WO2015126462A1 - Préparation de tensioactifs par métathèse croisée - Google Patents

Préparation de tensioactifs par métathèse croisée Download PDF

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WO2015126462A1
WO2015126462A1 PCT/US2014/059783 US2014059783W WO2015126462A1 WO 2015126462 A1 WO2015126462 A1 WO 2015126462A1 US 2014059783 W US2014059783 W US 2014059783W WO 2015126462 A1 WO2015126462 A1 WO 2015126462A1
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substituted
phenyl
linear
another embodiment
benzene
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PCT/US2014/059783
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Adam M. Johns
Richard L. Pederson
Rosemary Conrad KISER
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Materia, Inc.
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Priority claimed from PCT/US2014/033568 external-priority patent/WO2014169080A1/fr
Application filed by Materia, Inc. filed Critical Materia, Inc.
Publication of WO2015126462A1 publication Critical patent/WO2015126462A1/fr
Priority to US14/877,632 priority Critical patent/US9758445B2/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
    • C07C67/11—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond being mineral ester groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
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    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/32—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by introduction of halogenated alkyl groups into ring compounds
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    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
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    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
    • C07C29/124—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids of halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
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    • C07—ORGANIC CHEMISTRY
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    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/178—Unsaturated ethers containing hydroxy or O-metal groups
    • C07C43/1785—Unsaturated ethers containing hydroxy or O-metal groups having more than one ether bound
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    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
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    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
    • C—CHEMISTRY; METALLURGY
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    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/18—Carbon
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    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
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    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/24—Phosphines

Definitions

  • compositions comprising alkene benzenes compositions comprising alkene benzene sulfonates, methods for making alkene benzenes, methods for making alkene benzene sulfonates, compositions comprising alkylbenzenes, compositions comprising alkylbenzene sulfonates, methods for making alkylbenzenes, and methods for making alkylbenzene sulfonates.
  • compositions comprising substituted alkene benzenes compositions comprising substituted alkene benzene sulfonates, methods for making substituted alkene benzenes, methods for making substituted alkene benzene sulfonates, compositions comprising substituted alkylbenzenes, compositions comprising substituted alkylbenzene sulfonates, methods for making substituted alkylbenzenes, and methods for making substituted alkylbenzene sulfonates, where the benzene ring is substituted with one or more groups designated R*, where R* is defined herein.
  • This invention describes a process to produce 2- phenyl linear alkyl benzene sulfonates (2-PhLAS) by cross metathesis of alpha-methyl styrene (AMS) or 3- phenyl- 1 -butene (3PhlC/ t ) with a linear alpha olefin (AO) or a linear internal olefin (IO) to produce 2- phenyl linear alkene benzenes (2-PhLAeB).
  • the 2-phenyl linear alkene benzenes (2-PhLAeB) are hydrogenated and sulfonated by well-known methodologies to yield 2-phenyl linear alkylbenzene sulfonates (2-PhLAS).
  • This invention describes a process to produce substituted 2-phenyl linear alkyl benzene sulfonates (2-Ph*LAS), where the benzene ring is substituted with one or more groups designated R*, by cross metathesis of substituted alpha-methyl styrene (AM*S), where the benzene ring is substituted with one or more groups designated R*, or substituted 3 -phenyl- 1 -butene (3Ph* lC/ t ) where the benzene ring is substituted with one or more groups designated R*, with a linear alpha olefin (AO) or a linear internal olefin (IO) to produce substituted 2-phenyl linear alkene benzenes (2-Ph*LAeB), where the benzene ring is substituted with one or more groups designated R*, where R* is defined herein.
  • AO linear alpha olefin
  • IO linear internal olefin
  • the substituted 2-phenyl linear alkene benzenes (2-Ph*LAeB) are hydrogenated and sulfonated by well-known methodologies to yield substituted 2-phenyl linear alkylbenzene sulfonates (2-Ph*LAS).
  • 2-Phenyl linear alkylbenzene sulfonates (2-PhLAS) and substituted 2-phenyl linear alkylbenzene sulfonates (2-Ph*LAS) are high- efficiency surfactants useful in hand soaps, dish soaps, hard surface cleaners, laundry detergents, and in cleaning supplies.
  • this invention relates to compositions comprising 2-ethoxylated hydroxymethylphenyl linear alkyl benzenes and to compositions comprising 2-propoxylated hydroxymethylphenyl linear alkyl benzenes.
  • This invention also relates to methods of making 2- ethoxylated hydroxymethylphenyl linear alkyl benzenes and to methods of making 2-propoxylated hydroxymethylphenyl linear alkyl benzenes.
  • This invention also relates to the use of compositions comprising 2-ethoxylated hydroxymethylphenyl linear alkyl benzenes and to the use of compositions comprising 2-propoxylated hydroxymethylphenyl linear alkyl benzenes.
  • this invention relates to articles of manufacture comprising compositions comprising 2-ethoxylated hydroxymethylphenyl linear alkyl benzenes and to articles of manufacture comprising compositions comprising 2-propoxylated hydroxymethylphenyl linear alkyl benzenes.
  • 2-ethoxylated hydroxymethylphenyl linear alkyl benzenes and 2-propoxylated hydroxymethylphenyl linear alkyl benzenes are surfactants, more specifically non-ionic surfactants, useful in hand soaps, dish soaps, hard surface cleaners, laundry detergents, and in various cleaning supplies and detergents and detergent compositions.
  • 2-tolyl linear alkylbenzene sulfonates have been reported to have lower Krafft temperatures and superior hard water tolerance compared to commercial linear alkylbenzene sulfonate materials (U.S. Pat. No. 6,995,127).
  • U.S. Pat. App. Pub. No 2012/0213726 is incorporated by reference and describes bio- based linear alkyl phenyl sulfonates (linear alkylbenzene sulfonates) incorporating C 10 -C 14 olefins which at least 50% bio-based.
  • the bio-based C 10 -C 14 olefins may be produced by metathesis of seed oils as described in U.S. Pat. App. Pub. No US2010/0145086.
  • 2012/0213726 does not describe olefin metathesis of alpha-methyl styrene or 3 -phenyl- 1-butene to produce linear alkyl phenyl sulfonates (linear alkylbenzene sulfonates).
  • WO Pat. App. Pub. No. 2012/138423 is incorporated by reference and describes C 10 -C13 linear alkyl phenyl sulfonates (linear alkylbenzene sulfonates) having a particular alkyl group distribution.
  • This application describes using a particular C 10 -C13 olefin distribution to produce C 10 -C13 linear alkyl phenyl sulfonates (linear alkylbenzene sulfonates).
  • U.S. Pat. App. Pub. No. 2010/0145086 is incorporated by reference and is the seminal patent application describing the production of alpha olefins from alkenolysis of seed oils. It does not describe olefin metathesis of alpha-methyl styrene or 3 -phenyl- 1-butene to produce linear alkyl benzenes, linear 2-phenylalkylbenzenes, linear alkyl phenyl sulfonates, or linear alkylbenzene sulfonates.
  • 2-tolyl linear alkyl benzene sulfonates having enhanced hard water tolerance.
  • This patent does not produce 2-phenyl linear alkylbenzene sulfonates in >85% isomeric purity and does not describe olefin metathesis to produce 2-phenyl linear alkylbenzene sulfonates.
  • the resulting 2-tolyl linear alkyl benzene sulfonates predominantly comprise para-tolyl groups due to the ortholpara directing effects of methyl (alkyl) groups (combined with steric effects which disfavor ort/zo-substitution).
  • electron-withdrawing groups i.e.
  • tolylstyrenes are available as a mixture of approximately 60% meta- and 40% para-mct yX substitution, which will produce a 2-tolyl linear alkylbenzene sulfonate with the same 60% meta- and 40% para-me ⁇ hy ⁇ substitution, or in a nearly pure para-me ⁇ hy ⁇ form.
  • a surfactant particularly a surfactant for use as a detergent, have good solubility and/or good foaming ability in cold-hard water.
  • Hard water is defined as water that contains mineral salts (e.g., calcium and magnesium ions), where the mineral salts act to limit the ability a surfactant to produce foam or lather.
  • mineral salts e.g., calcium and magnesium ions
  • surfactants that have reduced foaming ability generally possess less cleaning power or detergency. In other words, surfactants that do not foam or lather are generally poor detergents.
  • Ionic surfactants are surfactants that possess ionic groups (e.g., sulfate groups).
  • non-ionic surfactants generally possess less foaming ability in hard water due to interactions with the mineral salts present in the hard water.
  • non-ionic surfactants are surfactants that do not have ionic groups.
  • Non-ionic surfactants as a result, generally do not react with nor are they affected by the mineral salts present in hard water.
  • few non-ionic surfactants which possess good solubility and/or good foaming ability in cold-hard water are known and even fewer are commercially available. Therefore, an ongoing need exists for non-ionic surfactants which possess good solubility and/or good foaming ability in cold- hard water.
  • detergent compositions are typically complex mixtures there is a need for a wide variety of surfactants (non-ionic and/or ionic) having various structures and properties.
  • the present invention relates to compositions comprising alkene benzenes, compositions comprising alkene benzene sulfonates, methods for making alkene benzenes, methods for making alkene benzene sulfonates, compositions comprising alkylbenzenes, compositions comprising alkylbenzene sulfonates, methods for making alkylbenzenes, and methods for making alkylbenzene sulfonates.
  • compositions comprising 2-phenyl linear alkene benzenes compositions comprising 2-phenyl linear alkene benzene sulfonates, compositions comprising 2-phenyl linear alkylbenzenes, and compositions comprising 2-phenyl linear alkylbenzene sulfonates, methods for making 2-phenyl alkene benzenes, methods for making 2-phenyl alkene benzene sulfonates, methods for making 2-phenyl alkylbenzenes, and methods for making 2-phenyl alkylbenzene sulfonates.
  • the present invention also relates to compositions comprising substituted alkene benzenes, compositions comprising substituted alkene benzene sulfonates, methods for making substituted alkene benzenes, methods for making substituted alkene benzene sulfonates, compositions comprising substituted alkylbenzenes, compositions comprising substituted alkylbenzene sulfonates, methods for making substituted alkylbenzenes, and methods for making substituted alkylbenzene sulfonates, where the benzene ring is substituted with one or more groups designated R*, where R* is defined herein.
  • compositions comprising substituted 2- phenyl linear alkene benzenes, compositions comprising substituted 2-phenyl linear alkene benzene sulfonates, compositions comprising substituted 2-phenyl linear alkylbenzenes, and compositions comprising substituted 2-phenyl linear alkylbenzene sulfonates, methods for making substituted 2-phenyl alkene benzenes, methods for making substituted 2-phenyl alkene benzene sulfonates, methods for making substituted 2-phenyl alkylbenzenes, and methods for making substituted 2-phenyl alkylbenzene sulfonates, where the benzene ring is substituted with one or more groups designated R*, where R* is defined herein.
  • substituted linear alkylbenzene sulfonate compositions comprising increased substituted 2-phenyl linear alkylbenzene sulfonate content compared to prior art compositions, where the benzene ring of the substituted linear alkylbenzene sulfonate compositions is substituted with one or more groups designated R*, where R* is defined herein.
  • the present invention provides a linear alkylbenzene sulfonate composition, where the 2-phenyl isomer content is at least 85% by weight based on the total weight of linear alkyl benzene sulfonate isomers.
  • the present invention provides a substituted linear alkylbenzene sulfonate composition, where the substituted 2-phenyl isomer content is at least 85% by weight based on the total weight of substituted linear alkyl benzene sulfonate isomers, where the benzene ring of the substituted linear alkylbenzene sulfonate is substituted with one or more groups designated R*, where R* is defined herein.
  • the present invention provides a linear alkylbenzene composition, where the 2-phenyl isomer content is at least 85% by weight based on the total weight of linear alkylbenzene isomers.
  • the present invention provides a substituted linear alkylbenzene composition, where the substituted 2-phenyl isomer content is at least 85% by weight based on the total weight of substituted linear alkylbenzene isomers, where the benzene ring of the substituted linear alkylbenzene is substituted with one or more groups designated R*, where R* is defined herein.
  • the present invention provides a linear alkylbenzene composition, where the 2-phenyl isomer content is at least 85% by weight based on the total weight of linear alkylbenzene isomers described in the general formula:
  • n is equal to any integer between 2 and 18.
  • the present invention provides a substituted linear alkylbenzene composition, where the substituted 2-phenyl isomer content is at least 85% by weight based on the total weight of linear alkylbenzene isomers described in the general formula: n is equal to any integer between 2 and 18, where the benzene ring of the substituted linear alkylbenzene is substituted with one or more groups designated R*, where R* is defined herein.
  • n is equal to any integer between 2 and 18, wherein an amount of 2-phenyl alkylbenzene isomer in such alkylbenzene sulfonate salts is greater than 85% by weight based on the total weight of the alkylbenzene sulfonates, where the 2-phenyl alkylbenzene isomer is prepared by forming a first composition comprising styrene, at least one hydrovinylation catalyst, and ethylene, subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form 3 -phenyl- 1-butene, forming a second composition comprising 3 -phenyl- 1-butene, at least one olefinic substrate, and at least one olefin metathesis catalyst, wherein the at least one olefinic substrate is selected from a linear alpha olefin, or a linear internal olefin, or a combination thereof, subjecting the second composition to conditions effective to promote a cross metathesis reaction to
  • the salt comprises an amount of the substituted 2-phenyl alkylbenzene isomer of alkylbenzenes described by the general formula:
  • n is equal to any integer between 2 and 18, wherein R* is defined herein, wherein an amount of substituted 2-phenyl alkylbenzene isomer in such alkylbenzene sulfonate salts is greater than 85% by weight based on the total weight of the alkylbenzene sulfonates, where the substituted 2-phenyl alkylbenzene isomer is prepared by forming a first composition comprising a substituted styrene, at least one hydrovinylation catalyst, and ethylene, where the benzene ring of the substituted styrene is substituted with one or more groups designated R*, where R* is defined herein; subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form substituted 3 -phenyl- 1 -butene, where the benzene ring of the substituted 3 -phenyl- 1 -butene is substituted with one or more groups designated R*, where R* is defined herein
  • n is equal to any integer between 2 and 18, wherein an amount of 2-phenyl alkylbenzene isomer in such alkylbenzene sulfonate salts is greater than 85% by weight based on the total weight of the alkylbenzene sulfonates, where the 2-phenyl alkylbenzene isomer is prepared by forming a composition comprising alpha-methyl styrene, at least one olefinic substrate, and at least one olefin metathesis catalyst, wherein the at least one olefinic substrate is selected from a linear alpha olefin, or a linear internal olefin, or a combination thereof, subjecting the composition to conditions effective to promote a cross metathesis reaction to form at least one 2-phenyl linear alkene benzene, subjecting the at least one 2-phenyl linear alkene benzene to conditions effective to promote olefin hydrogenation to form at least one 2-phenyl linear alkylbenzen
  • n is equal to any integer between 2 and 18, wherein R* is defined herein, wherein an amount of substituted 2-phenyl alkylbenzene isomer in such alkylbenzene sulfonate salts is greater than 85% by weight based on the total weight of the alkylbenzene sulfonates, where the substituted 2-phenyl alkylbenzene isomer is prepared by forming a composition comprising substituted alpha-methyl styrene, at least one olefinic substrate, and at least one olefin metathesis catalyst, wherein at least one olefinic substrate is selected from a linear alpha olefin, or a linear internal olefin, or a combination thereof, where the benzene ring of the substituted alpha-methyl styrene is substituted with one or more groups designated R*, where R* is defined herein; subjecting the composition to conditions effective to promote a cross metathesis reaction to form at least one substituted
  • n is equal to any integer between 2 and 18, wherein the amount of 2-phenyl isomer in such alkylbenzene sulfonate salts is greater than 85% by weight based on the total weight of the alkylbenzene sulfonates.
  • n is equal to any integer between 2 and 18, wherein R* is defined herein, wherein the amount of substituted 2-phenyl isomer in such alkylbenzene sulfonate salts is greater than 85% by weight based on the total weight of the alkylbenzene sulfonates.
  • the present invention provides a method of making 2-phenyl alkene benzenes, the method comprising forming a composition comprising at least one cross metathesis substrate, at least one olefinic substrate, and at least one olefin metathesis catalyst, and subjecting the composition to conditions effective to promote a cross metathesis reaction between the at least one cross metathesis substrate and at least one olefinic substrate.
  • the present invention provides a method of making substituted 2- phenyl alkene benzenes, where the benzene ring of the substituted 2-phenyl alkene benzenes is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a composition comprising at least one cross metathesis substrate, at least one olefinic substrate, and at least one olefin metathesis catalyst, and subjecting the composition to conditions effective to promote a cross metathesis reaction between the at least one cross metathesis substrate and at least one olefinic substrate.
  • the present invention provides a method of making 2-phenyl linear alkene benzenes, the method comprising forming a composition comprising at least one cross metathesis substrate, at least one olefinic substrate, and at least one olefin metathesis catalyst, wherein the at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, and subjecting the composition to conditions effective to promote a cross metathesis reaction between the at least one cross metathesis substrate and at least one olefinic substrate.
  • the present invention provides a method of making substituted 2- phenyl linear alkene benzenes, where the benzene ring of the substituted 2-phenyl linear alkene benzenes is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a composition comprising at least one cross metathesis substrate, at least one olefinic substrate, and at least one olefin metathesis catalyst, wherein at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, and subjecting the composition to conditions effective to promote a cross metathesis reaction between at least one cross metathesis substrate and at least one olefinic substrate.
  • the present invention provides a method of making alkene benzenes, the method comprising forming a composition comprising at least one cross metathesis substrate, at least one olefinic substrate, and at least one olefin metathesis catalyst, and subjecting the composition to conditions effective to promote a cross metathesis reaction to form cross metathesis products, where the cross metathesis products comprise at least one alkene benzene.
  • the present invention provides a method of making substituted alkene benzenes, where the benzene ring of the substituted alkene benzenes is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a composition comprising at least one cross metathesis substrate, at least one olefinic substrate, and at least one olefin metathesis catalyst, and subjecting the composition to conditions effective to promote a cross metathesis reaction to form cross metathesis products, where the cross metathesis products comprise at least one substituted alkene benzene.
  • the present invention provides a method of making alkyl benzenes, the method comprising forming a composition comprising at least one cross metathesis substrate, at least one olefinic substrate, and at least one olefin metathesis catalyst, and subjecting the composition to conditions effective to promote a cross metathesis reaction to form cross metathesis products where the cross metathesis products comprise at least one alkene benzene, and subjecting the at least one alkene benzene to conditions effective to promote olefinic hydrogenation.
  • the present invention provides a method of making substituted alkyl benzenes, where the benzene ring of the substituted alkyl benzenes is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a composition comprising at least one cross metathesis substrate, at least one olefinic substrate, and at least one olefin metathesis catalyst; subjecting the composition to conditions effective to promote a cross metathesis reaction to form cross metathesis products where the cross metathesis products comprise at least one substituted alkene benzene, where the substituted alkene benzene is substituted with one or more groups designated R*, where R* is defined herein; and subjecting at least one substituted alkene benzene to conditions effective to promote olefinic hydrogenation.
  • the present invention provides a method of making alkylbenzene sulfonates, the method comprising forming a composition comprising at least one cross metathesis substrate, at least one olefinic substrate, and at least one olefin metathesis catalyst, and subjecting the composition to conditions effective to promote a cross metathesis reaction to form cross metathesis products where the cross metathesis products comprise at least one alkene benzene, and subjecting the at least one alkene benzene to conditions effective to promote olefinic hydrogenation to form hydrogenation products where the hydrogenation products comprise at least one alkylbenzene, and subjecting the at least one alkylbenzene to conditions effective to promote aromatic sulfonation.
  • the present invention provides a method of making substituted alkylbenzene sulfonates, where the benzene ring of the substituted alkylbenzene sulfonates is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a composition comprising at least one cross metathesis substrate, at least one olefinic substrate, and at least one olefin metathesis catalyst; subjecting the composition to conditions effective to promote a cross metathesis reaction to form cross metathesis products where the cross metathesis products comprise at least one substituted alkene benzene, where the benzene ring of the substituted alkene benzene is substituted with one or more groups designated R*, where R* is defined herein; and subjecting at least one substituted alkene benzene to conditions effective to promote olefinic hydrogenation to form hydrogenation products where the hydrogenation products comprise at least one substituted alkylbenzene, where the benzene ring
  • the present invention provides a method of making 2-phenyl linear alkene benzenes, the method comprising forming a composition comprising at least one cross metathesis substrate, at least one olefinic substrate, and at least one olefin metathesis catalyst, wherein the at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, subjecting the composition to conditions effective to promote a cross metathesis reaction to form cross metathesis products, where the cross metathesis products comprise at least one 2-phenyl linear alkene benzene, and separating at least a portion of the at least one 2-phenyl linear alkene benzene from the cross metathesis products.
  • the present invention provides a method of making substituted 2- phenyl linear alkene benzenes, where the benzene ring of the substituted 2-phenyl linear alkene benzenes is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a composition comprising at least one cross metathesis substrate, at least one olefinic substrate, and at least one olefin metathesis catalyst, wherein at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof; subjecting the composition to conditions effective to promote a cross metathesis reaction to form cross metathesis products, where the cross metathesis products comprise at least one substituted 2-phenyl linear alkene benzene, where the benzene ring of the substituted 2-phenyl linear alkene benzenes is substituted with one or more groups designated R*, where R* is defined herein;
  • the present invention provides a method of making 2-phenyl linear alkene benzenes, the method comprising forming a first composition comprising styrene, at least one hydrovinylation catalyst, and ethylene, subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form hydrovinylation products, where the hydrovinylation products comprise 3 -phenyl- 1-butene, forming a second composition comprising the hydrovinylation products comprising 3 -phenyl- 1-butene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where the at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, and subjecting the second composition to conditions effective to promote a cross metathesis reaction between 3 -phenyl- 1-butene and the at least one olefinic substrate.
  • the present invention provides a method of making substituted 2- phenyl linear alkene benzenes, where the benzene ring is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a first composition comprising substituted styrene, at least one hydrovinylation catalyst, and ethylene, where the benzene ring of the substituted styrene is substituted with one or more groups designated R*, where R* is defined herein; subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form hydrovinylation products, where the hydrovinylation products comprise substituted 3 -phenyl- 1-butene, where the benzene ring of the substituted 3 -phenyl- 1-butene is substituted with one or more groups designated R*, where R* is defined herein; forming a second composition comprising the hydrovinylation products comprising substituted 3 -phenyl- 1-butene, at least
  • the present invention provides a method of making 2-phenyl linear alkene benzenes, the method comprising forming a first composition comprising styrene, at least one hydrovinylation catalyst, and ethylene, subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form hydrovinylation products, where the hydrovinylation products comprise 3 -phenyl- 1-butene, forming a second composition comprising the hydrovinylation products comprising 3 -phenyl- 1-butene, at least one olefmic substrate, and at least one olefin metathesis catalyst, where the at least one olefmic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, subjecting the second composition to conditions effective to promote a cross metathesis reaction to form cross metathesis products, where the cross metathesis products comprise at least one 2-phenyl linear alkene benzene, where the at least one 2-pheny
  • the present invention provides a method of making substituted 2- phenyl linear alkene benzenes, where the benzene ring of the substituted 2-phenyhl linear alkene benzenes is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a first composition comprising substituted styrene, at least one hydrovinylation catalyst, and ethylene, where the benzene ring of the substituted styrene is substituted with one or more groups designated R*, where R* is defined herein; subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form hydrovinylation products, where the hydrovinylation products comprise substituted 3 -phenyl- 1-butene, where the benzene ring of the 3 -phenyl- 1-butene is substituted with one or more groups designated R*, where R* is defined herein; forming a second composition comprising the hydrovinylation products comprising
  • the present invention provides a method of making 2-phenyl linear alkene benzenes, the method comprising forming a first composition comprising styrene, at least one hydrovinylation catalyst, and ethylene, subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form hydrovinylation products, where the hydrovinylation products comprise 3 -phenyl- 1-butene, separating at least a portion of the 3 -phenyl- 1-butene from the hydrovinylation products, forming a second composition comprising the separated 3 -phenyl- 1-butene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where the at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, subjecting the second composition to conditions effective to promote a cross metathesis reaction between 3 -phenyl- 1-butene and at least one
  • the present invention provides a method of making substituted 2- phenyl linear alkene benzenes, where the benzene ring of the substituted 2-phenyl linear alkene benzenes is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a first composition comprising substituted styrene, at least one hydrovinylation catalyst, and ethylene, where the benzene ring of the substituted styrene is substituted with one or more groups designated R*, where R* is defined herein; subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form hydrovinylation products, where the hydrovinylation products comprise substituted 3 -phenyl- 1-butene, where the benzene ring of the 3 -phenyl- 1-butene is substituted with one or more groups designated R*, where R* is defined herein; separating at least a portion of the substituted 3 -phenyl
  • the present invention provides a method of making 2-phenyl linear alkene benzenes, the method comprising forming a first composition comprising styrene, at least one hydrovinylation catalyst, and ethylene, subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form hydrovinylation products, where the hydrovinylation products comprise 3 -phenyl- 1-butene, separating at least a portion of the 3 -phenyl- 1-butene from the hydrovinylation products, forming a second composition comprising the separated 3 -phenyl- 1-butene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where the at least one olefin metathesis substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, subjecting the second composition to conditions effective to promote a cross metathesis reaction to form cross metathesis products, where the cross metathesis products comprise
  • the present invention provides a method of making substituted 2- phenyl linear alkene benzenes, where the benzene ring of the 2-phenyl linear alkene benzenes is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a first composition comprising substituted styrene, at least one hydrovinylation catalyst, and ethylene, where the benzene ring of the substituted styrene is substituted with one or more groups designated R*, where R* is defined herein; subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form hydrovinylation products, where the hydrovinylation products comprise substituted 3 -phenyl- 1-butene, where the benzene ring of the substituted 3 -phenyl- 1-butene is substituted with one or more groups designated R*, where R* is defined herein; separating at least a portion of the substituted 3 -phenyl
  • the present invention provides a method of making 2-phenyl linear alkyl benzenes, the method comprising forming a first composition comprising alpha-methyl styrene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where the at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, subjecting the first composition to conditions effective to promote a cross metathesis reaction to form cross metathesis products, where the cross metathesis products comprise at least one 2- phenyl linear alkene benzene, where the at least one 2-phenyl linear alkene benzene is derived from a cross metathesis reaction between alpha-methyl styrene and at least one olefinic substrate, and subjecting the cross metathesis products comprising at least one 2-phenyl linear alkene benzene to conditions effective to promote olefin hydrogenation.
  • the present invention provides a method of making substituted 2- phenyl linear alkyl benzenes, where the benzene ring of the 2-phenyl linear alkyl benzenes is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a first composition comprising substituted alpha-methyl styrene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, where the benzene ring of the substituted alpha-methyl styrene is substituted with one or more groups designated R*, where R* is defined herein; subjecting the first composition to conditions effective to promote a cross metathesis reaction to form cross metathesis products, where the cross metathesis products comprise at least one substituted 2-phenyl linear alkene benzene
  • the present invention provides a method of making 2-phenyl linear alkyl benzenes, the method comprising forming a first composition comprising alpha-methyl styrene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where the at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, subjecting the first combination to conditions effective to promote a cross metathesis reaction to form cross metathesis products, where the cross metathesis products comprise at least one 2- phenyl linear alkene benzene, where the at least one 2-phenyl linear alkene benzene is derived from a cross metathesis reaction between alpha-methyl styrene and at least one olefinic substrate, separating at least a portion of the at least one 2-phenyl linear alkene benzene from the cross metathesis products, subjecting the separated at least one 2-phen
  • the present invention provides a method of making substituted 2- phenyl linear alkyl benzenes, where the benzene ring of the 2-phenyl linear alkyl benzenes is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a first composition comprising substituted alpha-methyl styrene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, where the benzene ring of the substituted alpha-methyl styrene is substituted with one or more groups designated R*, where R* is defined herein; subjecting the first combination to conditions effective to promote a cross metathesis reaction to form cross metathesis products, where the cross metathesis products comprise at least one substituted 2-phenyl linear alkene benzene
  • the present invention provides a method of making 2-phenyl linear alkyl benzenes, the method comprising forming a first composition comprising alpha-methyl styrene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where the at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, subjecting the first combination to conditions effective to promote a cross metathesis reaction to form cross metathesis products, where the cross metathesis products comprise at least one 2- phenyl linear alkene benzene, where the at least one 2-phenyl linear alkene benzene is derived from a cross metathesis reaction between alpha-methyl styrene and at least one olefinic substrate, separating at least a portion of the at least one 2-phenyl linear alkene benzene from the cross metathesis products; subjecting the separated at least one 2-phen
  • the present invention provides a method of making substituted 2- phenyl linear alkyl benzenes, where the benzene ring of the substituted 2-phenyl linear alkyl benzenes is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a first composition comprising substituted alpha-methyl styrene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, where the benzene ring of the substituted alpha-methyl styrene is substituted with one or more groups designated R*, where R* is defined herein; subjecting the first combination to conditions effective to promote a cross metathesis reaction to form cross metathesis products, where the cross metathesis products comprise at least one substituted 2-phenyl linear alkene benz
  • the present invention provides a method of making 2-phenyl linear alkyl benzenes, the method comprising forming a first composition comprising styrene, at least one hydrovinylation catalyst, and ethylene, subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form hydrovinylation products, where the hydrovinylation products comprise 3 -phenyl- 1-butene, forming a second composition comprising the hydrovinylation products comprising 3 -phenyl- 1-butene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where the at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, subjecting the second composition to conditions effective to promote a cross metathesis reaction to form cross metathesis products, where the cross metathesis products comprise at least one 2-phenyl linear alkene benzene, where the at least one 2-pheny
  • the present invention provides a method of making substituted 2- phenyl linear alkyl benzenes, where the benzene ring of the substituted 2-phenyl linear alkyl benzenes is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a first composition comprising substituted styrene, at least one hydrovinylation catalyst, and ethylene, where the benzene ring of the substituted benzene is substituted with one or more groups designated R*, where R* is defined herein; subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form hydrovinylation products, where the hydrovinylation products comprise substituted 3 -phenyl- 1-butene, where the benzene ring of the substituted 3 -phenyl- 1-butene is substituted with one or more groups designated R*, where R* is defined herein; forming a second composition comprising the hydrovinylation products comprising substitute
  • the present invention provides a method of making 2-phenyl linear alkyl benzenes, the method comprising forming a first composition comprising styrene, at least one hydrovinylation catalyst, and ethylene, subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form hydrovinylation products, where the hydrovinylation products comprise 3 -phenyl- 1-butene, separating at least a portion of the 3 -phenyl- 1-butene from the hydrovinylation products, forming a second composition comprising the separated 3 -phenyl- 1-butene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where the at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, subjecting the second composition to conditions effective to promote a cross metathesis reaction to form cross metathesis products, where the cross metathesis products comprise at least
  • the present invention provides a method of making substituted 2- phenyl linear alkyl benzenes, where the benzene ring of the substituted 2-phenyl linear alkyl benzenes is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a first composition comprising substituted styrene, at least one hydrovinylation catalyst, and ethylene, where the benzene ring of the substituted styrene is substituted with one or more groups designated R*, where R* is defined herein; subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form hydrovinylation products, where the hydrovinylation products comprise substituted 3 -phenyl- 1-butene, where the benzene ring of the 3 -phenyl- 1-butene is substituted with one or more groups designated R*, where R* is defined herein; separating at least a portion of the substituted 3 -phenyl
  • the present invention provides a method of making substituted 2- phenyl linear alkyl benzenes, where the benzene ring of the substituted 2-phenyl linear alkyl benzenes is substituted with one or more groups designated R*, where R* is defined herein, whereas the substitution pattern of the substituted 2-phenyl linear alkyl benzenes is retained from the substitution pattern of the substituted 3 -phenyl- 1-butene, where the benzene ring of the substituted 3 -phenyl- 1-butene is substituted with one or more groups designated R*, where R* is defined herein, whereas the substitution pattern of substituted 3 -phenyl- 1-butene is that of the starting substituted styrene, where the benzene ring of the substituted styrene is substituted with one or more groups designated R*, where R* is defined herein.
  • tolylstyrene is a mixture of approximately 60% meta and 40% para methyl substitution, which will produce 3 -to lyl- 1-butene containing the same 60% meta and 40% para methyl substitution, which will produce 2-tolyl linear alkenylbenzene with the same 60% meta and 40% para methyl substitution, which will produce 2-tolyl linear alkylbenzene with the same 60% meta and 40% para methyl substitution and which will produce 2-tolyl linear alkylbenzene sulfonate with the same 60% meta and 40% para methyl substitution.
  • the present invention provides a method of making 2-phenyl linear alkyl benzenes, the method comprising forming a first composition comprising styrene, at least one hydrovinylation catalyst, and ethylene, subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form hydrovinylation products, where the hydrovinylation products comprise 3 -phenyl- 1-butene, separating at least a portion of the 3 -phenyl- 1-butene from the hydrovinylation products, forming a second composition comprising the separated 3 -phenyl- 1-butene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where the at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, subjecting the second composition to conditions effective to promote a cross metathesis reaction to form cross metathesis products, where the cross metathesis products comprise at least
  • the present invention provides a method of making substituted 2- phenyl linear alkyl benzenes, where the benzene ring of the substituted 2-phenyl linear alkyl benzenes is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a first composition comprising substituted styrene, at least one hydrovinylation catalyst, and ethylene, where the benzene ring of the substituted styrene is substituted with one or more groups designated R*, where R* is defined herein; subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form hydrovinylation products, where the hydrovinylation products comprise substituted 3 -phenyl- 1-butene, where the benzene ring of the 3 -phenyl- 1-butene is substituted with one or more groups designated R*, where R* is defined herein; separating at least a portion of the substituted 3 -phenyl
  • the present invention provides a method of making 2-phenyl linear alkyl benzene sulfonates, the method comprising forming a first composition comprising alpha- methyl styrene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where the at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, subjecting the first composition to conditions effective to promote a cross metathesis reaction to form cross metathesis products, where the cross metathesis products comprise at least one 2-phenyl linear alkene benzene, where the at least one 2-phenyl linear alkene benzene is derived from the cross metathesis reaction between alpha-methyl styrene and at least one olefinic substrate, separating at least a portion of the at least one 2-phenyl linear alkene benzene from the cross metathesis products, subjecting the separated at
  • the present invention provides a method of making substituted 2- phenyl linear alkyl benzene sulfonates, where the benzene ring of the 2-phenyl linear alkyl benzene sulfonates is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a first composition comprising substituted alpha-methyl styrene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, where the benzene ring of the substituted alpha-methyl styrene is substituted with one or more groups designated R*, where R* is defined herein; subjecting the first composition to conditions effective to promote a cross metathesis reaction to form cross metathesis products, where the cross metathesis products comprise at least one substituted 2-phen
  • the present invention provides a method of making substituted 2- phenyl linear alkyl benzene sulfonates, where the benzene ring of the substituted 2-phenyl linear alkyl benzene sulfonates is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a first composition comprising substituted styrene, at least one hydrovinylation catalyst, and ethylene, where the benzene ring of the substituted styrene is substituted with one or more groups designated R*, where R* is defined herein; subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form hydrovinylation products, where the hydrovinylation products comprise substituted 3-phenyl-l -butene, where the benzene ring of the substituted 3-phenyl-l -butene is substituted with one or more groups designated R*, where R* is defined herein; forming a second composition comprising substituted
  • the present invention provides a method of making 2-phenyl linear alkyl benzene sulfonates, the method comprising forming a first composition comprising styrene, at least one hydrovinylation catalyst, and ethylene, subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form 3 -phenyl- 1-butene, forming a second composition comprising 3 -phenyl- 1-butene, at least one olefinic substrate, and at least one olefin metathesis catalyst, wherein the at least one olefinic substrate is selected from a linear alpha olefin, or a linear internal olefin, or a combination thereof, subjecting the second composition to conditions effective to promote a cross metathesis reaction to form at least one 2-phenyl linear alkene benzene, subjecting the at least one 2- phenyl linear alkene benzene to conditions effective to promote olefin hydrogenation to form at least one 2-
  • the present invention provides a method of making substituted 2- phenyl linear alkyl benzene sulfonates, where the benzene ring of the substituted 2-phenyl linear alkyl benzene sulfonates is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a first composition comprising substituted styrene, at least one hydrovinylation catalyst, and ethylene, where the benzene ring of the substituted styrene is substituted with one or more groups designated R*, where R* is defined herein; subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form an substituted 3 -phenyl- 1-butene, where the benzene ring of the 3 -phenyl- 1-butene is substituted with one or more groups designated R*, where R* is defined herein; forming a second composition comprising substituted 3 -phenyl- 1 -
  • the present invention provides a method of making 2-phenyl linear alkyl benzene sulfonates, the method comprising forming a first composition comprising styrene, at least one hydrovinylation catalyst, and ethylene, subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form hydrovinylation products, where the hydrovinylation products comprise 3 -phenyl- 1 -butene, separating at least a portion of the 3 -phenyl- 1 -butene from the hydrovinylation products, forming a second composition comprising the separated 3 -phenyl- 1 -butene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where the at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, subjecting the second composition to conditions effective to promote a cross metathesis reaction to form cross metathesis
  • the present invention provides a method of making substituted 2- phenyl linear alkyl benzene sulfonates, where the benzene ring of the substituted 2-phenyl linear alkyl benzene sulfonates is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a first composition comprising substituted styrene, at least one hydrovinylation catalyst, and ethylene, where the benzene ring of the substituted styrene is substituted with one or more groups designated R*, where R* is defined herein; subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form hydrovinylation products, where the hydrovinylation products comprise substituted 3-phenyl- l -butene, where the benzene ring of the 3- phenyl- 1 -butene is substituted with one or more groups designated R*, where R* is defined herein; separating at least
  • the present invention provides a method of making 2-phenyl alkene benzene sulfonates, the method comprising forming a composition comprising sulfonated alpha- methyl styrene, at least one olefinic substrate, and at least one olefin metathesis catalyst, and subjecting the composition to conditions effective to promote a cross metathesis reaction.
  • the present invention provides a method of making substituted 2- phenyl alkene benzene sulfonates, where the benzene ring of the substituted 2-phenyl alkene benzene sulfonates is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a composition comprising sulfonated substituted alpha-methyl styrene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where the benzene ring of the substituted alpha-methyl styrene is substituted with one or more groups designated R*, where R* is defined herein; and subjecting the composition to conditions effective to promote a cross metathesis reaction.
  • the present invention provides a method of making 2-phenyl alkene benzene sulfonates, the method comprising forming a composition comprising sulfonated 3- phenyl- 1 -butene, at least one olefinic substrate, and at least one olefin metathesis catalyst, and subjecting the composition to conditions effective to promote a cross metathesis reaction.
  • the present invention provides a method of making substituted 2- phenyl alkene benzene sulfonates, where the benzene ring of the substituted 2-phenyl alkene benzene sulfonates is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a composition comprising sulfonated substituted 3 -phenyl- 1 -butene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where the benzene ring of the sulfonated substituted 3 -phenyl- 1 -butene is substituted with one or more groups designated R*, where R* is defined herein; and subjecting the composition to conditions effective to promote a cross metathesis reaction.
  • the present invention provides a method of making 2-phenyl linear alkene benzene sulfonates, the method comprising forming a composition comprising sulfonated alpha-methyl styrene, at least one olefinic substrate, and at least one olefin metathesis catalyst, wherein the at least one olefinic substrate is selected from at least one linear internal olefin, at least one linear alpha olefin, or a combination thereof, and subjecting the composition to conditions effective to promote a cross metathesis reaction.
  • the present invention provides a method of making substituted 2- phenyl linear alkene benzene sulfonates, where the benzene ring of the substituted 2-phenyl linear alkene benzene sulfonates is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a composition comprising sulfonated substituted alpha-methyl styrene, at least one olefinic substrate, and at least one olefin metathesis catalyst, wherein at least one olefinic substrate is selected from at least one linear internal olefin, at least one linear alpha olefin, or a combination thereof, where the benzene ring of the substituted alpha-methyl styrene is substituted with one or more groups designated R*, where R* is defined herein; and subjecting the composition to conditions effective to promote a cross metathesis reaction.
  • the present invention provides a method of making 2-phenyl linear alkene benzene sulfonates, the method comprising forming a composition comprising sulfonated 3- phenyl- 1 -butene, at least one olefinic substrate, and at least one olefin metathesis catalyst, wherein the at least one olefinic substrate is selected from at least one linear internal olefin, at least one linear alpha olefin, or a combination thereof, and subjecting the composition to conditions effective to promote a cross metathesis reaction.
  • the present invention provides a method of making substituted 2- phenyl linear alkene benzene sulfonates, where the benzene ring of the substituted 2-phenyl linear alkene benzene sulfonates is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a composition comprising sulfonated substituted 3 -phenyl- 1 -butene, at least one olefinic substrate, and at least one olefin metathesis catalyst, wherein the at least one olefinic substrate is selected from at least one linear internal olefin, at least one linear alpha olefin, or a combination thereof, where the benzene ring of the sulfonated substituted 3-phenyl-l -butene is substituted with one or more groups designated R*, where R* is defined herein; and subjecting the composition to conditions effective to promote a cross metathesis reaction.
  • the present invention provides a method of making 2-phenyl linear alkene benzene sulfonates, the method comprising forming a composition comprising sulfonated alpha-methyl styrene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where the at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, subjecting the composition to conditions effective to promote a cross metathesis reaction to form cross metathesis products comprising at least one 2-phenyl linear alkene benzene sulfonate, and separating at least a portion of the at least one 2-phenyl linear alkyl benzene sulfonate from the cross metathesis products.
  • the present invention provides a method of making substituted 2- phenyl linear alkene benzene sulfonates, where the benzene ring of the substituted 2-phenyl linear alkene benzene sulfonates is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a composition comprising sulfonated substituted alpha-methyl styrene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where the at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, where the benzene ring of the substituted alpha-methyl styrene is substituted with one or more groups designated R*, where R* is defined herein; subjecting the composition to conditions effective to promote a cross metathesis reaction to form cross metathesis products comprising at least one substituted 2-
  • the present invention provides a method of making 2-phenyl linear alkene benzene sulfonates, the method comprising forming a composition comprising sulfonated 3- phenyl- 1 -butene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where the at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, subjecting the composition to conditions effective to promote a cross metathesis reaction to form cross metathesis products comprising at least one 2-phenyl linear alkene benzene sulfonate, and separating at least a portion of the at least one 2-phenyl linear alkyl benzene sulfonate from the cross metathesis products.
  • the present invention provides a method of making substituted 2- phenyl linear alkene benzene sulfonates, where the benzene ring of the substituted 2-phenyl linear alkene benzene sulfonates is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a composition comprising sulfonated substituted 3 -phenyl- 1 -butene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where the at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, where the benzene ring of the substituted 3 -phenyl- 1 -butene is substituted with one or more groups designated R*, where R* is defined herein, subjecting the composition to conditions effective to promote a cross metathesis reaction to form cross metathesis products comprising
  • the present invention provides a method of making 2-phenyl linear alkyl benzene sulfonates, the method comprising forming a composition comprising sulfonated alpha-methyl styrene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where the at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, subjecting the composition to conditions effective to promote a cross metathesis reaction.
  • the present invention provides a method of making substituted 2- phenyl linear alkyl benzene sulfonates, where the benzene ring of the substituted 2-phenyl linear alkyl benzene sulfonates is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a composition comprising sulfonated substituted alpha-methyl styrene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where the at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, where the benzene ring of the substituted alpha-methyl styrene is substituted with one or more groups designated R*, where R* is defined herein; subjecting the composition to conditions effective to promote a cross metathesis reaction.
  • the present invention provides a method of making 2-phenyl linear alkylbenzene sulfonates, the method comprising forming a composition comprising sulfonated 3- phenyl- 1 -butene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where the at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, subjecting the composition to conditions effective to promote a cross metathesis reaction.
  • the present invention provides a method of making substituted 2- phenyl linear alkylbenzene sulfonates, where the benzene ring of the substituted 2-phenyl linear alkylbenzene sulfonates is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a composition comprising sulfonated substituted 3-phenyl-l- butene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where the at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, where the benzene ring of the substituted 3 -phenyl- 1 -butene is substituted with one or more groups designated R*, where R* is defined herein, and subjecting the composition to conditions effective to promote a cross metathesis reaction.
  • the present invention provides a method of making 2-phenyl linear alkylbenzene sulfonates, the method comprising forming a composition comprising sulfonated alpha-methyl styrene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where the at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, subjecting the composition to conditions effective to promote a cross metathesis reaction to form cross metathesis products where the cross metathesis products comprise at least one 2-phenyl linear alkene benzene sulfonate, where the at least one 2-phenyl linear alkene benzene sulfonate is derived from a cross metathesis reaction between alpha-methyl styrene sulfonate and at least one olefinic substrate, and subjecting the cross metathesis products comprising at least one 2-pheny
  • the present invention provides a method of making substituted 2- phenyl linear alkylbenzene sulfonates, where the benzene ring of the substituted 2-phenyl linear alkylbenzene sulfonates is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a composition comprising sulfonated substituted alpha-methyl styrene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where the at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, where the benzene ring of the substituted alpha-methyl styrene is substituted with one or more groups designated R*, where R* is defined herein; subjecting the composition to conditions effective to promote a cross metathesis reaction to form cross metathesis products where the cross metathesis products comprise at least one
  • the present invention provides a method of making 2-phenyl linear alkylbenzene sulfonates, the method comprising forming a composition comprising sulfonated 3- phenyl- 1 -butene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where the at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, subjecting the composition to conditions effective to promote a cross metathesis reaction to form cross metathesis products where the cross metathesis products comprise at least one 2-phenyl linear alkene benzene sulfonate, where the at least one 2-phenyl linear alkene benzene sulfonate is derived from a cross metathesis reaction between sulfonated 3 -phenyl- 1 -butene and at least one olefinic substrate, and subjecting the cross metathesis products comprising at
  • the present invention provides a method of making substituted 2- phenyl linear alkylbenzene sulfonates, where the benzene ring of the substituted 2-phenyl linear alkylbenzene sulfonates is substituted with one or more groups designated R*, where R* is defined herein, the method comprising forming a composition comprising sulfonated substituted 3-phenyl-l- butene, at least one olefinic substrate, and at least one olefin metathesis catalyst, where the at least one olefinic substrate is selected from at least one linear alpha olefin, at least one linear internal olefin, or a combination thereof, where the benzene ring of the substituted 3 -phenyl- 1 -butene is substituted with one or more groups designated R*, where R* is defined herein; subjecting the composition to conditions effective to promote a cross metathesis reaction to form cross metathesis products where the cross metathesis products comprise
  • compositions may be optionally hydrogenated to an alkyl benzene and/or optionally aromatically sulfonated.
  • compositions may be optionally aromatically sulfonated.
  • the present invention provides compositions having the following structure, ? wherein n > 3, where R* is defined herein, with the proviso that R* may not be -CH 3 . wherein the compositions may be optionally hydrogenated to a substituted alkyl benzene and/or optionally aromatically sulfonated.
  • the present invention provides compositions having the structures as shown in FIG. 5, FIG. 6, FIG. 7, and/or FIG. 8.
  • the present invention provides comp
  • the present invention provides compositions prepared by methods of the present invention, where the methods are described herein.
  • the present invention provides use of the compositions of the present invention.
  • the present invention provides use of the compositions of the present invention, including but not limited to, use as surfactants for use in, including but not limited to, hand soaps, dish soaps, hard surface cleaners, laundry detergents, and in cleaning supplies.
  • the present invention provides use of the compositions of the present invention, including but not limited to, use as fuels (e.g., diesel fuel and/or jet fuel) or fuel additives, lubricants, surfactants, cosmetics, flavors, fragrances, polymers, plastic additives, home and personal care products, or as precursors for preparing such materials.
  • fuels e.g., diesel fuel and/or jet fuel
  • fuel additives e.g., lubricants, surfactants, cosmetics, flavors, fragrances, polymers, plastic additives, home and personal care products, or as precursors for preparing such materials.
  • the present invention meets the need for non-ionic surfactants which possess good solubility and/or good foaming ability in cold-hard water.
  • the present invention relates to compositions comprising 2-ethoxylated hydroxymethylphenyl linear alkyl benzenes and to compositions comprising 2-propoxylated hydroxymethylphenyl linear alkyl benzenes.
  • This invention also relates to methods of making 2- ethoxylated hydroxymethylphenyl linear alkyl benzenes and to methods of making 2-propoxylated hydroxymethylphenyl linear alkyl benzenes.
  • This invention also relates to the use of compositions comprising 2-ethoxylated hydroxymethylphenyl linear alkyl benzenes and to the use of compositions comprising 2-propoxylated hydroxymethylphenyl linear alkyl benzenes.
  • this invention relates to articles of manufacture comprising compositions comprising 2-ethoxylated hydroxymethylphenyl linear alkyl benzenes and to articles of manufacture comprising compositions comprising 2-propoxylated hydroxymethylphenyl linear alkyl benzenes.
  • 2-ethoxylated hydroxymethylphenyl linear alkyl benzenes and 2-propoxylated hydroxymethylphenyl linear alkyl benzenes are surfactants, more specifically non-ionic surfactants, useful in hand soaps, dish soaps, hard surface cleaners, laundry detergents, and in various cleaning supplies and detergents and detergent compositions.
  • the present invention provides a composition comprising a compound of the formula:
  • the present invention provides a composition comprising a non-ionic surfactant of the formula:
  • the present invention provides a composition comprising a surfactant of the formula:
  • the present invention provides a composition comprising a compound of the formula: n is 2 to 18; m is 1 to 100; and R y is selected from hydrogen, Ci-C6 alkyl, or a protecting group.
  • the present invention provides a composition comprising a non- ionic surfactant of the formula:
  • the present invention provides a composition comprising a surfactant of the formula:
  • the present invention provides a composition comprising a compound of the formula:
  • n 2 to 11
  • the present invention provides a composition comprising a compound of the formula: wherein n is 2 to 18.
  • the present invention provides a composition comprising a compound of the formula:
  • n 2 to 18.
  • the present invention provides a composition comprising a 2- ethoxylated hydroxymethylphenyl linear alkyl benzene having the structure of the following formula:
  • the present invention provides a composition comprising a 2- propoxylated hydroxymethylphenyl linear alkyl benzene having the structure of the following formula:
  • the present invention provides a composition comprising a 2- bromomethylphenyl linear alkyl benzene having the structure of the following formula:
  • the present invention provides a composition comprising a 2- acetoxymethylphenyl linear alkyl benzene having the structure of the following formula:
  • n 2 to 18.
  • the present invention provides a composition comprising a 2- hydroxymethylphenyl linear alkyl benzene having the structure of the following formula:
  • n 2 to 18.
  • the present invention provides a method of making a 2- ethoxylated hydroxymethylphenyl linear alkyl benzene, comprising: forming a first composition comprising styrene, at least one hydrovinylation catalyst, and ethylene; subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form 3-phenyl-l-butene; forming a second composition comprising 3-phenyl-l-butene, at least one olefmic substrate, and at least one olefin metathesis catalyst; subjecting the second composition to conditions effective to promote a cross metathesis reaction to form at least one 2-phenyl linear alkene benzene; subjecting the at least one 2- phenyl linear alkene benzene to conditions effective to promote olefin hydrogenation to form at least one 2-phenyl linear alkylbenzene; subjecting the at least one 2-phenyl linear alkylbenzene to conditions effective to promote an aromatic bromomethylation
  • R z is selected from hydrogen, Ci - Ce alkyl, or a protecting group; LG is a leaving group; and m is 1 to 100.
  • the present invention provides a method of making a 2- ethoxylated hydroxymethylphenyl linear alkyl benzene, comprising: forming a first composition comprising styrene, at least one hydrovinylation catalyst, and ethylene; subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form 3-phenyl- l -butene; forming a second composition comprising 3-phenyl- l -butene, at least one olefmic substrate, and at least one olefin metathesis catalyst; subjecting the second composition to conditions effective to promote a cross metathesis reaction to form at least one 2-phenyl linear alkene benzene; subjecting the at least one 2- phenyl linear alkene benzene to conditions effective to promote olefin hydrogenation to form at least one 2-phenyl linear alkylbenzene; subjecting the at least one 2-phenyl linear alkylbenzene to conditions effective to promote an aromatic bro
  • the present invention provides a method of making a 2- propoxylated hydroxymethylphenyl linear alkyl benzene, comprising: forming a first composition comprising styrene, at least one hydrovinylation catalyst, and ethylene; subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form 3-phenyl- l -butene; forming a second composition comprising 3-phenyl- l -butene, at least one olefmic substrate, and at least one olefin metathesis catalyst; subjecting the second composition to conditions effective to promote a cross metathesis reaction to form at least one 2-phenyl linear alkene benzene; subjecting the at least one 2- phenyl linear alkene benzene to conditions effective to promote olefin hydrogenation to form at least one 2-phenyl linear alkylbenzene; subjecting the at least one 2-phenyl linear alkylbenzene to conditions effective to promote an aromatic bromo
  • the present invention provides method of making a 2- propoxylated hydroxymethylphenyl linear alkyl benzene, comprising: forming a first composition comprising styrene, at least one hydrovinylation catalyst, and ethylene; subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form 3-phenyl- l -butene; forming a second composition comprising 3-phenyl- l -butene, at least one olefmic substrate, and at least one olefin metathesis catalyst; subjecting the second composition to conditions effective to promote a cross metathesis reaction to form at least one 2-phenyl linear alkene benzene; subjecting the at least one 2- phenyl linear alkene benzene to conditions effective to promote olefin hydrogenation to form at least one 2-phenyl linear alkylbenzene; subjecting the at least one 2-phenyl linear alkylbenzene to conditions effective to promote an aromatic bromomethylation
  • R y is selected from hydrogen, d - Ce alkyl, or a protecting group; LG is a leaving group; and m is 1 to 100.
  • the present invention provides a method of making a 2- ethoxylated hydroxymethylphenyl linear alkyl benzene, comprising: subjecting at least one 2-phenyl linear alkylbenzene to conditions effective to promote an aromatic bromomethylation reaction to form at least one 2-bromomethylphenyl linear alkylbenzene; subjecting the at least one 2-bromomethylphenyl linear alkylbenzene to conditions effective to form at least one 2-hydroxymethylphenyl linear alkylbenzene; and contacting the at least o -hydroxymethylphenyl linear alkylbenzene with a
  • R z is selected from hydrogen, Ci - Ce alkyl, or a protecting group; LG is a leaving group; and m is 1 to 100.
  • the present invention provides a method of making a 2- ethoxylated hydroxymethylphenyl linear alkyl benzene, comprising: subjecting at least one 2-phenyl linear alkylbenzene to conditions effective to promote an aromatic bromomethylation reaction to form at least one 2-bromomethylphenyl linear alkylbenzene; contacting the at least one 2-bromomethylphenyl - ⁇ 0 ⁇ linear alkylbenzene with a compound having the structure of the formula m under conditions effective to form at least one 2-ethoxylated hydroxymethylphenyl linear alkyl benzene, wherein R z is selected from hydrogen, Q - C 6 alkyl, or a protecting group; and m is 1 to 100.
  • the present invention provides a method of making a 2- propoxylated hydroxymethylphenyl linear alkyl benzene, comprising: subjecting at least one 2-phenyl linear alkylbenzene to conditions effective to promote an aromatic bromomethylation reaction to form at least one 2-bromomethylphenyl linear alkylbenzene; and contacting the at least one 2- ar alkylbenzene with a compound having the structure of the formula conditions effective to form at least one 2-propoxylated hydroxymethylphenyl linear alkyl benzene, wherein R y is selected from hydrogen, d - Ce alkyl, or a protecting group; and m is 1 to 100.
  • the present invention provides method of making a 2- propoxylated hydroxymethylphenyl linear alkyl benzene, comprising: subjecting at least one 2-phenyl linear alkylbenzene to conditions effective to promote an aromatic bromomethylation reaction to form at least one 2-bromomethylphenyl linear alkylbenzene; subjecting the at least one 2-bromomethylphenyl linear alkylbenzene to conditions effective to form at least one 2-hydroxymethylphenyl linear alkylbenzene; and contacting the at least o -hydroxymethylphenyl linear alkylbenzene with a
  • R y is selected from hydrogen, Q - C 6 alkyl, or a protecting group; LG is a leaving group; and m is 1 to 100.
  • the present invention provides a use of a composition comprising a compound of the formula:
  • the present invention provides a use of a composition comprising a compound of the formula:
  • the present invention provides an article of manufacture comprising a compound of the formula:
  • the present invention provides an article of manufacture comprising a compound of the formula:
  • the present invention provides a method of making a 2- ethoxylated hydroxymethylphenyl linear alkyl benzene having the structure of the following formula: wherein R z is selected from hydrogen, d - alkyl, or a protecting group; n is 2 to 18; and m is 1 to 100, the method comprising: forming a first composition comprising styrene, at least one hydrovinylation catalyst, and ethylene; subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form 3 -phenyl- 1 -butene; forming a second composition comprising 3-phenyl- 1 -butene, at least one olefinic substrate, and at least one olefin metathesis catalyst; subjecting the second composition to conditions effective to promote a cross metathesis reaction to form at least one 2-phenyl linear alkene benzene; subjecting the at least one 2-phenyl linear alkene benzene to conditions effective to promote o
  • alkylbenzene with a compound having the structure of the formula under conditions effective to form at least one 2-ethoxylated hydroxymethylphenyl linear alkyl benzene, wherein R z is selected from hydrogen, d - e alkyl, or a protecting group; LG is a leaving group; and m is 1 to 100.
  • the present invention provides a method of making a 2- ethoxylated hydroxymethylphenyl linear alkyl benzene having the structure of the following formula:
  • R z is selected from hydrogen, d - alkyl, or a protecting group; n is 2 to 18; and m is 1 to 100, the method comprising: forming a first composition comprising styrene, at least one hydrovinylation catalyst, and ethylene; subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form 3 -phenyl- 1 -butene; forming a second composition comprising 3-phenyl- 1 -butene, at least one olefmic substrate, and at least one olefin metathesis catalyst; subjecting the second composition to conditions effective to promote a cross metathesis reaction to form at least one 2-phenyl linear alkene benzene; subjecting the at least one 2-phenyl linear alkene benzene to conditions effective to promote olefin hydrogenation to form at least one 2-phenyl linear alkylbenzene; subjecting the at least one 2-phenyl linear alkylbenzene to conditions effective to promote an aromatic brom
  • the present invention provides method of making a 2- propoxylated hydroxymethylphenyl linear alkyl benzene having the structure of the following formula:
  • R y is selected from hydrogen, d - Ce alkyl, or a protecting group; n is 2 to 18; and m is 1 to 100, the method comprising: forming a first composition comprising styrene, at least one hydrovinylation catalyst, and ethylene; subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form 3 -phenyl- 1 -butene; forming a second composition comprising 3-phenyl- 1 -butene, at least one olefmic substrate, and at least one olefin metathesis catalyst; subjecting the second composition to conditions effective to promote a cross metathesis reaction to form at least one 2-phenyl linear alkene benzene; subjecting the at least one 2-phenyl linear alkene benzene to conditions effective to promote olefin hydrogenation to form at least one 2-phenyl linear alkylbenzene; subjecting the at least one 2-phenyl linear alkylbenzene to conditions effective to promote an aromatic bro
  • the present invention provides method of making a 2- propoxylated hydroxymethylphenyl linear alkyl benzene having the structure of the following formula:
  • R y is selected from hydrogen, d - Ce alkyl, or a protecting group; n is 2 to 18; and m is 1 to 100, the method comprising: forming a first composition comprising styrene, at least one hydrovinylation catalyst, and ethylene; subjecting the first composition to conditions effective to promote a hydrovinylation reaction to form 3 -phenyl- 1 -butene; forming a second composition comprising 3-phenyl- 1 -butene, at least one olefinic substrate, and at least one olefin metathesis catalyst; subjecting the second composition to conditions effective to promote a cross metathesis reaction to form at least one 2-phenyl linear alkene benzene; subjecting the at least one 2-phenyl linear alkene benzene to conditions effective to promote olefin hydrogenation to form at least one 2-phenyl linear alkylbenzene; subjecting the at least one 2-phenyl linear alkylbenzene to conditions effective to promote an aromatic bro
  • the present invention provides a method of making a 2- ethoxylated hydroxymethylphenyl linear alkyl benzene having the structure of the following formula: wherein R z is selected from hydrogen, d - C alkyl, or a protecting group; n is 2 to 18; and m is 1 to 100, the method comprising: subjecting at least one 2-phenyl linear alkylbenzene to conditions effective to promote an aromatic bromomethylation reaction to form at least one 2-bromomethylphenyl linear alkylbenzene; subjecting the at least one 2-bromomethylphenyl linear alkylbenzene to conditions effective to form at least one 2-hydroxymethylphenyl linear alkylbenzene; and contacting the at least one -hydroxymethylphenyl linear alkylbenzene with a compound having the structure of the formula:
  • R z is selected from hydrogen, Ci - Ce alkyl, or a protecting group; LG is a leaving group; and m is 1 to 100.
  • the present invention provides a method of making a 2- ethoxylated hydroxymethylphenyl linear alkyl benzene having the structure of the following formula:
  • R z is selected from hydrogen, d - Ce alkyl, or a protecting group; n is 2 to 18; and m is 1 to 100, the method comprising: subjecting at least one 2-phenyl linear alkylbenzene to conditions effective to promote an aromatic bromomethylation reaction to form at least one 2-bromomethylphenyl linear alkylbenzene; and contacting the at least one 2-bromomethylphenyl linear alkylbenzene with a compound
  • the present invention provides method of making a 2- propoxylated hydroxymethylphenyl linear alkyl benzene having the structure of the following formula:
  • R y is selected from hydrogen, Q - C 6 alkyl, or a protecting group; n is 2 to 18; and m is 1 to 100, the method comprising: subjecting at least one 2-phenyl linear alkylbenzene to conditions effective to promote an aromatic bromomethylation reaction to form at least one 2-bromomethylphenyl linear alkylbenzene; subjecting the at least one 2-bromomethylphenyl linear alkylbenzene to conditions effective to form at least one 2-hydroxymethylphenyl linear alkylbenzene; and contacting the at least one henyl linear alkylbenzene with a compound having the structure of the formula under conditions effective to form at least one 2-propoxylated hydroxymethylphenyl linear alkyl benzene, wherein R y is selected from hydrogen, d - Ce alkyl, or a protecting group; LG is a leaving group; and m is 1 to 100.
  • the present invention provides method of making a 2- propoxylated hydroxymethylphenyl linear alkyl benzene having the structure of the following formula:
  • R y is selected from hydrogen, d - Ce alkyl, or a protecting group; n is 2 to 18; and m is 1 to 100, the method comprising: subjecting at least one 2-phenyl linear alkylbenzene to conditions effective to promote an aromatic bromomethylation reaction to form at least one 2-bromomethylphenyl linear alkylbenzene; and contacting the at least one 2-bromomethylphenyl linear alkylbenzene with a compound
  • R y is selected from hydrogen, d - C alkyl, or a protecting group; and m is 1 to 100.
  • FIG. 1 [000146]
  • alkyl refers to a linear, branched, or cyclic saturated hydrocarbon group typically although not necessarily containing 1 to about 24 carbon atoms, preferably 1 to about 12 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (Pr or n-Pr), isopropyl (i-Pr), n-butyl (Bu or n-Bu), isobutyl (i-Bu), t-butyl (t-Bu), octyl (Oct), decyl, and the like, as well as cycloalkyl groups such as cyclopentyl (Cp), cyclohexyl (Cy) and the like.
  • alkyl groups herein contain 1 to about 12 carbon atoms.
  • the term “lower alkyl” refers to an alkyl group of 1 to 6 carbon atoms
  • the specific term “cycloalkyl” refers to a cyclic alkyl group, typically having 4 to 8, preferably 5 to 7, carbon atoms.
  • substituted alkyl refers to alkyl substituted with one or more substituent groups
  • heteroatom-containing alkyl and “heteroalkyl” refer to alkyl in which at least one carbon atom is replaced with a heteroatom.
  • the terms “alkyl” and “lower alkyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkyl and lower alkyl, respectively.
  • alkylene refers to a difunctional linear, branched, or cyclic alkyl group, where "alkyl” is as defined above.
  • alkenyl refers to a linear, branched, or cyclic hydrocarbon group of 2 to about 24 carbon atoms containing at least one double bond, such as ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, tetracosenyl, and the like.
  • Preferred alkenyl groups herein contain 2 to about 12 carbon atoms.
  • lower alkenyl refers to an alkenyl group of 2 to 6 carbon atoms
  • cycloalkenyl refers to a cyclic alkenyl group, preferably having 5 to 8 carbon atoms.
  • substituted alkenyl refers to alkenyl substituted with one or more substituent groups
  • heteroatom-containing alkenyl and “heteroalkenyl” refer to alkenyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkenyl” and “lower alkenyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkenyl and lower alkenyl, respectively.
  • alkenylene refers to a difunctional linear, branched, or cyclic alkenyl group, where "alkenyl” is as defined above.
  • alkynyl refers to a linear or branched hydrocarbon group of 2 to about 24 carbon atoms containing at least one triple bond, such as ethynyl, n-propynyl, and the like. Preferred alkynyl groups herein contain 2 to about 12 carbon atoms.
  • lower alkynyl refers to an alkynyl group of 2 to 6 carbon atoms.
  • substituted alkynyl refers to alkynyl substituted with one or more substituent groups
  • heteroatom-containing alkynyl and “heteroalkynyl” refer to alkynyl in which at least one carbon atom is replaced with a heteroatom.
  • alkynyl and “lower alkynyl” include linear, branched, unsubstituted, substituted, and/or heteroatom-containing alkynyl and lower alkynyl, respectively.
  • alkynylene refers to a difunctional alkynyl group, where
  • alkynyl is as defined above.
  • alkoxy refers to an alkyl group bound through a single, terminal ether linkage; that is, an "alkoxy” group may be represented as -O-alkyl where alkyl is as defined above.
  • a "lower alkoxy” group refers to an alkoxy group containing 1 to 6 carbon atoms.
  • alkenyloxy and lower alkenyloxy respectively refer to an alkenyl and lower alkenyl group bound through a single, terminal ether linkage
  • alkynyloxy and “lower alkynyloxy” respectively refer to an alkynyl and lower alkynyl group bound through a single, terminal ether linkage.
  • aryl refers to an aromatic substituent containing a single aromatic ring or multiple aromatic rings that are fused together, directly linked, or indirectly linked (such that the different aromatic rings are bound to a common group such as a methylene or ethylene moiety).
  • Preferred aryl groups contain 5 to 24 carbon atoms, and particularly preferred aryl groups contain 5 to 14 carbon atoms.
  • Exemplary aryl groups contain one aromatic ring or two fused or linked aromatic rings, e.g., phenyl (Ph), naphthyl, biphenyl, diphenylether, diphenylamine, benzophenone, and the like.
  • Substituted aryl refers to an aryl moiety substituted with one or more substituent groups
  • heteroatom containing aryl and “heteroaryl” refer to aryl substituents in which at least one carbon atom is replaced with a heteroatom, as will be described in further detail herein.
  • aryloxy refers to an aryl group bound through a single, terminal ether linkage, wherein "aryl” is as defined above.
  • An "aryloxy” group may be represented as -O- aryl where aryl is as defined above.
  • Preferred aryloxy groups contain 5 to 24 carbon atoms, and particularly preferred aryloxy groups contain 5 to 14 carbon atoms.
  • aryloxy groups include, without limitation, phenoxy, o-halo-phenoxy, m-halo-phenoxy, p-halo-phenoxy, o-methoxy-phenoxy, m- methoxy-phenoxy, p-methoxy-phenoxy, 2,4-dimethoxy-phenoxy, 3,4,5-trimethoxy-phenoxy, and the like.
  • alkaryl refers to an aryl group with an alkyl substituent, and the term
  • alkaryl and aralkyl refers to an alkyl group with an aryl substituent, wherein “aryl” and “alkyl” are as defined above.
  • Preferred alkaryl and aralkyl groups contain 6 to 24 carbon atoms, and particularly preferred alkaryl and aralkyl groups contain 6 to 16 carbon atoms.
  • Alkaryl groups include, without limitation, p- methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7-dimethylnaphthyl, 7-cyclooctylnaphthyl, 3- ethyl-cyclopenta-l,4-diene, and the like.
  • aralkyl groups include, without limitation, benzyl, 2-phenyl-ethyl, 3 -phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4- benzylcyclohexyl, 4-phenylcyclohexylmethyl, 4-benzylcyclohexylmethyl, and the like.
  • alkaryloxy and “aralkyloxy” refer to substituents of the formula -OR wherein R is alkaryl or aralkyl, respectively, as just defined.
  • acyl refers to substituents having the formula -(CO)-alkyl, -(CO)-aryl, -(CO)- aralkyl, -(CO)-alkaryl, -(CO)-alkenyl, or -(CO)-alkynyl
  • acyloxy refers to substituents having the formula -0(CO)-alkyl, -0(CO)-aryl, -0(CO)-aralkyl, -0(CO)-alkaryl, -0(CO)-alkenyl, or - (CO)-alkynyl wherein "alkyl,” “aryl”, “aralkyl”, “alkaryl”, “alkenyl", and “alkynyl” are as defined above.
  • the acetoxy group (-0(CO)CH 3 ; often abbreviated as OAc) is a common example of an acyloxy group.
  • cyclic and ring refer to alicyclic or aromatic groups that may or may not be substituted and/or heteroatom containing, and that may be monocyclic, bicyclic, or polycyclic.
  • alicyclic is used in the conventional sense to refer to an aliphatic cyclic moiety, as opposed to an aromatic cyclic moiety, and may be monocyclic, bicyclic or polycyclic.
  • halo and halogen are used in the conventional sense to refer to a fluoro, chloro, bromo, or iodo substituent.
  • Hydrocarbyl refers to univalent hydrocarbyl radicals containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species, such as alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and the like.
  • lower hydrocarbyl refers to a hydrocarbyl group of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms
  • hydrocarbylene refers to a divalent hydrocarbyl moiety containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species.
  • lower hydrocarbylene refers to a hydrocarbylene group of 1 to 6 carbon atoms.
  • Substituted hydrocarbyl refers to hydrocarbyl substituted with one or more substituent groups
  • heteroatom-containing hydrocarbyl and “heterohydrocarbyl” refer to hydrocarbyl in which at least one carbon atom is replaced with a heteroatom
  • substituted hydrocarbylene refers to hydrocarbylene substituted with one or more substituent groups
  • heteroatom-containing hydrocarbylene and heterohydrocarbylene refer to hydrocarbylene in which at least one carbon atom is replaced with a heteroatom.
  • hydrocarbyl and hydrocarbylene are to be interpreted as including substituted and/or heteroatom-containing hydrocarbyl and hydrocarbylene moieties, respectively.
  • heteroatom-containing refers to a hydrocarbon molecule or a hydrocarbyl molecular fragment in which one or more carbon atoms is replaced with an atom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus or silicon, typically nitrogen, oxygen or sulfur.
  • heteroalkyl refers to an alkyl substituent that is heteroatom-containing
  • heterocyclic refers to a cyclic substituent that is heteroatom-containing
  • heteroaryl and “heteroaromatic” respectively refer to “aryl” and “aromatic” substituents that are heteroatom-containing, and the like.
  • heterocyclic group or compound may or may not be aromatic, and further that “heterocycles” may be monocyclic, bicyclic, or polycyclic as described above with respect to the term "aryl.”
  • heteroalkyl groups include without limitation alkoxyaryl, alkylsulfanyl-substituted alkyl, N-alkylated amino alkyl, and the like.
  • heteroaryl substituents include without limitation pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl, 1,2,4-triazolyl, tetrazolyl, etc.
  • heteroatom-containing alicyclic groups include without limitation pyrrolidino, morpholino, piperazino, piperidino, etc.
  • heterocyclic carbene refers to a neutral electron donor ligand comprising a carbene molecule, where the carbenic carbon atom is contained within a cyclic structure and where the cyclic structure also contains at least one heteroatom.
  • heterocyclic carbenes include "N- heterocyclic carbenes” wherein the heteroatom is nitrogen and "P-heterocyclic carbenes” wherein the heteroatom is phosphorus.
  • substituted as in “substituted hydrocarbyl,” “substituted alkyl,” “substituted aryl,” and the like, as alluded to in some of the aforementioned definitions, is meant that in the hydrocarbyl, alkyl, aryl, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more non-hydrogen substituents.
  • substituents include, without limitation: functional groups referred to herein as "Fn,” such as halo, hydroxyl, sulfhydryl, C 1 -C 24 alkoxy, C 2 -C 24 alkenyloxy, C 2 -C 24 alkynyloxy, C5-C 24 aryloxy, C6-C 24 aralkyloxy, C6-C 24 alkaryloxy, acyl (including C 2 - C 24 alkylcarbonyl (-CO-alkyl) and C6-C 24 arylcarbonyl (-CO-aryl)), acyloxy (-O-acyl, including C 2 -C 24 alkylcarbonyloxy (-O-CO-alkyl) and C6-C 24 arylcarbonyloxy (-O-CO-aryl)), C 2 -C 24 alkoxycarbonyl (- (CO)-O-alkyl), C 6 -C 24 aryloxycarbonyl (-(CO)-O
  • “functionalized olefin,” “functionalized cyclic olefin,” and the like, is meant that in the hydrocarbyl, alkyl, olefin, cyclic olefin, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more functional groups such as those described hereinabove.
  • the term “functional group” is meant to include any functional species that is suitable for the uses described herein. In particular, as used herein, a functional group would necessarily possess the ability to react with or bond to corresponding functional groups on a substrate surface.
  • the aforementioned functional groups may, if a particular group permits, be further substituted with one or more additional functional groups or with one or more hydrocarbyl moieties such as those specifically enumerated above.
  • the above mentioned hydrocarbyl moieties may be further substituted with one or more functional groups or additional hydrocarbyl moieties such as those specifically mentioned above.
  • the above-mentioned hydrocarbyl moieties may be further substituted with one or more functional groups or additional hydrocarbyl moieties as noted above.
  • ethenolysis refers to the cross metathesis of a substrate with ethylene.
  • ethenolysis of methyl oleate produces methyl 9-decenoate and 1-decene.
  • Burdett K.A.; Harris, L.D.; Margl, P.; Maughon, B.R.; Mokhtar-Zadeh, T.; Saucier, P.C.; Wasserman, E.P.
  • alkenolysis refers to a cross metathesis reaction where a terminal olefin is used in a cross metathesis reaction with an internal double bond to produce different terminal olefins, where the initial terminal olefin cannot be ethylene.
  • alkenolysis of methyl oleate with 1- butene produces methyl 9-decenoate, 1-decene, methyl-9-dodecenoate and 3-dodecene.
  • alkenolysis references see Schrodi, Y.; Pederson, R.L.; Kaido, H.; Tupy, M.J. US Pat. App.
  • Optional or “optionally” means that the subsequently described circumstance may or may not occur, so that the description includes instances where the circumstance occurs and instances where it does not.
  • the phrase "optionally substituted” means that a nonhydrogen substituent may or may not be present on a given atom, and, thus, the description includes structures wherein a non- hydrogen substituent is present and structures wherein a nonhydrogen substituent is not present.
  • linear when referring to a hydrocarbon or to an alkyl chain that is part of an alkylbenzene, whether the alkylbenzene is sulfonated or not, means a hydrocarbon comprising between 6 and 22 carbon atoms linked to one another to form a straight chain, wherein the carbon atoms of the straight chain may have only hydrogen atoms or a methyl group bonded to them as appendages.
  • branched alkyl when referring to a hydrocarbon or to an alkyl chain that is part of an alkylbenzene, whether the alkylbenzene is sulfonated or not, means a hydrocarbon comprising between 7 and 22 carbon atoms linked to one another to form a straight chain, wherein one or more of the carbon atoms of the straight chain may have a hydrogen atom or any alkyl group other than a methyl group (including without limitation, ethyl, propyl, and butyl groups), bonded to them as appendages.
  • branched alkylbenzene means a molecular species which comprises a branched alkyl chain appended to a benzene ring.
  • branched alkylbenzene sulfonate means a water soluble salt of a branched alkylbenzene that has been sulfonated.
  • 2-phenyl linear alkyl benzenes or "2-PhLAB” means a benzene ring having at least one linear alkyl group attached to it, where the linear alkyl group comprises any number of carbon atoms between 6 and 22 (including every integral number there between) linked to one another so as to form a straight chain, wherein the carbon atoms of the straight chain (longest continuous carbon chain) may have only hydrogen atoms, or one or two methyl groups bonded to them as appendages, and wherein the benzene ring is attached to the linear alkyl group at a carbon atom that is adjacent to the terminal carbon atom of the straight chain (longest continuous carbon chain).
  • the number of carbon atoms in the straight chain (longest continuous carbon chain) attached to the benzene ring is preferably 6 to 22, more preferably 7 to 16, and most preferably 9 to 14.
  • the benzene ring may also be substituted with one or more groups designated R*, where R* is C1-C12 alkyl, C5-C14 aryl, halo, amino, hydroxyl, alkoxy, acetoxy, nitro, cyano, substituted amino, napthyl, or biphenyl.
  • R* is C1-C12 alkyl, C5-C14 aryl, halo, nitro, cyano, acetoxy, hydroxyl, and amino. More preferably R* is Ci-Ce alkyl. Even more preferably R*is methyl.
  • the sulfonate group is attached to the benzene ring in the ortho, meta, or para-position with respect to the linear alkyl group.
  • Examples of sulfonated aryl rings (e.g., sulfonated benzene rings) are represented in Schemes 4 through 8.
  • 2-C4 to 2O-C40 refer to a short hand method of naming olefins.
  • the first number represents the position of the double bond and the subscript number after carbon represents the number of carbons on the chain.
  • 2-C4 stand for 2-butene
  • 3-Ce stands for 3-hexene
  • up to 2O-C40 stands for 20-tetracontene.
  • a leaving group is a molecular fragment that departs with a pair of electrons in heterolytic bond cleavage.
  • Leaving groups can be anions or neutral molecules.
  • Examples of common anionic leaving groups are halides such as chloride (CL), bromide (Br ) , and iodide ( ⁇ ), and sulfonate esters, such as tosylate (TsO ).
  • Examples of common neutral molecule leaving groups are water and ammonia.
  • the present invention provides a method of making 2-phenyl linear alkylbenzene sulfonates. More particularly, herein is described a method of making 2-phenyl linear alkene benzenes by cross metathesis of at least one cross metathesis substrate with at least one olefmic substrate in the presence of at least one olefin metathesis catalyst, where the at least one cross metathesis substrate is selected from alpha-methyl styrene, substituted alpha-methyl styrene, sulfonated alpha-methyl styrene (AMS), sulfonated substituted alpha-methyl styrene, 3 -phenyl- 1-butene (3PI1IC 4 ), substituted 3-phenyl-l- butene, sulfonated 3 -phenyl- 1-butene, and sulfonated substituted 3 -phenyl- 1-butene, where the at least one olefmic substrate is selected from at least
  • the 2-phenyl linear alkene benzene (2-PhLAeB or 2-Ph*LAeB) product is hydrogenated to yield 2-phenyl alkylbenzene.
  • the 2-phenyl linear alkylbenzene product is sulfonated to yield high isomeric purity 2-phenyl linear alkylbenzene sulfonate (2-PhLAS or 2-Ph*LAS), where the isomeric purity is at least 85% by weight based on the total weight of linear alkyl benzene sulfonate isomers.
  • Scheme 1 below shows a general synthesis of 2-phenyl linear alkyl benzene sulfonates using cross metathesis.
  • Hydrovinylation is an atom- efficient process to add ethylene to a double bond (see
  • R hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom- containing hydrocarbyl, and functional groups.
  • Ni(II) hydrovinylation complexes include:
  • NiCl 2 (PBu 3 ) 2 / AlEt 2 Cl [Dzhemilev, U. M.; Gubaidullin, L. Y.; Tolstikov, G. A. Bull. Acad. Sci. USSR 1976, 2009.] Ni(acac) 2 / Et 3 Al / BF 3 « OEt 2 / P(OPh) 3 [Azizov, A. G.; Mamedaliev, G. A.; Aliev, S. M.; Aliev, V. S. Azerb. Khim. Zh.
  • Pd(II) hydrovinylation complexes include:
  • PdCl 2 (PhCN) 2 [Barlow, M. G.; Bryant, M. J.; Haszeldine, R. N.; Mackie, A. G. J. Organomet. Chem. 1970, 21, 215.]
  • Pd(OAc) 2 / Et 2 P(CH 2 ) 3 PEt 2 / PTSA [Drent, E. US Patent 5,227,561, 1993. Kawamoto, K.; Tatani, A.; Imanaka, T.; Teranishi, S. Bull. Chem. Soc, Jpn.
  • Co(II) hydrovinylation complexes include:
  • Ru(II) hydrovinylation complexes include:
  • Scheme 3 shows a general preparation of 3 -phenyl- 1-butene (3PhlCz t ) by the hydrovinylation of styrene and a general preparation of substituted 3 -phenyl- 1-butene (3Ph* lCz t ) by the hydrovinylation of substituted styrene.
  • Examples of compounds useful in the hydrovinylation reaction include but are not limited to compounds which are also useful as cross metathesis substrates including substituted styrenic compounds, non-substituted styrenic compounds, substituted styrenes, non-substituted styrenes, substituted divmylbenzenes, non-substituted divmylbenzenes, substituted allylbenzenes, non-substituted allylbenzenes, sulfonated substituted styrenic compounds, sulfonated non-substituted styrenic
  • substituted styrenic compounds substituted styrenes, substituted divmylbenzenes, substituted allylbenzenes, sulfonated substituted styrenic compounds, sulfonated substituted styrenes, sulfonated substituted divmylbenzenes, and sulfonated substituted allylbenzenes may be ortho, meta, para substituted with various R* substituent groups, where R* is defined herein. Also combinations of various R* substituent groups may be present on the phenyl ring.
  • Preferred examples of unsubstituted compounds useful in the hydrovinylation reaction include styrene, and sulfonated styrene, where styrene is more preferred.
  • substituted styrenes useful in the hydrovinylation reaction include but are not limited to the ortho, meta or para substituted isomers of tolyl styrene, ethylstyrene, propylstyrene, isopropylstyrene, butylstyrene, sec-butylstyrene, isobutylstyrene, tert-butylstyrene, fluorostyrene, chlorostyrene, bromostyrene, iodostyrene, nitrostyrene, cyanostyrene, acetoxystyrene, hydroxystyrene, alkoxystyrene compounds, aminostyrene, and substituted aminostyrene compounds, styrenes derived from phenyl fused rings like naphthylstyrene and biphenylstyrene. Also combinations of
  • substituted styrenes useful in the hydrovinylation reaction include but are not limited to the ortho, meta or para substituted isomers of tolyl styrene, ethylstyrene, propylstyrene, isopropylstyrene, fluorostyrene, chlorostyrene, bromostyrene, iodostyrene, nitrostyrene, cyanostyrene, acetoxystyrene, hydroxystyrene, and aminostyrene. Also combinations of any of these various R* substituent groups may be present on the same phenyl ring. The R* substituent group may be substituted on the aromatic ring in one or more ortho, meta or para-positions.
  • substituted styrenes useful in the hydrovinylation reaction include but are not limited to the ortho, meta or para substituted isomers of tolyl styrene and ethylstyrene. Also combinations of any of these various R* substituent groups may be present on the same phenyl ring. The R* substituent group may be substituted on the aromatic ring in one or more ortho, meta or para- positions.
  • Alternative routes into 3 -phenyl- 1-butene and substituted 3 -phenyl- 1-butene include but not limited to; 1) nucleophilic substitution of methyl Grignard with a 3-phenyl-2-propenyl halide or substituted 3-phenyl-2-propenyl halide (Alexakis, A.; Backvall, J. E.; Krause, N.; Pamies, O.; Dieguez, M. Chem. Rev. 2008, 108, 2796; Trost, B. M.; Crawley, M. L. Chem. Rev. 2003, 103, 2921 ; Trost, B. M.; Van Vranken, D. L. Chem. Rev.
  • Additional hydrovinylation catalysts suitable for use in the present invention include hydrovinylation catalysts HV- 1 to HV- 16 shown in FIG. 1.
  • Preferred hydrovinylation catalysts suitable for the present invention include:
  • More preferred hydrovinylation catalysts suitable for the present invention include:
  • Cross metathesis substrates for use with the present invention include substituted and non-substituted styrenic compounds, substituted and non-substituted styrenes, substituted and non- substituted divinylbenzenes, substituted and non-substituted allylbenzenes, substituted and non- substituted 4-phenyl- 1 -butene, substituted and non-substituted alpha-methyl styrenes, sulfonated alpha- methyl styrenes, sulfonated substituted alpha-methyl styrenes, 3 -phenyl- 1-butenes, substituted 3-phenyl- 1-butenes, sulfonated 3-phenyl- 1-butenes, and sulfonated substituted 3 -phenyl- 1-butenes.
  • Preferred cross metathesis substrates for use with the present inventon include 3-phenyl- 1-butenes, substituted 3-phenyl- 1-butenes, More preferred cross metathesis substrates for use with the present invention include 3-phenyl- 1-butenes, substituted 3-phenyl- 1-butenes, 3 -to lyl- 1-butenes, alpha-methyl styrenes, and substituted alpha-methyl styrenes. 3 -phenyl- 1 -butene and 3 -tolyl-1 -butene may be prepared as described herein.
  • substituted AM*S refers to the aryl ring (benzene ring) of alpha-methyl styrene being substituted with one or more R* substituent groups (see Scheme 4).
  • sulfonated AMS and “sulfonated substituted AM*S” refers to the aryl ring
  • M x H, CH 3 , NH 4 + , Li + , Na + ,
  • substituted 3 -phenyl- 1-butene refers to the phenyl ring (benzene ring) of substituted 3 -phenyl- 1-butene being substituted with one or more R* substituent groups (see Scheme 6).
  • Examples of substituted 3 -phenyl- 1-butene produced in this reaction include but not limited to 3 -to lyl- 1-butene, 3 -ethylphenyl- 1-butene, 3 -propylphenyl- 1-butene, 3-isopropylphenyl-l- butene, 3 -butylphenyl- 1 -butene, 3 -sec-butylphenyl- 1 -butene, 3 -isobutylphenyl- 1 -butene, 3 -tert- butylphenyl- 1 -butene, 3 -fluorophenyl- 1 -butene, 3 -chlorophenyl- 1 -butene, 3 -bromophneyl- 1 -butene, 3 - iodophenyl- 1 -butene, 3 -nitrophneyl- 1 -butene, 3 -cyanopheny
  • Preferred examples of substituted 3 -phenyl- 1 -butene produced in this reaction include but not limited to 3 -tolyl-1 -butene, 3-ethylphenyl- l -butene, 3 -propylphenyl- 1 -butene, 3-isopropylphenyl-l- butene, 3 -fluorophenyl- 1 -butene, 3 -chlorophenyl- 1 -butene, 3 -bromophneyl- 1 -butene, 3-iodophenyl-l- butene, 3 -nitrophenyl- 1 -butene, 3 -cyanophenyl- 1 -butene, 3 - acetoxyphenyl- 1 -butene, 3 -hydroxyphenyl- 1 - butene, 3 -aminophenyl- 1 -butene, and styrenes derived from pheny
  • substituted 3 -phenyl- 1 -butene produced in this reaction include but not limited to 3 -tolyl-1 -butene and 3-ethylphenyl-l -butene. Also combinations of any of these various R* substituent groups may be present on the same phenyl ring. The R* substituent group may be substituted on the aromatic ring in one or more ortho, meta or para-positions.
  • M x H, CH 3 , NH 4 + , Li + , Na + ,
  • M x H, CH 3 , NH 4 + , Li + , Na + ,
  • Examples of sulfonated substituted 3 -phenyl- 1-butene produced in this reaction include but not limited to the sulfonate of 3-tolyl- l-butene, 3 -ethylphenyl- 1-butene, 3 -propylphenyl- 1-butene, 3- isopropylphenyl- 1 -butene, 3 -butylphenyl- 1 -butene, 3 -sec-butylphenyl- 1 -butene, 3 -isobutylphenyl- 1 - butene, 3 -tert-butylphenyl- 1 -butene, 3 -fluorophenyl- 1 -butene, 3 -chlorophenyl- 1 -butene, 3 -bromophneyl- 1 -butene, 3 -iodophenyl- 1 -butene, 3 -nitrophneyl-
  • Olefinic substrates for use with the present invention include internal olefins, alpha olefins, and combinations thereof.
  • Preferred, olefinic substrates for use with the present invention include linear internal olefins, linear alpha olefins, and combinations thereof.
  • the term "internal olefin” as used herein means an olefin wherein each of the olefinic carbons is substituted by at least one non-hydrogen substituent.
  • the non-hydrogen substituents are selected from hydrocarbyl, and substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups.
  • the internal olefin is therefore at least disubstituted, and may further include additional non-hydrogen substituents such that the internal olefin is tri- or tetra-substituted.
  • Each of the substituents on the internal olefinic carbons may be further substituted as described herein.
  • the internal olefin may be in the Z- or E-configuration.
  • the internal olefin may be a single compound or a mixture of compounds.
  • the internal olefin may comprise a single internal olefin or a plurality of internal olefins. A mixture of internal olefins may be used.
  • the internal olefin may be hydrophobic or hydrophilic, although in a preferred embodiment, the internal olefin is hydrophobic.
  • the internal olefin may be represented by the formula
  • R 1 or R n and either R in or w is H, such that the internal olefin is di-substituted.
  • either R 1 or R n and either R m or w is H, such that the internal olefin is di-substituted.
  • R n and w may be C 2 -C19 alkyl, where the carbon atoms in the alkyl chain may have only hydrogen atoms or a methyl group bonded to them.
  • the linear internal olefin may be in the Z- or E-configuration.
  • R" and R lv are C 3 to C 19 alkyl
  • M x H, CH 3 , NH 4 + , Li + , Na + , when R' and R IM are H and
  • K + , Cs + , Mg +2 , Ca +2 , or Sr +2 R" and R IV are C 3 to C 19 alkyl
  • linear internal olefins that may be used for the cross-metathesis partner with substituted alpha-methyl styrene (substituted AM*S) to produce 2-Ph*LAeB (substituted 2-phenyl alkenylbenzene) and 2-Ph*LAeS (substituted 2-phenyl alkenylbenzene sulfonate) are shown in Scheme 10.
  • R" and R lv are C 3 to C 19 alkyl
  • M x H, CH 3 , NH 4 + , Li + , Na + , when R and R are H and
  • K + , Cs + , Mg +2 , Ca +2 , or Sr +2 R" and R lv are C 3 to C 19 alkyl
  • Examples of preferred linear internal olefins that may be used for the cross metathesis with cross metathesis substrates such as alpha-methyl styrene (AMS), sulfonated AMS, substituted alpha- methyl styrene (AM*S), and sulfonated substituted AM*S include 2-butene, 3-hexene, 4-octene, 5- decene, 6-dodecene, 7-teradecene, 8-hexadecene, 9-octadecene, IO-C20, H-C22, 12- C24, 13- C26, 14-C28, 15- C 30 , 16- C 32 , 17- C 34 , 18- C 36 , 19-C 38 , and 20-C 40 .
  • AMS alpha-methyl styrene
  • AM*S substituted alpha- methyl styrene
  • AM*S substituted alpha- methyl styrene
  • Examples of more preferred linear internal olefins that may be used for the cross metathesis with cross metathesis substrates such as alpha-methyl styrene, and sulfonated alpha-methyl styrene, substituted alpha-methyl styrene, and sulfonated substituted alpha-methyl styrene include 5- decene, 6-dodecene, 7-teradecene, 8-hexadecene, 9-octadecene, IO-C20, H-C22, I -C24, and 13-C26-
  • Examples of the most preferred linear internal olefins that may be used for the cross metathesis with cross metathesis substrates such as alpha-methyl styrene, sulfonated alpha-methyl styrene, substituted alpha-methyl styrene, and sulfonated substituted alpha-methyl styrene include 9- octadecene, IO-C20, and I I-C22.
  • R" and R IV are C 2 to C 18 a
  • M x H, CH 3 , NH 4 + , Li + , Na + ,
  • R" and R lv are C 2 to C 18 alkyl
  • R and R are H and R" and R IV are C 2 to C 18 alkyl
  • R" and R IV are C 2 to C 18 alkyl K + , Cs + , Mg +2 , Ca +2 , or Sr +2
  • Examples of preferred linear internal olefins that may be used for the cross metathesis with cross metathesis substrates such as 3 -phenyl- 1 -butene, sulfonated 3 -phenyl- 1 -butene, substituted 3- phenyl- 1-butene, and sulfonated substituted 3 -phenyl- 1-butene include 2-butene, 3-hexene, 4-octene, 5- decene, 6-dodecene, 7-teradecene, 8-hexadecene, 9-octadecene, 10-C 2 o, H -C22, 12- C 24 , 13- C 26 , 14-C 2 8, 15- C 30 , 16- C 32 , 17- C 34 , 18- C 36 , 19-C 38 , and 20- C 40 .
  • Examples of more preferred linear internal olefins that may be used for the cross metathesis with cross metathesis substrates such as 3 -phenyl- 1-butene, sulfonated 3 -phenyl- 1-butene, substituted 3 -phenyl- 1 -butene, and sulfonated substituted 3 -phenyl- 1-butene include 5-decene, 6- dodecene, 7-teradecene, 8-hexadecene, 9-octadecene, 10-C 20 , 1 1-C 22 , 12-C 24 , and 13-C 2 6-
  • Examples of the most preferred linear internal olefins that may be used for the cross metathesis with cross metathesis substrates such as 3 -phenyl- 1-butene, sulfonated 3 -phenyl- 1-butene, substituted 3 -phenyl- 1-butene, and sulfonated substituted 3 -phenyl- 1 -butene include 8-hexadecene, 9- octadecene, 10-C 2 o.
  • the alpha olefin may be a single compound or a mixture of compounds.
  • the internal olefin may comprise a single alpha olefin or a plurality of alpha olefins. A mixture of alpha olefins may be used.
  • the alpha olefin may be hydrophobic or hydrophilic, although in a preferred embodiment, the alpha olefin is hydrophobic.
  • the alpha olefin may be wherein one olefinic carbon is unsubstituted and the other olefinic carbon is substituted with one or two non-hydrogen substituents.
  • the substituted olefinic carbon may therefore be mono-substituted or di-substituted.
  • the alpha olefin may comprise substituents selected from any of the substituents listed herein above.
  • the alpha olefin may comprises a substituent comprising 1 to about 20 carbon atoms, about 10 carbon atoms, or about 6 carbon atoms.
  • R x are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom- containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl and functional groups, provided that at least one of R and R is a non-hydrogen substituent. Furthermore, R and R may be linked to form a cycle.
  • R K and R x are independently selected from substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted heteroatom-containing C1-C20 alkyl, substituted or unsubstituted heteroatom-containing C2-C20 alkenyl, substituted or unsubstituted heteroatom-containing C2-C20 alkynyl, substituted or unsubstituted C5-C24 aryl, substituted or unsubstituted C5-C24 alkaryl, or substituted or unsubstituted C5-C24 aralkyl, substituted or unsubstituted heteroatom-containing C5-C24 aryl, substituted or unsubstituted heteroatom-containing C5-C24 alkaryl, substituted or unsubstituted heteroatom-containing C5-containing C5-C
  • R 11 is C 3 to C 19 alkyl
  • M x H, CH 3 , NH 4 + , Li + , Na + ,
  • R" is C 3 to C 19 alkyl
  • R" is C 3 to C-19 alkyl
  • M x H, CH 3 , NH 4 + , Li + , Na + , substituted 2-Ph*LAeS
  • R 1 is H
  • R 11 is C 3 to C 19 alkyl
  • linear alpha olefins that may be used for the cross-metathesis with cross metathesis substrates such as alpha-methyl styrene, sulfonated alpha-methyl styrene, substituted alpha- methyl styrene, and sulfonated substituted alpha-methyl styrene include 1-propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1 -tetradecene, 1 -pentadecene, 1 -hexadecene, 1-heptadecene, 1 -octadecene, 1 -nonadecene, and 1-eicosene.
  • Examples of preferred linear alpha olefins that may be used for the cross-metathesis with cross metathesis substrates such as alpha-methyl styrene, sulfonated alpha-methyl styrene, substituted alpha-methyl styrene, and sulfonated substituted alpha-methyl styrene include 1-hexene, 1-heptene, 1- octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, and 1 -tetradecene.
  • Examples of preferred linear alpha olefins that may be used for the cross-metathesis with cross metathesis substrates such as alpha-methyl styrene, sulfonated alpha-methyl styrene, substituted alpha-methyl styrene, and sulfonated substituted alpha-methyl styrene include terpenes and related isoprenoids.
  • Non-limiting examples of terpenes include alpha- or beta-farnesenes.
  • Examples of the most preferred linear alpha olefins that may be used for the cross- metathesis with cross metathesis substrates such as alpha-methyl styrene, sulfonated alpha-methyl styrene, substituted alpha-methyl styrene, and sulfonated substituted alpha-methyl styrene include 1- decene, 1-undecene and 1-dodecene.
  • R" is C 2 to C 18 alkyl
  • M x H, CH 3 , NH 4 + , Li + , Na + ,
  • R" is C 2 to C 18 alkyl
  • R M is C 2 to C 8 alkyl
  • R" is C 2 to C 8 alkyl
  • linear alpha olefins that may be used for the cross-metathesis with cross metathesis substrates such as 3 -phenyl- 1-butene, sulfonated 3 -phenyl- 1-butene, substituted 3 -phenyl- 1- butene, and sulfonated substituted 3 -phenyl- 1-butene include 1-propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1 -tetradecene, 1 - pentadecene, 1 -hexadecene, 1 -heptadecene, 1 -octadecene, 1 -nonadecene, and 1-eicosene.
  • Examples of preferred linear alpha olefins that may be used for the cross-metathesis with cross metathesis substrates such as 3 -phenyl- 1-butene, sulfonated 3 -phenyl- 1-butene, substituted 3-phenyl- 1 -butene, and sulfonated substituted 3 -phenyl- 1-butene include 1-hexene, 1-heptene, 1-octene, 1-nonene, 1- decene, 1-undecene, 1-dodecene, 1-tridecene, and 1 -tetradecene.
  • Examples of the most preferred linear alpha olefins that may be used for the cross- metathesis with cross metathesis substrates such as 3 -phenyl- 1-butene, sulfonated 3-phenyl- 1-butene, substituted 3 -phenyl- 1-butene, and sulfonated substituted 3 -phenyl- 1-butene include 1-nonene, 1-decene, and 1-undecene.
  • Methyl groups on the alkene backbone may improve solubility of PhLAS
  • Methyl groups on the alkene backbone improves solubility of PhLAS
  • examples of dimethyl substituted linear internal olefins that may be used for the cross metathesis with cross metathesis substrates such as alpha-methyl styrene, sulfonated alpha-methyl styrene, substituted alpha-methyl styrene, or sulfonated substituted alpha-methyl styrene, 3 -phenyl- 1-butene, sulfonated 3 -phenyl- 1-butene, substituted 3 -phenyl- 1-butene, sulfonated substituted 3 -phenyl- 1-butene include the self-metathesized methyl substituted linear alpha olefins, listed earlier, to yield symmetrical dimethyl linear internal olefins.
  • Examples of symmetrical dimethyl substituted linear internal olefins produced by self- metathesis of methyl substituted alpha olefins include 3-methylpent- l-ene to yield 3, 6-dimethyl-4- octene, 4-methylpent-l-ene to yield 2, 7-dimethyl-4-octene, 3-methylhex-l-ene to yield 4, 7-dimethyl-5- decene, etc.
  • Examples of symmetrical dimethyl substituted linear internal olefins that may be used for the cross metathesis with cross metathesis substrates such as 3 -phenyl- 1-butene, sulfonated 3-phenyl- 1-butene, substituted 3 -phenyl- 1-butene, or sulfonated substituted 3 -phenyl- 1-butene include dimethyl 3- hexene, dimethyl 4-octene, dimethyl 5-decene, dimethyl 6-dodecene, dimethyl 7-teradecene, dimethyl 8- hexadecene, dimethyl 9-octadecene, dimethyl IO-C20, dimethyl I I-C22, dimethyl I2-C24, dimethyl 13- C26, dimethyl 14-C28, dimethyl 15- C30, dimethyl I6-C32, dimethyl I7-C34, dimethyl I 8-C36, dimethyl 19-C38, and dimethyl 2O-
  • More preferred examples of symmetrical dimethyl substituted linear internal olefins that may be used for the cross metathesis with cross metathesis substrates such as 3 -phenyl- 1-butene, sulfonated 3 -phenyl- 1-butene, substituted 3-phenyl- l -butene, or sulfonated substituted 3-phenyl- l -butene include dimethyl 7-tetradecene, dimethyl 8-hexadecene, dimethyl 9-octadecene, dimethyl IO-C 20 , dimethyl 1 1-C 22 , dimethyl I2-C24, and dimethyl 13-C26-
  • Most preferred examples of symmetrical dimethyl substituted linear internal olefins that may be used for the cross metathesis with cross metathesis substrates such as 3-phenyl- l -butene, sulfonated 3-phenyl- l -butene, substituted 3-phenyl- l -butene, or sulfonated substituted 3-phenyl- l -butene include dimethyl 7-tetradecene, dimethyl 8-hexadecene, dimethyl 9-octadecene, dimethyl IO-C 20 , and dimethyl 1 1 -C 22 .
  • a mixture of 1-nonene, 1-decene, and 1-undecene subjected to cross-metathesis conditions will yield a mixture of 8-hexadecene (8-Ci 6 ), 8- heptadecene (8-Cn), 8-octadecene (8-Cig), 9-octadecene (9-Cig), 9-nonadecene (9-Ci 9 ) and 10-eicosene
  • any mixture of alpha olefins and branched alpha olefins, di-substituted and branched di-substituted olefin may be used. Therefore, any mixture of linear alpha olefins, methyl substituted linear alpha olefins, linear internal olefins, methyl substituted linear internal olefins, etc. may be used.
  • Examples of 2-phenyl linear alkene benzenes include 2-phenyl-2-hexene, 2-phenyl-3- hexene, 2-phenyl-2-heptene, 2-phenyl-3-heptene, 2-phenyl-2-octene, 2-phenyl-3-octene, 2-phenyl-2- nonene, 2-phenyl-3-nonene, 2-phenyl-2-decene, 2-phenyl-3-decene, 2-phenyl-2-undecene, 2-phenyl-3- undecene, 2-phenyl-2-dodecene, 2-phenyl-3-dodecene, 2-phenyl-2-tridecene, 2-phenyl-3-tridecene, 2- phenyl-2-tetradecene, 2-phenyl-3-tetradecene, 2-phenyl-2-pentadecene, 2-phenyl-3-pentadecene,
  • Examples of the more preferred 2-phenyl linear alkene benzenes include 2-phenyl-2- octene, 2-phenyl-3-octene, 2-phenyl-2-nonene, 2-phenyl-3-nonene, 2-phenyl-2-decene, 2-phenyl-3- decene, 2-phenyl-2-undecene, 2-phenyl-3-undecene, 2-phenyl-2-dodecene, 2-phenyl-3-dodecene, 2- phenyl-2-tridecene and 2-phenyl-3-tridecene.
  • Examples of the most preferred 2-phenyl linear alkene benzenes include 2-phenyl-2- undecene, 2-phenyl-2-dodecene, 2-phenyl-2-tridecene, 2-phenyl-3-undecene, 2-phenyl-3-dodecene, and 2-phenyl-3-tridecene.
  • Examples of substituted 2-phenyl linear alkene benzenes include substituted 2-phenyl-2-hexene, substituted 2- phenyl-3-hexene, substituted 2-phenyl-2-heptene, substituted 2-phenyl-3-heptene, substituted 2-phenyl- 2-octene, substituted 2-phenyl-3-octene, substituted 2-phenyl-2-nonene, substituted 2-phenyl-3-nonene, substituted 2-phenyl-2-decene, substituted 2-phenyl-3-decene, substituted 2-phenyl-2-undecene, substituted 2-phenyl-3-undecene, substituted 2-phenyl-2-dodecene, substituted 2-phenyl-3-dodecene, substituted 2-phenyl-2-tridecene, substituted 2-phenyl-3-
  • Examples of the more preferred substituted 2-phenyl linear alkene benzenes, where the benzene ring is substituted with one or more groups designated R*, include substituted 2-phenyl-2-octene, substituted 2-phenyl-3-octene, substituted 2-phenyl-2-nonene, substituted 2-phenyl-3-nonene, substituted 2-phenyl-2-decene, substituted 2-phenyl-3-decene, substituted 2-phenyl-2-undecene, substituted 2- phenyl-3 -undecene, substituted 2-phenyl-2-dodecene, substituted 2-phenyl-3-dodecene, substituted 2- phenyl-2-tridecene and substituted 2-phenyl-3-tridecene.
  • Examples of the most preferred substituted 2-phenyl linear alkene benzenes, where the benzene ring is substituted with one or more groups designated R*, include substituted 2-phenyl-2- undecene, substituted 2-phenyl-2-dodecene, substituted 2-phenyl-2-tridecene, substituted 2-phenyl-3- undecene, substituted 2-phenyl-3-dodecene, and substituted 2-phenyl-3-tridecene.
  • Examples of 2-PhLABs following hydrogenation are 2-phenyl-pentane, 2-phenyl-hexane,
  • Examples of the more preferred 2-PhLABs following hydrogenation are 2-phenyl-octane,
  • 2-phenyl-nonane 2-phenyl-decane
  • 2-phenyl-undecane 2-phenyl-dodecane
  • 2-phenyl-tridecane 2-phenyl-tridecane
  • Examples of the most preferred 2-PhLABs following hydrogenation are 2-phenyl- undecane, 2-phenyl-dodecane, and 2-phenyl-tridecane.
  • Examples of 2-Ph*LABs following hydrogenation are substituted 2-phenyl-pentane, substituted 2-phenyl-hexane, substituted 2-phenyl-heptane, substituted 2-phenyl-octane, substituted 2- phenyl-nonane, substituted 2-phenyl-decane, substituted 2-phenyl-undecane, substituted 2-phenyl- dodecane, substituted 2-phenyl-tridecane, substituted 2-phenyl-tetradecane, substituted 2-phenyl- pentadecane, substituted 2-phenyl-hexadecane, substituted 2-phenyl-heptadecane, substituted 2-phenyl- octadecane, substituted 2-phenyl-n
  • Examples of the more preferred 2-Ph*LABs following hydrogenation are substituted 2- phenyl-octane, substituted 2-phenyl-nonane, substituted 2-phenyl-decane, substituted 2-phenyl-undecane, substituted 2-phenyl-dodecane, and substituted 2-phenyl-tridecane.
  • Examples of the most preferred 2-Ph*LABs following hydrogenation are substituted 2- phenyl-undecane, substituted 2-phenyl-dodecane, and substituted 2-phenyl-tridecane.
  • alkene benzenes, alkylbenzenes, alkene benzene sulfonates, and alkyl benzene sulfonates may also be prepared by the methods described herein including without limitation alkene benzenes, functionalized alkene benzenes, branched alkene benzenes, substituted and non-substituted alkene benzenes, alkene benzene sulfonates, functionalized alkene benzene sulfonates, branched alkene benzene sulfonates, substituted and non- substituted alkene benzene sulfonates, alkylbenzenes, functionalized alkyl benzenes, branched alkylbenzenes, substituted and non-substituted alkylbenzenes, linear alkylbenzenes, functionalized linear alkyl benzenes, branched alkylbenzen
  • the cross metathesis substrate is soluble in the olefinic substrate.
  • the cross metathesis substrate may have a solubility of at least 0.25 M, at least 1 M, at least 3 M, or at least 5 M in the olefinic substrate.
  • the cross metathesis substrate and the olefinic substrate may also be miscible at all concentrations.
  • the cross metathesis substrate has a low solubility in the olefinic substrate, and the cross metathesis reaction occurs as an interfacial reaction. It should be noted that, when one or more of the reactants is solid or gaseous, the reactions may still be carried out in the liquid phase by dissolving any solid or gaseous reactants in the liquid reactants, or by employing a solvent, as described herein.
  • the olefinic substrate and/or cross metathesis substrate may be provided in the form of a gas.
  • the pressure of a gaseous cross-metathesis partner over the reaction solution is maintained in a range that has a minimum of about 10 psig, 15 psig, 50 psig, or 80 psig, and a maximum of about 250 psig, 200 psig, 150 psig, or 130 psig.
  • the reaction pressures are lowered till near atmospheric pressure and in particular till pressures slightly above atmospheric allow for a reduction in equipment costs compared to embodiments performed at high pressure (e.g., pressures greater than 250 psi).
  • the olefin metathesis reactions (e.g. cross metathesis) of the disclosure are catalyzed by any of the metathesis catalysts that are described herein.
  • the catalyst is typically added to the reaction medium as a solid, but may also be added as a solution wherein the catalyst is dissolved in an appropriate solvent. It will be appreciated that the amount of catalyst that is used (i.e., the "catalyst loading") in the reaction is dependent upon a variety of factors such as the identity of the reactants and the reaction conditions that are employed. It is therefore understood that catalyst loading may be optimally and independently chosen for each reaction.
  • the catalyst will be present in an amount that ranges from a low of about 0.1 ppm, 1 ppm, or 5 ppm, to a high of about 10 ppm, 15 ppm, 25 ppm, 50 ppm, 100 ppm, 200 ppm, 500 ppm, or 1000 ppm relative to the amount of the olefinic substrate.
  • Catalyst loading when measured in ppm relative to the amount of the olefinic substrate, is calculated using the equation
  • the amount of catalyst can be measured in terms of mol% relative to the amount of olefinic substrate, using the equation
  • the catalyst will generally be present in an amount that ranges from a low of about
  • 0.00001 mol%, 0.0001 mol%, or 0.0005 mol% to a high of about 0.001 mol%, 0.0015 mol%, 0.0025 mol%, 0.005 mol%, 0.01 mol%, 0.02 mol%, 0.05 mol%, or 0.1 mol% relative to the olefmic substrate.
  • the reactions of the disclosure are carried out under a dry, inert atmosphere.
  • a dry, inert atmosphere may be created using any inert gas, including such gases as nitrogen and argon.
  • the use of an inert atmosphere is optimal in terms of promoting catalyst activity, and reactions performed under an inert atmosphere typically are performed with relatively low catalyst loading.
  • the reactions of the disclosure may also be carried out in an oxygen-containing and/or a water- containing atmosphere, and in one embodiment, the reactions are carried out under ambient conditions. The presence of oxygen, water, or other impurities in the reaction may, however, necessitate the use of higher catalyst loadings as compared with reactions performed under an inert atmosphere.
  • the reactions of this invention can be run as to be completely atom efficient.
  • the ethylene generated can be used in the hydrovinylation reaction to yield 3 -phenyl- 1-butene.
  • Internal olefin cross metathesis with 3 -phenyl- 1-butene will yield 2-PhLAeB and an alpha olefin or ethylene.
  • the alpha olefin is recycled back into the internal olefin reaction, as shown in Scheme 17.
  • by-products may be form which can be recycled at the appropriate step, i.e. in III.
  • Cross Metathesis Reaction two 2-PhLAeB and ethylene may be formed; the ethylene is used in II. Hydrovinylation Reaction. The net result is no wasted carbon atoms in this invention.
  • R" is C 2 to C 18 alkyl
  • the reactions of this invention can be run as to be completely atom efficient.
  • the ethylene generated can be used in the hydrovinylation reaction to yield substituted 3 -phenyl- 1- butene.
  • Internal olefin cross metathesis with substituted 3 -phenyl- 1-butene will yield 2-Ph*LAeB and an alpha olefin or ethylene.
  • the alpha olefin is recycled back into the internal olefin reaction, as shown in Scheme 18.
  • by-products may be form which can be recycled at the appropriate step, i.e. in III.
  • R M is C 2 to C 18 alkyl
  • Scheme 19 shows an example of a general synthesis of 2-ethoxylated hydroxymethylphenyl linear alkyl benzenes (2-Ethoxylated (HM) PhLAB).
  • R z H, C -C 6 alkyl, or a protecting group
  • LG a leaving group
  • m is 1 to 100. In another embodiment, m is 2 to 50. In another embodiment, m is 4 to 25. In another embodiment, m is 4 to 15. In another embodiment, m is 1 to 4. In another embodiment, m is 1. In another embodiment, m is 2. In another embodiment, m is 3. In another embodiment, m is 4. In another embodiment, m is 2 to 4. In another embodiment, m is 3 to 4.
  • n is 2 to 18. In another embodiment, n is 6 to 12. In another embodiment, n is 6 to 10, and 12. In another embodiment n is 6. In another embodiment, n is 7. In another embodiment n is 8. In another embodiment n is 9. In another embodiment n is 10. In another embodiment n is 12. In another embodiment n is 9 to 12. In another embodiment, n is 9, 10, or 12.
  • the benzylic bromide group (-CH 2 Br) is shown as being generally capable of being in the ortho, meta, or para position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the benzylic bromide group is in the ortho position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the benzylic bromide group is in the meta position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the benzylic bromide group is in the para position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the position of the benzylic bromide group sets or fixes the position of the subsequent hydroxymethyl group and the ethoxylated hydroxymethyl group as well.
  • the benzylic bromide is in the para position on the aromatic (benzene) ring relative to the linear alkyl group, then the hydroxymethyl group and the ethoxylated hydroxymethyl group will also be in the para position on the aromatic (benzene) ring relative to the linear alkyl group.
  • R z is H, Ci-C 6 alkyl, or a protecting group. In another embodiment, R z is
  • R z is H, or C 1 -C4 alkyl, or a protecting group.
  • R z is H or C 1 -C4 alkyl.
  • R z is H, or C 1 -C3 alkyl.
  • R z is H, CH 3 , or a protecting group.
  • R z is H or CH 3 .
  • R z is H, CH 3 , CH 2 CH 3 , CH(CH 3 ) 2 , or CH 2 CH 2 CH 3
  • R z is H.
  • R z is CH 3 . Any of the protecting groups commonly used in the art may be employed.
  • protecting groups may be found, for example, in Greene et al., Protective Groups in Organic Synthesis, 3rd Ed. (New York: Wiley, 1999).
  • protecting groups include ethyl vinyl ether (EVE), tetrahydropyran (THP), tert-butyl dimethyl silyl ether (TBS), trimethylsilyl (TMS).
  • EVE ethyl vinyl ether
  • TBS tert-butyl dimethyl silyl ether
  • TMS trimethylsilyl
  • the protecting group is tetrahydropyran (THP) or tert-butyl dimethyl silyl ether (TBS).
  • the protecting group is tetrahydropyran (THP).
  • the protecting group is tert-butyl dimethyl silyl ether (TBS).
  • LG is a leaving group. Any suitable leaving group commonly used in the art may be employed. Examples of leaving groups include. In one embodiment, the leaving group is bromide, chloride, iodide, tosylate, mesylate, triflate, or phosphate. In another embodiment, the leaving group is bromide, chloride, or iodide. In another embodiment, the leaving group is bromide. In another embodiment the leaving group is tosylate, mesylate, triflate or phosphate.
  • Scheme 20 shows an example of a general synthesis of 2-ethoxylated hydroxymethylphenyl linear alkyl benzenes (2-Ethoxylated (HM) PhLAB).
  • R z H, C C 6 alkyl, or a protecting group
  • LG a leaving group
  • m is 1 to 100. In another embodiment, m is 2 to 50. In another embodiment, m is 4 to 25. In another embodiment, m is 4 to 15. In another embodiment, m is 1 to 4. In another embodiment, m is 1. In another embodiment, m is 2. In another embodiment, m is 3. In another embodiment, m is 4. In another embodiment, m is 2 to 4. In another embodiment, m is 3 to 4.
  • n is 2 to 18. In another embodiment, n is 6 to 12. In another embodiment, n is 6 to 10, and 12. In another embodiment n is 6. In another embodiment, n is 7. In another embodiment n is 8. In another embodiment n is 9. In another embodiment n is 10. In another embodiment n is 12. In another embodiment n is 9 to 12. In another embodiment, n is 9, 10, or 12.
  • the benzylic bromide group (-CH 2 Br) is shown as being generally capable of being in the ortho, meta, or para position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the benzylic bromide group is in the ortho position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the benzylic bromide group is in the meta position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the benzylic bromide group is in the para position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the position of the benzylic bromide group sets or fixes the position of the subsequent hydroxymethyl group and the ethoxylated hydroxymethyl group as well.
  • the benzylic bromide is in the para position on the aromatic (benzene) ring relative to the linear alkyl group, then the hydroxymethyl group and the ethoxylated hydroxymethyl group will also be in the para position on the aromatic (benzene) ring relative to the linear alkyl group.
  • R z is H, Ci-Ce alkyl, or a protecting group. In another embodiment, R z is
  • R z is H, or C 1 -C4 alkyl, or a protecting group.
  • R z is H or C 1 -C4 alkyl.
  • R z is H, or C 1 -C3 alkyl.
  • R z is H, CH 3 , or a protecting group.
  • R z is H or CH 3 .
  • R z is H, CH 3 , CH 2 CH 3 , CH(CH 3 ) 2 , or CH 2 CH 2 CH 3
  • R z is H.
  • R z is CH 3 . Any of the protecting groups commonly used in the art may be employed.
  • protecting groups may be found, for example, in Greene et al., Protective Groups in Organic Synthesis, 3rd Ed. (New York: Wiley, 1999).
  • protecting groups include ethyl vinyl ether (EVE), tetrahydropyran (THP), tert-butyl dimethyl silyl ether (TBS), trimethylsilyl (TMS).
  • EVE ethyl vinyl ether
  • TBS tert-butyl dimethyl silyl ether
  • TMS trimethylsilyl
  • the protecting group is tetrahydropyran (THP) or tert-butyl dimethyl silyl ether (TBS).
  • the protecting group is tetrahydropyran (THP).
  • the protecting group is tert-butyl dimethyl silyl ether (TBS).
  • LG is a leaving group. Any suitable leaving group commonly used in the art may be employed. Examples of leaving groups include. In one embodiment, the leaving group is bromide, chloride, iodide, tosylate, mesylate, triflate, or phosphate. In another embodiment, the leaving group is bromide, chloride, or iodide. In another embodiment, the leaving group is bromide. In another embodiment the leaving group is tosylate, mesylate, triflate or phosphate.
  • 2-(BM) PhLAB is an abbreviation for 2-bromomethylphenyl linear alkyl benzene.
  • 2-(HM) PhLAB is an abbreviation for 2-hydroxymethylphenyl linear alkyl benzene.
  • 2-ethoxylated (HM) PhLAB is an abbreviation for 2-ethoxylated hydroxymethylphenyl linear alkyl benzene.
  • Scheme 21 shows an example of a general synthesis of 2-ethoxylated hydroxymethylphenyl linear alkyl benzenes (2-Ethoxylated (HM) PhLAB).
  • R z H, C-
  • LG a leaving group
  • m is 1 to 100. In another embodiment, m is 2 to 50. In another embodiment, m is 4 to 25. In another embodiment, m is 4 to 15. In another embodiment, m is 1 to 4. In another embodiment, m is 1. In another embodiment, m is 2. In another embodiment, m is 3. In another embodiment, m is 4. In another embodiment, m is 2 to 4. In another embodiment, m is 3 to 4.
  • n is 2 to 18. In another embodiment, n is 6 to 12. In another embodiment, n is 6 to 10, and 12. In another embodiment n is 6. In another embodiment, n is 7. In another embodiment n is 8. In another embodiment n is 9. In another embodiment n is 10. In another embodiment n is 12. In another embodiment n is 9 to 12. In another embodiment, n is 9, 10, or 12.
  • the benzylic bromide group (-CH 2 Br) is shown as being generally capable of being in the ortho, meta, or para position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the benzylic bromide group is in the ortho position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the benzylic bromide group is in the meta position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the benzylic bromide group is in the para position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the position of the benzylic bromide group sets or fixes the position of the subsequent hydroxymethyl group and the ethoxylated hydroxymethyl group as well.
  • the benzylic bromide is in the para position on the aromatic (benzene) ring relative to the linear alkyl group, then the hydroxymethyl group and the ethoxylated hydroxymethyl group will also be in the para position on the aromatic (benzene) ring relative to the linear alkyl group.
  • R z is H, Ci-Ce alkyl, or a protecting group. In another embodiment, R z is
  • R z is H, or C 1 -C4 alkyl, or a protecting group.
  • R z is H or C 1 -C4 alkyl.
  • R z is H, or C 1 -C3 alkyl.
  • R z is H, CH 3 , or a protecting group.
  • R z is H or CH 3 .
  • R z is H, CH 3 , CH 2 CH 3 , CH(CH 3 ) 2 , or CH 2 CH 2 CH 3
  • R z is H.
  • R z is CH 3 . Any of the protecting groups commonly used in the art may be employed.
  • protecting groups may be found, for example, in Greene et al., Protective Groups in Organic Synthesis, 3rd Ed. (New York: Wiley, 1999).
  • protecting groups include ethyl vinyl ether (EVE), tetrahydropyran (THP), tert-butyl dimethyl silyl ether (TBS), trimethylsilyl (TMS).
  • EVE ethyl vinyl ether
  • TBS tert-butyl dimethyl silyl ether
  • TMS trimethylsilyl
  • the protecting group is tetrahydropyran (THP) or tert-butyl dimethyl silyl ether (TBS).
  • the protecting group is tetrahydropyran (THP).
  • the protecting group is tert-butyl dimethyl silyl ether (TBS).
  • LG is a leaving group. Any suitable leaving group commonly used in the art may be employed. Examples of leaving groups include. In one embodiment, the leaving group is bromide, chloride, iodide, tosylate, mesylate, triflate, or phosphate. In another embodiment, the leaving group is bromide, chloride, or iodide. In another embodiment, the leaving group is bromide. In another embodiment the leaving group is tosylate, mesylate, triflate or phosphate.
  • 2-(BM) PhLAB is an abbreviation for 2-bromomethylphenyl linear alkyl benzene.
  • 2-(HM) PhLAB is an abbreviation for 2-hydroxymethylphenyl linear alkyl benzene.
  • 2-ethoxylated (HM) PhLAB is an abbreviation for 2-ethoxylated hydroxymethylphenyl linear alkyl benzene.
  • Scheme 22 below shows an example of a general synthesis of 2-propoxylated hydroxymethylphenyl linear alkyl benzenes (2-propoxylated (HM) PhLAB).
  • R y H, C -C 6 alkyl, or a protecting group
  • LG a leaving group
  • terminal olefin having the structure of formula is not intended to be limiting, as other olefmic substrates may also be used as disclosed herein to prepare 2- phenyl linear alkenebenzenes (2PhLAeB).
  • m is 1 to 100. In another embodiment, m is 2 to 50. In another embodiment, m is 4 to 25. In another embodiment, m is 4 to 15. In another embodiment, m is 1 to 4. In another embodiment, m is 1. In another embodiment, m is 2. In another embodiment, m is 3. In another embodiment, m is 4. In another embodiment, m is 2 to 4. In another embodiment, m is 3 to 4.
  • n is 2 to 18. In another embodiment, n is 6 to 12. In another embodiment, n is 6 to 10, and 12. In another embodiment n is 6. In another embodiment, n is 7. In another embodiment n is 8. In another embodiment n is 9. In another embodiment n is 10. In another embodiment n is 12. In another embodiment n is 9 to 12. In another embodiment, n is 9, 10, or 12.
  • the benzylic bromide group (-CH 2 Br) is shown as being generally capable of being in the ortho, meta, or para position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the benzylic bromide group is in the ortho position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the benzylic bromide group is in the meta position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the benzylic bromide group is in the para position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the position of the benzylic bromide group sets or fixes the position of the subsequent hydroxymethyl group and the propoxylated hydroxymethyl group as well.
  • the benzylic bromide is in the para position on the aromatic (benzene) ring relative to the linear alkyl group, then the hydroxymethyl group and the propoxylated hydroxymethyl group will also be in the para position on the aromatic (benzene) ring relative to the linear alkyl group.
  • R y is H, Ci-C 6 alkyl, or a protecting group. In another embodiment, R y is
  • R y is H, or C 1 -C4 alkyl, or a protecting group.
  • R y is H or Q-C4 alkyl.
  • R y is H, or C 1 -C3 alkyl.
  • R y is H, CH 3 , or a protecting group.
  • R y is H or CH 3 .
  • R y is H, CH 3 , CH 2 CH 3 , CH(CH 3 ) 2 , or CH 2 CH 2 CH 3 .
  • R y is H.
  • R y is CH 3 . Any of the protecting groups commonly used in the art may be employed.
  • protecting groups may be found, for example, in Greene et al., Protective Groups in Organic Synthesis, 3rd Ed. (New York: Wiley, 1999).
  • protecting groups include ethyl vinyl ether (EVE), tetrahydropyran (THP), tert-butyl dimethyl silyl ether (TBS), trimethylsilyl (TMS).
  • EVE ethyl vinyl ether
  • TBS tert-butyl dimethyl silyl ether
  • TMS trimethylsilyl
  • the protecting group is tetrahydropyran (THP) or tert-butyl dimethyl silyl ether (TBS).
  • the protecting group is tetrahydropyran (THP).
  • the protecting group is tert-butyl dimethyl silyl ether (TBS).
  • LG is a leaving group. Any suitable leaving group commonly used in the art may be employed. Examples of leaving groups include. In one embodiment, the leaving group is bromide, chloride, iodide, tosylate, mesylate, triflate, or phosphate. In another embodiment, the leaving group is bromide, chloride, or iodide. In another embodiment, the leaving group is bromide. In another embodiment the leaving group is tosylate, mesylate, triflate or phosphate.
  • 2-(BM) PhLAB is an abbreviation for 2-bromomethylphenyl linear alkyl benzene.
  • 2-(HM) PhLAB is an abbreviation for 2-hydroxymethylphenyl linear alkyl benzene.
  • 2-propoxylated (HM) PhLAB is an abbreviation for 2-propoxylated hydroxymethylphenyl linear alkyl benzene.
  • Scheme 23 below shows an example of a general synthesis of 2-propoxylated hydroxymethylphenyl linear alkyl benzenes (2-propoxylated (HM) PhLAB).
  • R y H, C C 6 alkyl, or a protecting group
  • LG a leaving group
  • m is 1 to 100. In another embodiment, m is 2 to 50. In another embodiment, m is 4 to 25. In another embodiment, m is 4 to 15. In another embodiment, m is 1 to 4. In another embodiment, m is 1. In another embodiment, m is 2. In another embodiment, m is 3. In another embodiment, m is 4. In another embodiment, m is 2 to 4. In another embodiment, m is 3 to 4.
  • n is 2 to 18. In another embodiment, n is 6 to 12. In another embodiment, n is 6 to 10, and 12. In another embodiment n is 6. In another embodiment, n is 7. In another embodiment n is 8. In another embodiment n is 9. In another embodiment n is 10. In another embodiment n is 12. In another embodiment n is 9 to 12. In another embodiment, n is 9, 10, or 12.
  • the benzylic bromide group (-CH 2 Br) is shown as being generally capable of being in the ortho, meta, or para position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the benzylic bromide group is in the ortho position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the benzylic bromide group is in the meta position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the benzylic bromide group is in the para position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the position of the benzylic bromide group sets or fixes the position of the subsequent hydroxymethyl group and the propoxylated hydroxymethyl group as well.
  • the benzylic bromide is in the para position on the aromatic (benzene) ring relative to the linear alkyl group, then the hydroxymethyl group and the propoxylated hydroxymethyl group will also be in the para position on the aromatic (benzene) ring relative to the linear alkyl group.
  • R y is H, Ci-Ce alkyl, or a protecting group. In another embodiment, R y is
  • R y is H, or C 1 -C4 alkyl, or a protecting group.
  • R y is H or C 1 -C4 alkyl.
  • R y is H, or C 1 -C3 alkyl.
  • R y is H, CH 3 , or a protecting group.
  • R y is H or CH 3 .
  • R y is H, CH 3 , CH 2 CH 3 , CH(CH 3 ) 2 , or CH 2 CH 2 CH 3 .
  • R y is H.
  • R y is CH 3 . Any of the protecting groups commonly used in the art may be employed.
  • protecting groups may be found, for example, in Greene et al., Protective Groups in Organic Synthesis, 3rd Ed. (New York: Wiley, 1999).
  • protecting groups include ethyl vinyl ether (EVE), tetrahydropyran (THP), tert-butyl dimethyl silyl ether (TBS), trimethylsilyl (TMS).
  • EVE ethyl vinyl ether
  • TBS tert-butyl dimethyl silyl ether
  • TMS trimethylsilyl
  • the protecting group is tetrahydropyran (THP) or tert-butyl dimethyl silyl ether (TBS).
  • the protecting group is tetrahydropyran (THP).
  • the protecting group is tert-butyl dimethyl silyl ether (TBS).
  • LG is a leaving group. Any suitable leaving group commonly used in the art may be employed. Examples of leaving groups include. In one embodiment, the leaving group is bromide, chloride, iodide, tosylate, mesylate, triflate, or phosphate. In another embodiment, the leaving group is bromide, chloride, or iodide. In another embodiment, the leaving group is bromide. In another embodiment the leaving group is tosylate, mesylate, triflate or phosphate. [000324] In Scheme 23, 2-(BM) PhLAB is an abbreviation for 2-bromomethylphenyl linear alkyl benzene.
  • Scheme 24 shows an example of a general synthesis of 2-propoxylated hydroxymethylphenyl linear alkyl benzenes (2-propoxylated (HM) PhLAB).
  • R y H, C-
  • LG a leaving group
  • Scheme 24 Example of a general synthesis of 2-propoxylated hydroxymethylphenyl linear alkyl benzenes.
  • m is 1 to 100.
  • m is 2 to 50.
  • m is 4 to 25.
  • m is 4 to 15.
  • m is 1 to 4.
  • m is 1.
  • m is 2.
  • m is 3.
  • m is 4.
  • m is 2 to 4.
  • m is 3 to 4.
  • n is 2 to 18. In another embodiment, n is 6 to 12. In another embodiment, n is 6 to 10, and 12. In another embodiment n is 6. In another embodiment, n is 7. In another embodiment n is 8. In another embodiment n is 9. In another embodiment n is 10. In another embodiment n is 12. In another embodiment n is 9 to 12. In another embodiment, n is 9, 10, or 12.
  • the benzylic bromide group (-CH 2 Br) is shown as being generally capable of being in the ortho, meta, or para position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the benzylic bromide group is in the ortho position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the benzylic bromide group is in the meta position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the benzylic bromide group is in the para position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the position of the benzylic bromide group sets or fixes the position of the subsequent hydroxymethyl group and the propoxylated hydroxymethyl group as well.
  • the benzylic bromide is in the para position on the aromatic (benzene) ring relative to the linear alkyl group, then the hydroxymethyl group and the propoxylated hydroxymethyl group will also be in the para position on the aromatic (benzene) ring relative to the linear alkyl group.
  • R y is H, Ci-Ce alkyl, or a protecting group. In another embodiment, R y is
  • R y is H, or C 1 -C4 alkyl, or a protecting group.
  • R y is H or C 1 -C4 alkyl.
  • R y is H, or C 1 -C3 alkyl.
  • R y is H, CH 3 , or a protecting group.
  • R y is H or CH 3 .
  • R y is H, CH 3 , CH 2 CH 3 , CH(CH 3 ) 2 , or CH 2 CH 2 CH 3 .
  • R y is H.
  • R y is CH 3 . Any of the protecting groups commonly used in the art may be employed.
  • protecting groups may be found, for example, in Greene et al., Protective Groups in Organic Synthesis, 3rd Ed. (New York: Wiley, 1999).
  • protecting groups include ethyl vinyl ether (EVE), tetrahydropyran (THP), tert-butyl dimethyl silyl ether (TBS), trimethylsilyl (TMS).
  • EVE ethyl vinyl ether
  • TBS tert-butyl dimethyl silyl ether
  • TMS trimethylsilyl
  • the protecting group is tetrahydropyran (THP) or tert-butyl dimethyl silyl ether (TBS).
  • the protecting group is tetrahydropyran (THP).
  • the protecting group is tert-butyl dimethyl silyl ether (TBS).
  • LG is a leaving group. Any suitable leaving group commonly used in the art may be employed.
  • the leaving group is bromide, chloride, iodide, tosylate, mesylate, triflate, or phosphate.
  • the leaving group is bromide, chloride, or iodide.
  • the leaving group is bromide.
  • the leaving group is tosylate, mesylate, triflate or phosphate.
  • 2-(BM) PhLAB is an abbreviation for 2-bromomethylphenyl linear alkyl benzene.
  • 2-(HM) PhLAB is an abbreviation for 2-hydroxymethylphenyl linear alkyl benzene.
  • 2-propoxylated (HM) PhLAB is an abbreviation for 2-propoxylated hydroxymethylphenyl linear alkyl benzene.
  • Scheme 25 shows an example of a general synthesis of 2-ethoxylated hydroxymethylphenyl linear alkyl benzenes (2-Ethoxylated (HM) PhLAB).
  • R z H, C-
  • Scheme 25 Example of a general synthesis of 2-ethoxylated hydroxymethylphenyl linear alkyl benzenes.
  • m is 1 to 100.
  • m is 2 to 50.
  • m is 4 to 25.
  • m is 4 to 15.
  • m is 1 to 4.
  • m is 1.
  • m is 2.
  • m is 3.
  • m is 4.
  • m is 2 to 4.
  • m is 3 to 4.
  • n is 2 to 18. In another embodiment, n is 6 to 12. In another embodiment, n is 6 to 10, and 12. In another embodiment n is 6. In another embodiment, n is 7. In another embodiment n is 8. In another embodiment n is 9. In another embodiment n is 10. In another embodiment n is 12. In another embodiment n is 9 to 12. In another embodiment, n is 9, 10, or 12.
  • the benzylic bromide group (-CH 2 Br) is shown as being generally capable of being in the ortho, meta, or para position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the benzylic bromide group is in the ortho position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the benzylic bromide group is in the meta position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the benzylic bromide group is in the para position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the position of the benzylic bromide group sets or fixes the position of the subsequent hydroxymethyl group and the propoxylated hydroxymethyl group as well.
  • the benzylic bromide is in the para position on the aromatic (benzene) ring relative to the linear alkyl group, then the hydroxymethyl group and the propoxylated hydroxymethyl group will also be in the para position on the aromatic (benzene) ring relative to the linear alkyl group.
  • R z is H, Ci-Ce alkyl, or a protecting group. In another embodiment, R z is
  • R z is H, or C 1 -C4 alkyl, or a protecting group.
  • R z is H or C 1 -C4 alkyl.
  • R z is H, or C 1 -C3 alkyl.
  • R z is H, CH 3 , or a protecting group.
  • R z is H or CH 3 .
  • R z is H, CH 3 , CH 2 CH 3 , CH(CH 3 ) 2 , or CH 2 CH 2 CH 3 .
  • R z is H.
  • R z is CH 3 . Any of the protecting groups commonly used in the art may be employed.
  • protecting groups may be found, for example, in Greene et al., Protective Groups in Organic Synthesis, 3rd Ed. (New York: Wiley, 1999).
  • protecting groups include ethyl vinyl ether (EVE), tetrahydropyran (THP), tert-butyl dimethyl silyl ether (TBS), trimethylsilyl (TMS).
  • EVE ethyl vinyl ether
  • TBS tert-butyl dimethyl silyl ether
  • TMS trimethylsilyl
  • the protecting group is tetrahydropyran (THP) or tert-butyl dimethyl silyl ether (TBS).
  • the protecting group is tetrahydropyran (THP).
  • the protecting group is tert-butyl dimethyl silyl ether (TBS).
  • Scheme 26 shows an example of a general synthesis of 2-ethoxylated hydroxymethylphenyl linear alkyl benzenes (2-Ethoxylated (HM) PhLAB).
  • R z H, C-
  • m is 1 to 100. In another embodiment, m is 2 to 50. In another embodiment, m is 4 to 25. In another embodiment, m is 4 to 15. In another embodiment, m is 1 to 4. In another embodiment, m is 1. In another embodiment, m is 2. In another embodiment, m is 3. In another embodiment, m is 4. In another embodiment, m is 2 to 4. In another embodiment, m is 3 to 4.
  • n is 2 to 18. In another embodiment, n is 6 to 12. In another embodiment, n is 6 to 10, and 12. In another embodiment n is 6. In another embodiment, n is 7. In another embodiment n is 8. In another embodiment n is 9. In another embodiment n is 10. In another embodiment n is 12. In another embodiment n is 9 to 12. In another embodiment, n is 9, 10, or 12.
  • the benzylic bromide group (-CH 2 Br) is shown as being generally capable of being in the ortho, meta, or para position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the benzylic bromide group is in the ortho position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the benzylic bromide group is in the meta position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the benzylic bromide group is in the para position on the aromatic (benzene) ring relative to the linear alkyl group.
  • the position of the benzylic bromide group sets or fixes the position of the subsequent hydroxymethyl group and the propoxylated hydroxymethyl group as well.
  • the benzylic bromide is in the para position on the aromatic (benzene) ring relative to the linear alkyl group, then the hydroxymethyl group and the propoxylated hydroxymethyl group will also be in the para position on the aromatic (benzene) ring relative to the linear alkyl group.
  • R y is H, Ci-Ce alkyl, or a protecting group. In another embodiment, R y is
  • R y is H, or C 1 -C4 alkyl, or a protecting group.
  • R y is H or C 1 -C4 alkyl.
  • R y is H, or C 1 -C3 alkyl.
  • R y is H, CH 3 , or a protecting group.
  • R y is H or CH 3 .
  • R y is H, CH 3 , CH 2 CH 3 , CH(CH 3 ) 2 , or CH 2 CH 2 CH 3 .
  • R y is H.
  • R y is CH 3 . Any of the protecting groups commonly used in the art may be employed.
  • protecting groups may be found, for example, in Greene et al., Protective Groups in Organic Synthesis, 3rd Ed. (New York: Wiley, 1999).
  • protecting groups include ethyl vinyl ether (EVE), tetrahydropyran (THP), tert-butyl dimethyl silyl ether (TBS), trimethylsilyl (TMS).
  • EVE ethyl vinyl ether
  • TBS tert-butyl dimethyl silyl ether
  • TMS trimethylsilyl
  • the protecting group is tetrahydropyran (THP) or tert-butyl dimethyl silyl ether (TBS).
  • the protecting group is tetrahydropyran (THP).
  • the protecting group is tert-butyl dimethyl silyl ether (TBS).
  • Scheme 27 shows a general procedure for the alkoxylation of hydroxymethyl- substituted phenyl linear alkylbenzenes (2-(HM) PhLAB).
  • Hydroxymethyl-substituted linear alkylbenzenes (2-(HM) PhLAB) can be reacted with epoxides (ethylene oxide, propylene oxide, or mixtures thereof) in the presence of a catalytic amount of base (ex. KOH, NaOH, Ba(OH) 2 , Sr(OH) 2 , etc.) or Lewis acid (BF 3 , SnCl 4 , etc.) to afford a range of alkoxylation products.
  • base ex. KOH, NaOH, Ba(OH) 2 , Sr(OH) 2 , etc.
  • Lewis acid BF 3 , SnCl 4 , etc.
  • This invention is useful for the synthesis of high purity 2-PhLAB and high purity 2-
  • Ph*LAB by any suitable olefin metathesis catalyst.
  • Such metathesis reactions are not specifically limited, and include cross metathesis (CM), self-metathesis, ethenolysis, alkenolysis, and combinations thereof.
  • An Olefin metathesis catalyst according to the invention is preferably a Group 8 transition metal complex having the structure of formula (I) in which:
  • M is a Group 8 transition metal
  • L 1 , L 2 , and L 3 are neutral electron donor ligands
  • n 0 or 1 , such that L 3 may or may not be present;
  • n 0, 1, or 2;
  • k is 0 or 1 ;
  • X 1 and X 2 are anionic ligands
  • R 1 and R 2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups,
  • any two or more of X , X , L , L , L , R , and R can be taken together to form one or more cyclic groups, and further wherein any one or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2 may be attached to a support.
  • R 1 and R 2 may have the structure -(W ⁇ -U ⁇ " , in which W is selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene; U is a positively charged Group 15 or Group 16 element substituted with hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom- containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; V is a negatively charged counterion; and n is zero or 1. Furthermore, R 1 and R 2 may be taken together to form an indenylidene moiety.
  • Preferred catalysts contain Ru or Os as the Group 8 transition metal, with Ru particularly preferred.
  • a first group of catalysts are commonly referred to as First Generation Grubbs-type catalysts, and have the structure of formula (I).
  • M is a Group 8 transition metal
  • m is 0, 1, or 2
  • n, k, X 1 1 , V 1, V2, V 3, R 1 , and R 2 are described as follows.
  • n is 0 or 1
  • k is 0 or 1
  • L 1 and L 2 are independently selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, (including cyclic ethers), amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, substituted pyridine, imidazole, substituted imidazole, pyrazine, substituted pyrazine and thioether.
  • Exemplary ligands are trisubstituted phosphines.
  • Preferred trisubstituted phosphines are of the formula PR H1 R m R H3 , where R H1 , R H2 , and R H3 are each independently substituted or unsubstituted aryl or Ci-Cio alkyl, particularly primary alkyl, secondary alkyl, or cycloalkyl.
  • L 1 and L 2 are independently selected from the group consisting of trimethylphosphine (PMe 3 ), triethylphosphine (PEt 3 ), tri-n-butylphosphine (PBu 3 ), tri(ortho-tolyl)phosphine (P-o-tolyl 3 ), tri-tert-butylphosphine (P-tert-Bu 3 ), tri-sec-butylphosphine, tricyclopentylphosphine (PCp 3 ), tricyclohexylphosphine (PCy 3 ), triisopropylphosphine (P-i-Pr 3 ), trioctylphosphine (POct 3 ), triisobutylphosphine, (P-i-Bu 3 ), triphenylphosphine (PPh 3 ), tri(pentafluorophenyl)phosphine (P(C 6 F 5 ) 3 ), methyl
  • L 1 and L 2 may be independently selected from phosphabicycloalkane (e.g. monosubstituted 9-phosphabicyclo-[3.3.1]nonane, or monosubstituted 9-phosphabicyclo[4.2.1 ]nonane] such as cyclohexylphoban, isopropylphoban, ethylphoban, methylphoban, butylphoban, pentylphoban and the like).
  • phosphabicycloalkane e.g. monosubstituted 9-phosphabicyclo-[3.3.1]nonane, or monosubstituted 9-phosphabicyclo[4.2.1 ]nonane
  • phosphabicycloalkane e.g. monosubstituted 9-phosphabicyclo-[3.3.1]nonane, or monosubstituted 9-phosphabicyclo[4.2.1 ]nonane
  • X 1 and X 2 are anionic ligands, and may be the same or different, or are linked together to form a cyclic group, typically although not necessarily a five- to eight-membered ring.
  • X 1 and X 2 are each independently hydrogen, halide, or one of the following groups: C 1 -C 20 alkyl, C5-C 24 aryl, C 1 -C 2 0 alkoxy, C5-C 24 aryloxy, C 2 -C 2 0 alkoxycarbonyl, C6-C 24 aryloxycarbonyl, C 2 -C 24 acyl, C 2 -C 24 acyloxy, C 1 -C 2 0 alkylsulfonato, C5-C 24 arylsulfonato, C 1 -C 2 0 alkylsulfanyl, C5-C 24 arylsulfanyl, C 1 -C 20 alkylsulfinyl
  • X 1 and X 2 may be substituted with one or more moieties selected from C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C5-C 24 aryl, and halide, which may, in turn, with the exception of halide, be further substituted with one or more groups selected from halide, Ci-C 6 alkyl, Ci-C 6 alkoxy, and phenyl.
  • X 1 and X 2 are halide, benzoate, C 2 -C 6 acyl, C 2 -C 6 alkoxycarbonyl, Ci-C 6 alkyl, phenoxy, Ci-C 6 alkoxy, Ci-C 6 alkylsulfanyl, aryl, or Ci-C 6 alkylsulfonyl.
  • X 1 and X 2 are each halide, CF 3 C0 2 , CH 3 C0 2 , CFH 2 C0 2 , (CH 3 ) 3 CO, (CF 3 ) 2 (CH 3 )CO, (CF 3 )(CH 3 ) 2 CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethane-sulfonate (CF 3 S0 3 or commonly abbreviated as OTf).
  • X 1 and X 2 are each chloride.
  • R 1 and R 2 are independently selected from hydrogen, hydrocarbyl (e.g., Ci-C 2 o alkyl, C 2 -
  • R 1 and R 2 may also be linked to form a cyclic group, which may be aliphatic or aromatic, and may contain substituents and/or heteroatoms. Generally, such a cyclic group will contain 4 to 12, preferably 5, 6, 7, or 8 ring atoms.
  • R 1 is hydrogen and R 2 is selected from Ci-C 20 alkyl, C 2 -C 20 alkenyl, and C 5 -C 24 aryl, more preferably Ci-C 6 alkyl, C 2 -C 6 alkenyl, and C5-Q4 aryl. Still more preferably, R 2 is phenyl, vinyl, methyl, isopropyl, or t-butyl, optionally substituted with one or more moieties selected from Ci-C 6 alkyl, Ci-C 6 alkoxy, phenyl, and a functional group Fn as defined herein.
  • R 2 is phenyl or vinyl substituted with one or more moieties selected from methyl, ethyl, chloro, bromo, iodo, fluoro, nitro, dimethylamino, methyl, methoxy, and phenyl.
  • Any two or more (typically two, three, or four) of X , X , L , L , R , and R can be taken together to form a cyclic group, including bidentate or multidentate ligands, as disclosed, for example, in U.S. Patent No. 5,312,940, the disclosure of which is incorporated herein by reference.
  • any of X , X , L , L , L , R , and R are linked to form cyclic groups, those cyclic groups may contain 4 to 12, preferably 4, 5, 6, 7 or 8 atoms, or may comprise two or three of such rings, which may be either fused or linked.
  • the cyclic groups may be aliphatic or aromatic, and may be heteroatom-containing and/or substituted.
  • the cyclic group may, in some cases, form a bidentate ligand or a tridentate ligand. Examples of bidentate ligands include, but are not limited to, bisphosphines, dialkoxides, alkyldiketonates, and aryldiketonates.
  • a second group of catalysts commonly referred to as Second Generation Grubbs-type catalysts, have the structure of formula (I), wherein L 1 is a carbene ligand having the structure of formula (II)
  • X and Y are heteroatoms typically selected from N, O, S, and P. Since O and S are divalent, p is necessarily zero when X is O or S, q is necessarily zero when Y is O or S. However, when X is N or P, then p is 1 , and when Y is N or P, then q is 1. In a preferred embodiment, both X and Y are N;
  • Q 1 , Q 2 , Q 3 , and Q 4 are linkers, e.g., hydrocarbylene (including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene, such as substituted and/or heteroatom-containing alkylene) or -(CO)-, and w, x, y, and z are independently zero or 1, meaning that each linker is optional.
  • w, x, y, and z are all zero.
  • R 3 , R 3A , R 4 , and R 4A are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl.
  • X and Y may be independently selected from carbon and one of the heteroatoms mentioned above, preferably no more than one of X or Y is carbon.
  • L 2 and L 3 may be taken together to form a single bidentate electron-donating ligand.
  • R 1 and R 2 may be taken together to form an indenylidene moiety.
  • X 1 , X 2 , L 2 , L 3 , X and Y may be further coordinated to boron or to a carboxylate.
  • Q 4 can be taken together to form a cyclic group, and any one or more of X 1, X2, L2, L3, Q1, Q2, Q3, Q4, R1, R 2 , R 3 , R 3A , R 4 , and R 4A may be attached to a support.
  • any two or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , R 2 , R 3 , R 3A , R 4 , and R 4A can also be taken to be -A-Fn, wherein "A" is a divalent hydrocarbon moiety selected from alkylene and arylalkylene, wherein the alkyl portion of the alkylene and arylalkylene groups can be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, wherein the aryl portion of the arylalkylene can be substituted or unsubstituted, and wherein heteroatoms and/or functional groups may be present in either the aryl or the alkyl portions of the alkylene and arylalkylene groups, and Fn is a functional group, or together to form a cyclic group, and any one or more ofX , X , L , L , Q
  • R 4A are linked to form a cyclic group and at least one of X or Y is a nitrogen, or at least one of Q 3 or Q 4 is a heteroatom-containing hydrocarbylene or substituted heteroatom-containing hydrocarbylene, where at least one heteroatom is a nitrogen, are commonly referred to as N-heterocyclic carbene (NHC) ligands.
  • N-heterocyclic carbene (NHC) ligands are commonly referred to as N-heterocyclic carbene (NHC) ligands.
  • R 3A and R 4A are linked to form a cyclic group so that the carbene ligand has the structure of formula (IV)
  • R and R are as defined for the second group of catalysts above, with preferably at least one of R 3 and R 4 , and more preferably both R 3 and R 4 , being alicyclic or aromatic of one to about five rings, and optionally containing one or more heteroatoms and/or substituents.
  • Q is a linker, typically a hydrocarbylene linker, including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene linkers, wherein two or more substituents on adjacent atoms within Q may also be linked to form an additional cyclic structure, which may be similarly substituted to provide a fused polycyclic structure of two to about five cyclic groups.
  • Q is often, although not necessarily, a two-atom linkage or a three-atom linkage.
  • N-heterocyclic carbene (NHC) ligands and acyclic diammocarbene ligands suitable as L 1 thus include, but are not limited to, the following where DIPP or DiPP is diisopropylphenyl and Mes is 2,4,6-trimethylphenyl:
  • N-heterocyclic carbene (NHC) ligands and acyclic diammocarbene ligands suitable as L 1 thus include, but are not limited to the following:
  • R , R , R , R are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, or heteroatom containing hydrocarbyl, and where one or both of R W3 and R w4 may be in independently selected from halogen, nitro, amido, carboxyl, alkoxy, aryloxy, sulfonyl, carbonyl, thio, or nitroso groups.
  • N-heterocyclic carbene (NHC) ligands suitable as L 1 are further described in U.S. Pat. Nos. 7,378,528; 7,652, 145; 7,294,717; 6,787,620; 6,635,768; and 6,552,139 the contents of each are incorporated herein by reference.
  • Q is a two-atom linkage having the structure -CR U R 12 -
  • CR 13 R 14 - or -CR U CR 13 -, preferably -CR U R 12 -CR 13 R 14 -, wherein R 11 , R 12 , R 13 , and R 14 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups.
  • Examples of functional groups here include, without limitation, carboxyl, C1-C20 alkoxy, C5-C24 aryloxy, C2-C20 alkoxycarbonyl, C5-C24 alkoxycarbonyl, C2-C24 acyloxy, C1-C20 alkylthio, C5-C24 arylthio, C1-C20 alkylsulfonyl, and C1-C20 alkylsulfinyl, optionally substituted with one or more moieties selected from C1-C12 alkyl, C1-C12 alkoxy, C5-C14 aryl, hydroxyl, sulfhydryl, formyl, and halide.
  • R 11 , R 12 , R 13 , and R 14 are preferably independently selected from hydrogen, C1-C12 alkyl, substituted C1-C12 alkyl, C1-C12 heteroalkyl, substituted C1-C12 heteroalkyl, phenyl, and substituted phenyl.
  • any two of R 11 , R 12 , R 13 , and R 14 may be linked together to form a substituted or unsubstituted, saturated or unsaturated ring structure, e.g., a C4- C12 alicyclic group or a C 5 or Ce aryl group, which may itself be substituted, e.g., with linked or fused alicyclic or aromatic groups, or with other substituents.
  • any one or more of R 11 , R 12 , R 13 , and R 14 comprises one or more of the linkers.
  • R 3 and R 4 may be unsubstituted phenyl or phenyl substituted with one or more substituents selected from C1-C20 alkyl, substituted C1-C20 alkyl, C1-C20 heteroalkyl, substituted C1-C20 heteroalkyl, C 5 -C 2 4 aryl, substituted C 5 -C 2 4 aryl, C 5 -C 2 4 heteroaryl, C6-C24 aralkyl, C6-C24 alkaryl, or halide.
  • X 1 and X 2 may be halogen.
  • R 3 and R 4 are aromatic, they are typically, although not necessarily, composed of one or two aromatic rings, which may or may not be substituted, e.g., R 3 and R 4 may be phenyl, substituted phenyl, biphenyl, substituted biphenyl, or the like.
  • R 3 and R 4 are the same and are each unsubstituted phenyl or phenyl substituted with up to three substituents selected from C1-C20 alkyl, substituted C1-C20 alkyl, C1-C20 heteroalkyl, substituted C1-C20 heteroalkyl, C5-C24 aryl, substituted C5-C24 aryl, C5-C24 heteroaryl, C6-C24 aralkyl, C6-C24 alkaryl, or halide.
  • any substituents present are hydrogen, C1-C12 alkyl, C1-C12 alkoxy, C5-C14 aryl, substituted C5-C14 aryl, or halide.
  • R 3 and R 4 are mesityl (i.e. Mes as defined herein).
  • M, m, n, k, X 1 , X 2 , R 1 , and R 2 are as defined for the first group of catalysts
  • L 1 is a strongly coordinating neutral electron donor ligand such as any of those described for the first and second group of catalysts
  • L 2 and L 3 are weakly coordinating neutral electron donor ligands in the form of optionally substituted heterocyclic groups.
  • n is zero or 1 , such that L 3 may or may not be present.
  • L 2 and L 3 are optionally substituted five- or six-membered monocyclic groups containing 1 to 4, preferably 1 to 3, most preferably 1 to 2 heteroatoms, or are optionally substituted bicyclic or polycyclic structures composed of 2 to 5 such five- or six-membered monocyclic groups. If the heterocyclic group is substituted, it should not be substituted on a coordinating heteroatom, and any one cyclic moiety within a heterocyclic group will generally not be substituted with more than 3 substituents.
  • examples of L 2 and L 3 include, without limitation, heterocycles containing nitrogen, sulfur, oxygen, or a mixture thereof.
  • Examples of nitrogen-containing heterocycles appropriate for L 2 and L 3 include pyridine, bipyridine, pyridazine, pyrimidine, bipyridamine, pyrazine, 1,3,5-triazine, 1 ,2,4-triazine, 1,2,3-triazine, pyrrole, 2H-pyrrole, 3H-pyrrole, pyrazole, 2H-imidazole, 1,2,3-triazole, 1,2,4-triazole, indole, 3H-indole, lH-isoindole, cyclopenta(b)pyridine, indazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline, cinnoline, quinazoline, naphthyridine, piperidine, piperazine, pyrrolidine, pyrazolidine, quinuclidine, imidazolidine, picolylimine, purine, benzimidazole
  • Examples of sulfur-containing heterocycles appropriate for L 2 and L 3 include thiophene,
  • Examples of oxygen-containing heterocycles appropriate for L 2 and L 3 include 2H-pyran,
  • Examples of mixed heterocycles appropriate for L 2 and L 3 include isoxazole, oxazole, thiazole, isothiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,3,4-oxatriazole, 1,2,3,5- oxatriazole, 3H-l,2,3-dioxazole, 3H- l,2-oxathiole, 1,3-oxathiole, 4H- l,2-oxazine, 2H-l,3-oxazine, 1,4- oxazine, 1,2,5-oxathiazine, o-isooxazine, phenoxazine, phenothiazine, pyrano[3,4-b]pyrrole, indoxazine, benzoxazole, anthranil, and morpholine.
  • L 2 and L 3 ligands are aromatic nitrogen-containing and oxygen-containing heterocycles, and particularly preferred L 2 and L 3 ligands are monocyclic N-heteroaryl ligands that are optionally substituted with 1 to 3, preferably 1 or 2, substituents.
  • L 2 and L 3 ligands are pyridine and substituted pyridines, such as 3-bromopyridine, 4- bromopyridine, 3,5-dibromopyridine, 2,4,6-tribromopyridine, 2,6-dibromopyridine, 3-chloropyridine, 4- chloropyridine, 3,5-dichloropyridine, 2,4,6-trichloropyridine, 2,6-dichloropyridine, 4-iodopyridine, 3,5- diiodopyridine, 3,5-dibromo-4-methylpyridine, 3,5-dichloro-4-methylpyridine, 3,5-dimethyl-4- bromopyridine, 3,5-dimethylpyridine, 4-methylpyridine, 3,5-diisopropylpyridine, 2,4,6-trimethylpyridine, 2,4,6-triisopropylpyridine, 4-(fert-butyl)pyridine, 4-phenylpyridine, 3,5-diphenylpyridine, 3,5-dichloro-4
  • any substituents present on L 2 and/or L 3 are selected from halo, C 1 -C 20 alkyl, substituted C 1 -C 20 alkyl, C 1 -C 20 heteroalkyl, substituted C 1 -C 20 heteroalkyl, C 5 -C 24 aryl, substituted C5-C 24 aryl, C5-C 24 heteroaryl, substituted C5-C 24 heteroaryl, C6-C 24 alkaryl, substituted C6-C 24 alkaryl, C6-C 24 heteroalkaryl, substituted C6-C 24 heteroalkaryl, C6-C 24 aralkyl, substituted C6-C 24 aralkyl, C6-C 24 heteroaralkyl, substituted C6-C 24 heteroaralkyl, and functional groups, with suitable functional groups including, without limitation, C 1 -C 20 alkoxy, C5-C 24 aryloxy, C 2 -C 20 alkylcarbonyl, C6-C 24
  • Preferred substituents on L 2 and L 3 include, without limitation, halo, C 1 -C 12 alkyl, substituted C 1 -C 12 alkyl, C 1 -C 12 heteroalkyl, substituted C 1 -C 12 heteroalkyl, Cs-C ⁇ aryl, substituted C5-C14 aryl, C5-C14 heteroaryl, substituted C5-C14 heteroaryl, C6-C16 alkaryl, substituted C6-C16 alkaryl, C6-C16 heteroalkaryl, substituted C6-C16 heteroalkaryl, C6-C16 aralkyl, substituted C6-C16 aralkyl, C6-C16 heteroaralkyl, substituted C6-C16 heteroaralkyl, C 1 -C 12 alkoxy, C5-C14 aryloxy, C 2 -C 12 alkylcarbonyl, Ce- Ci 4 arylcarbonyl, C 2 -C 12 alkylcarbon
  • L 2 and L 3 may also be taken together to form a bidentate or multidentate ligand containing two or more, generally two, coordinating heteroatoms such as N, O, S, or P, with preferred such ligands being diimine ligands.
  • One representative bidentate ligand has the structure of formula (VI)
  • R 15 , R 16 , R 17 , and R 18 hydrocarbyl e.g., C C 2 o alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 5 -C 24 aryl, C6-C 2 4 alkaryl, or C6-C 2 4 aralkyl
  • substituted hydrocarbyl e.g., substituted Ci-C 2 o alkyl, C 2 -C 2 o alkenyl, C 2 -C 2 o alkynyl, C 5 -C 2 4 aryl, C6-C 2 4 alkaryl, or C6-C 2 4 aralkyl
  • heteroatom-containing hydrocarbyl e.g., Ci-C 20 heteroalkyl, C 5 -C 24 heteroaryl, heteroatom-containing C 6 -C 24 aralkyl, or heteroatom-containing C 6 - C 24 alkaryl
  • substituted heteroatom-containing hydrocarbyl e
  • a bidentate ligand or a tridentate ligand examples include, but are not limited to, bisphosphines, dialkoxides, alkyldiketonates, and aryldiketonates.
  • Preferred bidentate ligands are -P(Ph) 2 CH 2 CH 2 P(Ph) 2 - and -P(CH 3 ) 2 (CH 2 ) 2 P(CH 3 ) 2 -.
  • Tridentate ligands include, but are not limited to, (CH 3 ) 2 NCH 2 CH 2 P(Ph)CH 2 CH 2 N(CH 3 ) 2 .
  • X , X , L , L , L , R , and R are taken together to be cyclopentadienyl, indenyl, or fluorenyl, each optionally substituted with C 2 -C 2 o alkenyl, C 2 -C 2 o alkynyl, Ci-C 20 alkyl, C 5 -C 20 aryl, Ci-C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 5 -C 20 aryloxy, C 2 -C 20 alkoxycarbonyl, Ci-C 2 o alkylthio, Ci-C 2 o alkylsulfonyl, or Ci-C 2 o alkylsulfinyl, each of which may be further substituted with Ci-Ce alkyl, halide, Ci-Ce alkoxy or
  • X, L 1 , and L 2 are taken together to be cyclopentadienyl or indenyl, each optionally substituted with vinyl, Q-Cio alkyl, C 5 - C 2 o aryl, C1-C10 carboxylate, C2-C10 alkoxycarbonyl, C1-C10 alkoxy, or C5-C20 aryloxy, each optionally substituted with Ci-Ce alkyl, halide, Ci-Ce alkoxy or with a phenyl group optionally substituted with halide, Ci-Ce alkyl or Ci-Ce alkoxy.
  • X, L 1 and L 2 may be taken together to be cyclopentadienyl, optionally substituted with vinyl, hydrogen, methyl, or phenyl.
  • Tetradentate ligands include, but are not limited to 02C(CH2)2P(Ph)(CH 2 )2P(Ph)(CH 2 )2C02, phthalocyanines, and porphyrins.
  • M is a Group 8 transition metal, particularly Ru or Os, or, more particularly, Ru;
  • X 1 , X 2 , and L 1 are as previously defined herein for the first and second groups of catalysts
  • Y is a heteroatom selected from nil, N, O, S, and P; preferably Y is O or N;
  • R 5 , R 6 , R 7 , and R 8 are each, independently, selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, halogen-substituted amide, trifluoroamide,
  • n is 0, 1, or 2, such that n is 1 for the divalent heteroatoms O or S, and n is 2 for the trivalent heteroatoms N or P; and Z is a group selected from hydrogen, alkyl, aryl, functionalized alkyl, functionalized aryl where the functional group(s) may independently be one or more or the following: halogen, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, or borate; methyl, isopropyl, sec -butyl, t-butyl, neopentyl, benzyl, phenyl and trimethylsilyl; and wherein any combination or combinations of X , X , L ,Y, Z, R ,
  • L 1 , X 1 , X 2 , and M are as described for any of the other groups of catalysts.
  • Suitable chelating carbenes and carbene precursors are further described by Pederson et al. (U.S. Pat. Nos. 7,026,495 and 6,620,955, the disclosures of both of which are incorporated herein by reference) and Hoveyda et al. (U.S. Pat. No. 6,921,735 and WO0214376, the disclosures of both of which are incorporated herein by reference).
  • (III), or (V) are linked, such as styrenic compounds that also include a functional group for attachment to a support.
  • the functional group is a trialkoxysilyl functionalized moiety include, but are not limited to, the following:
  • complexes having linked ligands include those having linkages between a neutral NHC ligand and an anionic ligand, a neutral NHC ligand and an alkylidine ligand, a neutral NHC ligand and an L 2 ligand, a neutral NHC ligand and an L 3 ligand, an anionic ligand and an alkylidine ligand, and any combination thereof. While the possible structures are too numerous to list herein, some suitable structures based on formula (III) include:
  • transition metal carbene complexes include, but are not limited to:
  • M, X 1 , X V, V, V, R , and R are as defined for any of the previously defined four groups of catalysts;
  • r and s are independently zero or 1 ;
  • t is an integer in the range of zero to 5;
  • k is an integer in the range of zero to 1 ;
  • Y is any non-coordinating anion (e.g., a halide ion, BF 4 " , etc.);
  • Z 3 is any cationic moiety such as -P(R 2 )3 + or -N(R 2 ) 3 + ;
  • any two or more of X 1, X2, L1, L2, L3, Z1, Z2, Z3, R1, and R 2 may be taken together to form a cyclic group, e.g., a multidentate ligand, and wherein any one or more of X 1 , X 2 ,
  • L 1, L2, L3, Z1, Z2, Z3, R1, and R 2 may be attached to a support.
  • M is a Group 8 transition metal, particularly ruthenium or osmium, or more particularly, ruthenium;
  • X 1 , X 2 , L 1 and L 2 are as defined for the first and second groups of catalysts defined above;
  • R U1 , R u , RTM, R w , XT, and R are each independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, thioisocyanate, cyanato, thiocyanato, hydroxyl, ester, ether,
  • Group 8 transition metal complex of formula XIII is a Group 8 transition metal complex of formula (XIV):
  • R G7 , R G8 , R 09 , R G1 °, R GU , R G12 , R G13 , R G14 , R G15 and R G16 are as defined above for R G1 , R G2 , R G3 , R , R , and R for Group 8 transition metal complex of formula XIII or any one or more of the R G7 , R G8 , R 09 , R G1 °, R GU , R G12 , R G13 , R G14 , R G15 and R G16 may be linked together to form a cyclic group, or any one or more of the R G7 , R G8 , R G9 , R G1 °, R GU , R G12 , R G13 , R G14 , R G15 and R G16 may be attached to a support.
  • Group 8 transition metal complex of formula XIII is a Group 8 transition metal complex of formula (XV):
  • olefin metathesis catalysts that may be used in the invention disclosed herein, is a Group 8 transition metal complex comprising a Schiff base ligand having the structure of formula (XVI):
  • M is a Group 8 transition metal, particularly ruthenium or osmium, or more particularly, ruthenium;
  • X 1 and L 1 are as defined for the first and second groups of catalysts defined above;
  • Z is selected from the group consisting of oxygen, sulfur, selenium, NR JU , PR JU , AsR JU , and SbR JU ;
  • R J1 , R J2 , R J3 , R J4 , R J5 , R J6 , R J7 , R J8 , R J9 , R J1 °, and R JU are each independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate
  • Group 8 transition metal complex of formula (XVI) is a Group 8 transition metal complex comprising a Schiff base ligand having the structure of formula (XVII):
  • R J12 , R J13 , R J14 , R J15 , R J16 , R J17 , R J18 , R J19 , R J20 , and R J21 are as defined above for R J1 , R J2 , R J3 , R J4 , R J5 , and R J6 for Group 8 transition metal complex of formula XVI, or any one or more of the R J7 , R J8 , R J9 , R J1 °, R JU , R J12 , R J13 , R J14 , R J15 , R J16 , R J17 , R J18 , R J19 , R J20 , and R J21 may be linked together to form a cyclic group, or any one or more of the R J7 , R J8 , R J9 , R J1 °, R JU , R J12 , R J13 , R J14 , R J15 , R J16 , R J17 , R
  • Group 8 transition metal complex of formula (XVI) is a Group 8 transition metal complex comprising a Schiff base ligand having the structure of formula (XVIII): (XVIII)
  • olefin metathesis catalysts that may be used in the invention disclosed herein, is a Group 8 transition metal complex comprising a Schiff base ligand having the structure of formula (XIX):
  • M is a Group 8 transition metal, particularly ruthenium or osmium, or more particularly, ruthenium;
  • X 1 , L 1 , R 1 , and R 2 are as defined for the first and second groups of catalysts defined above;
  • Z is selected from the group consisting of oxygen, sulfur, selenium, NR K5 , PR K5 , AsR K5 , and SbR K5 ; m is 0, 1, or 2; and
  • R K1 , R K2 , R K3 , R K4 , and R K5 are each independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, thioisocyanate, cyanato, thiocyanato, hydroxyl, ester, ether,
  • catalysts of formulas (XVI) to (XIX) may be optionally contacted with an activating compound, where at least partial cleavage of a bond between the Group 8 transition metal and at least one Schiff base ligand occurs, wherein the activating compound is either a metal or silicon compound selected from the group consisting of copper (I) halides; zinc compounds of the formula Zn(R Y1 ) 2 , wherein R Y1 is halogen, Q-C 6 alkyl or aryl; tin compounds represented by the formula SnR Y2 R Y3 R Y4 R Y5 wherein each of R Y2 , R Y3 , R Y4 and R Y5 is independently selected from the group consisting of halogen, C -C 20 alkyl, C 3 -C 10 cycloalkyl, aryl, benzyl and C 2 -C7 alkenyl; and silicon compounds represented by the formula SiR Y6 R Y7
  • catalysts of formulas (XVI) to (XIX) may be optionally contacted with an activating compound where at least partial cleavage of a bond between the Group 8 transition metal and at least one Schiff base ligand occurs, wherein the activating compound is an inorganic acid such as hydrogen iodide, hydrogen bromide, hydrogen chloride, hydrogen fluoride, sulfuric acid, nitric acid, iodic acid, periodic acid, perchloric acid, HOCIO, HOCIO 2 and HOIO 3 .
  • an activating compound is an inorganic acid such as hydrogen iodide, hydrogen bromide, hydrogen chloride, hydrogen fluoride, sulfuric acid, nitric acid, iodic acid, periodic acid, perchloric acid, HOCIO, HOCIO 2 and HOIO 3 .
  • catalysts of formulas (XVI) to (XIX) may be optionally contacted with an activating compound where at least partial cleavage of a bond between the Group 8 transition metal and at least one Schiff base ligand occurs, wherein the activating compound is an organic acid such as sulfonic acids including but not limited to methanesulfonic acid, aminobenzenesulfonic acid, benzenesulfonic acid, / toluenesulfonic acid (also commonly referred to as tosic acid or PTSA), napthalenesulfonic acid, sulfanilic acid and trifluoromethanesulfonic acid; monocarboxylic acids including but not limited to acetoacetic acid, barbituric acid, bromoacetic acid, bromobenzoic acid, chloroacetic acid, chlorobenzoic acid, chlorophenoxyacetic acid, chloropropionic acid, cis-cinnamic acid, cyanoacetic acid, cyanoace
  • Non-limiting examples of catalysts that may be used to prepare supported complexes and in the reactions disclosed herein include the following, some of which for convenience are identified throughout this disclosure by reference to their molecular weight:
  • Ph represents phenyl
  • Cy represents cyclohexyl
  • Cp represents cyclopentyl
  • Me represents methyl
  • Bu represents n-butyl
  • t-Bu represents tert- butyl
  • z ' -Pr represents isopropyl
  • py represents pyridine (coordinated through the N atom)
  • Mes represents mesityl (i.e., 2,4,6-trimethylphenyl)
  • DiPP and DIPP represents 2,6-diisopropylphenyl
  • MiPP represents 2-isopropylphenyl.
  • catalysts useful to prepare supported complexes and in the reactions disclosed herein include the following: ruthenium (II) dichloro (3-methyl-2-butenylidene) bis(tricyclopentylphosphine) (C716); ruthenium (II) dichloro (3-methyl-2-butenylidene) bis(tricyclohexylphosphine) (C801); ruthenium (II) dichloro(phenylmethylene) bis(tricyclohexylphosphine) (C823); ruthenium (II) (l,3-bis-(2,4,6-trimethylphenyl)-2- imidazolidinylidene) dichloro (phenylmethylene) (triphenylphosphine) (C830); ruthenium (II) dichloro phenylvinylidene) bis(tricyclohexylphosphine) (C835); ruthenium
  • Still further catalysts useful in ROMP reactions, and/or in other metathesis reactions, such as ring-closing metathesis, cross metathesis, ring-opening cross metathesis, self-metathesis, ethenolysis, alkenolysis, acyclic diene metathesis polymerization, and combinations thereof, include the following structures:
  • transition metal complexes used as catalysts herein can be prepared by several different methods, such as those described by Schwab et al. (1996) J. Am. Chem. Soc. 1 18: 100- 1 10, Scholl et al. (1999) Org. Lett. 6:953-956, Sanford et al. (2001) J. Am. Chem. Soc. 123:749-750, U.S. Pat. No. 5,312,940, and U.S. Pat. No. 5,342,909, the disclosures of each of which are incorporated herein by reference. Also see U.S. Pat. Pub. No.
  • Preferred metal carbene olefin metathesis catalysts are Group 8 transition metal complexes having the structure of formula (I) commonly called “First Generation Grubbs” catalysts, formula (III) commonly called “Second Generation Grubbs” catalysts, or formula (VII) commonly called “Grubbs-Hoveyda” catalysts.
  • More preferred olefin metathesis catalysts have the structure of formula (I)
  • M is a Group 8 transition metal
  • L 1 , L 2 , and L 3 are neutral electron donor ligands
  • n 0 or 1 ;
  • n 0,1, or 2;
  • k is 0 or 1 ;
  • X 1 and X 2 are anionic ligands
  • R 1 and R 2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, wherein any two or more ofX , X , L , L , L , R , and R can be taken together to form one or more cyclic groups, and further wherein any one or more of X 1, X2, L 1, L2, L 3, R 1, and R 2 may be attached to a support;
  • M is a Group 8 transition metal
  • L 1 is a neutral electron donor ligand
  • X 1 and X 2 are anionic ligands
  • Y is a heteroatom selected from O or N;
  • R 5 , R 6 , R 7 , and R 8 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups;
  • n 0, 1 , or 2;
  • Z is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom- containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, wherein any combination of Y, Z, R 5 ,R 6 , R 7 , and R 8 can be linked to form one or more cyclic groups, and further wherein any combination of X 1 , X 2 , L 1 , Y, Z, R 5 ,R 6 , R 7 , and R 8 may be attached to a support.
  • Most preferred olefin metathesis catalysts have the structure of formula (I)
  • M is ruthenium
  • n 0;
  • n 0;
  • L 1 and L 2 are trisubstituted phosphines independently selected from the group consisting of tri-n-butylphosphine (Pn-Bu 3 ), tricyclopentylphosphine (PCps), tricyclohexylphosphine (PCy 3 ), triisopropylphosphine (P-i-Pr 3 ), triphenylphosphine (PPh 3 ), methyldiphenylphosphine (PMePh 2 ), dimethylphenylphosphme (PMe 2 Ph), and diethylphenylphosphine (PEt 2 Ph); or L 1 is an N- heterocyclic carbene selected from the group consisting of l,3-bis(2,4,6-trimethylphenyl)-2- imidazolidinylidene, 1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1 ,3-bis(2,6-di- iso
  • X 1 and X 2 are chloride:
  • M is ruthenium
  • L 1 is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine ( ⁇ - ⁇ 3 ⁇ 4 ⁇ ), tricyclopentylphosphine (PCps), tricyclohexylphosphine (PCV 3 ), triisopropylphosphine (P-i-Pr 3 ), triphenylphosphine (PPh 3 ), methyldiphenylphosphine (PMePh 2 ), dimethylphenylphosphine (PMe 2 Ph), and diethylphenylphosphine (PEt 2 Ph); or L 1 is an N-heterocyclic carbene selected from the group consisting of l,3-bis(2,4,6- trimethylphenyl)-2-imidazolidinylidene, l,3-bis(2,4,6-trimethylphenyl)imidazol-2- ylidene, l,3-bis(2,6-di-iso
  • X 1 and X 2 are chloride:
  • Y is oxygen
  • Pv 5 , Pv 6 , R 7 , and R 8 are each hydrogen
  • n 1 ;
  • Z is isopropyl
  • Suitable supports for any of the catalysts described herein may be of synthetic, semisynthetic, or naturally occurring materials, which may be organic or inorganic, e.g., polymeric, ceramic, or metallic. Attachment to the support will generally, although not necessarily, be covalent, and the covalent linkage may be direct or indirect. Indirect covalent linkages are typically, though not necessarily, through a functional group on a support surface. Ionic attachments are also suitable, including combinations of one or more anionic groups on the metal complexes coupled with supports containing cationic groups, or combinations of one or more cationic groups on the metal complexes coupled with supports containing anionic groups.
  • suitable supports may be selected from silicas, silicates, aluminas, aluminum oxides, silica-aluminas, aluminosilicates, zeolites, titanias, titanium dioxide, magnetite, magnesium oxides, boron oxides, clays, zirconias, zirconium dioxide, carbon, polymers, cellulose, cellulosic polymers amylose, amylosic polymers, or a combination thereof.
  • the support preferably comprises silica, a silicate, or a combination thereof.
  • a support that has been treated to include functional groups, inert moieties, and/or excess ligands. Any of the functional groups described herein are suitable for incorporation on the support, and may be generally accomplished through techniques known in the art. Inert moieties may also be incorporated on the support to generally reduce the available attachment sites on the support, e.g., in order to control the placement, or amount, of a complex linked to the support.
  • the metathesis catalysts that are described herein may be utilized in olefin metathesis reactions according to techniques known in the art.
  • the catalyst is typically added as a solid, a solution, or as a suspension.
  • the catalyst is suspended in a dispersing carrier such as mineral oil, paraffin oil, soybean oil, tri-isopropylbenzene, or any hydrophobic liquid which has a sufficiently high viscosity so as to permit effective dispersion of the catalyst, and which is sufficiently inert and which has a sufficiently high boiling point so that is does not act as a low-boiling impurity in the olefin metathesis reaction.
  • the amount of catalyst that is used i.e., the "catalyst loading" in the reaction is dependent upon a variety of factors such as the identity of the reactants and the reaction conditions that are employed. It is therefore understood that catalyst loading may be optimally and independently chosen for each reaction. In general, however, the catalyst will be present in an amount that ranges from a low of about 0.1 ppm, 1 ppm, or 5 ppm, to a high of about 10 ppm, 15 ppm, 25 ppm, 50 ppm, 100 ppm, 200 ppm, 500 ppm, or 1000 ppm relative to the amount of an olefinic substrate.
  • the catalyst will generally be present in an amount that ranges from a low of about
  • 0.00001 mol%, 0.0001 mol%, or 0.0005 mol% to a high of about 0.001 mol%, 0.0015 mol%, 0.0025 mol%, 0.005 mol%, 0.01 mol%, 0.02 mol%, 0.05 mol%, or 0.1 mol% relative to the olefmic substrate.
  • olefin metathesis catalysts suitable for use with the present invention include well-defined molybdenum and tungsten catalysts such as those developed by Schrock(Schrock, R.R. Chem. Rev. 2009, 109, 321 1 ; Hartford, B. Chemical & Engineering News, "Z-Selective Metathesis of Macrocycles", Volume 89, Issue 45, November 7, 201 1, page 1 1 ; Yu, M.; Wang, C; Kyle, A.F.; Jakubec, P.; Dixon, D.J.; Schrock, R.R.; Hoveyda, A.H. Nature, November 3, 2011, 479, 88); each of which is incorporated by reference, examples are shown in Scheme 11.
  • Ill-defined olefin metathesis catalysts can be dated back to the 1960's with the seminal report from Banks and Bailey of Phillips Petroleum describing an "olefin disproportionation" process catalyzed by Mo(CO)6, W(CO)6 and M0O 3 supported on alumina [Banks, R.L.; Bailey, G.C. Ind. Eng. Chem. Prod. Res. Dev. 1964, 170-173].
  • Ill-defined olefin metathesis catalysts are defined as metathesis catalysts where the metathesis active species in not well understood [Warwel, S.; Siekermann, V. Makromol. Chem., Rapid Commun.
  • Lummus Technology provides the support for the process, known as OCT® (Olefins Conversion Technology) which currently produces over 1.5 billion pounds of propylene per year [Wittcoff, H.; Reuben, B. G.; Plotkin, J. S. Industrial organic chemicals, 2 nd ed.; Wiley-Interscience, 2004; Mol, J. C. J. Mol. Catal. A: Chem. 2004, 213, 39- 45], all of which are incorporated by reference.
  • OCT® Oletcoff, H.; Reuben, B. G.; Plotkin, J. S. Industrial organic chemicals, 2 nd ed.; Wiley-Interscience, 2004; Mol, J. C. J. Mol. Catal. A: Chem. 2004, 213, 39- 45]
  • titanium metathesis catalysts include but not limited to Tebbe's reagent
  • zirconium metathesis catalysts include but not limited to ZrCl 4 /Et 3 Al and
  • vanadium metathesis catalysts include but not limited to V(acac) 3 /Et 3 AlCl, and VCl 4 /Et 3 Al.
  • molybdenum metathesis catalysts include but not limited to
  • rhenium metathesis catalysts include but not limited to Re 2 0 7 /Al 2 0 3 ,
  • osmium metathesis catalysts include but not limited to OsCl 3 3H 2 0/EtOH and Os0 4 in chlorobenzene 60°C.
  • iridium metathesis catalysts include but not limited to and excess of CF 3 C0 2 Ag, [(C 8 H 14 )2lr02CCF3]2, [(NH 4 ) 2 IrCl 6 /EtOH.
  • styrene (purity >99%), and diethylaluminum chloride in hexanes (1.0 M) were purchased from Sigma- Aldrich. 4-Methyl- 1 -pentene (purity 97%), 1-nonene (purity >90%), 1 -tetradecene (purity >90%), 3-undecanone (purity >97%), 1-undecene (purity 93%) were purchased from TCI. 1-octene (purity >97%) was purchased from Acros. 1-dodecene (purity >90%) was purchased from Fluka.
  • Olefin metathesis catalysts [l,3-Bis-(2,6-diisopropylphenyl)-2- imidazolidinylidene]dichloro(o-isopropoxyphenylmethylene) ruthenium (II) (C71 1); [l,3-bis-(2,4,6- trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2-butenylidene)(tricyclohexylphosphine) ruthenium (II) (C827); [l,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro
  • Oven temperature Starting temperature: 100 °C, hold time: 1 minute.
  • Carrier gas Helium Mean gas velocity: 31.3 ⁇ 3.5% cm/sec (calculated)
  • Reaction 1 Synthesis of 3 -phenyl- 1 -butene by hydrovinylation of styrene.
  • Reaction 6 Representative example for the synthesis of internal olefins from the self- metathesis of alpha olefins.
  • a 3 liter, 3 -neck round bottom flask was equipped with a magnetic stir bar and fitted with a reflux condenser, vacuum adapter, and a rubber septum. The flask was charged with 1-octene (1.00 kg, 8.91 mol) and subjected to full vacuum (4 mmHg) at 40 °C for 30 minutes. A solution of Grubbs metathesis catalyst C848 in dichloromethane (25 ppm) was added via syringe to the reaction mixture under vacuum.

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Abstract

La présente invention concerne des compositions comportant des alcène benzène linéaires 2-phényliques ou des alcènes benzène sulfonates linéaires 2-phényliques ou des alkylbenzènes linéaires 2-phényliques ou des alkylbenzènes sulfonates linéaires 2-phényliques, le cycle benzénique étant éventuellement substitué par un ou par plusieurs groupes désignés par R*, où R* est défini par les présentes, et des procédés de fabrication de celles-ci. L'invention concerne également des compositions, des procédés de fabrication, l'utilisation et des articles de manufacture comportant des alkylbenzènes linéaires hydroxyméthylphényliques 2-éthoxylés ou des alkylbenzènes linéaires hydroxyméthylphényliques 2-propoxylés.
PCT/US2014/059783 2013-04-09 2014-10-08 Préparation de tensioactifs par métathèse croisée WO2015126462A1 (fr)

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US9862698B2 (en) 2014-12-16 2018-01-09 Adt Pharmaceuticals, Inc. Indenyl compounds, pharmaceutical compositions, and medical uses thereof
US9931315B2 (en) 2014-12-16 2018-04-03 Adt Pharmaceuticals, Inc. Method of selectively inhibiting Ras-mediated tumor growth in humans
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US11198679B2 (en) 2014-12-16 2021-12-14 Adt Pharmaceuticals, Llc Method of treating or preventing Ras-mediated diseases
US9862698B2 (en) 2014-12-16 2018-01-09 Adt Pharmaceuticals, Inc. Indenyl compounds, pharmaceutical compositions, and medical uses thereof
US9931315B2 (en) 2014-12-16 2018-04-03 Adt Pharmaceuticals, Inc. Method of selectively inhibiting Ras-mediated tumor growth in humans
US10526307B2 (en) 2014-12-16 2020-01-07 Adt Pharmaceuticals, Llc Indenyl compounds, pharmaceutical compositions, and medical uses thereof
US10975054B2 (en) 2014-12-16 2021-04-13 Adt Pharmaceuticals, Llc Indenyl compounds, pharmaceutical compositions, and medical uses thereof
US10981886B2 (en) 2014-12-16 2021-04-20 Adt Pharmaceuticals, Llc Indenyl compounds, pharmaceutical compositions, and medical uses thereof
US11104658B2 (en) 2014-12-16 2021-08-31 Adt Pharmaceuticals, Llc Method of treating or preventing Ras-mediated diseases
US11130744B2 (en) 2014-12-16 2021-09-28 Adt Pharmaceuticals, Llc Indenyl compounds, pharmaceutical compositions, and medical uses thereof
US11407727B2 (en) 2014-12-16 2022-08-09 Adt Pharmaceuticals, Llc Indenyl compounds, pharmaceutical compositions, and medical uses thereof
CN106187713A (zh) * 2016-07-19 2016-12-07 南通市晗泰化工有限公司 烷基苯甲醇聚氧乙烯醚羟丙基烯丙基醚及衍生物及其制备方法
EP3638026A4 (fr) * 2017-06-08 2021-06-16 Huntsman Petrochemical LLC Tensioactifs polyphénylméthanol
US11186596B2 (en) 2018-04-26 2021-11-30 Adt Pharmaceuticals, Llc Anticancer indenes, indanes, azaindenes, azaindanes, pharmaceutical compositions and uses
US11680073B2 (en) 2018-04-26 2023-06-20 Adt Pharmaceuticals, Llc Anticancer indenes, indanes, azaindenes, azaindanes, pharmaceutical compositions and uses

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