'USO11655266B2 2) United States Patent (10) Patent No: US 11,655,266 B2 Schneider et al. 45) Date of Patent: May 23, 2023 (61) PLATINUM COMPLEXES HAVING (2) Us.e. PHINE, LIGANDS FOR CPC. CU7F 15/0093 (2013.01); Bor 3172409 (2013.01); HOLS 2231/321 2013.01), BOLL 2531/828 (201301) BINAPHTHYLDIPHO THE CATALYSIS OF TH HYDROXYCARBONYLATION OF ETHYLENICALLY UNSATURATE] COMPOUNDS (58) Fleld of Classification Seare CPC 2. COM 1510003 BOL 31/2408; CO7C 51/4 ‘ce application file for complete search history (71) Appicans EVONIK OPERATIONS GMI co ee Us. psTENTE DOCUMENTS (72) vento: Caron Sender, Monin am Rin (DE); Ralf Jackstell, Rostock (DE); 90 eetG24S BZ 12019 Dyballa et al. Mather Bete Onset Ncnogen—22UQNGHS AL 9302 Ying (DE); Robert Franke, Marl (DE) a FOREIGN PATENT DOCUMENTS (73) Assignee: EVONIK OPERATIONS GMBH, Bssen (DE) iP B388414 AL 102018 (4) Notice: Suibjoct to any disclaimer, the term of this (OTHER PUBLICATIONS patent is extended of adjusted under 35 ° TSC. 1540) by O days US. Appl No, 17/S44,144, le Dec. 7, 2021, Scheer US. Appl No. 754417, fle Dee. 7, 2021, Sohne US. AMD No, 17544227 led Dee 7, 2021, Yang et. European Search Report dated May 19,2021 for European Patent Appicaion No. 203127544 (5 pages in German ith Machine (21) Appl. Now 171844,284 (22) Filed: Dee. 7, 2021 Talon), Yang. otal generalpatinum-caalyzd alkorycatonyation of Prior Publication Data ‘etn. Chemical Comnticlions, 2020, vl. $6, pp. 235-5298, US 202210177506. Al Jun, 9, 2022 Primary Esaminer —Sikatl A Witherspoon (74) Attornes, Agent, or Firm — Smith, Ganbrell & G0) Foreign Application Priority Data Russell, EP Dee. 9, 2020 (EP) 20212784 (57) ABSTRACT Platinum complexes having binaphihyldiphosphine I (1) Int. C or the catalysis of the hydroxycarbonylation of ethyleni- COE i909 200601) linens cae ow 3124 {2o0801) core sid (2005.01) 13 Claims, No DrawingsUS 11,655,266 B2 1 PLATINUM COMPLEXES HAVING BINAPHTHYLDIPHOSPHINE LIGANDS FOR ‘THE. CATALYSIS OF THE, HYDROXYCARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS, Platinum complexes having binaphthykliphosphine Figands for the catalysis of the hydroxyearbonylation of ‘ethylenically unsaturated compounds “The present invention relates 10 platinum complexes having binaphihyldiphosphine ligands for the catalysis of the hydroxycarbonylation of ethylenically unsaturated com- pounds. ‘The bydroxycarbonylation of ethylenically unsaturated ‘compounds is a process of increasing. significance. A. hydroxycarbonylation is understood 10 mean te direct reac- tion of ethylenically unsaturated compounds such as olefins with carbon monoxide in the presence of ‘complex and a ligand to give the corresponding acids ‘Scheme |: General reaction equation of the bydroxyear- bonylation of an ethylenically unsaturated compound EP 3388414 AI describes a method of hydeofomylation ‘of eyelooctadiene (COD) using 4((1, 1°91 "-terpheny} yloxy)-S-dinapaho[2, 1-121 3.2}dioxaplosphepine. ‘A disadvantage of palladium is its high cost, ‘The technical problem addressed by the present invention js that of providing novel complenes having a less costly ‘tal than palladium as the central atom, The complexes are ditionally to achieve good conversions in hylrexycarho- nylations ‘This object is achieved by a complex according to claim 1 Complex comprising Pr and ae where R', R®, R', Rare cach independently selected from CC: )alkyl, (Cy-Ca)- heteroaryl The expression (C-Cy_)alkyl encompasses. straight. cain and branched alkyl groups having 1 © 12 earbon ‘atoms, These are preferably (Cy-Cyalkyl_ groups, more preferably (C,-C,)-alkyl, most preferably (C,-C,)-aikyl “The expression (Cy-Cay}-heteroaryl encompasses mon0= ‘or polyeyelie aromatic hydrocarbyl radicals having 6 +0 20, ‘earhon atoms, where one oF more of the carbon atoms tre replaced by heteroatoms. Preferred heteroatoms are NO and 8, The (CyCyy)eteroary] groups have 6 10 20, pref ral ora metal 2 0 o 2 erably 6014 and more preferably 6 010 ring atoms. Thus, or example, pyridyl in the context of this invention is @ heteroaryl radical ‘Suitable (C,-C}heteroary groups having at least six sing atoms are especially pyridyl, pyridazinyl, pyrimidyl pyrvinyl, benzofuranyl, indotyl, isoindoly! Tn one embodiment, at least two of the RY, R2, RY, R® radicals are a —(Cj-Caz)-heteroaryl radical having at least sx ring atoms, ‘In-one embodiment, the Rand R° radicals are each a Cy-Cy)-beteroary/| radical baving atleast six ring atoms. In ‘one embodiment, the R' and R* radicals are each 2 pyridyl Tn one embodiment, R? and R* are —(C)-Cy3)alkyl In one embodiment, R? and R* are tert-butyl In one embodiment, the compound (1 has the stuctare oO OO ‘The invention further relates 10 the use of a complex ccoring to the invention for eatalysis of a hydroxyearbo- ylation reaction Process comprising the process steps of ) initially charping an ethylenically unsaturated com- pound: ») adding a complex as described above, or ‘compound of formula (2) where RE, RY, Rare cach independently selected from ACC, allyl, —(Cy-Cap)- heteroaryl and a substance comprising Pt ©) adding an acid 4) feeding in CO; ©) heating the reaction mixture from a) 19 d), with conversion of the ethylenically unsaturated compound to carborglic acid In this process, process steps a), b), €) and d) can be effected in any desired sequence, Typically, however, the Addition of CO is effected after the oo-reactants have boca initially changed in steps a) toc). In addition, CO can also be fed in in two oF more steps, in sueh a way that, forUS 11,655,266 B2 3 ‘example, a portion ofthe CO is fst fe in, then the mixture js heated, and chen a further portion of CO is fed in, ‘The ethylenically unsaturated compounds used as reactant in the process according t the invention contain one or more ‘carbon-carbon double bonds. These compounds are also refered to hercinafter as olefins for simplification, The ‘double bonds may be terminal or inter. Inone variant of the proces, the ethylenically unsaturated ‘compound does not comprise any further funetional groups apart from carbon-carbon double bonds. none variant of the proces, th ethylenically unsaturated ‘compound is selected from: ethene, propene, I-butene, cis andor trans-2-butene, isobutene, 1 3-butadiene, L-pentene cis andlor trans-2-pentene, 2-methyl--butene, 3metbyl-1- butene, 2-methyl-2-hutene, hexene, tetramethylethylene heptene, I-octene, 2-octene, disn-butene, of mixtures thereat In one variant of the proces, the aed in process step e) is selected from: acetie acid, perchloric acid, sulfuric acid, Phosphoric acid, methylphosphonic acid, methanesulfonie ‘eid, ruoromethanesl fone aid ert-butanesulfonic acid, p-olvencsulfonic acid (PTSA), 2-hydroxypropane-2-sulfo- hic acid, 24,6-trimelhylbenzenesulfonie acid, dadecylsulfo- nie acid, camphorsulfonie acid. In one variant of the process the acid in process sep ©) is acetic acid (ACOH). none variant ofthe proces, the substance comprising PL js soleted from: platinum dichloride (PAC1,), platinum) acetylacetonate [PY(acae] platinum} acetate [PUOAC):], dichloro(1,S-cyelooctadiene}platinun(I) [Pu(cod),Cl.), bis (Gienzylidencacetoneyplatinu [P1(dba),],bisfactontrle) sichloroplatinum(l) [PA(CH,CN),Cl}.(Ginnamy! platinum, dichloride (Px(cinnamyDC.) ‘In one variant ofthe proces, the substance comprising PL Js solected from: platinum dichloride (PC1.), platinum) acetylacetonate [PY(acae platinum) acetate [PUOAC),] CO js fed inn step d) preferably at a partial CO pressure between 0.1 and 10 MPa (110 100 bar), preferably between {and 8 MPa (10 o 80 bur), more preferably between 2 and 6 MPa (20 to 60 bar). The reaction mixture is heated in step) of the process soconting fo the invention preferably toa temperature in the range from 60? C. to 160°C., preferably in the ringe from 80 to 140° C., more preferably in the range from 80 to 120° in onder to convert the ethylenically unsaturated com- pound to an ac The invention i to be illustrated in detail hereinafter by ‘8 working example, Conversion of I-octene to the acid Ply Lig, wae 0 aohan, Aco, Reaction conditions: I-oetene (1,0 mmol), PCI, (0.01 mmol, 1.0 mol °%), ligand: bidentate phosphine ligand (0.022 mmol, 22 mol %), sulfuric acid [0.3 M] 05 ml, ACOH (L$ ml) pressure (CO: 40 har, temperature: 120° C reaction time: 18 h o 4 The reaction was conducted in a process aeeording tothe invention with the ligand (1), and as a comparative experi- ‘meat withthe ligand (2): ‘The process according to the invention with ligand (1) gave a Yield of $0% here, In the comparative experiment with ligand (2), by contrast, only a yield of 268% was achieved The cost of Peis below that of Pd. Te object ie thus achieved by a complex aecording t the invention, “The invention claimed is 1. Complex comprising Pt and a compound of formula (1) where RY, RE, RY, RE are each independently selected from (CC ghalkyl, —{CeeCaa heteroaryl 2. Complex according to claim 1, ‘wherein at Teast two of the R', RE, R3, RY radicals are a obleteroaryl radical having at least six ring atoms. 3. Complex according to elim 4, ‘wherein the Rand R® radicals are each a —(Cy-Co) Ietercaryl radical having at lest six ring atoms, 4. Complex according to claim 1, ‘wherein the Rand R radicals are each 2-pyridyl 8. Complex according to claim 1, wherein R* and R* are —(C,-C, alkylUS 11,655,266 B2 5 6, Complex according to claim 1, wherein R? and R* ae tert-butyl 7. Complex according to claim 1, ‘wherein the compound (I) has the stractre (1: 8, Process comprising the process steps of: 8) initially charging’ an ethylenically unsstursted come pound: ‘by adling « complex according to claim 1, of ‘compound of formula (1) where RORY a and RY, RY are each independently selected! fom \rCya}alkyl, (CoC ag heteroaryl ance comprising Pt ©) adding an acid 4) feeding in CO; ©) heating the reaction mixture from a) 19 4), with ‘conversion of the ethylenically unsaturated compound to a carboxylic acid. 9. Process according to claim 8, ‘wherein the ethylenically unsaturated compound is selected from: ethene, propene, I-butene, cis- andor twans-2-hutene, isobutene, 1,3-butadiene, I-pentene, cise andlor " trans-2-pentene, — 2-methyl-l-butene, 3.meliy-1-butene, 2-melhy-2-butene, bexene, tera cliylethylene, heptene, L-oetene, 2-oetene, butene, oF mixtures thereof. 10, Process according to claim 8, ‘wherein the acid in process step ¢) i elected from: soe ‘cid, perchloric acid, sulle acid, phosphoric acid, methyphosphonic acid, methanesulfonic acid, triluo- romethanesblfonic acid, tert-butanesulfonie acid, p-oluenesulfonie acid (PTSA), 2-hydroxypropane- sulfonic acid, 2,46-rimethylbenzenesulfonie acid, Aodecylsulfonie acid, camphorsullonie aid 11, Process acconding to claim 8, ‘wherein the acid in process sep c) is acetic sci. 12, Process aecording to claim 8, \herwin the substance comprising PL is selected from: platinum dichloride (PIC), platinum(Il)acetylaceto- nate. [Pt(aeae),|, platinum) acetate [PHOAC),], dlichloro(1 S-cyelooetadiene)platinum(ll) [Picod). (Cl, bis(dibenzylideneacetone)platinum [PY(dba)s] bis {acctonitrileWichloroplatinumi(ll) —[PUCH,CN),C1) (Ginnamyplatinum dichloride [PYeinnamy)C1,) 13. Process according to claim 8, wherein the substance comprising Pt is selected from: platinum dichloride (PICL), platinum(It) acetylaceto- ‘ate [Pcoeae),] platinum( I) acetate [PUOAC).]