A convenient dealkylation of dialkyl phosphonates by chlorotrimethylsilane in the presence of sodium iodide

Morita, T

doi:10.1016/0040-4039(78)80021-5

Cited by 52 publications

(3 citation statements)

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“…Additionally, hydrolysis with bromotrimethylsilane (TMSBr) [56][57][58] was not successful. At this point, considering a seminal work by Morita [59], KuQuinone phosphonate ester hydrolysis has been performed with TMSBr in the presence of NaI (Table 3). In fact, because of the higher nucleophilicity of the iodide compared to other halides, trimethylsilyl intermediate formation is favored.…”

Section: Resultsmentioning

confidence: 99%

A Sustainable Improvement of ω-Bromoalkylphosphonates Synthesis to Access Novel KuQuinones

et al. 2021

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Owing to the attractiveness of organic phosphonic acids and esters in the pharmacological field and in the functionalization of conductive metal-oxides, the research of effective synthetic protocols is pivotal. Among the others, ω-bromoalkylphosphonates are gaining particular attention because they are useful building blocks for the tailored functionalization of complex organic molecules. Hence, in this work, the optimization of Michaelis–Arbuzov reaction conditions for ω-bromoalkylphosphonates has been performed, to improve process sustainability while maintaining good yields. Synthesized ω-bromoalkylphosphonates have been successfully adopted for the synthesis of new KuQuinone phosphonate esters and, by hydrolysis, phosphonic acid KuQuinone derivatives have been obtained for the first time. Considering the high affinity with metal-oxides, KuQuinones bearing phosphonic acid terminal groups are promising candidates for biomedical and photo(electro)chemical applications.

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Section: Resultsmentioning

confidence: 99%

A Sustainable Improvement of ω-Bromoalkylphosphonates Synthesis to Access Novel KuQuinones

et al. 2021

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“…Previously in the Foucher group, dansyl tags with organosilane, 177 phosphonate, 177 benzophenone 105 and vinyl 138 On the other hand, dealkylation of phosphonate esters with TMSX (X = Cl -, Br -, I -) occurs via a different mechanism whereby the halide ion acts as both the leaving group and the nucleophile in the reaction (Figure 1.57). [182][183][184] In the first step of the mechanism the acidic phosphoryl sp 3 oxygen reversibly attacks the electrophilic silicon of the silylhalide forming a charged phosphonium intermediate while displacing the halide. Irreversible substitution with the nucleophilic halide only occurs with the attack on the phosphonate alkyl group producing one equivalent of an alkyl halide and a mixed trimethylsilylated ester.…”

Section: Detection Of Qac In Solution and On Surfacesmentioning

confidence: 99%

Detection and antimicrobial activity of immobilized quaternary ammonium antimicrobial monolayers on porous and non-porous surfaces

Porosa¹

2023

Preprint

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This research describes the development of novel, environmentally-friendly, non-releasing contact-active thin film coatings by immobilizing the quaternary ammonium (QA) antimicrobial group on a multitude of surfaces. Various chemical anchors based on organosilanes (i.e. textiles, silica, oxide surfaces), organosulfur comprising of thiol (noble metals), organophosphorus comprising of phosphonate and phosphonic acid (i.e. stainless steel (SS), titanium (Ti)), and catechol (Ti, SS) monolayers are employed to attach the QA antimicrobial onto metal surfaces, while benzophenone photoactive crosslinkers containing QA groups are used to coat plastic surfaces (C-H surfaces, i.e. polyethylene (PE), silicone (Si), polyvinylchloride (PVC)). Surfaces treated with covalently attached antimicrobial coatings function by killing microbes on contact, preventing surface attachment, colonization and contamination without releasing the chemical into the environment. The advantages of this method of delivery of the antimicrobial include a lower cost of application, decreased antimicrobial resistance, lower toxicity and increased environmental safety. Samples prepared by an overnight immersion in an ethanolic solution of phosphorus containing quats followed by an overnight cure at 100oC showed the highest antimicrobial reduction versus electrospray application and no curing. Short chain phosphonic acid quats and the organosilane quat were inactive on titanium. Antimicrobial activity of long chain phosphonate quats prepared by dip coating and annealing on metal surfaces (Ti, SS, Al) was tested by growth enumeration in the dry state utilizing methods developed in the Wolfaardt lab. All samples showed a 100% reduction (106 cells) of viable Salmonella, Arthrobacter, S.aureus and P.aeroguinosa after 2 hrs of contact time and maintained their activity over 24 hrs versus the uncoated controls. To demonstrate the phosphonate quats were truly immobilized, Ti samples from the first trial were washed in distilled H2O, dried, and re-innoculated with 106 Anthrobacter colonies. No visible colonies of Anthrobacter remained after 2 hrs of contact time with the Ti surfaces indicating a contact killing mechanism at play.

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“…The hexadecyl-and octadecylphosphates were obtained by reaction of the respective alcohols with phosphorus oxychloride in hexane in the presence of triethylamine, similar to the method previously described (13). The hexadecyl-and octadecylphosphonates were prepared by the Michaelis-Arbuzov reaction of alkylbromides with triethylphosphite via the diethyl alkylphosphonates (14) and bis(trimethylsilyl) alkylphosphonates (15).…”

Section: Compoundsmentioning

confidence: 99%

1-β-d-Arabinofuranosylcytosine-5′-alkylphosphonophosphates and diphosphates: new orally active derivatives of ara-C

Brachwitz

Bergmann

Fichtner

et al. 1998

Journal of Lipid Research

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ara-Cytidine-5 Ј -alkylphosphonophosphates and the corresponding -diphosphates were found to be cytostatically active in vitro against the human mammary epithelial cell line H184 A1N4 and the human mammary tumor cell line MaTu. Our results indicate that the replacement of the diphosphate by the phosphonophosphate group has no influence on antiproliferative activity in this case. The compounds were more active than the corresponding cytidine phospholipid conjugates and related compounds lacking a cytostatically active nucleoside, the ara-C prodrug Cytoros, and were slightly less active than ara-C. The cytostatic effect was prevented by 2 Јdeoxycytidine indicating their action as prodrugs of ara-C. In contrast to ara-C, they increase [Ca 2 ϩ ] 1 in H184 A1N4 cells, pointing to a different mechanism of action in addition to their prodrug effect. In combination with phospholipid analogs, synergistic effects could be observed. Further studies within the disease-oriented in vitro Anticancer Screening Program of the National Cancer Institute show selectivity for certain cancer cell lines. The hexadecyl derivatives revealed a significant antitumor activity in vivo against the murine lymphatic leukemia P 388 cells being equally potent or even superior to ara-C. In contrast to ara-C, they were found to be orally active. Side effects measured as leukopenia and body weight reduction were less pronounced than with the parent drug.

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A convenient dealkylation of dialkyl phosphonates by chlorotrimethylsilane in the presence of sodium iodide

Cited by 52 publications

References 0 publications

A Sustainable Improvement of ω-Bromoalkylphosphonates Synthesis to Access Novel KuQuinones

A Sustainable Improvement of ω-Bromoalkylphosphonates Synthesis to Access Novel KuQuinones

Detection and antimicrobial activity of immobilized quaternary ammonium antimicrobial monolayers on porous and non-porous surfaces

1-β-d-Arabinofuranosylcytosine-5′-alkylphosphonophosphates and diphosphates: new orally active derivatives of ara-C

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