ORGANORUTHENIUM CARBIDE COMPLEXES AS PRECATALYSTS FOR OLEFIN METATHESIS

Abstract

Embodiments in accordance with the present invention encompass an organoruthenium compound of the formula (I) or formula (II):

##STR00001##

Wherein X, L, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, Ar.sub.1 and Ar.sub.2 are as defined herein. Also disclosed herein are the use of organoruthenium compound of the formula (I) or formula (II) as (pre)catalysts for the olefin metathesis reactions, as well as to the process for carrying out the olefin metathesis reaction.

Claims

1. A compound of the formula I: ##STR00027## wherein: X is chlorine, bromine or iodine; L is PR.sub.3, where each R is independently selected from the group consisting of isopropyl, sec-butyl, tert-butyl, cyclohexyl, bicyclo(C.sub.5-C.sub.10)alkyl, phenyl, benzyl, isopropoxy, sec-butoxy, tert-butoxy, cyclohexyloxy, phenoxy and benzyloxy; R.sub.1 is selected from the group consisting of methyl, ethyl, isopropyl, sec-butyl, tert-butyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl and substituted or unsubstituted naphthyl; Ar.sub.1 is selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl and substituted or unsubstituted naphthyl; wherein said substituents are selected from the group consisting of methyl, ethyl, iso-propyl, tert-butyl and phenyl; and with the proviso that when X is chlorine, R.sub.1 is not 2,4,6-trimethylphenyl.

2. The compound according to claim 1, wherein: X is chlorine or iodine; R.sub.1 and Ar.sub.1 are both substituted phenyl; and L is PR.sub.3, where each R is independently selected from the group consisting of isopropyl, sec-butyl, tert-butyl, cyclohexyl and phenyl.

3. The compound according to claim 1, wherein: X is chlorine; R.sub.1 and Ar.sub.1 are independently selected from the group consisting of phenyl, 2-methylphenyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-ethylphenyl, 2,4-diethylphenyl, 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-isopropylphenyl and 2,6-diisopropylphenyl; and L is tri(isopropyl)phosphine or tricyclohexylphosphine.

4. The compound according to claim 1, wherein: X is chlorine; R.sub.1 and Ar.sub.1 are independently selected from the group consisting of phenyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,4-diethylphenyl, 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-isopropylphenyl and 2,6-diisopropylphenyl; and L is tricyclohexylphosphine.

5. The compound according to claim 1, wherein: X is iodine; R.sub.1 and Ar.sub.1 are independently selected from the group consisting of 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diethylphenyl, 2,4,6-triethylphenyl and 2,6-diisopropylphenyl; and L is tricyclohexylphosphine.

6. The compound according to claim 1, which is selected from the group consisting of: ##STR00028## 1,3-bis(2,4,6-trimethylphenyl)-imidazolidin-2-ylidene-tricyclohexylphosphine-ruthenium carbide diiodide; ##STR00029## 1,3-bis(2,6-diisopropylphenyl)-imidazolidin-2-ylidene-tricyclohexylphosphine-ruthenium carbide dichloride; ##STR00030## 1,3-bis(2,6-diisopropylphenyl)-imidazolidin-2-ylidene-tricyclohexylphosphine-ruthenium carbide diiodide

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 in the presence of a chemical activator.

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

12. A compound of the formula II: ##STR00031## wherein: X is chlorine, bromine or iodine; L is PR.sub.3, where R is independently selected from the group consisting of isopropyl, sec-butyl, tert-butyl, cyclohexyl, bicyclo(C.sub.5-C.sub.10)alkyl, phenyl, benzyl, isopropoxy, sec-butoxy, tert-butoxy, cyclohexyloxy, phenoxy and benzyloxy; R.sub.2 and R.sub.3 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C.sub.1-C.sub.6)alkyl, (C.sub.6-C.sub.10)aryl, methoxy, ethoxy, linear or branched (C.sub.1-C.sub.6)alkoxy, (C.sub.6-C.sub.10)aryloxy, NHCO(C.sub.1-C.sub.6)alkyl, NHCO-perfluoro(C.sub.1-C.sub.6)alkyl, SO.sub.2N((C.sub.1-C.sub.6)alkyl).sub.2 and NO.sub.2; or R.sub.2 and R.sub.3 taken together with the carbon atom to which they are attached to form a (C.sub.3-C.sub.7)cycloalkyl ring; 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 linear or branched (C.sub.1-C.sub.6)alkyl; Ar.sub.2 is selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl and substituted or unsubstituted naphthyl; wherein said substituents are selected from the group consisting of methyl, ethyl, iso-propyl, tert-butyl and phenyl.

13. The compound according to claim 12, wherein: X is chlorine or iodine; each R.sub.2, R.sub.3, R.sub.4 and R.sub.5 is independently selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl and phenyl; Ar.sub.2 is substituted phenyl; and L is PR.sub.3, where each R is independently selected from the group consisting of isopropyl, sec-butyl, tert-butyl, cyclohexyl and phenyl.

14. The compound according to claim 12, wherein: X is chlorine; R.sub.2 and R.sub.3 taken together with the carbon atom to which they are attached to form a cyclopentyl, cyclohexyl or cycloheptyl ring; each R.sub.4 and R.sub.5 is independently selected from the group consisting of hydrogen, methyl, ethyl and iso-propyl; Ar.sub.2 is selected from the group consisting of phenyl, 2-methylphenyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-ethylphenyl, 2,4-diethylphenyl, 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-isopropylphenyl and 2,6-diisopropylphenyl; and L is tri(isopropyl)phosphine or tricyclohexylphosphine.

15. The compound according to claim 12, wherein: X is chlorine; each R.sub.2, R.sub.3, R.sub.4 and R.sub.5 independently is methyl or ethyl; Ar.sub.2 is selected from the group consisting of phenyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,4-diethylphenyl, 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-isopropylphenyl and 2,6-diisopropylphenyl; and L is tricyclohexylphosphine.

16. The compound according to claim 12, wherein: X is iodine; each R.sub.2, R.sub.3, R.sub.4 and R.sub.5 independently is methyl or ethyl; Ar.sub.2 is selected from the group consisting of 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diethylphenyl, 2,4,6-triethylphenyl and 2,6-diisopropylphenyl; and L is tricyclohexylphosphine.

17. The compound according to claim 1, which is selected from the group consisting of: ##STR00032## 1-(2,6-diethylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene-triisopropylphosphine ruthenium carbide dichloride; ##STR00033## 1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene-triisopropylphosphine ruthenium carbide dichloride; and ##STR00034## 1-(2,6-diethylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene-triisopropylphosphine ruthenium carbide diiodide.

18. A process for carrying out a metathesis reaction of olefins, comprising contacting at least one olefin with the compound of claim 12 as a procatalyst.

19. The process according to claim 18, wherein the metathesis reaction is carried out in an organic solvent.

20. The process according to claim 19, wherein the organic solvent is selected from the group consisting of dichloromethane, dichloroethane, toluene, ethyl acetate and a mixture in any combination thereof.

Description

EXAMPLE 1

[0138] ##STR00020##

[0139] To a solution of dimethyl 3-methylenecyclopropane-1,2-dicarboxylate (0.613 g, 3.6 mmol, 1.8 equiv.) in dry, deoxygenated dichloromethane (20 mL) complex (A-1) (1.698 g, 2 mmol, 1 equiv.) was added as solid. The mixture was refluxed under argon atmosphere for 2 h. After that time the mixture was cooled down to rt. From that point all operations were carried out in air atmosphere. Volume of the dichloromethane was reduced to ca. 5 mL and methanol (5 mL) was added. The remaining dichloromethane was slowly removed using rotary evaporator and crystals formed were filtered, washed with methanol (31 mL) and dried in vacuum. The title compound (IA) was obtained as yellow crystalline solid, 1.37 g (89%), and was characterized by NMR as follows:

[0140] .sup.1H NMR (601 MHz, CDCl.sub.3): 6.95 (s, 2H), 6.89 (s, 2H), 4.14-4.00 (m, 4H), 2.54 (s, 6H), 2.49 (s, 6H), 2.34-2.26 (m, 6H), 2.24 (s, 3H), 1.92-1.84 (m, 6H), 1.72-1.64 (m, 6H), 1.64-1.58 (m, 3H), 1.24-1.06 (m, 15H).

[0141] .sup.13C NMR (151 MHz, CDCl.sub.3): 479.2, 212.6, 212.0, 138.3, 138.2, 138.0, 137.9, 137.2, 136.8, 135.1, 129.3, 129.2, 128.4, 127.7, 126.1, 113.7, 53.4, 52.0, 51.9, 50.9, 50.8, 31.1, 31.0, 29.3, 27.9, 27.8, 26.3, 21.2, 20.9, 19.7, 18.7.

[0142] .sup.31P NMR (243 MHz, CDCl.sub.3): 34.1.

EXAMPLE 2

[0143] ##STR00021##

[0144] To a solution of complex (B-1) (1.71 g, 2 mmol, 1 equiv.) in dry, deoxygenated dichloromethane (20 mL) tricyclohexylphosphine (0.673 g, 2.4 mmol, 1.2 equiv.) was added as solid under argon atmosphere. The mixture was stirred for 10 min at rt and dimethyl 3-methylenecyclopropane-1,2-dicarboxylate (0.681 g, 4 mmol, 2 equiv.). The mixture was refluxed under argon atmosphere for 3 h. After that time the mixture was cooled down to rt. From that point all operations were carried out in air atmosphere. Volume of the dichloromethane was reduced to ca. 5 mL and methanol (5 mL) was added. The remaining dichloromethane was slowly removed using rotary evaporator and crystals formed were filtered, washed with methanol (31 mL) and dried in vacuum. The title compound (IC) was obtained as orange crystalline solid, 1.61 g (84%), and was characterized by NMR as follows:

[0145] .sup.1H NMR (601 MHz, CDCl.sub.3): 6.93 (s, 2H), 6.84 (s, 2H), 4.19-4.11 (m, 2H), 4.09-4.02 (m, 2H), 2.98-2.76 (br, 3H), 2.71 (s, 6H), 2.61 (s, 6H), 2.26 (s, 3H), 2.23 (s, 3H), 1.95 (br, 6H), 1.75-1.60 (m, 9H), 1.26-1.08 (m, 15H).

[0146] .sup.13C NMR (151 MHz, CDCl.sub.3): 475.8, 211.4, 210.9, 138.1, 137.9, 137.8, 137.7, 137.1, 135.8, 129.5, 129.4, 53.4, 52.5, 52.4, 51.6, 51.5, 33.9, 33.8, 30.5, 27.8, 27.8, 26.4, 22.7, 21.1, 21.0, 20.8.

[0147] .sup.31P NMR (243 MHz, CDCl.sub.3): 32.3.

EXAMPLE 3

[0148] ##STR00022##

[0149] To a solution of complex (B-2) (1.88 g, 2 mmol, 1 equiv.) in dry, deoxygenated dichloromethane (20 mL) tricyclohexylphosphine (0.673 g, 2.4 mmol, 1.2 equiv.) was added as solid under argon atmosphere. The mixture was stirred for 10 min at rt and dimethyl 3-methylenecyclopropane-1,2-dicarboxylate (0.442 g, 2.6 mmol, 1.3 equiv.). The mixture was refluxed under argon atmosphere for 18 h. After that time the mixture was cooled down to rt. From that point all operations were carried out in air atmosphere. Volume of the dichloromethane was reduced to ca. 5 mL and methanol (5 mL) was added. The remaining dichloromethane was slowly removed using rotary evaporator and crystals formed were filtered, washed with methanol (31 mL) and dried in vacuum. The title compound (ID) was obtained as orange crystalline solid, 1.74 g (84%), and was characterized by NMR as follows:

[0150] .sup.1H NMR (601 MHz, CDCl.sub.3): 7.38-7.30 (m, 1H), 7.29-7.20 (m, 3H), 7.18-7.10 (m, 2H), 4.30-4.12 (m, 4H), 3.90 (septet, J=6.6 Hz, 4H), 2.75 (q, J=11.9 Hz, 3H), 1.96-1.87 (m, 6H), 1.70-1.62 (m, 6H), 1.61-1.55 (m, 3H), 1.50 (d, J=6.5 Hz, 5H), 1.31 (dd, J=12.1, 6.7 Hz, 11H), 1.26-1.02 (m, 23H).

[0151] .sup.13C NMR (151 MHz, CDCl.sub.3): 471.2, 214.6, 214.1, 149.0, 147.7, 139.1, 135.9, 129.4, 129.2, 124.6, 123.6, 55.3 (2C), 53.8 (2C), 53.4, 34.4, 34.3, 30.7, 29.7, 28.2, 27.8, 27.7 (2C), 26.4, 26.2, 25.1, 23.4.

[0152] .sup.31P NMR (243 MHz, CDCl.sub.3): 32.8.

EXAMPLE 4

[0153] ##STR00023##

[0154] To a solution of complex (D-1) (1.16 g, 2 mmol, 1 equiv.) in dry, deoxygenated dichloromethane (20 mL) triisopropylphosphine (0.497 mL, 0.417 g, 2.6 mmol, 1.3 equiv.) was added followed by dimethyl 3-methylenecyclopropane-1,2-dicarboxylate (0.442 g, 2.6 mmol, 1.3 equiv.). The mixture was stirred at rt under argon atmosphere for 18 h. From that point all operations were carried out in air atmosphere. Volume of the dichloromethane was reduced to ca. 5 mL and methanol (5 mL) was added. The remaining dichloromethane was slowly removed using rotary evaporator and crystals formed were filtered, washed with methanol (31 mL) and dried in vacuum. The title compound (IIA) was obtained as yellow crystalline solid, 1.09 g (90%), and was characterized by NMR as follows:

[0155] .sup.1H NMR (601 MHz, CD.sub.2Cl.sub.2): 7.38-7.33 (m, 1H), 7.33-7.28 (2H), 2.85 (dq, J=14.7, 7.3 Hz, 2H), 2.73 (ddt, J=14.5, 11.0, 7.3 Hz, 3H), 2.53 (dq, J=14.8, 7.4 Hz, 2H), 2.09 (s, 2H), 1.73 (s, 6H), 1.38-1.30 (m, 24H), 1.17 (t, J=7.4 Hz, 6H).

[0156] .sup.13C NMR (151 MHz, CD.sub.2Cl.sub.2): 473.5, 265.7, 265.2, 142.7, 139.6, 129.0, 126.6, 80.9 (2C), 58.7, 58.6, 52.50 (2C), 31.2, 29.1, 25.5, 22.5, 22.4, 19.8, 14.9.

[0157] .sup.31P NMR (243 MHz, CD.sub.2C.sub.2): 40.6.

EXAMPLE 5

[0158] ##STR00024##

[0159] To a solution of complex (D-2) (1.51 g, 2.5 mmol, 1 equiv.) in dry, deoxygenated toluene (25 mL) triisopropylphosphine (0.621 mL, 0.521 g, 3.25 mmol, 1.3 equiv.) was added followed by dimethyl 3-methylenecyclopropane-1,2-dicarboxylate (0.553 g, 3.25 mmol, 1.3 equiv.). The mixture was stirred at 80 C. under argon atmosphere for 18 h. After that time the mixture was cooled down to rt. From that point all operations were carried out in air atmosphere. Toluene was evaporated in vacuum and the residue was re-dissolved in small amount of dichloromethane (ca. 7.mL). Methanol (7.mL) was added and dichloromethane was slowly removed using rotary evaporator. Crystals formed were filtered, washed with methanol (31.5 mL) and dried in vacuum. The title compound (IB) was obtained as yellow crystalline solid, 1.32 g (84%), and was characterized by NMR as follows:

[0160] .sup.1H NMR (601 MHz, C.sub.6D.sub.6): 7.20-7.17 (m, 2H), 7.15-7.12 (m, 1H), 3.26 (septet, J=6.4 Hz, 2H), 2.68 (ddt, J=14.5, 10.8, 7.3 Hz, 3H), 1.93 (s, 6H), 1.66 (s, 2H), 1.58 (d, J=6.3 Hz, 6H), 1.30-1.24 (m, 24H), 1.03 (s, 6H).

[0161] .sup.13C NMR (151 MHz, C.sub.6D.sub.6): 472.2, 268.3, 267.8, 147.8, 137.1 (2C), 130.00, 125.7, 79.8 (2C), 58.7 (2C), 52.3 (2C), 31.0, 30.2, 29.2, 27.7, 25.0, 22.6, 22.5, 20.0.

[0162] .sup.31P NMR (243 MHz, C.sub.6D.sub.6): 39.8.

EXAMPLE 6

[0163] ##STR00025##

[0164] To a solution of complex (B-3) (1.89 g, 2.5 mmol, 1 equiv.) in dry, deoxygenated dichloromethane (25 mL) tricyclohexylphosphine (0.841 g, 3 mmol, 1.2 equiv.) was added as solid under argon atmosphere. The mixture was stirred for 10 min at rt and dimethyl 3-methylenecyclopropane-1,2-dicarboxylate (0.553 g, 3.25 mmol, 1.3 equiv.). The mixture was refluxed under argon atmosphere for 2 h. After that time the mixture was cooled down to rt. From that point all operations were carried out in air atmosphere. Volume of the dichloromethane was reduced to ca. 7 mL and methanol (7 mL) was added. The remaining dichloromethane was slowly removed using rotary evaporator and crystals formed were filtered, washed with methanol (31.5 mL) and dried in vacuum. The title compound (B) was obtained as yellow crystalline solid, 1.81 g (85%), and was characterized by NMR as follows:

[0165] .sup.1H NMR (601 MHz, CDCl.sub.3): 7.48-7.06 (m, 6H), 4.34-3.98 (m, 4H), 3.90-3.35 (m, 4H), 2.30-2.19 (m, 3H), 1.89-1.80 (m, 6H), 1.65-1.00 (m, 48H).

[0166] .sup.13C NMR (151 MHz, CDCl.sub.3): 476.2, 215.0, 214.4, 149.1, 147.8, 138.8, 135.1, 129.3, 124.2, 123.5, 54.4, 53.7, 31.3, 31.2, 29.4, 29.3, 28.1, 27.7, 27.6, 27.4, 26.3, 25.8, 23.4, 23.1.

[0167] .sup.31P NMR (243 MHz, CDCl.sub.3): 35.4.

EXAMPLE 7

[0168] ##STR00026##

[0169] To a solution of complex (D-3) (1.1 g, 1.45 mmol, 1 equiv.) in dry, deoxygenated dichloromethane (15 mL) triisopropylphosphine (0.359 mL, 0.301 g, 1.88 mmol, 1.3 equiv.) was added followed by dimethyl 3-methylenecyclopropane-1,2-dicarboxylate (0.32 g, 1.88 mmol, 1.3 equiv.). The mixture was stirred at rt under argon atmosphere for 18 h. From that to point all operations were carried out in air atmosphere. Volume of the dichloromethane was reduced to ca. 5 mL and methanol (5 mL) was added. The remaining dichloromethane was slowly removed using rotary evaporator and crystals formed were filtered, washed with methanol (31 mL) and dried in vacuum. The title compound (IID) was obtained as orange crystalline solid, 0.945 g (83%), and was characterized by NMR as follows:

[0170] .sup.1H NMR (601 MHz, CD.sub.2Cl.sub.2): 7.34-7.26 (m, 3H), 3.30-3.12 (m, 5H), 2.66 (dq, J=14.9, 7.4 Hz, 2H), 2.11 (s, 2H), 1.87 (s, 6H), 1.41 (s, 6H), 1.37-1.31 (m, 18H), 1.22 (t, J=7.4 Hz, 6H).

[0171] .sup.31P NMR (243 MHz, CD.sub.2Cl.sub.2): 36.

[0172] 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.