4-Hydroxymethyl-3-nitro

Tris(hydroxymethyl)nitro- 3532C I(1)403A, N(1)354D TY7350000... 

Amin Hydroxymethyl-nitro-(2,2,2-trinitro-ethyl)- E14a/2, 73 (CH20/R-NH-N02)... 

Activated hydrogen atoms, prepared to react with formaldehyde to yield C-hydroxymethyl compounds, one finds in nitro-hydrocarbons at the carbon atom adjacent to the nitro group, in ketones at the carbon atom in alpha-position towards the carbonyl group, in certain phenol derivatives. However, the formaldehyde combined in these substances cannot be determined by the Tanenbaum method, as the hydroxymethyl group is fixed to the substances more or lees irreversibly. Accordingly C-hydroxymethyl compounds in general do not exhibit antimicrobial activity with the exception of the hydroxymethylated nitro-hydrocarbons, which under certain conditions (pH >7) release formaldehyde, though very slowly. As C-hydroxymethylated nitro-hydrocarbons... 

The hydroxymethylated nitro-hydrocarbons disposing of an activated halogen are described under 17. Compounds with activated halogen atoms . 

A-Containing Heterocycles. Nitroalkenes were reacted with TBDMSCI and DBU to afford A-silyloxyisoazoUdines through the intramolecular olefin cycloadditions of the nitronate intermediates. Only one diastereomer with three new consecutive stereogenic centers was isolated in good to excellent yield. Desi-lylation with TBAF and further spontaneous aerobic oxidation furnished the hydroxymethyl nitro compounds (eq 50). 1-Bromo-nitroalkanes, on the contrary, when treated with TBDMSCI and TEA, underwent the same cycloaddition reaction to produce the nitronates after in situ elimination of TBDMSBr (eq 51). ... 

On dehydration, nitro alcohols yield nitro-olefins. The ester of the nitro alcohol is treated with caustic or is refluxed with a reagent, eg, phthaUc anhydride or phosphoms pentoxide. A mil der method involves the use of methane sulfonyl chloride to transform the hydroxyl into a better leaving group. Yields up to 80% after a reaction time of 15 min at 0°C have been reported (5). In aqueous solution, nitro alcohols decompose at pH 7.0 with the formation of formaldehyde. One mole of formaldehyde is released per mole of monohydric nitro alcohol, and two moles of formaldehyde are released by the nitrodiols. However, 2-hydroxymethyl-2-nitro-l,3-propanediol gives only two moles of formaldehyde instead of the expected three moles. The rate of release of formaldehyde increases with the pH or the temperature or both. 

The nitro alcohols in Table 1 are manufactured in commercial quantities however, three of the five of them are used only for the production of the corresponding amino alcohols. 2-Methyl-2-nitro-l-propanol (NMP) is available as the crystalline soHd or as a mixture with siHcon dioxide. 2-Hydroxymethyl-2-nitro-1,3-propanediol is available as the soHd ( 9.15/kg), a 50% solution in water ( 2.33/kg), a 25% solution in water ( 1.41/kg), or as... 

Polymers. AH nitro alcohols are sources of formaldehyde for cross-linking in polymers of urea, melamine, phenols, resorcinol, etc (see Amino RESINS AND PLASTICS). Nitrodiols and 2-hydroxymethyl-2-nitro-l,3-propanediol can be used as polyols to form polyester or polyurethane products (see Polyesters Urethane polymers). 2-Methyl-2-nitro-l-propanol is used in tires to promote the adhesion of mbber to tire cord (qv). Nitro alcohols are used as hardening agents in photographic processes, and 2-hydroxymethyl-2-nitro-l,3-propanediol is a cross-linking agent for starch adhesives, polyamides, urea resins, or wool, and in tanning operations (17—25). Wrinkle-resistant fabric with reduced free formaldehyde content is obtained by treatment with... 

Stabilizers. Nitro alcohols can be used to prevent the decomposition of phenylenediarnine color-developing agents (27). 2-Hydroxymethyl-2-nitro-l,3-propanediol and 2-nitro-1-butanol have been used as additives for the stabilization of 1,1,1-trichloroethane. 

Other. 2-Nitro-1-butanol is an excellent solvent for many polyamide resins, cellulose acetate butyrate, and ethylceUulose. It can be utilized in paint removers for epoxy-based coatings. 2-Hydroxymethyl-2-nitro-l,3-propanediol is usebil for control of odors in chemical toilets. Its slow release of formaldehyde ensures prolonged action to control odor, and there is no reodorant problem which sometimes is associated with the use of free formaldehyde. 2-Hydroxymethyl-2-nitro-l,3-propanediol solutions are effective preservative and embalming fluids. The slow Uberation of formaldehyde permits thorough penetration of the tissues before hardening. 

Nitromethane. The nitroparaffins are used widely as raw materials for synthesis. Nitromethane is used to produce the nitro alcohol (qv) 2-(hydroxymethyl)-2-nitro-l,3-propanediol, which is a registered biocide useful for control of bacteria in a number of industrial processes. This nitro alcohol also serves as the raw material for the production of the alkanolamine (qv) 2-amino-2-(hydroxymethyl)-l,3-propanediol, which is an important buffering agent useful in a number of pharmaceutical appHcations. 

Furalazine, Acetylfuratrizine, Panfuran-S. Heating nitrovin in butanol or dimethylformamide at 100—130°C affords furalazine, 6-[2-(5-nitro-2-furanyl)ethenyl]-l,2,4-triazine-3-amine (34). An improved synthesis originates with 5-nitro-2-furancarboxaldehyde and acetone, proceeds through 4-(5-nitro-2-furanyl)-3-buten-2-one followed by a selenium dioxide oxidation to the pymvaldehyde hydrate, and subsequent reaction with aininoguariidine (35). Furalazine, acetylfuratrizine (36), and the A[-A/-bis(hydroxymethyl) derivative, Panfuran-S, formed from the parent compound and formaldehyde (37), are systemic antibacterial agents. 

Nifurtoinol. Treatment of nitrofurantoin with formaldehyde gives nihirtoinol, 3-hydroxymethyl-l-[5-nitro-2-furanyl)methyleneamino]-2,4-imidazohdinedione, a urinary tract antibacterial (46). The kinetics of decomposition of this dmg and its potential as a prodmg of nitrofurantoin have been reported (47). 

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... 

Tris-(hydroxymethyl)nitromethane [2-(hydroxymethyl)-2-nitro-l,3-propanediol] [126-11-4] M 151.1, m 174-175°(dec, tech grade), 214°(pure). Crystd from CHCl3/ethyl acetate or ethyl acetate/ benzene. It is an acid and a O.IM sol in H2O has pH 4.5. IRRITANT. 

Ultraviolet absorption spectra of tetrahy dro-1,3-oxazines do not show any maximum. Only after the introduction of a chromophoric group do bands appear. Thus 5-nitro derivatives show a strong maximum near 270 m/A, which is typical for a nitro group, and another one near 200 m(x which is probably also produced by the nitro group.In the instance of 5-nitro-5-hydroxymethyl derivatives, the absorption is much weakened this was explained by Urbanski in terms of a hydrogen bond between the hydroxyl and the nitro group. Other chromophores, such as C=0, C=NH, C—C, also cause the appearance of absorption maxima in the range 210-265 m/A and near 360... 

In d sumldf way, a-nitroselenides are prepared via the reacdon of nitronates with phenylse-lenyl bromide, which gives a new synthedc method of 1-nitroalkenes from nitroalkanes The sequence of ct-selenadon, nitro-aldol reacdon, and oxidadon provides a nsefid method for the preparadon of nitroalkenes with a hydroxymethyl group fEq 5 81 ... 

Chemicai Name 3-( Hydroxymethyl)-1 - [[ (5-nitro-2-furanyl) methylene] -amino] -2,4-imidazolidinedione... 

Diacyl peroxide] = [amine] = 1.0 x 10 mol/L,45 C HDMA p-hydroxymethyl-A/,A/-dimethylaniline NDMA p-nitro-A/,A/-dimethylani-line DMAB p-dimethylaminobenzaldehyde. 

COOC2H5 HN-Z — 2-Thiono-4-hydroxymethyl- 5-(4-nitro-phenyl)-I,3-thiazo-lidin6 91% d.Th. F 139-143°... 

Thiono-4-hydroxymethyl-5-(4-nitro-phenyl)- 213 2-Thiono-5-(4-nitro-phenyl)-4-athoxycarbonyl-tetrahydro- 213... 

Hydroxy-butyl)-l-( -hydroxy-benzyl)- 296 Hydroxylamino- 474, 682 4-Hydroxylamino-l-athylthio- 684 Hydroxylamino-alk(aryl)oxy- 684 2-Hydroxylamino-1 -isopropenyl- 698 4-Hydroxyl amino-1 -methyl- 683 4-Hydroxylamino-1 -methylthio- 684 2-Hydroxylamino-l-nitro- 562 2-Hydroxylamino-l-[penten-(l)-yl-(2)J- 698 4-Hydroxylamino-l-phenylthio- 684 4-Hydroxylamino-1 -sulfonyl- 683 Hydroxymethyl- 499... 

Dimethylamino-methyl)-2-hydroxymethyl-aus 2 -Carboxy-2-(dimethylaminocarbonyl)-biphenyl und Lithiumalanat 165 2,2 -Dinitro- 474, 476, 695 6,6 -Dinitro-2,2 -bis-[chlorcarbonyl]- 188 2,2 -Dinitro-4,4 -bis-[diathylamino]- 695 4,4 -Dinitro-2,2 -bis-rhydroxymethyl]- 213 6,6 -Dinitro-2,2 -bis-[hydroxymethyl]- 188 2,2 -Dinitro-4,4 -diamino- 695 6,6 -Dinitro-2,2 -diformyl- 694 4,4 -Dinitro-2,2 -dimethoxycarbonyl- 213 2,2 -Dinitro-4,4 -dimethyl- 695 6,6 -Dinitro-2 -formyl-2-carboxy- 694 2,2 -Dinitroso- 476 -4-hydroxamsaure-chlorid 537 4-(a-Hydroxy-benzyl)- 542 Methoxy- 678 2-Methyl- 556 Nitro- 672, 678 4-Nitro- 687... 

TFA) in DCM (dichloromethane). Linkers for carboxylic acids have also been designed to effect cleavage via photolysis (3-nitro-4-hydroxymethylbenzoic acid, ONb 14) [18] and flouridolysis (N-3 or 4) ((4-hydroxymethyl)-phenoxy-t-butylphenylsilyl)phenyl pentanedioic acid monoamide (PBs) 15 [19] and quinonemethide-based handle 16 [20] (Fig. 

---