3500
AHMEDMUSTAFA
AND SALAH
MOHAMED ABDEL
Alkylation of l-Benzhydryl-2-methyl-2-thiopseudourea.l-Benzhydryl-2-methyl-%thiopseudourea, 7.68 g. (0.03 mole), and methyl iodide, 6.4 g. (0.045 mole), were refluxed in 100 ml. of acetone with 2 g. (0.015 mole) of potassium carbonate for 1 hr. Some inorganic material was filtered off and the acetone filtrate was evaporated d o n n in ZWLUO a t room temperature to leave a thick oil residue. The residue was taken up in chloroform and the chlorclforIn wlution filtered to rcrnove more inorganic solidi. The
D . ~ Y E MZ A Y E D
1701.
79
chloroform was then evaporated down in vacuo a t room temperature and the residue taken up in B little isopropyl alcohol. Upon addition of dilute hydriodic acid t o the isopropyl alcohol solution, 4.0 g. of a solid hydroiodide salt, m.p. 102-164", precipitated. Two recrystallizations from an isopropyl alcohol-ether mixture gave a product, m.p. 173-171", which was identical in every way with l-benz~lydrvl-2,3-dimethyl-2-thiopseudourea hydroiodide.
MOSTREAL, CANADA
[CONTRIBUTION FROM THE DEPARTMENT O F CHEMISTRY,
FACULTY O F SCIENCE,
CAIRO UNIVERSITY]
Reactions with Mercaptans. IV. Reaction of Aromatic Thiols with 3(2H)Thianaphthenone- 1,l-dioxides and 2-Benzylidene-3 (2H)-thianaphthenone- 1- 1-dioxide BY AHMEDMUSTAFA AND SALAH MOHAMED ABDELDAYEM ZAYED RECEIVED NOVEMBER 19, 1956 The condensation reaction of 3(2H)-thianapht~ienone-l,l-dioxides( I ) with aromatic aldehydes has been investigated, 3(2N)-thianaphthenone-l,l-dioxidecondenses with benzaldehyde t o give 2-benzyIidene-3(2H)-thianaphthenone-l,1dioxide (IIa). The latter undergoes an addition reaction with thiophenol, yielding the thiol adduct believed to have structure VI. Aromatic thiols react with 3(~11)-tl~i~naphthenone-l,l-dioxides, in the presence of anhydrous zinc chloride and hydrogen chloride, t o yield the corresponding unsaturated sulfides VI1 which are readily oxidized to the sulfone derivatives e.g.,
VIII.
Aldehyde condensation products
of
3(2H)-
thianaphthenone-1,l-dioxide(Ia) have not previously been prepared, although I a has been known since 1912.' Weston and Suter2 were unable to condense benzaldehyde with Ia in an alkaline medium. We obtained well-defined crystalline products by the reaction of benzaldehyde with Ia and by that of p-nitrobenzaldehyde with 7-methyl-3(2H)thianaphthenone-1, 1-dioxide (Id). The analytical data indicate that one molecule of aldehyde condenses with one molecule of the thianaphthenone-1,l-dioxide with the elimination of one rnolecule of water. The structural assignments for these products are based on their participation in known reactions. When 2-benzylidene-3(2H)-thianaphthenone-1,l-dioxide (IIa) was treated with hydroxylIv IIIa, R = OH amine hydrochloride, the corresponding oxime of b, R = N H C e H 5 3(2H)-thianaphthenone-l,l-dioxide(IIIa)3 was obt ~ ~ i n e dThe . ~ treatment of IIa with phenylhydra- goes addition reaction with thiophenol in absence of zine gave the hydrazone of 3(2H)-thianaphthen- a catalyst to give a colorless adduct which can he one-1,l-dioxide (ITIb) .6 represented by V or VI. 2-Benzylidene-3(2H)-thianaphthenone reacted with phenylhydrazine to give [ lOH]-thianaphtheno- [3,2-b]-indole (IV), zia the Fischer indole ring closure of the resulting phenylhydrazone of 3( a l l )- t h i a n a p h t h e n ~ n e . ~ , ~ 'IT;e have also studied the addition, e . g . , of benzenethiol, to the double bond at position 2 which is conjugated with the unsaturated group in P-arylidene-3(2EO-thianaphthenone-1,1-dioxides. IIa,like the 2-arylideneindan-1,3-dione~,~ under(1) hi. Lanfry, Compl. v e n d . , 164, 519 (1912). ( 2 ) -4. 1' . Weston and C. h l . Suter, THISJOURNAL, 61, 389 (1039). ( 3 ) D. H . Hartough, "Compounds with Condensed Thiophene Rings,'' Interscience Publishers, Inc., ?Jew York, N. Y . , 1954, p. 160. (4) This reaction is similar to t h a t of hydroxylamine hydrochloride with 2-benzylideneindan-l,3-dione; cf. A. LIustafa and A . H . R . Harhash, THISJ O C R X A L , 7 8 , 1649 (1956). ( 5 ) E. W. McClelland and J. L. D'Silva, J . Ciiem. Soc., 227 (lSJ32). (6) C. E. Dagliesh and F. G . M a n n , i h i d , , 653 (1947). ( 7 ) A . L l i ~ s t o f a !hid.. . 1,770 (19,jl).
0 2
IT1
I n view of the well-established mechanism for the addition of thiols to analogous a&unsaturated
July 5, 1957
-
ACTIONOF AROMATIC THIOLS ON 3 (2H)-THIANAPHTHENONE-l, 1-DIOXIDES
compounds,8 structure VI is preferable. The fact that the adduct dissolves in cold aqueous sodium hydroxide solution with a yellow color and is liberated upon neutralization with ice-cold, dilute hydrochloric acid is also in accord with structure VI, When VI was heated above its melting point for a few minutes and then cooled, the styryl derivative I I a was regenerated. The ease of removal of the addend indicates that the substance is the result of simple addition and that no unexpected reaction has occurred. Attempts to oxidize VI with hydrogen peroxide in glacial acetic acid over a water-bath also led to the formation of IIa.g
I iArSH
3501
ZnClz HC1
VIIa, = R' = R,, = Ar = CeHa VI11 b , R = CHI; R' = R" = H ; Ar = C6H6 c, R = CHI; R' = R" = H ; Ar = C6H4CH3-p d, R " = CH3; R = R' = H ; Ar = C6Hs e, R" = C H J ; R = R' = H ; Ar = CeHaCH3-9 f , R" = C1; R = R' = H ; Ar = CBH6 g, R" = C1; R = R' = H ; Ar = C6HaCH3-p Reaction Of Aromatic with ( 2 H ) - thianaphthenone-1,l-dioxideslisted in Table I were preThianaphthenone-1 +dioxides (I).--It is generally pared from the corresponding 3(2H)-thianaphthenones which accepted that a ketone and a thiol react in the were obtained by known procedures.'e A solution of 5 g. to form a nlercaptal,io of the thianaphthenone in 30 i d . of glacial acetic acid was presence of an acid treated with 25 ml. of 30y0 hydrogen peroxide, and the reacaIthough scattered reports in the literature indicate tion mixture !vas heated (steam-bath) for 1 hr., with the that certain cyclic ketones, e.g., 4-cholesten-3-one" exception of &methyl- and 7-methyl-3(2H)-thianaphtheand other ketosteroids,I2 yield unsaturated sul- none, whereby oxidation was complete in 5 minutes. The reaction products, which separated on cooling, were crystalfides (enol thioethers) k e d from a suitable solvent as colorless crystals; they gave Recently,l3 it was observed that 2-methyl-lno color with concentrated sulfuric acid and a yellow color indanone and 2-methyl-1-tetralone react with thio- in alcoholic sodium hydroxide. phenol, under the conditions of the mercaptal reCondensation of: ( a ) 3(2H)-Thianaphthenone-l,l-dioxide action, to produce phenyl-2-methyl-3-indenyl SUI(Ia) with Benzaldehyde.-A mixture of 1 g. of Ia'i and 2 ml. of benzaldehyde Was heated for 3 hr. Over an oil-bath (140' fide and phenyl-2-methyl-3,4-dihydro-l-naphthyl temperature of bath). The reaction mixture was cooled t o sulfide, respectively. room temperature and triturated with 5 ml. of cold ethyl We have investigated the reaction of aromatic alcohol. The resulting pale yellow solid was crystallized thiols with 3(2H)-thianaphthenone-1,1-dioxides (I) from m.p. 148' (yellow melt). Anal. Calcd. for CisHioOaS: c, 66.66; H , 3.70; S,11.85. in the presence of anhydrous zinc chloride and hydrogen chloride and have obtained colorless prod- Found: C,66.32; H , 3 . 6 1 ; S, 11.56. 2-benzylidene derivative I I a was soluble in benzene to have structure Under butThis difficultly soluble in ether, cold alcohol and acetic acid. these experimental conditions, 2-methyl-3 (2m- I t developed a yellow color in concentrated sulfuric acid. thianaphthenone-1,l-dioxide(IX) did not react A solution of 0.5 g. of IIa in 20 ml. of glacial acetic acid was treated with 2 g. of sodium acetate and 0.5 g. of hywith thiols. droxylamine hydrochloride. The reaction mixture was reDesoxybenzoin14i' known t' form an unsaturated fluxed for 3 hr., cooled and then poured into ice-cold water. sulfide when treated with thiophenol. BY anal- The resulting substance was crystallized from dilute acetic ogy, a similar mechanism may be presented for acid (m.p. 246') and identified as the oxime of 3(2H)the formation of VI1 involving the addition of one thianaphthenone-l,l-dioxide (IIIa)I by a mixed 1n.p. dewith a sample of I I I a , obtained by the reaction mole of thiol to form' a hemimercaptal followed by termination of hydroxylamine hydrochloride with Ia under similar exelimination of water to give the unsaturated SUI- perimental conditions. fide VII. (b) 7-Methyl-3 (2H)-thianaphthenone-l,l-dioxide (Id) The unsaturated sulfides VII, listed in Table 11, with p-Nitrobenza1dehyde.--4 mixture of 1 g. of Id and 1 g. of the aldehyde was heated a t 160" for 2 hr. The solid are Oxidized by hydrogen peroxide in glacial residue obtained after cooling was washed thoroughly with acetic acid to give the corresponding sulfones,l2 hot benzene and then crystallized from nitrobenzene as yellow crystals (IIb), m.p. 265'. I I b was difficultly soluble listed in Table 111. \&'hen V I I ~was treated with aqueous sodium in most organic solvents and gave an orange solution in conacid. hydroxide and zinc dust, 2,3-dihydrothianaph- centrated Anal. Calcd. for C ~ ~ H I I X O S C S :, 58.36; H , 3.34; N, thene-1,l-dioxide and thiophenol were obtained.I5 4.26; S,9.72. Found: C, 57.97; H,3.31; N,4.03; S,9.39. Experimental Reaction of Thiophenol on 1Ia.-One g. of I I a was mixed 3(2H)-Thianaphthenone-l ,l-dioxides ,-The new 3 ( 2 ~ ) - with a slight excess over the calculated amount of the thiol in a test-tube, and the reaction mixture was heated a t 100" for 3 hr. The cooled reaction mixture was triturated with (8) T. Posner, Ber., 36, 809 (1902);B. H. Nicolet, THISJ O U R N A L , boiling light petroleum (b.p. 30-50", 50 ml.) when the oily 63, 3066 (1931); P.S. Bailey and J. C. Smith, J. O Y ~Chcm., . ai, 709 (1956); R. M. ROSSand F. w. Raths, THISJOURNAL, 73, 129 (1961); reaction product turned into solid powder. It was filtered, washed with hot light petroleum and crystallized from benR . M. Ross, H. L. Bushey and R. J. Rolih, i b i d . , 73,540 (1951); R. M. zene; m.p. 138", yield ca. 8 8 ~ o . Ross, ibid., 71, 3458 (1949). (9) w-p-Dinitrostyrene thiol adducts behaved similarly when treated Anal. Calcd. for C21HleO3S2: C , 66.31; H, 4.21; S, with hydrogen peroxide under the same conditions; d. A. Mustafa, 16.84. Found: c , 66.77; H , 4.50; S, 16.49. A. H . E. Harhash and M. Kamel, i b i d . , 77, 3860 (1955). The thiol adduct formed colorless crystals, dissolved (10) E. Baumann, B e y . , 18, 883 (1885). readily in hot benzene but was difficultly soluble in cold
.
uctsj
(11) S. Bernstein and L. Dorfman, THISJOURNAL, 68, 1152 (1946). (12) G. Rosenkranz. S. Kaufmann and J. Romo, i b i d . , 71, 3689 (1949). (13) E. Campaigne and R. D. Moss, i b i d . , 76, 1269 (1954). (14) E.Campaigne and J. R . Leal, i b i d . , 76, 1272 (1954). (15) Cf.the reduction of thianaphthene-1,l-dioxideby zinc dust and aqueous sodium hydroxide to yield 2,3-dihydrothianaphthene-I,1dioxide; F. Challenger and P. H. Clapham, J . Chem. SOL., 1615 (1948).
(16) 5-Methyl-: D.S.Tarbell, D . K. Fukushima and H . Dam, THIS 67, 1643 (1945); 6-methyL: A. Mustafa and S. M. A. D. Zayed, i b i d . , 78,6174 (1956);7-methyl- and 7-chloro-: C. E. Dalgliesh and F. G. Mann, J . Chem. SOL., 893 (1945); and 2-methyl-3(2H)thianaphthenone: C. Hansch and W. A. Blondon, T I ~ IJOURNAL, S 70, 1561 (1948). (17) F. G . Bordwell, B. B. Lampert and W. H . IrlcKellin, ibid., 71, 1702 (1949). JOURNAL,
350%
AHMED3fUSTAFA
.4ND S A L A H LTOHAMED
Vol. 79
ABDELDAYEM ZAYED
TABLE I NEW SULFONES (I) 3(2H)-Thianaphthenone1,l-dioxide
M.p.," OC.
Y!eld,
%
Ib
a
202 IC 190 Id 187 227 IC IXC Above 360 Melting points are uncorrected.
Carbon, 70 Calcd Found
Formula
Hydrogen, % Calcd. Found
Sulfur, % Calcd.
Found
16.32 15.81 4.08 3.99 55.10 54.83 42 CQHSO~S 16.32 16.01 4.08 4.02 55.30 48 CgHsOaS 55.10 16.32 15.88 4.08 4.09 55.10 54.73 45 CQHSOSS 14.78 15.06 2.31 43.82 2.31 44.34 56 CaH603SClb 16.32 16.03 4.01 54.92 4.08 54 CgHsOS 55.10 Calcd., C1, 16.39; found, 16.01. 2-~Methyl-3(2H)-thianaphtlicnone-l,l-dioxide.
TABLE I1 ~-!LRYLMERCAPTOTHIASAPHTHENE-~,~-DIOXIDES
3-Arylmercaptoderiv.
Mdp.,"
c.
Yield,
Color with concd.
%
HnSOi
Formula
Carbon, % Calcd. Found
VIIa 128 81 Yellow CiiH1002Sz 61.31 VIIb 126 79 Orange Ct~H1202S2 62.50 VIIC 144 72 Deep red C16Hl;O& 63.57 VIId 122 74 Yellow C16Hi20zSz 62.50 VIIe 124 71 Orange C16H1402S2 63.77 VIIf 134 82 Yellow C14Hg0&Clb 54.46 VIIg 142 76 Orange Ci6Hn0&ClC 55.81 All melting points are uncorrected. * Calcd., C1, 11.51; found, 10.95.
(\'II) Hydrogen. % Calcd. Found
Sulfur, % Calcd. Found
61.01 3.65 3.57 62.39 4.16 4.00 63.21 4.63 4.53 62.43 4.16 4.43 63.77 4.63 4.93 53.91 2.91 3.16 55.47 3.41 3.31 e Calcd., C1, 11.01; found,
23.36 22.22 21.19 22.22 21.19 20.74 19.84 10.82.
23.12 21.98 20.96 21.74 21.24 20.25 19.43
TABLE I11 OXIDATION P R O D U C T S Oxidation products
a
M.p,," OC.
Yield,
%
O F 3-.kRYLhIERCAPTOTHIANAPHTHENE-1
Formula
Carbon, % Calcd. Found
54.63 77 Ci4Hi604S2 54.90 VIIIa 155 55.99 VIIIb 68 CI~HIZOISZ 56.25 184 17.09 66 Ci6H1104S2 57.48 VIIIC 190 55.98 81 CijH120;Sz 56.25 VIIId 130 57.09 VIIIe 78 Ci~H1404S2 57.48 158 48.97 83 Cl,H904S2Clb 49.34 VIIIf 283 50.08 7
