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GB774794A - Quinone condensation products - Google Patents

Quinone condensation products

Info

Publication number
GB774794A
GB774794A GB35926/53A GB3592653A GB774794A GB 774794 A GB774794 A GB 774794A GB 35926/53 A GB35926/53 A GB 35926/53A GB 3592653 A GB3592653 A GB 3592653A GB 774794 A GB774794 A GB 774794A
Authority
GB
United Kingdom
Prior art keywords
thioureido
bis
quinone
guanidino
ureido
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
GB35926/53A
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.)
Bayer AG
Original Assignee
Bayer 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 Bayer AG filed Critical Bayer AG
Publication of GB774794A publication Critical patent/GB774794A/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C281/00Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
    • C07C281/16Compounds containing any of the groups, e.g. aminoguanidine
    • C07C281/18Compounds containing any of the groups, e.g. aminoguanidine the other nitrogen atom being further doubly-bound to a carbon atom, e.g. guanylhydrazones

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

Abstract

The invention comprises N-guanidino-N1-acylamino-p-quinone di-imides, wherein the quinone residue may optionally contain alkyl substituents of up to 3 carbon atoms, N : N1-bis - (N11 - acylamino - p - quinone - di - imido) derivatives of bis-guanides and N : N1-bis-(N11-guanidino-p-quinone-di-imido) derivatives of diamides, the acyl-amino groups being ureido, thioureido or carboxylic acid amido radicals; the invention comprises also salts and dihydro derivatives of these compounds. The products are made by reacting a p-quinone with an aminoguanidine to form a N-guanidino-p-quinone imide which is then reacted with a semicarbazide, thiosemicarbazide or carboxylic acid hydrazide, or alternatively by treating the quinone first with the acid hydrazide and then with the aminoguanidine, the reactants preferably being present in equimolecular quantities. For the preparation of the above bis-compounds, either the aminoguanidine is a bis-aminoguanidine, such as hexamethylene-1 : 6-bis-aminoguanidine, or the acyl hydrazide is a bis-compound such as hexamethylene-1 : 6-bis-thiosemicarbazide or the hydrazides of oxalic, succinic, adipic or terephthalic acid, preferably using 1/2 mol. of bis-reactant to each mol. of quinone and mono-hydrazide. The aminoguanidine may be unsubstituted or substituted, e.g. by alkyl or aryl groups, or the two nitrogen atoms of the guanidine configuration may be incorporated in a heterocyclic ring, as in 2-hydrazino-imidazoline or 1-methyl-2-hydrazino-1:4:5:6 - tetrahydropyrimidine. The dihydro derivatives are made by treating the condensation products with reducing agents such as zinc and hydrochloric acid, stannous chloride or sodium dithionite. The compounds are used as pharmaceuticals. The salts are preferably salts in which the acidic component is an acidic reacting therapeutic compound. Examples describe the preparation of N-guanidino-N1-substituted-p-benzoquinone di-imides in which the N1 - substituents are thioureido -, allyl - thioureido-, methyl-thioureido-, ethyl-thioureido-, propyl-thioureido-, butyl-thioureido-, isobutyl-thioureido-, tert.-butyl-thioureido-, cyclohexyl-thioureido-, benzyl-thioureido-, benzthiazolylamino-, p - nitrobenzoyl - amino -, cyano-acetyl-amino-, oxamoylamino-, benzamido-, p-chlorobenzamido-, 2:4-dichlorobenzamido-, phydroxybenzamido -, m - nitrobenzamido-, p - aminobenzamido-, isonicotinyl - amido -, ureido-, guanyl - ureido -, butyl - ureido - and phenyl-ureido-groups; also the preparation of N - (2 - imidazolinyl - amino) - N1 - thioureido - p-quinone-di-imide; hexamethylene - 1:6 - bis-(thioureido - quinonedi-imido - guanidine); N-(2 - imidazolinyl - amino) - N1 - (allyl - thioureido) - p - quinonedi-imide and bis - (N - guanidino - p - quinonedi-imido) - adipic acid diamide; salts and dihydro-derivatives of some of the above compounds are also described. Intermediates. N - Guanidino - quinone - monoimides and N - acylamino - quinone - monoimides in which the acyl groups are ureido, thioureido or carboxylic acid amide groups are formed as intermediates. Specified compounds include N - (2 - imidazolinyl - amino) - p - quinoneimide, hexamethylene - 1:6 - bis - (p - quinoneimido - guanidine) and N - guanidino - p - quinone-imides. 2-Hydrazino-imidazoline is prepared by the reaction of hydrazine and 2-ethylmercapto-2-imidazoline.ALSO:Dyestuffs and intermediates for dyes comprise N - guanidino - N1 - acylamino-p-quinone diimides, wherein the quinone residue may optionally contain alkyl groups of up to 3 carbon atoms as substituents, N:N1 - bis(N11 - acylamino - p - quinonediimido) derivatives of bis-guanides and N:N1 - bis(N11 - guanidino - p - quinone - diimido) derivatives of diamides, the acylamino groups being ureido, thioureido or carboxylic acid amido radicals; the invention comprises also salts and dihydro derivatives of these compounds. The products are made by reacting a p-quinone with an aminoguanidine to form a N-guanidino-p-quinone imide which is then reacted with a semicarbazide, thiosemicarbazide or carboxylic acid hydrazide, or alternatively by treating the quinone first with the acid hydrazide and then with the aminoguanidine, the reactants preferably being present in equimolecular quanties. For the preparation of the above bis-compounds, either the aminoguanidine is a bis-aminoguanidine, such as hexamethylene-1:6-bis-aminoguanidine, or the acyl hydrazide is a bis-compound such as hexamethylene - 1.6 - bis - thiosemicarbazide or the hydrazides of oxalic, succinic, adipic or terephthalic acid, preferably using 1/2 mol of bis-reactant to each mol of quinone and mono-hydrazide. The aminoguanidine may be unsubstituted or substituted, e.g. by alkyl or aryl groups, or the two nitrogen atoms of the guanidine configuration may be incorporated in a heterocyclic ring, as in 2-hydrazino-imidazoline or 1-methyl-2-hydrazino-1:4:5:6-tetrahydropyrimidine. The dihydro derivatives are made by treating the condensation products with reducing agents such as zinc and hydrochloric acid, stannous chloride or sodium dithionite. The compounds are used as pharmaceuticals. The salts are preferably salts in which the acidic component is an acidic reacting therapeutic compound. Examples describe the preparation of N-guanidino-N1-substituted-p-benzoquinone diimides in which the N1-substituents are thioureido-, allyl - thioureido-, methyl - thioureido-, ethyl - thioureido-, propyl - thioureido-, butyl - thioureido-, isobutyl - thioureido-, tert - butyl - thioureido-, cyclohexyl - thioureido, benzyl - thioureido, benzthiazolyl - amino-, p - nitrobenzoyl - amino -, cyanoacetyl - amino-, oxamoylamino-, benzamido-, p - chlorobenzamido-, 2 : 4 -dichlorobenzamido-, p - hydroxybenzamido-, m - nitrobenzamido-, p - aminobenzamido-, isonicotinyl - amido-, ureido-, guanyl - ureido-, butyl - ureido- and phenyl - ureido - groups; also the preparation of N-(2 - imidazolinyl - amino)-N1 - thioureido - p - quinone - diimide; hexamethylene - 1 : 6 - bis(thioureidoquinonediimido - guanidine); N-(2 - imidazolinyl-amino) - N1 - (allyl - thioureido)-p-quinonediimide and bis-(N-guanidino-p-quinonediimido)-adipic acid diamide; salts and dihydro-derivatives of some of the above compounds are also described. Intermediates. N-Guanidino quinonemonoimides and N-acylamino-quinonemonoimides in which the acyl groups are ureido, thioureido or carboxylic acid amide groups are formed as intermediates. Specified compounds include N-(2-imidazolinyl - amino) - p - quinone-imide, hexamethylene - 1:6 - bis - (p - quinone-imidoguanidine) and N-guanidino-p-quinoneimide. Hydrazino-imidazoline is prepared by the reaction of hydrazine and 2-ethylmercapto-2-imidazoline.ALSO:Pharmaceutical products having bactericidal or bacteriostatic activity comprise N-guanidino-N1 - acylamido - p - quinone diimides, wherein the quinone residue may optionally contain alkyl groups of up to 3 carbon atoms as substituents; N : N1 - bis (N11 - acylamino p - quinonediimido) derivatives of bis guanides; N : N1 - bis (N11-guanidino - p - quinonediimido) derivatives of diamides and salts and dihydro derivatives of these compounds, the acylamino groups being ureido, thioureido or carboxylic acid amido radicals (see Group IV(b)). In an example (8) a solution of 1 part of N-guanidino -N1-thioureido - p-quinonediimide and 1 or 2 parts of ascorbic acid is prepared and heated to effect reduction of the quinonediimide derivative to its dihydro derivative; the solutions are suitable for medical use.
GB35926/53A 1953-01-30 1953-12-24 Quinone condensation products Expired GB774794A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE774794X 1953-01-30

Publications (1)

Publication Number Publication Date
GB774794A true GB774794A (en) 1957-05-15

Family

ID=6686159

Family Applications (1)

Application Number Title Priority Date Filing Date
GB35926/53A Expired GB774794A (en) 1953-01-30 1953-12-24 Quinone condensation products

Country Status (1)

Country Link
GB (1) GB774794A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3069430A (en) * 1958-12-11 1962-12-18 Bayer Ag p-benzoquinone-monoguanylhydrazone-mono-[4-hydroxy-thiazolyl-(2)]-hydrazone and process
US3198767A (en) * 1961-03-17 1965-08-03 American Cyanamid Co Conjugated organic polymers
US4112120A (en) * 1975-04-17 1978-09-05 Imperial Chemical Industries Limited Methods and compositions for use in animal husbandry
US5053540A (en) * 1990-03-08 1991-10-01 The Goodyear Tire & Rubber Company Preparation of a para-aminodiphenylamine
US5068439A (en) * 1990-03-08 1991-11-26 The Goodyear Tire & Rubber Company N-substituted phenylenediamine compounds
WO1999052936A2 (en) * 1998-04-09 1999-10-21 Eisai Co., Ltd. Arginine peptide analogs useful as fibroblast growth factor antagonists
WO2005028431A1 (en) * 2003-09-22 2005-03-31 S.C. Terapia S.A. Process for the purification of 1,4-benzoquinone guanylhydrazone thiosemicarbazone (ambazone)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3069430A (en) * 1958-12-11 1962-12-18 Bayer Ag p-benzoquinone-monoguanylhydrazone-mono-[4-hydroxy-thiazolyl-(2)]-hydrazone and process
US3198767A (en) * 1961-03-17 1965-08-03 American Cyanamid Co Conjugated organic polymers
US4112120A (en) * 1975-04-17 1978-09-05 Imperial Chemical Industries Limited Methods and compositions for use in animal husbandry
US5053540A (en) * 1990-03-08 1991-10-01 The Goodyear Tire & Rubber Company Preparation of a para-aminodiphenylamine
US5068439A (en) * 1990-03-08 1991-11-26 The Goodyear Tire & Rubber Company N-substituted phenylenediamine compounds
WO1999052936A2 (en) * 1998-04-09 1999-10-21 Eisai Co., Ltd. Arginine peptide analogs useful as fibroblast growth factor antagonists
WO1999052936A3 (en) * 1998-04-09 2000-01-13 Eisai Co Ltd Arginine peptide analogs useful as fibroblast growth factor antagonists
WO2005028431A1 (en) * 2003-09-22 2005-03-31 S.C. Terapia S.A. Process for the purification of 1,4-benzoquinone guanylhydrazone thiosemicarbazone (ambazone)

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