JULY
1950
XOTUS
1021
scnting abont 7% of the total cell product. These wert identified by infrared and nuclear magnctic rtsonance (NMR) spectra, and by analysis of the methyl ester of the latter. Retention of the entire JOHN .4.YOUNG A N D RICHARD D. DRESDNER striicture in CF3SF4CF2COFis rather surprising, and indicates that fluorocarbon acids containing Received January 16, 1059 sulfur as well as those containing nitrogen' can be Pcrfluoroalkyl sulfur pentafluorides, R,SF5, react made by this method, although the yields in both with unsaturatcd fluorocarbon derivatives to add C ~ S C Sare quite poor. The most novel compound was a liquid (b.p. R p . and F. across the double b ~ n d , as ~ .shown ~ in 8 8 O , m.w. 352) whose analysis corresponded to Equations 1 and 2. (12F14S2, mol. wt. 354. The three possible structiirw CF3SFj + CF3CF=CF2 +CaF,, isomers (1) for this formula are CF3SF4CF2SFS(I), SF,CF&F, (111).The first can be CFaSF6 + CF3N=CFz +(CF3)$N (3) SF5 (11),and CF3SF4SF4CF3 ~liminatedon the basis of the NMR spectrum, I n hopes of extending the scope of this reac'tion which showed all the fluorines on carbon and 6 or 8 to more useful R, groups, it was decided to investi- of those on sulfur to be identical. The &value for gate the reaction of SF6CF2COFunder similar con- the single C-F peak (a triplet) was -5.5 (ref. ditions. Haszeldine4 has shown that electrochemical CFSCOOH). This is in the normal region for CF3 fluorination of thioglycollic acid gives an extremely attached to SF4 (CF3SF4CF2CF3 -9.8) and conlow yield of SF5CF2COF;however, since dialkyl siderably removed from that for CF2 between CF3 sulfides have been found to cleave during this and SF4 or SF5. Chemical shifts for the latter process to give good yields of RFSF5,5~eit was configuration run roughly from +15 to +25, on thought that the desired compound might be ob- the basis of information obtained in this laboratory tained by electrochemical fluorination of CH3- or from the literature,s concerning half a dozen comSCH2COCl. The absence of active hydrogens such pounds of this type. The resonance of the fluorine as -COOH and -SH in this compound would be on sulfur was quite complex, two of the peaks being expected to improve cell performance over that split into five or seven, but the &values of -95.5 shown by thioglycollic acid. The results of the and -116 correspond better with SF4 (-94.8, fluorination of CH3SCH2COC1are reported in this -123 in O(CF2CF2)zSF4)8 than with SFb (-118.7 paper. to 137.5).8Because of the symmetry, presence of Identification of thc materials obtained by frac- CF3and SFs in the same molecule is prohibited, and tioilation of thc crude cell product after conclusion structure 111, CFdSF&3F4CF,,is therefore the most of the run showcd that although considerable probable. This is the first reported instance of tlwo cleavugc had occurrcd, loss of the methyl group vicinal SF4 groups in a fluorocarbon derivative, done had not taken place. Thc two products and this compound cannot be made by electrofound in greatest abundance were CFBFb and chemical fluorination of dimethyl disulfide.6 (CF,),SF4. A large fraction was obtained which had values (b.p. 14-20', mol. wt. 211-228) near EXPERIMENTAL those rcported for SF5CF2COF (b.p. 22O, mol. wt. The apparatus and procodurcs for thc electrochemical 224), but by chromatographic separation it was fliiorination process have been previoiisly doscribcd.6,0 From found that this material was mcrely a mixture con- 615 g. of CI13RCH&OCI, matlc by mcttiylittion of thitr taining (CF3)zSF4and smaller amounts of unidenti- glycollic acid with methyl sulfatc and conversion to the acid fied incompletely fluorinated substances. chloride by means of either PCla or POC12,g a tot,al of 486 Two compounds were isolated which largely rc- g. product boiling above -80' WRS ot)tained, including :jO tained the original structure. These were CF,%- g. recovered its a second phase when t h e cell wits draiiictd after the run. The concentration of solute during the operaSF4CF2CF3 and CF3SF4CF2COF, each reprc- tion was roughly 2 mole %). Fractionation was porfornicd Electrochemical Fluorination of S-Methylthioglycollic Acid Chloride'
-~
( I ) This material was prrsented at tlic hrrctiiig-inlliniature of the Florida Section of thc American Chemical Society, Lakeland, Fla., May 9-10, 1058. The Tork was supported by the Office of Yaval Research, and reproduction of all or any part of this paper is prrmitted for purposcs of thc Unitcd States Government. ( 2 ) T?. n. Dresdner, J . Am. Chem. Soc., 77, 6033 (3055). (3) TI. J). I h s d n c r , J . Am. Chmz. SOC.,79, 69 ( 1 9 5 i ) . (4)13. N. Haszeldine and F. Nyman, J . Chem. Sac., 2684 (1958). ( 5 ) F. W. Hoffmann, T. C. Simmons, R. B. Beck, H. V. Holler, T. Katz, R. J. Koshar, E. R. Larson, J. E. Mulvmcy, F. E. Rogers, B. Singleton, and R. S. Sparks, J . Am. Chem. Sac., 79, 3424 (1957). (6) R . 1). Drcsdner arid J. A. Young, J. Ana. Chem. Sac., 81, 574 (195'3).
in columns appropriate for tjhc tcinpcr:iturcs involved :i11c1 psckcd with nickel helices. Although the five principal fr:m tions described hclow wrre thc only ones identified, forerun and intercuts were relatively large, and small amounts of material boiling as high as 35'/2 mm. were obtained. Fraction A . I3oiling point, -23 to -No, 64 g., mol. wt. 195, chromatographic purity 93%. The infrared spectrum of a c c n h elit W B S identical with that of CFSRF,, b.p. --20", mol. wt. 196.
( 7 ) J . A. Young anti R. D. Drcsdncr, J . Ana. Chem. Soc., 80, 1889 (1958).
(8) N. Muller, P. C. Laliterbur, and G. F. Svatos, J . Am. Chem. Sac., 79, 1043 (1057). (9) A. Mooradian, C. J . Cavallito, A. J. Bcrgman, 13. ,J. Imvson, and C. M. Suttcr, J . Am. Chem. SOC.,71, 3372 (1949).
1022
VOL. 24
NOTES
Fraction H . Boiling point 1G-20", 85 g., mol. wt. 219-228; of thc unsaturated kctoiie) with methoxyamine, reported4 for SF6CF2COF, b.p. 22", mol. wt. 224. Since a substituted hydroxylamines, or hydroxylaminc gas chromatograph showed four to six components over this boiling range a 2 g. sample was quantitatively chromato- has been reported to yield bisketoamines analogous graphed, using a stationary phase of the ethyl ester of Kel-F t o structure In2 acid 8114, on Celite. About 75% of this arnount, representRCHCH2C - A r ing approximately 63 g. of the whole fr:iction, was recovercd I /I as one peak, mol. wt,250, and was iderit,ificd as (C>F3),SF4 I d by comparison of its infrared spcctrum with that of known NOX I (C173)2SF+ b.p. Z O O , mol. wt. 246. The remainder of the RCIICH~C-A~ chromatographed material had an avwage mol. wt. of only
il
148.
Fraction C. Boiling point 47.5", 24 g., mol. wt. 297, purity 99%. An infrared spectrum shoaod all pcaks found in the spectrum of CF3SF4CF2CF3,b.p. 47.1 O , mol. wvt. 2!)ti, but also additional lines a t 10.80--10.85 arid 12.25, and an elemental analysis was therefore made. Anal. Calcd. for C3FleS:C, 12.2; F, 77.1; S, 10.8. Found: C, 12.4; F, 76.8; S, 11.0. Fmmlion I). Boiling point 55", 39 g., mol. wt. 279 (calcd. for CFZSI',CE'ZCOF274), purity 837&An infrared spectrum showed a sharp peak for -COP a t 5.27. Bccause of the impurities present, this cornpound was cwnvcrted for analysis to the methyl ester (67% yield) by rc.fluxing with mcthanol. The ester had b.p. 1 2 3 O , n:: 1.3259. Anal. Calcd. for C,H,H3O,: C, 16.8; F, 59.7; H, 1.1; S, 11.2. Found: C, 17.1; F, 59.0; 13, 1.1; S, 10.9. Principal infrared lines for these t,wo ne^ compounds are: CB,SF&F2COF 5.27, 7.80, 7.90-7.95, 8.06, 9.70, 10.12 (w), 10.83, 11.32 (w), 11.65--11.80, 12.50, 14.0(-14.05, 14.8514.95; CF3SF4CIp2COOCTT3 (in CCI,) 5.60, 6.95, 7.62, 8.008.05, 8.17, 8.63-8.73, 9.95, 11.90-12.00, 12.18, 14.50. Fraction E. Boiling point 87-8S0, 10 g., mol. wt. 352, n:," 1.2964, purity 95%. Refluxing with 3 0 % aqueoiis KOII did not change the mol. wt. and no sign of reaction was observed. Identified by XhIR, as discussed sbovc. Principle infrared lines for this compound are 7.95, 8.63, 10.85-11.05, 11.65-11.75, 12.75, 14.25-14.50. Anal. Calcd. for C2FI4S2:F, 75.2; S, 18.0; mol. wt. 354. I'ourid: F, 75.1; S, 18.0; mol. wt. 352.
Acknowledgment. The authors are indebted to Dr. Max Rogers of Michigan Statc Uiiivcrsity for the NMII. studies. DEPARTMENTS OF ClfEMIsTRY A S D ClIE31ICA1, E N G I N E E R I N G
UNIVERSITY OF FLORIIM GAINESYTI~LE, FLA.
Structure of the Reaction Product of Phenyl Vinyl Ketone and Hydroxylamine DONALD J. C A S E YAND ~ C. S. MARVEL Received January 19, 1959
Under the proper conditions, the reaction of certain a$-unsaturated aryl ketones (or a precursor (1) The work discussed herein was supported by Contracts A F 33(616)-:3772 and -5486 with the Materials Laboratory of Wright Air Development Center, Wright-Patterson Air Force Base, Ohio. Reproduction of this paper in whole or in part is permitted for any purpose of the United States Government. The paper is based on portions of a thesis submitted by Donald J. Casey to the Graduate College of the University of Illinois in partial fulfillment of the requirements of Doctor of Philosophy.
X
=
H or CI13 I
In line with this, Auwcrs and Muller3 have dcscribed a compound mclting at 140' to which thcy assigncd the structurc his@-benzoylcthyl)hydroxylamine (11). This material was preparcd from thc (C6~~jCCa2C~18)/-NOH
!
I1
corresponding dioxirne, which in turn resulted from the trratmcrit of p-chloropropiophenonc with free hydroxylamirie and exccss alkali. Shortly before this, Danilowa and D ~ 1 i l o ~had 4 reported a compound mclting a t 122.5' (obtained from the reaction of a 1:1 ratio of phenyl vinyl ketotic arid frw hydroxylamine) to which they assigned 6tructur.o 111. Both groups reported a compound melting at (C6H4COCII)2-XOII
I
CHs I11
153-154° which they described as the dioxime of the respectivc dicarbonyl compounds (I1 and 111). I n the present work, the reaction of phenyl vinyl ketone with hydroxylamine hydrochloride in thc presence of sodium acetate produced compounds which were demonstrated to be bis(p-bcnzoylethy1)hydroxylamine (TI),m.p. 120.5-121 O , or the dioxime (m.p. 148-149') of this compound. With hydroxylamine hydrochloride and sodium acetate the dicarbonyl compound could bc readily converted into the dioxime, but repeated recrystallizations from three different solvcnts failed to raise the melting point of the dioxime (148-149') to the value reported by Auwcrs3 and Daiiilowa.4 In ordcr to clarify the structure of thew compountls two similar conipoiinds were prepared for a comparativc nuclear magnetic resonance study; bis(P-benzoylethy1)niethoxyamine (IV) w a s produccd in 30/, yield from phenyl vinyl ketone and methoxyamine hydrochloride and bis [P-(p-methoxybenzoy1)ethylJ(2) (a) A. H. Blatt, J . Am. Chem. Soc., 61, 3494 (1939). (b) J. Thesing, A. Miiller, and G. ?rIichel, C h n . Rer., 88. 1027 (1955). (cl E. Profft, F. Rirnge, - and -4.Junar, J , prakt.'Chem.., (41, 1, 57 (1954). (3) K. v. Auwers and H. Muller. J . ~ r a k t Chem., . . .INFI, . 137,'102 (1933). (4)E. Venus Danilow8 and S. Danilony, J . Gen. C h m (U.S.S.R.), 2, 645 (1932); Chem. Abslr., 27, 16246 (1933). I
.
