Claims
- 1. A derivative of benzyl ether represented by the formula (I): ##STR55## wherein R is a straight-chain alkyl group having 4 to 10 carbon atoms, a branched alkyl group having 4 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, an alkyl group having 1 to 3 carbon atoms which is substituted with an alicyclic structure having 3 to 7 carbon atoms, a phenyl group or an aralkyl group having 7 to 9 carbon atoms:
- X.sup.1 is a halogen or an alkyl group having 1 to 3 carbon atoms;
- X.sup.2 is a hydrogen, a halogen or an alkyl group having 1 to 3 carbon atoms; and
- Z is a nitro group or an amino group;
- provided that when one of X.sup.1 and X.sup.2 is a halogen at the 4 position, the other at the 6 position is not a halogen; and further provided that when X.sup.1 is an ethyl group at the 4- or the 6-position and X.sup.2 is a hydrogen, R is not a phenyl group.
- 2. A derivative of benzyl ether represented by the formula (I): ##STR56## wherein R is a straight-chain alkyl group having 2 to 10 carbon atoms which is substituted with 3 to 19 fluorine atoms, or a branched alkyl group having 3 to 10 carbon atoms which is substituted with 3 to 19 fluorine atoms;
- X.sup.1 is a halogen or an alkyl group having 1 to 3 carbon atoms;
- X.sup.2 is a hydrogen, a halogen or an alkyl group having 1 to 3 carbon atoms; and
- Z is a nitro group or an amino group.
- 3. The derivative according to claim 2, wherein said derivative is 4-chloro-3-(2,2,2-trifluoroethoxy)methyl-1-nitrobenzene.
- 4. The derivative according to claim 2, wherein said derivative is 4-chloro-3-(2,2,3,3-tetrafluoropropoxy) methyl-1-nitrobenzene.
- 5. The derivative according to claim 2, wherein said derivative is 4-chloro-3-(2,2,3,3,3-pentafluoropropoxy) methyl-1-nitrobenzene.
- 6. The derivative according to claim 2, wherein said derivative is 4-chloro-3-(2,2,3,4,4,4-hexafluorobutoxy) methyl-1-nitrobenzene.
- 7. The derivative according to claim 2, wherein said derivative is 4-chloro-3-(2,2,3,3,4,4,4-heptafluorobutoxy)methyl-1-nitrobenzene.
- 8. The derivative according to claim 2, wherein said derivative is 3-(2,2,3,3,3-pentafluoropropoxy)methyl-4-methyl-1-nitrobenzene.
- 9. The derivative according to claim 2, wherein said derivative is 4-chloro-3-(2,2,2-trifluoroethoxy)methylaniline.
- 10. The derivative according to claim 2, wherein said derivative is 4-chloro-3-(2,2,4,4-tetrafluoropropoxy) methyl-aniline.
- 11. The derivative according to claim 2, wherein said derivative is 4-chloro-3-(2,2,3,3,3-pentafluoropropoxy) methyl-aniline.
- 12. The derivative according to claim 2, wherein said derivative is 4-chloro-3-(2,2,3,4,4,4-hexafluorobutoxy) methyl-aniline.
- 13. The derivative according to claim 2, wherein said derivative is 4-chloro-3-(2,2,3,3,4,4,4-heptafluorobutoxy)methyl-aniline.
- 14. The derivative according to claim 2, wherein said derivative is 3-(2,2,3,3,3-pentafluoropropoxy)methyl-4-methylaniline.
- 15. A derivative of benzyl ether represented by the formula (I): ##STR57## wherein R is a straight-chain alkyl group having 2 to 4 carbon atoms which is substituted with 3 to 7 fluorine atoms, X.sup.1 is a chlorine or a methyl group, and X.sup.2 is a hydrogen; and Z is a nitro group or an amino group.
Priority Claims (2)
| Number |
Date |
Country |
Kind |
| 62-54579 |
Mar 1987 |
JPX |
|
| 62-153031 |
Jun 1987 |
JPX |
|
CROSS-REFERENCE TO RELATED APPLICATION
The present invention is a continuation-in-part application of U.S. patent application Ser. No. 162,699 filed on Mar. 1, 1988, now U.S. Pat. No. 4,973,353.
The present invention relates to the derivative of benzyl ether represented by the formula (I): ##STR3## as an intermediate compound of the derivatives of 1,5-diphenyl-1H-1,2,4-triazole-3-carboxamide represented by the formula (II) having the excellent selective herbicidal activity. ##STR4##
In formula (I) and formula (II), R is a straight-chain alkyl group having 1 to 10 carbon atoms which is non-substituted or substituted with 1 to 19 fluorine atoms, a branched alkyl group having 3 to 10 carbon atoms which is non-substituted or substituted with 1 to 19 fluorine atoms, a cyclic alkyl group having 3 to 10 carbon atoms, an alkyl group having 1 to 3 carbon atoms which is substituted with an alicyclic structure having 3 to 7 carbon atoms, a phenyl group or an aralkyl group having 7 to 9 carbon atoms; X.sup.1 is a halogen or an alkyl group having 1 to 3 carbon atoms; X.sup.2 is a hydrogen, a halogen or an alkyl group having 1 to 3 carbon atoms; Y.sup.1 is a hydrogen or a fluorine; Y.sup.2 is a hydrogen or a fluorine; and Z is a nitro group or an amino group.
Rice, wheat and corn are the important farm products, and use of herbicides is essential for protecting these crops from harm by weeds so as to attain an increased yield.
It is known that the derivatives of 1,5-diphenyl-1H-1,2,4-triazole-3-carboxamide have a herbicidal activity. For instance, Japanese Patent Application Kokai (Laid-Open) No. 193406/82 discloses a herbicidal composition containing as its active ingredient a derivative of 1,2,4-triazole represented by the formula: ##STR5## wherein R.sub.1 is a hydrogen atom, a fluorine atom, a chlorine atom, an iodine atom, a lower alkyl group having 1 to 3 carbon atoms, an alkyl group substituted with fluorine, a nitro group or a methoxy group; R.sub.2 is a hydrogen atom, a chlorine atom or a methyl group; and R.sub.3 is a hydrogen atom or a methyl group.
Also, in Japanese Patent Application Kokai (Laid-Open) No. 98004/84 is disclosed a herbicidal composition containing a derivative of 1,2,4-triazole represented by the formula: ##STR6## wherein R.sub.1 and R.sub.2 represent independently a hydrogen atom, a halogen atom, an alkyl group or a halogenoalkyl group; R.sub.3 is a hydrogen atom, a halogen atom or an alkyl group; and R.sub.4 is a cyano, carbamoyl, thiocarbamoyl, N-alkylcarbamoyl, N-halogenoalkylcarbamoyl, N-methoxyalkylcarbamoyl, N-alkenylcarbamoyl, N-halogenoalkenylcarbamoyl, N-acylcarbamoyl, N-halogenoacylcarbamoyl or N-methylthiocarbamoyl group.
These derivatives, however, are still unsatisfactory in herbicidal activity and selectivity. Therefore, development of the compounds having high herbicidal activities and excellent selectivity enabling killing of weeds alone without doing any harm to the crops such as rice, wheat, corn, etc., has been strongly desired.
On the other hand, a derivative of benzyl ether represented by the formula: ##STR7## wherein R represents a straight chain alkyl group having 1 to 7 carbon atoms, isopropyl group, phenyl group, benzyl group, propynyl group and 2,2,2-trifluoroethyl group are known.
For example, these compounds are described in The Journal of the Chemical Society", Vol. 1954 (1954) Page 4127, Chekoslovenska Farmacie, Vol. 30 (1981) Page 184, U.S. Pat. No. 4,348,223 (1982), Journal of Pharmaceutical Sciences Vol. 56 (1976) Page 871, Chemical Abstracts, Vol 83 No. 92303 and Analytical Chemistry, Vol. 54 (1982) Page 529.
As a result of the present inventor's studies for providing a compound showing a high herbicidal activity but being practically harmless to such crops as rice, wheat and corn, it has been found that the derivative of benzyl ether represented by the formula (I) is useful as an intermediate compound of the derivatives of 1,5-diphenyl-1H-1,2,4-triazole-3-carboxy amide represented by the formula (II) having excellent selective herbicidal activities against grass weeds and, in particular, broadleaf weeds while doing no harm to such crops as rice, wheat and corn.
The object of the present invention is to provide the derivative of benzyl ether which is represented by the following formula (I) ##STR8## wherein R is a straight-chain alkyl group having 1 to 10 carbon atoms which is non-substituted or substituted with 1 to 19 fluorine atoms, a branched alkyl group having 3 to 10 carbon atoms which is non-substituted or substituted with 1 to 19 fluorine atoms, a cyclic alkyl group having 3 to 10 carbon atoms, an alkyl group having 1 to 3 carbon atoms which is substituted with an alicyclic structure having 3 to 7 carbon atoms, a phenyl group or an aralkyl group having 7 to 9 carbon atoms; X.sup.1 is a halogen or an alkyl group having 1 to 3 carbon atoms; X.sup.2 is a hydrogen, a halogen or an alkyl group having 1 to 3 carbon atoms; Z is a nitro group or an amino group; and which is useful as an intermediate compound of the derivatives of 1,5-diphenyl 1H-1,2,4-triazole-3-carboxamide represented by the formula (II) having the excellent selective herbicidal activity; ##STR9## wherein R is a straight-chain alkyl group having 1 to 10 carbon atoms which is non-substituted or substituted with 1 to 19 fluorine atoms, a branched alkyl group having 3 to 10 carbon atoms which is non-substituted or substituted with 1 to 19 fluorine atoms, a cyclic alkyl group having 3 to 10 carbon atoms, an alkyl group having 1 to 3 carbon atoms which is substituted with an alicyclic structure having 3 to 7 carbon atoms, a phenyl group or an aralkyl group having 7 to 9 carbon atoms; X.sup.1 is a halogen or an alkyl group having 1 to 3 carbon atoms; X.sup.2 is a hydrogen, a halogen or an alkyl group having 1 to 3 carbon atoms; Y.sup.1 is a hydrogen or a fluorine; and Y.sup.2 is a hydrogen or a fluorine.
The derivative of benzyl ether according to the present invention is a compound represented by the general formula (I): ##STR10## wherein R is a straight-chain alkyl group having 1 to 10 carbon atoms which is non-substituted or substituted with 1 to 19 fluorine atoms, a branched alkyl group having 3 to 10 carbon atoms which is non-substituted or substituted with 1 to 19 fluorine atoms, a cyclic alkyl group having 3 to 10 carbon atoms, an alkyl group having 1 to 3 carbon atoms which is substituted with an alicyclic structure having 3 to 7 carbon atoms, a phenyl group or an aralkyl group having 7 to 9 carbon atoms; X.sup.1 is a halogen or an alkyl group having 1 to 3 carbon atoms; X.sup.2 is a hydrogen, a halogen or an alkyl group having 1 to 3 carbon atoms; and Z is a nitro group or an amino group.
When Z is a nitro group, formula (I) is nitrobenzyl ether represented by formula (III), ##STR11## and
when Z is an amino group, formula (I) is the derivative of aniline represented by formula (IV). ##STR12##
In formula (III) and (IV), R, X.sup.1, X.sup.2 are as defined above.
A preferred compound represented by the general formula (I) is a compound in which R is a straight-chain alkyl group having 3 to 6 carbon atoms which is non-substituted or substituted with 3 to 12 fluorine atoms, a branched alkyl group having 4 to 7 carbon atoms which is non-substituted or substituted with 3 to 12 fluorine atoms, a cyclic alkyl group having 4 to 7 carbon atoms, an alkyl group having 1 to 3 carbon atoms which is substituted with an alicyclic structure having 3 to 7 carbon atoms, a phenyl group or an aralkyl group having 7 to 9 carbon atoms;
X.sup.1 is a halogen or an alkyl group having 1 to 3 carbon atoms; X.sup.2 is a hydrogen, a halogen or an alkyl group having 1 to 3 carbon atoms; and Z represents a nitro group or an amino group.
A further preferred compound represented by the general formula (I) is a compound in which R is a straight-chain alkyl group having 2 to 4 carbon atoms which is substituted with 3 to 7 fluorine atoms, X.sup.1 is a chlorine or a methyl group, X.sup.2 is a hydrogen; and Z represents a nitro group or an amino group.
More specifically, a preferred compound is exemplified by the following compounds:
Illustrative examples of the compounds of formula (II) and their physicochemical properties are shown in Table 1. The results of elemental analysis of these compounds are shown in Table 2.
The physicochemical properties of the formula (I) according to the present invention are shown in Table 3 and Table 4. By the way, these intermediates are the novel compounds.
Table 3 shows the physicochemical properties of the derivative of nitrobenzyl ether (III). ##STR29## wherein, R, X.sup.1 and X.sup.2 are as defined in formula (I).
Table 4 shows the physicochemical properties of the derivative of aniline (IV). ##STR39## wherein, R, X.sup.1 and X.sup.2 are as defined in formula (I).
All of compounds of formula (II) have the selective herbicidal activities described above and are therefore widely applicable as active ingredient for a herbicidal composition used in a paddy field and a crop field.
The compounds of formula (II) can be prepared from a process according to the following Reaction Scheme. 1. ##STR49## wherein R, X.sup.1, X.sup.2, Y.sup.1 and Y.sup.2 are as defined above.
A derivative of 2-phenyl-4-(phenylhydrazono)-2-oxazolin-5-one represented by the formula (V) is reacted with ammonia in an organic solvent such as acetone or toluene at a temperature of -10.degree. to 150.degree. C. for 0.1 to 20 hours. The resulting reaction mixture is acidified to pH 1-3 with hydrochloric acid, acetic acid or the like and then stirred at 0.degree. to 150.degree. C. for 0.1 to 20 hours to effect dehydration-cyclization. The process gives the compounds of formula (II) in a high yield.
The compound of formula (V) can be synthesized, for example, by a process according to the following Reaction Scheme 2. ##STR50## wherein R, X.sup.1, X.sup.2, Y.sup.1 and Y.sup.2 are as defined above.
A derivative of chloromethylnitrobenzene (VI) is etherified by, for example, reacting it with ROH in dimethylformamide or hexamethylphosphoramide in the presence of a hydrogen chloride acceptor such as KOH or NaH at a temperature of -10.degree. to 150.degree. C., preferably 0.degree. to 80.degree. C., for 0.1 to 20 hours, preferably 0.5 to 10 hours, to synthesize a derivative of nitrobenzyl ether (III) according to the present invention. This derivative of nitrobenzyl ether (III) is then reduced by a conventional method, for example, by adding thereto hydrazine hydrate in an alcohol solution thereof and heating the mixture under reflux in the presence of palladium-charcoal for 1 to 10 hours to obtain a derivative of aniline (IV) according to the present invention. Other reducing methods are also usable here, such as a method in which the derivative of nitrobenzyl ether (III) is reduced by using iron, zinc or tin in a solvent such as hydrochloric acid or acetic acid; a method where the derivative (III) is reduced by using colloidal sulfur or sodium sulfide in ethanol or hydrous ethanol; a method where the derivative (III) is reduced by the action of hydrazine in ethanol in the presence of ferric salt and active carbon; and a method in which the derivative (III) is catalytically reduced by hydrogen gas of ordinary pressure to 5 atom in a solvent such as ethanol or acetic acid in the presence of a catalyst such as Raney nickel, palladium carbon or platinum oxide.
Furthermore, a derivative of aniline (IV) can be prepared by catalytic reduction of a derivative of nitrobenzyl ether (III) in the presence of platinum or palladium catalyst poisoned by sulfur, morpholine or phosphorus compounds, too.
Then the derivative of aniline (IV) is converted into a diazonium salt (VII) by, for instance, using sodium nitrite in hydrochloric acid at a temperature of -10.degree. to 15.degree. C.
Separately, a derivative of 2-phenyl-2-oxazolin-5-one (IX) is synthesized by subjecting a derivative of hippuric acid (VIII) to dehydrating-cyclization in acetic anhydride at a temperature of 20.degree. to 100.degree. C., preferably 50.degree. to 90.degree. C., for 0.1 to 30 hours, preferably 0.1 to 3 hours. Then the diazonium salt (VII) is reacted with the derivative of 2-phenyl-2-oxazolin-5-one (IX) at a temperature of -50.degree. to 100.degree. C., preferably -30.degree. to 40.degree. C., for 0.01 to 20 hours, preferably 0.1 to 10 hours to obtain the compound represented by the formula (V).
The 1,5-diphenyl-1H-1,2,4-triazole-3-carboxamide derivatives can be used alone or in the various forms of composition such as wettable powder, emulsion, granules, powder, etc., with various types of carrier (diluent) and/or adjuvant commonly used in the preparation of agricultural chemicals.
The concentration of 1,5-diphenyl-1H-1,2,4-triazole-3-carboxamide derivative of the present invention in the compositions is preferably in the range of 0.1 to 50% by weight.
The 1,5-diphenyl-1H-1,2,4-triazole-3-carboxamide derivatives and the herbicidal composition containing such compounds as active ingredient are sprayed or spreaded on the soil of the field and/or the stalks and leaves of the plants by a known method so that the compound will be applied at a rate of preferably 0.1 to 500 g per 10 areas.
US Referenced Citations (11)
Foreign Referenced Citations (4)
| Number |
Date |
Country |
| 2412119 |
Sep 1974 |
DEX |
| 61-289066 |
Dec 1986 |
JPX |
| WO8704049 |
Jul 1987 |
WOX |
| 2120665B |
Dec 1983 |
GBX |
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| Entry |
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| STN International ACS No. 69885-62-7, p. 220, Mar. 27, 1992. |
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Divisions (1)
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Number |
Date |
Country |
| Parent |
162699 |
Mar 1988 |
|
Patent Grant
5162583
