Nucleophilic addition and displacement in the reaction of 2,4,6-trimethylphenoxide ion with 1,3,5-trinitrobenzene. An oxygen-bonded aryloxide σ-complex

1981 ◽  
Vol 59 (16) ◽  
pp. 2470-2474 ◽  
Author(s):  
Erwin Buncel ◽  
Robert Y. Moir ◽  
Albert R. Norris ◽  
Alain-Pierre Chatrousse
Keyword(s):  
Complex Formation ◽  
Dimethyl Sulfoxide ◽  
Nitro Group ◽  
Nucleophilic Addition ◽  
Thermodynamic Control ◽  
Definitive Evidence ◽  
Dimethyl Sulfoxide Solution ◽  
Diaryl Ether

Reaction of 1,3,5-trinitrobenzene with potassium 2,4,6-trimethylphenoxide in dimethyl sulfoxide solution leads to σ-complex formation concurrently with displacement of a nitro group. The results provide definitive evidence for σ-complex formation via the oxygen of aryloxide ion in this system, and contrast with the situation that obtains with phenoxide ion itself, which under corresponding conditions yields the carbon-bonded σ-complex as the product of thermodynamic control. Stereoelectronic factors in σ -complex formation and in the diaryl ether resulting from nitro displacement are also discussed.

The 1,3,5-Trinitrobenzene–Phenoxide σ-Complex. Ambident Phenoxide Ion in SNAr Systems

1975 ◽  
Vol 53 (24) ◽  
pp. 3761-3767 ◽  
Author(s):  
Erwin Buncel ◽  
Andrzej Jończyk ◽  
John G. K. Webb
Keyword(s):  
Dimethyl Sulfoxide ◽  
Product Formation ◽  
Mineral Acid ◽  
Thermodynamic Control ◽  
Aromatic Carbon ◽  
Dimethyl Sulfoxide Solution ◽  
A Minor ◽  
Ambident Nucleophile

1,3,5-Trinitrobenzene reacts with potassium phenoxide in dimethyl sulfoxide solution to yield a σ-complex in which bonding has occurred between the para carbon of the phenoxy moiety and an unsubstituted carbon of the nitroaromatic substrate. A minor proportion of ortho adduct is also obtained. When the reaction is performed in DMSO–MeOH (80:20, v/v) one obtains initially the methoxide adduct of TNB which is then smoothly transformed into the phenoxide adduct. The latter is stable to dilute mineral acid, unlike the former; formation of a σ-complex involving bonding between the phenoxy oxygen and a carbon of TNB is thereby excluded. The reaction represents the first instance of phenoxide ion acting as an ambident nucleophile towards aromatic carbon. The implication of this finding on the course of related SNAr reactions is discussed on the basis of kinetic and thermodynamic control of product formation.

Complex formation of peptide antibiotic Ro09-0198 with lysophosphatidylethanolamine: proton NMR analyses in dimethyl sulfoxide solution

Biochemistry ◽  
1990 ◽  
Vol 29 (1) ◽  
pp. 113-118 ◽  
Author(s):  
Kaori Wakamatsu ◽  
Se Young Choung ◽  
Tetsuyuki Kobayashi ◽  
Keizo Inoue ◽  
Tsutomu Higashijima ◽  
...  
Keyword(s):  
Complex Formation ◽  
Dimethyl Sulfoxide ◽  
Proton Nmr ◽  
Peptide Antibiotic ◽  
Dimethyl Sulfoxide Solution

Formation of spiro adduct from N-methyl-N-(2,4,6-trinitrophenyl)glycine anion

1989 ◽  
Vol 54 (2) ◽  
pp. 440-445 ◽  
Author(s):  
Vladimír Macháček ◽  
Alexandr Čegan ◽  
Miloš Sedlák ◽  
Vojeslav Štěrba
Keyword(s):  
Nmr Spectroscopy ◽  
Dimethyl Sulfoxide ◽  
Equilibrium Constant ◽  
Mole Fraction ◽  
Nucleophilic Addition ◽  
Adduct Formation ◽  
First Case ◽  
C Nmr

The intramolecular nucleophilic addition of N-methyl-N-(2,4,6-trinitrophenyl)glycine anion in methanol-dimethyl sulfoxide mixtures produces spiro[(3-methyl-5-oxazolidinone)-2,1'-(2',4',6'-trinitrobenzenide)]. The spiro adduct has been identified by means of 1H and 13C NMR spectroscopy. This is the first case when the formation of a Meisenheimer adduct with carboxylate ion is observed. Logarithm of the equilibrium constant of adduct formation increases linearly with the mole fraction of dimethyl sulfoxide in its mixture with methanol.

Vicarious nucleophilic amination of nitroquinolines with 4-amino-1,2,4-triazole

2008 ◽  
Vol 86 (7) ◽  
pp. 682-685 ◽  
Author(s):  
Barbara Szpakiewicz ◽  
Maria Grzegożek
Keyword(s):  
Dimethyl Sulfoxide ◽  
Nucleophilic Substitution ◽  
Nitro Group ◽  
Para Position ◽  
Basic Medium ◽  
Ortho Position ◽  
Vicarious Nucleophilic Substitution

3-, 5-, 6-, 7- and 8-Nitroquinolines react with 4-amino-1,2,4-triazole in basic medium (potassium tert-butoxide-dimethyl sulfoxide) giving amino products of the vicarious nucleophilic substitution (VNS) of hydrogen, predominantly at ortho position to the nitro group, except 8-nitroquinoline, which reacts at para position. Additionally, furazano[3,4-f]- and furazano[3,4-h]quinoline were obtained in the case of 5- and 8- nitroquinoline, respectively. 2-Nitroquinoline was aminated to 2-quinolino(1,2,4-triazol-4-yl)amine in these conditions.Key words: nitroquinolines, vicarious nucleophilic substitution (VNS), 4-amino-1,2,4-triazole.

scholarly journals Cathodic Deposition of Silver from Dimethyl Sulfoxide Solution

1973 ◽  
Vol 41 (12) ◽  
pp. 880-883 ◽  
Author(s):  
Shuta NAKAGAWA ◽  
Zenichiro TAKEHARA ◽  
Shiro YOSHIZAWA
Keyword(s):  
Dimethyl Sulfoxide ◽  
Cathodic Deposition ◽  
Dimethyl Sulfoxide Solution
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