1961
DOI: 10.1021/ja01466a041
|View full text |Cite
|
Sign up to set email alerts
|

N-Nitrosoamides. V. N-Nitrosoamides of Secondary Carbinamines; An Example of Intramolecular Inversion of Configuration1

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
1
1
1
1

Citation Types

0
10
0
1

Year Published

1967
1967
2015
2015

Publication Types

Select...
7
2

Relationship

0
9

Authors

Journals

citations
Cited by 40 publications
(11 citation statements)
references
References 0 publications
0
10
0
1
Order By: Relevance
“…Other data suggest that N-nitrosoamides derived from branched amines likely rearrange through slightly different pathways that may involve secondary carbocations and tight ion pairs. [11,12,13] Related pathways for N-nitrosoamides derived from linear amines may explain the occasional formation of rearranged ester and rearranged elimination products when highly polar solvents, especially acetic acid, are used. N-nitrosodichloroacetamides, which are not as electron deficient as the trifluoroanalogues, avoid these problems by being stable to the conditions of the nitrosylation step and being able to be extracted from the acetic acid solvent into a nonpolar solvent that enables a cleaner rearrangement.…”
Section: Mechanismmentioning
confidence: 99%
“…Other data suggest that N-nitrosoamides derived from branched amines likely rearrange through slightly different pathways that may involve secondary carbocations and tight ion pairs. [11,12,13] Related pathways for N-nitrosoamides derived from linear amines may explain the occasional formation of rearranged ester and rearranged elimination products when highly polar solvents, especially acetic acid, are used. N-nitrosodichloroacetamides, which are not as electron deficient as the trifluoroanalogues, avoid these problems by being stable to the conditions of the nitrosylation step and being able to be extracted from the acetic acid solvent into a nonpolar solvent that enables a cleaner rearrangement.…”
Section: Mechanismmentioning
confidence: 99%
“…The diol in compound 11 was protected using 2,2-dimethoxypropane in acetone containing camphorsulfonic acid to give 12 in 85% yield (16). The corresponding dicarboxylic acid (14) was prepared in essentially quantitative yield by reacting compound 12 with dinitrogen tetraoxide (26) and anhydrous sodium acetate in dichloromethane (27,28) to provide the bis-[N-nitrosoamide] (13), which was hydrolyzed with lithium hydroxide and hydrogen peroxide (29,30) to furnish the dicarboxylic acid (14). Activation of 14 with N,N-disuccinimidyl carbonate delivered the corresponding activated bissuccinimidyl ester (15) in 95% yield (16).…”
Section: Chemistrymentioning
confidence: 99%
“…Zur 25 Pericyclische Mechanismen uber einen Drei-oder Fiinfring-tfbergangszustand sind bei 7 nicht rnit den 180-Befun-den zu vereinbaren, die ein partielles Aquilibrieren zeigen. Die Abhangigkeit der Reaktionsgeschwindigkeit vom Losungsmittel und vor allem vom Acylrest in 7 spricht fur eine Heterolyse im geschwindigkeitsbestimmenden Schritt.…”
Section: Versuche Mit '"0-indizierten Eduktenunclassified
“…C 65.05 H 8.45 N 16.87 3.1.1.4.3,3-Dimethyl-2-azabicyclo[2.2.2]oct-5-en-hydrochlorid (4) 1/6: 5.4, 1/7a: 2.5, 1/7b: 2.5, 4/5: 6.6, 4/6: 0.8, 4/8a: 2.5, 4/8b: 2.5, 5/6: 8.1, 7a/7b: 12.5, 7a/ 8a: 9.5, 7a/8b: 5.7, 7b/8a: 2.5, 7b/8b: 12.5, 8a/8b: 12.5 Hz. (22), 122 (7), 109 (8), 94 (loo), 80 (25), 79 (19), 58 (67).…”
Section: Warnungmentioning
confidence: 99%