DE1024511B - Process for the preparation of cyclopentenyl-substituted ketones - Google Patents

Description

Process for the preparation of cyclopentenyl-substituted ketones The invention relates to a process for the preparation of cyclic ketones.

The process according to the present invention is characterized in that a compound of the general formula in the presence of a compound of the general formula in which Fi, Rov R3 and R, denote hydrogen or an acyclic hydrocarbon radical with a maximum of 7 carbon atoms and the substituents Rl-R4 are identical in both compounds, heated to 130 to 160 °.

Acyclic hydrocarbon radicals are both saturated as well as unsaturated aliphatic hydrocarbon radicals, such as. B. methyl, ethyl, Isopropyl, n-butyl, allyl or propargyl radicals are to be understood.

The alcohols of the general formula (II) used as starting materials can be obtained by condensation of a ketone of the general formula in which Ri, R2, R3 and R4 have the meaning given above, are obtained with an alkali metal acetylide in liquid ammonia and hydrolysis of the condensation product obtained.

The acetoacetic acid esters of the general formula (I) can be obtained by condensation the alcohols of the general formula (II) are prepared with diketene.

Carrying out the method according to the present invention expediently happens so that one. a mixture of equal amounts by weight of the Starting compounds of the general formulas (I) and (II) to 130 to 160 °, preferably 150 to 155 °, heated. The reaction takes place with evolution of carbon dioxide. The heating of the reaction mixture is expediently continued until until the carbon dioxide development stops.

The reaction product can be obtained by fractional distillation of the reaction mixture to be isolated. The isolation and purification of the end product can also be done by The reaction mixture is taken up in petroleum ether, the solution is extracted with alkali bicarbonate solution to remove acidic by-products, wash the organic phase with water and fractional distillation can be carried out under reduced pressure.

The products obtainable by the process according to the invention are new compounds which have the following general formula: The radicals Ri, R2, R3 and R4 have the meaning given above. These new compounds have characteristic odor notes that are reminiscent of violet and iris fragrances; they are used as fragrances, e.g. B. can be used in the manufacture of perfumes, soaps and, more generally, of perfumed products.

The invention is illustrated in the following examples.

Example 1 A mixture of 236 g of racemic 3, 7-dimethylocten- (6) -in- (1) -ol- (3) (Dehydrolinalol) and 236 g [3, 7-Dimethylocten- (6) -in- (1) -yl- (3)] - acetoacetate (manufactured by condensation of diketene with racemic dehydrolinalol) is by means of a Oil bath heated to about 150 with vigorous stirring. There is a slow development of carbon dioxide, which runs out after about 8 hours. You then interrupt the Apply heat and cool the reaction mixture. By fractional distillation of the Reaction mixture in vacuo gives 4- [2-methyl-5-isopropenylcyclopenten- (1) -yl- (1)] -butanone- (2); Bp 0.5 = 72 to 75 °; nD25 = 1.4800; Semicarbazone (from 50% ethanol), melting point 136 ° ; 4-phenylsemicarbazone (from 50 °, 10% ethanol), m.p. 101 °; 2,4-Dinitrophenylhydrazone (from ethanol). M.p. 87.5 °.

Example 2 A three-necked flask with a volume of 11 is charged a mixture of 250 g of racemic 3, 6, 7-trimethylocten- (6) -in- (l) -ol- (3) and 250 g of [3, 6, 7-trimethylocten- (6) -in- (1) -yl- (3)] -acetoacetate [prepared by condensation of diketene with racemic 3, 6, 7-trimethylocten- (6) -in- (l) -ol- (3)]. The flask is then heated in an oil bath to 150 ° in such a way that carbon dioxide is released escapes from the reaction mixture. When the carbon dioxide development stops, will the reaction mixture diluted with 300 cm3 petroleum ether, several times with saturated aqueous sodium bicarbonate solution extracted to extract acidic by-products, and then washed neutral with water. The organic layer is over calcium sulfate dried and subjected to fractional vacuum distillation. The at Kp. l = 68 to 70 ° over distilling fraction represents the desired product, namely 4- [2,5-dimethyl-5-isopropenylcyclopenten- (1) -yl- (1)] -butanone- (2); s2Ds = 1.4839; Semicarbazone, m.p. 151 to 152 °.

Example 3 A three-necked flask with a volume of 11 is charged a mixture of 250 g of 3, 7-dimethylnonene- (6) -in- (1) -ol- (3) and 250 g of racemic [3, 7-Dimethylnonene- (6) -in- (1) -yl- (3)] - acetoacetate [produced by condensation of diketene with racemic 3, 7-dimethylnonene- (6) -in- (1) -ol- (3)]. The piston will then heated in an oil bath to 150 to 155 ° in such a way that carbon dioxide is mixed with a Speed of about 0.1 minor hour escapes from the reaction mixture. To The development of carbon dioxide ceases for 8 hours. The reaction mixture is with 300 cm3 of petroleum ether diluted several times with saturated aqueous sodium bicarbonate solution extracted to extract acidic by-products, and then washed neutral with water. The organic layer is dried over calcium sulfate and fractionated Subjected to vacuum distillation. The fraction distilling over at bp 0.6 = 88 to 89 ° represents the desired product, namely 4- {2-methyl-5- [buten- (2) -yl- (2)] - cyclopentene- (1) -yl- (1)} - butanone- (2), represents; it ,,, = 1.4828; Semicarbazone, m.p. 122 °.

The starting materials used in this example, the 3, 7-dimethylnonene- (6) -in- (1) -ol- (3) and the [3, 7-dimethylnonene- (6) -in- (1) -yl- (3)] -acetoacetate can be used as follows are prepared: Treat 3-methylpentene- (l) -ol- (3) using concentrated Hydrochloric acid, the 1-chloro-3-methylpentene (2) obtained condenses with ethyl acetoacetate in in the presence of sodium methylate, saponified and decarboxylated the 3-carbethoxy-6-methylocten- (5) -one- (2) by means of alcoholic potassium hydroxide or hydrochloric acid, the condenses 6-Alethylocten- (5) -one- (2) obtained, boiling point = 65 °; stD5 = 1,4412, with sodium acetylide in liquid ammonia and hydrolyzes the condensation product with aqueous sulfuric acid ; one obtains 3, 7-dimethylnonene- (6) -in- (1) -ol- (3), Kp lo = 895; st2D = 1,4612.

By condensation with diketene in a mixture of petroleum ether, Pyridine and acetic acid are used to obtain the r3, 7-dimethylnonen- (6) -in- (1) -yl- (3)] acetoacetate; w = 1,4653.

Example 4 A three-necked flask with a volume of 11 is charged a mixture of 278 g of 3, 7, 9-trimethyldecen- (6) -in- (1) -ol- (3) and 278 g of racemic [3,7,9-Trimethyldecen- (6) -in- (1) -yl- (3)] -acetoacetate, prepared by condensation of diketene with 3, 7, 9-trimethyldecen- (6) -in- (1) -ol- (3)]. The piston will then heated in an oil bath at 150 to 155 ° in such a way that carbon dioxide is removed from the reaction mixture escapes. After 8 hours, the evolution of carbon dioxide has ended. The reaction mixture is diluted with 300 cm3 petroleum ether, several times with saturated aqueous sodium bicarbonate solution extracted and then washed neutral with water. The organic layer is over Calcium sulfate dried and subjected to fractional vacuum distillation.

The fraction which distills over at bp 03 = 96 to 99 ° represents that desired product, namely 4- {2-methyl-5- [4-methylpentene- (2) -yl- (2) -] - cyclopentene- (1) -yl- (1)} - butanone- (2), dar; nD25 = 1.4773; Phenylsemicarbazone, m.p. 136 °.

The starting materials used in this example, the 3, 7, 9-trimethyldecen- (6) -in- (1) -ol- (3) and the [3, 7, 9-trimethyldecen- (6) -in- (1) -yl- (3)] -acetoacetate, can be prepared as follows: Treat 3, 5-dimethylhexen- (1) -ol- (3) with concentrated hydrochloric acid, the 1-Clilor-3, 5-dimethylhexene-obtained condenses (2), it "'= 1.448, with ethyl acetoacetate in the presence of sodium ethylate, saponifies and decarboxylates the 3-cabethoxy-6, 8-dimethylnonen- (5) -one- (2) using alcoholic potassium hydroxide or hydrochloric acid, the obtained condenses 6, 8-dimethylnonene- (5) -one- (2), bp 35 = 120D; nD25 = 1.4432; 2, 4-Dinitrophenylhvdrazone, M.p. 47 °; Semicarbazone, melting point 114 °, with sodium acetylide in liquid ammonia and hydrolyzes the condensation product with aqueous sulfuric acid; you get 3, 7, 9-trimethyldecen- (6) -in- (1) -ol- (3), bp 35 = 72 °; rao = 1,4598. By condensation with diketene in a mixture of petroleum ether, pyridine and acetic acid is obtained thereof [3, 7, 9-trimethyldecen- (6) -in- (1) -yl- (3)] -acetoacetate; 7t2DS = 1,4636.

Example 5 A three-necked flask with a volume of 11 is charged a mixture of 264 g of 3, 7-dimethyl-4-wthylocten- (6) -in- (1) -ol- (3) and 264 g of racemic [3, 7-Dimethyl-4-ethylocten- (6) -in- (1) -yl- (3)] - acetoacetate [manufactured by Condensation of diketene with 3, 7-dimethyl-4-ethylocten- (6) -in- (1) -ol- (3)]. Of the The flask is then heated in an oil bath to 150 to 155 ° in such a way that carbon dioxide is released escapes from the reaction mixture. When the carbon dioxide development stops, will the reaction mixture diluted with 300 cm3 petroleum ether, several times with saturated extracted aqueous sodium bicarbonate solution and then washed neutral with water. The organic layer is dried over calcium sulfate and fractionated Subjected to vacuum distillation. The fraction distilling over at bp 0 = 90 to 92 ° represents that desired product, namely 4- [2-methyl-3-ethyl-5-isopropenylcyclopenten- (1) -yl- (1)] -butanone- (2) represents; ; 1 15 = 1.4785; Semicarbazone, m.p. 97.5 °.

The starting materials used in this example, the 3, 7-dimethyl-4-äthyIocten- (6) -in- (1) -ol- (3) and the [3, 7-dimethyl-4-ethylocaten- (6) -in- (1) -yl- (3)] - acetoacetate, can be prepared as follows: One condenses [l, 1-Dimethylpropen- (2) -yl- (1)] - acetoacetate with ethyl bromide in the presence of sodium ethylate, decarboxylated the (dimethylvinylcarbinyl) -a-ethyl acetoacetate obtained, b.p. o. s = 46 to 51 ° ; nD25 = 1.4332, by heating to 160 to 170 °, the resulting condenses 3-ethyl-6-methylhepten- (5) -one- (2), bp 7 = 69 to 70 °; 2D5 = 1,4401, with sodium acetylide in liquid ammonia and hydrolyzes the condensation product with aqueous sulfuric acid ; you get 3, 7-dimethyl-4-äthylocten- (6) -in- (l) -ol- (3), bp.1 = 69 to 70 ' ; 11 = 1, 4669. By condensation with diketene in a mixture of petroleum ether, Pyridine and acetic acid are obtained therefrom [3, 7-dimethyl-4-äthylocten- (6) -in- (1) -yl- (3)] acetoacetate; nD25 = 1,4701.

Example 6 A three-necked flask with a volume of 11 is charged a mixture of 276 g of 3, 7-dimethyl-4-allylocten- (6) -in- (1) -ol- (3) and 276 g of racemic [3, 7-Dimethyl-4-allylocten- (6) -in- (1) -yl- (3)] - acetoacetate [manufactured by Condensation of diketene with 3, 7-dimethyl-4-allylocten- (6) -in- (1) -ol- (3)]. Of the The flask is then heated in an oil bath to 150 ° in such a way that carbon dioxide is removed from the Reaction mixture escapes. When the evolution of carbon dioxide ceases, the reaction mixture becomes diluted with 300 cm3 petroleum ether, several times with saturated aqueous sodium bicarbonate solution extracted and then washed neutral with water. The organic layer is over Calcium sulfate dried and subjected to fractional vacuum distillation. The at Isp. 0.3 = 90 to 92 ° over distilling fraction represents the desired Product, namely 4- [2-methyl-3-allyl-5-isopropenylcyclopenten- (1) -yl- (1)] -butanone- (2), dar; 5IDS = = 1,4888; Semicarbazone, m.p. 119 to 120 °.

The starting materials used in this example, the 3, 7-dimethyl-4-allylocten- (6) -in- (1) -ol- (3) and the [3, 7-dimethyl-4-allylocten- (6) -in- (1) -yl- (3)] -acetoacetate, can like are prepared as follows: [1,1-Dimethylpropen- (2) -yl- (1)] -acetoacetate is condensed with allyl bromide in the presence of sodium ethylate, the (dimethylvinylcarbinyl) -a-allylacetoacetate obtained is decarboxylated, Kpeo, 2 = 53 to 59 °; nD = 1, 4475, by heating to 160 to 170 °, condensed the resulting 3-allyl-6-methylhepten- (5) -one- (2), boiling point 7 = 81 to 82 °; it "= 1, 4550, with sodium acetylide in liquid ammonia and hydrolyzes the condensation product with aqueous sulfuric acid; one receives 3, 7-dimethyl-4-allylocten- (6) -in- (1) -ol- (3), b.p. 0, = 72 to 74 °; nDS = 1, 4771. By condensation with diketene in one Mixture of petroleum ether, pyridine and acetic acid is obtained therefrom [3, 7-dimethyl-4-allylocten- (6) -in- (1) -yl- (3)] acetoacetate; no = 1, 4,781.

Example 7 A three-necked flask with a volume of 11 is charged a mixture of 274 g of 3, 7-dimethyl-4-propargylocten- (6) -in- (1) -ol- (3) and 274 g racemic [3,7-dimethyl-4-propargylocten- (6) -in- (1) -yl- (3)] acetoacetate [produced by condensation of diketene with 3, 7-dimethyl-4-propargylocten- (6) -in- (1) -ol- (3)]. The flask is then heated to 150 ° in an oil bath such that Carbon dioxide escapes from the reaction mixture.

When the evolution of carbon dioxide ceases, the reaction mixture will diluted with 300 cm3 petroleum ether, several times with saturated aqueous sodium bicarbonate solution extracted and then washed neutral with water. The organic layer is over Calcium sulfate dried and subjected to fractional vacuum distillation. The fraction distilling over at Kip. ,,, = 101 to 103 ° represents the desired Product, namely 4- [2-methyl-3-propargyl-5-isopropenylcyclopenten- (1) -yl- (1)] -butanone- (2), dar; nD25 = 1,4952; Semicarbazone, m.p. 110-111 °.

The starting materials used in this example, the 3, 7-dimethyl-4-propargylocten- (6) -in- (1) -ol- (3) and the [3, 7-dimethyl-4-propargylocten- (6) -in- (1) -yl- (3)] -acetoacetate, can like are prepared as follows: [1,1-Dimethylpropen- (2) -yl- (1)] -acetoacetate is condensed with propargyl bromide in the presence of sodium ethylate, the decarboxylated (Dimethylvinylcarbinyl) -a-propargylacetoacetate, KpsoSs = 70 °; nDS = 1,454, through Heating to 160 to 170 °, the resulting 3-propargyl-6-methylheptene condenses (5) -on- (2), bp 13 = 100 to 103 °, nll = 1,4639, with sodium acetylide in liquid Ammonia and hydrolyzes the condensation product with aqueous sulfuric acid; one obtains 3, 7-dimethyl-4-propargylocten- (6) -in- (1) -ol- (3), boiling point 0.7 = 83 bis 86 °; nD25 = 1, 4645. By condensation with diketene in a mixture of petroleum ether, Pyridine and acetic acid are obtained therefrom [3, 7-dimethyl-4-propargylocten- (6) -in- (1) -yl- (3)] acetoacetate; nD25 = 1,4840.

Example 8 A three-necked flask with a volume of 11 is charged a mixture of 278 g of 3, 7-dimethyl-4-ethylnonen- (6) -in- (1) -ol- (3) and 278 g of racemic [3, 7-Dimethyl-4-ethylnonen- (6) -in- (1) -yl- (3)] - acetoacetate [produced by condensation of diketene with 3, 7-dimethyl-4-ethylnonene- (6) -in- (1) -ol- (3)]. The piston will then heated in an oil bath to 150 to 155 ° in such a way that carbon dioxide from the reaction mixture escapes. When the evolution of carbon dioxide ceases, the reaction mixture is with 300 cm3 of petroleum ether diluted several times with saturated aqueous sodium bicarbonate solution extracted and then washed neutral with water. The organic layer is over Calcium sulfate dried and subjected to fractional vacuum distillation. The fraction which distills over at bp 0 = 494 ° represents the desired product, namely 4-l2-methyl-3-ethyl-5- [buten- (2) -yl- (2)] -cyclopenten- (1) -yl- (l)} - butanone- (2), dar, nD25 = 1, 4830 4830 semicarbazone, m.p. 125 to 126 °.

The starting materials used in this example, the 3, 7-dimethyl-4-äthylnonen- (6) -in- (l) -ol- (3) and the [3, 7-dimethyl-4-ethylnonene- (6) -in- (1) -yl- (3)] - acetoacetate, can be prepared as follows: Ethylmethylvinylcarbinol is treated with Diketene in a mixture of petroleum ether, pyridine and acetic acid, condenses that [3-methylpentene- (1) -yl- (3)] acetoacetate obtained, boiling point 0.9 = 58 to 60 °; nD25 = 1.4426, with ethyl bromide in the presence of sodium ethylate, the (ethylmethylvinylcarbinyl) -a-ethyl acetoacetate obtained is decarboxylated, Bp p, 2 = 57 to 62 °; nD25 = 1, 4415, by heating to 160 to 170 °, condensed the resulting 3-ethyl-6-methylocten- (5) -one- (2), b.p. 22 = 104 °; nD5 = = 1, 4450, with sodium acetylide in liquid ammonia and hydrolyzes the condensation product with aqueous sulfuric acid; you get3, 7 dimethyl-4-ethylnonene- (6) -in- (1) -ol- (3), Bp 1,4 = 82 to 84 °; nD25 = 1,4682.

By condensation with diketene in a mixture of petroleum ether, Pyridine and acetic acid are obtained therefrom [3, 7-Dimethyl-4-ethylnonene- (6) -in- (1) -yl- (3)] acetoacetate ; 1, 4703.

Example 9 A three-necked flask with a volume of 11 is charged a mixture of 290 g of 3, 7-dimethyl-4-allylnonen- (6) -in- (1) -ol- (3) and 290 g of racemic 73,7-Dimethyl-4-allylnonen- (6) -in- (1) -yl- (3)] acetoacetate [produced by condensation of diketene with 3, 7-dimethyl-4-allylnonen- (6) -in- (1) -ol- (3)]. The piston will then heated in an oil bath to 150 to 155 ° in such a way that carbon dioxide from the reaction mixture escapes. When the evolution of carbon dioxide ceases, the reaction mixture is with 300 cm3 of petroleum ether diluted several times with saturated aqueous sodium bicarbonate solution extracted and then washed neutral with water. The organic layer is over Calcium sulfate dried and subjected to fractional vacuum distillation. The fraction distilling over at a boiling point of 0.7 = 107 to 110 ° is the desired one Product, namely 4- {2-methyl-3-allyl- [buten- (2) -yl- (2)] -cyclopenten- (1) -yl- (1)} - butanone- (2), dar; nD25 = 1.4898; Semicarbazone, m.p. 122 °.

The starting materials used in this example, the 3, 7-dimethyl-4-al; lylnonen- (6) -in- (1) -ol- (3) and the [3, 7-dimethyl-4-allylnonen- (6) -in- (1) -yl- (3)] -acetoacetate, can like are prepared as follows: [3-methylpentene- (1) -yl- (3)] -acetoacetate is condensed with allyl bromide in the presence of sodium ethylate, the (ethylmethylvinylcarbinyl) -a-allylacetoacetate obtained is decarboxylated, Bp 0.7 = 75 to 80 °; iz = 1.4532, condensed by heating to 160 to 170 ° the resulting 3-allyl-6-methylocten- (5) -one- (2) with sodium acetylide in liquid ammonia and hydrolyzes the condensation product with aqueous sulfuric acid ; 3, 7-dimethyl-4-alylnonen- (6) -in- (1) -ol- (3), boiling point 0.6 = 83 to 85 °; z2D5 = 1, 4780. By condensation with diketene in a mixture of petroleum ether, Pyridine and acetic acid are obtained therefrom [3, 7-dimethyl-4-allylnonen- (6) -in- (1) -yl- (3)] acetoacetate; nDS = 1,4792.

For the production of the raw materials, protection is provided within the framework of the present invention not claimed.

Claims (2)

PATENT CLAIMS: 1. Process for the preparation of cyclopentenyl-substituted ketones of the general formula in which R1, RD, R3 and RX denote hydrogen or an acyclic hydrocarbon radical with at most 7 carbon atoms, characterized in that expediently equal amounts by weight of a compound of the general formula and a compound of the general formula in which the radicals R. i, Rg, Rg and R4 have the above meaning and the same radicals Ri to R4 are identical in both compounds, heated to 130 to 160 °, preferably 150 to 155 °, expediently until the development of isolenic dioxide has ceased. 2. The method according to claim 1, characterized in that one [3, 7-dimethylocten- (6) -in- (1) -yl- (3)] - acetoacetate in the presence of 3, 7-dimethylocten- (6) -in- (1) -ol- (3), [3, 6, 7-trimethylocten- (6) -in- (1) -yl- (3)] - acetoacetate in countermart of 3, 6, 7-trimethylocten- (6) -in- (1) -ol- (3), [3, 7-dimethylnonene- (6) -in- (1) -yl- (3)] - acetoacetate in the presence of 3, 7-dimethylnonene- (6) -in- (1) -ol- (3), [3, 7, 9-trimethyldecen- (6) -in- (l) -yl- (3)] - acetoacetate in the presence of 3, 7, 9-trimethyldecen- (6) -in- (1) -ol- (3) and [3, 7-dimethyl-4-allylocten- (6) -in- (1) -yl- (3)] - acetoacetate in the presence of 3, 7-dimethyl-4-allylocten- (6) -in- (1) -ol- (3) heated.