Process for preparing TCD-diamine
View Patent ↗A process for preparing 3(4),8(9)-bis(aminomethyl)tricycle-[5.2.1.0 2,6 ]decane by hydroformylating dicyclopentadiene with subsequent reductive amination wherein the hydroformylation of dicyclopentadiene is carried out in two stages, and, in a first hydroformylation stage, the reaction is effected 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 to give 8(9)-formyltricyclo[5.2.1.0 2,6 ]dec-3-ene, and, in a second hydroformylation stage, the thus obtained 8(9)-formyltricyclo[5.2.1.0 2,6 ]dec-3-ene is converted, in a homogeneous organic phase in the presence of transition metal compounds of group VIII of the Periodic Table of the Elements to 3(4),8(9)-bisformyltricyclo[5.2.1.0 2,6 ]decane
1. A process for preparing 3(4),8(9)-bis(aminomethyl)tricycle-[5.2.1.0 2,6 ]decane by hydroformylating dicyclopentadiene with subsequent reductive amination, comprising reacting dicyclopentadiene, in a first hydroformylation stage in a heterogeneous reaction system using an aqueous solution of transition metal compounds, containing water-soluble organic phosphorus (III) compounds in complex-bound form selected from the group consisting of sulfonated triarylphosphines of the formula (I)
in which Ar 1 , Ar 2 and Ar 3 are individually aryl groups of 6 to 14 carbon atoms, the substituents Y 1 , Y 2 and Y 3 are individually selected from the group consisting of alkyl and alkoxy of 1 to 4 carbon atoms, chlorine, bromine, hydroxyl, cyanide, nitro, and NR 1 R 2 in which the R 1 and R 2 are individually hydrogen, or alkyl of 1 to 4 carbon atoms, in which m is selected from the group 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 , n 3 are individually integers from 0 to 3, and at least one of n 1 , n 2 and n 3 equal to or treater than 1; sulfonated diphosphines of the formula (II)
in which n 4 and n 5 are individually 0 to 1, and the sulfonated diphosphines of the formula (II) up to six SO 3 M groups, and M is selected from the group consisting of ammonium, a monovalent metal and an equivalent of a polyvalent metal and; sulfonated diphosphines of the formula (III)
in which n 6 , n 7 , n 8 and n 9 are individually 0 or 1, and the sulfonated diphosphines of the formula (III) contain from four to eight SO 3 M groups, and M is selected from the group consisting of ammonium, a monovalent metal and an equivalent of a polyvalent metal; 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 hydrogen and carbon monoxide to give 8(9)-formyltricyclo[5.2.1.0 2,6 ]dec-3-ene, then separating the organic phase from the aqueous phase and subsequently converting the thus obtained 8(9)-formyltricyclo[5.2.1.0 2,6 ]dec-3-ene, in a second hydroformylation stage in a homogeneous organic phase in the presence of transition metal compounds of group VIII of the Periodic Table of Elements at temperatures of from 70 to 140° C. and pressures of from 5 to 35 MPa by reacting with hydrogen and carbon monoxide, to 3(4),8(9)-bisformyltricyclo[5.2.1.0 2,6 ]decane and subsequently reductively aminating the thus obtained 3(4),8(9)-bisformyltricyclo-[5.2.1.0 2,6 ]decane to give 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0 2,6 ]decane.
2. The process as claimed in claim 1 , wherein 8(9)-formyl-tricyclo[5.2.1.0 2,6 ]dec-3-ene obtained in the first hydroformylation stage is distilled before use in the second hydroformylation stage.
3. The process as claimed in claim 1 , wherein, in the second hydroformylation stage, the reaction is effected in the presence of organic phosphorus (III) compounds.
4. The process as claimed in claim 1 , wherein in formula (I), Ar 1 , Ar 2 and Ar 3 are phenyl, m 1 , m 2 , m 3 are each 0, n 1 , n 2 , n 3 are each 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.
5. The process of claim 1 , wherein the transition metal compounds, used in the first hydroformylation stage, of group VIII of the Periodic Tale of the Elements are compounds of a member selected from the group consisting of rhodium, cobalt, iridium, nickel, palladium, platinum, iron and ruthenium.
6. The process of claim 1 , wherein the transition metal compounds, used in the second hydroformylation stage, of group VIII of the Periodic Table of the Elements are compounds of a member of the group consisting of rhodium, cobalt, iridium, nickel, platinum, palladium, iron and ruthenium.
7. The process of claim 1 , wherein the transition metal compounds, used in the first and second hydroformylation stage, of group VIII of the Periodic Table of the Elements are compounds of rhodium.
8. The process of claim 1 , wherein the temperature in the first hydroformylation stage is from 100 to 150° C., and the pressure is from 1 to 6 MPa.
9. The process of claim 1 , wherein the temperature in the second hydroformylation stage is from 80 to 130° C., and the pressure is from 10 to 30 MPa.
10. The process of claim 7 , wherein the rhodium concentration in the first hydroformylation stage is from 20 to 1000 ppm by weight, based in each case on the aqueous catalyst solution.
11. The process of claim 1 , wherein from 10 to 300 mol of phosphorus in the form of the water-soluble organic phosphorus compound are used per mole of rhodium in the first hydroformylation stage.
12. The process of claim 7 , wherein the rhodium concentration in the second hydroformylation stage is from 5 to 100 ppm by weight, based on the homogeneous reaction mixture.
13. The process of claim 11 , wherein the rhodium concentration in the second hydroformylation stage is from 5 to 1000 ppm by weight, based in each case on the homogeneous reaction mixture, and from 5 to 200 mol of phosphorus in the form of organic phosphorus compounds are used per mole of rhodium.