Search

US-12623985-B2 - Selective terminal CH alumination of saturated hydrocarbons

US12623985B2US 12623985 B2US12623985 B2US 12623985B2US-12623985-B2

Abstract

Disclosed herein is the selective functionalization of one or more hydrocarbons ranging from the longest macromolecules to methane as the smallest. Functionalization is achieved through C—H activation of the one or more hydrocarbons and is carried out by the catalytic complex described herein. Also disclosed is the compound of formula (I) and the compound of formula (II).

Inventors

  • Aaron David Sadow
  • Jessica RODRIGUEZ
  • Uddhav KANBUR
  • Frederic A. PERRAS
  • Alexander L. PATERSON
  • Andrew KOCEN
  • Geoffrey W. Coates
  • Anne M. LaPointe
  • Massimiliano Delferro
  • Ryan A. HACKLER

Assignees

  • IOWA STATE UNIVERSITY RESEARCH FOUNDATION, INC.
  • CORNELL UNIVERSITY
  • UCHICAGO ARGONNE, LLC

Dates

Publication Date
20260512
Application Date
20221108

Claims (20)

  1. 1 . A method of functionalizing a hydrocarbon comprising: providing a compound of formula (I): Al(R 1 ) 3 (I); providing a compound of formula (II): Met(R 2 ) n @support (II); providing one or more hydrocarbons; wherein R 1 is independently selected at each occurrence thereof from the group consisting of C 6 -C 10 aryl and C 1 -C 10 alkyl; Met is selected from the group consisting of zirconium, titanium, hafnium, scandium, yttrium, lanthanum, and lutetium; R 2 is C 1 -C 4 alkoxy; n is 1, 2, 3, or 4; and support is alumina or sil ica/alumina; contacting the compound of f ormula (I) with the compound of formula (II) to form a complex; contacting the complex with one or more hydrocarbons in a reaction mixture under reaction conditions effective to functionalize the one or more hydrocarbons, wherein R 1 is a group that does not produce a hydride under the reaction conditions; and recovering the functionalized one or more hydrocarbons.
  2. 2 . The method of claim 1 , wherein R 1 is independently selected at each occurrence thereof from the group consisting of methyl, ethyl, n-propyl, n-butyl, t-butyl, n-pentyl, n-octyl, and phenyl.
  3. 3 . The method of claim 2 , wherein R 1 is ethyl.
  4. 4 . The method of claim 1 , wherein Met is zirconium.
  5. 5 . The method of claim 1 , wherein R 2 is —OtBu.
  6. 6 . The method of claim 1 , wherein n is 3.
  7. 7 . The method of claim 1 , wherein the support is silica/alumina.
  8. 8 . The method of claim 1 , wherein the compound of formula (I) is selected from the group consisting of AlMe 3 , AlEt 3 , AliBu 3 , and AlPh 3 .
  9. 9 . The method of claim 8 , wherein the compound of formula (I) is AlEt 3 .
  10. 10 . The method of claim 1 , wherein the compound of formula (II) is selected from the group consisting of Zr(OMe) n @SiO 2 —Al 2 O 3 , Zr(OEt) n @SiO 2 —Al 2 O 3 , Zr(OnPr) n @SiO 2 —Al 2 O 3 , Zr(OiPr) n @SiO 2 —Al 2 O 3 , Zr(OnBu) n @SiO 2 —Al 2 O 3 , Zr(OCH 2 CHMe 2 ) n @SiO 2 —Al 2 O 3 , and Zr(OtBu) n @SiO 2 —Al 2 O 3 .
  11. 11 . The method of claim 8 , wherein the compound of formula (II) is Zr(OtBu) 3 @SiO 2 —Al 2 O 3 .
  12. 12 . The method of claim 8 , wherein the compound of formula (II) is Zr(OtBu) 2 @SiO 2 —Al 2 O 3 .
  13. 13 . The method of claim 1 , wherein the one or more hydrocarbons is selected from the group consisting of methane, one or more C 2 -C 30 hydrocarbons, one or more C 31 -C 100 hydrocarbons, one or more C 101 -C 150 hydrocarbons, one or more C 150 -C 200 hydrocarbons, high density polyethylene (HDPE), low density polyethylene (LDPE), polyethylene (PE), polypropylene, high molecular weight isotactic polypropylene (iPP), linear low density polyethylene (LLDPE), polyethylene-polypropylene-copolymers polystyrene (PS), polystyrene 1000 (PS 1000), polyalphaolefin-10, polyalphaolefins, hydrocarbon oils, hydrocarbon waxes, paraffin wax, mineral oils, synthetic oils, and mixtures thereof.
  14. 14 . The method of claim 13 , wherein the one or more C 2 -C 30 hydrocarbons is selected from the group consisting of dodecane, eicosane, and mixtures thereof.
  15. 15 . The method of claim 13 , wherein the one or more hydrocarbons is high density polyethylene (HDPE).
  16. 16 . The method of claim 1 , wherein the step of contacting the complex with one or more hydrocarbons under conditions effective to functionalize the one or more hydrocarbons is carried out by: adding an electrophile to the reaction mixture to form a functional group on one or more primary carbons of the one or more hydrocarbons.
  17. 17 . The method of claim 16 , wherein the electrophile is selected from the group consisting of O 2 , CO 2 , electrophilic halogen, diethyl azodicarboxylate, n-chlorosuccinimide, n-bromosuccinimide, n-iodosuccinimide, ICl, pyridine N-oxide, H 2 O 2 , organic peroxides, and a combination thereof.
  18. 18 . The method of claim 16 , wherein the functional group is selected from the group consisting of alcohol, carboxylic acid, halide, alkyl aluminum, aryl aluminum, and a combination thereof.
  19. 19 . The method of claim 1 , wherein the step of contacting the complex with one or more hydrocarbons under conditions effective to functionalize the one or more hydrocarbons further comprises: carrying out catalytic chain growth of the one or more hydrocarbons in the presence of olefins.
  20. 20 . The method of claim 1 , wherein the step of contacting the complex with one or more hydrocarbons under conditions effective to functionalize the one or more hydrocarbons further comprises: carrying out an organometal-catalyzed cross-coupling reaction.

Description

This application claims the priority benefit of U.S. Provisional Patent Application Ser. No. 63/277,040 filed Nov. 8, 2021, which is hereby incorporated by reference in its entirety. GOVERNMENT INTERESTS This invention was made with government support under DOE Contract No. DE-AC02-07CH11358 and DOE Contract No. DE-AC02-06CH11357, both awarded by U.S. Department of Energy. The government has certain rights in the invention. FIELD The present application is directed to a catalyst and its use for the selective functionalization of hydrocarbons. BACKGROUND Catalytic methods for the direct introduction of heteroatom functionality into aliphatic hydrocarbons engage oxidations, carbenoid or nitrenoid insertions, or C—H bond dehydrogenative elementation chemistry such as borylation to transform inexpensive chemical feedstocks into value-added products. These methods typically have been developed for activation and transformation of small molecules, such as the oxidation of methane to methanol or the oxidation of cyclohexane to cyclohexanol, or the borylation of aromatic compounds to allow cross-coupling in shortened synthetic routes. These small-molecule C—H bond activations can also be adapted for post-synthesis functionalization of polyolefins to provide functional-group-containing polymers. Such polymers combine the useful physical properties of polyolefins with chemical reactivity needed to improve barrier properties, create adhesive films, or conjugate chains to functional materials to benefit food and biomedical security. This approach, in combination with melt processing, could also allow repurposing of discarded single-use plastics, which are majority contributors to the polymer waste crisis, as new materials with improved biodegradable characteristics. Recent advances in polyolefin post-synthesis functionalization have relied upon these existing catalytic or radical chemistries, with the processes needing to develop mild conditions to avoid chain cleavage or cross linking from reactions that often accompany C—H bond activations. C—H borylation of polyolefins is catalyzed by molecular rhodium precursors with bis(pinacolato)diboron to provide borylated polyolefins, which are subsequently oxidized to give hydroxy-terminated side chains. Catalytic oxidations, giving hydroxylated polyolefins, and radical functionalization are typically governed by reactant bond strength and rates rebound vs chain scission. Alternatively, functional groups are typically introduced into polystyrene during its synthesis, rely upon heteroatom-containing styrene monomers, rather than post-polymerization conversions. New, organometallic-catalyzed C—H bond activations that avoid single-electron steps leading to chain scission or crosslinking, could also provide the selectivity needed to create value from myriad polyolefin materials. Aluminum-based reagents are attractive for C—H bond functionalization, particularly in conversions of the massive quantity of currently discarded single-use polyolefins, due to their elemental availability, atom-economical direct syntheses from simple substances (e.g., Al, H2 and alkenes gives alkylaluminums), and wide-ranging and versatile use in synthetic manufacturing. For example, alkylaluminum species can be oxidized with O2 to give alcohols, carboxylated with CO2 to give carboxylic acids, protonated with weak acids to form alkanes, halogenated with electrophilic halogen sources such as I2 to give alkyl halides, used as activators or chain transfer agents in alkene polymerizations, and for carbon-carbon bond formations including carboaluminations or cross-coupling reactions. Unfortunately, hydrocarbon functionalizations utilizing such reagents are surprisingly limited, and catalytic C—H bond aluminations are unknown with commercial alkylaluminum reactants or in conversions of aliphatic C—H bonds. Instead, the only examples involve palladium-catalyzed reactions of diketiminate-supported aluminum(I) or dihydride reagents to give arylaluminum products. New C—H bond alumination reactions employing commercial alkylaluminum reagents for transformations of saturated hydrocarbons could be advantageous for the direct functionalization of polyolefins, as well as other hydrocarbons, to directly provide polar-functional-group-containing compounds. The present application relates to overcoming deficiencies in the art. SUMMARY One aspect of the present application relates to a method of functionalizing a hydrocarbon comprising: providing a compound of formula (I): Al(R1)3  (I) providing a compound of formula (II): Met(R2)n@support  (II) providing one or more hydrocarbons; wherein R1 is independently selected at each occurrence thereof from the group consisting of C6-C10 aryl and C1-C10 alkyl;Met is a transition metal or lanthanide series metal;R2 is independently selected at each occurrence thereof from the group consisting of C1-C10 alkoxy, C6-C10 aryloxy, (C6-C10-aryl)o-C1-C10-alkoxy, (C1-C10-alkyl)p-C