CA1252468A

CA1252468A - Herbicidal 5-amino-3-oxo-4-(substituted-phenyl)-2,3- dihydrofuran and derivatives thereof

Info

Publication number: CA1252468A
Application number: CA000456115A
Authority: CA
Inventors: Carl E. Ward
Original assignee: Individual
Current assignee: Bayer CropScience SA
Priority date: 1983-06-17
Filing date: 1984-06-07
Publication date: 1989-04-11
Also published as: CH659651A5; ES8602733A1; ES533473A0; ATA192984A; NL8401876A; GB2142629A; GB8415480D0; IT1175507B; IT8421432A1; ES8604916A1; KR910005893B1; ES544949A0; AR243517A1; AT389305B; ES544951A0; NL193833C; AU570466B2; GB2142629B; IT8421432A0; NL193833B

Abstract

ABSTRACT OF THE DISCLOSURE
5-Amino-3-oxo-4-(substituted-phenyl)-2,3-dihydrofuran and derivatives thereof. The compounds generally exhibit both pre-emergence and post-emergence phytotoxicity and are useful as herbicides and also at low dosages as plant growth regulating agents.

Description

lZ~iiZ~i8 HER~3ICI DAL 5-AMINO-3-OXO-4--t ~;IJ13~;TITUTED-PHENYL)-

2, 3-DIHYDROFURAN AND DERIVATIVES TIIERI~:OF' _ ACKGROUND OF THE INVEN'rION
This invention relates to 5-amino-3-oxo-4-~substituted-phenyl)-2,3-dihydro~uran derivatives and to the use of such compounds as herbicides and plant growth regulators.
Chemiker-Zeitung 10~ (1980) No. 10, Pages 302-303, is an academic paper disclosing the ring closure of l-(dimethylamino)-2,4-diphenyl-1-buten-3,4-dione to yield 5-dimethylamino-2,4-diphenyl-2,3-dihydro-furan. British Patent No. 1,521,092, discloses certain

3-phenyl-5-substituted-4(1H)-pyrid-ones or -thiones as herbicides. Japanese Patent Application 13,710/69 (Chemical Abstracts 71:61195e) discloses the generLc formula for 5-amino-3-oxo-4-~phenyl and halophenyl)-2,3-dihydrofuran and specifically discloses 5-amino-3-oxo-4-(phenyl and 4-chlorophenyl)-2,3-dihydro~urans. Japanese Patent No. 19090 (Chernical Abstracts 69P10352e) discloses certain 2,3-dihydrothiophenes as phanmaceuticals.
Helvetica Chemica Acta, Volume 56, Pages 362-378 (1383) discloses 5-N-cyclopropyl-4-phenyl-2-methoxycarbonyl-methylene-3-furanone as part of an academic chemical synthesis discussion. U.S. Patent No. 4,441,910 discloses herbicidal ureidosulfonylfurans and ureidosulfonylthio-phenes.
SUMtlARY OE THE INVENTION
The uresent invention provides compounds having both pre-emergence and post-emergence herbicidal activity and having especially good pre-emergence activity ayainst a broad spectrum of both broad-leaf weeds and grassy weeds. At lower application rates the compounds also exhibit plant growth regulatiny properties.

~,~
.

~z~

The compounds of the present invent.ion can be re-presented by the following formula:

Y ~\ , O

(I) wherein R is lower alkyl having l through 4 carbon atoms; cycloalkyl having 3 through 7 carbon atoms, lower alkenyl; haloalkyl having l through 4 carbon atoms and l through 3 halo atoms independently selected from the group of fluoro, chloro, bromo or iodo; haloalkenyl having 2 through 4 carbon atoms and l through 3 halo atoms inde-pendently selected from the group of fluoro, chloro, bromo, or iodo; lower alkoxyalkyl wherein the alkoxy and alkyl moiety thereof independently have l through 3 carbon atoms; lower alkylthioalkyl wherein the alkyl moieties independently have l through 3 carbon atoms; phenyl, naphth-l-yl, inden-l-yl; 4-fluorophenyl; arylalkylene having l through 3 carbon atoms in the alkylene moiety and wherein said aryl moiety is phenyl, naphth-l-yl or inden-l-yl; or substituted aryl or arylalkylene selected from the group having the formulas:

R~ R5 R4 R5 -(R3) ~ ; (R ). ~

R7 R6 R9 ~ - R ; or ,~
. ,~, .

~S;~4~t3 01 -3- 61g36-1612 -(R3) ~R6 R8 \R7 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 an alkylene having 1 through 3 carbon atoms;
Rl is hydrogen or alkyl having 1 through 4 carbon atoms;
R2 is hydroyen, allcyl 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 all<oxyalkyl wherein the alkoxy and alkyl moieties independently have 1 through 3 carbon atoms or alkylthioalkyl wherein the alkyl moieties independently have 1 through 3 carbon atoms;
or Rl and R2 toyether with the nitrogen to which they are joined for~.a saturated or unsaturated - nitroyen heterocycle haviny from 4 through 6 ring atoms one of which is nitrogen and the remainder of which are carbon atoms;
X is hydroyen, lower alkyl, lower alkoxy, halo, or trifluoromethyl and can be at any available posi-tion on the phenyl ring; and Y is lower alkyl, lower alkoxy; halo; lower haloalkyl having 1 through 4 ~2~

carbon atoms and 1 to 3 of the same or different halo atoms; lower haloalkoxy having 1 through 4 carbon 05 atoms and 1 through 3 of the same or different halo atoms; or lower haloalkylthio having 1 through 4 carbon atoms and 1 through 3 of the same or different halo atoms; with the proviso that when Y is halo then R, Rl and R2 are not all hydrogen and the further proviso that when Y is other than trifluoromethyl and X is other than hydrogen, and Rl is hydroyen and R2 is hydrogen then R is methyl, ethyl, propyl, 2-halo-phenyl, 2-lower alkylphenyl or 4-fluorophenyl.
The invention also comprises compatible salts of the compound oE Formula (I), for example salts 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 of the amino hydrogen.
The compounds of Formula (I) exist as keto <_>
enol isomers. The compounds also have an asymmetric carbon atom and can also exist as optical isomers. In some instances the compounds also exist as geometric isomers. The above formula is intended to encompass the respective individual isomers as well as mixtures thereof and the respective isomers as well as mixtures thereof are encompassed within the invention.
It has also been discovered that the presence o~
a 3-trifluoromethyl substituent on the 4-phenyl group of the compounds of the present invention gen0rally very substantially enhances herbicidal activity.
In a further aspect the inven-tion provides a herbicidal composition comprising a compatible carrier and a herbicidally effective amount of the compounds of 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 lZ~ k~3 the foliage of such veyetation with a herbicidally effec-tive amount of the compound(s) of Formula (I) and/or 05 compatible salts thereof.
In another aspect, the present invention pro-vides a plant growth regulating composition comprising a 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 the normal growth pattern of said plants~
The present invention also provides a method for regulating plant growth which comprises treating ths growth medium and/or the foliage of such vegetation with a plant yrowth 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 plants.
The present invention also provides chemical intermediates and processes for preparing the compounds of Formula (I).
The invention will be ~urther described herein-below.
FURTH~R DESCXIPTION OF THE
INVENTION AND THE PREFERRED EMBODIME~TS
Illustrations of typical compounds of Formula (I) of the prasent invention can be had by refer-ence to Examples 2, 3, 6-10 set forth hereinbelow on Pages 24-30 and 33-51. In terms of substituents, the preferred compounds are those wherein R is lower alkyl, aryl or substituted aryl, more preferably methyl, ethyl, propyl, phenyl or substituted phenyl, and especially phenyl, monomethylphenyl or monohalophenyl, more especially methyl, ethyl, n-propyl, 2-halophenyl, 2-lower alkylphenyl, or 4-fluorophenyl; Rl and R2 are inde-pendently hydrogen, methyl, ethyl or n-propyl, and more preferably one of Rl or R2 is hydrogen and the other is hydrogen, methyl, ethyl or n-propyl, preferably hydrogen~
methyl or ethyl, especially methyl; X is hydrogen and/or Y
is 3-trifluoromethyl or 3-halo, especially 3-i8 trifluoromethyl. Most preferably the compounds contain a combination of two or more preferred substituents.
05 The compounds of Formula (I) wherein Rl and R2 are each hydrogen and R is aryl or substituted aryl can be conveniently prepared by the following schematically represented process:

X X

Y CHCCH2Z' > Y , ~

CN H2N o Z' (A) (I') wherein X and Y are as defined hereinabove;
and Z' is aryl, or substituted aryl.
Rearrangement of Compound (A) to Compound (I') can be conveniently effected by contacting Compound (~) with a halogen, preferably bromine, and a liquid carboxy-lic acid in the presence of an inert organic solvent.
Typically, this process is conducted at tempera-tures in the range of about from 0 to 1~0C, preferably about from 20 to 30C, for about from 4 to 36 hours, preferably about from 18 to 24 hours, using about from 1.0 to 10.0, preferably 1.0 to 1.1 moles of halogen per mole of Compound (A). Suitable liquid carboxylic acids which can be used include, for example, acetic acid, propionic acid, butyric acid, formic acid, and the like. By using excess carboxylic acid, the excess can serve as solvent or liquid carrier for this reaction system. Other organic solvents which can be used include, for example, liquid halogenated alkanes, for example, methylene chloride, carbon tetrachloride, chloroform, 1,2-dichloroethane;
liquid aromatics, for example, benzene, toluene; liquid alkyl ethers, for example, diethylether, dimethyl, sulfoxide, dimethylforamide, and the like, and compatible mixtures thereof.

s~

01 ~7~

Best results are obtained using bromine as the halogen, although chlorine and iodine could also be used.
05 The starting materials OL Formula (A) can be prepared by the following schematically represented process:

r~
CH2CN + Z'-CH2-C-ORl - > (A) (C) wherein Rl is lower alkyl, aryl (e.g. phenyl) or arylalkylene (e.g. benzyl), and Z', Y and X are as defined hereinabove.
This process can be conveniently effected by contacting Compound (B) with Compound (C), and a strong base, 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, preferably 1.0 to 1.2 moles of Compound (C) per mole of Compound (s).
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 s~rong 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 axample, methanol, ethanol, and propanol) tetrahydrofuran, dimethoxyethane, dioxane, and the like, and compatible mixtures thereof. Conveniently, the alkali metal alkanolate is prepared in situ by reacting an alkali metal 'l'h~

with excess alkanol which in turn serves as solvent for the above reaction.
05 The starting materials of Formulas (8) and tC) are generally known materials and can be prepared by known procedures, or obvious modifications thereof (i.e., substitution of appropriate startin~ materials), The preparation of Compound (B) is for example described in Org. Syn. Coll., Volume l, 107 (1941), and the preparation of Compound (C) is described in Ory. Syn. Coll., Volume l, 270 (1941).
The compounds of Formula ~I) wherein Rl and R2 are each hydrogen can be prepared via the general process schematically represented by the followin~ overall reaction e~uation:

r :H2CN + R-C-C-OR5 - > ~ ~ + R5OH

~B) (E) t wherein R, and X and Y are as defined hereinabove; and R5 is lower alkyl, aryl (e.g.
phenyl) or arylalkylene te.g. hen~yl).
This process can be conveniently effected by contacting Compound (B) with Compound (E), and a strony base (e.g. sodium methoxide, sodium ethoxide), preferably in an inert organic solvent.
Typically, this process is conducted at ~empera-tures in the ranye of about from 0 to 100C, preEerably 75 to 85C for about from 5 to 3G hours, preferably 18 to 2~ hours, using about from 1.0 to 10.0, preferably l.0 to l.2 moles of Compound (E) per mole of Compound (B~.
Suitable inert organic solvents which can be used include, ~or example, lower allcanols (e.g. methanol, ethanol, ~0 9 1 ~

propanol, etc.); tetrahydrofuran; dimethoxyethane, dioxane; and the like, and compatible mixtures thereof.
Suitable bases which can be used for this process include those bases previously described with respect to the reaction of Compound (B) with Compound (C).
The hydroxy esters of formula (E) are generally known compounds and can be prepared by known procedures or by obvious modi~ications thereof (e.g., by using appropriately substituted starting materials).
The compounds of Formula I wherein Rl and R2 are hydrogen and R is alkyl, cycloalkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, arylalkylene, substituted arylalkylene or alkenylalkyl (e.g., _CH2CH=CH) can also be conveniently prepared by the following schematically represented process:

/~CHC-CHR' ' ' ~ cyclizing agent -~
y CN OR ~
O

H2N R'~
(I''') wherein R''' is alkyl, cycloalkyl, alkoxyalkyl, alkoxy, alkylthioalkyl, arylalkylene, substituted arylalkylene or alkenyl and R10 is lower alkyl, preferably methyl.
This process can be conveniently effected by contact-ing Compound (A') with a cyclizing agent, under reactiveconditions, preferably in an inert organic solvent.

01 -10~

Typically, this process is conducted at tempera-tures in the range of about from 0 to 200C, preferably 05 about from 115 to 120C, for about from 10 to 120 minutes, preferably 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 acids, for example, sulfuric acid, hydrogen chloride, hydrogen bromide, trifluoroacetic acid, methane sulfonic acid, and the like. Best results are typically obtained using anhydrous sulfuric acid. Suitable inert organic solvents which can be used include, for example, acetic acid, propionic acid, butyric acid, toluene, xylene, and the like, and compati~le mixtures thereof.
The starting materials of formula (A') can be prepared via the following schematically represented process:
X X

CHCH2OR10 _ > Ç ~ C - C-CH2R10 CN CN O
y y (B' ) / (B' ' ) /

X L /
~ eM+ ~
C - C - CH - OR10 R~X~ ~ (A') _/ I e~M ' C N
(B' ' ' ) wherein R''' and R10 are as defined hereinabove;
X' is chloro, bromo or iodo and M and M' are independently sodium or lithium.

~ Z~ i8 Although this process is schematically shown as three steps, the steps are typically and conveniently o5 conducted in situ. Also as is conventional with such reactions the reactions are preferably conducted under substantially anhydrous condition under an inert gas (e.g., nitrogen).
In the first step of this process compound (B') is contacted with a non-nucleophilic base, preferably in an inert organic solvent. This step is typically conducted at temperatures in the range of about from 0-25C for about from 1/2 to 3 hours using about from 1 to 2, preferably 1 to 1.3, mole e~uivalents of non-nucleo-philic base per mole of compound (B'). Suitable non-nucleophilic bases which can be used include, for example, alkali metal hydrides, e.g., sodium hydride, potassium hydride, etc.; alkali metal amides, e.g., lithium bis(trimethylsilyl)amide; sodium bis(trimethylsilyl)amide;
potassium bis(trimethylsilyl)amide; lithium diethylamide, lithium diisopropyl amide; sodium dimethylamide, and the like. Sodium hydride is generally preferred as it has given very good results and is readily commercially available. The alkali metal amides, and also of course the alkali metal hydrides, are generally known compounds and can be prepared by known procedures, or obvious modifications thereof. For example, the alkali metal amides can be prepared by the reaction of a secondary amine with an alkyl alkali metal.
Suitable inert organic solvents, which can be used, include, for example, tetrahydrofuran, dioxane, dimethoxyethane, diethyl ether, diisopropyl ether, and the like and compatible mixtures thereof.
The second step can be effected by contacting compound (B'') with an alkyl base preferably in an inert organic solvent. As before noted, this process step is preferably conducted in situ with the reaction product mixture of the first step. Typically the second step is conducted at temperature ranges of about from -78 to 0C
for about from 1 to 4 hours using about from 1 to 2, preferably 1 to 1.3 mole equivalents of alkyl base per mole o~ compound (B''). Suitable alkyl bases which can be 05 used include for example alkyl-alkali metals, alkyl Grignard reagents, and the like. Preferably n-butyl-lithium is used as it gives good results and is readily commercially available. Suitable solvents which can be used include those listed above with respect to the first step and the like.
The third step can be effected by contacting compound (B''') with the appropriate R''' halide having the desired R' ' ' group, preferably in an inert organic solvent. The third step is also typically conducted ln situ with the reaction product mixture of the second step.
The third step of this process is typically conducted at temperatures in the range of about from -30 to 30C, preferably 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 R' ' 'X' per mole o~
B'''. Suitable inert organic solvents include those given above with respect to the first step of this process, and the like. The R' ' 'X' halides are generally known com-pounds and can be prepared by known procedures or obvious modifications thereof (e.g., substitution of appropriate reactants and solvents).
The starting materials of Formula (B') can be prepared by the following schematically represented process:

X

~ CH2CN + RllOCCH2OR10 > (B') (B) (C') wherein Rll is lower alkyl (preferably methyl) and R10, Y and X are as defined hereinabove.
This process can be conveniently effected by ~;~s~

contacting Compound (B) with Compound (C'), and a strong base under reactive conditions, preferably in an inert 05 organic solvent.
Typically, this process is conducted using the same conditions as described hereinabove with respect to the preparation of Compound (A) save that reactant C' is used in place of reactant C. The reactants of Formula C' are simple alkyl alkoxyacetate esters, for example,~methyl methoxyacetate. The preparation of such compounds is well known to the art.
The compound of Formula (I) wherein one or both of Rl and R2 are substituted can be pr~pared by alkylation of the amino group of the corresponding compounds for formula I'':

X X

~ ~ R2 z,. > ~ O

H\NJ~ Rl ,~

25(I ") (I''') wherein R, Rl, X and Y are as defined here-inabove; and R2 is as defined for R2 but is not hydrogen; and R2 z~ is an alkylation agent having the appropriate R2 or appropriate Rl group if dialkylation is desired.
This process can be effected by contacting Compound (I'') with a suitable alkylation agent capable of alkylating primary or secondary amino groups.
For example, this can be effected by contacting Compound (I'') with R2 iodide or bromide, preferably in an inert organic solvent and preferably in the presence of a scavenger base. Typically, this process is conducted at temperatures in the range of about from 0 to 100C, preferably 20 to 45C for about from 1.0 to 72.0, preferably 2.0 to 18.0 hours. Where it i5 desired to monoalkylate, then typically about from 1.0 to 1.1 moles 05 of R2 halide reactant is used per mole of Compound (I''). Where it is desired to alkylate both amino hydrogens, then typically about from 1.9 to ~.0 moles of R2 halide are used per mole of Compound (I''). In the case where it is desired to prepare the compound wherein R2 is alkoxyalkyl or alkylthioalkyl, it is preferred to use a large excess of R2 halide even where monoalkylation is desired; for example 3 to 6 moles of R2 z~ per mole of I''. Further alkylation can be effected in a second step if desired. Also variation in Rl and R2 can be effected by first alkylating only one of the two amino hydrogens and then alkylating the second amino hydrogen with an alkylating agent having a different R2 group. The compounds wherein Rl and R2 together with the amino nitrogen atoms form a saturated heterocycle can be prepared by using the appropriate ~ (CH2)2_5-Z'', wherein Z'' is Cl or Br alkylating agent. The RlR2N
unsaturated heterocycle can be prepared by using the appropriate c1s-alkenyl dihalide, wherein one of the halo atoms is on each of the terminal alkenyl carbon. ~uitable inert organic so1vents which can be used, include, for example, li~uid halogenated alkanes; for example, methylene chloride, carbon tetrachloride, or dichloro-ethane; also useful are tetrahydrofuran and the like.
Suitable scavenger bases which can be used include, for example, the bases described hereinabove with respect to the reaction of Compound (B) with Compound ~C).
The compounds of Formula (I "'~ wherein Rl is lower alkyl (e.g. methyl) and R2 is hydrogen or lower alkyl, are advantageously prepared using dialkyl sulfate as the alkylating agent. This can be conveniently effected by contacting the compound of Formula I wherein one or both of Rl and/or R2 are hydrogen with the desired lower alkyl sulEate in the presence of a strong base and preferably in an inert organic solvent in the presence of a phase transfer agent. Typically, this process is con-~2~

ducted at temperatures in the range of about from 0 to 100C, preferably 20 to 45C, using about from 1.0 to oS 4.0 moles of dialkyl sulfate per mole of Compound I. An excess, typically about 2.5 mole of base is used. Prefer-ably, this process is also conducted in an inert organic solvent such as, for example, methylene chloride, carbon tetrachloride, dichloroethane, tetrahydrofuran, and the like.
Suitable strong bases which can be used include, 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 chloride, tetra-n-butylammonium chloride, methyltrioctyl-ammonium chloride, and the like.
The compatible salts of Formula (I) can be ~o prepared by conventional procedures for example by treating the compound of Formula (I) wherein Rl and/or R2 are hydrogen with a suitable strong base such as, for example, n-butyllithium, sodium hydride, potassium hydride, and the like, having the desired cation, by con-~5 ventional procedures to yield the corresponding Rl and/orR2 cation salts. The enolate salts can be prepared by treating the Rl and/or R2 cation salts with base via conventional procedures. Additional variations in the salt cation can also be effected via ion exchanye with an ion exchange resin having the desired cation.
General Process Conditions In the above-described processes, it is gener-ally preferable to separate the respective products before 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, for example, recrystallization and chromatography.
Suitable separation and purification procedures are~ for ~ lZS2~

example, illustrated in the Examples set forth hereinbelow.
05 Generally, the reactions described above are conducted as liquid phase reaction and hence pressure is 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 - 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 be used. Optimum reaction conditions (e.g., temperature, reaction time, mol ratios, solvents, etc.) may vary with the particular reagents or organic solvents used but can 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 ~S differences in physical properties between the geometric lsomers .
Definitlons As used herein the following terms have the following meanings unless expressly stated to the contrary:
The term "lower alkyl" refers to both straight-and branched-chain alkyl groups having a total of from 1 through ~ carbon atoms and includes primary, secondary and tertiary alkyl groups. Typical lower alkyls include, for 3S example, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl.
The term "alkylene" refers to both straiyht chained and branched chained alkylene groups and includes, for example, sz~

-CH2-; -CH2-CH2-, -CH~CH2- and the like.
05 The term "lower alkenyl" refers to alkenyl groups having 2 through 6, preferably 2 through 4, carbon atoms and includes, for example, vinyl, l-propenyl, 2-propenyl, 1-methylvinyl, l-butenyl, 2-methylprop-1-enyl and the like.
The term "lower alkoxy" refers to the group -OR' wherein R' is lower alkyl.
The term "lower alkylthiol' refers to the group -SR' wherein R' is lower alkyl.
The term "lower alkoxyalkyl" refers to the group R'OR''- wherein R' and R'' are independently straight chain or branched chain alkyl groups haviny 1 through 3 carbon atoms~
The term "lower alkylthioalkyl" reEers 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 the group O
R'OCR''-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, chloro, bromo and iodo.
The term "lower haloalkyl" refers to haloalkyl compounds ha~ing 1 through 4 carbon atoms and 1 through 3 halo atoms independently selected from the group of fluoro, chloro, bromo and iodo. Preferably the lower haloalkyl group has 1 or 2 carbon atoms.
The term "lower haloalkoxy" refers to "lower ~ ~Z~4~`~8 Ol -18- 61936-1612 alkoxy" groups having l throu(3h 3 halo atoms independently selected from the group of fluoro, chloro, bromo or iodo.
oS The term "aryl" refers to aryl groups haviny 6 throuyh 10 carbon atoms and includes, for example, phenyl, naphthyl, indenyl. Typically the aryl group will be phenyl or naphthyl as compounds haviny such groups are more readily available commercially than other aryl ; lO compounds.
The term "substituted aryl" refers to aryl groups having 1 through 3 substituents independently ,~ : selected from the group of lower alkyl, lower alkoxy, halonitro, or haloalkyl having 1 through 3 carbon atoms lS and l through 3 halo atoms. Typical substituted aryl groups include, for example, 2-fluorophenyl, 2-chlorophenvl, 2,6-dimethylphenyl, 4-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 ArR3- wherein Ar is aryl and R3 is alkylene having 1 through 3 carbon atoms and includes both straight-chained and branched-chained alkylenes, for example, methylene, ethyl, l-methylethyl, and pro~yl.
The term "(substituted aryl)alkylene" or "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 "saturated nitrogen heterocycle" as used herein with respect to Rl and R~ of formula I refers to the yroups having the formula:

~2c~ CH2 (CH2)n wherein n is l, 2, or 3.

,~,.. .

01 -19- ~1936-1612 The term "unsaturated nitrogen heterocycle" as used herein with respect to Rl and R2 of formula I refer 05 to the groups having the formulas:

I
N N N
~,~ L ~ ~

~ ~ ~ N~ ~

The term "compatible salts" refers to salts which do not significantly alter the herbicidal properties of the parent compound. Suitable salts include cation salts such as, for example, the cation salts of lithium, sodium, potassium, alkali earth metals, ammonia, quater-nary ammoniu~ salts, and the like.
The term "room temperature" or "ambient temperature" refers to about 20-25C.
Utility The compounds of Formula (I) exhibit both pre-emergence and post-emergence herbicidal activity and exhibit especially good pre-emergence herbicidal activity.
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 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 is contacted and the extent of contact. The optimum dosage can also vary with the general location, or environment ~e.g., sheltered areas such as greenhouses ~ compared to exposed areas such as fields), and type and degree of control desiredO Generally, Eor both pre- and .~ ,.

~l -20-post-emergent control, the present compounds are applied at rates of about from 0.02 to 60 kg/ha, preferably about OS from 0.02 to lO kg/ha.
Also, although in theory the compounds can be applied undiluted, in actual practice they are generally applied as a composition or formulation comprising an effective amount of the compound(s) and an acceptable car-rier. An acceptable or compatible carrier (agriculturallyacceptable carrier) is one which does not significantl~
adversely affect the desired biological effect achieved by 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) o mixtures thereof.
Concentrates can also be made having high concentrations designed for dilution prior -to application. The carrier can be a solid, liquid, or aerosol. The actual composi-tions can take the form of granules, powders, dusts, solutions, emulsions, slurries, aerosols, and the like.
Suitable solid carriers which can be used include, for example, natural clays (such as kaolin, atta-pulgite, montmorillonite, etc.), talcs, pyrophyllite, diatomaceous silica, synthetic fine silica, calcium aluminosilicate, tricalcium phosphate, and the like.
Also, organic materials, such as, for example, walnut shell flour, cotton-seed hulls, wheat flour, wood flour, wood bark flour, and the like can also be used as carriers. Suitable liquid diluents which can be used include, for example, water, organic solvents (e.g., hydrocarbons such as benzene, toluene, dimethylsulfoxide, kerosene, diesel fuel, fuel oil, petroleum naphtha, etc.), and the like. Suitable aerosol carriers which can b0 used include conventional aerosol carriers such as halogenated alkanes, etc.
The composition can also contain various promoters and surface-active agents which enhance the rate of transpo~t of the active compound into the plant tissue such as, for example, organic solvents, wetting agents and oils, and in the case of compositions designed for pre-emergence application agents which reduce the leachability of 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 active compounds.
1~ At reduced dosages the compounds of the present invention also exhibit plant growth regulatiny 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 herbicidal compositions can also be used. Depending on the d~sired 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, and insecticides. Typically, the plant growth regulating composition will contain a to~al 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. h'herein, unless expressly stated to th0 con-trary, all temperatures and temperature ranges refer to the Centigrade system and the term "ambient" or "room temperature" refers to about 20-25C. 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 of reagent equal in moles, to the moles of the preceding or succeeding reactant racited in that example in terms of finite moles or finite weight or volume. Where given, proton~magnetic resonance spectrum Z~8 (p.m.r. or n.m.r.) were determined at 60 m~z, signals are assigned as singlets ts), broad singlets (bs), doublets 05 (d), double doublets (dd), triplets (t), double triplets (dt), quartets (q), and multiplets (m); and cps refers to cycles per second. Also where necessary examples are repeated to provide additional starting material for sub-sequent examples.
EXAMP~ES
Example 1 (3-Trifluoromethylphenyl)-benzylcarbonyl-acetonitrile In this example, 4.91 g of metallic sodium was added to ~10 ml of anhydrous ethanol at room temperature and stirred until all of the sodium dissolved. A mixture containing 18.75 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 ~or about 18 hours. The mixture was then poured into 300 ml water and extracted three times with ethyl ather.
The pH of the extracted agueous layer was adjusted to a pE~
of about 1 with aqueous 10 wt. ~ hydrochloric acid and again extracted three times with ethyl ether. The organic layer was washed twice with saturated aqueous sodium bicarbonate, dried over magnesium sulfate and evaporated to dryness under vacuum affording 22.6 g of the title compound.
Similarly, by adapting the above procedure using the appropriately substituted-phenyl acetonitrile and ethyl-substituted phenyl acetate starting materials, the following compounds can be prepared:
(5-chloro-3-trifluoromethylphenyl)-benzylcarbonyl-acetonitrile;
(4-chloro-3-trifluoromethylphenyl)-benzylcarbonyl-acetonitrile;
(2-bromo-3-trifluorcmethylphenyl)-benzyl-! carbonyl-acetonitrile;
(6-fluoro-3-trifluoromethylphenyl)-benzyl carbonyl-acetonitrile;
(4-methyl-3-trifluoromethylphenyl)-benzyl-carbonyl-acetonitrile;

~S~8 : -23-(5-methoxy-3-trifluoromethylphenyl)-benzyl-carbonyl-acetonitrile;
(6-methyl-3-trifluoromethylphenyl)-benzyl-05 carbonyl-acetonitrile;
(3,5-di-trifluoromethylphenyl)-benzylcarbonyl-acetonltrile;
(3-difluoromethoxyphenyl)-benzylcarbonyl-acetonitrile;
(3-trifluoromethoxyphenyl)-benzylc~rbonyl-acetonitrile;
(3-trifluoromethylphenyl)-(4-fluorobenzyl-carbonyl)-acetonitrile;
(3-trifluoromethylphenyl)-1-naphthylmethylene-acetonitrile;
~ (2-chloro-3-methylphenyl)-benzylcarbonyl-: acetonitrile;
~4-ethyl-3-methylphenyl)-benzylcarbonyl-acetonitrile;
(5-methoxy-3-chlorophenyl)-benzylcarbonyl-acetonitrile;
(3-iodophenyl)-benzylcarbonyl-acetonitrile;
(3-difluorornethylthiophenyl)-benzylcarbonyl-acetonitrile;
(3-trifluoromethylthiophenyl)-benzylcarbonyl-acetonitrile;
(3,5-diethoxyphenyl)-benzylcarbonyl-aceto-nitrile;
(3-bromophenyl)-(2-nitrobenzylcarbonyl)-aceto-nitrile;
(2-chloro-3-methylphenyl)-benzylcarbonyl-acetonitrile;
(3-brorno-2-ethylphenyl)-naphth-1-ylmethylene-carbonyl-acetonitrile;
(2,3-dimethylphenyl)-beta-naphth-1-ylmethyl-carbonyl-acetonitrile;
(3-chlorophenyl)-benzylcarbonyl-acetonitrile;
(3-methylphenyl)-benzylcarbonyl-acetonitrile;
(3-t-butoxyphenyl)-benzylcarbonyl-acetonitrile;

(3-propylphenyl)-benzylcarbonyl-acetonitrile;
(3-bromophenyl)-benæylcarbonyl-acetonitrile;
05 (3-iodophenyl)-(3-nitrobenzylcarbonyl)-acetonitrile;
(3-trifluoromethylphenyl)-(2,3-dichlorobenzyl-carbonyl)-acetonitrile;
(3-methoxyphenyl)-1-naphthylmethylenecarbonyl-acetonitrile;
(3-trifluoromethyl)-(3-chloro-8-fluoronaphth-1-ylmethylenecarbonyl)-acetonitrile;
(3-trifluoromethyl)-[(2-trifluoromethyl-3-methyl-8-methoxy-napth-1-yl)methylenecarbonyl]-aceto-nitrile;
(3-trifluoromethyl)-(inden-1-ylmethylene-carbonyl)-acetonitrile; and (3-trifluoromethyl)-(2-fluoroinden-1-yl-methylenecarbonyl)-acetonitrile.
Example 2 2-Phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran In this example a solution containing 21.8 g of (3-trifluoromethylphenyl)-benzylcarbonyl-acetonitrile, dissolved in 60 ml of acetic acid was treated dropwise with a solution of 12.65 g of bromine in 20 ml of glacial acetic acid. The reaction mixture was stirred for about 16 hours at room temperature. The reaction mixture was poured into 250 ml of water and the resulting mixture was extracted three times with ethyl ether. The organic extracts were washed with saturated aqueous sodium bicar-bonate, dried over magnesium sulfate and concentrated in vacuo to yield 8,4 g of white solid which was dried affording 7.0 g of the title compound.
Similarly, by adapting the above procedure to the compounds listed in Example 1, the following compounds can be prepared:
2-phenyl-3-oxo-4-(5-chloro-3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrofuran;

1;2S~

2-phenyl-3-oxo-4-(4-chloro-3-tr.ifluoromethyl-phenyl)-5-amino-2,3-dihydrofuran;
OS 2-phenyl-3-oxo-4-(2-bromo-3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(6-fluoro-3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(4-methyl-3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(5-methoxy-3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(6-methyl-3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-~3,5-di-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(3-difluoromethoxyphenyl)-5-amino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(3-trifluoromethoxyphenyl)-5-~o amino-2,3-dihydrofuran;
2-(4-fluorophenyl)-3-oxo-4-(3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrofuran;
2-~1-naphthyl)-3-oxo-4-(3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(2-chloro 3-methylphenyl)-5-amino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(4-ethyl-3-methylphenyl)-5-amino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(5-methoxy-3-chlorophenyl)-5-amino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(3-iodo2henyl)-5-amino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(3-difluoromethylthiophenyl)-5 amino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(3-trifluoromethylthiophenyl)-5-amino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(3,5-diethoxyphenyl)-5-amino-2,3-dihydrofuran;
2-(2-nitrophenyl)-3-oxo-4-~3-bromophenyl)-5-amino-2,3-dihydrofuran;

2-phenyl-3-oxo-4-(2 chloro-3-methylphenyl)-5-amino-2,3-dihydrofuran;
05 2~ naphthyl)-3-oxo-4-(3-bromo-2-ethylphenyl)-5-amino-2,3-dihydrofuran;
2-(1-naphthyl)-3-oxo-4-(2,3-dimethylphenyl)-5-amino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(3-chlorophenyl)-5-amino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(3-methylphenyl)-5-amino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(3-butoxyphenyl)-5-amino-2,3-dihydro~uran;
2-phenyl-3-oxo-4-(3-propylphenyl)-5-amino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(3-bromophenyl)-5-amino-2,3-dihydrofuran;
2-(3-nitrophenyl)-3-oxo-~-(3-iodophenyl)-5-amino-2,3-dihydrofuran;
2-(2,3-dichlorophenyl)-3-oxo-4-(3-trifluoro-methylphenyl)~5-amino-2,3-dihydrofuran;
2-(1-naphthyl)-3-oxo-4-(3-methoxyphenyl)-5-amino-2,3-dihydrofuran;
2-(3-chloro-8-fluoronaphth-1-yl)-3-oxo-4-(3-tri-fluoromethylphenyl)-5-amino-2,3-dihydrofuran;
2-(2-trifluoromethyl-3-methyl-8-methoxy-naphth-l-yl)-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydroEuran;
2-inden-1-yl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran; and 2-(2-fluoroinden-1-yl) 3-oxo-4-(3-trifluoro-methylphenyl)-5-amino-2,3-dihydrofuran.
Example 3 2-Methyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran, A dry, 500-ml, three-neck, round-bottom flask equipped with a mechanical stirrer, addition funnel and a reflux condenser was charged with 100 ml of ethanol. To the stirred solvent were added 3.5 g of sodium. After all lZ~Z~;8 the metal had dissolved, a solution of 13.0 g of ethyl L-(+)-lactate and 18.5 g of m-trifluoromethylphenyl-05 acetonitrile in 30 ml of ethanol was added dropwise to the reaction mixture. The mixture became a deep red and after the addition was complete, the mixture was heated at reflux o~ernight (about 18 hours). The mixture was then cooled to room temperature and added to 300 ml of water and the resulting mixture was acidified (pH about 1) with 10% hydrochloric acid. The mixture was then extracted with ether (three times) and the organic extracts were washed (two times) with saturated aqueous sodium bicar-bonate, dried over magnesium sulfate and concentrated in vacuo to yield a thick oil. This oil was taken up in a mixture of ether/petroleum ether and the desired compound crystallized as a yellow powder. Two crops of crystals were collected to afford a total of 4.7 y of the title compound.
Similarly, by adapting the above procedure usin~
the corresponding appropriately substituted starting materials the Eollowiny compounds can be prepared:
2-ethyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran;
2-ethyl-3-oxo-4-(5-chloro-3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrofuran;
2-cyclopentyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran;
2-vinyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran;
2-allyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran;
2-allyl-3-oxo-4-(2-methoxy-3-triEluoromethyl-phenyl)-5-amino-2,3-dihydrofuran;
2-trifluoromethyl-3-oxo-4-(3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrofuran;
2-methyl-3-oxo-4-(3-difluoromethoxyphenyl)-5-amino-2,3-dihydrofuran;
2-methyl-3-oxo-4-(3-trifluoromethoxyphenyl)-5-amino-2,3-dihydrofuran;

01 -2~-2-(2-chlorovinyl)-3-oxo-4-(3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrofuran;
052-(2-chlorovinyl)-3-oxo-4-(5-propoxy-3-tri-fluoromethylphenyl)-5-amino-2,3-dihydrofuran;
2-methyl-3-oxo-4-(2-methoxy-3-chlorophenyl)-5-amino-2,3-dihydrofuran;
2-ethyl-3-oxo-4-(2-chloro-3-fluorophenyl)-5-10amino-2,3-dihydrofuran;
2-vinyl-3-oxo-4-(3-methyl-4-methoxyphenyl)-5-amino-2,3-dihydrofuran;
2-allyl-3-oxo-4-(3,6-dimethylphenyl)-5 amino-2,3-dihydrofuran;
lS2-trifluoromethyl-3-oxo-4-(3-trifluoromethyl-4-bromophenyl)-5-amino-2,3-dihydrofuran;
2-(2-chlorovinyl)-3~oxo-4-(3-nitro-4-methylphenyl)-5-amino 2,3-dihydrofuran;
2-methyl-3-oxo-4-(3-methoxyphenyl)-5-amino 2,3-20dihydrofuran;
2-methyl-3-oxo-4-(3-difluoromethylthiophenyl)-5-amino-2,3-dihydrofuran;
2-methyl-3-oxo-4-(3-trifluoromethylthiophenyl)-5-amino-2,3-dihydrofuran;
252-ethyl-3-oxo-4-(3-chlorophenyl)-5-amino-2,3-dihydrofuran;
2-vinyl-3-oxo-4-(3-methylphenyl)-5-amino-2,3-dihydrofuran;
2-allyl-3-oxo-4-~3,5 di(trifluoromethyl)-30phenyl]-5-amino-2,3-dihydrofuran;
2-trifluoromethyl-3-oxo-4-(4-fluorophenyl)-5-amino-2,3-dihydrofuran;
2-(2-chlorovinyl)-3-oxo-4-(2-bromophenyl)-3-oxo-5-amino-2,3-dihydrofuran;
352-propyl-3-oxo-4-(2-methoxy-3-chlorophenyl)-5-amino-2,3-dihydrofuran;
2-butyl-3-oxo-4-(2-chloro-3-fluorophenyl)-5-amino-2,3-dihydrofuran;
2-vinyl-3-oxo-4-(3-chloro-4-methoxyphenyl)-5-40amino-2,3-dihydrofuran;

S~ ;B

-29- 61g36-1612 2-allyl-3~oxo-4-(3,5-dimethylphenyl)-5-amino-2,3-dihydrofuran;
2-(trifluoromethyl)-3-oxo-4-(3-tri-fluoromethyl-5-bromophenyl)-5-amino-2,3-dihydrofuran;
2-(2-chlorovinyl)-3-oxo-4-(3-fluoro-4-methyl-phenyl)-3~oxo-5-amino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(3-methoxyphenyl)-5-amino-2,3-di-hydrofuran;
2-methyl-3-oxo-4-(3,5-difluorophenyl)-5-amino-2,3-dihydrofuran;
2-vinyl-3-oxo-4-(3,5-diethylphenyl)-5-amino-2,3-dihydrofuran;
2-allyl-3-oxo-4-(3-propoxyphenyl)-5-amino-2,3-di-hydrofuran;
2-trifluoromethyl-3-oxo-4-(3-fluorophenyl)-5-amino-2,3-dihydrofuran;
2-propyl-3~oxo-4-(3-bromophenyl)-3-oxo-5-amino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(2-iodo-3-fluorophenyl)-5-amino-2,3-dihydrofuran;
2-benzyl-3-oxo-4-(2-isopropoxy-3-trifluoro-methyl-phenyl)-5-amino-2,3-dihydrofuran;
2-(3-chlorophenyl)-3-oxo-4-(2,3-dimethylphenyl)-5-amino-2,3-dihydrofuran;
2-naphth-1-yl-3-oxo-4-(3-trifluoromethyl-4-bromo-phenyl)-5-amino-2,3-dihydrofuran;
2-(3-methylphenyl)-3-oxo-4-(3-butyl-4-methylphenyl)-3-oxo-5-amino-2,3-dihydrofuran;

2-(3-fluorophenyl)-3-oxo-4-(3-chlorophenyl)-5-amino-2,3-dihydrofuran;

SZ ~i8 - 29a - 61936-1612 2-(2,3,5-trifluorophenyl)-3-oxo-4-(3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrofuran;
2-(3-methylnapth-1-yl)-3-oxo-4-(3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrofuran;
2-(1-chlorovinyl)-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran;
2-fluoromethyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran;

~ ` lZS~4~3 2-methoxymethylene-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran;
2-propoxymethylene-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran;
2-ethoxymethylene-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran;
2-(2-methoxypropyl)-3-oxo-4-(3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrofuran;
2-methylthiomethylene-3-oxo-4-(3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrofuran; and 2-(1-propylthioethyl)-3-oxo-4-(3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrofuran.
Example 4 (3-Trifluoromethylphenyl)-methoxyacetyl-acetonitrile_ In this example 5.6 grams of metallic sodium was added to 120 ml of anhydrous ethanol at room temperature under a nitrogen atmosphere resulting in the evolution of hydroyen.
After evolution of hydrogen was completed a mixture containing 20 30 g of (3-trifluoromethylphenyl)-acetonitrile and 18.5 g of methyl methoxyacetate in anhydrous ethanol was added and the resulting mixture refluxed for 3 to 4 hours. The mixture was then added to 300 ml of water and extracted three times with petroleum ether. The remaining aqueous phase was acidified with aqueous 10~ hydrochloric acid to about pH 1 and extracted three times with ethyl ether. The ethyl ether extracts were combined, washed twice with saturated aqueous sodium bi-carbonate, dried over magnesium sulfate and concentrated by evaporation. The concentrate was evaporated under high vacuum affording an oil which was triturated with ethyl ether. This mixture was -then filtered to remove solids and the filtrate ~!

s~
- 30a - 61936~1612 evaporated under vacuum affording 36.9 g of the title compound as a brown solid.
Similarly, by adapting the above procedure but using other (substituted and disubstituted phenyl) acetonitriles in place of ~3-trifluoromethylphenyl)acetonitrile ~SZ~

the corresponding substituted and disubstituted phenyl analogs of the title compound can be prepared.
05 Example 5 (3-Trifluoromethylphenyl)-2-methoxvisovaleryl-acetonitrile In this example 10 g o t3-trifluoromethyl-phenyl)-methoxyacetyl-acetonitrile was added dropwise to a slurry of 1.8~ g of sodium hydride in 20 ml of tetra-hydrofuran at about 0C under a nitroyen atmosphere, resulting in the evolution of hydrogen. After no further evolution of hydroyen was observed, the mixture was cooled to about -78C and 24.3 ml of 1.6M n-butyllithium in hexane was added dropwise. The mixture was stirred for 1-1/2 hours at -78C and then stirred at about 0-4C for twenty minutes. After this 3.9 ml (about 6.6~ g) of 2-iodopropane was added dropwise and the mixture stirred overnight (about 14-16 hours). The mixture was then added to water, acidified with aqueous 10% hydrochloric acid and extracted three times with ethyl ether. The ~xtracts were combined, dried over magnesium sulfate and concentrated under vacuum affording 11.4 g of the title compound as an oil.
Similarly, by adapting the same procedure but using the appropriate alkyl, aryl or substituted aryl, iodide, bromide, or chloride in place of iodopropane the following compounds can be prepared:
(3-trifluoromethylphenyl)-(2~methoxy-3-phenylpropionyl)acetonitrile7 (3-trifluoromethylphenyl)-~2-methoxy-3-(2-fluorophenyl)propionyl]acetonitrile;
(3-trifluoromethylphenyl)~[2-methoxy-3-(3-methylphenyl)propionyl]acetonitrile;
(3-trifluoromethylphenyl)-[2-methoxy-3-(2-ethoxyphenyl)propionyllacetonltrile;
(3-trifluoromethylphenyl)-[2-methoxy-3-(3-nitrophenyl)propionyl]acetonitrile;
(3-trifluoromethylphenyl)-[2-methoxy-3-(2-trifluoromethylphenyl)propionyl]acetonitrile;

~zs;~

(3-trifluoromethylphenyl)-[2-methoxy-3-(2-chloro-3-propylphenyl)propionyl]acetonitrile;
05 (3-trifluoromethylphenyl)-[2-methoxy-3-(2-nitro-3-methoxyphenyl)propionyl]acetonitrile;
(3-trifluoromethylphenyl)-[2-methoxy-3-(2-fluoro-3-2',2'-dichloroethylphenyl)propionyl]acetonitrile;
(3-trifluoromethylphenyl)-[2-methoxy-3-(2,3-dichloro-6-methylphenyl)propionyl]acetonitrile;
(3-trifluoromethylphenyl)-(2-methoxy-4-phenylbutyryl)acetonitrile;
(3-trifluoromethylphenyl)-[2-methoxy-5-(2-bromophenyl)valeryl]acetonitrile;
(3-trifluoromethylphenyl)-(2-methoxy-3-methyl-4-phenylbutyryl)acetonitrile;
(3-trifluoromethyl)~(2-methoxy-3-naphth-1-ylpropionyl)acetonitrile;
(3-trifluoromethyl)-[2-methoxy-3-(2-fluoronaphth-l-yl)propionyl]acetonitrile;
(3-trifluoromethyl)-[2-methoxy-3-~3-butylnaphth-l-yl)propionyl]acetonitrile;
(3-trifluoromethyl)-[2-methoxy-3-(5-methoxynaphth-l-yl)propionyl]acetonitrile;
(3-trifluoromethyl)-[2-methoxy-3-(6-nitronaphth-l-yl)propionyl]acetonitrile;
(3-trifluoromethyl)-[2-methoxy-3-(7-trifluoro-methylnaphth-l-yl)propionyl]acetonitrile;
(3-trifluoromethyl)-[2-methoxy-3-(2-chloro-8-methylnaphth-l-yl)propionyl]acetonitrile;
(3-trifluoromethyl)-[2-methoxy-3-(3-methoxy-5-nitro-7-fluoromethylnaphth-1-yl)propionyl]acetonitrile;
(3-trifluoromethyl)-(2-methoxy-4-naphth-1-ylbutyryl)acetonitrile;
(3-trifluoromethyl)-[2-methoxy-5-(8-fluoronaphth-l-yl)valeryl]acetonitrile;
(3-trifluoromethyl)-[2-methoxy-3-methyl-3-~7-methoxynaphth-l-yl)propionyl]acetonitrile;
(3-trifluoromethylphenyl)-(2-methoxy-3-inden-1-ylpropionyl)acetonitrile; and

4~

(3-trifluoromethylphenyl)-[2-methoxy-3-~2-fluoro-inden-l-yl)propionyl]acetonitrile.
Similarly, by adapting the above procedure using other (mono or disubstituted phenyl)-(methoxyacetyl)ace-to-nitriles in place of (3-trifluoromethylphenyl)-(2-methoxy-acetyl)acetonitrile the corresponding mono or disubstituted phenyl derivatives of the above compounds can be prepared.
Example 6 2-Isopropyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran In this example, a mixture containing 11.4 g of (3-trifluoromethylphenyl)-(2-methoxyisovaleryl)acetonitrile and 7.8 g of concentrated sulfuric acid in 50 ml of acetic acid was warmed to reflux for 30 minutes and -then concentrated by evaporation under vacuum. The concentrate was mixed with di-ethylether, washed three times with lN aqueous sodium hydroxide, dried over magnesium sulfate and concentrated by evaporation affording an oil. The oil was triturated in 20%
(vol.) ethyl acetate:80% petroleum ether and allowed to stand overnight (14-16 hours). The solids were collected by filtra-tion and washed three times with 20% (vol.) ethyl acetate:80%
petroleum ethyl affording 2.9 g of the title compound.
Similarly, by adapting the above procedure using 3-trifluromethylphenyl-dimethoxyacetyl-acetonitrile, which can be prepared via the procedure of Example 1, and the other compound products indicated in Example 5 -the following compounds can be prepared:

2-methoxy-5-oxo-4-(3-trifluoromethylphenyl~-5-amino-2,3-dihydrofuran-2-benzyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran;
2-(2-fluorobenzyl)-3-oxo-4-(3-trifluoromethyl-- 33a - 61936-1612 phenyl)-5-amino-2,3-dihydrofuran;
2-(3-methylbenzyl)-3-oxo-4-(3-trifluoromethyl-: phenyl)-5-amino-2,3-dihydrofuran;
2-(2-ethoxybenzyl)-3-oxo-4-(3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrofuran, 2-(3-nitrobenzyl)-3-oxo-4-(3-trifluoromethylphenyl)-

5-amino-2,3-dihydrofuran;

`` ~Z~ ;8 01 ~34~

2-(4-fluorobenzyl)-3-oxo-4-(3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrofuran;
05 2-(2-trifluoromethylbenzyl)-3-oxo-4-(3-tri-fluoromethylphenyl)-5-amino-2,3-dihydrofuran;
2-(2-chloro-3-propylphenyl)-3-oxo-4-(3-tri-fluoromethylphenyl)-S-amino-2,3-dihydrofuran;
2-(2-nitro-3-methoxyphenyl)-3-oxo-4-(3-tri-fluoromethylphenyl)-5-amino-2,3-dihydrofuran;
2-(2-fluoro-3-2 7 ~ 2'-dichloroethylbenzyl)-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran;
2-(2,3-dichloro-6-methylbenzyl)-3-oxo-4-(3-tri-fluoromethylphenyl)-5-amino-2,3-dihydrofuran;
2-(beta-phenethyl)-3-oxo-4-(3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrofuran;
2-[3-(2-bromophenyl)propyl]-3-oxo-4-(3-tri-fluoromethylphenyl)-5-amino-2,3-dihydrofuran;
2-[1-methyl-2-(phenyl)ethyl]-3-oxo-4-(3-tri-fluoromethylphenyl)-5-amino-2,3-dihydrofuran;
2-naphth-1-ylmethylene-3-oxo-4-(3-trifluoro-methylphenyl)-5-amino-2r3-dihydrofuran;
2-(2-fluoronaphth-1-ylmethylene)-3-oxo-4-(3-tri-fluoromethylphenyl)-5-amino-2,3-dihydrofuran;
2-(3-butylnaphth-1-ylmethylene)-3-oxo-4-(3-tri- .
fluoromethylphenyl)-5-amino-2,3-dihydrofuran;
2-(5-methoxynaphth-1-ylmsthylene)-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran;
2-(6-nitronaphth-1-ylmethylene)-3-oxo-4-(3-tri-fluoromethylphenyl)-5-amino-2,3-dihydrofuran;
2-(7-trifluorometnylnaphth-1-ylmethylene)-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran;
2-(2-chloro-8-methylnaphth-1-ylmethylene)-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran;
2-(3-methoxy-5-nitro~7-fluoromethylnaphth-1-yl)-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydro-furan;
2-(beta-naphth-1-ylethyl)-3-oxo-4-(3-trifluoro-methylphenyl)-5-amino-2,3-dihydrofuran;

-`~ 12~

2-[beta-(8-fluoronaphth-1-yl)ethyl]-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran;
05 2-[1-(7-methoxynaphth-1-yl)ethyl]-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran;
2-inden-1-ylmethylene-3-oxo-4-(3-trifluoro-methylphenyl)-5-amino-2,3-dihydrofuran; and 2-(2-fluoroinden-1-ylmethylene)-3-oxo-4-(3-tri-fluoromethylphenyl)-5-amino-2,3-dihydrofuran.
Similarly, by adapting the above procedure using the corresponding mono- and disubstituted analogs of the starting material for the above compounds the corre-sponding 4-(3-methylphenyl); 4-(3-beta-fluoroethoxy-phenyl); 4-(3-diEluoromethylenethiophenyl~; 4-(3-chlorophenyl); 4-(2-bromo-3-trifluoromethylphenyl)- and 4-(2-methyl-3-difluoromethylenethiophenyl analogs of the above compounds can be preparedO
Example 7 2-Phenyl-3 oxo-4-(-3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran In this example about 1 g of solid sodium hydroxide in 4.0 ml of water was added to a mixture of 3 9 of 2 phenyl-3-oxo-4-(3-trirluoromethylphenyl)-5-amino-2,3-dihydrofuran in 50 ml of methylene chloride at room temperature followed by the addition of 1.19 9 of dimethyl sulfate and 0.21 g oE benzyltriethyl ammonium chloride.
The resulting two-phase mixture was stirred at room tem-perature for about two hours and then washed three times with water, dried over magnesium sulfate and then concen-trated by evaporatiGn under vacuum~ The residue was then purified by chromatography over silica gel eluting with mixtures of tetrahydrofuran and chloroform affording the title compound.
Similarly, by adapting the above procedure using the products listed in Examples 2, 3 and 6 as starting materials, the corresponding 5-methylamino homologs thereof can be prepared, for example:
2-phenyl 3-oxo-4-l5-chloro-3-trifluoromethyl-phenyl)-5-methylamino-2,3~dihydrofuran;

5Z~i8 2-phenyl-3-oxo-4-(4-chloro-3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrofuran;
05 2-phenyl-3-oxo-4-(2-bromo-3-trifluoromethyl-phenyl)-5~methylamino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(6-fluoro-3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(4-methyl-3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(5-methoxy-3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(6-methyl-3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(3,5-di-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran;
: 2-phenyl-3-oxo-4-(3-difluoromethoxyphenyl)-5-; methylamino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(3-trifluoromethoxyphenyl)-5-methylamino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(3-trifluoromethylthiophenyl)-S-methylamino-2,3-dihydrofuran;
2-(4-fluorophenyl) 3-oxo-4-(3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrofuran;
2-(1-naphthyl)-3-oxo-4-(3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(2-chloro-3-methylphenyl)-5-methylamino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(4-ethyl-3-methylphenyl)-5-methylamino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(5-methoxy-3-chlorophenyl)-5-methylamino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(3-iodophenyl)-5-methylamino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(3-difluoromethylthiophenyl)-5-methylamino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(3-trifluoromethylthiophenyl)-5-methylamino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(3l5-diethoxyphenyl)-5-methylamino-2,3-dihydrofuran;

- 3LZ~ 8 01 ~37~

2-(2-nitrophenyl)-3-oxo-4-(3-bromophenyl)-5-methylamino-2,3-dihydrofuran;
05 2-phenyl-3-oxo-4-(2-chloro-3-methylphenyl)-5-methylamino-2,3-dihydrofuran;
2-(1-naphthyl)-3-oxo-4-(3-bromo-2-ethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-(1-naphthyl)-3-oxo-4-(2,3-dimethylphenyl)-5-methylamino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(3-chlorophenyl)-5-methylamino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(3-methylphenyl)-5-methylamino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(3-butoxyphenyl)-5-methylamino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(2-propylphenyl)-5-methylamino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(3-bromophenyl)-5-methylamino-2,3-dihy~rofuran;
2-~3-nitrophenyl)-3-oxo-4-(3-iodophenyl)-5-methylamino-2,3-dihydrofuran;
2-(2,3-dichlorobenzyl)-3-oxo-4-(2-trifluoro-methylphenyl)-5-methylamino-2,3-dihydrofuran~
2-(1-naphthyl)-3~oxo 4-(3-methoxyphenyl)-5-methylamino-2,3-dihydrofuran;
2-(3-chloro-8-fluoronaphth-1-yl) 3-oxo-4-(3-trifluoromethylphenyl)-S-methylamino-2,3-dihydrofuran;
2-(2-trifluoromethyl-3-methyl-8-methoxynaphth-1-yl)-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofur,ln;
2-inden-1-yl-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran;
2-(2-fluoroinden-1-yl)-3-oxo-4-(3-trifluoro-methylphenyl)-5-methylamino-2,3-dihydrofuran;
2-methyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran;
2-ethyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran;

S~;B

2-ethyl-3-oxo-4-(5-chloro-3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrofuran;
05 2-cyclopentyl-3-oxo-4-(3-trifluorome~hylphenyl)-5-methylamino-2,3-dihydrofuran;
2-vinyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran;
2-allyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran;
2-allyl-3-oxo-4-(2-methoxy-3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrofuran;
2-trifluoromethyl-3-oxo-4-(3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrofuran;
2-methyl-3-oxo-4-(3-difluoromethoxyphenyl)-5-methylamino-2,3-dihydrofuran 2-methyl-3-oxo-4-(3-trifluoromethoxyphenyl)-5-methylamino-2,3-dihydrofuran;
2-(2-chlorovinyl)-3-oxo-4-(3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrofuran;
2-(2-chlorovinyl)-3-oxo-4-(5-nitro-3-tri~luoro-methylphenyl)-5-methylamino-2,3-dihydrofuran;
2-methyl-3-oxo-4-(2-methoxy-3-chlorophenyl)-5-methylamino-2,3-dihydrofuran;
2-ethyl-3-oxo-4-(2-chloro-3-fluorophenyl)-5-methylamino-2,3-dihydrofuran;
2-vinyl-3-oxo-4-(3-methyl-4-methoxyphenyl)-5-methylamino-2,3-dihydrofuran;
2-allyl-3~oxo-4-(3,6-dimethylphenyl)-5-methylamino-2,3-dihydrofuran;
2-trifluoromethyl-3-oxo-4-(3-trifluoromethyl-4-bromophenyl)-5-methylamino-2,3-dihydrofuran;
2-(2-chloro~inyl)-3-oxo-4-(3-nitro-4-methyl-phenyl)-3-oxo-5-methylamino-2,3-dihydrofuran;
2-methyl-3-oxo-4-(3-methoxyphenyl)-5-methyl-amino-2,3-dihydrofuran;
2-methyl-3-oxo-4-(3-difluoromethylthiophenyl)-5-methylamino-2,3-dihydrofuran;
2-methyl-3-oxo-4-(3-trifluoromethylthiophenyl)-5-methylamino-2,3, dihydrofuran;

~S~

01 -39~

2-ethyl-3-oxo-4-(3-chlorophenyl)-5-methylamino-2,3-dihydrofuran;
05 2-vinyl-3-oxo-4-(3-methylphenyl~-5-methylamino-2,3-dihydrofuran;
2-allyl-3-oxo-4-[3,5-di(trifluoro~.ethyl)phenyl]-5-methylamino-2,3-dihydrofuran;
2-trifluoromethyl-3-oxo-4-(4-fluorophenyl)-5-methylamino-2,3-dihydrofuran;
2-(2-chlorovinyl)-3-oxo-4-(2-bromophenyl)-3-oxo-5-methylamino~2,3-dihydrofuran;
2-propyl-3-oxo-4-(2-methoxy-3-chlorophenyl)-5-methylamino-2,3-dihydrofuran;
2-butyl-3-oxo-4-(2-chloro-3-fluorophenyl)-5-methylamino-2,3-dihydrofuran;
2-vinyl-3-oxo-4-(3-chloro-4-methoxyphenyl)-5-methylamino-2,3-dihydro~uran;
2-allyl-3-oxo-4-(3,6-dimethylphenyl)-5-methylamino-2,3-dihydrofuran 2-trifluoromethyl-3-oxo-4-(3-trifluoromethyl-5-bromophenyl)-5-methylamino-2,3-dihydrofuran;
2-(2-chlorovinyl)-3-oxo-4-(3-fluoro-4-methyl-phenyl)-3-oxo-5-methylamino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(3-methoxyphenyl)-5-methyl-amino-2,3-dihydrofuran;
2-methyl-3-oxo-4-(3,5-difluorophenyl)-5-methylamino-2,3-dihydrofuran;
2-vinyl-3-oxo-4-(3,5-diethylphenyl)-5-methyl-amino-2,3-dihydrofuran;
2-allyl-3-oxo-4-(3-propoxyphenyl)-S-msthylamino-2,3-dihydrofuran;
2-tri~luoromethyl-3-oxo-4-(3-fluorophenyl)-5-m~thylamino-2,3-dihydrofuran;
2 propyl-3-oxo-4-(2-bromophenyl)-3-oxo-5-methyl-amino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(2-iodo-3-fluorophenyl)-5-methylamino-2~3-dihydrofuran;
2-benzyl-3-oxo-4-(2-isopropoxy-3-trifluoro-methylphenyl) 5-methylamino-2,3-dihydrofuran;

-~0- 6193~-1612 r 2-(3-chlorophenyl)-3-oxo-4-(2,3-dimethylphenyl)-5-methylamino-2,3-dihydrofuran;
2-naphth-1-yl-3-oxo-4-(3-trifluoromethyl-4-bromo-phenyl)-5-methylamino-2,3-dihydrofuran;
2-(3-methylphenyl)-3-oxo-4-(3-butyl-4-methylphenyl)-3~oxo-5-methylamino-2,3-dihydrofuran;
2-(3-fluorophenyl)-3-oxo-4-(3-chlorophenyl)-5-methylamino-2,3-dihydrofuran;
2-(2,3,5-trifluorophenyl)-3-oxo-4-(3-trifluoro-methylphenyl)-5-methylamino-2,3-dihydrofuran; and 2-(3-methylnaphth-1-yl)-3-oxo-4-(3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrofuran;
2-(l-chlorovinyl)-3-oxo-4-(3-trifluoromethylphenyl)-5 -methylamino-2,3-dihydrofuran;
2-fluoromethyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran;
2-methoxymethylene-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-di.hy-lrofuran;
2-propoxymethylene-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran;
2-ethoxymethylene-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran;
2-(2-methoxypropyl)-3-oxo-4-(3-trifluorome-thyl-phenyl)-5-methylamino-2,3-dihydrofuran;
2-methylthiomethylene-3-oxo-4-(3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrofuran; and 2-(1-propylthioethyl)-3-oxo-4-(3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrofuran.

2-benzyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methyl-amino-2,3-dihydrofuran;

- 40a - 61936-1612 2-(2-fluorobenzyl)-3-oxo-4-(3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrofuran, 2-(3-methylbenzyl)-3-oxo-4-(3-trifluoromethyl-phenyl~-5-methylamino-2,3-dihydrofuran;
2-(2-ethoxybenzyl)-3-oxo-4-(3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrofuran;
2-(3-nitrobenzyl)-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran;

1~S~ 8 2-(4-fluorobenzyl)-3-oxo-4-(3-trifluoromethyl-phenyl)-5-methylamino-2,3-dihydrofuran;
OS 2-(2-trifluoromethylbenzyl)-3-oxo-4-(3-tri-fluoromethylphenyl1-5-methylamino-2,3-dihydrofuran;
2-(chloro-3-propylphenyl)-3-oxo-4-(3-trifluoro-methylphenyl)-5-methylamino-2,3-dihydrofuran;
2-(2-nitro-3-methoxyphenyl)-3-oxo-4-(3-tri-fluoromethylphenyl)-5-methylamino-2,3-dihydrofuran;
2-(2-fluoro-3-2',2'-dichloroethylbenzyl)-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran;
2-(2l3-dichloro-6-methylbenzyl)-3-oxo-4-(3-tri-fluoromethylphenyl)-5-methylamino-2,3-dihydrofuran;
2-(beta-phenethyl)-3-oxo-4-(3-trifluoromethyl-phenyl~-5-methylamino-2,3-dihydrofuran;
2- E 3-~2-bromophenyl)propyl]-3-oxo-4-(3-tri-fluoromethylphenyl)-5-methylamino-2,3-dihydrofuran;
~0 2-[1-methyl 2-(phenyl)ethyll-3-oxo-~-~3-tri-fluoromethylphenyl)-5-methylamino-2,3-dihydrofuran;
2-naphth-1-ylmethylene-3-oxo-4-(3-trifluoro-methylphenyl)-5-methylamino-2,3-dihydrofuran;
2-(2-fluoronaphth-1-ylmethylene)-3-oxo-4~(3-tri-fluoromethylphenyl)-5-methylamino-2,3-dihydrofuran;
2-(3-butylnaphth-1-ylmethylene)-3-oxo-4-(3-tri-fluoromethylphenyl)-5-methylamino-2,3-dihydrofuran;
2-(5-methoxynaphth-1-ylmethylane)-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran;
2 (6-nitronaphth-1-ylmethylene)-3-oxo-4-(3-tri-fluoromethylphenyl)-5-methylaminc-2,3-dihydrofuran;
2-(7-trifluoromethylnaphth-1-ylmethylene)-3-oxo-4-(3-trifluoromethylphenyl)-5 methylamino-2,3-dihydrofuran;
2-(2-chloro-8-methylnaphth-l-ylmethylene)-3 4-(3-trifluoromethylphenyl)-5-methylamino-2,3 dihydrcfuran;
2-(3-methoxy-5-nitro-7-fluoromethylr.aphth-1-yl)-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran;

- ~2 - ~ 61936-161~
"
0l 2-methoxy-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dih~drofuran;
2-(beta-nauhth-l-ylethyl)-3-oxo-4-(3-triEluoro-methylphenyl)-5-methylamino-2,3-dihydrofuran;
05 2-[beta-(8-fluoronaphth-l-yl)ethyl]-3-oxo-4-t3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran;
2-[l-(7-methoxynaphth-l-yl)ethyl]-3-oxo-4-~3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran;
2-inden-l-ylmethylene-3-oxo-~ -trifluoro-methylphenyl)-5-methylamino-2,3-dihydrofuran; and 2-(2-fluoroinden-l-ylmethylene)-3-oxo-4-(3-tri fluoromethylphenyl~-5-methylamino-2,3-dihydrofuran.
Similarly, by approximately doubliny the amount of dimethylsulfate and increasiny the reaction time, the corresponding 5-dimethylamino homoloys oE the above compounds can be prepared. Similarly, by using diethylsulfate in place of dimethylsulphate the corresponding 5-ethylamino and 5-diethylamino homologs of the above compounds can be prepared.
Exam~le 8 2-~2-Fluorophenyl)-3-oxo-4-(3-triEluoro-methylp3henyl)-5-allylamino-2~3-dihydrofuran One gram o~ sodium hydroxide in 9.0 ml oE water was added to a mixture of 4.0 g of 2-(2-fluorophen~ 3-oxo-~-~3-trifluoromethylphenyl) 5-amino-2,3-dihydrouran in 80 ml of methylene chloride at room temperature oll~wed by the addition of l.'t'~ y oE allyl bromide and 0.~7 g o benzyltriethylammoniull chloride. Th~ re5ultincJ
two-phase mixture was stirred at room temperature Eor about 18 hours after which time it was washed three times with water, dried Gver maynesium sulfate and concentrated in vacuo. The residue was purifie~ by chromatography over silica gel eluting with chloroform to yield 2.5 g of the title compound.
Similarly, by applying this procedure to the products listed in Examples 2, 3 and 6, the correspQndiny 5-allylamino analogs thereof can be prepared. Similarly, by approximately doubliny the amount of allyl bromide and sodium hydroxide, the correspondiny 5-diallylamino analoys thereoE can be prepared.

. _~

3~
i~J

1~2~

01 ~43~

In a like manner, by using ethyl bromide in place of allyl bromide, the corresponding 5-ethylamino and ~5 5-diethylamino 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 - lG of alkyl bromide the corresponding 5-methoxymethylamino, 5-ethylthiomethylamino, 5~methoxycarbonylmethylamino, 5-'l-methoxycarbonylpropylamino), 5-piperidin-1-yl and 5-pyrrol-l-yl analo~s of the products listed in Examples 2, 3 and 6 can be prepared for example:
2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-msthoxymethylamino-2,3-dihydrofuran;
2-methyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methoxymethylamino-2,3-dihydrofuran;
2-ethyl-3-oxo-4-(3-tri1uoromethylphenyl)-5-methoxymethylamino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-ethylthiomethylamino-2,3-dihydrofuran;
2-methoxy-3--oxo-4-(3-trifluoromethylphenyl)-5-ethylthiomethylamino-2,3-dihydrofuran;
2-methyl-3-oxo-4-(3-trifluoromethylphenyl)-5-et.hylthiomethylamino-2,3-dihydrofuran;
2-ethoxymethylene-3-oxo-~-(3-trifluoromethyl-phenyl)-5-ethylthiomethylamino-2,3-dihydrofuran;
2-ethyl-3-oxo-4-(3-trifluoromethylphenyl)~5-ethylthiomethylamino-2,3-dihydrofuran;
2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methoxycarbonylmethylamino-2,3-dihydrofuran;
2-methyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methoxycarbonylmethylamino-2,3-dihydrofuran;
2-methylthiomethylene-3-oxo-4-(3-trifluoro~
methylphenyl)-5-methoxycarbonylmethylamino-2,3-dihydrofuran;
2-ethyl-3-oxo-4-(3-trifluoromethylphenyl)-S-methoxycarbonylmethylamino-2,3-dihydrofuran;

~2S~

01 ~44~

2-phenyl 3-oxo-4-~3-trifluoromethylphenyl~-5-(l-methoxycarbonylprop-l-yl)amino-2,3 dihydrofuran;
05 2-methyl-3-oxo-4-(3-trifluoromethylphenyl)-5-(1-methoxycarbonylprop-l-yl)amino-2,3 dihydrofuran;
2-fluoro-3-oxo-4-(3-trifluoromethylphenyl)-5-(1-methoxycarbonylprop-l-yl)amino-2,3-dihydrofuran;
2-ethyl-3-oxo-4-(3-trifluoromethylphenyl)-5-(1-methoxycarbonylprop-1-yl)amino-2,3-dihydrofuran;
2-naphth-l-yl-3-oxo-4-(3-trifluoromethylphenyl)-5~ methox~carbonylprop-1-yl)amino-2,3-dihydrofuran;
2-inden-1-yl-3-oxo-4-(3-trifluoromethylphenyl)-5-(l-methoxycarbonylprop-1-yl)amino-2,3-dihydrofuran, 2-phenyl-3-oxo-4--(3-trifluoromethylphenyl)-5-piperidin-l-yl-2,3-dihydrofuran; and 2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-pyr~ol-l-yl-2,3-dihydrofuran, etc.
Similarly, by applying the above procedures using the 5-methylamino products of Example 7 as starting materials, the corresponding 5-(~-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-thoxycarbonylpropylamino) analogs can be prepared.
Example 9 Lithium salt of 2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran (R =-CH3, R2--Li) In this example, 5.4 ml of 1.6M n-butyllithium in hexane was added dropwise to a stirred solution containing 2~36 g of 2-phenyl-3-oxo-4-(3-trifluoromethyl-phenyl)-5-amino-2,3-dihydrofuran in 25 ml of tetrahydro-furan at -30C. The resulting mixture was stirred for 20 minutes and then concentrated in vacuo affording 2.8 g of the title compound as a light brown solid. Elemental analysis: calculated, C-63.74, H-3.84, N-4.13; found, C-61.82, H-4.90, ~-3.48.

~L~2S;~;8 01 ~45~

Similarly, by adapting the above procedure, the - corresponding lithium salts of the compounds of 05 Examples 2-5 can also be prepared.
Example 10 The compounds listed in Table A hereinbelow were prepared using the appropriate starting materials and the appropriate procedures described in the Examples hereinabove.

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~ In this example, the compounds of ~b~e-~ were `~ 05 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 ~ ~ 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 m9 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.
Seeds of the test vegetation were planted in a pot of soil and the test solution was sprayed uniformly onto the soil surface either at a dose of 27.5 micrograms/cm2 or in some instances as indicated in Table 1 hereinbelow, certain of the compounds were tested at a lower dosage of l5.6 micrograms/cm2. The pot was watered and placed in a greenhouse. The pot was watered intermittently and observed for seedling emergence, health of emerging seedlings, etcO, for a 3-week period. At the end of this period, the herbicidal effectiveness of the compound was rated based on the physiological obser-vations. A 0-to-lO0 scale was used, 0 representing no phytotoxicity, lO0 representing complete kill. The results of these tests are summarized in Table 1.
Post-Emergent Herbicidal_Test The test compound was formulated in the same manner as described above ~or 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) -~ 12S~

(approximately 15 to 25 plants per pot) at a dose of 27.5 microgram/cm2~ After the plants had dried, they were 05 placed in a greenhouse and then watered intermittently at their bases as needed. The plants were observad periodically for phytotoxic effects and physiological and 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 Table 2.

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a ~s ~ ~) Z _, ~ ¦ ~ u E ~3 ~ o o o o o o o u o o o o o o o ~o ~1 5~: a) Ll O ~`I ~ ~ ~ r~
~ o 5 o u~

O _ u S ! ~ o o o o o o o n o o o o o o ~

~ V~ ~ v ~ ooooooo~oooo~no o ~ S ~
a:~ dP a~

~ ~oOo~oou oooooo~o E~ Z J ~_) 'J C~
O

_~ ~ O 11~ 0 ~f~
O O

i~S~

As can be seen from the above Table l, the compounds of the invention generally exhibit a broad spec~
05 trum of excellent pre-emergence phytotoxic activity and : especially so Compounds Nos. 2, 4, 7, 9, 12, 14, 16, 22~
Moreover, as shown by Table 2 the compounds also generally exhibit post-emergence phytotoxic activity against broad-leaf plants and in some instances also against grasses, especially so Compound Nos. 7, 9, 12, 14, 16, 22 and 23.
Also, it can be seen that the corresponding Comparison Compounds had much poorer activity than the corresponding compounds of the present invention.
Obviously, many modifications and variations of the invention described hereinabove and below can be made without departiny from the essence and scope thereof.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compound having the formula:

(I) wherein R is lower alkyl, cycloalkyl having 3 through 7 carbon atoms; 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 independently selected from the group of fluoro, chloro, bromo, or iodo; lower alkoxyalkyl 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-1-yl, inden-1-yl; 4-fluorophenyl; arylalkylene having 1 through 3 carbon atoms in the alkylene moiety and wherein the aryl moiety is phenyl, naphth-1-yl or inden-1-yl; or R is 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 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 alklylthioalkyl;
R1 and R2 together with the nitrogen atom to which they are joined form a saturated or unsatu-rated nitrogen heterocycle having 4 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 1 through 4 carbon atoms and 1 through 3 of the same or different halo atoms, with the proviso that when Y is halo then R, R1 and R2 are not all hydrogen and the further proviso that when Y is other than trifluoro-methyl and X is other than hydrogen, 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. The compound of Claim 1 wherein one of R1 or R2 is hydrogen, methyl, ethyl or propyl.

3. The compound of Claim 1 wherein one of R1 or R2 is methyl or ethyl and the other is hydrogen, methyl or ethyl.

4. The compound of Claim 1 wherein one of R1 or R2 is hydrogen and the other is methyl, ethyl or propyl.

5. The compound of Claim 1 wherein X is hydrogen.

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 1 wherein R is phenyl, naphth-1-yl, 4-fluorophenyl or substituted aryl.

9. The compound of Claim 8 wherein R is phenyl, naphthyl or a monosubstituted phenyl.

10. The compound of Claim 9 wherein R is phenyl, halophenyl, or lower alkylphenyl.

11. The compound of Claim 10 wherein R is phenyl, 4-fluorophenyl, 2-halophenyl, or 2-lower alkylphenyl.

12. The compound of Claim 11 wherein X is hydrogen and R1 and R2 are independently selected from the group of hydrogen, methyl or ethyl.

13. The compound of Claim 1 wherein R is lower alkyl, cycloalkyl, lower alkenyl, haloalkyl or halo-alkenyl.

14. The compound of Claim 13 wherein one of R1 or R2 is hydrogen, methyl or ethyl and the other is methyl or ethyl.

15. The compound of Claim 14 wherein R is methyl, ethyl or propyl.

16. The compound of Claim 15 wherein one of R1 or R2 is hydrogen and the other is methyl or ethyl.

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

18. A compound having the formula:

(I) wherein R is lower alkyl, cycloalkyl having 3 through 7 carbon atoms; lower alkenyl; halo-alkyl 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 independently selected from the group of fluoro, chloro, bromo, or iodo; 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-1-yl, inden-1-yl; 4-fluorophenyl; aryl-alkylene having 1 through 3 carbon atoms in the alkylene moiety and wherein the aryl moiety is phenyl, naphth-1-yl or inden-1-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;
R1 and R2 together with the nitrogen atom to which they are joined form a saturated or unsatu-rated nitrogen heterocycle having 4 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 compatible salts thereof.

19. The compound of Claim 18 wherein R1 and R2 are independently hydrogen, methyl or ethyl.

20. The compound of Claim 19 wherein one of R1 or R2 is methyl or ethyl and the other is hydrogen, methyl or ethyl.

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

22. The compound of Claim 19 wherein X is hydrogen and R is phenyl, naphthyl, 4-fluorophenyl, 2-halophenyl or 2-lower alkylphenyl.

23. The compound of Claim 22 wherein one of R1 or R2 is hydrogen and the other is hydrogen methyl or ethyl.

24. The compound of Claim 23 wherein R is phenyl, 2-fluorophenyl 2-chlorophenyl or 2-methylphenyl.

25. The compound of Claim 23 wherein R is phenyl.

26. The compound of Claim 23 wherein R is phenyl and one of R1 or R2 is hydrogen and the other is methyl.

27. The compound of Claim 23 wherein R is phenyl and one of R1 or R2 is hydrogen and the other is ethyl.

28. The compound of Claim 18 wherein R is lower alkyl, cycloalkyl, lower alkenyl, lower haloalkyl or lower haloalkenyl.

29. The compound of Claim 28 wherein R1 and R2 are inde-pendently hydrogen, methyl or ethyl.

30. The compound of Claim 29 wherein R is methyl, ethyl or propyl.

31. The compound of Claim 30 wherein one of R1 or R2 is hydrogen and the other is methyl or ethyl and X is hydrogen.

32. The compound of Claim 29 wherein X is hydrogen.

33. The compound of Claim 18 wherein X is hydrogen.

34. The compound of Claim 5 wherein Y is a lower haloalkyl having 1 or 2 carbon atoms.

35. A compound having the formula:

wherein Y is trifluoromethyl, chloro, or bromo, and R1 is hydrogen or methyl when Y is trifluoromethyl and R1 is methyl or ethyl when Y is chloro or bromo.

36. A herbicidal composition comprising a herbicidally effective amount of a compound according to Claim 1 as an active ingredient in admixture with a diluent or carrier.

37. A composition according to Claim 36 wherein such com-pound is a compound according to Claim 2 or 3.

38. A composition according to Claim 36 wherein such com-pound is a compound according to Claim 4 or 5.

39. A composition according to Claim 36 wherein such com-pound is a compound according to Claim 6 or 7.

40. A composition according to Claim 36 wherein such com-pound is a compound according to Claim 8 or 9.

41. A composition according to Claim 36 wherein such com-pound is a compound according to Claim 10 or 11.

42. A composition according to Claim 36 wherein such com-pound is a compound according to Claim 12 or 13.

43. A composition according to Claim 36 wherein such com-pound is a compound according to Claim 14 or 15.

44. A composition according to Claim 36 wherein such com-pound is a compound according to Claim 16 or 17.

45. A composition according to Claim 36 wherein such com-pound is a compound according to Claim 18 or 19.

46. A composition according to Claim 36 wherein such com-pound is a compound according to Claim 20 or 21.

47. A composition according to Claim 36 wherein such com-pound is a compound according to Claim 22 or 23.

48. A composition according to Claim 36 wherein such com-pound is a compound according to Claim 24 or 25.

49. A composition according to Claim 36 wherein such com-pound is a compound according to Claim 26 or 27.

50. A composition according to Claim 36 wherein such com-pound is a compound according to Claim 28 or 29.

51. A composition according to Claim 36 wherein such com-pound is a compound according to Claim 30 or 31.

52. A composition according to Claim 36 wherein such com-pound is a compound according to Claim 32 or 33.

53. A composition according to Claim 36 wherein such com-pound is a compound according to Claim 34 or 35.

54. A method for preventing or destroying plants or regu-lating the growth of plants which comprises applying a herbici-dally or plant growth regulating effective amount of a compound according to Claim 1 to a foliage or potential growth medium of said plants.

55. A method according to Claim 54 wherein such compound is a compound according to Claim 2 or 3.

56. A method according to Claim 54 wherein such compound is a compound according to Claim 4 or 5.

57. A method according to Claim 54 wherein such compound is a compound according to Claim 6 or 7.

58. A method according to Claim 54 wherein such compound is a compound according to Claim 8 or 9.

59. A method according to Claim 54 wherein such compound is a compound according to Claim 10 or 11.

60. A method according to Claim 54 wherein such compound is a compound according to Claim 12 or 13.

61. A method according to Claim 54 wherein such compound is a compound according to Claim 14 or 15.

62. A method according to Claim 54 wherein such compound is a compound according to Claim 16 or 17.

63. A method according to Claim 54 wherein such compound is a compound according to Claim 18 or 19.

64. A method according to Claim 54 wherein such compound is a compound according to Claim 20 or 21.

65. A method according to Claim 54 wherein such compound is a compound according to Claim 22 or 23.

66. A method according to Claim 54 wherein such compound is a compound according to Claim 24 and 25.

67. A method according to Claim 54 wherein such compound is a compound according to Claim 26 or 27.

68. A method according to Claim 54 wherein such compound is a compound according to Claim 28 or 29.

69. A method according to Claim 54 wherein such compound is a compound according to Claim 30 or 31.

70. A method according to Claim 54 wherein such compound is a compound according to Claim 32 or 33.

71. A method according to Claim 54 wherein such compound is a compound according to Claim 34 or 35.

72. A method for preparing the compound of Claim 1 wherein R is phenyl, naphth-1-yl, inden-1-yl or a substituted aryl as defined in Claim 1, and R1 and R2 are each hydrogen, which com-prises the step of contacting the corresponding compound having the formula:
(A) wherein X and Y are as defined in Claim 1, and Z' corresponds to the desired R aryl or substituted aryl substituent, with a halogen selected from the group consis-ting of chlorine, bromine and iodine and a liquid carboxylic acid thereby producing the corresponding compound of formula I.

73. The method of Claim 72 wherein said method is conduc-ted in an inert organic solvent at temperatures in the range of about from 0 to 100°C and said halogen is bromine.

74. The method of Claim 73 wherein excess liquid carboxy-lic acid is used as said inert organic solvent.