Zur nucleophilen substitution von 3-halogen-λ3-phosphorinen mit alkalimetallamiden

Märkl, Gottfried; Hock, K.

doi:10.1016/s0040-4039(00)94039-5

Cited by 14 publications

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“…Although the first β‐functional phosphinine, a 3‐phosphaphenol, was synthesized by Märkl et al as early as 1977,1 only a few such compounds are known,2 particularly if we exclude a series of polyfunctional derivatives obtained by [4+2] cycloaddition between 1‐phosphadienes or synthetic equivalents and functional alkynes 3. As a result, the reactivity of this class of compounds is almost unexplored 4. Herein, we describe a straightforward access to such compounds from the readily available phospholide ions.…”

Section: Methodsmentioning

confidence: 99%

One‐Pot Conversion of Phospholide Ions into β‐Functional Phosphinines

Grundy

Mathey

2005

Angew Chem Int Ed

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Although the first b-functional phosphinine, a 3-phosphaphenol, was synthesized by Märkl et al. as early as 1977, [1] only a few such compounds are known, [2] particularly if we exclude a series of polyfunctional derivatives obtained by [4+2] cycloaddition between 1-phosphadienes or synthetic equivalents and functional alkynes.[3] As a result, the reactivity of this class of compounds is almost unexplored.[4] Herein, we describe a straightforward access to such compounds from the readily available phospholide ions.In 1997, we described a simple method which converts aunsubstituted into a-functional phospholides.[5] This method has been applied to the synthesis of 2-acylphospholides.[6] In the course of a systematic investigation of the reactivity of these species, we discovered that their reaction with dihalomethanes unexpectedly leads to the formation of 3-acylphosphinines (Scheme 1).The whole sequence takes place at room temperature or below. The reaction is best run with dibromomethane. The 3-functional phosphinines appear to be the sole products of the transformation as determined by monitoring the reaction mixture by 31 P NMR spectroscopy. Whatever the nature of the b-substituent, the 31 P resonance signal is observed at d = 188 AE 1 ppm (CDCl 3 ) as for the 3-unsubstituted species. [7] This observation underlines the weakness of the electronic interaction between phosphorus and the functional meta substituent. The phosphinines are purified by chromatography on silica gel or by distillation in a Kugelrohr apparatus. They were completely characterized by NMR spectroscopy and mass spectrometry. The final yields of isolated products based on the starting 1-phenyl-3,4-dimethylphosphole (three reactions in one pot) remain modest (8-20 %), probably because of substantial losses during the purification procedure. We have also checked that the conversion into phosphinine does not take place in the absence of the functional substituent.Since we had no precise idea about the mechanism of formation of these functional phosphinines, we decided to investigate various possibilities by DFT calculations at the B3LYP/6-311 + G(d,p) level [8] using the Gaussian 03 package.[9] We decided to check the possibility of a carbenoid mechanism. We admitted the formation of a carbenoid species by deprotonation of the P-CH 2 X unit of the initially formed 1-haloalkylphosphole. The process was modeled using the anion derived from 1-chloromethyl-2-acetylphosphole. The theoretical investigation of the reaction pathway suggested that the conversion into phosphinine proceeded by the initial opening of the phosphole ring, to give the 1-chloro-6-acetyl-2-phosphahexatriene anion as a first intermediate. The transition state (one imaginary frequency) between the phosphole and the phosphahexatriene anions was computed to lie 25.3 kcal mol À1 higher in energy than the starting phosphole anion (zero-point energy (ZPE) included). Thus, this mechanism was discarded because it needed too much energy to be operative at RT and provided no explanation ...

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Section: Methodsmentioning

confidence: 99%

One‐Pot Conversion of Phospholide Ions into β‐Functional Phosphinines

Grundy

Mathey

2005

Angew Chem Int Ed

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“…4.83 N 9.15 Gef. C 65.22 H 4.85 N 9.14 1 ,l-Dimethoxy-2,6-diphenyl-i3-phosphinin-4-carb~lde~yd (7): Der bereits beschriebene Aldehyd '3) 2,4,6-Triphenyl-L3-phosphinin aus 1,1 -Dimethoxy-2,4,6-triphenyl-L-'-phosphinin: 760 mg (1.97 mmol) 1 ,l-Dimethoxy-2,4,6- In analoger Weise wird 2,4,6-Tri-tert-butyl-1,l-dimethoxy-hSphosphinin zu 2,4,6-Tri-tert-buty1-A3- 4'-Methylenbis (2,6-diphenyl-13-phosphinin) (6): 316 mg (0.5 mmol) 4d werden, wie zuvor beschrieben in 6 ml 1,2-Dimethoxyethan mit i. Hochvak. getrocknetem LiI.3 H 2 0 (376 mg, 2.0 mmol) 12 h geriihrt, wobei die Losung tiefrot wird.…”

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λ³‐Phosphinine mit einer funktionellen Gruppe an C‐4

Dimroth

Kaletsch

1987

Chem. Ber.

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Bisher unbekanntc Dcrivate des L3-Phosphinins rnit einer funktionellen Gmppc an C-4, wie CN (lo), COICHJ (11) odcr CHFN (3, sowio 4,4'-M.ethyknbis(2,6phenyl-k3-phosphinin) (6) werden unter milden Bedingunfin durch reduktive Abspaltung der beiden Methoxylgruppen vom Phosphoratom aus den Csubstituierten 1,1 -Dimcthoxy-2,bdiphenyl-~'-phosphininen (2, 7) crhalten. Die neucn X'-Phosphinine sind kristalline, mit Ausnahme von 6 luftbcstandige Verbindungen, deren analytische und spektroskopische D a t a in Tab. 1 und 2 angegeben sind.h3-Phosphinine rnit einer funktionellen Gruppe sind bis vor kurzem weder durch eine unmittelbare Synthese, wie ihre Aryl-oder Alkyl-Derivate'), noch aus dem nicht substituierten h3-Phosphininz) erhalten worden3). Mark1 und Mitarbb. konnten aber aus Derivaten des l-tert-Butyl-1,2-dihydrophosphinins4) oder des 1 -tert-Butyl-1 -chlor(oder -brom)-h5-phosphinins5) durch Thermolyse bei 200-270°C an C-3 durch OH, C1 oder Br substituierte 5-Phenylh3-phosphinine erhalten. Mit Li-Dialkylamiden lieBen sich Halogen-Derivate auch in 3-(Dialkylamino)-5-phenyl-h3-phosphinine iiberfiihren6). l-tert-Butyl-l-chlor-3-phenyl-4-pivaloyl-hs-phosphinin ergibt beim Erhitzen auf 250-270°C 3-Phenyl-4-pivaloyl-h3-phosphinin, das durch sein NMR-Spektrum charakterisiert wurde ' 1.In letzter Zeit wurde auch iiber Diels-Alder-Reaktionen von Phosphoralkenen rnit Butadien-Derivaten berichtet, die zu hydrierten Phosphininen mit funktionellen Gruppen fuhren. Diese gehen unter milden Bedingungen in funktionell substituierten h3-Phosphinine iiber, die isoliert und durch ihre NMR-und Massenspektren nachgewiesen wurden * ! Wir berichten hier uber einige Versuche, bei denen durch reduktive Abspaltung der 1,l-Dimethoxy-Gruppen von h3-Phosphinin-Derivaten unter milden Bedingungen h3-Phosphinin-Derivate erhalten wurden. Vorversuche rnit 1,lDimethoxy-2,4,6-triphenyl-und rnit 2,4,6-Tri-tert-butyl-1,1-dimethoxy-h5-phosphinin, die sich fast quantitativ aus den h3-Phosphinin-Derivaten uber ihre QuecksilberdiacetatKomplexe mit Methanol bilden'), hatten ergeben, daD sie sich -nach der Abspaltung einer Methylgruppe aus einer der beiden Methoxygruppen am Phosphoratom durch Salzsaure zu den 1,2-(und 1,4-)Dihydro-1-methoxy-1-0x0-h5- Hitherto unknown derivatives of k3-phosphiniaes with a functional substituent at C-4. such as CN (10). C 9 C H 3 (11). or CH2CN (5). as well as 4,4'-mcthylencbis(2,6diphenyl-X3-phosphinine) (6) a n prepared under mild conditions by reductive elimination of both methoxyl groups from tbe phosphorus atom of the 4-substituted l,ldimethoxy-2,~iphenyl-L~-pbosphinines (2, 7). The new k'-phosphinincs are crystalline and exapt for 6 air-stable compounds, whose analytical and spectroscopic data are reported in the Tables 1 and 2.Dimethylanilin an die CHZ-Gruppe zu 3a-e, von denen 3b und e bisher nicht dargestellt waren. Andererseits laDt sich 2 auch in waDrigem Acetonitril oder 1,2-Dimethoxy-

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Phosphorus Heterocycles

Mathey

2011

Modern Heterocyclic Chemistry

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Figure 23.1 The three isomers of the phosphole system (A-C) and the phospholide ion (D).2072j 23 Phosphorus Heterocycles shown with 1-alcoxyphospholes, which are relatively flat with a negligible delocalization [12]. Contrary to phospholes, the structure of phospholide ions reflects their high aromaticity. For example, the planar 2,3,4,5-tetramethylphospholide with Li(TMEDA) þ as the counterion displays the following parameters [13]: P-C, 1.715 A ; C¼C, 1.396 A ; CÀC, 1.424 A ;

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Zur nucleophilen substitution von 3-halogen-λ3-phosphorinen mit alkalimetallamiden

Cited by 14 publications

References 4 publications

One‐Pot Conversion of Phospholide Ions into β‐Functional Phosphinines

One‐Pot Conversion of Phospholide Ions into β‐Functional Phosphinines

λ³‐Phosphinine mit einer funktionellen Gruppe an C‐4

Phosphorus Heterocycles

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Zur nucleophilen substitution von 3-halogen-λ3-phosphorinen mit alkalimetallamiden

Cited by 14 publications

References 4 publications

One‐Pot Conversion of Phospholide Ions into β‐Functional Phosphinines

One‐Pot Conversion of Phospholide Ions into β‐Functional Phosphinines

λ3‐Phosphinine mit einer funktionellen Gruppe an C‐4

Phosphorus Heterocycles

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λ³‐Phosphinine mit einer funktionellen Gruppe an C‐4