GB803362A - New imidazolium compounds and process for their manufacture - Google Patents

New imidazolium compounds and process for their manufacture

Info

Publication number
GB803362A
GB803362A GB1957/55A GB195755A GB803362A GB 803362 A GB803362 A GB 803362A GB 1957/55 A GB1957/55 A GB 1957/55A GB 195755 A GB195755 A GB 195755A GB 803362 A GB803362 A GB 803362A
Authority
GB
United Kingdom
Prior art keywords
ethylene
benzimidazyl
compound
quaternated
formula
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
Application number
GB1957/55A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Ciba AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ciba AG filed Critical Ciba AG
Publication of GB803362A publication Critical patent/GB803362A/en
Expired legal-status Critical Current

Links

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
    • 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
    • C07D235/08—Radicals containing only hydrogen and carbon 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
    • C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
    • 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
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
    • C07D277/66—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2 with aromatic rings or ring systems directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/102—The polymethine chain containing an even number of >CH- groups two heterocyclic rings linked carbon-to-carbon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Paper (AREA)
  • Detergent Compositions (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The invention comprises new imidazolium compounds of formula <FORM:0803362/IV (b)/1> in which the two residues A are the same or different aromatic nuclei which may be substituted and in which two adjacent carbon atoms are linked to the two imidazole nitrogen atoms, R is an alkyl or aralkyl residue which may be substituted, R1 is hydrogen or an alkyl, aryl or aralkyl residue which may be substituted, R3 is a divalent bridge member which contains at least one double bond and which forms with the <FORM:0803362/IV (b)/2> double bonds of the imidazole rings an uninterrupted series of conjugated double bonds, m and n are 1 or 2 and X is an anion. They are prepared by reacting an arylimidazole of formula <FORM:0803362/IV (b)/3> with a compound which is capable of quaternating an imidazole nitrogen atom. "A" may be, for example, a naphthalene or benzene residue; R1 may be a phenyl residue, an aralkyl residue such as benzyl or menaphthyl, or preferably an alkyl radical having from 1 to 4 carbon atoms, a hydroxy alkyl group such as hydroxyethyl, or a hydrogen atom; R3 may be, for example, <FORM:0803362/IV (b)/4> or <FORM:0803362/IV (b)/5> Suitable quaternating agents are, for example, methyliodide, ethyl bromide, isopropyl chloride, sec.-butyl bromide, dodecyl bromide, epichlorhydrin, dimethyl sulphate, benzyl halides, benzyl halides substituted in the nucleus, for example by halogen, alkyl or alkoxy groups such as p-chlorobenzyl chloride, menaphthyl chloride, aryl sulphonic acid esters, especially those of the benzene series containing alkyl groups having from 1 to 4 carbon atoms and also compounds which contain a water-solubilizing group, such as halogen alkyl- or aralkyl sulphonic acids. When salts of the imidazoles of the above formula are used as starting materials alkylene oxides, such as ethylene oxide, propylene oxide or glycide, or alcohols having from 1 to 4 carbon atoms, can be used for quaternation. The quaternation may be carried out by heating the components to 50-200 DEG C., if desired, under pressure. Inert solvents such as alcohols, dioxane, monomethyl glycol, benzene, toluene, nitrobenzene or mixtures of these may be used. The new compounds may be used as brightening agents. In the examples: (a) a ,b -di-[N-methyl-benzimidazyl-(2)]-ethylene is treated with p-toluene sulphonic acid ethyl ester to give the compound of formula <FORM:0803362/IV (b)/6> if the N-benzyl substituted compound is used as starting material instead of the N-methyl compound the corresponding benzyl-substituted product is obtained; similarly the methyl ester of p-toluene sulphonic acid may be used instead of the methyl ester; (b) a ,b - di - [benzimidazyl-(2)]-ethylene is reacted with p-toluene sulphonic acid ethyl ester to give the compound of formula <FORM:0803362/IV (b)/7> a compound of similar properties is obtained when instead of the a ,b -di-(benzimidazyl-(2)]-ethylene 6,61-dimethyl or 6,61-dichloro-a ,b -di - [benzimidazyl - (2)] - ethylene is used; (c) a - [benzylimidazyl - (2)] - b - [N - hydroxyethyl-benzimidazyl-(2)]-ethylene is treated with dimethyl sulphate to give the quaternated compound; (d) 1,4-di-[benzimidazyl-(2)]-benzene is quaternated with dimethyl sulphate; (e) a ,b -di-[benzimidazyl-(2)]-ethylene is quaternated with dimethyl sulphate; (f) a ,b -di-[N-methylbenzimidazyl-(2)]-ethylene dihydrochloride is quaternated by treating with methanol; (g) a ,b - di - [N - methylbenzimidazyl - (2)] - ethylene is quaternated by treating with dimethyl sulphate; (h) a ,b -di-[N-methyl-benzimidazyl-(2)]-ethylene is quaternated by treating with ethyl chloride; (j) 2,5-di-[benzimidazyl-(2)]-furane is quaternated by treating with p-toluene sulphonic acid ethyl ester; (k) an aqueous solution of the compound obtained in (b) is boiled under reflux to give the compound of formula <FORM:0803362/IV (b)/8> (l) potassium iodide is added to the product of (k) to give a compound of formula <FORM:0803362/IV (b)/9> if potassium perchlorate is used instead of the iodide the corresponding perchlorate is obtained; and (m) a ,b -di-[benzimidazyl-(2)]-ethylene disulphonic acid is treated with dimethyl sulphate to give the corresponding quaternated compound. Specification 803,361 is referred to.ALSO:The invention comprises new imidazolium compounds of formula: <FORM:0803362/IV (c)/1> in which the two groups A are the same or different aromatic nuclei which may be substituted and in which two adjacent carbon atoms are linked to the two imidazole nitrogen atoms, R is an alkyl or aralkyl residue which may be substituted, R1 is hydrogen or an alkyl, aryl or aralkyl residue which may be substituted, R3 is a divalent bridge member containing at least one double bond which forms with the >C = N double bonds of the imidazole rings an uninterrupted series of conjugated double bonds, e.g. -CH = CH- , -CH = CH - CH = CH-or <FORM:0803362/IV (c)/2> or m is 1 or 2, and X is an anion. They may be prepared by reacting the compound <FORM:0803362/IV (c)/3> or a salt thereof with a compound which is capable of quaternating an imidazole nitrogen atom, e.g. alkyl halides, epichlorhydrin, dimethyl sulphate, benzyl halides, benzyl halides substituted in the nucleus, menaphthyl chloride, aryl sulphonic acid esters and halogen alkyl or aralkyl sulphonic acids. When the salts of the imidazoles are used as starting materials alkylene oxides or alcohols having from one to four carbon atoms may be used as quaternating agents. In the examples: (a) a ,b -di-[N-methyl-benzimidazyl-(2)]-ethylene is quaternated with p-toluene sulphonic acid ethyl ester to give the compound of formula <FORM:0803362/IV (c)/4> Similar compounds are obtained by substituting a ,b - di - [N - benzyl - benzimidazyl (2)] - ethylene for the di-N-methyl compound or p-toluene sulphonic acid methyl ester for the ethyl ester; (b) a ,b -di-[benzimidazyl-(2)] ethylene is treated with p-toluene sulphonic acid ethyl ester to give the compound of formula <FORM:0803362/IV (c)/5> Similar compounds can be obtained if instead of a ,b - di - [benzimidazyl - (2)] ethylene, 6,61 - dimethyl - or 6,61 - dichloro - a ,b - di [benzimazyl - (2)] ethylene is used; (c) a - [benzimidazyl - (2)] - b - [N - hydroxyethylbenzimidazyl-(2)] ethylene is quaternated with dimethyl sulphate; (d) a ,b -di-[N-methyl-benzimidazyl-(2)]-ethylene dihydrochloride is quaternated by treating with methanol; (e) a ,b -di[N-methylbenzimidazyl-(2)] ethylene is quaternated by treating with dimethyl sulphate; (f) a ,b -di-[N-methyl-benzimidazyl-(2)]-ethylene is quaternated by treating with ethyl chloride; (g) the product of which the formula is given in (b) is boiled in aqueous solution under reflux to give <FORM:0803362/IV (c)/6> (h) the product in (g) is treated with potassium iodide to give the compound of formula <FORM:0803362/IV (c)/7> the corresponding perchlorate is obtained if potassium perchlorate is used instead of potassium iodide; and (j) a ,b -di-[benzimidazyl-(2)]-ethylene disulphonic acid is quaternated by treating with dimethyl sulphate. Specification 803,361 is referred to.
GB1957/55A 1954-01-22 1955-01-21 New imidazolium compounds and process for their manufacture Expired GB803362A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH803361X 1954-01-22

Publications (1)

Publication Number Publication Date
GB803362A true GB803362A (en) 1958-10-22

Family

ID=4537832

Family Applications (2)

Application Number Title Priority Date Filing Date
GB1957/55A Expired GB803362A (en) 1954-01-22 1955-01-21 New imidazolium compounds and process for their manufacture
GB1956/55A Expired GB803361A (en) 1954-01-22 1955-01-21 A process and products for the improvement of the optical properties of organic material

Family Applications After (1)

Application Number Title Priority Date Filing Date
GB1956/55A Expired GB803361A (en) 1954-01-22 1955-01-21 A process and products for the improvement of the optical properties of organic material

Country Status (6)

Country Link
BE (2) BE535064A (en)
CH (2) CH327723A (en)
DE (1) DE955683C (en)
FR (2) FR1119854A (en)
GB (2) GB803362A (en)
NL (2) NL194182A (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3019221A (en) * 1959-06-15 1962-01-30 American Cyanamid Co Styryl-bisbenzimidazole brighteners
DE1161725B (en) * 1959-10-10 1964-01-23 Bayer Ag Fungicidal plant protection product
BE627309A (en) * 1962-01-22
CH459210A (en) * 1962-03-09 1968-07-15 Ciba Geigy Process for the preparation of halomethyloxazole derivatives
DE1287585B (en) * 1963-12-13 1969-01-23 Hoechst Ag Process for the preparation of benzimidazolium compounds

Also Published As

Publication number Publication date
FR1119855A (en) 1956-06-26
NL97577C (en)
CH327723A (en) 1958-02-15
CH332387A (en) 1958-08-31
BE535065A (en)
DE955683C (en) 1957-01-10
FR1119854A (en) 1956-06-26
GB803361A (en) 1958-10-22
NL194182A (en)
BE535064A (en)

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