Phenols, reaction with phosphorus

Fluorophosphites are prepared by a two step sequence. The initial step is the reaction of phenolic materials with phosphorus trichloride to prepare a chlorophosphite intermediate. The chlorophosphite is then treated with a fluoride source to convert the chloro- intermediate into the desired fluorophosphite product. Many different fluoride sources have been described in the literature including anhydrous hydrogen fluoride, anhydrous potassium fluoride, and antimony trifluoride. While any of these fluoride sources can be used successfully, we have found that antimony trifluoride (10) works well for small scale, lab preparations. 

Replacement of the hydroxyl group in a phenol by halogen cannot be accomplished by reaction with the hydrogen halides as in the case of alcohols, and reaction with phosphorus halides gives only low yields of halogenobenzenes (except in the case of nitrophenols), the main product being a phosphite or phosphate ester. 

Thiation is used predominantly for the synthesis of annelated thiazoles (e.g., (109)—(111)) from heterocyclic acylamides bearing either adjacent phenol or halogen substituents (Equations (33)— (35)) (70KGS1624, 77KGS1495, 87KGS410). The thieno[3,2-c]isothiazolium perchlorate (113) was obtained from the 2-benzoyl-3-(phenylamino)thiophene (112) by sequential reaction with phosphorus pentasulfide and perchloric acid (Equation (36)) <77CJC1123>. 

The 4-monosubstituted phosphabenzene (102) has been obtained from the corresponding 1,4-dihydrostannin by reaction with phosphorus tribromide. Phosphorins having one carbon- and one oxygen-linked substituent on phosphorus may be made directly by the reaction of phosphorins (103) with diazo-alkanes in the presence of alcohols or phenols. ... 

Zinc chloride has been used in place of aluminum chloride for the reaction of polyhydric phenol ethers with phosphorus trichloride, suitable working up again giving the tertiary phosphines. The resulting ZnCl2 complexes are successfully decomposed by aqueous ammonia.157... 

Triaryl phosphates are produced from the corresponding phenols (usually mixtures) by reaction with phosphorus oxychloride, usually in the presence of a catalyst (94,95). Tricresyl phosphate was originally made from petroleum-derived or coal-tar-derived cresylic acids (cresols). Discovery of the neurotoxicity of the ortho-cresyl isomers led manufacturers to select cresols having very little ortho-isomer. 

Naphthol and 3 moles of phenol mixed with phosphorus trisulfide prepared by igniting a mixture of 2 moles of P with 3 moles of S, heated slowly to 150°, kept 30 min. at this temp., then the temp, raised until it reaches 400° with distillation of the product -> naphthalene. Y 67%.— The reaction might be useful in the synthesis of polycyclic hydrocarbons, phenol being used as coreactant. F. e. s. W. N. Moulton and C. G. Wade, J. Org. Chem. 26, 2528 (1961) method cf. A. Geuther, A. 221, 55 (1883). 

A mixture of monolauryl phosphate sodium salt and triethylamine in H20 was treated with glycidol at 80°C for 8 h to give 98% lauryl 2,3-dihydro-xypropyl phosphate sodium salt [304]. Dyeing aids for polyester fibers exist of triethanolamine salts of ethoxylated phenol-styrene adduct phosphate esters [294], Fatty ethanolamide phosphate surfactant are obtained from the reaction of fatty alcohols and fatty ethanolamides with phosphorus pentoxide and neutralization of the product [295]. A double bond in the alkyl group of phosphoric acid esters alter the properties of the molecule. Diethylethanolamine salt of oleyl phosphate is effectively used as a dispersant for antimony oxide in a mixture of xylene-type solvent and water. The composition is useful as an additive for preventing functional deterioration of fluid catalytic cracking catalysts for heavy petroleum fractions. When it was allowed to stand at room temperature for 1 month it shows almost no precipitation [241]. 

The reaction with disubstituted formamides and phosphorus oxychloride, called the Vilsmeier or the Vilsmeier-Haack reaction,is the most common method for the formylation of aromatic rings. However, it is applicable only to active substrates, such as amines and phenols. An intramolecular version is also known.Aromatic hydrocarbons and heterocycles can also be formylated, but only if they are much more active than benzene (e.g., azulenes, ferrocenes). Though A-phenyl-A-methyl-formamide is a common reagent, other arylalkyl amides and dialkyl amides are also used. Phosgene (COCI2) has been used in place of POCI3. The reaction has also been carried out with other amides to give ketones (actually an example of 11-14),... 

Numerous preparative methods have been reported for these acids and their salts and ester derivatives.1 4 Dithiophosphoric acids are accessible from the reaction of phosphorus pentasulfide with alcohols or phenols (Equation 18). Dithiophosphinic acids can be prepared from thiophosphinic chlorides and sodium hydrosulfide (Equation 19), although the phenyl derivative is better prepared using a modified Friedel-Crafts reaction in which phosphorus pentasulfide is reacted with benzene in the presence of anhydrous aluminium trichloride (Equation 20). 

Diselenophosphates have been much less investigated than the analogous dithiophosphates, but some interesting chemistry was revealed. The reactions of phosphorus(V) selenide, P2Se5, with alcohols and phenols produce diseleno-phosphoric acid diesters, (RO)2P(Se)SeH, the parent compounds of di-selenophosphato anionic ligands. The free acids are not stable and should be immediately converted to metal salts or complexes. 

Triaryl esters can be prepared by a variety of methods. For example, by allowing 3 mol. of the phenol to react with 1 mol. of phosphorus oxychloride for several hours. Organic bases such as aniline, dimethylaniline and pyridine have been used to neutralize the hydrogen chloride formed in the reaction.3 Alternatively, the phenols may be converted into the sodium phenoxides4 and then allowed to react with phosphorus oxychloride. 

The rate of reaction of phosphorus oxychloride with phenols to produce triaryl phosphates is increased by the addition of quaternary ammonium salts and the reaction temperature can be reduced without loss of overall yield [1,2]. The analogous reaction between phenoxide anions and thiophosphoryl chloride produces aryl phosphoro-dichloridothoates [3]. As with the acylation of enolizable (3-dicarbonyl compounds (3.3.12), phosphorylation leads to the predominant formation of the E-O-phos-phoryiated derivatives [4,5]. 

The preparation of metal dithiophosphate complexes usually involves the reaction of metal halides or acetates with dithiophosphoric acids or their salts. The metal complexes are generally purified by repeated fractional crystallization from halocarbon solvents such as chloroform. The reactions of mixtures of alcohols and alcohols and phenols with phosphorus(V) sulfide allegedly,... 

The spirocyclic phosphazenes (138) resulting from the reaction with 2-azidoalcohols dimerize <82TL853>. In the adducts of phenols with a heterodiene function in the 2-position <77ZN(B)84l> the phosphorus atom also becomes the center of a tricyclic system (139) (Scheme 45). 

In the reaction with 2-hydroxy derivatives of benzaldehyde, acetophenone, and benzophenone, the phenol group adds to the l N bond, the carbon atom of the carbonyl group inserts into the P-NMe bond, and the phosphorus atom becomes oxidized to give (140) (Equation (15)) <96CB>. 

The BBrs reaction with 1. l-dimethoxy-2.4.6-di-tert-butyl-4-(4 -methoxyphenyl)-X -phosphorin 200 leads to cleavage of both methoxy groups in addition to the methoxy group at the phosphorus, the 4 -methoxy group is attacked. The 2-hydro-4-(4 -hydroxyphenyl)-phosphinic acid methyl ester 201 can be methylated with methyl iodide in methanol/sodium methylate at the phenolic group, leading to 202, which can also be prepared by hydrogen peroxide oxidation of 2.6-di-tert-butyl-4-(4 -methoxy phenyl)-X -phosphorin 204 to 203, followed by diazomethane methylation (see Table 13, p. 61). 

---