TY - JOUR
T1 - 220 MHz nuclear magnetic resonance analysis and selective deuteriodeprotonation of benzo[a]pyrene and 6-methylbenzo[a]pyrene
AU - Cavalieri, E.
AU - Calvin, M.
N1 - Funding Information:
sulphuric [2H2]acid (1.5 ml) at 5-10' and left for120 s. The deep red solution was then poured intodeuteriated water (10 ml) and chloroform (5 ml), previouslylo E. Cavalieri and M. Calvin, Proc. Nut. Acad. Sci. U.S.A.,1971, 68, 1251.chilled, with the temperature maintained below 17". Thechloroform layer was separated and the aqueous layer wasextracted again with chloroform (5 ml). The total organicsolution was washed with deuteriated water (5 ml), dried(Na,SO,), and evaporated. The residue (ca. 20 mg) wasdissolved in [2H]chlor~form (1 ml) and its spectrum wasrecorded.(b) Compound (1) (25 mg) was dissolved in conc. sulphuric[2H2]acid (1.5 ml) at room temperature and then stirred for60 s. The same procedure as (a) was then followed.(c) The same conditions as (b) were used; compound (1)was left for 120, 180, 240, or 480 s in sulphuric [2H2]acid.Deuteriodeprotonation of 6-Methylbenzo[a]py~ene (2) .-Compound (2) (30 mg) was dissolved in sulphuric [2H2]a~id(1.5 ml) and left for 120 s at room temperature with stirring.The solution became green. The same procedure as in(a) was followed. Results (Figure 4) show the absence ofthe H-3 signal at 7-95 and the H-1 signal at 8-11 p.p.m.This research was supported in part by the U.S. AtomicEnergy Commission. One of the authors (E. C.) was arecipient of a Damon Runyon Cancer Research Fellowship,1968-1970. We thank Dr. Melvin P. Klein and Dr. AlgisAlkaitis for discussions.[1/360 Received, 22nd March, 1971111 L. F. Fieser and E. B. Hershberg, J . Amer. Chem. Soc.,12 Huang-Minlon, J . Amer. Chem. Soc., 1946, 68, 248.1938, 60, 2562
PY - 1972
Y1 - 1972
N2 - An analysis of the 220 MHz magnetic resonance spectra of the carcinogenic benzo[a]pyrene (1) and 6-methylbenzo[a]pyrene (2) is presented. A study of proton exchange in sulphuric [2H2]acid is used to determine the specific positions of electrophilic substitution. Electrophilic attack on compound (1) takes place predominantly at the 6-position, and then at the 1- and 3-positions, whereas in compound (2) the most active positions are C-1, C-3, and C-5, with C-5 the least active of the three.
AB - An analysis of the 220 MHz magnetic resonance spectra of the carcinogenic benzo[a]pyrene (1) and 6-methylbenzo[a]pyrene (2) is presented. A study of proton exchange in sulphuric [2H2]acid is used to determine the specific positions of electrophilic substitution. Electrophilic attack on compound (1) takes place predominantly at the 6-position, and then at the 1- and 3-positions, whereas in compound (2) the most active positions are C-1, C-3, and C-5, with C-5 the least active of the three.
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U2 - 10.1039/P19720001253
DO - 10.1039/P19720001253
M3 - Article
AN - SCOPUS:0012332594
SN - 1472-7781
SP - 1253
EP - 1256
JO - Journal of the Chemical Society, Perkin Transactions 1
JF - Journal of the Chemical Society, Perkin Transactions 1
ER -