CA1076588A - Acyclic, alicyclic and aromatic n-substituted halo-substituted 2-pyrrolidinones and their utility as herbicides - Google Patents

Abstract

ACYCLIC, ALICYCLIC AND AROMATIC N-SUBSTITUTED

Abstract of the Disclosure Acyclic, alicyclic, N-substituted halo-2-pyrrolidinones having the formula in which Q is oxygen or sulfur; R is lower alkyl, haloalkyl, alkenyl, cycloalkyl, cyclo-alkylalkyl, benzyl and chlorobenzyl; X is hydrogen or chlorine, Y is chlorine or bromine and Z is chlorine or bromine, provided that when R is allyl, Y and Z are each chlorine or bromine, and provided that when R is cyclo-hexyl, X is other than chlorine; and mono-cyclic aromatic N-substituted halo-2-pyrrolidinones having the formula in which X is hydrogen, chlorine or methyl;
Y is hydrogen, chlorine or bromine, Z is chlorine or bromine; R2 is alkyl or hydrogen;

R is hydrogen, alkyl, acetyl, chlorine, bromine, fluorine, iodine, trifluoromethyl, nitro, cyano, alkoxy, alkylthio, alkylsulfinyl, alkyl-sulfonyl, trifluoromethylthio, trifluoromethyl-sulfinyl, trifluoromethylsulfonyl, pentafluoro-propionamido, or 3-methylureido; and R1 is hydro-gen, alkyl, chlorine or trifluoromethyl. The compounds of this invention are prepared by a novel process and are useful as herbicides.

Description

~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 ;, .
'. ' 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 - ~

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.

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 .

~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 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
':

, 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-'' ' '' ~ 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.

'.

5~8 TABLE I

X O

~~\ N-R

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 .
~ .
.. ~

. .
~ .

.. ... . : ~ . . . .
. . : .,': . :

The following compounds correspond to the formula: ~

X I ,.
y C C R
~ >~
Z fH - f CH

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* :
' ~

, . :: ' , ' ': . , ~al7~i5~

TABLE I (continued~
m.p. 0C.
COMPOUND R R or n3 38 H C1 Cl H 3-CF3 4-C1 1.5263 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. ~
; ' :

~.

,. .
, -~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 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 ~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 ' ~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~-.:
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~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.

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~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 ;

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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 ~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.

. ~ ,, .
.:

Claims (86)

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

1. A compound having the formula in which Q is oxygen or sulfur; R is lower alkyl, alkenyl, haloalkyl, cycloalkyl, cycloalkyalkyl, benzyl and chloro-benzyl; X is hydrogen or chlorine; Y is chlorine or bromine, and Z is chlorine or bromine; provided that when R is allyl, Y and Z are each chlorine or bromine, and provided that when R is cyclohexyl, X is other than chlorine.

2. The compound according to Claim 1 in which Q is oxygen, R is lower alkyl, X is hydrogen, Y is chlorine and Z
is chlorine.

3. The compound according to Claim 1 in which Q is oxygen, R is alkenyl, X is hydrogen, Y is chlorine and Z is chlorine.

4. The compound according to Claim 3 in which R is allyl.

5. The compound according to Claim 1 in which Q is oxygen, R is alkenyl, X is chlorine, Y is chlorine and Z is chlorine.

6. The compound according to Claim 1 in which Q is oxygen, R is alkyl, X is chlorine, Y is chlorine and Z is chlorine.

7. The compound according to Claim 1 in which Q is oxygen, R is cycloalkyl, X is hydrogen, Y is chlorine and Z is chlorine.

8. The compound according to Claim 1 in which Q is sulfur, R is alkenyl, X is hydrogen, Y is chlorine and Z is chlorine.

9. The compound according to Claim 1 in which Q is oxygen, R is alkenyl, X is hydrogen, Y is bromine and Z is bromine.

10. The compound according to Claim 1 in which Q is oxygen, R is benzyl, X is hydrogen, Y is chlorine and Z is chlorine.

11. The compound according to Claim 1 in which Q is oxygen, R is haloalkyl, X is hydrogen, Y is chlorine and Z
is chlorine.

12. The compound according to Claim 1 in which Q is oxygen, R is cycloalkylalkyl, X is hydrogen, Y is chlorine and Z is chlorine.

13. The compound according to Claim 1 in which Q is oxygen, R is chlorobenzyl, X is hydrogen, Y is chlorine, and Z is chlorine.

14. A compound according to Claim 1 in which said compound has a cis-isomer configuration.

15. A compound according to Claim 1 in which said compound has a trans-isomer configuration.

16. A compound having the formula in which X is hydrogen, chlorine or methyl; Y is hydrogen, chlorine or bromine, Z is chlorine 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-propionamido or 3-methylureido; and R1 is hydrogen, alkyl, chlorine or trifluoromethyl.

17. The compound according to Claim 16 in which X is hydrogen, Y is chlorine, Z is chlorine, R, R1 and R2 are each hydrogen.

18. The compound according to Claim 16 in which X is chlorine, Y is chlorine, Z is chlorine, R, R1 and R2 are each hydrogen.

19. The compound according to Claim 16 in which X is methyl, Y is chlorine, Z is chlorine, R, R1 and R2 are each hydrogen.

20. The compound according to Claim 16 in which X is hydrogen, Y is chlorine, Z is chlorine, R2 is hydrogen, R is methyl, acetyl, chlorine, bromine, fluorine, iodine, trifluoro-methyl, nitro, cyano, trifluoromethylthio, trifluoromethyl-sulfinyl, trifluoromethylsulfonyl, alkylthio, alkylsulfinyl, alkylsulfonyl, pentafluoropropionamido, or 3-methylureido, and R1 is hydrogen.

21. The compound according to Claim 20 in which R is 3-fluorine.

22. The compound according to Claim 20 in which R is 3-chlorine.

23. The compound according to Claim 20 in which R is 3-trifluoromethyl.

24. The compound according to Claim 20 in which R is 3-cyano.

25. The compound according to Claim 20 in which R is 3-trifluorothio.

26. The compound according to Claim 20 in which R is 3-trifluorosulfinyl.

27. The compound according to Claim 20 in which R is 3-trifluorosulfonyl.

28. The compound according to Claim 20 in which R is 3-methylsulfonyl.

29. The compound according to Claim 20 in which R is 3-bromine.

30. The compound according to Claim 20 in which R is 3-iodine.

31. The compound according to Claim 20 in which said compound is the cis-isomer configuration.

32. The compound according to Claim 31 in which R is 3-trifluoromethyl.

33. The compound according to Claim 20 in which said compound is the trans-isomer configuration.

34. The compound according to Claim 33 in which R is 3-trifluoromethyl.

35. The compound according to Claim 16 in which X is hydrogen, Y is chlorine, Z is chlorine, R2 is hydrogen, R is alkyl and R1 is alkyl.

36. The compound according to Claim 16 in which X is chlorine, Y is chlorine, Z is chlorine, R2 is hydrogen, R is chlorine, trifluoromethyl or cyano, and R1 is hydrogen or chlorine.

37. The compound according to Claim 36 in which R is 3-tri-fluoromethyl and R1 is hydrogen.

38. The compound according to Claim 16 in which X is methyl, Y is chlorine, Z is chlorine, R2 is hydrogen, R is 3-trifluoromethyl and R1 is hydrogen.

39. The compound according to Claim 16 in which X is hydrogen, Y is chlorine, Z is chlorine, R is 3-trifluoromethyl and R1 is 4-chlorine.

40. The compound according to Claim 16 in which X is hydrogen, Y is chlorine, Z is chlorine, R is 3-trifluoromethyl and R1 is 5-trifluoromethyl.

41. The compound according to Claim 16 in which X is hydrogen, Y is hydrogen, Z is chlorine, R is methyl, acetyl, chlorine, bromine, fluorine, iodine, trifluoromethyl, nitro, cyano, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, alkylthio, alkylsulfinyl, alkylsul-fonyl, pentafluoropropionamido, or 3-methylureido, and R1 and R2 are each hydrogen.

42. A method for controlling the growth of undesirable vegetation which comprises applying to at least one of (a) such undesirable vegetation and (b) their habitat, an herbicidally effective amount of a compound having the formula in which Q is oxygen or sulfur; R is lower alkyl, alkenyl, haloalkyl, cycloalkyl, cycloalkylalkyl, benzyl and chlorobenzyl;
X is hydrogen or chorine; Y is chlorine or bromine, and Z is chlorine or bromine; provided that when R is allyl, Y and Z

are each chlorine or bromine, and provided that when R is cyclohexyl, X is other than chlorine.

43. A method according to Claim 42 in which Q is oxygen, R is lower alkyl, X is hydrogen, Y is chlorine and Z is chlorine.

44. A method according to Claim 42 in which Q is oxygen, R is alkenyl, X is hydrogen, Y is chlorine and Z is chlorine.

45. A method according to Claim 44 in which R is allyl.

46. A method according to Claim 42 in which Q is oxygen, R is alkenyl, X is chlorine, Y is chlorine and Z is chlorine.

47. A method according to Claim 42 in which Q is oxygen, R is alkyl, X is chlorine, Y is chlorine and Z is chlorine.

48. A method according to Claim 42 in which Q is oxygen, R is cycloalkyl, X is hydrogen, Y is chlorine and Z
is chlorine.

49. A method according to Claim 42 in which Q is sulfur, R is alkenyl, X is hydrogen, Y is chlorine and Z is chlorine.

50. A method according to Claim 42 in which Q is oxygen, R is alkenyl, X is hydrogen, Y is bromine and Z is bromine.

51. A method according to Claim 42 in which Q is oxygen, R is benzyl, X is hydrogen, Y is chlorine and Z is chlorine.

52. A method according to Claim 42 in which Q is oxygen, R is haloalkyl, X is hydrogen, Y is chlorine and Z
is chlorine.

53. A method according to Claim 42 in which Q is oxygen, R is cycloalkylalkyl, X is hydrogen, Y is chorine and Z is chlorine.

54. A method according to Claim 42 in which Q is oxygen, R is chlorobenzyl, X is hydrogen, Y is chlorine and Z is chlorine.

55. A method for controlling the growth of undesirable vegetation which comprises applying to at least one of (a) such undesirable vegetation and (b) their habitat, an herbicidally effective amount of a compound having the formula in which X is hydrogen, chlorine or methyl; Y is hydrogen, chlorine or bromine, Z is chlorine 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, penta-fluoropropionamido, or 3-methylureido; and R1 is hydrogen, alkyl, chlorine or trifluoromethyl.

56. The method according to Claim 55 in which X is hydrogen, Y is chlorine, Z is chlorine, R, R1 and R2 are each hydrogen.

57. The method according to Claim 55 in which X is chlorine, Y is chlorine, Z is chlorine, R, R1 and R2 are each hydrogen.

58. The method according to Claim 55 in which X is methyl, Y is chlorine, Z is chlorine, R, R1 and R2 are each hydrogen.

59. The method according to Claim 55 in which X is hydrogen, Y is chlorine, Z is chlorine, R2 is hydrogen, R is methyl, acetyl, chlorine, bromine, fluorine, iodine, trifluoro-methyl, nitro, cyano, trifluoromethylthio, trifluoromethylsul-finyl, trifluoromethylsulfonyl, alkylthio, alkylsulfinyl, alkylsulfonyl, pentafluoropropionamido, or 3-methylureido;
and R1 is hydrogen.

60. The method according to Claim 59 in which R is 3-fluorine.

61. The method according to Claim 59 in which R is 3-chlorine.

62. The method according to Claim 59 in which R is 3-trifluoromethyl.

63. The method according to Claim 59 in which R is 3-cyano.

64. The method according to Claim 59 in which R is 3-trifluorothio.

65. The method according to Claim 59 in which R is 3-trifluorosulfinyl.

66. The method according to Claim 59 in which R is 3-trifluorosulfonyl.

67. The method according to Claim 59 in which R is 3-methylsulfonyl.

68. The method according to Claim 59 in which R is 3-bromine.

69. The method according to Claim 59 in which R is 3-iodine.

70. The method according to Claim 59 in which said compound is the cis-isomer configuration.

71. The method according to Claim 70 in which R is 3-trifluoromethyl.

72. The method according to Claim 59 in which said compound is the trans-isomer configuration.

73. The method according to Claim 72 in which R is 3-trifluoromethyl.

74. The method according to Claim 55 in which X is hydrogen, Y is chlorine, Z is chlorine, R2 is hydrogen, R is alkyl and R1 is alkyl.

75. The method according to Claim 55 in which X is chlorine, Y is chlorine, Z is chlorine, R2 is hydrogen, R is chlorine, trifluoromethyl or cyano, and R1 is hydrogen or chlorine.

76. The method according to Claim 75 in which R is 3-trifluoromethyl and R1 is hydrogen.

77. The method according to Claim 55 in which X is methyl, Y is chlorine, Z is chlorine, R2 is hydrogen, R is 3-trifluoromethyl and R1 is hydrogen.

78. The method according to Claim 55 in which X is hydrogen, Y is chlorine, Z is chlorine, R2 is hydrogen, R is 3-trifluoromethyl and R1 is 4-chlorine.

79. The method according to Claim 55 in which X is hydrogen, Y is chlorine, Z is chlorine, R2 is hydrogen, R is 3-trifluoromethyl and R1 is 5-trifluoromethyl.

80. The method of preparing acyclic and alicyclic N-substituted halo-2-pyrrolidinones of the formula in which R is lower alkyl, haloalkyl, alkenyl, cycloalkyl, cycloalkylalkyl, benzyl and chlorobenzyl; X is hydrogen or chlorine; Y is chlorine or bromine, and Z is chlorine or bromine; which comprises the rearrangement reaction of an N-alkenyl haloacyl amide of the formula in which R, X, Y and Z are as above-defined, in the presence of a catalytic amount of ferrous ion at a temperature of between about 50°C and about 190°C., and recovery of the resulting product.

81. The method of preparing acyclic and alicyclic N-substituted halo-2-pyrrolidinones of the formula in which R is lower alkyl, haloalkyl, alkenyl, cycloalkyl, cycloalkylalkyl, benzyl and chlorobenzyl; X is hydrogen or chlorine; Y is chlorine or bromine, and Z is chlorine or bromine, which comprises the rearrangement reaction of an N-alkenyl haloacyl amide of the formula in which R, X, Y and Z are as above-defined, in the presence of a catalytic amount of ferrous ion which ferrous ion catalyst source is selected from ferrous chloride, ferrous bromide, iron metal, ferrocene, and ferrous acetonyl acetonate, in the presence of a high boiling solvent at a temperature of between about 50°C. and about 190°C., and recovery of the resulting product.

82. The method of Claim 81 in which the compound wherein R is allyl, X is hydrogen, Y is chlorine and Z is chlorine is prepared from in the presence of diethylene glycol dimethyl ether.

83. The method of preparing monocyclic aromatic N-substituted halo-2-pyrrolidinones having the formula in which X is hydrogen, chlorine or methyl; Y is hydrogen, chlorine or bromine, Z is chlorine 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-propionamido, or 3-methylureido; and R1 is hydrogen, alkyl, chlorine or trifluoromethyl, which comprises the rearrangement reaction of an N-alkenyl haloacyl amide of the formula in which X, Y-, Z, R, R1 and R2 are as above defined, in the presence of a catalytic amount of ferrous ion, which ferrous ion catalyst source is selected from ferrous chloride, ferrous bromide, iron metal, ferrocene and ferrous acetonyl acetonate, said reaction is carried out at a temperature of between about 50°C. and about 190°C., and recovery of the resulting product.

84. The method of preparing monocyclic aromatic N-substituted halo-2-pyrrolidinones having the formula in which X is hydrogen, chlorine or methyl; Y is hydrogen, chlorine or bromine, Z is chlorine 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, penta-fluoropropionamido, or 3-methylureido; and R1 is hydrogen, alkyl, chlorine or trifluoromethyl, which comprises the rearrangement reaction of an N-alkenyl haloacyl amide of the formula in which X, Y, Z, R, R1 and R2 are as above defined, in the presence of a catalytic amount of ferrous ion which ferrous ion catalyst source is selected from ferrous chloride, ferrous bromide, iron metal, ferrocene and ferrous acetonyl acetonate, and high boiling solvent at a temperature of between about 50°C. and about 190°C., and recovery of the resulting product.

85. A compound selected from the group consisting of the formula:

in which Q is oxygen or sulfur; R is lower alkyl, alkenyl, haloalkyl, cycloalkyl, cycloalkylalkyl, benzyl and chlorobenzyl;
X is hydrogen or chlorine; Y is chlorine or bromine and Z is chlorine or bromine; provided that when R is allyl, Y and Z
are each chlorine or bromine, and provided that when R is cyclohexyl, X is other than chlorine; and of the formula:

in which X1 is hydrogen, chlorine or methyl; Y1 is hydrogen, chlorine or bromine, Z is chlorine or bromine; R2 is alkyl or hydrogen; R3 is hydrogen, alkyl, acetyl, chlorine, bromine, fluorine, iodine, trifluoromethyl, nitro, cyano, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, pentafluoro-propionamido or 3-methylureido; and R1 is hydrogen, alkyl, chlorine or trifluoromethyl.

86. The method of preparing acyclic and alicyclic N-substituted halo-2-pyrrolidinones of the formula in which R is lower alkyl, haloalkyl, alkenyl, cycloalkyl, cycloalkylalkyl, benzyl and chlorobenzyl; X is hydrogen or chlorine; Y is chlorine or bromine, and Z is chlorine or bromine; or monocyclic aromatic N-substituted halo-2-pyrrolidinones having the formula in which X1 is hydrogen, chlorine or methyl; Y1 is hydrogen, chlorine or bromine, Z is chlorine or bromine; R2 is alkyl or hydrogen; R3 is hydrogen, alkyl, acetyl, chlorine, bromine, fluorine, iodine, trifluoromethyl, nitro, cyano, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, pentafluoro-propionamido, or 3-methylureido; and R1 is hydrogen, alkyl, chlorine or trifluoromethyl; which method is selected from the group consisting of the rearrangement reaction of an N-alkenyl haloacyl amide of the formula in which R, X, Y and Z are as above-defined, in the presence of a catalytic amount of ferrous ion at a temperature of between about 50°C. and about 190°C., and recovery of the resulting acyclic or alicyclic product; or which comprises the rearrangement reaction of an N-alkenyl haloacyl amide of the formula in which X1, Y1, Z, R3, R1 and R2 are as above defined, in the presence of a catalytic amount of ferrous ion, which ferrous ion catalyst source is selected from ferrous chloride, ferrous bromide, iron metal, ferrocene and ferrous acetonyl acetonate, said reaction is carried out at a temperature of between about 50°C. and about 190°C., and recovery of the resulting monocyclic product.