156276-23-2

Upstream product

• 127709-19-7 methyl 4-fluoro-α-hydroxyphenylacetate 
• 5781-53-3 monomethyl oxalyl chloride 
• 352-13-6 4-flourophenylmagnesium bromide 
• 219564-79-1 methyl 2-diazo-2-(4-fluorophenyl)acetate 
• 553-90-2 Dimethyl oxalate 
• 67-56-1 methanol 
• 403-42-9 1-(4-fluorophenyl)ethanone 
• 7542-64-5 α,α-Dibromo-4'-fluoroacetophenone 
• 460-00-4 1-Bromo-4-fluorobenzene 
• 100891-10-9 methyl p-fluorocinnamate 
• 403-32-7 (4-fluorophenyl)glyoxal 
• 424801-69-4 C₁₀H₆F₄O₂ 
• 4640-67-9 3-(4-fluorophenyl)-3-oxopropionitrile 
• 34837-84-8 4-fluorobenzeneacetic acid methyl ester 

Downstream Products

• 32222-46-1 (4-fluoro-phenyl)-hydroxy-acetic acid methyl ester 
• 63096-35-5 (4-fluoro-phenyl)-hydroxy-acetic acid methyl ester 
• 81941-86-8 6-(4-fluorophenyl)-3-methylmercapto-as-triazin-5-one 
• 125923-59-3 methyl difluoro(4-fluorophenyl)acetate 
• 60300-84-7 methyl α-benzyloxyphenylacetate 
• 1152322-66-1 C₁₉H₂₈FNO₄Si 
• 127709-19-7 methyl 4-fluoro-α-hydroxyphenylacetate 

Relevant academic research and scientific papers

Tris(pentafluorophenyl)borane-Catalyzed Oxygen Insertion Reaction of α-Diazoesters (α-Diazoamides) with Dimethyl Sulfoxide

A tris(pentafluorophenyl)borane-catalyzed oxidation reaction of α-diazoesters (α-diazo amides) with dimethyl sulfoxide has been developed. The reaction proceeds under metal free conditions to afford a series α-ketoesters and α-ketoamides. The synthetic utility of this protocol is demonstrated through synthetic transformations and scaled-up synthesis. (Figure presented.).

Unraveling two pathways for NHPI-mediated electrocatalytic oxidation reaction

Two pathways for N-hydroxyphthalimide (NHPI)-mediated electrocatalytic oxidation using phenylacetate derivatives as template substrates were first reported for benzylic C[sbnd]H oxidation to oxygenated and non-oxygenated products. DFT calculation indicates that the hydrogen-atom transfer (HAT) process between phthalimido-N-oxyl (PINO) and substrate is a rate-determined step. Aromatic α-keto esters and 2-((1,3-dioxoisoindolin-2-yl)oxy)-2-aryl acetate obtained by cross-coupling between benzylic radical and PINO can be selectively synthesized through controlling the concentration of PINO radical. This method provides a deep understanding for selective weak C[sbnd]H oxidation using NHPI as redox mediator.

Tandem Photoredox-Chiral Phosphoric Acid Catalyzed Radical-Radical Cross-Coupling for Enantioselective Synthesis of 3-Hydroxyoxindoles

A photochemical protocol that couples diarylamines and α-ketoesters to afford the chiral 3-hydroxyoxindoles through tandem photoredox and chiral phosphoric acid catalysis is developed. The reaction involves an enantioselective photochemical radical-radical cross-coupling process. The chiral phosphoric acid is discovered to play crucial roles by decreasing the reductive potentials of α-ketoesters and stereocontrolling the downstream asymmetric radical-radical cross-coupling via the formation of pentacoordinate complex.

Amphiphilic fluorine-containing benzoyl formate photoinitiator suitable for LED photopolymerization and preparation method of amphiphilic fluorine-containing benzoyl formate photoinitiator

The invention discloses an amphiphilic fluorine-containing benzoyl formate photoinitiator suitable for LED photopolymerization, relates to the field of photosensitive macromolecules, and aims to solve the problems that an existing photoinitiator is poor in initiation performance under the irradiation of an LED light source and limited in application in the field of deep polymerization. The chemical structural general formula of the photoinitiator is shown in the specification, wherein R1 is selected from hydrogen, C1-C16 aliphatic groups, aralkyl, ether and aryl, R2, R3, R4, R5 and R6 are selected from hydrogen, fluorine and trifluoromethyl, but R2, R3, R4, R5 and R6 cannot be hydrogen at the same time. The invention also provides a preparation method of the photoinitiator and application of the photoinitiator in a photopolymerization system. The photoinitiator has the beneficial effects that the photoinitiator has proper absorption capacity in a visible light region, not only ensures higher photopolymerization rate under an LED light source, but also can be applied to deep polymerization, in addition, the photoinitiator is suitable for oily and water-based photopolymerization systems, does not contain ions, is wider in application range, and facilitated the development of the LED photopolymerization industry.

Photoinduced Diverse Reactivity of Diazo Compounds with Nitrosoarenes

A diverse reactivity of diazo compounds with nitrosoarene in an oxygen-transfer process and a formal [2 + 2] cycloaddition is reported. Nitosoarene has been exploited as a mild oxygen source to oxidize an in situ generated carbene intermediate under visible-light irradiation. UV-light-mediated in situ generated ketenes react with nitosoarenes to deliver oxazetidine derivatives. These operationally simple processes exemplify a transition-metal-free and catalyst-free protocol to give structurally diverse α-ketoesters or oxazetidines.

Preparation method of alpha-ketoester compound

The invention discloses a preparation method of an alpha-ketone ester compound. The method specifically comprises the following operation steps: adding raw materials alpha-diazo ester and an organic photocatalyst into a reaction flask, then adding an organic solvent, and reacting for 2-12 hours in air at room temperature under the irradiation of a visible light lamp; after the reaction is monitored by thin-layer chromatography (TLC), stopping the reaction, and extracting a reaction solution by using ethyl acetate; concentrating the extracting solution under reduced pressure to obtain a crude product, and performing column chromatography separation on the crude product to obtain the alpha-diazonium ester compound. According to the preparation method, clean visible light is used as reaction energy, cheap organic dye is used as a photocatalyst, air is used as a green oxidizing agent and an oxygen source, and the preparation method has the advantages of simplicity and convenience in operation, no metal residue and mild reaction conditions.

Visible-Light-Induced Catalyst-Free Carboxylation of Acylsilanes with Carbon Dioxide

Intermolecular carbon-carbon bond formation between acylsilanes and carbon dioxide (CO2) was achieved by photoirradiation under catalyst-free conditions. In this reaction, siloxycarbenes generated by photoisomerization of the acylsilanes added to the C═O bond of CO2 to give α-ketocarboxylates, which underwent hydrolysis to afford α-ketocarboxylic derivatives in good yields. Control experiments suggest that the generated siloxycarbene is likely to be from the singlet state (S1) of the acylsilane and the addition to CO2 is not in a concerted manner.

Preparation method for rapidly generating alpha-ketone ester through iodine-mediated alpha-diazonium ester oxidation

The invention relates to the field of research of ketone ester compounds, in particular to a preparation method for rapidly generating alpha-ketone ester through iodine-mediated alpha-diazo ester oxidation, the preparation method comprises the following steps: in an organic solvent, stirring alpha-diazo ester and iodine elementary substance as raw materials at room temperature for about half an hour to obtain the alpha-ketone ester compound. According to the method, transition metal does not need to be used as a catalyst, a strong oxidant does not need to be used, only under the room temperature condition, the low-toxicity and cheap iodine elementary substance is used as the oxidant, and the alpha-keto ester is generated through efficient oxidation of the alpha-diazonic acid ester. The method has the advantages that the reaction time is short (about 0.5 hour), the universality is high, the alpha-diazonic acid ester with electron donating groups or electron withdrawing groups can achieve medium to excellent yield (80%-99%), a greener alternative approach is represented, and a new general synthesis route is provided for efficient preparation of alpha-ketoester.

Methyl Benzoylformate Derivative Norrish Type I Photoinitiators for Deep-Layer Photocuring under Near-UV or Visible LED

We designed and prepared a series of methyl benzoylformate (MBF) derivatives Norrish type I photoinitiators (MBFs) for light-emitting diode (LED)-induced photopolymerization through computer simulation. The potential photolysis mechanism of MBFs under LED at 405 nm was explored by steady-state photolysis, nuclear magnetic resonance, and electron spin resonance. The as-synthesized photoinitiator dimethyl 1,4-dibenzoylformate (DM-BD-F) can efficiently initiate free radical photopolymerization of acrylate monomers under LED irradiation at 405 nm. Moreover, we predicted well the photoinitiating capability of MBFs through the cleavage exothermy (ΔH) calculated by triplet bond dissociation energy (BDE) and triplet energy (ET). Significantly, based on the weak absorption of MBFs at 405 nm, MBFs were successfully applied to deep-layer photocuring and the curing depth reached 6.5 cm after the irradiation of LED at 405 nm for 30 s. This research provides a new idea and efficient strategy for the molecular design of photoinitiators for deep-layer photocuring.

Copper(I)-catalyzed aerobic oxidation of α-diazoesters

A practical Cu-catalyzed oxidation of α-diazoesters to α-ketoesters using molecular oxygen as an oxidant has been developed. Both electron-poor and electron-rich aryl α-diazoesters are suitable substrates and provide the α-ketoesters in good yields. In this oxidative system, α-diazo-β-ketoesters are also compatible as substrates but unexpectedly furnish α-ketoesters via C-C bond cleavage, rather than the vicinal tricarbonyl products.