53772-44-4

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.

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.

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.

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.

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.

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 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.

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.

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.

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.

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.

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.

A new type of oxidation-reduction condensation using in situ formed alkoxydiphenylphosphines (i.e., diphenylphosphinite esters), easily available 1,4-benzoquionone and carboxylic acids provides a new and efficient method for the preparation of alkyl carboxylates from the corresponding alcohols under mild and neutral conditions. Further, the yields of the corresponding inverted carboxylates were equally high in the case of chiral secondary or tertiary alcohols.

A new type of oxidation-reduction condensation by using tetrafluoro-1,4-benzoquinone (fluoranil), alcohols and alkoxydiphenylphosphines, in situ formed from nBuLi-treated alcohols and chlorodiphenylphosphine, proceeded smoothly to afford the corresponding symmetrical or unsymmetrical ethers in good to high yields.

Various carboxylic benzyl esters were obtained in high yields by way of oxidation-reduction condensation in which benzyloxydiphenylphosphine (BDPP), having been prepared easily from chlorodiphenylphosphine and benzyl alcohol, was treated with various carboxylic acids in the presence of 2,6-dimethyl-1,4-benzoquinone(DMBQ) under mild conditions.

Photochemical reactions (λ irr = 54 nm) of substituted benzyldiphenylphosphine oxides 1a-e have been investigated in benzene and acetonitrile. α-Cleavage from the singlet excited state is proposed as the primary process, and products formed bot

Diphenylchlorophosphine and diethylchlorophosphite react with acetylacetone to generate intermediate phosphine enolates 3 which are quenched with O-diethylboryl derivatives and then oxidized with hydrogen peroxide to give diphenylphosphinates 4 and diethylphosphates 5. - Keywords: Phosphorylation, Diphenylphosphinates, Diethylphosphates, O-Diethylboryl Intermediates

Pyrolysis of 2,2-diphenyl-2-methoxy derivatives of the title compounds in the gas phase gives phosphinates or phosphinamidates derived from the substrate by formal loss of methylene.Control experiments show that the reaction involves radical cleavage initiated by rupture of the oxazaphosph(V)ole ring.Pyrolysis of 3-aryl-2,2-dimethoxy-2-phenyl derivatives of the title compounds under similar conditions results in the formation of 3-aryl-2,3-dihydro-2-oxo-2-phenyl-1,3,2-benzoxazaphospholes.No significant products could be isolated from 2,2,2-trimethoxy derivatives, though vigorous conditions were required for their complete breakdown.The pyrolysis of the corresponding 2,2-diphenyl-2-ethoxy, 2,2-diethoxy-2-phenyl, and 2,2,2-triethoxy compounds gave higher yields of similar products, possibly via a six-centre concerted elimination.