THERMAL AND PHOTODEGRADATION OF PHOTOCHROMIC SPIROINDOLINENAPHTHOOXAZINES AND SPIROINDOLINENAPHTHOPYRANS - REACTION WITH NUCLEOPHILES - TRAPPING OF THE MEROCYANINE ZWITTERIONIC FORM
V. Malatesta et al., THERMAL AND PHOTODEGRADATION OF PHOTOCHROMIC SPIROINDOLINENAPHTHOOXAZINES AND SPIROINDOLINENAPHTHOPYRANS - REACTION WITH NUCLEOPHILES - TRAPPING OF THE MEROCYANINE ZWITTERIONIC FORM, Journal of the American Chemical Society, 119(15), 1997, pp. 3451-3455
Adducts of the zwitterionic (ZW) form of merocyanine (MC) of five phot
ochromic spirooxazines (SO) and spiropyrans (SP) have, for the first t
ime, been prepared photochemically or thermally through a trapping rea
ction of metastable MC with trimethylsilyl cyanide (TMSCN) in dichloro
methane. The adducts (ZWAs) form easily and are obtained in almost qua
ntitative yields. X-ray diffraction analysis of ZWA of spirooxazine 2
shows that in the adduct the planes of the indolyl and naphthyl moieti
es form a ca. 29 degrees angle. The adduct crystallizes in the monocli
nic space group P2(1)/n with a = 22.663(4) Angstrom, b = 8.234(1) Angs
trom, c = 14.455(2) Angstrom, beta = 104.72(1)degrees, V = 2637.4(7) A
ngstrom(3), and D-calcd = 1.1476 Mg/m(3) for Z = 4. Least-squares refi
nement of the model based on 1986 reflections (F > 4 sigma(F)) converg
ed to a final R = 0.066 and R-W = 0.068. ZWAs form through an unpreced
ented, clean, and regioselective Michael-type 1,6-addition of TMSCN to
either a strongly polarized quinoidal MC form or its charge-separated
zwitterionic limit structure. No evidence for the more common 1,2- an
d/or 1,4-addition has been found. The observed high reactivity of SOs
and SPs with nucleophiles may contribute to the reported limited durab
ility of these classes of photochromes.