Reactions of phosphorus-containing compounds with diazo-compounds and carbenes

Khaskin, B. A.; Molodova, O. D.; Torgasheva, N. A.

doi:10.1070/rc1992v061n03abeh000947

Cited by 7 publications

(5 citation statements)

References 8 publications

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“…An example of the first case involves the formation of dihydrobenzofurans by a regiospecific route in reactions of o -quinone diazides with vinyl ethers under thermal conditions . On the other hand, retention of nitrogen in azo-coupling reactions are often observed …”

Section: Introductionmentioning

confidence: 99%

Quinone Diazides and Enaminones as a Source of New Azo Compounds with Potential Nonlinear Optical Properties

Figueiredo

Kascheres

1997

J. Org. Chem.

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Section: Introductionmentioning

confidence: 99%

Quinone Diazides and Enaminones as a Source of New Azo Compounds with Potential Nonlinear Optical Properties

Figueiredo

Kascheres

1997

J. Org. Chem.

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“…39 On the other hand, retention of nitrogen in azo-coupling reactions is often observed. 40 This type of reaction is widely used in industry for the synthesis of hydroxyazo dyes. 41 Since quinone diazides, especially nitro-substituted ones, are very sensitive to light we decided to try a onepot procedure in the reactions with enaminones in order to avoid contact of the reacting mixture with light.…”

Section: Reaction Of Enaminones With Diazoquinones Nonlinear Opticalmentioning

confidence: 99%

The chemistry of enaminones, diazocarbonyls and small rings: our contribution

Kascheres¹

2003

J. Braz. Chem. Soc.

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“…Contrary to N,O-containing LBs, phosphines react with diazo compounds forming thermodynamically stable adducts–phosphazines. , The reaction of trivalent phosphorus and diazo group is known to be reversible and equilibrium may be shifted by the variation of reaction conditions and structures of both phosphine and diazo compound. In particular, adduct of TPP and MDA, methyl ( E )-2-((triphenyl-λ-phosphanylidene)hydrazono)acetate, exhibits moderate thermodynamic stability (Table ), therefore, the equilibrium is right shifted at room temperature: …”

Section: Results and Discussionmentioning

confidence: 99%

Nature of Lewis Base Catalysis of 1,3-Dipolar Cycloaddition of Methyl Diazoacetate to Methyl Acrylate; NMR Kinetic Spectroscopy and DFT Study

et al. 2017

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The effect of Lewis base (LB) in the domino reaction between methyl diazoacetate and methyl acrylate has been studied. This domino process is initialized by a [3+2]-cycloaddition reaction to generate 3H-pyrazoline followed by a subsequent 1,3-H shift reaction forming 1H-pyrazoline as the more stable isomer. The rate of the first step is not sensitive to the presence of LBs (THF, Py, DMAP, DBU, and triphenylphosphine) as it was evidenced by kinetic nuclear magnetic resonance spectroscopy and quantum chemical modeling. LBs manifest remarkable catalytic effect on the second step of the reaction only acting as proton acceptor. DFT calculations reveal fine correlation between enthalpy of proton transfer from trans-3H-pyrazoline to LB and basic strength of the latter described in terms of BF-affinity scale. Under conditions of LB catalysis the reaction rate of the first step (methyl diazoacetate and methyl acrylate interaction) limits the rate of 3H → 1H pyrazoline isomerization and, therefore, restricts catalytic efficiency of LB. An alternative mechanism for catalysis of the 1,3-dipolar cycloaddition through formation of triazene-like intermediate during reaction of diazo acetate with LB and following Michael addition of intermediate to alkene was carefully analyzed. This reaction scheme was not confirmed in our experiments.

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Reactions of phosphorus-containing compounds with diazo-compounds and carbenes

Cited by 7 publications

References 8 publications

Quinone Diazides and Enaminones as a Source of New Azo Compounds with Potential Nonlinear Optical Properties

Quinone Diazides and Enaminones as a Source of New Azo Compounds with Potential Nonlinear Optical Properties

The chemistry of enaminones, diazocarbonyls and small rings: our contribution

Nature of Lewis Base Catalysis of 1,3-Dipolar Cycloaddition of Methyl Diazoacetate to Methyl Acrylate; NMR Kinetic Spectroscopy and DFT Study

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