The Phosphonation of Aromatic Compounds with Phosphoric Anhydride¹

Abstract

Benzene, chlorobenzene, c-xylene and naphthalene are phosphonated by hexagonal phosphoric anhydride in a temperature range of about 275-325°. A primary reaction product is formed by addition of one molecule of the aromatic compound to one molecule of P4Oio with opening of a covalent P-O bond. In the cases of chlorobenzene, o-xylene and naphthalene there are also formed secondary reaction products which are phosphonic anhydrides of the type (ArPCbb. The primary reaction products are insoluble in the aromatic compound while the secondary ones are soluble. Both the primary and the secondary products give the phosphonic acid when hydrolyzed and the phosphonic dichloride when chlorinated with phosphorus pentachloride.

Water-Soluble Phosphated Graphene: Preparation, Characterization, Catalytic Reactivity, and Adsorption Property

“…Thus, these combined reactants were tested to produce in situ active phosphate reagents (Figure S3). These combined reactants have lower hazardous effects than PCl x and produce activated phosphorus derivatives simultaneously as the phosphorylation reaction proceeds. ,, Nevertheless, except using the PCl x reagents, PPGO has been formed as the major product (Figure S4). According to the mentioned reasons and with utilization of the respective references, PCl 3 was chosen as an advantageous reagent for the synthesis of WS-PGO.…”

Arylphosphonic Acid‐Functionalized Polyelectrolytes as Fuel Cell Membrane Material

“…Surely most attractive from an economical point of view would be the arylphosphonation by reaction of an aromatic substrate with P 4 O 10 . This reaction, which corresponds to the well‐known sulfonation with SO 3 , has been applied to the synthesis of low‐molecular‐weight compounds, e.g., phenylphosphonic acid as shown in Scheme 85…”

The reaction of dithiadiphosphetane disulfides with dienes, alkenes and thioaldehydes

“…In the 13 C NMR spectrum of 15 only one carbon environment, other than those due to phenyl and ferrocenyl groups, was present indicating that the product cannot be a thiazaphosphetane, as this would have two 1 H and 13 C signals outside the ferrocenyl and aromatic areas. Considering the 1 H and 13 C NMR spectroscopic data and the molecular ion at m/z 492 ( 12 C 24 1 H 23 56 Fe 31 P 32 S 3 ) the structure 15 containing a dithiophospholane ring was assigned (eqn. ( 9)).…”

“…9). The formation of this heterocycle did pose a 99.20(6) 118.18 (7) 112.20 (7) 112.7(1) 103.9 (1) mechanistic challenge, as a C-C bond is formed and 15 cannot be rationalised as being an adduct of thiobenzaldehyde and the dithiophosphine ylide. One suggestion as to the mechanism would be the [2 ϩ 2] cycloaddition of thiobenzaldehyde with the dithiophosphine ylide followed by a second [2 ϩ 2] cycloaddition.…”

“…dev. from the P(1)-P(2)-S(2)-N(1) mean plane 0.36 Å for N (1)] with the carbon substituent on the nitrogen atom lying only 0.09 Å out of the plane of the…”