3- Methyl-l -phenyl-3-phospholene

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. 

Methyl-l-phenyl-3-phospholene, 152 Methyl phenyl sulfide, 89... 

Reaction of 2,3-dimethyl-1,3-butadiene with methyl acetoacetate is carried out with PdCl2 as a catalyst in the presence of sodium phenoxide. When triphenylphos-phine is employed, a 1 2 adduct is obtained. On the other hand, the use of 3-methyl-l-phenyl-A3-phospholene (168) at 100 °C causes formation of a 1 1 adduct to give... 

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. 

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) ... 

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. 

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). 

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. 

Going one stage further phospholes present distinctive features on account of the aromatic character <1967 78 1969,77) this property is clearly reflected in the values of the coupling constants. The relevant data for 1-methyl phospholes have been published (1969>77) and are shown in 98 these are obviously contrary to the trends previously reported for 2-phospholenes in which 2/(P-CH) < 3/(PCCH). However, these are in agreement with observations on l-phenyl-2,5-dimethylphosphole (99)(1967 70) and on l-phenyl-3,4-dimethylphosphole (100) (1969,20) in the latter compound both couplings mentioned have been found to be of the same sign. 

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. 

The 2- and 3-phospholenes are prepared by the McCormack reaction and are good candidates as starting materials for the preparation of five-and six-membered phosphorus heterocycles [25-27]. From l-methoxy-3-methyl-2-phospholene 64 or l-methoxy-2,3-diacetoxy-3-methylphospholane 67, l-aryoxy-3-methyl-2-phospholenes 66a-c (Scheme 19), or l-aryoxy-2,3-diacetoxy-3-methylphospholane 69 (Scheme 20) with a substituted phenyl group at phosphorus, or l-aryl-3-methyl-2-phospholenes 71a-g (Scheme 21) are prepared by a substitution reaction and/or a Grignard coupling reaction [28,29]. 

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. 

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