Process for preparing TCD-monenal
View Patent ↗A process for selectively hydroformylating dicyclopentadiene to 8(9)-formyltricyclo-[5.2.1.0 2,6 ]dec-3-ene in a heterogeneous reaction system using an aqueous solution of transition metal compounds, containing water-soluble organic phosphorus(III) compounds in complex-bound form, of group VIII of the Periodic Table of the Elements, wherein the water-soluble organic phosphorus(III) compounds are alkali metal or alkaline earth metal salts of sulfonated arylphosphines and aryldiphosphines.
1. A process for preparing 8(9)-formyltricyclo[5.2.1.0 2,6 ]dec-3-ene by hydroformylating dicyclopentadiene in a heterogeneous reaction system using an aqueous solution of transition metal compounds, containing water-soluble organic phosphorus(III) compounds in complex-bound form, of group VIII of the Periodic Table of the Elements at temperatures of from 70 to 150° C. and pressures of from 0.5 to 10 MPa with synthesis gas, which comprises using, as the water-soluble organic phosphorus(III) compounds selected from the group consisting of
A) sulfonated triarylphosphines
in which Ar 1 , Ar 2 and Ar 3 are individually aryl of 6 to 14 carbon atoms, Y 1 , Y 2 and Y 3 are individually selected from the group consisting of alkyl or alkoxy of 1 to 4 carbon atoms, chlorine, bromine, hydroxyl, cyanide, nitro and —NR 1 R 2 in which R 1 and R 2 are consisting of lithium, sodium, potassium, magnesium, calcium and barium, m 1 , m 2 and m 3 are individually integers from 0 to 5, n 1 , n 2 and n 3 are individually integers from 0 to 3, at least one n 1 , n 2 and n 3 being equal to or greater than 1;
B) sulfonated diphosphines of the formula
in which n 4 and n 5 are individually 0 or 1, the compound of formula (II) containing up to six —SO 3 M groups, and M is a monovalent metal or the equivalent of a monovalent metal; and
C) sulfonated diphosphines of the formula
in which n 6 , n 7 , n 8 and n 9 are individually 0 to 1, the compound of formula (III) containing from four to eight —SO 3 M, and M is a monovalent metal or the equivilant of a polyvalent metal.
2. The process of claim 1 , wherein the resulting 8(9)-formyltricyclo[5.2.1.0 2,6 ]dec-3-ene is distilled.
3. The process of claim 1 , wherein Ar 1 , Ar 2 , Ar 3 are phenyl, m 1 , m 2 , and m 3 are 0, n 1 , n 2 , n 3 are individually 0 or 1 and n 1 +n 2 +n 3 together add up to 1 to 3, and the sulfonate groups are in the meta-position.
4. The process of claim 1 , wherein the transition metal compounds of group VIII of the Periodic Table of the Elements used are compounds of a metal selected from the group consisting of rhodium, cobalt, iridium, nickel, palladium, platinum, iron or ruthenium.
5. The process of claim 1 , wherein the transition metal compounds of group VIII of the Periodic Table of the Elements used are compounds of rhodium.
6. The process of claim 1 , wherein the reaction temperature is from 100 to 150° C. and the pressure is from 1 to 6 MPa.
7. The process of claim 1 , wherein the rhodium concentration is from 20 to 1000 ppm by weight, based in each case on the aqueous catalyst solution.
8. The process of claim 1 , wherein from 10 to 300 mol of phosphorous in the form of the water-soluble organic phosphorous compound are used per mole of rhodium.
9. The process of claim 6 wherein the reaction temperature is 110 to 140° C. and the pressure is 1.5 to 5 Mpa.
10. The process of claim 7 wherein the rhodium concentration is 50 to 800 ppm by weight.
11. The process of claim 7 wherein the rhodium concentration is 100 to 600 ppm by weight.
12. The process of claim 8 wherein the amount of phosphorous is 50 to 150 mol.