DE2262343A1 - METHOD FOR MANUFACTURING KETONES - Google Patents

Description

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509 Leverkusen, Bayerwerk Zg / Ku

1 9JEL

Process for the production of ketones ■

The invention relates to a method 25 for the production of Ketones from aromatic or heterocyclic aldehydes and unsaturated compounds by reaction in the presence of cyanide ions.

It has been found that ketones are obtained in good yields if aromatic or heterocyclic aldehydes are used with unsaturated ones Compounds of the general formula

R ¹

in the

R, R ^ and R

C = C

are identical or different and represent hydrogen, an optionally substituted aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radical or a carbon ester group and represent the nitrile radical (CN), the group -CO- R ⁵ or the group -CO-OR ^ stands,

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in which

5
R is an optionally substituted aliphatic,

means cycloaliphatic, araliphatic, aromatic or heterocyclic radical, and

12 3 U 1 ^ P R and R and / or R and R or R and R · ^ and / or R and

4 2 5
R or R and R ^ together with the carbon atoms substituted by them can also form a carbocyclic or heterocyclic ring,
in the presence of cyanide ions.

In general the inventive process in the temperature range between -10 and "+100 ⁰ C, preferably from about 10-75 ⁰ C, in particular between 20 and 50 ⁰ C performed '.

As an aliphatic radical (R, R, R and R ^) are optionally substituted, straight-chain or branched aliphatic radicals with up to 12, preferably up to 6 carbon atoms, called, 'for example hexyl and pentyl radicals, the butyl, Isobutyl, tert. Butyl, propyl, isopropyl, ethyl and Methyl radical.

As cycloaliphatic radicals (R, R, R ^ and R ^) are such with up to 18, preferably 12, in particular 5 to 7 carbon atoms mentioned, but preferably the cyclohexyl radical.

As optionally substituted araliphatic radicals (R, R, R and R), those with up to 18 »are preferred named up to 12 carbon atoms, the aliphatic part preferably containing up to 6 carbon atoms and the aromatic part Part is preferably a naphthyl or phenyl radical.

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1 2 ^ Optionally substituted aromatic radicals (R, R, R- ³ and R -, ^ are, for example, those with up to 18 carbon atoms, preferably the phenyl and naphthyl radical.

As an optionally substituted heterocyclic radical (R, R, R ^ and R ^) come in particular 5- and 6-membered heterocyclic radical in question, which can still be fused to a benzene ring. As heteroatoms are for example nitrogen, oxygen and sulfur. These heteroatoms can be in the heterocyclic rings be present once or several times and then also be the same or different. Examples of heterocycles are named: pyrrole, furan, thiofen, indole, coumaran, thionaphthene, Pyridine, pyrone, oxazole, imidazole, benzoxazole, benzimidazole, benzthiazole, quinoline, isoquinoline.

The heterocyclic ring systems (such as those mentioned above, for example) can also be completely or partially hydrogenated.

When the radicals R and R and / or R ^ and R or R and R- ³

2 4 2 5
and / or R and R or R and R together with the carbon atoms substituted by them form a ring, this ring can be both carbocyclic and heterocyclic, heterocyclic ring systems having the same scope of meaning as described above for the radicals R,

2 3 5
R, R and R ^ is described. The carbocyclic radicals are preferably 5- and 6-membered rings, that is, the cyclophentane and cyclohexane ring, as well

Can contain double bonds and, in the event that R and Br together form a ring, must contain at least one double bond.

As substituents of the optionally substituted aliphatic, cycloaliphatic, araliphatic and / or aromatic radicals come from halogen (fluorine, bromine, chlorine, iodine)

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preferably chlorine, the cyano group, the nitro group, the optionally mono- or disubstituted amino group, alkyl radicals, preferably with up to 6 carbon atoms, aryl radicals, preferably the phenyl radical, the hydroxyl group, alkoxy, Alkylthio, carbon ester and thiocarbon ester groups, preferably with up to 6 carbon atoms, as well as alkyl and aryl carbonyl groups and alkyl and arylthiocarbonyl groups.

The aromatic and heterocyclic aldehydes which are used for the process according to the invention correspond generally of the general formula

R ⁶ - C - H

Il II

in the

R stands for an optionally substituted aromatic or heterocyclic radical,

6th

The aromatic radicals (R) given above for R, R,

3 5
R and R mentioned, also with regard to the possible substituents in question.

The heterocyclic radical (R) are 5- and 6-membered ones heterocyclic rings in question, which can still be fused to a benzene ring. As heteroatoms are for example nitrogen, oxygen and sulfur are mentioned. These heteroatoms can be in the heterocyclic rings be present once or several times and then also be the same or different. Examples of heterocycles are called:

Pyrrole, furan, thiophene, indole, coumaran, thionaphthene, pyridine, Pyrone, oxazole, imidazole, benzoxazole, benzimidazole, benzthiazole, Quinoline, isoquinoline, carbazole, benzofuran, dibenzofuran.

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The heterocyclic radicals (R) can furthermore be substituted in the same way as the aromatic radicals (R, R, R and R) could be.

In general, the reaction is carried out as follows:

The aromatic or heterocyclic aldehyde is used in one Solvent dissolved and mixed with a cyanide and stirred for a short time, the temperature of the mixture in general increases slightly.

The unsaturated compound of the general formula I is then slowly dissolved, if appropriate, in a solvent added with stirring and, after the addition was complete, continued stirring for about the same time. After the reaction has ended the reaction product is isolated in a manner known per se.

In general, it is advantageous to add water to the reaction mixture for separating off the cyanide and to add the separate organic phase. Depending on the solubility of the solvent used and the reaction product in water it can be advantageous to extract the aqueous phase with an organic solvent. From the united organic phases, the reaction product is then isolated in a manner known per se, e.g. by stripping off the solvent, Distill. The reaction product isolated in this way can also continue to be used in a manner known per se, for example by Recrystallization, distillation, chromatography can be further purified.

In general, the reaction is carried out in a solvent carried out, polar solvents are particularly suitable for this; for example: methanol, Ethanol, isopropanol, dioxane, acetonitrile, dimethylformamide,

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Dimethyl sulfoxide, hexamethylphosphoric acid amide.

Dimethylformamide and dimethyl sulfoxide are preferred
used.

However, it can be carried out without a solvent. An excess of a starting material can also be used as a solvent Find use. .

It is not absolutely necessary to use anhydrous solvents, but these are preferred.

The amount of cyanide ions present in the reaction is not of critical importance. Catalytic amounts of less than 1 mol percent, based on the aldehyde, are sufficient.
In general, the process according to the invention is carried out in the presence of relatively large amounts of cyanide ions; it is about 5 to 100, preferably 10 to 50, in particular about
50 mol% based on the aldehyde. It is also possible,
to work in the presence of a large amount of cyanide ions.

The known cyanides can be used as cyanides.
The cyanides of the alkali metals, in particular potassium cyanide and sodium cyanide, are preferably used.

The cyanides can be used undried; preferred however, they are dried in a known manner, e.g. over KOH, before use.

The aromatic and heterocyclic aldehydes that can be used for the process of the invention are
known. For example:

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Benzaldehyde, 4-chlorobenzaldehyde, 2-chlorobenzaldehyde, 4-bromobenzaldehyde, 4-iodobenzaldehyde, 4-fluorobenzaldehyde, 2-, 3- and 4-nitrobenzaldehyde, 2,4-dinitro-benzaldehyde, salicylaldehyde, 2-, 3- and 4-methoxybenzaldehyde, 4-carbethoxybenzaldehyde, 2-, 3- and 4-methylbenzaldehyde, 2-, 3- and 4-Ethy! Benzaldehyde, <> (- and ß-naphthaldehyde, furfural, pyrrole-2-aldehyde, Indole-3-aldehyde, carbazole-4-aldehyde ^ benzofuran-2-aldehyde, Thiophene-3-aldehyde, pyrazole-3-aldehyde, imidazole-4-aldehyde, Benzimidazole-3-aldehyde, oxazole-4-aldehyde, pyridine-2-aldehyde, Pyridine-3-aldehyde, pyridine-4-aldehyde, 2-methylpyridine-3-aldehyde, Quinoline-5-aldehyde, quinoline-2-aldehyde, Isoquinoline-1-aldehyde, uracil-6-aldehyde.

It is also possible to use the benzoins of the general formula instead of the free aldehydes

HO.

₆ II ₆

R ^b - c - c - fr,

OH

in the

R - has the meaning given above,

to be used as starting material, since these are split back into the free aldehydes under the reaction conditions.

Likewise are the unsaturated compounds of the general form! I, which can be used for the process according to the invention, are known. For example:

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Methyl vinyl ketone, phenyl vinyl ketone, ß-naphthyl vinyl ketone, Benzalacetone, Dibenzal-acetone, Benzalplnakolin, 1-Benzalcyclopentanone- (2), Benzalacetophenone, 4'-nitro-chalcone, 4'-dimethylamino-chalcone, 2-hydroxy-4'-methyl chalcone, ß-pyridyl-ß-styryl-ketone, 3-nitrochalcone, p-anisal-cyclopentanone, Furfural acetone, 1 - (<x -pyridyl) -3-phenyl-propenone- (3), Mesityl oxide, cyclopentenone, cyclohexenone, 1-benzalcyclQ-pentanone- (2),

Acrylic acid esters, crotonic acid esters, maleic acid esters, cinnamic acid ester, <? o-pyridyl acrylic acid ester, furfurylidene acetic acid ester, Cyclohexene (1) carboxylic acid ester, p-nitrocinnamic acid ester;

Acrylonitrile, methacrylonitrile, croton nitrile, cinnamonitrile, cyclopentane (1) carboxylic acid nitrile.

Instead of the JJ ₁ ßunsaturated ketones of the general formula corresponding to the general formula I

R ¹ - CH = CH - C - R ⁵ III

Il
0

in the

1 5
R and R the above. Mannich bases of the general formula can also have meaning

R ⁸

^, N - CH ₉ -CH ₉ - CR ⁵ IV

_7/2 ² Il

R '0

in the

7 R '

R and R are the same or different and are aliphatic A radical with up to 6, preferably up to 3 carbon atoms, in particular the methyl radical, or together with the nitrogen atom for a 5- or

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β-membered ring and R ^ has the meaning given above,

can be used, since these are unsaturated under reaction conditions with elimination of the corresponding secondary amine Connection respond.

Examples of such Mannich bases are: N, N-dimethyl-ß-benzoylethylamine, N- (3-oxobutyl) piperidine, Ν, Ν-diethyl-ß-pivaloyl-ethylamine.

According to the reaction equation ^ equimolar amounts of aldehyde and unsaturated compound of formula I react. In general, however, an excess of aldehyde is used. In general, it can be chosen arbitrarily. The process according to the invention is generally not influenced by this. It will expediently be approximately up to 100 % . An excess of about one third is preferably used.

If the corresponding benzoin is used as the starting material instead of the aldehyde, its molar amount is because of the equivalence only half of the otherwise used molar amount of aldehyde.

The unsaturated compound of the formula I can also optionally be used in excess.

The example of benzaldehyde and acrylonitrile is what is according to the invention Procedure explained in the following formula:

CH + CH, = CH - CN - »ί *. Lt-C - CH, - CH, - CN

CN 'O -

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The ketones which can be obtained by the process according to the invention correspond to the general formula

R ¹ H
R ⁶ - C - C - C - R ⁴

in the

R, R, R, R and R have the meaning given above.

The ketones which can be obtained by the process according to the invention are valuable intermediates.

In the following examples, elemental analyzes are indicated the percent sign is omitted according to the usual notation.

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The NaCN used in the following examples was powdered beforehand and dried over KOH in a desiccator.

The abs used in the examples below. Dimethylformamide was dried by distillation over calcium hydride. ■

example 1

In a 500 ml four-necked flask with a dropping funnel, stirrer, KOH drying tube and internal terraometer, 320 ml of abs. Dimethylformamide, 23.5 g (0.4 mol) of freshly distilled benzaldehyde and 9.8 g (0.2 mol) of sodium cyanide were introduced. After the sodium cyanide has been added to the reaction mixture, a weak exothermic reaction occurs, the temperature rising ^{from 30 °} C. to 34 ^{° C.} The mixture is stirred for 15 minutes at an ^{internal temperature of 30 °} C. and a solution of 15.9 g (0.3 mol) of freshly distilled acrylonitrile and 80 ml of abs is added dropwise over the course of one hour. Dimethylformamide into the reaction mixture at the same temperature. The mixture is stirred for 1 1/4 hour at the same temperature. Then the very creamy reaction mixture is poured into 800 ml of water and shaken well. The aqueous solution is extracted twice with 200 ml of chloroform each time and two times with 100 ml of chloroform each time. The combined chloroform solutions are washed well with water, dried over MgSO ^ and the chloroform is distilled off. Seed crystals are added to the residue. The ß-benzoylproplonitrile then crystallizes out immediately. It is suctioned off and washed with ethanol. 26.6 g of β-benzoylpropionitrile with a melting point: 69 ^° C. are obtained. From the mother liquor, even by further cooling in

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22623A3

Dry ice-acetone bath no further precipitation can be achieved. The concentrated mother liquor is therefore subjected to vacuum distillation, with a further amount of the reaction product being able to be isolated.

Yield: 37.6 g (79 % of theory) ß-benzoylpropionitrile. After recrystallization from ethanol, melting point: 74 ^° C.

Example 2

Analogously to the procedure described in Example 1, 42.5 g (0.2 mol) of benzoin (melting point: 131 ^° C.), 320 ml of abs. Dimethylformamide and 9.8 g NaCN (dried) (0.2 mol) combined. When NaCN is added to the reaction mixture, a weak exothermic reaction also occurs. Then a solution of 15.9 (0.3 mol) freshly distilled acrylonitrile and 80 ml abs. Dimethylformamide was added dropwise. The reaction mixture shows the same external phenomena as in the reaction between benzaldehyde and acrylonitrile. The crude product (62 g) is subjected to distillation. After the first runnings have been distilled off (1.6 g with a faint odor of benzaldehyde), 35.1 g of β-benzoylpropionitrile are obtained. Kp .: 139-143 ⁰ C / 0.5 mm Hg, m.p .: 65-66 ⁰ C.

Example 3

In a 500 ml four-necked flask with two dropping funnels, stirrer, KOH drying tube and internal thermometer, 200 ml of abs. Dimethylformamide and 1.0 g (0.02 mol) of sodium cyanide were submitted. A solution of 56.2 g (0.4 mol) of p-chlorobenzaldehyde and 120 ml of abs. Dimethylformamide, added dropwise at 35 ° O within 3/4 hour. Here, eiph forms a creamy product. The mixture is stirred for a further 15 minutes.

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Another solution of 15.9 g (0.3 mol) of freshly distilled acrylonitrile and 80 ml is added to this reaction mixture Dimethylformamide was added dropwise at an internal temperature of 34-35 ° C. within 1 1/2 hours. The same is left for 1 1/2 hours Stir temperature. Towards the end of the reaction, a very creamy product is formed again. About 1 liter of water is then added to the reaction mixture and the mixture is shaken well, with a reddish greasy product precipitates, which is suctioned off.

The mother liquor is extracted twice with 20 ml of chloroform. The chloroform solutions are washed with water and the chloroform is distilled off. 9.2 g of an oily product are obtained from which crystals later precipitate. Since an exact separation of the suctioned off reaction product by crystallization is not possible, the reaction product chloroform is dissolved. The chloroform solution is washed with water, dried over MgSO / and then the solvent is distilled off. The crude product (67.9 g) is subjected to distillation. 182 ⁰ C / 0.5 mm Hg ß-p-Chlorbenzoylpropionitril - 178 are obtained in the SDP.. Recrystallization from ethanol gave a pure product with a melting point of 72 ° -73 ° C., which was identified on the basis of the analytical data and comparison with a sample prepared in another way.

Example 4

Analogously to the procedure described in the examples, 56.2 g (0.4 mol) of p-chlorobenzaldehyde in 120 ml of abs. Dissolved dimethylformamide, slowly added dropwise to a mixture of 9.8 g (0.2 mol) NaCN and 200 ml dimethylformamide. A solution of 34.3 g (0.3 mol) of freshly distilled Crotonsäureäthylester and 80 ml of DMF is then slowly added dropwise at 35 ⁰ C over 2 1/2 hours to this reaction mixture.

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The mixture is stirred for 2 1/2 hours at the same temperature, added Then the reaction mixture with twice the amount of water, extracted with chloroform, washes the combined Chloroform solutions wash well with water, dry over MgSO ^ and the chloroform is distilled off. 79 g of crude product are subjected to distillation.

Yield: 43 g (56% of theory) ß-p-Chlorbenzoylbuttersäureäthylester Kp .: 121 ⁰ C / 0.2 mm Hg, m.p .: 39 ° C
C ₁₃ H ₁₅ O ₃ Cl (254.72) calcd. C 61.30 H 5.94

Found C 61.13 H 5.80

Example 5

Analogously to the procedure described in Example 3, 28.1 g (0.2 mol) of chlorobenzaldehyde are dissolved in 100 ml of dimethylformamide dissolved, slowly to a mixture of 4.9 g (0.1 mol) NaCN and 100 ml abs. Dimethylformamide was added dropwise.

Then a solution of 21.9 g (0.15 mol) of benzalacetone and 100 ml of abs. Dimethylformamide slowly added dropwise.

The mixture is left to stir for 4 hours at the same temperature, then twice the amount of water is added to the reaction mixture, extracted with chloroform, washed thoroughly with water, dried over MgSO ^ and the chloroform is distilled off. 49 g of crude product are subjected to distillation. Yield: 38.4 g (89.5 % of theory) 1,4-Dioxo-1- [4-chlorophenyf] -2-phenyl-pentane bp .; 164 ^° C / 1.5 mm Hg, m.p .: 64 ^° C (ethanol) C ₁₇ H ₁₅ O ₂ Cl (286.76) calc .: C 71.20 H 5.28 Cl 12.36

Found: C 71.53 H 5.33 Cl

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Example 6

Analogously to the procedure described in Example 3, a solution of 21.2 g (0.2 mol) of benzaldehyde and 100 ml of abs. Dimethylformamide within 1/2 hour to a mixture of 4.9 g (0.1 mol) of NaCN and 100 ml of abs. Dimethylformamide dripped. The mixture is then allowed to stir at 35 ° C. for 11/2 hours. A solution of 21.9 g (0.15 mol) of benzalacetone and 100 ml of dimethylformamide is then slowly added dropwise at 35 ⁰ C in 3 1/2 hours. Stirring is continued for 3 1/2 hours at the same temperature stir, then R _e offset action mixture with twice the amount of water and worked up analogously to Example 5 on. 43.5 g of crude product are obtained, from which 25.2 g of 1,4-dioxo-i, 2-diphenylpentane (67 % of theory ) are obtained by distillation.

Kp .: 166 ⁰ C / 0.4 mm Hg .. mp: 60 - 61 ⁰ C C ₁₇ H ₁₆ O ₂ (252.3) Calc .: C 80.92 H 6.39

Found: C 80.62 H 6.50

Example 7

Analogous to the procedure described in Example 3, a solution of 21.2 g (0.2 mol) of benzaldehyde and 75 ml of abs. DMSO within 1/2 hour to a mixture of 0.98 g (0.02 mol) NaCN or KCN and 75 ml abs. Dimethyl sulfoxide was added dropwise. The mixture is then allowed to stir ^{at 35 ° C. for 1/2 hour.} A solution of 29.2 g (.0.2 mol) of benzalacetone and 75 ml of abs. Eimethylsulfoxid was added dropwise. The mixture is left to stir for a further 1/2 hour and worked up as in Example 5.
Yield 37.3 g (69 % of theory) 1,4-di oxo-1,2 -diphenylpentane.

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Example 8/6

Analogously to the procedure described in Example 3, a solution of 42.5 g (0.4 mol) of freshly distilled benzaldehyde and 125 ml of abs. Dimethylformamide was slowly added dropwise to a mixture of 19t6 g NaCN (0.4 mol) and 125 ml dimethylformamide. The mixture is stirred for 21 hours at an ^{internal temperature of 35 °} C., a creamy product being formed. Now, within 2.5 hours, a solution of 54.3 g (0.3 mol) of ethyl crotonate uride 150 ml of abs. Dimethylformamide are added dropwise at 35 ⁰ C. The mixture is left to stir at the same temperature for a further 3 hours and then twice the amount of water is added to the reaction mixture and the reaction mixture is worked up as in Example 3.

The crude product is subjected to distillation, 23.8 g of ß-benzoylbutyric acid ethyl ester (36% of theory) being obtained.

Bp .: 128 - 135 ⁰ C / 1.2 mm Hg
Example 9

Analogous to the procedure described in Example 3, a solution of 42.5 g (0.4 mol) of freshly distilled benzaldehyde is used and 125 ml abs. Dimethylformamide to a mixture of 19 »6 g NaCN (0.4 mol) and 125 ml of abs. Dimethylformamide dripped. The mixture is stirred at 35 ° C. for 12 hours. Now is within 2 hours a solution of 51.6 g (0.3 mol) of freshly distilled maleic acid diethyl ester and 150 ml of abs. Dimethylformamide 35 ° C added dropwise.

The mixture is left to stir at the same temperature for a further 2 hours and worked up as in Example 5. The crude product is subjected to distillation, 27-5 g of ethyl benzoylsuccinate (33 % of theory ) being obtained.

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^ 22G2343 V-

Yield: 27.5 g (33 # _{e of} theory)
Bp .: 150 - 16O ⁰ C / 0.8 mm Hg.

Example 10 - '

Analogous to the procedure described in Example 3 is a solution of 56.2 g (0.4 mol) of p-chlorobenzaldehyde and 120 ml abs. Dimethylformamide slowly to a mixture of 9.8 g (0.2 mol) NaCN and 200 ml abs. Dimethylformamide dripped.

A solution of 51.6 g (0.3 mol) of Irish distilled maleic acid diethyl ester and 80 ml of abs is then added to this reaction mixture within 4 hours. Dimethylformamide are added dropwise at 35 ⁰ C. The mixture is stirred for 4 hours at the same temperature, then the reaction mixture is mixed with twice the amount of water and worked up as in Example 5.

The residue is subjected to distillation, 32.5 g of ethyl p-chloro-benzoylsuccinate being obtained. (34.5 f> d. Th.) Receives. , '"·

Example 11

Analogously to the procedure described in Example 3, a solution of 28.1 g (0.2 mol) of p-chlorobenzaldehyde and 100 ml Ethanol (abs.) Was added dropwise within 1/2 hour. The mixture is left to stir for half an hour at the same temperature.

A solution of 31.2 g (0.15 mol) of benzalacetophenone and 100 ml of abs is then added over the course of 2 hours. Ethanol is slowly added dropwise at 35 ⁰ C. The mixture is left to stir for 2 hours at the same temperature, then twice the amount of water is added to the reaction mixture and the procedure is as in Example 5. '..

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57.1 g of crude product are obtained from the 42.6 g (80 % of theory , J> 1,4-dioxo-1- (p-chlorophenyl) -2,4-diphenyl-butane) as a white product by crystallization in ethanolic solution crystalline «product can be isolated.
Ip .: 92-93 ⁰ O

Example 12

Analogously to the procedure described in Example 3, 27.2 g (0.2 mol) of p-methoxybenzaldehyde, 9.8 g (0.2 mol) of NaCN and 140 ml of abs. Dimethylformamide combined. The mixture is stirred internal temperature, the reaction mixture overnight at 7O ⁰ C. It is then cooled to 35 ⁰ C, and then dropwise within 1 hour, a solution of 5.3 g (0.1 mol) of freshly destillertem from acrylonitrile and 70 ml of abs. Dimethylformamide at the same temperature too. The mixture is left to stir for one hour at the same temperature, then twice the amount of water is added to the reaction mixture and the reaction mixture is worked up as in Example 9.

The crude product is subjected to distillation, with 11.4 g of β- (4-methoxyphenyl) propionitrile. (60.4 1 » d. Th) can be obtained.
Bp. Ι 196 - 198 ⁰ C / 0.6 mm Hg
Fp.ϊ 94 ⁰ C

Example 13

Analogously to the procedure given in Example 3, j

a solution of 38.4 g (0.4 mol) of freshly distilled -.!

Furfural and 100 ml abs. Dimethylformamide within 45 minutes

th to a mixture of 9.8 g (0.2 mol) NaCN and 200 ml \

Section. Dimethylformamide was added dropwise at 35 ° C. The mixture is left to stir for 15 minutes. Then within 1 hour

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a solution of 15.9 g (0.3 mol) of freshly distilled acrylonitrile at 35 ⁰ C are added dropwise. The mixture is stirred for 11/4 hours at the same temperature and then twice the amount of water is added to the reaction mixture. Since the reaction product cannot be extracted very easily with chloroform, it is carefully acidified with dilute sulfuric acid and worked up as described in Example 5.

The reaction product is subjected to distillation, 13.6 g of β-furoylpropionitrile (3Z ~% of theory ) being obtained.

Bp .: ^{133-136 0} C / 1 mm Hg mp, i76 ^O C. Example 14

Analogously to the "procedure described in Example 3", a solution of 38.4 g (0.4 mol) of freshly distilled furfural and 125 ml of absolute dimethylformamide is converted into a mixture of 9.8 g (p , _2 mol) of NaCN and 125 ml of abs. dimethylformamide was added dropwise. the mixture is stirred for half an hour at 35 ⁰ C. then, within 11/2 hours, a solution of 43.8 g (0.3 times) and 150 ml of abs benzalacetone The mixture is stirred for 11/2 hours at the same temperature, twice the amount of water is then added to the reaction mixture and it is worked up as described in Example 5. From 83.5 g of crude product, 32.1 g of 1, 4-Dioxo-1-furyl-2-phenylpentane (44% of theory) isolated.

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Analogously to the procedure described in Example 3, a solution of 19.2 g (0.2 mol) of freshly distilled furfural and 100 ml of abs. Dimethylformamide within 1 hour at 35 ° C to a mixture of 4.9 g (0.1 mol) of NaCN and 100 ml of abs. Dimethylformamide is added dropwise. The mixture is left to stir at 35 ^° C. for a further 1/2 hour. Then a solution of 31.2 g (0.15 mol) of benzalacetophenone and 100 ml of abs. Dimethylformamide was added dropwise. The mixture is left to stir for 2 hours at the same temperature, then twice the amount of water is added to the reaction mixture and it is worked up as in Example 5 .

This gives 51.2 g of crude product from the crystallization in ethanolic solution, 38.8 g of 1,4-dioxo-1-fury1-2,4-diphenyl butane (84.5 $> d. Th.) Are isolated.

Fpr: 115 - 116 ° C 16 .33) Ber. C. 78 , 93 H 5 , 30 ^C 2O ^H 16 ° 3 (304 Found C. 79 , 11 H 5 , 49 example

Analogously to the procedure described in Example 3, a solution of 42.5 g (0.4 mol) of freshly distilled benzaldehyde and 125 ml of abs. Dimethylformamide slowly to a mixture of 19.6 g (0.4 mol) NaCN and 125 ml abs. Dimethylformamide dripped. The mixture is stirred for 2 hours at an ^{internal temperature of 35 °} C., a creamy product being formed. .

Now, within 3 hours, a solution of 52.8 g (0.3 mol) Cinnamic acid ethyl ester and 150 ml of abs. Dimethylformamide 35 ° C added dropwise. The same is left for 3 hours

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Stir temperature and work up as in Example 5.

By distilling the crude product 12 °, 6 g of 4-0x0-3,4-diphenyl-butyric acid ethyl ester (15 # d. Th.) isolated"

Example 17

Analogously to the procedure described in Example 3, a solution of 21.2 g (0.2 mol) of benzaldehyde and 100 ml of abs. Dimethylformamide was added dropwise within 1/2 hour to a mixture of 9.8 g (Ov, 2 mol) NaCN and 100 ml absolute dimethylformamide. The mixture is left to stir at 35 ° C. for a further 2 1/2 hours. A solution of 26.6 g (0.15 mol) of dimethyl-β-benzoyl-ethylamine and 100 ml of abs is then slowly added over a period of 2 hours. Dimethylformamide was added dropwise. The mixture is stirred for 2 hours at the same temperature and then the reaction mixture is mixed with three times the amount of water, the reaction product precipitating immediately; After cooling in an ice bath, the precipitated product is filtered off with suction and washed well with water. 34 * 3 g of crude product are isolated. After recrystallization from ethanol, 21.6 g (60.5 % d * th.) Of Mbenzoylätiian are isolated ϊ mp *: 143 ⁰ g

Example 18

Analogously to the procedure given in Example 3, a solution of 21.2 g (δ.2 mol) of freshly distilled benzaldehyde and 100 ml of abs. Dimethylformamide within 1/2 hour to a mixture of 9.8 g (0.2 mol) NaCN and 100 ml of abs. Dimethylformamide dripped. The mixture is left to ^{stir at 35 °} C. for a further 1/2 hour.

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A solution of 19.8 g (0.15 mol) of phenyl vinyl ketone and 100 ml of abs. Of dimethylformamide was slowly added dropwise at 35 ⁰ C.

The mixture is stirred for a further hour at the same temperature and three times as much are added to the reaction mixture Amount of water and work up as in Example 17 · 35.2 g of crude product are obtained.

Yield: 23.5 g (65.5 % of theory) Dibenfcoyläthanj Mp .: 143 ° C

Example 19

Analogous to the procedure described in Example 3 is a solution of 5.35 g (0.05 mol) of pyfidine aldehyde (2) and 30 ml of abs. Dimethylformamide within 45 minutes to one Mixture of 2.45 g (0.05 mol) NaCN and 30 ml abs dimethylformamide dripped *

The mixture is stirred for 1 1/4 hours at the same temperature. Then within 2 hours iine a solution of 7.9 g (0.038 mol) of benzalacetophenone and 40 ml of abs. Dimethylformamide was added dropwise. The mixture is left for 2 hours. Allowed to stir at the same temperature, then the reaction mixture versetit with twice the amount of water and worked up as in Example 5.

There are 8.1 g 1 _f 4-dioxo-i- (2-pyridyl) -2,4-diphenyl butane (67.5 $ d. Ih.) Is isolated by fractional crystallization of 12.9 g of crude product in ethanol.

C ₂₁ H ₁₇ NO ₂ (315.35) Calc .: C 79.98 H'5.49 t 4.44

Found: C 80.15 H 5.6f i 4.45

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Example 20

Analogously to the procedure described in Example 3, a solution of 5.35 g (0.05 mol) of pyridinaldehyde (3) and 30 ml of abs. Dimethylformamide is added dropwise within 1/2 hour at 35 ^° C. to a mixture of 2.45 g (0.05 mol) NaCN and 30 ml absolute dimethylformamide. The mixture is stirred for 21/2 hours at the same temperature.

Then, within 1 hour, a solution of 6.73 g (0.038 mol) of dimethyl-ß-benzoyl-ethylene amine and

40 ml abs. Dimethylformamide was added dropwise. The mixture is left to stir for 3 hours at the same temperature, then twice the amount of water is added to the reaction mixture and the reaction mixture is worked up as in Example 5.

9.6 g of crude product are obtained, which are subjected to distillation. 3.2 g of 1,4-dioxo-1- (pyridy.l-3) -4-phenyl-butane are obtained (35 # d.Th) received.

Kp .: 205-215 ⁰ C / 0.4 mm Hg

M.p .: 1.02-103 ° C (from ethanol). . '

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In a 5OO ml four-neck flask with stirrer, dropping funnel, KOH drying tube and internal thermometer, freshly distilled water is added to a solution of 23.5 g (0.4 mol). Benzaldehyde in 320 ml of dimethylformamide (abs.) 2 g (approx. 0.04 mol) of sodium cyanide were added.

In the course of 15 Hin. the internal temperature rises from 25 ° to 30 ° C, and the mixture turns yellow-green.

Is then added dropwise within ejlrier hour, a solution of 15.9 g (0.3 mol) of acrylonitrile and 80 ml of dimethylformamide (abs.) At 30 ⁰ C in the reaction mixture. After a further 75 minutes, the batch is poured into 800 ml of water and shaken well.

It is extracted twice with 200 ml of chloroform each time and twice with 100 ml of chloroform each, washes the chloroform extracts thoroughly with water, dry over Na ^ SO ^ and distilled then take off chloroform.

The brown residue is subjected to vacuum distillation:

Kp 135 ° - 140 ⁰ C / 0.1 mm Hg. \

Dan üontillat is then recrystallized from ethanol. Is obtained in this case 24.3 g (51 # of theory) of ß-Benzoylpropionitril as colorless crystals of mp. 74 ⁰ C.

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Claims (10)

Patent claims: j). Process for the production of ketones, characterized in that that one aromatic or heterocyclic aldehydes with unsaturated compounds of the general formula R ¹ in the 12 3 "■ R, R and R are identical or different and ^{:. :} for hydrogen, an optionally substituted one aliphatic cycloaliphatic, araliphatic aromatic or heterocyclic radical or a Carbon ester group stand and R for the nitrile residue. (CN), the group -CO- R ^ or the group -CO-OR ^ is in which Br denotes an optionally substituted aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radical, and where ..., '''"' 1 2/3 4 1 " ³ I P R and R and / or R and R - or "-R- and Tr and / or R and 4 2 5 R or R and R ^ together with those substituted by them Carbon atoms can also form a carbocyclic or heterocyclic ring. in the presence of cyanide ions. A., 1AJ765. '- 25 - A fi-ä B.2BJΛ 1 J5J OBIGiNAL INSPECTED 2. The method according to claim 1, characterized in that ^ ' the benzoins of the general formula are used instead of the free aldehydes R ⁰ - C - CH - R I " OH sets in,
in the R stands for an optionally substituted aromatic or heterocyclic radical. 3. The method according to claim 1, characterized in that. instead of the general formula I use the same formula • Ay, ß-unsaturated ketones of the general formula R ¹ - CH = CH ₁ - C - R ⁵ III in the R is hydrogen, an optionally substituted aliphatic, cycloaliphatic!}, Araliphatic ₇ aromatic or heterocyclic radical or a carbonate group and Nester R ^ an optionally substituted aliphatic, means cycloaliphatic, araliphatic, aromatic or heterocyclic radical. Le A 14 763 - 26 - Mannich bases the general formula 5 ·· 2262343 R ⁸ ^ N _{- CH 2} - C ^R · ο in the 5
R has the meaning given above and R 'and R are an aliphatic radical or together with the nitrogen atom for a 5- or 6-membered Stand ring, used. ' 4. Process according to Claims. 1 to 3 »characterized in that that one works in a polar solvent; «* ■ 5. Process according to Claims 1 to 4, characterized in that that one cyanide ions in the form of sodium or potassium cyanide used. ■ '. 6. Process according to Claims 1 to 5, characterized in that sodium or potassium cyanide is used in an equimolar amount based on the aldehyde used. 7. ß-p-Chlorobenzoylbutyric acid ethyl ester _{8.1 y} 4 ~ Dioxo-1i ^ -chlorophenyl + Z-phenyl-pentane 9. 1,4-Dloxo-1,2-diphenyl-pentari 10. 1,4-Dioxo-i-furyl-2,4-diphenyl-butane Le AJ4 76 5 ORIGINAL INSPECTED