SYNTHESIS OF SOME NEW 8-QUINOLINYLOXY-5-SULFONAMIDE

Full text of DOI:10.1135/cccc19940957

New Compounds
957
SYNTHESIS OF SOME NEW 8-QUINOLINYLOXY-5-SULFONAMIDE
DERIVATIVES
Ali A. ABDEL HAFEZ, Ahmed A. GEIES, Zeinab A. HOZIEN and Zarif H. KHALIL
Chemistry Department,
Faculty of Science, Assiut University, Assiut 71516, Egypt
Received June 18, 1993
Accepted September 3, 1993
5-Sulfonyl-8-quinolinol1 was used for the synthesis of various derivatives. This attempt
was directed by knowledge that 8-quinolinol was utilized in the synthesis of biologi-
cally active heterocycles as bactericides, fungicides and bioregulators2 – 4
.
The biological and pesticidal activity of 1,3,4-oxadiazoles5 – 7, as well as the pharma-
cological interest of the quinoline moiety, are well known, too.
EXPERIMENTAL
All melting points are uncorrected. 1H NMR spectra were measured on EM-360 90 MHz spec-
trometer using TMS as an internal standard. IR spectra were recorded in KBr on a Pye–Unicam SP
200-G spectrometer. Elemental analyses were determined on a Perkin–Elmer 240 C microanalyzer.
5,8-Disubstituted Quinolines I; General Procedure
Equimolar quantities of 2-chloro malonic acid derivative (0.01 mol) was added to an alcoholic so-
dium salt of 5-piperidino(morpholino)sulfonyl-8-quinolinol and the reaction mixture was heated
under reflux for 5 h. The precipitated product was filtered off, washed with water and recrystallized
from ethanol.
5,8-Disubstituted Quinolines II – IV; General Procedure
A mixture of I (0.001 mol) and hydrazine hydrate (0.001 mol) or phenylhydrazine (0.001 mol) in an
alcoholic sodium ethoxide solution (0.04 g of sodium in 10 ml ethanol) was refluxed on a water bath
for 8 h. The reaction mixture was filtered off, the filtrate was cooled and neutralized with acetic acid.
The product was crystallized from ethanol.
5,8-Disubstituted Quinolines V – VII; General Procedure
A mixture of I (0.001 mol), hydroxylamine hydrochloride (0.0025 mol) and pyridine (10 ml) was
refluxed for 5 h. The reaction mixture was cooled, neutralized with hydrochloric acid and product
recrystallized from methanol.
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

958
Abdel Hafez, Geies, Hozien, Khalil:
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

New Compounds
959
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

960
Abdel Hafez, Geies, Hozien, Khalil:
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

New Compounds
961
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

962
Abdel Hafez, Geies, Hozien, Khalil:
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

New Compounds
963
5,8-Disubstituted Quinolines VIII – X; General Procedure
A mixture of I (0.001 mol), urea or thiourea (0.001 mol) in an alcoholic sodium ethoxide (0.02 g Na
in 10 ml of ethanol) was heated under reflux on a water bath for 7 h. The reaction mixture was
cooled, neutralized with hydrochloric acid and the precipitate was filtered off, washed with water,
collected and recrystallized from ethanol.
Ethyl (5-Dimethylaminosulfonyl-8-quinolinyloxy)acetate (XIa)
A mixture of 5-dimethylaminosulfonyl-8-hydroxyquinoline (0.01 mol), ethyl chloroacetate (0.01 mol)
and fused sodium acetate (3 g) in ethanol (100 ml) was refluxed for 6 h. On cooling, the crystalline
solid thus formed was collected and recrystallized from ethanol.
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

964
Abdel Hafez, Geies, Hozien, Khalil:
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

New Compounds
965
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

966
Abdel Hafez, Geies, Hozien, Khalil:
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

New Compounds
967
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

968
Abdel Hafez, Geies, Hozien, Khalil:
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

New Compounds
969
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

970
Abdel Hafez, Geies, Hozien, Khalil:
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

New Compounds
971
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

972
Abdel Hafez, Geies, Hozien, Khalil:
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

New Compounds
973
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

974
Abdel Hafez, Geies, Hozien, Khalil:
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

New Compounds
975
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

976
Abdel Hafez, Geies, Hozien, Khalil:
5-Dimethylaminosulfonyl-8-quinolinyloxyacethydrazide (XIb)
A mixture of XIa (0.01 mol) and hydrazine hydrate (0.01 mol) in absolute ethanol (50 ml) was re-
fluxed for 4 h. The reaction mixture was cooled in an ice bath and diluted with water (50 ml). The
precipitate was filtered off and recrystallized from benzene.
N1-Benzylidene-(5-dimethylaminosulfonyl-8-quinolinyloxymethyl) Carbohydrazides XII
A mixture of XIb (0.01 mol) and respective aromatic aldehyde (0.01 mol) in ethanol (50 ml) was
refluxed for 2 h. The precipitate formed on cooling was collected and recrystallized from ethanol.
2-Aryl-5-(5-dimethylaminosulfonyl-8-quinolinoxymethyl)-1,3,4-oxadiazoles XIII
A mixture of XII (0.01 mol), anhydrous sodium acetate (0.01 mol) and glacial acetic acid (20 ml)
was heated under reflux for 3 h. The reaction mixture was concentrated and cooled. The precipitated
product was filtered off, dried and crystallized from ethanol.
4-Acetyl-5-aryl-2-(5-dimethylaminosulfonyl-8-quinolinyloxymethyl)-1,3,4-oxadiazolines XIV
A mixture of XIII (0.01 mol) and acetic anhydride (5 ml) was heated under reflux for 1 h. Excess of
acetic anhydride and acetic acid was distilled off under reduced pressure and the residue was recry-
stallized from ethanol.
General Method for the Synthesis of Azo Compounds XV
4-Substituted benzenesulfamoyldiazonium chlorides were prepared by diazotization of 0.05 mol of
4-aminobenzenesulfonyl derivatives, dissolved in a mixture of water (20 ml) and HCl (3 ml) with
sodium nitrite at 5 °C. The diazonium chlorides were used immediately, without separation, for the
synthesis of the corresponding azo compounds.
To a solution of XIIIe (0.01 mol) in sodium hydroxide solution (40 ml, 20%), the appropriate dia-
zonium salt was added portionwise with stirring. The temperature was maintained at 5 °C, and stir-
ring was continued for 1 h. The reaction mixture was kept at ambient temperature for a further 1 h,
during which time the product precipitated. This was filtered, washed with water, dried and recrystal-
lized from benzene.
Preparation of Chloroacetates XVI
A solution of 5-piperidino(morpholino)sulfonyl-8-quinolinol1 (0.01 mol) was dissolved in dry py-
ridine (100 ml) and chloroacetyl chloride (0.01 mol) was added dropwise. The reaction mixture was
stirred for 4 h at room temperature. The precipitate was filtered off and recrystallized from petroleum
ether.
Preparation of Compounds XVII
A solution of 5-piperidino(morpholino)-8-quinolinol (0.01 mol) was dissolved in alcoholic potassium
hydroxide (0.56 g KOH in 30 ml absolute ethanol), then chloroacetic acid (0.01 mole was added
portionwise. The solution was heated under reflux for 10 h, then cooled and acidified with dilute
hydrochloric acid (5 ml concentrated HCl in 20 ml H2O). The precipitate was filtered off and recry-
stallized from ethanol to yield XVIIa or XVIIb, respectively.
A mixture of the acid XVIIa or XVIIb, respectively (0.01 mol) was dissolved in dry benzene
(50 ml) and thionyl chloride (3 ml) was added. The reaction mixture was heated under reflux for 5 h.
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

New Compounds
977
The excess of solvent and thionyl chloride was removed under reduced pressure and the precipitate
was recrystallized from petroleum ether to give XVIIc or XVIId, respectively.
Preparation of Compounds XVIII – XX
5-Sulfonamido-8-chloroacetoxyquinoline and/or 5-sulfonamido-8-quinolinoxyacetyl chloride was dis-
solved in 30 ml of dry benzene. To the solution of XVIa or XVIb, respectively the arylmercaptan
(0.01 mol) was added portionwise and the mixture was heated under reflux for 10 h. The solvent was
removed under reduced pressure and the products XVIII were recrystallized from ethanol.
Similarly compounds XIX were prepared from XVIIc or XVIId, respectively.
α-Mercaptoacetates XIX (0.01 mol) were dissolved in glacial acetic acid (25 ml) and the calculated
volume of hydrogen peroxide was added dropwise. The reaction mixture was left 72 h at room tem-
perature, then poured into ice cold water and the products XX were recrystallized from dioxane.
Preparation of Sulfonamides XXI and XXII
Compounds XVIa, XVIb, XVIIc or XVIId (0.01 mol) and 4-amino-4′-substituted benzene sulfonamides
(0.01 mol) in dry benzene (20 ml) were heated under reflux for 8 h. The solvent was removed under
reduced pressure and the products were recrystallized from ethanol.
REFERENCES
1. Abdel Hafez A. A.: J. Chem. Technol. Biotechnol. 55, 95 (1992).
2. Khalil Z. H., Abdel Hafez A. A., Yanni A. S., Moharam A. M.: Bull. Chem. Soc. Jpn. 61, 4143
(1988).
3. Khalil Z. H., Yanni A. S., Khalaf A. A., Abdel Hafez A. A., Abdou R. F.: Bull. Chem. Soc. Jpn.
61, 1345 (1988).
4. Khalil Z. H., Abdel Hafez A. A., Geies A. A., Kamal El-Deen A. M.: Bull. Chem. Soc. Jpn. 64,
668 (1991).
5. Mazzone G., Bonina F., Arrigo Rina R.: Science 35, 31 (1980).
6. Kalsi R., Bhalla T. N., Parmar S. S., Barthwall J. P.: Pharmacology 39, 103 (1989).
7. Kubo H., Hamura I., Osuga S., Sato R.: Zasso Kenkyn 8, 42 (1969); Chem. Abstr. 73, 108594
(1970).
Collect. Czech. Chem. Commun. (Vol. 59) (1994)