By Gould R.F. (ed.)
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Presents accomplished insurance of the kinds of mark downs gone through by way of a few of the periods of natural chemistry. Discusses mark downs in response to what bond or practical team is lowered by means of diverse reagents. offers specific recognition to selective mark downs which are appropriate for the relief of 1 specific form of bond or functionality with no affecting different bonds or features found in an identical molecule.
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6 2. I 34 AKIRA SEKlGUCHl AND HlDEKl SAKURAI R A A (25) (29) I$: R (26) RO R hvhv (A (A = 360-380 > 460 nm) nm)* )$fR R R+ R (30) R SCHEME 20 double bonds. The large negative activation entropy suggests the significant decrease of the freedom in the transition state to form 25. All attempts to trap the hexasila-Dewar benzene 29 with methanol or sulfur failed, probably due to the rapid intramolecular reaction to regenerate 25. Irradiation of hexagermaprismane26 (R = 2,6-i-Pr&H3) also produced new absorption bands at 342,446, and 560 nm due to hexagerma-Dewar benzene 30 at low temperature.
BuMezSiSi)8(15), silyl substituents decrease the strain in the polyhedrane (14). Thus, the synthesis of tetrasilatetrahedrane has been accomplished by use of the "supersilyl" group (tert-Bu3Si)(10). The dehalogenation of tert-Bu3Si-SiC13 with sodium at 80°C led to the formation of various products: 1,2-bis(supersilyl)disilane (31) and tris(supersi1yl)cyclotrisilane (32). N + benzene 80 'C (31) I tricycle[ I . 02,4]tetrasilane(34) as yellow-orange crystals in 57% yield (Scheme 21). The reaction mechanism for 34 is not clear.