Neighbouring group participation by a carbonyl group in the hydrolysis of methyl benzil-2-carboxylates

1992 ◽  
pp. 5 ◽  
Author(s):  
Keith Bowden ◽  
Faisal P. Malik
Keyword(s):  
Carbonyl Group ◽  
Group Participation ◽  
Neighbouring Group Participation ◽  
Hydrolysis Of

Dihydrotestosterone with an Ammonium Centre in the Position 16β

1997 ◽  
Vol 62 (4) ◽  
pp. 656-664 ◽  
Author(s):  
Barbora Slavíková ◽  
Alexander Kasal ◽  
Miloš Buděšínský
Keyword(s):  
Quaternary Ammonium ◽  
Water Soluble ◽  
High Yield ◽  
Partial Hydrolysis ◽  
Amino Group ◽  
Alternative Synthesis ◽  
Group Participation ◽  
Neighbouring Group Participation ◽  
Hydrolysis Of

In an alternative synthesis of 17β-hydroxy-16β-(piperidin-1-yl)-5α-androstan-3-one (4), neighbouring group participation between a 17β-carbonyloxy group and the 16β-amino group was used and a high yield partial hydrolysis of 3β,17β-diacetoxy-16β-(piperidin-1-yl)-5α-androstane (11) was developed. Interference of the neighbouring group participation was also apparent in another 17β-acetoxy derivative - in oxidation of compound 12 to 13. Compound 4 was converted into water-soluble derivatives, i.e. quaternary ammonium derivatives 17 to 20.

DFT study on the hydrolysis of metsulfuron-methyl: A sulfonylurea herbicide

2018 ◽  
Vol 17 (08) ◽  
pp. 1850050 ◽  
Author(s):  
Qiuhan Luo ◽  
Gang Li ◽  
Junping Xiao ◽  
Chunhui Yin ◽  
Yahui He ◽  
...  
Keyword(s):  
Free Energy ◽  
Water Molecule ◽  
Carbonyl Group ◽  
Energy Barrier ◽  
Density Functional ◽  
Free Energy Barrier ◽  
Functional Theory ◽  
Metsulfuron Methyl ◽  
Catalytic Role ◽  
Hydrolysis Of

Sulfonylureas are an important group of herbicides widely used for a range of weeds and grasses control particularly in cereals. However, some of them tend to persist for years in environments. Hydrolysis is the primary pathway for their degradation. To understand the hydrolysis behavior of sulfonylurea herbicides, the hydrolysis mechanism of metsulfuron-methyl, a typical sulfonylurea, was investigated using density functional theory (DFT) at the B3LYP/6-31[Formula: see text]G(d,p) level. The hydrolysis of metsulfuron-methyl resembles nucleophilic substitution by a water molecule attacking the carbonyl group from aryl side (pathway a) or from heterocycle side (pathway b). In the direct hydrolysis, the carbonyl group is directly attacked by one water molecule to form benzene sulfonamide or heterocyclic amine; the free energy barrier is about 52–58[Formula: see text]kcal[Formula: see text]mol[Formula: see text]. In the autocatalytic hydrolysis, with the second water molecule acting as a catalyst, the free energy barrier, which is about 43–45[Formula: see text]kcal[Formula: see text]mol[Formula: see text], is remarkably reduced by about 11[Formula: see text]kcal[Formula: see text]mol[Formula: see text]. It is obvious that water molecules play a significant catalytic role during the hydrolysis of sulfonylureas.

scholarly journals Neighbouring Group Participation in the Methanolysis of a Vicinal Diepoxide

1999 ◽  
Vol 23 (6) ◽  
pp. 356-357
Author(s):  
James R. Hanson ◽  
Peter B. Hitchcock ◽  
Ismail Kiran
Keyword(s):  
Hydroxy Group ◽  
Group Participation ◽  
Neighbouring Group Participation

The tetracyanoethylene catalysed methanolysis of 17β-acetoxy-4β,5β:6α,7α-diepoxyandrostane afforded 17β-acetoxy-4α,7α-oxido-5β-hydroxy-6β-methoxyandrostane in which the methanolysis product of the 6α,7α-epoxide has participated in the cleavage of the 4β,5β-epoxide; the reaction is modified however by an adjacent 3β-hydroxy group.

Sign in / Sign up

Export Citation Format

Share Document