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CA2386069A1 - Indolyl-3-glyoxylic acid derivatives as antitumor agents - Google Patents

Indolyl-3-glyoxylic acid derivatives as antitumor agents Download PDF

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Publication number
CA2386069A1
CA2386069A1 CA002386069A CA2386069A CA2386069A1 CA 2386069 A1 CA2386069 A1 CA 2386069A1 CA 002386069 A CA002386069 A CA 002386069A CA 2386069 A CA2386069 A CA 2386069A CA 2386069 A1 CA2386069 A1 CA 2386069A1
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group
groups
indol
glyoxylamide
pyridin
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CA002386069A
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French (fr)
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CA2386069C (en
Inventor
Bernd Nickel
Thomas Klenner
Gerald Bacher
Thomas Beckers
Peter Emig
Jurgen Engel
Erik Bruyneel
Gunter Kamp
Kirsten Peters
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Ziopharm Oncology Inc
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Priority claimed from DE19946301A external-priority patent/DE19946301A1/en
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00Medicinal preparations containing organic active ingredients
    • A61K31/33Heterocyclic compounds
    • A61K31/395Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
    • A61K31/40Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having five-membered rings with one nitrogen as the only ring hetero atom, e.g. sulpiride, succinimide, tolmetin, buflomedil
    • A61K31/403Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having five-membered rings with one nitrogen as the only ring hetero atom, e.g. sulpiride, succinimide, tolmetin, buflomedil condensed with carbocyclic rings, e.g. carbazole
    • A61K31/404Indoles, e.g. pindolol
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P35/00Antineoplastic agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P35/00Antineoplastic agents
    • A61P35/02Antineoplastic agents specific for leukemia
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P35/00Antineoplastic agents
    • A61P35/04Antineoplastic agents specific for metastasis
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P9/00Drugs for disorders of the cardiovascular system

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  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Medicinal Chemistry (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Epidemiology (AREA)
  • Oncology (AREA)
  • Engineering & Computer Science (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Cardiology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Hematology (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Indole Compounds (AREA)

Abstract

The invention relates to the use of N-substituted indol-3- glyoxylamides of general formula (I) for treating tumors, in particular, in cases of drug resistance and metastatic carcinoma, and as angiogenesis inhibitors having distinctly fewer side effects, in particular, distinctly lower neurotoxicity . The invention also relates to medicaments containing the inventive compounds .

Claims (13)

1. Use of N-substituted indol-3-gloxylamides [sic]
of the general formula 1 as antitumor agents according to main patent application 19 814 838.0 for tumor treatment in particular in the case of pharmaceutical resistance and metastasizing carcinoma, and as angiogenesis inhibitors, with markedly lower side effects in particular markedly lower neurotoxicity where the radicals R, R1, R2, R3, R4 and Z have the following meaning:
R = hydrogen, (C1-C6)-alkyl, where the alkyl group can be mono- or polysubstituted by the phenyl ring and this phenyl ring, for its part, can be mono- or polysubstituted by halogen, (C1-C6)-alkyl, (C3-C7)-cycloalkyl, by carboxyl groups, carboxyl groups esterified with C1-C6-alkanols, trifluoro-methyl groups, hydroxyl groups, methoxy groups, ethoxy groups, benzyloxy groups, and by a benzyl group which is mono- or polysubstituted in the phenyl moiety by (C1-C6) -alkyl groups, halogen atoms or trifluoromethyl groups, R is furthermore the benzyloxycarbonyl group (Z group) or the tertiary butoxycarbonyl radical (Boc radical), furthermore the acetyl group.
R1 can be the phenyl ring which is mono- or poly-substituted by (C1-C6) -alkyl, (C1-C6) -alkoxy, cyano, halogen, trifluoromethyl, hydroxyl, benzyloxy, nitro, amino, (C1-C6)-alkylamino, (C1-C6)-alkoxycarbonylamino and by the carboxyl group or by the carboxyl group esterified with C1-C6-alkanols, or is a pyridine structure of the formula 2 and its N-oxide [sic]
and its N-oxide, where the pyridine structure is alternatively bonded to the ring carbon atoms 2, 3 and 4 and can be substituted by the substituents R5 and R6. The radicals R5 and R6 can be identical or different and have the meaning (C1-C6)-alkyl, and the meaning (C3-C7) -cycloalkyl, (C1-C6) -alkoxy, nitro, amino, hydroxyl, halogen and trifluoro-methyl and are furthermore the ethoxycarbonylamino radical and the group carboxyalkyloxy in which the alkyl group can have 1-4 C atoms.
R1 can furthermore be a 2- or 4-pyrimidinyl heterocycle, where the 2-pyrimidinyl ring can be mono- or polysubstituted by the methyl group, furthermore the 2-, 3-, 4- and 8-quinolyl structure substituted by (C1-C6)-alkyl, halogen, the nitro group, the amino group and the (C1-C6) -alkyl amino radical, a 2-, 3- or 4-quinolylmethyl group, where the ring carbons of the pyridylmethyl radical of the quinolyl group and of the quinolylmethyl radical can be substituted by (C1-C6) -alkyl, (C1-C6) -alkoxy, nitro, amino and (C1-C6)-alkoxycarbonylamino.
R1 can furthermore be, in the case where R = hydrogen, the methyl or benzyl group and the benzyloxycarbonyl radical (Z radical), the tert-butoxycarbonyl radical (BOC radical) and the acetyl group, the following radicals:

-CH2COOH; -CH(CH3) -COOH ; - (CH3) 2-CH- (CH2)2-CH-COO;
H3C-H2C-CH (CH3) -CH (COOH)-; HO-H2C-CH (COOH) -;
phenyl-CH2-CH(COOH)-; (4-imidazolyl)-CH2-CH-COOH)-;
HN=C (NH2) -NH- (CH2)3 -CH(COOH)-; H2N- (CH2)4 -CH(COOH)-;
H2N-CO-CH2-CH- (COOH)-; HOOC(CH2)2-CH(COOH)-;
R1 can furthermore be, in the case where R is hydrogen, the Z group, the BOC radical, the acetyl or the benzyl group, the acid radical of a natural or unnatural amino acid, e.g. the .alpha.-glycyl, the .alpha.-sarcosyl, the .alpha.-alanyl, the .alpha.-leucyl, the .alpha.-isoleucyl, the .alpha.-seryl, the .alpha.-phenylalanyl, the .alpha.-histidyl, the .alpha.-prolyl, the .alpha.-arginyl, the .alpha.-lysyl, the .alpha.-asparagyl and the .alpha.-glutamyl radicals, where the amino groups of the respective amino acids can be present in unprotected or protected form. Possible protective groups for the amino function are the carbobenzoxy radical (Z radical) and the tert-butoxycarbonyl radical (BOC radical) as well as the acetyl group. In the case of the asparagyl and glutamyl radical claimed for R1, the second, unbonded carboxyl group is present as a free carboxyl group or in the form of an ester with C1-C6-alkanols, e.g. as a methyl, ethyl or as a tert-butyl ester.
R1 can furthermore be the allylaminocarbonyl-
2-methylprop-1-yl group.
R and R1 can furthermore, together with the nitrogen atom to which they are bonded, form a piperazine ring of the formula 3 or a homopiperazine ring, if R1 is an aminoalkylene group in which R7 is an alkyl radical, a phenyl ring which can be mono- or polysubstituted by (C1-C6) -alkyl, (C1-C6) -alkoxy, halogen, the nitro group, the amino function and by the (C1-C6)-alkylamino group. R, is furthermore the benzhydryl group and the bis-p-fluorobenzylhydryl group.
R2 can be hydrogen or the (C1-C6) -alkyl group, where the alkyl group is mono- or polysubstituted by halogen and phenyl, which for its part can be mono- or polysubstituted by halogen, (C1-C6)-alkyl, (C3-C7)-cycloalkyl, carboxyl groups, carboxyl groups esterified with C1-C6-alkanols, trifluoromethyl groups, hydroxyl groups, methoxy groups, ethoxy groups or benzyloxy groups. The (C1-C6)-alkyl group applying for R2 can furthermore be substituted by the 2-quinolyl group and the 2-,
3- or 4-pyridyl structure, which can both each be mono- or polysubstituted by halogen, (C1-C4) -alkyl groups or (C1-C4) -alkoxy groups. R2 is furthermore the aroyl radical, where the aryl moiety on which this radical is based is the phenyl ring, which can be mono- or polysubstituted by halogen, (C1-C6) -alkyl, (C3-C7) -cycloalkyl, carboxyl groups, carboxyl groups esterified with C1-C6-alkanols, trifluoromethyl groups, hydroxyl groups, methoxy groups, ethoxy groups or benzyloxy groups.
R3 and R4 can be identical or different and are hydrogen (C1-C6) -alkyl, (C3-C7) -cycloalkyl, (C1-C6) -alkanoyl, (C1-C6) -alkoxy, halogen or benzyloxy. R3 and R4 can furthermore be the nitro group, the amino group, the (C1-C4)-mono- or dialkyl-substituted amino group, and the (C1-C6) -alkoxycarbonylamino function or (C1-C6) -alkoxycarbonylamino- (C1-C6) -alkyl function.
Z is O or S
2. Use of N-substituted indole-3-gloxylamides [sic] according to Claim 1 general formula la for tumor treatment in particular in the case of pharmaceutical resistance and metastasizing carcinoma, and as angiogenesis inhibitors with lower side effects, in particularly markedly lower neurotoxicity where the radicals R = hydrogen R1 = 4-pyridyl, 4-fluorophenyl R2 = benzyl, 4-chlorobenzyl, 4-fluorobenzyl, 3-pyridylmethyl, 4-bromobenzyl R3 and R4 = hydrogen and Z is oxygen.
3. Pharmaceutical composition for tumor treatment in particular in the case of pharmaceutical resistance and metastasizing carcinoma, and as angiogenesis inhibitors with lower side effects in particular markedly lower neurotoxicity characterized in that they contain at least one of the compounds of the general formula 1 or 1a if appropriate also they [sic] as acid addition salts, for example as salts of mineral acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, salts of organic acids, such as, for example, acetic acid, lactic acid, malonic acid, maleic acid, fumaric acid, gluconic acid, glucuronic acid, citric acid, embonic acid, methanesulfonic acid, trifluoroacetic acid, succinic acid and 2-hydrop0xyethanesulfonic [sic] acid and possible [sic], their N-oxides.
4. Use of N-substituted indole-3-glyoxylamides of the general formula 1 or 1a and their physiologically tolerable acid addition salts for the production of antitumor agents for use in particular in the case of pharmaceutical resistance and metastasizing carcinoma, and as angiogenesis inhibitors with markedly lower side effects in particular markedly lower neurotoxicity, to be specific in particular of the following compounds or their salts with physiologically tolerable acids or if possible their N-oxides:
D 24241 N-(pyridin-4-yl)-[1-(4-fluorobenzyl)indol-3-yl]
glyoxylamide D 24843 N-(pyridin-4-yl)-(1-benzylindol-3-yl) glyoxylamide D 24850 N-(4-fluorophenyl)-[1-(3-pyridylmethyl)indol-3-yl] glyoxylamide D 24851 N-(pyridin-4-yl)-[1-(4-chlorobenzyl)indol-3-yl]
glyoxylamide D 25505 N-(pyridin-4-yl)-[1-(4-fluorobenzyl)indol-3-yl]
glyoxylamide HCL [sic]
5. Antitumor agent comprising as active compound one or more N-substituted indole-3-gloxylamides [sic]
according to the general formula 1 or 1a and, if appropriate, their physiologically tolerable acid addition salts of antitumor agents for use in particular in the case of pharmaceutical resistance and metastasizing carcinoma, and as angiogenesis inhibitors with markedly lower side effects in particular markedly lower neurotoxicity but in particular one or more compounds according to Claim 4.
6. Antitumor agents for tumor treatment in particular in the case of pharmaceutical resistance and metastasizing carcinoma, and as angiogenesis inhibitors with lower side effects in particular markedly lower neurotoxicity, to be specific in particular comprising as active compound D 24241 N-(pyridin-4-yl)-(1-(4-fluorobenzyl)indol-3-yl]
glyoxylamide or its hydrochloride
7. Antitumor agents for tumor treatment in particular in the case of pharmaceutical resistance and metastasizing carcinoma, and as angiogenesis inhibitors with markedly lower side effects in particular markedly lower neurotoxicity, to be specific in particular comprising as active compound D 24843 N-(pyridin-4-yl)-(1-benzylindol-3-yl)glyoxyl-amide
8. Antitumor agents for tumor treatment in particular in the case of pharmaceutical resistance and metastasizing carcinoma, and as angiogenesis inhibitors with markedly lower side effects in particular markedly lower neurotoxicity, to be specific in particular comprising as active compound D 24850 N-(4-fluorophenyl)-[1-(3-pyridylmethyl)indol-3-yl]glyoxylamide
9. Antitumor agents for tumor treatment in particular in the case of pharmaceutical resistance and metastasizing carcinoma, and as angiogenesis inhibitors with markedly lower side effects in particular markedly lower neurotoxicity, to be specific in particular comprising as active compound D 24851 N-(pyridin-4-yl)-[1-(4-chlorobenzyl)indol-3-yl]
glyoxylamide
10. Antitumor agents for tumor treatment in particular in the case of pharmaceutical resistance and metastasizing carcinoma and as angiogenesis inhibitors with markedly lower side effects in particular markedly lower neurotoxicity comprising as active compound one or more N-substituted indole-3-gloxylamides [sic]
according to the general formula 1 or 1a and, if appropriate, their physiologically tolerable acid addition salts and, if possible, N-oxides, but in particular one or more compounds according to Claims 4 and 6 to 8 and a pharmaceutically utilizable vehicle and/or diluent or excipient in the form of tablets, coated tablets, capsules, solutions for infusion or ampoules, suppositories, patches, powder preparations which can be employed by inhalation, suspensions, creams and ointments.
11. Use of N-substituted indole-3-glyoxylamides of the general formula 1 or 1a and their physiologically tolerable acid addition salts as angiogenesis inhibitors, to be specific in particular of the following compounds or their salts with physiologically tolerable acids or if possible their N-oxides:
D 24241 N- (pyridin-4-yl) - [1-(4-fluorobenzyl) indol-3-yl]
glyoxylamide D 24843 N-(pyridin-4-yl)-(1-benzylindol-3-yl)glyoxyl-amide D 24850 N-(4-fluorophenyl)-[1-(3-pyridylmethyl)indol-3-yl]glyoxylamide D 24851 N-(pyridin-4-yl)-[1-(4-chlorobenzyl)indol-3-yl]
glyoxylamide D 25505 N-(pyridin-4-yl)-[1-(4-fluorobenzyl)indol-3-yl]
glyoxylamide HCL [sic]
12. Use of N-substituted indole-3-glyoxylamides of the general formula 1 or 1a and their physiologically tolerable acid addition salts for use in particular in the case of pharmaceutical resistance and as a replacement for antitumor agents which are no longer active on account of resistance formation in particular of the compounds D 24241 N-(pyridin-4-yl)-[1-(4-fluorobenzyl)indol-3-yl]
glyoxylamide D 24843 N-(pyridin-4-yl)-(1-benzylindol-3-yl)glyoxyl-amide D 24850 N-(4-fluorophenyl)-[1-(3-pyridylmethyl)indol-3-yl]glyoxylamide D 24851 N-(pyridin-4-yl)-[1-(4-chlorobenzyl)indol-3-yl]
glyoxylamide D 25505 N-(pyridin-4-yl)-[1-(4-fluorobenzyl)indol-3-yl]

glyoxylamide HCL
13. Use of N-substituted indole-3-glyoxylamides of the general formula 1 or 1a and their physiologically tolerable acid addition salts for use in particular in the case of pharmaceutical resistance in fixed or free combination with known antitumor agents and as a replacement for antitumor agents which are no longer active on account of resistance formation in particular of the compounds D 24241 N-(pyridin-4-yl)-[1-(4-fluorobenzyl)indol-3-yl]
glyoxylamide D 24843 N-(pyridin-4-yl)-(1-benzylindol-3-yl)glyoxyl-amide D 24850 N-(4-fluorophenyl)-[1-(3-pyridylmethyl)indol-3-yl]glyoxylamide D 24851 N-(pyridin-4-yl)-[1-(4-chlorobenzyl)indol-3-yl]glyoxylamide D 25505 N-(pyridin-4-yl)-[1-(4-fluorobenzyl)indol-3-yl]glyoxylamide HCL
CA2386069A 1999-09-28 2000-09-26 Indolyl-3-glyoxylic acid derivatives as antitumor agents Expired - Fee Related CA2386069C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19946301A DE19946301A1 (en) 1998-04-02 1999-09-28 Antitumor agents and angiogenesis inhibitors having low neurotoxicity, comprise indole-3-glyoxylamide derivatives, are effective against resistant and metastasis-forming carcinomas
DE19946301.8 1999-09-28
PCT/EP2000/009390 WO2001022954A2 (en) 1999-09-28 2000-09-26 Indolyl-3-glyoxylic acid derivatives serving as antitumor agents

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CA2386069A1 true CA2386069A1 (en) 2001-04-05
CA2386069C CA2386069C (en) 2012-08-14

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GEP20043250B (en) 2004-06-25
WO2001022954A2 (en) 2001-04-05
EE200200169A (en) 2003-04-15
DE50015879D1 (en) 2010-04-15
PL364811A1 (en) 2004-12-13
BG106639A (en) 2002-12-29
SK287533B6 (en) 2011-01-04
CA2386069C (en) 2012-08-14
AU7782900A (en) 2001-04-30
AU783436B2 (en) 2005-10-27
PL199576B1 (en) 2008-10-31
CZ303246B6 (en) 2012-06-20
KR20030019295A (en) 2003-03-06
CN1376064A (en) 2002-10-23
ES2342042T3 (en) 2010-07-01
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