CA1218074A - Lactones - Google Patents
LactonesInfo
- Publication number
- CA1218074A CA1218074A CA000347185A CA347185A CA1218074A CA 1218074 A CA1218074 A CA 1218074A CA 000347185 A CA000347185 A CA 000347185A CA 347185 A CA347185 A CA 347185A CA 1218074 A CA1218074 A CA 1218074A
- Authority
- CA
- Canada
- Prior art keywords
- formula
- butyl
- hal
- chlorine
- haloacid
- 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
- 150000002596 lactones Chemical class 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 16
- -1 inorganic acid halide Chemical class 0.000 claims abstract description 12
- 150000002148 esters Chemical class 0.000 claims abstract description 9
- 150000004820 halides Chemical class 0.000 claims abstract 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 4
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical class OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims 3
- 150000007522 mineralic acids Chemical class 0.000 claims 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical compound C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000000749 insecticidal effect Effects 0.000 abstract description 3
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 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 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- KGANAERDZBAECK-UHFFFAOYSA-N (3-phenoxyphenyl)methanol Chemical compound OCC1=CC=CC(OC=2C=CC=CC=2)=C1 KGANAERDZBAECK-UHFFFAOYSA-N 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 125000000950 dibromo group Chemical group Br* 0.000 description 2
- PIUGWHOPZWEXQQ-UHFFFAOYSA-N ethyl 4,6,6-trichloro-3,3-dimethylhex-5-enoate Chemical compound CCOC(=O)CC(C)(C)C(Cl)C=C(Cl)Cl PIUGWHOPZWEXQQ-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- OGFAWKRXZLGJSK-UHFFFAOYSA-N 1-(2,4-dihydroxyphenyl)-2-(4-nitrophenyl)ethanone Chemical compound OC1=CC(O)=CC=C1C(=O)CC1=CC=C([N+]([O-])=O)C=C1 OGFAWKRXZLGJSK-UHFFFAOYSA-N 0.000 description 1
- OHAMOQALFCXZBV-UHFFFAOYSA-N 2,2-dichloroethenyl 2,2-dimethylcyclopropane-1-carboxylate Chemical compound CC1(C)CC1C(=O)OC=C(Cl)Cl OHAMOQALFCXZBV-UHFFFAOYSA-N 0.000 description 1
- FXGRUJBGHMYOQE-UHFFFAOYSA-N 4,6,6-trichloro-3,3-dimethylhex-5-enoyl chloride Chemical compound ClC(=O)CC(C)(C)C(Cl)C=C(Cl)Cl FXGRUJBGHMYOQE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- PKNLWLCURZNADF-UHFFFAOYSA-N hex-5-enoyl chloride Chemical compound ClC(=O)CCCC=C PKNLWLCURZNADF-UHFFFAOYSA-N 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- HFRXJVQOXRXOPP-UHFFFAOYSA-N thionyl bromide Chemical compound BrS(Br)=O HFRXJVQOXRXOPP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT
"Lactones"
Esters of 3-.beta.,.beta.-dihalovinyl-2,2-dimethylcyclopropane-1-carboxylic acids are prepared from 4-.beta.,.beta.-dihalovinyl-3, 3-dimethyl butyrolactone by reaction with an inorganic acid halide to open the lactone ring with formation of the corresponding 4-haloacid halide, which with alcohols affords the corresponding 4-haloacid ester which is cyclised by bases to give the above product. The products are intermediate for insecticidal esters and the process offers fewer stages and higher yields than the processes hitherto described or used.
"Lactones"
Esters of 3-.beta.,.beta.-dihalovinyl-2,2-dimethylcyclopropane-1-carboxylic acids are prepared from 4-.beta.,.beta.-dihalovinyl-3, 3-dimethyl butyrolactone by reaction with an inorganic acid halide to open the lactone ring with formation of the corresponding 4-haloacid halide, which with alcohols affords the corresponding 4-haloacid ester which is cyclised by bases to give the above product. The products are intermediate for insecticidal esters and the process offers fewer stages and higher yields than the processes hitherto described or used.
Description
~ ~ Dx', 28041/A
This invention relates to a process for the preparation of cyclopropane carboxylic acid esters, According to the present invention there is provided a process by which esters of the formula:
~ = CH Cl3 y/ \CEI--cl ~ CH3 ~ R
CO2Rl wherein R1 is a lower alkyl group, R is a hydrogen atom or a cyano,carboxy, methyl, ethyl, isopropyl, n-propyl, tert-butyl, n-butyl, carboxymethyl or cyanoms~hyl group and each Y is a chlorine or bromine atom, are prepared by treating a lactone o~ formula ~H3 \ C=CH - CH- ~ - -CH3 ~ o/IR
wherein R and Y have the previously de~ined meanings, with an acid chloride or bromide and treating the product with an alcohol of the formula RlOH and a base.
This process proceeds in three stages which may be carried out. if desired, especially in respect o-E the first and second stages, withou~ isolation of the inter-mediate products, Each .individual stage, and the two combinations of successive stages, are also features of the inven-tion, In the first stage of the process the lactone ring is opened and the appropriate 3,3-dimethyl-4-chloro (or bromo)- 6,$-dichloro (or dibromo) hex-5-enoyl chloride (or bromide) is obtained, In this stage it is preferred that R be a hydrogen atom or a methyl, ethyl, isopropyl, n-propyl, tert-butyl, n-bu-tyl, carboxymethyl or cyano-methyl group~
The first stage of the process is conveniently carried out using at least a molar amount, and preferably not more than 1,5 molar amounts, of acid chloride or bromide at a temperature between ambient and the boiling point of the reaction mixture, As acid chloridesor bromides there may be mentioned especially inorganic acid chlorides such as thionyl chloride, phosphorous pentachloride and phosphorus oxychloride, which provide hexenjoyl` chloride having a 4-chloro substituent, and inorganic acid bromides such as thionyl bromide and phosphorus pentabromide, which provide acid bromides having a 4~bromo substituent, The second stage of the process, treatment with the alcohol of the formula RlOH, is preferably carried out without isolation of the product of the first stage.
The alcohol is preferably used in excess, for example 1,5 molar proportions, and a reaction temperature from ambient to the boiling point of the reaction mixture may conveniently be used. The alcohol RlOH is preferably methanol or ethanol.
The product of the second stage, the ester of the acid of which the acid chlo.ride resulted from the first stage, may if desired be isolated by conventional means, for example removal of excess alcohol, RlOH, and distilla-tion under reduced pressure, but it is not usually necessary to carry out such isolation before carrying out the third stage, The third stage, treatment with the base, may be carried out at a temperature between ambient and the boiling point of the reaction mixture using a solvent conveniently the alcohol, RlOH, The base is preferably an alkali metal alkoxide, for example NaORl, but may be another alkoxida or sodium hydroxide in ethanol, ~ he amount of base is preferably from 2.0 to 3,0 molar equivalents, The cyclopropanecarboxylic ester may be isolated by conventional means, for example neutralisation by the addition of e.g, dilute sulphuric acid, separation from the residue of any salt, removal of excess alcohol by distillation, addition to water and extraction with a water-immiscible so].vent, After removal of the solvent the product may be purified by distillation under reduced pressure.
The cyclopropanecarboxylic ester may be converted into an insecticidal ester by known means, for example an ester .interchange reaction with e,g, m-phenoxybenzyl alcohol using a catalyst uuch as potassium tert,-butoxide or may be converted into for example the corres-ponding acid or acid chloride which may then be esterifiedwith e,g, m-phenoxybenzyl alcohol, The process of the inventiOn affords a route to insecticidal esters of 3~ dichloro~or dibromo) vinyl-2,2-dimethylcycloproparle-~-~arboxylic acids which has fewer stages and gives higher yields than the routes hitherto described or used.
The invention is illustxated but not limited by the following examples in which all parts and percentages are by weight unless stated otherwise.
ExamPle ,1 29.08 Parts of thionyl chloride were added dropwise with stirring at room temparature to 20.8 parts of 2~ dichlorovinyl)-3,3-dimethyl~5-oxotetrahydrofuran, The mixture was boiled or 1 hour after which the unreacted thionyl chloride was distilled o~f to give crude 3,3-dimethyl-4,6,6-trichlorohex 5-enoyl chloride 20 Parts of ethanol were then added dropwise, the temperature being maintained at below 30C and the mixture was then refluxed for 1 hour. The product was dis-tilled under reduced pressure giving 15.28 parts of ethyl 4,6,6 trichloro-3,3-dimethylhex-5-enoate, which contained a minor amount of unchanged lactone Example 2 A slurry of 11.2 parts of potassium t-butoxide in 200 parts of toluene wa~ added 510wly to 13.7 parts of ethyl 4,6,6 trichloro-3,3-dimethyl-hex-5-enoate stirred at below 0C and stirred at below 0C for a further 1 hour.
The mixture was neutralised to pH 6 with concentxated hydrochloric acid Water was added to dissolve the precipitated salt and the toluene layer separated. The water layer was extracted again with toluene and the toluene then removed from the combined extracts giving in nearly theoretical yield the mixed cis and trans forms of ethyl 3~ dichlorovinyl-2,2-dimethylcyclopropanecarboxylate.
_a,..
This invention relates to a process for the preparation of cyclopropane carboxylic acid esters, According to the present invention there is provided a process by which esters of the formula:
~ = CH Cl3 y/ \CEI--cl ~ CH3 ~ R
CO2Rl wherein R1 is a lower alkyl group, R is a hydrogen atom or a cyano,carboxy, methyl, ethyl, isopropyl, n-propyl, tert-butyl, n-butyl, carboxymethyl or cyanoms~hyl group and each Y is a chlorine or bromine atom, are prepared by treating a lactone o~ formula ~H3 \ C=CH - CH- ~ - -CH3 ~ o/IR
wherein R and Y have the previously de~ined meanings, with an acid chloride or bromide and treating the product with an alcohol of the formula RlOH and a base.
This process proceeds in three stages which may be carried out. if desired, especially in respect o-E the first and second stages, withou~ isolation of the inter-mediate products, Each .individual stage, and the two combinations of successive stages, are also features of the inven-tion, In the first stage of the process the lactone ring is opened and the appropriate 3,3-dimethyl-4-chloro (or bromo)- 6,$-dichloro (or dibromo) hex-5-enoyl chloride (or bromide) is obtained, In this stage it is preferred that R be a hydrogen atom or a methyl, ethyl, isopropyl, n-propyl, tert-butyl, n-bu-tyl, carboxymethyl or cyano-methyl group~
The first stage of the process is conveniently carried out using at least a molar amount, and preferably not more than 1,5 molar amounts, of acid chloride or bromide at a temperature between ambient and the boiling point of the reaction mixture, As acid chloridesor bromides there may be mentioned especially inorganic acid chlorides such as thionyl chloride, phosphorous pentachloride and phosphorus oxychloride, which provide hexenjoyl` chloride having a 4-chloro substituent, and inorganic acid bromides such as thionyl bromide and phosphorus pentabromide, which provide acid bromides having a 4~bromo substituent, The second stage of the process, treatment with the alcohol of the formula RlOH, is preferably carried out without isolation of the product of the first stage.
The alcohol is preferably used in excess, for example 1,5 molar proportions, and a reaction temperature from ambient to the boiling point of the reaction mixture may conveniently be used. The alcohol RlOH is preferably methanol or ethanol.
The product of the second stage, the ester of the acid of which the acid chlo.ride resulted from the first stage, may if desired be isolated by conventional means, for example removal of excess alcohol, RlOH, and distilla-tion under reduced pressure, but it is not usually necessary to carry out such isolation before carrying out the third stage, The third stage, treatment with the base, may be carried out at a temperature between ambient and the boiling point of the reaction mixture using a solvent conveniently the alcohol, RlOH, The base is preferably an alkali metal alkoxide, for example NaORl, but may be another alkoxida or sodium hydroxide in ethanol, ~ he amount of base is preferably from 2.0 to 3,0 molar equivalents, The cyclopropanecarboxylic ester may be isolated by conventional means, for example neutralisation by the addition of e.g, dilute sulphuric acid, separation from the residue of any salt, removal of excess alcohol by distillation, addition to water and extraction with a water-immiscible so].vent, After removal of the solvent the product may be purified by distillation under reduced pressure.
The cyclopropanecarboxylic ester may be converted into an insecticidal ester by known means, for example an ester .interchange reaction with e,g, m-phenoxybenzyl alcohol using a catalyst uuch as potassium tert,-butoxide or may be converted into for example the corres-ponding acid or acid chloride which may then be esterifiedwith e,g, m-phenoxybenzyl alcohol, The process of the inventiOn affords a route to insecticidal esters of 3~ dichloro~or dibromo) vinyl-2,2-dimethylcycloproparle-~-~arboxylic acids which has fewer stages and gives higher yields than the routes hitherto described or used.
The invention is illustxated but not limited by the following examples in which all parts and percentages are by weight unless stated otherwise.
ExamPle ,1 29.08 Parts of thionyl chloride were added dropwise with stirring at room temparature to 20.8 parts of 2~ dichlorovinyl)-3,3-dimethyl~5-oxotetrahydrofuran, The mixture was boiled or 1 hour after which the unreacted thionyl chloride was distilled o~f to give crude 3,3-dimethyl-4,6,6-trichlorohex 5-enoyl chloride 20 Parts of ethanol were then added dropwise, the temperature being maintained at below 30C and the mixture was then refluxed for 1 hour. The product was dis-tilled under reduced pressure giving 15.28 parts of ethyl 4,6,6 trichloro-3,3-dimethylhex-5-enoate, which contained a minor amount of unchanged lactone Example 2 A slurry of 11.2 parts of potassium t-butoxide in 200 parts of toluene wa~ added 510wly to 13.7 parts of ethyl 4,6,6 trichloro-3,3-dimethyl-hex-5-enoate stirred at below 0C and stirred at below 0C for a further 1 hour.
The mixture was neutralised to pH 6 with concentxated hydrochloric acid Water was added to dissolve the precipitated salt and the toluene layer separated. The water layer was extracted again with toluene and the toluene then removed from the combined extracts giving in nearly theoretical yield the mixed cis and trans forms of ethyl 3~ dichlorovinyl-2,2-dimethylcyclopropanecarboxylate.
_a,..
Claims (6)
1. A process for the preparation of cyclopropane carboxylic acid esters of the formula:
wherein R1 is a lower alkyl group, R is a hydrogen atom or a cyano, carboxy, methyl, ethyl, isopropyl, n-propyl, tert-butyl, n-butyl, carboxymethyl or cyanomethyl group and each Y is a chlorine or bromine atom, which comprises treating a lactone of the formula:
wherein R and Y have the previously defined meanings, with an inorganic acid chloride or bromide and treating the product with an alcohol of the formula R1OH and a base.
wherein R1 is a lower alkyl group, R is a hydrogen atom or a cyano, carboxy, methyl, ethyl, isopropyl, n-propyl, tert-butyl, n-butyl, carboxymethyl or cyanomethyl group and each Y is a chlorine or bromine atom, which comprises treating a lactone of the formula:
wherein R and Y have the previously defined meanings, with an inorganic acid chloride or bromide and treating the product with an alcohol of the formula R1OH and a base.
2. A process for the preparation of a 4-haloacid halide of the formula:
Y2C=CH.CH Hal.C(CH3)2CHR.COHal wherein R and Y have the meanings stated in Claim 1 and Hal represents a chlorine or bromine atom, which comprises treating a lactone of the formula:
with an inorganic acid chloride or bromide.
Y2C=CH.CH Hal.C(CH3)2CHR.COHal wherein R and Y have the meanings stated in Claim 1 and Hal represents a chlorine or bromine atom, which comprises treating a lactone of the formula:
with an inorganic acid chloride or bromide.
3. A process as claimed in Claim 2 wherein R is a hydrogen atom or a methyl, ethyl, isopropyl, n-propyl, tert-butyl, n-butyl, carboxymethyl or cyanomethyl group.
4. A process for the preparation of a haloacid ester having the formula:
Y2C = CH.CH Hal.C(CH3)2.CHR.CO2R1 wherein R1, R and Y have the meanings stated in Claim 1 and Hal represents a chlorine or bromine atom which comprises carrying out in succession the process of Claim 2 and treating the 4-haloacid halide having the formula defined in Claim 2 with an alcohol of the formula R1OH.
Y2C = CH.CH Hal.C(CH3)2.CHR.CO2R1 wherein R1, R and Y have the meanings stated in Claim 1 and Hal represents a chlorine or bromine atom which comprises carrying out in succession the process of Claim 2 and treating the 4-haloacid halide having the formula defined in Claim 2 with an alcohol of the formula R1OH.
5. The process of reacting V
with R'OH, to produce the compound II of formula:
wherein Hal is chlorine or bromine R1 is loweralkyl.
with R'OH, to produce the compound II of formula:
wherein Hal is chlorine or bromine R1 is loweralkyl.
6. The process of reacting VI
with C2H5OH to produce the compound IV of formula:
with C2H5OH to produce the compound IV of formula:
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000347185A CA1218074A (en) | 1975-07-11 | 1980-03-06 | Lactones |
| CA000509681A CA1233832A (en) | 1975-07-11 | 1986-05-21 | Lactones |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB29253/75 | 1975-07-11 | ||
| GB29253/75A GB1527989A (en) | 1975-07-11 | 1975-07-11 | 4-dihalovinyl-3,3-dimethylbutyrolactones and their use in the production of insecticides |
| CA256,648A CA1090360A (en) | 1975-07-11 | 1976-07-09 | Lactones |
| CA000347185A CA1218074A (en) | 1975-07-11 | 1980-03-06 | Lactones |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA256,648A Division CA1090360A (en) | 1975-07-11 | 1976-07-09 | Lactones |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000509681A Division CA1233832A (en) | 1975-07-11 | 1986-05-21 | Lactones |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1218074A true CA1218074A (en) | 1987-02-17 |
Family
ID=25668325
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA256,648A Expired CA1090360A (en) | 1975-07-11 | 1976-07-09 | Lactones |
| CA000347185A Expired CA1218074A (en) | 1975-07-11 | 1980-03-06 | Lactones |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA256,648A Expired CA1090360A (en) | 1975-07-11 | 1976-07-09 | Lactones |
Country Status (1)
| Country | Link |
|---|---|
| CA (2) | CA1090360A (en) |
-
1976
- 1976-07-09 CA CA256,648A patent/CA1090360A/en not_active Expired
-
1980
- 1980-03-06 CA CA000347185A patent/CA1218074A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CA1090360A (en) | 1980-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4127604A (en) | Process for the preparation of acetic acid derivatives | |
| WO2022199378A1 (en) | Synthetic method of bempedoic acid active pharmaceutical ingredient | |
| CA1218074A (en) | Lactones | |
| US4310464A (en) | Lactones | |
| CA1116178A (en) | Production of chrysanthemic acid esters and homologues thereof | |
| GB2081714A (en) | Cyclohexylcarboxylic acid derivatives | |
| CA1233832A (en) | Lactones | |
| US3922296A (en) | Novel process for the preparation of cyclopentane-1, 2-diones and intermediates therefor | |
| JPH0129783B2 (en) | ||
| IE43461B1 (en) | Cyclopropane derivatives | |
| US4508913A (en) | Dialkoxymethyl-butyrolactones | |
| CA2092347A1 (en) | Process for the production of tetronic acid alkyl esters | |
| HU182688B (en) | Process for preparing esters of4-cyano-4-halo-3,3-dimethyl-butyric acid | |
| US5183908A (en) | Process for the preparation of substituted furanones | |
| EP0306096B1 (en) | Process for preparing diphenyl ethers | |
| US4155929A (en) | Process for the preparation of an acetonitrile derivative | |
| US4562282A (en) | 4-Methyl-3-formyl-pentanoic acid esters | |
| US4007216A (en) | 2-Methoxy-4-methyl-3-oxo-cyclopent-1-ene-1,4-dicarboxylic acid esters | |
| EP0016505B1 (en) | Process for the preparation of dihalovinyl compounds | |
| EP0022607B1 (en) | Process for the preparation of halogenated hydrocarbons | |
| JP2720934B2 (en) | Process for producing 3- (2-chloro-2- (4-chlorophenyl) -vinyl) -2,2-dimethylcyclopropanecarboxylic acid | |
| CA1081251A (en) | Process for the preparation of 3-alkyl-cyclopentane-1, 2-diones, and itermediates therefor | |
| SU594095A1 (en) | Method of preparing 2,2,2-trichlor-1-o-chlorphenylethanol | |
| GB2065118A (en) | 2-(2',2'-dichloro-3',3',3'-trifluoropropyl)- and 2-(2',2',3'-trichloro-3',3'-difluoropropyl)-4-chlorocyclobutan-1-ones | |
| US4334091A (en) | Process for preparing halovinyl cyclopropane carboxylic acid salts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |