CA1088543A - HERBICIDAL .beta.-PHENYL-4-PIPERIDINONES AND- DIHYDROPYRIDINONES - Google Patents

Abstract

Abstract of the Disclosure A class of 4-piperidinones and corresponding di-hydropyridinones having a phenyl substituent at one .beta.-position, an alkyl, alkenyl or propargyl group at the 1-position and an optional substituent at the other .beta.-position are broad-spectrum herbicides. The compounds bear a meta-substituent on the phenyl ring, and are particularly suited for use as herbicides in cotton culture. The novel com-pounds are prepared by reducing the corresponding 4(1H)-pyridinones.

Description

HER3ICIDAL ~-PHENYL-4-PIPERIDINONES
- AND -DIHYDROPYRIDINONES
This invention belongs to the field of agricultural chemistry, and provides to the art new herbicides and herbi-cidal methods.
It has long been established that herbicides are necessary to the most economical and productive use of the land. Herbicides are in demand for use in killing and con-trolling weeds growing in cropland, and also for killing and controlling unwanted vegetation of all kinds, such as in fallow land and on industrial property~
Despite the great amount of research effort which has been expended in agricultural chemistry, herbicides closely related to the compounds of formula (I), (II) or (III) have not been previously discovered. The polyhalo-pyridinones, which have two or more chlorin~ atoms as well as other alkyl and halo substituents on the pyridine rings, are known herbicides, but are obviously ~uite distant from the present novel compounds.
Organic chemists have explored the piperidinones and dihydropyridinones to a degree. For example, Leonard et al., J. Am. Chem. Soc. 79, 156-60 (1957), disclosed 3,5-di(substituted-benzyl and benzylidene)-4-piperidinones, which are not herbicides.
Settimj et al. have worked with piperidinones, and have disclosed the unsubstituted 3,5-diphenyl-1-methyl-4-piperidinone. Gazz. Chim. Ital. 96, 604-11 (1966), C.A. -65, 8913g (1966); Gazz. Chim. Ital. 96, 311-24 (1966), C.A. - -67, 64261b (1967); Gazz. Chim. Ital. 100, 703-25 (1970), C.A. 74, 41752t (1971).
_ 3 ~ `

A series of l-substituted ~-phenyl-4-piperidinones and -dihydropyridinones are herbicides active against a wide ~-range of weeds. Many of the compounds are new and are here disclosed for the first time. Herbicidal methods making use ~.
of the compounds, which are particularly useful in cotton culture, are also disclosed. -The novel compounds are of one of the general formulae :;:

\ ~ / \ R~

\ / , R ' '~f,''` ,"
.' ..
(I) (II) ~,~ .
wherein R i; methyl or ethyl;
R is ~
hydrogen, .

phenoxy, :
phenylthio, ~.-Cl-C4 alkoxy, :~.
Cl-C4 alkylthio, ~.
Cl-C4 alkyl, :
phenyl or phenyl monosubstituted with chloro or fluoro;
R2 is bromo, fluoro or trifluoromethyl;
R3 is Cl-C3 alkyl, C2-C3 alkenyl or propargyl;

~88543 R4 is `~
hydrogen, phenoxy, phenylthio, ~`~
Cl-C4 alkyl, ~ ~:
Cl-C4 alkoxy, Cl-C4 alkylthio, phenyl or ;.
phenyl monosubstituted with - -chloro, -~
bromo, fluoro, . ~-trifluoromethyl, :
Cl-C3 alkyl or ~' Cl-C3 alkoxy;

chloro, ~ ;
bromo, fluoro, trifluoromethyl, .
Cl-C3 alkyl or .
Cl-C3 alkoxy;
either X and Xl combine to form a carbon-carbon bond and x2 and X3 are hydrogen atoms, or X and Xl are hydrogen atoms and x2 and X3 combine to form a carbon-carbon bond.
: The novel compounds of formulae (I) and (II) are prepared by reducing a compound of one of the general formulae ~`

' 3543 - ~:
;; A
R2 ~ x,, ~ \f \~R~ 15~.~ f~b , .,~, .
i .~.. ~,.
.. . ~ . ...
(IV) (V) ~.
wherein the various symbols are defined as before with an 10 aluminium or boron hydride.
The herbicidal method for controlling noxious vegetation comprises applying to an area containing said noxious vegetation a compound of the general formula .

Re~ _ ' R ~.

wherein R6 is C}-C3 alkyl, C2-C3 alkenyl or propargyl; -~
:~ R is hydrogen, ~: -.,, ?
phenoxy, phenylthio, ..
Cl-C4 alkyl, ~........................................................................ . ..
Cl-C4 aIkoxy~
: Cl-C4 alkylthio, phe-nyl or ,. , . , ,, . _ .

10885~3 "

phenyl monosubstituted with chloro, bromo, fluoro, `
trifluoromethyl, -Cl-C3 alkyl or ~`.
Cl-C3 alkoxy;
R8 i5 ,.
chloro, -~
bromo, fluoro, `~ .
trifluoromethyl, .. .
Cl-C3 alkyl or Cl-C3 alkoxy; - :
. ~; .-. :
each of X4 and X5 is hydrogen, or X4 and ~ : .
XS combine to form a carbon-carbon bond;
each of x6 and X7 ls hydrogen, or x6 and ~ .
X7 comblne to form a carbon-carbon bonds provlded that no more than one of ~X4 and 20 X5) and (X6 and X7) form a bond. ~- -. In the above five formulae, the general chemlcal terms are u~ed ln thelr usual mean~ngs ln the : s organic chemical art~ For example, the terms Cl-C3 ..
Ii . I j ~ ~, . . alkoxy, Cl-C3 alkyl, Cl-C4 alkyl, Cl-C4 alkoxy~ Cl-C
alkylthio~and C2-C3 alkenyl refer to such groups as :-~
. methoxy, ethoxy, isopropoxy, methylthio, ethylthio, propylthio, methyl, ethyl, propyl, .
,~, ~ ... .. . .. . .. . . . . . . . . .

1~88$43 vinyl, allyl, l-propenyl, butyl, t-butyl, isobutyl, butoxy and isobutylthio. ;-Agricultural chemists will immediately under~tand ~-~
that the addition of commonly-used ~ubstituents to the -~
compounds of formula (I), (II) or (III) is e~pected to produce active compounds equivalent to those explicitly described herein. For example, such substituents as halogen `-atoms, Cl-C3 alkoxy, alkylthio and alkyl groups, and tri-fluoromethyl groups, as well as functional groups ~uch a~
hydroxy, alkoxycarbonyl and cyano groups, may be added to the compound~. In particular, the phenoxy and phenylthio `
Rl, R4 and R7 groups may be ~ub~tituted with such group~
particularly with halogen atom~, methyl and methoxy group~ ~
and trifluoromethyl groups, with the expectation of pro- . -ducing piperidinones and dihydropyridinones equivalent to the other compounds described herein.
It will al~o be understood that acid addition ~ -~alt~ of the compound~ of formulae ~I), tII) and (III) may be made and u~ed for the control of weed~. For example, 20 ~uch salts as hydrochlorides, hydrobromides, hydrofluorides, sulfate~, nitrate~, toluenesulfonates, methanesulfonatés, trifluoromethanesulfonates and the like are often used in agricultural chemistry. Salts of the compound~ of formulae (I), (II) and (III) are made in the usual manner by simple contact of the compound with the acid in a solvent ~uch a~ -an aqueous alçohol.
`~ It will be understood that the present invention *
may be practiced in various ways, making use of different ~ .

:~ X-4427A _j_ ~ `~ ' ' .

i~8~3 cla~ses of compounds of formula (I), (II) or (III). In such manners of practicing the invention, variou~ classes of compound~ may be u~ed in carrying out the herbicidal methods, and making use of the herbicidal composition~, of thi~
invention. For example, the following cla~ses of compounds are contemplated, as new compositions in the case of com-pounds of formulae (I) and ~ , and for use in herbicidal method~ and compositions in all cases.
l) Compounds of formula (I); .

2) compounds of formula (II);
compound~ of formula (I) wherein:
8) Rl iQ hydrogen, alkyl, phenyl or substituted phenyl;
4) Rl is hydrogen, phenoxy, phenylthio, phenyl or sub~tituted phenyl;
5) Rl is phenoxy, phenylthio, phenyl or sub-stituted phenyl;
6) Rl i~ hydrogen, alkyl, alkoxy or alkylthio;
7) Rl i~ alkyl, alkoxy or alkylthio;
8) Rl is hydrogen, alkoxy, alkylthio, alkyl, phenyl or sub~tituted phenyl;
compounds of formula (II) wherein: ~.
9) R is alkyl or alkenyl;
10) R3 is alkyl;
ll) R3 is alkenyl or propargyl;
12) R4 i~ slkyl, phenyl or ~ub~tituted phènyl;
13) R4 i8 hydrogen, phenoxy, phenylthio, phenyl ~:
or sub~tituted phenyl;
- -.

~ 35~3 14) R4 is phenoxy, phenylthio, phenyl or sub~
stituted phenyl;
15) R4 is hydrogen, alkyl, alkoxy or alkylthio;
16) R4 is alkyl, alkoxy or alkylthio;
17) R4 is hydrogen, alkyl, phenyl or phenyl ~;~
mono~ub~tituted with chloro, bromo, fluoro, ; :-trifluoromethyl, methyl or methoxy;
18) RS is chloro, bromo, fluoro, trifluoromethyl, ~ :
methyl or methoxy;
19) the compounds as de~cribed by subparagraphs 9 and 12; ~ .
20) the compounds as described by ~ubparagraphs 9 and 13; -,~
.. I ~, 21) the compounds as described by ~ubparagraph~ 9 ...
and 14; ~~' 22) the compounds as described by subparagrapho 9 and 15; i .
23) the compound~ a~ de~cribed by subparagraph~ 9 and 16;
24) the compounds as described by subparagraphs 9 . and 17; .
25) the compounds a~ described by ~ubparagraph~
10 and 12; .:
: : :
~ 26) the compounds as described by subparagraphs :: . 10 and 13; -.
27) the compounds aJ de~cribed by subparagr~phs ` ~ ` 10 and 14;
28) the compound~ as de-cribed by Jubparagraphs . - . 10 and lS;

~:` ` X-4427A -9- :
,~

- ' 1088~;43 29) the compounds as described by subparagraphs 10 and 16;
30) the compounds as described by subparagraphs 10 and 17;
31) the compounds as described by subparagraphs 11 and 12 32) the compounds as de~cribed by subparagraphs .
11 and 13;
33) the compounds as described by ~ubparagraph~
11 and 14; - .-34) the compound6 a~ described by subparagraph~ ;
11 and 15;
35) the compounds a~ described by subparagraphs 11 and 16;
36) the compounds as de~cribed by subparagraphJ
11 and 17; . :~ -37) the compounds as described by subparagraphs ~ ;
9, 12 and 18; :
38) the compounds as described by subparagraphs 9, 13 and 18; ~' 39) the compounds as described by ~ubparagraphs ~:~
9, 14 and 18;
40) the compounds as described by ~ubparagraph~ .
9, 15 and 18;
41) the compounds as described by subparagraphs --:`
9, 16 and 18; -42) the compounds a~ described by subparagraphs -~
~ 1 9, 17 and 18;
- :
, ~ . .
~ ~ X-4427A -10-~: `

~ - -.

~, ~88S43 43) the compounds a~ de~cribed by subparagraph~
10, 12 and 18;
- 44) the compounds a~ described by subparagraphs 10, 13 and 18;
45) the compounds as described by subparagraphs 10, 14 and 18;
46) the compounds as de~cribed by ~ubparagraphs 10, 15 and 18;
47) the compounds as described by subparagraphs < ~
10, 16 and 18; ~' 48) the compounds a~ described by subparagraphs 10, 17 and 18; ~:
49) the compounds as described by subparagraphs 11, 12 and 18; ~ .
50) the compounds as described by subparagraphs 11, 13 and 18;
.~
51) the compounds as described by ~ubparagraphs 11, 14 and 18;
52) the compounds as described by subparagraphs 11, 15 and 18;
53) the compound~ as desaribed by subparagraphs : .
11, 16 and 18;
54) the compounds as described by subparagraph~
11, 17 and 18;
h bicidal compositions u~ing compound~ of formula ~III) wherein:
. 55) X4, X5, x6 and X7 all are hydrogen atoms;
56) one of (X4 and X5) and.(X6 and X7) forms a : bond;
. ~ .
, .; ~
.: . :
~ ' :
. , .

1~88543 57) R6 iq alkyl or alkenyl; ;`
58) R6 i~ alkenyl or propargyl;
59) R6 i8 alkyl:
60) R7 is hydrogen, alkyl, phenyl or substituted phenyl;
61) R7 i~ hydrogen, alkyl, phenyl or phenyl monosubstituted with chloro, bromo, fluoro, trifluoromethyl, methyl or methoxy; .
62) R7 is hydrogen, phenoxy, phenylthio, phenyl or substituted phenyl;
63) R7 is phenoxy, phenylthio, phenyl or sub-stituted phenyl;
64) R7 i8 hydrogen, alkyl, alkoxy or alkylthio;
65) R7 i# alkyl, alkoxy or alkylthio; ~ :
66) R7 is alkyl, phenyl or phenyl substituted s with chloro or fluoroi :
67) R8 i~ chloro, bromo, fluoro, trifluoromethyl, methyl or methoxy; ~. `
68) the compound~ as described by subparagraphs r 55 and 57; ` :--69) the compounds as describea by subparagraph~
55 and 58;
70) the compound~ as described by ~ubparagraph~
55 and 59; :
71) the compounds as described by subparagraphs ~.
56 and 57;
72) the compounds as described by subparaqraphs .
` 56 and 58;
~ 73) the compounds as described by subparagraphs : ~ 56 and 59;

' , , lG885~3 74) the compound.~ a~ described by ~ubparagraphs ~ e 55 and 67;
. , 75) the compounds as described by subparagraphs 56 and 67;
76) the compounds as described by subparagraphs :- -55 and 60~
77) the compounds as described by ~ubparagraphs 55 and 61; ,~ :., ,, ~ .
78) the compounds as deJcribed by ~ubparagraphs .-~
55 and 62;
79) the compounds as described by 6ubparagraphJ
55 and 63;
80) the compound~ a~ described by ~ubparagraphs -~-55 and 64;
81) the compound~ a~ de~crlbed by subparagraphs '~
55 and 65; ~ ~! S,i~.`
'.
82) the compound~ a~ described by ~ubparagraph-55 and 665 ,~
83) the compound~ as de~cribed by ~ubparagraph~
56 and 60;
84) the compound~ as described by subparagraphs ~:: . 56 and 61; .:.
85) the compounds as described by ~ubparagraphs 56 and 62;
: ~ , ~ 86) the co~pounds as described by ~ubparagraph~ ;
~ -56 and 63; . . `.
. 87) the compounds a~ described by ~ubparagraphJ
56-a-nd. 64 X-4427A~ -13 lG13~5~3 88) the c~mpound~ a~ de~cribed by 6ubparagraphs 56 and 65:
89) the compound~ as described by subparagraph~
56 and 66;
90) the compounds as described by ~ubparagraphs 57 and 60; ' 91) the compounds as described by subparagraphs 57 and 61; ~ -9Z) the compound~ as described by subparagraphs ~ :
57 and 62; :.
93) the compounds as described by 8ubparagraphs 57 and 63; .
94) the compounds as described by subparagraphs 57 and 64; -~
95) the compounds as described by subparagraphs 57 and 65; .
96) the compounds as described by subparagraphs :' 57 and 66; `~
97) th~ compounds as described by subparagraphs 20. 58 and 60; .
98) the compounds a~ described by subparagraph~
58 and 61; -.,.
99) the compound~ as de~cribed by subparagraphs ~ :~
58 and 62:
100) the compounds a~ described by subparagraphs 58 and 63;
.101) the co~pound~ as described by ~ubparagraphs : 58 and 64; ~.
~: .

.~

' .
.
..

~, .

~ 088S~13 102) the compound~ a~ deJcribed by subparagraphs 58 and 65; -103) the compounds as described by subparagraph~ ;
58 and 66;
104) the compounds a~ described by ~ubparagraphs 59 and 60; ~ :
105) the compounds as de wribed by ~ubparagraphs 59 and 61;
106) the compounds as described by subparagraphs 59 and 62: ~ ;
107) the compounds as described by subparagraph~ ~ -59 and 63; ~.
108) the compounds as de~cribed by ~ubparagraph~
59 and 64;
109) the compound~ a~ de~cribed by ~ubparagraphs : 59 and 65; .
110) the compound~ as described by subparagraph~
59 and 66;
111) the ¢ompound~ as de~cribed by ~ubparagraphs 57 and 67;
112) the compound~ a~ described by ~ubparagrapb~
58 and 67;
113) the compound~ a~ described by ~ubparagraphs ~- 59 and 67;
114) the compound~ as de~cribed by ~ubparagraphs ~;-60 and 67J :
- 115) the compounds as described by ~ubparagraph~
, . - .
:~ ~ ! - 61 and 67;

~ ~ ~ X-4427A . -15- :
. . . .
, ~, -:
, ~', ' "_ , ...... ,. .. ,,,,, , . .. ,.. ~, . ,.,., , . - , , , . . .-,,, ., ,. . . ,..... ,; , ,-, - -

3 ~ ~
116) the compounds as described by ~ubparagraphs -62 and 67; ;
117) the compounds as described by subparagraphs . :~
63 and 67; ~r' 118) the compounds as de~cribed by subparagraphs 64 and 67; ~`
119) the compounds as described by subparagraphs 65 and 67;
120) the compounds as described by subparagraph~
66 and 67;
121) the compounds as described by subparagraphs 55, S7 and 60;
122) the compounds a~ described by ~ubparagraphs SS, 57 and 61;
123) the compounds as described by 3ubparagraphs 55, 57 and 62;
124) the compounds as described by 3ubparagraphs 5S, 57 and 63;
125) the compounds as described by subparagraphs - :~
55, 57 and 64; . :
126) the compounds as described by subparagraphs 55, 57 and 65;
127) the compounds as described by ~ubparagraph~
55, 57 and 66;
128) the compounds as described by subparagraph~
55, 58 and 60;
129) the compounds a~ described by subparagraphs - . . - .
55, 58 and 61; , .

: . -: X-4427A -16-1~85~3 130) the compounds a~ descrLbed by ~ubparagraphs 55, 58 and 62;
131) the compounds as described by subparagraph~
55, 58 and 63;
132) the compounds as described by subparagraphs 55, 58 and 64;
133) the compounds as described by ~ubparagraphs 55, 58 and 65;
134) the compounds as described by subparagraphs .
55, 58 and 66;
135) the compounds as described by subparagraphs 55, 59 and 60; -136) the compounds as described by ~ubparagraphs SS, 59 and 61;
137) the compounds as described by subparagraphs 55, 59 and 62; ~ ~
138) the compounds as described by ~ubparagraphs ~ -SS, S9 and 63;
139) the compounds as described by ~ubparagraphs 55, 59 and 64; ~ . . .:
140) the compounds as described by subparagraphs 55, 59 and 65;
141) the compounds as described by ~ubparagraphs 55, 59 and 66;
142) the compounds as described by subparagraphs ~`:
56, S7 and 60; :
143) the compounds as described by ~ubparagraphs 56, 57 and 61:

~ ' ~:~ X-4427A -17-: ' ~

~ ' .

.
~ .

1~885~3 144) the compound~ as described by aubpara~raphs 56, 57 and 62; - .
145) the compounds as described by subparagraphs -~.
56, 57 and 63;
146) the compounds as described by 6ubparagraph~
56, 57 and 64; ~
147) the compounds a~ described by ~ubparagraphs : ~.
56, 57 and 65;
148) the compounds as de~cribed by ~ubparagraphs 56, 57 and 66; . :
149) the compounds as described by subparagraph~ - :
56, 58 and 60; . ~;
150) the compound~ aQ de~cribed by ~ubparagraphs 56, 58 and 61; . ;~
. .
151) the compounds as de~cribed by subparagraphs 56, 58 and 62; .
152) the compounds as described by ~ubparagraph~ -.
56, 58 and 63; `
153) the compounds as described by subparagraph~
56, 58 and 64;
154) thé compounds as described by ~ubparagraphs ~ - -., S6, 58 and 65; ~ ' 155) the compound~ as described by ~ubparagraph~
;;. .
56, 58 and 66;
156) the compounds as described by aubparagrapha ~;
56, 59 and 60; .,.. ~
:-;
157) the compounds as described by ~ubparagraphs ~ ~:
: 56, S9 and 61; -~:~ X-4427A -18- - -.~
; . ~ ". .
~ -, ," ' :~ .
:.- ", 1i~88543 153) the compounds as described by ~ubparagraphs 56, S9 and 62;
159) the compounds as described by subparagraphs 56, 59 and 63; -160) the compounds as described by subparagraphs 56, 59 and 64;
161) the compounds as described by subparagraphs 56, S9 and 65;
162) the compounds as described by subparagraphs 1056, 59 and 66;
163) the compounds as described by subparagraphs S5, 57, 60 and 67;
164) the compounds as described by 3ubparagraphs 55, 57, 61 and 67;
165) the compounds as described by subparagraphs 55, 57, 62 and 67;
166) the compounds as described by subparagraphs 55, 57, 63 and 67;
167) the compounds as described by subparagraphs 2055, 57, 64 and 67;
168) the compounds as described by subparagraphs 55, 57, 65 and 67;
169) the compound~ as described by ~ubparagraphs 55, 57, 66 and 67; ;
170) the compounds as described by ~ubparagraph~ :
55, 58, 60 and 67;
171) the compounds as described by subparagraphs 55, 58, 61 and 67:

X-4427A -19- -.

1~88S43 172) the compounds as deqcribed by subparagraph~
55, 58, 62 and 67; ~~
173) the compounds as described by subparagraphs 55, 58, 63 and 67;
174~ the compounds as described by ~ubparagraphs 55, 58, 64 and 67;
175) the compounds as described by ~ubparagraphs 55, 58, 65 and 67; `
.
176) the compounds as described by subparagraphs 55, 58, 66 and 67;
177) the compounds as described by ~ubparagraphs 55, 59, 60 and 67; ~`
178) the compounds as described by ~ubparagraphs 55, 59, 61 and 67; `~
179) the compounds as described by subparagraph~
55, 59, 62 and 67; -180) the compounds as described by subparagraph~
~ t 55, 59, 63 and 67; ,'~ .
181) the compound~ a~ described by ~ubparagraphs 55, 59, 64 and 67; .- ~
182) the compound~ as described by subparagraphs j ,-55, 59, 65 and 67;
183) the compounds a~ described by subparagraph~ . .
SS, 59, 66 and 67;
184) the compounds a~ described by ~ubparagraph~
~,` :.. - .
!~' ' 56, 57, 60 and 67; .:
~: 185) the compounds as de~cribed by subparagraphs 56, 57, 61 and 67;

'~ :

~ .

186) the compounds as described by subparagraph~
56, 57, 62 and 67; ;:
187) the compounds as de~cribed by subparagraphs 56, 57, 63 and 67; -~
188) the compounds as described by ~ubparagraphs 56, 57, 64 and 67; ~-189) the compounds as described by subparagraphs ;~
56, 57, 65 and 67;
190) the compounds as described by subparagraphs 1056, 57, 66 and 67;
191) the compounds as described by Qubparagraphs 56, 58, 60 and 67;
192) the compounds as described by subparagraph~ ;
56, 58, 61 and 67; - `
193) the compounds as described by subparagraphs 56, 58, 62 and 67;
194) the compounds as described by subparagraphs . :~
56, 58, 63 and 67; .
195) the compounds as described by subparagraphs .,:;
2056, 58, 64 and 67;
196) the compounds as described by eubparagraphs 56, 58, 65 and 67; :, 197~ the compounds as described by ~ubparagraph~
- 56, 58, 66 and 67;
198) the compounds as described by subparagraph~ -56, 59, 60 and 67;
199) the compounds as described by eubparagraph~
56, 59, 61 and 67;

:

1~88S43 200) the compounds as de~cribed by subparagraphs 56, 59, 62 and 67;
201) the compound~ as described by subparagraph~
56, 59, 63 and 67;
202) the compounds a~ described by subparagraphs 56, 59, 64 and 67;
203) the compounds as described by subparagraphs ., ~
56, 59, 65 and 67;
204) the compounds as described by subparagraphs 56, 59, 66 and 67. ~ ~ ;
In order to assure that agricultural chemi~ts ~ ' understand and can obtain the compounds of formula (I), (II) ~ ~
or (III), a number of typical compounds will be named. ~ .
2,3-dihydro-3-(3-methylphenyl)-5-phenyl-1-vinyl- . ~
; j~

4(lH)-pyridinone 2,3-dihydro-1-ethyl-3,5-bis(3-methylphenyl)- c,- .
4(lH)-pyridinone I . :
3-(2-chlorophenyl)-5-(3-chlorophenyl)-2,3-di- -hydro-l-propargyl-4~lH)-pyridinone 2,3-dihydro-5-(3-fluorophenyl)-3-phenoxy-1-(1-propenyl)-4(lH)-pyridinone -;-~
2,3-dihydro-3-~3-ethylphenyl)-1-i~opropyl-5-phenylthio-4(lH)-pyridinone :~ .
2,3-dihydro-5-(4-methylphenyl)-1-propyl-3-(3- -.- .`
, . ,, ::.
trifluoromethylphenyl)-4(lH)-pyridinone . ~-2,3-dihydro-3-methyl-5-~3-propoxyphenyl)-1- .
propyl-4(lH)-pyridinone . .. ~ :
2,3-dih~ydro-3-(3-methoxyphenyl)-5-methoxy-1- . -methyl-4(1H)-pyridinone .

X-4:427A -22-_ ' :. . .

5-~3-bromophenyl)-2,3-dihydro-1-ethyl-3-(4-fluorophenyl)-4(1H)-pyridinone l-allyl-2,3-dihydro-5-t3-ethoxyphenyl)-3-t2-methylphenyl)-4(lH)-pyridinone 2,3-dihydro-5-ethoxy-1-ethyl-3-(3-propylphenyl)-4(lH)-pyridinone 2,3-dihydro-5-t3-isopropylphenyl)-1-methyl-3-propyl-4(lH)-pyridinone -:
5-(4-bromophenyl)-2,3-dihydro-3-(3-ethoxyphenyl)-1-isopropenyl-4(lH)-pyridinone 5-~3-chlorophenyl)-2,3-dihydro-3-propoxy-1-propyl-4(lH)-pyridinone 2,3-dihydro-5-(3-methoxyphenyl)-1-(1-propenyl)-3-(2-propylphenyl)-4(lH)-pyridinone 2,3-dihydro-5-(3-fluorophenyl)-1-isopropyl-3-(3-trifluoromethylphenyl)-4(lH)-pyridinone 2,3-dihydro-1-ethyl-5-propyl-3-t3-trifluoromethyl-phenyl)-4tlH)-pyridinone 2,3-dihydro-3-ethylthio-1-propyl-5-(3-propyl-phenyl)-4(lH)-pyridinone l-allyl-2,3-dihydro-5-~4-ethylphenyl)-3-~3-i~o-propoxyphenyl)-4tlH)-pyridinone 2,3-dihydro-5-(3-ethoxyphenyl)-3-(3-isopropyl-phenyl)-l-vinyl-4(lH)-pyridinone 3-t3-bromophenyl)-2,3-dihydro-5-i~opropylthio-1-propyl-4(lH)-pyridinone 3-(2-bromophenyl)-2,3-dihydro-5-(3-ethoxyphenyl)-l-propargyl-4(lH)-pyridinone . .
~ ' las~s43 2,3-dihydro-1-methyl-3,5-bi~(3-trifluoromethyl-phenyl)-4(lH)-pyridinone l-propyl-3-phenyl-5-(3-trifluoromethylphenyl)-4-piperidinone 3-(4-chlorophenyl)-1-ethyl-5-(3-fluorophenyl)-4- ~ -piperidinone . - :
3-~3-fluorophenyl)-5-~2-fluorophenyl)-1-methyl- :- :
4-piperidinone 3-~3-bromophenyl)-1-ethyl-5-phenyl-4-piperidinone 3-(3-fluorophenyl)-1-methyl-5-phenoxy-4-piperi-dinone ; -3-(3-bromophenyl)-1-ethyl-5-phenylthio-4-piperi-dinone -3-methoxy-1-methyl-5-(3-trifluoromethylphenyl)-4-piperidinone 3-~3-bromophenyl)-1-methyl-5-propylthio-4-piperidinone l-ethyl-3-~3-fluorophenyl)-4-piperidinone 3-(2-chlorophenyl)-5-(3-fluorophenyl)-1-methyl-20 4-piperidinone .
3-(3-bromophenyl)-1-ethyl-5-propyl-4-piperidinone 3-(3-fluorophenyl)-S-methoxy-l-methyl-4-piperi- -dinone 3-(3-bromophenyl)-1-methyl-4-piperidinone :~
3-~3-bromophenyl)-5-ethoxy-1-methyl-4-piperidinone 3-~3-fluorophenyl)-5-i~opropylthio-1-methyl-4-piperidinone 3-(3-bromophenyl)-1,5-diethyl-4-piperidinone ~ . ''"'' 1~88S43 3-ethylthio-1-methyl-5-(3-trifluoromethylphenyl)-4-piperidinone 3-(3-fluorophenyl)-1-methyl-5-methylthio-4-piperidinone 3-(3-fluorophenyl)-1-methyl-5-propoxy-4-piperi-dinone -3-(3-fluorophenyl)-5-isopropoxy-1-methyl-4-piperidinone ~
3-(3-chlorophenyl)-1-ethyl-5-(3-fluorophenyl)- . :
10 4-piperidinone '~- :
3-(3-fluorophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4-piperidinone 3-(3-bromophenyl)-1-ethyl-5-isopropyl-4-piperi- :~
dinone 3-(3-fluorophenyl)-1,5-dimethyl-4-piperidinone 1,3-dimethyl-5-(3-trifluoromethylphenyl)-4-piperidinone 3-(3-chlorophenyl)-5-(3-fluorophenyl)-1-methyl-4-piperidinone ;
3-isopropyl-1-methyl-5-(3-trifluoromethylphenyl)-4-piperidinone l-ethyl-3-(4-fluorophenyl)-5-(3-trifluoromethyl-phenyl)-4-piperidinone 3-(3-chlorophenyl)-5-(2-methylphenyl)-1-propyl-4-piperidinone 3-(3-methoxyphenyl)-1-vinyl-4-piperidinone 3-~3-ethylphenyl)-1-i~opropyl-5-(4-propylphenyl1-4-piperidinone ;~ ~ . .....

: . , .
. ' .

io88s43 -l-allyl-3-phenoxy-5-(3-propylphenyl)-4-piperi- ~ -dinone l-ethyl-3-(3-methoxyphenyl)-5-~3-methylphenyl)-4-piperidinone - , 3-(3-i~opropoxyphenyl)-S-methyl~hio-l-propargyl-4-piperidinone .-'f .:
3-(4-bromophenyl)-5-(3-ethoxyphenyl)-1-(1-pro- : ~
penyl)-4-piperidinone --3-(2-ethylphenyl)-5-(3-propoxyphenyl)-1-vinyl-4-piperidinone 3-ethoxy-5-(3-methylphenyl)-1-propargyl-4-piperi~
dinone -~
3-i~opropyl-5-(3-isopropylphenyl)-1-(1-propenyl)- ~ -4-piperidinone 3-(3-chlorophenyl)-5-phenylthio-1-~1-propenyl)-4-piperidinone .
l-isopropenyl-3-methyl-5-(3-propylphenyl)-4- , piperidinone l-i~opropyl-3-~3-isopropylphenyl)-5-phenyl-4- ~ .
20 piperidinone :.
. 3-(3-methoxyphenyl)-1-propyl-5-(2-trifluoromethyl-phenyl)-4-piperidinone .
3-ethylthio-1-ethyl-5-~3-propoxyphenyl)-4-piper-idinone l-allyl-3-(3-ethylphenyl)-5-propoxy-4-pLperidinone . -3-(3-i-opropoxyphenyl)-1-(1-propenyl)-4~piperi- :.
dinone .
3-(4-ethoxyphenyl)-5-(3-ethoxyphenyl)-1-isopro- ;~
penyl-4-piperidinone . - ~;
. ~: - , . .
~ - X-4427A -26- ~ ~
, , ,, ~ .
'~ .. ' ' 10~8S43 l-allyl-3-~3-methoxyphenyl)-5-propylthio-4-piperidinone 3-(3-chlorophenyl)-1-methyl-5-(2-propoxyphenyl)-4-piperidinone 3-~3-ethylphenyl)-1-vinyl-4-piperidinone 3-(3-i~opropoxyphenyl)-5-phenoxy-1-propyl-4- ;
piperidinone 3-(3-isopropoxyphenyl)-5-(3-propylphenyl)-1-propargyl-4-piperidinone -1-isopropenyl-3-(3-isopropylphenyl)-5-phenyl-4- ~'. -piperidinone 3-ethyl-1-~1-propenyl)-5-~3-methylphenyl)-4-piperidinone 2,3-dihydro-3-~3-ethylphenyl)-1-ethyl-4(lH)- -pyridinone 2,3-dihydro-3-ethyl-5-~3-i~opropoxyphenyl)-1- :
(l-propenyl)-4~lH)-pyridinone .
2,3-dihydro-1-methyl-5-(3-methylphenyl)-3-~4-propoxyphenyl)-4~lH)-pyridinone ' 5-~3-bromophenyl)-2,3-dihydro-1-isopropyl-3-(2-isopropylphenyl)-4~1H)-pyridinone 2,3-dihydro-5-~3-fluorophenyl)-1-vinyl-4~lH)-pyridinone 2,3-dihydro-3-(3-ethylphenyl)-5-(3-methoxyphenyl)-l-vinyl-4(1H)-pyridinone 2,3-dihydro-3-~4-i~opropoxyphenyl)-5-(3-trifluoro- ~-methylphenyl)-l-propargyl-4(lH)-pyridinone 2,3-dihydro-1-isopropenyl-5-isopropyl-3-(3-iso-propylphenyi)-4(1H)-pyridinone .. : ' .
~ X-4427A -27-- ' .

1~885~3 2,3-dihydro-1-ethyl-3-~4-trifluoromethylphenyl)- ~ -5-(3-trifluoromethylphenyl)-4(lH)-pyridinone :
2,3-dihydro-3-ethyl-S-~3-methylphenyl)-1-(1-pro-penyl)-4(lH)-pyridinone l-allyl-2,3-dihydro-5-(3-propylphenyl)-4(lH)-pyridinone ~:
3-(3-chlorophenyl)-2,3-dihydro-5-(2-ethoxyphenyl)- ~ .
l-vinyl-4(lH)-pyridinone `~
2,3-dihydro-S-(3-methoxyphenyl)-3-phenylthio~
10 propargyl-4(lH)-pyridinone u 2,3-dihydro-3-phenoxy-5-phenyl-1-(1-propenyl)- .
4(lH)-pyridinone 2,3-dihydro-5-phenyl-3-(3-trifluoromethylphenyl)-l-vinyl-4(lH)-pyridinone 3-butoxy-1-methyl-5-(3-trifluoromethylphenyl)-4-piperidinone :.
3-~utylthio-1-ethyl-5-(3-fluorophenyl)-4-piperi-dinone 3-(t-butyl)-1-ethyl-5-(3-trifluoromethylphenyl)- :
20 4-piperidinone .: -3-(3-bromophenyl)-5-isobutyl-1-propyl-4-piperi- -~ -dinone 2,3-dihydro-3-isobutoxy-1-isopropyl-5-~3-methyl-phenyl)-4(lH)-pyridinone :
5-butyl-2,3-dihydro-1-isopropyl-3-~3-propoxy- ,~
phenyl)-4(lB)-pyridinone 3-(3-ethoxyphenyl)-5-isobutylthio-1-vinyl-4-: ;piperidinone ' ' .. :, ~ . , ' ' ', , . .

,:

2,3-dihydro-5-(3-ethylphenyl)-3-i~obutylthio-1-propargyl-4(lH)-pyridinone l-allyl-3-(t-butoxy)-5-~3-chlorophenyl)-4- ;
piperidinone S-(t-butylthio)-2,3-dihydro-1-propyl-3-(3-propylphenyl)-4(lH)-pyridinone 3-butyl-1-ethyl-5-(3-isopropylphenyl)-4-piperi- - -dinone 3-butoxy-2,3-dihydro-5-~3-chlorophenyl)-1-pro~
pargyl-4(lH)-pyridinone The compound~ of formulaé (I), (II) and ~III) are made by various known processe~. The piperidinones can be made, a~ taught by Settimj et aI., Gazz. Chim. Ital. 96, 604-11 (1966), by the conden~ation of 1-ethoxycarbonyl-1,3-diphenyl-2-propanone~ with formaldehyde and primary amines to form the corresponding piperidinones. ~his proces~, of course, i~ not usable to form the dihydropyridinones.
The piperidinones, particularly the 3,5-diphenyl-piperidinones, may be made from correspondingly substituted bi~pidinones. The reaction was explained by Gottarelli, Tetrahedron Letters, 2813-16 (1965), who showed the prepara-tion of piperidinones from bi~pidinone~ by ~imple reaction ;
with alkali or w~th ~odium sulfide.
Both the piperidinones and dihydropyridinone~ arebest made by the reduction of the corresponding 4~1H)-pyridinones with lithium aluminum hydride. The reduction wa~ described in general by Tamura et al., Chem. Ind.
(London), 168-69 (1972). -,~, . . ..
~ X--427A -29- ~ -, . ' ~ 8543 The pyridinone starting compounds are prepared by -- -processes which are, in general, presently known in the art.
Benary and Bitter, Ber. 61, 1058 (192~) taught the synthesis of an intermediate disodium salt of l,S-dihydroxy- -2,4-diphenyl-1,4-pentadien-3-one by the condensation of 1,3-diphenyl-2-propanone with ethyl formate in the pre~ence of sodium methoxide. The intermediate pentadienone is neutralized with strong acid to form 3,5-diphenyl-4-pyrone. `-Reaction of the pyrone with ammonium acetate at an elevated temperature produces 3,5-diphenyl-4(lH)-pyridinone.
Alternatively, 3,5-diphenyl-4(lH)-pyridinone- can be prepared by the reaction of an appropriately ring-~ubstituted 1,3-diphenyl-2-propanone with formamide and formamidine acetate. Reaction at reflux temperature pro-duces the corresponding 3,5-diphenyl-4(lH)-pyridinone, which is reacted with a halide of the desired l-sub~tituent in the `~ ~-presence of a suitable strong base to form the de~ired ~tartin~ compound.
The preferred synthesis of the pyridinones is adapted from the method~ of Benary and Bitter and of El-Kholy et al., J. Hetero. Chem. 10, 665-67 (1973). An appropriately substituted 1-phenyl-2-propanone i~ formylated at low temperature with sodium methoxide and ethyl formate ln ether, and the product is treated with an amine sa}t of the desired 1-substituent in aqueous medium. The resulting intermediate is predominantly a 1-amino-2-phenyl-1-buten-3-- one. Some pyridinone is also formed at this step, as re-ported by El-Kholy et al. The butenone is reformylated a~
~' ~ ' ' ' :, ~

,.

. , .

1~88543 before, and spontaneously cyclizes to form the l-substituted-3-phenyl-4(1H)-pyridinone.
The starting 2-propanones may be prepared by ~yntheses in the literature. For example, see Coan et al., J. Am. Chem. Soc. 76, 501 (1954); Sullivan et al., ~Di~odium Tetracarbonylferrate," American Laboratory 49-56 (June 1974); Collman et al., "Synthesis of Hemifluorinated Xetones u~ing Disodium Tetracarbonylferrate," J. Am. Chem. Soc. 95, 2689-91 (1973); Collman et al., "Acyl and Alkyl Tetracar-bonylferrate Complexes as Intermediates in the Synthe~is ofAldehydes and Ketones,~ J. Am. Chem. Soc. 94, 2516-18 (1972).
The general synthesis methods of the pyridinones proceed from either ketone starting compounds or from car-bonyl halides. The general process is the sæme, whichever ;~
starting compound is used. The general process will be di~cussed fir~t, and reagents and reaction conditions will then be explained in detail.
The synthesis proceeds through an intermediate ofthe formula ~ ~ ~ C - C - C - R (VI) R1 o wherein Ql and g2 independently are 2 hydrogen atom~, = CHOH, or an ~lkali metal ~alt thereo~, ., .
= CNN(R )2 or = CHNHR12, provided that only one of Ql and Q2 is = CHNHR12, 1~88S~3 R i~ a R2, R5 or ~8 group R~ a Rl, R4 or R7 group R12 is a R, R3 or R6 group.
The R9 groups independently are Cl-C3 alkyl, or the R qroup~ combine with the nitrogen atom to which they are attached to form pyrrolidino, piperidino, morpholino, N-methylpiperazino and the like.
The -CHOH group~, which may be in the form of alkali metal ~alt~, are provided by reaction with formylating agents which will be defined below. The =CHN~R9)2 groups are provided by reaction with aminoformylating agents, and -the -CHNHR12 group~ are provided by exchanging ~ither zCHOH -group~ or ~CHN(R9)2 groups with amine~ of the formula R12NH2 . .;, The lntermediates de~cribed above are prepared from either ketone~ or carbonyl halide~, a~ will be ex- ~, plained below. When Ql and Q2 each are 2 hydrogen atom~
the pyridinone~ are prepared by either ~ -1. reacting with a formylating or amino-formylating agent; -~
2. roacting again with a formylating or amino-for-ylating agent; and 3. reacting with an amine of the formula R12NH2;
or 1. reacting with a formylating or amino-formylating agent;
- 2. reacting with an amine of the formula R12NH2; A,' ; and 3. reacting again with a formylating or amino-~ ~ - formylating agent.
- ~ X-4427A -32-.

~ ;

1~885~3 When one of Ql and Q2 is either =CHOH or =CHN~R9)2, and the other i8 2 hydrogen atoms, the pyridinones are prepared by either 1. reacting with a formylating or aminoformylating agent; and 2. reacting with an amine of the formula R12NH2;
or 1. reacting with an amine of the formula R12NH2;
and 2. reacting with a formylating or aminoformylating agent.
When each of Ql and Q2 are either =CHOH or =CHN(R9)2, the pyridinones are prepared by reacting with an amine of the formula R12NH2. -The variations of the synthesis, and the prepa-ration of the intermediate~, will be sketched below.
When the proce~s starts with a ketone of the general formula ~ ~ ~ CH - C - CH2 - R -~c- ,.

the first step is the formylation or aminoformylation of one of the methylene qroups. If a formylating agent is u~ed, a ~, ketone of the formula B.
~ / ~ C - C - CH - R

R
is produced. Reaction with an aminoformylatinq agent pro-, duces an enaminoketone such as (C) below.

X-4427A -33_ , - ' ~88543 C. o C- CH - R~
1 0~ tRe) 2NCH
R
Organic chemists will understand that, although - ~
the sketche~ above ~how the first formylation or amino- -formylation a~ occurring on a certain side of the ketone, it may in fact occur on either side of the ketone, depending on -~
the activating characteri~tics of R10 and Rll. The course of the reaction i~, the ~,ame in either case. It will also ~e ~-understood that, in many in~tances, the product of the x - .
formylation or aminoformylation step will actually be a ~.
mixture containing the two posJible monosu~stituted com-pounds and the di~ubstituted compound.
The monosubstituted product i~ formylated or :
aminoformylated again, and exchanged with an amine of the formula R12NH2. ~he s,teps may be performed in either order. ~;
If the exchange is performed first, the intermediate product i~, an en~minoketone of the formula D. C ~ - C - CH2 - R1 , o~ R1 2HNCH
R
Elth-r formylation or aminoformylation of the above enamino-ketone affords the pyridinone product, a~ the intermediate - cyclize~ a8 ~oon as the second group is introduced on the .. .
other methylene group. ~}
A~ternatively, either of compou~s ~B) or (C~ may , . . .
~ be either formylated or aminoformylated to prov~de inter-, ~ mediates of any of the formulae below.

, ~,, , "
~ X-4427A -34- ~

:, .

:

, lQ885~3 C - C - C - R~ 1 ' C~/ " 11 . .: ~.

\, ~/ 11 11 ~0/ HOCH HCN(RD)2 `
R . -.

C- C- C- R11 ~
_,/ 11 11 ~ ~
~0~ ~R~)2NCH HCN(R~)2 ., It will be understood that the compound similar to ~F), wherein the formyl and aminoformyl groups are reversed, i8 equivalent in all respects to compound (F). Pyridinone~ are 17 ~ .
formed from any of the above three intermediates by simple contact of the intermediate with an amine of the formula When the starting compound i8 a carbonyl halide, .;:.
~ .
the process proceeds essentially a~ described above, except ~. :.
for ~ fir~t tep performed as foll~ws: ~
O .',' ~:' H. ~ I~
~ / --CHz --G--Halo I (R~)2NCH=CH - R11 _ .,.
R~ ~ . ~ .
O ,'' ~:

~ HCN(R~)z .
: It will be understood that reaction (H) can also be per-formed in the opposite manner, a~ ~hown below:

~ ' ~ ` .. .

~ X-4427A - -35- .

- . .
- , :

1~88543 ~ CHCCHN(R~)s ~ Halo - C - CHs - R11 -R1o~ c . . I ; .

-C - C - CH2 - R11 ~ , ~
~)2NCH . , , It is al~o possible to form intermediates using ~ ;
pho~gene as the carbonyl halide when the 3- and 5-~ubsti-tuents of the pyridinone are identical.
1 0 . :
~ -CH=CH-N(R~)2 CC 1 2 r~ c ~
10/ c ~R~ 2NCH HCN(R~)z ~R10 The enaminoketones formed in equation~ ~H), (I) ~ and ~J) above are identical to the intermediates de~cribed -~ in ~C) and ~G) above, and are converted to the pyridinone~
~8 d-~¢ribed above.
Alternatively, it i~ po~Jible to prepare the 1-un-ubJtituted pyridinones by using NH3 in p}ace of R12NH2 in the process, or by u~ing the proce~ of Benary and -Bitter. The pyridinone is then alkylated at the l-po~ition with a halide of R12 according to common procedures.
As a chomlst would expect, the amine~, R12NH2, may be used in tho form of salt~, preferably hydrohalide salt~,~including h~ rochlorides, hydrobromide~ and the like.
Such -alt~ are often more convenient than the free amines.

, ~ ~

The formylating agents u~ed 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 . ~:
I l 0~ (C1 -C6 a l ky l ) or c-/

Similar formylations are discussed in Organic -SYntheses 300-02, Collective Vol. III ~1955).
The e~ters are used in the presence of strong ba~es, 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 ba~es as diazabicyclononane and diazabicy-cloundecane are ~180 useful.
Rsactions with formylating agents are performed in ;' aprotic solvents such as are regularly used in chemical synthesis. Ethyl ether is usually the preferred solvent.
Ethers in general, including ~olvents ~uch a~ ethyl propyl ether, ethyl butyl ether, 1,2-dimethoxyethane and tetra-hydrofuran, aromatic solvents such as benzene and xylene, and alksnes such as hexane and octane can be used as formyla-tion ~olvents.
Because of the strong base~ used in the formyla-tion reactions, low temperatures produce the best yields.

~' ' , ' ' ..
X-4427A _37_ .: . .

: .

- 10885~3 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 from about 1 to about 24 hours are adequate for -economic yields in the formylation reaction~.
The aminoformylating agents used in these synthe-~es may be any compounds capable of reacting with an active methylene group to introduce a =CHN(R9)2 group, or its acid addition salt. Such agents are chosen from among s-triazine, the orthoformamides, HClN(R )2]3 the formate ester aminals, Q3 _ R13 HCIN~R )2]2 the formamide acetals Q3 _ R13 HCN~R )2 the tris~formylamino)methanes, H
HC(NHCH)3 and the formiminium halides, HC=N(R9)2Halo Halo Q3~in the ~tructures above represents oxygen or ~ulfur, and R13 represents Cl-C6 alkyl or phenyl.
' -- .

1~88543 U~eful references on the aminoformylating agents include DeWolfe, Carboxylic Acid Derivatives 420-506 (Academic Press 1970), and Ulrich, Chemi~try of Imidoyl Halides 87-96 (Plenum Pre~s 1968). Bredereck et al. have written many paper~ 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 (1973); Ber. 97, 3397-406 (1964);
Ann. 762, 62-72 (1972); Ber. 97, 3407-17 (1964); Ber. 103~
210-21 (1970); Angew. Chem. 78, 147 (1966); Ber. 98, 2887-96 0 (1965); Ber. 96, 1505-14 (1963); Ber. 104, 3475-85 (1971); --Ber. 101, 41-50 (1968); Ber. 106, 3725-31 (1973); and Angew.
Chem. Int'l. Ed. 5, 132 (1966) . Other notable papers on the subject include Kreutzberger et al., Arch. der Pharm. 301, 881-96 (196g), and 302, 362-75 (1969), and Weingarten et al., J. Org. Chem. 32, 3293-94 (1967).
Aminoformylations are usually carried out without solvent, at elevated temperatures from about 50C. to about 200C. Solvents such as dimethylformamide are sometimes u~ed, howevor, particularly when it is desirable to raise the boiling point of the reaction mixture.
The exchange reaction~ with R12NH2 are best per-form d in protic ~olvents of which allcanol~ are preferred and ethanol iB most appropriate. ~emperatures from a~sout -20C. to about 100C. can be used for the exchange re-actions Room temperature is ~ati-factory and is preferred.
In general, intermediate compounds ln the ~yn-thesi~ are not purified, but are simply used in~succe~sive steps after separation by extraction, neutralization or removal of exces~ solvent or reactant as appropriate.

~- X-4427A -39-10885~3 The enamine acylation reactions, H-J, are per-formed in the presence of bases such as tertiary amines, alkali metal carbonates, magnesium oxide and the like, and in aprotic solvents as described above.
In some instances, as organic chemi~ts will understand, it is necessary to apply additional synthetic steps after the pyridinone has been formed. For example, it i8 convenient to form compounds having an alkoxy R5 or R8 substituent by first making the corresponding hydroxy-sub~tituted compound, and then substituting on the oxygenatom.
The compounds of formula (I), ~II) or ~III) are most efficiently formed from the corresponding 4(lH)-pyridinones by reduction with lithium aluminum hydride. The reaction i8 carried out by ~imple contact of the starting compound with the reducing agent in a solvent. The reaction may be performed at room temperature, or it may be accelerated by heating the reaction mixture moderately. In general, temperatures from about 0C. to about 50C. can be used. In addition to lithium aluminium hydride other aluminium or boron hydrides may be used, for example sodium borohydride, sodium cyanoborohydride, lithium aluminium tri-t-butoxy-hydride, sodium aluminium bis(methoxyethoxy)hydride and lithium triethylborohydride.
Solvents for the reaction may be any of the typical inert organic reaction solvents, of which diethyl - ether i~ preferred. Other ethers, including tetrahydrofuran ~ and isopropyl ether, alkanes including hexane and octane, :

~ X-4427A -40-1~88543 and aromatics such a~ benzene and xylene, are also usable solvents.
As one would of course expect, reduction of the pyridinone~ produces a mixture of products. First one, and then the other, of the two double bonds ln the pyridinone ring are reduced ~y the reaction. Necessarily, the reaction produce~ a proportion of the 2,3-dihydropyridinone, a pro-portion of the 5,6-dihydropyridinone, and a proportion of ~- ~
the piperidinone. The products are readily separated ac- -cording to the usual methods. Column chromatography is u~ually the preferred method of separation.
It i~ believed that the above description of the synthesis iB adequate to enable an organic chemist to prepare any compound of formula (I), ~II) or (III). The following specific examples are provided merely as as~i~tance to the chemist, to assure that all of the compounds are ;-accesQible.
In the examples below, the product~ were identi-fied by elemental microanalysis, thin-layer chromatography, nuclear magnetic resonance analysis, infrared analysi~
ultraviolet analysis, and mass spectroscopy as wa~ required or convenient in each case.
All temperature~ in the example~ below are on the Celsius scale.
Example 1 --2,3-dihydro-1-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridinone Example 2 2,3-dihydro-1-methyl-5-phenyl-3-(3-tri$1uoromethylphenyl)-4(lH)-pyridinone .

.
~ .

Example 3 l-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4-piperidinone A 556 g~ portion of 1-phenyl-3-(3-trifluoromethyl-phenyl)-2-propanone was added to 4000 ml. of tetrahydrofuran containing 284 g. of sodium methoxide at 10-15. The addition was carried out over a 20 minute period with constant stirring while the temperature was held below 15, and the mixture was then stirred for 15 minutes more. Then 370 g. of ethyl formate was added over a 30 minute period, - ;
and the complete mixture was stirred 1 hour more at 10-15.
A second portion of 296 g. of ethyl formate was then added slowly and the mixture wa~ stirred overnight while it was allowed to warm to room temperature.
A solut$on of 336 g. of methylamine hydrochloride -~
in 1300 ml. of water wa~ then added, and the mixture wa~ -stirred for 1/2 hour more. The phases were then allowed to separate, and the organic layer was concentrated under vacuum. The re~idue was dissolved in methylene chloride, dried over ~odium ~ulfate and concentrated to an oil, which weighed 723 g.
The oil was added to 4000 ml. of tetrahydro~uran, 284 g. of sodium methoxide wa~ added, and the proce-s de-scribed above wa~ repeated, using the ~ame weight~ of ethyl formate and of méthylamine hydrochloride. The oily re~idue obtained from evaporation of the reaction mixture was di~-~olved in methylene ¢hloride, washed with water and dried over sodium sulfate. The methylene chloride was evaporated under vacuum, and the residue crystallized upon standinq. A
small amount of diethyl ether was added to form a thick ~' ' ' '' .
.

,' ': .
.

lOB8543 slurry which was chilled overnight. Filtration of the chilled slurry produced 430 g. of 1-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridinone, m.p. 153. -A 21 g. portion of the above intermediate was -~
di~olved in 500 ml. of diethyl ether and 5 g. of lithium aluminum hydride was added. The mixture was ~tirred at reflux temperature for 3 hours, and excess hydride was decompo~ed by adding successively 5 ml. of water, 15 ml. of 15 percent -~odium hydroxide solution and 5 ml. more of water. The react$on mixture wa~ then cooled and stirred overnight, and filtered through anhydrous magnesium sulfate.
The filtrate wa~ concentrated under vacuum to produce an oil which wa~ ~eparated by chromatography over a silica gel column.
The various fractions were eluted with benzene-ethyl acetate mixtures. The 5th and 6th fractions obtained contained primaril~ the two dihydro compounds, which were ~ep~rated by additional ~tages of chromatography to obtain about 4.3 g. of the compounds of Examples 1 and 2. The com~
pound~ were identified by nuclear magnetic resonance analysis and by mas~ ~pectroscopy, which indicated a molecular weight of 331 for each.
About 4.1 g. of the compound of Example 3, m.p.
86.5-87.5, was obtained from the 7th, 8th and 9th fraction~. -Theoretical Found C68.46~ 68.t9~
H5.44 5.49 ;
N4.20 4.37 - --, .:~ . ~ .

~: -'.

': . :...... '...

1~88543 Example 42,3-dihydro-1-methyl-3-~3-methylphenyl)-5-phenyl-4(lH)-pyridinone Example S
2,3-dihydro-1-methyl-5-(3-methylphenyl)-3-phenyl-4(lH)-pyridinone Example 6 l-methyl-3-(3-methylphenyl)-5-phenyl-4-piperidinone A 22.8 g. portion of 1-(3-methylphenyl)-3-phenyl-2-propanone was reacted with ethyl formate and methylamine hydrochloride as de~cribed in Examples 1-3 to produce 7 g.
of l-methyl-3-(3-methylphenyl)-5-phenyl-4(lH)-pyridinone.
The above intermediate pyridinone was reduced with 2 g. of lithium aluminum hydride in 100 ml. of diethyl ether as described in Examples 1-3.
The second fraction obtained by column chromato-graphy on ~ilica gel with benzene-ethyl acetate was the piperidinone of Example 6, m,p. 100-103, yield 1.5 g. -Theoretical Found C 81.10% 80.98 H 8.24 8.00 N 4.98 4.87 The first fractions off the column contained the compounds of Examples 4 and 5, which were separated by further stages of chromatography with benzene-ethyl acetate.
The yield of the compound of Example 4 was about 500 mg., and it wa~ identified by nuclear magnetic resonance analysi~
and ma-~ spectro-copy. About 750 mg. of the product of ':

- ~88543 Example 5 was obtained. The product had a melting point of 72-76 and the elemental microanaly~is was as follows.
Theoretical Found C82.28~ 82.Z3%
H6.90 7.00 N5.05 4.83 Example 7 3,5-bis(3-fluorophenyl)-1-methyl-4-piperidinone A 10.5 g. portion of 1,3-bis(3-fluorophenyl)-2-10 propanone wa~ mixed with 16.2 g. of formaldehyde and 8 g. of -40 percent aqueou~ methylamine solution in 75 ml. of de-natured ethanol. The mixture was stirred at reflux tem-perature overnight, cooled and filtered. The recovered solids were ~dentified as 13 g. of essentially pure 3,5-bis~3-fluorophenyl)-N,N-dimethylbispidinone.
A 7.1 g. portion of the bispidinone was combined with 2.8 g. of hydroxylamine hydrochloride and 3.3 g. of sodium methoxide in 50 ml. of 75 percent aqueous acetic acid. The mixture was stirred at reflux for 6 hours, cooled, and partially evaporated under vacuum to remove most of the acetic acid. The concentrated solution was poured into a large amount of water and extracted with chloroform. The organic extract wa~ dried over magnesium sulfate and con-centrated under vacuum. The residue waQ made basic with aqueous sodium hydroxide and extracted aqain with chloro-form. Evaporat~on of the chloroform extract under vacuum ~ -. , . produced 0.7 g. of 3,5-bis(3-~luorophenyl)-l-methy7-4-piper-idinone, molecular weight 301 by mass spectro~copy. - -';'' ~ -'; '~
' , X-4427A -45- -~

10885~3 Example 8 2,3-dihydro-3-(4-fluorophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridinone Example 9 2,3-dihydro-5-(4-fluorophenyl)-1-methyl-3-(3-trifluoromethyl-phenyl)-4(lH)-pyridinone Example 10 3-(4-fluorophenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4-piperidinone A 28 g. portion of 1-~4-fluorophenyl)-3-(3-trifluoromethylphenyl)-2-propanone was reacted with ethyl formate and methylamine hydrochloride as described in ExampleQ 1-3 to produce 10 g. of 3-(4-fluorophenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridinone.
The above pyridinone was reduced with 2 g. of lithium aluminum hydride as described in Examples 1-3.
The various products were separated by chromatography as i-described above to produce about 0.8 g. each of the three compounds named in the heading, which were identified as 20 follows.
Example 8, m.p. 89-91.
Theoretical Found C 65.33% 65.06 H 4.33 4.24 N 4.01 3.89 Exampl2 9, molecular weight 349 by mass ~pectroscopy.

', 1~88543 Example 10, m.p. 84-85.
Theoretical Found C 64.96% 65.18%
H 4.84 4.79 N 3.99 3.95 Example 11 3,5-bis~3-chlorophenyl)-2,3-dihydro-1-methyl-4(1H)-pyridinone Example 12 3,5-bis~3-chlorophenyl)-1-methyl-4-piperidinone A 10 g. portion of 1,3-bis(3-chlorophenyl)-2~
propanone was reacted with ethyl formate and methylamine hydrochloride to produce 7 g. of 3,5-bi~(3-chlorophenyl)- ~
l-methyl-4(lH)-pyridinone. A 6.4 g. portion of the pyri- , ;
dinone was reduced with 2 g. of lithium aluminum hydride and the products were sepa~ated by chromatography a~ described in the examples above. The yields were about 0.8 g. of Example 11, and 1.5 g. of Example 12. ~ ;
Example 11, m.p. 140.
Theoretical Found 20 C 64.49% 64.s8%
H 5.41 5.77 N 4.18 4.07 , Example 12, m.p. 79. ,-~heoretical Found -C 64.68% 64.94%
~ 5.13 5.25 -~ N 4.19 4.24 Example 13 5-~(3-bromophenyl)-2,3-dihydro-1-methyl-3-phenyl-4~lH)-pyridinone ' ' ' ` ' 1~88543 Example 13a 3-(3-bromophenyl)-2,3-dihydro-1-methyl-5-phenyl-4(lH)-pyridinone Example 14 3-(3-bromophenyl)-1-methyl-5-phenyl-4-piperidinone A 10 g. portion of 3-(3-bromophenyl)-1-methyl-S-phenyl-4(lH)-pyridinone was made from 22 g. of the cor-responding 2-propanone as described in Examples 1-3. The pyridinone was reduced with 2 g. of lithium aluminum hydride as described in the examples above, and the reaction mixture wa~ chromatographed as described above with benzene-ethyl acetate mixture~. The combined yield of the compound~ of Examples 13 and 13a was 4 g., molecular weight 341 by mass spectroscopy. The yield of the compound of Example 14 was O.S g., molecular weight by mass spectroscopy 343.
Example 15 5-(3-chlorophenyl)-3-(4-chlorophenyl)-2,3-dihydro-1-methyl-4(1~)-pyridinone Example 16 3-(3-chlorophenyl)-5-(4-chlorophenyl)-2,3-dihydro-1-methyl-4(lH)-pyridinone Example 17 3-(3-chlorophenyl)-5-(4-chlorophenyl)-1-methyl-4-piperidinone A 10 g. portion of 3-(3-chlorophenyl)-5-(4-chloro-phenyl)-l-methyl-4(1H)-pyridinone was made from 33.6 g. of the corresponding 2-propanone by the procedures of Examples 1-3. The pyridinone was reduced with lithium aluminum hydride and the reaction mixture was separated by chroma-tography as described in the examples above. The products 1~88543 of Examples 15 and 16 were obtained a~ a mixture containing both, combined yield 2.1 g., m.p. 125.5.
Theoretical Found C 65.00% 65.15%
H 4.55 4.65 N 4.22 4.31 The compound of Example 17 wa~ obtained in a yield of 1.8 g.
m.p. 118.5-126.5.
Theoretical Found C64.68~ 64.45~
H 5.13 4.93 ~-N 4.19 4.32 Example 18 ~~
5-(4-chlorophenyl)-2,3-dihydro-1-methyl-3-~3-trifluoromethyl-phenyl)-4(lH)-pyridinone Example 19 .: ,, 3-(4-chlorophenyl)-2,3-dihydro-1-methyl-5-~3-trifluoromethyl-ph-nyl)-4(lH)-pyridinone ~, Example 20 -20 3-(4-chlorophenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4-piperidinone A 15 g. portion of 1-(4-chlorophenyl)-3-(3-trifluoromethyIphenyl)-2-propanone waa reacted with ethyl formate and methylamine hydrochloride to prepare 10 g. of 3-(4-chlorophenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyrldinone. The intermediate pyridinone was reduced with lithium aluminum hydride. Column chromatographic separation of the reaction mixture on a silica gel column as --; ~ described in the examples above produced about 0.5 g. of the ,;~: -~ X-4427~ _49_ -. ~ , ':

~88543 compound of Example 18, m.p. 122.5, about 1.1 g. of the compound of Example 19, m.p. 113.5, and about 1.3 g. of the compound of Example 20, m.p. 115.5.
Example 18 Theoretical Found C 62.39% 62.68~ ~ -H 4.13 4.10 N 3.83 3.75 Example 19 Theoretical Found C 62.39% 62.11%
H 4.13 4.36 N 3.83 3.83 Example 20 Theoretical Found C 62.05% 61.75% -H 4.66 4.74 N 3.81 3.86 Examplé 21 20 3-(2-chlorophenyl)-2,3-dihydro-1-methyl-5-~3-trifluoro-methylphenyl)-4~lH)-pyridinone Example 22 5-(2-chlorophenyl)-2,3-dihydro-1-methyl-3-~3-trifluoro- -methylphenyl)-4(lH)-pyridinone Example 23 3-~2-chlorophenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4-piperidinone Ten g. of 3-(2-chlorophenyl)-1-methyl-5-(3-tri-fluoromethylphenyl)-4(lH)-pyridinone was prepared ~rom 35 q.

, .
~ X-442iA ~ -50-1~}88543 of l-(2-chlorophenyl)-3-(3-trifluoromethylphenyl)-2-propanone by reaction with ethyl formate and methylamine hydrochloride as de~cribed in Examples 1-3. The pyridinone -~wa~ reduced with 2 g. of lithium aluminum hydride and exces~
hydride was decomposed and the product worked up and chromato-graphed as described in Examples 1-3. The recovered yield~
were about 1.3 g. of a mixture of the compounds of Examples 21 and 22, which were identified by mass spectroscopy with --an indicated molecular weight of 365. About 2.1 g. of the compound of Example 23 was recovered, m.p. 90-92. The elemental analysis of Example 23 was as follows.
Theoretical Found ~
C62.0s% 62.06% ~;
H 4.66 4.68 ;~ -~
N 3.81 3.74 Example 24 2,3-dihydro-3-~3-methoxyphenyl)-1-methyl-5-phenyl-4(lH)-pyridinone Example 25 -- '... :
2,3-dihydro-5-(3-methoxyphenyl)-1-methyl-3-phenyl-4t-lH)-pyridinone Example 26 3-(3-methoxyphenyl)-1-methyl-5-phenyl-4-piperidinone A 54 g. portion of 1-(3-methoxyphenyl)-3-phenyl-2-propanone was reacted with ethyl formate and methylamine hydrochloride as described in Examples 1-3 to prepare 10 g.
~- of 3-(3-methoxyphenyl)-1-methyl-5-phenyl-4(lH)-pyridinone, :
~ which was reduced with 2 g. of lithium aluminum hydride.

-.

.

1~88543 ~he reaction mixture was worked up as in the examples abo~e and chromatographed over a silica gel column. Aboùt 1.4 g.
of a mixture of the compoundQ of Examples 24 and 25 wa~
o~tained, an oil which was identified by mass spectroscopy --~
a~ having a molecular weight of 293. About 1.3 g. of the ~
piperidinone of Example 26 was recovered, which had an -~;
indicated molecular weight of 295 by mass ~pectroscopy. ~`
Example 27 2,3-dihydro-1-ethyl-3-phenyl-5-~3-trifluoromethylphenyl)-4(lH)-pyridinone Example 28 2,3-dihydro-1-ethyl-5-phenyl-3-(3-trifluoromethylphenyl)- ~ ~
. - . - - . .
4(lH)-pyridinone ! ~ -`
Example 29 -l-ethyl-3-phenyl-5-(3-trifluoromethylphenyl)-4-piperidinone .~, An 11.5 g. portion of 1-phenyl-3-(3-trifluoro-methylphenyl)-2-propanone was reacted with ethyl format~ and ethylamine hydrochloride as described in Examples 1-3 to produce 6.8 g. of 1-ethyl-3-phenyl-5-(3-trifluoromethyl- , -phenyl)-4(1H)-pyridinone, which waQ reduced with 2 g. ~f lithium aluminum hydride a~ described above. After column chromatography as described in the examples above, the ;--products of Examples 27 and 28 were recovered a~ a m.lxture.
., :- .,, Mass spectroscopy of the mixture showed a molecular weight of 345, and the yield was 1.2 g. The molecular weight o the product of Example 29 wa- indicated a~ 347 by mas~ -peC~ro-copy~ yi-ld 1.9 g.

~ ~ J ~

~ X-4427A ~ -52-, . ..

10885~3 Example _ 2,3-dihydro-5-ethyl-1-methyl-3-(3-trifluoromethylphenyl)-411H)-pyridinone Example 31 2,3-dihydro-3-ethyl-1-methyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridinone Example 32 3-ethyl-1-methyl-5-(3-trifluoromethylphenyl)-4-piperidinone `
Seventy q. of l-piperidino-l-butene and 77 g. of triethylamine were di~olved in 1500 ml. of diethyl ether at 0. A 112 g. portion of 3-trifluoromethylphenylacetyl chloride dis,~olved in 700 ml. of diethyl ether was added dropwis,e, and the mixture wa~, stirred for 2 hours at 0 after completion of the addition. The mixture was then evaporated to dryness under vacuum, and the residue was taken up in methylene chloride. The solution was wa~hed with water, dried and evaporated to an oily residue.
The above residue was combined with 500 ml. of dimethylformamide dimethyl acetal and heated at reflux temperature for 12 hours. The mixture was then evaporated under vacuum, and the residue was mixed with 700 ml. of denatured othanol and 150 g. of methylamine hydrochloride. ' The ethanol ~olution was heated at reflux for 12 hours more and evaporated to dryae~,~,. The residue was taken up in methylene chloride, wa~hed with water, dried, and evaporated -to drynes~ again. The res~due was slurriea in diethyl ether and filtered. Separation of the ~olids by column chromato-- gra~phy on ~,ilica gel produced 10"5 g. of 3-ethyl-1-methyl-5-(3-trifluoromethylphenyl)-4l1H)-pyridinone.

~X-4427A -S3-: -.

1~?88543 The pyridinone intermediate wa~ reduced with 2 g.
of lithium aluminum hydride and worked up and chromato-graphed as described in the examples above. The products of Examples 30 and 31 were isolated as a mixture, with a com-bined yield of 1.2 g. Mass spectroscopy of the product showed an indicated molecular weight of 283. The product of Example 32, 2.6 g., had a molecular weight of 285 by ma~s spectroscopy.
Example 33 1-allyl-2,3-dihydro-5-phenyl-3-(3-trifluoromethylphenyl)-4~lH)-pyridinone Example 34 l-allyl-2,3-dihydro-3-phenyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridinone Example 35 l-allyl-3-phenyl-5-(3-trifluoromethylphenyl)-4-piperidinone Twenty g. of l-phenyl-3-(3-trifluoromethylphenyl)-2-propanone wa8 reacted with ethyl formate and allylamine hydrochloride a~ de~cribed in Examples 1-3 to obtain 10.8 g.
of 1-allyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridinone, which wa~ reacted with 2 g. of lithium aluminum hydride a~ described in Examples 1-3. The reaction mixture was worked up and chromatographed as descr$bed in the examples above to obtain 1.2 g. of the products of Examples 33 and 34 a8 a mixture. The compounds were identified by mass spectroscopy, which showed an indicated molecular ~ weight of 357. A yield of 1. O g. of the compound of Example ; 35 was obtained, which 8hswed a mass spectroscopy molecular . .
~ weight of 359.
; ' ~ '.-.X-4427A -54- ~
.

Example 36 2,3-dihydro-1-methyl-3-(3-trifluoromethylphenyl)-4(lH)-pyridinone ;~
Example 36a 2,3-dihydro-1-methyl-5-(3-trifluoromethylphenyl)-4(1~
pyridinone `
Example 37 l-methyl-3-(3-trifluoromethylphenyl)-4-piperidinone A mixture of 50 g. of 3-trifluoromethylphenyl acetone and 100 ml. of dimethylformamide dimethyl acetal in 200 ml. of dimethylformamide was stirred at reflux tem-perature for S days. ~he excess volatile ingredients were then removed under vacuum and the re~idual oil was taken up in 200 ml. of ethanol. One hundred g. of methylamine hydrochloride was added and the mixture wa~ refluxed over-night. After cooling, precipitated amine was filtered off and the filtrate was evaporated under vacuum. The residual oil was taken up in methylene chloride and wa~hed twice with 300 ml. portion~ of water and once with 400 ml. of saturated NaCl solution. The organic solution was then dried over magnesium sulfate and evaporated under vacuum to an oily residue which was taken up in 400 ml. of diethyl ether, cooled and filtered. The ~olids were recrystallized from i~opropyl ether-methylene chloride to produce 10 g. of l-methyl-3-~-trifluoromethylphenyl)-4~lH)-pyridinone.
The above pyridinone~was reduced with lithium aluminum hydride and the reaction mixture wa~ worked up and chromatographed as de~cribed in the examples above. About ~ ' ' .,'.
~ X-4427A -55-1~88S43 l.S g. of the product of Example 36 was obtained, m.p.
64-65C.
TheoreticalFound C 61.17% 60.96%
H 4.74 4.70 N 5.49 5.51 About l.S g. of the product of Example 37 was obtained, and was found to have an indicated molecular .
weight by ma~s ~pectroscopy of 257. The product of Example 36a was recovered ~n the amount of 0.15 g.
The compounds described above have been tested in a number of herbicidal te~t ~ystem~ to determine the range of their herbicidal efficacy. The results produced by the compound~ in the repre~entative tests reported below are exemplary of the outstanding activity of the compounds.
Compound application rate~ are expre~ed in kilo-grams of the compound per hectare of land (kg./ha.) through-out this specification and claim~.
Blank spaces in the table~ below indicate that the compound Wa# not tested again~t the named specie~. In ~ome ~nstances, the results of testing a compound repeatedly -agaln~t a plant pecies have been averaged.
~ ntreated control plant~ or plots were included in all te~t~. Ratings of the control produced by the compound~
wer- made by comparison of the treated plant~ or plot~ with the controls. -~ ~ , ~ .
..

~ ~ ~ ;X--4427A -56-~ ' ' , .

Test I
broad ~pectrum greenhouse te~t Square plastic pots were filled with a ~terilized sandy loam soil and were planted to seeds of tomato, large crabgrass and pigweed. Each pot was individually fertilized.
Test compounds were applied postemergence to ~ome pots and preemergence to others. Postemergence application~ -of the compounds were sprayed over the emerged plant~ about 12 days after the seeds were planted. Preemergence ap-plication~ were sprayed on the ~oil the day after the seedswere planted.
Each test compound wa~ di~solved in 1:1 acetone:
ethanol at the rate of 2 g. per 100 ml. The ~olution also contained about 2 g. per 100 ml. of an anionic-nonionic surfactant blend. One ml. of the solution was diluted to 4 ml. with deionized water, and 1-1~2 ml. of the reaulting solution was applied to each pot, resulting in an application rate of 16.8 kg./ha. of test compound.
Ater the compounds were applied, the pots were moved to the greenhouse, watered as nece~sary, and observed and rated about 10-13 days after appl~cation of the com-pounds. Untreated control plants were used a~ ~tandard- in every test.
The table below reports results of testing typical compound~ of formulae (I), (Ii) and (IIT). The compounds are identified by their exampl- numbers above.
Herbicidal effect wa~ rated on a 1-5 scale, where . . .
1 indicates normal plants, and 5 indicates death of the ~- plant- or no emergence.

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Te~t 2 seven-species greenhouse test The test was conducted in general like the test described in Test 1. In this test, the seeds were planted in flat metal trays, rather than in pots. The compounds were formulated according to the procedure above, except that about 6 g./100 ml. of the compound was dissolved in the ~urfactant-containing solvent, and about 1 part of the organic ~olution was diluted with 12 parts of water before application to the trays. The compounds were applied at the rate of 9.0 ~g./ha., and the results of testing against the species named below were as follows.

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. ~ , 1~88S43 Test 3 multiple-species greenhouse test In general, the test method was the ~ame as the method of the test above. Various compounds were tested preemergence and postemergence at different application rates which are indicated in the tables below. A number of additional weed and crop species were used in the preemer-gence tests as is shown in the table. Typical results were as follows.

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1~88543 Test 4 -yellow nut~edge test Typical compounds were evaluated in the greenhouse against yellow nut~edge in a te~t method which followed in general the method of Test 1, except that the acetone-ethanol ~olution contained about l.S g./100 ml. of the test compound. Both preemergence and postemergence te~t~ of the compounds were made, and rates of from 0.28 to 9.0 kg./ha.
were applied in some instance~. The 1-5 rating scale was used in tests at 9.0 kg./ha., while tests at lower appli-cation rates were rated in percent control of the weed. The test compounds were incorporated in the soil for te~ting preemergence at rates below 9.0 kg./ha. The results of testing typical compounds are presented in the table below.
Table 5 Compound of Rate Pre- Post-Experiment No. kg./ha. emergence emergence 1~ 9.0 5 4 2~ 2.2 100~ 75%
1~ 0.56 80% 40%
~*
2 0.28 70%
3 9.0 5 4 3 2.2 95~ 7~
3 0.56 80~ 40%
3 0.28 60%

6 9.0 2 2

7 9.0 5 4 * Tested as a mixtur-.

- :

.

1~88543 Test 5 broadleaf weed test A number of typical compounds were tested in the greenhouse against broadleaf weeds which are repre~entative of families of weeds which exhibit resi~tance to many known herbicides. The te~t method was generally the ~ame as the method of Test 4, except that only preemergence surface ap-plications of the compounds were made. All compounds were te~ted at 9.0 kg./ha. The 1-5 rating ~cale wa~ u~ed.
Table 6 ~- ;
Compound ~-of Garden Example Huckle- Sickle- Common Prickly ~-NO. ~r~y__ pod Ragweed Sida 1~ - . ', ,-.
j 5 5 6 3 3 4 ~

* Te~ted a~ a mixtùre.
20 Test 6 ~ ;
fourteen-species test -This greenhou~e te~t wa~ performed to evaluate typical compounds of the invention against a number of crop and weed pecie~. The compounds w-re test-d at variou~ -rates as indicated in the table below. In all ca~es, the ~ -compound~ were applie~ preemerqencé to the test plants and were either incorporated in the soil before the seed~ were - ;~
planted, or ~urface-appl~ed aftér planting. In general, the ' ' ~ - .

.

1~88543 formulation of the compounds and planting and observation of the test plants proceeded according to the method of Test 4, except that the compounds were di~solved in acetone-ethanol at 1 g./100 ml. concentration. A 0-10 rating ~cale was used, where 0 indicates normal plants, and 10 ind~cates dead plants or no emergence.

, ~ , .
. .

.

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s~elg ~
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~, :~; X-4427A -72-' .

1~885~3 The broad-~pectrwm activity of the compounds of formulae (I), (II) and (III) i8 clearly illu~trated by the above examples. The test result~ point up the efficacy of the compounds against annual grasses, the relatively easily-controlled broadleaves such as pigweed, and the more re-sistant broadleaves such as nightshades. Plant ~cientists will recognize that the exemplified activity of the com-pounds shows that the compounds are broadly effective against herbaceous weeds.
As the above test results demonstrate, an im-portant embodiment of this invention is a method of reducing the vigor of unwanted herbaceous plants which compr1ses contacting the plants with an herbicidally-effective amount of one of the compounds described above. In ~ome instance~, as is clear from the test results, the whole population of the contacted plant ~8 killed. In other instances, part of the plants are killed and part of them are in~ured, and in st~ll other instances ~ none of the plant~ are kllled but are merely injured by application of the compound. It will be understood that reducing the vigor of the unwanted plant population by injuring the indivtdual plants, or by Xilllnq part and injuring part, is beneficial even though ~ome part of the plant population survives application of the com-pound. The plant~, the vigor o$ which has been reduced, are unusually ~uscepti~le to the stresses, such a~ disea~e, drought, lack of nutrients and 80 forth, which normally afflict plants.
Thus, the treated plants, even though they surviv-appIication of the compound, are likely to expire due to .

~88543 stress of the environment. Further, if the treated plants are growing in cropland, the crop, growing normally, tends to shade out the treated plants of reduced vigor. The crop, therefore, has a great advantage over the treated unwanted plants in the competition for nutrients and sunlight. Still t further, when the treated plants are growing in fallow land, or industrial property which is desired to be bare, the fact that their vigor is reduced necessarily tends to minimize the treated plants' consumption of water and nutrients, and ~ -~
al~o minimizes the fire hazard and nuisance which the plantspresent.
~ he compounds are herbicidally effective when applied both preemergence and postemergence. Thus, they can be applied to the 80il to kill and injure weed~ by soil contact when the weed seeds are germinating and emerging, and can also be used to kill and injure growing weed~ by ~/ -direct contact with the exposed portions of the weeds.
Preemergence application of the compounds, wherein the unwanted herbaceous plants are contacted with the compound through application to the ~oil, is preferred. Seeds of unwanted plants, which are contacted with the compound~ by soil application, are here regarded as plants.
Preemergence applications of the compounds are effective, as the examples show, whether the compounds-are applied to the ~urface of the ~oil or are incorporated in the soil.
The preferred compounds, which are also the compounds wlth which the herbicidal method is preferably carried out, are the following.

~X-4427A -74-1~88543 2,3-dihydro-1-methyl-3-(3-methylphenyl)-5-phenyl-4(lH)-pyridinone.
2,3-dihydro-1-methyl-5-(3-methylphenyl)-3-phenyl-4(lH)-pyridinone.
2,3-dihydro-1-methyl-3-phenyl-5-(3-trifluoro-methylphenyl)-4(lH)-pyridinone.
2,3-dihydro-1-methyl-5-phenyl-3-(3-trifluoro-methylphenyl)-4(lH)-pyridinone.
2,3-dihydro-3-(4-fluorophenyl)-1-methyl-S-(3-trifluoromethylphenyl)-4(lH)-pyridinone.
2,3-dihydro-5-(4-fluorophenyl)-1-methyl-3-(3-trifluoromethylphenyl)-4(lH)-pyridinone.
3-(4-chlorophenyl)-2,3-dihydro-1-methyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridinone.
l-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4-piperidinone.
As the examples above illustrate, the compounds are acceptably ~afe to a number of crops, such a~ peanut~, soybean, sorghum, wheat and rice when applied at proper rates and at appropriate times. It will be noted that the compounds are particularly and notably harmle~s to cotton in the exemplified experiments. Because of the safety with which this crop may be treated with the compounds, the use of the method to reduce the vigor of unwanted plants in cotton cropland is a preferred embodiment of the invention.
The best application rate of a given compound of formula ~III) for the control of a given plant varies, of course, depending upon the method of compound application, ~ 1~88S43 climate, soil texture, water and organic matter contents of the ~oil and other factors known to those ~killed in plant ~cience. It will be found, however, that the optimum ap-plication rate iB in the range of from about 0.25 to about 20 kg./ha. in virtually every case. The optimum rates will usually be found to be within the preferred range of from about 1 to about 10 kg./ha.
The time when the compounds should be applied to the soil or the unwanted plants is widely variable, ~ince the compound~ are effective both preemergence and post-emergence. At lea~t some control will result from appli- ;~
cation of the compound~ at any time when plants are growing or germinating. They may also be applied to the soil during a dormant sea~on to kill weeds germinating during the following warm season.
When the compounds are used for weed control in an annual crop, it is usually be~t 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 incor- -20 porated, it will usually be applied and incorporated im- -mediately before planting. If it is to be surface applied, it is usually simplest to apply the compound immediately after planting.
~he compounds are applied to the soil or to .
emerged planta in the manners usual in agriculture. ~hey may be applied to the soil in the form of either water-dispersed or granular formulations, the preparation of which will be discussed below. U~ually, water-disper~ed .
., ~ .

~ X-4427A -76-. ..

1~88543 formulations will be used for the application of the com-pound~ to emerged weed~. The formulation~ are applied with any of the many types of sprayers and granular applicator~
which are in wide use for the distribution of agricultural chemicals over soil or ~tanding vegetation. When a compound is to be soil-incorporated, any of the usual ~oil incorpora-tion equipment, such a~ the di~c harrow, the power-driven rotary hoe and the liko, are effective.
The compound~ are useful for the control of aquatic weeds, as well a~ terrestrial unde~ired plants.
Such aquatic weeds a~ duckweed, water milfoil, hydrilla and the like are controlied when the compound~ are disper-ed in the infested water at concentrations in the r~nge of from about 0.1 to about 10 p.p.m. by weight. The compound- are applied to water in the form of thé ~ame type~ o herbicid~l compositions used for other herbicidal uses.
The compound~ are normally uQed in the form of the herbicidal compo~itions which are an important embodiment of ~he invention. An herbicidal composition comprise~ a compound useful in controlling unwanted plant~ and an in~rt carrier. In general, the compositions are formulated in the manners uqual in agricultural chemistry, and are novel only beaau~e of the vital presence of the herbicidal compound.
Very often, the compounds are formulated a~ con-centrated compo~itions which are applied either to the ~oil or the foliage in the form of water dispersions or emulsion~ -containing in the range of from about 0.1 percent to about 5 percent of the compound. Water-dispersible or emul~ifiable - ,~, ~ X-4427A -77-.

compositions are either solids usually known as wettable powders, or liquids usually known as emulsifiable concen-trate~. Wettable powders comprise an intimate, finely-divided mixture of the compound, an inert carrier and sur-factants. The concentration of the compound is usually from about 10 percent to about 90 percent. The inert carrier i8 `~ :
usually chosen from among the attapulgite clays, the kaolin clays, the montmorillonite clays, the diatomaceous earths or the purified silicates. Effective surfactants, comprising from about 0.5 percent to about 10 percent of the wettable powder, are found among the sulfonated lignins, the con-densed naphthalenesulfonates, the naphthalenesulfonates, the ~-alkylben2enesulfonates, the alkyl sulfates and nonionic -~
surfactants such as ethylene oxide adducts of phenol.
Typical emulsifiable concentrates of the compounds comprise a convenient concentration of the compound, such as -from about 100 to about 500 g. per liter of liquid, di~-solved in an inert carrier whi¢h i~ a mixture of water-immiscible solvent and emulsifiers. Useful organic ~olven*s include the aromatics, especially the xylenes, and the petroleum fractions, especially the high-boiling naphthalenic and olefinic portions of petroleum. Many other organic solvents may also be used such as the terpenic solYent~ ~ and the complex alcohols such as 2-ethoxyethanol. Suitable emulsifiers for emulsifiable concentrates are chosen from the same types of surfactants used for wettable powders.
When a compound i~ to be applied to the soil, as for a preemergence application of the compound, it i8 con-- venient to use a granular formulation. Such a formulation .

1~88543 `-typically eompri-o- the compound di-persed on a granular inort earrier ~ueh as coarsely ground elay The particle ~ize of granules usually ranges from about 0 1 to about 3 mm The usual formulation proeo~ for granule~ eompri~o-di~olving the eompound in an inexpon-ive olvont and applying the ~olution to the carrier in an appropriato solids mixer Somewhat le~ oeonomieally, the eo~pound may be di~per~ed in a dough eomposed of damp elay or other inert carrier, whieh i~ thon dried and eoar~ely ground to produe-the de~ired granular produet It ha- boeome eu-tom-ary in agrieultural ehemi-try to apply two or even moro agrieultural ehamiealJ ~i~ul-taneou~ly in ordor to eontrol weed~ of many diff-rent typ--, or weods and other pest~, with a ingl- applieation of ehemieals The eompound- of formula (III) lend them~elv -well to eombination with othor agrieultural eh~miaal- and may u-efully bo eombin-d with inseetieides, fungieide~, nomatieide~ and other herbieido~ aJ may be dosirable ~nd eonvonient - ' .' -~, ''.

X-4427A _79_ -

Claims (11)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A compound of one of the general formulae or (I) (II) wherein R is methyl or ethyl;

R1 is hydrogen, phenoxy, phenylthio, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkyl, phenyl or phenyl monosubstituted with chloro or fluoro;
R2 is bromo, fluoro or trifluoromethyl;
R3 is C1-C3 alkyl, C2-C3 alkenyl or propargyl;
R4 is hydrogen, phenoxy, phenylthio, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, phenyl or phenyl monosubstituted with chloro, bromo, fluoro, trifluoromethyl, C1-C3 alkyl or C1-C3 alkoxy;
R5 is chloro, bromo, fluoro, trifluoromethyl, C1-C3 alkyl or C1-C3 alkoxy;
either X and X1 combine to form a carbon-carbon bond and x2 and X3 are hydrogen atoms, or X and X1 are hydrogen atoms and x2 and X3 combine to form a carbon-carbon bond.

2. A compound of Claim 1 of formula I.

3. A compound of Claim 2 wherein R1 is hydrogen, alkyl, phenyl or substituted phenyl.

4. The compound of Claim 1 or 3 which is 1-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4-piperidinone.

5. A compound of Claim 1 of formula II.

6. A compound of Claim 5 wherein R3 is alkyl or alkenyl.

7. A compound of Claim 6 wherein R4 is hydrogen, alkyl, phenyl or phenyl monosubstituted with chloro, bromo, fluoro, trifluoromethyl, methyl or methoxy.

8. A compound of Claim 6 wherein R5 is chloro, bromo, fluoro, trifluoromethyl, methyl or methoxy.

9. The compound of Claim 1 or 8 which is any one of the following compounds:
2,3-dihydro-1-methyl-3-(3-methylphenyl)-5-phenyl-4(1H)-pyridinone 2,3-dihydro-1-methyl-5-(3-methylphenyl)-3-phenyl-4(1H)-pyridinone 2,3-dihydro-1-methyl-3-phenyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridinone 2,3-dihydro-1-methyl-5-phenyl-3-(3-trifluoro-methylphenyl)-4(1H)-pyridinone 2,3-dihydro-3-(4-fluorophenyl)-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridinone 2,3-dihydro-5-(4-fluorophenyl)-1-methyl-3-(3-trifluoromethylphenyl)-4(1H)-pyridinone 3-(4-chlorophenyl)-2,3-dihydro-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridinone

10. A process for the preparation of a compound of one of the general formulae or (I) (II) wherein the various symbols are defined as in Claim 1 which comprises reducing a compound of one of the general formulae or (IV) (V) wherein the various symbols are defined as in Claim 1 with an aluminium or boron hydride.

11. A herbicidal method of controlling noxious vegetation which comprises applying to an area containing said noxious vegetation a compound of the general formulae (I) or (II) as claimed in claim 1, 2 or 5.