10419-87-1

Upstream product

• 56-23-5 tetrachloromethane 
• 80654-02-0 phosphorous acid benzyl ester-diphenyl ester 
• 101-02-0 triphenyl phosphite 
• 100-44-7 benzyl chloride 
• 80733-03-5 dineopentyl phenyl phosphite 
• 100-39-0 benzyl bromide 
• 4712-55-4 diphenyl hydrogen phosphite 
• 1666-17-7 benzaldehyde p-toluenesulfonylhydrazone 
• 100-51-6 benzyl alcohol 
• 620-05-3 iodomethylbenzene 

Downstream Products

• 128587-62-2 3-styryl-furan 
• 91-57-6 2-Methylnaphthalene 
• 55137-99-0 benzylphosphonofluoridic acid 

Relevant academic research and scientific papers

Direct18F-Labeling of Biomolecules via Spontaneous Site-Specific Nucleophilic Substitution by F-on Phosphonate Prostheses

We describe a high radiochemical yield late-stage direct 18F-labeling of bare biomolecules containing common active groups. Spontaneity and site-selectivity are attributed to the remarkably higher rates of nucleophilic substitution reactions on phosphonates than on other electrophiles by F- at various hydrogen bond forms. Rapid access to many medicinally significant 18F-labeled biomolecules is achieved at 21-68% radiochemical yields and 35.9-55.1 GBq μmol-1 molar activities both manually or automatically.

Umpolung Difunctionalization of Carbonyls via Visible-Light Photoredox Catalytic Radical-Carbanion Relay

The combination of photoredox catalysis with the Wolff-Kishner (WK) reaction allows the difunctionalization of carbonyl groups by a radical-carbanion relay sequence (photo-Wolff-Kishner reaction). Photoredox initiated radical addition to N-sulfonylhydrazones yields α-functionalized carbanions following the WK-type mechanism. With sulfur-centered radicals, the carbanions are further functionalized by reaction with electrophiles including CO2 and aldehydes, whereas CF3 radical addition furnishes a wide range of gem-difluoroalkenes through β-fluoride elimination of the generated α-CF3 carbanions. More than 80 substrate examples demonstrate the broad applicability of this reaction sequence. A series of investigations including radical inhibition, deuterium labeling, fluorescence quenching, cyclic voltammetry, and control experiments support the proposed radical-carbanion relay mechanism.

Alcohol-based Michaelis-Arbuzov reaction: An efficient and environmentally-benign method for C-P(O) bond formation

The famous Michaelis-Arbuzov reaction is extensively used both in the laboratory and industry to manufacture tons of widely-used organophosphoryl compounds every year. However, this method and the modified Michaelis-Arbuzov reactions developed recently still have some limitations. We now report a new alcohol-version of the Michaelis-Arbuzov reaction that can provide an efficient and environmentally-benign method to address the problems of the known Michaelis-Arbuzov reactions. That is, a wide range of alcohols can readily react with phosphites, phosphonites, and phosphinites to give all the three kinds of phosphoryl compounds (phosphonates, phosphinates, and phosphine oxides) using an n-Bu4NI-catalyzed efficient C-P(O) bond formation reaction. This general method can also be easily scaled up and used for further synthetic transformations in one pot.

Synthesis of dialkyl and diaryl benzylphosphonates through a ZnI 2-mediated reaction

Several trialkyl and two triaryl phosphites have been tested for their reactivity in the zinc iodide mediated conversion of benzyl alcohol to the corresponding phosphonates. Most react smoothly to afford the desired phosphonate diesters, including hindered and nonracemic phosphites. The implications of this reactivity on the reactions involved in the transformation are discussed.

DBU-promoted alkylation of alkyl phosphinates and H-phosphonates

The alkylation of alkyl phosphinates and some H-phosphonate diesters is promoted by the base DBU. Only more reactive alkyl halides react in preparatively useful yields. However, the method provides easy access to important H-phosphinate building blocks, without the need for a protecting group strategy or metal catalysts. The reaction is conveniently conducted at, or below, room temperature. The preparation of methyl-H-phosphinate esters is particularly interesting as it avoids the heretofore more common use of methyldichlorophosphine MePCl2.

Base-induced photorearrangements from 3-styrylfurans to 2-methylnaphthalenes

Irradiation of 3-(4-substituted styryl)furans in basic media yielded a series of 7-substituted-2-methylnaphthalenes, including methoxy, isopropyl, ethyl, methyl, fluoro, and cyano substituents. This base-induced photorearrangement involves cis-trans photoisomerization, 6e photocyclization, base-induced elimination, and a Norrish Type I photoreaction and is a novel method to synthesize unsymmetrical 2,7-disubstituted naphthalenes.

Palladium(0)-catalyzed benzylation of H-phosphonate diesters: An efficient entry to benzylphosphonates

A new, efficient method for the synthesis of benzylphosphonate diesters via a palladium(0)-catalyzed cross-coupling reaction between benzyl halides and H-phosphonate diesters, using Pd(OAc)2 as a palladium source and Xantphos as a supporting ligand, has been developed. Georg Thieme Verlag Stuttgart.

A concise method for synthesis of diaryl aryl- or alkylphosphonates

A convenient method has been developed to synthesize diaryl arylphosphonates from triaryl phosphites, triethyl phosphite, and aromatic halides. The new method relies on the triethyl phosphite assisted nickel catalyzed Arbuzov reaction and can be applied to synthesize certain diaryl alkylphosphonates without catalysts.

Quasiphosphonium Intermediates. Part 3. Preparation, Structure, and Reactivity of Alkoxyphosphonium Halides in the Reaction of Neopentyl Diphenylphosphinite, Dineopentyl Phenylphosphinite, and Trineopentyl Phosphite with Halogenomethanes and the Effect of Phenoxy-substituenst on the ...

The reactions of neopenthyl diphenylphosphinite with chloro-, bromo-, or iodo-methane and of dineopentyl phenylphosphphonite with bromo- or iodo-methane yield crystalline alkoxyphosphonium halides.In deuteriochloroform these intermediates decompose by a first-order process which involves rate-determining collapse of the phosphonium halide ion-pair with SN2-type fission of the alkyl-oxygen bond.Rates for chloride, bromide, and iodide are similar.In a more ionising medium (deuterioacetonitrile) dissociation leads to stabilisation of the intermediates and to deviation from first-order decomposition.Previously determined X-ray diffraction data for the bromides, together with relative rates of decomposition in deuteriochloroform for intermediates in the series Phn(RO)3-nP+MeX- (n = 0,1, or 2) suggest that the stability and reactivity of alkoxyphosphonium intermediates are determined largely by inductive rather than mesomeric effects of ligands.The presence of phenoxy-substituents on phosphorus may cause a tendency towards SN1-type fission of the alkyl-oxygen bond in certain circumstances.