IL41766A - Diphenyl ethers and their use as herbicides - Google Patents

Diphenyl ethers and their use as herbicides

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Publication number
IL41766A
IL41766A IL41766A IL4176673A IL41766A IL 41766 A IL41766 A IL 41766A IL 41766 A IL41766 A IL 41766A IL 4176673 A IL4176673 A IL 4176673A IL 41766 A IL41766 A IL 41766A
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Israel
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trifluoro
compound
alkoxy
tolyl
carbon atoms
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IL41766A
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IL41766A0 (en
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Rohm & Haas
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Priority claimed from US234656A external-priority patent/US3888932A/en
Priority claimed from US331719A external-priority patent/US3928416A/en
Application filed by Rohm & Haas filed Critical Rohm & Haas
Publication of IL41766A0 publication Critical patent/IL41766A0/en
Publication of IL41766A publication Critical patent/IL41766A/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/07—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms
    • C07C205/11—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms having nitro groups bound to carbon atoms of six-membered aromatic rings
    • C07C205/12—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms having nitro groups bound to carbon atoms of six-membered aromatic rings the six-membered aromatic ring or a condensed ring system containing that ring being substituted by halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
    • C07C205/35—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C205/36—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
    • C07C205/38—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the oxygen atom of at least one of the etherified hydroxy groups being further bound to a carbon atom of a six-membered aromatic ring, e.g. nitrodiphenyl ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/39—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups
    • C07C205/42—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups having nitro groups or esterified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C205/43—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups having nitro groups or esterified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
    • C07C205/57—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C205/59—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton the carbon skeleton being further substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C275/32—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by singly-bound oxygen atoms
    • C07C275/34—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by singly-bound oxygen atoms having nitrogen atoms of urea groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C275/36—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by singly-bound oxygen atoms having nitrogen atoms of urea groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring with at least one of the oxygen atoms further bound to a carbon atom of a six-membered aromatic ring, e.g. N-aryloxyphenylureas
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

1423376 Diphenylether derivatives ROHM & HAAS CO 13 March 1973 [14 March 1972 (2) 12 Feb 1973 (2)] 11954/73 Heading C2C The invention comprises compounds of the formula where X is hydrogen, halogen, trihalomethyl, C 1 -C 4 alkyl or cyano and (i) Y is halogen, trihalomethyl or, except where X is chlorine, hydrogen and Z is hydrogen or (ii) Y is hydrogen, halogen or trihalomethyl and Z is alkoxy, alkoxyalkoxy, hydroxyalkoxy, carboxyalkoxy, carbalkoxyalkoxy, halogen, alkylthio, alkyl, amino substituted with a dialkylcarbamoyl group, one or two alkyl groups, an alkylcarbonyl group or a carbalkoxy group, carboxy, carbalkoxy, carboxyalkyl or carbalkoxyalkyl. The compounds may be prepared by reacting a suitably substituted phenol or the potassium or sodium salt thereof with a halobenzene compound, or by introducing a substituent into a diphenyl ether. The compounds may be used as herbicides. [GB1423376A]

Description

am wiD'wni o»»nn ο»ιηκ V'JB'T Novel dlphenyl ethere and their use as herbicidee ROHM AND HAAS COMPANY 0· 39945 This invention concerns novel compounds which show activity as herbicides, to novel herbicidal compositions which contain these compounds, and to new methods of controlling weeds with these herbicidal compositions.
Certain diphenyl ethers have been shown to be effective weed control agents. However, the herbicidal effectiveness of a given diphenyl ether cannot be predicted from an examination of the substituent groups attached to the phenyl rings in the ether, and often quite closely related compounds will have quite different weed control abilities. Various diphenyl ethers may have overlapping or complementary areas of activity or selectivity, and can thus be useful in .combination to control a variety of weeds upon application of a single composition. Furthermore, the diphenyl ethers heretofore disclosed as herbicides are not completely effective. An ideal herbicide should give selective weed control, over the full growing season, with a single administration at low rates of application. It should be able to control all common weeds by killing them as the seed, the germi-. nating seed, the seedling, and the growing plant. At the same time, the herbicide should not be phytotoxic to the crops to which it is applied and should decompose or otherwise be dissipated so as not to poison the soil permanently. 41766-2 The known diphenyl ether herbicides fall short of these ideals, and it would thus be desirable to have new herbicides which show even more selective control of undesirable plants among desirable crop plants or which complement the known diphenyl ethers in activity.
In accordance with the present invention, there is provided a new class of novel diphenyl ethers having the formula wherein X is hydrogen; halogen, preferably fluorine or chlorine; trifluoromethyl; (C^-C^) alkyl and preferably methyl; or cyano, Y is hydrogen or halogen, preferably fluorine or chlorine, and, Z is hydrogen or a substituent group or atom as defined below.
The known diphenyl ether herbicides fall short of these ideals, and it would thus be desirable to have new herbicides which show even more selective control of undesirable plants among desirable crop plants or which complement the known diphenyl ethers in activity.
In accordance with the present invention, there is provided a new class of novel diphenyl ethers having the formula wherein X is hydrogen; halogen, preferably fluorine or chlorine; trifluoromethyl; (C^-C^) alkyl and preferably methyl; or cyano, Y is hydrogen or halogen, preferably fluorine or chlorine, and, Z is hydrogen or a substituent group or atom as defined below^with the proviso that X Y and n»yo Z cannot all be hydrogen. 41766/3 When Z is other than hydrogen, it represents: (1) alkoxy, (2) alkoxyalkoxy having 1 to 4 carbon atoms in each alkoxy moiety, (3) hydroxyalkoxy of up to 4 carbon atoms, (4) carboxy(C^-C^)^alkoxy, in free acid or salt form, (5) carbal-koxyalkoxy (-OR'COOR) containing up to 4 carbon atoms in each alkoxy group, (6) halogen, preferably chlorine or fluorine, (7) (C^-Cg) alkyl, (8) amino substituted with two alkyl groups contributing a total of up to 6 carbon atoms (e.g. a di(C^-C3alkyl)-amino group), an alkylcarbonyl group of u to 4 carbon atoms, (9) carboxy in free acid or salt form, or (10) carbalkoxy of up to 5 carbon atoms.
Alternatively when Z is other than hydrogen, it represents: (1) an alkoxy group of 1 to 4 carbon atoms substituted with a dialkylamino group having up to 4 carbon atoms, a trifluoromethyl, a (C^-C^)alkylcarbonyl, a halo-substituted (C1-C4)alkylcarbonyl, an epoxy, a (Cj-C^alkylthio, a (C1-C4)alkylsulfonyl,a carbamoyl, a mono-or di- (C^-Cj)alkyl-carbamoyl, a(C2-C4)alkenyl or a (C2-C4)alkynyl group, (2) a dihydroxy(C1-C4)-alkoxy group, (3) morpholino, (4) (Cj-C^)-alkyl I (Cj-C^-hydroxyalkyl or (Cj-C^alkylcarbamoyl] amino, (5) (C^C^jJ-alkylcarbamoylamino, (6) (Cj-C^hydroxyalkyl, (7) mono- or di-iC^-C^) alkylthiocarbonylamino, (8) cyano, (9) (Cg-C^)-> alkanoyloxy (-OCOR), (10) carbamoyloxy(-0C0NH2) , (ll) alkyl-carbamoyloxy (-0C0NHR) having up to 6 carbon atoms, (12) hydroxy or (13) amino.
In the above definitions of the Z substituent, R represents an alkyl group, and R' represents a divalent alkylene group. The alkyl or alkylene portion of the alkyl-containing X and Z substituents can be either straight- or branched-chain.
When Z in Formula I is hydrogen, typically X is halogen or cyano and Y is hydrogen or halogen. For example, X may be chlorine and Y hydrogen. 41766/2 Examples of the compounds of the invention embraced by Formula I include: LIST A afa,a-trifluoro-p_-tolyl-4-nitrophenyl ether, 2,a,a,a-tetrafluoro-p_-tolyl-4-nitrophenyl ether, ·, 2-bromo-a,a,a-trifluoro-£-tolyl-4-nitrophenyl ether, 2-chloro-a,a,a-trifluoro-£-tolyl-4-nitrophenyl ether, a,a,a-trifluoro-2-iodo-£-tolyl-4-nitrophenyl ether, 2, 6-dichloro-a,a,a-trifluoro-£-tolyl-4-nitrophenyl ether 2-chloro-6,a,a,a-tetrafluoro-£-tolyl-4-nitrophenyl ether 2-cyano-a,a,a-trifluoro-£-tolyl-4-ni rophenyl ether, 2-cyano-6,a,a,a-'tetrafluoro-£-tolyl-4-nitrophenyl ether, 2-cyano-6-chloro-a,a,a-trifluoro-£-tolyl-4-nitrophenyl ether, a,a,aja'ta tf-hexafluoro-2,4-xylyl-4-nitrophenyl ether, 6-chloro-a,a,.ata^a'/Qc"^hexafluoro-2,4-xylyl-4-nitrophenyl ether, 4 4 4 a ,a ,a -trifluoro-2,4-xylyl-4-nitrophenyl ether, 2-buty1-a,a,a-1rif1uoro-£-to1y1-4-nitropheny1 ether, 2-chloro-6-ethyl-a,a,a-trifluoro-£-tolyl*-4-nitrophenyl etter, ' ' LIST B 2-chloro-a,a,a-trifluoro~£-;tolyl~4-nitro-m-tolyl ether, 2-bromo-a,a,a-trifluoro-p_-tolyl-3-butyl-4-nitrophenyl ehter, 2,a,a,a-tetrafluoro-£-tolyl-4-nitro-3- -propoxyphenyl ether. 41766/ 2 Examples of the compounds of the invention embraced by Formula I include: LIST A . ; 2, a, a, a-tetrafluoro-£-tolyl-4-nitrophenyl ether, ·. 2-bromo-a, α,α-trifluoro-p_-tolyl-4-nitrophenyl ether, 2-chloro-a,a,a-trifluoro-p_-tolyl-4-nitrophenyl ether, a,a,a-trifluoro-2-iodo-_-tolyl-4~nitrophenyl ether, 2, 6-dichloro-a,a,a-trifluoro-p_-tolyl-4-nitrophenyl ether, 2-chloro-6,a,a,a-tetrafluoro-p_-tolyl-4-nitrophenyl ether, 2-cyano-a, a , a-trifluoro-p_-tolyl-4-nitrophenyl ether, 2-cyano-6 , α,α,α-tetrafluoro-p_-tolyl-4-nitrophenyl ether, 2-cyano-6-chloro-a,a,a-trifluoro-p_-toly1-4-nitrophenyl ether, α,α,α,α'Λ'/α ΐθχβίluoro-2,4-xylyl-4-nitrophenyl ether, 6-chloro-a,a,.a,a^ «-hexafluoro-2,4-xylyl-4-nitrophenyl ether, 4 4 4 a ,a ,a -trifluoro-2,4-xylyl-4-nitrophenyl ether, 2-butyl-a, a,a-trifluoro-p_-tolyl-4-nitrophenyl ether, 2-chloro-6-ethy1-a, a,a-trifluoro-£-tolyl-4~nitrophenyl ethar, \ LIST B 2-chloro-a, , a-trifluoro-£~.toiyl»4-nitro-m-tolyl ether, 2-bromo-a, a, a-trifluoro-£-tolyl-3-butyl-4-nitrophenyl ehter, 2 , a , , a-tetrafluoro-£-tolyl-4-nitro-3-iv-propoxyphenyl ether. 41766/2 2-chloro-6,a,a,a-tetrafluoro-£-tolyl-3-methylthio-4-nitro-phenyl ether, 2-chloro-a,a,a-trifluoro-£-tolyl-3-ethoxy-4-nitrodiphenyl ether, a,a,a-trifluoro-2-iodo-£-tolyl-3-ethoxy-4-nitrophenyl ether, ' 2,6-dichloro-a,a,a-trifluoro-£-tolyl-4-nitro-3-n-propoxy-phenyl ether, a,a,a,a^aja^exafluoro-2,4-xylyl-3-n-butoxy-4-nitrophenyl ether, 2-cyano-a,a,a-trifluoro-£-tolyl-3-ethoxy-4-nitrophenyl ether, 2-chloro-6-cyano-a,a,a-trifluoro-p_-tolyl-4-nitro-3-n-propoxyphenyl ether, 2-cyano-a,a,a-trifluoro-p_-tolyl-3-carboxy-4-nitrophenyl ether 2, 6-dibromo-a,a,a-trifluoro-p_-tolyl-3-methoxymethoxy-4-nitrophenyl ether, 2-chloro-a,a,a-trifluoro-£-tolyl-3-( 2-hydroxyethoxy) -4-nitrophenyl ether, 2,a,a,a-tetrafluoro-£-tolyl-4-nitro-3-n-propylaminophenyl ether, 2-chloro-a,a,a-trifluoro-£-tolyl-3-dime(thylamino-4-nitro-phenyl ether, 41766/2 2-cyano-a,a,a-trifluoro-£-tolyl-3-carbethoxy-4-nitrophenyl ether, 2,6-dichloro-a,a,a-trifluoro-£- toiylT3-carbethoxy-4-nitro-phenyl ether, 2-ethyl-a,a,a-trifluoro-£-tolyl-3-( 2-carboxy ethoxy)-4-nitrophenyl ether, α,α,α,α' ,α' ,α'-hexafluoro-2,4-xylyl-3-carbethoxymethyl-4-n;Ltrophenyl ether, 2-cyano-a,a,a-trifluoro-£-tolyl-3-( 2-carboxy propyl )-4-nitrophenyl ether, 2-a,a,a-tetrafluoro-£-tolyl-3-carbethoxymethoxy-4-nitro-phenyl e.ther, 2-chloro-a,a,a-trifluoro-£-tolyl-3-( 3, 3-diethylureido)-4-nitrophenyl ether, 2-chloro-6-cyano-a,a,a-trifluoro-£-tolyl-3-acetamido-4-nitrophenyl ether, 2-chloro-a,a,a-tr4,fl oro-£-tolyl-3-carbethoxyamino-4-nitrophenyL ether, . 2-chloro-a,a,a-trifluoro-£-tolyl-3-chloro-4-nitrophenyl ether, LIST C tolyl- 2-chloro-a, , a-trifluoro-p/3-hydroxy-4-nitrophenyl ether, 2-chlorp-a,a,a-trifluoro-£-tolyl-3-propyl -4-nitrophenyl ether 2-bromo-a, a, a-trifluoro-£-tolyl-3-butylnyloxy- 4-nitrophenyl ether, 2-cyano-a,a,a-trifluoro-£-tolyl-3- (2-methyl) propynyloxy-4-nitrophenylether , 2, 6-dichloro-a,a,a-trifluoro-£-tolyl-3-( 2, 2, 2-trifluoro) ethoxy-4-nitrophehyl ether, 2-chloro-a,a,a-trifluoro-p_-tolyl-3-( 2-dimethylaminoetho xy)-4-nitrophenyl ether, 2-bromo-a,a,a-trifluoro-p_-tolyl-3-acetoxy-4-nitrophenyl ether, -hexafluoro-2 , 4-xylyl-3-( 2-hydroxyethyl amino )-4-nitrophenyl ether, 4 4 4 a ,a , a -trifluoro-2-,4-xylyl-3-amino-4-n trophenyl ether, 2-chloro-a,a,a-trifluoro-£-tolyl-3-morpholino-4-nitrophenyl ether, 2-cyano-a,a,a-trifluoro-_-tolyl-3-(N-methylcarbamoyloxy)-4-nitrophenyl ether, 2-chloro-6,a,a,a-tetrafluoro-p_-tolyl-3-propionamido-4-nitrophenyl ether, 2-chloro-a,a,a-trifluoro-£-tolyl-3-chloroacetamido-4-nitrophenyl ether, a^i , a^ ,α^-trifluoro-2 , 4-xylyl-3-( 2 , 3-epoxypropoxy)-4-nitrophenyl ether, 2-chloro-a,a,a-trifluoro-£-tolyl-3-( 2 , 3-dihydroxypropoxy)-4-nitrophenyl ether, 2-cyano-a,a,a-trifluoro-£-tolyl-3-( 2-methylthioethoxy)-4-nitrophenyl ether, 2-chloro-a,a,a-trifluoro-£-tolyl-3-( l-ethyl-3-methylurei-do) 4-nitrophenyl ether, · 2-bromo-a,a,a-trifluoro-p_-tolyl- 3-( 2-methylsulfonylethoxy) -4-nitrophenyl ether, -f- 41766/2 α,α,α,α' ,α' ,a'-hexafluoro-2,4-xylyl-3-( 3-methylureido)-4-nitrophenyl ether, 2-cyano-a,a,a-trifluoro-£-tolyl-3-ethylthiocarbonylamido-4-nitrophenyl ether, 2-cyanoHX,a,a-trifluoro-p_-tolyl-3-cyano-4-nitrophenyl ether, 2,6-dichloro-a,a,a-trifluoro-p_-tolyl-3-carboxy-4-ni.tro-phenyl ether, 2-chloro-a,a,a-trd,fluoro-£-tolyl-3-( -carbamoylethoxy)-4-nitrophenyl ether, 2-bromo-a,oc,a-trifluoro-_-tolyl-3-( 3-oxobutoxy)-4-nitrophenyl ether, and the like.
The invention also provides a method of controlli i.e. inhibiting or completely suppressing, weeds in a growth medium which comprises applying a herbicide (a) to the growth medium prior to emergence of the weeds therefrom or (b) to the weed seedlings in a growth medium., the herbicide being applied in an amount sufficient to cpntrol the growth of the weeds, wherein there is applied as herbicide a compound as defined by formula I. Usually the growth medium contains ΟΓ· is to 'be planted with an agronomic crop.
/ The novel diphenyl ethers of the invention are useful both as preemergence and as postemergence herbicides. Preemergence herbicides are ordinarily used to treat the soil in which the desired crop is to be planted by application either before seeding, during seeding, or, as in most applications, after seeding and before the crop emerges. Post-emergence herbicides are those which are applied after the plants have emerged and during their growth period.
An isomer of one of the compounds of the invention, namely the isomer 2-nitro-4-trifluoromethylphenyl 4-chlorophenyl ether has been disclosed as a herbicide in U.S. Patent No. 3,420,892 but this compound does not possess the herbicidal activity of its isomer within the scope of the invention, i.e. the compound 2-chloro-4-trifluoromethylphenyl 4-nitrophenyl ether. Thus, the latter compound not only possesses broad spectrum preemergence and postemergence activity, especially at economically low and ecologically important low rates of application (e.g. at ¾ and ■J lb. /acre) but also the latter compound possesses unexpected activity against a number of troublesome weed species which are not controlled at all by the prior art isomer.
Among the crops on which the diphenyl ethers of the invention can be advantageously employed are, for example, cotton, soybeans, peanuts, safflower, beans, -11- peas, carrots, corn, wheat, and other cereal crops.
Diphenyl ethers of the invention are useful for controlling weeds in rice crops. When used in trans-planted rice crops, the ethers can be applied either preemergence or post-emergence to the weeds-that is, they can be applied to the growth medium of the transplanted plants either before the weed plants have emerged or while they are in their early stages of growth. The ethers can be applied to the growth medium either before or after the rice has been transplanted to that medium.
The diphenyl ethers of the invention can be applied in any amount which will give the required aontrol of weeds. A preferred rate of application of the herbicides of the invention is from about 0.1 to about 12, and most preferably about 0.25 to 4, pounds of the diphenyl ether per acre.
Under some conditions, the diphenyl ethers of the invention may be advantageously incorporated into the soil or other growth medium prior to planting a crop. This incorporation can be carried out by any convenient means, including by simple mixing with the soil, by applying the diphenyl ether to the surface of the soil and then disking or dragging into the soil to the desired depth, or by employing a liquid carrier to accomplish the necessary penetration and impregnation.
A diphenyl ether of the invention can be applied to the growth medium or to plants to be treated either by itself or, as is generally done, as a component in a herbicidal composition or formulation which also comprises an agronomically acceptable carrier. By agronomically acceptable carrier is meant any substance which can be used to dissolve, disperse, or diffuse a herbicidal compound in the composition without impairing the effectiveness of the herbicidal compound and which by itself has no detrimental effect on the soil, equipment, crops, or agronomic environment. Mixtures of the diphenyl ethers of the invention may also be used in any of these herbicidal formulations. The herbicidal compositions of the invention can be either solid or liquid formulations or solutions. For example, the diphenyl ethers can be formulated as wettable powders, emulsifiable concentrates, dusts, granular formulations, aerosols, or flowable emulsion concentrates. In such formulations, the compounds are extended with a liquid or solid carrier and, when desired^ suitable sufactants are incorporated.
In general, the invention includes a method of preparing a herbicidal composition by bringing a herbicidal compound into a form suitable for this purpose, e.g. with the use of a solid and/or liquid carrier, a 13 surface active agent, adhesive agent or other pesticide, wherein the herbicidal compound employed is one or more of the aforementioned trihalomethyl .diphenyl ethers.
It is usually desirable, particularly in post-emergence applications, to include adjuvants, such as wetting agents, spreading agents, dispersing agents, stickers, adhesives, and the like, in accordance with agricultural practices. Examples' of adjuvants which are commonly used in the art can be found in the John W.
McCutcheon, Inc. publication "Detergents and Emulsifiers Annual" . ( .
The diphenyl ether compounds of this invention can be dissolved in any appropriate solvent. Examples of solvents which are useful in the practice of this invention include alcohols, ketones, aromatic hydrocarbons, halogenated hydrocarbons, dimeth lformamide, dioxane, dimethyl sulfoxide, ,and the like. Mixtures of these solvents can also be used. The concentration of the solution can vary from about 2% to about 98% by weight with a preferred range being about 25% to about 75% by wei For the preparation of emulsifiable concentrates, the diphenyl ether can be dissolved in organic sol-vents, such as benzene, tolue'ne, xylene, methylated naphthalene ,corn oil, pine oil, o-dichlorobenzene, isophorone, cyclohexanone, methyl oleate, and the like, or in mixtures, of these solvents, together with an emulsifying agent which permits dispersion in water. Suitable emul-sifiers include, for example, the ethylene oxide derivatives of alkylphenols or long-chain alcohols, mercap-tans, carboxylic acids", and reactive amines and partially esterified polyhydric alcohols. Solvent-soluble sulfates or sulfonates, such as the alkaline earth salts or amine salts of alkylbenzenesulfonates and the fatty alcohol sodium sulfates, having surface-active properties can be used as emulsifiers either alone or in conjunction with an ethylene oxide reaction product. .
Flowable emulsion concentrates are formulated similarly to the emulsifiable concentrates , and include, in addition to the above components, water and a stabilizing agent such as a water-soluble cellulose derivative or a water-soluble salt of a polyacrylic acid. The concentra-tion of the active ingredient in emulsifiable concentra- by weight tes is usually about 10% to 60 /and in flowable emulsion concentrates, this can be as high as about 75%. by weight ettable powders suitable for spraying, can be prepared by admixing the compound with a finely divided solid, such as clays, inorganic silicates and carbonates and silicas and incorporating wetting agents, sticking agents, and/or dispersing agents in such mixtures. The concentration of active ingredients in such formulations Is usually in the range of about 201 to 98%, preferably about 40% to 75% by weight. A dispersing agent can constitute about 0.5% to about 3% by weight of the corjposition, and a wetting agen can constitute f om about 0.1% to about 5% by weigh y of the composition.
Dusts can be prepared by mixing the compounds of the invention with finely divided inert solids which nay be organic or inorganic in nature. Materials useful for this purpose include, for example, botanical flours, silicas, silicates, carbonates and clays. One convenient method of preparing a dust is to dilute a wettablo powder with a finely divided carrier. Dust concentrates containing about 20% to 80% by weight of the active ingredient ar ccaanonly made and are subsequently diluted to about 1% to 10% by weight use concentration.
Granular formulations can be prepared by izo xegnating a solid such as granular fuller' a earth, vermiculite, ground com cobs, seed hulls, including bran or other grain-hulls, or similar material, solution of one or more of the diphenyl ethers i a volatile organic solvent can be sprayed or mixed with the granular solid and the solvent then removed by evporation* The granular material can have any suitable size, with a preferable size range of 16 to 60 mesh (US Stan ard Sieve Series) . The diphenyl ether will usually comprise about 2 to 15% of the granular formulation. -16- 41766/2 The diphenyl ethers of the invention can also be mixed with fertilizers or fertilizing materials before their application. In one type of solid fertilizing composition in which the diphenyl ethers can be used, particles of a fertilizer or fertilizing ingredients, such as ammonium sulfate, ammonium nitrate, or ammonium phosphate, can be coated with one or more of the ethers.
The solid diphenyl ethers and solid fertilizing material can also be admixed in mixing or blending equipment, or they can be incorporated with fertilizers in granular formulations. Any relative proportion of diphenyl ether and fertilizer can be used which is suitable for the crops and weeds to be treated. The diphenyl ether will by weight commonly be from about 5% to about 25%/of the fertilizing composition. These compositions provide fertilizing materials which promote the rapid growth of desired plant and at the same time control the growth of undesired plants.
The diphenyl ethers of the invention can be applied as herbicidal sprays by methods commonly employed, such as conventional high-gal lonage hydraulic sprays, low gallonage sprays, airblast spray, aerial sprays and dusts. For low volume applications a solution of the compound is usually used. The dilution and rate of application will usually depend upon factors as the type of equipment employed, the method of application, the area to be treated and the type and stage of develop of the weeds. 41766/2 For some applications, it may be desirable to add one or more other herbicides along with diphenyl. ethers of the invention. Examples of othe herbicides which can be incorporated to provide additional advan-tages and effectiveness include: LIST D Carboxylic Acids and Derivatives 2, 3, 6,-trichlorobenzoic acid and its salts 2, 3, 5 , 6-tetrachlorobenzoic acid and its salts 2-methoxy-3, 5 , 6-trichlorobenzoic acid and its salts 2-methoxy-3, 6-dichlorobenzoic acid and its salts 2-methyl-3, 6-dichlorobenzoic acid and its salts 2.3-dichloro-6-methylbenzoic acid and its salts 2.4-dichlorophenoxyacetic acid and its salts and esters 2.4.5-trichlorophenoxyacetic acid and its salts and esters 2-methyl-4-chlorophenoxyacetic acid and its salts and esters r '' · 2-( 2,4,5-trichlorophenoxy)propionic acid and its salts and esters 4-( 2, 4-dichlorophenoxy)butyric acid and its salts and esters 4-( 2-methyl-4-chlorophenoxy)butyric acid and its salts and esters 2.3.6-trichlorophenylace ic acid and its salts 3, 6-endoxohexahydrophthallc acid dimethyl 2,3,5,6,-tetrachloroterephthalate trichloroacetic acid and its salts 2.2-dichloropropionic acid and its salts 2.3-dichloroisobutyric acid and its salts Carbamic Acid Derivatives ethyl N ,N-di(n-propyl ) thiolcarbamate propyl N,N-di(n-propyl ) thiolcarbamate ethyl N-ethyl-N-(n-butyl ) thiolcarbamate propyl N-ethyl-N-( n-butyl ) thiolcarbamate 2-chloroallyl N ,N-diethyldithiocarbamate N-methyldithiocarbamic acid salts ethyl 1-hexamethyleneiminecarbothiolate isopropyl N-phenylcarbamate . . isopropyl N-(m-chlorophenyl ) carbamate 4-chloro-2-butynyl N-(m-chlorophenyl ) carbamate methyl N-( 3, 4-dichlorophenyl ) carbamate Phenols dinitro-o-( sec-butyl ) henol and its salts pentachlorophenol and its salts Substituted Ureas 3-( 3 , 4-dichlorophenyl ) - , 1-dimethylurea 3-phenyl- , 1-dimethylurea 3_( 3 , 4-dichlorophenyl ) -3-methoxy-l , 1-dimethylurea 3-(4-chlorophenyl )-3-methoxy†l, 1-dimethylurea 3-( 3, 4-dichlorophenyl )-l-n-butyl-l-methylurea 3-( 3 , 4-dichlorophenyl ) -l-methoxy-l-methylurea 3-( 4-chlorophenyl ) -l-methoxy-l-methylurea 3-( 3, 4-dichlorophenyl )-l, , 3-trimethylurea 3-( 3, 4-dichlorophenyl l-diethylurea dichloral urea 4 Substituted Triazines 2-chloro-4 , 6-bis ( ethylamino ) -s-triazine 2-chloro-4-ethylamino-6-isopropylamino-s_-triazine 2-chloro-4 , 6-bis ( methoxypropylamino ) -s-triazine 2-methoxy-4, 6-bis ( isopropylamino) -s-triazine 2-chloro-4-ethylamino-6-( 3-methoxypropylamino) -s-triazine 2-methylmercapto-4 , 6-bis ( isopropylamino ) -s-triazine 2-methylmercapto-4 , 6-bis ( ethylamino ) -s_-triazine 2-methylmercapto-4-ethylamino-6-isopropylamino-s_-triazine 2-chloro-4 , 6-bis ( isopropylamino ) -s-triazine 2-methoxy-4 , 6-bis ( ethylamino ) s-triazine 2-methoxy-4-ethylamino-6-isopropylamino- The 4-trifluoromethyl-4'-nitrophenyl ethers of the invention can be prepared by any process known per se for analogous compounds, e.g. by a process which includes the step of reacting at an elevated temperature a suitable substituted halobenzene, particularly a chlorinated or fluorinated benzene, with (a) a suitable phenolic compound, such as a substituted phenol, e.g. resorcinol, in the presence of an alkaline agent or (b) a potassium or sodium salt of such a phenolic compound.
The following examples will further illustrate this invention but are not intended to limit it in any way. In Table I, typical diphenyl ether* of the invention (where Z = H) are listed with their melting points and elemental analyses. Specific, illustrative preparations of the compounds of Examples 1 to 3 and 6 to 8 are described after Table I.
In Table II, further typical diphenyl ethers of the invention are listed, with their melting points and elemental analyses. Specific, illustrative preparations of the compounds of Examples 3Z, 7Z, 19Z, 1Z, 25Z, 26Z, ¾9Z, 51Z, 55Z and 56Z, are described after Table II, the letter Z being added to denote compounds in which Z represents a group or atom other than hydrogen. - 23 TABLE I Diphenyl Ethers - Physical Data CF Example No. X Y m.p. (b.p. )°C % 1 CN H , 93-98 found 54 req s, 54 2 CI H 67-70 found 49 C13H7C1F3N03 req s. 49 3 F H (95-98/0.35 mm) found 51 C13H7F4N03 req S' 51 • 4 Br H 86-87 ' found 43 C13H?BrF3N03 req s. 43 5 H H .47-48 found 55 C13H8F3N03 req S' 55 6 CI Cl 83-86 found 44 C.0H,-C1 F_NO. rea s. 44 13 6· 2 3 3 7 CH H 58-63.5 found 56 56 C14H10F3NO3 req s< 8 CF- H 72-73 found 48 14H7F6N03 req s. 47 •¾Br - 25 - Example No. X Y m.p. (b.p.)°C %C 1 CN H 93-98 found 54. req s 54.
CI H 67-70 found 49. 49.
C13H7C1F3N03 req S H (95-98/0.35 mm) found 51.
C13H7F4N03 req s 51.
Br H 86-87 ' found 43.
C -H BrF_NO req s 43.
-K- -H- 47 48 -found --5-5 CI CI 83-86 found 44. 44.
C13H6C12F3N03 req s 7 CH H · 58-63.5 found '3 56. 56.
C14H10F3NO3 req s 8 CF. H 72-73 found 48. req s 47.
C14H7F6N03 ►¾Br - 25 - Example 1 Preparation of 2-cyano-a,a,a-trifluoro-ii-tolyl-4-nitro-phenyl ether A solution of potassium hydroxide (3,2g. 0.05 mple of 89.3% purity) and p_-nitrophenol (7.0 g. 0.05 mole) in methanol (25; ml.) is stripped under reduced pressure. The residue is dissolved in sulfolane, 4-chloro-3-cyano-a,oc,a-trifluorotoluene (10.3 g. 0.05 mole) added, and the resulting solution heated at 150°C for five hours. After cooling, the solution is diluted with benzene (350 ml.) washed with water (6 X 250 ml.), dried, and the solvent removed. The residue (12.5 g.) is recrystallized from isopropanol to give 2-cyano-a,a,a-trifluoro-£-tolyl-4-nitrophenyl ether (7.6g., 49%) m.p. 93-98°C.
Example 2 Preparation of 2-chloro-a,oc,a-trifluoro-]D-tolyl-4-nitrophenyl ether la) 2-Chloro-a,a,oc-trifluoro-p_~cresol Chlorine gas is passed through a flow meter into a solution of α,α,α-trifluoro-p_-cresol (4.05 g. 0.025 mole) in ethylene dichloride (200 ml.) at 0°C. until the theoretical volume has been absorbed. The solvent is stripped off and the residue distilled to give 2-chloro-a,a,a-trifluoro-p_-cresol (3.5 g. 71%) b. p. 80-82°C. at 33 mm.
Ib) 2-Chloro-oc,α,α-trifluoro-p_-tolyl-4-nitrophenyl ether , Potassium hydroxide (1.08 g. 0.0166 mole, 86% pure) is dissolved in methanol (10 ml.) and a solution of 2-chloro-a,oc,oc~trifluoro-p_-cresol (3.27 g. 0.0166 mole) in methanol added. The solvent is removed under pressure and sulfolane (100 ml.) added followed by p_-fluoronitrobenzene (2.34 g., 0.0166 mole) and the mixture heated at 130-150°C. for seven hours. After cooling, the solution is poured into water (200 ml.) and extracted with benzene. The extract is dried, filtered through activated silica gel (lOg.) and the solvent removed. The residue is taken up in isopropanol/ hexane (1:3) cooled to -20°C, decanted from an oily precipitate, and the solvents stripped off. The residue (2.9 g.) is distilled to give 2-chloro-a,oc,a-trifluoro-£-tolyl-4-nitrophenyl ether (1.6 g. 31%) b.p. 23-85°C/ 0.3 mm which when induced to crystallize has a melting range of 62-68*0. An impurity isolated from a preparation following this procedure has been identified as 4-carbomethoxy-2-chlorophenyl-4-nitrophenyl ether.
Ila) 2-Chloro-a,a,o-trifluoro-p_-tolyl phenyl ether ' Potassium phenoxide,' prepared by stripping a solution of phenol (4.7 g. 0.05 moles) and potassium hydroxide (3.3g. 0.05 moles 86.2% purity) in methanol (20ml.) is dissolved in sulfolane (75g.), and 3,4- 9.7 dichloro-o,a,oc-trifluorotoluene (10.8 g., 0.05 mole) added. The mixture is heated at 170°C. overnight then cooled, diluted with benzene (250 ml.), and washed with water (3 X 600 ml . ) . The organic phase is dried, filtered through activated silica gel (20 g.) and the solvent removed. The residue (12.4 g.) i distilled to give 2-chloro-a,a,oc-trifluoro-p_-tolyl phenyl ether (9.9 g. 72%) b.p. 85-90°C/0.25 mm. contaminated with about 5% of 6-chloro-a,a,oc-trifluoro m-tolyl phenylether.
Found: C, 57.13; H, 3.09; C , 13.17; F, 20.86 Calculated " for C13HgC F30;Q57.27; H, 2.95; C , 13.00; F, 20.91. lib) 2-Chloro-a,a,oc-trifluoro-p_-tolyl-4-nitrophenyl ether A mixture of fuming nitric acid (10 g. 0.16 mole) and concentrated sulfuric acid (10 g.) is added With ^vigorous stirring to 2-chloro-oc,a,a-trifluoro-p_- tolyl-phenylether (27.3 g. 0.01 mole) initially at 75 °C, maintaining a rate of addition such that the temperature does not rise above 85 °C. After stirring at 80°C. for one half hour, further mixed acid (5 g. + 5 g.) is added and the mixture stirred for fifteen minutes, cooled, diluted with water, and extracted with benzene (2 X 200 ml.). The extract is washed with water and bicarbonate solution, dried, and the solvent removed. - 23 - The residue (29.1 g.) is recrystallized from isopropa-nol to give 2-chloro-a,oc,oc-trifluoro-p_-tolyl-4-nitro-phenyl ether (12.7 g. 40%) m.p. 67-70°C. Analytical and spectroscopic data confirm the identity of the products from Routes I and II.
Example 3 Preparation of 2, α,α,α-Tetrafluoro-p_-tolyl-4-nitrophe-nyl ether a) 2-Amino-a,cfoc-trifluoro-p_-tolylphenyl ether 2-Nitro-a,a,a-trifluoro-p_-tolylphenyl ether (57.0 g., 0.209 mole) is dissolved in ethanol (200 ml.) and shaken in an atmosphere of hydrogen in a Parr apparatus in the presence of platinum oxide (100 mg.) until uptake is complete. The catalyst is removed by filtration and the solvent stripped off to give 2-amirio α,α,α-trifluoro-p_-tolyl phenylether (50.3 g. 99%) which. is used without further purification.
Found: C, 61.76; H, 3.65; F, 22.35; N, 5.52. Calculated for C13H1QF3NO; Cf 61.66; H, 3.98; F, 22.51; N, 5.53 b) 2,a,oc,cx-tetrafluoro-p_-tolylphenyl ether 2-Amino-a,oc,cx-tr ifluoro-p_-tolylphenyl ether (25.3g. 0.1 mole) is added to concentrated hydrochloric acid (100 ml.) and the mixture cooled to -15°C. A solution of sodium nitrite. (7.5 g. 0.1 + mole) in water (5 ml.) is added dropwise with stirring, and after a total of . 41766/2 2 hours at -15 °C, the diazonium chloride solution is filtered and treated with a solution of sodium fluo— borate (25 g. 0.2 + mole) in water (30' ml.) and the dense fluoborate salt filtered off and washed with ethanol and ether, then air dried, yield 23.0 g., decomposition point /"«-/190oC. The salt is then added portionwise to. a flask maintained in an oil bath at 200°C, and when decompositio is complete, the residue is taken up in benzene (150 ml.), washed with water (4 x 100 ml.), dried, and the solvent removed. The residue (10.3 g.) was extracted with isopropanol/hexane to give a residue which on distillation gives 2,α,.α,α-tetrafluoro-£-tolylphenyl e.^her ('3.4 g. 14%), b.p. 90°C/0.25 mm. c) 2,a,a,a,-tetrafluoro-p_-tolyl-4-nitrophenyl ether The ether described in part (b) above is nitrated by the procedure described in Example 2 above for 2-chloro- , , -trifluoro-_-tolyl-4-nitrophenyl ether .
Example 6 Preparation of 2 , 6-Dichloro- ,a, -trifluoro-p_-tolyl-4-nitrophenyl ether a) , 3,4-Dichloro-o,a,a-trifluoro-5-nitro toluene and 3,4-dichloro-a,a,a-trifluoro-6-nitro toluene A mixture of 3,4-dichloro-a,a,a-trifluorotoluene (430 g., 2.0 moles), concentrated sulphuric acid (1200 ml) and concentrated nitric acid (1200 ml, excess) was . stirred at 90-100 °C for one half hour^!. The mixture was then cooled" and the acid phase discarded. The organic phase was washed with water, dilute sodium bicarbonate solution, potassium carbonate solution, dried; and distilled to give an approximately equal mixture (456 g., 89%) of 3* 4-dichloro-a,a,a-trifluoro-5-nitrotoluene and 3, 4-dichloro-ot,a,a-trifluoro-6-nitrotoluene, b.p. 86 °C/ 3mm. b) 2-Chloro-a , , cc-trifluoro-6-nitro-p-tolylphenyl ether A solution of potassium hydroxide (43.2g. of 86% pure, 0.665 moles) in water (20 ml.) was added slowly to a mixture of phenol (62.5 g., 0.665 mole) and the product from (a) above (450 g. total, equivalent to 0.665 mole of 3, 4-dichloro-a,a,a-trifluoro-5-nitro toluene) in sulfolane (300 ml.) at 30-68 °C with stirring. After stirring at 42-68 °C for a total of one hour the mixture was diluted with hexane (400 ml.) and water (600 ml.). The resulting layers were separated and the aqueous phase extracted once with hexane. The combined organic phases were washed with water and dilute caustic soda solution, dried and the solvent removed. The residue (471.3 g. ) was distilled through a vacuum jacketed Vigreux column. No. 1 (272.2 g. ) bp^l00°C/0.2 mm. consisted essentially of un-reacted 3, 4-dichloro-ot,a, Example 7 4 4 4 Preparation of a ,a ,a -trifluoro-2 , 4-xylyl-4-nitrophenyl ether a) 2-Brorao-a,a,a-trifluoro-p-tolylphenyl ether A solution of 3-bromo-4-chloro-a,a,a-trifluoro-toluene (143 g. , 0.55 mol ), potassium phenoxide (72.6 g. 0.55 mol), in sulfolane (200 ml.) is heated and stirred 3 hours at 165-170° C. The solution is cooled. Benzene (250 ml.) and hexane (250 ml.) are added, and the solution washed with dilute sulfuric acid (500 ml.), the solvent removed, and the oil distilled to give 2-bromo-a,a, Example 8 Preparation of α,α,α,α' ,α' ,a,-hexafluoro-2,4-xylyl-4-nitrophenyl ether - - a) α,α,α,α' ,α· , α » -hexafluoro-2 , 4-xylylphenyl ether A solution of potassium phenoxide (15.0 g. 0.1 m)"and 4-chloro-a,a,a,a',a*Jhexafluoro-m-xylene in sulfolane (50 ml.) is heated 60 hours at 140-160°C. The solution is cooled and benzene (400 ml.) and hexane (250 ml.) are added and the solution washed twice with water (1 liter, 500 ml.), twice with 10% sodium carbonate solution (/ i-OO ml. each), and water, dried, filtered through activated silica gel (rv-/25 g.), the solvents removed, and the residue distilled to give a, a, a, a« ,α' ,α' -hexafluoro-2, 4-xylylphenyl ether (22.4 g. , 73%) b.p. 81-85 "C. miii. b) α,α,α,α' ,α' ,α' -hexafluoro-2, 4xylyl-4-nitrophenyl ether α,α,α,α· ,α' ,α' -Hexafluoro-2 , 4-xylyl-phenyl ether (16.1 g. 0.0525 mol), concentrated sulfuric acid (12 ml. 0.22 mol), concentrated nitric acid (12 ml. 0.19 mol) and ethylene dichloride (65 ml) are stirred 30 minutes at room temperature and allowed to separate. The ethylene dichloride layer is washed with water, 10% sodium carbonate solution, and water and the solvent removed. The residual oil is dissolved in hexane, filtered through activated silica gel g. ) and the solvent removed to give α,α, ct , α· , α' ,α· -hexafluoro-2, 4-xylyl-4-nitrophenyl ether (11.4 g. 62%) m.p. 72-73°C.
Examples 9-14 Following the procedures of Examples 1 to 3, other diphenyl ethers of formula I are prepared. Among the compounds which are prepared by these procedures ares LIST E 6-chloro-a,α, ,a· ,a• ■hexafluoro-2,4-xylyl-4-nitropheny1 ether, 2- It should be noted that the diphenyl ethers of the invention can also be named correctly using different systems of nomenclature. For example, the diphenyl ether of Example 1 can also be named as 2-cyano-4-trifluoromethyl~ 4' -nitrodipheny1 ether. -37- TABLE II Diphenyl Ethers-Physical D A Example NO. X Y Z mm..pp.. ((°°CC)) %C ¾H 1Z H H . OC2H5 7722--7755 ffoouunndd 54.67 3.7 rreeqqss.. 55.05 3.70 2Z Cl H 0CH3 9955--110000 ffoouunndd 48.78 2.8 rreeqqss.. 48.33 2.6 3Z - Cl . H °C2H5 8833--8844 ffoouunndd 49.85 3.3 rreeqqss.. 49.80 3.0 4Z Cl H 0C3H?-i 4499..55--5511 ffoouunndd 51.02 3.5 rreeqqss.. 51.18 3.4 5Z Cl H 0C H_-n 7755--7766 '' ffoouunndd 5 511..3366 3 3..6600 reqs. 51.18 3.49 6Z Cl H OC4H9-n 51-52 Found 52.01, 4.0 reqs. 52.42 3.8 - 38 - TABLE Il.( cont'd) Example No. X Y Z m.p.(°C) %C 7Z . CN H OC2H5 143-145 found 54.84 reqs. 52.18 8Z CN H OC3H?-n 96.5-98 found 55.70 reqs. 55.74 9Z CN H ' CH3 86-88.5 found 55.95 reqs. 55.90 10Z CI H OH 68-70 found 47.07 reqs. 46.79 11Z CI H OCH2CF3 78-80 found 43.30 reqs. 43.35 12Z H OCH2CK=CH2 76-78.5 found 51.76 reqs. 5.42 13Z H 0CH2C=CH 89-93 found 51.83 reqs. 51.70 14Z Cl H OCH2CH2C=CCH3 93-94 found 53.99 reqs. 54.10 15Z Cl K OCK2CK2CH 76-77 found 47.53 reqs. 47.70 16Z ci K OCH2CH2OC2H5 62-64 found 50.75 reqs. 50.32 17Z ci H OCH2CH2 (CH3)2 oil found 50.30 reqs.. 50.44 Example No. X Y Z m.p. (°C) 18Z CI H OCOCK- 85-89 found reqs. 19Z Ci H HC HC 82-83 found reqs. 20Z CI H N(CH-) 82-83 . found reqs. 21Z ci H N(C Hc-) • 170 °C/0.01mm found reqs. 22Z ci H NHCH.CH-OH 85-87 found reqs. 23Z ci K 0CH_C0 H 94-96 found reqs. 24Z ci H CCH-CO-C-H- 76-77 found reqs. 25Z ci H · 0CH(CH-)C0 H 108-109 found. reqs. 26Z ci H 0CH(CH_)C0 C Hc- 71-72.5 found reqs. 27Z Cl H NH_ 85.5-89.5 found reqs. 28Z ci H •180-185/' found 0.04 mm reqs. * boiling point TABLE II (cont'd) Example No. X Y Z, rn.p. ( °C) 29Z -CI H OCH2CH2C;CH 104-105 .5 fo re 30Z i H. OCH(CH3)C»CH 40-42 fo re 31Z CI H OCH2CH2COCH3 74-76 fo re 32Z ci H 0CH(CH3)C6CH3 oil fo re 33Z CI H . OCONHCH3 85-88 fo re 34Z ci •H HCOC2H5 oil fo re 35Z ci H NHCCCH2C1 oil fo re 36Z ci H CH3 •135 °C/ fo 0.08mm re 37Z ci H c *153°C/ fo 0.24mm re 38Z i H OCH2 VZH2 49-53 fo re 39Z ci H OCH2CHOHCH2OH 59-64 fo re • boiling point _ 41 _ TABLE II (cont'd) Example No. X Y z m.p. (°C) 51Z CI H OCH(CH3)CONH2 108-111 found reqs. 52Z Gl H OCH(CH,)CONHCH3 121-126 found reqs. 53Z CI H OCH(CH3)CON(CH3)2 83-85 found reqs. 54Z ci H (C2H5)CH2CH2OH found reqs. 55Z C'l H N(C2H5)CONHCH3 127. 5-128. 5 found reqs. 56Z ci C OC2H5 100. 5-102 found, reqs.
Example 3Z Preparation of 2-Chloro-oc , a , a-trifluoro-p-tolyl-3-ethoxy-4-nitrophenyl ether Method A a) 1, 3-Bis( 2-Chloro-a, a, α-trifluoro-p_-tolyloxy)benzene A solution of potassium hydroxide (3.26 g. 0.05 mole, 85%) in water (^- 3g. ) is added slowly dropwise to a solution of resorcinol (2.75 g. 0.025 mole) and 3,4-dichloro-a, a, a-trifluorotoluene (10.75 g. 0.05 mole) in ■ , sulfolane (125 ml.) at 150-160 °C. , with stirring. When the addition is complete, the strongly colored reaction mixture is stirred at 150-160 °C. overnight, then cooled, diluted with benzene (200 ml.), and washed cautiously with water (700 ml.). Hexane (200 ml.) is added and the mixture washed with water (600 ml.), dilute sulfuric acid (600 ml.), dilute sodium hydroxide solution (600 ml.), and water (600 ml.), dried, and the s olvent removed to give 1, 3-bis ( 2-chloro-a , a , a-trifluoro-jD-tolyloxy Jbenzene (8.6 g. 65%) b.p. 160-70 °C./0.1 mm. b) 1, 3-Bis( 2-chloro-a, a , a-trifluoro-£-tolyloxy ) -4- nitrobenzene 1, 3-Bis(2-chloro-a, a, a-trifluoro-£-tolyloxy)-benzene (12g. 0.0255 mole) is added to a mixture of concentrated nitric acid (12 g. ) and sulfuric acid (15g.) at 5°C. The temperature is then allowed to rise to 25-30°C. with manual stirring and mild ice bath cooling and after 10-20. minutes , the oil solidifies. The mixture is taken up in wate /benzene (400 ml)/hexane (400 ml.) and the organic phase is washed with water, dried, filtered through activated silica gel («v 20 g.), and the solvents removed. The residue is recrystallized from isopropanol to give 1, 3-bis ( 2-chloro-a,ot,a-trifluoro-£-tolyloxy )-4-nitrobenzene, (7.4 g. 56%) m.p. 110-111.5°C. c ) 2-Chloro-a,a,a-trifluoro-£-tolyl-3-ethoxy-4-nitro- phenyl ether A 10% solution of potassium hydroxide in etha-nol (10 ml) is added to a solution of 1, 3-bis (2-chloro- , ,α-trifluoro- -tolyloxy )-4-nitrobenzene (2g. 0.0039 mole) in dioxane (20 ml). After forty minutes at room temperature, the solution is heated to 45°C for eight minutes, then cooled, diluted with benzene (50 ml) and hexane (50 ml) and washed with water (3 X 100 ml), dried, and the solvents removed. The residue is recrystallized from isopropanol to give 2-chloro-a,oc,a-trifluoro-jD-tolyl-3-ethoxy-4-nitrophenylether (1.21 g. 86%) m.p. 83-84°C.
Method B a) 2-Chloro-oo,a,a-t ifluoro-p-tolyl-3-hydroxyphenyl ether ' A mixture of the di-potassium salt of resorcinol (186.3 g., 1 mol), 3, 4-dichloro-a,a,a-trifluorotoluene (53.7 g. , 0.25 mol), and sulfolane (100 ml) is stirred for 30 hours at 140-160°C.
Benzene (500 ml) and water (200 ml) are added and the organic phase is washed with water (3 X 200 ml), diluted with, hexane (500 ml) and washed again with vater, dried, filtered through activated silica gel (15 g, ) , the solvents removed, and the residue distilled to give 2-chloro-a,a,a-trifluoro-jo-tol l-3-hydroxyphenyl ether (45.1 g., 62%) b.p. 112-124°C. /0.3 mm. b ) 2-Chloro-a,a,a-'trifluoro-p-tolyl-3-acetoxyphenyl ether A mixture of 2-chloro-a,0Cs,a-trifluoro-j-tolyl-3-hydroxyphenylether (184 g. ) and acetic anhydride (334 g. ) is heated on a steam bath for .1 hour and cooled. The mixture is washed with 5% sodium carbonate solution ( 2X 500 ml) 'and distilled to give 2-chloro-oo,a,a-trifluoro-j-tolyl-3-acetoxyphenyl ether (84 g. , 40%) b.p. 107-117°C. /0.09 mm. c ) 2-Chloro-a,oc,a-trifluoro-_p_-tolyl-3-acetoxy-4-nitro phenyl ether A solution of 2-chloro-a,c,a-trifluoro- -tol l-3-acetoxyphenyl ether (249 g. , 0.75 mol) in 1, 2-dichloro-ethane (1200 ml.) is stirred 2.2 hours at 20-30°'C. with a cooled mixture of concentrated sulfuric acid (276 g.) and . nitric acid, 70% (227 g.). Hexane (700 ml.) is added and the oil layer washed once with water, 3 times with dilute sodium bicarbonate, and once more with water, dried, filtered through activated silica gel (^40 g.), the solvents removed.
The product is crystallized from hexane-benzene to give „2-chloro-a,a,a-trifluoro-j -tolyl-3--acetoxy-4-nitrophenyl ether (207.5 g., 73%) m.p. 83-89°C. d) 2-Chloro-a,a,o-trifluoro-£-tolyl-3-hydroxy-4- nitrophenyl ether A solution of.2-chloro-oc,a,a-trifluoro-p-tolyl-3~acetoxy-4-nitrophenyl ether (204.9 g., 0.545 mol) in methanol (2900 ml.) is stirred 1 hour at 20°C. with potassium carbonate (103 g., 0.745 mol). Ninety per cent of the methanol is removed; and benzene (1 liter), 7-8%-su.lfuric acid solution (1600 ml.) are added and stirred 1.5 hours at 25°C. The oil layer is washed twice more with water (200 ml. each), dried, filtered through activated silica gel (40 g.), the solvents removed, and the residue crystallized in hexane to give 2-chloro- , ,α-trifluoro-_-tolyl-3-hydroxy~4-nitrophenyl ether (165.3 g. 90%) m.p. 68.5-73°C. e) 2-Chloro-oo,oc,a-trifluoro-£-tolyl-3-ethoxy-4~nitro- phenyl ether A solution of 2-chloro-a.,a,a-trifluoro-£-tri-fluoro-£-tolyl-3~hydroxy-4-nitrophenyl ether (60 g«, 0.018 mol, 73% pure) and dimethylformamide (100 g.) is converted to the potassium phenoxide and stirred with ethyl bromide (35 g., 032 mol) 3 hours at 60°C. and 5 hours at 80°Co Perchlorethylene (150 g.) is added and the solution washed twice with water (v-250 ml. each) at 50°Co 4-7 The solvents are removed to give 2-chloro-a,a,a-trifluo-ro-£-tolyl-3-ethoxy-4-nitrophenyl ether (56 g., 83%, 71% pure) .
Example 7Z Preparation of 2-Cyano-a,a,a-trifluoro-£-tolyl-3-ethoxy-4-nitrophenyl ether A solution of potassium hydroxide (2.6 g., 0.04 mole) 87.3% pure and 3-ethoxy-4-nitrophenol (7.3 g., 0.04 mole) in methanol (30 ml) is stripped to dryness under reduce pressure. A residue of potassium 3-ethoxy-4-nitro-phenoxide is dissolved in sulfolane (200 g.) and 4-chloro-3-cyano-benzotrifluoride (8.2 g. , 0.04 mole) is added. Gas-liquid chromotography shows the reaction to be complete after stirring at 110°C for 4 1/2 hours and 135°C for 2 1/2 hours. The reaction mixture is cooled and poured into deionized water and the precipitate which forms is filtered off and air dried. Recrystallization from isopropanol yields 2-cyano~a,a,a-trifluoro-jD-tolyl-3~ethoxy-4-nitrophenyl ether (7.4 g. 53%) m.p. 143-145°C.
Example 19Z Preparation of 2-Chloro-oc,a,a-trifluoro-p_-tolyl-3-ethyl-am no-4-nitrophenyl ether A solution of l,-3-bis(2-chloro-a, fot-trifluoro-£-tolyloxy-4-nitrobenzene (12.8 g. 0.025 mol), and ethyl-amine (6.7 g. 0.15 mol ) in dioxane (120 ml.) is heated in a pressure bottle 4.5 hours at.50-55°C. and 4.3 hours at 90-95 °Co Benzene (200 ml), hexane (70 ml.) and water (500 ml) are added and the organic phase is washed with water (500 ml), 10% sodium bicarbonate solution (200 ml) and water (200 ml), dried, filtered through activated silica gel (25 g.), the solvents removed, and the residue is crystallized from hexane to give 2-chloro-x,a,a-trifluoro-£-tolyl-3-ethylamino-4-nitrophe~ nyl ether (7.9 g. 88%) m.p. 82-83°C.
Example 212 Preparation of 2-Chloro-oc,oc,a-trifluoro-j -tolyl-3-diethylamino-4-nitrophenyl ether A solution of 1, 3-bis( 2-chloro-oc,a,cx-trifluoro-£-tolyloxy)-4-nitrobenzene (1208 g« 0.025 ol) in p-dioxane (130 m ). is heated under reflux for 26 hours at 65-95°Cc with diethylamine (50 g, 0.66 mol). Benzene 500 ml) are added followed by hexane Cr^*70 ml) and the oil layer is separated, washed with water (500 ml), 10 % sodium bicarbonate solution (200 ml), and water (200 ml), dried, filtered through activated silica gel ( ^25 g.), the solvents removed.
The residual oil is distilled in vacuo to give 2-chloro-α,α,α-trifluoro-jo-tolyl-3-diethylarnino-4-nitrophenyl ether (8.15 g. 84%)b.p. 180-190°C./0.01 mm.
Example 25Z / Preparation of 2-Chloro-a,a,oc-trifluoro-£-tolyl-3- ( l-carboxyethoxy)-4-nitrophenyl ether , 2-Chloro-oc,a,a~trifluoro-£-tolyl-3-( 1-carbe- thoxy-ethoxy)~4-nitrophenyl ether (8.6 g. 0.02 mol), potassium hydroxide 86% (2.6 g. 0.04 mol), ethanol (8 ml.), dioxane (8 ml.), and water (100 ml.) are heated at 90-95°C. for 30 minutes. Ether (200 ml) and water (200 ml) are added and the mixture acidified with dilute sulfuric acid, the water layer extracted three times with ether (200 ml. each), dried, and the ether removed to give 2-chloro~o,a,oo-trifluoro-£-tolyl- 3-( l-carboxyethoxy)-4-nitrophenyl ether (6.4 g. 79%) Example 26Z Preparation of 2-Chloro-oc,a,a-trifluoro-]tolyl-3-( 1- carbethoxyethoxy)-4-nitrophenyl ether Potassium 2-nitro-5-( 2-chloro-cx,a,a-trifluoro £-tolyloxy)phenoxide (7.4 g. 0.02 mol), ethyl 2-bromo- propionate (3.6 g„ 0.02 mol) and sulfolane (50 ml) are heated 1.5 hours at 90-95°C, Benzene (100 ml.) and hexane (100 ml) are added and the solution is washed with dilute sodium carbonate solution then with water, dried, and the solvents removed. The residue is crystal lized from pentane to give 2-chloro-o,oc,α-trifluoro~£- tolyl"3«(l-carbethoxyethoxy)-4-nitrophenyl ether (6.2 g„, 71%) m.p. 71-74 °C.
S - 43 - 41766/2 Example 49Z Preparation of 2-chloro-a,a,a-trifluoro-j -tolyl-3-carbo-methoxy-4-nitrophenyl ether a) 3-Cya.no-4-nitrofluorobenzene m-fluorobenzonitrile (96.8 g., 0.8 mole) is added in two and one-half hours to a mixture of .concen trated sulfuric acid (GOO ml.) and potassium nitrate (80.9 g., 0.8 mole) at 3-6°C„, then allowed to warm to 25°Co The mixture is poured over cracked ice (3000 ml) extracted with chloroform (5 x 250 ml), dried and the solvent removed0 ' r . -51- Της residue is extracted with pentane and dried to give 3-cyaho-4-nitrofluorobenzene (115 g., 86.5 %) rr p. 102-104°C.' 1 b) 2-Chloro-o, ,α-trifluoro-£-tolyl-3-cyano-4-nitro- phenyi ether • The potassium phenoxide of 2-chloro-o,oc,a-tri-fluoro~£-cresol (13.5 g. 0.0688 mole) prepared in sulfo-lane at 5°C. is added to a- solution of 3-cyano-4—nitro-fluoro-benzene (11.4 g-. , 0.0688 mole) in sulfolane at 120 °C. in four hours, stirred 18 hours and cooled.
Benzene (200 ml) and hexane (100 ml) are added and the solution is water washed (5 x .250 ml), dried, filtered and the solvents removed. The residue is crystallized to give 2-chloro~a,a,a-£~tolyl~3~cyano-4-nitrophenyl ether (16c3 g., 69%) m.pe- 95-l03°C. 85% pure. c) 2-Chloro-a,a,oo-trifluoro- ~tolyl-3-carboxy-4-nitro- phenyl ether 2-Chloro- ,a,o .trifluoro-£-tolyl-3-cyano-4-nitrophenyl ether (11.2 g..0.0327 mole), acetic acid (25 ml), and hydrobromic acid (12 ml. of 47.8% purity) are heated at 120 °C, in a pressure bottle, for two days, poured over cracked ice and extracted v/ith benzene (2 x 150 rnl). The benzene solution is dried, filtered, the solvent removed, and the residue crystallized from pentane to give 2-chloro-oc,a,a-trifluoro-jD-tolyl- 3-carboxy- 4-nitrophenyl ether (7.5 g. 63.5%) m.p. 140-150°C. 85% d) 2-Chloro-cc,a,a-trifluoro-£-tolyl-3-carbomethoxy- 4-nitrophenylether Hydrogen chloride is bubbled through a solution of 2-chloro-x,a,a-trifluoro-£-tolyl-3-carboxy-4-nitrophenyl ether (2.3 g. 0.0064 mole) in methanol (50 ml) for ten hours at 32 °C., stirred overnite and the solvent removed to give 2-chloro-a,oc,cx-trifluoro-£-tolyl-3-carbomethoxy-4-nitrophenyl ether (1.5 g. 40%) Example 5 z Preparation of 2-chloro-c,a,o-trifluoro-£-tolyl-3-( l-carbamoylethoxy)-4-n:Ltrophenyl ether a) 2-Chloro-oc,a,a-trifluoro-p_-tolyl-3-( 1-chloroformylethoxy)-4-nitrophenyl ether · 2-Chloro-a, ,a-trifluoro-£-tolyl-3-( 1-carbo-xyethoxy)-4-nitrophenyl ether (34.8 g. 0.086 mol), thionyl chloride (20.4 g. 0.172 mol), and benzene (150 ml), are stirred 5 hours at 95°C0 and sixteen hours at 25°C. The benzene is removed to give 2-chloro-a,o,a-trifluoro-£-tolyl-3-( 1-chloroformylethoxy) -4-nitrophe-nyl ether (33.4 g. 92%). b) 2-Chloro-a,a,a-trifluoro-£-tolyl-3-( 1-carbamoyle- thoxy)-4-nitrophenyl ether A solution of 2-chloro- ,a,cx-.trifluoro-£-tolyl-3-( 1-chloroformylethoxy)-4-nitrophenyl ether (4.2 g. 0.01 mol) in ether (50 ml) is added to an ether solu tion (200 ml) saturated with gaseous ammonia at zero temperatures. After 30 minutes, water (100 ml) is added S3 and the ether layer separated. The aqueous phase is extracted with ether ( 3 x 200 ml) and the combined extracts dried, filtered through activated silica gel ( 20 g.), and the solvent removed to give 2-chloro-a,a,a-trif-luoro-£-toly-'l-3-( l~carbamoylethoxy)-4-nitro- -phenyl ether (2.4 g. 60%) m.p. 108-.111 °C0 Example 55Z Preparation of 2-Chl0ro-ct,a,oc-trifluoro-jo-tolyl-3-( 3-methyl- -ethylureido) -4-nitrophenyl ether a) · 2-Chloro-a,a,a-trifluoro-£-tolyl-3-(N-ethylchloro- form-amido) -4-nitrophenyl ether A .mixture of 2-chloro-x,o,a-trifluoro-p_-tolyl-3-ethylamino-4-nitro phenyl ether (3.6 g. 0.01 mol), phosgene (18.9 g. 0.19 mol), 2,6-lutidine (2.2 g. 0.02 mol), and benzene (/Vl30 ml), are heated in a pressure bottle 64 hours at 90-95°C. The mixture is cooled, filtered and the solvent removed"~to give 2-chloro-o,a,a-trifluoro-£-toly1-3-(N-ethyl-chloroformamido)-4-nitrophenyl ether. b) 2-Chloro-a,a,a-trifluoro-£-tolyl-3-( 3-methyl-l- ethylureido)-4-n trophenyl ether A solution of 2-chloro-x,a,a-trifluoro-p_-tolyl-3-(N-ethylchloroformamide)-4-nitrophenyl ether (4.4 g., 0.01 mol), methylamine (3.3 g. 0.11 mol) and benzene ml.) is allowed to stand twenty-five minutes at zero °Ce, filtered, and the solvent removed.
Benzene ( 00 ml) and hexane (50 ml) are added and the solution is washed with water (100 ml.) and aqueous 10% sodium carbonate solution (2 x 100 ml.), dried, and' the product absorbed on activated silica gel (/^25 g.). The product is eluted with a mixture of benzene (400 ml) and methanol (40 ml) the solvents removed and the product recrystallized to give 2-chloro> α,α,α-trifluoro-j -tolyl-3-( 3~methyl-l-ethylureido)-4-nitrophenyl ether (2.6 g. 62%) m.p. 127.5-128.5°C.
Example 56Z Preparation of 2 , 6-Dichloro-oc,a,oc-trifluoro-p_-tolyl-3-ethoxy-4-nitrophenyl ether a) 3 , 4-Dichloro-5-nitro-o,a,oc~trifluorotoluene 3 , 4-Dichloro-a,a,a-trifluorotoluene (862 g. 4.0 mols) is added to a stirred ^mixture of concentrated sulfuric acid (4400 g.) and nitric acid (3400 g.) at 35 °Co The mixture is stirred 70 minutes at 95°C<, and allowed to separate . The oil layer is washed once with water and twice with 5% sodium carbonate solution, dried, and fractionally distilled to give 3 , 4-dichloro-5-.nitro-oc,a,a-trifluorotoluene (188 g. 18%) b.p. 115-118°C./15 mm., 88% pure. b) 5-Amino-3 ,4-dichloro-a,a,a-trifluorotoluene- 500 ml. of an ethanolic solution containing 3 , 4-dichloro-5-nitro-a,a,a-trifluorotoluene (188 g, . GS ■ - 5¾ - 0.72mol), and platinum oxide (Adam's catalyst) (0.2 g.) is reduced at room temperature in a low pressure hydro-genatiori apparatus to give 5-Amino-3 , 4—dichloro-α,α ,o-trifluorotoluene (129.9 g. 78%) b.p. 65-70°C./l-2 mm. c) 3,4, 5-Trichloro-a,a, -trifluorotoluene A solution of sodium nitrite (39 g.) in water (85 ml.) is added over 1 hour to a solution of 5-amino-3, 4-dichloro-a,a,a-trifluorotoluene ( 17.5 g., 0.51 mol) in .1700 ml. 'concentrated hydrochloric acid at ~6°C. and the solution stirred for 1 hour then filtered. The filtrate dsadded to a solution of cuprous chloride (76.5 g.) in concentrated hydrochloric acid (500 ml) over 5 minutes at 0° to 8°C. and gradually heated to 80°Co over 80 minutes. The reaction mixture is cooled • to 35°Ce and extracted with hexane (2 x 300 ml). The extract is washed with water, 2% sodium hydroxide solution, dried and distilled to give 3,4,5-trichloro-a,a, a-trifluorotoluene (70 g. , 55%) b.p. 82-86°C./10 mm, 95% pure. d) 1,3-Bis( 2,6-dichloro-a,a,a-trifluoro-p-tolyl- oxy)benzene A mixture of 3,4,5-trichloro-oc,a,a-trifluorotoluene (10 g. 0.04 mol), and the dipotassium salt of ,3-dihydroxybenzene (4 g. 0.021 mol) in 150 ml. sul-folane is stirred and heated 70 minutes at ^120°C. The cooled reaction mixture is diluted with benzene (350 ml.) and washed once with water (100 ml.). Hexane (200 ml.) is added, and the solution washed with water (3 x 500 ml) dried, filtered through activated silica gel (fv»25 g.), and the solvents removed. The residual oil is crystallized from a mixture of pentane and benzene to give 1, 3-bis( 2, 6-dichloro-a,a,o-trifluoro-jD-tolyloxy) benzene (5.3 g. 49%) m.p. 121-122°C. e) 1, 3-Bis( 2, 6-dichloro-a,a,a-trifluoro-jo-tolyloxy)-4- nitrobenzene A cooled mixture of concentrated sulfuric acid (6.5 ml.) and nitric acid (4.4 ml.)is added with stirring to an ice cold solution of 1, 3-bis( 2, 6-dichloro-a,oc,a-tri-fluoro-£-tolyloxy.) -benzene (11.1 g. 0.021 mol) in ,2-dichl rethane (30 ml). After thirty minutes at room temperature, .the phases are allowed to separate and the organic phase washed twice with water. Benzene (200 ml) is added and the solution washed twice with dilute sodium carbonate solution, dried, filtered through activated silica gel (Λ 25 g.), and the solvents removed. The residual crystals are triturated with pentane, filtered, and dried to obtain 1, 3-bis( 2, 6-dichloro-a,a,a-trifluoro-£-tolyloxy)-4-nitrobenzene (9.9 g., 82%) m.p. 137.5-140.5°C, 90% pure. f ) 2, 6-Dichloro-a,a,a-trifluoro-£-tolyl-3-ethoxy-4- nitrophenyl ether A solution of potassium hydroxide, 86% (1.9 g., 0.029 mol) in ethanol (20 ml) is added to a solution of 1, 3-bis( 2, 6-dichloro-a,a,a-trifluoro-p_-tolyloxy)-4- nitrobenzene (8.0 g., 0.014 mol) in p-dioxane (70 ml) and warmed 1 hour at 50°C. The solution is cooled and benzene (Λ^250 ml) is added and crystals of potassium 2-nitro-5-( 2 , 6-dichloro-a, ,a-trifluoro-p_-tolyloxy) phenoxide (2.9 g. 52%) are collected. Treatment with acid yields the free phenol, 2, 6-dichloro-a,a,a-trifluo- ro-p_-tolyl-3-hydroxy-4-nitrophenyl ether (2.0 g. 40%) m.p. 84.5-86.5°C. This phenol (1.7g. 0.0046 mol) is reconverted to the potassium salt, dissolved in dimethylfor- mamide (20 ml) and treated with ethyl iodide (1.2 g. 0.0077 mol) 2.5 hours at 50-70°C. The reaction mixture is diluted with benzene (<~Ί00 ml) and hexane (^50 ml), washed with water ( 3 x 100 ml), dried, filtered through activated silica gel (^IS g.), and the solvents removed to give 2, 6-dichloro-a,a,a-trifluoro-£-tolyl-3- ethoxy-4-nitrophenyl ether (0.8 g. 44%) m.p. 100.5- 102°C.
From the filtrate of the 2.9 g. of phenoxide there is recovered ethyl 2,>6-dichloro-a,a,a-trifluoro-p_-tolyl ether (3.0 g. 82%) b.p. 78°C./5 mm, and an additional amount of the product 2, 6-dichloro-a,a,a-trifluoro-£-tolyl-3-ethoxy-4-nitrophenyl ether (0.35 g. , 6%) m.p. 88-93°C.
/ Examples 57 to 72 Following the procedures of Examples 1Z et seq . other diphenyl ethers of Formula I are prepared. Among the compounds which are prepared by these procedures are: LIST F α,α,α,α' ,α' ,α'-hexafluoro-2,4-xylyl-3-ethoxy-4-nitrophenyl ether, ' ,a4 ,a4-trifluoro-2 , 4-xylyi-3-n-propoxy-4-nitrophenyl ether, . 2-chloro-6,a,a,a-tetrafluoro-£-tolyl-3-ethyl-4-nitrophe- nyl ether, 2-iodo-a,a,a-trifluoro-£-tolyl-3-methoxy-4-nitrophenyl ether, 2-chloro-6-cyano-a,a,a-trifluoro-£-tolyl-3-methylthio-4- nitarophenyl ether, 4 4 4 2-bromo-a ,a ,a -trifluoro-4-, 6-xylyl-3-ethoxy-4-nitro- pheny 1 ether, 2-chloro-a,a,a,a' ,α' ,a'-hexafluoro-4, 6-xylyl-3-methoxy- 4-nitrophenyl ether, 2-bromo-a,a,a-trifluoro-£-tolyl-3-ethoxy-4-nitrophenyl ether, 2-chloro-a,a,a-trifluoro-£-tolyl-3-n-butyl-4-nitrophenyl ether, and / ' - 59 - LIST G 2-chloro-a,a,a-trifluoro-£-tolyl-3-bromo-4-nitrophenyl ether,- " 2-cyano-a,a,a-trifluoro-£-tolyl-3-acetoxy-4-nitrophenyl ether, 2-bromo-cx,a,a-trifluoro-p_- tolyl-3-diethylamino-4-nitro- phenyl ether, ' 2,6-dichloro-a,a,o-trifluoro-£-tolyl-3-ethylamino-4- nitrophenyl ether, 2-cyano-a,a,a-trifluQro-p_-tolyl-3-(l-carbethoxyethpxy)- 4-nitrophenol ether, 2-cyano-a,a,a-trifluoro-p_-tolyl-3-carbomethoxy-4-nitro- phenyl ether, 2-bromo-cx,a,a-trifluoro-p_-tolyl-3-carboxy-4-nitrophenyl ether.
These diphenyl ethers have erbicidal properties.
Examples 73-80 The following eight examples show the preparation of representative salts of the invention. a) Sodium 5-(2-Chloro-4-trifluoromethylphenoxy)-2-nitro- benzoate ■ ; , 5-(2-Chloro- -trifluoromethylphenox )-2-nitrobenzoic acid (1.7 g, 0.0047 mole) is dissolved in methanol (25 ml) and sodium hydroxide ( .7 ml of I N NaOH in methanol, 0.0047 mole) is added rapidly. The solvent is then removed in vacuo to give 1.9- g -of-product-that-decomposes at 217°C. b) Dimethylammonium 5-(2-Chloro-4-trifluoromethylphenoxy)- 2-nltrobenzoate 5-(2-Chloro-4-trifluoromethylphenoxy)-2-nitrobenzoic acid (2.0 g) is dissolved in toluene and an excess of anhydrous ; dimethylamine is bubbled into the reaction mixture, the solvent J removed in vacuo and the residue triturated with cold diethyl ether to give 1.1 g of product . • c) 2-Ethylhexyl )ammonium 5-(2-Chloro-4-trifluoromethyl- • phenoxy)-2-nitrobenzoate ' ' . 5-(2-Chloro-4-trifluoromethylphenoxy)-2-nitrobenzolc | acid (4.0 g, 0.011 mole) is dissolved in glyme (25 ml) and 2-ethylhexylamine (1.4 g, 0.011 mole) is added rapidly with , stirring at room temperature. After a short time the solvent is removed in vacuo to give a semi-solid that is triturated repeatedly with petroleum ether (bp. 30-60°C) and the solid product (5.1 g) melts at 82-8°C. Anal . Calcd. for C22¾61F3N205: C, 53.8J; H, 5-3 ; N, 5-71; CI, J.22; F, 11.61. Pound: C, 52.81; H, 5-18; N, 5*98; CI, 6.70; F. 11.27. i d) Tris-(2-hydroxyethyl)ammonium 5-(2-Chloro-4-trifluoro- methylphenoxy)-2-nltrobenzoate 5-(2-Chloro-4-trifluoromethylphenoxy)-2-nitrobenzoic acid (3.0 g, Ο.ΟΟ83 mole) is dissolved in glyme (20 ml) and a solution of triethanolamine (1.35 g> 0.0091 mole) in glyme (5 ml) is added rapidly while stirring at room temperature.
After stirring for a few hours the solvent is removed in vacuo, , the product is triturated repeatedly with petroleum ether (bp 30-60°C.) and dried to a weight of 2.5 g. Anal. Calcd. for C20¾2ClF5N20g: C, 47.02; H, 4.34; CI, 6.39; N, 5-^8; F, 11.15.· Found: C, 47-08; H, 4.78; CI, 6.48; N, 5.21; F, 10.16. e) Dicyclohexylammonium 5-(2-Chloro-4-trifluoromethylphenoxy)- 2-nltrobenzoate 5-(2-Chloro-4-trifluoromethylphenoxy)-2-nitrobenzoic acid (3-0 g, Ο.ΟΟ85 mole) is dissolved in glyme (20 ml) and dicyclohexylamine (1.64 g, 0.0091 mole) is added at room temperature while stirring. The solvent is removed in vacuo, the residue triturated with petroleum ether (bp 30-60°C. ) and dried to give 2.7 g of product, mp 197-9°0· Anal. Calcd. for C26H^0C1F5N205: C, 57-51; H, 5- 6 N, 5-15; Cl, 6.53; F, 10.49. Found C, 57,25; H, 5-71; N, 5-55, Cl, 6.40; F, 10.24. f. t-Octylammonium 5-(2-Chloro-4-trifluDromethylphenoxy)- 2-nitrobenzoate 5-(2-Chloro-4-trifluorcmethylphenoxy)-2-nitrobenzoic acid "(3..0 g, Ο.ΟΟ83 mole) is dissolved in glyme (20 ml) and t-octylamine (l;17 g, Ο.ΌΟ91 mole) is added rapidly while stirring. The solvent is removed in vacuo and the residue tri-turated with petroleum either (bp 30-60°C.) and dried to give 2.8 g of product, mp l40-57°C Anal. Calcd. for C22¾4C1F3N2°5: C> 53-82; H, 5*33; N, 5-70; Cl, 7.22: F, 11.6l.
Found: C, 53-50; H,'"5-37; N, 6.06; Cl, 6.87; F, 11.10. g) 2-Hydroxyethylamm0nium 5-(2-Chloro-4-trifluoromethyl- phenoxy)-2-nltrobenzoate A 20 aqueous solution of the salt is prepared by pulver-ing 5-(2-chloro-4-trifluoromethyl(phenox )-2-nitrobenzoic acid (22.2 g, 90$ pure) and slurrying it in water (62.8 g) . To this is added ethanolaraine (4.0 g, 10 purity) until a resultant pH of 8.0 is obtained. The slurry is then diluted further with water (11 g) to give tte desired aqueous concentration.
Similarly prepared (using the proper amine or metal hydroxide) are aqueous solutions of the following salts of 5-(2-chloro- -trifluoromethylphenoxy)-2-nitrobenzoic acid: Bls-(2-hydroxyethyl)ammonium salt Tris-(2-hydroxyethyl )ammonium salt Sodium salt Potassium salt h) Benzyitrimethyiammonium 5-(2-Chloro-4-trifluoromethyl- phenoxy)-2-nitrobenzoate A 20$ aqueous methanolic solution of the salt is prepared by slurrying 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro-benzoic acid (22.2 g, 90 pure) in water (50 g) and adding a 40$ solution of benzyitrimethyiammonium methoxide (-27 g) in methanol to pH 8. Additional water (0.8 g) is then added to give the desired concentration.
The following Examples A-D show the herbicidal properties of the diphenyl ethers of the invention.
Example A This example shows the herbicidal activity diphenyl ethers of the invention towards a number of common weeds. Using the procedure described below, diphenyl ethers were evaluated for control of the following weeds : .
At 10 pounds per acre: Monocots Dicots barnyardgrass (Echinochloa crus. ) bindweed ( Convolvulus arvensis ) crabgrass (Digiteria spp) curly dock ( Rumex crispus ) nutsedge (Cyperus esculentus) yelvetleaf (Abutilon theophrasis) wild oats (Avena Fatua) wild mustard (Brassica haber) at 2 and 4 pounds per acre: Monocots barnyardgrass (Echinochloa crusqalli) • *Bermudagrass (Cyanodon dactylon) crabgrass (Diqitaria spp.) •downy brome (Bromus tectorum) foxtail (asbaria faberii) Johnsongrass (Sorghum halepense) nutsedge (Cyperus esculentus) quackgrass (Agropyron repens) •ryegrass (Lolium perenne) / •wild oats (Avena fatua) •yellow millet (Panicum miliaceum) - 61 - 41766/2 Dicots bindweed (Convolvulus arvensis) cocklebur (Xanthium pensylvanicum) ••caffeeweed (Sesbania macrocarpa) 'curly dock (Rumex crispus) •lambsquarters (Chenopodium album) morningglory (Iopmoea purpurea) •pigweed (Amaranthus retroflexus) ♦•ragweed (Ambrosia artemisiifolia ) *smartweed (Polygonum pensylvanicum) ••tomato (Lycopersicon esculentum) velvetleaf (Abutilon theophrasti) •wild carrot (Daucus carota) •wild mustard (Brassica haber) , JExamples 1 to 5 only Examples 6 to 8 only The following test procedure is employed. Seeds of selected crops and weeds are planted in soil in flats.
For preemergence tests, the flats are treated with the test compound immediately after the planting, For post- emergence tests, the seed are allowed to germinate, and after two weeks the flats are treated with the test compound. The compound to be evaluated is dissolved in acetone, diluted with water, and sprayed over the flats t using a carrier volume equivalent to 50 US. gallons per acre . ' - 62 - at the rate of application (pounds per acre, lb/A.) specified in the tables. About two weeks after the application of the test compound, the state of growth of the plants is observed and the phytotoxic effect of the com- v pound is evaluated. Table III gives the average percent control achieved by the test compounds in terms of the percent of the plants which are killed by the compounds.
TABLE III HERBICIDAL ACTIVITY ' (% control) Compound of Preemerqence Postemerqence Example No lb. /A. 10 2 10 4 2 1 M* 96 82 71 99 75 74 D* 97 52 51 100 74 81 2 M 77 96 96 100 99 92 D 97 100 88 100 92 85 3 - M 94 96 100 87 D 95 71 100 77 4 M 87 99 100 94 D 100 83 100 94 "Π -5 - ra 0_ —7-3- 7-3— — 9L_ t yD —D Q—→9 9 49— M 100 86 D 100 99 M 86 75 34 46 D 85 73 73 92 *M - Monocots; D - Dicots - 63 - at the rate of application (pounds per acre, lb/A.) specified in the tables. About two weeks after the application of the test compound, the state of growth of the plants is observed and the phytotoxic effect of the compound is evaluated. t able III gives the average percent control achieved by the test compounds in terms of the percent of the plants which are killed by the compounds.
TABLE III HERBICIDAL ACTIVITY (% control) Example No lb. /A. 10 4 2 10 4 2 1 M* 96 82 71 99 75 74 D* 97 52 51 100 74 81 2 M 77 96 96 100 99 92 D 97 100 88 100 92 85 3 94 96 100 87 D 95 71 100 77 4 M 87 99 100 94 D 100 83 100 94 5 M 0 73 77 19 D 0 39 90 49 6 M 100 86 D 100 99 7 M 86 75 34 46 D 85 73 73 92 8 M 81 72 . 24 35 D 82 78 70 73 •M - Monocots; D - Dicots - 63 - 41766/2 Example B This example shows the selective herbicidal activity of diphenyl ethers of the invention in a number of agronomic crops. Following the test procedure of Example Ά , diphenyl ethers of the invention are evaluated for significant tolerance (as shown by 50% or less kill of the test crop at levels of application which give more than 50% kill of many or all of the weeds of Example A towards some or all of the following common agronomic crops (not all compounds tested against all crops): alfalfa, snapbeans, corn, cotton, cucumbers, peanuts, rape, rice, soybeans, tomatoes, and wheat.
Tolerance to snapbeans in preemergence applications is shown by the compounds of Examples 1,2 and 6. Tolerance to corn in preemergence applications is shovm by the compounds of Examples 1,2 and in postemergence applications by the compounds of Examples 1,2 and 6.
Tolerance to cotton in preemergence applications is shown by the compounds of Examples 1,2 and 6 and in posterner-gemce or layby applications by the compound of Example 1. Tolerance to peanuts in preemergemce application is shown by the compounds of Examples 1 and 2. Tolerance to soybeans in preemergence application is shown by the compounds of Examples 1 and 2 and in postemergence or layby application by the compound, of Example 2. Tolerance to rice in preemergence applications is shown by the compounds of Examples 1 and 2 and in postemergence 41766/2 applications or in applications on transplanted rice by the compounds of Examples 1,2, and 8. Tolerance to wheat in preemergence and postemergence applications is shown by. the compounds of Examples 1,2, and Example g This example shows the herbicidal activity of diphenyl ethers of the invention towards a number of common weeds. Using the procedure described below, diphenyl ethers were evaluated for control of the following weeds: < At 10 pounds per acre: Monocots Ί ' barnyardgrass (Echinochloa crusqalli) crabgrass (Diqitaria spp) nutsedgje (Cyperus esculentus) wild oats (Avena fatua) Dicots bindweed (Convolvulus arvensis) curly dock (Rumex crispus) velvetleaf (Abutilon theophrasti) wild mustard (Brassica haber) At .2 and 4 pounds per acre: - 65 - Monocots barnyardgrass (Echinochloa crusgalli) * •Bermudagrass (Cynodon dactylon) crabgrass (Diqitaria . spp. ) •downy brome (Bromus tectorum) foxtail (Setaria faberii) Johhsongrass (Sorghum halepense) nutsedge (Cyperus esculentus) quackgrass (Aqropyron repens) ♦ryegrass (Lollum perenne) •wild oats (Avena fatua) •yellow millet (Panicum milliaceum) Dicots bindweed (Convolvulus arvensis) cocklebur (Xanthium pensylvanicum) ••coffeeweed (Sesbania macrocarpa) •curly dock (Rumex crispus) •lambsquarters (Chenopodium album) morningglory (Ipomoea purpurea) •pigweed (A aranthus retroflexus) ••ragweed (Ambrosia artemisiifolia ) •smartweed (Polygonum pensylvanicum) ••tomato (Lycopersicon esculentum) velvetleaf (Abutilon theophrasti) •wild carrot (Daucus carota) •wild mustard (Brassica haber) •Examples 1Z to 9Z only ••Examples 10Z to 56Z only 41766/2 The following test procedure is employed. Seeds of selected crops and weeds are planted in soil irt flats. For preemergence tests, the flats are treated with the test compound immediately after the planting. For postemergence test, the seeds are allowed to germinate, and after two weeks the flats are treated with the test compound. The compound to be evaluated is dissolved in acetone, diluted with water, and sprayed over the flats using a carrier U.S. volume equivalent to 50/gallons per acre at the rate of application (pounds per acre, lb/A.) specified in the tables. About two weeks after the application of the test compound, the state of growth of the plants is observed and the phytotoxic effect of the compound is evaluated. Table IV gives the average percent control achieved by the test compounds in terms of the percent of the plants which are killed by the compounds.
TABLE IV HERBICIDAL ACTIVITY (% control) Compound of Preemerqence Postmerqence Example No. lb. /A. 10 4 2 10 4 . 2 , z . Μ· 42 76 82 57 D* 35 45 100 58 2Z M 97 97 100 99 D 100 80 100 100 3Z 1 . 99 89 • •84 100 99 +96 D 100 99 •*66 100 100 +97 4Z M 98 - 80 D 100 100 5Z M 97 84 100 99 D 100 78 100 100 6Z M 65 77 97 .91 D 70 55 lob 94 7Z M 61 65 65 100 75 82 • D 60 57 54 100 77 80 6 8Z M 8 1 52 85 48 35 D 82 57 46 100 80 66 9Z M 99 90 81 100 97 82 D 92 66 67 100 81 75 10Z M 70 66 67 7 D 100 70 98 85 11Z M 81 88 82 100 D 98 99 99 100 12Z M 86 72 77 99 D 96 93 100 100 13Z M 76 '78 77 100 D 90 72 98 100 14Z M 64 30 61 91 D 78 22 94 100 ·* 1/4 lb. /A. + 1/2 lb. /A. - 68 - f TABLE IV (cont'd) Compound of Preemerqence Postemerqence Example No. lb. /A. K _4 2 _4 2 , 15Z 'M 99 68 79 76 D 100 90 . 99 94 16Z M 86 67 77 8? D 94 75 96 94 17Z .M 51 20 45 39 84 31 89 98 18Z M 67 99 28 28 D 100 100 86 98 - 19Z M 91 77 84 94 D 96 91 98 97 20Z M 88 80 78 80 D 99 93 88 97 21Z M . 91 79 74 90 D 99 90 96 94 2Z_ M 72 63 60 70 D * 98 77 99 100 23Z M 90 55 82 71 D 64 87 100 100 24Z M 91 62 86 84 D 68 97 99 100 25Z M 87 40 97 88 D 88 93 100 100 26Z M 98 75 99 93 D 100 99 100 100 2.7Z M 76 74 82 99 D 98 90 100 100 28Z M 74 79 73 73 D 95 79 99 100 29Z M 74 66 79 97 D 73 84 100 100 - 69 - TABLE IV (cont'd) Compound of Preemerqence Postemerqerice Example No.. lb. /A . 4 2 4 2 30Z M 81 78 75 91 D 99 94 100 100 31Z M 74 68 " 61 68 D 99 69 100 100 32Z M 86 81 86 100 D 100 81 100 100 33Z M 5 3 79 32 65 , D 99 74. 98 100 ' 34Z M 35 83 32 47 D 5 2 85 89 90 , 35 Z ' M 40 60 45 63 D 40 72 98 80 36Z M' 93 100 87 94 D 100 100 , 100 98 37Z M 99 100 92 100 D 100 100 100 100 . 38Z . M 47 62 43 51 D 86 68 98 58 39Z M 65 77 64 61 D 99 80 98 100 40Z M 86 88 64 81 D 9 2 98 100 100 41Z M 60 84 71 56 D · 96 62 95 94 42Z M 62 83 38 63 D 80 60 98 88 43Z M 0 99 2 61 D /48 100 47 80 44Z M 66 0 60 7 D 96 17 98 10 45Z M 13 68 17 5 3 D 58 77 88 78 - 70 - 41766/2 TABLE IV (cont'd) Compound of Preemerqence Pos emerqence Example No. lb. /A. 4 2 " • 2 46Z M 0 34 0 0 D - 20 87 30 4 47Z M 61 80 11 24 D 40 80 72 84 48Z M 99 100 75 84 D . 97 100 100 97 49Z M 92 100 86 77 D 95 100 100 · 100 • 50Z M 90 98 97 100 D 83 100 100 100 51Z . M . 79 96 75 86 D 100 100 100 98 52Z M 79 98 87 ' 93 D 67 .75 100 100 53Z M • 98 98 79 81 D 83 100 100 100 54Z M 83 98 79 71 D 75 98 100 100 55Z M 91 69 31 D 73 95 96 56Z M 91 100 99 100 D 83 100 100 99 M -- Monocots; D nDicots Example J?..
This example shows the selective herbicidal activity of diphenyl ethers of the invention in a number of agronomic crops. Following the general test procedure of Example C , diphenyl ethers are evaluated for significant tolerance (as shown by 50% or less kill of the - 71 - 41766/2 test crop at levels of application which give more than 50% kill of many or all of the weeds of Example C towards some or'?ll of the following common agronomic crops (not all . compounds tested against all crops): alfalfa, snapbeans, corn, cotton, cucumbers, peanuts, rape, rice, safflower, · soybeans , tomatoes, and wheat.
Tolerance to snapbeans in preernergence applications is shown by the compounds of Examples 4Z and 26Z. Tolerance to corn in preernergence applications is shown by the compounds of Examples 4Z,' 11Z, 19Z, 21Z, 34Z, 40Z, 52Z, and 54Z and in post-emergence applications by the compounds of Examples 4Z, 18Z, 19Z, 21Z, 26Z, 34Z, 36Z, 40Z, 49Z, 52Z, 53Z, 54Z, and 56Z, Tolerance to cotton in preernergence applications is shown by the compounds of Examples 3Z, 4Z, and 30Z, and in postemergence or layby applications by the compound of Example 3Z. Tolerance to peanuts in preernergence applications is shown by the compounds of Examples 3Z, 19Z, 21Z, 30Z, 34Z, 36Z, 40Z 48Z, 49Z, 50Z, 52Z, 53Z, arid 56Z and in postemergence applications by the compounds of Examples 4Z, 18Z, 342 36Z, 37Z, 40Z, 48Z, 5όΖ, and 54Z. Tolerance to rice in preernergence applications is anown by the compounds of Examples 4Z, 19Z, 21Z, 30Z, 34Z, 40Z, 52Z and 54Z and in postemergence applications or in applications on transplanted rice by the compounds of Examples' 3Z, 11Z, 18Z, 20Z, 30Z, 34Z, 40Z, 48Z, 53Z, and 54Z.
Tolerance to safflower in preemergence applications is shown by the compound of Example 3Z. Tolerance to soybeans in preemergence applications is shown by the compounds' of Examples 3Z, 4Z, HZ, 18Z, 19Z, ' 21Z, 26Z, 30Z, 34Z, 40Z, 48Z, 49Z, 50Z, 52Z, 53Z, and 54Z, in postemergence or layby applications by the compound of Examples 3Z and 34Z. Tolerance to wheat in preemergence applications is shown by 'the compounds of Examples 4Z, 18Z, 19Z, 26Z, 34Z, 40Z, 50Z, 54Z and 56Z and in postemergence applications by the compounds of Examples 4Z, 18Z, 21Z, 30Z, 34Z, 36Z, 48Z, and 54Z. - 73 - 41766/4

Claims (2)

1. CLAIMS 1· A herbicidal compound of the formula wherein, X is hydrogen, halogen, trifluoromethyl , (C^-C^Ja or cyano, Y is hydrogen or halogen, and Z is hydrogen or a substi uent group or atom selected from: (1) (C.-Cf) alkoxy, (2) alkoxyalkoxy having 1 to 4 carbon 1' 6 atoms in each alkoxy moiety, (3) hydroxy (C^^) alkoxy , (4) carboxy (C-^-C^) alkoxy in free acid or salt form, (5) carbalkoxy (C1~C4)^alkoxy having up to 4 carbon atoms in th ester alkoxy group, (6) halogen, (7) (C-^-C^ ) alkyl , (8) amino substituted with two alkyl groups having a total of up to 6 carbon atoms or an alkylcarbonyl group of up to 4 carbon atoms, (9) carboxy in free acid or salt form, or (10) carbalkoxy of up to 5 carbon atoms. - 74 - (ll) a (C^-C^) alkoxy group substituted with a dialkylnm ί ;io of up to k carbon atoms, a trifluoromethyl , a ( C 1~C^ ) a Iky1 - carbonyl, a halo-substituted (C j-C^ ) alkylcarbonyl , an .epoxy, a (C^-C^) alkylthio, a (C^-C^) alkylsulfonyl , a carbamoyl, a a (Cj-C^) alkylcarbamoyl , a di (C ^-C^ ) alkylcarbamoyl ,/_ ( C^-C^ ) - alkenyl or/(C2-C^) alkynyl group, { 12 ) a dihydroxy (C 1-C^ ) - alkoxy group, (13) morpholino , (14) (^-C^) alkyl ~~(C ^C^ ) - hydroxyalkyl or (C 1~C^ ) alkylcarbamoyl amino , (15) (C^C^)- alkylcarbamoylamino , (l6) (Cj-C^ Jhydroxyalkyl , (17) mono- or di(C1-C^)alkylthiocarbonylamino, (18) cyano, (19) (c2~C-i^~ alkanoyloxy, (20) carbamoylox , (21) alkylcarbamoyloxy having ΐΠ up to 6 carbon atoms, (22) hydroxy or (23) amino., with ^ ?l V 0 the proviso that X, Y and Z cannot all be hydrogen.
2. A compound according to Claim 1 in which X and Y are as defined in Claim 1 and Z is hydrogen., with the proviso ; j · , . :t that X, Y and Z cannot all be hydrogen. 3· A compound according to Claim 2 in which X is halogen or cyano and Y is hydrogen or halogen. 4. A compound according to Claim 3 in which X is chlorine and Y is hydrogen. 5. A compound of the formula set forth in Claim 1 .In which X and are as defined in Claim 1 but in which Z is (1) (C^-C^) alkoxy, (2) alkoxyalkoxy having 1 to k carbon atoms in each alkoxy moiety, (3) hydroxy (C 1~C^ ) alkoxy, ( ) carboxy(C1-C1t)alkoxy, (5) carbalkoxyiC^C^alkoxy having up to carbon atoms in the ester alkoxy group, (6) halogen, (7) (C^C^) alkyl, (8) amino substituted with two alkyl groups having a total of up to 6 carbon atoms or an alkylcarbonyl group of up to A carbon atoms, (9) carboxy or (lO) carbalkoxy of up to 5 carbon atoms. 6. ' A compound according to Claim 5» wherein X is 41766/3 (ll) a (C^-C^) alkoxy group substituted with a dialkylamino of. up to k carbon atoms, a trifluoromethyl , a (C^-C^)alkyl- carbonyl, a halo-substituted (C^-C^Jalkylcarbonyl , an ,epoxy 2. λ compound according to Claim 1 in which X and Y are as defined in Claim 1 and Z is hydrogen · 3· A compound according to Claim 2 in which X is halogen or cyano and Y is hydrogen or halogen. 4· A compound according to Claim 3 in which X is chlorine and Y is hydrogen. 5· A compound of the formula set forth in Claim 1 in which X and Y are as defined in Claim 1 but in which Z is (l) (Cj-Cg) alkoxy, (2) alkoxyalkoxy having 1 to 4 carbon atoms in each alkoxy moiety, (3) hydroxy(C^-C^) alkoxy, (4) carboxyiCj-C^) alkoxy, (5) carbalkoxy(C j-C^) alkoxy having up to 4 carbon atoms in the ester alkoxy group, (6) halogen, (7) (C^-C^)alkyl , (8) amino substituted with two alkyl group having a total of up to 6 carbon atoms or an alkylcarbonyl group of up to 4 carbon atoms, (9) carboxy or (lO) carbalkox of up. to 5 carbon atoms. ' I 6. A compound according to Claim 5» wherein X is halogen and Y is hydrogen. ' φ. , A compound according to Claim wherein X is chlorine. . A compound according to Claim » wherein X is chlorine, Y is hydrogen and Z is alkoxy. 9j¾. A compound according to Claim wherein Z is ethoxy. 5 10^· A compound according to Claim fi, wherein X is chlorine, Y is hydrogen and Z is carbalkoxy or carbal- koxyalkoxy. wherein Z is ( 1-carbethoxy) ethoxy. 12/4/4. A compound of the formula set forth in Claim 1 in which X and Y are as defined in Claim 1 but in which Z is (l) a (C^-C^) alkoxy group substituted with a dialkylamino gr of up to 4 carbon atoms, a trifluoromethyl , a (C^-C^alkyl- carbonyl, a halo-substituted (C^C^Jalkylcarbonyl, an epbxy, a (C^C^) alkylthio, a (C^C^) alkylsulfonyl , a carbamoyl, a (C -C. ) alkylcarbamoyl, a diiC.-C^alkylcarbamoyl,/ (Cg-C^)- alkenyl alkoxy group, (3) morpholino, (¾) (C^C^) alkyl ~(C1-C¾)- hydroxyalkyl or alkylcarbamoylamino, (6) (C^C^ )hydroxyalkyl , (7) mono- or di(C1-CZt)alkylthiocarbonylamino, (8) cyano, (9) (C2—C^)— alkanoyloxy, (10) carbamoyloxy, (ll) alkylcarbamoyloxy having up to 6 carbon atoms, (12) hydroxy or (13) amino. 13 . A compound according to Claim being any of those compounds disclosed in foregoing Lists A or E with the ex- 4 ception of the compound claimed in Claim -76- 41766/3 ^ 14· A compound according to Claim 5» being any of those compounds disclosed in foregoing Lists B or F or Table II, Examples 1Z to Z but excluding the compounds claimed in Claims 8 and 10. 15· A compound as claimed in Claim 1, "being any one of th individual compounds disclosed in the foregoing description but excluding those compounds claimed in Claims 4» 9» 11» 13 and 14. 16· A method for the preparation of a 4-trifluoromethyl 4 '-nitrodiphenyl ether according to Claim 2 vrhich includes the step of reacting at an elevated temperature a substitut halobenzene with (a) a phenolic compound in the presence of an alkaline agent or (b) a potassium or sodium salt of a phenolic compound. 17. A method according to Claim .6 » wherein the ring substituents required in the diphenyl ether end product are present in said substituted halobenzene and in said phenolic compound or salt of the latter. 18. A method according to Claim 16, wherein all the ring substituents required in the diphenyl ether end product are not present in said substituted halobenzene and in said phenolic compound or salt of the latter and wherein the missing ring substituent ( s ) is or are then introduced into the reaction product of the substituted halobenzene and said phenolic compound or salt of the latter. 19. A method according to Claim 17, ^wherein said phenolic compound, or salt thereof, contains at least one of the groups or atoms CF^, X and Y required in the diphenyl ether end product. - 77 - 2 20 1 7 ψ i~ · A method according to Claim to, wherein said substituted halobenzene contains at least one of the groups or atoms CF^ , X and Y required in the diphenyl ether end product. 5 201. A method according to Claim 2^0, wherein said substituted halobenzene contains a CF^- group and two halogen atoms in the positions meta and para to the CF_ group. 22 1 7 £Λ· A method according to Claim ^p, wherein said phenolic compound, or salt thereof," contains the nitro group required in the diphenyl ether end product. 23 1 7 A method according to Claim wherein said substituted halobenzene contains the nitro group required in the diphenyl ether end product. 24 k · method for the preparation of a ¾-trifluoromethyl- ¾' -nitrodiphenyl ether according to Claim 1 which comprises nitrating a diphenyl ether having all the ring substituents required in the end product except for the k*-nitro substituent . 25 24 A method according to Claim wherein the diphenyl ether subjected to nitration is prepared by a method accordant to Claim 15· 26 A method for the preparation of a ¾-trifluoro- 5/ methyl-¾ '-nitrodiphenyl ether according to Claim A which includes the step of reacting at an elevated temperature a substituted halobenzene with (a) a phenolic compound in the presence of an alkaline agent or (b) a potassium or sodium salt of a phenolic compound. - 78 - - n - 41766/3 27· A method according to Claim 26, wherein all the ring substituents required in the diphenyl ether end product are not present in said substituted halobenzene and in said phenolic compound or salt of the latter and the missing ring substituent ( s ) is or are then introduced into the reaction product of the substituted halo- benzene and said phenolic compound or salt of the latter. 28. A method according to Claim 26, 'wherein said substituted halobenzene contains at least one of the groups or atoms CF^, X and Y required in the diphenyl ether end product. 29· A method according to Claim 28,^ wherein said substituted halobenzene contains the CF^ group and two halogen atoms in the positions meta and para to the CF^ group. 30. A method according to Claim 26»' wherein said phenolic compound, or salt thereof, contains at least one of the groups Og and Z required in the diphenyl ether end product. 31. A method for the preparation of a 4-trif.luoromethyl- * -nitrodiphenyl ether according to Claim 5 which includes the step of nitrating a diphenyl ether lacking a .'-nitro substituent. 32. A method according to Claim 31, wherein the diphenyl ether subjected to nitration is prepared by a method according to Claim 26. 33. A. method for the preparation of compounds as claimed in Claim 1, being a method substantially as hereinbefore described in any of Examples 1 to 3, 6 to 8, 3Z, 7Z, 19Z, 21Z, 25Z, 26Z, 49Z, 51Z, 55Z and 56Z. - 79 - 3j , A herbicidal composition comprising a herbicidal 1 5 compound according to any of Claims l-jf^ and an agronomi- cally acceptable carrier, surface active agent, adhesive agent or other herbicide, 35 h* A method of controlling weeds in a growth medium which comprises applying a herbicide (a) to the growth medium prior to emergence of weeds therefrom or (b) to weed seedlings in a growth medium, the herbicide being applied in an amount sufficient to control the growth of the weeds, wherein there is applied as herbicide a compound according to any of Claims 36 35 flpm A method according to Claim wherein the growth medium contains or is to be planted with an agronomic crop. 37 36 A method according to Claim wherein the herbicide is incorporated in the growth medium prior to planting the crop and prior to the emergence of the weeds from the growth medium, p 3 *]7. · A method according to Claim ^ 31^, wherein the agronomic crop is cotton, soybeans, peanuts, safflower, beans, peas, carrots or a cereal crop, 39 35 -38 $βο A method according to any of Claims J^-fJ% wherein the herbicide is applied at a rate of 0,1 to 12 pounds per acre, 40 35 $0. A method according to Claim substantially as hereinbefore described with reference to each of the tests reported in Examples A-D,
IL41766A 1972-03-14 1973-03-13 Diphenyl ethers and their use as herbicides IL41766A (en)

Applications Claiming Priority (4)

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US23465172A 1972-03-14 1972-03-14
US234656A US3888932A (en) 1972-03-14 1972-03-14 Herbicidal 4-trifluoromethyl-4-nitrodiphenyl ethers
US05/331,947 US4076741A (en) 1972-03-14 1973-02-12 Herbicidal 4-trifluoromethyl-4-nitrodiphenyl ethers
US331719A US3928416A (en) 1972-03-14 1973-02-12 Herbicidal 4-trifluoromethyl-4{40 nitrodiphenyl ethers

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IL41766A0 IL41766A0 (en) 1973-05-31
IL41766A true IL41766A (en) 1977-04-29

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GB (1) GB1423376A (en)
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Families Citing this family (21)

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USRE32216E (en) * 1969-04-25 1986-07-29 Rhone-Poulenc Agrochimie Salts of substituted phenoxybenzoic acids, compositions of the same and herbicidal use thereof
USRE32243E (en) * 1969-04-25 1986-09-09 Rhone-Poulenc Agrochimie Esters of substituted phenoxybenzoic acids, compositions of the same and herbicidal use thereof
USRE32215E (en) * 1971-02-11 1986-07-22 Rhone-Poulenc Agrochimie Substituted phenoxybenzoic acids compositions of the same and herbicidal use thereof
JPS5436209B2 (en) * 1972-10-24 1979-11-08
EG11593A (en) * 1973-07-03 1980-07-31 Bayer Ag Halogenated 4-trifluiromethyl-4-cyano-diphenyl-ethers process for their preparation and their use as herbicides
JPS5724761B2 (en) * 1973-12-19 1982-05-26
JPS5068800U (en) * 1973-10-22 1975-06-19
JPS50123824A (en) * 1974-03-15 1975-09-29
JPS50132125A (en) * 1974-04-12 1975-10-20
JPS5173126A (en) * 1974-12-23 1976-06-24 Mitsui Toatsu Chemicals SATSUSOZAI
JPS545033A (en) * 1977-06-15 1979-01-16 Mitsui Toatsu Chem Inc Herbicides
DE2938595A1 (en) * 1979-09-24 1981-04-23 Celamerck Gmbh & Co Kg, 6507 Ingelheim METHOD FOR PRODUCING DIPHENYL ETHERS
DE2942930A1 (en) * 1979-10-24 1981-05-27 Basf Ag, 6700 Ludwigshafen SUBSTITUTED UREAS, THEIR PRODUCTION AND USE AS HERBICIDES
DE3045805A1 (en) 1980-12-05 1982-07-08 Basf Ag, 6700 Ludwigshafen DIPHENYL ETHER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS HERBICIDES
DE3269621D1 (en) * 1981-08-07 1986-04-10 Ciba Geigy Ag Phenoxyphenyl-aminocarboxylic-acid derivatives, their preparation, compositions containing them and their use
JP2801181B2 (en) * 1983-01-10 1998-09-21 キヤノン株式会社 Sheet reversing device
FR2549047B1 (en) * 1983-07-12 1986-03-21 Rhone Poulenc Agrochimie NOVEL HERBICIDES DERIVED FROM ARYLOXYBENZENES CARBONIMIDES
CA1274843A (en) * 1984-05-18 1990-10-02 Yoshiharu Hayashi 2-nitro-5-(2'-chloro-4'- trifluoromethylphenoxy)phenylacetic ester, thioester and amide, process for preparation thereof, herbicidal composition, and method for destruction of undesirable weeds
HU193466B (en) * 1984-11-12 1987-10-28 Budapesti Vegyimuevek Fungicidal composition comprising 2-nitrobenzoic acid derivative as active substance
JPS63157065U (en) * 1987-04-02 1988-10-14
IL133454A0 (en) * 1998-12-23 2001-04-30 Rohm & Haas Preparation of diphenylethers

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FR1602719A (en) * 1968-11-22 1971-01-18 Herbicidal diphenylether/pheny urea compos - ition

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RO77037A (en) 1981-08-30
NL7303590A (en) 1973-09-18
FR2175997B1 (en) 1977-02-04
IL41766A0 (en) 1973-05-31
SU713520A3 (en) 1980-01-30
IE37575B1 (en) 1977-08-31
IT983545B (en) 1974-11-11
SE416544B (en) 1981-01-19
PH18682A (en) 1985-08-29
JPS5825641B2 (en) 1983-05-28
GB1423376A (en) 1976-02-04
IE37575L (en) 1973-09-14
FR2175997A1 (en) 1973-10-26
LU67204A1 (en) 1973-09-14
CH567359A5 (en) 1975-10-15
AU467605B2 (en) 1975-12-04
AU5328973A (en) 1974-09-19
OA04348A (en) 1980-01-31
NL174825B (en) 1984-03-16
TR18291A (en) 1976-12-28
AR208495A1 (en) 1977-02-15
HU172709B (en) 1978-11-28
KE2734A (en) 1977-05-27

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