4457-41-4

Upstream product

• 65-85-0 benzoic acid 
• 582-25-2 Potassium benzoate 
• 100-11-8 1-bromomethyl-4-nitro-benzene 
• 619-73-8 4-nitrobenzyl chloride 
• 17688-44-7 S-(benzoxazol-2-yl) thiobenzolate 
• 33388-23-7 3-benzoyl-2(3H)-benzoxazolethione 
• 54769-36-7 N-benzoyloxybenzotriazole 
• 81235-20-3 3-(benzothiazol-2-ylthio)-1,2-benzisothiazole 1,1-dioxide 
• 149-30-4 2-Mercaptobenzothiazole 
• 81245-06-9 3-(benzoxazol-2-ylthio)-1,2-benzisothiazole 1,1-dioxide 
• 2382-96-9 2-sulfanyl-1,3-benzoxazole 
• 139259-98-6 p-nitrobenzyl N-acetoxybenzogydroxamate 
• 2678-54-8 ketene diethyl acetal 
• 93-97-0 benzoic acid anhydride 

Downstream Products

• 619-73-8 4-nitrobenzyl chloride 
• 1070881-23-0 C₁₆H₁₅NO₃ 
• 6750-04-5 propargyl benzoate 
• 65-85-0 benzoic acid 

Relevant academic research and scientific papers

Nitroreductase-activated nitric oxide (NO) prodrugs

Due to the involvement of nitric oxide (NO) in numerous and diverse physiological processes, site-directed delivery of therapeutic NO in order to minimize unwanted side-effects is necessary. O2-(4-Nitrobenzyl) diazeniumdiolates are designed as

KMnO4-catalyzed chemoselective deprotection of acetate and controllable deacetylation-oxidation in one pot

A novel and efficient protocol for chemoselective deacetylation under ambient conditions was developed using catalytic KMnO4. The stoichiometric use of KMnO4 highlighted the dual role of a heterogeneous oxidant enabling direct access to aromatic aldehydes in one-pot sequential deacetylation-oxidation. The reaction employed an alternative solvent system and allowed the clean transformation of benzyl acetate to sensitive aldehyde in a single step while preventing over-oxidation to acids. Use of inexpensive and readily accessible KMnO4 as an environmentally benign reagent and the ease of the reaction operation were particularly attractive, and enabled the controlled oxidation and facile cleavage of acetate in a preceding step. This journal is

Catalytic conversion of ketones to esters: Via C(O)-C bond cleavage under transition-metal free conditions

The catalytic conversion of ketones to esters via C(O)-C bond cleavage under transition-metal free conditions is reported. This catalytic process proceeds under solvent-free conditions and offers an easy operational procedure, broad substrate scope with excellent selectivity, and reaction scalability. This journal is

A metal-free approach for the synthesis of amides/esters with pyridinium salts of phenacyl bromides via oxidative C–C bond cleavage

An efficient, simple, and metal-free synthetic approach for the N- and O-benzoylation of various amines/benzyl alcohols with pyridinium salts of phenacyl bromides is demonstrated to generate the corresponding amides and esters. This protocol facilitates the oxidative cleavage of a C–C bond followed by formation of a new C–N/C–O bond in the presence of K2CO3. Various pyridinium salts of phenacyl bromides can be readily transformed into a variety of amides and esters which is an alternative method for the conventional amidation and esterification in organic synthesis. High functional group tolerance, broad substrate scope and operational simplicity are the prominent advantages of the current protocol.

Base-Promoted Amidation and Esterification of Imidazolium Salts via Acyl C-C bond Cleavage: Access to Aromatic Amides and Esters

Imidazolium salts have been effectively employed as suitable acyl transfer agents in amidation and esterification in organic synthesis. The weak acyl C(O)-C imidazolium bond was exploited to generate acyl electrophiles, which further react with amines and alcohols to afford amides and esters. The broad substrate scope of anilines and benzylic amines and base-promoted conditions are the benefits of this route. Interestingly, phenol, benzylic alcohols, and a biologically active alcohol can also be subjected to esterification under the optimized conditions.

Systematic Evaluation of Sulfoxides as Catalysts in Nucleophilic Substitutions of Alcohols

Herein, a method for the nucleophilic substitution (SN) of benzyl alcohols yielding chloro alkanes is introduced that relies on aromatic sulfoxides as Lewis base catalysts (down to 1.5 mol-%) and benzoyl chloride (BzCl) as reagent. A systematic screening of various sulfoxides and other sulfinyl containing Lewis bases afforded (2-methoxyphenyl)methyl sulfoxide as optimal catalyst. In contrast to reported formamide catalysts, sulfoxides also enable the application of plain acetyl chloride (AcCl) as reagent. In addition, it was demonstrated that weakly electrophilic carboxylic acid chlorides like BzCl promote Pummerer rearrangement of sulfoxides already at room temperature. This side-reaction also provided the explanation, why sulfoxide catalyzed SN-reactions of alcohols do not allow the effective production of aliphatic and electron deficient chloro alkanes. Comparison experiments provided further insight into the reaction mechanism.

Azodicarboxylate-free esterification with triphenylphosphine mediated by flavin and visible light: method development and stereoselectivity control

Triphenylphosphine (Ph3P) activated by various electrophiles (e.g., alkyl diazocarboxylates) represents an effective mediator of esterification and other nucleophilic substitution reactions. We report herein an aza-reagent-free procedure using flavin catalyst (3-methyl riboflavin tetraacetate), triphenylphosphine, and visible light (448 nm), which allows effective esterification of aromatic and aliphatic carboxylic acids with alcohols. Mechanistic study confirmed that photoinduced electron transfer from triphenylphosphine to excited flavin with the formation of Ph3P+ is a crucial step in the catalytic cycle. This allows reactive alkoxyphosphonium species to be generated by reaction of an alcohol with Ph3P+ followed by single-electron oxidation. Unexpected stereoselectivity control by the solvent was observed, allowing switching from inversion to retention of configuration during esterification of (S)- or (R)-1-phenylethanol; for example with phenylacetic acid, the ratio shifting from 10?:?90 (retention?:?inversion) in trifluoromethylbenzene to 99.9?:?0.1 in acetonitrile. Our method uses nitrobenzene to regenerate the flavin photocatalyst. This new approach to flavin re-oxidation has also been successfully proved in benzyl alcohol oxidation, which is a “standard” process among flavin-mediated photooxidations.

Zn-Catalyzed tert-Butyl Nicotinate-Directed Amide Cleavage as a Biomimic of Metallo-Exopeptidase Activity

A two-step catalytic amide-to-ester transformation of primary amides under mild reaction conditions has been developed. A tert-butyl nicotinate (tBu nic) directing group is easily introduced onto primary amides via Pd-catalyzed amidation with tert-butyl 2-chloronicotinate. A weak base (Cs2CO3 or K2CO3) at 40-50 °C can be used provided that 1,1′-bis(dicyclohexylphosphino)ferrocene is selected as ligand. The tBu nic activated amides subsequently allow Zn(OAc)2-catalyzed nonsolvolytic alcoholysis in tBuOAc at 40-60 °C under neutral reaction conditions. The activation mechanism is biomimetic: the C3-ester substituent of the pyridine in the directing group populates the trans-conformer suitable for Zn-chelation, C=Oamide-Zn-Ndirecting group, and Zn-coordinated alcohol is additionally activated as a nucleophile by hydrogen bonding with the acetate ligand of the catalyst. Additionally, the acetate ligand assists in intramolecular O-to-N proton transfer. The chemoselectivity versus other functional groups and compatibility with challenging reaction partners, such as peptides, sugars, and sterols, illustrates the synthetic applicability of this two-step amide cleavage method. The tBu nic amides do not require purification before cleavage. Preliminary experiments also indicate that other weak nucleophiles can be used such as (hetero)arylamines (transamidation) as exemplified by 8-aminoquinoline.

Graphene Oxide: An Efficient Acid Catalyst for the Construction of Esters from Acids and Alcohols

Graphene oxide was found to be an efficient and reusable acid catalyst for the esterification reaction. A wide range of aliphatic and aromatic acids and alcohols were compatible with the standard conditions and afforded the corresponding products in good yields. The heterogeneous catalyst can be easily recovered and recycled in dichloro-ethane solvent with good catalytic activity.

Metal-Free Oxidative Cross Esterification of Alcohols via Acyl Chloride Formation

A novel metal-free oxidative cross esterification of alcohols has been achieved using trichloroisocyanuric acid as an oxidant. The alcohols were converted in situ into their corresponding acyl chlorides, which were then reacted with primary and secondary aliphatic, benzylic and allylic alcohols and phenols. A wide variety of esters was obtained in satisfactory yields.