CA1280752C - Herbicidal 5-amino-3-oxo-4-substituted-phenyl)-2,3- dihydrothiophene and derivatives thereof - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

5-Amino-3-oxo-4-(3-substituted-phenyl)-2,3-dihydrothiophene and derivatives thereof of the formula I

(I)

Description

;2 HERBICIDAL 5-AMINO-3-OX0-4-(SUBSTITUTED-PHENYL)-2,3-DIHYDROTHIOPHENE AND DERIVATIVES THEREOF

BACKGROUND OF THE INVENTION
This invention relates -to 5-amino-3-oxo-4-(sub-stituted-phenyl)-2,3-dihydrothiophene derivatives and to the use of such compounds as herbicides and plant growth regulators.
Japanese Patent No. ]9090 (Chemical Abstracts 69P10352e) generical]y discloses certa~n 5-amino-3-oxo-4-(phenyl or 10 halophenyl)-2,3-dihydrothiophenes, including 5-amino-3-oxo-4-(phenyl and 4-chlorophenyl)-2,3-dihydro-thiophenes, as pharmaceu-ticals. Based on Chem. Abstracts 95: 24799e, Russian Patent SU
767105, discloses 5-amino-3-oxo-4-(4-methoxyphenyl)-2,3-dihydro-thiophene.
Chemiker-Zeitung 104 (1980) No. 10, Pages 302-303, is an academic paper disclosing the ring closure of l-(dimethyl-amino`)-2~4-diphenyl-l-buten-3~4-dione to yield 5-dimethyl-amino-2,4-diphenyl-2,3-dihydrofuran. British Patent No. 1,521,092, disc]oses certain 3-phenyl-5-substituted-4(1H)-pyrid-ones or -thiones as herbicides. Japanese Patent Application 13,710/69 (Chemical Abs-tracts 71:61195e) discloses 5-amino-3-oxo-4-(phenyl or 4-chlorophenyl)-2,3-dihydroEurans and Japanese Patent No. 68/21423 discloses p-(2-amino-4,5-dihydro-4-oxo-3-thienyl)-benzene sulfon;c acid. ~Ielvetica Chemlca Acta, Volume 66, Pages 362-378 (1983) discloses 5-N-cyc]opropyl-4-phenyl-2-methoxy-carbonylmethylene-3-furanone as part of an academic chemical ~ " ~j `1 t~

" 1,2"~t7~X
- 2 - 61936-16~2 synthesis discusslon. U.S. Patent No. 4,441,910 discloses herbicidal ureldosulfonylfu~ans and ureidosulfonylthiophenes.
In my co-pending Canadian application Serial No.
4S6,115, filed June 7, 1984, I disclose certain herbicidal 5-amino-3-oxo-4-(subs-ti-tuted phenyl)-2,3-dihydrofurans and derivatives thereof.
SUMMARY OF THE INVENTION
The present invention provides compounds having both pre-emergence and post~emeryence herbicidal activity and having especially good pre-emergence activity against a broad spectrum of both broad-leaf weeds and grassy weeds. At lower application ra-tes the compounds can be applied as plant growth regulators.
The compounds of the present invention can be represented by the following formula:

1~1 Y
R2 ~ ~ (I) R ()n wherein n is 0, 1, ar 2; R is lower alkyl having L
through 4 carbon atoms; cycloalkyl having 3 -through 7 carbon atoms, (cycloalkyl)alkylene havlng 3 through 7 carbon atoms in the cyc]oalkyl moiety and 1 through 3 carbons in the alkylene moiety;
lower alkenyl; haloalkyl having 1 through ~ carbon atoms and 1 through 3 halo a-toms independently selected from the group of fluoro, chloro, bromo or iodo; haloalkenyl having 2 through 4 5~
- 2a - 61936-1682 carbon atoms and l through 3 halo atoms at the terminal carbon atom, which halo atoms are independently selected froM the group of fluoro, chloro, bromo, or iodo; lower alkoxy; lower alkylthio;
lower alkoxyalkyl wherein the alkoxy and alkyl moiety thereof independently have 1 through 3 carbon atoms; lower alklylthioalkyl wherein the alkyl moieties independently have 1 through 3 carbon atoms; phenyl, naphth-l-yl, .inden-l-yl; 4-fluorophenyl;
arylalkylene having 1 through 3 carbon atoms in the alkylene moiety and wherein said aryl moiety is phenyl, naphth-l-yl or inden-l-yl; or substituted ~.~

8~t~

aryl or arylalkylene selected from the group having the formulas:

'V ~' -(R3) ~ o~; (R3) ~
R7~ R6R9 ~ R6 ; or -(R3) ~ 1 0 ~
~ 6 ~ R

wherein one, two or three of R4, R5, R6' R7, R8, and R9 are independently selected from the group of lower alkyl, lower alkoxy, halo, nitro, or haloalkyl having 1 through 3 carbon atoms and 1 through 3 of the same or different halo atoms, and the remainder of R4, R5, R6, R7, R8 and R9 are hydrogen; and R3 is a single bond or an alkylene having 1 through 3 carbon atoms;
R1 is hydrogen or alkyl having 1 through 4 carbon atoms;
R2 is hydrogen, alkyl having 1 through 4 carbon atoms, alkenyl having 3 or 4 carbon atoms, alkoxy-carbonylalkyl having from 1 through 4 carbon atoms in the alkoxy moiety and from 1 through 4 carbon atoms in the alkyl moiety; alkoxyalkyl wherein the alkoxy and alkyl moieties independently have 1 through 3 7~2 carbon atoms, or alkylthioalkyl wherein the alkyl moieties independently have 1 through 3 carbon atoms; or Rl and ~2 toge-ther with the nitrogen to which they are joined form a saturated or unsaturated nitrogen heterocycle having from 3 through 6 ring atoms one of which is nitrogen and the remainder of which are carbon atoms;
X is hydrogen, lower alkyl, lower alkoxy, halo, or trifluoromethyl and can be at any avai.lable position on the phenyl ring; and 0 ~ i5 lower alkyl; lower alkoxy; halo; lower haloallcyl having 1 through 4 carbon a-toms, and 1 through 3 of the same or different halo atoms; lower haloalkoxy having 1 through 4 carbon atoms and 1 through 3 of the same or different halo atoms, or lower haloalkylthio having 1 through 4 carbon atoms and l through 3 of the same or different halo atoms; with the proviso that when Y is other than tri.fluoromethyl and Rl is hydrogen and R2 is hydrogen then R is methyl, ethyl, propyl, 2-halophenyl, 2-lower alkylphenyl or 4-fluorophenyl.
The invent;.on al.so comprises compatible salts oE the compound of Formula (I), for example sal-ts obtained via replacement of the amino hydrogen (i.e., Rl and R2 is hydrogen) with a compatible cation or enolation of -the 3-oxo group following replacement oE the ~mino hydrogen.
The compounds of Formul.a I can exist as oxo-enol tautomers. The compounds of Formula (I) also have an asymmetric carbon atom and when n=l have an asymmetric sulfur and can exist c~t~

5~
- 4a - 61936-1682 as optical isomers and/or diastereomers. The above formula is intended to encompass the respective -tautomers and optical and geometric isomers where they exist as well as mixtures -thereoE and the respective isomers as well as mixtures thereof are encompassed within the invent;.on.

~.~

S~
Ol ~5-It has also been discovered that generally thepresence of a 3-trifluorometh~l substituent on the 05 4-phenyl group of the compounds of the present invention very substantially enhances herbicidal activity.
In a further aspect the invention provides a herbicidal composition comprising a compatible carrier and a herbicidally effective amount of the compounds of 10 Formula (I), or compatible salts thereof, or mixtures thereof.
The present invention also provides a method for preventing or controlling the growth of unwanted vegeta-tion, which comprises treating the growth medium and/or 15 the foliage of such vegetation with a herbicidally effec-tive amount of the compound(s) of Formula (I) and/or com-patible salts thereof.
In another aspect, the present invention pro-vides a plant growth regulating composition comprising a ~0 compatible carrier and a plant growth regulating amount of the compound of Formula (I), compatible salts of Formula (I), or mixtures thereof, effective to alter ~he normal growth pattern of said plants.
-~ The present invention also provides a method for 25 regulating plant growth which comprises treating the growth medium and/or the foliage of such vegetation with a plant growth regulating effective amount of the com-pound(s) of Formula (I) and/or compatible salts thereof, effective to alter the normal growth pattern of said 30 plants.
The present invention also provides chemical intermediates and processes for preparing the compounds of Formula (I).
The invention will be further described herein-35 below.

Ol -6~ 5~

FURTHER DESCRIPTION OF THE
INVENTION AND THE PREFERRED EMBODIMENTS
05 Illustrations of typical compounds of Formula (I) of the present invention can be had by refer-ence to Examples 1, 3-8 set forth hereinbelow on Pages 29-31, 33-54. In terms of substituents, the pre-ferred compounds are those wherein R is hydrogen, methyl, lO ethyl, propyl, phenyl or monosubstituted phenyl, more preferably, methyl, ethyl, n-propyl, phenyl or monohalo-or monomethyl-substituted phenyl, and especially ethyl, n-propyl; phenyl, 2-chlorophenyl, 2-methylphenyl and 2-fluorophenyl, n is preferably 0, Rl and R2 are preferably 15 independently hydrogen, methyl, ethyl or n-propyl, and more preferably one of Rl or R2 is hydrogen and the other is methyl, ethyl or n-propyl, preferably methyl or ethyl;
Y is preferably lower haloalkyl and especially trifluoro-methyl. X is generally preferably hydrogen. The prefer-20 red compounds have at least one preferred substituent(preferably the Y substituent) and more preferabl~ have a combination of preferred substituents.
Synthesis The compounds of Formula (I) wherein Rl and R2 25 are each hydrogen can be prepared by the following sche-matically represented process:

X X
I

30 ~ O R ~ ~ O
fHCC-SCH3 ~ cyclizing agent > ~ ~
CN H2N S~R
(A) (Ia) wherein X, Y, and R are as defined hereinabove.
This process can be conveniently effected by contacting Compound (A) with a cyclizing agent, under reactive conditions, preferably in the presence of an 40 inert organic solvent.

01 ~7~

Typically, this process is conducted at tempera-tures in the range oE about from 0 to 200C, pre~erably 05 about from 115 to 120C, for about from 10 to 120 minutes, pre~erably about from 10 to 30 minutes, using about from 1 to 10, preferably 1 to 2 moles of cyclizing agent per mole of Compound (A). Suitable cyclizing agents which can be used include, for example, strong anhydrous acid, for 10 example, sulfuric acid, hydrogen ehloride, hydrogen bromide, trifluoroaeetic acid, methane sulfonic aeid, and the like. Suitable organie solvents whieh can be used inelude, for example, aeetie aeid, propionie aeid, butyrie aeid, toluene, xylene, and the like, and compatible 15 mixtures thereof.
Best results are obtained using anhydrous sul~uric acid as the eyelizing agent.
The starting materials of Formula A wherein R is hydrogen, lower alkyl, eyeloalkyl, alkoxy, alkoxyalkyl, 20 alkylthioalkyl, lower haloalkyl, lo~er haloalkenyl, arylalkylene, substituted arylalkylene or alkenylalkyl (e.g., -CH2CH=CH) ean be prepared by the following schematieally represented overall reaetion equ~tion:
X
O H

CN (1) /
~ (A') X
~' O H
r ~ e ~ I 2M~
~ ~ C - C-C-SCH3 R'X; ~ (A wherein R=R') 35CN (A'') wherein X' is chloro, bromo, or iodo (preferably iodo); M is sodium or lithium, R' is hydrogen, lower ~0 ~`~ -8- ~2~ 75~

alkyl, cycloalkyl, alkoxy, alkoxyalkyl, alkylthio-alkyl, lower haloalkyl, lower haloalkenyl aryl-05 alkylene, substituted arylalkylene or alkenylalkyl;
and ~ and Y are as defined hereinabove.
This process is conveniently conducted in two steps by first contacting compound (A') with an alkali metal amide (preferably [(CH3)3Si]2NeLi~) under reactive 10 conditions to form an intermediate dianion salt. Step 1 is preferably conducted in an inert organic solvent. In the seconcl step, preferably conducted in situ, the reac-tion product of the first step (i.e., A'') is contacted with the appropriate R'X', under reactive conditions to 15 yield the desired R substitution. This reaction is also preferably conducted in an inert organic solvent. Also, both steps of this process are preferably conducted under anhydrous conditions under an inert atmosphere such as, for example, nitrogen.
Typically, step 1 of this process is conducted at temperatures in the range of about from -100 to 25Ct preferably about from -78 to 25C, for about from 1/2to 5 hours, preferably l/2to 11/2hours, using about ~rom 1 to 5 moles, preferably 2 to 2.5 moles, of alkali metal amide salt per mole of compound A. Suitable alkali metal amides which can be used include, ~or example, lithium bis(tri-methylsilyl)amide (i.e. [(CH3)3Si]2NeLi~); sodium bis(trimethylsilyl)amide; potassium bis(trimethyl-silyl)amide; lithium diethylamide; lithium diisopropyl-amide; sodium dimethylamide, and the like. The alkalimetal amides are generally known compounds and can be prepared by known procedures, or obvious modiEications thereof, Eor example, by the reaction of a secondary amine with n-butyl alkali metal. Lithium bis(trimethylsilyl)-3S amide is preferred as it gives very good results and canbe conveniently obtained Erom commercial sources. Suit-able inert solvents, which can be used, include, for exam-ple, tetrahydroEuran, dioxane, dimethoxyethane, diethyl ether, diisopropyl ether, and the like and compatible mixtures thereof.

01 _9_ ~2~ 7~

The second step of this process is typically conducted at temperatures in the range of about from -30 05 to 30C, preEerably, 22 to 25C for about from 1 to 18 hours, preferably 1 to 5 hours using about from 1 to 10 moles, preferably 1 to 1.5 moles of RX' per mole of ~'.
The R'X' halides are generally known compounds and can be prepared by known procedures or obvious modifications thereof (e.g., substitution of appropriate reactants and solvents).
The starting materials of Formula (A') can be prepared by the following schematically represented process:

X

~ H2CN + CH3S-CH2-C-oR5 -> (A') (B) (C) wherein R5 is lower alkyl (e.g., methyl or ethyl) , aryl (e.gO phenyl) or arylalkylene (e.g.
benzyl); and, Y and X are as defined hereinabove.
This process can be conveniently effected by contacting Compound (B) with Compound (C), and a strong base under reactive conditions, preferably in an inert organic solvent.
Typically, this process is conducted at tempera-tures in the range of about from 0 to 100C, preferably 75 to 85C, for about from 5 to 36 hours, preferably 18 to 24 hours, using about from 1.0 to 10.0, preerably 1.0 to 1.2 moles of Compound (C) per mole of Compound (B).
Typically, about from 1.0 to 10.0 moles of base are used per mole of Compound (C).
Suitable strong bases which can be used include, for example, alkali metal alkanolates, for example, sodium methoxide, sodium ethoxide, potassium ethoxide, sodium hydride, potassium hydride, and the like. The strong base ol --lo-- ~ 75~

should preferably be one which does not yield water as a by-product in this reaction system.
05 Suitable inert solvents which can be used include, for example, lower alkanols (for example, methanol, ethanol, and propanol) tetrahydrofuran, dimethoxyethane, dioxane, and the like, and compatible mixtures thereo~. Conveniently, the alkali metal 10 alkanolate is prepared in situ by reacting an alkali metal with excess alkanol which in turn serves as solvent ~or the above reaction.
The starting materials of Formulas (B) and (C) are generally known materials and can be prepared by known 15 procedures, or obvious modifications thereof (i.e., sub-stitution of appropriate starting materials). The pre-paration of Compound (B) is for example described in Org. Syn. Coll., Volume 1, 107 (1941), and the preparation of Compound (C) is described in Methoden Der Organischen 20 Chemie (Houben-Weyl) vol. IX page 107 (1955).
A general procedure for preparing the starting materials of Formula A can be made by the following schematically represented by the overall reaction equation:

X
R O
y ~CH2CN +CH3S-CH--C-oR5 ~ (A) (B) (C' ) wherein R, X, and Y are as defined hereinabove and R5 is lower alkyl, pre-ferably methyl.
This process can be conveniently effected by contacting Compound (B) with Compound (C'), and a strong base, under reactive conditions, preferably in an inert organic solvent.
Typically, this process is conducted at tempera-tures in the range of about from 0 to 100C, preferably 0~ 2~ 75~2 75 to 85C for about from 5 to 36 hours, preferably 18 to 24 hours, using about from 1.0 to 10.0, preferably 1.0 to os 1.2 moles of Compound (C') per mole of Compound (B). This process can also be conveniently conducted at room temper~
ature. Typically, about from 1.0 to 10.0 moles of base are used per mole of Compound (C').
Suitable strong bases which can be used include, 10 Eor example, alkali metal alkanolates, for example, sodium methoxide, sodium ethoxide, potassium ethoxide, sodium hydride, potassium hydride, and the like. The strong base should preferably be one which does not yield water as a by-product in this reaction system.
Suitable inert solvents which can be used include, for example, lower alkanols (for example, methanol, ethanol, and propanol) tetrahydrofuran, dimethoxyethane, dioxane, and the like, and compa-tible mixtures thereof. Conveniently, the alkali metal 20 alkanolate is prepared in situ by reacting an alkali metal with excess alkanol which in turn serves as solvent for the above reaction.
As pointed out above, the starting materials of Formula B are known compounds or can be prepared by 25 obvious modifications of known procedures. The starting materials of formula C' can be prepared by the following schematically represented overall reaction equation:

R O
1"
~-CHCoR5 ~ CH3SH > (C') (D) (E) wherein ~ is chloro or bromo and R and R5 are as defined hereinabove.
This process can be conveniently effected by contacting Compound (D) with methyl mercaptan (E) under reactive conditions preferably in an inert organic solvent and in the presence of a scavenger base to react with the 40 hydrogen halide by-product of the reaction.

` 01 -12- ~2~0~7~

Typically, this process is conducted at temper-atures in the range of about from 0-40C, preferably 05 0-25C, using about from 0 8 to 2 moles, preferably 1.1 to 1.5 moles of methyl mercaptan per mole of Compound (D).
Suitable solvents which can be used include for example methylene chloride, tetrahydrofuran, 1,2~dichloroethane, chloroform, carbon tetrachloride and the like and 10 compatible mixtures thereof. Suitable scavenger bases which can be used include, for example, triethylamine;
pyridine; methylpyridine; 1,5-diazabicyclo [4.3.0] nonene;
1,8-diazabicyclo [5.4.0] undec-7-ene; sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium 15 hydroxide, alkali metal alkoxides (e.g., sodium methoxide, potassium ethoxide) and the like. Typically about 0.9 to 1.5 mole equivalents of scavenger base are used per mole of Compound (D).
The starting materials of Formula (D) can be 20 prepared by applying the procedure described in Org. Syn.
Coll. Vol. III, 381 (1955) using the appropriate starting materials. The starting materials of Formula (D) wherein R - phenyl or substituted phenyl can also be prepared via the following schematically representPd overall reaction 25 equation:

RCH2CoR5 ~ ~ > (D) O I o (F) (G) wherein R, R5 and Z are as defined hereinabove.
This process can be conveniently conducted by contactin~ Compound F with N-bromo or chloro-succinimide (G) under reactive conditions preferably in an inert organic solvent.
Typicall~, this process is conducted at temper-40 atures in the range of about from 40 to 100C, preferably .. .

~ 13~ 75~

60 to 80C, using about from 0.9 to 1.5 moles of the N-halosuccinimide (G) per mole of Compound (F). Suitable 05 solvents which can be used include, for example, carbon tetrachloride; 1,2~dichloroethane, methylene chloride, chlorobenzene, chloroform, and the like and compatible mixtures thereof.
The starting materials of Formula F are generally known materials and can be prepared by known procedures, or obvious modifications thereoE (i.e., sub-stitution of appropriate starting materials). A
preparation for Compound (F) is described in Org. Syn.
Coll., Volume 1, 270 (1941). N-bromo and N-chloro-succinimide are, of course, well known commercialcompounds.
The compounds of Formula (I) wherein Rl and R2 are each hydrogen and R is aryl or substituted aryl are preferably prepared via the following schematically represented process:

X X

25 ~ ~ IHC CH2 > ~ ~ C - C - CHR6 2M~

Y Y
(A") / X

(Ib~) wherein R6 is aryl or substituted aryl, M is an alkali metal anion, and X and Y are as defined here-inabove.

5~2 This process is conveniently conducted in twosteps by first contacting compound A" with an alkali metal S amide under reactive conditions, preferably in an inert organic solvent or organic carrier liquid. The reaction product of the first step can then be contacted with elemental sulfur, conveniently in situ, under reactive conditions.
The first step is typically conducted at temper-atures in the range of about from -78 to 25C, preferably -30 to 22C, for about from 1/2 to 5 hours, preferably about rom 1/2to 2 hours, using abouk from 2 to 10 moles, pref-erably 2 to 2.5 moles, of alkali metal amide per mole of compound A". Suitable alkali amides and organic solvents or carrier liquids which can be used include those described with respect to alkali metal reaction previously described hereinabove.
The second step of this process can then be effected by contacting the reaction product of the first step with elemental sulfur, preferably in an organic solvent or organic carrier liquid and most conveniently is conducted in situ. This step is typically conducted at temperatures in the range of about from 20 to 30C, preferably 22 to 25C, for about from 1 to 2~ hours, preferably 18 to 24 hours, using about from 1 to 5, preferably 1 to 1.1 moles of elemental sulfur per mole of compound A". Suitable inert organic solvents or organic carrier liquids include those described with respect to the first step of this process.
The starting materials of formula A" can be prepared via the following schematically represented over-all reaction equation:

X
R6 o CH2CN + H2C - C-oR5 ~ (A") / (B) (C') y 01 -15- ~2 ~7~2 wherein R5 and R6 are as defined hereinabove.
This process can be effected in the same manner ~5 as described hereinabove with respect to the reaction of compounds B and C but replacing compound C with compound C'. This process can also be used to prepare the correponding analogs of A" wherein R6 is lower alkoxy or haloalkoxy by using the corresponding R6 alkoxy or lO haloalkoxy analog of C'.
The compound of Formula (I) wherein one or both of Rl and R2 are lower alkyl or lower alkenyl and n=0 can be prepared by alkylation (or alkenylation) of the amino group:
X X

\N ~ R

(Ib) (Ic) wherein R, Rl, and X are as defined hereinabove;
R is as defined for R2 but is not hydrogen3 and R3Z' is an alkylation agent having the desired R group or Rl group if dialkylation is desired.
This process can be effected by contacting Compound (Ib) under reactive conditions with a suitable alkylation agent capable of alkylating primary or secondary amino groups.
For example, this can be effected by contacting Compound ~Ib) with a R3 halide, preferably R3I or R3Br, preferably in an inert organic solvent and preferably in the presence of a scavenger base and a phase transfer agent. Typically, this process is conducted at tempera-tures in the range o about from 0 to 100C, preferably 20 to 45C for about Erom 1.0 to 72.0, preferably 2.0 to 01 -16- 1~ 8~ ~2 18.0 hours~ Where it is desired to monoalkylate, typi-cally about from 1.0 to 1.1 molas of R3Z' reactant is used 05 per mole of Compound (Ib). Where it is desired to dialkylate, typically about from 1.9 to 4.0 moles o~ R3Z' are used per mole of Compound (Ib). In the case where it is desired to prepare the compound wherein R3 is alkoxyalkyl or alkylthioalkyl, it is preferred to use a 10 large excess of R3 halide even where monoalkylation is desired; for example 3 to 6 moles oE R3Z' per mole of Ib. Further alkylation can be effected in a second step if desired~ Variation in Rl and R2 can be effected by first alkylation of only one of the two amino hydrogens 15 and then alkylating the second amino hydrogen with an alkylating agent having a different R3 alkyl or alkenyl group. The compounds wherein Rl and R2 together with the amino nitrogen atoms form a saturated heterocycle can be prepared by using the appropriate Z''-(CH2)2_5-Z', wherein 20 Zll and Z' are I or Br alkylating agent. The RlR2N
unsaturated heterocycle can be prepared by using the appropriate cis-alkenyl dihalide, wherein one of the halo atoms is on each o~ the terminal alkenyl carbons.
Suitable inert organic solvents which can be 25 used, include, for example, liquid halogenated alkanes, for example, methylene chloride, carbon tetrachloride, dichloroethane; tetrahydrofuran and the like. Suitable scavenger bases include, for example, alkali hydroxides or the bases described hereinabove with respect to the 30 reaction of Compound (B) with Compound (C). Suitable phase transfer agents are agents which transfer hydrophilic ions into a lipophilic organic medium and include, for example, benzyl triethylammonium chloride, tetra-n-butylammonium chloride, methyltrioctylammonium 35 chloride, and the like.
The compounds of Formula (Ic) wherein R3 is lower alkyl (e.g. methyl) and Rl is hydroge~ or lower alkyl, are advantageously prepared using dialkyl sulEate as the alkylating agent. This can be conveniently 40 effected by contacting the compound of Formula (Ib) with 01 -17- ~28V~5~

the desired lower alkyl sulfates in the presence of a strong base and preferably in an inert organic solvent in 05 the presence o~ a phase transfer agent. Typically, this process is conducted at temperatures in the range of abou~
from 0 to 100C, preerably 20 to 45C, using about from 1.0 to 4.0 moles of dialkyl sulfate per mole of Compound (I'). An excess, typically about 2.5 mole of 10 base is used. Preferably, this process is also conducted in an inert organic solvent such as, for example, tetrahydrofuran, carbon tetrachloride, dichloroethane, and the like.
Suitable strong bases which can be used include, 15 for example, sodium hydroxide, potassium hydroxide, sodium ethoxide, sodium carbonate, potassium carbonate, and the like. Suitable phase transfer agents are agents which transfer hydrophilic ions into a lipophilic organic medium and include, for example, benzyl triethylammonium 20 chloride, tetra-n-butylammonium chloride, methyltrioctyl-ammonium chloride, and the like.
My colleagues M. Haire, et al., have discovered that conducting the alkyl iodide and alkyl sulfate alkylation processes using an inert organic solvent in 25 which the base is insoluble (for example, using potassium carbonate or sodium hydroxide in methylene chloride) in the absence of a phase transfer agent improves the selestivity of ~he process for monoalkylation. The speed of the reaction is increased by using a phase transfer 30 agent (e.g., benzyl triethylammonium chloride) but selectivity is lost. The process is further improved by using a phase transfer agent which functions as both the phase transfer agent and the base, such as benzyltrimethyl ammonium hydroxide.
The alkylation etc., can also be felicitously effected via the procedure of my colleague P. Pomidor, by contacting co~npound Ib with the desired aqueous R3 primary amine, in methanol or ethanol at elevated temperatures (e.g., 90-120C) and pressures (e.g., 4-8 atmospheres).
~0 .. . .

~1 -18-The sulfoxide and sulfones of the invention can be conveniently prepared:

y~/ O y~/ O

~ I oxidation ~ Rl ~ R

lOl,N S R 2,N
()n' (Ia) wherein R, Rl, R2, X and Y are as defined herein above and n' is 1 or 2.
Any suitable oxidation procedùre can be used to effect the oxidation. Basically, the same procedure is used to prepare the sulfoxides and sulfones with the exception of the severity of the reaction conditions 20 and/or the amount of the oxidizing agent.
In the case of the sulfoxides (n'=l) the oxidation can be effected by contacting the corresponding compound of formula Ia with about from 1.0 to 1.5 moles o~
oxidizing agent under reactive conditions preferably in an inert organic solvent. Typically, the oxidation is conducted at temperatures in the range of about from 0 to 45C, preferably 20 to 25C for about from 1.0 to 48.0 hours, preferably 12.0 to 24.0 hours, uslng about from l.0 to 2.0 moles, preferably 1.0 to 1.5 moles of oxidizing 30 agent per mole of compound Ia.
In the case of the sulfones (n'=2) the reaction is typically conducted at temperatures in the range oE
about from 0 to 45C, preferably 20 to 25C, for about from 24 to 72 hours, preEerably 24 to 48 hours using about from 1.0 to 6.0 moles, preferably 2.0 to 4.0 moles of starting materials per mole of compound Ia.
Suitable oxidizing agents which can be used include, for example, m-chloroperbenzoic acid, hydrogen peroxide, sodium periodate, potassium permanganate, peracetic acid, and the like. Suitable solvents which can 01 -19- ~ 2 ~7~

be used include, for example, methylene chloride, chloro-form, carbon tetrachloride, acetic acid, water, and the ~5 like, and compatible mixtures thereof.
The compatible salts of Formula (I) can be pre pared by conventional procedures by tr0ating the compound of Formula (I) with a suitable strong base such as, for example, n-butyllithium, sodium hydride, potassium 10 hydride, and the like, having the desired cation, by con-ventional procedures. The enolate salts can be prepared by treating the Rl and/or R2 cation salts with base in accordance with conventional procedures. Additional variations in the salt cation can also be effected via ion 15 exchange with an ion exchange resin having the desired cation.
G0neral Process Conditions In the above-described processes, it is gener-ally preferable to separate the respective products before 20 proceeding with the next step in the reaction sequence, except where described as an in situ step or unless other-wise expressly stated. These products can be recovered from their respective reaction product mixtures by any suitable separation and purification procedure, such as, 25 for example, recrystallization and chromatography. Suit-able separation and purification procedures are, for exam-ple, illustrated in the Examples set forth hereinbelow.
Generally, the reactions described above are conducted as liquid phase reactions and hence pressure is 30 generally not significant except as it affects temperature (boiling point) where reactions are conducted at reflux.
Therefore, these reactions are generally conducted at pressures of about from 300 to 3,000 mm of mercury and conveniently are conducted at about atmospheric or ambient 35 pressure.
It should also be appreciated that where typical or preferred process conditions (e.g., reaction tempera-tures, times, mole ratios of reactants, solvents, etc.) have been given, that other process conditions could also 40 be used. Optimum reaction conditions (e.g., temperature, -20- ~ 7 S~

reaction time, mol ratios, solvents, etc.) may vary with the particular reagents or organic solvents used but can 05 be determined by routine optimization procedures.
Where optical isomer mixtures are obtained, the respective optical isomers can be obtained by conventional resolution procedures. Geometric isomers can be separated by conventional separation procedures which depend upon 10 differences in physical properties between the g00metric isomers.
Definitions As used herein the following terms have the following meanings unless expressly stated to the 15 contrary The term "lower alkyl" refers to both straight-and branched-chain alkyl groups having a total of from 1 through 4 carbon atoms and includes primary, secondary and tertiary alkyl groups. Typical lower alkyls include, for 20 example, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl.
The term "alkylene" refers to both straight chained and branched chained alkylene groups. The term "lower alkylene" refers to alkylenes having 1 through 4 25 carbon atoms and includes, for example, -CH2-; -CH2-CH2-; -CH2CH2- and the like.
The term "lower alkenyl" refers to alkenyl 30 groups having 2 through 6, preferably 2 through 4, carbon atoms and includes, for example, vinyl, l-propenyl, 2-propenyl, l-methylvinyl, l-butenyl, 2-methylprop-1-enyl and the like.
The term "lower alkoxy" refers to the group -OR' 35 wherein R' is lower alkyl.
The term "lower alkylthio" refers to the group -SR' wherein R' is lower alkyl.
The term "lower alkoxalkyl" refers to the group R'OR''- wherein R' and R'' are independently straight ~0 ~' -21~ 75~

chain or branched chain alkyl groups having l through 3 carbon atoms.
05 The term "lower alkylthioalkyl" refers to the group R'SR" - wherein R' and R'' are independently straight chain or branched chain alkyl groups having 1 through 3 carbon atoms.
The term "lower alkoxycarbonylalkyl" refers to 10 the group o R'OCR''-15 wherein R' is lower alkyl and R " is alkylene having 1 through 4 carbon atoms and can be straight or branched chained. Typical alkoxycarbonylalkyl groups include for example, -CH2C(O)OCH3; -CH(CH3)C(O)OC2H5, and the like.
The term "halo" refers to the group of fluoro, 20 chloro, bromo and iodo.
The term "lower haloalkyl" refers to haloalkyl compounds having 1 through 4 carbon atoms and 1 through 3 halo a~oms independently selected from the group of fluoro, chloro, bromo and iodo. Preferably the lo~er 25 haloalkyl group has 1 or 2 carbon atoms.
The term "lower haloalkoxy" refers to "lower alkoxy" groups having 1 through 3 halo atoms independently selècted from the group of fluoro, chloro, bromo or iodo.
The term "aryl" refers to aryl groups having 6 30 through 10 carbon atoms and includes, ~or example, phenyl, naphthyl, indenyl. Typically the aryl group will be phenyl or naphthyl as compounds having such groups are more readily available commercially than other aryl compounds.
The term "substituted aryl" refers to aryl groups having 1 through 3 substituen~s independently selected from the group of lower alkyl, lower alkoxy, halonitro, or haloalkyl having 1 through 3 carbon atoms and 1 through 3 halo atoms. Typical substituted aryl -22- ~2~7S~

groups include, for example, 2-fluorophenyl, 2-chlorophenyl, 2,6-dimethylphenyl, ~-fluorophenyl, 2-methylphenyl, 2-chloro,3-chloromethylphenyl, 2-nitro,5-methylphenyl, 2,6-dichlorophenyl, 3-trifluoromethylphenyl, 2-methoxyphenyl, 2-bromonaphth-1-yl, 3-methoxyinden-1-yl, and the like.
The term "arylalkylene" refers to the group 10 ArR3 - wherein Ar is aryl and R3 is alkylene having 1 through 3 carbon atoms~ R3 includes both straight-chained and branched-chained alkylenes, for example, methylene, ethyl, l-methylethyl, and propyl.
The term "(substituted aryl)alkylene" or 15 "ring-substituted arylalkylene" refers to the group Ar'R3 - wherein Ar' is substituted aryl and R3 is alkylene as defined with respect to arylalkylene.
The term "cycloalkyl" refers to cycloalkyl groups having 3 through 7 carbon atoms, for example 20 cyclopropyl, cyclopentyl, cyclohexyl or the like.
The term "(cycloalkyl)alkylene" refers to the group Y'R3 wherein Y' is cycloalkyl and R3 is alkylene as defined hereinabove with respect to arylalkylene.
The term "saturated nitrogen heterocycle" as 25 used herein with respect to Rl and R2 of formula I refers to the groups having the formula:

3~ / N \

& J
(CH2)n whereirl n is 1, 2, or 3.
The term "unsaturated nitrogen heterocycle" as used herein with respect to Rl and R2 oE formula I refer to the groups having the formulas:

01 -23- ~ 8~7 32 N N N N~

I l l I

~ ~ ~ and The term "compatible salts" refers to salts which do not significantly adversely alter the herbicidal 15 properties of the parent compound. Suitable salts include cation salts such asl for example, the cation salts of lithium, sodium, potassium, alkali earth metals, ammonia, quaternary ammonium salts, and the like.
The term "room temperature" or "ambient 20 temperature" refers to about 20-25C.
Utilit~
The compounds of Formula (I) exhibit both pre-emergence and post-emergence herbicidal activity and exhibit especially good pre-emergence herbicidal 25 activity. Also by varying the dosage rate certain of the compounds exhibit acceptable safety with respect to certain broadleaf crops, notably soybean crops, while retaining a broad spectrum of pr0-emergence herbicidal activity against both broadleaf weeds and grasses.
Generally, for post-emergent applications, the herbicidal compounds are applied directly to the foliage or other plant parts. For pre-emergence applications, the herbicidal compounds are applied to the growth medium, or prospective growth medium, for the plant. The optimum 35 amount of the herbicidal compound or composition will vary with the particular plant species, and the extent of plant growth, if any, and the particular part of the plant which i5 contacted and the extent of contact. The optimum dosage can also vary with the general location, or ~0 environment (e.g., sheltered areas such as greenhouses -24- ~ 752 compared to exposed areas such as fields), and type and degree of contr~l desired. Generally, for both pre- and 05 post-emergent control, the present compounds are applied at rates of about from 0002 to 60 kg/ha, preferably about from 0.02 to 10 kg/ha.
Also, although in theory the compounds can be applied undiluted, in actual practice they are generally 10 applied as a composition or formulation comprising an effective amount of the compound(s) and an acceptable car-rier. An acceptable or compatible carrier (agriculturally acceptable carrier) i5 one which does not significantly adversely af~ect the desired biological effect achieved by 15 the active compounds, save to dilute it. Typically, the composition contains about from 0.05 to 95% by weight of the compound of Formula (I) or mixtures thereof. Concen-trates can also be made having high concentrations designed for dilution prior to application. The carrier 20 can be a solid, liquid, or aerosol. The actual composi-tions can take the form of granules, powders, dusts, solu-tions, emulsions, slurries, aerosols, and the like.
Suitable solid carriers which can be used include, for example, natural clays (such as kaolin, atta-25 pulgite, montmorillonite, etc.), talcs, pyrophyllite,diatomaceous silica, synthetic fine silica, calcium alu-minosilicate, tricalcium phosphate, and the like. Also, organic materials, such as, for example, walnut shell flour, cotton-seed hulls, wheat flour, wood flour, wood 30 bark flour, and the like can also be used as carriers.
Suitable liquid diluents which can be used include, Eor example, water, organic solvents (e.g., hydrocarbons such as benzene, toluene, dimethylsulfoxide, kerosene, diesel fuel, fuel oil, petroleum naphtha, etc.), and the like.
35 Suitable aerosol carriers which can be used include con~
ventional aerosol carriers such as halogenated alkanes, etc.
The composition can also contain various promo-ters and surface-active agents which enhance the rate of transport of the active compound into the plant tissue ~ -25- ~8~7~

such as, for example, organic solvents, wetting agents and oils, and in the case of compositions designed for pre-05 emergence application agents which reduce the leachabilityof the compound or otherwise enhance soil stability.
The composition can also contain various compatible adjuvants, stabilizers, conditioners, insecti-cides, fungicides, and if desired, other herbicidally 10 active compounds.
At reduced dosages the compounds o~ the present invention also exhibit plant growth regulating activity and can be used to alter the normal growth pattern of green plants.
The compounds of Formula (I) can be applied as plant growth regulators in pure form, but more pragmatic-ally, as in the case of herbicidal application, are applied in combination with a carrier. The same types of carriers as set forth hereinabove with respect to the 20 herbicidal compositions can also be used. Depending on the desired application, the plant growth regulating com-position can also contain, or be applied in combination with other compatible ingredients such as desiccants, defoliants, surface-active agents, adjuvants, fungicides, 25 and insecticides. Typically, the plant growth regulating composition will contain a total of about from 0.005 to 90 wt. % of the compound(s) of Formula (I) depending on whether the composition is intended to be applied directly or diluted first.
A further understanding of the invention can be had in the following non-limiting Preparation and Examples. Wherein, unless expressly stated to the con-trary, all temperatures and temperature ranges refer to the Centigrade or Celcius system and the term "ambient" or "room temperature" refers to about 20-25~C. The term "percent" or "%" refers to weight percent and the term "mole" or "moles" refers to gram moles. The term "equivalent" refers to a quantity oE reagent equal in moles, to the moles of the preceding or succeeding reac-tan~ recited in that example in terms of finite moles or 01 -26- ~2~5~

finite weight or volume. ~here given, proton-magnetic resonance spectrum (p.m.r. or n.m.r.) were determined at 05 60 mHz, signals are assigned as singlets (s), broad singlets (bs), doublets (d), double doublets (dd), trip-lets (t), double triplets (dt), quartets (q), and multi-plets (m); and cps refers to cycles per second. Also where necessary preparations and examples are repeated to 10 provide additional starting material for subsequent examples.
PREPARATIONS AND EXAMPLES

(3-Trifluoromethylphenyl)-benzylcarbonyl-acetonitrile In this example, 4.91 g of metallic sodium was added to lL0 ml of anhydrous ethanol at room temperature and stirred until all of the sodium dissolved. A mixture containing 18.76 g of (3-trifluoromethylphenyl) aceto-nitrile and 21.73 g of ethyl phenylacetate was then added dropwise and the resulting mixture was stirred at reflux for about 18 hours. The mixture was then poured into 300 ml water and then extracted three times with ethyl ether. The pH of the extracted aqueous layer was then adjusted to a pH of about 1 with aqueous 10 wt. % hydro-chloric acid and then again extracted three times with ethyl ether. The organic layer was then washed twice with sa~urated aqueous sodium bicarbonate, dried over magnesium sulfate and evaporated to dryness under vacuum affording 22.6 g of the title compound.
Similarly, by applying the above procedure using the appropriately substituted-phenyl acetonitrile and ethyl-substituted acetate starting materials, the following compounds can be prepared:
(5-chloro-3-trifluoromethylphenyl)-benzylcar-3 bonyl-acetonitrile;
(4-chloro-3-trifluoromethylphenyl)-benzylcar-bonyl-acetonitrile;
(2-bromo-3-trifluoromethylphenyl)-benzylcar-bonyl-acetonitrile;

01 -27- ~X8~7~

(6-fluoro-3-trifluoromethylphenyl)-benzylcar-bonyl-acetonitrile;
05 (4-methyl-3-trifluoromethylphenyl) benzylcar-bonyl-acetonitrile;
(5-methoxy-3-trifluoromethylphenyl)-benzylcar-bonyl-acetonitrile;
(6-iodo-3-tri~luoromethylphenyl)-benzylcarbonyl-10 acetonitril~;
(3,5-di-tri~luoromethylphenyl)-benzylcarbonyl-acetonitrile;
(3-trifluoromethylphenyl)-(2,6-difluorobenzyl-carbonyl)-acetonitrile;
(3-trifluoromethylphenyl)-(3-iodobenzyl)-aceto-nitrile;
(3-trifluoromethylphenyl~-naphth-1-ylmethylene-acetonitrile;
(3-trifluoromethylphenyl)-(2-methylnaphth-1-20 ylmethylene)-acetonitrile;
(3-trifluoromethylphenyl)-(3-ethoxynaphth-1-ylmethylene)-acetonitrile;
(3-n-butylphenyl)-benzylcarbonyl-acetonitrile;
(3-n-butoxyphenyl)-benzylcarbonyl-acetonitrile;
(3-trifluoromethylthiophenyl)-benzylcarbonyl-acetonitrile;
(3-difluoromethoxyphenyl)-benzylcarbonyl-aceto-nitrile;
(3-chloromethylthiophenyl)-benzylcarbonyl-aceto-nitrile;
(3-bromophenyl)-(2-ni-trobenzylcarbonyl)-aceto-nitrile;
(2-chloro-3-propylphenyl)-(6-nitronaphth-1-ylmethylene)-acetonitrile;
(3-bromo-2-ethylphenyl)-naphth-1-yl~ethylene-acetonitrile;
. (3,6-difluorophenyl)-beta-naphth-1-ylethyl-acetonitrile;
(3-iodo-4-methylphenyl)-(2,7-difluoronaphth-1-ylmethylene)-acetonitrile;

01 -28~ 75~

(3-chlorophenyl)-benzylcarbonyl-acetonitrile;
[3-(2-fluoropropylthio)phenyl]-benzylcarbonyl-05 acetonitrile;
(3-t-butoxyphenyl)-benzylcarbonyl-acetonitrile;
[3-(2,3-dichloropropylthiophenyl)-ben~yl-carbonyl acetonitrile;
(3-bromophenyl)-benzylcarbonyl-acetonitrile;
(3-iodophenyl)-(2,3-dinitrobenzylcarbonyl)-acetonitrile;
(3-1ùorophenyl)-(8-trifluoromethylnaphth-1-ylmethylene)-acetonitrile;
(3-isopropoxyphenyl)-2-naphthylmethylene-aceto-15 nitrile;
(3-fluorophenyl)-(6-butyl-8-chloronaphth-1-ylmethylene-acetonitrile;
(3-trifluoromethylphenyl)-(3-nitronaphth-1-ylmethylene)-acetonitrile.
(3-iodophenyl)-(3-nitrobenzylcarbonyl)-acetonitrile;
(3-trifluoromethylphenyl)-(2,3-dichlorobenzyl-carbonyl)-acetonitrile;
(3-methoxyphenyl)-1-naphthylmethylenecarbonyl-25 acetonitrile;
(3-trifluoromethyl)-(3-chloro-8-fluoronaphth-1-ylmethylenecarbonyl)-acetonitrile;
: (3-trifluoromethyl)-[(2-trifluoromethyl-3-methyl-8-methoxy-naphth-1-yl)methylenecarbonyl]-aceto-nitrile;
(3-trifluoromethyl)-(inden-1-ylmethylene-carbonyl)-acetonitrile; and ~3-trifluoromethyl)-(2-fluoroinden-1-yl-methylenecarbonyl)-acetonitrile.
Similarly, by applying the same procedure to the appropriate ethyl alkoxy substituted acetate the corresponding alkoxy acetonitrile analogs of the above compounds can be prepared, for example:
(3-trifluoromethylphenyl)-dimethoxyacetyl-acetonitrile;

01 -29- ~ ~ 8~ 5 (3-triEluoromethylphenyl)-(butoxy-methoxyacetyl)-acetonitrile, etc.
05 The alkoxy compounds can be converted to the corresponding 2-alkoxy compounds of the invention via the procedure described in Example 3A hereinbelow.
Example 1 2-Phenyl-3-oxo-4-(3-trifluoromethylphenyl)-~ 5-amino-2,3-dihYdrothiophene u In this example a solution containing 2.0 g of (3-trifluoromethylphenyl)-benzylcarbonyl-acetonitrile in 30 ml of tetrahydrofuran was added dropwise to 13.2 ml of a 1 molar mixture o lithium bis(trimethylsilyl)amide 15 under anhydrous conditions at -70C. The resulting mixture was stirred for ten minutes and then allowed to rise to room temperature and stirred for another 20 minutes. 0.21 g of powdered elemental sulfur was then admixed therewith and the resulting mixture stirred for 20 about 18 hours. The mixture was then added to 200 ml of aqueous saturated ~,lmonium chloride solution and then extracted three times with ethyl ether. The combined ether extracts were dried over magnesium sulfate and then concentrated by evaporation under vacuum affording 1.8 g ; 25 Of a crude solid of the title compound. The crude solid was chromatographed on silica gel eluting with 30% vol.
ethyl acetate:70% petroleum ether to afford 0.4 g of the title compound.
Similarly, by applying the above procedure to 30 the compounds listed in Preparation 1, the following compounds can be prepared:
2-phenyl-3-oxo-4-(5-chloro-3-triEluoromethyl-phenyl)-5-amino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-(4-chloro-3-trifluoromethyl-35 phenyl)-5-amino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-(2-bromo-3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-(6-fluoro--3-tri1uoromethyl-phenyl)-5-amino-2,3-dihydrothiophene;

" 01~30- ~'~8~75~

2-phenyl-3-oxo-4-(4-methyl-3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrothiophene;
052-phenyl-3-oxo-4-(5-methoxy-3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-(6-iodo-3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-(3,5-di-trifluoromethylphenyl)-10 S-amino-2,3-dihydrothiophene;
2-(2-nitrophenyl)-3-oxo-4-(3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrothiophene;
2-(3-iodophenyl)-3-oxo-4-(3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrothiophene;
152-(naphth-1-yl)-3-oxo-4-(3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrothiophene;
2-(2-methylnaphth-1-yl)-3-oxo-4-(3-trifluoro-methylphenyl)-5-amino-2,3-dihydrothiophene;
2-(3-ethoxynaphth-1-yl)-3-oxo-4-(3-trifluoro-20 methylphenyl)-5-amino-2,3-dihydrothiophene; and 2-phenyl-3-oxo-4-(3-n-butylphenyl)-5-amino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-(3-n-butoxyphenyl)-5-amino-2,3-dihydrothiophene;
252-phenyl-3-oxo-4-(3-trifluoromethylthiophenyl)-5-amino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-(3-difluoromethoxyphenyl)-5-amino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-(3-chloromethylphenyl)-5-amino-2,3-dihydrothiophene;
2-(2-nitrophenyl)-3-oxo-4-(3-bromophenyl)-5-amino-2,3-dihydrothiophene;
2-(6-nitronaphth-1-yl)-3-oxo-4-(2-chloro-3-propylphenyl)-5-amino-2,3-dihydrothiophene;
352-(naphth-1-yl) 3-oxo-4-(3-bromo-2-ethylphenyl)-5-amino-2,3-dihydrothiophene;
2-(naphth-1-yl)-3-oxo-4-(3,6-difluorophenyl)-5-amino-2,3-dihydrothiophene;
2-(2,7-difluoronaphth-1-yl)-3-oxo-4-(3-iodo-4-methylphenyl)-5-amino-2,3-dihydrothiophene;

~,ao7~'~

2-phenyl-3-oxo-4-(3-chlorophenyl)-5-amino-2,3-dihydrothiophene;
052-phenyl-3-oxo-4-[3(2-fluoropropylthio)phenyl]-5-amino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-(3-t-butoxyphenyl)-5-amino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-[3-(2,3-dichloropropylthio-10 phenyl)]-5-amino-2,3-dihydrothiophene;
2-phenyl-3-oxo 4-(3-bromophenyl)-5-amina-2,3-dihydrothiophene;
2-(2,3-dinitrophenyl)-3-oxo-4-(3-iodophenyl)-5-amino-2,3-dihydrothiophene;
152-(8-trifluoromethylnaphth-1-yl)-3-oxo-4-(3-fluorophenyl)-5-amino-2,3-dihydrothiophene;
2-(naphth-1-yl)-3-oxo-4-(3-isopropoxyphenyl)-5-amino-2,3-dihydrothiophene;
2-(6-butyl-8-chloronaphth-1-yl)-3-oxo-4-(3-20 fluorophenyl)-5-amino-2,3-dihydrothiophene;
2-(3-nitronaphth-1-yl)-3-oxo-4-(3-triEluoro-methylphenyl)-5-amino-2,3-dihydrothiophene;
2-(3-nitrophenyl)-3-oxo-4-(3-iodophenyl)-5-amino-2,3-dihydrothiophene;
252-(2,3-dichlorophenyl~-3-oxo-4-(3-trifluoro-methylphenyl)-5-amino-2,3-dihydrothiophene;
2-(1-naphthyl)-3-oxo-4-(3-methoxyph~nyl)-5-amino-2,3-dihydrothiophene;
2-(3-chloro-8-fluoronaphth-1-yl-3-oxo-4-(3-tri-30 fluoromethylphenyl)-5-amino-2,3-dihydrothiophene;
2-(2-trifluoromethyl-3-methyl-8-methoxy-naphth-l-yl)-3-oxo-4-(3-triEluoromethylphenyl)-5-amino-2,3-dihydrothiophene;
2-inden-1-yl-3-oxo-4-(3-triEluoromethylphenyl)-5-amino-2,3-dihydrothiophene; and 2-(2-fluorcinden-1-yl)-3~oxo-4-(3-trifluoro-methylphenyl)-5-amino-2,3-dihydrothiophene.

~O

Ol -32- ~ 7~2 Example 2 (3-Trifluoromethylphenyl)-(2-methyl-05 thiopropionyl)-acetonitrile In this example 6~0 g of (3-trifluoromethyl-phenyl)-(methylthioacetyl)-acetonitrile in 15 ml of tetra-hydrofuran was added dropwise to 43.96 ml of a 1 molar solution of lithium bis(trimethylsilyl)amide, i.e.
[(CH3)3Si]2NeLi~, under anhydrous conditions at -70C.
The temperature of the resulting mixture was allowed to rise to room temperature and it was then stirred at room temperature for 45 minutes. 3.12 g of methyl iodide was then slowly added and the resulting mixture stirred 15 overnight (about 12-16 hours) under a nitrogen atmosphera. The mixture was added to 200 ml of saturated ammonium chloride solution and then extracted three times with ethyl ether. The ether extracts were combined, dried over magnesium sulfate and concentrated in vacuo yielding a crude oily residue. The residue was chromatographed on silica gel eluting with 70:30 vol. hexane:ethyl acetate yielding 2.9 g of the title compound as an oil.
Similarly, by following the same procedure using the appropriately substituted phenyl-(methylthioacetyl)-acetonitrile and the appropriate R iodide, the correspond-ing star~ing materials for Example 3, hereinbelow, can be prepared.
Example 2A
(3-Trifluoromethylphenyl)-(2-phenyl-~ 2-methylthiopropionyl)-acetonitrile i In this example a mixture containing 12 g of t3-trifluoromethylphenyl)-acetonitrile and 14 g of methyl alpha-thiomethylphenylacetate was added to a stirred slurry at room temperature containing 3.4 g of sodium hydride in 150 ml of tetrahydrofuran. The mixture was stirred for 11/2hours at room temperature under a nitrogen atmosphere. The mixture was then added to 250 ml of water extracted twice with ether. The organic (THF ~ ether) layer was then washed twice with water. The aqueous layers were combined and then acidified to pH 1 with 10%
hydrochloric acid, extracted three times with ether, , . , .: ;. , ~X8~1~S2 washed with saturated aqueous sodium bicarbonate solution, dried over magnesium sulfate and evaporated under vacuum 05 affordiny 6~5 g of the title compound as a brown oil.
Similarly, by following the same procedure using the correspondingly substituted starting materials the starting materials for the product listed in Example 3A
hereinbelow can be made.
Example 3 2-Methyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrothioph_ne In this example, about 2.0 ml of conGentrated (98 wt%) suluric acid was added ~o a mixture containing 2.9 g of (3-trifluoromethylphenyl)-(2-methylthiopro-pionyl)-acetonitrile in 20 ml of acetic acid at room temperature. The mixture was then warmed to reflux and re~luxed for thirty minutes. The mixture was then concentrated by evaporation under vacuum. The concentrate was then chromatographed over silica gel eluting with a mixture of 2%, vol., acetone in methylene chloride affording 0.85 g of the title compound.
Similarly, by following the same procedure using the corresponding appropriately substituted starting mate-rials the following compounds can be prepared:
2-ethyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrothiophene;
2-vinyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3~dihydrothiophene;
2-(n-propyl)-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrothiophene;
2-(n-butyl)-3-oxo-~-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrothiophene;
2-allyl-3-oxo-4-(2-methoxy-3-triEluoromethyl-phenyl)-5-amino-2,3-dihydrothiophene;
2-trifluoromethyl-3-oxo-4-(3-trifluoromethyl-~henyl)-5-amino~2,3-dihydrothiophene;
2-(2-chlorovinyl)-3-oxo-4-(5-nitro-3-trifluoro-methylphenyl)-3-oxo-5-amino-2,3-dihydrothiophene;

01-34- ~Z8~75~

2-methyl-3-oxo-4-(2-methoxy-3-chlorophenyl)-5-amino-2,3-dihydrothiophene;
- 052-(n-propyl)-3-oxo-4-(3-difluoromethoxyphenyl)-5-amino-2,3-dihydrothiophene;
2-methyl-3-oxo-4-(3-difluoromethoxyphenyl)-5-amino-2,3-dihydrothiophene;
2-ethyl-3-oxo-4-(2-chloro-3-fluorophenyl)-5-10 amino-2,3-dihydrothiophene;
2-vinyl-3-oxo-4-(3-propoxyphenyl)-5-amino-2,3-dihydrothiophene;
2-allyl-3-oxo-4-(3-butylthiophenyl)-5-amino-2,3-dihydrothiophene;
lS2-trifluoromethyl-3-oxo-4-(3-trifluoromethyl-4-bromophenyl)-5-amino-2,3-dihydrothiophene;
2-(2-chlorovinyl)-3-oxo-4-(3-chloromethylthio-4-methylphenyl)-3-oxo-5-amino-2,3-dihydrothioph~ne;
2-methyl-3-oxo-4-[3-(4-fluorobutyl)phenyl]-5-amino-2,3-dihydrothiophene;
2-ethyl-3-oxo-4-(3-chlorophenyl)-5-amino-2,3-dihydrothiophene;
2-vinyl-3-oxo-4-(3-butylphenyl)-5-amino-2,3-dihydrothiophene;
252-allyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrothiophene;
2-triEluoromethyl-3-oxo-4-(3,4-di1uorophenyl)-5-amino-2,3-dihydrothiophene;
2-ethyl-3-oxo-4-(2-chloro-3-fluorophenyl)-5-amino-2,3-dihydrothiophene;
2-vinyl-3-oxo-4-(2-nitro-3-butoxyphenyl)-5-amino-2,3-dihydrothiophene;
2-allyl-3-oxo-4-~2-methyl-3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrothiophene;
352-(trifluoromethyl)-3-oxo-4-(3-tri1uoromethyl-4-bromophenyl)-5-amino-2,3-dihydrothiophene;
. 2-(2-chlorovinyl)-3-oxo-4-(3-nitro-3-propyl-phenyl)-3-oxo-5-amino-2,3-dihydrothiophene;
2-hexyl-3-oxo-4-(3-fluoromethylthiophenyl)-5-amino-2,3-dihydrothiophene;

01 -35- 1'~8~

2-propyl-3-oxo-4-(3-iodophenyl)-3-oxo-5-amino-2,3-dihydrothiophene;
~5 2-isopropyl-3-oxo-4-(2-chloro-3-fluorophenyl) 5-amino-2,3-dihydrothiophene;
2-ethyl-3 oxo-4-(3-difluoromethoxyphenyl)-5-amino-2,3-dihydrothiophene;
2-cyclohexyl-3-oxo-4-(3-trifluoromethylphenyl)-~0 5-amino-2,3-dihydrothiophene;
2-(2-trifluoromethylbenzyl)-3-oxo-4-(3-tri-Eluoromethylphenyl)-5-amino-2,3-dihydrothiophene;
2-(beta-naphth-1-ylethyl)-3-oxo-4-(3-trifluoro-methylphenyl)-5-amino-2,3-dihydrothiophene;
2-(2-fluoro-3-2',2'-dichloroethylbenzyl)-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrothiophene;
2-(2,3-dichloro-6-methylbenzyl)-3-oxo-4-(3-tri-fluoromethylphenyl)-5-amino-2,3-dihydrothiophene;
2-(beta-phenethyl)-3-oxo-4-(3-trifluoromethyl-20 phenyl)-5-amino-2,3-dihydrothiophene;
2-[3-(2-bromophenyl)propyl]-3-oxo-4-(3-tri-luoromethylphenyl)-5-amino-2,3-dihydrothiophene;
2-[1-methyl-2-(phenyl)ethyl]-3-oxo-4-(3-tri-fluoromethylphenyl)-5-amino-2,3-dihydrothiophene;
2-naphth-1-ylmethylene-3-oxo-4-(3-trifluoro-methylphenyl)-5-amino-2,3-dihydrothiophene, 2-(2-fluoronaphth-1-ylmethylene)-3-oxo-4-(3-tri-fluoromethylphenyl)-5-amino-2,3-dihydrothiophene;
2-cyclopropylmethylene-3-oxo-4-(3-trifluoro-30 methylphenyl)-5-amino-2,3-dihydrothiophene;
2-(3-butylnaphth-1-ylmethylene)-3-oxo-4-(3-tri-fluoromethylphenyl)-5-amino-2,3-dihydrothiophene;
2-(5-methoxynaphth-1-ylmethylene)-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrothiophene;
2-(6-nitronaphth-1-ylmethylene)-3-oxo-4-(3-tri fluoromethylphenyl)-5-amino-2,3-dihydrothiophene;
2-(7-trifluoromethylnaphth-1-ylomethylene)-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydro-thiophene;
~0 01 -36- ~Z B~ 5Z

2-(2-chloro-8-methylnaphth-1-ylmethylene)-3-o~o-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrothiophene;
05 2-[beta-(8-fluoronaphth-1-yl)ethyl]-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrothiophene:
2-[1-(7-methoxynaphth-1-yl)ethyl]-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrothiophene;
2-inden-1-ylmethylene-3-oxo-4-(3-trifluoro-10 methylphenyl)-5-amino-2,3-dihydrothiophene;
2-(2-fluoroinden-1-ylmethylene)-3-oxo-4-(3-tri-fluoromethylphenyl)-5-amino-2,3-dihydrothiophene;
2 methoxymethylene-3-oxo-4-(3-trifluorornethyl-phenyl)-5-amino-2,3-dihydrothiophene;
2-cyclopentylethylene-3-oxo-4-(3-trifluoro-methylphenyl)-5~amino-2,3-dihydrothiophene;
2-propoxymethylene-3-oxo-4-(3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrothiophene;
2-ethoxymethylene-3-oxo-4-(3-trifluoromethyl-20 phenyl)-5-amino-2,3-dihydrothiophene;
2-(2-methoxypropyl)-3-oxo-4-(3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrothiophene;
2-methylthiomethylene-3-oxo-4-(3-trifluoro-methylphenyl)-5-amino-2,3-dihydrothiophene; and 2-(1-propyl~hioethyl)-3-oxo-4-(3-trifluoro-methylphenyl)-5-amino-2,3-dihydrothiophene.
Example 3A
2-Phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrothiophene In this example a mixture containing 10.8 g of (3-trifluoromethylphenyl)-(2-phenyl-2-methylthiopro-pionyl)-acetonitrile and 10 ml of concentrated sulfuric acid in 50 ml of acetic acid i9 warmed to reflux and refluxed for 20 minutes. The mixture was then concen-35 trated under vacuum thereby removing most of the acetic acid. The concentrate was added to ethyl acetate, washed twice with lN aqueous sodium hydroxide, then twice with saturated a~ueous sodium bicarbonate, and dried over magnesium sulfate. The dried mixture was concentrated by 40 vacuum evaporation affording 7 g of a crude dark oil of 01 ~37~

the title compound. The ~rude oil was chromatographed eluting within 1:1 by vol. of hexane:ethyl acetate, 05 affording 1.6 g of the title compound.
Similarly, by following the same procedure using the corresponding starting materials the following compounds can be prepared:
2-me-thoxy-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrothiophene;
2-t3,4-dichlorophenyl)-3-oxo-4-(3-trifluoro-methylphenyl)-5-amino-2,3-dihydrothiophene;
2-naphthyl-3-oxo-4-(3-trifluoromethyl-4-bromophenyl)-5-amino-2,3-dihydrothiophene;
2-(3-methylbenzylphenyl)-3-oxo-4-(3-methoxy-4-methylphenyl)-3-oxo-5-amino-2,3-dihydrothiophene;
2-(3-fluorophenyl)-3-oxo-4-(3-chlorophenyl)-5-amino-2,3-dihydrothiophene;
2-(2-fluorobenzyl)-3-oxo-4-(3-methylphenyl)-5-~ amino-2,3-dihydrothiophene;
2-(3-chlorobenzyl)-3-oxo-4-(3-butylthiophenyl)-5-amino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-(3-beta-chloroethylphenyl)-5-amino-2,3-dihydrothiophene;
2-methoxy-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrothiophene;
2-n-butoxy 3-oxo-4-(3-tri1uoromethylphenyl)-5-amino-2,3-dihydrothiophene;
2-(1-naphthyl)-3-4-(3-methoxyphenyl)-5-amino-2,3-dihydrothiophene;
2-(3-chloro-8-fluoronaphth-1-yl)-3-oxo-4-(3-trifluoromethylphenyl-5-amino-2,3-dihydrothiophene;
2-(2-trifluoromethyl-3-methyl-8-methoxynaphth-1-yl)-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrothiophene;
2-inden-1-yl-3-oxo-~-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrothiophene;
2-(2-fluoroinden-1-yl)-3-oxo-4-(3-tri1uoro-methylphenyl)-5-amino-2,3-dihydrothiophene;

-38- ~i28~7SiZ

2-(2-chloro-3-propylphenyl)-3-o~o-4-(3-tri-fluoromethylphenyl-5-amino-2,3-dihydrothiophene;
05 2-(2-nitro-3-methoxyphenyl)-3-oxo-4-(3-tri-fluoromethylphenyl)-5-amino-2,3-dihydrothiophene; and 2-(3-methoxy-5-nitro-7-fluoromethylnaphth-1-yl)-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydro-thiophene;
Example 4 2-Phenyl-3-oxo-4-(-3-trifluoromethylphenyl)-5-methylamlno-2,3-dihYdrothiophene This example illustrates a procedure which can be used to prepare the substituted amine derivatives of 15 the present invention~
In this example about 1 g of solid sodium hydroxide in 4.0 ml of water is added to a mixture containing 4.6 9 of 2-phenyl-3-oxo-4-(3-trifluoromethyl-phenyl)-5 amino-1,2-dihydrothiophene in 80 ml of methylene 20 chloride at room temperature followed by the addition of 1.73 g of dimethyl sulfate and 0.21 g of benzyltriethyl ammonium chloride. The resulting two-phase mixture was stirred at room temperature for about 18 hours and was then washed three times with water, dried over magnesium 25 sulfate and then concentrated by evaporation under vacuum. The residue was purified by chromatography over silica gel eluting with 1%, vol., tetrahydrofuran in chloroform affording 1.8 g of the title compound.
Similarly, by following the same procedure using 30 the products listed in Examples 1 and 3 as starting mate-rials, the corresponding 5-methylamino homologs thereof can be prepared, for example:
2-phenyl-3-oxo-4-(5-chloro-3-triflueromethyl-phenyl)-5-methylamino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-(4-chloro-3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-~2-bromo-3-triEluoromethyl-phenyl)-5-methylamino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-(6-fluoro--3-trifluoromethyl-40 phenyl)-5-methylamino-2,3-dihydrothiophene;

-~ 32~

2-phenyl-3-oxo-4-(4-methyl-3-tri~luoromethyl-phenyl)-5-methylamino-2,3-dihydrothiophene;
05 2-phenyl-3-oxo-4-(5-methoxy-3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-(6-iodo-3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-(3,5-di-tri1uoromethylphenyl)-10 5-methylamino-2,3-dihydrothiophene;
2-(2-nitrophenyl)-3 oxo-4-(3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrothiophene;
2-(3-iodophenyl)-3-oxo-4-(3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrothiophene;
2-(naphth-1-yl)-3-oxo-4-(3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrothiophene;
2-(2-methylnaphth-1-yl)-3-oxo-4-(3-trifluoro-methylphenyl)-5-methylamino-2,3-dihydrothiophene;
2-~3-ethoxynaphth-1-yl)-3-oxo-4-(3-trifluoro-~0 methylphenyl)-5-methylamino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-(3-n-butylphenyl)-5-methyl-amino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-(3-n-butoxyphenyl)-5-methylamino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-(3-trifluoromethylthiophenyl)-5-methylamino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-(3-difluoromethoxyphenyl)-5-methylamino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-(3-chloromethylphenyl)-5-30 methylamino-2,3-dihydrothiophene;
2-(2-nitrophenyl)-3-oxo-4-(3-bromophenyl)-5-methylamino-2,3-dihydrothiophene;
2-(6-nitronaphth-1-yl)-3-oxo-4-(2-chloro-3-propylphenyl)-S-methylamino-2,3-dihydrothiophene;
2-(naphth-1-yl)-3-oxo-4-(3-bromo-2-ethylphenyl)-5-methylamino-2,3-dihydrothiophene;
. 2-(naphth-1-yl)-3-oxo-4-(2,3-difluorophenyl)-5-methylamino-2,3-dihydrothiophene;
2-(2,7-difluoronaphth-1-yl)-3-oxo-4-(3-iodo-4-40 methylphenyl)-5-methylamino-2,3-dihydrothiophene;

01 ~40- ~Z ~7 ~
2-phenyl-3-oxo-4-(3-chlorophenyl)-5-methylamino-2,3-dihydrothiophene;
05 2-phenyl-3-oxo-4-[3-(2-fluoropropylthio~phenyl~-5-methylamino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-(3-t-butoxyphenyl)-5-methyl~
amino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-[3-(2,3-dichloropropylthio-10 phenyl)]-5-methylamino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-(3-bromophenyl)-5-methylamino-2,3-dihydrothiophene;
2-(2,3-dinitrophenyl)-3-oxo-4-(3-iodophenyl)-5-methylamino-2,3-dihydrothiophene;
2-(8-trifluoromethylnaphth-1-yl)-3-oxo-4-(3-fluorophenyl)-5-methylamino-2,3-dihydrothiophene;
2-(naphth-1-yl)-3-oxo-4-(3-isopropoxyphenyl)-5-methylamino-2,3-dihydrothiophene;
2-(6-butyl-8-chloronaphth-1-yl)-3-oxo-4-(3 20 fluorophenyl)-5-methylamino-2,3-dihydrothiophene;
2-(3-nitronaphth-1-yl)-3-oxo-4-(3-fluorophenyl)-5-methylamino-2,3-dihydrothiophene;
2 (3-nitrophenyl)-3-oxo-4(3-iodophenyl)-5-methylamino-2,3-dihydrothiophene;
2-(2,3-dichlorophenyl)-3-oxo-4-(3-trifluoro-methylphenyl)-5-methylamino-2,3-dihydrothiophene;
2-(1-naphthyl)-3-oxo-4-(3-methoxyphenyl)-5-methylamino-2,3-dihydrothiophene;
2-(3-chloro-8-fluoronaphth-1-yl)-3 oxo-4-(3-tri-30 fluoromethylphenyl)-5-methylamino-2,3-dihydrothiophene;
2-(2-trifluoromethyl-3-methyl-8-methoxy-naphth-l-yl)-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrothhiophene;
2-inden-1-yl-3-oxo-4-(3-trifluoromethylphenyl)-35 5-methylamino-2,3-dihydrothiophene;
2-(2-Eluoroinden-1-yl)-3-oxo-4-(3-trifluoro-methylphenyl)-5-methylamino-2,3-dihydrothiophene;
2-methyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrothiophene;

-41~ 807~

2-ethyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrothiophene;
052-ethyl-3-oxo-4-,3-difluoromethoxyphenyl)-5-methylamino-2,3-dihydrothiophene;
2-(n-propyl-3-oxo-4-(3-difluoromethoxyphenyl)-5-methylamino-2,3-dihydrothiophene;
2-vinyl-3-oxo-4-(3-trifluoromethylphenyl)-5-10 methylamino-2,3-dihydrothiophene;
2-(n-propyl)-3-oxo-4-(3-trifluoromethylphenyl)-S-methylamino-2,3-dihydrothiophene;
2-(n-butyl)-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrothiophene;
152-allyl-3-oxo-4-(2-methoxy-3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrothiophen~;
2-trifluoromethyl-3-oxo-4-t3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrothiophene;
2-(2-chlorovinyl)-3-oxo-4-(5-nitro-3-trifluoro-20 methylphenyl)-3-oxo-5-methylamino-2,3-dihydrothiophene;
2-methyl-3-oxo-4-(2-methoxy-3-chlorophenyl)-S-methylamino-2,3 dihydrothiophene;
2-ethyl-3-oxo-4-(2-chloro-3-fluorophenyl)-5-methylamino-2,3-dihydrothiophene;
252-vinyl-3-oxo-4-(3-propoxyphenyl)-S-methylamino-2,3-dihydrothiophene;
2-methyl-3-oxo-4-(3-difluoromethoxyphenyl)-5-: methylamino-2,3-dihydrothiophene;
2-allyl-3-oxo-4-(3-butylthiophenyl)-5-methyl-30 amino-2,3-dihydrothiophene;
2-trifluoromethyl-3-oxo-4-(3-trifluoromethyl-4-bromophenyl)-5-methylamino-2,3-dihydrothiophene;
2-(2-chlorovinyl)-3-oxo-4-(3-chloromethylthio-4-methylphenyl)~3-oxo-5-methylamino-2,3-dihydrothiophene;
352-methyl-3-oxo-4-[3-(4-fluorobutyl)phenyl]-5-methylamino-2,3-dihydrothiophene;
. 2-ethyl-3-oxo-4-(3-chlorophenyl)-5-methylamino-2,3-dihydrothiophene;
2-vinyl-3-oxo-4-~3-butylphenyl)-5-methylamino-2,3-dihydrothiophene;

~2a~7s2 2-allyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrothiophene;
05 2-trifluoromethyl-3-oxo-4-(3,4-difluorophenyl)-5-methylamino-2,3-dihydrothiophene;
2-(2-chlorovinyl)-3-oxo-4-(3-bromophenyl)-3-oxo-5-methylamino-2,3-dihydrothiophene;
2-cyclopropylmethylene-3-oxo-4-(3-trifluoro-10 methylphenyl)-5-methylamino-2~3-dihydrothiophene;
2-cyclopentylethylene-3-oxo-4-(3-trifluoro-methylphenyl)-5-methylamino-2,3-dihydrothiophene;
2-methyl-3-oxo-4-(2-methoxy-3-chlorophenyl)-5-methylamino-2,3-dihydrothiophene;
2-ethyl-3-oxo-4-(2-chloro-3-~luorophenyl)-5-methylamino-2,3-dihydrothiophene;
2-vinyl-3-oxo-4-(2-nitro-3-butoxyphenyl)-5-methylamino-2,3-dihydrothiophene;
2-allyl-3-oxo-4-(2-methyl-3-trifluoromethyl-20 phenyl)-5-methylamino-2,3-dihydrothiophene;
2-(trifluoromethyl)-3-oxo-4-(3-trifluoromethyl-4-bromophenyl)-5-methylamino-2,3-dihydrothiophene;
2-(2-chlorovinyl)-3-oxo-4-(3-nitro-3 propyl-phenyl)-3-oxo-5-methylamino-2,3-dihydrothiophene;
2-hexyl-3-oxo-4-(3-fluoromethylthiophenyl)-5-methylamino-2,3-dihydrothiophene;
2-propyl-3-oxo-4-(3-iodophenyl)-3-oxo-5-methyl-amino-2,3-dihydrothiophene;
2-isopropyl-3-oxo-4-(2-chloro-3-fluorophenyl)-S-30 methylamino-2,3-dihydrothiophene;
2-cyclohexyl-3-oxo-4-(3-tri1uoromethylphenyl)-5-methylamino-2,3-dihydrothiophene;
2-(2-trifluoromethylbenzyl)-3-oxo-4-(3-tri-fluoromethylphenyl)-5-methylamino-2,3-dihydrothiophene;
2-(beta-naphth-1-ylethyl)-3-oxo-4-(3-trifluoro-methylphenyl)-5-methylamino-2,3-dihydrothiophene;
. 2-(2-fluoro-3-2',2'-dichloroethylbenzyl ! -3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydro-thiophene;

2807~
01 _43_ 2-(2,3-dichloro-6-methylbenzyl)-3-oxo-4-(3-tri-fluoromethylphenyl)-5-methylamino-2,3-dihydrothiophene;
05 2-(beta-phenethyl)-3-oxo-4-(3-tri~luoromethyl-phenyl)-5-methylamino-2,3-dihydrothiophene;
2-[3-(2-bromophenyl)propyl]-3-oxo-4-(3-tri-fluoromethylphenyl)-5-methylamino-2,3-dihydrothiophene;
2-[1-methyl-2-(phenyl)ethyl]-3-oxo-4-(3-tri-10 fluoromethylphenyl)-5-methylamino-2,3-dihydrothiophene;
2-naphth-1-ylmethylene-3-oxo-4-(3-trifluoro-methylphenyl)-5-methylamino-2,3-dihydrothiophene;
2-(2-fluoronaphth-1-ylmethylene)-3-oxo-4-(3-tri-fluoromethylphenyl)-5-methylamino-2,3-dihydrothiophene;
2-(3-butylnaphth-1-ylmethylene)-3-oxo-4-(3-tri-1uoromethylphenyl)-5-methylamino-2,3-dihydrothiophene;
2-(5-methoxynaphth-1-ylmethylene)-3-oxo-4-(3-trifluoromethylphenyl~-5-methylamino-2,3-dihydrothiophene;
2-(6-nitronaphth-1-ylmethylene)-3-oxo-4-(3-tri-20 fluoromethylphenyl)-5-methylamino-2,3-dihydrothiophene;
2-(7-trifluoromethylnaphth-1-ylomethylene)-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydro-thiophene;
2-(2-chloro-8-methylnaphth-1-ylmethylene)-3-oxo-25 4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydro-thiophene;
2-[beta-(8-~luoronaphth-1-yil)ethyl]-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrothiophene;
2-[1-(7-methoxynaphth-1-yl)ethyl]-3-oxo-4-(3-30 trifluoromethylphenyl)-5-methylamino-2,3-dihydrothiophene;
2-inden 1-ylmethylene-3-oxo-4-(3-tri1uoro-methylphenyl)-5-methylamino-2,3-dihydrothiophene;
2-(2-fluoroinden-1-ylmethylene)-3-oxo-4-(3-tri-fluoromethylphenyl)-5-methylamino-2,3-dihydrothiophene;
2-methoxymethylene-3-oxo-4-(3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrothiophene;
2-propoxymethylene-3-oxo-4-(3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrothiophene;
2-ethoxymethylene-3-oxo-4-(3-trifluoromethyl-~ phenyl)-5-methylamino-2,3-dihydrothiophene;

01 ~44~ ~ Z ~7 5~

2-(2-methoxypropyl)-3-oxo-4-(3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrothiophene;
05 2-methylthiomethylene-3-oxo-4-~3-trifluoro-methylphenyl)-5-methylamino-2,3-dihydrothiophene; and 2-(1-propylthioethyl~-3-oxo-4-(3-tri1uoro-methylphenyl)-5-methylamino-2,3-dihydrothiophene.
2-(3,4-dichlorophenyl)-3-oxo-4-(3-trifluoro-10 methylphenyl)-5-methylamino-2~3-dihydrothiophene;
2-naphthyl-3-oxo-4-(3-trifluoromethyl-4-bromophenyl)-5-methylamino-2,3-dihydrothiophene;
2 (3-methylbenzylphenyl)-3-oxo-4-(3-methoxy-4-methylphenyl)-3-oxo-5-methylamino-2,3-dihydrothiophene;
2-(3-fluorophenyl)-3-oxo-4-(3-chlorophenyl)-5-methylamino-2,3-dihydrothiophene;
2-(2-fluorobenzyl)-3-oxo-4-(3-methylphenyl)-5-methylamino-2,3-dihydrothiophene;
2-(3-chlorobenzyl)-3-oxo-4-(3-butylthiophenyl)-20 5-methylamino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-(3-beta-chloroethylphenyl)-5-methylamino-2,3-dihydrothiophene;
2-methoxy-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrothiophene;
: 25 2-n-butoxy-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrothiophene;
2-(1-naphthyl)-3-4-(3-methoxyphenyl)-5-methylamino-2,3-dihydrothiophene;
2-(3-chloro-8-fluoronaphth-1-yl)-3-oxo-4-(3-30 trifluoromethylphenyl)-5-methylamino-2,3-dihydrothiophene;
2-(2-tri1uoromethyl-3-methyl-8-methoxynaphth-1-yl)-3-oxo-4-(3-trifluoromethylphenyl)-5~methylamino-2,3-dihydrothiophene;
2-inden-1 yl-3-oxo-4-(3-triEluoromethylphenyl)-35 5-methylamino-2,3-dihydrothiophene;
2-(2-fluoroinden-1-yl)-3-oxo-4-(3-trifluoro-methylphenyl)-5-methylamino-2,3-dihydrothiophene;
2-(2-chloro-3-propylphenyl)-3-oxo-4-(3-tri--fluoromethylphenyl-5-methylamino-2,3-dihydrothiophene;
: 40 01 -45- ~28~7~

2-(2-nitro-3-methoxyphenyl)-3-oxo-4-(3-tri-fluoromethylphenyl)-5-methylamino-2,3-dihydrothiophene;
05 and 2-(3-methoxy-5-nitro-7-fluoromethylnaphth~l-yl)-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrothiophene;
Similarly, by approximately doubling the amount 10 of dimethylsulfate and increasing the reaction time, the corresponding 5-dimethylamino homologs thereof can be prepared. By using diethylsulfate in place of dimethyl-sulate the corresponding 5-ethylamino and 5-diethylamino homologs of the above compounds can be prepared.
Example 5 2-(2-Fluorophenyl)-3-oxo-4-(3-trifluoro-meth~lphenyl)-5 allylamino-2,3-dihydrothiophene This example illustratas a general procedure which can be used to prepare 5-substituted amino compounds 20 of the present invention.
One gram of sodium hydroxide in 4~0 ml of water is added to a mixture of 4.0 g of 2-(2 fluorophenyl)-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-1,2-dihydrothio-phene in 80 ml of methylene chloride at room temperature 25 followed by the addition o~ 1.37 g of allyl bromide and 0.27 g of benzyltriethylammonium chloride. This will result in a two-phase mixture. The mixture is stirred at room temperature for about 18 hours after which time it is washed three times with water, dried over magnesium 30 sulfate and concentrated in vacuo. The residue can be purified by chromatography over silica gel to yield the title compound.
Similarly, by applying this procedure to the products listed in Examples 1 and 2, the corresponding 5-allylamino analogs thereof can be prepared. Similarly, by approximately doubling the amount of allyl bromide and sodium hydroxide, the corresponding 5-diallylamino analogs thereof can be prepared.

~0 -46- ~ ~ 8075~

In a like manner, by usin~ ethyl bromide in place of allyl bromide, the corresponding 5-ethyl and 05 5-diethyl analogs can be prepared.
Similarly, by following the same procedure by respectively using methoxymethyl bromide, ethylthiomethyl bromide, methyl bromoacetate, methyl 2-bromobutyrate, 1,5-dibromopentane, and cis-1,4-dibromobut-1,3-diene in place 10 of alkyl bromide the corresponding 5-methoxymethylamino, 5-ethyilthiomethylamino, 5-methoxycarbonylmethylamino, 5-(l-methoxycarbonyl propylamino), 5-piperidin-1-yl and 5-pyrrol-l-yl analogs of the products llisted in Examples 2, 3 and 6 can be prepared ~or example:
2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methoxymethylamino-2,3-dihydrothiophene;
2-methyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methoxymethylamino-2,3-dihydrothiophene;
2-ethyl-3-oxo-4-(3-trifluoromethylphenyl)-5-20 methoxymethylamino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-ethylthiomethylamino-2,3-dihydrothiophene;
2-methoxy-3~oxo-4-(3-trifluoromethylphenyl)-5-ethylthiomethylamino-2,3-dihydrothiophene;
2-methyl-3-oxo-4-(3-trifluoromethylphenyl)-S-ethylthiomethylamino-2,3-dihydrothiophene;
2-ethoxymethylene-3-oxo-4-(3-trifluoromethyl-phenyl)-S-ethylthiomethylamino-2,3-dihydrothiophene;
2-ethyl-3-oxo-4-(3-trifluoromethylphenyl)-5-30 ethylthiomethylamino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methoxycarbonylmethylamino-2,3-dihydrothiophene;
3-methyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methoxycarbonylmethylamino-2,3-dihydrothiophene;
2-methylthiomethylene-3-oxo-4-(3-trifluoro-methylphenyl)-S-methoxycarbonylmethylamino-2,3-dihydro-thiophene;
2-ethyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methoxycarbonylmethylamino-2,3-dihydrothiophene;

01 ~47- ~2 ~O ~S~

2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-(1-methoxycarbonylprop-l-yl)amino-2,3-dihydrothiophene;
o5 2-methyl-3-oxo-4-(3-trifluoromethylphenyl)-5-(1-me~hoxycarbonylprop-1-yl)amino-2l3-dihydrothiophene;
2-fluoro-3-oxo-4-(3-trifluoromethylphenyl)-5-(1-methoxycarbonylprop-l-yl)amino-2,3-dihydrothiophene;
2-ethyl-3-oxo-4-(3-trifluoromethylphenyl)-5-(1-10 methoxycarbonylprop-1-yl)amino-2,3-dihydrothiophene;
2-naphth-1-yl-3-oxo-4-(3-trifluoromethylphenyl)-5~ methoxycarbonylprop-1-yl)amino-2,3-dihydrothiophene;
2-inden-1-yl-3-oxo-4-(3-trifluoromethylphenyl)-5-(1-methoxycarbonylprop-1-yl)amino-2,3-dihydrothiophene;
2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-piperidin-l-yl-2,3-dihydrothiophene; and 2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-pyrrol-l-yl-2,3-dihydrothiophene, etc.
Similarly, by applying the above procedures 20 using the 5-methylamino products of Example 4 as starting materials, the corresponding 5-(N-methyl-N-allylamino), 5-(N-methyl-N-ethylamino), 5-(N-methyl-N-methoxymethyl-amino), 5-(N-methyl-N-ethylthiomethylamino), 5-(N-methyl-N-methoxycarbonylmethylamino), and 5-(N-methyl-N-l'-me-5 thoxycarbonylpropylamino) analogs can be prepared.Example 6 2-Phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dih~drothiophene oxide CF3 ~
11~

In this example 1.75 g of 2-phenyl-3-oxo-4-(3-tri1uoromethylphenyl)-5-amino-1,2-dihydrothiophene was dissolved in 35 ml of methylene chloride at room tempera-ture. To the resultiny solution was admixed dropwise a 4 solution of 1.53 g of 80~ m-chloroperbenzoic acid in 35 ml 01 -~8~ 80752 o~ methylene chloride. The reaction mixture was stirred overnight (about 18 hours) at room temperature after which 05 time it was washed three times with aqueous sodium thiosulfate solution, one time with lN hydrochloric acid, one time with water, one time with saturated aqueous sodium bicarbonate and one time with brine. The organic phase was dried over magnesium sulfate and concentrated ln 10 vacuo to give 1.86 g o~ brown foam which was chromato-graphed on silica eluted with 50/50 petroleum ether/ethyl-acetate yielding 1.03 g of the title compound.
Similarly, the corresponding dihydrothiophene oxides o~ the thiophene products listed in Examples 1, 3-5 15 can be prepared via the same procedure but using the corresponding dihydrothiophenes of Examples 1, 3-5 as starting materials.
Example 6A
2-Phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-~,3-dihydrothiophene dioxide / N ~ S

The title compound can be prepared via the starting material described hereinabove in Example 4, 30 using the procedure described in Example 6, but doubling the amount o~ m-chloroperbenzoic acid.
The corresponding dihydrothiophene dioxide analogs oE the products llsted in Examples 1, 3-5 can be prepared via the same procedure using the corresponding 35 dihydrothiophene starting materials.

`; ~ 7~;~

Example 7 Lithium salt of 2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrothiophene Thls example illustrates a procedure which can be used to prepare the cation salts of the present invention.
In this examp].e, 6.6 ml of 1.6M n-butyllithium in hexane is added dropwise to a stirred solution containing 2.86 g of 2-phenyl-3-oxo-4-(3~-trifluoromethylphenyl)-5-methyl-amino-2,3 dihydrothiophene in 25 ml of tetrahydrofuran at -30C. The resulting mixture is stirred for 20 minutes and then concentrated in vacuo to afford the title compound.
Similarly, by following the same procedure, the corresponding lithium salts of the compounds of Examples 1, and 3-5 can also be prepared.
Example 8 The compounds listed in Tables A and B hereinbelow were prepared using the appropriate starting materials in procedures described in the Examples hereinabove. A number of comparison compounds were also prepared using similar procedures. These comparison compounds include among others the reference compounds 5-amino-3-oxo-~-pheny]-2,3-dihydrothiophene, 5-amino-3-oxo-4-(2-fluorophenyl)-2,3-dihydrothiophene and 5-amino-3-oxo-~-(2-chloro-phenyl)-2,3-dihydro-thiophene. The compar:ison compounds are reported in Table C here~nbelow.

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01 ~55~ ~'~ 8~ 75 Example 9 In this example, the compounds of Tables A and B
05 and the comparison compounds of Table C, hereinabove, were respectively tested using the procedures described herein~
below for pre-emergent and post-emergent activity against a variety of grasses and broad-leaf plants including one grain crop and one broad-leaf crop~ The compounds tested are identified by compound number in Tables A, B and C
hereinabove.
Pre-Emergent Herbicide Test Pre-emergence herbicidal activity was determined in the following manner.
Test solutions of the respective compounds were prepared as follows:
355.5 mg of test compound was dissolved in 15 ml of acetone. 2 ml of acetone containing llO mg of a non-ionic surfactant was added to the solution. 12 ml of this stock solution was then added to 47.7 ml of water which contained the same nonionic surfactant at a concentration of 625 mg/l. In the case where the test material used is not essentially pure compound the amount of material used is adjusted to provide the desired concentration of com-pound.
Seeds of the test vegetation were planted in apot of soil and the test solution was sprayed uniformly onto the soil surface either at a dose of 27.5 micro-grams/cm2 or in some instances as indicated in Table 1 hereinbelow, certain of the compounds were tested at a lower dosages. The pot was watered and placed in a greenhouse. The pot was watered intermittently and observed for seedling emergence, health o emerging seedlings, etc., for a 3-week period. At the end of this period, the herbicldal ef~ectiveness of the compound was rated based on the physiological observations. A 0-to-100 scale was used, 0 representing no phytotoxicity, 100 representing complete kill. The results of these tests are summarized in Table 1.

-56~ 75~

Post-Emergent Herbicidal Test The test compound was formulated in the same 05 manner as described above for the pre-emergent test.
This formulation was uniformly sprayed on 2 similar pots containing plants 2 to 3 inches tall (except wild oats, soybean and watergrass which were 3 to 4 inches tall) (approximately lS to 25 plants per pot) at a dose of 10 27.5 micrograms/cm2 or in some cases at lower dosages as footnoted in Table 2. After the plants had dried, they were placed in a greenhouse and then watered intermit-tently at their bases as needed. The plants were observed periodically for phytotoxic effects and physiological and 15 morphological responses to the treatment. After 3 weeks, the herbicidal effectiveness of the compound was rated based on these observations. A 0-to-100 scale was used, 0 representing no phytotoxicity, 100 representing complete kill. The results of these tests are summarized in 20 Table 2.

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As can be seen from the above Table 1, the com~
pounds oE the invention generally exhibit a broad spectrum 05 of excellent pre-emergence phytotoxic ac~ivity and espe-cially so Compounds Nos. 7-9, 13-18, 38, 39 and 46. Also certain of these compounds exhibited reduced phytotoxicity with respect to soybean while retaining excellent pre-emergent phytotoxicity with respect to both broadleaf and 10 grassy weeds. As shown by Table 2 a number of the compounds also exhibited from modest to very good post-emergence phytotoxicity but are primarily pre-emergence herbicides. In contrast to this it can be seen that none of the comparison compounds exhibited any pre-emergence herbicidal activity whatsoever and only three of the comparison compounds (and none of the reference compounds) exhibited any post-emergence activity and this was at a very low level. Also, as can be seen from Table 1 the compounds of the invention having a 4-t3-trifluoromethyl-20 phenyl) substitutent and/or a 5-methylamino exhibited substantially superior phytotoxicity.
Obviously, many modifications and variations of the invention described hereinabove and below can be made without departing from the essence and scope thereof.
~5 ~0

Claims (39)

1. A compound having the formula:

(I) wherein n is 0, 1 or 2; R is lower alkyl, cycloalkyl having 3 through 7 carbon atoms; (cycloalkyl)alkylene having 3 through 7 carbon atoms in the cycloalkyl moiety and 1 through 3 carbon atoms in the alkylene moiety; lower alkenyl; haloalkyl having 1 through 4 carbon atoms and 1 through 3 halo atoms independently selected from the group of fluoro, chloro, bromo or iodo; haloalkenyl having 2 through 4 carbon atoms and 1 through 3 halo atoms at the terminal carbon atom, which halo atoms are independently selected from the group of fluoro, chloro, bromo, or iodo; lower alkoxy; lower alkylthio; lower alkoxy-alkyl wherein the alkyl and alkoxy moieties independently have 1 through 3 carbon atoms;
alkylthioalkyl wherein the alkyl moieties independently have 1 through 3 carbon atoms; phenyl, naphth-l-yl, inden-l-yl;
4-fluorophenyl; arylalkylene having 1 through 3 carbon atoms in the alkylene moiety and wherein the aryl moiety is phenyl, naphth-l-yl or inden-l-yl; or R a substituted aryl or substituted arylalkylene selected from the group having the formulas:

wherein one, two or three of R4, R5, R6, R7, R8, and R9 are independently selected from the group of lower alkyl, lower alkoxy, halo, nitro, or haloalkyl having 1 through 3 carbon atoms and 1 through 3 of the same or different halo atoms, and the remainder of R4, R5, R6, R7, R8 and R9 are hydrogen; and R3 is a single bond or alkylene having 1 through 3 carbon atoms;
R1 is hydrogen or alkyl having 1 through 4 carbon atoms;
R2 is hydrogen, alkyl having 1 through 4 carbon atoms, alkenyl having 3 or 4 carbon atoms, lower alkoxycarbonylalkyl having from 1 through 4 carbon atoms in the alkoxy moiety and from 1 through 4 carbon atoms in the alkyl moiety; lower alkoxyalkyl wherein the alkoxy and alkyl moieties independently have 1 through 3 carbon atoms, or lower alkylthio-alkyl wherein the alkyl moieties independently have 1 through 3 carbon atoms; or R1 and R2 together with the nitrogen atom to which they are joined form a saturated or unsatu-rated nitrogen heterocycle having 3 through 6 ring atoms one of which is nitrogen and the remainder are carbon atoms;
X is hydrogen, lower alkyl, lower alkoxy, halo, or trifluoromethyl and can be at any available position on the phenyl ring; and Y is lower alkyl, lower alkoxy, halo, lower haloalkyl having 1 through 4 carbon atoms and 1 through 3 of the same or different halo atoms, lower haloalkoxy having 1 through 4 carbon atoms and 1 through 3 of the same or different halo atoms, or lower haloalkylthio having l through 4 carbon atoms and 1 through 3 of the same or different halo atoms, with the proviso that when Y is other than trifluoromethyl and R1 and R2 are each hydrogen then R is methyl, ethyl, propyl, 2-halophenyl, 2-lower alkylphenyl or 4-fluorophenyl; and compatible salts thereof.

2. A compound having the formula:

(I) wherein n is 0, 1, or 2; R is lower alkyl, cycloalkyl having 3 through 7 carbon atoms; (cycloalkyl)alkylene having 3 through 7 carbon atoms in the cycloalkyl moiety and 1 through 3 carbon atoms in the alkylene moiety; lower alkenyl, haloalkyl having 1 through 4 carbon atoms and 1 through 3 halo atoms independently selected from the group of flouro, chloro, bromo or iodo; haloalkenyl having 2 through 4 carbon atoms and 1 through 3 halo atoms at the terminal carbon atom, which halo atoms are independently selected from the group of fluoro, chloro, bromo, or iodo; lower alkoxy;
lower alkylthio; lower alkoxyalkyl wherein the alkyl and alkoxy moieties independently have 1 through 3 carbon atoms; lower alkylthioalkyl wherein the alkyl moieties independently have 1 through 3 carbon atoms; phenyl, naphth-l-yl, inden-l-yl;
4-fluorophenyl; arylalkylene having 1 through 3 carbon atoms in the alkylene moiety and wherein the aryl moiety is phenyl, naphth-l-yl or inden-l-yl; or R is a substituted aryl or substituted arylalkylene selected from the group having the formulas:

or wherein one, two or three of R4, R5, R6, R7, R8, and R9 are independently selected from the group of lower alkyl, lower alkoxy, halo, nitro, or haloalkyl having 1 through 3 carbon atoms and 1 through 3 of the same or different halo atoms, and the remainder are hydrogen; and R3 is a single bond or alkylene having 1 through 3 carbon atoms;

R1 is hydrogen or alkyl having 1 through 4 carbon atoms;
R2 is hydrogen, alkyl having 1 through 4 carbon atoms, alkenyl having 3 or 4 carbon atoms, lower alkoxycarbonylalkyl, lower alkoxyalkyl or lower alkylthioalkyl; or R1 and R2 together with the nitrogen atom to which they are joined form a saturated or unsatu-rated nitrogen heterocycle having 3 through 6 ring atoms one of which is nitrogen and the remainder are carbon atoms;
X is hydrogen, lower alkyl, lower alkoxy, halo, or trifluoromethyl and can be at any available position on tha phenyl ring;
and compatible salts thereof.

3. The compound of Claim 2 wherein R1 and R2 are independently selected from the group of hydrogen, methyl, ethyl or propyl.

4. The compound of Claim 3 wherein R is methyl, ethyl or n-propyl.

5. The compound of Claim 4 wherein one of R1 or R2 is hydrogen or methyl and the other is hydrogen, methyl or ethyl.

6. The compound of Claim 2 wherein X is hydrogen.

7. The compound of Claim 3 wherein X is hydrogen.

8. The compound of Claim 4 wherein X is hydrogen.

9. The compound of Claim 2 wherein R is methyl, ethyl, n-propyl, butyl, phenyl or a monosubstituted aryl.

10. The compound of Clalm 9 wherein R is phenyl or monosubstituted phenyl.

11. The compound of Claim 10 wherein R is phenyl, monohalophenyl, or mono lower alkylphenyl.

12. The compound of Claim 10 wherein X is hydrogen.

13. The compound of Claim 1 wherein said compound is selected from the group having the formula:

wherein R, R1, R2 and X are as defined in Claim 1;
and compatible cation salts thereof.

14. The compound of Claim 13 wherein R1 and R2 are independently hydrogen or methyl or ethyl.

15. The compound of Claim 13 wherein R is methyl, ethyl, propyl or n-butyl.

16. The compound of Claim 13 wherein X is hydrogen.

17. The compound of Claim 16 wherein R1 and R2 are independently hydrogen, methyl, or ethyl.

18. The compound of Claim 17 wherein R1 is methyl, ethyl, or propyl.

19. The compound of Claim 18 wherein R is methyl and one of R1 or R2 is hydrogen and the other is methyl.

20. The compound of Claim 18 wherein R is ethyl and one of R1 or R2 is hydrogen and the other is methyl.

21. The compound of Claim 18 wherein R is n-propyl and one of R1 and R2 is hydrogen and the other is methyl.

22. The compound of Claim 16 wherein R is methyl, ethyl or n-propyl and one of R1 or R2 is hydrogen and the other is methyl.

23. The compound of Claim 14 wherein R is phenyl, 2-halophenyl, 4-fluorophenyl, or 2-lower alkylphenyl.

24. The compound of Claim 14 wherein R is phenyl, 2-fluorophenyl, 4-fluorophenyl, 2-methylphenyl.

25. The compound of Claim 23 wherein R1 and R2 are independently hydrogen or methyl and X is hydrogen.

26. The compound of Claim 25 wherein R is 4-fluoro-phenyl.

27. The compound of Claim 25 wherein R is phenyl.

28. The compound of Claim 25 wherein R is 2-methyl-phenyl.

29. The compound of Claim 25 wherein R is phenyl, 2-methylphenyl, 2-fluorophenyl, 2-chlorophenyl or 4-fluoro-phenyl.

30. A herbicidal composition comprising a herbici-dally effective amount of a compound according to Claim 1, or mixtures of such compounds, and a compatible carrier.

31. A herbicidal composition comprising a herbici-dally effective amount of a compound according to Claim 22, or mixtures thereof, and a compatible carrier.

32. A method for controlling plants which comprises applying a herbicidally effective amount of a compound according to claim 1, or mixtures thereof, to the foliage or growth medium or potential growth medium of said plants.

33. A method for controlling plants which comprises applying a herbicidally effective amount of a compound according to claim 22, or mixtures thereof, to the foliage or growth medium or potential growth medium of said plants.

34. A plant growth regulating composition comprising a plant growth regulating effective amount of a compound according to claim 1 in admixture with a diluent or carrier.

35. A method for regulating the growth of plants which comprises applying to the foliage of said plants or their growth medium an amount. of a compound according to claim 1, or mixtures thereof, effective to alter the growth pattern of such plants.

36. The compound of claim 1 wherein R is methyl, ethyl, propyl, phenyl or monosubstituted phenyl.

37. The compound of claim 1 wherein R1 and R2 are independently selected from the group of hydrogen, methyl, ethyl or propyl.

38. The compound of claim 1 wherein one of R1 or R2 is hydrogen and the other is methyl or ethyl.

39. The compound of claim 38 wherein R is methyl, ethyl, phenyl, 2-halophenyl, or 2-lower alkylphenyl.