J . Org. Chem. 1982,47,4347-4348 Table I. Yields f r o m Reaction o f 1 - N a p h t h y l l i t h i u m with C a r b o n M o n o x i d e u
the integrated areas of their vinyl signals in the 'H NMR spectra (60 MHz).
Acknowledgment. We are especially appreciative of synthetic work in connection with this project performed by K. Nukada and 'H NMR (200 MHz) measurements by Dr. Y. Oba, Tohoku University. Registry No. 1, 82730-02-7; 2, 82730-03-8; 3, 82679-53-6; 4, 82729-99-5; 5,82679-54-7; 6,82730-00-5; 7,82730-01-6; 8,40420-35-7; naphthalene, 91-20-3; 1,3-cyclohexadiene, 592-57-4; 9,lO-dihydro9,10-ethenoanthracene,2734-13-6; 2-naphthaldehyde, 66-99-9; xanthone, 90-47-1; acetophenone, 98-86-2; acetone, 67-64-1.
oc-
2a
3a
-78 0
22.7
71.26
25
The reported yields represent p e r c e n t conversion. 96.1% in HMPT/THF ( 2 0 : 8 0 , v/v).
(I
Table 11. Yields f r o m Reaction o f (2,6-Dimethylphenyl)lithium with C a r b o n Monoxideu "C
N. Sbarbati Nudelman* and P a b l o O u t u m u r o Departamento de Quimica Orgcinica, Facultad de Ciencias Exactas y Naturales, Uniuersidad de Buenos Aires, Pab. 11, P.3, Ciudad Uniuersitaria, 1428 Buenos Aires, Argentina Received March 2, 1982
The insertion reaction of carbon monoxide into a twocenter, two-electron metal-carbon bond is an extremely important transformation in organometallic chemistrya2 Attention has recently focused on organometallic complexes of early transition metals3y4and actinide^.^^^ We recently reported the convenient insertion reaction of CO into the metal-carbon bond of phenyllithium to obtain a,a-diphenylacetophenonein a high yield (94%)' and the usefulness of the insertion reaction for the production of diphenylalkyl carbinoh8 With the aim of exploring the scope of these interesting reactions, the behavior of 1naphthyl- (la) and (2,6-dimethylphenyl)lithium(lb) under several reaction conditions was examined. Only two products are formed (eq l), and, in this sense, the reaction
ArLi
1
+
CO
-
0
II
ArCAr
2
f
Pi
Arc-CAr
(1)
3
a, Ar = 1 - n a p h t h y l ; b, A r = 2,6-dimethylphenyl
differs considerably from the previously studied reaction of phenyllithium with carbon monoxide in ethyl ether, for which several products were i s ~ l a t e d . ~The reaction of (1)Presented in part at the 2nd Argentine Meeting on Physical Organic Chemistry, V. Giardino, Cbrdoba, Argentina, Oct 1981. (2) (a) Parshall, G. W. "Homogeneous Catalysis"; Wiley: New York, 1980, Chapter 5. (b) Eisenberg, E.; Hendrickaon, D. E. Adu. Catal. 1979, 28, 79. (3) (a) Wolczanski,P. T.; Bercaw, H. E. Acc. Chem. Res. 1980,13,121 and references therein. (b) Calderazzo, F. Angew. Chem., Int. E d . Engl. 1977, 12, 299. (4) (a) Marsella, J. A.; Caulton, K. G. J. Am. Chem. SOC.1980, 102, 1747. (b) Wood, C. D.; Schrock, R. R. Ibid. 1979,101,5421. (c) Barcaw, J. E. Adu. Chem. Ser., 1978, No. 167, 136. (5) Fagan, P. J.; Manriquez, J. M Marks, T. J. "Organometallics of the f Elements"; Manriquez, T. J., Fisher, R. D., Eds.; Reidel: Dordrecht, Holland, 1979; Chapter 4. (6) (a) Fagan, P. J.; Manriquez, J. M.; Vollmer, S. H.; Day, C. S.; Day, V. W.; Marks, T. J. J.Am. Chem. SOC.1981,103,2206. (b)Fagan, P. J.; Manriquez, J. M.; Marks, T. J.; Day, V. W.; Vollmer, S. H. Ibid. 1980,102, 5393. (7) Nudelman, N. S.; Vitale, A. A. Org. Prep. Proced. 1981, 13, 144. (8) Nudelman, N. S.; Vitale, A. A. J. Org. Chem. 1981,46, 4625.
0022-3263/82/ 1947-4347$01.25/0
2a 3a 2a 3a 2a 3a 32.7 58.2 3 2 . 9 61.1 57.2 34.7 55.0 40.0
