US 8,557,933 B2Granted

Methods for preparation of pyridylamines and their use in oligomerization reactions

AssigneeExxonMobil Chemical Patents Inc.

InventorsJohn Robert Hagadorn, Timothy Marlow Boller, Steven Douglas Brown, Gary Michael Diamond, Keith Anthony Hall, James Martin Longmire, Lily Joy Ackerman, Susan Jessica Schofer, Eric Lee Kuiokalani Dias, Andrew Cottone, III, Carl Edgar Whittle

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Abstract

Alternate methods for preparing functionalized pyridyl-amine products from pyridinyl starting materials are provided herein. These alternately-prepared functionalized pyridyl-amines can be used as ligands or ligand precursors in catalytic compositions, e.g., in oligomerization reactions. Methods for such reactions are also provided herein.

Claims14

Dependent claims

A method for forming an olefin oligomer using a pyridylamine-containing catalytic composition, comprising the steps of:

(a) synthesizing, and optionally purifying, a functionalized pyridyl-amine product by:
(i) providing a di-substituted pyridine reactant having the following formula:
where Xb, Xc, and Xd are each independently selected from hydrogen and optionally substituted linear, branched, cyclic, heterocyclic, and/or aromatic hydrocarbyl, where at least one of Xa and Xe is a halide, where Xa and Xe can be the same or different, and where, when one of Xa and Xe is not a halide, the one of Xa and Xe that is not a halide is an optionally substituted aryl moiety;
(ii) selectively activating one of the Xa and Xe halide moieties on the di-substituted pyridine under conditions sufficient to form an activated and substituted pyridine intermediate;
and
(iii) reacting the activated and substituted pyridine intermediate with one or more other reactants, said one or more other reactants including an imine and/or an iminium compound having the following formulas:
under conditions sufficient to form the functionalized pyridyl-amine product in a single reaction step;
(b) forming a metal-ligand precursor by contacting the pyridyl-amine product with a metal precursor compound, and optionally also with an activator;
(c) contacting an olefin feed with said metal-ligand precursor under reaction conditions sufficient to produce an effluent comprising a trimerized and/or tetramerized olefin product;
and
(d) optionally isolating and/or purifying the trimerized and/or tetramerized olefin product.

8 more elements

A method for forming an olefin oligomer using a pyridylamine-containing catalytic composition, comprising the steps of:

(a) synthesizing a functionalized pyridyl-amine product by:
(i) providing a di-substituted pyridine reactant having the following formula:
where Xb, Xc, and Xd are each independently selected from hydrogen and optionally substituted linear, branched, cyclic, heterocyclic, and/or aromatic hydrocarbyl, and where both of Xa and Xe are halides;
(ii) selectively activating one of the Xa and Xe halide moieties on the di-substituted pyridine under conditions sufficient to form a mono-metallated, halo-substituted pyridine intermediate by contacting it with a hydrocarbyl-mixed metal organometallic compound having a hydrocarbyl portion and a mixed metal portion;
(iii) reacting the mono-metallated, halo-substituted pyridine intermediate with one or more other reactants under conditions sufficient to form a halo-substituted pyridinyl aldehyde intermediate;
(iv) arylating the halo-substituted pyridinyl aldehyde intermediate by contacting it with an optionally substituted aryl-dihydroxyborane under conditions sufficient to form an (optionally substituted aryl)-substituted pyridinyl aldehyde intermediate;
and
(v) aminating the (optionally substituted aryl)-substituted pyridinyl aldehyde intermediate by contacting it with one or more other reactants under conditions sufficient to form the functionalized pyridyl-amine product;
(b) forming a metal-ligand precursor by contacting the pyridyl-amine product with a metal precursor compound, and optionally also with an activator;
(c) contacting an olefin feed with said metal-ligand precursor under reaction conditions sufficient to produce an effluent comprising a trimerized and/or tetramerized olefin product;
and
(d) optionally isolating and/or purifying the trimerized and/or tetramerized olefin product.

9 more elements

A method for forming an olefin oligomer using a pyridylamine-containing catalytic composition, comprising the steps of:

(a) synthesizing a functionalized pyridyl-amine product by:
(i) providing a di-substituted pyridine reactant having the following formula:
where Xb, Xc, and Xd are each independently selected from hydrogen and optionally substituted linear, branched, cyclic, heterocyclic, and/or aromatic hydrocarbyl, and where both of Xa and Xe are halides;
(ii) selectively activating one of the Xa and Xe halide moieties on the di-substituted pyridine under conditions sufficient to form a mono-metallated, halo-substituted pyridine intermediate;
(iii) reacting the mono-metallated, halo-substituted pyridine intermediate with one or more other reactants under conditions sufficient to form a halo-substituted pyridinyl aldehyde intermediate;
(iv) arylating the halo-substituted pyridinyl aldehyde intermediate by contacting it with an optionally substituted aryl-dihydroxyborane under conditions sufficient to form an (optionally substituted aryl)-substituted pyridinyl aldehyde intermediate;
(v) aminating the (optionally substituted aryl)-substituted pyridinyl aldehyde intermediate by contacting it with one or more other reactants under conditions sufficient to form the crude functionalized pyridyl-amine product;
(vi) treating the crude functionalized pyridyl-amine product with an acid to form a functionalized pyridyl-ammonium product salt;
(vii) triturating the functionalized pyridyl-ammonium product salt to remove impurities;
and
(viii) treating the isolated, functionalized pyridyl-ammonium product salt with a base to form a purified functionalized pyridyl amine product;
(b) forming a metal-ligand precursor by contacting the pyridyl-amine product with a metal precursor compound, and optionally also with an activator;
(c) contacting an olefin feed with said metal-ligand precursor under reaction conditions sufficient to produce an effluent comprising a trimerized and/or tetramerized olefin product;
and
(d) optionally isolating and/or purifying the trimerized and/or tetramerized olefin product.

12 more elements

Dependencies are inferred from the claim text.

Facts

Application: 13/486,483Filed 1 Jun 2012 · division
Priority: 20 Sep 2007
Published: US 2012/0238713 A120 Sep 2012
Granted: 15 Oct 2013
Term ends: Not estimatedThe source records don’t support an estimate.

Classification2 codes

C07D 213/38
Radicals substituted by singly-bound nitrogen atoms: having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
C07D
Heterocyclic compounds

Family

Application60/973,965Us provisional application · filed 20 Sep 2007
Application12/192,843Parent of this division · filed 15 Aug 2008
US 2012/0238713 A1Pre-grant publication · published 20 Sep 2012
US 8,212,047 B2Parent of this division
US 2009/0082573 A1Published application
US 8,557,933 B2This patent

From the US filing history. Foreign family members aren’t listed.