Dimethyl(1-diazo-2-oxopropyl)phosphonate

• CAS: 90965-06-3
• Catalog Number: ACM90965063
• Category: Main Products
• Molecular Weight: 192.11
• Molecular Formula: C₅H₉N₂O₄P
• Synonyms: (Z)-1-diazonio-1-dimethoxyphosphorylprop-1-en-2-olate
• IUPAC Name: (Z)-1-diazonio-1-dimethoxyphosphorylprop-1-en-2-olate
• SMILES: CC(=C([N+]#N)P(=O)(OC)OC)[O-]
• InChI Key: SQHSJJGGWYIFCD-UHFFFAOYSA-N
• Density: 1.28
• Exact Mass: 192.03000

Case Study

Palladium-Catalyzed Coupling Reaction of Dimethyl (1-Diazo-2-Oxopropyl)Phosphonate To Produce Organophosphonates

Zhou, Yujing, et al. The Journal of Organic Chemistry 80.12 (2015): 6109-6118.

Researchers have established a successful synthesis method using palladium catalysis to produce organophosphonates through the reaction of α-diazo phosphonates with either benzyl or allyl halides.
Procedure for synthesizing α-diazo arylmethylphosphonates 1a-k:
The synthesis started with Pd(PPh3)4 (116 mg, 5 mol%) and K2CO3 (552 mg, 4.0 mmol) along with aryl iodide (2.0 mmol) being suspended in a 25 mL flask with combined methanol (5 mL) and toluene (5 mL) mixture at room temperature. The reaction mixture received dimethyl (1-diazo-2-oxopropyl)phosphonate (499 mg, 1.3 equiv) and was stirred at room temperature for 5 hours. The mixture underwent filtration through a silica gel column with ethyl acetate as the eluent before its volatile components were removed through reduced pressure. The crude product was purified by column chromatography (silica gel) to yield the final compounds 1a-k.
The palladium-catalyzed coupling of α-diazo arylmethylphosphonates:
Under a nitrogen atmosphere inside a 10 mL Schlenk tube, researchers mixed Pd(OAc)2 (2.2 mg, 5 mol%) with P(2-furyl)3 (9.3 mg, 20 mol%) dimethyl (diazo(phenyl)methyl) phosphonate (0.20 mmol) and benzyl or allyl halide (0.25 mmol) using toluene (2 mL) as the solvent. The mixture received 40.4 mg of (iPr)2NH (0.40 mmol), which was then stirred at 80 °C for 5 hours. The solution passed through a silica gel column and was eluted using ethyl acetate before solvent removal occurred under vacuum conditions. The crude residue was further purified using preparative thin-layer chromatography to produce the final products.

Dimethyl(1-Diazo-2-Oxopropyl)Phosphonate for the Synthesis of Quinoline Derivatives

Thakare, Prashant P., et al. Journal of Heterocyclic Chemistry 57.11 (2020): 3918-3929.

Researchers successfully synthesized novel quinoline derivatives 6a-t by combining 4-(4-ethynyl-1-phenyl-1H-pyrazol-3-yl)quinoline (4a-d) with different substituted benzyl azides (5a-e) using a click reaction. The alkyne compounds 4a-d were synthesized through a Bestmann-Ohira reaction between 1-phenyl-3-(quinolin-4-yl)-1H-pyrazole-4-carbaldehyde and dimethyl(1-diazo-2-oxopropyl)phosphonate.
General Procedures
The preparation of 4-(4-ethynyl-1-phenyl-1H-pyrazol-3-yl)quinoline (4a) involved stirring an ice-cold mixture containing 1-phenyl-3-(quinolin-4-yl)-1H-pyrazole-4-carbaldehyde (2a, 1.5g, 0.005mol), dimethyl(1-diazo-2-oxopropyl)phosphonate (1.25g, 0.0065mol), and K2CO3 (1.39g, 0.01mol) dissolved in dry methanol (20 mL) at room temperature for 24 hours. The solvent removal process started with a rotary evaporator after TLC analysis verified completion of the reaction. An 80 mL water solution dissolved the residue before extraction with three 25 mL ethyl acetate portions. Following brine washing and sodium sulfate drying, the organic phase underwent vacuum distillation. The product compound 4a was isolated using a hexane:ethyl acetate (7:3) mixture as the eluent which gave 0.65 g (44% yield). Compounds 4b-d were synthesized using the same procedure that was previously detailed.

Methanolysis of dimethyl (1-diazo-2-oxopropyl)phosphonate

Ohira, Susumu. Synthetic Communications 19.3-4 (1989): 561-564.

Dimethyl (1-diazo-2-oxopropyl)phosphonate is converted to dimethyl (diazomethyl)phosphonate and can be used for the synthesis of enol ethers or alkynes without isolation.
Potassium carbonate is added to a solution of dimethyl (1-diazo-2-oxopropyl)phosphonate and a carbonyl compound in anhydrous methanol at 0°C under argon protection. The mixture is stirred at 0°C for 30 minutes and then at room temperature for 2-13 hours. After adding saturated aqueous ammonium chloride solution and pentane, the organic layer is separated, dried (Na2SO4) and evaporated. The product is separated by silica gel column chromatography using pentane or pentane-dichloromethane as eluent to obtain the product.

Dimethyl (1-diazo-2-oxopropyl)phosphonate converted into fluorinated phosphonates

Zhou, Yujing, Yan Zhang, and Jianbo Wang. Organic & Biomolecular Chemistry 14.44 (2016): 10444-10453.

The α-diazoaryl methylphosphonates generated from dimethyl (1-diazo-2-oxopropyl)phosphonate can be used to prepare various fluorinated phosphonates through a double functionalization reaction. By using different fluorinating agents, the diazo functional group (RR'C=N2) was successfully converted to RR'CF2, RR'CHF, RR'CFBr or RR'CFNR"2 groups. Various fluorinated organophosphorus compounds were easily obtained from a common type of precursors in high to excellent yields.
The diazo compounds were prepared according to the palladium-catalyzed cross-linking method of dimethyl (1-diazo-2-oxopropyl)phosphonate with aryl iodide. Pd(PPh3)4 (116 mg, 5 mol%), K2CO3 (552 mg, 4.0 mmol, 2.0 equiv) and aryl iodide (2.0 mmol, 1.0 equiv) were suspended in methanol (5 mL) and toluene (5 mL) in a 25 mL flask under normal temperature atmosphere. Then Dimethyl (1-diazo-2-oxopropyl)phosphonate (499 mg, 2.6 mmol, 1.3 equiv) was added. The mixture was filtered through a short path of silica gel, eluted with ethyl acetate, and the filtrate was evaporated in vacuo to remove the volatile substances. The crude residue was purified by column chromatography (silica gel, petroleum ether: EtOAc = 1:1) to obtain the final product.

Synthesis of vinylphosphonates from dimethyl (1-diazo-2-oxopropyl)phosphonate

Zhou, Yujing, et al. The Journal of Organic Chemistry 80.12 (2015): 6109-6118.

An efficient method for the synthesis of organic phosphonates was developed by coupling α-diazophosphonates produced from dimethyl (1-diazo-2-oxopropyl)phosphonate with benzyl or allylic halides. This method allows the facile and high-yield synthesis of trisubstituted vinylphosphonates with a variety of functional groups with excellent stereoselectivity. In addition, using a similar strategy, α-substituted vinylphosphonates can also be synthesized via the palladium-catalyzed coupling reaction of N-tosylhydrazone with aryl bromides. The migratory insertion of palladium carbene is considered to be the key step in this reaction.
Pd(PPh3)4 (116 mg, 5 mol%), K2CO3 (552 mg, 4.0 mmol) and aryl iodide (2.0 mmol) were suspended in methanol (5 mL) and toluene (5 mL) in a 25 mL flask at room temperature. Dimethyl(1-diazo-2-oxopropyl)phosphonate (499 mg, 1.3 eq.) was then added and the resulting solution was stirred at room temperature for 5 h. The mixture was filtered through a short path of silica gel, eluting with ethyl acetate, and the filtrate was evaporated in vacuo to remove volatiles.

Dimethyl(1-diazo-2-oxopropyl)phosphonate for reducing carbohydrates

Thiéry, Jean-Christophe, Catherine Fréchou, and Gilles Demailly. Tetrahedron Letters 41.33 (2000): 6337-6339.

The aldose derivatives react with dimethyl(diazomethyl)phosphonate, which is generated in situ by methane decomposition, to produce sugar-1-ethanol derivatives. This synthesis has two main advantages: it is a one-step synthesis and tolerates free hydroxyl groups.
2,3-5,6-di-O-isopropylated-d-mannose 1 and K2CO3 in methanol solution were added dropwise for 8 h. The reaction mixture was cooled. After neutralization with HCl, it was concentrated under reduced pressure. The residue was taken up in a mixture of water and ethyl acetate. After decantation, the organic phase was dried over sodium sulfate and concentrated under reduced pressure. Chromatography on silica, eluent hexane:acetylene esters allowed the separation of the acetylene derivative 2 with an efficiency of 84%.

Custom Q&A

What is the molecular formula of Dimethyl(1-diazo-2-oxopropyl)phosphonate?

The molecular formula is C5H9N2O4P.

What are the synonyms of Dimethyl(1-diazo-2-oxopropyl)phosphonate?

The synonyms include Ohira-Bestmann Reagent, Bestmann reagent, Ohira's reagent, and more.

Is Dimethyl(1-diazo-2-oxopropyl)phosphonate flammable?

Yes, it is flammable.

Is Dimethyl(1-diazo-2-oxopropyl)phosphonate toxic?

Yes, it is acute toxic.

What is the IUPAC name of Dimethyl(1-diazo-2-oxopropyl)phosphonate?

The IUPAC name is 1-diazo-1-dimethoxyphosphorylpropan-2-one.

What is the InChI of Dimethyl(1-diazo-2-oxopropyl)phosphonate?

The InChI is InChI=1S/C5H9N2O4P/c1-4(8)5(7-6)12(9,10-2)11-3/h1-3H3.

What is the InChIKey of Dimethyl(1-diazo-2-oxopropyl)phosphonate?

The InChIKey is SQHSJJGGWYIFCD-UHFFFAOYSA-N.

What is the CAS number of Dimethyl(1-diazo-2-oxopropyl)phosphonate?

The CAS number is 90965-06-3.

What is the molecular weight of Dimethyl(1-diazo-2-oxopropyl)phosphonate?

The molecular weight is 192.11 g/mol.

What is the European Community (EC) number of Dimethyl(1-diazo-2-oxopropyl)phosphonate?

The EC number is 692-521-0.