FR2575471A1 - PYRONE-3-CARBOXAMIDE COMPOUNDS AND THEIR APPLICATION FOR INHIBITING PLANT GROWTH - Google Patents

Abstract

COMPOUNDS OF THE PYRONE-3-CARBOXAMIDE TYPE OF FORMULA: (CF DRAWING IN BOPI) IN WHICH R IS AN ALKYL GROUP AND R IS AN ALKYL GROUP OR A HALOGEN. THESE COMPOUNDS MAY BE USED TO INHIBIT PLANT GROWTH.

Description

-2575471

  The present invention relates to novel compounds which are part of the pyrone-3-carboxamide compounds,

  in particular 2,6-dimethyl-4-oxo-4H-pyran-3-

  carboxamides. The compounds of the present invention exhibit an activity inhibiting the growth of plants and

  are also useful as intermediaries for the prepa-

  ration of drugs or chemicals for use in agriculture.

  Some compounds belonging to 2,6-dimethyl-4-

  oxo-4H-pyran-3-carboxamides have been mentioned in the literature.

  Indeed, it is known that the treatment of o-halogeno-

  acetanilides (2-chloro-, 2-bromo-, 2,4-dichloro or 2,5-dichloro- compound) by polyphosphoric acid for 1 hour

  at 140 ° C gave the halogenated derivatives of 2,6-dimethyl-4-oxo

  Corresponding N-phenyl-4H-pyranecarboxamide (A.K. Mallams and S.S. Islaelstam, J. Org Chem., 29, 3548 (1964), A.K. Mallams, J. Org Chem, 29, 3555 (1964)). This process using the polyphosphoric acid has been applied to other acetoacatanilides (2-fluoro-, 2-piperidino-, 2-hexahydroazepinyl-, 2-morpholino-, 2-pyrrolidinyl- or

  similar) to obtain the 2,6-dimethyl-

  Corresponding 4-oxo-4H-pyran-3-carboxamide [(R. Garner

  and H. Suschitzky, J. Chem. Soc., (C), 186 (1966) 1.

  The product formed by the reaction between p-nitro-

  aniline and dicetene was identified as 2,6-dimethyl-N- (4-nitrophenyl) -4-oxo-4H-pyran-3-carboxamide (Kato and Kubota, Yakugakuzassi, 87, 1212 (1967) J.) ,

  N- (2-chlorophenyl) -2,6-dimethyl-4-oxo-4H- was obtained.

  pyran-3-carboxamide by treatment of 2,6-dimethyl-

  4-oxo-4H-pyran-3-carboxylic acid with thionyl chloride followed by reaction with o-chloroaniline, or by heating

  p-nitrophenyl ester of 2,6-dimethyl-4-oxoacetate

  4H-pyran-3-carboxylic acid and o-chloroaniline

  4.3 hours at 110 ° C (Toda, Yakuqakuzassi, 87, 1351 (1967)].

  This literature describes pyrone-3- type compounds

  carboxamide which have been obtained by the reaction of 4-amino

  tropolones with dicetene. Japanese Patent Publication No. 45 (1970) -31663 also discloses a process for the preparation of 2,6-dimethyl-4oxo-4H-pyran-3-carboxamides, which comprises the reaction of isocyanates and diketene in the presence of an acid catalyst, the application of which is described in

  examples for the preparation of 2,6-dimethyl-4-oxo-N-

  phenyl-4H-pyran-3-carboxamide, 2,6-dimethyl-N- (2-methyl)

  phenyl) -4-oxo-4H-pyran-3-carboxamide, N- (2-chlorophenyl) -

  2,6-dimethyl-4-oxo-4H-pyran-3-carboxamide, 2,6-dimethyl-

  N- (2-nitrophenyl) -4-oxo-4H-pyran-3-carboxamide, N- (2.5-

  dichblorophényl) -2,6-dimethyl-4-oxo-4H-pyran-3-carboxamide,

  of! oxo-4H-2,6-dimethyl-N- (3-nitrophenyl) -4-oxo-4H-

  pyran-3-carboxamide and 2,6-dimethyl-N- (4-methylphenyl) -

4-oxo-4H-pyran-3-carboxamide.

  In addition, 2,6-dimethyl-4-oxo-N-phenyl-4H-pyran

  3-carboxamide, N- (4-methoxyphenyl) -2,6-dimethyl-4-oxo

  4H-pyran-3-carboxamide and N- (4-chlorophenyl) -2,6-dimethyl-

  4-oxo-4H-pyran-3-carboxamide have been described as the products of the reaction between 3-morpholino-crotonanilide compounds and diketene [Kato et al.,

Yakuqakuzassi, 101, 43 (1981)]. -

  In addition, pyrone-type compounds have been described.

  3-carboxamide which correspond, respectively, to ....

  Tropones (H. Toda and S. Seto, Chem Pharm Bull., 19, 1477 (1971)), to aminopyridines CT Kato et al., Chem Pharm Bull, 20, 133 (1972); cit., 28, 2129 (1980), HL Yale et al., J. Heterocyclic Chem., 14, 637 (1977)) and at

  2-amino-1,3,4-thiodiazoles [R.F. Lauer et al., J. Hetero

cyclic Chem., 13, 291 (1976)).

  In Japanese Patent Publication No. 45 (1970) -31663

  mentioned above, it is revealed that 2,6-dimethyl

  4-oxo-4H-pyran-3-carboxamides are useful as agricultural chemicals such as rice sheath rust control agent, nematicide or acaricide, or as med-caments such as antiviral or However, no data are available to confirm these facts. As indicated above, there has been no report on the pyrone-3-carboxamide compounds represented by the formula (I) of the present invention. , no indication

  suggesting their inhibitory activity of vEQetal Growth.

  The present invention provides compounds of formula (T) and salts thereof

2JCTX (-

7.-o C

CH3 CH 3

  In the formula (I), R 1 is an alkyl group and R 2

  is an alkyl group or a halogen.

  In the present invention, the term "alkyl group" refers to alkyl groups preferably containing from 1 to 5 carbon atoms. Similarly, for R2, 'halogen' means

  preferably fluorine, chlorine or bromine.

  With respect to R 1 and R 2, examples of preferred alkyl groups are methyl, ethyl or

  isopropyl, and the preferred halogen example is chlorine.

  The compound of formula (I) of the present invention is generally prepared in good yield by reacting a butyrylanilide derivative of formula (II):

CO3H / CH8

N N

/ J CO 0NHI

JUCONHX ()

CH3

  In which R1 and R2 have the same meanings as in formula (I), with the diketene or the adduct

  of it with acetone, namely 2,2,6-trimethyl-4H-

  1,3-dioxin-4-one. In addition, the butyrylanilide derivative of formula (II) can be easily prepared by reacting the derivative

  corresponding acetoacetanilide type with N, N-dimethyl-

  hydrazine under dehydrogenation condensation conditions.

  generation according to a conventional method. The intermediate product of formula (II) is preferably used after isolation and purification, but it can be used directly, as

  this is the case for the reaction mixture mentioned above.

  The reaction of the compound of formula (II) with diketene or with 2,2,6-trimethyl-4H-1,3-dioxin-4-one is carried out by heating in a suitable solvent. The solvents are preferably those in which the desired compounds are less soluble at low temperature. As such

  solvents, use is advantageously made of aromatic hydrocarbons

  such as benzene, toluene, xylene and the like.

  The temperature of the reaction is from 60 to 130 ° C. in the case where diketene is used, and from 100 to 140 ° C. in the case

  2,2,6-trimethyl-4H-1,3-dioxin-4-one is used.

  The present invention is illustrated by the following nonlimiting and descriptive examples. Inhibiting activities are also indicated in the reference examples.

  plant growth of the compounds of the invention.

  Related specific compounds, in addition to the compounds indicated in the examples, are furthermore:

  N- (3-chloro-2-methylphenyl) -2,6-dimethyl-4-oxo-4H-

pyran-3-carboxamide,

  2,6-dimethyl-N- (2,4-dimethylpbhenyl) -4-oxo-4H-pyran-3-

  carboxamide, 2,6-dimethyl-N- (2,5-dimethylphenyl) -4-oxo-4H-pyran-3-carboxamide.

Example 1

  N- (2,6-diethylphenyl) -2,6-dimethyl-4-oxo-4H-pyran

  3-carboxamide AOHIa C21H / A mixture of 25.0 g (90.8 mmol) of N- (2,6-diethylphenyl) -3- (N, N-dimethyllydrazono) butyrylamide was heated under reflux (m.p. 108.5 ° C., recrystallized in hexane) and 130 ml of toluene, with a solution of 28.4 g (200 mmol) added dropwise over a period of 30 minutes.

  2,2,6-trimethyl-4H-1,3-dioxin-4-one in 70 ml of toluene.

  The mixture was further heated under reflux for 2 hours.

  After distilling off the solvent, 200 ml of ethyl ether was added to the residue. We mixed carefully

  and the mixture was filtered to remove insoluble materials

  lubles. The filtrate was concentrated to give a residue.

  The residue was chromatographed to remove strongly polar impurities. The resulting product was recrystallized from hexane to give 20.2 g (74% yield) of the title compound. The physical properties are shown in Table 1. The figures in the "Evaluation" column in Table 1 were obtained as follows: A vehicle was prepared by mixing 50 parts (by weight) of talc, 25 parts of bentonite, 2 parts Solpole-9047 (Toho Chemical Co Ltd, Japan) and 3 parts SolpolE-5039 (Toho Chemical Co Ltd, Japan). Parts of a test compound and 200 parts of the vehicle were mixed to obtain a 20% wettable powder, and then the powder was dispersed in distilled water to obtain dispersions.

  at the specified concentrations.

  Oryza sativa L., Echinochloa crus-galli L. and Raphanus sativus L. seeds were germinated in a capsule in which the dispersion was added. After culturing for 7 days in a box maintained at 25 C by thermostat, illuminated with fluorescent tubes, the growth of the plants was examined. In the "Evaluation" column of Table 1,? means: no effect, 2: 25% inhibition of growth, 3: 50% inhibition of growth, 4: 75% growth inhibition and 5% inhibition of growth

of the growth.

Exemr2.t 2

  N- (2,3-dimethylphenyl) -2,6-dimethyl-4-oxo-4H-

pyran-3-carboxamide

'

CONH

<V CH3 CH3

  CH 3 CH 2 was stirred for 8 hours at 60 ° C.

  mixture of 10.3 g (50 mmol) of N- (2,3-dimethylphenyl) -3-

  oxo-butanamide, 4.50 g (75 mmol) of N, N-dimethylhistine and 60 ml of toluene. Then the unreacted N, N-dimethylhydrazine and the water produced, together with

  ml of toluene were removed from the reaction

  distillation. 10.5 g (125 mmol) of diketene were added dropwise to the remaining solution over a period of 5 minutes while refluxing. The mixture was further refluxed for 2 hours and then cooled to room temperature. The resulting crystals were filtered off, washed and dried to give 8.63 g.

  (yield: 64%) of the desired compound.

  N- (2-chloro-6-methylphenyl) -2,6-dimethyl-4-oxo-4H-

  The desired compound was prepared by the same method as that described in Example 2, using as starting materials N- (2-chloro-6-methylphenyl). -3-oxobutanamide

  and M, N-dimethylhydrazine. (Yield: 45%).

Example 4

  N- (2,6-dimethylphenyl) -2,6-dimethyl-4-oxo-4H-pyran

-3-carboxamide CH3 o

[CONHI

CHS CHSCH

OHa-8 O CH8.

  The title compound was prepared by the same method as that described in Example 2, using as starting materials N- (2,6-dimethylphenyl) -3-oxo-butanamide and the

  N, N-dimethyl hydrazine. (Yield: 63%).

Example 5

  N- (2-ethyl-6-methylphenyl) -2,6-dimethyl-4-oxo-4H-

  pyran-3-carboxamide D CON-ii case C0 N.K5

CHS.OESC2H3 __

  C: ## STR2 ## The desired compound was prepared from

  N- (2-ethyl-6-methylphenyl) -3-oxo-butanamide and N, N-dimethyl-

  hydrazine, by the same method as described in

Example 2. (Yield: 58%).

T A B L E A U T

  NMR (c) iwcea) Evaluation Exemplt Substitute1 mcil3 In _ ___jSubstituant. 1 (r ((C) conc. Plants No.

1 J 12 .. xi | N H the r-dic = l (P p-) 1 {.1e.itc R '). 11 tiCn 5 rWyle (KBf) XYZ 2- (C2115 2.80 (s) 6.24s (I 1.17 (7,611) IG5 20 I 2 3 I 1,00 3,5- 8 4,5 6 - 12.2 9 () s_2.61 (q.4l 1675 4 l) I 2 (CIa 2.88 (s) 2.28 (s 611) 164.5 20 II 3 2 6.281s) 11.66 174.5 -175.5 - (, 11s3 2.28 (S) 1675 i _0 _ 2 4 2 -ce I 2.8 (OS) 2.28 (S, 311) 1655 20 1 2 a. IsI 1, 1.4 0 1I5.0-l, 18.0 6 .. 2.28 (s) .. 678 1 .__ 0 _ 2 _ _ 2 - CI32.79 ( S) 2.2 4 (s S6I.) 1650 20 1 I 4 6.2 2Is 1 1.18 111.5-1 2.0. _: _ 2, 8 (s) _.._____ 1 678.0 ___ __8 ... _ _ .. _ 2 - CzIIs2,8 (s), 1,18 t, garlic) 1653 2 0 I 4 I 6,2as 1 97 224 (s, 3I) 57,0-- 8.5 6 - (1I 32.28 (S) 2.6 (q 211) 1683 (q 1) 2,6-dimethyl-4-oxo-N-phenyl-4H-pyrrolidone-3-carboxylic acid; 1 Exelnple (as known) 100 I 1 X Oryza sdtiva L. Echinochloa crus-galli L. Z: Raphanus sativus L. -10

Claims (6)

  1 - Pyrone-3-carboxamide compounds of formula (I): o CONE R2 CH CH3 R1   wherein R1 is an alkyl group and R2 is a group alkyl or halogen.   2 - Compounds according to claim 1, wherein the alkyl groups represented by R and R2 have from 1 to 5 carbon atoms.   Compounds according to claim 1, wherein the halogen represented by R2 is fluorine, chlorine or bromine.   4 - Compounds according to claim 1, wherein the alkyl groups represented by R1 and R2 are groups methyl, ethyl or isopropyl.   - Compounds according to claim 1, in   which halogen represented by R2 is chlorine.   6 - Composition inhibiting plant growth   rate, comprising as active ingredient a compound according to   any of claims 1 to 5.   7 - Use of a compound according to one   Claim 1 to 5 for inhibiting growth Plant.