Pyridinol 6-methyl

Elming, N. Clauson-Kaas, N. 6-Methyl-3-pyridinol from 2-hydroxymethyl-5-aminomethyl-furan, Acta Chem. Scand., 1956, 10, 1603-1605. 

Pyridines and pyrroles can be formed in different pathways by Mail-lard reaction. The formation of 5-methyl pyrrole aldehyde and 6-methyl-3-pyridinole has been observed by Nyhammar et al (17) by the reaction of isotope labelled 3-deoxyosone with glycine. The 3-deoxy-hexosone represents an -dicarbonyl compound and in this way the Strecker degradation occurs. Another pathway is the reaction of fu-rans with ammonia. Under roast conditions, we have obtained primarily the corresponding pyrrole, whereas we found the corresponding py-... 

The products can be separated conveniently by sublimatography . " 6-Methyl-3-pyridinol (MI-273) can be prepared directly from furfurylamine and formalin in hydrochloric acid or by way of 2-aminanethyl-5-hydroxy-methylfuran. ... 

Irradiation of pyridine-1-oxides in the gas phase with ultraviolet light can lead to deoxygenation. In benzene the pyridine and some phenol are often formed. Other products include 3-pyridinols, 2-pyridones, and 2-formyl- or acylpyr-2-Picoline-l-oxide gives small amounts of both 2- and 6-methyl-3-pyridinol, in addition to other products. Irradiation of... 

The course of alkylation of 2- and 6-substituted-3-pyridinols is subject 10 a steric effect. Sodium salts of 3-pyridinol in ethanol are N-alkylated by methyl bromo- or iodoacetate. However, 2-bromo-3-pyridinol is N-alkylated by methyl and ethyl iodide in dimethylformamide but is 0-alkylated by haloacetates to XII-563 (Rj = Br, R = H). 2-Bromo-6-methyl-3-pyridinol (XH-562, Rj = Br, R = CH3) is A-alkylated by methyl and ethyl iodide and 6>-alkylated by diazomethane, but reacts with bromoacetic acid in chlorobenzene to give 3-hydroxy-6-methyl-2-pyridone (XII-565), possibly via 2-(a-bromoacetoxy)-6-methyl-3-pyridinol (XII-S64). With 6-methyl-2-methylthio-3-pyridinol (XII-562 Rj = CH3S, R = CH3), A-alkylation should be favored electronically, particularly by electron release by the 2-methylthio group. However, quaternization is difficult even with the simple alkyl halides and only 0-alkylation is observed when methyl iodoacetate is used. ... 

Methyl-3-pyridinol is brominated in pyridine to give 2-bromo- and then 2,4-dibromo-6-methyl-3-pyridinol. lodination with sodium iododichloride gives 2-iodo-6-methyl-3-pyridinol. lodination of 2-(/7-substituted phenyl)-3-pyri-dinols (Xn-665 R = H, CHj, C Hs, CH(CH3)2. C(CH3)3, Q, OCHj) gives 2-aiyl-6-iodo-3-pyridinols. This should be contrasted with nitration of these pyridinols, which occurs first on the phenyl group " (Section II1.2.D.,... 

Ethyl-6-methyl-3-pyridinol, aminomethylation of, 813 5-Ethyl-l-Tttethyl-2-pyridone, hydroxymethylation of, 015 Ethyl nicotinoylacetate, in... 

Methyl-3-pyridinol, Sll aminomethylation of, 811 from 2-aminomethyl-5-hydroxy-... 

Bis-(6-methyl-3-pyridinol) (23), a pyridine analogue of biphenyl, shows intense fluorescence, which suggests that there is some quinonoid character. The structure consists of discrete planar molecules, which display... 

Cl2H1oNg, 3,6-Di-(2-pyridyl)-1,4-dihydro-1,2,4,5-tetrazine, 42B, 187 C12H12N2O2, 2,2 -Bis(6-methyl-3-pyridinol), 37B, 131 C12H12N2O2S2 0.5 CuHbO, Bis-3-hydroxy-6-methylpyridyl-2,2 -disul-fide hemi(tetrahydrofuran), 43B, 289... 

Ru(6-methyl-2-pyridinolate)2(PPh3)2, 2,795 4, 466 RuC48H44C12P4 RuCl2(PHPh2)4,4, 378 RuC4sH44N03P 2... 

C H, N02 13287-64-4) see Pyridinol carbamate 6-methyl-2-pyridinemethanol acetate (ester) 1-oxide (GjHjiNOj) sec Pyridinol carbamate... 

Scheme 19.—Mechanism for Formation of 2-Acetylpyrrole and 2-Methyl-3-pyridinol.

Pyridinol carbamate has been used as an anri-inflammatory/anti-arteriosderotic. This compound 2,6-pyridinedimethanol-bis-(N-methyl carbamate) is also known as Anginin. See rhe formula below1. 

The fragmentation of 2-acylpyrroles (6) and 3-pyridinols (7) on electron impact (El) has been elucidated and is shown for L -7 in Figure 7. The two numbers under each ion are the m/z values expected with the label at the alternative positions, the latter number within parantheses corresponding to labelled methyl carbon. Where the two m/z values differed, the peak at the first one always predominated in the El mass spectra of the labelled (J-7 obtained on GC/MS analysis of Extracts 1 and 3. This was in complete accordance with the 1 5C-NMR spectrometric results, but for several reasons the mass spectrometric results were less accurate and did not exclude up to 15 % of the label in the respective methyl groups. Most important, the spectra showed clusters of peaks at consecutive m/z values, including those of interest. The content was calculated by means of a computer program based on the somewhat doubtful assumption that ions in the same cluster differed only in hydrogen content and/or isotopic composition. 

It is not requisite that the anion eliminated in the step 19 to 20 be a hydroxyl ion, because acid hydrolysis of 5-amino-5-deoxy-l,2-0-isopropylidene - 3 - O - (methylsulfonyl )-a- D -xylofuranose likewise yields 3-pyridinol (21). On subjection to acid hydrolytic conditions which remove the 2V-acetyl group, such N-acetyl derivatives as 5-acetamido-5-deoxy-a-D-xylopyranose (see p. 167) are immediately transformed, through 17, into 3-pyridinol (21). Furthermore, acid hydrolysis of methyl 5-acetamido-5-deoxy-2,3,4-tri-0-methyl-a-D-... 

The reaction of 5-amino-5-deoxy-l,2-0-isopropylidene-a-D-xylo-furanose (15) with methanolic hydrogen chloride (0.5 %), under careful exclusion of moisture, results in a mixture of the anomers of methyl 5-amino-5-deoxy-D-xylofuranoside, from which the /8-D anomer crystallizes. The five-membered ring-structure was proved by the results of periodate oxidation and by the infrared spectrum of the tetraacetate, which shows a band for NH. A methyl pyranoside was not found, and 3-pyridinol (21) was formed only in traces. A spontaneous ring-enlargement, such as is observed under similar conditions with 1,2-O-isopropylidene-5-thio-a-D-xylofuranose (see p. 208), is not possible in this instance. Stabilization as the methyl fiiranoside is, apparently, so rapid that the secondary reaction (leading to the pyranose form) does not occur. If water (several percent) is added to the reaction mixture, glycoside formation is hindered, and a large proportion of 3-pyridinol is formed. ... 

C4H10S methyl propyl sulfide 3877-15-4 -112 98 1.1274 2 4261 C5H4BrNO 2-bromo-3-pyridinol 6602-32-0 25.00 1.7203 2... 

In addition to the above-described alkyl phosphates, a few less common metabolites can be mentioned, e.g. 3,5,6-trichloro-2-pyridinol (TCP). TCP is a major product of esterase cleavage of the OPi chlorpyrifos and chlopyrifos-methyl." ° Urinary TCP, like other... 

---