Synthesis of Chiral and Non-chiral Phosphites Containing the Hexafluoroisopropoxy Group

Dakternieks, Dainis; Röschenthaler, Gerd‐Volker; Schmutzler, Reinhard

doi:10.1515/znb-1978-0509

Cited by 16 publications

(7 citation statements)

References 9 publications

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“…The presence of strongly electron-accepting substituents on phosphorus should be a factor increasing the thermal stability of such compounds. Thus, the dihalogenphosphoranes 4 containing three l-trifluoromethyl-2,2,2-trifluoroethoxy groups are notable for their high thermal stability [4]. The comparatively high electron-withdrawing properties of the a,a,o-trihydropolyfluoroalkyloxy groups on the phosphites 8 gave us reason to believe in the possibility for obtaining rather stable dihalogenophosphoranes 7 in their reactions with halogens and pseudohalogens.…”

Section: Resultsmentioning

confidence: 99%

“…The comparatively high electron-withdrawing properties of the a,a,o-trihydropolyfluoroalkyloxy groups on the phosphites 8 gave us reason to believe in the possibility for obtaining rather stable dihalogenophosphoranes 7 in their reactions with halogens and pseudohalogens. The phosphites 8 react with chlorine or bromine at low temperature to form the corresponding adducts 7 , which, unlike the phosphoranes 4 [4], decompose at room temperature. At the same time, the adducts 7 are rather stable in solutions at -4O"C, and that enables them to be applied successfully in various synthetic procedures (Scheme 3).…”

Section: Resultsmentioning

confidence: 99%

“…At the same time, the adducts' structures are determined by the relative electronaccepting abilities of the substituents. The phosphorane structure is typical only of compound 4 containing the most electron-accepting 1 -trifluoromethyl-2,2,2-trifluoroethyl substituents [4].…”

Section: +Roh Et3nmentioning

confidence: 99%

“…The data on stereochemistry and molecular dynamics are rarely available. In this report we have attempted to illustrate the experimental data on the above-mentioned problems with examples of the phosphoranes of the types 1-6 (Scheme 1) Ar 0-PC 1 , , 1 2 3 4 5 6 SCHEME 1…”

Section: Introductionmentioning

confidence: 99%

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Polyhalogenalkoxy(aryloxy)chloro‐ and bromophosphoranes

Markovsky¹,

Kozlov²,

Shermolovich³

1991

Heteroatom Chemistry

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The data on the synthesis, stereochemistry, and molecular dynamics of alkoxy(ary1oxy)halogenphosphoranes of acyclic structure, as well as of halogenphosphoranes containing the pentacoordinate phosphorus atom in the 1,4,2-dioxophospholane cycle and the node of bicyclo[2.2.2]octane system, are systematized. The influence of spatial properties of polyhalogenalkyl substituents on thermal stability and structure of adducts from tris(po1yhalogenalkyI) phosphites with chlorine and bromine is ascertained. The eflect of the phosphorus atom inclusion into the cycle and node of the bicyclooctane system on its pentacoordinate state stability is investigated.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: +Roh Et3nmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Polyhalogenalkoxy(aryloxy)chloro‐ and bromophosphoranes

Markovsky¹,

Kozlov²,

Shermolovich³

1991

Heteroatom Chemistry

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“…In the presence of two alkyl substituents at the P(III) atom, its fluoro alkoxy-derivatives form the quasi-phosphonium salts 81 These salts do not decompose up to 100-140 °C, which is due, according to the authors, to the electron-accepting influence of the CF3 groups on the a-carbon atom.…”

Section: A Oxidation Reactionsmentioning

confidence: 98%

Fluoroalkoxy-derivatives of trivalent phosphorus: synthesis and reactivity

Миронов¹,

Konovalova²,

Burnaeva³

et al. 1996

Russ. Chem. Rev.

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ContentsI. Introduction 935 II. The influence of fluorine-containing substituents on the properties of the P(III) atom. Photoelectron 935 spectroscopic and electrochemical data III. Synthesis of fluoroalkoxy-derivatives of P(III) 938 IV. Reactions of fluoroalkyl phosphites 948 V. Conclusion 966 Abstract. The review surveys and gives a systematic account of the electronic structures, syntheses, and chemical properties of fluoroalkyl derivatives of trivalent phosphorus (phosphites, thiophosphites, and amidophophites). The methods of preparation and reactivities of fluoroalkyl phosphites are compared with those of unsubstituted phosphites. The bibliography includes 420 references.

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Über 2‐tert‐Butyl‐1,3,2λ⁵‐dioxaphospholane und 2‐tert‐Butyl‐1,2λ⁵‐oxaphosphetane

et al. 1979

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Durch oxidative Addition von Hexafluoraceton an die Phosphor(II1)-Verbindungen 1 c -g werden die 1,3,2h5-Dioxaphospholane 2c, 2d, 2f und 2g bzw. das 1,2h5-Oxaphosphetan 3 gebildet; 2d lagert sich thermisch in das entsprechende 1,2h5-Oxaphosphetan 4 um. Die Phosphole 5 und 6 entstehen aus Hexafluorbiacetyl und Phosphinigsaureestern. Mit Hilfe der "F-NMRSpektroskopie wurden dynamische Effekte untersucht. Bei dem Phosphoran 2c tritt magnetische Nichtaquivalenz sowohl der CF,-Gruppen des Dioxaphospholan-Ringsystems als auch der des (CF,),CHO-Restes auf. Die analogen Verbindungen 7 -9 wurden zur vergleichenden Betrachtung herangezogen und der EinfluD der raumerfullenden tert-Butylgruppe am Phosphor studiert. On 2-tert-B~tyl-l,3,2~~-dioxaphospholanes and 2-tert-Butyl-1,2iS-oxaphosphetanesOxidative addition of hexafluoroacetone to the phosphorus(II1) compounds 1 c -g furnished the 1,3,2h5-dioxaphospholanes 2c, 26, 2f, 2g, and the 1,2h5-oxaphosphetane 3, respectively; 2d undergoes thermal rearrangement to the corresponding 1,2h5-oxaphosphetane 4. The phospholes 5 and 6 are formed from hexafluorobiacetyl with phosphinous acid esters. I9F NMR spectroscopy was employed to investigate dynamic effects in the compounds obtained. For the phosphorane 2c magnetic nonequivalence of the CF, groups of the dioxaphospholane ring system as well as of those of the (CF3)2CH0 group was observed. The related compounds 7 -9 were studied for comparison, and the influence of the bulky tert-butyl groups at phosphorus was investigated. Phosphor(II1)-Verbindungen vom Typ MePR'R2 addieren Hexafluoraceton unterBildung von 1,3,2hs-Dioxaphospholanen (R' = R2 = F": R' = R2 = OCH(CF3),2.3': R' = Me, R2 = F234)), von 1,3,4hs-Dioxaphospholanen (R' = Me, R2 = C1 'I: R' = Me, R2 = F2,4i); R' = Me, R2 = C16); R' = Me, RZ = OCH(CF,),"), die dann entstehen, wenn CH3-oder CHz-Reste direkt an Phosphor gebunden sind ').In der vorliegenden Arbeit wird untersucht, welchen EinfluIj der Ersatz einer Methylgruppe in MePR'R' durch den raumlich anspruchsvollen teut-Butylrest auf die Struktur und die dynamischen Eigenschaften der zur erwartenden Verbindungen mit pentakoordiniertem Phosphor hat. Der Vergleich wird auch auf Phosphole ausgedehnt, die aus den Phosphinigsaureestern tBu(Me)POCH(CF,), und Me,POCH(CF,), durch Anlagerung von Hexafluorbiacetyl entstehen ').0 Verlag Chemie, GmbH, D-6940 Weinheim, 1979 R2 = F4)) und von 1,2h5-Oxaphosphetanen (R' = RZ = OCH(CF,)22.3': R' = M e,

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Synthesis of Chiral and Non-chiral Phosphites Containing the Hexafluoroisopropoxy Group

Abstract: Abstract A series of new phosphorus (III) compounds containing the hexafluoroisopropoxide group has been synthesised by reacting halophosphines with lithium hexafluoroisopropoxide. The phosphites ButPX[OCH(CF3)2] (where X = F, Cl), ButMeP[OCH(CF3)2] and C6H5PF[OCH(CF3)2] … Show more

Cited by 16 publications

References 9 publications

Polyhalogenalkoxy(aryloxy)chloro‐ and bromophosphoranes

Polyhalogenalkoxy(aryloxy)chloro‐ and bromophosphoranes

Fluoroalkoxy-derivatives of trivalent phosphorus: synthesis and reactivity

Über 2‐tert‐Butyl‐1,3,2λ⁵‐dioxaphospholane und 2‐tert‐Butyl‐1,2λ⁵‐oxaphosphetane

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Synthesis of Chiral and Non-chiral Phosphites Containing the Hexafluoroisopropoxy Group

Abstract: Abstract A series of new phosphorus (III) compounds containing the hexafluoroisopropoxide group has been synthesised by reacting halophosphines with lithium hexafluoroisopropoxide. The phosphites ButPX[OCH(CF3)2] (where X = F, Cl), ButMeP[OCH(CF3)2] and C6H5PF[OCH(CF3)2] … Show more

Cited by 16 publications

References 9 publications

Polyhalogenalkoxy(aryloxy)chloro‐ and bromophosphoranes

Polyhalogenalkoxy(aryloxy)chloro‐ and bromophosphoranes

Fluoroalkoxy-derivatives of trivalent phosphorus: synthesis and reactivity

Über 2‐tert‐Butyl‐1,3,2λ5‐dioxaphospholane und 2‐tert‐Butyl‐1,2λ5‐oxaphosphetane

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Über 2‐tert‐Butyl‐1,3,2λ⁵‐dioxaphospholane und 2‐tert‐Butyl‐1,2λ⁵‐oxaphosphetane