4909-81-3

Basic information

• Product Name: Benzoic acid (S)-1-methylpropyl ester
• Synonyms: (+)-Benzoic acid (S)-sec-butyl ester;Benzoic acid (1S)-1-methylpropyl ester;Benzoic acid (S)-1-methylpropyl ester;Benzoic acid (S)-sec-butyl ester
• CAS NO: 4909-81-3
• Molecular Formula: C₁₁H₁₄O₂
• Molecular Weight: 178.23
• Mol File: 4909-81-3.mol

Chemical Properties

• Appearance: /
• CAS DataBase Reference: Benzoic acid (S)-1-methylpropyl ester(CAS DataBase Reference)
• NIST Chemistry Reference: Benzoic acid (S)-1-methylpropyl ester(4909-81-3)
• EPA Substance Registry System: Benzoic acid (S)-1-methylpropyl ester(4909-81-3)

Safety Data

• Hazardous Substances Data: 4909-81-3(Hazardous Substances Data)

Upstream product

• 92787-70-7 O-benzoyl-N-iso-butylhydroxylamine 
• 65496-03-9 2-Diazobutane 
• 65-85-0 benzoic acid 
• 100-52-7 benzaldehyde 
• 78-92-2 iso-butanol 
• 56544-11-7 1-ethylethenyl benzoate 
• 56544-13-9 1-methyl-1-propenyl benzoate 
• 56544-12-8 but-2-en-2-yl benzoate 
• 27350-45-4 (S)-sec-butyl diphenylphosphinite 
• 4909-81-3 s-butyl benzoate 
• 582-25-2 Potassium benzoate 
• 64-17-5 ethanol 
• 50896-54-3 (S)-(+)-1-methylpropyl p-toluenesulfonate 
• 98-88-4 benzoyl chloride 

Downstream Products

• 4221-99-2 (S)-2-butanol 
• 14898-79-4 (2R)-butan-2-ol 
• 3306-36-3 (1R)-1-methylpropyl benzoate 
• 1485-70-7 N-benzylbenzamide 

Relevant articles and documents

Oxidative esterification of alcohols by a single-side organically decorated Anderson-type chrome-based catalyst

The direct esterification of alcohols with non-noble metal-based catalytic systems faces great challenges. Here, we report a new chrome-based catalyst stabilized by a single pentaerythritol decorated Anderson-type polyoxometalate, [N(C4H9)4]3[CrMo6O18(OH)3C{(OCH2)3CH2OH}], which can realize the efficient transformation from alcohols to esters by H2O2oxidation in good yields and high selectivity without extra organic ligands. A variety of alcohols with different functionalities including some natural products and pharmaceutical intermediates are tolerated in this system. The chrome-based catalyst can be recycled several times and still keep the original configuration and catalytic activity. We also propose a reasonable catalytic mechanism and prove the potential for industrial applications.

N-Aroylbenzotriazoles as Efficient Reagents for o-Aroylation in Absence of Organic Solvent

N-Aroylbenzotriazoles have been shown to be efficient reagents for esterification in the absence of organic solvent. Grinding of N-aroylbenzoytiazoles with twofold excess of alcohols for a couple of hours at room temperature gave corresponding esters in high percentage of yields.

Metal nitrate-catalyzed one-pot oxidative esterification of benzaldehyde with hydrogen peroxide in alcoholic solutions at room temperature

The activity of metal nitrate catalysts was investigated in the oxidative esterification reactions of benzaldehyde with hydrogen peroxide. Several types of metal nitrates (alkaline, alkaline earth, and transition metals) were evaluated as catalysts. Among the assessed salts, Fe(NO3)3 was the most efficient catalyst toward the formation of the target product (i.e., benzoic alkyl ester). In methyl alcohol, benzaldehyde was selectively oxidized to benzoic acid and then esterified to methyl benzoate. The efficiency of the catalyst was correlated with its higher Lewis acidity character, which was established through the pH measurements of methanolic solutions of the soluble metal nitrate salts. The influence of main variables of the reaction, such as catalyst load, temperature, and reactant stoichiometry, was investigated. The size of the carbon chain and steric hindrance played an essential role in the reaction selectivity. While methyl and ethyl alcohols selectively provided ester as the main product (ca. 70-75%) and acetal as the subproduct, the other alcohols gave ester, hemiacetal, and benzoic acid, which was formed in the least amount. The use of an inexpensive catalyst, a green oxidant, mild conditions, and short reaction times were the positive aspects of this one-pot process. The high TON (ca. 900) is evidence of the high catalytic activity of Fe(NO3)3. It is noteworthy that this methodology does not rely upon ligands and other additives.

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.

Aldehydes as potential acylating reagents for oxidative esterification by inorganic ligand-supported iron catalysis

The oxidative esterification of various aldehydes with alcohols could be achieved by a heterogeneous iron(iii) catalyst supported on a ring-like POM inorganic ligand under mild conditions, affording the corresponding esters, including several drug molecules and natural products, in high yields. ESI-MS and control experiments demonstrated that POM-FeV(O) was the active catalytic species and the plausible mechanism was presented. More importantly, the 6th run of the iron catalyst recycles shows only a slight decrease in the yield.

Derivatization of secondary aliphatic alcohols to picolinates - A new option for HPLC analysis with chiral stationary phase

Derivatization of secondary alcohols (R1R2CHOH) to benzoates has frequently employed to determine enantiomer ratios using HPLC with chiral stationary phase (CSP). However, a small difference in substituents (R1, R2) often results in insufficient separation. To find an alternative derivatization that detects such a small difference, picolinates (2-pyridyl-CO2CHR1R2) possessing Me/Et, Me/vinyl, Me/acetylenic, Et/n-Pr, and n-Pr/allyl substituents were prepared and separation efficiency was compared with that of benzoates (PhCO2CHR1R2). Eight commercially available CSPs containing carbamates or benzoates of cellulose and amylose were examined to find that retention factors (k'1 and k'2) and resolution (Rs) of picolinates were greater than those of the corresponding benzoates and that good to excellent Rs values (≥1.25) were recorded over a wide range of CSPs.

Cobalt-entrenched N-, O-, and S-tridoped carbons as efficient multifunctional sustainable catalysts for base-free selective oxidative esterification of alcohols

We report the synthesis of sustainable and reusable non-noble transition-metal (cobalt) nanocatalysts containing N-, O-, and S-tridoped carbon nanotube (Co@NOSC) composites. The expensive and benign carrageenan served as the source of carbon, oxygen, and sulfur, whereas urea served as the nitrogen source. The material was prepared via direct mixing of precursors and freeze-drying followed by carbonization under nitrogen at 900 °C. Co@NOSC catalysts comprising a Co inner core and outer electron-rich heteroatom-doped carbon shell were thoroughly characterized using various techniques, namely, TEM, HRTEM, STEM elemental mapping, XPS, BET, and ICP-MS. The utility of the Co@NOSC catalyst was explored for base-free selective oxidative esterification of alcohols to the corresponding esters under mild reaction conditions; excellent conversions (up to 97%) and selectivities (up to 99%) were discerned. Furthermore, the substrate scope was explored for the cross-esterification of benzyl alcohol with long-chain alcohols (up to 98%) and lactonization of diols (up to 68%). The heterogeneous nature and stability of the catalyst facilitated by its ease of separation for long-term performance and recycling studies showed that the catalyst was robust and remained active even after six recycling experiments. EPR measurements were performed to deduce the reaction mechanism in the presence of POBN (α-(4-pyridyl-1-oxide)-N-tert-butylnitrone) as a spin-trapping agent, which confirmed the formation of CH2OH radicals and H radicals, wherein the solvent plays an active role in a nonconventional manner. A plausible mechanism was proposed for the oxidative esterification of alcohols on the basis of EPR findings. The presence of a cobalt core along with cobalt oxide and the electron-rich N-, O-, and S-doped carbon shell displayed synergistic effects to afford good to excellent yields of products.

Broad Scope Synthesis of Ester Precursors of Nonfunctionalized Chiral Alcohols Based on the Asymmetric Hydrogenation of α,β-Dialkyl-, α,β-Diaryl-, and α-Alkyl-β-aryl-vinyl Esters

The catalytic asymmetric hydrogenation of trisubstituted enol esters using Rh catalysts bearing chiral phosphine-phosphite ligands (P-OP) has been studied. Substrates covered comprise α,β-dialkyl, α-alkyl-β-aryl, and α,β-diarylvinyl esters, the corresponding hydrogenation products being suitable precursors to prepare synthetically relevant chiral nonfunctionalized alcohols. A comparison of reactivity indicates that it decreases in the order: α,β-dialkyl > α-alkyl-β-aryl > α,β-diaryl. Based on the highly modular structure of P-OP ligands employed, catalyst screening identified highly enantioselective catalysts for α,β-dialkyl (95-99% ee) and nearly all of α-alkyl-β-aryl substrates (92-98% ee), with the exception of α-cyclohexyl-β-phenylvinyl acetate which exhibited a low enantioselectivity (47% ee). Finally, α,β-diarylvinyl substrates showed somewhat lower enantioselectivities (79-92% ee). In addition, some of the catalysts provided a high enantioselectivity in the hydrogenation of E/Z mixtures (ca. Z/E = 75:25) of α,β-dialkylvinyl substrates, while a dramatic decrease on enantioselectivity was observed in the case of α-methyl-β-anisylvinyl acetate (Z/E = 58:42). Complementary deuteration reactions are in accord with a highly enantioselective hydrogenation for both olefin isomers in the case of α,β-dialkylvinyl esters. In contrast, deuteration shows a complex behavior for α-methyl-β-anisylvinyl acetate derived from the participation of the E isomer in the reaction.

METHOD OF CONVERTING ALCOHOL TO HALIDE

The present invention relates to a method of converting an alcohol into a corresponding halide. This method comprises reacting the alcohol with an optionally substituted aromatic carboxylic acid halide in presence of an N-substituted formamide to replace a hydroxyl group of the alcohol by a halogen atom. The present invention also relates to a method of converting an alcohol into a corresponding substitution product. The second method comprises: (a) performing the method of the invention of converting an alcohol into the corresponding halide; and (b) reacting the corresponding halide with a nucleophile to convert the halide into the nucleophilic substitution product.

Application of γ-Valerolactone as an Alternative Biomass-Based Medium for Aminocarbonylation Reactions

γ-Valerolactone (GVL) was proposed as a renewable, nontoxic reaction medium with negligible vapor pressure for homogeneous Pd-catalyzed aminocarbonylation reactions. Iodobenzene as a model substrate and its 4-substituted derivatives were converted to the corresponding 2-ketocarboxamides with high conversions and chemoselectivities in γ-valerolactone. The effect of carbon monoxide pressure and reaction temperature on the conversion and selectivities were studied in the range 1–50 bar and 25–100 °C, respectively. The highest conversion and selectivity was achieved at 25 bar and 50 °C for iodobenzene in GVL for 24 h.