IP Library › Granted Patent US 12,600,737
Granted Patent B2
US 12,600,737 · App. 18/995,170 · Granted Apr 14, 2026

Bidentate phosphite ligands, catalytic compositions containing such ligands, and catalytic processes utilizing such catalytic compositions

Inventors: Benjamin David Herzog (Wichita, KS); William J. Tenn, III (Beaumont, TX)
Assignee: INV Nylon Chemicals Americas, LLC
C07F9/145C07C253/10C07F15/04
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 12,600,737
App. No.
18/995,170
Granted
Apr 14, 2026
Kind
B2
Abstract

A bidentate phosphite ligand comprises a backbone having a structure of acenaphthene-1,2-diol in which the hydrogen atoms of the hydroxyl groups have each been replaced by a P(OR 1 ) 2 group, where R 1 is an aryl radical. When combined with a transition metal, such as nickel, the ligand provides a catalyst complex useful in hydrocyanation and other reactions.

Claims (18)

1 . A process for the hydrocyanation of an organic compound containing at least one olefinic group comprising reacting the organic compound with hydrogen cyanide in the presence of a catalyst complex comprising a bidentate phosphite ligand and at least one transition metal, wherein the bidentate phosphite ligand comprises a backbone having a structure of acenaphthene-1,2-diol in which the hydrogen atoms of the hydroxyl groups have each been replaced by a P(OR 1 ) 2 group, wherein R 1 is an aryl radical optionally substituted with methyl.

2 . The process of claim 1 , wherein the organic compound comprises 1,3-butadiene.

3 . The process of claim 1 , wherein the organic compound comprises 3-pentenenitrile.

4 . The process of claim 1 , wherein each R 1 group is an aryl substituted with methyl.

5 . The process of claim 1 , wherein the bidentate phosphite ligand has the following structure:

6 . The process of claim 1 , wherein the at least one transition metal comprises nickel.

7 . The process of claim 1 , wherein a product of the hydrocyanation is an unsaturated compound having no more than one carbon-carbon double bond, wherein the process further comprises double bond isomerization of the unsaturated compound having no more than one carbon-carbon double bond comprising contacting the monoethylenically unsaturated compound with the catalyst complex.

8 . The process of claim 7 , wherein the unsaturated compound having no more than one carbon-carbon double bond comprises 2-methyl-3-butenenitrile.

9 . A process for double bond isomerization of an unsaturated compound having no more than one carbon-carbon double bond comprising contacting the compound with a catalyst complex comprising a bidentate phosphite ligand and at least one transition metal, wherein the bidentate phosphite ligand comprises a backbone having a structure of acenaphthene-1,2-diol in which the hydrogen atoms of the hydroxyl groups have each been replaced by a P(OR 1 ) 2 group, wherein R 1 is an aryl radical optionally substituted with methyl.

10 . The process of claim 9 , wherein the compound comprises 2-methyl-3-butenenitrile.

11 . The process of claim 9 , wherein each R 1 group is an aryl substituted with methyl.

12 . The process of claim 9 , wherein the bidentate phosphite ligand has the following structure:

13 . The process of claim 9 , wherein the at least one transition metal comprises nickel.

14 . A bidentate phosphite ligand comprising a backbone having a structure of acenaphthene-1,2-diol in which the hydrogen atoms of the hydroxyl groups have each been replaced by a P(OR 1 ) 2 group, wherein R 1 is an aryl radical optionally substituted with methyl.

15 . The bidentate phosphite ligand of claim 14 , wherein each R 1 group is an aryl substituted with methyl.

16 . The bidentate phosphite ligand of claim 14 , having the following structure:

17 . A catalyst complex comprising the bidentate phosphite ligand of claim 14 and at least one transition metal.

18 . The catalyst complex of claim 17 , wherein the at least one transition metal comprises nickel.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 27, 2025
From: HERZOG, BENJAMIN DAVID; TENN, WILLIAM J., III
To: INV NYLON CHEMICALS AMERICAS, LLC
Reel/Frame 070343/0123 →
Priority Claims (1)
GB 2215077 · Oct 13, 2022 · national
Continuity (2)
Provisional Application 63394315 · Aug 2, 2022
Related Publication 20260015370A1 · Jan 15, 2026
References Cited (107)
US 3496217A · Drinkard, Jr. · 1970 [cited by applicant]
US 3496218A · Drinkard, Jr. · 1970 [cited by applicant]
US 3631191A · Kane · 1971 [cited by applicant]
US 3655723A · Drinkard, Jr. · 1972 [cited by applicant]
US 3846461A · Shook · 1974 [cited by applicant]
US 3847959A · Shook · 1974 [cited by applicant]
US 3903120A · Shook, Jr. · 1975 [cited by applicant]
US 4467116A · Van Leeuwen et al. · 1984 [cited by applicant]
US 4774353A · Hall · 1988 [cited by applicant]
US 4874884A · Mckinney · 1989 [cited by applicant]
US 5512696A · Kreutzer · 1996 [cited by applicant]
US 5663369A · Kreutzer · 1997 [cited by applicant]
US 5688986A · Tam · 1997 [cited by applicant]
US 5717126A · Paciello et al. · 1998 [cited by applicant]
US 5723641A · Tam · 1998 [cited by applicant]
US 5821378A · Foo · 1998 [cited by applicant]
US 5847191A · Bunel · 1998 [cited by applicant]
US 5910600A · Urata · 1999 [cited by applicant]
US 6121184A · Druliner · 2000 [cited by examiner]
US 6812352B2 · Kreutzer et al. · 2004 [cited by applicant]
US 6852661B1 · Ahlers et al. · 2005 [cited by applicant]
US 7531693B2 · Gebeyehu et al. · 2009 [cited by applicant]
US 7906688B2 · Brammer et al. · 2011 [cited by applicant]
US 9011691B2 · Tenn et al. · 2015 [cited by applicant]
US 9040733B2 · Moerbe et al. · 2015 [cited by applicant]
US 9040735B2 · Aki et al. · 2015 [cited by applicant]
US 9050591B2 · Fraga-dubreuil · 2015 [cited by applicant]
US 9221852B2 · Forsyth · 2015 [cited by applicant]
US 9932298B2 · Vos · 2018 [cited by applicant]
US 10143999B2 · Fraga-dubreuil et al. · 2018 [cited by applicant]
US 10537885B2 · Medhekar · 2020 [cited by applicant]
US 10759741B2 · Aki et al. · 2020 [cited by applicant]
US 20030135014A1 · Radu et al. · 2003 [cited by applicant]
US 20030144440A1 · Gagne et al. · 2003 [cited by applicant]
US 20030144559A1 · Hess et al. · 2003 [cited by applicant]
US 20060052624A1 · Galland et al. · 2006 [cited by applicant]
US 20060100455A1 · Galland et al. · 2006 [cited by applicant]
US 20220242891A1 · Zhang · 2022 [cited by applicant]
DE 102005061642A1 · 2006 [cited by applicant]
EP 1344770A1 · 2003 [cited by applicant]
EP 2243763B1 · 2014 [cited by applicant]
GB 1417554A · 1975 [cited by applicant]
JP 2007203269A · 2007 [cited by applicant]
KR 20220025310A · 2022 [cited by applicant]
WO 9514659A1 · 1995 [cited by applicant]
WO 9906146A2 · 1999 [cited by applicant]
WO 9906357A1 · 1999 [cited by applicant]
WO 9952632A1 · 1999 [cited by applicant]
WO 0134612A2 · 2001 [cited by applicant]
WO 0240491A1 · 2002 [cited by applicant]
WO 2004007435A2 · 2004 [cited by applicant]
WO 2004024684A2 · 2004 [cited by applicant]
WO 2004050588A2 · 2004 [cited by applicant]
WO 2012033556A1 · 2012 [cited by applicant]
WO 2013181095A1 · 2013 [cited by applicant]
Bugerenko et al., “Structure of reaction products of alkylhalosilanes with sodium dialkyl phosphites”, Zhumal Obshchei Khimii, 2023, 1 page (Abstract Only). [cited by applicant]
Chivers et al., “Lithiation of Tris(alkyl- and arylamido)orthophosphates EP[N(H)R]3(E ) O, S, Se): Imido Substituent Effects and PdE Bond Cleavage”, Inorganic Chemistry, vol. 42, No. 13, 2003, pp. 3994-4005. [cited by applicant]
Das et al., “Carbohydrate recognition: Enantioselective spirobifluorene diphosphonate receptors”, Tetrahedron Letters, vol. 38, Issue 21, May 26, 1997, pp. 3675-3678. [cited by applicant]
Harold Hart, “Iptycenes, cuppedophanes and cappedopha”, Department of Chemistry, Michigan State University, Pure & Applied Chern., vol. 65, No. 1, 1993, pp. 27-34. [cited by applicant]
International Preliminary Report on Patentability received for PCT Application No. PCT/IB2023/055290, mailed on Dec. 5, 2024, 6 pages. [cited by applicant]
International Preliminary Report on Patentability received for PCT Application No. PCT/IB2023/055292, mailed on Dec. 5, 2024, 7 pages. [cited by applicant]
International Preliminary Report on Patentability received for PCT Application No. PCT/IB2023/057665, mailed on Feb. 13, 2025, 8 pages. [cited by applicant]
International Preliminary Report on Patentability received for PCT Application No. PCT/IB2023/057666, mailed on Feb. 13, 2025, 7 pages. [cited by applicant]
International Preliminary Report on Patentability received for PCT Application No. PCT/IB2023/057667, mailed on Feb. 13, 2025, 9 pages. [cited by applicant]
International Preliminary Report on Patentability received for PCT Application No. PCT/IB2023/057668, mailed on Feb. 13, 2025, 11 pages. [cited by applicant]
International Preliminary Report on Patentability received for PCT Application No. PCT/IB2023/057673, mailed on Feb. 13, 2025, 7 pages. [cited by applicant]
International Preliminary Report on Patentability received for PCT Application No. PCT/IB2023/057675, mailed on Feb. 13, 2025, 11 pages. [cited by applicant]
International Preliminary Report on Patentability received for PCT Application No. PCT/IB2023/057677, mailed on Feb. 13, 2025, 7 pages. [cited by applicant]
International Search Report and Written Opinion received for PCT Application No. PCT/IB2023/055290, mailed on Aug. 29, 2023, 7 pages. [cited by applicant]
International Search Report and Written Opinion received for PCT Application No. PCT/IB2023/055292, mailed on Aug. 29, 2023, 9 pages. [cited by applicant]
International Search Report and Written Opinion received for PCT Application No. PCT/IB2023/057665, mailed on Nov. 7, 2023, 11 pages. [cited by applicant]
International Search Report and Written Opinion received for PCT Application No. PCT/IB2023/057666, mailed on Nov. 8, 2023, 9 pages. [cited by applicant]
International Search Report and Written Opinion received for PCT Application No. PCT/IB2023/057667, mailed on Nov. 28, 2023, 12 pages. [cited by applicant]
International Search Report and Written Opinion received for PCT Application No. PCT/IB2023/057668, mailed on Nov. 27, 2023, 15 pages. [cited by applicant]
International Search Report and Written Opinion received for PCT Application No. PCT/IB2023/057673, mailed on Apr. 29, 2024, 9 pages. [cited by applicant]
International Search Report and Written Opinion received for PCT Application No. PCT/IB2023/057675, mailed on Mar. 5, 2024, 15 pages. [cited by applicant]
International Search Report and Written Opinion received for PCT Application No. PCT/IB2023/057677, mailed on Nov. 30, 2023, 9 pages. [cited by applicant]
Joss Pepe Strache, “Studies on Enantioselective Nickel-Catalyzed Hydrocyanation and Chromane Natural Products”, 2023, 295 pages. [cited by applicant]
Kee et al., A new class of chelating diphosphite: Synthesis and complexation of the silylated diphosphites [(R1O)2PO] 2SiR2R3 (R1 = Me, Et; R2 , R3 = Me, Ph, H, Ch CH2), Polyhedron, vol. 11, Issue 1, 1992, pp. 135-137. [cited by applicant]
Li et al., “Design and Synthesis of a Novel Triptycene-based Ligand for Modeling Carboxylate-Bridged Diiron Enzyme Active Sites”, NIH Public Access, Org Lett., vol. 13, Issue 19, 2011, pp. 5052-5055. [cited by applicant]
Li et al., “Facile Synthesis of Enantiopure 1,1′ -Spirobiindane-7,7′ -diol and Its 4,4′ -Derivatives: Application in Enantioselective Addition of Diethylzinc to Aromatic Aldehydes”, Synthesis, No. 17, 2004, pp. 2805-280… [cited by applicant]
Maji et al., “Cyclometalated complexes derived from calix[4]arene bisphosphites and their catalytic applications in cross-coupling reactions”, Journal of Organometallic Chemistry, vol. 696, Issue 20, Oct. 1, 2011, pp. 3… [cited by applicant]
Maji et al., “Palladium and platinum complexes of chiral and achiral calix[4]arene bisphosphite ligands”, Polyhedron, vol. 27, Issue 17, Nov. 25, 2008, pp. 3519-3527. [cited by applicant]
N. S. Imyanitov, “Cone angle of ligands—Group IV and V compounds”, Koordinatsionnaya Khimiya, 1985, vol. 11, No. 9, 1 page (Abstract Only). [cited by applicant]
Paciello et al., “Chelated Bisphosphites with a Calix[4]arene Backbone: New Ligands for Rhodium-Catalyzed Low-Pressure Hydroformylation with Controlled Regioselectivity”, vol. 38, Issue 13-14, pp. 1920-1923. [cited by applicant]
Panayiotis V. Ioannou, “Synthesis of arsinolipids: II. A non-isosteric analogue of fully acylated cardiolipin”, Chemistry and Physics of Lipids, vol. 117, Issues 1-2, Aug. 2002, pp. 7-18. [cited by applicant]
Shahlai et al., “Synthesis of Supertriptycene and Two Related Iptycenes”, The Journal of Organic Chemistry, vol. 56, Issue 24, 1991, pp. 6905-6912. [cited by applicant]
Smith et al., “Toward the Rhodium-Catalyzed Bis-Hydroformylation of 1,3-Butadiene to Adipic Aldehyde”, Organometallics, vol. 30, 2011, pp. 3643-3651. [cited by applicant]
Sood et al., “Phosphorus-Based p-tert-Butylcalix[5]arene Ligands”, Inorganic Chemistry, vol. 43, No. 9, 2004, pp. 2975-2980. [cited by applicant]
Steyer et al., “Bis-phosphites and bis-phosphinites based on distally-functionalised calix[4]arenes: coordination chemistry and use in rhodium-catalysed, low-pressure olefin hydroformylation”, Dalton Transactions, 2005,… [cited by applicant]
Sum et al., “Synthesis, characterization and reactivity of the silylated diphosphites [(R1O)2PO]2SIR2R3 (R1double bond Me, Et; R2, R3double bond Me, Ph, H, CHdouble bondCH2). Crystal structure of [MnBr(CO)32SiMe2]”, Pol… [cited by applicant]
Thiel et al., “A Simple Nickel Catalyst Enabling an E-Selective Alkyne Semihydrogenation”, Chemistry—A European Journal, vol. 26, 2020, pp. 1597-1603. [cited by applicant]
Wassenaar et al., “INDOLPhosphole and INDOLPhos Palladium—Allyl Complexes in Asymmetric Allylic Alkylations”, Organometallics, vol. 28, 2009, pp. 2724-2734. [cited by applicant]
Yu et al., “Enantioselective Nickel-Catalyzed Migratory Hydrocyanation of Nonconjugated Dienes”, Angew. Chem Int Ed Engl., vol. 59, 2020, pp. 21436-21441. [cited by applicant]
Yu et al., “Highly Enantioselective Nickel-Catalyzed Hydrocyanation of Disubstituted Methylenecyclopropanes Enabled by TADDOL-basedDiphosphite Ligands”, Organic Letters, vol. 22, Issue 2, 2020, pp. 594-597. [cited by applicant]
Yu et al.,“Regio-, Chemo-, and Enantioselective Ni-Catalyzed Hydrocyanation of 1,3-Dienes”, Organic Letters, vol. 23, Issue 3, 2021, pp. 930-935. [cited by applicant]
Trishin et al., “Interaction of Aryldichlorophosphines and Aryldichlorophosphites with Primary Aromatic Amines”, Journal of General Chemistry, vol. 49, 1979, 14 pages (Including English Translation). [cited by applicant]
Chesterton et al., “Making the Baskets: Synthesis of Calixarenes”, Chapter 2, Apr. 23, 2025, pp. 10-31. [cited by applicant]
Bagher, et al., “Introduction to Radio Active Materials”, International Journal of Renewable and Sustainable Energy, vol. 3, No. 3, 2014, pp. 59-67. [cited by applicant]
Baker, et al., “Chelating Diphosphite Complexes of Nickel(0) and Platinum(0): their Remarkable Stability and Hydrocyanation Activity”, Journal of the Chemical Society, Chemical Communications, 1991, pp. 803-804. [cited by applicant]
Baker, et al., “Chiral aryl diphosphites: a new class of ligands for hydrocyanation catalysis”, Journal of the Chemical Society, Chemical Communications, 1991, pp. 1292-1293. [cited by applicant]
Green, M.L.H., “A New Approach to the Formal Classification of Covalent Compounds of the Elements”, Journal of Organometallic Chemistry, vol. 500, 1995, pp. 127-148. [cited by applicant]
Greenwood, et al., “Chemistry of Elements”, School of chemistry, Chapters 20-25, 1997, pp. 944-1112. [cited by applicant]
Kruger, et al., “Synthesis and Molecular Structure of Chiral Bis(1,3,2-dioxaphospholanes)”, Zeitschrift fuer Anorganische and Allgemeine Chemie, 2000, 626(10), pp. 2228-2234. [cited by applicant]
Patil, et al., “ Exploration and Investigation of Periodic Elements for Electrocatalytic Nitrogen Reduction”, Department of Chemistry, 2020, 44 Pages. [cited by applicant]
Plant, et al., “Radioactivity and Radioelements”, In Journal of Pollutants, Human Health and the Environment: A Risk Based Approach, 2011, pp. 115-146. [cited by applicant]
Zhang, et al., “Recent progress in transition-metal-catalyzed hydrocyanation of nonpolar alkenes and alkynes”, Organic & Biomolecular Chemistry, 2020, pp. 391-399. [cited by applicant]