26537-19-9

Basic information

• Product Name: Methyl 4-tert-butylbenzoate
• Synonyms: 4-hydroxyphenylglyoxylicacidsodiumsalt;Benzoic acid, 4-(1,1-dimethylethyl)-, methyl ester;Benzoic acid, p-tert-butyl-, methyl ester;butylbenzoicacidmethylester;Methyl p-tert-butylbenzoate;RARECHEM AL BF 0269;P-TERT-BUTYLBENZOIC ACID METHYL ESTER;TIMTEC-BB SBB000305
• CAS NO: 26537-19-9
• Molecular Formula: C₁₂H₁₆O₂
• Molecular Weight: 192.25
• EINECS: 247-768-5
• Product Categories: Aromatic Esters;Acids & Esters;OPLAS;C12 to C63;Carbonyl Compounds;Esters;Building Blocks;C12 to C63;Carbonyl Compounds;Chemical Synthesis;Organic Building Blocks
• Mol File: 26537-19-9.mol
• Article Data: 68

Chemical Properties

• Boiling Point: 122-124 °C9 mm Hg(lit.)
• Flash Point: >230 °F
• Appearance: Clear colorless to yellow/Liquid
• Density: 0.995 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.0144mmHg at 25°C
• Refractive Index: n20/D 1.51(lit.)
• Storage Temp.: Sealed in dry,Room Temperature
• Water Solubility: 35mg/L at 20℃
• CAS DataBase Reference: Methyl 4-tert-butylbenzoate(CAS DataBase Reference)
• NIST Chemistry Reference: Methyl 4-tert-butylbenzoate(26537-19-9)
• EPA Substance Registry System: Methyl 4-tert-butylbenzoate(26537-19-9)

Safety Data

• Safety Statements: 24/25
• WGK Germany: 3
• TSCA: Yes
• Hazardous Substances Data: 26537-19-9(Hazardous Substances Data)

Usage

Uses

1. Used in Chemical Synthesis:
Methyl 4-tert-butylbenzoate is used as an important intermediate for organic synthesis, particularly in the synthesis of tris(4-tert-butylphenyl)methyl chloride and avobenzone, an ingredient in sunscreen products.
2. Used in Plastics Industry:
Methyl 4-tert-butylbenzoate is used as an additive in the production of PVC heat stabilizers and PP nucleating agents. It enhances the luster, color, and drying time of the resin, as well as improves its chemical resistance.
3. Used in Coatings Industry:
As an alkyd resin modifier, Methyl 4-tert-butylbenzoate improves the luster, color, and drying time of the resin, and enhances its chemical resistance.
4. Used in Lubricants and Cutting Oils:
The ammonium salt of Methyl 4-tert-butylbenzoate can improve the performance of friction parts and prevent rust, making it suitable for use as additives in cutting oils and lubricants.
5. Used in Polymer Stabilization:
The sodium, barium, and zinc salts of Methyl 4-tert-butylbenzoate can be used as polymer stabilizers and nucleating agents, contributing to the stability and performance of various polymers.

Synthesis method

The synthesis method of P-tert-butyl benzoic acid includes: The oxidation method of liquid phase solvent, take acetic acid as solvent, lead acetate as oxidant and synthesize p-tert-butyl benzoic acid at low temperature. Liquid non-solvent oxidation method: there is no need of any solvent; take cobalt acetate and sodium bromide as a catalyst and apply air oxidation at 170e temperature to obtain the final products. High temperature gas phase oxidation method, in the presence of catalyst, high temperature lead to vaporization and oxidation of p-tert-butyl toluene to generate p-tert-butyl benzoic acid. Recently, we found that there is no need of any catalyst if using cheap nitric acid as the oxidant for oxidation of p-tert-butyl toluene to get the crude t-butyl benzoic acid, followed by being dissolved with sodium hydroxide to remove organic impurities and insoluble matter, and then being acidified to obtain pure p-tert-butyl benzoic acid. This method has good selectivity and low energy consumption, and can avoid the shortcomings of air oxidation method such as low oxidation conversion rate, thus having great practical value. Preparation of crude p-tert-butyl benzoic acid: To a 500 mL autoclave, add 26 mL (0.2 mol, 29.6 g) of p-tert-butyltoluene, 26 mL 68% nitric acid (0.4 mol, 37 g) and 2.5 mL of water. The reaction stirrer was started and the temperature was raised to 180e. The reaction lasted for 8 hour followed by cooling with cool water. Open the reactor with most of the solid being deposited on the bottom of the reactor and attached to the reactor cooling tube in a small amount. The solid was collected, filtered and dried to give 34.5 g with a yield of 95.5%. The purification of P-tert-butylbenzoic acid Weigh 10 g of sodium hydroxide and add 90 mL of water to prepare a 10% sodium hydroxide solution. Add the above solid into it. After being sufficiently dissolved, the filtrate was adjusted to pH 3 with hydrochloric acid, and a large amount of crystals would be precipitated at this time. The solution was allowed to stand for 33.4 g with a yield of 98.2%. The product was analyzed by infrared spectroscopy, displaying the characteristic peaks of p-tert-butylbenzoic acid. The content was 98.4% by HPLC analysis with a melting point of 164~166e (literature values 164~165e).

The effect of nitric acid concentration, reaction temperature and reaction time on the synthesis of products

Effect of nitric acid concentration on the product A series of nitric acid concentration experiments were carried out at two temperatures. The reaction temperature of curve 1 was 160e and the reaction temperature of curve 2 was 180e. The product content was obtained by liquid chromatography (HPLC) normalization. It can be seen that with the decrease of nitric acid concentration, the content of p-tert-butylbenzoic acid increased, the concentration of nitric acid decreased to about 10%. When the temperature reached 180e, the content reaches the highest value. When the concentration of nitric acid was higher than 50%, we couldn’t obtain the desired product. In addition, in this experiment, it could also be seen the impact of temperature on the product. The content in the series of high temperature was significantly higher than that of the low temperature series. The effect of reaction temperature on the product Considering the effect of reaction temperature, we selected the concentration of nitric acid at 10%. The effect of temperature on the product was that the reactant could not get the desired product at the reflux temperature. With the increase of temperature, the product content exhibits an increasing trend. At 170e, the content reaches the highest value with further increasing the temperature having almost no effect on the content. The effect of reaction time on the reaction A large number of experiments have found that the reaction time only affects the reaction conversion rate, without affecting product selectivity. That is, it does not affect the content of the product and only affects the yield of the product. In the experiment, it can be clearly seen of that the reaction time is not enough when the reactor floating above a layer of liquid organic matter, the analysis is the raw material of tert-butyl toluene. From the analysis of the data, we can see that the reaction temperature has the greatest influence on the yield. Considering various factors, we selected the reaction conditions as: the temperature: 180e, reaction time: 8h and nitric acid concentration: 10%. According to this condition, the content of p-tert-butylbenzoic acid was 98.4% and the yield was 95.5%.

Synthesis Reference(s)

Tetrahedron, 42, p. 553, 1986 DOI: 10.1016/S0040-4020(01)87454-8

InChI:InChI=1/C12H16O2/c1-12(2,3)10-7-5-9(6-8-10)11(13)14-4/h5-8H,1-4H3

Upstream product

• 186581-53-3 diazomethane 
• 98-73-7 4-(1,1-dimethylethyl)benzoic acid 
• 253185-03-4 tert-butylbenzene 
• 57031-51-3 Methyl-tert.-butylperoxyoxalat 
• 67-56-1 methanol 
• 877-65-6 p-tert-butylbenzyl alcohol 
• 98-51-1 4-tert-butyltoluene 
• 77-76-9 2,2-dimethoxy-propane 
• 76471-78-8 4,4'-di-tert-butylbenzil 
• 3972-65-4 1-bromo-4-tert-butylbenzene 
• 201230-82-2 carbon monoxide 
• 110-05-4 di-tert-butyl peroxide 
• 75-91-2 tert.-butylhydroperoxide 
• 431-47-0 trifluoroacetic acid-methyl ester 

Downstream Products

• 25163-88-6 2-(4-tert-butylphenyl)propene 
• 108463-08-7 1<4-(1,1-dimethylethyl)phenyl>-3-(1,2,3,4-tetrahydro-1-oxo-2-naphthalenyl)-1,3-propanedione 
• 82652-18-4 1-(4-(tert-butyl)phenyl)-2-(methylsulfonyl)ethanone 
• 87848-15-5 3-(4-tert-Butylphenyl)-2,4-dimethyl-3-pentanol 
• 98-86-2 acetophenone 
• 76471-78-8 4,4'-di-tert-butylbenzil 
• 123356-27-4 (Z)-1,1'-(1,2-ethenediyl)bis(4-butyl)benzene 
• 122884-20-2 1-(4-tert-Butyl-phenyl)-2-[1-phenyl-imidazolidin-(2E)-ylidene]-ethanone 
• 877-65-6 p-tert-butylbenzyl alcohol 
• 197964-93-5 (4-tert-Butyl-phenyl)-bis-(3,5-dibromo-phenyl)-methanol 
• 27541-51-1 tris(4-(tert-butyl))phenylmethane 
• 7050-16-0 tris(4-t-butylphenyl)methyl chloride 
• 143998-20-3 4-[tris-(4-tert-butylphenyl)methyl]phenol 
• 143998-21-4 mono-p-phenyl ether of di(ethylene glycol) 

Relevant articles and documents

Dual Nickel/Photoredox-Catalyzed Deaminative Cross-Coupling of Sterically Hindered Primary Amines

We report a method to activate α-3° amines for deaminative arylation via condensation with an electron-rich aldehyde and merge this reactivity with nickel metallaphotoredox to generate benzylic quaternary centers, a common motif in pharmaceuticals and natural products. The reaction is accelerated by added ammonium salts. Evidence is provided in support of two roles for the additive: inhibition of nickel black formation and acceleration of the overall reaction rate. We demonstrate a robust scope of amine and haloarene coupling partners and show an expedited synthesis of ALK2 inhibitors.

Method for catalytically synthesizing methyl p-tert-butylbenzoate based on deep eutectic solvent

The invention discloses a method for preparing methyl p-tert-butylbenzoate based on a deep eutectic solvent catalyst (PTSA-DES), and the catalyst PTSA-DES is prepared by mixing choline chloride and p-toluenesulfonic acid; the methyl p-tert-butylbenzoate i

Activity of a New Chromium(III) Complex with a Pentadentate (N3O2) Schiff-Base Ligand in the Reaction of Carbon Dioxide with Propylene Oxide

Abstract: The reaction of carbon dioxide with propylene oxide was carried out in the presence of a new pentadentate chromium complex, dichloro[2,6-diacetylpyridine bis(4-tert-butylbenzoylhydrazone)]chromium(III). The reaction kinetics was studied under different reaction conditions (temperature, pressure, and catalyst concentration). Optimal conditions for the synthesis of cyclic carbonate in the presence of the new chromium complex were found. The effective activation energy of the formation of cyclic carbonate was determined. The catalyst activity significantly depended on the substituent R in a 2,6-diacetylpyridine bis(4-R-benzoylhydrazone) ligand.

Kinetic study on the reaction of p-tert-butylbenzoic acid with methanol catalyzed by deep eutectic solvent based on choline chloride

The synthesis of methyl p-tert-butylbenzoate using deep eutectic solvent (DES) as a green catalyst was studied in this work. Four DESs were prepared by combining choline chloride (ChCl) and p-toluenesulfonic acid monohydrate (PTSA) with different molar ratios (1:1–3). It was found that ChCl-1.5PTSA with a molar ratio of 1:1.5 was superior to other DESs both in physical properties and catalytic performance. Therefore, it was selected to carry out the kinetic experiments. The effects of stirring speed, temperature, molar ratio of methanol to p-tert-butylbenzoic acid, and catalyst loading on the conversion of p-tert-butylbenzoic acid were discussed. In addition, the reaction kinetics of p-tert-butylbenzoic acid and methanol with ChCl-1.5PTSA as catalyst was explored in the temperature range of 332.15–349.15 K, and the experimental data were well fitted by pseudo-homogeneous model. Moreover, the recyclability of ChCl-1.5PTSA was evaluated. The result shows that the catalyst could be easily separated from the reaction system without any extractant, and the performance of the catalyst remains stable in multiple times recycling. Therefore, ChCl-1.5PTSA is expected to be an efficient and environmentally friendly catalyst for the methyl esterification of p-tert-butylbenzoic acid with a bright future in industrial application.

Hydroxyl radical-mediated oxidative cleavage of CC bonds and further esterification reaction by heterogeneous semiconductor photocatalysis

A hydroxyl radical-mediated aerobic cleavage of alkenes and further sequence esterification reaction for the preparation of carbonyl compounds have been developed by using tubular carbon nitride (TCN) as a general heterogeneous photocatalyst under an oxygen atmosphere with visible light irradiation. This protocol has an excellent substrate scope and gives the desired aldehydes, ketones and esters in moderate to high yields. Importantly, this metal-free procedure employed photogenerated hydroxyl radicals in situ as green oxidation active species, avoiding the present additional initiators. The reaction could be carried out under solar light irradiation and was applicable to large-scale reactions. Furthermore, the recyclable TCN catalyst could be used several times without a significant loss of activities.

Mild Copper-Catalyzed Addition of Arylboronic Esters to Di- tert -butyl Dicarbonate: An Easy Access to Methyl Arylcarboxylates

An efficient copper-catalyzed addition of arylboronic esters to (Boc) 2O was developed. The reaction can be conducted under exceedingly mild conditions and is compatible with a variety of synthetically relevant functional groups. It therefore represents a useful alternative route for the synthesis of methyl arylcarboxylates. A preliminary mechanistic study indicated the involvement of an addition-elimination mechanism.

Copper-catalyzed oxidative methyl-esterification of 5-hydroxymethylfurfural using TBHP as an oxidizing and methylating reagent: A new approach for the synthesis of furan-2,5-dimethylcarboxylate

Catalytic conversion of 5-hydroxymethylfurfural (HMF) into furan-2,5-dimethylcarboxylate (FDMC) is of great significance in the production of polyethylene furanoate (PEF), a renewable biomass-derived polymer that can replace the fossil dependent polyethylene terephthalate (PET). Herein, for the first time, we report the synthesis of FDMC from oxidative methyl-esterification of HMF using tert-butyl hydroperoxide (TBHP) as an oxidizing and methylating reagent catalyzed by mesoporous alumina nanospheres-embedded with CuO nanoparticles (CuO/m-Al2O3). The CuO/m-Al2O3 catalysts with different copper contents were prepared by evaporation-induced self-assembly of a structure-directing agent (Pluronic P-123). The decomposition of P-123 during calcination in air results into the formation of a mesoporous structure with highly dispersed CuO nanoparticles. The as-prepared 6-CuO/m-Al2O3 exhibits excellent catalytic activity towards oxidative methyl-esterification of HMF into FDMC with 92% yield and turnover frequency (TOF) of 0.56 h?1. Furthermore, oxidative methyl-esterification of a range of substrates through SP3 C[sbnd]H bond functionalization has also been demonstrated using the same catalyst.

Methoxylation of Acyl Fluorides with Tris(2,4,6-trimethoxyphenyl)phosphine via C-OMe Bond Cleavage under Metal-Free Conditions

Acyl fluorides are subjected to methoxylation with tris(2,4,6-trimethoxyphenyl)phosphine (TMPP) to afford the corresponding methyl esters in good to excellent yields. This transformation is featured by C(sp2)-OMe bond cleavage under metal-free conditions. Unprecedented utilization of TMPP as a methoxylating agent realized the installation of an OMe group into the desired products.

Discovery of [1,2,4]triazole derivatives as new metallo-β-lactamase inhibitors

The emergence and spread of metallo-β-lactamase (MBL)-mediated resistance to β-lactam antibacterials has already threatened the global public health. A clinically useful MBL inhibitor that can reverse β-lactam resistance has not been established yet. We here report a series of [1,2,4]triazole derivatives and analogs, which displayed inhibition to the clinically relevant subclass B1 (Verona integron-encoded MBL-2) VIM-2. 3-(4-Bromophenyl)-6,7-dihydro-5H-[1,2,4]triazolo [3,4-b][1,3]thiazine (5l) manifested the most potent inhibition with an IC50 (half-maximal inhibitory concentration) value of 38.36 μM. Investigations of 5l against other B1 MBLs and the serine β-lactamases (SBLs) revealed the selectivity to VIM-2. Molecular docking analyses suggested that 5l bound to the VIM-2 active site via the triazole involving zinc coordination and made hydrophobic interactions with the residues Phe61 and Tyr67 on the flexible L1 loop. This work provided new triazole-based MBL inhibitors and may aid efforts to develop new types of inhibitors combating MBL-mediated resistance.

Palladium-Catalyzed Chlorocarbonylation of Aryl (Pseudo)Halides Through In Situ Generation of Carbon Monoxide

An efficient palladium-catalyzed chlorocarbonylation of aryl (pseudo)halides that gives access to a wide range of carboxylic acid derivatives has been developed. The use of butyryl chloride as a combined CO and Cl source eludes the need for toxic, gaseous carbon monoxide, thus facilitating the synthesis of high-value products from readily available aryl (pseudo)halides. The combination of palladium(0), Xantphos, and an amine base is essential to promote this broadly applicable catalytic reaction. Overall, this reaction provides access to a great variety of carbonyl-containing products through in situ transformation of the generated aroyl chloride. Combined experimental and computational studies support a reaction mechanism involving in situ generation of CO.