Pyrazole-glycolic acid amide derivatives as herbicides

Abstract

Pyrazole-glycolic acid amides of the following formula (1) (in which R.sup.1 to R.sup.5 each represent a hydrogen atom or a substituent having a broad definition), and herbicides containing them. The compounds have a high herbicidal effect against paddy weeds, especially Echinochloa crus-galli, while highly safe for paddy rice plants. ##STR1##

Description

This application is 371 of PCT/JP92/01476 filed on Nov. 12, 1995.

TECHNICAL FIELD

The present invention relates to novel pyrazole-glycolic acid amide derivatives and to herbicides containing them as the active ingredients.

BACKGROUND ART

At present, a lot of herbicides have been put to practical use as those applicable to paddy fields, and they are popularly used as single products or combination products.

Herbicides may be applied to various kinds of paddy weeds. A lot of herbicides effective against annual broad-leaved weeds are known, and herbicides effective against perennial weeds are increasing in these several years.

However, since Echinochloa crus-galli, which is one serious paddy weed and which grows mostly in large areas of paddy fields, belongs to the same family of Gramineae as a paddy rice plant belongs to, herbicides which are effective against only, Echinochloa crus-galli, especially those that have grown tall, without injuring paddy rice plants at all are not almost known.

As the prior art relating to compounds which are similar to the compounds of the present invention with respect to their chemical structures, compounds having a glycolic acid amide moiety bonded to the 2-position of a benzothiazole ring have been disclosed in JP-A 54-154762, compounds having the same moiety bonded to a 5-membered aromatic mono-cyclic ring containing an oxygen atom or a sulfur atom along with from 1 to 3 nitrogen atoms have been disclosed in JP-A 55-147267, compounds having the same moiety bonded to the 5-position of a tetrazole ring have been disclosed in JP-A 56-86175, and compounds having the same moiety bonded to the 5-position of an isoxazole ring have been disclosed in JP-A 63-152367. However, compounds having a glycolic acid amide moiety bonded to a pyrazole ring, such as those of the present invention, are not known at all up to the present and are novel compounds.

DESCRIPTION OF THE INVENTION

We, the present inventors have continued assiduous studies for many years so as to develop herbicides that are selectively effective against only harmful weeds without injuring important crop plants, while having investigated a lot of compounds with respect to their herbicidal activity so as to create herbicidal compounds which have a higher herbicidal activity and a broader selectivity in the activity. As a result, we have found that pyrazole-glycolic acid amide derivatives of the following formula (1) (hereinafter referred to as compounds of the present invention) have a high herbicidal activity against Echinochloa crus-galli and other paddy weeds, while having a high safety for paddy rice plants, and that the derivatives are effective even when a small amount of them is used. On the basis of these findings, we have completed the present invention. ##STR2## wherein

R.sup.1 represents a hydrogen atom, a C.sub.1-6 alkyl group, a C.sub.3-6 cycloalkyl group, a C.sub.2-4 alkenyl group, a C.sub.2-4 alkynyl group, a C.sub.3-6 cycloalkyl-substituted C.sub.1-2 alkyl group, a C.sub.1-4 haloalkyl group, a di-C.sub.1-4 alkylamino-C.sub.1-4 alkyl group, a C.sub.1-4 alkoxy-C.sub.1-4 alkyl group, a C.sub.1-4 alkylthio-C.sub.1-4 alkyl group, a C.sub.1-4 alkylsulfinyl-C.sub.1-4 alkyl group, a C.sub.1-4 alkylsulfonyl-C.sub.1-4 alkyl group, a phenyl-substituted C.sub.1-4 alkyl group, a phenyl group (optionally substituted by one or more substituents selected from a C.sub.1-4 alkyl group, a C.sub.1-4 haloalkyl group, a C.sub.1-4 alkoxy group, a cyano group, a nitro group and a halogen atom), a C.sub.1-4 alkoxy group, a C.sub.1-4 haloalkoxy group, a benzyloxy group, a C.sub.1-4 alkylthio group, a benzylthio group, a C.sub.1-4 alkylsulfinyl group, a C.sub.1-4 alkylsulfonyl group, a di-C.sub.1-4 alkylsulfamoyl group, a cyano group, a halogen atom, a di-C.sub.1-4 alkylamino group or a nitro group;

R.sup.2 represents a hydrogen atom, a C.sub.1-6 alkyl group, a C.sub.3-6 cycloalkyl group, a C.sub.2-4 alkenyl group, a C.sub.2-4 alkynyl group, a C.sub.3-6 cycloalkyl-substituted C.sub.1-2 alkyl group, a C.sub.1-4 haloalkyl group, a C.sub.1-4 alkylcarbonyl-C.sub.1-4 alkyl group, a C.sub.1-4 alkoxycarbonyl-C.sub.1-4 alkyl group, a di-C.sub.1-4 alkylamino-C.sub.1-4 alkyl group, a C.sub.1-4 alkoxy-C.sub.1-4 alkyl group, a C.sub.1-4 alkoxy-C.sub.1-4 alkoxy-C.sub.1-4 alkyl group, a C.sub.1-4 alkylthio-C.sub.1-4 alkyl group, a C.sub.1-4 alkylsulfinyl-C.sub.1-4 alkyl group, a C.sub.1-4 alkylsulfonyl-C.sub.1-4 alkyl group, a phenyl-substituted C.sub.1-4 alkyl group, a phenyl group (optionally substituted by one or more substituents selected from a C.sub.1-4 alkyl group, a C.sub.1-4 haloalkyl group, a C.sub.1-4 alkoxy group, a cyano group, a nitro group and a halogen atom), a naphthyl group, a pyridyl group (optionally substituted by one or more substituents selected from a C.sub.1-4 alkyl group, a C.sub.1-4 haloalkyl group, a C.sub.1-4 alkoxy group, a cyano group, a nitro group and a halogen atom), a C.sub.1-4 alkylcarbonyl group, a C.sub.1-4 alkylaminocarbonyl group, a di-C.sub.1-4 alkylaminocarbonyl group, a C.sub.1-4 alkoxycarbonyl group, a C.sub.1-4 alkylsulfonyl group or a di-C.sub.1-4 alkylsulfamoyl group;

R.sup.3 represents a hydrogen atom, a C.sub.1-6 alkyl group, a C.sub.3-6 cycloalkyl group, a C.sub.2-4 alkenyl group, a C.sub.2-4 alkynyl group, a phenyl group (optionally substituted by one or more substituents selected from a C.sub.1-4 alkyl group, a C.sub.1-4 haloalkyl group, a C.sub.1-4 alkoxy group, a cyano group, a nitro group and a halogen atom), a cyano group, a halogen atom or a nitro group;

R.sup.4 and R.sup.5 independently represent a hydrogen atom, a C.sub.1-6 alkyl group, a C.sub.3-6 cycloalkyl group, a C.sub.2-4 alkenyl group, a C.sub.2-4 alkynyl group, a C.sub.3-6 cycloalkyl-substituted C.sub.1-2 alkyl group, a C.sub.1-4 alkoxy-C.sub.1-4 alkyl group, a phenyl-substituted C.sub.1-4 alkyl group (in which the phenyl moiety may be optionally substituted by one or more substituents selected from a C.sub.1-4 alkyl group, a C.sub.1-4 haloalkyl group, a C.sub.1-4 alkoxy group, a cyano group, a nitro group and a halogen atom), a phenyl group (optionally substituted by one or more substituents selected from a C.sub.1-4 alkyl group, a C.sub.1-4 haloalkyl group, a C.sub.1-4 alkoxy group, a cyano group, a nitro group and a halogen atom), a pyridyl-substituted C.sub.1-4 alkyl group (in which the pyridyl moiety may be optionally substituted by one or more substituents selected from a C.sub.1-4 alkyl group, a C.sub.1-4 haloalkyl group, a C.sub.1-4 alkoxy group, a cyano group, a nitro group and a halogen atom), a pyridyl group (optionally substituted by one or more substituents selected from a C.sub.1-4 alkyl group, a C.sub.1-4 haloalkyl group, a C.sub.1-4 alkoxy group, a cyano group, a nitro group and a halogen atom), a naphthyl group, a naphthyl-substituted C.sub.1-4 alkyl group, a C.sub.1-4 alkoxy group (provided that both R.sup.4 and R.sup.5 must not be alkoxy groups), a cyano-C.sub.1-4 alkyl group, a C.sub.1-4 alkylcarbonyl group, a C.sub.1-4 alkoxycarbonyl group, a C.sub.1-4 alkoxycarbonyl-C.sub.1-4 alkyl group or a C.sub.1-4 alkylsulfonyl group; and

R.sup.4 and R.sup.5 may form, along with the nitrogen atom to which they bond, a 3-membered to 9-membered ring; and the ring may have one or more oxygen atoms, sulfur atoms, nitrogen atoms, carbonyl groups, sulfonyl groups or unsaturated bonds, the ring may be substituted by a C.sub.1-4 alkyl group, a C.sub.1-4 alkoxy group, a hydroxyl group, a halogen atom, a C.sub.1-4 haloalkyl group, a C.sub.1-4 alkoxycarbonyl group, a phenyl group or a benzyl group, the ring may be crosslinked with a C.sub.1-4 alkylene, and the ring may be condensed with a benzene ring.

Examples of the substituents R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 in the compounds of the present invention are mentioned hereunder, while the definitions of the abbreviated expressions used therein are mentioned below.

Me: methyl group

Et: ethyl group

Pr-n: normal propyl group

Pr-iso: isopropyl group

Bu-n: normal butyl group

Bu-iso: isobutyl group

Bu-sec: secondary butyl group

Bu-tert: tertiary butyl group

Pen-n: normal pentyl group

Hex-n: normal hexyl group

Pr-cyc: cyclopropyl group

Bu-cyc: cyclobutyl group

Pen-cycl: cylopentyl group

Hex-cyc: cyclohexyl group

Ph: phenyl group

Py: pyridyl group

Naph: naphthyl group

Examples of the substituent R.sub.1 in the compounds of the present invention:

H, Me, Bt, Pr-n, Pr-iso, Bu-n, Bu-iso, Bu-sec, Bu-tert, Pen-n, Hex-n, Hex-iso, Pr-cyc, Bu-cyc, Pen-cyc, Hex-cyc, CH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 CH.dbd.CHMe, CH.sub.2 CH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 C.tbd.CH, CH.sub.2 C.tbd.CMe, CH.sub.2 Pr-cyc, CH.sub.2 Bu-cyc, CH.sub.2 Pen-cyc, CH.sub.2 Hex-cyc, CH.sub.2 CH.sub.2 Pr-cyc, CH.sub.2 F, CH.sub.2 Cl, CH.sub.2 Br, CH.sub.2 I, CHF.sub.2, CHCl.sub.2, CHBr.sub.2, CF.sub.3, CCl.sub.3, CBr.sub.3, CClF.sub.2, CF.sub.3 CH.sub.2, CF.sub.3 CF.sub.2 CF.sub.2, Cl CH.sub.2 CH.sub.2 CH.sub.2, ClCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2, CH.sub.2 NMe.sub.2, CH.sub.2 NEt.sub.2, CH.sub.2 N(Pr-n).sub.2, CH.sub.2 N(Pr-iso).sub.2, CH.sub.2 N(Bu-n).sub.2, CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 NMe.sub.2, CH.sub.2 OMe, CH.sub.2 OEt, CH.sub.2 OPr-n, CH.sub.2 OBu-n, CH.sub.2 OBu-iso, CH.sub.2 OBu-sec, CH.sub.2 OBu-tert, CH.sub.2 CH.sub.2 OMe, CH.sub.2 CH.sub.2 OEt, CH.sub.2 CH.sub.2 OPr-n, CH.sub.2 CH.sub.2 CH.sub.2 OMe, CH.sub.2 CH.sub.2 CH.sub.2 OEt, CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OMe, CH.sub.2 SMe, CH.sub.2 SEt, CH.sub.2 SPr-n, CH.sub.2 SBu-n, CH.sub.2 CH.sub.2 CH,CH.sub.2 SMe, CH.sub.2 S(O)Me, CH.sub.2 S(O)Et, CH.sub.2 S(O)Pr-n, CH.sub.2 S(O)Bu-n,, CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 S(O)Me, CH.sub.2 SO.sub.2 Me, CH.sub.2 SO.sub.2 Et, CH.sub.2 SO.sub.2 Pr-n, CH.sub.2 SO.sub.2 Bu-n, CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 SO.sub.2 Me, CH.sub.2 Ph, CHMePh, CMe.sub.2 Ph, Ph, 2-Cl-Ph, 3-Cl-Ph, 4-Cl-Ph, 2,4-Cl-Ph, 2-F-Ph, 3-F-Ph, 4-F-Ph, 2-F-4-Cl-Ph, 2-Br-Ph, 3-Br-Ph, 4-Br-Ph, 2-Me-Ph, 3-Me-Ph, 4-Me-Ph, 2,4-Me.sub.2 -Ph, 2,6-Me.sub.2 -Ph, 2-MeO-Ph, 3-MeO-Ph, 4-MeO-Ph, 2-CF.sub.3 -Ph, 3-CF.sub.3 -Ph 4-CF.sub.3 -Ph, 3,5-Cl.sub.2 -Ph, 2,6-Cl.sub.2 -Ph, 2,3-Cl.sub.2 -Ph, 2,4,6-Cl.sub.3 -Ph, 2,3,5-Cl.sub.3 -Ph, 2,3,4-Cl.sub.3 -Ph, 2-NO.sub.2 -Ph, 2-CN-Ph, OMe, OEt, OPr-n, OPr-iso, OBu-n, OBu-iso, OBu-tert, OCH.sub.2 F, OCBrF.sub.2, OCHF.sub.2, OCF.sub.3, OCH.sub.2 CH.sub.2 Cl, OCH.sub.2 CH.sub.2 CH.sub.2 CHCl, OCH.sub.2 Ph, SMe, SEt, SPr-n, SPr-iso, SBu-n, SBu-iso, SBu-tert, SCH.sub.2 Ph, S(O)Me, S(O)Et, S(O)Pr-n, S(O)Pr-iso, S(O)Bu-n, SO.sub.2 Me, SO.sub.2 Et, SO.sub.2 Pr-n, SO.sub.2 Pr-iso, SO.sub.2 Bu-n, SO.sub.2 NMe.sub.2, SO.sub.2 NEt.sub.2, SO.sub.2 N(Pr-n).sub.2, SO.sub.2 N(Bu-n).sub.2, CN, F, Cl, Br, I, NMe.sub.2, NEt.sub.2, N(Pr-n).sub.2, N(Pr-iso).sub.2, N(Bu-n).sub.2, NO.sub.2

Examples of the substituent R.sup.2 in the compounds of the present invention:

H, Me, Bt, Pr-n , Pt-iso, Bu-n, BU-iso, Bu-sec, Bu-tert, Pen-n, Hex-n, Pr-cyc, Bu-cyc, Pen-cyc, Hex-cyc, CH.sub.2 CH.vertline.CH.sub.2. CH.sub.2 CH.vertline.CHMe, CH.sub.2 CH.sub.2 CH.vertline.CH.sub.2, CH.sub.2 C.tbd.CH.sub.2 C.tbd.CMe, CH.sub.2 Pr-cyc, CH.sub.2 Bu-cyc, CH.sub.2 Pen-cyc, CH.sub.2 Hex-cyc, CH.sub.2 CH.sub.2 Pr-cyc, CH.sub.2 F, CH.sub.2 Cl, CH.sub.2 Br, CH.sub.2 I, CHF.sub.2, CHCl.sub.2, CHBr.sub.2, CF.sub.3, CCl.sub.3, CBr.sub.3. CClF.sub.2, CF.sub.3 CH.sub.2, CF.sub.3 CF.sub.2, CF.sub.3 CF.sub.2 CF.sub.2, ClCH.sub.2 CH.sub.2 CH.sub.2, ClCH.sub.2 CH.sub.2 CH.sub.2, CH.sub.2, CH.sub.2 COMe, CH.sub.2 COBt, CH.sub.2 COPr-n, CH.sub.2 COPr-iso, CH.sub.2 COBu-n, CHMeCOMe, CHMeCOBt, CHMeCOPr-n, CH.sub.2 CH.sub.2 CH.sub.2 COMe, CH.sub.2 CO.sub.2 Me, CH.sub.2 CO.sub.2 Bt,CH.sub.2 CO.sub.2 Pr-n, CH.sub.2 CO.sub.2 Pr-iso, CH.sub.2 CO.sub.2 Bu-n, CHMeCO.sub.2 Me, CHMeCO.sub.2 Bt, CHMeCO.sub.2 Pr-n, CH.sub.2 CH.sub.2 CH.sub.2 CO.sub.2, CH.sub.2 NMe.sub.2, CH.sub.2 NBt.sub.2, CH.sub.2 N(Pr-n).sub.2, CH.sub.2 N(Pr-iso).sub.2, CH.sub.2 N(Bu-n).sub.2, CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 NMe.sub.2, CH.sub.2 OMe, CH.sub.2 OBt, CH.sub.2 OPr-n, CH.sub.2 OBu-n, CH.sub.2 OBu-iso, CH.sub.2 OBu-sec, CH.sub.2 OBu-tert, CH.sub.2 CH.sub.2 OMe, CH.sub.2 CH.sub.2 OBt, CH.sub.2 CH.sub.2 OPr-n, CH.sub.2 CH.sub.2 CH.sub.2 OMe, CH.sub.2 CH.sub.2 CH.sub.2 OBt, CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OMe, CH.sub.2 OCH.sub.2 CH.sub.2 OMe, CH.sub.2 OCH.sub.2 CH.sub.2 OBt, CH.sub.2 SBt, CH.sub.2 SPr-n, CH.sub.2 SBu-n, CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 SMe, CH.sub.2 S(O)Me, CH.sub.2 S(O)Bt, CH.sub.2 S(O)Pr-n, CH.sub.2 S(O)Bu-n, CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 S(O)Me, CH.sub.2 SO.sub.2 Me, CH.sub.2 SO.sub.2 Bt, CH.sub.2 SO.sub.2 Pr-n, CH.sub.2 SO.sub.2 Bu-n, CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 SO.sub.2 Me, CH.sub.2 Ph, CHMePh, CMe.sub.2 Ph, Ph, 2-Cl-Ph, 3-Cl-Ph, 4Cl-Ph, 2,4-Cl.sub.2 Ph, 2-F-Ph, 3-F-Ph, 4-F-Ph, 2-F-4-Cl-Ph, 2-Br-Ph, 3-Br-Ph, 4-Br-Ph, 2-Me-Ph, 3-Me-Ph, 4-Me-Ph, 2,4-Me.sub.2 Ph, 2,6-Me.sub.2 -Ph, 2-MeO-Ph, 3-MeO-Ph, 4-MeO-Ph, 2-CF.sub.3 -Ph, 3CF.sub.3 -Ph, 4-CF.sub.3 -Ph, 3,5-Cl.sub.2 -Ph, 2,6-Cl.sub.2 -Ph, 2,3-Cl.sub.2 -Ph, 2,4,6-Cl.sub.3 -Ph, 2,3,5-Cl.sub.3 Ph, 2,3,4-Cl.sub.3 Ph, 2-Cl-4-CF.sub.3 -Ph, 2,6-Cl.sub.2 -4-CF.sub.3 -Ph,

2-NO.sub.2 -Ph, 2-CN-Ph, 3-CN-Ph, 4-CN-Ph, 1-Naph, 2-Naph, COMe, COBt, COPr-n, COPr-iso, COBu-n, CONHMe, CONHBt, CONHPr-n, CONHPr-iso, CONHBu-n, CONMe.sub.2, CONBt.sub.2, CON(Pr-n).sub.2, CON(Pr-iso).sub.2, CON(Bu-n).sub.2, CO.sub.2 Me, CO.sub.2 Bt, CO.sub.2 Pr-n, CO.sub.2 Pr-iso, CO.sub.2 Bu-n, SO.sub.2 Me,SO.sub.2 Bt, SO.sub.2 Pr-n, SO.sub.2 Pr-iso, SO.sub.2 Bu-n, SO.sub.2 NMe.sub.2, SO.sub.2 NBt.sub.2, SO.sub.2 N(Pr-n).sub.2, SO.sub.2 N(Bu-n).sub.2, 2,5-Cl.sub.2 -Ph, 3,4-Cl.sub.2 -Ph, 2,4-(NO.sub.2).sub.2 -Ph, 3-NO.sub.2 -Ph, 4-NO.sub.2 -Ph, 2-Py, 3-Py, 4-Py, 3-Cl-2-Py, 4Cl-2-Py, 5Cl-2-Py, 6-Cl-2-Py, 3-F-2-Py, 4-F-2-Py, 5-F-2-Py, 6F-2-Py, 3-Br-2-Py, 4-Br-2-Py, 5-Br-2-Py, 6-Br-2-Py, 3-CF.sub.3 -2Py, 4CF.sub.3 -2-Py, 5-CF.sub.3 -2-Py, 6-CF.sub.2 -Py, 3-Cl-5-CF.sub.3 -2Py, 3Me-2-Py, 4Me-2-Py, 5-Me-2-Py, 6-Me-2-Py, 3-NO.sub.2 2-Py, 4-NO.sub.2 -2-Py, 5-NO.sub.2 -Py, 6-NO.sub.2 -2-Py, 3-Py, 4-Py

Examples of the substituent R.sup.3 in the compounds of the present invention:

CN, F, Cl, Br, I, NO.sub.2, H, Me, Bt, Pr-n, Pr-iso, Bu-n, Bu-iso, Bu-sec, Bu-tert, Pen-n, Hex-n, Hex-iso, Pr-cyc, Bu-cyc, Pen-cyc, Hex-cyc, CH.sub.2 CH.vertline.CH.sub.2, CH.sub.2 CH.dbd.CHMe, CH.sub.2 CH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 C.tbd.CH, CH.sub.2 C.tbd.CMe, Ph, 2-Cl-Ph, 3-Cl-Ph, 4-Ph, 2,4-Cl.sub.2 -Ph, 2-F-Ph, 3-F-Ph, 4-F-Ph, 2F-4-Cl-Ph, 2-Br-Ph, 3-Br-Ph, 4-Br-Ph, 2-Me-Ph, 3-Me-Ph, 4-Me-Ph, 2,4-Me.sub.2 -Ph, 2,6-Me.sub.2 -Ph, 2-MeO-Ph, 3MeO-Ph, 4MeO-Ph, 2-CF.sub.8 -Ph, 3-CF.sub.8 -Ph, 4-CF.sub.8 -Ph, 3,5-Cl.sub.2 -Ph, 2,6-Cl.sub.2 -Ph, 2,3-Cl.sub.2 -Ph, 2,4,6-Cl.sub.8 -Ph, 2,3,5-Cl.sub.3 2,3,4-Cl.sub.3 -Ph, 2-NO.sub.2 -Ph, 2-CN-Ph

Examples of the substituents R.sup.4 and R.sup.5 in the compounds of the present invention: H, Me, Bt, Pr-n, Pr-iso, Bu-n, Bu-iso, Bu-sec, Bu-tert, CHMeCHMe.sub.2, Pen-n, Hex-n, Hex-iso, Pr-cyc, Bu-cyc Pen-cyc, Hex-cyc, CH.sub.2 Pr-cyc, CH.sub.2 Bu-cyc, CH.sub.2 Hex-cyc, CH.sub.2 CH.sub.2 Pr-cyc, CH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 CH.vertline.CHMe, CH.sub.2 CH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 C.tbd.CH, CH.sub.2 C.tbd.CMe, CH.sub.2 Ome CH.sub.2 OBt, CH.sub.2 OPr-n, CH.sub.2 OBu-n, CH.sub.2 OBu-iso, CH.sub.2 OBu-sec, CH.sub.2 OBu-tert, CH.sub.2 CH.sub.2 Ome CH.sub.2 CH.sub.2 OBt, CH.sub.2 CH.sub.2 OPr-n, CH.sub.2 CH.sub.2 CH.sub.2 OMe, CH.sub.2 CH.sub.2 CH.sub.2 OBt, CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OMe, Ph, 2Cl-Ph, 3-Cl-Ph, 4-Cl-Ph, 2,4-Cl.sub.2 -Ph, 3,5-Cl.sub.2 -Ph, 2,6-Cl.sub.2 -Ph, 2,3-Cl.sub.2 -Ph, 2,5-Cl.sub.2 -Ph, 2-F-Ph, 3-F-Ph, 4-F-Ph, 2-F-4-Cl-Ph, 2-Br-Ph, 3-Br-Ph, 4-Br-Ph, 2-Me-Ph, 3-Me-Ph, 4-Me-Ph, 2,4-Me.sub.2 Ph, 3,5-Me.sub.2 -Ph, 2,6-Me.sub.2 -Ph, 2,3-Me.sub.2 Ph, 2,5Me.sub.2 -Ph, 2-MeO-Ph, 3-MeO-Ph, 4-MeO-Ph, 2-CF.sub.8 -Ph, 3-CF.sub.8 -Ph, 4-CF.sub.8 -Ph, 2,4,6-CL.sub.8 -Ph, 2,3,5-Cl.sub.8 -Ph, 2,3,4-Cl.sub.8 Ph, 2-NO.sub.2 -Ph, 2-CN-Ph, CH.sub.2 -Ph, OMe, OBt, OPr-n, OPr-iso, OBu-n, OBu-iso, OBu-tert, SO.sub.2 Bt, SO.sub.2 Pr-n, SO.sub.2 Pr-iso, SO.sub.2 Bu-n, COMe, COBt, COPr-iso, COBu-n, CO.sub.2 Me, CO.sub.2 Bt, CO.sub.2 Pr-n, CO.sub.2 Pr-iso, CO.sub.2 Bu-n, CH.sub.2 CO.sub.2 Me, CH.sub.2 CO.sub.2 Bt, CH.sub.2 CO.sub.2 Pr-n, CH.sub.2 CO.sub.2 Bu-n, CHMeCO.sub.2 Me, CHMeCO.sub.2 Bt, CH.sub.2 CH.sub.2 CO.sub.2 Me, CH.sub.2 CH.sub.2 CH.sub.2 CO.sub.2 Me, CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CO.sub.2 Me, CH(Pr-iso)CO.sub.2 Me, CH(Bu-sec)CO.sub.2 Me, CH(Bu-iso)CO.sub.2 Me, CH(CH.sub.2 Ph)CO.sub.2 Me, CH.sub.2 CH.sub.2 CN, 1 Naph, 2-Naph, CH.sub.2 -1-Naph, CH.sub.2 -2-Naph, CH.sub.2 Ph, CHMePh, CMe.sub.2 Ph, CH.sub.2 -Cl-Ph, CH.sub.2 -3-Cl-Ph, CH.sub.2 -4-Cl-Ph, 2-Py, 6-MeO-2-Py, 6-Cl-2-Py, 6F-2-2-Py, 5-CF.sub.8 -2-Py, 3-Cl-5-CF.sub.8 -2-Py, 3-Py, 4-Py, CH.sub.2 -5-Cl-2-Py, CH.sub.2 -6-Cl-3-Py Examples of saturated 5-membered to 7-membered rings to be formed by the substituents R.sup.4 and R.sup.5 along with the nitrogen atom to which they bond in the compounds of the present invention: ##STR3##

The compounds of the present invention may be produced easily in accordance with anyone of the following reaction schemes 1 to 4.

Reaction Scheme 1: ##STR4## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 have the same definitions as those mentioned above, and Z represents a halogen atom.

Precisely, a 5-halogenopyrazole (2) is reacted with a glycolic acid amide (3) in the presence of a base to produce the compound (1) of the present invention. As the base, usable are inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium hydride, etc.; or organic bases such as pyridine, triethylamine, DBU, etc. This reaction may progress even in the absence of a solvent but, if desired, may be conducted in the presence of a solvent. The solvent usable in the reaction is not specifically defined, provided that it is inert to the reaction. As the usable solvents, for example, mentioned are aliphatic or aromatic hydrocarbons such as hexane, cyclohexane, benzene, toluene, etc.; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, etc.; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; nitriles such as acetonitrile, propionitrile, etc.; acid amides such as dimethylformamide, dimethylacetamide, etc.; sulfones such as dimethylsulfoxide, sulforane, etc.; and organic bases such as pyridine, etc. The reaction temperature may be freely selected from the range between -50.degree. C. and 150.degree. C. but is preferably within the range between 0.degree. C. and 60.degree. C.

Reaction Scheme 2: ##STR5## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and Z have the same definitions as those mentioned above.

Precisely, a 5-hydroxypyrazole (4) is reacted with a halogenoacetamide (5) in the presence of a base to produce the compound (1) of the present invention. As the base and the solvent, those mentioned for the reaction scheme 1 shall be referred to. The reaction temperature may be freely selected from the range between -50.degree. C. and 150.degree. C. but is preferably within the range between 0.degree. C. and 100.degree. C.

Reaction Scheme 3: ##STR6## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 have the same definitions as those mentioned above, and X represents a nitro group or a halogen atom.

Precisely, a 5-hydroxypyrazole (6) is reacted with a halogenoacetamide (5) in the presence of a base to give a pyrazole-glycolic acid amide (7). As the base, the solvent and the reaction temperature, those mentioned for the reaction scheme 1 shall be referred to. The amide (7) is then treated with a nitrating agent such as a mixed acid or the like or with an electrophilic halogenating agent such as chlorine, bromine, sulfuryl chloride, N-chlorosuccinimide, N-bromosuccinimide, etc., to produce the compound (1') of the present invention.

Reaction Scheme 4: ##STR7## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and Z have the same definitions as those mentioned above, and Y represents a C.sub.1-6 alkyl group or a phenyl group.

Precisely, a 5-hydroxypyrazole (4) is reacted with a halogenoacetate (8) in the presence of a base to give a pyrazole-glycolate (9). As the base, the solvent and the reaction temperature, those mentioned for the reaction scheme 1 shall be referred to. The ester (9) is then hydrolyzed and halogenated to give an acid chloride (11), which is reacted with an amine (12) to produce the compound (1) of the present invention.

Regarding the staring materials to be used in the above-mentioned reactions, 5-chloro-4-nitropyrazoles (2, Z=Cl) may be produced with reference to U.S. Pat. No. 3,282,954 (1966), etc.; 5-bromo-4-nitropyrazoles (2, Z=Br) may b produced with reference to Journal of Organic Chemistry Vol. 51, page 4656 (1986), etc.; and 5-hydroxy-4-nitropyrazoles (4) may be produced with reference to Chemiche Berichte, Vol. 74, page 1420 (1941), etc.

Examples of producing the compounds of the present invention are mentioned hereunder, which, however, are not intended to restrict the scope of the present invention.

Example 1: (1) Production of 3,5-dichloro-1-methylpyrazole: ##STR8##

113 g (0.58 mol) of 3,5-dichloro-1-methylpyrazole-4-carboxylic acid were heated at 300.degree. C. and distilled to give 51 g of a crude oil, which were dissolved in 200 ml of chloroform and washed with water. After removal of the solvent, 44 g of the intended product were obtained by distillation. This had a boiling point of 172.degree. to 173.degree. C.

(2) Production of 3,5-dichloro-1-methyl-4-nitropyrazole: ##STR9##

A solution of 8.5 g (56 mmol) of 3,5-dichloro-1-methylpyrazole in acetic anhydride (15 ml) was added dropwise to a mixed acid comprising 20 ml of concentrated sulfuric acid and 6 g of fuming nitric acid, at 20.degree. C. or lower. After stirred for 48 hours at room temperature, this was poured into 300 ml of water with ice, whereupon the crystals thus precipitated were taken out by filtration, washed with water and dried to obtain 5.68 g of the intended product. This .had a melting point of 84.degree. to 88.degree. C.

(3) Production of N-methyl-N-phenyl-2-(3-chloro-1-methyl-4-nitropyrazol-5-yloxy)acetamide: ##STR10##

0.63 g (3.2 mmol) of 3,5-dichloro-1-methyl-4-nitropyrazole and 0.53 g (3.2 mmol) of N-methyl-N-phenylglycolic acid amide were dissolved in 5 ml of DMF, and 0.18 g (3.2 mmol) of powdery potassium hydroxide were added thereto. After this was stirred for 0.5 hours at room temperature, 20 ml of water were added thereto. This was extracted two times each with 20 ml of benzene, the resulting extract was washed with water and dried with anhydrous sodium sulfate. Then, the solvent was removed by distillation. A small amount of diisopropyl ether was added to the resulting residue, and the crystals thus precipitated were taken out by filtration and dried to obtain 0.7 g of the intended product. This had a melting point of 104.degree. to 105.degree. C.

Example 2: (1) Production of 3-trifluoromethyl-1-methyl-5-hydroxy-4-nitropyrazole: ##STR11##

10 g (60 mmol) of 3-trifluoromethyl-1-methyl-5-hydroxypyrazole were dissolved in 30 ml of concentrated sulfuric acid, and 7 ml of 60% nitric acid were dropwise added thereto at 10.degree. C. or lower. After stirred for 2 hours at room temperature, this was poured into 300 ml of water with ice, whereupon the crystals thus precipitated were taken out by filtration, washed with water and dried. The thus-obtained crystals were washed with a mixture of diisopropyl ether and diethyl ether and dried to obtain 5.5 g of the intended pure product. This had a melting point of 93.degree. to 94.degree. C.

(2) Production of N-methyl-N-phenyl-2-(3-trifluoromethyl-1-methyl-4-nitropyrazol-5-yloxy)acetamide: ##STR12##

1.0 g (4.7 mmol) of 3-trifluoromethyl-1-methyl-5-hydroxy-4-nitropyrazole and 0.95 g (5.2 mmol) of N-methyl-N-phenylchloroacetamide were dissolved in 10 ml of DMF, and 0.29 g (5.2 mmol) of powdery potassium hydroxide were added thereto and stirred for 5 hours at 80.degree. C. After this was cooled, 30 ml of water were added thereto. Then, this was extracted two times each with 30 ml of benzene. The resulting extract was washed with water and de-watered with anhydrous sodium sulfate. The solvent was removed by distillation, and an oily residue was obtained. The residue was pulified by preparative high performance liquid chromatography to obtain 0.04 g of the intended product. This was oily.

Example 3: Production of 2-[4-chloro-1-(2,5-dichlorophenyl)-3-trifluoromethylpyrazol-5-yloxy)acetopiperidide: ##STR13##

0.8 g (2.4 mmol) of 4-chloro-1-(2,5-dichlorophenyl)-3-trifluoromethyl-5-hydroxypyrazole and 0.56 g (2.2 mmol) of chloroacetopiperidide were dissolved in 4 ml of DMF, and 0.5 g (3.6 mmol) of potassium carbonate were added thereto and stirred for 4 hours at 80.degree. C. After cooled, 50 ml of water were added thereto. Then, this was extracted two times each with 50 ml of diethyl ether. The resulting extract was washed with water and a saturated saline solution in order and then de-watered with anhydrous magnesium sulfate. The solvent was then removed by distillation. The residue was purified by silica gel column chromatography (using chloroform as the eluent) to obtain 0.42 g of the intended product. This had a melting point of 61.degree. to 62.degree. C.

Example 4: (1) Production of 2-(3-trifluoromethylpyrazol-5-yloxy)acetopiperidide: ##STR14##

6.0 g (40 mmol) of 3-trifluoromethyl-5-hydroxypyrazole and 6.4 g (39 mmol) of chloroaceto-piperidide were dissolved in 40 ml of DMF, and 8.2 g (59 mmol) of potassium carbonate were added thereto and stirred for 4 hours at room temperature. After stirred for further 2 hours at 50.degree. C., this was cooled. 200 ml of water were added thereto, and this was extracted two times each with 200 ml of ethyl acetate. The resulting extract was washed with a saturated saline solution and de-watered with anhydrous magnesium sulfate. Then, the solvent was removed by distillation. Diethyl ether was added to the residue, whereupon the crystals thus precipitated were taken out by filtration and dried to obtain 3.6 g of the intended product. This had a melting point of 154.degree. to 156.degree. C.

(2) Production of 2-(3-trifluoromethyl-1-propargylpyrazol-5-yloxy)acetopiperidide: ##STR15##

0.8 g (2.9 mmol) of 2-(3-trifluoromethylpyrazol-5-yloxy)acetopiperidide and 0.34 g (2.9 mmol) of propargyl bromide were dissolved in 4 ml of DMF, and 0.6 g (4.3 mmol) of potassium carbonate were added thereto and stirred for 18 hours at room temperature. 50 ml of water were added thereto, and this was extracted two times each with 50 ml of diethyl ether.

The resulting extract was washed with water and a saturated saline solution in order and de-watered with anhydrous magnesium sulfate. Then, the solvent was removed by distillation. The residue was purified by silica gel column chromatography (using chloroform as the eluent) to obtain 0.75 g of a mixture comprising the intended product and its isomer of 2-(5-trifluoromethyl-1-propargylpyrazol-3-yloxy) acetopiperidide.

In the next step, the mixture was used directly as it was.

(3) Production of 2-(4-chloro-3-trifluoromethyl-1-propargylpyrazol-5-yloxy)acetopiperidide: ##STR16##

0.75 g (2.4 mmol) of the mixture of isomers, that had been obtained in (2), were dissolved in 4 ml of chloroform, and 0.19 g (1.4 mmol) of sulfuryl chloride were added dropwise thereto at 0.degree. C. After this was stirred for 2 hours at 0.degree. C., 20 ml of water with ice were added thereto. This was then extracted two times each with 20 ml of chloroform. The resulting extract was washed with an aqueous 10% sodium hydrogencarbonate solution and a saturated saline solution in order and de-watered with anhydrous magnesium sulfate. Then, the solvent was removed by distillation. The residue was purified by thin layer silica gel chromatography (using ethyl acetate/n-hexane=1/1 as the developer) to obtain 0.35 g of the intended product. This had a melting point of 78.degree. to 79.degree. C. The 2-(5-trifluoromethyl-1-propargylpyrazol-3-yloxy)acetopiperidide contained in the starting material was unreacted and recovered as an oily substance of 0.35 g.

Example 5: (1) Production of ethyl 2-(4-chloro-3-trifluoromethyl-1-phenylpyrazol-5-yloxy)acetate: ##STR17##

28 g (107 mmol) of 4-chloro-3-trifluoromethyl-5-hydroxy-1-phenylpyrazole and 19.5 g (117 mmol) of ethyl bromoacetate were dissolved in 150 ml of acetonitrile, and 28 g (203 mmol) of potassium carbonate were added thereto and refluxed for one hour.

After cooled, the solid was filtrated out and the solvent was removed by distillation. 150 ml of chloroform were added to the residue, which was washed with water and de-watered with anhydrous sodium sulfate. Then, the solvent was removed by distillation, and 37 g of the intended product were obtained. This was oily.

(2) Production of 2-(4-chloro-3-trifluoromethyl-1-phenylpyrazol-5-yloxy)acetic acid: ##STR18##

37 g (106 mmol) of ethyl 2-(4-chloro-3-trifluoromethyl-1-phenylpyrazol-5-yloxy)acetate were dissolved in 100 ml of ethanol, and 40 ml of an aqueous solution of 8.5 g (213 mmol) of sodium hydroxide were added thereto. After this was stirred for one hour at room temperature, the solvent was removed by distillation and the residue was dissolved in 300 ml of water. The resulting aqueous solution was washed with 100 ml of benzene and then made acidic (pH 1) with concentrated hydrochloric acid. This was extracted three times each with 100 ml of chloroform, and the resulting extract was washed with water and de-watered with anhydrous sodium sulfate. Then, the solvent was removed by distillation and 33 g of the intended product were obtained. This had a melting point: of 93.degree. to 96.degree. C.

(3 ) Production of 2-(4-chloro-3-trifluoromethyl-1-phenylpyrazol-5-yloxy)acetyl chloride: ##STR19##

80 ml of thionyl chloride were added to 23 g (72 mmol) of 2-(4-chloro-3-trifluoromethyl-1-phenylpyrazol-5-yloxy)acetic acid and heated under reflux for 1.5 hours. The thionyl chloride was removed by distillation under reduced pressure, and 24 g of the intended product were obtained. This was oily.

(4) Production of N,N-diallyl-2-(4-chloro-3-trifluoromethyl-1-phenylpyrazol-5-yloxy) acetamide: ##STR20##

0.8 g (8.2 mmol) of diallylamine were dissolved in 10 ml of THF and 1.3 g (3.8 mmol) of 2-(4-chloro-3-trifluoromethyl-1-phenylpyrazol-5-yloxy)acetyl chloride were added thereto and stirred for one hour at room temperature. The reaction mixture was extracted by adding 50 ml of water, 100 ml of chloroform and several drops of concentrated hydrochloric acid thereto. The chloroform layer was washed with water and de-watered with anhydrous sodium sulfate. Then, the solvent was removed by distillation. The residue was purified by silica gel column chromatography (using chloroform as the eluent) to obtain 1.3 g of the intended product. This was oily.

By the same methods as those of the above-mentioned examples, the compounds mentioned in Table 1 below were produced, where the structural formulae and the physical data of the compounds produced are shown along with those of the compounds produced in the above-mentioned examples. The definitions of the symbols used in Table 1 are mentioned below. ##STR21##

TABLE 1______________________________________ Physical Properties (meltingNo. R.sup.1 R.sup.2 R.sup.3 N R.sup.4 R.sup.5 point, .degree.C.)______________________________________1 Cl Me NO.sub.2 Q.sub.1 104.about.1052 CF.sub.3 Me NO.sub.2 Q.sub.1 Oily3 Cl Me NO.sub.2 Q.sub.3 129.about.1304 Cl Me NO.sub.2 Q.sub.6 152.about.1535 Cl Me NO.sub.2 Q.sub.31 Oily6 Me Me NO.sub.2 Q.sub.1 108.about.1107 Me Me NO.sub.2 Q.sub.3 137.about.1398 Me Me NO.sub.2 Q.sub.6 126.about.1279 Me Me NO.sub.2 Q.sub.31 97.about.9810 H Me NO.sub.2 Q.sub.1 92.about.9311 NO.sub.2 Me NO.sub.2 Q.sub.1 86.about.8912 NO.sub.2 Me NO.sub.2 Q.sub.8 134.about.13513 NO.sub.2 Me NO.sub.2 Q.sub.6 128.about.13014 NO.sub.2 Me NO.sub.2 Q.sub.31 Oily15 Br Me NO.sub.2 Q.sub.1 117.about.12216 CF.sub.3 Me Cl Q.sub.1 65.about.6617 Cl Me CN Q.sub.1 Oily18 Cl Me NO.sub.2 Q.sub.8 149.about.15119 Cl Me NO.sub.2 Q.sub.15 163.about.16520 Cl Me NO.sub.2 Q.sub.17 Oily21 Cl Me NO.sub.2 Q.sub.42 Oily22 Cl Me NO.sub.2 Q.sub.7 131.about.13223 Cl Me NO.sub.2 Q.sub.12 206.about.20724 Cl Me NO.sub.2 Q.sub.14 124.about.12525 Cl Me NO.sub.2 Q.sub.9 104.about.10526 Cl Me NO.sub.2 Q.sub.10 105.about.10627 Cl Me NO.sub.2 Q.sub.11 112.about.11328 Cl Me NO.sub.2 Q.sub.4 99.about.10129 Cl Me NO.sub.2 Q.sub.5 107.about.10830 Cl Me NO.sub.2 Q.sub.13 177.about.17831 Cl Me NO.sub.2 Q.sub.27 Oily32 Cl Me NO.sub.2 Q.sub.24 Oily33 CF.sub.3 Me Cl Q.sub.9 88.about.8934 CF.sub.3 Me Cl Q.sub.10 62.about.6335 CF.sub.3 Me Cl Q.sub.11 91.about.9236 CF.sub.3 Me Cl Q.sub.12 148.about.14937 CF.sub.3 Me Cl Q.sub.14 105.about.10638 CF.sub.3 Me Cl Q.sub.6 105.about.10739 CF.sub.3 Me NO.sub.2 Q.sub.6 136.about.13740 CF.sub.3 Me Br Q.sub.1 Oily41 CF.sub.3 Me Br Q.sub.24 Oily42 CF.sub.3 Me Br Q.sub.6 104.about.10643 Br Me NO.sub.2 Q.sub.6 82.about.8644 Br Et NO.sub.2 Q.sub.6 Oily45 Br Pr-iso NO.sub.2 Q.sub.6 Oily46 Me Me Cl Q.sub.1 59.about.6047 Et Me Cl Q.sub.1 65.about.6648 Pr-n Me Cl Q.sub.1 Oily49 Pr-cyc Me Cl Q.sub.1 Oily50 CF.sub.2 Cl Me Cl Q.sub.1 75.about.7651 H Me Cl Q.sub.1 Oily52 H Et Cl Q.sub.1 68.about.7053 Cl Me CN Q.sub.6 114.about.11554 Pr-n Me NO.sub.2 Q.sub.1 91.about.9555 Pr-n Me NO.sub.2 Q.sub.6 75.about.7856 Pr-n Me NO.sub.2 Q.sub.3 66.about.7057 Ph Me Cl Q.sub.1 Oily58 CF.sub.3 Me NO.sub.2 Q.sub.10 100.about.10159 CF.sub.3 Me NO.sub.2 Q.sub.24 Oily60 CF.sub.3 Me NO.sub.2 Q.sub.31 Oily61 CF.sub.3 CF.sub.2 Me Cl Q.sub.6 78.about.8062 CF.sub.3 Ph Cl Q.sub.6 Oily63 CF.sub.3 Ph Cl Q.sub.31 67.about.6864 CF.sub.3 Ph Cl Q.sub.10 85.about.8665 CF.sub.3 Ph Cl Q.sub.24 106.about.10866 CF.sub.3 Ph Cl Q.sub.23 Oily67 CF.sub.3 2-Py Cl Q.sub.31 108.about.10968 CF.sub.3 CF.sub.2 Me Cl Q.sub.27 Oily69 CF.sub.3 Me Cl Q.sub.27 Oily70 CF.sub.3 Me Cl Q.sub.13 131.about.13271 3-ClPh Me Cl Q.sub.6 Oily72 CF.sub.3 Ph Cl Q.sub.32 74.about.7573 CF.sub.3 Ph Cl Q.sub.2 129.about.13074 CF.sub.3 2-MePh Cl Q.sub.31 82.about.8375 CF.sub.3 3-MePh Cl Q.sub.31 Oily76 CF.sub.3 4-MePh Cl Q.sub.31 86.about.8777 CF.sub.3 Ph Cl Q.sub.1 79.about.8078 CF.sub.3 2-ClPh Cl Q.sub.31 53.about.5479 CF.sub.3 3-ClPh Cl Q.sub.31 64.about.6580 CF.sub.3 4-ClPh Cl Q.sub.31 Oily81 CF.sub.3 Ph Cl Q.sub.19 Oily82 CF.sub.3 2-ClPh Cl Q.sub.23 Oily83 CF.sub.3 3-ClPh Cl Q.sub.23 Oily84 CF.sub.3 4-ClPh Cl Q.sub.23 Oily85 CF.sub.3 2-BrPh Cl Q.sub.23 93.about.9486 CF.sub.3 2-NO.sub.2Ph Cl Q.sub.23 Oily87 CF.sub.3 2-FPh Cl Q.sub.23 72.about.7388 CF.sub.3 4-FPh Cl Q.sub.23 74.about.7589 CF.sub.3 Ph Cl Q.sub.42 69.about.7190 CF.sub.3 Ph Cl Q.sub.43 Oily91 CF.sub.3 Ph Cl Q.sub.37 93.about.9492 CF.sub.3 Ph Cl Q.sub.46 Oily93 CF.sub.3 4-CF.sub.3Ph Cl Q.sub.23 61.about.6294 CF.sub.3 4-NO.sub.2Ph Cl Q.sub.23 83.about.8495 CF.sub.3 4-MeOPh Cl Q.sub.23 102.about.10496 CF.sub.3 2,4-Cl.sub.2Ph Cl Q.sub.23 107.about.10897 CF.sub.3 Ph Cl Q.sub.29 Oily98 CF.sub.3 Me NO.sub.2 Q.sub.23 73.about.7499 Cl Me NO.sub.2 Q.sub.23 93.about.94100 CF.sub.3 Ph Cl Q.sub.25 Oily101 CF.sub.3 Ph Cl Q.sub.26 Oily102 CF.sub.3 Ph Cl Q.sub.28 105.about.106103 CF.sub.3 Me Cl Q.sub.23 Oily104 CF.sub.3 Ph Cl Q.sub.18 Oily105 CF.sub.3 Ph Cl Q.sub.49 Oily106 CF.sub.3 Ph Cl Q.sub.50 Oily107 CF.sub.3 3-CF.sub.3Ph Cl Q.sub.23 68.about.69108 CF.sub.3 2-Py Cl Q.sub.23 105.about.106109 CF.sub.3 Ph Cl Q.sub.21 120.about.121110 CF.sub.3 Ph Cl Q.sub.38 133.about.134111 CF.sub.3 Ph Cl Q.sub.52 Oily112 CF.sub.3 Ph Cl Q.sub.53 Oily113 CF.sub.3 Ph Cl Q.sub.17 Oily114 CF.sub.3 Ph Cl Q.sub.36 130.about.131115 Me Ph Cl Q.sub.23 65.about.66116 CF.sub.3 3-FPh Cl Q.sub.23 Oily117 CF.sub.3 3,4-Cl.sub.2Ph Cl Q.sub.23 75.about.76118 CF.sub.3 3-CF.sub.3Ph Cl Q.sub.23 Oily119 CF.sub.3 Ph Cl Q.sub.33 137.about.138120 CF.sub.3 Ph Cl Q.sub.34 62.about.63121 CF.sub.3 Ph Cl Q.sub.35 118.about.119122 CF.sub.3 2,5-Cl.sub.2Ph Cl Q.sub.23 61.about.62123 CF.sub.3 CH.sub.2 Ph Cl Q.sub.23 72.about.73124 CF.sub.3 Ph Br Q.sub.23 59.about.60125 CF.sub.3 Ph Cl Q.sub.48 86.about.87126 CF.sub.3 Ph Cl Q.sub.51 84.about.85127 CF.sub.3 Ph Cl Q.sub.44 Oily128 CF.sub.3 Ph Cl Q.sub.39 89.about.90129 CF.sub.3 Ph Cl Q.sub.40 85.about.86130 CF.sub.3 Et Cl Q.sub.23 Oily131 CF.sub.3 Et Cl Q.sub.31 Oily132 CF.sub.3 Pr-n Cl Q.sub.23 Oily133 CF.sub.3 3-MePh Cl Q.sub.19 Oily134 CF.sub.3 Ph Cl Q.sub.30 62.about.63135 CF.sub.3 Ph Cl Q.sub.22 Oily136 CF.sub.3 Pr-n Cl Q.sub.1 Oily137 CF.sub.3 Bu-tert Cl Q.sub.23 72.about.73138 CF.sub.3 Ph Cl Q.sub.20 Oily139 CF.sub.3 Pr-n Cl Q.sub.31 Oily140 CF.sub.3 3-Cl-5-CF.sub.3 -2-Py Cl Q.sub.23 Oily141 CF.sub.3 Ph Cl Q.sub.54 Oily142 CF.sub.3 Ph Cl Q.sub.41 57.about.58143 CF.sub.3 Pr-iso Cl Q.sub.23 Oily144 CF.sub.3 Ph Cl Q.sub.45 Oily145 CF.sub.3 Ph Cl Q.sub.16 95.about.96146 Cl Ph Cl Q.sub.23 Oily147 CF.sub.3 1-NaPh Cl Q.sub.23 Oily148 CF.sub.3 CH.sub.2 CCH Cl Q.sub.23 78.about.79149 CF.sub.3 Ph Cl Q.sub.47 Oily150 H Me H Q.sub.1 77.about.78151 CF.sub.3 Me H Q.sub.24 Oily152 CF.sub.3 Me H Q.sub.1 100.about.102153 Pr-cyc Me H Q.sub.1 97.about.99154 Me Me H Q.sub.1 84.about.85155 H Et H Q.sub.1 Oily156 ClF.sub.2 C Me H Q.sub.1 82.about.83157 Pr-iso Me H Q.sub.1 50.about.51158 Et Me H Q.sub.1 78.about.79159 3-ClPh Me H Q.sub.6 112.about.113160 CF.sub.3 2-Py H Q.sub.31 109.about.110161 CF.sub.3 2-Py H Q.sub.23 125.about.126162 Me Ph H Q.sub.23 76.about.77163 CF.sub.3 H H Q.sub.23 154.about.156164 CF.sub.3 Ph Cl Q.sub.55 Oily165 CF.sub.3 Ph Cl Q.sub.56 Oily166 CF.sub.3 Ph Cl Q.sub.57 94.about.95167 CF.sub.3 Ph Cl Q.sub.58 111.about.112168 CF.sub.3 Ph Cl Q.sub.59 Oily169 CF.sub.3 CH.sub.2 CH.sub.2 CN H Q.sub.1 79.about.81170 CF.sub.3 Ph Cl Q.sub.60 Oily171 CF.sub.3 3,5-Cl.sub.2Ph Cl Q.sub.23 68.about.69172 CF.sub.3 3,5-Cl.sub.2Ph H Q.sub.23 108.about.110173 CF.sub.3 Ph Cl Q.sub.61 Oily174 CF.sub.3 CH.sub.2 CH.sub.2 CN Cl Q.sub.1 68.about.69175 CF.sub.3 Hex-cyc H Q.sub.6 Oily176 CF.sub.3 Ph Cl Q.sub.62 67.about.69177 Cl Ph H Q.sub.23 96.about.98178 CF.sub.3 Hex-cyc Cl Q.sub.6 Oily179 Ph Ph H Q.sub.23 139.about.140180 Ph Ph Cl Q.sub.23 105.about.106181 CF.sub.3 Ph Cl Q.sub.63 Oily182 CF.sub.3 Ph Cl Q.sub.64 88.about.90183 CF.sub.3 Hex-cyc H Q.sub.23 81.about.82184 CF.sub.3 CH.sub.2 CHCH.sub.2 Cl Q.sub.23 Oily185 CF.sub.3 Ph Cl Q.sub.65 Oily______________________________________

Examples of the compounds of the present invention are shown in the following Table 2, Table 3 and Table 4 along with the compounds produced in the above-mentioned examples, which, however, are not intended to restrict the scope of the present invention. The definitions of the abbreviated expressions used therein are mentioned below.

Me: methyl group

Et: ethyl group

Pr-n: normal propyl group

Pr-iso: isopropyl group

Bu-n: normal butyl group

Bu-iso: isobutyl group

Bu-sec: secondary butyl group

Bu-tert: tertiary butyl group

Pen-n: normal pentyl group

Hex-n: normal hexyl group

Pr-cyc: cyclopropyl group

Bu-cyc: cyclobutyl group

Pen-cyc: cylopentyl group

Hex-cyc: cyclohexyl group

Ph: phenyl group

TABLE 2__________________________________________________________________________ ##STR22## ##STR23## ##STR24## ##STR25## ##STR26## ##STR27## ##STR28## ##STR29## ##STR30## ##STR31## ##STR32## ##STR33## ##STR34## ##STR35## ##STR36## ##STR37## ##STR38## ##STR39## ##STR40## ##STR41## ##STR42## ##STR43## ##STR44## ##STR45## ##STR46## ##STR47## ##STR48## ##STR49## ##STR50## ##STR51## ##STR52## ##STR53## ##STR54## ##STR55## ##STR56## ##STR57## ##STR58## ##STR59## ##STR60## ##STR61## ##STR62## ##STR63## ##STR64## ##STR65## ##STR66## ##STR67## ##STR68## ##STR69## ##STR70## ##STR71## ##STR72## ##STR73## ##STR74## ##STR75## ##STR76## ##STR77## ##STR78## ##STR79## ##STR80## ##STR81## ##STR82## ##STR83## ##STR84## ##STR85## ##STR86## ##STR87## ##STR88## ##STR89## ##STR90## ##STR91## ##STR92## ##STR93## ##STR94## ##STR95## ##STR96## ##STR97## ##STR98## ##STR99## ##STR100## ##STR101## ##STR102## ##STR103## ##STR104## ##STR105## ##STR106## ##STR107## ##STR108## ##STR109## ##STR110## ##STR111## ##STR112## ##STR113## ##STR114## ##STR115## ##STR116## ##STR117## ##STR118## ##STR119## ##STR120## ##STR121## ##STR122## ##STR123## ##STR124## ##STR125## ##STR126## ##STR127## ##STR128## ##STR129##R.sup.1 R.sup.2__________________________________________________________________________H MeH EtH Pr-nH Pr-isoH CH.sub.2 Pr-cycH CH.sub.2 CHCH.sub.2H CH.sub.2 CCHH CH.sub.2 FH CHF.sub.2H CF.sub.3H CH.sub.2 OMeH SO.sub.2 MeH SO.sub.2 NMe.sub.2H PhH CH.sub.2 PhH CO.sub.2 MeH COMeH CONMe.sub.2H CH.sub.2 CO.sub.2 MeH CHMeCO.sub.2 EtH CH.sub.2 COMeMe MeMe EtMe Pr-nMe Pr-isoMe CH.sub.2 Pr-cycMe CH.sub.2 CHCH.sub.2Me CH.sub.2 CCHMe CH.sub.2 FMe CHF.sub.2Me CF.sub.3Me CH.sub.2 OMeMe SO.sub.2 MeMe SO.sub.2 NMe.sub.2Me PhMe CH.sub.2 PhMe CO.sub.2 MeMe COMeMe CONMe.sub.2Me CH.sub.2 CO.sub.2 MeMe CHMeCO.sub.2 EtMe CH.sub.2 COMeCl MeCl EtCl Pr-nCl Pr-isoCl Bu-nCl Pen-nCl Hex-nCl CH.sub.2 Pr-cycCl CH.sub.2 CHCH.sub.2Cl CH.sub.2 CCHCl CH.sub.2 FCl CHF.sub.2Cl CF.sub.3Cl CH.sub.2 OMeCl SO.sub.2 MeCl SO.sub.2 NMe.sub.2Cl PhCl CH.sub.2 PhCl CO.sub.2 MeCl COMeCl CONMe.sub.2Cl CH.sub.2 CO.sub.2 MeCl CHMeCO.sub.2 EtCl CH.sub.2 COMeBr MeBr EtBr Pr-nBr Pr-isoBr CH.sub.2 Pr-cycBr CH.sub.2 CHCH.sub.2Br CH.sub.2 CCHBr CH.sub.2 FBr CHF.sub.2Br CF.sub.3Br CH.sub.2 OMeBr SO.sub.2 MeBr SO.sub.2 NMe.sub.2Br PhBr CH.sub.2 PhBr CO.sub.2 MeBr COMeBr CONMe.sub.2Br CH.sub.2 CO.sub.2 MeBr CHMeCO.sub.2 EtBr CH.sub.2 COMeNO.sub.2 MeNO.sub.2 EtNO.sub.2 Pr-nNO.sub.2 Pr-isoNO.sub.2 CH.sub.2 Pr-cycNO.sub.2 CH.sub.2 CHCH.sub.2NO.sub.2 CH.sub.2 CCHNO.sub.2 CH.sub.2 FNO.sub.2 CHF.sub.2NO.sub.2 CF.sub.3NO.sub.2 CH.sub.2 OMeNO.sub.2 SO.sub.2 MeNO.sub.2 SO.sub.2 NMe.sub.2NO.sub.2 PhNO.sub.2 CH.sub.2 PhNO.sub.2 CO.sub.2 MeNO.sub.2 COMeNO.sub.2 CONMe.sub.2NO.sub.2 CH.sub.2 CO.sub.2 MeNO.sub.2 CHMeCO.sub.2 EtNO.sub.2 CH.sub.2 COMeCF.sub.3 MeCF.sub.3 EtCF.sub.3 Pr-nCF.sub.3 Pr-isoCF.sub.3 Bu-nCF.sub.3 Pen-nCF.sub.3 Hex-nCF.sub.3 Bu-tertCF.sub.3 CH.sub.2 Pr-cycCF.sub.3 CH.sub.2 CHCH.sub.2CF.sub.3 CH.sub.2 CCHCF.sub.3 CH.sub.2 FCF.sub.3 CHF.sub.2CF.sub.3 CF.sub.3CF.sub.3 CH.sub.2 OMeCF.sub.3 SO.sub.2 MeCF.sub.3 SO.sub.2 NMe.sub.2CF.sub.3 PhCF.sub.3 CH.sub.2 PhCF.sub.3 CO.sub.2 MeCF.sub.3 COMeCF.sub.3 CONMe.sub.2CF.sub.3 CH.sub.2 CO.sub.2 MeCF.sub.3 CHMeCO.sub.2 EtCF.sub.3 CH.sub.2 COMeEt MeEt Pr-isoEt EtEt CHF.sub.2Et CF.sub.3Et CH.sub.2 OMeEt PhEt CH.sub.2 PhEt CO.sub.2 MeEt COMeEt CH.sub.2 CO.sub.2 MeMeO MeMeO EtMeO Pr-isoMeO CH.sub.2 OMeMeO PhMeS MeMeS EtMeS Pr-isoMeS CH.sub.2 OMeMeS PhF MeF EtF Pr-isoF CH.sub.2 OMeF PhPr-n MePr-n EtPr-n Pr-isoPr-n CH.sub.2 OMePr-n PhPr-iso MePr-iso EtPr-iso Pr-isoPr-iso CH.sub.2 OMePr-iso PhPr-cyc MePr-cyc EtPr-cyc Pr-isoPr-cyc CH.sub.2 OMePr-cyc PhCH.sub.2 F MeCH.sub.2 F EtCH.sub.2 F Pr-isoCH.sub.2 F CH.sub.2 OMeCH.sub.2 F PhCH.sub.2 Cl MeCH.sub.2 Cl EtCH.sub.2 Cl Pr-isoCH.sub.2 Cl CH.sub.2 OMeCH.sub.2 Cl PhCHF.sub.2 MeCHF.sub.2 EtCHF.sub.2 Pr-isoCHF.sub.2 CH.sub.2 OMeCHF.sub.2 PhCClF.sub.2 MeCClF.sub.2 EtCClF.sub.2 Pr-isoCClF.sub.2 CH.sub.2 OMeCClF.sub.2 PhCF.sub.3 CF.sub.2 MeCF.sub.3 CF.sub.2 EtCF.sub.3 CF.sub.2 Pr-isoCF.sub.3 CF.sub.2 CH.sub.2 OMeCF.sub.3 CF.sub.2 PhCF.sub.3 CF.sub.2 CF.sub.2 MeCF.sub.3 CF.sub.2 CF.sub.2 EtCF.sub.3 CF.sub.2 CF.sub.2 Pr-isoCF.sub.3 CF.sub.2 CF.sub.2 CH.sub.2 OMeCF.sub.3 CF.sub.2 CF.sub.2 PhCH.sub.2 OMe MeCH.sub.2 OMe EtCH.sub.2 OMe Pr-isoCH.sub.2 OMe CH.sub.2 OMeCH.sub.2 OMe PhCH.sub.2 SMe MeCH.sub.2 SMe EtCH.sub.2 SMe Pr-isoCH.sub.2 SMe CH.sub.2 OMeCH.sub.2 SMe PhPh MePh EtPh Pr-isoPh CH.sub.2 OMePh PhOCHF.sub.2 MeOCHF.sub.2 EtOCHF.sub.2 Pr-isoOCHF.sub.2 CH.sub.2 OMeOCHF.sub.2 PhBu-n MeBu-iso MeBu-sec MeBu-tert MePen-n MeHex-n MeHex-iso MeBu-cyc MePen-cyc MeHex-cyc MeCH.sub.2 Pr-cyc MeCH.sub.2 Bu-cyc MeCH.sub.2 Pen-cyc MeCH.sub.2 Hex-cyc MeCH.sub.2 CH.sub.2 Pr-cyc MeCH.sub.2 CHCH.sub.2 MeCH.sub.2 CHCHMe MeCH.sub.2 CH.sub.2 CHCH.sub.2 MeCH.sub.2 CCH MeCH.sub.2 CCMe MeOEt MeOPr-n MeOPr-iso MeOBu-n MeOBu-iso MeOBu-tert MeOCH.sub.2 F MeOCBrF.sub.2 MeOCF.sub.3 MeOCH.sub.2 CH.sub.2 Cl MeOCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 Cl MeSEt MeSPr-n MeSPr-iso MeSBu-n MeSBu-iso MeSBu-tert MeS(O)Me MeS(O)Et MeS(O)Pr-n MeS(O)Pr-iso MeS(O)Bu-n MeSO.sub.2 Me MeSO.sub.2 Et MeSO.sub.2 Pr-n MeSO.sub.2 Pr-iso MeSO.sub.2 Bu-n MeSO.sub.2 NMe.sub.2 MeSO.sub.2 NEt.sub.2 MeSO.sub.2 N(Pr-n).sub.2 MeSO.sub.2 N(Pr-iso).sub.2 MeSO.sub.2 N(Bu-n).sub.2 MeI MeCN MeNMe.sub.2 MeNEt.sub.2 MeN(Pr-n).sub.2 MeN(Pr-iso).sub.2 MeN(Bu-n).sub.2 MeCH.sub.2 Br MeCH.sub.2 I MeCHCl.sub.2 MeCHBr.sub.2 MeCCl.sub.3 MeCBr.sub.3 MeCF.sub.3 CH.sub.2 MeClCH.sub.2 CH.sub.2 CH.sub.2 MeClCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 MeCH.sub.2 OEt MeCH.sub.2 OPr-n MeCH.sub.2 OBu-n MeCH.sub.2 OBu-iso MeCH.sub.2 OBu-sec MeCH.sub.2 OBu-tert MeCH.sub.2 CH.sub.2 OEt MeCH.sub.2 CH.sub.2 OMe MeCH.sub.2 CH.sub.2 OEt MeCH.sub.2 CH.sub.2 OPr-n MeCH.sub.2 CH.sub.2 CH.sub.2 OMe MeCH.sub.2 CH.sub.2 CH.sub.2 OEt MeCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OMe MeCH.sub.2 SEt MeCH.sub.2 SPr-n MeCH.sub.2 SBu-n MeCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 SMe MeCH.sub.2 S(O)Me MeCH.sub.2 S(O)Et MeCH.sub.2 S(O)Pr-n MeCH.sub.2 S(O)Bu-n MeCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 S(O)Me MeCH.sub.2 SO.sub.2 Me MeCH.sub.2 SO.sub.2 Et MeCH.sub.2 SO.sub.2 Pr-n MeCH.sub.2 SO.sub.2 Bu-n MeCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 SO.sub.2 Me MeCH.sub.2 NMe.sub.2 MeCH.sub.2 NEt.sub.2 MeCH.sub.2 N(Pr-n).sub.2 MeCH.sub.2 N(Pr-iso).sub.2 MeCH.sub.2 N(Bu-n).sub.2 MeCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 NMe.sub.2 Me2-ClPh Me3-ClPh Me4-ClPh Me2,4-Cl.sub.2Ph Me2-FPh Me3-FPh Me4-FPh Me2-F-4-ClPh Me2-BrPh Me3-BrPh Me4-BrPh Me2-MePh Me3-MePh Me4-MePh Me2,4-Me.sub.2Ph Me2,6-Me.sub.2Ph Me2-MeOPh Me3-MeOPh Me4-MeOPh Me2-CF.sub.3Ph Me3-CF.sub.3Ph Me4-CF.sub.3Ph MeCH.sub.2 Ph MeOCH.sub.2 Ph MeSCH.sub.2 Ph MeCl Bu-isoCl Bu-secCl Bu-tertCl CH.sub.2 Bu-cycCl CH.sub.2 Pen-cycCl CH.sub.2 Hex-cycCl CH.sub.2 CH.sub.2 Pr-cycCl CH.sub.2 CHCHMeCl CH.sub.2 CH.sub.2 CHCH.sub.2Cl CH.sub.2 CCMeCl CH.sub.2 ClCl CH.sub.2 BrCl CH.sub.2 ICl CHCl.sub.2Cl CHBr.sub.2Cl CCl.sub.3Cl CBr.sub.3Cl CClF.sub.2Cl CF.sub.3 CH.sub.2Cl CF.sub.3 CF.sub.2Cl CF.sub.3 CF.sub.2 CF.sub.2Cl ClCH.sub.2 CH.sub.2 CH.sub.2Cl ClCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2Cl SO.sub.2 EtCl SO.sub.2 Pr-nCl SO.sub.2 Pr-isoCl SO.sub.2 Bu-nCl SO.sub.2 NEt.sub.2Cl SO.sub.2 N(Pr-n).sub.2Cl SO.sub.2 N(Pr-iso).sub.2Cl SO.sub.2 N(Bu-n).sub.2Cl CH.sub.2 OEtCl CH.sub.2 OPr-nCl CH.sub.2 OBu-nCl CH.sub.2 OBu-isoCl CH.sub.2 OBu-secCl CH.sub.2 OBu-tertCl CH.sub.2 CH.sub.2 OMeCl CH.sub.2 CH.sub.2 OEtCl CH.sub.2 CH.sub.2 OPr-nCl CH.sub.2 CH.sub.2 CH.sub.2 OMeCl CH.sub.2 CH.sub.2 CH.sub.2 OEtCl CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OMeCl CH.sub.2 OCH.sub.2 CH.sub.2 OMeCl CH.sub.2 OCH.sub.2 CH.sub.2 OEtCl CH.sub.2 SEtCl CH.sub.2 SPr-nCl CH.sub.2 SBu-nCl CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 SMeCl CH.sub.2 S(O)EtCl CH.sub.2 S(O)Pr-nCl CH.sub.2 S(O)Bu-nCl CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 S(O)MeCl CH.sub.2 SO.sub.2 EtCl CH.sub.2 SO.sub.2 Pr-nCl CH.sub.2 SO.sub.2 Bu-nCl CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 SO.sub.2 MeCl CH.sub.2 NEt.sub.2Cl CH.sub.2 N(Pr-n).sub.2Cl CH.sub.2 N(Pr-iso).sub.2Cl CH.sub.2 N(Bu-n).sub.2Cl CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 NMe.sub.2Cl 2-ClPhCl 3-ClPhCl 4-ClPhCl 2,4-Cl.sub.2PhCl 2-FPhCl 3-FPhCl 4-FPhCl 2-F-4-ClPhCl 2-BrPhCl 3-BrPhCl 4-BrPhCl 2-MePhCl 3-MePhCl 4-MePhCl 2,4-Me.sub.2PhCl 2,6-Me.sub.2PhCl 2-MeOPhCl 3-MeOPhCl 4-MeOPhCl 2-CF.sub.3PhCl 3-CF.sub.3PhCl 4-CF.sub.3PhCl CH.sub.2 PhBr Bu-nBr Bu-isoBr Bu-secBr Bu-tertBr Pen-nBr Hex-nBr CH.sub.2 Bu-cycBr CH.sub.2 Pen-cycBr CH.sub.2 Hex-cycBr CH.sub.2 CH.sub.2 Pr-cycBr CH.sub.2 CHCHMeBr CH.sub.2 CH.sub.2 CHCH.sub.2Br CH.sub.2 CCMeBr CH.sub.2 ClBr CH.sub.2 BrBr CH.sub.2 IBr CHCl.sub.2Br CHBr.sub.2Br CCl.sub.3Br CBr.sub.3Br CClF.sub.2Br CF.sub.3 CH.sub.2Br CF.sub.3 CF.sub.2Br CF.sub.3 CF.sub.2 CF.sub.2Br ClCH.sub.2 CH.sub.2 CH.sub.2Br ClCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2Br SO.sub.2 EtBr SO.sub.2 Pr-nBr SO.sub.2 Pr-isoBr SO.sub.2 Bu-nBr SO.sub.2 NEt.sub.2Br SO.sub.2 N(Pr-n).sub.2Br SO.sub.2 N(Pr-iso).sub.2Br SO.sub.2 N(Bu-n).sub.2Br CH.sub.2 OEtBr CH.sub.2 OPr-nBr CH.sub.2 OBu-nBr CH.sub.2 OBu-isoBr CH.sub.2 OBu-secBr CH.sub.2 OBu-tertBr CH.sub.2 CH.sub.2 OMeBr CH.sub.2 CH.sub.2 OEtBr CH.sub.2 CH.sub.2 OPr-nBr CH.sub.2 CH.sub.2 CH.sub.2 OMeBr CH.sub.2 CH.sub.2 CH.sub.2 OEtBr CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OMeBr CH.sub.2 SEtBr CH.sub.2 SPr-nBr CH.sub.2 SBu-nBr CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 SMeBr CH.sub.2 S(O)EtBr CH.sub.2 S(O)Pr-nBr CH.sub.2 S(O)Bu-nBr CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 S(O)MeBr CH.sub.2 SO.sub.2 EtBr CH.sub.2 SO.sub.2 Pr-nBr CH.sub.2 SO.sub.2 Bu-nBr CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 SO.sub.2 MeBr CH.sub.2 NEt.sub.2Br CH.sub.2 N(Pr-n).sub.2Br CH.sub.2 N(Pr-iso).sub.2Br CH.sub.2 N(Bu-n).sub.2Br CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 NMe.sub.2Br 2-ClPhBr 3-ClPhBr 4-ClPhBr 2,4-Cl.sub.2PhBr 2-FPhBr 3-FPhBr 4-FPhBr 2-F-4-ClPhBr 2-BrPhBr 3-BrPhBr 4-BrPhBr 2-MePhBr 3-MePhBr 4-MePhBr 2,4-Me.sub.2PhBr 2,6-Me.sub.2PhBr 2-MeOPhBr 3-MeOPhBr 4-MeOPhBr 2-CF.sub.3PhBr 3-CF.sub.3PhBr 4-CF.sub.3PhBr CH.sub.2 PhCl CO.sub.2 EtCl CO.sub.2 Pr-nCl CO.sub.2 Pr-isoCl CO.sub.2 Bu-nCl COEtCl COPr-nCl COPr-isoCl COBu-nCl CONHEtCl CONHPr-nCl CONHPr-isoCl CONHBu-nCl CONEt.sub.2Cl CON(Pr-n).sub.2Cl CON(Pr-iso).sub.2Cl CON(Bu-n).sub.2Cl CH.sub.2 CO.sub.2 EtCl CH.sub.2 CO.sub.2 Pr-nCl CH.sub.2 CO.sub.2 Pr-isoCl CH.sub.2 CO.sub.2 Bu-nCl CHMeCO.sub.2 Pr-nCl CH.sub.2 CH.sub.2 CH.sub.2 CO.sub.2 MeCl CH.sub.2 COEtCl CH.sub.2 COPr-nCl CH.sub.2 COPr-isoCl CH.sub.2 COBu-nCl CHMeCOMeCl CHMeCOEtCl CHMeCOPr-nCl CH.sub.2 CH.sub.2 CH.sub.2 COMeBr CO.sub.2 EtBr CO.sub.2 Pr-nBr CO.sub.2 Pr-isoBr CO.sub.2 Bu-nBr COEtBr COPr-nBr COPr-isoBr COBu-nBr CONHEtBr CONHPr-nBr CONHPr-isoBr CONHBu-nBr CONEt.sub.2Br CON(Pr-n).sub.2Br CON(Pr-iso).sub.2Br CON(Bu-n).sub.2Br CH.sub.2 CO.sub.2 EtBr CH.sub.2 CO.sub.2 Pr-nBr CH.sub.2 CO.sub.2 Pr-isoBr CH.sub.2 CO.sub.2 Bu-nBr CHMeCO.sub.2 Pr-nBr CH.sub.2 CH.sub.2 CH.sub.2 CO.sub.2 MeBr CH.sub.2 COEtBr CH.sub.2 COPr-nBr CH.sub.2 COPr-isoBr CH.sub.2 COBu-nBr CHMeCOMeBr CHMeCOEtBr CHMeCOPr-nBr CH.sub.2 CH.sub.2 CH.sub.2 COMeH 2-ClPhH 3-ClPhH 4-ClPhH 2,4-Cl.sub.2PhH 2-FPhH 3-FPhH 4-FPhH 2-F-4-ClPhH 2-BrPhH 3-BrPhH 4-BrPhH 2-MePhH 3-MePhH 4-MePhH 2,4-Me.sub.2PhH 2,6-Me.sub.2PhH 2-MeOPhH 3-MeOPhH 4-MeOPhH 2-CF.sub.3PhH 3-CF.sub.3PhH 4-CF.sub.3PhH CH.sub.2 PhMe 2-ClPhMe 3-ClPhMe 4-ClPhMe 2,4-Cl.sub.2PhMe 2-FPhMe 3-FPhMe 4-FPhMe 2-F-4-ClPhMe 2-BrPhMe 3-BrPhMe 4-BrPhMe 2-MePhMe 3-MePhMe 4-MePhMe 2,4-Me.sub.2PhMe 2,6-Me.sub.2PhMe 2-MeOPhMe 3-MeOPhMe 4-MeOPhMe 2-CF.sub.3PhMe 3-CF.sub.3PhMe 4-CF.sub.3PhMe CH.sub.2 PhCF.sub.3 2-ClPhCF.sub.3 3-ClPhCF.sub.3 4-ClPhCF.sub.3 2,4-Cl.sub.2PhCF.sub.3 2-FPhCF.sub.3 3-FPhCF.sub.3 4-FPhCF.sub.3 2-F-4-ClPhCF.sub.3 2-BrPhCF.sub.3 3-BrPhCF.sub.3 4-BrPhCF.sub.3 2-MePhCF.sub.3 3-MePhCF.sub.3 4-MePhCF.sub.3 2,4-Me.sub.2PhCF.sub.3 2,6-Me.sub.2PhCF.sub.3 2-MeOPhCF.sub.3 3-MeOPhCF.sub.3 4-MeOPhCF.sub.3 2-CF.sub.3PhCF.sub.3 3-CF.sub.3PhCF.sub.3 4-CF.sub.3PhCF.sub.3 CH.sub.2 Ph3,5-Cl.sub.2Ph Me2,6-Cl.sub.2Ph Me2,3-Cl.sub.2Ph Me2,4,6-Cl.sub.3Ph Me2,3,5-Cl.sub.3Ph Me2,3,4-Cl.sub.3Ph Me2-NO.sub.2Ph Me2-CNPh MeH Pr-cycH Bu-cycH Pen-cycH Hex-cycH 3,5-Cl.sub.2PhH 2,6-Cl.sub.2PhH 2,3-Cl.sub.2PhH 2,4,6-Cl.sub.3PhH 2,3,5-Cl.sub.3PhH 2,3,4-Cl.sub.3PhH 2-NO.sub.2PhH 2-CNPhH 2-Cl-4-CF.sub.3PhH 2,6-Cl.sub.2 -4-CF.sub.3PhH 2,5-Cl.sub.2PhH 3,4-Cl.sub.2PhH 2,4-(NO.sub.2).sub.2PhH 3-NO.sub.2PhH 4-NO.sub.2PhH 2-PyH 3-PyH 4-PyH 3-Cl-2-PyH 4-Cl-2-PyH 5-Cl-2-PyH 6-Cl-2-PyH 3-F-2-PyH 4-F-2-PyH 5-F-2-PyH 6-F-2-PyH 3-Br-2-PyH 4-Br-2-PyH 5-Br-2-PyH 6-Br-2-PyH 3-CF.sub.3 -2-PyH 4-CF.sub.3 -2-PyH 5-CF.sub.3 -2-PyH 6-CF.sub.3 -2-PyH 3-Cl-5-CF.sub.3 -2-PyH 3-Me-2-PyH 4-Me-2-PyH 5-Me-2-PyH 6-Me-2-PyH 3-NO.sub.2 -2-PyH 4-NO.sub.2 -2-PyH 5-NO.sub.2 -2-PyH 6-NO.sub.2 -2-PyMe Pr-cycMe Bu-cycMe Pen-cycMe Hex-cycMe 3,5-Cl.sub.2PhMe 2,6-Cl.sub.2PhMe 2,3-Cl.sub.2PhMe 2,4,6-Cl.sub.3PhMe 2,3,5-Cl.sub.3PhMe 2,3,4-Cl.sub.3PhMe 2-NO.sub.2PhMe 2-CNPhMe 2-Cl-4-CF.sub.3PhMe 2,6-Cl.sub.2 -4-CF.sub.3PhMe 2,5-Cl.sub.2PhMe 3,4-Cl.sub.2PhMe 2,4-(NO.sub.2).sub.2PhMe 3-NO.sub.2PhMe 4-NO.sub.2PhMe 2-PyMe 3-PyMe 4-PyMe 3-Cl-2-PyMe 4-Cl-2-PyMe 5-Cl-2-PyMe 6-Cl-2-PyMe 3-F-2-PyMe 4-F-2-PyMe 5-F-2-PyMe 6-F-2-PyMe 3-Br-2-PyMe 4-Br-2-PyMe 5-Br-2-PyMe 6-Br-2-PyMe 3-CF.sub.3 -2-PyMe 4-CF.sub.3 -2-PyMe 5-CF.sub.3 -2-PyMe 6-CF.sub.3 -2-PyMe 3-Cl-5-CF.sub.3 -2-PyMe 3-Me-2-PyMe 4-Me-2-PyMe 5-Me-2-PyMe 6-Me-2-PyMe 3-NO.sub.2 -2-PyMe 4-NO.sub.2 -2-PyMe 5-NO.sub.2 -2-PyMe 6-NO.sub.2 -2-PyCl Pr-cycCl Bu-cycCl Pen-cycCl Hex-cycCl 3,5-Cl.sub.2PhCl 2,6-Cl.sub.2PhCl 2,3-Cl.sub.2PhCl 2,4,6-Cl.sub.3PhCl 2,3,5-Cl.sub.3PhCl 2,3,4-Cl.sub.3PhCl 2-NO.sub.2PhCl 2-CNPhCl 2-Cl-4-CF.sub.3PhCl 2,6-Cl.sub.2 -4-CF.sub.3PhCl 2,5-Cl.sub.2PhCl 3,4-Cl.sub.2PhCl 2,4-(NO.sub.2).sub.2PhCl 3-NO.sub.2PhCl 4-NO.sub.2PhCl 2-PyCl 3-PyCl 4-PyCl 3-Cl-2-PyCl 4-Cl-2-PyCl 5-Cl-2-PyCl 6-Cl-2-PyCl 3-F-2-PyCl 4-F-2-PyCl 5-F-2-PyCl 6-F-2-PyCl 3-Br-2-PyCl 4-Br-2-PyCl 5-Br-2-PyCl 6-Br-2-PyCl 3-CF.sub.3 -2-PyCl 4-CF.sub.3 -2-PyCl 5-CF.sub.3 -2-PyCl 6-CF.sub.3 -2-PyCl 3-Cl-5-CF.sub.3 -2-PyCl 3-Me-2-PyCl 4-Me-2-PyCl 5-Me-2-PyCl 6-Me-2-PyCl 3-NO.sub.2 -2-PyCl 4-NO.sub.2 -2-PyCl 5-NO.sub.2 -2-PyCl 6-NO.sub.2 -2-PyBr Pr-cycBr Bu-cycBr Pen-cycBr Hex-cycBr 3,5-Cl.sub.2PhBr 2,6-Cl.sub.2PhBr 2,3-Cl.sub.2PhBr 2,4,6-Cl.sub.3PhBr 2,3,5-Cl.sub.3PhBr 2,3,4-Cl.sub.3PhBr 2-NO.sub.2PhBr 2-CNPhBr 2-Cl-4-CF.sub.3PhBr 2,6-Cl.sub.2 -4-CF.sub.3PhBr 2,5-Cl.sub.2PhBr 3,4-Cl.sub.2PhBr 2,4-(NO.sub.2).sub.2PhBr 3-NO.sub.2PhBr 4-NO.sub.2PhBr 2-PyBr 3-PyBr 4-PyBr 3-Cl-2-PyBr 4-Cl-2-PyBr 5-Cl-2-PyBr 6-Cl-2-PyBr 3-F-2-PyBr 4-F-2-PyBr 5-F-2-PyBr 6-F-2-PyBr 3-Br-2-PyBr 4-Br-2-PyBr 5-Br-2-PyBr 6-Br-2-PyBr 3-CF.sub.3 -2-PyBr 4-CF.sub.3 -2-PyBr 5-CF.sub.3 -2-PyBr 6-CF.sub.3 -2-PyBr 3-Cl-5-CF.sub.3 -2-PyBr 3-Me-2-PyBr 4-Me-2-PyBr 5-Me-2-PyBr 6-Me-2-PyBr 3-NO.sub.2 -2-PyBr 4-NO.sub.2 -2-PyBr 5-NO.sub.2 -2-PyBr 6-NO.sub.2 -2-PyCF.sub.3 Pr-cycCF.sub.3 Bu-cycCF.sub.3 Pen-cycCF.sub.3 Hex-cycCF.sub.3 3,5-Cl.sub.2PhCF.sub.3 2,6-Cl.sub.2PhCF.sub.3 2,3-Cl.sub.2PhCF.sub.3 2,4,6-Cl.sub.3PhCF.sub.3 2,3,5-Cl.sub.3PhCF.sub.3 2,3,4-Cl.sub.3PhCF.sub.3 2-NO.sub.2PhCF.sub.3 2-CNPhCF.sub.3 3-CNPhCF.sub.3 4-CNPhCF.sub.3 CHMePhCF.sub.3 CMe.sub.2 PhCF.sub.3 2-Cl-4-CF.sub.3PhCF.sub.3 2,6-Cl.sub.2 -4-CF.sub.3PhCF.sub.3 2,5-Cl.sub.2PhCF.sub.3 3,4-Cl.sub.2PhCF.sub.3 2,4-(NO.sub.2).sub.2PhCF.sub.3 3-NO.sub.2PhCF.sub.3 4-NO.sub.2PhCF.sub.3 2-PyCF.sub.3 3-PyCF.sub.3 4-PyCF.sub.3 3-Cl-2-PyCF.sub.3 4-Cl-2-PyCF.sub.3 5-Cl-2-PyCF.sub.3 6-Cl-2-PyCF.sub.3 3-F-2-PyCF.sub.3 4-F-2-PyCF.sub.3 5-F-2-PyCF.sub.3 6-F-2-PyCF.sub.3 3-Br-2-PyCF.sub.3 4-Br-2-PyCF.sub.3 5-Br-2-PyCF.sub.3 6-Br-2-PyCF.sub.3 3-CF.sub.3 -2-PyCF.sub.3 4-CF.sub.3 -2-PyCF.sub.3 5-CF.sub.3 -2-PyCF.sub.3 6-CF.sub.3 -2-PyCF.sub.3 3-Cl-5-CF.sub.3 -2-PyCF.sub.3 3-Me-2-PyCF.sub.3 4-Me-2-PyCF.sub.3 5-Me-2-PyCF.sub.3 6-Me-2-PyCF.sub.3 3-NO.sub.2 -2-PyCF.sub.3 4-NO.sub.2 -2-PyCF.sub.3 5-NO.sub.2 -2-PyCF.sub.3 6-NO.sub.2 -2-PyBu-n PhBu-iso PhBu-sec PhBu-tert PhPen-n PhHex-n PhHex-iso PhBu-cyc PhPen-cyc PhHex-cyc PhCH.sub.2 Pr-cyc PhCH.sub.2 Bu-cyc PhCH.sub.2 Pen-cyc PhCH.sub.2 Hex-cyc PhCH.sub.2 CH.sub.2 Pr-cyc PhCH.sub.2 CHCH.sub.2 PhCH.sub.2 CHCHPh PhCH.sub.2 CH.sub.2 CHCH.sub.2 PhCH.sub.2 CCH PhCH.sub.2 CCMe PhOEt PhOPr-n PhOPr-iso PhOBu-n PhOBu-iso PhOBu-tert PhOCH.sub.2 F PhOCBrF.sub.2 PhOCF.sub.3 PhOCH.sub.2 CH.sub.2 Cl PhOCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 Cl PhSEt PhSPr-n PhSPr-iso PhSBu-n PhSBu-iso PhSBu-tert PhS(O)Me PhS(O)Et PhS(O)Pr-n PhS(O)Pr-iso PhS(O)Bu-n PhSO.sub.2 Me PhSO.sub.2 Et PhSO.sub.2 Pr-n PhSO.sub.2 Pr-iso PhSO.sub.2 Bu-n PhSO.sub.2 NMe.sub.2 PhSO.sub.2 NEt.sub.2 PhSO.sub.2 N(Pr-n).sub.2 PhSO.sub.2 N(Pr-iso).sub.2 PhSO.sub.2 N(Bu-n).sub.2 PhI PhCN PhNMe.sub.2 PhNEt.sub.2 PhN(Pr-n).sub.2 PhN(Pr-iso).sub.2 PhN(Bu-n).sub.2 PhCH.sub.2 Br PhCH.sub.2 I PhCHCl.sub.2 PhCHBr.sub.2 PhCCl.sub.3 PhCBr.sub.3 PhCF.sub.3 CH.sub.2 PhClCH.sub.2 CH.sub.2 CH.sub.2 PhClCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 PhCH.sub.2 OEt PhCH.sub.2 OPr-n PhCH.sub.2 OBu-n PhCH.sub.2 OBu-iso PhCH.sub.2 OBu-sec PhCH.sub.2 OBu-tert PhCH.sub.2 CH.sub.2 OEt PhCH.sub.2 CH.sub.2 OMe PhCH.sub.2 CH.sub.2 OEt PhCH.sub.2 CH.sub.2 OPr-n PhCH.sub.2 CH.sub.2 CH.sub.2 OMe PhCH.sub.2 CH.sub.2 CH.sub.2 OEt PhCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OMe PhCH.sub.2 SEt PhCH.sub.2 SPr-n PhCH.sub.2 SBu-n PhCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 SMe PhCH.sub.2 S(O)Me PhCH.sub.2 S(O)Et PhCH.sub.2 S(O)Pr-n PhCH.sub.2 S(O)Bu-n PhCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 S(O)Me PhCH.sub.2 SO.sub.2 Me PhCH.sub.2 SO.sub.2 Et PhCH.sub.2 SO.sub.2 Pr-n PhCH.sub.2 SO.sub.2 Bu-n PhCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 SO.sub.2 Me PhCH.sub.2 NMe.sub.2 PhCH.sub.2 NEt.sub.2 PhCH.sub.2 N(Pr-n).sub.2 PhCH.sub.2 N(Pr-iso).sub.2 PhCH.sub.2 N(Bu-n).sub.2 PhCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 NMe.sub.2 Ph2-ClPh Ph3-ClPh Ph4-ClPh Ph2,4-Cl.sub.2Ph Ph2-FPh Ph3-FPh Ph4-FPh Ph2-F-4-ClPh Ph2-BrPh Ph3-BrPh Ph4-BrPh Ph2-MePh Ph3-MePh Ph4-MePh Ph2,4-Me.sub.2Ph Ph2,6-Me.sub.2Ph Ph2-MeOPh Ph3-MeOPh Ph4-MeOPh Ph2-CF.sub.3Ph Ph3-CF.sub.3Ph Ph4-CF.sub.3Ph PhCH.sub.2 Ph PhOCH.sub.2 Ph PhSCH.sub.2 Ph PhBu-n 2-PyBu-iso 2-PyBu-sec 2-PyBu-tert 2-PyPen-n 2-PyHex-n 2-PyHex-iso 2-PyBu-cyc 2-PyPen-cyc 2-PyHex-cyc 2-PyCH.sub.2 Pr-cyc 2-PyCH.sub.2 Bu-cyc 2-PyCH.sub.2 Pen-cyc 2-PyCH.sub.2 Hex-cyc 2-PyCH.sub.2 CH.sub.2 Pr-cyc 2-PyCH.sub.2 CHCH.sub.2 2-PyCH.sub.2 CHCHMe 2-PyCH.sub.2 CH.sub.2 CHCH.sub.2 2-PyCH.sub.2 CCH 2-PyCH.sub.2 CCMe 2-PyOEt 2-PyOPr-n 2-PyOPr-iso 2-PyOBu-n 2-PyOBu-iso 2-PyOBu-tert 2-PyOCH.sub.2 F 2-PyOCBrF.sub.2 2-PyOCF.sub.3 2-PyOCH.sub.2 CH.sub.2 Cl 2-PyOCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 Cl 2-PySEt 2-PySPr-n 2-PySPr-iso 2-PySBu-n 2-PySBu-iso 2-PySBu-tert 2-PyS(O)Me 2-PyS(O)Et 2-PyS(O)Pr-n 2-PyS(O)Pr-iso 2-PyS(O)Bu-n 2-PySO.sub.2 Me 2-PySO.sub.2 Et 2-PySO.sub.2 Pr-n 2-PySO.sub.2 Pr-iso 2-PySO.sub.2 Bu-n 2-PySO.sub.2 NMe.sub.2 2-PySO.sub.2 NEt.sub.2 2-PySO.sub.2 N(Pr-n).sub.2 2-PySO.sub.2 N(Pr-iso).sub.2 2-PySO.sub.2 N(Bu-n).sub.2 2-PyI 2-PyCN 2-PyNMe.sub.2 2-PyNEt.sub.2 2-PyN(Pr-n).sub.2 2-PyN(Pr-iso).sub.2 2-PyN(Bu-n).sub.2 2-PyCH.sub.2 Br 2-PyCH.sub.2 I 2-PyCHCl.sub.2 2-PyCHBr.sub.2 2-PyCCl.sub.3 2-PyCBr.sub.3 2-PyCF.sub.3 CH.sub.2 2-PyClCH.sub.2 CH.sub.2 CH.sub.2 2-PyClCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 2-PyCH.sub.2 OEt 2-PyCH.sub.2 OPr-n 2-PyCH.sub.2 OBu-n 2-PyCH.sub.2 OBu-iso 2-PyCH.sub.2 OBu-sec 2-PyCH.sub.2 OBu-tert 2-PyCH.sub.2 CH.sub.2 OEt 2-PyCH.sub.2 CH.sub.2 OMe 2-PyCH.sub.2 CH.sub.2 OEt 2-PyCH.sub.2 CH.sub.2 OPr-n 2-PyCH.sub.2 CH.sub.2 CH.sub.2 OMe 2-PyCH.sub.2 CH.sub.2 CH.sub.2 OEt 2-PyCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OMe 2-PyCH.sub.2 SEt 2-PyCH.sub.2 SPr-n 2-PyCH.sub.2 SBu-n 2-PyCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 SMe 2-PyCH.sub.2 S(O)Me 2-PyCH.sub.2 S(O)Et 2-PyCH.sub.2 S(O)Pr-n 2-PyCH.sub.2 S(O)Bu-n 2-PyCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 S(O)Me 2-PyCH.sub.2 SO.sub.2 Me 2-PyCH.sub.2 SO.sub.2 Et 2-PyCH.sub.2 SO.sub.2 Pr-n 2-PyCH.sub.2 SO.sub.2 Bu-n 2-PyCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 SO.sub.2 Me 2-PyCH.sub.2 NMe.sub.2 2-PyCH.sub.2 NEt.sub.2 2-PyCH.sub.2 N(Pr-n).sub.2 2-PyCH.sub.2 N(Pr-iso).sub.2 2-PyCH.sub.2 N(Bu-n).sub.2 2-PyCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 NMe.sub.2 2-Py2-ClPh 2-Py3-ClPh 2-Py4-ClPh 2-Py2,4-Cl.sub.2Ph 2-Py2-FPh 2-Py3-FPh 2-Py4-FPh 2-Py2-F-4-ClPh 2-Py2-BrPh 2-Py3-BrPh 2-Py4-BrPh 2-Py2-MePh 2-Py3-MePh 2-Py4-MePh 2-Py2,4-Me.sub.2Ph 2-Py2,6-Me.sub.2Ph 2-Py2-MeOPh 2-Py3-MeOPh 2-Py4-MeOPh 2-Py2-CF.sub.3Ph 2-Py3-CF.sub.3Ph 2-Py4-CF.sub.3Ph 2-PyCH.sub.2 Ph 2-PyOCH.sub.2 Ph 2-PySCH.sub.2 Ph 2-PyCl Bu-tertCl Bu-isoCl Bu-secCl 3-CNPhCl 4-CNPhCl CHMePhCl CMe.sub.2 PhBr 3-CNPhBr 4-CNPhBr CHMePhBr CMe.sub.2 PhCF.sub.3 Bu-isoCF.sub.3 Bu-secCF.sub.3 CH.sub.2 Bu-cycCF.sub.3 CH.sub.2 Pen-cycCF.sub.3 CH.sub.2 Hex-cycCF.sub.3 CH.sub.2 CH.sub.2 Pr-cycCF.sub.3 CH.sub.2 CHCHMeCF.sub.3 CH.sub.2 CH.sub.2 CHCH.sub.2CF.sub.3 CH.sub.2 CCMeCF.sub.3 CH.sub.2 ClCF.sub.3 CH.sub.2 BrCF.sub.3 CH.sub.2 ICF.sub.3 CHCl.sub.2CF.sub.3 CHBr.sub.2CF.sub.3 CCl.sub.3CF.sub.3 CBr.sub.3CF.sub.3 CClF.sub.2CF.sub.3 CF.sub.3 CH.sub.2CF.sub.3 CF.sub.3 CF.sub.2CF.sub.3 CF.sub.3 CF.sub.2 CF.sub.2CF.sub.3 ClCH.sub.2 CH.sub.2 CH.sub.2CF.sub.3 ClCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2CF.sub.3 SO.sub.2 EtCF.sub.3 SO.sub.2 Pr-nCF.sub.3 SO.sub.2 Pr-isoCF.sub.3 SO.sub.2 Bu-nCF.sub.3 SO.sub.2 NEt.sub.2CF.sub.3 SO.sub.2 N(Pr-n).sub.2CF.sub.3 SO.sub.2 N(Pr-iso).sub.2CF.sub.3 SO.sub.2 N(Bu-n).sub.2CF.sub.3 CH.sub.2 OEtCF.sub.3 CH.sub.2 OPr-nCF.sub.3 CH.sub.2 OBu-nCF.sub.3 CH.sub.2 OBu-isoCF.sub.3 CH.sub.2 OBu-secCF.sub.3 CH.sub.2 OBu-tertCF.sub.3 CH.sub.2 CH.sub.2 OMeCF.sub.3 CH.sub.2 CH.sub.2 OEtCF.sub.3 CH.sub.2 CH.sub.2 OPr-nCF.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OMeCF.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OEtCF.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OMeCF.sub.3 CH.sub.2 OCH.sub.2 CH.sub.2 OMeCF.sub.3 CH.sub.2 OCH.sub.2 CH.sub.2 OEtCF.sub.3 CH.sub.2 SEtCF.sub.3 CH.sub.2 SPr-nCF.sub.3 CH.sub.2 SBu-nCF.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 SMeCF.sub.3 CH.sub.2 S(O)EtCF.sub.3 CH.sub.2 S(O)Pr-nCF.sub.3 CH.sub.2 S(O)Bu-nCF.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 S(O)MeCF.sub.3 CH.sub.2 SO.sub.2 EtCF.sub.3 CH.sub.2 SO.sub.2 Pr-nCF.sub.3 CH.sub.2 SO.sub.2 Bu-nCF.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 SO.sub.2 MeCF.sub.3 CH.sub.2 NEt.sub.2CF.sub.3 CH.sub.2 N(Pr-n).sub.2CF.sub.3 CH.sub.2 N(Pr-iso).sub.2CF.sub.3 CH.sub.2 N(Bu-n).sub.2CF.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 NMe.sub.2CF.sub.3 CO.sub.2 EtCF.sub.3 CO.sub.2 Pr-nCF.sub.3 CO.sub.2 Pr-isoCF.sub.3 CO.sub.2 Bu-nCF.sub.3 COEtCF.sub.3 COPr-nCF.sub.3 COPr-isoCF.sub.3 COBu-nCF.sub.3 CONHEtCF.sub.3 CONHPr-nCF.sub.3 CONHPr-isoCF.sub.3 CONHBu-nCF.sub.3 CONEt.sub.2CF.sub.3 CON(Pr-n).sub.2CF.sub.3 CON(Pr-iso).sub.2CF.sub.3 CON(Bu-n).sub.2CF.sub.3 CH.sub.2 CO.sub.2 EtCF.sub.3 CH.sub.2 CO.sub.2 Pr-nCF.sub.3 CH.sub.2 CO.sub.2 Pr-isoCF.sub.3 CH.sub.2 CO.sub.2 Bu-nCF.sub.3 CHMeCO.sub.2 Pr-nCF.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 CO.sub.2 MeCF.sub.3 CH.sub.2 COEtCF.sub.3 CH.sub.2 COPr-nCF.sub.3 CH.sub.2 COPr-isoCF.sub.3 CH.sub.2 COBu-nCF.sub.3 CHMeCOMeCF.sub.3 CHMeCOEtCF.sub.3 CHMeCOPr-nCF.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 COMe__________________________________________________________________________ TABLE 3__________________________________________________________________________ ##STR130## ##STR131## ##STR132## ##STR133## ##STR134## ##STR135## ##STR136## ##STR137## ##STR138## ##STR139## ##STR140## ##STR141##R.sup.4 R.sup.5__________________________________________________________________________Et PhPr-n PhPr-iso PhBu-n PhBu-iso PhBu-sec PhBu-tert PhPen-n PhHex-n PhHex-iso PhPr-cyc PhBu-cyc PhPen-cyc PhHex-cyc PhCH.sub.2 Pr-cyc PhCH.sub.2 Bu-cyc PhCH.sub.2 Pen-cyc PhCH.sub.2 Hex-cyc PhCH.sub.2 CH.sub.2 Pr-cyc PhCH.sub.2 CHCH.sub.2 PhCH.sub.2 CHCHMe PhCH.sub.2 CH.sub.2 CHCH.sub.2 PhCH.sub.2 CCH PhCH.sub.2 CCMe PhOMe PhOEt PhOPr-n PhOPr-iso PhOBu-n PhOBu-iso PhOBu-tert PhSO.sub.2 Me PhSO.sub.2 Et PhSO.sub.2 Pr-n PhSO.sub.2 Pr-iso PhSO.sub.2 Bu-n PhCH.sub.2 OMe PhCH.sub.2 OEt PhCH.sub.2 OPr-n PhCH.sub.2 OBu-n PhCH.sub.2 OBu-iso PhCH.sub.2 OBu-sec PhCH.sub.2 OBu-tert PhCH.sub.2 CH.sub.2 OMe PhCH.sub.2 CH.sub.2 OEt PhCH.sub.2 CH.sub.2 OPr-n PhCH.sub.2 CH.sub.2 CH.sub.2 OMe PhCH.sub.2 CH.sub.2 CH.sub.2 OEt PhCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OMe PhCH.sub.2 CH.sub.2 OMe CH.sub.2 CH.sub.2 OMeMe 3-ClPhMe 4-ClPhMe 2,4-Cl.sub.2PhMe 3,5-Cl.sub.2PhMe 2,3-Cl.sub.2PhMe 2,5-Cl.sub.2PhMe 3-FPhMe 4-FPhMe 2-F-4-ClMe 2-BrPhMe 3-BrPhMe 4-BrPhMe 3-MePhMe 4-MePhMe 2,4-Me.sub.2PhMe 3,5-Me.sub.2PhMe 2,6-Me.sub.2PhMe 2,3-Me.sub.2PhMe 2,5-Me.sub.2PhMe 2-MeOPhMe 3-MeOPhMe 4-MeOPhMe 2-CF.sub.3PhMe 3-CF.sub.3PhMe 4-CF.sub.3PhMe CH.sub.2 PhEt EtPr-n Pr-nPr-iso Pr-isoBu-n Bu-nH PhMe OMeMe OEtMe OBu-nMe 2,4,6-Cl.sub.3PhMe 2,3,5-Cl.sub.3PhMe 2,3,4-Cl.sub.3PhMe 2-NO.sub.2PhMe 2-CNPhMe MeMe EtMe Pr-isoMe Bu-isoMe Bu-secEt Pr-nEt Pr-isoEt Bu-nEt Bu-isoEt Bu-secPr-n Pr-isoPr-n Bu-nPr-n Bu-isoPr-n Bu-secBu-n Bu-isoBu-n Bu-secBu-iso Bu-isoBu-iso Bu-secBu-sec Bu-secOMe CH.sub.2 CHCH.sub.2OMe CH.sub.2 CHCHOEt CH.sub.2 CHCH.sub.2OEt CH.sub.2 CHCHMe HMe Bu-tertMe Hex-isoMe Pr-cycMe Bu-cycMe CHMeCHMe.sub.2Me Pen-cycMe Hex-cycMe CH.sub.2 Pr-cycMe CH.sub.2 Bu-cycMe CH.sub.2 Pen-cycMe CH.sub.2 Hex-cycMe CH.sub.2 CH.sub.2 Pr-cycMe CH.sub.2 CHCHMeMe CH.sub.2 CH.sub.2 CHCH.sub.2Me CH.sub.2 CCMeMe CH.sub.2 OMeMe CH.sub.2 OEtMe CH.sub.2 OPr-nMe CH.sub.2 OBu-nMe CH.sub.2 OBu-isoMe CH.sub.2 OBu-secMe CH.sub.2 OBu-tertMe CH.sub.2 CH.sub.2 OMeMe CH.sub.2 CH.sub.2 OEtMe CH.sub.2 CH.sub.2 OPr-nMe CH.sub.2 CH.sub.2 CH.sub.2 OMeMe CH.sub.2 CH.sub.2 CH.sub.2 OEtMe CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OMeMe OPr-nMe OPr-isoMe OBu-isoMe OBu-tertMe SO.sub.2 MeMe SO.sub.2 EtMe SO.sub.2 Pr-nMe SO.sub.2 Pr-isoMe SO.sub.2 Bu-nMe COMeMe COEtMe COPr-nMe COPr-isoMe COBu-nMe CO.sub.2 MeMe CO.sub.2 EtMe CO.sub.2 Pr-nMe CO.sub.2 Pr-isoMe CO.sub.2 Bu-nMe CH.sub.2 CO.sub.2 MeMe CH.sub.2 CO.sub.2 EtMe CH.sub.2 CO.sub.2 Pr-nMe CH.sub.2 CO.sub.2 Bu-nMe CHMeCO.sub.2 MeMe CHMeCO.sub.2 EtMe CH.sub.2 CH.sub.2 CO.sub.2 MeMe CH.sub.2 CH.sub.2 CH.sub.2 CO.sub.2 MeMe CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CO.sub.2 MeMe CH(Pr-iso)CO.sub.2 MeMe CH(Bu-sec)CO.sub.2 MeMe CH(Bu-iso)CO.sub.2 MeMe CH(CH.sub.2 Ph)CO.sub.2 MeMe CH.sub.2 CH.sub.2 CNMe 1-NaphMe 2-NaphMe CH.sub.2 -1-NaphMe CH.sub.2 -2-NaphMe CH.sub.2 PhMe CHMePhMe CMe.sub.2 PhMe CH.sub.2 -2-ClPhMe CH.sub.2 -3-ClPhMe CH.sub.2 -4-ClPhMe 2-PyMe 6-MeO-2-PyMe 3-MeO-2-PyMe 6-Cl-2-PyMe 6-F-2-PyMe 5-CF.sub.3 -2-PyMe 3-Cl-5-CF.sub.3 -2-PyMe 3-PyMe 4-PyMe CH.sub.2 -5-Cl-2-PyMe CH.sub.2 -6-Cl-3-PyH HH EtH Pr-nH Pr-isoH Bu-nH Bu-isoH Bu-secH Bu-tertH CHMeCHMe.sub.2H Pen-nH Hex-nH Hex-isoH Pr-cycH Bu-cycH Pen-cycH Hex-cycH CH.sub.2 Pr-cycH CH.sub.2 Bu-cycH CH.sub.2 Pen-cycH CH.sub.2 Hex-cycH CH.sub.2 CH.sub.2 Pr-cycH CH.sub.2 CHCH.sub.2H CH.sub.2 CHCHMeH CH.sub.2 CH.sub.2 CHCH.sub.2H CH.sub.2 CCHH CH.sub.2 CCMeH CH.sub.2 OMeH CH.sub.2 OEtH CH.sub.2 OPr-nH CH.sub.2 OBu-nH CH.sub.2 OBu-isoH CH.sub.2 OBu-secH CH.sub.2 OBu-tertH CH.sub.2 CH.sub.2 OMeH CH.sub.2 CH.sub.2 OEtH CH.sub.2 CH.sub.2 OPr-nH CH.sub.2 CH.sub.2 CH.sub.2 OMeH CH.sub.2 CH.sub.2 CH.sub.2 OEtH CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OMeH 2-ClPhH 3-ClPhH 4-ClPhH 2,4-Cl.sub.2PhH 3,5-Cl.sub.2PhH 2,6-Cl.sub.2PhH 2,3-Cl.sub.2PhH 2,5-Cl.sub.2PhH 2-FPhH 3-FPhH 4-FPhH 2-F-4-ClPhH 2-BrPhH 3-BrPhH 4-BrPhH 2-MePhH 3-MePhH 4-MePhH 2,4-Me.sub.2PhH 3,5-Me.sub.2PhH 2,6-Me.sub.2PhH 2,3-Me.sub.2PhH 2,5-Me.sub.2PhH 2-MeOPhH 3-MeOPhH 4-MeOPhH 2-CF.sub.3PhH 3-CF.sub.3PhH 4-CF.sub.3PhH 2,4,6-Cl.sub.3PhH 2,3,5-Cl.sub.3PhH 2,3,4-Cl.sub.3PhH 2-NO.sub.2PhH 2-CNPhH CH.sub.2 PhH OMeH OEtH OPr-nH OPr-isoH OBu-nH OBu-isoH OBu-tertH SO.sub.2 MeH SO.sub.2 EtH SO.sub.2 Pr-nH SO.sub.2 Pr-isoH SO.sub.2 Bu-nH COMeH COEtH COPr-nH COPr-isoH COBu-nH CO.sub.2 MeH CO.sub.2 EtH CO.sub.2 Pr-nH CO.sub.2 Pr-isoH CO.sub.2 Bu-nH CH.sub.2 CO.sub.2 MeH CH.sub.2 CO.sub.2 EtH CH.sub.2 CO.sub.2 Pr-nH CH.sub.2 CO.sub.2 Bu-nH CHMeCO.sub.2 MeH CHMeCO.sub.2 EtH CH.sub.2 CH.sub.2 CO.sub.2 MeH CH.sub.2 CH.sub.2 CH.sub.2 CO.sub.2 MeH CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CO.sub.2 MeH CH(Pr-iso)CO.sub.2 MeH CH(Bu-sec)CO.sub.2 MeH CH(Bu-iso)CO.sub.2 MeH CH(CH.sub.2 Ph)CO.sub.2 MeH CH.sub.2 CH.sub.2 CNH 1-NaphH 2-NaphH CH.sub.2 -1-NaphH CH.sub.2 -2-NaphH CH.sub.2 PhH CHMePhH CMe.sub.2 PhH CH.sub.2 -2-ClPhH CH.sub.2 -3-ClPhH CH.sub.2 -4-ClPhH 2-PyH 6-MeO-2-PyH 3-MeO-2-PyH 6-Cl-2-PyH 6-F-2-PyH 5-CF.sub.3 -2-PyH 3-Cl-5-CF.sub.3 -2-PyH 3-PyH 4-PyH CH.sub.2 -5-Cl-2-PyH CH.sub.2 -6-Cl-3-Py__________________________________________________________________________ TABLE 4__________________________________________________________________________ ##STR142## ##STR143## ##STR144## ##STR145## ##STR146## ##STR147## ##STR148## ##STR149## ##STR150## ##STR151## ##STR152## ##STR153##__________________________________________________________________________

In Table 4, NR.sup.4 R.sup.5 represents: ##STR154##

The dose of the compounds of the present invention to be applied to agricultural land, etc. varies, depending on the scene to which they are applied, the time when they are applied, the method by which they are applied, the weeds which shall be terminated by them and the crop plants which they shall protect from harmful weeds, etc. In general, it is suitably from 0.001 to 50 kg/ha (hectare) or so, preferably from 0.01 to 10 kg/ha or so, as the amount of the active ingredient.

If desired, the compounds of the present invention may be combined with other herbicides, various insecticides, fungicides, plant growth regulators, synergism agents, etc. at the time of formulations or applications.

In particular, they are preferably combined with other herbicides, whereby the dose of them to be used may be reduced so that the costs of the herbicidal products containing them may be lowered and, additionally, their herbicidal spectra may be broadened due to the synergistic effect of the added chemicals so that the combined products may have a higher herbicidal effect. To prepare such combined products, plural known herbicides may be combined with the compounds of the present invention.

As herbicides which may be combined with the compounds of the present invention, for example, mentioned are the compounds described in Farm Chemicals Handbook (1990).

As chemicals which are preferably combined with the compounds of the present invention, for example, mentioned are pyrazosulfuron ethyl (common name), bensulfuron methyl (common name), cinosulfuron (common name) and imazosulfuron (common name).

In addition to these, the following chemicals may also be combined with the compounds of the present invention:

Pretilachlor (common name), esprocarb (common name), pyrazolate (common name), pyrazoxyfen (common name), benzofenap (common name), dymron (common name), bromobutide (common name), naproanilide (common name), clomeprop (common name), CNP (common name), chlomethoxynil (common name), bifenox (common name), oxadiazon (common name), mefenacet (common name), butachlor (common name), butenachlor (common name), dithiopyr (common name), benfuresate (common name), pyributicarb (common name), benthiocarb (common name), dimepiperate (common name), molinate (common name), butamifos (common name), quinclorac (common name), cinmethylin (common name), simetryn (common name), SAP (bensulide - common name), dimethametryn (common name), MCPA, MCPB, 2',3'-dichloro-4-ethoxymethoxybenzanilide (HW-52 as test name), 1-(2-chlorobenzyl)-3-(.alpha.,.alpha.-dimethylbenzyl)urea (JC-940 as test name), N-[2'-(3'-methoxy)-thienylmethyl]-N-chloroacetyl-2,6-dimethylanilide (NSK-850 as test name), etc.

Where the compounds of the present invention are used as herbicide, in general, they may be mixed with pertinent carriers, for example, solid carriers such as clay, talc, bentonite, diatomaceous earth, white carbon, etc. or liquid carriers such as water, alcohols (e.g., isopropanol, butanol, benzyl alcohol, furfuryl-alcohol, etc.), aromatic hydrocarbons (e.g., toluene, xylene, etc.), ethers (e.g., anisole, etc.), ketones (e.g., cyclohexanone, isophorone, etc.), esters (e.g., butyl acetate, etc.), acid amides (e.g., N-methylpyrrolidone, etc.) or halogenated .hydrocarbons (e.g., chlorobenzene, etc.). If desired, they may be prepared into various practical formulations, including liquid formulation, emulsifiable concentrate, wettable powder, dry flowable powder, flowable liquid, dust, granule, etc., optionally along with surfactant, emulsifier, dispersing agent, penetration promoter, adhesion promoter, tackifier, anti-freezing agent, anti-caking agent, stabilizer, etc.

Where the compounds of the present invention are formulated into herbicidal granules to be applied to paddy fields, for example, usable are kaolinite, montmorillonite, diatomaceous earth, bentonite, talc, clay, calcium carbonate, calcium sulfate, ammonium sulfate, etc., as the solid carriers, and alkylbenzenesulfonates, polyoxyethylene alkylaryl ethers, ligninesulfonates, alkylsulfosuccinates, polyoxyethylene fatty acid esters, naphthalenesulfonates, polyoxyethylene alkylaryl ether sulfates, alkylamine salts, tripolyphosphates, etc., as the surfactants. The content of these surfactants in the herbicidal granules is not specifically defined but is, in general, desirably within the range of from 0.05 to 20 parts by weight relative to 100 parts by weight of the granules. If desired, the granules may contain a decomposition inhibitor such as epoxidated soybean oil, etc.

Next, examples of formulations of herbicidal products containing the compounds of the present invention are mentioned below, which, however, are not limitative. In the following examples, all "parts" are by weight.

______________________________________Wettable Powder:______________________________________Compound of this invention 5 to 80 pts.Solid carrier 10 to 85 pts.Surfactant 1 to 10 pts.Others 1 to 5 pts.______________________________________

As others, for example, mentioned are anti-caking agent, etc.

______________________________________Emulsifiable concentrate:Compound of this invention 1 to 30 pts.Liquid carrier 30 to 95 pts.Surfactant 5 to 15 pts.Flowable Liquid:Compound of this invention 5 to 70 pts.Liquid Carrier 15 to 65 pts.Surfactant 5 to 12 pts.Others 5 to 30 pts.______________________________________

As others, for example, mentioned are anti-freezing agent, tackifier, etc.

______________________________________Granular Wettable Powder (dry flowable powder):Compound of this invention 20 to 90 pts.Solid Carrier 10 to 60 pts.Surfactant 1 to 20 pts.Granules:Compound of this invention 0.1 to 10 pts.Solid carrier 90 to 99.9 pts.Others 1 to 5 pts.Formulation Example 1: Wettable PowderCompound No. 1 of this invention 20 pts.Zeeklite A 76 pts.(kaolin clay, trade name by Zeeklite Co.)Sorpol 5039 2 pts.(mixture of nonionic surfactant and anionicsurfactant, trade name by Toho Chemical Co.)Carplex (anti-caking agent) 2 pts.(white carbon, trade name by ShionogiPharmaceutical Co.)______________________________________

The above-mentioned components were homogeneously blended and powdered to give a wettable powder.

______________________________________Formulation Example 2: Wettable Powder______________________________________Compound No. 1 of this invention 40 pts.Zeeklite A 54 pts.(kaolin clay, trade name by Zeeklite Co.)Sorpol 5039 2 pts.(mixture of nonionic surfactant and anionicsurfactant, trade name by Toho Chemical Co.)Carplex (anti-caking agent) 4 pts.(white carbon, trade name by ShionogiPharmaceutical Co.)______________________________________

The above-mentioned components were homogeneously blended and powdered to give a wettable powder.

______________________________________Formulation Example 3: Emulsifiable concentrate______________________________________Compound No. 1 of this invention 5 pts.Xylene 75 pts.Dimethylformamide 15 pts.Sorpol 2680 5 pts.(mixture of nonionic surfactant and anionicsurfactant, trade name by Toho Chemical Co.)______________________________________

The above-mentioned components were homogeneously blended to give an emulsion.

______________________________________Formulation Example 4: Flowable Liquid______________________________________Compound No. 1 of this invention 25 pts.Agrisole S-710 10 pts.(nonionic surfactant, trade name by Kaoh Co.)Runox 1000C 0.5 pts.(anionic surfactant, trade name by TohoChemical Co.)Aqueous 1% Rodopol water 20 pts.(tackifier, trade name by Rhone-Poulenc Co.)Water 44.5 pts.______________________________________

The above-mentioned components were homogeneously blended to give a flowable liquid.

______________________________________Formulation Example 5: Flowable Liquid______________________________________Compound No. 1 of this invention 40 pts.Agrisole S-710 10 pts.(nonionic surfactant, trade name by Kaoh Co.)Runox 1000C 0.5 pts.(anionic surfactant, trade name by TohoChemical Co.)Aqueous 1% Rodopol water 20 pts.(tackifier, trade name by Rhone-Poulenc Co.)Water 29.5 pts.______________________________________

The above-mentioned components were homogeneously blended to give a flowable liquid.

______________________________________Formulation Example 6: Granular Wettable Powder(dry flowable powder)______________________________________Compound No. 1 of this invention 75 pts.Isobam No. 1 10 pts.(anionic surfactant, trade name by KurarayIsoprene Chemical Co.)Vanilex N 5 pts.(anionic surfactant, trade name by SanyoKokusaku Pulp Co.)Carplex #80 10 pts.(white carbon, trade name by ShionogiPharmaceutical Co.)______________________________________

The above-mentioned components were homogeneously blended and finely powdered to give a dry flowable powder.

______________________________________Formulation Example 7: Granule______________________________________Compound No. 1 of this invention 1 pts.Bentonite 55 pts.Talc 44 pts.______________________________________

The above-mentioned components were blended and powdered, and a small amount of water was added thereto,stirred, further blended and kneaded. Using an granulator, the mixture was granulated and dried to give granules.

______________________________________Formulation Example 8: Granule______________________________________Compound No. 1 of this invention 1.0 pts.Compound (A) 0.07 pts.DBSN 3 pts.Epoxidated Soybean Oil 1 pts.Bentonite 30 pts.Talc 64.93 pts.______________________________________

The above-mentioned components were blended and powdered, and a small amount of water was added thereto and kneaded. Using an extrusion granulator, the mixture was granulated and dried to give granules.

Compound (A) is pyrazosulfuron ethyl (common name); and DBSN is sodium dodecylbenzenesulfonate.

Where the above-mentioned wettable powder, emulsion, flowable liquid and granular wettable powder are actually used, they are diluted with water to 1/50 to 1/1000 dilutions, and the dilution may be applied in a dose of from 0.001 to 50 kg/ha, preferably from 0.01 to 10 kg/ha, as the active ingredient.

The herbicides containing the compounds of the present invention may be applied to paddy fields both for soil treatment and for foliage treatment.

As examples of paddy weeds, mentioned are weeds of the family Alismataceae such as Alisma canaliculatum, Sagittaria trifolia, Sagittaria pygmaea, etc.; weeds of the family Cyperaceae such as Cyperus difformis, Cyperus serotinus, Scirpus juncoides, Eleocharis kuroguwai, etc.; weeds of the family Scrothulariaceae such as Lindemia pyxidaria, etc.; weeds of the family Potenderiaceae such as Monochoria vaginalis, etc.; weeds of the family Potamogetonaceae such as Potamogeton distinctus, etc.; weeds of the family Lythraceae such as Rotala indica, etc.; and weeds of the family Gramineae such as Echinochloa crus-galli, etc.

The compounds of the present invention are also usable as herbicides for soil treatment, soil incorporation treatment and foliage treatment. Furthermore, they may also be applied to control various weeds in non-agricultural fields, such as playgrounds, vacant lands, railroad sides, etc., in addition to agricultural and horticultural fields such as paddy fields, upland fields, orchards, etc.

The following test examples concretely demonstrate the usefulness of the compounds of the present invention as herbicides.

Test Example 1: Test of compounds of the invention as to their herbicidal effect, by soil treatment under paddy field condition:

An Alluvium soil was put in 1/5000 are-Wagner pots, and water was added thereto to knead the soil therein. Accordingly, a paddy field condition was prepared, having a depth of water of 4 cm. Seeds of Echinochloa crus-galli, Monochoria vaginalis, Rotala indica and Scirpus juncoides were sown mixedly in the pots, and 2.5 leaves-stage rice plants were transplanted therein. The pots were put in a greenhouse at 25.degree. to 30.degree. C. so as to grow the plants. On the first day after the seeding, pre-determined doses of the compounds of the present invention, that had been prepared into herbicidal formulations in accordance with the formulation examples mentioned above, were applied on the water surfaces in the pots. Three weeks after the application, the herbicidal effect of the test compounds against the rice plants and the weeds was checked. The effect was evaluated by 5-rank evaluation, in which "0" means that the compound had no influence on the plants while "5" means that the plants were completely withered. The test results are shown in Table 5 below.

Test Example 2: Test of compounds of the invention as to their herbicidal effect, by foliage treatment under paddy field condition.

An Alluvium soil was put in 1/5000 are-Wagner pots, and water was added thereto to knead the soil therein. Accordingly, a paddy field condition was prepared, having a depth of water of 4 cm. Seeds of Echinochloa crus-galli, Monochoria vaginalis, Rotala indica and Scirpus juncoides were sown mixedly in the pots, and 2.5 leaves-stage rice plants were transplanted therein. The pots were put in a greenhouse at 25.degree. to 30.degree. C. so as to grow the plants. After the weeds of Echinochloa crus-galli, Monochoria vaginalis, Rotala indica and Scirpus juncoides had grown to one leaf- to two leaves-stage and the rice plants to four leaves-stage, pre-determined amount of the compounds of the present invention, that had been prepared into herbicidal formulations in accordance with the formulation examples mentioned above, were applied over the plants in the pots. Three weeks after the application, the herbicidal effect of the test compounds against the rice plants and the weeds was checked. The effect was evaluated in the same manner as in Test Example 1. The test results are shown in Table 6 below.

In the following tables, A means Echinochloa crus-galli; B means Scirpus juncoides, C means Monochoria vaginalis, D means Rotala indica, and a means rice plants.

TABLE 5______________________________________ Amount of CompoundCompound No. g/a A B C D a______________________________________1 10 5 5 5 5 02 10 5 5 5 4 03 10 5 5 5 5 04 10 5 5 5 5 05 10 5 5 5 5 07 10 5 5 5 4 08 10 5 5 4 2 09 10 5 5 5 4 010 10 5 4 5 2 011 10 5 4 5 5 012 10 5 2 5 4 013 10 5 4 5 4 014 10 5 4 5 4 016 10 5 5 5 4 018 10 5 4 4 4 019 10 5 4 4 4 022 10 5 5 5 5 025 10 5 5 5 5 026 10 5 5 5 5 027 10 5 5 5 5 033 10 5 5 5 5 034 10 5 5 5 5 037 10 5 5 4 4 038 10 5 5 4 4 039 10 5 5 5 5 040 10 5 5 4 4 044 10 5 5 4 5 045 10 5 5 5 4 050 10 5 5 4 4 055 10 5 5 4 4 057 10 5 5 4 5 058 10 5 5 5 5 059 10 5 5 5 5 060 10 5 5 5 5 061 10 5 5 4 4 062 10 5 5 5 4 063 10 5 5 5 4 064 10 5 5 5 4 065 10 5 5 5 4 066 10 5 5 5 4 067 10 5 5 5 5 087 10 5 5 5 5 088 10 5 5 5 5 092 10 5 5 5 5 095 10 5 5 4 4 097 10 5 5 5 5 098 10 5 5 5 4 099 10 5 5 5 5 0100 10 5 5 5 5 0101 10 5 5 5 5 0104 10 5 5 5 4 0105 10 5 5 5 4 0106 10 5 5 5 4 0107 10 5 5 5 4 0108 10 5 5 5 5 0116 10 5 5 5 4 0124 10 5 5 5 5 0125 10 5 5 5 5 0127 10 5 5 5 5 0128 10 5 5 4 4 0133 10 5 5 5 5 0136 10 5 5 5 5 0138 10 5 5 5 4 0146 10 5 5 5 5 0149 10 5 5 5 5 0170 10 5 5 5 4 0171 10 5 5 5 4 0173 10 5 5 5 5 0174 10 5 5 5 4 0______________________________________ TABLE 6______________________________________ Amount of CompoundCompound No. g/a A B C D a______________________________________4 10 5 4 4 3 034 10 5 4 4 4 038 10 5 4 3 4 059 10 5 4 4 2 063 10 5 4 4 4 065 10 5 5 4 4 066 10 5 5 4 4 088 10 5 5 4 4 092 10 5 4 4 4 098 10 5 4 5 5 099 10 5 4 5 4 0100 10 5 4 5 4 0101 10 5 5 5 4 0105 10 5 4 4 4 0107 10 5 4 4 4 0108 10 5 4 4 4 0125 10 5 4 5 4 0128 10 5 4 4 4 0134 10 5 4 4 4 0136 10 5 5 5 4 0138 10 5 4 4 4 0146 10 5 5 5 5 0149 10 5 5 5 5 0173 10 5 5 5 5 0174 10 5 4 5 3 0______________________________________

Claims

1. A pyrazole-glycolic acid amide of formula (1): ##STR155## wherein R.sup.1 represents a C.sub.1-4 haloalkyl group, a cyano group, or a halogen atom;

R.sup.2 represents an unsubstituted phenyl group or an unsubstituted pyridyl group;

R.sup.3 represents a halogen atom;

R.sup.4 and R.sup.5 form, along with the nitrogen atom to which they bond, a 5-membered to 8-membered ring, wherein the ring may contain one or more nitrogen atoms and the ring may be substituted by a C.sub.1-4 alkyl group.

2. A herbicidal composition comprising one or more pyrazole-glycolic acid amide(s) as claimed in claim 1 as the active ingredient(s).

3. A method for controlling or inhibiting the growth of weeds by applying thereto a herbicidally effective amount of one or more pyrazole-glycolic acid amide(s) as claimed in claim 1.