Oxetane hydroxymethyl

Methyl-3-oxetanemethanol 3-Oxetanemethanol, 3-methyl- (9) (3143-02-0) N-Benzyloxycarbonyl-L-serIne 3-methyl-3-(hydroxymethyl)oxetane ester L-Serine, N-[(phenylmethoxy)carbonyl]-, (3-methyl-3-oxetanyl)methyl ester (14) (206191-42-6) Cesium carbonate Carbonic acid, dicesium salt (8, 9) (534-17-8)... 

The chemoselective isomerization of secondary amide-substituted oxetanes 535 in the presence of Lewis acids gave 5-hydroxymethyl-5,6-dihydro-47/-l,3-oxazines 536 in moderate to fairly good yields (Equation 63). The isomerization was dependent on the substituent on the amide nitrogen atom, since tertiary amide analogs of 535 afforded dioxazabicyclo[2.2.2]octane derivatives under similar conditions <1998CC43, 2002T7049>. 

The synthesis of AMO involves treatment of 3,3-bis(chloromethyl) oxetane (BCMO) with sodium azide in the DMF medium at 85 °C for 24 h. Similarly, AMMO which is a monofunctional analog of AMO is synthesized by the azidation of chloro/tosylate product of 3-hydroxymethyl-3-methyl oxetane (HyMMO) with sodium azide in DMF medium at elevated temperatures. These energetic monomers are readily polymerized to liquid curable prepolymers with the help of boron trifluoride etherate/l,4-butanediol initiator system and the outlines of synthesis [147-150] of poly(BAMO) [Structure... 

Cross-linked, insoluble PEG can be prepared by copolymerizing PEG with epi-chlorohydrin [107,160] or with the tosylate of 3-methyl-3-(hydroxymethyl)oxetane [161,162], These supports are highly permeable and hydrophilic, and enable the use of... 

Sodium hydride (0.383 mol) was suspended in 200 ml of DMF, treated with the dropwise addition of trifluoroethanol (0.383 mol), and stirred for 30 minutes. This mixture was further treated with a solution of 3,3-bis-(hydroxymethyl)oxetane di-p-toluenesulfonate (0.073 mol) in 50 ml of DMF. The mixture was then heated to 75°C for 64 hours, poured into water, and extracted twice with CH2CI2. The combined extracts were washed with brine, 2% aqueous HCl, water, dried using MgS04, and... 

Bis(hydroxymethyl)dihydroisocodeine (108) (Scheme 2.15, p. 44) provided an intermediate that could be converted to analgesic oxetanes (e.g., 110) and to other, similar series (Schemes 2.16 and 2.17) all described earlier. Kotick(283) extended this work into series of 14-hydroxydihydrocodeines and 14-hydroxydihydromorphines. Here a facile cyclization between the 7/3-tosyl-oxymethylene moiety and the 14/3-OH occurred that denied access to... 

Cydopropan (tert.-Butylperoxy-methyl)-l-hydroxymethyl- E13/1, 380 (Oxetan + R-O-OH)... 

Potassium permanganate oxidation of S-hydroxymethyl-S-methyloxetane gave the potassium salt of S-methyl-S-oxetane carboxylic acid in 56% yield. ... 

The most versatile method involves rearrangement of an acylated hydroxymethyloxetane catalyzed by boron trifluoride etherate (13. 17). The triols are readily converted to the required hydroxymethyl oxetanes via pyrolysis of the carbonate esters (18) and then to the acylated hydroxymethyloxetanes with acid chlorides. 

Irradiation of 0.05 M l-(2-methyl-2-propenyl)-2.5-pyrrolidinedione (3) in acetonitrile with a 120-W low-pressure mercury lamp for about 120 h gives, after evaporation of the solvent, the oxetane 4 as an oily product almost quantitatively. After a prolonged heating at about 100 C, the oxetane decomposes to the starting material. By treatment with aqueous acid the oxetane is converted to 6-hydroxymethyl-6-methyI-2,5-azepanedione (5). 

It is proposed that this reaction involves an acid-activated formaldehyde intermediate (i.e., in the form of hydroxymethyl carbonium ion ) that electrophilically attacks the olefinic double bond to form an oxetane oxonium or a three-member bridged... 

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