May, I951
I,% AND 2,6-NAPHTHOQUINONEbISULFONIMIDES [CONTRIBUTION FROM
THE NOYES
Quinone Imides. VII.
2219
CHEMICAL LABORATORY, UNIVERSITY O F ILLINOIS]
1,2- and 2,6-Naphthoquinone Disulfonimides
BY ROGERADAMSAND R. A. WANKEL I t has been demonstrated that the 1,2-and 2,6-naphthylenedibenzenesulfonarnidescan be oxidized to the corresponding iiaphthoquinone dibenzenesulfonimides. Lead tetraacetate in benzene is the most satisfactory oxidizing agent for the former and purified lead dioxide in benzene for the latter. Both quinone diimides are readily reduced to the corresponding diamides and add various reagents such as hydrogen chloride, morpholine and thiophenol in a manner similar to other quinone diimides previously described.
The quinone imides previously described have oxidation was effected by means of freshly prebeen limited to the sulfonyl derivatives of various pared lead dioxide in boiling benzene, a superb reagent recently described by Kuhn and Hammer.2 9-phenylenediamines,la 1,4-naphthylenediamine~~~ and p-aminopheno1sld as well as to certain acyl 2,6-Naphthoquinone dibenzenesulfonimide is and aroyl derivatives of p-phenylenediamines. lb readily reduced to the corresponding naphthyleneThe study has now been extended to the benzene- diamide. It adds hydrogen chloride, morpholine sulfonyl derivatives of 1,2- and 2,6-naphthylene- and thiophenol to give the chloro, morpholino and phenylmercapto derivatives, respectively, of naphdiamines. thylene-2,6-dibenzenesulfonamide.The position of the groups was not established since no appropriate reference compounds were available. An attempted oxidation of l-benzenesulfonROUSN*~ amido-2-naphthol to the corresponding monoimide failed. I I1 Ultraviolet absorption spectra data on the 1,2-, The 1,2-diimide (I) was formed preferably by the 1,4- and the 2,6-naphthoquinone dibenzenethe oxidation of the appropriate disulfonamide by sulfonimides are shown in Table I. It is significant means of lead tetraacetate in hot benzene, although that all three have strong maxima at 219 mp and lead tetraacetate in acetic acid or freshly prepared at about 240 mp. lead dioxide in hot benzene, achieved the same TABLE I result but in lower yields. 1,fZ-Naphthoquinone ULTRAVIOLET ABSORPTION SPECTRA OF NAPHTHOQUINONE dibenzenesulfonimide is an orange crystalline comDIIMIDES pound, stable under ordinary conditions. It Naphthoquinone exhibits the same reactions as the 1,4-isomer. dibenzenesulfonimide X in mp E X 10-3 max. It is reduced to the diamide by means of hydrogen 1,2219 33.3 and a platinum catalyst. Upon addition of hy240 27.0 drogen chloride in chloroform solution, 4-chloro350 10 6 naphthylene-l,2-dibenzenesulfonamide is formed, 1,4219 33 9 the structure of which was established by an in233 36.4 dependent synthesis from 4-chloro-2-nitro-1-naph273 6.3 thylamine through reduction to the diamine and 11.8 304 benzenesulfonation. Morpholine also adds, pre2,6219 27.8 sumably with formation of the 4-morpholinonaph243 26.3 thylene-l,2-dibenzenesulfonamide. Thiophenol, on Experimental the other hand, did not add to the 1,2-naphtho2-Benzenesulfonamido-1-naphthylamine Hydrochloride. quinone dibenzenesulfonimide but was oxidized -The reduction of 15 g. of benzenesulfonyl-2-amino-lwith simultaneous reduction of the quinone diimide nitronaphthalene$ was carried out in 40 ml. of absolute to the naphthylenediamide. Oxidation of the ethanol with 0.3 g. of platinum oxide under hydrogen a t 4-chloronaphthylene-1,2-dibenzenesulfonamide to 40 p.s.i. The reaction was complete after shaking for three Filtration, followed by addition of 150 ml. of dry the 4-chloro-l,2-naphthoquinonedibenzenesulfon- hours. ether and saturation with dry hydrogen chloride, gave a imide took place readily but the latter compound brown precipitate which was collected on a filter. Recrysfailed to add hydrogen chloride and is apparently tallization from methanol (Darco) and dry ether gave colorresistant to addition reactions under the conditions less crystals, m.p. 185-186" (cor.). The yield was 10.7 g. (71%) . employed. Anal. Calcd. for C1eHlbC1N302S: C, 57.39; H, 4.52. Naphthylene-2,6-dibenzenesulfonamidewas oxiC, 57.38; H, 4.76. dized by lead tetraacetate in benzene but the crys- Found: of talline quinone diimide (11) decomposed rapidly 8.0Naphthylene-l,2-dibenzenesulfonamide.-Treatment g. of 2-benzenesulfonamido-1-naphthylamine hydroon standing. Apparently this accelerated decom- chloride with 20 ml. of pyridine and 3.1 g. of benzenesulposition must be ascribed to the acetic acid or fonyl chloride at refluxing temperature for one hour gave a brown precipitate when poured into 100 ml. of dilute hydrolead diacdate in the reaction mixture, for a stable chloric acid. Filtration followed by recrystallization from deep orange crystalline product resulted when the 8879 formic acid (Darco) gave colorless crystals, m.p. 160-
M=NSO,R
(1) (a) R. Adams and A. S. Nagarkatti, THISJOURNAL, 12, 4601 (1950); (b) R. Adams and J. L. Anderson, i b i d . , 12, 5154 (1950); ( c ) R.Adams and R. A. Wankel, i b i d . , 13, 131 (1951); (d) R. Adams and J. H. Looker, i b i d . , 13, 1145 (1961); (e) R. Adams and K. R. Eilar, i b i d . , 78, 1149 (1951); (f) R. Adams and C. R. Walter, i b i d . , 73, 1152 (1951).
161 (cor.). The yield was 7.3 g. (70%). Anal. Calcd. for G2H18N2O4S2: C, 60.25; H, 4.14; N, 6.39. Found: C, 60.38; H, 4.29; N, 6.21. (2) R. Kuhn and 1. Hammer, Bcr., 83,413 (1950); 84,91 (1951). (3) G.T.Morgan and W.Godden, J . Chem. Soc.. 91, 1714 (1910).
2220
ROGERADAMSAND K. -1. WANKEL
VOl. 73
1,Z-Naphthoquinone Dibenzenesulfonimide.-A suspension of 1.O g. of naphthylene-l,2dibenzenesulfonamide in 25 ml. of benzene was stirred for 2 hours a t refluxing temperature with 1.0 g. of dry lead tetraacetate. After thorough cooling followed by filtration, the product was precipitated from the benzene filtrate by the addition of 125 ml. of petroleum ether (b.p. 35-40 ") . Recrystallization from benzene and cyclohexane or from glacial acetic acid gave orange needles, m.p. 171-172" (cor.). The yield was 0.71
1-Benzenesulfonamido-2-naphthol.-A mixture of 10.O g. of 1-amino-2-naphthol hydrochloride dissolved in 25 ml. of pyridine was treated with 9.1 g. of benzenesulfonyl chloride. Considerable heat was evolved and a dark brown coloration occurred. After standing a t room temperature for 12 hours, the mixture was added to 100 ml. of dilute hydrochloric acid, stirred well, cooled and the crude product collected on a filter. Recrystallization from hot benzene (Darco) gave white needles, 1n.p. 168-169" (cor.). The yield was 11.0 g. (70%). g. (72%). i l n a l . Calcd. for CP?H~SSBO&: C, 60.52; H, 3.70. A?ZUl. C&d. for C I ~ H I ~ N O ~C, S : 64.20; H, 4.38. Found: C, 60.62; H, 3.58. r>ourld: C , 64.24; H, 4.50. This diimide was also prepared by using lead tetraacetate This compound gives no precipitate with dry hydrogen in acetic acid and freshly prepared lead dioxide in refluxing chloride in ether, hence benzenesulfonyl chloride must have benzene. The yields in both cases were lower. reacted with the amino group and not the hydroxyl group. -4 solution of 1,2-naphthoquinone dibenzenesulfonimide TWOattempts t o oxidize 1-benzenesulfonamido-2-naphthol in methanol was reduced t o naphthylene-l,2dibenzenesul- t o the 1,2-naphthoquinone-l-monobenzenesulfonimidein Fonamide using platinum oxide catalyst and hydrogen a t 40 boiling acetic acid with lead tetraacetate failed entirely; 1l.s.i. only the original amide was recovered unchanged. Two attempts to add thiopheriol t o 1,2-naphthoquinone Naphthylene-2,6-dibenzenesulfonamide.-A solution of tiihenzenesulfonimide in glacial acetic acid and in chloroform 1.0 g. of 2,6-naphthylenediamine in 15 ml. of pyridine was gave only the reduced product, naphthylene-l,2-dibenzene- treated with 2.3 g. of benzenesulfonyl chloride. Considersulfonamide. able heat was cvolveti and a dark purple coloration occurred. 4-Chloronaphthylene-l ,24ibenzenesulfonamide .-( A) After standing at room temperature overnight, the solution A solution of 0.4 g. of 1,2-naphthoquinone dibenzenesulfon- WLS pourvd iiito In0 rril. of dilute hydrochloric acid, cooled imide in 10 ml. of acetic acid was treated with dry hydrogen iu an icc-bath, arid the purple product collected on a filter. chloride. Ilccolorizatiori took place immediately and after Recrystallization froin 95'% ethanol (Darco) gave colorless standing for one hour, the product was precipitated with cry.;t:ils. m.p. 245-246 (cor.). The yield was 2.5 g. (90%). \rater. Recrystallization from Bo/, formic acid gave white A l u u l . CaIcd. for CI?H~~K&S.:C, (Xl.25; H , 1.11; K, cry-st:ils,1ii.p. 225" (cor.). The yield mas 0.4 g. (85%). i Found: C, 00.29; 11, 4.23; S,6.56. Ancii. Calcd. for C22HI?ClP'j20&: C, 55.57; H, 3.62; 2,6-Naphthoquinone Dibenzenesulf0nimide.-A mixture 9,5.92. Found: C, 56.06; H, 3.78; N, 5.79. of 0.50 g. of naphthylene-2,6dibenzenesulfonamideand 2.0 (€3) A solution of 1.0 g. of 4-chloro-2-nitro-1-naphthyl- 1:. of freshly prepared lead dioxide* was added t o 25 ml. of atnine4 in 10 ml. of glacial acetic acid was reduced catalytic- boiling benzene. After stirring a t refluxing temperature ally with platinum oxide and hydrogen a t 40 p.s.i. Fil- for 20 minutes, the solution was quickly cooled and filtered. tration followed by addition of 50 rnl. of dryetherand satura- Treatment of the filtrate with 100 ml. of petroleum ether tion with dry hydrogen chloride gave a brown precipitate (b.p. 35-40 ") gave an orange-brown precipitate. Recrysxhich wits collected on a filter. Recrystallization from tallization from benzene and cyclohexane gave dark orange methaiiol arid ether g l i r c 0.9 g. of the diamine hydrochloride. needles, m . p . 166-187" (cor.). The yield was 0.36 g. This salt WLS dissolved in 8 ml. of pyridine and treated uith (73%). 1.3 g. of 1)eiizeiiesulfoiiyl chloride. After standing 12 hours, Ancil. Calcd. for CZ~H&ZO&: c, 60.53; H, 3.70; the brown solution TVLIS stirred into 50 ml. of dilute hydroK,6.42. Found: C,60.77; H,3.85; N,6.53. chloric gicid. After thorough cooling, the product was colCatalytic reduction of 2,6-naphthoquinone dibenzeneIwted on a filter. rZfter thrce recrystallizations from 88yo formic acid, the wliitt. product inelted at 225'. The nivlt - sulfotiitnide in methanol, using platinum oxide and hydrogen at 4n p.s.i., gave naphthylene-2,6-dibenzenesulfoniiig point was not tlepressed whrn mired with 20% of the :tmidr in 70% yield. Attempted addition of thiophenol in compound prepared 11y method ( A ) . The infrared spcctra benzene as the solvent gave only a semi-solid from which no of the two products were ideutiwl. 4-ChlOr0-1,2-naphthoquinone Dibenzenesulfonimide .- A crystalline material could be isolated. 4 (?) -Chloronaphthylene-2,6-dibenzenesulfonamide.-A suspension of 0.5 g . of 4-chloronaphthylerir-1 ,2-dibenzenesulfonimide aiid 0 . 3 g. of lead tetraacetate in 3 ml. of glacial solution of 0.3 g. of 2,6-naphthoquinone dibenzenesulfonacetic acid was stirred a t 5i)" for 45 minutes. After thor- imide in 25 ml. of benzene was treated with excess dry hyough coolintz. the Droduct was collected on a filter and re- drogen chloride. Decolorization occurred in five minutes. cr&tallized-from glacial acetic acid; orange needles, n1.p. After standing one hour, 100 ml. of petroleum ether (b.p. 35-40') was added with stirring. Filtration, followed by 193-194" (cor.). The yield was 0.27 g. (55%). Anal. Calcd. for C?.?HI~CISLO&:C, 56.10; 11, 3.12; recrystallization from 95% ethanol (Darco) , gave a white product, m.p. 193-194' (cor.). The yield was 0.22 g. S ,5.95. Found: C, 53.86; 11, 3.38; N, 5.78. (67%). This compound did not zitid hydrogen chloride c-ithcr i i i A ~ o l . Calcd. for Cz2HllClNsO&: C, 65.87; H, 3.62. gl.icial acetic acid or chloroform as solvents. I~ound:C, 55.68; H, 3.85. 4 -Morpholinonaphthylene - 1,2-dibenzenesulfonamide 4 (?) -Morpholinonaphthylene-2,6-dibenzenesulfonamide. A solution of 0 . 3 g. of 1,2-naphthoqnitione dibenzenesulforiiinide in 5 nil. of glacial acetic acid was treated with 0.5 -- X solution of 2,6-naphthoquinone dibenzenesulfonimide rril. of inorpholiiit.. After standing overnight, the crutic i i i 15 ml. of benzene was treated with 0.30 g. of morpholinc. 1)~colorizationoccurred in two minutes. After standing product was precipitated by the addition of 1 0 ml. of water. After collecting on a filter the brown precipit'ite was dis- 24 hours, the benzene was removed under reduced pressure solved in 10 ml. of 10% aqueous sodium hydrouide (Darco) . l i n t 1 the residue dissolved in 10 ml. of acetic acid. After Filtration, followed by acidification with acrtic acid, gavp a trt atment with charcoal, the gray product was precipitated by the addition of 20 ml. of water. Recrystallization from light gray product. Recrystallization from BOYo ethanolwater gave white crystals, m . p . 7&7%5' (cor.). The. yield 70% ethanol-water gave white crystals, m.p 182-183" (cor.). The yield was 0.25 g. (69%). was 0.47 g. (82%). Anal. Calcd. for Cz&126N~0sSz: C, 59.63; H, 4.81; Anal. Calcd. for C Z ~ H E , N ~ ( ~C,& ~59.63; : H,4.81; K,8.04. Found: C, 59.64; H , 5.04; X, 7.92. N , 8.02. Found: C, 59.53; H, 4.62; N, 7.92. (4) H. H. Hodgeon and
S. Birtwell, J. Chem. Soc., 321 (1943).
URBANA, ILLINOIS
RECEIVED OCTOBER27, 1950
