Imidazoazines

• US 5,658,857 A
• Filed: 08/08/1995
• Issued: 08/19/1997
• Est. Priority Date: 02/15/1993
• Status: Expired due to Fees

• Current Assignee: Bayer AG
• Original Assignee: Bayer AG
• Inventors: Santel, Hans-Joachim, Dollinger, Markus, Andree, Roland
• Primary Examiner(s): DENTZ, BERNARD I
• Application Number:
  US08/500,993
• Time in Patent Office: 742 Days
• Field of Search: 546/121, 544/184, 544/236, 544/281, 544/350, 504/228, 504/236, 504/246
• US Class Current: 504/228
• CPC Class Codes: A01N 43/90 having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
• CPC Class Codes: C07D 471/04 Ortho-condensed systems

Abstract

The invention relates to new imidazoazines of the general formula (I) ##STR1## in which R¹, R², R³, R⁴, R⁵, R⁶, A, D, E and G have the meanings given in the description, to processes for their preparation, and to their use as herbicides.

Claims

1. An imidazoazine of the formula ##STR17## in which R¹ represents hydrogen, halogen, cyano, carboxyl, carbamoyl, nitro, alkyl, halogenoalkyl, alkoxy or halogenoalkoxy,

R² represents hydrogen, halogen, cyano, carboxyl, nitro, hydroxyl, mercapto, amino, carbamoyl, sulpho, sulphamoyl, chlorosulphonyl, or represents in each case optionally substituted alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy, alkinyloxy, alkylthio, alkenylthio, alkinylthio, alkylsulphinyl, alkylsulphonyl, alkylaminosulphonyl, dialkylaminosulphonyl, alkylamino, dialkylamino, alkenylamino, alkinylamino, alkylsulphonylamino, N-alkylalkylsulphonylamino, alkoxycarbonyl, alkoxyaminosulphonyl, N-alkyl-alkoxy-aminosulphonyl, arylsulphonylamino, arylalkylsulphonylamino, N-alkyl-arylsulphonylamino, N-alkyl-arylalkylsulphonylamino, arylaminosulphonyl, arylalkylaminosulphonyl, N-alkyl-arylaminosulphonyl or N-alkyl-arylalkylaminosulphonyl,

R³ represents hydrogen, halogen, cyano, carboxyl, amino, hydroxyl, carbamoyl, nitro, or represents in each case optionally substituted alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy, alkinyloxy, alkylthio, alkenylthio, alkinylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, alkenylamino, alkinylamino, alkylsulphonylamino or alkoxycarbonyl,

R⁴ represents hydrogen, halogen, cyano, alkyl or halogenoalkyl,

R⁵ represents hydrogen, halogen, cyano, alkyl or halogenoalkyl,

R⁶ represents halogen, cyano, nitro, amino, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino or dialkylamino,

A represents nitrogen or the group C--R⁷,

D represents nitrogen or the group C--R⁸,

E represents nitrogen .or the group C--R⁹ and

G represents nitrogen or the group C--R¹⁰,

where R⁷, R⁸, R⁹ and R¹⁰ are identical or different and in each case represent hydrogen, halogen, cyano, carboxyl, carbamoyl, nitro, or in each case optionally substituted alkyl, phenyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino or alkoxycarbonyl,

or an acid addition product thereof,

with the proviso that at least one of the radicals R¹ to R⁵ is other than hydrogen and that the following compounds are excepted by disclaimer:

3-Bromo-2-(4-methylsulphonyl-phenyl)-imidazo-[1,2-a]-pyridine, 3-bromo-2-(4-formyl-phenyl)-imidazo-[1,2-a]-pyridine, 3-bromo-2-(4-nitro-phenyl)-imidazo-[1,2-a]-pyridine, 3-chloro-2-(4-bromo-phenyl)-imidazo-[1,2-a]-pyridine, 3-chloro-2-(4-chloro-phenyl)-imidazo-[1,2-a]-pyridine, 3-chloro-2-(4-methoxy-phenyl)-imidazo-[1,2-a]-pyridine, 3-bromo-2-(4-bromo-phenyl)-imidazo-[1,2-a]-pyridine and 3-bromo-2-(4-methoxy-phenyl)-imidazo-[1,2-a]-pyridine.

2. An imidazoazine according to claim 1, characterized in that

R¹ represents hydrogen, fluorine, chlorine, bromine, cyano, carboxyl, carbamoyl, nitro, or represents alkyl or alkoxy, each of which has 1 to 4 carbon atoms and each of which is optionally substituted by fluorine or chlorine,

R² represents hydrogen, fluorine, chlorine, bromine, cyano, carboxyl, carbamoyl, nitro, hydroxyl, mercapto, amino, sulpho, sulphamoyl, chlorosulphonyl, or represents alkyl, alkoxy, alkylthio or alkylamino, each of which has 1 to 6 carbon atoms and each of which is optionally substituted by fluorine, chlorine, cyano, carboxyl, carbamoyl or C₁ -C₄ -alkoxy-carbonyl,

R² furthermore represents alkenyl, alkinyl, alkenyloxy, alkinyloxy, alkenylthio, alkinylthio, alkenylamino or alkinylamino, each of which has 3 to 6 carbon atoms and each of which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, carbamoyl or C₁ -C₄ -alkoxy-carbonyl,

R² furthermore represents alkylsulphinyl, alkylsulphonyl, alkylsulphonylamino, N-alkyl-alkylsulphonylamino, alkylaminosulphonyl, dialkylaminosulphonyl, alkoxyaminosulphonyl, N-alkyl-alkoxyaminosulphonyl, dialkylamino or alkoxycarbonyl, each of which has up to 6 carbon atoms in the alkyl groups and each of which is optionally substituted by fluorine or chlorine,

R² furthermore represents in each case optionally substituted phenylsulphonylamino, phenyl-C₁ -C₄ -alkylsulphonylamino, N--C₁ -C₄ -allcyl-phenylsulphonylamino, N--C₁ -C₄ -alkyl-phenyl-C₁ -C₄ -alkyl-sulphonylamino, phenylaminosulphonyl, phenyl-C₁ -C₄ -alkyl-aminosulphonyl, N--C₁ -C₄ -alkyl-phenylaminosulphonyl or N--C₁ -C₄ -alkyl-phenyl-C₁ -C₄ -alkyl-aminosulphonyl, it being possible for the phenyl groups in each case optionally to contain the following substituents:

fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxyl, amino, carboxyl, carbamoyl, and in each case optionally fluorine and/or chlorine-substituted C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl, C₁ -C₄ -alkylsulphonyl, C₁ -C₄ -alkoxycarbonyl or phenyl,

R³ represents hydrogen, fluorine, chlorine, bromine, cyano, carboxyl, amino, hydroxyl, carbamoyl, nitro, or represents alkyl, alkoxy, alkylthio or alkylamino, each of which has 1 to 6 carbon atoms and each of which is optionally substituted by fluorine, chlorine, cyano, carboxyl, carbamoyl or C₁ -C₄ -alkoxy-carbonyl,

R³ furthermore represents alkenyl, alkinyl, alkenyloxy, alkinyloxy, alkenylthio, alkinylthio, alkenylamino or alkinylamino, each of which has 3 to 6 carbon atoms and each of which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, carbamoyl or C₁ -C₄ -alkoxy-carbonyl, or represents alkylsulphinyl, alkylsulphonyl, alkylsulphonylamino or alkoxycarbonyl, each of which has up to 6 carbon atoms and each of which is optionally substituted by fluorine or chlorine,

R⁴ represents hydrogen, fluorine, chlorine, bromine, cyano, or represents alkyl having 1 to 6 carbon atoms which is optionally substituted by fluorine or chlorine,

R⁵ represents hydrogen, fluorine, chlorine, bromine, cyano, or represents alkyl having 1 to 4 carbon atoms which is optionally substituted by fluorine or chlorine,

R⁶ represents chlorine, bromine, iodine, cyano, nitro, amino, or represents alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino or dialkylamino, each of which has 1 to 6 carbon atoms in the alkyl groups,

A represents nitrogen or the group C--R⁷,

D represents nitrogen or the group C--R⁸,

E represents nitrogen or the group C--R⁹ and

G represents nitrogen or the group C--R¹⁰,

where R⁷, R⁸, R⁹ and R¹⁰ are identical or different and each of which represents hydrogen, fluorine, chlorine, bromine, cyano, carboxyl, carbamoyl, nitro, or in each case optionally fluorine- or chlorine-substituted alkyl, phenyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino or alkoxycarbonyl, the alkyl radicals in each case containing 1 to 6 carbon atoms, with the proviso that at least one of the radicals R¹ to R⁵ is other than hydrogen and with the exception of the compounds excluded in claim 1 by disclaimer, and

or an acid addition product thereof wherein said addition product is formed with a protonic acid.

3. An imidazoazine according to claim 1, characterized in that

R¹ represents hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl or trifluoromethyl,

R² represents hydrogen, fluorine, chlorine, bromine, cyano, carboxyl, carbamoyl, nitro, hydroxyl, mercapto, amino, sulpho, sulphamoyl, chlorosulphonyl, or represents methyl, ethyl, propyl, methoxy, ethoxy, propoxy, methylthio, ethylthio, propylthio, methylamino, ethylamino or propylamino, each of which is optionally substituted by fluorine, chlorine, cyano, carboxyl, carbamoyl, methoxycarbonyl or ethoxycarbonyl,

R² furthermore represents allyl, propargyl, allyloxy, propargyloxy, allylthio, propargylthio, dimethylamino, allylamino or propargylamino, each of which is optionally substituted by fluorine, chlorine, cyano, carboxyl, methoxycarbonyl or ethoxycarbonyl, or represents methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, methylsulphonylamino, ethylsulphonylamino, n- or i-propylsulphonylamino, methylaminosulphonyl, ethylaminosulphonyl, n- or i-propylaminosulphonyl, dimethylaminosulphonyl, diethylaminosulphonyl, dipropylaminosulphonyl, phenylsulphonylamino, tolylsulphonylamino, phenylaminosulphonyl, tolylaminosulphonyl, methoxycarbonyl or ethoxycarbonyl, each of which is optionally substituted by fluorine or chlorine,

R³ represents hydrogen, fluorine, chlorine, bromine, cyano, carboxyl, amino, hydroxyl, carbamoyl, nitro, or represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, propoxy, methylthio, ethylthio, propylthio, methylamino, ethylamino or propylamino, each of which is optionally substituted by fluorine, chlorine, cyano, carboxyl, carbamoyl, methoxycarbonyl or ethoxycarbonyl,

R³ furthermore represents allyl, propargyl, allyloxy, propargyloxy, allylthio, propargylthio, allylamino or propargylamino, each of which is optionally substituted by fluorine, chlorine, cyano, carboxyl, methoxycarbonyl or ethoxycarbonyl, or represents methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, methylsulphonylamino, ethylsulphonylamino, methoxycarbonyl or ethoxycarbonyl, each of which is optionally substituted by fluorine or chlorine,

R⁴ represents hydrogen, fluorine, chlorine, bromine, cyano, methyl, ethyl or trifluoromethyl,

R⁵ represents hydrogen, fluorine, chlorine, bromine, cyano, methyl, ethyl or trifluoromethyl,

R⁶ represents chlorine, bromine, cyano, nitro, amino, methoxy, ethoxy, methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, methylamino or dimethylamino,

A represents nitrogen or the group C--R⁷,

D represents nitrogen or the group C--R⁸,

E represents nitrogen or the group C--R⁹, and

G represents nitrogen or the group C--R¹⁰,

where R⁷, R⁸, R⁹ and R¹⁰ are identical or different and in each case represent hydrogen, fluorine, chlorine, bromine, cyano, carboxyl, carbamoyl, nitro, or in each case optionally fluorine- or chlorine-substituted methyl, ethyl, n- or i-propyl, phenyl, methoxy, ethoxy, methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, methylamino, ethylamino, dimethylamino, diethylamino, methoxycarbonyl or ethoxycarbonyl,

with the proviso that at least one of the radicals R¹ to R⁵ is other than hydrogen and with the exception of the compounds excluded in claim 1 by disclaimer, or an acid addition product wherein said product is formed with a hydrohalic acid.

4. An imidazoazine according to claim 1, characterized in that

A represents the group C--R⁷,

D represents the group C--R⁸,

E represents the group C--R⁹ and

G represents the group C--R¹⁰,

where R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ have the meanings mentioned in claim 1,

with the proviso that at least one of the radicals R¹ to R⁵ is other than hydrogen and with the exception of the compounds excluded in claim 1 by disclaimer.

5. An imidazoazine according to claim 3, characterized in that

A represents the group C--R⁷,

D represents the group C--R⁸,

E represents the group C--R⁹ and

G represents the group C--R¹⁰,

where R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ have the meanings mentioned in claim 1,

with the proviso that at least one of the radicals R¹ to R⁵ is other than hydrogen and with the exception of the compounds of excluded by disclaimer.

6. A process for the preparation of the imidazoazines of the formula ##STR18## in which R¹, R², R³, R⁴, R⁵, R⁶, A, D, E and G have the meanings given in claim 1,

where R⁷, R⁸, R⁹ and R¹⁰ are identical or different and in each case represent hydrogen, halogen, cyano, carboxyl, carbamoyl, nitro, or in each case optionally substituted alkyl, phenyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino or alkoxycarbonyl,

and acid addition products of the compounds of the formula (I),

with the proviso that at least one of the radicals R¹ to R⁵ is other than hydrogen and that the following compounds are excepted by disclaimer:

3-bromo-2-(4-methylsulphonyl-phenyl)-imidazo-[1,2-a]-pyridine, 3-bromo-2-(4-formyl-phenyl)-imidazo-[1,2-a]-pyridine, 3-bromo-2-(4-nitro-phenyl)-imidazo[1,2-a]-pyridine, 3-chloro-2-(4-bromo-phenyl)-imidazo-[1,2-a]-pyridine, 3-chloro-2-(4-chloro-phenyl)-imidazo-[1,2-a]-pyridine, 3-chloro-2-(4-methoxy-phenyl)-imidazo-[1,2-a]-pyridine, 3-bromo-2-(4-bromo-phenyl)-imidazo-[1,2-a]pyridine and 3-bromo-2-(4-methoxy-phenyl)-imidazo-[1,2-a]-pyridine,

characterized in that,

(a) in the event that, in formula (I), R⁶ represents halogen or nitro and R¹, R², R³, R⁴ and R⁵ as well as A, D, E and G have the abovementioned imidazoazines of the general formula (II) ##STR19## in which R¹, R², R³, R⁴, R⁵, A, D, E and G have the abovementioned meanings,

are reacted with halogenating agents or nitrating agents, if appropriate in the presence of inert diluents, or in that,

(b) in the event that, in formula (I), R⁶ represents amino, cyano, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino or dialkylamino and R¹, R², R³, R⁴, R⁵, A, D, E and G have the abovementioned meanings,

halogenated imidazoazines of the general formula (Ia) ##STR20## in which X represents halogen and

R¹, R², R³, R⁴, R⁵, A, D, E and G have the abovementioned meanings, are reacted with ammonia or with alkali metal cyanides or with alcohols, alkylmercaptans, alkylamines or dialkylamines or with their alkali metal salts, if appropriate in the presence of diluents, and, if appropriate--to prepare corresponding alkylsulphinyl or alkysulphonyl compounds--, the product is subsequently oxidized by customary methods, and when, if appropriate--to prepare acid addition products of the compounds of the formula (I)--, the compounds obtained in accordance with process (a) or (b) are reacted with acids by customary methods.

7. An imidazoazine according to claim 2 wherein the protonic acid is HCl, HBr, Hl, H₂ SO₄, methanesulphonic acid, benzenesulphonic acid, p-tolunesulphonic acid and napththalene-1,5-disulphonic acid.

8. An imidazoazine according to claim 3, wherein the hydrohalic acid is HCl or HBr.

9. A herbicidal composition which comprises an effective amount of an imidazoazine according to claim 1 and an inert carrier.

10. A method of combatting undesired plants which comprises applying to said plants or to their environment an effective amount of a compound according to claim 1.

11. A compound according to claim 1, wherein the compound is ##STR21##