Phenoxy acetylene

To improve the processability of PPQ, appropriate phenylquinox-aline oligomers were end-capped with acetylenic groups using 3-(3,4-diaminophenoxy)phenylacetylene (43) or 4-(3- and 4-ethynyl-phenoxy)benzil (44, 45) (Eq. 10). The processability was improved but at the sacrifice of the thermooxidative stability. In general, cured acetylene-terminated heterocyclic polymers are less stable in a thermooxidative environment than the parent linear polymer. 

Various forms of radiation have been used to produce ions in sufficient quantitites to yield neutral products for subsequent analysis. In principle, it should be possible to use intense beams of UV below ionization threshold for this purpose. To date, however, efforts to collect neutrals from resonant multiphoton ionization (REMPI) have not succeeded. In one experiment, 1 mbar of gaseous -propyl phenyl ether was irradiated at room temperature with a 0.1 W beam of 266 nm ultraviolet (from an 800 Hz laser that gives 8 n pulses) concurrent with a 0.5 W beam at 532 nm. The beams were intense enough not only to ionize the ether in the mass spectrometer, but also to excite it so that it expels propene. After several hours of irradiation < 10% of the starting material remained. Production of carbon monoxide and acetylene (decomposition products of the phenoxy group) could be detected by infrared absorption spectroscopy, but the yield of neutral propene (as measured by NMR spectroscopy) was infinitesimal. 

Thus, the reaction of mixed (phenylthio)alkylcuprates with 9-BBN overcomes the problem associated with (1) the thermal instability of phenoxy- and tert-bu-toxyalkylcuprates, (2) the low reactivity of mixed acetylenic cuprates, and (3) the wasting of one R group of the homocuprates. 

Another efficient method to prepare chiral propargylamines 42 using a multicomponent process is by alkylation of in situ formed propargyl imines from alkynals 40 and o-phenoxy aniline (11c) by dialkylzinc derivatives 41 in the presence of a chiral ligand, for instance a dipeptide, and a Lewis acid salt, as depicted in Scheme 11.16 [48], Furthermore, the synthesis of A-aryl propargyl amines can be also performed by the alkynylation using dimethylzinc and terminal acetylenes of several aldehydes and o-methoxyaniline catalyzed by (l/ ,25)-A-bis(p-methoxybenzyl)norephedrine and phenylacetylene (52-93%, 79-97% ee) [49],... 

---