JPS60351B2 - 3-phenyl-4(IH) pyridone and pyridinethiones and their salts - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to 3-phenyl-4(IH) pyridones and pyridinethios and salts thereof, and more particularly, the present invention belongs to the field of agricultural chemistry and provides herbicides for pre-emergence treatment and post-emergence treatment. New 3-Phenyl-5 one-layer sliding door useful as
4(IH)-Pyridone and pyridinethio and salts thereof.

Since weed control is a critical step in the process of obtaining maximum crop yield, herbicides are now established as an important tool for farmers, and new and improved herbicidal compounds are still in demand. ing.

However, although much research has been conducted in the field of agricultural chemistry, no active compound closely related to the objective compound (1) described below in the present invention has been discovered so far.

Polyhalopyridones (having two or more chlorines on the pyridine ring in addition to other alkyl substituents and halogen substituents) are known as herbicides, but they are also known as active compounds (1) of the present invention. are clearly completely different compounds. In the field of organic chemistry, pyridones have traditionally been explored rather extensively.

For example, Ishibe et al. reported on the rearrangement of 3,5-diphenyl-1,2,6-trimethyl-4(IH)-pyridone (The Journal of the American Chemical Society, No. 95, pp. 3396-3397). 19
73), but such compounds are not herbicides. Leonard et al. 3,5-dibenzyl-1-methyl-4 (I
reported on the synthesis of H)-pyridones (which are also not compounds with herbicidal activity). (See The Journal of the American Chemical Society, Vol. 77, 1852-1855 (1955 hand)). Leonard et al. also reported on 3,5-di(substituted penzylidene)tetrahydro-4-pyridones. (
(See The Journal of the American Chemical Society, Vol. 79, pp. 156-160 (1957)). However, these compounds do not have herbicide activity. Wright et al. 2,6-diphenyl-1-
A number of 4-pyridone compounds have been reported, including methyl-4(IH)-pyridone and related compounds with phenyl ring substituents.

(See The Journal Op O, Gannick Chemistry No. 25, 538-546 (King 1960)). recently"
An interesting article was published by Elukhouri et al. (Journal of Heteropsychology).

(See Chemistry No. 1 Boto 665-667 (Published by King September 7, 1973)). 105-dihydroxy-204-diphenyl-104-pentadiene-
The synthesis of 3,5-diphenyl-1-methyl-4(IH)-pyridone and related compounds is described, consisting of the reaction of 3-one sodium salt with methylamine. The present invention describes novel 3-phenyl-5-substituted-4(IH)-herbicides having activity against a significantly wide variety of weeds.
The present invention provides pyridones (and thiones) and their salts (herbicides that are particularly effective on cotton fields).

The novel compounds of the present invention include compounds represented by the following general formula and salts thereof: where X represents oxygen or sulfur.

R is alkyl having 1 to 3 carbon atoms, 1 carbon number having a substituent
-3 alkyl (substituents are halogen, sia/or carboxy), alkenyl having 2 to 3 carbon atoms, alkoxy to acetoxy having 1 to 3 carbon atoms, or dimethylamino. However, the number of carbon atoms in R does not exceed 3. RI individually represents halogen, alkyl having 1 to 8 carbon atoms, alkyl having 1 to 8 carbon atoms substituted with halogen, alkenyl having 2 to 8 carbon atoms L
Cycloalkylalkyl having 4 to 8 carbon atoms, 1 to 3 carbon atoms
alkanoyloxy, alkylsulfonyloxy having 1 to 3 carbon atoms, phenyl, nitrocyano, hydroxy,
Hydroxy "alkoxycarbonyl having 1 to 3 carbon atoms, 10-R3" 1S-R3, 1SO-R3 or S02-
represents R3 (R3 is alkyl having 1 to 12 carbon atoms, alkyl having 1 to 12 carbon atoms substituted with halogen, "substituent 1
Alkyl having 1 to 12 carbon atoms (substituent is phenyl or cyano), phenyl, monosubstituted phenyl (substituent is nitro), cycloalkylalkyl having 4 to 8 carbon atoms, alkenyl having 2 to 12 carbon atoms, halogen Alkenyl having 2 to 12 carbon atoms or alkynyl having 2 to 12 carbon atoms substituted with . However, the number of carbon atoms in R3 does not exceed 12. R2 is halogen, hydrogen, cyano, carbon number 1-3
Alkoxycarbonyl "alkyl having 1 to 6 carbon atoms, alkyl having 1 to 6 carbon atoms having a substituent (substituent is halogen or alkoxy having 1 to 3 carbon atoms), 3 to 6 carbon atoms
cycloalkyl, cycloalkyl with 3 to 6 carbon atoms having a substituent (substituent is halogen), cycloalkenyl with 4 to 6 carbon atoms, phenyl (alkyl with 1 to 3 carbon atoms)
"Frill, naphthyl, thienyl, 10-R4" 1S-R
4, one SO-R4, one S02-R4 or (R
4 is alkyl having 1 to 3 carbon atoms, alkyl having 1 to 3 carbon atoms substituted with halogen, alkenyl having 2 to 3 carbon atoms substituted with halogen, benzyl, phenyl, or a substituent (The substituent is halogen or alkoxy having 1 to 3 carbon atoms).

R5 is the group represented by the pupil substituent RI above;
I is a group selected independently. ). m and n each represent 0, 1 or 2. However, when x is oxygen, R is methyl, and R2 is unsubstituted phenyl, m represents 1 or 2. Among the compounds (1) of the object of the present invention, compounds represented by the following formula are preferable. Methoxy ~ q and p are individually 0, 1 or 2, R7 is individually halogen, carbon number 1
~3 alkyl t trifluoro.

Methyl or alkoxy having 1 to 3 carbon atoms, R8 individually represents halogen, trifluoromethyl, alkoxy having 1 to 3 carbon atoms, or R8 is o- and m-
When present in position, together with the phenyl ring to which they are attached, they form a 1-naphthyl group. ]. Formula; [In the formula, R "RI and R2 have the same meanings as above.

] Compounds represented by the above are also preferred target compounds in the present invention, and among these, compounds in which RI is trifluoromethyl are most preferred. In the formulas herein, common chemical terms are used in their usual meaning.

For example, alkyl having 1 to 3 carbon atoms, alkenyl having 2 to 3 carbon atoms, alkynyl having 2 to 3 carbon atoms, alkoxy having 1 to 3 carbon atoms, alkyl having 1 to 8 carbon atoms, alkenyl having 2 to 8 carbon atoms, carbon Alkynyl having 2 to 8 carbon atoms "Alkyl having 1 to 6 carbon atoms, alkenyl having 2 to 6 carbon atoms, and alkynyl having 2 to 6 carbon atoms include, for example, methyl, ethyl, isopropyl, vinyl, allyl, methoxytoisopropoxy, pro/ Gurugyl, isobutyl, hexyl, octyl, 11
1-dimethylbentyl, 2-octenyl, bentyl, 3
-hexynyl t1-ethyl-2-hexenyl, 3-octynyl, 5-heptenyl, 1-propyl-3-butynyl, including crotyl, etc. Cycloalkyl having 3 to 6 carbon atoms, cycloalkenyl having 4 to 6 carbon atoms, for example Includes cyclopropyl, cyclobutyl, cyclohexyl, cyclobutenyl, cyclobentenyl, cyclohexadienyl, etc.

Cycloalkylalkyl having 4 to 8 carbon atoms includes, for example, cyclopropylmethyl, L-cyclobutylmethyl, cyclohexylmethyl, cyclohexylethyl, and the like.

Examples of alkanoyloxy having 1 to 3 carbon atoms include formyloxy, acetoxy, and phthalate.

Includes ropionyloxy and the like. Alkoxycarbonyl having 1 to 3 carbon atoms includes, for example, methoxycarbonyl, ethoxycarbonyl to isopropoxycarbonyl, and the like.

Alkylsulfonyloxy having 1 to 3 carbon atoms includes, for example, methylsulfonyloxy, propylsulfonyloxy, and the like.

Halogen includes fluorine, chlorine, bromine, iodine, and the like.

The object compound (1) of the present invention forms its acid addition salt, and such salts are also useful object compounds in the present invention.

Preferred salts are the hydrohalides (eg, hydroiodides, hydrobromides, hydrochlorides, hydrofluorides), and the sulfonates are particularly preferred. Such salts include sulfonates, methylsulfonates and toluenesulfonates. Next, specific examples of preferred compounds among the compounds represented by formula (1) will be given.

1-Methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, 3-(3-fluorophenyl)-1-methyl-5-phenyl-4(I
H)-pyridone, 3-(3-chlorophenyl)-1-methyl-5-phenyl-4(IH)-pyridone, 345-bis(3-chlorophenyl)-1-methyl-4(IH)
-Pyridone, 31 (3-k.

Lofenyl)-5-(3-fluorophenyl)-1-methyl-4(IH)-pyridone, 1-methyl-3-(3-
methylphenyl)-5-phenyl-4(IH)-pyridone, 3,5-diphenyl-1-methyl-4(IH)-pyridone "1-methyl-3,5-bis(3-trifluoromethylphenyl)-4( IH)-pyridone, 3-(3-
fromophenyl)-1-methyl-5-phenyl-4(I
H) Pyridone, 3-(3-methoxyphenyl)-1-methyl-5-phenyl-4(IH)-pyridone, 3-(3-methoxyphenyl)-1-methyl-5-phenyl-4(IH)-pyridone,
-ethoxyphenyl)-1-methyl-5-phenyl-4
(IH)-pyridone, 1-methyl-3-phenyl 51(3-propoxyphenyl)-4(IH)-pyridone,
3-(3-isobutoxyphenyl)-1-methyl-5
-Phenyl-4(IH)-pyridone, 1-methyl-3-phenyl 5-[3-(1,1,2,2-tetrafluoroethoxy)phenyl]-4(IH)-pyridone, 3.
5-pis(3-fluorophenyl)-1-methyl-4(
IH)-pyridone, 3-(2-chlorophenyl)-1-
Methyl-5-(3-trifluoromethylphenyl)-4
(IH)-pyridone, 3-(3-chloro.

phenyl)-1-methyl-5-1(3-trifluoromethylphenyl)-4(IH)-pyridone, 3-(4-chlorophenyl)-1-methyl-51(3-trifluoromethylphenyl)-4( IH)-pyridone, 3-(2-fluorophenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, 3-(3
-fluorophenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, 3-(4-fluorophenyl)-1-methyl-5-(3-trifluoromethylphenyl) )-4(IH)-pyridone,
3-(3-k.

lophenyl)-5-(4-chlorophenyl)-1-methyl-4(IH)-pyridone, 1-ethyl-3-phenyl m5-(3-trifluoromethylphenyl)-4(IH)
)-pyrido, n, 1-allyl-3-phenyl 51 (3
-trifluoromethylphenol)-4(IH)-pyridone, 1-methyl-3-(3-trifluoromethylphenol)-4(IH)-pyridone, 3-Qlo-1-methyl-5-( 3-trifluoromethylphenyl)-4(IH
)-pyridone “3-furomo-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone,
103-Dimethyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone 3-ethyl-1-methyl-5-(3-trifluoromethylphenyl)-4(I
H)-pyridone, 3-isopropyl-1-methyl-5-
(3-trifluoromethylphenyl)-4(IH)-pyridone "1-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridinethione, 1-methyl -3-(2-methylphenyl)-5-(3
-trifluoromethylphenyl)-4(IH)-pyridone "3-methoxym1-methyl-5-phenyl 4(I
H)-pyridone to 1-methyl-3-(3-methyl-4-methoxyphenyl)-5-phenyl-4(IH)-pyridone, 1-methyl-3-(3-methylphenyl)-5-
(3-trifluoromethylphenyl)-4(IH)-pyridone, 1-methyl-3-(4-methylphenyl)-5
Yama(3-trifluoromethylphenyl)-4(IH)-
Pyridone “3-(3-methoxycarbonylphenyl)-
1-methyl-5-(4-methylphenyl)-4(IH)
-pyridone, 3-(3-methoxycarbonylphenyl)
-1-methyl-5-(3-methylphenyl)-4(IH
)-pyridone, 3-(3-furomo-4-methylphenyl)-1-methyl-5-phenyl-4(IH)-pyridone, 3-methoxy-1-methyl-5-(3-trifluoromethylphenyl)-4( IH)-pyridone, 1-methyl-3-(3-nitrophenyl)-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, 1-methyl-3-(3-phenylsulfonylphenyl)-5- Phenyl-4(IH)-pyridone, 3-(4-fromophenyl)-1-methyl-5-(3-methylphenyl)-4
(IH)-pyridone "3-(4-chloro-2-fluorophenyl)-1-methyl-5-phenyl-4(IH)-
Pyridone, 3-(304-dichlorophenyl)-1-methyl-5-1(3-trifluoromethylphenyl)-4(
IH)-pyridone, 1-methyl-3-(3o4-dimethylphenyl)-5-phenyl-4(IH)-pyridone,
1-Methyl-3-(3,5-dimethylphenyl)-5-
Phenyl-4(IH)-pyridone, 3-(3-butylphenyl)-1-methyl-5-phenyl-4(IH)-pyridone, 1-methyl-3-(2o5-dimethylphenyl)-5-phenyl-4(IH) -Pyridone, 1M methyl-3-(204-dimethylphenyl)-5-phenyl-
4(IH)-pyridone, 1-methyl-3-(3-trifluoromethylphenyl)-5-(4-trifluoromethylphenyl)-4(IH)-pyridone "1-methyl-3
-Phenoxy-5-(3-trifluoromethylphenyl)-4(IH)-pyridone~. Trivalent ethoxycarbonyl-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, 3.5
-bis(3,5 dichlorophenyl)-1-methyl-4(
IH)-pyridone, 1-methyl-3-phenyl-5-(
3-phenylthiophenyl)-4(IH)-pyridone,
3-(3o4-dichlorophenyl)-1-methyl-1(3-methylphenyl)-4(IH)-pyridone, 3-(314-dichlorophenyl)-15-(3,4-dimethylphenyl)-1 -Methyl-4(IH)-pyridone t1
-Methyl-3-phenylthio5-(3-trifluoromethylphenyl)-4(IH)-pyridone, 3-(2.
4-dichlorophenoxy)-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone,
1-Methyl-3-(2-thienyl)-5-1(3-trifluoromethylphenyl)-4(IH)-pyridone, 3-
(3-carboxyphenyl)-1-methyl-5-phenyl-4(IH)-pyridone and the like.

There are the following similar methods for producing the compound (1) of the present invention by applying the secondary method. That is, 1.3
Condensation of -diphenyl-2-propanone with ethyl formate in the presence of sodium methoxide gives L1,5-dihydroxy-2,4-diphenyl-114-pentadien-3-one disodium salt (Benally and Bitter: Chemical・Berichte der 1 Deutschen. Hemischen Gesellschaft Volume 61 10 balls page (19
(See 2 Mother King). The obtained pentagenon compound is neutralized with a strong acid to form 3,5-diphenyl-4-pyrone. This pyrone compound and ammonium acetate are reacted at heating temperature to form the desired 3,5-diphenyl-4(IH)-pyridone. Similarly, by reacting a suitable ring-substituted 1,3-diphenyl-2-propanone with formamide and formamidine hydrochloride at reflux temperature, the corresponding 3,5-
Diphenyl-4(IH)-pyridones are obtained. The desired compound (1) can be obtained by reacting this pyridone compound with a halogen compound having the desired 1-substituent in the presence of a suitable strong base. Compound of the present invention (1
) can be produced by the following method.

That is, the formula: [wherein R1, R2 and m have the same meanings as above.

] One of QI and Q2 has two hydrogen atoms, and the other has =CHNHY (Y is hydrogen, hydroxy, alkyl having 1 to 3 carbon atoms, or having a substituent having 1 to 3 carbon atoms).
3 alkyl (substituent is halogen, cyano, or carboxy), alkenyl having 2 to 3 carbon atoms, 1 to 3 carbon atoms
alkoxy or dimethylamino. However, the number of carbon atoms in Y does not exceed 3. ), the ring is opened with a formylating agent or an aminoformylating agent, or QI
and Q2 are both individually =CHOH or =CHN(
R9) 2 (both R9s may individually be alkyl having 1 to 3 carbon atoms, or both R9s together with the nitrogen atom to which they are bonded may be pyrrolidi/, piberidino, morpholino or N-methylpivera) represents dino), the ring is closed with a compound represented by the formula: YNH2 (Y has the same meaning as above) or an acid addition salt thereof, and the formula: [wherein x, Y, R
1, R2 and m have the same meanings as above.

], and then in the case of compound (V) where Y is hydrogen or hydroxy, it is alkylated or esterified, respectively, to obtain the corresponding product where Y is R, and if necessary, X is The product (1), which is oxygen, is
The object compound (1) of the present invention can be obtained by treating with the compound (1) to obtain a product (1) in which X is sulfur.

As is clear from the above description, the object compound (1) can be produced by the following two methods in the present invention.

That is, the formula; [wherein R1, R2 and m have the same meanings as above.

], where both QI and Q2 are each individually of the formula: :CHOH or =CHN(R9)
2 [In the formula, R9 has the same meaning as above.

], the formula; YNH2 [In the formula, “Y” has the same meaning as above.

] to produce a compound (V). Then, in the case of a product (y) in which Y is hydrogen or hydroxy, this is alkylated or esterified, respectively, to form a compound (V) in which Y is R. A method for producing the target compound (1), which comprises obtaining the corresponding compound and optionally treating a compound in which X is oxygen with P5.

formula; [In the formula, R1 "R2 and m have the same meanings as above.

] where one of QI and Q2 has two hydrogen atoms and the other is formula 3;

], the compound (y) is prepared by closing with a formylating agent or an aminoformylating agent, and then in the case of a product (V) where Y is hydrogen or hydroxy, this is respectively Alkylated or esterified, Y
A process for producing the target compound (stand), which comprises obtaining the corresponding compound in which is R, and optionally treating a compound in which X is oxygen with P2S5.

One embodiment of the above ring-opening reaction is to react a compound (W) in which both QI and Q2 are two hydrogen atoms each with formamide or 18395-triazine.
The method consists of preparing an intermediate (y) in which is hydrogen and then alkylating it to obtain the corresponding target compound (ear).

This embodiment also converts formamide into formamidine.
The method consists of using it together with acetate. Preferred operations for synthesizing the object compound of the present invention are carried out by the method of Benally and Bitterhada and the method of Collie et al.

That is, a suitably substituted phenyl-2-propanone is formylated by reaction with sodium methoxide and ethyl formate in ether at low temperature and the product is treated with an amine salt of the desired tether in an aqueous medium. The majority of the compound obtained is 1-(R-amino)-2-phenyl-1-butesol-3-one (blood).Some pyridone compounds are formed in this step as reported by Ellukhouri et al. The compound can be reformylated as described above and subjected to spontaneous occlusion to obtain the 1-monosubstituted-3-phenyl-4(IH)-pyridone compound (Z). When Y in the process of the present invention is hydrogen, "YN The 1-unsubstituted pyrrolidone intermediate (V) was obtained by the operation of Benary and Bittuichi, using NH3 in place of the base, and the 1-position of this intermediate was then converted to R-halide or dialkyl sulfate by conventional methods. By alkylating,
The object compound (car) of the present invention can be produced.

Alternatively, the 1-unsubstituted pyro!i-done intermediate (V) is converted to a 4-halo or 4-alkoxy derivative, respectively, by reacting with a halogenating agent or an alkylating agent.

Suitable halogenating agents in this reaction include, for example, POC
13 to PO 3, Sasa Ci5, etc. Examples of the Q-alkylating agent include methyl trifluoromethanesulfonate, methyl fluorosulfonate, and alkyl halides in the presence of a base.The resulting four-plate halo or four-plate alkoxy compound is then reacted with Fujiichi halide. 1. A general monolayer 4-substituted pyridinium salt is obtained, and the desired compound (leather) can be produced by hydrolyzing this salt with acetic acid or an alkali metal hydroxide. Rasa Takahashi Famasutecal. Bulletin (Japan) Volume 1? 0~
? (See page 4 (1g53 King)). As is clear from chemical knowledge, the amines represented by RNH2 in the method of the present invention are used in the form of their salts, preferably hydrohalides (including hydrochloride, tohydrobromide, etc.). I can do something. Such salts are now preferred over free amines. The forkylating agent in the process of the invention can be selected from the reagents commonly used for that reaction.

A preferred formylating agent is a formate represented by the following formula. (alkyl having 1 to 5 carbon atoms) or (organic for formylation).

Synthesis. Collective volume neck “300~
See page 302 (King 1953). The above esters are used in the presence of a strong base, preferably an alkali metal alkoxide (eg sodium methoxide, potassium ethoxide, lithium propoxide, etc.).

Other bases may also be used, such as, for example, alkali metal hydrides, alkali metal amides or inorganic bases (e.g., alkali metal carbonates, alkali metal hydroxides). Also useful are diazabicyclononane and diazabicycloundecane. The reaction operation with the formylating agent is carried out in an aprotic solvent such as those commonly used in chemical reactions.

The preferred solvent is usually ethyl ether. Ethers (generally including ethyl propyl butyl ether, 182-dimethoxychetane, tetrahydrofuran, etc.), aromatic solvents (benzene, xylene, etc.) and alkanes (hexane to octane, etc.) can also be used as formylation solvents. can be used. Since a strong base is used in the formylation reaction, the best yields can be obtained at low temperatures.

A temperature range of about 125 to 10 loo C is preferred. However, even after the reaction has partially proceeded, the reaction mixture can be flooded to room temperature to complete the reaction. In the formylation reaction, a reaction time of about 1 to 24 hours is suitable to obtain an economical yield. The amimeformylating agent used in the synthesis method of the present invention is reacted with an active methylene group to =CHN(R
9) It may be a compound capable of introducing two groups or an acid addition salt thereof.

Such reagents can be selected from the following compounds; Formamide acetal represented by the formula: Tris(formylamino)methane represented by the formula: Formiminium halide represented by the formula: etc. [In the above formula, Pi is oxygen or sulfur, and R1o has 1 to 6 alkyl or phenyl, hal represents halogen.

R9 has the same meaning as above. ] Useful literature on aminoformylating agents is Tricarboxylic G Acid by Douolf.

Derivatives (Academic. Press (197th move)
Publication) pp. 420-506 and Ulrich: Chemistry 8 of Convex Imidoyle 9 Harize (Published by Plenum 6 Press (Military 96 Gunte)) 8? Examples include pages 96 to 96.
Brederek et al. have described the above reagents and their reactions in numerous publications. The most representative ones are as follows: Berichte also Der. Mischenshin Gesellschaft Vol. 101, pp. 4048-56 (1
Volume 97, pp. 3732-42 (1972 prison), Vol. 97, pp. 3407-406 (19th year)
1 sword page (Ju964) "102nd page 2io-21 (
i97 Hokooh) Toth G Fukuro Ai 288? -96 pages (1968 Jin) also 9th competition weights 1505-i4 pages (i963 Wang), 50th
Volume 4, pp. 3475-85 (1971) "Vol. ioi, 41
~50 pages (Kan 9 Iso year entry io ax cover 3Pne 5~3 army pages (i
G? Gakuimo). Annaren. Dear Mother, Me No.? 62 ships 62
~? 2 (1972 King). Angebante Mother Hemi - 7th Bag Lid 14 Sword Palace (196 & King). Angebante. Hemy International. Edition Volume 5, 32 pages (196
mother king). Some of the notable Ike literature on the subject is:
Kreuzberger et al.'s description (Archif' der 8 Falmai. und G Berichte 8 der Deutschen. Q Parmatsueuitigen Gesellschaft Volume 301 Satoshi 1~
96 (1968), Vol. 302, pp. 362-75 (1
96 Monomo)) and Weingarten et al.'s description (The Journal of Organic Chemistry - No. 32 Lid. 3)
293-94 (1967)). Aminoformylation is typically carried out without the use of solvents in approximately 50 to
It will be held for 200oo.

However, especially when it is desired to raise the boiling point of the reaction mixture, a solvent such as dimethylformamide is used. However, when aminoformylating with formiminium halide, an aprotic solvent similar to the solvent for the formylation is used at about 0 to 500 C, preferably at room temperature. In addition, in such aminoformylation, if necessary,
Halide solvents such as chloroform, methylene chloride can be used. For the exchange reaction with YNH2, a protic solvent (alkanol is preferred, and ethanol is most suitable).

) is most conveniently carried out. The reaction temperature in this exchange reaction may be about 120 to 1100°C, and room temperature is the most satisfactory and preferred temperature.The starting material (W) and intermediates in the method of the present invention can be obtained by the method shown below. Formula: [wherein R1, R2 and m have the same meanings as above.

] is reacted with a formylating agent or an aminoformylating agent. When a formylating agent is used in the above reaction, the formula is as follows: [In the formula, R1, R2 and m have the same meanings as above.

] A ketone intermediate is obtained. When using an aminoformylating agent, the formula: [wherein R1, R2, m and R9 have the same meanings as above.

] is obtained. Although the initial formylation or aminoformylation described above is shown in formulas (K) and (X) as occurring on certain side chains of the ketone structure, in reality these reactions are dependent on the activities of RI and R2. It is understood from chemical knowledge that this occurs on either side of the ketone depending on its chemical properties.

The reaction process is the same in either case. It is also to be understood that the product in this formylation or aminoformylation step is actually a mixture comprising two possible mono-substituted compounds and one di-substituted compound. This monosubstituted product is further formylated or aminoformylated and subjected to an exchange reaction with an amine of the formula YNH2.

Both steps can be performed in either order. When the exchange reaction is carried out first, the intermediate product has the formula: [wherein R1, R2, m and Y have the same meanings as above.

] is an enaminoketone. By formylating or aminoformylating this enaminoketone (which can also be represented by formula (VO)), as soon as this second group is introduced into the other methylene group, the ring is closed and a pyridone product is formed as an intermediate. is obtained.The above compound (X
) or (phantom) can be formylated or aminoformylated to obtain the following compounds.

formula: [In the formula, R1, R2, m and R9 have the same meanings as above.

] A compound in which the positions of the formyl group and aminoformyl group in the starting material (Xm) are reversed is equivalent to compound (Xm) in all respects. These three starting materials (
The object compound (1) of the present invention can be obtained by simply contacting the starting material (represented by the formula ()) with an amine compound represented by the formula: YNH2. The 2-propanone starting material (side) can be obtained by the synthetic method described in the following literature:

For example, Cohn et al.: The Journal of the American Chemical Society, No. 7, page 501 (19
Year of the Rat). Sullivan et al.: Disodium Tetracarbonyl Phyllate (American Laboratory), pp. 49-56 (French June 197). Colman et al.: Synthesis of Hemifluorinated Ketones Using Disodium Tetracarbonyl Ferrate (The Journal of the American Chemical Society No. 9)
5, pp. 2689-91 (1973)). Colman et al.: Acyl and alkyl tetracarbonylferate combinations as intermediates in the. Synthesis of aldehydes and
Ketones (The Journal of the American Chemical Society Group Volume 2516-18 (1972)
Year)). Further, the starting material (X) and equivalent materials can be obtained by the method shown in the following formula.

■ [In the formula, Hal represents a halogen.

R1, R2, m and R9 have the same meanings as above. ] In contrast to the bad method above, the method 'B} below is used. Emitting substance (X)
You can also get

(B} [In the formula, R1, R2, m and R9 are as defined above.

] Pyridone In the case where the 3- and 5-substituents in the target compound (1) are the same, the starting material (W) in which QI and P are the same can be obtained by using phosgene as the carbonyl halide. [C} [In the formula, R1, m and R9 have the same meanings as above.

]. In general, the starting material in the process of the invention is separated without purification by extraction, neutralization or removal of excess solvent, or after separation of the reactive mystery agent as appropriate.
Used in the next process. The above acylation reaction (A to C) of enamine is carried out in the above-mentioned non-brotonic solvent.
It is carried out in the presence of a base such as a grade amine, an alkali metal carbonate, magnesium oxide, etc.

In some cases, it may be necessary to perform supplementary synthetic operations after forming the pyridone compound.

For example, after preparing RI- and R5-hydroxy substituted compounds, substituents are introduced on the oxygen atom to form RI- and R5-hydroxy substituted compounds such as alkoxy, alkanoyloxy, etc.
It is advantageous to obtain corresponding compounds with -substituents. Pyridinethione compound (1) can be easily obtained by treating the corresponding pyridone compound (1) with P-5 in pyridine under reflux temperature conditions according to a conventional method.

The 1-acetoxy compound of formula (1) can be obtained by first preparing the corresponding 1-hydroxypyridone using hydroxylamine as the amine and esterifying this with acetic anhydride.

The other one-layer fusuma body is used when manufacturing pyridones.
It can be obtained by appropriately selecting the Y substituent in N. The preparation examples shown below are provided to enable those skilled in the art to reliably and easily prepare desired compounds encompassed by formula (1).

Although these production examples disclose various production methods for compound (1), it must be understood that any method can be adopted with or without appropriate modifications depending on the type of compound. Must be. Temperatures are in °C and nuclear magnetic resonance spectra (NM old) are given in cycles per second (cps), measured at 60 MHz with tetramethylsilane as internal standard.

Moreover, the melting point (MP) shows the value measured with a heat block.
Example 1 below shows an example in which a target compound is produced using a compound (skin) by a preferred synthetic method.

Production Example 1 1.5 hours of 1,3-diphenyl-2-propanone was mixed with 20 portions of dimethylformamide and 1.0 hours of tris(formylamino)methane, stirred at reflux temperature for 3 hours, and then cooled to approximately room temperature. and injected into water.

The precipitate was filtered, suspended in chloroform, and filtered.
The residual solid was washed first with water and then with chloroform,
- 5-diphenyl-4(IH)-pyridone (m.p. greater than 335 qo) 100 c was obtained. The salt compounds described below were prepared by forming the free base compound according to the general method of Example 29 below and contacting it with the appropriate acid in an aqueous solvent.

Production Example 2 1-Methyl-3,5-diphenyl-4(IH)-pyridone hydroiodide, m. p. 110 pm C, yield 100%
.

Production Example 3 1-Methyl-3,5-diphenyl-4(IH)-pyridone hydrochloride, m. p. 187-194qC, yield 100
%.

Example 1 Tetrahydrofuran 284 and sodium methoxide 284
Add 10% of 1-(3-trifluoromethylphenyl)-3-phenyl-2-propanone to a solution consisting of 556% of
-1500 for 20 minutes and stirred for 15 minutes.

Further 370 ml of ethyl formate was added for 30 minutes and the mixture was stirred at 10-1500 ml for 1 hour. An additional 296 g of ethyl formate was added to the above mixture for 30 minutes, and the reaction mixture was warmed to room temperature and stirred overnight. Furthermore, add 336 ml of a solution of methylamine hydrochloride in 1 ml of water, and
The phase mixture was stirred at 3000 for 30 minutes.
Further, the mixture was extracted with methylene chloride, and the extracts were combined and concentrated under reduced pressure to give 1-methylamino-2-phenyl-4-(3-trifluoromethylphenyl)-1-
Puten-3-one and 1-methylamino-4-phenyl-
An oily residue consisting of 2-(3-trifluoromethylphenyl)-1-buten-3-one was obtained. The residue was reacted in the same manner as above, dissolved in methylene chloride, washed with water, and dried.

After drying, the solvent was distilled off to give a solid product of 430 mm (yield: 65 mm).
%) was obtained. Infrared analysis, nuclear magnetic resonance (hereinafter referred to as NM), purified products recrystallized from ethyl ether,
1-Methyl-3-phenyl-5-(3-trifluoromethylphenyl)-
It was confirmed that it was 4(IH)-pyridone (melting point 153-155 qo). The elemental analysis values are as follows: Theoretical value association Actual value 黍G 69.30 69.48 days
4.29 4.42N 4.25
4.27 The following compounds were produced in the same manner as in Example 1 above.

Example 2 1-Methyl-315-bis(3-trifluoromethylphenyl)-4(IH)-pyridone, m. P.

152-15400, yield 39%.

Example 3 3-Phenyl-1-(2.2.2-trifluoroethyl)-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, quartet centered at NMR25&ps, aromatic proton 420 46&pS
, yield 46%.

Example 4 3-(3-bromophenyl)-15-(3-chlorophenyl)-1-methyl-4(IH)-pyridone.m. P. 1
92oo, yield 23%.

Example 5 3-(3-chlorophenyl)-5-(4-chlorophenyl)-1-methyl-4(IH)-pyridone.m. P. 1
70 to 17 are ○, yield 26%.

Example 63-(2-fluorophenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(IH
)-pyridone, m. p. 152-154 qo, yield 20
%.

Example 73-(2-cro.

phenyl)-15-(3-chlorophenyl)-1-methyl-4(IH)-pyridone m. P. 160-161℃,
Yield 15%. Example 83-(3-methoxyphenyl)
-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m. p. 113~115o
o, yield 7%.

Example 93-(4-chlorophenyl)-1-methyl-
5-(3-trifluoromethylphenyl)-4(IH)
- Pyridone, m. p. 153-155 pm ○, yield 26%
.

Example 101-aryl-3-phenyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone,
m. P. 107-109 pm, yield 38%.

Example 113-(4-isopropylphenyl)-1-methyl-5-phenyl-4(IH)-pyridone, m. P
．． 159°C, yield 60%.

Example 12 3-(2-chlorophenyl)-1-methyl-5-(3-
trifluoromethylphenyl)-4(IH)-pyridone, m. p. 191-19C, yield 14%.

Example 133-(3-fluorophenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(I
H)-pyridone, m. p. 94-96°C, yield 13%.

Example 14 3-(4-fluorophenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(I
H)-pyridone, m. p. 133-1 oak. 0, yield 29
%.

Example 153-(4-methoxyphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(I
H)-pyridone, m. p. 162-165 qo, yield 3
3%.

The following example shows the reaction of an enaminoketone of formula (X) with an amine to form a compound of formula (skin), which is then reacted with an aminoformylation reagent to synthesize the desired pyridone (1). This explains the method. Example 16 Enaminoketone, i.e. 2-phenyl-1-diethylamino -4-(3-methylthiophenyl)-1-buten-3-one was obtained.

Dissolve the above enaminoketone in 300ml of ethanol,
After 20 minutes of methylamine hydrochloride was mixed and stirred for about 2 hours, the solvent was evaporated. The residue was extracted with ethyl ether and washed with water. The organic layer was dried over anhydrous sodium sulfate and evaporated to dryness to yield 1-methylamino-4-(3-methylthiophenyl)-2-phenyl-1-buten-3-one. The residue was mixed with 50 ml of dimethylformamide dimethyl acetal, refluxed for 20 hours, and poured into water. Extracted first with ether and then with methylene chloride, washed with water, dried, and evaporated to dryness to obtain 1-methyl-3
-(3-methylthiophenyl)-5-phenyl-4(I
H)-Pyridone 9. NM old 144227cp
s, aromatic protons 420-440, 442-45 P
The following compounds were obtained by the same method as So.

Compounds of Examples 17 and 18 were prepared by oxidizing the compound of Example 16 with m-chlorobenzoic acid. Example 17 1-Methyl-3-(3-methylsulfinylphenyl)
-5-phenyl-4(IH)-pyridone m. P. 16
1-16400, yield 57%.

Example 181-Methyl-3-(3-methylsulfonylphenyl)-5-phenyl-4(IH)-pyridone.
m. P. 176-181°C, yield 31%.

Example 191-Methyl-3-phenyl-5-(4-trifluoromethylphenyl)-4(IH)-pyridone,
m. P. 164-166oC, yield 16%.

The following example illustrates a modification of the process starting with a carbonyl halide, in which the enaminoketone (X) is subjected to an exchange reaction with an amine to produce the compound (skin), which is then formylated. This will explain the process of obtaining pyridone (1). Example 20 Enaminoketone, i.e., 4- (3-benzyloxyphenyl)-1-diethylamino-2-phenyl-1-butene-
I got 3-on.

The above 13 min. did. The extract was washed with diluted hydrochloric acid and further washed with water, and the organic layer was separated, dried, filtered, and evaporated to dryness. The resulting intermediate 4-(3-benzyloxyphenyl)-1-methyl-amino-2-phenyl-1-buten-3-one was dissolved in 125 volumes of ethyl ether. The solution was cooled to 500 ℃ and 12 hours of sodium methoxide was added. While maintaining the temperature at about 500 °C, 50 °C of ethyl formate was gradually added, and the mixture was stirred while gradually raising the temperature to room temperature. The reaction mixture was evaporated to dryness, the residue was extracted with chloroform, the extract was washed with water and dried. The product was purified by chromatography on silica gel using a mixture of ethyl acetate and hexane (50:50) as an eluent, and the fractions were collected and evaporated to dryness. Recrystallized from ethyl acetate for 1.5 min to give 3-(3-benzyloxyphenyl)-1-methyl-5-phenyl-4(IH)-
Pyridone (m.p. 158-160 qo) was obtained. The following exemplified compounds were obtained using the same method as in Example 20 above. Example 21 1-methyl-3-phenyl-5-(2-thienyl)-
4(IH)-pyridone, m. p. 147-148°C, yield 6%.

Example 22 3-(3-isobutylphenyl)-1-methyl-5-phenyl-4(IH)-pyridone, NMR54147cp
s doublet, 11Xps septate, aromatic proton 420-46 ratio pS.

Example 23 1-Methyl-3-(3-nitrophenyl)-5-phenyl-4(IH)-pyridone, m. p. 135-136.
500, yield 33%.

Example 23A 1-Methyl-3-allylthio-5-(3-trifluoromethylphenyl)-4(IH)-pyridone.m. P. 7
4-7500, yield 5%.

Example 2 set 31 (4-chloro-3-trifluoromethylphenyl)
-1-methyl-5-phenoxy-4(IH)-pyridone, m. p. 130-131°C, yield 27%.

Example 2 1-Methyl-3-phenyl-5-allylthio-4(IH)-pyridone, m. p. 136-138q
o, yield 15%.

The following example shows a method for producing pyridone by the formamidine acetate method and further alkylating the 1-position.

Example 24 10 days of 1-(2,4-dichlorophenyl)-3-phenyl-2-probanone was heated at reflux for 3 hours in 75 degrees of formamide with 10 days of formamidine acetate, and the mixture was placed on ice. Pour and add more water.

After the ice melts, filter, wash the separated solid with ether,
Dissolved in ethanol. After decolorization with charcoal and recrystallization, compound 1.39, which was confirmed to be 3-(2,4-dichlorophenyl)-5-phenyl-4(IH)-pyridone by infrared analysis and NMR analysis, was obtained. Add the above pyridone to a solution of 60% dimethyl sulfoxide in 50% sodium hydride and heat until the pyridone dissolves.

Add methyl iodide and reduce to 0. After stirring for an hour, it was poured into water and filtered. Extract the solid material with methylene chloride,
Dry over magnesium sulphate and evaporate to dryness. The residue was recrystallized from benzene-hexane, and 3-(2,4-dichlorophenyl)-1 was determined by NM ash analysis and infrared analysis.
-Methyl-5-phenyl-4(IH)-pyridone (m.
p. Compound 1.1, which was confirmed to be 202-204q0), was obtained. The elemental analysis values are as follows:
Theoretical value (%) Actual value (multiple) C 66.68 66.84 days 3.83 4.05 N 4.09 4.01 The compounds illustrated below were produced by the general method of Example 24.

The 1-unsubstituted pyridone intermediate was made in part by the literature method of Benally and Bitter, supra. Example 25 3,5-diphenyl-1-ethyl-4(IH)-pyridone, m. p. 171°C, yield 75%.

Example 261-allyl-3,5-diphenyl-4(I
H)-pyridone, m. p. 174qo, yield 79%.

Example 27 3.5-diphenyl-1-isopropyl-4(IH)-pyridone, m. p. 15 or 0, yield 15%
.

Example 281-cyanomethyl-3,5-diphenyl-4(IH)-pyridone, m. p. Pine 1 to mouse ○, yield 5
5%.

The following example relates to a modified formylation method, in which the starting material ketoso of formula (W) is diformylated to form compound (W).
) is obtained, and subjected to an exchange reaction with an amine to obtain pyridone.
Example 29 100 parts of 1,3-diphenyl-2m bropanone were dissolved in 35 parts of ethyl formate and added to a solution of 25 parts of sodium methoxide and 500 parts of ethyl ether from 0 to 500 over 30 minutes.

Warm the mixture to room temperature and stir overnight.
460 g of 5-dihydroxy-2,4-diphenyl-1,4-bentadien-3-one dinatriwam salt was obtained.
This was used unpurified in the next step. 20 minutes of the above unpurified salt was added to 75 degrees of water containing 20 hours of propylamine and 5M concentrated hydrochloric acid, and the mixture was stirred at room temperature. After stirring for several hours, the mixture was extracted with ethyl ether and the aqueous layer was dried.

The residue was extracted with chloroform, the organic extract was dried,
Recrystallized from benzene-hexane to give 3.
5-diphenyl-1-propyl-4(IH)-pyridone (m.p. 172-17400) was obtained. The following compounds were prepared by the general method of Example 29. Example 30 3,5-diphenyl-1-methoxy-4 (IH)-pyridone, m. p. 16?0, yield 95%.

Example 31 3-(3-fluorophenyl)-1-methyl-5-phenyl-4(IH)-pyridone, m. p. 1
33.5°C, yield 69%.

Example 32 3-(4-Fromophenyl)-1-methyl-5-phenyl-4(IH)pyridone, m.p. 172°C, yield 63%.

Example 33 3-(4-methoxyphenyl)-1-methyl-5-phenyl-4(IH) river pyridone, m. p. 165°C, yield 32%.

Example 34 3-(3-chlorophenyl)-1-methyl-5-phenyl-4(IH)-pyridone, m. p. 172.5°C, yield 27%.

Example 35 3-(4-chlorophenyl)-1-methyl-5-phenyl-4(IH)-pyridone, m. p. 141.5°C, yield 76%.

Example 36 1-methyl-3-(1-naphthyl)-5-phenyl-4
(IH)-pyridone, NMR 204, 483 ps, aromatic proton 430-47 ps, yield 12%.

Example 37 3,5-bis(3-chlorophenyl)-1-methyl-4
(IH)-pyridone (m.p. 164-1670), yield 59%.

Example 1-Methyl-3-(3-methylphenyl)-5-phenyl-4(IH)-pyridone (complex containing 0.5 mol of benzene), m.p. p. 79.5 qo, yield 25%.

Example 391-methyl-3-(4-methylphenyl)
-5-phenyl-4(IH)-pyridone, m. p. 14
4.5°C, yield 28%.

Example 40 1-Methyl-3-(2-methylphenyl)-5-phenyl-4(IH)-pyridone, NMR 133201 cps
, aromatic protons 420-440, 442-46 ps
, yield 16%.

Example 41 3-(4-fluorophenyl)-1-methyl-5-phenyl-4(IH)-pyridone, m. p. 166°C, yield 60%.

Example 42 1-Methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone.m. P. 15
2 to 15 are C, yield 52%.

Example 433-(3-methoxyphenyl)-1-methyl-5-phenyl-4(IH)-pyridone, 200,2
2 ratio ps, aromatic protons 420-440, 442-4
6 ratio ps, yield 33%.

Example 44 3-(3,4-dichlorophenyl)-1-methyl-5-phenyl-4(IH)-pyridone, m. P. 166.5
°C, yield 54%.

Example 45 3-(215-dichlorophenyl)-1-methyl-5-phenyl-4(IH)-pyridone, m. P. 155.5
qo, yield 22%.

Example 46 3-(2-chlorophenyl)-1-methyl-5-phenyl-4(IH)-pyridone, m. p. 145) 0, yield 29%.

Example 47 3.

5-bis(3-fluorophenyl)-1-methyl-4(
IH)-pyridone, m. p. 149-151℃, yield 6
0%.

Example 48 3-(3-chlorophenyl)-15-(3-fluorophenyl)-1-methyl-4(IH)-pyridone, m. p.
145-146oo, yield 64%.

Example 493-1 (3.5-jiku.

(lofenyl)-1-methyl-5-phenyl-4 (IH)
- Pyridone, m. P. 131-135 qo, yield 28%
. Example 50315-bis(3-bromophenyl)-1-methyl-4(IH)-pyridone, m. p. 216.
5qo, yield 43%.

Example 51 3-(3-fromophenyl)-1-methyl-5-phenyl-4(IH)-pyridone, m. p. 17〆○, yield 3
8%.

Example 52 3-(2-fluorophenyl)-1-methyl-5-phenyl-4(IH)-pyridone, m. p. 165°C, yield 19%.

Example 53 3-(3-fromophenyl)-1-methyl-5-(3-
trifluoromethylphenyl)-4(IH)-pyridone, m. p. 151-15 0, yield 37%.

Example 541-(1-carboxyethyl)-3-phenyl-5-(3-trifluoromethylphenyl)-4(
IH)-pyridone, m. p. 236-2370, yield 1
3%.

Example 551-dimethylamino-3,5-diphenyl-4(IH)-pyridone, m. p. 14 ○, yield 94
%.

Example 561-methyl-3-(2-naphthyl)-5-
Phenyl-4(IH)-pyridone, m. p. 101-1
05'C, yield 45%.

Example 57 1-ethyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone.m. P. 98
~100 qo, yield 66%.

Example 583-Phenyl-1-propyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, NMR60, 23 ps triplet, 11 ps sexplet, yield 42%.

Example 59 1-methoxy-3-phenyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, NM old 24
Pillow PSo Example 60 3-(3-chlorophenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m. p. 133-135°C, yield 28%.

Example 61 3-(4-biphenylyl)-1-methyl-5-phenyl-4(IH)-pyridone, m-p. 186
~190°C, yield 1%.

Example 62 3-(3-biphenylyl)-1-methyl-5-phenyl-4(IH)-pyridone, m. p. 186-190℃,
Yield 2%.

The following examples demonstrate the synthesis of pyridones by diaminoformylation of ketones and exchange reaction with amines.

Example 63 A mixture of 26.8 μm of phenylacetone, 71.4 μm of dimethylformamide dimethyl acetal and 100 μm of anhydrous dimethylformamide was refluxed for 5 days and evaporated to dryness under reduced pressure.

Analysis of the residual red oil revealed that it was 1,5-bis(dimethylamino)-2-phenyl-1,4-bentadiene-3.
-one (approximately 75%) and the corresponding monoaminoformylated product (approximately 25%). Yield 3
0 evening. This material was used unpurified in the next step. Dissolve the above mixture in 100' of denatured ethanol and
After adding 100 ml of methylamine hydrochloride and refluxing overnight, the solvent was removed under reduced pressure.

The residue was taken up in methylene chloride and washed with water and then with saturated aqueous sodium chloride salt solution. The washed organic layer was dried using magnesium sulfate, the solvent was distilled off under reduced pressure, and the remaining oil was shaken with ethyl ether. The solid precipitated from ether was further washed with ether, air dried, and recrystallized from isopropyl ether-methylene chloride to give purified 1-methyl-3-phenyl-4(IH)-pyridone (m.p. )1M was obtained. Example
The product of Example 63 was dissolved in 100ml of water and bromine water was added dropwise until no more precipitate formed.

The precipitate was removed by filtration, washed with water, air dried, and recrystallized from ethanol to give 3-furomo-1-methyl-5-phenyl-4(IH)-pyridone (m.p. 195-19
70) was obtained. The following compound was prepared according to Example 63 or my method. Example 65 3-promo 1-methyl-5-(3-trifluoromethyl)-4(IH)-pyridone, m. p. 167-169
oo, yield 76%.

Example 66 1-Methyl-3-(3-trifluoromethylphenyl)
-4(IH)-pyridone, 12yo, yield 16%.

Example 67 3-chloro-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m. P. 170
~17 years old ○, yield 67%.

Example 68 3-(3-carboxyphenyl)-1-methyl-5-phenyl-4(IH)-pyridone hydrochloride, m. p. 26
6-2 porridge.

○, yield 10%. Example 693-(3-cyanophenyl)-1-methyl-5-phenyl-4(IH)-pyridone, m. p. 164-16 is o, yield 33%.

Example 70 3-(3-ethoxycarbonylphenyl)-1-methyl-5-phenyl-4(IH)-pyridone m. P. 16
7-168°C, yield 11%.

Example 713.5-bis(3-cyanophenyl)-1
-methyl-4(IH)-pyridone, m. p. 322-3
27q0, yield 22%.

Example 72 1-methyl-3-phenyl-5-(3-thienyl)-4
(IH)-pyridone, NMR 204, 49 ps, aromatic proton 430-46 ps, yield 34%.

Example 72A 1-Methyl-3-(2-methylphenyl)-5-(3-trifluoromethylphenyl)-4(IH)-pyridone "m.p. 144-1470, yield 5%.

Example 7 waves 1-methyl-3-(3-methylphenyl)
-5-(3-trifluoromethylphenyl)-4(IH
)-pyridone, m. p. 155-157℃, yield 2.4
%. Example 7 P1-methyl-3-(4-methylphenyl)-5-(3-
trifluoromethylphenyl)-4(IH)-pyridone, m. p. 154-156 qo, yield 6%.

Example 7 5-(3-methoxycarbonylphenyl)
-1-methyl-3-(4-methylphenyl)-4(IH
)-pyridone, m. p. 85°C to 50°C, yield 5%.

Example 7 Group 51 (3-methoxycarbonylphenyl)
-1-methyl-3-(3-methylphenyl)-4(IH
)-pyridone, m. p. 180-18yC, yield 1%.

Example 7 is 3-methoxy-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone,
m. P. 173-1750C, yield 18%. Example 7
Ko31(4-bromophenyl)-1-methyl-5-(3
-methylphenyl)-4(IH)-pyridone, m. P.
201-204oC, yield 21%.

Example 7 is 3-(3,4-dichlorophenyl)-1-
Methyl-5-1 (3-trifluoromethylphenyl)-4
(IH)-pyridone, m. p. 109-11 is 0, yield 4%.

Example 721 3.5-bis(3,5-dichlorophenyl)-1-methyl-4(IH)-pyridone, m. p. 275-278 0, yield 14%.

Example ? Phantom 3-(314-dichlorophenyl)-1-methyl-51(3-methylphenyl)-4(IH)-pyridone, mass vector MI=Milk 2 "Yield 10%.

Example 7 Ice 3-(3,4-dichlorophenyl)-5-(3,4-dimethylphenyl)-1-methyl-4(IH
) - Pyridone "m.p. 150-15 C, yield 6%.

Example 743-(3-chlorophenyl)-1-methyl-5-(2-methylphenyl)-4(IH)-pyridone.m. P. 171-17yo, yield 12%.

Example 72 3-(4-fromophenyl)-1-methyl-5-1(3-trifluoromethylphenyl)-4(I
H)-pyridone, m. p. 144-14bi0, yield 30
%.

The following compound is obtained by refluxing the above compound in 60% sulfuric acid. Example 7 is 3-(4-bromophenyl)-5-(3-carboxyphenyl)-1-methyl-4(IH)-pyridone, m. p
．． 259-26chi0, yield 50%.

The following compounds are obtained in the same manner as in Example 63. Example 7 Phantom 3-(3-chlorophenyl)-1-methyl-5-(4-
trifluoromethylphenyl)-4(IH)-pyridone, m. p. 147-151°C, yield 2%.

Example 7 is 3-(2-methylphenyl)-5-(4-
methylphenyl)-1-methyl-4(IH)-pyridone, m. P. 151-15400, yield 6%. Example 7
3-(3-methylphenyl)-5-(4-methylphenyl)-1-methyl-4(IH)-pyridone.m. P.
155-1570, yield 28%.

Example 7 Kitsune 31 (2-chlorophenyl)-51 (2-
methylphenyl)-1-methyl-4(IH)-pyridone m. P. 87-91°C, yield 1%.

Example 7 $ 1-methyl-3,5-bis(4-methylphenyl)-4
(IH)-pyridone, m. p. 212-214q0, yield 3%.

1-methyl-3-(3-chlorophenyl)-5-(3.
4-dichlorophenyl)-4(IH)-pyridone, m.
p. 107-110 qo, yield 10%.

Example 72U1-Methyl-3-(3,4-dichlorophenyl)-5-(2-methylphenyl)-4(IH)-
Pyridone, m. p. 103-106 pm ○, yield 10%.
Example 72V1-Methyl-31-(2-chlorophenyl)-15-1(3,4-dichlorophenyl)-4(IH)-pyridone, m. p. 169-171°C, yield 25%. Example 72W1-methyl-3-(3-bromophenyl)
-5-1(3,4-dichlorophenyl)-4(IH)-pyridone, m. p. 152-15400, yield 10%.

Example 7 is 1-methyl-3-(3,5-dichlorophenyl)-5-(3-trifluoromethylphenyl)-4
(IH)-pyridone, m. p. 156-160oC, yield 30%.

Example 72Y 1-methyl-3-(3-bromophenyl)-5-(3-
methylphenyl)-4(IH)-pyridone m. P. 1
44-1470, yield 3%.

Example 7Z1-Methyl-3,5-bis(3-methylphenyl)-4(IH)-pyridone, m. p. 148-1
50pm, yield 8%.

Example 7 Secretion A 1-methyl-3-(3-fluorophenyl)-51(2
-5-dimethylphenyl)-4(IH)-pyridone, mass vector skin = 307, yield 10%.

Example 7 Steal B 3-(3-bromophenyl)-1-methyl-5-(2-methylphenyl)-4(IH)-pyridone mass vector MI=353 Yield 2%.

Example 7-order C3-(3-fromophenyl)-5-(2
-chlorophenyl)-1-methyl-4(IH)-pyridone, m. P. 177-i7 movement ○, yield 10%.

Example 7 D3-(2-bromophenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(I
H)-pyridone, m. p. 197-19 pi○, yield 15
%.

Example 7 Group E3-(2,3-dimethoxyphenyl)-1-methyl-51(3-trifluoromethylphenyl)
-4(IH)-pyridone, m. p. 153-155 pm
, yield 20%.

Example 7 is F3-(2-methoxyphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(
IH)-pyridone, m. p. 193-196℃ "Yield 1
0%.

Example 7th G3-(2-ethylphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(I
H)-pyridone, m. p. 123-125 qo, yield 1
5%.

Example 7 Group Day 3-(3-promo-4-methylphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m. p. 158-161
q○, yield 30%.

Example 7211 3-(3-ethoxy4-methoxyphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(
IH) - pyridone, mass vector MI = 403 yield 1
0%.

Example 7 Fox K 3-(1-methoxyethyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, mass vector skin = 311, yield 1%.

The following examples illustrate the case where the corresponding enaminoketone (X) is aminoformylated to form the compound (of) and further exchanged with an amine to produce pyridone.

Example 73 1.92 dimethylaminoacrylonitrile and 1.6
The pyridine mixture was dissolved in 25% ethyl ether at 0°C, and a 3.08% solution of phenylacetyl chloride in ethyl ether 25% was added dropwise, and after the dropwise addition was completed, the mixture was stirred at 0°C for 2 hours.

It was dried under reduced pressure, and the residue was taken up in methylene chloride, washed with water, dried, and dried again. The crystals were collected in a furnace and recrystallized from isopropanol to obtain 2-cyano-1-dimethylamino-4-phenyl-1-buten-3-one 400-9. The above mixture of 300 g of enaminoketone and 10 g of dimethylformamide dimethyl acetal was heated under reflux for 12 hours and evaporated under reduced pressure.

To the residue were added 25 kg of denatured ethanol and 1 night of methylamine hydrochloride, and the mixture was heated under reflux for over 12 hours to dryness. The residue was taken up in methylene chloride, washed with water, dried and evaporated to dryness, triturated in ethyl ether and filtered. Recrystallize with isopropyl ether-acetone to obtain 260-9-3-cyano-
1-Methyl-5-phenyl-4(IH)-pyridone, (
m. p. 209-2103C) were obtained. The compounds in the following examples were obtained by the general method of Example 73 above. Example 74 1,3-dimethyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m. p. 130-13
rC, yield 12%.

Example 75 1,3-dimethyl-5-phenyl-4(IH)-pyridone, m. p. 111-11y0, yield 8%.

Example 76 3-(3-chlorophenyl)-1,5-dimethyl-4(IH)-pyridone, m. p. 143-14
3.5 pm, yield 6%.

Example 77 3-ethyl-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m. P. 95.
5-96. y0, yield 7%.

Example 783-Cyclohexyl-1-methyl-5-(
3-trifluoromethylphenyl)-4(IH)-pyridone, m. p. 174-175 qo, yield 40%.

Example 793-isopropyl-1-methyl-5-(3
-trifluoromethylphenyl)-4(IH)-pyridone, m. p. Satoshi. 5-99. yo, yield 10%.

Example 803-hexyl-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone,
m. P. 89.5-90.5 pm ○, yield 7%.

Example 813-penzyl-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone.
m. P. Satoshi~100q0, yield 18%.

Example 823-Butyl-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m
．． P. 2.5-84 qo, yield 9%.

Example 83 3-(3-cyclohexenyl)-1-methyl-5-(3
-trifluoromethylphenyl)-4(IH)-pyridone, m. p. 194-195°C, yield 43%.

Example 841-Methyl-3-propyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone,
m. P. 45-470, yield 3%.

Example 85 1-Methyl-3-(4-nitrophenyl)-5-phenyl-4(IH)-pyridone, m. p. 212-214o
o, yield 48%.

Example 86 3,5-bis(3,4-dimethoxyphenyl)-1-methyl-4(IH)-pyridone, m. p. 182-184
oo, yield 1%.

Example 87 3-ethoxycarbonyl-1-methyl-5-phenyl-4(IH)-pyridone, m.p. p. 107-1 female °C, yield spot %.

Example 88 3-(2-furyl)-1-methyl-5-phenyl-4(
IH)-pyridone, m. p. 191-19 ○, yield 6
9%.

Example 89 3-cyano-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m. P. 228
~229oo, yield 40%.

Example 903-(3,4-dimethoxyphenyl)-1
-methyl-5-phenyl-4(IH)-pyridone, m.
P. 1 milk to 1570, yield 4%.

Example 91 3-(3,4-dibromocyclohexyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(IH
)-pyridone hydrobromide, m. p. 196~1 group℃
, yield 26%.

Produced by bromination of the corresponding 3-(3-cyclohexenyl) form. Example Rudder 3-(3-isoprobenylphenyl)-1-methyl-5-phenyl-4(IH)-pyridone, NM old 125 214, 302, 327 cps, aromatic broton 420-47 ratio ps, yield 4% .

Example 93 3-(3-ethylphenyl)-1-methyl-5-phenyl-4(IH)-pyridone, m. p. 135-137C
OL yield 5%.

Example 94 3-(3-hexylphenyl)-1-methyl-5-phenyl-4(IH)-pyridone, m. p. 93-9500
, yield 6%.

Example 95 3-(4-ethylphenyl)-1-methyl-5-phenyl-4(IH)-pyridone, m-p. 143-14yo
, yield 6%.

Example 96 3-(3-cyclohexylmethylphenyl)-1-methyl-5-phenyl-4(IH)-pyridone.m. P. 1
47-14 were o, yield 9%.

Example 971-Methyl-3-phenyl-5-benzylthio-4(IH)-pyridone, m. p. 155-157
0, yield 36%.

Example 98 1-Methyl-3-phenyl-5-phenylthio 4(I
H)-pyridone, m. p. 164-16y0, yield 18
%.

Example 99 1-Methyl-3-phenoxy-5-phenyl-4 (IH
)-pyridone, m. p. 176-177qC, yield 19
%.

Example 100 1-Methyl-3-phenyl-5-phenylsulfonyl-4(IH)-pyridone, m. p. 218-220°C, yield 50%.

Produced by oxidizing the corresponding phenylthio compound with m-chlorobenzoic acid.

Example 10 3-(4-methoxy-3-methylphenyl)-1-methyl-5-phenyl-4(IH)-pyridone m. P. 1
57-160qC, yield 2.5%.

In Example 10, 3-(3-bromo-4-methylphenyl)-1-methyl-5-phenyl-4(IH)-pyridone m. P. 168-170oo, yield 13%.

Example 10 dishes 1-methyl-3-(3-nitrophenyl)-15-1(3-trifluoromethylphenyl)-4(I
H)-pyridone, m. p. 209-211℃, yield 51
%.

Example 10 Female 1-Methyl-3-phenyl-5-(3-phenylthiophenyl)-4(IH)-pyridone, mass vector MI=369, yield 8%.

Oxidation of the above compound with hydrogen peroxide in acetic acid gives the following compound.

Example 10 Misaki 1-Methyl-3-phenyl-5-(3-phenylsulfonylphenyl)-4(IH)-pyridone.m. P. 65
~7 is 0, yield 48%.

Example 10 Taka31 (2-chloro4-fluorophenyl)-1-methyl-5-phenylene-4(IH)-pyridone m. P. 1
90-19 is ○, yield is 5%.

Example 100 days 3-(3,4-dimethylphenyl)-1-methyl-5-phenyl-4(IH)-pyridone, m
．． p. 108-111°C, yield 5%.

Example 1001 3-(3,5-dimethylphenyl)-1-methyl-5-phenyl-4(IH)-pyridone, m. P. 148-1
50pm, yield 10%.

Example 100J3-(3-butylphenyl)-1-methyl-5-phenyl-4(IH)-pyridone, m. p.
87-89°C, yield 6%.

Example 100K 3-(2,5-dimethylphenyl)-1-methyl-5-phenyl-4(IH)-pyridone m. p. 188-19
000, yield 4%.

Example 10 Blood 3-(2,4-dimethylphenyl)-1-methyl-5-phenyl-4(IH)-pyridone, m.p. P. 153-1
5530, yield 3%.

M of Example 10 1-Methyl-3-phenoxy-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m. P. 1
44-145 qo, yield 15%.

Example 10 dishes 3-ethoxycarbonyl-1-methyl-
5-(3-trifluoromethylphenyl)-4(IH)
- pyridone, m. p. 151-1520, yield 62%.

1-Methyl-3-(3-trifluoromethylphenyl)-5-phenylthio-4(IH)-pyridone of Example 10, m. p. 164-165 qo, yield 18%. Example 10 1-methyl-3-(2-thienyl)-5-(
3-trifluoromethylphenyl)-4(IH)-pyridone, m. p. 185-1860C, yield 84%.

Example 100R3-ethylthio-1-methyl-5-phenyl-4(IH)-pyridone, m. p. 94-95q
C, yield 40%.

Example 10 3-ethylthio-1-methyl-5-(3
-trifluoromethylphenyl)-4(IH)-pyridone m. P. 84-85oo, yield 40%.

Example 100T3-(5-bromo-2-fluorophenyl)-1-methyl-5-phenyl-4(IH)-pyridone.m. P. 148-15000, yield 6%.

Example 100U1-methyl-3-(5nitro-2-
methylphenyl)-5-phenyl-4(IH)-pyridone m. P. 185-1870, yield 5%.

Example 100V3-cyano-5-(2,5-dimethoxyphenyl)-1-methyl-4(IH)-pyridone, m
．． P. 209-211°C, yield 4%.

Example low 3-(2,6-dichlorophenyl)-1-methyl-5-enyl-4(IH)-pyridone, m.P. 223-2
2600, yield 20%.

Example 100 x 3-ethoxycarbonyl-1-methyl-5-phenyl-4(IH)-pyridone, m.p. p. 10
7-1 female °C, yield 68%.

Example 100Y 1-Methyl-3-propylthio-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m. p.
101-10〆○, yield 25%.

Example iOMA1-methyl-3-methylthio5-(
3-trifluoromethylphenyl)-4(IH)-pyridone m. P. 121-12 is ○, yield is 20%.

Example 10 Female B1-Methyl-3-(3-trifluoromethylphenyl)-5-(4-trifluoromethylphenyl)-4(IH)-pyridone, m. p. 110-11
3pm, yield 10%.

Example 10 dishes D 3-(3,4-dimethoxyphenyl)-1-methyl-5
-(3-trifluoromethylphenyl)-4(IH)-pyridone, m. p. 148-150 qo, yield 10%.

Example 10 Cape E3-(5-fluoro-2-iodophenyl)-1-methyl-5-phenyl-4(IH)-pyridone and 3-(2-fluoro-5-fluorophenyl)
-1-Methyl-5-phenyl-4(IH)-pyridone mixture, m. p. 211-21400, yield 7
%.

Example 10 valent F 3-pendylthio 1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m. p.
121-12〆0, yield 40%.

In Example 10, G1.3-diethyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m.
p. 67-700○, yield 3%.

Example 100HH 3-(4-chloro-3-trifluoromethylphenyl)
-5-ethoxy-1-methyl-4(IH)-pyridone,
m. p. 158-159 ○, yield 15%.

Example 100111-methyl-3-isof.

o Pyrthio 5-(3-trifluoromethylphenyl)
-4(IH)-pyridone, m. p. 93~℃, yield 3
2%. Example 100JJ3-(4-chloro-3-trifluoromethylphenyl)-5-ethylthio-1-methyl-4(IH)-pyridone, m. p. 115-116q
o, yield 11%.

Example 100KK3-(4-chloro-3-trifluoromethylphenyl)-1-methyl-5-phenyl-4(
IH)-pyridone, m. p. 154-155℃, yield 1
7%.

Example 10 L3-(4-penzyloxyphenyl)
-1-Methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, amorphous, yield 10%.

The following compound is obtained by hydrogenating the compound of Example 10 in acetic acid in the presence of a hydrogenation catalyst of 5% palladium on carbon. Example 100 MM 3-(4-hydroxyphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m.p. p
．． 162-1630, yield 50%.

Example 100NN3-(2,5-dimethylphenyl)
-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m. p. 165-1670
0, yield 2%.

Example 10 ○ 3-(3,5-dimethylphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m. p. 160-163oo, yield 6%.

Example 100PP 3-(2.4-jikuro.

phenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m. p. 139
~142 qo, yield 11%. Q of Example 10 1-Methyl-3-phenyl-5-(2-trifluoromethylphenyl)-4(IH)-pyridone.m. P. 1 dose ~171℃, yield 14%.

Example 100RR1-Methyl-3-(2-trifluoromethylphenyl)-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m. p. 135-1
Spots.

0, yield 24%.

Example 105S Rusan; ~ Urarachiuma;: Mosanyusan 4 (IH)-pyridone, m. p. 150-1 bulb °C, yield 15%.

Example 100rT 3-(3-iodophenyl)-1-methyl-51(3-
trifluoromethylphenyl)-4(IH)-pyridone-m. p. 178-181°C, yield 15%.

Example 100UU3-ethyl-1-methyl-5-(3
-methoxyphenyl)-4(IH)-pyridone, yield 5
%, mass vector MI=243.

Example 100VV 1-Methyl-3-(3-yomdophenyl)-5-phenyl-4(IH)-pyridone, m-p. i90~193q
o, yield 8%.

Example 100WW 1-methyl-3-(4-methoxyphenoxy)-5-(
3-trifluoromethylphenyl)-4(IH)-pyridone, m. p. 119-12000, yield 25%.

Example 100XX1-methyl-3-(2-chloro-4
-fluorophenyl)-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m. p. 183～
186°C, yield 20%.

The following compound is obtained by oxidizing the compound of Example 10 with hydrogen peroxide in methylene dichloride at about 0°C.

Example 100YY 3-ethylsulfonyl-1mmethyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m.
p. 196-1°C, yield 70%.

Example 10 Z1-methyl-31 (4-chloro-3-trifluoro.

methylphenyl)-5-trifluoromethyl-4(IH
)-pyridone, m. p. IM~165 qo, yield 2%.
Example 10MB 1-methyl-3-(4-chloro-3-trifluoromethylphenyl)-5-propyl-4(IH)-pyridone,
m. p. 141-1420, yield 8%.

Example 10MC1-methyl-3-isopropylthio-
5-(4-chloro-3-trifluoromethylphenyl)
-4(IH)-pyridone, m. p. 127-129pm ○
, yield 15%.

Example 100AD 1-Methyl-3-(4-chloro-3-trifluoromethylphenyl)-5-propylthio 4(IH)-pyridone, m. p. 128-13 pi0, yield 15%.

Example 10ME1-methyl-3-(4-chloro-3-
trifluoromethylphenyl)-5-(2-thienyl)
-4(IH)-pyridone, m. p. 166-1 Iso℃, yield 10%.

Example 10MF 3-Ethyl-1-methyl-5-(4-k.

Rho-3-trifluoromethylphenyl)-4(IH)-
Pyridone, m. p. 121-123 qo, yield 1%. Example LO ship G1-Methyl-3-(2,4-dimethylphenyl)-5-(3-trifluoromethylphenyl)-
4(IH)-pyridone, m. p. 128-13ro, yield 6%.

Example 100AH 3-isopropoxy-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-piIJdon, mass vector MI=311, yield 1%.

Example 100AI1-methyl-3-(4-chlorophenoxy)-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m. p. 90-91℃, yield 1
5%.

Example 100AJ1-Methyl-3-(3-methylthiophenyl)-5-(3-trifluoromethylphenyl)
-4(IH)-pyridone, m. p. 150-15yC,
Yield 25%.

The following compound is prepared by oxidizing the compound of Example 10 Ship J in pyridine at room temperature with hydrogen peroxide. Example 100AK 1-methyl-3-(3-methylsulfonylphenyl)-
5-(3-trifluoromethylphenyl)-4(IH)
- pyridone, m. p. 180-18300, yield 20%
.

The following compound is obtained by oxidizing the compound of Example 10 with sodium periodate in aqueous ethanol for 16 hours at room temperature.

Example 10ML 3-ethylsulfinyl-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m
．． p. 146-14 is o, yield 82%.

Example 100AN3-(4-methoxyphenyl)-1
-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m. p. 160-16 zo○, yield 40%.

Example 100AO3-(2,3-dichlorophenoxy)-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m. p. 200-20〆C, yield 30%.

Example 10 Ship P 3-(3,5-dichlorophenoxy)-1-methyl-5
-(3-trifluoromethylphenyl)-4(IH)-
Pyridone, m. p. 128-130oo, yield 30%.

Example 10MQ3-(3,4-dichlorophenoxy)
-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m. p. 127-129q
o, yield 20%.

Example 10MR3-(4-chloro-3-trifluoromethylphenyl)-1-methyl-5-isopropyl-4
(IH)-pyridone, m. p. 85-870, yield 25
%.

Example 100AS3-(2,5-dichlorophenoxy)-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m. p. 162-1 I.

○, yield 28%. Example 100AT 1-methyl-3-(3-trifluoromethylphenyl)
-5-trifluoromethylthio-4(IH)-pyridone, m. p. 122-124oo, yield 21%.

Example 10 Fertilization A1-methyl-3-trifluoromethylsulfonyl-5-(3-trifluoromethylphenyl)
-4(IH)-pyridone, m. p. 155-157℃,
Yield 1%.

Example 10 Fertilizer C 1-methyl-3-(3-trifluoromethylphenyl)
-5-(3-trifluoro.

Methylthiophenyl)-4(IH)-pyridone, NMR
Multiplet 8.0-7.1ppm; Singlet 3
．． 27 ppm, yield 1%. Example 10 Female D 1-methyl-3-(3-trifluoromethylphenyl)
-5-(3-trifluoromethylsulfonylphenyl)
-4(IH)-pyridone, m. p. 164-16 is 0,
Yield 1%.

Example 100BE 1-Methyl-3-(2,2,2-trifluoro.

ethoxy)-5-(3-trifluoromethylphenyl)
-4(IH)-pyridone, NMR multiplet 8.0
~7.1 ppm; quartet 4.6 pPm; singlet 3.7 ppm, yield 1%. Example 10 Ship F 1-Methyl-3-(2-nitrophenyl)-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m. p. 230-2320, yield 10%.

The following example describes a method for formylating enaminoketone (X) to obtain compound (W), which is then subjected to an exchange reaction with an amine to obtain pyridone. Example
101 3.5 evening N・N-diethylstyrylamine and 2.16
from methoxyacetyl chloride in the presence of triethylamine in the presence of triethylamine, i.e., 1-diethylamino-4-methoxy-2-phenyl-1-butene-3.
-on (5 nights) was prepared.

The above enaminoketone was dissolved in 50% tetrahydrofuran.
Mix with sodium methoxide for 3.2 nights at 0°C, 4.
4 hours of ethyl formate was added dropwise.

After stirring for 3 hours, 25 portions of 40% aqueous methylamine were added followed by 5 portions of methylamine hydrochloride.

Stir overnight at room temperature, remove the solvent under reduced pressure, take up the residue in methylene chloride, wash with water and then with saturated brine,
Dry. The solvent was removed under reduced pressure, the residue was triturated with ethyl ether, and recrystallized from isopropyl ether-methylene chloride to give 3-methoxy-1-methyl-5-phenyl-4(IH)-pyridone (m .p.153-155qo
) I got one night. The following compounds were produced in the same manner. Example 101A 3-ethoxy-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m. P. 13
1 to 133 ○, yield 17%.

The following examples illustrate the preparation of 3-hydroxyphenyl substituted products and other substituted products obtained therefrom. Example 102 One day of the resultant of Example 20 was dissolved in 250% acetic acid, and 5%
% palladium on carbon was added thereto, and after hydrogenation for about 45 minutes, it was filtered and the filtrate was dried.

Recrystallized from ethyl acetate-hexane to obtain 3-(3-hydride).
xyphenyl)-1-methyl-5-phenyl-4 (IH)
-Pyridone (m.p. 223 ~ always o) 0.45 ml was obtained. 3
Two volumes of 1-(3-methoxyphenyl)-1-methyl-5-phenyl-4(IH)-pyridone were mixed with 15 volumes of pyridine hydrochloride, heated under reflux for about 1 hour, and then poured into a large amount of water to form a precipitate. was separated by filtration.

Recrystallized from ethanol-ethyl ether to give 3-(3-hydroxyphenyl)-1-methyl-5-phenyl-
1.1 of 4(IH)-pyridone was obtained. An additional 0.65 min was recovered by concentrating the supernatant. The following compound was obtained in the same manner as in Example 102.

Example 103 3-cyclohexyl-5-(3-hydroxyphenyl)
-1-methyl-4(IH)-pyridone, m. P. 155
~165 pm, yield 13%.

Example 104 Product 3 in Example 102.

Add 2 parts to a suspension of 0.86 parts of sodium hydride and 50 parts of dimethyl sulfoxide, stir at room temperature, and add 3 parts to
．． Added 50% ethyl iodide.

The mixture was stirred for 2.5 hours, then poured into water and extracted with ethyl acetate. The extract was washed with dilute hydrochloric acid and then with water, dried, filtered, and concentrated under reduced pressure to give 3-(3-ethoxyphenyl)-1-methyl-5-phenyl-4(
IH)-pyridone (m.p. 133-135)2.
I got 2 nights. The following example was carried out in a manner similar to Example 104. Example 105 3-(3-allyloxyphenyl)-1-methyl-5-phenyl-4(IH)-pyridone (NM old) 211,2
7 ratio ps, wide peak 296-328341-3783
99-45&ps, yield 10%.

Example 1063-[3-(1-fluoro-n2-iodovinyloxy)phenyl]-1-methyl-5-phenyl-4(IH)-pyridone, NMR 21 ps, broad peak 270-316 ps, aromatic proton 416-46 ps, The rate is 67%.

Example 107 3-(3-impropoxyphenyl)-1-methyl-5
- Phenyl 4 (IH) - Pyridone, NM old 81, 20
9, 27 ps, aromatic proton 401-4 pS,
Yield 18%.

Example 108 3-(3-cyanomethoxyphenyl)-1-methyl-5
-Phenyl-4 (Bait)-Pyridone, NM Town 207, 27
&ps, aromatic protons 396-456 pS, yield 6%
.

Example 109 3-(3dodecyloxyphenyl)-1-methyl-5
-Phenyl-4(IH)-pyridone, Nha rudder 52, 20
7. 234cps, wide peak 60-122cps
, aromatic broton 396-461 cps, yield 26%.

Example 110 1-Methyl-3-[3-(4nitrophenoxy)phenyl]-5-phenyl-4(IH)-pyridone, NMR222, 4 approximately. &ps, aromatic protons 414-46 $ps, yield 14%.

Example 111 1-Methyl-3-(3-methylsulfonyloxyphenyl)-5-phenyl-4(IH)-pyridone, NMR
18f 21$ps, aromatic proton 422-47Xp
S, yield 20%.

Example 112 1-Methyl-3-phenyl-5-[3-(1, 1, 2,
2-tetrafluoroethoxy)phenyl]-4(IH)
- pyridone, m. p. 119-12100, yield 84%
.

Produced by using tetrafluoroethylene in the presence of potassium hydroxide. Example 113 3-(3-acetoxyphenyl)-1-methyl-5-phenyl-4(IH)-pyridone, NMR 134, 21 ps, aromatic proton 415-46 ps, yield 28%
.

Manufactured by using acetic anhydride. Example 114 3-(3-hexyloxyphenyl)-1-methyl-5
-Phenyl-4(IH)-pyridone, NMR53" 2
14, 23 ps, broad peak 60-12 ps, aromatic protons 402-46 ps, yield 55%.

Example 115 3-(3-decyloxyphenyl)-1-methyl-5-
Phenyl-4 (IH) - Pyridone, NM old 53 "21
1,239 ps, broad peak 62-12 ps, aromatic proton 404-467 cps, yield 24%.

Example 116 1-Methyl-3-phenyl-5-(3-propoxyphenyl)-4(IH)-pyridone, NM Town 54101.5
208 23XpS, aromatic broton 400-46th ps, yield 31%.

Example 117 1-Methyl-3-phenyl-5-(3-propargyloxyphenyl)-4(IH)-pyridone, NMR150
21 ears ps, broad peak 280-28 & ps, aromatic proton 430-470 yield 6%.

Example 1183-(3-cyclohexylmethoxyphenyl)-1-methyl-5-phenyl-4(IH)-pyridone, NM old 214, 22 ps, broad peak 35-1
2 ps, aromatic protons 402-46 ps, yield 1
6%.

Example 119 1-Methyl-3-(3-octyloxyphenyl)-5
-Phenyl-4(IH)-pyridone, NM old 52, 21
8, 23 $ps, broad peak unevenness 12 Zps, aromatic protons 403-467 cps, yield 19%.

Example 120 1-Methyl-3-(3-phenoxyphenyl)-5-phenyl-4(IH)-pyridone, NMR, 21 ps,
Aromatic proton 410-47 ps, yield anchor %.

The following example starts with a ketone, which is formylated to form compound (K), then aminoformylated to obtain compound (K), and finally exchanged with an amine to produce pyridone. This explains the method.

Example 121 12 hours of sodium methoxide was suspended in 150 minutes of ethyl ether, cooled in an ice bath, and 28 hours of 1-phenyl-3-(3-trifluoromethylphenyl)-2-bropanone was added. Ta.

Ethyl formate was added dropwise to the bottom of the fly frame, and the mixture was gradually warmed to room temperature overnight. This was extracted with water, and the aqueous layer was made acidic with diluted hydrochloric acid, and then extracted with methylene chloride. The organic layer was extracted with dilute sodium hydroxide solution, and the aqueous layer was made acidic with dilute hydrochloric acid and extracted with methylene chloride. The extract was dried and evaporated to dryness under reduced pressure to produce mainly 1-hydroxy-2-phenyl-4-(
An oil consisting of 3-trifluoromethylphenyl)-1-buten-3-one was obtained. After heating 11 minutes of the above intermediate with 20 grams of dimethylformamide dimethyl acetal on a steam bath for 1 hour and drying the reaction mixture under reduced pressure,
The residue was taken up in 150' of ethanol.

10 hours of methylamine hydrochloride and 20 minutes of 40% aqueous methylamine were added and heated to reflux overnight then evaporated under reduced pressure to give an oil.

The oil was taken up in chloroform, washed with water and dried over sodium sulfate. The solvent was removed under reduced pressure, and the residue was triturated with ethyl ether and filtered to give 1-methyl-3-phenyl-(3-trifluoromethylphenyl)-(
IH)-pyridone (m.p. 153-155 pm) was obtained. The following example describes a method starting from a ketone, aminoformylating to obtain compound (X), formylating this to produce compound (W), and further subjecting it to an exchange reaction with an amine to obtain pyridone. It is something to do. Example 122 1-(3-Trifluoromethylphenyl)-3-phenyl-2-propanone was mixed with dimethylformamide dimethyl acetal and heated over a steam heater using a trap to remove the ethanol formed. .

After continued heating overnight, evaporation produced mainly 1-dimethylamino-4-phenyl-2-(3-trifluoromethylphenyl)-1-buten-3-one and 1-dimethylamino-2-phenyl-4-(3-trifluoromethylphenyl)-1-buten-3-one. An oil consisting of -trifluoromethylphenyl)-1-buten-3-one was obtained. Example 1
The above intermediate 5 was formylated using ethyl formate in the presence of sodium methoxide based on the method of Example 21.

The formylate was dissolved in ethanol and treated with 50% methylamine hydrochloride and 20% aqueous methylamine. The mixture was stirred overnight at reflux temperature, then the solvent was removed under reduced pressure and 100% aqueous methylamine was added. ' water was added to the residue and extracted with ethyl cable. The ether extract was dried over sodium sulfate and evaporated to dryness.
(IH)-pyridone (m.p. 153-155 qo) was obtained. In the example below, the ketone is tris(formylamino)
This describes a method for producing 1-unsubstituted pyridones by reaction with methane, in which the product is alkylated to obtain compound (1).

The following example describes a method for formylating a ketone to obtain a compound (K), then replacing it with an amine to produce a compound (skin), and further aminoformylating it to obtain a pyridone. .

Example 124 Formylation of 1-phenyl-3-(3-trifluoromethylphenyl)-2-propanone was carried out based on the method of Example 121.

The product was dissolved in 50 ml of ethanol, 20 ml of 40% aqueous methylamine was added, kept at room temperature overnight, and dried under reduced pressure to give a viscous oil. This oil was mixed with 10' of dimethylformamide dimethyl acetal and heated on a steam stove overnight using a trap to remove the ethanol formed. The reaction mixture was dried under reduced pressure, the residue was triturated with ether, filtered, and the solid was recrystallized from acetone-ethyl ether to give 1-methyl-3-phenyl-5- fluoromethylphenyl)-4(
IH)-pyridone (m.p. 153-15500) was obtained. The following compounds were produced in the same manner.

Example 124D 3-ethylthio-5-(2-chloro5-trifluoromethylphenyl)-1-methyl-4(IH)-pyridone, m. p. 127-12 pa○, yield 15%.

Example 12 3-(2-chloro-5-trifluoromethylphenyl)-1-methyl-5-phenyl-4(IH
)-pyridone, m. p. 150-1520, yield 30%
.

Example 1243-(2-chloro-5-trifluoromethylphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, NMR peak, multiplet 8.0-7. 2Ppm; singlet 3.57ppm, yield 40%.

The following example describes a method for producing compound (1) by chlorination at the 4-position of a 1-unsubstituted pyridone, followed by 1-alkylation and hydrolysis.

Example 125 3-Phenyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone 39 (synthesized using the method of Benally and Bitter) with dimethylformamide on POC 13 and 5 of 100 for 3 hours The mixture was refluxed and excess POC13 was distilled off under reduced pressure.

The residue was taken up in chloroform, poured into cold water, stirred until it reached room temperature, and then extracted with chloroform. The extract was washed with dilute sodium hydroxide solution, dried and evaporated to dryness under reduced pressure, and the residue was recrystallized from hexane to give 4
-chloro-3-phenyl-5-(3-trifluoromethylphenyl)pyridine was obtained. The above compound 2 was dissolved in 20 volumes of chloroform, 10 wZ of methyl chloride was added, and the mixture was allowed to stand for 4 days.

This was evaporated to dryness and the residue was recrystallized from chloroform-hexane to obtain 4-chloro-3-phenyl-5-(3-trifluoromethylphenyl)-1-methyl-pyridinium aiodide. . The above intermediate was dissolved in methanol, the solution was made alkaline with sodium hydroxide solution, refluxed for 1 hour, cooled, and the solid was filtered off to give 1-methyl-3-phenyl-5-( 3-trifluoromethylphenyl)-4(IH)-pyridone (m.p. 153-1
5yo) was obtained. The following examples illustrate the 1-alkylation of 1-unsubstituted pyridones by reaction with methylating reagents.

Example 126 3-Phenyl-1-(3-trifluoromethylphenyl)-4(IH)-pyridone was suspended in 30 ml of tabletop chloroform and 6 ml of methyl trifluoromethanesulfonate was added.

After stirring for 3 hours, 10 more sulfonic acid esters were added and stirred overnight.

The next morning, the reaction mixture was poured into aqueous sodium carbonate solution and
It was filtered and the solid was washed with chloroform. The organic layer of the filtrate was separated, dried using magnesium sulphate and evaporated. The residue was an oily gum, which was confirmed by NMR analysis to be pure 3-phenyl-5-(3-trifluoromethylphenyl)-1-methyl-4-methoxypyridinium trifluoromethanesulfonate. The above residue was mixed with 30 minutes of desktop ethanol and 3 hours of concentrated hydrochloric acid and refluxed for 2 hours with stirring.

The reaction mixture was concentrated under reduced pressure and taken up in methylene chloride. After washing this with an aqueous sodium carbonate solution and drying the organic layer again under reduced pressure, the residue was triturated with ethyl acetate. The solid (combined with the product to be separated later) and the ethyl acetate solution were separated, the solution was concentrated under reduced pressure, and the residue was
It was mixed with 0' of ethanol and 10' of 10% sodium hydroxide solution and stirred at reflux temperature for 2 hours.
This was poured into water, the impurities were separated by filtration, and recrystallized from acetone to 1-methyl-3-phenyl-5-(3
-trifluoromethyl-phenyl)-4(IH)-pyridone (m.p. 152-15 is C) was obtained. The following example describes the use of formate aminal as the aminoformylation reagent in the process. Example 127 1-phenyl-3-(3-trifluoromethylphenyl)-2-propanone (15 min.) was kept on ice for 70 min.
A solution of t-butoxy)-di(dimethylamino)methane in ethyl ether was added, warmed to evaporate the ether, and heated on a steam stove for a further 2 hours.

The volatiles were evaporated under reduced pressure and the residue was mixed with 15 ml of methylamine hydrochloride, 40 ml of 40% aqueous methylamine and 200 ml of ethanol, heated on a steam stove for 6 hours and evaporated to dryness. I let it happen. The residue was taken up in water and extracted with methylene chloride. The extract was washed with water, dried,
Ethyl acetate: Chromatography on silica gel using benzene yielded 0.9 m of 1-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone (m. p.1
52-156°C). The following example illustrates the use of formiminium halide to aminoformylate a starting propanone.

Example 128 An aminoformylation reagent was obtained by adding dropwise 30 ml of dimethylformamide to 150 ml of chloroform containing 20 ml of phosgene at 0°C.

This was followed by 10 minutes of 1,3-bis-(3-chlorophenyl)-2-bropanone. Add solution of Roform 50, 3
After an hour of fermentation, 50 portions of 40% aqueous methylamine were added. Chloroform was evaporated from the mixture, and 200
Added 50' of ethanol and 50' of 40% aqueous methylamine. The mixture was refluxed overnight, and the next morning the product was extracted as described in the example above and sequentially subjected to silica gel chromatography using methyl acetate mixtures with increasing methanol content. -bis(3-chlorophenyl)-1-methyl-4(IH)-pyridone0
．． 85 m.p. 164-167o0 was obtained. The column was subsequently eluted with methanol and 4-chloro-3,5-bis(3-chlorophenyl)-1 was determined by tNMR.
-A compound fixed with methylpyridinium chloride was obtained. The above compound was hydrolyzed with an ethanolic sodium hydroxide aqueous solution at reflux temperature, diluted with water, filtered in an oven,
Additional amounts of pyridone were obtained by recrystallization from acetone-ethyl ether. The following example shows a method for producing 1-acetoxy compound (1). Example 12
9 2.49 3,5-diphenyl-1-hydroxy-4(IH)-pyridone was prepared according to the method of Example 29 using hydroxylamine as the aminating reagent.

After adding the pyridone to 25 parts of acetic anhydride and heating the mixture over a steam bath for about an hour, the volatiles were evaporated under reduced pressure and the residue was washed with benzene and then chloride.
Recrystallized from roform-hexane, 1-acetoxy 3
・5-diphenyl-4(IH)-pyridone (m.p.1
97-19900) 2.1 evening was obtained. The following compounds were produced in the same manner.

Example 12 Salmon 1-acetoxy-3-phenyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m. p.
232-235q○, yield 5%.

The following example shows a typical method for producing pyridinethiones (1). Example 132 3,5-diphenyl-1 obtained by the method of Example 1
-Methyl-4(IH)-pyridone (100 g) was mixed with 100 g (510 g) of pyridine in pyridine and refluxed for 2 hours.

I poured it into a large amount of water and prayed for an hour. The mixture was filtered and the solid was recrystallized from ethanol to give 3,5-diphenyl-1-methyl-4(IH)-pyridinethione (m.p.
．． 1 road ~ 17100) 9.8 evening was obtained. The following compounds were produced in the same manner.

Example 132A 3-(3-bromophenyl)-1-methyl-5-phenyl-4(IH)-pyridinethione, m. P. 185-1
Spots.

0, yield 59%.

Example 13 $ 1-Methyl-3-(4-chlorophenyl)--(3-
trifluoromethylphenyl)-4(IH)-pyridinethione, m. p. 239-24 0, yield 25%.

Example 13 1-Methyl-3-(3-methylphenyl)-5-1(3-trifluoromethylphenyl)-4(IH)-pyridinethione, m. p. 193-196°C, yield 50%.

Example 13 Fox 1-methyl-3-(2-methylphenyl)-5-(3-
trifluoromethylpheni)-4(IH)-pyridinethione, m.

p. 193-19℃, yield 35%. Example 13 Bait 1-methyl-3-propyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridinethione, m. p
．． 145-14 0, yield 40%.

Example 13 is 1-methyl-3-phenoxy-5-(3
-trifluoromethylphenyl)-4(IH)-pyridinethione, m. p. 127-131°C, yield 40%.

Example 13 Momme 3-ethylthio 1-methyl-5-(3
-trifluoromethylphenyl)-4(IH)-pyridinethione, m. p. 136-13 children○, yield 55%.

Example 13 is 3-ethoxy-1-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridinethione, m. p. 153-155°C, yield 5%.

The following typical pyridinethiones were prepared according to the general method of Example 132. Example 1333・5-bis(3
-chlorophenyl)-1-methyl-4(IH)-pyridinethione m. p. 210-212°C, yield 86%.

Example 134 3-(3-chlorophenyl)-1-methyl-5-phenyl-4(IH)-pyridinethione, m. P. 130-1
33 ○, yield 71%.

Example 1351-Methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridinethione, m. p. 21000, yield 70%.

The following compound was prepared by refluxing the compound of Example 1 in 60% sulfuric acid for 4 hours. Example 13 Matsu 3-(3-carboxyphenyl)-1-methyl-5-phenyl-4(IH)-pyridone, m. p. 265-26
700, yield 75%.

Example 136 Compound (1) produced in Examples 1 to 23 can also be produced by the method of Example 29.

Example 137 Compounds (1) produced in Examples 24 to 122 can also be produced by the method of Example 1.

Compound (1) was subjected to various herbicidal tests to determine their herbicidal effects.

Typical test results are shown below. The amount of test compound used is expressed in kilograms of the compound used per hectare of ground (k9'ha). Blanks in the table below indicate that no tests were conducted.

In addition, some of the values are average values. Untreated control plants or plots were used in all tests, and percentage inhibition by test compounds was determined by comparison. In the tests of Examples 138 to i42, plants were
It was rated as 5th grade.

The 1st grade indicates a normal plant, and the 5th grade indicates a dead plant or a non-germinating plant.
10 indicates a normal plant, and 10 indicates a dead or non-germinated plant. The tests of Examples 146-147 and 152 were evaluated as percentage of plants controlled by the drug, and the grade used in the test of Example 151 is indicated in the description of that example. EXAMPLE 138 Broad Spectrum Greenhouse Test Square plastic pots were filled with sterile sandy loam and planted with tomato, stingray, and purslane seeds, and each pot was individually fertilized.

The test compound was then applied to some pots after germination and to others before germination, in the former case approximately 12 hours after sowing.
The test compounds were applied to the germinated plants and, in the latter case, to the soil the day after sowing.

Each test compound was then mixed with acetone:ethanol (1
1) Dissolved at a rate of 2 parts per 100 parts of the anionic-nonionic surfactant mixture, and the solution contained about 2 parts per 100 parts of the anionic-nonionic surfactant mixture.

This solution 1' was diluted to 4' with deionized water and the resulting solution 1.5' was applied to each pot. This is a similar application rate when the test compound was used at an application rate of 16.8k9/ha. After application of the active compound, the pot is placed in a greenhouse and watered with the required amount of water for approximately 10 to 13 minutes.
Observation and evaluation were conducted after 1 day. In addition, untreated control plants were prepared as evaluation standard plants in all tests. 1st
The table shows the test results for the representative target compound [1].

The test compound names are the same as the compounds obtained in the examples indicated by the numbers. Table 1 Example 139 Greenhouse test on 7 types of plants The same test as in Example 138 above was conducted.

However, in this test, a metal flat plate was used instead of a pot, and the seeds were sown in this. Similar to Example 1 except that the test compound is dissolved in a solvent containing a surfactant at a ratio of about 6 parts/100 parts and about 1 part of this organic solution is diluted with 12 parts of water before being applied to the plate. The test drug was prepared by the following procedure. The test compound thus prepared was
It was applied at a ratio of a. The test results for various plants are
Shown in the table. TABLE 2 EXAMPLE 140 GREENHOUSE TEST ON MULTIPLE PLANT TYPES Test methods are generally the same as those described above.

Various target compounds [1] were used as test compounds, and pre-germination and post-germination treatments were carried out at different usage rates shown in the following table. In the pre-emergence treatment test, additional types of weeds and crops were tested. The results of the pre-germination treatment test are shown in Table 3, and the results of the post-germination treatment test are shown in Table 4. Table 3 (Pre-germination treatment) Table 4 Example 141 Test against yellow nut edge Dissolve approximately 1.5 minutes/100 of a typical target compound [1] as a test compound in acetone-ethanol, and add this organic solution. Before application, 1 part was diluted with 9 parts of water, and the herbicidal effect of the target compound [1] on yellow nut edge was tested in a greenhouse using the same test method as in Example 1.

Both pre-emergence and post-emergence treatments were tested at an application rate of 9.0k9'ha.

The test results are shown in Table 5. Table 5 Example 142 Test against broad-leaved weeds The herbicidal effects of representative target compounds on representative broad-leaved weeds of families that exhibit resistance to many known herbicides were tested in a greenhouse.

The test compound was applied at 9.0 k9/ha prior to emergence and the test was conducted in a manner generally similar to Example 141. 6th result
Shown in the table. Table 6 Example 143 Test on 14 lotus plants containing test compound in soil In this test, representative compound (1) was evaluated against agricultural crops and weeds.

The target compound (1) was tested in various proportions shown in Table 7 in a greenhouse. Before sowing seeds, all compounds were mixed into the soil and used as a pre-germination treatment for plants. The compound was dissolved in acetone-ethanol overnight at a concentration similar to 100% and then diluted with water immediately before application, and the compound was prepared and the test plants were planted and observed in the same manner as in Example 141. Ta. The results are shown in Table 7. Table 7 Example 144 Greenhouse test on 14 crabs Weeds In this test, the test compound (1) was applied to the soil surface to perform a pre-germination treatment on the test plants.

Test methods are generally similar to Example 141. Table 8 shows the proportions of compounds used and the results. Different compounds were tested on different plants. TABLE 8 EXAMPLE 145 Test Compounds in Soil In this test, the compound of interest was incorporated into the soil prior to sowing and tested generally according to the method of Example 141.

Table 9 shows the results of tests conducted on various plants using various compounds at different usage rates. 9th
Table Example 146 Soil surface spray test on collective crops Weed seeds were artificially sown in the test plots, and a field screening test was conducted to test representative objective compound (1) on representative crops.

Seeds of the No. 1 dominant crop are sown in stripes on medium to heavy soil of the Midwest type. Immediately after sowing the pus crop seeds, the active compound is applied in a strip across the streaks. The inside of this band is about 1,
Let the length of the stripes of agricultural products in one section be 1. The compound is applied as in Example 139 in the form of an aqueous suspension onto the soil surface. All test plots will be seeded with crop seeds and covered with weed seeds of Portulaca purslane and Psyllium vulgare just before application of the compound. For comparison with the treated plots, a control plot for the sheath treatment is provided. Thirty-nine days after sowing seeds and applying compound treatment, a plant science expert observed the weed suppression rate (%) and crop injury rate (%).
) to evaluate. The obtained results are shown in Section 1. 1st
0 Table Example 147 The target compound (1
) was immediately mixed into the soil using a rotary cultivator, and after these treatments, seeds of agricultural crops and weeds were immediately sown, and tests were conducted. The results are shown in Table 11.

Table 1 Example 148 Test on perennial weeds Compound (1) was tested on representative perennial weeds.

The active compound was formulated according to the method of Example 1. Greenhouse soil was placed in a plastic pot, and Western bindweed, Bermuda grass, Johnson grass, and Aspen grass were planted in it, and the above-mentioned compound was applied to it. Western bindweed was planted with rootstocks obtained from wild plants, johnson grass and sycamore grass were planted with rhizomes obtained from wild plants, and bermuda grass was planted with seasoned branches taken from a greenhouse. After weeding, immediately apply the above compound (
(formulated product) was applied uniformly over the pot, and the soil was lightly watered.

Each pot was fertilized for several days after this treatment. Pots were kept in a greenhouse and plants were observed 5 weeks after compound application. The results of evaluating the degree of suppression of weeds on a scale of 0 to 10 are shown below. A post-emergence treatment test of the above compound was also conducted on similar weeds.

In this test, weeds were allowed to grow for 30 to 60 days after the plants were tagged before compound application. Prior to compound application, the plants were trimmed to a height of 4 to 8 inches, and the western bindweed branches were trimmed at the terminals that contacted the pot. The results of observing the plants 4 weeks after the treatment are shown in the table below.
Example 149 Test on perennial weeds The types of weeds, treatment conditions, etc. in this test are as in Example 1.
It is similar to that of No. 48.

Weeds were observed about 4 weeks after the compound was applied, and the results of the pre-germination treatment are shown in the table below. The results of post-emergence treatment tests are shown below.

Example 150 Mesquite Test The objective compound (1) was tested on mesquite trees grown in a greenhouse.

When grown 5 to 12 inches tall, transplant the tree into a 1 gallon customer metal pot.

After the tree has started to grow vigorously in the pot, the target compound is applied wet to the soil. The compound to be used was prepared by dissolving it in acetone:ethanol in the same manner as in Example 138, and then suspending an appropriate amount of this solution in 25 parts of water.
Apply this to each pot. The mesquite trees were observed approximately 90 days after application of the compound and the results compared to the control test on a scale of 0-10 are shown below. Example 151 Grapefruit Test The target compound was tested in a grapefruit orchard in a tropical climate.

The tree is grown in a growing bed using sandy soil and watered with sprinklers. The active compound is applied when the tree is approximately two years old. The beauty compound is formulated in the same manner as for Example 1 paper, and is surface-sprayed on a one-skin square area of the soil around each tree.

The results of evaluating the degree of crop damage to trees on a scale of 0 to 10 approximately one week after application of the compound are shown below.

Furthermore, the degree of weed suppression was observed approximately one week after spraying the compound. The results are expressed as a suppression rate (%) compared to the number of weeds growing in an untreated control plot, and are shown in the following table. Example 152 Test for suppressing purple nut edge in cotton cultivation The following test was conducted in a cotton crop field where purple nut edge was flourishing.

They cultivated cotton without making ditches in the flat clay fields of the subtropical climate. The target compound is dispersed in water as an 80% hydrating agent, and this is mixed into the soil immediately before cotton planting.
The crops and weeds were observed approximately 8 weeks after the compound was applied, and the results were calculated as crop injury rate (%) or weed suppression rate (%).
) as shown in the table below. Example 153 Weed suppression test in coffee cultivation A test was conducted under the same conditions as in Example 152 by applying the target compound to an existing coffee farm.

However, the compound was sprayed on the surface of the soil. No injury to coffee was observed when crops were observed approximately 6 weeks and approximately 4 months after application of the compound in amounts not exceeding 2k9' ha.

In this test, excellent suppressive effects were observed on weeds such as annual herbaceous plants, annual broad-leaved plants, Paraguayan starburst, Bristle starburst, Hairy beggar tex, Thousand sandbar, and/or prunutsedge. From the above Examples, it is clear that the compounds of the present invention have excellent broad-spectrum activity as herbicides.

Judging from the examples, the target compound exhibits a herbicidal effect on annual herbaceous plants, relatively easily inhibits broad-leaved plants such as Portulaca, and has a herbicidal effect on nightshades, nightshades, etc.
Broadleaf plants such as ragweed, sicklepod, etc. are somewhat difficult to kill. In addition, the target compound suppresses perennial weeds such as johnson grass, sycamore grass, western bindweed, bermuda grass, nutsedge, etc., which are very difficult to control. The target compounds also suppress algae and aquatic weeds (eg coontil, hydrilla, etc.). Furthermore, the target compounds kill woody plants such as mesquite, which is an economically harmful plant in dry climate conditions. Based on this fact, when woody plants are not required as agricultural crops, the compounds of the present invention can be used to suppress such undesirable woody plants. Furthermore, as botanically clear from the Examples, the target compound exhibits herbicidal effects against all types of weeds. However, a preferred embodiment of the weeding method is to implement a method that selectively kills herbaceous weeds.

It is a remarkable feature that the target compound exhibits herbicidal effects in both pre-emergence and post-emergence treatments.

Therefore, the compound of interest can be applied to the soil in order to contact the soil and kill the weeds when the weed seeds germinate. The target compound can also be used to kill germinated weeds by contacting exposed parts of weed plants. When the target compound is used by pre-emergence treatment, the weeds die either during germination or within a short period after germination. The compound (1) of the present invention can be effectively brought into contact with aquatic weeds by suspending or dissolving it in water in which aquatic weeds grow, or by applying it to subaqueous soil in which weeds take root.

Since the compounds of the invention have a significant herbicidal effect, the method of using them to control weeds is an important embodiment of the invention. This embodiment consists in a selective weeding method comprising contacting weeds with a herbicidally effective amount of the target compound (1). For the purpose of the present invention, the weed seeds that are brought into contact with the compound of the present invention by pre-germination treatment can be regarded as the weed plants themselves. As shown in the examples, the pre-germination treatment effect is obtained whether the target compound is applied to the soil surface or mixed into the soil. As is clear from the examples, many of the target compounds are safely acceptable for agricultural crops such as peanuts, soybeans, sugar beets, wheat, and tree crops when used in appropriate proportions and at appropriate times. Many of the target compounds are derived from paddy rice,
It is surprisingly safe for both upland rice and transplanted rice. It is noteworthy that there was no particularly significant harm to cotton in the experiments shown in Examples. Since cotton can be safely treated with the target compound, it is a preferred embodiment of the present invention to adopt a method for exterminating weeds in cotton fields due to this safety. The object compound (1) of the present invention can be used in an appropriate amount to completely inhibit plants. Such suppression methods are currently preferred when agricultural land is to be kept fallow for a period of time, or for applications on industrial properties or traffic surfaces. Since the target compounds can control perennial weeds and woody plants, they are particularly useful as general control agents for plants. Weeding methods that utilize efficacy to selectively exterminate weeds are noteworthy. The term weed is used herein in a non-restrictive sense, but also broadly to refer to undesirable or non-desirable plants, such as poisonous plants. For example, in a cotton field, the method of the present invention can be applied to eliminate not only plants that are not desired per se, such as johnson grass, ragweed, etc., but also other invasive crops that are not desired in the cotton field. As plant scientists recognize, herbicides must be used in the correct dosages to achieve selective control of weeds. Compound (1) of the present invention relative to the total amount of weeds
The proportion of weeds controlled by using a compound depends on the type of weed, the type of compound itself used and its amount.

In many cases, all weeds can be eradicated. In some cases, some of the weeds are killed and some of the weeds are injured, as shown in some examples.

Even when some of the weeds are killed and others are injured, it is effective and beneficial to use some of the compounds of the present invention. Simply injuring weeds is beneficial because surrounding normally growing crops cover the injured and slow-growing weeds, creating shade and causing them to wither. The best amount of a target compound to use to control a target weed depends, of course, on how the compound is used, climatic conditions, ± hair type, soil water and organic matter content, and other factors known to plant science. Dependent.

However, in virtually all cases it has been found that the optimum rate of use of the compounds of the invention is about 0.025-20 kg/ha. Typically, optimum usage rates are preferably in the range of about 0.025 to 5k9/ha. When the target compound is to be applied to the soil or when a wide range of weed species are involved, it is effective to treat the compound by both pre-emergence and post-emergence treatments. Application of the compound of interest at some point during the germination or development of the weeds can provide at least some suppressive effect on the weeds. Furthermore, by applying the target compound to the weeds in advance during their dormant period, it is possible to kill weeds that are about to germinate during the coming warm season. When using a target compound to control weeds in an annual crop, it is usually best to apply the compound in a pre-emergence treatment when the crop is shielded.

When a target compound is mixed into soil, it is usually mixed into the soil immediately before shading crops. When applying to the soil surface, it is usually easiest to apply immediately after planting. Application of the compound of interest of the invention to the soil or to germinating weeds is carried out according to customary agrotechnical methods.

The target compound can be applied to the soil in water-dispersed or granular form. The method for preparing such a dosage form is as described below. Usually, a water-dispersed dosage form is used when applying the target compound to germinated weeds. Chemicals can be applied using a variety of sprayers or granule spreaders that are widely used to apply pesticides to soil or growing plants. When mixing the target compound into the soil, it is effective to use a conventional soil cultivator such as a desk harrow or a rotary hoe operated by power. The object compound (1) of the present invention is usually used in the form of a herbicidal composition, and this composition is an important aspect of the present invention.

The herbicidal composition of the present invention consists of the active compound (1) and an inert carrier. Generally such compositions are formulated by conventional agrochemical methods and are novel only because of the presence of new herbicidal compounds. The compound (1) of the present invention can be prepared in the form of a concentrated composition and then prepared in the form of an aqueous dispersion or emulsion containing about 0.1 to 5% of the active compound. Spray on Aoi side.

Compositions that can be dispersed or emulsified in water are solids, commonly known as wettable powders, or liquids, commonly known as emulsions. These concentrated compositions are used having compositions in the following ranges: Ingredients Weight (%) Compound of the Invention (1) 10-80 Surfactant 3-10 Inert Carrier
87-10 hydrating powders consist of a finely divided mixture of the target compound, an inert carrier, and a surfactant.

The concentration of the target compound is usually about 10-90%. Inert carriers are usually selected from clays such as attapulgite, kaolin, montmorillonite, diatomaceous earth, and purified silicates. Effective surfactants include sulfonated lignin, condensed naphthalene sulfonate, naphthalene sulfonate, alkylbenzene sulfonate, alkyl sulfate, and nonionic surfactants (such as ethylene oxide adducts of phenol). The content is about 0.5 to 10% in the wettable powder. A typical emulsion consists of a convenient concentrate dissolved in an inert carrier (a mixture of water-immiscible solvents and emulsifiers) at a rate of about 100 to 500 mg/liquid. Useful organic solvents include aromatic compounds (particularly xylene), petroleum fractions (particularly the high boiling naphthalene and olefinic portions of petroleum). Many other organic solvents can also be used, such as terbenic solvents, alcohol complexes (eg 2-ethoxycetanol). Suitable emulsifiers for emulsion preparation can be selected from surfactants of the same type as those used for wettable powder preparation. When applying the compound of the present invention to soil for pre-germination treatment, it is preferable to use a granular preparation.

Such agents typically consist of a dispersion of the target compound on a granular inert body (eg, coarsely ground clay). The particle size is typically about 0.1 to 3 ribs. A conventional granule formulation process consists of dissolving the target compound in an inexpensive solvent and mixing this solution with the spoil in a suitable solids mixer. The granular composition is usually formulated with each component in the following proportions: Component Weight (%) Compound (1) of the present invention 1 to 10 Surfactant
0-2 inert carrier
99-88 Although somewhat less economical, the desired granular composition can be produced by dispersing the target compound in a dough of wet clay or other inert carrier, which is then dry-milled. .

Claims (1)

[Claims] 1 Formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X represents oxygen or sulfur. R is alkyl having 1 to 3 carbon atoms, 1 carbon number having a substituent
-3 alkyl (substituent is halogen, cyano or carboxy), alkenyl having 2 to 3 carbon atoms, alkoxy having 1 to 3 carbon atoms, acetoxy or dimethylamino. However, the number of carbon atoms in R does not exceed 3. R^1 individually represents halogen, alkyl having 1 to 8 carbon atoms, alkyl having 1 to 8 carbon atoms substituted with halogen, alkenyl having 2 to 8 carbon atoms, cycloalkylalkyl having 4 to 8 carbon atoms, and 1 to 8 carbon atoms. ~
3 alkanoyloxy, alkylsulfonyloxy having 1 to 3 carbon atoms, phenyl, nitro, cyano, carboxy, hydroxy, alkoxycarbonyl having 1 to 3 carbon atoms,
-O-R^3, -S-R^3, -SO-R^3 or S
O_2-R^3 (R^3 is alkyl having 1 to 12 carbon atoms, alkyl having 1 to 12 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms having one substituent (the substituent is phenyl or cyano), phenyl, monosubstituted phenyl (substituent is nitro), cycloalkylalkyl having 4 to 8 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms substituted with halogen, or having 2 to 12 carbon atoms substituted with halogen. 2-12 alkynyl, provided that R^3 does not exceed 12 carbon atoms). R^2 is halogen, hydrogen, cyano, alkoxycarbonyl having 1 to 3 carbon atoms, 1 carbon number
-6 alkyl, alkyl having 1 to 6 carbon atoms having a substituent (substituent is halogen or alkoxy having 1 to 3 carbon atoms), cycloalkyl having 3 to 6 carbon atoms, having 3 to 6 carbon atoms having a substituent Cycloalkyl (substituent is halogen),
Cycloalkenyl having 4 to 6 carbon atoms, phenyl (alkyl having 1 to 3 carbon atoms), furyl, naphthyl, thienyl, -
O-R^4, -S-R^4, -SO-R^4, -SO_
2-R^4 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R^4 is alkyl with 1 to 3 carbon atoms, alkyl with 1 to 3 carbon atoms substituted with halogen, or ▲with 2 to 3 carbon atoms) Alkenyl, alkenyl having 2 to 3 carbon atoms substituted with halogen, benzyl, phenyl, or phenyl having a substituent (the substituent is halogen or alkoxy having 1 to 3 carbon atoms), and R^5 is the above substituent R. It is a group selected from the groups indicated by ^1, independently of R^1.). m and n each represent 0, 1 or 2. However, when X is oxygen, R is methyl, and R^2 is an unsubstituted phenyl group, m represents 1 or 2. ] 3-
Phenyl-4(IH) pyridone and pyridinethiones and salts thereof. 2 Formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X is oxygen or sulfur, R^0 is alkyl having 1 to 3 carbon atoms, alkenyl having 2 to 3 carbon atoms, acetoxy or methoxy, q and p are individually 0, 1 or 2, R^
7 is individually halogen, alkyl having 1 to 3 carbon atoms, trifluoromethyl or alkoxy having 1 to 3 carbon atoms, R^8
are individually halogen, trifluoromethyl, carbon number 1-3
represents alkoxy, or R^8 represents two of which are o-
and when present in the m-position, together with the phenyl ring to which they are attached, form a 1-naphthyl group. ]. 3-phenyl-4(IH) pyridone and pyridinethione and salts thereof according to claim 1, which are represented by: 3 Formulas: ▲ Numerical formulas, chemical formulas, tables, etc.
or carboxy), alkenyl having 2 to 3 carbon atoms, alkoxy having 1 to 3 carbon atoms, acetoxy or dimethylamino. However, the number of carbon atoms in R does not exceed 3. R^1 individually represents halogen, alkyl having 1 to 8 carbon atoms, alkyl having 1 to 8 carbon atoms substituted with halogen, alkenyl having 2 to 8 carbon atoms,
Cycloalkylalkyl having 4 to 8 carbon atoms, 1 to 3 carbon atoms
alkanoyloxy, alkylsulfonyloxy having 1 to 3 carbon atoms, phenyl, nitro, cyano, carboxy,
Hydroxy, alkoxycarbonyl having 1 to 3 carbon atoms, -
O-R^3, -S-R^3, -SO-R^3 or -S
O_2-R^3 (R^3 is alkyl having 1 to 12 carbon atoms, alkyl having 1 to 12 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms having one substituent (the substituent is phenyl or cyano), phenyl, monosubstituted phenyl (substituent is nitro), cycloalkylalkyl having 4 to 8 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms substituted with halogen, or carbon It is alkynyl of number 2 to 12.). R^2 is halogen, hydrogen, cyano, alkoxycarbonyl having 1 to 3 carbon atoms, alkyl having 1 to 6 carbon atoms, and 1 carbon having a substituent.
~6 alkyl (substituent is halogen or carbon number 1~
3 alkoxy), cycloalkyl having 3 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms having a substituent (the substituent is halogen), cycloalkenyl having 4 to 6 carbon atoms, phenyl-(having 1 to 3 carbon atoms) alkyl), frill, naphthyl,
Thienyl, -O-R^4, -S-R^4, -SO-R^
4, -SO_2-R^4 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ~3 alkenyl, halogen-substituted alkenyl having 2 to 3 carbon atoms,
Benzyl, phenyl or phenyl having a substituent (substituent is halogen or alkoxy having 1 to 3 carbon atoms)
and R^5 is a group independently selected from the groups represented by the substituent R^1 above. ). n represents 0, 1 or 2. ] 3-phenyl-4(IH)pyridone and its salts according to claim 1.