40291-39-2

Usage

Uses

Used in Chemical Synthesis:
ETHYL O-TOLYLACETATE is used as a chemical intermediate for the preparation of β-o-tolylethyl alcohol by Bouveault's method. This application takes advantage of its reactivity and ability to undergo specific chemical transformations, contributing to the synthesis of desired compounds in the chemical industry.

InChI:InChI=1/C11H14O2/c1-3-13-11(12)8-10-7-5-4-6-9(10)2/h4-7H,3,8H2,1-2H3

Upstream product

• 57408-55-6 orthoacetic acid diethyl ester-benzyl ester 
• 22364-68-7 2-tolylmethylnitrile 
• 64-17-5 ethanol 
• 201230-82-2 carbon monoxide 
• 7341-24-4 2-methylbenzyl mercaptan 
• 644-36-0 o-methylphenylacetic acid 
• 95-46-5 2-methylphenyl bromide 
• 681-94-7 ethyl 2-(tributylstannyl)acetate 
• 141-52-6 sodium ethanolate 
• 552-45-4 1-chloromethyl-2-methylbenzene 
• 555-75-9 aluminum ethoxide 
• 89-92-9 2-methylbenzyl bromide 
• 7647-01-0 hydrogenchloride 
• 16419-60-6 2-Methylphenylboronic acid 

Downstream Products

• 16793-90-1 1-(2-bromoethyl)-2-methylbenzene 
• 859195-37-2 methyl-(2-methyl-phenethyl)-malonic acid diethyl ester 
• 727-94-6 (1H-indol-3-yl)(o-tolyl)methanone 
• 66644-67-5 ethyl 2-methylbenzoylformate 
• 91670-47-2 (Z)-3-(2-Methyl-benzoylamino)-2-o-tolyl-acrylic acid 
• 91632-45-0 2,5-Di-o-tolyl-[1,3]oxazin-6-one 
• 91632-31-4 4-o-Tolyl-2H-isoxazol-5-one 
• 428500-95-2 p-methoxyphenyl 3-O-[(2-azidomethyl)phenylacetyl]-4,6-O-benzylidene-2-deoxy-2-phthalimido-β-D-glucopyranoside 
• 428500-94-1 p-methoxyphenyl 3-O-[(2-azidomethyl)phenylacetyl]-2-deoxy-2-phthalimido-β-D-glucopyranoside 
• 428500-96-3 methyl 6-O-[(2-azidomethyl)phenylacetyl]-2,3,4-tri-O-benzyl-α-D-glucopyranoside 
• 428500-98-5 methyl 2,3,4-tri-O-acetyl-6-O-[(2-azidomethyl)phenylacetyl]-α-D-glucopyranoside 
• 428500-97-4 3-O-(2-azidomethyl)phenylacetyl-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose 
• 428501-02-4 ethyl 2-(2-(azidomethyl)phenyl)acetate 
• 24331-94-0 1,4-dihydro-3(2H)-isoquinolinone 

Relevant academic research and scientific papers

Photoassisted Cross-Coupling Reaction of α-Chlorocarbonyl Compounds with Arylboronic Acids

A Suzuki-Miyaura cross-coupling reaction of α-chloroacetates or α-chloroacetamides with arylboronic acids is made possible by visible-light irradiation. This reaction provides a useful method for the synthesis of α-arylacetates and α-arylacetamides from chlorides under mild reaction conditions. An indole-3-acetic acid derivative that is the key intermediate of the plant hormone auxin can be synthesized from 1-Boc-indole in two steps by combining an iridium-catalyzed C-H borylation and a palladium-catalyzed cross-coupling reaction.

Enantioselective Desymmetrization of 2-Aryl-1,3-propanediols by Direct O-Alkylation with a Rationally Designed Chiral Hemiboronic Acid Catalyst That Mitigates Substrate Conformational Poisoning

Enantioselective desymmetrization by direct monofunctionalization of prochiral diols is a powerful strategy to prepare valuable synthetic intermediates in high optical purity. Boron acids can activate diols toward nucleophilic additions; however, the design of stable chiral catalysts remains a challenge and highlights the need to identify new chemotypes for this purpose. Herein, the discovery and optimization of a bench-stable chiral 9-hydroxy-9,10-boroxarophenanthrene catalyst is described and applied in the highly enantioselective desymmetrization of 2-aryl-1,3-diols using benzylic electrophiles under operationally simple, ambient conditions. Nucleophilic activation and discrimination of the enantiotopic hydroxy groups on the diol substrate occurs via a defined chairlike six-membered anionic complex with the hemiboronic heterocycle. The optimal binaphthyl-based catalyst 1g features a large aryloxytrityl group to effectively shield one of the two prochiral hydroxy groups on the diol complex, whereas a strategically placed "methyl blocker"on the boroxarophenanthrene unit mitigates the deleterious effect of a competing conformation of the complexed diol that compromised the overall efficiency of the desymmetrization process. This methodology affords monoalkylated products in enantiomeric ratios equal or over 95:5 for a wide range of 1,3-propanediols with various 2-aryl/heteroaryl groups.

Expedient discovery for novel antifungal leads: 1,3,4-Oxadiazole derivatives bearing a quinazolin-4(3H)-one fragment

Developing novel fungicide candidates are intensively promoted by the rapid emergences of resistant fungi that outbreak on agricultural production. Aiming to discovery novel antifungal leads, a series of 1,3,4-oxadiazole derivatives bearing a quinazolin-4(3H)-one fragment were constructed for evaluating their inhibition effects against phytopathogenic fungi in vitro and in vivo. Systematically structural optimizations generated the bioactive molecule I32 that was identified as a promising inhibitor against Rhizoctonia solani with the in vivo preventative effect of 58.63% at 200 μg/mL. The observations that were captured by scanning electron microscopy and transmission electron microscopy demonstrated that the bioactive molecule I32 could induce the sprawling growth of hyphae, the local shrinkage and rupture on hyphal surfaces, the extreme swelling of vacuoles, the striking distortions on cell walls, and the reduction of mitochondria numbers. The above results provided an indispensable complement for the discovery of antifungal lead bearing a quinazolin-4(3H)-one and 1,3,4-oxadiazole fragment.

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.

Coupling of Reformatsky Reagents with Aryl Chlorides Enabled by Ylide-Functionalized Phosphine Ligands

The coupling of aryl chlorides with Reformatsky reagents is a desirable strategy for the construction of α-aryl esters but has so far been substantially limited in the substrate scope due to many challenges posed by various possible side reactions. This limitation has now been overcome by the tailoring of ylide-functionalized phosphines to fit the requirements of Negishi couplings. Record-setting activities were achieved in palladium-catalyzed arylations of organozinc reagents with aryl electrophiles using a cyclohexyl-YPhos ligand bearing an ortho-tolyl-substituent in the backbone. This highly electron-rich, bulky ligand enables the use of aryl chlorides in room temperature couplings of Reformatsky reagents. The reaction scope covers diversely functionalized arylacetic and arylpropionic acid derivatives. Aryl bromides and chlorides can be converted selectively over triflate electrophiles, which permits consecutive coupling strategies.

N-Heterocyclic Carbenes as Key Intermediates in the Synthesis of Fused, Mesoionic, Tricyclic Heterocycles

Coupling between 5-bromoimidazo[1,5-a]pyridinium salts and malonate or arylacetate esters leads to a facile and straightforward access to the new mesoionic, fused, tricyclic system of imidazo[2,1,5-cd]indolizinium-3-olate. Mechanistic studies show that the reaction pathway consists of nucleophilic aromatic substitution on the cationic, bicyclic heterocycle by an enolate-type moiety and in the nucleophilic attack of a transient free N-heterocyclic carbene (NHC) species on the ester group; the relative order of these two steps depends on the nature of the starting ester. This work highlights the valuable implementation of free NHC species as key intermediates in synthetic chemistry, beyond their classical use as stabilizing ligands or organocatalysts.

Aromatic Claisen Rearrangements of Benzyl Ketene Acetals: Conversion of Benzylic Alcohols to (ortho-Tolyl)acetates

Claisen rearrangements of benzyl vinyl ethers are much less facile than those of aliphatic allyl vinyl ethers, and their synthetic utility has remained relatively unexplored. A one-pot procedure is reported for the generation and Claisen rearrangement of benzyl vinyl ethers that contain an activating α-alkoxy substituent on the vinyl group. A [3,3]-sigmatropic mechanism was supported by trapping of the intermediate isotoluene in an intramolecular Alder–ene reaction.

Mechanistic studies on gold-catalyzed direct arene c-h bond functionalization by carbene insertion: The coinage-metal effect

The catalytic functionalization of the Csp2-H bond of benzene by means of the insertion of the CHCO2Et group from ethyl diazoacetate (N2= CHCO2Et) has been studied with the series of coinage-metal complexes IPrMCl (IPr = 1,3-bis- (diisopropylphenyl)imidazol-2-ylidene) and NaBArF 4 (BArF 4 = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate). For Cu and Ag, these examples constitute the first use of such metals toward this transformation, which also provides ethyl cyclohepta-2,4,6-trienecarboxylate as a byproduct from the so-called Buchner reaction. In the case of methyl-substituted benzenes, the reaction exclusively proceeds onto the aromatic ring, the Csp3-H bond remaining unreacted. A significant coinage-metal effect has been observed, since the gold catalyst favors the formation of the insertion product into the Csp2-H bond whereas copper and silver preferentially induce the formation of the cycloheptatriene derivative. Experimental studies and theoretical calculations have explained the observed selectivity in terms of the formation of a common Wheland intermediate, resembling an electrophilic aromatic substitution, from which the reaction pathway evolves into two separate routes to each product.

Modular Synthesis of Arylacetic Acid Esters, Thioesters, and Amides from Aryl Ethers via Rh(II)-Catalyzed Diazo Arylation

One-pot formation of arylacetic acid esters, thioesters, and amides via Rh(II)-catalyzed arylation of a Meldrum's acid-derived diazo reagent with electron-rich arenes is described. The methodology was used to efficiently synthesize an anticancer compound.

Iron and manganese catalysts for the selective functionalization of arene C(sp2)-H bonds by carbene insertion

The first examples of the direct functionalization of non-activated aryl sp2 C-H bonds with ethyl diazoacetate (N2CHCO2Et) catalyzed by Mn- or Fe-based complexes in a completely selective manner are reported, with no formation of the frequently observed cycloheptatriene derivatives through competing Buchner reaction. The best catalysts are FeII or MnII complexes bearing the tetradentate pytacn ligand (pytacn= 1-(2-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane). When using alkylbenzenes, the alkylic C(sp3)-H bonds of the substituents remained unmodified, thus the reaction being also selective toward functionalization of sp2 C-H bonds. Exclusive catalysis: Iron- and-manganese-based catalysts selectively functionalize the C(sp2)-H bonds of benzene or alkylbenzenes through the formal insertion of the CHCO2Et group from N2CHCO2Et (see scheme). When using alkylbenzenes, the alkylic C(sp3)-H bonds of the substituents remain unmodified.