C-Bis hydroxymethylation

Compound 200e provides one example in which a pair of calixarenes are intermolecularly joined by a pair of upper rim to lower rim bridges. Other examples of upper rim to upper rim bridging are illustrated by (a) 215a, obtained in 48% yield by treating p-A,C-bis(hydroxymethyl)calix[4]arene with p-A,C-bis(chloromethyl)calix[4]arene in the presence of (b) 215b and... 

C,C -Bis(hydroxymethyl)neocarborane (LXI), prepared from the interaction of paraformaldehyde and dilithioneocarborane, is oxidized by aqueous alkaline potassium permanganate to the parent neocarborane (335). 

Polyhydric alcohol mercaptoalkanoate esters are prepared by reaction of the appropriate alcohols and thioester using -toluenesulfonic acid catalyst under nitrogen and subsequent heating (16,17). Organotin mercapto esters are similarly produced by reaction of the esters with dibutyltin oxide (18). Pentaerythritol can be oxidized to 2,2-bis(hydroxymethyl)hydracryhc acid [2831-90-5] C H qO, ... 

Ethyleneurea Resins. One of the most widely used resins during the 1950s and 1960s was based on dimethylolethyleneurea [136-84-5] (l,3-bis(hydroxymethyl)-2-imidazohdinone) commonly known as ethyleneurea resin. This resin [28906-87-8] is most convenientiy prepared from urea, ethylenediamine, and formaldehyde. 2-Imidazohdinone [120-93-4] (ethyleneurea) is first prepared by the reaction of excess ethylenediamine [107-15-3] wiih. urea (38) in an aqueous medium at about 116°C. 

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. 

Colorless phosphate ester surfactants were also prepared by treating P4O,0 with an organic OH-containing compound in the presence of a phosphinic acid color inhibitor, e.g., bis(hydroxymethyl)phosphinic acid color inhibitor. Thus, 558 parts dodecanol containing 2.4 parts of phosphinic acid color inhibitor was treated with 142 parts P4O10 at 100-135°C. The phosphate ester surfactant had a VCS color value of 1, whereas a sample prepared without the color inhibitor had a VCS color value of 5. Twenty-eight similar surfactants were prepared using various alcohols and alcohol-alkylene oxide condensates [22]. 

Die Bildung cyclischer Ather bei der Reduktion cyclischer Carbonsaure-anhydride mit Lithiumalanat wird der sauren Aufarbeitung zugeschrieben (s. S. 203)1 . In Ausnahmefallen werden auch mit Natriumboranat in Hy-droxyl-Gruppen-freiem Medium cyclische Ather7 erhalten. Wahrend Naphthalin-l,2-dicarbonsaure-anhydrid mit Diboran ausschlieBlich zum I.2-Bis-[hydroxymethyl]-naphthalin (63% d. Th.) reduziert wird, erhalt man aus Naphthalin-1,8-dicarbonsaure-anhydrid nur 111,3H- (Naphtho-[ 1,8a,8-c,d]-pyran) (40% d.Th.) ... 

The preferred initiator is stannous octoate in catalytic amount [95, 96] and polymerizations occur in bulk at 110°C or in toluene. The synthesis was expanded to stars with 40 and 48 arms by means of a hyperbranched poly(2,2 -bis(hydroxymethyl)propionicacid) or classical dendrimer, respectively [97],... 

The hydrogenation of HMF in the presence of metal catalysts (Raney nickel, supported platinum metals, copper chromite) leads to quantitative amounts of 2,5-bis(hydroxymethyl)furan used in the manufacture of polyurethanes, or 2,5-bis(hydroxymethyl)tetrahydrofuran that can be used in the preparation of polyesters [30]. The oxidation of HMF is used to prepare 5-formylfuran-2-carboxylic acid, and furan-2,5-dicarboxylic acid (a potential substitute of terephthalic acid). Oxidation by air on platinum catalysts leads quantitatively to the diacid. [32], The oxidation of HMF to dialdehyde was achieved at 90 °C with air as oxidizing in the presence of V205/Ti02 catalysts with a selectivity up to 95% at 90% conversion [33]. 

The bath temperature should not exceed 100°C in order to prevent contamination of the product with the his(hydroxymethyl) derivative of di-tert-butyl malonate. The product exhibits single peaks in the H Will spectrum (CDClj, 250 MHz at 1.51 and 5.25 ppm and contains approximately 6% of di-tert-butylmalonate as indicated by a peak at 1.47 ppm. Contamination by the bis(hydroxymethyl) derivative is Indicated by a peak at 1.48 ppm. 

Amino-2-metbyl-1 -propanediol 2-Ammo-2-meibyl-l, -dihydroxy-propane or Bis(hydroxymethyl )metbyl-aminometbane called in Beil /3-Amino-j8-methyl-trimethylenglykol), HO-CH,—C(NH )-CH. OH ... 

One of the pathways to synthesis of a,a -dehydronaphtho[c f)-thiapyrans 383a-d includes step-by-step heterocyclization of peri-bis-bromomethyl, peri-bis-hydroxymethyl, or peri-bis-hydroxybenzyl-... 

Enantioselective enzymatic transesterifications have been successfully used for the synthesis of optically active silanes with the silicon atom as the center of chirality. As shown in Scheme 20, the prochiral bis(hydroxymethyl)silanes 86 and 88 were transformed into the corresponding chiral dextrorotatory isobutyrates (+)-87 and (+)-89, respectively, using Candida cylindracea lipase (CCL, E.C. 3.1.1.3) as the biocatalyst73. For these bioconversions, methyl isobutyrate was used as solvent and acylation agent. When using acetoxime isobutyrate as the acylation agent and Chromobacterium viscosum lipase (CVL ... 

Andreu, C. Villarroya, J.-P. Garcia-Gastaldi, A. Medio-Simon, M. Server-Carrio, J. Varea, T. Enzymatic esterification of bicyclic meso-diols derived from 2,5-bis(hydroxymethyl)-furan. An enantioselective Diels-Alder reaction equivalent. Tetrahedron Asymmetry 1998,... 

Treatment of 2,2-bis-hydroxymethyl-propan-l-ol with diethyl carbonate and then with potassium thiocyanate at 180 °C gave 3-hydroxymethyl-3-methylthietane in 38% yield (Equation 22) <1996CB97>. 

Note This process affords (extranuclear) hydroxyalkyl-l,8-naphthyridines. Dimethyl l,8-naphthyridine-2,7-dicarboxylate gave 2,7-bis(hydroxymethyl)-1,8-naphthyridine (12) [NaB(OMe)3H, THF, CH2C12, 25°C 55% or NaBH4, EtOH, 25°C 19%].473... 

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