Hydroxy formic acid

While hydroxy formic acid is the simplest of the hydroxy mono-carboxy acids it will not be discussed here because, as may be seen if the formula is examined, it corresponds to the hypothetical carbonic acid, H2CO3. 

As hydroxy formic acid is undoubtedly identical with carbonic acid it will be studied later as the latter compound (p. 425). 

We see, therefore, that carbonyl chloride may be considered as either the mono-acid chloride of chlor formic acid or the di-acid chloride of carbonic acid, which means that carbonic acid may also be considered as hydroxy formic acid. The following formulas show this relationship... 

Addition of a hydroxy group to alkynes to form enol ethers is possible with Pd(II). Enol ether formation and its hydrolysis mean the hydration of alkynes to ketones. The 5-hydroxyalkyne 249 was converted into the cyclic enol ether 250[124], Stereoselective enol ether formation was applied to the synthesis of prostacyclin[131]. Treatment of the 4-alkynol 251 with a stoichiometric amount of PdCl2, followed by hydrogenolysis with formic acid, gives the cyclic enol ether 253. Alkoxypalladation to give 252 is trans addition, because the Z E ratio of the alkene 253 was 33 1. 

PurpurogaHin (5), a red-brown to black mordant dye, forms from electrolytic and other mild oxidations of pyrogaHol (1). The reaction is beHeved to proceed through 3-hydroxy-(9-benzoquinone (2) and 3-hydroxy-6-(3,4,5-trihydroxyphenyl)-(9-benzoquinone (3). The last, in the form of its tautomeric triketonic stmcture, represents the vinylogue of a P-diketone. Acid hydrolysis leads to the formation of (4), foHowed by cyclization and loss of formic acid... 

An enzyme-catalyzed appHcation has been used to prepare the enantiomers of hydroxy-substituted tetrahydroisoquinolines (160). The synthesis of ( V)-reticuline [485-19-8] (30) has been reported using similar methodology (161). The substitution of formic acid and paraformaldehyde in this method leads to lower reaction temperatures, freedom from hydrolysis of protective groups, and improved yields (162). 

Organic acids may inhibit growth when present in the undissociated form because of their abiHty to change the pH inside the ceU. The most efficient are benzoic acid and sorbic acid, but formic, acetic, and propionic acid also have this effect. The parabens, ie, -hydroxy benzoic acid esters, are also used because of their antimicrobial effect over a broad pH range. 

The thermal condensetion of p-benzyloxyphenylacetic acid and of 3-methoxy-4-hydroxy-phenethylamine occurs and gives, with a yield of 86% to 92%, the N-(3-methoxy4-hydroxy-phenethyl-p-benzyloxyphenylacetamide from this latter, by cyclization according to Bischler-Napieralski with phosphorus oxychloride in acetonitrile, followed by reduction with sodium borohydride, there is obtained with a yield of 75% to 80% the 1-(p-benzyloxybenzyl)-6-meth-oxy-7-hydroxy-1,2,3,4-tetrahydroisoquinoline, which is methylated with formaldehyde and formic acid giving 1 (p-benzyloxybenzyl)-2-methyl-6-methoxy-7-hydroxy-1,2,3,4-tetrahydro-isoquinoline with a yieid of 90%. 

However, when we oxidized malonaldehyde (56) in the conditions just described for triose reductone, although formic acid and carbon dioxide were produced in high yields, the periodate consumption was erratic. Similar results were obtained with deoxy sugars. This discrepancy may be caused by the incomplete enolization of the first intermediate, hydroxy malonaldehyde —i.e. tartronic dialdehyde (5,22,32), to triose reductone, or may concern the hydroxylation step itself. 

Other preparations and isolations. If damp methylenedi(nitroformamide) is allowed to stand for several days, the odor of formic acid is noticed, and MEDINA can be isolated from the residue (Ref 11, p 14). The details of scale-up to 150 lb batches, including exp details and flow sheets, and further scale-up with the aim of prodn of 1000 lbs are given. The report describes a fume-off and fire which occurred during the S3rd run. The cause was attributed to a stuck valve which allowed nitric acid to build up in the reactor (Ref 13, p 57). In Ref 16, p 73 there are cost analysis data for pilot plant and large scale prodn, flow sheet for a proposed coml plant, and material balances. The action of acet anhydr on N,Nf-bis(hydroxy-methyl)MEDlNA regenerates MEDINA (Ref 6) the diNa salt of N. N trinitrotrimethylene-diamine, on warming with me ale, ppts the Na salt of MEDINA... 

Acyl groups are common in bacterial polysaccharides. The parent acids are fatty acids, hydroxy acids, and amino acids. The simplest acid, formic acid, has only been found as the amide. The occurrence of O-formyl groups had been reported, but proved to be incorrect. A-Formyl groups have been found in different polysaccharides for example, in the 0-specific side-chains of the LPS from Yersinia enlerocolitica 0 9, which are composed of 4,6-dideoxy-4-formamido-D-mannopyranosyl residues. The formyl group can assume two main conformations, s-cis (41) and s-trans (42), which are... 

On the other hand, refluxing 9 in formic acid for 5 h afforded the N-formyl derivative 11 in high yield. Acetylation of 9 by refluxing in acetic acid, afforded acetic acid N -(2-(7-hydroxy-2-oxo-2H-chromen-4-yl)-acetyl)-hydrazide 12 in good yield. Compound 13 was also obtained by refluxing 9 with 3-(2-bromoacetyl)-4-hydroxy-2H-chromen-2-one in ethanol. Reaction of compound 9 with phenyl isothiocyanate in ethanol at room temperature gave 4-phenyl-1 - (7-hydroxy-2-oxo-2 H-chromen-4-acetyl- )thiosemicarbazide 14. 

Hydroxy-3-methoxybenzaldehyde, Thallium(III) nitrate See Thallium(III) nitrate Formic acid, etc. 

Amino(phenyl)methylenemalonate (1424) was hydrolyzed by heating in boiling aqueous formic acid for 30 min to give hydroxy(phenyl)methy-lenemalonate (1425) (85TL2603). 

Photolytic. Anticipated products from the reaction of allyl chloride with ozone or OH radicals in the atmosphere are formaldehyde, formic acid, chloroacetaldehyde, chloroacetic acid, and chlorinated hydroxy carbonyls (Cupitt, 1980). 

Thermolysis of D-fructose in acid solution provides 11 and 2-(2-hydrox-yacetyl)furan (44) as major products. Earlier work had established the presence of 44 in the product mixtures obtained after acid-catalyzed dehydrations of D-glucose and sucrose. Eleven other products were identified in the D-fructose reaction-mixture, including formic acid, acetic acid, 2-furaldehyde, levulinic acid, 2-acetyl-3-hydroxyfuran (isomaltol), and 4-hydroxy-2-(hydroxymethyl)-5-methyl-3(2//)-furanone (59). Acetic acid and formic acid can be formed by an acid-catalyzed decomposition of 2-acetyl-3-hydroxyfuran, whereas levulinic acid is a degradation prod-uct of 11. 2,3-Dihydro-3,5-dihydroxy-6-methyl-4//-pyran-4-one has also been isolated after acid treatment of D-fructose.The pyranone is a dehydration product of the pyranose form of l-deoxy-D-eo f o-2,3-hexodiulose. In aqueous acid seems to be the major reaction product of the pyranone. 

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