GB2151625A - Process for the preparation of 3,5-ethano-2-2,4-dodecadienoates - Google Patents
Process for the preparation of 3,5-ethano-2-2,4-dodecadienoates Download PDFInfo
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Abstract
3,5-Ethano-2,4-dodecadienoates of the general formula /I/, <IMAGE> wherein R<1> represents a straight-chained or branched C1-4 alkyl or a C2-4 alkynyl group, X stands for a hydrogen atom or a straight-chained or branched C1-4 alkoxy group, Y denotes hydrogen, or X and Y together represents a double bond can be obtained as follows: a./ where R<1> is a C1-4 alkyl group, an anion derived from a phosphoric acid derivative of the general formula /III/, <IMAGE> (wherein R<1> and R<2> each represent a straight-chained or branched C1-4 alkyl group) and a base in a dipolar-aprotic or protic solvent, is reacted with a compound of the general formula /II/, <IMAGE> preferably at a temperature between 20 DEG C and 90 DEG C; and b./ where R<1> represents a C2-4 alkynyl group, an ester of the general formula /I/, wherein R<1> is a C1-4 alkyl group, is reacted with a base in an alcohol or in the mixture of an alcohol and water, the carboxylic acid thus obtained is halogenated, and the resulting halide is reacted with a C2-4 alkynol. Compounds of general formula (I) are effective in controlling many insect species.
Description
SPECIFICATION
Process for the preparation of 3,5-ethano-2,4-dodecadienoates
The invention relates to a process for the preparation of 3,5-ethano-2,4-dodecadienoates of the general formula (I),
wherein
R' represents a straight-chained or branched C1 4 alkyl or a C24 alkynyl group,
X stands for a hydrogen atom or a straight-chained or branched C, 4 alkoxy group,
Y denotes hydrogen, or
X and Y together represents a double bond.
The compounds of the general formula (I) are useful for the control of insects.
Ethyl [(E)-3,5-ethano-7,1 1-dimethyl-2,4-dodecadienoate], a representative of the compounds of the general formula (I), showed remarkable potency on different insect species [C.A. Henrick,
J.N. Labovitz, V.L. Graves and G.B. Staal: Bioorg. Chem.], 235-250(1978)3. Its effectivity against yellow-fever mosquito (Aedes aegypti) is three times, against greater wax moth (Galleria mellonella) is ten times, against yellow mealworm (Tenebrio molitor) and tobacco budworm (Heliothis virescens) is a hundred times and against house fly (Musca domestica) is a thousand times as high as that of Hydroprene (trademark Altozar). The other derivatives of the general formula (I) are also highly effective in controlling many insect species. The (E) isomers are far mor effective than the (Z) isomers.
For the preparation of the dodecadienoates of the general formula (I) two methods have been published (USA patent specifications Nos. 4 058 666 and 4 000 174). The starting substances of both processes are the 2-cyclopentenone derivatives of the general formula (II),
wherein X and Y are as defined above.
According to the first of these processes the 2-cyclopentenones of the general formula (II) are reacted with lithium salts derived from alkyl [trimethylsilylacetates3. According to the other known method 3-(2,6-dimethylheptyl)-cyclopent-2-en-1-one, a representative of the compounds of the general formula (II), is converted with a mixture of lithium diisopropylamide and ethyl acetate into ethyl (7,1 1-dimethyl-3,5-ethylene-3-hydroxy-4-dodecenoate), which is then reacted with phosphoryl chloride.
In both processes a 1:1 mixture of the (E) and (Z) isomers is obtained, which is subjected to thin layer chromatography to obtain the individual isomers.
A serious disadvantage of the known processes is the unfavourable isomeric ratio (1:1).
Besides, these methods are uneconomical because of the expensive reactants [e.g. alkyl(trimethylsilylacetate), alkyl lithium].
The aim of the present invention is to provide a synthesis devoid of the above drawbacks, which is economical also on an industrial scale.
It has been found that the compounds of the general formula (I) can be obtained with a favourable isomeric ratio proceeding as follows:
a.) To prepare a subgroup of the compounds having the general formula (I), wherein R' represents a straight-chained or branched alkyl group and X and Y are as defined above, an anion derived from a phosphoric acid derivative of the general formula (III),
wherein R' and R2 each represent a straight-chained or branched C14 alkyl group, with a base in a dipolar-aprotic or protic solvent, is reacted with a compound of the general formula (it).
wherein X and Y are as defined above, preferably at a temperature between 20"C and 90"C; or
b.) to prepare a subgroup of the compounds having the general formula (I), wherein R1 represents a C24 alkynyl group and X and Y are as defined above, an ester of the general formula (I), wherein R' stands for a straight-chained or branched C14 alkyl group and X and Y are as defined above, is reacted with a base in an alcohol or in the mixture of an alcohol and water, the carboxylic acid thus obtained is halogenated, and the halide thus obtained is reacted with a C24 alkynol.
In the reaction an isomeric mixture containing 70 to 75% of 2(E) isomer and 25 to 30% of 2(Z) isomer is formed, which is separated into the individual isomers by column chromatography.
The compounds of the general formula (II) used as starting substances for the process described in variant a.) are known and can be prepared e.g. as specified in Hungarian patent specification No. 180 635. The phosphoric acid derivatives of the general formula (Ill) can be derived from trialkyl phosphites via an Arbuzow reaction with haloacetic acid esters [B A.
Arbazew: Pure Appl. Chem. 9, 307/1964)].
The anions derived from the compounds of the general formula (III) can be formed with inorganic or organic bases (e.g. metal alcoholates, hydrides, alkali amides, alkyl or aryl lithium or potassium metal). It is preferable to use metal alcoholates, such as sodium ethylate or potassium tert. butylate. The reaction is carried out in a dipolar-aprotic or protic solvent or in the mixture thereof. As dipolar-aprotic solvent preferably dimethylformamide, hexamethylphosphorus triamide or dimethyl sulfoxide can be used. As protic solvents, preferably alkanols are used. The reaction is preferaly performed at a temperature between 20"C and 90on.
According to variant b.) of the process according to the invention the alkynyl esters of the general formula (I) are produced. For this purpose the corresponding alkyl esters are reacted with a base in an alcohol or in the mixture of an alcohol and water. As base inorganic bases (e.g. alkali hydroxides or carbonates) can be used. The acid thus obtained is halogenated by methods known per se, finally the resulting halide is reacted with a C24 alkynol, preferably in an apolar solvent. As apolar solvent, preferably benzene, pentane, hexane or cyclohexane are used.
ihe invention is illustrated in detail by the aid of the following non-limiting Examples:
Example 1
Preparation of isopropyl UE)-3,5-etliano-7, 11-dimethyl-2,4-dodecadienoate] [1; R' = (CH3)2CH,
X=Y= H]
0.9 g (0.008 mole) of potassium tert. butylate is suspended in 8 ml of anhydrous dimethylformamide, and a solution of 1.88 g (0.008 mole) of isopropyl (diethoxyphosphoryl acetate) [III; R1 = (CH3)2CH, R2 = CH3-CH21 in 8 ml of anhydrous dimethylformamide is added to it under argon.The reaction mixture is stirred for half an hour at room temperature and a solution of 0.83 g (0.004 mole) of 3-(2,6-dimethylheptyl)-2-cyclopentenone in 5 ml of an hydros dimethylformamide is added to it, and the mixture is stirred at 70"C for 6 hours. The dimethylformamide is distilled off in vacuo, the residue is taken up in 1 5 ml of ice-water, extracted five times with a total amount of 100 ml of ether, the ethereal phases are combined, washed with water and saturated sodium chloride solution, dried over magnesium sulfate and the solvent is distilled off.
According to high-pressure liquid chromatography the product thus obtained contains a 72:28 ratio of the (E) and (Z) isomers, which are separated by low-pressure column chromatography (Kieselgel G, hexane-ethyl acetate 95:5, 1-1.5 bar).
Yield of the (E) isomer: 0.57 g (48.6%) Ref = 0.38 (hexane-ethyl acetate 95:5) HPLC column: CH romsil 10 ym, L = 300 mm, dp = 4.6 mm, Du Pont 830, detection 254
nm, F = 2 cm3 (min.Ap = 300 PSI, eluent: hexane-ethyl acetate 97: 3] tR = 5 min.
IR (NaCI): 1710 (CO), 1620 (C = C), 1470, 1385, 1370, 1260,
1200, 1140, 1105, 1000, 965, 830 cm~1.
'H-NMR (CCl4): 8 0.75 (9H, d, J = 6 Hz, 3CH2, 1.1 (6H, d,
J = 6 Hz, 2CH3), 1.2-2.95 (14H, m, 6CH2,
2CH), 4.71 (1H, q, J = 6 Hz, O-CH), 5.3
(1H,mc,C2C=CH), 5.75 (1H, mc,C4C=CH).
Yield of the (Z) isomer: 0.20 9 (17%)
Rf=0.46 tR=6.1 min.
IR(NaCI): 1705, 1615, 1470, 1390, 1370, 1265, 1200, 1140,
1105, 995, 965, 830cm-1.
H-NMR (CCl4): S 0.75 (9H, d, J = 6 Hz, 3CH3), 1.1 (6H, d,
J = 6Hz, 2CH3), 1.2-2.95 (14H, m, 6CH2, 2CH), 4.7 (1 H, q, J = 6 Hz, OCH), 5.2
(1H,mc,C2C=CH),6.9(1H,mc,C4C=CH).
Example 2
Preparation of ethyl [(E)-3,5-ethano-7,11-dimethyl-2,4-dodecadienoate] (I; R1 = CH3-CH2, X = Y = H)
To a suspension of 2.42 9 (0.02 mole) of potassium tert. butylate in 15 ml of anhydrous dimethylformamide a solution of 4.48 9 (0.02 mole) of ethyl (diethoxyphosphoryl acetate) (III; R' = R2 = CH3CH2) in 10 ml of anhydrous dimethylformamide is added, and the reaction mixture is stirred under argon for half an hour. Then a solution of 1.46 9 (0.007 mole) of 3-(2,6dimethylheptyl)-2-cyclopentenone (II; X = Y = H) in 10 ml of dimethylformamide is added to the mixture, and it is stirred at 60 C for 10 hours.The solvent is distilled off in vacuo, the reCiclue is taken up in 25 ml of ice-water, extracted 3 times with a total amount of 100 ml of ether, the ether phases are combined, washed with water and brine, dried over magnesium sulfate and the solvent is distilled off.
According to high-pressure liquid chromatography the residual product contains a 70:30 ratio of the (E) and (Z) isomers, which are separated by low-pressure column chromatography (Kieselgel 60, 0.02-0.2; hexane-ethyl acetate 95:5, 1-1.5 bar).
Yield of the (E) isomer: 0.89 9 (45.5%)
R4 = 0.2 (hexane-ethyl acetate 95:5) tR = 10.83 min (hexane-dichloromethane 98: 2) 'H-NMR (CDCl3): 8 0.87 (9H, d, J = 6 Hz, 3CH3), 1.28 (3H, t J = 7 Hz, CH3), 1.1-2.6 (1 2H, m, 5CH), 3.04 (2H, m, CH2), 4.1 5 (2H, q, J = 7 Hz, 0-CH2),
5.63 (1H, t, J= 1.5Hz, C2 C=CH), 6.0 (1H,
m, C4 C = CH).
Ms: M+ 278 (75), 233 (23), 193 (44), 166 (100), 138 (31),
120(21), 91(38), 77 (14), 71(23), 57(41), 43
(64).
Yield of the (Z) isomer: 0.34 9 (17.3%)
Rf=0.3 tR= 16.0 min.
'H-NMR (CDCl3): # 0.86 (9H, d, J = 6 Hz, 3CH3), 1.28 (3H, t, J = 7 Hz, CH3), 1.1-2.7 (14H, m, 6CH2, 2CH),
4.15 (2H, q, J = 7 Hz, OCH2), 5.45 (1H, m,
C2 C=CH), 7.12 (1H, m, C4 C=CH).
Ms: M+ 278 (75), 233 (23), 193 (44), 166 (100), 138 (31),
120(21), 91(38), 77 (14), 71(23), 57 (41), 43
(64).
Example 3
Preparation of ethyl [(E)-3,5-ethano-7, 1 t-dimethyl-1 l-methoxy2,4-dodecadienoatej (I; R1=CH3-CH2, X = OCH3, Y = H)
To a suspension of 2.24 9 (0.02 mole) of potassium tert. butylate in 10 ml of anhydrous dimethylformamide a solution of 4.48 g (0.02 mole) of ethyl (diethoxyphosphoryl acetate) (Ill; R1 = R2 = CH3-CH2) in 10 ml of anhydrous dimethylformamide is added, and the suspension thus obtained is stirred under nitrogen for half an hour. Then a solution of 2.38 g (0.01 mole) of 3-(2,6-dimethyl-6-methoxyheptyl)-2-cyclopentenone (ill; X = OCH3, Y = H) in 10 ml of anhydrous dimethylformamide is added to the mixture and it is stirred at 70"C for 8 hours.The solvent is distilled off in vacuo, the residue is taken up in 30 ml of ice-water, extracted five times with a total amount of 100 ml of ether, the ethereal phases are combined, washed successively with water and brine, dried over magnesium sulfate and the solvent is distilled off.
According to high-pressure liquid chromatography the residual product contains a 72:28 ratio of the (E) and (Z) isomers, which are separated by column chromatography (Kieselgel G, hexaneacetone 7:3).
Yield of the (E) isomer: 1.45 g (46.9%) R,= = 0.45 (hexane-acetone 7:3) tR = 1.4 min. (hexane-ethyl acetate 95:5) H-NMR (CCI4): S 0.85 (3H, d, J = 6 Hz, CH3), 1.0 (6H, s,
2CH3), 1.2 (3H, t, J = 7 Hz, CH3), 1.15-2.8
(13H, m, 6CH2, CH), 3.0 (3H, s, OCH3), 4.0
(2H, q, J = 7 Hz, OCH2), 5.5 (1 H, m, C2 C = CH),
5.9 (1H, m, C4 C = CH).
Yield of the (Z) isomer: 0.54 g (17.4%) Ref=0.5 tR = 2.9 min.
H-NMR (CCl4): S 0.8 (3H, d, J = 6 Hz, Cm2), 1.1-2.8 (13H, m,
6CH2, CH), 0.95 (6H, s, 2CH3), 1.25 (3H, t,
J = 7 Hz, CH3), 2.95 (3H, s, OCH2), 4.0 (2H, q,J=7Hz,0CH2),5.4(1H, m, C2C=CH),7.05 (1H, m, C4 C = CH).
Example 4
Preparation of isopropyl f(E)-3,5-ethano-7, 11--dimethyl-1 1-methoxy-2,4-dodecadienoate] [1;
R' = (CH3)2-CH, X = OCH3, Y = H]
To a suspension of 2.24 g (0.02 mole) of potassium tert. butylate in 15 ml of anhydrous hexamethylphosphorus triamide a solution of 4.76 g (0.02 mole) of isopropyl (diethoxyphosphoryl acetate) [III; R1 = (CH3)2CH, R2 = CH3-CH2] in 10 ml of anhydrous hexamethylphosphorus triamde is added, and the mixture is stirred at room temperature for half an hour, under argon.
Then a solution of 2.38 g (0.01 mole) of 3-(2,6-dimethyl-6-methoxyheptyl)-2-cyclopentenone (ill; X = OCH3, Y = H) in 10 ml of anhydrous hexamethylphosphorus triamide is added to it, and the mixture is stirred at 70"C for 8 hours. The solvent is distilled off in vacuo, the residue is taken up in ice-water, extracted five times with a total amount of 100 ml of ether, the ethereal phases are combined, washed with water and saturated sodium chloride solution, dried over magnesium sulfate and the solvent is distilled off.
According to high-pressure liquid chromatography the residual product contains a 70:30 ratio of the (E) and (Z) isomers, which are separaed by column chromatography (Kieselgel 60, hexane-acetone 7:3).
Yield of the (E) isomer: 1.4 9 (43.3%)
R4 = 0.37 (hexane-ethyl acetate 91:9) tR = 5 min. (hexane-ethyl acetate 97:3)
IR (NaCI): 1705 (CO), 1615 (C = C), 1470, 1385, 1365, 1260, 1205, 1105, 1080, 995cm-'.
'H-NMR (CCI4): 50.9 (3H, d, J = 6Hz, CH3), 1.1 (6H, d, J = 6 Hz, 2CH3), 1.2 (6H, s, 2CH3), 1.2-2.8 (13H,
m 6CH2, CH), 2.95 (3H, s, OCH2), 4.9 (1 H, J = 6 Hz, OCH), 5.55(1 H, m, C2 C = CH), 6.0
(lH, m, C4 C=CH).
Yield of the (Z) isomer: 0.62 g (19.2%) Rf= 0.43 tR=6.1 min.
IR (NaCI): 1700 (CO), 1610 (C = C), 1460, 1385, 1365,
1260, 1205, 1080, 990 cm ~ ' .
'H-NMR (CCl4): 50.95 (3H, d, J = 6Hz, CH3), 1.1 (6H, d, J = 6 Hz, 2CH3), 1.2 (6H, s, 2CH2), 1.2-2.8 (13H,
m, 6CH2, CH), 2.9 (3H, s, OCH3), 4.9 (1H, q, J = 6 Hz, -OCH), 5.4(1 H, m, C2 C = CH), 7.2 (1H, m, C4 C = CH).
Example 5
Preparation of ethyl F(E)-3, 5-ethano-7, 1 1-dimethyl- 1 1-methoxy-2,4-dodecadienoate] (I,
R1 = CH2-CH2, X = OCH3, Y = H)
To a solution of 1.6 g (0.02 mole) of sodium ethylate in 10 ml of ethanol a solution of 4.48 g (0.02 mole) of ethyl (diethoxyphosphoryl acetate) (III; R' = R2 = CH2-CH3) in 1 5 ml of anhydrous ethanol is added, and the mixture is stirred at room temperature for half an hour, under argon. Then a solution of 2.38 g (0.01 mole) of 3-(2,6-dimethyl-6-methoxyheptyl)-2cyclopentenone (ill; X = SOCH2, Y = H) in 10 ml of anhydrous ethanol is added to it, and the reaction mixture is stirred at 70"C for 8 hours.The solvent is distilled off in vacuo, the residue is taken up in 25 ml of ice-water, extracted thrice with a total amount of 90 ml of ether, the extracts are combined, washed successively with water and brine, dried over magnesium sulfate and the solvent is distilled off in vacuo.
According to liquid chromatography the residual product contains a 70:30 ratio of the (E) and (Z) isomers. After separation by column chromatography 1.22 g (39.5%) of (E) and 0.48 g (15.5%) of (Z) isomer are obtained. The compounds are identical to the products prepared according to Example 3.
Example 6
Preparation of isopropyl f(E)-3, 5-ethano-7, 1 1-dimethyl- 1 1 -methoxy-2, 4-dodecadienoate] [I;
R' = (CH2)2CH, X = SOCH2, Y = H]
To a suspension of 2.24 g (0.02 mole) of potassium tert. butylate in 1 5 ml of anhydrous dimethylformamide a solution of 5.3 g (0.02 mole) of isopropyl (diisopropoxyphosphoryl acetate) [III; R' = R2 = (CH2)2CH] in 10 ml of anhydrous dimethylformamide is added, and the mixture is stirred at room temperature for half an hour, under nitrogen.Then a solution of 2.38 9 (0.01 mole) of 3-(2,6-dimethyl-6-methoxyheptyl)-2-cyclopentenone (ill; X = OCH3, Y = H) in 10 ml of anhydrous dimethylformamide is added to it, and the reaction mixture is stirred at 70"C for 6 hours. The dimethylformamide is distilled off in vacuo, the residue is taken up in icewater, extracted with ether, the ethereal extract is washed successively with water and brine, dried over magnesium sulfate and the solvent is distilled off.
According to liquid chromatography the residual product contains a 75:25 ratio of the (E) and (Z) isomers, which are separated by low-pressure column chromatography.
Yield of the (E) isomer: 1.55 g (48.0%)
Yield of the (Z) isomer: 0.53 g (16.4%)
The compounds are identical to the products prepared according to Example 4.
Example 7
Preparation of propargyl f(E)-3,5-ethano-7, 1 1-dimethyl-l 1-methoxy-2, 4-dodecadienoate] [I;
R' = CH=C-CH2, X = OCH3, Y = H)
1.5 g (0.00465 mole) of isopropyl ((E)-3,5-ethano-7,1 1-dimethyl-1 1-methoxy-2,4-dodecadie- noate] [I; R1 = (CH3)2CH, X = OCH3, Y = H] are dissolved in the mixture of 10 ml of methanol and 7 ml of 5N sodium hydroxide solution, and the reaction mixture is warmed on a water-bath of 90"C for 2 hours, under vigorous stirring. Then it is cooled, the alcohol is distilled off in vacuo and the aqueous solution is extracted with ether. The aqueous phase is acidified with 5% sulfuric acid solution under cooling and extracted with ether.The ethereal solution is dried over magnesium sulfate, the solvent is distilled off, the residual carboxylic acid is dissolved in 6 ml of anhydrous dimethylformamide and 0.6 g (0.005 mole) of thionyl chloride is added to it, under cooling. The reaction mixture is stirred at 35"C for half an hour, cooled to room temperature and 50 ml of pentane are added to it. The upper pentane phase is separated, and 0.31 g (0.32 ml, 0.0055 mole) of propargyl alcohol is added to the pentaneous acid chloride solution, under cooling. The mixture is stirred at room temperature for one hour, washed successively with water, 2N sodium hydroxide solution and water again, dried over magnesium sulfate and the solvent is distilled off.
According to liquid chromatography the residual product (1.0 9, 67%) contains a 60:40 ratio of the (E) and (Z) isomers, which are separated by column chromatography.
Yield of the (E) isomer: 0.46 g (31%) tR = 12 min (hexane-methylene chloride-ethyl acetate:83:16:1) 'H-NMR (CCl4): 50.8 (3H, d, J = 6 Hz, CH3), 1.0 (6H, s, 2CH3),
1.05-1.5(7H, 3CH2,CH), 1.9-2.1 (6H, m, 3CH2), 2.2(1 H, t, J = 2 Hz, C = CH), 2.98 (3H, s, OCHA), 4.5 (2H, d, J = 2 Hz, O-CH2), 5.45 (1 H, m, C2 C = CH), 5.9 (1H, m, C4 C = CH).
Ms: M+ 318 (1), 286 (13), 263 (3), 203(7), 147 (6), 91
(18), 73 (100), 55 (23), 41(21), 39 (11).
Yield of the (Z) isomer: 0.23 g (15.5%) tR= 14 min.
H-NMR (CC14) 5 0.8 (3H, d, J = 6 Hz, CH3), 1.0 (6H, s,
2CH3), 1.05-1.5 (7H, 3CH2, CH), 1.9-2.1
(6H, m, 3CH2), 2.25 (1 H, t, J = 2 Hz, C = CH),
3.0 (3H, s, OCH3), 4.55 (2H, d, J = 7 Hz,
O-CH2), 5.3 (1 H, m, C2 C = CH), 7.0 (1 H, m, C4 C = CH).
Claims (8)
1. A process for the preparation of 3,5-ethano-2,4-dodecadienoates of the general formula (1),
wherein
R' represents a straight-chained or branched C1-4 alkyl or a C24 alkynyl group,
X stands for a hydrogen atom or a straight-chained or branched C14 alkoxy group,
Y denotes hydrogen, or
X and Y together represent a bond, characterized by
a.) to prepare a subgroup of the compounds having the general formula (I), wherein R' represents a straight-chained or branched alkyl group and X and Y are as defined above, reacting an anion derived from a phosphoric acid derivative of the general formula (III),
wherein R1 and R2 each represent a straight-chained or branched C1-4 alkyl group, with a base in a dipolaraprotic or protic solvent, with a compound of the general formula (Il),
wherein X and Y are as defined above, preferably at a temperature between 20 C and 90 C; or
b.) to prepare a subgroup of the compounds having the general formula (I), wherein R' represents a C24 alkynyl group and X and Y are as defined above, reacting an ester of the general formula (I), wherein R' stands for straight-chained or branched C1-4 alkyl group and X and Y are as defined above, with a base in an alcohol or in the mixture of an alcohol and water, halogenating the carboxylic acid thus obtained, and reacting the halide thus obtained with a C24 alkynol.
2. A process as claimed in variant a.) of claim 1, characterized by using a metal alcoholate, preferably sodium ethylate or potassium tert. butylate as base.
3. A process as claimed in variant a.) of claim 1, characterized by using dimethylformamide or hexamethylphosphorus triamide as dipolar-aprotic solvent.
4. A process as claimed in variant a.) of claim 1, characterized by using an alkanol as protic solvent.
5. A process as claimed in variant b.) of claim 1, characterized by using inorganic bases, preferably an alkali hydroxide, as base.
6. A process as claimed in variant b.) of claim 1, characterized by using propargyl alcohol as alkynol.
7. A process as claimed in claim 1 substantially as hereinbefore described in any one of
Examples 1 to 7.
8. A compound of the general formula I, wherein X, Y and R' are as defined in claim 1, when made by a process in any one of claims 1 to 7.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
HU834362A HU193546B (en) | 1983-12-21 | 1983-12-21 | Process for production of derivatives of 3,5-ethan-2,4-dedecadiene acid |
Publications (2)
Publication Number | Publication Date |
---|---|
GB8432497D0 GB8432497D0 (en) | 1985-02-06 |
GB2151625A true GB2151625A (en) | 1985-07-24 |
Family
ID=10967753
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB08432497A Withdrawn GB2151625A (en) | 1983-12-21 | 1984-12-21 | Process for the preparation of 3,5-ethano-2-2,4-dodecadienoates |
Country Status (9)
Country | Link |
---|---|
JP (1) | JPS60214758A (en) |
DE (1) | DE3447727A1 (en) |
ES (1) | ES8605758A1 (en) |
FI (1) | FI845080L (en) |
FR (1) | FR2557100A1 (en) |
GB (1) | GB2151625A (en) |
HU (1) | HU193546B (en) |
IT (1) | IT1177468B (en) |
NL (1) | NL8403886A (en) |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4000174A (en) | 1974-04-29 | 1976-12-28 | Zoecon Corporation | Novel compounds |
US4058666A (en) * | 1975-06-25 | 1977-11-15 | Zoecon Corporation | 3,5-Lower alkylene carboxylic esters |
CH616077A5 (en) * | 1976-06-30 | 1980-03-14 | Firmenich & Cie |
-
1983
- 1983-12-21 HU HU834362A patent/HU193546B/en unknown
-
1984
- 1984-12-20 IT IT24141/84A patent/IT1177468B/en active
- 1984-12-20 FR FR8419526A patent/FR2557100A1/en not_active Withdrawn
- 1984-12-20 JP JP59267567A patent/JPS60214758A/en active Pending
- 1984-12-20 FI FI845080A patent/FI845080L/en not_active Application Discontinuation
- 1984-12-21 ES ES538925A patent/ES8605758A1/en not_active Expired
- 1984-12-21 DE DE19843447727 patent/DE3447727A1/en not_active Withdrawn
- 1984-12-21 GB GB08432497A patent/GB2151625A/en not_active Withdrawn
- 1984-12-21 NL NL8403886A patent/NL8403886A/en not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
DE3447727A1 (en) | 1985-07-04 |
IT8424141A0 (en) | 1984-12-20 |
NL8403886A (en) | 1985-07-16 |
JPS60214758A (en) | 1985-10-28 |
HUT37909A (en) | 1986-03-28 |
FI845080L (en) | 1985-06-22 |
IT1177468B (en) | 1987-08-26 |
HU193546B (en) | 1987-10-28 |
ES8605758A1 (en) | 1986-04-16 |
FR2557100A1 (en) | 1985-06-28 |
GB8432497D0 (en) | 1985-02-06 |
FI845080A0 (en) | 1984-12-20 |
ES538925A0 (en) | 1986-04-16 |
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Legal Events
Date | Code | Title | Description |
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WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |