Geevers, J.

Trompen, W.P.

English

University of Twente Research Information

Tetrahedron Lettora No. 18, pp 1691 - 1692, 1974. Per-n Press. Printed ill &ertBritaia. REACTION OF N-CRLORO FORWIMIDOYL CHLORIDES WITH DISULFIDES 1) J. Geevers and W.P. Trompenx Twente University of Technology, Enschede, The Netherlands (Received in BE 24 February 1974; aooepted for publioation 27 Waroh 1974) The reactions of disulfides with various N-halogen compounds have been repor- ted by several authors. Generally cleavage of the sulfur-sulfur bond occurs and a sulfur-nitrogen bond is formed. Depending on the N-halogen compound, a single bond2) or a double bond3) may be formed. This paper deals with the reaction of some N-chloro formimidoyl chlorides with dimethyl disulfide and with diphenyl- disulfide respectively; N-methylthio or N-phenylthio formimidoyl chlorides are formed according to the following reaction scheme: R 'C=N-Cl + R'S-SR' __c R Cl' 'C=N-SR' Cl' + RISC1 (1) I-VIII Bifunctional N-chloro formimidoyl chlorides react in an analogous way: The same chloride is catalytical Cl Cl 'C=N-Cl 'C=N-SR' I + ZR'S-SR' - I + 2R'SCl (2) Cl' C=N-Cl C=N-SR' Cl' IX-X Cl Cl )C=N-Cl C12C\ + 2R'S-SR' - )c=N-SRI (3) Cl ,C=N-Cl C12C\c=N_sR, + 2R'SC1 Cl' XI-XII reaction products are obtained in a comparable yield, when sulfuryl added to a mixture of the nitrile and a disulfide in the presence of amounts of chloride anions 4, (except for the gaseous nitriles). 9 2R-CEN + R'S-SR' + S02C12 L 2 R 'C=N-SR' + SO2 a./ Experimental procedure: Reactions 1, 2 and 3: Equivalent amounts of the N-chloro formimidoyl and the disulfide were mixed at room temperature. After some time an 1691 (4) chloride5) orange 1692 No. 18 colour was observed in the reaction mixture, due to the formation of the sul- fenyl chloride. After being kept at room temperature overnight, the reaction mixture was distilled to remove the sulfenyl chloride formed. The residue was distilled or recrystallized to yield the N-methylthio or the N-phenylthio formimidoyl chloride. Reaction 4: Equivalent amounts of the nitrile (liquid) and disulfide and DMF (0,5%) as a catalyst were mixed at room temperature. Sulfuryl chloride was added dropwise. The reaction mixture was treated as above. Reactions with gaseous ni- triles (excess) were performed in a Carius tube. Compounds prepared: R, R', yield, physical constants and specific experimental requirements given. From reaction 1: I: Cl, II: Cl, III: CC13' IV: CC13' v: CaN, VI: C:N, VII: CCl2-CaN, VIII: CC12-CrN, From reactions 2 IX: x: XI: XII: From reaction 4: CH3 I 87%, b.p.13 : 37 0 20 = , nD 1.5409, CH2C12 solvent. c6H5, 90%,.b.p.3 : 104-lOSo, ng" = 1.6210. CH3, 848, b.p.1 : 57O, ng" = 1.5688. COHN, 83%, b.p.O 3: 113', . ng" = 1.6273, DMF catalyst. CH3, 20 63%, b.p.12 : 60-62O, nD = 1.5542. c6r.i5, 81%, b.p.0.3: 106-108O, m.p.: 41-43O from P.E. 40-60°. CH.,, 94%, b.p., : 74O, nz" = 1.5522. L c6H;, 728, b.p.1 oU : 136 , m.p.: 55-56 0 from P.E. 60-80°, DMF cat and 3: CH3, 63%, m.p. ISO-15lo from P.E. 80-100°, C6H5, 54%, m.p. 180-181° from P.E. 80-100°. CH2C12 solvent. 47%, b.p.1: 123-125O, m.p. 65-67O from P.E. 60-80°. C6~5, 60%, m.p.: 66-68O from P.E. 60-80°, CH2C12 solvent and (starting compound and yield given) [ DMF catalyst. I: ClCzN, less than 5%; cyanuric chloride is formed. II: ClCzN, 10% (impure); cyanuric chloride is formed. III: CC13CzN, 82%. IV: CC13C:N, 77%. V: (CZN)~, 62%. VI: (CeNj2, lo%, X as impurity. VII: CC12(CsN)2r 84%. VIII: CC12(CrN)2, 90%. IX: V, 27%. X: (CZN)~, 20%. X: VI, 38%. x1: VII, 18%. x11: CC12(C~N)2, less than 5%: VIII is formed. All compounds showed elemental analyses and spectroscopic properties in agreement with the proposed structures. References: 1) 2) 3) 4) 5) Addition of chlorine to the cyanogen bond VI. Part V: J. Geevers and W.P. Trompen, Tetrahedron Letters 1974, preceding paper. W.Groebel, Chem.Ber. 93, 284 (1960); M.T.Cuzzoni and T.Pietra Lissi, Farmaco, Ed.Sci. 19. 981 (1964E H.J.Emel&s and B.W.Tattershall, J.Inorg,Nucl.Chem. 28, 18237i966): ‘K.H.B&hel and A.Conte, Chem.Ber. 100, 1248 (1967). J.R.Alexander and H.McCombie, J.Chem.Soc. 1932, 2087; E.S.Levchenk,> and L.V. Seleznenko, Eh.Org.Ehim. 5, 485 and 492 (1970). This procedure was first used by M.S.A.Vrijland of our laboratory fcr the addition of sulfenvl chlorides to the cyanogen bond in sulfonyl cyandes. Results to be published. W.P.Trompen, J.Geevers and J.Th.Hackmann, Rec.Trav.Chim. 90, 458 (1971). 

Reaction of N-chloro formimidoyl chlorides with disulfides

J. Geevers

W.P. Trompen

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Tetrahedron Letters

18237i966): ‘K.H.B&hel and A.Conte,

5) Addition of chlorine to the cyanogen

E.S.Levchenk,>

M.T.Cuzzoni and T.Pietra Lissi,

https://doi.org/10.1016/S0040-4039(01)82555-7

Reaction of N-chloro formimidoyl chlorides with disulfides

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