100281-28-5

Upstream product

• 177902-37-3 1-bromo-2-(2,4,6-tri-t-butylphenyl)-2-phosphaethenyllithium 
• 74-88-4 methyl iodide 
• 100281-23-0 [(dibromomethylene)(2,4,6-tri-tertbutylphenyl)phosphine] 
• 84751-28-0 2-(2,4,6-tri-tert-butylphenyl)-1,1-bis(trimethylsilyl)phosphaethene 
• 177902-37-3 (E)-1-Bromo-2-(2,4,6-tri-tert-butylphenyl)-2-phosphaethenyllithium 

Downstream Products

• 123542-40-5 Eth-(Z)-ylidene-(2,4,6-tri-tert-butyl-phenyl)-phosphane 
• 1211351-65-3 (Z)-1-(2,4,6-tri-tert-butylphenyl)(2-benzyl-2-methyl-1-phosphaethene) 
• 123542-45-0 (2,4,6-tert-butylphenyl)(2,2-dimethylphosphaethene) 
• 1439388-97-2 (E)-2-methyl-2-ethenyl-1-(2,4,6-tri-t-butylphenyl)-1-phosphaethene 
• 536702-93-9 (Z)-2-methylsulfanyl-1-(2,4,6-tri-t-butylphenyl)-1-phosphapropene 
• 122279-50-9 1-(2,4,6-tri-tert-butylphenyl)-1-phosphaallene 
• 634588-60-6 (E)-2-methyl-3,3-diphenyl-1-(2,4,6-tri-t-butylphenyl)-1,3-diphosphapropene 
• 472967-64-9 C₂₀H₃₂LiP 
• 870622-01-8 C₂₀H₃₂Cl₂P₂ 
• 870622-04-1 1,3,5-tri-tert-butyl-2-(1-dibutylphosphanyl-ethylidenephosphanyl)-benzene 
• 870622-02-9 1,3,5-Tri-tert-butyl-2-[1-(di-p-tolyl-phosphanyl)-eth-(E)-ylidenephosphanyl]-benzene 
• 870622-03-0 2-[1-[Bis-(4-methoxy-phenyl)-phosphanyl]-eth-(E)-ylidenephosphanyl]-1,3,5-tri-tert-butyl-benzene 
• 472967-63-8 pentacarbonyl((Z)-2-bromo-1-(2,4,6-tri-t-butylphenyl)-1-phosphapropene)tungsten⁽⁰⁾ 
• 472967-66-1 1,6-bis(2,4,6-tri-t-butylphenyl)-1,6-bis(pentacarbonyltungsten⁽⁰⁾)-1,6-diphosphahexa-1,5-diene 

Relevant academic research and scientific papers

Phosphorus centers of different hybridization in phosphaalkene-substituted phospholes

Phosphole-substituted phosphaalkenes (PPAs) of the general formula Mes P=C(CH3)-(C4H2P(Ph))-R 5a-c (Mes=2,4,6-tBu 3Ph; R=2-pyridyl (a), 2-thienyl (b), phenyl (c)) have been prepared from octa-1,7-diyne-substituted phosphaalkenes by utilizing the Fagan-Nugent route. The presence of two differently hybridized phosphorus centers (σ2,λ3 and σ3, λ3) in 5 offers the possibility to selectively tune the HOMO-LUMO gap of the compounds by utilizing the different reactivity of the two phosphorus heteroatoms. Oxidation of 5a-c by sulfur proceeds exclusively at the σ3,λ3-phosphorus atom, thus giving rise to the corresponding thioxophospholes 6a-c. Similarly, 5a is selectively coordinated by AuCl at the σ3,λ3-phosphorus atom. Subsequent second AuCl coordination at the σ2, λ3-phosphorus heteroatom results in a dimetallic species that is characterized by a gold-gold interaction that provokes a change in π conjugation. Spectroscopic, electrochemical, and theoretical investigations show that the phosphaalkene and the phosphole both have a sizable impact on the electronic properties of the compounds. The presence of the phosphaalkene unit induces a decrease of the HOMO-LUMO gap relative to reference phosphole-containing π systems that lack a P=C substituent.

Alternative synthesis and structures of C-monoacetylenic phosphaalkenes

An alternative synthesis of C-monoacetylenic phosphaalkenes trans-Mes*P=C(Me)(C≡CR) (Mes* = 2, 4, 6-tBu 3Ph, R = Ph, SiMe3) from C-bromophosphaalkenes cis-Mes*P=C(Me)Br using standard Sonogashira coupling conditions is des

Preparation and properties of kinetically stabilized phosphaethene derivatives carrying the methylsulfanyl group

1-Methylsulfanyl-2-(2,4,6-tri-t-butylphenyl)-2-phosphaethenyllithiums, prepared from (Z)-2-bromo-2-methylsulfanyl-1-(2,4,6-tri-t-butylphenyl)-1-phosphaethene, displayed an E/Z isomerization upon warming to room temperature. The copper-mediated coupling reaction afforded (Z,Z)-2,3-bis(methylsulfanyl)-1,4-diphosphabuta-1,3-diene. The reaction of the phosphaethenyllithiums with dimethyl disulfide and iodomethane gave the corresponding bis(methylsulfanyl)phosphaethene and a methylated E-isomer, respectively. On the other hand, the latter methylated Z-isomer was alternatively prepared from (Z)-2-bromo-1-(2,4,6-tri-t-butylphenyl)-1-phosphapropene. Both methylated E- and Z-isomers were allowed to react with W(CO)5(thf) to give the corresponding pentacarbonyltungsten(0) complexes, either of which was deprotonated to give the 3-phospha-2-propenyllithium derivative leading to the formation of a homocoupled (Z,Z)- 1,6-diphosphahexa-1,5-diene complex. Some key compounds were analyzed by X-ray crystallography, revealing the effect of the methylsulfanyl group on the structures. A straightforward preparation of 1-(2,4,6-tri-t-butylphenyl)-1-phosphaallene as well as its carbonyltungsten(0) complex is also described.

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.

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.