ChemInform Abstract: ZUR UMSETZUNG DES DIAETHYLCHLORPHOSPHINS MIT KETONEN

Nurtdinov, S. Kh.; Khairullin, R. S.; Zykova, T. V.; Tsivunin, V. S.; Kamai, G. Kh.

doi:10.1002/chin.197210354

Cited by 3 publications

(3 citation statements)

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“…Simple enones 57 or acryloyl chlorides 60 were shown to produce, respectively methyl substituted or chlorinated oxaphospholenes 59 or 61 when treated with dialkyl halophosphites (Scheme ). In almost the same way, thiocarbonyl compounds gave rise to oxaphospholenes in a reaction with trimethylsilyl dimethyl phosphite…”

Section: Synthetic Routes Towards Oxaphospholenes and Benzoxaphospholmentioning

confidence: 93%

Fifty Years of (Benz)oxaphospholene Chemistry

Berton

Heugebaert

Virieux

et al. 2017

Chemistry A European J

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The first synthesis of benzoxaphospholenes dates back to the 1960s. Since then,t he structuralv ariety of reported (benz)oxaphospholenesh as steadily increased. Organophosphorusc ompounds have caught the interesto fs ynthetic chemists for ac ouple of decades now because of their interesting biological properties. Oxaphospholenes,i n particular,c ould serve as carbohydrate mimetics, and benzoxaphospholenes have been reported to possess bactericidal, insecticidal, herbicidal, and fungistatical properties. Transesterification reactions and addition of phosphorus nucleophiles to carbonylc ompoundsw ere reaction types that led to the production of the first (benz)oxaphospholenes.When it was discovered that allenylphosphonates could easily be obtainedf rom propargyl alcohols and dialkylh alophosphites, the electrophile-induced cyclization reaction of these allenylphosphonate precursors resulted in ah uge boom in the amounto fr eports on oxaphospholene synthesis. To this day,t his methodi ss till frequently used. Ring-closing metathesis and Horner-Wadsworth-Emmons reactions have also provent heir potentialf or the preparation of oxaphospholenes. In recent years, Pd, Rh and Au-catalysis have made their entry,g enerating (benz)oxaphospholenes from a wide variety of simple substrates. Ac ouple of miscellaneous methods are summarized at the end of the Review.[a] J.

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Section: Synthetic Routes Towards Oxaphospholenes and Benzoxaphospholmentioning

confidence: 93%

Fifty Years of (Benz)oxaphospholene Chemistry

Berton

Heugebaert

Virieux

et al. 2017

Chemistry A European J

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“…This approach is based on the reaction of accessible phosphorus-containing heterocycles having two P-C bonds, in particular 2-alkyl(aryl)-3,3,5-trimethyl-2,3-dihydro-1,2λ 5 -oxaphosphole 2-oxides like I [8][9][10][11], with Grignard compounds. Hydrolysis of the reaction mixture gives targeted (1-methyl-4-oxopent-2-yl)phosphine oxides II in more than 95% yield.…”

Section: Short Communicationsmentioning

confidence: 99%

A simple synthetic approach to unsymmetrically substituted (γ-oxoalkyl)phosphine oxides

et al. 2010

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SHORT COMMUNICATIONSPhosphine oxides and phosphines having a chiral phosphorus atom, including optically active compounds, are successfully used as ligands for metalcomplex catalysts in organic and asymmetric synthesis [1][2][3]; some derivatives are known as pesticides and biologically active substances [4]. However, more extensive application of these compounds is seriously limited due to complexity of methods for the preparation of phosphine oxides and phosphines with three different substituents, especially with those containing additional functional groups. Taking into account continuously growing demands for such compounds, development of accessible procedures for their synthesis remains to be important (see, e.g., [3][4][5][6][7]). Most known procedures require the use of expensive reagents and are complex and laborious; isolation of intermediate and final products is often difficult. Either racemates are obtained with subsequent optical resolution or stereoselective syntheses are necessary.We proposed a new and simple synthetic approach to unsymmetrically substituted phosphine oxides containing an oxo group as additional functional substituent in the γ-position with respect to the phosphorus atom. This approach is based on the reaction of accessible phosphorus-containing heterocycles having two P-C bonds, in particular 2-alkyl(aryl)-3,3,5-trimethyl-2,3-dihydro-1,2λ 5 -oxaphosphole 2-oxides like I [8][9][10][11], with Grignard compounds. Hydrolysis of the reaction mixture gives targeted (1-methyl-4-oxopent-2-yl)phosphine oxides II in more than 95% yield. Due to specific structure of the initial dihydrophosphole oxides (they possess one exo-and one endocyclic P-C bond and reactive endocyclic P-O bond), the third P-C bond is formed with high chemoselectivity with no any side process. As a result, the products are formed in high yields and with high purity. The structure of phosphine oxides II thus obtained was confirmed by IR, 1 H, 31 P, and 13 C NMR, and mass spectra. 4-[Ethyl(methyl)phosphoryl]-4-methylpentan-2-one (IIa).Compound Ia, 5.7 g (35.6 mmol), was added dropwise to the Grignard compound prepared according to standard procedure from 1.3 g (54.2 mmol) of magnesium and 4.1 ml (5.9 g, 54.2 mmol) of ethyl bromide in 100 ml of diethyl ether. When the addition was complete, the mixture was heated to the boiling point under vigorous stirring over a period of 1 h, cooled to 20°C, and neutralized under vigorous stirring at the boiling point by adding in succession 30 ml of water and 5 ml of hydrochloric acid. The organic phase was separated, the aqueous phase was extracted with methylene chloride (2 × 100 ml), the extracts were combined with the organic phase, the solvent was distilled off, and the residue was dried under reduced pressure (12 mm) at 100°C. Yield 6.6 g (98%), light brown oily substance. IR spectrum, cm -1 : I, R 1 = Me (a), Ph (b); II, R 1 = Me, R 2 = Et (a), Pr (b); R 1 = Ph, R 2 = PhCH 2 (c).

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“…9 The Michaelis chloride 2 is another easily accessible heterocycle containing one endocyclic phosphorus-carbon bond. 10 Earlier we found that the interaction of the compounds 1 with Grignard reagents leads to the formation of phosphine oxides 4a-e. 12,13 The reaction gives rise to the substitution of both exocyclic P-Cl and endocyclic P-O bonds and allows us to obtain the phosphine oxides with the hydroxy-group in δ-position to the phosphorus atom (Scheme 1). Z-Configuration of double bond of the alkenyl fragment is predetermined by the initial phosphorinine structure.…”

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confidence: 99%