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Revision as of 23:56, 14 February 2024 edit51.155.110.141 (talk) →Organic synthesis: added an example of use as a dehydrating agent, with source← Previous edit Latest revision as of 17:52, 31 July 2024 edit undoSmokefoot (talk | contribs)Autopatrolled, Extended confirmed users, Pending changes reviewers, Rollbackers74,690 edits →Organic synthesis: replace patent (not RS) with ref to thiocyanuric acid, and replace white-spacey image with line eq 
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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.<ref name=Ullmann/> Many ] also incorporate a triazine ring. They are also manufactured by way of the chloride displacement reaction shown above.<ref name="ashford" /><ref name="TappeHelmling2000">{{cite book|last1=Tappe|first1=Horst|title=Ullmann's Encyclopedia of Industrial Chemistry|last2=Helmling|first2=Walter|last3=Mischke|first3=Peter|last4=Rebsamen|first4=Karl|last5=Reiher|first5=Uwe|last6=Russ|first6=Werner|last7=Schläfer|first7=Ludwig|last8=Vermehren|first8=Petra|year=2000|doi=10.1002/14356007.a22_651|isbn=978-3527306732}}</ref> 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.<ref name=Ullmann/> Many ] also incorporate a triazine ring. They are also manufactured by way of the chloride displacement reaction shown above.<ref name="ashford" /><ref name="TappeHelmling2000">{{cite book|last1=Tappe|first1=Horst|title=Ullmann's Encyclopedia of Industrial Chemistry|last2=Helmling|first2=Walter|last3=Mischke|first3=Peter|last4=Rebsamen|first4=Karl|last5=Reiher|first5=Uwe|last6=Russ|first6=Werner|last7=Schläfer|first7=Ludwig|last8=Vermehren|first8=Petra|year=2000|doi=10.1002/14356007.a22_651|isbn=978-3527306732}}</ref>


==Reactivity==
⚫ ==Organic synthesis==
⚫ The chloride centers are easily replaced. ]s give ] derivatives, for example in the synthesis of ]s:<ref>{{cite journal | title = 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 | author = Abdellatif Chouai | author2 = Eric E. Simanek | name-list-style = amp | journal = ] | year = 2008 | volume = 73 | pages = 2357–2366 | doi = 10.1021/jo702462t | pmid = 18307354 | issue = 6| s2cid = 24304872 }}</ref><ref>Reagent: ], amine ]: ]</ref>
:{{chem2|(ClCN)3 + R2NH -> (R2NCN)3 + 3 HCl }}

It reacts with ] to give ] ({{chem2|(S\dCNH)3}}).<ref name=Atw>{{cite journal |doi=10.1021/ic0103188 |title=Chemistry of 2,4,6-Trimercapto-1,3,5-triazine (TMT): Acid Dissociation Constants and Group 2 Complexes |date=2001 |last1=Henke |first1=Kevin R. |last2=Hutchison |first2=Aaron R. |last3=Krepps |first3=Matthew K. |last4=Parkin |first4=Sean |last5=Atwood |first5=David A. |journal=Inorganic Chemistry |volume=40 |issue=17 |pages=4443–4447 |pmid=11487353 }}</ref>

⚫ ===Organic synthesis===
Cyanuric chloride is employed as a ] in ] for the conversion of alcohols into alkyl chlorides,<ref>{{cite journal | journal = ] | volume = 35 | issue = 11 | pages = 3967-3968 | year = 1970 | doi = 10.1021/jo00836a088 | author = Stanley R. Sandler | title = Cyanuric chloride. A novel laboratory hydrochlorinating reagent for alcohols}}</ref> and carboxylic acids into acyl chlorides:<ref>{{cite journal | journal = ] | volume = 20 | issue = 32 | pages = 3037–3040 | year = 1979 | doi = 10.1016/S0040-4039(00)71006-9 | author = K. Venkataraman | author2 = D. R. Wagle | name-list-style = amp | title = Cyanuric chloride : a useful reagent for converting carboxylic acids into chlorides, esters, amides and peptides}}</ref> Cyanuric chloride is employed as a ] in ] for the conversion of alcohols into alkyl chlorides,<ref>{{cite journal | journal = ] | volume = 35 | issue = 11 | pages = 3967-3968 | year = 1970 | doi = 10.1021/jo00836a088 | author = Stanley R. Sandler | title = Cyanuric chloride. A novel laboratory hydrochlorinating reagent for alcohols}}</ref> and carboxylic acids into acyl chlorides:<ref>{{cite journal | journal = ] | volume = 20 | issue = 32 | pages = 3037–3040 | year = 1979 | doi = 10.1016/S0040-4039(00)71006-9 | author = K. Venkataraman | author2 = D. R. Wagle | name-list-style = amp | title = Cyanuric chloride : a useful reagent for converting carboxylic acids into chlorides, esters, amides and peptides}}</ref>
:] :]


It is also used as a dehydrating agent, e.g. in the conversion of ] to ],<ref>{{cite journal | journal = ] | volume = 8 | pages = 657-658 | year = 1980 | doi = 10.1055/s-1980-29160 | author = George A. Olah | author2 = Subhash C. Narang | author3 = Alexander P. Fung | author4 = B. G. Balaram Gupta | name-list-style = amp | title = Synthetic Methods and Reactions; 82. Cyanuric Chloride, a Mild Dehydrating Agent in the Preparation of Nitriles from Amides}}</ref> and for the activation of carboxylic acids for reduction to alcohols. Heating with ] gives "Gold's reagent" Me<sub>2</sub>NCH=NCH=NMe<sub>2</sub><sup>+</sup>Cl<sup>−</sup>, which is a versatile source of aminoalkylations and a precursor to heterocycles.<ref>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}}</ref><ref>{{OrgSynth | collvol = 7 | collvolpages = 197 | prep = cv7p0197 | year = 1990 | author = John T. Gupton | author2 = Steven A. Andrews | title = β-Dimethylaminomethylenation: ''N'',''N''-Dimethyl-''N''<nowiki>'</nowiki>-p-tolylformamidine}}</ref> It is also used as a dehydrating agent, e.g. in the conversion of ] to ],<ref>{{cite journal | journal = ] | volume = 8 | pages = 657-658 | year = 1980 | doi = 10.1055/s-1980-29160 | author = George A. Olah | author2 = Subhash C. Narang | author3 = Alexander P. Fung | author4 = B. G. Balaram Gupta | name-list-style = amp | title = Synthetic Methods and Reactions; 82. Cyanuric Chloride, a Mild Dehydrating Agent in the Preparation of Nitriles from Amides}}</ref> and for the activation of carboxylic acids for reduction to alcohols. Heating with ] gives "Gold's reagent" Me<sub>2</sub>NCH=NCH=NMe<sub>2</sub><sup>+</sup>Cl<sup>−</sup>, which is a versatile source of aminoalkylations and a precursor to heterocycles.<ref>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}}</ref><ref>{{OrgSynth | collvol = 7 | collvolpages = 197 | prep = cv7p0197 | year = 1990 | author = John T. Gupton | author2 = Steven A. Andrews | title = β-Dimethylaminomethylenation: ''N'',''N''-Dimethyl-''N''<nowiki>'</nowiki>-p-tolylformamidine}}</ref>

⚫ The chloride centers are easily replaced by ]s to give ] derivatives, for example in the synthesis of ]s:<ref>{{cite journal | title = 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 | author = Abdellatif Chouai | author2 = Eric E. Simanek | name-list-style = amp | journal = ] | year = 2008 | volume = 73 | pages = 2357–2366 | doi = 10.1021/jo702462t | pmid = 18307354 | issue = 6| s2cid = 24304872 }}</ref><ref>Reagent: ], amine ]: ]</ref>
:]

It is also employed the synthesis of an experimental ] ligand.:<ref>{{Ref patent
|country=WO
|number=03101980
|status= application
|title=1,3,5-TRIAZINE DERIVATIVES AS LIGANDS FOR HUMAN ADENOSINE-A3 RECEPTORS
|pubdate=2003-12-11
|fdate=
|pridate=
|invent1=
|assign1=
}} (Reagent number two: ], base ])</ref>

:]


Cyanuric chloride can also be used as an alternative to ] in the ].<ref>{{cite journal | last1 = De Luca | first1 = L. | last2 = Giacomelli | first2 = G. | last3 = Procheddu | first3 = A | year = 2001 | title =A Mild and Efficient Alternative to the Classical Swern Oxidation| journal = J. Org. Chem. | volume = 66| issue = 23| pages = 7907–7909 | doi=10.1021/jo015935s| pmid = 11701058 }}</ref> Cyanuric chloride can also be used as an alternative to ] in the ].<ref>{{cite journal | last1 = De Luca | first1 = L. | last2 = Giacomelli | first2 = G. | last3 = Procheddu | first3 = A | year = 2001 | title =A Mild and Efficient Alternative to the Classical Swern Oxidation| journal = J. Org. Chem. | volume = 66| issue = 23| pages = 7907–7909 | doi=10.1021/jo015935s| pmid = 11701058 }}</ref>

Latest revision as of 17:52, 31 July 2024

Cyanuric chloride
Skeletal formula of cyanuric chloride
Ball-and-stick model of the cyanuric chloride molecule
Names
IUPAC name 2,4,6-Trichloro-1,3,5-triazine
Other names Trichlorotriazine
s-Triazine trichloride
Cyanuryl chloride
TCT
Identifiers
CAS Number
3D model (JSmol)
Beilstein Reference 124246
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.003.287 Edit this at Wikidata
EC Number
  • 203-614-9
PubChem CID
RTECS number
  • XZ1400000
UNII
UN number 2670
CompTox Dashboard (EPA)
InChI
  • InChI=1S/C3Cl3N3/c4-1-7-2(5)9-3(6)8-1Key: MGNCLNQXLYJVJD-UHFFFAOYSA-N
  • InChI=1/C3Cl3N3/c4-1-7-2(5)9-3(6)8-1Key: MGNCLNQXLYJVJD-UHFFFAOYAQ
SMILES
  • Clc1nc(Cl)nc(Cl)n1
Properties
Chemical formula C3Cl3N3
Molar mass 184.40 g·mol
Appearance White powder
Odor pungent
Density 1.32 g/cm
Melting point 144–148 °C (291–298 °F; 417–421 K)
Boiling point 192 °C (378 °F; 465 K)
Solubility in water hydrolyzes
Solubility in organic solvents soluble
Solubility in THF 0.34 g/mL
Solubility in CHCl3 0.17 g/mL
Structure
Crystal structure monoclinic
Hazards
GHS labelling:
Pictograms GHS05: CorrosiveGHS06: ToxicGHS07: Exclamation mark
Signal word Danger
Hazard statements H302, H314, H317, H330
Precautionary statements 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 four-colored diamondHealth 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 1W
Flash point Non-flammable
Lethal dose or concentration (LD, LC):
LD50 (median dose) 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 , 100 kPa). checkY verify (what is  ?) Infobox references
Chemical compound

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. Cyanuric chloride is the main precursor to the popular but controversial herbicide atrazine.

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

In 2005, approximately 200,000 tons were produced.

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 + RNH3Cl

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

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. Many reactive dyes also incorporate a triazine ring. They are also manufactured by way of the chloride displacement reaction shown above.

Reactivity

The chloride centers are easily replaced. Amines give melamine derivatives, for example in the synthesis of dendrimers:

(ClCN)3 + R2NH → (R2NCN)3 + 3 HCl

It reacts with hydrosulfide to give thiocyanuric acid ((S=CNH)3).

Organic synthesis

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

It is also used as a dehydrating agent, e.g. in the conversion of amides to nitriles, and for the activation of carboxylic acids for reduction to alcohols. Heating with DMF gives "Gold's reagent" Me2NCH=NCH=NMe2Cl, which is a versatile source of aminoalkylations and a precursor to heterocycles.

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

See also

References

  1. Cyanuric chloride at Chemicalland21.com
  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. ^ 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. 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.
  6. Reagent: DIPEA, amine protective group: BOC
  7. Henke, Kevin R.; Hutchison, Aaron R.; Krepps, Matthew K.; Parkin, Sean; Atwood, David A. (2001). "Chemistry of 2,4,6-Trimercapto-1,3,5-triazine (TMT): Acid Dissociation Constants and Group 2 Complexes". Inorganic Chemistry. 40 (17): 4443–4447. doi:10.1021/ic0103188. PMID 11487353.
  8. Stanley R. Sandler (1970). "Cyanuric chloride. A novel laboratory hydrochlorinating reagent for alcohols". J. Org. Chem. 35 (11): 3967–3968. doi:10.1021/jo00836a088.
  9. 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.
  10. 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.
  11. 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
  12. John T. Gupton; Steven A. Andrews (1990). "β-Dimethylaminomethylenation: N,N-Dimethyl-N'-p-tolylformamidine". Organic Syntheses; Collected Volumes, vol. 7, p. 197.
  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.
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