Sequential dehydrochloride coupling of trichlorophosphine with 2,6-di-isopropylaniline: aminophosphine precursors to phosphetidines

Burford, Neil; Cameron, T. Stanley; Conroy, Korey D.; Ellis, Bobby D.; Macdonald, Charles L. B.; Ovans, Robyn; Phillips, Andrew D.; Ragogna, Paul J.; Walsh, Denise

doi:10.1139/v02-161

Cited by 34 publications

(51 citation statements)

References 11 publications

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“…Depending on the stoichiometry, the amount and kind of base, solvent, temperature, etc., the reaction can be carried out stepwise either via aminobis(dichloro)phosphanes or aminodichlorophosphanes. [40][41][42][43][44][45][46][47][48][49][50][51][52][53][54][55][56] These reactions can be referred to as base-induced sequential dehydrochlorination or, in general, as cyclocondensation processes.…”

Section: Resultsmentioning

confidence: 99%

Activation of Small Molecules by Phosphorus Biradicaloids

Hinz

Kuzora

Rosenthal

et al. 2014

Chemistry A European J

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The reactivity of biradicaloid [P(μ-NTer)]2 was employed to activate small molecules bearing single, double, and triple bonds. Addition of chalcogens (O2 , S8 , Sex and Tex ) led to the formation of dichalcogen-bridged P2 N2 heterocycles, except from the reaction with molecular oxygen, which gave a P2 N2 ring featuring a dicoordinated P(III) and a four-coordinated P(V) center. In formal [2πe+2πe] addition reactions, small unsaturated compounds such as ethylene, acetylene, acetone, acetonitrile, tolane, diphenylcarbodiimide, and bis(trimethylsilyl)sulfurdiimide are readily added to the P2 N2 heterocycle of the biradicaloid [P(μ-NTer)]2 , yielding novel heteroatom cage compounds. The synthesis, reactivity, and bonding of the biradicaloid [P(μ-NTer)]2 were studied in detail as well as the synthesis, properties, and structural features of all addition products.

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Section: Resultsmentioning

confidence: 99%

Activation of Small Molecules by Phosphorus Biradicaloids

Hinz

Kuzora

Rosenthal

et al. 2014

Chemistry A European J

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“…When phosphorus trichloride is treated with a suspension of lithiated primary amine in a ratio of 2-3, the reaction initially forms a mixture of BnNHPCl 2 (doublet d 158 ppm, J = 50 Hz) and trimeric (BnNPCl) 3 (d 134, 125 and 104 ppm) and (BnNPCl) 2 (d 227) [16,17]. Treatment of this mixture with triethylamine deprotonates the hydrochloride byproduct from the first step to complete the slow formation of the P 4 (NR) 6 structure.…”

Section: New Ligandsmentioning

confidence: 99%

A growing family: New structures of coordination polymers containing adamantane-shaped phosphorus–nitrogen cage ligands

Spore

Rizzo

Noll

et al. 2010

Inorganica Chimica Acta

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“…[1] Herein, we report the synthesis and full characterization of the first dichlorocyclodibismadiazane.A typical route to cyclodipnictadiazanes is the facile HCl elimination, between primary amines and trichloropnictanes to give aminopnictanes. However, the isolation of the amination products is complicated because of the coincident formation of monoaminodichloro-, diaminochloro-, and trisaminopnictanes, [11] as well as the possibility for formation of the iminopnictanes. It is known, that the formation of a specific aminopnictane, iminopnictane or its dimer, the cyclodipnictadiazane, can be influenced by the presence of specific substituents (depending on the steric strain) on the amine and by the use of lithium amides rather than amines.…”

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confidence: 99%

Dichlorocyclodibismadiazane

2010

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Four-membered pnictogen-nitrogen heterocycles of the type [ClE(m-NR)] 2 (E = element of Group 15) are known as 1,3-dichlorocyclo-1,3-dipnicta(III)-2,4-diazanes.[1] Especially the phosphorus species play a major role in preparative phosphorus-nitrogen chemistry, for example, in the preparation of macrocycles, polymers, main-group complexes, and ringtransformation reactions or the generation of cyclic binary PN cations. [2][3][4] As early as 1894 Michaelis and Schroeter discovered the first cyclo-1,3-diphospha(III)-2,4-diazane when they treated aniline hydrochloride with an excess of PCl 3 for two days under reflux [Eq. (1)].[5] However, they thought they had isolated the monomeric species, C 6 H 5 À N = P À Cl. Today we know that the dimer represents the stable form of phenyl substituted 1,3-dichlorocyclo-1,3-diphospha(III)-2,4-diazane. [2a, 3, 6, 7] The chemistry of the heavier pnictogen analogues (As, Sb, Bi) of this classic inorganic E 2 N 2 ring system has only slowly been developed in the last 50 years. [8][9][10] The simplest cyclodipnicta(III)diazanes are the dichloro derivatives, [ClE-(m-NR)] 2 , (A, Scheme 1) and are only known for E = P, As, and Sb, while bis(organoamino) derivatives B and bis(dimethylamino) derivatives C are observed for the whole series E = P-Bi.[1] The slow progress, especially in the chemistry of Bi 2 N 2 ring systems compared to that of P 2 N 2 rings can be attributed to the lability of BiÀN bonds. Hence, Chivers et al. pointed out, that "The discovery of a suitable synthesis of dichloro derivatives of type A for bismuth would be a significant step forward".[1] Herein, we report the synthesis and full characterization of the first dichlorocyclodibismadiazane.A typical route to cyclodipnictadiazanes is the facile HCl elimination, between primary amines and trichloropnictanes to give aminopnictanes. However, the isolation of the amination products is complicated because of the coincident formation of monoaminodichloro-, diaminochloro-, and trisaminopnictanes, [11] as well as the possibility for formation of the iminopnictanes. It is known, that the formation of a specific aminopnictane, iminopnictane or its dimer, the cyclodipnictadiazane, can be influenced by the presence of specific substituents (depending on the steric strain) on the amine and by the use of lithium amides rather than amines. [1] In this context, it was of interest to study the effect of a bulky group, such as the terphenyl group (Ter = 2,6-Mes 2 C 6 H 3 , Mes = 2,4,6-Me 3 C 6 H 2 ) [12] on the reaction products. To obtain 1,3-dichloro-2,4-di(m-terphenyl)cyclo-1,3-dibisma-2,4-diazane, [TerNÀBiCl] 2 , in a two-step reaction, first the dichloro(m-terphenylamino)bismutane (1) had to be prepared in the reaction of terphenylaniline, TerNH 2 , with n-BuLi in the presence of BiCl 3 [Eq. (2)] at ambient temperatures. This reaction gave 1 as a red, crystalline solid in over 80 % yield (m.p. 189 8C (decomp)). The second step included a complex reaction of 1 in THF with DBU (1,8-diazabicyclo-[5.4.0]undec-7-ene) at low temp...

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Sequential dehydrochloride coupling of trichlorophosphine with 2,6-di-isopropylaniline: aminophosphine precursors to phosphetidines

Cited by 34 publications

References 11 publications

Activation of Small Molecules by Phosphorus Biradicaloids

Activation of Small Molecules by Phosphorus Biradicaloids

A growing family: New structures of coordination polymers containing adamantane-shaped phosphorus–nitrogen cage ligands

Dichlorocyclodibismadiazane

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