Oxidative reactions of azines

Солдатенков, А. Т.; Bekro, I. A.; Soldatova, S. A.; Glover, E. E.; Temesgen, A. V.; Kuleshova, L. N.; Khrustalev, Victor N.; Sergeeva, N. D.

doi:10.1007/bf02503786

Russ Chem Bull

1997

DOI: 10.1007/bf02503786

|View full text |Cite

Oxidative reactions of azines

А. Т. Солдатенков

I. A. Bekro

S. A. Soldatova

et al.

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...

Citation Types

Supporting

Mentioning

Contrasting

Year Published

1998

2014

Publication Types

Select...

Article4

Relationship

Self Cite0

Independent4

Authors

Journals

Cited by 4 publications

(3 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In our recent work 1,2 on the oxidative transformation of the notorious neurotoxin THP 1 3 and its analogues we have discovered a novel C sp 3 -C sp 3 coupling reaction between tetrahydropyridines and compounds containing an activated methyl group such as acetone, methyl aryl ketones and nitromethane. In the presence of potassium permanganate the THP nucleus in this unusual reaction is attacked by the CH acid at the allylamine position 2 leading to the formation of 2-R-methylideneTHP.…”

mentioning

confidence: 99%

Oxidative coupling and unusual hydroxymethylation of 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine in the presence of dicyanomethane

Солдатенков

Temesgen

Kuleshova

et al. 1998

Mendeleev Communications

View full text Add to dashboard Cite

mentioning

confidence: 99%

Oxidative coupling and unusual hydroxymethylation of 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine in the presence of dicyanomethane

Солдатенков

Temesgen

Kuleshova

et al. 1998

Mendeleev Communications

View full text Add to dashboard Cite

“…2 Compound 3b was prepared by hydroxylation of 2b in aqueous MeCN (2b:KMnO 4 = 1:1.5) at 0 °C, 2 h; yield 45%, mp 220-222 °C. 3 One-pot oxodihydroxylation of 1b in aqueous MeCN (1b:KMnO 4 = 1:1.5) at 20 °C yielded 65% of 3b in 2 h. 3 Compound 4a was obtained from one-pot oxidation of 1a•HCl in acetone (1a•HCl:KMnO 4 = 1:1.5) at 20 °C, 2 h; yield 85%, colourless oil, R f 0.73 in acetone. 4 4a was also obtained from oxidation of 3a in MeCN (3a:KMnO 4 = 1:1.5) at 50 °C, 0.5 h; yield 34%.…”

mentioning

confidence: 99%

“…In the 1 H NMR spectrum of the amide 4b a double set of N(Me)CHO group signals are observed. 1 H NMR, d: 2.92 and 3.12 (s, 2×1.5H, Me), 3.3 (t, 2H, 1-CH 2 , 2 J 6.0 Hz, 3 J 6.0 Hz), 3.8 (t, 2H, 2 J 6.0 Hz, 3 J 6.0 Hz), 7.75 and 8.85 (dd, 2×2H, AA' BB', 2 J 4.5 Hz, 3…”

mentioning

confidence: 99%

Cascade and stepwise oxidation of 4-phenyl- and 4-(γ-pyridyl)tetrahydropyridines

Солдатенков

Temesgen

Bekro

et al. 1998

Mendeleev Communications

View full text Add to dashboard Cite

ChemInform Abstract: Oxidative Reactions of Azines. Part 5. Ketodihydroxylation and Coupling of 4‐(γ‐Pyridyl)‐1,2,5,6‐tetrahydropyridines with Acetone. Molecular and Crystal Structure of 3,4‐Dihydroxy‐4‐(γ‐pyridyl)‐1‐ethylpiperidine‐2‐one.

Солдатенков¹,

Bekro²,

Soldatova³

et al. 1998

ChemInform

View full text Add to dashboard Cite

Oxidative coupling of l-alkyl(benzyl)-4-(y-pyri.dyl)-l,2,5,6-tetrahydropyridines with acetone in the presence of KMnO 4 follows two pathways and yields both I-R-2-(acetylmethy[ene)tetrahydropyridines and 1-R-3,4-dihydroxypiperidin-2-ones. When acetonitrile is used instead of acetone, the reaction under similar conditions occurs as selective ketodihydroxylation of the starting piperideines yielding l-R-3,4-dihydroxy-4-(y-pyridyl)piperidin-2-ones. The molecular and ccystal structures of one of these products (R = Et) was studied by X-ray diffraction analysis.Key words: oxidative coupling, ketodihydroxylation, 1-R-4-(~,-pyridyl)-l,2,5,6-tetrahydropyridines, 1-R-3,4-dihydroxy-4-('t-pyridyl)piperidin-2-ones, 1-R-2-acetylmethylene-4-(7-pyridyl)-l,2,5,6-tetrahydropyridines; NMR, X-ray diffraction analysis; molecular and crystal structures.Previously, 1,z in a study dealing with modification of the Wagner oxidation, we discovered a new reaction, namely, oxidative C--C-coupling of ct-methylketones with 4-aryltetrahydropyridines resulting in the formation of 2-acylmethylene derivatives of tetrahydropyridine. When acetone was used as the methyl-active component, 2-(acetylmethylene)tetrahydropyridines were isolated in yields of up to 70%.This condensation was carried out in the presence of KMnO 4 under mild conditions (-25 ~ and could be complicated by dihydroxylation of the double bonds in the initial tetrahydropyridines. This was not observed in our experiments, which is in agreement with the data 3 that 4-phenyltetrahydropyridines are inert under conditions of the Wagner reaction. However, when we studied the possibility of coupling of acetonitrile with 4-aryltetrahydropyridines, we obtained 4-phenyl-3,4-dihydroxypiperidin-2-ones a in good yields and with high regioselectivity rather than the coupling products, and in the case of bulky 4-[2.2]paracyclophanyl substituent, the reaction yielded tetrahydropyridin-2-one, s " For part 4, see Ref. 1 The present study dealing with the reaction of 4-heterylpiperideines was stimulated by the fact that the course and the extent of the oxidative transformations of 4-aryltetrahydropyridines in aqueous acetone and in aqueous acetonitrile in the presence of KlVlnO 4 are appreciably influenced by the nature of the methylactive component, the temperature of the reaction, and the character of the substituent at C(4) in 3-piperideine. As the heterocyclic substituent, we chose the 7-pyridyl group, which increases both the polarization of the double bond and the CH-acidity of the methylene group in the allylamine fragment of the piperideine and is thus favorable for the formation of dihydroxylactams or for oxidative coupling. If these reactions occur by radical mechanisms, the pyridyl nucleus could inhibit oxidative processes, especially C--C-coupling. The transformations studied in this work are shown in Scheme 1. The following initial tetrahydropyridines were used: 1-methyl-(5), t-ethyl-(6), and l-benzyl-4-(7-pyridyl)-1,2,5,6-tetrahydropyridines (7). These compounds were synthesized by t...

show abstract

scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.

Contact Info

customersupport@researchsolutions.com

10624 S. Eastern Ave., Ste. A-614

Henderson, NV 89052, USA

This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.

Blog Terms and Conditions API Terms Privacy Policy Contact Cookie Preferences Do Not Sell or Share My Personal Information

Made with 💙 for researchers

Part of the Research Solutions Family.

Oxidative reactions of azines

Cited by 4 publications

References 1 publication

Oxidative coupling and unusual hydroxymethylation of 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine in the presence of dicyanomethane

Oxidative coupling and unusual hydroxymethylation of 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine in the presence of dicyanomethane

Cascade and stepwise oxidation of 4-phenyl- and 4-(γ-pyridyl)tetrahydropyridines

ChemInform Abstract: Oxidative Reactions of Azines. Part 5. Ketodihydroxylation and Coupling of 4‐(γ‐Pyridyl)‐1,2,5,6‐tetrahydropyridines with Acetone. Molecular and Crystal Structure of 3,4‐Dihydroxy‐4‐(γ‐pyridyl)‐1‐ethylpiperidine‐2‐one.

Contact Info

Product

Resources

About