Papergrams.-Two hystems which have hcru fount1 to separate neomycin and neamine 011 the papergram are (1 ) n-butanol 50 parts by volume, water 25 parts, acetic acid 8.5 parts, and ( 2 ) 50 parts by volume, Rater 1,j parts, acetic acid ,j part?;. Rcwlutioti of the bases is 01)tairied whether thesr arc applied a s thc hydrochlorittrs or : I \ the salts of ~-(p'-hydrosyphciiylazo)-l~ctizciicsulfoiiic acid. The location of the bases is determined cithcr by sprxying the dried sheet with ninhydrin reagent or by incubating the developeti sheet 011 a11 agar plate seeded \vitIi L: microorganism. The crystalline p-( p'-hydroxyphenylazo)-henzenesulfonates of neomycin A and methanolysis product 1 (neamine) were run side by side on Whatman paper nurnhcr 1 i l l descending fashion i i i the butanol system and the distniice from the origin tletcrmined after a aO-iiour period of time. This distance ivas identical as shown in Table I . The same compounds were run asceridingly in the propanol system and gave identical Rr values as listed in Table i THESQUIBB IXSTITI?TE FOR %lEDIC.\I, KESEAKCII SEW RRI:SS\YICK. S . J . .~
Derivatives of Sulfenic Acids. VIIS Addition of Sulfenyl Halides to Olefins BY SORMAX KHAR.\SCEI,CHARLES M. B ~ E S S STRASHUX RECEIVED hxARCH 1, 1952
SUVNER
1.
In a previous the characterization Of a series of olefins via 2,1-dinitrobenzenesulfenyl chloride (I) was reported, and the reaction involved was discussed. Six new examples of this reaction are now in The cVstal1ine products may serve as useful derivatives.
fiecl with assurance to be the expected B-halo suifides, 2-bromocyclohexyl 2'-nitrophenyl sulfide. Application of Markownikoff's rule, considering the polarity of the sulfenyl halides as ArS6+X6--, suggests the most probable structures for the 1: 1 to the unsprnlnetricalopen-chain olefins of
I. ",l-Diriitroberizenesulfenyl bromide was obtained by reaction of I with potassium bromide (S arid &ion of bromine on 2,J-dinitrothiop . The preparation of this sulfenyl bro(T5mid low yield, by brominolysis of 2,4-dinitrophenyl disulfide, was mentioned previously,3 but its analysis and syntheses have not been recorded. Experimental Adducts of Table I.-Known procedures were used to prepare Z,~-dinitrobenzenesulfetiyl chloride3 and 2-nitrobenzenesulfenyl bromide . 4 The preparation of 2,4-dinitrobenzenesulfeny 1 bromide is given below. Additions to the olefins were made in glacial acetic acid by the general technique previously described.' U'ith the sulfenyl bromides, the reaction mixtures were heated on the steam-bath for five to ten minutes, then let stand a t room temperature for one day, rather than heating until a negative test for the sulfenyl bromide was obtained. The olefins used were either the purified commercial products, or were prepared by standard methods. Yields of the crude adducts were generally 6i)-80'%, and purifications were effected by recrystallization
fg. of Irin 25oml. of; benzene ~ was~Bromide,-A ~ ~ solution ~ ~of ;,? ~ ~ ~ shaken with 30 g. of dry poium bromide for 24 hours.
The orange solution w:~$
TABLE 1 REACTIOSS OF SULFESTL HALIDESWITH OLEFINS
Analyses,d Sulfenyl" halidr
Olefin
Product
M.p., OC.']
C
Calcri.
H
? ;,
C
Found
I1
Allyl bromide I CyHsO,&BrCIS 110--11l C 30.40 2.27 30.48 2.32 34.41 3 , 08 I CyHqOdSrCI?S 110-111 34.74 2.59 Allyl chloridc 45.31 2.48 45.05 2.70 I CIIHIOO~SICIL? 1r3-151 9-Chlorostyrene 39.96 3.66 39.89 3.60 I1 C1~H~30J~BrS 1 17-1 18 Cyclohexene 52.71 3.i1 3 , .59 52.68 I CieHiaOiX?CIS 156-157 1,4-Dihydronaphthalene 52.88 3.81 3.84 l,+Dihydronaphthalene 111 C16HldO&BrS 94-96 52.75 51.37 3.27 51 .36 3.16 Indene I CijHii01S\;?ClS 126.5-127 44.06 3.13 2.87 142-143 -43.86 Styrene I1 CI~H,,04S~BrS 37. 49 2.79 2.83 1t i i - - 1ti9 37. 4.5 I CioHgOeStClS Vinylacetic acid I, 2,4-Dinitrobenzenesulfenyl chloride; 11, 2,4-dinitrobenzenesulfenyl bromide: I I I, 2-nitrobenzenesulfenyl bromide. The melting point of a mixture of the adducts of I to allyl chloride and allyl broniide Melting points are not corrected. was not depressed-suggesting formation of mixed crystals. Analogous behaviors appear to be involved in the adducts of I and TI with cyclohexene and styrene. The melting points of the adducts of I with these olefins, previously recorded, are essentially the same (117-118" and 143-143.5')' as those of the similar adducts of I1 (see above); melting points of mixtures of the corresponding pairs were not appreciably depressed. il \Ye arr indebted to Dr. A. Elek and Mr. J. Pirie for the micro:tnalyses.
While additions of sulfenyl chlorides t o olefins are already well known, formation of 2-chloroethyl 2'-bromocyclohexyl sulfide from 2-chloroethanesulfenyl bromide and cyclohexene appears to be the only recorded addition of a sulfenyl bromide to an olefin.? The adducts of 2,-Ldinitrobenzenesulfenyl bromide (11) with cyclohexene and styrene, as well as the adduct of 2-nitrobenzenesulfenyl bromide (111) with 1 ,-Mihydronaphthalene, are now reported. Independent proofs of structure for the products of Table I were not made. The structures of the 1 . I adducts of I and 111 with l,,l-dihydronaphthalrile, as well a s o f I 1 with cycloheuerie, may be speci\ I ) U Kharasch and ,L) l< i I n i o l l P i 11
C \I I
01,
h e i \ (/l
