DE3427146A1 - NEW PYRIDON DERIVATIVES - Google Patents

Description

3427H6

Troisdorf, June 29, 1984 Process for the production of these compounds. H ^ CCH ₃ Aryl residues. Ί OZ 84036 Dr.Sk/Bd PyiidDnderivate invention by the DYIMAMIT NOBEL AKTIENGESELLSCHAFT Formula (I) characterized fr Troisdorf district Cologne In this formula, the radical R can stand for 5 New Pyridon Deriuate hydrogen The present invention relates to new pyridone derivatives straight-chain or branched alkyl radicals and In or 10 the a) c) b) 15th 20th 25th

The alkyl radicals can be of any chain length; preferred they contain 1 to θ carbon atoms, but they can also have up to 1S carbon atoms. The alkyl radicals can also be substituted be; the main substituents are aryl radicals, e.g. the phenyl radical, which is optionally substituted by alkyl groups or halogen can be, or a carboxylic acid ester residue in question before The substituents in oC-position to the nitrogen atom are added or arranged at the end, but with a different substitution pattern react in the same way.

It is also possible that the alkyl on one carbon atom chain four different substituents are present, so that this carbon atom is an optically active center. Of the The term optically active center also includes structures with dissymmetry such as atropisomerism.

The phenyl and naphthyl radicals are mainly suitable as aryl radicals. These radicals can also be substituted on the nucleus by halogen or by C ₁ to C 1 -alkyl radicals.

The new compounds are produced either from 3, ⁱ t-dihydro- ⁱ t, ⁱ + -dimethyl-oC-pyrones or from 5-oxa-pentanoic acid-

1 1 derivatives, each of which is reacted with amines of the formula HpIMR, in which R has the meaning given above.

Accordingly, in addition to ammonia, alkylamines with up to 1B carbon atoms, which may also be substituted, are suitable as amines. Preferred Substituents are the phenyl group or a carboxylic acid ester radical. The phenyl group can be substituted with alkyl or halogen (e.g. chlorine or bromine). üJenn the used Amine contains an asymmetric carbon atom, a Bptisch active form of the amine can also be used, in which case one then an optically active pyridone is also obtained.

3427U 6

The reaction proceeds faster in the presence of acids as a catalyst. Preferred catalysts are aromatic sulfonic acids, such as, for example, p-toluenesulfonic acid, or the anhydrous metal halides known as Lewis acids in the narrower sense, such as Al Cl ₃ , Fe Cl ₃ , BF 3. But phosphoric acids can also be used as catalysts, such as H-, Po,. However, the addition of a catalyst is mandatory.

If the ct-pyrones mentioned are used as starting materials the reaction already takes place at room temperature. Warming increases the rate of the reaction; one can heat the reaction mixture to temperatures of up to 250.degree.

The Dihydro-cC-Pyrone, used as starting materials correspond to the formula

Cu

they can, for example, according to that described in DE-DS 29 52 068 l / experienced to be produced.

The conversion between the oC pyrone and the amine runs at any V / ratios of the reactants to each other in the desired direction. Preferably, however, the C (pyran used in excess, the excess can be up to 100 mol%. After implementation, the excess can -, -. Pyran is easily separated from the desired pyridone by distillation and be regained.

When used as Ausgangspradukte for preparing the novel 5-pyridones DXO-pentanoic acid derivatives, corresponding to these, _c of the formula O = CH-CH "- C -CH ₀ -COO R ² in which R ² is hydrogen

² / \ -

H ₃ C CH ₃

3427U 6

1 or represents alkyl radicals with 1 to B carbon atoms. In this case, the reaction temperature is preferably between ßü and 250 ^D C and the reactants are preferably used in a stoichiometric ratio to one another.

The new pyridones are predominantly high-boiling compounds. You can therefore benefit from the starting products and any resulting By-products can be easily purified by distillation. The implementation can therefore generally be absent be carried out by solvents.

However, it is also possible to use the implementation to produce the To carry out new Uerbindungen in the presence of solvents, this is particularly recommended when the new compounds are crystalline or the amine to be used is not in the form of a liquid is present. Suitable solvents are mainly those compounds in which the resulting in the reaction Illasser is insoluble and in the form of an azeotropic mixture can be removed by distillation with the solvent from the reaction vessel. Examples of suitable solvents are aliphatic ethers, aromatic, possibly nuclear chlorinated, hydrocarbons or straight-chain or branched alkanes. as possible representatives of these groups of substances are: dimethyl ether, benzene, toluene, xylene, chlorobenzene, hexane or isooctane.

The new pyridones are valuable intermediates in the manufacture of reeficticides and pharmaceuticals. You can, for example, by reaction with halogen and alkali metal alcoholate in an alcohol to give 3-azabcyclo 03.1.0 JJ -hexane derivatives of the formula H ₃ C CH ₃

(R ³ S = C ₁ -C C alkyl) 0 ^{1 b}

further processed analogously to the known cyclopropanecarbanoic acid ester acetals Starting products for the manufacture of insecticides with a pyrethruid structure are.

example 1

A mixture of 117 g of aniline, 316 g of 4,4-dimethyl-3,4-dihydrooC-pyrone and D, 5 g of p-tallow sulfonic acid is heated to 80 ° C. for 18 hours. Then Uird in a vacuum, the reaction mixture prominent destil- ^. At 40 to 5 ° C. (0.1 torr), 112 g of unreacted 4,4-dimethyl-3,4-dihydra-OC-pyrone pass over. After a fraction is added, the N-phenyl-4,4-dimethyl-3,4-dihydro-OC-pyridone ^{distills at 120 to 125 D C (0.1 Torr).} Yield 193g (80.16%).

Nuclear Magnetic Resonance Spectrum (90 MHz, CDCl ₃ ): CT (ppm) = 1.14 (6 H); 2.52 (2H); 5.10, 6.14 (2H); 7.16 - 7.40 (5H).

Example 2

,, -. A mixture of 2.4 g of aniline and 4 g of 3,3-dimethyl-5-oxo-pentanoic acid Uird in the presence of 1-p Taluolsulfonsäure mg to 120 ^D C heated. The toluene which is distilled off is passed through an H ₂ O separator which is filled with molecular sieve and then returned to the reactor. After a reaction time of 18 hours, the batch is worked up as in Example 1. 1 g of N-phenyl-4,4- dimethyl-3 _l 4-dihydro-OC-pyridone.

Example 3

A mixture of 11.8 g of aniline and 20 g of 3,3-dimethyl-5-oxo-pentansäuremethylester is heated in the presence of 1 mg of p-toluenesulfonic acid at 90 ^D C. After a reaction time of 18 hours, it is worked up analogously to Example 1. 8.2 g of IM-phenyl-4,4-dimethyl-3,4-dihydro-Ot-pyridone are obtained.

Example 4

_{4 g of gaseous NH 3} are passed into a mixture of 76 g of 4,4-dimethyl-3,4-dihydro-OC-pyrone, 0.5 g of p-toluenesulfonic acid and 155 g of toluene. The mixture is then stirred for 24 hours at room temperature and the batch is then worked up by distillation. At 118 to 125 ^D C / 1 Torr, 22.1 g of 4,4-dimethyl-

3427U6

Λ 3,4-dihydro-OC-pyridone over, which after cooling down to room temperature and 0.5 g p-tallow sulfonic acid (/ (ppm): 1.01 (3 H); 1.04 (3 H); temperature become crystalline (m.p. : 55 to 56 ⁰ C). Then it is distilled (2 H); 4.93 & 5.75 (2H); 7, NMR spectrum (90 MHz, CDCl ₃ ) .flTCppm). 1.08 (6H); 2.31 (2nd worked; after a preliminary run the N- (Ot- phenylethyl) 5 4.91 (1H); 5.99 (1H); 8.84 (1H). dimethyl-3,4-dihydro-OC-pyridone at 150 ° C / 1 Torr above. -3.6 4-Tue- Example 5 (Yield 760 g) Ljerder A mixture made 463 g of d (+) - QC-phenylethylamine, 964 g of 4, IMMR spectrum (90 MHz, CDCl ₃ ): 1 on- methyl-3,4-dihydro-cC-pyran 1.51 (3H); 6.01 (1H); 2.40 -4.4- 10 Heated to 80 ^D C for 12 hours. (5H). 20th
Specific rotation: C £ = H); 27 15th 20th 25th 30th 35

Claims (3)

Troisdorf, June 29, 1984 OZ 84036 Dr.Sk/Bd patent claims 1. Pyridone's formula > 1 in which R stands for hydrogen or, optionally substituted, alkyl or aryl radicals. 2. pyridones according to claim 1, in which the radical R is at least contains an optically active center. 3. Process for the preparation of pyridones according to claim 1 or 2, characterized in that dihydro-cC-pyrones of the form (II) 0 ^ 0 with an amine of the formula H, KE ¹ (III), in which R has the meaning given in claim 1. 3427U6 k. Process for the preparation of pyridanes according to Claim 2, characterized in that 5-oxa-pentanoic acid derivatives of the formula (IU), CO ₂ B? in which R stands for hydrogen or alkyl radicals with 1 to θ C atoms is, reacted with an amine of the formula III.