N-Hydroxymethylation

Carbazole, 2-hydroxy-reactions with citral, 4, 235 Carbazole, 2-hydroxy-9-methyl-synthesis, 4, 294 Carbazole, N-hydroxymethyl-as metabolite of carbazole, 1, 230 Carbazole, N-isopropyl-PE spectroscopy, 4, 190 Carbazole, A7-methyl- N NMR, 4, 175 X-ray spectroscopy, 4, 163 Carbazole, 1-nitro-synthesis, 4, 282 Carbazole, tetrahydro-dehydrogenation, 4, 282, 312 synthesis, 4, 107, 337, 353 Carbazole, 1,2,3,4-tetrahydro-reduction, 4, 255, 256 synthesis, 4, 312, 325, 352 Carbazole, 1,2,3,4-tetrahydro-1 -oxo-synthesis, 4, 337 Carbazole, 9-trifluoroacetyl-synthesis, 4, 218 Carbazole, vinyl-polymers, 1, 275, 301 Carbazole, 9-vinyl-copolymer... 

A one-pot conversion of benzyl alcohols to benzyl fluorides by treatment of the alcohols with a combination of methanesulfonyl fluoride, cesium fluoride and 18-crown 6 ether in tetrahydrofuran has been repotted The reaction involves mesylation of the alcohols followed by cleavage of the resultant mesyl esters with a fluoride ion The reaction has been extended also to certain heterocycles bearing the N hydroxymethyl group [43] (equation 31)... 

It forms a complex with dioxane contg 2 moles of TNMe to one of dioxane, mp 44—4.5°, bp at 8mm, 61—2° (Ref 19a, p 33). It reacts with aromatic dlazonium salts to give compds of the type ArN NC(N02)3. The compds are relatively unstable and their expl props have not been examined (Ref 12). It reacts with N-hydroxymethyl compds to form adducts of the type RNHCH2C(N02)3. The same compds are formed from TNMe, formaldehyde, and the amine or from trinitroethanol and the amine (Ref 31). It forms complexes with N-contg heterocyclics whose expl props have not been examined (Ref 42). It forms complexes with benzene and methylbenzenes. The formation constants for these complexes vary from 8.46 for the benzene complex to 279.4 for the hexa methylbenzene complex (Ref 49)... 

Bei N-Aryl-carbamidsaureestern werden dagegen die N-Hydroxymethyl-amine erhalten z.B.1 ... 

Natriumboranat reduziert dagegen N-Alkyl-barbitursauren unter Ringspaltung, so wirdz. B. aus 1,3-Dime-thyl-5,5-dibenzyl-barbitursaure liber die N-Hydroxymethyl-ureido-Zwischenstufe das 3-Phenyl-2-benzoyl-propanol erhalten5. 

CN [4S-(4a,4aa,5aa,6p, 12aa)]-7-chloro-4-(dimethylamino)-1,4,4a,5,5a,6,11,12a-octahydro-3,6,10,12,J2a-pentahydroxy-N-(hydroxymethyl)-6-methyl-1,11 -dioxo-2-naphthacenecarboxamide... 

A. N-(Hydroxymethyl)acetamide. A solution of 10 g. (0.07 mole) of anhydrous potassium carbonate in 137 g. of a 36-38% solution of formaldehyde (1.7 moles) in water (Note 1) is prepared in a 2-1., round-bottomed flask, and lOOg. (1.7 moles) of... 

The 8-methyl-8,14-cycloberbine 364, derived from the protoberberine 324 via the betaine 363, was reduced with sodium borohydride or lithium aluminum tri-tert-butoxyhydride to give a diastereoisomeric mixture of cis-and trans-alcohols (7.8 1 or 1 7.8, respectively) (Scheme 64).t)n exposure to formaldehyde the mixture underwent N-hydroxymethylation and subsequent intramolecular substitution on the aziridine ring to give the oxazolidine 365. Removal of the hydroxyl group in 365 was accomplished by chlorination followed by hydrogenolysis with tributyltin hydride. Reductive opening of the oxazolidine 366 with sodium cyanoborohydride afforded ( )-raddeanamine (360), which has already been converted to ochotensimine (282) by dehydration. 

Fig. 8.20. Two-step activation ofN-[(acyloxy)methyl] prodrugs, a) Cleavage of the ester bond, which may be enzymatic and/or nonenzymatic, is followed by decomposition of the N-(hy-droxymethyl) intermediate, b) For (V-(hydroxymethyl) derivatives of amides and imides, the decomposition is base-catalyzed, c) For N-(hydroxymethyl) derivatives of amines, the decomposition can be uncatalyzed or undergo acid or base catalysis (modified from [214]).

These and other interesting results allow quantitative insight into the rate of breakdown of N-(hydroxymethyl) compounds (i.e., carbinolamines (hemi-aminals)), the reaction mechanisms of which we examined in Sect. 8.7.3 (see, in particular, Fig. 8.20) [80 - 82], These carbinolamines, we recall, are major metabolic intermediates in oxidative N-dealkylation reactions resulting from cytochrome P450 catalyzed hydroxylation of the C-atom adjacent to the... 

Copolymers of acrylic acid with N-(hydroxymethyl)-, N-(2-hydroxyethyl)-, and N-(2-hydroxypropyl)acrylamlde were prepared In mole ratios of 3 1 [acrylic acid/... 

Carboxy substituted diazepines 226 and 229 react with phenyl isocyanate to afford pyrimido diones 227 and 230, correspondingly (Scheme 48, Section 3.1.1.3 (1993JHC897)). N-Hydroxymethylation on an indole ring annulated to benzaze-pinone, as well as formation of the corresponding carbamate and urea, has been described (2004MI1076). 

Furthermore, (L)-proline and paraformaldehyde give (L)-N-hydroxymethyl-proline (as the iminium carboxylate -i- H2O) upon large scale milling and stoichiometric millings of imidazole (0 °C) or benzimidazole (r. t.) with (HCHO) quantitatively provide the corresponding solid 1-imidazolylmethanols [22]. 

HYDR0XY-3-METHYL-1-PHENYL- (43108-74-3), 65, 5, 12 N-Hydroxymethylphthalimide Phthalimide, N-(hydroxymethyl)- ... 

Die C-Hydroxymethylierung mit Formaldehyd scheint bei 1-unsubstituierten Imidazolen iiber die N-Hydroxymethyl-Verbindungen zu verlaufen, die im Fall von 4 5)-Methyl-imidazol bzw. 2-Alkyl-4(5)-methyl-imidazolen unter milden Reaktionsbedingungen (Toluol, 50°) isoliert wer-den konnen730. Durch Behandeln mit konz. Salzsaure konnen diese 1-Hydroxymethyl-Verbin-dungen in 4(5)-Hydroxymethyl-imidazole umgclagert werden730. 

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