Verkade base: Difference between revisions
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In [[chemistry]], |
In [[chemistry]], the '''Verkade base''' (or '''Verkade superbase''') is a powerful [[superbase]] with the formula P(MeNCH<sub>2</sub>CH<sub>2</sub>)<sub>3</sub>N. A colorless oil, it is an [[aminophosphine]] although its inventor John Verkade called it '''proazaphosphatrane'''. The trimethyl derivative or 2,5,8,9-tetraza-1-phosphabicyclo[3.3.3]undecane is the simplest.<ref>{{cite journal|doi=10.1002/047084289X.rn00702.pub2|title=Proazaphosphatrane|journal=Encyclopedia of Reagents for Organic Synthesis|year=2012|last1=Verkade|first1=John G.|last2=Urgaonkar|first2=Sameer|isbn=978-0471936237 }}</ref> Diverse analogues of the Verkade base are known, e.g. with [[isopropyl group]]s in place of methyl. |
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==Synthesis and reactions== |
==Synthesis and reactions== |
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:P(NMe<sub>2</sub>)<sub>3</sub> + (MeNHCH<sub>2</sub>CH<sub>2</sub>)<sub>3</sub>N → P(MeNCH<sub>2</sub>CH<sub>2</sub>)<sub>3</sub>N + 3 Me<sub>2</sub>NH |
:P(NMe<sub>2</sub>)<sub>3</sub> + (MeNHCH<sub>2</sub>CH<sub>2</sub>)<sub>3</sub>N → P(MeNCH<sub>2</sub>CH<sub>2</sub>)<sub>3</sub>N + 3 Me<sub>2</sub>NH |
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The principal reaction of the Verkade base is [[protonation]]. The proton is attacked by the Verkade base at phosphorus, which induces the formation of a [[transannular]] P-N bond. The product exemplifies the structure of an [[atrane]]. |
The principal reaction of the Verkade base is [[protonation]]. The proton is attacked by the Verkade base at the phosphorus atom within, which induces the formation of a [[transannular]] P-N bond. The product exemplifies the structure of an [[atrane]]. |
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[[image:VerkadeProtn.svg|thumb|290 px|left|Protonation of Verkade base.]] |
[[image:VerkadeProtn.svg|thumb|290 px|left|Protonation of Verkade base.]] |
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The [[conjugate acid]] [HP(MeNCH<sub>2</sub>CH<sub>2</sub>)<sub>3</sub>N]<sup>+</sup> has a [[pKa|pK<sub>a</sub>]] of 32.9 in [[acetonitrile]]. For comparison, the conjugate acid of [[triethylamine]] has a pK<sub>a</sub> near 17 in acetonitrile. Owing to its ability to [[deprotonate]] weak carbon acids, the Verkade base catalyzes a variety of [[condensation reaction]]s. |
The [[conjugate acid]] [HP(MeNCH<sub>2</sub>CH<sub>2</sub>)<sub>3</sub>N]<sup>+</sup> of the base has a [[pKa|pK<sub>a</sub>]] of 32.9 in [[acetonitrile]]. For comparison, the conjugate acid of [[triethylamine]] has a pK<sub>a</sub> near 17 in acetonitrile. Owing to its ability to [[deprotonate]] weak carbon acids, the Verkade base catalyzes a variety of [[condensation reaction]]s. |
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==Related compounds== |
==Related compounds== |
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Revision as of 17:42, 19 September 2023
3N.svg)
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| Names | |
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| Preferred IUPAC name
2,8,9-Trimethyl-2,5,8,9-tetraza-1-phosphabicyclo[3.3.3]undecane | |
| Identifiers | |
3D model (JSmol)
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| ChemSpider | |
PubChem CID
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| UNII | |
CompTox Dashboard (EPA)
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| Properties | |
| C9H21N4P | |
| Molar mass | 216.269 g·mol−1 |
| Appearance | colorless oil |
| Boiling point | 263.9 °C (507.0 °F; 537.0 K) |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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In chemistry, the Verkade base (or Verkade superbase) is a powerful superbase with the formula P(MeNCH2CH2)3N. A colorless oil, it is an aminophosphine although its inventor John Verkade called it proazaphosphatrane. The trimethyl derivative or 2,5,8,9-tetraza-1-phosphabicyclo[3.3.3]undecane is the simplest.[1] Diverse analogues of the Verkade base are known, e.g. with isopropyl groups in place of methyl.
Synthesis and reactions
The Verkade base is generated by the reaction of N,N,N-trimethyltren with tris(dimethylamino)phosphine:[2]
- P(NMe2)3 + (MeNHCH2CH2)3N → P(MeNCH2CH2)3N + 3 Me2NH
The principal reaction of the Verkade base is protonation. The proton is attacked by the Verkade base at the phosphorus atom within, which induces the formation of a transannular P-N bond. The product exemplifies the structure of an atrane.
The conjugate acid [HP(MeNCH2CH2)3N]+ of the base has a pKa of 32.9 in acetonitrile. For comparison, the conjugate acid of triethylamine has a pKa near 17 in acetonitrile. Owing to its ability to deprotonate weak carbon acids, the Verkade base catalyzes a variety of condensation reactions.
Related compounds
Phosphazenes are phosphorus(V) derivatives with the formula RN=P(NR2)3.
References
- ^ Verkade, John G.; Urgaonkar, Sameer (2012). "Proazaphosphatrane". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rn00702.pub2. ISBN 978-0471936237.
- ^ Schmidt, H.; Lensink, C.; Xi, S. K.; Verkade, J. G. (1989). "New Prophosphatranes: Novel intermediates to five-coordinate phosphatranes". Zeitschrift für Anorganische und Allgemeine Chemie. 578: 75–80. doi:10.1002/zaac.19895780109.