53772-44-4Relevant academic research and scientific papers
Method for preparing photoinitiator, namely TPO and simultaneously preparing byproduct, namely benzyl chloride
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Paragraph 0021; 0023; 0025-0026, (2020/06/02)
The invention provides a method for preparing a photoinitiator, namely TPO and simultaneously preparing a byproduct, namely benzyl chloride. The method provided by the invention avoids the problem ofrecovery of a large amount of organic waste gas, namely chloroethane and the like in production of the TPO, and also avoids the problem of serious pollution caused by a large amount of the byproduct,namely chlorine in production of the benzyl chloride. The benzyl chloride is an important chemical raw material for preparing a photoinitiator 369, so the method disclosed by the invention greatly reduces the production cost. Meanwhile, the whole process is low in preparation cost, simple in operation process, safe and easily-controllable in reaction process and easy to realize large-scale production.
Half-sandwich ruthenium(ii) complexes with tethered arene-phosphinite ligands: Synthesis, structure and application in catalytic cross dehydrogenative coupling reactions of silanes and alcohols
González-Fernández, Rebeca,Crochet, Pascale,Cadierno, Victorio
, p. 210 - 222 (2019/12/28)
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.
Synthesis of trifluoromethylated compounds from alcohols via alkoxydiphenylphosphines
Li, Jun-Li,Yang, Xian-Jin,Wang, Yanan,Liu, Jin-Tao
supporting information, p. 254 - 259 (2015/09/02)
The transformation of hydroxyl group in benzyl or allyl alcohols to trifluoromethyl was achieved via the reaction of the corresponding alkyloxydiphenylphosphine and CuCF3, generated in situ from methyl fluorosulfonyldifluoroacetate and CuI, under mild conditions. A plausible mechanism was proposed on the basis of experimental results.
Camphorquinone: A new and efficient oxidant for the preparation of 2-thio-substituted benzothiazoles from alcohols by oxidation-reduction condensation
Pluempanupat, Wanchai,Temyarasilp, Parinthorn,Widhalm, Michael,Chavasiri, Warinthorn
, p. 418 - 430 (2014/06/10)
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.
Lewis acid or alkyl halide promoted rearrangements of phosphor- and phosphinimidates to N,N-disubstituted phosphor- and phosphinamidates
Wilkening, Ina,Del Signore, Giuseppe,Ahlbrecht, Wiebke,Hackenberger, Christian P. R.
experimental part, p. 2709 - 2720 (2011/10/18)
In this paper, we describe the synthesis of N,N-disubstituted phosphor- and phosphinamidates via alkyl halide or Lewis acid catalyzed rearrangements of phosphor- or phosphinimidates. Furthermore, we introduce a novel one-pot procedure for the synthesis of N,N-disubstituted phosphoramidates which prevents the isolation of potentially explosive alkyl azide derivatives. In this reaction sequence, several alkyl halides are converted in situ into the corresponding azides and reacted with phosphites to generate phosphorimidates. Final addition of a catalytic amount of Lewis acid to the mixture affords the N,N-disubstituted phosphoramidates in good to excellent overall yields. 1 Introduction 2 Synthesis of N,N-Disubstituted Phosphor- and Phosphinamidates 2.1 Alkyl Halide Catalyzed Rearrangement of Phosphin- and Phosphorimidates 2.2 Lewis Acid Catalyzed Rearrangement of Phosphin- and Phosphorimidates 2.3 One-Pot Procedure for the Formation of N,N-Disubstituted Phosphoramidates from Alkyl Halides 3 Conclusion. Georg Thieme Verlag Stuttgart - New York.
A convenient method for the synthesis of dialkyl ethers by alkylation of alcohols using phosphinimidates in the presence of a catalytic amount of trimethylsilyl triflate
Aoki, Hidenori,Mukaiyama, Teruaki
, p. 1255 - 1264 (2007/10/03)
An alkylation reaction of alcohols with alkyl N-(methylsulfonyl) diphenylphosphinimidates proceeded smoothly in the presence of a catalytic amount of trimethylsilyl triflate (Me3SiOTf) in DME at room temperature and the corresponding ethers were afforded in good to high yields. An alkyl N-(methylsulfonyl)diphenylphosphinimidate can be prepared easily from an alkyl diphenylphosphinite and methanesulfonyl azide, and is isolated without tedious operation. Moreover, it is easy to handle and can be stored for several months at room temperature because of its air- and moisture-resistant character. Also, one-pot tertiary alkylations of alcohols by using t-alkyl diphenylphosphinites and diphenoxyphosphoryl azide proceeded efficiently in the presence of a catalytic amount of Me3SiOTf in cyclohexane/CH 2Cl2 at 0°C or -10°C, and gave the corresponding tertiary alkyl ethers in good yields. By following these methods, various ethers having alkali-sensitive functional groups can be prepared easily.
Cyanation of alcohols with diethyl cyanophosphonate and 2,6-dimethyl-1,4-benzoquinone by a new type of oxidation-reduction condensation
Masutani, Kouta,Minowa, Tomofumi,Hagiwara, Yoshiaki,Mukaiyama, Teruaki
, p. 1106 - 1117 (2007/10/03)
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.
Efficient methods for the preparation of alkyl-aryl and symmetrical or unsymmetrical dialkyl ethers between alcohols and phenols or two alcohols by oxidation-reduction condensation
Shintou, Taichi,Mukaiyama, Teruaki
, p. 7359 - 7367 (2007/10/03)
Oxidation-reduction condensation via alkoxydiphenylphosphines (diphenylphosphinite esters) (1), generated in situ from chlorodiphenylphosphine (2) and alcohols, 2,6-dimethyl-1,4-benzoquinone (3), and phenols proceeds smoothly to afford alkyl-aryl ethers in good to high yields under neutral conditions. In a similar fashion, a new and efficient method for the preparation of symmetrical or unsymmetrical dialkyl ethers in good to high yields is established via tetrafluoro-1,4-benzoquinone (fluoranil) (4), alcohols, and 1 formed in situ from nBuLi-treated alcohols and 2. This method is applicable also to the etherification of chiral secondary or tertiary alcohols with retention or inversion of configurations. The inverted ethers are afforded by treating chiral alkoxydiphenylphosphines and achiral alcohols, while the reaction of achiral alkoxydiphenylphosphines and chiral alcohols forms retained ethers.
Efficient method for the preparation of inverted alkyl carboxylates and phenyl carboxylates via oxidation-reduction condensation using 2,6-dimethyl-1,4-benzoquinone or simple 1,4-benzoquinone
Shintou, Taichi,Fukumoto, Kentaro,Mukaiyama, Teruaki
, p. 1569 - 1579 (2007/10/03)
Oxidation-reduction condensation using in situ formed alkoxydiphenylphosphines, 2,6-dimethy-1,4-benzoquinone, and carboxylic acids provides a useful method for the preparation of inverted tertiary alkyl carboxylates from the corresponding chiral tertiary alcohols under mild and neutral conditions. Similarly, it has afforded alkyl carboxylates successfully in good-to-high yields by the combined use of alkoxydiphenylphosphines having primary, secondary, or tertiary alkoxy groups, carboxylic acids, and simple 1,4-benzoquinone. When chiral secondary or tertiary alcohols are used, the corresponding inverted secondary or tertiary alkyl carboxylates are also obtained in good-to-high yields. In addition, a convenient method for the preparation of phenyl carboxylates in high yields has been established by utilizing oxidation-reduction condensation in toluene at 110 °C using phenoxydiphenylphosphines in situ-formed from phenols and chlorodiphenylphosphine, 2,6-dimethyl-1,4-benzoquinone, and carboxylic acids.
Preparation of nitriles from primary alcohols by a new type of oxidation-reduction condensation using 2,6-dimethyl-1,4-benzoquinone and diethyl cyanophosphonate
Mukaiyama, Teruaki,Masutani, Kouta,Hagiwara, Yoshiaki
, p. 1192 - 1193 (2007/10/03)
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.
