Cyanuric chloride

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Cyanuric chloride
Structural formula
Ball-and-stick model
Identifiers
CAS number 108-77-0 YesY
PubChem 7954
ChemSpider 7666 YesY
EC number 203-614-9
UN number 2670
ChEBI CHEBI:58964 YesY
RTECS number XZ1400000
Jmol-3D images Image 1
Properties
Molecular formula C3Cl3N3
Molar mass 184.41 g mol−1
Appearance White powder
Odor pungent
Density 1.32 g/cm3
Melting point 154 °C (309 °F; 427 K)
Boiling point 192 °C (378 °F; 465 K)
Solubility in water hydrolyzes
Solubility in organic solvents soluble
Structure
Crystal structure monoclinic
Hazards
MSDS ICSC 1231
EU Index 613-009-00-5
EU classification Very toxic (T+)
Harmful (Xn)
Corrosive (C)
R-phrases R14, R22, R26, R34, R43
S-phrases (S1/2), S26, S28, S36/37/39, S45, S46, S63
NFPA 704
Flammability code 0: Will not burn. E.g., water Health code 3: Short exposure could cause serious temporary or residual injury. E.g., chlorine gas Reactivity code 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g., calcium Special hazard W: Reacts with water in an unusual or dangerous manner. E.g., cesium, sodiumNFPA 704 four-colored diamond
Flash point Non-flammable
LD50 485 mg/kg (rat, oral)
Related compounds
Related triazines Cyanuric acid
Cyanuric fluoride
Cyanuric bromide
Trichloroisocyanuric acid
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
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Infobox references

Cyanuric chloride is an organic compound with the formula (NCCl)3. This white solid is the chlorinated derivative of 1,3,5-triazine. It is the trimer of cyanogen chloride.[1] Cyanuric chloride is the main precursor to the popular but controversial herbicide atrazine.

Production[edit]

Cyanuric chloride is prepared in two steps from hydrogen cyanide via the intermediacy of cyanogen chloride, which is trimerized at elevated temperatures over a carbon catalyst:

HCN + Cl2 → ClCN + HCl
Cyanurchloride Synthesis V.1.svg

In 2005, approximately 200,000 tonnes were produced.[2]

Industrial Uses[edit]

It is estimated that 70% of cyanuric chloride is used in the preparation of the triazine-class pesticides, especially atrazine. Such reactions rely on the easy displacement of the chloride with nucleophiles such as amines:

(ClCN)3 + 2 RNH2 → (RNHCN)(ClCN)2 + RNH3+Cl-

Other triazine herbicides, such as simazine, anilazine and cyromazine are made in an analogous way.[3]

Cyanuric chloride is also used as a precursor to dyes and crosslinking agents. The largest class of these dyes are the sulfonated triazine-stilbene optical brighteners (OBA) or fluorescent whitening agents (FWA) commonly found in detergent formulas and white paper.[2] Many reactive dyes also incorporate a triazine ring. They are also manufactured by way of the chloride displacement reaction shown above.[3][2]

Organic synthesis[edit]

In one specialized application, cyanuric chloride is employed as a reagent in organic synthesis for the conversion of alcohols and carboxylic acids into alkyl and acyl chlorides, respectively:[4]

Synthesis of acyl chlorides with cyanuric chloride.png

It is also used as a dehydrating agent and for the activation of carboxylic acids for reduction to alcohols. Heating with DMF gives "Gold's reagent" Me2NCH=NCH=NMe2+Cl-, which is a versatile source of aminoalkylations and a precursor to heterocycles.[5][6]

The chloride centers are easily replaced by amines to give melamine derivatives, for example in the synthesis of dendrimers:[7][8]

Cyanuric chloride based dendrimer

It is also employed the synthesis of an experimental adenosine receptor ligand.:[9]

Example use cyanuric chloride in pharma WO 03101980 patent

Cyanuric Chloride can also be used as an alternative to oxalyl chloride in the Swern oxidation.[10]

References[edit]

  1. ^ Cyanuric chloride at Chemicalland21.com
  2. ^ a b c Klaus Huthmacher, Dieter Most "Cyanuric Acid and Cyanuric Chloride" in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH, Weinheim. doi:10.1002/14356007.a08_191.
  3. ^ a b Ashford's Dictionary of Industrial Chemicals, 3rd edition, 2011, pages 2495-8
  4. ^ K. Venkataraman, and D. R. Wagle (1979). "Cyanuric chloride : a useful reagent for converting carboxylic acids into chlorides, esters, amides and peptides". Tet. Lett. 20 (32): 3037–3040. doi:10.1016/S0040-4039(00)71006-9. 
  5. ^ Probst, D. A.; Hanson, P. R.; Barda, D. A. "Cyanuric Chloride" in Encyclopedia of Reagents for Organic Synthesis, 2004, John Wiley & Sons. doi:10.1002/047084289X.rn00320
  6. ^ John T. Gupton; Steven A. Andrews (1990), "β-Dimethylaminomethylenation: N,N-Dimethyl-N'-p-tolylformamidine", Org. Synth. ; Coll. Vol. 7: 197 
  7. ^ Abdellatif Chouai and Eric E. Simanek (2008). "Kilogram-Scale Synthesis of a Second-Generation Dendrimer Based on 1,3,5-Triazine Using Green and Industrially Compatible Methods with a Single Chromatographic Step". J. Org. Chem. 73 (6): 2357–2366. doi:10.1021/jo702462t. PMID 18307354. 
  8. ^ Reagent: DIPEA, amine protective group: BOC
  9. ^ WO application 03101980, "1,3,5-TRIAZINE DERIVATIVES AS LIGANDS FOR HUMAN ADENOSINE-A3 RECEPTORS", published 2003-12-11  (Reagent number two: norephedrine, base DIPEA)
  10. ^ http://pubs.acs.org/doi/abs/10.1021/jo015935s De Luca, L.; Giacomelli, G.; Procheddu, A. J. Org. Chem. 2001, 7907.