Claims
- 1. A compound having the formula ##STR67## in which R.sub.1 is naphthyl, optionally substituted by up to 2 halogens; or phenyl, optionally substituted by one or more of: C.sub.2 -C.sub.5 carboalkoxy, C.sub.1 -C.sub.4 alkylsulfonyl, C.sub.1 -C.sub.4 haloalkylsulfonyl, C.sub.2 -C.sub.5 alkylcarbonyl, C.sub.2 -C.sub.4 alkenyl, C.sub.3 -haloalkenoxy, C.sub.1 -C.sub.4 haloalkylthio, C.sub.3 -C.sub.6 cycloalkyl, phenyl, monosubstituted phenyl, pyridyloxy, C.sub.2 -C.sub.4 alkyleneoxy, C.sub.1 -C.sub.4 alkylenedioxy, C.sub.1 -C.sub.3 haloalkylenedioxy, C.sub.2 -C.sub.4 alkylene, amido, nitro, cyano, up to two C.sub.1 -C.sub.4 alkylthio groups, up to three C.sub.1 -C.sub.4 alkoxy groups, up to three C.sub.1 -C.sub.4 haloalkoxy groups, up to three C.sub.1 -C.sub.4 alkyl groups, up to three C.sub.1 -C.sub.4 haloalkyl groups, or up to five halogens;
- R.sub.2 is cyclopropyl, optionally substituted by one or 4 methyl groups or up to 2 halogens; and
- R.sub.3 is ##STR68## in which m is 0 or 1; A, B and C are each carbon or nitrogen, provided that A, B and C are not all nitrogen and if two of A, B and C are nitrogen, then A and C are nitrogen;
- R.sub.4 is hydrogen, monohalo or dihalo;
- R.sub.6 is hydrogen, methyl, fluoro or ethynyl; and
- R.sub.7 is ##STR69## in which D and E are each carbon or nitrogen provided that both D and E are not nitrogen, and further provided that if any of A, B or C is nitrogen, then D and E are both carbon; and
- R.sub.5 is hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, trifluoromethyl, cyano, C.sub.1 -C.sub.4 alkylthio, C.sub.1 -C.sub.4 alkylsulfonyl, or mono- or polyhalo; ##STR70## in which R.sub.8 is hydrogen or halogen; or ##STR71## in which (i) R.sub.9 is 4-fluoro, 4-methoxymethyl, or 4-propargyl, and R.sub.10 is fluoro or
- (i) R.sub.9 is 3- or 4-allyl, 3- or 4-propargyl, or 3- or 4-(mono- or dihalo)allyl, and R.sub.10 is hydrogen or fluoro; ##STR72## (d) 4-phenoxy-2-butyn-2yl; (e) 4-(benzyloxy)benzyl;
- (f) 4-(4-fluorobenzyloxy)benzyl; ##STR73## (h) 4-(4-trifluoromethyl-2-pyridyloxy)benzyl; provided that: R.sub.1 is not 2,3-dichlorophenyl, 2,6-difluorophenyl, 2,6-di(C.sub.1 -C.sub.4 alkyl)phenyl, 2,4,6-tribromophenyl or 2,4,6-tri(C.sub.1 -C.sub.4 alkoxy)phenyl.
- 2. A compound according to claim 1 further in which R.sub.1 is not 2,6-disubstituted phenyl, 2,3,6-trisubstituted phenyl or 2,4,6-trisubstituted phenyl.
- 3. A compound according to claim 1 in which R.sub.1 is ##STR74## wherein R.sub.11 is hydrogen, halogen, C.sub.1 -C.sub.4 pl alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkylthio, C.sub.1 -C.sub.4 haloalkoxy, C.sub.1 -C.sub.4 haloalkylthio, C.sub.2 -C.sub.5 carboalkoxy, C.sub.2 -C.sub.5 alkylcarbonyl, nitro or cyano; R.sub.12 is hydrogen, halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, C.sub.1 -C.sub.4 alkylthio, C.sub.1 -C.sub.4 haloalkylthio, C.sub.3 -haloalkenoxy, nitro, cyano, C.sub.2 -C.sub.5 alkylcarbonyl, C.sub.1 -C.sub.4 alkylsulfonyl or C.sub.2 -C.sub.5 carboalkoxy; and R.sub.13 is hydrogen, halogen, C.sub.1 -C.sub.4 haloalkyl or C.sub.1 -C.sub.4 alkoxy, or R.sub.11 and R.sub.12 taken together are C.sub.2 -C.sub.4 alkylene, C.sub.1 -C.sub.4 alkyleneoxy, C.sub.1 -C.sub.4 alkylenedioxy or halo-C.sub.1 -C.sub.3 alkylenedioxy; and R.sub.14 is hydrogen or fluoro; provided that R.sub.11, R.sub.12 and R.sub.13 are not all hydrogen.
- 4. A compound according to claim 3 in which R.sub.13 is hydrogen and R.sub.11 and R.sub.12 are other than hydrogen.
- 5. A compound according to claim 3 in which R.sub.11 and R.sub.13 are hydrogen.
- 6. A compound according to claim 3 in which R.sub.12 and R.sub.13 are hydrogen.
- 7. A compound according to claim 3 in which R.sub.12 is a C.sub.1 -C.sub.2 polyhaloalkoxy group containing at least one fluorine atom and R.sub.13 is hydrogen or halogen.
- 8. A compound according to claim 7 in which R.sub.11 is halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.1 haloalkyl, C.sub.1 -C.sub.4 alkoxy or C.sub.1 -C.sub.4 haloalkoxy; R.sub.13 is hydrogen; and R.sub.14 is halogen.
- 9. A compound according to claim 3 in which R.sub.12 is trifluoromethoxy and R.sub.11, R.sub.13 and R.sub.14 are all hydrogen.
- 10. A compound according to claim 3 in which R.sub.11 is chloro, R.sub.12 is fluoro, R.sub.13 is hydrogen and R.sub.14 is hydrogen.
- 11. A compound according to claim 1 in which R.sub.2 is cyclopropyl, monomethyl-substituted cyclopropyl or tetramethyl-substituted cyclopropyl.
- 12. A compound according to claim 1 in which R.sub.3 is ##STR75## wherein m is 0 or 1, A and B are independently nitrogen or carbon, provided that A and E are not both nitrogen; R.sub.4 is hydrogen or halo; R.sub.5 is hydrogen, mono- or polyhalo, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, trifluoromethyl, cyano, or C.sub.1 -C.sub.4 alkylthio; and R.sub.6 is hydrogen or methyl.
- 13. A compound according to claim 3 in which R.sub.3 has the formula ##STR76## in which A is nitrogen or carbon and R.sub.4 and R.sub.5 are each independently hydrogen or halogen.
- 14. A compound according to claim 13 in which A is carbon, and R.sub.4 and R.sub.5 are both hydrogen.
- 15. A compound according to claim 13 in which A is carbon, R.sub.4 is hydrogen and R.sub.5 is halogen.
- 16. A compound according to claim 15 in which R.sub.5 is fluoro.
- 17. A compound according to claim 13 in which A is carbon, R.sub.4 is halogen and R.sub.5 is hydrogen.
- 18. A compound according to claim 17 in which R.sub.4 is fluoro.
- 19. A compound according to claim 13 in which A is carbon and R.sub.4 and R.sub.5 are both halogen.
- 20. A compound according to claim 19 in which R.sub.4 is fluoro and R.sub.5 is chloro.
- 21. A compound according to claim 19 in which R.sub.4 and R.sub.5 are both fluoro.
- 22. A method for controlling insects comprising applying to an insect, the locus of an insect or a locus at which insecticidal control is desired, an insecticidally effective amount of a compound according to claim 1.
- 23. A method for controlling insects according to claim 22 in which the insect is a member of the order Lepidoptera.
- 24. A method for controlling insects comprising applying to an insect, the locus of an insect, or a locus at which insecticidal control is desired, an insecticidally effective amount of a compound according to claim 3.
- 25. A method for controlling insects comprising applying to an insect, the locus of an insect or a locus at which insecticidal control is desired, an insecticidally effective amount of a compound according to claim 13.
- 26. An insecticidal composition comprising (a) an insecticidally effective amount of a compound according to claim 1; and (b) an insecticidally suitable diluent or carrier.
CROSS REFERENCE TO RELATED APPLICATIONS
This is a continuation-in-part of application Ser. No. 263,605, filed Oct. 31, 1988 and of application Ser. No. 264,746, filed Oct. 31, 1988, both of which are continuations-in-part of application Ser. No. 122,877, filed Nov. 17, 1987 now abandoned.
This invention relates to a series of novel imidate insecticides distinguished by the general formula ##STR2## in which
R.sub.1 is an optionally substituted aryl group in which the substituents are halo, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkoxy, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkylthio, C.sub.3 -C.sub.6 cycloalkyl, nitro, C.sub.1 -C.sub.4 haloalkyl, C.sub.2 -C.sub.5 carboalkoxy, C.sub.1 -C.sub.4 alkylthio, cyano, C.sub.1 -C.sub.4 alkysulfonyl, C.sub.1 -C.sub.4 haloalkylsulfonyl, C.sub.2 -C.sub.5 alkylcarbonyl, C.sub.2 -C.sub.4 alkyleneoxy, C.sub.1 -C.sub.2 perhaloalkyleneoxy, C.sub.1 -C.sub.4 alkylenedioxy, C.sub.1 -C.sub.3 halo-substituted alkylenedioxy, phenyl, mono-substituted phenyl, pyridyloxy, C.sub.2 -C.sub.4 alkylene, C.sub.2 -C.sub.4 alkenyl, C.sub.3 -haloalkenoxy, and/or amido;
R.sub.2 is cyclopropyl or mono- or poly- or halo- or methyl-substituted cyclopropyl; and
R.sub.3 is (a) an optionally substituted 3-phenoxyphenalkyl, 3-phenoxypyridylalkyl, 3-(pyridyloxy)phenalkyl, 3-phenylaminophenalkyl, 3-benzylphenalkyl or benzyloxyphenalkyl moiety; (b) a benzylfuranylmethyl moiety; (c) a 3- or 4-substituted benzyl or tetrafluorobenzyl moiety; (d) 4-phenoxy-2-butyn-2-yl; (e) 2-methyl-3-phenylbenzyl; or (f) 4-(4-trifluoromethyl-2-pryidyloxy) benzyl.
Compounds of this invention demonstrate activity in controlling various types of insects, including lepidoptera, hemiptera and coleoptera, particularly in foliar application.
Another aspect of this invention involves insecticidal compositions comprising an insecticidally effective amount of a compound of the invention with an insecticidally suitable diluent or carrier.
In another aspect, this invention involves a method for controlling insects by administration of an insecticidally effective amount of a compound or composition of this invention to a locus where control is desired.
The term "insects" as used herein refers to the broad and commonly understood usage rather than to those creatures which in the strict biological sense are classified as insects. In addition to those belonging to the class Insecta, this term includes some classes of acarids such as mites and the like.
More particularly, the compounds of formula (I) are those in which:
R.sub.1 is a naphthyl, optionally substituted by up to 2 halogens; or phenyl, optionally substituted by one or more of the following: C.sub.2 -C.sub.5 carboalkoxy, C.sub.1 -C.sub.4 alkylsulfonyl, C.sub.1 -C.sub.4 haloalkylsulfonyl, C.sub.2 -C.sub.5 alkylcarbonyl, C.sub.2 -C.sub.4 alkenyl, C.sub.3 -haloalkenoxy, C.sub.1 -C.sub.4 haloalkylthio, C.sub.3 -C.sub.6 cycloalkyl, phenyl, monosubstituted phenyl, pyridyloxy, C.sub.2 -C.sub.4 alkyleneoxy, C.sub.1 -C.sub.2 perhaloalkyleneoxy, C.sub.1 -C.sub.4 alkylenedioxy, C.sub.1 -C.sub.3 halo-alkylenedioxy, C.sub.2 -C.sub.4 alkylene, amido, nitro, cyano, up to two C.sub.1 -C.sub.4 alkylthio groups, up to three C.sub.1 -C.sub.4 alkoxy groups, up to three C.sub.1 -C.sub.4 haloalkoxy groups, up to three C.sub.1 -C.sub.4 alkyl groups, up to three C.sub.1 -C.sub.4 haloalkyl groups, or up to five halogens; R.sub.2 is cyclopropyl, optionally substituted by up to 4 methyl groups or up to 2 halogens; and
R.sub.3 is: ##STR3## in which m is 0 or 1;
A, B and C are each carbon or nitrogen, provided that A, B and C are not all nitrogen and if two of A, B and C are nitrogen, then A and C are nitrogen;
R.sub.4 is hydrogen, monohalo or dihalo;
R.sub.6 is hydrogen, methyl, fluoro or ethynyl; and
R.sub.7 is ##STR4##
in which D and E are each carbon or nitrogen provided that both D and E are not nitrogen, and further provided that if any of A, B or C is nitrogen, then D and E are both carbon; and
R.sub.5 is hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, trifluoromethyl, cyano, C.sub.1 -C.sub.4 alkylthio, C.sub.1 -C.sub.4 alkylsulfonyl, or mono- or polyhalo; ##STR5##
in which R.sub.8 is hydrogen or halogen; or ##STR6## in which
(i) R.sub.9 is 4-fluoro, 4-methoxymethyl, or 4-propargyl, and R.sub.10 is fluoro or
(ii) R.sub.9 is 3- or 4-allyl, 3- or 4-propargyl, or 3- or 4-(mono- or dihalo)allyl, and R.sub.10 is hydrogen or fluoro; ##STR7##
(d) 4-phenoxy-2-butyn-2yl;
(e) 3-bromo-4-fluorobenzyl;
(f) 4-(benzyloxy)benzyl;
(g) 4-(4-fluorobenzyloxy)benzyl; ##STR8##
(j) 4-(4-trifluoromethyl-2-pyridyloxy)benzyl.
R.sub.1 is not 2,3-dichlorophenyl, 2,6-difluorophenyl, 2,6-di(C.sub.2 -C.sub.4 alkyl)phenyl, 2,4,6-tribromophenyl or 2,4,6-tri(C.sub.1 -C.sub.4 alkoxy)phenyl.
A more preferred class of compounds are those in which R.sub.1 does not contain substituents at both ortho positions on the phenyl ring, i.e., in which R.sub.1 does not contain a 2,6-disubstitution, 2,3,6-trisubstitution, or a 2,4,6-trisubstitution on the phenyl ring.
An even more preferred class is that in which the phenyl ring of R.sub.1 is substituted at the 3-, 4-, and/or 5-positions, including mono-, di- and tri-substituted phenyl compounds, as well as phenyl compounds having a 3,4-alkylene, alkyleneoxy, perhaloalkyleneoxy, alkylenedioxy, or haloalkylenedioxy substitution. Such compounds more particularly have the formula ##STR9## in which R.sub.2 and R.sub.3 are as defined about; R.sub.11 is hydrogen, halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkylthio, C.sub.1 -C.sub.4 haloalkoxy, C.sub.1 -C.sub.4 haloalkylthio, C.sub.2 -C.sub.5 carboalkoxy, C.sub.2 -C.sub.5 alkylcarbonyl, nitro or cyano; R.sub.12 is hydrogen, halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, C.sub.1 -C.sub.4 alkylthio, C.sub.1 -C.sub.4 haloalkylthio, nitro, cyano, C.sub.2 -C.sub.5 alkyl- carbonyl, C.sub.1 -C.sub.4 alkylsulfonyl or C.sub.2 -C.sub.5 carboalkoxy; and R.sub.13 is hydrogen, halogen, C.sub.1 -C.sub.4 haloalkyl or C.sub.1 -C.sub.4 alkoxy, or R.sub.11 and R.sub.12 taken together are C.sub.2 -C.sub.4 alkylene, C.sub.2 -C.sub.4 alkyleneoxy, C.sub.1 -C.sub.4 alkylenedioxy or halo-C.sub.1 -C.sub.3 alkylenedioxy; and R.sub.14 is hydrogen or fluoro; provided that R.sub.11, R.sub.12 and R.sub.13 are not all hydrogen.
One especially preferred subclass of such compounds is that in which R.sub.11 is as defined above, and most preferably is halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy or C.sub.1 -C.sub.4 haloalkoxy; R.sub.12 is a C.sub.1 -C.sub.2 polyhaloalkoxy group containing at least one fluorine atom; and R.sub.13 is hydrogen or halogen. Examples of such polyhaloalkoxy groups are difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, difluorobromomethoxy, and 1,1,2,2-tetrafluoroethoxy. Preferably R.sub.14 is hydrogen. In one such type of compound, R.sub.11 is chloro, R.sub.12 is trifluoromethoxy and R.sub.13 and R.sub.14 are both hydrogen.
Also of interest are compounds having a 2,5-, 2,3,4- or 2,4,5-substitution pattern.
As used herein, these terms have the following meanings:
"Haloalkyl", "haloalkoxy" and similar terms include groups substituted by one or more of the same or different halogens.
"Alkyleneoxy" and "alkylenedioxy" refer to linking groups having 1 or 2 oxygen atoms, respectively, and at least one carbon atom (optionally substituted) in a chain. The alkyleneoxy moieties have 1-4, preferably 2-4, carbon atoms in this chain and include, for instance, ethyleneoxy (--O--C.sub.2 H.sub.4 --), dihalomethyleneoxy, dihaloethyleneoxy, and the like. Alkylenedioxy moieties include methylenedioxy (--O--CH.sub.2 --O--), 1,2-ethylenedioxy (--O--C.sub.2 H.sub.4 --O--), mono- or di-halomethylenedioxy (a methylenedioxy group in which one or both hydrogens are replaced by a halogen) and isopropylenedioxy (--O--C(CH.sub.3).sub.2 --O--).
The term "carboalkoxy" refers to a group having the formula ##STR10## in which R.sub.15 is an alkyl group. The carbon atom content of the carboalkoxy group is meant to include the carbon atom of the carbonyl moiety in that group. Thus, C.sub.2 -carboalkoxy refers to carbomethoxy, etc. Similarly, the carbon atom content of an alkylcarbonyl group includes the carbon atom in the carbonyl moiety. The simplest member of this group is thus acetyl, CH.sub.3 C(O)--.
When R.sub.1 represents a phenyl ring substituted by a second phenyl ring, the second phenyl ring may be unsubstituted or mono-substituted in which the substituent is halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, nitro, cyano, C.sub.1 -C.sub.4 alkylsulfonyl, C.sub.1 -C.sub.4 haloalkylsulfonyl, or C.sub.1 -C.sub.4 alkylenedioxy (optionally further substituted by up to 2 halogens).
Terms defining halogenated groups such as "haloalkyl", "haloalkoxy", "haloalkenyl", "haloalkenoxy" and the like include mono- and polyhalogenated groups of the indicated number of carbon atoms. In polyhalogenated groups the halogens may be the same or different.
For the various subgroups falling within the general definition of R.sub.3, preferred types are:
For R.sub.4 : hydrogen and 2-,4- or 6-monohalo, particularly monochloro or monofluoro;
For R.sub.5 : 2-,3- or 4-halo, 2,4-, 3,4- or 3,5-dihalo, particularly difluoro, pentahalo, particularly pentafluoro, 4-trifluoromethyl, 4-methyl, 4-methoxy, 4-methylthio and 4-methylsulfonyl.
The following are examples of specific embodiments of groups falling within the definition of R.sub.3. For convenience in specifying positions of substitution of compounds of the type ##STR11## the position of attachment of the group ##STR12## was given the number 1 and the position of attachment of group R.sub.7, the number 3. When A, B or C was a nitrogen atom, the compounds were designated pyrid-2-yl, pyrid-6-yl or pyrid-4-yl, respectively.
Compounds of this invention in general are prepared by reaction of an imidoyl halide (preferably chloride) with an alkali metal alkoxide according to the general reaction: ##STR13## in which M is an alkali metal, preferably sodium or potassium and Hal is a halogen, particularly chloro or bromo.
This reaction is conducted at a temperature of from about -70.degree. C. to about +65.degree. C., most preferably at about room temperature, for a time which may range from about 5 minutes to about 24 hours. The reaction is conducted in the presence of a solvent, for example, an aromatic hydrocarbon such as benzene, toluene, or xylene, or an ether, such as diethyl ether, diisopropyl ether, diisoamyl ether, dibutyl ether, furan, 1,3-dimethoxyethane, or tetrahydrofuran (preferably tetrahydrofuran). In some instances, apparent to those skilled in the art, it is advantageous to add the solution of the alkali metal alkoxide to a solution of the imidoyl halide or to use substantial excesses of alkoxide. The resulting product may be recovered by conventional techniques.
The alkoxide R.sub.3 OM is produced by reaction of an appropriate alcohol, such as 3-phenoxybenzyl alcohol, with an alkali metal-containing base, for instance, an alkali metal hydride (e.g., potassium or preferably sodium hydride) in the presence of a solvent such as that used in reaction of the alkali metal alkoxide with the imidoyl halide. In general, this reaction is conducted at reflux temperature under an inert atmosphere for a time which may range up to about 2 hours.
The alcohols, if not commercially available, can be prepared according to known methods such as those described in the following references: U.S. Pat. Nos. 4,256,893, 4,261,920, and 4,329,518; and Volume 7 of the test "Chemie der Pflanzenschutz und Schadlingsbekampfungsmittel" (phenoxybenzyl, phenoxypyridyl and pyridyloxybenzyl type alcohols); Elliott et al., J. Chem. Soc. (C), 1971, pp 2551-1554 (5-benzyl-2-furanylmethanol), Pesticide Science 14, 560-570 (1983) (2-methyl-3-phenylbenzyl alcohol); U.S. Pat. No. 4,594,355; British patent No. 2,122,616; U.S. Pat. No. 4,370,346; European patent applications Nos. 196,156 and 271,240; and J. Sci. Food & Agriculture, 18, 167 (1967) for various substituted benzyl alcohols; European patent application 211,561 for 3-phenylaminobenzyl alcohols; Swiss patent No. 549,342 for 4-phenoxy-2-butyn-1-ol; and Japanese patent No. 49-27331 for 1-(3-phenoxyphenyl)-2propyn-1-ol.
The imidoyl halide may be prepared from a starting amine having the formula R.sub.1 NH.sub.2 or amide having the formula ##STR14## depending on availability. The amines are either generally available or may be prepared by procedures known in the art; for example, those described in "Compendium of Organic Synthetic Methods", Harrison et al. (Wiley-Interscience, N.Y., 1971).
The amides, if not available, may be produced by reaction of the amine with an appropriate acid chloride having the formula ##STR15## The temperature of this reaction ranges from about -40.degree. C. to about +80.degree. C. Suitable solvents include hydrocarbon solvents such as toluene and chlorinated hydrocarbon solvents such as methylene chloride, chloroform, carbon tetrachloride, ethylene dichloride, tetrachloroethane and the like, preferably methylene chloride. This reaction is conducted in the presence of a base, preferably a tertiary amine. Suitable bases include triethylamine, quinoline, dimethylaniline, diethylaniline, and pyridine. Triethylamine is the preferred base. The resulting amide is recovered and purified by conventional means.
The imidoyl halide may be prepared from the amide by reacting it with a halogenating agent such as phosphorus pentachloride or phosgene in an organic solvent such as that utilized in the amide production (preferably methylene chloride) or alternatively using phosphorus oxychloride as the solvent. The reaction is carried out under an inert atmosphere for a time which may be up to 24 hours, preferably from 1 to 24 hours, at a temperature of from about 0.degree. C. to about 110.degree. C. Before the imidoyl chloride-containing product is passed to the final step, all substances, such as phosphorus oxychloride or hydrogen chloride, which can react with the alkoxide in the final step, should be removed. This can generally be accomplished by evaporation or distillation.
Alternatively, the compounds of this invention may be prepared by a two-step process indicated as follows:
In the first step, the appropriate alcohol (for instance a phenoxybenzyl alcohol) is mixed with a nitrile having the formula R.sub.2 CN at a temperature of from about -20.degree. C. to about +40.degree. C. Then, a solution of a mineral acid such a hydrochloric, hydrobromic, sulfuric or phosphoric acid (preferably hydrochloric acid) dissolved in a suitable organic solvent is added at temperatures from about -5.degree. to about 40.degree. C., preferably 0.degree. C., then stirred at room temperature, to produce the corresponding imidate salt. Suitable solvents for this reaction include aromatic hydrocarbons such as benzene, toluene, or xylene and ethers such as diethyl ether, diisopropyl ether, diamyl ether, furan, tetrahydrofuran and dioxane (preferably dioxane). Time for the reaction may be up to 52 hours. The imidate salts are novel and constitute an aspect of this invention.
In the second step, the imidate salt is suspended in an organic solvent such as that utilized in the previous step, preferably benzene, and reacted with an amine having the formula R.sub.1 NJ.sub.2. The mixture is reacted, optionally with stirring, at a temperature of between about -50.degree. and +80.degree. C., most preferably at room temperature, for a period of time necessary to conduct the reaction, which may be up to 120 hours. The final imidate product may be recovered as in process (A).
A third process may be used for producing the compounds of this invention. This process proceeds by way of an intermediate ketenimine, which may be prepared from the amide or from the imidoyl halide. In the first case, the amide (prepared for instance, as described in process (A) is reacted with an inexpensive base and a trivalent phosphorus compound, preferably triphenylphosphine. The base is preferably a tertiary amine such a triethylamine. The reaction is carried out at a temperature of from about -10.degree. C. to 40.degree. C. in the presence of a halogen, preferably chlorine or bromine, and an aromatic or chlorinated hydrocarbon solvent such as benzene, toluene, xylene, methylene chloride, ethylene dichloride, chloroform, carbon tetrachloride, tetrachloroethane and the like, preferably methylene chloride. The reaction may then be conducted under reflux temperature of the solvent and the ketenimine recovered according to methods known in the art.
Alternatively, the ketenimine may be prepared by reaction of the imidoyl halide with a base, as just described, but no halogen or trivalent phosphorus compound present.
In the second step of this process, the ketenimine is reacted with an alcohol having the formula R.sub.3 OH in the presence of a solvent, preferably an ether solvent, such a diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran or 1,2-dimethoxyethane and an alkali metal base such as potassium or sodium hydride, preferably sodium hydride. This reaction is conducted under reflux for a time as necessary which may be up to 48 hours, preferably from about 2 to about 10 hours, at the end of which the reaction mixture is cooled and the imidate product recovered as described above.
This process can be depicted by the general scheme: ##STR17## in which R.sub.1, R.sub.2 and R.sub.3 are as previously described and R.sub.16 is a 1,2-ethylene group optionally substituted by up to 4 methyl groups or up to 2 halogens.
Ketenimines ##STR18## are novel.
This process may be used as an alternative to Process (A) for preparation of compounds of this invention from alcohols (R.sub.3 OH) which are sensitive to, and could be adversely affected (e.g. decomposed) by, strong bases such as the alkali metal-containing bases (e.g. alkali metal hydrides) used to prepare the alkoxides (R.sub.3 OM). Alcohols which may be sensitive to such strong bases include phenoxypyridyl alkanols, alpha-ethynyl alcohols (R.sub.6 is ethynyl) such as 1-(3-phenoxyphenyl)-2-propyn-1-ol and tetrafluoropropargylbenzyl alcohol.
Compounds of this type may be made by direct reaction of the alcohol with the imidoyl chloride in the presence of a tertiary amine base and a reaction-promoting amount of a 4-di(lower alkyl)aminopyridine, preferably 4-dimethylaminopyridine.
Tertiary amines which may be used in this process include trialkylamines such as trimethyl-, triethyl-, tri-n-butylamine and the like, including tertiary amines having mixed alkyl groups, N,N-dialkylanilines such as N,N-dimethylaniline, pyridine and various substituted pyridines. Preferred tertiary amines, primarily for economic reasons, are triethylamine, N,N-dimethylaniline and pyridine. The tertiary amine may even be an additional amount of the promoter 4-di(lower alkyl)aminopyridine, over and above that amount needed for promoting the reaction.
The tertiary amine is preferably used in a stoichiometric amount with respect to the alcohol, but may be used in excess of that amount. The promotor 4-di(lower alkyl)aminopyridine may be used in an amount from about 0.05 to about 1 equivalent per equivalent of alcohol, preferably from about 0.05 to about 0.15 equivalent per equivalent, most preferably about 0.1.
This process is preferably conducted at temperatures of from about 20.degree. C. to about 50.degree. C. Lower temperatures may be used, but the reaction rate would be much slower. The process is carried out in the presence of an inert solvent such as an aromatic hydrocarbon (for instance, benzene, toluene or xylene), chlorinated solvent (such as methylene chloride, ethylene dichloride or chlorobenzene) or an ether (such as diethyl ether, dioxane or tetrahydrofuran).
While this process is particularly suitable for producing compounds from base-sensitive alcohols, it may be used to produce compounds of this invention in general from other alcohols as described.
Alpha-fluorophenoxybenzyl compounds are made from the alphafluorobenzyl halide (preferably bromide) rather than the alcohol by reaction with an amide, R.sub.1 NHCOR.sub.2, in the presence of a halide ion binding agent such as silver oxide or a silver salt, and an inert solvent. Reaction temperatures are from about -20.degree. C. to about 100.degree. C.
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Continuation in Parts (3)
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Number |
Date |
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| Parent |
263605 |
Oct 1988 |
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| Parent |
264746 |
Oct 1988 |
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| Parent |
122877 |
Nov 1987 |
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Patent Grant
4994488
