94-46-2

Usage

Preparation

By transesterification of methyl benzoate and isoamyl alcohol in the presence of potassium isoamylate; also by heating benzyl chloride and isoamyl acetate.

Metabolism

Benzoic acid is metabolized in the mammalian body after conjugation with glycine to form hippuric acid and benzoylglucuronic acid, which are excreted in the urine(Williams, 1959).

InChI:InChI=1/C12H16O2/c1-10(2)8-9-14-12(13)11-6-4-3-5-7-11/h3-7,10H,8-9H2,1-2H3

Upstream product

• 93-58-3 benzoic acid methyl ester 
• 123-51-3 i-Amyl alcohol 
• 98-08-8 α,α,α-trifluorotoluene 
• 93-89-0 benzoic acid ethyl ester 
• 643-94-7 o-phenylene dibenzoate 
• 5435-44-9 (E)-3-Ureido-but-2-enoic acid ethyl ester 
• 3741-66-0 Ethyl benzoyl carbonate 
• 94-01-9 resorcinol dibenzoate 
• 122842-83-5 1,4-bis-benzoyloxy-2-chloro-benzene 
• 123-92-2 3-methyl-1-butyl acetate 
• 555-75-9 aluminum ethoxide 
• 100-52-7 benzaldehyde 
• 590-86-3 isovaleraldehyde 
• 98-88-4 benzoyl chloride 

Downstream Products

• 532-32-1 sodium benzoate 
• 105-68-0 isoamyl propionate 
• 25183-19-1 isopentyl cyclohexanecarboxylate 
• 563-45-1 3-Methyl-1-butene 
• 65-85-0 benzoic acid 
• 71-43-2 benzene 
• 1130025-28-3 5-methoxy-3,3-dimethyl-5-oxo-4-phenylpentyl benzoate 
• 5205-04-9 (3-hydroxy-3-methylbutyl) benzoate 
• 1009091-33-1 2-azido-2-methylbutyl benzoate 

Relevant academic research and scientific papers

LiHMDS: Facile, highly efficient and metal-free transesterification under solvent-free condition

Transesterification is one of the important organic reactions employed in numerous industrial as well as laboratory applications for the synthesis of various esters. Herein, we report a rapid, highly efficient, and transition metal-free transesterification reaction in the presence of LiHMDS under solvent-free conditions. The transesterification reaction was carried out with three different benzoate esters and a wide range of primary and secondary alcohols (from C3-C18) in good to excellent yields (45 examples). By considering the commercial role of esters, this method will be promising for the facile synthesis of esters in industry-relevant applications.

Enolate-Based Regioselective Anti-Beckmann C-C Bond Cleavage of Ketones

The Baeyer-Villiger or Beckmann rearrangements are established methods for the cleavage of ketone derivatives under acidic conditions, proceeding for unsymmetrical precursors selectively at the more substituted site. However, the fragmentation regioselectivity cannot be switched and fragmentation at the less-substituted terminus is so far not possible. We report here that the reaction of ketone enolates with commercial alkyl nitrites provides a direct and regioselective way of fragmenting ketones into esters and oximes or ω-hydroxyimino esters, respectively. A comprehensive study of the scope of this reaction with respect to ketone classes and alkyl nitrites is presented. Control over the site of cleavage is gained through regioselective enolate formation by various bases. Oxidation of kinetic enolates of unsymmetrical ketones leads to the otherwise unavailable "anti-Beckmann"cleavage at the less-substituted side chain, while cleavage of thermodynamic enolates of the same ketones represents an alternative to the Baeyer-Villiger oxidation or the Beckmann rearrangement under basic conditions. The method is suited for the transformation of natural products and enables access to orthogonally reactive dicarbonyl compounds.

Zn-Mediated Hydrodeoxygenation of Tertiary Alkyl Oxalates

Herein we describe a general, mild, and scalable method for hydrodeoxygenation of readily accessible tertiary alkyl oxalates by Zn/silane under Ni-catalyzed conditions. The reduction method is suitable for an array of structural motifs derived from tertiary alcohols that bear diverse functional groups, including the synthesis of a key intermediate en route to estrone.

Hydrogenation of alkenes via cooperative hydrogen atom transfer

Radical hydrogenation via hydrogen atom transfer (HAT) to alkenes is an increasingly important transformation for the formation of thermodynamic alkane isomers. Current single-catalyst methods require stoichiometric oxidant in addition to hydride (H-) source to function. Here we report a new approach to radical hydrogenation: cooperative hydrogen atom transfer (cHAT), where each hydrogen atom donated to the alkene arrives from a different catalyst. Further, these hydrogen atom (H?) equivalents are generated from complementary hydrogen atom precursors, with each alkane requiring one hydride (H-) and one proton (H+) equivalent and no added oxidants. Preliminary mechanistic study supports this reaction manifold and shows the intersection of metal-catalyzed HAT and thiol radical trapping HAT catalytic cycles to be essential for effective catalysis. Together, this unique catalyst system allows us to reduce a variety of unactivated alkene substrates to their respective alkanes in high yields and diastereoselectivities and introduces a new approach to radical hydrogenation.

Metal catalyst-free photo-induced alkyl C-O bond borylation

Metal catalyst free, blue visible light-induced C-O bond borylation of unactivated tertiary alkyl methyl oxalates has been developed to furnish tertiary alkyl boronates. From the secondary alcohols activated with imidazolylthionyl, moderate yields of boronates were attained under standard photo-induced conditions. Preliminary mechanistic studies confirmed the involvement of a (DMF)2-B2cat2 adduct that weakly absorbs light at 437 nm so as to initiate a Bcat radical. A radical-chain process is proposed wherein the alkyl radical is engaged. This journal is

Method for reductive hydrogenation of tertiary alkyl alcohol

The invention discloses a method for reductive hydrogenation of tertiary alkyl alcohol. The method comprises the following steps: using oxalic ester prepared from tertiary alkyl alcohol in advance asa raw material, reacting at 40-60 DEG C for 8-12 hours under the actions of a nickel source, a ligand, a hydrogen donor, a reducing agent, an additive and a solvent to obtain a product of reductive hydrogenation of tertiary alkyl alcohol. Tertiary alkyl oxalate prepared from tertiary alkyl alcohol is used as a reaction precursor, zinc powder/magnesium chloride is used as a medium for catalytic reduction of non-activated tertiary alkyl oxalate, nickel promotes breakage of C-O bonds of oxalate, and diphenyl silane is used as a hydrogen donor for preparation of a reduction product. According to the method, the adopted catalyst metal is cheap, the raw materials are simple and easy to obtain, the reaction is mild and one-step, the steps are simple, the operation is safe, the yield is high, andthe cost is low.

Iron-Catalyzed Reductive Vinylation of Tertiary Alkyl Oxalates with Activated Vinyl Halides

We present herein a rare and efficient method for the creation of vinylated all carbon quaternary centers via Fe-catalyzed cross-electrophile coupling of vinyl halides with tertiary alkyl methyl oxalates. The reaction displays excellent functional group tolerance and broad substrate scope, which allows cascade radical cyclization and vinylation to afford complex bicyclic and spiral structural motifs. The reaction proceeds via tertiary alkyl radicals, and the putative vinyl-Br/Fe complexation appears to be crucial for activating the alkene and enabling a possibly concerted radical addition/C-Fe forming process.

Pd-Colloids-Catalyzed/Ag2O-Oxidized General and Selective Esterification of Benzylic Alcohols

Palladium colloids obtained from the degradation of Hermann–Beller palladacycle proved to be an efficient catalytic system in combination with silver oxide as a selective oxidant for the oxidative esterification of differently substituted benzyl alcohols in MeOH as solvent. Excellent reactivity exhibited by the catalytic system also allowed the alcoholic coupling partner to be changed from MeOH to a wide range of alcohols having diverse functionalities. The mildness of the developed protocol also made it possible to employ propargyl alcohol as the coupling partner without any observation of any interference of the terminal alkyne. Selective oxidative coupling of a primary alcoholic functional group over secondary in the case of glycols and glycerols was also made possible using the developed catalyst system. To test the relevancy of Pd/Ag combined catalysis mixed Pd/Ag colloids were synthesized, characterized by TEM, XRD and XPS and applied to oxidative-esterification successfully.

Safe and Facile Access to Nonstabilized Diazoalkanes Using Continuous Flow Technology

Despite the high synthetic potential of nonstabilized diazo compounds, their utilization has always been hampered by stability, toxicity, and safety issues. The present method opens up access to the most reactive nonstabilized diazoalkanes. Among diazo compounds, nonstabilized alkyl diazo compounds are the least represented because of their propensity to degrade during preparation. The continuous flow oxidation process of hydrazones on a silver oxide column afforded an output stream of base- and metal-free pure diazo solution in dichloromethane. Starting from innocuous ketones and aldehydes, this methodology allows the production of a broad range of unprecedented diazoalkanes compounds in excellent yields, while highlighting their synthetic potential and the possibility of safe large-scale diazo production.

Visible-Light-Promoted Activation of Unactivated C(sp3)-H Bonds and Their Selective Trifluoromethylthiolation

Selective functionalization of ubiquitous C(sp3)-H bonds using visible light is a highly challenging yet desirable goal in organic synthesis. The development of such processes relies on both rational design and serendipitous discoveries from innovative tools such as screening technologies. Applying a mechanism-based screening strategy, we herein report photoredox-mediated hydrogen atom transfer catalysis for the selective activation of otherwise unactivated C(sp3)-H bonds, followed by their trifluoromethylthiolation, which has high potential as a late-stage functionalization tool. The generality of this method is exhibited through incorporation of the trifluoromethylthio group in a large number of C(sp3)-H bonds with high selectivity without the need for an excess of valuable substrate.