The method of obtaining n-(1-propenyl)ndimethylacetamide

 

(57) Abstract:

The invention relates to organic chemistry, in particular to a method for producing N-(1-propenyl)ndimethylacetamide by isomerization of N-(2-propenyl)ndimethylacetamide in the presence of catalytically active carbonyl complex of the VIII group metals at room temperature. As catalytically active carbonyl complex use of carbonyl complex of osmium General formula HOs3(OCNR'R)(CO)10where R', R" are H, alkyl, aralkyl, alkenyl in various combinations, in the environment of an organic solvent and concentration of the original amide and the cluster is 2 to 6 and 0.13 to 0.3 mol/l, respectively. The technical result is simplification and expansion of the used catalysts. 2 C.p. f-crystals, 1 table.

The invention relates to organic chemistry, in particular to a method for producing N-(1-propenyl)ndimethylacetamide by isomerization of N-(2-propenyl)ndimethylacetamide in the presence of a metal complex cluster catalyst.

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N-(1-propenyl)ndimethylacetamide is representative of the class of enamides, which are widely used in organic chemistry for the synthesis of various types of connections. The most important use of N-(1-propenyl)ndimethylacetamide and its analogues - fotonica is used alkene are precursors of alkaloids and many other natural compounds ([1] G. R. Lenz , Synthesis, 1978, p. 489).

A method of obtaining N-(1-propenyl)ndimethylacetamide of propylidene-bis-ndimethylacetamide CH3CH2CH(NHCOCH3)2when terminalarea the disproportionation latest in a vacuum of 40 mm RT. tbsp. at a temperature of 220oC (oil bath) ([2] Ben - Ishi D., Giger R., Tetrahedron Lett., 1965, No. 50, p. 4523). Yield 65%.

The disadvantages of this method are unsafe process conditions, the need for appropriate equipment to maintain the desired temperature and pressure and the inaccessibility of the original diamide, which must be obtained from propanal and N-methylacetamide.

The closest analogue is the prototype of the proposed method is a method of isomerization of N-(2-propenyl)ndimethylacetamide N-(1-propenyl)ndimethylacetamide in the presence in the solution as a catalyst managername carbonyl iron complex Fe(CO)5(5 weight %) in combination with UV irradiation[3] Hubert A. J. , Moniotte P., G. Goebbels, Warin R, Teyssie P. J. Chem. Soc., Perkin II, 1973, N 14, p. 1954). The process is carried out in the absence of solvent at room temperature for 20 hours While the transformation of the original amide passes by 60%. At the end of the process, the reaction mass is shaken with chloride of iron III is about N-(2-propenyl)ndimethylacetamide and the product N-(1-propenyl)ndimethylacetamide - is distilled over under vacuum while heating, and the composition of the mixture is analyzed by IR - and NMR-spectra.

The disadvantages of this method are the complexity of the process, due to the need of UV irradiation and the use of appropriate technical equipment, as well as the insecurity of the process associated with extremely high volatility and toxicity of PENTACARBONYL iron, its ability distillation (in the form of vapour to form a flammable mixture with air oxygen.

In addition, the difficulty lies in the separation and purification of the obtained product.

Complication of the process is the contamination of the reaction mixture, the solid amorphous products of transformation of PENTACARBONYL iron in the result of exposure: partially into noncarbonyl iron Fe2(CO)9and , partially, decomposition products, such as the free metal and oxides. In addition, at the end of the process the reaction mass contains the remains unreacted source amide as a result of incomplete conversion of the substrate, which creates additional difficulties at the stage of extraction and purification of the product. A bad mixture is filtered, the chromatography was carried out, planting, Perekrest the NECS volatile components from a semi-solid mass in vacuum by heating. Get N-(1-propenyl)ndimethylacetamide, polluted source N-(2-propenyl)ndimethylacetamide.

The objective of the invention is a simplified method of obtaining N-(1-propenyl)ndimethylacetamide and the expansion of the used catalysts for the isomerization of N-(2-propenyl)ndimethylacetamide N-(1-propenyl)ndimethylacetamide.

The problem is solved in that in the method of obtaining N-(1-propenyl)ndimethylacetamide by isomerization of N-(2-propenyl)ndimethylacetamide in the presence of catalytically active carbonyl complex of a metal of group VIII at room temperature as this catalytically active complex use of carbonyl cluster complex of osmium General formula HOs3(OCNR'R)(CO)10where R', R" is a hydrogen atom, alkyl, aralkyl, alkenyl in various combinations, the process is conducted in the medium of an organic solvent at a concentration of N-(2-propenyl)ndimethylacetamide and cluster complex of osmium, equal to 2 to 6 mol/l and 0.13 to 0.3 mol/l, respectively.

The problem is solved also by the fact that as an organic solvent used or benzene or chlorinated hydrocarbons, or ethers, while the relative content of the cluster metal complex catalyst is 4.7 to 10.7 mol. %.

the Plex metal used carbonyl cluster complex of osmium General formula HOs3(OCNR'R)(CO)10where R', R" is a hydrogen atom, alkyl, aralkyl, alkenyl in various combinations, the process is conducted in the medium of an organic solvent at a concentration of N-(2-propenyl)ndimethylacetamide and cluster complex of osmium, equal to 2 to 6 mol/l and 0.1 - 0.3 mol/l, respectively;

as the organic solvent used or benzene or chlorinated hydrocarbons, or ethers, while the relative content of the cluster metal complex catalyst is 4.7 to 10.7 mol.%.

These carbonyl cluster Os3the complexes are solid crystalline substances stable in air at room temperature and when heated to 100 - 125oC (unlike the prototype, where Fe(CO)3is a liquid substance that is oxidized in air to oxides, extremely volatile and toxic).

They can be easily cleaned from impurities or to separate from the desired product by using recrystallization, chromatographic purification, extraction, and can take an accurately weighed sample of these complexes and to prepare a solution of a given concentration (in contrast to the prototype, where, on the one hand, the complex liquid and volatile, and it is therefore difficult to measure e is gotovit standard solution and remove the required number of complex in the form of aliquots). Until the end of the experiment the concentration of the complex remains unchanged, because the complex does not decompose (unlike the prototype). All this allows to control the process and provide reliable reproducible results.

As it is possible to completely isomerizate the original N-(2-propenyl)ndimethylacetamide N-(1-propenyl)ndimethylacetamide, this target product does not require additional refinement of the original amide (unlike the prototype, where the product is obtained in a mixture with the original Amida). After chromatographic separation from the complex, the target product is a pure individual connection.

In the reaction complex does not undergo decomposition or transformation into other systems, so it is (in contrast to the prototype) can be isolated from the reaction mixture in an unchanged form and reused, which is very important to save.

Up to the present time on the catalytic activity of carbonyl cluster osmaevyh complexes HOs3(OCNR'R)(CO)10in the reactions of isomerization of N-(2-propenyl)ndimethylacetamide or its analogues was not known, and they have not been used for these purposes. From the examples and tables of this application, however, it is necessary that such A specified. When this method is economical, convenient, safe, and the target product is obtained in the individual condition and with almost quantitative yield (99 %).

Usually to increase the activity of the metal complex catalyst of the process is conducted by heating, or by additional irradiation. In this case, a sufficiently high activity cluster osmanaga complex eliminates the need for additional activation process by increasing the temperature or radiation (in contrast to the prototype), which avoids accumulation in the reaction mixture of decomposition products or by-products due to side processes. The method presented in the examples.

Example 1 (typical)

The hitch-N-(2-propenyl)ndimethylacetamide (0.1 - 0.25 g) add calculated at a given concentration (2 to 6 mol/l) volume (0,35 - 0,45 ml) pre-cleaned and dried the appropriate organic solvent (method of monitoring the reaction by NMR method must be used which does not contain hydrogen atoms solvents or deuterated chloroform CDCl3, methylene chloride CD2Cl2, diethyl ether {2IN3}2O, etc. or carbon tetrachloride which SUB>3complex to create a given concentration of 0.13 to 0.3 mol/l) and maintain the relative molar content of 4.7 to 10.7 mol.%) this metal complex catalyst. The solution is placed in a vial for taking NMR spectra, incubated at room temperature and record the spectrum as far as possible every 15-20 hours until complete disappearance of the signals of the original N-(2-propenyl)ndimethylacetamide. The reaction time is recorded.

Example 2 (typical)

Analogously to example 1 to prepare a solution (in a conventional organic solvent, and a few more solution - within 2 to 3 ml) of N-(2-propenyl)ndimethylacetamide in a mixture with the specified carbonyl complex and maintain the solution at room temperature. The reaction course is monitored chromatographic - reduction spots the source of N-(2-propenyl)ndimethylacetamide on the chromatographic plate or its complete disappearance. The reaction time is recorded. For separation of the target product from the complex solvent pumped in vacuo without heating and the residue chromatographic on column using cyclohexane with the addition of methylene chloride. Collect two separate factions - N-(1-propenyl)ndimethylacetamide and previously introduced into the solution and octav solids weighed to control. The full time isomerization ranges from 70 to 170 h, depending on the actual concentrations of each of the reactants and the relative molar content of the complex catalyst (mol.%). From the selected solvent dependence of the reaction time is weak. Loss of product in the process of separating from the reaction mixture a minor, and the output is close to quantitative (~ 99%).

Examples obtain the N-(1-propenyl)ndimethylacetamide presented in the table.

1. The method of obtaining N-(1-propenyl)ndimethylacetamide by isomerization of N-(2-propenyl)ndimethylacetamide in the presence of catalytically active carbonyl complex of a metal of group VIII, at room temperature, characterized in that the catalytically active carbonyl complex use of carbonyl cluster complex of osmium General formula

HOs3(OCNR'R)(CO)10,

where R', R" are H, alkyl, aralkyl, alkenyl in various combinations,

the process is conducted in the medium of an organic solvent at a concentration of N-(2-propenyl)ndimethylacetamide and cluster complex of osmium, is 2 to 6 and 0.13 to 0.3 mol/l, respectively.

2. The method according to p. 1, characterized in that the organic solvent used or benzene or chlorinated the same time, the relative content of the cluster complex of osmium in the reaction mixture is 4.7 to 10.7 mol.%.

 

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