ORGANORUTHENIUM COMPLEXES AS PRECATALYSTS FOR OLEFIN METATHESIS

Abstract

Embodiments in accordance with the present invention encompass an organoruthenium compound of the formula I: (I) wherein X, Y, L.sub.1, L.sub.2, R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are as defined herein. Also disclosed herein are the use of organoruthenium compound of the formula I as (pre)catalysts for the olefin metathesis reactions, as well as to the process for carrying out the olefin metathesis reaction.

##STR00001##

Claims

1. A compound of the formula I: ##STR00026## wherein: ##STR00027## is a monovalent anionic bidentate ligand; Y is oxygen or sulfur; L.sub.2 is a neutral ligand; R.sub.1 is selected from the group consisting of hydrogen, (C.sub.1-C.sub.20)alkyl, (C.sub.2-C.sub.20)alkenyl, (C.sub.2-C.sub.20)alkynyl and (C.sub.6-C.sub.10)aryl; R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are the same or different and each independently selected from the group consisting of hydrogen, halogen, (C.sub.1-C.sub.16)alkyl, (C.sub.1-C.sub.16)alkoxy, (C.sub.1-C.sub.16)perfluoroalkyl, (C.sub.3-C.sub.7)cycloalkyl, (C.sub.2-C.sub.16)alkenyl, (C.sub.6-C.sub.14)aryl, (C.sub.6-C.sub.14)perfluoroaryl, (C.sub.3-C.sub.12)heterocyclyl, —OR.sub.6, —NO.sub.2, —COOH, —COOR.sub.6, —CONR.sub.6R.sub.7, —SO.sub.2NR.sub.6R.sub.7, —SO.sub.2R.sub.6, —CHO, —COR.sub.6, wherein R.sub.6 and R.sub.7 are the same or different and each independently selected from the group consisting of (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)perfluoroalkyl, (C.sub.6-C.sub.14)aryl, (C.sub.6-C.sub.14)perfluoroaryl; or wherein two or more of R.sub.2, R.sub.3, R.sub.4 and R.sub.5 taken together with the carbon atoms to which they are attached to form a substituted or unsubstituted, fused (C.sub.4-C.sub.5)carbocyclic ring, or a substituted or unsubstituted, fused aromatic ring.

2. The compound according to claim 1, wherein: Y is oxygen; R.sub.1 is hydrogen; R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl and —NO.sub.2; ##STR00028## is of the formula 2: ##STR00029## wherein: a and b are integers from 0 to 5; each R.sub.8 and R.sub.9 may be the same or different and independently of the other selected from the group consisting of hydrogen, halogen, (C.sub.1-C.sub.16)alkyl, (C.sub.1-C.sub.16)alkoxy, (C.sub.1-C.sub.16)perfluoroalkyl, (C.sub.3-C.sub.7)cycloalkyl, (C.sub.2-C.sub.1)alkenyl, (C.sub.6-C.sub.14)aryl, (C.sub.6-C.sub.14)perfluoroaryl, (C.sub.3-C.sub.12)heterocyclyl, —OR.sub.6, —NO.sub.2, —COOH, —COOR.sub.6, —CONR.sub.6R.sub.7, —SO.sub.2NR.sub.6R.sub.7, —SO.sub.2R.sub.6, —CHO, —COR.sub.6, wherein R.sub.6 and R.sub.7 are the same or different and each independently selected from the group consisting of (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)perfluoroalkyl, (C.sub.6-C.sub.14)aryl, (C.sub.6-C.sub.14)perfluoroaryl.

3. The compound according to claim 1, wherein: Y is oxygen; R.sub.1 is hydrogen; R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl and —NO.sub.2; L.sub.2 is a ligand of the formula 3a or 3b: ##STR00030## wherein: R.sub.10 and R.sub.11 are the same or different and each independently selected from the group consisting of (C.sub.1-C.sub.12)alkyl, (C.sub.3-C.sub.12)cycloalkyl, (C.sub.2-C.sub.12alkenyl and substituted or unsubstituted (C.sub.6-C.sub.14)aryl; R.sub.12 R.sub.13, R.sub.14 and R.sub.15 are the same or different and each independently selected from the group consisting of hydrogen, (C.sub.1-C.sub.12)alkyl, (C.sub.3-C.sub.12)cycloalkyl, (C.sub.2-C.sub.12)alkenyl, (C.sub.6-C.sub.14)aryl, optionally substituted with at least one of (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)perhaloalkyl, (C.sub.1-C.sub.6)alkoxy or halogen; or R.sub.12, R.sub.13, R.sub.14, R.sub.15 may optionally join together with the carbon atoms to which they are attached to form a substituted or unsubstituted, fused (C.sub.4-C.sub.8)carbocyclic ring, or a substituted or unsubstituted, fused aromatic ring.

4. The compound according to claim 1, wherein: ##STR00031## is selected from the group consisting of: a group of the formula 2a: ##STR00032## a group of the formula 2b: ##STR00033## a group of the formula 2c: ##STR00034## a group of the formula 2d: ##STR00035## a group of the formula 2e: ##STR00036## and a group of the formula 2f: ##STR00037##

5. The compound according to claim 1, wherein: L.sub.2 is selected from the group consisting of: ##STR00038##

6. The compound according to claim 1, which is selected from the group consisting of: ##STR00039##

7. A process for carrying out a metathesis reaction of olefins, comprising contacting at least one olefin with the compound of claim 1 as a procatalyst.

8. The process according to claim 7, wherein the metathesis reaction is carried out in an organic solvent.

9. The process according to claim 8, wherein the organic solvent is selected from the group consisting of dichloromethane, dichloroethane, toluene, ethyl acetate and a mixture in any combination thereof.

10. The process according to claim 7, wherein the metathesis reaction is carried out without any solvent.

11. The process according to claim 7, wherein the metathesis reaction is carried out in the presence of a chemical activator.

12. The process according to claim 7, wherein the chemical activator is a Bronsted or Lewis acid or a halo-derivative of alkane or silane.

13. The process according to claim 12, wherein the activator is hydrogen chloride, chlorotrimethylsilane or p-toluenesulfonic acid.

14. The process according to claim 7, wherein the metathesis reaction is a ring-opening metathetic polymerization of dicyclopentadiene.

15. The process according to claim 14, wherein the (pre)catalyst of the general formula 1 is added in the solid form to dicyclopentadiene.

16. The process according to claim 12, wherein the polymerization reaction is initiated by heating the mixture of dicyclopentadiene and the (pre)catalyst of the general formula 1 to a temperature of 30° C. or higher.

17. The process according to claim 5, wherein the metathesis reaction is carried out at a temperature of from 20 to 120° C.

18. The process according to claim 5, wherein the metathesis reaction is carried out in a period of from 1 minute to 24 hours.

19. The process according to claim 5, wherein the metathesis reaction is carried out in the presence of an additive promoting formation of cross bonds.

20. The process according to claim 5, wherein the metathesis reaction is carried out using the amount of the (pre)catalyst equal to or less than 1000 ppm.

Description

EXAMPLE 2

[0079] ##STR00020##

[0080] Solution of potassium tert-pentoxide in toluene (1.7 M, 2.09 mL, 1.22 eq) was added to the solution of imine 3 (0.80 g, 1.22 eq) in tetrahydrofuran (27 mL) and the resulted mixture was stirred at 40° C. for 20 min. Next LatMet-PPh.sub.3 (2.36 g, 2.91 mmol, 1 eq) was added and reaction was continued for 20 min. Solvents were evaporated to dryness, the residue was dissolved in cyclohexane:ethyl acetate 95:5 mixture (Eluent 1) and filtered through a short pad of silica gel (Eluent 1.fwdarw.cycylohexane:ethyl acetate 9:1 [Eluent 2]). Crude product was crystallized from dichloromethane/methanol mixture, brown crystals, 1.81 g, 84%.

[0081] .sup.1H NMR (600 MHz, CD.sub.2Cl.sub.2) δ ppm: 15.19 (s, 1H), 7.41 (s, 1H), 7.21 (ddd, J=8.7, 6.8, 1.9 Hz, 1H), 7.21 (ddd, J=8.7, 6.8, 1.9 Hz, 1H), 7.09 (bs, 1H), 7.04 (d, J=8.8 Hz, 2H), 6.91 (dd, J=7.8, 1.9 Hz, 1H), 6.88 (d, J=7.5 Hz, 2H), 6.72-6.68 (m, 2H), 6.43-6.41 (m, 2H), 6.33 (dd, J=7.4, 1.5 Hz, 1H), 6.25 (dd, J=7.6, 1.7 Hz, 1H), 6.10 (ddd, J=7.5, 6.6, 1.0 Hz, 1H), 5.94 (d, J=8.5 Hz, 1H), 4.11-4.04 (m, 1H), 3.92-3.75 (m, 3H), 2.68 (s, 3H), 2.48 (s, 3H), 2.38 (s, 3H), 2.31 (s, 6H), 1.70 (s, 3H), 1.12 (s, 2H), 0.90 (s, 3H).

[0082] .sup.13C NMR (150 MHz, CD.sub.2Cl.sub.2) δ ppm: 287.7, 222.2, 181.3, 169.8, 164.0, 149.9, 148.4, 139.9, 139.7, 139.1, 138.1, 137.3, 136.1, 134.7, 132.9, 132.0, 130.8, 130.4, 129.9, 129.8, 129.7, 129.2, 127.5, 126.9, 124.8, 124.1, 122.3, 119.4, 116.2, 113.3, 111.2, 51.7, 51.1, 21.4, 18.9, 18.5, 18.2, 17.5, 16.5.

EXAMPLE 3

[0083] ##STR00021##

[0084] Solution of potassium tert-pentoxide in toluene (1.7 M, 1.51 mL, 1.15 eq) was added to the solution of imine 4 (0.65 g, 1.15 eq) in tetrahydrofuran (22 mL) and the resulted mixture was stirred at 40° C. for 20 min. Next LatMet-PPh.sub.3 (1.81 g, 2.23 mmol, 1 eq) was added and reaction was continued for 20 min. Solvents were evaporated to dryness, the residue was dissolved in cyclohexane:ethyl acetate 95:5 mixture (Eluent 1) and filtered through a short pad of silica gel (Eluent 1.fwdarw.cycylohexane:ethyl acetate 9:1 [Eluent 2]). Crude product was crystallized from dichloromethane/methanol mixture, brown crystals, 1.36 g, 80%.

[0085] .sup.1H NMR (600 MHz, CD.sub.2Cl.sub.2) δ ppm: 15.16 (s, 1H), 7.46 (s, 1H), 7.21 (ddd, J=8.8, 6.8, 1.9 Hz, 1H), 7.12 (bs, 1H), 7.05-7.03 (m, 2H), 6.93-6.88 (m, 3H), 6.80 (t, J=7.6 Hz, 1H), 6.68 (ddd, J=8.4, 6.7, 1.7 Hz, 1H), 6.43-6.37 (m, 3H), 6.22 (dd, J=7.7, 1.7 Hz, 1H), 6.08 (ddd, J=7.4, 6.6, 0.9 Hz, 1H), 5.89 (d, J=8.4 Hz, 1H), 4.12-3.99 (m, 1H), 3.89-3.73 (m, 3H), 2.67 (s, 3H), 2.51 (s, 3H), 2.40 (s, 3H), 2.32 (d, J=24.8 Hz, 6H), 2.27-2.14 (m, 3H), 1.20-1.13 (m, 3H), 1.02 (dq, J=15.2, 7.6 Hz, 1H), 0.86 (t, J=7.5 Hz, 3H), 0.49 (t, J=7.6 Hz, 3H).

[0086] .sup.13C NM R (150M Hz, CD2Cl2) δ ppm: 287.7, 222.5, 181.2, 169.9, 164.2, 148.4, 148.3, 140.1, 139.9, 138.9, 138.1, 137.7, 137.3, 136.1, 136.0, 134.8, 132.9, 130.7, 130.4, 129.8, 129.7, 129.2, 125.2, 125.2, 124.1, 122.5, 119.0, 116.2, 113.3, 113.3, 111.1, 51.7, 51.1, 26.1, 23.6, 21.5, 21.4, 18.5, 18.2, 16.5, 15.8, 14.8.

EXAMPLE 4

[0087] ##STR00022##

[0088] Solution of potassium tert-pentoxide in toluene (1.7 M, 0.89 mL, 1.22 eq) was added to the solution of imine 5 (0.42 g, 1.22 eq) in tetrahydrofuran (12 mL) and the resulted mixture was stirred at 40° C. for 20 min. Next LatMet-PPh.sub.3 (1.0 g, 1.23 mmol, 1 eq) was added and reaction was continued for 20 min.

[0089] Solvents were evaporated to dryness, the residue was dissolved in cyclohexane:ethyl acetate 95:5 mixture (Eluent 1) and filtered through a short pad of silica gel (Eluent 1.fwdarw.cycylohexane:ethyl acetate 9:1 [Eluent 2]). Crude product was crystallized from dichloromethane/methanol mixture, brown crystals, 0.64 g, 65%.

[0090] .sup.1H NMR (600 MHz, CD.sub.2Cl.sub.2) δ ppm: 15.40 (s, 1H), 7.45 (s, 1H), 7.19 (ddd, J=8.7, 6.8, 1.9 Hz, 1H), 7.15 (bs., 1H), 7.06 (bs., 1H), 6.99 (dd, J=7.9, 1.5 Hz, 1H), 6.96 (d, J=8.7 Hz, 1H), 6.87 (dd, J=7.8, 1.9 Hz, 1H), 6.82-6.79 (m, 1H), 6.76-6.68 (m, 1H), 6.66 (ddd, J=8.3, 6.6, 1.6 Hz, 1H), 6.46-6.36 (m, 3H), 6.19 (dd, J=7.7, 1.7 Hz, 1H), 6.04-5.96 (m, 2H), 4.14-3.93 (m, 1H), 3.88-3.79 (m, 2H), 3.75 (bs, 1H), 3.06 (sept, J=6.8 Hz, 1H), 2.67 (s, 2H), 2.44 (s, 6H), 2.30 (s, 7H), 1.51 (d, J=6.6 Hz, 3H), 1.42 (sept, J=6.9 Hz, 1H), 1.13 (s., 3H), 0.82 (d, J=6.8 Hz, 3H), 0.52 (d, J=6.8 Hz, 3H), 0.44 (d, J=6.7 Hz, 3H)

[0091] .sup.13C NMR (150 MHz, CD.sub.2Cl.sub.2) δ ppm: 287.2, 221.8, 181.3, 169.8, 165.0, 164.9, 148.0, 146.4, 142.3, 141.3, 139.8, 138.7, 138.1, 136.2, 132.9, 130.4, 130.2, 130.0, 129.6, 129.2, 125.5, 124.6, 123.5, 122.6, 122.0, 119.0, 115.8, 113.2, 110.6, 51.9, 50.7, 29.6, 26.9, 26.3, 25.5, 23.2, 22.7, 21.4, 18.5, 18.3, 16.5.

EXAMPLE 5

[0092] ##STR00023##

[0093] Solution of potassium tert-pentoxide in toluene (1.7 M, 1.33 mL, 1.22 eq) was added to the solution of imine 6 (0.51 g, 1.22 eq) in tetrahydrofuran (18 mL) and the resulted mixture was stirred at 40° C. for 20 min. Next LatMet-PPh.sub.3 (1.5 g, 1.85 mmol, 1 eq) was added and reaction was continued for 20 min. Solvents were evaporated to dryness, the residue was dissolved in cyclohexane:ethyl acetate 95:5 mixture (Eluent 1) and filtered through a short pad of silica gel (Eluent 1.fwdarw.cycylohexane:ethyl acetate 9:1 [Eluent 2]). Crude product was crystallized from dichloromethane/methanol mixture, brown crystals, 1.11 g, 60%.

[0094] .sup.1H NMR (600 MHz, CD.sub.6) δ ppm: 15.35 (s, 1H), 7.37 (d, J=8.7 Hz, 2H), 7.29-2.27 (m, 1H), 7.01 (ddd, J=8.3, 6.7, 1.7 Hz, 1H), 6.83 (s, 1H), 6.68 (d, J=7.8 Hz, 2H), 6.62 (s, 1H), 6.59 (bs, 1H), 6.53 (s, 1H), 6.44-6.42 (m, 3H), 6.40-6.39 (m, 2H), 6.32 (bs, 1H), 5.50 (s, 1H), 4.28 (s, 1H), 3.42-3.31 (m, 2H), 3.28-3.19 (m, 2H), 3.18-3.11 (m, 2H), 3.11-3.01 (m, 2H), 2.69 (s, 6H), 2.53-2.49 (m, 3H), 2.17-2.08 (m, 3H), 1.99-1.88 (m, 2H), 1.33 (s, 3H), 1.08 (s, 1H).

[0095] .sup.13C NMR (150 MHz, C.sub.5D.sub.6) δ ppm: 223.1, 137.6, 137.5, 136.3, 134.3, 132.9, 130.6, 130.3, 129.7, 129.6, 129.2, 123.9, 113.4, 111.3, 53.4, 51.1, 21.2, 21.0, 18.8, 18.3, 18.1, 16.6.

EXAMPLE 6

[0096] ##STR00024##

[0097] Solution of potassium tert-pentoxide in toluene (1.7 M, 6.74 mL, 1.1 eq) was added to the suspension of salt 1 (4.72 g) in toluene (80 mL). Resulted mixture was stirred at room temperature for 30 min and then placed in oil bath at temperature of 80° C. After 10 min Ind.0 (9.24 g, 10.4 mmol, 1 eq, C.sub.Ind.0 0.12 M) was added and the mixture was stirred for 10 min. Next 7 (2.8 g, 1.5 eq) and triphenylphosphine (2.73 g, 1.0 eq) were added. Reaction mixture was stirred at 80° C. for 90 min, then cooled down to room temperature and filtered through a short pad of silica gel (eluent: toluene). Crude product was purified by crystallization and double recrystallization from dichloromethane/methanol mixture, dark green solid, 3.5 g, 39% yield.

EXAMPLE 7

[0098] ##STR00025##

[0099] Solution of potassium tert-pentoxide in toluene (1.7 M, 0.52 mL, 1.25 eq) was added to the solution of imine 5 (0.42 g, 1.22 eq) in tetrahydrofuran (12 mL) and the resulted mixture was stirred at 45° C. for 20 min. Next nitro-LatMet-PPh.sub.3 0.6, 0.7 mmol, 1 eq) was added and reaction was continued for 20 min. Solvents were evaporated to dryness. The obtained dark solid was purified by double recrystallization from dichloromethane/methanol mixture, black crystals, 0.69 g, 94%.

[0100] .sup.1H NMR (600 MHz, CD.sub.2Cl.sub.2) δ ppm: 16.08 (s, 1H), 7.63 (dd, J=9.3, 2.8 Hz, 1H), 7.48 (s, 1H), 7.24 (m, 2H), 7.16 (s, 1H), 7.09 (s, 1H), 7.03-6.99 (m, 2H), 6.90 (dd, J=8.2, 1.8 Hz, 1H), 6.87-6.83 (m, 1H), 6.68 (s, 1H), 6.48-6.44 (m, 2H), 6.32 (s, 1H), 5.97 (d, J=9.3 Hz, 1H), 4.18-4.05 (m, 1H), 3.92-3.80 (m, 3H), 3.04 (sept, J=6.8 Hz, 1H), 2.62 (s, 3H), 2.43 (s, 6H), 2.23 (s, 6H), 1.51 (d, J=6.7, 3H), 1.33 (dt, J=13.5, 6.7 Hz, 1H), 1.26 (s, 3H), 0.87 (d, J=6.8 Hz, 3H), 0.53 (d, J=6.9 Hz, 3H), 0.43 (d, J=6.8 Hz, 3H).

[0101] .sup.13C NMR (151 MHz, CD.sub.2Cl.sub.2) δ ppm: 289.8, 219.9, 185.5, 169.8, 165.8, 145.8, 145.8, 142.12, 142.1, 141.2, 139.8, 139.4, 139.2, 137.9, 137.4, 136.7, 136.4, 133.8, 133.5, 130.2, 129.9, 129.6, 126.2, 125.9, 124.5, 123.1, 122.3, 118.5, 118.3, 114.8, 113.9, 51.8, 50.9, 29.7, 26.8, 26.3, 25.6, 23.1, 22.7, 21.4, 21.4, 18.8, 18.5, 18.1, 16.8.

EXAMPLE 8

[0102] Two formulations were prepared. Formulation A: 5 mL of DCPD (6% m/m TCPD), LatMet-PCy.sub.3 (1.228 mg, 40 ppm in 50 μL of dry toluene). Formulation B: 5 mL of DCPD (6% m/m TCPD), hydrogen chloride solution in THF (0.75 M, 40 μL, 800 ppm). Formulation B was added to Formulation A, results:

TABLE-US-00001 Time [min] observations 0 Formulations A and B were mixed 2:20 End of gelation, gel point 3:00 Change in refractive index, discoloration, 205° C. 3:05 Smokes 3:15 T.sub.max = 210° C.

EXAMPLE 9

[0103] Two formulations were prepared. Formulation A: 5 mL of DCPD (6% m/m TCPD), 1c (1.176 mg, 40 ppm in 50 μL of dry toluene). Formulation B: 5 mL of DCPD (6% m/m TCPD), hydrogen chloride solution in THF (0.75 M, 60 μL, 1200 ppm). Formulation B was added to Formulation A, results:

TABLE-US-00002 Time [min] observations 0 Formulations A and B were mixed 0:12 End of gelation, gel point 0:20 Change in refractive index, discoloration, 207° C., smokes 0:25 T.sub.max = 210° C.

[0104] Although the invention has been illustrated by certain of the preceding examples, it is not to be construed as being limited thereby; but rather, the invention encompasses the generic area as hereinbefore disclosed. Various modifications and embodiments can be made without departing from the spirit and scope thereof.