Patent Application: US-79375005-A

Abstract:
objects of the present invention are the compounds of formula i their pharmaceutically acceptable salts , enantiomeric forms , diastereoisomers and racemates , the preparation of the above - mentioned compounds , medicaments containing them and their manufacture , as well as the use of the above - mentioned compounds in the control or prevention of illnesses such as cancer .

Description:
as used herein , the term “ alkyl ” means a saturated , straight - chain or branched - chain hydrocarbon containing from 1 to 4 , preferably 1 or 2 , carbon atoms , such as methyl , ethyl , n - propyl , isopropyl , n - butyl , 2 - butyl , t - butyl . as used herein , the term “ alkoxy ” means an alkyl group as defined above which is connected via an oxygen (— o —) atom . as used herein , the term “ alkylsulfonyl ” means an alkyl group as defined above which is connected via — s ( o ) 2 —. as used herein , the term “ acyl ” means an alkyl group as defined above which is connected via a carbonyl (— c ( o )—) group . if said alkyl group is substituted one or several times by halogen , it is preferably substituted by fluorine or chlorine , especially by fluorine . examples are difluoromethyl , trifluoromethyl , 2 , 2 , 2 - trifluoroethyl , perfluorethyl and the like . the term “ halogenated alkyl ” as used herein means an alkyl group as defined above which is substituted one or several times by halogen , preferably by fluorine or chlorine , especially fluorine . examples are difluoromethyl , trifluoromethyl , 2 , 2 , 2 - trifluoroethyl , 2 , 2 , 2 - trifluoro - 1 - methyl - ethyl , perfluorethyl , and the like , preferably trifluoromethyl and 2 , 2 , 2 - trifluoro - 1 - methyl - ethyl , especially 2 , 2 , 2 - trifluoro - 1 - methyl - ethyl or especially trifluoromethyl . the term “ halogenated alkoxy ” as used herein means an alkoxy group as defined above which is substituted one or several times by halogen , preferably by fluorine or chlorine , especially fluorine . examples are difluoromethoxy , trifluoromethoxy , 2 , 2 , 2 - trifluoroethoxy , perfluoroethoxy and the like , especially trifluoromethoxy . the term “ halogen ” as used herein means fluorine , chlorine , bromine and iodine , preferably fluorine , chlorine or bromine and more preferred fluorine and chlorine . the term “ phenylalkyl ” as used herein means an alkyl group as defined above , in which one of the hydrogen atoms is replaced by a phenyl group . examples of phenylalkyl groups are benzyl , 1 - phenylethyl , 2 - phenylethyl , 3 - phenylpropyl and the like , preferably benzyl and 1 - phenylethyl . the term “ heteroaryl ” means a mono - or bicyclic aromatic ring selected from pyridyl , thienyl , benzimidazolyl , pyrimidyl , thiazolyl , quinolyl , pyridazinyl , pyrazinyl , oxazolyl , quinazolinyl , indolyl , benzothiophenyl or benzofuranyl , especially from pyridyl , thienyl , benzimidazolyl , pyrimidyl , thiazolyl , quinolyl or pyridazinyl , and more preferred from pyridyl , thienyl or benzimidazolyl . the term “ cycloalkyl ” means a monocyclic saturated hydrocarbon ring with 3 to 7 , preferably 4 to 6 and more preferably 5 to 6 , ring atoms . examples of such saturated carbocyclic groups are cyclopropyl , cyclobutyl , cyclopentyl , cyclohexyl and cycloheptyl , preferably cyclopropyl , cyclopentyl and cyclohexyl . in the definition of r 1 , — y - cycloalkyl is preferably — y - cyclopropyl . in the definition of r 2 , cycloalkyl is preferably cyclopropyl , cyclobutyl , cyclopentyl or cyclohexyl ; more preferably cyclopropyl , cyclopentyl or cyclohexyl and still more preferably cyclobutyl , cyclopentyl or cyclohexyl . the term “ heterocyclyl ” means a saturated , monocyclic hydrocarbon ring with 5 to 6 ring atoms which contains up to 3 , preferably 1 or 2 heteroatoms selected independently from n , o or s and the remaining ring atoms being carbon atoms . such saturated heterocyclic group can be optionally substituted one to three times , preferably one or two times by ( c 1 - c 4 ) alkyl or ( c 1 - c 4 ) acyl , which are defined as above , preferably by methyl or acetyl . examples of such saturated heterocyclic groups are pyrrolidinyl , morpholinyl , piperazinyl , n - methyl - piperazinyl , piperidyl or n - acetyl - piperidyl and the like , preferably morpholinyl , n - methyl - piperazinyl or n - acetyl - piperidyl , more preferably morpholinyl , n - methyl - piperazinyl and still more preferably morpholinyl . if r 1 is phenyl , said phenyl is optionally substituted one or several times , preferably one or two times , at the ortho , meta or para position . if r 1 is heteroaryl , said heteroaryl is optionally substituted one or several times , preferably one or two times . the compounds of formula i can exist in different tautomeric forms and in variable mixtures thereof . all tautomeric forms of the compounds of formula i and mixtures thereof are an objective of the invention . for example , if a in the definition of formula is ═ n —, the imidazole part of pyridyl - imidazole ring system of formula i can exist in two tautomeric forms as shown here below : an embodiment of the invention are the compounds according to formula i , wherein another embodiment of the invention are the compounds according to formula i , wherein another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with halogen , cyano , nitro , amino , — c ( o ) oh , heterocyclyl , — o - heterocyclyl , — s ( o ) 2 nh 2 , — x - alkyl or — y - cycloalkyl ; wherein the alkyl group is optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfonyl . another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with halogen , cyano , nitro , amino , — c ( o ) oh , heterocyclyl , — o - heterocyclyl , — s ( o ) 2 nh 2 , — x - alkyl or — y - cycloalkyl ; wherein the alkyl group is optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; and another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with halogen , cyano , nitro , amino , — c ( o ) oh , heterocyclyl , — o - heterocyclyl , — s ( o ) 2 nh 2 , — x - alkyl or — y - cycloalkyl ; wherein the alkyl group is optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; and another embodiment of the invention are the compounds according to formula i , wherein r 1 is a heteroaryl group optionally substituted with halogen , nitro , amino , heterocyclyl or - z - alkyl ; wherein the alkyl group is optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl . another embodiment of the invention are the compounds according to formula i , wherein r 1 is a heteroaryl group optionally substituted with halogen , nitro , amino , heterocyclyl or - z - alkyl ; wherein the alkyl group is optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; and another embodiment of the invention are the compounds according to formula i , wherein r 1 is a heteroaryl group optionally substituted with halogen , nitro , amino , heterocyclyl or - z - alkyl ; wherein the alkyl group is optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; and another embodiment of the invention are the compounds according to formula i , wherein an embodiment of the invention are the compounds according to formula i , wherein r 2 is alkyl , halogenated alkyl , alkenyl , alkynyl or cycloalkyl ; and a is ═ n —. another embodiment of the invention are the compounds according to formula i , wherein r 2 is alkyl , halogenated alkyl , alkenyl , alkynyl or cycloalkyl ; and a is ═ ch —. another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with halogen , cyano , nitro , amino , — c ( o ) oh , heterocyclyl , — o - heterocyclyl , — s ( o ) 2 nh 2 , — x - alkyl or — y - cycloalkyl ; wherein the alkyl group is optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; and another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with halogen , cyano , nitro , amino , — c ( o ) oh , heterocyclyl , — o - heterocyclyl , — s ( o ) 2 nh 2 , — x - alkyl or — y - cycloalkyl ; wherein the alkyl group is optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; r 2 is alkyl , halogenated alkyl , alkenyl , alkynyl or cycloalkyl ; and a is ═ n —. another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with halogen , cyano , nitro , amino , — c ( o ) oh , heterocyclyl , — o - heterocyclyl , — s ( o ) 2 nh 2 , — x - alkyl or — y - cycloalkyl ; wherein the alkyl group is optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; r 2 is alkyl , halogenated alkyl , alkenyl , alkynyl or cycloalkyl ; and a is ═ ch —. another embodiment of the invention are the compounds according to formula i , wherein r 1 is a heteroaryl group optionally substituted with halogen , nitro , amino , heterocyclyl or - z - alkyl ; wherein the alkyl group is optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; and another embodiment of the invention are the compounds according to formula i , wherein r 1 is a heteroaryl group optionally substituted with halogen , nitro , amino , heterocyclyl or - z - alkyl ; wherein the alkyl group is optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; r 2 is alkyl , halogenated alkyl , alkenyl , alkynyl or cycloalkyl ; and a is ═ n —. another embodiment of the invention are the compounds according to formula i , wherein r 1 is a heteroaryl group optionally substituted with halogen , nitro , amino , heterocyclyl or - z - alkyl ; wherein the alkyl group is optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; r 2 is alkyl , halogenated alkyl , alkenyl , alkynyl or cycloalkyl ; and a is ═ ch —. another embodiment of the invention are the compounds according to formula i , wherein wherein the phenyl group is optionally substituted one or several times by halogen , alkyl , alkoxy , halogenated alkyl , halogenated alkoxy or cyano . an embodiment of the invention are the compounds according to formula i , wherein wherein the phenyl group is optionally substituted one or several times by halogen , alkyl , alkoxy , halogenated alkyl , halogenated alkoxy or cyano ; and another embodiment of the invention are the compounds according to formula i , wherein wherein the phenyl group is optionally substituted one or several times by halogen , alkyl , alkoxy , halogenated alkyl , halogenated alkoxy or cyano ; and another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with halogen , cyano , nitro , amino , — c ( o ) oh , heterocyclyl , — o - heterocyclyl , — s ( o ) 2 nh 2 , — x - alkyl or — y - cycloalkyl ; wherein the alkyl group is optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; and wherein the phenyl group is optionally substituted one or several times by halogen , alkyl , alkoxy , halogenated alkyl , halogenated alkoxy or cyano . another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with halogen , cyano , nitro , amino , — c ( o ) oh , heterocyclyl , — o - heterocyclyl , — s ( o ) 2 nh 2 , — x - alkyl or — y - cycloalkyl ; wherein the alkyl group is optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; wherein the phenyl group is optionally substituted one or several times by halogen , alkyl , alkoxy , halogenated alkyl , halogenated alkoxy or cyano ; and another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with halogen , cyano , nitro , amino , — c ( o ) oh , heterocyclyl , — o - heterocyclyl , — s ( o ) 2 nh 2 , — x - alkyl or — y - cycloalkyl ; wherein the alkyl group is optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; wherein the phenyl group is optionally substituted one or several times by halogen , alkyl , alkoxy , halogenated alkyl , halogenated alkoxy or cyano ; and another embodiment of the invention are the compounds according to formula i , wherein r 1 is a heteroaryl group optionally substituted with halogen , nitro , amino , heterocyclyl or - z - alkyl ; wherein the alkyl group is optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; and wherein the phenyl group is optionally substituted one or several times by halogen , alkyl , alkoxy , halogenated alkyl , halogenated alkoxy or cyano . another embodiment of the invention are the compounds according to formula i , wherein r 1 is a heteroaryl group optionally substituted with halogen , nitro , amino , heterocyclyl or - z - alkyl ; wherein the alkyl group is optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; wherein the phenyl group is optionally substituted one or several times by halogen , alkyl , alkoxy , halogenated alkyl , halogenated alkoxy or cyano ; and another embodiment of the invention are the compounds according to formula i , wherein r 1 is a heteroaryl group optionally substituted with halogen , nitro , amino , heterocyclyl or - z - alkyl ; wherein the alkyl group is optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; wherein the phenyl group is optionally substituted one or several times by halogen , alkyl , alkoxy , halogenated alkyl , halogenated alkoxy or cyano ; and another embodiment of the invention are the compounds according to formula i , wherein another embodiment of the invention are the compounds according to formula i , wherein another embodiment of the invention are the compounds according to formula i , wherein another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group ; and r 2 is alkyl or halogenated alkyl ; and a is ═ n —. such compounds , for example , may be selected from the group consisting of : ( 2 - phenyl - 1h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid isopropyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid isobutyl ester ; ( 2 - phenyl - 1h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid propyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid tert - butyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid 2 , 2 - dimethyl - propyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid 1 - ethyl - propyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid sec - butyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid ethyl ester ; and ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid 2 , 2 , 2 - trifluoro - 1 - methyl - ethyl ester . another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group ; and r 2 is alkyl or halogenated alkyl ; and a is ═ ch —. such compounds , for example , may be selected from the group consisting of : another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group ; and r 2 is alkenyl or alkynyl ; and a is ═ n —. such compounds , for example , may be selected from the group consisting of : another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group ; and r 2 is alkenyl or alkynyl ; and a is ═ ch —. such compounds , for example , may be selected from the group consisting of : another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group ; and r 2 is cycloalkyl ; and a is ═ n —. such compounds , for example , may be selected from the group consisting of : another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group ; and r 2 is cycloalkyl ; and a is ═ ch —. another embodiment of the invention are the compounds according to formula i , wherein wherein the phenyl group is optionally substituted one or several times by halogen , alkyl , alkoxy , halogenated alkyl , halogenated alkoxy or cyano ; and another embodiment of the invention are the compounds according to formula i , wherein wherein the phenyl group is optionally substituted one or several times by halogen , alkyl , alkoxy , halogenated alkyl , halogenated alkoxy or cyano ; and another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group substituted with halogen , cyano , nitro , amino , — c ( o ) oh or — s ( o ) 2 nh 2 another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group substituted with halogen , cyano , nitro , amino , — c ( o ) oh or — s ( o ) 2 nh 2 ; and a is ═ n —. another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group substituted with halogen , cyano , nitro , amino , — c ( o ) oh or — s ( o ) 2 nh 2 ; and a is ═ ch —. another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group substituted with halogen , cyano , nitro , amino , — c ( o ) oh or — s ( o ) 2 nh 2 ; r 2 is alkyl ; and a is ═ n —. such compounds , for example , may be selected from the group consisting of : [ 2 -( 4 - sulfamoyl - phenyl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; [ 2 -( 4 - nitro - phenyl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; [ 2 -( 4 - amino - phenyl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; [ 2 -( 3 - nitro - phenyl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; and [ 2 -( 3 - amino - phenyl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester . another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group substituted with halogen , cyano , nitro , amino , — c ( o ) oh or — s ( o ) 2 nh 2 ; r 2 is alkyl ; and a is ═ ch —. another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group substituted with halogen , cyano , nitro , amino , — c ( o ) oh or — s ( o ) 2 nh 2 ; and r 2 is alkyl . another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group substituted with heterocyclyl or — o - heterocyclyl . another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group substituted with heterocyclyl or — o - heterocyclyl ; and a is ═ n —. another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group substituted with heterocyclyl or — o - heterocyclyl ; and a is ═ ch —. another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group substituted with heterocyclyl or — o - heterocyclyl ; r 2 is alkyl ; and a is ═ n —. another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group substituted with heterocyclyl or — o - heterocyclyl ; r 2 is alkyl ; and a is ═ ch —. another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group substituted with heterocyclyl or — o - heterocyclyl ; and r 2 is alkyl . another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with — x - alkyl ; wherein the alkyl group are optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfonyl . another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with — x - alkyl ; wherein the alkyl group are optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; and another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with — x - alkyl ; wherein the alkyl group are optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; and another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with — x - alkyl ; wherein the alkyl group are optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; and another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with — x - alkyl ; wherein the alkyl group are optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; x is a single bond , — nr —, — o — or — s —; r 2 is alkyl ; and a is ═ n —. such compounds , for example , may be selected from the group consisting of : { 2 -[ 4 -( 2 - methoxy - ethoxy )- phenyl ]- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl }- carbamic acid isopropyl ester ; { 2 -[ 3 -( 2 - methoxy - ethoxy )- phenyl ]- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl }- carbamic acid isopropyl ester ; { 2 -[ 4 -( 2 - diethylamino - ethoxy )- phenyl ]- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl }- carbamic acid isopropyl ester ; { 2 -[ 4 -( 2 - diethylamino - ethoxy )- phenyl ]- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl }- carbamic acid isopropyl ester ; acetic acid salt ; [ 2 -( 4 - methylsulfanyl - phenyl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; and [ 2 -( 3 - methylsulfanyl - phenyl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester . another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with — x - alkyl ; wherein the alkyl group are optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; x is a single bond , — nr —, — o — or — s —; r 2 is alkyl ; and a is ═ ch —. such compounds , for example , may be selected from the group consisting of : another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with — x - alkyl ; wherein the alkyl group are optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; x is — nrc ( o )—, — c ( o ) nr —, — ch 2 — s ( o ) 2 nh —, — s ( o ) 2 nh —, — nhs ( o ) 2 —, — s ( o ) 2 — or — s ( o )—; r 2 is alkyl ; and a is ═ n —. such compounds , for example , may be selected from the group consisting of : another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with — x - alkyl ; wherein the alkyl group are optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; x is — nrc ( o )—, — c ( o ) nr —, — ch 2 — s ( o ) 2 nh —, — s ( o ) 2 nh —, — nhs ( o ) 2 —, — s ( o ) 2 — or — s ( o )—; r 2 is alkyl ; and a is ═ ch —. such compounds , for example , may be selected from the group consisting of : [ 2 -( 3 - acetylamino - phenyl )- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl ]- carbamic acid 2 , 2 - dimethyl - propyl ester ; [ 2 -( 4 - acetylamino - phenyl )- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl ]- carbamic acid 2 , 2 - dimethyl - propyl ester ; [ 2 -( 3 - acetylamino - phenyl )- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl ]- carbamic acid ethyl ester ; [ 2 -( 3 - acetylamino - phenyl )- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl ]- carbamic acid isopropyl ester ; and [ 2 -( 3 - acetylamino - phenyl )- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl ]- carbamic acid isobutyl ester . another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with — x - alkyl ; wherein the alkyl group are optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; x is a single bond , — nr —, — o — or — s —; r 2 is alkenyl ; and a is ═ ch —. another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with — x - alkyl ; wherein the alkyl group are optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; x is — nrc ( o )—, — c ( o ) nr —, — ch 2 — s ( o ) 2 nh —, — s ( o ) 2 nh —, — nhs ( o ) 2 —, — s ( o ) 2 — or — s ( o )—; r 2 is alkenyl ; and a is ═ ch —. such compounds , for example , may be selected from the group consisting of : another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with — x - alkyl ; wherein the alkyl group are optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; x is a single bond , — nr —, — o — or — s —; r 2 is phenylalkyl , wherein the phenyl group is optionally substituted one or several times by halogen , alkyl , alkoxy , halogenated alkyl , halogenated alkoxy or cyano ; and such compounds , for example , may be selected from the group consisting of : another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with — x - alkyl ; wherein the alkyl group are optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl ; x is — nrc ( o )—, — c ( o ) nr —, — ch 2 — s ( o ) 2 nh —, — s ( o ) 2 nh —, nhs ( o ) 2 —, — s ( o ) 2 — or — s ( o )—; r 2 is phenylalkyl , wherein the phenyl group is optionally substituted one or several times by halogen , alkyl , alkoxy , halogenated alkyl , halogenated alkoxy or cyano ; and such compounds , for example , may be selected from the group consisting of : another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with — y - cycloalkyl . another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with — y - cycloalkyl ; and a is ═ n —. another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with — y - cycloalkyl ; and a is ═ ch —. another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with — y - cycloalkyl ; r 2 is alkyl . another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with — y - cycloalkyl ; r 2 is alkyl ; and a is ═ n —. another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted with — y - cycloalkyl ; r 2 is alkyl ; and a is ═ ch —. another embodiment of the invention are the compounds according to formula i , wherein r 1 is a pyridyl , thienyl or benzimidazolyl group optionally substituted with halogen , nitro , amino , heterocyclyl or - z - alkyl ; wherein the alkyl group is optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfanyl . another embodiment of the invention are the compounds according to formula i , wherein r 1 is a pyridyl , thienyl or benzimidazolyl group optionally substituted with halogen , nitro , amino , heterocyclyl or - z - alkyl ; wherein the alkyl group is optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfonyl ; and another embodiment of the invention are the compounds according to formula i , wherein r 1 is a pyridyl , thienyl or benzimidazolyl group optionally substituted with halogen , nitro , amino , heterocyclyl or - z - alkyl ; wherein the alkyl group is optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfonyl ; and another embodiment of the invention are the compounds according to formula i , wherein r 1 is a pyridyl group optionally substituted with halogen , nitro , amino , heterocyclyl or - z - alkyl ; wherein the alkyl group is optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfonyl ; and another embodiment of the invention are the compounds according to formula i , wherein r 1 is a pyridyl group optionally substituted with halogen , nitro , amino , heterocyclyl or - z - alkyl ; wherein the alkyl group is optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfonyl ; and such compounds , for example , may be selected from the group consisting of : another embodiment of the invention are the compounds according to formula i , wherein r 1 is a pyridyl group optionally substituted with halogen , nitro , amino , heterocyclyl or - z - alkyl ; wherein the alkyl group is optionally substituted one or several times by halogen , hydroxy , alkoxy , amino , alkylamino , dialkylamino or alkylsulfonyl ; another embodiment of the invention are the compounds according to formula i , wherein r 1 is a thienyl or benzimidazolyl group optionally substituted with - z - alkyl ; z is a single bond ; and r 2 is alkyl . another embodiment of the invention are the compounds according to formula i , wherein r 1 is a thienyl or benzimidazolyl group optionally substituted with - z - alkyl ; z is a single bond ; r 2 is alkyl ; and a is ═ n —. such compounds , for example , may be selected from the group consisting of : [ 2 -( 1h - benzoimidazol - 5 - yl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; [ 2 -( 1h - benzoimidazol - 5 - yl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; acetic acid salt ; [ 2 -( 1h - benzoimidazol - 5 - yl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; hydrogen chloride salt ; ( 2 - thiophen - 2 - yl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid isopropyl ester ; and ( 2 - thiophen - 3 - yl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid isopropyl ester . another embodiment of the invention are the compounds according to formula i , wherein r 1 is a thienyl or benzimidazolyl group optionally substituted with - z - alkyl ; z is a single bond ; r 2 is alkyl ; and a is ═ ch —. another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted one to three , preferably one or two times with halogen , nitro , amino , — c ( o ) oh , heterocyclyl , — s ( o ) 2 nh 2 , — x - alkyl ; or a heteroaryl group optionally substituted one or two times with halogen , heterocyclyl or - z - alkyl ; and all alkyl groups are optionally substituted one or two times by hydroxy , alkoxy or dialkylamino ; x is — nr —, — o —, — s —, — nhs ( o ) 2 —, — s ( o ) 2 —, — s ( o )—, — nrc ( o )— or — c ( o ) nr —; z is a single bond or — nr —; r is hydrogen or alkyl , wherein the alkyl is optionally substituted one or two times by alkoxy ; and r 2 is alkyl , halogenated alkyl , alkenyl , alkynyl , cycloalkyl or phenylalkyl , wherein the phenyl group is optionally substituted one or two times by halogen . such compounds , for example , may be selected from the group consisting of : ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid 1 - methyl - prop - 2 - ynyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid 1 - methyl - but - 2 - ynyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid cyclobutyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid 1 , 3 - dimethyl - butyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid 1 , 2 - dimethyl - propyl ester ; { 2 -[ 3 -( 3 - methoxy - propionylamino )- phenyl ]- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl }- carbamic acid isopropyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid ( e )- 1 - methyl - but - 2 - enyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid 1 , 2 - dimethyl - allyl ester { 2 -[ 4 -( 4 - methyl - piperazin - 1 - yl )- phenyl ]- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl }- carbamic acid isopropyl ester ; { 2 -[ 3 -( 2 - hydroxy - ethyl )- phenyl ]- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl }- carbamic acid isopropyl ester ; [ 2 -( 6 - morpholin - 4 - yl - pyridin - 3 - yl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; [ 2 -( 4 - methanesulfonyl - phenyl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; [ 2 -( 4 - methanesulfinyl - phenyl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; [ 2 -( 3 - methylsulfonyl - phenyl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; [ 2 -( 3 , 4 - difluoro - phenyl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; ( 2 -{ 4 -[ bis -( 2 - methoxy - ethyl )- amino ]- 3 - fluoro - phenyl }- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid isopropyl ester ; 3 -( 6 - isopropoxycarbonylamino - 3h - imidazo [ 4 , 5 - b ] pyridin - 2 - yl )- benzoic acid ; { 2 -[ 3 -( 2 - methoxy - 1 - methoxymethyl - ethylcarbamoyl )- phenyl ]- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl }- carbamic acid isopropyl ester ; { 2 -[ 3 -( 3 - methoxy - propylcarbamoyl )- phenyl ]- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl }- carbamic acid isopropyl ester ; [ 2 -( 2 - chloro - pyridin - 4 - yl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; and { 2 -[ 2 -( 3 - methoxy - propylamino )- pyridin - 4 - yl ]- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl }- carbamic acid isopropyl ester . another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted one to three , preferably one or two times with — x - alkyl ; wherein the alkyl group is optionally substituted one or two times by alkoxy ; x is — o — or — nrc ( o )—; r is hydrogen ; r 2 is alkyl , alkenyl or phenylalkyl , wherein the phenyl group is optionally substituted one or two times by chlorine ; and a is ═ ch —. such compounds , for example , may be selected from the group consisting of : ( 2 - phenyl - th - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl )- carbamic acid isopropyl ester ; { 2 -[ 3 -( 2 - methoxy - ethoxy )- phenyl ]- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl }- carbamic acid isopropyl ester ; ( 2 - phenyl - 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl )- carbamic acid 2 , 2 - dimethyl - propyl ester ; { 2 -[ 4 -( 2 - methoxy - ethoxy )- phenyl ]- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl }- carbamic acid ethyl ester ; { 2 -[ 4 -( 2 - methoxy - ethoxy )- phenyl ]- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl }- carbamic acid allyl ester ; { 2 -[ 3 -( 2 - methoxy - ethoxy )- phenyl ]- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl }- carbamic acid ethyl ester ; { 2 -[ 3 -( 2 - methoxy - ethoxy )- phenyl ]- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl }- carbamic acid allyl ester ; ( 2 - phenyl - 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl )- carbamic acid benzyl ester ; { 2 -[ 3 -( 2 - methoxy - ethoxy )- phenyl ]- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl }- carbamic acid isobutyl ester ; { 2 -[ 3 -( 2 - methoxy - ethoxy )- phenyl ]- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl }- carbamic acid 2 - chloro - benzyl ester ; ( 2 - phenyl - 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl )- carbamic acid ethyl ester ; ( 2 - phenyl - 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl )- carbamic acid 2 - chloro - benzyl ester ; ( 2 - phenyl - 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl )- carbamic acid allyl ester ; ( 2 - phenyl - 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl )- carbamic acid isobutyl ester ; { 2 -[ 3 -( 2 - methoxy - ethoxy )- phenyl ]- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl }- carbamic acid 2 , 2 - dimethyl - propyl ester ; { 2 -[ 3 -( 2 - methoxy - ethoxy )- phenyl ]- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl }- carbamic acid benzyl ester ; { 2 -[ 4 -( 2 - methoxy - ethoxy )- phenyl ]- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl }- carbamic acid isopropyl ester ; { 2 -[ 4 -( 2 - methoxy - ethoxy )- phenyl ]- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl }- carbamic acid benzyl ester ; { 2 -[ 4 -( 2 - methoxy - ethoxy )- phenyl ]- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl }- carbamic acid isobutyl ester ; [ 2 -( 3 - acetylamino - phenyl )- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl ]- carbamic acid isopropyl ester ; [ 2 -( 4 - acetylamino - phenyl )- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl ]- carbamic acid allyl ester ; [ 2 -( 3 - acetylamino - phenyl )- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl ]- carbamic acid 2 - chloro - benzyl ester ; [ 2 -( 3 - acetylamino - phenyl )- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl ]- carbamic acid benzyl ester ; [ 2 -( 3 - acetylamino - phenyl )- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl ]- carbamic acid 2 , 2 - dimethyl - propyl ester ; [ 2 -( 4 - acetylamino - phenyl )- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl ]- carbamic acid 2 , 2 - dimethyl - propyl ester ; [ 2 -( 3 - acetylamino - phenyl )- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl ]- carbamic acid ethyl ester ; [ 2 -( 3 - acetylamino - phenyl )- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl ]- carbamic acid allyl ester ; and [ 2 -( 3 - acetylamino - phenyl )- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl ]- carbamic acid isobutyl ester . another embodiment of the invention are the compounds according to formula i , wherein r 1 is a phenyl group optionally substituted one to three , preferably one or two times with fluorine , nitro , amino , — c ( o ) oh , heterocyclyl , — s ( o ) 2 nh 2 , — x - alkyl ; wherein the alkyl group is optionally substituted one or two times by hydroxy , alkoxy or dialkylamino ; x is — nr —, — o —, — s —, — nhs ( o ) 2 —, — s ( o ) 2 —, — s ( o )—, — nrc ( o )— or — c ( o ) nr —; r is hydrogen or alkyl , wherein the alkyl is optionally substituted one or two times by alkoxy ; r 2 is alkyl , halogenated alkyl , alkenyl , alkynyl , cycloalkyl or phenylalkyl , wherein the phenyl group is optionally substituted one or two times by halogen ; and a is ═ n —. such compounds , for example , may be selected from the group consisting of : ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid 1 - methyl - allyl ester ; ( 2 - phenyl - 1h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid isopropyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid cyclohexyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid isobutyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid allyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid tert - butyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid cyclopentyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid ethyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid sec - butyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid 1 - ethyl - propyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid 2 , 2 , 2 - trifluoro - 1 - methyl - ethyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid 2 , 2 - dimethyl - propyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid 1 - phenyl - ethyl ester ; ( 2 - phenyl - 1h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid propyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid 1 - methyl - prop - 2 - ynyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid 1 - methyl - but - 2 - ynyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid cyclobutyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid 1 , 3 - dimethyl - butyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid 1 , 2 - dimethyl - propyl ester ; { 2 -[ 3 -( 3 - methoxy - propionylamino )- phenyl ]- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl }- carbamic acid isopropyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid ( e )- 1 - methyl - but - 2 - enyl ester ; ( 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid 1 , 2 - dimethyl - allyl ester ; { 2 -[ 4 -( 2 - diethylamino - ethoxy )- phenyl ]- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl }- carbamic acid isopropyl ester ; { 2 -[ 3 -( 2 - methoxy - ethoxy )- phenyl ]- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl }- carbamic acid isopropyl ester ; { 2 -[ 4 -( 2 - methoxy - ethoxy )- phenyl ]- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl }- carbamic acid isopropyl ester ; [ 2 -( 3 - nitro - phenyl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester [ 2 -( 4 - morpholin - 4 - yl - phenyl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; { 2 -[ 4 -( 4 - methyl - piperazin - 1 - yl )- phenyl ]- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl }- carbamic acid isopropyl ester ; { 2 -[ 3 -( 2 - hydroxy - ethyl )- phenyl ]- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl }- carbamic acid isopropyl ester ; [ 2 -( 4 - nitro - phenyl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; [ 2 -( 4 - sulfamoyl - phenyl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; [ 2 -( 4 - methylsulfanyl - phenyl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; [ 2 -( 3 - amino - phenyl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; [ 2 -( 4 - amino - phenyl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; [ 2 -( 3 - acetylamino - phenyl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; [ 2 -( 3 - methanesulfonylamino - phenyl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; [ 2 -( 3 - methylsulfinyl - phenyl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; [ 2 -( 3 - methylsulfonyl - phenyl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; [ 2 -( 4 - methanesulfonyl - phenyl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; [ 2 -( 4 - methanesulfinyl - phenyl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; [ 2 -( 3 , 4 - difluoro - phenyl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; ( 2 -{ 4 -[ bis -( 2 - methoxy - ethyl )- amino ]- 3 - fluoro - phenyl }- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid isopropyl ester ; 3 -( 6 - isopropoxycarbonylamino - 3h - imidazo [ 4 , 5 - b ] pyridin - 2 - yl )- benzoic acid ; { 2 -[ 3 -( 2 - methoxy - 1 - methoxymethyl - ethylcarbamoyl )- phenyl ]- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl }- carbamic acid isopropyl ester ; and { 2 -[ 3 -( 3 - methoxy - propylcarbamoyl )- phenyl ]- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl }- carbamic acid isopropyl ester . another embodiment of the invention are the compounds according to formula i , wherein r 1 is a heteroaryl group optionally substituted one or two times with chlorine , heterocyclyl or - z - alkyl ; and the alkyl groups are optionally substituted one or two times by alkoxy ; z is a single bond or — nr —; r is hydrogen ; r 2 is alkyl ; and a is ═ n —. such compounds , for example , may be selected from the group consisting of : ( 2 - thiophen - 2 - yl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid isopropyl ester ; ( 2 - thiophen - 3 - yl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid isopropyl ester ; [ 2 -( 2 - methyl - pyridin - 4 - yl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; [ 2 -( 6 - methyl - pyridin - 3 - yl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; [ 2 -( 1h - benzoimidazol - 5 - yl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; [ 2 -( 2 - chloro - pyridin - 4 - yl )- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- carbamic acid isopropyl ester ; and { 2 -[ 2 -( 3 - methoxy - propylamino )- pyridin - 4 - yl ]- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl }- carbamic acid isopropyl ester . still another embodiment of the invention is a process for the manufacture of the compounds of formula i , wherein wherein a and r 1 have the significance as given in formula i above , wherein r 2 has the significance given above for formula i , ( b ) said compound of formula i is isolated from the reaction mixture , and the derivatives of the general formula i or a pharmaceutically acceptable salt thereof , may be prepared by any process known to be applicable for the preparation of chemically - related compounds by the one skilled in the art . such processes , when used to prepare the derivatives of formula i , or a pharmaceutically - acceptable salt thereof , are provided as a further feature of the invention and are illustrated by the following representative examples of scheme 1 and 2 , in which , unless otherwise stated r 1 , r 2 and a have the significance given herein before for formula i . necessary starting materials may be obtained by standard procedures of organic chemistry . the preparation of such starting materials is described within the accompanying examples . alternatively necessary starting materials are obtainable by analogous procedures to those illustrated which are within the ordinary skill of an organic chemist . in scheme 1 , r 1 and r 2 have the significance as given above for formula i and y is bromine ( for the route via step 2a ) or nitro ( for the route via step 2b ). step 1a : condensation of an aromatic aldehyde with a 2 , 3 - diamino - pyridine derivative of formula iv can carried out at elevated temperatures from 60 to 200 ° c . in a suitable solvent like acetonitrile , nitrobenzene , n , n - dimethylformamide ( dmf ), dimethylsulfoxide ( dmso ), xylene , or methoxyethanol , optionally in the presence of an oxidizing agent like oxygen or an iron ( iii ) salt or sulfur , or 2 , 3 - dichloro - 5 , 6 - dicyano - p - benzoquinone ( ddq ). step 1b : the condensation with an aromatic carboxylic acid , or a suitable derivative thereof , with a 2 , 3 - diamino - pyridine derivative of formula iv can be achieved at temperatures in the range of 100 - 220 ° c . with a condensation reagent like polyphosphoric acid , pocl 3 , or p 4 o 10 , optionally in mixture with methane sulfonic acid . step 2a : in the compounds of formula v - a , wherein y is bromine , such bromine can be replaced by an amino group by heating in aqueous ammonia in the presence of a catalyst like cuso 4 or cui . a solubilizing co - solvent like n - methylpyrrolidone ( nmp ) or dimethyl acetamide can be added , and the reaction is carried out at temperatures of 100 - 180 ° c . in a closed vessel . alternatively , the amino functionality may be introduced in protected form as a tert .- butoxycarbonylamino substituent via coupling under standard hartwig / buchwald conditions ( for example , with a base like sodium tert . butoxide and a palladium catalyst like pd 2 ( dba ) 3 and a phosphine ligand like tri - tert . butyl phosphane ). step 2b : for the compounds of formula v - a , wherein y is nitro , the reduction of the nitro group is accomplished by standard conditions such as heterogeneous hydrogenation with pd on charcoal as the catalyst , in solvents like methanol , ethanol , tetrahydrofuran ( thf ), or ethyl acetate , at room temperature or up to 80 ° c . ; or by homogeneous hydrogenation with a pd catalyst and triethyl ammonium formate in a solvent like methanol at reflux conditions . the reduction can also be carried out with base metals like iron or tin in acidic media like acetic acid or aqueous hcl , from room temperature to 120 ° c . another suitable reductant would be ammonium sulfide in water or methanol , or tin ( ii ) chloride in dmf . step 3 : acylation of the amino moiety on the compounds of formula ii - a can be done with an appropriate chloroformate in an inert solvent like dichloromethane , toluene , tetrahydrofuran ( thf ), n - methylpyrrolidone ( nmp ), or dimethyl acetamide , or pyridine , optionally in the presence of a base like pyridine , triethyl amine , or di - isopropyl ethyl amine . suitable temperatures are in the range of − 20 ° c . to 100 ° c . if an excess of chloroformate is used , simultaneous acylation on the heterocyclic core can occur , e . g . on n - 1 or n - 3 . such a bis - acylated intermediate can be cleaved easily to the desired mono - acylated compound by subsequent treatment with ammonia in water or methanol at room temperature . in scheme 2 , r 1 and r 2 have the significance as given above for formula i . step 4 : an ethynyl - arene can be coupled with 3 - bromo - 5 - nitro - pyridin - 2 - ylamine under standard conditions of the so called sonogashira reaction , with a copper catalyst like cui or cucl , and a palladium catalyst like pdcl 2 ( pph 3 ) 2 or pdcl 2 ( phcn ) 2 / ptbu 3 , and a base like triethyl amine or di - isopropyl amine , in an inert solvent like tetrahydrofuran ( thf ), dioxane , n , n - dimethylformamide ( dmf ), or acetonitrile . the reaction proceeds at room temperature or higher , up to 160 ° c . alternatively , the ethynyl - arene may first be converted into a more reactive alkynyl - zn or — sn derivative by procedures known in the art : the ethynyl - arene is deprotonated with a strong base like butyl lithium to form an alkynyl - li intermediate which is reacted with zncl 2 or bu 3 sncl to yield the desired zinc or tin intermediate . these may subsequently be coupled to the bromopyridine under standard cross coupling conditions , for instance by catalysis by a palladium phosphine complex like pd ( pph 3 ) 4 or pdcl 2 ( pph 3 ) 2 or pd 2 ( dba ) 3 / ptbu 3 in solvents like dimethyl acetamide , thf , or toluene . step 5 : cyclisation of the alkyne intermediate to form a pyrrole ring can be achieved by treatment with a base like potassium tert . butoxide , potassium hydride , or sodium ethoxide in an inert solvent like nmp , thf , or dmf , or ethanol , at temperatures in the range from room temperature to reflux . alternatively , the base can be replaced by a catalyst like cui . step 6 and step 7 : these step are analogous to step 2b and step 3 under scheme 1 above . certain substituents on the group r 1 may not be inert to the conditions of the synthesis sequences described above and may require protection by standard protecting groups known in the art . for instance , an amino or hydroxyl group maybe protected as a tert .- butoxycarbonyl derivative . alternatively , some substituents may be derived from others at the end of the reaction sequence . for instance , a compound of formula i may be synthesized bearing a nitro - or an ethoxycarbonyl or an alkylsulfanyl substituent on the group r 1 , which substituents are finally converted to an amino -, acylamino -, or alkylsulfonylamino substituent , or to a carboxamide substituent , or to an alkylsulfinyl or alkylsulfonyl substituent by standard procedures . the compounds of the general formula i can contain one or several chiral centers and can then be present in a racemic or in an optically active form . the racemates can be separated according to known methods into the enantiomers . for instance , diastereomeric salts which can be separated by crystallization are formed from the racemic mixtures by reaction with an optically active acid such as e . g . d - or l - tartaric acid , mandelic acid , malic acid , lactic acid or camphorsulfonic acid . alternatively separation of the enantiomers can also be achieved by using chromatography on chiral hplc - phases which are commercially available . the compounds according to the present invention may exist in the form of their pharmaceutically acceptable salts . the term “ pharmaceutically acceptable salt ” refers to conventional acid - addition salts or base - addition salts that retain the biological effectiveness and properties of the compounds of formula i and are formed from suitable non - toxic organic or inorganic acids or organic or inorganic bases . acid - addition salts include for example those derived from inorganic acids such as hydrochloric acid , hydrobromic acid , hydroiodic acid , sulfuric acid , sulfamic acid , phosphoric acid and nitric acid , and those derived from organic acids such as p - toluenesulfonic acid , salicylic acid , methanesulfonic acid , oxalic acid , succinic acid , citric acid , malic acid , lactic acid , fumaric acid , and the like . base - addition salts include those derived from ammonium , potassium , sodium and , quaternary ammonium hydroxides , such as for example , tetramethylammonium hydroxide . the chemical modification of a pharmaceutical compound into a salt is a technique well known to pharmaceutical chemists in order to obtain improved physical and chemical stability , hygroscopicity , flowability and solubility of compounds . it is for example described in stahl , p . h ., and wermuth , g ., ( editors ), handbook of pharmaceutical salts , verlag helvetica chimica acta ( vhca ), zürich ( 2002 ) or bastin , r . j ., et al ., organic proc . res . dev . 4 ( 2000 ) 427 - 435 . the compounds according to this invention and their pharmaceutically acceptable salts can be used as medicaments , e . g . in the form of pharmaceutical preparations . the pharmaceutical preparations can be administered orally , e . g . in the form of tablets , coated tablets , dragées , hard and soft gelatine capsules , solutions , emulsions or suspensions . the administration can , however , also be effected rectally , e . g . in the form of suppositories , or parenterally , e . g . in the form of injection solutions . the above - mentioned pharmaceutical preparations can be obtained by processing the compounds according to this invention with pharmaceutically inert , inorganic or organic carriers . lactose , corn starch or derivatives thereof , talc , stearic acids or its salts and the like can be used , for example , as such carriers for tablets , coated tablets , dragées and hard gelatine capsules . suitable carriers for soft gelatine capsules are , for example , vegetable oils , waxes , fats , semi - solid and liquid polyols and the like . depending on the nature of the active substance no carriers are , however , usually required in the case of soft gelatine capsules . suitable carriers for the production of solutions and syrups are , for example , water , polyols , glycerol , vegetable oil and the like . suitable carriers for suppositories are , for example , natural or hardened oils , waxes , fats , semi - liquid or liquid polyols and the like . the pharmaceutical preparations can , moreover , contain preservatives , solubilizers , stabilizers , wetting agents , emulsifiers , sweeteners , colorants , flavorants , salts for varying the osmotic pressure , buffers , masking agents or antioxidants . they can also contain still other therapeutically valuable substances . an embodiment of the invention is a medicament containing one or more compounds according to formula i as active ingredients together with pharmaceutically acceptable adjuvants . another embodiment of the invention is said medicament for the treatment of diseases mediated by an inappropriate activation of src family tyrosine kinases . another embodiment of the invention is said medicament for the treatment of inflammatory -, immunological -, cns disorders or bone diseases . another embodiment of the invention is said medicament for the treatment of cancer . another embodiment of the invention is the use of one or more compounds according to formula i for the manufacture of medicaments for the treatment of diseases mediated by an inappropriate activation of src family tyrosine kinases . another embodiment of the invention is the use of one or more compounds according to formula i for the manufacture of medicaments for the treatment of cancer . another embodiment of the invention is the use of one or more compounds according to formula i for the manufacture of medicaments for the treatment of inflammatory -, immunological -, cns disorders or bone diseases . another embodiment of the invention is the use of one or more compounds according to formula i as src family tyrosine kinase inhibitors . another embodiment of the invention is the use of one or more compounds according to formula i as cell signaling - regulating and anti - proliferating agents . another embodiment of the invention is the use of one or more compounds according to formula i for the treatment of inflammatory -, immunological -, cns disorders or bone diseases . another embodiment of the invention is the use of one or more compounds of formula i according to formula i for the treatment of cancer . a pharmaceutical preparation was obtained e . g . by using the following procedure : 1 . weigh 4 . 0 g glass beads in custom made tube gl 25 , 4 cm ( the beads fill half of the tube ). 2 . add 50 mg compound , disperse with spatulum and vortex . 3 . add 2 ml gelatin solution ( weight beads : gelatin solution = 2 : 1 ) and vortex . 4 . cap and wrap in aluminium foil for light protection . 5 . prepare a counter balance for the mill . 6 . mill for 4 hours , 20 / s in a retsch mill ( for some substances up to 24 hours at 30 / s ). 7 . extract suspension from beads with two layers of filter ( 100 μm ) on a filter holder , coupled to a recipient vial by centrifugation at 400 g for 2 min . 8 . move extract to measuring cylinder . 9 . repeat washing with small volumes ( here 1 ml steps ) until final volume is reached or extract is clear . 10 . fill up to final volume with gelatin and homogenise . the above described preparation yields micro - suspensions of the compounds of formula i with particle sizes between 1 and 10 μm . the suspensions are suitable for oral applications and were used in the in vivo pharmacokinetic testings described below . the activity of the compounds according to this invention as inhibitors for the src - family tyrosine kinases was shown by using the following assay . src - inhibitor - assay parameters : reaction mixture : atp 5 μm peptide ( ro + ja133 - ro ): 10 μm ja133 - ro 196 nm ro 9 . 8 μm pt66 230 ng / ml assay buffer : 4 mm mgcl2 2 mm tcep 50 mm hepes 0 . 1 % tween 20 ph 7 . 3 enzyme : 2 . 5 u / ml inhibitor : max . 25 μm min . 0 . 42 nm material : eu - labelled phosphotyrosine antibody : for lck cisbio mab pt66 - k , for src eg & amp ; g wallac pt66 eu - w1024 ( all commercially available ). peptides : ro : nh 2 - a - e - e - e - i - y - g - e - f - e - a - k - k - k - k - conh 2 , and ja133 - ro : ja133 - g - aminocaprylic acid - a - e - e - e - i - y - g - e - f - e - a - k - k - k - k - conh 2 , wherein ja133 is lightcycler - red 640 - n - hydroxy succinimide ester ; whereby both peptides were synthesized by an optimized solid phase peptide synthesis protocol ( merrifield , fed . proc . fed . amer . soc . exp . biol . 21 ( 1962 ) 412 ) on a zinsser smp350 peptide synthesizer . shortly , the peptide was assembled on 160 mg ( 22 . 8 μmol scale ) of a rink - linker modified polystyrene solid phase by repeatedly conjugating an twenty fold excess of amino acids each protected by temporary piperidine labile fmoc - and permanent acid labile tert - bu -, boc - and o - tert - bu - groups depending on the side chain function . the substrate sequence aeeeiygefeakkkk was n - terminal additionally mounted with the spacer amino acids aminocaprylic acid and glycin . after cleavage of the n - terminal temporary protecting group the still attached and protected peptide was labeled with a 1 . 5 fold amount of lightcycler - red 640 - n - hydroxy succinimide ester ( purchased from roche diagnostics gmbh ) and triethylamine . after 3 hrs . the resin was washed with dimethylformamide and isopropanol until the eluates of the blue resin got colourless . the fully protected and labeled peptide was removed from the solid phase and released from the permanent protecting groups by treatment with a mixture of 80 % trifluoroacetic acid , 10 % ethanedithiol , 5 % thioanisol and 5 % water . the substrate was finally isolated by a preparative reverse phase hplc purification . the purification yielded 12 . 2 mg rp - hplc single peak pure blue material ( lyophilisate ). the identity was proven by maldi mass spectroscopy [ 2720 . 0 ]. enzymes : upstate lck ( p56 lck , active ), upstate src ( p60 c - src , partially purified ) were purchased from ubi , upstate biotech , inc .. time - resolved fluorescence assay : reader : perkin elmer , wallac viktor 1420 - 040 multilabel counter ; liquid handling system : beckman coulter , biomek 2000 . atp , tween ™ 20 , 4 -( 2 - hydroxyethyl )- 1 - piperazineethanesulfonic acid ( hepes ) were purchased from roche molecular biochemicals , mgcl 2 and mncl 2 were purchased from merck eurolab , tris ( 2 - carboxyethyl ) phosphine hydrochloride ( tcep ) was purchased from pierce , 384 well low volume fluorescence plates was purchased from falcon . at first the enzyme is pre - incubated for 15 min . at 15 ° c . in aqueous solution with corresponding amounts of inhibitors according to this invention . then the phosphorylation reaction is started by adding a reaction mixture , containing atp , peptide and pt66 , and subsequent shaking . the proceeding of this reaction is immediately monitored using time resolved fluorescence spectroscopy in a suitable well plate reader . the ic 50 - values can be obtained from the reaction rates by using a non - linear curve fit ( xlfit software ( id business solution ltd ., guilford , surrey , uk )) ic50 src ic50 lck example - no . [ μm ] [ μm ] 6 - 1 0 . 039 0 . 791 2 - 4 0 . 185 1 . 343 1 - 11 0 . 228 5 . 0 - 10 . 0 1 - 1 , 1 - 2 , 1 - 9 , 1 - 10 , 1 - 13 , 0 . 010 - 0 . 500 0 . 100 - 9 . 000 1 - 14 , 1 - 15 , 1 - 16 , 1 - 17 , 1 - 22 , 2 - 1 , 2 - 3 , 2 - 5 , 2 - 8 , 2 - 9 , 3 - 1 , 3 - 2 , 3 - 4 , 3 - 7 , 5 - 1 , 5 - 2 , 7 - 1 , 8 - 1 , 8 - 2 , 8 - 4 , 9 - 1 , 9 - 3 , 9 - 4 , 9 - 5 , 9 - 8 , 9 - 17 , 9 - 19 , 9 - 20 , 9 - 23 , 9 - 25 , 9 - 2810 - 1 , 10 - 2 , 11 - 2 , 11 - 3 , 12 - 1 1 - 10 , 1 - 12 , 1 - 19 , 3 - 2 , 9 - 3 , 0 . 500 - 1 . 500 2 . 000 - 9 . 000 11 - 1 the following examples and references are provided to aid the understanding of the present invention , the true scope of which is set forth in the appended claims . it is understood that modifications can be made in the procedures set forth without departing from the spirit of the invention . 2 , 3 - diamino - 5 - nitropyridine was prepared as described in cai , s . x ., et al , j . med . chem . 40 ( 1997 ) 3679 - 3686 . to 83 mg 3 - buten - 2 - ol ( 1 . 15 mmol ) in 2 ml dichloromethane were added at 0 ° c . 136 mg triphosgene . 91 mg pyridine were added dropwise and stirring was continued for 1 hr at room temperature . the resulting solution was used directly for the next step . the substituted benzaldehydes used are known in the art and prepared by literature procedures , for instances as described for 4 - morpholino - benzaldehyde in magdolen , p ., et al , tetrahedron 5 ( 2001 ) 4781 - 4785 , or as described below : 4 . 82 g potassium hydroxide were dissolved in 70 ml ethanol and treated with 8 . 46 g ( 2 - chloro - ethyl )- diethyl - amine hydrochloride . the mixture was stirred until everything was dissolved , then 5 . 0 g benzaldehyde were added and refluxed for 16 hrs . the mixture was diluted with water and extracted with ethyl acetate , and the organic phases washed several times with caustic soda . after drying and evaporation of the solvent the crude product was used without further purification . 2 . 14 g ( 7 . 52 mmol ) 2 -[ 2 -( 3 - bromo - phenyl )- ethoxy ]- tetrahydro - pyran in 9 ml dry thf were cooled to − 78 ° c . and treated dropwise with 9 . 87 ml of 1 . 6m solution of butyl lithium in hexane ( 15 . 79 mmol ). after stirring for 30 min , 2 . 31 g ( 31 . 58 mmol ) n , n - dimethylformamide were added dropwise and stirring was continued for another 15 min at − 78 ° c . the mixture was slowly warmed to room temperature and stirred for and another 60 min . water and dichloromethane were added , the organic phase separated , and the aqueous phase extracted several times with dichloromethane . the combined organic phases were dried , evaporated and the residue purified by chromatography on silica in ethyl acetate heptane mixtures . yield 1 . 66 g of the title compound as a pale yellow oil . 0 . 76 g ( 7 . 31 mmol ) 3 - methoxypropionic acid in 10 ml dry dmf were treated with 1 . 25 g ( 7 . 71 mmol ) 1 , 1 ′- carbonyl - diimidazole and stirred for 1 hr at room temperature . 1 . 00 g 3 - aminobenzylalcohol were added and stirring was continued over night . the solvent was removed and the residue chromatographed on silica in ethyl acetate , yielding 1 . 26 g n -( 3 - hydroxymethyl - phenyl )- 3 - methoxy - propionamide . the above 1 . 26 g n -( 3 - hydroxymethyl - phenyl )- 3 - methoxy - propionamide were dissolved in 50 ml acetone , 12 . 60 g manganese dioxide were added and the mixture stirred at room temperature over night . the mixture was filtered and the filtrate evaporated and further purified by chromatography on silica in ethyl acetate / heptane mixtures . yield 0 . 77 g of the title compound as a colourless oil . substituted phenyl - acetylenes were prepared by acylation of 3 - or 4 - amino - phenylacetylene by literature procedures , as described in u . s . pat . no . 4 , 162 , 265a , or by alkylation of 3 - or 4 - hydroxyphenylacetylene by literature procedures . for instance , 3 - hydroxyphenylacetylene ( 237 mg , 2 mmol ) was heated with 2 - bromoethylmethylether ( 0 . 23 ml , 2 . 4 mmol ) and potassium carbonate ( 322 mg , 2 . 4 mmol ) in acetone ( 5 ml ) to 110 ° c . in a microwave oven ( cem discover ) for 45 minutes . water ( 1 ml ) was added to the mixture and the whole was extracted with dichloromethane ( 2 × 25 ml ). the combined organics were dried over mgso 4 , filtered and concentrated in vacuo to afford a brown oil . the oil was purified by column chromatography ( sio 2 , dichloromethane ) to afford 3 -( 2 - methoxyethoxy ) phenylacetylene as a colourless oil ( 247 mg , 70 % yield ). 1 h - nmr ( 400 mhz ; cdcl 3 ): δ = 7 . 23 ( 1h , dd , j 8 . 8 , 8 . 0 ), 7 . 08 ( 1h , dt , j 7 . 6 , 1 . 2 ), 7 . 04 ( 1h , dd , j 1 . 48 , 2 . 7 ), 6 . 94 ( 1h , ddd , j 1 . 0 , 2 . 6 , 8 . 3 ), 4 . 11 ( 2h , t , j 4 . 6 ), 3 . 74 ( 2h , t , j 4 . 6 ), 3 . 45 ( 3h , s ), 3 . 05 ( 1h , s ). alternatively , 4 -( 2 - methoxyethoxy ) phenylacetylene was prepared from the corresponding iodobenzene and trimethylsilylacetylene by sonogashira coupling , as described for 4 - methoxyphenylacetylene in tsuji , m ., j . org . chem . 68 ( 2003 ) 9589 - 9597 - supporting information s . 1 - 36 - http :// pubs . acs . org / subscribe / journals / joceah / suppinfo / jo035090f / jo035090fsi2003 0918 — 025110 . pdf . acetic anhydride ( 13 . 8 ml , 144 mmol ) was added dropwise to a solution of 3 - ethynylaniline ( 14 . 0 g , 120 mmol ) and 4 -( dimethylamino -) pyridine ( dmap ) ( 1 . 5 g , 12 mmol ) in tetrahydrofuran ( 300 ml ). the mixture was stirred at room temperature for 2 hours , water ( 100 ml ) was added to the mixture and the whole was extracted with dichloromethane ( 2 × 250 ml ). the combined organics was washed with 10 % citric acid ( 100 ml ) followed by saturated sodium bicarbonate solution ( 100 ml ), dried over mgso 4 , filtered and concentrated in vacuo to afford 3 -( acetylamino ) phenylacetylene as a yellow solid ( 18 . 3 g , 96 %). 1 h - nmr ( 400 mhz ; cdcl 3 ): δ = 7 . 62 ( 1h , s ), 7 . 53 ( 1h , d , j 7 . 7 ), 7 . 41 ( 1h , br . s ), 7 . 28 - 7 . 22 ( 2h , m ), 3 . 06 ( 1h , s ), 2 . 17 ( 3h , s ). 3 . 00 g 6 - chloronicotinic acid in 24 ml dry acetonitrile were mixed with 16 . 6 ml morpholine and heated to reflux for 48 hrs . the mixture was evaporated under vacuum and the residue dissolved in water . the crude product was precipitated by addition of 10 % aqueous acetic acid , isolated by filtration and washed with water and methanol to give 1 . 83 g of the title compound . 14 . 05 g 2 , 3 - diamino - 5 - nitropyridine and 9 . 68 g benzaldehyde in 250 ml nitrobenzene were heated to 140 - 150 ° c . for 15 hrs . the solvent is removed by vacuum distillation and the residue is dispersed in ethyl acetate , filtered , and the filter residue washed thoroughly with ethyl acetate . 12 . 0 g 6 - nitro - 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridine were dissolved in 1 l acetic acid . 18 g iron powder were added and the mixture heated to 80 ° c . with stirring . after 2 hrs the mixture was cooled to room temperature and filtered over celite . the celite pad was washed with methanol and the combined filtrates were evaporated . the residue was dissolved methanol / dichloromethane 1 : 1 and filtered over silica . the filtrate was concentrated to a volume of 100 ml , the resulting precipitate collected by filtration and washed with methanol . 80 mg 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - ylamine ( 0 . 38 mmol ,) in 3 ml dry pyridine were treated with a solution of 3 - buten - 2 - yl chloroformate in dichloromethane . the mixture was stirred at room temperature over night , diluted with 1 ml water and stirred for another hr . the solvents were evaporated and the residue was dispersed in water with sonication , filtered , and the filter residue washed thoroughly with water and ether . 1 h - nmr ( 400 mhz , d 6 - dmso ): δ = 13 . 05 ( broad s , 1h ); 9 . 67 ( broad s , 1h ); 8 . 15 ( s , 1h ); 7 . 96 ( d , 3h ); 7 . 37 - 7 . 28 ( m , 3h ); 5 . 80 - 5 . 71 ( m , 1h ); 5 . 10 ( m , 2h ); 4 . 96 ( d , 1h ); 1 . 13 ( d , 3h ). the following examples were obtained in analogous fashion as described for example 1 - 1 : example - melting no . systematic name 1 h - nmr point (° c .) 1 - 2 ( 2 - phenyl - 1h - ( 400 mhz , d 6 - dmso ): imidazo [ 4 , 5 - δ = 13 . 46 ( s ) and 13 . 00 ( s , b ] pyridin - 6 - yl )- together 1h ); 9 . 82 ( broad s ) carbamic acid and 9 . 69 ( broad s , together isopropyl ester 1h ); 8 . 36 ( d , 1h ); 8 . 38 - 8 . 15 ( m , 3h ); 7 . 60 - 7 . 52 ( m , 3h ); 4 . 94 ( hep , 1h ); 1 . 28 ( d , 6h ). 1 - 3 ( 2 - phenyl - 3h - ( 400 mhz , d 6 - dmso ): imidazo [ 4 , 5 - δ = 13 . 45 ( s ) and 12 . 98 ( s , b ] pyridin - 6 - yl )- together 1h ); 9 . 84 ( broad s ) carbamic acid and 9 . 71 ( broad s , together cyclohexyl ester 1h ); 8 . 37 ( s , 1h ); 8 . 18 ( broad s , 3h ); 7 . 57 - 7 . 51 ( m , 3h ); 4 . 68 ( m , 1h ); 1 . 93 ( m , 2h ); 1 . 74 ( m , 2h ); 1 . 53 - 1 . 20 ( m , 6h ). 1 - 4 ( 2 - phenyl - 3h - ( 400 mhz , d 6 - dmso ): imidazo [ 4 , 5 - δ = 13 . 46 ( s ) and 13 . 00 ( s , b ] pyridin - 6 - yl )- together 1h ); 9 . 90 ( broad s ) carbamic acid and 9 . 78 ( broad s , together isobutyl ester 1h ); 8 . 37 ( d , 1h ); 8 . 23 - 8 . 15 ( m , 3h ); 7 . 60 - 7 . 52 ( m , 3h ); 3 . 92 ( d , 2h ); 1 . 96 ( m , 1h ); 0 . 96 ( d , 6h ). 1 - 5 ( 2 - phenyl - 3h - ( 400 mhz , d 6 - dmso ) imidazo [ 4 , 5 - 13 . 40 ( broad s ) and 13 . 05 ( broad s , b ] pyridin - 6 - yl )- together 1h ); 9 . 93 ( broad s , carbamic acid allyl 1h ); 8 . 37 ( s , 1h ); 8 . 18 ( s , ester 3h ); 7 . 59 - 7 . 48 ( m , 3h ); 6 . 07 - 5 . 97 ( m , 1h ); 5 . 39 ( d , 1h ); 5 . 26 ( d , 1h ); 4 . 66 ( d , 2h ). 1 - 6 ( 2 - phenyl - 3h - ( 400 mhz , d 6 - dmso ) imidazo [ 4 , 5 - 13 . 45 ( broad s ) and 12 . 95 ( broad s , b ] pyridin - 6 - yl )- together 1h ); 9 . 61 ( broad s ) carbamic acid tert - and 9 . 46 ( broad s , together butyl ester 1h ); 8 . 37 ( s , 1h ); 8 . 15 ( m , 3h ); 7 . 55 ( m , 3h ); 1 . 51 ( s , 9h ). 1 - 7 ( 2 - phenyl - 3h - ( 400 mhz , d 6 - dmso ): imidazo [ 4 , 5 - δ = 13 . 42 ( s ) and 13 . 00 ( s , b ] pyridin - 6 - yl )- together 1h ); 9 . 80 ( broad s ) carbamic acid and 9 . 68 ( broad s , together cyclopentyl ester 1h ); 8 . 36 ( s , 1h ); 8 . 18 ( s , 3h ); 7 . 57 - 7 . 52 ( m , 3h ); 5 . 14 ( m , 1h ); 1 . 89 ( m , 2h ); 1 . 71 ( m , 4h ); 1 . 61 ( m , 2h ). 1 - 8 ( 2 - phenyl - 3h - ( 400 mhz , d 6 - dmso ): imidazo [ 4 , 5 - δ = 13 . 20 ( broad s , 1h ); b ] pyridin - 6 - yl )- 9 . 82 ( broad s , 1h ); 8 . 36 ( s , 1h ); carbamic acid ethyl 8 . 18 ( broad s , 3h ); ester 7 . 58 - 7 . 55 ( m , 3h ); 4 . 17 ( broad d , 2h ); 1 . 28 ( broad s , 3h ). 1 - 9 ( 2 - phenyl - 3h - ( 400 mhz , d 6 - dmso ): imidazo [ 4 , 5 - δ = 13 . 46 ( broad s ) and b ] pyridin - 6 - yl )- 13 . 00 ( broad s , together 1h ); carbamic acid sec - 9 . 83 ( broad s ) and 9 . 70 ( broad s , butyl ester together 1h ); 8 . 37 ( s , 1h ); 8 . 19 ( m , 3h ); 7 . 58 - 7 . 50 ( m , 3h ); 4 . 78 ( hex , 1h ); 1 . 61 ( m , 2h ); 1 . 26 ( d , 3h ); 0 . 94 ( t , 3h ). 1 - 10 ( 2 - phenyl - 3h - ( 400 mhz , d 6 - dmso ): imidazo [ 4 , 5 - δ = 13 . 40 ( broad s , 1h ); b ] pyridin - 6 - yl )- 9 . 81 ( broad s , 1h ); 8 . 39 ( s , 1h ); carbamic acid 1 - 8 . 19 ( m , 3h ); 7 . 59 - 7 . 51 ( m , ethyl - propyl ester 3h ); 4 . 68 ( m , 1h ); 1 . 60 ( m , 4h ); 0 . 92 ( t , 6h ). 1 - 11 ( 2 - phenyl - 3h - ( 400 mhz , d 6 - dmso ): imidazo [ 4 , 5 - δ = 10 . 27 ( broad s , 1h ); 8 . 42 ( s , b ] pyridin - 6 - yl )- 1h ); 8 . 20 ( m , 3h ); carbamic acid 7 . 60 - 7 . 53 ( m , 3h ); 5 . 47 ( m , 1h ); 2 , 2 , 2 - trifluoro - 1 - 1 . 46 ( d , 3h ). methyl - ethyl ester 1 - 12 ( 2 - phenyl - 3h - ( 400 mhz , d 6 - dmso ): imidazo [ 4 , 5 - δ = 13 . 30 ( broad s , 1h ); b ] pyridin - 6 - yl )- 9 . 80 ( broad s , 1h ); 8 . 39 ( s , 1h ); carbamic acid 2 , 2 - 8 . 19 ( m , 3h ); 7 . 58 - 7 . 54 ( m , dimethyl - propyl 3h ); 3 . 85 ( s , 2h ); 0 . 98 ( s , ester 9h ). 1 - 13 ( 2 - phenyl - 3h - ( 400 mhz , d 6 - dmso ): imidazo [ 4 , 5 - δ = 13 . 25 ( broad s , 1h ); b ] pyridin - 6 - yl )- 9 . 95 ( broad s , 1h ); 8 . 36 ( s , 1h ); carbamic acid 1 - 8 . 18 ( m , 3h ); 7 . 58 - 7 . 51 ( m , phenyl - ethyl ester 3h ); 7 . 51 - 7 . 42 ( m , 4h ; 7 . 32 ( t , 1h ); 5 . 86 ( q , 1h ); 1 . 57 ( d , 3h ). 1 - 14 ( 2 - phenyl - 1h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid propyl ester 1 - 15 ( 2 - phenyl - 3h - ( 400 mhz , d 6 - dmso ): imidazo [ 4 , 5 - δ = 13 . 49 ( broad s ) and b ] pyridin - 6 - yl )- 13 . 25 ( broad s , together 1h ); carbamic acid 1 - 10 . 09 ( broad s ) and 9 . 96 ( broad s , methyl - prop - 2 - together 1h ); 8 . 37 ( d , 1h ); ynyl ester 8 . 23 - 8 . 17 ( m , 3h ); 7 . 56 ( m , 3h ); 5 . 44 ( q , 1h ); 3 . 59 ( s , 1h ); 1 . 52 ( d , 3h ). 1 - 16 ( 2 - phenyl - 3h - ( 400 mhz , d 6 - dmso ): imidazo [ 4 , 5 - δ = 13 . 48 ( broad s ) and b ] pyridin - 6 - yl )- 13 . 05 ( broad s , together 1h ); carbamic acid 1 - 10 . 03 ( broad s ) and 9 . 90 ( broad s , methyl - but - 2 - ynyl together 1h ); 8 . 36 ( d , 1h ); ester 8 . 22 ( d , 1h ); 8 . 17 ( m , 2h ); 7 . 60 - 7 . 51 ( m , 3h ); 5 . 42 ( q , 1h ); 1 . 85 ( s , 3h ); 1 . 49 ( d , 3h ). 1 - 17 ( 2 - phenyl - 3h - ( 400 mhz , d 6 - dmso ): imidazo [ 4 , 5 - δ = 13 . 25 ( broad s , 1h ); b ] pyridin - 6 - yl )- 9 . 85 ( broad s , 1h ); 8 . 36 ( s , 1h ); carbamic acid 8 . 18 ( d , 3h ); 7 . 55 ( m , 3h ); cyclobutyl ester 4 . 99 ( m , 1h ); 2 . 31 ( m , 2h ); 2 . 08 ( m , 2h ); 1 . 77 ( q , 1h ); 1 . 62 ( m , 1h ). 1 - 18 ( 2 - phenyl - 3h - ( 400 mhz , d 6 - dmso ): imidazo [ 4 , 5 - δ = 9 . 82 ( broad s ) and b ] pyridin - 6 - yl )- 9 . 69 ( broad s , together 1h ); carbamic acid 1 , 3 - 8 . 37 ( d , 1h ); 8 . 18 ( m , 3h ); dimethyl - butyl 7 . 56 ( m , 3h ); 4 . 93 ( m , 1h ); ester 1 . 80 - 1 . 51 ( m , 4h ); 1 . 37 ( m , 1h ); 1 . 26 ( d , 3h ); 0 . 92 ( d , 6h ). 1 - 19 ( 2 - phenyl - 3h - ( 400 mhz , d 6 - dmso ): imidazo [ 4 , 5 - δ = 13 . 44 ( broad s ) and b ] pyridin - 6 - yl )- 13 . 02 ( broad s , together 1h ); carbamic acid 1 , 2 - 9 . 77 ( broad s , 1h ); 8 . 38 ( s , 1h ); dimethyl - propyl 8 . 18 ( s , 3h ); 7 . 54 ( m , 3h ); ester 4 . 67 ( m , 1h ); 1 . 95 ( m , 1h ); 1 . 21 ( d , 3h ); 0 . 95 ( d , 6h ). 1 - 20 { 2 -[ 3 -( 3 - methoxy - ( 400 mhz , d 6 - dmso ): propionylamino )- δ = 10 . 16 ( s , 1h ); 9 . 83 ( broad s ) phenyl ]- 3h - and 9 . 70 ( broad s , together imidazo [ 4 , 5 - 1h ); 8 . 51 ( s , 1h ); 8 . 36 ( s , b ] pyridin - 6 - yl }- 1h ); 8 . 18 ( s , 1h ); 7 . 81 ( s , carbamic acid 1h ); 7 . 69 ( s , 1h ); 7 . 48 ( t , isopropyl ester 1h ); 4 . 94 ( m , 1h ); 3 . 66 ( t , 2h ); 3 . 27 ( s , 3h ); 2 . 60 ( t , 2h ); 1 . 29 ( d , 6h ). tetrahydrofuran ( thf ) fff 32 mg 3 - penten - 2 - ol ( 0 . 38 mmol ,) in 1 ml dry dichloromethane were treated at 0 ° c . with 62 mg 1 , 1 ′- carbonyl - diimidazole . the mixture was stirred at 0 ° c . for 2 hrs . 80 mg 2 - phenyl - 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - ylamine ( 0 . 38 mmol ,) in 0 . 5 ml n - methylpyrrolidone ( nmp ) were added and the mixture stirred over night at room temperature . 1 ml water was added , the precipitate filtered , and the filter residue washed thoroughly with water and ether and further purified by chromatography . 1 h - nmr ( 400 mhz , d 6 - dmso ): δ = 13 . 08 ( broad s , 1h ); 9 . 81 ( broad s , 1h ); 8 . 35 ( s , 1h ); 8 . 18 ( d , 3h ); 7 . 59 - 7 . 50 ( m , 3h ); 5 . 77 ( m , 1h ); 5 . 59 ( dd , 1h ); 5 . 27 ( m , 1h ); 1 . 67 ( d , 3h ); 1 . 34 ( d , 3h ). the following example was obtained in analogous fashion as described for example 1 - 21 : 1 h - nmr ( 400 mhz , d 6 - dmso ): δ = 13 . 45 ( broad s ) and 13 . 00 ( broad s , together 1h ); 9 . 93 ( broad s ) and 9 . 80 ( broad s , together 1h ); 8 . 37 ( d , 1h ); 8 . 21 ( d ) and 8 . 16 ( d , together 3h ); 7 . 60 - 7 . 51 ( m , 3h ); 5 . 23 ( q , 1h ); 5 . 03 ( s , 1h ); 4 . 90 ( s , 1h ); 1 . 78 ( s , 3h ); 1 . 36 ( d , 3h ). 3 . 31 g 5 - bromo - 2 , 3 - diaminopyridine and 3 . 90 g 4 -( 2 - diethylamino - ethoxy ) benzaldehyde in 120 ml nitrobenzene were heated to 140 - 150 ° c . for 24 hrs . the solvent was removed by vacuum distillation . the residue was dispersed in ethyl acetate and the crude product was isolated by filtration and washed thoroughly with more ethyl acetate . to 250 mg of the product from example 2 - 1a ) in 1 ml n - methylpyrrolidone ( nmp ) were added 32 mg copper sulfate pentahydrate and 3 . 1 ml conc . ammonia . the mixture was heated in a capped glass vial in a microwave oven at 151 ° c . and 18 bar for 5 hrs . after cooling , the mixture was diluted with methanol , filtered , and evaporated . the residue was transferred in water onto a short column of rp ( c - 18 ) silica and eluted with water . evaporation of the eluent gave 105 mg of the title product . 100 mg of the product of example 2 - 1b ) in 4 ml dry pyridine were treated at room temperature with 0 . 92 ml of a 1m solution of isopropyl chloroformate in toluene . stirring was continued for 15 hrs . the mixture was evaporated , re - dissolved in 3 ml methanol and 1 ml of conc . ammonia were added . after stirring for 1 hr at room temperature , the mixture was again evaporated and the residue purified by preparative hplc - ms ( meoh / h 2 o / hoac eluent ). 1 h - nmr ( 500 mhz , d 6 - dmso ): δ = 13 . 00 ( broad s , 1h ); 9 . 66 ( broad s , 1h ); 8 . 32 ( s , 1h ); 8 . 11 ( broad d , 3h ); 7 . 11 ( broad d , 2h ); 4 . 94 ( m , 1h ); 4 . 11 ( t , 2h ); 2 . 82 ( t , 2h ); 2 . 58 ( m , not separated from dmso ); 1 . 29 ( d , 6h ); 0 . 99 ( t , 6h ). the following examples were obtained in analogous fashion as described for example 2 - 1 : example - systematic melting point no . name 1 h - nmr (° c .) 2 - 2 { 2 -[ 3 -( 2 - ( 400 mhz , d 6 - dmso ): methoxy - δ = 13 . 42 ( broad s ) and ethoxy )- 12 . 97 ( broad s , together 1h ); phenyl ]- 3h - 9 . 82 ( broad s ) and 9 . 68 ( broad s , imidazo [ 4 , 5 - together 1h ); 8 . 37 ( s , 1h ); b ] pyridin - 6 - yl }- 8 . 18 ( s , 1h ); 7 . 79 ( broad s ) and carbamic acid 7 . 74 ( broad s , together 2h ); isopropyl ester 7 . 47 ( m , 1h ); 7 . 11 ( m , 1h ); 4 . 94 ( m , 1h ); 4 . 21 ( broad s , 2h ); 3 . 72 ( broad s ; 2h ); 3 . 32 ( s , not separated from h2o ); 1 . 29 ( d , 6h ). 2 - 3 { 2 -[ 4 -( 2 - ( 400 mhz , d 6 - dmso ): methoxy - δ = 9 . 80 ( broad s ) and 9 . 65 ( broad ethoxy )- s , together 1h ); 8 . 32 ( s , 1h ); phenyl ]- 3h - 8 . 13 ( m , 3h ); 7 . 14 ( m , 2h ); imidazo [ 4 , 5 - 4 . 94 ( m , 1h ); 4 . 20 ( broad s , b ] pyridin - 6 - yl }- 2h ); 3 . 70 ( broad s ; 2h ); carbamic acid 3 . 32 ( s , not separated from h2o ); isopropyl ester 1 . 28 ( d , 6h ). 2 - 4 [ 2 -( 3 - nitro - ( 400 mhz , d 6 - dmso ): phenyl )- 3h - δ = 13 . 48 ( broad s , 1h ); imidazo [ 4 , 5 - 9 . 74 ( broad s , 1h ); 8 . 94 ( s , 1h ); b ] pyridin - 6 - yl ]- 8 . 53 ( d , 1h ); 8 . 34 ( s , 1h ); 8 . 28 ( m , carbamic acid 1h ); 8 . 16 ( s , 1h ); 7 . 80 ( t , 1h ); isopropyl ester 4 . 86 ( m , 1h ); 1 . 21 ( d , 6h ). 2 - 5 [ 2 -( 4 - ( 400 mhz , d 6 - dmso ): morpholin - 4 - yl - δ = 13 . 14 ( broad s ) and phenyl )- 3h - 12 . 70 ( broad s , together 1h ); imidazo [ 4 , 5 - 9 . 74 ( broad s ) and 9 . 62 ( broad s , b ] pyridin - 6 - yl ]- together 1h ); 8 . 29 ( s , 1h ); carbamic acid 8 . 06 ( m , 3h ); 7 . 09 ( d , 2h ); 4 . 93 ( m , isopropyl ester 1h ); 3 . 76 ( broad s , 4h ); 3 . 27 ( broad s ; 4h ); 1 . 28 ( d , 6h ). 2 - 6 ( 2 - thiophen - 2 - ( 400 mhz , d 6 - dmso ): yl - 3h - δ = 13 . 50 ( broad s ) and imidazo [ 4 , 5 - 13 . 00 ( broad s , together 1h ); b ] pyridin - 6 - yl )- 9 . 81 ( broad s ) and 9 . 67 ( broad s , carbamic acid together 1h ); 8 . 33 ( broad d , isopropyl ester 1h ); 8 . 12 ( broad d , 1h ); 7 . 91 ( d ) and 7 . 84 ( d , together 1h ); 7 . 78 ( m , 1h ); 7 . 26 ( m , 1h ); 4 . 93 ( m , 1h ); 1 . 28 ( d , 6h ). 2 - 7 ( 2 - thiophen - 3 - m . p . 342 ° c . yl - 3h - ( decomposition ) imidazo [ 4 , 5 - b ] pyridin - 6 - yl )- carbamic acid isopropyl ester 2 - 8 { 2 -[ 4 -( 4 - ( 400 mhz , cd 3 od ): methyl - δ = 8 . 26 ( s , 2h ); 8 . 03 ( d , 2h ); 7 . 13 ( d , piperazin - 1 - yl )- 2h ); 5 . 02 ( m , 1h ); 3 . 45 ( broad phenyl ]- 3h - s , 4h ); 2 . 86 ( broad s , 4h ); imidazo [ 4 , 5 - 2 . 54 ( s , 3h ); 1 . 34 ( d , 6h ). b ] pyridin - 6 - yl }- carbamic acid isopropyl ester was prepared as described for example 2 - 1 starting from 5 - bromo - 2 , 3 - diaminopyridine and 3 -[ 2 -( tetrahydro - pyran - 2 - yloxy )- ethyl ]- benzaldehyde . 210 mg ( 0 . 62 mmol ) 2 -{ 3 -[ 2 -( tetrahydro - pyran - 2 - yloxy )- ethyl ]- phenyl }- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - ylamine were dissolved in 2 ml dry n - methylpyrrolidone ( nmp ) and cooled to 0 ° c . 0 . 683 ml of a 1m solution of iso - propyl chloroformate in toluene ( 0 . 683 mmol ) were added and stirring was continued for 10 min at 0 ° c . and for further 3 hrs at room temperature . the solvents were removed under vacuum and the residue taken up in 3 ml methanol and 1 ml conc . aqueous ammonia . the mixture was stirred for 1 hr at room temperature before it was evaporated . the residue was purified by chromatography on silica in ethyl acetate methanol mixtures , yielding 55 mg of the deprotected hydroxyethyl title compound . 1 h - nmr ( 400 mhz , d 6 - dmso ): δ = 13 . 40 ( s ) and 12 . 94 ( s , together 1h ); 9 . 81 ( broad s ) and 9 . 68 ( broad s , together 1h ); 8 . 35 ( d , 1h ); 8 . 17 ( s , 1h ); 8 . 03 - 7 . 96 ( m , 2h ); 7 . 46 ( q , 1h ); 7 . 38 ( d , 1h ); 4 . 94 ( m , 1h ); 4 . 71 ( m , 1h , exchanges with d2o ); 3 . 69 ( m , 2h ); 2 . 83 ( m , 2h ); 4h ); 1 . 29 ( d , 6h ). 0 . 30 g 5 - bromo - 2 , 3 - diaminopyridine and 0 . 212 g 2 - methyl - pyridine - 4 - carboxylic acid were heated in 3 g polyphosphoric acid at 160 ° c . with stirring for 16 hrs . the mixture was diluted with water and insoluble components removed by filtration . water was evaporated from the filtrate and the residue dispersed in pyridine . again , insoluble components were removed by filtration and the filtrate evaporated . the obtained residue was washed thoroughly with water and dried . obtained from 3 - 1a ) and ammonia analogous to example 2 - 1b ). purification by chromatography on silica in methanol / dichloromethane mixtures . obtained from 3 - 1b ) and isopropyl chloro formate analogous to example 2 - 1 . 1 h - nmr ( 400 mhz , d 6 - dmso ): δ = 13 . 74 ( broad s ) and 13 . 29 ( broad s , together 1h ); 9 . 90 ( broad s ) and 9 . 75 ( broad s , together 1h ); 8 . 64 ( t , 1h ); 8 . 43 ( s , 1h ); 8 . 24 ( s , 1h ); 8 . 02 ( s ) and 7 . 96 ( s , together 1h ); 7 . 92 ( d ) and 7 . 86 ( d , together 1h ); 4 . 95 ( m , 1h ); 2 . 58 ( s , 3h ); 1 . 29 ( d , 6h ). the following examples were obtained in analogous fashion as described for example 3 - 1 : example - no . systematic name 1 h - nmr 3 - 2 [ 2 -( 6 - methyl - pyridin - 3 - yl )- ( 400 mhz , d 6 - dmso ): 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - δ = 13 . 58 ( s ) and 13 . 10 ( s , together 1h ); yl ]- carbamic acid isopropyl 9 . 85 ( broad s ) and 9 . 70 ( broad s , ester together 1h ); 9 . 24 ( s ) and 9 . 19 ( s , together 1h ); 8 . 42 - 8 . 34 ( m , 2h ); 8 . 20 ( s , 1h ); 7 . 46 ( t , 1h ); 4 . 94 ( m , 1h ); 2 . 56 ( s , 3h ); 1 . 28 ( d , 6h ). 3 - 3 [ 2 -( 3 - methylsulfanyl - ( 400 mhz , d 6 - dmso ): phenyl )- 3h - imidazo [ 4 , 5 - δ = 9 . 83 ( broad s ) and 9 . 72 ( broad s , b ] pyridin - 6 - yl ]- carbamic acid together 1h ); 8 . 37 ( s , 1h ); 8 . 18 ( s , isopropyl ester 1h ); 8 . 04 ( m , 1h ); 7 . 93 ( m , 1h ); 7 . 50 ( m , 1h ); 7 . 40 ( broad d , 1h ); 4 . 94 ( m , 1h ); 2 . 59 ( s , 3h ); 1 . 28 ( d , 6h ). 3 - 4 [ 2 -( 4 - nitro - phenyl )- 3h - ( 400 mhz , d 6 - dmso ): imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- δ = 13 . 35 ( broad s , 1h ); 9 . 85 ( broad s , 1h ); carbamic acid isopropyl ester 8 . 43 ( broad s , 5h ); 8 . 26 ( s , 1h ); 4 . 94 ( m , 1h ); 1 . 29 ( d , 6h ). 3 - 5 [ 2 -( 1h - benzoimidazol - 5 - yl )- ( 400 mhz , cd 3 od ): δ = 8 . 47 ( s , 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - 1h ); 8 . 33 ( m , 3h ); 8 . 10 ( d , 1h ); yl ]- carbamic acid isopropyl 7 . 80 ( d , 1h ); 5 . 03 ( m , not ester separated from h2o ); 1 . 35 ( d , 6h ). 3 - 6 [ 2 -( 4 - sulfamoyl - phenyl )- 3h - ( 400 mhz , cd 3 od ): imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- δ = 8 . 35 ( broad s , 2h ); 8 . 20 ( d , 2h ); carbamic acid isopropyl ester 8 . 02 ( d , 2h ); 5 . 02 ( m , not separated from h2o ); 1 . 35 ( d , 6h ). 3 - 7 [ 2 -( 6 - morpholin - 4 - yl - ( 400 mhz , d 6 - dmso ): pyridin - 3 - yl )- 3h - δ = 9 . 69 ( broad s , 1h ); 8 . 91 ( s , 1h ); imidazo [ 4 , 5 - b ] pyridin - 6 - yl ]- 8 . 30 ( s ) and 8 . 26 ( d , together 2h ); carbamic acid isopropyl ester 8 . 10 ( s , 1h ); 7 . 01 ( d , 1h ); 4 . 93 ( m , 1h ); 3 . 72 ( broad s , 4h ); 3 . 60 ( broad s , 4h ); 1 . 28 ( d , 6h ). 1 . 0 g 2 , 3 - diamino - 5 - nitropyridine and 1 . 125 g 4 - methylsulfanylbenzoic acid in 20 ml polyphosphoric acid were heated to 160 ° c . with stirring for 15 hrs . the mixture was cooled and poured into water . the ph was adjusted to 4 - 5 by addition of sodium hydroxide and the precipitate collected by filtration . the filtration residue was stirred in 50 ml pyridine at 60 ° c ., cooled and insoluble components removed by filtration . the filtrate was evaporated and the residue used without further purification in the next steps . 0 . 656 g of the nitro compound from example 4 - 1a ) and 0 . 326 g of powdered tin were suspended in a mixture of 20 ml water and 10 ml conc . hcl and stirred at 80 ° c . after 3 hrs the mixture was cooled to room temperature , diluted with 50 ml methanol and filtered . the filtrate was further diluted with 50 ml water and adjusted to ph ˜ 12 by addition of ammonia . resulting precipitate was again filtered off over a small pad of silica , and the filtrate was evaporated . the residue was dissolved in methanol / dichloromethane 2 : 1 and filtered once more over a pad of silica . the filtrate was finally evaporated and the residue used as such without further purification for the next step . 30 mg from example 4 - 1b ) were dissolved in 0 . 5 ml dry n - methylpyrrolidone ( nmp ) and cooled in an ice bath . 0 . 08 ml of a 1m solution of isopropyl chloro formate in toluene were added . after stirring for 30 min , the temperature was raised to room temperature . after another 2 hrs , 0 . 2 ml conc . ammonia were added and the mixture was stirred 30 min . the solvents were removed under vacuum and the residue was purified by preparative hplc - ms . 1 h - nmr ( 400 mhz , d 6 - dmso ): δ = 13 . 40 ( broad s ) and 12 . 92 ( broad s , together 1h ); 9 . 75 ( broad s , 1h ); 8 . 34 ( s , 1h ); 8 . 16 - 8 . 10 ( m , 3h ); 7 . 43 ( d , 2h ); 4 . 94 ( m , 1h ); 2 . 57 ( s , 3h ); 1 . 28 ( d , 6h ). 89 mg of the nitro - phenyl derivative from example 2 - 4 in 5 ml tetrahydrofuran ( thf ) and 5 ml methanol were hydrogenated over 33 mg 10 % pd on charcoal at room temperature for 45 min . the catalyst was filtered off and washed with methanol . the filtrate was evaporated and the residue purified by chromatography on silica in methanol / dichloromethane mixtures . 1 h - nmr ( 400 mhz , d 6 - dmso ): δ = 13 . 24 ( broad s ) and 12 . 78 ( broad s , together 1h ); 9 . 79 ( broad s ) and 9 . 65 ( broad s , together 1h ); 8 . 33 ( broad s , 1h ); 8 . 14 ( s , 1h ); 7 . 45 ( m , 1h ); 7 . 30 ( m , 1h ); 7 . 20 ( m , 1h ); 6 . 70 ( d , 1h ); 5 . 33 ( broad s , 2h ); 4 . 93 ( m , 1h ); 1 . 28 ( d , 6h ). the following examples were obtained in analogous fashion as described for example 5 - 1 : example - no . systematic name 1 h - nmr 5 - 2 [ 2 -( 4 - amino - phenyl )- 3h - ( 400 mhz , cd 3 od ): imidazo [ 4 , 5 - b ] pyridin - 6 - δ = 8 . 23 ( broad s , 2h ); 7 . 87 yl ]- carbamic acid ( broad s , 2h ); 6 . 80 ( broad s , isopropyl ester 2h ); 5 . 00 ( m , not separated from h2o ); 1 . 34 ( d , 6h ). 10 mg of the product from example 5 - 1 were dissolved in 1 ml dry pyridine and 7 μl acetyl chloride were added at room temperature . after stirring over night , the solvent was evaporated and the residue dissolved in 3 ml methanol . 1 ml conc . ammonia were added and the mixture stirred for 1 hr at room temperature . 1 h - nmr ( 400 mhz , d 6 - dmso ): δ = 13 . 10 ( broad s , 1h ); 10 . 25 ( s , 1h ); 9 . 92 ( broad s ) and 9 . 80 ( broad s , together 1h ); 8 . 57 ( s , 1h ); 8 . 45 ( s , 1h ); 8 . 27 ( s , 1h ); 7 . 89 ( broad s , 1h ); 7 . 79 ( m , 1h ); 7 . 57 ( t , 1h ); 5 . 02 ( m , 1h ); 2 . 19 ( s , 3h ); 1 . 38 ( d , 6h ). 45 mg of the product from example 5 - 1 were dissolved in 1 ml dry nmp and cooled to 0 ° c . 18 . 3 mg methylsulfonylchloride were added and the mixture was stirred for 1 hr at 0 ° c . and another hr at room temperature . 12 μl ( 1 equivalent ) pyridine were added and stirring was continued for another 60 min . after addition of 0 . 1 ml conc . hcl , the solvent was removed under vacuum and the residue purified by chromatography on c - 18 rp silica in methanol water mixtures . 97 mg meta - chloro perbenzoic acid ( 70 %) were dissolved in 10 ml dichloromethane and dried by filtration over sodium sulfate . this solution was added to a suspension of 150 mg of the product from example 3 - 3 in 20 ml dichloromethane at room temperature . after 3 hrs the solvent was removed and the residue purified by chromatography on silica . 1 h - nmr ( 400 mhz , d 6 - dmso ): δ = 13 . 20 ( broad s , 1h ); 9 . 80 ( broad s , 1h ); 8 . 50 ( s , 1h ); 8 . 39 ( s , 1h ); 8 . 31 ( d , 1h ); 8 . 21 ( s , 1h ); 7 . 83 - 7 . 75 ( m , 2h ); 4 . 95 ( m , 1h ); 2 . 84 ( s , 3h ); 1 . 29 ( d , 6h ). 210 mg oxone were added to a suspension of 130 mg of the product from example 3 - 3 in 20 ml methanol and 0 . 5 ml water . the mixture was stirred at room temperature for 30 min , then evaporated and the residue chromatographed on silica , eluting first with ethyl acetate , followed by ethyl acetate / methanol mixtures . 1 h - nmr ( 400 mhz , d6 - dmso ): δ = 13 . 72 ( broad s ) and 13 . 30 ( broad s , together 1h ); 9 . 87 ( broad s ) and 9 . 73 ( broad s , together 1h ); 8 . 76 ( s ) and 8 . 69 ( s , together 1h ); 8 . 51 ( m , 1h ); 8 . 48 ( s , 1h ); 8 . 23 ( s , 1h ); 8 . 07 ( m , 1h ); 7 . 86 ( m , 1h ); 4 . 95 ( m , 1h ); 2 . 51 ( s , not separated from dmso ); 1 . 29 ( d , 6h ). the following examples were obtained in analogous fashion as described for example 8 - 2 : example - melting no . systematic name 1 h - nmr point (° c .) 8 - 3 [ 2 -( 4 - ( 400 mhz , d 6 - dmso ): methanesulfonyl - δ = 9 . 85 ( broad s , 1h ); phenyl )- 3h - 8 . 42 ( broad s , 3h ); 8 . 24 imidazo [ 4 , 5 - ( s , 1h ); 8 . 12 ( d , 2h ); b ] pyridin - 6 - yl ]- 4 . 95 ( m , 1h ); 2 . 53 ( s , carbamic acid not separated from isopropyl ester dmso ); 1 . 29 ( d , 6h ). 8 - 4 [ 2 -( 4 - ( 400 mhz , d 6 - dmso ): methanesulfinyl - δ = 13 . 20 ( broad s , 1h ); phenyl )- 3h - 9 . 80 ( broad s , 1h ); 8 . 37 imidazo [ 4 , 5 - ( m , 3h ); 8 . 21 ( s , 1h ); b ] pyridin - 6 - yl ]- 7 . 87 ( d , 2h ); 4 . 95 ( m , 1h ); carbamic acid 2 . 82 ( s , 3h ); 1 . 29 ( d , 6h ). isopropyl ester 1 . 83 g 2 - amino - 3 - bromo - 5 - nitropyridine 0 . 29 g pdcl 2 ( pph 3 ) 2 and 79 mg cui were mixed in 36 ml dry thf and 3 . 45 ml triethylamine and 1 . 12 g phenylacetylene were added . stirring was continued at room temperature for 12 hrs , then the solvent was removed and the residue purified by flash chromatography on silica in ethyl acetate / heptane eluent . 0 . 843 g potassium tert . butylate in 15 ml dry nmp were treated with a solution of 0 . 855 g of the product from example 9 - 1a ) in 15 ml nmp . the mixture was stirred at room temperature for 12 hrs , and then transferred onto a short column of ca . 150 g silica . the product was eluted sequentially with heptane , then heptane / ethyl acetate 1 : 1 . product containing fractions were collected and evaporated , and the residue dispersed in water . filtration and washing of the filter residue with water and heptane yielded 0 . 55 g of the title product . 200 mg of the product from example 9 - 1b ) in 15 ml methanol were hydrogenated over 40 mg 10 % pd on charcoal at room temperature for 2 . 5 hrs . the mixture was filtered and the product purified by chromatography on c - 18 rp silica in methanol water . 130 mg of the product from example 9 - 1c ) were dissolved in 2 . 18 ml dry nmp and cooled to 0 ° c . one equivalent ( 0 . 607 ml ) of a 1m solution of iso - propyl chloroformate in toluene were added dropwise and stirring was continued for 10 min at 0 ° c ., and another 3 hrs at room temperature . 0 . 5 ml methanol and 0 . 5 ml conc . ammonia were added and the mixture was stirred for 1 hr at room temperature . finally the solvents were removed under vacuum and the residue purified by preparative hplc - ms . 1 h - nmr ( 400 mhz , d 6 - dmso ): δ = 12 . 05 ( s , 1h ); 9 . 51 ( broad s , 1h ); 8 . 23 ( s , 1h ); 8 . 07 ( s , 1h ); 7 . 92 ( d , 2h ); 7 . 46 ( t , 2h ); 7 . 34 ( t , 1h ); 6 . 89 ( s , 1h ); 4 . 92 ( m , 1h ); 1 . 28 ( d , 6h ). 3 -( 2 - methoxy - ethoxy )- phenylacetylene ( 6 . 3 g , 36 mmol ) was added to a solution of triethylamine ( 1 . 92 ml , 14 mmol ), 2 - amino - 3 - bromo - 5 - nitropyridine ( 4 g , 18 mmol ), pdcl 2 ( pph 3 ) 2 ( 966 mg , 1 . 38 mmol ) and cui ( 262 mg , 1 . 38 mmol ) in anhydrous tetrahydrofuran ( 80 ml ) in the dark . the mixture was stirred at room temperature for 48 hours then concentrated in vacuo and dissolved in dichloromethane ( 150 ml ). the organic solution was washed with water ( 25 ml ), dried over mgso 4 , filtered and concentrated in vacuo to 20 % of its original volume and heptane ( 20 ml ) was then added . the resultant yellow solid was filtered and dried to give 3 -[ 3 -( 2 - methoxy - ethoxy )- phenylethynyl ]- 5 - nitro - pyridin - 2 - ylamine ( 4 . 2 g , 74 % yield ). 1 h - nmr ( 400 mhz , d 6 - dmso ): δ = 8 . 89 ( 1h , d , j 2 . 7 ), 8 . 34 ( 1h , d , j 2 . 7 ), 7 . 39 ( 1h , m ), 7 . 35 ( 1h , d , j 8 . 0 ), 7 . 30 ( 1h , dt , j 1 . 0 , 7 . 6 ), 7 . 04 ( 1h , ddd , j 1 . 0 , 2 . 6 , 8 . 2 ), 4 . 15 ( 2h , t , j 4 . 5 ), 3 . 69 ( 2h , t , j 4 . 5 ), 3 . 34 ( 3h , s ). potassium tert - butoxide ( 1 . 18 g , 10 . 5 mmol ) was added to a solution of 3 -[ 3 -( 2 - methoxy - ethoxy )- phenylethynyl ]- 5 - nitro - pyridin - 2 - ylamine ( 1 . 57 g , 5 mmol ) in a 2 : 1 mixture of tetrahydrofuran and dimethylformamide ( 75 ml ). the mixture was heated at 70 ° c . for 16 hours then the tetrahydrofuran was removed in vacuo . the mixture was poured onto a pad of silica and eluted with ethyl acetate then 10 % methanol in ethyl acetate . the organics were concentrated in vacuo to 5 % of their original volume and water ( 30 ml ) was added . the resultant orange solid was filtered and dried to afford 2 -[ 3 -( 2 - methoxy - ethoxy )- phenyl ]- 5 - nitro - 1h - pyrrolo [ 2 , 3 - b ] pyridine ( 1 . 3 g , 83 %). 1 h - nmr ( 400 mhz , d 6 - dmso ): δ = 12 . 88 ( 1h , s ), 9 . 04 ( 1h , d , j 2 . 6 ), 8 . 77 ( 1h , d , j 2 . 6 ), 7 . 52 - 7 . 50 ( 2h , m ), 7 . 36 ( 1h , app . t , j 8 . 1 , 7 . 8 ), 7 . 18 ( 1h , s ), 6 . 95 ( 1h , dd , j 1 . 8 , 8 . 1 ), 4 . 15 ( 2h , t , j 4 . 6 ), 3 . 65 ( 2h , t , j 4 . 6 ), 3 . 25 ( 3h , s ). to a mixture of 2 -[ 3 -( 2 - methoxy - ethoxy )- phenyl ]- 5 - nitro - 1h - pyrrolo [ 2 , 3 - b ] pyridine ( 7 . 1 mmol , 2 . 2 g ) and iron powder ( 6 . 7 g ) in ethanol ( 50 ml ) was added hcl ( conc .) ( 0 . 7 ml ) and water ( 5 ml ). the mixture was heated at 70 ° c . for 3 hours then cooled and filtered through celite ®. the solvent was removed in vacuo and the residue dissolved in ethyl acetate ( 30 ml ), washed with saturated sodium bicarbonate ( 15 ml ), dried over mgso 4 , filtered and concentrated in vacuo . the crude product was purified by column chromatography ( sio 2 , ethyl acetate ) to afford 2 -[ 3 -( 2 - methoxy - ethoxy )- phenyl ]- 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - ylamine ( 1 . 2 g , 60 %). 1 h - nmr ( 400 mhz , d 6 - dmso ): δ = 11 . 62 ( 1h , s ), 7 . 78 ( 1h , d , j 2 . 0 ), 7 . 53 - 7 . 50 ( 2h , m ), 7 . 38 ( 1h , app . t , j 8 . 0 ), 7 . 13 ( 1h , d , j 2 . 3 ), 6 . 93 ( 1h , dd , j 1 . 7 , 8 . 0 ), 6 . 75 ( 1h , d , j 2 . 0 ), 4 . 8 ( 2h , br . s ), 4 . 24 ( 2h , t , j 4 . 6 ), 3 . 76 ( 2h , t , j 4 . 6 ), 3 . 40 ( 3h , s ). the above amino compound was acylated with isopropyl chloroformate as described for example 9 - 1 to yield the title compound . 1 h - nmr ( 400 mhz , d 6 - dmso ): δ = 12 . 00 ( s , 1h ); 9 . 52 ( broad s ; 1h ); 8 . 22 ( broad s , 1h ); 8 . 06 ( broad s , 1h ); 7 . 52 ( s ) and 7 . 49 ( s , together 2h ); 7 . 36 ( t , 1h ); 6 . 92 ( broad s , 2h ); 4 . 92 ( m , 2h ); 4 . 20 ( t , 2h ); 3 . 71 ( t , 2h ); 1 . 28 ( d , 6h ). the following examples were obtained in analogous fashion as described for example 9 - 2 : melting example - no . systematic name 1 h - nmr point (° c .) 9 - 3 ( 2 - phenyl - 1h - ( 400 mhz , d 6 - dmso ): pyrrolo [ 2 , 3 - δ = 11 . 94 ( s , 1h ); 9 . 45 ( broad s , b ] pyridin - 5 - yl )- 1h ); 8 . 14 ( broad s , 1h ); carbamic acid 2 , 2 - 7 . 97 ( broad s , 1h ); 7 . 83 ( d , dimethyl - propyl 2h ); 7 . 37 ( t , 2h ); 7 . 25 ( t , ester 1h ); 6 . 80 ( s , 1h ); 3 . 73 ( s , 2h ); 0 . 87 ( s , 9h ). 9 - 4 { 2 -[ 4 -( 2 - methoxy - ( 400 mhz , cd 3 od ): ethoxy )- phenyl ]- 1h - δ = 8 . 15 ( broad s , 1h ); pyrrolo [ 2 , 3 - 8 . 06 ( broad s , 1h ); 7 . 79 ( d , 2h ); b ] pyridin - 5 - yl }- 7 . 06 ( d , 2h ); 6 . 69 ( s , 1h ); carbamic acid ethyl 4 . 23 ( q ) and 4 . 19 ( t , ester together 4h ); 3 . 79 ( t , 2h ); 3 . 46 ( s , 3h ); 1 . 35 ( t , 3h ). 9 - 5 { 2 -[ 4 -( 2 - methoxy - ( 400 mhz , cd 3 od ): ethoxy )- phenyl ]- 1h - δ = 8 . 08 ( broad s , 1h ); pyrrolo [ 2 , 3 - 7 . 99 ( broad s , 1h ); 7 . 71 ( d , 2h ); b ] pyridin - 5 - yl }- 6 . 98 ( d , 2h ); 6 . 62 ( s , 1h ); carbamic acid allyl 5 . 96 ( m , 1h ); 5 . 32 ( d , 1h ); ester 5 . 18 ( d , 1h ); 4 . 60 ( d , 2h ); 4 . 12 ( t , 2h ); 3 . 71 ( t , 2h ); 3 . 38 ( s , 3h ). 9 - 6 { 2 -[ 3 -( 2 - methoxy - ( 400 mhz , d 6 - dmso ): ethoxy )- phenyl ]- 1h - δ = 11 . 88 ( s , 1h ); 9 . 46 ( broad s ; pyrrolo [ 2 , 3 - 1h ); 8 . 09 ( broad s , 1h ); b ] pyridin - 5 - yl }- 7 . 92 ( broad s , 1h ); 7 . 39 ( s ) carbamic acid ethyl and 7 . 36 ( s , together 2h ); ester 7 . 23 ( t , 1h ); 6 . 78 ( m , 2h ); 4 . 07 - 3 . 99 ( m , 4h ); 3 . 58 ( t , 2h ); 1 . 14 ( t , 3h ). 9 - 7 { 2 -[ 3 -( 2 - methoxy - ( 400 mhz , d 6 - dmso ): ethoxy )- phenyl ]- 1h - δ = 12 . 23 ( s , 1h ); 9 . 92 ( broad s ; pyrrolo [ 2 , 3 - 1h ); 8 . 43 ( broad s , 1h ); b ] pyridin - 5 - yl }- 8 . 26 ( broad s , 1h ); 7 . 73 ( s ) carbamic acid allyl and 7 . 70 ( s , together 2h ); ester 7 . 57 ( t , 1h ); 7 . 14 - 7 . 11 ( m , 2h ); 6 . 27 - 6 . 17 ( m , 1h ); 5 . 59 ( d , 1h ); 5 . 46 ( d , 1h ); 4 . 84 ( d , 2h ); 4 . 40 ( t , 2h ); 3 . 92 ( t , 2h ). 9 - 8 ( 2 - phenyl - 1h - pyrrolo [ 2 , 3 - b ] pyridin - 5 - yl )- carbamic acid benzyl ester 9 - 9 { 2 -[ 3 -( 2 - methoxy - ( 400 mhz , d 6 - dmso ): ethoxy )- phenyl ]- 1h - δ = 11 . 89 ( s , 1h ); 9 . 48 ( broad s ; pyrrolo [ 2 , 3 - 1h ); 8 . 11 ( broad s , 1h ); b ] pyridin - 5 - yl }- 7 . 94 ( broad s , 1h ); carbamic acid 7 . 41 - 7 . 38 ( m , 2h ); 7 . 24 ( t , 1h ); isobutyl ester 6 . 81 - 6 . 78 ( m , 2h ); 4 . 07 ( t , 2h ); 3 . 78 ( d , 2h ); 3 . 59 ( t , 2h ); 1 . 83 ( m , 1h ); 0 . 84 ( d , 6h ). 9 - 10 { 2 -[ 3 -( 2 - methoxy - ( 400 mhz , d 6 - dmso ): ethoxy )- phenyl ]- 1h - δ = 12 . 04 ( s , 1h ); 9 . 85 ( broad s ; pyrrolo [ 2 , 3 - 1h ); 8 . 24 ( broad s , 1h ); b ] pyridin - 5 - yl }- 8 . 08 ( broad s , 1h ); carbamic acid 2 - 7 . 63 - 7 . 48 ( m , 4h ); 7 . 47 - 7 . 33 ( m , chloro - benzyl ester 3h ); 6 . 94 - 6 . 90 ( m , 2h ); 5 . 27 ( s , 2h ); 4 . 20 ( t , 2h ); 3 . 71 ( d , 2h ). 9 - 11 ( 2 - phenyl - 1h - ( 400 mhz , d 6 - dmso ): pyrrolo [ 2 , 3 - δ = 12 . 05 ( s , 1h ); 9 . 58 ( broad s ; b ] pyridin - 5 - yl )- 1h ); 8 . 23 ( broad s , 1h ); carbamic acid ethyl 8 . 06 ( broad s , 1h ); 7 . 93 ( d , ester 2h ); 7 . 47 ( t , 2h ); 7 . 35 ( t , 1h ); 6 . 90 ( s , 1h ); 4 . 16 ( 6 , 2h ); 1 . 27 ( t , 3h ). 9 - 12 ( 2 - phenyl - 1h - ( 400 mhz , d 6 - dmso ): pyrrolo [ 2 , 3 - δ = 12 . 07 ( s , 1h ); 9 . 85 ( broad s ; b ] pyridin - 5 - yl )- 1h ); 8 . 24 ( broad s , 1h ); carbamic acid 2 - 8 . 09 ( broad s , 1h ); 7 . 93 ( d , chloro - benzyl ester 2h ); 7 . 64 - 7 . 32 ( m , 7h ); 6 . 91 ( s , 1h ). 9 - 13 ( 2 - phenyl - 1h - ( 400 mhz , d 6 - dmso ): pyrrolo [ 2 , 3 - δ = 12 . 28 ( s , 1h ); 9 . 93 ( broad s ; b ] pyridin - 5 - yl )- 1h ); 8 . 44 ( broad s , 1h ); carbamic acid allyl 8 . 28 ( broad s , 1h ); 8 . 14 ( d , ester 2h ); 7 . 69 ( t , 2h ); 7 . 57 ( t , 1h ); 7 . 12 ( s , 1h ); 6 . 23 ( m , 1h ); 5 . 60 ( d , 1h ); 5 . 47 ( d , 1h ); 4 . 85 ( d , 2h ). 9 - 14 ( 2 - phenyl - 1h - ( 400 mhz , d 6 - dmso ): pyrrolo [ 2 , 3 - δ = 12 . 05 ( s , 1h ); 9 . 56 ( broad s ; b ] pyridin - 5 - yl )- 1h ); 8 . 23 ( broad s , 1h ); carbamic acid 8 . 06 ( broad s , 1h ); 7 . 93 ( d , isobutyl ester 2h ); 7 . 47 ( t , 2h ); 7 . 35 ( t , 1h ); 6 . 90 ( s , 1h ); 3 . 90 ( d , 2h ); 1 . 95 ( m , 1h ); 0 . 96 ( d , 6h ). 9 - 15 { 2 -[ 3 -( 2 - methoxy - ( 400 mhz , d 6 - dmso ): ethoxy )- phenyl ]- 1h - δ = 12 . 21 ( s , 1h ); 9 . 77 ( broad s ; pyrrolo [ 2 , 3 - 1h ); 8 . 45 ( broad s , 1h ); b ] pyridin - 5 - yl }- 8 . 27 ( broad s , 1h ); carbamic acid 2 , 2 - 7 . 74 - 7 . 70 ( m , 2h ); 7 . 57 ( t , 1h ); dimethyl - propyl 7 . 14 - 7 . 11 ( m , 2h ); 4 . 40 ( t , ester 2h ); 4 . 03 ( s , 2h ); 3 . 91 ( t , 2h ); 1 . 18 ( d , 9h ). 9 - 16 { 2 -[ 3 -( 2 - methoxy - ( 400 mhz , d 6 - dmso ): ethoxy )- phenyl ]- 1h - δ = 12 . 03 ( s , 1h ); 9 . 76 ( broad s ; pyrrolo [ 2 , 3 - 1h ); 8 . 23 ( broad s , 1h ); b ] pyridin - 5 - yl }- 8 . 07 ( broad s , 1h ); carbamic acid benzyl 7 . 53 - 7 . 33 ( m , 8h ); 6 . 94 - 6 . 91 ( m , ester 2h ); 5 . 19 ( s , 2h ); 4 . 20 ( t , 2h ); 3 . 71 ( t , 2h ). 9 - 17 { 2 -[ 4 -( 2 - methoxy - ( 400 mhz , cd 3 od ): ethoxy )- phenyl ]- 1h - δ = 8 . 11 ( broad s , 1h ); pyrrolo [ 2 , 3 - 8 . 05 ( broad s , 1h ); 7 . 79 ( d , 2h ); b ] pyridin - 5 - yl }- 7 . 06 ( d , 2h ); 6 . 69 ( s , 1h ); carbamic acid 4 . 99 ( m , not separated from isopropyl ester h2o ) 4 . 20 ( t , 2h ); 3 . 80 ( t , 2h ); 3 . 46 ( s , 3h ); 1 . 34 ( d , 6h ). 9 - 18 { 2 -[ 4 -( 2 - methoxy - ( 400 mhz , cd 3 od ): ethoxy )- phenyl ]- 1h - δ = 8 . 16 ( broad s , 1h ); pyrrolo [ 2 , 3 - 8 . 08 ( broad s , 1h ); 7 . 79 ( d , 2h ); b ] pyridin - 5 - yl }- 7 . 46 ( d , 2h ); 7 . 42 - 7 . 32 ( m , carbamic acid benzyl 3h ); 7 . 06 ( d , 2h ); 6 . 69 ( s , ester 1h ); 5 . 23 ( s , 2h ); 4 . 20 ( t , 2h ); 3 . 80 ( t , 2h ); 3 . 46 ( s , 3h ); 1 . 34 ( d , 6h ). 9 - 19 { 2 -[ 4 -( 2 - methoxy - ( 400 mhz , cd 3 od ): ethoxy )- phenyl ]- 1h - δ = 8 . 16 ( broad s , 1h ); pyrrolo [ 2 , 3 - 8 . 06 ( broad s , 1h ); 7 . 79 ( d , 2h ); b ] pyridin - 5 - yl }- 7 . 06 ( d , 2h ); 6 . 69 ( s , 1h ); carbamic acid 4 . 20 ( t , 2h ); 3 . 97 ( d , 2h ); isobutyl ester 3 . 80 ( t , 2h ); 3 . 46 ( s , 3h ); 2 . 02 ( m , 1h ); 1 . 03 ( d , 6h ). was prepared analogously to example 9 - 2 starting from 3 -( acetylamino ) phenylacetylene . in the preparation of the intermediate n -[ 3 -( 5 - nitro - 1h - pyrrolo [ 2 , 3 - b ] pyridin - 2 - yl )- phenyl ]- acetamide by cyclization reaction an higher equimolar amount of base ( potassium tert - butoxide ) as in example 2 - 2 is needed : potassium tert - butoxide ( 2 . 25 g , 20 mmol ) was added to a solution of n -[ 4 -( 2 - amino - 5 - nitro - pyridin - 3 - ylethynyl )- phenyl ]- acetamide ( 1 . 48 g , 5 mmol ) in a 2 : 1 mixture of tetrahydrofuran and dimethylformamide ( 75 ml ). the mixture was heated at 70 ° c . for 16 hours then the tetrahydrofuran was removed in vacuo . the mixture was poured onto a pad of silica and eluted with 10 % methanol in ethyl acetate . the organics were concentrated in vacuo to 5 % of their original volume and water ( 30 ml ) was added . the resultant orange solid was filtered and dried to afford n -[ 3 -( 5 - nitro - 1h - pyrrolo [ 2 , 3 - b ] pyridin - 2 - yl )- phenyl ]- acetamide ( 1 . 01 g , 68 %). 1 h - nmr ( 400 mhz , d 6 - dmso ): δ = 12 . 97 ( 1h , s ), 10 . 17 ( 1h , s ), 9 . 16 ( 1h , d , j 2 . 5 ), 8 . 94 ( 1h , d , j 2 . 5 ), 8 . 24 ( 1h , s ), 7 . 70 ( 1h , d , j 7 . 8 ), 7 . 63 ( 1h , d , j 8 . 2 ), 7 . 50 ( 1h , app . t , j 7 . 9 ), 7 . 10 ( 1h , s ), 2 . 15 ( 3h , s ). the above nitro compound was reduced to the amino compound and subsequently acylated with isopropyl chloroformate as described in example 9 - 1 to yield the title compound . 1 h - nmr ( 400 mhz , d 6 - dmso ): δ = 12 . 03 ( s , 1h ); 10 . 05 ( broad s ; 1h ); 9 . 53 ( broad s , 1h ); 8 . 22 ( broad s , 1h ); 8 . 06 ( broad s , 2h ); 7 . 56 ( t , 2h ); 7 . 39 ( t , 1h ); 6 . 73 ( s , 1h ); 4 . 92 ( heptett , 1h ); 2 . 09 ( s , 3h ); 1 . 28 ( d , 6h ). the following examples were obtained in analogous fashion as described for example 9 - 20 : melting example - no . systematic name 1 h - nmr point (° c .) 9 - 21 [ 2 -( 4 - acetylamino - ( 400 mhz , d 6 - dmso ): phenyl )- 1h - δ = 11 . 81 ( s , 1h ); 9 . 94 ( s ; 1h ); pyrrolo [ 2 , 3 - 9 . 54 ( broad s , 1h ); b ] pyridin - 5 - yl ]- 8 . 05 ( broad s , 1h ); 7 . 88 ( broad s , carbamic acid allyl 1h ); 7 . 70 ( d , 2h ); 7 . 52 ( d , ester 2h ); 6 . 65 ( s , 1h ); 5 . 87 ( m , 1h ); 5 . 24 ( d , 1h ); 5 . 11 ( d , 1h ); 4 . 49 ( d , 2h ); 1 . 93 ( s , 3h ). 9 - 22 [ 2 -( 3 - acetylamino - ( 400 mhz , d 6 - dmso ): phenyl )- 1h - δ = 12 . 06 ( s , 1h ); 10 . 06 ( broad pyrrolo [ 2 , 3 - s ; 1h ); 9 . 84 , ( broad s , 1h ); b ] pyridin - 5 - yl ]- 8 . 23 ( broad s , 1h ); 8 . 10 ( s ) carbamic acid 2 - and 8 . 07 ( s , together 2h ); chloro - benzyl ester 7 . 64 - 7 . 50 ( m , 4h ); 7 . 46 - 7 . 35 ( m , 3h ); 6 . 74 ( s , 1h ); 5 . 27 ( s , 2h ); 2 . 09 ( s , 3h ). 9 - 23 [ 2 -( 3 - acetylamino - ( 400 mhz , d 6 - dmso ): phenyl )- 1h - δ = 12 . 05 ( s , 1h ); 10 . 06 ( broad pyrrolo [ 2 , 3 - s ; 1h ); 9 . 75 , ( broad s , 1h ); b ] pyridin - 5 - yl ]- 8 . 23 ( broad s , 1h ); 8 . 09 ( s ) carbamic acid benzyl and 8 . 07 ( s , together 2h ); ester 7 . 56 ( t , 2h ); 7 . 49 - 7 . 34 ( m , 6h ); 6 . 74 ( s , 1h ); 5 . 19 ( s , 2h ); 2 . 09 ( s , 3h ). 9 - 24 [ 2 -( 3 - acetylamino - ( 400 mhz , d 6 - dmso ): phenyl )- 1h - δ = 11 . 89 ( s , 1h ); 9 . 91 ( s , 1h ); pyrrolo [ 2 , 3 - 9 . 43 ( broad s ; 1h ); b ] pyridin - 5 - yl ]- 8 . 09 ( broad s , 1h ); 7 . 93 ( broad s , carbamic acid 2 , 2 - 2h ); 7 . 44 ( d , 1h ); 7 . 39 ( d , dimethyl - propyl 1h ); 7 . 25 ( t , 1h ); 6 . 59 ( s , ester 1h ); 3 . 68 ( s , 2h ); 1 . 95 ( s , 3h ); 0 . 83 ( s , 9h ). 9 - 25 [ 2 -( 4 - acetylamino - ( 400 mhz , d 6 - dmso ): phenyl )- 1h - δ = 11 . 92 ( s , 1h ); 10 . 07 ( s , 1h ); pyrrolo [ 2 , 3 - 9 . 53 ( broad s ; 1h ); b ] pyridin - 5 - yl ]- 8 . 19 ( broad s , 1h ); 8 . 02 ( broad s , carbamic acid 2 , 2 - 1h ); 7 . 83 ( d , 2h ); 7 . 65 ( d , dimethyl - propyl 2h ); 6 . 78 ( s , 1h ); 3 . 81 ( s , ester 2h ); 2 . 06 ( s , 3h ); 0 . 96 ( s , 9h ). 9 - 26 [ 2 -( 3 - acetylamino - ( 400 mhz , d 6 - dmso ): phenyl )- 1h - δ = 11 . 87 ( s , 1h ); 9 . 89 ( broad s ; pyrrolo [ 2 , 3 - 1h ); 9 . 42 ( broad s , 1h ); b ] pyridin - 5 - yl ]- 8 . 05 ( broad s , 1h ); carbamic acid ethyl 7 . 90 ( broad s , 2h ); 7 . 41 ( d , 1h ); ester 7 . 37 ( d , 1h ); 7 . 22 ( t , 1h ); 6 . 57 ( s , 1h ); 3 . 98 ( q , 2h ); 1 . 92 ( s , 3h ); 1 . 11 ( t , 3h ). 9 - 27 [ 2 -( 3 - acetylamino - ( 400 mhz , d 6 - dmso ): phenyl )- 1h - δ = 12 . 05 ( s , 1h ); 10 . 05 ( broad pyrrolo [ 2 , 3 - s ; 1h ); 9 . 70 ( broad s , 1h ); b ] pyridin - 5 - yl ]- 8 . 22 ( broad s , 1h ); carbamic acid allyl 8 . 07 ( broad s , 2h ); 7 . 56 ( t , 2h ); ester 7 . 39 ( t , 1h ); 6 . 74 ( s , 1h ); 6 . 03 ( m , 1h ); 5 . 39 ( d , 1h ); 5 . 26 ( d , 1h ); 4 . 64 ( d , 2h ); 2 . 09 ( s , 3h ). 9 - 28 [ 2 -( 3 - acetylamino - ( 400 mhz , d 6 - dmso ): phenyl )- 1h - δ = 12 . 03 ( s , 1h ); 10 . 05 ( broad pyrrolo [ 2 , 3 - s ; 1h ); 9 . 59 ( broad s , 1h ); b ] pyridin - 5 - yl ]- 8 . 22 ( broad s , 1h ); carbamic acid 8 . 07 ( broad s , 2h ); 7 . 57 ( t , 2h ); isobutyl ester 7 . 39 ( t , 1h ); 6 . 73 ( s , 1h ); 3 . 90 ( d , 2h ); 2 . 09 ( s , 3h ); 1 . 98 m , 1h ); 0 . 96 ( d , 6h ). 1 . 00 g 2 , 3 - diamino - 5 - nitro - pyridine and 0 . 95 g 3 , 4 - difluorobenzaldehyde were stirred in 60 ml nitrobenzene at 160 ° c . for 26 hrs . the solvent was removed under vacuum and the residue dissolved in 40 ml pyridine at 60 ° c . the solution was cooled in an ice bath . precipitated product was isolated by filtration and dried to yield 0 . 5 g of the title product . 60 mg of the above nitro compound were hydrogenated for 2 hrs at room temperature in a mixture of 15 ml methanol and 15 ml thf over palladium on charcoal . the catalyst was filtered off and the filtrate evaporated to give 56 mg of the title compound , which was used directly in the next reaction step . 50 mg ( 0 . 16 mmol ) of the above amino compound in 1 ml dry nmp were treated at room temperature dropwise with 0 . 16 ml ( 0 . 16 mmol ) of a 1m solution of isopropyl chloroformate in toluene . after stirring for 3 hrs the solvents were removed under vacuum and the residue purified by preparative hplc / ms , yielding 30 mg of the title product . 1 h - nmr ( 400 mhz , d 6 - dmso ): δ = 9 . 87 ( broad s ) and 9 . 74 ( broad s , together 1h ); 8 . 38 ( s , 1h ); 8 . 20 ( m , 2h ); 8 . 04 ( broad d , th ); 7 . 67 ( q , 1h ); 4 . 94 ( m , th ); 1 . 29 ( d , 6h ). 0 . 5 g 2 -( 3 , 4 - difluoro - phenyl )- 6 - nitro - 3h - imidazo [ 4 , 5 - b ] pyridine , 0 . 1 ml nmp and 0 . 51 g bis ( 2 - methoxyethyl )- amine were heated to 170 ° c . with stirring for 18 hrs . volatile materials were removed under vacuum and the residue purified by chromatography , first on silica in dichloromethane / methanol mixtures , and subsequently by preparative hplc . the above nitro compound was hydrogenated to the amino compound and subsequently reacted with isopropyl chloroformate as described for 10 - 1 to give the title product . 1 h - nmr ( 400 mhz , cd 3 od ): δ = 8 . 27 ( broad s , 2h ); 7 . 79 ( m , 2h ); 7 . 14 ( t , th ); 5 . 02 ( m , 1h ); 3 . 61 ( m , 8h ); 3 . 35 ( s , not separated from meoh ); 1 . 35 ( d , 6h ). was prepared starting from 3 - carboxybenzaldehyde and 2 , 3 - diamino - 5 - nitropyridine as described for 10 - 1 . in the final step , after reacting with isopropyl chloroformate in nmp , the reaction mixture was treated with 100 mg sodium hydroxide and 1 ml water for 1 hr at room temperature . the crude product was precipitated by addition of 30 ml water and filtered off . it was further purified by dissolving in 50 ml aqueous sodium carbonate solution and washing with dichloromethane . the carbonate solution was acidified to ph 2 - 3 by addition acetic acid and hcl , and extracted with dichloromethane . the dichloromethane phase was evaporated to give 61 mg of the title product . 1 h - nmr ( 400 mhz , d 6 - dmso ): δ = 13 . 50 ( broad s , 1h ); 9 . 76 ( broad s , 1h ); 8 . 84 ( s , 1h ); 8 . 37 ( s ) and 8 . 33 ( d , together 2h ); 8 . 21 ( s , 1h ); 8 . 05 ( d , 1h ); 7 . 60 ( t , 1h ); 4 . 94 ( m , 1h ); 1 . 29 ( d , 6h ). 25 mg ( 0 . 07 mmol ) of the acid from example 11 - 1 in 1 ml dry dmf were treated with 18 mg ( 0 . 11 mmol ) 1 , 1 ′- carbonyl - diimidazole at room temperature for 2 hrs . 13 mg ( 0 . 11 mmol ) 2 - amino - 1 , 3 - dimethoxypropan were added and stirring was continued for 4 hrs . the solvent was removed under vacuum , the residue dissolved in dichloromethane and washed with aqueous sodium carbonate solution . the dichloromethane phase was evaporated and the residue purified by chromatography on silica in dichloromethane / methanol mixtures . 1 h - nmr ( 400 mhz , d 6 - dmso ): δ = 9 . 80 ( broad s , 1h ); 8 . 67 ( s , 1h ); 8 . 49 ( broad s , 1h ); 8 . 38 ( s , 1h ); 8 . 29 ( d , 1h ); 8 . 20 ( s , 1h ); 7 . 98 ( d , 1h ); 7 . 66 ( t , 1h ); 4 . 95 ( m , 1h ); 4 . 35 ( m , 1h ); 3 . 49 ( m , 4h ); 3 . 29 ( s , not separated from h 2 o ); 1 . 29 ( d , 6h ). 1 h - nmr ( 400 mhz , d 6 - dmso ): δ = 13 . 12 ( broad s ) and 12 . 00 ( broad s , together 1h ); 9 . 78 ( broad s , 1h ); 8 . 66 ( broad s , 2h ); 8 . 38 ( s , 1h ); 8 . 29 ( d , 1h ); 8 . 20 ( s , 1h ); 7 . 95 ( d , 1h ); 7 . 65 ( t , 1h ); 4 . 95 ( m , 1h ); 3 . 41 - 3 . 30 ( t and m , not separated from h 2 o ); 3 . 26 ( s , 3h ); 1 . 80 ( m , 2h ); 1 . 29 ( d , 6h ). was prepared as described for example 4 - 1 , starting from 2 - chloropyridine - 4 - carboxylic acid and 2 , 3 - diamino - 5 - nitropyridine . was prepared by reduction of the above nitro compound with iron powder as described for example 1 - 1 . was prepared from the above amino compound and isopropyl chloroformate as described for example 10 - 1 . 1 h - nmr ( 400 mhz , d 6 - dmso ): δ = 13 . 90 ( broad s ) and 12 . 43 ( broad s , together 1h ); 9 . 95 ( broad s ) and 9 . 81 ( broad s , together 1h ); 8 . 61 ( s , 2h ); 8 . 46 ( s , 1h ); 8 . 27 ( s , 1h ); 8 . 18 ( broad s ( and 8 . 12 ( broad s , together 1h ); 4 . 95 ( m , 1h ); 1 . 29 ( d , 6h ). 1 . 20 g ( 4 . 35 mmol ) 2 -( 2 - chloro - pyridin - 4 - yl )- 6 - nitro - 3h - imidazo [ 4 , 5 - b ] pyridine in 12 ml dry nmp and 1 . 18 g ( 13 mmol ) 3 - methoxypropylamine were heated to 200 ° c . in a closed vessel in a microwave reactor for 30 min . the solvent was removed under vacuum and the residue dissolved in a mixture of 20 ml ethyl acetate and 30 ml 5 % aqueous hcl . the hcl phase was separated and brought to alkaline ph by addition of conc . ammonia . the alkaline aqueous phase was extracted with dichloromethane , and the organic phases were combined and dried . evaporation and chromatography of the residue on silica in ethyl acetate / methanol mixtures gave 480 mg of the title product . the above nitro compound was reduced with iron powder as described in example 1 - 1 and purified by chromatography on silica in ethyl acetate / methanol mixtures . yield 360 mg of the title product { 2 -[ 2 -( 3 - methoxy - propylamino )- pyridin - 4 - yl ]- 3h - imidazo [ 4 , 5 - b ] pyridin - 6 - yl }- carbamic acid isopropyl ester 170 mg ( 0 . 57 mmol ) of the above amino compound were dissolved in 3 ml nmp and treated at 0 ° c . with 0 . 855 ml of a 1m solution ( 0 . 85 mmol ) of isopropyl chloroformate in toluene . stirring was continued at room temperature for 2 hrs , then methanol and a few ml of conc . ammonia were added and the mixture was stirred for another hr . evaporation and chromatography on silica in ethyl acetate / methanol mixtures gave 88 mg of the title product . 1 h - nmr ( 400 mhz , d 6 - dmso ): δ = 13 . 59 ( s ) and 13 . 08 ( s , together th ); 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