101-94-0

Basic information

• Product Name: p-Tolyl phenylacetate
• Synonyms: 4-METHYLPHENYL PHENYLACETATE;4-CRESYL PHENYLACETATE;FEMA 3077;P-TOLYL PHENYLACETATE;P-TOLYL A-TOLUATE;PHENYLACETIC ACID P-CRESYL ESTER;PHENYLACETIC ACID P-TOLYL ESTER;P-CRESYL A-TOLUATE
• CAS NO: 101-94-0
• Molecular Formula: C₁₅H₁₄O₂
• Molecular Weight: 226.27
• EINECS: 202-990-1
• Product Categories: Pharmaceutical Raw Materials;Alphabetical Listings;Flavors and Fragrances;Q-Z
• Mol File: 101-94-0.mol

Chemical Properties

• Melting Point: 74-76 °C(lit.)
• Boiling Point: 148 °C / 1.5mmHg
• Flash Point: 122.3 °C
• Appearance: /
• Density: 1.108 g/cm³
• Vapor Pressure: 2.33E-05mmHg at 25°C
• Refractive Index: 1.569
• Storage Temp.: Sealed in dry,Room Temperature
• Merck: 14,2585
• CAS DataBase Reference: p-Tolyl phenylacetate(CAS DataBase Reference)
• NIST Chemistry Reference: p-Tolyl phenylacetate(101-94-0)
• EPA Substance Registry System: p-Tolyl phenylacetate(101-94-0)

Safety Data

• WGK Germany: 2
• RTECS: CY1679750
• Hazardous Substances Data: 101-94-0(Hazardous Substances Data)

Usage

Uses

Used in Perfumery Industry:
p-Tolyl phenylacetate is used as an ingredient in jasmine, narcissus, hyacinth, lily, and jonquille perfume compositions for its sweet, honey-like flavor and tenacious lily, hyacinth, narcissus odor.
Used as a Fixative:
p-Tolyl phenylacetate is used as a fixative in perfumery to help extend the longevity of the fragrance.
Used in Soap and Household Products Industry:
p-Tolyl phenylacetate is used as a fragrance ingredient in soaps and household products to provide a pleasant scent.

Preparation

From p-cresol and phenylacetic acid by esterification, or by heating phenylacetyl chloride with freshly distilled p-cresol.

InChI:InChI=1/C15H14O2/c1-12-7-9-14(10-8-12)17-15(16)11-13-5-3-2-4-6-13/h2-10H,11H2,1H3

Synthetic route

p-cresol (106-44-5) + 3-phenylethanoic dithioperoxyanhydride (15088-78-5) → p-tolyl phenylacetate (101-94-0)

Conditions	Yield
With dmap; triethylamine In dichloromethane at 20℃; for 2h;	90%

p-cresol (106-44-5) + N,N,N-­trimethyl-­1-­phenylmethanaminium trifluoromethanesulfonate (260783-80-0) + carbon monoxide (201230-82-2) → p-tolyl phenylacetate (101-94-0)

Conditions	Yield
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; sodium carbonate; triphenylphosphine In toluene at 100℃; under 760.051 Torr; for 8h; Schlenk technique;	83%

phenylacetic acid (103-82-2) + p-cresol (106-44-5) → p-tolyl phenylacetate (101-94-0)

Conditions	Yield
acid activated Indian bentonite catalyst In o-xylene for 4h; Heating;	80%
With PPA
With trichlorophosphate
With Amberlyst15 In neat (no solvent) at 90℃; Kinetics; Activation energy; Catalytic behavior; Reagent/catalyst; Time; Concentration; Temperature; Green chemistry;
With Fuller's Earth at 190℃;

phenylacetic acid (103-82-2) + tris(p-methylphenyl) borate (14643-62-0) → p-tolyl phenylacetate (101-94-0)

phenylacetic anhydride (1555-80-2) + p-cresol (106-44-5) → p-tolyl phenylacetate (101-94-0)

p-cresol (106-44-5) + phenylacetyl chloride (103-80-0) → p-tolyl phenylacetate (101-94-0)

α-p-tolyloxy-cinnamic acid → carbon dioxide (124-38-9) + p-tolyl phenylacetate (101-94-0) + styryl-p-tolyl ether (66694-13-1, 66694-16-4, 32546-88-6) + CO

Conditions	Yield
at 260 - 270℃;

phenylacetic acid (103-82-2) → p-tolyl phenylacetate (101-94-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: acetic acid anhydride View Scheme
Multi-step reaction with 2 steps 1: N,N-dimethyl-formamide; oxalyl dichloride / dichloromethane / 20 °C 2: sodium hydroxide / water / 2 h View Scheme

phenylacetyl chloride (103-80-0) → p-tolyl phenylacetate (101-94-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: tetrabutylammomium bromide; sodium sulfide / toluene; water / 1 h / 20 °C 2: dmap; triethylamine / dichloromethane / 2 h / 20 °C View Scheme

N,N'-dimethylbenzylamine (103-83-3) → p-tolyl phenylacetate (101-94-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: diethyl ether / 0.5 h / 0 °C 2: (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; triphenylphosphine; sodium carbonate / toluene / 8 h / 100 °C / 760.05 Torr / Schlenk technique View Scheme

p-tolyl phenylacetate (101-94-0) → 1-(2-hydroxy-4-methylphenyl)-2-phenylethan-1-one (2491-34-1)

Conditions	Yield
With Nafion-Na(1+) 117 membrane In water for 7h; Irradiation;	100%
Product distribution; Mechanism; Ambient temperature; Irradiation; photolysis on NaY zeolite;	100 % Spectr.

p-tolyl phenylacetate (101-94-0) + benzylamine (100-46-9) → N-benzylphenylacetamide (7500-45-0)

Conditions	Yield
With tetra-(n-butyl)ammonium iodide In dichloromethane Ambient temperature; electrolized at -1.7 V at 50 mA;	93%

propylamine (107-10-8) + p-tolyl phenylacetate (101-94-0) → N-(n-propyl)phenylacetamide (64075-36-1)

Conditions	Yield
With tetra-(n-butyl)ammonium iodide In dichloromethane Ambient temperature; electrolyzed at -1.7 V at 50 mA;	85%

p-tolyl phenylacetate (101-94-0) → 1-(2-hydroxy-5-methylphenyl)-2-phenylethanone (24258-63-7)

Conditions	Yield
With methanesulfonic acid; Methanesulfonic anhydride at 65℃; Fries rearrangement; Inert atmosphere; regioselective reaction;	81%
With aluminium trichloride at 130℃;
With aluminium trichloride 1.) CS2, 2.) 130-140 deg C, 3 h; Yield given. Multistep reaction;
With aluminum (III) chloride In chlorobenzene at 80℃;
With aluminum (III) chloride In chlorobenzene at 130℃; for 3h; Fries Phenol Ester Rearrangement;

p-tolyl phenylacetate (101-94-0) + 2-(3,4-dimethoxyphenyl)-ethylamine (120-20-7) → N-(3,4-dimethoxyphenethyl)-phenyl acetamide (4876-02-2)

Conditions	Yield
With tetra-(n-butyl)ammonium iodide In dichloromethane Ambient temperature; electrolyzed at1.7 V at 50 mA;	80%

p-tolyl phenylacetate (101-94-0) + rac-methylbenzylamine (618-36-0) → (S)-2-phenyl-N-(1-phenylethyl)acetamide (17194-90-0)

Conditions	Yield
With tetra-(n-butyl)ammonium iodide In dichloromethane Ambient temperature; electrolyzed at -1.7 V at 50 mA;	65%

p-tolyl phenylacetate (101-94-0) + aniline yellow (60-09-3) → 2-Phenyl-N-(4-phenylazo-phenyl)-acetamide (108133-62-6)

Conditions	Yield
With tetra-(n-butyl)ammonium iodide In dichloromethane Ambient temperature; electrolyzed at -1.7 V at 50 mA;	54%

p-tolyl phenylacetate (101-94-0) → 1-(2-hydroxy-4-methylphenyl)-2-phenylethan-1-one (2491-34-1) + (benzyloxy)benzene (946-80-5) + 1,1'-(1,2-ethanediyl)bisbenzene (103-29-7) + phenol (108-95-2)

Conditions	Yield
In acetonitrile Product distribution; Mechanism; Ambient temperature; Irradiation;	A 79.7 % Spectr. B 3.3 % Spectr. C 8.5 % Spectr. D 6.8 % Spectr.

p-tolyl phenylacetate (101-94-0) → toluene (108-88-3) + phenol (108-95-2)

Conditions	Yield
Product distribution; Mechanism; Ambient temperature; Irradiation; photolysis on ZSM-5 zeolite;	A 100 % Spectr. B 73.0 % Spectr.

aluminium trichloride (7446-70-0) + p-tolyl phenylacetate (101-94-0) → 1-(2-hydroxy-5-methylphenyl)-2-phenylethanone (24258-63-7)

Conditions	Yield
at 135℃;

p-tolyl phenylacetate (101-94-0) → 3-Dimethylamino-1-(2-hydroxy-5-methyl-phenyl)-2-phenyl-propan-1-one (119304-62-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: 1.) AlCl3 / 1.) CS2, 2.) 130-140 deg C, 3 h 2: 1.) HCl / 1.) EtOH, H2O, 60-70 deg C, 15 min, 2.) EtOH, H2O, reflux, 6 h View Scheme

p-tolyl phenylacetate (101-94-0) → 3-Diethylamino-1-(2-hydroxy-5-methyl-phenyl)-2-phenyl-propan-1-one (119304-61-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: 1.) AlCl3 / 1.) CS2, 2.) 130-140 deg C, 3 h 2: 1.) HCl / 1.) EtOH, H2O, 60-70 deg C, 15 min, 2.) EtOH, H2O, reflux, 6 h View Scheme

p-tolyl phenylacetate (101-94-0) → 1-(2-Hydroxy-5-methyl-phenyl)-2-phenyl-3-pyrrolidin-1-yl-propan-1-one (119304-60-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: 1.) AlCl3 / 1.) CS2, 2.) 130-140 deg C, 3 h 2: 1.) HCl / 1.) EtOH, H2O, 60-70 deg C, 15 min, 2.) EtOH, H2O, reflux, 6 h View Scheme

p-tolyl phenylacetate (101-94-0) → 1-(2-Hydroxy-5-methyl-phenyl)-2-phenyl-3-piperidin-1-yl-propan-1-one (119304-59-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: 1.) AlCl3 / 1.) CS2, 2.) 130-140 deg C, 3 h 2: 1.) HCl / 1.) EtOH, H2O, 60-70 deg C, 15 min, 2.) EtOH, H2O, reflux, 6 h View Scheme

p-tolyl phenylacetate (101-94-0) → 1-(2-Hydroxy-5-methyl-phenyl)-3-morpholin-4-yl-2-phenyl-propan-1-one (119304-58-4)

Conditions	Yield
Multi-step reaction with 2 steps 1: 1.) AlCl3 / 1.) CS2, 2.) 130-140 deg C, 3 h 2: 1.) HCl / 1.) EtOH, H2O, 60-70 deg C, 15 min, 2.) EtOH, H2O, reflux, 6 h View Scheme

p-tolyl phenylacetate (101-94-0) → C16H14O2

Conditions	Yield
Multi-step reaction with 2 steps 1: aluminum (III) chloride / chlorobenzene / 80 °C 2: trifluoroacetic acid; diisopropylamine / tetrahydrofuran / 67 °C View Scheme

p-tolyl phenylacetate (101-94-0) → 1-(2-hydroxy-5-methylphenyl)-2,3-diphenylpropan-1-one

Conditions	Yield
Multi-step reaction with 2 steps 1: aluminum (III) chloride / chlorobenzene / 80 °C 2: potassium carbonate / N,N-dimethyl acetamide / 20 °C View Scheme

p-tolyl phenylacetate (101-94-0) → 1-(2-hydroxy-5-methylphenyl)-2-phenyl-3-(o-tolyl)propan-1-one

Conditions	Yield
Multi-step reaction with 2 steps 1: aluminum (III) chloride / chlorobenzene / 80 °C 2: potassium carbonate / N,N-dimethyl acetamide / 20 °C View Scheme

p-tolyl phenylacetate (101-94-0) → C23H22O2

Conditions	Yield
Multi-step reaction with 2 steps 1: aluminum (III) chloride / chlorobenzene / 80 °C 2: potassium carbonate / N,N-dimethyl acetamide / 20 °C View Scheme

Upstream product

• 103-82-2 phenylacetic acid 
• 106-44-5 p-cresol 
• 14643-62-0 tris(p-methylphenyl) borate 
• 1555-80-2 phenylacetic anhydride 
• 103-80-0 phenylacetyl chloride 
• 15088-78-5 3-phenylethanoic dithioperoxyanhydride 
• 103-83-3 N,N'-dimethylbenzylamine 
• 260783-80-0 N,N,N--trimethyl--1--phenylmethanaminium trifluoromethanesulfonate 
• 201230-82-2 carbon monoxide 

Downstream Products

• 24258-63-7 1-(2-hydroxy-5-methylphenyl)-2-phenylethanone 
• 64075-36-1 N-(n-propyl)phenylacetamide 
• 4876-02-2 N-(3,4-dimethoxyphenethyl)-phenyl acetamide 
• 108133-62-6 2-Phenyl-N-(4-phenylazo-phenyl)-acetamide 
• 17194-90-0 N-[(1S)-1-phenylethyl]-benzeneacetamide 
• 7500-45-0 N-benzylphenylacetamide 
• 2491-34-1 1-(2-hydroxy-4-methylphenyl)-2-phenylethan-1-one 
• 946-80-5 (benzyloxy)benzene 
• 103-29-7 1,1'-(1,2-ethanediyl)bisbenzene 
• 108-95-2 phenol 
• 108-88-3 toluene 
• 119304-58-4 1-(2-Hydroxy-5-methyl-phenyl)-3-morpholin-4-yl-2-phenyl-propan-1-one 
• 119304-59-5 1-(2-Hydroxy-5-methyl-phenyl)-2-phenyl-3-piperidin-1-yl-propan-1-one 
• 119304-60-8 1-(2-Hydroxy-5-methyl-phenyl)-2-phenyl-3-pyrrolidin-1-yl-propan-1-one 

Relevant articles and documents

Ion-exchange resin catalysis in benign synthesis of perfumery grade p-cresylphenyl acetate from p-cresol and phenylacetic acid

p-Cresylphenyl acetate is a very important perfume that finds wide applications and possesses an organoleptic character similar to those of honey, nuts, and butter. It is produced by mineral acid-catalyzed esterification of p-cresol with phenylacetic acid. Use of homogeneous acid catalysts leads to posttreatment pollution problems apart from the quality-related issues. The current work is focused with an eco-friendly and benign catalytic process, employing the solid acid catalysts such as dodecatungstophosphoric acid (DTP) supported on K-10 clay, ion-exchange resins, sulfated zirconia, etc. for esterification of p-cresol with phenylacetic acid to p-cresylphenyl acetate. The order of catalytic activity was found to be Amberlyst-15 ≈ Indion-125 > 20% w/w DTP/K-10 > sulfated zirconia. Indion-125 was used for further experiments. It was observed that the catalyst has excellent reusability and that the reaction was 100% selective towards p-cresylphenyl acetate. A pseudo-first-order kinetic model was built up to fit the experimental data, and the apparent activation energy was found to be 9.56 kcal/mol.

Synthesis of 7-hydroxy-6H-naphtho[2,3-c]coumarinviaa TsOH-mediated tandem reaction

A concise and efficient method for the synthesis of 7-hydroxy-6H-naphtho[2,3-c]coumarin using available 1-(2-hydroxyphenyl)-2-phenylethanone and Meldrum's acid has been developed. This transformation involved a tandem aldol reaction/lactonization/Friedel-Crafts reaction to form a lactone ring and a benzene ring. It showed high atom economy with water and acetone as the byproducts. Mechanism studies demonstrated two roles of Meldrum's acid: (i) as the reagent for the tandem reaction, and (ii) as the catalyst for the Friedel-Crafts reaction. Moreover, the hydroxyl group of 7-hydroxy-6H-naphtho[2,3-c]coumarin was further functionalized efficiently by arylethynyl, aryl, and cyano groups to furnish D-π-A compounds with excellent fluorescence emissions (ΦF= 0.14-0.78).

Palladium-catalyzed carbonylation of benzylic ammonium salts to amides and esters: Via C-N bond activation

An efficient palladium-catalyzed carbonylation reaction of readily available quaternary ammonium salts with CO is reported for the first time to afford arylacetamides and arylacetic acid esters via benzylic C-N bond cleavage. This protocol features mild reaction conditions under atmospheric pressure of CO, a redox-neutral process without an additional oxidant, and a broad substrate scope for various kinds of amines, alcohols and phenols.

C-H Functionalization via Remote Hydride Elimination: Palladium Catalyzed Dehydrogenation of ortho-Acyl Phenols to Flavonoids

Although deprotonation of electron-poor C-H bonds to carbon anions with bases has long been known and widely used in organic synthesis, the hydride elimination from electron-rich C-H bonds to carbon cations or partial carbocations for the introduction of nucleophiles is a comparatively less explored area. Here we report that the carbonyl β-C(sp3)-H bond hydrogens of ortho-acyl phenols could be substituted by intramolecular phenolic hydroxyls to form O-heterocycles, followed by dehydrogenation of the O-heterocycle into flavonoids. The cascade reaction is catalyzed by Pd/C without added oxidants and sacrificing hydrogen acceptors.

Diacyl Disulfide: A Reagent for Chemoselective Acylation of Phenols Enabled by 4-(N,N-Dimethylamino)pyridine Catalysis

A general and excellent acylation reagent, diacyl disulfide, was uncovered for efficient ester formation enabled by DMAP (4-(N,N-dimethylamino)pyridine) catalysis. This protocol offered a promising synthetic platform on site-selective acylation of phenolic and primary aliphatic hydroxyl groups, which greatly expanded the realm of protecting group chemistry. The importance of the reagent was also reflected by its excellent moisture tolerance, high efficiency, and potential in synthetic chemistry and biologically meaningful natural product modification.

Direct esterification of carboxylic acids with p-cresol catalysed by acid activated Indian bentonite

Acid activated Indian bentonite (AAIB) catalyst is used for the first time to esterify various carboxylic acids with p-cresol in average to excellent yields. Optimisation studies have been carried out for p-cresyl stearate synthesis. The catalyst is recoverable and recyclable.

REGIOSELECTIVITY OF COMPLEXATIONS OF SUBSTITUTED PHENYL BENZOATES AND PHENYL PHENYLACETATES WITH Cr(CO)6

Selectivity of complexation of substituted phenyl benzoates is very low.In most cases, comparable yields of both regioisomeric complexes are isolated.Exception is 4-chlorophenyl ester, where benzoic acid moiety is complexed nearly exclusively.Very high regioselectivity of complexation was observed with substituted phenyl phenylacetates.The substituent of substituted phenols has not any effect on the complexation, and only phenylacetic acid moiety is complexed.This observation supports the recently proposed mechanism of the catalytic activity of the esters at arene complexation.

Alkaline Hydrolysis of Aryl Phenylacetates and Aryl 4-Nitrophenylacetates. Evidence consistent with an Elimination-Addition Mechanism

Hydrolysis of the substituted phenyl esters of phenylacetic acid is found to be first order each in the ester and hydroxide ion.Hydrolysis is catalysed by general bases and the catalytic coefficients for the substituted phenoxides obey the Broensted relation with β +0.49.The rate of hydrolysis of the esters of 4-nitrophenylacetic acid is independent of in the range employed.Both series of reactions exhibit low solvent isotope effect and high sensitivity to substituents in the leaving group .These datasuggest an E1cB mechanism for the hydrolysis.The keten intermediate envisaged for such a mechanism has been trapped as the anilide when the reactions are conducted in aniline buffers, without any effect on the rate of hydrolysis for variations in .An increase in the DMSO content in the solvent decreases the rate of hydrolysis of the esters of 4-nitrophenylacetic acid, which is explained by an (E1cB)anion mechanism for the hydrolysis.Transfer to aqueous DMSO results in rate accelerations for the esters of phenylacetic acid which can be accounted for by either an (E1cB)Bion pair or (E1cB)reversible mechanism for the hydrolysis.