Phosphoryl trifluoride

J(PQ) and J(PN)). Trends in J(P170) have been used to study the protonation of phosphoryl tribromide, phosphoryl trifluoride and dif1uorophosphoric acid. Nitric acid had a greater protonation power than Hammett acidity functions indicated.77 This coupling has been the subject of a semiempirical sum over states theoretical study.7 ... 

A comprehensive review of the preparation, reactions, and n.m.r. spectra of phosphorus-fluorine compounds has appeared. This year s literature has been notable for the first detailed applications of ab initio SCF-MO calculations to the problems of bonding in halogenophosphines and their derivatives. - Comparison of the results of such theoretical calculations with experimental data obtained from photoelectron spectra shows a good correlation in the case of phosphorus trichloride and phosphoryl chloride, and of phosphorus trifluoride and its borane complex. ... 

Compound (1) phosphorylates phosphate monoesters and alcohols, although with the latter a considerable excess of alcohol is necessary to obtain satisfactory yields. In the absence of mercuric ions the milder phosphorylating species (3) can be isolated which converts monoalkyl phosphates to pyrophosphate diesters in good yield but does not react appreciably with alcohols unless catalytic amounts of boron trifluoride are added. Amine salts of (3) are converted to phosphoramidates on heating. In the presence of silver ions, O-esters of thiophosphoric acid behave as phosphorylating agents and a very mild and convenient procedure suitable for preparing labile unsymmetrical pyrophosphate diesters, such as the... 

Less common addition reactions such as the bromination of trifhioromethyl-substi-tuted butatrienes [30] or the reaction of tetrafluoroallene with boron trifluoride have also been reported [283]. Especially the interaction of phosphorylated allenes with electrophiles was summarized in a review by Alabugin and Brel [8], whereas Smadja [284] published a more general overview about the electrophilic addition to allenic derivatives. 

Nakagome and co-workers effected the successful cyclization of N-ethyl-N-arylaminomethylenemalonates (749) in poly phosphoric acid, prepared from orthophosphoric acid and phosphorus pentoxide in polyphosphate ester (PPE), prepared from phosphorus pentoxide and anhydrous diethyl ether in chloroform in phosphoryl chloride on the action of boron trifluoride etherate on the action of acetic anhydride and concentrated sulfuric acid or on the action of phosphorus pentoxide in benzene [71GEP2033971, 71JHC357 76JAP(K) 18440]. Depending on the work-up process, l-ethyl-4-oxoquinoline-3-carboxylates (750, R1 = Et), l-ethyl-4-oxoquinoline-3-carboxylic acids (750, R2 = H) and 3-ethoxycarbonyl-4-chloroquinolinium iodides (751) were obtained. Only the cyclization of... 

Reaction with phosphorus trichloride yields phosphorus trifluoride and with phosphoryl fluoride and sulfur trioxide, the product is phosphorus penta-fluoride ... 

Phosphorus tricyanide, 1339 Phosphorus trifluoride, 4333 Phosphorus triiodide, 4631 Phosphoryl chloride, 4143... 

The Wittig-Homer reaction between C-metallated a-phosphoryl sulfides and carbonyl compounds provides a common route to a,P-unsaturated sulfides, but one which usually results in poor yields of the desired product when enolisable ketones are used. Stephan et al. have investigated the role of boron trifluoride in promoting the Wittig-Horner reaction of enolisable ketones, which usually follows a two-step process the initial condensation of the anion followed by an elimination step. It was found that when the second step occurred at a slow rate then addition of boron triflouride was necessary for completion. ... 

Rast molecular wEiom- determination Isoquinuclidone (set Dowtherm.) Rearranoements Beckmann p-Acetamldobanzanasuironyl chloride. Boron trifluoride. Formic acid (see Hypochloroua acid). Iodine pentafluoride. Phosphoryl chloride. Poly-phosphoric acid. p-Toluenesulfonyl chtorlda. Trlfluoroacetlc anhydride. 

Whereas the Friedel-Crafts alkylations require only catalytic quantities of the Lewis acidic AICI3 catalyst, Friedel-Crafts acylations of phenols require excess Lewis acids, due to the complex formation of the Lewis acids with the hydroxyl group . Boron trifluoride-phosphoryl chloride, in stoichiometric amounts, is used for the Fridel-Crafts reaction of phenol with /3,/S-dimethylacrylic acid to give the acrylophenone. ... 

Preparation.1 A solution of dibromocyanoacetamide and cyanoacetamide in ethanol is refluxed for 5 hrs. in the presence of boron trifluoride etherate. yield 74%. Use in phosphorylation.1 a... 

Dimethyl sulfite,813 boron trifluoride,148 814 815 aromatic sulfonyl chlorides,816 and phosphoryl chloride817 have also proved their value for catalysing esterifications. 

Polyhydric phenols react with carboxylic acids even in the presence of zinc chloride520 or boron trifluoride and hydrogen fluoride.569 A mixture of zinc chloride and phosphoryl chloride has been recommended527,528 as a very efficient and mild agent for condensation of variously substituted phenols with malonic acid derivatives this leads to 4-hydroxycoumarins without isolation of the intermediates 527,528... 

Boron trifluoride catalyses the 1,3-phosphotropic rearrangement of the a-phosphorylated imine (65) to give (66).35 This reaction takes place at room temperature, whereas the uncatalysed reaction requires heating to 150-2000C. High yields of the addition products (67) have been obtained from the reaction of carbon-centred radicals with diphenylvinylphosphine oxide.36 Radical addition to the chiral phosphine oxides (68) using Barton s method provides diastereomeric ratios of up to 9 1 in the case of (69). 

Two methylene-bridged phosphoryl fluorides, CH2(POF2)a and CHgCCOF)-(POFa), have been prepared by fluorinating the corresponding chlorides with either antimony or arsenic trifluorides. 

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