2290 J . Org. ('hem., Vol. 44, No. 13, 1979
Notes (1961).
For bis-(p-metnoxyhenzoyl)diazine(IC,96%): m p 133-134 " C (lit.]I ];I2 " C ) . Preparation of 1,2-Diazetidines 2a-c. A solution of 4.6 g (50.0 mtnol) 0 1 quadricyclane and 16.8 mmol of the appropriate diaroyldiazine la-c in 200 m L of acetonitrile was refluxed for the following periods of time: 1.5 h for la, 3 h for Ib, and 24 h for IC. Removal of'
Determination of the stereospecificity in 1,2-diazetidine products 2 is impossible since rapid consecutive nitrogen inversions equilibrate all possible cis and trans diasteri~mers.~ J. C. Mitchell, M. S. Thesis, Southern Illinois University, Edwardsvllle, 111. H. H. Hatt, "Organic Syntheses", Collect. Vol. 2, A . H Blatt, Ed., Wiley, New York, 1943. p 208. L. Horner and W. Naumann, Justus Liebigs Ann. Chem.. 587, 93 (1954). J. E. Leffler and W. B. Bond, J. Am. Chem. Soc., 78, 335 (1956).
sc~lventand excess quadricyclane a t reduced pressure afforded crude 1 .?--diazetidines 2a-c in yields in excess of 90?& Recrystallization from c a r t m i tetrachloride afforded analytically pure 1,2-diazetidines in 90, 65,and 60?0 yields for 2a, 2b, and 2c, respectively. For ~i,4-bii~p-~trifluoromethyl)benzoyl]-:1,4-diazatricyclo~ 4 . ~ . 1 . 0 ' ~ s ] t i o n - ~ -(2a): ~ : n em p 220-221 "C; 'H N M R (CDCI:]) 6 7.90 id. 4 H. J = 9 Hz), 7.37 ( d ,4 H . J = 9 Hz), 5.95 (broads, 2 H), 4.42 (s, 2 H ) , 2.98 (broad c , 2 H). 2.25 (d, 1 H, J = 9 Hz), 1.77 (d, 1 H, J = 9 Hz); '"F N M R (CDCI,;)05 36.81( s ) ;IR ( K B r ) 1685 cm-' (C=O), no N H . Anal. Calcd for C'Z:IHl(;F~N~O~: C, 59.23; H, 3.46; N, 6.01. Found: C , ,79,28; H. 3.24; N , 5.90. For :i.4-dibenz~~yl-;~,4-tiiazatricyclo[4,2.l.O~~~]non-7-ene (2b): m p 211-212 "C; 'H N M R (CDC1:3) 8 7.57--8.09 (m, 10 H), 6.10 (broad s, ~ H H ) . 1 . 4 9 ( s , 2 H ~ . : 1 . 0 8 i h r o a d s , 2 € ~ ) , 2 . 3 8 ( d11 ,lH H,zJ) =, l . 7 8 id. 1 H. J = 11 Hx); IR (KBrl 1680 cm-' (C=O). no N H . Anal. Calcd X 3 4 : H , 5.49; N , 8.48. Found: C. 76.01; H, 5.22:
2,3-DimethylenebutadieneDianion: Convenient Procedure for Allylic Metalation of Conjugated Dienes Joseph J. Bahl, Robert B. Bates,* and Bernard Gordon I11
Department o,f Chemistry, Uniuersit? of Arizona, Tucson, Arizona 85721 For :i,4-bis(p-rnethoxybenzoyl)-3,4-diazatricyclo[4.2.l.Oz~s]non7-ene (2c): m p 190-191 "C: 'H N M R (CDC13 (6 7.97 (d, 4 H, J = 9 Hz), Receiiled January 22, 1979 ' 7 . 0 5 ( d , 4 H . J =t ~ H z ) , 6 . 1 O ( b r o a d s , 2 H ) , 4 . 4 7 ( ~ , 2 H ) , 3 . 9 5 ( ~ , 6 H ) , :2,:i8 rd. 1 H. J = 10 Hzi, 1.85 (d, 1 H, J = 10 Hzj; IR (KBr) 1670 cm-I While 2,3-dimethylenebutadiene dianion (1) has been C=O), no NH. Anal. Ca , ~ H ~ ? N ZC,O70.75; ~ : H, 5.68; N, 7.71. formally present as a ligand of iron in a complex,' efforts to Found: C , 70.52; H,5.56 prepare alkali metal salts of it by metalation of 2,3-dimethKinetic Measurements. Solutions of 0.01 M in la-c and 0.1 R.I in ylbutadiene with base-solvent systems such as n-butyllithquadricyclane in acetonitrile o r carbon tetrachloride were tightly stoppered in roui-id-bottom flasks and heated at 60 f. 1 "C in a therium-tetramethylethylenediamine have failed due to faster mostatically controlled water bath. Aliquots were withdrawn at varaddition to its conjugated diene system. This rapid addition I ( I U S intervals and immediately quenched a t -78 "C. Analyses for to 1,3-dienes has made the much less accessible 1,4-dienes the unreacted la-c were performed by Fisible spectroscopy on a Cary-14 usual precursors of pentadienyl carbanions,' though 1,3-dienes ~ ~ l t r a v i o l e t ~ ~ v i sspectrometer ible at the wavelengths shown in Table can be used with KNH?/NH3 with its temperature and pres1. Pseudo-first-order rate constants were determined graphically over sure limitations.,' We wish to report that Lochmann's base a t least three half-lives for the disappearance of la-c. Second-order rate constants ii (shown in Table I) were determined by dividing the mixture n-butyllithium-KO-t -Bu4 metalates 2,3-dimethylol)serired pseudo-first-order rate constants by initial quadricyclane butadiene smoothly to dianion 1 and in addition gives penconcentration a n < irepresent the average of a t least two runs. Firstorder rat,e consta i t s at 60 "C for thcb unimolecular decomposition of la-c in the absence of quadricyclane account for less than 5% of the ~ihservedpseudo-first-order rate constant in the presence of the hydrocarbon.
N.8.16.
1
Acknowledgment. The authors wish to thank the donors of the Petroleum Research Fund, administered by the A4mericanChemical Society, and the Office of Research and Projects at Southern Illinois University a t Edwardsville for support of this research. Registry No.--la, 69780-57-0; 1b, 959-31-9; IC, 38192-16-4; 2a, 69580-58-1;2b, 69180-59-2;Zc, 69780-60-5; 3a, 69780-61-6;3b, 78784-8;3c, 849-821: p- (trif1uoromethyl)benzoyl chloride, 329-15-7; benzoyl chloride. 98-88-4: p-methoxybenzoyl chloride, 100-07-2; hydrazine, 302-01 -2; quadricyclane, 278-06-8.
References and Notes ( 1 ) See, for example, (a)P. G. Gassman and K. Mansfield. Chem. Commun., 391 (1965):(b) J. Am. Chem. SOC.,90, 1517, 1524(1968j;(c) R. Noyori. T. Suzuki, Y. Kumagai, and H. Takaya. ibid., 93, 5896 (1971):(d)N. A. Porter and D. W. Gilmore, ibid., 99, 3503 (1977). (2) See, for example, (a) A . Cairncrossand E. P. Blanchard, J. Am. Chem. Soc., 88, 496 (1966) (b) R. Noyori, T. Suzuki, Y. Kumagai, and H. Takaya, ibid., 93, 5894 (1971);(c) P. G. Gassman and T. Nakai, ibid., 93, 5897 (1971); (d) E. Lee-Ruff and G. Just, Can. J. Chem., 46, 1887 (1968);(e) M. Pomerantz, R. N. Wilke, G. W. Gruber. and U. Roy, J. Am. Chem. Soc., 94,2752
(19721. (3) See, for example, (a) C. D. Smith, J, Am. Chem. SOC.,88, 4273 (1966); (b) I. Tabushi, K. Yamamura. and 2. Yashida. ibid., 94, 1787 (1972);(c) D. M. Lemal, ibid, 91, 5688 (1969);(d) H. Prinzbach and J. Rivier, Angew. Chem., lnt. Ed. Engl., 6, 1069 (1967);(e) H. Prinzbach, Pure Appl. Chem., 16, 17 (1968); (f) G. Kaupp and H. Prinzbach, Chem. Ber., 104, 182 (1971). (4) I . Tabushi and I
