Dichlorophosphorylation of Adamantanols and 1-Adamantylcarbinols in Trifluoroacetic Acid

Ерохина, Е. В.; Shokova, E. A.; Luzikov, Yu. N.; Ковалев, В. В.

doi:10.1055/s-1995-3999

Cited by 12 publications

(6 citation statements)

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“…Direct phosphorylation of diamantane yields a mixture of apical monodiamantylphosphonic and didiamantylphosphinic acid chlorides . For the selective preparation of the medial diamantane phosphonic dichlorides ( 1 ), we utilized two different procedures previously developed for adamantane, namely phosphorylation in either sulfuric or trifluoroacetic acids (Scheme ) . Utilizing 1-diamantyl derivatives 2 (X = Br or OH) prepared in accordance with our previously developed procedures, target 1 was obtained in high preparative yields and was characterized using nuclear magnetic resonance (NMR) spectroscopy (see Experimental Procedures and Supporting Information for details).…”

Section: Resultsmentioning

confidence: 99%

Covalent Attachment of Diamondoid Phosphonic Acid Dichlorides to Tungsten Oxide Surfaces

Fabbri

Yurchenko

et al. 2013

Langmuir

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Diamondoids (nanometer-sized diamond-like hydrocarbons) are a novel class of carbon nanomaterials that exhibit negative electron affinity (NEA) and strong electron-phonon scattering. Surface-bound diamondoid monolayers exhibit monochromatic photoemission, a unique property that makes them ideal electron sources for electron-beam lithography and high-resolution electron microscopy. However, these applications are limited by the stability of the chemical bonding of diamondoids on surfaces. Here we demonstrate the stable covalent attachment of diamantane phosphonic dichloride on tungsten/tungsten oxide surfaces. X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared (FTIR) spectroscopy revealed that diamondoid-functionalized tungsten oxide films were stable up to 300-350 °C, a substantial improvement over conventional diamondoid thiolate monolayers on gold, which dissociate at 100-200 °C. Extreme ultraviolet (EUV) light stimulated photoemission from these diamondoid phosphonate monolayers exhibited a characteristic monochromatic NEA peak with 0.2 eV full width at half-maximum (fwhm) at room temperature, showing that the unique monochromatization property of diamondoids remained intact after attachment. Our results demonstrate that phosphonic dichloride functionality is a promising approach for forming stable diamondoid monolayers for elevated temperature and high-current applications such as electron emission and coatings in micro/nano electromechanical systems (MEMS/NEMS).

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Section: Resultsmentioning

confidence: 99%

Covalent Attachment of Diamondoid Phosphonic Acid Dichlorides to Tungsten Oxide Surfaces

Fabbri

Yurchenko

et al. 2013

Langmuir

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“…Hydroxydiamantanes 2a,b were converted to the corresponding chlorophosphonates 3ad, 3bd, 3ac, and 3bc through the phosphorylation reaction in trifluoroacetic acid [17,18] utilizing PhPCl 2 and AdPCl 2 as phosphorylating agents (Scheme 2). Chlorophosphonates 3ad, 3bd, 3ac, and 3bc were further reduced with LiAlH 4 in tetrahydrofuran to give phosphines 4ad, 4bd, 4ac, and 4bc.…”

Section: Resultsmentioning

confidence: 99%

P-Stereogenic diamondoid phosphines

Butova¹,

Bahonsky²,

Yurchenko³

et al. 2020

J. org. pharm. chem.

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P-Stereogenic diamondoid phosphines Despite diamondoid phosphines have found many synthetic applications and are even available commercially the chemistry of chiral diamondoid phosphines remains largely unexplored. Aim. To develop the convenient preparative method for the preparation of sterically-congested P-stereogenic secondary diamodoidyl phosphines as potential organocatalysts and ligands in the asymmetric synthesis. Results and discussion. A convenient method for the synthesis of P-stereogenic diamondoid phosphines with high yields through the phosphorylation of hydroxydiamondoids in trifluoroacetic acid followed by the reduction of the corresponding asymmetric chlorophosphonates has been proposed. The secondary phosphines obtained form stable complexes with borane that can be used to separate diamondoid phosphines into enantiomers. Experimental part. The experimental procedures for the preparation of 1-and 4-diamantyl-1-adamantyland phenylphosphines were developed; the structures of new compounds were confirmed by NMR and HRMS spectral data. Conclusions. A number of P-stereogenic mixed diamondoidylaryl phosphines and the secondary phosphines containing exclusively diamondoid substituents has been prepared. A degree of steric bulkiness is determined by the combination of diamondoid substituents around a phosphorus atom where 1-diamantyl derivatives are the most sterically-congested. The compounds obtained are potential ligands in asymmetric catalysis.

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“…Yield 0.33 g (95%), white solid, mp 143-145°C. 1 [5-(Adamantan-1-yl)-2-hydroxyphenyl](morpholin-4-yl)methanone (15). A mixture of acid 7a (1.36 g, 5 mmol) and thionyl chloride (2 mL, 28 mmol) was refluxed for 1 h. Excess thionyl chloride was distilled off under reduced pressure at 30°C, and the oily residue was treated with anhydrous benzene, followed by evaporation (3×10 mL).…”

Section: -[3-(3-tert-butyl-4-hydroxyphenyl)adamantan-1-yl]-2-hydroxybenzoic Acid (14c)mentioning

confidence: 99%

“…We previously showed that adamantylation of various carbon, nitrogen, and phosphorus nucleophiles with 1-hydroxy-and 1-bromoadamanes in trifluoroacetic acid (TFA) is an efficient method of synthesis of C-adamantylated arenes [9], heterocycles [10], adamantylalkylcarbinols [11], olefins [12,13], N-(3-R-ada mantan-1-yl) amides [14], and 3-R-adamantan-1-ylphosphonic dichlorides [15]. The present work was aimed at synthesizing adamantyl-substituted salicylic acids.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Adamantylated Salicylic Acids

Shokova

Ковалев

2021

Russ J Org Chem

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5-[3(4)-R-Adamantan-1-yl]salicylic acids [R = H, Alk, Ar, OH, NHC(S)NH 2 ] have been synthesized by electrophilic substitution reactions of hydroxy-and bromoadamantanes with salicylic acid, as well as by reactions of 5-(3-hydroxyadamantan-1-yl)salicylic acid with carbon and nitrogen nucleophiles, in trifluoroacetic acid. The possibility of selective hydroxylation of the adamantane fragment in 5-(adamantan-1-yl)salicylic acid with sulfuric acid in trifluoroacetic anhydride has been demonstrated.

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Dichlorophosphorylation of Adamantanols and 1-Adamantylcarbinols in Trifluoroacetic Acid

Cited by 12 publications

References 0 publications

Covalent Attachment of Diamondoid Phosphonic Acid Dichlorides to Tungsten Oxide Surfaces

Covalent Attachment of Diamondoid Phosphonic Acid Dichlorides to Tungsten Oxide Surfaces

P-Stereogenic diamondoid phosphines

Synthesis of Adamantylated Salicylic Acids

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