Sulfonyl esters. 2.

CS cleavage in some substitution reactions of nitrobenzenesulfonates

JAMES CLAYTON BAUM, JIMAT BOLHASSAN, RICHARD FRANCIS LANGLER,' PAUL JOSEPH PUJOL, AND RAJ KUMAR RAHEJA Department of Chemistry, Florida Institute of Technology, Melbourne, FL 32901-6988, U.S.A. Received May 23, 1989' JAMES CLAYTON BAUM, JIMAT BOLHASSAN, RICHARD FRANCIS LANGLER, PAUL JOSEPH PUJOL, and RAJ KUMAR RAHEJA. Can. J. Chem. 68, 1450 (1990). An attempt to explore aromatic sulfonate esters as agents for the condensation of alcohols with mercaptans revealed an unusual process for sulfonate esters: CS bond rupture. Two mechanistic possibilities for CS bond rupture are explored: (i) radical anion intermediacy via single electron transfer and (ii) nucleophilic aromatic substitution. Both experiments and molecular orbital computations are presented to support the conclusion that nucleophilic aromatic substitutions are occurring. Key words: sulfonyl esters, nitrobenzenesulfonates, CS bond rupture. JAMES CLAYTON BAUM, JIMAT BOLHASSAN, RICHARD FRANCIS LANGLER, PAUL JOSEPH PUJOLet RAJ KUMAR RAHEJA. Can. J. Chem. 68, 1450 (1990). Lorsqu'on a essay6 d'utiliser les esters d'acides sulfoniques aromatiques comme agents de condensation des alcools avec les mercaptans, on a observe une reaction inusitee pour ce type de compost, B savoir une rupture de la liaison CS. On a explore deux possibilites mtcanistiques pour expliquer ces scissions : (i) un intermtdiaire radical-anion se formant par le transfert d'un seul electron et (ii) une reaction de substitution aromatique nuclCophile aromatique. On presente des experiences ainsi que des calculs d'orbitales moltculaires qui suggerent que les rCactions se produisent par le biais de substitutions aromatiques nuclCophiles. Mots c l b : esters d'acides sulfoniques, nitrobenzknesulfonates, rupture de la liaison CS. [Traduit par la revue]

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Introduction
W e recently reported ( 1 ) that phenyl methanesulfonate induces the condensation of p-tolyl mercaptan with primary alcohols, as shown in eq. [I]. Further study of this chemistry led to the observation that p-nitrophenyl methanesulfonate condensed with the mercaptan leaving the alcohol largely unused (eq. [2]). [I J PhOS02CH3 + CH3H * s 2 NaH

131

+ CH~--@SH ~ O P

CH3CH20H

2 NaH HMPA

o~N--@s--@-cH~

1 (63%)
[4] Ph2CHS020Ar

+ CHICHIOH

+
s o

Ph 2CHOAr + SO2

HMPA + CH~-~&SCH~CH~

[5]

+ ~CH O3 + P s~

HMPA t

NaH

C H ~ G - S - ~ S O ~ O P

CH3CH20H

2 NaH HMPA

CH~*-S-@NO~
1

In an attempt to examine nitro-substituted sulfonates that might induce alcohol-mercaptan condensation, a study of the chemistry of a linkage isomeric nitrophenyl sulfonate 2 was undertaken.

Results and discussion

Reaction of 2 with ethanol and p-tolyl mercaptan furnished the surprising results shown in eq. [ 3 ] .There appears to be only one example of a sulfonate ester substitution reaction leading to CS bond rupture (2) (see eq. [4]). There are, however, several known examples of C S bond rupture in reactions of related '~uthor to whom correspondence may be addressed at the Department of Chemistry, Mount Allison University, Sackville, N.B., Canada EOA 3C0. 2~evision received April 18, 1990.
Rimed in Canada 1 Irnprirnt au Canada

sulfonyl-containing structures (3, 4). Repetition of the eq. [3] reaction in the absence of ethanol permitted the isolation of 1 in the same yield, along with a modest yield of 3. Thus a role for ethanol in the formation of 1 can be dismissed from consideration. The unexpected C S rupture in the reactions of 2 with mercaptide anions prompted us to examine nitroaryl sulfonates to establish the relative propensities for C S and CO rupture. The behaviour of the ideal dinitrosulfonate ester 4 was modelled with the aid of the linkage isomeric dinitrosulfonates 5 a and 5 b . T h e reactions of these dinitrosulfonate esters with p-tolyl mercaptide anions in H M P A are depicted below. Assuming that methyl substitution diverts x% of product formation to the other ring, a simple calculation on the results in eqs. [6] and [7] leads to the conclusion that the ratio of the yields of 1 formed by CS rupture to the yields of 1 formed by C O rupture would be ca. 19:1 in the hypothetical reaction of 4 with p-tolyl mercaptide anions! Two reasonable mechanisms may b e advanced to account

BAUM ET A L

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for the surprisingly facile CS bond rupture observed for the reactions of the bis(nitroary1) sulfonates 5 a , 5 b . Reaction might proceed through a Meisenheimer complex (A) as shown in Scheme 1. ~lternativelv, could transfer an .. the merca~tideanion electron to the sulfonate ester, converting it into the corresponding radical anion as depicted in Scheme 2. T O explore scheme 1, semi-empirical molecular orbital computations were carried out on the linkage isomers 5a and 5 b . The ZINDO calculated LUMOs, presented in Fig. 1, indicate that nucleophilic attack should occur preferentially on the sulfonyl-substituted phenyl ring in accord with experiment. Given that hard-soft acid-base arguments ( 5 ) militate against nucleophilic attack by mercaptide anions (soft) at nitrogen or sulfur (hard), the computations suggest a straightforward choice between soft acid sites: nitro-bearing carbon and sulfonyl-bearing carbon. Sulfonyl-bearing carbon has the larger LUMO coefficient, indicating that attack there will lead to a more strongly stabilized transition state (5). This analysis should also satisfactorily rationalize the results portrayed in eq. [51. In contrast to the reaction of 5 a , 5 b undergoes a modest amount of nucleophilic attack on the nitrophenoxy ring. This

may be rationalized by an examination of the NLUMO of 56 (6). The preferred soft acid site on that ring is the oxygenbearing carbon (NLUMO coefficient: -0.319) rather than the nitro-bearing carbon (NLUMO coefficient: -0.176). The computed difference in energies between the NLUMO and the LUMO for 5a is 0.443 eV. The corresponding value for 5b is 0.279 eV, suggesting a relative enhancement for the role of the NLUMO in the chemistry of 5 b . ZINDO calculations were ~erformedon 4 and its radical anion 4;. These computations were intended to reveal the nature and propensities of the radical anion in order to assess the viability of the Scheme 2 mechanism. Figure 2 presents selected bond length changes computed for the conversion 4 + 4'. The greatest contractions in bond length are computed for those bonds which are actually ruptured during one or more of the reactions reported herein. d n this basisthe Scheme 2 mechanism seems improbable. It is our view that the substitution reactions reported in eqs. [3], [6], and [7] proceed through Meisenheimer complexes ai portrayed in the Scheme 1 mechanism. However, aryl sulfonates can be drawn into electron transfer reactions (7, 8).

Relative yield:

(I 1%)

Relative yield:

(89%)

CAN. J. CHEM.VOL. 68, 1990

Single electron transfer

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Equation [8] presents a final nitroaryl sulfonate ester - mercaptide anion r e a ~ t i o n . ~ In the eq. [8] reaction, it seems extremely likely that the mesylate group is replaced first so that both products arise via the intermediacy of 10. The formation of 9 is an appropriate reaction for a SET mechanism similar to the one outlined in Scheme 2. In conclusion, it appears that nitroaromatic compounds may be involved in reactions proceeding through radical anions or in reactions proceeding through Meisenheimer complexes. Introduction of a sulfonate linkage onto a nitro-bearing phenyl ring appears to shift pathway preference toward nucleophilic aromatic substitution.

FIG. 1. ZINDO calculated lowest unoccupied molecular orbitals for 5a and 5b.

Computational methods All computations were performed using the ZINDO molecular orbital method (9). The ZINDO program is available as part of the QUIPU molecular modelling package from the Quantum Theory Project, University of Florida. The ground state geometries were obtained at the INDO11 level, including d-orbitals on sulfur and using a BFGS updated Hessian search with Newton-Raphson optimization. The restricted Hartree-Fock method was used for the closed shell neutral molecule. For the radical anion (open shell) system, an unrestricted Hartree-Fock calculation with annihilation was employed. The INDOIS option was employed to determine the HOMO and LUMO eigenvalues and eigenvectors using Matago-Nishimoto repulsion integrals and fixed ground state geometries.
3 ~ i n c this e reaction was conducted early in our research program, an equivalent of ethanol was present to check for p-tolyl ethyl sulfide formation.

FIG.2. Some calculated bond length changes (A) induced by conversion of 4 into 4'.

BAUM ET A L

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ZINDO calculated structural parameters for dimethyl sulfone are closer to experimental values than those obtained by 3-21G computations (10). ZINDO spectroscopic predictions agree
well with experimentally determined ultraviolet spectra on a series of five substituted phenyl methanesulfonates. ZINDO spectroscopic predictions were systematically superior to those obtained by C N D O / U V computations.

Experimental
General The ir spectra were recorded on a Perkin-Elmer 237B grating spectrophotometer. Ultraviolet spectra were run on a Beckman DU-2 s&ctrophotometer. The nmr spectra were obtained on a Varian EM360A instrument using TMS as the internal standard. Melting points were determined on a Gallenkamp MFB-595 capillary melting point apparatus and are uncorrected. Preparation o f phenyl p-nitrobenzenesulfonate 2 A solution of phenol (0.43 g, 4.5 mmol) and triethylamine (0.45 g, 4.5 mmol) in pyridine (50 mL) was cooled with an ice/water bath. p-Nitrobenzenesulfonyl chloride (1.0 g, 4.5 mmol) was added in small portions. The ice/water bath was removed and the reaction mixture stirred overnight. Chloroform extraction followed by acid washing gave crude sulfonate ester (0.98 g). The crude was recrystallized from methanol affording colorless crystals (0.67 g, 2.4 mmol, 54%, mp 118.1-118.6"C). The product had Rf 0.66 on analytical tlc plates when developed with chloroform; ir (CHC13): 1540, 1390, 1355, and 1150 cm-I; nmr (CDCl3) 8: 8.36 (2H, d, J = 8 Hz), 8.06 (2H, d, J = 8 Hz), 7.30 (3H, m), and 6.96 (2H, m). Anal. calcd. for CI2H9NO5S:C 51.60, H 3.24; found: C 51.58, H 3.22. Reaction of 2 with ethoxide and p-tolyl mercaptide anions Sodium hydride (0.65 g, 27 mmol) was suspended in H M P A ~ (30 mL). A solution of absolute ethanol (0.63 g, 13 mmol) in HMPA (10 mL) was added dropwise over 5 min. The reaction mixture was stirred at ambient temperature for 5 min. A solution of p-tolyl mercaptan (1.71 g, 13 mmol) in HMPA (10 mL) was added dropwise over 10 min. The reaction mixture was stirred at ambient temperature for 5 min. The nitrosulfonate 2 (3.82 g, 13 mmol) was added and the reaction mixture stirred at ambient temperature for 2 h. After about 10 min the homogeneous reaction mixture was rust colored. The reaction mixture was poured into water (400 mL) containing 10% HCl (5 mL). The resultant mixture was extracted with diethyl ether (three 100-mL aliquots). The wet organic layer was concentrated. The residue was added to water (100 mL) and the resultant mixture
4~~~~ is hexamethylphosphoramide [(CH3)2N]3P0. HMPA is toxic and carcinogenic (11).

washed with diethyl ether (three 100-mL aliquots). The combined ether layers were extracted with 2.5% NaOH (two 100-mL portions). The organic layer was dried (MgS04) and concentrated, yielding crude p-nitrophenyl p-tolyl sulfide 1 (3.79 g). The crude was recrystallized from methanol, affording impure nitrosulfide 1 (2.71 g). The recrystallized nitrosulfide was chromatographed on silica gel (250 g) employing carbon tetrachloride elution (100-mL fractions). Fractions 11-1 8 were combined and concentrated, furnishing clean nitrosulfide 1 (2.130 g, 8.6 mmol, 63%). After recrystallization from methanol, the chromatographed nitrosulfide was shown to be identical to previously obtained material (2) by ir, nrnr, tlc, mp, and mixture mp. Reaction o f 2 with p-tolyl mercaptide anions Sodium hydride (0.36 g, 15 mmol), p-tolyl mercaptan (1.73 g, 13 mmol), and the nitrosulfonate 2 (3.82 g, 13 mmol) were reacted in HMPA (40 mL) as above. The crude was subjected to column chromatography on silica gel (400 g) employing hexanes, carbon tetrachloride, and chlorofom as sequential eluants. Nitrosulfide 1 (2.23 g, 9.1 mmol, 66.7%) was obtained along with a sulfonate ester mixture (1.67 g). The mixture was chromatographed on silica gel (200 g) employing 1:l carbon tetrachloride/chloroform elution. Sulfide-sulfonate ester 3 (0.78 g, 2.1 mmol, 16%) was obtained. After recrystallization from methanol, the product had mp 52.3-53.SC, Rf, 0.75 upon development with 1:l chloroform/carbon tetrachloride; ir (CHC13); 1380 and 1180 cm- ' ; nmr (CDC13)8: 7.6 (2H, d, J = 9 Hz), 7.25 (6H, m), and 2.40 (3H, s); ms m/e: 356 (M, 33.9%), 263 (26%), 199 (100%), and 184 (64%). Anal. calcd. for CI9Hl6o3S2:C 64.02, H 4.52; found: C 64.15, H 4.36. Fractions 13-19 were combined and concentrated, giving unchanged nitrosulfonate 2 (0.47 g). Preparation of the dinitrosulfonate ester 5 a p-Nitro-m-methylphenol(0.69 g, 4.5 mmol), triethylamine (0.45 g, 4.5 mmol), and p-nitrobenzenesulfonyl chloride (0.99 g, 4.5 mmol) in pyridine (50 mL), reacted as above, gave recrystallized 5 a (0.85 g, 2.5 mmol, 56%, mp 131.4-132.2"C). The product had Rf 0.25 on analytical tlc plates when developed with 1:1 carbon tetrachloride/ chloroform; ir (CHC13): 1540, 1395, 1350, and 1190 cm-I; nrnr (CDCI,) 8: 8.40 (2H, d, J = 8 Hz), 8.06 (2H, d, J = 8 Hz), 7.90 (lH, d, J = 8 Hz), 6.96 (2H), and 2.35 (3H, s); ms m/e: 338 ( ~ t , 3.2%), 321 (31.8%), and 122 (100%). Anal. calcd. forCI3Hl0N207S: C46.15,H2.97;found:C46.10,H2.81. Preparation o f p-nitro- m -methylphenyl benzenesulfonate p-Nitro-m-methylphenol (5.00 g, 32 mmol), triethylamine (3.30g, 32 mmol), and benzenesulfonyl chloride (5.75 g, 32 mmol) were reacted in pyridine (50 mL) following the procedure outlined for the preparation of phenyl p-nitrobenzenesulfonate 2.

1454

CAN. 1. CHEM.VOL. 68. 1990

The crude nitrosulfonate was recrystallized from methanol, affording nitrosulfonate (6.85 g, 23 mmol, 71%, mp 75-76C). The product had Rf 0.67 on analytical tlc plates developed with 1:l chloroform/ carbon tetrachloride; ir (CHC1,): 1525, 1382, 1348, and 1190 cm-' ; nmr (CDC13) 6: 7.40 (8H, m), 2.53 (3H, s); ms m/e: 293 ( M t , 0.35%) and 77 (100%). Anal. calcd. for CI3HllNO5S:C 53.23, H 3.78; found: C 53.21, H 3.72. Preparation o f p-nitro-m-methylphenyl benzyl sufjide Sodium hydride (0.41 g, 17 mmol) was added to HMPA (30 mL). A solution of benzyl thiol(2.1 mL, 16 mmol) in HMPA (10 mL) was added dropwise over 5 min. p-Nitro-m-methyl-phenylbenzenesulfonate (5.00 g, 17 mmol) was added and the reaction mixture stirred at ambient temperature for 2 h. The reaction mixture was subjected to the extraction procedure outlined under "Reaction of 2 with ethoxide and p-tolyl mercaptide anions". Crude product was chromatographed on silica gel (400 g) employing carbon tetrachloride elution followed by chloroform elution. Dibenzyl disulfide (0.63 g) was isolated. The p-nitro-m-methylphenyl benzyl sulfide so obtained was recrystallized from methanol, furnishing clean yellow needles (0.85 g, 3.3 mmol, 20%, mp 58.3-59.2"C). The nitrosulfide had Rf 0.51 on analytical tlc plates developed with carbon tetrachloride; ir (CHCI3): 1525 and 1340 cm-' ; nmr (CDC13)6: 7.86 (lH, d), 7.20 (7H, m), 4.16 (2H, s), and 2.53 (3H, s); ms m/e: 259 (Mt , 10%) and 91 (100%). Anal. calcd. for Cl4HI3NO2S: C 64.84, H 5.05; found: C 64.77, H 4.96. Preparation o f p-nitro-m-methyl benzenesulfonyl chloride p-Nitro-m-methylphenyl benzyl sulfide (3.99 g, 15 mmol) was suspended in a solution of glacial acetic acid (25 mL) and water (3 mL). Chlorine (ca. 200 mL/min) was bubbled through the mixture for 3.75 g. Icelwater cooling was used as required to maintain the reaction temperature below 30C. Chloroform extraction followed by base washing gave a crude residue. The residue was rectified at reduced pressure, yielding p-nitrom-methyl benzenesulfonyl chloride (2.73 g, 11 mmol, 75%, bp 142148"C/1.6 Torr) (1 Torr = 133.3 Pa). p-Nitro-m-methyl benzenesulfonyl chloride had ir (CHC13): 1540, 1385, 1355, and 1175 cm-'; nmr (CDCI,) 6: 8.10 (3H, s) and 2.70 (3H, s). Preparation o f 5b p-Nitrophenol(0.61 g, 4.3 mmol), triethylarnine (0.47 g, 4.6 mmol), and p-nitro-m-methylbenzene sulfonyl chloride (1.03 g, 4.3 mmol) were reacted in pyridine (50 mL). Procedure and work-up were the same as those outlined for the preparation of the dinitrosulfonate ester 5a. Recrystallized 5b (0.69 g, 2.0 mmol, 46%, mp 120-121C) had Rf 0.34 on analytical tlc plates developed with 3:2 carbon tetrachloride/methylene chloride; ir (CHCI,): 1530, 1400, 1350, and 1175 cm-'; nmr (CDCI,) 6: 8.30 (2H, d), 7.96 (3H, m), 7.23 (2H, d), and 2.66 (3H, s); ms m/e: 338 (Mf, 27%), 200 (100%), and 136 (78%). Anal. calcd. for C13H1&207S: C 46.15, H 2.97; found: C 46.21, H 2.68. Reaction o f dinitrosulfonate 5 a with p-tolyl mercaptide anions Sodium hydride (0.05 g, 2.2 mmol) was added to HMPA (10 mL). A solution of p-tolyl mercaptan (0.29 g, 2.3 mmol) in HMPA (5 mL) was added dropwise. The dinitrosulfonate 5a (0.75 g, 2.2 mmol) was added and the reaction mixture stirred for 2 h. The reaction mixture was subjected to the extraction procedure outlined under "Reaction of 2 with ethoxide and p-tolyl mercaptide anions". Crude product was chromatographed on silica gel (30 g), affording a mixture of p-tolyl disulfide and the nitrosulfide 1 (0.21 g). The mixture was rechromatographed on silica gel (25 g), furnishing clean nitrosulfide 1 (0.11 g). Preparation o f p-nitro-m-methylphenyl p-tolyl sulfrde 6 Sodium hydride (0.32 g, 13 mmol) was suspended in HMPA (30 mL). p-Tolyl mercaptan (1.69 g, 13.7 mmol) in HMPA (10 mL) was added dropwise over 5 min. p-Nitro-m-methylphenyl benzene-

sulfonate (4.00 g, 13.6 mmol) was added and the reaction mixture stirred at ambient temperature for 2 h. The reaction mixture was subjected to the same extraction procedure as the 5a mixture. Crude product was chromatographed on silica gel (400 g), affording p-tolyl disulfide (0.80 g, 3.2 mmol) and the nitrosulfide 6 (1.51 g, 5.8 mmol, 43%, mp 45.6-45.9"C). The nitrosulfide 6 had Rf 0.63 on analytical tlc plates developed with carbon tetrachloride; ir (CHCI,): 1510 and 1340 cm-'; nmr (CDCI,) 6: 7.86 (lH, d), 7.16 (6H, m), 2.50 (3H, s), and 2.33 (3H, s); ms m/e: 259 ( M t , 100%), 198 (29%), and 123 (14%). Anal. calcd. for CI4Hl3NO2S: C 64.84, H 5.05; found: C 64.71, H 4.98. Reaction of dinitrosulfonate 5b with p-tolyl mercaptide anions Sodium hydride (0.05 g, 2.3 mmol) was suspended in HMPA (10 mL). A solution of p-tolyl mercaptan (0.26 g, 2.1 mmol) in HMPA (5 mL) was added dropwise over 1 min. The dinitrosulfonate ester 5b (0.70 g, 2.0 mmol) was added and the reaction mixture stirred at ambient temperature for 2 h. The reaction mixture was subjected to the same extraction procedure as the 5 a and 6 mixtures. The crude product was chromatographed on silica gel (70 g), affording p-tolyl disulfide (0.13 g, 0.5 mmol) and a mixture containing p-nitro-m-methylphenyl p-tolyl sulfide 6 (0.07 g) and p-nitrophenyl p-tolyl sulfide 1 (0.009 g). The sulfide mixture was homogeneous on tlc. The sample was split in half. The presence of each sulfide was confirmed by the addition of 15-mg aliquots of each sulfide, which induced the expected changes for appropriate signals in the nmr spectra of the mixtures. Preparation o f o-dibrorno-p-nitrophenyl methanesulfonate 7 o-Dibromo-p-nitrophenol(4.98g, 16 mmol), triethylamine (1.70 g, 16 mmol), and methanesulfonyl chloride (1.93 g, 16 mmol) were reacted in dry pyridine (25 mL). Procedure and work-up were the same as those outlined under "Preparation of the dinitrosulfonateester 5a". Recrystallized o-dibromo-p-nitrophenyl methanesulfonate (3.83 g, 10 mmol, 61%, mp 135-136C) had Rf 0.77 on analytical tlc plates developed with chloroform; ir (CHCl,): 1540, 1390, 1355, and 385 (s, e 172), 270 (e 7352), and 1190 cm-I; uv (CH30H) A,,: 224 (e 16 176) nm; nmr (CDC13) 6: 8.46 (2H, s) and 3.56 (3H, s). Anal. calcd. for C7H5Br2N05S:C 22.42, H 1.34; found: C 22.44, H 1.30. Reaction o f 7 with ethoxide and p-tolyl mercaptide anions Sodium hydride (0.66 g, 27 mmol) was added to HMPA (30 mL). A solution of ethanol (0.62 g, 13 mmol) in HMPA (10 mL) was added dropwise over 5 min. Upon completion of the addition, a solution of p-tolyl mercaptan (1.71 g, 13 rnmol) in HMPA (10 mL) was added dropwise over 5 min. The nitrodibromomesylate (5.24 g, 14 mmol) was added and the reaction mixture stirred at ambient temperature for 2 h. The reaction color changed from khaki to red, then to yellow, and finally orange within the first 15 min. The orange color persisted until the end of the reaction. The reaction mixture was subjected to the extraction procedure outlined under "Reaction of 2 with ethoxide and p-tolyl mercaptide anions". The crude residue was twice chromatographed on silica gel, affording pale yellow crystals of 3,4,5-tris(thio-p-tolyl)nitrobenzene 8 (0.73 g, 1.4 mmol, 32%). Upon recrystallization from methanol the product had mp 144-144SC, Rf 0.40 on analytical tlc plates developed with carbon tetrachloride; ir (CHCI3):1520 and 1340 cm-' ; uv (CH30H) A : , 395 (s, e 2060), 375 (e 2681), 253 (e 56666), and 207 (e 157 575); nmr (CDC1,) 6: 7.2 (14H, m), 2.43 (6H, s), and 2.36 (3H, s). Anal. calcd. for C27H23N02S3: C 66.22, H 4.73; found: C 66.30, H 4.60. In addition, colorless crystals of 2,6-dibromo-1,4-bis(thio-p-tolyl) benzene 9 (0.76 g, 1.5 rnmol, 23%) were obtained. Upon recrystallization from methanol the product had mp 93.5-94"C, Rf 0.35 on analytical tlc plates developed with hexanes; ir (CHC13): 1560 and 1500 cm-'; uv (CH30H) Am: 300 (e 9070), 275 (E 18 5001, and

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BAUM ET AL.

1455

220 ( e 31 111); nmr (CDC13) 6: 7.20 (lOH, rn), 2.33 (3H, s), and 2.23 (3H, s). Anal. calcd. for C20H16Br2SZ: C 50.01, H 3.35; found: C 49.95, H 3.33.

Acknowledgements
The authors acknowledge the guidance of one of the referees in producing the final form of the experimental part of this manuscript. Professor M. Zemer has kindly provided access to the ZINDO program utilized in the computational part of this study. 1. R. F. LANGLER and N. A. MORRISON. Can. J. Chem. 65, 2385 (1987). 2. J. F. KING and M. ASLAM. Can. J. Chem. 57, 3278 (1979). 3. (a) B. A. KENTand S. SMILES. J. Chem. Soc. 422 (1934); (b) W. J. EVANS and S. SMILES. J. Chem. Soc. 181 (1935).

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W. R. HARDSTAFF, D. G. KAY, R. F. LANGLER, 4. (a) H. 0. FONG, R. H. MORSE,and D. N. SANDOVAL. Can. J. Chern. 57, 1206 (1979); (b) J. F. KINGand K. C. KHEMANI. Can. J. Chern. 63, 619 (1985). 5. I. FLEMING. Frontier orbitals and. organic chemical reactions. Wiley, New York. 1976. 6. ( a ) G. KLOPMAN. J. Am. Chern. Soc. 90, 223 (1968); (b) L. SALEM. J. Am. Chem. Soc. 90, 543 (1968); 90,553 (1968): 7. K. A . DURKIN, R. F. LANGLER, and N. A. MORRISON. Can. J. Chem. 66, 3070 (1988). D. A. 8. J. C. CARNAHAN, JR., W. D. CLOSSON, J. R . GANSON, JUCKETT, and K. S. QUAAL. J. Am. Chern. Soc. 98,2526 (1976). 9. J. RIDLEY and M. ZERNER. Theor. Chim. Acta, 32, 111 (1973). W. T. HEHRE, D. J. DEFREES, 10. W. J. PIETRO,M. M. FRANCL, J. Am. Chern. Soc. 104, 5039 J. A. POPLE,and J . S. BINKLEY. (1982). 11. N. I. SAX. Dangerous properties of industrial materials. Van Nostrand Rheinhold, New York. 1979. p. 721.
\ ,