A Convenient Synthesis of Triphenylphosphine Acylimides Using<i>N</i>-Lithiated Triphenylphosphine Imide

Cristau, Henri‐Jean; Manginot, Eric; Torreilles, E.

doi:10.1055/s-1991-26471

Cited by 27 publications

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“…To compare the structure of 3 with those of lighter pnictogen counterparts, an iminophosphorane 6 , an iminoarsorane 8 , and imino-λ 5 -stibanes 10a − c were prepared by the oxidative condensation of triphenylphosphane ( 5 ), triphenylarsane ( 7 ), and tris(2,4,6-trimethylphenyl)stibane ( 11 ) with 2b in the presence of diethyl azodicarboxylate and by treating triarylstibane oxides 9a,b with trichloroacetonitrile in CH 2 Cl 2 (Scheme ). Despite the presence of ortho -substituent groups, compounds 10a,b are extremely moisture sensitive and readily decompose to give the corresponding oxides 9a,b under ambient conditions.…”

Section: Resultsmentioning

confidence: 99%

“…[(Trichloroacetyl)imino]triphenylphosphorane (6): mp 184−186 °C (lit . mp 183−184 °C); 1 H NMR δ 7.46−7.66 (m, 9H), 7.79 (dd, 6H, J = 12.5, 7.7 Hz); 13 C NMR δ 126.4 ( 1 J PC = 100.3 Hz), 128.9 ( 3 J PC = 12.4 Hz), 132.9 ( 4 J PC = 3.0 Hz), 133.1 ( 2 J PC = 10.2 Hz), 170.1 ( 2 J PC = 5.6 Hz, CO); IR ν C  O 1638; FABMS m / z 422 ([M + H] + ; 35 Cl × 3).…”

Section: Methodsmentioning

confidence: 99%

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Synthesis, Structure, and Reactions of (Acylimino)triaryl-λ⁵-bismuthanes: First Comparative Study of the (Acylimino)pnictorane Series

et al. 2001

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The synthesis, structure, and reactions of (acylimino)triaryl-lambda(5)-bismuthanes and a comparative study of the structure and reactivity of a series of (acylimino)pnictoranes are reported. Treatment of ortho-substituted triarylbismuth dichlorides 1 (Ar(3)BiCl(2); Ar = 2-MeC(6)H(4), 2-MeOC(6)H(4), 2,4,6-Me(3)C(6)H(2)) with amides 2 (H(2)NCOR; R = CF(3), CCl(3), 3,5-(CF(3))(2)C(6)H(3)) in the presence of 2.2 equiv of KO-t-Bu in dichloromethane afforded (acylimino)triaryl-lambda(5)-bismuthanes 3 (Ar(3)Bi=NCOR) in yields of 77-96%. The ortho-substituted aryl ligands and the electron-withdrawing N-substituents afford kinetic and thermodynamic stabilization, respectively, to the reactive Bi=N bond. The structures and properties of a series of (acylimino)pnictoranes (Ar(3)M=NCOR and H(3)M=NCOCF(3); M = P, As, Sb, Bi) are compared by IR and (13)C and (15)N NMR, X-ray crystallography, and ab initio molecular orbital calculations. It was found that the contribution of the M(+)-N=C-O(-) canonical form becomes more prominent and the single-bond character of the M=N bond increases progressively as the pnictogen atom becomes heavier. The Bi=N bond of (acylimino)-lambda(5)-bismuthanes 3 possesses a highly polarized single-bond character, probably due to the differences in orbital size and electronegativity between the bismuth and nitrogen atoms. Thermal decomposition of (aroylimino)triaryl-lambda(5)-bismuthane 3f (o-Tol(3)Bi=NCOAr; Ar = 3,5-(CF(3))(2)C(6)H(3)) produces a gel in dry conditions or aniline 12 (ArNH(2)) in slightly wet conditions with a good recovery of tris(2-methylphenyl)bismuthane (4a). It is likely that the aryl isocyanate 13 (ArNCO) is produced during the thermolysis via a concerted C --> N migration of the Ar group with an elimination of the triarylbismuthonio group as bismuthane 4a. (Acylimino)triaryl-lambda(5)-bismuthanes 3 oxidize 1,1,2,2-tetraphenylethanediol, benzenethiol, methanol, and ethanol to benzophenone, diphenyl disulfide, methyl formate, and acetaldehyde, respectively, in two different reaction pathways depending on the structure of the substrates. Compound 3d (o-Tol(3)Bi=NCOCCl(3)) transfers the nitrenoid moiety to triphenylphosphane, triphenylarsane, and tris(2-methylphenyl)stibane to give the corresponding (acylimino)pnictoranes (Ar(3)M=NCOCl(3); M = P, As, Sb) and 4a, suggesting that 3d is thermodynamically much less stable than their lighter pnictogen counterparts. The copper-catalyzed decomposition of 3 (o-Tol(3)Bi=NCOR) afforded N-acyl-o-toluidines 18 (o-TolNHCOR) via a Bi --> N migration of the tolyl group. The observed reactivities of (acylimino)triaryl-lambda(5)-bismuthanes 3 demonstrate a good leaving ability of the bismuthonio group.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Synthesis, Structure, and Reactions of (Acylimino)triaryl-λ⁵-bismuthanes: First Comparative Study of the (Acylimino)pnictorane Series

et al. 2001

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“…The aminophosphonium salt 3 was prepared by the published procedure [9]. This compound was converted into 1 and 4 as reported [9].…”

Section: Methodsmentioning

confidence: 99%

“…Each ethyl ester 9, 11, or 14 (4.2 mmol) was added to a 50 mL dry THF solution of 4 (4.2 mmol) [prepared in situ from 1 (1.5 g, 4.2 mmol) [9]], at 20ЊC under a nitrogen atmosphere. The mixture was warmed to 50ЊC for the time indicated in Tables 1 and 2.…”

Section: N-substituted Phosphinimines 10 12 13 15 and 16mentioning

confidence: 99%

Use of Ph3P=N-Li: Synthesis of ?,?-unsaturated nitriles from ?,?-unsaturated esters via the formation of N-(?,?-unsaturated acyl) phosphinimines

1999

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The reaction of Ph3P=NLi with various α,β‐unsaturated esters gives access to new N‐(α,β‐unsaturated acyl) phosphinimines, which can undergo intramolecular aza‐Wittig reactions (at 65–110°C) to afford the corresponding nitriles. The structures of all new compounds were established by elementary analyses, IR, 1H‐, 13C‐, and 31P‐NMR spectroscopy. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 49–54, 1999

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“…68,128 Similarly, owing to its high nucleophilicity, the azayldiide 112 can be readily acylated not only with acyl chlorides or acid anhydrides, but also with esters or carbonates to give the corresponding iV-acyl phosphinimines 115 and 116 (Scheme 23). 129 Reactions of azayldiide 112 take place easily and without any transyluration process with various heteroatomic electrophiles to give an easy one-pot preparation for a large range of N-substituted phosphinimines which are valuable precursors in phosphorus or sulfur chemistry (Scheme 24).128…”

Section: Lithium Aminophosphonium Azayldiidesmentioning

confidence: 99%

Synthetic Applications of Metalated Phosphonium Ylides

Cristau¹

1994

Chem. Rev.

149

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A Convenient Synthesis of Triphenylphosphine Acylimides UsingN-Lithiated Triphenylphosphine Imide

Cited by 27 publications

References 0 publications

Synthesis, Structure, and Reactions of (Acylimino)triaryl-λ⁵-bismuthanes: First Comparative Study of the (Acylimino)pnictorane Series

Synthesis, Structure, and Reactions of (Acylimino)triaryl-λ⁵-bismuthanes: First Comparative Study of the (Acylimino)pnictorane Series

Use of Ph3P=N-Li: Synthesis of ?,?-unsaturated nitriles from ?,?-unsaturated esters via the formation of N-(?,?-unsaturated acyl) phosphinimines

Synthetic Applications of Metalated Phosphonium Ylides

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A Convenient Synthesis of Triphenylphosphine Acylimides UsingN-Lithiated Triphenylphosphine Imide

Cited by 27 publications

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Synthesis, Structure, and Reactions of (Acylimino)triaryl-λ5-bismuthanes: First Comparative Study of the (Acylimino)pnictorane Series

Synthesis, Structure, and Reactions of (Acylimino)triaryl-λ5-bismuthanes: First Comparative Study of the (Acylimino)pnictorane Series

Use of Ph3P=N-Li: Synthesis of ?,?-unsaturated nitriles from ?,?-unsaturated esters via the formation of N-(?,?-unsaturated acyl) phosphinimines

Synthetic Applications of Metalated Phosphonium Ylides

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Synthesis, Structure, and Reactions of (Acylimino)triaryl-λ⁵-bismuthanes: First Comparative Study of the (Acylimino)pnictorane Series

Synthesis, Structure, and Reactions of (Acylimino)triaryl-λ⁵-bismuthanes: First Comparative Study of the (Acylimino)pnictorane Series