The formation of azoxyalkanes in reactions of some organometallic reagents with N-nitroso-O,N-dialkylhydroxylamines: the nonphotochemical synthesis of an acyclic (E)-azoxyalkane
Abstract:Azoxyalkanes were found to be regiospecifically formed in the reactions of some alkyllithium and Grignard reagents with N-nitroso-O,N-dialkylhydroxylamines. Remarkably, although (Z)-stereomers were usually produced, in one case the (E)-isomer was predominant.
“…Stevens 19 later perfected the preparation of azoxy compounds from the O 2 -tosylated acyl diazeniumdiolates (eq 39), although radical side reactions can interfere in some solvents (but apparently not in all cases). Interestingly, the O 1 -alkyl diazeniumdiolates, reacting via their nitrosohydroxylamino form, produce azoxy compounds with the oxygen on the opposite nitrogen from those above with excellent regiospecificity (eq 40), and alkyllithium reagents may also be used …”
Section: Reaction With Nucleophiles (Including Hydrolysis/solvolysis)mentioning
confidence: 99%
“…Interestingly, the O 1 -alkyl diazeniumdiolates, reacting via their nitrosohydroxylamino form, produce azoxy compounds with the oxygen on the opposite nitrogen from those above with excellent regiospecificity (eq 40), and alkyllithium reagents may also be used. 174…”
Section: Reaction With Nucleophiles (Including Hydrolysis/ Solvolysis)mentioning
Joseph A. Hrabie received his entire education in the New York City public school system, including his Ph.D. degree in Chemistry (1981) under the guidance of Professor William F. Berkowitz at Queens College of the City University of New York. After postdoctoral research with Professor Herbert O. House at the Georgia Institute of Technology, he moved to the National Cancer Institute at Frederick and is currently a Senior Scientist with SAIC−Frederick, the primary NCI contractor at the site. In addition to many scientific publications, his continuing interest in nitric oxide chemistry has resulted in 15 U.S. patents. Larry K. Keefer received his B.A. degree from Oberlin College and his Ph.D. degree in Chemistry (1965) under the guidance of Professor Gloria G. Lyle at the University of New Hampshire. He held research positions at the Chicago Medical School and the University of Nebraska College of Medicine before coming to the National Cancer Institute in 1971. He and his colleagues in the NCI's Chemistry Section, Laboratory of Comparative Carcinogenesis, are intensively studying the chemistry and pharmacology of the diazeniumdiolates as nitric oxide sources for biomedical applications.This section contains a description of reactions that are used preparatively as well as those that do not
“…Stevens 19 later perfected the preparation of azoxy compounds from the O 2 -tosylated acyl diazeniumdiolates (eq 39), although radical side reactions can interfere in some solvents (but apparently not in all cases). Interestingly, the O 1 -alkyl diazeniumdiolates, reacting via their nitrosohydroxylamino form, produce azoxy compounds with the oxygen on the opposite nitrogen from those above with excellent regiospecificity (eq 40), and alkyllithium reagents may also be used …”
Section: Reaction With Nucleophiles (Including Hydrolysis/solvolysis)mentioning
confidence: 99%
“…Interestingly, the O 1 -alkyl diazeniumdiolates, reacting via their nitrosohydroxylamino form, produce azoxy compounds with the oxygen on the opposite nitrogen from those above with excellent regiospecificity (eq 40), and alkyllithium reagents may also be used. 174…”
Section: Reaction With Nucleophiles (Including Hydrolysis/ Solvolysis)mentioning
Joseph A. Hrabie received his entire education in the New York City public school system, including his Ph.D. degree in Chemistry (1981) under the guidance of Professor William F. Berkowitz at Queens College of the City University of New York. After postdoctoral research with Professor Herbert O. House at the Georgia Institute of Technology, he moved to the National Cancer Institute at Frederick and is currently a Senior Scientist with SAIC−Frederick, the primary NCI contractor at the site. In addition to many scientific publications, his continuing interest in nitric oxide chemistry has resulted in 15 U.S. patents. Larry K. Keefer received his B.A. degree from Oberlin College and his Ph.D. degree in Chemistry (1965) under the guidance of Professor Gloria G. Lyle at the University of New Hampshire. He held research positions at the Chicago Medical School and the University of Nebraska College of Medicine before coming to the National Cancer Institute in 1971. He and his colleagues in the NCI's Chemistry Section, Laboratory of Comparative Carcinogenesis, are intensively studying the chemistry and pharmacology of the diazeniumdiolates as nitric oxide sources for biomedical applications.This section contains a description of reactions that are used preparatively as well as those that do not
“…3 Their reduction leads to corresponding alkoxyamines 4 whereas reaction with organolithium compounds and Grignard reagents is known to form azoxyalkanes. 5 In the last decade N-nitroso derivatives of N,O-disubstituted hydroxylamines have been drawing attention as isosteric biomimetics of unstable carcinogenic a-hydroxynitrosoamines generated from nitrosoamines in vivo. In this connection their thermolysis and hydrolysis have been investigated by Kano and Anselme.…”
1,2-Bis(N-alkoxy-N-nitroso)amines 7 obtained by nitrosation of the corresponding 1,2-bisalkoxyamines 4 were smoothly converted into 1-alkoxy-4,5-dihydro-1,2,3-triazole 2-oxides 8 under reflux in methanol in high yields. 4H-1,2,3-Triazole 2-oxides 9, a novel type of triazole oxides, and 2-hydroxy-2H-1,2,3-triazoles 10 were obtained by the reaction of 1-alkoxy-4,5-dihydro-1,2,3-triazole 2-oxides 8 with sodium methoxide.
Durch Umsetzung der Nitrosohydroxylamine (I) mit Alkyl‐Li bzw. Grignardverbindungen (II) werden die Z‐konfigurierten Titelverbindun‐ gen (III) erhalten; im Falle von (Ib) + (IIa) wird neben (IIIa) auch dessen E‐Isomeres (IV) gebildet (Diskussion).
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