Photochemical retro-aldol type reactions of nitrobenzyl derivatives. Mechanistic variations in the elimination of nitrobenzyl carbanions from nitrobenzyl derivatives on photolysis

1986 ◽  
Vol 64 (9) ◽  
pp. 1949-1951 ◽  
Author(s):  
Peter Wan ◽  
S. Muralidharan

The photochemical retro-aldol type reactions of several nitrobenzyl derivatives are reported. The reactions are observed only in aqueous solution with quantum efficiencies being pH dependent for several derivatives, consistent with the existence of several mechanistic pathways for reaction. The primary photochemical event is believed to involve the generation of a nitrobenzyl carbanion, which acts as a photolabile leaving group in these reactions, and the generation of an oxocarbocation (or oxocarbocation-derived) fragment.

Author(s):  
Juan Yu ◽  
Chaoqun Xu ◽  
Chuanwei Lu ◽  
Qian Liu ◽  
Jifu Wang ◽  
...  

Preparation and application of sustainable polymers derived from renewable resources are of great significance. The aim of this study is to synthesize a kind of sustainable polymeric micelles from rosin and vegetable oils via atom transfer radical polymerization (ATRP) and to investigate the doxorubicin delivery properties of these micelles. Dehydroabietic acid–based poly lauryl methacrylate (DA-PLMA) with narrow PDI of 1.13 was prepared in a well-controlled process using rosin as an ATRP initiator. Thereafter, carboxylic groups were introduced to form poly methacrylic acid (PMAA) moieties in DA-PLMA polymer via acid hydrolysis. The resulted DA-PLMA-PMAA could self-assemble in water to form pH-dependent polymeric micelles with a diameter of ∼65 nm and PDI as low as 0.105. Owing to the existence of rosin, DA-PLMA-PMAA micelles also showed self-fluorescence properties. In addition, Dox-loaded micelles were prepared in aqueous solution with the drug-loading capacity as high as 16.0% and showed sustained-release characteristics. These results demonstrate great promise for designing polymeric micellar from rosin and vegetable oils.


2017 ◽  
Vol 295 (8) ◽  
pp. 1343-1349 ◽  
Author(s):  
Juraj Škvarla ◽  
Rahul K. Raya ◽  
Mariusz Uchman ◽  
Jiří Zedník ◽  
Karel Procházka ◽  
...  

2017 ◽  
Vol 7 (1) ◽  
Author(s):  
Qingju Liu ◽  
Li Chen ◽  
Zhikun Zhang ◽  
Bibai Du ◽  
Yating Xiao ◽  
...  

2012 ◽  
Vol 30 (7) ◽  
pp. 1490-1496 ◽  
Author(s):  
Rongqing Li ◽  
Chunlei Wang ◽  
Shuhong Xu ◽  
Zhuyuan Wang ◽  
Haibao Shao ◽  
...  

1973 ◽  
Vol 26 (6) ◽  
pp. 1235 ◽  
Author(s):  
SC Chan ◽  
SF Chan

The second-order rate constants for the thallium(III)-induced aquation of cis-[Co(en)2(RNH2)Cl]2+ cations, where R is H, Me, Et, Prn, and Pri, have been measured in aqueous solution over a range of temperatures, and the activation parameters calculated. The kinetic results are discussed in terms of a rapid pre-equilibrium formation of an activated complex Co-Cl-Tl, followed by a simple rate-determining aquation in which TlCl2+ acts as the leaving group, although the alternative possibility of a rate-determining attack by Tl3+ cannot be excluded. In the case of R = H, the investigations have been extended to the corresponding bromo cation which reacts some 50 times faster than its chloro analogue.


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