Cleavage of C=N derivatives and Oxidation of Thiols in Water under Neutral Conditions with 1,4-dichloro-1,4-diazoniabicyclo[2,2,2]octane bischloride

Abstract

1,4-Diazabicyclo[2,2,2]octane (DABCO) is easily chlorinated and gives a complex which efficiently converts aliphatic and aromatic oximes, phenylhydrazones and semicarbazones to their corresponding carbonyl compounds in water at 50°C in high yield. This reagent can also be used for conversion of thiols to their compounding disulfide under the same reaction conditions. DABCO is quantitatively recovered which can be rechlorinated and reused several times.

Keywords

1,4-dichloro-1,4-diazoniabicyclo[2,2,2]octane bischloride oximes phenylhydrazones semicarbazones deprotection thiols oxidation

References

Greene

T.W.

, and Wuts

P.G.

, Protective Groups in Organic Synthesis, 3rd edn., Wiley: New York, 1999, p. 352.

S.K.

, Synth. Commun., 2004, 34, 2751.

Nagarapu

, Ravirala

, and Akkewar

, Synth. Commun., 2002, 32, 2195.

Ryu

, and Miyazato

, Bull. Chem. Soc. Jpn., 2004, 77, 1407.

S.K.

, Org. Chem. Lett., 2005, 2, 77.

Zhang

G.S.

, and Chai

, Synth. Commun., 2000, 30, 1849.

Shirini

, Zolfigol

M.A.

, Safari

, Mohammadpoor-Baltork

, and Mirjalili

B.F.

, Tetrahedron Lett., 2003, 44, 7463.

Chrisman

, Blankinship

M.J.

, Taylor

, and Harris

C.E.

, Tetrahedron Lett., 2001, 42, 4775.

Ranu

B.C.

, and Sakar

D.C.

, J. Org. Chem., 1988, 53, 878.

10.

Krishnaveni

N.S.

, Surendra

, and Nageswar

Y.V.D.

, Synthesis-Stuttgart, 2003, 13, 1968.

11.

(a) Oae

, Ed. Organic Sulfur Chemistry: Structure and Mechanism; CRC Press: Boca Raton, FL, 1991; (b) R.J. Cremlyn, An Introduction to Organosulfur Chemistr,; Wiley & Sons: New York, 1996; (c) A. Ogawa, Y. Nishiama, N. Kambe, S. Murai and N. Sonoda, Tetrahedron Lett., 1987, 28, 3271; (d) S. Antebi and H. Apler, Tetrahedron Lett., 1985, 26, 2609.

12.

Dhar

D.N.

, and Bag

A.K.

, Ind. J. Chem. 1984, 23B, 974.

13.

(a) Noureldin

N.A.

, Caldwell

, Hendry

, and Lee

D.G.

, Synthesis, 1998, 11, 1587; (b) H. Firouzabadi, M. Naderi, A. Sardarian and M. Vessal, Synth. Commun., 1983, 13, 611; (c) T.J. Wallace, J. Org. Chem., 1966, 31, 1217; (d) K.T. Liu and Y. Tong, Synthesis, 1978, 9, 669; (e) A. McKillop and D. Koyuncu, Tetrahedron Lett, 1990, 31, 5007; (f) A.R. Ramesha and S. Chandrasekran, J. Org. Chem., 1994, 59, 1354.

14.

(a) Narender

, Reddy

M.S.

, Kumar

, Nageswar

Y.V.D.

, and Rao

K.R.

, Tetrahedron Lett, 2005, 46, 1971; (b) H. Tohama, T. Maegawa, S. Takizawa and Y. Kita, Adv. Synth. Catal., 2002, 344, 328; (c) S.P. Chavan and P. Soni, Tetrahedron Lett., 2004, 45, 3161.

15.

Heravi

M.M.

, Tajbakhsh

, Habibzadeh

, and Ghasemzadeh

, Phosphorus, Sulfur and Silicon, 2001, 176, 195.

16.

(a) Heravi

M.M.

, Tajbakhsh

, Habibzadeh

, and Ghassemzadeh

, Phosphorus, Sulfur Silicon, 2002, 177, 2299; (b) M.M. Heravi, D. Ajami, M. Tajbakhsh and M. Ghassemzadeh, Monatsh. Chem., 2000, 131, 1109; (c) M.M. Heravi, D. Ajami, B. Mohajerani, M. Tajbakhsh, M. Ghassemzadeh and K. Tabarhydar, Monatsh. Chem., 2001, 132, 881.

17.

(a) Tajbakhsh

, and Habibzadeh

, J. Chem. Res., 2006, 539; (b) M. Tajbakhsh and S. Habibzadeh, J. Chem. Res., 2007, 259.

18.

Aldrich Catalogue/Handbook of Fine Chemicals, 1992–1993.

19.

(a) Drabowicz

, and Mikolajczyk

, Synthesis, 1980, 32; (b) V.I. Cohen, J. Org. Chem., 1977, 42, 2510; (c) M. Huang and C.C. Chan, Synthesis, 1982, 1091; (d) S. Raghavan, A. Rgender, S.C. Joseph and M. Rasheed, Synth. Commun., 2001, 31, 1477; (e) N.A. Noureldin, M. Caldwel, J. Hendry and D.G. Lee, Synthesis, 1980, 32; (f) M.M. Khodae, I. Mohammadpoor-Baltork and K. Nikoofar, Bull. Kor. Chem. Soc., 2003, 24, 885.