Cyanuric chloride

Last updated
Cyanuric chloride
Cyanuric chloride.png
Cyanuric chloride 3D ball.png
Names
IUPAC name
2,4,6-Trichloro-1,3,5-triazine
Other names
Trichlorotriazine
s-Triazine trichloride
Cyanuryl chloride
TCT
Identifiers
3D model (JSmol)
124246
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.003.287 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 203-614-9
PubChem CID
RTECS number
  • XZ1400000
UNII
UN number 2670
  • InChI=1S/C3Cl3N3/c4-1-7-2(5)9-3(6)8-1 Yes check.svgY
    Key: MGNCLNQXLYJVJD-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C3Cl3N3/c4-1-7-2(5)9-3(6)8-1
    Key: MGNCLNQXLYJVJD-UHFFFAOYAQ
  • Clc1nc(Cl)nc(Cl)n1
Properties
C3Cl3N3
Molar mass 184.40 g·mol−1
AppearanceWhite powder
Odor pungent
Density 1.32 g/cm3
Melting point 144–148 °C (291–298 °F; 417–421 K)
Boiling point 192 °C (378 °F; 465 K)
hydrolyzes
Solubility in organic solventssoluble
Solubility in THF 0.34 g/mL
Solubility in CHCl3 0.17 g/mL
Structure
monoclinic
Hazards
GHS labelling:
GHS-pictogram-acid.svg GHS-pictogram-skull.svg GHS-pictogram-exclam.svg
Danger
H302, H314, H317, H330
P260, P261, P264, P270, P271, P272, P280, P284, P301+P312, P301+P330+P331, P302+P352, P303+P361+P353, P304+P340, P305+P351+P338, P310, P320, P321, P330, P333+P313, P363, P403+P233, P405, P501
NFPA 704 (fire diamond)
NFPA 704.svgHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazard W: Reacts with water in an unusual or dangerous manner. E.g. sodium, sulfuric acid
3
0
1
W
Flash point Non-flammable
Lethal dose or concentration (LD, LC):
485 mg/kg (rat, oral)
Safety data sheet (SDS) ICSC 1231
Related compounds
Related triazines
Cyanuric acid
Cyanuric fluoride
Cyanuric bromide
Trichloroisocyanuric acid
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

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.

Contents

Production

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 tons were produced. [2]

Industrial uses

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] [4]

Organic synthesis

Cyanuric chloride is employed as a reagent in organic synthesis for the conversion of alcohols into alkyl chlorides, [5] and carboxylic acids into acyl chlorides: [6]

Synthesis of acyl chlorides with cyanuric chloride.png

It is also used as a dehydrating agent, e.g. in the conversion of amides to nitriles, [7] 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. [8] [9]

The chloride centers are easily replaced by amines to give melamine derivatives, for example in the synthesis of dendrimers: [10] [11]

Cyanuric chloride based dendrimer.svg

It is also employed the synthesis of an experimental adenosine receptor ligand.: [12]

TriazineDerivativePharma.svg

Cyanuric chloride can also be used as an alternative to oxalyl chloride in the Swern oxidation. [13]

See also

Related Research Articles

The Friedel–Crafts reactions are a set of reactions developed by Charles Friedel and James Crafts in 1877 to attach substituents to an aromatic ring. Friedel–Crafts reactions are of two main types: alkylation reactions and acylation reactions. Both proceed by electrophilic aromatic substitution.

<span class="mw-page-title-main">Cyanohydrin</span> Functional group in organic chemistry

In organic chemistry, a cyanohydrin or hydroxynitrile is a functional group found in organic compounds in which a cyano and a hydroxy group are attached to the same carbon atom. The general formula is R2C(OH)CN, where R is H, alkyl, or aryl. Cyanohydrins are industrially important precursors to carboxylic acids and some amino acids. Cyanohydrins can be formed by the cyanohydrin reaction, which involves treating a ketone or an aldehyde with hydrogen cyanide (HCN) in the presence of excess amounts of sodium cyanide (NaCN) as a catalyst:

In organic chemistry, an acyl chloride is an organic compound with the functional group −C(=O)Cl. Their formula is usually written R−COCl, where R is a side chain. They are reactive derivatives of carboxylic acids. A specific example of an acyl chloride is acetyl chloride, CH3COCl. Acyl chlorides are the most important subset of acyl halides.

In organic chemistry, a nitrile is any organic compound that has a −C≡N functional group. The name of the compound is composed of a base, which includes the carbon of the −C≡N, suffixed with "nitrile", so for example CH3CH2C≡N is called "propionitrile". The prefix cyano- is used interchangeably with the term nitrile in industrial literature. Nitriles are found in many useful compounds, including methyl cyanoacrylate, used in super glue, and nitrile rubber, a nitrile-containing polymer used in latex-free laboratory and medical gloves. Nitrile rubber is also widely used as automotive and other seals since it is resistant to fuels and oils. Organic compounds containing multiple nitrile groups are known as cyanocarbons.

<span class="mw-page-title-main">Acyl halide</span> Oxoacid compound with an –OH group replaced by a halogen

In organic chemistry, an acyl halide is a chemical compound derived from an oxoacid by replacing a hydroxyl group with a halide group.

<span class="mw-page-title-main">Oxalyl chloride</span> Chemical compound

Oxalyl chloride is an organic chemical compound with the formula Cl−C(=O)−C(=O)−Cl. This colorless, sharp-smelling liquid, the diacyl chloride of oxalic acid, is a useful reagent in organic synthesis.

In chemistry, a trimer is a molecule or polyatomic anion formed by combination or association of three molecules or ions of the same substance. In technical jargon, a trimer is a kind of oligomer derived from three identical precursors often in competition with polymerization.

In organic chemistry, hydrocyanation is a process for conversion of alkenes to nitriles. The reaction involves the addition of hydrogen cyanide and requires a catalyst. This conversion is conducted on an industrial scale for the production of precursors to nylon.

<span class="mw-page-title-main">Triazine</span> Aromatic, heterocyclic compound

Triazines are a class of nitrogen-containing heterocycles. The parent molecules' molecular formula is C3H3N3. They exist in three isomeric forms, 1,3,5-triazines being common.

1,3,5-Triazine, also called s-triazine, is an organic chemical compound with the formula (HCN)3. It is a six-membered heterocyclic aromatic ring, one of several isomeric triazines. S-triazine—the "symmetric" isomer—and its derivatives are useful in a variety of applications.

Cyanogen bromide is the inorganic compound with the formula (CN)Br or BrCN. It is a colorless solid that is widely used to modify biopolymers, fragment proteins and peptides, and synthesize other compounds. The compound is classified as a pseudohalogen.

Stephen aldehyde synthesis, a named reaction in chemistry, was invented by Henry Stephen (OBE/MBE). This reaction involves the preparation of aldehydes (R-CHO) from nitriles (R-CN) using tin(II) chloride (SnCl2), hydrochloric acid (HCl) and quenching the resulting iminium salt ([R-CH=NH2]+Cl−) with water (H2O). During the synthesis, ammonium chloride is also produced.

A cyanogen halide is a molecule consisting of cyanide and a halogen. Cyanogen halides are chemically classified as pseudohalogens.

The Kulinkovich reaction describes the organic synthesis of substituted cyclopropanols through reaction of esters with dialkyl­dialkoxy­titanium reagents, which are generated in situ from Grignard reagents containing a hydrogen in beta-position and titanium(IV) alkoxides such as titanium isopropoxide. This reaction was first reported by Oleg Kulinkovich and coworkers in 1989.

<span class="mw-page-title-main">Cyanuric fluoride</span> Chemical compound

Cyanuric fluoride or 2,4,6-trifluoro-1,3,5-triazine is a chemical compound with the formula (CNF)3. It is a colourless, pungent liquid. It has been used as a precursor for fibre-reactive dyes, as a specific reagent for tyrosine residues in enzymes, and as a fluorinating agent.

<span class="mw-page-title-main">Methanesulfonic anhydride</span> Chemical compound

Methanesulfonic anhydride (Ms2O) is the acid anhydride of methanesulfonic acid. Like methanesulfonyl chloride (MsCl), it may be used to generate mesylates (methanesulfonyl esters).

<span class="mw-page-title-main">Trifluoroacetic anhydride</span> Chemical compound

Trifluoroacetic anhydride (TFAA) is the acid anhydride of trifluoroacetic acid. It is the perfluorinated derivative of acetic anhydride.

<span class="mw-page-title-main">4-Toluenesulfonyl chloride</span> Chemical compound

4-Toluenesulfonyl chloride (p-toluenesulfonyl chloride, toluene-p-sulfonyl chloride) is an organic compound with the formula CH3C6H4SO2Cl. This white, malodorous solid is a reagent widely used in organic synthesis. Abbreviated TsCl or TosCl, it is a derivative of toluene and contains a sulfonyl chloride (−SO2Cl) functional group.

<span class="mw-page-title-main">DMTMM</span> Chemical compound

DMTMM is an organic triazine derivative commonly used for activation of carboxylic acids, particularly for amide synthesis. Amide coupling is one of the most common reactions in organic chemistry and DMTMM is one reagent used for that reaction. The mechanism of DMTMM coupling is similar to other common amide coupling reactions involving activated carboxylic acids. Its precursor, 2-chloro-4,6,-dimethoxy-1,3,5-triazine (CDMT), has also been used for amide coupling. DMTMM has also been used to synthesize other carboxylic functional groups such as esters and anhydrides. DMTMM is usually used in the chloride form but the tetrafluoroborate salt is also commercially available.

<span class="mw-page-title-main">Cyanuric bromide</span> Chemical compound

Cyanuric bromide is a heterocyclic compound with formula C3N3Br3. It contains a six-membered ring of alternating nitrogen and carbon atoms, with a bromine atom attached to each carbon. It is formed by the spontaneous trimerisation of cyanogen bromide.

References

  1. ↑ Cyanuric chloride at Chemicalland21.com
  2. 1 2 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. 1 2 Ashford's Dictionary of Industrial Chemicals, 3rd edition, 2011, pages 2495-8
  4. ↑ Tappe, Horst; Helmling, Walter; Mischke, Peter; Rebsamen, Karl; Reiher, Uwe; Russ, Werner; Schläfer, Ludwig; Vermehren, Petra (2000). Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a22_651. ISBN   978-3527306732.
  5. ↑ Stanley R. Sandler (1970). "Cyanuric chloride. A novel laboratory hydrochlorinating reagent for alcohols". J. Org. Chem. 35 (11): 3967–3968. doi:10.1021/jo00836a088.
  6. ↑ K. Venkataraman & D. R. Wagle (1979). "Cyanuric chloride : a useful reagent for converting carboxylic acids into chlorides, esters, amides and peptides". Tetrahedron Lett. 20 (32): 3037–3040. doi:10.1016/S0040-4039(00)71006-9.
  7. ↑ George A. Olah; Subhash C. Narang; Alexander P. Fung & B. G. Balaram Gupta (1980). "Synthetic Methods and Reactions; 82. Cyanuric Chloride, a Mild Dehydrating Agent in the Preparation of Nitriles from Amides". Synthesis . 8: 657–658. doi:10.1055/s-1980-29160.
  8. ↑ 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
  9. ↑ John T. Gupton; Steven A. Andrews (1990). "β-Dimethylaminomethylenation: N,N-Dimethyl-N'-p-tolylformamidine". Organic Syntheses .; Collective Volume, vol. 7, p. 197
  10. ↑ Abdellatif Chouai & 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. S2CID   24304872.
  11. ↑ Reagent: DIPEA, amine protective group: BOC
  12. ↑ WOapplication 03101980,"1,3,5-TRIAZINE DERIVATIVES AS LIGANDS FOR HUMAN ADENOSINE-A3 RECEPTORS",published 2003-12-11 (Reagent number two: norephedrine, base DIPEA)
  13. ↑ De Luca, L.; Giacomelli, G.; Procheddu, A (2001). "A Mild and Efficient Alternative to the Classical Swern Oxidation". J. Org. Chem. 66 (23): 7907–7909. doi:10.1021/jo015935s. PMID   11701058.
This page is based on this Wikipedia article
Text is available under the CC BY-SA 4.0 license; additional terms may apply.
Images, videos and audio are available under their respective licenses.