Note: Descriptions are shown in the official language in which they were submitted.
~137~5~3~
This invention relates to certain novel N-substituted
halo-2-pyrrolidinones ~also known as azacyclopentan-3-ones)
which are prepared by a novel process and which are useful as
herbicides. More specifically, this invention relates to
certain acyclic, alicyclic and monocyclic aromatic or phenyl
2- or N-substituted halo-2-pyrrolidinones, to their prepar- :~.
ation and utility of the compounds as herbicides~
The compounds comprising the instant class of
compounds of the acyclic and alicyclic type correspond to the
. 10 general formula: ;
X Q .
Y C C .
¦ > N-R
Z C~2 C 2 ;
H
. ~',
in which Q is oxygen or sulfur; R is lower alkyl, alkenyl,
haloalkyl, cycloalkyl, cycloalkyla:Lkyl.j benzyl and chloro-
.
benzyl; X is hydrogen or chlorine; Y is chlorine or bromine,
and Z is chlorine or bromine: pro~ided that when R is allyl r
: Y and Z are each chlorine or bromine, and provided that when
R is cyclohexyl, X is other than chlorine.
The compounds comprising the instant class of compounds
of the monocyclic, aromatic or phenyl type, correspond to
the general formula:
X O
li l
;- 7 \N~R
Z CH - CI CH/ \,~ 1
., R2 H ~: :
:
.,
.
- ' ' ~ ''. '
~651~8
in which. X is hydrogen, chlorine or methyl; Y is hydrogen,
chlorine or bromine; Z is chIori.ne or bromine; R2 is alkyl or
hydrogen; R is hydrogen, alkyl, acetyl, chlorine, bromine,
fluorine, iodine, trifluoromethyl, nitro, cyano, alkoxy,
alkylthio, alkylsulfinyl, alkylsulfonyl, trifluoromethylthio,
trifluoromethylsulfinyl, trifluoromethylsulfonyl, pentafluoro-
propi.onamido, or 3-methylureido; and Rl is hydrogen, alkyl,
chlorine or trifluoromethyl.
In the above description, the following preferred
embodime.nts are intended for the various substituent groups:
Lower alkyl preferably includes, unless otherwise provided
for, those members which contain from 1 to 6 carbon atoms,
incluslve, in both straight chain and branched chain config-
urations, for example, methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, amyl, isoamyl, hexyl and isohexyl, and
the like; by the term "haloalkyl" is meant those previously
described alkyl members having 1 to 6 carbon atoms, having
in addition one or more halogen substitutions such as mono,
di, tri, tetra and ~ fluoro, chloro, bromo or iodo, alkenyl
: 20 preferably includes, unless otherwise provided for, those
members which contain at least one olefinic double bond and .
contains from 3 to 6 carbon atoms, inclusive; for example,
allyl, methallyl, ethallyl, l-butenyl, 3-butenyl, 2-methyl- :~
l-butenyl, l-pentenyl, 2-pentenyl, 3-pentenyl, 2-methyl-1- :
pentenyl, l-hexenyl, 2-hexenyl, 3-hexenyl and the like;
cycloalkyl preferably includes from 3 to 7 carbon atoms,
inclusive, for example, cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl and the like; cycloalkylalkyl preferably includes
` those members having a total carbon content of from 4 to 8
30 carbon atoms, inclusive, including for example, cyclopropyl-
methyl, cycloproplethyl, cyclobutylmethyl, cyclopentylmethyl,
--4--.
~76S~8
cyclohexylmethyl and the like. ~or various substituent
groups having alkyl, or an alkyl member as in alkoxy, alkyl-
thio, alkylsulfinyl, or alkylsulfonyl, unless otherwise
provided for, those members contain from 1 to 4 carbon atoms,
inclusive, in both straight chain and branched chain config-
uratlons, for example, methyl~ ethyl, n-propyl, isopropyl,
n-butyl, isobutyl and the like.
As a consequence of the presence of unsymmetrically
substituted carbon centers in certain of the compounds within
the scope of this invention, it is recognized that the
possibility exists for cis-trans or geometric isomerism. Such
cls-trans isomers are stereoisomers whose structures differ
only with respect to the arrangement of certain "rigidly"
positioned atoms or groups relative to a specified plane of
reference. The plane of reference herein is the pyrrolidinone
- ring. In specifying cis-trans configurations in a monocyclic
compound, any of the ring positions having non-identical
groups are considered to assign relative configurations.
Using the pictoral connotation for representing these relative
2Q positions in structural formulas, the pyrrolidinone ring -
system is considered flat. The atoms or groups under con-
sideration are described as cls when they are on the same
side of the plane and trans when they are on opposite sides
of the plane (see Gilman's, Organic Chemistry, Vol. I, ;
p. 477~.
The compounds of this invention have been found to be
active herbicides of a general type. That is/ members of the
class have been found to be herbicidally effective against a
wide range of plant species. A method of controlling undesir
able vegetation of the present invention comprises applying an
herbicidally effective amount of the above-described compounds
to the area or plant locus where control is desired.
!
~ ' . ' . . ' . : ,' '
- - \
~C37~5~
An herbicide is used herein to mean a compound whi.ch
c:ontrols or modifies the growth of plants. By a "growth
controlling amount" is meant an amount of compound which
causes a modifying effect upon the growth of plants. Such
modifying effects include all deviations from natural :
development, for example, kï.lling, retardation, defoliation,
desiccation, regulation, stunting, tillering, stimulation,
dwarfing and the like. By "plants", it is meant germinant
seeds, emerging seedl;ngs, and established vegetation,
including the roots and above-ground portions.
~ The intermediates for the preparation of the N-mono
; cyclic aromatic halo-2-pyrrolidinones are the unsaturated N-
alkenyl haloacyl anilides obtained by the acylation of the
appropriate unsaturated N-alkenyl anilides. Suitable anilines,
~ that are not commercially available, may be prepared by a
number of methods reported in various sources of the chemical
literature and various reviews on the subject such as
"Synthetic Organic Chemistry" ~y Wagner and Zook, Chapter 2~,
John Wiley and Sons, New York, 1961. In the examples to
2Q follow, a specific example of the preparation of an inter-
medi.ate unsaturated N-alkenyl haloacyl anilide is described.
The mono-cyclic aromatic N-substituted halo-2-pyrroli-
dinones are prepared by several different methods, depending
upon the nature of the starting materials and products desired.
A preferred method not heretofore disclosed or known in the
prior art is the rearrangement reaction of an N-alkenyl
containing haloacyl amide in the presence of a catalytic amount
of ferrous ion~ The use of a solvent is desirable to
facilitate processing of the reaction and to aid in the
~ 30 agitation by providing adequate volume, as well as solubil-
; i.zing the reagents. The preferred solvents include those
which are high boiling and which do not interfere with the
--6~
.
-
~L~37~8~
reaction, for example, dlethylene glycol dimethyl ether,
dimethyl formamide, dimethyl acetamide, dimethylsulfoxide,
mesi.tylene and the like. Ferrous ion catalyst sources may
be provided from various reagents, for example, ferrous
chloride, ferrous brom.ide, iron metal, ferrocene, ferrous ~;
acetonyl acetonate and th.e like.
The intermediates for the preparation of th.e N-substi- :
tu~ed halo-2-pyrrolidinones are the unsaturated haloacyl
amides obtained by the acylation of the appropriate unsaturated
amines~ Unsaturated amines, that are not commercially
available, may be prepared by methods reported in various .
souxces of the chemical literature and various reviews on the
subject such as "Synthetic Organic Chemistry" by Wagner and
Zook, Chapter 24, John Wiley and Sons, New York, 1961. In the
examples to follow, a specific example of the preparation of
an intermediate unsaturated haloacyl amide is described.
The acyclic and alicyclic N--substituted halo-2-pyrroli-
dinones are prepared by several different methods, depending
upon the nature of the staring materials and products desired.
A preferred method not heretofore disclosed or known in the .
prior art is the rearrangement reaction of an N-alkenyl
containing haloacetamide in the presence of a catalytic amount ~ : .
of ferrous ion. The use of a solvent is desirable to
facilitate processing of the reaction and to aid in the
agitation by providing adequate volume, as well as solubil- .-.
izing the reagents. The preferred solvents include those
. which are high boiling and whi.ch.do not interfere wi.th the
reaction, for example, diethylene glycol dimethyl ether,
dimethyl formamide, dimethyl acetami.de, dimethylsulfoxide,
mesitylene and the lLke. Ferrous ion catalyst sources
may be provided from various reagents, for example, ferrous
chloride, ferrous bromide, iron metal, ferrocene, ferrous
--7--
;, .
'. '
1~7~5~8
acetonyl acetonate and the like.
Since the reaction is a rearrangement of the unsatur-
I ated haloacylamide in the presence of a catalytic amount of
ferrous ion, the amounts of reagents is not critical. The
reactïon is preferably conducted at reflux temperatures. The
temperatures for the reaction are best de~ined between about
room temperature and the reflux temperature for the solvent
if one is employed. Preferably, the reaction temperature is
between about 50C. to about 190C., more preferably, the
temperature range is between about 125C. to about 170C.
At the elevated temperatures, the reaction as described
hereinabove proceeds rapidly to yield the desired product.
In each instance after the reaction is complete, the
recovery is carried out by normal work-up procedures, such
as crystallization, sublimation, distillation and the like.
Generally, the reaction for the acyclic and alicyclic
N-substituted compounds of this invention can be represented
by the following equation.
~ O X O
` D I il
~ CXY C Y C C -
;~ \ N-R Fe ~ ¦ \ N-R
high bolling
CH2 CH - CH/2 solvent 2 CH----CH/
wherein X, Y, Z and R are defined as above.
Generally, the reaction for the mono~cyclic or
phenyl N-substituted compounds of this invention can be
represented by the following equation:
:
~ -8-
~765E~ ~
o ~ :
CXY cD .
Z N ~
R2CH CH 2 1 high boiling solvent >
D
Y - - C C
! N - ~
CHZ CH CH2
R2 ~ :
:
wherein Xt Y~ Z~ R, Rl and R2 are defined as above.
The compounds of the present invention and intermediates
therefor are more particularly illustrated by the following
examples which describe their preparation. Following the
examples is a table of compounds which are prepared according
to the procedures described herein.
EXAMPLE A
Pre~aration o~ Intermediate N-allyl-N-butyl dichloroacetamide
from allyl-n-butyl amine.
Allyl-n-butyl amine prep~aration. Fifty grams of
N-allyl butyramide, prepared by the reaction of allyl amine
with butyryl chlorlde, was dissolved in 100 ml. of benzene and
admitted dropwise to a stirred solution of 168 g. of sodium
bis (2-methoxy ethoxy) aluminum hydride (Red Al)~ in 300 ml.
of benzene at reflux under a nitrogen atmosphere. Reflux was `~'
maintained for an hour after addition was complete after which
the mixture was cooled and added dropwise to a solution
prepared from 200 ml. of 50 per cent sodium hydroxide and 300
g. of crushed ice. ~he aqueous layer was extracted with three
lO0 ml. portions of benzene and the combined benzene extracts -;
_9_
:
,
76581~
were dried over magnesium sulfate and the product converted
to the hydrochloride with excess 20 per cent ethereal
hydrochloric acid. The hydrochloride salt was filtered off
and dried. Yield was 35.4 g. and the salt was used without
further purification.
N-allyl-N-butyl dichloroacetamide preparation. Ten
and five-tenths grams of allyl-n-butyl amine hydrochloride
was added to lO0 ml. of methylene chloride followed by 14.5 g.
of triethylamine. The mixture was stirred in a wa-ter bath at
room temperature while 10.4 g. of dichloroacetyl chloride was
added dropwise, and stirring was continued for 30 minutes after
addition was complete. The mixture was washed and the solvent
stripped under vacuum. Yield was 13 g., n30 1.4603. The
intermediate was used without further purification to prepare
Compound No. 12 (Example VII).
XAMPLE I
Preparation of N-allvl-3-chloro-4-chloromethyl-2-pyrrolidinone
Twenty and eight-tenths grams of N,N-diallyl dichloro-
acQtamide was mixed with 25 g. of diethylene glycol dimethyl
ether (diglyme), l g. of ferrous chloride (FeCl2-4H2O) added
and the mixture was heated at reflux for 30 minutes. The
conversion was monitored by the appearance of a new carbonyl
peak at ~ 5O8 microns in the infrared. An additional gram of
ferrous chloride ~FeC12 4H2O) was added and heating was
continued for an additional 30 minutes. The reaction mixture
was diluted with methylene chloride, washed with water and
dried and stripped. The dark liquid product was distilled
under vacuum to give 8.4 g. of light yellow oil, b.p. 124-
127C. at 0.25 mm. nD 1.4850.
The proton and carbon-13 ~MR spectra indicate that
the product is a mixture of-cls and trans isomers with a
ratio of 2:1, cis to trans.
--10--
5~
EXAMPLE II
Preparation of l-allyl-3-bromo-4-bromomethyl-2-pyrrolidinone
Ten and nine-tenths grams of N,N-diallyl-dibromo-
acetamide was added to 15 ml. of diglyme followed by 1 g. of
anhydrous ferrous bromide. The mixture was heated at reflux
and the conversion to pyrro]idinone checked by GLPC. When
conversion was complete, the product was diluted with methylene
chloride, washed with water, dried over anyhdrous magnesium ~-
sulfate and treated with silica gel to remove tarry material.
The solvent was stripped under vacuum to give 8.1 g. of
product, nD 1.5350.
EXAMPLE III
Preparation of N-allyl-3-chloro-4-chloromethyl-2-pyrrolidi-
nonethione
Six and two-tenths grams of N-allyl-3-chloro-4-chloro-
methyl-2-pyrrolidinone was dissolved in 100 ml. of methylene
chloride and 10 g. of phosphorus pentasulfide in two 5 gram
portions was added about an hour apart while the mixture
was allowed to stir at room temperature overnight. The
mixture was filtered to remove solids and stripped to give
5 g. of liquid containing some precipitated solid. This was
taken up in pentane, filtered to remove solids and stripped.
There was obtained 3 g. of the product, an oil, nD 1.5487.
Examination of the infrared spectrum showed almost no carbonyl
absorption at~5.8 microns.
EXAMPLE IV
Preparation of N-pro~yl-3-chloro-4-chloromethYl-2-pyrrolidinone
This compound can be prepared by the rearrangement of
; N-allyl--N-propyl dichloro acetamide or by reduction of N-allyl- -
3-chloro-4-chloromethyl-2-pYrrolidinone as shown below.
T~enty and eight-tenths grams of N-allyl-3-chloro-4
chloromethyl-2-pyrrolidinone was dissolved in 150 ml. of
. .
~7~58~
ethanol and 150 mg. platinum oxide was added. The mixture
was shaken under hydrogen gas at 48 psi until hydrogen uptake
was complete (22 minutes~. The mixture was treated with a few
grams of Dicalite and filtered to remove the catalyst and the
solvent stripped under vacuum. Yield was 21 g. of product,
nD 1.4748.
EXAMPLE V
Preparation of N-benzyl-3-chloro-4-chloromethyl-2-pyrrolidinone
Eleven and one-tenth grams of N-allyl-N-benzyl dichloro-
acetamide was dissolved in 12 ml. of diglyme and 1 g. of
anhydrous ferrous chloride added. The mixture was heated at
reflux under nitrogen until conversion to the pyrrolidinone
was complete as indicated by GLPC. The mixture was diluted
with methylene chloride, washed with 5 per cent hydrochloric
acid, separated, dried over an~ydrous magnesium sulfate,
treated with activated carbon and Florisil and stripped
under vacuum. Yield was 6 g. of the title compound, nD
1.5387.
EXA~PLE VI
Preparation of N-cyclopropylmethyl-3-chloro-4-chloromethyl-2-
p~vrrolidinone
Twelve and one-tenth grams of N-allyl-N-cyclopropyl-
methyl dichloroacetamide was dissolved in 15 ml~ of diglyme
and 1 g. of anhydrous ferrous chloride addedO The mixture was
heated at reflux under a nitrogen atmosphere for 25 minutes
and conversion checked by GLPC. When conversion was complete,
the diglyme was stripped off under vacuum and the mixture
dissolved in benzene, washed with 5 per cent hydrochloric acid,
separated,dried over anhydrous magnesium sulfate, treated
with activated carbon, filtered through Florisil and the
solvent removed under vacuum. Yield was 8.8 g. of product,
nD 1.4922.
-~2-
EXAMPLE VII
.. .
Preparation of N-butyl-3-chloro-4-chloromethyl-2-pyrrolidinone
Eleven grams of N-allyl-N-butyl dichloroacetamide was
dissolved in 15 ml. of diglyme and 1 g. of anhydrous ferrous
chloride was added. The mixture was heated to reflux in a
nitrogen atmosphere for 25 minutes and the conversion monitored
by gas-liquid partition chromatograph (GLPC~. The diglyme was
stripped off under vacuum and the mîxture diluted with ~enzene,
washed with 5 per cent hydrochloric acid, dried over anhydrous
magnesium sulfate and treated with activated carbon to remove
tarry by-products and filtered through Florisil. The solvent
was stripped under vacuum to give 8.1 g. of product, n30
1.4731.
EXAMPLE B
Preparation of Intermediate N-allyl-m-trifluoromethyl aniline
from m-trifluoromethyl acetanilide.
N-allyl-m-trifluoromethyl aniline preparation. m-tri-
fluoromethyl acetanilide was prepared from the aniline by
reaction with acetic anhydride. The acetanilide, 192 g., -
was dissolved in 300 ml. of tetrahydrofuran (THF) and added
dropwise with stirring to a slurry of sodium hydride. 24 g.,
in 200 ml. of THF under a nitrogen atmosphere at ambient
temperature. When hydrogen evolution stopped, allylbromide,
121 g., was added and the mixture was allowed to reflux for
1 hour and stir overnigh~. The mixture was filtered and
stripped under vacuum and the residue diluted with methylene
chloride, washed with wate~r, dried and stripped under vacuum.
Yield was 205 g. of product, N-allyl-m trifluoromethyl
acetanilide~ n30 1.4532. The product was of sufficient
purity to be used in the next step, without further purifi-
- cation.
The product was added to 20 a ml. of concentrated
-13-
.
~7~
hydrochloric acid with 250 ml. of water. The 2-phase system
was heated to reflux with stirring until a clear solution
resulted in about 2 hours. The mixture was cooled and the
product crystallized out. The mixture was treated with 50%
sodium hydroxide with cooling to liberate the N-allyl anilide
which was extracted with methylene chloride, dried over
magnesium sulfate and stripped to give 170 g. of product.
Since gas liquid partition chromatography (GLPC) indicated
only 85% purity, the material was dissolved in ether and
reprecipitated as the hydrochlorlde with 20% ethereal
hydrochloric acid. Yield was 173 g., m.p. 104-106~C.
N-allyl-m-trifluoromethyl-dichloroacetanilide prepara-
tion. Twenty-three and eight tenths grams of N-allyl m-
trifluoromethyl aniline hydrochloride was suspended in 200
ml. of methylene chloride, 21 g. of triethylamine was added
and the mixture stirred in a water bath at room temperature
while 15 g. of dichloroacetyl chloride was added dropwise.
After stirring about 30 minutes, after addition was complete,
the mixture was washed with dilute ~ 1% sodium hydroxide,
dilute ~1% hydrochloric acid and water, separated and dried
over magnesium sulfate and the solvent stripped under vacuum.
The product was dissolved in ether and treated with 10 g. of
20% ethereal hydrochloric acid, the precipitate filtered off
and the ether stripped under vacuum to give 25 g. of product,
n30 1.4740.
EXAMPLE VIII
_eparation of N-m-trifluoromethylphenyl-3-chloro-4-chloro-
methyl-2-pyrrolidinone.
Thirty milliliters of ethylene glycol dimethyl ether
(diglyme) was added to 2 g. of ferrous chloride ~FeC12 4H2O~
and heated to the boiling point under a nitrogen blanket and
10 g. of a water-diglyme mixture was removed. To this was
-14-
11D7~5~1~
added 12.5 g. of N-allyl-m-trifluoromethyl dichloroacetanilide
and heating was continued for 15 minutes at reflux and the
conversion to product was determined by GLPC. When conversion
was complete tabout 3Q minutes of reflux), the mixture was
cooled, diluted with methylene chloride, washed with 5~
hydrochloric acid, separated, dried with magnesium sulfate,
treated with activated carbon and Florisil, filtered and the
solvent removed under vacuum. Yield was 10 g. of oil, n30
1.50320
As noted above, stereoisomers are possible in the
compounds which possess carbon atoms in the pyrrolidinone
ring having non-identical groups attached thereto. The
compound of this example is one such compound and is used as
an example of the separation, identification and later
herbicidal activity of the cis and trans configurations.
The compound from the above procedure, an oil, n30
; 1.5032, was allowed to stand overnight and a portion crystal-
lized. This material was triturated with carbon disulfide
and a slurry of crystals was obtained. The crystals were
removed by filtering the slurry. This was identified by N~R
to be the trans configuratïon (I). m.p. 54-55C.
Upon chilling the carbon disulfide filtrate, a further
crop of crystals was obtained. After separation and drying,
these crystals were identified by NMR to have the cis
configuration (II), m.p. 79-80C.
oH
oCl o
CF3 CO - C CP3 / Cl
(I) TRANS (II) ~IS
':
-15-
,
7~5~3
EXAMPLE IX
Preparation of N-m-chlorophenyl-3-chloro-4-chloromethy1-2-
pyrrolidinone.
Two grams of FeC12 4H2O was suspended in 30 ml. of
diglyme and heated to reflux under a nitrogen atmosphere while
10 g. of water-diglyme mixture were distilled off. N-allyl
m-chloro-dichloroacetanilide, 11.1 g., was added and heating
continued for 20 minutes and the extent of reaction determined
by GLPC. When conversion was complete (20 minutes), the
mixture was cooled, diluted with methylene chloride and washed
with 5% hydrochloric acid, separated, dried over magnesium
sulfate, treated with Florisil and activated carbon, filtered
and the solvent stripped under vacuum. The product, a thick
dark oil~ crystallized on standing and was purified by
recrystallization from carbon tetrachloride. Yield was 2.9
g. of product, m.p. 93-94C.
EXAMPLE X
Preparation of N-phenyl-3,3-dichloro-4-chloromethyl=2-
pyrrolidinone.
2Q One gram of FeC12 4~I2O was suspended in 25 ml. of
diglyme and 20 g. of N-allyl-trichloroacetanilide was added
and the mixture was heated at reflux under nitrogen. After
15 minutes, conversion to product was complete and the
mixture was diluted with benzene and washed with water. The
product crystallized from benzene solution and was filtered
off. A sample was recrystallized from ethanol, giving an m.p.
of 133-134C.
EXAMPLE XI
Preparation of N-m-trifluoromethylphenyl-3-bromo-4-bromo-
methyl-2-pyrrolidinone.
.
One gram of anhydrous ferrous bromide (FeBr2~ was
suspended in 15 ml. of diglyme, 9.6 g. of N-allyl-m-
-16-
'' ' ''
~ 7~
trifluoromethyl dibromoacetanilïde was added and the mixture
was heated to reflux under a nitrogen atmosphere for 15
minutes. The mixture was cooled, diluted with methylene
chloride, extracted with water and 5~ hydrochloric acid
solution, dried, treated with florisil, filtered and the
solvent stripped under vacuum. ~ield was 7.6 g. of a dark
liquid.
EXA~PLE XII
Preparation of N-m-nitrophenyl-3~chloro-4-chloromethyl-2-
pyrrolidinone.
A mixture of 10.1 g. of N-allyl-m-nitro-dichloroacet-
anilide, 15 ml. of diglyme and 1 g. of anhydrous ferrous
chloride (FeC12) was heated at reflux under nitrogen for 1
hour and cooled. The mixture was diluted with benzene, washed -
with 5~ hydrochloric acid and the solution treated with
magnesium sulfate and activated carbon, filtered through a
pad of Florisil and the solvent stripped under vacuum. The
product, 6 g. of a thick oil, solidified on standing.
Trituration with ether gave 3 g. of crystalline solid, m.p.
102-104C.
The following is a table of compounds which are
prepared according to the aforementioned procedures. Compound
numbers have been assigned to them and are used for
identification throughout the balance of the specification.
'.
-17-
5~8
TABLE I
X O
Y --C 11
~~\ N-R
Z CH2 C CH2
H
COMPOUND n30 or
NUMBER R X Y Z_ Q b. p. C.
1 CH CH - CH HCl Cl O 125/0.25 mm.
2 CH2CH=CH2 C1C1 C1 O 1.4938
3 C2H5 HC1 C1 O 1.4720
4 C2H5 C1C1 C1 O 1.4735
C - C6H11 HCl Cl O 1. 4788
6 CH2CH=CH2 HC1 C1 S 1.5487
7 CH3 HC1 C1 O 1.4860
3 7 HC1 C1 O 1.4748
CH2=CHCH2 HBr Br O 1. 5350
CH2BrCHBrCH2 H C1 C1 O 1.5633 ;~
11 n C5 11 HC1 C1 O 1.4700
12 n-C4H9 HC1 C1 O 1.4731
13 i~C4Hg HCl Cl O 1. 4720
14 DCH2 HC1 C1 O 1.4922
6 5 2 HC1 C1 O 1.5387
16 p-Cl - C6H5CH2 H C1 C1 O 1.5502
.
~ .
.. ~
--1 8--
. .
~ .
.. ... . : ~ . . . .
. . : .,': . :
588
The following compounds correspond to the formula: ~
X I ,.
y C C R
~ >~
Z fH - f CH
R2 H
COMPOUND R R m-p-30~C
NUMBER X Y Z 2 R 1 r nD
17 H Cl Cl H H H 85-90
18 Cl Cl Cl H H H 133-134
19 H ClCl H 2-CH3 6-CH3 semi-solld*
H ClCl H 3-Cl H 93-94
21 H ClCl H 4-Cl H 100-102
22 H ClCl H 3-CF3 H 1.5032 -;
23 CH3 ClCl H H H 79-88
24 Cl ClCl H 3-Cl 4-Cl 119-121
Cl ClCl H 3-CF3 H 100-102
26 CH3 ClCl H 3-CF3 H 76-78
27 H ClCl H 4-CH3 H 100-104
28 H ClCl H 3-F H 60-63
29 H BrBr H 3-CF3 H dark liquid*
H ClCl H 3-C1 4-C1 119-121
31 H ClCl H 3-NO2 H 102-104
32 H ClCl H 3-C1 5-C1 80-gq
33 H ClCl CH3 CF3 - 1.5020 ~. :
34 H ClCl H 3-CN H 1.5550 ~ .
Cl ClCl H 3-Cl 5-Cl 1.5795
36 Cl ClCl CH3 3-CF3 H 1.5122
37 Cl ClCl H: 3-CN H dark red
liquid* :
' ~
--19--
, . :: ' , ' ': . ,
~al7~i5~
TABLE I (continued~
m.p. 0C.
COMPOUND R R or n3
NUMBER X Y Z 2 R 1 D
38 H C1 Cl H 3-CF3 4-C1 1.5263
39 C1 C1 C1 H 3-CF3 4-C1 109-112
H Cl C1 H 3-CF3S H 1.5328
41 H C1 C1 H 3-CH3S H 1.5974
42 H C1 C1 H 3-CF3SO H 1.5248
43 H Cl Cl H 3-CH3SO H 1.5763
44 H Cl Cl H 3-CH3SO2 H glass*
H C1 Cl H 3-CF3SO2 H 1.5228
46 H Cl Cl H 3-CF3 5-CF3 1.4690
47 H C1 Cl H 3-CH30 H 95_99
48 H C1 Cl H 3-CH3CO H 117-121
49 H Cl C1 H 3-CH3 H 89-91
H H C1 H 3-CF3 H 1.4993
51 H C1 Cl H 3-Br H 103-105
52 H Cl Cl H 2-Cl H 1.5530
? 53 H Cl Cl H 3-I H 107-109
54 H C1 Cl H 4-CM30 H 123-125
H Cl Cl H 2-CF3 H 1.4910 `~
56 H Cl Cl H 3-C2F5CONH H 130-132
57 H Cl Cl H 3-CH3NHCONH H 170-172
58 (cis~ H Cl Cl H 3-CF3 H 79-80
59~trans~H Cl Cl H 3-CF3 54-55
;'' : '' '
* = Structure confirmed by infrared analysis. ~
; ' :
-20-
~.
,. .
,
-
~7658~3
The foregoing compounds may be designated:
1. 1-allyl-3 chloro-4-chloromethyl-2-pyrrolidinone
2. 1-allyl-3,3-dichloro-4-chloromethyl-2-pyrrolidinone
3. 1-ethyl-3-chloro-4-chloromethyl-2-pyrrolidinone
4. 1-ethyl-3,3-dichloro-4-chloromethyl-2-pyrrolidinone
5. 1-cyclohe~yl-3-chloro-4-chloromethyl-2-pyrrolidinone
6. 1-allyl-3-chloro-4-chloromethyl-2-pyrrolidinonethione
7. 1-methyl-3-chloro-4-chloromethyl-2-pyrrolidinone
8. 1-propyl-3-chloro-4-chloromethyl-2-pyrrolidinone
9. 1-allyl-3-bromo-4-bromomethyl-2-pyrrolidinone
10. N-2,3-dibromopropyl-3-chloro-4-chloromethyl-2
pyrrolidinone
11. N-amyl-3-chloro-4-chloromethyl-2-pyrrolidinone
12. N-butyl-3-chloro-4-chloromethyl-2-pyrrolidinone
13. N-isobutyl-3-chloro-4-chloromethyl-2-pyrrolidinone
14. N-cyclopropylmethyl-3-chloro-4-chloromethyl-2-
pyrrolidinone
15. N-benzyl-3-chloro-4-chloromethyl-2-pyrrolidinone
16. N-p-chlorobenzyl-3-chloro-4-chloromethyl-2-
pyrrolidinone
17. 1-phenyl-3 chloro-4-chloromethyl-2-pyrrolidinone
18. l-phenyl 3,3-dichloro-4-chloromethyl-2-pyrrolidinone
19. 1-(2',6'-dimethylphenyl)-3-chloro-4-chloromethyl 2-
pyrrolidinone
20. 1-m-chlorophenyl-3-chloro-4-chloromethyl-2-pyrrolidinone
21. 1-p-chlorophenyl-3-chloro-4-chloromethyl-2-pyrrolidinone
22. 1-m-trifluoromethylphenyl-3-chloro-4-chloromethyl-2-
pyrrolidinone -`
23. 1-phenyl-3-chloro-3-methyl-4-chloromethyl-2-
pyrrolidinone
24. 1(3',4'-dichloropheny1~3,3-dichloro-4-chloromethyl-2-
pyrrolidinone
25. 1-m-trifluoromethyl-3,3-dichloro-4-chloromethyl-2-
pyrrolidinone
-21-
7~5~
26. N-m-trifluoromethylphenyl-3-chloro-3-methyl-3-chloro-
methyl-2 pyrrolidinone
27. 1-p-tolyl-3-chloro-4-chloromethyl-2-pyrrolidinone
28. 1-m-fluorophenyl-3-chloro-4-chloromethyl-2-pyrrolidinone
29. N-m-trifluoromethyl-3-bromo-4-bromomethyl-2-pyrrolidinone
30. N-3',4'-dichlorophenyl-3-chloro-4-chloromethyl-2-
pyrrolidinone
31. N-m-nitrophenyl-3-chloro-4-chloromethyl-2-pyrrolidinone
32. ~-3',5'-dichlorophenyl-3-chloro-4-chloromethyl-2-
pyrrolidinone
33. N-m-trifluoromethylphenyl-3-chloro-4~ chloroethyl)-2-
pyrrolidinone
34. N-m-cyanophenyl-3-chloro-4-chloromethyl-2-pyrrolidinone
35. N-3,5-dichlorophenyl-3,3-dichloro-4-chloromethyl-2-
pyrrolidinone -;
36. N-m-trifluoromethylphenyl-3,3-dichloro-4(1-chloroethyl)-
2-pyrrolidinone
37. N-m-cyanophenyl-3,3-dichloro-4-chloromethyl-2-
pyrrolidinone
38. N-3'-trifluoromethyl-4'-chlorophenyl-3-chloro-4-
chloromethyl-2-pyrrolidinone
39. N 3'-tri~luoromethyl-4'-chlorophenyl-3,3-dichlorO-4-
chloromethyl-2-pyrrolidinone
40. N-(m-trifluoromethylthiophenyl)-3-chloro-4-chloromethyl-
2-pyrrolidinone
41. N(m-methylthiophenyl)-3-chloro~4-chloromethyl-2-
pyrrolidinone
42. N(m-trifluoromethyl sulfinylphenyl)-3-chloro-4-chloro-
methyl-2-pyrrolidinone
43. N-(m-methylsulfinylphenyl)-3-chloro-4-chloromethyl-2-
pyrrolidinone
44. N(m-methylsulfonylphenyl~-3-chloro-4-chloromethyl-2-
; pyrrolidinone
45. NCm-trifluoromethylsulfonylphenyl~ 3-chloro-4-chloro-
methyl-2-py-rrolidinone
-22-
~7~i8~
46. N(3',5'-bis-trifluoromethylphenyl~-3-chloro-4-chloro-
methyl-2-pyrrolidinone
47. N-m-methoxyphenyl-3-chloro-4-chloromethyl 2-
pyrrolidinone
48. N-m-acetylphenyl-3-chloro-4-chloromethyl-2-pyrrolidinone
49. N-m-tolyl-3-chloro-4-chloromethyl-2-pyrrolidinone
50. N-m-trifluoromethylphenyl-4-chloromethyl-2-pyrrolidinone
51. N-m-bromophenyl-3-chloro-4-chloromethyl-2-pyrrolidinone
52. N-o-chlorophenyl-N-3-chloro-4-chloromethyl-2-
pyrrolidirIone
53. N-m-iodophenyl-3-chloro-4-chloromethyl~2-pyrrolidinone
54. N-p-methoxyphenyl-3-chloro-4-chloromethyl-2- -
pyrrolidinone
55. o-trifluoromethyl-3-chloro-4-chloromethyl-2-
pyrrolidinone
- 56. N(m-pentafluoro propionamido phenyl) 3-chloro-4-
chloromethyl-2-pyrrolidinone
57. N(m-methylureidophenyl) 3-chloro-4-chloromethyl-2-
pyrrolidinone
58. cis 1-m-trifluoromethylphenyl-3-chloro-4 chloromethyl-
2-pyrrolidinone
59. trans 1-m-trifluoromethylphenyl-3-chloro-4-chloro-
methy1-2-pyrrolidinone
' ~ .
HERBICIDAL SCREENING TESTS
As previously mentioned, the herein described compounds
produced in the above-described manner are phytotoxic
compounds which are useful and valuable in controlling various
plant species. Compounds of this invention are tested as
herbicides in the following manner.
Pre-emergence Herbiclde Screening Test
Using an analytical balance, 20 mg. of the compound to
be tested is weighed out on a piece of glassine weighing paper.
The paper and compound are placed in a 30 ml. wide-mouth
bottle and 3 ml. of acetone containing 1% Tween 2 ~ (polyoxy-
ethylene s~rbitan monolaurate~ is added to dissolve the
'
-23-
~765i~8
compound. If the material is not soluble in acetone, another
solvent such as water, alcohol or dimethylformamide (DMF) is
used instead. When DMF is used, only 0.5 ml. or less is used
to dissolve the compound and then another solvent is used to
make the volume up to 3 ml. The 3 ml. of solution is sprayed
uniformly on the soil contained in a small flat one day
after planting weed seeds in the flat of soil. An atomizer
is used to apply the spray using compressed air at a pressure
of 5 lb./sq. inch~ The rate of application is 8 lb./acre
and the spray volume is 143 gallons per acre.
On the day preceding treatment, the flat which is 7
inches long, 5 inches wide and 2.75 inches deep, is filled to
a depth of 2 inches with loamy sand soil. Seeds of seven
different weed species are planted in individual rows using
one species per ro~ across the width of the flat. The seeds
are covered with soil so that they are planted at a depth of
0.5 inch. Ample seeds are planted to give about 20 to 50
seedlings per row after emergence depending on the size of
the plants.
2Q The seeds used are foxtail (Setaria spp.) - FT; water-
grass ~Echinochloa crusgalli) - WG; red oat (Avena sativa) -
RO; redroot pigweed (Amaranthus retroflexus) - PW; mustard
(srassica juncea) - MD; curly dock (R~lmex crispus) - CD; and
hairy crabgrass (Digitaria sanguinalis) - CG.
After treatment, the flats are placed in the greenhouse
at a temperature of 70 to 85F. and watered by sprinkling.
Two weeks after treatment, the degree of injury or control is
determined by comparison with untreated check plants of the -
same age. The injury- ratlng from 0 to 100% is recorded for
each species as per cent control with 0% representing no
injury and 100% representing complete kill.
-2~-
.:
. . , , ~
~7~5~
Post-emergence Herbicide Screening Test
Seeds of six plant species, including hairy crabgrass
(CG), watergrass (WG~, red oat (RO), mustard (MD), curly dock
(CD~ and Pinto beans lPh~aseolus vulgaris~ (BN), are planted in
the flats as described above for pre-emergence screening. The
fla-ts are planted in the greenhouse at 70 to 85F. and watered
daily with a sprinkler. About lQ to 14 days after planting,
when the primary leaves of the bean plants are almost fully
expanded and the first trifoliate leaves are just starting to
.
form, the plants are sprayed. The spray is prepared by
weighing out 20 mg. of the test compound, dissolving it in
5 ml. of acetone containing 1% Tween 20~ (polyoxyethylene
sorbitan monolaurate~ and then adding 5 ml. of water. The
solution is sprayed on the foliage using an atomizer at an
air pressure of 5 lb./sq. inch. The spray concentration is
0.2~ and the rate is 8 lb./acre. The spray volume is 476
gallons per acre.
The results of these tests are shown in Table II.
. .
~ .
; . .
-25-
.
.
.. , .: ,
~7658~3
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--27--
~76588 :
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-29-
~7~5~38
Compounds 58 (cis~ and 59 (trans~ were bioassayed in
the herbicide screen employing the pre-emergence surface
technique. The following results in Table III were obtained at
0~25 lb/A, 0.5 lb/A ana 1.0 lb/A. A mixture of approximately
40% cls and 60% trans is included for comparison and to show the
preferred activity of the cis-configuration.
TABLE III
COMPOUND/ Rate Avg.
CONFIGURATION ~l~/A~ CG FT WG WO PB ~MG COT GR BL -
58 - cis 0.25lQ0100 80 101 2040 20 73 7
0.5 100100 99 601 5030 20 90 33
1.0 100100 100 801801 70 50 95 7
59 - trans 0.259710 20 0 0 0 0 32 0
0.5 9870 40 1 0 52 0
1.0 100100 80 10120 0 0 73 7
Mixture 0.25100100 60 0 ¦10 0 0 65 3
~40:60~ 0.5 100100 90 3040 ~0 10 80 23
.0 100100 100 60 ~ 50 20 40 43
.( .
CG, FT, WG and WO = crabgrass, foxtail, watergrass and
; 20 wild oats
PB, AMG and COT = pinto bean, annual morning g~lory (Ipomoea
purpurea), and cotton (Ipomoea trichocarpa)
The compounds of the present invention are used as pre-
emergence or post-emergence herbicides and are applied in a
variety of ways at various concentrations. In practice, the
. . ~ , .
compounds are formulated with an inert carrier, utilizing methods
well known to those skilled in the art, thereby making them
suitable for application as dusts, sprays, or drenches and the
like, in the form and manner required. The mixtures can be
`~ 30 dispersed in water with the aid of a wetting agent or they can
be employed in organic liquid compositions, oil and water, water
in oil emulsions, with or without the addition oE wetting, dis-
persing or emulsifying agents. An herbicidally effective amount
depends upon the nature of the seeds or plants to be controlled
;
-30-
., .
:. ' :
~- - . ~. ...
~6~
and the rate of application varies from 0.10 to approximately
50 pounds per acre. The concentration of a compound of the
present invention, constituting an effective amount in the
best mode of administration in the utility disclosed, is
readily determinable by those skilled in the art.
The phytotoxic compositions of this invention employing
an herbicidally effective amount of the compound described
herein are applied to the plants in the conventional manner.
The present invention contemplates methods of selectively
killing, combatting or controlling undesired plants which
comprises applying to at least one of (a) such weeds and (b)
their habitat, that is, the locus to be protected, an herbicid-
; ally effective or toxic amount of the particular active
compound alone or together with a carrier or adjuvant. Thus,
the dust and liquid compositions can be applied to the plant
by the use of power dusters, boom and hand sprayers and spray
dusters. The compositions can also be applied from airplanes
as a dust or a spray because they are effective in very low
dosages. In order to modify or control growth of germinating
seeds or emerging seedlings, as a typical example, the dust and
liquid compositions are applied to the soil according to
conventional methods and are distributed in the soil to a
depth of at least one-half inch below the soil surface. It is
not necessary that the phytotoxic compositions be admixed with
~ the soil particles and these compositions can be applied merely
;~ by spraying or sprinkling the surface of the soil. The
phytotoxic compositlons of this invention can also be applied
by addition to irrigation water supplied to the field to be
treated. This method of application permits the penetration of
the compositions into the soil as the water is absorbed
therein. Dust compositions, granular compositions or liquid
formulations applied to the surface of the soil can be
-31-
~7~8~ :
distributed below the surface of the soil by conventional
means such as discing, dragging or mixing operations.
The phytotoxic compositïons of this invention can also
contain other additaments, for e~ample, fertilizers, pesticides ;:
and th.e like, used as adjuvant or in combination with any of
the above-described adjuvants. Other phytotoxlc compounds
useful in combination with. the above-described compounds
include, for example, 2,4-dich~lorophenoxyacetic acids, 2,4,5- .
trich.lorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic
acid and the salts~ esters and amides thereof; triazine
derivatives, such as 2,4-bis(3-methoxypropylamino)-6-methyl- .
thio-s-triazine; 2-chloro-4-ethyl-amino-6-isopropylamino-s-
triazine, and 2-ethylamino-4-isopropyl-amino-6-methylmercapto-
s-triazine, urea derivatives, such as 3-(3,4-dichlorophenyl)-
l,l-dimethyl urea and acetamides such as N,N-diallyl-oC -
chloroacetamide, N-(o~-chloroacetyl)hexamethyleneimine, and
N,N-diethyl- ~-bromoacetamide, and the like; benzoic acids
such as 3-amino-2,5-dichlorobenzoic; and thiocarbamates, such
as S-propyl dipropylthiocar~amate; S-ethyldipropylthiocar-
bamate; S-ethyl hexahydro-lH-azepine-l-carbothioate and the
like. Fertilizers useful in combination with the active
ingredients include, for example, ammonium nitrate, urea and
superphosphate. Other useful additaments include materials in
wh.ich plant organisms take root and grow, such as compost,
manure, humus, sand and the like.
Various ch.anges and modi~icati.ons are possible with.out
departing from the spirt and scope of the invention described
herein and will be apparent to those skilled in the art to
which it pertains. It is accord.ingly intended that the
present invention sh.all only be limited by the scope of the
claims.
-32-
. ~ ,, .
.:
