A Rapid, Convenient, Solventless Green Approach for the Synthesis of a-Hydroxyphosphonates by Grinding

Kong, Dulin; Liu, Ren-Die; Li, Guo-Zhu; Zhang, Peng-Wei; Wu, Mingshu

doi:10.14233/ajchem.2014.16606

Cited by 15 publications

(10 citation statements)

References 9 publications

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“…Although a number of green variations were developed for the synthesis of the phosphonates under discussion, in these approaches the reaction conditions were green only with respect to the catalyst and the lack of solvents. The work-up involved the extensive use of solvents as extractants, eluants in chromatography and as media for recrystallizations (Kumar et al, 2012;Nandre et al, 2012;Kong et al, 2014;Kulkarni et al, 2013;Ramananarivo et al, 2013;Santhisudha et al, 2015;Liu et al, 2014). Keglevich and co-workers could, however, elaborate a green method, when the hydroxyphosphonate simply crystallized out in a pure form from the reaction mixture.…”

Section: Introductionmentioning

confidence: 99%

The typical crystal structures of a few representative α-aryl-α-hydroxyphosphonates

et al. 2019

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The crystal structures of seven -aryl--hydroxyphosphonates synthesized by the Pudovik reaction of substituted benzaldehydes and dialkyl phosphites, namely dimethyl [(hydroxy)(phenyl)methyl]phosphonate, C 9 H 13 O 4 P, dimethyl [(3,4-dimethoxyphenyl)(hydroxy)methyl]phosphonate, C 11 H 17 O 6 P, dimethyl (1-hydroxy-1-phenylethyl)phosphonate, C 10 H 15 O 4 P, dimethyl [1-hydroxy-1-(4nitrophenyl)ethyl]phosphonate, C 10 H 14 NO 6 P, dibenzyl [hydroxy(2-nitrophenyl)methyl]phosphonate, C 21 H 20 NO 6 P, dibenzyl [(3-chlorophenyl)(hydroxy)methyl]phosphonate, C 21 H 20 ClO 4 P, and dibenzyl [hydroxy(4-methylphenyl)methyl]phosphonate, C 22 H 23 O 4 P, were studied to gain a better understanding of the organization in this type of molecule in the solid state. The crystals obtained for this series of compounds show a balance between C-OHÁ Á ÁO P chain-linked packing and the dimeric types of hydrogen-bond bridges of intermolecular pairs of such functions. The description is based on primary graph-set descriptors. Using graph-set descriptors one level deeper (i.e. secondary graph sets of the C-HÁ Á ÁO type) revealed a similarity in the graph-set descriptors, suggesting a fine interplay of substituent-and shape-dependent effects on strong-weak interactions. It seems that the formation of chains or dimers is governed not only by the presence of a tertiary C atom, but also by the nature and crowding of the ortho substituents of the -aryl group.

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Section: Introductionmentioning

confidence: 99%

The typical crystal structures of a few representative α-aryl-α-hydroxyphosphonates

et al. 2019

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“…In the latter case, an extraction was inserted before the crystallization step in the work-up procedure [ 29 ]. In agreement with the requirements of environmentally friendly approaches, green activation methods, such as microwave (MW) irradiation [ 30 , 31 ] and grinding [ 32 , 33 ] were also employed in the synthesis of α-hydroxyphosphonates 1 . According to a MW-assisted procedure, the reaction of benzaldehydes and diethyl phosphite was carried out without the use of any catalyst or solvent ( Table 1 /Entry 10) [ 30 ], while another method combined MW irradiation with sodium carbonate as the base ( Table 1 /Entry 11) [ 31 ].…”

Section: Synthetic Routes Towards α-Hydroxyphosphonatesmentioning

confidence: 99%

“…According to a MW-assisted procedure, the reaction of benzaldehydes and diethyl phosphite was carried out without the use of any catalyst or solvent ( Table 1 /Entry 10) [ 30 ], while another method combined MW irradiation with sodium carbonate as the base ( Table 1 /Entry 11) [ 31 ]. Na 2 CO 3 was also used efficiently in another protocol, when the contact among the reaction components was promoted by grinding ( Table 1 /Entry 12) [ 32 ]. The drawback of the method is the complicated work-up procedure comprising washing, extraction, and finally recrystallization.…”

Section: Synthetic Routes Towards α-Hydroxyphosphonatesmentioning

confidence: 99%

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Synthesis and Reactions of α-Hydroxyphosphonates

Rádai

Keglevich

2018

Molecules

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This review summarizes the main synthetic routes towards α-hydroxyphosphonates that are known as enzyme inhibitors, herbicides and antioxidants, moreover, a number of representatives express antibacterial or antifungal effect. Special attention is devoted to green chemical aspects. α-Hydroxyphosphonates are also versatile intermediates for other valuable derivatives. O-Alkylation and O-acylation are typical reactions to afford α-alkoxy-, or α-acyloxyphosphonates, respectively. The oxidation of hydroxyphosphonates leads to ketophosphonates. The hydroxy function at the α carbon atom of hydroxyphosphonates may be replaced by a halogen atom. α-Aminophosphonates formed in the nucleophilic substitution reaction of α-hydroxyphosphonates with primary or secondary amines are also potentially bioactive compounds. Another typical reaction is the base-catalyzed rearrangement of α-hydroxy-phosphonates to phosphates. Hydrolysis of the ester function of hydroxyphosphonates leads to the corresponding phosphonic acids.

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“…These methods mainly employed simple and inexpensive oxides/bases/salts as catalysts, including aluminum oxide, magnesium oxide, barium hydroxide, sodium carbonate, potassium hydrogen sulfate, and inorganic phosphates, as well as triethylamine or piperazine . In a few cases, the components were activated by grinding or microwave (MW) irradiation . The new, environmentally friendly protocols emphasize the lack of solvent during the reaction; however, the use of volatile organic compounds could not be eliminated from the workup process, as it comprised intensive use of solvents in operations like extraction, column chromatography, and recrystallization.…”

Section: Introductionmentioning

confidence: 99%

Green synthesis and cytotoxic activity of dibenzyl α‐hydroxyphosphonates and α‐hydroxyphosphonic acids

Rádai

Szeles

Kiss

et al. 2018

Heteroatom Chemistry

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A series of dibenzyl α‐hydroxyphosphonates and the corresponding α‐hydroxyphosphonic acids, mostly new compounds, have been synthesized. The dibenzyl α‐hydroxyphosphonates have been obtained in the Pudovik reaction of substituted benzaldehydes and dibenzyl phosphite in the presence of triethylamine as the catalyst. The amount of the solvent was minimized during the reaction, and the workup involved crystallization from the reaction mixture. A new protocol was developed to transform the dibenzyl 1‐hydroxyphosphonates to the corresponding phosphonic acids by catalytic hydrogenation. The derivatives prepared were screened as potential cytotoxic agents against Mes‐Sa human uterine sarcoma cell line.

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A Rapid, Convenient, Solventless Green Approach for the Synthesis of a-Hydroxyphosphonates by Grinding

Cited by 15 publications

References 9 publications

The typical crystal structures of a few representative α-aryl-α-hydroxyphosphonates

The typical crystal structures of a few representative α-aryl-α-hydroxyphosphonates

Synthesis and Reactions of α-Hydroxyphosphonates

Green synthesis and cytotoxic activity of dibenzyl α‐hydroxyphosphonates and α‐hydroxyphosphonic acids

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