Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Patent
1999-08-06
2000-08-01
Richter, Johann
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
568306, C07C20500
Patent
active
060969296
ABSTRACT:
The preparation of aromatic ketones substituted with a thioether group at the ortho position is accomplished by the initial reaction of an aromatic nucleus substituted with a halide and an ortho nitro group with a nitroalkane in the presence of a hydroxide base. The resulting ortho-nitroalkyl nitroarene compound is converted to the corresponding ortho-nitroaryl ketone by an oxidative Nef reaction. The aromatic nitro group of the ortho-nitroaryl ketone is replaced with a thioether group by reaction with a thiolate anion, most preferably under phase-transfer conditions. Aromatic ketones may be used to prepare various pharmaceutical and herbicidal compounds.
REFERENCES:
patent: 3845133 (1974-10-01), Cohen
patent: 5344992 (1994-09-01), Drewes et al.
patent: 5502256 (1996-03-01), Hagedorn et al.
CA:104:148709 abs of Tetrahedron Lett by Danikiewicz 26(30) pp3599-600, 1985.
Chemical Reviews vol. 55 pp 137-155 pp 137-155 "The Nef Reaction" by Noland, 1955.
Reid et al., "Addition of Nitroalkanes to Ortho-Halo-Nitrobenzenes, A New Synthesis of 4-Chloro-7-(Trifluoromethyl) Quinoline", Tetrahedron Letters, vol. 31, No. 8, pp. 1093-1096, 1990.
Kirillov et al., "Substitution of the Chlorine Atom in 2,4-Dinitro-Chlorobenzene by the 2-R-5-Nitro-1, 3-Dioxanyl Residue," translated fron Zhurnal Organicheskoi Khimii, vol. 23, No. 3, pp. 585-588 (1987).
Bretherick, L., "Bretherick's Handbook of Reactive Chemical Hazards; Fourth Edition", Butterworths, pp. 1693-1694 (1990).
Danikiewicz et al., "Direct Nitromethylation of Nitroaphthalene and its Heteroanalogues, A New Method for Functionlization of Nitroarenes", Tetrahedron Letters, vol. 26, No. 30, pp. 3599-3600 (1985),.
Olah et al., "Synthetic Method and Reactions; 89. Improved Transformation of Nitro Compounds into Carbonyl Compounds by Hydrogen Peroxide/Potassium Carbonate", Synthesis, pp. 662-663 (1980).
Evans, T.L., "Phase Transfer Catalyzed Melt Synthesis of Diaryl Sulfide", Synthetic Communications, 14(5), pp. 435-443 (1984).
Brunelle, D.J., "Preparation of Alkyl Aryl Sulfides via Phase-Transfer Catalyzed Displacement of Aromatic Chloride by Alkyl Thiolates", J. Org. Chem., vol. 49, pp. 1309-1311 (1984).
Degani et al., "S,S-Dialkyl Dithiocarbonates as a Convenient Source of Alkanethiolate Anions in Phase-Transfer-Catalysis Systems: An Improved Synthesis of Organic Sulfides", Synthesis, pp. 630-632 (1983).
Reeves et al., "Phase Transfer Catalysis Preparation of Aryl Thioethers", Synthetic Communications, vol. 12, No. 13, pp. 1071-1079 (1982).
Landini et al, "Nucleophilic Aromatic Substitution Reactions under Phase-Transfer Conditions. Synthesis of Alkyl Aryl Sulfides from Isomeric Dichlorobenzenes and Thiolates," J. Org. Chem., vol. 48, pp. 604-605 (1983).
Shner et al., "Phase-Transfer Catalysis of the Reduction of Aromatic Nitro Compounds with Sodium Sulfide", Zhurnal Organicheskoi Khimi, vol. 25, No. 4, pp. 879-880 (1989).
Coombes et al., "On the Synthesis of 2-methylchromene-4-thione and 2-methyl-1-thiochromone", Phosphorous and Sulfur, vol. 14, No. 2, pp. 139-142 (1983).
March, Jerry, "Advanced Organic Chemistry", John Wiley & Sons, Eds. New York, pp. 886-887 (1992).
Bartlett, et al., "A Mild, Oxidative Nitro-to Carbonyl Conversion and a New Prostaglandin Synthon", Tetrahedron Letters, No. 4, pp. 331-334 (1977).
Blake, Esq. Michael J.
Eastman Kodak Company
Gwinnell Harry J.
Richter Johann
Vollano Jean F
LandOfFree
Process for the preparation of thioether-substituted aromatic ke does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Process for the preparation of thioether-substituted aromatic ke, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Process for the preparation of thioether-substituted aromatic ke will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-665564