944-95-6

Upstream product

• 21615-34-9 2-Methoxybenzoyl chloride 
• 67-63-0 isopropyl alcohol 
• 529-28-2 4-iodoanisol 
• 201230-82-2 carbon monoxide 
• 579-75-9 2-Methoxybenzoic acid 
• 683-60-3 sodium isopropylate 

Downstream Products

• 162285-45-2 (2-methoxyphenyl)di(1-naphthyl)methanol 
• 612-16-8 (2-methoxyphenyl)methanol 
• 64655-62-5 (2-methoxyphenyl)(diphenyl)methanol 

Relevant academic research and scientific papers

Efficient synthesis of esters through oxone-catalyzed dehydrogenation of carboxylic acids and alcohols

Since esters are important organic synthesis intermediates, an environmentally friendly oxone catalyzed-esterification of carboxylic acids with alcohols has been developed. A series of carboxylic acid esters are obtained in high yield. This strategy requires mild reaction conditions, providing an attractive alternative for the construction of valuable carbonyl esters. Electron-rich and electron-deficient groups are compatible with the standard conditions and a variety of substrates are demonstrated. Moreover, the reaction could easily be adapted to typical prodrugs, drugs and gram-scale synthesis.

AMIDATION METHOD AND ESTERIFICATION METHOD USING SULFONIC ACID HALIDE

PROBLEM TO BE SOLVED: To provide a safe and economical method for rapidly synthesizing amides and esters in high yield. SOLUTION: There is provided a method for amidating an amine or a derivative thereof using a sulfonic acid halide, where a sulfonic acid halide is allowed to act as an activator on a carboxylic acid or a derivative thereof to synthesize an active ester, and the active ester is reacted with an amine or a derivative thereof as a nucleophile to amidate the amine or the derivative thereof to obtain a corresponding amide or a derivative thereof. In a similar manner, a sulfonic acid halide is allowed to act as an activator on a carboxylic acid or a derivative thereof to synthesize an active ester, and the active ester is reacted with an alcohol or a derivative thereof as a nucleophile to esterify the alcohol or the derivative thereof to obtain a corresponding ester or a derivative thereof. SELECTED DRAWING: Figure 1 COPYRIGHT: (C)2016,JPO&INPIT

Base-induced mechanistic variation in palladium-catalyzed carbonylation of aryl iodides

A mechanism, which is distinct from the traditional one when sodium alkoxide was used instead of tertiary amines, was proposed for the alkoxycarbonylation of aryl iodides. The catalytic cycle was composed of oxidative addition, subsequent ArPdOR formation, CO insertion to Pd-OR, and final reductive elimination of ArPdCOOR. The kinetic simultaneity of the formation of deiodinated side product from the aryl iodide and aldehyde from corresponding alcohol provided strong evidence for the existence of ArPdOR species. The observation of thioether, as the other competitive product in palladium catalyzed thiocarbonylation of aryl iodides and sodium alkylthiolate, also indicate the possibility of metathesis between ArPdl and sodium alkylthiolate. Preliminary kinetic studies revealed that neither oxidative addition nor reductive elimination was rate limiting. DFT calculation displayed preference for CO insertion into Pd-OR bond. The advantage of this novel mechanism had been demonstrated in the facile alkoxycarbonylation and thiocarbonylation. The ethoxycarbonylation of aryl iodides under room temperature and balloon pressure of CO in the presence of EtONa were examined, and good to high yields were obtained; the t-butoxycarbonylation reactions in the presence of t-BuONa were achieved, and the alkylthiocarbonylation (including the t-butylthiocarbonylation) of aryl iodides in the presence of sodium alkylthiolate were also investigated.

Alkoxycarbonylation of aryl iodides using gaseous carbon monoxide and pre-pressurized reaction vessels in conjunction with microwave heating

The microwave-promoted alkoxycarbonylation of aryl iodides using reaction vessels pre-pressurized with carbon monoxide is reported. Reactions are performed using 0.1 mol% palladium acetate as catalyst, DBU as base and are complete within 20-30 min. A range of aryl iodide substrates can be converted to the corresponding esters using this methodology. Primary and secondary alcohols work well whereas a tertiary alcohol substrate proves less reactive. The potential for scale-up of the reaction has also been explored. The Royal Society of Chemistry.

Alkoxycarbonylation reactions performed using near-stoichiometric quantities of CO

Alkoxycarbonylation reactions using near-stoichiometric quantities of carbon monoxide gas are presented. The reactions are performed using microwave heating which, as well as the inherent advantages of rate acceleration, offers a convenient method for loading vessels with gases. Georg Thieme Verlag Stuttgart.

Convenient Synthesis of Biphenyl-2-carboxylic Acids via the Nucleophilic Aromatic Substitution Reaction of 2-Methoxybenzoates by Aryl Grignard Reagents

Nucleophilic aromatic substitution (SNAr) of 2-methoxybenzoic esters derived from 2,6-dialkylphenols by aryl Grignard reagents affords 1,1'-biphenyl-2-carboxylates in excellent yields by proper choice of the bulk of the 2,6-dialkyl-substituents. The phenoxyl protecting groups can be easily removed from the resulting biphenyl-2-carboxylates to the free acids by treatment with potassium hydroxide in aqueous ethanol (2,4,6-trimethylphenyl and 2,6-diisopropylphenyl esters) or sodium methoxide in toluene-hexamethylphosphoric triamide (2,6-di-t-butyl-4-methylphenyl esters). The regioselective biphenyl coupling reaction via the SNAr process is utilized for the key-step construction of the biphenyl skeleton in a formal synthesis of cannabinol.