Metathesis catalysts and reactions using the catalysts

Abstract

The invention relates to a method of forming an olefin from a first olefin and a second olefin in a metathesis reaction, comprising step (i): (i) reacting the first olefin with the second olefin in the presence of a compound that catalyzes said metathesis reaction such that the molar ratio of said compound to the first or the second olefin is from 1:500 or less, and the conversion of the first or the second olefin to said olefin is at least 50%, characterized in that as compound that catalyzes said metathesis reaction a compound of the following formula is used: ##STR00001## wherein M is Mo or W; R.sup.1 is aryl, heteroaryl, alkyl, or heteroalkyl; optionally substituted; R.sup.2 and R.sup.3 can be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl; optionally substituted; R.sup.5 is alkyl, alkoxy, heteroalkyl, aryl, heteroaryl, silylalkyl, silyloxy, optionally substituted; and R.sup.4 is a residue R.sup.6—X—, wherein X═O and R.sup.6 is aryl, optionally substituted; or X═S and R.sup.6 is aryl, optionally substituted; or X═O and R.sup.6 is (R.sup.7, R.sup.8, R.sup.9)Si; wherein R.sup.7, R.sup.8, R.sup.9 are alkyl or phenyl, optionally substituted; or X═O and R.sup.6 is (R.sup.10, R.sup.11, R.sup.12)C, wherein R.sup.10, R.sup.11, R.sup.12 are independently selected from phenyl, alkyl; optionally substituted; and to the catalysts used in the method.

Claims

1. A method of forming an olefin product in a metathesis reaction from a feedstock comprising a first olefin and a second olefin, wherein said feedstock further comprises at least one by-product selected from the group consisting of water, alcohols, aldehydes, peroxides, hydroperoxides, peroxide decomposition products, protic materials, polar materials, Lewis basic catalyst poisons, and mixtures thereof, the method comprising step (i), and subsequent to step (i), the following step (ii): (i) at least partially removing said at least one by-product from the feedstock to form a purified feedstock by subjecting said feedstock to (1) a chemical purification step or (2) both a physical purification step and a chemical purification step, wherein the physical purification step comprises subjecting said feedstock to at least one of a distillation step or an adsorption step; and wherein the chemical purification step comprises subjecting said feedstock to a chemical reaction wherein said feedstock is subjected to an anhydride of an organic acid or an organometallic compound of aluminum; (ii) reacting the first olefin with the second olefin in the presence of a compound that catalyzes said metathesis reaction such that the molar ratio of said compound to the first or the second olefin is less than 1:500, and the conversion of the first or the second olefin to said olefin product is at least 30%; wherein the compound that catalyzes said metathesis reaction has the following general Formula (A): ##STR00112## wherein M=Mo or W; R.sup.1 is aryl, heteroaryl, alkyl, or heteroalkyl, each of which is optionally substituted; R.sup.2 and R.sup.3 are the same or different and are alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl, each of which is optionally substituted, or hydrogen; R.sup.5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, each of which is optionally substituted; and R.sup.4 is a residue R.sup.6—X—, wherein X═O and R.sup.6 is aryl, optionally substituted; or X═S and R.sup.6 is aryl, optionally substituted; or X═O and R.sup.6 is (R.sup.7)(R.sup.8)(R.sup.9)Si; wherein R.sup.7, R.sup.8, R.sup.9 are alkyl or phenyl, each of which is optionally substituted; or X═O and R.sup.6 is (R.sup.10)(R.sup.11)(R.sup.12)C, wherein R.sup.10, R.sup.11, R.sup.12 are independently selected from optionally substituted phenyl or optionally substituted alkyl; or X═O and R.sup.6 is a quinoline-8-yl, optionally substituted; or X═O and R.sup.6 is triphenylmethyl; tri(4-methyphenyl)methyl; 1,1,1,3,3,3-hexafluoro-prop-2-yl; or 9-phenyl-fluorene-9-yl; or R.sup.4 and R.sup.5 are linked together and are bound to M via oxygen, respectively; or wherein the compound that catalyzes said metathesis reaction is selected from one of the following structures: 280, 281, 289, 290, or 291: ##STR00113## and wherein the organometallic compound of aluminum of step (i) is of formula R.sub.1R.sub.2R.sub.3Al, wherein said R.sub.1, R.sub.2, and R.sub.3 in the organometallic compound of aluminum are independently selected from aliphatic, cyclic, or alicyclic residues having from 1 to 10 carbon atoms, or from aromatic residues having from 6 to 10 carbon atoms; and wherein the compound that catalyzes said metathesis reaction is added to the purified feedstock in portions, or is added at a rate of 0.01 to 10 ppmwt per hour to the purified feedstock.

2. The method of claim 1, wherein the organometallic compound of aluminum is trioctyl aluminum.

3. The method of claim 1, wherein the organometallic compound of aluminum is a trialkyl aluminum compound, and wherein the feedstock is subjected to the trialkyl aluminum compound for a period of from 10 to 80 h.

4. The method of claim 1, wherein the feedstock is subjected to the organometallic compound of aluminum, and wherein the organometallic compound of aluminum is added to the first and the second olefin at a rate of from 0.01 to 10 ppmwt organometallic compound of aluminum per hour.

5. The method of claim 1, wherein in the compound of general Formula (A): M=Mo or W; R.sup.1 is aryl or adamant-1-yl, each of which is optionally substituted; R.sup.2 is —C(CH.sub.3).sub.2C.sub.6H.sub.5 or —C(CH.sub.3).sub.3; R.sup.3 is H; R.sup.5 is alkoxy, heteroaryl, silyloxy, or aryloxy, each of which is optionally substituted; and R.sup.4 is a residue R.sup.6—X—, wherein X═O and R.sup.6 is phenyl substituted with up to five substituents independently selected from alkyl, phenoxy, phenyl, halogen, each of which is optionally substituted; or X═O and R.sup.6 is 8-(naphthalene-1-yl)-naphthalene-1-yl, optionally substituted; or X═O and R.sup.6 is 8-phenylnaphthalene-1-yl, optionally substituted; or X═O and R.sup.6 is quinoline-8-yl, optionally substituted; or X═S and R.sup.6 is phenyl substituted with up to five substituents independently selected from alkyl, phenoxy, phenyl, halogen, each of which is optionally substituted; or X═O and R.sup.6 is triphenylsilyl, optionally substituted; or triisopropylsilyl; or X═O and R.sup.6 is triphenylmethyl, optionally substituted; or X═O and R.sup.6 is 9-phenyl-fluorene-9-yl; or X═O and R.sup.6 is 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yl, or 2-methyl-1,1,1,3,3,3-hexafluoro-prop-2-yl; or X═O and R.sup.6 is t-butyl; or wherein in the compound of general Formula (A): M=Mo or W; R.sup.1 is selected from 1-(2,6-dimethylphenyl), 1-(2,6-diisopropylphenyl), 1-(2,6-di-t-butylphenyl), 1-(2,6-dichlorophenyl), adamant-1-yl; R.sup.2 is —C(CH.sub.3).sub.2C.sub.6H.sub.5 or —C(CH.sub.3).sub.3; R.sup.3 is H; R.sup.5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 2-methyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 9-phenyl-fluorene-9-yloxy; 2,6-diphenylphenoxy; t-butyloxy; and R.sup.4 is R.sup.6—X—, wherein X═O and R.sup.6 is phenyl substituted with up to five substituents independently selected from alkyl, alkoxy, phenoxy, phenyl, halogen, each of which is optionally substituted; or X═O and R.sup.6 is 8-(naphthalene-1-yl)-naphthalene-1-yl, optionally substituted; or X═O and R.sup.6 is 8-phenylnaphthalene-1-yl, optionally substituted; or X═O and R.sup.6 is quinoline-8-yl, optionally substituted; or X═S and R.sup.6 is phenyl substituted with up to five substituents independently selected from alkyl, phenoxy, phenyl, halogen, each of which is optionally substituted; or X═O and R.sup.6 is triphenylsilyl; or triisopropylsilyl; or X═O and R.sup.6 is triphenylmethyl or tri(4-methylphenyl)methyl; or X═O and R.sup.6 is 9-phenyl-fluorene-9-yl; or X═O and R.sup.6 is 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yl; or 2-methyl-1,1,1,3,3,3-hexafluoro-prop-2-yl; or X═O and R.sup.6 is t-butyl.

6. The method of claim 1, wherein in the compound of general Formula (A): M=Mo or W; R.sup.1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R.sup.2 is —C(CH.sub.3).sub.2C.sub.6H.sub.5 or —C(CH.sub.3).sub.3; R.sup.3 is H; R.sup.5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 2-methyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 9-phenyl-fluorene-9-yloxy; 2,6-diphenylphenoxy; t-butyloxy; and R.sup.4 is R.sup.6—X—, wherein X═O and R.sup.6 is phenyl which bears two substituents in ortho position with respect to O, or which bears at least three substituents, from which two substituents are in ortho position with respect to O and one substituent is in para position with respect to O; or X═O and R.sup.6 is 8-(naphthalene-1-yl)-naphthalene-1-yl, optionally substituted; or X═O and R.sup.6 is 8-phenylnaphthalene-1-yl, optionally substituted; or X═O and R.sup.6 is quinoline-8-yl, optionally substituted; or X═O and R.sup.6 is triphenylsilyl; or triisopropylsilyl; X═O and R.sup.6 is triphenylmethyl or tri(4-methylphenyl)methyl; or X═O and R.sup.6 is 9-phenyl-fluorene-9-yl; or X═O and R.sup.6 is 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yl; or 2-methyl-1,1,1,3,3,3-hexafluoro-prop-2-yl; or X═O and R.sup.6 is t-butyl.

7. The method of claim 1, wherein the compound is selected from the following structures: ##STR00114## ##STR00115## ##STR00116## ##STR00117## ##STR00118## ##STR00119## ##STR00120## ##STR00121## ##STR00122## ##STR00123## ##STR00124## ##STR00125## ##STR00126## ##STR00127## ##STR00128## ##STR00129## ##STR00130## ##STR00131## ##STR00132## ##STR00133## ##STR00134## ##STR00135## ##STR00136## ##STR00137## ##STR00138## ##STR00139## ##STR00140## ##STR00141## ##STR00142## ##STR00143## ##STR00144## ##STR00145## ##STR00146## ##STR00147## ##STR00148## ##STR00149## ##STR00150## ##STR00151## ##STR00152## ##STR00153## ##STR00154## ##STR00155## ##STR00156## ##STR00157## ##STR00158## ##STR00159## ##STR00160## ##STR00161## ##STR00162## ##STR00163## ##STR00164## ##STR00165## ##STR00166## ##STR00167## ##STR00168## ##STR00169## ##STR00170## ##STR00171## ##STR00172## ##STR00173## ##STR00174## ##STR00175## ##STR00176## ##STR00177## ##STR00178## ##STR00179##

8. The method of claim 1, wherein in the compound of general Formula (A): M=Mo or W; R.sup.1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-di-t-butylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R.sup.2 is —C(CH.sub.3).sub.2C.sub.6H.sub.5 or —C(CH.sub.3).sub.3; R.sup.3 is H; R.sup.5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 2-methyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 9-phenyl-fluorene-9-yloxy; 2,6-diphenylphenoxy; t-butoxy; and R.sup.4 is R.sup.6—X—, wherein X═O and R.sup.6 is phenyl which bears at least two substituents, or which bears two substituents in ortho position with respect to O, or which bears two substituents in ortho position with respect to O and a substituent in para position with respect to O; or X═O and R.sup.6 is triphenylsilyl, optionally substituted; or X═O and R.sup.6 is triphenylmethyl, optionally substituted; or X═O and R.sup.6 is 9-phenyl-fluorene-9-yl; or X═O and R.sup.6 is 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yl or 2-methyl-1,1,1,3,3,3-hexafluoro-prop-2-yl; or X═O and R.sup.6 is t-butyl; with the proviso that the following compounds are excluded: M=Mo; R.sup.1=2,6-diisopropylphenyl; R.sup.2═—C(CH.sub.3).sub.2C.sub.6H.sub.5; R.sup.3═H; R.sup.5=2,5-dimethylpyrrol-1-yl; R.sup.4=2,6-diphenylphenoxy; M=Mo; R.sup.1=2,6-diisopropylphenyl; R.sup.2═—C(CH.sub.3).sub.2C.sub.6H.sub.5; R.sup.3═H; R.sup.5=2,5-dimethylpyrrol-1-yl; R.sup.4=2,3,5,6-tetraphenylphenoxy; M=W; R.sup.1=2,6-diisopropylphenyl; R.sup.2═—C(CH.sub.3).sub.2C.sub.6H.sub.5; R.sup.3═H; R.sup.5=2,5-dimethylpyrrol-1-yl; R.sup.4=triphenylsilyloxy; M=Mo; R.sup.1=2,6-diisopropylphenyl; R.sup.2═—C(CH.sub.3).sub.2C.sub.6H.sub.5; R.sup.3═H; R.sup.5=2,5-dimethylpyrrol-1-yl; R.sup.4=triphenylsilyloxy; and M=W; R.sup.1=2,6-diisopropylphenyl; R.sup.2═—C(CH.sub.3).sub.2C.sub.6H.sub.5; R.sup.3═H; R.sup.5=2,5-dimethylpyrrol-1-yl; R.sup.4= ##STR00180## wherein TBS is t-butyldimethylsilyl, and ##STR00181## wherein R.sup.19 is F, Cl, Br, or I; or wherein M=Mo or W; R.sup.1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R.sup.2 is —C(CH.sub.3).sub.2C.sub.6H.sub.5 or —C(CH.sub.3).sub.3 or adamant-1-yl; R.sup.3 is H; R.sup.5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyoxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 9-phenyl-fluorene-9-yloxy; and R.sup.4 is selected from ##STR00182## wherein TBS is t-butyldimethylsilyl; ##STR00183## wherein Me=methyl; or wherein M=Mo or W; R.sup.1 is 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R.sup.2 is —C(CH.sub.3).sub.2C.sub.6H.sub.5 or —C(CH.sub.3).sub.3 or adamant-1-yl; R.sup.3 is H; R.sup.5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 9-phenyl-fluorene-9-yloxy; and R.sup.4 is selected from 2,6-diphenylphenoxy, 2,3,5,6-tetraphenylphenoxy, 2,6-di(tert.-butyl)phenoxy; 2,6-di(2,4,6-triisopropylphenyl)phenoxy; with the proviso that the following compounds are excluded: M=Mo; R.sup.1=2,6-diisopropylphenyl; R.sup.2═—C(CH.sub.3).sub.2C.sub.6H.sub.5; R.sup.3═H; R.sup.5=2,5-dimethylpyrrol-1-yl; R.sup.4=2,6-diphenylphenoxy; and M=Mo; R.sup.1=2,6-diisopropylphenyl; R.sup.2═—C(CH.sub.3).sub.2C.sub.6H.sub.5; R.sup.3═H; R.sup.5=2,5-dimethylpyrrol-1-yl; R.sup.4=2,3,5,6-tetraphenylphenoxy; or wherein M=Mo or W; R.sup.1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R.sup.2 is —C(CH.sub.3).sub.2C.sub.6H.sub.5 or —C(CH.sub.3).sub.3 or adamant-1-yl; R.sup.3 is H; R.sup.5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 9-phenyl-fluorene-9-yloxy; and R.sup.4 is a residue R.sup.6—X—, wherein X═O and R.sup.5 is triphenylsilyl; with the proviso that following compounds are excluded: M=W; R.sup.1=2,6-diisopropylphenyl; R.sup.2═—C(CH.sub.3).sub.2C.sub.6H.sub.5; R.sup.3═H; R.sup.5=2,5-dimethylpyrrol-1-yl; R.sup.4=triphenylsilyloxy; and M=Mo; R.sup.1=2,6-diisopropylphenyl; R.sup.2═—C(CH.sub.3).sub.2C.sub.6H.sub.5; R.sup.3═H; R.sup.5=2,5-dimethylpyrrol-1-yl; R.sup.4=triphenylsilyloxy; or wherein M=Mo or W; R.sup.1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl; R.sup.2 is —C(CH.sub.3).sub.2C.sub.6H.sub.5 or —C(CH.sub.3).sub.3 or adamant-1-yl; R.sup.3 is H; R.sup.5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 9-phenyl-fluorene-9-yloxy; and R.sup.4 is a residue R.sup.6—X—, wherein X═O and R.sup.6 is triphenylmethyl; tri(4-methyphenyl)methyl; 1,1,1,3,3,3-hexafluoro-prop-2-yl; or 9-phenyl-fluorene-9-yl.

9. The method of claim 1, wherein in the compound of general Formula (A): M=Mo or W; R.sup.1 is aryl, heteroaryl, alkyl, or heteroalkyl, each of which is optionally substituted; R.sup.2 and R.sup.3 are the same or different and are alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl, each of which is optionally substituted, or hydrogen; R.sup.5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, each of which is optionally substituted; and R.sup.4 is a residue R.sup.6—X—, wherein X═O and R.sup.6 is a phenyl ring which is at least substituted in 4-position with respect to O.

10. The method of claim 9, wherein the substituent of residue R.sup.6 in 4-position is selected from the group consisting of: halogen, dialkylamino, cyano, optionally substituted alkyl, optionally substituted alkyloxy, optionally substituted aryl, optionally substituted aryloxy; wherein further substituents of residue R.sup.6 are the same or are different from the substituent in 4-position and are independently selected from the group consisting of: halogen, dialkylamino, cyano, optionally substituted alkyl, optionally substituted alkyloxy, optionally substituted aryl, optionally substituted aryloxy; or wherein R.sup.1 is phenyl or alkyl, each of which is optionally independently substituted with halogen, C.sub.1-4 dialkylamino, C.sub.1-4 alkyl, C.sub.1-4 alkyloxy, phenyl, phenyloxy, each of which is optionally substituted; R.sup.2 and R.sup.3 are the same or different and are hydrogen, C(CH.sub.3).sub.3, or C(CH.sub.3).sub.2C.sub.6H.sub.5; R.sup.5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy, 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 2-methyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 2,6-diphenylphenoxy; 9-phenyl-fluorene-9-yloxy; t-butyloxy; and the substituent of residue R.sup.6 in 4-position is selected from the group consisting of: halogen, C.sub.1-4 dialkylamino, C.sub.1-4 alkyl, C.sub.1-4 alkyloxy, phenyl, phenyloxy, each of which is optionally substituted; and further substituents of residue R.sup.6 are the same or are different from the substituent in 4-position and are independently selected from the group consisting of halogen, C.sub.1-4 dialkylamino, C.sub.1-4 alkyl, C.sub.1-4 alkyloxy, phenyl, phenyloxy, each of which is optionally substituted; or wherein R.sup.6 is a phenyl ring which is substituted in 2- and 4-position independently with halogen and in 6-position with phenyl, which optionally is substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy; or phenyl or phenoxy optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy, respectively; or wherein R.sup.6 is a phenyl ring which is substituted in 2- and 6-position by substituents via carbon atoms, and in 4-position by a substituent via any atom; or wherein R.sup.6 is a phenyl ring which is substituted in 4-position with bromine and in 2-, 3-, 5- and 6-position with phenyl, respectively, wherein said phenyl residues are independently substituted with fluoro, chloro, bromo, dimethylamino, diethylamino, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, methoxy, ethoxy, propyloxy, butyloxy, t-butyloxy, trifluoromethyl, phenyl optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy; phenoxy optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy.

11. The method of claim 1, wherein in the compound of general Formula (A): M=Mo or W; R.sup.1 is aryl, heteroaryl, alkyl, or heteroalkyl, each of which is optionally substituted; R.sup.2 and R.sup.3 are the same or different and are alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl, each of which is optionally substituted, or hydrogen; R.sup.5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, each of which is optionally substituted; and R.sup.4 is a residue R.sup.6—X—, wherein X═O and R.sup.6 is a phenyl ring which is substituted in 2- and 6-position with phenyl, respectively, optionally substituted; or wherein in the compound of general Formula (A): M=Mo or W; R.sup.1 is aryl, heteroaryl, alkyl, or heteroalkyl, each of which is optionally substituted; R.sup.2 and R.sup.3 are the same or different and are alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl, each of which is optionally substituted, or hydrogen; R.sup.5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, each of which is optionally substituted; and R.sup.4 is [8-(naphthalene-1-yl)-naphthalene-1-yl]oxy, optionally substituted; or wherein in the compound of general Formula (A): M=Mo or W; R.sup.1 is aryl, heteroaryl, alkyl, or heteroalkyl, each of which is optionally substituted; R.sup.2 and R.sup.3 are the same or different and are alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl, each of which is optionally substituted, or hydrogen; R.sup.5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, each of which is optionally substituted; and R.sup.4 is (8-phenylnaphthalene-1-yl)oxy, optionally substituted.

12. The method of claim 1, wherein the first olefin has a terminal olefinic double bond, and the second olefin has a terminal olefinic double bond, wherein the first and the second olefin are identical; or wherein the first and the second olefin are different from one another; or wherein the first olefin has an internal olefinic double bond and the second olefin is ethylene; or wherein the first olefin is a cyclic olefin and the second olefin is a cyclic olefin, wherein the first and the second olefin are identical or are different from one another.

13. A method of increasing the reactivity of a compound of Formula (A): ##STR00184## wherein M=Mo or W; R.sup.1 is aryl, heteroaryl, alkyl, or heteroalkyl, each of which is optionally substituted; R.sup.2 and R.sup.3 are the same or different and are alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl, each of which is optionally substituted, or hydrogen; R.sup.5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, each of which is optionally substituted; and R.sup.4 is a residue R.sup.6—X—, wherein X═O and R.sup.6 is aryl, optionally substituted; or X═S and R.sup.6 is aryl, optionally substituted; or X═O and R.sup.6 is (R.sup.7)(R.sup.8)(R.sup.9)Si; wherein R.sup.7, R.sup.8, R.sup.9 are alkyl or phenyl, each of which is optionally substituted; or X═O and R.sup.6 is (R.sup.10)(R.sup.11)(R.sup.12)C, wherein R.sup.10, R.sup.11, R.sup.12 are independently selected from optionally substituted phenyl or optionally substituted alkyl; or X═O and R.sup.6 is a quinoline-8-yl, optionally substituted; or R.sup.4 and R.sup.5 are linked together and are bound to M via oxygen, respectively; or structures 280, 281, 289, 290, or 291: ##STR00185## that catalyzes a metathesis reaction of a feedstock comprising a first and a second olefin such that the molar ratio of said compound to the first or the second olefin is less than 1:500, and the conversion of the first or the second olefin is at least 30%, wherein said feedstock further comprises at least one by-product selected from the group consisting of water, alcohols, aldehydes, peroxides, hydroperoxides, peroxide decomposition products, protic materials, polar materials, Lewis basic catalyst poisons, and mixtures thereof, the method comprising step (i), and, subsequent to step (i), the following step (ii): (i) at least partially removing said at least one by-product from the feedstock to form a purified feedstock by subjecting said feedstock to a chemical purification step, wherein the chemical purification step comprises: subjecting said feedstock to a chemical reaction wherein said feedstock is subjected to an anhydride of an organic acid or an organometallic compound of aluminum; (ii) reacting the first olefin with the second olefin in the presence of said compound that catalyzes said metathesis reaction, and wherein the organometallic compound of aluminum of step (i) is of formula R.sub.1R.sub.2R.sub.3Al, wherein said R.sub.1, R.sub.2, and R.sub.3 in the organometallic compound of aluminum are independently selected from aliphatic, cyclic, or alicyclic residues having from 1 to 10 carbon atoms, or from aromatic residues having from 6 to 10 carbon atoms; and wherein the compound that catalyzes said metathesis reaction is added to the purified feedstock in portions, or is added at a rate of from 0.01 to 10 ppmwt per hour to the purified feedstock.

Description

EXAMPLES

(1) 1. Synthesis of Catalysts

(2) All reactions were carried out in owen—(120° C.) dried glassware under an inert atmosphere of N2 unless otherwise stated. Alcohols were dried by azeotropic distillation with C.sub.6D.sub.6 prior to use in reactions with Mo- or W-based reagents. .sup.1H NMR were recorded on a Varian XL-200 (200 MHz) spectrometer. Chemical shifts are reported in ppm from tetramethylsilane with the tetramethylsilane resonance as the internal reference (δ0.00). Data are reported as follows: chemical shift, integration, multiplicity (s=singulet, d=doublet, t=triplet, hept=heptate, br=broad, m=multiplet).

Example 1 N-[(2,5-dimethyl-1H-pyrrol-1-yl)(2-methyl-2-phenylpropylidene)2,4,6-triphenylphenoxymolybdenumylidene]-2,6-bis(propan-2-yl)aniline (Novel Compound 44)

(3) In a N2-filled glovebox, a 100 mL pear-shaped flask with magnetic stirbar was charged with N-[bis(2,5-dimethyl-1H-pyrrol-1-yl)(2-methyl-2-phenylpropylidene)-molybdenumylidene]-2,6-bis(propan-2-yl)aniline (959.5 mg, 1.6 mmol) and Et.sub.2O (16 mL). A 30 mL vial was charged with 2,4,6-triphenylphenol (522.8 mg, 1.6 mmol) and Et.sub.2O (4 mL). The Mo-bis(pyrrolide) solution was allowed to stir and the phenol solution was added to it by pipet. The vial containing the phenol was rinsed with Et.sub.2O (2 mL), which was similarly transferred to the reaction mixture. After 2 h at 22° C., volatiles were removed under reduced pressure and the resulting red oil was triturated with n-pentane (10 mL) to afford an orange precipitate. The flask was sealed and allowed to cool to −38° C. (glovebox freezer) for 12 h. The orange precipitate was collected by vacuum filtration and washed with cold pentane (˜5 mL) to afford the titled compound as an orange powder (1.1 g, 1.3 mmol, 82.8% yield). .sup.1H NMR (200 MHz, C.sub.6D.sub.6): δ 11.42 (1H, s), 7.63-7.56 (8H, m), 7.22-6.88 (17H, m), 6.10 (2H, s), 3.13 (2H, hept), 2.25 (6H, br s), 1.54 (3H, s), 1.21 (3H, s), 0.96 (6H, d), 0.84 (6H, d).

Example 2: 2,6-dichloro-N-[(2,5-dimethyl-1H-pyrrol-1-yl)(2,2-dimethylpropylidene)4-fluoro-2,6-diphenylphenoxytungstenylidene]aniline (Novel Compound 63)

(4) In a N2-filled glovebox, a 100 mL pear-shaped flask with magnetic stirbar was charged with N-[bis(2,5-dimethyl-1H-pyrrol-1-yl)(2,2-dimethylpropylidene)tungstenylidene]-2,6-dichloroaniline (1.5 g, 2.5 mmol) and Et.sub.2O (19 mL). A 30 mL vial was charged with 4-fluoro-2,6-diphenylphenol (658.3 mg, 2.5 mmol) and Et.sub.2O (6 mL). The W-bis(pyrrolide) solution was allowed to stir and the phenol solution was added to it by pipet. The vial containing the phenol was rinse with Et.sub.2O. (2 mL), which was similarly transferred to the reaction mixture. After 2 h at 22° C., volatiles were removed under reduced pressure and the resulting orange solid was triturated with n-pentane (15 mL) to afford a yellow precipitate. The flask was sealed and allowed to cool to −38° C. (glovebox freezer) for 12 h. The orange precipitate was collected by vacuum filtration and washed with cold pentane (˜5 mL) to afford the titled compound as an orange powder (1.6 g, 2.1 mmol, 83.3% yield). .sup.1H NMR (200 MHz, C.sub.6D.sub.6): δ 8.06 (1H, s), 7.39-7.35 (4H, m), 7.10-6.78 (10H, m), 6.18 (1H, t), 6.13 (2H, s), 2.17 (6H, s), 1.00 (9H, s).

(5) The compounds were characterized by means of 1H NMR spectroscopy and the respective shift (ppm) of the respective alkylidene H (C.sub.6D.sub.6) as set forth in the following Table 1:

(6) TABLE-US-00002 TABLE 1 Compounds used as catalyst for metathesis reactions according to the invention Compound Formula ppm   1 C46H50MoN2O 11.38   2 C44H48MoN2OSi 12.07   3 C29H37BrCl2N2OW 10.17   4 C33H46Cl2N2OW 10.36   5 C30H40Cl2N2O2W 10.33   6 C44H46MoN2O 11.96   7 C41H56MoN2O 13.04   8 C42H42MoN2O 11.31   9 C44H48MoN2O 10.98  10 C58H58MoN2O 11.42  11 C58H57BrMoN2O 11.51  12 C54H50MoN2O 11.22  13 C54H49BrMoN2O 11.28  14 C46H49BrMoN2O 11.27  15 C42H41BrMoN2O 11.24  16 C56H55BrMoN2O 11.03  17 C40H53BrMoN2O 12.94  18 C44H62MoN2O 13.00  19 C41H56MoN2O2 13.03  20 C33H32Cl2N2OSiW 9.23  21 C35H36Cl2N2OSiOW 8.97  22 C46H52N2OSiW 9.00  23 C47H52MoN2O 10.69  24 C46H52MoN2OSi 11.93  26 C45H48MoN2O 11.34  26 C38H42Br2Cl2N2O2W 9.85  27 C36H36Cl2N2OW 7.73  28 C45H46MoN2O 11.02  29 C47H50MoN2O 10.92  30 C36H34Cl2N2OW 7.80  31 C37H42F6MoN2O 12.29  32 C58H55Br3MoN2O 11.77  33 C44H45BrMoN2O 11.85  34 C44H45FMoN2O 11.88  35 C52H61FMoN2O 11.57  36 C46H49FMoN2O 11.29  37 C50H57FMoN2O 11.62  38 C40H39F12MoNO2 12.34  39 C33H34F6MoN2O 12.50  40 C36H31F12MoNO2 12.28  41 C45H48MoN2O 11.96  42 C47H52MoN2O 11.40  43 C50H50MoN2O 11.98  44 C52H54MoN2O 11.41  45 C43H44MoN2O 10.95  46 C56H57MoNO2Si2 11.08  47 C43H42MoN2O 11.08  48 C58H53MoNO2 10.25  49 C58H59NO2Si2W 7.94  50 C54H51MoNO2Si2 11.22  51 C34H32Cl2N2OW  52 C34H30Cl2N2OW  53 C58H56Br2MoN2O 11.63  54 C54H48Br2MoN2O 11.46  55 C49H58Br2N2O2W 9.82; 9.79  66 C54H70Br2N2O2SiW 9.46; 9.43  57 C47H50N2OW 7.94  58 C36H38Br2Cl2N2O2W 9.95; 9.74  59 C40H54MoN2O 13.01  60 C54H47Br3MoN2O 11.55  61 C39H42Cl2N2OW 7.68  62 C29H38Cl2N2OW 10.30  63 C35H33Cl2FN2OW 8.06  64 C41H38Cl2N2OW 8.17  65 C34H32Cl2N2OW 9.09  66 C39H34Cl2N2OW 9.13  67 C33H29Cl2FN2OW 8.98  68 C33H29BrCl2N2OW 8.98  69 C39H41Cl2FN2OW 8.64  70 C30H40Cl2N2OW 10.32  71 C.sub.32H.sub.40F.sub.6MoN.sub.2O 12.40  72 C.sub.30H.sub.35F.sub.12MoNO.sub.2 12.09  73 C.sub.36H.sub.46MoN.sub.2O.sub.3 11.93  74 C.sub.34H.sub.40Cl.sub.2MoN.sub.2O 12.54  75 C.sub.34H.sub.37F.sub.5MoN.sub.2O 12.69  76 C.sub.54H.sub.70Br.sub.2MoN.sub.2O.sub.2Si  77 C.sub.49H.sub.58Br.sub.2MoN.sub.2O.sub.2 12.78; 12.76  78 C.sub.54H.sub.62Br.sub.2MoN.sub.2O.sub.2Si 12.91; 11.58  79 C.sub.49H.sub.50Br.sub.2MoN.sub.2O.sub.2 12.83; 11.64  80 C.sub.52H.sub.66Br.sub.2MoN.sub.2O.sub.2Si 12.89; 12.87  81 C.sub.47H.sub.54Br.sub.2MoN.sub.2O.sub.2 12.80; 12.58  82 C.sub.42H.sub.49MoNO.sub.2 11.72  83 C.sub.42H.sub.47Br.sub.2MoNO.sub.2 12.42  84 C.sub.44H.sub.45F.sub.6MoNO.sub.2 11.62  85 C.sub.58H.sub.55MoNO.sub.2 11.48  86 C.sub.47H.sub.53Br.sub.2F.sub.6MoNO.sub.3 12.32; 12.25  87 C.sub.43H.sub.54Br.sub.2Cl.sub.2N.sub.2O.sub.2SiW 9.78; 9.16  88 C.sub.40H.sub.54MoN.sub.2O 12.24  89 C.sub.48H.sub.51MoNO.sub.4 11.20  90 C.sub.30H.sub.47MoNO.sub.2 11.27  91 C.sub.51H.sub.68MoN.sub.2O.sub.2 12.48  92 C.sub.54H.sub.70Br.sub.2MoN.sub.2O.sub.2Si 12.89; 12.41  93 C.sub.50H.sub.62Br.sub.2MoN.sub.2O.sub.2S1 12.98; 12.94  94 C.sub.37H.sub.43MoN.sub.3O 12.07  95 C.sub.56H.sub.70F.sub.6MoN.sub.2O.sub.2Si 12.90; 12.42  96 C.sub.60H.sub.69MoNO.sub.2 11.06  97 C.sub.35H.sub.38F.sub.6MoN.sub.2O.sub.2 13.66  98 C.sub.70H.sub.88MoN.sub.2O.sub.2Si 11.6  99 C.sub.54H.sub.56F.sub.8MoN.sub.2O.sub.2Si 12.15; 12.09 100 C.sub.49H.sub.44F.sub.8MoN.sub.2O.sub.2 12.02; 11.99 101 C.sub.51H.sub.66Cl.sub.2N.sub.2OW 102 C.sub.52H.sub.68Br.sub.2MoN.sub.2O.sub.2Si 12.52; 12.87 103 C.sub.26H.sub.27F.sub.12MoNO.sub.2 12.12 104 C.sub.45H.sub.50Br.sub.2MoN.sub.2O.sub.2 13.13; 12.75 106 SC.sub.38H.sub.38Br.sub.2MoNO.sub.2 12.87 106 C.sub.50H.sub.54Br.sub.2MoN.sub.2O.sub.2Si 12.85; 11.67 107 C.sub.65H.sub.78MoN.sub.2O.sub.2Si 12.0; 11.57 108 C.sub.52H.sub.62F.sub.6MoN.sub.2O.sub.2Si 12.87; 12.8 109 C.sub.47H.sub.56Br.sub.2MoN.sub.2O.sub.2 13.00; 12.59 110 C.sub.52H.sub.60Br.sub.2MoN.sub.2O.sub.2Si 12.80; 12.47; 11.22 111 C.sub.60H.sub.63Br.sub.4MoNO.sub.4 12.78 112 C.sub.28H.sub.33F.sub.12MoNO.sub.2 11.85; 13.10 113 C.sub.54H.sub.68F.sub.6MoN.sub.2O.sub.2Si 12.63; 12.23; 12.93 114 C.sub.40H.sub.45Br.sub.2MoNO.sub.2 12.97 115 C.sub.70H.sub.90MoN.sub.2O.sub.2Si 11.23; 11.67 116 C.sub.62H.sub.69Br.sub.4MoNO.sub.4 12.57 117 C.sub.72H.sub.83Br.sub.4MoNO.sub.4Si.sub.2 12.64 118 C.sub.62H.sub.84MoN.sub.2O 12.16 119 C.sub.41H.sub.50Br.sub.2Cl.sub.2N.sub.2O.sub.2SW 10.01; 9.98 120 C.sub.42H.sub.41FMoN.sub.2O 11.22 121 C.sub.48H.sub.46MoN.sub.2O 11.33 122 C.sub.48H.sub.53FMoN.sub.2O 11.51 123 C47H41BrCl2N2OW Overlap with aromatic protons 124 C47H39Br3Cl2N2OW Overlap with aromatic protons 125 C.sub.50H.sub.52MoN.sub.2O 10.95 126 C.sub.44H.sub.47BrMoN.sub.2O 10.85 127 C.sub.50H.sub.59FMoN.sub.2O 10.91 128 C.sub.24H.sub.22Cl.sub.2F.sub.6N.sub.2OW 9.58 129 C.sub.37H.sub.42F.sub.6N.sub.2OW 9.23 130 C.sub.35H.sub.33BrCl.sub.2N.sub.2OW 8.04 131 C.sub.41H.sub.45Cl.sub.2FN.sub.2OW 8.37 132 C.sub.52H.sub.54N.sub.2OW 8.51 133 C.sub.46H.sub.49FN.sub.2OW 8.37 134 C.sub.46H.sub.49BrN.sub.2OW 8.4 135 C.sub.52H.sub.61FN.sub.2OW 8.63 136 C.sub.58H.sub.55Br.sub.3N.sub.2OW 8.79 137 C.sub.26H.sub.42Cl.sub.2N.sub.2OSiW 9.53 138 C.sub.37H.sub.58MoN.sub.2OSi 12.43 139 C.sub.56H.sub.53BrMoN.sub.2O 11.82 140 C.sub.43H.sub.44MoN.sub.2O 11.32 141 C.sub.45H.sub.50MoN.sub.2O 10.98 142 C.sub.36H.sub.36Cl.sub.2N.sub.2OW 8.14 143 C56H54MoN2O 11.39 144 C58H58N2OW 8.42 145 C.sub.56H.sub.51Br.sub.3MoN.sub.2O 11.59 146 C.sub.42H.sub.39F.sub.3MoN.sub.2O 10.89 147 C.sub.49H.sub.57Br.sub.2F.sub.3MoN.sub.2O.sub.2Si 12.37 148 C.sub.48H.sub.53Br.sub.2F.sub.5MoN.sub.2O.sub.2Si 12.24 149 C.sub.41H.sub.35F.sub.5MoN.sub.2O 10.92 150 C.sub.44H.sub.47FMoN.sub.2O 10.84 151 C40H46N2OW 8.72 152 C29H30Cl2N2OW 8.72 153 C40H46MoN2O 11.49 154* C47H42Cl2N2OW 7.86 155 C41H56N2OW 10.28 156 C41H56N2O2W 10.28 157 C40H53BrN2OW 10.18 158 C44H62N2OW 10.27 159 C46H51N3OW 9.23 160 C48H55N3OW 8.42 161 C46H51MoN3O 11.97 162 C48H55MoN3O 11.33 163 C44H45FN2OW 9.14 164 C45H48N2OW 9.22 165 C50H57FN2OW 8.94 166 C50H50N2OW 9.23 167 C35H35Cl2N3OW 9.1 168 C37H39Cl2N3OW 8.13 169 C46H53MoN3O 10.94 170 C44H47MoN3O 11.27 171 C52H66Br2N2O2SiW 10.26; 10.04 172 C47H54Br2N2O2W 9.97; 9.72 173 C44H45BrN2OW 9.11 174 C62H82N2OW 9.95 175 C59H73F3MoN2O 12.31 176 C33H30Cl2N2OW 9.08 177 C44H46N2OW 9.21 178 C35H34Cl2N2OW 8.15 179 C46H50N2OW 8.48 *In case of compound 154 a different chemical shift of the alkylidene signal of the complex (7.86 ppm) was detected than described in the literature US 20110077421, WO 2011040963 (11.04 ppm) which is unusually high for that kind of complexes. Compounds 180 to 291 were also characterized by means of 1H NMR spectroscopy and the respective shift (ppm) of the respective alkylidene H (C.sub.6D.sub.6) as set forth in the respective formulas. Additionally, the formula weight is indicated.
2. Screening of Various Compounds in Ring Closure Metathesis (RCM) of diethyl diallylmalonate According to the Following Scheme 1:

(7) ##STR00107##

(8) Metathesis catalysts were tested in RCM of diethyl diallylmalonate. The reaction was characterized by the conversion data. Compounds 1, 10 and 154 are known compounds, compounds 11, 42, 123, 142, 162, 168, 178 are novel. Results are summarized at Table 2.

(9) TABLE-US-00003 TABLE 2 Results of diethyl diallylmalonate (1) self-metathesis in the presence of different metathesis catalysts at 760 Torr Molar ratio Cat. Catalyst/ T Time c Conv. Entry No. olefin (° C.) [h] Solvent (mol/L) (%) 1 10 1:2500 25° C. 4 h toluene 1 85 2 11 1:2500 25° C. 4 h toluene 1 87 3 154 1:2500 25° C. 4 h toluene 1 99 4 123 1:2500 25° C. 4 h toluene 1 98 5 1 1:2500 25° C. 4 h toluene 1 51 6 178 1:2500 25° C. 4 h toluene 1 97 7 42 1:2500 25° C. 4 h toluene 1 58 8 142 1:2500 25° C. 4 h toluene 1 99 9 162 1:2500 25° C. 4 h toluene 1 71 10 168 1:2500 25° C. 4 h toluene 1 98 Conversion = [(area of diethyl cyclopent-3-ene-1,1-dicarboxylate 2)/(area of diethyl cyclopent-3-ene-1,1-dicarboxylate 2 ) + (area of diethyl diallylmalonate 1)] without calibration.

(10) Entry 1-2, 4-9: All manipulation was performed under the inert atmosphere of the glovebox. Diethyl diallylmalonate (2.5 mmol, 604 μL) (substrate) was measured into a 10 ml glass vial and dissolved in toluene (abs 1.9 mL). 0.1 M stock solution (1 μmol, 10 μL) of the catalyst was added at r.t. and the vial was capped with a perforated cap to vent out the evolving ethylene. The reaction mixture was stirred at the same temperature for 4 h then it was taken out from the glovebox and its volume was diluted to 10 mL with EtOAc. 1 mL of this solution was poured onto the top of a silica column (1.0 mL) and eluted with EtOAc (10 mL). The collected eluate was analyzed by GCMS.

(11) Entry 3: The manipulation was performed under the inert atmosphere of the glovebox. Diethyl diallylmalonate (2.5 mmol, 604 μL) was measured into a 10 ml glass vial and dissolved in toluene (abs 1.9 mL). 0.05 M stock solution (1 μmol, 20 μL) of catalyst 154 was added at r.t. and the vial was capped with a perforated cap to vent out the evolving ethylene. The reaction mixture was stirred at the same temperature for 4 h then it was taken out from the glovebox and its volume was diluted to 10 mL with EtOAc. 1 mL of this solution was poured onto the top of a silica column (1.0 mL) and eluted with EtOAc (10 mL). The collected eluate was analyzed by GCMS.

(12) Materials: Diethyldiallylmalonate was purchased from Sigma-Aldrich. It was purged with nitrogen and transferred to the glovebox. It was percolated twice on 2×25 weight % activated alumina, and stored on molecular sieve.

(13) All reactions under the glovebox were carried out in ovendried (140° C.) glassware under an inert atmosphere of N2 unless otherwise stated. All catalyst was used as 0.1 M stock solution in C.sub.6D.sub.6 or benzene except 154 which was used as a 0.05 M solution in C.sub.6D.sub.6. GCMS chromatograms were recorded on a Shimadzu GC2010 Plus instrument

(14) 3. Screening of Various Compounds in Homo Cross Metathesis (HCM) of 2-allylphenylacetate

(15) Preparation of 2-allylphenylacetate According to Scheme 2

(16) ##STR00108##

(17) 2-allylphenol (0.5 mol) was dissolved in CH.sub.2Cl.sub.2 (1 L) under nitrogen. Et.sub.3N (139 mL, 1 mol) and DMAP (1.83 g, 0.015 mol) were added in one portion. The mixture was cooled to 0° C. with an ice bath and acetic anhydride was added to it drop-wise, keeping the temperature below 10° C. The reaction mixture was stirred for 2 h at 0-5° C. and monitored by TLC (10% EtOAc in heptane). The ice bath was removed, the reaction mixture was extracted with water (2×500 mL) and brine (300 mL). The solvent was evaporated and the product was purified by vacuum distillation (bp: 101° C. at 11 torr). The main fraction was purged with nitrogen; transferred into a nitrogen filled glovebox and filtered through on activated alumina pad (20 weight %) to afford 2 as a transparent liquid. (50 mL, 58.6%). GC-MS: 99.6%, [allylphenol traces (0.037%) are also detected], .sup.1H NMR (200 MHz, Chloroform-d): δ 2.23 (s, 3H), 3.23 (s, 2H), 4.94-4.98 (m, 1H), 5.03-5.04 (m, 1H), 5.73-5.93 (m, 1H), 6.94-7.22 (m, 4H), consistent.

(18) Before metathesis reaction the substrate was further stirred with 0.037-0.1 mol % triethylaluminium (r.t. during 1 h) to deactivate free phenol and water traces.

(19) 2-allylphenylacetate was subjected to HCM according to Scheme 3

(20) ##STR00109##

(21) Metathesis catalysts were tested in HCM of 2-allylphenylacetate using different substrate/catalyst ratios. The reaction was characterized by the conversion data. Catalysts according to the invention were compared to known compounds 1 and 10. Prior to the metathesis reaction, novel compound 2 was purified by means of Et.sub.3Al.

(22) Compound 162 gave a remarkable result. A higher conversion was detected than in case of the known compound 1 for a high loading with olefin. Compounds 11, 42 and 162 are novel. Results are summarized at Table 3.

(23) TABLE-US-00004 TABLE 3 Results of allylphenylacetate (2) self-metathesis in the presence of different metathesis catalysts at 760 Torr Et.sub.3Al Molar .sup.c Z/E Additive ratio T Time .sup.bConv. Isomer Entry Cat. (mol %) cat/olefin (° C.) [h] [%] TON ratio 1 11 0.1 1:1 000 r.t. 2.5 93 456 17/83 2 1 0.085 1:1 000 r.t. 2.5 92 453 20/80 3 42 0.085 1:1 000 r.t. 2.5 90 441 20/80 4 162 0.085 1:1 000 r.t. 2.5 95 464 16/84 5 10 0.085 1:10 000 r.t. 2.5 64 3144 19/81 6 11 0.085 1:10 000 r.t. 2.5 66 3218 21/79 7 1 0.085 1:10 000 r.t. 2.5 48 2340 24/76 8 42 0.085 1:10 000 r.t. 2.5 44 2161 22/78 9 162 0.085 1:10 000 r.t. 2.5 67 3299 18/82 .sup.bConversion = [area of (1,4-di(2-acetyloxyphenyl)-2-butene 3) × 2)/area of ((1,4-di(2-acetyloxyphenyl)-2-butene 3) × 2 + area of 2-allylphenylacetate 2)]. (based on calibrated GCMS data) .sup.cThe E/Z isomers were separable in GC. The E isomer could be isolated by flash chromatography and characterized by NMR. TON = Turn Over Number.
Experimental:

(24) Entry 1. All manipulation was performed under the inert atmosphere of the glovebox. 2-allylphenylacetate was pretreated with 0.1 mol % Et.sub.3Al (25 weight % in toluene). The pretreated substrate stock solution (171 μl, 1 mmol) was measured into a 4 ml glass vial. 0.1 M stock solution of catalyst 11 (1 μmol, 10 μL) was added at r.t. and the vial was capped with a perforated cap to vent out the evolving ethylene. The reaction mixture was stirred at the same temperature for 2.5 h. The reaction mixture was taken out from the glovebox and quenched with ethyl acetate. Internal standards, mesitylene (c=60 mg/mL) and pentadecane (c=60 mg/mL) were added, the solution was poured onto the top of a silica column (1.0 mL) and eluted with EtOAc (10 mL). The collected eluate was analyzed by GCMS. Conversion: 93%, TON: 456, Z/E Isomer ratio: 17/83

(25) Entry 9. All manipulation was performed under the inert atmosphere of the glovebox. 2-Allylphenylacetate was pretreated with 0.085 mol % Et.sub.3Al (25 weight % in toluene). The pretreated substrate stock solution (1711 μl, 10 mmol) was measured into a 10 ml glass vial. 0.1 M stock solution of compound 162 (1 μmol, 10 μL) was added at r.t. and the vial was capped with a perforated cap to vent out the evolving ethylene. The reaction mixture was stirred at the same temperature for 2.5 h. The reaction mixture was taken out from the glovebox and quenched with ethyl acetate. Internal standards, mesitylene (c=60 mg/mL) and pentadecane (c=60 mg/mL) were added and the volume of the mixture was diluted to 10 mL. 1 mL of the solution was poured onto the top of a silica column (1.0 mL) and eluted with EtOAc (10 mL). The collected eluate was analyzed by GCMS. Conversion: 67%, TON: 3299, Z/E Isomer ratio: 18/82

(26) General:

(27) All reactions under the glovebox were carried out in owendried (140° C.) glassware under an inert atmosphere of N.sub.2 unless otherwise stated. All catalyst was used as 0.1 M stock solution in C.sub.6D.sub.6 or benzene.

(28) TLC was performed on 0.25 mm Merck silica gel 60 F.sub.254 plates and visualized under UV light (254 nm) and iodine vapor. GCMS chromatograms were recorded on a Shimadzu GC2010 Plus instrument. .sup.1H NMR were recorded on a Varian XL-200 (200 MHz) spectrometer. Chemical shifts are reported in ppm from tetramethylsilane with the tetramethylsilane resonance as the internal reference (δ 0.00). Data are reported as follows: chemical shift, integration, multiplicity (s=singulet, d=doublet, t=triplet, hept=heptate, br=broad, m=multiplet).

(29) 4. Screening of Various Compounds in a Homo Cross Metathesis Reaction (HCM) of allylbenzene at different catalyst loadings according to the following Scheme 4:

(30) ##STR00110##
4.1 Purification of Crude Allylbenzene by Physicochemical Pretreatment

(31) Crude allylbenzene (substrate) was distilled under atmospheric pressure. Its peroxide content was determined by titration and found to be 0.01 mol %. Then the substrate was percolated on 20 weight % activated aluminum oxide 90 (active basic). By that method hydroperoxide content could be decreased under the detection limit and water content under 5 ppms. The percolated substrate was stored over molecular sieve and applied in self-metathesis reaction using different catalysts.

(32) The reaction was tested with novel compound 11 using different molar ratios of catalyst/substrate. Results are summarized at Table 4. The selected catalyst gives practically complete conversion after 1 h.

(33) TABLE-US-00005 TABLE 4 Results of allylbenzene (1) self-metathesis in the presence of novel compound 11 Cat/ Time Conv..sup.a E/Z Entry Subs. T (° C.) [h] [%] ratio.sup.b 1 1:1 000 r.t. 1 97 85/15 2 1:1 000 r.t. 18 >99 86/14 3 1:5 000 r.t. 1 97 86/14 4 1:5 000 r.t. 4 100 87/13 5 1:10 000 r.t. 1 94 86/14 6 1:10 000 r.t. 4 97 87/13 7 1:20 000 r.t. 1 93 89/11 8 1:20 000 r.t. 2 95 88/12 9 1:20 000 r.t. 4 96 89/11 .sup.aConversion = [(area of 1,4-diphenylbutene 2) × 2/((area of 1,4-diphenylbutene 2) ×) 2 + area of allylbenzene 1]. .sup.bThe E/Z isomers were separable in GC. The mixture was measured by .sup.1H NMR, and the chemical shifts of isomers were compared to the literature data. The major component was found to be the E isomer. .sup.dthe catalyst was used from 0.1M stock solution in C.sub.6D.sub.6 or benzene

(34) The reaction was carried out with further catalysts as presented at Table 5 below. Compound 10 is known, compounds 11, 21, 30, 32, 36, 42 are novel.

(35) TABLE-US-00006 TABLE 5 Selected results of allylbenzene (1) self-metathesis in the presence of various catalyst T Time E/Z Entry Cat. Cat./Subs. (° C.) [h] Conv..sup.a[%] ratio.sup.b 1 10 1:20 000 r.t. 2 90 91/9 2 11 1:20 000 r.t. 2 95 88/12 3 21 1:20 000 r.t. 2 63 57/43 4 30 1:20 000 r.t. 2 41 26/74 5 32 1:20 000 r.t. 2 83 90/10 6 36 1:20 000 r.t. 2 92 87/13 7 42 1:20 000 r.t. 2 85 89/11 .sup.aConversion = [(area of 1,4-diphenylbutene 2) × 2/((area of 1,4-diphenylbutene 2) ×) 2 + area of allylbenzene 1]. .sup.bThe E/Z isomers were separable in GC. The mixture was measured by 1H NMR, and the chemical shifts of isomers were compared to the literature data. The major component was found to be the E isomer.
Experimental:

(36) Reactions in Table 5 were performed according to the following protocol: All manipulation was performed under the inert atmosphere of the Glove-Box. Allylbenzene (20 mmol, 2650 μL) was measured into a 10 ml glass vial. 0.1 M stock solution (1 μmol, 10 μL) of the catalyst was added at r.t. and the reaction mixture is stirred at the same temperature for 2 h. 100 μl sample was taken out from the Glove-Box and quenched with 2 mL EtOAc. The solution was poured onto the top of a silica column (1.0 mL) and eluted with EtOAc (10 mL). From the collected elute 200 μL was analyzed by GCMS.

(37) 4.2 Purification of Allylbenzene by a Chemical Purification Step: Reaction of By-Products with Trioctyl Aluminum

(38) Allylbenzene was purchased from Sigma-Aldrich (A29402-100 ML, Lot No.: 55496LMV, Certificate of analysis: 99.9%). In house GCMS analysis: 99.64% allylbenzene, 0.27% cinnamaldehyde, 0.07% unknown impurities. Hydroperoxide content: 0.68 mol % by titration. Water content by KF titration: 973 ppm, 0.63 mol %.

(39) Crude allylbenzene was pretreated with different amount of Oc.sub.3Al. After pretreatment the crude substrate was applied in metathesis reaction. The reaction was characterized by the conversion data and the necessary amount of Oc.sub.3Al could be optimized.

(40) 0.8-1.2 mol % Oc.sub.3Al efficiently removed impurities. The optimum was not determined because of the high conversion in each point. Results with known catalyst 1 are listed at Table 6.

(41) TABLE-US-00007 TABLE 6 Application of Oc3Al pretreatment in allylbenzene self-metathesis in the presence of 100 mol ppm of catalyst 1 Oc.sub.3Al Conv. E/Z Entry [mol %] [%].sup.a TON ratio.sup.b 1 0.2 0 0 — 2 0.4 0 0 — 3 0.5 0 0 — 4 0.6 2 78 67/33 5 0.7 37 1872 89/11 6 0.8 88 4407 88/12 7 0.9 96 4810 87/13 8 1 95 4753 86/14 9 1.1 96 4800 86/14 10 1.2 96 4817 86/14 11 1.3 12 608 85/15 12 1.4 2 98 75/25 13 1.5 0 0 — Allylbenzene quality: crude, hydroperoxide/water content = 0.68%/0.63%, Additive: Oc3Al (25 weight % in hexane), Pretreatment conditions: 18 h stirring at r.t, Catalyst: 1, S/C = 10 000, Metathesis conditions: 4h, r.t. .sup.aConversion = [(area of 1,4-diphenylbutene 2) × 2/((area of 1,4-diphenylbutene 2) ×) 2 + area of allylbenzene 1]. .sup.bThe E/Z isomers were separable in GC.

(42) Table 7 presents the application of Oc.sub.3Al pretreatment in allylbenzene self-metathesis in the presence of 50 mol ppm of known catalyst 1 and novel catalysts 178, 162, 168, 183, 184 and 123:

(43) TABLE-US-00008 TABLE 7 Application of Oc3Al pretreatment in allylbenzene (1) self- metathesis in the presence of 50 mol ppm catalysts Oc.sub.3Al Conversion [%].sup.a Entry [mol %] 1 178 162 168 183 184 11 123 1 0.9 91 18 48 64 48 85 34 90 2 1 95 83 91 92 58 94 88 92 3 1.10 85 91 90 92 85 93 91 91 4 1.20 12 90 11 87 77 87 82 93 Pretreatment conditions: 18 h stirring at r.t, Catalyst/substrate = 1:20 000, Metathesis conditions: 4 h, r.t.

(44) Table 8 presents the effect of the pretreatment time. It was found that under the given conditions the reaction goes to completion practically in 2-4 h.

(45) TABLE-US-00009 TABLE 8 Study of the effect of pretreatment time of crude allylbenzene in self-metathesis catalyzed by known catalyst 1 Purification time Conv. E/Z [h] [%].sup.b TON ratio.sup.c 1 74 3677 88/12 2 91 4531 87/13 3 90 4524 87/13 4 92 4605 87/13 18 96 4810 87/13 Allylbenzene quality: crude, hydroperoxide/water content = 0.68%/0.63%, Additive: 0.9 ml % Oc3Al (25 weight % in hexane),catalyst: 1, Catalyst/Substrate = 1: 10 000, Metathesis conditions: 4h, r.t. .sup.aConversion = [(area of 1,4-diphenylbutene 2) × 2/((area of 1,4-diphenylbutene 2) ×) 2 + area of allylbenzene 1]. .sup.cThe E/Z isomers were separable in GC.
Experimental:

(46) If catalyst/substrate=1:10 000, (100 mol ppm catalyst), reactions in Table 7 and Table 8 were performed according to the following protocol: All manipulation was performed under the inert atmosphere of the Glove-Box. 662 μl (5 mmol) of allylbenzene (H.sub.2O content 973 ppm, 0.63%, peroxide content 0.68%) was measured into a 5 ml glass vial. Oc.sub.3Al (25% sol. in hexane) was added to it and the mixture was stirred for 1-18 h. Then 0.1 M stock solution (5 μl, 1 μmol, 100 mol ppm) of the catalyst was added at r.t. and the reaction mixture is stirred at the same temperature for 4 h. Then the reaction mixture was taken out of the glovebox and quenched with 100 μL MeOH. Internals standards were added: mesitylene in EtOAc and pentadecane (1 mL, c=60 mg/mL). The volume was diluted to 5 mL. 1 mL of this solution was poured onto the top of silica column 1 (mL) and eluted with EtOAc (10 mL). From the collected elute 100 μL is analyzed by GC or GCMS.

(47) If catalyst/substrate=1:20 000, (50 mol ppm catalyst), reactions in Table 7 were performed according to the following protocol: All manipulation was performed under the inert atmosphere of the Glove-Box. 1362 μl (10 mmol) of allylbenzene (H.sub.2O content 973 ppm, 0.63%, peroxide content 0.68%) was measured into a 10 ml glass vial. Oc.sub.3Al (25% sol. in hexane) was added to it and the mixture was stirred for 18 h. Then 0.1 M stock solution (5 μl, 0.5 μmol, 50 mol ppm) of the catalyst was added at r.t. and the reaction mixture is stirred at the same temperature for 4 h. Then the reaction mixture was taken out of the glovebox and quenched with 100 μL MeOH. Internals standards were added: mesitylene in EtOAc and pentadecane (1 mL, c=60 mg/ml). The volume was diluted to 10 mL. 1 mL of this solution was poured onto the top of silica column 1 (mL) and eluted with EtOAc (10 mL). From the collected elute 100 μL is analyzed by GC or GCMS.

(48) Trioctylaluminum, which allows a safe handling, efficiently destroys impurities in allylbenzene substrate and allows to reach high conversion even at such a low catalyst loading as of 50 mol ppm.

(49) 5. Screening of Compounds in Ring Closing Metathesis (RCM) of Diethyl Diallylmalonate (DEDAM) Depending on Purification

(50) Crude diethyl diallylmalonate was purchased from Sigma-Aldrich, its water content by Karl-Fischer titration was 346 weight ppm (0.46 mol %). The solution of the crude substrate was pretreated (stirred) with Oc.sub.3Al then applied in RCM reaction using novel compound 11 as catalyst under standard conditions.

(51) Diethyl diallylmalonate was pre-dried on 20 weight % molecular sieve for 24 h. Its water content was decreased from 346 weight ppm (0.46 mol %) to 14.7 weight ppm, 0.019 mol %. Without Oc.sub.3Al purification no metathesis reaction could be performed (Table 9, entry 1). After 0.175 mol % trioctyl aluminum treatment the metathesis could be performed at high conversion (Table 9, entry 8)

(52) TABLE-US-00010 TABLE 9 Results of diethyl diallylmalonate (1) RCM reaction after predrying the substrate on molecular sieve and subsequent Oc3Al pretreatment (purification) Water of content of Amount substrate Oc.sub.3Al Purification Conv. Entry [mol %] [mol %] time [h] Cat. No. [%].sup.b 1 0.019 0 1 11 3 2 0.019 0.025 1 11 6 3 0.019 0.05 1 11 6 4 0.019 0.075 1 11 2 5 0.019 0.1 1 11 9 6 0.019 0.125 1 11 51 7 0.019 0.15 1 11 62 8 0.019 0.175 1 11 74 9 0.019 0.2 1 11 66 .sup.bConversion = [(area of diethyl cyclopent-3-ene-1,1-dicarboxylate 2)/(area of diethyl cyclopent-3-ene-1,1-dicarboxylate 2) + (area of diethyl diallylmalonate (1)] without calibration. Pretreatment conditions: CDEDAM = 1M in toluene, 0-0.2% Oc3Al, 1h, r.t. Metathesis conditions:catylst/substrate = 1:2500, catalyst 11 loading = 400 mole ppm, 4h, r.t.

(53) Table 10 shows the results of the improved conversion if purification period is prolonged:

(54) TABLE-US-00011 TABLE 10 Results of diethyl diallylmalonate (1) RCM reaction after Oc.sub.3Al purification time using 24 h purification time Water Amount content of of substrate additive Purification Cat. Conv. Entry [mol %] Additive [mol %] time [h] No. [%] 1 0.82 Oct.sub.3Al 0 24 11 0 2 0.82 Oct.sub.3Al 0.25 24 11 3 3 0.82 Oct.sub.3Al 0.5 24 11 89 4 0.82 Oct.sub.3Al 0.75 24 11 90 5 0.82 Oct.sub.3Al 1 24 11 96 6 0.82 Oct.sub.3Al 1.25 24 11 96 7 0.82 Oct.sub.3Al 1.5 24 11 52 8 0.82 Oct.sub.3Al 1.75 24 11 1 .sup.bConversion = [(area of diethyl cyclopent-3-ene-1,1-dicarboxylate 2)/(area of diethyl cyclopent-3-ene-1,1-dicarboxylate 2) + (area of diethyl diallylmalonate (1)] without calibration. Purification conditions: C.sub.DEDAM = 1M in toluene, 0-1.75% Oc.sub.3Al; 24 h, r.t. Metathesis conditions: catalyst/substrate = 1:2500, 11 catalyst loading = 400 mole ppm, 4 h, r.t.
6. Screening of Compound 11 in Homo Cross Metathesis (HCM) of allyl benzene, Depending on Purification and Addition Mode of Catalyst

(55) Allyl benzene containing 973 ppm (0.6 mol %) of water was pretreated with 1 mole % of Oc.sub.3Al for a period of 18 h. Subsequent to the purification, 33 mole % of novel compound 11 was added in one batch. After a period of 4 h, the conversion was 81%.

(56) The experiment was repeated with the difference that the pretreatment time was extended to 60 h, and that the catalyst was added in four portions of 8.25 mole %, respectively. After a period of 2 h subsequent to the addition of the first portion, the conversion was 38%. Then the second portion was added. After further 2 h, the conversion was 84%. Then the third portion was added. After further 2 h, the conversion was 93%. Then the last portion was added. After further 2 h, the conversion was 94%.

(57) 7. Screening of Various Compounds in Ethenolysis

(58) Performance of catalysts was compared in ethenolysis of purified unsaturated triglycerides. The purification method was a chemical pretreatment with trialkylaluminum. Triglyceride was subjected to ethylene at a temperature of 50° C. and a pressure of 10 bar for 18 hours using various amounts of catalyst.

(59) Metathesis reaction was characterized by the conversion data. As the catalysts were used in the same amount [1000 ppm (weight)—250 ppm (weight)—25 ppm (weight) respectively], their molar ratio is depending on their molecular weight. Normalized conversion was obtained by linear extrapolation of real conversion calculated from real molar quantity.

(60) Table 11 shows the superior results of novel catalysts 123 and 124 in which R.sup.6 is phenyl substituted with phenyl in 2-, 3-, 5- and 6-position, and 4-position is substituted with bromine compared to known catalyst 154, which bears hydrogen in 4-position of the phenyl moiety.

(61) TABLE-US-00012 TABLE 11 Compound 154 123 124 C.sub.1000 ppm (weight) catalyst [%] 61 84 79 C.sub.norm 1000 ppm (weight) catalyst [%] 63 94 102 C.sub.250 ppm (weight) catalyst [%] 39 49 C.sub.norm 250 ppm (weight) catalyst [%] 44 63

(62) Table 12 shows the results of catalysts in which R.sup.6 is a phenyl ring which is substituted in 2-, 4- and 6-position, wherein the 2- and 6-position are substituted by substituents via a carbon atom, and the substituent in 4-position may be attached to the phenyl ring via any atom. Compound 113 is known, the other compounds are novel.

(63) TABLE-US-00013 TABLE 12 Compound 130 188 113 131 184 114 142 168 C.sub.1000 ppm (weight) catalyst [%] 49 85 65 93 97 47 82 84 C.sub.norm 1000 ppm (weight) catalyst [%] 69 76 57 90 90 44 72 76 C.sub.250 ppm (weight) catalyst [%] 92 55 49 51 C.sub.norm 250 ppm (weight) catalyst [%] 89 51 42 46

(64) Table 13 shows the results of further catalysts in which R.sup.6 is a phenyl ring which is substituted in 2-, 4- and 6-position, wherein the 2- and 6-position are substituted by substituents via a carbon atom, and the substituent in 4-position is fluorine. Compounds 35, 122, 127, 131 and 135 are novel

(65) TABLE-US-00014 TABLE 13 Compound 127 122 35 135 131 C.sub.1000 ppm (weight) catalyst [%] 87 87 77 76 93 C.sub.norm 1000 ppm (weight) catalyst [%] 81 78 74 80 90

(66) Table 14 shows the results of novel catalysts 178 and 233 in which R.sup.6 is a phenyl ring which is substituted in 2- and 6-position via a phenyl moiety.

(67) TABLE-US-00015 TABLE 14 Compound 178 233 C.sub.1000 ppm (weight) catalyst [%] 82 87 C.sub.norm 1000 ppm (weight) catalyst [%] 70 87 C.sub.250 ppm (weight) catalyst [%] 46 C.sub.norm 250 ppm (weight) catalyst [%] 39
8. Screening of Various Compounds Bearing a [8-(naphthalene-1-yl)-naphthalene-1-yl]oxy ligand or a (8-phenlynaphthalene-1-yl)oxy ligand as R.sup.4

(68) Table 15 shows the efficacy of the novel compounds 192, 196, 214, 216, 217, 220, 246, 247, 269, 288 in the homo cross metathesis of methyldecenoate (HCM of DAME), in the homo cross metathesis of allylbenzene (HCM of DAME), in the ring closing metathesis of diethyl diallylmalonate (RCM of DEDAM) and in ethenolysis of unsaturated glycerides. S/C is molar ratio of the substrate to catalyst):

(69) TABLE-US-00016 TABLE 15 Catalyst activity in different metathesis reactions Conversion (%) Conversion Conversion in HCM Conversion (%) in (%) in of DAME, (%) in RCM of TG loading: HCM of AB DEDAM 400 ethenolysis 50 ppm mole 50 ppm mole ppm mole 1000 (S/C = (S/C = (S/C = ppm 20000/1) 20000/1) 2500/1) weight 192 26 12 87 54 196 81 3 >99 93 220 73 68 >99 217 13 25 >99 44 214 76 81 >99 97 218 20 35 42 58 216 88 72 >99 97 247 14 8 246 not tested 20 11 20 288 not tested not tested not tested not tested 269 not tested 5 9 36

(70) Table 16 shows the efficacy of novel catalysts 207, 208, 214, 216, 220 in HCM of allylbenzene. Allylbenzene was physicochemically treated before metathesis reaction, which means that it was percolated on an activated basic alumina layer (20 weight %). Then it was allowed to stand on 20% molecular sieve at least 1 day before metathesis reaction.

(71) TABLE-US-00017 TABLE 16 Compound 207 214 208 220 216 C .sub.50 ppm (mole catalyst loading 82 81 83 68 72 [%]
9. Screening of Compounds Bearing 2,6-diphenyl phenols and 2-Br-6-arylphenols as Ligand R.sup.4 in HCM of Allylbenzene Using a Chemically Treated Substrate

(72) HCM reactions were carried out in a glovebox atmosphere at r.t. for 4 h in a vented vial. Typical substrate/catalyst ratios are: 20 000=50 ppm mole catalyst loading, 30 000=33 ppm mole catalyst loading. After the reaction was quenched by “wet” EtOAc samples were filtered through on a silica layer and analysed by GCMS-FID. The used catalysts are all novel.

(73) Results are summarized at Table 17:

(74) TABLE-US-00018 TABLE 17 Compound 162 183 178 168 184 C .sub.50 ppm (mole catalyst loading) 91 58 83 92 94 [%] C .sub.33 ppm (mole catalyst loading) 21 9 63 60 79 [%]
10. Screening of Compounds Bearing a 2,3,5,6-tetraphenylphenoxy moiety as Ligand R.sup.4 in HCM of methyl decenoate (DAME) Using a Physically Pretreated Substrate According to Scheme 5

(75) ##STR00111##

(76) The substrate was purified by a physical treatment method, i.e. percolation on activated alumina layer. The reaction was characterized by the conversion data. Data are summarized in Table 18.

(77) TABLE-US-00019 TABLE 18 Compound 10 11 32 154 123 124 C .sub.50 ppm (mole catalyst loading) not 94 75 60 90 80 [%] tested C .sub.33 ppm (mole catalyst loading) 79 80 77 not 68 67 [%] tested

(78) Compounds 10, 11 and 32 are Mo-complexes, whereas compounds 154, 123 and 124 are W-complexes. Compounds 10 and 154 are known, compounds 11, 32, 123 and 124 are novel.

(79) Compound 10 has a 2,3,5,6-tetraphenlyphenoxy compound as ligand R.sup.4, whereas compound 11 is the respective 4-bromo-2,3,5,6-tetraphenylphenoxy compound and compound 32 is the 4-bromo-2,6-di(4-bromophenyl)-3,5-diphenylphenoxy analogue. R.sup.1 in each case is 2,6-diisopropylphenyl.

(80) Compound 154 bears a 2,3,5,6-tetraphenylphenoxy residue as ligand R.sup.4, whereas compound 123 is the respective 4-bromo-2,3,5,6-tetraphenylphenoxy compound and compound 124 the 4-bromo-2,6-di(4-bromophenyl)-3,5-diphenylphenoxy analogue. R.sup.1 in each case is 2,6-dichlorophenyl.

(81) The new catalysts exhibit excellent activity.