2.4.6- Trichloro-l,3,5-triazine cyanuric chloride

A variety of oximes 255 undergo the Beckmann rearrangement upon treatment with 2,4,6-trichloro-l,3,5-triazine (cyanuric chloride, 256) in A,A-dimethylformamide (DMF, 257) at room temperature in excellent yields (equation 77). 

Trichloro-l,3.5-triazine (cyanuric chloride, 5) can be converted using a sixfold excess of sulfur tetrafluoride at 250 C into 2,4,6-trifluoro-l,3,5-triazine (cyanuric fluoride, 6) with lower proportions of sulfur tetrafluoride, cyanuric chlorofluorides are formed.191... 

A more recent modification was reported by Giacomelli and De Luca wherein oxalyl chloride has been replaced by 2,4,6-trichloro[l,3,5]triazine (cyanuric chloride, TCT) as the activator.16 The authors cite the dangerous toxicity and moisture sensitivity of oxalyl chloride as a motive for their work, the exclusion of which also means that the reaction can be carried out between -30 and 0 °C. Alcohols and. V-protected a-amino alcohols were converted to the corresponding ketones and aldehydes. 

Column 250 x 4.6 CSP-4 (Prepare as follows. Add a solution of 1.07 g L-valyl-L-valyl-L-valine isopropylester (Bunseki Kagaku 1979, 28, 125) in 30 mL dry dioxane (Caution Di-oxane is a carcinogen ) dropwise to a mixture of 2.2 g2,4,6-trichloro-l,3,5-triazine(cyanuric chloride) in 20 mL dry dioxane stirred at 0°, add 3 g anhydrous sodium carbonate at room temperature, stir, filter, evaporate to give a colorless solid. Dissolve 8.3 g of this solid in 30 mL dry dioxane, add 2 g N-(2-aminoethyl)-3-aminopropyltrimetho3ysilane, add 1.5 g anhydrous sodium carbonate, reflux with stirring for 40 h, filter, add 3 g dried 10 p.m Li-Chrosorb Si 100, reflux with slow stirring for 10 h, cool, filter. Wash the solid with dioxane, MeOH, and diethyl ether, dry imder reduced pressure (J.Chromatogr. 1984, 292, 427).) Mobile phase Hexane 1,2-dichloroethane EtOH trifluoroacetic acid 62.5 35 0.625 0.25 Detector UV... 

Cyanuric chloride (TCT, 2,4,6-trichloro-l,3,5-triazine) [108-77-0] M 184.4, m 146-149 , 154 , h 190 . Crystd from CCI4 or pet ether (b 90-100°), and dried under vacuum. Recrystd twice from anhydrous benzene immediately before use [Abuchowski et al.J Biol Chem 252 3582 1977]. 

Cyanuric chloride [2,4,6-trichloro-l,3,5-triazine (59)] is the basis of three major industrial applications triazine herbicides, triazine dyes, and optical whitening agents. It is not, however, made commercially by chlori-... 

Cyanuric chloride, see 2,4,6-Trichloro-l,3,5-triazine, 1038 Cyclic poly(ethylene oxides), 0830... 

Chloro-l,3,5-triazines and cyanuric chloride (2,4,6-trichloro-l,3,5-triazine) are the commonest starting materials for the synthesis of many 1,3,5-triazine derivatives.10,12,14,18,19,21 Cyanuric chloride behaves like an acid chloride the chlorine atoms can be replaced sequentially but with increasing difficulty as nucleophilic attack is progressively hindered by the presence of more electron-donating substituents. The reaction mechanism is dependent on the reaction... 

Synthesis of 1,3,5-triazine cannot be achieved by catalytic hydrogenation of cyanuric chloride (2,4,6-trichloro-l,3,5-triazine), probably due to poisoning of the catalyst by 1,3,5-triazine.36,37 When one, two or all of the chlorine atoms of cyanuric chloride are replaced by amino, methoxy, methylsulfanyl or alkyl groups, reduction with hydrogen iodide and phospho-nium iodide, sodium in liquid ammonia, or catalytic hydrogenation, e.g. to give 1, can be accomplished.38-46 Reduction with zinc in acetic acid could not be achieved.44. 

Cyanuric chloride (2,4,6-trichloro-l,3,5-triazine) resembles the nitrogen analog of an acid chloride (imidoyl chloride). The chlorine atoms can be replaced sequentially using different reaction conditions. The rate of reaction for such processes which involve cyanuric chloride or other chlorotriazines is dependent on solubility, temperature, actual ring substitution, the catalyst used and the nature of the nucleophile. Several reviews on the chemistry of cyanuric chloride reactions are reported.54 66... 

Triazines, formerly symmetric or 5-triazines, have been known for almost 200 years, and are, like many heterocyclic compounds, often referred to by trivial names. Common trivial names used include cyanuric acid (2,4,6-trihydroxy-l,3,5-triazine (1)), cyanurates (2,4,6-trialkoxy-1,3,5-triazines (2)), cyanuryl chloride (2,4,6-trichloro-l,3,5-triazine (3)), isocyanurates (1,3,5-trialkyl-... 

Triazinyl-containing sulfonamides 367 and 368, obtained from cyanuric chloride (2,4,6-trichloro-l,3,5-triazine) and amino-benzenesulfonamides 366, followed by treatment with water, MeNH2, or ROH, act as highly effective inhibitors of the zinc-containing enzyme, carbonic anhydrase (CA, EC 4.2.1.1) (Scheme 82) <2005BML3102>. 

Triazine Derivatives. Various 1,3,5-triazines have extremely valuable properties as herbicides. It was stated in 1984 that they constitute the most important class of heterocyclic compounds in all of agrochemistry. The most prominent is atrazine, which at high concentration is a total herbicide, but at lower concentrations is useful for preemergence control of weeds. Many ttiazines have been investigated, and several have appeared on the market. Some of these are shown in Figure 11.3. All are based on the sequential displacement of chlorine from cyanuric chloride (2,4,6-trichloro-l,3,5-triazine, Chapter 6) with nucleophiles. 

The coupling reagent 2,4,6-trichloro-l,3,5-triazine (TCT, a cyanuric chloride) was found to be an inexpensive way to prepare lV)N -di-Boc-protected guanidines using the di-Boc-thiourea (09SL3368). The active guanidinylating agent was determined to be N,iV -di-Boc-carbodiimide upon treatment with iV-methylmorpholine. 

Cyano-l,2,3-tris(difluoroamino)propane, 1428a Cyanuric acid, see 2,4,6-Trihydroxy-1,3,5-triazine, 1115 Cyanuric chloride, see 2,4,6-Trichloro-1,3,5-triazine, 1035 Cyclo-o%o-butadiynyl-2,3-dioxocyclobutenylidene, see Oligo(octacarbondioxide), 3103 f Cyclobutane, 1575... 

Cyanuric chloride (2,4,6-trichloro-sym-l,3,5-triazine chloro-triazine trichloro-cyanidine). This is widely available. A high-purity (99%) compound should be used. It is a very reactive compound, and must be stored at 2-8°C in an anhydrous environment. It should be recrystallized in petroleum ether (see Note 1). Hazards Poison, lachrymator, and irritant to eyes, skin and respiratory system. May be harmful if swallowed. Toxicity data LD50 485 mg/kg oral, rat. Should be handled in a fume hood with safety glasses and gloves, and treated as a possible cancer hazard. 

The synthesis, characterization, and energetic properties of various heterocycles containing azide groups are reported. Compound 105 is prepared by the reaction of cyanuric chloride with sodium azide. The preparation of 106 utilizes the conversion of a pyrazole derivative by reaction with hydrazine to form the hydrazo intermediate which is subsequently reacted with NaN02. 2,5,8-Trichloro-s-heptazine is converted quantitatively into 2,5,8-triazido-s-heptazine (107) with trimethylsilyl azide. The nucleophilic reaction of hydrazine with 4,4, 6,6 -tetra(chloro)hydrazo-l,3,5-triazine... 

---