1864-94-4

Usage

Uses

Used in Chemical Synthesis:
Phenyl formate is used as a reagent in the palladium-catalyzed carbonylation of aryl, alkenyl, and allyl halides. This reaction is an important method for the synthesis of various organic compounds, including pharmaceuticals, agrochemicals, and fine chemicals.
Used in Formylation of Amines:
Phenyl formate is also used as a reagent for the formylation of amines. The reaction involves the conversion of amines to their corresponding formate esters, which can be further used in the synthesis of various organic compounds, including pharmaceuticals and agrochemicals.

InChI:InChI=1/C7H6O2/c8-6-9-7-4-2-1-3-5-7/h1-6H

Upstream product

• 64-18-6 formic acid 
• 1174-72-7 tetraphenoxysilane 
• 13165-73-6 phenyl chlorosulphinate 
• 18145-35-2 formic acid silicic acid-anhydride 
• 71-43-2 benzene 
• 108-95-2 phenol 
• 141-53-7 sodium formate 
• 1493-02-3 formyl fluoride 
• 26944-31-0 N,N-Diformylacetamide 
• 274-09-9 Methylenedioxybenzene 
• 1988-17-6 m-nitrophenyl formate 
• 3229-70-7 phenolate 
• 1865-01-6 (4-nitrophenyl) formate 
• 16204-37-8 3,6-diphenyl-1,2,4,5-tetraoxane 

Downstream Products

• 58780-17-9 5-(2-formyl-6-methoxy-1,2,3,4,5,8-hexahydro-isoquinolin-1-ylmethyl)-2-methoxy-phenol 
• 54186-36-6 1-(2'-bromo-4'-methoxy-5'-hydroxybenzyl)-2-formyl-1,3,4,6,7,8-hexahydroisoquinolin-6-one 
• 762-75-4 tert-butyl formate 
• 74007-24-2 1-(2'-bromo-4'-methoxy-5'-hydroxybenzyl)-2-formyl-1,3,4,5,7,8-hexahydroisoquinolin-6-one 
• 120-80-9 benzene-1,2-diol 
• 123-31-9 hydroquinone 
• 108-46-3 recorcinol 
• 108-95-2 phenol 
• 89683-20-5 4-hydroxyphenyl formate 
• 110851-12-2 catechol monoformate 
• 89683-19-2 formyl resorcinol 
• 97098-70-9 Formic acid phenyl ester; compound with GENERIC INORGANIC NEUTRAL COMPONENT 
• 64-18-6 formic acid 
• 17130-63-1 2-hydroxymethylene-5α-cholestan-3-one 

Relevant academic research and scientific papers

Understanding the efficacy of N,N-dimethylformamide and oxalyl chloride combination as chemoselective O-formylating agent: An unified experimental and theoretical study

We have developed a simple but efficient synthetic protocol for the O-formylation of a wide range of aromatic hydroxyl/phenolic substrates using an N,N-dimethylformamide (DMF) and oxalyl chloride [(COCl)2] combination in dichloromethane (DCM) as solvent at ambient temperature. The DMF/(COCl)2combination was found to be highly chemoselective for the aromatic/phenolic hydroxyl group over aliphatic hydroxyl or aromatic amine/thiol groups. This chemoselectivity of DMF/(COCl)2combination towards O-formylation of aromatic alcohols was explained on the basis of outcomes of both experimental and density functional theory–based theoretical studies.

Urchin-like Nb2O5 hollow microspheres enabling efficient and selective photocatalytic C–C bond cleavage in lignin models under ambient conditions

Selective cleavage of robust C?C bonds to harvest value-added aromatic oxygenates is an intriguing but challenging task in lignin depolymerization. Photocatalysis is a promising technology with the advantages of mild reaction conditions and strong sustainability. Herein, we show a novel urchin-like Nb2O5 hollow microsphere (U-Nb2O5 HM), prepared by one-pot hydrothermal method, are highly active and selective for Cα?Cβ bond cleavage of lignin β-O-4 model compounds under mild conditions, achieving 94% substrate conversion and 96% C?C bond cleavage selectivity. Systematic experimental studies and density functional theory (DFT) calculations revealed that the superior performance of U-Nb2O5 HMs arises from more exposed active sites, more efficient free charge separation and the active (001) facet, which facilitates the activation of Cβ?H bond of lignin models and generate key Cβ radical intermediates by photogenerated holes, further inducing the Cα?Cβ bond cleavage to produce aromatic oxygenates. This work could provide some suggestions for the fabrication of hierarchical photocatalysts in the lignin depolymerization system.

One-Pot Transformation of Lignin and Lignin Model Compounds into Benzimidazoles

It is a challenging task to simultaneously achieve selective depolymerization and valorization of lignin due to their complex structure and relatively stable bonds. We herein report an efficient depolymerization strategy that employs 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) as oxidant/catalyst to selectively convert different oxidized lignin models to a wide variety of 2-phenylbenzimidazole-based compounds in up to 94 % yields, by reacting with o-phenylenediamines with varied substituents. This method could take full advantage of both Cβ and/or Cγ atom in lignin structure to furnish the desirable products instead of forming byproducts, thus exhibiting high atom economy. Furthermore, this strategy can effectively transform both the oxidized hardwood (birch) and softwood (pine) lignin into the corresponding degradation products in up to 45 wt% and 30 wt%, respectively. Through a “one-pot” process, we have successfully realized the oxidation/depolymerization/valorization of natural birch lignin at the same time and produced the benzimidazole derivatives in up to 67 wt% total yields.

The Trityl Cation Embedded into a [7]Helicene-Like Backbone: Preparation and Application as a Lewis Acid Catalyst

The synthesis of a helically chiral carbenium ion is reported. The new motif is essentially a trityl cation embedded into a [7]helicene-like framework. The key step in its preparation establishes the π-extended fluorenone system in one step by an unprecedented palladium-catalyzed carbonylative annulation of a 4,4′-biphenanthryl-3,3′-diyl precursor. The racemic form of the new carbon Lewis acid was found to catalyze a representative set of reactions typically promoted by the trityl cation.

Synthesis of Indoles by Reductive Cyclization of Nitro Compounds Using Formate Esters as CO Surrogates

Alkyl and aryl formate esters were evaluated as CO sources in the Pd- and Pd/Ru-catalyzed reductive cyclization of 2-nitrostyrenes to give indoles. Whereas the use of alkyl formates requires the presence of a ruthenium catalyst such as Ru3(CO)12, the reaction with phenyl formate can be performed by using a Pd/phenanthroline complex alone. Phenyl formate was found to be the most effective CO source and the desired products were obtained in excellent yields, often higher than those previously reported using pressurized CO. The reaction tolerates many functional groups, including sensitive ones like a free aldehydic group or a pendant pyrrole. Detailed experiments and kinetic studies allow to conclude that the activation of phenyl formate is base-catalyzed and that the metal doesn't play a role in the decarbonylation step. The reactions can be performed in a single thick-walled glass tube with as little as 0.2 mol-% palladium catalyst and even on a 2 g scale. The same protocol can be extended to other nitro compounds, affording different heterocycles.

Oxidative α-C-C Bond Cleavage of 2° and 3° Alcohols to Aromatic Acids with O2at Room Temperature via Iron Photocatalysis

The selective α-C-C bond cleavage of unfunctionalized secondary (2°) and tertiary alcohols (3°) is essential for valorization of macromolecules and biopolymers. We developed a blue-light-driven iron catalysis for aerobic oxidation of 2° and 3° alcohols to acids via α-C-C bond cleavages at room temperature. The first example of oxygenation of the simple tertiary alcohols was reported. The iron catalyst and blue light play critical roles to enable the formation of highly reactive O radicals from alcohols and the consequent two α-C-C bond cleavages.

Visible-light-induced oxidative lignin c-c bond cleavage to aldehydes using vanadium catalysts

Lignin is the largest carrier of aromatics on earth, and its depolymerization can afford value-Added aromatic products. Direct cleavage of the C-C bonds in lignin linkages is significant, but it is challenging to obtain low-molecular-weight aromatic monomers. Herein, using vanadium catalysts under visible light, we selectively cleave the C-C bonds in β-1 and β-O-4 interlinkages occluded in lignin models and extracts by an oxidative protocol. Visible light irradiation triggered single electron transfer between the substrate and the catalyst, which further induced the selective Cα-Cβ bond cleavage and generated the final aromatic products through radical intermediates. Using this photocatalytic chemistry, the reactivity of lignin models and the selectivity of Cα-Cβ bond cleavage were significantly improved. More importantly, this protocol affords aromatic monomers through the fragmentation of organosolv lignins even at room temperature, indicating the potential of photocatalytic C-C bond cleavage of lignin linkages under ambient conditions.

The formyloxyl radical: Electrophilicity, C-H bond activation and anti-Markovnikov selectivity in the oxidation of aliphatic alkenes

In the past the formyloxyl radical, HC(O)O, had only been rarely experimentally observed, and those studies were theoretical-spectroscopic in the context of electronic structure. The absence of a convenient method for the preparation of the formyloxyl radical has precluded investigations into its reactivity towards organic substrates. Very recently, we discovered that HC(O)O is formed in the anodic electrochemical oxidation of formic acid/lithium formate. Using a [CoIIIW12O40]5- polyanion catalyst, this led to the formation of phenyl formate from benzene. Here, we present our studies into the reactivity of electrochemically in situ generated HC(O)O with organic substrates. Reactions with benzene and a selection of substituted derivatives showed that HC(O)O is mildly electrophilic according to both experimentally and computationally derived Hammett linear free energy relationships. The reactions of HC(O)O with terminal alkenes significantly favor anti-Markovnikov oxidations yielding the corresponding aldehyde as the major product as well as further oxidation products. Analysis of plausible reaction pathways using 1-hexene as a representative substrate favored the likelihood of hydrogen abstraction from the allylic C-H bond forming a hexallyl radical followed by strongly preferred further attack of a second HC(O)O radical at the C1 position. Further oxidation products are surmised to be mostly a result of two consecutive addition reactions of HC(O)O to the CC double bond. An outer-sphere electron transfer between the formyloxyl radical donor and the [CoIIIW12O40]5- polyanion acceptor forming a donor-acceptor [D+-A-] complex is proposed to induce the observed anti-Markovnikov selectivity. Finally, the overall reactivity of HC(O)O towards hydrogen abstraction was evaluated using additional substrates. Alkanes were only slightly reactive, while the reactions of alkylarenes showed that aromatic substitution on the ring competes with C-H bond activation at the benzylic position. C-H bonds with bond dissociation energies (BDE) ≤ 85 kcal mol-1 are easily attacked by HC(O)O and reactivity appears to be significant for C-H bonds with a BDE of up to 90 kcal mol-1. In summary, this research identifies the reactivity of HC(O)O towards radical electrophilic substitution of arenes, anti-Markovnikov type oxidation of terminal alkenes, and indirectly defines the activity of HC(O)O towards C-H bond activation.

MATRIX METALLOPROTEINASE (MMP) INHIBITORS AND METHODS OF USE THEREOF

Hydantoin based compounds useful as inhibitors of matrix metalloproteinases (MMPs), particularly macrophage elastase (MMP-12) are described. Also described are related compositions and methods of using the compounds to inhibit MMP-12 and treat diseases mediated by MMP-12, such as asthma, chronic obstructive pulmonary disease (COPD), emphysema, acute lung injury, idiopathic pulmonary fibrosis (IPF), sarcoidosis, systemic sclerosis, liver fibrosis, nonalcoholic steatohepatitis (NASH), arthritis, cancer, heart disease, inflammatory bowel disease (IBD), acute kidney injury (AKI), chronic kidney disease (CKD), Alport syndrome, and nephritis.

PROCESS FOR MAKING FORMIC ACID UTILIZING LOWER-BOILING FORMATE ESTERS

Disclosed is a process for recovering formic acid from a formate ester of a C3 to C4 alcohol. Disclosed is also a process for producing formic acid by carbonylating a C3 to C4 alcohol, hydrolyzing the formate ester of the alcohol, and recovering a formic acid product. The alcohol may be dried and returned to the reactor. The process enables a more energy efficient production of formic acid than the carbonylation of methanol to produce methyl formate.