2644
SEBASTIAN AND TI
J. Org. Chem., Vol.36, No. 8,1970 SCHEME Va
SCHEME IV 'Of
I
m/e 198
J II Ph--P:
m/e 199
1
-(CH,),C=CH,
'OH
c1 m/e 272(274)
OH
I Ph-P:'
Cl
m/e 216(218)
1
-CH,
-(CH,),C=CH,
m/e 143
i +
I
I
OH
OH
m/e 201 (203)
m/e 142
\
'O+ Ph--P-
It I
C(CHJ,
m/e 166
OH
The mass numbers in parenthesis denote the ion containing
m/e 183
87~1.
spectra of diarylphosphinic acids, lo confirm that we isolated arylalkylphosphinic acids and not the compounds originally reported. The principal peaks of the mass spectrum of p-tbutylphenyl-t-butylphosphinyl chloride with sizes relative to the base peak 216 are 274 ( l l ) , 272 (30), 218 (43), 203 (24), 201 (83), 181 (6), and 166 (4%). Meta-
stable ions are observed a t 189, 187 with a broad peak a t 171.8, and correspond to the transitions 218 -+ 203, 216 -+ 201 and 272 --L 216, and 274 218, respectively. Scheme V illustrates this pattern.
Registry No.-111, 25097-42-1 ; IV, 4923-86-8; Y, 25097-44-3 ; aluminum chloride, 7446-70-0; t-butylbenzene, 98-06-5; phosphorus trichloride, 7719-12-2.
Conformation of the Sodium Salts of 4-Phenylbutyric Acid and w-Phenyloctanoic Acid in Aqueous Solution
JOHN F. SEBASTIAN~ AND n l m A Ti Department of Chemistry, M i a m i University, Oxjord, Ohio 46066 Received October 83, 1969 The conformations of the sodium salts listed in the title have been investigated in deuterium oxide by nuclear magnetic resonance spectroscopy. The conformation of 4-phenylbutyric acid sodium salt has been found to exist in the anti form with respect to the P,y carbon-carbon bond. The data do not permit the establishment of a unique conformation for sodium w-phenyloctanoate, but possible conformations are delineated.
The nature and extent of the intermolecular and the intramolecular interaction of two or more apolar moieties in water continues to be a subject of extensive and lively investigation. 2-11 The elucidation of these interactions is crucial to an understanding of molecular conformations and reaction mechanisms in aqueous solution. Over the past few yeah many investigators have examined the nature, structure, and the effect on reactiv(1) To whom inquiries should be sent. (2) W. Kauzmann, Advan. Protein Chem., 14, 1 (1959). (3) G. Nemethy and H. A. Scheraga, J . Phys. Chem., 66, 1773 (1962). (4) I. M. Klotz, Fed. Proc., Fed. Amer. SOC.Exp. Biol., 24, Suppl. 15, 5-24 (1965). (5) H. Inoue and T. Nakagawa, J . Phys. Chem., 70, 1108 (1966). (6) P. Mukerjee, ibid., 69, 2821 (1965). (7) N. Muller and R. H. Birkhahn, ibid., 71, 957 (1967). (8) R. H. Conrad and L. Brand, Biochemistry, 7, 777 (1968). (9) D. M. Crothers and D. I. Ratner, ibid., 7, 1823 (1968). (10) D. S. Olander and A. Holtaer, J. Amer. Chem. Soc., 90, 4549 (1968). (11) M. P. Sohweizer, A. D. Broom, P. 0. P. Ts'O, and D. P. Hollis, ibid., 90, 1042 (1068).
ity of micelle^.^^'^^^-^^ However, the conformations of the molecular constituents of micelles have received relatively little attention. It has been fairly well established in a number of cases that a t concentrations below the critical micelle concentration (cmc), intermolecular association can occur.6'16 We have initiated a study of w-phenylalkylcarboxylic acid salts in aqueous solution with the goal of obtaining information regarding the conformations of the anions a t concentrations below the cmc. Our approach makes use of the phenyl ring as a conformational probe. The magnetic anisotropy arising from the ring current of the phenyl ring will affect the chemical shifts of any protons located in the (12) R. Haque, J . Phys. Chem., T2, 3056 (1968). (13) R. B. Dunlap and E. H. Cordes, J . Amer. Chem. Soc., 90, 4395 (1968), and referenoes cited therein. (14) L. R. Romsted and E. H. Cordes, ibid.,90, 4404 (1968). (15) E'. M. Menger and C. E. Portnoy, ibid., 90, 1875 (1968). (16) P. Mukerjee, K. J. Mysels, and C. I. Dulin, J . Phys. Chem., 62, 1390 (1958).
J. OTg. Chem., Vo1.56,No. 8,1070
4-PHENYLBUTYRIC ACIDAND w-PHENYLOCTANOIC ACID
2645
TABLE I CHEMICAL SHIFTSOF
THE
ACIDSIN DEUTERIUM OXIDEAND CARBON TETRACHLORIDE Chemical shifts, ppma
Compd
Solvent (pD)
Concn, M b
-CsHa
-CHzCsHa
-CHz-C
