Reaction with cyanuric chloride

Macrocyclic lactonization. co-Hydroxy acids are converted into the corresponding lactones by reaction with cyanuric chloride and triethylaminc in acetone or acetonitrile at 25°.1 Isolated yields of 13-, 16-, 17-, and 19-membered lactones are 70, 68, 85, and 33%, respectively. An example is the lactonization of aleuritic acid (I) to the lactone acetonide 2. 

If methyleneindoline-o)-aldehydes are condensed with cyclic amines substituted by an amino group in the aromatic ring, dyes are obtained that can be dimerized either by reaction with cyanuric chloride in a molar ratio of 2 1 or with phosgene. On account of their high substantivity these dyes are suitable for dyeing bleached sulfite pulp [22],... 

Similarly, dyes 40 and 41 are prepared by condensing 2,5-diaminobenzenesulfonic acid with bromamine acid, which reacts first at the less hindered amino group, followed by a reaction with cyanuric chloride to introduce the reactive group. These steps produce dye 41 and... 

Figure 14-1 Functionalization and activation of electrode materials, a) silanization of supports bearing hydroxylic groups b) reaction with cyanuric chloride c) activation with cyanogen bromide d) binding via amide bonds after activation with 1,1-carbonyldiimidazole e) activation with good leaving groups such as tresyl chloride f) formation of Schiff bases between aldehyde groups on the support and amino groups at the biomolecule g) activation of carboxylic groups with carbodiimides or h) via the acid chlorides.

Sucrose has been activated by reaction with cyanuric chloride to yield a [ dsucrose-dichlorotriazine adduct which was stable for at least six hours and which could be covalently linked to low density lipoprotein.A general method utilizing radiolabelled sucrose covalently linked to protein is described for assessment of the degradation of metabolized proteins. 

A. P. Purdy, E. Houser, C. F. George, Polyhedron 1997,16,3671-3679. Lithium dicyanamide, its reactions with cyanuric chloride, and the crystal structures of LiN(CN)2(MeCN)2 and LiCNiCsHsNlj. 

Reactions with cyanuric chloride Isonitriles from formamides s. 17, 546... 

Even polyalkoxy-s-triazines are quite prone to nucleophilic substitution. For example, 2,4,6-trimethoxy-s-triazine (320) is rapidly hydrolyzed (20°, dilute aqueous alkali) to the anion of 4,6-dimethoxy-s-triazin-2(l )-one (331). This reaction is undoubtedly an /S jvr-4r2 reaction and not an aliphatic dealkylation. The latter type occurs with anilines at much higher temperatures (150-200°) and with chloride ion in the reaction of non-basified alcohols with cyanuric chloride at reflux temperatures. The reported dealkylation with methoxide has been shown to be hydrolysis by traces of water present. Several analogous dealkylations by alkoxide ion, reported without evidence for the formation of the dialkyl ether, are all associated with the high reactivity of the alkoxy compounds which ai e, in fact, hydrolyzed by usually tolerable traces of water. Brown ... 

Bifunctional catalysis in nucleophilic aromatic substitution was first observed by Bitter and Zollinger34, who studied the reaction of cyanuric chloride with aniline in benzene. This reaction was not accelerated by phenols or y-pyridone but was catalyzed by triethylamine and pyridine and by bifunctional catalysts such as a-pyridone and carboxylic acids. The carboxylic acids did not function as purely electrophilic reagents, since there was no relationship between catalytic efficiency and acid strength, acetic acid being more effective than chloracetic acid, which in turn was a more efficient catalyst than trichloroacetic acid. For catalysis by the carboxylic acids Bitter and Zollinger proposed the transition state depicted by H. 

Preparation of Reagent and Labelling Procedures. The structure of F-D [2-(2,4-diazobicyclo-2,2,2-octyl)-4-(5-aminofluoresceinyl)-6-morpholinyl 1,3,5-triazine] has been confirmed by its FAB-MS, IR, and H-NMR spectra (9). Briefly, F-D was synthesized by the treatment of fluorescamine isomer I with cyanuric chloride, then reaction with morpholine and DABCO (l,4-diazobicyclo-2,2,2-octane), as illustrated... 

By suitable choice of reaction conditions the chloro substituents of cyanuric chloride (11.10) can be replaced in a stepwise fashion. In the first step DAS reacts with cyanuric chloride at a temperature in the 0-20 °C range, ideally at pH 5-6. In the second step an amine or alcohol (R, 11) reacts within the range 20-50 °C under neutral or slightly alkaline... 

The manufacture of several important brighteners containing alkoxytriazine groups, such as the DAS derivative of highest substantivity in Table 11.1, does not follow the conventional sequence. The first step involves reaction of cyanuric chloride with excess methanol and excess acid acceptor, usually sodium bicarbonate. Under acidic conditions this reaction takes a quite different course and can become dangerously violent (Scheme 11.4). 

In the preparation of other DAST brighteners it may be advantageous to avoid reacting DAS with cyanuric chloride in the first step. It is difficult to suppress the reactivity of the second chloro substituent completely and undesirable by-products of the general type 11.11 can be eliminated if DAS is made to react with a dichlorotriazine intermediate in the second step. Very careful control of the reaction conditions, especially in steps 1 and 2, is also necessary in order to avoid formation of partially hydrolysed by-products such as structures 11.12 and 11.13. 

The selective replacement of chlorine in cyanuric chloride by the 3,7-dioxa-r-l-azabicyclo[3,3,0]oct-5-yl-methoxy group through the Williamson method has been described <06T7319>. The reactions of cyanuric chloride with some amine nucleophiles have been described under very mild conditions <06H807>. 

Gotoh, Y., Tsukada, M., and Minoura, N. (1993) Chemical modification of silk fibroin with cyanuric chloride-activated polyethylene glycol Analysis of reaction site by 1H-NMR spectroscopy and conformation of the conjugates. Bioconjugate Cbem. 4, 554-559. 

Selecting a sulphonated dye molecule containing an amino group as the nucleophile leads directly to a dichlorotriazine dye. In certain cases a suitable intermediate may be condensed with cyanuric chloride and then the chromogenic grouping is synthesised from this reaction product. Both of these routes are illustrated in a simple way for Cl Reactive Red 1 (7.1) in Scheme 7.7. In these dyes the electronic effects responsible for the lability of the chloro substituents are muted by feedback of electrons from the electron-donating imino bridging... 

Coburn " synthesized 2,4,6-tris(picrylamino)-l,3,5-triazine (TPM) (190) from the reaction of aniline with cyanuric chloride followed by nitration of the product with mixed acid. Treatment of TPM (190) with acetic anhydride-nitric acid leads to Al-nitration and the isolation of the corresponding tris-nitramine. The high thermal stability of TPM (m.p. 316 °C) coupled with its facile synthesis and low sensitivity to impact has led to its large scale manufacture in the US by Hercules Inc. China has reported a low-cost synthetic route to TPM but this has a limited production capacity. 

Agrawal and co-workers synthesized the insensitive triazine-based explosive PL-1 (193) from the reaction of cyanuric chloride (191) with 3,5-dichloroaniline (192), followed by nitration and displacement of the chloro groups with ammonia in acetone. PL-1 (193) (VOD 7861 m/s, d = 2.02 g/cm, DTA exotherm at 335 °C) has overall comprehensive properties close to TATB. 

Zollinger (61AG125) investigated the reaction of cyanuric chloride with aniline in benzene, and showed that it is catalyzed by both acid and base. The reaction proceeds via the complexes (57) and (58) in acidic and basic conditions respectively (Scheme 39) (61HCA812). The preparation of 2,4,6-triamino-l,3,5-triazines from the mono-chloro derivative (59) is readily effected in dipolar aprotic solvents, but there is no reaction under the same conditions in acetone-water (73BSF2112). 

Loew and Weis (76JHC829) reported that two equivalents of cyanuric chloride react with hydrazine to form (60). There have been several reports of the reactions of cyanuric chloride with a variety of heterocycles, as illustrated in Scheme 40 (73JCS(P2)2075,75T1879). 

Budziarek and Hampson <71JCS(C)ll67> reported that the reaction between cyanuric chloride and 3-hydroxy-2-naphthanilide occurs in base with an O- triazine to AA-triazine rearrangement (Scheme 42). A stable triazine peroxide (66) has been synthesized from (65) and hydrogen peroxide (77CI(L)232), and (65) forms a novel adduct with the cyclopentadienyl anion (Scheme 43) (68HCA249). 

Triazines with three different substituents are formed by variations on the above methods. There is no efficient route to trialkyl or triaryl derivatives, although the reaction of acylimidates and amidines has met with some success (see Section 2.20.4.6.2). In general the best routes available are as follows, (a) Substitution reactions of cyanuric chloride, (b) The condensation of Af-cyanoamidine with chloromethyliminium salts, (c) 2-Aryl-1,3,5-triazin-2-ones may be efficiently prepared by ring closure reactions on AT-(a-chloroalky-lidene)carbamoyl chloride and amidines (see Section 2.20.4.4.1). 

Reaction of cyanuric chloride [108-77-0] with ethyleneimine yields triethylenemelamine [51-18-3] (172). 

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