CS239425B1 - Alfa-acylderivatives of lactames omega-aminiacides and method of theier preparation - Google Patents

Description

This invention relates to lactam alpha-eeyl derivatives and to a process for their preparation. The formation of analogs, which are cyclic beta-katoamides or beta-ketoimides, is believed to be the product of side reactions of activators or growth centers in the anionic polymerization of omega-amino acid lactams (see, e.g., J. Sebenda in Comprehensive Chemical Kinetics. Vol. 15). radical Polymerization (ed. CH Bamford, CFH Tipper, Elsevier, New York 1976, p. 409). However, they have not yet been synthesized or isolated from enamels of lactam polymerization. Another type of cyclic ketoamide, namely cyclopentanone-2-carboxylic acid N-hexylamides and cyclohexenone-2-carboxylic acid N-hexylamides, has been prepared previously (DH Johnson; J. Chem. Soc. 1958, 1624; F. Wiloth, E. Schindler; Chem. Ber 100,

2375 (1967).

The present invention provides alpha-acyl derivatives of the omega-amino acid lactams of the general formula

X

N-C = O / (i).

(CH 1) CR'COCAr - * - <ch ₂ > b wherein R ¹ is methyl or hydrogen, Ar is an aromatic radical containing 6 to 14 carbon atoms, which may be unsubstituted or substituted by alkyl or alkoxy groups, in each case β 1 to C5 ^C> is halogen, cyano or nltroskuplnou, X is hydrogen or ArCO where Ar is as hereinbefore defined, Y is a single bond, oxygen, sulfur or a group CHS ² or Cr |, wherein R ² is alkyl of 1 or 5 to 5 carbon atoms or phenyl, and the eman has a value of 0 to 10, wherein (m + n) is greater than or equal to one.

It has now been found that compounds of formula I wherein R ¹ is methyl or hydrogen,

Ar is an aromatic radical having from 6 to 14 carbon atoms which may be unsubstituted or substituted by alkyl or alkoxy groups in each case having from 1 to 5 carbon atoms, halogen, cyano- or nitro-group, X is ArCO wherein Ar is as defined above, X is

A single chemical bond, oxygen, sulfur, or a CHR or CR 8 group, wherein R is an alkyl of 1 to 5 carbon atoms or phenyl, and the amine is 0 to 10, wherein (m + n) - 1 may be prepared according to of the invention from a compound of formula II,

Ar = C = O

NN · -c = O (OH ₂ ) _n CR 4 H (II),

- < ^CH 2> m wherein R ¹ , Ar, Y, m and n are as defined above and compounds of formula I wherein R ¹ ,

Ar, Y, m and n are as defined above and X is hydrogen from these compounds in a manner that is also an object of the present invention.

The process for the preparation of the compounds of the formula I according to the invention is characterized in that ee is treated with a metallating agent, for example an alkali metal hydride or an organometallic of the formula RMe, in which R ¹ , Ar, Y, m and n are as defined above. R is an alkyl or aryl having 1 to 10 carbon atoms or an aliphatic dialkylamine residue and He is an alkali metal, in an aprotic solvent at a temperature of 173 to 313 ° C, preferably at a temperature of 193 to 253 K, and the corresponding metaloderivative of compound II is acylated arco kprbexylové acids wherein Ar is as defined above, to give a compound of formula I wherein X is Arco R ^1, Ar, Y, m and n are as defined above, which, after neutralization or acidification is isolated by conventional means.

A compound of formula I, wherein X e is hydrogen, R ^1, Ar, Y, m and n are as defined above are prepared according to the invention of compounds of formula I wherein X is Arco R ^1,

Ar, Y, m and n have the same meaning, by aminolysis with a primary or secondary aliphatic amine containing 1 to 36 carbon atoms, or with a polymer containing primary amine groups, the aminolysis being carried out with an isolated compound of formula I wherein X is ArCO and R ¹ , Ar , Y, m and n are as defined above, or directly with the reaction mixture after preparation of the compound.

Up to now, it has been known that metalation and subsequent substitution takes place in tertiary aromatic or heteroaromatic amides on the nucleus, preferably at the ore position to the kerbonyl group (see, e.g., P. Beak, RA Brown: J. Org. Chem. 47, 34 (1982) ): H. Iwao, K. K. Hahalanabis, M. Watanabe, S. 0. de Sliva, V. Snieckus: Tetrehedron 39, 1955 (1983)). Although the starting compounds of formula (II) are also tertiary aromatic amides, the kerbonyl group of the cycle directs metalation in this case to its vicinity.

Here, a competitive reaction is the oxygenation of the carbenyl group, or rather the formation of an ambivalent anion, which may be preferentially substituted on oxygen under certain conditions (see, for example, W. L. Le Neble: Synthesis, 970, 1). The latter reaction is, in the case of the starting compounds of the general formula (II), the subject of CS. Certificate No. 239 426.

For the preparation of the compounds of the formula I according to the invention, the starting compounds of the formula II may be those N-acylated omega-amino acid lactam derivatives in which the carbon atom adjacent to the exocyclic carbonyl does not carry a hydrogen atom and cannot be metalated and subsequently substituted, especially N-benzoyl derivatives of lactams, e.g. N-benzoyl-2-pyrrolidone, N-benzoyl-4,4-dimethyl-2-azetidinone, N-benzoyl- _c- caprolactam, N-benzoyl-8-octanlactam, N-benzoyl- 2-piperidone, 1-benzoyl-12-dodecanlactam, N-benzoyl-6,6-dimethyl-c-ceprolactam, N-benzoyl-2-methyl-E-caprolactam, N-benzoyl-3-oxa-E-caprolactam, and the like, and further N-acyl derivatives derived from substituted benzoic acids, naphthalenecarboxylic acids, and heterocyclic carboxylic acids such as pyridine carboxylic acids, thiophenecarboxylic acids, etc.

The metallating agents used in the preparation according to the invention are metal hydrides and amides, e.g. sodium hydride and potassium amide, alkyls and aryl metals, in particular n-butyllithium, tert-butyllithium, methyllithium, naphthylnathyl, preferably in the presence of cryptands or tetramethylethylenediamine. metals such as lithium dimethylamide or lithium diisopropylamide.

The reaction takes place in inert solvents, preferably of bipolar nature, such as tetrahydrofuran, 1,2-dimethoxyethane, 1,4-dioxane, or aliphatic and aromatic hydrocarbons, which allow working at low temperatures.

The substitution of the metal derivatives can be carried out according to the invention with halides, in particular chlorides or anhydrides of the above aromatic and heteroaromatic carboxylic acids, for example benzoyl chloride, benzoic anhydride, 4-methoxybenzoyl chloride, 3-chlorobenzoyl chloride acids etc.

The preparation of compounds of formula I wherein X is hydrogen from compounds of formula I wherein X is an ArCO group as defined above is carried out according to the invention using aliphatic primary amines such as methylamine, butylamine, octylemine, cyclohexylamine,

1,6-diaminohexane, secondary amines such as piperazine, dimethylamine, diisopropylamine, or polymers bearing amino groups such as 1- (3-aminopropyl) -1- (3-aminopropyloxy) poly (oxyethylene), polyethyleneimine and the like.

The alpha-acyl derivatives of the lactams of the invention can be used as monomers and comonomers in the preparation of polyamides or as activators in the anionic polymerization of lactams.

The preparation process of the present invention is illustrated in more detail by the following non-limiting examples and conditions.

He did

To cm @ 2 of absolute tetrahydrofuran, 2.6 cm @ 2 (0.018 mol) of diisopropylamine were added under an inert atmosphere, the solution was cooled to 263 K, and 18 cm @ 1 of n-butyllithium solution of 1 niol.cm was added thereto. ^. After 10 minutes, the mixture was cooled to 197 K in an acetone / solid carbon dioxide bath and 3.92 g (0.018 mol) of N-benzoyl-c-caprolactam in 15 cm @ 3 of absolute tetrahydrofuran were gradually added thereto with stirring. After two hours of methanation at 197 K, 2.40 cm @ 3 of benzoyl chloride was added to the mixture, and the mixture was cooled and stirred for an additional hour and then for one hour under gradual heating to 298 K. The reaction mixture was diluted with benzene, shaken with dilute hydrochloric acid and water. dried over anhydrous magnesium sulfate, evaporated and crystallized from acetone. The yield was 2.45 g of N, .alpha.-dlbenzoyl-c-caprolectam (1,2-dibenzoyl-6-hexanlactam), i.e. 84.6% of theory whose structure was confirmed by elemental analysis. , mass spectrum and equivalent of basic hydrolysis, *

mp 464-465 K.

Example 2

In the procedure of Example 1, 0.020 mol of phenyllithium in pentane solution was used to mete. The yield was 1.31 g of H, .alpha.-dibenzoyl-.epsilon.-caprolactam.

Example 3

Following the procedure of Example 1, metalation and substitution was carried out with other N-benxoyllactams, namely N-benzoyl-2-pyrrolidone, S-benzoyl-2-piperidone, H-benzoyl-8-octanlactam and N-benzoyl-12-dodecanlactam. The prepared compounds, their yields and melting points are given in Table 1.

Table!

Prepared compound Yield,% t. t., K Ν, α-Dibenzoyl-2-pyrrolidone 78.6 398 to 399 Ν, α-dibenzoyl-2-piperldone 55.3 392 to 393 Ν, α-Dibenzoyl-8-octanlactam 53.0 420 to 422 Ν, N -dibenzoyl-12-dodecenlactam 54.7 373 to 375

Example 4

By the procedure of Example 1, α, β-dibenzoyl-ε-caprolactam was prepared except that the metalation was performed with sodium hydride in the presence of tetramethylethylenediamine.

Yield 31.2% of theory. ⁵

Example 5

Following the procedure of Example 1, N- (4-toluyl) -c-caprolactam was metallized and 4-nitrobenzoyl chloride was used for substitution. 62% of N- (4-toluoyl) -? - (4-nitrobenzoyl) -? - caprolactam was obtained.

Example6 «

The Ν, α-dibenzoyl-8-octanlactam prepared according to Example 3 was dissolved in 4 cnP of benzene in an amount of 0.853 g (0.002 44 mol), 0.347 g octylamine (0.002 68 mol) was added and the mixture was heated at 323 K for 7 hours. The reaction mixture was diluted with benzene, shaken with dilute hydrochloric acid and water, dried over anhydrous sulfate and evaporated to dryness. The residue, after dilution with diethyl ether, α-benzoyl-8-octanlactam yielded 0.514 g, or 85.8% of the theoretical yield. The structure of the product was confirmed by elemental analysis, mass and 1 H-NMR spectra; melting point after crystallization from acetone 482 to 483 K.

Example 7

Following the procedure of Example 6, the other N, α-dibenzoyllactams prepared according to Examples 1 and 3 were aminolysed. The prepared compounds, their yields and melting points are shown in Table 2.

Table 2

Prepared compound Yield,% t. t., K α-benzoyl-2-pyrrolidone 76.3 395 to 396 α-benzoyl-2-piperidone 32.0 390 to 391 α-benzoyl-6-caprolactam 57.7 467 to 468 with α-benzoyl-12-dodecenlact 41.2 479 to 480

Example

The N, α-dibenzoyl-1-caprolactam prepared according to Example 1 was dissolved in an amount of 0.321 g (0.0010 mol) in a solution containing 5 cm @ 3 of N-methyl-2-pyrrolidone and 1 g of 1- (3-aminopropyl) -o > - (3-aminopropyloxy) poly (oxyethylene) having a molecular weight of 800 and an amino group content of 2.2 mol.kg -1. The solution was heated at 353 K for 10 hours, diluted with 30 cm &lt; 3 &gt; of water and the precipitate formed was separated and recrystallized from acetone: yield

0.180 g (83% of theory) of .alpha.-benzoyl-c-caprolactam.

Claims (8)

OF THE INVENTION 1, Alpha-acyl derivatives of lactams of omega-amino acids of the general formula I, (I), ^(ch X CR COAr Wm wherein R ¹ is methyl or hydrogen, Ar is an aromatic radical having 6 to 14 carbon atoms, which may be unsubstituted or substituted by alkyl or alkoxy groups of 1 to 5 carbon atoms each, halogen, cyano or nitro, X is hydrogen or a group ArCO, wherein Ar is as defined above, Y is a single bond, oxygen, sulfur, or CHR ² or CR 8, wherein R ² is an alkyl of 1 to 5 carbon atoms or phenyl, and the amine is 0 to 10, m + n is equal to or greater than one. 2. A process for the preparation of an alpha-acyl derivative of the general formula I according to claim 1, wherein X is an ArCO group as defined above, characterized in that the compound of the general formula II is: AifCO AND N - (CH ₂ ) _n CR'H ^(CH 2> m (II), wherein R ¹ , Ar, Y, m and n are as defined in point 1, with a metal reagent selected from the group consisting of hydrides, amides, organometallic compounds of formula RMe, wherein R is an alkyl or aryl of 1 to 10 carbon atoms or an aliphatic dialkylamine residue and is an alkali metal, in an aprotic organic solvent at a temperature of 193 to 253 K and the resulting compound II is arylized with a carboxylic acid halide or anhydride ArCOOK Ar 1 is as defined above, and the resulting compound of formula 1 wherein X is an ArCO group as defined above is isolated after neutralization or acidification. 3. A process for the preparation of an alpha-acyl derivative of the general formula I according to claim 1, wherein X is hydrogen, characterized in that the alpha-ecyl derivative prepared according to point 2 is treated with a primary or secondary aliphatic amine containing 1 to 36 carbon atoms or a polymer containing amino groups. wherein the alpha-acyl derivative prepared according to throw 2 is used in an isolated state or directly in the reaction mixture prepared according to the method of point 2. 4. A process according to claim 2 wherein the compound of formula II is selected from the group consisting of N-benzoyl-6-caprolectam, N-baneoyl-8-octanlactam, N-benzoyl-12-dodecanlactam, N-benzoyl- 2-pyrrolidone, N-bensoyl-2-methyl-ε-caprolactam, N-benzoyl-2-piperidone and N-benzoyl-4-allcyl-2-azetidinone. 5. A process according to claim 2, wherein the metallating agent is an organometallic compound of the formula R1L, wherein R is methyl, ethyl, n-hutyl, isobutyl, phenyl, diethylamino or diisopropylamino. 6. Process according to claim 2, characterized in that the preparation is carried out in tetrahydrofuran, 1,2-dimethoxyethane, diethyl ether, 1,4-dioxane or mixtures thereof at a temperature of 193 to 253 K. 7. A process according to claim 3, wherein an amine selected from the group consisting of methylamine, ethylamine, propylamine, butylamine, octylamine, dodecylamine, diethylamine and piperazine is used. 8. A process according to claim 3, wherein the polymer is an amino group of 1- (3-aminopropyl) -? - (3-aminopropyloxy) poly (oxyethylene) having an average molecular weight of 300 to 20,000.