100281-31-0

Upstream product

• 177902-37-3 (E)-1-Bromo-2-(2,4,6-tri-tert-butylphenyl)-2-phosphaethenyllithium 
• 93746-68-0 2,4,6-tri-tert-butylphenyl-P=C(Br)SiMe₃ 
• 92957-41-0 Dibromomethyl-(2,4,6-tri-tert-butyl-phenyl)-phosphane 
• 100281-23-0 [(dibromomethylene)(2,4,6-tri-tertbutylphenyl)phosphine] 
• 83115-12-2 (2,4,6-tri-tert-butylphenyl)phosphine 
• 84751-28-0 2-(2,4,6-tri-tert-butylphenyl)-1,1-bis(trimethylsilyl)phosphaethene 
• 118281-77-9 (Diiodomethylene)(2,4,6-tri-tert-butylphenyl)phosphine 
• 75-25-2 Bromoform 
• 79074-00-3 2,4,6-tri-t-butylphenylphosphonous dichloride 

Downstream Products

• 156696-16-1 Bromo(dibromomethyl)(2,4,6-tri-tert-butylphenyl)phosphane 
• 99364-92-8 (E)-benzylidene(2,4,6-tri-tert-butylphenyl)phosphane 
• 112150-07-9 Dimethyl-[4-(2,4,6-tri-tert-butyl-phenylphosphanylidenemethyl)-phenyl]-amine 
• 84114-18-1 1-(2,4,6-tri-tert-butylphenyl)-1-phosphaethene 
• 123542-40-5 Eth-(Z)-ylidene-(2,4,6-tri-tert-butyl-phenyl)-phosphane 

Relevant academic research and scientific papers

Formation of 6,8-di-tert-butyl-3,4-dihydro-4,4-dimethyl-1-phosphanaphthalene by the reaction of 2,2-dibromo-1-(2,4,6-tri-tert-butylphenyl)-1-phosphaethene with butyllithium

Sterically crowded 1-bromo-2-(2,4,6-tri-tert-butylphenyl)-2-phosphaethenyllithium gave 6,8-di-tert-butyl-3,4-dihydro-4,4-dimethyl-1-phosphanaphthalene by intramolecular insertion of an intermediary phosphinidene carbene species into one of the C-H bonds of the two o-tert-butyl groups.

The synthetic potential of C-halophosphaalkenes

Methodologies for the functionalization of phosphaalkenes Mes*P=CHal2 were developed. Lithiation with n-butyllithium yielded carbenoids Mes*P=CLiHal which were reacted with various electrophiles such as acid chlorides, carbonyl compounds, and metal halides. The dihalophosphaalkenes were also converted to monohalophosphaalkenes; the latter proved to be suitable for Stille-type cross coupling reaction with Grignard reagents. New phosphaalkenes of the type (E)-Mes*P=C(H)Ar with a variety of functionalities were obtained in high yield and isomeric purity.

C-Halophosphaalkenes: probing the range of stability and reactivity towards bromine

The importance of steric protection for the stability of phosphaalkenes RP=CI2 (6) was investigated by varying the size of group R.The phosphaalkene IsP=CI2 (6b) (Is = 2,4,6-triisopropylphenyl) could be prepared in 15percent isolated yield by reaction of IsPCl2 and HCI3 with two equivalents of lithium diisopropylamide, in analogy to the synthesis of the stable, sterically more protected, Mes*P=CI2 (6a) (Mes* = 2,4,6-tri-tert-butylphenyl).If the steric protection on the phosphorus eas decreased further (R = Es = 2,4,6-triethylphenyl, R = Mes = 2,4,6-trimethylphenyl), the substitution products RP(Cl)N(i-Pr)2 (R = Es (9c) or Mes (9d)) were formed as main products, in addition to thermally unstable phosphaalkenes EsP=CI2 (6c) and MesP=CI2 (6d).The structures of 9c-d were corroborated by independent synthesis from RPCl2 and two equivalents of diisopropylamine.The reaction of 6a with bromine gave an E/Z mixture of the C-bromo-C-iodophoaphaalkene (EZ)-Mes*P=CBrI (E/Z-10).Further reaction with bromine proceeded via Mes*P=CBr2 (5a) and finally led to Mes*P(Br)(CHBr2) (12).

SYNTHESIS AND REACTIVITY OF P-SUPERMESITYL-C-HALOPHOSPHAALKENES

The synthesis of the title compounds in high yield via a new route are presented and their reaction with n-butyllithium and subsequent functionalisations is discussed.

SYNTHESE UND REAKTIONEN DER 2,4,6-TRI-TERT-BUTYLPHENYLDIHALOGENMETHYLENPHOSPHANE1

The synthesis of dihalogenated phosphaalkanes 2a,b is reported.After metallation with n-BuLi they could be substituted by halogenated compounds.

REAKTIONEN DES 2,4,6-TRI-TERT-BUTYLPHENYLPHOSPHANS

The reaction of phosphaalkene 1 with ozone, sulfur and selenium yields the phosphoranes 2, 3 and 4.The methylene halogene substituted phosphaalkene 5 is formed with bromine.The bipyramidal iron carbonyl complexes 8 and 9 are obtained by reaction of 1 and 7 with Fe2(CO)9.