Phosphan 2- -propyl

Phosphane, Dimethyl- (3.3.3-trifluoro-propyl)- ElOb,. 676 (En + HPR2)... 

Phosphane Bis-[tiifluoromethvl]-(hexiilluoro-2-trinuoromcthyl-propyl)- ElOb,. 677 [F -propene + [Pg.633]

Bis-[2-cyan-propyl]-ethyl-phosphanoxid " 15,7 g (0,18 mol) 2-Methyl-acrylamid werden portionsweise unter Riihren in einer Argonatmosphare so zu 30,1 g (0,18 mol) Chlor(2-cyan-propyl)-ethyl-phosphan gegeben, daB die Temp, zwischen 40 bis 60° bleibt. Es bildet sich eine kristalline, hygroskopische Masse (Imminium-Salz Schmp. 139-141°), die beim Erhitzen auf 130—140° Chlorwasserstoff abspaltet anschlieBend wird destilliert Ausbeute 27,6 g (71%) Sdp. 205-20675 10 2 Torr (6,5 10 3 kPa). 

Chirales Methyl-phenyl-propyl-phosphan wird von Salpetersaure unter Inversion und von Distickstofftetroxid unter Retention mit partieller Racemisierung zu Methyl-phenyl-pro-... 

Vollig analog werden aus Dichlor-methyl- und Dichlor-propyl-phosphan die entspre-chenden [(Benzyl-carboxymethyl-amino)-methyl]-methyl- (100%) bzw. -propyl-phos-phinsaure-Hydrochloride (83%) erhalten53. 

Bis-[2-methyl-propyl]-phosphan und Dibutyldisulfan reagieren unter Sauerstoff-Aus-schluB in siedendem Benzol in fast quantitativer Ausbeute zu Bis-[2-methyl-propyl]-di-thiophosphinsaure-butylester und Butan989 ... 

Bis-[2-methyl-propyl]-dithiophosphinsaure-butylestt r H 26,7 g (0,15 mol) Dibulyldisulfan und 17,2 g (0,12 mol) Bis-[2-methyl-propyl]-phosphan werden 16 Stdn. in 150 ml Benzol unter Argon zum RiickfluB erhitzt. Nach Abziehen des Losungsmittcls i.Vak. wird destilliert Ausbeute 30,4 g (97%) Sdp. 97-10370,05 Torr (7 Pa). 

Bis-[4-cblor-phenyl]- Xll/1, 272 Bis-[2-cyan-ethyl]- XII/1, 271 Bis-[2-cyan-etbyl]- -benzylester XII/1, 283 Bis-[4-methyl-pbcnyl]- XII/1, 272 Bis-[4-metbyl-pbenyl]- -butylester E2, 270 Bis-[2-methyl-propyl]- -butylester E2, 268, 269 aus Dibutyldisulfan und Bis-[2-metbyl-propyl]-phosphan E2, 269... 

Diphenyl-(l-mcthoxy-3-phenyl-allyl)- E2, 14 Diphcnyl-(2-methoxy-propyl)- E2, 14 Diphenyl-(5-methoxy-2-tctrahydrofuryl)- E2, 14 Diphenyl-methyl- XI1/1, 137, 142, 148, 150, 152, 238 E2, 16, 34, 42, 64, 148 aus Diphenyl-methoxy-phosphan und Azo-methan (Belichtung) E2, 26 aus Triphenyl-phosphan und Dimethylsulfat XII/1, 145... 

Diphenyl-(1-phenyl-propyl)- E2, 147 Diphenyl-(2-phcnyl-vinyl)- E2, 66 Diphenyl-[2-(/ranv-2-phcnyl-vinyl)-phenyl)-aus Diphenyl-(2-phenyl-ethinyl)-phosphan und wasserhaltigem Ethanol E2, 48 Diphenyl-(phthalimino-methyl)- E2, 22 Diphenyl-piperidinomethyl- XII/1, 155 Diphenyl-1-propinyl- E2, 76 Diphenyl-tosyloxymethyl- El, 513 Diphenyl-(3-trialkylsik>xy-a]]yD- E2, 27 Diphenyl-trichlormethyl- XII/1, 151 F.2, 23 (Z)-Diphenyl-(3-triethylsilyloxy-allyl)- E2, 27 (Z)-Diphenyl-(3-triethylsilyloxy-2-butenyl)-aus Diphenyl-methoxy-phosphan und Chlor-triethyl-silan/3-Oxo-l-butcn E2, 27 Diphenyl-trifluoracctyl- E2, 8, 19, 42 Diphenyl-(2,2,2-lrifluor-ethyl)- E2, 16 Diphenyl-(l,l,3-trimethyl-2-butenyl)- E2, 71 Diphenyl-(trimethylsilyl-methyl)- E2, 22, 66 Diphcnyl-(l-trimethylsilyloxy-alkyl)- E2, 26 Diphenyl-triphenylmethyl-XlI/1,151 Diphenyl-(triphenylstannyl-methyl)-... 

Hydroxy-(l-methyl-heptyloxy)- XII/2, 6 Hydroxy-(4-methyl-pentyl)- El, 271 Hydroxy-(4-methyl-phenyl)- E2, 295 Hydroxy-(2-methyl-propyl)- XII/1, 295 Hydroxy-( 1-methyl-l-propylamino-ethyl)-aus Dihydroxy-phosphan, Propylamin und Aceton Xll/1, 300... 

Phosphan Tris-[3-hydroxy-propyl]-El, 118 (PH3 + Allyl-OH) Phosphonsaure Methan- -dibutyl-ester XII/1, 462... 

Phosphan (2,2-Dimethyl- 1-methy-len-propyl)-(2,2-dimethyl-propyliden)- E19b, 1823 [Carben-CH-rnsertion (intra)/Ringspal-tung]... 

The selectivity of butadiene cyclooligomerization in the presence of bis(l,5-cyclooctadiene)-nickel(0) varies with the phosphane added, e.g., monophosphanes, such as (S)-ter/-butyl(iso-propyl)phenylphosphane and (- )-dimethyl(phenyl)phosphane, or diphosphanes, such as Diop. In all cases, 1,5-cyclooctadiene is preferentially formed, along with 4-vinylcyclohexene, ill a 4.5-6 1 ratio. The optical purity of the 4-vinylcyclohexene reaches 12% at a monophosphane/ nickel ratio of about 8 1 and is much lower with Diop57. The use of various 1,3,2-dioxaphospho-lanes with bulky substituents leads to a significant improvement in product selectivity (favoring 4-vinylcyclohexene over 1,5-cyclooctadiene in a ratio of up to 1 0.3) and in the enantioselectiv-ity. The best Optical yield (35% ee, later corrected to 24% ee58) was obtained with a nickel complex of diethyl 2-toT-butyl-l,3,2-dioxaphospholane-4,5-dicarboxylate (1) at 20 C57. 

In contrast to unfunctionalized ketones, Wilkinson-type catalysts are quite effective in the hydrogenation of 2-oxo esters. With in situ catalysts consisting of [Rh(cod)Cl]2 2 and a proline derived chelate phosphane BPPM 3l4, quantitative hydrogenation of 2-oxo esters to (7 )-2-hydroxy esters was achieved. Dry benzene or dry tetrahydrofuran as solvent were superior to alcohols usually used in hydrogenation reactions with Wilkinson-type catalysts. While methyl 2-oxopropanoate was reduced to methyl (R)-2-hydroxypropanoate in only 66% eel5, propyl and 2-methylpropyl 2-oxopropanoate gave the (R)-alcohols with 76% and 71 % ee, respectively (Table 2)15,10. 

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