Synlett 2006(13): 2156-2157  
DOI: 10.1055/s-2006-948185
SPOTLIGHT
© Georg Thieme Verlag Stuttgart · New York

Cyanuric Chloride: Trichloro-1,3,5-triazine

Kishan P. Haval*
Division of Organic Chemistry (Synthesis), National Chemical ­Laboratory, Pune 411 008, Maharashtra, India
e-Mail: kp.haval@ncl.res.in;

Further Information

Publication History

Publication Date:
09 August 2006 (online)

Biographical Sketches

Kishan P. Haval completed his B.Sc. and M.Sc. degrees from Swami Ramanand Teerth Marathwada University, Nanded, Maharashtra, ­India. He was awarded a gold medal for standing first in the M.Sc. course at Nanded University. He also received the Vice-Chancellor gold medal for highest marks amongst all faculty rank holders. He ­received a research fellowship after qualifying for the CSIR National Eligibility Test (NET) and joined the research group of Dr. N. P. Argade at the National Chemical Laboratory, Pune, India. He qualified for the State Eligibility Test (SET) for lectureship and the Graduate Aptitude Test in Engineering (GATE). His work towards his Ph.D. focuses on the total synthesis of bioactive natural products and development of new synthetic methodologies for the synthesis of monoalkyl- and dialkyl-substituted maleic anhydrides.

Introduction

Trichloro-1,3,5-triazine (cyanuric chloride) has been known since 1827. It has occupied an important place in organic synthesis because of its easy availability, low cost and clean selective reactions. It is commercially available and can also be conveniently synthesized by trimerization of cyanogen chloride. [1] The reactivity of ­cyanuric chloride with amines, alcohols, thiols and ­phenols has been widely put to use [2] in the synthesis of dyes, herbicides, insecticides, fungicides, pesticides, drugs and in the preparation of immobilized enzymes, a new class of polypode ligands and chiral stationary phases for GLC and HPLC. It has also been used for the synthesis of N-protected chiral α -aminonitriles, [3] as a mild reducing agent for carboxylic acids to alcohols, [4] in the synthesis of 4-(4,6-dimethoxy[1,3,5]triazin-2-yl)-4-methylmorpholinium chloride (DMTMM), [5] dendrimers, [6] macro­cyclic scaffolds, [7] as a mild and efficient alternative to the classical Swern oxidation, [8] in the preparation of acyl azides, [9] acyl chlorides [10] and chiral monochloro-s-triazine reagents for liquid chromatographic separation of amino acid enantiomers. [11] 2,4,6-Trisubstituted triazines have been used as antimalarial and antibacterial agents. [12] Recently, cyanuric chloride has been used for the synthesis of cyanuric acid bridged porphyrin-porphyrin dyads, [13] calixarenes [14] and benzoxazinones. [15]

Abstracts

(A) Cyanuric chloride is an excellent coupling reagent for the ­efficient transfer of diazomethane to a carboxylic acid. Preparation of diazoketones using carboxylic acids and the triazine reagent is considerably more convenient than classical diazo transfer ­protocols. [16]

(B) Cyanuric chloride has been used in an easy and convenient synthesis of Weinreb amides and hydroxamates. [17]

(C) Cyanuric chloride is a highly effective catalyst for the organocatalytic Beckmann rearrangement under reflux in acetonitrile or nitromethane. [18]

(D) Efficient conversion of alcohols and β-amino alcohols to the corresponding chlorides (and bromides) can be carried out at room temperature in methylene chloride, using cyanuric chloride and N,N-dimethyl formamide. This procedure can also be applied to optically active carbinols. [19]

(E) Efficient conversion of primary alcohols to the corresponding formate esters can be carried out at room temperature in methylene chloride, using cyanuric chloride and N,N-dimethyl formamide in the presence of lithium fluoride. This is a useful method for selectively protecting primary hydroxyl groups. [20]

(F) Starting from maleanilic and maleamic acids, recently we have reported a facile general approach to kinetically controlled iso­maleimides using cyanuric chloride as a decent dehydrating agent with 85-95% yields. [21]

(G) Very recently, simple and efficient access to alkyl- and dialkyl-substituted maleimides has been demonstrated by us using ­cyanuric chloride as a dehydrating agent via the new contrathermodynamic rearrangement of (E)-alkylidinesuccinimides to alkyl­maleimides. [22]

    References

  • 1 Kaminski ZJ. Peptide Science  2000,  55:  140 
  • 2 Menicagli R. Malanga C. Peluso P. Synth. Commun.  1994,  24:  2153 
  • 3 Maetz P. Rodriguez M. Tetrahedron Lett.  1997,  38:  4221 
  • 4 Falorni M. Porcheddu A. Taddei M. Tetrahedron Lett.  1999,  40:  4395 
  • 5 Falchi A. Giacomelli G. Porcheddu A. Taddei M. Synlett  2000,  275 
  • 6a Zhang W. Simanek EE. Org. Lett.  2000,  2:  843 
  • 6b Steffensen MB. Simanek EE. Org. Lett.  2003,  5:  2359 
  • 7 Löwik DWPM. Lowe CR. Eur. J. Org. Chem.  2001,  2825 
  • 8 De Luca L. Giacomelli G. Porcheddu A. J. Org. Chem.  2001,  66:  7909 
  • 9 Bandgar BP. Pandit SS. Tetrahedron Lett.  2002,  43:  3413 
  • 10 Luo G. Xu L. Poindexter GS. Tetrahedron Lett.  2002,  43:  8909 
  • 11 Brückner H. Wachsmann M. J. Chromatogr. A  2003,  998:  73 
  • 12a Agarwal A. Srivastava K. Puri SK. Chauhan PMS. Bioorg. Med. Chem. Lett.  2005,  15:  531 
  • 12b Srinivas K. Srinivas U. Rao VJ. Bhanuprakash K. Kishore KH. Murty USN. Bioorg. Med. Chem. Lett.  2005,  15:  1121 
  • 13 Carofiglio T. Varotto A. Tonellato U. J. Org. Chem.  2004,  69:  8121 
  • 14 Wang M.-X. Yang H.-B. J. Am. Chem. Soc.  2004,  126:  15412 
  • 15 Khajavi MS. Shariat SM. Heterocycles  2005,  65:  1159 
  • 16 Forbes DC. Barrett EJ. Lewis DL. Smith MC. Tetrahedron Lett.  2000,  41:  9943 
  • 17 De Luca L. Giacomelli G. Taddei M. J. Org. Chem.  2001,  66:  2534 
  • 18 Furuya Y. Ishihara K. Yamamoto H. J. Am. Chem. Soc.  2005,  127:  11240 
  • 19 De Luca L. Giacomelli G. Porcheddu A. Org. Lett.  2002,  4:  553 
  • 20 De Luca L. Giacomelli G. Porcheddu A. J. Org. Chem.  2002,  67:  5152 
  • 21 Haval KP. Mhaske SB. Argade NP. Tetrahedron  2006,  62:  937 
  • 22 Haval KP. Argade NP. Tetrahedron  2006,  62:  3557 

    References

  • 1 Kaminski ZJ. Peptide Science  2000,  55:  140 
  • 2 Menicagli R. Malanga C. Peluso P. Synth. Commun.  1994,  24:  2153 
  • 3 Maetz P. Rodriguez M. Tetrahedron Lett.  1997,  38:  4221 
  • 4 Falorni M. Porcheddu A. Taddei M. Tetrahedron Lett.  1999,  40:  4395 
  • 5 Falchi A. Giacomelli G. Porcheddu A. Taddei M. Synlett  2000,  275 
  • 6a Zhang W. Simanek EE. Org. Lett.  2000,  2:  843 
  • 6b Steffensen MB. Simanek EE. Org. Lett.  2003,  5:  2359 
  • 7 Löwik DWPM. Lowe CR. Eur. J. Org. Chem.  2001,  2825 
  • 8 De Luca L. Giacomelli G. Porcheddu A. J. Org. Chem.  2001,  66:  7909 
  • 9 Bandgar BP. Pandit SS. Tetrahedron Lett.  2002,  43:  3413 
  • 10 Luo G. Xu L. Poindexter GS. Tetrahedron Lett.  2002,  43:  8909 
  • 11 Brückner H. Wachsmann M. J. Chromatogr. A  2003,  998:  73 
  • 12a Agarwal A. Srivastava K. Puri SK. Chauhan PMS. Bioorg. Med. Chem. Lett.  2005,  15:  531 
  • 12b Srinivas K. Srinivas U. Rao VJ. Bhanuprakash K. Kishore KH. Murty USN. Bioorg. Med. Chem. Lett.  2005,  15:  1121 
  • 13 Carofiglio T. Varotto A. Tonellato U. J. Org. Chem.  2004,  69:  8121 
  • 14 Wang M.-X. Yang H.-B. J. Am. Chem. Soc.  2004,  126:  15412 
  • 15 Khajavi MS. Shariat SM. Heterocycles  2005,  65:  1159 
  • 16 Forbes DC. Barrett EJ. Lewis DL. Smith MC. Tetrahedron Lett.  2000,  41:  9943 
  • 17 De Luca L. Giacomelli G. Taddei M. J. Org. Chem.  2001,  66:  2534 
  • 18 Furuya Y. Ishihara K. Yamamoto H. J. Am. Chem. Soc.  2005,  127:  11240 
  • 19 De Luca L. Giacomelli G. Porcheddu A. Org. Lett.  2002,  4:  553 
  • 20 De Luca L. Giacomelli G. Porcheddu A. J. Org. Chem.  2002,  67:  5152 
  • 21 Haval KP. Mhaske SB. Argade NP. Tetrahedron  2006,  62:  937 
  • 22 Haval KP. Argade NP. Tetrahedron  2006,  62:  3557