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| | Silane, trimethyl[(methyleneoxidoamino)oxy]- Basic information |
| | Silane, trimethyl[(methyleneoxidoamino)oxy]- Chemical Properties |
| Boiling point | 134.0±23.0 °C(Predicted) | | density | 0.904±0.06 g/cm3(Predicted) | | solubility | Sol pentane and in all nonprotic common organic solvents. | | pka | -1.74±0.53(Predicted) |
| | Silane, trimethyl[(methyleneoxidoamino)oxy]- Usage And Synthesis |
| Physical properties | R1 = C5H11, R2 = H, R3Si = TBDMS: bp
80–90 °C/0.02 mmHg. R1R2 = (CH2)5, R3Si = TBDMS: bp
150 °C/0.01 mmHg. A more complete list of silyl nitronates is
given by Torssell. | | Uses | Trimethylsilyl Methanenitronate reacts with alkenes in a 1,3-dipolar cycloaddition reaction; undergo Bu4NF-mediated diastereoselective carbonyl addition to
aldehydes; react with alkyllithium reagents to give oximes; oxidative coupling leads to 1,2-dinitro alkanes; cross coupling
with silyl enol ethers or enamines gives β-nitro carbonyl
derivatives; conversion of thiocarbonyl to carbonyl groups; can be converted into carbonyl compounds (cf. Nef reaction). It participates in the reactions of Silyl Nitronates with C–C Bond Formation, Reactions of Silyl Nitronates with Strong Base, Functionalization Reactions of Silyl Nitronates, Conversion of Thioketones to Ketones, Silyl Nitronate Reactivity Pattern, and other uses. | | Preparation | A large number of silylation conditions
can be applied to primary or secondary nitroalkanes,including:
R3SiCl/Et3N (or Ag+ or Li2S), R3SiOTf, LDA/R3SiCl,
R3SiCl/DBU, silylated amides, etc. The first reports were
published by Ioffe, Tartakovskii, and their colleagues in the
early 1970s. The silyl nitronates are isolated by nonaqueous
workup and purified by bulb-to-bulb distillation, with the TBDMS
derivatives being much more thermally stable than the
TMS derivatives. From crystal structure analyses and NMR
studies it is concluded that the silyl group migrates rapidly from
one nitronate oxygen to the other and that the more stable configuration
of silyl nitronates derived from primary nitroalkanes is (E). |
| | Silane, trimethyl[(methyleneoxidoamino)oxy]- Preparation Products And Raw materials |
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