34966-53-5

Upstream product

• 67-56-1 methanol 
• 36930-95-7 2,2,2-trichloro-1-(4-methylphenyl)ethanone 
• 5781-53-3 monomethyl oxalyl chloride 
• 108-88-3 toluene 
• 17640-25-4 methyl 2,2-dichloro-2-methoxyacetate 
• 4294-57-9 para-methylphenylmagnesium bromide 
• 122-00-9 para-methylacetophenone 
• 13305-13-0 methyl (+/-)-α-hydroxy-α-(4-methylphenyl)acetate 
• 553-90-2 Dimethyl oxalate 
• 39687-95-1 isocyanoacetic acid methyl ester 
• 585526-04-1 N-(4-methoxy-4-methylcyclohexa-2,5-dien-1-ylidene)-4-methylbenzenesulfonamide 
• 599-86-0 4-methyl-N-(4-methylphenyl)benzenesulfonamide 
• 766-97-2 4-n-methylphenylacetylene 
• 1075-47-4 4-methylphenylglyoxal 

Downstream Products

• 33131-25-8 3-Methyl-2-p-tolyl-but-2-enoic acid methyl ester 
• 57699-36-2 cis-2,3-bis(carbomethoxy)-p,p'-dimethylstilbene oxide 
• 81316-43-0 trans-2,3-bis(carbomethoxy)-p,p'-dimethylstilbene oxide 
• 139021-97-9 2-p-Tolyl-[1,3]dithiane-2-carboxylic acid methyl ester 
• 13305-13-0 methyl (+/-)-α-hydroxy-α-(4-methylphenyl)acetate 
• 99-75-2 4-methyl-benzoic acid methyl ester 
• 1043605-44-2 (S)-(+)-methyl 2-hydroxy-2-(4-methylphenyl)-propionate 
• 127393-69-5 (R)-(-)-methyl 2-hydroxy-2-(4-methylphenyl)propanoate 
• 1034852-92-0 methyl 2-(2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene)-2-p-tolylacetate 

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.).

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.

Silyl Cyanopalladate-Catalyzed Friedel-Crafts-Type Cyclization Affording 3-Aryloxindole Derivatives

3-Aryloxindole derivatives were synthesized through a Friedel-Crafts-type cyclization. The reaction was catalyzed by a trimethylsilyl tricyanopalladate complex generated in situ from trimethylsilyl cyanide and Pd(OAc) 2. Wide varieties of diethyl phosphates derived from N -arylmandelamides were converted almost quantitatively into oxindoles. When N, N -dibenzylamide was used instead of an anilide substrate, a benzo-fused δ-lactam was obtained. An oxindole product was subjected to substitution reactions to afford 3,3-diaryloxindoles with two different aryl groups.

Copper on charcoal: Cu0nanoparticle catalysed aerobic oxidation of α-diazo esters

By using a charcoal supported nano Cu0catalyst (Cu/C), a highly efficient oxidation of α-diazo esters to α-ketoesters with molecular oxygen as the sole oxidant has been developed. In the presence of the Cu/C catalyst, 2-aryl-α-diazo esters with both electron-donating and electron-withdrawing groups can be oxidized to the corresponding α-ketoesters efficiently. Furthermore, this Cu/C catalyst can catalyse the reaction of aryl α-diazo ester with water to form aryl ketoester, 2-aryl-2-hydroxyl acetate ester and 2-aryl acetate ester. In this case, water is split by α-diazo ester, and the diazo group is displaced by the oxygen or hydrogen atom in water. Mechanistic investigation showed that the reaction of α-diazo ester with oxygen proceeds through a radical pathway. In the presence of 2,2,6,6-tetramethyl piperidine nitrogen oxide, the reaction of α-diazo ester with oxygen is dramatically inhibited. Furthermore, the reaction of α-diazo ester with water is investigated by an isotopic tracer method, and GCMS detection showed that a disproportionation reaction occurred between α-diazo ester and water.

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 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.

Stoichiometric Photochemical Carbene Transfer by Bamford–Stevens Reaction

The photolysis of diazoalkanes is a timely strategy to conduct carbene-transfer reactions under mild and metal-free reaction conditions, and has developed as an important alternative to conventional metal-catalyzed carbene-transfer reactions. One of the major limitations lies within the rapidly occurring side reaction of the carbene intermediate with remaining diazoalkane molecules that result in the use of an excess of the reaction partner and thus impacts on the reaction efficiency. Herein, we describe a protocol that takes advantage of the in situ generation of donor–acceptor diazoalkanes by Bamford–Stevens reaction. Following this strategy, the concentration of the diazoalkane reaction partner can be minimized to reduce unwanted side reactions and to now conduct photochemical carbene transfer reactions under stoichiometric reaction conditions. We have explored this approach in the C?H and N?H functionalization and cyclopropanation reaction of N-heterocycles and could demonstrate the applicability of this method in 51 examples.

Novel methyl benzoylformate photoinitiator and preparation method thereof

The invention relates to the technical field of organic synthesis, in particular to a novel methyl benzoylformate photoinitiator and a preparation method thereof. The emission wavelength range of LEDlight sources used in the market at present is 365 nm or above, while, the maximum absorption wavelength of a traditional photoinitiator MBF is 255 nm, and as a result, the wavelength of the traditional photoinitiator MBF is not matched with the emission wavelength of the LED light sources. In order to enable the maximum absorption wavelength of the MBF photoinitiator to be matched with the main emission wavelength range of the LED light sources, the invention provides the novel methyl benzoylformate photoinitiator and the preparation method thereof. The compound is obtained by condensation reaction of a carbonyl functionalized methyl benzoylformate derivative containing double alpha H and a ketone compound; the maximum absorption wavelength of the compound can reach 365 nm or above; and the compound is matched with the LED light sources used on the market and has good commercial application prospects.

Novel synthesis method of alpha-carbonyl acid ester

The invention discloses a novel synthesis method of alpha-carbonyl acid ester. The method comprises the following steps: carrying out chlorination reaction on an alpha-methylene-containing nitrile compound and chlorine to obtain dichloronitrile, reacting the dichloronitrile product in a sulfuric acid and water system to obtain formyl cyanide, then acquiring an imino sulfate compound in the same reaction system, and finally performing esterification to obtain the target product. The adopted reaction raw materials are wide in sources and low in price, highly toxic solid sodium cyanide can be prevented from being used in the prior art, the method is environmentally friendly, and the method is easy to operate, mild in condition and easy to industrialize.

Cobalt-Catalyzed Transfer Hydrogenation of α-Ketoesters and N-Cyclicsulfonylimides Using H2O as Hydrogen Source

A Co-catalyzed effective transfer hydrogenation of various α-ketoesters and N-cyclicsulfonylimides by safe and environmentally benign H2O as hydrogen source is described. The reaction used easily available and easy to handle zinc metal as a reductant. Interestingly, the catalytic system does not require ligand for reduction of N-cyclicsulfonylimides. (Figure presented.).