GB874209A - Improvements relating to the production of benzimidazolylidene compounds and the resulting products - Google Patents
Improvements relating to the production of benzimidazolylidene compounds and the resulting productsInfo
- Publication number
- GB874209A GB874209A GB39631/57A GB3963157A GB874209A GB 874209 A GB874209 A GB 874209A GB 39631/57 A GB39631/57 A GB 39631/57A GB 3963157 A GB3963157 A GB 3963157A GB 874209 A GB874209 A GB 874209A
- Authority
- GB
- United Kingdom
- Prior art keywords
- benzimidazole
- methyl
- group
- nitro
- aldehyde
- 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.)
- Expired
Links
- -1 benzimidazolylidene compounds Chemical class 0.000 title abstract 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 abstract 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 8
- DQOSJWYZDQIMGM-UHFFFAOYSA-N 1H-benzimidazole-2-carbaldehyde Chemical compound C1=CC=C2NC(C=O)=NC2=C1 DQOSJWYZDQIMGM-UHFFFAOYSA-N 0.000 abstract 6
- 238000005282 brightening Methods 0.000 abstract 6
- 239000003795 chemical substances by application Substances 0.000 abstract 6
- 239000003054 catalyst Substances 0.000 abstract 5
- 230000005494 condensation Effects 0.000 abstract 5
- 238000009833 condensation Methods 0.000 abstract 5
- 125000004093 cyano group Chemical group *C#N 0.000 abstract 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 abstract 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 abstract 4
- 150000001408 amides Chemical class 0.000 abstract 4
- 150000001875 compounds Chemical class 0.000 abstract 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 4
- GKKCIDNWFBPDBW-UHFFFAOYSA-M potassium cyanate Chemical compound [K]OC#N GKKCIDNWFBPDBW-UHFFFAOYSA-M 0.000 abstract 4
- LDZYRENCLPUXAX-UHFFFAOYSA-N 2-methyl-1h-benzimidazole Chemical compound C1=CC=C2NC(C)=NC2=C1 LDZYRENCLPUXAX-UHFFFAOYSA-N 0.000 abstract 3
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 abstract 3
- 150000002391 heterocyclic compounds Chemical class 0.000 abstract 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 abstract 3
- 230000003287 optical effect Effects 0.000 abstract 3
- 150000002894 organic compounds Chemical class 0.000 abstract 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 3
- 239000000376 reactant Substances 0.000 abstract 3
- 150000003839 salts Chemical group 0.000 abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 3
- IPNPFISPYWNXBR-UHFFFAOYSA-N 1-ethyl-2-methylbenzimidazole Chemical compound C1=CC=C2N(CC)C(C)=NC2=C1 IPNPFISPYWNXBR-UHFFFAOYSA-N 0.000 abstract 2
- ZYYSUWBRKYMQRN-UHFFFAOYSA-N 1-methyl-2-methylsulfonyl-4-nitrobenzene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1S(C)(=O)=O ZYYSUWBRKYMQRN-UHFFFAOYSA-N 0.000 abstract 2
- SIRPHJCQZYVEES-UHFFFAOYSA-N 1-methylbenzimidazole-2-carbaldehyde Chemical compound C1=CC=C2N(C)C(C=O)=NC2=C1 SIRPHJCQZYVEES-UHFFFAOYSA-N 0.000 abstract 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 abstract 2
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical class CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 abstract 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 abstract 2
- 239000002253 acid Substances 0.000 abstract 2
- 150000001299 aldehydes Chemical class 0.000 abstract 2
- 125000000217 alkyl group Chemical group 0.000 abstract 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 abstract 2
- 125000003277 amino group Chemical group 0.000 abstract 2
- 229920002678 cellulose Polymers 0.000 abstract 2
- 239000001913 cellulose Substances 0.000 abstract 2
- 150000003950 cyclic amides Chemical class 0.000 abstract 2
- SIEILFNCEFEENQ-UHFFFAOYSA-N dibromoacetic acid Chemical compound OC(=O)C(Br)Br SIEILFNCEFEENQ-UHFFFAOYSA-N 0.000 abstract 2
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 abstract 2
- 235000019439 ethyl acetate Nutrition 0.000 abstract 2
- 150000004820 halides Chemical class 0.000 abstract 2
- 150000002576 ketones Chemical class 0.000 abstract 2
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract 2
- 229920002239 polyacrylonitrile Polymers 0.000 abstract 2
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 abstract 2
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 abstract 2
- 229940124530 sulfonamide Drugs 0.000 abstract 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical class NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 abstract 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 abstract 1
- 150000000183 1,3-benzoxazoles Chemical class 0.000 abstract 1
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical class O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 abstract 1
- ZIOUQTZLLSBGDM-UHFFFAOYSA-N 1-ethylbenzimidazole-2-carbaldehyde Chemical compound C1=CC=C2N(CC)C(C=O)=NC2=C1 ZIOUQTZLLSBGDM-UHFFFAOYSA-N 0.000 abstract 1
- XNCMQRWVMWLODV-UHFFFAOYSA-N 1-phenylbenzimidazole Chemical compound C1=NC2=CC=CC=C2N1C1=CC=CC=C1 XNCMQRWVMWLODV-UHFFFAOYSA-N 0.000 abstract 1
- XSWVFEQKZFUULO-UHFFFAOYSA-N 2-bromo-2,2-dichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Br XSWVFEQKZFUULO-UHFFFAOYSA-N 0.000 abstract 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 abstract 1
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 abstract 1
- ZDTXQHVBLWYPHS-UHFFFAOYSA-N 4-nitrotoluene-2-sulfonic acid Chemical compound CC1=CC=C([N+]([O-])=O)C=C1S(O)(=O)=O ZDTXQHVBLWYPHS-UHFFFAOYSA-N 0.000 abstract 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 abstract 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- 229920000742 Cotton Polymers 0.000 abstract 1
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 abstract 1
- HHLFWLYXYJOTON-UHFFFAOYSA-N Glyoxylic acid Natural products OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 abstract 1
- 239000004677 Nylon Substances 0.000 abstract 1
- 239000004952 Polyamide Substances 0.000 abstract 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical class C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 abstract 1
- 125000004036 acetal group Chemical group 0.000 abstract 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 abstract 1
- 150000008065 acid anhydrides Chemical class 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 230000003213 activating effect Effects 0.000 abstract 1
- 125000002252 acyl group Chemical group 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- 229940111121 antirheumatic drug quinolines Drugs 0.000 abstract 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 abstract 1
- 239000002585 base Substances 0.000 abstract 1
- 150000001555 benzenes Chemical class 0.000 abstract 1
- 150000001556 benzimidazoles Chemical class 0.000 abstract 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 abstract 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 abstract 1
- 239000004327 boric acid Substances 0.000 abstract 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- 150000001733 carboxylic acid esters Chemical class 0.000 abstract 1
- 239000003518 caustics Substances 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 235000014113 dietary fatty acids Nutrition 0.000 abstract 1
- 238000004043 dyeing Methods 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 abstract 1
- 239000004744 fabric Substances 0.000 abstract 1
- 239000000194 fatty acid Substances 0.000 abstract 1
- 229930195729 fatty acid Natural products 0.000 abstract 1
- 150000004665 fatty acids Chemical class 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 150000002829 nitrogen Chemical class 0.000 abstract 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 abstract 1
- 229920001778 nylon Polymers 0.000 abstract 1
- 125000000962 organic group Chemical group 0.000 abstract 1
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 abstract 1
- 229920002647 polyamide Polymers 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 abstract 1
- 150000003218 pyrazolidines Chemical class 0.000 abstract 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 abstract 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract 1
- 150000003222 pyridines Chemical class 0.000 abstract 1
- 150000003230 pyrimidines Chemical class 0.000 abstract 1
- 150000003248 quinolines Chemical class 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 abstract 1
- 239000001117 sulphuric acid Substances 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 210000002268 wool Anatomy 0.000 abstract 1
- 235000005074 zinc chloride Nutrition 0.000 abstract 1
- 239000011592 zinc chloride Substances 0.000 abstract 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
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
- C07D235/12—Radicals substituted by oxygen atoms
-
- 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
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
- C07D235/10—Radicals substituted by halogen atoms or nitro radicals
-
- 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
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
- C07D235/14—Radicals substituted by nitrogen atoms
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
Benzimidazolylidene compounds are prepared by condensing a benzimidazole-2-aldehyde, unsubstituted in the benzene ring, with an organic compound containing an activated methyl or methylene group and having the general formula X-CH2-Y as hereinafter defined, if necessary in the presence of an acid or basic condensation catalyst, with splitting off of water. The organic compounds containing an activated methyl or methylene group are those in which X represents an electrophilic group such as a carbonyl, carboxyl, carboxylic ester, carboxylic amide, cyano, nitro or organic ammonium group, an aromatic-heterocyclic containing tertiary nitrogen, or a negatively substituted-aromatic isocyclic radical, and Y represents hydrogen, an inert organic group or an electrophilic group. Specified compounds include acetophenone, phenylacetic acid, benzyl cyanide, cyano acetic esters and amides, open and cyclic 1:3-diketones, malonic esters and amides including cyclic amides such as 1:3-diketo pyrazolidines, acyl acetic esters and amides including cyclic amides such as the 5-pyrazolones, heterocyclic compounds containing an activated methyl group in the o- or p-position to a tertiary N atom, preferably in the form of a cyclammonium salt form, such as methylsubstituted pyridines, pyrimidines, pyridazine, pyrazine, azophenanthrene, quinolines, benzthiazoles, benzoxazoles and benzimidazoles, and 4-nitro-1-methyl benzenes having a negative group in the 2-position, e.g. an alkyl sulphonyl, sulphonic acid ester, sulphonamide or cyano group. The benzimidazole-2-aldehydes may be 1-substituted by, for example, lower alkyl groups such as inter alia methyl, butyl, cyano-, hydroxy- or ethoxy-ethyl groups. The condensation is effected under the usual conditions for the condensation of an aldehyde with an active-methyl or -methylene compound. Suitable catalysts are nitrogen bases, caustic alkalies, alkali metal alcoholates, zinc chloride, boric acid, fluoboric acid, sulphuric acid and hydrogen chloride. In some cases a reactant serves as catalyst (of Examples 9, 10 and 14). The water formed may be removed by an entrainer or a fatty acid anhydride. The products obtained from the heterocyclic compounds containing an activated methyl group are optical brightening agents. The compounds obtained from the 4-nitro-1-methyl benzenes may be converted into brightening agents by reducing the nitro-group and then reacting the amino group with an acylating agent, potassium cyanate or a cyanuric halide. The compounds prepared from araliphatic ketones may be reacted with aryl hydrazines to give fluorescent 1:3-diaryl-5-benzimidazolyl-pyrazolines. In the examples, benzimidazole-2-aldehyde is condensed with (1) 2-methyl sulphonyl-4-nitro toluene, the product being reduced to the amino-compound which is reacted with acetic anhydride or potassium cyanate, (4) acetophenone, (5) 1:2-dimethyl benzimidazole, (6) 1-ethyl-2-methyl benzimidazole or (12) 1-b -hydroxy ethyl-2-methyl benzimidazole; 1-methyl benzimidazole-2-aldehyde is condensed with (2) 4-nitro-2-methyl sulphonyl toluene, the product being reduced to the corresponding amino compound which is reacted with acetic anhydride, potassium cyanate or diglycollic acid anhydride, (3) the phenyl ester of 4-nitro toluene-2-sulphonic acid, the product being saponified and reduced to convert the nitro-group to -NH2 which is then acylated, (5) 2-methyl benzimidazole, (6) 1:2-dimethyl benzimidazole, (7) 2:5-dimethyl benzoxazole yield a product existing in cis- and trans-forms which are separated, the cis-form being converted into the optical brightening trans-form on heating, (8) quinaldine, (9) 1:2-dimethyl quinolinium iodide, (10) 2 : 3 - dimethyl - benzthiazolium iodide, (12) 1-b -hydroxy ethyl -2-methyl benzimidazole and (14) 1-ethyl-2-methyl benzimidazole, part being in hydrochloride form as catalyst; (11) 1-ethyl benzimidazole-2-aldehyde is condensed with 1:2-dimethyl benzimidazole and (13) 1-phenyl benzimidazole is condensed with 1:2-dimethyl or 2-methyl benzimidazole. Other 2-methyl benzimidazole reactants are specified containing chlorine in the benzene ring. Benzimidazole-2-aldehyde reactants are prepared by reacting suitable 1:2-diamino benzenes with glyoxylic acid alkyl ester dialkyl acetals and then saponifying the acetal group or by condensing the diamino benzenes or their hydrohalic salts with dichloro- or dibromo-acetic acid and saponifying the resulting 2-dihalo benzimidazole.ALSO:Optical brightening and sometimes dyeing of such materials as wool, fibres of cellulose, polyacrylonitriles, polyesters and polyamides, and cotton and nylon fabrics is effected by means of benzimidazolyl compounds prepared by condensing a benzimidazole- 2-aldehyde, unsubstituted in the benzene ring, with an organic compound containing an activated methyl or methylene group which is (1) a heterocyclic compound having a methyl group in the o-or p-position to a tertiary nitrogen atom in the ring, this nitrogen preferably being in the form of a cyclammonium salt, such as a methyl substituted pyridine, pyrimidine, pyradazine, pyrazine, quinoline, azophenanthrene, benzoxazole, benzthiazole or benzimidazole, (2) an araliphatic ketone, the product then being condensed with an aryl hydrazine to yield a fluorescent 1 : 3-diaryl- 5-benzimidazolyl-pyrazoline, or (3) a nitro-toluene having an activating negative substituent such as an alkyl sulphonyl, sulphonic acid ester, sulphonamide or cyano group, the resulting nitro styryl-benzimidazole product being converted into the desired brightening agent by reduction of the nitro-group to the amino-group followed by reaction of the latter with an acylating agent, e.g. acetic anhydride or diglycolic acid anhydride, or with a cyanuric halide or potassium cyanate. The condensation of the benzimidazole- 2-aldehyde is effected with splitting-out of water, if necessary with the aid of a basic or acidic condensation catalyst. The aldehyde may be substituted in the 1-position by, for example, a lower alkyl, hydroxyethyl, methoxy- or ethoxy ethyl, cyanoethyl or hydroxypropyl group. Numerous examples of the brightening agents are given. The compounds prepared from 1-methylbenzimidazole- 2-aldehyde and 1 : 2-dimethyl-quinolinium iodide and 2 : 3-dimethyl-benzthiazolium iodide dye cellulose and polyacrylonitrile fibres a fluorescent yellow colour.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH874209X | 1956-12-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB874209A true GB874209A (en) | 1961-08-02 |
Family
ID=4544271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB39631/57A Expired GB874209A (en) | 1956-12-21 | 1957-12-20 | Improvements relating to the production of benzimidazolylidene compounds and the resulting products |
Country Status (4)
| Country | Link |
|---|---|
| CH (1) | CH348967A (en) |
| DE (1) | DE1077222B (en) |
| FR (1) | FR1195348A (en) |
| GB (1) | GB874209A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007091056A2 (en) * | 2006-02-07 | 2007-08-16 | The University Of York | Bicyclic compounds and their use |
| US20150166571A1 (en) * | 2010-05-26 | 2015-06-18 | Sunovion Pharmaceuticals Inc. | Heteroaryl Compounds and Methods of Use Thereof |
| CN108047139A (en) * | 2017-11-13 | 2018-05-18 | 云南民族大学 | A kind of chalcone-benzimidazole salt compound and its preparation |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1419330A1 (en) * | 1962-06-09 | 1970-02-19 | Hoechst Ag | Optical brighteners |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE883286C (en) * | 1942-12-23 | 1953-07-16 | Ciba Geigy | Process for the preparation of diimidazoles |
| NL61062C (en) * | 1942-12-23 |
-
1956
- 1956-12-21 CH CH348967D patent/CH348967A/en unknown
-
1957
- 1957-12-20 FR FR1195348D patent/FR1195348A/en not_active Expired
- 1957-12-20 DE DEG23589A patent/DE1077222B/en active Pending
- 1957-12-20 GB GB39631/57A patent/GB874209A/en not_active Expired
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007091056A2 (en) * | 2006-02-07 | 2007-08-16 | The University Of York | Bicyclic compounds and their use |
| WO2007091056A3 (en) * | 2006-02-07 | 2008-01-03 | Univ York | Bicyclic compounds and their use |
| US20150166571A1 (en) * | 2010-05-26 | 2015-06-18 | Sunovion Pharmaceuticals Inc. | Heteroaryl Compounds and Methods of Use Thereof |
| US9834564B2 (en) * | 2010-05-26 | 2017-12-05 | Sunovion Pharmaceuticals Inc. | Substituted quinolines as PDE-10 inhibitors |
| US10562916B2 (en) | 2010-05-26 | 2020-02-18 | Sunovion Pharmaceuticals, Inc. | Substituted quinoxalines as PDE-10 inhibitors |
| CN108047139A (en) * | 2017-11-13 | 2018-05-18 | 云南民族大学 | A kind of chalcone-benzimidazole salt compound and its preparation |
| CN108047139B (en) * | 2017-11-13 | 2023-04-28 | 云南民族大学 | Chalcone-benzimidazole salt compound and preparation thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CH348967A (en) | 1960-09-30 |
| FR1195348A (en) | 1959-11-17 |
| DE1077222B (en) | 1960-03-10 |
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