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Organic syntheses vol 58 - Sheppard W.A.

Sheppard W.A., Buchi G.H. Organic syntheses vol 58 - Wiley, 1978. - 123 p.
Download (direct link): organicsynthesesvol581978.pdf
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1. Institut fur Organische Chemie der Justus Liebig-Universitat, 6300 Giessen, Germany. Dr. Seebach’s present address: Eidg. Techische Hochschule, Laboratorium fur Organische Chemie, Universitatsstrabe 16, CH-8092 Zurich, Switzerland.
2. H. Druckrey, R. Preussmann, S. Ivankovic, and D. Schmaehl, Z. Krebsforsch, 69, 103 (1967).
3. P. N. Magee and J. M. Barnes, Advan. Cancer Res., 10, 163 (1967).
4. M. Greenblatt and W. Lijinsky, J. Nat. Cancer Inst., 48, 1687 (1972).
5. J. Kapfhammer and A. Matthes, Hoppe-Seylers 7,. Physiol. Chem., 223, 43 (1933).
6. S. O. Winthrop and L. G. Humber, J. Org. Chem., 26, 2834 (1961).
7. A. M. Likhosherstov, K. S. Raevskii, A. S. Lebedeva, A. M. Kritsyn, and A. P. Skoldinov, Khim. Farm. Zh., 1, 30 (1967) [C.A., 67, 90,642w (1967)].
8. Review: D. Seebach and D. Enders, Angew. Chem., 87, 1 (1975); Angew. Chem. Int. Ed. Engl., 14, 15 (1975). Preliminary communications: D. Seebach and D. Enders, Angew. Chem.. 84, 350, 1186, 1187 (1972); Angew. Chem. Int. Ed. Engl., 11, 301, 1101, 1102 (1972); D. Seebach, D. Enders, B. Renger, and W. Bruegel, Angew. Chem., 85, 504 (1973); Angew. Chem. Int. Ed. Engl., 12, 495 (1973). Full papers with experimental detail: D. Seebach and D. Enders, J. Med. Chem., 17, 1225 (1974); Chem. Ber., 108, 1293 (1975); D. Seebach, D. Enders, and B. Renger, Chem. Ber., 110, 1852 (1977); B. Renger, H.-O. Kalinowski, and D. Seebach, Chem. Ber., 110, 1866 (1977); D. Seebach, D. Enders, R. Dach, and R. Pieter, Chem. Ber., 110, 1879 (1977); B. Renger and D. Seebach, Chem. Ber., 110, 2334 (1977).
9. D. Seebach and M. Kolb, Chem. Ind. London, 687 (1974), 910 (1975).
10. R. R. Fraser and Ň. B. Grindley, Can. J. Chem., 53, 2465 (1975); R. R. Fraser, Ň. B. Grindley, and S. Passannanti, Can. J. Chem., 53, 2473 (1975); D. H. R. Barton, R. D. Bracho, A. A. L. Gunatilaka, and D. A. Widdowson, J. Chem. Soc., Perkin Trans. I, 579 (1975); J. E. Baldwin, S. E. Branz, R. F. Gomez, P. L. Kraft, A. J. Sinskey, and S. R. Tannenbaum, Tetrahedron Lett., 333 (1976). R. R. Fraser and S. Passananti, Synthesis, 540 (1976).
Appendix
Chemical Abstracts Nomenclature (Collective Index Number; Registry Numbers)
2-(Diphenylhydroxymethyl)pyrrolidine: 2-Pyrrolidinemethanol,
a,a-diphenyl-, ( + )- (8,9); (22348-32-9)
Pyrrolidine (8,9); (123-75-1)
N-Nitrosopyrrolidine: Pyrrolidine, 1-nitroso- (8,9); (930-55-2) Ethyl nitrite: Nitrous acid, ethyl ester (8,9); (109-95-5)
122
ORGANIC SYNTHESES—VOL. 58
Lithium diisopropylamide: Diisopropylamine, lithium salt (8); 2-Propanamine, N-(l-methylethyl)-, lithium salt (9); (4111-54-0) Lithium, butyl- (8,9); (109-72-8)
Diisopropylamine (8); 2-Propanamine, N-(l-methylethyl)- (9); (108-18-9)
Benzophenone (8); Methanone, diphenyl- (9); (119-61-9)
Lithium aluminum hydride: Aluminate (1-), tetrahydro-, lithium (8); Aluminate (1-), tetrahydro-, lithium, (T-4)- (9); (16853-85-3)
OXIDATION OF ALCOHOLS BY METHYL SULFIDE-/V-CHLOROSUCCINIMIDE-TRIETHYL AMINE:
4- ferf-BUTYLCY CLOHEX ANONE
[Cyclohexanone, 4-(l,l-dimethylethyl)-]
Cautionl See benzene warning, p. 168.
A 1-1., three-necked, round-bottomed flask is equipped with a mechanical stirrer (Note 1), a thermometer, a dropping funnel, and an argon-inlet tube. The flask is charged with 8.0 g. (0.060 mole) of N-chlorosuccinimide (Notes 2 and 3) and 200 ml. of toluene (Note 4). While a continuous positive argon pressure is maintained, the solution is stirred and cooled to 0°, and 6.0 ml. (0.10 mole) of methyl sulfide (Note 2) is added. A white precipitate appears immediately after addition of the sulfide. The mixture is cooled to -25° using a carbon tetrachloride-dry ice bath (Note 5), and a solution of 6.24 g. (0.04 mole) of 4-feri-butylcyclohexanol (mixture of cis and trans) (Note 2) in 40 ml. of toluene is added dropwise over 5 minutes (Note 6). The stirring is continued for 2 hours at —25° (Note 5), and then a solution of 6.0 g. (0.06 mole) of
1. methyl sulfide-
N-chlorosuccinimide,
Submitted by E. J. Corey,1 C. U. Kim,2 and P. F. Misco2 Checked by S. Yamamoto and W. Nagata
1. Procedure
OXIDATION OF ALCOHOLS
123
triethylamine (Note 2) in 10 ml. of toluene is added dropwise over
3 minutes (Note 7). The cooling bath is removed; after 5 minutes 400 ml. of ethyl ether is added (Note 8). The organic layer is washed with 100 ml. of 1% aqueous hydrochloric acid and then twice with two 100-ml. portions of water (Note 9) and dried over anhydrous magnesium sulfate. The solvents are evaporated under reduced pressure. The residue is transferred to a 50-ml., round-bottomed flask and distilled bulb to bulb at 120° (25 mm.) to yield 5.54-5.72 g. (90-93%) of 4-ferf-butylcyclohexanone, m.p. 41-45° (Note 10).
2. Notes
1. Efficient magnetic stirring could be used as well.
2. The submitters used N-chlorosuccinimidc, 4-fert-butyl-cyclohexanol, methyl sulfide, and triethylamine, available from Aldrich Chemical Company, Inc., without further purification.
The checkers used cis- and trans-4-ferf-butylcyclohexanol (36:64) obtained from E. Merck A G, Darmstadt, methyl sulfide obtained from Tokyo Kasei Kogyo Co., Ltd., and triethylamine obtained from Wako Pure Chemical Industries, Ltd., without further purification.
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