Phospholene oxide 3-methyl-1 -phenyl

Im Gegensatz zu Phosphol-Derivaten erhalt man mit 3-Methyl-l-phenyl-4,5-dihydro-phospholen und aromatischen Carbonsaure-chloriden 3-Methyl- /-phenyl-4,5-dihydro-phosphol-1 -oxid und einen aromatischen Aldehyd292. Offensichtlich wird aus der apicalen Position des intermediaren Phosphorans der Aroyl-Rest verdrangt. Die Reaktion laBt sich zur gezielten Synthese von aromatischen Aldehyden aus Acylchloriden verwenden (Alternative zur Rosenmund-Reaktion) ... 

To address this concern uretonimine-modified isocyanates with improved low-temperature properties were prepared using 4,4 -diphenylmethane diisocyanate catalyzed with 3-methyl-l-phenyl-3-phospholene-l-oxide. The formation of uretonimine was consistently higher than uretdione formation using this catalyst. The uretonimine-modified isocyanate can be stored at temperatures substantially lower than ambient temperature while still remaining liquid. In addition it is soluble in melted 4,4 -diphenylmethane diisocyanate. 

A reactor was charged with 93.80% 4,4 -diphenylmethane diisocyanate, 6.20% 2,4 -diphenylmethane diisocyanate, and 3-methyl-1 -phenyl-3-phospholene-1 -oxide (6 ppm) as catalyst and then heated for 6 hours at 110°C. Trifluoromethanesulfonic acid (50 ppm) was then added to quench the reaction. The mixture was then cooled to 50°C and the product isolated having a 29.5% isocyanate content. 

Rosthauser et al. (4) used l-methyl-3-phospholene-l-oxide to prepare and isolate oligomeric diisocyanates containing dicarbodiimides using 4,4 -diphenyl-methane diisocyanate. Diisocyanates containing dicarbodiimides were also prepared by Takahashi et al. (5) using 3-methyl-l-phenyl-2-phospholene-l-oxide as the reaction catalyst. 

Dibromo-3-methyl-l-phenylphospholane 1-oxide (125) prepared from l-phenyl-3-methyl-2-phospholene 1-oxide and bromine in the presence of... 

Two-Step Process. A mixture composed of 100 g of 4,4 -diphenylmethane diisocyanate and 1.1 g of l-phenyl-3-methyl-l-phospholene oxide is stirred for 3 minutes at room temperature. After carbon dioxide is evolved 4.0 g of 2,4,6-tris(dimethylaminomethyl) phenol is added into the reaction mixture. The mixture generates a reaction exotherm and expands to form a foamed product. After curing at 125°C for one hour, the resultant foam is colorless and posesses low friability. 

A foam was prepared firom polymeric isocyanate (134 pbw) 3,3, 4,4 -benzophenonetetracarboxylic dianhydride (45 pbw) epoxy novolak resin (20 pbw) wetting agent (1 pbw) methanol (2.5 pbw) N,N, N -tris(dimethylaminopropyl)-s-hexahydrotriazine (2.5 pbw) triethylenediamine (2.5 pbw) and l-phenyl-3-methyl-2-phospholene 1-oxide (2.5 pbw). 

For catalyzed dimerization of phenyl isocyanate to diphenylcarbodiimide, see 3-Methyl-1 -ethyl-3-phospholene-1 -oxide. 

An efficient method for preparation of aromatic and aliphatic carbodiimides involves the reaction of an Isocyanate with 3-methyl-1-phenyl-S-phospholene-1-oxide, the most readily prepared catalyst of Us type. ... 

ALDEHYDES Bis(4-methylpiperazinyl)aluminum hydride. Di(r) -cyclopentadienyl)-(chloro)hydridozitconium(IV). Dihalobis(triphenylphosphine)paIIadium(H). 7,8-Dimethyl-l,5-dihydro-2,4-benzodithiepin. Grignard reagents. Lithium bis(ethylene-dioxyboryOmethide. 3-Methyl-I-phenyl-2-phospholene. 2-Methyl-2-thiazoline. Methylthioacetic acid. 3-Methylthio-l,4-diphenyl-s-triazium iodide. Sodium meth-oxide. Methylthiomethyl N,N-dimethyldithiocarbamate. Sodium tetracarbonylferrate(II). Tetra-n-butylammonium borohydride. Triethylallyloxysilane. N,4,4-Trimethyl-2-oxazolinium iodide. 

Toluene diisocyanate (TDI), 54 C2CI4, 500 1 -Phenyl-3-methyl-phospholene oxide. 120 4 — b... 

MDI, 675, + Phenylisocyanate, 71.4 C2CU 3-Methyl-1 -phenyl-2-phospholene 1-oxide, 1.87 120 4 e... 

Isophorone diisocyanate, 231.2, and butyl isocyanate, 68.8 Amylacetate, 270 1 -Phenyl-3-methyl-2-phospholene oxide, 30 g of 10% soln in xylene 140 26 g... 

Polycarbodi-imides have been prepared from isocyanates using 1-phenyl-3-methyl-2-phospholene-l-oxide as catalyst. ... 

V. Ujj, J. Schindler, T. Novak, M. Czugler, E. Fogassy, G. Keglevich, Coordinative resolution of 1-phenyl- and l-naphthyl-3-methyl-3-phospholene 1-oxides with calcium hydrogen 0,0 -dibenzoyl-(2R,3R)-tartrate or calcium hydrogen 0,0 -di-p-toluyl-(2R,3R)-tartrate, Tetrahedron Asymmetry 19 (2008) 1973-1977. 

The reaction is usually carried out at high temperatures (of about 200°C) in a polar solvent, such as tetramethylene sulfone, and the polyamide formation can be accelerated by the addition of l-phenyl-3-methyl-2-phospholene 1-oxide as catalyst. However, in the case of a two-step process, the reaction time of the first step must be carefully controlled, since the catalyst can also play a role in the formation of carbodiimides from two terminal isocyanate groups [36], These carbodiimides can then further react and lead to crosslinking [36], In most cases [34-39], the polymers are prepared with 4,4 -methylene bis(phenyl-isocyanate) (MDI), using adipic acid, isophtahc acid, azelaic acid, or a mixture of two of them (in order to accelerate the solubilization of the polyamide phase in the solvent) and a polyether based on tetramethylene oxide, ethylene oxide, or a mixture of propylene oxide and ethylene oxide. 

Isocyanates have been shown to undergo a high jdeld reaction with carboxylic acids to afford amides. Polymerization of aromatic diisocyanates with aromatic dicarboxylic acids was carried out in the presence of 3-methyl-l-phenyl-2-phospholene 2-oxide to afford aramids (7). The polymerization was carried out in sulfolane at 200 C. Polymers with inherent viscosities of up to 1.8 dL/g were obtained. 

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