DE3037188A1 - 2-Phenyl-benzimidazole derivs. prodn. - by reaction of tri:chloromethyl-benzene cpds. with ortho-phenylene-di:amine derivs. in the presence of an alcoholate - Google Patents
2-Phenyl-benzimidazole derivs. prodn. - by reaction of tri:chloromethyl-benzene cpds. with ortho-phenylene-di:amine derivs. in the presence of an alcoholateInfo
- Publication number
- DE3037188A1 DE3037188A1 DE19803037188 DE3037188A DE3037188A1 DE 3037188 A1 DE3037188 A1 DE 3037188A1 DE 19803037188 DE19803037188 DE 19803037188 DE 3037188 A DE3037188 A DE 3037188A DE 3037188 A1 DE3037188 A1 DE 3037188A1
- Authority
- DE
- Germany
- Prior art keywords
- formula
- alcoholate
- trichloromethyl
- groups
- substituents
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- DWYHDSLIWMUSOO-UHFFFAOYSA-N 2-phenyl-1h-benzimidazole Chemical compound C1=CC=CC=C1C1=NC2=CC=CC=C2N1 DWYHDSLIWMUSOO-UHFFFAOYSA-N 0.000 title abstract description 6
- 150000001412 amines Chemical class 0.000 title 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 title 1
- 125000001424 substituent group Chemical group 0.000 claims abstract description 13
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 claims abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 4
- 150000001298 alcohols Chemical class 0.000 claims abstract description 4
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- -1 trichloromethyl aromatic compound Chemical class 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 230000000295 complement effect Effects 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 7
- XEMRAKSQROQPBR-UHFFFAOYSA-N (trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=CC=C1 XEMRAKSQROQPBR-UHFFFAOYSA-N 0.000 abstract description 4
- 229940035676 analgesics Drugs 0.000 abstract description 2
- 239000000730 antalgic agent Substances 0.000 abstract description 2
- 230000000507 anthelmentic effect Effects 0.000 abstract description 2
- 239000000575 pesticide Substances 0.000 abstract description 2
- 229920002480 polybenzimidazole Polymers 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- UXGJAOIJSROTTN-UHFFFAOYSA-N 2-[4-(4-chlorophenoxy)phenyl]-3h-benzimidazole-5-carboxamide Chemical compound N1C2=CC(C(=O)N)=CC=C2N=C1C(C=C1)=CC=C1OC1=CC=C(Cl)C=C1 UXGJAOIJSROTTN-UHFFFAOYSA-N 0.000 abstract 1
- 229940124339 anthelmintic agent Drugs 0.000 abstract 1
- 239000000921 anthelmintic agent Substances 0.000 abstract 1
- 125000004429 atom Chemical group 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 abstract 1
- 239000003381 stabilizer Substances 0.000 abstract 1
- ZBZJXHCVGLJWFG-UHFFFAOYSA-N trichloromethyl(.) Chemical compound Cl[C](Cl)Cl ZBZJXHCVGLJWFG-UHFFFAOYSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000005840 aryl radicals Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- WHEVDDQAPKQQAV-UHFFFAOYSA-N 2-[4-(1h-benzimidazol-2-yl)phenyl]-1h-benzimidazole Chemical compound C1=CC=C2NC(C3=CC=C(C=C3)C=3NC4=CC=CC=C4N=3)=NC2=C1 WHEVDDQAPKQQAV-UHFFFAOYSA-N 0.000 description 1
- HSTOKWSFWGCZMH-UHFFFAOYSA-N 3,3'-diaminobenzidine Chemical compound C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 HSTOKWSFWGCZMH-UHFFFAOYSA-N 0.000 description 1
- FHOXCSDDMCCTPM-UHFFFAOYSA-N 6-nitro-2-phenyl-1h-benzimidazole Chemical compound N1C2=CC([N+](=O)[O-])=CC=C2N=C1C1=CC=CC=C1 FHOXCSDDMCCTPM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- ZZYXNRREDYWPLN-UHFFFAOYSA-N pyridine-2,3-diamine Chemical class NC1=CC=CN=C1N ZZYXNRREDYWPLN-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/20—Two benzimidazolyl-2 radicals linked together directly or via a hydrocarbon or substituted hydrocarbon radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Verfahren zur Herstellung von 2-ArylbenzimidazolenProcess for the preparation of 2-arylbenzimidazoles
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von 2-Arylbenzimidazolen durch Umsetzung von Trichlormethylaromaten oder Bis-(trichlormethyl )-aromaten, die gegebenenfalls weitere bei der Reaktion inerte Substituenten haben können mit 1,2-Diaminen oder Tetraminen mit Paaren von zueinander in 1,2-Stellung stehenden Aminogruppen, die ebenfalls weitere bei der Reaktion inerte Substituenten haben können, in alkoholischer Lösung in Gegenwart von Älkohblaten.The present invention relates to a method for producing 2-Arylbenzimidazoles by converting trichloromethylaromatics or bis- (trichloromethyl ) aromatics, which may have other inert substituents in the reaction can with 1,2-diamines or tetramines with pairs of one another in the 1,2-position standing amino groups, which also have other substituents which are inert in the reaction can have, in alcoholic solution in the presence of Älkohblaten.
2-Arylbenzimidazole sind auf verschiedenen Wegen zugänglich, so z.B. durch Kondensation von aromatischen l,2-Diaminen mit aromatischen Carbonsäuren bzw. deren Derivaten, Die Darstellung von 2-Arylbenzimidazolen aus Trichlormethylaromaten und o-Phenylamin oder 3,3'-Diaminobenzidin ist bekannt (C.A. 81 (1974) 169478 v), wobei in Lösungsmitteln wie Tetrahydrofuran7 Benzol, Pyridin oder Methanol in Gegenwart von Basen wie Triethylamin oder Pyridin gearbeitet wird. Die hierbei erhaltenen Produkte fallen teilweise stark verunreinigt an und die Ausbeuten sind unbefriedigend.2-Arylbenzimidazoles are available in a number of ways, e.g. by condensation of aromatic 1,2-diamines with aromatic carboxylic acids or their derivatives, the preparation of 2-arylbenzimidazoles from trichloromethylaromatics and o-phenylamine or 3,3'-diaminobenzidine is known (C.A. 81 (1974) 169478 v), whereby in solvents such as tetrahydrofuran7 benzene, pyridine or methanol in The presence of bases such as triethylamine or pyridine is used. The Some of the products are highly contaminated and the yields are unsatisfactory.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von 2-Arylbenzimidazolen der allgemeinen Formel worin R gleiche oder ungleiche bei der Reaktion unverändert bleibende Substituenten, a die Zahlen O bis 4, A den ergänzenden Rest der ein oder rsehrkern-Gen aromatischen Substituento in denen R1 bis R6 Wasserstoff oder gleiche bzw. ungleiche Reste R, b die Zahlen 0 bis 5 und B Wasserstoff oder R oder im Falle des erganzenden Restes (I) gegebenenfalls eine in m- oder p-StellunC zur ersten Benzimidizolgruppe stehende weitere Benzimidazolgruppe bedeuten und gegebenenfalls im Rest (I) einer der Substituenten R1 bis R4 und das zugehörige Kohlenstoffatom durch Stickstoff ersetzt ist, oder sich zwei benachbarte der Rest R1 bis R4 gemeinsam zu einem aromatischen carbozyklischen bzw. ein Stickstoffatom enthaltenden Ring ergänzen, welches dadurch gekennzeichnet ist, daß ein aromatisches 1,2-Diamin der Formel wori.n RI bis R6 die angegebene Bedeutung haben und in der Formel (2 a) gegebenenfalls einer der Substituenten R1 bis R4 und das zugehörige Kohlenstoffatom durch Stickstoff ersetzt ist oder sich zwei benachbarte der Reste R1 bis R4 gemeinsam zu einem aromatischen carbozyklischen bzw. ein Stickstoffatom enthaltenden Ring ergänzen, mit einem Trichlormethylaromaten der Formel od er, im Falle von Diaminen der Formel ( 2 a) mit Bis-(trichlormethyl) -aromaten der Formel worin die Substltuenten R und die Zahlen a und b die an gegebene Bedei,tung haben, in alkoholischer Lösung in Gegenwart eines Alkoholats ulfigeset zt werden.The invention relates to a process for the preparation of 2-arylbenzimidazoles of the general formula where R is the same or different substituents which remain unchanged in the reaction, a is the numbers 0 to 4, A is the complementary radical of the single or very core-gene aromatic substituents in which R1 to R6 are hydrogen or identical or different radicals R, b are the numbers 0 to 5 and B is hydrogen or R or, in the case of the supplementary radical (I), optionally a further benzimidazole group in the m or p position of the first benzimidizole group and optionally in the radical (I) one of the substituents R1 to R4 and the associated carbon atom has been replaced by nitrogen, or two adjacent radicals R1 to R4 combine to form an aromatic carbocyclic ring or ring containing a nitrogen atom, which is characterized in that an aromatic 1,2-diamine of the formula wori.n RI to R6 have the meaning given and in formula (2a) optionally one of the substituents R1 to R4 and the associated carbon atom has been replaced by nitrogen or two adjacent radicals R1 to R4 combine to form an aromatic carbocyclic or a Complete the ring containing nitrogen atom with a trichloromethyl aromatic compound of the formula or, in the case of diamines of the formula (2a) with bis (trichloromethyl) aromatics of the formula in which the substituents R and the numbers a and b have the given meaning, are ulfigeset zt in alcoholic solution in the presence of an alcoholate.
Überraschenderweise ließ sich die Ausbeute dieser Umsetzund durch Verwendung des Alkohol/Alkoholatsystems gegenüber dem bekannten Verfahren erheblich steigern, so z.B. bei 2-Phenylbenzimidazol von 59 % auf 94 %. Das vorliegende Verfahren zeichnet sich außer durch seine hohe Ausbeute durch einfache Reaktionsführung aus.Surprisingly, the yield of this reaction passed through Use of the alcohol / alcoholate system compared to the known process is considerable increase, e.g. with 2-phenylbenzimidazole from 59% to 94%. The present proceedings is characterized not only by its high yield but also by its simple conduct of the reaction.
Als Substituenten R und R1 bis R6, d.h. als bei der Reaktion unverändert bleibende Reste können besonders Halogene bevorzugt Chlor oder gegebenenfalls Brom, Alkylgruppen mit 1 bis 8, insbesondere 1 bis 3 Kohlenstoffatomen, Nitregruppen oder alle Carboxyl- bzw. Alkoxycarbonylreste -COOH bzw. -C00-Alk mit 1 bis 8, insbesondere 1 bis 3 Kohlenstoffatomen in der Alkylgruppe oder gegebenenfalls Acylgruppen wie die Acetylgruppe, Arylreste, wie besonders ein kernige Arylreste, oder Arylalkylreste mit der genannten Anzahl der Kohlenstoffatome verwendet werden.As substituents R and R1 to R6, i.e. as unchanged in the reaction Remaining residues can be particularly halogens, preferably chlorine or optionally bromine, Alkyl groups having 1 to 8, in particular 1 to 3 carbon atoms, nitrene groups or all carboxyl or alkoxycarbonyl radicals -COOH or -C00-Alk with 1 to 8, in particular 1 to 3 carbon atoms in the alkyl group or optionally acyl groups such as the acetyl group, aryl radicals, such as, in particular, a nuclear aryl radicals, or arylalkyl radicals with the stated number of carbon atoms can be used.
Soweit die Substituenten R bzw. R1 bis R6 vorhanden sind, ist die Anzahl am jeweiligen Ring bevorzugt 1 bis 2, im Falle von Chlor oder Brom auch bevorzugt bis zur maximalen Zahl a bzwb b am jeweiligen Rings Soweit Stickstoff in den Ausgangsstoffen 2 a bis 2 c enthalten ist, kommen besonders Diamino-pyridine sowie -chinoline in Frage.As far as the substituents R or R1 to R6 are present, is The number on the respective ring is preferably 1 to 2, also preferred in the case of chlorine or bromine up to the maximum number a or b on the respective ring As far as nitrogen in the starting materials 2 a to 2 c is included, especially diamino-pyridines and -quinolines come in Question.
Die Durchführung der Reaktion erfolgt bevorzugt so, daß das aromatische 1,2-Diamin in einem Alkohol/Alkoholat-Gemisch vorgelegt und der Trichlormethylaromat kontinuierlich oder in Portionen unter Kühlung zugegeben wird.The reaction is preferably carried out so that the aromatic 1,2-diamine presented in an alcohol / alcoholate mixture and the trichloromethyl aromatic is added continuously or in portions with cooling.
Das Molverhältnis von Trichlormethylgruppen der II Tetrachlor methyl- und Bis-(trichlormethyl)-aromaten zu den Diaminen bzw. zum Paar orthoständiger Aminogruppen in den Bisdiaminen soll 0,8 bis 1,2 zu 1, vorzugsweise 0,95 bis 1,0 zu 1 betragen.The molar ratio of trichloromethyl groups of the II tetrachloromethyl and bis (trichloromethyl) aromatics to the diamines or to the pair of ortho amino groups in the bisdiamines should be 0.8 to 1.2 to 1, preferably 0.95 to 1.0 to 1.
Das Molverhältnis von Trichlormethylgruppen zu Alkoholat beträgt etwa 1 zu ).,0 bis 4,5 , vorzugsweise 1 zu 3,0 bis 3,3. The molar ratio of trichloromethyl groups to alcoholate is about 1 to)., 0 to 4.5, preferably 1 to 3.0 to 3.3.
Als Alkohole finden die Alkylalkohole mit 1 bis 4 tohlenstoffatomen Verwendung, bevorzugt Methanol und Aethanol.The alcohols are the alkyl alcohols with 1 to 4 carbon atoms Use, preferably methanol and ethanol.
Als Alkoholate kommen vorzugsweise die zu den Alkoholen korrespondierenden Alkoholate zur Anwendung. Als Alkoholat wird aus Kostengründen das Natriumalkoholat bevorzugt, doch können auch andere Alkali- oder Erdalkalialkoholate eingesetzt werden.Preferred alcoholates are those corresponding to the alcohols Alcoholates for use. Sodium alcoholate is used as the alcoholate for reasons of cost preferred, but other alkali or alkaline earth metal alcoholates can also be used.
Die Reaktion wird bevorzugt in einfacher Weise bei Normaldruck durchgeführt, doch ist auch Arbeiten bei tr"berdruck bis 25 bar nicht ausgeschlossen. Die Reaktion temperatur wird nach oben somit im allgemeinen durch den Siedepunkt des Lösungsmittels begrenzt. Die Rückflußtemperatur von Methanol von 650C erwies sich als im allgemeinen ausreichend, höhere Temperaturen können aber auch angewandt werden. Die Reaktionszeit beträgt 1 bis 24 Stunden, vorzugsweise 2 bis 10 Stunden. The reaction is preferably carried out in a simple manner at normal pressure, however, working at an overpressure of up to 25 bar is not ruled out. The reaction temperature is thus generally increased by the boiling point of the solvent limited. The reflux temperature of methanol at 650C prove to be generally sufficient, but higher temperatures can also be used will. The reaction time is 1 to 24 hours, preferably 2 to 10 hours.
Die Reaktion von Bis-(trichlormethyl)-aromaten mit den Tetraminen der Formeln 2 b und 2 c ist unzweckmäßig, da uneinheitliche teils polymere Produkte gebildet werden und soll daher hier ausgeschlossen sein.The reaction of bis (trichloromethyl) aromatics with the tetramines of formulas 2 b and 2 c is unsuitable because of inconsistent, partly polymeric products are formed and should therefore be excluded here.
2-Phenylbenzimidazole finden Verwendung z.B. zur Her -stellung hochtemperaturbeständiger Stoffe ("Polybenzimidazole"), als W-Stabilisator für Polyester, als Analgetikum, Anthelmintikum und als Pestizid.2-Phenylbenzimidazoles are used e.g. for the production of high temperature resistant Substances ("polybenzimidazoles"), as UV stabilizers for polyester, as analgesics, Anthelmintic and as a pesticide.
Die folgenden Beispiele dienen der weiteren Erläuterung der Erfindung.The following examples serve to further illustrate the invention.
Beispiel 1 2-Phenylbenzimidazol Zu einer Lösung von 21,6 g (0,2 mol) o-Phenylendiamin und 32,4 g (0,6 mol) Natriummethylat in 100 ml Methanol werden 39,1 g (0,2 mol) Benzotrichlorid zudosiert und 7 Stunden unter Stickstoff zum Rückfluß erhitzt. Das Methanol wird abgezogen, der Rückstand zur Entfernung des Natriumchlorids mit Wasser digeriert und aus Ethanol umkristalli siert.Example 1 2-Phenylbenzimidazole To a solution of 21.6 g (0.2 mol) o-Phenylenediamine and 32.4 g (0.6 mol) of sodium methylate in 100 ml of methanol 39.1 g (0.2 mol) of benzotrichloride were metered in and refluxed for 7 hours under nitrogen heated. The methanol is drawn off, the residue to remove the sodium chloride Digested with water and recrystallized from ethanol.
Ausbeute: 36,5 g (94 % d.Th.) Schmp. 288 - 9000 Molekülmasse (massenspektroskopisch ): 194 Beispiel 2 5-flethyl-2-phenylb enzimidazol Analog Beispiel 1 wurden 24,4 g (0,2 mol) 4-Methyl-ophenylendiamin mit 32,4 g (0,6 mol) Natriummethylat und 39,1 g (0,2 mol) Benzotrichlorid in 100 ml Methanol umgesetzt.Yield: 36.5 g (94% of theory) melting point 288-9000 molecular weight (by mass spectroscopy ): 194 Example 2 5-flethyl-2-phenylbenzimidazole Analogously to Example 1, 24.4 g (0.2 mol) of 4-methyl-ophenylenediamine with 32.4 g (0.6 mol) of sodium methylate and 39.1 g (0.2 mol) of benzotrichloride reacted in 100 ml of methanol.
Ausbeute: 34,1 g (82 % d.Th.) Schmp.: 243 -Nolekülmasse ( massenspektroskopisch ): 208 Beispiel 3 5-Nitro-2-phenylbenzimidazol Analog Beispiel 1 wurden 15,3 g (0,1 mol) 4-Nitro-ophenylendiamin mit 16,2 g (0,3 mol) Natriummethylat und 19,6 g (0,1 mol) Benzotrichlorid in 50 ml Methanol umgesetzt.Yield: 34.1 g (82% of theory) melting point: 243 molecular weight (by mass spectroscopy ): 208 Example 3 5-Nitro-2-phenylbenzimidazole Analogously to Example 1, 15.3 g (0.1 mol) 4-nitro-ophenylenediamine with 16.2 g (0.3 mol) sodium methylate and 19.6 g (0.1 mol) benzotrichloride reacted in 50 ml of methanol.
Ausbeute: 16,9 g (71 % d.Th.) Schmp.: 192 - 400 Mol ekülmas s e ( massenspektriskopisch): 239 Beispiel 4 1,4-Bis [benzimidazol-2-yl] benzol Analog Beispiel 1 wurden 21,6 g (0,2 mol) p-Phenylendiamin mit 32,4 g (0,6 mol) Natriummethylat und 31,3 g (0,1 mol) 1,4-Di(trichlormethyl-)benzol umgesetzt. Eine Reinigung erfolgte durch Säulenchromatographie an Kieselgel.Yield: 16.9 g (71% of theory) m.p .: 192 - 400 mol ekülmas s e ( mass spectroscopic): 239 Example 4 1,4-bis [benzimidazol-2-yl] benzene Analogously to Example 1, 21.6 g (0.2 mol) of p-phenylenediamine with 32.4 g (0.6 mol) sodium methylate and 31.3 g (0.1 mol) 1,4-di (trichloromethyl) benzene reacted. Purification was carried out by column chromatography on silica gel.
Ausbeute: 18,0 g ( 58 % d.h.) Molekülmasse ( massenspektroskopisch): 310Yield: 18.0 g (58% i.e.) Molecular mass (by mass spectroscopy): 310
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803037188 DE3037188A1 (en) | 1980-10-02 | 1980-10-02 | 2-Phenyl-benzimidazole derivs. prodn. - by reaction of tri:chloromethyl-benzene cpds. with ortho-phenylene-di:amine derivs. in the presence of an alcoholate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803037188 DE3037188A1 (en) | 1980-10-02 | 1980-10-02 | 2-Phenyl-benzimidazole derivs. prodn. - by reaction of tri:chloromethyl-benzene cpds. with ortho-phenylene-di:amine derivs. in the presence of an alcoholate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE3037188A1 true DE3037188A1 (en) | 1982-04-29 |
Family
ID=6113397
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19803037188 Withdrawn DE3037188A1 (en) | 1980-10-02 | 1980-10-02 | 2-Phenyl-benzimidazole derivs. prodn. - by reaction of tri:chloromethyl-benzene cpds. with ortho-phenylene-di:amine derivs. in the presence of an alcoholate |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE3037188A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999011627A1 (en) * | 1997-09-05 | 1999-03-11 | Ortho-Mcneil Pharmaceutical, Inc. | 2-substituted phenyl-benzimidazole antibacterial agents |
-
1980
- 1980-10-02 DE DE19803037188 patent/DE3037188A1/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999011627A1 (en) * | 1997-09-05 | 1999-03-11 | Ortho-Mcneil Pharmaceutical, Inc. | 2-substituted phenyl-benzimidazole antibacterial agents |
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