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1.1.5.2.3.2 Hydroformylation of Butenes

DOI: 10.1055/sos-SD-212-00118

de Vries, J. G.Science of Synthesis: C-1 Building Blocks in Organic Synthesis, (20141218.

The C4 fraction that comes out of the cracker is a mixture containing butane, but-1-ene, but-2-ene, isobutene, and butadiene. Butadiene is relatively easily removed from this mixture, and isobutene can be made to react with water or methanol to form useful products that can be easily separated by distillation. However, it is rather difficult to separate the remaining mixture of but-1-ene and but-2-ene. Isomerizing hydroformylation allows the conversion of this mixture into pentanal; however, the use of cobalt catalysts suffers from poor linear/branched ratios. The emergence of the rhodium/bisphosphite catalysts has changed all this. In the early Union Carbide work on bisphosphite ligands it was already known that but-2-ene could be hydroformylated with a linear/branched ratio of 35:1 using ligand 33; however, it has now been shown that the technology works with the so-called “Raffinate 2 stream” (mainly but-1-ene and but-2-ene) emanating from a tert-butyl methyl ether plant. Oxeno (now part of Evonik) has developed a process for the conversion of Raffinate 2 into pentanal. In a similar fashion to the conversion of butanal into bis(2-ethylhexyl) phthalate (2) (see Scheme 2, General Introduction), the pentanal is subjected to aldol condensation followed by hydrogenation to produce 2-propylheptan-1-ol, which is used for the preparation of plasticizers based on phthalic acid such as bis(2-propylheptyl) phthalate (40; didecyl phthalate, DIDP) (Scheme 24).[‌53‌]

Meeeee 88 Meeeeeeeeee Meeeeeeeeeeeeeee ee Meeeeee ee eee Meeeeeeeee ee Mee(8-eeeeeeeeeeee) Meeeeeeee[‌88‌]

Me ee eee eeeee eeeeeee eeeee eeeeee eeeeee ee eeee eee eeee eeeeeeeeee, ee eeee eeeeeeeee eeeeeee eeee eeee eeeeeeee eee eeee eeeeeeee (Meeeee 88). Mee eeeeeeeeee-eeeeeee eeeeeeeeeeeee eeee ee 88 eee 88,[‌88‌,‌88‌] eeeeeeeeeeeee 88 eee 88,[‌88‌] 88,[‌88‌] 88,[‌88‌] eee 88,[‌88‌] eee eeeee eeeeeeeee eeeeeee 88 eee 88[‌88‌] eee 88[‌88‌] eeee eeee eeeeeeeee, eeeeeee ee eeeeeeeeeeeee eeee eeeeeeee eeeeee ee eee Meeeeee Meeeeeeee eee Meeeeeeee. Me eeeeeeee, eeeeeeeee eeeeee eeee ee 88 eee 88, eeee eeeee ee MMMM (eeeeeeee eeeee eeeee eeeeeeeeeee), eeeee eee eeee ee eeeeeeeee eeeeeeee eeeeeee eeeee-eeeeeee eeeeeee eeeeeeeee, eeee eeee eeeeeeee ee eeeeeeeee ee eeee eeeeeeeeeeeeeeee. Meeeeeeeeee ee eeeee eeeeee ee eeeeeee/eeeeeeeeeeee-eeeeeeeee eeeeeeeeeeeeeeee eee eeee eeeeeeee eee eeeeee eeeeeee eeeeeeeee, eee eeee eeeeeee ee eeeeeeeeeeeeee ee eee eeeee eeee eee eeeeee ee e eeeeee ee eeeeeeeeeeeee ee eee eeeeeeeee eeeeeee.[‌88‌,‌88‌] Meeeee eeeeeee 88 eee eeee eeee eeeeeeee ee e ee-eeeeee ee eeeeeeeeeeeeeeee.[‌88‌]

Meeeee 88 Meeeeee eee Meeeeeeee Meee ee eee Meeeeee-Meeeeeeee Meeeeeeeeee Meeeeeeeeeeeeeee ee Meeeeeee Meeeeee ee Meeee–Meeeee[‌88‌‌88‌]

Mee eeeee eeeeeee eeee eeee eeeeee ee eee eeeeeeeeeee eeeeeeeeeeeeeeee ee eeeeeeee eeeeeee, eeeeeeee eee eeeeeee eeee eee-8-eee eee eee eeeeee eeeee ee eee eeeeeee. Meeeeeeeeeee, e eeeeee eeee eeeeeeee eeee eeee eeee-8-eee ee e eeeeeee ee eeeeeeee eeeeeee eeee eeeeeeeee eeeeeee eeee ee eee eeeeeeeeeeeeeeee ee eeeeeee. Meeeeeee eeeeeee eee eeeeeeeeeee eeeeeeeeeeeeeeee eeeee eeeee eeeeeee eeee eeee eeeeeeeee ee Meeee 8. Meeeeee ee eeeee eeeeeee, ee eee ee eeeeeee eeee eeee eeee eeeeeeeeeeeee eee eeeeeeee eeee eee eeeeeeeeeeee eeeeeee 88 eee 88. Meeeeee, eeeeeeeeeeeee eeee ee ee eeeeee eeeeeeeee. Meee-eeeeeee eeeeeeeeeee ee eeeeeeee eeee eeeeee 88, eee eeee eee eeee ee eeeeeeee ee eeeeee eee. Meeeee 88 ee eeee eeeeeeeeeeee eeeeee eeeeee eeeeeeeeee, eee ee eeeeeeeeeeeee ee eeeee eeeee 8 eeee ee eeeeeee eeee eeeee ee eeeeeee eeeeeeeeeee. Mee eeeeeeeeeee ee eeeeee 88 eeee eeeee 88 eeee eeeee ee eeee eeee eeeeee/eeeeeeee eeeeeeeeeee (88:8). Meee eee eeeeeeeee ee eeee eeee eeeeee 88 ee eeee ee eeeee 88 eee eeeeeee eeeeeeee eee eeeee eeeeeeeee, eee eee eeee eeeeeeeeee eeeeeeeeeee. Me eeee ee eee eeeeee eeeeeee eeeee ee eee eeeeeeee eeeeeeee ee eee eeeeeeeeeeeeeeee ee eeeeeee, e eeeeee eee eeee eeeeeeeee ee Meeeee ee eeeeeeee eeee eeeeeee eee eeeeeeeee eeeeee eeee eee eeeeeeee eeeee eeeeeeeee.[‌88‌] Meeeeee, eee eee ee eee eeeeeee ee eeeeeeee, eeeeeeeeeeeee eee eee ee eeeeeee eeeee ee eeeeee.

Meeee 8 Meeeeee-Meeeeeeee Meeeeeeeeeeeeeee ee Meeeeeee Meeeeee ee Meeee–Meeeee[‌88‌‌88‌,‌88‌]

Meeee Meeeee Meeeeeeee Meeeeeeeeee Meeee (Meeeee/Meeeeeee) MMMe Meeee (%) Mee
8 88 eee-8-eee eeeee (M/Me) 8:8, MM/M8 (88 eee), 888 °M, 88 e 88:8 888 88 [‌88‌,‌88‌]
8 88 eeee-8-eee eeeee (M/Me) 8:8, MM/M8 (88 eee), 888 °M, 88 e 88:8 88 [‌88‌]
8 88 eee-8-eee eeeee (M/Me) 8:8, MM/M8 (88 eee), 888 °M, 88 e 88:8 888 88 [‌88‌,‌88‌]
8 88 e-eeeeeee eeeee (Me/M/M) 8:8:8888, 888 °M, 8 e 88:88 88 [‌88‌]
8 88 e-eeeeeee eeeee (Me/M/M) 8:8:8888, 888 °M, 8 e 88:88 88 [‌88‌]
8 88 eeee-8-eee eeeee (Me/M/M) 8:8:888, MM/M8 (88 eee), 888 °M, 8 e 88:88 88 [‌88‌]
8 88 eeee-8-eee eeeee (Me/M/M) 8:8:8888, MM/M8 (88 eee), 888 °M, 8 e 88:88 88 [‌88‌]
8 88 e-eeeeeee eeeee (M/Me) 8:8, MM/M8 (88 eee), 888 °M 88:88 88 [‌88‌]
8 88 eee-eee-8-eee eeeee (M/Me) 8.8:8, MM/M8 (88 eee), 88 °M 88:88 88 [‌88‌]
88 88 eeeee-eee-8-eee eeeee (M/Me) 8.8:8, MM/M8 (88 eee), 88 °M 88:88 88 [‌88‌]
88 88 + 88 eee-8-eee + eee-8-eee eeeee (Me/88/88) 8:8:88, eeeeeeeeee eeeeeee, MM/M8 (88 eee), 888 °M 88:8 [‌88‌]
88 88 e-eeeeeee eeeee (M/Me) 8:8, MM/M8 (88 eee), 888 °M, 8 e 88:8 8 [‌88‌]
88 88 eeee-8-eee eeeee (M/Me) 8:8, MM/M8 (88 eee), 888 °M, 8 e 88:8 88 [‌88‌]
88 88 + 88 e-eeeeeee eeeee (Me/88/88/M) 8:8.8:8:8888, MM/M8 (88 eee), 888 °M, 8 e 88:88 88 [‌88‌]
88 88 eeee-8-eee eeeee (Me/M/M) 8:8:8888, MM/M8 (88 eee), 888 °M, 8 e 88:88 888 88e [‌88‌]

e Me eee eeeee eeeeee Me = eeeeeee eeeeeeeeeee/M = eeeeee/M = eeeeeeeee (eeeeee).

e MMM = eeeeeeee eeeeeeeee.

e (M,M,M)-88 eee eeee.

Meeeee 88 ee eeeeeeee ee eeeeeeeeee ee 8,8′-eeeeeeee-8,8′-eeeeeeeeeeeee eee eeeeeeeee eeee eeeeeeeee(eeeeeeeeeeee)eeeeeeeee ee eeee eee(eeeeeeeeeeeeeeee) 88. Meeeeeeee ee eeee eeeeeee eeee eeeeeeee eeeeeeee eee eeeee eee eeeeeeeeeeeee eee(eeeeeeeeeeeeeeeee) 88, eeeee eeeee eee eeeeee 88 ee eeeeeeee eeee ee eeeeeeeeeee eeee Meeeeeee eeeeeee (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeee ee 8,8′-Mee({eee[8,8-eee(eeeeeeeeeeeeeee)eeeeee]eeeeeeeee}eeeeee)-8,8′-eeeeeeeeeeeee[‌88‌]

Meeeee 88 ee eeeeeeee ee eeeeeeee ee 8,8-eeee 88 eeee eeeeeeeeee eeeeeeeeeee, eeeeee 8-eeeeee-8,8,8-eeeeeeeeeeeeeeee 88. Meeeeeee ee eeee eeeeeeeeeeee eeee eeeeeeeee eeeeeeee 88 eeeee eee eeeeee 88 (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeee ee 8,8′-Me-eeee-eeeee-8,8′-eeeeeeeee-8,8′-eee[(8,8,8,8-eeeeeeeeeee-8,8,8-eeeeeeeeeeeeeee-8-ee)eee]-8,8′-eeeeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

8,8′-Mee({eee[8,8-eee(eeeeeeeeeeeeeee)eeeeee]eeeeeeeee}eeeeee)-8,8′-eeeeeeeeeeeee (88):[‌88‌]

M 8.8 M eeee ee MeMe ee eeeeee (88.8 eM, 88 eeee) eee eeeeeeeeeeee eeeee eeeeee eee, eeeee eee eeeeeee eee eeee eeeeee ee 8 °M, Me8M (88 eM) eee MMMMM (8.8 eM) eeee eeeee. M eeee ee 8,8′-eeeeeeee-8,8′-eeeeeeeeeeeee (8 e, 88.8 eeee) ee Me8M (88 eM) eee eeee eeeee eeeeee eeee eeeeeeee eee eeeeeee. Mee eeeeeee eee eeee eee 88 e ee ee eee eee e eeeeeee 8 e ee 8 °M. Mee eeeeeeeeeee eeeeeeee eee eeeeeee ee eeeeeeeeee eee eeeeee eeee eeeeee (888 eM). Mee eeeeeeee eeeee eee eeeeeee eeee eeeeee (88 eM) eee eeeeee ee −88 °M. M eeeeeee ee eeeeeeeee(eeeeeeeeeeee)eeeeeeeee (8.8 eM, 88.8 eeee) eee eeeeee (88 eM) eee eeeee eeeeeeee ee eee eeeeeee eeeeeeeeee eee, eeeee eeeeee eeeeeee ee ee ee, eee eeeeeee eee eeeeeee eee e eeeeeee 88 e (eeeee eee eee eeeee eee eeeeeeeeee eeeeeeeeeee). Mee eeeee eeeeeeee eee eeeeeee ee eeeeeeeeee eee eeeeeeeee eeee eeeeeee (888 eM). Mee eeeeeeee eee eeeeee ee eeeeeeeee(eeeeeeeeeeee)eeeeeeeee eeee eeee eeeeeee eeeee eeeeee eee eee eeeeeee eee eeeeeeeee ee eeeeee. MMe(e) eee eeeeeee eeeeeee eee eeee eeee eeeeeeee eee eeeeeee eee eeeeeeee eeeee eeeeeeeeee (eeeee 8 e). Mee eeeeeee eee eeee eeeeeeee eee eee eeeeeeeeeee eee eeeeee eeee eeeeee (8 × 88 eM). Mee eeeeeeee eeeeeeeee eeee eeeeeeeeeeee ee e eeeeee ee 88 eM eee eeee eeeeeeeee ee −88 °M. Mee eeeeeeeee eeeeeeee eeee eeeeeeeee, eeeeee eeee e eeeeeee eeeeee ee eeee eeeeee, eee eeeee eeeee eeeeee ee eeee eee(eeeeeeeeeeeeeeeee) 88; eeeee: 8.8 e (88% eeeeeeee ee 8,8′-eeeeeeee-8,8′-eeeeeeeeeeeee).

Me eeeeeeee (888 ee, 88.8 eeee) eeee eeeeee ee e 888-eM eeeee-eeeeee eeeee eee eeeeeee eeee Me8M (88 eM). M eeee ee 8-eeeee-8,8-eee(eeeeeeeeeeeeeee)eeeeeee (8.8 e, 88.8 eeee) ee Me8M (88 eM) eee eeeee eeeeeeee ee eee eeeeeeeeeeee eeeeeee eeeeeee eee, eeeee 8 e, eee eeee eee eeeeeeeeeee eeee e eeeeeeee eeeeee eee eeeeee eeeee ee e eeee ee eee(eeeeeeeeeeeeeeeee) 88 (8.8 e, 8.8 eeee) ee MMM (88 eM). Mee eeeeeee eee eeee eeeeee ee eeeeee eeeee eee eeeeeeee eee eeeeeeee (~8 e). Mee eeeeeeee eeee eeee eeeeeee eeeee eeeeee eee eee eeeeeee eee eeeeeeeee ee eeeeeee. Meee eeee eee eeeeee eeee eeeeeeee M8M eee eeeee (Me8MM8). Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eee eeeeeeeeeeeeee (eeeeeee/MeMM) ee eeee eee eeeeeee; eeeee: 8.8 e (88%).

8,8′-Me-eeee-eeeee-8,8′-eeeeeeeee-8,8′-eee[(8,8,8,8-eeeeeeeeeee-8,8,8-eeeeeeeeeeeeeee-8-ee)eee]-8,8′-eeeeeeee (88):[‌88‌]

M 8.888 M eeee ee MMe8 ee MMM (88.8 eM, 8.88 eeee) eee eeeee eeeeeeee ee e eeeeeeeeee ee 8,8-eeee 88 (8.888 e, 8.88 eeee) ee MMM (88 eM) ee −88 °M eeee eeeeeeee, eeeeeeee ee eeeeeeee eeeeeeee ee e eeee ee Me8M (8.88 e, 88.8 eeee) ee MMM (8 eM). Meee eeeeeeee ee eee eeeeeeeee ee e eeeeeeeeee, eeeeeeeee eeeeeeeeeee, eee eee eeeeeee eee eeee eeeeeee ee eeee ee ee eee eee eeeeeee ee eeee eeeeeeeeeee eee e eeeeeee 8 e. Mee eeeeeee eee eeee eeeeeeee eeeeeee e M8 eeee eee eee eeeeeeee eee eeeee ee 88 °M ee 88 eeee eeeeeeee eee 8.8 e. Mee eeeeeee eeeeeee eee eeeee ee ee eeeeeee (88 eM) eee eeee eeeeeeee eee eeeeeeee eeeeeee e M8 eeee, eee eeeeeeee eee eeeeeeeeeeee ee 88 eeee eee eeeeeeeeeeee eeeee ee e eeee eeeeeeeeeee ee 88 °M eee 8.8 eeee eee 8 e. Meee eeee 8-eeeeee-8,8,8-eeeeeeeeeeeeeeee 88 ee e eeeeee eeeeeee eeeeee eeeee eeeee eeeeeeeee eeeeeee (8.8 eeeee); eeeee: 8.88 e (88% ee eeeeeeeeeee eeeee, eeeeeeeeee ee eee eeeeeee eeeeee).

M 8 M eeee ee MeMe ee eeeeeee (8 eM, 8 eeee) eee eeeee eeeeeeee ee eeee 88 (8.888 e, 8 eeee)[‌88‌] ee MMM (8 eM) ee −88 °M eeee eeeeeeee. Mee eeeeeee eee eeeeeee ee −88 °M eee 88 eee eee eeee eeeeeee ee eeee ee ee. M eeee ee 8-eeeeee-8,8,8-eeeeeeeeeeeeeeee 88 (8.88 e, 8.8 eeee) ee MMM (88 eM) eee eeee eeeee eeeeeeee eee, eeeee eeeeeeee eeeeeeeee ee 88 °M, eee eeeeeee eee eeeeeee ee 8.8 eeee. Mee eeeeeee eeeeeeee eee eeeeeee eeee eeeeeee (88 eM) eee eeeeeeee, eee eee eeeeeee ee eee eeee eee eeeeee eeee eeeeeee. Mee eeeeeeeee eeee eeeeeeee eeee eeeeeeeeeeee ee 8.8 eeee eee eee eeeeeee eee eeeee ee 88 °M eee 8 e. Mee eeeee eeeeeeee eee eeeee ee ee MeMM (88 eM) eee eeeeee eeeeeee eeeee e eeeee eeee eee eeeeeeee. Me eeeeeee, eee eeeeeee 88 eeeeeeeeeeee eee eee eeeeeee ee eeeeeeeeee. Mee eeeeeeeee eeeeeee eee eeeee eee ee 88 °M eee 8.8 eeee eeeeeeee eeee 8 e ee eeee eee eeeeeee; eeeee: 8.8 e (88%).

Meeeeee eee 8-Meeeeeeeeeeeee (Meeee 8, Meeee 8); Meeeeeeeeeeeeeee ee Meee-8-eee eeee Meeeee 88:[‌88‌]

MMMMMMM: Meeeee eeeeeeee ee eeeeeeeee eeeeeeeee eee eeeee, eee eeeeeeee ee eeeeee eeeeeeeeeeeeee eee eeeeeee eeee ee e eeee.

M eeeeeeee ee Me(eeee)(MM)8 (8.88 ee, 8.8 µeee) eee eeeeee 88 (88 ee, 88.8 µeee) ee eeeeeee (88 eM) eee eeeeeee eeee eeeeeeeee (8 eM; eeeeeeee eeeeeeee) eee eeee-8-eee (8 eM, 88.8 eeee). Meee eeeeeee eee eeeee ee eee eeeeeeeee, eeeee eee eeeeeeeeeeee eeeeeeeeeee ee 8 eee eeee eeeeee (MM/M8 8:8). Mee eeeeeeeee eee eeee eeeeee ee 888 °M eee eee eeeeeeee eeeeeeee ee 88 eee. Meeee 88 e, eee eeeeeeeee eee eeeeee ee ee eee eeee eee eee eeeeeeee eee eeeeeeee. M eeeeee eee eeeee eeeeeeeeeee, eeeeeeee ee MM, eee eeeee ee eeeeeee eeeeeee; eeeee: 88%; eeeee (eeeeee/eeeeeeee) 88:8.

Meeeeee eee 8-Meeeeeeeeeeeee (Meeee 8, Meeee 88); Meeeeeeeeeeeeeee ee Meee-8-eee eeee Meeeee 88:[‌88‌]

MMMMMMM: Meeeee eeeeeeee ee eeeeeeeee eeeeeeeee eee eeeee, eee eeeeeeee ee eeeeee eeeeeeeeeeeeee eee eeeeeee eeee ee e eeee.

M 8.888 eM eeee ee Me(eeee)(eee) ee eeeeeee (88 eM, 88.8 µeee) eee eeeeee ee e 888-eM eeeeeeeee eeeee eeeee, eeeeeeee ee eeeeee 88 (8 eeeee eeeeeeee ee Me). Mee eeeeee ee eee eeee eee eeeeeeee ee 88 eM ee eeeeeeee ee eeeeeee eee, eeeee eeeeeee ee eee eeeeeeeee, eee eeeee eeeeeeeeee eee eeeeeeee ee MM/M8 (88 eee) eee eee eeeeeee eee eeeeeee. Mee eeeeeeeee eee eeeeee ee 888 °M eee eee MM/M8 eeeeeeee eee eeeeeeee ee 88 eee. Meeee e eeeeeeee eeeee eeeeeeee ee eee eeeeeeeee, eeee-8-eee (88 eM) eee eeeeeeee eeeee 8 eee eeeeeeeeeeee eee eee eeeeeeee ee eee eeeeeeeee eee eeeeeeee ee 88 eee. Meeee eeeeeeee ee 888 °M eee 88 eee eee 8 e, eee eeeeeeeee eee eeeeee ee eeeeeee eeeeeeeeeee eee eee eeeeeeee eee eeeeeeee. Meeeeeeeee, eeeee, eee eeeeeeeeeee eee eeeeeee eeee eeeeeeeeee ee MM. Meeeeeeeee eee 88% eee eeeeeee eee eeeeee eeee e eeeeee/eeeeeeee eeeee ee 88:8.

References


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