description 1
- BEMACEBIURPVCG-UHFFFAOYSA-N 2-(2,2-dichloroethenyl)-1,1,3-trimethylcyclopropane Chemical compound CC1C(C=C(Cl)Cl)C1(C)C BEMACEBIURPVCG-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- GXUQMKBQDGPMKZ-UHFFFAOYSA-N 2-hydroxy-2-(3-phenoxyphenyl)acetonitrile Chemical compound N#CC(O)C1=CC=CC(OC=2C=CC=CC=2)=C1 GXUQMKBQDGPMKZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- YMGUBTXCNDTFJI-UHFFFAOYSA-M cyclopropanecarboxylate Chemical compound [O-]C(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 231100001225 mammalian toxicity Toxicity 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Abstract
Compounds of the general formula in which R<1> and R<2> in each case stand for an alkyl group having 1 to 4 carbon atoms or together form an alkylene group having up to 5 carbon atoms, X<1> and X<2> in each case stand for a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or for a halogen atom or, with one another, form an alkylene group having up to 5 carbon atoms or X<1> denotes a hydrogen atom and X<2> is a monohalovinyl, dihalovinyl or dimethylvinyl group and R stands for a methyl or ethyl group, are prepared. A procedure is used in which a cyclopropanenitrile of the general formula is reacted with methanol or ethanol under substantially anhydrous conditions at a temperature from 80 to 200 DEG C and in the presence of a mineral acid as a reaction catalyst and of a scavenging agent for the ammonia formed during the reaction. The compounds of the formula I are intermediates for the preparation of synthetic pyrethroids.
Description
This invention relates to a process for the preparation of methyl and ethyl esters of cyclopropane carboxylic acids.
Substituted cyclopropane carboxylic acids are useful intermediates in the preparation of pesticidally-active esters thereof, especially the 3-phenoxybenzyl and alphacyano-3-phenoxybenzyl esters; these pesticidally active compounds, the so-called synthetic pyrethroids, have exceptionally good insecticidal properties whilst possessing a very low mammalian toxicity. This combination of properties makes them of considerable interest to the agrochemical industry and much effort has been expended in determining economic routes to these synthetic pyrethroids, especially to the manufacture of substituted cyclopropane carboxylic acids which hitherto have no established synthetic routes available in the literature. m a search for economic routes to the cyclopropane acid the Applicant has successfully managed to synthesise the substituted cyclopropanenitrile but hitherto has been unable to convert satisfactorily the nitrile into the corresponding acid or ester.
The Applicant has attempted alcoholysis in the presence of an acid catalyst according to the many recommendations in standard text books but found that the yields of the corresponding alkyl ester were very poor and often resulted in the production of large quantities of lactones and other by-products. 713 0 ίο It is known to convert nitriles into esters by means of the Pinner Reaction (see Houben-Weyl Handbuch der Organischen Chemie H. Heneka, Book 8, p. 536-539 (1952) and Chemical Reviews Robert Roger and Douglas Neilson, p. 181—18U (1961)), involving the action of an alkanol and hydrogen bromide or chloride on a nitrile at ambient or lower temperatures under anhydrous conditions and hydrolysing the resulting watersensitive iminoether. In the case of cyclopropane nitriles, however, the Pinner Reaction conditions had no effect even after a period of 2h hours.
Surprisingly, the Applicant has now found that a modification of the Pinner conditions has resulted in a simple conversion of a substituted cyclopropane nitrile into the methyl or ethyl ester thereof.
The present invention, therefore, provides a process for the manufacture of a compound having the following general formula:- COOR H (I) (wherein each of and Rg is independently an alkyl group of 1 to 4 carbon atoms or R^ and Rg together represent an alkylene group of up to 5 carbon atoms; each of X^ and Xg is independently a hydrogen atom, an alkyl group of 1 to t carbon atoms or a. halogen atom, or X^ and Xg together represent an alkylene group of up to 5 carbon atoms; or X1 is a hydrogen atom and Xg is a itonohalovinyl group, a dihalovinyl group or a dimethyIvinyl group; and R is a methyl or ethyl group) which comprises reacting a cyclopropane nitrile having the general formula:- (ni with methanol or ethanol under substantially anhydrous conditions at a temperature in the range 80° to 200°C and in the presence of sulphuric acid acting as reaction catalyst and as scavenger for ammonia produced during the reaction.
Preferably the reaction temperature is maintained in the range 100°C to 200°C, more preferably in the range 14o°C to 200°C. With reaction mixtures employed in the process according to the invention, temperatures in the required range will not usually be obtainable at atmospheric pressure, and thus higher IQ pressures, for example in the range 1 to 10 atmospheres will often have to be used; generally speaking pressures in the range 1 to 5 atmospheres have been found to be sufficient.
It has been founi necessary to employ substantially anhydrous conditions, that is to say, conditions under which the amount of water present during the reaction is kept to a minimum for example, below about 5% by weight of the reaction mixture, preferably below 1% and suitably below 0.5% by weight of the reaction mixture. For example the reaction will tolerate the water normally present in concentrated sulphuric acid (2% by weight) at the concentrations of acid employed in the process, provided that the alcohol and the nitrile reactants are substantially dry.
As the reaction proceeds, ammonia is generated thereby neutralising the acid catalyst, and thus sufficient quantities of the acid must he present in order to provide the necessary catalytic action. In general terms, the amount of acid (based on the nitrile) present in the process according to the invention should lie in the range 3l1 to 1:1 by weight.
In the alcoholysis reaction, the Applicant has found that only ethanol and methanol under the conditions defined hereinbefore provide the corresponding ester of the nitrile of general formula II in satisfactory yields and in the substantial absence of unwanted by-products. Ethanol is the preferred reagent 713 0 because of the relatively short reaction time involved in ethanolysis according to the invention and also because of the economic attraction of using such a readily available product.
In the compounds of general formula I preferably R^ and B^ are methyl groups; X^ and X2 are chlorine or bromine atoms or methyl groups; or X^ is a hydrogen atom and Xg is a dichlorovinyl group, a dihromovinyl group, a difluorovinyl group, a chlorofluorovinyl group, or a dimethylvinyl group; and R is methyl or ethyl.
As has been stated hereinbefore, the alcoholysis reaction enables a cyclopropane nitrile to be converted into the corresponding methyl or ethyl ester which may then be converted to a synthetic pyrethroid via the free acid or the acid chloride by reaction with 3-phenoxybenzyl alcohol or alphacyano-3-phenoxybenzyl alcohol. The following nitriles are the most important in that they are intermediates for the pyrethroids of greatest pesticidal activity:2.2.3.3- tetramethylcyclopropane nitrile: 3.3- dimethy1-2-(2,2-dimethylvinylCyclopropane nitrile; 3.3- dimethyl-2-(2,2-dichlorovinyl)cyclopropane nitrile; and 3.3- dimethyl-2-(2,2-dibromovinyl)cyclopropane nitrile.
It will be appreciated that, since the nitrile starting materials and the ester end-products in the process according to the invention possess asymmetric carbon atoms, the nitriles and esters can exist in a corresponding number of stereoisomeric forms. The process according to the invention, therefore, also includes the manufacture of compounds of formula (I) which are in the form of single stereoisomers or mixtures thereof.
The invention is further illustrated by reference to the following Examples, Example I Preparation of methyl 3.3 dimethyl-2-(2,2-dichlorovinyl) cyclopropane earboxylate A mixture of 2.0 g (0.1] mol) of substantially d’-y 3,3dimethyl-2-(2,2~dichlorovinyl)cyclopropane nitrile and 12 ml of a sulphuric acid/methanol solution (20? weight of concentrated sulphuric acid, in dried methanol) was autoclaved at 100°C (5 atmospheres) for 32 hours. Water was then added and the product extracted, with methylene chloride. The organic phase was washed with dilute sodium bicarbonate, dried over magnesium sulphate and evaporated to give methyl 3j3-dimethyl-2-(2,2dichlorovinyl)cyclopropane carboxylate (95% conversion; 100% selectivity to the methyl ester).
Examples II-IV Preparation of ethyl 3,3-diinethyl-2-(2,2-diehlorovinyl) cyclopropane carboxylate The procedure of Example I was repeated using ethanol rather than methanol as the alcoholysis reagent and using various concentrations of the nitrile. The reaction conditions and the results are shown in Table A. w t> iw o o 0) CQ .9 S & o Λ o o kO o TABLE A W 4) 4) ii iw ®> 3 Λ CQ P< (0 (0 4) O h s fk -P S Cw^ 8S -=r σ ω OJ W o λ o CJ Φ H •r) h P & ii & o H O H Λ o r-| >» Λ P 4) a Λ 07130 Comparative Examples A number of comparative experiments were carried out employing methanol, ethanol, isopropanol, and ιι-butanol as the alcoholysis reagent and three different acid catalysts; the same nitrile (DCTIT) as used in the preceding Examples was employed.
The reaction conditions and results are shown in Table B.
It will be seen that the yields of DCVA-ester are considerably lower than those produced by the process according to the invention and are invariably accompanied hy unwanted by-products, especially the corresponding amide and a lactone by-product, the latter probably resulting from acid-catalysed ring opening followed by alcoholysis and ring closure to form a lactone. Moreover in the case of ethanolysis the reaction time is also much longer than the process employed in Examples II to IV. 713 0 COMPARATIVE EXPERIMENTS .%) data) Lactone by-product 1 LA Vt CM Cd t— cn ti CM ft υ A Α Α Ο !3τ, * § φ ft ίζ} U Be •g3 W U. WK 3 o CM o O co ti 1 Α § 1 h r· CM CM ^--· Ο ft w fl > 1 ft ο o s h A ft «Η β o ft ti *·* ΈΛ X **. «. o ift O ft- O IA O LA IA cn o ti co CM A ti - ti ti £ la o' cn O o o o •η n) 3 4) ti ^z ft VO O o •rt o CM ΰ g ti ti k ft B ti e< ti o <** •rt ft ti » Ί ft IA O Ο β ti rrt 3 co o IA □ CM ft- CO IA ti Ed ft ffi on O *d Ό ti ft- ft- ft· ft· o o o o CO fi ft CQ to ft ti Si Si woj W -fl on w CM ft CM ft tri 5>, to ao a •P ft • > □ Co o o o o •ti ft CJ o a + g β « ti » w O o 0 0 o o o o 0 o rd o o rd g 0 3 0 rd rd g ft o ti 0 O 3 o ft o ti 43 o q § § s F-t ft a ft ti ft ft ft f ti ft ft ft O 3 fl ft ti ti β ti ti •rt ___- •p · —. «—» ft 0 X—\ • rt •rt r> r"* 'S j? 525 • id •rt •rd ί» « **** ft o A g* rd & o k rd ft I Cd Λ δ ΐ s Λ A cn •p •Zi c ft a ti I ft ω ύ) Ή ft •rl s o ft h ω ΰ ti U ti *σ Ό ti ti s σ* -Η ft £ ft φ δ U2 Φ Pt rd b 0 0 O β rt ti ft & a 3 ft β ft ft ft ft ti ft ft 'ϋ ft ti ο •rt rd ti O ft ft ft O o c3 Ό ti ω ω o ti ft CM Cd ft ft μ κ ti ti β Fd •rt 3 ti o o ft s β β O ti 0 0 0 ft ti ti o o o ., ,—. ,-V ti £ o *d ti
Claims (6)
1. A process for the manufacture of a compound having the following general formula:- ΙΟ (wherein each of R 1 and Rg.is independently an alkyl group of 1 to U carhon atoms or R^ and Rg together represent an alkylene group of up to 5 carbon atoms; each of X^ and Xg is independently a hydrogen atom, an alkyl group of 1 to H carbon atoms, or a halogen atom, or X^ and Xg together represent an alkylene group of up to 5 carbon atoms; or X^ is a hydrogen atom and Xg is a monohalovinyl group, a dihalovinyl group or a dimethylvinyl grot®; and R is a methyl or ethyl group) which comprises reacting a cyclopropane nitrile having the general formula:- with methanol or ethanol under substantially anhydrous conditions at a temperature in the range 80° to 200°C and in the presence c£ sulphuric acid acting as reaction catalyst and. as scavenger for ammonia produced during the reaction. 471
2. A process according to claim -1 wherein the reaction temperature is in the range 300® to 200°C.
3. A process according to claim 1 or 2 wherein the reaction is carried out at a pressure in the range 1 to 5 atmospheres.
4. A process according to any one of the preceding claims wherein the amount of water present in the reaction mixture is below If by weight thereof.
5. A process according to any one of the preceding claims wherein and are methyl groups; and X £ are chlorine or bromine atoms or methyl groups; or is a hydrogen atom and X„ is a dichlorovinyl group, a dibromovinyl group, a difluorovinyl group, a chlorofluorovinyl group, or a dimethylvinyl group; and R is methyl or ethyl. 6. A process according to any one of the preceding claims wherein the cyclopropane nitrile of formula (II) Is:2.2.3.3- tetramethylcyclopropane nitrile; 3.3- dimethy1-2-(2,2-dimethylvinyl)cyclopropane nitrile; 3.3- dimethy1-2-(2,2-di chlorovinyl)cyclopropane nitrile; or 3.3- dimethyl-2-(2,2-dibromovinyl)cyclopropane nitrile. 7. A process according to claim 3 substantially as hereinbefore described with reference to Examples I to XV,
6. Compounds of the general formula (I) when prepared according fc the process claimed in any one of the preceding claims. Dated this the 18th day of
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB30470/77A GB1599888A (en) | 1977-07-20 | 1977-07-20 | Preparation of methyl and ethyl esters of cyclopropane carboxylic acids |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IE781441L IE781441L (en) | 1979-01-20 |
| IE47130B1 true IE47130B1 (en) | 1983-12-28 |
Family
ID=10308187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE1441/78A IE47130B1 (en) | 1977-07-20 | 1978-07-18 | Preparation of methyl and ethyl esters of cyclopropane carboxylic acids |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPS5422345A (en) |
| BE (1) | BE868901A (en) |
| BR (1) | BR7804637A (en) |
| CA (1) | CA1123004A (en) |
| CH (1) | CH635064A5 (en) |
| DE (1) | DE2831555A1 (en) |
| DK (1) | DK158343C (en) |
| FR (1) | FR2398042A1 (en) |
| GB (1) | GB1599888A (en) |
| IE (1) | IE47130B1 (en) |
| IT (1) | IT1097870B (en) |
| LU (1) | LU79993A1 (en) |
| NL (1) | NL7807658A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ185635A (en) * | 1976-11-18 | 1980-04-28 | Ici Ltd | Preparation of 3-dihalovinyl-2,2-dimethylcyclopropane carboxylic acid derivatives |
| AU4839279A (en) * | 1978-07-18 | 1980-01-24 | Imperial Chemical Industries Ltd. | Cyclopropane carboxylic acids |
| JPS5793493U (en) * | 1980-11-28 | 1982-06-09 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1553818A (en) * | 1975-07-24 | 1979-10-10 | Nat Res Dev | Synthesis of cyclopropane carboxylic acids |
| NZ185635A (en) * | 1976-11-18 | 1980-04-28 | Ici Ltd | Preparation of 3-dihalovinyl-2,2-dimethylcyclopropane carboxylic acid derivatives |
-
1977
- 1977-07-20 GB GB30470/77A patent/GB1599888A/en not_active Expired
-
1978
- 1978-06-22 CA CA306,002A patent/CA1123004A/en not_active Expired
- 1978-07-11 BE BE1008978A patent/BE868901A/en not_active IP Right Cessation
- 1978-07-18 DK DK321978A patent/DK158343C/en not_active IP Right Cessation
- 1978-07-18 IT IT25820/78A patent/IT1097870B/en active
- 1978-07-18 CH CH774278A patent/CH635064A5/en not_active IP Right Cessation
- 1978-07-18 BR BR7804637A patent/BR7804637A/en unknown
- 1978-07-18 LU LU79993A patent/LU79993A1/en unknown
- 1978-07-18 FR FR7821245A patent/FR2398042A1/en active Granted
- 1978-07-18 NL NL7807658A patent/NL7807658A/en not_active Application Discontinuation
- 1978-07-18 JP JP8682978A patent/JPS5422345A/en active Granted
- 1978-07-18 IE IE1441/78A patent/IE47130B1/en not_active IP Right Cessation
- 1978-07-18 DE DE19782831555 patent/DE2831555A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE2831555C2 (en) | 1987-09-10 |
| DK158343B (en) | 1990-05-07 |
| DE2831555A1 (en) | 1979-02-01 |
| LU79993A1 (en) | 1979-04-09 |
| NL7807658A (en) | 1979-01-23 |
| JPS5422345A (en) | 1979-02-20 |
| CH635064A5 (en) | 1983-03-15 |
| BE868901A (en) | 1979-01-11 |
| DK321978A (en) | 1979-01-21 |
| CA1123004A (en) | 1982-05-04 |
| FR2398042A1 (en) | 1979-02-16 |
| FR2398042B1 (en) | 1983-04-29 |
| DK158343C (en) | 1990-10-01 |
| IE781441L (en) | 1979-01-20 |
| IT1097870B (en) | 1985-08-31 |
| JPS6145612B2 (en) | 1986-10-08 |
| BR7804637A (en) | 1979-04-17 |
| GB1599888A (en) | 1981-10-07 |
| IT7825820A0 (en) | 1978-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| GB1070322A (en) | Process for the preparation of 6-formyloxy caproic acids and derivatives thereof | |
| US2093695A (en) | Process for the preparation of carboxylic acid esters | |
| US3397223A (en) | Preparation of cyclopropane derivatives | |
| IE47130B1 (en) | Preparation of methyl and ethyl esters of cyclopropane carboxylic acids | |
| US4001309A (en) | Method of preparing polyfluoroalkyl group containing compounds | |
| CA1127658A (en) | Esters of cyclopropane carboxylic acid derivatives and process for their preparation | |
| US3823160A (en) | Preparation of ether adducts of n-vinyl-2-pyrrolidone | |
| US3923835A (en) | Process for making 4-butyrolactone | |
| US4042616A (en) | Preparation of cyclopropanecarboxylates | |
| US4382894A (en) | Production of α-cyanobenzyl esters | |
| US2265946A (en) | Preparation of aliphatic organic esters | |
| HU181632B (en) | Process for preparing pyrethroid ester derivatives | |
| EP0926117A1 (en) | Preparation of isopulegol | |
| US3941827A (en) | Preparation of halogenated nitriles | |
| KR840000461A (en) | Method for preparing carboxylic acid and ester | |
| GB2038325A (en) | Preparation of esters of cyclopropanecarboxylic acids | |
| US4234507A (en) | Process for preparing cyanohydrin esters | |
| US3634487A (en) | Method of producing acrylonitrile | |
| GB2026483A (en) | Cyclopropane derivatives | |
| JPS6160822B2 (en) | ||
| US4218398A (en) | Process for producing dimethylformamide | |
| US2095612A (en) | Dichloro-alkyl ethers | |
| US2884454A (en) | thf punnttftiftn of mono- | |
| US3781336A (en) | Method for producing methacrylic acid and its esters | |
| US3984462A (en) | Process for producing dodecanedioic acid dimethyl |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Patent lapsed |