Process for preparing di-, tri- and polyamines by homogeneously catalyzed alcohol amination

Abstract

Process for preparing primary amines which have at least one functional group of the formula (CH.sub.2NH.sub.2) and at least one further primary amino group by alcohol amination of starting materials having at least one functional group of the formula (CH.sub.2OH) and at least one further functional group (X), where (X) is selected from among hydroxyl groups and primary amino groups, by means of ammonia with elimination of water, wherein the reaction is carried out homogeneously catalyzed in the presence of at least one complex catalyst comprising at least one element selected from groups 8, 9 and 10 of the Periodic Table and also at least one donor ligand.

Claims

1. A process for preparing a primary amine comprising a functional group of formula (CH.sub.2NH.sub.2) and a further primary amino group by alcohol amination, the process comprising reacting a starting material having a functional group of formula (CH.sub.2H) and a further functional group (X), with ammonia with elimination of water, wherein (X) is selected from the group consisting of a hydroxyl group and a primary amino group, and the reacting is homogeneously catalyzed in the presence of a complex catalyst comprising an element selected from groups 8, 9 and 10 of the Periodic Table and also a donor ligand, wherein the complex catalyst has formula I: ##STR00033## wherein L.sup.1 and L.sup.2 are each independently selected from the group consisting of PR.sup.aR.sup.b, NR.sup.aR.sup.b, sulfide, SH, S(O)R, C.sub.5-C.sub.10-heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S, AsR.sup.aR.sup.b, SbR.sup.aR.sup.b and an N-heterocyclic carbene of formula II or III: ##STR00034## L.sup.3 is a monodentate two-electron donor selected from the group consisting of CO, PR.sup.aR.sup.bR.sup.c, NO.sup.+, AsR.sup.aR.sup.bR.sup.c, SbR.sup.aR.sup.bR.sup.c, SR.sup.aR.sup.b, RCN, RNC, N.sub.2, PF.sub.3, CS, pyridine, thiophene, tetrahydrothiophene and an N-heterocyclic carbene of formula II or III; R.sup.1 and R.sup.2 are both hydrogen or together with carbon atoms to which they are bound form a phenyl ring which together with the quinolinyl unit of formula I forms an acridinyl unit; R, R.sup.a, R.sup.b, R.sup.c, R.sup.3, R.sup.4 and R.sup.5 are each independently unsubstituted or at least monosubstituted C.sub.1-C.sub.10-alkyl, C.sub.3-C.sub.10-cycloalkyl, C.sub.3-C.sub.10-heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O and S, C.sub.5-C.sub.10-aryl or C.sub.5-C.sub.10-heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S, wherein substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH.sub.2 and C.sub.1-C.sub.10-alkyl; Y is a monoanionic ligand selected from the group consisting of H, F, Cl, Br, I, OCOR, OCOCF.sub.3, OSO.sub.2R, OSO.sub.2CF.sub.3, CN, OH, OR and N(R).sub.2, or an uncharged molecule selected from the group consisting of NH.sub.3, N(R).sub.3 and R.sub.2NSO.sub.2R; X.sup.1 represents one, two, three, four, five, six or seven substituents on an atom of the acridinyl unit or one, two, three, four or five substituents on an atom of the quinolinyl unit, where plural X.sup.1 are selected independently from the group consisting of hydrogen, F, Cl, Br, I, OH, NH.sub.2, NO.sub.2, NC(O)R, C(O)NR.sub.2, OC(O)R, C(O)OR, CN, and a borane derivative that can be obtained from the catalyst of formula I by reaction with NaBH.sub.4, and unsubstituted or at least monosubstituted C.sub.1-C.sub.10-alkoxy, C.sub.1-C.sub.10-alkyl, C.sub.3-C.sub.10-cycloalkyl, C.sub.3-C.sub.10-heterocyclyl comprising a heteroatom selected from N, O and S, C.sub.5-C.sub.10-aryl and C.sub.5-C.sub.10-heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S, wherein substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH.sub.2 and C.sub.1-C.sub.10-alkyl; and M is iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium or platinum.

2. The process according to claim 1, wherein R.sup.1 and R.sup.2 are both hydrogen and the complex catalyst has formula (IV): ##STR00035##

3. The process according to claim 1, wherein R.sup.1 and R.sup.2 together with carbon atoms to which they are bound form a phenyl ring which together with the quinolinyl units of formula I forms an acridinyl unit and the complex catalyst has formula (V): ##STR00036##

4. The process according to claim 1, wherein the complex catalyst is selected from the group of catalysts of formulae (VI), (VII), (VIII), (IX), (X), (XI), (XII) and (XIII): ##STR00037## ##STR00038##

5. The process according to claim 1, wherein the complex catalyst has formula (XIVa): ##STR00039##

6. The process according to claim 1, wherein the complex catalyst has formula (XIVb): ##STR00040##

7. The process according to claim 1, wherein the complex catalyst has formula (XV): ##STR00041## wherein L.sup.1 and L.sup.2 are each independently selected from the group consisting of PR.sup.aR.sup.b, NR.sup.aR.sup.b, sulfide, SH, S(O)R, C.sub.5-C.sub.10-heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S, AsR.sup.aR.sup.b, SbR.sup.aR.sup.b and an N-heterocyclic carbene of formula (II) or (III): ##STR00042## L.sup.3 is a monodentate two-electron donor selected from the group consisting of CO, PR.sup.aR.sup.bR.sup.c, NO.sup.+, AsR.sup.aR.sup.bR.sup.c, SbR.sup.aR.sup.bR.sup.c, SR.sup.aR.sup.b, RCN, RNC, N.sub.2, PF.sub.3, CS, pyridine, thiophene, tetrahydrothiophene and an N-heterocyclic carbene of formula (II) or (III); R.sup.1 and R.sup.2 are both hydrogen or together with carbon atoms to which they are bound form a phenyl ring which together with the quinolinyl unit of formula (XV) forms an acridinyl unit; R, R.sup.a, R.sup.b, R.sup.c, R.sup.3, R.sup.4 and R.sup.5 are each independently unsubstituted or at least monosubstituted C.sub.1-C.sub.10-alkyl, C.sub.3-C.sub.10-cycloalkyl, C.sub.3-C.sub.10-heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O and S, C.sub.5-C.sub.10-aryl or C.sub.5-C.sub.10-heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S, wherein substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH.sub.2 and C.sub.1-C.sub.10-alkyl; and X.sup.1 represents one, two, three, four, five, six or seven substituents on an atom of the acridinyl unit or one, two, three, four or five substituents on an atom of the quinolinyl unit, where plural X.sup.1 are selected independently from the group consisting of hydrogen, F, Cl, Br, I, OH, NH.sub.2, NO.sub.2, NC(O)R, C(O)NR.sub.2, OC(O)R, C(O)OR, CN, a borane derivative that can be obtained from the catalyst of formula (XV) by reaction with NaBH.sub.4, and unsubstituted or at least monosubstituted C.sub.1-C.sub.10-alkoxy, C.sub.1-C.sub.10-alkyl, C.sub.3-C.sub.10-cycloalkyl, C.sub.3-C.sub.10-heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O and S, C.sub.5-C.sub.10-aryl and C.sub.5-C.sub.10-heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S, wherein substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH.sub.2 and C.sub.1-C.sub.10-alkyl.

8. The process according to claim 1, wherein the complex catalyst has formula (XVIa): ##STR00043##

9. The process according to claim 1, wherein Y in the complex catalyst is selected from the group consisting of H, F, Cl and Br.

10. The process according to claim 1, wherein L.sup.3 in the complex catalyst is CO.

11. The process according to claim 1, wherein (X) is selected from functional groups of formulae (CH.sub.2OH) and (CH.sub.2NH.sub.2).

12. The process according to claim 1, wherein the starting material is diethylene glycol.

13. The process according to claim 1, wherein the starting material is a diol selected from the group consisting of ethylene glycol, diethanolamine, polytetrahydrofuran and 1,4-butanediol.

14. The process according to claim 1, wherein the donor ligand is a phosphorus donor ligand.

15. The process according to claim 1, wherein M is Ru.

16. The process according to claim 1, wherein M is Ir.

17. The process according to claim 1, wherein M is Ru or Ir, and the donor ligand is a phosphorus donor ligand.

18. The process according to claim 1, wherein the starting material is a triol or a polyol.

19. The process according to claim 1, wherein the starting material is at least one triol selected from the group consisting of glycerol, trimethylolpropane and triethanolamine.

.Iadd.20. The process according to claim 1, wherein the starting material is at least one polyol selected from the group consisting of pentaerythritol, glucose, mannose, fructose, ribose, deoxyribose, galactose, fucose, rhamnose, sucrose, lactose, cellulose, maltose, amylose, xanthan and polyvinyl alcohols. .Iaddend.

Description

EXAMPLES

General Method for the Catalytic Amination of Alcohols by Means of Ammonia According to the Invention

(1) Catalyst complex XIVb (for preparation, see below, weighed out under an inert atmosphere), solvent (such an amount that the total solvent volume is 50 ml) and the alcohol to be reacted were placed under an argon atmosphere in a 160 ml Parr autoclave (stainless steel V4A) having a magnetically coupled inclined blade stirrer (stirring speed: 200-500 revolutions/minute). The indicated amount of ammonia was introduced at room temperature either in precondensed form or directly from the pressurized NH.sub.3 gas bottle. If hydrogen was used, this was effected by iterative differential pressure metering. The steel autoclave was electrically heated to the temperature indicated and heated for the time indicated while stirring (500 revolutions/minute) (internal temperature measurement). After cooling to room temperature, venting the autoclave and outgassing the ammonia at atmospheric pressure, the reaction mixture was analyzed by GC (30m RTX5 amine 0.32 mm 1.5 m). Purification of the particular products can, for example, be carried out by distillation. The results for the amination of 1,4-butanediol (table 1a, 1b), diethylene glycol (table 2) and monoethylene glycol (table 3), 2,5-furandimethanol (table 4), alkyldiols (table 5), 1,4-bis(hydroxymethyl)-cyclohexane (table 6) and aminoalcohols (table 7) are given below.

(2) Synthesis of the Catalyst Complex XIVb

(3) ##STR00022##

a) Synthesis of 4,5-bis(dicyclohexylphosphinomethyl)acridine

(4) A solution of 4,5-bis(bromomethyl)acridine.sup.1 (5.2 g, 14.2 mmol) and dicyclohexylphosphine (8.18 g, 36.8 mmol) in 65 ml of anhydrous, degassed methanol was heated at 50 C. under an inert argon atmosphere for 66 hours. After cooling to room temperature, triethylamine (5.72 g, 56.7 mmol) was added and the mixture was stirred for 1 hour. Evaporation of the solvent gave a whitish yellow solid in a red oil. Extraction by means of 340 ml of MTBE and concentration of the filtrate gave a reddish brown oil (.sup.1H NMR: mixture of product & HPCy.sub.2). Taking up in a little warm MTBE followed by addition of ice-cooled methanol resulted in precipitation of a yellow, microcrystalline solid. Oscillation and drying under reduced pressure gave air sensitive 4,5-bis(dicyclohexylphosphinomethyl)acridine (2.74 g, 33%) as a yellow powder. .sup.1H NMR (360.63 MHz, d8-toluene): [ppm]=8.07 (s, 1H, H9), 7.91 (d, J=8.3 Hz, 2H, ArH), 7.42 (d, J=8.3 Hz, 2H, ArH), 7.21 (dd, J=8.3 Hz, J=7.2 Hz, 2H, ArH), 3.89 (bs, 4H, CH.sub.2P), 1.96-1.85 (m, 8H, Cy-H), 1.77-1.54 (m, 20H, Cy-H), 1.26-1.07 (m, 16H, Cy-H). .sup.31P{.sup.1H} NMR (145.98 MHz, d8-toluene): [ppm]=2.49 (s, CH.sub.2P(Cy).sub.2).

b) Synthesis of the Catalyst Complex XIVb

(5) 4,5-bis(dicyclohexylphosphinomethyl)acridine (1855 mg, 3.1 mmol) and [RuHCl(CO)(PPh.sub.3).sub.3].sup.2 (2678 mg, 2.81 mmol) were heated at 70 C. in 80 ml of degassed toluene for 2 hours. The resulting dark brown solution was evaporated to dryness, the residue was slurried in 320 ml of hexane and isolated by filtration. Drying under reduced pressure gave the catalyst complex XIVb (1603 mg, 75%) as an orange-brown powder. .sup.1H NMR (360.63 MHz, d8-toluene): [ppm]=8.06 (s, 1H, H9), 7.43 (d, J=7.6 Hz, 2H, ArH), 7.33 (d, J=6.5 Hz, 2H, ArH), 7.06-7.02 (m, 2H, ArH), 5.02 (d, J=11.9 Hz, 2H, CHHPCy.sub.2), 3.54 (d, J=12.2 Hz, 2H, CHHPCy.sub.2), 2.87 (bs, 2H, P(C.sub.aH(CH.sub.2).sub.5).sub.2), 2.54 (bs, 2H, P(C.sub.bH(CH.sub.2).sub.5).sub.2), 2.18 (bs, 2H, Cy-H), 1.88-1.85 (m, 8H, Cy-H), 1.65 (bs, 6H, Cy-H), 1.42-1.35 (m, 14H, Cy-H), 1.17-0.82 (m, 12H, Cy-H), 16.29 (t, J=19.1 Hz, 1H, RuH). .sup.31P{.sup.1H} NMR (145.98 MHz, d8-toluene): [ppm]=60.89 (s, CH.sub.2P(Cy).sub.2). [1] J. Chiron, J. P. Galy, Synlett, 2003, 15. [2] Literature instructions: Inorganic Syntheses 1974, 15, 48. See also: T. Joseph, S. S. Deshpande, S. B. Halligudi, A. Vinu, S. Ernst, M. Hartmann, J. Mol. Cat. (A) 2003, 206, 13-21.

(6) TABLE-US-00001 TABLE 1a Reaction of 1,4-butanediol T Time NH.sub.3 Reaction Selectivity.sup.c) No.sup.a) Solvent [ C.] [h] [eq].sup.d) pressure [bar] Further condition Conversion.sup.b) a b c 1 Toluene 155 12 6 44 0.2 mol % of KOtBu 43.3 60.1 12.1 18.7 2 Toluene 155 12 6 41 1.0 mol % of KOtBu 37.0 61.9 11.4 18.7 3 Toluene 155 24 9 51 87.0 50.3 14.8 30.8 4 Toluene 155 60 6 57 5 bar of H.sub.2 injected cold 58.7 62.2 18.8 18.3 5 p-Xylene 180 12 6 51 100.0 0.6 51.0 43.6 6 p-Xylene 180 12 6 47 5.0 mol % of water 99.9 0.7 46.7 48.6 .sup.a)conditions unless indicated otherwise: 50 ml of solvent, batch size 25 mmol of 1,4-butanediol, 0.1 mol % of catalyst complex XIVb (per alcohol group), .sup.b)evaluation by GC (% by area), .sup.c)product selectivity determined by GC, .sup.d)molar equivalents of NH.sub.3 per OH function on the substrate

(7) TABLE-US-00002 TABLE 1b Reaction of 1,4-butanediol Selectivity.sup.c) Solvent T Time NH.sub.3 Reaction- Conversion.sup.b) a b c No.sup.a) (waterfree) [ C.] [h] [eq].sup.d) pressure [bar] Further conditions.sup.e) [%] [%] [%] [%] 1 Toluol 155 12 6 46.1 0.2 mol % KOH (aq. 20%) 59.25 59.14 16.42 19.89 2 Toluol 155 15 6 42.0 96.06 17.90 14.20 62.10 3 Toluol 155 24 6 40.2 98.92 8.60 20.38 64.91 4 Toluol 180 2 6 52.7 91.52 36.35 25.76 35.39 5 Toluol 180 9 6 48.0 100.00 0.12 19.90 73.67 6 Toluol 180 12 6 69.7 5 bar H2 94.19 30.09 37.23 31.62 7 Toluol 180 12 6 81.9 10 bar H2 89.85 36.24 35.41 27.66 8 Dioxane 180 12 6 44.3 100.00 1.15 23.79 71.23 9 THF 180 12 6 46.9 100.00 0.00 17.03 77.33 10 THF 180 12 9 62.3 100.00 0.00 20.16 71.30 11 THF 180 12 6 71.7 5 bar H2 99.87 2.41 26.28 67.55 .sup.a)condition unless indicated otherwise: 50 ml solvent, batch size 25 mmol 1,4-butanediol; .sup.b)evaluation by GC (% by area), .sup.c)product selectivity determined by GC; .sup.d)molar equivalents NH.sub.3 per OH function on the substrate; .sup.e)mol % based on the OH functions on the substrate

(8) TABLE-US-00003 TABLE 2a Reaction of diethylene glycol T Time NH.sub.3 Reaction Selectivity.sup.c) No.sup.a) Solvent [ C.] [h] [eq].sup.d) pressure [bar] Further condition Conversion.sup.b) a b c 1 Toluene 155 12 6 40 79.0 51.4 23.8 12.9 2 Toluene 155 12 6 43 82.4 55.3 20.1 10.9 3 Toluene 155 12 6 42 0.2 mol % of KOtBu 69.8 41.8 31.9 14.3 4 Toluene 155 12 6 43 1.0 mol % of KOtBu 60.4 44.7 25.8 14.8 5 Toluene 155 60 6 58 5 bar of H2 66.5 57.1 31.0 9.9 6 p-Xylene 155 12 6 38 1.0 mol % of water 77.5 52.9 21.6 16.9 7 p-Xylene 155 12 6 41 5 mol % of water 84.0 49.0 21.1 12.8 8 p-Xylene 155 15 6 46 77.5 49.1 23.7 13.1 9 p-Xylene 155 24 6 44 96.3 17.0 48.6 19.9 10 p-Xylene 155 24 6 53 1.0 mol % of water 84.6 51.8 20.8 12.9 11 p-Xylene 180 12 6 50 100.0 0.4 46.1 27.9 12 p-Xylene 180 12 6 50 5 mol % of H2O 100.0 0.4 48.2 27.4 .sup.a)conditions unless indicated otherwise: 50 ml of solvent, batch size 25 mmol of diethylene glycol, 0.1 mol % of catalyst complex XIVb (per alcohol group); .sup.b)evaluation by GC (% by area); .sup.c)product selectivity determined by GC; .sup.d)molar equivalents of NH.sub.3 per OH function on the substrate; .sup.f)batch size 35 mmol of diethylene glycol in 70 ml of solvent

(9) TABLE-US-00004 TABLE 2b Reaction of diethylene glycol Solvent T Time NH.sub.3 Reaction Conversion.sup.b) Selectivity.sup.c) No..sup.a) (waterfree) Catalyst [ C.] [h] [eq].sup.d) pressure (bar) Further conditions.sup.e) [%] a [%] b [%] c [%] 1 Toluol XIVb 155 12 2.0 12.3 83.52 37.60 13.93 25.58 2 Toluol XIVb 155 12 6 40.9 0.2 mol % KOH (aq. 20%) 73.94 39.35 37.29 15.28 3 Toluol XIVb 155 24 6 43.6 97.31 18.10 36.58 21.66 4 Toluol XIVb 155 15 6 45.7 0.05 mol % XIVb 95.97 17.66 40.46 26.67 5 Toluol XIVb 155 12 6 65.5 5 bar H2 61.84 69.16 18.61 8.01 6 Toluol XIVb 155 12 6 36.0 25 g t-Butanol, 25 ml Toluol 86.90 44.98 26.76 15.52 7 Toluol XIVb 165 12 6 45.1 98.22 12.52 40.92 21.86 8 Toluol XIVb 170 12 6 45.7 99.81 4.39 43.66 26.02 9 Toluol XIVb 180 2 6 47.2 0.2 mol % XIVb 95.81 19.45 41.17 19.87 10 Toluol XIVb 180 9 6 45.5 100.00 0.75 39.21 29.46 11 Toluol XIVb 180 12 6 37.7 100.00 0.00 32.75 38.67 12 Toluol XIVb 180 12 6 69.7 5 bar H2 96.05 20.68 54.70 16.64 13 Toluol XIVb 180 12 6 75.6 10 bar H2 86.11 35.73 47.22 13.77 14 Dioxane XIVb 155 12 6 38.0 68.17 65.02 20.29 9.21 15 Dioxane XIVb 180 12 6 34.1 99.66 4.65 40.23 34.65 16 THF XIVb 155 12 6 41.0 70.97 54.46 19.41 11.95 17 THF XIVb 155 12 9 51.9 81.65 53.75 23.60 13.51 18 THF XIVb 180 12 6 49.1 100.00 0.00 42.48 41.98 19 Toluol XIVa 155 12 6 40.7 68.02 69.62 9.60 9.52 20 Toluol XIVa 155 24 6 42.1 77.16 43.54 20.09 15.10 .sup.a)conditions unless indicated otherwise: 50 ml of solvent, batch size 25 mmol of diethylene glycol, 0.1 mol % of catalyst complex XIVa or XIVb (per alcohol group); .sup.b)evaluation by GC (% by area); .sup.c)product selectivity determined by GC; .sup.d)molar equivalents of NH.sub.3 per OH function on the substrate; .sup.e)mol % based on the OH function on the substrate

(10) TABLE-US-00005 TABLE 3a Reaction of MEG (monoethylene glycol) T Time NH.sub.3 Reaction Selectivity.sup.c) No..sup.a) Solvent [ C.] [h] [eq].sup.d) pressure (bar) Further conditions Conversion.sup.b) a b c 1 Toluene 155 12 6 42 0.2 mol % of KOtBu 62.9 47.5 25.0 0.5 2 Toluene 155 12 6 41 1 mol % of KOtBu 75.9 39.9 26.8 0.3 3 Toluene 155 12 6 44 19.3 48.3 21.8 0.6 4 Toluene 155 12 6 42 17 eq. of water 21.6 55.6 36.4 0.0 .sup.a)conditions unless indicated otherwise: 50 ml of solvent, batch size 25 mmol of monoethylene glycol, 0.1 mol % of catalyst complex XIVb (per alcohol group), .sup.b)evaluation by GC (% by area), .sup.c)product selectivity determined by GC, .sup.d)molar equivalents of NH.sub.3 per OH function on the substrate

(11) TABLE-US-00006 TABLE 3b Reaction of MEG (monoethylene glycol) Selectivity.sup.c) Solvent T Time NH.sub.3 Reaction Conversion.sup.b) a b c No..sup.a) (waterfree) catalyst [ C.] [h] [eq].sup.d) pressure (bar) Further conditions') [%] [%] [%] [%] 1 Toluol XIVb 155 12 6 39.8 0.2 mol % KOH (aq, 20%) 59.98 41.02 22.73 12.92 2 Toluol XIVb 180 12 6 46.8 94.72 11.00 19.72 44.48 3 Toluol XIVb 180 12 6 47.4 1 mol % KOtBu 100.00 0.66 21.17 49.04 4 Toluol XIVb 180 12 6 66.1 5 bar H2 85.23 15.49 26.30 45.17 5 p-Xylol XIVb 155 24 6 45.8 45.78 43.94 18.28 0.22 6 THE XIVb 155 12 6 41.7 2 mol % KOtBu 56.85 47.52 18.66 1.98 7 THF XIVb 180 12 6 47.2 88.49 10.02 22.50 46.63 8 Toluol XIVa 180 24 6 28.0 100.00 6.39 11.51 60.53 9 Toluol XIVa 155 12 6 40.8 1 mol % KOtBu 50.47 52.84 19.81 4.31 .sup.a)conditions unless indicated otherwise: 50 ml of solvent, batch size 25 mmol of monoethylene glycol, 0.1 mol % of catalyst complex XIVa or XIVb (per alcohol group); .sup.b)evaluation by GC (% by area); .sup.c)product selectivity determined by GC; .sup.d)molar equivalents of NH.sub.3 per OH function on the substrate; .sup.e)mol % based on the OH functions on the substrate

(12) TABLE-US-00007 TABLE 4 Reaction of 2,5-furandimethanol Selectivity.sup.c) Solvent T Time NH.sub.3 Reaction Conversion.sup.b) a b No..sup.a) (waterfree) Catalyst [ C.] [h] [eq].sup.d) Pressure (bar) [%] [%] [%] 1 THF XIVb 140 21 6 35.2 100.00 0.40 96.36 2 THF XIVb 150 6 6 38.8 100.00 7.14 87.75 3 THF XIVb 150 12 6 40.4 100.00 0.27 84.44 4 THF XIVb 150 18 6 37.1 100.00 0.31 94.15 5 t-amylalcohol XIVb 140 9 6 31.4 99.59 9.55 84.97 6 t-amylalcohol XIVb 150 5 6 37.1 100.00 2.70 90.10 7 t-amylalcohol XIVb 150 18 6 37.9 100.00 0.00 95.60 .sup.a)conditions unless indicated otherwise: 50 ml of solvent, batch 25 mmol of 2,5-furandimethanol, 0.1 mol % of catalyst complex XIVb (per alcohol group); .sup.b)evaluation by GC (% by area); .sup.c)product selectivity determined by GC; .sup.d)molar equivalents of NH.sub.3 per OH function on the substrate

(13) TABLE-US-00008 TABLE 5 Reaction of alkyldiols 0 Selectivity.sup.c) Solvent T Time NH.sub.3 Reaction Conversion.sup.b) a b c No..sup.a) Alcohol (waterfree) catalyst [ C.] [h] [eq].sup.d) Pressure (bar) [%] [%] [%] [%] 1 1,3-propanediol Toluol XIVb 135 12 6 41.1 99.73 8.95 35.79 2 1,5-pentanediol Toluol XIVb 180 12 6 44.1 80.51 58.26 19.24 15.13 3 1,6-hexanediol Toluol XIVb 155 12 6 34.0 100.00 1.14 91.38 0.51 4.sup.e) 1,9-nonanediol THF XIVb 150 24 6 15.0 97.70 10.60 74.60 5 1,10-decanediol Toluol XIVb 155 12 6 44.3 95.19 1.36 93.25 6 C.sub.36-diol THF XIVb 155 12 6 38.2 Amine number (AZ).sup.f): 197 AZ (primary amines): 196 AZ (secondary Amines) < 1 AZ (tertiary amines): 1 .sup.a)conditions unless indicated otherwise: 50 ml of solvent, batch size 25 mmol of alkyldiol, 0.1 mol % of catalyst complex XIVb (per alcohol group); .sup.b)evaluation by GC (% by area); .sup.c)product selectivity determined by GC; .sup.d)molar equivalents of NH.sub.3 per OH function on the substrate; .sup.e)batch size: 50 mmol 1,9-nonanediol in a 100 ml autoclave; .sup.f)definition of amine number (AZ), see Thieme Rompp Chemielexikon

(14) TABLE-US-00009 TABLE 6 Reaction of 1,4-bis(aminomethyl)cyclohexane Selectivity.sup.c) Solvent T Time NH.sub.3 Reaction- Conversion.sup.b) a b No..sup.a) Alcohol (waterfree) Catalyst [ C.] [h] [eq].sup.d) pressure [bar] [%] [%] [%] 1 1,4-bis(hydroxymethyl)cyclohexane THF XIVb 155 12 6 45.5 100.00 0.63 94.35 .sup.a)50 ml solvent, 25 mmol 1,4-(bishydroxymethyl)cyclohexane, 0.1 mol %catalyst complex XIVb (per alcohol group); .sup.b)evaluation by GC (% by area); .sup.c)product selectivity determined by GC; .sup.d)molar equivalents NH.sub.3 per OH function on the substrate

(15) TABLE-US-00010 TABLE 7 Reaction of ,-alkanol amines Selectivity.sup.c) Solvent T Time NH.sub.3 Reaction Conversion.sup.b) a b No..sup.a) Alcohol (waterfree) catalyst [ C.] [h] [eq].sup.d) pressure [bar] [%] [%] [%] 1 3-aminopropane-1-ol Toluol XIVb 135 12 6 35.2 45.54 46.98 2.sup.e) 4-aminobutane-1-ol THF XIVb 180 12 6 24.8 77.21 9.48 85.24 3 2-(2-aminoethoxy)ethanol Toluol XIVb 155 15 6 41.7 41.01 50.29 24.58 4 monoaminoethanol Toluol XIVb 155 15 6 42.3 72.86 69.39 12.28 5 monoaminoethanol Toluol XIVb 180 12 6 71.5 95.92 66.17 19.25 .sup.a)conditions unless indicated otherwise: 50 ml of solvent, batch size 25 mmol of alkanol amine, 0.1 mol % of catalyst complex XIVb (per alcohol group); .sup.b)evaluation by GC (% by area); .sup.c)product selectivity determined by GC, .sup.d)molar equivalents of NH.sub.3 per OH function on the substrate; .sup.d)batch size: 50 mmol in 300 ml-autoclave