GB2100728A - 3-substituted-2- cyclopentenone derivatives - Google Patents
3-substituted-2- cyclopentenone derivatives Download PDFInfo
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- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
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- C07C45/66—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups by dehydration
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- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
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Abstract
3-Substituted-2-cyclopentenone derivatives of the general formula (I> <IMAGE> wherein R<1> and R<2> represent independently from each other a hydrogen atom or a straight-chained or branched C1-4 alkyl group, R<3> stands for a hydrogen atom or a C1-4 alkoxy group, Y represents hydrogen, or R<3> and Y together represent an oxygen atom or a double bond, are prepared by a) reacting a 2,5-dodecanedione derivative of the general formula (II), <IMAGE> with an alkali or alkaline-earth hydride or a lithium-(di-C1-6 alkyl amide) in an aprotic solvent, and reacting further the compound of the general formula (III) thus obtained, <IMAGE> with an acid; or b) reacting a compound of the general formula (III) with a base. The compound of the general formula (I) are - with the exception of one derivative - new and they serve as intermediates for the preparation of derivatives possessing valuable insect control activity.
Description
SPECIFICATION
Process for the preparation of 3-substituted-2cyclo-pentenone derivatives
The invention relates to a process for the preparation of 3-substituted-2-cyclopentenone derivatives of the general formula (I),
wherein
R' and R2 represent independently from each other a hydrogen atom or a straight-chained or branched C,, alkyl group,
R3 stands for a hydrogen atom or a C,, alkoxy group,
Y represents hydrogen, or
R3 and Y together represent an oxygen atom or a double bond.
The compounds of the general formula (I) can serve as intermediates for the preparation of the derivatives of the general formula (IV),
wherein
R', R2, R3 and Y have the same meanings as above, and R is a straight-chained or branched alkyl group.
The latter compounds are useful for the control of insects.
One of the compounds of the general formula (I), wherein R1, R2, R3 and Y each stand for hydrogen, is known. The other derivatives of the general formula (I) have not so far been described.
In accordance with the invention even the known derivative is prepared by a new procedure.
The only known derivative of the general formula (I) was used for the preparation of the compounds of the general formula (IV), wherein
R1, R2, R3 and Y each represent hydrogen atom and R4 is ethyl group [C. A. Henrick and al.: Bioorg.
Chem. 7, 235(1978)]. The authors have found that the compound thus prepared is highly effective in controlling many insect species. Its effectivity against yellow-fever mosquito (Aedes aegypti) is twice, against greater wax moth (Galleria mellonelia) is ten times, against yellow mealworm (Tenebrio monitor) and tobacco budworm (Heliothis virescens) is a hundred times, against house fly (Musca domestica) is a thousand times as high as that of Hydroprene.
For the preparation of the cyclopentenone derivatives used as intermediates two methods are known [Bioorganic Chemistry 7, 235 (1978)].
According to the first of these processes 2,6dimethyl-1-heptene was used as starting substance. It was reacted with diborane to yield the corresponding trialkylborane. The latter compound was reacted first with bromine, then with sodium methoxide. The 1-bromo-2,6dimethylheptane thus obtained was converted into Grignard reagent with magnesium metal in ether, and then reacted with 3-methoxycyclopent 2-en-1 -one prepared from 1,3-cyclopentanedione with diazomethane. Finally water was split off from the 3-(2,6-dimethylheptyl) cyclopent-2-en-1 -one thus obtained with acid to result the cyclopentenone derivative of the general formula (I) (wherein R=R2=R3=Y=H) in a poor yield (13 %).
This process is uneconomic because of the expensive starting substances and reactants (diborane, diazomethane) and the very low yield.
Besides, the method is unsuitable for the preparation of compounds of the general formula (I) containing an alkoxy group [(ll): R3=O-alkyl] because of the well-known acid sensitivity of the compounds containing such a group.
According to an improved method of C. A.
Henrick et al., 2,6-dimethyl-1-heptene was used as starting substance. This compound was hydroborated into 1-hydroxy-2,6-dimethyl- heptane, which was converted into 1-chloro-2,6dimethylheptane with thionyl chloride. This chloro compound was converted with lithium metal into the corresponding alkyllithium derivative, which was then reacted with 2-cyciopentenone obtained by brominating cyclopentanone and subsequently splitting off hydrogen bromide from the compound thus obtained. The 1-hydroxy-1 (2,6-dimethylheptyl)-2-cyclopentene thus prepared was oxidized with chromic acid (chrome oxide and sulfuric acid) in ethereal solution to obtain the cyclopentenone derivative of the general formula (I), wherein R1, R2, R3 and Y each respresent hydrogen. Though the yield of this process is higher than that of the previous one, it has several disadvantages.Beside the fact that it requires expensive starting substances and reactants, this synthesis is not suitable for the preparation of derivatives containing an alkoxy group (that is compounds of the general formula (I), wherein R3 is alkoxy) because of the strongly acidic reagents used in two reaction steps.
The aim of the present invention is to provide a simple and economic synthesis for the preparation of the compounds of the general formula (I), which can be used for the production of the known (R1=R2=R3=H, R4=ethyl) and the new compounds of the general formula (IV) possessing valuable biological properties.
It has been found, that both the known derivative and the new ones of the general formula (I) can be produced in fewer reaction steps from the new 2,5-dodecanedione derivatives of the general formula (II),
wherein
R', R2, R3 and Y are as defined above, by a.) reacting a 2,5-dodecanedione derivative of
the general formula (II)-wherein R1, R2, R3
and Y are as defined above-with an alkali
or alkaline-earth hydride or a lithium-(di-C1e alkyl amide) in an aprotic, preferably ether
type solvent, and reacting the compound of
the general formula (III) thus obtained
wherein
R1, R2, R3 and Y are as defined above, with an acid; or
b.) reacting a compound of the general formula (ill) wherein R1, R2, R3 and Y are as defined
above, with a base, preferably in a solvent, and optionally separating the thus-obtained compound of the general formula (I) from the reaction mixture.
When carrying out the reaction with an alkali hydride, preferably sodium or potassium hydride is used. As lithium-(di-C16 alkyl amide), preferably lithium-(diethyl amide) or lithium (diisopropyl amide) is used.
When proceeding according to variant a.) of the invention, preferably ether-type solvents (such as diethyl ether, dioxane, tetrahydrofurane, etc.) are used as aprotic solvents.
The intermediate of the general formula (III) obtained according to variant a.) need not be isolated; it can be converted into the desired compound of the general formula (I) without external measures, by the effect of the catalytic amount of acid present in the reaction mixture.
When proceeding as described in variant b.) of the process according to the invention, a compound of the general formula (III) is reacted with a base. The reaction is preferably carried out in an organic solvent. As base, preferably alkali or alkaline-earth hydroxides or hydrides are used.
When proceeding according to variant a.) of the process according to the invention and using an alkali or alkaline-earth hydride, the reaction may be carried out at a temperature between -200C and 800C, preferably between 0 C and 30"C. When a lithium-(di-C1~6 alkyl amide) is used, one proceeds at lower temperatures, preferably between C and -800C, particularly between -300C and -700C. Whether a metal hydride or a lithium-(di-C18 alkyl amide) is used, the reaction is carried out preferably under inert gas.
According to our investigations, the compounds of the general formula (II) serving as starting substances for the process described in variant a.) are prepared from a citronellal derivative of the general formula (V),
wherein
R', R2, R3 and Y are as defined above, which can be produced from the commercially available citronellal by known methods.For the preparation of the compounds of the general formula (II), a compound of the general formula (V) is reacted with methyl vinyl ketone of the formula (Vl),
in the presence of a catalytic amount of a thiazolium salt of the general formula (VII),
wherein
R5 represents a straight-chained or branched C15 alkyl group, a 2-hydroxyethyl group or a benzyl group, Re is hydrogen or C13 alkyl,
R7 stands for a straight-chained or branched C14 alkyl or a 2-hydroxyethyl group, and
X- is a halide ion.
The reaction is optionally carried out in an organic solvent-preferably in anhydrous dioxane-at a temperature not too high, preferably between 650C and 800C. Related to the amount of the catalyst, at least one equivaient of base-preferably trialkylamine-is used. The product is isolated from the reaction mixture by extraction or by vacuum distillation.
The term "alkyl group" used in the specification and claims refers to straight-chained or branched alkyl groups (e.g. methyl, ethyl, npropyl, isopropyl or n-butyl). The term alkoxy" relates to straight-chained or branched alkoxy groups containing 1 to 4 carbon atoms (e.g. methoxy, ethoxy, n-propoxy or isobutoxy.
The "halide ion" can be chloride, bromide or iodide ion, and it represents preferably chloride ion.
The invention is illustrated by the following
Examples of non-limiting character:
Example 1
Preparation of 7,11 -dimethyl-1 1 -methoxy-2,5- cyclododecanedione [(II): R'=R2=Y=H;
R3=OCH3]
A mixture of 37.3 g (0.2 mole) of 7-methoxy6,7-di-hydrocitroneilal [(V): R1=R2=Y=H; R3=oCH3], 21 g (0.3 mole) of distilled methyl vinyl ketone (Vl) and 5 g (0.02 mole) of 3-benzyl5-(2-hydroxyethyl)-4-methylthiazolium chloride [(VI I): R5=benzyl, R6=CH3, R7=-CH2-CH2-OH, X=CI] is warmed to 70"C, 3.64 g (5 ml, 0.036 mole) of anhydrous triethylamine are added, and the reaction mixture is stirred at 75OC for 16 hours, under argon. Then it is cooled, poured onto a mixture of 150 ml of 5% by weight aqueous sulfuric acid solution and 15 g of ice, then extracted twice with a total amount of 300 ml of dichloromethane. The extract is washed successively with 20 ml of water, 20 ml of 5% sulfuric acid solution, 20 ml of water, and dried over magnesium sulfate. The solvent is distilled off, and the residue is distilled under reduced pressure (0.2 mmHg).
Yield: 23 g (44.9%)
B.p.: 110-1 140C/0.2 mm.
Analysis: C15H2803 (256.37)
Calculated: C%=70.26 H%=11.15
Found: C%=69.98 H%=11.00 IR(NACI): 1715, 1460, 1400, 1380, 1360,
1150,1070 cm-'.
1H-NMR(CCl4): 0.9 (3H, d, J=6 Hz, CH3), 1.1
(6H, s, 2CH3), 1.3 (6H, mc, 3CH2), 2.1 (3H, s, CH3), 2.58 (4H, s, 2CH2), 3.08 (3H, s, OCH3).
Ms: M+ 256 (2%), m/e 241 (10), 226(15), 225 (20), 210(10), 186(25), 131(8), 99 (90), 73 (100), 43 (95).
Example 2
Preparation of 3-(2,6-dimethyl-6-methoxy heptyl )-3-hydroxycyclopentanone [(Ill): R1=R2=Y=H; R3=OCH3] and 3-(2,6-dimethyl-6methoxyheptyl)-2-cyclopentenone [(I):
R=R=Y=H; R =OCH3]
To a suspension of 0.5 9 (0.0176 mole) of sodium hydride (80% by weight oily suspension) in 20 ml of anhydrous ether a solution of 2.56 g (0.01 mole) of 7,11-dimethyl-11-methoxy-2,5- dodecanedione [(ll); R1=R2=Y=H, R3=OCH3] in 10 ml of anhydrous ether is dropped under argon, within half an hour, under stirring. Then the mixture is stirred at room temperature for 6 hours.
Finally it is poured onto icy water, the organic phase is separated, the aqueous phase is extracted with 20 ml of ether, the organic phases are combined and washed with water, dried over magnesium sulfate, the solvent is distilled off, and the residual oily product is purified by chromatography (Kieselgel G; benzene-methanol
10:0.2).
3-(2,6-Dimethyl-6-methoxyheptyl)-3-hydroxycyclopentanone
Yield: 0.80 9 (31.3 %)
Rf=0.25 (benzene-methanol 10.1)
IR(NaCl): 3410, 1720, 1460, 1380, 1350,
1230, 1140, 1060 cm-1.
'H-NMR(CDCI3): 0.9 (3H, d, J=6 Hz, CH3), 1.05
(6H, s, 2CH3), 1.3 (6H, mc, 3CH2), 2.1 (4H, mc, 2CH2), 2.55 (2H, mc, CH2), 3.05 (3H, s, OCH3), 3.55 (1 H, mc, it can be changed to
deuterium, OH).
Ms: M+ 256 (1%), m/e 238 (2), 207 (37), 206 (2), 188(11), 183(3), 150(2), 135(3), 123
(4), 109(5), 108(4), 96(3), 93(5), 91(7), 85 (8), 81(5), 73 (100).
3-(2,6-Dimethyl-6-methoxyheptyl)-2-cyclopentenone
Yield: 0.45 g (18.9%) Rf=0.47 (benzene-methanol 10.1).
Analysis: C15H2 O2 (238.36)
Calculated: C%=75.58 H%=11.00
Found: C%=75.07 H%=10.72
IR(NaCl): 1705, 1615, 1460, 1430, 1400,
1380, 1360, 1270, 1240, 1160, 1070
cm-1.
1H-NMR(CCl4):0.9 (3H, d, J=6 Hz, CH3), 1.05
(6H, s, 2CH3), 1.3 (6H, mc, 3CH2), 2.3 (6H,
mc+m, 3CH2), 3.03 (3H, s, OCH3), 5.75 (1 H, m,=CH).
Ms: M+ 238 (1%), M/e 223 (1),207 (3), 165
(4), 151(2), 135(2), 124(3), 123(7), 109 (3), 108 (2), 96 (8), 95 (7), 93 (4), 85 (11), 81(8), 73 (100).
As side-product, 0.24 g (10.08%) of 2-(1,5dimethyl-5-methoxyhexyl)-3-methyl-2-cyclopentenone was formed.
R1=0.64 (benzene-methanol 10:1).
Analysis: C1sH2ssO2 (238.36)
Calculated: C%=75.58 H%=11.0
Found: C%=75.42 H%=11.21
IR(NaCI): 1690, 1630, 1460, 1380, 1360,
1200, 1070 cm-1.
'H-NMR(CDCI3): 1.05 (6H, s, 2CH3), 1.1-1.7
(10H, m, 3CH2, CH, CH3), 2 (3H, s, CH3), 2.4
(4H, m, 2CH2), 3.02 (3H, s, OCH3).
Ms: M+ 238 (2%), m/e 223 (1), 206 (5), 151
(10), 150 (7), 135 (7), 124 (6), 123 (6),
109 (3), 95 (4), 93 (4), 91(3), 85 (2), 81
(6), 73 (100).
Example 3
Preparation of 3-(2,6-dimethyl-6-methoxyheptyl)-2-cyclopentenone [(I): R1=R2=Y=H, R3=OCH3] To a stirred suspension of 2 9 (0.36 mole) of sodium hydride (80% oily suspension) in 30 ml of anhydrous ether a solution of 5.12 g (0.02 mole) of 7,11 -dimethyl- 11 -methoxy-2,5-dodecane- dione [(ll): R'=R2=Y=H, R3=OCH3] in 200 ml of anhydrous ether is dropped within half an hour, under nitrogen, and the suspension thus obtained is stirred further for 12 hours at room temperature. Then the reaction mixture is poured onto a mixture of 20 ml of 5% aqueous hydrochloric acid solution and 30 g of ice.The organic phase is separated, the aqueous phase is extracted with 30 ml of ether, the organic extracts are combined, washed with water, dried over magnesium sulfate, and the solvent is distilled off.
The residual product is dissolved in a mixture of 25 ml of ethanol and 50 ml of 0.5 N sodium hydride, and the solution is refluxed for 2 hours.
Then the reaction mixture is cooled to room temperature, extracted twice with a total amount of 100 ml of ether, the ethereal extract is washed with 20 ml of saturated sodium chloride solution, dried over magnesium sulfate, the solvent is distilled off, and the residual oil is purified by column chromatography (Kieselgel 60; benzenemethanol 10:0.2).
Yield: 2.16 g (45.38%), the compound is identical with the product prepared according to
Example 2.
Example 4
Preparation of 3-(2,6-dimethyl-6-methoxyheptyl)-2-cyclopentenone [(I): R1=R2=Y=H, R3=OCH3]
To a stirred solution of 1.3 g (0.013 mole) of anhydrous diisopropylamine and 10 ml of hexamethylphosphorus triamide in 30 ml of tetrahydrofurane held at -650C a 15% by weight solution of 0.9 g (0.014 mole) of butyl lithium in hexane is added under argon, and the mixture is stirred further at -300C for half an hour. Then it is cooled to -65 C, and a solution of 2.56 g (0.01 mole) of 7,11-methoxy-2,5-dodecanedione [(ll): R'=R2=Y=H, R3=OCH3J in 30 ml of anhydrous tetrahydrofurane is dropped within 2 hours. The mixture is stirred at -65 C for one hour, allowed to warm up to room temperature, and stirred further for 3 hours.
The reaction mixture is poured onto water and extracted twice with a total amount of 100 ml of ether. The ethereal extract is washed with water and saturated sodium chloride solution, dried over magnesium sulfate, the solvent is distilled off, and the residue is purified by column chromatography (Kieselgel 60; benzene-methanol 10:0.2).
Yield: 1.0 g (42%), the compound is identical with the product prepared according to Example 2.
Example 5
Preparation of 3-(2,6-dimethyl-6-methoxy heptyl )-2-cyclopentenone [(I): R1=R2=Y=H, R3=OCH3]
1.2 g (0.0047 mole) of 3-(2,6-dimethyl-6methoxy heptyl)-3-hydroxycyclopentenone [(III):
R'=R2=Y=H, R3=OCH3] are dissolved in a mixture of 25 ml of ethanol and 25 ml of 0.5 N sodium hydroxide, and the mixture is boiled for 2 hours.
Then it is cooled to room temperature and extracted twice with a total amount of 100 ml of ether. The ethereal extracts are combined, washed with water and saturated sodium chloride solution, dried over magnesium sulfate, the solvent is distilled off, and the residue is purified by column chromatography (Kieselgel 40, benzene-methanol 10:0.05).
Yield: 0.7 g (63%), the compound is identical with the product prepared according to Example 2.
Example 6
Preparation of 7,1 1-dimethyl-2,5-dodecane- dione [(II): R'=R2=R3=Y=H)
To a solution of 19.5 g (0.125 mole) of dihydrocitronellal [(V): R'=R2=R3=Y=H].14 g (0.2 mole, 16 ml) of freshly distilled methyl vinyl ketone (Vl) and 2.0 g (0.01 mole) of 3-ethyl-5-(2hydroxyethyl )-4-methylthiazolium chloride [(VI I): R5=C2H5, R6=CH3, R7=-CH2-CH2-OH, X-=CI-] in 50 ml of anhydrous dioxane 1.82 g (0.018 mole, 2.5 ml) of triethylamine are added, and the mixture is held on a water bath of 80 C for 24 hours. Then it is cooled, the separated precipitate is filtered off, the solvent is distilled off, and the residue is distilled under reduced pressure (1 mmHg).
Yield: 11 9 (48.7%) B.p.: 103-105 C/0.2 mm; 128130CC/1 mm.
nd25=1.442
Analysis C14H2eO2 (226.35)
Calculated: C%=74.28 H%=11.58
Found: C%=73.96 H%=11.32 IR(NaCl): 1715, 1460, 1380, 1360, 1140,
1080 cm-1.
'H-NMR(CCI4): 0.9 (9H, d, J=6 Hz, 3CH3), 1.2 (6H, mc, 3CH2), 2.1 (3H, s, CH3), 2.2 (2H, m,
CH2), 2.58 (4H, s, 2CH2).
Ms: M+ 226 (5%); m/e 114(100), 113 (29),
99 (46), 71(90), 56 (36).
Example 7
Preparation of 3-(2,6-dimethylheptyl)-3hydroxycyclopentanone[(III): R=R=R =Y=H] and 3-(2,6-dimethylheptyl )-2-cyclopentenone
[(I): R1=R2=R3=y=H] To a stirred suspension of 1.0 g (0.033 mole) of sodium hydride (80% by weight oily suspension) in 40 ml of anhydrous ether a solution of 3.0 g (0.013 mole) of 7,1 1-dimethyl- 2,5-dodecanedione [(Ill: R'=R2=R3=Y=H] in 10 ml of anhydrous ether is dropped within half an hour, under argon, and the reaction mixture is stirred further for 10 hours at room temperature.
Then it is poured onto a mixture of 20 ml of 5% aqueous hydrochloric acid solution and 40 g of ice and extracted twice with a total amount of
100 ml of ether. The extracts are combined, washed with water and saturated sodium chloride solution, dried over magnesium sulfate, the solvent is distilled off, and the residue is purified
by column chromatography (Kieselgel G; benzene
methanol 10:0.05).
3-(2,6-Dimethylheptyl)-3-hydroxycyclo
pentanone:
Yield: 0.72 g (24.5%)
Rf=0.28 (benzene-methanol 10:0.1).
IR(NaCl): 3410, 1720, 1460, 1380, 1360, 1220 cm-'.
'H-NMR(CDCI3): 0.9 (9H, d and d, J=6 Hz, 3CH3), 1.28 (6H, mc, 3CH2), 2.3 (8H, mc, 4CH2), 3.35 (1 H, m, it can be changed into
deuterium, OH).
3-(2,6-Dimethylheptyl)-2-cyclopentenone
Yield: 1.1 g (40.62%)
Rf=0.62 (benzene-methanol 10:0.2).
Analysis: C,4H24O (208.33)
Calculated: C%=80.70 H%=1 1.61 Found: C%=80.49 H%=1 1.42 IR(NaCI): 1705, 1615, 1460, 1380, 1360,
1250, 1150, 1090 cm-1.
'HNMR(CDCI3): 0.9 (9H, d and d, J=6Hz, 3CH3), 1.3 (6H, mc, 3CH2), 2.4 (6H, mc 3CH2), 5.95 (1H, m, =CH).
2-(1,5-Dimethylhexyl)-3-methyl-2-cyclopentenone (by-product)
Yield: 0.29 g (10.74%)
Rf=0.83 (benzene-methanol 10:0.2)
Analysis: C14H24O (208.33)
Calculated: C%=80.70 H%=11.61
Found: C%=80.64 H%=11.47
IR(NaCl): 1705, 1615, 1460, 1380, 1250, 1150, 1090cm1.
'H-NMR(CDC13): 0.9 (6H, d, J=6, Hz, 2CH, 1
1.8 (10h, m, 3CH2, CH, CH3), 2 (3H, s, CH3),
2.35 (5H, mc, 2CH CH).
Example 8
Preparation of 3-(2,6-dimethylheptyl)-2-cyclopentenone [(I): R=R2=R3=Y=H]- To a solution of 1.3 g (0.013 mole) of anhydrous diisopropylamine and 5 ml of hexamethylphosphorus triamide in 20 ml of anhydrous tetrahydrofurane, a 15% butyl-lithium solution in hexane containing 0.9 g (0.014 mole) of butyl-lithium, is added under vigorous stirring at -65 C, under argon, and the mixture is stirred further at -30 C for 20 minutes. Then it is cooled to -65 C, and a solution of 2.26 g (0.01 mole) of 7,11 -dimethyl-2,5-dodecanedione [(ll): R=R=R =Y=H] in 20 ml of anhydrous tetrahydrofurane is dropped within 2 hours. The mixture is stirred at -650C for one hour, allowed to warm up to room temperature and stirred further for 6 hours.Then it is poured onto water and extracted twice with a total amount of 100 ml of ether. The ethereal extracts are washed with water, saturated sodium chloride solution, dried over magnesium sulfate, the solvent is distilled off, and the residue is purified by column chromatography (Kieselgel 60, benzene-methanol 10:0.05).
Yield: 0.91 g (43.75%), the product is identical with the compound prepared according to
Example 2.
Example 9
Preparation of 7,11 -dimethyl-1 0-dodecene- 2,5-dione [(II): R'=R2=H, R3+Y=double bond]
To a solution of 15.4 g (0.1 mole) of citroneilal [(V); R1=R2=H, R3+Y= double bond], 14 g (0.2 mole, 16 ml) of freshly distilled methyl vinyl ketone (IV) and 3.1 g (0.01 mole) of 3-ethoxyethyl 5-(2-hydroxyethyl)-4-methyl-thiazoliu m bromide [(VI I): R5=C2H5OCH2CH2, R5=CH3] in 40 ml of anhydrous dioxane 1.82 g (0.018 moles) of anhydrous triethylamine are added, and the mixture is stirred on an oil bath of 80 C for 24 hours, under argon. Then it is cooled, the separated precipitate is filtered off, the solvent is distilled off, and the residue is distilled in vacuo.
Yield: 10.5 g (46.8%)
B.p.: 105-107 C/0.2 mmHg
nD25=1.470
IR(NaCl): 1715, 1460, 1380, 1360 cm-1.
NMR(CCl4): 0.9 (3H, d, J=6Hz, CH3), 1.2 (12H, mc, 3CH2 and 2CH3), 2.1 (3H, s, CH3), 2.58
(4H, s, 2CH2), 5.1 (1H, m, =CH).
Ms: M+ 224 (10%), m/e 206 (19), 166 (66),
153 (13), 141 (42), 114 (16), 110 (49), 99 (100), 71(44), 69(71), 55(39), 43(90), 41 (71).
Example 10
Preparation of 3-(2,6-d imethyl-5-heptenyl-2cyclopentenone [(I): R1=R2=H, R3+Y=double bond]
To a vigorously stirred mixture of 2.6 g (0.026 mole) of anhydrous diisopropylamine, 10 ml of hexamethylphosphorus triamide and 40 ml of an hydros tetrahydrofurane a 15% by weight solution of butyllithium in hexane containing 1.8 g (0.028 mole) of butyllithium, is added at -65 C, under argon, and the mixture is stirred at -30 C for half an hour. Then it is cooled to a temperature below -60 C, and a solution of 4.5 g (0.02 mole) of 7,11 -dimethyl-1 0-dodecene-2,5-dione [(I I): R1=R2=H, R3+Y=double bondj in 30 ml of anhydrous tetrahydrofurane is added within 2 hours.The reaction mixture is stirred at -65 C for one hour, then allowed to warm up to room temperature and stirred further for 8 hours.
Then it is poured onto water, extracted twice with a total amount of 100 ml of ether, the extracts are combined, washed with water and saturated sodium chloride solution, dried over magnesium sulfate, the solvent is distilled off, and the residue is purified by column chromatography (Kieselgel 60, benzene-methanol 10:0.05).
Yield: 1.4 g (34%)
Rf=0.7 (benzene-methanol 10:0.3)
IR(NaCl): 1705, 1615, 1460, 1380, 1250,
1150, 1090 cm-1 1H-NMR(COl4): 0.9 (3H, d, J=6 Hz, CH3), 1.2 (12H,mc, 3OH2 and 2CH3), 2.3 (6H, mc,
3CH2), 5.1 (1H, m, =CH).
Example 11
Preparation of 7,1 1-dimethyl-1 1-ethoxy-2,5- dodecanedione [(II): R=R=Y=H, R =OCH2CH3]
A mixture df 20 g (O.1 mole) of 7-ethoxy6,7-dihydrocitronellal [(V): R=R=Y=H, R3=OCH2CH3], 10.5 g (0.15 mole) of distilled methyl vinyl ketone (Vl) and 2.5 g (0.01 mole) of 3-benzyl-5-(2-hydroxyethyl)-4-methylthiazolium chloride [(VII): R5=benzyl, R6=CH R7=-CH2OH2OH, X=CI] is heated to 70 C, 1.8 g (2.5 ml, 0.018 mole) of anhydrous triethylamine are added, and the reaction mixture is stirred under nitrogen on an oil bath of 75 C for 16 hours. Then it is cooled to room temperature, poured into a mixture of 100 ml of 2.5% aqueous sulfuric acid solution and 25 g of ice, and extracted twice with a total amount of 150 ml of dichloromethane.The extract is washed with water, 5% aqueous sulfuric acid solution, water again, dried over magnesium sulfate, the solvent is distilled off, and the residual oily product is distilled in vacuo.
Yield: 11.6 g (42.96%)
B.p.: 112-11 4oC/0.2 mm
Analysis: C16H3003 (270.40)
Calculated: C%=71.07 H%=11.18 Found: C%=70.86 H%=10.80
IR(NaCl): 1715, 1460, 1380, 1360, 1150,
1070 cm-1 H-NMR(CCI4): 0.9 (3H, d, J=6 Hz, CH3), 1.3
(15H, mc, 3CH2, 3CH3, 2.1 (3H, s, CH3), 2.55
(4H, s,2CH2),3.6 (2H, q, J=6 Hz, OCH2).
Example 12
Preparation of 3-(2,6-dimethyl-6-ethoxyheptyl)-2-cyclopentenone [(I): R1=R2=Y=H, R3=@CH2CH3] To a mixture of 2.6 g (0.026 mole) of anhydrous diisopropylamine and 10 ml of hexamethylphosphorous triamide in 50 ml of anhydrous tetrahydrofurane cooled to -65 C under nitrogen, a 15% by weight solution of butyllithium in heltane containing f.8 g (0.028 mole) of butyllithium, is added, and the reaction mixture is stirred at a temperature below 30a0 for half an hour.Then it is cooled to -65 C, and a solution of 5.4 g (0.02 mole) of 7,1 1-dimethyl- 1 1-ethoxy-2,5-dodecane-dione [(ll): R1=R2=Y=H, R3--O0H2CH3] in 20 ml of anhydrous tetrahydrofurane is dropped within 2 hours. The mixture is stirred at 65a0 for one hour, allowed to warm up to room temperature and stirred further for 8 hours. Then it is poured on to water and extracted twice with a total amount of 100 ml of ether. The extracts are combined, washed with water and saturated sodium chloride solution, dried over magnesium sulfate, the solvent is distilled off, and the residue is purified by column chromatography (Kieselgel 60, benzene-methanol 10:0.1).
Yield: 1.9 g (37.7%)
Rf=0.53 (benzene-methanol 10:1)
Analysis: C16H28O2 (252.38)
Calculated: C%=76.14 H%=11.18 Found: C%=75.91 H%=10.89 IR(NaCl): 1705, 1615, 1460, 1380, 1270,
1240, 1155, 1065 cm-1.
1H-NMR(CDCl4): 0.9 (3H, d, J=6 Hz, CH3), 1.05
(6H, s,2CH3),1.3 (9H, mc, 3CH2, CH3), 2.3
(6H, mc, m, 3CH2), 3.6 (2H, q, J=6 Hz, OCH2), 5.78 (1 H, m, =CH).
Claims (14)
1. A process for the preparation of 3substituted-2-cyclopentenone derivatives of the general formula (I),
wherein
R' and R2 represent independently from each other a hydrogen atom or a straight-chained or branched Ca~4 alkyl group,
R3 stands for a hydrogen atom or a C1-4 alkoxy group,
Y represents hydrogen, or
R3 and Y together represent an oxygen atom or a double bond, characterized by
a.) reacting a 2,5-dodecanedione derivative of
the general formula (II),
wherein
R', R2, R3 and Y are as defined above, with an alkali or alkaline-earth hydride or a lithium-(di C,-6 alkyl amide) in an aprotic, preferably ether-type solvent, and reacting further the compound of the general formula (III) thus obtained,
wherein
R', R2, R3 and Y are as defined above, with an acid; or
b.) reacting a compound of the general formula (III), wherein R', R2, R3 and Y have the same
meanings as above, with a base,
and optionally separating the thus-obtained compound of the general formula (I) from the reaction mixture.
2. A process according to variant a.) of claim 1, characterized by reacting a compound of the general formula (II) with an alkali hydride, preferably sodium hydride.
3. A process according to variant a.) of claim 1, characterized by using lithium-(diethyl amide) or lithium(diisopropyl amide) as lithium-(di-C1-8 alkyl amide).
4. A process according to variant b.) of claim 1, characterized by using an alkali or alkaline-earth hydroxide, preferably sodium hydroxide, as base.
5. A process according to variant a.) of claim 1, characterized by carrying out the reaction with a metal hydride in an aprotic solvent, preferably in ether.
6. A process according to variant a.) of claim 1, characterized by carrying out the reaction with a lithium(di-O1 alkyl amide) in a mixture of tetrahydrofurane and hexamethylphosphorus triamide.
7. Compounds of the general formula (I),
wherein
R1 and R2 represent independently from each other a hydrogen atom or a straight-chained or branched C14 alkyl group,
R3 stands for a hydrogen atom or a C,, alkyl group, Y represents hydrogen, or
R3 and Y together represent an oxygen atom or a double bond, with the proviso that at least one of the symbols R', R2, R3 and Y is other than hydrogen.
8. 3-(2,6-Dimethyl-6-methoxyheptyl)-2cyclopentenone.
9. 3-(2,6-Dimethyl-5-heptenyl)-2-cyclopentenone.
10. 3-(2,6-Dimethyl-6-ethoxyheptyl)-2-cyclo- pentenone.
11. A process as claimed in claim 1 substantially as herein described with reference to any one of Examples 2 to 5, 7, 8, 10 and 12.
12. A compound of the general formula (I) wherein R', R2, R3 and Y are as defined in claim 1, when prepared by a process as claimed in any one of claims 1 to 6 or claim 11.
13. A process for the preparation of 2,5dodecanedione derivatives of the general formula (II) wherein R', R2, R3 and Y are as defined in claim 1, which comprises reacting a citronellal derivative of the general formula (V) with methyl vinyl ketone in the presence of a catalytic amount of a thiazolium salt of the general formula (VII)
wherein
R5 represents a straight-changed or branched
C1-5 alkyl group, a 2-hydroxyethyl group or a benzyl group, R6 is hydrogen or C13 alkyl,
R7 stands for a straight-changed or branched
C1-4 alkyl or a 2-hydroxyethyl group, and
X- is a halide ion.
14. A process as claimed in claim 13 substantially as herein described with reference to any one of Examples 1,6,9 and 11.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HU163181A HU180635B (en) | 1981-06-02 | 1981-06-02 | Process for producing 3-substituted-2-cyclopentanoe derivatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2100728A true GB2100728A (en) | 1983-01-06 |
| GB2100728B GB2100728B (en) | 1985-05-30 |
Family
ID=10955414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08215936A Expired GB2100728B (en) | 1981-06-02 | 1982-06-01 | 3-substituted -2- cyclopentenone derivatives |
Country Status (5)
| Country | Link |
|---|---|
| CS (1) | CS231994B2 (en) |
| FR (1) | FR2506757A1 (en) |
| GB (1) | GB2100728B (en) |
| HU (1) | HU180635B (en) |
| PL (1) | PL135844B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024003176A1 (en) | 2022-06-29 | 2024-01-04 | Givaudan Sa | Organic compounds |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4000174A (en) * | 1974-04-29 | 1976-12-28 | Zoecon Corporation | Novel compounds |
-
1981
- 1981-06-02 HU HU163181A patent/HU180635B/en not_active IP Right Cessation
-
1982
- 1982-06-01 CS CS405982A patent/CS231994B2/en unknown
- 1982-06-01 PL PL23670782A patent/PL135844B1/en unknown
- 1982-06-01 GB GB08215936A patent/GB2100728B/en not_active Expired
- 1982-06-02 FR FR8209546A patent/FR2506757A1/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024003176A1 (en) | 2022-06-29 | 2024-01-04 | Givaudan Sa | Organic compounds |
| WO2024000260A1 (en) * | 2022-06-29 | 2024-01-04 | Givaudan Sa | Organic compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| CS231994B2 (en) | 1985-01-16 |
| HU180635B (en) | 1983-03-28 |
| GB2100728B (en) | 1985-05-30 |
| PL135844B1 (en) | 1985-12-31 |
| PL236707A1 (en) | 1983-04-11 |
| FR2506757A1 (en) | 1982-12-03 |
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