849604-79-1

Upstream product

• 60-12-8 2-phenylethanol 
• 6840-01-3 (dimethylamino)(diphenyl)phosphine 
• 1079-66-9 chloro-diphenylphosphine 

Downstream Products

• 94-47-3 2-Phenylethyl benzoate 
• 645-59-0 dihydrocinnamonitrile 
• 7501-05-5 N-(2-phenylethyl)phthalimide 
• 93366-73-5 2-(phenethylthio)benzo[d]thiazole 
• 52374-24-0 N-(4-nitrobenzenesulfonyl)-2-phenylethylamine 

Relevant academic research and scientific papers

Half-sandwich ruthenium(ii) complexes with tethered arene-phosphinite ligands: Synthesis, structure and application in catalytic cross dehydrogenative coupling reactions of silanes and alcohols

The preparation of the tethered arene-ruthenium(ii) complexes [RuCl2{η6:κ1(P)-C6H5(CH2)nOPR2}] (R = Ph, n = 1 (9a), 2 (9b), 3 (9c); R = iPr, n = 1 (10a), 2 (10b), 3 (10c)) from the corresponding phosphinite ligands R2PO(CH2)nPh (R = Ph, n = 1 (1a), 2 (1b), 3 (1c); R = iPr, n = 1 (2a), 2 (2b), 3 (2c)) is presented. Thus, in a first step, the treatment at room temperature of tetrahydrofuran solutions of dimers [{RuCl(μ-Cl)(η6-arene)}2] (arene = p-cymene (3), benzene (4)) with 1-2a-c led to the clean formation of the corresponding mononuclear derivatives [RuCl2(η6-p-cymene){R2PO(CH2)nPh}] (5-6a-c) and [RuCl2(η6-benzene){R2PO(CH2)nPh}] (7-8a-c), which were isolated in 66-99% yield. The subsequent heating of 1,2-dichloroethane solutions of these compounds at 120 °C allowed the exchange of the coordinated arene. The substitution process proceeded faster with the benzene derivatives 7-8a-c, from which complexes 9-10a-c were generated in 61-82% yield after 0.5-10 h of heating. The molecular structures of [RuCl2(η6-p-cymene){iPr2PO(CH2)3Ph}] (6c) and [RuCl2{η6:κ1(P)-C6H5(CH2)nOPiPr2}] (n = 1 (10a), 2 (10b), 3 (10c)) were unequivocally confirmed by X-ray diffraction methods. In addition, complexes [RuCl2{η6:κ1(P)-C6H5(CH2)nOPR2}] (9-10a-c) proved to be active catalysts for the dehydrogenative coupling of hydrosilanes and alcohols under mild conditions (r.t.). The best results were obtained with [RuCl2{η6:κ1(P)-C6H5(CH2)3OPiPr2}] (10c), which reached TOF and TON values up to 117 600 h-1 and 57 000, respectively.

Camphorquinone: A new and efficient oxidant for the preparation of 2-thio-substituted benzothiazoles from alcohols by oxidation-reduction condensation

A convenient one-pot procedure for the preparation of various 2-thio-substituted benzothiazoles from alcohols and benzothiazole-2-thiol utilizing camphorquinone-mediated oxidation-reduction condensation is disclosed. The condensation between benzothiazole-2-thiol and alkyl diphenylphosphinites, generated in situ from alcohols and chlorodiphenylphosphine, proceeded smoothly in the presence of camphorquinone to furnish the corresponding benzothiazoles in good to moderate yields.

Cyanation of alcohols with diethyl cyanophosphonate and 2,6-dimethyl-1,4-benzoquinone by a new type of oxidation-reduction condensation

Cyanation of various alcohols by a new type of oxidation-reduction condensation is described. Primary alkyl diphenylphosphinites, 2,6-dimethyl-1,4-benzoquinone (DMBQ), and diethyl cyanophosphonate gave the corresponding nitriles in high yields. During the above experiment on cyanation of 4-phenylbutan-2-ol, the unexpected formation of a mixture of nitrile and isocyanide was observed. After careful examination of the reaction conditions, selective synthesis of isocyanides from secondary alcohols was successfully accomplished by the use of zinc oxide (ZnO) as an additive. Reaction of tertiary alcohols provided the corresponding isocyanides exclusively in the absence of an additive. Cyanation of optically active alcohols was tried in order to clarify the stereochemistry of this reaction, and the reaction was thus proved to proceed with the inversion of configuration.

Preparation of nitriles from primary alcohols by a new type of oxidation-reduction condensation using 2,6-dimethyl-1,4-benzoquinone and diethyl cyanophosphonate

Cyanation of alkoxydiphenylphosphines, in situ prepared from nBuLi and various primary alcohols, with 2,6-dimethyl-1,4- benzoquinone (DMBQ) and diethyl cyanophosphonate provided the corresponding nitriles in high yields.

Preparation of various carboxylic acid esters from bulky alcohols and carboxylic acids by a new type oxidation-reduction condensation using 2,6-dimethyl-1,4-benzoquinone

A new-type oxidation-reduction condensation by using 2,6-dimethyl-1,4-benzoquinone (DMBQ), carboxylic acids and in situ formed alkoxydiphenylphosphines (1) including the bulky alkoxy group-substituted ones proceeded smoothly to afford the corresponding carboxylic acid esters in good to high yields. Alkoxydiphenylphosphines were formed in situ by treating either N,N-dimethylaminodiphenylphosphine (Ph2PNMe2) with primary or secondary alcohols or chlorodiphenylphosphine with the lithium salts of primary, secondary and tertiary alcohols.

Efficient method for the preparation of carboxylic acid alkyl esters or alkyl phenyl ethers by a new-type of oxidation-reduction condensation using 2,6-dimethyl-1,4-benzoquinone and alkoxydiphenylphosphines

A new-type of oxidation-reduction condensation proceeded smoothly to afford carboxylic acid alkyl esters or alkyl phenyl ethers in good to high yields by combined use of alkoxydiphenylphosphines (1) having primary, bulky secondary or tertiary alkoxy groups, a mild quinone-type oxidant such as 2,6-dimethyl-1,4-benzoquinone (DMBQ) and carboxylic acids or phenols. Generally, alkoxydiphenylphosphines were prepared easily from chlorodiphenylphosphine (2) and alcohols in the presence of pyridine, and were isolated by distillation. On the other hand, the phosphines 1 were also prepared in situ from N,N-dimethylaminodiphenylphosphine (3a) and primary or secondary alcohols while primary, bulky secondary or tertiary alkoxydiphenylphosphines were alternatively formed in situ by adding 2 to the "BuLi-treated alcohols in order to perform the above reactions by a one-pot procedure from alcohols and nucleophiles. The reaction of thus formed 1, DMBQ and carboxylic acids or phenols afforded the corresponding alkylated products, including hindered secondary and tertiary alkylated ones, in good to high yields at room temperature. In the case of using chiral secondary alcohols, the corresponding carboxylic acid alkyl esters were obtained as well in high yields with perfect inversion of stereochemistry by SN2 replacement.