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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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132
ORGANIC SYNTHESES—VOL. 58
Though the cross-coupling of monohaloalkenes proceeds stereo-specifically (entry 8),ã1 that of 1,2-dihaloethylenes proceeds non-stereospecifically, yielding a (-Z)-alkene, the stereoselectivity being dependent on the nature of the phosphine ligand in the catalyst (entry 9).11 Sterically hindered aryl Grignard reagents also react with ease (entry ll).9
The couplings are usually exothermic, and care must be taken not to add the phosphine-nickel catalyst to a mixture of a Grignard reagent and an organic halide, particularly in a large-scale preparation. For example the addition of a small amount of [Ni(dppp)Cl2] to a mixture of vinyl chloride and 4-chlorophenylmagnesium bromide in ethyl ether at 0° led, after a few minutes’ induction period, to an uncontrollable, violent reaction.
1. Department of Synthetic Chemistry, Faculty of Engineering, Kyoto University, Kyoto 606, Japan.
2. G. R. VanHecke and W. D. Horrocks, Jr., Inorg. Chem., 5, 1968 (1966).
3. M. Ogawa and G. Tanaka, J. Chem. Soc. Jap., Ind. Chem. Sect., 58, 696 (1955).
4. Â. B. Eisner and H. E. Strauss, J. Chem. Soc., 583 (1957).
5. K. Tamao, K. Sumitani, and M. Kumada, J. Amer. Chem. Soc., 94, 4374 (1972); R. J. P. Corriu and J. P. Masse, J Chem Soc., Chem. Commun., 144 (1972); K. Tamao, K. Sumitani, Y. Kiso, M. Zembayashi, A. Fujioka, S. Kodama, I. Nakajima, A. Minato, and M. Kumada, Bull. Chem. Soc. Jap., 49, 1958 (1976).
6. For example, G. E. Coates, M. L. H. Green, and K. Wade, “Organometallic Compounds,” Vol. 2, 3rd ed., Methuen and Co., London, 1968; W. Mowat, A. Shortland, G. Yagupsky, N. J. Hill, M. Yagupsky, and G. Wilkinson, J. Chem. Soc., Dalton Trans., 533 (1972); P. S. Braterman and R. J. Cross, Chem. Soc. Rev., 2, 271 (1973).
7. K. Tamao, Y. Kiso, K. Sumitani, and M. Kumada, J. Amer. Chem. Soc., 94, 9268
(1972); Y. Kiso, K. Tamao, and M. Kumada, J. Organometal. Chem., 50, C12 (1973).
8. G. Consiglio and C. Botteghi, Helv. Chim. Acta, 56, 460 (1973); Y. Kiso, K. Tamao, N. Miyake, K. Yamamoto, and M. Kumada, Tetrahedron Lett., 3 (1974); T. Hayashi, M. Tajika, K. Tamao, and M. Kumada, J. Amer. Chem. Soc., 98, 3718 (1976).
9. K. Tamao, A. Minato, N. Miyake, T. Matsuda, Y. Kiso, and M. Kumada, Cftem. Lett., 133 (1975).
10. K. Tamao, S. Kodama, T. Nakatsuka, Y. Kiso, and M. Kumada, J. Amer. Chem. Soc., 97, 4405 (1975).
11. K. Tamao, M. Zembayashi, Y. Kiso, and M. Kumada, J. Organometal. Chem., 55, C91
(1973).
12. H. B. Kagan and T. P. Dang, J. Amer. Chem. Soc., 94, 6429 (1972).
Appendix
Chemical Abstracts Nomenclature (Collective Index Number; Registry Numbers)
Magnesium (8,9); (7439-95-4)
1-Bromobutane: Butane, 1-bromo- (8,9); (109-65-9)
CROSS-COUPLING OF GRIGNARD REAGENTS
133
1.2-Dichlorobenzene: Benzene, o-dichloro- (8); Benzene, 1,2-dichloro- (9); (95-50-1)
1 -Butyl-2-chlorobenzene: Benzene, l-butyl-2-chloro- (8,9); (15499-29-3)
1.2-Dibutylbenzene: Benzene, o-dibutyl- (8); Benzene, 1,2-dibutyl- (9); (17171-73-2)
2-Propanol (8,9); (67-63-0)
Cyclohexanone (8,9); (108-94-1)
Vinyl chloride: Ethylene, chloro- (8); Ethene, chloro- (9); (75-01-4)
Z-Stilbene: Stilbene (8); Benzene, l,l'-(l,2-ethenediyl)bis- (9); (588-59-0); (E) (103-30-0); (Z)(645-49-8)
Ethylene, 1,2-dichloro- (8); Ethene, 1,2-dichloro- (9); (540-59-0); (E) (156-60-5); (Z) (156-59-2)
[Ni{(—)-diop}Cl2], (—)-diop = 2,3-0-isopropylidene-2,3-dihydroxy-l,4-bis(diphenylphosphino)butane: Nickel, dichloro[[(2,2-dimethyl -1,3 - dioxolane - 4,5 - diyl)bis(methylene)]bis[diphenylphos -phine]]- (8,9); (51899-83-3); Nickel, dichloror[(2,2-dimethyl-l,3-dioxolane - 4,5 - diyl)bis(methylene)]bis[diphenylphosphine] - P,P'] -(¦8,9); (41677-72-9)
4-Chlorophenylmagnesium bromide: Magnesium, bromo(p-chloro-phenyl)- (8); Magnesium, bromo(4-chlorophenyl)- (9); (873-77-8) Ni(dmpe)Cl2: Nickel, dichloro[ethylenebis[dimethylphosphine]]-
(8); Nickel, dichloro[l ,2-ethanediylbis[dimethylphosphine]-P,P']-
(9); (14726-53-5)
Ni(dppe)Cl2: Nickel, dichloro[ethylcnebis[diphenylphosphine]]-
(8); Nickel, dichloro[l ,2-ethanediylbis[diphenylphosphine]P,P']-(SP-4-2)- (9); (14647-23-5); cis- (19978-63-3)
Ni(dppp)Cl2: Nickel, dichloro[trimethylenebis[diphenylphosphine]]-
(8); Nickel, dichloro[l,3-propanediylbis[diphenylphosphine]-P,P']-
(9); (15629-92-2)
1.3-Bis(diphenylphosphino)propane: Phosphine, trimethylenebis-[diphenyl- (8); Phosphine, l,3-propanediylbis[diphenyl- (9); (6737-42-4)
[¹(Ð(ÑáÍ5)ç)2Ñ12]: Nickel, dichlorobis(triphenylphosphine)- (8,9); (14264-16-5)
RADICAL ANION ARYLATION: DIETHYL PHENYLPHOSPHONATE
(Phosphonic acid, phenyl-, diethyl ester)
Î
1. Procedure
Cautionl See benzene warning, p. 168.
A 2-1., three-necked, round-bottomed flask is fitted with an ammonia condenser (Note 1) with an outlet protected by a soda-lime drying tube, a dropping funnel, a nitrogen inlet, and a magnetic stirrer. As a slow stream of nitrogen is passed through the system, the condenser is charged with solid carbon dioxide and
2-propanol, the funnel is briefly removed, about a liter of liquid ammonia is added straight from a commercial cylinder (Note 2), and the funnel is replaced. Bright, freshly-pared sodium metal (11.8 g., 0.51 mole) is added, and the mixture turns blue. Diethyl phosphonate (70.4 g., 0.51 mole) (Note 3) is cautiously added dropwise to the sodium in ammonia in the manner of a titration; the endpoint is the change from blue to colorless (Note 4). Iodobenzene (52.4 g., 0.26 mole) (Note 5) is slowly added, and the solution takes on a slight yellowish tint (Note 6). The dropping funnel is replaced by a stopper, the frost is wiped off the outside of the flask with a towel dampened with acetone, and the whole system is mounted in a photochemical reactor of adequate design (Note 7). Cautionl The lamps must be shielded to prevent exposure of the eyes or skin to ultraviolet radiation. The flask is irradiated for
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