CA1075697A - 3-phenyl-5-substituted-4(1h)-pyridones(thiones) - Google Patents
3-phenyl-5-substituted-4(1h)-pyridones(thiones)Info
- Publication number
- CA1075697A CA1075697A CA305,980A CA305980A CA1075697A CA 1075697 A CA1075697 A CA 1075697A CA 305980 A CA305980 A CA 305980A CA 1075697 A CA1075697 A CA 1075697A
- Authority
- CA
- Canada
- Prior art keywords
- methyl
- pyridone
- phenyl
- trifluoromethylphenyl
- methylphenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/69—Two or more oxygen atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/68—One oxygen atom attached in position 4
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/70—Sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/70—Sulfur atoms
- C07D213/71—Sulfur atoms to which a second hetero atom is attached
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/84—Nitriles
- C07D213/85—Nitriles in position 3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/89—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to the ring nitrogen atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pyridine Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Abstract of the Disclosure A class of novel 3-phenyl-4(1H)-pyridones and pyridinethiones which are broad-spectrum herbicides are described herein. The new compounds are characterized by a small substituent on the nitrogen, and usually bear a 5-substituent chosen from a class described herein. The phenyl ring may be substituted. The compounds are effective herbicides when applied both before and after the emergence of weeds, and are particularly useful for the control of weeds in cotton or rice cropland.
Description
10756~3~
This invention belongs to the field of agricul-tural chemistry, and provides to the art new preemergence and postemergence' herbicides, and compositions and methods of applying the compounds for the contro:L of weeds. Since the control of weeds is known to be a vital step in the maximization of crop yields, herbicides are now established as vital tools of the farmer and new and improved herbicidal compounds are in constant demand.
Despite the great amount of research which has been performed in the field of agricultural chemistry, active compounds closely related to the compoun~s of formula I herein have not been previously discovered. The poly- ~`
halopyridones, which have two or more chlorine atoms as well as other alkyl and halo substituents on the pyridine ring, are known herbicides, but are obviously quite distinct from the compounds of formula I.
The organic chemical art has explored the pyri-dones rather extensively. For examplei Ishibe et al~, J.
Am. Chem. Soc. 95, 3396-3397 (1973), disclosed a rearrange-20 ment of 3,5-diphenyl-1,2,6-trimethyl-4(1~)-pyridone. Such compounds, however, are not herbicides. Leonard et al., J.
Am. Chem. Soc. 77~ 1852-1855 (1955) ~ taught the synthesis of 3,5-dibenzyl-1-methyl-4(lH)-pyridones, which compounds also ` `~
have no herbicidal~activity. The same principal author also ~ .
disclosed 3,5-di(substituted-benzylidene)tetrahydro-4-pyridones, J. Am. Chem. Soc. 79, 156-160 (1957)o These compounds also have no herbicidal activity.
, ` , '`
, ~30 X-4097K ~ -2-~ : ' ' ' ' ' . . ' ' : .
' . ' ' ' , ' ' ~ ., ' . ~
' ,, , : .~ ' ~ ' `' ' , :
Light et al., J. Org. Chem. 25, 538-54~ ~1960), taught a number of 4-pyridone compounds including 2,6-diphenyl-l-methyl-4(lH)-pyridone, and related compounds bearing phenyl-ring substituents, none of which are her-bicidally active.
An interesting recent ar~icle was published by El-Kholy et al. in J. Hetero. Chem. 10, 665-667~(published September 7, 1973). El-Kholy described a synthesis of 3,5-diphenyl-l-methyl-4(lH)-pyridone and related compounds by ~ -the reaction with methylamine of the sodium salt of 1,5-dihydroxy-2,4-diphenyl-1,4-pentadien-3-one.
A series of novel 3-phenyl-4(1H)-pyridones(thiones) are herbicides which are active against an unusually wide range of weeds are disclosed in copending Canadian Application Serial No. 233,945, filed August 22, 1975.
New methods and compositions for applying the compounds for the control of weeds, which methods are particularly useful in cotton or rice cropland, are also disclosed.
The novel compounds are of the general formula X
Rl ~ - J ~l ...
R
wherein: X is oxygen or sulfur, R is methyl, ethyl, acetoxy or hydroxy;
the Rl groups independently are halo; Cl-C~
alkyl; Cl-C4 alkyl substituted with halo; nitro;
carboxy; hydroxy; Cl-C2 alkoxycarbonyl;
-o-R3; ~ S-R3; -So-R3; or -5O2-R ;
_ 3 _ . .
g~
R3 is Cl-C2 alkyl; C1-C2 alkyl substituted wi-th halo; benæyl; or phenyli R iS cyano; Cl-C3 alkox~fcarbonyl; Cl-C4 alkyl;
Cl-C~ alkyl subsiituted wllh halo, hydroxy or Cl-C3 alkoxy; thienyl; -O-R~ S-R4; -So-R4;
-So2-R , or ` ,..
\~_ GXR5 ' .
R4 is C1-C6 alkyl; Cl-C6 alkyl substituted with hydroxy or haLo; C2-C4 alkenyl; benzyl; ph nrl; or phenyl substituted with trifluoromethyl, halo, Cl-C3 alkyl, nitro, C1-C3 alkylthio or Cl-C3 .
alkoxy;
the R5 groups independently are nalo; Cl-C4 alkyl;~Cl-C4 alkyl substituted with halo; nitro; ~:
carboxy; hydroxy; Cl-C2 alkoxycarbonyl; _o-~6; ~:
-S-R6; -SO-R6; or -502-R6;
. R6 is Cl-C2 alkyl; Cl-C2 alkyl substituted . ~: with halo; benæyl; or phenyl;
m and n independently are 0, 1 or 2; provided that when X is oxygen, R is methyl, and R2 is unsubstituted phenyl, then m is 1 or 2;
: ~and the acLd addition salts thereof.
:
: 30 ~ ~
X-4097K _4_ : . :
:
. .
!
~7~7 The present invention relates to a group of novel and useful compounds which geneLally fall within the scope of Serial No. 233,945. These compounds are selected from:
l-methyl-3-(3-nitrophenoxy)-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, 3-(4-methoxy-3-methylphenylJ-:L-methyl-5-phenyl-4(lH)-pyridone, . 3-(3-bromo-4-methylphenyl)-1-methyl-5-phenyl-4(lH)-pyridone, 1-methyl-3-(3-nitrophenyl)-5-(3-trifluoromethyl-2henYl)-4(lH)-pyridone, l-methyl-3-phenyl-5-(3-phenylthiophenyl)-4(lH)-pyridone, i l-methyl-3-phenyl-5-(3-phenylsulfonylphenyl)-4(1H)-pyridone, 3-(2-chloro-4-fluorophenyl)-1-methyl-5-phenyl-4(lH)-pyridone, 3-(3,4-dimethylphenyl)-1-methyl-5-phenyl-4(lH)-pyridone, 3-(3,5-dimethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 3-(3-butylphenyl)-1-methyl-5-phenyl-4(lH)-pyridohe, 3-(2,5-dimethylphenyl)-1-methyl-5-phenyl-4(1E~)-pyridone, 3-(2,4-dimethylphenyl?-1-methyl-5-phenyl-4(lH) pyridone, l-methyl-3-phenoxy-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, .
,~, ~
. ....:
. ~ - .. .... .. .
~75~97 3-ethoxycarbonyl-l-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, l-methyl-3-(3-trlfluoromethylphenyl)-5-phenyl-thio-4(lH)-pyridone, 3-(2,4-dichlorophenoxy)-l-methyl-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, l-methyl-3-(2-thienyl)-5-(3-trifluoromethyl- :~
phenyl)-4(lH)-pyridone, :
3-ethylthio-1-methyl-5-phenyl-4(lH)-pyridone, .
3-ethylthio-1-methyl-5-(3-trifluoromethylphenyl)~
4(lH)-pyridone, :
3-ethylsulfonyl-1-methyl-5-(3-trifluoromethyl- ~
phenyl)-4(lH)-pyridone, :
3-ethylsulfinyl-1-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, 3-(5-bromo-2-fluorophenyl)-1-methyl-5-phenyl-4(lH)-pyridone, l-methyl-3-(5-nitro-2-methylphenyl)-5-phenyl-4(lH)-pyridone, 3-cyano-5-(2,5-dimethoxyphenyl)-l-methyl-4(lH)-: pyridone, 3-(2 t 6-dichlorophenyl)-l-methyl-5-phenyl-4(1~)-pyridone, 3~ethoxycarbonyl-l-methyl-5-phenyl-4(1HJ-pyridone, l-methyl-3-propylthio-5-(3-trifluoromethylphenyl)-4(lH)-pyridone, -~.
:~ 3-butylthio-1-methyl-5-(3-trifluoromethylphenyl)- :
; 4~(1H)-pyridone, ~ ~
, . .
30~:
~.,.;,,~ . :
.. , .. ~ .
. ; .. .
: ' , ~ '' , - .' ' . ,: ,. ' ' ...... . . .
7S~ 7 1-methyl-3-methylthio-5-(3-tri~luoromethylphenyl) 4(lH)-pyridone, l-methyl-3-(3-trifluoromethylphenyl)-5-(4-tri-fluoromethylphenyl)-4(lH)-pyridone, l-methyl-3-(3-trifluoromethylphenyl)-S-trifluoro-methylthio-4(lH)-pyridone, 3-(3,4-dimethoxyphenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, 3-(5-fluoro-2-iodophenyl)-1-methyl-5-phenyl-4(lH)-pyridone, 3-(2-bromo-5-fluorophenyl)-1-methyl-5-phenyl-4(lH)-pyridone, 3-benzylthio-1-methyl-5-(3-tri~luoromethylphenyl)-4(lH)-pyridone, 3-(4-benzyloxyphenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, 1,3-diethyl 5-(3-trifluoromethylphenyl)-4(1H)- ;-pyridone, 3-(4-hydroxyphenyl)-1 methyl-5-(3-trifluoromethyl-20 phenyl)-4(lH)-pyridone, .
3-(4-chloro-3-trifluoromethylphenyl)-5-ethoxy-1-methyl-4(lH)-pyridone, l-methyl-3-isopropylthio-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, 3-(4-chloro-3-trifluorome~hylphenyl)-5-ethylthio-l-methyl-4(lH)-pyridone, 3-(4-chloro-3-trifluoromethylphenyl)-1-methyl-5-phenyl-4(lH)-pyridone, :
~ ~ . ~ :
::
'~
~75~97 3-(2,5-dimethylphenyl)-1-methyl-5-(3-tri~luoro-methylphenyl)-4(lH)-pyridone, 3-(3,5-dimethylphenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1~)-pyridone, 3-(2,4-dichlorophenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, l-methyl-3-phenyl-5-(2-trifluoromethylphenyl)-4(lH)-pyridone, l-methyl-3-(2-trifluoromethylphenyl)-5-(3-tri-fluoromethylphenyl)-4(lH)-pyridone, 3-(3,4-dimethylphenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, 3-(3-iodophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, 3-ethyl-1-methy.l-5-(3-methoxyphenyl)-~(lH)-pyridone, l-methyl-3-(3-iodophenyl)-5-phenyl-4(lH)-pyridone, l-methyl-3-(4-methoxypheno~y)-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, 1-methyl-3-(2-chloro-4-fluorophenyl)-5-(3-tri-fluoromethylphenyl)-4(lH)-pyridone, l-methyl-3~(4-chloro-3-trifluoromethylphenyl)-5-triflu~romethyl-4(lH)-pyridone, ~:
l-methyl-3-(4-chloro-3-trifluoromethylphenyl)-5-propyl-4(lH)-pyridone, :
l-methyl-3-~sopropylthio-5-(4-chloro-3-trifluoro-methylphenyl)-4(lH)-pyridone, :
l-methyl-3-(4-chloro-3-trifluoromethylphe~yl)-5-propylthio 4(lH)-pyrldone, ~, : ' 56~
1-methyl-3-(4-chloro-3-trifluoromethylphenyl)-5-(2-thienyl)-4(lH)-pyridone, 3-ethyl-1-methyl~5-(4-chloro-3-trifluoromethyl-phenyl)-4(lH)-pyridone, l-methyl-3-(2,4-dimethylphenyl)-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-isopropoxy-1-methyl-5-(3-trifluoromethylphenyl~- :
4(1~)-pyridone, l-methyl-3-(4-chlorophenoxy)-5-(3-trifluorométhyl-10 phenyl)-4(lH)-pyridone, ~.. ,;. `
l-methyl-3-(3-methylthiophenyl)-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, l-methyl~.3-(3-methylsulfonylphenyl)-5-(3-tri-fluoromethylphenvl)-4(lH)-pyridone, l-methyl-3-(3-trifluoromethylphenoxy)-5-(3-tri-fluoromethylphenyl)-4(lH)-pyridone, 3-~4-methoxyphenyl)-1-methyl-5-(3-trifluoromethyl- :
phenyl)-4(1H)-pyridone, 3-(2,3 dichlorophenoxy)-1-methyl-5-(3-trifluoro- ' methylphenyl)-4(1H)-pyridon,e, 3-(3,5-dichlorophenoxy)-1-methyl-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, ~ 3-(3,4-dichlorophenoxy)-1-methyl 5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, 3-(4-chloro-3-trifluoromethylphenyl)-1-methyl-5- .... ,. .
isopropyl-4(lH) pyridone, 3-(2,5-dichlorophenoxy)-1-methyl-5-(3-trifluoro-methyl~henyl)-4(lH)-pyridone, , _ 9 _ :, .
, ~ ~ .
.. .. . . ...
S~g~
5-(3-methoxycarbonylphenyl)-l~methyl-3-(3-methylphenyl)-4(lH)-pyridone, 3-methoxy-1-methyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridone, 3-(4-bromophenyl)-1-methyl-5-(3-methylphenyl)-4(lH)-pyridone, 3-(3,4-dichlorophenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, 3,5-bis(3,5-dichlorophenyl)-1-methyl-4(lH)-pyridone/
3-(3,4-dichlorophenyl)-1-methyl-5-(3-methyl-phenyl)-4(lH)-pyridone, 3-(3,4-dichlorophenyl)-5-(3,4-dimethylphenyl)-l-methyl-4(1H)-pyridone, 3-(3-ch}orophenyl)-1-methyl-5-(2-methylphenyl)-4(lH)-pyridone, 3-(4-bromophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, 3-(4-bromophenyl)-5-(3-carboxyphenyl) l-methyl-4(lH)-pyridone, 3-(3-chlorophenyl)-1-methyl-S-(4-trifluoromethyl-phenyl)-4(lH)-pyridone, 3-(2-methylphenyl)-S-(4-methylphenyl)-1-methyl-4(lH)-pyridone, 3-(3-methylphenyl)-5-(4-methylphenyl)-1-methyl-4(lH)-pyridone, 3-(2-chlorophenyl)-5-(2-methylohenyl)-1-me~h~
4(1H)-pyridone, :. :
. ~
..... . .
.
~7~ 7 . .
l-methyl-3-(4-methylthiophenoxy)-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, 3-isobutylthio-1-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, 3-t-butylthio-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-s-butylthio-1-methyl-5-(3-trifluoromethyl-phenyl)-.4(1H)-pyridone, l-methyl-3-(4-nitropheno~y)-5-(3-trifluoromethyl-phenyl)-4(1~)-pyridone, 3-ethyl-1-hydroxy-S-(3-trifluoromethylphenyl)- . :
4(lH)-pyridone, l-methyl-3-trifluoromethylsulfonyl-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, l-methyl-3-(3-trifluorome~hylphenyl)-5-t3-tri-fluoromethylthiophenyl)-4(lH)-pyridone, l-methyl-3-(3-trifluoromethylphenyl)-5-(3-tri-fluoromethylsulfonylphenyl)-4(1Hj-pyridone, l-methyl-3-(2,2,2-trifluoroethoxy)-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, l-methyl-3-(2-nitrophenyl)-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, ' l-methyl-3-(3-methyLphenyl)-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, l-methyl-3-(2-methylphenyl)-5-(3-tri.~luoromethyl-phenyl)-4(lH)-pyridone, l-methvl-3-(4~methylpheryl)-5-(3-tr fluoro~ thyl- ~.
.. ..
phenyl)-4(lH)-pyridone, 5-(3-methoxycarbonylphenyl)-1-methyl-3-(4--methyl-~30 phenyl)-4(1~)-pyridone, ~1~756~7 l-methyl-3,5-bis(4-methylphenyl)-4(lH)-pyridone, l-methyl-3-!3-chlorophenyl)-s-(3,4-dichloro-phenyl)-4(lH)-pyridone, l-methyl-3-(3,4-dichlorophenyl)-5-(2-methyl-phenyl)-4(lH)-pyridone, l-methyl-3-(2-chlorophenyl)-5-(3,4-dichloro-phenyl)-4(lH)-pyridone, l-methyl-3-(3-bromophenyl)-5-(3,4-dichlorophenyl)-4(lH)-pyridone, 1-methyl-3-(3,5-dichlorophenyl)-5-(3-tri~luoro-methylphenyl)-4(lH)-pyridone, l-methyl-3-(3-bromophenyl)-5-(3-methylphenyl)-4(lH)-pyridone, l-methyl-3,5-bis(3-methylphenyl)-4(1H)-pyridone, l-methyl-3-(3-fluorophenyl)-5-(2,5-dimethyl-phenyl)-4(lH)-pyridone, 3-(3-bromophenyl)-1-methyl-5-(2-methylphenyl)-4(lH)-pyridone, 3-(3-bromophenyl)-5-(2-chlorophenyl)-1-methyl-2a 4(lH)-pyridone, 3-(2-bromophenyl)-1-methyl-5-(3-trifluoromethyl~
phenyl)-4(1H)-pyrldone, ~ 3-~2,3-dimethoxyphenyl)-1-methyl-S-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-(2-methoxyphenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, ~:
3-(2-ethylphenyl)-1-methyl-5-(3-trifluoromethyl- `
phenyl)-4(lH)-pyridone, 3-(3 bromo-4-methylphenyl)-1-methyl-5-(3-tri-fluoromethylphenyl)-4(lH)-pyridone, .. . .
~756g7 3-(3-ethoxy-4-methoxyphenyl)-1-methyl-5-~3-tri-fluoromethylphenyl)-4(1~)-pyridone, 3-(1-hydroxyethyl)-1-methyl-5 (3-trifluoromethyl-phenyl)-4(lX)-pyridone, 3-(1-methoxyethyl)-1-methyl-S--(3-trifluorome~hyl~
phenyl)-4(lH)-pyridone, l-ethyl-3,5-bis(3-trifluoromet:hylphenyl)-4(lH)-pyridone, l-methyl-3-ethoxy-5-(3-trifluoromethylphenyl)-4(lH)-pyridone, l-methyl-3-(4-chloro-3-trifluoromethylphenyl)-5-phenoxy-4(lH)-pyridone, l-methyl-3-allylthio-5-(3-trifluoromethylphenyl)-4(1~ pyridone, l-methyl-3-methoxy-5-phenyl-4(lH)-pyridone, l-methyl-3-(1-methylbutylthio)-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, 3-(2-hydro.Yypropyl)-l-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, 1-methyl-3-(2-methyl-2-propenylthio)-5-(3-tri-fluoromethylphenyl)-4(1H)-pyridone, 3-ethylthio-S-(2-chloro-5-trifluoromethylphenyl)- :
l-meth~1-4(lH)-pyridone, i-(2-chloro-5-trifluoromethylphenyl)-1-methyl~
5-phenyl-4(1H)-pyridone, 3-(2-chloro-5-trifluoromethylphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, ~ :
~0 - 13 - ::
q ' ' ~7569~
l-hydroxy-3-phenyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridone, 3-(3-carboxyphenyl)-l-me~hyl-5-phenyl-4(lH)-pyridone, l-acetoxy-3-phenyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, l-methyl-3-(3-bromophenyl)-5-phenyl-4(lH)-pyridinethione, l-methyl-3-(4-chlorophenyl)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridinethione, l-methyl-3-(3-methylphenyl)-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridinethione, l-methyl-3-(2-methylphenyl)-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridinethione, l-methyl-3-propyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridinethione, l-methyl-3-phenoxy-5-(3-trifluoromethylphenyl)-4(1H)-pyridinethione, :
3-e~hylthio-l-methyl-5-(3--trifluoromethylphenyl)-4(lH)-pyridinethione, 3-ethoxy-l-methyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridinethione.
.
. - 14 -The compounds of formula I are prepared by re- :
acting a compound of the formula a~ C-C--C-R2 RlX- = ~/ Q1 Q2 II
wherein Rl, R2 and m are defined as before, and one of Ql and Q is 2 hydrogen atoms and the other is =CHNHY wherein Y
is hydrogen; hydroxy; methyl; or ethyl; with an agent selected from the group consisting of a formylating agent, and an aminoformylating agent;
or reacting a compound of Formula II wherein Ql and Q2 are independently selected from the group consisting of =CHOH and =CHN(R )2 ... .
in which the R7~groups independently are Cl-C3 alkyl, or the : : R7 groups combine with the nitrogen atom to which they are attached to form pyrrolidino, piperidino, morpholino or N- .
: 20 methylpiperazino;
.. . .
: with a compound of the formula H ; :
wherein Y is defined as before, or an acid addition salt thereof, and, if tbe group =CHN(R )~ is derived from a formiminium halide, hydrolyzing with aqueous base or acid to provide a compound of the formula ~:
"
~: ::, .`
:' ' ~
~ 30 :
- X 4097K -&~
:
~g~756~7 Y
optionally followed by alkylating or esterifying the compound of Formula III wherein Y is hydrogen or hydroxy respectively to provide the corresponding compound wherein Y
is R; and when the compounds of Formula I are desired wherein X
is sulfur, treating the compounds of Formula I where1n X is oxygen with P2S5;
and, if desired, recovering the product in the form of an acid addition salt .
. A preferred group of compounds comprises those ~:
wherein m represents 1, and the single Rl group is located at the meta positIon of the phenyl ring to which it lS :
attached. Highly preferred compounds are those of the above ~.
20 group wherein I~l represents trifluoromethyl. : :
A particularly preferred class of compounds are those of the formula X
Il ~ ~9~ R IV
R : N
R1(3 . ' :
,' ' ' ' wherein X represents oxygen or sulfur;
1 .
1'''~,~.
.~ ' , ', ~ :
~ ' 7S~'7 R1n represents methyl or ethyl;
R represents hydrogen, trifluoromethyl, C'l-C3 alkyl, halo, me-thoxy or methylthio;
R represents Cl-C4 alkyl, C1-C3 alkoxy, C1-C3 alkylthio, phenyl, yhenoxy, phenylthio, or phenyl, phenox~
or phenylthio monosubstituted with trifluoromethyl, C1-C3 alkyl, halo, methoxy or methylthio.
The compounds described above can form acid addition salts, and such salts are useful embodiments of the invention. The preferred salts are the hydrohalides such as hydroiodides, hydrobromides, hydrochlorides and hydro-fluorides. Salts of the sulfonic acids are also particu-larly desirable. Such salts include sulfonates, methyl-sulfonates and toluenesulfonates.
A preferred embodiment of the synthesis of -the compounds of Formula I is adapted from the methods of El-Kholy et al., cited above. An appropriately substituted l-phenyl-2-propanone is formylated at low temperature with sodium methoxide and ethyl formate in ether, and the product -~
ls treated with an amine salt of the desired R substituent in aqueous rnedium. The resulting intermediate is predom-inantly a l-(R-amino)-2-phenyl-1-buten-3-one of formula IIo Some pyridone is also formed at -this step, as reported by ~l-Kholy et al. The butenone is reformylated as beforej and spontaneously cyclizes to form the l-substituted~3-phenyl-4(lH3-pyridone of formula I.
Another preferred synthesis is similar to the above, but uses an initial aminoformylation step instead of .
X-4097K -~-`''~ , '.
--..
'' . ' .
7S~i~3~7 forlllylatioll. A preferrecl alnitlororlllylatioll acJe~l is a formiminium halide, sw~h as the reaction product oE phos~ene an(l ~limetlly:lformamide. The propanone is di-aminoformylated, and the intermediate is exchanged with an amine or an amine salt of the R substituent and hydrolyzed with acid or alkali to form the l-substituted-3-phenyl-4(lH)-pyridone.
As a chemist would expect, the amines, YNH2, may be used in the form of salts, preferably hydrohalide salts, -~
including hydrochlorides, hydrobromides and the like. Such salts are oEten more convenient than the free amines.
The formylatlng agents used in the process are chosen from the common agents used for such reactions. The preferred agents are esters of formic acid of the formulae O
Il .
C~-O-- (C ~Cr a ~ ky l ) or C--o~
.
Similar formylations are discussed in Organic Syntheses 300-02 (Collective Vol. III 1955).
The esters are used in the presence of strong bases, of which alkali metal alkoxides are preferred, such as sodium methoxide, potassium ethoxide and lithium pro-poxide. Other bases may also be used, including alkali metal hydrides, alkali metal amides, and inorganic bases including alkali metal carbonates and hydroxides. Such strong organic base~s as-diazabicyclononane and diazabicyclo-undecane are also useful.
, ' ' /~
X-4097K -~
" ' :::
.
~L~75~37 Reactions with formylating agents are per~orllle~ in aprotic solvents such as are regularly used in chemical synthesis. ~thyl ether is usually the preferred solvent.
Ethers in general, including solvents such as ethyl propyl ether, ethyl butyl ether, 1,2-dimethoxyethane and tetra-hydrofuran, aroma~tic solvents such as benzene and xylene, and alkanes such as hexane and octane can be used as for-mylation solvents. ~ :
Because of the strong bases used in the formyla-1~ tion reactions, low temperatures produce the best yields.
Reaction at temperatures in the range of from about -25C.
to about 10C. is preferred. The reaction mixture may be allowed to warm to room temperature, however, after the reaction has proceeded part way to completion. Reaction times Erom about i to about 24 hours are adequate for - economic yields in the formylation reactions. ; ;
The aminoformylating agents used in these synthe-ses may be any compounds capable of reacting with an active methylene group to introduce a =CHN(R )2 group, or its acid addition salt~ Such agents are chosen from among the orthoEormamides, HC[N(R )2]3 the formate ester aminals, Q - R
HC[~(R )2]2 the formamide acetals, .
, :::
.::
' ~
:
, . . . .
~ ~7569'7 Q3_ _Rll I )2 Q3 Rll the tris(formylamino)methanes, ~C(NHCH)3 and the formiminium halides, ~-HC=W(R )2Halo Halo Q in the structures above represents oxygen or su1fur, and R represents Cl-C6 alkyl or phenyl.
- Useful references on the aminoformylating agents include DeWolfe, Carboxylic Acid Derivatives 420-506 (~cademic Press 1970), and Ulrlch, Chemistry o~ :[midoyl llalides 87-96 (Plenum Press 1968). ~redereck et al. have written many papers on such agents and reactions, of which the following are typical~ Ber. 101, 4048-56 (1968); Ber.
104, 2709-26 (1971); Ber. 106, 3732-42 (1373); Ber. 97, 3397-406 (1964)i Ann. 762j 62-72 (1972); ser. 97, 3407-17 (1964~); B . 103, 210-21 (1970); Angew. Chem. 78, 147 (1966); Ber. 98, 2887-96 (1965); Ber. 96, 1505-14 (1963);
~er. 104, 3475-85 (1971); Ber. 101, 41-50 (1568~; Ber. 106, 3725-31 (1973); and Angew. Chem. Int'1. Ed. 5, 132 ~1966).
, Other notable papers on the subject include Kreutzberger et ~-~al., Arch. der Pharm. 30I, 88I-96 (1968), and 302, 362-75 ~ ~-.
(1969), and Welnqarten et al. r J. ~. Chem. 32, 3293-94 ; ~ ~ (1967).
.: .
~IX 4097K
: ~:: ~ : : :. : : -. .. ..
: ' ~ ' " . . ' .
~` ~L6)75~ 7 ~ ~
- Aminoformyla-tions are usually carried out wi-thout solvent, at elevated temperatures from about 50C. to abou-t 200C. Solvents such as dimethylformamide are sometimes used, however, particularly when it is desirable -to raise the boiling point of the reaction mixture.
When aminoformylating with formiminium halides, however, aprotic solvents, such as described above in the description of solvents for formylation, are used at tem-peratures from about 0C. to about 50C., preferably at room temperature. Halogenated solvents such as chloroform and methylené chloride can also be used in such aminoformyla- `
tions if desired.
The exchange reactions with YNH2 are best per-formed in protic solven-ts of which alkanols are preferred and ethanol is most appropriate. Temperatures Erom about -20C. to about 100C. can be used for the exchange re-actions. Room temperature is satisfactory and is preferred.
The starting materials of formula II may be pre-pared by reacting a compound of the formula
This invention belongs to the field of agricul-tural chemistry, and provides to the art new preemergence and postemergence' herbicides, and compositions and methods of applying the compounds for the contro:L of weeds. Since the control of weeds is known to be a vital step in the maximization of crop yields, herbicides are now established as vital tools of the farmer and new and improved herbicidal compounds are in constant demand.
Despite the great amount of research which has been performed in the field of agricultural chemistry, active compounds closely related to the compoun~s of formula I herein have not been previously discovered. The poly- ~`
halopyridones, which have two or more chlorine atoms as well as other alkyl and halo substituents on the pyridine ring, are known herbicides, but are obviously quite distinct from the compounds of formula I.
The organic chemical art has explored the pyri-dones rather extensively. For examplei Ishibe et al~, J.
Am. Chem. Soc. 95, 3396-3397 (1973), disclosed a rearrange-20 ment of 3,5-diphenyl-1,2,6-trimethyl-4(1~)-pyridone. Such compounds, however, are not herbicides. Leonard et al., J.
Am. Chem. Soc. 77~ 1852-1855 (1955) ~ taught the synthesis of 3,5-dibenzyl-1-methyl-4(lH)-pyridones, which compounds also ` `~
have no herbicidal~activity. The same principal author also ~ .
disclosed 3,5-di(substituted-benzylidene)tetrahydro-4-pyridones, J. Am. Chem. Soc. 79, 156-160 (1957)o These compounds also have no herbicidal activity.
, ` , '`
, ~30 X-4097K ~ -2-~ : ' ' ' ' ' . . ' ' : .
' . ' ' ' , ' ' ~ ., ' . ~
' ,, , : .~ ' ~ ' `' ' , :
Light et al., J. Org. Chem. 25, 538-54~ ~1960), taught a number of 4-pyridone compounds including 2,6-diphenyl-l-methyl-4(lH)-pyridone, and related compounds bearing phenyl-ring substituents, none of which are her-bicidally active.
An interesting recent ar~icle was published by El-Kholy et al. in J. Hetero. Chem. 10, 665-667~(published September 7, 1973). El-Kholy described a synthesis of 3,5-diphenyl-l-methyl-4(lH)-pyridone and related compounds by ~ -the reaction with methylamine of the sodium salt of 1,5-dihydroxy-2,4-diphenyl-1,4-pentadien-3-one.
A series of novel 3-phenyl-4(1H)-pyridones(thiones) are herbicides which are active against an unusually wide range of weeds are disclosed in copending Canadian Application Serial No. 233,945, filed August 22, 1975.
New methods and compositions for applying the compounds for the control of weeds, which methods are particularly useful in cotton or rice cropland, are also disclosed.
The novel compounds are of the general formula X
Rl ~ - J ~l ...
R
wherein: X is oxygen or sulfur, R is methyl, ethyl, acetoxy or hydroxy;
the Rl groups independently are halo; Cl-C~
alkyl; Cl-C4 alkyl substituted with halo; nitro;
carboxy; hydroxy; Cl-C2 alkoxycarbonyl;
-o-R3; ~ S-R3; -So-R3; or -5O2-R ;
_ 3 _ . .
g~
R3 is Cl-C2 alkyl; C1-C2 alkyl substituted wi-th halo; benæyl; or phenyli R iS cyano; Cl-C3 alkox~fcarbonyl; Cl-C4 alkyl;
Cl-C~ alkyl subsiituted wllh halo, hydroxy or Cl-C3 alkoxy; thienyl; -O-R~ S-R4; -So-R4;
-So2-R , or ` ,..
\~_ GXR5 ' .
R4 is C1-C6 alkyl; Cl-C6 alkyl substituted with hydroxy or haLo; C2-C4 alkenyl; benzyl; ph nrl; or phenyl substituted with trifluoromethyl, halo, Cl-C3 alkyl, nitro, C1-C3 alkylthio or Cl-C3 .
alkoxy;
the R5 groups independently are nalo; Cl-C4 alkyl;~Cl-C4 alkyl substituted with halo; nitro; ~:
carboxy; hydroxy; Cl-C2 alkoxycarbonyl; _o-~6; ~:
-S-R6; -SO-R6; or -502-R6;
. R6 is Cl-C2 alkyl; Cl-C2 alkyl substituted . ~: with halo; benæyl; or phenyl;
m and n independently are 0, 1 or 2; provided that when X is oxygen, R is methyl, and R2 is unsubstituted phenyl, then m is 1 or 2;
: ~and the acLd addition salts thereof.
:
: 30 ~ ~
X-4097K _4_ : . :
:
. .
!
~7~7 The present invention relates to a group of novel and useful compounds which geneLally fall within the scope of Serial No. 233,945. These compounds are selected from:
l-methyl-3-(3-nitrophenoxy)-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, 3-(4-methoxy-3-methylphenylJ-:L-methyl-5-phenyl-4(lH)-pyridone, . 3-(3-bromo-4-methylphenyl)-1-methyl-5-phenyl-4(lH)-pyridone, 1-methyl-3-(3-nitrophenyl)-5-(3-trifluoromethyl-2henYl)-4(lH)-pyridone, l-methyl-3-phenyl-5-(3-phenylthiophenyl)-4(lH)-pyridone, i l-methyl-3-phenyl-5-(3-phenylsulfonylphenyl)-4(1H)-pyridone, 3-(2-chloro-4-fluorophenyl)-1-methyl-5-phenyl-4(lH)-pyridone, 3-(3,4-dimethylphenyl)-1-methyl-5-phenyl-4(lH)-pyridone, 3-(3,5-dimethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 3-(3-butylphenyl)-1-methyl-5-phenyl-4(lH)-pyridohe, 3-(2,5-dimethylphenyl)-1-methyl-5-phenyl-4(1E~)-pyridone, 3-(2,4-dimethylphenyl?-1-methyl-5-phenyl-4(lH) pyridone, l-methyl-3-phenoxy-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, .
,~, ~
. ....:
. ~ - .. .... .. .
~75~97 3-ethoxycarbonyl-l-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, l-methyl-3-(3-trlfluoromethylphenyl)-5-phenyl-thio-4(lH)-pyridone, 3-(2,4-dichlorophenoxy)-l-methyl-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, l-methyl-3-(2-thienyl)-5-(3-trifluoromethyl- :~
phenyl)-4(lH)-pyridone, :
3-ethylthio-1-methyl-5-phenyl-4(lH)-pyridone, .
3-ethylthio-1-methyl-5-(3-trifluoromethylphenyl)~
4(lH)-pyridone, :
3-ethylsulfonyl-1-methyl-5-(3-trifluoromethyl- ~
phenyl)-4(lH)-pyridone, :
3-ethylsulfinyl-1-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, 3-(5-bromo-2-fluorophenyl)-1-methyl-5-phenyl-4(lH)-pyridone, l-methyl-3-(5-nitro-2-methylphenyl)-5-phenyl-4(lH)-pyridone, 3-cyano-5-(2,5-dimethoxyphenyl)-l-methyl-4(lH)-: pyridone, 3-(2 t 6-dichlorophenyl)-l-methyl-5-phenyl-4(1~)-pyridone, 3~ethoxycarbonyl-l-methyl-5-phenyl-4(1HJ-pyridone, l-methyl-3-propylthio-5-(3-trifluoromethylphenyl)-4(lH)-pyridone, -~.
:~ 3-butylthio-1-methyl-5-(3-trifluoromethylphenyl)- :
; 4~(1H)-pyridone, ~ ~
, . .
30~:
~.,.;,,~ . :
.. , .. ~ .
. ; .. .
: ' , ~ '' , - .' ' . ,: ,. ' ' ...... . . .
7S~ 7 1-methyl-3-methylthio-5-(3-tri~luoromethylphenyl) 4(lH)-pyridone, l-methyl-3-(3-trifluoromethylphenyl)-5-(4-tri-fluoromethylphenyl)-4(lH)-pyridone, l-methyl-3-(3-trifluoromethylphenyl)-S-trifluoro-methylthio-4(lH)-pyridone, 3-(3,4-dimethoxyphenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, 3-(5-fluoro-2-iodophenyl)-1-methyl-5-phenyl-4(lH)-pyridone, 3-(2-bromo-5-fluorophenyl)-1-methyl-5-phenyl-4(lH)-pyridone, 3-benzylthio-1-methyl-5-(3-tri~luoromethylphenyl)-4(lH)-pyridone, 3-(4-benzyloxyphenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, 1,3-diethyl 5-(3-trifluoromethylphenyl)-4(1H)- ;-pyridone, 3-(4-hydroxyphenyl)-1 methyl-5-(3-trifluoromethyl-20 phenyl)-4(lH)-pyridone, .
3-(4-chloro-3-trifluoromethylphenyl)-5-ethoxy-1-methyl-4(lH)-pyridone, l-methyl-3-isopropylthio-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, 3-(4-chloro-3-trifluorome~hylphenyl)-5-ethylthio-l-methyl-4(lH)-pyridone, 3-(4-chloro-3-trifluoromethylphenyl)-1-methyl-5-phenyl-4(lH)-pyridone, :
~ ~ . ~ :
::
'~
~75~97 3-(2,5-dimethylphenyl)-1-methyl-5-(3-tri~luoro-methylphenyl)-4(lH)-pyridone, 3-(3,5-dimethylphenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1~)-pyridone, 3-(2,4-dichlorophenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, l-methyl-3-phenyl-5-(2-trifluoromethylphenyl)-4(lH)-pyridone, l-methyl-3-(2-trifluoromethylphenyl)-5-(3-tri-fluoromethylphenyl)-4(lH)-pyridone, 3-(3,4-dimethylphenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, 3-(3-iodophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, 3-ethyl-1-methy.l-5-(3-methoxyphenyl)-~(lH)-pyridone, l-methyl-3-(3-iodophenyl)-5-phenyl-4(lH)-pyridone, l-methyl-3-(4-methoxypheno~y)-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, 1-methyl-3-(2-chloro-4-fluorophenyl)-5-(3-tri-fluoromethylphenyl)-4(lH)-pyridone, l-methyl-3~(4-chloro-3-trifluoromethylphenyl)-5-triflu~romethyl-4(lH)-pyridone, ~:
l-methyl-3-(4-chloro-3-trifluoromethylphenyl)-5-propyl-4(lH)-pyridone, :
l-methyl-3-~sopropylthio-5-(4-chloro-3-trifluoro-methylphenyl)-4(lH)-pyridone, :
l-methyl-3-(4-chloro-3-trifluoromethylphe~yl)-5-propylthio 4(lH)-pyrldone, ~, : ' 56~
1-methyl-3-(4-chloro-3-trifluoromethylphenyl)-5-(2-thienyl)-4(lH)-pyridone, 3-ethyl-1-methyl~5-(4-chloro-3-trifluoromethyl-phenyl)-4(lH)-pyridone, l-methyl-3-(2,4-dimethylphenyl)-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-isopropoxy-1-methyl-5-(3-trifluoromethylphenyl~- :
4(1~)-pyridone, l-methyl-3-(4-chlorophenoxy)-5-(3-trifluorométhyl-10 phenyl)-4(lH)-pyridone, ~.. ,;. `
l-methyl-3-(3-methylthiophenyl)-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, l-methyl~.3-(3-methylsulfonylphenyl)-5-(3-tri-fluoromethylphenvl)-4(lH)-pyridone, l-methyl-3-(3-trifluoromethylphenoxy)-5-(3-tri-fluoromethylphenyl)-4(lH)-pyridone, 3-~4-methoxyphenyl)-1-methyl-5-(3-trifluoromethyl- :
phenyl)-4(1H)-pyridone, 3-(2,3 dichlorophenoxy)-1-methyl-5-(3-trifluoro- ' methylphenyl)-4(1H)-pyridon,e, 3-(3,5-dichlorophenoxy)-1-methyl-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, ~ 3-(3,4-dichlorophenoxy)-1-methyl 5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, 3-(4-chloro-3-trifluoromethylphenyl)-1-methyl-5- .... ,. .
isopropyl-4(lH) pyridone, 3-(2,5-dichlorophenoxy)-1-methyl-5-(3-trifluoro-methyl~henyl)-4(lH)-pyridone, , _ 9 _ :, .
, ~ ~ .
.. .. . . ...
S~g~
5-(3-methoxycarbonylphenyl)-l~methyl-3-(3-methylphenyl)-4(lH)-pyridone, 3-methoxy-1-methyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridone, 3-(4-bromophenyl)-1-methyl-5-(3-methylphenyl)-4(lH)-pyridone, 3-(3,4-dichlorophenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, 3,5-bis(3,5-dichlorophenyl)-1-methyl-4(lH)-pyridone/
3-(3,4-dichlorophenyl)-1-methyl-5-(3-methyl-phenyl)-4(lH)-pyridone, 3-(3,4-dichlorophenyl)-5-(3,4-dimethylphenyl)-l-methyl-4(1H)-pyridone, 3-(3-ch}orophenyl)-1-methyl-5-(2-methylphenyl)-4(lH)-pyridone, 3-(4-bromophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, 3-(4-bromophenyl)-5-(3-carboxyphenyl) l-methyl-4(lH)-pyridone, 3-(3-chlorophenyl)-1-methyl-S-(4-trifluoromethyl-phenyl)-4(lH)-pyridone, 3-(2-methylphenyl)-S-(4-methylphenyl)-1-methyl-4(lH)-pyridone, 3-(3-methylphenyl)-5-(4-methylphenyl)-1-methyl-4(lH)-pyridone, 3-(2-chlorophenyl)-5-(2-methylohenyl)-1-me~h~
4(1H)-pyridone, :. :
. ~
..... . .
.
~7~ 7 . .
l-methyl-3-(4-methylthiophenoxy)-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, 3-isobutylthio-1-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, 3-t-butylthio-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-s-butylthio-1-methyl-5-(3-trifluoromethyl-phenyl)-.4(1H)-pyridone, l-methyl-3-(4-nitropheno~y)-5-(3-trifluoromethyl-phenyl)-4(1~)-pyridone, 3-ethyl-1-hydroxy-S-(3-trifluoromethylphenyl)- . :
4(lH)-pyridone, l-methyl-3-trifluoromethylsulfonyl-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, l-methyl-3-(3-trifluorome~hylphenyl)-5-t3-tri-fluoromethylthiophenyl)-4(lH)-pyridone, l-methyl-3-(3-trifluoromethylphenyl)-5-(3-tri-fluoromethylsulfonylphenyl)-4(1Hj-pyridone, l-methyl-3-(2,2,2-trifluoroethoxy)-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, l-methyl-3-(2-nitrophenyl)-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, ' l-methyl-3-(3-methyLphenyl)-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, l-methyl-3-(2-methylphenyl)-5-(3-tri.~luoromethyl-phenyl)-4(lH)-pyridone, l-methvl-3-(4~methylpheryl)-5-(3-tr fluoro~ thyl- ~.
.. ..
phenyl)-4(lH)-pyridone, 5-(3-methoxycarbonylphenyl)-1-methyl-3-(4--methyl-~30 phenyl)-4(1~)-pyridone, ~1~756~7 l-methyl-3,5-bis(4-methylphenyl)-4(lH)-pyridone, l-methyl-3-!3-chlorophenyl)-s-(3,4-dichloro-phenyl)-4(lH)-pyridone, l-methyl-3-(3,4-dichlorophenyl)-5-(2-methyl-phenyl)-4(lH)-pyridone, l-methyl-3-(2-chlorophenyl)-5-(3,4-dichloro-phenyl)-4(lH)-pyridone, l-methyl-3-(3-bromophenyl)-5-(3,4-dichlorophenyl)-4(lH)-pyridone, 1-methyl-3-(3,5-dichlorophenyl)-5-(3-tri~luoro-methylphenyl)-4(lH)-pyridone, l-methyl-3-(3-bromophenyl)-5-(3-methylphenyl)-4(lH)-pyridone, l-methyl-3,5-bis(3-methylphenyl)-4(1H)-pyridone, l-methyl-3-(3-fluorophenyl)-5-(2,5-dimethyl-phenyl)-4(lH)-pyridone, 3-(3-bromophenyl)-1-methyl-5-(2-methylphenyl)-4(lH)-pyridone, 3-(3-bromophenyl)-5-(2-chlorophenyl)-1-methyl-2a 4(lH)-pyridone, 3-(2-bromophenyl)-1-methyl-5-(3-trifluoromethyl~
phenyl)-4(1H)-pyrldone, ~ 3-~2,3-dimethoxyphenyl)-1-methyl-S-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-(2-methoxyphenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, ~:
3-(2-ethylphenyl)-1-methyl-5-(3-trifluoromethyl- `
phenyl)-4(lH)-pyridone, 3-(3 bromo-4-methylphenyl)-1-methyl-5-(3-tri-fluoromethylphenyl)-4(lH)-pyridone, .. . .
~756g7 3-(3-ethoxy-4-methoxyphenyl)-1-methyl-5-~3-tri-fluoromethylphenyl)-4(1~)-pyridone, 3-(1-hydroxyethyl)-1-methyl-5 (3-trifluoromethyl-phenyl)-4(lX)-pyridone, 3-(1-methoxyethyl)-1-methyl-S--(3-trifluorome~hyl~
phenyl)-4(lH)-pyridone, l-ethyl-3,5-bis(3-trifluoromet:hylphenyl)-4(lH)-pyridone, l-methyl-3-ethoxy-5-(3-trifluoromethylphenyl)-4(lH)-pyridone, l-methyl-3-(4-chloro-3-trifluoromethylphenyl)-5-phenoxy-4(lH)-pyridone, l-methyl-3-allylthio-5-(3-trifluoromethylphenyl)-4(1~ pyridone, l-methyl-3-methoxy-5-phenyl-4(lH)-pyridone, l-methyl-3-(1-methylbutylthio)-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, 3-(2-hydro.Yypropyl)-l-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, 1-methyl-3-(2-methyl-2-propenylthio)-5-(3-tri-fluoromethylphenyl)-4(1H)-pyridone, 3-ethylthio-S-(2-chloro-5-trifluoromethylphenyl)- :
l-meth~1-4(lH)-pyridone, i-(2-chloro-5-trifluoromethylphenyl)-1-methyl~
5-phenyl-4(1H)-pyridone, 3-(2-chloro-5-trifluoromethylphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, ~ :
~0 - 13 - ::
q ' ' ~7569~
l-hydroxy-3-phenyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridone, 3-(3-carboxyphenyl)-l-me~hyl-5-phenyl-4(lH)-pyridone, l-acetoxy-3-phenyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, l-methyl-3-(3-bromophenyl)-5-phenyl-4(lH)-pyridinethione, l-methyl-3-(4-chlorophenyl)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridinethione, l-methyl-3-(3-methylphenyl)-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridinethione, l-methyl-3-(2-methylphenyl)-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridinethione, l-methyl-3-propyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridinethione, l-methyl-3-phenoxy-5-(3-trifluoromethylphenyl)-4(1H)-pyridinethione, :
3-e~hylthio-l-methyl-5-(3--trifluoromethylphenyl)-4(lH)-pyridinethione, 3-ethoxy-l-methyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridinethione.
.
. - 14 -The compounds of formula I are prepared by re- :
acting a compound of the formula a~ C-C--C-R2 RlX- = ~/ Q1 Q2 II
wherein Rl, R2 and m are defined as before, and one of Ql and Q is 2 hydrogen atoms and the other is =CHNHY wherein Y
is hydrogen; hydroxy; methyl; or ethyl; with an agent selected from the group consisting of a formylating agent, and an aminoformylating agent;
or reacting a compound of Formula II wherein Ql and Q2 are independently selected from the group consisting of =CHOH and =CHN(R )2 ... .
in which the R7~groups independently are Cl-C3 alkyl, or the : : R7 groups combine with the nitrogen atom to which they are attached to form pyrrolidino, piperidino, morpholino or N- .
: 20 methylpiperazino;
.. . .
: with a compound of the formula H ; :
wherein Y is defined as before, or an acid addition salt thereof, and, if tbe group =CHN(R )~ is derived from a formiminium halide, hydrolyzing with aqueous base or acid to provide a compound of the formula ~:
"
~: ::, .`
:' ' ~
~ 30 :
- X 4097K -&~
:
~g~756~7 Y
optionally followed by alkylating or esterifying the compound of Formula III wherein Y is hydrogen or hydroxy respectively to provide the corresponding compound wherein Y
is R; and when the compounds of Formula I are desired wherein X
is sulfur, treating the compounds of Formula I where1n X is oxygen with P2S5;
and, if desired, recovering the product in the form of an acid addition salt .
. A preferred group of compounds comprises those ~:
wherein m represents 1, and the single Rl group is located at the meta positIon of the phenyl ring to which it lS :
attached. Highly preferred compounds are those of the above ~.
20 group wherein I~l represents trifluoromethyl. : :
A particularly preferred class of compounds are those of the formula X
Il ~ ~9~ R IV
R : N
R1(3 . ' :
,' ' ' ' wherein X represents oxygen or sulfur;
1 .
1'''~,~.
.~ ' , ', ~ :
~ ' 7S~'7 R1n represents methyl or ethyl;
R represents hydrogen, trifluoromethyl, C'l-C3 alkyl, halo, me-thoxy or methylthio;
R represents Cl-C4 alkyl, C1-C3 alkoxy, C1-C3 alkylthio, phenyl, yhenoxy, phenylthio, or phenyl, phenox~
or phenylthio monosubstituted with trifluoromethyl, C1-C3 alkyl, halo, methoxy or methylthio.
The compounds described above can form acid addition salts, and such salts are useful embodiments of the invention. The preferred salts are the hydrohalides such as hydroiodides, hydrobromides, hydrochlorides and hydro-fluorides. Salts of the sulfonic acids are also particu-larly desirable. Such salts include sulfonates, methyl-sulfonates and toluenesulfonates.
A preferred embodiment of the synthesis of -the compounds of Formula I is adapted from the methods of El-Kholy et al., cited above. An appropriately substituted l-phenyl-2-propanone is formylated at low temperature with sodium methoxide and ethyl formate in ether, and the product -~
ls treated with an amine salt of the desired R substituent in aqueous rnedium. The resulting intermediate is predom-inantly a l-(R-amino)-2-phenyl-1-buten-3-one of formula IIo Some pyridone is also formed at -this step, as reported by ~l-Kholy et al. The butenone is reformylated as beforej and spontaneously cyclizes to form the l-substituted~3-phenyl-4(lH3-pyridone of formula I.
Another preferred synthesis is similar to the above, but uses an initial aminoformylation step instead of .
X-4097K -~-`''~ , '.
--..
'' . ' .
7S~i~3~7 forlllylatioll. A preferrecl alnitlororlllylatioll acJe~l is a formiminium halide, sw~h as the reaction product oE phos~ene an(l ~limetlly:lformamide. The propanone is di-aminoformylated, and the intermediate is exchanged with an amine or an amine salt of the R substituent and hydrolyzed with acid or alkali to form the l-substituted-3-phenyl-4(lH)-pyridone.
As a chemist would expect, the amines, YNH2, may be used in the form of salts, preferably hydrohalide salts, -~
including hydrochlorides, hydrobromides and the like. Such salts are oEten more convenient than the free amines.
The formylatlng agents used in the process are chosen from the common agents used for such reactions. The preferred agents are esters of formic acid of the formulae O
Il .
C~-O-- (C ~Cr a ~ ky l ) or C--o~
.
Similar formylations are discussed in Organic Syntheses 300-02 (Collective Vol. III 1955).
The esters are used in the presence of strong bases, of which alkali metal alkoxides are preferred, such as sodium methoxide, potassium ethoxide and lithium pro-poxide. Other bases may also be used, including alkali metal hydrides, alkali metal amides, and inorganic bases including alkali metal carbonates and hydroxides. Such strong organic base~s as-diazabicyclononane and diazabicyclo-undecane are also useful.
, ' ' /~
X-4097K -~
" ' :::
.
~L~75~37 Reactions with formylating agents are per~orllle~ in aprotic solvents such as are regularly used in chemical synthesis. ~thyl ether is usually the preferred solvent.
Ethers in general, including solvents such as ethyl propyl ether, ethyl butyl ether, 1,2-dimethoxyethane and tetra-hydrofuran, aroma~tic solvents such as benzene and xylene, and alkanes such as hexane and octane can be used as for-mylation solvents. ~ :
Because of the strong bases used in the formyla-1~ tion reactions, low temperatures produce the best yields.
Reaction at temperatures in the range of from about -25C.
to about 10C. is preferred. The reaction mixture may be allowed to warm to room temperature, however, after the reaction has proceeded part way to completion. Reaction times Erom about i to about 24 hours are adequate for - economic yields in the formylation reactions. ; ;
The aminoformylating agents used in these synthe-ses may be any compounds capable of reacting with an active methylene group to introduce a =CHN(R )2 group, or its acid addition salt~ Such agents are chosen from among the orthoEormamides, HC[N(R )2]3 the formate ester aminals, Q - R
HC[~(R )2]2 the formamide acetals, .
, :::
.::
' ~
:
, . . . .
~ ~7569'7 Q3_ _Rll I )2 Q3 Rll the tris(formylamino)methanes, ~C(NHCH)3 and the formiminium halides, ~-HC=W(R )2Halo Halo Q in the structures above represents oxygen or su1fur, and R represents Cl-C6 alkyl or phenyl.
- Useful references on the aminoformylating agents include DeWolfe, Carboxylic Acid Derivatives 420-506 (~cademic Press 1970), and Ulrlch, Chemistry o~ :[midoyl llalides 87-96 (Plenum Press 1968). ~redereck et al. have written many papers on such agents and reactions, of which the following are typical~ Ber. 101, 4048-56 (1968); Ber.
104, 2709-26 (1971); Ber. 106, 3732-42 (1373); Ber. 97, 3397-406 (1964)i Ann. 762j 62-72 (1972); ser. 97, 3407-17 (1964~); B . 103, 210-21 (1970); Angew. Chem. 78, 147 (1966); Ber. 98, 2887-96 (1965); Ber. 96, 1505-14 (1963);
~er. 104, 3475-85 (1971); Ber. 101, 41-50 (1568~; Ber. 106, 3725-31 (1973); and Angew. Chem. Int'1. Ed. 5, 132 ~1966).
, Other notable papers on the subject include Kreutzberger et ~-~al., Arch. der Pharm. 30I, 88I-96 (1968), and 302, 362-75 ~ ~-.
(1969), and Welnqarten et al. r J. ~. Chem. 32, 3293-94 ; ~ ~ (1967).
.: .
~IX 4097K
: ~:: ~ : : :. : : -. .. ..
: ' ~ ' " . . ' .
~` ~L6)75~ 7 ~ ~
- Aminoformyla-tions are usually carried out wi-thout solvent, at elevated temperatures from about 50C. to abou-t 200C. Solvents such as dimethylformamide are sometimes used, however, particularly when it is desirable -to raise the boiling point of the reaction mixture.
When aminoformylating with formiminium halides, however, aprotic solvents, such as described above in the description of solvents for formylation, are used at tem-peratures from about 0C. to about 50C., preferably at room temperature. Halogenated solvents such as chloroform and methylené chloride can also be used in such aminoformyla- `
tions if desired.
The exchange reactions with YNH2 are best per-formed in protic solven-ts of which alkanols are preferred and ethanol is most appropriate. Temperatures Erom about -20C. to about 100C. can be used for the exchange re-actions. Room temperature is satisfactory and is preferred.
The starting materials of formula II may be pre-pared by reacting a compound of the formula
2~ / IV
m ':
wherein:
Rl, R2 and m are defined as before, ~ `
with an agent selected from the group consisting of : . . : ' ' ~ a formylating agent, and ~`
:: - .
an aminoformylating agent. `~
.
,. ,: , ' - ' . . . ~ . .
~756~7 If a formylating agent is used, a ketone inter--mediate of the formula 1~ . ,o~ O
~ -C--C--(,112--R' V
\o~------u/ 11 :, HOCH
is produced. Reaction with an aminoformylating agent produces an enaminoketone such as VI below. --2~ -----um~ C--CHz--R
~====9/ ~ VI
(R )zN H
Organic chemists will understand that, although formulae V and VI show the first formylation or amino-formylation as occurring on a certain side of the ketone, it may in fact occur on either side of the ketone, depending on the activatiny characteristics of Rl and R2. The course of the reaction is the same in either case. It will also be understood that, in many instances, the product of the formylation or aminoformylation step will actually be a mixture containing the two possible monosubstituted com~
. .
pounds and the disubstituted compound.
I'he monosubstituted product is formylated or aminoformylated again, and exchanged with an amine of the : .
formula YNH2. The steps may be performed in either order.
If the exchange is performed~first, the intermediate product is an enaminoketone of the formula '~ '.,.. ;.. , ~. "'.' ' ~: . .
m ':
wherein:
Rl, R2 and m are defined as before, ~ `
with an agent selected from the group consisting of : . . : ' ' ~ a formylating agent, and ~`
:: - .
an aminoformylating agent. `~
.
,. ,: , ' - ' . . . ~ . .
~756~7 If a formylating agent is used, a ketone inter--mediate of the formula 1~ . ,o~ O
~ -C--C--(,112--R' V
\o~------u/ 11 :, HOCH
is produced. Reaction with an aminoformylating agent produces an enaminoketone such as VI below. --2~ -----um~ C--CHz--R
~====9/ ~ VI
(R )zN H
Organic chemists will understand that, although formulae V and VI show the first formylation or amino-formylation as occurring on a certain side of the ketone, it may in fact occur on either side of the ketone, depending on the activatiny characteristics of Rl and R2. The course of the reaction is the same in either case. It will also be understood that, in many instances, the product of the formylation or aminoformylation step will actually be a mixture containing the two possible monosubstituted com~
. .
pounds and the disubstituted compound.
I'he monosubstituted product is formylated or aminoformylated again, and exchanged with an amine of the : .
formula YNH2. The steps may be performed in either order.
If the exchange is performed~first, the intermediate product is an enaminoketone of the formula '~ '.,.. ;.. , ~. "'.' ' ~: . .
3 a ; ~ % ,2 ~ X-4097X
~ .
'' :' -'.,-~7~
",~ . t) -C--t~--cl~.2__~2 V1 YIINO
I..ither iorn~ylation or aminoformylation oi- the above enamino-ketone, which also can be represented by Eormula II, affords the pyridone product, as the intermediate cyclizes as soon as the second group is introduced on the other methylene group.
~ Either of compounds V or VI may be either for-mylated or aminoformylated to provide intermediates of any of the Eormulae below.
j~l . . O
m /~ --t~--C--ii~
=~=~ ~iOi~ 01-1 VIII ..
, O
~' ~ ii .
HOeil HCN(R7)2 IX
':
R l O
C__C c__R2 ,, -,, (R )~NOii H~N(R )2 .
It will be understood that the compound similar to IX, wherein the ~ormyl and aminoformyl groups are reversed, is equlvalent in all respects to compound IX. Pyridones are ;~ formed from any of the above three intermediates, which can all be represented by formula II, by simple contact of .
~: the intermediate wlth an amine of the formula YNH2. : -. :: :
30 : .. .
: : ~3 ::~ X-40~7K ~
~7~9'7 '~`he starting 2-propanones of Formula lV may ~e ~repared by syntheses in the litera-ture. ~or example, see Coan et al., J. Am. Chem. Soc. 76, 501 (1954); Sullivan et al., "Disodium Tetracarbonylferrate", American L,aboratory 49-56 (June 1974); Collman et al., "Synthesis of Hemiflu-orinated Ketones using Disodium Tetracarbonylferrate," J.
Am. Chem. Soc. 95, 2689-91 (1973); Col:Lman et al., "Acyl and Alkyl Tetracarbonylferrate Complexes as Intermediates in the Synthesis of Aldehydes and Ketones", J. Am. Chem. Soc. 94, 10 2516-18 (1972~.
The compounds of formula VI also are prepared as follows: - -R 1 ~, ~ O
(A). ~ ~ ~--CHx---C---Halo ~ (R7)zNCH=CH--R
~===----0 11 IICN(R~)2 It will be under stood that reaction (A) can also be per-formed in the opposite manner, as shown below:
R~ 0 (B). ~ ~ --CH=CHN(R~)2 ~ llal --C--CH2--R' ~_____ / I . :
____- I
(R7)2N 1H : :
It is also possible to form the starting materials of formula II wherein both Ql and Q2 are identical by using X-4097K ~
~ . ..
^ ' ,' ,:
~5~7 ~hos<Jene as the carbonyl halide when the 3- and 5-substi-tuents oF the pyridone product of formula I are identlcal.
(C) . ~ C`I =CH--N(R7)2 -~
Rm~ Rm /
In general, intermediate compounds in the syn-thesis are not purified, but are simply used in successive steps after separation by extraction, neutralization or removal of excess solvent or reactant as appropriate.
The enamine acylation reactions, A-C, are per-formed in the presence of bases such as tertiary amlnes, alkali metal oarbonates, magnesium oxide and the like, and in aprotic solvents as described above.
In some instances, as organic chemists will understand, it is necessary to apply additional synthetic steps after the pyridone compound has been formed. For example, it is convenient to form compounds having alkoxy and like Rl and R5 substituents by first making the corre-sponding hydroxy-substituted compound, and then suhstituting -on the oxygen atom.
The pyridinethiones of formula I are readily : .
prepared by the treatment of the corresponding pyridones with P2S5 in pyridine at reflux temperature, according to known methods.
` 30 - .
, . . . . .
~ ,, .. , ,.,, ~ . " , . .
Tl~e l-acetoxy compounds of ~ormula 1 are ma(le ~)y li~st makin(l tho correspon(iing l-hydroxypyriclone, using N112~11 as the amine, and esterifying it with acetic an-hydride. The other l-substituents are provided by appro-priate Y substituents on -the amines, YNH~, used to prepare the pyridones.
The followiny preparàtive examples are presented to assure that those skilled in organic chemistry can obtain any desired compound of formula I.
The examples below show the various processes by which compounds of formula I have been made. It will be understood, however, that all of the various processes can be used, with appropriate variations, to make any compound of formula I.
Many exemplary compounds are indicated as made by the yeneral process of a previous exemplary compound. In such instances, an ordinarily skilled organic chemist will readily see the minor changes to the exemplary process which will be needed to prepare the other exemplary compounds.
Temperatures are given in degrees Centigrade (~C.). Nuclear magnetic resonance spectra (NMR) were determined on a 60-mega~ertz instrument using tetramethyl-silane as an internal reference and are indicated in cycles per second (CPS3~ Melting points (mOp.j were determined by using a thermal block.
~: ~ %~ :
~X-4097K -~6-:' ~ , ' .
~'756~7 ~ e first series of examples illustrate the varia-tiOII of the process wherein a compound of formula II which is an enaminoketone oE formula VI is prepared, and is then arninoformylated and aminated with a compound of the formula YNH2 to form the pyridone of formula I. Preparation 1 below illustrates the formation of the enaminoketone.
Preparation 1 1-dimethylamino-4-(3-nitrophenoxy)-2-(3-trifluoro-methylphenyl)-l-buten-3-one -A mixture of 7.29 g. of N-diethyl-3-trifluoro-methylstyrylamine and 2.4 g. of pyridine in 100 ml. of -~ -diethyl ether was cooled to 0C., and 6.45 g. of 3-nitro-phenoxyacetyl chloride was added in 60 ml. of diethyl ether dropwise. The mixture was stirred at 0C. for two hours after the addition was complete, and was then stirred at room temperature for 16 hours. The reaction mixture was filtered, and the filtrate was evaporated under vacuum. The residue was taken up in dichloromethane, washed with water, dried over magnesium sulfate and evaporated under vacuum.
Example 1 l-methyl-3-(3-nitrophenoxy)-5-(3-trifluoromethyl-phenyl)-4(1~)-pyridone The residue from Preparation 1 was heated under reflux for 10 hours with 50 ml. of dimethylformamide dlmethyl acetal. The reaction mixture was then concentrated under vacuum, and the residual oil was taken up in 100 ml. of ethanol. A 10 g. portion of methylamine hydrochloride was added, and the mixture was heated under reflux for 10 hours.
The reaction mixture was then evaporated under vacuum, and X-4097K ~_ .
~75~;~7 . .
the residue was taken up in dichloro~ethane, washed with water and then with saturated sodium chloride solution, dried over maynesium sulfate and evaporated under vacuum -to a dark oil. The residual oil was chromatographed over silica gel with benzene, and then with benzene containing increasing amounts of ethyl acetate. The product was eluted by 80%
benzene/20% ethyl acetate. The product-containing fractions were combined and evaporated under vacuum to an oil. The oil was triturated with isopropyl ether and recrystallized .~, .::
from isopropyl ether/dichloromethane. The yield was 2.9 g.
of the pyridone named above, m.p. 171-172C.
- The following exemplary compounds were made by processes similar to that of Example 1. Chemists will understand the minor alterations necessary to prepare the various compounds.
Example 2 3-(4-methoxy-3-methylphenyl)-1-methyl-5~phenyl-
~ .
'' :' -'.,-~7~
",~ . t) -C--t~--cl~.2__~2 V1 YIINO
I..ither iorn~ylation or aminoformylation oi- the above enamino-ketone, which also can be represented by Eormula II, affords the pyridone product, as the intermediate cyclizes as soon as the second group is introduced on the other methylene group.
~ Either of compounds V or VI may be either for-mylated or aminoformylated to provide intermediates of any of the Eormulae below.
j~l . . O
m /~ --t~--C--ii~
=~=~ ~iOi~ 01-1 VIII ..
, O
~' ~ ii .
HOeil HCN(R7)2 IX
':
R l O
C__C c__R2 ,, -,, (R )~NOii H~N(R )2 .
It will be understood that the compound similar to IX, wherein the ~ormyl and aminoformyl groups are reversed, is equlvalent in all respects to compound IX. Pyridones are ;~ formed from any of the above three intermediates, which can all be represented by formula II, by simple contact of .
~: the intermediate wlth an amine of the formula YNH2. : -. :: :
30 : .. .
: : ~3 ::~ X-40~7K ~
~7~9'7 '~`he starting 2-propanones of Formula lV may ~e ~repared by syntheses in the litera-ture. ~or example, see Coan et al., J. Am. Chem. Soc. 76, 501 (1954); Sullivan et al., "Disodium Tetracarbonylferrate", American L,aboratory 49-56 (June 1974); Collman et al., "Synthesis of Hemiflu-orinated Ketones using Disodium Tetracarbonylferrate," J.
Am. Chem. Soc. 95, 2689-91 (1973); Col:Lman et al., "Acyl and Alkyl Tetracarbonylferrate Complexes as Intermediates in the Synthesis of Aldehydes and Ketones", J. Am. Chem. Soc. 94, 10 2516-18 (1972~.
The compounds of formula VI also are prepared as follows: - -R 1 ~, ~ O
(A). ~ ~ ~--CHx---C---Halo ~ (R7)zNCH=CH--R
~===----0 11 IICN(R~)2 It will be under stood that reaction (A) can also be per-formed in the opposite manner, as shown below:
R~ 0 (B). ~ ~ --CH=CHN(R~)2 ~ llal --C--CH2--R' ~_____ / I . :
____- I
(R7)2N 1H : :
It is also possible to form the starting materials of formula II wherein both Ql and Q2 are identical by using X-4097K ~
~ . ..
^ ' ,' ,:
~5~7 ~hos<Jene as the carbonyl halide when the 3- and 5-substi-tuents oF the pyridone product of formula I are identlcal.
(C) . ~ C`I =CH--N(R7)2 -~
Rm~ Rm /
In general, intermediate compounds in the syn-thesis are not purified, but are simply used in successive steps after separation by extraction, neutralization or removal of excess solvent or reactant as appropriate.
The enamine acylation reactions, A-C, are per-formed in the presence of bases such as tertiary amlnes, alkali metal oarbonates, magnesium oxide and the like, and in aprotic solvents as described above.
In some instances, as organic chemists will understand, it is necessary to apply additional synthetic steps after the pyridone compound has been formed. For example, it is convenient to form compounds having alkoxy and like Rl and R5 substituents by first making the corre-sponding hydroxy-substituted compound, and then suhstituting -on the oxygen atom.
The pyridinethiones of formula I are readily : .
prepared by the treatment of the corresponding pyridones with P2S5 in pyridine at reflux temperature, according to known methods.
` 30 - .
, . . . . .
~ ,, .. , ,.,, ~ . " , . .
Tl~e l-acetoxy compounds of ~ormula 1 are ma(le ~)y li~st makin(l tho correspon(iing l-hydroxypyriclone, using N112~11 as the amine, and esterifying it with acetic an-hydride. The other l-substituents are provided by appro-priate Y substituents on -the amines, YNH~, used to prepare the pyridones.
The followiny preparàtive examples are presented to assure that those skilled in organic chemistry can obtain any desired compound of formula I.
The examples below show the various processes by which compounds of formula I have been made. It will be understood, however, that all of the various processes can be used, with appropriate variations, to make any compound of formula I.
Many exemplary compounds are indicated as made by the yeneral process of a previous exemplary compound. In such instances, an ordinarily skilled organic chemist will readily see the minor changes to the exemplary process which will be needed to prepare the other exemplary compounds.
Temperatures are given in degrees Centigrade (~C.). Nuclear magnetic resonance spectra (NMR) were determined on a 60-mega~ertz instrument using tetramethyl-silane as an internal reference and are indicated in cycles per second (CPS3~ Melting points (mOp.j were determined by using a thermal block.
~: ~ %~ :
~X-4097K -~6-:' ~ , ' .
~'756~7 ~ e first series of examples illustrate the varia-tiOII of the process wherein a compound of formula II which is an enaminoketone oE formula VI is prepared, and is then arninoformylated and aminated with a compound of the formula YNH2 to form the pyridone of formula I. Preparation 1 below illustrates the formation of the enaminoketone.
Preparation 1 1-dimethylamino-4-(3-nitrophenoxy)-2-(3-trifluoro-methylphenyl)-l-buten-3-one -A mixture of 7.29 g. of N-diethyl-3-trifluoro-methylstyrylamine and 2.4 g. of pyridine in 100 ml. of -~ -diethyl ether was cooled to 0C., and 6.45 g. of 3-nitro-phenoxyacetyl chloride was added in 60 ml. of diethyl ether dropwise. The mixture was stirred at 0C. for two hours after the addition was complete, and was then stirred at room temperature for 16 hours. The reaction mixture was filtered, and the filtrate was evaporated under vacuum. The residue was taken up in dichloromethane, washed with water, dried over magnesium sulfate and evaporated under vacuum.
Example 1 l-methyl-3-(3-nitrophenoxy)-5-(3-trifluoromethyl-phenyl)-4(1~)-pyridone The residue from Preparation 1 was heated under reflux for 10 hours with 50 ml. of dimethylformamide dlmethyl acetal. The reaction mixture was then concentrated under vacuum, and the residual oil was taken up in 100 ml. of ethanol. A 10 g. portion of methylamine hydrochloride was added, and the mixture was heated under reflux for 10 hours.
The reaction mixture was then evaporated under vacuum, and X-4097K ~_ .
~75~;~7 . .
the residue was taken up in dichloro~ethane, washed with water and then with saturated sodium chloride solution, dried over maynesium sulfate and evaporated under vacuum -to a dark oil. The residual oil was chromatographed over silica gel with benzene, and then with benzene containing increasing amounts of ethyl acetate. The product was eluted by 80%
benzene/20% ethyl acetate. The product-containing fractions were combined and evaporated under vacuum to an oil. The oil was triturated with isopropyl ether and recrystallized .~, .::
from isopropyl ether/dichloromethane. The yield was 2.9 g.
of the pyridone named above, m.p. 171-172C.
- The following exemplary compounds were made by processes similar to that of Example 1. Chemists will understand the minor alterations necessary to prepare the various compounds.
Example 2 3-(4-methoxy-3-methylphenyl)-1-methyl-5~phenyl-
4(lH)-pyridone, m.p. 157-160C.j yield 2.5% ~ --Example 3 3-(3-bromo-4-methylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 168-170C., yield 13%
Example 4 l-methyl-3-(3-nitrophenyl)-5-(3-trifluoromethyl-phenyl)-4(1H)~pyridone, m.p. 209-211C.l yield 51%
Example 5 l-methy1-3-phenyl-5-(3-phenylthiophenyl)-4(1H)-pyr1done, mass spectrometry MI, 369, yield 8%
, X-4097K ~ ~9 ; ;~ ~ '' ' ' ' ' ,- ,' ' ~7S6~7 The following compound was prepared by oxidizing the compound above with hydrogen peroxide in acetic acid.
Example 6 l-methyl-3-phenyl-5-(3-phenylsulfonylphenyl)-4(1H)-pyridone, m.p. 65-72C., yield 48%
The fo11Owlng compounds are also prepared by fol-lowing the process of Example 1.
Exam~le 7 3-(2-chloro-4-fluorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 190-192C.j yield 5 Example_8 3-(3,4-dimethylphenyl)-1-methyl-5-phenyl-4(lH)-pyridone, m.p. 108-111C., yield S~
Example 9 3-~3,5-dimethylpheny1)-1-methyi-5-phenyl-4(1H)-pyridone, m.p. 148-150C., yield 10~ ~ ;
EXample 10 3-(3-butylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone,~m.p. 87-89C., yield 6 Example 11 3-~2,5-dimethylphenyl)-1-methyl~5-phenyl-4(1H)~
pyridone, m.p. 1~88~190C., yield 4%
Example 12 , - : , ~ .
3~(2,4~dimethylphenyl)-1-methyl-5~phenyl-4(1H)-; pyrLdone, m.p 153-155C., yield 3%
~: ~ " . : , ~ Example 13 :
:l~methyl-3-ph0noxy-5-(3~trifluoromethylphenyl)--; 4~1H)~pyridone, m.p. 144-145C., yield 15%
:, ~: ~ , , ;30 ~ ~ 2~
-X-4097K ~9_ ~: : .
:
~7S697 .e~.Y~ e l~
3-etlloxy~arl~onyl~ lethyl-5-(3-tri~luoromeLhyl- .. ,.,.. :; :.' ~henyl)-4(1lt)-pyridone, m.p. 151-152C., yield 6290 Example lS
l-methyl-3-(3-trifluoromethylphenyl)-5-phenyl-thio-4(lH)-pyridone, m.p. 164-165C., yield 18%
Example 16 3-(2,4-dichlorophenoxy~-1-methyl-S-(3-trifluoro-::
methylphenyl)-4(lH)~pyridone, m.p. 129-130C., yield 40% ~--Exam~le 17 1-methyl-3-(2-thienyl)-$-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, m.p. 185-186C., yield 84%
Example 18 .
3-ethylthio-1-methyl-5-phenyl-4(lH)-pyridone, m.p.
94-95C., yield 40%
Example 19 .
3-ethylthio-1-methyl-5-(3-trifluoromethylphenyl)-4(1~j-pyridone, m.p. 84-85C., yield 40%
The following exemplary compound was prepared by , oxidation of the compound of Example 19 with hydrogen ~peroxide in methylene dichloride at about 0C.
Example 20 :
3-ethylsulfonyl-1-methyl-5-(3-trifluoromethyl--~ ~ phenyl)-4(1H~-pyridone, m.p. 196-198C., yield 70%
:
:
The following compound was prepared by oxidizing the compound of~E~ample 19 with sodium periodate in aqueous ethanol at room temperature for 16 hours. - ~;
: . ;
` 30 ... . . . . . .. . . . . .. .... .. . . .. ... ...
`
~L~7S6~7 -:
Example 21 3-ethylsulfinyl-1-methyl-5-(3-trifluoromethy]-phenyl~-4(1H)-pyridone, m.p 146-148C., yield 82%
The following compounds were also made by the process of Example 1.
Example 22 3-(5-bromo-2-fluorophenyl)-1-methyl-5-phenyl-4~1ll)-pyridone, m.p. 148-150C., yield 6'~, ExampLe 23 1-methyl-3-(5-nitro-2-methylphenyl)-5 phenyl-4(lH)-pyridone, m.p. 185-187C., yield 5%
Example 24 3-cyano-5-(2,5-dimethoxyphenyl)-1-methyl-4(lH)-pyridone, m.p. 209-211C., yield 4% -~
Example 25 3-(2,6-dichlorophenyl)-1-methyl-5-phenyl-4(lH)-pyridone, m.p. 223-226C., yield 20%
Examnle 26 ;~ 3-ethoxycarbonyl-1-methyl-5-phenyl-4(lH)-pyridone, m.p. 107-10`8C., yield 68%
Example 27 . .
l-methyl-3-propylthio-5 (3-trifluoromethylphenyl)-4~(1H)-pyridone, m.p. 101-102C., yield 25%
Example 28 ~: .
~ 3-buty1thio-1-methyl-5-(3-triflu~romethylphenyl)--~ ~ 4(1H)-pyridone, m.p. lOg-110C., yield 35%
Example 29 methyl-3-methylthio-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 121-122C., yield 20%
.
X-4097K ~ ~Q~
- , ,i,, :, :~ ~ ''~ ' i ''.
- '- :
- ! .
~ ~L)7~9~ ~
:.
h`xample 30 I-methyl-3-(3-trifluoromethylphenyl)-5-(4-tri-fluoromethylphenyl)-4(1~l)-pyridone, m.p. 110-113C., yield 1 0 '~ ",, Example 31 l-methyl-3-(3-trifluoromethylphenyl)-S-trifluoro-methylthio-4~lH)-pyridone, m.p. 122 124C., yield 21% ~-Example 32 3-(3,4-dimethoxyphenyl)-1-methyl-5-(3-trifluoro- -methylphenyl)-4(1H)-pyridone, m.p. 148-150C., yield 10 Example_33 Mixture of 3-(5-fluoro-2-iodophenyl)-1-methyl-5- ~` `
phenyl-4(lH)-pyridone and 3-(2-bromo-5-fluorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, mixed m.p. 211-214C., yield 7%
Example 34 3-benzylthio-1-methyl-5-(3-trifluoromethylphenyl)-4(1Hj-pyridoné, m.p. 121-122C., yield 40 Example 35 3-(4-benzyloxyphenyl)-1-methyl-5-(3-trifluoro-methylphenyl~-4(lH)-pyridone, amorphous, yield 10%
Examplé 36 , 1,3-dlethyl-5-(3-trifluoromethylphenyl)-4(1H~
: pyri done , m . p . 67-70C., yield 3~
The~ compound below was prepared by the hydro-genation of Exa~mple 35 in acetic acid in the presence of 5%
palladium on carbon hydrogenatlon catalyst.
::
~ -40g~K
A ~ ~
. ~ ~ .... .
. . .
~756~7 . .
l~am~le_37 3-(4-hydroxyphenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, m.p. 162-163C., yleld 50-'~
The ~eneral process of Example 1 was used to prepare the compounds below.
Example 38 3-(4-chloro-3-trifluoromethylphenyl)-5-ethoxy-1-methyl-4(1~)-pyridone, m.p. 158-i59C., yield 15%
Example 39 1-methyl-3-isopropylthio-S-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, m.p. 93-94C., yield 32 Example 40 3-~4-chloro-3-trifluoromethylphenyl)-5-ethylthio-l-methyl-4(lH)-pyridone, m.p. 115-116QC., yield 11%
Example 41 3-(4-chloro-3-trifluoromethylphenyl)-1-methyl-; 5-phenyl-4(1H)-pyridone, m.p. 154-155C., yield 17%
Example 42 3-(2j5-dimethylphenyl)-1-methyl-5-(3-trifluoro-20 methylphenyl)-4(lH)-pyridone, m.p. 165-i67C., yield 2%
..
Example 43 3-(3,5-dimethylphenyl)~l-methyl-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, m.p. 160-163C., yield 6%
Example 44 3-(2,4-dichlorophenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, m.p. 139-142C., yield 11%
. .
Example 45 methyl-3-ph~nyl-5-(2-trifluoromethylphenyl)-4(1H)-pyrldone, m.p. 168-171C., yield 14%
~ : : ..
~30 X~4097K ~
, ,: :
:;
` 1075G97 , Lxample 46 _ l-methyl-3-(2-trifluoromethylphenyl)-5-(3-tri-Eluo omethylphenyl)-4(1ll) pyridone, m.p. 135-138C., yield 24'~
Example 47 3 (3,4-dimethylphenyl)-1-methyl-5-(3-trifluoro- - ``
methylphenyl)-4(lH)-pyridone, m.p. 150-153C., yield 15%
Example 48 3-(3-iodophenyl)-1-methyl-5-(3-trifluoromethyl-10phenyl)-4(1~11-pyridone, m.p. 178-181C., yield 15%
Example 49 3-ethyl-1-methyl-5-(3-methoxyphenyl)-4(lH)-pyridone, yield 5~, mass spectroscopy MI, 243 Example 50 l-methyl-3-(3-iodophenyl)-5-phenyl-4(lH)-pyridone, m.p. 190-193C., yield 8 -Example 51 `
l-methyl-3-(4-methoxyphenoxy)-5-(3-trifluoro-methylphenyl?-4(1H)-pyridone, m.p. 119-120C., yield 25 20Example 52 l-methyl-3-(2-chloro-4-fluorophenyl)-5-(3~tri-. :
fluoromethylphenyl)-4(lH)-pyridone, m.p. 183-186C., yield `
.
20~ ` -xample 53 .~
~ methyl-3-(4-chloro-3-trifluoromethylphenyl)-5- ``
.
trifluoromethyl-4(lH)-pyr~done, m.p. 164-165C., yield 2 Example 54 -methyl-3-(4-chloro-3-trifluoromethylphenyl)-5-propyl-4(1H)-pyridone, m.p. 141-142C., yield 8~ -~;~ X-4097K _~4_ '`
:~ ~ ` ` ~ : , :,'.
, ~ ^ --~07S6~7 lx~ e 55 l-me-thy1-3-iso~ropylthio-')-(4-cl~loro-~-tril~Luoro-methylphenyl)-4(1ii)-pyridone, m.p. 127-129C., yield 15 Example 56 1-methyl-3-(4-chloro-3-trifluoromethylphenyl)-5-propylthio~4(1H)-pyrldone, m.p. 128-130C., yield 15%
Example 57 l-methyl-3-(4-chloro-3-trifiuoromethylphenyl)-
Example 4 l-methyl-3-(3-nitrophenyl)-5-(3-trifluoromethyl-phenyl)-4(1H)~pyridone, m.p. 209-211C.l yield 51%
Example 5 l-methy1-3-phenyl-5-(3-phenylthiophenyl)-4(1H)-pyr1done, mass spectrometry MI, 369, yield 8%
, X-4097K ~ ~9 ; ;~ ~ '' ' ' ' ' ,- ,' ' ~7S6~7 The following compound was prepared by oxidizing the compound above with hydrogen peroxide in acetic acid.
Example 6 l-methyl-3-phenyl-5-(3-phenylsulfonylphenyl)-4(1H)-pyridone, m.p. 65-72C., yield 48%
The fo11Owlng compounds are also prepared by fol-lowing the process of Example 1.
Exam~le 7 3-(2-chloro-4-fluorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 190-192C.j yield 5 Example_8 3-(3,4-dimethylphenyl)-1-methyl-5-phenyl-4(lH)-pyridone, m.p. 108-111C., yield S~
Example 9 3-~3,5-dimethylpheny1)-1-methyi-5-phenyl-4(1H)-pyridone, m.p. 148-150C., yield 10~ ~ ;
EXample 10 3-(3-butylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone,~m.p. 87-89C., yield 6 Example 11 3-~2,5-dimethylphenyl)-1-methyl~5-phenyl-4(1H)~
pyridone, m.p. 1~88~190C., yield 4%
Example 12 , - : , ~ .
3~(2,4~dimethylphenyl)-1-methyl-5~phenyl-4(1H)-; pyrLdone, m.p 153-155C., yield 3%
~: ~ " . : , ~ Example 13 :
:l~methyl-3-ph0noxy-5-(3~trifluoromethylphenyl)--; 4~1H)~pyridone, m.p. 144-145C., yield 15%
:, ~: ~ , , ;30 ~ ~ 2~
-X-4097K ~9_ ~: : .
:
~7S697 .e~.Y~ e l~
3-etlloxy~arl~onyl~ lethyl-5-(3-tri~luoromeLhyl- .. ,.,.. :; :.' ~henyl)-4(1lt)-pyridone, m.p. 151-152C., yield 6290 Example lS
l-methyl-3-(3-trifluoromethylphenyl)-5-phenyl-thio-4(lH)-pyridone, m.p. 164-165C., yield 18%
Example 16 3-(2,4-dichlorophenoxy~-1-methyl-S-(3-trifluoro-::
methylphenyl)-4(lH)~pyridone, m.p. 129-130C., yield 40% ~--Exam~le 17 1-methyl-3-(2-thienyl)-$-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, m.p. 185-186C., yield 84%
Example 18 .
3-ethylthio-1-methyl-5-phenyl-4(lH)-pyridone, m.p.
94-95C., yield 40%
Example 19 .
3-ethylthio-1-methyl-5-(3-trifluoromethylphenyl)-4(1~j-pyridone, m.p. 84-85C., yield 40%
The following exemplary compound was prepared by , oxidation of the compound of Example 19 with hydrogen ~peroxide in methylene dichloride at about 0C.
Example 20 :
3-ethylsulfonyl-1-methyl-5-(3-trifluoromethyl--~ ~ phenyl)-4(1H~-pyridone, m.p. 196-198C., yield 70%
:
:
The following compound was prepared by oxidizing the compound of~E~ample 19 with sodium periodate in aqueous ethanol at room temperature for 16 hours. - ~;
: . ;
` 30 ... . . . . . .. . . . . .. .... .. . . .. ... ...
`
~L~7S6~7 -:
Example 21 3-ethylsulfinyl-1-methyl-5-(3-trifluoromethy]-phenyl~-4(1H)-pyridone, m.p 146-148C., yield 82%
The following compounds were also made by the process of Example 1.
Example 22 3-(5-bromo-2-fluorophenyl)-1-methyl-5-phenyl-4~1ll)-pyridone, m.p. 148-150C., yield 6'~, ExampLe 23 1-methyl-3-(5-nitro-2-methylphenyl)-5 phenyl-4(lH)-pyridone, m.p. 185-187C., yield 5%
Example 24 3-cyano-5-(2,5-dimethoxyphenyl)-1-methyl-4(lH)-pyridone, m.p. 209-211C., yield 4% -~
Example 25 3-(2,6-dichlorophenyl)-1-methyl-5-phenyl-4(lH)-pyridone, m.p. 223-226C., yield 20%
Examnle 26 ;~ 3-ethoxycarbonyl-1-methyl-5-phenyl-4(lH)-pyridone, m.p. 107-10`8C., yield 68%
Example 27 . .
l-methyl-3-propylthio-5 (3-trifluoromethylphenyl)-4~(1H)-pyridone, m.p. 101-102C., yield 25%
Example 28 ~: .
~ 3-buty1thio-1-methyl-5-(3-triflu~romethylphenyl)--~ ~ 4(1H)-pyridone, m.p. lOg-110C., yield 35%
Example 29 methyl-3-methylthio-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 121-122C., yield 20%
.
X-4097K ~ ~Q~
- , ,i,, :, :~ ~ ''~ ' i ''.
- '- :
- ! .
~ ~L)7~9~ ~
:.
h`xample 30 I-methyl-3-(3-trifluoromethylphenyl)-5-(4-tri-fluoromethylphenyl)-4(1~l)-pyridone, m.p. 110-113C., yield 1 0 '~ ",, Example 31 l-methyl-3-(3-trifluoromethylphenyl)-S-trifluoro-methylthio-4~lH)-pyridone, m.p. 122 124C., yield 21% ~-Example 32 3-(3,4-dimethoxyphenyl)-1-methyl-5-(3-trifluoro- -methylphenyl)-4(1H)-pyridone, m.p. 148-150C., yield 10 Example_33 Mixture of 3-(5-fluoro-2-iodophenyl)-1-methyl-5- ~` `
phenyl-4(lH)-pyridone and 3-(2-bromo-5-fluorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, mixed m.p. 211-214C., yield 7%
Example 34 3-benzylthio-1-methyl-5-(3-trifluoromethylphenyl)-4(1Hj-pyridoné, m.p. 121-122C., yield 40 Example 35 3-(4-benzyloxyphenyl)-1-methyl-5-(3-trifluoro-methylphenyl~-4(lH)-pyridone, amorphous, yield 10%
Examplé 36 , 1,3-dlethyl-5-(3-trifluoromethylphenyl)-4(1H~
: pyri done , m . p . 67-70C., yield 3~
The~ compound below was prepared by the hydro-genation of Exa~mple 35 in acetic acid in the presence of 5%
palladium on carbon hydrogenatlon catalyst.
::
~ -40g~K
A ~ ~
. ~ ~ .... .
. . .
~756~7 . .
l~am~le_37 3-(4-hydroxyphenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, m.p. 162-163C., yleld 50-'~
The ~eneral process of Example 1 was used to prepare the compounds below.
Example 38 3-(4-chloro-3-trifluoromethylphenyl)-5-ethoxy-1-methyl-4(1~)-pyridone, m.p. 158-i59C., yield 15%
Example 39 1-methyl-3-isopropylthio-S-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, m.p. 93-94C., yield 32 Example 40 3-~4-chloro-3-trifluoromethylphenyl)-5-ethylthio-l-methyl-4(lH)-pyridone, m.p. 115-116QC., yield 11%
Example 41 3-(4-chloro-3-trifluoromethylphenyl)-1-methyl-; 5-phenyl-4(1H)-pyridone, m.p. 154-155C., yield 17%
Example 42 3-(2j5-dimethylphenyl)-1-methyl-5-(3-trifluoro-20 methylphenyl)-4(lH)-pyridone, m.p. 165-i67C., yield 2%
..
Example 43 3-(3,5-dimethylphenyl)~l-methyl-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, m.p. 160-163C., yield 6%
Example 44 3-(2,4-dichlorophenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, m.p. 139-142C., yield 11%
. .
Example 45 methyl-3-ph~nyl-5-(2-trifluoromethylphenyl)-4(1H)-pyrldone, m.p. 168-171C., yield 14%
~ : : ..
~30 X~4097K ~
, ,: :
:;
` 1075G97 , Lxample 46 _ l-methyl-3-(2-trifluoromethylphenyl)-5-(3-tri-Eluo omethylphenyl)-4(1ll) pyridone, m.p. 135-138C., yield 24'~
Example 47 3 (3,4-dimethylphenyl)-1-methyl-5-(3-trifluoro- - ``
methylphenyl)-4(lH)-pyridone, m.p. 150-153C., yield 15%
Example 48 3-(3-iodophenyl)-1-methyl-5-(3-trifluoromethyl-10phenyl)-4(1~11-pyridone, m.p. 178-181C., yield 15%
Example 49 3-ethyl-1-methyl-5-(3-methoxyphenyl)-4(lH)-pyridone, yield 5~, mass spectroscopy MI, 243 Example 50 l-methyl-3-(3-iodophenyl)-5-phenyl-4(lH)-pyridone, m.p. 190-193C., yield 8 -Example 51 `
l-methyl-3-(4-methoxyphenoxy)-5-(3-trifluoro-methylphenyl?-4(1H)-pyridone, m.p. 119-120C., yield 25 20Example 52 l-methyl-3-(2-chloro-4-fluorophenyl)-5-(3~tri-. :
fluoromethylphenyl)-4(lH)-pyridone, m.p. 183-186C., yield `
.
20~ ` -xample 53 .~
~ methyl-3-(4-chloro-3-trifluoromethylphenyl)-5- ``
.
trifluoromethyl-4(lH)-pyr~done, m.p. 164-165C., yield 2 Example 54 -methyl-3-(4-chloro-3-trifluoromethylphenyl)-5-propyl-4(1H)-pyridone, m.p. 141-142C., yield 8~ -~;~ X-4097K _~4_ '`
:~ ~ ` ` ~ : , :,'.
, ~ ^ --~07S6~7 lx~ e 55 l-me-thy1-3-iso~ropylthio-')-(4-cl~loro-~-tril~Luoro-methylphenyl)-4(1ii)-pyridone, m.p. 127-129C., yield 15 Example 56 1-methyl-3-(4-chloro-3-trifluoromethylphenyl)-5-propylthio~4(1H)-pyrldone, m.p. 128-130C., yield 15%
Example 57 l-methyl-3-(4-chloro-3-trifiuoromethylphenyl)-
5-(2-thienyl)-4(lH)-pyridone, m.p. 166-168C., yield 10 10Example 58 3-ethyl-1-methyl-5-(4-chloro-3-trifluoromethyl-phenyl)-4(lH)-pyridone, m.p. 121-123C., yield 1'~
EXample 59 l-methyl-3-(2,4-dimethylphenyl)-5~(3-trlfluoro- ;
methylphenyl)-4(lH)-pyridone, m.p. 128-131C., yield 6% i ~:
'" i Example 60 3-isopropoxy-1-methyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridone, mass spectroscopy MI, 311, yield 1 Example 61 .
201-methyl-3-(4-chlorophenoxy)-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, m.p. 90-91C., yield 15 Example 62 l-methyl-3-(3-methylthiophenyl~-5-(3-trifluoro-.
methylphenyl)-~4(1H)-pyridone, m.p. 150-153C., yield 25 -The followin~ compound was prepared by oxidation .. . . .
of the compound of Example 62 with hydrogen peroxide in pyridine at room temperature.
i .
. ,' X-4097K ~
: -, 69~
Exam~_e 63 l-methyl-3-(3-methylsulfonylphenyl)-5-(3-tri-fluoromethylphenyl)-4(1~1)-pyridone, m.p. 180-183C., yield 20'-~
The general process of Examp:Le 1 was used to prepare the following compounds.
Example 64 l-methyl-3-(3-trifluoromethylphenoxy)-5-(3-tri-fluoromethylphenyl)-4(lH)-pyridone, m.p. 93-95C., yield 40%
Example 65 3-(4-methoxyphenyl)-1-methyl-5-(3-trifluoromethyl- :
phenyl)-4(lH)-pyridone, m.p. 160-162C., yield 40%
Example 66 , 3-(2,3-dichlorophenoxy)-1-methyl-5-(3-trifluoro-~methylphenyl)-4(lH)-pyridone, m.p. 200-202C., yield 30%
Example 67 ~ !, ' ' ~
3-(3,5-dichlorophenoxy)-1-methyl-5-(3-trifluoro- ~ :
methylphenyl)-4(1H)-pyridone, m.p. 128-130C., yield 30%
',~
Example 68 ~ ~
3-(3j4-dichlorophenoxy)-1-methyl-5-(3-trifluoro- :
. . ~ .
methylphenyl)-4(lH)-pyridone, m.p. 127-129C~, yield 20~ ;
Example 69 3-(4-chloro-3-trifluoromethylphenyl)-1-methyl-5-sopropyl-4(1Hj~-pyridone, m p~ 85-87C., yield 25%
Example 70 3-(2,5-dichlorophenoxy)-1-methyl-5-(3-tri'luoro-: . . .
~ methylphenyl)-4tlHj-pyridone~ m.p. 162-164C., yield 28%
30 ~
~ X-4097K -~6-~: :: : .
~ ~ ' ' ,. ':
: ~
- .
- . : . : . ~ . . . . .. . .
:1~7~;6~7 Example 71 l-methyl-3-(4-methylthiophenoxy)-5-(3-trifluoro-metllylphenyl)-4(1ll)-;~yridone, m.p. 138-140C., yield 17%
Example 7 ?
3-isobutylthio-1-methyl-5-(3-trifluor~methyl-phenyl)-4(1Hj-pyridone, mass spectroscopy ~I~ 341, yield 1%
Example 73 3-t-butylthio-1-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, m.p. 124-125C., yield 1%
Example_74 3-s-butylthio-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, mass spectroscopy MI, 341, yield 1%
Example 75 l-methyl-3-(4-nitrophenoxy)-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, m.p. 160-161C., yield 21 : . . .
Example 75A
3-ethyl-1-hydroxy-5-(3-trifluoromethylphenyl)-4(lH)-pyridone, m.p. 134-136C., yield 1%
Example 76 ~ `
1-methyl~3-trifluoromethylsulfonyl-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, m.p. 155-157C., yield 15 Example 77 l-methyl-3-(3-trifluoromethylphenyl)-5-(3-tri-fluoromethylthiophenyl)-4(1H)-pyridone, NMR multiplet at 8.0-7 1 ppm; singlet at 3.27 ppm, yield 1%
; ExampIe 78 l-methyl-3-(3-trifluoromethylphenyl)-5-(3-tri-fluoromethylsulfonylphenyl)-4(1H)-pyridone; m.p. 164-166C., yield 1%
;30 X-4097K;
`
. ~ . - , ' , .`"~ ~`'~ ' :~. `
` ~ILIL~7S6~7 Example 79 1-methyl-3-(2,2~2-trifluoroethoxy)-5-(3--trif]uoro-methylphenyl)-4~1~-l)-pyridone, NMR multiplet at 8.0-7.1 ppm;
quartet at 4.6 ppm; singlet at 3.7 ppm, yieLd 1 Example 79A
l-methyl-3-(2-nitrophenyl)-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, m.p. 230-232C., yield 10 The following group of examples illustrates the preparation of compounds by the aminoformylation of a ketone of formula IV to prepare a bis(aminoformylated) compound of formula II, which is then reacted with an amine of the formula YNH2 to prepare the desired pyridone of formula I.
Preparation_2 ~
1,5-di(dimethylamino)-2-(3-methylphenyl)-4- -(3-trifluoromethylphenyl)-1,4-pentadien -3-one . : .
A 4.5 g. portion of 1-(3-methylphenyl)-3-(3-trifluoromethylphenyl)-2-propanone was combined with 20 ml.
of dimethylformamide dimethyl acetal and heated under reflux -for 16 hours. The reactlon mix~ure was then concentrated under vacuum to obtain an oily residue.
Example 80 l-methyl-3-(3-methylphenyl)-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone The residue from Preparation 2 was taken up in 100 ml. of methanol, and 10 g. of methylamine hydrochloride .
was~added. The mixture was heated under reflu~ for 16 hours, and was then concentrated under vacuum. The residue was takén up in chloroform, and washed with water and with dilute hydrochloric acid. The solution was then passed over ~ ~ .
; X-4097K
~ ? ~ ~ ~
-~ ~7S~
a silica ~3el chromato~raphic column, and eluted with 1:1 benzene/ethyl ~cetate. The product-containing fr~ctions were combined and evaporated to dryness under vacuum. I'he residue was triturated with hexane and recrystallized to obtain 0.4 g. of the product named above, m.p. 155-157C.
The following exemplary compounds were made by processes essentially similar to Example 80 above.
Example 81 l-methyl-3-(2-methylphenyl)-5-(3-trifluoromethyl-phenyl)-4(lfl)-pyridone, m.p. 144-147C., yield S~
Example 82 -l-methyl-3-(4-methylphenyl)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, m.p. 154-156C., yield 6 Example 83 5-(3-methoxycarbonylphenyl)-1-methyl-3-(4-methyl-phenyl)-4(lH)-pyridone, m.p. 85-88C., yield 5% ~ ;
Example 84 5-(3-methoxycarbonylpheny1)-1-methyl-3-(3-methylphenyl)-4(lH)-pyridone, m.p. 180-183C., yield 1~ -Example 85 3-methoxy-1-methyl-S-(3~trifluoromethylphenyl)-4(1H)-pyridone, m.p. 173-175C., yield 18 Example 86 3-(4-bromophenyl)-1-methyl-5-(3-methylphenyl)-. :
4(1H)-pyridone, m.p. 201-204C., yield 21 Example 87 3-(3j4-dichlorophenyl)-1-methyl-5-(3-trifluoro-methylph~enyl)-4(1H)-pyridone, ~.p. 109-112C., yield 4~ ;~
:. :
X-4097K ~-, ~ .:
:
.
,, , - - , , : . ...
EXample 59 l-methyl-3-(2,4-dimethylphenyl)-5~(3-trlfluoro- ;
methylphenyl)-4(lH)-pyridone, m.p. 128-131C., yield 6% i ~:
'" i Example 60 3-isopropoxy-1-methyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridone, mass spectroscopy MI, 311, yield 1 Example 61 .
201-methyl-3-(4-chlorophenoxy)-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, m.p. 90-91C., yield 15 Example 62 l-methyl-3-(3-methylthiophenyl~-5-(3-trifluoro-.
methylphenyl)-~4(1H)-pyridone, m.p. 150-153C., yield 25 -The followin~ compound was prepared by oxidation .. . . .
of the compound of Example 62 with hydrogen peroxide in pyridine at room temperature.
i .
. ,' X-4097K ~
: -, 69~
Exam~_e 63 l-methyl-3-(3-methylsulfonylphenyl)-5-(3-tri-fluoromethylphenyl)-4(1~1)-pyridone, m.p. 180-183C., yield 20'-~
The general process of Examp:Le 1 was used to prepare the following compounds.
Example 64 l-methyl-3-(3-trifluoromethylphenoxy)-5-(3-tri-fluoromethylphenyl)-4(lH)-pyridone, m.p. 93-95C., yield 40%
Example 65 3-(4-methoxyphenyl)-1-methyl-5-(3-trifluoromethyl- :
phenyl)-4(lH)-pyridone, m.p. 160-162C., yield 40%
Example 66 , 3-(2,3-dichlorophenoxy)-1-methyl-5-(3-trifluoro-~methylphenyl)-4(lH)-pyridone, m.p. 200-202C., yield 30%
Example 67 ~ !, ' ' ~
3-(3,5-dichlorophenoxy)-1-methyl-5-(3-trifluoro- ~ :
methylphenyl)-4(1H)-pyridone, m.p. 128-130C., yield 30%
',~
Example 68 ~ ~
3-(3j4-dichlorophenoxy)-1-methyl-5-(3-trifluoro- :
. . ~ .
methylphenyl)-4(lH)-pyridone, m.p. 127-129C~, yield 20~ ;
Example 69 3-(4-chloro-3-trifluoromethylphenyl)-1-methyl-5-sopropyl-4(1Hj~-pyridone, m p~ 85-87C., yield 25%
Example 70 3-(2,5-dichlorophenoxy)-1-methyl-5-(3-tri'luoro-: . . .
~ methylphenyl)-4tlHj-pyridone~ m.p. 162-164C., yield 28%
30 ~
~ X-4097K -~6-~: :: : .
~ ~ ' ' ,. ':
: ~
- .
- . : . : . ~ . . . . .. . .
:1~7~;6~7 Example 71 l-methyl-3-(4-methylthiophenoxy)-5-(3-trifluoro-metllylphenyl)-4(1ll)-;~yridone, m.p. 138-140C., yield 17%
Example 7 ?
3-isobutylthio-1-methyl-5-(3-trifluor~methyl-phenyl)-4(1Hj-pyridone, mass spectroscopy ~I~ 341, yield 1%
Example 73 3-t-butylthio-1-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, m.p. 124-125C., yield 1%
Example_74 3-s-butylthio-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, mass spectroscopy MI, 341, yield 1%
Example 75 l-methyl-3-(4-nitrophenoxy)-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, m.p. 160-161C., yield 21 : . . .
Example 75A
3-ethyl-1-hydroxy-5-(3-trifluoromethylphenyl)-4(lH)-pyridone, m.p. 134-136C., yield 1%
Example 76 ~ `
1-methyl~3-trifluoromethylsulfonyl-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, m.p. 155-157C., yield 15 Example 77 l-methyl-3-(3-trifluoromethylphenyl)-5-(3-tri-fluoromethylthiophenyl)-4(1H)-pyridone, NMR multiplet at 8.0-7 1 ppm; singlet at 3.27 ppm, yield 1%
; ExampIe 78 l-methyl-3-(3-trifluoromethylphenyl)-5-(3-tri-fluoromethylsulfonylphenyl)-4(1H)-pyridone; m.p. 164-166C., yield 1%
;30 X-4097K;
`
. ~ . - , ' , .`"~ ~`'~ ' :~. `
` ~ILIL~7S6~7 Example 79 1-methyl-3-(2,2~2-trifluoroethoxy)-5-(3--trif]uoro-methylphenyl)-4~1~-l)-pyridone, NMR multiplet at 8.0-7.1 ppm;
quartet at 4.6 ppm; singlet at 3.7 ppm, yieLd 1 Example 79A
l-methyl-3-(2-nitrophenyl)-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, m.p. 230-232C., yield 10 The following group of examples illustrates the preparation of compounds by the aminoformylation of a ketone of formula IV to prepare a bis(aminoformylated) compound of formula II, which is then reacted with an amine of the formula YNH2 to prepare the desired pyridone of formula I.
Preparation_2 ~
1,5-di(dimethylamino)-2-(3-methylphenyl)-4- -(3-trifluoromethylphenyl)-1,4-pentadien -3-one . : .
A 4.5 g. portion of 1-(3-methylphenyl)-3-(3-trifluoromethylphenyl)-2-propanone was combined with 20 ml.
of dimethylformamide dimethyl acetal and heated under reflux -for 16 hours. The reactlon mix~ure was then concentrated under vacuum to obtain an oily residue.
Example 80 l-methyl-3-(3-methylphenyl)-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone The residue from Preparation 2 was taken up in 100 ml. of methanol, and 10 g. of methylamine hydrochloride .
was~added. The mixture was heated under reflu~ for 16 hours, and was then concentrated under vacuum. The residue was takén up in chloroform, and washed with water and with dilute hydrochloric acid. The solution was then passed over ~ ~ .
; X-4097K
~ ? ~ ~ ~
-~ ~7S~
a silica ~3el chromato~raphic column, and eluted with 1:1 benzene/ethyl ~cetate. The product-containing fr~ctions were combined and evaporated to dryness under vacuum. I'he residue was triturated with hexane and recrystallized to obtain 0.4 g. of the product named above, m.p. 155-157C.
The following exemplary compounds were made by processes essentially similar to Example 80 above.
Example 81 l-methyl-3-(2-methylphenyl)-5-(3-trifluoromethyl-phenyl)-4(lfl)-pyridone, m.p. 144-147C., yield S~
Example 82 -l-methyl-3-(4-methylphenyl)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, m.p. 154-156C., yield 6 Example 83 5-(3-methoxycarbonylphenyl)-1-methyl-3-(4-methyl-phenyl)-4(lH)-pyridone, m.p. 85-88C., yield 5% ~ ;
Example 84 5-(3-methoxycarbonylpheny1)-1-methyl-3-(3-methylphenyl)-4(lH)-pyridone, m.p. 180-183C., yield 1~ -Example 85 3-methoxy-1-methyl-S-(3~trifluoromethylphenyl)-4(1H)-pyridone, m.p. 173-175C., yield 18 Example 86 3-(4-bromophenyl)-1-methyl-5-(3-methylphenyl)-. :
4(1H)-pyridone, m.p. 201-204C., yield 21 Example 87 3-(3j4-dichlorophenyl)-1-methyl-5-(3-trifluoro-methylph~enyl)-4(1H)-pyridone, ~.p. 109-112C., yield 4~ ;~
:. :
X-4097K ~-, ~ .:
:
.
,, , - - , , : . ...
6~7 Example 88 3,5-bis(3,5-dichlorophenyl)-1-methyl-4(1 pyridone, m.p. 275-278C., yield 14 E:xample 89 3-(3,4-dichlorophenyl)-1-methyl-5-(3-methyl-phenyl)-4(lH)-pyridone, mass spectrometry MI, 342, yield 10%
Example 90 -.
3-(3,4-dichlorophenyl)-5-(3,4-dimethylphenyl)- -l-methyl-4(1H)-pyridones~ m.p. 150-152C., yield 6%
.
Exampl _91 3-(3-chlorophenyl)-1-methyl-5-(2-methylphenyl)-4(1H)-pyridone, m.p. 171 173C., yield 12%
Example 92 3-(4-bromophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, m.p. 144-146C., yield 30~ -The following compound was produced by refluxing the compound above in 60% sulfuric acid.
~, Example 93 3-(4-bromophenyl)-5-(3-carboxyphenyl)-1-methyl-4(lH)-pyridone, m.p. 259-263C., yield 50%
The ~ollowing compounds were made by the process of Example 80.
Example 94 ; 3-(3-chlorophenyl)-1-methyl-5-(4-trifluoromethyl-phenyl)-4~(1H)-pyr1done, m.p. 147-151C., yield 2 Example 95 :: . .
3-(2-methylphenyl)-5-(4-methylphenyl)-1-methyl-4(lH)-pyr1done, m.p. 151-154C.l yield 6%
X-40~/K
, :
:
$~ 7S6g~7 Example 96 3-(3-mcthyl~)henyl)-5-(4-methylpherlyl)-1-methyL-4(111)-~yridone, m.p. 155-157C., yield 28%
Example 97 3-(2-chlorophen~ 5-(2-methylphenyl)-1-methyl-4(lH)-pyridone, m.p. 87-91C., yield 1 - Example 98 l-methyl-3j5-bis(4-methylphenyl)-4(1H)-pyridone, m.p. 212-214C., yield 3%
10Example 99 1 methyl-3-(3-chlorophenyl)-5-(3,4-dichloro-phenyl)-4(1H)-pyr1done, m.p. 107-110C., yield 10% ;
Example 100 l-methyl-3-(3,4-dichlorophenyl~-5-(2-methyl-phenyl)-4(lH)-pyridone, m.p. 103-106C., yield 10 .: ..
Example 101 l-methyl-3-(2-chlorophenyl)-5-(3,4-dichloro-phenyl)-4(lH)-pyridone, m.p. 169-171C., yield 25 ~: .
Example 102 201-methyl-3-(3-bromophenyl)-5-(3,4-dichlorophenyl)-4(1H)-pyridone,~m.p. 152-154C., yield 10~ ;
Example 103 ethyl-3-(3,5-dichlorophenyl)-5-(3-trifluoro- ;~-~
methylphenyl)-4(1H)-pyridone, m.p. I56-160C~, yiel~ 30 Example 104 methyl-3-(3-bromophenyl)-s-(3-methylphenyl) 4~(1H)-pyridone~, m.p. 144-147C., yield 3%
:
30 ~
;; . :
-. ., :
~7S697 .
Example 105 1-methyl-3,5-bis(3-methylphenyl)-4(lH)-pyridone, m.p. 148-150C., yield 8%
Example 106 l-methyl-3-(3-fluorophenyl)-5-(2,5-dimethyl-phenyl)-4(lH)-pyridone, mass spectroscopy MI, 307, yield 10 Example_107 3-(3-bromophenyl)-1-methyl-S-(2-methylphenyl)-4(1H)-pyridone, mass spectroscopy MI, 353, yield 2 Example_108 3-(3-bromophenyl)~5-(2-chlorophenyl)-1-methyl~
4(lH)-pyridone, m.p. 177-179C., yield 10 Example 109 3-(2-bromophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, m.p. 197-199C., yield 15%
Example 110 ~-3-(2,3~dimethoxyphenyl)--1-methyl~5~(3-trifluoro-methylphenyl)-4(lH)-pyridone, m.p. 153-155C., yield 20%
Example-lll .
3-(2~methoxyphenyl)-1-methyl-5-(3-trifluoromethyl~
phenyl)-4(lH)-pyridone, m.p. 193~196C., yield 10 Example 112 . .: . . .
3-(2~ethylphenyl)~1-methyl-5-(3-trifluoromethyl- ;
: ~ phenyl?:-4 (lH)-pyridone, m.p. 123-125C., yield 15~ :
Example 113 3-(3-bromo-4-methylp~enyl)-1-methyl-5-(3-tri-fluoromethylphenyl)-4~lH)~pyridone~ m.p. 158-161C., yield 30%
.
~: , . .
, ;~
. . ..
: ~ ~ : '' ' , .. :
:, . ~ ~ . . .
~L~;37S6~37 :
Example 114 3-(3-ethoxy-4-methoxyphenyl)-1-methyl-5-(3-tri-fluoromethylphenyl)-4(1ll)-pyridone, mass spectroscopy MI, 403, yield 10~ -Example 115 3~ hydroxyethyl)-1-methyl-5-(3-trifluoromethyl~
phenyl)-4(lH)-pyridone, mass spectroscopy MI, 297, yield 1~ -Example 116 3-~1-methoxyethyl)-1-methyl-5-(3-trifluoromethyl- ;
10phenyl)-4(lH)-pyridone, mass spectroscopy MI, 311, yield 1%
The following preparation and example illustrates the preparation of compounds of formula I by a variation of -the process in which a propanone of formula IV is formylated, exchanged with an amine, and formylated again to form the pyridone of formula I. `:~
Preparation 3 2,4-bis(3-trifluoromethylphenyl~-1-m thylamino- `
l-buten-3-one ~ A mixture of 2.2 g. of 1,3-bis(3-trlfluoromethyl- ;
2G phenyl)-2-propanone was combined with 1 g. of sodium methoxide -. . ~
in 50 ml. of methyl formate. The mixture was allowed to ~ ~`
stand overnight at room temperature, and was then evaporated to~dryness under vacuum. To the residue was added 3 g. of ethylamine hydrochloride as an aqueous solution. The solution was extracted with ethyl acetate, and the extract ~ -was evaporated~to dryness. ~ ~
~ : .
Example 117 l-ethyl-3,5-bis(3-tr~fluoromethylphenyl~-4(1H)-pyridone ,, , ., ...
~7S6~7 The L)roduct from Preparation 3 was treated with sodium methoxide and ethyl formate as described in Prep-aration 3. After the reaction mixture had been allowed to stand for four hours, it was evaporated to dryness and treated again with ethylamine hydrochloride in water as described in Preparation 3. The reaction mixture was then extracted with ethyl acetate and crystallized by addition of hexane to obtain 0.85 g. of the above named product, m.p.
185C.
The following preparation and example illustrates the synthesis of compounds of formula I by the reaction with an amine of a co~pound of formula II wherein Ql is an aminoformyl group and Q2 is a formyl group.
Preparation 4 l-diethylamino-5-hydroxy-4-ethoxy-2-~3-trifluoro-methylphenyl)-1,4-pentadien-3-one An enamine was formed by the process of Prep-aration 1 from 4.86 g. of N-diethyl-3-trifluoromethylstyryl- ~;
amine and 2.44 g. of ethoxyacetyl chloride. To the enamine -`
20 in 75 ml. of tetrahydrofuran at 0C. was added 3.2 g. of sodium methoxlde and 4.4 g. of ethyl formate. The mixture was stirred for 3 hours to prepare the above-named inter-mediate compound.
Example 118 l-methyl-3-ethoxy-5-(3-trifluoromethylphenyl)-4(lH-)-pyridone The product solution from Preparation 4 was com-.
~b1ned with 50 ml. of 40%~aqueous methylamine, and 5 g. of methylamine hydrochloride. The solution was stirred over-4~
X-4097K ~3~_ ~ .
~75697 :~
night at room temperature, and was then evaporated td dryness under vacuum. The residue was taken up in dichloromethane, washed with water and dried over magnesium sulfate. The sol~tion was filtered, and the dark residue was tritura-ted in cold isopropyl ether. The product was recrystalli~ed from isopropyl ether/dichloromethane to obtain 1.6 g. of the desired product, m.p. 131-133C.
The next group of examples demonstrates the preparation of compounds of formula I by a variation of the process wherein a compound of formula II wherein one of and Q2 represents an aminoformyl group wherein the amino substituent is Y, is reacted with a formylating agent to prepare the desired product.
, Preparation 5 l-methylamino-2-(4-chloro-3-trifluoromethyl-phenyl)-4-phenoxy-1-buten-3-one An acylated enamine was prepared according to the process of Preparation 1 from 5.6 g. of 4-chloro-3-tri- '~`
f1uoromethyl-N-diethylstyrylamine and 3.4 g. of phenoxy-acetyl chloride. The resulting acylated enamine of formula -VI was suspended in 100 ml. of ethanol and treated with ;~
50 ml. of 40X aqueous methylamine. The reaction mixture was stirred for 30 minutes, and was then concentrated under vacuum. The concentrated residue was taken up in 600 ml. of :. . .
~ diethyl ether, washed with water and dried over magnesium . . .
~sulfate. The reaction mixture was then evaporated to dryness.
: ~ ' . ' ' : ' -: ',.' x-4097~ _~p ~ ?
~ . ....... ..
~7~j~917 Example 119 l-methyl-3-(4-chloro-3-trifluoromethylphenyl)-5-phenoxy-4(lil)-pyridone The product of Preparation 5 was taken up in 100 ml. of dichloromethane, and 50 ml. of ethyl forma-te and 10 g. of sodium methoxide were added. 'rhe reaction mixture was stirred for 40 minutes, 5 g. of add:itional sodium methoxide was added~ and the mixture was stirred for 16 hours. The solution was then washed with dilute hydro-chloric acidj with dilute sodium hydroxide, and with sat-urated sodium chloride solution. It was then dried over . :, magnesium sulfate and evaporated under vacuum to give 6 g.
of an oil. The oil was purified by chromatography over silica gel, eluting with 1:1 ethyl acetate/toluene. The yield was 2.06 g. of the product named above, m.p. 130-131C.
.
The following exemplary compounds were made according to the process described in Example 119 above.
Example 120 methyl-3-allylthio-5-(3-trifluoromethylphenyl~-~20 ~4(1H)-pyridone, m.p. 74-75C., yield 5%
. .
Example 121 1-methyl-3-methoxy-5-phenyl-~4(lH)-pyridone, m.p. :
153-155C., yield 10%
The~following example illustrates the variation of the process wherein the compound of formula I is formed by .
the reaction with an aminoformylating agent of a compound of ~ ;
formula II wherein Ql is an aminoformyl group, substituted , with the group Y.
-~ X-4d9~7K -~3 : : . ~ :
.
~75~97 Example 122 l-~ethyl-3-(1-methylbutylthio)-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone A portion of l-methylamino-4-(1-methylbutylthio)-2 (3-trifluoromethylphenyl)-1-buten-3-one was prepared . , .
according to the process of Preparation 5. To the inter- -mediate, in 150 ml. of toluene was added 5 ml. of dimethyl-formamide dimethyl acetal, and the mixture was heated at reflux for 24 hours. The reaction mixture was then evap-orated to an oil under vacuum, the oil was purified by chromatography, and the purified product was found to be 1.5 g., about 10%, of the product named above, a liquid, i~entified by mass spectroscopy by which the molecular ion was found to be 355.
~he following exemplary compounds were made by the ;~
same synthetic scheme used for Example 122.
Example 123 3-(2-hydroxypropyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, m.p. 99-102C., yield 10%
Example 124 . .
l-methyl-3-(2-methyl-2-propenylthio)-5-(3-tri-fluoromethylphenyl)-4(lH)-pyridone, m.p. 86-88C., yield 10%
Example 125 --: .: . ,.
~ 3-ethylthio-5-(2-chloro-5-trifluoromethylphenyl)- ~
.
l-methyl-4(IH)-pyridonej m.p. 127-129C., yield 15~ i Exam~le 126 3-(2-chloro-5-trifluoromethylphenyl)-1-methyl-.
5-phenyl-4(1~)-pyridone, m.p. 150-152C., yield 30 ~ ~ 47 : !
, ".
~75~
~xample 127 3-(2-chloro-5-trifluoromethylphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, NMR peaks, a multiplet at 8.0-7.2 ppm; a singlet at 3.57 ppm, yield 40 The following group of examples illustrate the preparation of compounds of formula I by the reaction of an ~:
amine of the formula YNH2 with an intermediate of formula II
wherein one of Ql ïs a formyl group, and the other is an aminoformyl group.
Preparation 6 l-diethylamino-5-hydroxy-2-phenyl-4-(3-trifluoro-methylphenyl)-1,4-pentadien-3-one A 10 g. portion of 1-hydroxy-4-phenyl-2-(3-trifluoromethylphenyl)-l-buten-3-one, made according to the process of Preparation 3, was combined with an excess of dimethylformamide diethyl acetal and heated under reflux for 12 hours. The reaction mixture was then cooled, and con-centrated under vacuum to obtain the above-named inter-mediate.
~ Example 128 ~
l-hydroxy-3-phenyl-5-(3-trifluoromethylphenyl)-4(lHj-pyridone The intermediate rom Preparation 6 was dissolved in ethanol and combined with 10 g. of hydroxyamine hydro-chlorlde. The mixture was heated under reflux for 6 hours, and cooled, whereupon the product crystalIized. It was filtered away from the reaction mixture and recrystallized from ethanol/hexane to obtain 2.0 g. of the above-named ~: :
product, m.p. 240-243C. ~ ~-~ ~ -, ~
'' ' ' , ~ .
,' 1~37S69~
The followin~ examples were made a~corciirl-J to tl~
proccss of ~Xample 128.
~xam~le 129 3-(3-carboxyphenyl)-1-methyl-5-phenyl-4(lH)-pyridone, m-.p. 265-267C., yieid 1 The following compound was made according to the process shown in Example 128, and then esterified.
Example 130 . .
l-acetoxy-3-phenyl-5-t3-trifluoromethylphenyl)-4(lH)-pyridone, m.p. 232-235C., yield 5~
The followin~ cJroups of examples demonstrate the prep.iration of yyridinethiones.
Example 131 i :
l-methyl-3-(3-bromophenyl)-5-phenyl-4(1H)-pyridinethione ,:
A 5 ~. portion of 1-methyl-3-(3-bromophenyl)- ~ -5-phenyl-4(lH)-pyridone was combined with 5 y. of phosphorus pentasulfide in pyridine, and heated under reflux for 2 hours. The mIxture was then poured slowly into water and 20 filtered. The solids were air dried and crystallized ~rom ;
ethanol to obtain 3.1 ~. o~ th~ above-named product, m.p.
85 188~C.
Example~132 -l-methyl-3-(4-chIorophenyl)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridinethione, m.p. 239-242C., yield 25 Example 133 ~ 1-methyl-3-(3-methylphenyl)-5-(3-trifluoromethyl-phen~ 4(1H)-pyridinethione, m.p. 193-196C., yield 50%
~: , , .
~30 :
:~ ,, l . . . .
., ' ' '. . ' . .. ,. .- . .~, . ~ .,, .. . : , ... . . .
. . . . . ~ ............ . . . . . . . . ... .
~75~7 ~::
,, .;
Example 134 l-methyl-3-(2~methylphenyl)-5-(3-trifluoromethyl-phenyl)-4 (lEI) -pyridinethione, m.p. 193-195~C., yield 35%
Example 135 l-methyl-3-propyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridinethione, m.p. 145-148C., yield 40~ -Example 136 ~ -l-methyl-3-phenoxy-5-(3-trifluoromethylphenyl)-4(1H)-pyridinethione, m.p. 127-131C., yield 40%
10Example 137 3-ethylthio-1-methyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridinethione, m.p. 136-138C., yield 55%
Example 138 3-ethoxy-1-methyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridinethione~ m.p. 153-155C., yield 5% ~;
The compounds of Examples 80-138 are also made by the process of Example 1.
The compounds of Examples 1-79 and 117-138 are .
also made by the process of Example 80.
20The compounds of Examples 1-116 and 118-138 are also made by the process of Example 117.
The compounds of Examples 1-117 and 119-138 are also made by the process of Example 118. -The compounds of Example~ 1-118 and 122-138 are also made by~the process of Example 119.
: . , .- : . ,,, . :
The compounds of Examples 1-12i and 128-138 are also made by the process of Example 122.
The compounds of Examples 1-127 and 131-138 are ~also made by the process of Example 128.
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Compound application rates are expressed in kilo- -~grams of the compound per hectare of land (kg./ha.) through-out this speciEication and claims.
Blank spaces in the tables below indicate that the compound was not tested against the named species. In some .....
instances, the results of testing a compound repeatedly agaihst a plant species have been averaged.
Untreated control plants or plots were included in all tests. Ratings of the control produced by the compounds were made by comparison of the treated plants or plots with the controls.
In the tests, plants were rated on a 1-5 scale, on which 1 indicates normal plants and S indicates dead plants .
or no emergence.
~ Flat metal trays were filled with a sterilized sandy loam soil and were planted to seeds of the plants named in the table below. Each flat was individually fer-tilized.
.
Test compounds were applied postemergence to some flats and preemergence to others. Postemergence applica-tions of the compounds were sprayed aver the emerged plants ' : ' : ' '. .
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Each test compound was dissolved in 1:1 ace-tone:ethanol at the rate of 6 g. per 100 ml. The solution also contained about 2 g. per 100 ml. of an anionic-non-ionic surfactant blend. One ml. of the solution was diluted to 12 ml. with deionized water, and the resulting solution was applied ~o each flat ~o provide an application rate of 9.0 kg.jha. of test compoundO
After the compounds were applied, the pots were moved to the greenhouse, watered as necessary, and observed and rated about 10-13 days after application of the com-pounds. Untreated control plants were used as standards in every test.
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756~7 In another test, NATO rice and barnyard grass were seeded in large metal pots, and pyridone compounds were applied, according to three different methods. In all of th~ test methods, the compounds were formulated as 50 per-cent wettable powders.
A. The test compounds named below were incor-porated into the top 8 cm. of soil in the pots according to the application rates named in the table below. The rice ~
and b~rnyard grass seed were then planted 1.8-2.5 cm. deep. ~`
The~pots were watered daily until the rice plants were 5-8 cm. tall, and then 5-8 cm. of flood water was added to the pots and maintained throughout the test.
B. The pots were filled with soil, and barnyard grass seeds were planted as above. From 5 to 8 cm. of flood water was added to the pots, and rice seedlings were trans~
planted in;to the pots. The test compounds were sprayed over the water three days after the rice plants were transplanted.
C. The test compounds were incorporated into the ~-~top 8 cm. of soil, and ~arnyard grass seeds were planted 20 ~ 1.8-2.5 Gm. deep. From S to 8 cm. of flood water was then added to the pots, and rice seedlings were transplanted into the pots 5 days after treatment.
About 3 weeks after the tests were established, injury to the rice and control of the barnyard grass were measured on an~0-l~ scale where O indicates normal plants and 10 indicatea comp}ete kill. The results are shown in the table below.~
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~(~7569'7 Field tests against representative aquatic weeds were carried out in artificial ponds about 1 meter in diameter and 1/2 meter deep. The ponds contained a layer of earth at the bottom, and were filled with water. Represen~
tative aquatic weeds were planted in the ponds, and com-pounds of this invention were added at application rates named in the table below. The application rates were calculated as parts per million by weight of the total amount of water in each pond. Three weeks, 7 weeks and 12 weeks after the ponds were treated with the test compounds, the percent weed control of eàch species was measured, and -the control is reported in the table below as a mean of the three evaluations of each weed.
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Example 90 -.
3-(3,4-dichlorophenyl)-5-(3,4-dimethylphenyl)- -l-methyl-4(1H)-pyridones~ m.p. 150-152C., yield 6%
.
Exampl _91 3-(3-chlorophenyl)-1-methyl-5-(2-methylphenyl)-4(1H)-pyridone, m.p. 171 173C., yield 12%
Example 92 3-(4-bromophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, m.p. 144-146C., yield 30~ -The following compound was produced by refluxing the compound above in 60% sulfuric acid.
~, Example 93 3-(4-bromophenyl)-5-(3-carboxyphenyl)-1-methyl-4(lH)-pyridone, m.p. 259-263C., yield 50%
The ~ollowing compounds were made by the process of Example 80.
Example 94 ; 3-(3-chlorophenyl)-1-methyl-5-(4-trifluoromethyl-phenyl)-4~(1H)-pyr1done, m.p. 147-151C., yield 2 Example 95 :: . .
3-(2-methylphenyl)-5-(4-methylphenyl)-1-methyl-4(lH)-pyr1done, m.p. 151-154C.l yield 6%
X-40~/K
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$~ 7S6g~7 Example 96 3-(3-mcthyl~)henyl)-5-(4-methylpherlyl)-1-methyL-4(111)-~yridone, m.p. 155-157C., yield 28%
Example 97 3-(2-chlorophen~ 5-(2-methylphenyl)-1-methyl-4(lH)-pyridone, m.p. 87-91C., yield 1 - Example 98 l-methyl-3j5-bis(4-methylphenyl)-4(1H)-pyridone, m.p. 212-214C., yield 3%
10Example 99 1 methyl-3-(3-chlorophenyl)-5-(3,4-dichloro-phenyl)-4(1H)-pyr1done, m.p. 107-110C., yield 10% ;
Example 100 l-methyl-3-(3,4-dichlorophenyl~-5-(2-methyl-phenyl)-4(lH)-pyridone, m.p. 103-106C., yield 10 .: ..
Example 101 l-methyl-3-(2-chlorophenyl)-5-(3,4-dichloro-phenyl)-4(lH)-pyridone, m.p. 169-171C., yield 25 ~: .
Example 102 201-methyl-3-(3-bromophenyl)-5-(3,4-dichlorophenyl)-4(1H)-pyridone,~m.p. 152-154C., yield 10~ ;
Example 103 ethyl-3-(3,5-dichlorophenyl)-5-(3-trifluoro- ;~-~
methylphenyl)-4(1H)-pyridone, m.p. I56-160C~, yiel~ 30 Example 104 methyl-3-(3-bromophenyl)-s-(3-methylphenyl) 4~(1H)-pyridone~, m.p. 144-147C., yield 3%
:
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;; . :
-. ., :
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Example 105 1-methyl-3,5-bis(3-methylphenyl)-4(lH)-pyridone, m.p. 148-150C., yield 8%
Example 106 l-methyl-3-(3-fluorophenyl)-5-(2,5-dimethyl-phenyl)-4(lH)-pyridone, mass spectroscopy MI, 307, yield 10 Example_107 3-(3-bromophenyl)-1-methyl-S-(2-methylphenyl)-4(1H)-pyridone, mass spectroscopy MI, 353, yield 2 Example_108 3-(3-bromophenyl)~5-(2-chlorophenyl)-1-methyl~
4(lH)-pyridone, m.p. 177-179C., yield 10 Example 109 3-(2-bromophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, m.p. 197-199C., yield 15%
Example 110 ~-3-(2,3~dimethoxyphenyl)--1-methyl~5~(3-trifluoro-methylphenyl)-4(lH)-pyridone, m.p. 153-155C., yield 20%
Example-lll .
3-(2~methoxyphenyl)-1-methyl-5-(3-trifluoromethyl~
phenyl)-4(lH)-pyridone, m.p. 193~196C., yield 10 Example 112 . .: . . .
3-(2~ethylphenyl)~1-methyl-5-(3-trifluoromethyl- ;
: ~ phenyl?:-4 (lH)-pyridone, m.p. 123-125C., yield 15~ :
Example 113 3-(3-bromo-4-methylp~enyl)-1-methyl-5-(3-tri-fluoromethylphenyl)-4~lH)~pyridone~ m.p. 158-161C., yield 30%
.
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Example 114 3-(3-ethoxy-4-methoxyphenyl)-1-methyl-5-(3-tri-fluoromethylphenyl)-4(1ll)-pyridone, mass spectroscopy MI, 403, yield 10~ -Example 115 3~ hydroxyethyl)-1-methyl-5-(3-trifluoromethyl~
phenyl)-4(lH)-pyridone, mass spectroscopy MI, 297, yield 1~ -Example 116 3-~1-methoxyethyl)-1-methyl-5-(3-trifluoromethyl- ;
10phenyl)-4(lH)-pyridone, mass spectroscopy MI, 311, yield 1%
The following preparation and example illustrates the preparation of compounds of formula I by a variation of -the process in which a propanone of formula IV is formylated, exchanged with an amine, and formylated again to form the pyridone of formula I. `:~
Preparation 3 2,4-bis(3-trifluoromethylphenyl~-1-m thylamino- `
l-buten-3-one ~ A mixture of 2.2 g. of 1,3-bis(3-trlfluoromethyl- ;
2G phenyl)-2-propanone was combined with 1 g. of sodium methoxide -. . ~
in 50 ml. of methyl formate. The mixture was allowed to ~ ~`
stand overnight at room temperature, and was then evaporated to~dryness under vacuum. To the residue was added 3 g. of ethylamine hydrochloride as an aqueous solution. The solution was extracted with ethyl acetate, and the extract ~ -was evaporated~to dryness. ~ ~
~ : .
Example 117 l-ethyl-3,5-bis(3-tr~fluoromethylphenyl~-4(1H)-pyridone ,, , ., ...
~7S6~7 The L)roduct from Preparation 3 was treated with sodium methoxide and ethyl formate as described in Prep-aration 3. After the reaction mixture had been allowed to stand for four hours, it was evaporated to dryness and treated again with ethylamine hydrochloride in water as described in Preparation 3. The reaction mixture was then extracted with ethyl acetate and crystallized by addition of hexane to obtain 0.85 g. of the above named product, m.p.
185C.
The following preparation and example illustrates the synthesis of compounds of formula I by the reaction with an amine of a co~pound of formula II wherein Ql is an aminoformyl group and Q2 is a formyl group.
Preparation 4 l-diethylamino-5-hydroxy-4-ethoxy-2-~3-trifluoro-methylphenyl)-1,4-pentadien-3-one An enamine was formed by the process of Prep-aration 1 from 4.86 g. of N-diethyl-3-trifluoromethylstyryl- ~;
amine and 2.44 g. of ethoxyacetyl chloride. To the enamine -`
20 in 75 ml. of tetrahydrofuran at 0C. was added 3.2 g. of sodium methoxlde and 4.4 g. of ethyl formate. The mixture was stirred for 3 hours to prepare the above-named inter-mediate compound.
Example 118 l-methyl-3-ethoxy-5-(3-trifluoromethylphenyl)-4(lH-)-pyridone The product solution from Preparation 4 was com-.
~b1ned with 50 ml. of 40%~aqueous methylamine, and 5 g. of methylamine hydrochloride. The solution was stirred over-4~
X-4097K ~3~_ ~ .
~75697 :~
night at room temperature, and was then evaporated td dryness under vacuum. The residue was taken up in dichloromethane, washed with water and dried over magnesium sulfate. The sol~tion was filtered, and the dark residue was tritura-ted in cold isopropyl ether. The product was recrystalli~ed from isopropyl ether/dichloromethane to obtain 1.6 g. of the desired product, m.p. 131-133C.
The next group of examples demonstrates the preparation of compounds of formula I by a variation of the process wherein a compound of formula II wherein one of and Q2 represents an aminoformyl group wherein the amino substituent is Y, is reacted with a formylating agent to prepare the desired product.
, Preparation 5 l-methylamino-2-(4-chloro-3-trifluoromethyl-phenyl)-4-phenoxy-1-buten-3-one An acylated enamine was prepared according to the process of Preparation 1 from 5.6 g. of 4-chloro-3-tri- '~`
f1uoromethyl-N-diethylstyrylamine and 3.4 g. of phenoxy-acetyl chloride. The resulting acylated enamine of formula -VI was suspended in 100 ml. of ethanol and treated with ;~
50 ml. of 40X aqueous methylamine. The reaction mixture was stirred for 30 minutes, and was then concentrated under vacuum. The concentrated residue was taken up in 600 ml. of :. . .
~ diethyl ether, washed with water and dried over magnesium . . .
~sulfate. The reaction mixture was then evaporated to dryness.
: ~ ' . ' ' : ' -: ',.' x-4097~ _~p ~ ?
~ . ....... ..
~7~j~917 Example 119 l-methyl-3-(4-chloro-3-trifluoromethylphenyl)-5-phenoxy-4(lil)-pyridone The product of Preparation 5 was taken up in 100 ml. of dichloromethane, and 50 ml. of ethyl forma-te and 10 g. of sodium methoxide were added. 'rhe reaction mixture was stirred for 40 minutes, 5 g. of add:itional sodium methoxide was added~ and the mixture was stirred for 16 hours. The solution was then washed with dilute hydro-chloric acidj with dilute sodium hydroxide, and with sat-urated sodium chloride solution. It was then dried over . :, magnesium sulfate and evaporated under vacuum to give 6 g.
of an oil. The oil was purified by chromatography over silica gel, eluting with 1:1 ethyl acetate/toluene. The yield was 2.06 g. of the product named above, m.p. 130-131C.
.
The following exemplary compounds were made according to the process described in Example 119 above.
Example 120 methyl-3-allylthio-5-(3-trifluoromethylphenyl~-~20 ~4(1H)-pyridone, m.p. 74-75C., yield 5%
. .
Example 121 1-methyl-3-methoxy-5-phenyl-~4(lH)-pyridone, m.p. :
153-155C., yield 10%
The~following example illustrates the variation of the process wherein the compound of formula I is formed by .
the reaction with an aminoformylating agent of a compound of ~ ;
formula II wherein Ql is an aminoformyl group, substituted , with the group Y.
-~ X-4d9~7K -~3 : : . ~ :
.
~75~97 Example 122 l-~ethyl-3-(1-methylbutylthio)-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone A portion of l-methylamino-4-(1-methylbutylthio)-2 (3-trifluoromethylphenyl)-1-buten-3-one was prepared . , .
according to the process of Preparation 5. To the inter- -mediate, in 150 ml. of toluene was added 5 ml. of dimethyl-formamide dimethyl acetal, and the mixture was heated at reflux for 24 hours. The reaction mixture was then evap-orated to an oil under vacuum, the oil was purified by chromatography, and the purified product was found to be 1.5 g., about 10%, of the product named above, a liquid, i~entified by mass spectroscopy by which the molecular ion was found to be 355.
~he following exemplary compounds were made by the ;~
same synthetic scheme used for Example 122.
Example 123 3-(2-hydroxypropyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, m.p. 99-102C., yield 10%
Example 124 . .
l-methyl-3-(2-methyl-2-propenylthio)-5-(3-tri-fluoromethylphenyl)-4(lH)-pyridone, m.p. 86-88C., yield 10%
Example 125 --: .: . ,.
~ 3-ethylthio-5-(2-chloro-5-trifluoromethylphenyl)- ~
.
l-methyl-4(IH)-pyridonej m.p. 127-129C., yield 15~ i Exam~le 126 3-(2-chloro-5-trifluoromethylphenyl)-1-methyl-.
5-phenyl-4(1~)-pyridone, m.p. 150-152C., yield 30 ~ ~ 47 : !
, ".
~75~
~xample 127 3-(2-chloro-5-trifluoromethylphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, NMR peaks, a multiplet at 8.0-7.2 ppm; a singlet at 3.57 ppm, yield 40 The following group of examples illustrate the preparation of compounds of formula I by the reaction of an ~:
amine of the formula YNH2 with an intermediate of formula II
wherein one of Ql ïs a formyl group, and the other is an aminoformyl group.
Preparation 6 l-diethylamino-5-hydroxy-2-phenyl-4-(3-trifluoro-methylphenyl)-1,4-pentadien-3-one A 10 g. portion of 1-hydroxy-4-phenyl-2-(3-trifluoromethylphenyl)-l-buten-3-one, made according to the process of Preparation 3, was combined with an excess of dimethylformamide diethyl acetal and heated under reflux for 12 hours. The reaction mixture was then cooled, and con-centrated under vacuum to obtain the above-named inter-mediate.
~ Example 128 ~
l-hydroxy-3-phenyl-5-(3-trifluoromethylphenyl)-4(lHj-pyridone The intermediate rom Preparation 6 was dissolved in ethanol and combined with 10 g. of hydroxyamine hydro-chlorlde. The mixture was heated under reflux for 6 hours, and cooled, whereupon the product crystalIized. It was filtered away from the reaction mixture and recrystallized from ethanol/hexane to obtain 2.0 g. of the above-named ~: :
product, m.p. 240-243C. ~ ~-~ ~ -, ~
'' ' ' , ~ .
,' 1~37S69~
The followin~ examples were made a~corciirl-J to tl~
proccss of ~Xample 128.
~xam~le 129 3-(3-carboxyphenyl)-1-methyl-5-phenyl-4(lH)-pyridone, m-.p. 265-267C., yieid 1 The following compound was made according to the process shown in Example 128, and then esterified.
Example 130 . .
l-acetoxy-3-phenyl-5-t3-trifluoromethylphenyl)-4(lH)-pyridone, m.p. 232-235C., yield 5~
The followin~ cJroups of examples demonstrate the prep.iration of yyridinethiones.
Example 131 i :
l-methyl-3-(3-bromophenyl)-5-phenyl-4(1H)-pyridinethione ,:
A 5 ~. portion of 1-methyl-3-(3-bromophenyl)- ~ -5-phenyl-4(lH)-pyridone was combined with 5 y. of phosphorus pentasulfide in pyridine, and heated under reflux for 2 hours. The mIxture was then poured slowly into water and 20 filtered. The solids were air dried and crystallized ~rom ;
ethanol to obtain 3.1 ~. o~ th~ above-named product, m.p.
85 188~C.
Example~132 -l-methyl-3-(4-chIorophenyl)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridinethione, m.p. 239-242C., yield 25 Example 133 ~ 1-methyl-3-(3-methylphenyl)-5-(3-trifluoromethyl-phen~ 4(1H)-pyridinethione, m.p. 193-196C., yield 50%
~: , , .
~30 :
:~ ,, l . . . .
., ' ' '. . ' . .. ,. .- . .~, . ~ .,, .. . : , ... . . .
. . . . . ~ ............ . . . . . . . . ... .
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Example 134 l-methyl-3-(2~methylphenyl)-5-(3-trifluoromethyl-phenyl)-4 (lEI) -pyridinethione, m.p. 193-195~C., yield 35%
Example 135 l-methyl-3-propyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridinethione, m.p. 145-148C., yield 40~ -Example 136 ~ -l-methyl-3-phenoxy-5-(3-trifluoromethylphenyl)-4(1H)-pyridinethione, m.p. 127-131C., yield 40%
10Example 137 3-ethylthio-1-methyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridinethione, m.p. 136-138C., yield 55%
Example 138 3-ethoxy-1-methyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridinethione~ m.p. 153-155C., yield 5% ~;
The compounds of Examples 80-138 are also made by the process of Example 1.
The compounds of Examples 1-79 and 117-138 are .
also made by the process of Example 80.
20The compounds of Examples 1-116 and 118-138 are also made by the process of Example 117.
The compounds of Examples 1-117 and 119-138 are also made by the process of Example 118. -The compounds of Example~ 1-118 and 122-138 are also made by~the process of Example 119.
: . , .- : . ,,, . :
The compounds of Examples 1-12i and 128-138 are also made by the process of Example 122.
The compounds of Examples 1-127 and 131-138 are ~also made by the process of Example 128.
~ 30 ~ ~ ~ 5~
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~7~697 ,.., ",,~ . . , The compounds described above have been tested in a number of herbicidal test systems to determine the range of their herbicidal efficacy. The outs-tanding results produced by the compounds in the representative tests reported below are exemplary of the outstanding activity of the compounds.
Compound application rates are expressed in kilo- -~grams of the compound per hectare of land (kg./ha.) through-out this speciEication and claims.
Blank spaces in the tables below indicate that the compound was not tested against the named species. In some .....
instances, the results of testing a compound repeatedly agaihst a plant species have been averaged.
Untreated control plants or plots were included in all tests. Ratings of the control produced by the compounds were made by comparison of the treated plants or plots with the controls.
In the tests, plants were rated on a 1-5 scale, on which 1 indicates normal plants and S indicates dead plants .
or no emergence.
~ Flat metal trays were filled with a sterilized sandy loam soil and were planted to seeds of the plants named in the table below. Each flat was individually fer-tilized.
.
Test compounds were applied postemergence to some flats and preemergence to others. Postemergence applica-tions of the compounds were sprayed aver the emerged plants ' : ' : ' '. .
,:
sl .:
. . ': : .
:'"
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about 12 days after the seeds were planted. Preemer(J~nce applications were sprayed on the soil the day a r ter thc~
seeds were planted.
Each test compound was dissolved in 1:1 ace-tone:ethanol at the rate of 6 g. per 100 ml. The solution also contained about 2 g. per 100 ml. of an anionic-non-ionic surfactant blend. One ml. of the solution was diluted to 12 ml. with deionized water, and the resulting solution was applied ~o each flat ~o provide an application rate of 9.0 kg.jha. of test compoundO
After the compounds were applied, the pots were moved to the greenhouse, watered as necessary, and observed and rated about 10-13 days after application of the com-pounds. Untreated control plants were used as standards in every test.
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756~7 In another test, NATO rice and barnyard grass were seeded in large metal pots, and pyridone compounds were applied, according to three different methods. In all of th~ test methods, the compounds were formulated as 50 per-cent wettable powders.
A. The test compounds named below were incor-porated into the top 8 cm. of soil in the pots according to the application rates named in the table below. The rice ~
and b~rnyard grass seed were then planted 1.8-2.5 cm. deep. ~`
The~pots were watered daily until the rice plants were 5-8 cm. tall, and then 5-8 cm. of flood water was added to the pots and maintained throughout the test.
B. The pots were filled with soil, and barnyard grass seeds were planted as above. From 5 to 8 cm. of flood water was added to the pots, and rice seedlings were trans~
planted in;to the pots. The test compounds were sprayed over the water three days after the rice plants were transplanted.
C. The test compounds were incorporated into the ~-~top 8 cm. of soil, and ~arnyard grass seeds were planted 20 ~ 1.8-2.5 Gm. deep. From S to 8 cm. of flood water was then added to the pots, and rice seedlings were transplanted into the pots 5 days after treatment.
About 3 weeks after the tests were established, injury to the rice and control of the barnyard grass were measured on an~0-l~ scale where O indicates normal plants and 10 indicatea comp}ete kill. The results are shown in the table below.~
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~(~7569'7 Field tests against representative aquatic weeds were carried out in artificial ponds about 1 meter in diameter and 1/2 meter deep. The ponds contained a layer of earth at the bottom, and were filled with water. Represen~
tative aquatic weeds were planted in the ponds, and com-pounds of this invention were added at application rates named in the table below. The application rates were calculated as parts per million by weight of the total amount of water in each pond. Three weeks, 7 weeks and 12 weeks after the ponds were treated with the test compounds, the percent weed control of eàch species was measured, and -the control is reported in the table below as a mean of the three evaluations of each weed.
, .
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.
:30 X,4097K
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t~i . - ' , .
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S69~7 ~
The outstanding broad-spectrum activity of the compounds of Formula I is clearly illustrated by the above examples. The examples point up the efficacy of the compounds against annual grasses, the relatively easily-controlled broadleaves such as pigweed, and the more dif-ficult to kill broadleaves such as the nightshades, ragweed `~
and sicklepod. Further, the compounds control such peren-nial weeds as johnsongrass, quackgrass, bindweed, bermuda-grass and nutsedge, which are very difficult to control.
The compounds also control algae and aquatic weeds, such as - soontail, hydrilla and the like. Still further, the com-pounds kill such woody plants as mec;quite, which is an economicaily harmful weed in arid climates. Thus, plant scientists will recognize that the compounds can be used to control undesirable woody plants where such plants are not wanted. Plant scientists will recognize that the exempli-fied activity of the compounds shows that the compounds are effective against all types of weeds.
A preferred embodiment of the herbicidal method, however, is the use of the method to selectively kill herbaceous weeds.
Most unusually, the compounds are herbicidally effective when applied both preemergence and postemergence.
Thus, they can be applied to the soil to kill weeds by soil contact when the weed seeds are germinating and emerging, and can also be used to kill emerged weeds by direct contact with the exposed portions of the weedu When the compounds are~applied preemergence, the weeds are~killed either during germination or shortly after emergence.
~ ~J , X-4097K ~b~
~175~97 :
The compounds are effectively brought in-to contact with aquatic weeds by either suspending or dissolving the compound in the water in which the weeds grow, or by applying the compound to the sub-aqueous soil in which -the weeds are rooted.
Because of the outstanding efficacy of the com-pounds, a method of using the compounds for killing weeds is an important embodiment of the present invention. This embodiment is a method of selectively killin~ weeds which comprises contacting the weeds with an herbicidally-effective amount of one of the compounds described above.
In the context~of this invention, weed seeds, which are con-tacted wlth the compounds through preemergence applications o~ the compounds, are regarded as weeds.
Preemergence applications of the compounds are effective, as the examples show, whether the compounds are applied to the surface of the soil or are incorporated in , the soil.
As the examples above illustrate, many of the compounds are acceptably safe to~a number of crops, such as peanuts, soybean, sorghum, wheat and tree crops when applied at~proper rates and at appropriate times. It will be noted that the compoùnds are particularly and notably harmless to :
cotton. Because of the safety with which this crop may be treated with the compounds, the use of the method to kill weeds in ootton cropIand is a preferred embodiment of the ~ -invention. ~
- .
.
X-4097K ~ ~b~
- ~
'. -,:
. :, F~; ~ . . .
, ~.;; ' ~.~t75697 Observation of the data above shows that the compounds are also notably safe to rice. Accordingly, use of the method to kill weeds in rice cropland, and particularly in rice cropland in flooded transplant culture, is a pre-ferred embodiment of the invention.
The compounds can also be used, at appropriate application rates, for the total control of vegetation.
Such control is often desired, as for keeping cropland fallow for a time, or on industrial property and rights-of-way~ The compounds' ability to control perennial weeds and woody plants makes them particularly valuable total - vegetation control agents.
The method is notable for its ability selectively to kill weeds. The term weeds is not used here in a re-strictive sènse, but is used to refer broadly to undesired and undesirable plants. For example3 the method may be used in cotton cropland to kill not only plants which are un-desirable per se, such as johnsongrass and ragweed, but also volunteer crop plants which are undesirable in a cotton field. It wlll be understood that the proper application rates must be used to achieve selective control of weeds, as plant scientists are well aware.
. .
me proportion of the weed population which is killed by an application of one of the compounds depends upon the species of the weed and the identity and amount of the compound appIied. In many instances, of course, the . ~
~hole population is killed. In other instances, part of the ~ `
X-4097K -~a- ~ ~
'~ :
~7St~7 weeds are killed and part are lnjured, as some of the examples above illustrate. It will be understood that an application of one of the compounds is effective and bene-ficial, even though only part of the weed population is killed and another part of the population is injured. The - mere injury of a weed iB beneficial, because the surrounding crop, growing normally, shades out ~he slow-growing injured weed.
The be~t application rate of a given compound of the invention for the control of a given weed varies, of course, depending upon the method of compound application, cllmaté, sotl type, water and organic matker contents of the soil and other factors known to those ski~led in plant aience. It will be found, however, that the optimum application rate is in the range ~f from about 0.1 to about 20 kg./ha. in virtually every case. The optimum rates will u~ually be found to be within the preferred range of from about 0.1 to abo~t 5 kg./ha. Another preferred range, for .. . .
flooded~transplant rice cropland, is from about 0.025 to abo~t 2 kg./ha.
The time when the compounds should be applied to the soil or th~ weedg is widely variable, since the com-.
~pounds axe efective both preemergence and postemergence.
At least some control of weeds will result from application ~of~the c~mpounds at any ~time when weeds are growing or ge~-inating. They ma~ also be applied to the soil during a . .
dormant ~season to kill weeds germinatlng during the fol-low m g warm sea~son.
X-4097K~ -b4~
q. . , ':
:, ~ . . . , :
:' ' : ' ' : :- .
- . . . . ~ ~ ,.
~L~756~7 The compounds' efficacy against aquatic weeds is analogous to the efficacy against terrestrial weeds. The compounds are effective at the same rates of application described above in the general descripti.on oE the herbicidal method. Accordingly, the herbicidal met:hod of this inven-tion is effective against aquatic weeds, and is carried out in killing aquatic weeds in the same manner that it is used to kill weeds in general. :
When the compounds are used for weed control in an annual crop, it is usually best to apply a preemergence application of the compound to the soil at the time the crop is being~planted. If the compound is to be soil incorporated, it will usually be applied and incorporated immediately before planting. If it is to be surface applied, it is usually simplest to apply the compound immediately after ~
planting.
The compounds are applied to the soil or to.:: :
emerged weeds in the manners usual in agriculture. They may be applied to the soil in the form of.either water-dispersed :.
or granular formulations, the preparation of which will be discussed below. Usually, water-dispersed formulations will be used for the application of the compounds to emerged weeds. The formulAtions are applied with.any of the many :
types of sprayers and granular appl.icators which are in wide :
. use for the dlstribution of agricultural chemicals over soil : :
or standing vegetation, When a compound is to be soil-incor- .~
~ ,; . . .
porated, any of the usual soil incorporation equipment, such ..
. .
: : 7~' X-4097K : -b-,~
, 1~)7S69~ -as the disc harrow, the power-driven rotary hoe and the like, are effective.
The compounds are normally used in the practice of the method of this invention in the form of the herbicidal compositions which are an important embodiment of the in-vention. An herbicidal composition of this invention com-prises a compound of the invention and an inert carrier. In general, the compositions are formulated in the manners usual in agricultural chemistry, and are novel only because of the vital presence of the novel herbicidal compound.
Very often, the compounds are formulated as con-centrated compositions which are applied either to the soil or the foliage in the form of water dispersions or emulsions containing in the range of from about 0.1 percent to about 5 :
percent of the compound. Water-dispersible or emulsifiable compositions are either solids usually known as wettable powders, or liquids usually k~own as emulsifiable concen-: . .
trates. Wettable powders comprise an intimate, finely-divided mixture of the compound, an inert carrier and sur-: 2a factants. The concentration of the compound is usually from about 10 percent to about 90 percent. The inert carrier is usually chosen from among the attapulgite clays, the kaolin clays, the montmorillonite clays, the diatomaceous earths or ~-~
~;~ the purified silicates. Effective surfactants, comprising ~;
rom about 0.5 percent to about 10 percent of the wettable powder, are found among the sulfonated lignins, the con-densed naph~halenèsul~onates, the naphthalenesulfonates, the 3d ::
;~ ~ ;X-4097K
. ~ ~
'' ' ~ ; `~':,.
~75~9~7 alkylbenzenesulfonates, the alkyl sulfates and nonionic sur-factants such as ethylene oxide adducts of phenol.
Typical emulsifiable concentrates of the new com-pounds comprise a convenient concentration of the compound, such as from about 100 to about 500 g. per liter of liquid, dissolved in an inert carrier which is a mixture of water-lmmiscible solvent and emulsifiars. Useful organic solvents include the aromatics, especially the xylenes, and the petroleum fractions, especially the high-boiling naphthalenic and olefinic portions of petroleumO Many other organic solvents may also be used such as the terpenic solvents, and the complex alcohols such as 2-ethoxyethanol. Suitable emul~ifiers for emulsifiable concentrates are chosen from the same types of surfactants used ~or wettable powders.
A special type of emulslfiable concentrate com-position is used to form invert emulsions. Such emulsions have the aqueous phase dispersed in the oil phase, and have been used for some years in the agricultural chemical industry. They are particularly useful in postemergent and aquat1c applications of the compounds, since they adhere very well to foliage, and do not rapidly disperse in water.
Thus, by slmple ad~ustment of the density, an invert emul-sion can be accurately placed at the top or bottom of a body of water. Invert emulsion compositlons usually include an inverting oil, a mixture of solvents and surfactan s specially balanced t~ make invert emulsions when combined with water.
See U.S. Patent 3,197/229.
:: '' X-4d97K~
.' .
~' :
. , . , ... : ... . . :
69~
Another special type of composition which can be useful for application to water, as for flooded rice or aquatic weed applications, is one which forms a hydrophobic film. Such a composition, when applied to water, tends to spread itself evenly over the water surface, thereby achieving even application of the herbicide, despite any inaccuracy in applying the composition. Such compositions are usually based on a hydrophobic Iiquid, such as xylene, for example, in whlch the herbicide is dissolved or suspended.
~ When a compound is to be applied to the soil, as for a preemergence application of the compound, it is con-venient to use a granular formulation. Such a formulation , . :.
typically comprises the compound dispersed on a granular inert carrier such as coarsely ground clay. The particle size of granules usually ranges from about 0.1 to about 3 mm. The usual formulation process for granules comprises dissolving the compound in an inexpensive solvent and applying the solution to the carrier in an appropriate solids mixer. Somewhat less economically, the compound may be dispersed in a dough composed of damp clay or other inert ; ~ ~ carrier, which is then dried and coarsely ground to produce the desired granular product. Granules are also particu-larly useful in aquatic weed applications.
It has become customary in agricultural chemistry to apply two or even morè agricultural chemicals simul-taneously in ordsr to control weeds of many different types, or;~weeds;and o her pests, with a single appliaation of chem-icàls. The compounds of this invention lend themselves X-4097K~ b~
` ~75~;97 well to combination with other a~ricultural chemicals and may use~ully be combined with insecticides, fun~icides, nematicides and other herbicides as may be desirable and convenient.
'` ' .
. :
:. . .
'' ' -:
~ , "~',, - '~
, .. .
::: .
:~ .
:, : . . . .. . . -, , .: ~:
,, ,:, . ... . . ... . . ... . .. ... . . ...... ...
X-40~97K ~
j, . : : .
; ~ .
.., ~ . . ~ ....... ` . . . . . . . . . . .
S69~7 ~
The outstanding broad-spectrum activity of the compounds of Formula I is clearly illustrated by the above examples. The examples point up the efficacy of the compounds against annual grasses, the relatively easily-controlled broadleaves such as pigweed, and the more dif-ficult to kill broadleaves such as the nightshades, ragweed `~
and sicklepod. Further, the compounds control such peren-nial weeds as johnsongrass, quackgrass, bindweed, bermuda-grass and nutsedge, which are very difficult to control.
The compounds also control algae and aquatic weeds, such as - soontail, hydrilla and the like. Still further, the com-pounds kill such woody plants as mec;quite, which is an economicaily harmful weed in arid climates. Thus, plant scientists will recognize that the compounds can be used to control undesirable woody plants where such plants are not wanted. Plant scientists will recognize that the exempli-fied activity of the compounds shows that the compounds are effective against all types of weeds.
A preferred embodiment of the herbicidal method, however, is the use of the method to selectively kill herbaceous weeds.
Most unusually, the compounds are herbicidally effective when applied both preemergence and postemergence.
Thus, they can be applied to the soil to kill weeds by soil contact when the weed seeds are germinating and emerging, and can also be used to kill emerged weeds by direct contact with the exposed portions of the weedu When the compounds are~applied preemergence, the weeds are~killed either during germination or shortly after emergence.
~ ~J , X-4097K ~b~
~175~97 :
The compounds are effectively brought in-to contact with aquatic weeds by either suspending or dissolving the compound in the water in which the weeds grow, or by applying the compound to the sub-aqueous soil in which -the weeds are rooted.
Because of the outstanding efficacy of the com-pounds, a method of using the compounds for killing weeds is an important embodiment of the present invention. This embodiment is a method of selectively killin~ weeds which comprises contacting the weeds with an herbicidally-effective amount of one of the compounds described above.
In the context~of this invention, weed seeds, which are con-tacted wlth the compounds through preemergence applications o~ the compounds, are regarded as weeds.
Preemergence applications of the compounds are effective, as the examples show, whether the compounds are applied to the surface of the soil or are incorporated in , the soil.
As the examples above illustrate, many of the compounds are acceptably safe to~a number of crops, such as peanuts, soybean, sorghum, wheat and tree crops when applied at~proper rates and at appropriate times. It will be noted that the compoùnds are particularly and notably harmless to :
cotton. Because of the safety with which this crop may be treated with the compounds, the use of the method to kill weeds in ootton cropIand is a preferred embodiment of the ~ -invention. ~
- .
.
X-4097K ~ ~b~
- ~
'. -,:
. :, F~; ~ . . .
, ~.;; ' ~.~t75697 Observation of the data above shows that the compounds are also notably safe to rice. Accordingly, use of the method to kill weeds in rice cropland, and particularly in rice cropland in flooded transplant culture, is a pre-ferred embodiment of the invention.
The compounds can also be used, at appropriate application rates, for the total control of vegetation.
Such control is often desired, as for keeping cropland fallow for a time, or on industrial property and rights-of-way~ The compounds' ability to control perennial weeds and woody plants makes them particularly valuable total - vegetation control agents.
The method is notable for its ability selectively to kill weeds. The term weeds is not used here in a re-strictive sènse, but is used to refer broadly to undesired and undesirable plants. For example3 the method may be used in cotton cropland to kill not only plants which are un-desirable per se, such as johnsongrass and ragweed, but also volunteer crop plants which are undesirable in a cotton field. It wlll be understood that the proper application rates must be used to achieve selective control of weeds, as plant scientists are well aware.
. .
me proportion of the weed population which is killed by an application of one of the compounds depends upon the species of the weed and the identity and amount of the compound appIied. In many instances, of course, the . ~
~hole population is killed. In other instances, part of the ~ `
X-4097K -~a- ~ ~
'~ :
~7St~7 weeds are killed and part are lnjured, as some of the examples above illustrate. It will be understood that an application of one of the compounds is effective and bene-ficial, even though only part of the weed population is killed and another part of the population is injured. The - mere injury of a weed iB beneficial, because the surrounding crop, growing normally, shades out ~he slow-growing injured weed.
The be~t application rate of a given compound of the invention for the control of a given weed varies, of course, depending upon the method of compound application, cllmaté, sotl type, water and organic matker contents of the soil and other factors known to those ski~led in plant aience. It will be found, however, that the optimum application rate is in the range ~f from about 0.1 to about 20 kg./ha. in virtually every case. The optimum rates will u~ually be found to be within the preferred range of from about 0.1 to abo~t 5 kg./ha. Another preferred range, for .. . .
flooded~transplant rice cropland, is from about 0.025 to abo~t 2 kg./ha.
The time when the compounds should be applied to the soil or th~ weedg is widely variable, since the com-.
~pounds axe efective both preemergence and postemergence.
At least some control of weeds will result from application ~of~the c~mpounds at any ~time when weeds are growing or ge~-inating. They ma~ also be applied to the soil during a . .
dormant ~season to kill weeds germinatlng during the fol-low m g warm sea~son.
X-4097K~ -b4~
q. . , ':
:, ~ . . . , :
:' ' : ' ' : :- .
- . . . . ~ ~ ,.
~L~756~7 The compounds' efficacy against aquatic weeds is analogous to the efficacy against terrestrial weeds. The compounds are effective at the same rates of application described above in the general descripti.on oE the herbicidal method. Accordingly, the herbicidal met:hod of this inven-tion is effective against aquatic weeds, and is carried out in killing aquatic weeds in the same manner that it is used to kill weeds in general. :
When the compounds are used for weed control in an annual crop, it is usually best to apply a preemergence application of the compound to the soil at the time the crop is being~planted. If the compound is to be soil incorporated, it will usually be applied and incorporated immediately before planting. If it is to be surface applied, it is usually simplest to apply the compound immediately after ~
planting.
The compounds are applied to the soil or to.:: :
emerged weeds in the manners usual in agriculture. They may be applied to the soil in the form of.either water-dispersed :.
or granular formulations, the preparation of which will be discussed below. Usually, water-dispersed formulations will be used for the application of the compounds to emerged weeds. The formulAtions are applied with.any of the many :
types of sprayers and granular appl.icators which are in wide :
. use for the dlstribution of agricultural chemicals over soil : :
or standing vegetation, When a compound is to be soil-incor- .~
~ ,; . . .
porated, any of the usual soil incorporation equipment, such ..
. .
: : 7~' X-4097K : -b-,~
, 1~)7S69~ -as the disc harrow, the power-driven rotary hoe and the like, are effective.
The compounds are normally used in the practice of the method of this invention in the form of the herbicidal compositions which are an important embodiment of the in-vention. An herbicidal composition of this invention com-prises a compound of the invention and an inert carrier. In general, the compositions are formulated in the manners usual in agricultural chemistry, and are novel only because of the vital presence of the novel herbicidal compound.
Very often, the compounds are formulated as con-centrated compositions which are applied either to the soil or the foliage in the form of water dispersions or emulsions containing in the range of from about 0.1 percent to about 5 :
percent of the compound. Water-dispersible or emulsifiable compositions are either solids usually known as wettable powders, or liquids usually k~own as emulsifiable concen-: . .
trates. Wettable powders comprise an intimate, finely-divided mixture of the compound, an inert carrier and sur-: 2a factants. The concentration of the compound is usually from about 10 percent to about 90 percent. The inert carrier is usually chosen from among the attapulgite clays, the kaolin clays, the montmorillonite clays, the diatomaceous earths or ~-~
~;~ the purified silicates. Effective surfactants, comprising ~;
rom about 0.5 percent to about 10 percent of the wettable powder, are found among the sulfonated lignins, the con-densed naph~halenèsul~onates, the naphthalenesulfonates, the 3d ::
;~ ~ ;X-4097K
. ~ ~
'' ' ~ ; `~':,.
~75~9~7 alkylbenzenesulfonates, the alkyl sulfates and nonionic sur-factants such as ethylene oxide adducts of phenol.
Typical emulsifiable concentrates of the new com-pounds comprise a convenient concentration of the compound, such as from about 100 to about 500 g. per liter of liquid, dissolved in an inert carrier which is a mixture of water-lmmiscible solvent and emulsifiars. Useful organic solvents include the aromatics, especially the xylenes, and the petroleum fractions, especially the high-boiling naphthalenic and olefinic portions of petroleumO Many other organic solvents may also be used such as the terpenic solvents, and the complex alcohols such as 2-ethoxyethanol. Suitable emul~ifiers for emulsifiable concentrates are chosen from the same types of surfactants used ~or wettable powders.
A special type of emulslfiable concentrate com-position is used to form invert emulsions. Such emulsions have the aqueous phase dispersed in the oil phase, and have been used for some years in the agricultural chemical industry. They are particularly useful in postemergent and aquat1c applications of the compounds, since they adhere very well to foliage, and do not rapidly disperse in water.
Thus, by slmple ad~ustment of the density, an invert emul-sion can be accurately placed at the top or bottom of a body of water. Invert emulsion compositlons usually include an inverting oil, a mixture of solvents and surfactan s specially balanced t~ make invert emulsions when combined with water.
See U.S. Patent 3,197/229.
:: '' X-4d97K~
.' .
~' :
. , . , ... : ... . . :
69~
Another special type of composition which can be useful for application to water, as for flooded rice or aquatic weed applications, is one which forms a hydrophobic film. Such a composition, when applied to water, tends to spread itself evenly over the water surface, thereby achieving even application of the herbicide, despite any inaccuracy in applying the composition. Such compositions are usually based on a hydrophobic Iiquid, such as xylene, for example, in whlch the herbicide is dissolved or suspended.
~ When a compound is to be applied to the soil, as for a preemergence application of the compound, it is con-venient to use a granular formulation. Such a formulation , . :.
typically comprises the compound dispersed on a granular inert carrier such as coarsely ground clay. The particle size of granules usually ranges from about 0.1 to about 3 mm. The usual formulation process for granules comprises dissolving the compound in an inexpensive solvent and applying the solution to the carrier in an appropriate solids mixer. Somewhat less economically, the compound may be dispersed in a dough composed of damp clay or other inert ; ~ ~ carrier, which is then dried and coarsely ground to produce the desired granular product. Granules are also particu-larly useful in aquatic weed applications.
It has become customary in agricultural chemistry to apply two or even morè agricultural chemicals simul-taneously in ordsr to control weeds of many different types, or;~weeds;and o her pests, with a single appliaation of chem-icàls. The compounds of this invention lend themselves X-4097K~ b~
` ~75~;97 well to combination with other a~ricultural chemicals and may use~ully be combined with insecticides, fun~icides, nematicides and other herbicides as may be desirable and convenient.
'` ' .
. :
:. . .
'' ' -:
~ , "~',, - '~
, .. .
::: .
:~ .
:, : . . . .. . . -, , .: ~:
,, ,:, . ... . . ... . . ... . .. ... . . ...... ...
Claims (40)
1. A compound which is any of the following:
1-methyl-3-(3-nitrophenoxy)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-(4-methoxy-3-methylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 3-(3-bromo-4-methylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 1-methyl-3-(3-nitrophenyl)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 1-methyl-3-phenyl-5-(3-phenylthiophenyl)-4(1H)-pyridone, 1-methyl-3-phenyl-5-(3-phenylsulfonylphenyl)-4(1H)-pyridone, 3-(2-chloro-4-fluorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 3-(3,4-dimethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 3-(3,5-dimethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 3-(3-butylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 3-(2,5-dimethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 3-(2,4-dimethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 1-methyl-3-phenoxy-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 3-ethoxycarbonyl-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 1-methyl-3-(3-trifluoromethylphenyl)-5-phenyl-thio-4(1H)-pyridone, 3-(2,4-dichlorophenoxy)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 1-methyl-3-(2-thienyl)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-ethylthio-1-methyl-5-phenyl-4(1H)-pyridone, 3-ethylthio-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 3-ethylsulfonyl-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-ethylsulfinyl-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-(5-bromo-2-fluorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 1-methyl-3-(5-nitro-2-methylphenyl)-5-phenyl-4(1H)-pyridone, 3-cyano-5-(2,5-dimethoxyphenyl)-1-methyl-4(1H)-pyridone, 3-(2,6-dichlorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 3-ethoxycarbonyl-1-methyl-5-phenyl-4(1H)-pyridone, 1-methyl-3-propylthio-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 3-butylthio-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 1-methyl-3-methylthio-5-(3 trifluoromethylphenyl)-4(1H)-pyridone, 1-methyl-3-(3-trifluoromethylphenyl)-5-(4-tri-fluoromethylphenyl)-4(1H)-pyridone, 1-methyl-3-(3-trifluoromethylphenyl)-5-trifluoro-methylthio-4(1H)-pyridone, 3-(3,4-dimethoxyphenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-(5-fluoro-2-iodophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 3-(2-bromo-5-fluorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 3-benzylthio-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 3-(4-benzyloxyphenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 1,3-diethyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 3-(4-hydroxyphenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-(4-chloro-3-trifluoromethylphenyl)-5-ethoxy-1-methyl-4(1H)-pyridone, 1-methyl-3-isopropylthio-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-(4-chloro-3-trifluoromethylphenyl)-5-ethylthio-1-methyl-4(1H)-pyridone, 3-(4-chloro-3-trifluoromethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 3-(2,5-dimethylphenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-(3,5-dimethylphenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-(2,4-dichlorophenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 1-methyl-3-phenyl-5-(2-trifluoromethylphenyl)-4(1H)-pyridone, 1-methyl-3-(2-trifluoromethylphenyl)-5-(3-tri-fluoromethylphenyl)-4(1H)-pyridone, 3-(3,4-dimethylphenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-(3-iodophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-ethyl-1-methyl-5-(3-methoxyphenyl)-4(1H)-pyridone, 1-methyl-3-(3-iodophenyl)-5-phenyl-4(1H)-pyridone, 1-methyl-3-(4-methoxyphenoxy)-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 1-methyl-3-(2-chloro-4-fluorophenyl)-5-(3-tri-fluoromethylphenyl)-4(1H)-pyridone, 1-methyl-3-(4-chloro-3-trifluoromethylphenyl)-5-trifluoromethyl-4(1H)-pyridone, 1-methyl-3-(4-chloro-3-trifluoromèthylphenyl)-5-propyl-4(1H)-pyridone, 1-methyl-3-isopropylthio-5-(4-chloro-3-trifluoro-methylphenyl)-4(1H)-pyridone, 1-methy1-3-(4-chloro-3-trifluoromethylphenyl)-5 propylthio-4(1H)-pyridone, 1-methyl-3-(4-chloro-3-trifluoromethylphenyl)-5-(2-thienyl)-4(1H)-pyridone, 3-ethyl-1-methyl-5-(4-chloro-3-trifluoromethyl-phenyl)-4(1H)-pyridone, 1-methyl-3-(2,4-dimethylphenyl)-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-isopropoxy-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 1-methyl-3-(4-chlorophenoxy)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 1-methyl-3-(3-methylthiophenyl)-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 1-methyl-3-(3-methylsulfonylphenyl)-5-(3-tri-fluoromethylphenyl)-4(1H)-pyridone, 1-methyl-3-(3-trifluoromethylphenoxy)-5-(3-tri-fluoromethylphenyl)-4(1H)-pyridone, 3-(4-methoxyphenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-(2,3-dichlorophenoxy)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-(3,5-dichlorophenoxy)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-(3,4-dichlorophenoxy)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-(4-chloro-3-trifluoromethylphenyl)-1-methyl-5 isopropyl-4(1H)-pyridone, 3-(2,5-dichlorophenoxy)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 1-methyl-3-(4-methylthiophenoxy)-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-isobutylthio-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-t-butylthio-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-s-butylthio-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 1-methyl-3-(4-nitrophenoxy)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-ethyl-1-hydroxy-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 1-methyl-3-trifluoromethylsulfonyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 1-methyl-3-(3-trifluoromethylphenyl)-5-(3-tri-fluoromethylthiophenyl)-4(1H)-pyridone, 1-methyl-3-(3-trifluoromethylphenyl)-5-(3-tri-fluoromethylsulfonylphenyl)-4(1H)-pyridone, 1-methyl-3-(2,2,2-trifluoroethoxy)-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 1-methyl-3-(2-nitrophenyl)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 1-methyl-3-(3-methylphenyl)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 1-methyl-3-(2-methylphenyl)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 1-methyl-3-(4-methylphenyl)-5-(3-trif1uoromethyl-phenyl)-4(1H) pyridone, 5-(3-methoxycarbonylphenyl)-1-methyl-3-(4-methyl-phenyl)-4(1H)-pyridone, 5-(3-methoxycarbonylphenyl)-1-methyl-3-(3-methylphenyl)-4(1H)-pyridone, 3-methoxy-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 3-(4-bromophenyl)-1-methyl-5-(3-methylphenyl)-4(1H)-pyridone, 3-(3,4-dichlorophenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3,5-bis(3,5-dichlorophenyl)-1-methyl-4(1H)-pyridone, 3-(3,4-dichlorophenyl)-1-methyl-5-(3-methyl-phenyl)-4(1H)-pyridone, 3-(3,4-dichlorophenyl)-5-(3,4-dimethylphenyl)-1-methyl-4(1H)-pyridone, 3-(3-chlorophenyl)-1-methyl-5-(2-methylphenyl)-4(1H)-pyridone, 3-(4-bromophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-(4-bromophenyl)-5-(3-carboxyphenyl)-1-methyl-4(1H)-pyridone, 3-(3-chlorophenyl)-1-methyl-5-(4-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-(2-methylphenyl)-5-(4-methylphenyl)-1-methyl-4(1H)-pyridone, 3-(3-methylphanyl)-5-(4-methylphenyl)-1-methyl-4(1H)-pyridone, 3-(2-chlorophenyl)-5-(2-methylphenyl)-1-methyl-4(1H)-pyridone, 1-methyl-3,5-bis(4-methylphenyl)-4(1H)-pyridone, 1-methyl-3-(3-chlorophenyl)-5-(3,4-dichloro-phenyl)-4(1H)-pyridone, 1-methyl-3-(3,4-dichlorophenyl)-5-(2-methyl-phenyl)-4(1H)-pyridone, 1-methyl-3-(2-chlorophenyl)-5-(3,4-dichloro-phenyl)-4(1H)-pyridone, 1-methyl-3-(3-bromophenyl)-5-(3,4-dichlorophenyl)-4(1H)-pyridone, 1-methyl-3-(3,5-dichlorophenyl)-5-(3-trif1uoro-methylphenyl)-4(1H)-pyridone, 1-methyl-3-(3-bromophenyl)-5-(3-methylphenyl)-4(1H)-pyridone, 1-methyl-3,5-bis(3-methylphenyl)-4(1H)-pyridone, 1-methyl-3-(3-fluorophenyl)-5-(2,5-dimethyl-phenyl)-4(1H)-pyridone, 3-(3-bromophenyl)-1-methyl-5-(2-methylphenyl)-4(1H)-pyridone, 3-(3-bromophenyl)-5-(2-chlorophenyl)-1-methyl-4(1H)-pyridone, 3-(2-bromophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-(2,3-dimethoxyphenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-(2-methoxyphenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-(2-ethylphenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-(3-bromo-4-methylphenyl)-1-methyl-5-(3-tri-fluoromethylphenyl)-4(1H)-pyridone, 3-(3-ethoxy-4-methoxyphenyl)-1-methyl-5-(3-tri-fluoromethylphenyl)-4(1H)-pyridone, 3-(1-hydroxyethyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-(1-methoxyethyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 1-ethyl-3,5-bis(3-trifluoromethylphenyl)-4(1H)-pyridone, 1-methyl-3-ethoxy-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 1-methyl-3-(4-chloro-3-trifluoromethylphenyl)-5-phenoxy-4(1H)-pyridone, 1-methyl-3-allylthio-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 1-methyl-3-methoxy-5-phenyl-4(1H)-pyridone, 1-methyl-3-(1-methylbutylthio)-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-(2-hydroxypropyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 1-methyl-3-(2-methyl-2-propenylthio)-5-(3-tri-fluoromethylphenyl)-4(1H)-pyridone, 3-ethylthio-5-(2-chloro-5-trifluoromethylphenyl)-1-methyl-4(1H)-pyridone, 3-(2-chloro-5-trifluoromethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 3-(2-chloro-5-trifluoromethylphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 1-hydroxy-3-phenyl-5-(3 trifluoromethylphenyl)-4(1H)-pyridone, 3-(3-carboxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 1-acetoxy-3-phenyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 1-methyl-3-(3-bromophenyl)-5-phenyl-4(1H)-pyridinethione, 1-methyl-3-(4-chlorophenyl)-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridinethionel 1-methyl-3-(3-methylphenyl)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridinethione, 1-methyl-3-(2-methylphenyl)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridinethione, 1-methyl-3-propyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridinethione, 1-methyl-3-phenoxy-5-(3-trifluoromethylphenyl)-4(1H)-pyridinethione, 3-ethylthio-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridinethione, 3-ethoxy-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridinethione.
1-methyl-3-(3-nitrophenoxy)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-(4-methoxy-3-methylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 3-(3-bromo-4-methylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 1-methyl-3-(3-nitrophenyl)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 1-methyl-3-phenyl-5-(3-phenylthiophenyl)-4(1H)-pyridone, 1-methyl-3-phenyl-5-(3-phenylsulfonylphenyl)-4(1H)-pyridone, 3-(2-chloro-4-fluorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 3-(3,4-dimethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 3-(3,5-dimethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 3-(3-butylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 3-(2,5-dimethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 3-(2,4-dimethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 1-methyl-3-phenoxy-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 3-ethoxycarbonyl-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 1-methyl-3-(3-trifluoromethylphenyl)-5-phenyl-thio-4(1H)-pyridone, 3-(2,4-dichlorophenoxy)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 1-methyl-3-(2-thienyl)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-ethylthio-1-methyl-5-phenyl-4(1H)-pyridone, 3-ethylthio-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 3-ethylsulfonyl-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-ethylsulfinyl-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-(5-bromo-2-fluorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 1-methyl-3-(5-nitro-2-methylphenyl)-5-phenyl-4(1H)-pyridone, 3-cyano-5-(2,5-dimethoxyphenyl)-1-methyl-4(1H)-pyridone, 3-(2,6-dichlorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 3-ethoxycarbonyl-1-methyl-5-phenyl-4(1H)-pyridone, 1-methyl-3-propylthio-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 3-butylthio-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 1-methyl-3-methylthio-5-(3 trifluoromethylphenyl)-4(1H)-pyridone, 1-methyl-3-(3-trifluoromethylphenyl)-5-(4-tri-fluoromethylphenyl)-4(1H)-pyridone, 1-methyl-3-(3-trifluoromethylphenyl)-5-trifluoro-methylthio-4(1H)-pyridone, 3-(3,4-dimethoxyphenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-(5-fluoro-2-iodophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 3-(2-bromo-5-fluorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 3-benzylthio-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 3-(4-benzyloxyphenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 1,3-diethyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 3-(4-hydroxyphenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-(4-chloro-3-trifluoromethylphenyl)-5-ethoxy-1-methyl-4(1H)-pyridone, 1-methyl-3-isopropylthio-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-(4-chloro-3-trifluoromethylphenyl)-5-ethylthio-1-methyl-4(1H)-pyridone, 3-(4-chloro-3-trifluoromethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 3-(2,5-dimethylphenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-(3,5-dimethylphenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-(2,4-dichlorophenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 1-methyl-3-phenyl-5-(2-trifluoromethylphenyl)-4(1H)-pyridone, 1-methyl-3-(2-trifluoromethylphenyl)-5-(3-tri-fluoromethylphenyl)-4(1H)-pyridone, 3-(3,4-dimethylphenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-(3-iodophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-ethyl-1-methyl-5-(3-methoxyphenyl)-4(1H)-pyridone, 1-methyl-3-(3-iodophenyl)-5-phenyl-4(1H)-pyridone, 1-methyl-3-(4-methoxyphenoxy)-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 1-methyl-3-(2-chloro-4-fluorophenyl)-5-(3-tri-fluoromethylphenyl)-4(1H)-pyridone, 1-methyl-3-(4-chloro-3-trifluoromethylphenyl)-5-trifluoromethyl-4(1H)-pyridone, 1-methyl-3-(4-chloro-3-trifluoromèthylphenyl)-5-propyl-4(1H)-pyridone, 1-methyl-3-isopropylthio-5-(4-chloro-3-trifluoro-methylphenyl)-4(1H)-pyridone, 1-methy1-3-(4-chloro-3-trifluoromethylphenyl)-5 propylthio-4(1H)-pyridone, 1-methyl-3-(4-chloro-3-trifluoromethylphenyl)-5-(2-thienyl)-4(1H)-pyridone, 3-ethyl-1-methyl-5-(4-chloro-3-trifluoromethyl-phenyl)-4(1H)-pyridone, 1-methyl-3-(2,4-dimethylphenyl)-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-isopropoxy-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 1-methyl-3-(4-chlorophenoxy)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 1-methyl-3-(3-methylthiophenyl)-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 1-methyl-3-(3-methylsulfonylphenyl)-5-(3-tri-fluoromethylphenyl)-4(1H)-pyridone, 1-methyl-3-(3-trifluoromethylphenoxy)-5-(3-tri-fluoromethylphenyl)-4(1H)-pyridone, 3-(4-methoxyphenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-(2,3-dichlorophenoxy)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-(3,5-dichlorophenoxy)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-(3,4-dichlorophenoxy)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-(4-chloro-3-trifluoromethylphenyl)-1-methyl-5 isopropyl-4(1H)-pyridone, 3-(2,5-dichlorophenoxy)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 1-methyl-3-(4-methylthiophenoxy)-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-isobutylthio-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-t-butylthio-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-s-butylthio-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 1-methyl-3-(4-nitrophenoxy)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-ethyl-1-hydroxy-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 1-methyl-3-trifluoromethylsulfonyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 1-methyl-3-(3-trifluoromethylphenyl)-5-(3-tri-fluoromethylthiophenyl)-4(1H)-pyridone, 1-methyl-3-(3-trifluoromethylphenyl)-5-(3-tri-fluoromethylsulfonylphenyl)-4(1H)-pyridone, 1-methyl-3-(2,2,2-trifluoroethoxy)-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 1-methyl-3-(2-nitrophenyl)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 1-methyl-3-(3-methylphenyl)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 1-methyl-3-(2-methylphenyl)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 1-methyl-3-(4-methylphenyl)-5-(3-trif1uoromethyl-phenyl)-4(1H) pyridone, 5-(3-methoxycarbonylphenyl)-1-methyl-3-(4-methyl-phenyl)-4(1H)-pyridone, 5-(3-methoxycarbonylphenyl)-1-methyl-3-(3-methylphenyl)-4(1H)-pyridone, 3-methoxy-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 3-(4-bromophenyl)-1-methyl-5-(3-methylphenyl)-4(1H)-pyridone, 3-(3,4-dichlorophenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3,5-bis(3,5-dichlorophenyl)-1-methyl-4(1H)-pyridone, 3-(3,4-dichlorophenyl)-1-methyl-5-(3-methyl-phenyl)-4(1H)-pyridone, 3-(3,4-dichlorophenyl)-5-(3,4-dimethylphenyl)-1-methyl-4(1H)-pyridone, 3-(3-chlorophenyl)-1-methyl-5-(2-methylphenyl)-4(1H)-pyridone, 3-(4-bromophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-(4-bromophenyl)-5-(3-carboxyphenyl)-1-methyl-4(1H)-pyridone, 3-(3-chlorophenyl)-1-methyl-5-(4-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-(2-methylphenyl)-5-(4-methylphenyl)-1-methyl-4(1H)-pyridone, 3-(3-methylphanyl)-5-(4-methylphenyl)-1-methyl-4(1H)-pyridone, 3-(2-chlorophenyl)-5-(2-methylphenyl)-1-methyl-4(1H)-pyridone, 1-methyl-3,5-bis(4-methylphenyl)-4(1H)-pyridone, 1-methyl-3-(3-chlorophenyl)-5-(3,4-dichloro-phenyl)-4(1H)-pyridone, 1-methyl-3-(3,4-dichlorophenyl)-5-(2-methyl-phenyl)-4(1H)-pyridone, 1-methyl-3-(2-chlorophenyl)-5-(3,4-dichloro-phenyl)-4(1H)-pyridone, 1-methyl-3-(3-bromophenyl)-5-(3,4-dichlorophenyl)-4(1H)-pyridone, 1-methyl-3-(3,5-dichlorophenyl)-5-(3-trif1uoro-methylphenyl)-4(1H)-pyridone, 1-methyl-3-(3-bromophenyl)-5-(3-methylphenyl)-4(1H)-pyridone, 1-methyl-3,5-bis(3-methylphenyl)-4(1H)-pyridone, 1-methyl-3-(3-fluorophenyl)-5-(2,5-dimethyl-phenyl)-4(1H)-pyridone, 3-(3-bromophenyl)-1-methyl-5-(2-methylphenyl)-4(1H)-pyridone, 3-(3-bromophenyl)-5-(2-chlorophenyl)-1-methyl-4(1H)-pyridone, 3-(2-bromophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-(2,3-dimethoxyphenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-(2-methoxyphenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-(2-ethylphenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-(3-bromo-4-methylphenyl)-1-methyl-5-(3-tri-fluoromethylphenyl)-4(1H)-pyridone, 3-(3-ethoxy-4-methoxyphenyl)-1-methyl-5-(3-tri-fluoromethylphenyl)-4(1H)-pyridone, 3-(1-hydroxyethyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 3-(1-methoxyethyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 1-ethyl-3,5-bis(3-trifluoromethylphenyl)-4(1H)-pyridone, 1-methyl-3-ethoxy-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 1-methyl-3-(4-chloro-3-trifluoromethylphenyl)-5-phenoxy-4(1H)-pyridone, 1-methyl-3-allylthio-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 1-methyl-3-methoxy-5-phenyl-4(1H)-pyridone, 1-methyl-3-(1-methylbutylthio)-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone, 3-(2-hydroxypropyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone, 1-methyl-3-(2-methyl-2-propenylthio)-5-(3-tri-fluoromethylphenyl)-4(1H)-pyridone, 3-ethylthio-5-(2-chloro-5-trifluoromethylphenyl)-1-methyl-4(1H)-pyridone, 3-(2-chloro-5-trifluoromethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 3-(2-chloro-5-trifluoromethylphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 1-hydroxy-3-phenyl-5-(3 trifluoromethylphenyl)-4(1H)-pyridone, 3-(3-carboxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, 1-acetoxy-3-phenyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, 1-methyl-3-(3-bromophenyl)-5-phenyl-4(1H)-pyridinethione, 1-methyl-3-(4-chlorophenyl)-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridinethionel 1-methyl-3-(3-methylphenyl)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridinethione, 1-methyl-3-(2-methylphenyl)-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridinethione, 1-methyl-3-propyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridinethione, 1-methyl-3-phenoxy-5-(3-trifluoromethylphenyl)-4(1H)-pyridinethione, 3-ethylthio-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridinethione, 3-ethoxy-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridinethione.
2. The compound of Claim 1 which is 3-(4-chloro-3-trifluoromethylphenyl)-5-ethoxy-1-methyl-4(1H)-pyridone.
3. The compound of Claim 1 which is 1-methyl-3-(4-chloro-3-trifluoromethylphenyl)-5-propyl-4(1H)-pyridone.
4. The compound of Claim 1 which is 3-ethyl-l-methyl-5-(4-chloro-3-trifluoromethylphenyl)-4(1H)-pyridone.
5. The compound of Claim 1 which is 3-(4-chloro-3-trifluoromethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone.
6. The compound of Claim 1 which is 3-(2-chlorophenyl)-5-(3-chlorophenyl)-1-methyl-4(1H)-pyridone.
7. The compound of Claim 1 which is 3-(3-bromophenyl)-5-(3-chlorophenyl)-1-methyl-4(1H)-pyridone.
8. The compound of Claim 1 which is 3-(3-bromophenyl)-1-methyl-5-(2-methylphenyl)-4(1H)-pyridone.
9. The compound of Claim 1 which is 3-(3-chlorophenyl)-1-methyl-5-(2-methylphenyl)-4(1H)-pyridone.
10. The compound of Claim 1 which is 1-methyl-3,5-bis(3-methylphenyl)-4(1H)-pyridone.
11. The compound of Claim 1 which is 1-methyl-3-allylthio-5-(3-trifluoromethylphenyl)-4(1H)-pyridone.
12. The compound of Claim 1 which is 3-ethyl-sulfinyl-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone.
13. The compound of Claim 1 which is 1-methyl-3-(3-trifluoromethylphenyl)-5-trifluoromethylthio-4(1H)-pyridone.
14. The compound of Claim 1 which is 1-methyl-3-(2-chloro-4-fluorophenyl)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone.
15. The compound of Claim 1 which is 3-(2,5-dimethylphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone.
16. The compound of Claim 1 which is 3-(3,4 dimethylphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone.
17. The compound of Claim 1 which is 3-(2-bromophenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone.
18. The compound of Claim 1 which is 1-methyl-3-(2-methylphenyl)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone.
19. The compound of Claim 1 which is 3-(2-ethylphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone.
20. The compound of Claim 1 which is 1-methyl-3-(2-trifluoromethylphenyl)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone.
21. The compound of Claim 1 which is 3-(2-methoxyphenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone.
22. The compound of Claim 1 which is 3-(3-bromophenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone.
23. The compound of Claim 1 which is 1-methyl-3-(3-methylphenyl)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone.
24. The compound of Claim 1 which is 1-methyl-3-(4-methylphenyl)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone.
25. The compound of Claim 1 which is 1-methyl-3-propyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone.
26. The compound of Claim 1 which is 3-methoxy-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone.
27. The compound of Claim 1 which is 3-ethoxy-1-methyl-5-(3 trifluoromethylphenyl)-4(1H)-pyridone.
28. The compound of Claim 1 which is 3-isopro-poxy-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone.
29. The compound of Claim 1 which is 1-methyl-3-phenoxy-5-(3-trifluoromethylphenyl)-4(1H) pyridone.
30. The compound of Claim 1 which is 3-ethyl-thio-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone.
31. The compound of Claim 1 which is 1-methyl-3-propylthio-5-(3-trifluoromethylphenyl)-4(1H)-pyridone.
32. The compound of Claim 1 which is 1-methyl-3-isopropylthio-5-(3-trifluoromethylphenyl)-4(1H)-pyridone.
33. The compound of Claim 1 which is 1-methyl-3-(3-methylthiophenyl)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone.
34. The compound of Claim 1 which is 1,3-diethyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone.
35. The compound of Claim 1 which is 1-ethyl-3,5-bis(3-trifluoromethylphenyl)-4(1H)-pyridone.
36. The compound of Claim 1 which is 1-methyl-3-(3-trifluoromethylphenyl)-5-(3-trifluoromethylthiophenyl)-4(1H)-pyridone.
37. The compound of Claim 1 which is 1-methyl-3-(2,2,2-trifluoroethoxy)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone.
33. The compound of Claim 1 which is 3-isopropyl-1-methyl-5-(4-chloro-3-trifluoromethylphenyl)-4(1H)-pyridone.
39. The compound of Claim 1 which is 1-methyl-3-(3-trifluoromethylphenyl)-5-trifluoromethylthio-4(1H)-pyridone.
40. The compound of Claim 1 which is 3-(1-hydroxyethyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/810,219 US4152136A (en) | 1974-08-28 | 1977-06-27 | 3-Phenyl-5-substituted-4(1H)-pyridones(thiones) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1075697A true CA1075697A (en) | 1980-04-15 |
Family
ID=25203294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA305,980A Expired CA1075697A (en) | 1977-06-27 | 1978-06-22 | 3-phenyl-5-substituted-4(1h)-pyridones(thiones) |
Country Status (16)
| Country | Link |
|---|---|
| AT (1) | AT362613B (en) |
| BE (1) | BE868393A (en) |
| BG (4) | BG30168A4 (en) |
| CA (1) | CA1075697A (en) |
| FR (1) | FR2395996A2 (en) |
| GB (1) | GB2029403B (en) |
| GR (1) | GR70237B (en) |
| GT (1) | GT197852905A (en) |
| IE (1) | IE47202B1 (en) |
| IN (1) | IN149651B (en) |
| IT (1) | IT1113145B (en) |
| LU (1) | LU79873A1 (en) |
| MW (1) | MW1778A1 (en) |
| RO (3) | RO80037A (en) |
| ZA (1) | ZA783650B (en) |
| ZM (1) | ZM5878A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ197027A (en) * | 1980-05-12 | 1984-03-16 | Rohm & Haas | 4-oxo-2-phenyl-nicotinic acids salts and esters and growth regulating compositions |
| US4936904A (en) * | 1980-05-12 | 1990-06-26 | Carlson Glenn R | Aryl-4-oxonicotinates useful for inducing male sterility in cereal grain plants |
| US4714492A (en) * | 1980-05-12 | 1987-12-22 | Rohm And Haas Company | Certain 2-phenyl-4-oxo-nicotinates and their use for inducing male sterility in a cereal grain plant |
| EP0067511A3 (en) * | 1981-05-19 | 1983-04-06 | Imperial Chemical Industries Plc | Method of inducing tillering using pyridine derivatives, and some of the pyridines themselves, process for preparing them and agricultural compositions containing them |
| DE3531773A1 (en) * | 1985-09-06 | 1987-03-19 | Bayer Ag | 3.5 DISUBSTITUTED 4-PYRIDONE |
| GB9005518D0 (en) * | 1990-03-12 | 1990-05-09 | Wellcome Found | Heterocyclic compounds |
| US5403934A (en) * | 1990-03-12 | 1995-04-04 | Burroughs Wellcome Co. | Heterocyclic compounds |
| US5567698A (en) * | 1995-02-15 | 1996-10-22 | Bristol-Myers Squibb Company | Pyridinium thiomethyl substituted chepholosporin derivatives |
| WO2023232673A1 (en) * | 2022-06-01 | 2023-12-07 | Syngenta Crop Protection Ag | Herbicidal derivatives |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL47938A (en) * | 1974-08-28 | 1979-07-25 | Lilly Co Eli | 3-pjenyl-5-substituted-4(1h)-pyridones and pyridine thiones |
-
1975
- 1975-08-27 AT AT563277A patent/AT362613B/en not_active IP Right Cessation
-
1978
- 1978-03-31 MW MW17/78A patent/MW1778A1/en unknown
- 1978-05-25 IN IN567/CAL/78A patent/IN149651B/en unknown
- 1978-06-21 RO RO78102053A patent/RO80037A/en unknown
- 1978-06-21 RO RO78102054A patent/RO80699A/en unknown
- 1978-06-21 RO RO7894426A patent/RO75145A/en unknown
- 1978-06-22 FR FR7818746A patent/FR2395996A2/en active Granted
- 1978-06-22 CA CA305,980A patent/CA1075697A/en not_active Expired
- 1978-06-22 ZM ZM58/78A patent/ZM5878A1/en unknown
- 1978-06-23 BE BE1008944A patent/BE868393A/en not_active IP Right Cessation
- 1978-06-24 GR GR56592A patent/GR70237B/el unknown
- 1978-06-26 IT IT24972/78A patent/IT1113145B/en active
- 1978-06-26 GT GT197852905A patent/GT197852905A/en unknown
- 1978-06-26 IE IE1265/78A patent/IE47202B1/en unknown
- 1978-06-26 LU LU79873A patent/LU79873A1/xx unknown
- 1978-06-26 ZA ZA783650A patent/ZA783650B/en unknown
- 1978-06-27 BG BG7841633A patent/BG30168A4/en unknown
- 1978-06-27 BG BG7841632A patent/BG30176A4/en unknown
- 1978-06-27 BG BG7840220A patent/BG29870A3/en unknown
- 1978-06-27 BG BG7841631A patent/BG30175A4/en unknown
- 1978-09-01 GB GB7835305A patent/GB2029403B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| BG30175A4 (en) | 1981-04-15 |
| GR70237B (en) | 1982-09-01 |
| ZM5878A1 (en) | 1979-04-23 |
| IT7824972A0 (en) | 1978-06-26 |
| BE868393A (en) | 1978-12-27 |
| FR2395996B2 (en) | 1983-08-05 |
| RO80037A (en) | 1982-10-26 |
| ZA783650B (en) | 1980-02-27 |
| GB2029403B (en) | 1982-10-27 |
| AT362613B (en) | 1981-06-10 |
| GT197852905A (en) | 1979-12-18 |
| IT1113145B (en) | 1986-01-20 |
| LU79873A1 (en) | 1978-12-07 |
| IE47202B1 (en) | 1984-01-11 |
| RO80699A (en) | 1982-12-06 |
| IN149651B (en) | 1982-03-06 |
| GB2029403A (en) | 1980-03-19 |
| BG30176A4 (en) | 1981-04-15 |
| BG29870A3 (en) | 1981-02-16 |
| ATA563277A (en) | 1980-10-15 |
| FR2395996A2 (en) | 1979-01-26 |
| IE781265L (en) | 1978-12-27 |
| BG30168A4 (en) | 1981-04-15 |
| RO75145A (en) | 1981-01-30 |
| MW1778A1 (en) | 1979-05-09 |
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