AU4270585A - Herbicidal crotonic acid derivatives - Google Patents

Description

PATE:NTS ACT 1952

APPLICATION FOR A STANDARD PATENT

,qgEqyRO$,RESEARCH COMPANY, of 200 Bush Street, San Francisco, elbolxlma California 94104, MR,

United States of 7nerica

hereby apply for the grant of a Standard Patent for an invention entitled:

which is described in the accompanying crovmplete -specification.

Details of basic application(s):- Number Convention _Country Date

623,050 ted States of America Unit, 21 June, 1984

Tfbe address for serviee is care of DAVIES COLLISON, Patent Attorneys, of 1 Little Collins Street, Melbourne, in the State of Vioeloria, Commonwealth of Australia.'- Dated this 21st day of May 19

gw- e4w To* THlE COMMISSIONER OF PATENTS 11 (a member of the firm of DAVIES COLLISON for and on behalf of the Applicant).

Davies Collison, Melbourne and Canberra.

COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 DECLARATION IN SUPPORT OF CONVENTION OR NON-CONVENTION APPLICATION FOR A PATENT

In support of the Application made for a patent for an invention sert title of invention, entitled- "HERBICIDAL H- DROXYPROP-2rYL 5-(2,4-DiSUn3STITUTED- PHENOXY) -2-SUBSTITUTED PHENOXY) CROTOSATE DERIVATIVIES" insert full name(s) and address(es) I James A. Buchanan, Jr. of decluranw(s) being the appli- cant($) or pctsonl(s) authorized to oft555 Market Street, San Franciscu, sign on behtiff of an applican.t California, United States of America company.

Cross out whichever of paragraphs I(a) or I does not apply do solemnly and sincerely declare as follows> 1, a) relates to application made by individual(s) 1(b) rolatea to applIcation made or(b) I am authorized by CHEVRON RESEARCH COMPANY by cmtyan5 insert name of applicc company.

Cross out) hichever of paragraphs the for the patent to make this declaration on its behalf. 214) or 2 b) doea not apply 4hoi- 2(s) tell%"ken to application made 2. .entes by ln'nor(s) We-afe selatea to application made or(b) DAVID CHEONG KING CHAN, a citizen of the United by company(s) or person(s) who States of lAmerica, residing at 305 Ridgeview Drive, are not inventor(a); inscrt full name(a) and address(ec) of inven- Petalumna, California 94i952, United States of America,

the actual inventor.....of tile invention and the facts upon which the applicant

entitled to make the application are as follows CHEVRON RESEARCH COMPANY 1& Ehb a§§ignio of the intvention and the r'ight to apply for Stats manner in Which applicant(s) derive (tiofrom Inventor(s) Letters Patent therefor in Australia from the said DAVID CREONG KING CHAN

Cross out paragraphs 3* and 4 3. The basic application as defined, by Section 141 of the Act was made for non-ece9ention applications. For co's~ention applications, in United States. of Americ n h 21st ay of June 1984t Insert bjAlc country(s) followed by date(%) and basic applicant(s). by. ,.DaVid.Cheong King..Chan. in the

on the by

4. Tile basic application.......referred to in paragraph 3 of 'this Declaration the first application.......made in a Convention country in respect of the invention the subject of the application. Insert place and datr of signature. Declared at San Fr'ancisco, this 29th day of April 1985 California, U.S.A. of declacant(s) (no Sig4nature ait~station requ~ired)

Note! Initial all alterations.

DAVIES COLLISON, MELBOURNE and CANBERRA.

U T.TrT hhT. T4VtwwwYVP'?P-2- YT. 4- r 2 ,4-DISUBSTITUTED-

(12) AUSTRALIAN PATENT ABSTRACT (19) AU (11) AU-A-42705/85

(54) HERBICIDAL CROTONIC ACID DERIVATIVES (71) CHEVRON RESEARCH COMPANY (22) 21.5.85 (24) 21.6.84 (21) 42705/85 (31) 623050 (32) 21.6.84 (33) US (43) 2.1.8C (51)4 C07C 69/736 C07C 79/355 A01N 39/02 (72) DAVID CHEONG KING CHAN (74) DM (57) Claim 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 example, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, The term "halo" or "halogen atom" or "halide" refers to the group of fluoro, chloro, bromo and iodo. T-e term "compatible salts" or "compatible cat- ions" refers to salts which do not significant-ly alter the herbicidal properties of the parent compound. Suitable salts include cation salts such as, for example, the cat- ion salts of lithium, sodium, potassium, alkali earth metals, ammonia, quaternary ammonium salts, and the like.

./2

D 3 21 MD

=105/59/7

(11) AU-A-42705/85 -2- A compound having the formula:

X

Y 0 Z O CH 3

O-CH-C CHCO-CHCH 2 0H

2 R1

wherein R and R 2 are independently hydrogen or lower alkyl; X is halo; Y is halo or trifluoromethyl; and Z is nitro or halo; and compatible salts thereof.

A method for preventing or destroying plants which comprises applying a herbicidally effective amount of the compound of Claim 1, or mixtures thereof, to the foliage or potential growth medium of said plants.

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

=105/59/8

-s-lv~r ana t-anverra.

C C m M 0 N W E A L T 11 OF AU0S TRA L IA

PATENTS ACT 1952

COMPLETE SPECIFICATION

(0r-igina1)-

FOR OFFICE USE

Class Int. Class Application Number: Lodged:

Complete Specification-Lodged: Accep ted: Published:

Priority:

Related Art:

ii X-7Osj11

Name of-Applicant: CHEVRON RESEARCH COMPANY

Address of Applicant: 200 Bush Street, San Francisco, California 94104, United States of America

Actual Inventor(s): DAVID CIVONG KYNG CHAN

-Address for Service: DAVIES COLLISON, Patent Attorneys, I.Little Collins Street, Melbourne, 3000.

Complete specification for the invention entitled: "HERBICIDAL~ HYDROXYPROP-2-YL 4- 4-DISUflSTITUTED- PHENOXY) -2-SUBSTITUTED PHENOXY) CROTONATE DERIVA~TIVES"

Tile following statement is a f ull description of th"'Is invention, ~.nludngthe best method of performing it known to us

HERBICIDAL HYDROXYPROP-2-YL 4-[5-(2,4-DISUBSTITUTED- PHENOXY)-2-SUBSTITUTED PHENOXY] CROTONATE DERIVATIVES

BACKGROUND OF THE INVENTION This invention relates to hydroxyprop-2-yl (2,4-disubstituted phenoxy)-2-substituted phenoxy] crotonates and to the use of such compounds as herbicides. At lower dosage rates, the compounds can be applied as plant growth regulators. A number of diphenoxy type herbicides are described in various publications. For example, U.S. Patent No. 4,163,661 discloses herbicidal alkyl esters of 4-methyl-4-[4-(4-trifluoromethylphenoxy)-phenoxy] crotonic acid; U.S. Patent No. 4,093,446 discloses herbicidal 4-trifluoromethyl-4'-nitrodiphenyl-2'-alkoxyethers and U.S. Patent No. 4,134,753 discloses herbicidal 4-halo-4'- nitro-3'-alkanoyloxy diphenyl ethers. Other diphenoxy ether herbicides are described in U.S. Patent 4,221,581 and published German application 2 905 458. U.S. Patent No. 4,419,123 discloses multisubstituted diphenoxy ether herbicides and set forth an extensive testing of various substituents which may be meta to the phenoxy linkage. In my prior U.S. Patent 4,414,017 and British Patent No. 2,079,271, I disclosed herbicidal esters and salts of 4-[5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro- phenoxyl-crotonic acid. European Patent Application No. 34,120 of Meyer et al, published August 19, 1981, also discloses similar compounds and the 2-chlorophenoxy ana- logs thereof. SUMMARY OF THE INVENTION The present invention provides herbicidal com- pounds having both pre- and post-emergence activity against both grassy weeds and broad-leaf plants. The compounds have especially excellent pre-emergence activity against broad-leaf plants and have sufficient selectivity that they may be effectively and safely apply to control broad-leaf weeds in certain grassy crops; notably rice.

The compounds of the present invention can be represented by the generic formula:

X 4

Y O 2Z '6 R R2 O CH 3 "O-CH-C=CHCOCH-CH 2 0H (I)

wherein R1 and R2 are independently hydrogen or lower alkyl having 1 through 4 carbon atoms; X is halo; Y is halo or trifluoromethyl; and Z is nitro or halo. Compatible salts of the above compounds are also encompassed within the invention. The compounds have an asymmetric carbon atoms and can exist as optical isomers. The compounds also exist as geometric isomers with respect to the double bond. 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. In a further aspect, the invention provides a herbicidal composition comprising a compatible carrier and

a herbicidally effective amount of the compounds of Formula or compatible salts thereof, or mixtutes 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 the foliage of such vegetation with a herbicidally effec- ti'ie amount of the compound(s) of Formula and/or com- patible 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 compatible salts of Formula 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 the growth medium and/or the foliage of such vegetation with a plant growth regulating effective amount of the com- pound(s) of Formula 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 The invention will be further described herein- below. FURTHER DESCRIPTION OF THE INVENTION AND THE PREFERRED EMBODIMENTS Illustrations of typical compounds of Formula of the present invention can be had by reference to Examples 1 and 2, set forth hereinbelow on pages 10 and 13. In terms of substituents, the preferred compounds are those wherein Y is trifluoromethyl, X is chloro, Z is 1 2 nitro or chloro, more preferably nitro. R and R are independently hydrogen, methyl or ethyl. More preferably, 1 2 one of R or R is hydrogen and the other is hydrogen, or methyl. Most preferably, R 1 is methyl and R 2 is hydrogen. The preferred compounds have at least one preferred sub- stituent and more preferably have a combination of two or more preferred substituents. The compounds of the present invention can be conveniently prepared via reaction of the corresponding di(phenoxy)crotonic acid analogs with propylene oxide. This can be schematically represented by the overall reac- tion equation: y 0 Z H 2 C--CHCH 3 I 0I, (B) 0-CHC=CHCOH I I R R2 wherein R 1 R2 X, Y and Z are as defined here- inabove. This preparation can be effected by contacting Compound with Compound (propylene oxide) under reactive conditions preferably in an inert organic solvent. It has further been found that good results are obtained when the reaction is further conducted in the presence of a trimethylsulfoxonium halide (e.g.,trimethyl- sulfoxonium iodide). It is conjectured that this improves the reaction by forming the alkyl ester of Compound (A) and liberating hydrogen halide, because the alkyl ester is more readily converted to an alcohol than the acid. More- over, hydrogen halides catalyze the conversion to the alcohol. Typically, this process is conducted at tempera- tures in the range of about from 200 to 150 0 C, preferably 78' to 105°C for about from 1 to 48 hours, preferably, 8 to 24 hours using about from 1 to 25 moles, preferably 1 to 10 moles of propylene oxide per mole of Compound Where a trimethylsulfoxonium halide is used, typically about from 0.10 to 1 mole, preferably 0.15 to 0.50 mole are used per mole of Compound Typically, trimethylsulfoxonium iodide or bromide is used. Suitable inert organic solvents which can be used include, for example, ethanol, dichloromethane, toluene, 1,2-di- methoxyethane, and the like and compatible mixtures thereof. The starting materials of Formula are gener- ally known compounds and can be prepared by known procedures or obvious modification thereof via the substi- tution of appropriate solvents and appropriately substi- tuted starting materials. The compounds of Formula A wherein Z is nitro, are, for example, generally described in my prior U.S. Patent No. 4,414,017. The compounds of Formula A wherein Z is chloro are generally described in published European Patent Application 34120. The compatible salts of Formula can be pre- pared by conventional procedures. For example, the salts can. be prepared by treating the compound of Formula (I) with a suitable base, such as, for example, n-butyl- lithium, sodium hydride, potassium hydride, and the like, having the desired cation, to yield the corresponding salt. Additional variations in the salt cation can also be effected via ion exchange with an ion exchange resin having the desired cation. General Process Conditions In the above-described processes, it isgenerally 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 reactioa product mixtures by any suitable separation and purification procedure, such as, for example, recrystallization and chromatography. Suit- able separation and purification procedures are, for exa-n- ple, illustrated in the Examples set forth hereinbelow. 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 reactiontempera- tures, times, mole ratios of reactants, solvents, etc.)

,ihP1~~3(~

01 -6-

have been given, that other process conditions could also be used. Optimum reaction conditions 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 differences in physical properties between the geometric isomers. Definitions 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 4 carbon atoms and includes primary, secondary and tertiary alkyl groups. Typical lower alkyls include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl. The term "halo" or "halogen atom" or "halide" refers to the group of fluoro, chloro, bromo and iodo. The term "compatible salts" or "compatible cat- ions" 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 cat- ion salts of lithium, sodium, potassium, alkali earth metals, ammonia, quaternary ammonium salts, and the like. The term "room temperature" or "ambient tempera- ture" refers to about 20-25 0 C. Utility The compounds of Formula exhibit both pre-emergence and post-emergence herbicidal activity and exhibit especially good herbicidal activity against broad- leaf plants. Generally, for post-emergent applications, the herbicidal compounds are applied directly to the foliage

01 -7-

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 sheltered areas such as greenhouses compared to exposed areas such as fields), and type and degree of control desired. Generally, for both pre- and post-emergent control, the present compounds are applied at rates of about from 0.02 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 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) is one which does not significantly 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 or mixtures thereof. Concen- trates 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, solu- tions, 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 alumi- nosilicate, 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 hydrocarbons such as benzene, toluene, dimethylsulfoxide, kerosene, diesel fuel, fuel oil, petroleum naphtha, etc.), and the like. Suitable aerosol carriers which can be used include con- ventional aerosol carriers such as halogenated alkanes, etc. The composi- on can also contain various promo- ters and surface-active agents which enhance the rate of transport 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 compat- ible adjuvants, stabilizers, conditioners, insecticides, fungicides, and if desired, other herbicidally active compounds. At reduced dosages the compounds of the present invention can be used to alter the normal growth pattern of plants. The compounds of Formula 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 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, and insecticides. Typically, the plant growth regulating composition will contain a total of about from 0.005 to wt. of the compound(s) of Formula 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 Example(s). Wherein, unless expressly stated to the

S-9-

contrary, all temperatures and temperature ranges refer to the Centigrade system and the term "ambient" or "room temperature" refers to about 20-25 0C. 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 recited in that example in terms of finite moles or finite weight or volume. Where given, proton-magnetic resonance spectrum or were determined at 60 mHz, signals are assigned as singlets broad singlets doublets double doublets triplets double triplets quartets and multiplets and cps refers to cycles per second. Also where necessary examples are repeated to provide additional starting material for sub- iequent examples. FXAMPLES Example 1 3-Hydroxyprop-2-yl-4-[5-(2-chloro-4-trifluoro- methylphenoxy)-2-nitrophenoxy]-4-methylcrotonate In this example, a mixture containing 10.9 g of 4-[5-(2-cloro-4-trifluoromethylphenoxy)-2-nitrophenoxy]-4- methylcrotonic acid, 10 g of propylene oxide and 1 g of trimethylsulfoxonium iodide in 150 ml of ethanol was refluxed for 24 hours and then filtered. The filtrate was evaporated and the residue redissolved in ethyl ether and again evaporated. The residue was chromatographed over silica gel eluting with mixtures of ethyl ether and petro- leum ethers affording the title compound as an oil Elemental Analysis Carbon: Calc. 51.49%, Found 51.66%; Hydrogen: Calc. 3.92%, Found 4.32%; Nitrogen: Calc. 2.86%, Found 2.86%. Similarly, by applying the above procedures to the corresponding crotonic acid analogs, the following compounds can be prepared: 3-hydroxyprop-2-yl 4-[5-(2-fluoro-4-trifluoromethyl- phenoxy)-2-nitrophenoxy]-4-methilcrotonate; 3-hydroxyprop-2-yl 4- 5-(2-bromo-4-trifluoromet'nyl- phenoxy)-2-nitrophenoxy] -4-me thyicrotonate; 3-hydroxyprop-2-yl 4- 2-iodo--4-trifluoromethyl- phenoxy)-2-nitropherioxy]-4-mhethylcrotonate; 3-hydroxyprop-2-yl 4- 2-chloro-4-fluorophenoxy)-2- nitrophenoxyl-4-methylcrotonate; 3-hydroxyprop-2-y. 4- 2-iodo--4-chlorophenoxy)-2- nitrophenoxy] -4-mnethylcrotonate; 3-hyciroxyprop-2-yl 4- 2-fluoro-4-bromophenoxy) -2- nitrophenoxy] -4-methyicrotonate; 3-hydroxyprop-2-yl 4-[5-(2,4-dichlorophenoxy)-2- nitroohenoxyl-4-methylcrotonate; 3-hydroxyprop-2j4 4- [5-1 2.4-difluorophenoxy)-2- -4-inethylcrotonate; 3-hy'droxyprop-2-y. 4-15-(2-chloro-4-trifluoromethyl- phenoxy) -2-nitrophenoxyl -crotonate; 3-hydroxyprop-2-yl 4- 2-iodo-4-trifluoromethyl- phenoxy )-2-nitrophenoxy] -crotonate; 3-hydroxyprop-2-y. 4- 2-iodo-4-trifluoromethyl- phenoxy)-2-nitrophenoxy] -crotonate; 3-hydroxyprop-2-yl 4-15-(2-chloro-4-fluorophenoxy)-2- nitroph-enoxyl -crotonate; 3-hydroxyprop-2-yl 4- 2-chl1-:o-4-trifluoromethyl- phenoxy )-2-nitrophenoxyl -3-methyicrotonate; 3-hydroxyprop-2-yl 4- 2-bromo-4-iodophenoxy)-2- nitrophenoxy] -3-methylcrotonate; 3-hydroXyprop-2-yl 4- [5-(2-chloro-4-trifluoromethyl- phenoxy )-2-nitrophenoxyl -4-ethylcrotonate; 3-hydroxyprop-2-yl 4-[L5- (2-chioro-4-trifluoromethyl- phenoxy )-2-nitrophenoxyl -3-ethyicrotonate; 3-hydroxyprop-2-yl 4- [5-(2-chloro-4-trifJluoromethyl- phenoxy )-2-aitrophenoxyl -4-propyicrotonate; 3-hydroxyprop-2-yl 4- [5-(2-chloro-4-trifluoromethy1- phenoxy)-2-nitrophenoxy] -3-butylc'rotr<-, 3-hydroxyprop- -yl 4- 2-chloro-4-trifluoromethyl- phenoxy -2-nitrophenoxy I-4-isopropyicrotonate; 3-hydroxyprop-2-yl 4- (2-chloro-4-trifluoromethyl- phenoxy )-2-nitrophenoxy 11-3-t-butylcrotonate;

)tonate; 3-hydroxyprop-2-yl 4- 2-chloro-4-trifluoromethyl- '-4-trifluoromethyl- phenoxy)-2-nitrophenoxy] 4-dimethyicrotonate, 'tonate; 05' 3-hydroxyprop-2-yl 4- (2-chloro-4-trifluorometb-il- >ro-4-fluorophenoxy phenoxy)-2-nitrophenoxy] 4-dibutyicrotonate;, 3-hydroxyprnp-2-yl 4- [5-(2-chloro-4-trifluoromethyl- 4 -chlorophenoxy phenoxy)-2-nitrophenoxyl -ethyl-4-propylcrotoflate; hydroxyprop-2-yl 4- [5-(2-chloro-4-trifluoromethyl-. >ro-4-bromophenoxy) -2- 10 phenoxy)-2-chJlorophenoxy] -4-methylcrotoriate; 3-hydroxyprop-2-yl 4-15- (2-broio-4-trifluorometh-b- chlorophenoxy 1-2- phenoxy )-2-chlorophenoxy] -4-methyicrotonate; 3-hydroxyprop-2-y- 4-[I5-(2-iodo-4-trifluoromethy]l- fluorophenoxy phenoxy) )-2-chlorophenoxyl -4-methylcrotonate; 3-hydroxyprop-2-yl 4- (2-chloro-4-fluorophenoxy)-2- ro-4--trifluoromethyl- chlorophenoxy] -4-met hyicrotonate; 3-hydroxyprop-1--yl 4- 2-iodo-4-chloropheloxy)-2- -4-trifluoromethyl- cilorophenoxy] -4-methyicrotonate; 3-hydrox~yprop-2--yl 4- (2-fluoro-4-bromopheloxy)-2- -4-trifluoromethyl- 20 chiorophenoxyl -4-methyicrotonate; 3-hydroxypron-2-yl 4- (2,4-dichlorophenoxy)-2-ch10- ro-4-fluorophenoxy rophenoxy] -4-methyicrotonate; 3-bydroxyprop-2-yl4- 4-difluorophenoxy) -2-chlo- o- 4 -trifluorome thyl- ropheno.-y) -4-methyicrotonate; tonate; 25 3-hydroxyprop-2,--yl 4-[5-(2-chloro-4-trifluoromfethyl- o-4-iodophenoxy) -2- phenoxy )-2-chlorophenoxy] -crotonate; 3-hydroxyprop-2-yl 4- 2-iodo-4-trifuoromethyl- ro-4-tri fJuorome thy 1- pcienoxy)-2-chlorophenoxyI -crotonate; :flate; 3-hydroxyprop-2-yl 4- (2-iodo-4-tritJ-uoromethy- ro-4-tri fluoromethyl- 30 phenoxy)-2-chlorophenoxyl -crotonate; :)nate; 3-hydroxyprop-2-yl 4- (2-chloro-4-fluorophenoxy)-2- co- 4 -trifluoromethyl- chlorophenoxy] -crotonate; tonate; 3-hydroxyprop-2-yl 4- (2-chloro-4-trifluoromethyl- co 4 -trifluoromethyl- 15 phercy)-2-chlorophenoxy]-3-atethylcrotofate; 3-hydroxyprop-2-yl 4-f 5- (2-bromo-4-iodophenoxy)-2- ro- 4 -tri fluoromethyl- chiorophenoxyl -3-methyicrotonate; ::rotonate; 3-hydroxyprop-2-yl 4- [5-(2-chloro-4-trifluoromethyl- o- 4 -trifluoromethyl- pheno)-2-chloropheflCxyJ4-ethylcrotonate; )tonate;- 40 3-hydroxyprop-2--yl 4-[5-(2-chloro-4-trifluoromethy.-- phtec-oxy 2-chlorophenoxy.- 3-ethyicrotonate;

-19-

The compound of Claim 8 wherein X is chioro and

01 -1

3-hydroxyprop-2-y1 4- [5-(2-chlor'o-4-trifluoromethyl- phenoxy)-2-nitrophenoxy]-3 ,4-dimethylcrotonate; 3-hydroxyprop-2-yl 4- (2-chloro-4 ',trifluoromethy1- phenoxy)-2-nitrophenoxy]-3 ,4-dibutylcrotonate; 3-hydroxyprop-2-yl 4- [5-(.2-cbioro-4-trifluoromethyl- phenoxy)-2-nitrophenoxy]-3-ethyl-4-propylcrotonate; hydroxyprop-2-yi 4- 2-chloro',.-4-trifluoromethyl- phenoxfr-2-chlor6phenoxy] -4-methylocrotonate; 3-hydroxyprop-2-y. 4- (2-bromo-4-trifluoromethyl- phenoxy)-2-chlor-op.henoxyJ -4-methyicrotonate; 3-hydroxyprop-2-yl 4- [5-(2-iodo-4-trifluoromethyl- phenoxy) )-2-ohlorophenoxy]-4-methlylcrotonate; -hydroxyprop-2-yl 4- 2-chloro-4--fluorophenoxy)-2- chiorophenoxy] -4-me thyicrotonate; 3-hvdroxyprop-2-kii 4- 2-iodo-4-chlorophenoxy)-2- chiorophenoxy] -4-me thyicrotonate; 203-hydroxyprop-2-yJ 4- (2-f luoro-4-.bromophenoxy)-2- chior .ophenoxy]-4-methylcrotonate; 3-hydroxyprop-2-yl 4- [5-(2,4-dichlorophenoxy)-2-chlo- rophenoxy] -47methylcrotoiate; 3-hydroxyprop-2-y14- [5-C 2,4-difluorophenoxy)-2-chlo- rophenoxy] -4-methylcrotonate; 3-hydroxyprop-2-yl 4- 2-chloro-4-trifluoromethyl- phenoxy)-2-chlorophenoxy] -crotonate; 3-hydroxyprop-2-yl 4- [5-C 2-iodo-4-trifluoromethyl- phenoxy)-2-chlorophenoxy] -crotonate; .3-hydroxyprop-2-y. 4- (2-iodo-4-trifluoromethyl-

3-hydroxyprop-2-yi 4- (2-chloro-4-fluorophenoxy *chlorophenoxy-croton ,te;- 3-hydroxyprop-2-yl 4- (2-chioro- 4-trifluoromethyl- phenoxy)-2--chlorophenoxy1-3-methylcrot Inate; 3-,hydroxyprop-2-yl 4- (2-bromc-4-iodophanoxy)-2- chlorophenoxy] -3-me thylcrf nxate; 3-hydroxyprop-2-y-I 4- [5-(2-chloro-4-trifluoromethyl- phenoxy )-2-chloropheioxyj -4-ethyicrotonate;

3-hydroxyprop-2-yl 4- [5-(2-chloro-4-trifluoromethyl- phenoxy)-2-chlorophenoxyl',-3-ethylcrotonate;

01 -12-

3-hydroxyprop-2-yl4- (2-chloro-4-trifluoromethyl- -pherioxy)-2-chiorophenoxy] -4-propyicrotonate; 3-hydroxyprop-2-yl 4- (2-chloro-4-trifluorornethyl- phenoxy)-2-chlorophenoxy] -3-butylcrotonate; 3-hydroxyprop-2-yl 4- (2-chloro-4-trifluoromethyl- phenoxy )-2-chiorophenoxyl-4-isopropyicrotonate; 3-hydroxyprop--2-yl 4- (2-chloro-4-trifluorome thy 1- phenoxy )-2-chlorophenoxy] -3-t-butylcrotonate; 3-hydroxyprop-2-yl 4- (2-chloro-4-trifluoromethyl- phenoxy)-2-chlorophenoxyl -3 ,4-dimethylcrotonate; 3-hydroxyprop-2-yl 4- (2-chloro-4-trifluoromethy 1- phenoxy )-2-chiorophenoxyl 4-dibutyicrotonate; 3-hydroxyprop-2-yl 4- (2-chloro-4-trifluoromethyl- phenoxy)-2-chlorophenoxyl-3-ethyl-4-propylcrotonate. Example 2 Sodium salt of 3-hydroxyprop-2-yl-4- (2-chloro-4- trifluoromethylphenoxy)-2-nitrophenoxy] 2-me thy icrotonate The title compound can be prepared by the following procedure* 0.54 g of sodium hydride is added portion- wise to a stirred solution containing 5.5 gm (0.0112 mole) of 3-hydroxyprop-2-yl-4- 2-chloro-4-trifluoromethyl- phenoxy)-2-nitrophenoxyl-2-methylcrotonate in 100 ml of anhydrous ethyl ether at room temperature under a nitrogen atmosphere. After the evolution hydrogen ceases two drops of ethanol are added to destroy unreacted sodium hydride. The reaction mixture is filtered through magnesium sulfate. The filtrate is then evaporated, under vacuum, to afford the title compound as the residue. Similarly, by applying the above procedure to the compounds illustrated in Example 1, the corresponding sodium salts thereof can be prepared.

El

Example 3 In this example, the title compound of Example 1 was tested 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 using the procedures described hereinbelow. Pre-Emergent Herbicide Test Pre-emergence herbicidal activity was determined in the following manner. A test solution of the compound was prepared as follows: 355.5 mg of test compound was dissolved in 15 ml of acetone. 2 ml of acetone containing 110 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/1. Seeds of the test vegetation were planted in a pot of soil and the test solution was sprayed uniformly onto the soil surface at a dose of 27.5 micrograms/cm 2 The pot was watered and placed in a greenhouse. The pot was watered intermittently and observed for seedling emer- gence, health of emerging seedlings, etc., for a 3-week period. At the end of this period, the herbicidal effec- tiveness of the compound was rated based on the physiolo- gical 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. Post-Emergent Herbicidal Test The test compound was formulated in the same 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 15 to 25 plants per pot) at a dose of 27.5 microgram/cm 22 After the plants had dried, they were placed in a greenhouse and then watered intermittently at their bases as needed. The plants were observed periodic- ally for phytotoxic effects and physiological and morpho- logical 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.

TABLE 1

Pre-Emnergence Herbicidal Activity Application Rate: 27.5 micrograms/cm 2 unless otherwise noted

Broad-Leaf Plants Compound Phytotoxicity %phytotoxicitk- No. Lambsquarter Mustard Pigweed Soybean Watergrass Crabgrass Wild oats Rice 1 100 100 100 100 ition comprising a regulating amount of

TABLE 1 Pre-Emergence Herbicidal AS H- 0 Application Rate: 27.5 micrograms/cm 2 ur Broad-Leaf Plants Compound Phytotoxicity (D No. Lambsguarter Mustard Pigweed Soybean iWa

100 100 100 100

CD 0 0 CD xC0 ti ti1 t

I,.

0

CD

CD~

CD

0 rr (D

S S S S S S S S S S S 555 S S S S S S .55 S 0* 5 S. S S S S S S 55 5 5@ S 555 S S S S S S S 5 65-5 S 555 5 55* ally known compounds and can be prepared by known

TABLE 1

Pre-Emergence Herbicidal Activity

Application Rate: 27.5 micrograms/cm 2 unless otherwise noted

Broad-Leaf Plants Grasses Phytotoxicity Phytotoxicity Lambsquarter Mustard Pigweed Soybean Watergrass Crabgrass Wild Oats Rice

100 100 100 100 100 93 93

a a a 0 a.. a a a a. S S a S S S S a aes a. a a 0. a a S 0 0 5 a. a a. 0 a tao a a a a a a a. a~ S a OS. S *tS 0 aa a a a

TABLE 2

Post-Emergence Herbicidal Activity

Application Rate: 27.5 micrograms/cm 2 unless otherwise noted

Broad-Leaf Plants Grasses Compound Phytotoxicity Phytotoxicity No. Lambsquarter Mustard Pigweed Soybean Watergrass Crabgrass Wild Oats Rice

1 100 100 100 45 50 35 50

A

.,react jontempera- Generally, for post-emergent applications, the herbicidal compounds are applied directly to the foliage .ts, solvents, etc.)

-16-

TABLE 2

Post-Emergence Herbicidal Ac

Application Rate- 27.5 micrograms/cm 2 un

Broad-Leaf Plants Compound Phytotoxicity No. Lambsguarter Mustard Pigweed Soybean 'Wat

100 100 100

S 0@9 S 9** 99 .9.9 9 99 9 @09 9 9 S. 9 9 0 99 09 9 99. 9 9 9 059 9 990 9 9 9 t applications, the flour, cotton-seed hulls, wheat flour, wood flour, wood ctly to the foliage bark flour, and the iike can also be used as carriers. Suitable liquid d iluents which can be used include, for

-16-

TABLE 2

Post-Emergence Herbicidal Activity Application Rate: 27.5 micrograms/cm 2 unless otherwise noted

Broad-Leaf Plants Grasses Phytotoxicity Phytotoxicity Lambsguarter Mustard Pigweed Soybean Watergrass Crabgrass Wild Oats Rice 100 100 100 45

S S S o 5 SOS SOS S S S S 55 S SO U S S S S SSS 55 S 5S S S S S S S *o S S 0, SOO S S SS SO 0 0 S 555 5 5 S S S

01 Obviously, many modifications and variations of the invention described hereinabove and below in the claim8 can be made without departing from the essence and scope thereof.

o

r-r

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ai:

On

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,paration and 3-hydroxyprop-.2-yl 4- (2-bromno-4-trifluoromethy1. .y stated to the

is and variations of id below in the rom the essence and

7/4

Claims (19)

nate; phenoxy)-2-nitrophenoxy]-3-t-butylcrotonate; 4-trifluoromethyl- -18- THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS

1. A compound having the formula:

0 CH 3

O-CH-C=CHCO-CHCH 2OH

2 RiI R2

wherein R1 and R2 are independently hydrogen or lower alkyl;

7I X is halo; Y is halo or trifluoromethyl; and Z is nitro or halo; and compatible salts thereof.

2. The compound of Claim 1. wherein Y is trifluoro- me thy

3. The compound of Claim 1 wherein X is chloro.

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

The compound of Claim 4 wherein R2 is hydr cen.

6. The compound of Claim 5 wherein R is methyl or eth; I

7. The compound of Claim 6 wherein R 1 is methyl.

8. The compound of Claim 7 wherein Y is trifluoro- methyl,

9. The compound of Claim 8 wherein X is chloro and Z is nitro.

The compound of Claim 8 wherein X is chloro and Z is chloro.

11. The compound of Claim 1 wherein Z is nitro.

12. The compound of Claim 1 wherein Z is chloro.

13. A herbicidal conmsition comprising a herbici- dally effective amount of the compound of Claim 1, or mixtures thereof, and a compatible carrier.

14. A herbicidal composition comprising a herbici- dally e.*ictive amount of the compound of Claim 9, or mixt !s thereof, and a compatible carrier.

A method for preventing or destroying plants which comprises applying a herbicidally effective amo'nt of the compound of Claim 1, or mixtures thereof, to the foliage or potential grow medium of said plants.

16 A method for preventing or destroying plants which comprises apolying a herbicidally effective amount of the compound of Claim 9, or mixtures thereof, to the foliage or potential growth medium of said plants.

17, A plant growth regulating composition which comprises an amount of the compound of Claim 1, or mix- tures thereof, effective to alter the growth pattern of plants.

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

Sv

19. A compound of claim 1 or a composition comprising

a said compound, or methods for the use thereof,

substantially as hereinbefore described with reference

to the Examples.

The steps, features, compositions and compounds

referred to or indicated in the specification and/or

claims of this application, individually or collectively,

and any and all combinations of any two or more of

said steps or features.

Dated this 20th day of May, 1985

CHEVRON RESEARCH COMPANY By its Patent Attorneys DAVIES COLLISON t* uoromethy 1- ion comprising rith reference

Lfld compounds

ttzion and/or

or collectively,

)r more of

May, 1985