MXPA98008524A

MXPA98008524A - Processes to produce hidroxialdehi

Info

Publication number: MXPA98008524A
Application number: MXPA/A/1998/008524A
Authority: MX
Inventors: Robert Bryant David; Lee Packett Diane; James Schreck David; Robert Briggs John; Carl Eisenschmid Thomas; Damar Olson Kurt; Gardner Phillips Ailene; Bruce Tjaden Erick; Sakharam Guram Anil; Susan Bragham Elaine
Original assignee: Union Carbide Chemicals & Plastics Technology Corp
Priority date: 1996-04-24
Filing date: 1998-10-15
Publication date: 1999-04-27

Abstract

The present invention relates: in part to processes for producing one or more substituted or unsubstituted hydroxyaldehydes, e.g. 6-hydroxyhexanals, which comprises subjecting one or more of the substituted or unsubstituted alkadienes e.g. butadiene, to reductive hydroformylation in the presence of a reductive hydroformylation catalyst, e.g. a complex metal catalyst-organophosphorus coordinating group, and hydroformylation in the presence of a hydroformylation catalyst e.g. a complex metal catalyst-organophosphorus coordinating group, to produce one or more substituted or unsubstituted hydroxyaldehydes. Substituted or unsubstituted hydroxyaldehydes produced by the processes of this invention undergo additional reactions to provide the desired derivatives thereof, e.g., epsilon caprolactone. This invention is also related in part to reaction mixtures containing one or more of the substituted or unsubstituted hydroxyaldehydes as the main product (s) of the reaction.

Description

"PROCESSES TO PRODUCE HIDROXIALDEHYDES" BRIEF COMPENDIUM OF THE INVENTION TECHNICAL FIELD This invention is related in part to processes to selectively produce one or more hydroxial substituted or unsubstituted, eg, 6-hydroxyhexanals. This invention also relates in part to reaction mixtures containing one or more substituted or unsubstituted hydroxyaldehydes, e.g. 6-hydroxyhexanals, as the main reaction product (s).

BACKGROUND OF THE INVENTION Hydroxyaldehydes, e.g., 6-hydroxyhexanals, are valuable intermediates that are useful, for example, in the production of epsilon caprolactone, epsilon caprolactam, adipic acid and 1,6-hexanediol. The processes currently used to produce hydroxyaldehydes have several disadvantages. For example, the starting materials used to produce 6-hydroxyhexanals are relatively expensive. In addition, the selectivity of 6-hydroxyhexanals in the processes of the prior art, - They have been low. Accordingly, it would be desirable to selectively produce hydroxyaldehydes from a relatively inexpensive starting material and by a process that can be used commercially.

EXHIBITION OF THE INVENTION It has been found that alkadienes or pentenales can be converted to linear hydroxyaldehydes at high selectivities. It has also been found that unsaturated alcohols, eg, alcohols possessing internal olefinic unsaturation, can be hydroformylated in hydroxyaldehydes, eg, terminal aldehydes, at high ratios of normal isomer: branched, eg, 3-penten-1-oles hydrosformylated at 6. -Hydroxyhexanals in high ratios of normal isomer: branched. In particular, it has surprisingly been discovered that butadiene can be converted to linear 6-hydroxyhexanals, e.g., 6-hydroxyhexanal, by employing catalysts having reductive hydroformylation / hydroformylation / isomerization capabilities. This invention relates to processes for producing one or more substituted or unsubstituted hydroxyaldehydes, eg, 6-hydroxyhexanals which comprises subjecting one or more of the substituted or unsubstituted alkadienes, eg, butadiene, to reductive hydroformylation in the presence of a hydroformylation catalyst reductive, vg a complex metal catalyst-organophosphorus coordinating group, hydroformylation in the presence of a hydroformylation catalyst, e.g., a complex metal catalyst-organophosphorus coordinating group, to produce one or more substituted or unsubstituted hydroxyaldehydes. This invention also relates to processes for producing one or more substituted or unsubstituted hydroxyaldehydes, eg, 6-hydroxyhexanals, which comprises subjecting one or more substituted or unsubstituted pentenales to reductive hydroformylation in the presence of a reductive hydroformylation catalyst, eg, a complex metal catalyst-organophosphorus coordinating group, in order to produce one or more substituted or unsubstituted hidoxialdehydes. This invention further relates to processes for producing one or more substituted or unsubstituted hydroxyaldehydes, eg, 6-hydroxyhexanals, which comprises subjecting one or more substituted or unsubstituted unsaturated alcohols, preferably having at least four carbon atoms, eg , penten-1-ols, to hydroformylation in the presence of a hydroformylation catalyst, eg, a complex metal catalyst-organophosphorus coordinating group, in order to produce one or more substituted or unsubstituted hydroxyaldehydes. This invention is still further related to processes for producing one or more substituted or unsubstituted hydroxyaldehydes, eg, 6-hydroxyhexanals, which comprises: (a) subjecting one or more of the substituted or unsubstituted alkadienes, eg, butadiene, to reductive hydroformylation in the presence of a reductive hydroformylation catalyst, eg, a complex metal catalyst-organophosphorus coordinating group, to produce one or more substituted or unsubstituted unsaturated alcohols; and (b) subjecting one or more of the substituted or unsubstituted unsaturated alcohols to hydroformylation in the presence of a hydroformylation catalyst, eg, a complex metal catalyst-organophosphorus coordinating group, in order to produce one or more of the substituted hydroxyaldehydes or not replaced. The reductive hydroformylation reaction conditions in step (a), and the hydroformylation reaction conditions in step (b), may be the same or different, and the reductive hydroformylation catalyst in step (a) and the catalyst hydroformylation in step (b) may be the same or different. This invention also relates to processes for producing one or more substituted or unsubstituted hydroxyaldehydes, eg, 6-hydroxyhexanals, which comprises reacting one or more of the substituted or unsubstituted alkadienes, eg, butadienes, with carbon monoxide and hydrogen, in the presence of a complex metal catalyst-coordinating group, eg, a complex metal catalyst-organophosphorus coordinating group, and an optionally free coordinating group to produce one or more substituted or unsubstituted unsaturated alcohols, eg, penten-1-ols , and reacting one or more substituted or unsubstituted unsaturated alcohols with carbon monoxide and hydrogen, in the presence of the complex metal catalyst-coordinating group, eg, a complex metal catalyst-organophosphorus coordinating group, and optionally a free coordinating group to produce one or more substituted or unsubstituted hydroxyaldehydes. In a preferred embodiment, the complex metal-coordinator group catalysts are complex metal catalysts-organophosphorus coordinating group. This invention also relates to processes for producing one or more substituted or unsubstituted hydroxyaldehydes, eg, 6-hydroxyhexanals, which comprises reacting one or more of the substituted or unsubstituted pentenales with carbon monoxide and hydrogen, in the presence of a catalyst metal complex-coordinating group, eg, a complex metal catalyst-organophosphorus coordinating group, and optionally a free coordinating group, to produce one or more substituted or unsubstituted hydroxyaldehydes. In a preferred embodiment, the complex catalyst metal-coordinator group is a complex metal catalyst-organophosphorus coordinating group. This invention still further relates to processes for producing one or more substituted or unsubstituted hydroxyaldehydes, eg, 6-hydroxyhexanals, which comprises reacting one or more substituted or unsubstituted unsaturated alcohols, preferably having at least four carbon atoms. carbon, eg, penten-1-ols, with carbon monoxide and hydrogen in the presence of a complex catalyst metal-coordinating group, eg, a complex metal catalyst-organophosphorus coordinating group and optionally a free coordinating group to produce one or more than substituted or unsubstituted hydroxyaldehydes. This invention also relates to processes for producing one or more substituted or unsubstituted hydroxyaldehydes, eg, 6-hydroxyhexanals, which comprises: (a) reacting one or more of the substituted or unsubstituted alkadienes, eg, butadienes, with monoxide carbon and hydrogen in the presence of a complex metal catalyst-coordinating group, eg, a complex metal catalyst-organophosphorus coordinating group and an optionally free coordinating group to produce one or more substituted or unsubstituted unsaturated alcohols, eg, penten-1 -ols, and (b) reacting one or more substituted or unsubstituted unsaturated alcohols with carbon monoxide and hydrogen in the presence of a complex catalyst metal-coordinator group, eg, a complex metal catalyst-organophosphorus coordinating group, and an optionally free coordinating group for producing one or more of the substituted or unsubstituted hydroxyaldehydes. The reductive hydroformylation reaction conditions in step (a), and the hydroformylation reaction conditions in step (b) may be the same or different, and the reductive hydroformylation catalyst in step (a) and the hydroformylation catalyst in step (b) may be the same or different. This invention is further related in part to a process for producing an intermittently or continuously generated reaction mixture, comprising: (1) one or more substituted or unsubstituted 6-hydroxyhexanals, e.g., 6-hydroxyhexanal; (2) optionally one or more substituted or unsubstituted penten-1-ols, eg, cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol, trans -3-penten-l-ol and / or 4-penten-l-ol; (3) optionally one or more substituted or unsubstituted 5-hydroxypentanals, and / or cyclic lactol derivatives thereof, e.g., 2-methyl-5-hydroxypentanal; (4) optionally one or more substituted or unsubstituted 4-hydroxybutanales and / or cyclic lactol derivatives thereof, e.g., 2-ethyl-4-hydroxybutanal; (5) optionally one or more substituted or unsubstituted pentan-1-oles; (6) optionally one or more substituted or unsubstituted valeraldehydes; (7) optionally one or more substituted or unsubstituted pentenales, e.g., cis-2-pentenal, trans-2-pentenal, cis-3-pentenal, trans-3-pentenal and / or 4-pentenal; (8) optionally one or more 1,6-hexanedioles, substituted or unsubstituted, e.g., adipaldehyde; (9) optionally one or more substituted 1, 5-pentanedial, e.g., 2-methylglutaraldehyde; (10) optionally one or more substituted 1,4-butanedials, e.g., 2,3-dimethylsuccinaldehyde and 2-ethylsuccinaldehyde; and (11) one or more substituted or unsubstituted butadienes, e.g., butadiene; where the weight ratio of component (1) to the sum of components (2), (3), (4), (5), (6), (7), (8), (9) and ( 10) is greater than about 0.1, preferably greater than about 0.25, and preferably especially preferred greater than about 1.0; and the weight ratio of the component (11) to the sum of the components (1), (2), (3), (4), (5), (6), (7), (8), (9) ) and (10) is from about 0 to about 100, preferably from about 0.001 to about 50; which process comprises reacting one or more substituted or unsubstituted butadienes, eg, butadiene, with carbon monoxide and hydrogen in the presence of a complex metal catalyst-coordinating group, eg, a complex metal catalyst-organophosphorus coordinating group, and an optionally free coordinating group for producing one or more substituted or unsubstituted penten-1-ols, and reacting one or more substituted or unsubstituted penten-1-ols with carbon monoxide and hydrogen, in the presence of a complex metal catalyst - coordinating group eg, a complex metal catalyst-organophosphorus coordinating group, and optionally a free coordinating group for producing the reaction mixture generated intermittently or continuously. In a preferred embodiment, the complex metal-coordinator group catalysts are complex metal catalysts-organophosphorus coordinating group. This invention still further relates in part to a process for producing an intermittently or continuously generated reaction mixture comprising: (1) one or more substituted or unsubstituted 6-hydroxyhexanals, e.g., 6-hydroxyhexanal; (2) optionally one or more substituted or unsubstituted penten-1-ols, eg, cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol, trans -3-penten-l-ol and / or 4-penten-l-ol; (3) optionally one or more substituted or unsubstituted 5-hydroxypentanalnes and / or cyclic lactol derivatives thereof, e.g., 2-me-il-5-hydroxypentanal; (4) optionally one or more substituted or unsubstituted 4-hydroxybutanales, and / or cyclic lactol derivatives thereof, e.g., 2-ethyl-4-hydroxybutanal; (5) optionally one or more substituted or unsubstituted pentan-1-oles; (6) optionally one or more substituted or unsubstituted valeraldehydes; and (7) one or more substituted or unsubstituted pentenales, e.g., cis-2-pentenal, trans-2-pentenal, cis-3-pentenal, trans-3-pentenal and / or 4-pentenal; - wherein the weight ratio of component (1) to the sum of components (2), (3), (4), (5) and (6) is greater than about 0.1, preferably greater than about 0.25, and especially preferably greater than about 1.0; and the weight ratio of the component (7) to the sum of the components (1), (2), (3), (4), (5) and (6) is from about 0 to about 100, preferably from about 0.001 to about 50; which process comprises reacting one or more substituted or unsubstituted pentenales with carbon monoxide and hydrogen, in the presence of a complex metal catalyst-coordinating group eg, a complex metal catalyst-organophosphorus coordinating group, and optionally a free coordinating group to produce a reaction mixture generated intermittently or continuously. In a preferred embodiment, the complex catalyst metal-coordinator group is a complex metal catalyst-organophosphorus coordinating group. This invention also relates in part to a process for producing an intermittently or continuously generated reaction mixture comprising: (1) one or more substituted or unsubstituted 6-hydroxyhexanals, e.g., 6-hydroxyhexanal; (2) one or more substituted or unsubstituted penten-1-ols, eg, cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol, 3-penten-l-ol and / or 4-penten-l-ol; (3) optionally one or more substituted or unsubstituted 5-hydroxypentanals and / or the cyclic lactol derivatives thereof, e.g., 2-methyl-5-hydroxypentanal; (4) optionally one or more substituted or unsubstituted 4-hydroxybutanales and / or cyclic lactol derivatives thereof, e.g., 2-ethyl-4-hydroxybutanal; and (5) optionally one or more substituted or unsubstituted valeraldehydes; wherein the weight ratio of component (1) to the sum of components (3), (4) and (5) is greater than about 0.1, preferably greater than about 0.25, most preferably greater than about 1.0; and the weight ratio of component (2) to the sum of components (1), (3), (4) and (5) is from about 0 to about 100, preferably from about 0.001 to about 50; The process of which comprises reacting one or more of the substituted or unsubstituted penten-1-ols with carbon monoxide and hydrogen, in the presence of a metal complex catalyst and a coordinating group, eg, a complex metal catalyst. organophosphorus coordinating group, and optionally a free coordinating group - 1 - to produce the reaction mixture generated intermittently or continuously. This invention is further related in part to a process for producing an intermittently or continuously generated reaction mixture comprising: (1) one or more 6-hydroxyhexanals, substituted or unsubstituted, e.g., 6-hydroxyhexanal; (2) optionally one or more penten-1-oles, substituted or unsubstituted, eg, cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol, trans-3-penten-1-ol and / or 4-penten-1-ol; (3) optionally one or more substituted or unsubstituted 5-hydroxypentanals, and / or cyclic lactol derivatives thereof, e.g., 2-methyl-5-hydrsxypentanal; (4) optionally one or more substituted or unsubstituted 4-hydroxybutanales, and / or cyclic lactol derivatives thereof, e.g., 2-ethyl-4-hydroxybutanal; (5) optionally one or more substituted or unsubstituted pentan-1-oles; (6) optionally one or more substituted or unsubstituted valeraldehydes; (7) optionally one or more substituted or unsubstituted pentenales, e.g., cis-2-pentenal, trans-2-pentenal, cis-3-pentenal, trans-3-pentenal and / or 4-pentenal; (8) optionally one or more substituted or unsubstituted 1, 6-hexanodiales, e.g., adipaldehyde; (9) optionally one or more substituted 1, 5-pentanediods, e.g., 2-methylglutaraldehyde; (10) optionally one or more substituted 1,4-butanedials, e.g., 2, 3-dimethylsuccinaldehyde and 2-ethylsuccinaldehyde; and (11) one or more substituted or unsubstituted butadienes, e.g., butadiene; where the weight ratio of component (1) to the sum of components (2), (3), (4), (5), (6), (7), (8), (9) and ( 10) greater than about 0.1, preferably greater than about 0.25, most preferably greater than about 1.0; and the weight ratio of the component (11) to the sum of the components (1), (2), (3), (4), (5), (6), (7), (8), (9) and (10) is from about 0 to 100, preferably from about 0.001 to about 50; which process comprises: (a) reacting one or more of substituted or unsubstituted butadienes, eg, butadiene, with carbon monoxide and hydrogen, in the presence of a complex metal catalyst-coordinating group, eg, a complex metal catalyst; organophosphorus coordinating group, and an optionally free coordinating group to produce one or more substituted or unsubstituted penten-1-oles, and (b) reacting one or more substituted or unsubstituted penten-1-oles with carbon monoxide and hydrogen , in the presence of a complex metal catalyst-coordinating group eg, a complex catalyst metal-organophosphorus coordinating group, and optionally a free coordinating group to produce the reaction mixture generated intermittently or continuously. The reductive hydroformylation reaction conditions in step (a) and the hydroformylation reaction conditions in step (b) may be the same or different, and the reductive hydroformylation catalyst in step (a) and the hydroformylation catalyst in step (b) may be the same or different. This invention is still additionally related to a process for producing a reaction mixture comprising one or more substituted or unsubstituted hydroxyaldehydes, eg, 6-hydroxyhexanals, which process comprises reacting one or more substituted or unsubstituted alkadienes, eg , butadienes, with carbon monoxide and hydrogen, in the presence of a complex catalyst metal-coordinator group, eg, a complex metal catalyst-organophosphorus coordinating group, "and optionally a free coordinating group for producing one or more substituted or unsubstituted unsaturated alcohols, eg penten-1-ols, and reacting one or more substituted or unsubstituted unsaturated alcohols with carbon monoxide and hydrogen, in the presence of a complex catalyst metal-coordinator group, eg, a complex metal catalyst-organophosphorus coordinating group, and optionally a free coordinating group for producing the reaction mixture comprising one or more substituted or unsubstituted hydroxyaldehydes. The complex metal-coordinating group catalysts are complex metal catalysts-organophosphorus coordinating group This invention also relates to a process for producing a reaction mixture comprising one or more substituted or unsubstituted hydroxyaldehydes, eg, 6-hydroxyhexanals, whose process involves reacting one or more substituted pentenales or not ubstituted with carbon monoxide and hydrogen, in the presence of a complex catalyst metal-coordinating group, eg, a complex metal catalyst-organophosphorus coordinating group, and optionally a free coordinating group to produce the reaction mixture comprising one or more hydroxyaldehydes substituted or unsubstituted. In a preferred embodiment, the complex catalyst metal-coordinator group is a complex metal catalyst-organophosphorus coordinating group.

This invention is further related to a process for producing a reaction mixture comprising one or more substituted or unsubstituted hydroxyaldehydes, eg, 6-hydroxyhexanals, which process comprises reacting one or more unsaturated or unsubstituted unsaturated alcohols, having preference for at least four carbon atoms, eg, penten-1-ols, with carbon monoxide and hydrogen, in the presence of a complex catalyst metal-coordinating group, eg, a complex metal catalyst-organophosphorus coordinating group, and optionally a free coordinating group for producing the reaction mixture comprising one or more substituted or unsubstituted hydroxyaldehydes. This invention still further relates to a process for producing a reaction mixture comprising one or more substituted or unsubstituted hydroxyaldehydes, eg, 6-hydroxyhexanals, which process comprises: (a) reacting one or more substituted or unsubstituted alkadienes, eg, butadienes, with carbon monoxide and hydrogen, in the presence of a complex catalyst metal-coordinating group, eg, a complex metal catalyst-organophosphorus coordinating group, and an optionally free coordinating group, to produce one or more unsaturated alcohols substituted or unsubstituted, eg, penten-1-ols, and (b) reacting one or more substituted or unsubstituted unsaturated alcohols with carbon monoxide and hydrogen in the presence of a complex catalyst metal-coordinating group, eg, a catalyst metal complex-organophosphorus coordinating group, and optionally a free coordinating group to produce the reaction mixture that co It comprises one or more substituted or unsubstituted hydroxyaldehydes. The reductive hydroformylation reaction conditions in step (a) and the hydroformylation reaction conditions in step (b) may be the same or different, and the reductive hydroformylation catalyst in step (a) and the hydroformylation catalyst in step (b) they may be the same or different. The processes of this invention can achieve high selectivities of alkadienes, pentenales and penten-1-oles in 6-hydroxyhexanals, ie, selectivities of penten-1-oles in 6-hydroxyhexanals of at least 10 weight percent and up to 85 percent by weight or greater can be achieved by the processes of this invention. Also, the processes of this invention can achieve high ratios of normal isomer: branched, e.g. butadiene hydroformylated reductively / hydroformylated in 6-hydroxyhexanals at high ratios of normal isomer: branched.

- This invention also relates in part to the intermittently or continuously generated reaction mixture, which comprises: (1) one or more substituted or unsubstituted 6-hydroxyhexanals, e.g., β-hydroxyhexanal; (2) one or more substituted or unsubstituted penten-1-ols, eg, cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol, 3-penten-l-ol and / or 4-penten-l-ol; (3) optionally one or more substituted or unsubstituted 5-hydroxypentanals, and / or cyclic lactol derivatives thereof, e.g., 2-methyl-5-hydroxypentanal; (4) optionally one or more substituted or unsubstituted 4-hydroxybutanales and / or the cyclic lactol derivatives thereof, e.g., 2-ethyl-4-hydroxybutanal; (5) optionally one or more substituted or unsubstituted valeraldehydes; wherein the weight ratio of the component (1) to the sum of the components (3), (4) and (5), greater than about 0.1, preferably greater than about 0.25, particularly preferably greater than about 1.0; and the weight ratio of component (2) to the sum of components (1), (3), (4) and (5), is from about 0 to about 100, preferably from about 0.001 to about 50; - - This invention also relates in part to the intermittently or continuously generated reaction mixture comprising: (1) one or more substituted or unsubstituted 6-hydroxyhexanals, e.g., 6-hydroxyhexanal; (2) optionally one or more substituted or unsubstituted penten-1-ols, eg, cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol, trans -3-penten-l-ol and / or 4-penten-l-ol; (3) optionally one or more substituted or unsubstituted 5-hydroxypentanals and / or cyclic lactol derivatives thereof, e.g., 2-methyl-5-hydroxypentanal; (4) optionally one or more substituted or unsubstituted 4-hydroxybutanales, and / or cyclic lactol derivatives thereof, e.g., 2-ethyl-4-hydroxybutanal; (5) optionally one or more substituted or unsubstituted pentan-1-oles; (6) optionally one or more substituted or unsubstituted valeraldehydes; and - (7) optionally one or more substituted or unsubstituted pentenales, e.g., cis-2-pentenal, trans-2-pentenal, cis-3-pentenal, trans-3-pentenal and / or 4-pentenal; wherein the weight ratio of the component (1) to the sum of the components (2), (3), (4), (5) and (6), is greater than - about 0.1, preferably greater than about 0.25, most preferably greater than about 1.0; and the weight ratio of the component (7) to the sum of the components (1), (2), (3), (4), (5) and (6), is from about 0 to about 100, preferably This invention is still in part related to an intermittently or continuously generated reaction mixture comprising: (1) one or more substituted or unsubstituted 6-hydroxyhexanals, eg, 6-hydroxyhexanal; (2) optionally one or more substituted or unsubstituted penten-1-ols, eg, cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol, trans -3-penten-l-ol and / or 4-penten-l-ol; (3) optionally one or more substituted or unsubstituted 5-hydroxypentanals and / or cyclic lactol derivatives thereof, e.g., 2-methyl-5-hydroxypentanal; (4) optionally one or more substituted or unsubstituted 4-hydroxybutanales, and / or cyclic lactol derivatives thereof, e.g., 2-ethyl-4-hydroxybutanal; (5) optionally one or more substituted or unsubstituted pentan-1-oles; (6) optionally one or more substituted or unsubstituted valeraldehydes; and (7) optionally one or more substituted or unsubstituted pentenales, e.g., cis-2-pentenal, trans-2-pentenal, cis-3-pentenal, trans-3-pentenal and / or 4-pentenal; (8) optionally one or more 1,6-hexanedioles, substituted or unsubstituted, e.g., adipaldehyde; (9) optionally one or more substituted 1, 5-pentanediods, e.g., 2-methylglutaraldehyde; (10) optionally one or more substituted 1,4-butanedials, e.g., 2, 3-dimethylsuccinaldehyde and 2-ethylsuccinaldehyde; and (11) one or more substituted or unsubstituted butadienes, eg, butadiene, wherein the weight ratio of the component (1) to the sum of the components (2), (3), (4), (5), (6), (7), (8), (9) and (10) is greater than about 0.1, preferably greater than about 0.25, especially preferably greater than about 1.0; and the weight ratio of the component (11) to the sum of the components (1), (2), (3), (4), (5), (6), (7), (8), (9) ) and (10) is from about 0 to about 100, preferably from about 0.001 to about 50; This invention also relates in part to a reaction mixture comprising one or more substituted or unsubstituted hydroxyaldehydes, eg, 6-hydroxyhexanals, wherein the reaction mixture is prepared by a process comprising reacting one or more substituted alkadienes or unsubstituted, eg, butadienes, with carbon monoxide and hydrogen, in the presence of a complex catalyst metal-coordinating group, eg, a complex metal catalyst-organophosphorus coordinating group, and an optionally free coordinating group to produce one or more substituted or unsubstituted unsaturated alcohols, eg, penten-1-ols, and reacting one or more unsubstituted or unsubstituted unsaturated alcohols with carbon monoxide and hydrogen, in the presence of a complex catalyst metal-coordinating group, eg, a complex metal catalyst-organophosphorus coordinating group, and optionally a free coordinating group, to produce a reaction mixture comprising one or more substituted or unsubstituted hydroxyaldehydes. In a preferred embodiment, the complex metal-coordinator group catalysts are complex metal catalysts-organophosphorus coordinating group. This invention is also related in part to a reaction mixture comprising one or more - substituted or unsubstituted hydroxyaldehydes, eg, 6-hydroxyhexanals, wherein the reaction mixture is prepared by a process comprising reacting one or more substituted or unsubstituted pentenales with carbon monoxide and hydrogen, in the presence of a complex metal catalyst -group coordinator, eg, a complex metal catalyst-organophosphorus coordinating group, and optionally a free coordinating group for producing the reaction mixture, comprising one or more substituted or unsubstituted hydroxyaldehydes. In a preferred embodiment, the complex catalyst metal-coordinator group is a complex metal catalyst-organophosphorus coordinating group. This invention also relates in part to a reaction mixture comprising one or more substituted or unsubstituted hydroxyaldehydes, eg, 6-hydroxyhexanals, wherein the reaction mixture is prepared by a process comprising reacting one or more substituted unsaturated alcohols. or unsubstituted, preferably having at least four carbon atoms, eg, penten-1-ols, with carbon monoxide and hydrogen, in the presence of a complex metal catalyst-coordinating group, eg, a complex metal catalyst -organophosphorus coordinating group, and optionally a free coordinating group for producing the reaction mixture, comprising one or more substituted or unsubstituted hydroxyaldehydes. This invention also relates in part to a reaction mixture comprising one or more substituted or unsubstituted hydroxyaldehydes, eg, 6-hydroxyhexanals, wherein the reaction mixture is prepared by a process comprising: (a) reacting one or more substituted or unsubstituted alkadienes, eg, butadienes, with carbon monoxide and hydrogen, in the presence of a complex metal catalyst-coordinating group, eg, a complex metal catalyst-organophosphorus coordinating group, and optionally a free coordinating group, to produce one or more substituted or unsubstituted unsaturated alcohols, eg, penten-1-ols, and (b) to react one or more substituted or unsubstituted unsaturated alcohols with carbon monoxide and hydrogen in the presence of a complex metal catalyst. coordinating group, eg, a complex metal catalyst-organophosphorus coordinating group, and optionally a free coordinating group to produce the reaction mixture comprising one or more substituted or unsubstituted hydroxyaldehydes. The reductive hydroformylation reaction conditions in step (a) and the hydroformylation reaction conditions in step (b) may be the same or different, and the reductive hydroformylation catalyst in step (a) and the hydroformylation catalyst in step (b) they may be the same or different. The reaction mixtures of the invention are different, since the processes for their preparation achieve the generation of large selectivities of 6-hydroxyhexanals in a way that can be properly employed in a commercial process for the manufacture of 6-hydroxyhexanals. In particular, the reaction mixtures of this invention are distinct since the processes for their preparation allow the production of 6-hydroxyhexanals in relatively high yields without generating large amounts of by-products, e.g., pentanols and valeraldehyde.

DETAILED DESCRIPTION The reductive hydroformylation processes of this invention include but are not limited to converting one or more of the substituted or unsubstituted pentenales and converting one or more of the substituted or unsubstituted alkadienes to one or more substituted or unsubstituted penten-1-ols. . As used herein, the term "reductive hydroformylation" is intended to include but not be limited to all permissible hydroformylation, hydrogenation and isomerization processes that include converting one or more of the substituted or unsubstituted pentenales into one or more of substituted or unsubstituted 1, 6-hydroxyhexanals and of converting one or more of the substituted or unsubstituted alkadienes into one or more of the substituted or unsubstituted pente-1-ols. Generally, the reductive hydroformylation step or step comprises reacting one or more substituted or unsubstituted pentenales with carbon monoxide and hydrogen, in the presence of a catalyst to produce one or more substituted or unsubstituted 1, 6-hydroxyhexanals and make reacting one or more alkadienes substituted or unsubstituted with carbon monoxide and hydrogen in the presence of a catalyst to produce one or more substituted or unsubstituted penten-1-ols. The reductive hydroformylation processes of this invention can be carried out in one or more steps of steps preferably a one-step process. The hydroformylation, hydrogenation and isomerization reactions can be carried out in any permissible sequence in order to produce one or more substituted or unsubstituted 1, 6-hydroxyhexanals or penten-1-ols. Exemplary hydroformylation steps or steps include, but are not limited to the following: (a) converting one or more substituted or unsubstituted alkadienes into one or more substituted or unsubstituted pentenales; and (b) converting one or more substituted or unsubstituted penten-1-oles into one or more substituted or unsubstituted 6-hydroxyhexanals. Exemplary hydrogenation steps include, but are not limited to converting one or more of the substituted or unsubstituted pentenales into one or more of the substituted or unsubstituted penten-1-ols. Exemplary isomerization steps include, but are not limited to the following: (a) converting one or more of the two substituted or unsubstituted and / or 3-pentenales pentenales to one or more substituted or unsubstituted 4-pentenales, and ( b) converting one or more substituted or unsubstituted 2-penten-1-oles and / or 3-penten-1-oles into one or more substituted or unsubstituted 4-penten-1-oles. Suitable reductive hydroformylation reaction conditions-and appropriate reductive hydroformylation processing techniques and catalysts include those described below for hydroformylation and hydrogenation steps or steps. The steps or steps of hydroformylation and hydrogenation in the processes of this invention can be carried out as described below.

Although it is not desired to be bound to any specific reaction mechanism, it is believed that the total reductive hydroformylation reaction generally proceeds in one or more steps or steps. This invention is not intended to be limited in any way by any specific reaction mechanism but rather encompasses all permissible hydroformylation, hydrogenation and isomerization processes as described herein Steps or Stages of Hydroformylation Hydroformylation processes involve the production of aldehydes, e.g., 6-hydroxyhexanals or pentenales, by reacting an olefinic compound, e.g. penten-1-ols, or an alkadiene, with carbon monoxide and hydrogen in the presence of a complex catalyst metal-coordinating group and optionally a free coordinating group in a liquid medium which also contains a solvent for the catalyst and the coordinating group. The processes can be carried out in a continuous single-pass mode in a continuous or more preferred gas recycling manner in a continuous liquid catalyst recycle manner as will be described below. The hydroformylation processing techniques employable herein may correspond to any of the techniques of - known processes such as those employed preferably in conventional liquid catalyst recycling hydroformylation reactions. As used herein, the term "hydroformylation" is intended to include but not be limited to all permissible hydroformylation processes that involve converting one or more of the substituted or unsubstituted olefinic compounds or alkadienes into one or more substituted aldehydes or not replaced. Generally, the hydroformylation step or step comprises reacting one or more substituted or unsubstituted pentenols with carbon monoxide and hydrogen in the presence of a catalyst to produce one or more substituted or unsubstituted 6-hydroxyhexanals, and reacting one or more alkadienes substituted or unsubstituted with carbon monoxide and hydrogen, in the presence of a catalyst to produce one or more substituted or unsubstituted pentenales. The hydroformylation reaction mixtures employable herein include any solution derived from any corresponding hydroformylation process which may contain at least a certain amount of four different main ingredients or components, i.e. the product is aldehyde, a complex metal catalyst. coordinating group, optionally a free coordinating group, and an organic solubilizing agent for the catalyst and the free coordinating group, the ingredients corresponding to those employed and / or produced by the hydroformylation process from which the starting material of the the hydroformylation reaction mixture. By the term "free coordinating group" is meant the coordinating group which is not complexed with (adheres to or binds to) a metal, e.g., rhodium atom, of the complex catalyst. It should be understood that the hydroformylation reaction mixture compositions employable herein may contain and will usually contain small amounts of additional ingredients such as those that have already been deliberately employed in the hydroformylation process or formed in situ during that process . Examples of these ingredients that may also be present include an unreacted olefin or alkadiene starting material, carbon monoxide and hydrogen gases, and products of in situ formed type, such as saturated hydrocarbons and / or unreacted isomerized olefins. corresponding to olefin or alkadiene starting materials, and high boiling temperature liquid aldehyde condensation byproducts, as well as other inert co-solvent type materials or hydrocarbon additives, if employed.

- Catalysts useful in the hydroformylation process include complex metal-coordinator group catalysts. The permissible metals that constitute the metal-coordinating group complexes include Group 8, 9, and 10 metals that are selected from rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt), osmium (Os) and mixtures thereof, the preferred metals being rhodium, cobalt, iridium and ruthenium, most preferably rhodium, cobalt and ruthenium, especially rhodium. The permissible coordinating groups include, for example, coordinating groups of organo-arsenic, organophosphorus and organo-antimony or mixtures thereof, preferably organophosphorus coordinating groups. The permissible organophosphorus coordinating groups that constitute the metal-coordinating group complexes include organophosphines, eg, mono-, di-, tri- and poly- (organophosphines), and organosphosphites, eg, mono-, di-, tri- and poly- - (organophosphites). Other permissible organophosphorus coordinating groups include, for example, organophosphonites, organophosphinites, aminophosphines and the like. Still other permissible coordinating groups include, for example, coordinating groups that contain a heteroatom as described in the North American Patent Application Serial Number (D-17646-1), - filed on March 10, 1997, the exhibition of which is incorporated herein by reference. The mixtures of these coordinating groups can be used if desired in the complex catalyst metal-coordinating group and / or the free coordinating group and these mixtures can be the same or different. This invention is not intended to be limited in any way by the permissible organophosphorus coordinating groups or mixtures thereof. It will be noted that the satisfactory practice of this invention does not depend and is not based on the exact structure of the species of the metal complex-coordinating group, which may be present in its mononuclear, dinuclear and / or higher nuclearity forms. Of course, the exact structure is not known. Although it is not intended here to be bound by any theory or mechanistic dissertation, it seems that the catalytic species can consist essentially, in its simplest form, of the metal in complex combination with the coordinating group and the carbon monoxide when use The term "complex" as used herein and in the claims means a coordination compound formed by the union of one or more electronically rich molecules or atoms, capable of existing independently with one or more atoms or molecules electronically deficient, each of which is capable of existing independently. For example, the coordinating groups employable herein, ie, the organophosphorus coordinating groups, may possess one or more phosphorus donor atoms, each having an electron pair available or not shared that each is capable of forming a covalent bond. independently coordinated or possibly agreed (eg, through chelation) with the metal. Carbon monoxide (which is also appropriately classified as a coordinating group) can also be present and complexed with the metal. The final composition of the complex catalyst may also contain an additional coordinating group, e.g., hydrogen or an anion that satisfies the coordination sites or nuclear charge of the metal. Additional illustrative coordinating groups include, e.g. halogen (Cl, Br, I), alkyl, aryl, substituted aryl, acyl, CF3, C2F5, CN, (R) 2PO and RP (0) (OH) 0 (wherein each R is the same or different and is a radical of substituted or unsubstituted hydrocarbon, eg alkyl or aryl), acetate, acetylacetonate, SO4, BF4, PFg, N0, NO3, CH3O, CH2 = CHCH2, CH3CH = CHCH2, C6H5CN, CH3CN, NO, NH3, pyridine, (C2H5 ) 3N, _ mono-olefins, diolefins and triolefins, tetrahydrofuran, and the like. Of course, it should be understood that the complex species are preferably free of any additional organic coordinating group or anion which could contaminate the catalyst and which have an undue detrimental effect on the functioning of the catalyst. It is preferred, in the hydroformylation reactions catalyzed by the metal-coordinating group complex that the active catalysts be free of halogen and sulfur directly linked to the metal, even though this may not be absolutely necessary, The complex metal catalysts-coordinating group Preferred include complex rhodium catalysts-organophosphine coordinating group and rhodium complex catalysts-organophosphite coordinating group. The number of coordination sites available in these metals is well known in the art. Therefore, the catalytic species may comprise a complex catalytic mixture, in its monomeric, dimeric or higher nuclearity forms, which are preferably characterized by at least one phosphorus-containing molecule formed in complex by metal, e.g., rhodium. As mentioned above, it is considered that the catalytic species of the preferred catalyst that is employed in the hydroformylation reaction can be complexed with carbon monoxide to hydrogen in addition to the organophosphorus coordinating groups, in view of carbon monoxide and the hydrogen gas employed by the hydroformylation reaction.

Among the organophosphines which can serve as the coordinating group of the metal-organophosphine complex catalyst and / or the free organophosphine coordinating group of the starting materials of the hydroformylation reaction mixture are the triorganophosphines, trialkylphosphines, alkyldiallylphosphines, dialkylarylphosphines, dicycloalkylarylphosphines, cycloalkyl-diarylphosphines, triaralkylphosphines, tricioalkylphosphines, and triarylphosphines, alkyl and / or aryl diphosphines and bisphosphine mono-oxides, as well as ionic triorganophosphines containing at least one ionic residue which is selected from the salts of sulfonic acid, carboxylic acid, Phosphonic acid and quaternary ammonium compounds, and the like. Of course, any of the hydrocarbon radicals of these non-ionic and ionic tertiary organophosphines can be substituted, if desired, with any appropriate substituent that does not unduly detrimentally affect the desired result of the hydroformylation reaction. The organophosphine coordinating groups which can be used in the hydroformylation reaction and / or in the methods for their preparation are known in the art. The illustrative triorganophosphine coordinating groups can be represented by the formula: where each? * X is the same or different and is a radical of - substituted or unsubstituted monovalent hydrocarbon, e.g., an alkyl or aryl radical. Suitable hydrocarbon radicals may contain from 1 to 24 carbon atoms or more. Illustrative substituent groups that may be present on the aryl radicals include, v.gr, alkyl radicals, alkoxy radicals, silyl radicals such as -Si (R2) 3, - amino radicals such as -N (R2); acyl radicals such as -C (0) R2; carboxy radicals such as -C (0) OR2; acyloxy radicals such as -OC (0) R2; amido radicals such as -C (0) N (R2) 2 and -N (R2) C (O) R2; ionic radicals such as -SO ^ M, wherein M represents atoms or cationic inorganic or organic radicals; sulfonyl radicals such as -S02R2; ether radicals such as -OR2; sulfinyl radicals such as -SOR2; sulfenyl radicals such as -SR2 as well as halogen, nitro, cyano, trifluoromethyl and hydroxy radicals, and the like, wherein each R2 individually represents the same or different substituted or unsubstituted monovalent hydrocarbon radical, with the proviso that amino substituents, such as -N (R) 2, each R 2 taken together can also represent a divalent linking group that forms a heterocyclic radical with the nitrogen atom and in the amido substituents such as C (0) N (R ) 2 and -N (R2) C (0) R2 each R2 linked to N can also be hydrogen. Illustrative alkyl radicals include, e.g., methyl, ethyl, propyl, butyl, and the like. Exemplary aryl radicals include, e.g., phenyl, naphthyl, diphenyl, phlorophenyl, difluorophenyl, benzoyloxyphenyl, carboethoxyphenyl, acetylphenyl, ethoxyphenyl, phenoxyphenyl, hydroxyphenyl; carboxyphenyl, trifluoromethylphenyl, methoxyethylphenyl, acetamidophenyl, dimethylcarbamylphenyl, tolyl, xylyl and the like. Illustrative specific organophosphines include, eg, trimethylphosphine, tris-p-tolylphosphine, tris-p-methoxyphenylphosphine, tris-p-fluorophenylphosphine, tris-p-chlorophenylphosphine, tris-dimethylaminophenylphosphine, propyldiphenylphosphine, t-butyldiphenylphosphine, n-butyldiphenylphosphine, n-hexylphenylphosphine , cyclohexyldiphenylphosphine, dicyclohexylphenylphosphine, tricyclohexylphosphine, tribenzylphosphine, DTOP, ie (4R, 5R) - (-) - O-isopropylidene-2,3-dihydroxy-1,4-bis (diphenylphosphino) butane, and / or (4S, 5S) - (+) - O-isopropylidene-2,3-dihydroxy-1,4-bis (diphenylphosphino) butane and / or (4S, 5R) - (-) - O-isopropylidene-2,3-dihydroxy-1 , 4-bis (diphenylphosphino) butane, substituted or unsubstituted bicyclic bisphosphines such as 1,2-bis (1,4-cyclooctylenphosphino) ethane, 1,3-bis (1,4-cyclooctylenphosphino) propane, 1, 3-bis (1,5-cyclooctylphosphino) propane and 1,2-bis (2,6-dimethyl-1,4-cyclooctylenphosphino) ethane, substituted or unsubstituted bis (2,2'-diphenylphosphinomethyl) biphenyl as bis (2,2'-diphenylphosphinomethyl) biphenyl and bis. { 2, 2'-di (4-fluorophenyl) phosphinomethyl} biphenyl, xantho, thixantphos, bis (diphenylphosphino) ferrocene, bis (diisopropylphosphino) ferrocene, bis (diphenylphosphino) ruthenocene, as well as the alkali metal and alkaline earth metal salts of the sulfonated triphenylphosphines, eg, (tri-m-sulfophenyl) phosphine and (m-sulfophenyl) diphenylphosphine and the like. More particularly, the illustrative etal-organophosphine complex catalysts and illustrative free organophosphine coordinating groups include v. g., those disclosed in the Patents North American Numbers 3,527,809; 4,148,830; 4,247,486; 4,283,562; 4,400,548; 4,482,749, 4,861,918; 4,694,109; 4,742,178; 4,851,581; 4,824,977; 5,332,846; 4,774,362; and Patent Application WO Number 95/30680, published November 16, 1995; the exhibits of which are incorporated herein by reference. The organophosphites which can serve as the coordinating group of the complex metal catalyst-organophosphite coordinating group and / or the free coordinating group of the processes and mixtures of the reaction product of this invention, can be of the achiral type (optically inactive) or chiral (optically active) and are well known in the art. Among the organophosphites which can serve as the coordinating group of the organophosphite complex catalyst and / or the free organophosphite coordinating group of the starting materials of the hydroformylation reaction mixture are the monoorganophosphites, diorganophosphites, triorganophosphites and organopoliphosphites. The organophosphite coordinating groups employable in this invention and / or methods for their preparation are already known in the art. Representative monoorganophosphites may include those having the formula: (II) wherein R represents a substituted or unsubstituted trivalent hydrocarbon radical containing from 4 to 40 carbon atoms or more, such as tricyclic acyclic and trivalent cyclic radicals, eg, trivalent alkylene radicals such as those derived from 1, 2, 2-trimethylolpropane and the like, or trivalent cycloalkylene radicals such as those derived from 1,3,5-trihydroxycyclohexane, and the like. These monoorganophosphites can be described in greater detail, e.g., in U.S. Patent No. 4,567,306, the disclosure of which is incorporated herein by reference. Representative diorganophosphites may include those having the formula: (III) wherein R 4 represents a substituted or unsubstituted divalent hydrocarbon radical containing from 4 to 40 carbon atoms or more and represents a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 18 carbon atoms or more. Representative substituted and unsubstituted monovalent hydrocarbon radicals represented by W in the above formula (III) include alkyl and aryl radicals, while the representative substituted and unsubstituted divalent hydrocarbon radicals, represented by R ^, include divalent acyclic radicals and divalent aromatic radicals. Exemplary divalent acyclic radicals include, eg, alkylene, alkylene-oxy-alkylene, alkylene-NX-alkylene where X is hydrogen or a substituted or unsubstituted monovalent hydrocarbon radical, alkylene-S-alkylene radicals, and cycloalkylene radicals and similar Especially preferred divalent acyclic radicals are the divalent alkylene radicals such as those more fully disclosed, e.g., in U.S. Patent Nos. 3,415,906 and 4,567,302 and the like, the teachings of which are incorporated herein by reference. Illustrative divalent aromatic radicals include, eg, arylene, bisarylene, arylene-alkylene, arylene-alkylene-arylene, arylene-oxy-arylene, arylene-NX-arylene, wherein X is as defined above, arylene-S -arlene, and arylene-S-alkylene and the like. Most preferably R ^ is a divalent aromatic radical such as is more fully disclosed, e.g., in U.S. Patent Nos. 4,599,206 and 4,717,775, and - similar, the exhibits of which are incorporated herein by reference. Representative of the especially preferred class of diorganophosphites are those of the formula: wherein W is as defined above, each Ar is the same or different and represents a substituted or unsubstituted aryl radical, each y is the same or different and is a value of 0, 1, Q represents a divalent connection group that is selected from -C (R5) 2-, -O-, -S-, -NR6-, Si (R7) ) 2_ Y -CO-, where each R ^ is the same or different and represents hydrogen, alkyl radicals having 1 to 12 carbon atoms, phenyl, tolyl and anisyl, R6 represents hydrogen or a methyl radical, each R7 it is the same or different and represents hydrogen or a methyl radical, and ra is a value of 0 or 1. These diorganophosphites are described in greater detail, eg, in U.S. Patent Nos. 4,599,206 and 4,717,775, the expositions of which are incorporated in the present by reference. 'Representative triorganophosphites can include those that have the formula: wherein each R8 is the same or different and is a substituted or unsubstituted monovalent hydrocarbon radical, e.g., an alkyl or aryl radical. Suitable hydrocarbon radicals may contain from 1 to 24 carbon atoms or more and may include those described above for Rl in formula (I) Representative organopolyphosphites contain two or more tertiary phosphorus atoms (trivalent) and may include those that have the formula: wherein X1 represents a substituted or unsubstituted n-valent hydrocarbon connecting radical containing from 2 to 40 carbon atoms, each PA9 is the same or different and is a divalent hydrocarbon radical containing from 4 to 40 carbon atoms, every R! 0 is equal or - - different and is a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 24 carbon atoms, a and b are the same or different and each has a value from 0 to 6, with the proviso that the sum of a + b is 2 to 6 and n is equal to a + b. Of course it will be understood that when a has a value of 2 or more, each radical of R ° can be the same or different, and when b has a value of 1 or more, each radical Rl "can also be the same or different. of representative n-valent hydrocarbon connection (preferably -divalent) represented by XX as well as representative divalent hydrocarbon radicals, represented by R 9 cited above, include both acyclic radicals and aromatic radicals such as alkylene, alkylene-Qm-alkylene, cycloalkylene , arylene, bisarylene, arylene-alkylene and arylene- (CH2) and -Qm- (CH2) and ~ arylene, and the like in which Q, me and are as defined above for formula (IV). especially preferred represented by X ^ and R9 above are divalent alkylene radicals, while especially preferred aromatic radicals represented by X ^ and R9 previously cited on divalent arylene and bisarylene radicals as disclosed more fully, - e.g., in U.S. Patent Nos. 3,415,906; 4,567,306; 4,599,206; 4,769,498; 4,717,775; 4,885,401; 5,202,297; 5,264,616 and 5,364,950 and the like, the expositions of which are incorporated herein by reference. Representative monovalent hydrocarbon radicals, represented by each radical R ^ -u referred to above, include alkyl and aromatic radicals. Illustrative preferred organopolyphosphites may include bisphosphites such as those of formulas (VII) to (IX) which are presented below: (IX) - where each R9, R ^? and X - ^ - of the formulas (VII) to (IX) are the same as defined above for the formula (VI). Preferably, each R 9 and X 1 represents a divalent hydrocarbon radical which is selected from alkylene, arylene, arylene-alkylene-arylene, and bisarylene, while each R 10 represents a monovalent hydrocarbon radical which is selected from the alkyl and aryl radicals . The phosphite coordinating groups of these formulas (VI) to (IX) may be found disclosed, e.g., in U.S. Patent Nos. 4,668,651; 4,748,261; 4,769,498; 4,885,401; 5,202,297; 5,235,113; 5,254,741; 5,264,616; 5,312,996; 5,364,950; and 5,391,801; The exhibits of all of which are incorporated herein by reference. Representative of the especially preferred classes of organobisphosphites are those of the following formulas (X) to (XII): (X) - where Ar, Q, R9, R10, X1, m and y are as defined in the foregoing. Most preferably X1 represents Tin divalent radical of aryl- (CH 2) y- (Q) m- (CH 2) y -aryl, wherein each and individually has a value of 0 or 1; ~ m has a value of 0 or 1 and Q is -0-, -S- or -C (R5) 2- where each R5 is the same or different and represents a radical of _? hydrogen or methyl. Especially preferably each alkyl radical of the groups R 10 above - defined ___ can contain from 1 to 24 carbon atoms and each aryl radical from the previously defined Ar, X ^ -, R9 and R ^ u = X ^ groups of the formulas above - '- Cited (VI) to (XII) may contain from 6 to 18 carbon atoms, and those radicals may be the same or different, while the preferred alkylene radicals of X1 may contain from 2 to 18 carbon atoms, and the preferred alkylene radicals of R9 may contain from 5 to 18 carbon atoms. In addition, preferably, the divalent Ar radicals and the divalent aryl radicals of [alpha] of the abovementioned formulas are phenylene radicals wherein the connection group represented by - (CH-2) and- (Q) m- (CH2 ) and -, is linked to the phenylene radicals in positions remaining in the ortho position with respect to the oxygen atoms of the formulas connecting the phenylene radicals with their phosphorus atom of the formulas. It is also preferred that any substituent radical when present in these phenylene radicals is linked in the para and / or ortho position of the phenylene radicals with respect to the oxygen atom which links the given substituted phenylene radical to its phosphorus atom. Further, if desired, any organophosphite in the above-mentioned formulas (VI) to (XII) can be an ionic phosphite, that is, it can contain one or more ionic residues which are selected from the group consisting of: SO3M where M represents an inorganic or organic cation, - - PO3M wherein M represents an inorganic or organic cation, N (RH) 3X wherein each R ^ is the same or different and represents a hydrocarbon radical containing from 1 to 30 carbon atoms, eg, alkyl, aryl radicals, alkaryl, aralkyl, and cycloalkyl and X2 represents an inorganic or organic anion, - C02M wherein M represents an inorganic or organic cation. as described, e.g., in the North American Patents Numbers 5,059,710; 5,113,022, 5,114,473 and 5,449,653, the expositions of which are incorporated herein by reference. Thus, if desired, these phosphite coordinating groups may contain from 1 to 3 of these ionic residues, while it is preferred that only one of these ionic residues be substituted at any given aryl residue in the phosphite coordinating group when the coordinating group contains more than one of these ionic residues. As appropriate counter-ions, M and X2 for the anionic residues of the ionic phosphites may be mentioned hydrogen (ie, a proton), the alkali and alkaline earth metal cations, e.g., lithium, sodium, potassium, cesium, rubidium, calcium, barium - - magnesium and strontium, the ammonium cation, the quaternary ammonium cations, the phosphonium cations, the arsonium cations and the iminium cations. Suitable anionic groups include, for example, sulfate, carbonate, phosphate, chloride, acetate, oxalate and the like. Of course any of the radicals R9, R10, X2 and Ar of these nonionic and ionic organophosphites of the formulas (VI) to (XII) mentioned above can be substituted if desired with any appropriate substituent containing from 1 to 30 carbon atoms. carbon that does not unduly detrimentally affect the desired result of the hydroformylation reaction. The substituents which may be present in these radicals, in addition to the corresponding hydrocarbon radicals, are the alkyl, aryl, aralkyl, alkaryl and cyclohexyl substituents which may include, for example, silyl radicals such as -Si (R12) 3, amino such as -N (R) 2; phosphine radicals such as -aryl-P (R12) 2; acyl radicals such as -C (0) R12; acyloxy radicals such as -OC (0) R 12; amido radicals such as -CON (R12) and -N (R12) COR12; sulfonyl radicals such as -S02R12; alkoxy radicals such as -OR12; sulfinyl radicals such as -SOR12; Subrenil radicals such as -SR12; phosphonyl radicals such as -P (O) (R12) 2; as well as, halogen, nitro, cyano, trifluoromethyl, hydroxy radicals, and the like, wherein each radical R12 is the same or different, and represents a monovalent hydrocarbon radical having from 1 to 18 carbon atoms (eg, alkyl radicals) , aryl, aralkyl, alkaryl and cyclohexyl), with the proviso that amino substituents such as -N (R1) 2, each Rl2 taken together can also represent a divalent linking group that forms a heterocyclic radical with the nitrogen atom and in amido substituents such as C (0) N (R12) 2 and -N (R12) C (0) R12 each R12 bonded to N can also be hydrogen. Of course it should be understood that any of the groups of substituted or unsubstituted hydrocarbon radicals that constitute a specific determined organophosphite may be the same or different. More specifically illustrative substituents include primary, secondary and tertiary alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, butyl, secondary butyl, tertiary butyl, neo-pentyl, n-hexyl, amyl, secondary amyl, tertiary amyl. , iso-octyl, decyl, octadecyl and the like; aryl radicals such as phenyl, naphthyl and the like; aralkyl radicals such as benzyl, phenylethyl, triphenylmethyl, and the like; alkaryl radicals such - as tolyl, xylyl and the like; alicyclic radicals such as ciciopentyl, cyclohexyl, 1-methylcyclohexyl, cyclooctyl, cyclohexylethyl, and the like; alkoxy radicals such as methoxy, ethoxy, propoxy, t-butoxy, -OCH2-CH2OCH3, - (OCH2CH2) 2OCH3, -OCH2CH2) 3OCH3, and the like; aryloxy radicals such as phenoxy and the like; as well as the silyl radicals such as -Si (CH3) 3, -Si (OCH3) 3, -Si (03 ^) 3, and the like; amino radicals such as -NH 2, -N (CH 3) 3) 2-NHCH 3, -NH (C 2 H 5) and the like; arylphosphine radicals such as -P (CgH5) 2, and the like; acyl radicals such as -C (0) CH3, -C (0) C2H5, -C (0) CgH5, and the like; carbonyloxy radicals such as -C (0) 0CH3 and the like; oxycarbonyl radicals such as -0 (CO) CgH5, and the like; amido radicals such as -CONH2, -CON (CH3) 2, -NHC (0) CH3, and the like; sulfonyl radicals such as -S (O) 2 C 2 H 5 and the like; sulfinyl radicals such as -S (0) CH 3 and the like; sulfenyl radicals such as -SCH3, -SC2H5, -SC5H5, and the like; phosphonyl radicals such as -P (O) (C6H5) 2, -P (O) (CH3) 2, -P (O) (C2H5) 2, -P (O) (C3H7) 2, -P (O) (C4H9) 2, -P (O) (C6H13) 2, -P (0) CH3 (C6H5), -P (O) (H) (C6H5) and the like. Specific illustrative examples of these organophosphite coordinating groups include the following: 2-t-butyl-4-u-ethoxyphenyl (3,3'-di-t-butyl-5,5'-dimethoxy-1, 1'ifenyl) -2, 2 '-diil) phosphite which has the formula: Coordinating Group A methyl (3,3'-di-t-butyl-5,5'-dimethoxy-1,1 '-biphenyl-2,2'-diyl) phosphite having the formula: Coordinating Group B 6, 6 * - [[4,4'-bis (1,1-dimethylethyl) - [1, 1-binaphthyl] -2, 2'-diyl] -bis (oxy)] bisdibenzo [d, f] [1, 3, 2] -dioxaphosphepin having the formula: Coordinating Group C 6, 6 '[[3, 3'-bis (1,1-dimethylethyl) -5,5'-dimethoxy- [1,1'-biphenyl] -2,2'-diyl] bis (oxy)] bis-dibenzo [d, f] [1,3,2] dioxaphosphepin having the formula: Coordinating Group D 6, 6'- [[3,3 ', 5, 5' -tetrakis (1,1-dimethylpropyl) - [1,1 '-bifinyl] -2, 2'-diyl] bis (oxy) ] bis-dibenzo [d, f] [1,3, 2] dioxaphosphepin having the formula: Coordinating Group E 6, 6 '- [[3, 3', 5, 5 '-tetrakis (1,1-dimethylethyl) -1,1' -biphenyl] -2,2 '- * - diyl] bis (oxy)] bis- dibenzo [d, f] [1,3,2] -dioxaphosphepin having the formula Coordinating Group F (2R, 4R) -di [2,2 '- (3,3', 5, 5'-tetrakisoter-amyl-1,1'-biphenyl)] -2, 4-pentyldiphosphite having the formula: _ Coordinating Group G (2R, 4R) -di [2, 2 '- (3, 3', 5, 5 '-tetrakis-tert-butyl-1,1'-biphenyl)] -2, 4-pentyldiphosphite having the formula Coordinating Group H (2R, R) -di [2,2'- (3,3'-di-amyl-5,5'-dimethoxy-1,1'-biphenyl)] -2,4-pentyldiphosphite having the formula: Coordinating Group I (2R, 4R) -di [2, 2 '- (3, 3' -di-tert-butyl-5, 5'-dimethyl-1, 1 '• if enyl)] -2, 4-pentyldiphosphite having the formula Coordinating Group J (2R, 4R) -di [2, 2 '- (3, 3' -di-tert-butyl-5, 5 * -dietoxy-1, 1 I-biphenyl)] -2, 4-pentyldiphosphite having the formula : Coordinating Group K (2R, 4R) -di [2, 2 '- (3, 3'-di-tert-butyl-5,5'-diethyl-1,1'-biphenyl)] -2,4-pentyldiphosphite having the formula: Coordinating Group L (2R, 4R) -di [2, 2 '- (3, 3'-di-tert-butyl-5,5'-dimethoxy-1,1' biphenyl)] -2,4-pentyldiphosphite having the formula: Coordinating Group M 6- [[2 '- [(4,6-bis (1,1-dimethylethyl) -1,3,2-benzodioxaphosphol-2-yl) oxy] -3,3'-bis (1,1-dimethylethyl) -5,5'-dimethoxy [1,1'-biphenyl] -2-yl] oxy] -4,8-bis (1,1-dimethylethyl) -2,10-dimethyloxydibenzo [d, f] [1, 3 , 2] dioxaphosphepin that has the formula Coordinating Group N 6- [[2 '- [1, 3,2-benzodioxafosfol-2-yl) oxy] 3,3'-bis (1,1-dimethylethyl) -5,5'-dimethoxy [1,1'] -biphenyl] -2-yl] oxy] -4, 8, bis (1,1-dimethylethyl) -2, 10-dimethoxydibenzo [d, f] [1,3,2] dioxaphosphepin having the formula Coordinating Group O 6- [[2 '- [(5,5-Dimethyl-1,3, 2-dioxaphosphine-2-yl) oxy] -3,3'-bis (1,1-dimethylethyl) -5, 5'-dimethoxy [1,1'-biphenyl] -l-yl] oxy] -4,4-bis (1,1-dimethylethyl) -2,10-dimethoxydibenzo [d, f] [1, 3, 2] dioxaphosph epine that has the formula Coordinating Group P 2 '[[4, 8-bis (1,1-dimethylethyl) -2, 10-dimethoxydibenzo [d, f] [1,3,2] -dioxaphosphepin-6-yl] oxy] -3, 3 '-bis (1,1-dimethylethyl) -5,5'-dimethoxy [1,1-biphenyl] -2-yl-bis (4-hexylphenyl) ester of phosphoric acid having the formula: Coordinating Group Q 2- [[2- [[4, 8, -bis (1,1-dimethylethyl), 2, 10-dimethoxydibenzo- [d, f] [1,3,2] dioxophosphenpin-6-yl] oxy] -3 - (1,1-dimethylethyl) -5-methoxyphenyl] methyl] -4-methoxy, 6- (1,1-dimethylethyl) phenyldiphenyl ester of phosphoric acid having the formula: 3-methoxy-l, 3-cyclohexamethylene-tetrakis [3,6-bis (1, 1-dimethylethyl) -2-naphthalenyl] ester of phosphoric acid having the formula: Coordinating Group S 2,5-bis (1,1-dimethylethyl) -1,4-phenylene tetrakis [2,4-bis (1, 1-dimethylethyl) phenyl] ester of phosphoric acid having the formula: Coordinating group T methylene-2, 1-phenylene tetrakis [2,4-bis (1,1-dimethylethyl) phenyl] ester of phosphoric acid having the formula: Q ~ 8 > Coordinating Group U [1,1-biphenyl] -2,2-diyl] tetrakis [2- (1, 1-dimethylethyl) -4-methoxyphenyl] ester of phosphoric acid having the formula: Coordinating Group V Still other illustrative organophosphorus coordinating groups useful in this invention include those disclosed in the North American Patent Application Serial Number (D-17459-1), filed on the same date as the present disclosure of which is incorporated herein. by reference. The complex metal-coordinator group catalysts employable in this invention can be formed by methods known in the art. The complex metal-coordinating group catalysts may be in homogeneous or heterogeneous form. For example, the preformed metal hydride carbonyl-organophosphorus coordinating group catalysts can be prepared and introduced into the reaction mixture by a hydroformylation process. More preferably, the complex metal-coordinator group catalysts can be derived from a metal catalyst precursor that can be introduced into the reaction medium for in situ formation of the active catalyst. For example, rhodium catalyst precursors such as rhodium dicarbonyl acetylacetonate, Rh203, Rh4 (CO) 2 2, Rhg (CO) gg, Rh (N 3 3) 3 and the like can be introduced into the reaction mixture together with the organophosphorus coordinating group for the in situ formation of the active catalyst. In a preferred embodiment of this invention, rhodium dicarbonyl acetylacetonate is used as a rhodium precursor and is reacted in the presence of a solvent with the organophosphorus co-coordinator to form a complex rhodium precursor-catalytic organophosphorus coordinating group which it is introduced into the reactor together with an excess of the free organophosphorus coordinating group for the in situ formation of the active catalyst. In any event, it is sufficient for the purposes of this invention and the carbon monoxide the hydrogen and the organophosphorus compound to be all coordinating groups which are capable of forming in complex with the metal and which is present an active catalyst of metal-organophosphorus coordinating group. in the reaction mixture under the conditions used in the hydroformylation reaction. More particularly, a catalyst precursor composition consisting essentially of a metal complex precursor catalyst-solubilized coordinator group, an organic solvent and a free coordinating group can be formed. These precursor compositions can be prepared by forming a solution of a metal starting material, such as metal oxide, hydride, carbonyl or a salt, eg, a nitrate, which may or may not be in complex combination with a coordinating group as defined at the moment. Any suitable metal starting material can be used, e.g. rhodium dicarbonyl acetylacetonate Rh203, Rh4 (CO)] _2 'Rhg (CO)? g, Rh (N? 3) 3, and the rhodium carbonyl hydrides of the organophosphorus coordinating group. The carbonyl and organophosphor coordinating groups, if not already formed in complex with the starting metal, can be complexed with the metal either before or in situ, during the hydroformylation process. By way of illustration, the precursor composition of the preferred catalyst of this invention consists essentially of a precursor complex carbonyl catalyst of rhodium-grouped organophosphorus coordinator, a solvent and a free organophosphorus coordinating group prepared by forming a solution of rhodium dicarbonyl acetylacetonate. , an organic solvent and a coordinating group as defined herein. The organophosphorus coordinating group readily replaces one of the carbonyl coordinating groups of the rhodium acetylacetonate complex precursor at room temperature as evidenced by the evolution of carbon monoxide gas. This substitution reaction can be facilitated by heating the solution if desired. Any suitable organic solvent may be employed wherein both the rhodium dicarbonyl acetylacetonate complex precursor and the complex precursor of the rhodium organophosphorus coordinating group are soluble. The precursor amounts of the rhodium complex catalyst, the organic solvent and the organophosphorus coordinating group, and their preferred embodiments present in these catalyst precursor compositions can obviously correspond to those amounts that can be used in the hydroformylation process of the invention. Experience has shown that the acetylacetonate coordinating group of the precursor catalyst is replaced by hydroformylation with a different coordinating group, eg, hydrogen, carbon monoxide or the organophosphorus coordinating group, in order to form the active complex catalyst as explained above. foregoing. In a continuous process, the acetylacetonate which is released from the precursor catalyst under the hydroformylation conditions is removed from the reaction medium with aldehyde produced and thus there is no form that is detrimental to the hydroformylation process. The use of these preferred rhodium complex catalytic precursor compositions provides a simple economical and efficient method for handling the rhodium precursor metal and the initiation of hydroformylation. Accordingly, the complex metal-coordinator group catalysts used in the process of this invention consist essentially of a metal formed in complex with carbon monoxide and a coordinating group, the coordinating group (formed in complex) being bound to the metal of a chelated and / or non-chelated. In addition, the terminology "consists essentially of", as used herein, does not exclude but rather includes the hydrogen formed in complex with the metal in addition to the carbon monoxide and the coordinator. further, this terminology does not exclude the possibility of other organic coordinating groups and / or anions that could also be trained in - complex with metal. Materials in quantities that improperly detrimentally contaminate or inappropriately deactivate the catalyst are undesirable and therefore the most desirable catalyst is free of contaminants such as halogen bound to the metal (e.g., chlorine, and the like) even though this It may not be absolutely necessary. Hydrogen and / or carbonyl coordinating groups of a complex metal catalyst-active organophosphorus coordinating group may be present as a result of being coordinating groups linked to a precursor catalyst, and / or as a result of in situ formation, eg, due to the hydrogen and carbon monoxide gases employed in the hydroformylation process of this invention. As will be seen, the hydroformylation reactions involve the use of a complex catalyst metal-coordinator group as described herein. Of course, mixtures of these catalysts can be used if desired. The mixtures of the hydroformylation catalysts and the catalysts and the hydrogenation described below can be used, if desired. The amount of the metal complex catalyst-coordinating group present in the reaction medium of a given hydroformylation reaction need only be that minimum amount necessary to provide the desired concentration of desired metal to be employed and which will provide the basis for minus the catalytic amount of metal necessary to catalyze the specific hydroformylation reaction involved as disclosed, eg, in the aforementioned patents. In general, the concentration of the catalyst can vary from several parts per million to several percentages by weight. The organophosphorus coordinating groups can be employed in the aforementioned catalysts in a molar ratio generally of about 0.5: 1 or less to about 1000: 1 or greater. The concentration of the catalyst will depend on the hydroformylation reaction conditions and the solvent employed. In general, the concentration of the organophosphorus coordinating group in the hydroformylation reaction mixtures may vary from about 0.005 percent to 25 percent, based on the total weight of the reaction mixture. Preferably, the concentration of the coordinating group is between 0.01 percent and 15 percent by weight, and especially preferably is about 0.05 percent and 10 percent by weight on that basis. In general, the concentration of the metal in the hydroformylation reaction mixtures can be as high as 2000 parts per million by weight or more, based on the weight of the reaction mixture. Preferably, the concentration of the metal is between about 50 and 1000 parts per million by weight based on the weight of the reaction mixture, and especially preferably between about 70 and 800 parts per million by weight, based on the weight of the the reaction mixture. In addition, of the complex catalyst metal-coordinating group, a free coordinating group (i.e., a coordinating group that has not been complexed with the rhodium metal) can also be present in the hydroformylation reaction medium. The free coordinating group may correspond to any of the coordinating groups defined above, discussed as employable herein. It is preferred that the free coordinating group be the same as the coordinating group of the complex catalyst metal-coordinator group employed. However, these coordinating groups do not need to be equal in any given process. The hydroformylation reaction may involve up to 100 moles, or more, of the free coordinating group per mole of the metal, in the hydroformylation reaction medium. Preferably, the hydroformylation reaction is carried out in the presence of about 0.25 to about 50 moles of the coordinating phosphorus, and more preferably about 0.5 to about 30 moles of the coordinate phosphorus per mole of the metal present in the reaction medium.; these amounts of coordinating phosphorus being the sum of both the amount of coordinating phosphorus that is bound (complexed) with the rhodium metal present and the amount of free coordinate phosphorus (not formed in complex) present. Of course, if desired, the coordinating replenishment or additional phosphorus can be supplied to the reaction medium of the hydroformylation reaction at any time and in any appropriate manner, v.gr, to maintain a predetermined level of the free coordinating group in the medium of reaction. As indicated above, the hydroformylation catalyst may be in heterogeneous form during the reaction and / or during the separation of the product. These catalysts are particularly advantageous in the hydroformylation of olefins or alkadienes to produce high boiling or thermally sensitive aldehydes so that the catalyst can be separated from the products by filtration or decantation at low temperatures. For example, the rhodium catalyst can be fixed to a support so that the catalyst retains its solid form during both the hydroformylation and separation steps, ie soluble in a liquid reaction medium at high temperatures and then precipitated during cooling. As an illustration, the rhodium catalyst can be impregnated in any solid support, such as inorganic oxides, (e.g., alumina, silica, titania or zirconia) carbon or ion exchange resins. The catalyst can be supported on, or intercalated within the pores of, a zeolite or glass; The calthaliser can also be dissolved in a liquid film, coating the pores of the zeolite or the glass. These zeolite-supported catalysts are particularly advantageous for producing one or more of the regioisomeric aldehydes at high selectivity as determined by the pore size of the zeolite. The technique for supporting the catalysts in solids, such as incipient moisture, which is already known to those skilled in the art. The solid catalyst formed in this way may still be complexed with one or more of the coordinator groups defined above. Descriptions of these solid catalysts can be found, for example, in: J. Mol. Cat. 1991, 70 363-368; Catal. Lett. 1991, 8, 209-214; J. Organomet. Chem, 1991, 403, 221-227; Nature, 1989, 339, 454-455; J. Catal. 1985, 96, 563-573; J. Mol. Cat. 1987, 39, 243-259.

The rhodium catalyst can be attached to a thin film or a membrane support, such as cellulose acetate or polyphenylene sulfone, as described, for example in J. Mol. Cat. 1990, 63, 213-221. The rhodium catalyst can be attached to an insoluble polymer support via a coordinating organophosphorus containing group, such as a phosphine or phosphite, incorporated in the polymer. These coordinating groups supported by polymer. they are well known and include those commercially obtainable species such as triphenylphosphine supported on divinylbenzene / polystyrene. The supported coordinating group is not limited by the selection of the polymer or the species that contains the phosphor incorporated in it. Descriptions of the polymer-supported catalysts can be found, for example, in: J. Mol. Cat. 1993, 83, 17-35; Chemtech 1983, 46; J. Am. Chem. Soc. 1987, 109, 7122-7127. In the heterogeneous catalysts described above, the catalyst can remain in its heterogeneous form throughout the process of hydroformylation and separation of the catalyst. In another embodiment of the invention, the catalyst can be supported on a polymer which, due to the nature of its molecular weight, is soluble in the reaction medium at elevated temperatures, but precipitates on cooling, thereby facilitating the separation of the catalyst of the reaction mixture. These "soluble" polymer-supported catalysts are described, for example in: Polymer, 1992, 33, J. Org. Chem. 1989, 54, 2726-27-30. When the rhodium catalyst is in a heterogeneous or sustained form, the reaction can be carried out in the gas phase. Particularly preferably, the reaction is carried out in the aqueous suspension phase due to the high boiling temperatures of the products and to avoid the decomposition of the aldehydes produced. The catalyst can then be separated from the produced mixture by filtration or decantation. Substituted and unsubstituted alkadiene starting materials useful in hydroformylation reactions include, but are not limited to, conjugated aliphatic diolefins represented by the formula: Rl R2 CH2 = C - C = CH2 (XIII: wherein R] _ and R2 are the same or different and are hydrogen, halogen or a substituted or unsubstituted hydrocarbon radical. The alkadienes can be linear or - branched and may contain substituents (e.g., alkyl groups, halogen atoms, amino groups or silyl groups). Illustrative of the appropriate alkadiene starting materials are butadiene, isoprene, dimethylbutadiene and cyclopentadiene. Particularly preferably, the alkadiene starting material is butadiene itself (CH2 = CH-CH = CH2). For the purposes of this invention, the term "alkadiene" is intended to include all permissible substituted and unsubstituted conjugated diolefins including all permissible mixtures comprising one or more of the substituted or unsubstituted conjugated diolefins. Illustrative of the substituted or unsubstituted alkadienes (including alkadiene derivatives) include those permissible substituted and unsubstituted alkadienes described in Kirk-Othmer, Encyclopedia of Chemical Technology, Fourth Edition, 1996, the pertinent portions of which are incorporated herein. by reference. The hydroformylation reaction conditions may include any of the hydroformylation conditions of the appropriate type used hitherto to produce aldehydes. For example, the total gas pressure of hydrogen, carbon monoxide and olefin or alkadiene as the starting compound of the hydroformylation process may vary from about .0703 to about 703 kilograms per absolute square centimeter. Generally the hydroformylation process is operated at a total gas pressure of hydrogen, carbon monoxide and olefin or the alkadiene starting compound of less than about 105.45 kilograms per absolute square centimeter and more preferably less than about 70.30 kilograms per square centimeter absolute, the minimum total pressure being predominantly limited by the amount of reagents necessary to obtain a desired reaction rate. The total pressure employed in the hydroformylation reaction may generally vary from about 1.41 to about 210.90 kilograms per absolute square centimeter preferably from about 3.52 to 105.45 kilograms per absolute square centimeter. The total pressure of the hydroformylation process will depend on the specific catalyst system used. More specifically, the partial pressure of carbon monoxide from the hydroformylation process can generally range from about .0703 to about 210.90 kilograms per absolute square centimeter, and preferably from about .211 to about 105.45 kilograms per absolute square centimeter, while the partial pressure of hydrogen can generally vary from about .0703 to about 210.90 kilograms per absolute square centimeter, and preferably from about .211 to about 105.45 kilograms per absolute square centimeter. In general, the molar ratio of carbon monoxide to gaseous hydrogen can vary from about 100: 1 or greater to about 1: 100 or less, with the preferred molar ratio of carbon monoxide to hydrogen gas being from about 1:10 to about 10. :1. The partial pressures of carbon monoxide and hydrogen will depend in part on the specific catalyst system employed. The partial pressure of carbon monoxide must be sufficient for the hydroformylation reaction, e.g., of an alkadiene to pentenal, to occur at an acceptable rate. The hydrogen partial pressure must be sufficient for the hydroformylation reaction and / or hydrogenation to occur at an acceptable, but not so high, regime for the hydrogenation of butadiene or the isomerization of pentenales to undesired isomers to occur. It will be understood that carbon monoxide and hydrogen can be used separately, in admixture with one another, ie, synthesis gas, or they can be produced in situ in part, under the reaction conditions.

In addition, the hydroformylation process can be carried out at a reaction temperature and can be used from about 20 ° C to about 200 ° C, preferably from about 50 ° C to about 150 ° C, and especially preferably from about 65 ° C. ° C at approximately 115 ° C. The temperature must be sufficient for the reaction to occur (which may vary with the catalyst system used), but not so high that decomposition of the coordinating group or catalyst occurs. At elevated temperatures (which may vary with the catalyst system used), isomerization of pentenales into unwanted isomers may occur. Of course it will also be understood that the hydroformylation reaction conditions employed will be regulated by the type of the desired aldehyde product. In the alkdiene hydroformylation step, the hydroformylation reaction of alkadiene can be carried out at a partial pressure of conversion of alkadiene and / or carbon monoxide sufficient to selectively produce the pentenales and penten-1-ols, respectively. In certain cases, it has been found that the partial pressure of carbon monoxide in the hydroformylation reaction system of alkadiene is higher than the partial pressure of hydrogen, and the conversion of the pentenal intermediates to the hydrogenated and bishydroformylated byproducts is suppressed . It is believed that these reactions are inhibited by carbon monoxide. It has also been found that when the hydroformylation reaction of alkadiene is carried out with incomplete butadiene conversion, the conversion of pentenal intermediates into bishydroformylated byproducts is suppressed. In general, the alkadiene conversion can vary from about 1 weight percent to about 100 weight percent, preferably from about 10 weight percent to about 100 weight percent, and especially preferably about 25 weight percent, and most preferably about 25 weight percent. percent by weight to about 100 weight percent, based on the total weight of the alkadiene fed to the reaction. While not wishing to be bound by any specific theory, it is believed that butadiene is preferably formed in complex with the complex catalyst metal-coordinating group acting as an inhibitor for the hydroformylation of the pentenal intermediates. The partial conversion of butadiene can be achieved by a short reaction time, a low total pressure, a low catalyst concentration and / or a low temperature. The high butadiene concentrations are especially useful in the hydroformylation process of this invention. - 1 In the reductive hydroformylation process of penten-1-ol of this invention, the reductive hydroformylation reaction of penten-1-ol can be carried out at a conversion of penten-1-ol and / or a partial pressure of carbon monoxide sufficient to selectively produce the 1,6-hexanediols. However, in the reductive hydroformylation reaction of penten-1-ol, the conversion of penten-1-ol may be complete or incomplete, and the partial pressure of carbon monoxide may be higher or lower than the partial pressure of hydrogen, as described above. To allow maximum levels of 3-pentenales and / or 4-pentenales and to minimize the 2-pentenales, it is desirable to maintain some partial pressure of alcadiene or when the conversion of alcadiene is complete, the partial pressure of carbon monoxide should be sufficient to prevent or minimize the referral vg the isomerization and / or hydrogenation of the substituted or unsubstituted 3-pentenales. In one embodiment, the hydroformylation of alkadienes is carried out at a partial pressure of alkadiene and / or a partial pressure of carbon monoxide sufficient to prevent or minimize the derivation, e.g. isomerization and / or hydrogenation of substituted or unsubstituted 3-pentenales. In another embodiment, the hydroformylation of alkadiene e.g. butadiene is carried out at a partial pressure of alkadiene greater than 0 kilogram per square centimeter, preferably greater than 352 kilogram per square centimeter and particularly preferably greater than 633 kilogram per square centimeter; and a partial pressure of carbon monoxide greater than 0 kilogram per square centimeter, preferably greater than 1.76 kilograms per square centimeter and especially preferably greater than 7.03 kilograms per square centimeter. The hydroformylation reaction is also carried out in the presence of water or an organic solvent for the complex metal catalyst-coordinating group and the free coordinating group. Depending on the specific catalyst and the reagents employed, suitable organic solvents include, for example, alcohols, alkanes, alkenes, alkynes, ethers, aldehydes, aldehyde condensation byproducts of higher boiling temperature, ketones, esters, amides, tertiary amines, compounds aromatic and similar. Any suitable solvent that does not unduly detrimentally interfere with the proposed hydroformylation reaction may be employed and these solvents may include those disclosed hitherto, commonly employed in known metal-catalyzed hydroformylation reactions. The - - Mixtures of one or more different solvents can be used if desired. In general, with respect to the production of aldehydes it is preferred to use aldehyde compounds corresponding to the desired aldehyde products which it is desired to produce, and / or the liquid condensation by-products of aldehyde of higher boiling temperature, such as solvents. main organic as is common in the art. These aldehyde condensation byproducts can also be preformed if desired and used accordingly. Exemplary preferred solvents usable in the production of aldehydes include ketones (eg ketone and methylethyl ketone), esters (eg ethyl acetate), hydrocarbons (eg toluene), nitrohydrocarbons (eg nitrobenzene), ethers (eg tetrahydrofuran (THF) and glyme ), 1,4-butanediols and sulfolane. Suitable solvents are disclosed in US Pat. No. 5,132,996. The amount of the solvent employed is not critical to the present invention and only needs to be that amount sufficient to solubilize the catalyst and the free coordinating group of the hydroformylation reaction mixture to be treated. Generally, the amount of the solvent may vary from about 5 weight percent to about 99 weight percent or more, based on the total weight of the starting material of the hydroformylation reaction mixture.

- The reductive hydroformylation process can also be carried out in the presence of a promoter. As used herein, the term "promoter" means an organic and inorganic compound with a pKa ionizable hydrogen of from about 1 to about 35. Illustrative promoters include, for example, protic solvents, organic and inorganic acids, alcohols, water , phenols, thiols, thiophenols, nitroalkanes, ketones, nitriles, amines (eg pyrroles and diphenylamine), amides (eg acetamide), mono-, di- and tri-alkylammonium salts and the like. The promoter may be present in the reductive hydroformylation reaction mixture either alone or incorporated in the structure of the coordinating group, either as the complex catalyst of the metal coordinating group or as a free coordinating group, or in the alkadiene structure. The desired promoter will depend on the nature of the metal coordinating groups of the metal complex catalysts and coordinator group. In general, a catalyst with an acyl linked to the more basic metal or other intermediate will require a lower concentration and / or a less acidic promoter. In general, the amount of the promoter can vary from about 10 parts per million plus or minus to about 99 weight percent or more, based on the total weight of the starting materials of the reductive hydroformylation process mixture.

In one embodiment of the invention, the hydroformylation reaction mixture may consist of one or more liquid phases, e.g. a polar phase and a non-polar phase, these processes are often advantageous, for example, for separating catalyst products and / or reagents by dividing at any phase. In addition, the selectivities of the product that depend on the properties of the solvent can be increased by carrying out the reaction in that solvent. A well-known application of this technology is the hydroformylation of the aqueous phase of olefins using sulfonated phosphine coordinating groups for the rhodium catalyst. A process carried out in the aqueous solvent is particularly advantageous for the preparation of aldehydes, because the products can be separated from the catalyst by extraction in an organic solvent. Alternatively, aldehydes, particularly pentenales, adipaldehydes and 6-hydroxyhexanal, which tend to undergo autocondensation reactions, are expected to stabilize in an aqueous solution such as aldehyde hydrates. As described herein, the phosphorus-containing coordinating group for the rhodium hydroformylation catalyst may contain any of a number of substituents, such as cationic or anionic substituents, which will cause the catalyst to be - soluble in a polar phase, e.g. Water. Optionally, a phase transfer catalyst can be added to the reaction mixture to facilitate the transport of catalyst, reagents or products, in the desired solvent phase. The structure of the coordinating group or the phase transfer catalyst is not critical and will depend on the selection of the conditions and reaction solvent and the desired products. When the catalyst is present in a multiphase system, the catalyst can be separated from the reactants and / or products by conventional methods, such as extraction or decantation. The reaction mixture itself may consist of one or more phases. Alternatively, the multiphase system can be treated at the end of the reaction by for example the addition of a second solvent, in order to separate the catalyst products. See, for example, U.S. Patent No. 5,180,854, the disclosure of which is incorporated herein by reference. In one embodiment of the process of this invention, an olefin can be hydroformylated together with an alkadiene, using the above-described complex metal-coordinator group catalysts. In these cases, an aldehyde derivative of the olefin is also produced together with the pentenales. It has been found that alkadiene reacts to form a complex with the metal more rapidly than certain of the olefins and that it requires more forced conditions to hydroform itself by itself than certain of the olefins. The mixtures of different olefinic starting materials can be used, if desired, in the hydroformylation reactions. More preferably, the hydroformylation reactions are especially useful for the production of pentenales by hydroformylation alkadienes in the presence of alpha-olefins containing 2 to 30, preferably 4 to 20 carbon atoms, including isobutylene and internal olefins containing from 4 to 20 carbon atoms as well as the mixtures of the starting material of these alpha-olefins and internal olefins. Commercial alpha-olefins containing 4 or more carbon atoms may contain small amounts of corresponding internal olefins and / or their corresponding saturated hydrocarbon and that these commercial olefins do not necessarily have to be purified thereof before hydroformylation. Illustrative of other olefinic starting materials include alpha-olefins, internal olefins, 1,3-dienes, alkyl alkenoates, alkenyl alkanoates, alkenylalkyl ethers, alkenols, alkenes and the like, e.g. ethylene, propylene, 1-butene, l-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1- hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-ecosengine, 2-butene, 2-methylpropene (isobutylene), 2-methylbutene, 2-pentene, 2-hexene, 3-hexane, 2-heptene, cyclohexene , propylene dimers, propylene trimers, propylene tetramers, piperylene, isoprene, 2-ethyl-1-hexene, 2-octene, styrene, 3-phenyl-1-propene, 1,4-hexadiene, 1,7-octadiene , 3-cyclohexyl-l-butene, allyl alcohol, allylic butyrate, hex-l-en-4-ol, oct-l-en-4-ol, vinyl acetate, allylic acetate, 3-butenyl acetate, propionate vinyl, allyl propionate, methyl methacrylate, vinylethyl ether, vinylmethyl ether, vinyl cyclohexene, allylethyl ether, methyl pentenoate, n-propyl-7-octenoate, pentenales, eg 2-pentenal, 3-pentenal and 4-pentenal; penten-1-oles e.g. 2-penten-1-ol, 3-penten-1-ol and 4-penten-1-ol; 3-butenonitrile, 3-pentenenitrile, 5-hexanamide, 4-methyl styrene, 4-isopropyl styrene, 4-tertiary butyl styrene, alpha-methyl styrene, 4-butyl tertiary-alpha-methyl styrene, 1, 3-diisopropenylbenzene, eugenol, isoeugenol, safrole, iso-safrole, anethole, 4-allylanisole, indene, limonene, beta-pinene, dicyclopentadiene, cyclooctadiene, camphene, linalool and the like. Other exemplary olefinic compounds may include, for example, p- isobutylstyrene, 2-vinyl-6-methoxynaphthylene, 3-ethenylphenylphenyl ketone, 4-ethenylphenyl-2-thienyl ketone, 4-ethenyl-2-fluorobiphenyl, 4- (1,3-dihydro-l-oxo-2H-isoindole) -2-yl) styrene, 2-ethenyl-5-benzoylthiophene, 3-ethenylphenylphenyl ether, propenylbenzene, isobutyl-4-propenylbenzene, phenylvinyl ether and the like. Other olefinic compounds include substituted aryl ethylenes as described in U.S. Patent Number 4,329,507, the disclosure of which is incorporated herein by reference. As indicated above, it is generally preferred to carry out the hydroformylation process of this invention in a continuous manner. In general, continuous hydroformylation processes are well known in the art and may involve: (a) hydroformylating the olefinic or alkadiene starting material (s) with carbon monoxide and hydrogen in a liquid homogeneous reaction mixture comprising a solvent, the complex metal catalyst-coordinating group and the free coordinating group; (b) maintaining favorable reaction temperature and pressure conditions for the hydroformylation of the olefinic or alkadiene starting material (s); (c) supplying replacement amounts of the olefinic or alkadiene starting material (s), carbon monoxide and hydrogen in the reaction medium as these - reagents are used; and (d) recovering the desired aldehyde hydroformylation product (s) in any desired manner. The continuous process can be carried out in a single-pass mode, ie, wherein a vaporous mixture comprises the olefinic or alkadiene starting material (s) and the vaporized aldehyde product is removed from the liquid reaction mixture from where the aldehyde product and the olefinic or alkadiene starting material (s) are recovered, carbon monoxide and hydrogen are supplied to the liquid reaction medium for the next single pass without recycling the starting material (s) alkadiene olefinic, unreacted However, it is generally desirable to employ a continuous process that involves either a liquid and / or gas recycling process. These types of recycling process are well known in the art and can involve the liquid recycling of the solution of the complex metal catalyst-coordinating group separated from the desired aldehyde reaction product (s), as disclosed in e.g. in U.S. Patent Number 4,148,830 or a gas cycle process such as disclosed in e.g. in U.S. Patent Number 4,247,486, as well as a combination of the liquid and gas recycling process if desired. The disclosures of U.S. Patent Nos. 4,148,830 and 4,247,486 are hereby incorporated by reference thereto. The especially preferred hydroformylation process of this invention comprises a continuous liquid catalyst recycling process. The substituted and unsubstituted pentenal intermediates that can be prepared by the processes of this invention include one or more of the following: cis-2-pentenal, trans-2-pentenal, cis-3-pentenal, trans-3-pentenal and / or 4-pentenal, including mixtures of one or more of the aforementioned pentenales. Illustrative of the appropriate pentenales replaced and not replaced (including pentene derivatives) include those permissible substituted and unsubstituted pentenales which are described in Kirk-Othmer, Encyclopedia of Chemical Technology, Fourth Edition, 1996, the pertinent portions of which are incorporated herein by reference. The substituted and unsubstituted 6-hydroxyhexanal products that can be prepared by the processes of this invention include, for example, 6-hydroxyhexanal and substituted 6-hydroxyhexanals (eg 2-methyl-6-hydroxyhexanal and 3,4-dimethyl-6). -hydrohexanal and the like) including mixtures of one or more of the aforementioned 6-hydroxyhexanals. Illustrative of the appropriate substituted or unsubstituted 6-hydroxyhexanals (including 6-hydroxyhexanal derivatives) include those permissible substiuuted and unsubstituted 6-hydroxyhexanals described in Kirk-Othmer, Encyclopedia of Chemical Technology, Fourth Edition, 1996, the pertinent portions of which are incorporated herein by reference. As indicated above, the hydroformylation reactions may involve a method of recycling the liquid catalyst. These methods for recycling the liquid catalyst are known as disclosed in e.g. in U.S. Patents Numbers 4,668,651; 4,774,361; 5,102,505 and 5,110,990. For example, in these liquid catalyst recycling processes, the common practice is to continuously or intermittently remove a portion of the liquid reaction product medium it contains, e.g. the aldehyde product, the solubilized coordinating metal complex catalyst complex, the free coordinating group and an nic solvent, as well as the byproducts produced in situ by hydroformylation, e.g. the aldehyde condensation byproducts, etc., and the unreacted olefinic or alkadiene starting material, carbon monoxide and hydrogen (synchronization gas) dissolved in the medium, from the hydroformylation reactor to a distillation zone e.g. a vaporizer / separator wherein the desired aldehyde product is distilled in one or more stages under normal, reduced or elevated pressure, as appropriate, and separated from the liquid medium. The desired, vaporized or distilled aldehyde product thus separated can then be condensed and recovered in any conventional manner, as discussed above. The remaining non-volatilized liquid waste containing the complex metal catalyst-coordinating group, the solvent, the free coordinating group and usually a certain amount of the undistilled aldehyde product is then recycled again with or without additional treatment as desired, together with any by-products and non-volatilized gaseous reactants that could still be dissolved in the recycled liquid waste, in any conventional manner desired, to the hydroformylation reactor, as disclosed herein in the aforementioned patents. In addition, the reactive gases removed in this manner by distillation of the vaporizer can also be recycled back to the reactor if desired. In one embodiment of this invention, the aldehyde mixtures can be separated from the other components of the crude reaction mixtures wherein the aldehyde mixtures are produced by any suitable method. Suitable separation methods include, for example, solvent extraction, crystallization, distillation, vaporization, phase separation, evaporation of the clean film, evaporation of the falling film and the like. It may be desired to remove the aldehyde products from the crude reaction mixture as they are formed through the use of entrapment agents as described in Patent Application of the Published Patent Cooperation Treaty Number WO 88/08835. One method for separating the aldehyde mixtures from the other components of the crude reaction mixtures is by membrane separation. This membrane separation can be achieved as noted in U.S. Patent No. 5,430,194 and Copending US Patent Application Serial No. 08 / 430,790, filed May 5, 1995, both incorporated herein by reference. The subsequent hydrogenation of the aldehyde mixtures can be carried out without the need to separate the aldehydes from the other components of the crude reaction mixtures. As indicated above, upon conclusion of (or during) the process of this invention, the desired pentenales can be recovered from the reaction mixtures used in the process of this invention. For example, the recovery techniques disclosed in U.S. Patent Nos. 4,148,830 and 4,247,486 can be used. For example, in a continuous liquid catalyst recycling process, the portion of the mixture of - liquid reaction (containing the pentenal product, catalyst, etc.) removed from the reactor can be passed to a vaporizer / separator where the desired aldehyde product can be separated through distillation, in one or more stages, under normal pressure reduced or elevated liquid reaction solution, condensed and collected in a receiver of the product and further purified if desired. The remaining non-volatilized catalyst containing the liquid reaction mixture can then be recycled back to the reactor as can, if desired, any of the other volatile materials e.g. unreacted olefin or alkadienes, together with any hydrogen and carbon monoxide dissolved in the liquid reaction after separation thereof from the condensed pentenal product e.g. by distillation in any conventional manner. It is generally desirable to employ an organophosphorus coordinating group whose molecular weight exceeds that of the higher boiling point aldehyde oligomer byproduct corresponding to the pentenales or hydroxyhexanals that are produced in the hydroformylation process. Another appropriate recovery technique is solvent extraction or crystallization. It is generally preferred to separate the desired pentenales or hydroxyhexanals from the reaction mixture containing the catalyst under reduced pressure and at low temperatures, in order to avoid possible degradation of the organosphosphorus coordinating group and the reaction products. When an alpha-mono-olefin reagent is also employed, the aldehyde derivative thereof can also be separated by the aforementioned methods. More particularly, the distillation and separation of the desired aldehyde product from the solution of the product containing the complex metal catalyst-coordinating group can be carried out at any desired temperature. Generally, it is recommended that this distillation be carried out at relatively low temperatures such as below 150 ° C and most preferably at a temperature within the range of about 50 ° C to about 130 ° C. It is also generally recommended that this distillation of the aldehyde be carried out under reduced pressure e.g. a total gas pressure that is considerably lower than the total gas pressure used during hydroformylation, when aldehydes of low boiling temperature are involved (e.g., 5 and 6 carbon atoms) or vacuum when high boiling temperature aldehydes are involved (e.g., 7 carbon atoms or more). For example, a common practice is to subject the average liquid reaction product removed from the hydroformylation reactor to a reduction in pressure in order to volatilize a considerable portion of the unreacted gases dissolved in the liquid medium which now contains a gas concentration. of synthesis much lower than that which was present in the hydroformylation reaction medium to the distillation zone, eg the vaporizer / separator, wherein the desired aldehyde product is distilled. In general, distillation pressures ranging from vacuum pressures to a total gas pressure of approximately 3.52 kilograms per square centimeter gauge should be sufficient for most purposes. Particularly, when carrying out the process of this invention in a continuous liquid recycling mode employing an organophosphite coordinating group, undesirable acidic byproducts (eg hydroxyalkylphosphonic acid) may result due to the reaction of the organophosphite coordinating group and the aldehydes through the course of the process. The formation of these by-products undesirably decreases the concentration of the coordinating group. These acids are frequently insoluble in the reaction mixture and this insolubility can lead to precipitation of an undesirable gelatinous byproduct and can also promote the autocatalytic formation of the additional acidic by-products. The coordinating groups of - - organopoliphosphite used in the process of this invention have good stability against the formation of these acids. However, if this problem occurs, the stream of the liquid reaction effluent from a continuous liquid recycling process can be passed before (or preferably after) the separation of the desired hydrogenated hydrocarbon product from it through any suitable weakly basic anion exchange resin such as a bed of amine resin Amberlyst (R), eg Amberlyst (R) A-21 and the like, to remove some or all of the undesirable acidic byproducts prior to their re-incorporation into the hydroformylation reactor. If desired, more than one base anion exchange resin bed e.g. a series of these beds, and any of these beds can be easily removed and / or replaced as required or as desired. Alternatively, if desired, any part or all of the recycle stream of the acid-contaminated catalyst can be periodically removed from the continuous recycling operation, and the contaminated liquid removed in this manner is treated in the same manner as stated above for eliminate or reduce the amount of the acidic by-product before reusing the liquid containing the catalyst, in the hydroformylation process. Also, any other suitable method for removing these acidic by-products from the hydroformylation process of this invention can be employed, if desired such as by extraction of the acid with a weak base (e.g., sodium bicarbonate). The processes useful in this invention may involve improving the stability of the. catalyst of any organic dissolved organophosphite-rhodium complex, the hydroformylation process of liquid recycling aimed at producing aldehydes of the olefinic unsaturated compounds that may undergo deactivation of the catalyst due to the recovery of the aldehyde product by separation or evaporation from the product solution of reaction containing the organic solubilized rhodium-organopoliphosphite complex catalyst and the aldehyde product, the improvement carried out the vaporization-separation in the presence of a heterocyclic nitrogen compound. See, for example, Copending US Patent Application Serial No. 08 / 756,789, filed on November 26, 1996, the disclosure of which is incorporated herein by reference. The processes useful in this invention may involve improving the hydrolytic stability of the organosphosphite coordinating group and hence the catalyst stability of any hydroformylation process catalyzed by the rhodium complex-organic solubilized organophosphite coordinating group, directed to produce aldehydes of the olefinic unsaturated compounds, the improvement comprising treating at least a portion of a solution of the complex catalyst of solubilized organophosphite-rhodium-coordinating group which is derived from the process and which also contains acidic phosphorus compounds formed during the hydroformylation process, with an aqueous stabilizing solution in order to neutralize and remove at least a certain amount of the acidic phosphorus compounds from the catalyst solution, and then return the solution of the treated catalyst to the hydroformylation reactor. See, for example, Copending US Patent Applications Serial Nos. 08 / 756,501 and 08 / 753,505, both filed on November 26, 1996, the disclosures of which are incorporated herein by reference. In one embodiment of this invention, deactivation of the complex metal-organopolysosphorus coordinating group catalysts caused by an inhibiting or contaminating organomonophosphorus compound can be reversed or at least minimized by carrying out the hydroformylation processes in a reaction region wherein the hydroformylation reaction rate is of the negative or reverse order in carbon monoxide and optionally in one or more of the following conditions: at a temperature such that the temperature difference between the fluid temperature of the reaction product and the temperature of the inlet refrigerant is sufficient to prevent and / or decrease the cycling of the partial pressure of carbon monoxide, the partial pressure of hydrogen, the total reaction pressure, the hydroformylation reaction rate and / or the temperature during the hydroformylation process; at a conversion of carbon monoxide sufficient to prevent and / or reduce the cycling of the partial pressure of the carbon monoxide, the partial pressure of the hydrogen, the total reaction pressure, the hydroformylation reaction rate and / or the temperature during the hydroformylation process; at a hydrogen conversion sufficient to prevent and / or reduce the cycling of the carbon monoxide partial pressure, the hydrogen partial pressure, the total reaction pressure, the hydroformylation reaction rate and / or the temperature during that process. hydroformylation; and a conversion of the unsaturated olefinic compound sufficient to prevent and / or reduce the cycling of the partial pressure of the carbon monoxide, the partial pressure of hydrogen, the total reaction pressure, the hydroformylation reaction rate and / or the temperature during that hydroformylation process. See, for example, Copending US Patent Application Serial No. 08 / 756,499, filed on November 26, the disclosure of which is incorporated herein by reference.

STEPS OR HYDROGENATION STAGES Hydrogenation processes may involve converting one or more substituted or unsubstituted pentanels into one or more substituted or unsubstituted penten-1-ols. Generally, the hydrogenation step or step comprises reacting one or more substituted or unsubstituted pentenales with hydrogen in the presence of a catalyst, in order to produce one or more substituted or unsubstituted penta-1-oles. Illustrative of the appropriate hydrogenation processes are described for example in U.S. Patent Nos. 5,004,845, 5,003,110, 4,762,817 and 4,876,402, the teachings of which are incorporated herein by reference. As used herein, the term "hydrogenation" is intended to include, but is not limited to all permissible hydrogenation processes including those involved with reductive hydroformylation and will include but not be limited to converting one or more of the pentenales substituted or not substituted in one or more of the substituted or unsubstituted penten-1-oles. The pentenales useful in the hydrogenation process are known materials and can be prepared by the hydroformylation step described above or by a conventional method. Reaction mixtures comprising pentenales may be useful herein. The amount of pentenales compounded in the hydrogenation step is not narrowly critical and can be any amount sufficient to produce penten-1-ols, preferably at large selectivities. The reactants and the reaction conditions for the hydrogenation reaction step are known in the art. The specific hydrogenation reaction conditions are not narrowly critical and can be any of the effective hydrogenation conditions sufficient to produce one or more penten-1-ols. The reactors can be stirred tanks, tubular reactors and the like. The exact reaction conditions will be regulated by the best compromise between achieving high catalyst selectivity, activity, duration and ease of operation as well as the intrinsic reactivity of the starting materials in question and the stability of the starting materials, and the product of desired reaction to the reaction conditions. The recovery and purification can be by any appropriate means and should include distillation, phase separation, extraction, absorption, membrane crystallization, formation of the derivative and the like. The specific hydrogenation reaction conditions are not narrowly critical and can be any of the effective hydrogenation processes sufficient to produce one or more penten-1-ols. The combination of relatively low temperatures and low hydrogen pressures, as will be described below, can provide good reaction rates and high product selectivities. The hydrogenation reaction can continue in the presence of water without considerable degradation of the hydrogenation catalyst. The hydrogenation reaction can be carried out at a temperature of about 0 ° C to 180 ° C, for a period of about 1 hour or less to about 12 hours or more with the longer time being used at a lower temperature, preferably of about 25 ° C to about 140 ° C for about 1 hour or less, up to about 8 hours or more, and especially preferably at a temperature of about 50 ° C to 125 ° C for 1 hour or less to about 3 hours or more .

The hydrogenation reaction can be carried out through a wide range of hydrogen pressures ranging from about 3.52 kilograms per square centimeter gauge to about 730 kilograms per square centimeter gauge, preferably from about 14.06 kilograms per square centimeter gauge to about 105.45 kilograms per square centimeter gauge. It is especially preferred to carry out the hydrogenation reaction at hydrogen pressures of about 35.15 kilograms per square centimeter gauge to about 70.35 kilograms per square centimeter gauge. The preferred reaction is carried out in the liquid or vapor states or mixtures thereof, more preferably, in the liquid state. The transfer hydrogenation can be used to hydrogenate an aldehyde in an alcohol. In this process, the hydrogen required for the reduction of the aldehyde is obtained by dehydrogenation of an alcohol in an aldehyde or ketone. The transfer hydrogenation can be catalyzed by a variety of catalysts, both homogeneous and heterogeneous. For example, a common catalyst is an aluminum isopropoxide and a common alcohol is isopropanol. This system has the advantage that the ketone, resulting acetone is volatile and can be easily removed from the reaction system by vaporization. Since hydrogenation transfer is usually a limited process in equilibrium, the removal of the volatile product can be used to boost the reaction to completion. The ketone produced in this process can be hydrogenated in a separate step and recycled to the transfer hydrogenation reaction if desired. Other suitable catalysts for the transfer hydrogenation reaction include those known heterogeneous hydrogenation and dehydrogenation catalysts which are described below. Useful homogeneous catalysts include, for example, aluminum alkoxides and halides, zirconium, ruthenium and rhodium. The hydrogenation reaction can be carried out known hydrogenation catalysts in conventional amounts. Illustrative of suitable hydrogenation catalysts include, for example, Raney-type compounds such as Raney nickel and Raney nickel and modified; nickel promoted by molybdenum, nickel promoted by chromium, nickel promoted by cobalt, platinum, palladium, iron, cobalt molybdate in alumina; copper chromite; copper chromite promoted by barium; tin-copper coupling; zinc-copper coupling; aluminum-cobalt; aluminum-copper; aluminum-nickel; platinum; nickel; cobalt; ruthenium; rhodium; iridium; palladium; Rhenium copper; magnesium yttrium; lanthanide metals such as lanthanum and cerium; platinum / zinc / iron; platinum / cobalt; Cobalt of Raney; osmium and similar. The preferred catalysts are nickel, platinum, cobalt, rhenium and palladium. The hydroformylation and hydrogenation reaction conditions may be the same or different and the hydroformylation and hydrogenation catalysts may be the same or different. Suitable catalysts useful in both hydroformylation and hydrogenation reactions include, for example, rhodium free of coordinating group, rhodium promoted by phosphine, rhodium promoted by amine, cobalt, cobalt promoted by phosphine, ruthenium and palladium catalysts promoted by phosphine. The mixtures of the hydrogenation catalysts and the hydroformylation catalysts described above can be used, if desired. As indicated above, the hydrogenation catalyst may be homogeneous or heterogeneous. The amount of catalyst used in the hydrogenation reaction depends on the specific catalyst employed and may vary from about 0.01 weight percent or less to about 10 weight percent or more of the total weight of the starting materials. The illustrative pente-1-ol, substituted and unsubstituted intermediates that can be prepared by the processes of this invention include one or more of the following: cis-2-penten-1-ol, trans-2-penten-1-ol , cis-3-penten-1-ol, trans-3-penten-ol and / or 4-penten-1-ol, including mixtures comprising one or more of the aforementioned penten-1-ols. Illustrative of the appropriate substituted and unsubstituted penten-1-oles (including those derived from penten-1-ols) include those substituted and unsubstituted permissible penten-1-ols which are described in Kirk-Othmer, Encyclopedia of Chemical Technology, Fourth Edition, 1996, the relevant portions of which are incorporated herein by reference. As indicated above, the substituted and unsubstituted penten-1-oles produced by the hydrogenation step of this invention can be separated by conventional techniques, such as distillation, extraction, precipitation, crystallization, membrane separation, phase separation or other means appropriate. For example, a crude reaction product may be subjected to distillation-separation at atmospheric or reduced pressure through a packed distillation column. Reactive distillation can be useful to carry out the hydrogenation reaction step. A one-step process involving the reductive hydroformylation of one or more of the substituted or unsubstituted alkadienes to produce one or more substituted or unsubstituted 6-hydrohexanals is disclosed in U.S. Patent Application Serial Number (D) 17488-1), filed on the same date as the present one, the disclosure of which is incorporated herein by reference.Another process involving the production of one or more hydroxyaldehydes substituted or unsubstituted by hydrocarbylation / hydroformylation is given to In the North American Patent Application Serial Number (D-17779), filed on the same date as the present one, the disclosure of which is incorporated herein by reference.A modality of this invention relates to a process for producing one or more substituted or unsubstituted 6-hydroxyhexanals comprising: (a) subjecting one or more of the substituted or unsubstituted alkadienes vg b utadiene, to reductive hydroformylation in the presence of a reductive hydroformylation catalyst, e.g. a complex metal catalyst-organophosphorus coordinating group for producing one or more substituted or unsubstituted unsaturated alcohols comprising 3-penten-1-ols, 4-penten-1-ol and / or 2-penten-1-ols; (b) optionally separating the 3-penten-l-oles, 4-penten-l-ol and / or 2-penten-l-oles from the reductive hydroformylation catalyst; and (c) subjecting one or more of the substituted or unsubstituted unsaturated alcohols comprising 3-penten-l-oles, 4-penten-ol and / or 2-penten-oles by hydroformylation, in the presence of a hydroformylation catalyst, vg a complex catalyst of metal-coordinating organosphosphorus group, to produce one or more substituted or unsubstituted 6-hydroxyhexanals. The reaction conditions in steps (a) and (c) may be the same or different, and the reductive hydroformylation catalyst in step (a) and the hydroformylation catalyst in step (c) may be the same or different. Still another embodiment of this invention relates to a process for producing one or more substituted or unsubstituted 6-hydroxyhexanals comprising: (a) subjecting one or more of the substituted or unsubstituted alkadienes, e.g. butadiene to reductive hydroformylation in the presence of a reductive hydroformylation catalyst e.g. a complex metal catalyst-organophosphorus coordinating group, to produce one or more of the substituted or unsubstituted unsaturated alcohols comprising 3-penten-1-ols, 4-penten-1-ol and / or 2-penten-1 oles; - - (b) optionally separating the penten-1-oles, 4-penten-1-ol and / or 2-penten-1-oles from the reductive hydroformylation catalyst; (c) optionally submitting the 2-penten-l-oles and / or 3-penten-l-oles and isomerization in the presence of a heterogeneous or homogeneous olefin isomerization catalyst in order to partially or completely isomerize the 2-penten-l -ols and / or 3-penten-l-oles in 3-penten-l-oles and / or 4-penten-l-ol; and (d) subjecting one or more of the substituted or unsubstituted unsaturated alcohols comprising 2-penten-1-ols, 3-penten-1-ols and / or 4-penten-1-ol to hydroformylation in the presence of a catalyst hydroformylation vg a complex metal catalyst-organophosphorus coordinating group to produce one or more substituted or unsubstituted 6-hydroxyhexanals. The reaction conditions in steps (a) and (d) may be the same or different, and the reductive hydroformylation catalyst in step (a) and the hydroformylation catalyst in step (d) may be the same or different. The olefin isomerization catalyst in step (c) can be any of a variety of homogeneous or heterogeneous transition metal-based catalysts (particularly Ni, Rh, Pd, Pt, Co, Ru or Ir), - or it can be a heterogeneous or homogeneous acid catalyst (particularly any acidic zeolite, polymeric resin, or a source of H +, any of which can be modified with one or more of the transition metals). These olefin isomerization catalysts are known in the art and isomerization can be carried out by conventional methods known in the art. As used herein, the term "isomerization" is intended to include, but not be limited to, all permissible isomerization processes that involve converting one or more of the 2-penten-1-oles and / or 3-penten-1- substituted or unsubstituted oles in one or more of the substituted or unsubstituted 4-penten-1-oles. When the processes of this invention are carried out in two stages (i.e., producing first 2-penten-1-ols, 3-penten-1-ols and / or 4-penten-ol under a set in conditions and then reducing a 6-hydroxyhexanal of the 2-penten-l-oles, 3-penten-l-oles and / or 4-penten-l-ol under another set of conditions), it is preferred to carry out the first stage at a temperature of 75 ° C at 110 ° C, and at a total pressure of 17.58 kilograms per square centimeter at 70.30 kilograms per square centimeter and carry out the second stage at a temperature of 60 ° C to 120 ° C and a pressure of .352 kilogram per square centimeter to 35.15 kilograms per square centimeter. Equal or different catalysts can be used in the first and second stages. The other conditions may be the same or different in both stages. The processes of this invention can be operated through a wide range of reaction regimes (m / L / H = product moles / liter of the reaction solution / hour). Typically, the reaction regimes are at least 0.01 m / L / H or higher, preferably at least 0.1 m / L / H or higher, and most preferably at least 0.5 m / L / H or higher. Higher reaction rates are usually preferred from an economic point of view, e.g. a smaller reactor size, etc. Substituted and unsubstituted hydroxyaldehyde products (e.g., 6-hydroxyhexanals) have a broad scale of utilities that are well known in the art, e.g. they are useful as intermediates in the production of epsilon caprolactone, epsilon caprolactam, adipic acid and 1,6-hexanediol. The processes of this invention can be carried out using, for example, a fixed bed reactor, a fluid bed reactor, a continuous stirred tank reactor (CSTR) or a slurry reactor. The optimal size and configuration of the catalysts 14 - it will depend on the type of reactor used. Usually, for fluid bed reactors, a small spherical catalyst particle is preferred for easy fluidization. With fixed bed reactors, larger catalyst particles are preferred so that the back pressure inside the reactor remains reasonably low. The processes of this invention can be carried out intermittently or continuously with recycling of the unconsumed starting materials if required. The reaction can be carried out in a single reaction zone or in a plurality of reaction zones, in series or in parallel or it can be carried out intermittently or continuously in an elongated tubular zone or a series of these zones. The construction materials used must be inert to the starting materials during the reaction, and the manufacture of the equipment must be able to withstand the temperatures and pressures of the reaction. The means for introducing and / or adjusting the amount of starting materials or ingredients introduced intermittently or continuously into the reaction zone during the course of the reaction can be conveniently used in processes especially to maintain the desired molar ratio of the starting materials . The reaction steps can be carried out by incremental addition of one of the starting materials to the other.

- Likewise, the reaction steps can be combined by the joint addition of the starting materials. When the complete conversion is not desired or can not be obtained, the starting materials can be separated from the product, for example, by distillation, and the starting materials then recycled back to the reaction zone. The processes can be carried out either in reaction equipment lined with glass, stainless steel or similar type. The reaction zone may be equipped with one or more internal and / or external heat exchanger (s) in order to control undue temperature fluctuations, or to prevent any of the possible "escape" reaction temperatures. The processes of this invention may be carried out in one or more steps or steps. The exact number of steps or stages of reaction will be regulated by the best compromise between achieving high catalyst selectivity, activity, duration and ease of operability as well as the iontrinsectivity of the starting materials in question, and the stability of the starting materials and the desired reaction product at the reaction conditions. In one embodiment, the processes useful in this invention can be carried out in a multi-stage reactor such as that described for example, in the co-pending US Patent Application Number of - Series 08 / 757,743, filed on November 26, 1996, the exhibition of which is incorporated herein by reference. Multistage reactors can be designed with internal physical barriers that create more than one theoretical reactive stage per vessel. In fact, it's like having a number of reactors inside a single vessel of the continuous stirred tank reactor. Multiple reactive steps within a single vessel is an effective cost way to use the reactor vessel volume. Significantly reduce the number of containers that would otherwise be required to achieve the same results. A smaller number of containers reduces the total capital required and maintenance costs with separate containers and agitators. The substituted and unsubstituted hydroxyaldehydes e.g. the 6-hydroxyhexanals, produced by the processes of this invention can further undergo reaction (s) to provide the desired derivatives thereof. These permissible derivatization reactions can be carried out in accordance with conventional procedures known in the art. Exemplary derivatization reactions include, for example, hydrogenation, esterification, etherification, amination, alkylation, dehydrogenation, reduction, acylation, condensation, carboxylation, - carbonylation, oxidation, cyclization, silylation and the like, including permissible combinations thereof. Preferred derivatization reactions and 6-hydroxyhexanal derivatives include, for example, reductive amination to provide hexamethylene diamine, oxidation to provide adipic acid, oxidation and cyclization to provide epsilon caprolactone, oxidation, cyclization and amination to provide epsilon caprolactone and hydrogenation or reduction to provide 1,6-hexanediols. This invention is not intended to be limited in any way by the patented bypass reactions and the permissible derivatives of substituted and unsubstituted 6-hydroxyhexanals. For the purposes of this invention, the term "hydrocarbon" is intended to include all permissible compounds having at least one hydrogen and one carbon atom. These allowable compounds may also have one or more heteroatoms. In a broad aspect, the permissible hydrocarbons include acyclic (with or without heteroatoms) and cyclic, branched and unbranched, carbocyclic and aromatic and non-aromatic heterocycles which can be substituted or unsubstituted. As used in this, the term "substituted" is intended to include all permissible substituents of the organic compounds unless otherwise indicated. In a broad aspect, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic substituents of the organic compounds. Exemplary substituents include for example alkyl, alkyloxy, aryl, aryloxy, hydroxy, hydroxyalkyl, amino, aminoalkyl, halogen and the like wherein the number of carbon atoms can vary from 1 to about 20 or more, preferably from 1 to about 12. The permissible substituents may be one or more of the same or different appropriate organic compounds. This invention is not intended to be limited in any way by the permissible substituents of the organic compounds. For the purposes of this invention, the chemical elements are identified according to the Periodic Table of the Elements, reproduced in "Basic Inorganic Chemistry" by A. Albert Cotton, Geoffrey Wilkinson and Paul L. Gaus, published by John Wiley and Sons Ine , Third Edition, 1995. Certain of the following examples are provided to further illustrate this invention.

Example 1 A catalyst solution consisting of 0.019 grams of rhodium dicarbonyl acetylacetonate (300 parts per million rhodium), 0.31 gram of Coordinating Group F identified above (rhodium coordinator group ratio of 5: 1) and 25 milliliters of tetrahydrofuran were charged to a reactor with a capacity of 100 milliliters. Butadiene (1.5 milliliters) was charged to the reactor as the liquid under pressure. The reaction was heated to 95 ° C and pressurized to 17.58 kilograms per square centimeter with 4: 1 carbon monoxide: hydrogen. After one hour, the solution was analyzed by gas chromatography to determine the composition of the product. The butadiene had converted to 37 weight percent. The products consisted of 75 weight percent of 3-pentenales, 2 weight percent of 2-pentas, 6 weight percent of 4-pentenal, 2 weight percent of valeraldehyde and 5 weight percent of adipaldehyde.

Example 2 A catalyst solution consisting of 0.019 gram of rhodium dicarbonyl acetylacetonate (300 parts per million rhodium), 0.31 gram of Coordinating Group F identified above (coordinator group to rhodium ratio of 5: 1) and 25 milliliters of diglima were loaded into a reactor reactor with a capacity of 100 milliliters. Butadiene (7 milliliters) was charged to the reactor as a liquid under pressure. The reaction was heated to 95 ° C and pressurized to 70.30 kilograms per square centimeter gauge with 4: 1 carbon monoxide: hydrogen. The solution was analyzed by chromatography of. gas at intervals to determine the composition of the product. The results are shown in Table A below.

Table A Time of 3-pentenales 4-pentenal 2-pentenales Reaction (% in weight) (% in weight) (% in weight) (minutes) 75 11 1 30 74 8 3 60 68 3 5 90 55 7 120 36 '6 Table A (continued) Time of Valeraldehyde Dialdehyde Adipaldehyde Reaction (% by weight) branched (% by weight) (minutes) (% by weight) 2 8 30 1 3 10 60 2 5 15 90 9 8 19 120 24 11 22 Example 3 A catalyst solution consisting of 0.135 gram of rhodium dicarbonyl acetylacetonate (300 parts per million rhodium), 3 grams of Coordinating Group F identified above (rhodium coordinator group ratio of 3.6: 1) and 150 milliliters of tetrahydrofuran were loaded in a Parr autocalve of 300 milliliter capacity. Butadiene (100 milliliters) was charged as a liquid under pressure. The reaction mixture was heated to 95 ° C and pressurized to 96.24 kilograms per square centimeter with 4: 1 carbon monoxide: hydrogen. The reaction was periodically repressed at 64.68 kilograms per square centimeter - with synchronization gas (1: 1 carbon monoxide: hydrogen) to compensate for that absorbed by the solution. After 4 hours, the mixture was analyzed by gas chromatography to determine the composition of the product. The products consisted of 80 percent by weight of pentenales, 11 percent by weight of valeraldehyde and 4 percent by weight of adipaldehyde.

Example 4 A catalyst solution consisting of 0.012 gram of rhodium dicarbonyl acetylacetonate (200 parts per million rhodium), 0.47 gram of Coordinating Group E identified above (rhodium coordinator group ratio, 12: 1) and 15 milliliters of Tetrahydrofuran were loaded in a Parr reactor with a capacity of 100 milliliters. Butadiene (2 milliliters) was charged to the reactor as a liquid under pressure. The reaction mixture was heated to 95 ° C and pressurized to 35.15 kilograms per square centimeter gauge with 1: 1 carbon monoxide: hydrogen. The reaction rate was determined by monitoring the synchronization gas consumption regime (1: 1 carbon monoxide: hydrogen). The reaction rate was found to be 0.4 mol / liter-hour. After 2 hours of reaction, the solution is- analyzed by gas chromatography to determine the composition of the product. The butadiene became 95 weight percent. The products consisted of 75 percent by weight of 3-pentenales, 3 percent by weight of 4-pentenal, 5 percent by weight of 2-pentenales, 7 percent by weight of valeraldehyde, 1 percent by weight of branched dialdehyde and 9 weight percent adipaldehyde.

Example 5 A catalyst solution consisting of 0.012 gram of rhodium dicarbonyl acetylacetonate (200 parts per million rhodium), 0.47 gram of Coordinating Group D identified above (ratio of coordinator group to rhodium equal 14: 1) and 15 milliliters of Tetrahydrofuran were loaded in a Parr reactor with a capacity of 100 milliliters. The butadiene (2 milliliters) was charged to the reactor as a liquid under pressure. The reaction mixture was heated to 95 ° C and pressurized to 35.15 kilograms per square centimeter gauge with 1: 1 carbon monoxide: hydrogen. "The reaction rate was determined by monitoring the synchronization gas consumption regime (1: 1 carbon monoxide: hydrogen) .The reaction rate was found to be 1.2 moles per - - liter-hour. After 2 hours of reaction, the solution was analyzed by gas chromatography to determine the composition of the product. The butadiene had become 68 weight percent. The products consisted of 70 percent by weight of 3-pentenales, 8 percent by weight of 4-pentenal, 8 percent by weight of 2-pentenales, 8 percent by weight of valeraldehyde, 1 percent by weight of branched dialdehyde and 5 weight percent adipaldehyde.

Example 6 A catalyst solution consisting of 0.19 gram of rhodium dicarbonyl acetylacetonate (300 parts per million rhodium), 0.42 gram of the Coordinating Group illustrated below (ratio of coordinator group to rhodium equal 6: 1), 2.29 grams of N-methylpyrrolidinone (as an internal standard) and 25 milliliters of tetrahydrofuran were loaded into a Parr reactor of 100 milliliter capacity. The butadiene (3 milliliters) was charged to the reactor as a liquid under pressure. The reaction mixture was heated to 95 ° C and pressurized to 35.15 kilograms per square centimeter gauge with 1: 1 carbon monoxide: hydrogen. After 2 hours of reaction, the solution was analyzed by gas chromatography to determine the composition of the product. The butadiene had become 33 weight percent. The products consisted of 87 percent by weight of 3-pentenales, 3 percent by weight of 2-pentenales, 4 percent by weight of 4-pentenales and 7 percent by weight of valeraldehyde.

Example 7 A catalyst solution consisting of 0.019 gram of rhodium dicarbonyl acetylacetonate (300 parts per million rhodium), 0.88 gram of the Coordinating Group illustrated below (coordinating group relationship to rhodium equal 10-15: 1), 2.19 grams of N-methylpyrrolidinone (as an internal standard) and 25 milliliters of tetrahydrofuran were loaded into a Parr reactor of 100 milliliter capacity. The butadiene (3 milliliters) was charged to the reactor as a liquid under pressure. The reaction was heated to 95 ° C and pressurized to 35.15 kilograms per square centimeter gauge with 1: 1 carbon monoxide: hydrogen. After 2 hours of reaction, the solution was analyzed by gas chromatography to determine the composition of the product. The butadiene had become 33 weight percent. The products consisted of 80 percent by weight of 3-pentenales, 8 percent by weight of 4-pentenal, 4 percent by weight of 2-pentenales and 8 percent by weight of valeraldehyde.

Example 8 A catalyst solution consisting of 0.019 gram of rhodium dicarbonyl acetylacetonate (300 parts per million rhodium), 0.09 gram of the Group Coordinator illustrated below (ratio of coordinator group to rhodium equal 1.5: 1) and 25 milliliters of tetrahydrofuran, were loaded into a Parr reactor with a capacity of 100 milliliters. The butadiene (1 milliliter) was charged to the reactor as a liquid under pressure. The reaction mixture was heated to 95 ° C and pressurized to 35.15 kilograms per square centimeter gauge with 4: 1 carbon monoxide: hydrogen. After 1 hour the solution was analyzed by gas chromatography to determine the composition of the product. Butadiene had become 51 percent by weight. The products consisted of 79 weight percent of 3-pentenales, 12 weight percent of 4-pentenal and 5 percent of butenes.

Example 9 in penteal weight, 27 weight percent valeraldehyde and - - A catalyst solution consisting of 0.016 gram of rhodium dicarbonyl acetylacetonate and 2.089 grams of Coordinating Group F, identified above (ratio of rhodium-coordinating group equal 3.6: 1) and 160 milliliters of tetraglim were loaded into a Parr autoclave with a capacity of 300 milliliters. Butadiene (35 milliliters) was charged as a liquid under pressure. The reaction was heated to 95 ° C and pressurized to 63.27 kilograms per square centimeter with 4: 1 carbon monoxide: hydrogen. The reaction mixture was periodically re-pressed to 63.27 kilograms per square centimeter with synchronization gas (1: 1 carbon monoxide: hydrogen) to compensate for that amount absorbed by the solution. After 2.5 hours, the reactor was cooled and reloaded with 35 milliliters of butadiene and the reaction was repeated. A total of 3 butadiene charges of 35 milliliters were reacted in order to provide sufficient material for the distillation. The mixture was analyzed by gas chromatography to determine the composition of the product. The hydroformylation products consisted of 53 percent by weight of pentene, 27 percent by weight of valeraldehyde and 12 percent by weight of adipaldehyde. The mixture produced was distilled at 260 milliliters of mercury through an Oldershaw column of 25 trays. The best products of - distillation of the crudes collected at a tray temperature at 225 ° C consisted of 77 weight percent pentenales.

Example 10 A catalyst solution consisting of 0.019 gram of rhodium dicarbonyl acetylacetonate (300 parts per million rhodium), 0.18 gram of the Triphenylphosphine Coordinating Group (ratio of rhodium coordinating group equal 10: 1) and 25 milliliters of tetrahydrofuran was charged to a Parr reactor with a capacity of 100 milliliters. Butadiene (1 milliliter) was charged to the reactor as a liquid under pressure. The reaction was heated to 95 ° C and pressurized to 35.15 kilograms per square centimeter gauge with 1: 1 carbon monoxide: hydrogen. After 1 hour the solution was analyzed by gas chromatography to determine the composition of the product. The butadling had become approximately 60 weight percent. The products consisted of 82 weight percent of 3-pentenales, 9 weight percent of 4-pentenal, 5 weight percent of valeraldehyde and 4 weight percent of butenes. After two hours of reaction time, the products consisted of 69 weight percent of 3- pentenales, 3 weight percent of 4-pentenal, 12 weight percent of valeraldehyde, 5 weight percent of adipaldehyde, 4 weight percent of methylglutaraldehyde, 3 weight percent of butenes and 2 weight percent of 2-methylbutyraldehyde.

Example 11 A catalyst solution consisting of 0.032 gram of rhodium dicarbonyl acetylacetonate (500 parts per million rhodium), 0.12 gram of a tris (2-cyanoethyl) phosphine coordinating group (rhodium coordinating group ratio equal 5: 1) and 25 milliliters of tetrahydrofuran was charged to a Parr reactor of 100 milliliter capacity. Butadiene (3 milliliters) was charged to the reactor as a liquid under pressure. The reaction mixture was heated to 110 ° C and pressurized to 70.30 kilograms per square centimeter gauge with 1: 1 carbon monoxide: hydrogen. After 2 hours of reaction the solution was analyzed by gas chromatography to determine the composition of the product. Butadling became approximately 68 weight percent. The products consisted of 54 percent by weight of 3-pentenales, 5 percent by weight of 4-pentenal, 3 percent by weight of 2-pentenales, 27 percent by weight of valeraldehyde and 7 percent by weight of 2 -methylbutyraldehyde.

Example 12 A catalyst solution consisting of 0.019 gram of rhodium dicarbonyl acetylacetonate (300 parts per million rhodium), 0.20 gram of the diphenyl (o-methoxyphenyl) phosphine coordinating group (rhodium coordinating group ratio of 10: 1) and 25 milliliters of tetrahydrofuran were loaded into a Parr reactor of 100 milliliter capacity. The butadiene (3 milliliters) was charged to the reactor as a liquid under pressure. The reaction mixture was heated to 95 ° C and pressurized to 35.20 kilograms per square centimeter gauge with 1: 1 carbon monoxide: hydrogen. After 1 hour the solution was analyzed by gas chromatography to determine the composition of the product. The butadling had become approximately 50 weight percent. The products consisted of 74 percent by weight of 3-pentenales, 10 percent by weight of 4-pentanal, 6 percent by weight of valeraldehyde and 8 percent by weight of butenes.

Example 13 - A catalyst solution consisting of 0.019 gram of rhodium dicarbonyl acetylacetonate (300 parts per million rhodium), 0.24 gram of a bis (diphenylphosphino) propane coordinating group (rhodium coordinating group ratio of 8: 1) and 25 milliliters of tetrahydrofuran were loaded in a Parr reactor with a capacity of 100 milliliters. The butadiene (3 milliliters) was charged to the reactor as a liquid under pressure. The reaction mixture was heated to 95 ° C and pressurized to 35.15 kilograms per square centimeter gauge with 1: 1 carbon monoxide: hydrogen. After 2 hours of reaction the solution was analyzed by gas chromatography to determine the composition of the product. Butadiendo had become 50 percent by weight. The products consisted of only aldehydes of five carbon atoms, without dialdehyde present.

Example 14 A catalyst solution consisting of 0.018 gram of rhodium dicarbonyl acetylacetonate (300 parts per million rhodium), 0.16 gram of the isopropyldiphenylphosphine coordinator group (rhodium coordinator group ratio of 5: 1) and 25 milliliters of tetrahydrofuran were charged to a Parr reactor - - capacity of 100 milliliters. Butadiene (1 milliliter) was charged to the reactor as a liquid under pressure. The reaction mixture was heated to 95 ° C and pressurized to 35.15 kilograms per square centimeter gauge with 1: 1 carbon monoxide: hydrogen. After 2 hours of the reaction, the solution was analyzed by gas chromatography to determine the composition of the product. The butadling had become about 46 weight percent. The products consisted of 79 percent by weight of 3-pentenales, 9 percent by weight of 4-pentenal, 5 percent by weight of valeraldehyde and 5 percent by weight of butenes.

Example 15 A catalyst solution consisting of 0.018 gram of rhodium dicarbonyl acetylacetonate (300 parts per million rhodium), 0.08 gram of the bis (diphenylphosphino) ferrocene coordinating group (rhodium coordinating group ratio of 2: 1) and 25 milliliters of Tetrahydrofuran were loaded in a Parr reactor with a capacity of 100 milliliters. Butadiene (1 milliliter) was charged to the reactor as a liquid under pressure. The reaction mixture was heated to 75 ° C and pressurized to 70.30 kilograms per square centimeter gauge with 10: 1 carbon monoxide hydrogen. After 2 hours of reaction, the solution was analyzed by gas chromatography to determine the composition of the product. Butadiendo had become approximately 54 percent. The products consisted of 74 percent by weight of 3-pentenales and 25 percent by weight of 4-pentenal.

Example 16 A catalyst solution consisting of 0.019 gram of rhodium dicarbonyl acetylacetonate (300 parts per million rhodium), 0.31 gram of Coordinating Group F (ratio of rhodium coordinating group of 5: 1) and 10 microliters of trimethylphosphine coordinating group ( rhodium coordinating group ratio of 2: 1) and 25 milliliters of toluene were loaded in a Parr reactor with a capacity of 100 milliliters. Butadiene (10 milliliters) was charged to the reactor as a liquid under pressure. The reaction mixture was heated to 110 ° C and pressurized to 70.30 kilograms per square centimeter gauge with 1: 1 carbon monoxide hydrogen. After 2 hours the solution was analyzed by gas chromatography to determine the composition of the product. Butadiendo had become 80 percent by weight. The products consisted of 53 percent by weight of 3-pentenales, 13 by - weight percent 2-pentene, 4 weight percent 4-pentenal, 8 weight percent valeraldehyde, 8 weight percent adipaldehyde and 7 weight percent butenes.

Example 17 A catalyst solution consisting of 0.019 gram of rhodium dicarbonyl acetylacetonate (300 parts per million rhodium), 0.12 gram of Coordinating Group F identified above (rhodium coordinator group ratio of 2: 1), 0.09 gram of the coordinating group of tris (p-tolyl) phosphine (ratio of coordinating group to rhodium of 4: 1) and 25 milliliters of tetrahydrofuran were loaded in a Parr reactor with a capacity of 100 milliliters. The butadiene (3 milliliters) was charged to the reactor as a liquid under pressure. The reaction mixture was heated to 95 ° C and pressurized to 35.15 kilograms per square centimeter gauge with 1: 1 carbon monoxide: hydrogen. After 2 hours the solution was analyzed by gas chromatography to determine the composition of the product. The butadiene had become 80 weight percent. The products consisted of 51 percent by weight of 3-pentenales, 5 by - - weight percent 2-pentenales, 26 weight percent valeraldehyde and 15 weight percent adipaldehyde.

Example '18 A catalyst solution consisting of 0.05 gram of (bicyclo [2.2.1] epta-2.5-diene) [1, 1 '-bis (diphenylphosphino) ferrocene] rhodium (I) perchlorate (250 parts per million rhodium) in 25 milliliters of tetrahydrofuran was charged in a Parr reactor with a capacity of 100 milliliters. The butadiene (3 milliliters) was charged to the reactor as a liquid under pressure. The reaction mixture was heated to 95 ° C and pressurized to 28.12 kilograms per square centimeter with 1: 1 carbon monoxide: hydrogen. After 1 hour of reaction the solution was analyzed by gas chromatography to determine the composition of the product. The butadling had become approximately 50 weight percent. The products consisted of 28 percent by weight of 3-pentenales, 36 percent by weight of 4-pentenal, 7 percent by weight of 2-pentenales, 8 percent by weight of valeraldehyde and 21 percent by weight of products of low molecular weight, possibly butenes.

- Example 19 - A catalyst solution consisting of 0.05 gram of (bicyclo [2.2.1] hepta-2.5-diene) [1,1 '-bis (diphenylphosphino) ferrocene] rhodium (I) perchlorate (250 parts per million rhodium) in 25 milliliters of tetrahydrofuran was loaded in a Parr reactor with a capacity of 100 milliliters. The butadiene (3 milliliters) was charged to the reactor as a liquid under pressure. The reaction mixture was heated to 95 ° C and pressurized to 35.15 kilograms per square centimeter gauge with 10: 1 carbon monoxide: hydrogen. After 1 hour of reaction the solution was analyzed by gas chromatography to determine the composition of the product. The butadiene had become approximately 25 weight percent. The products consisted of 17 weight percent of 3-pentenales, 34 weight percent of 4-pentenal and 43 weight percent of low molecular weight products, possibly butenes.

Example 20 A catalyst solution consisting of 0.02 gram of bis (bicyclo [2.2.1] hepta-2.5-diene) rhodium (I) perchlorate / bis (diphenylphosphino) ferrocene (250 parts per million rhodium) and 0.03 gram of bis (diphenylphosphino) Ferrocene in 25 milliliters of tetrahydrofuran was loaded in - a Parr reactor with a capacity of 100 milliliters. Butadiene (3 milliliters) was charged to the reactor as a liquid under pressure. The reaction mixture was heated to 95 ° C and pressurized to 35.15 kilograms per square centimeter with 1: 1 carbon monoxide: hydrogen. After 30 minutes of reaction the solution was analyzed by gas chromatography to determine Xa composition of the product. Buffering conversion was not determined. The products consisted of 38 weight percent of 3-pentenales, 43 weight percent of 4-pentenal and 20 weight percent of low molecular weight products, possibly butenes.

Example 21 A catalyst solution consisting of 0.018 gram of rhodium dicarbonyl acetylacetonate (300 parts per million rhodium), 0.035 gram of a coordinating group of (4R, 5R) - (-) - O-isopropylidene-2,3-dihydroxy- 1, 4-bis (diphenylphosphino) butane (ratio of coordinating group to rhodium of 1: 1) and 25 milliliters of tetrahydrofuran was charged in a Parr reactor with a capacity of 100 milliliters. The butadiene (3 milliliters) was charged to the reactor as a liquid under pressure. The reaction was heated to 95 ° C and pressurized to 17.58 kilograms per square centimeter gauge with 4: 1 monoxide of - carbon: hydrogen. After 30 minutes of reaction the solution was analyzed by gas chromatography to determine the composition of the product. The products consisted of 57 percent by weight of 3-pentenales and 32 percent by weight of 4-pentenal. After two hours of reaction, the butadiene had become approximately 83 weight percent. The products consisted of 53 percent by weight of 3-pentenales, 8 percent by weight of 4-pentenal, 3 percent by weight of valeraldehyde, 6 percent by weight of branched dialdehyde and 22 percent by weight of adipaldehyde.

Example 22 A catalyst solution consisting of 0.018 gram of rhodium dicarbonyl acetylacetonate (300 parts per million rhodium), 0.035 gram of the coordinating group of (4R, 5R) - (-) - O-isopropylidene-2,3-dihydroxy-1 , 4-bis (diphenylphosphino) butane (ratio of coordinating group to rhodium of 10: 1) and 25 milliliters of tetrahydrofuran was loaded in a Parr reactor with a capacity of 100 milliliters. The butadiene (3 milliliters) was charged to the reactor as a liquid under pressure. The reaction mixture was heated to 95 ° C and pressurized to 35.15 kilograms per square centimeter gauge with 1: 1 carbon monoxide hydrogen. After 2 hours of reaction the solution was analyzed by gas chromatography to determine the composition of the product. The butadiene had become more than 90 weight percent. The products consisted of 41 percent by weight of 3-pentenales, 3 percent by weight of 2-pentenales, 8 percent by weight of valeraldehyde, 10 percent by weight of branched dialdehydes and 24 percent by weight of adipaldehyde.

Examples 23-41 In a stirred high-pressure reactor with a capacity of 100 milliliters, 0.25 millimole of rhodium dicarbonyl acetylacetonate (I), 0.9 millimole of trialkylphosphine, which is defined in Table B below, was charged with 3 milliliters of butadiene. milliliters of a solvent as defined in Table B, and 1 milliliter of diglyme, as an internal standard. The reactor was pressurized to from .352 to .703 kilogram per square centimeter of hydrogen / carbon monoxide in a ratio of 1/1 and heated to the desired temperature indicated in Table B. At the desired temperature, the reactor was pressurized. to the desired hydrogen / carbon monoxide ratio indicated in Table B, and the gas collected was monitored. After a decrease in pressure of 10 percent, the reactor was again pressurized to the initial value with hydrogen / carbon monoxide in a ratio of 1/1. Samples of the reaction mixture were sampled in small flasks cooled with dry ice through the sampling line at scheduled intervals and analyzed by gas chromatography. At the end of the 90 minute reaction period, the gases were discharged and the reaction mixture was drained. The details and additional results of the analyzes are shown in Table B.

Table B Ex. Solvent / P Temp.

No. (° C) 23 Ethanol Triethylphosphine 60 24 Ethanol Triethylphosphine 80 Ethanol Triethylphosphine 80 26 Ethanol Triethylphosphine 80 27 Octanol Trioctylphosphine 80 28 3-Pentene Trioctylphosphine 80 29 Hexanediol Trioctylphosphine 80 Pyrrole Trioctylphosphine 80 31 Ethanol Tributylphosphine 80 32 Phenol / THF Trioctylphosphine 80 33 t-Butanol Triethylphosphine 120 34 Ethanol Trimethylphosphine 120 Ethanol Diethyl-para-N, N-80 dimethylphenylphosphine 36 Ethanol / Acetonitrile Triethylphosphine 80 37 Ethanol / Tetraglima Triethylphosphine 80 38 Diphenylamine Trioctylphosphine 80 39 Acetamide Trioctylphosphine 80 40 Methylacetamide Trioctylphosphine 80 41 N-Methylformamide Trioctylphosphine 80 - - Table B (Continued) Ex. H2 / CO Conversion of Selectivity Rate (%) of No. (kg / cm2) Butadiene m / L / H 3 and 4 pentenoles (%) 23 21.09 / 21.09 27 0.2 92 24 21.09 / 21.09 90 1.6 87 25 35.15 / 35.15 87 1.3 91 26 5.24 / 5.24 75 0.3 71 27 42.18 / 14.06 98 1.9 88 28 42.18 / 14.06 89 nd 90 29 21.09 / 21.09 65 nd 93 30 42.18 / 14.06"90 1.4 88 31 21.09 / 21.09 55 1.0 70 32 42.18 / 14.06 84 2.0 55 33 17.58 / 17.58 99 nd 38 (15 min rxn, time) 34 17.58 / 17.58 97 nd 42 (2h rxn, time) 42.18 / 14.06 70 1.2 64 36 21.09 / 21.09 68 1.1 82 37 21.09 / 21.09 64 1.0 91 38 42.18 / 14.06 80 0.8"54 39 42.18 / 14.06 85 0.9 34 40 -42.18 / 14.06 73 0.8 59 41 42.18 / 14.06 33 0.1 19 - - Examples 42-48 In a stirred high-pressure reactor with a capacity of 100 milliliters, 0.25 millimole of rhodium of rhodium dicarbonyl acetylacetonate (I), 0.9 millimole of trialkylphosphine was charged as defined in Table C below., 3 milliliters of butadiene, 26 milliliters of ethanol and 1 milliliter of diglyme as the internal standard. The reactor was pressurized with .352 -.703 kilogram per square centimeter of hydrogen / carbon monoxide in a ratio of 1/1 and heated to 80 ° C. At the desired temperature, the reactor was pressurized to the desired ratio of hydrogen / carbon monoxide noted in Table C, and the collected gas was monitored. After a decrease in pressure of 10 percent, the reactor was again pressurized to the initial value with hydrogen / carbon monoxide in a ratio of 1/1. The samples of the reaction mixture were placed in small flasks cooled in dry ice through the sampling line at the programmed intervals and analyzed by gas chromatography. At the end of the 120 minute reaction period, the gases were discharged and the reaction mixture was drained. The details and additional results of the analyzes are shown in Table C.

- - Table C Ex, Phosphine H2 / CO Conver- Selective Regime No, (kg / cm2) sion of (m / L / h) dad () buta3 and 4 diene Pentenoles (%) 42 t-butyldiethyl 21.09 / 21.09 60 0.8 13 phosphine 43 t-butyldiethyl 56.24 / 14.06 69 1.1 19 phosphine 44 cyclohexyl- 21.09 / 21.09 76 0.7 75 diethyl phosphine 45 cyclohexyl- 56.24 / 14.06 82 1.4 80 diethyl phosphine 46 n-butyldiethyl- 21.09 / 21.09 77 1.1 82 phosphine 47 diethylphenyl 14.06 / 56.34 53 0.9 77 phosphine 48 ethyldiphenyl- 14.06 / 56.34 38 0.6 27 phosphine Example 49 A magnetically stirred autoclave with a capacity of 160 milliliters was purged with 1: 1 H2 / CO and charged with - a catalyst solution consisting of 0.1125 gram (0.44 millimole) rhodium dicarbonyl acetylacetonate (I), 0. 3515 grams (2.94 millimoles) of P (CH2CH2CH2OH) 3, and 44.1 grams of tetrahydrofuran. The autoclave was pressurized with 2.81 kilograms per square centimeter gauge of 1: 1 H2 / CO and heated to 80 ° C. 6 milliliters were charged (3.73 grams) of 1,3-butadiene with a regulated supply pump and the reactor was pressurized at 70.30 kilograms per square centimeter with 1: 1 H2 / CO. The reaction mixture was maintained at 80 ° C under a pressure of 70.30 kilograms per square centimeter of 1: 1 H2 / CO. The samples of the reaction mixture taken after 90 minutes and 170 minutes gave the results indicated in Table D below: Table D Temp. H2 / CO Conversion Selectivity regime (%) 2 (min. ¡(° C) (kg / cm of butadiene (m / L / H) 3 and 4-methylbenzenetrcycline) (I) 90 80 35.15 / 35.15 81 0.7 66 170 80 35.15 / 35.15 96 - 0. 4 - 72 Example 50 - A magnetically stirred autoclave with a capacity of 160 milliliters was purged with 1: 1 H2 / CO and charged with a catalyst solution consisting of 0.1126 gram (0.44 millimole) of rhodium dicarbonyl acetylacetonate (I), 0.6120 gram (1.69 millimoles) ) of P (CH2CH2CH2OH) 3 and 39.9 grams of ethanol. The autoclave was pressurized with 2.81 kilograms per square centimeter gauge of 1: 1 H2 / CO and heated to 80 ° C. 6 milliliters (3.73 grams) of 1,3-butadiene were charged with a regulated supply pump and the reactor was pressurized at 70.30 kilograms per square centimeter gauge with 1: 1 H2 / CO. The reaction mixture was maintained at 80 ° C under 70.30 kilograms per square centimeter of 1: 1 H2 / CO. The samples of the reaction mixture taken after 15 and 43 minutes gave the results indicated in Table E, which are presented below.

Table E Temp. H2 / CO Conversion Selectivity Regimen () 2 (mm.) (° C) (kg / cm) butadiene (m / L / H) 3 and 4-pentene manométpca) (%) 15 80 35.15 / 35.15 53 2.6 70 43 80 35.15 / 35.15 89 1.5 Example 51 A stirred high-pressure reactor with a capacity of 100 milliliters was charged with 0.12 millimole of rhodium dicarbonyl acetylacetonate (I), 2.2 millimoles of triphenylphosphine, 1.5 milliliters of cis-3-pentenol, 26 milliliters of ethyl alcohol and 1 milliliter of diglima, as an internal standard. The reactor was pressurized with .352 kilogram per square centimeter of carbon monoxide and hydrogen at a ratio of 1: 1, heated to 105 ° C, and then pressurized to 2.11 kilograms per square centimeter with carbon monoxide and hydrogen. A sample of the reaction mixture after 0.5 hour was taken and then analyzed by gas chromatography. The details of the reaction are indicated in Table F, which is presented below.

Example 52 A high-capacity stirred reactor with a capacity of 100 milliliters was charged with 0.25 millimole of rhodium dicarbonyl acetylacetonate (I), 4.9 millimoles of triphenylphosphine, 1.5 milliliters of cis-3-pentenol, 26 milliliters of tetrahydrofuran and 1 milliliter of diglyme , as an internal standard. The reactor was pressurized to .703 kilogram per square centimeter of carbon monoxide and hydrogen at a ratio of 1: 1, heated to 75 ° C, and then - It was pressurized to 3.52 kilograms per square centimeter of carbon monoxide and hydrogen. Samples of the reaction mixture were taken during time zero and after 5.5 hours and then analyzed by gas chromatography. At the end of the reaction (5.5 hours) the gases were discharged and the reaction mixture was drained. The details of the reaction are indicated in Table F.

Example 53 A high-capacity stirred reactor with a capacity of 100 milliliters was charged with 0.22 millimole of rhodium dicarbonyl acetylacetonate (I), 4.4 millimoles of triphenylphosphine, 1.5 milliliters of cis-3-pentenol, 26 milliliters of ethyl alcohol and 1 milliliter of diglima, as an internal norm. The reactor was pressurized with .703 kilogram per square centimeter of carbon monoxide and hydrogen in a ratio of 1: 1, heated to 75 ° C, and then pressurized to 3.52 kilograms per square centimeter of carbon monoxide and hydrogen. The samples of the reaction mixture were taken during time zero and after 20 hours and then analyzed by gas chromatography. At the end of the reaction (20 hours) the gases were discharged and the reaction mixture was drained. The details of the reaction are disclosed in Table F.

Example 54 A high-capacity stirred reactor with a capacity of 100 milliliters was charged with 0.25 millimole of rhodium dicarbonyl acetylacetonate (I), 4.9 millimoles of triphenylphosphine, 1.5 milliliters of cis-3-pentenol, 26 milliliters of tetrahydrofuran and 1 milliliter of diglyme , as an internal standard. The reactor was pressurized with .352 kilogram per square centimeter of carbon monoxide and hydrogen in a ratio of 1: 1, heated to 100 ° C, and then pressurized to 2.11 kilograms per square centimeter of carbon monoxide and hydrogen. The samples of the reaction mixture were taken during time zero and after 1.5 hours, and then analyzed by gas chromatography. At the end of the reaction (1.5 hours) the gases were discharged and the reaction mixture was drained. The details of the reaction are indicated in Table F.

Example 55 A high stirred high pressure reactor with a capacity of 100 milliliters was charged with 0.27 millimole of rhodium dicarbonyl acetylacetonate (I), 0.29 millimole of (R) - (+) -2, 2'-bis (diphenylphosphino) - 1, 1'-biphenyl, 1.5 milliliters of cis-3-pentenol, 26 milliliters of tetrahydrofuran and 1 milliliter of diglyme, as an internal standard. The reactor was pressurized to .703 kilogram per square centimeter of carbon monoxide and hydrogen in a ratio of 1: 1, heated to 75 ° C, and then pressurized to 8.44 kilograms per square centimeter of carbon monoxide and hydrogen. Samples of the reaction mixture were taken during time zero and after 2 hours and then analyzed by gas chromatography. At the end of the reaction (2 hours) the gases were discharged and the reaction mixture was drained. The details of the reaction are indicated in Table F.

Table F Ex. Metal Solvent Group Temp. CO / H2 No. C? < ordinator (° C) (kg / cm2) 51 Rh PP EtOH 105 _ 1.05 / 1.05 52 Rh PP THF 75 1.76 / 1.76 53 Rh TPP EtOH 75 1.76 / 1.76 54 Rh TPP THF 100 -1.05 / 1.05 55 Rh BINAP THF 75 4.22 /4.22 - - Table C (Continued) Ex. Conversion Regime C5a C5b Et5L Me6L 6- No. of Pent. (%) (M / l - h) (%) (%) (%) (%) (51 18 nd 14 37 7 15 25 52 63 0.06 1 7 34 47 10 53 40 0.01 2 12 36 34 14 54 40 0.15 13 47 3 11 15 55 35 0.10 6 83 0 9 1 Conversion of Pent. = conversion of cis-3-pentenol; C5a = 1-pentenol + valeraldehyde + 2-pentenol; C5b = trans-3-pentenol + 4-pentenol; Et 5 L = 2-ethylbutyrolactol; Me6L = 2-methylvalerolactol; 6-HH = 6-hydroxyhexanal; TPP = triphenylphosphine; BINAP = (R) - (+) -2, 2'-bis (diphenylphosphino) -1, 1'-biphenyl; EtOH = ethyl alcohol; THF tetrahydrofuran.

Example 56 A stirred high-pressure reactor with a capacity of 100 milliliters was charged with 0.10 millimole of rhodium dicarbonyl acetylacetonate (I), approximately 0.20 millimole of 2,2'- (bis-diphenyl-phosphinomethyl) -1, 1'-biphenyl, 1 milliliter of sodium hydroxide. -pentenol, 26 milliliters of ethanol and 1 milliliter of diglyme, - - as an internal standard. The reactor was pressurized with .352 - .703 kilogram per square centimeter of 1/1 hydrogen / carbon monoxide and heated to 90 ° C. At 90 ° C, the reactor was pressurized at 17.58 kilograms per square centimeter with 1/1 hydrogen / carbon monoxide and stirred for one hour. The reactor gases were discharged and the reaction mixture was drained and analyzed by gas chromatography. 6-hydroxyhexanal was formed at 97 percent selectivity.

Examples 57-60 In a high-capacity stirred reactor with a capacity of 100 milliliters, 0.07 millimole of rhodium dicarbonyl acetylacetonate (I), 0.35 millimole of a diphosphite coordinating group was loaded as identified in Table G below. is illustrated in the previous specification, 25 milliliters of tetrahydrofuran and 0.25 milliliter of diglyme, as an internal standard. The reactor was pressurized with 3.52 kilograms per square centimeter of hydrogen / carbon monoxide in a ratio of 1/1 and heated to the temperature in Table G. At the desired temperature, 1.0 milliliter of 3-pentenol and the reactor were added. was pressurized to the desired hydrogen / carbon monoxide pressures signaled in the - Table G. After a 5 percent decrease in reactor pressure, the reactor was again pressurized to the initial value with hydrogen / carbon monoxide in a ratio of 1/1. At the end of the 120 minute reaction period, the gases were discharged and the reaction mixture was drained and analyzed by gas chromatography. The details and additional results of the analyzes are shown in Table G.

Table G Ex. Gpo. Temp Coordinator H2 / CO Conversion of Selectivity to 2 No. of bisphosphite (° C) (kg / cm) 3-pentenol (%) 6-hydroxyhexanal (%) 57 Coordinating Group F 85 7.03 / 7.03 68 60 58 Coordinating Group F 95 14.06 / 3.52 94 59 59 Coordinating Group D 85 7.03 / 7.03 44 65 60 Coordinating Group D 95 24.31 / 12.19 _ 52 58 Examples 61-65 In a stirred high-pressure reactor with a capacity of 100 milliliters, 0.07 millimole of rhodium dicarbonyl acetylacetonate (I), 0.35 millimole of a bisphosphite coordinating group was charged as identified in Table H presented below and that is illustrated below, and in the previous specification, 25 milliliters of tetrahydrofuran and 0.5 milliliter of diglyme - as an internal standard. The reactor was pressurized with 3.52 kilograms per square centimeter of hydrogen / carbon monoxide in a ratio of 1/1 and heated to 95 ° C. At the desired temperature, 1.0 milliliter of 3-pentenol was added and the reactor was pressurized at 35.15 kilograms per square centimeter with hydrogen / carbon monoxide in a ratio of 1/1. After a 5 percent decrease in reactor pressure, the reactor was re-pressurized to the initial value with hydrogen / carbon monoxide in a ratio of 1/1. At the end of the 120 minute reaction period, the gases were discharged and the reaction mixture was drained and analyzed by gas chromatography. The details and additional results of the analyzes are disclosed in Table H.

Table H Ex. Coordinating Group Conversion of Selectivity to Blsphosphite no. 3-pentenol (%.}. 6-hydroxyhexanal (%) 61 Coordinating Group W 20 59 62 Coordinating Group X 50 59 63 Coordinating Group E 67 55 64 Coordinating Group Y 92 44 65 bis (di-t-butyl) phenol (f-enylene glycol-P) 2 ethylidene 54 29 - Coordinating Group Coordinating Group X Coordinating Group Ethylene bis (di-t-butyl) phenol (phenylene glycol-P) 2 Examples 66-69 A magnetically stirred autoclave with a capacity of 100 milliliters with N2 was purged for 30 minutes and charged with a solution consisting of 3 milliliters of 3-pentenol, 26 milliliters of tetrahydrofuran, the co-coordinator group Z identified below and Rh dicarbonyl acetylacetonate. (I) in quantities that are listed in Table I below. The autoclave was pressurized with 60 percent to 80 percent of the total amount of 1: 1 hydrogen / carbon monoxide and heated to the temperature mentioned in Table I. The total amount of 1: 1 hydrogen / monoxide The carbon content was as follows: Example 67 - 7.03 kilograms per square centimeter of hydrogen and 7.03 kilograms per square centimeter of carbon monoxide; Example 68 - 7.03 kilograms per square centimeter of hydrogen and 7.03 kilograms per square centimeter of carbon monoxide; Example 69 - 3.52 kilograms per square centimeter of hydrogen and 3.52 kilograms per square centimeter of carbon monoxide; Example 70 - 7.03 kilograms per square centimeter of hydrogen and 7.03 kilograms per square centimeter of carbon monoxide. After having reached the appropriate temperature, the autoclave was pressurized to the total amount of hydrogen / carbon monoxide 1: 1 described above. The reaction mixture was maintained isothermally under 1: 1 hydrogen / carbon monoxide. Samples of the reaction mixture that were taken after 150 minutes - provided the results mentioned in Table I. The selectivities were determined by gas chromatography and are referred to as normal response factors. 0.94 gram (7.02 millimoles) of diglyme was used as a standard for internal gas chromatography in the reaction mixture. Table I Ex. Temp. Gpo. CoordiRh (C02) Conversion of Selectivity Regime No. (° C) nador Z (acac) 3-pentenol (m / L / h) of 6-hydroxy (g) (g) hexanal (%) 66 85 0.355 0.02 13% 0.5 46.7 67 90 1.07 0.07 74% 0.70 54.3 68 105 0.14 0.02 96% 0.96 61.2 69 95 0.35 0.02 38% 0.41 54.4 Coordinating Group Z Example 70 Dodecacarbonyl from tetratrarium (52.3 milligrams) and Coordinating Group F (1.17 grams) were dissolved in tetraglima (80 milliliters). To this were added nonane (1.07 grams) as the internal standard for gas chromatography and cis-3-pentenol (25.8 grams). The mixture was charged in a stirred Parr autoclave of 300 milliliter capacity and 14.06 kilograms per square centimeter of synthesis gas (1: 1 carbon monoxide: hydrogen) was added. The reactor temperature was raised to 95 ° C, synthesis gas was added to the reactor to bring the pressure to 35.15 kilograms per square centimeter gauge. The reaction was operated for 157 minutes before stopping. The gas chromatography analysis of the reaction mixture showed the following composition: valeraldehyde (23.7%), trans-3-pentenol (8.7%), cis-3-pentenol (13.6%), hydroxyaldehyde branched (5.6%) and 6-hydroxyhexanal (52.2%). The identity of the linear and branched aldehydes was confirmed by gas chromatography / infrared spectroscopy mass spectroscopy. Even though the invention has been illustrated by certain of the foregoing examples, it will not be construed as being limited thereto; rather, the invention encompasses the generic area as disclosed in the foregoing. Different modalities and modifications can be made without deviating from the spirit and scope of it.

Claims

R E I V I N D I C A C I O N E S:

1. A process for producing one or more substituted or unsubstituted hydroxyaldehydes, comprising subjecting one or more substituted or unsubstituted alkadienes to reductive hydroformylation, in the presence of a reductive hydroformylation catalyst and hydroformylation in the presence of a hydroformylation catalyst to produce one or more of the substituted or unsubstituted hydroxyaldehydes.

2. The process for producing one or more substituted or unsubstituted hydroxyaldehydes comprising subjecting one or more substituted or unsubstituted pentenales to reductive hydroformylation, in the presence of a reductive hydroformylation catalyst in order to produce one or more substituted or unsubstituted hydroxyaldehydes.

3. A process for producing one or more substituted or non-substituted hydroxyaldehydes comprising subjecting one or more unsaturated or unsubstituted unsaturated alcohols having at least 4 carbon atoms to hydroformylation in the presence of a hydroformylation catalyst to produce one or more hydroxyaldehydes replaced or not replaced.

4. A process for producing one or more substituted or unsubstituted hydroxyaldehydes comprising: (a) subjecting one or more of the substituted or unsubstituted alkadienes to reductive hydroformylation in the presence of a reductive hydroformylation catalyst in order to produce one or more substituted unsaturated alcohols or unsubstituted, and (b) subjecting one or more subtitled or unsubstituted unsaturated alcohols to hydroformylation in the presence of a hydroformylation catalyst in order to produce one or more substituted or unsubstituted hydroxyaldehydes.

5. The process of claim 4, wherein the unsubstituted or substituted alkadiene comprises butadiene, unsubstituted or unsubstituted unsaturated alcohols comprise cis-3-penten-1-ol, trans-3-penten-1-ol, 4- penten-l-ol, cis-2-penten-l-ol and / or trans-2-penten-l-ol, and the substituted or unsubstituted hydroxyaldehydes comprise 6-hydroxyhexanol.

The process of claim 4, wherein the reductive hydroformylation reaction conditions in step (a), and the hydroformylation reaction conditions in step (b) may be the same or different, and the reductive hydroformylation catalyst in step (a) and the hydroformylation catalyst in step (b) may be the same or different.

7. The process of claims 1, 2, 3 and 4, wherein the reductive hydroformylation catalyst and the hydroformylation catalyst comprise a complex catalyst metal-coordinator group.

The process of claim 7, wherein the complex catalyst metal-coordinator group comprises a metal that is selected from a Group 8, 9 and 10 metal formed in complex with an organophosphorus coordinating group that is selected from the coordinating group of mono-, di-, tri- and poly- (organophosphine).

The process of claim 7, wherein the complex catalyst metal-coordinating group comprises a metal selected from a Group 8, 9 and 10 of the metal formed in complex with an organophosphorus coordinating group selected from: i) a triorganophosphine coordinating group represented by the formula: wherein each R1 is the same or different and is a substituted or unsubstituted monovalent hydrocarbon radical; - (ii) a monoorganophosphite represented by the formula: 3 wherein R represents a substituted or unsubstituted trivalent hydrocarbon radical containing from 4 to 40 carbon atoms or more; (iii) a diorganophosphite represented by the formula: 4 wherein R represents a substituted or unsubstituted divalent hydrocarbon radical containing from 4 to 40 carbon atoms or more and represents a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 18 carbon atoms or more; (iv) a trioxganophosphite represented by the formula: - - wherein each R is the same or different and is a substituted or unsubstituted monovalent hydrocarbon radical; and (v) an organopoliphosphite containing two or more tertiary (trivalent) phosphorus atoms represented by the formula: wherein X represents an unsubstituted n-valent hydrocarbon connecting radical containing from 2 to 9 carbon atoms, each R is the same or different and is a divalent hydrocarbon radical containing from 4 to 40 carbon atoms, each R is the same or different and is a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 24 carbon atoms, a and b may be the same or different and each has a value from 0 to 6, with the proviso that the sum of a + b is 2 to 6 and n is equal to a + b. -

10. The process of claims 1, 2, 3 and 4, which is carried out at a temperature of about 50 ° C to 150 ° C and a total pressure of about 1.41 kilograms per square centimeter gauge at about 210.90 kilograms per square centimeter gauge .

The process of claims 1, 2, 3 and 4, wherein the process intermittently or continuously generates a reaction mixture comprising: (1) one or more substituted or unsubstituted 6-hydroxyhexanals; (2) optionally one or more substituted or unsubstituted penten-1-ols; (3) optionally one or more substituted or unsubstituted 5-hydroxypentanals and / or the cyclic lactol derivatives thereof; (4) optionally one or more substituted or unsubstituted 4-hydroxybutanales and / or the cyclic lactol derivatives thereof; (5) optionally one or more substituted or unsubstituted pentan-1-oles; (6) optionally one or more substituted or unsubstituted valeraldehydes; (7) optionally one or more substituted or unsubstituted pentenales; (8) optionally one or more 1,6-substituted or unsubstituted hexanodials; (9) optionally one or more substituted 1,5-pentanedioles; (10) optionally one or more substituted 1,4-butanedials; (11) one or more substituted or unsubstituted butadienes; where the weight ratio of component (1) to the sum of components (2), (3), (4), (5), (6), (7), (8), (9) and (10) is greater than about 0.1; and the weight ratio of the component (11) to the sum of the components (1), (2), (3), (4), (5), (6), (7), (8), (9) and (10) is from about 0 to about 100 or a reaction mixture comprising: (1) one or more substituted or unsubstituted 6-hydroxyhexanals; (2) one or more substituted or unsubstituted penten-1-oles; (3) optionally one or more substituted or unsubstituted 5-hydroxypentanals, and / or the cyclic lactol derivatives thereof; (4) optionally one or more substituted or unsubstituted 4-hydroxybutanales, and / or the cyclic lactol derivatives thereof; and (5) optionally one or more substituted or unsubstituted valeraldehydes; wherein the weight ratio of the component (1) to the sum of the components (3), (4) and (5) is greater than about 0.1; and the weight ratio of component (2) to the sum of components (1), (3), (4) and (5) is from about 0 to about 100.

12. A process for producing a reaction mixture that comprises one or more substituted or unsubstituted hydroxyaldehydes whose process comprises the process of claims 1, 2, 3 and 4.

13. A process for producing one or more substituted or unsubstituted 6-hydroxyhexanals comprising: (a) submitting one or more than the substituted or unsubstituted alkadienes to reductive hydroformylation in the presence of a reductive hydroformylation catalyst to produce one or more substituted or unsubstituted unsaturated alcohols comprising 3-penten-1-ols, 4-penten-1-ol and / or 2-penten-l-oles. (b) optionally separating the 3-penten-1-oles, 4-penten-1-ol and / or 2-penten-1-oles from the reductive hydroformylation catalyst; and (c) subjecting one or more of the substituted or unsubstituted unsaturated alcohols comprising 3-penten-1-ols, 4-penten-1-ol and / or 2-penten-1-oles to hydroformylation, in the presence of a hydroformylation catalyst in order to produce one or more substituted or unsubstituted 6-hydroxyhexanals.

The process of claim 13, wherein the reductive hydroformylation conditions in step (a) and the hydroformylation conditions in step (c) are the same or different, and the reductive hydroformylation catalyst in step (a) , and the hydroformylation catalyst in step (c) are the same or different.

15. A process for producing one or more substituted or unsubstituted 6-hydroxyhexanals comprising: (a) subjecting one or more substituted or unsubstituted alkadienes to reductive hydroformylation in the presence of a reductive hydroformylation catalyst, to produce one or more alcohols substituted or unsubstituted unsaturates comprising 3-penten-1-ols, 4-penten-1-ol and / or 2-penten-1-ols. (b) optionally separating the 3-penten-l-oles, 4-penten-l-ol and / or 2-penten-l-oles from the reductive hydroformylation catalyst; and (c) optionally subjecting 2-penten-l-oles and / or 3-penten-l-oles to isomerization in the presence of a heterogeneous or homogeneous olefin isomerization catalyst to partially or completely isomerize the 2-penten-oles and / o the 3-penten-l-oles in 3-penten-l-oles and / or 4-penten-l-ol; and (d) subjecting one or more of the substituted or unsubstituted unsaturated alcohols comprising 2-penten-1-ols, 3-penten-1-ols and / or 4-penten-1-ol to hydroformylation, in the presence of a hydroformylation catalyst to produce one or more substituted or unsubstituted 6-hydroxyhexanals.

The process of claim 15, wherein the reductive hydroformylation conditions in step (a), and the hydroformylation conditions in step (c) are the same or different, and the reductive hydroformylation catalyst in step (a) ), and the hydroformylation catalyst in step (d) are the same or different.

17. A composition produced by the processes of claims 1, 2, 3 and 4, comprising: (1) one or more substituted or unsubstituted 6-hydroxyhexanals; (2) optionally one or more substituted or unsubstituted penten-1-ols; (3) optionally one or more substituted or unsubstituted 5-hydroxypentanals and / or cyclic lactol derivatives thereof; (4) optionally one or more substituted or unsubstituted 4-hydroxybutanales and / or cyclic lactol derivatives thereof; (5) optionally one or more substituted or unsubstituted pentan-1-oles; (6) optionally one or more substituted or unsubstituted valeraldehydes; (7) optionally one or more substituted or unsubstituted pentenales; (8) optionally one or more 1,6-substituted or unsubstituted hexanodials; (9) optionally one or more substituted 1,5-pentanedioles; (10) optionally one or more substituted 1,4-butanedials; and (11) one or more substituted or unsubstituted butadienes; where the weight ratio of component (1) to the sum of components (2), (3), (4), (5), (6), (7), (8), (9) and ( 10) is greater than about 0.1; and the weight ratio of the component (11) to the sum of the components (1), (2), (3), (4), (5), (6), (7), (8), (9) ) and (10) is from about 0 to about 100; or a composition comprising: (1) one or more substituted or unsubstituted 6-hydroxyhexanals; (2) optionally one or more substituted or unsubstituted penten-1-ols; (3) optionally one or more substituted or unsubstituted 5-hydroxypentanals and / or the cyclic lactol derivatives thereof; (4) optionally one or more substituted or unsubstituted 4-hydroxybutanales and / or the cyclic lactol derivatives thereof; (5) optionally one or more substituted or unsubstituted pentan-1-oles; (6) optionally one or more substituted or unsubstituted valeraldehydes; and (7) one or more substituted or unsubstituted pentenales; wherein the weight ratio of the component (1) to the sum of the components (2), (3), (4), (5), and (6), is greater than about 0.1; and the weight ratio of the component (7) to the sum of the components (1), (2), (3), (4), (5) and (6) is from about 0 to about 100; or a composition comprising: (1) one or more substituted or unsubstituted 6-hydroxyhexanals; (2) one or more substituted or unsubstituted penten-1-oles; (3) optionally one or more substituted or unsubstituted 5-hydroxypentanals and / or the cyclic lactol derivatives thereof; (4) optionally one or more substituted or unsubstituted 4-hydroxybutanales and / or the cyclic lactol derivatives thereof; and (5) optionally one or more substituted or unsubstituted valeraldehydes; wherein the weight ratio of the component (1) to the sum of the components (3), (4), and (5), is greater than about 0.1; and the weight ratio of component (2) to the sum of components (1), (3), (4), and (5) is from about 0 to about 100.

18. A reaction mixture comprising one or more hydroxyaldehydes substituted or unsubstituted in which the reaction mixture is prepared by the process of claims 1, 2, 3 and 4.

19. The processes of claims 1, 2, 3 and 4, further comprising the step of deriving one or more of the substituted or unsubstituted hydroxyaldehydes wherein the derivatization reaction comprises hydrogenation, esterification, etherification, amination, alkylation, dehydrogenation, reduction, acylation, condensation, carboxylation, carbonylation, oxidation, cyclization, silylation and allowable combinations of the same.

20. A derivative of one or more of the substituted or unsubstituted hydroxyaldehydes of claim 19.