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    7-Norbornadienyl Carbonium Ion: Department

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    juan jose
    This document reports on the preparation and NMR spectrum of the 7-norbornadienyl carbonium ion. Key findings include: 1) Treatment of 7-norbornadiene with thionyl chloride yielded 7-norbornadienyl chloride, which was dissolved in sulfur dioxide and reacted with silver tetrafluoroborate to form the stable 7-norbornadienyl carbonium ion. 2) The NMR spectrum of the ion at -10°C consisted of four distinct peaks in a 2:2:2:1 ratio, consistent with structure I proposed by Winstein and Ordronneau as the non-classical carbonium ion intermediate. 3) The data eliminate any

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    7-Norbornadienyl Carbonium Ion: Department

    Uploaded by

    juan jose
    35 views1 page
    This document reports on the preparation and NMR spectrum of the 7-norbornadienyl carbonium ion. Key findings include: 1) Treatment of 7-norbornadiene with thionyl chloride yielded 7-norbornadienyl chloride, which was dissolved in sulfur dioxide and reacted with silver tetrafluoroborate to form the stable 7-norbornadienyl carbonium ion. 2) The NMR spectrum of the ion at -10°C consisted of four distinct peaks in a 2:2:2:1 ratio, consistent with structure I proposed by Winstein and Ordronneau as the non-classical carbonium ion intermediate. 3) The data eliminate any

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    This document reports on the preparation and NMR spectrum of the 7-norbornadienyl carbonium ion. Key findings include: 1) Treatment of 7-norbornadiene with thionyl chloride yielded 7-norbornadienyl chloride, which was dissolved in sulfur dioxide and reacted with silver tetrafluoroborate to form the stable 7-norbornadienyl carbonium ion. 2) The NMR spectrum of the ion at -10°C consisted of four distinct peaks in a 2:2:2:1 ratio, consistent with structure I proposed by Winstein and Ordronneau as the non-classical carbonium ion intermediate. 3) The data eliminate any

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    35 views1 page

    7-Norbornadienyl Carbonium Ion: Department

    Uploaded by

    juan jose
    This document reports on the preparation and NMR spectrum of the 7-norbornadienyl carbonium ion. Key findings include: 1) Treatment of 7-norbornadiene with thionyl chloride yielded 7-norbornadienyl chloride, which was dissolved in sulfur dioxide and reacted with silver tetrafluoroborate to form the stable 7-norbornadienyl carbonium ion. 2) The NMR spectrum of the ion at -10°C consisted of four distinct peaks in a 2:2:2:1 ratio, consistent with structure I proposed by Winstein and Ordronneau as the non-classical carbonium ion intermediate. 3) The data eliminate any

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    Dec.

    5, 1960 COMMUNICAT
    'IONS TO THE EDITOR 6199

    absorption bands of the nucleic acids and poly-


    nucleotides.
    We acknowledge the skillful technical assistance
    of M. Capecchi.s
    (S) This work was supported by grants from the National Science
    Foundation and the National Cancer Institute.
    DEPARTMENT OF BIOLOGY
    MASSACHUSETTS INSTITUTE OF TECHNOLOGY
    The other peaks of the spectrum can be reason-
    CAMBRIDGE39, MASSACHUSETIS ALEXANDEE RICH
    INSTITUTE
    OF MOLECULAR BIOPHYSICS ably assigned to: remaining olefin, bridgehead
    FLORIDASTATE UNIVRRSITY MICHAELKASIA and bridge hydrogens, respectively. For com-
    TALLAHASSEE,FLORIDA parison, we have determined the n.m.r. spectrum of
    RECEIVEDSEPTEMBER 19, 1960 7-uorbornadienyl chloride in sulfur dioxide. The
    olefinic hydrogens appear at 3.2 and 3.4 T with the
    THE 7-NORBORNADIENYL CARBONIUM ION lower field peak being an incompletely resolved
    sir: triplet. The bridgehead hydrogens are at 6.3
    and the bridge hydrogen at 5.8.
    Recent investigations into the solvolysis of a
    number of norbornenyl derivatives have been
    characterized by the postulation of non-classical
    carbonium ions as intermediates. The preparation
    of a stable bridged carbonium ion from 7-norborna-
    dienyl chloride has now permitted for the first
    time direct structural evidence to be obtained about
    these interesting species. Heretofore, structural
    evidence relating to these carbonium ion inter-
    mediates has been inferred from kinetic and product
    analyses. For example, the remarkable enhance- Fig. 1.--N.m.r. spectrum of 7-norbornadienyl fluoroborate
    ment of the rate of solvolysis of anti-7-norbomenyl in sulfur dioxide at -10'. Peak positions are given in
    tosylate compared to the 7-norbornyl derivative p,p.m. relative to tetrametbylsilane as 10.00.
    has been ascribed to participation of the a electrons The sulfur dioxide solution appeared to be
    of the double bond to give a stabilized non-classi- stable a t -10" but became deep brown in color
    cal carbonium ion intermediate.' More recently, on standing a t room temperature for a short
    Winstein and Ordronneau2 have reported that period. The absence of skeletal rearrangements
    7-norbomadienyl chloride solvolyzes cu. lo3 faster was indicated by the exclusive conversion of the
    than anti-7-norbomenyl chloride and suggested carbonium ion to the known 7-norbomadienyl
    several possible non-classical structures for the acetate' on addition of acetic acid to the sulfur
    intermediate carbonium ion. We wish to report dioxide solution.
    the preparation and n.m.r. spectrum of this ion.
    Treatment of 7-norbornadieno13 with thionyl BELLTELEPHONE LAEORATORIES
    Munnny HILL,NEWJERSEY PAUL R.STORY
    chloride in ether gave 7-norbornadienyl chloride,l Ka. 1644
    CONTRIBUTION
    which was dissolved in sulfur dioxide at -80" CHEMISTRYLABORATORY
    STERLING
    and slowly added to a similar solution of silver YALEUNIVERSITY MARTINSAUNDERS
    CONN.
    NEW HAVEN.
    tetrafluoroborate.' The silver chloride which pre-
    cipitated immediately was filtered off leaving a OCTOBER20, 1960
    RECEIVED
    colorless solution. The ultraviolet spectrum a t
    -80" showed no absorption above 330 mp, the
    cut-off wave length of liquid sulfur dioxide.
    The n.m.r. spectrum of this solution at -10"
    (Fig. 1) consists of four distinct peaks in the ratio
    2 :2 :2 :1 showing partially resolved spin-spin fine Sir:
    structure. We have assigned these peaks to the In relation to recent studies by Grenthe and
    7-hydrogen, the bridgehead hydrogens and two Fernelius2 on the solution stability of a number of
    diferenl pairs of olefinic hydrogens. The peak rare earth chelates, i t was of interest to make a
    at 2.4 T seems to consist of two overlapping study of the magnetic properties of some of these
    triplets suggesting that the normal norbornadiene compounds. The magnetic susceptibilities of the
    olefin triplet6is split by coupling with one additional acetylacetonates of Pr, Nd, Gd, Tb, Dy, Ho, Er,
    hyrlro~en with coupling constant about 5 C.P.S. Tm, and Yb, all of the same general formula M-
    The above data, which definitely eliminate any (acac)a.HIO (prepared according to Stites, et d 3 ) ,
    symmetrical structure, are consistent with struc- and ethylenediaminetetraacetates of Pr, Nd and
    ture I, which was among those structures pro- Gd of the formula Na[M(EDTA)].8H20 (obtained
    posed by Winstein and Ordronneau.' from Professor T. Moeller; for preparation see
    (1) S. Winstein. M. Shsfausky, C. Norton and R. B. Woodward. (1) The authors wish t o thank the Office of Naval RerXPreh for
    THISJooaml., 77,4181 (1955). financial aid under Contract No. NONR 05024. sod the National
    ( 2 ) S. Winstein and C.Mronneau. ibid.. 8s. 2084 (1960). Seience Foundation for support under Grnot No. 9928.
    (2) P. R . Story. I . Ora. Chsm.. in press. (2) I . rhnthe and W.C. Fernelim, J . A m . Chon. Sr..to he pab-
    (4) <;. A. Olah and H. W. Quinn. J . Inor!. N x r l . C h m . . 8 , 295 lished.
    (3) I. <.: S i t e s . C. N. MrCarfhy and 1,. 1.. Quill, ibid., TO, 5172
    (1418).

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