Method for preparing 3-bromoadmantyl-1-alkyl(aryl)-ketones

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of 3-bromoadamantyl-1-alkyl(aryl)-ketones of the general formula: , wherein that can be used as intermediate substances for synthesis of some biologically active compounds. Method involves interaction of 1,3-dehydroadamantane with α-bromoketones of the following order: α-bromoacetone, α-bromoacetophenone, α-bromocyclohexanone in the mole ratio of reagents = 1:(2-3), respectively, in absolute diethyl ether medium, at temperature 34-40°C for 3-4 h. Method provides preparing the claimed compounds with high yield.

EFFECT: improved method of synthesis.

3 ex

 

The invention relates to the chemistry of adamantane derivatives, and in particular to a new method of obtaining 3-bromodiphenyl-1-alkyl(aryl)ketones of General formula

which may be of interest as intermediates in the synthesis of some biologically active substances.

The known method of synthesis of 3-bromo-1-adamantanecarbonyl [Stetter N., Mayer J. Chem.Ber. 1962, 95, 667] and 3-bromo-1-adamantylamine acid [Bott, K. Chem.Ber. 1968, 101, 564-573] by direct synthesized 1-adamantanecarbonyl or 1-adamantylamine acids in the presence or in the absence of a catalyst.

The disadvantage of this method is the limited number of synthesized compounds, so that in this way it is impossible to obtain the claimed compounds of structural formula; requires chemical conversion with the help of which you can obtain the claimed compounds, but which are also not described in the literature.

Closest to the proposed invention is a method of obtaining 3-bromodiphenyl-1-acetone from 1,3-dibromobutane and isopropenylacetate in the presence of aluminum bromide as the catalyst exit 76% (RF Patent No. 2221769. SS 49/115, 49/15, 45/46. Publ. 22.24.2002].

The disadvantages of this method is the need to use significant amounts of aluminum bromide and solvent, the necessary stage, the neutral is Itachi and washing of the catalyst, who is lost and is not subject to regeneration. In addition, this method are only one of the compounds of the claimed structural formulas.

The task of the invention is to develop technological molestating method of synthesis of 3-bromodiphenyl-1-alkyl(aryl)ketones, flowing with high yield by source adamantane.

The technical result is the expansion of the range of chemical compounds, in particular obtaining new 3-bromodiphenyl-1-alkyl(aryl)ketones with high output.

The technical result is achieved in a new method of obtaining 3-bromodiphenyl-1-alkyl(aryl)ketones of General formula

using the adamantane derivative, characterized in that as adamantane derivative use 1,3-dehydroalanine, the process lies in the interaction of 1,3-dehydroalanine with α-bracketname from a number: α-bromoacetone, α-bromoacetophenone, α-bromocyclohexane, when the molar ratios of the reagents, respectively 1:2-3, in an environment of absolute diethyl ether at a temperature 34-40°C for 3-4 hours.

The essence of the method is the reaction for the preparation of 3-bromodiphenyl-1-alkyl(aryl)ketones by the reaction of joining 1,3-dehydroalanine relevant to the ith α -bromoketones.

The reaction is based on previously unknown properties of 1,3-dehydroalanine to interact liaison carbon-halogen bonds in the aliphatic, alicyclic and fatty-aromatic ketones containing bromine in α-position to a carbonyl group. The reaction is unknown, as the literature contains no information about the interaction of 1,3-dehydroalanine with α-bracketname or related compounds, as well as missing information on obtaining and properties of the claimed compounds of structural formulas. Interaction is possible due to the high mobility of the bromine atom in α-bracketing created electroreceptors influence located at the nearest methylene (methyl) group, carbonyl group.

The method is as follows.

To 2-3-fold molar excess of the appropriate α-brometea poured a solution of 1,3-dehydroalanine in boiling inert solvent (diethyl ether), while there is an exothermic effect. A solution of 1,3-dehydroalanine and α-brometea in diethyl ether is heated for 3-4 hours at the boiling temperature of the reaction mixture (34-40° (C), after which the solvent and excess of the original α-brometea distilled off in a water jet vacuum pump. It is possible to regenerate the original α-bromoketones of Potema distillation from the reaction mixture and the organization of recycling with the addition of the calculated amount of fresh α -brometea. Synthesized 3-bromodiphenyl-1-alkyl(aryl)ketones purified by vacuum distillation. The outputs of these products are 59-86%.

As studies have shown, the optimum condition for the reaction accession α-bromoketones to 1,3-dehydroalanine is its implementation in an environment of absolute diethyl ether at a molar ratio of 1,3-dehydroalanine : α-Bratton = 1:2-3. The use of the stoichiometric ratio has resulted in a slight decrease of the yield of the target products due to possible homopolymerization 1,3-dehydroalanine and incomplete conversion. A further increase in excess of α-brometea did not affect the yield of the target product was impractical due to Lacrimarum action α-bromoketones. The optimal reaction temperature is 34-40°to carry out synthesis in boiling diethyl ether. Rising temperatures and the use of more high-boiling solvents is impractical in connection with a sufficiently high reaction rate and low thermal stability of most α-bromoketones. The optimal treatment duration is 3-4 hours. Thus, there was complete conversion of 1,3-dehydroalanine.

The structure of the synthesized compounds was confirmed by NMR1N-spectroscopy and elemental Ana is Isom.

The invention is illustrated by the following examples.

Example 1.

3-Bromodiphenyl-1-acetone

To 9 g (of 0.066 mol) α-bromoacetone in an atmosphere of dry nitrogen at room temperature was added dropwise a solution of 3 g (0,022 mol) svezheosazhdennoi 1,3-dehydroalanine (ratio of 1,3-DCA : α-bromoacetone = 1:3) in 20 ml of absolute diethyl ether, after which the reaction mixture is boiled at a temperature of 34-40°C for 3 hours, after which the solvent and excess α-bromoacetone removed by distillation in a water jet vacuum pump, the residue is distilled in vacuum and obtain 3.7 g (0,0136 mol, 62%) 3-bromodiphenyl-1-acetone. TKip.=196-197°C /20 mm Hg, n20D1.5358. An NMR spectrum1N, δ, ppm: 1,45, 1,63, 2,09 (14 H, substituted-1,3), and 2.27 (3H, CH3), 2,32 (2H, CH2C(O)).

Found, %: C 57,64, N 6,93, Br 29,55. With13H19OBr. Calculated, %: C 57,56, N 7,01, Br 29,52.

Example 2.

2-(3-Bromodiphenyl-1)cyclohexanone

To 9,74 g (by 0.055 mol) α-bromocyclohexane in an atmosphere of dry nitrogen at room temperature was added dropwise a solution of 3 g (0,022 mol) svezheosazhdennoi 1,3-dehydroalanine (ratio of 1,3-DCA : α-bromocyclohexane = 1: 2,5) in 20 ml of absolute diethyl ether, after which the reaction mixture is boiled at a temperature of 34-40°C for 4 hours, after which it the solvent and excess α bromocyclohexane removed by distillation in a water jet vacuum pump, the residue is distilled in vacuum and get Android 4.04 g (0,013 mol, 59%) of 2-(3-bromodiphenyl-1)of cyclohexanone in the form of a viscous oil that crystallizes upon standing. TKip=245-247°C /20 mm RT. Art. an NMR Spectrum1N, δ, ppm: 1,19-2,30 (14 H, substituted-1,3+6N, -(CH2)3-), 2,16, 2,203 (1+2N, - SNA(O)CH2-).

Found, %: C 61,80, N 7,32, Br 25,77. With16H23OBr. Calculated, %: C 61,74, N 7,39, Br 25.72.

Example 3.

(3-Bromodiphenyl-1-methyl)phenylketone.

To 6.0 g (0.03 mol) of ethyl ether α-bromoacetophenone in an atmosphere of dry nitrogen at room temperature was added dropwise a solution of 2 g (0.015 mol) svezheosazhdennoi 1,3-dehydroalanine (ratio of 1,3-DCA : α-bromoacetophenone = 1:2) in 15 ml of absolute diethyl ether, after which the reaction mixture is boiled at a temperature of 34-40°C for 3 hours, after which the solvent and excess α-bromoacetophenone removed by distillation in a water jet vacuum pump, the residue is distilled in vacuum and get 4.1 g (0,0123 mol, 82%) (3-bromodiphenyl-1-methyl)phenylketone. TKip=248-249°C/10 mm Hg NMR Spectrum1N, δ, ppm: 1,12, 1,62, 2,01, 2,20 (14 H, substituted-1,3); to 2.66 (2H, CH2C(O)); 7,34, 7,42, 7,81 (3 m 2+1+2N, C6H5).

Found, %: C 64,93, N 6,24, Br 24,07. C18H21OBr. Calculated, %: C 64,86, N Of 6.31, Br To 24.02.

You the odes

Developed a new one-step method for the preparation of 3-bromodiphenyl-1-alkyl(aryl)ketone, to obtain the claimed compounds of structural formula with high yields. The structure of the obtained compounds was confirmed by NMR1H-spectroscopy and elemental analysis.

The method of obtaining 3-bromodiphenyl-1-alkyl(aryl)ketones of General formula

using the adamantane derivative, characterized in that as adamantane derivative use 1,3-dehydroalanine, the process lies in the interaction of 1,3-dehydroalanine with α-bracketname from a number: α-bromoacetone, α-bromoacetophenone, α-bromocyclohexane, when the molar ratios of the reagents, respectively 1:2-3, in an environment of absolute diethyl ether at a temperature 34-40°C for 3-4 hours



 

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