Rearrangement in the Reaction of α-Halogenonaphthalenes with Lithium Diethylamide

Gilman, Henry; Crounse, Nathan N.; Massie, Samuel P.; Benkeser, Robert A.; Spatz, S. M.

doi:10.1021/ja01228a015

Cited by 38 publications

(14 citation statements)

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“…The synthetic protocol leading to the new homoleptic lanthanide(III) tris(guanidinate) complexes [ c ‐C 2 H 4 NC(N i Pr) 2 ] 3 Ln consisted of a bottom‐up approach starting with aziridine as illustrated in Scheme . In the first step, commercially available aziridine ( 1 ) was metalated according to a published procedure using n ‐butyllithium in n ‐hexane/diethyl ether solution . Unsolvated N ‐lithioaziridine ( 2 ) could be isolated as a white, air‐ and moisture‐sensitive solid.…”

Section: Resultsmentioning

confidence: 99%

Two Series of New Volatile Rare‐Earth Metal Tris(guanidinates) and Tris(amidinates)

Tutacz

Harmgarth

Zörner

et al. 2018

Zeitschrift anorg allge chemie

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Two series of new volatile, homoleptic lanthanide(III) tris(guanidinate) and tris(amidinate) complexes were synthesized and fully characterized. Treatment of anhydrous rare‐earth metal(III) chlorides, LnCl3, with three equiv. of the aziridine‐derived lithium guanidinate Li[c‐C2H4NC(NiPr)2] (3) afforded the new homoleptic tris(guanidinate) complexes [c‐C2H4NC(NiPr)2]3Ln (4) (Ln = Sc, Pr, Nd, Sm, Eu, Ho, Tm) in good yields (68–80 %). In a similar manner, the homoleptic tris(amidinate) complexes [iPrC(NiPr)2]3Ln (6) Ln = Sc, Ce, Pr, Nd, Tb, Dy, Er, Yb) were prepared from LnCl3 and the all‐isopropyl‐substituted lithium amidinate Li[iPrC(NiPr)2] (5) in a molar ratio of 1:3. Variable‐temperature 1H NMR studies of the paramagnetic derivatives 4Pr–4Tm revealed Curie‐type behavior. 1H NMR spectroscopic data of complexes 6 indicated severe steric crowding due to the presence of nine isopropyl groups in these molecules. The molecular and crystal structures of eight title compounds (4Sc, 4Pr, 4Nd, 4Sm, 4Eu, 4Ho, 4Tm, and 6Er) were determined through single‐crystal X‐ray diffraction studies. All complexes 4 exhibit similar molecular structures, comprising distorted octahedral molecular structures with small bite angles. Sublimation temperatures of 4 at 0.05 mbar were determined to be in the range between 151 °C (4Eu) and 194 °C (4Tm), whereas the complexes 6 sublime in the temperature range between 140 °C (6Sc) and 180 °C (6Ce), so that the use of these precursors in future ALD or CVD studies appears feasible.

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Section: Resultsmentioning

confidence: 99%

Two Series of New Volatile Rare‐Earth Metal Tris(guanidinates) and Tris(amidinates)

Tutacz

Harmgarth

Zörner

et al. 2018

Zeitschrift anorg allge chemie

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“…N-aziridinyllithium, C 2 H 4 NLi 2, was prepared by metalation of 1 using n BuLi in analogy to a published procedure. [6] 1 H NMR (400 MHz) and 13 C NMR (100.6 MHz) were recorded in [D8]THF solutions on a Bruker DPX 400 spectrometer at 258C. Chemical shifts were referenced to TMS.…”

Section: Methodsmentioning

confidence: 99%

“…[4] Aziridine (ethylenimine, C 2 H 4 NH (1)) is commercially available, but it can also be easily prepared from b-aminoethylsulfuric acid and 40 % sodium hydroxide solution following an established procedure. [5] The required N-aziridinyllithium, C 2 H 4 NLi (2), was first reported by Gilman et al, [6] and has been frequently employed as reagent in organic and organometallic syntheses. [7] Its preparation according to Scheme 1 involves treatment of aziridine (1) with n-butyllithium in n-hexane/diethyl ether solution.…”

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confidence: 99%

The First Aziridinylguanidinates: New Precursors for Potentially Volatile Metal Guanidinates

Tutacz¹,

Syre²,

Hrib³

et al. 2014

Aust. J. Chem.

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The first lithium-aziridinylamidinates, Li[(C2H4N)C(NR)2]·THF (R = iPr (3), Cy (4); iPr = isopropyl, Cy = cyclohexyl), have been prepared by addition of N-aziridinyllithium, C2H4NLi (2), to either N,N′-diisopropylcarbodiimide or N,N′-dicyclohexylcarbodiimide. The cyclohexyl derivative 4 was crystallised from both diethyl ether (Et2O) and THF to afford the crystalline solvent adducts {Li[(C2H4N)C(NR)2]·S}2 (4: S = THF; 4a: S = Et2O) which were structurally characterised by X-ray diffraction. In the solid state, these lithium-aziridinylamidinates comprise ladder-type dimeric molecular structures.

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“…[32] The acetate counterion not only traps the aryl cation intermediate, forming the acetate product, but also abstracts a proton to form 2,5-di-tert-butylbenzyne. 1,2-Naphthyne has been prepared as an intermediate by 1,2 HX elimination from halonaphthalenes by a strong base [33] and in matrix photodecarboxylation experiments. [34] All naphthynes found in matrix trapping experiments possess singlet multiplicities.…”

Section: Singlet/triplet Natures Of the Product-forming Intermediatesmentioning

confidence: 99%

Photochemical Generation and Reactivity of Naphthyl Cations: cine Substitution

et al. 2007

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The photochemical solvolyses of naphthalen-1-yl(phenyl)-iodonium tetrafluoroborate and naphthalen-2-yl(phenyl)-iodonium tetrafluoroborate in methanol regiospecifically yield the naphthalen-1-and -2-yl ethers but afford scrambled 1-and 2-phenylnaphthalene Friedel-Crafts products. It is demonstrated that singlet naphthyl cations account for the formation of the naphthyl ethers, but that the cine substitu-

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Rearrangement in the Reaction of α-Halogenonaphthalenes with Lithium Diethylamide

Cited by 38 publications

References 0 publications

Two Series of New Volatile Rare‐Earth Metal Tris(guanidinates) and Tris(amidinates)

Two Series of New Volatile Rare‐Earth Metal Tris(guanidinates) and Tris(amidinates)

The First Aziridinylguanidinates: New Precursors for Potentially Volatile Metal Guanidinates

Photochemical Generation and Reactivity of Naphthyl Cations: cine Substitution

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