Amine benzotriazole

Benzotriazole-related methodology publications appeared in 2006. Reaction of 1-formylbenzotriazole with triphenylphosphine/carbon tetrachloride afforded l-(2,2-dichlorovinyl)benzotriazole, where lithiation followed addition of electrophiles gave a variety of functionalized M-(ethynyl)benzotriazoles <06T3794>. Novel mono- and symmetrical di-/V-hydroxy- and IV-aminoguanidines were readily prepared from the reaction of diverse hydroxylamines or hydrazines with reagent classes di(benzotriazol-l-yl)methanimine, (bis-benzotriazol-1 -y 1-methy lene)amines, benzotriazole-1 -carboxamidines, benzotriazole-1 -... 

Similarly, aldehyde o-aminophenylhydrazones, available by reduction of the nitro precursors, are converted in the absence of oxygen into 2-substituted benzimidazoles. The reaction is acid catalysed and, although complicated experimentally, gives good yields (67 87%), providing a useful alternative when the 2 substituent may be sensitive. When oxygen is not excluded, benzotriazines form instead 102J. In addition, only fair yields of 1-aminobenzimidazoles are obtained by acid-catalyscd cyclization of N-(o-nitroanilino)-substituted aliphatic amines. Benzotriazoles and benzotriazole... 

Disubstituted pyrrolidinonesJ 1-Substituted 5-(l-benzotriazolyl)pyirolidinones are available in one step from primary amines, benzotriazole, and 2,5-dimethoxy-2,5-dihydrofuran. The benzotriazolyl group is readily replaced by nucleophiles. 

Benzotriazole is a key component in the conversion of aldehydes to sec-alkyl primary amines. Benzotriazole is reacted with pivalaldehyde in the presence of SOCI2 and NaN3 to generate the a-azidobenzotriazole (96) in 42% yield. Sequential treatment of intermediate (96) with i) (CsH5)3P and CjHsMgBr in ether and ii) hydrolysis of the phospho-nium intermediate yields the primary amine (97) [94SC(24)2955]. 

When reacted with dimethyl acetylenedicarboxylate, the amines produced ben-zotriazolylaminobutendioates 188 accompanied by A-benzotriazolyl substituted 2-pyridones only in the case of 5-amino-2-methyl-2//-benzotriazole, the triazolo-9,10-dihydrobenzo[d]azepine and an unusual cyclization product, triazolo-2-oxindole (convertible into 2-methyltriazolo[4,5-/]carbostyril-9-carboxylate) were formed. The quinolones 189 were aromatized to chloroesters 190 these in turn were hydrolyzed to chloroacids 191 and decarboxylated to 9-chlorotriazolo[4, 5-/]quinolines 192 (Scheme 58) (93H259). The chlorine atom could be replaced with 17 various secondary amines to give the corresponding 9-aminoalkyl(aryl) derivatives 193, some of which exhibit both cell selectivity and tumor growth inhibition activity at concentrations between 10 and 10 " M (95FA47). 

In the presence of DCC, 140 is allowed to react with both l-hydroxy-5-nitroindole (36) and 1-hydroxy-1,2,3-benzotriazole (141). Interestingly, their corresponding active esters, 142 and 143, are obtained in excellent yields as stable crystalline compounds. Both compounds are found to react with variety of nucleophiles, such as alcohols and amines, to produce 144 and 145 in good to excellent yields, as can be seen from the typical examples shown in Scheme 22 (2001H2361). As aresult, it becomes possible to produce various kinds of derivatives of wasabi phytoalexin utilizing 142 and 143. 

A-Substituted 11-oxo-l l//-pyrido[2,l-6]quinazoline-6-carboxamides were prepared from 11-oxo-l l//-pyrido[2,l-6]quinazoline-6-carboxylic acids and amines in the presence of (/-Pr)2EtN and benzotriazol-l-yloxytris(dimethy-lamino)phosphonium hexafluorophosphate in CH2CI2 (98MIP1, 98MIP2, 99USP5908840, 99USP5914327). 

Boilers and steam systems Steel steam lines can be inhibited by the use of a volatile amine-based inhibitor such as ammonia, morpholine or cyclohexylamine introduced with the feedwater. It passes through the boiler and into the steam system, where it neutralizes the acidic conditions in pipework. The inhibitor is chemically consumed and lost by physical means. Film-forming inhibitors such as heterocyclic amines and alkyl sulphonates must be present at levels sufficient to cover the entire steel surface, otherwise localized corrosion will occur on the bare steel. Inhibitor selection must take into account the presence of other materials in the system. Some amine products cause corrosion of copper. If copper is present and at risk of corrosion it can be inhibited by the addition of benzotriazole or tolutriazole at a level appropriate to the system (see also Section 53.3.2). 

Section 13.7). There are other systems (benzotriazole brighteners in copper, aldehyde-amine brighteners in tin) which enhance corrosion resistance. 

An alternative approach towards the PASP synthesis of isocyanides was developed by Bradley [100,101]. It involved the use of a polymer-supported sul-fonyl chloride in the presence of base to afford the dehydration of formamides (Scheme 21). The formamides required could be easily prepared by reaction of the corresponding amines with a formylated benzotriazole resin. Opti-... 

A few aromatic amines do not react e.g. -substituted diamines yield benzotriazoles that cannot couple [1]. 

Moreover, a dramatic increase of the reaction rate was observed when the coupUng of aromatic imines mediated by samariiun diiodide was carried out in the presence of both water and a tertiary amine or tetramethylethylene-diamine (TMEDA) [29], causing the almost instantaneous formation of the 1,2-diamine, although with undetermined diastereoselectivity. Similarly, the samarium diiodide promoted reductive coupling of iminiiun ions formed in situ by reacting ahphatic aldehydes with secondary amines and benzotriazole occurred at temperatures as low as - 70 °C [30]. Even in this case a mixture of diastereomers with undetermined ratio was obtained nevertheless, the item of diastereoselectivity induced by a chiral amine (auxiliary) is worthy of investigation. 

FD-MS is also an effective analytical method for direct analysis of many rubber and plastic additives. Lattimer and Welch [113,114] showed that FD-MS gives excellent molecular ion spectra for a variety of polymer additives, including rubber accelerators (dithiocar-bamates, guanidines, benzothiazyl, and thiuram derivatives), antioxidants (hindered phenols, aromatic amines), p-phcnylenediamine-based antiozonants, processing oils and phthalate plasticisers. Alkylphenol ethoxylate surfactants have been characterised by FD-MS [115]. Jack-son et al. [116] analysed some plastic additives (hindered phenol AOs and benzotriazole UVA) by FD-MS. Reaction products of a p-phenylenediaminc antiozonant and d.v-9-lricoscnc (a model olefin) were assessed by FD-MS [117],... 

Products Driving forces Threats Hindered amine technology, benzotriazoles, benzophenones Consumer demand most resin systems Reducing volume, surface coating, higher-performing resins... 

The initial route to taranabant relied on a late stage amide bond coupling between racemic amine rac-2 and pyridine acid 3 mediated by (benzotriazol-l-yloxy)tripyr-rolidinophosphonium hexafluorophosphate (Py-Bop), followed by chiral HPLC separation of the product to afford a single enantiomer (Scheme 9.1). 

Traceless linker 60 based on a benzotriazole scaffold was reacted with amines and aldehydes to produce Mannich-type amine products [69]. Final product release was achieved by treatment with Grignard reagents (Scheme 29). 

The recently prepared benzotriazole-l-carboxamidinium tosylate represents a convenient reagent for conversion of amines to guanidines in moderate to good yields. The presence of the benzotriazole moiety causes the compound to be more reactive than pyrazole-1 -carboxamidinium hydrochloride [ni... 

Figure 1. Formation of carbonyl groups in 0.1 mm PP films as a function of irradiation time in Xenotest 150 (13). (UVA)2-(2 -hydroxy-3, 5 -di-tert-butylphenyl)-5-chloro-benzotriazole (Ni-Comp) Nickelf2,2 -thiobis-(4-tert-octylphenolate)]-n-butyl-amine (Benzoate) 2,4-di-tert-butylphenyl-3,5-di-tert-buty 1-4-hydroxy-benzoate (HALS) Bis-(2,2,6,6-tetramethyl-piperidinyl-4)sebacate.

Light/UV stabilisers Benzophenones, benzotriazoles, hindered amines... 

The reaction of benzotriazoles with aryl halides catalyzed by a mixture of Pd(dppe)Cl2 (DPPE = bis-(diphenylphosphino)ethane) or Pd(dppf)Cl2, copper(I)iodide or copper(II)carboxylates, and a phase-transfer catalyst has been shown to proceed in good yield in DMF solvent.104 Both copper and palladium were required for these reactions to occur at the N-l position in high yields. Similar results for the coupling of amines with aryliodonium salts in aqueous solvent were observed.105... 

Alkylation of benzotriazole with (chloromethyl)trimethoxysilane 99 provides a mixture of its derivatives 98 and 100 in a ratio of 1 3. In a reaction with tris-(2-hydroxyethyl)amine, compound 100 is converted to derivative 101 in nearly quantitative yield. Compound 98 reacts with tris-(2-hydroxyethyl)amine similarly (Scheme 6) <2003ARK(xiii) 125, 2003CHE1639>. 

Michael addition of (benzotriazol-l-yl)acetonitrile 557 to a,[)-unsatu rated ketones followed by heterocyclization provides new means for preparation of 2,4,5-trisubstituted pyridines. The reaction is catalyzed by bases. In the presence of secondary amines, a nucleophilic attack of amine on the CN group in adduct 556 initiates the cyclization to tetrahydropyridine 558 that subsequently eliminates water and benzotriazole to give pyridine 559. Analogously, in the presence of NaOH, pyridone 560 forms, via intermediate 561 (Scheme 88) <1997JOC6210>. 

In solution, l-(ot-aminoalkyl)benzotriazoles 562 are in equilibrium with iminium cation 563 and hence with their benzotriazole-2-yl isomers 564 (Scheme 89). Protonation or complexation of the benzotriazolyl moiety (e.g., Mg, Zn, B, A1 reagents) facilitates the transformation. Intermediate iminium cations 563 can be trapped by nucleophiles providing synthetic pathways to various amines. Many such reactions are described in CHEC-II(1996) <1996CHEC-11(4)1 >, and some newer results are compiled in reviews <2005T2555>. 

---