PROCEDURE FOR THE PRODUCTION OF NEW BENZIMIDAZOL-2 - DERIVATIVES AND YOUR SALTS

The invention concerns a procedure for the production of new Benzimidazol-2-derivate of the formula N R, - X-pH CR \ n R2 (D where R veresterte or amidierte a if necessary Carboxygruppe or or a veresterte Bydroxymethylgruppe verätherte if necessary is, R, an aliphatic, cyclo-aliphatic, aromatic, araliphatic, hetero-cyclic or heterccyclisch aliphatfschen remainder represents, R2 for hydrogen or an aliphatic remainder stands, and pH the remainder of R, - X containing 1,2-Phenylengruppe represents, X Niederalkyliden or a direct connection means, and pharmaceutical usable salts of connections of the formula (I) with salt-forming characteristics, under the condition that B - X-pH ven in 4und/oder 5-Stellung by methyl substituiertern 1,2-Phenylen is different, if R Carbexy, Carbamyl or Hydroxymethyl represents and H2 hydrogen meant, and procedures for their production. The invention concerns for example a procedure for the production of connections of the formula (I), where R, RL, und' R the indicated meanings have and either X Methylen meant pH, whereby Ri exhibits at least 2 Eehlenstoffatome, if pH is otherwise uasubstituiert, R2 ethyl meant and R represents Acetoxymethyl, or a direct connection means X, whereby R exhibits at least 2 Kohlensteffatome, if pH iat otherwise unsubstituiert, and R - X-pH of 1,2-Phenylen substituted in 4und/oder S-position by methyl is different, if R Carboxy, Carbamyl or Hydroxymethyl and B2 hydrogen means, and salts of such connections with salt-forming characteristics, procedures for its production, these containing pharmaceutical preparations and their Use as drugs. In connection with the available description contained with “down” designated organic remainders and compounds in particular to and with 7, preferably to and with 4 Kohlenstoffatemen. In verestertem Carboxy and veräthertem Hydroxymethyl R the verätherte Hydrexygruppe means for example one by an aliphatic or araliphatic remainder, like an aliphatic or araliphatic hydrocarbon remainder substituted if necessary, verätherte hydroxy group, e.g. appropriate Niederalkoxy or Phenylniederalkoxy. Substituents of Niederalkoxy are among other things Hydroxy, Niederalkexy and/or Diniederalkylamino, and such from Phenylaiederalkoxy, e.g. Niederalkyl, Niederalkoxy and/or halogen, whereby one or more Substitueaten can be present. In amidiertem Carboxy the amino group means menosubstituiertes by Niederalkyl more menooder disubstituiertes or by Niederalkylen disubstituiertes Amino for example if necessary by Hydroxy. In verestertem Hydroxymethyl R the veresterte hydroxy group means verestertes Hydroxy, e.g. appropriate Niederalkanoyloxy for example with a carbonic acid, like an aliphatic or aromatic carbonic acid or if necessary by Niederalkyl, Niedezalkoxy and/or resounding gene substituted Benzoyloxy. Niederalkanoyloxy is e.g. Acetoxy, Propionyloxy, Butyryloxy, Isobutyryloxy, Valeroyloxy, Caproyloxy or Pivaloyloxy. Aliphatic, cyclcaliphatische, aromatic and araliphatic remainders of R and/or R2 are primarily if necessary substituted aliphatic, cyclo-aliphatic, aromatic or araliphatic throat hydrogen remainders, like appropriate Niederalkyl, Niederalkenyl, Cyclealkyl, Phenyl, Naphthyl or Phenylniederalkyl. Substituents are e.g. Hydrexy, Niederalkoxy, Niederalkyloder Phenylthio, Niederalkanoder Benzolsulfinyl, or Niederalkanoder benzene sulphonyl, in particular ven Niederalkyl R as well as Niederalkyl R2, furthermore Niederalkyl, Niederalkoxy and/or halogen, in particular from Phenyl or Phenylniederalkyl R z. Heterocyclyl in a hetero-cyclic or hetero-cyclic-aliphatic remainder of R, is primarily monocyclisches Heterocyclyl of an aromatic character with a Heteroatom, like oxygen, sulfur or nitrogen, as ring member, like Furyl, Thienyl or Pyridyl. In an hetero-cyclic-aliphatic remainder of R, the aliphatic part is e.g. an appropriate aliphatic hydrocarbon remainder, in particular Niederalkyl. Niederalkyliden X is for example Methylen. Except by the remainder of R, - X can be 1,2-Phenylen additionally, among other things by Niederalkyl, Niederalkoxy, Hydroxy and/or Balogen, simple or several times substituted. Niederalkoxy meant e.g. Methoxy, Äthoxy, n-Propyloxy, Isopropyloxy, n-Butyloxy, Isobutyloxy, tert. Butyloxy, I0 n-Pentyloxy or n-Hexyloxy. Phenylniederalkoxy is e.g. Benzyloxy or ioder 2-Pheny [äthoxy. Hydraulic XY, Niederalkoxybzw. Diniederalkylaminoniederalkoxy is in particular 2und/oder 3-Hydroxy-niederalkoxy, e.g. 2-Hydroxyäthoxy, 3-Hydroxypropyloxy or 2,3-Dihydroxy-propyloxy, as well as 2oder 3-Niederalkoxy-uiederalkoxy, e.g. 2-Methoxyäthoxy, 2thoxyäthoxy or 3-Methoxypropyloxy, and/or Diniederalkylaminoniederalkoxy, e.g. Dimethylamino or Diäthylaminoäthoxy. Niederalkyl is e.g. methyl, ethyl, n-Propyl, Isopropyl, n-butyl, Isobutyl, tert. Butyl, n-Pentyl, n-Hexyl or n-Heptyl. In particular halogen with atomic number to and with 35, i.e. fluorine, chlorine or bromine is halogeneous. Niederalkylen is e.g. 1,4-Butylen, 1,5-Pentylen or 1,6-Hexylen. Niederalkenyl is e.g. Vinyl, 1-Methyl-vinyl, 1-Äthyl-viny [, allyl, 2oder 3-Methyl-allyl or 3,3-Dimethyl-allyl. Cycloalkyl preferably contains 3 to 8 ring atoms and is e.g. Cyolopropyl, Cyclopeutyl, cyclohexyl, Cycloheptyl or Cycloootyl. Niederalkylthio is e.g. MethyIthio or Äthylthio, while Niederalkansulfinyl and " Niederalkansulfonyl e.g. Methansulfinyl, Äthansulfinyl, Methansulfony [or thansulfonyl mean. By Niederalkylthio, Niederalkansulfinyl or Niederalkansulfonyl substituted Niederalkyl is e.g. Methylthiooder Äthylthiomethyl, Ioder 2-Methylthiooder blazes to 2thylthioäthyl, or 2oder 3-Methylthiooder 2oder 3-Äthylthiopropyl, Methansulfinyloder thansuIfinylmethyl, ioder 2-Methansulfonyloder Ioder 2-Äthansulfonyl-äthyl, or 2oder 3-Methansulfonyl or 2oder 3-Äthansulfonylpropyl. By Phenylthio, Benzolsulfinyl or benzene sulphonyl substituted Niederalkyl is e.g. Phenylthio, 'Benzolsulfinyloder benzene sulphonyl methyl, or 1oder 2-Phenylthio, ioder 2-Benzolsulfinyl, or ioder 2-Benzo [sulphonyl ethyl. Phenylniederalkyl is e.g. benzyle, 1oder 2-Phenyläthyl or i, 2oder 3-Phenylpropyl. Furyl is e.g. 2-Furyl, and Thienyl 2-Thienyl, during Pyridyl 2, 3oder 4-Pyridyl to e.g. be can. Furylniederalkyl, Thienylniederalkyl and Pyridylniederalkyl are in particular according to substituted methyl remainders, like Furfuryl, 2-Thienyl or Picolyl, e.g. 2oder 4-Pyridylmethyl. Salts are e.g. such from connections of the formula (1), where R stands for Carboxy, with bases. Such salts are in particular pharmaceutical usable, not-toxic salts, like Alkalimetalloder alkaline earth metal, e.g. sodium, potassium, Magnesiumoder of calcium salts, furthermore ammonium salts with ammonia or amines, like Niederalkylaminen, e.g. tri methyl amine or tri ethyl amine, or mineral-sour salts of connections of the formula (1) with basic Seitenkette, e.g. appropriate hydraulic halides, like - chloride. The new connections show valuable pharmakologische characteristics. In particular they exhibit antiallergische effects, e.g. at the rat in doses method descriptive from approximately 10 to for instance i00 mg/kg with oral administration in the passive cutaneous Anaphylaxie test (PCA reaction), that similar to from Goose and Blair, Immunology, Bd.16, 3,749 (1969), are accomplished, to be proven to be able, whereby the passive cutaneous after Anaphylaxie of Ovary, Prog. S0 Allergy, Bd.5, S.459 (1958) is produced, descriptive procedures. The antiallergische, in particular the degranulationshemmende, effect can in one in vitro attempt also on the basis the histamine release from Peritonealzellen of the rat during immunologically induced release (whereby e.g. with Nippostrongylus brasiliensis infestierte Batten is used) and during chemically induced release (whereby this is caused e.g. with one polymer of N-4-Methoxy-phenyläthyl-N-methyl - amine) to be determined. Those connections erhRltliohen according to invention are therefore as if asthma restrains from allergischen reactions, e.g. in the treatment and Prophyla×e of allergischen illnesses, like asthma, both extrinsic and intrinsic, or other allergy schen illnesses, like allergischer Rhinitis, e.g. Heufieher, Konjunktivitis, or allergischer Dermatitis, e.g. Urticaria or Ekzeme, usable. Invention concerns in particular procedures for production of connections formula (I), where R for free Garboxy or Hydroxymethyl, as if Hydro×ygruppe Niederalkoxy, Hydroxyniederalkoxy, Niederalkoxyniederalkoxy or DiniederaIkylaminoniederalkoxy exhibiting verestertes Garboxy or veräthertes Hydroxymethyl, when amino group Amino, Hydroxyamino, Niederalkytamino, Diniederalkylamino or Niederalkylenamino exhibiting amidiertes Carboxy stands if necessary or as veresterte hydroxy group NiederalkanoyIoxy or by Niederalkyl, Niederalkoxy and/or halogen substituted Bonzoyloxy exhibiting verestertes Hydrexymethyl, verätherte R if necessary by Niederalkoxy, Niederalkylthio, Niederalkansulfinyl, Niederalkansulfonyl, Phenylthio, Benzolsulfinyl or benzene sulphonyl substituted Niederalkyl, Niederalkenyl, Cyaloalkyl, if necessary in the Phenylteil through b/iederalkyl, Niederalkoxy or halogen substituted Phenyl or Phenylniederalkyl, Furyl, Thienyl or Pyridyl, or Furylniederalkyl, Thenylniederalkyl or Pyridylniederalkyl meant, X Methylen meant, R2 hydrogen or Niederalkyl represents, and pH for the remainder of R - Xenthaltende and by Niederalkyl, Niederalkoxy, Hydroxy and/or halogen substituted 1,2-Phenylen stands if necessary, e.g. such, in which Bz exhibits at least 2 carbon atoms, if pH is otherwise unsuhstituiert, represents R2 ethyl meant and 1 Acetoxymethyl, and pharmaceutical usable-salts the connections mentioned, where B stands for Carboxy. The invention concerns in particular a procedure for the production of connections the formula (1), where R for free Carboxy, as if verätherte hydroxy group Niederalkoxy or Hydroxyniederalkoxy with to and with 4 carbon atoms, e.g. Methoxy, Äthoxy, 2-Hydroxyäthoxy or 2,3 - - Dihydroxypropyloxy, exhibiting verestertes Carboxy, or as amino group Amino or Hydroxyamino, Niederalkylamino or Diniederalkylamino, where Niederalkylbis contains and with 4 Kohlonstoffatome, e.g. Methylamino, thylamino, Dimethylamino or Diäthylamino, exhibiting amidiertes Garboxy stands or Hydroxymethyl, as if hydroxy group Niederalkoxy with up to 4 carbon atoms, e.g. Methoxy or Äthoxy, or Diniederalkylaminoniederalkoxy with in each case verätherte up to 4 carbon atoms in Alkylbzw. Alkoxyteil, like Dimethylaminoäthoxy, exhibiting veräthertes Hydroxymethyl or as veresterte hydroxy group Niederalkanoyloxy with up to 7 carbon atoms, e.g. Aeetoxy, Propionyloxy or Pivaleyloxy, or if necessary by Niederalkyl, e.g. methyl, Niederalkoxy, e.g. Methoxy, and/or halogen, e.g. chlorine, substituted Benzoyloxy exhibiting 3s veresterte Hydroxymethyl meant, R Niederalkyl with to and with 7 carbon atoms, e.g. methyl, ethyl, n-Propyl, Isopropyl, n-butyl, Isobutyl, tert. Butyl, n-Pentyl, Neopentyl, n-Hexyl or n-Heptyl, Niederalkoxy, Niederalkylthio, Niederalkansulfinyloder Niederalkansulfonyl niederalkyl, where the individual Niederalkylreste to and with 4 contains carbon atoms, e.g. Methoxy, Xthoxy, Methylthio, Äthylthio, Methansulfinyl, Äthansulfinyl, Methansulfonyl or thansulfonylmethyl, 1oder 2-Methoxy, 1oder 2-Äthoxy, Ioder 2-Methylthio, Ioder 2thylthio, ioder 2-Methansulfinyl, Ioder 2thansulfinyl, 1oder 2-Methansulfonyloder 1oder 2-Äthansulfonyläthyl, or i, 2oder 3-Methoxy, i, 2oder 3thoxy, 1, 2oder 3-Methylthio, l, 2oder.q-Äthylthio, 1, 2oder 3-Methansulfinyl, i, 2oder 3thansulfinyl, 1, 2oder 3-Methansulfonyloder 1, 2oder 8thansulfonylpropyl, Phenylthio, Benzolsulfinyl4s or benzene sulphonyl leather alkyl, where the Niederalkylrest to and with 4 I (ehlenstoffatome, e.g. Phenylthio, Benzolsulfinyloder benzene sulphonyl methyl, Ioder 2-Phenylthio, Ioder 2-Benzolsulfinyloder 1oder 2-Benzolsulfonyläthyl, or i, 2oder 3-Phenylthio, 1, 2oder contains • q-Benzolsulfinyloder i, 2oder 3-Benzolsulfonylpropyl, Niederalkenyl m [t to and with 5 carbon atoms, e.g. 1-Methyloder l-ethyl-vinyl or allyl, Gyoloalkyl with to and with 7 Kohlenstoffso flavours, e.g. Cyclopropyl or Gyclohexyl, giving skin by Niederalkyl with to and with 4 carbon atoms, e.g. methyl, Niederalkoxy with to and with 4 carbon atoms, e.g. Methoxy, and/or halogen with atomic number to and with 35, e.g., chlorine or bromine, substituted Phenyl or Phenylniederalkyl with to and with 4 carbon atoms in the Niederalkylrsst, e.g. Bsnzyl or Ioder 2-Phenyläthyl, Furyl, Thienyl or Pyridyl, e.g. 2-Furyl, 2-Thlenyl or 2, 3oder 4-Pyridyl, or Furyl, Thienyloder Pyridyl niederalkylmit to and with 4 carbon atoms in the Niederalkylrest, e.g. Furfuryl, 2-Thlenyl or 2oder 4-Picolyl, meant, X Methylen , if R= means hydrogen or Niederalkyl with to and with 4 carbon atoms, e.g. methyl, represents, and pH that the remainder of the formula R, - Xenthaltende, if necessary by Niederalkyl with to and along 4 carbon atoms, e.g. methyl, Niederalkoxy with up to and with 4 carbon atoms, e.g. Methoxy, Hydroxy and/or halogen with atomic number to and with 35, e.g. chlorine or bromine, substituted 1,2-Phenylen represents, how the remainder of the formula R, - Xirgendeine for substitution suitable position, preferably the 4oder 5-Ste! lung the 1,2-Phenylenrestes, e.g. such takes, in which ton of R exhibits, at least 2 carbon atoms, if pH is otherwise unsubstituiert, R= ethyl meant and R represents Acetoxymethyl, and pharmaceutical usable salts of the connections mentioned. where R stands for Carboxy. The invention concerns primarily a procedure for the production of connections of the formula DL-x,--Left C-n, R3 R' (la) where R' stands on the one hand primarily for Carboxy or furthermore for as verätherte Bydroxygruppe Niederalkoxy with to and with 4 carbon atoms, e.g. Methoxy or Äthoxy, exhibiting verestertes Carboxy and on the other hand primarily Hydroxymethyl verätherte or furthermore than Ilydroxygruppe Niederalkoxy with up to 4 carbon atoms, e.g. Methoxy or Äthoxy, exhibiting veräthertes Hydroxymethyl represents, and where R [Niederalkyl with to and tert with 7 carbon atoms, e.g. methyl, ethyl, n-Propyl, n-butyl. Butyl, Cyeloalkyl with to and with 6 ring carbon atoms, e.g. Cyelopropyl or cyclohexyl or Phenyl represents. X' Methylen meant, R' for hydrogen or Niederalkyl with up to 4 carbon flavour, e.g. methyl, stands, and R3 hydrogen, Niederalkyl with to and with 4 carbon atoms, e.g. methyl, Niederalkoxy with to and with 4 carbon atoms, e.g. Methoxy, or halogen with atomic number to and with 35, e.g. chlorine, means, whereby the remainder of the formula R - X' and the group of R3, if this from hydrogen is different, preferably the 5und the 6-Stellung of the Benzimidazo [ring take, and pharmaceutical usable salts of connections of the formula (Ia), in which R' for Carbox stands, with bases. The invention concerns primarily connections of the formula (Ia), where R' for Carboxy or for as verätherte hydroxy group Niederalkoxy with to and with 4 carbon atoms, e.g. Methoxy or thoxy, exhibiting verestertes Carboxy stands, and where R - X' Niederalkylmlt 2 to 7 carbon atoms, e.g. ethyl, n-Propyl, Isopropyl, n-butyl, n-Pentyl or n-Hexyl, Cycloalkylmethyl with to and with 6 ring Kohl material atoms, e.g. meant Cyclopropyloder Cyelohexylmethyl, or benzyle, for R' for hydrogen or in particular for Niederalkyl with to and with 4 carbon atoms, e.g. methyl stands, R, hydrogen or Niederalkyl with up to 4 carbon atoms, e.g. methyl, Niederalkoxy with to and with 4 carbon atoms, e.g. Methoxy, or halogen with atomic number to and with 35, e.g. chlorine, means, whereby the remainders of R - X' and R preferably dis 5bzw. 6-Stellung of the Benzimidazolringes take, and pharmaceutical usable salts of connections of the formula (Ia), in which R' for Carboxy stand, with bases as drug, these containing pharmaceutical preparations, their use as drugs as well as connections of the formula (Ia). The invention concerns in all first line a procedure for the production of connections of the formula (Ia), where R' Carboxy, Hydroxymethyl or Niederalkoxycarbonyl or Niederalkoxymethyl with altogether up to 5 carbon atoms, e.g. Methoxy or Äthoxycarbonyl or methyl, means, R' X' Niederalkyl with up to 8, for example with up to 5, carbon atoms, e.g. Methyl, ethyl, n-Propyl, Isepropyl, n-butyl, Isobuty] or n-Pentyl, meant and R' and RA independently hydrogen or Niederalkyl with up to 4 carbon atoms, like methyl, represent, and pharmaceutical usable salts of connections of the formula (Ia), in which R' for Carboxy stand, with which condition that a group of methyls of R - X' not the 5 (6) - position of the Benzlmidazolringes takes, if R hydrogen or in 6 [5) - position bound methyl is, R' hydrogen and R' Carboxy or Hydroxymethyl represents. The invention e.g. concerns connections of the formula (Ia) in all first line, where R' stands either for Carboxy or for Niederalkoxycarbonyl with altogether up to 5 carbon atoms, like Methoxyoder Äthoxycarbonyl, and where R - represents X' Niederalkylmit to and with 7 carbon atoms, e.g. methyl, ethyl, n-Propyl, Isopropyl, n-butyl, n-Pentyl or n-Hexyl, and represent R' and R3 Niederalkyl with to and with 4 carbon atoms, e.g. methyl, whereby the remainder of R - X' the 5und of the Niederalkylrest R-S the 6-Stellung of the Benzimidazolringes takes, and salts of such connections, in which R' Carboxy is. The invention concerns a procedure for the production of connections of the formula (Ia), where R' for Carboxy stands, R' Niederalkylmit up to 7, e.g. with up to 4, carbon atoms, like methyl, in all first line furthermore ethyl, n-Propyl, Isopropyl or n-butyl, represents, meant, Rä for hydrogen and R-S hydrogen or Niederalkyl with up to 4 carbon atoms, like methyl, stands for X' Methylen represents, whereby the remainder of R - X' the 5und a Niederalkylrest R3 the 8-Stellung of the Benzimidazolringes takes, as well as procedures for their production, which connections mentioned and pharmaceutical usable salts of such connections, in which Rr Carhoxy means. The invention concerns in particular a procedure for the production of the connections of the formula (I) specified in the examples. The new connections can be manufactured in actually well-known way. So one can e.g. receive it, by one a connection of the formula NH-X, R, - X-pH, (IL) NX ONE 2 1 R2 where one of the remainders of X, and X2 a group of the formula - C (=O) - R and the other hydrogen mean, or a salt of it cyolisiert, and if desired, a so available connection into another connection of the formula (1) and/or a received free salzbiidende connection into a salt or a received salt converts into the free connection or into another salt transferred. When salts of basic materials of the formula [II) for example acid addition salts, like hydraulic halides, come e.g. the hydrochlorides, from connections, in which R if necessary means veräthertes or verestertes Hydroxymethyl, and/or Alkalimetalloder of ammonium salts, e.g. sodium salts, from connections, in which R Carboxy means, into consideration. The Cyclisierung takes place in usual way, with more normal or in particular for the production of connections, in which R means veräthertes Hydroxymethyl if necessary, increased temperature, e.g. with approximately 50 to for instance IB0°C, particularly with approximately 110 to 1400C, if required in present one drinks condensation means, like a hydrogen halide acid, e.g. from hydrochloric acid, and/or a water-binding means, e.g. from DicycIohexylcarbodiimid, and favourably under inert gas, e.g. under nitrogen. The understanding procedure variant is in particular suitable for the production of connections of the formula (1) meant in those R if necessary veräthertes Hydroxymethyl, which afterwards comfortably in usual way into other connections of the formula (I) to be transferred can. The basic materials of the formula (IL) are appropriately manufactured in situ, for example by one an appropriate 1,2-Phenylendiamin, which by the remainder of R - Xsubstituiert is and if necessary still further substituents contained can, i.e. a connection of the formula (IIa) or an acid addition salt a reactive derivative, preferably esters, suitable of it, e.g. its hydrochloride, with an acid of the formula R-COOH (IIb) or, like Niederalkylester, amide, anhydride, like Säurehalogenid, Iminoäther, like Iminoniederalkyläther or Iminoester, like Iminochlorid, of it, e.g. with the preferably verätherten glycol acid or with Chlorbzw. Bromine oxalic acid ethyl ester, converts, if required in presence of a Lösungsoder of diluent, like a Niederalkanols, e.g. from methanol or Äthanel, and/or under warming up to approximately to for instance 160°C, e.g. on for instance ll0 to for instance 140°C. The 1,2-Phenylendiamine which can be used for it as basic materials knows for example by usual reduction, e.g. conversion with a chemical reducing agent “like sodium dithionite, or with been suitable activated hydrogen, like by a precious metal catalyst in basic environment, e.g. by Raney nickel in ethanol or ethanol, catalytically activated hydrogen, which will receive appropriate 1,2-Nitranilin-Verbindung. In a modification of this method one knows also this 1,2-Nitranilin-Zwischenprodukt with the acid, e.g. with Glykoloder oxalic acid, mentioned above, or with a suitable derivative of it, e.g. with a Äthoxyessigsäureoder chlorine oxalic acid down alkyl esters, convert ünd afterwards the Nitrogruppe, e.g. with hydrogen in presence of Baney nickel, to reduce. The 1.2-Nitranilinverbindungen which can be used for the production of the basic materials of the formula (IL) can be manufactured, if it does not admit is, e.g. on the basis of the appropriate Chlorb8nzolen the formula H-PhH-CI, by replacing these in usual way, e.g. with conversion with a connection of the formula R, - X-Hal or R - X-OH and/or with an appropriate alkene or Cyeloalken to presence of aluminum chloride, which so available connection of the formula R, - and the so available chlorine nitro compound of the formula blank-X-pH (Cl) nitrates X-PhH-CI with nitric acid/Sohwefelsäure - NOz with ammonia or an amine of the formula RzNHz converts. A preferential execution form of the managing described procedure consists of that one a connection of the formula /NH2 R, - X-pH-- NHRz (IIa) with an acid of the formula R-COOH (IIb) or a suitable functional derivative of it converts, and if desired, a so available connection into another connection of the formula (1) and/or received free salt screen end converts a connection into a salt or a received salt into the free connection or into another salt transferred. Suitable ones functional derivatives of acids of the formula (llb) e.g. are thereby their ester, like Niederalkylester, amides or anhydrides, like Säurehalogenide. As acids of the Formol (IIb) and their functional derivatives which can be used in the managing procedure variant for example the glycol acid and Chlorbzw verätherte if necessary come. Bromine oxalic acid ethyl ester in consideration. The conversion takes place in particular in presence of a Lösungsoder of diluent, like a Niederalkanols, e.g. from methanol or ethanol, if required under warming up to approximately 50 to 16O°C, e.g. on approximately 110 to for instance 140°C. Available a according to invention connection of the formula (I) can in actually well-known way into another connection the formula (I) umge changes become. So one can in a connection of the formula (I), where R stands for Carboxy, this in actually well-known ester procedures into a veresterte Carboxygruppe to convert. So one knows N, N-Dimethylform e.g. by treating with a suitable Diazoverbindung, like a Diazoniederalkan, with a suitable N, N-Diniederalkylformamidacetal, e.g. amiddiäthylaeetal or N, N-dimethylformamide-methosulfat, or a Oxoniumsalz, how with a Trinlederalkyloxonlum - tetrafluoroborat or - hexafluorophosphat, with a carbonate or a Pyrocarbonat, e.g. with Diäthyl (pyro) like Diniederalkylsulfit or Triniederalkylphosphit, in presence of a suitable drink carbonate, or with organic sulfite or Phosphlt, means, like p-Toluolsulfonsäure, or with an alcohol in presence of a suitable Kandensationsmittels, like a dehydratisierenden means, e.g. Dicyclohexylcarbodiimid, or, for the formation of a Hydroxyniederalkylgruppe, with a Epoxyniederalkan, e.g. thylenoxyd, esters. Furthermore one knows a connection of the formula (I}, where a free group of carboxyls of R in Salzform, e.g. in the alkali metal, is present like sodium salt form, with a reactive ester of an alcohol, e.g. with a strong acid, like an appropriate halide, e.g. chloride, a bromide or an iodide, or Sehwefelsäureester, or a connection of the formula (I), where a free group of carboxyls of R in an anhydride form, preferably as Halogenoarbonyl, is present e.g. Chlorcarbonylgruppe, which one e.g. by treating a connection of the formula (I), where R stands for Carboxy, with a Balogenierungsmittel, e.g. Thionylohlorid, to form, with a metal alcoholate or an alcohol in presence of one can convert acid-binding base, and in such a way to a connection of the formula (I} arrive where for verestertes Carboxy stands for R. If necessary “existing substituents in functionally modified form can be present and then in a connection of the formula in a ester reagent (I), where R stands e.g. for substituted Niederalkoxyaarbonyl, in which substituent in functionally modified form it is present, to be set free. So one can e.g. use the 2,3-Epoxy-propylchlorid as ester reagent and later hydrolyze in the received ester a 2,3-Epoxy-propyloxygruppierung R to the desired 2,3-Dihydroxy-propyloxygruppierung. In a connection of the formula (I), where R for verestertes Carboxy, e.g. also p-Nitrobzw. 2,4-Dinitrophenoxyoder - benzyloxycarbonyl, can this stands by transesterification, e.g. by treating with an alcohol, if required into presence of a suitable transesterification catalyst, like an alkali metal, e.g. Natriumoder of potassium alkanolate, substituted if necessary, into another veresterte Carboxygruppe being converted. In a received connection of the formula (I), where R stands for free, anhydridisiertes or verestertes Carboxy, this can be converted into actually well-known way furthermore into Carbamyl substituted if necessary. So one knows a connection of the formula (I), where a group of carboxyls of R in an anhydride form, in particular as Halogencarbonyl, Chlorcarbonylgruppe, or in veresterter form is e.g. present, with ammonia, Hydroxylamin or a primary or secondary amine to treat and so to connections of the formula (I) to arrive, where R stands for Carbamyl substituted if necessary. Furthermore one knows the ammonium salt or an amine salt of a connection of the formula (I), where R stands for Carboxy, by Dehydratisieren with a suitable Dehydratisierungsmittel, as sulfuric acid, into a connection of the formula (I) to transfer, where R means substituted Carbamyl if necessary. The mentioned connections, in which R is in halide form vorließendes Carboxy, can on the basis of connections of the formula (I), where R stands for Carboxy, by treating with a Thionylhalogenid, like Thionylchlorid, to be manufactured. If B2 is hydrogen, these can to connections of the formula R - pH C 0 y I I C N Oy pH-n, dimerisieren. Such an intermediate product knows e.g. by treating with a suitable alcoholate, like an alkali metal, e.g. Natriumoder potassium alcoholate, or with an alcohol in presence of a mineral acid, e.g. hydrogen chloride, or with ammonia, Hydroxylamin or a primary or a secondary to [n. into a connection of the formula (I) übergefflhrt, where B stands if necessary for verestertes Carboxy and/or substituted Carbamyl. In a connection of the formula (I) can one a veresterte group of carboxyls or a Carbamylgruppe R substituted if necessary in usual way into the free group of carboxyls transfer, e.g. by hydrolysis, normally in an alkaline medium, like by treating with water in presence of a Alkalimetalloder of alkaline earth metal hydroxide, e.g. sodium hydroxide. In a connection of the formula (I), where B2 stands for hydrogen, this, e.g. by treating with a reactive ester of an appropriate alcohol, can being e.g. replaced like to a halide, in presence of a base, an alkali metal alcoholate, by an aliphatic remainder. Furthermore Is or a Carboxygruppe B available veresterte if necessary in Halogenidoder Salzform can be reduced by conversion with a light alloy boron hydride or with hydrogen to presence of a hydrogenation catalyst to Hydroxymethyl. For the reduction veresterten of a if necessary or as alkali metal, like sodium salt, available Carboxygruppe one uses preferably a light alloy hydride, like a Boran, e.g. Diboran or the Borantetrahydrofurankomplex or a Diloichtmetallhydrid, like lithium aluminum hydride, sodium boron hydride or Natriumcyanoborhydrid. Halogencarbonylgruppen such as Chlorcarbonyl one reduces verzugsweise with hydrogen in presence of palladium, preferably on a carrier, like barium sulfate, and if required a schwefelhaltigen Cokatalysators, e.g. from thiourea. Furthermore one can in a connection of the formula (] [). where R stands for Hydroxymethyl, this in usual way, e.g. by conversion with a veräthernden means, into a verätherte Hydroxymethylgruppe transfer. Veräthernde means are for example reactive esters of appropriate alcohols, for example their ester with inorganic acids, like chlorine, bromine or hydriodic acid or sulfuric acid, or with organic sulfone acids, e.g. with methane, benzene, p-Brombenzoloder p-Toluolsulfonsäure, furthermore of appropriate 1,2-Dielen derived Epoxyde. The conversion with the veräthernden mentioned to average can take place in usual way, for example in presence of an alkali metal hydride or - alcoholate, z, B. from sodium hydride or Natriummethanolat, or by using the too veräthernde connection as salt, e.g. sodium salt. Furthermore one can in a connection of the formula (1), in R Hydroxymethyl, this is in usual way esters, e.g. by direct Veresterung with an appropriate carbonic acid $5 in presence of a mineral acid, e.g. from hydrochloric acid or sulfuric acid, or by conversion with a reactive derivative, e.g. an anhydride, how the anhydride or chloride, or an ester, how Niederalky! - or o-Nitrophenyl, 2,4-Dinitrophonyloster, the carbonic acid, if required in present one drink or above all basic l (ondensationsmittels, during the conversion with a Säureanhydrid, e.g. of Pyridin, and during the conversion with a Säureanhydrid, e.g. of Pyridin, and during the conversion with an ester, e.g. an alkali metal, as Natriumoder of potassium alcoholate transfer, into a veresterte Hydroxymethylgruppe B. In addition, the Verätherung and/or Veresterung of a Hydroxymethylgruppe can be accomplished in such a way that one transfers these first in usual way, e.g. with phosphorus tri bromide or Thionylchlorid, into a group of halogen methyls and afterwards with an alkali metal, e.g. the sodium alcoholate, of the appropriate alcohol, or an alkali metal, e.g. the sodium salt of the appropriate carbonic acid converts. If necessary veresterte Hydroxymethylgruppen B one knows further to Carboxygruppen and verätherte Hydroxymethylgruppen to veresterten Carboxygruppen to oxidize. The oxidation can be accomplished in actually well-known way, e.g. by conversion with oxidizing s a heavy metal compound, on the basis of Hydroxymethyl preferably with a chrome Vloder manganese Vllenthaltenden oxidizing connection, e.g. with chrome tri oxide or in particular potassium permanganate, on the basis of veräthertem Hydroxym8thyl R furthermore with a manganese IVenthaltenden connection, with manganese dioxide. One preferably works in presence of a suitable Lösungsoder of diluent, e.g. from acetone or Pyridin, or a preferably aqueous mixture of it if necessarily under cooling or warming up, e.g. in a temperature range from approximately 0 to for instance 80°C. Received one free salt screen end connections of the formula [I) can in on slch well-known way into salts be transferred, acids e.g. with a base or with a suitable salt of a carbonic acid and bases with a mineral acid, usually in presence of a Lösungsoder Verdünnungsm [ttels. Received salts can be converted into actually well-known way into the free connections, e.g. by treating with a sour reagent, like a mineral acid. The connections, including their salts, can be received also in form of its hydrates, or the solvent used for the crystallization einschlieften. Due to the close relationship between the new connections in free form and in form of their salts if necessary also the appropriate salts and/or free connections are to be understood in the preceeding and in the following by the free connections or their salts sinnund purpose in accordance with. The invention concerns also those execution forms of the procedure, with which one eaktionsbedingungen a basic material under the l in an educated manner or in form of a derivative, if necessary a salt, used. With proceeding the invention such basic materials are preferably used, which lead to that initially as particularly valuable described connections. Available the according to invention connections of the formula (I) and its salts can be used in the form of pharmaceutical preparations. With the pharmaceutical preparations according to invention acts it see around such to enteralen, like oral, nasalen or rektalen, as well as parenteral or topischen administration at Warmblüter, which contain the pharmakologischen active substance alone or together with a pharmaceutical applicable substrate. The dosage of the active substance depends on the Warmblüter species, the age and the individual condition, as well as on the application way. The new pharmaceutical preparations contain e.g. to approximately 95%, preferably from approximately to approximately 90% the active substance. Pharmaceutical preparations are e.g. such topisch in dose unit forms, like dragees, tablets, caps or Suppositorien, as well as ampuls, furthermore InhaIationspräparate, furthermore and local (e.g. to insufflation) usable pharmaceutical preparations. The pharmaceutical preparations are manufactured in actually well-known way, e.g. by means of conventional mixture, granulation, Dragier, L6sungsoder lyophilization procedure. So one can receive pharmaceutical preparations for oral application, by combining the active substance with firm carrier materials, a received mixture if necessary granulated, and the mixture and/or. Granulates, if desired or necessary, after addition of suitable auxiliary materials, to tablets or dragee cores processes. Suitable carrier materials are in particular fillers, like sugars, e.g. lactose, saccharose, Mannit or Sorbit, cellulose preparations and/or calcium phosphates, e.g. Trioaleiumphosphat or calcium hydraulic gene phosphate, furthermore bonding agents, like starch pastes using e.g. Polyvinylpyrrolidon, agar, Alginsäure or a salt of it, transverseinterlaced by corn, wheat, Reisoder potato strength, gel, Traganth, methyl cellulose and/or Polyvinylpyrroliden, and/or, if erwflnscht, explosive, like the above-mentioned strengths, furthermore Carboxymethylstärke, like Natriumalginat. Aid, e.g. silicic acid, talc, stearic acid or salts of it, like Magnesiumoder Calciumstearat, and/or PL glycol. Dragee cores will with suitable, if necessary - ii - Nr.364830 gastric juice-resistant upper courses to provide, whereby one concentrated among other things sugar solutions, which Arab rubber, talc, Polyvinylpyrrolidon, PL glycol and/or titanium dioxide contain if necessary, Laeklösungen in suitable organic solvents or solvent mixtures or, for the production of gastric juice-resistant upper courses, solutions of suitable cellulose preparations, like Acetylcellulosephthalat or Hydroxypropylmethyleellulosephthalat, used. Coloring materials or pigments, e.g. for identification or for the marking of different active substance doses, can be attached to the tablets or dragee coats. Further, orally applicable pharmaceutical preparations are Steekkapseln from gel, as well as soft, closed caps from gel and a softener, like Glycerin or Sorbitol. The putting caps know the active substance in form of granulates, e.g. in the mixture with fillers, like lactose, bonding agents, like strengths, and/or lubricants, like talc or magnesium stearate, and of Stahilisatoren contain if necessary. In soft caps the active substance is preferably in suitable liquids, like fat oils, Paraff [nöl or liquid PL glycols, solved or suspended, whereby stabilizers can be likewise caused. As rektal applicable pharmaceutical preparations Suppositorien are e.g. possible, which consist of a combination of the active substance with a Suppositoriengrundmasse. As Suppositoriengrundmasse are suitable e.g. natural or synthetic Triglyceride, paraffin hydrocarbons, PL glycols or higher Alkanole. Furthermore also gel Rektalkapseln can be used, the one combination of the active substance with a basic dimension enthelten; when GrundZ0 of mass materials come e.g. liquid Trlglycerlde, PL glycols or paraffin hydrocarbons in Frage° are suitable for the parenteral administration primarily aqueous solutions of an active substance in water-soluble form, e.g. a water-soluble salt, furthermore suspensions of the active substance, like appropriate oily injection suspensions, whereby one greases suitable lipophilic solvents or vehicles, as oils, e.g. Sesamöl, or synthetic Fettsäuroester, e.g. Äthylol4at or Triglyceride, used, or aqueous Injektienssuspensionen, whatever viscosity-increasing materials, e.g. Natriumcarboxymethylosllulose, Sorbit and/or Dextran and if necessary contain StabiIisatoren. Inhalation preparations lür the treatment of the respiratory system by nasale or buccale VerabreJchung are e.g. aerosols or sprays, which can distribute the pharmakologischen active substance in form of a propellant or in the form of drops of a password or a suspension. Preparations with propellant-distributing characteristics contain a liquid propulsion gas with a boiling point under the ambient temperature, as well as, except the active substance usually if desired, carrier materials, like liquid or firm niehtlonische or anionisohe surface-active means and/or firm diluent. Preparations, in which the pharmakologische active substance in solution is present, contain a suitable propellant, furthermore, except this if necessary, an additional solvent and/or a stabilizer. In place of the propulsion gas also compressed air can be used, whereby this can be produced by means of suitable Verdichtungsund relaxation device as required, pharmaceutical preparations for topische and local use is e.g. for the treatment of the skin lotions and Cremen, which contain a liquid or semifeste oil LN Wasseroder water in oil emulsion, and ointments (whereby such preferably contain a preservative), for the treatment of the eyes eye drops, which contain the active connection in aqueous or oily solution, and eye ointments, which are preferably manufactured in sterile form, for the treatment of the nose propellant, aerosols and spray (similar described the above for the treatment of the respiratory system), as well as rough propellants, those by fast Inhalieren through the nostrils to be given, and nose drops, which contain the active connection in aqueous or oily solution, or for the local treatment of the mouth Lutschbonbens, which the active connection £n one generally from sugar and rubber arabicum or Tragakanth formed mass to contain, which taste material can be added, as well as Pastillen, which contain the active material in an inert mass, e.g. from gel and Glycerin or sugar and rubber arabieum. The new connections of the formula (I) or salts of it as pharmakologisch active connections, in particular as Antiallergika; preferably in the form of pharmaceutical preparations find use. The daily dose, which is given to a Warmblüter by approximately 70 kg, amounts to depending upon application form, from approximately 2 to approximately 7000 mg. The following examples illustrate the invention it described above are however these to its extent in no way to limit. Temperatures are indicated in centigrades. Example 1: 23 g raw 4-Butyl-l, 2-phenylen-diamin are shifted with 20,8 g Äthoxyessigsäure and heated up 98 min to 130°. One lets cooling, takes up with acetic acid ethyl ester, washes with sodium hydrogencarbonate solution and afterwards three times with water, more dryly over sodium sulfate, I0 filtered and evaporates under decreased pressure to dry ones. The arrears are chromatographiert at 800 g silicagel with chloroform as Laufmittel. After little advance one receives the 2-Äthoxymethyl-5-butyl-benzimidazol, stop in the main parliamentary group. 55 to 59°. The raw material can be manufactured as follows: A solution of 18,3 g 4-Chlor-butyrophenon in 108 ml sulfuric acid of -20° is shifted within 5 min with -9.0 to -15° with a mixture of ä0 ml sulfuric acid and 21 ml dipping nitric acid, whereby everything goes into solution. One agitates with -15 to -10o 45 min after, pours on i000 g ice, sucks off, washes with Wassser after, takes up to chloroform, washes with satisfied Natriumbicarbonatlösung and twice with water, dries over sodium sulfate, filtered and evaporates to dry ones. The Eindampfrückstand is digested with 9.5 ml methanol. One receives the 4-Chlor-3-nitro-butyrophenon from the Smp. 52 to 54°. On a solution of 29. , 8 g 4-Chlor-3-nitro-butyrophenon in 300 ml ethanol are pressed on in autoclaves 50 g ammonia. 10 h are cooled down, ahgesaugt warmed up to 1800, after the cooling warmed up to ambient temperature under decreased pressure to dry ones evaporated, with 200 ml 2n hydrochloric acid 1 h to 80 to 90°, by addition by ice to 15° and washed afterwards with water. The Nutsohgut is taken up to 100O ml Methylenohlorld, over sodium sulfate g dries, restricted, with petroleum ether (boiling range 60 to 80°) shifted and completely evaporated the Methylenohlorid. The 4-Amino-3-nitro-butyrophenon crystalline failed is sucked off and dried in the vacuum. It melts with 128 to 129°. 19.9 g 4-Amino-3-nitro-butyrophenon in approximately 808 ml ethanol and 15 ml 12,8%iger äthanorischer hydrochloric acid are solved and after addition from palladium 5% on coal (2 g) hydrogenated with approximately 30 to 35° up to the admission of ii, 2 1 hydrogen. The catalyst is ahfiltriert and the Fi! stepped under decreased pressure evaporated. The arrears are taken up to ethers, getrecknet and evaporated over sodium sulfate. One receives the 4-Butyl-1,2-phenylendiamin, which can be converted without further cleaning further. Example 2: g 5-Butyl-6-methyl-2-methylaminoanilin-bis-hydrochlorid are solved in 150 ml 2n hydrochloric acid, shifted with 15,6 g Äthoxyessigsäure and heated up 5 h to the return flow. One lets cooling, transferred with ice, makes alkaline with concentrated caustic soda solution and extracts three times with acetic acid ethyl ester. The excerpt is washed twice with water, evaporated over sodium sulfate dried t” o and more utner decreased pressure to dry ones. One receives the 2-Äthoxymethyl-5-butyl1,6-dimeth} /l-benzimidazol, to stop. 46 to 49°. The raw material can be received as follows: The yellow suspension ven 900 ml 3-Chlor-toluol and 367.5 aluminum chloride (finely pulverized) within i h with 266 g butter acid chloride is shifted. During the Zutropfens hydrogen chloride gas develops; the reaction is exothermic (one lets the temperature rise to 78°) and the aluminum chloride dissolves. After completion of the addition of the butter acid chloride the reaction mixture up to stopping the gassing is held with 70° (about 45 min), cools then on 50 " and fills on 2500 g ice. Two equal beginnings each are collected and extracted with Esslgsäureäthylester; the organic excerpt is washed twice with 2n hydrochloric acid, once with a satisfied aqueous Natrlumchloridlösung, twice with a Zn and once with a satisfied aqueous sodium chlorid solution, distilled dried and evaporated aqueous sodium carbonate solution, the so erhaltliche brown, oily arrears: one receives the mixture of the 4-Ghlor-2-m thyl butyrophenons and the 2-Chlor-4-methyl-butyrophenons with 160 to 184°/19 mbar, concentrated sulfuric acid [1275 valley), by means of a carbon dioxide/chloroform mixture on -20 to -25° cooled, under good agitating within i0 min drop by drop with 285,5 g of the mixture by 4-Chlor-2-methyl-butyrophenon and 2-Chlor-4-methyl-butyrophenon is shifted. The developed solution becomes with -20 to -250 within 80 min with a mixture sulfuric acid concentrated of 240 ml and 75 ml 100%iger sulfuric acid [D: 1,52) treat and afterwards during 15 min further-agitated, whereby one lets the temperature increase to -150. One fills ice water on 8000 ml: the failed oil is extracted with chloroform. The organic excerpt is washed once with an aqueous sodium hydrogencarbonate solution and once with water, dried and evaporated over sodium sulfate. The arrears are solved in the double quantity hot I0 methanol and left untouched during 16 h. The crystalline precipitation is filtered off, washed with cold water and dried at 130 mbar and ambient temperature during 18 h. One receives so the 4-Chlor-2-methyl-5-nitro-butyrophenon, which melts with 71 to 72°. One mixture of 24,1 g 4-Chlor-2-methyl-5-nitro-butyrophenon and 250 ml 33 igen solution of Methylamln in ethanol at ambient temperature are left untouched; the crystalline raw material dissolves slowly, whereby 6elbfärbung enters. The reaction is weak exothermic; one cools therefore with a Wasserbad, in order to prevent a too strong escaping from Methylamin to. After 20 min enters complete solution, it begins a precipitation to fail. One leaves untouched during 16 h at ambient temperature and evaporates then under decreased pressure to dry ones. The arrears are shifted, through-vibrated with diethylether (for instance 10B0 valley), ice and Natriumcarbonat and separated the organic layer. This is washed twice with water and the aqueous solution is back-washed with diethylether. The united organic solutions are dried, filtered over sodium sulfate and evaporated on a volume of approximately 300 ml, diluted and cooled then with 100 ml petroleum ethers. The yellow, crystalline 2-Methyl-4-methylamino -5-nitro-butyrophenon fails, is filtered off, with petroleum ether washed and at air more getrockner, Fp. I07 to 108°. The Üborführung of 4-Chlor-2-methyl-5-nitro-butyrophenon in 4-Amino-2-methyl-5-methylamino - butyrophenon can be accomplished also as follows, whereby one can proceed also from a raw Isomerengemiseh. 241 g of deer chlorine methyl nitrobutyrophenon [about 75 industrial union at 4-Chlor-2-methyl-5-nitro-butyrophenon) are suspended in 1200 ml ethanol and shifted with 1200 ml 33%iger methyl amine solution, on which under exothermic reaction dissolution takes place. One leaves 2 days untouched, evaporates under vermlndertem pressure to dry ones, transferred with 000 ml 2n hydrochloric acid and warms up 1 h to 80 to 90°. One cools the Methylenehlorid down by addition of ice on approximately 150, sucks the crystalline precipitation off, washes with water after, takes up to dichloromethane, more dryly over sodium sulfate, evaporates under decreased pressure, last under addition from Cyclohoxan and petroleum ether (Siedebereieh 60 to 80°), cools and sucks the 2-Methyl-4-methylamino-5-nitrobutyrophenon of the stop. I05 to I07° off. 23.0 g 2-Methyl-4-methylamino-5-nitro-butyrophenon are solved S%iger äthanolischer hydrochloric acid in 240 ml ethanol and 57 ml 12, with 5 of iger palladium coal (7.4 g) shifted and hydrogenated with to 350 up to the admission of 11,6 l hydrogen. One filtered from the catalyst, evaporates under decreased pressure to the Troekne, suspended in toluol, distills the water azeotrop off and filters the crystals of the 4-Butyl-0-methyl-2-methylamino-anilin-bis-hydrochlorid of the stop. over off 1600. Example 3: 4s 45 g raw 4-Butyl-2-methylamino-anilin-bishydrochlorid are solved in 200 ml 2n hydrochloric acid, shifted with 23,4 g Äthoxyessigsäure and heated up 2 h to the return flow. One lets cooling, adds up to the clearly alkaline reaction concentrated caustic soda solution and extracts three times with acetic acid ethyl ester. The excerpts are combined, dried twice washed with water, over sodium sulfate, evaporated under decreased pressure. The Eindampfrückstand is recrystallized from little petroleum ether. One receives the 2thoxymethyl-5-butyl-l-methyl-benzimidazol from the Smp. 55 to 580. The raw material can be manufactured in similar way as in example 2 descriptive on the basis of Chlorbenzol over 4-Chlorbutyrophenon and 4-Chlor-3-nitrobutyrophenon. Example 4: In similar way as in example one keeps I descriptive furthermore: 5-Butyl-benziraidazol-2-carbonsäureäthylester. Stop. 129 to 130c, 5-Butyl-l, 6-dimethyl-benzimidazol - carbonic acid ethyl ester, Smp. 56 to 57°, 5-Butyl-la-methyl-benzimidazol-2-carbonsäureäthylester, stop, 49 to 50°, 5-Butyl-l, 6-dimethyl-benzimidazol-2-methanol, stop. 90 to 92°, and 5-Butyl-l, 6-dimethyl-benzimidazol-2-carbonsäure, stop. 51 to 52°. Example 5: 0.8 g sodium are solved in 150 ml ethanol. Then first 10.0 g 2-Äthoxymethyllo -5-butyl-benzimidazol, solved in 500 ml, is caused to ethanol and after 30 min Bühren at ambient temperature 8.0 g Methylamin in 75 ml ethanol. 20 h i ambient temperature are evaporated agitated, to the Treckne, with Ess [more gsäureäthylester taken up, with little water washed, over sodium salt getroeknet and under decreased pressure again evaporated. The crystalline arrears are recrystallized from acetic acid ethyl ester. SE on receives the 2-Äthoxymethyl-5-butyl-l-methyl - benzimidazol from the Smp. 55 bls 58°. Example 6: In 100 ml ethanol 0.5 g sodium are solved. In the received Natriumäthanolatlösung 6.25 g 2thoxymethyl-5-butyl-benzimldazol are in addition-given. One lets 30 min agitate with Raumtemperatut, gives 3 g dimethyl sulfate in addition and heats 4 h up on 60°. Then one loads cooling, giel) t on ice and vibrates with ethyl acetate out. The excerpt is dried over sodium sulfate, evaporated to dry ones and recrystallized the crystalline Eindampfrückstand twice from ethyl acetate. One receives 2thoxymethyl-5-buty! - l-methyl-benzimldazol of the stop. 57 to 58°. Example 7: 0.2 g 1,6-Dimethyl-5-butyl-benzimidazol-2-carbensäureäthylester are suspended in 4 ml n-caustic soda solution and I ml ethanol and agitated 15 min at ambient temperature. Ethanol is taken off under decreased pressure and the solution staying of the sodium salt of the 1,6-Dimethyl -5-butyl-henzimidazol is acidified - carbonic acid with 2n acetic acid. The failed 1,6-Dimethyl -5-butyl-benzimidazol-2-earbonsäure is filtered off, washed with water and dried at ambient temperature. It melts over 105o Zers.). Example 8: 8.9 g 2-Äthoxymethyl-5-butyl-l-methyl-benzimidazol are solved in 180 ml acetone and 9 ml water, shifted with l0 g potassium permanganate and agitated 2 h at ambient temperature. Then about 7 h to the Bfickfluß is heated up, whereby in approximately halfhour distances in each case 2 g potassium permanganate are admitted (altogether 22 g). One lets cooling, filtered over Diatomeenerde, evaporates under decreased pressure to dry ones and takes up to acetic acid ethyl esters. The solution is out-vibrated with sodium bisulphite solution, washed twice with water, dried over sodium sulfate and evaporated under decreased pressure. The Eindampfrückstand becomes at K [donkey gel with a mixture from same parts of CH! oroform, petroleum ether and acetic acid ethyl ester as Laufmittel chromatographiert. One receives the 5-Butyl-la-methyl-benzimidazol-2-carbonsäureäthylester from the stop. 49 to 50°.