O-Hydroxymethyl compounds

O-HYDROXYMETHYL COMPOUNDS 3.1.2. Benzylalcoholmono(poly)hemiformal (BHF) C6H5-CH2-0-(CH20)xH x= 1.5 153... 

O-HYDROXYMETHYL COMPOUNDS 3.1.5. (2-(2-butoxyethoxy)ethoxy)methanol C9H20O4... 

O-HYDROXYMETHYL COMPOUNDS 3.1.6. (3-Iodopropargyl)-(4-chlorophenyl) formal C10H8CIIO2... 

Borohydride reduction of 3-aryl-l,2-benzisothiazole 1,1-dioxides gives the 2,3-dihydro compounds 73JMC1170). Reduction of either 2-methylsaccharin or 2-hydroxymethylsac-charin with lithium aluminum hydride gives the same product, iV-methyl-o-hydroxymethyl-benzenesulfonamide (73AHC(15)233). 

Metabolism studies showed that the major metabolites of the components of ivermectin in cattle, sheep, and rats were 24-hydroxymethyl compounds, whereas major metabolites in swine were 3-0-desmethyl compounds. Identification of the 24-hydroxymethyl metabolites has not been yet achieved in swine, whereas identification of Hie 3-O-desmetlryl metabolites has not been made possible in cattle or sheep (54, 55). Recent metabolism studies (56) in cattle, swine, and rats have indicated, however, diat the metabolism of avermectins was qualitatively similar for all three species. There were quantitative differences both between species and between compounds for a given species, but all three species produced... 

Most possibilities and most examples in the syntheses of 1,4-dihydro-3(2//)-isoquinolinone (2) and its derivatives involve the cyclization of the corresponding arylacetic acid derivatives. The opportunity arises from the lactam structure of compound 2. With suitable reagents, different o-aminomethyl-, o-hydroxymethyl-, or o-chloromethyl-phenylacetic acid derivatives (25LA225 66JPR12 69CJC864 84JHC297) and o-hydroxymethyl phenylacetonitriles (85S114) can be cyclized. 

In addition to the preparation of a- and /3-hydrastine described above from the betaine (64), another conversion of a tetrahydroberberine into hydrastine has been reported. Acetylophiocarpine, on treatment with ethyl chloroformate, gives the acetoxy-derivative of (88), which can be hydrolysed to the hydroxymethyl compound and then oxidized to the aldehyde by pyridinium perchlorate. Hydrolysis of the acetoxyl group afforded the hemi-acetal (93 R = H), conversion of which into the mixed acetal (93 R = Et) protected the aldehyde system during reduction of N—C02Et to NMe by lithium aluminium hydride. Hydrolysis of the acetal, followed by oxidation, then gave a-hydrastine, and a similar sequence of reactions starting from O-acetyl-13-epi-ophiocarpine afforded / -hydrastine.119 Methods of synthesis of alkaloids of this group have been reviewed.120... 

NIOSH has developed independent methodologies for acrolein and formaldehyde which recommend the use of reagent-coated adsorbent tubes to collect the aldehydes as stable derivatives. The formaldehyde sampling tubes contain Chromosorb 102 adsorbent coated with N-benzy-lethanolamine (BEA) which reacts with formaldehyde vapor to form a stable o) olidine compound. The acrolein sampling tubes contain XAD-2 adsorbent coated with 2-(hydroxymethyl) piperidine (2-HMP) which reacts with acrolein vapor to form a different, stable oxazolidine derivative. Acrolein does not appear to react with BEA to give a suitable reaction product. Therefore, the formaldehyde procedure cannot provide a common method for both aldehydes. However, formaldehyde does react with 2-HMP to form a very suitable reaction product. It is the quantitative reaction of acrolein and formaldehyde with 2-HMP that provides the basis for this evaluation. 

Although the CSDP acid method was easily applicable to o-methoxy-substituted alcohol 22 (entry 11), o-methyl-substituted alcohol 23 could not be enantioresolved as the CSDP acid esters because of the small difference between o-methyl and hydrogen groups. So, the indirect method was adopted as follows. o-Hydroxymethyl-diphenylmethanol 24 was enantioresolved as CSDP esters, where the primary alcohol moiety was esterified, and the AC of the second-eluted ester was determined by X-ray crystallography (entry 12). Enantiopure alcohol (7 )-(+)-24 was then converted into the target compound (R)-(—)-23. It should be noted that the AC of alcohol 23 was originally proposed on the basis of an asymmetric reaction mechanism, but it was revised later by this study. The data of alcohols 25 and 26 indicate that the HPLC separation as CSDP esters is easier for silyl ethers (entries 13 and 14). ... 

Minisci reactions have also been applied to these compounds. formation by exposure to w-CPBA and O-methylation with Meerwein s reagent converted 54 into 55. Nucleophilic attack of the hydroxymethyl radical, generated with ammonium sulfate, provides an alternate route to 2-hydroxymethyl pyridines 56. 

Analysis of the Murchison meteorite led to a completely different type of phosphorus compound the only phosphorus-containing compounds found were alkanephos-phonic acids. Spurred on by these results, de Graaf et al. (1995) irradiated mixtures of o-phosphorous acid in the presence of formaldehyde, primary alcohols or acetone with UV light (low pressure Hg lamp, 254 nm with a 185-nm component) and obtained phosphonic acids, including hydroxymethyl and hydroxyethyl phosphonic acids, which had been found in the Murchison meteorite. Alkanephosphonic acids can be derived from phosphorous acid, with a P-H bond being replaced by a P-C bond. 

---