Triethylamine Triols

Introduce to the round-bottomed flask triol 14 (7.7 g), triethylamine (22 mL) and CH2CI2 (300 mL). Cool the solution at 0°C with an ice bath. Start the stirring and place the addition funnel on the reaction flask. 

When BuSi(0SiMe20H)3 is heated, poly-condensation is immediately started, forming many different products. In order to synthesize low-molecular condensates, we have reacted BuSi(OSlMe2Cl)3 with one equivalent of the triol BuSi(0H)3 using triethylamine as HCl captor (compare also Eq. 2) the cage like BuSi(0SiMe20)3Si Bu is formed in 60% yield. In Fig. 3 the result of an X-ray structure analysis is depicted. Bicyclic molecules with the same skeleton of atoms but with different substituents are known [20,21]. 

Imidate chemistry published by Barrett and co-workers [6] around that time was subsequently found to effect clean conversion of triol 16 into dihydrobenzofuran 18. Thus, 16 was converted into the bisimidate 17, which quickly cyclized to 18 upon treatment with triethylamine. Under phase transfer reaction conditions, 18 was cleanly converted into our desired olefin 5. From this chemistry, a process was designed which afforded a 75% yield of 5 from dihydronaphthol in four steps with a minimum number of unit operations and only two intermediate isolations [7]. 

Transformation of commercial PEO diamines into the corresponding diisocya-nates 386 by reaction with stoichiometric amounts of triphosgene in refluxing dichloromethane, both in the presence and absence of triethylamine, and the subsequent condensation of these bifunctional oligomers with commercial PEO triols resulted in the aforementioned novel polymeric structures. 

The preparation of etherdiol 1 and triol 4 was carried out in multistep routes according to the reported procedures (8, 9). As summarized in Scheme I, the synthesis of acrylic esters, 2 and 5, was carried out in a fluorocarbon solvent such as Freon 113 by the reaction of alcohols, 1 and 4, with aoyloyl chloride and an amine acid acceptor such as triethylamine. Other attempts to esterify the fluoroalcohols directly with acrylic acid or acrylic anhydride were not successful (10). Product purification by distillation was not feasible because of the temperature required, but purification by percolation of fluorocarbon solutions through neutral alumina resulted in products, 2 and 5, of good purity identified by TLC, proton-1 NMR and IR. 

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