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 (1): ##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)perhaloalkyl, (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)perhaloaryl, (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)perhaloalkyl, (C.sub.6-C.sub.14)aryl, (C.sub.6-C.sub.14)perhaloaryl; 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.8)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)perhaloalkyl, (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)perhaloaryl, (C.sub.6-C.sub.12)heterocyclyl, OR.sub.s, 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)perhaloalkyl, (C.sub.6-C.sub.14)aryl, (C.sub.6-C.sub.14)perhaloaryl.

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.12)alkenyl 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 2e: ##STR00035## a group of the formula 2f: ##STR00036##

5. The compound according to claim 1, wherein: L.sub.2 is selected from the group consisting of: ##STR00037##

6. The compound according to claim 1, which is selected from the group consisting of: ##STR00038##

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 (pre)catalyst.

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 11, wherein the chemical activator is selected from the group consisting of a Bronsted acid, a Lewis acid, a halo-derivative of alkane and a halo-derivative of silane.

13. The process according to claim 11, wherein the chemical activator is selected from the group consisting of hydrogen chloride, chlorotrimethylsilane and 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 formula (1) is added in the solid form to dicyclopentadiene.

16. The process according to claim 14, wherein the polymerization reaction is initiated by heating a mixture of dicyclopentadiene and the (pre)catalyst of the formula (1) to a temperature of 30? C. or higher.

17. The process according to claim 7, wherein the metathesis reaction is carried out at a temperature of from 20 to 120.sup.9 C.

18. The process according to claim 7, wherein the metathesis reaction is carried out in a period of from 1 minute to 24 hours.

19. The process according to claim 7, wherein the metathesis reaction is carried out in the presence of an additive promoting formation of cross bonds.

20. The process according to claim 7, wherein the metathesis reaction is carried out using the amount of the (pre)catalyst equal to or less than 1000 ppm.

Description

(1) In some embodiments, the metathesis reaction is carried out without any solvent. In some other embodiments, the metathesis reaction is carried out in the presence of a chemical activator. In general, the chemical activator is a Bronsted or Lewis acid or a halo-derivative of alkane or silane. Non-limiting examples of such activators include hydrogen chloride, chlorotrimethylsilane or p-toluenesulfonic acid.

(2) In some embodiments, the metathesis reaction is a ring-opening metathetic polymerization of dicyclopentadiene.

(3) In yet some other embodiments, the (pre)catalyst of the general formula (I) is added in the solid form to dicyclopentadiene.

(4) In one embodiment, the polymerization reaction is initiated by heating the mixture of dicyclopentadiene and the (pre)catalyst of the general formula (I) to a temperature of 30? C. or higher.

(5) In some embodiments, the starting material contains at least 94 wt. % of dicyclopentadiene.

(6) In another embodiment, the metathesis reaction is carried out at a temperature of from 20 to 120? C. In yet another embodiment, the metathesis reaction is carried out in a period of from 1 minute to 24 hours.

(7) In some embodiments, the metathesis reaction is carried out in the presence of an additive promoting formation of cross bonds.

(8) In one embodiment, the metathesis reaction is carried out using the amount of the (pre)catalyst equal to or less than 1000 ppm.

(9) Throughout the description of the invention and patent claims, if ppm (parts per million) units are used with relation to amount of substance, these are on a weight basis.

(10) Since the inventors do not wish to be bound by any particular mechanism of catalysis, the (pre)catalyst term is used to indicate that the compound according to the invention may be either the catalyst itself or a precursor of the active species being the actual catalyst.

(11) The definitions of groups not defined below should have the broadest meanings known in the art.

(12) The term optionally substituted means that one or more hydrogen atoms of the group in question have been replaced with the specified groups, provided that such a substitution results in formation of a stable compound.

(13) The term halo or halogen represents an element selected from F, Cl, Br, I.

(14) The term alkyl concerns a saturated, straight-chain or branched-chain hydrocarbon substituent having the specified number of carbon atoms. The non-limiting examples of alkyls are: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl.

(15) The term alkoxy concerns the alkyl substituent, as defined above, bound via an oxygen atom.

(16) The term perfluoroalkyl represents the alkyl, as defined above, wherein all hydrogens have been replaced with halogen atoms, where the halogen atoms may be identical or different.

(17) The term cycloalkyl concerns a saturated mono- or polycyclic hydrocarbon substituent having the specified number of carbon atoms. The non-limiting examples of a cycloalkyl substituent are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.

(18) The term alkenyl concerns a non-cyclic, straight or branched hydrocarbon chain having the specified number of carbon atoms and containing at least one carbon-carbon double bond. The non-limiting examples of alkenyls are: vinyl, allyl, 1-butenyl, 2-butenyl.

(19) The term aryl concerns an aromatic mono- or polycyclic hydrocarbon substituent having the specified number of carbon atoms. The non-limiting examples of aryl are: phenyl, mesityl, anthracenyl.

(20) The term heterocyclyl concerns aromatic as well as non-aromatic cyclic substituents having the specified number of carbon atoms, wherein one or more carbon atoms have been replaced with a heteroatom such as nitrogen, phosphorus, sulfur, oxygen, provided that there are no two directly connected oxygen or sulphur atoms in the ring. Non-aromatic heterocyclyls can contain from 4 to 10 atoms in the ring, whereas aromatic heterocyclyls must have at least 5 atoms in the ring. The benzo-fused systems also belong to heterocyclyls. The non-limiting examples of non-aromatic heterocyclyls are: pyrrolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, tetrahydropyranyl, dihydropyranyl, tetrahydrothiopyranyl, piperidinyl, morpholinyl, thiomorpholinyl, 2-pyrrolinyl, indolinyl. The non-limiting examples of aromatic heterocyclyls are: pyridinyl, imidazolyl, pyrimidinyl, pyrazolyl, triazolyl, pyrazinyl, furyl, thienyl. The above-mentioned groups may be bound via a carbon atom or a nitrogen atom. For example, the substituent obtained by binding pyrrole may be either pyrrol-1-yl (N-bound) or pyrrol-3-yl (C-bound).

(21) The term neutral ligand concerns a substituent having no electrical charge, capable of co-ordinating to a ruthenium atom. The non-limiting examples of such ligands are: N-heterocyclic carbene ligands, amines, imines, phosphines and oxides thereof, alkyl and aryl phosphites and phosphates, ethers, alkyl and aryl sulfides, co-ordinated hydrocarbons, haloalkanes and haloarenes. The term neutral ligand encompasses also N-heterocyclic compounds; their non-limiting examples are: pyridine, 4-(N,N-dimethylamino)pyridine (DMAP), 3-bromopyridine, piperidine, morpholine, pyridazine, pyrimidine, pyrazine, piperazine, 1,2,3-triazole, 1,3,4-triazole, 1,2,3-triazine and 1,2,4-triazine.

(22) The term anionic ligand concerns the substituent capable to co-ordination with a metal center, bearing an electrical charge capable to compensate the charge of the metal center, wherein such a compensation may be complete or partial. The non-limiting examples of anionic ligands are: fluoride, chloride, bromide or iodide anions, carboxylic acid anions, alcohol and phenol anions, thiol and thiophenol anions, (organo)sulfuric and (organo)phosphoric acid anions as well as anions of esters thereof.

(23) The term bidentate anionic ligand (X-L.sub.1) means that the neutral ligands L.sub.1 is bound together with anionic ligand, X, resulting in the formation of bidentate ligands. Similarly, various bidentate ligands are also possible with the combination of X and L.sub.1. The non-limiting examples of multidentate ligands are: a bidentate ligand (X.sub.1-L.sub.1), a tridentate ligand (X.sub.1-L.sub.1-L.sub.2). The non-limiting examples of such ligands are: anion of 2-hydroxyacetophenone, anion of acetylacetone and aryliminoaryloxy group as described hereinabove.

(24) The term carbene concerns a molecule containing a neutral carbon atom having the valence number of 2 and two non-paired valence electrons. The term carbene encompasses also carbene analogues, wherein the carbon atom is replaced with another chemical element such as: boron, silicon, nitrogen, phosphorus, sulfur. The term carbene relates particularly to N-heterocyclic carbene (NHC) ligands. The non-limiting examples of the NHC ligands are:

(25) ##STR00017##

(26) The non-limiting examples of preferred agents promoting formation of cross bonds are tert-butyl peroxide, di-tert-butyl peroxide, and also mixtures thereof.

(27) The following examples describe the procedures used for the preparation of the compounds of this invention and their use in olefin metathesis. The following examples are only intended to illustrate the invention and to explain its particular aspects. The activity of the catalyst 1c according to the invention was compared to the LatMet-PCy.sub.3, its structure is presented below:

(28) ##STR00018##

(29) DCPD contains 6% m/m tricyclopentadiene (TCPD), tricyclohexylphosphine, solution of lithium bis(trimethylsilyl)amide, solution of potassium tert-pentoxide, hydrogen chloride solution in THF are commercially available. Compounds 1-7 were prepared according to literature procedures. All reactions were carried out under argon. The toluene was washed with citric acid, water, dried with 4 ? molecular sieves and deoxidized with argon. The THF was dried with 4 ? molecular sieves and deoxidized with argon.

EXAMPLE 1

(30) ##STR00019##

(31) Solution of lithium bis(trimethylsilyl)amide in toluene (1 M, 12.4 mL, 1.1 eq) was added to the suspension of salt 1 (5.11 g, 1.15 eq) in toluene (82 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 (10.0 g, 11.3 mmol, 1 eq, C.sub.Ind.0 0.12 M) was added and the mixture was stirred for 10 min. Next 2 (2.27 g, 1.5 eq) was added and after additional 30 min triphenylphosphine was added (1.48 g, 0.5 eq). 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 recrystallization from dichloromethane/n-heptane mixture, green solid, 4.2 g, 46% yield.

EXAMPLE 2

(32) ##STR00020##

(33) 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%.

(34) .sup.1H NMR (600 MHz, CD.sub.2Cl.sub.2) ? 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).

(35) .sup.13C NMR (150 MHz, CD.sub.2Cl.sub.2) ? 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

(36) ##STR00021##

(37) 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%.

(38) .sup.1H NMR (600 MHz, CD.sub.2Cl.sub.2) ? 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).

(39) .sup.13C NM R (150M Hz, CD2Cl2) ? 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

(40) ##STR00022##

(41) 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. 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%.

(42) .sup.1H NMR (600 MHz, CD.sub.2Cl.sub.2) ? 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)

(43) .sup.13C NMR (150 MHz, CD.sub.2Cl.sub.2) ? 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

(44) ##STR00023##

(45) 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%.

(46) .sup.1H NMR (600 MHz, CD.sub.6) ? 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).

(47) .sup.13C NMR (150 MHz, C.sub.5D.sub.6) ? 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

(48) ##STR00024##

(49) 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

(50) ##STR00025##

(51) 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%.

(52) .sup.1H NMR (600 MHz, CD.sub.2Cl.sub.2) ? 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).

(53) .sup.13C NMR (151 MHz, CD.sub.2Cl.sub.2) ? 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

(54) 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 ?L of dry toluene). Formulation B: 5 mL of DCPD (6% m/m TCPD), hydrogen chloride solution in THF (0.75 M, 40 ?L, 800 ppm). Formulation B was added to Formulation A, results:

(55) 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

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

(57) 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.

(58) 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.