Catalysis of Organic..

Puckette 372 1 Mixed 2- 71% Nonyl Aldehydes L/B = 0.91octenes3 7 1-Octene 98% Nonyl Aldehydes L/B = 1.964 Bis(2-methylphenyl)chlorophosphiteTrans-2-Octene2-Methyl-1-octanal, 2-Ethyl-1-heptanal, & 2-Propyl-1-hexanal.L/B = 0.155 Bis(2-methylphenyl)chlorophosphite1,7-OctadieneFour Dialdehydes(99.3% total; 40.4%1,10-decanedialdehyde).No monoaldehydes.a All runs performed in autoclaves as described in references 9 and 11.In summary, chlorophosphites and fluorophosphites represent a new and viableclass of ligands for the hydroformylation reaction and behave much like traditionaltriorganophosphorus ligands. The halophosphites are easy to obtain andsurprisingly stable under process conditions.Experimental SectionLigands – 2,2'-Ethylidenebis (4,6-di-tert-butylphenyl) fluorophosphite (1) waspurchased from Aldrich Chemical Company. The remaining chlorophosphite andfluorophosphite ligands were prepared by literature procedures or by minormodifications of the published procedures (10). All ligands were characterized by1 H NMR, 31 P NMR and mass spectroscopy.Bench Unit Testing – The physical description of the bench unit and operation of theunit has been described in reference 9.AcknowledgementsAlthough many people have contributed to the success of this project, a few deservespecial mention: Ginette Struck Tolleson as a co-worker, Tom Devon as a co-workerand mentor, Jimmy Adams and Sue Gray for bench unit operations and EastmanChemical Company for permission to publish this work.References1. L. H. Slaugh and R. D. Mullineaux, U.S. Pat. No. 3,239,566, to Shell OilCompany (1966).2. R. L. Pruett and J. A. Smith, US Pat. 3,527,809 to Union Carbide Corporation(1970).