DE2458702A1 - PROCESS FOR PREPARING A NEW SUBSTITUTED KETONE - Google Patents

Description

DR. MULLER-BORE DIPL.-ING. GROENING

DIPL.-CHEM. DR. DEUFEL DIPL.-CIIEM. DR. SCHÖN

DIPL.-PHYS. HERTEL

9 L R P, 7 Π 9

PATENT Attorneys £ H V 0 / U £

S / K 19-43

Kuraray Co., Ltd., Tokyo / Japan Process for the production of a new substituted ketone

The invention relates to a method for producing a substituted one Ketones by urea substitution of an organic halide with a ketone in the presence of an alkali metal hydroxide as well a catalyst. In particular, the invention is concerned with an improved method of making a substituted one Ketones by reacting an organic halide

with a ketone with an active hydrogen on the cd carbon atom (with respect to the carbonyl group) in the presence of an alkali metal hydroxide and a certain phosphonium salt.

There are processes for the preparation of a substituted ketone by reacting an organic halide with a corresponding one Ketone with an active hydrogen atom on the cC carbon atom (with respect to the carbonyl group) in the presence of an alkali metal hydroxide and a catalyst are known. These The reaction can be reproduced as follows:

• I MnH> C-CO-C-

-C-Hal + <>CH-CO-C-> I '+ M · Hal + Ii ₀ O

, ^x ι catalyst ' _{-C- έ} 2

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MUNICH 86. SIEBERTSTR. 4, POST BOX 860 720, CABLE: RHEINPATENT, TEI .: (089) 4710 70/70 TELEX 5-22

wherein Hal represents a halogen atom and M represents an alkali metal means.

For example, in US Pat. No. 2,644,843, the reaction of an allyl methyl ketone with an alkyl halide in the presence of a Alkali metal hydroxide described. GB-PS 851 658 also describes the preparation of 6-methyl-5-hepten-2-one (hereinafter referred to as "methylheptenone") from 1-chloro-3-methyl-2-butene (hereinafter referred to as "prenyl chloride") and acetone. When performing this procedure is however, the yield is very low. For example, it is 43% in the case of using potassium hydroxide and 20% in the case of the use of sodium hydroxide (according to the aforementioned GB-PS). In "Journal of Organic Synthetic Chemistry", Japan, 28, 54 (1970) stated by Yuki Gosei-Kagaku that the Process according to the above-mentioned GB-PS, as our own experiments have shown, a substituted ketone in one yield yields of only 35% when potassium hydroxide is used and in a yield of only 5% when sodium hydroxide is used. It is also stated that the addition of dimethylformamide, dimethyl sulfoxide or the like increases the yield elevated. US Pat. No. 3,668,255 states that the addition of the amine compounds described therein increases the yield increases.

DT-OS 2 356 866.3 states that the addition of a certain phosphonium salt when carrying out the mentioned reaction markedly increases the yield of a substituted ketone. It is stated there that there is a It is advantageous to carry out on an industrial scale to add water to the reaction system from the start of the reaction, when a certain phosphonium salt is used as a catalyst

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will. This information is in contrast to the following explanations with regard to the state of the art.

The reaction is inevitably accompanied by the formation of water, as indicated above, so that it it is practically impossible to keep the reaction in an absolutely anhydrous state from the beginning to the end. It was assumed that water should be removed from the reaction system at the beginning of the reaction because of the presence of large amounts of water markedly worsened the reaction yield. In order to overcome these difficulties, it has been customary to use those in the starting materials To limit the amount of water contained and to add the alkali metal hydroxide in solid form to the reaction system.

In Japanese Patent Publication 40 (1965) -22 251, which US Pat. No. 3,668,255, it is stated that the state of dryness of the appropriate starting materials in Presence of an amine catalyst is not critical and in most cases the reaction will not be affected by the presence of less than 2 moles of water per 1 mole of an organic halide is adversely affected. It should be noted, however, that when performing all the examples the said patent publication the reactions in substantially anhydrous state were initiated.

The invention is based on the finding that the reaction of prenyl chloride with acetone in the presence of an alkali metal hydroxide is deteriorated by a very small amount of water existing in the acetone, and further, the reaction yields clearly through the addition of potassium iodide, sodium iodide, dimethy I-sulfone, SuIfolan, tri-n-butylphosphine oxide, methylamine, dimethylamine, Trimethylamine, ethylamine, cyclohexylamine and ammonium

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Chloride can be reduced. This means that there is a decrease in yield must be accepted due to the presence of water in these substances. Taking into account that the manufacturing cost if the thorough drying of the starting materials is omitted, then it is understood that the allowable amount of water existing in the reaction system is not more than 2 moles based on 1 mole of the organic Halide, when performing the known methods.

In DT-OS 2 356 866.3 it is stated that not only the reaction runs even in the presence of water, but rather also in the presence of water if a molar ratio is maintained Water / organic halide of not less than 2 and preferably 2.0 to 10.0 initially is feasible, with a substituted ketone can be obtained in a yield similar to that of the reaction obtained in the absence of Water is carried out at the beginning. This means that when carrying out the method described in the above-mentioned DT-OS an alkali metal hydroxide in the form of an aqueous solution instead of introducing water in the amount specified above can be carried out into the reaction system. Furthermore, the reaction is reproducible, with the reaction rate is uniform and the reaction proceeds smoothly. Therefore, this method is of industrial advantage because it is a Control of the reaction temperature allows the process to be safe makes, the device used is simple and allows a continuous operation. It also offers more Advantages, which are discussed in more detail below.

In carrying out the process, the alkali metal hydroxide need not be used in powder or flake form, it can rather, they can be used in pellet form or in the form of an aqueous solution, i.e. in a form that can be used as an industrial product is readily available. This is how it works

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■ - 5 -

Feeding an alkali metal hydroxide, especially in the form of an aqueous solution, to the reaction system is very easy, and the working conditions of the staff are also improved.

When an alkali metal hydroxide is added to the reaction system in an anhydrous state or in an almost anhydrous state, then Occasionally an alkali metal hydroxide sticks in solid form to the bottom of the reaction vessel, so that its effective consumption is prevented. In order to overcome this difficulty, the reaction system must be carefully monitored, in particular it may be necessary to stir the contents of the reaction vessel. This problem is alleviated by the use of a Alkali metal hydroxide dissolved in an aqueous solution.

The allowable amount of water contained in the starting material can be increased considerably in this process, with recovery and reuse as well of the unreacted ketone to save production costs is possible.

In many cases, when this process is carried out, the amount of a ketone required to make a substituted one is required Ketones lower compared to the other known methods.

It has now been found that the above-mentioned phosphonium salt is hardly stable under the reaction conditions, especially in an aqueous alkaline solution, so that therefore the used catalyst loses its activity during the reaction. To this disadvantage of the method discussed above to eliminate proposes the invention as a catalyst to carry out the mentioned reaction a phosphonium salt of the general formula:

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where R is a substituted or unsubstituted cyclohexyl group, R ^{1 is} a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group having not less than 5 carbon atoms, or a substituted or unsubstituted aralkyl group having not less than 7 is carbon atoms, P is a phosphorus atom, and X is an anion which is ^{capable of dissociating from (R-PR 1} ) in an aqueous solution.

In the phosphonium salt of the present invention, R may be a cycle hexyl group, an alkyl-substituted cyclohexyl group having an alkyl group having 1 to 18 carbon atoms or the like as a substituent. R ¹ may be an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms which has an alkyl group having 1 to 18 carbon atoms as a substituent, an aralkyl group having 7 to 30 carbon atoms, or the like. X stands for any anion which is ^{able to dissociate from (R-PR 1} ) in an aqueous environment, for example for Cl, Br, ύ, OH, NO ~

ClO ", CH ₃ COO", SCN ", 0

S η

₃ SOCH ₃ , p- S "

OCH ₃

CH ₃ SPS ", -0
0

or similar.

O ₃ N

According to the invention, as phosphonium salts, for example

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24S8702

the following are used: Tricyclohexylmethy! phosphonium, Tricyclohexylä: hy ! phosphonium, tricyclohexyl-n-buty! phosphonium, Tricyclohexylisobuty! Phosphonium, Tricyclohexyl-n-propylphosphonium, Tricyclohexylisopropy! Phosphonium, Tricyclohexylamylphosphonium, Tricyclohexylhexy! Phosphonium, Tricyclohexylheptylphosphonium, Tricyclohexyldecy! Phosphonium, Tricyclohexyllaurylphosphonium, Tricyclohexyltetradecylphosphonium, Tricyclohexylhexadecy! Phosphonium, TricyclohexyIsteary! Phosphonium, Tetracyclohexy! Phosphonium, Tricyclohexylbenzy! Phosphonium, Tri-4-methylcyclohexy-ethylhosphonium, tri-4-methylcyclohexyln-buty-phosphonium or similar.

According to the invention, the specified phosphonium salts can be used alone or in combination of two or more of these salts can be used. The phosphonium salt is generally in a Concentration from about 0.001 to 20 mole percent and preferably used in a concentration of approximately 0.005 to 1.0 mol%, based on the amount of the organic halide.

The above-mentioned phosphonium salts, according to the invention can be used, can be easily from the organic layer by concentrating after separating the organic Recover the layer from the aqueous layer after the completion of the reaction by adding an appropriate one Amount of a precipitating agent such as an ether or a non-polar hydrocarbon or less Use of a cation exchange resin. The recovered catalyst has the same catalytic activity as in its original state, as tests have shown. This fact, which is evidenced by experimental results, is unexpected in view of the fact that other phosphonium salts which do not carry a cyclohexyl group often under the reaction conditions are unstable, especially in an aqueous alkaline solution, so that they reduce their catalytic activity

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to lean. In contrast, the inventive phosphonium salts, that are used as catalysts can be used economically because they are recovered and reused can be. Furthermore, the phosphonium salts have such an excellent catalytic activity that they im can generally be used in amounts which are only a few tenths of the amounts of the other phosphonium salts.

The molar ratio of the organic halide to the ketone can vary considerably, for example between 2: 1 and 1: 2Θ, with a molar ratio of a ketone to an organic halide generally being preferred is set between about 3 and about 10.

In the event that the reaction starts in the absence or presence of a small amount of water, an alkali metal hydroxide becomes preferably in an amount of not less than 1.1 moles based on 1 mole of the organic halide is added therewith substituted ketone is obtained in good yield. In particular, if a large amount of water according to the Preferred conditions given below is used, an alkali metal hydroxide is added in an amount that is not below 2 moles based on 1 mole of the organic halide, the amount being not less than 0.3 mole based on 1 mole of water. The preferred amount of an alkali metal hydroxide is about 2.5 to 4 moles per 1 mole of the organic halide and about 0.35 to 0.85 moles per 1 mole of water. In general, there is no need to use an alkali metal hydroxide in an amount of more than 5 moles per 1 mole of an organic halide as well as in an amount of more than 1 mole per 1 mole of water.

Satisfactory results can then be achieved ^ if Sodium hydroxide is used as an alkali metal hydroxide. This

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Hydroxide is cheaper than potassium hydroxide, which is also used either in place of or in addition to sodium hydroxide. The alkali metal hydroxide can be added to the reaction system in the form of a solid separate from water, but it can also be added as an aqueous Solution with 40 to 75% by weight are added, the advantage being achieved that the supply of the alkali metal hydroxide to the reaction system made very simple, in addition, the working conditions of the staff can be improved and in general the reaction yield and the reaction rate can be increased.

The reaction temperature varies between 0 and 150 ° C. and preferably between 40 and 80 ° C to achieve an optimal reaction rate and a favorable reaction yield. The reaction can be carried out under atmospheric pressure if the reaction mixture is not at a temperature up to the reaction temperature boils. If appropriate, the reaction can also be carried out either under reduced or increased pressure. At the temperature at which at least one component the reaction mixture boils, the reaction can be more expedient Way to be carried out under reflux at atmospheric pressure. Are starting materials with a particularly low boiling point is used, the reaction can be carried out in a sealed system under reduced pressure.

The time required to complete the reaction depends on the starting materials, the reaction temperature and the desired conversion, but in general the reaction will last as long continued until practically all of the organic halide is consumed. Usually the organic halide in the Reaction system practically complete in 10 minutes to a few Consumed 10 minutes.

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According to one embodiment of the invention, conventional Liquid phase reaction methods and devices can be used. In most cases, the mix is first an organic halide and a ketone. It is not necessary to remove the water from the mixture, since water present in the mixture does not affect the reaction. The alkali metal hydroxide preferably in an aqueous solution is present, can be added before or after the addition of the phosphonium salt to initiate the reaction will.

Since the supply of the starting materials is completed within a period of a few minutes to a few tens of minutes, the order in which the raw materials are added only plays a subordinate role, if at all, in terms of reaction rate and yield. As can be seen from the above, means the "initiation of the reaction" that an organic halide, a ketone, an alkali metal hydroxide and water (if the Reaction is carried out in an anhydrous state, no water is added to the reaction system) is supplied to the reaction system and the temperature is increased to a certain predetermined value. A narrower interpretation of this term is not intended.

The reaction is usually carried out until practically the whole amount of the organic halide fed has been consumed. After the reaction is complete, an alkyl metal halide is formed by reacting the alkali metal hydroxide with a hydrogen halide is formed by reacting the organic halide with a ketone has been generated, or a mixture thereof with an unreacted alkali metal hydroxide (if a small amount Water is added) precipitated in the reaction liquid.

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Usually water is added to the reaction liquid, to dissolve the alkali metal halide or the aforesaid mixture and to decompose a residue of organic halide. The resulting liquid separates into two layers, an organic layer and an aqueous layer. the Organic layer is subjected to a further separation process, for example distillation, to give the product to separate. The unreacted acetone recovered in this process is recycled. Contains the reaction liquid an unreacted starting material with a relatively low boiling point, such as acetone, at any convenient time after the reaction is complete and before the liquid is separated into an organic one and into an aqueous layer, then the unreacted material can be recovered by evaporation. Furthermore, the Reaction liquid comprising an alkali metal hydroxide or a mixture thereof with an unreacted alkali metal hydroxide contains in the form of a precipitate, filtered, whereupon the FiI-occurred is separated into an organic and an aqueous layer. The generated ketone is separated from the organic layer. If an unreacted alkali metal hydroxide is present as an aqueous solution in the filtrate, then the aqueous Layer separated from the reaction liquid is again supplied to the reaction system and again to be carried out of the next cycle, if applicable. The aqueous layer is concentrated and / or with a fresh alkali metal hydroxide used for a new use.

The organic halide and the ketone used as the starting material do not need any compounds to carry out the invention be with a particularly reactive chemical structure. Examples of organic halides are alkyl halide, such as for example methyl chloride, methyl bromide, ethyl chloride, ethyl

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bromide, propyl chloride, propyl bromide, butyl chloride, octyl chloride as well as octyl bromide, alkenyl halides such as 1-chloro-3-butene, citronellyl chloride, allyl halides, for example Allyl chloride and allyl bromide, methallyl chloride, crotyl chloride, geranyl bromide, farnesyl chloride and phytyl chloride, Propargy! Halides, such as propargyl chloride, Cyclohexyl halides and benzyl halides. The iodides corresponding to the above examples can also be used will.

Ketones which are used to carry out the process according to the invention are suitable are those having at least one active hydrogen atom on the carbon atom of the ^ -position with respect to the carbonyl group. Examples are alkyl ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, Methyl isobutyl ketone, ethyl butyl ketone, methyl amyl ketone, methyl isoamyl ketone and methylhexyl ketone, unsaturated ketones such as mesityl oxide, allyl acetone, methylheptenone and ionone, aliphatic cyclic ketones such as cyclopentanone, cyclohexanone and cycloheptanone, Camphor, acetophenone and phenyl acetone. The substituted ones Ketones, which are made by reacting the organic halide with a ketone, are useful as Perfumes or as synthetic intermediates. For example, methylheptenone is suitable, which is produced by reacting Prenyl chloride is made with acetone, especially as a synthetic intermediate for making vitamin E as well as an intermediate product in the manufacture of perfumes.

example 1

In a 200 ml round bottom flask fitted with a thermometer, a A reflux condenser and a stirrer are provided, 10.46 g of 1-chloro-3-methyl-2-butene (hereinafter referred to as "prenyl chloride") , 51 ml acetone, sodium hydroxide (three times the molar amount,

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based on the prenyl chloride) as a powder or as aqueous Solution, where the water / prenyl chloride molar ratio is between 0 and 10, and 0.438 g of tricyclohexylethylphosphonium iodide (1 mol%, based on the amount of prenyl chloride) are added, whereupon the mixture is stirred vigorously for a period of 5 hours under reflux of the acetone. After completion to the reaction, 40 ml of water are added to the resulting mixture to dissolve the precipitated sodium chloride. Jie Yield, based on the theoretical amount, is determined by quantitative analysis of methylheptenone in the organic layer determined by gas chromatography. The results are plotted in the form of curve 1 in the accompanying FIG.

The same reactions are repeated using the following catalysts in an amount of 1 mol%, based on prenyl chloride, can be used under the same conditions. The results are shown in FIG.

Catalyst: tri-n-butylphosphine (curve 3) ammonium chloride (curve 4) Hydroxyethylamine (curve 2)

. As can be seen clearly from Figure 1, methylheptenone is independently in a good yield ^thereof: obtained if water is contained in the reaction system, if Tricyclohexyläthylphosphoniumjodid is used as catalyst.

Example 2

A mixture of 10.45 g of _{prenyl chloride, 34.8 ml of CH 3} COCH, 18.46 g of a 65% strength aqueous sodium hydroxide solution, 0.0218 g (CyClO-C ₆ H ₁₁ ) -PC ₂ H ₅ J (0.05 mol% based on the amount

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of prenyl chloride) and n-decane (standard that is used to carry out the gas chromatography measurement), the mixture vigorously for a period of time / on 4 Is stirred for hours under reflux of acetone.

The same reactions are repeated under the same conditions, using 1 mol%, (based on the amount of prenyl chloride) of (nC ₄ H ₉ ) ₃ PC ₂ H ₅ Br, (^ C ₄ H ₉ J ₄ PBr, ^ - C ₄ H ₉ ) ₃ PCH ₂ CH = C (CH ₃ ) ₂ C1 or (Ph) _PCH _o C, H _c Br is used.

3 pounds. DD

After completion of the reaction, the yield of methylheptenone will be and the conversion in the same way as in Example 1 was determined. The results are summarized in Table I:

Table I catalyst

(CyClO-C ₆ H ₁₁ J ₃ PC ₂ H ₅ J

PC ₂ H ₅ Br

Yield to
Methylheptenone,% Sales, % 63.5 99.8 27.5 40.0 44.2 63.6 2.7 3.6 O 0

(nC ₄ H ₉ ) ₃ PCH ₂ CH = C (CH ₃ ) ₂ C1 (C ₆ H ₅ J ₃ PCH ₂ C ₆ H ₅ Br

Comments: (CyCIo-C ₆ H ₁₁ J ₃ PC ₂ H ₅ J is used in an amount of 0.05 mol%, based on the amount of prenyl chloride, while all other phosphonium salts each in an amount of 1 mol% (on the same basis) can be used.

Examples 3 to 9

In the same reaction vessel that was used in Example 1 a mixture of 10.46 g of prenyl chloride, 34.8 ml

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CH-COCH-, 18.46 g of a 65% aqueous sodium hydroxide solution and 0.05 mol% of the phosphonium salt given below (based on the amount of prenyl chloride), whereupon the mixture vigorously for a period of 5 Is stirred for hours under reflux of acetone. After completion of the reaction, the yield, based on the theoretical Amount determined in such a way that the methylheptenone is analyzed qualitatively by gas chromatography.

Example catalyst: R ₃ PR ¹ X yield of methylheptenone,% RR ¹ X

3 4 5 6 7 8 9 10

11

^C 2 ^H 5 J 64.1 J 61.2 HC ₄ H ₉ Br 60.5 ⁿ - ^C 6 ^H 13 Br 59.8 J 60.1 ^C 12 ^H 25 Br 58.6 C ₁₈ H ₃₇ J 59.0 Cz-Hr-CH «
whether 2 Br 54.3 ^C 2 ^H 5 J 55.2

Example 12

10.46 g of prenyl chloride, 34.8 ίαΐ acetone, 18.46 g of 65% NaOH and 0.439 g (CyClO-CcH ₁₁ KPC ₉ H ₁ -J (1 mol%, based on the amount of prenyl chloride), whereupon the mixture is stirred vigorously for a period of 3 hours under acetone reflux

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- 16 determined in the usual way and found to be 51.6% and 94.3% respectively.

The same reaction is carried out under the same conditions such that 0.678 g of Cn-C ₄ H _{9 I 4} PBr (2 mol% based on the amount of prenyl chloride) are reacted over a period of 3 hours. The methylheptenone yield and the conversion of the prenyl chloride are found to be 61.2% and 99.0%, respectively. Then, 10.45 g of prenyl chloride _{, 7 ml of CH 3 COCH 3} and 4 g of NaOH are supplied to the reaction system, and the mixture is reacted for 3 hours in the same manner as described above. The yield of methylheptenone and the conversion of the prenyl chloride are found to be 13.6% and 34.0%, respectively.

Example 13

After completion of a repeated reaction using (CyClo-C ₆ H ₁₁ ) ₃ PC „H ₅ I according to Example 12 as a catalyst, 30 ml of HO are added in order to dissolve the precipitated sodium chloride. Then the organic layer is separated from the aqueous layer. After the acetone has been distilled off from the organic layer, 10 ml of ethyl ether are added to obtain a precipitate. The precipitate obtained is filtered. This gives crystals which are then washed with ethyl ether. After drying under reduced pressure, 0.27 g of crystals are obtained.

The reaction is carried out over a period of 2 hours using the product thus obtained as a catalyst carried out under the same conditions as in Example 12. The yield of MethylheptenDn and the conversion of the Prenyl chloride is determined in the usual way and found to be 64.5% and 98.5%, respectively.

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Example 14

250 ml of a concentrated hydrochloric acid are added to 154.3 g of linalool at 5 ° C., whereupon 100 ml of heptane are added. After separation, the organic phase is washed with three 50 ml portions of water. 407 g of acetone, 18.64 g of a 65% strength aqueous sodium hydroxide solution and 3.28 g (Cyclo-CgH ....) - P ^ nC ₄ H ₉ Br are added to the resulting solution, whereupon the mixture is heated for a period of time is refluxed for 3 hours. 300 ml of water are added to the reaction mixture and the organic layer is separated off. After the solvent has been distilled off under reduced pressure, 87.3 g of geranyl acetone are obtained (yield 45%).

Example 15

72.1 g of methyl ethyl ketone, 19.1 g of allyl chloride, 80 g of a 50% strength aqueous sodium hydroxide solution and 1.07 g of (Cyclo-CgH ..) ₃ P (CH ₃ ) .... are placed in a 500 ml autoclave , whereupon the mixture is reacted at 65 ° C for 4 hours with stirring. 13.1 g of 1-methylallylacetone are obtained, which can be determined quantitatively by subjecting the reaction mixture to gas chromatography (yield 53%).

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Claims (12)

- 18 claims 1. Process for the preparation of a substituted ketone by Reaction of an organic halide with a ketone with an active hydrogen atom on the (^ carbon atom with respect to the Carbonyl group in the presence of an alkali metal hydroxide and a phosphonium salt as a catalyst, characterized in that that as a catalyst a phosphonium salt of the general formula: R ₃ PR ¹ X is used, wherein R is a substituted or unsubstituted cyclohexyl group, P is a phosphorus atom, R ^{1 is} a substituted or unsubstituted alkyl group, a cycloalkyl group with not less than 6 carbon atoms or an aralkyl group with not less than 7 carbon atoms, and X is an anion. 2. The method according to claim 1, characterized in that a phosphonium salt of the formula given is used in which R stands for a cyclohexyl or 4-methylcyclohexyl group and R ^{1 is} an alkyl group with 1 to 18 carbon atoms, a benzyl group or a cyclohexyl group. 3. The method according to claim 1, characterized in that a phosphonium salt of the formula given is used in which X is Cl ", Br", J ~, OH ~ or NO ₃ ". 4. The method according to claim 1, characterized in that the phosphonium salt in a concentration of 0.001 to 20 mol%, based on the organic halide, is used. 5. The method according to claim 1, characterized in that the 609813/1008 Phosphonium salt in a concentration of 0.005 to 1.0 mol%, based on the organic halide, is used. 6. The method according to claim 1, characterized in that the reaction in the presence of water at a molar ratio Water / organic halide from 2.0 to 10.0 and in the presence of an alkali metal hydroxide in an amount from 0.35 to 0.85 mol, based on 1 mol of water, is initiated. 7. The method according to claim 1, characterized in that the reaction at e:
is carried out. the reaction at a temperature between 0 and 150 ° C 8. The method according to claim 1, characterized in that the reaction using an organic halide as well as a ketone having an active hydrogen atom on the CC carbon atom with respect to the carbonyl group in a molar ratio from 2: 1 to 1:20 is initiated. 9. The method according to claim 1, characterized in that the organic halide used from an alkyl halide, an alkenyl halide, an ally halide, a propargyl halide, a cyclohexyl halide or a benzyl halide. 10. The method according to claim 1, characterized in that the organic halide used consists of prenyl chloride. 11. The method according to claim 1, characterized in that the ketone used with an active hydrogen atom on the O & carbon atom with respect to the carbonyl group of one Alkyl ketone, an unsaturated ketone, an alicyclic ketone, camphor, acetophenol or phenyl acetone. 609813/100 8 12. The method according to claim 1, characterized in that the ketone used with an active hydrogen atom on the oC carbon atom with respect to the carbonyl group consists of acetone. 6098 13/1 008