Efficient Preparation of Isothiocyanates From Dithiocarbamates Using Bromineless Brominating Reagent

REFERENCES

• Singh , C. B. ; Ghosh , H. ; Murru , S. ; Patel , B. K. Hypervalent iodine(III)–mediated regioselective N-acylation of 1,3-disubstituted thioureas . J. Org. Chem. 2008 , 73 , 2924 – 2927 .
   PubMed Web of Science ®Google Scholar
• (a) Ghosh , H. ; Yella , R. ; Nath , J. ; Patel , B. K. Desulfurization mediated by hypervalent iodine(III): A novel strategy for the construction of heterocycles . Eur. J. Org. Chem . 2008 , 6189 – 6196 ; (b) Ghosh , H. ; Yella , R. ; Ali , A. R. ; Sahoo , S. K. ; Patel , B. K. An efficient synthesis of cyanamide from amine promoted by a hypervalent iodine(III) reagent . Tetrahedron Lett. 2009 , 50 , 2407 – 2410 .
   Web of Science ®Google Scholar
• Nath , J. ; Ghosh , H. ; Yella , R. ; Patel , B. K. Molecular iodine–mediated preparation of isothiocyanates from dithiocarbamic acid salts . Eur. J. Org. Chem . 2009 , 1849 – 1851 .
   Google Scholar
• (a) Bora , U. ; Bose , G. ; Chaudhuri , M. K. ; Dhar , S. S. ; Gopinath , R. ; Khan , A. T. ; Patel , B. K. Regioselective bromination of organic substrates by tetrabutylammonium bromide promoted by V2O5-H2O2: An environmentally favorable synthetic protocol. Org. Lett. 2000, 2, 247–249; (b) Chaudhuri , M. K. ; Khan , A. T. ; Patel , B. K. ; Dey , D. ; Kharmawophlang , W. ; Lakshmiprabha , T. R. ; Mandal , G. C. An environmentally benign synthesis of organic ammonium tribromides (QATB) and bromination of selected organic substrates by tetrabutylammonium tribromide (TBATB). Tetrahedron Lett. 1998, 39, 8163–8166; (c) Avramoff , M. ; Weiss , J. ; Schächter , O. The brominating properties of tetramethylammonium tribromide. J. Org. Chem. 1963, 28, 3256–3258; (d) Kajigaeshi , S. ; Kakinami , T. ; Tokiyama , H. ; Hirakawa , T. ; Okamoto , T. Bromination of phenols by use of benzyltrimethylammonium tribromide. Chem. Lett. 1987, 4, 627–630; (e) Jordan , A. D. ; Luo , C. ; Reitz , A. B. Efficient conversion of substituted aryl thioureas to 2-aminobenzothiazoles using benzyltrimethylammonium tribromide. J. Org. Chem. 2003, 68, 8693–8696; (f) Kajigaeshi , S. ; Kakinami , T. ; Tokiyama , H. ; Yamasaki , H. ; Hirakawa , T. ; Okamoto , T. Synthesis of dibromoacetyl derivatives by use of benzyltrimethylammonium tribromide. Bull. Chem. Soc. Jpn. 1987, 60, 2667–2668; (g) Salazar , J. ; Dorta , R. Pentylpyridinium tribromide: A vapor pressure free room-temperature ionic liquid analogue of bromine. Synlett 2004, 1318–1320; (h) Tanaka , K. ; Shiraishi , R. ; Toda , F. A new method for stereoselective bromination of stilbene and chalcone in a water suspension medium. J. Chem. Soc., Perkin Trans. 1 1999, 3069–3070; (i) Markovic , R. ; Baranac , M. ; Dzambaski , Z. Sequential bromination–rearrangement of push–pull thiazolidines induced by pyridinium hydrobromide perbromide under homogeneous reaction conditions. Heterocycles 2004, 63, 851–860; (j) Fischer, L. F.; Fiecher, M. Reagents for Organic Synthesis; Wiley: New York, 1967; p. 967; (k) Reeves , W. P. ; Lu , C. V. ; Schulmeier , B. ; Jonas , L. ; Hatlevik , O. Selective bromination of aromatic ethers with pyridinium hydrobromide perbromide. Synth. Commun. 1998, 28, 499–505; (l) Paquet, L. A. (Ed.). Encyclopedia of Reagent for Organic Synthesis; Wiley: New York, 1995; vol. 6, pp. 4738, 4370; (m) Muathen , H. A. 1,8-Diazabicyclo[5.4.0]undec-7-ene hydrobromide perbromide: A new mild stable brominating agent for aromatic compounds. J. Org. Chem . 1992, 57, 2740–2741; (n) Zolfigol , M. A. ; Chehardoli , G. ; Salehzadeh , S. ; Adams , H. ; Ward , M. D. {[K.18-Crown-6]Br3}n: A unique tribromide-type and columnar nanotube-like structure for the oxidative coupling of thiols and bromination of some aromatic compounds. Tetrahedron Lett . 2007, 48, 7969–7973.
   PubMed Web of Science ®Google Scholar
• (a) Kavala , V.; Naik, S. ; Patel , B. K. A new recyclable ditribromide reagent for efficient bromination under solvent-free condition . J. Org. Chem. 2005 , 70 , 4267 – 4271 ; (b) Kavala , V. ; Naik , S. ; Patel , B. K. A new recyclable ditribromide reagent for efficient bromination under solvent free condition . J. Org. Chem. 2005 , 70 , 6556 .
   PubMed Web of Science ®Google Scholar
• (a) Naik , S. ; Kavala , V. ; Gopinath , R. ; Patel , B. K. 1′-(Ethane-1,2-diyl)dipyridinium bistribromide (EDPBT) as a recyclable catalyst for acylation . Arkivoc 2006 , 11 , 21 – 36 ; (b) Kavala , V. ; Murru , S. ; Das , G. ; Patel , B. K. Syntheses and regiochemistry of enol addition to 9-phenyl-9H-xanthen-9-ol . Tetrahedron 2008 , 64 , 3960 – 3965 ; (c) Kavala , V. ; Murru , S. ; Patel , B. K. ; Das , G. Self-assembled superstructure of xanthene derivatives . J. Chem. Crystallogr. 2007 , 37 , 527 – 535 ; (d) Singh , C. B. ; Murru , S. ; Kavala , V. ; Patel , B. K. It is “thiazolidene-2-imine” and not imidazole-2-thione as the reaction product of 1-benzoyl-3-phenylthiourea with Br2/enolizable ketone . Org. Lett. 2006 , 8 , 5397 – 5399 ; (e) Singh , C. B. ; Murru , S. ; Kavala , V. ; Patel , B. K. 3-Aryl-1-benzoylthioureas with α-bromoketones in water form 2-N-benzoyl-3-arylthiazol-2(3H)-imines, not 3-aryl-1-benzoylimidazoline-2-thiones . J. Chem. Res . 2007 , 136 – 137 ; (f) Murru , S. ; Singh , C. B. ; Kavala , V. ; Patel , B. K. A convenient one-pot synthesis of thiazol-2-imines: Application in the construction of pifithrin analogues . Tetrahedron 2008 , 64 , 1931 – 1942 ; (g) Murru , S. ; Kavala , V. ; Singh , C. B. ; Patel , B. K. A one-pot synthesis of 1,4-dithiins and 1,4-benzodithiins from ketones using the recyclable reagent 1,1′-(ethane-1,2-diyl)dipyridinium bistribromide (EDPBT) . Tetrahedron Lett. 2007 , 48 , 1007 – 1011 ; (h) Ghosh , H. ; Singh , C. B. ; Murru , S. ; Kavala , V. ; Patel , B. K. A new facile synthetic method for the construction of 1,3-oxathiolan-2-ylidenes . Tetrahedron Lett. 2008 , 49 , 2602 – 2606 ; (i) Zolfigol , M. A. ; Chehardoli , G. ; Ghaemi , E. ; Madrakian , E. ; Zare , R. ; Azadbakht , T. ; Niknam , K. ; Mallakpour , S. N-Bromo reagent–mediated oxidation of urazoles to their corresponding triazolinediones under mild and heterogeneous conditions . Monatsh. Chem. 2008 , 139 , 261 – 265 .
   Web of Science ®Google Scholar
• (a) Xiao , D. ; Powolny , A. A. ; Singh , S. V. Benzyl isothiocyanate targets mitochondrial respiratory chain to trigger reactive oxygen species-dependent apoptosis in human breast cancer cells. J. Biol. Chem . 2008, 283, 30151–30163; (b) Cuddihy , S. L. ; Brown , K. K. ; Thomson , S. J. ; Hampton , M. B. Induction of apoptosis by phenethyl isothiocyanate in cells overexpressing Bcl-XL. Cancer Lett. 2008, 271, 215–221; (c) Wang , L. G. ; Liu , X. M. ; Fang , Y. ; Dai , W. ; Chiao , F. B. ; Puccio , G. M. ; Feng , J. ; Liu , D. ; Chiao , J. W. De-repression of the p21 promoter in prostate cancer cells by an isothiocyanate via inhibition of HDACs and c-Myc. Int. J. Oncol. 2008, 33, 375–380; (d) Stoner , G. D. ; Dombkowski , A. A. ; Reen , R. K. ; Cukovic , D. ; Salagrama , S. ; Wang , L.-S. ; Lechner , J. F. Carcinogen-altered genes in rat esophagus positively modulated to normal levels of expression by both black raspberries and phenylethyl isothiocyanate. Cancer Res. 2008, 68, 6460–6467; (e) Bones , A. M. ; Rossiter , J. T. The myrosinase–glucosinolate system: Its organisation and biochemistry. Physiol. Plant. 1996, 97, 194–208; (f) Zhang , Y. ; Tang , L. ; Gonzalez , V. Selected isothiocyanates rapidly induce growth inhibition of cancer cells. Mol. Cancer Ther. 2003, 2, 1045–1052; (g) Xiao , D. ; Vogel , V. ; Singh , S. V. Benzyl isothiocyanate–induced apoptosis in human breast cancer cells is initiated by reactive oxygen species and regulated by Bax and Bak. Mol. Cancer Ther. 2006, 5, 2931–2945; (h) Xu , K. ; Thornalley , P. J. Studies on the mechanism of the inhibition of human leukaemia cell growth by dietary isothiocyanates and their cysteine adducts in vitro. Biochem. Pharmacol. 2000, 60, 221–231; (i) Mukherjee , A. K. ; Ashare , R. Isothiocyanates in the chemistry of heterocycles. Chem. Rev. 1991, 91, 1–24; (j) Stephensen , H. ; Zaragosa , F. Resin-bound isothiocyanates and their synthetic equivalents as intermediates for the solid-phase synthesis of substituted thiophenes. J. Org. Chem . 1997, 62, 6096–6097; (k) Al-Hourani , B. J. ; Banert , K. ; Gomaa , N. ; Vrobel , K. Synthesis of functionalized thiazoles via attack of heterocyclic nucleophiles on allenyl isothiocyanates. Tetrahedron 2008, 64, 5590–5597; (l) Fajkusova , D. ; Pazdera , P. Unexpected formation of benzothiazoles in the synthesis of new heterocycles: Benzo-1,2,4-dithiazines. Synthesis 2008, 1297–1305; (m) Wu , Y.-J. ; Zhang , Y. An efficient one-pot synthesis of 3-substituted-5-amino-1,2,4-thiadiazoles from isothiocyanates and amidines. Tetrahedron Lett. 2008, 49, 2869–2871; (n) Thiel , O. R. ; Bernard , C. ; King , T. ; Dilmeghani-Serna , M. ; Bostick , T. ; Larson , R. D. ; Faul , M. M. Practical synthesis of a vanilloid receptor-1 antagonist. J. Org. Chem. 2008, 73, 3508–3515.
   PubMedGoogle Scholar
• (a) Heckl , S. ; Sturzu , A. ; Regenbogen , M. ; Beck , A. ; Feil , G. ; Gharabaghi , A. ; Echner , H. A novel polyarginine containing smac peptide conjugate that mediates cell death in tumor and healthy cells . Med. Chem. 2008 , 4 , 348 – 354 ; (b) Meng , F. ; Manjula , B. N. ; Smith , P. K. ; Acharya , S. A. PEGylation of human serum albumin: Reaction of PEG-phenyl-isothiocyanate with protein . Bioconjug. Chem. 2008 , 19 , 1352 – 1360 ; (c) Ladden , M. J. W. ; Ling , X. Y. ; Gang , T. ; Bula , W. P. ; Gardeniers , H. J. G. E. ; Reinhoudt , D. N. ; Huskens , J. Multivalent binding of small guest molecules and proteins to molecular printboards inside microchannels . Chem. Eur. J. 2008 , 14 , 136 – 142 ; (d) Vishwanath , V. A. ; Nclntosh , J. M. Synthesis of fluorescent analogs of alpha-conotoxin MII . Bioconjug. Chem. 2006 , 17 , 1612 – 1617 ; (e) Guo , X. ; Meyerhoff , M. E. Synthesis of N-acetylneuraminyl-alpha 2,3(6) lactose-malate dehydrogenase conjugate for detecting sialic acid terminal groups on glycoproteins via homogeneous lectin-based enzyme-linked binding assay . Appl. Biochem. Biotech. 1997 , 68 , 41 – 56 ; (f) Lerchen , H.-G. ; Baumgarten , J. ; Piel , N. ; Kolb-Bachofen , V. Lectin-mediated drug targeting: Discrimination of carbohydrate-mediated cellular uptake between tumor and liver cells with neoglycoconjugates carrying fucose epitopes regioselectivity modified in the 3-position . Angew Chem. Int. Edn. 1999 , 38 , 3680 – 3683 ; (g) Laulia , P. ; Chan-park , M. B. ; Yan , Y. ; Wang , S. Q. ; Li , C. M. ; Lam , Y. C. Stretched cavity-assisted molding of micrometer and submicrometer photopolymerized hydrogel particles . Small 2008 , 4 , 69 – 76 ; (h) Dong , S. ; Roman , M. Fluorescently labeled cellulose nanocrystals for bioimaging applications . J. Am. Chem. Soc. 2007 , 129 , 13810 – 13811 ; (i) Schubert , W. ; Bonnekoh , B. ; Pommer , A. J. ; Philipsen , L. ; Boeckelmann , R. ; Malykh , Y. ; Gollnick , H. ; Friedenberger , M. ; Bode , M. ; Dress , A. W. M. Analyzing proteome topology and function by automated multidimensional fluorescence microscopy . Nat. Biotechnol. 2006 , 24 , 1270 – 1278 .
   PubMed Web of Science ®Google Scholar
• Dyer , E. ; Johnson , T. B. Nitro and amino triphenylguanidines . J. Am. Chem. Soc. 1932 , 54 , 777 – 787 .
   Google Scholar
• (a) Kim , S. ; Yi , K. Y. Di-2-pyridyl thionocarbonate: A new reagent for the preparation of isothiocyanates and carbodiimides . Tetrahedron Lett. 1985 , 26 , 1661 – 1664 ; (b) Gottfried , R. A convenient preparation of isothiocyanates . Angew. Chem. Int. Ed. 1966 , 5 , 963 – 964 ; (c) Kim , S. ; Yi , K. Y. 1,1′-Thiocarbonyldi-2,2′-pyridone: A new useful reagent for functional-group conversions under essentially neutral conditions . J. Org. Chem . 1986 , 51 , 2613 – 2615 .
   Web of Science ®Google Scholar
• (a) Larsen , C. ; Stelliou , K. ; Harpp , D. N. Organic sulfur chemistry, 25: Thiocabonyl transfer reagents. J. Org. Chem. 1978, 43, 337–339; (b) Larsen , C. ; Harpp , D. N. Thiocarbonyl transfer reagent chemistry, 3: Selective displacements with formaldehyde hydrazones and other nucleophiles. J. Org. Chem. 1981, 46, 2465–2466.
   Web of Science ®Google Scholar
• (a) Boas , U. ; Jakobsen , M. H. A new synthesis of aliphatic isothiocyanates from primary amines, convenient for in-situ use . J. Chem. Soc., Chem. Commun . 1995 , 1995 – 1996 ; (b) Boas , U. ; Pedersen , B. ; Christensen , J. B. Tetramethyl fluoro formamidinium hexafluorophosphate: An improved synthesis and some new uses . Synth. Commun. 1998 , 28 , 1223 – 1231 ; (c) Boas , U. ; Gertz , H. ; Christensen , J. B. ; Heegaard , P. M. H. Facile synthesis of aliphatic isothiocyanates and thioureas on solid phase using peptide coupling reagents . Tetrahedron Lett. 2005 , 45 , 269 – 272 ; (d) Molina , P. ; Alajarin , N. ; Arques , A. Convenient improved syntheses of isocyanates and isothiocyantes from amines . Synthesis 1982 , 596 – 597 .
   Google Scholar
• Wong , R. ; Dolman , S. J. Isothiocyanates from tosyl chloride–mediated decomposition of in situ generated dithiocarbamic acid salts . J. Org. Chem. 2007 , 72 , 3969 – 3971 .
   PubMed Web of Science ®Google Scholar
• Munch , H. ; Hansen , J. S. ; Pittelkow , M. ; Christensen , J. B.; Boas, U. A new efficient synthesis of isothiocyanates from amines using di-tert-butyl dicarbonate . Tetrahedron Lett. 2008 , 49 , 3117 – 3119 .
   Web of Science ®Google Scholar
• Li , G. ; Tajima , H. ; Ohtani , T. An improved procedure for the preparation of isothiocyanates from primary amines by using hydrogen peroxide as the dehydrosulfurization reagent . J. Org. Chem. 1997 , 62 , 4539 – 4540 .
   PubMed Web of Science ®Google Scholar
• Hodgkins , J. E. ; Reeves , W. P. The modified kaluza synthesis, III: The synthesis of some aromatic isothiocyanates . J. Org. Chem. 1964 , 29 , 3098 – 3099 .
   Web of Science ®Google Scholar
• (a) Atwood , J. L. ; Junk , P. C. ; May , M. T. ; Robinson , K. D. Synthesis and x-ray structure of [H3O+·18-crown-6] [Br−Br−Br−]. A compound containing both H3O+ and a linear and symmetrical ion crystallized from aromatic solution . J. Chem. Crystallogr . 1994 , 24 , 243 – 245 ; (b) Andersen , O. ; Roemming , C. The crystal structure of benzenediazonium tribromide . Acta Chem. Scand. 1962 , 16 , 1882 – 1889 .
   Web of Science ®Google Scholar
• (a) Evindar , G. ; Batey , R. A. Parallel synthesis of a library of benzoxazoles and benzothiazoles using ligand-accelerated copper-catalyzed cyclizations of ortho-halobenzanilides . J. Org. Chem. 2006 , 71 , 1802 – 1808 ; (b) Evindar , G. ; Batey , R. A. Copper- and palladium-catalysed intramolecular aryl guanidinylation: An efficient method for the synthesis of 2-aminobenzimidazoles . Org. Lett. 2003 , 5 , 133 – 136 ; (c) Murru , S. ; Patel , B. K. ; Bras , J. L. ; Muzart , J. Copper(I)-catalyzed synthesis of substituted 2-mercapto benzimidazoles . J. Org. Chem. 2009 , 74 , 2217 – 2220 .
   PubMed Web of Science ®Google Scholar
• Le Count , D. J. ; Dewsbury , D. J. ; Grundy , W. An improved synthesis of pyridyl isothiocyanates and thioureas . Synthesis 1977 , 582 – 583 .
   Google Scholar
• SMART, SAINT, and XPREP. Siemens Analytical X-ray Instruments Inc. : Madison , Wisc. , 1995 .
   Google Scholar
• Sheldrick , G. M. SADABS: Empirical Absorption and Correction Software ; University of Gottingen, Institut fur Anorganische Chemieder Universitat : Gottingen , Germany , 1999–2003 .
   Google Scholar
• Sheldrick , G. M. SHELXS-97 ; University of Gottingen : Gottingen , Germany , 1997 .
   Google Scholar
• Shan , W. G. ; Bian , G. F. ; Su , W. K. ; Liang , X. R. A facile one-pot preparation of isothiocyanates from N-formamides and sulfur powder with bis(trichloromethyl) carbonate . Org. Prep. Proced. Int. 2004 , 36 , 283 – 286 .
   Web of Science ®Google Scholar
• (a) Tsogoeva , S. B. ; Yalalov , D. A. ; Hateley , M. J. ; Weckbecker , C. ; Huthmacher , K. Asymmetric organocatalysis with novel chiral thiourea derivatives: Bifunctional catalysts for the Strecker and nitro-Michael reactions. Eur. J. Org. Chem . 2005, 4995–5000; (b) Isobe , T. ; Fukuda , K. ; Tokunaga , T. ; Seki , H. ; Yamaguchi , K. ; Ishikawa, T. Modified guanidines as potential chiral superbases, 2: Preparation of 1,3-unsubstituted and 1-substituted 2-iminoimidazolidine derivatives and a related guanidine by the 2-chloro-1,3-dimethylimidazolinium chloride-induced cyclization of thioureas. J. Org. Chem. 2000, 65, 7774–7778.
   Google Scholar
• Varaprasad , C. V. N. S. ; Barawkar , D. ; El Abdellaoui , H. ; Chakravarty , S. ; Allan , M. ; Chen , H. ; Zhang , W. ; Wu , J. Z. ; Tam , R. ; Hamatake , R. ; Lang , S. ; Hong , Z. Discovery of 3-hydroxy-4-carboxyalkylamidino-5-arylamino-isothiazoles as potent MEK1 inhibitors . Bioorg. Med. Chem. Lett. 2006 , 16 , 3975 – 3980 .
   PubMed Web of Science ®Google Scholar