(Benzene-1,3,5-triyl)tris[phosphine] (C6H3(PH2)3) and (benzene-1,3,5-triyl)tris[phosphonic acid] (C6H3[P(O)(OH)2]3). Absence of hydrogen bonding in solid primary phosphines

Stephan A. Reiter, Bernd Assmann, Stefan D. Nogai, Norbert W. Mitzel, Hubert Schmidbaur

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The prolonged photo-Arbuzov reaction (3 weeks, Hg lamp) of 1,3,5-trichloro-benzene with a large excess of trimethyl phosphite (as a solvent) at 50° gives moderate yields of dimethyl (3,5-dichlorophenyl)phosphonate (1; 14.5%), tetramethyl (5-chloro-1,3-phenylene)bis[phosphonate] (2; 35.4%), and hexamethyl (benzene-1,3,5-triyl)tris[phosphonate] (3: 30.1%). The products can be separated by fractional distillation. Acid hydrolysis of the esters gives almost quantitative yields of the corresponding phosphonic acids 4-6. Reduction of the esters 1-3 by LiA1H4 in tetrahydrofuran affords the primary phosphines (3,5-dichlorophenyl)phosphine (7; 46.5%), (5-chloro-1,3-phenylene)bis[phosphine] (8; 34.5%) and (benzene-1,3,5-triyl)tris[phosphine] (9; 25.2% yield). In the crude reduction products from 2 (preparation of 8) and from 3 (preparation of 9), (3-chlorophenyl)phosphine and (1,3-phenylene)bis[phosphine], respectively, are observed as by-products. All compounds are characterized by standard analytical, spectroscopic, and (for 1, 7, and 8) structural techniques. The arrangement of the molecules in the crystal structures of 7 and 8 suggest that H-bonding between the primary arylphosphines is virtually insignificant for the packing of the components. This is in marked contrast to the importance of H-bonding for the supramolecular chemistry of arylamines. The new primary polyphosphines and polyphosphonic acids are to be employed in the construction of extended arrays.

Original languageEnglish
Pages (from-to)1140-1150
Number of pages11
JournalHelvetica Chimica Acta
Issue number4
StatePublished - 2002
Externally publishedYes


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