Cyclische Diazoverbindungen, I. Herstellung und Umsetzungen von Diazirinen

Schmitz, Ernst; Ohme, R.

doi:10.1002/cber.19610940834

Cited by 118 publications

(45 citation statements)

References 14 publications

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“…The melting point of compound 3 (103 °C) coincided with that given in Ref. 6. 13 C NMR without proton decoupling (CDCl 3 ), δ: 24.4 (t, С(3), С(5), 1 J = 129.4 Hz); 24.6 (t, С(4), 1 J = 129.3 Hz); 35.7 (t, С(2), С(6), 1 J = 128.0 Hz); 56.9 (s, C(1), 2 J = 5.1 Hz).…”

Section: Methodssupporting

confidence: 55%

Electrochemical synthesis of pentamethylenediazirine

et al. 2006

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Electrochemical synthesis of pentamethylenediazirine at the Pt/Ti anode was conducted. The reaction is reversible. The rate constants of the direct and reverse processes were estimated. The product and current yields of the target compound approach to 100%.Diazirines are efficient sources of carbenes. 1 For in stance, photolysis of pentamethylenediazirine 1 under high pressure affords cyclohexene 2 in high yield (Scheme 1). 2 Scheme 1Usual methods for the synthesis of diazirines are the oxidation of the corresponding diaziridines with mercury oxide, bichromate, silver oxide, and others.In the present work, compound 1 was synthesized by the electrochemical oxidation of pentamethylenedi aziridine 3 (Scheme 2). 3,4 Scheme 2The oxidation products of compound 3 in an undi vided cell using the Pt/Ti anode were analyzed by 1 H, 13 С NMR and UV spectroscopy. The analysis showed that the oxidation of compound 3 affords up to 50% of compound 1 without formation of by products. The UV spectra of the electrolyte containing a mixture of com pounds 1 and 3 coincided with the published 5 spectra of compound 1. The UV spectra of a solution of compound 3 oxidized in an undivided cell upon passing different amounts of electricity are shown in Fig. 1. When the content of compound 1 increases monotonically, the con tent of compound 3 decreases, correspondingly, to some limiting value (Fig. 2) equal approximately to 50%, which can be due to reversibility of the process in an undivided cell. This conclusion was completely confirmed by the electrolysis of the initial compound in a diaphragm di vided cell loaded with a mixture of equal amounts of compounds 1 and 3. In the presence of a diaphragm, the initial substrate in this mixture can be oxidized with al most 100% conversion, i.e., until the initial substrate dis appeared completely (Fig. 3).Using the data presented in Fig. 3, we estimated the rate constant of substrate oxidation in the direct path way (k) by the first order equationwhere С 0 and С t are the initial concentration of com pound 3 and its concentration to the moment t. The k value was 0.12 h -1 . The curve for the consumption of compound 3 calculated by the first order equation with k = 0.12 h -1 is shown in Fig. 3. Since in the absence of a diaphragm and in equilibrium the contents of the initial * Dedicated to Academician O. M. Nefedov on the occasion of his 75th birthday.

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Section: Methodssupporting

confidence: 55%

Electrochemical synthesis of pentamethylenediazirine

et al. 2006

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“…Es wurden keine weiteren Versuche zur Isolierung des reinen Diarnins unternomrnen. (28): Eine Losung von 0.55 g (5 rnmol) 28 in 50 rnlO.1 N HCI wird in der oben beschriebenen Weise elektroreduziert. Cyclohexanon wurde gaschrornatographisch ermittelt.…”

Section: Ergebnisse Der Praparativen Elektroreduktion Einiger Hydraziunclassified

Studien zum Vorgang der Wasserstoffübertragung, 52. Zur Kenntnis der elektroreduktiven Spaltung der N ‐ N‐Bindung

Horner

Jordan

1978

Justus Liebigs Ann. Chem.

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Am Beispiel von 35 Hydrazinderivaten wird die elektroreduktive Spaltung polarographisch und praparativ untersucht. Es wurde gefunden: 1) Beim mono-, tri-und tetrabenzoylierten Hydrazin 9, 11 bzw. 12 verschiebt sich das Potential proportional der Anzahl der Benzoylgruppen nach positiveren Werten. Beim symmetrischen l ,2-Dibenzoylhydrazin (10) wird das Halbstufenpotential El/*bedingt durch H-Verbruckung und mesomere Stabilisierungstark nach negativen Werten verschoben. -2) Bei den cyclischen Hydrazinderivaten 14 -16 werden die E,,,-Werte sowohl in Abhangigkeit von der Ringspaltung als auch durch cis-Fixierung der Benzoylgruppen noch zusatzlich nach positiveren Werten verlagert. -3) Uberfiihrung eines N-Atoms der Hydrazinogruppe in ein Oniumzentrum durch Alkylierung oder Protonierung hat eine positive Verschiebung des Halbstufenpotentials zur Folge. -4) Praparativ wird gezeigt, da8 bei der Elektroreduktion aller untersuchter Beispiele die N -N-Bindung als elektroaktiver Bereich reduktiv aufgespalten wird [Ausnahme: 3,6(1H,2H)-Pyridazindion ( S ) ] . Die Elektroreduktion von 1,2-Dibenzoyl-1,2diazaspiro[2.5]octan (14) fuhrt zu N,N'-(1 ,I-Cyclohexyliden)bis(benzamid). Ausgehend von den bicyclischen Hydraziniumsalzen 25 und 27 konnen elektroreduktiv 1 -Methyl-l,5-diazacyclooctan und 1 -Methyl-1,6-diazacyclodecan erhalten werden. Studies on the Occurrence of Hydrogen Transfer, 52'). -The Electroreductive Cleavage of the N -N Bond 2 )Electroreductive cleavage of a series of 35 hydrazine derivatives has been studied under polarographic and preparative conditions. The results show: 1) In mono-, tri-and tetrabenzoyl substituted hydrazines, 9, 11 and 12, respectively, the half-wave potential increasing along the series proportionally with the number of benzoyl groups. In the case of the symmetrical 1,2dibenzoylhydrazine (10) the value of El/, is shifted to a much more negative potential due to mesomeric and hydrogen bonding effects. -2) In the cyclic hydrazines 14 -16 the El,, values shift to more positive potentials dependent on the ring strain and the extent of cis-configuration of the benzoyl groups. -3) Replacement of one nitrogen atom by an onium centre by protonation or alkylation results in a shift of El,, to more positive values. -4) On a preparative scale, the N -N bond of all examples investigated undergoes reductive fission [exception: 3,6(1H,2H)pyridazinedione (S)]. Electroreduction of 1,2-dibenzoyl-l,2-diazaspiro[2,5]octane (14) affords N,N' -(1, I-cyclohexylidene)bis(benzamide). 1 -Methyl-1,5-diazacyclooctane and 1 -methyl-l,6diazacyclodecane can be isolated from the bicyclic hydrazinium salts 25 and 27, respectively. *) Korrespondenz bitte an diesen Autor richten. ) Theodor Wieland in freundschaftlicher Verbundenheit zum 65. Geburtstag gewidmet. *) M . Jordan, Diplomarbeit, Univ. Mainz 1975.

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“…Decomposition of Phenylmethyldiazirine (4) Schmitz and Ohme (14) reported that the thermal decomposition of phenylmethyldiazirine 4 in nitrobenzene gave styrene. This is to be contrasted with Overberger and Anselme's results (15) for which they reported that the thermal decomposition of 1-phenyl-diazoethane 5 gave acetophenone azine as the only product.…”

Section: Decomposition Of Phenyl-n-butyldiazirine (1)mentioning

confidence: 99%

“…Synthesis of Phenylmethyldiazirine (4) Phenylmethyldiazirine, 4, was synthesized from the N-benzylmethylphenylketimine in the manner of Schmitz and Ohme (14). The final yield of diazirine (colorless) was 23%, based on the starting ketimine.…”

Section: Photolysis Of Phenyl-n-butyldiazirine (I) In Benzene;mentioning

confidence: 99%

Consecutive reactions in the thermal decomposition of phenylalkyldiazirines

Liu¹,

Jennings²

1977

Can. J. Chem.

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. Can. J. Chem. 55,3596 (1977). The thermal decomposition of phenyl-n-butyldiazirine and of phenylmethyldiazirine in DMSO and in HOAc have been investigated over the temperature range 80-130°C. The intermediate diazo compounds, 1-phenyl-1-diazopentane and 1-phenyldiazoethane respectively have been detected and isolated. The decomposition of phenyl-n-butyldiazirine and the subsequent decomposition of its product, 1-phenyl-1-diazopentane, are an illustration of consecutive reactions. The kinetic parameters for the isomerization and decomposition reactions have been determined. The isomerization of phenylmethyldiazirine to 1-phenyldiazoethane is first order and probably unimolecular but the kinetics for the subsequent reactions of 1-phenyldiazoethane are complicated by several competing rate processes. Chem. 55,3596 (1977). On ttudie la dtcomposition thermique entre 80 et 130°C du phtnyl-3 n-butyl-3 diazirine et du phenyl-3 mtthyl-3 diazirine dans le DMSO et I'acide acttique. Les composts diazo intermtdiaires sont respectivemei~t le phtnyl-1 diazo-l pentane et le phenyl-1 diazo-1 tthane. Ces derniers ont t t t dktectts et isolts. La dtcomposition du phtnyl-3 n-butyl-3 diazirine et la dtcomposition ulttrieure de son intermtdiaire le phtnyl-1 diazo-1 pentane sont un bon exemple de rtactions successives. On determine les paramktres cinttiques pour les rtactions d'isomtrisation et de decomposition. L'isomtrisation du phtnyl-3 methyl-3 diazirine en phtnyl-1 diazo-1 tthane est d'ordre 1 et probablement unimoltculaire, mais les cinttiques des rtactions ulttrieures du phenyl-1 diazo-1 tthane sont compliqutes par plusieurs processus qui entrent en compttition.[Traduit par le journal]

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Cyclische Diazoverbindungen, I. Herstellung und Umsetzungen von Diazirinen

Cited by 118 publications

References 14 publications

Electrochemical synthesis of pentamethylenediazirine

Electrochemical synthesis of pentamethylenediazirine

Studien zum Vorgang der Wasserstoffübertragung, 52. Zur Kenntnis der elektroreduktiven Spaltung der N ‐ N‐Bindung

Consecutive reactions in the thermal decomposition of phenylalkyldiazirines

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