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WO2025165570A1 - Pré-catalyseur de platine (iv) fonctionnalisé par benzyle ou allyle - Google Patents

Pré-catalyseur de platine (iv) fonctionnalisé par benzyle ou allyle

Info

Publication number
WO2025165570A1
WO2025165570A1 PCT/US2025/011564 US2025011564W WO2025165570A1 WO 2025165570 A1 WO2025165570 A1 WO 2025165570A1 US 2025011564 W US2025011564 W US 2025011564W WO 2025165570 A1 WO2025165570 A1 WO 2025165570A1
Authority
WO
WIPO (PCT)
Prior art keywords
independently
phenyl
dimethyl
alkyl
vinyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2025/011564
Other languages
English (en)
Inventor
Jonathan AXTELL
Mary E. Garner
Souvagya BISWAS
Sukrit MUKHOPADHYAY
Bizhong Zhu
Myoungbae LEE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Dow Silicones Corp
Original Assignee
Dow Global Technologies LLC
Dow Silicones Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies LLC, Dow Silicones Corp filed Critical Dow Global Technologies LLC
Publication of WO2025165570A1 publication Critical patent/WO2025165570A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic Table

Definitions

  • the present invention relates to a photoactivated benzyl or allyl functionalized platinum(IV) (Pt(IV)) pre-catalyst, particularly for hydrosilylation reactions.
  • Hydrosilylation is commonly used in the silicones industry for the synthesis of silicone polymers and cross-linked materials.
  • UV-initiated hydrosilylation using a photoactive pre-catalyst is becoming more popular as the energy input needed to trigger the reaction is low relative to thermally activated approaches.
  • Pt(IV) species such as cyclopentadienyltrimethylplatinum and its analogs are known as photoactive pre-catalysts (see US 4,510,094; US 8,088,878; and US 10,392,479) for hydrosilylation; Pt(IV) decomposes under UV irradiation to form the catalytically active Pt(0) species.
  • these known pre-catalysts are often undesirably volatile, and reactions using these pre-catalysts tend to be sluggish. There is a need, therefore, to discover pre-catalysts that enhance reactivity and that exhibit favorable volatility profiles.
  • the present invention is a compound of Formula 1: where x is from 0 to 5; each R 1 is independently C 1 -C 6 -alkyl or phenyl; each R 2 is independently H, methyl, ethyl, or phenyl; and R 3 is either of the following fragments: where each R 4 is C1-C6-alkyl, trifluoromethyl, C1-C6-alkoxy, y, (vinyl)silyl, or C2-C12- alkenyl; each R 6 is independently C1-C6-alkyl, trifluoromethyl, C1-C6-alkoxy, NO2, acetyl, halo, dimethyl(vinyl)silyl, or C2-C12-alkenyl; and each y is independently from 0 to 5.
  • the present invention addresses a need in the art by providing a nonvolatile Pt(IV) pre-catalyst that decomposes rapidly to the catalytically active Pt(0) state under light irradiation.
  • the present invention is a compound of Formula 1: Formula 1 where x is from 0 to 5; each R 1 is independently C1-C6-alkyl or phenyl; each R 2 is independently H, methyl, ethyl, or phenyl; and R 3 is either of the following fragments: where each R 4 is C 1 -C 6 -alkyl, trifluoromethyl, C1-C6-alkoxy, NO2, acetyl, halo, aryl-(R 6 )y, dimethyl(vinyl)silyl, or C2-C12- alkenyl; each R 6 is independently C 1 -C 6 -alkyl, trifluoromethyl, C 1 -C 6 -alkoxy, NO 2
  • Drahnak recites (Cp)dimethylbenzylplatinum (column 4, line 58, (Cp)Me2BzPt) as a representative compound of the invention; nevertheless, no details of its preparation are disclosed; consequently, the present inventors have been unable to prepare (Cp)Me2BzPt and its analogs, without extensive experimentation not taught or suggested by Drahnak. It has now been discovered that the compound of the present invention can be prepared using the following steps.
  • an alkali metal cyclopentadiene such as sodium cyclopentadiene (Na-Cp) is contacted with R 1 -Br to form an alkyl or phenyl substituted cyclopentadiene (R 1 )x-Cp.
  • R 1 groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups.
  • (R 1 )x-Cp is then contacted with an alkali metal bis(tetramethylsilyl)amide such as potassium or sodium bis(tetramethylsilyl)amide or with an alkyl lithium such as n-butyl lithium to form the alkali metal salt of (R 1 )x-Cp (Intermediate A):
  • a tolyl-functionalized Grignard reagent such as (o-tolyl)magnesium bromide can be contacted with a halide-functionalized dimethyl(vinyl)silyl compound such as chlorodimethyl(vinyl)silane to form a tolyl-functionalized dimethyl(vinyl)silyl compound, which can then be treated with a brominating agent such as N-bromosuccinimide (NBS) in the presence of a radical initiator such as azobisisobutyronitrile (AIBN) to generate a dimethyl(vinyl)silyl-functionalized brom
  • NBS N
  • the compound of Formula 1 where R 3 is phenyl-(R 5 )y can be prepared as follows: Norbornadiene dimethyl platinum (II) (NBD)PtMe 2 is dissolved in a suitable donor solvent such as pyridine, then contacted with a benzyl bromide (Br-C(R 2 )2phenyl(R 5 )y) where y is 0 to 5, preferably, 1, 2, or 3, then contacted with Intermediate A in the same reaction vessel to form a compound of the present invention.
  • each R 1 is preferably independently C1-C4-alkyl or phenyl
  • each R 2 is preferably H.
  • each R 5 is independently methyl, trifluoromethyl, nitro, but-3-ene-1-yl, methoxy, or aryl-(R 6 )y, where aryl is phenyl, naphthyl, or anthracenyl.
  • Specific examples of compounds of this embodiment of the present invention include the following:
  • the alkenyl group can be prepared analogously, by contacting the (NBD)PtMe 2 /pyridine mixture with a bromoalkene such as 1-bromo-3-methylbut-2-ene under similar reaction conditions to form the following compound: where each R 1 is preferably and each R 2 is preferably H.
  • the present invention is a method comprising the steps of contacting a solution of norbornadiene dimethyl platinum (II) and an N-donor solvent such as pyridines or quinolines with Br-C(R 2 )2phenyl(R 5 )y under conditions suitable for forming an oxidative addition intermediate, then contacting the oxidative addition intermediate with Intermediate A under conditions suitable for forming the compound of Formula 1.
  • y is from 0 to 5.
  • Suitable pyridines include pyridine, 4-methylpyridine, 4-t-butylpyridine, 4-methoxypyridine, and 4-dimethylaminopyridine.
  • Suitable quinolines include quinoline, 8-methylquinoline, and 8-methoxyquinoline.
  • the compound of the present invention is a Pt(IV) pre-catalyst that exhibits excellent efficiency for promoting UV-triggered hydrosilylation chemistry.
  • the relatively low vapor pressure of the pre-catalyst is also beneficial because the amount of pre-catalyst needed to initiate hydrosilylation is lower due to its decreased volatility.
  • Cp refers to an unsubstituted cyclopentadiene ring
  • Cp* refers to a pentamethyl substituted cyclopentadiene ring
  • Me Cp refers to a monomethyl substituted cyclopentadiene ring
  • 2,6-Me2Bz refers to 2,6-dimethylbenzyl
  • 4-CF3Bz refers to 4-trifluoromethylbenzyl
  • 3-Me-2-Bu refers to 3-methylbut-2-enyl
  • 2-BuBz refers to 2-(but-3-en- 1-yl)benzyl
  • 2-PhBz refers to 2-phenylbenzyl
  • 2-SiMe2ViBz refers to 2-dimethyl(vinyl)silyl.
  • the resulting gray suspension was allowed to warm to ambient temperature and stirred vigorously for 4 h.
  • the reaction mixture was then removed from the glove box and diluted with deionized water (25 mL).
  • the resulting biphasic mixture was transferred to a separatory funnel and the organic layer was washed with water (2 x 10 mL) and brine (2 x 10 mL).
  • the organic layer was collected, concentrated on silica gel, and purified by column chromatography using 100% hexanes as the mobile phase. Fractions 3-5 were combined and concentrated to a colorless liquid. Yield: 2.33 g, 34.0 %.
  • reaction mixture was then heated at 70 °C for 18 h. After cooling to ambient temperature, the reaction mixture was filtered through a Celite pad atop a disposable PTFE filter frit. The pad was washed with hexanes (2 x 15 mL). The combined washes and filtrate were then concentrated onto silica gel and purified by ISCO chromatography using 100 % hexanes at the mobile phase. The desired product was isolated from fractions 3-9. Yield: 1.12 g, 25.8 %.
  • Example 2 Preparation of Cp*PtMe2(4-CF3Bz) (NBD)PtMe 2 (60 mg, 0.189 mmol) was combined with pyridine (5 mL) in a 20-mL vial equipped with a magnetic stir bar and stirred for 10 min in a nitrogen-filled glovebox. 4-Trifluoromethylbenzyl bromide (45 mg, 0.189 mmol) was then added to the mixture and stirring was continued for 1.5 h, after which time LiCp* (34 mg, 2.36 mmol) was added. The mixture was heated to 45 °C and stirring was continued overnight.
  • Example 3 Preparation of Cp*PtMe2(3-Me-2-Bu) (NBD)PtMe2 (67 mg, 0.211 mmol) and pyridine (5 mL) were charged into a 20-mL vial equipped with a stirring bar and stirred for 10 min in a nitrogen-filled glovebox. Prenyl bromide (25 ⁇ L, 0.211 mmol) was then added and the mixture was stirred for 1.5 h, after which time LiCp* (39 mg, 0.275 mmol) was added. The mixture was heated to 45 °C and stirring was continued overnight. The red mixture was dried in vacuo, charged with CH2Cl2, and filtered through a Florisil pad.
  • Example 4 Preparation of Me CpPtMe2(2-BuBz) (NBD)PtMe2 (0.118 g, 0.37 mmol, 1 equiv) and pyridine (3 mL) were charged into a 20-mL vial equipped with a magnetic stir bar and stirred for 20 min at ambient temperature in a nitrogen glove box.
  • 1-(Bromomethyl)-2-(but-3-en-1-yl)benzene 0.084 g, 0.37 mmol, 1 equiv
  • pyridine 0.084 g, 0.37 mmol, 1 equiv
  • Li Me Cp (0.038 g, 0.45 mmol, 1.2 equiv) was added to the reaction mixture directly as a solid at ambient temperature.
  • the reaction mixture was stirred at ambient temperature for 1 h, whereupon the reaction mixture was passed through a Celite pad and a 0.45- ⁇ m PTFE syringe filter.
  • the Celite pad was rinsed with hexanes (2 x 3 mL) and the washings were combined with the filtrate. The volatiles were then removed in vacuo and the purple residue was stored at -25 °C for 18 h.
  • Li Me Cp (0.040 g, 0.47 mmol, 1.2 equiv) was added to the reaction mixture directly as a solid at ambient temperature.
  • the reaction mixture was allowed to continue stirring at ambient temperature for 1 h, whereupon the volatiles were removed in vacuo. Hexanes was added to the residue, affording a suspension that was then stirred for 1 h at ambient temperature.
  • the suspension was then passed through a Florisil pad and a 0.45- ⁇ m PTFE syringe filter. The filtration pad was rinsed with hexanes (2 x 5 mL) and combined with the filtrate. The extraction and filtration were repeated two more times.
  • Examples 1-6 Pre-catalysts were combined separately with methyl trimethoxy silane (XIAMETERTM OFS-6070 Silane (MTM)). Each pre-catalyst + MTM mixture was added to a pre-mixed blend of a vinyl-terminated polydimethylsiloxane (XIAMETERTM RBL-9119 Polymer (Polymer 1)) and a trimethylsilyl-terminated methylhydrosiloxane-dimethylsiloxane copolymer (DOWSILTM 6-3570 Polymer (Polymer 2). Each composition was mixed at 2000 rpm for 30 s.
  • Table 1 illustrates the formulations.
  • Formulation 1 used the compound of Example 1;
  • Formulation 2 used the compound of Example 2, etc.
  • Pre-catalyst + Solvent amounts were tuned to achieve a concentration of elemental Pt of 18 ppm for each formulation.
  • the pre-catalyst concentration in MTM refers to the weight % concentration of the pre-catalyst.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)

Abstract

La présente invention concerne un composé de formule (1) : dans laquelle R1, R2, R3, et x sont tels que définis dans la description. Le composé de la présente invention est utile en tant que pré-catalyseur pour des réactions d'hydrosilylation.
PCT/US2025/011564 2024-01-31 2025-01-14 Pré-catalyseur de platine (iv) fonctionnalisé par benzyle ou allyle Pending WO2025165570A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202463627502P 2024-01-31 2024-01-31
US63/627,502 2024-01-31

Publications (1)

Publication Number Publication Date
WO2025165570A1 true WO2025165570A1 (fr) 2025-08-07

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Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (2)

Country Link
TW (1) TW202532425A (fr)
WO (1) WO2025165570A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4510094A (en) 1983-12-06 1985-04-09 Minnesota Mining And Manufacturing Company Platinum complex
US8088878B2 (en) 2008-01-25 2012-01-03 Wacker Chemie Ag Hydrosilylation reactions activated through radiation
US10392479B2 (en) 2014-08-26 2019-08-27 Wacker Chemie Ag Platinum complexes and their use in compounds that can be cross-linked by a hydrosilylation reaction

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4510094A (en) 1983-12-06 1985-04-09 Minnesota Mining And Manufacturing Company Platinum complex
US8088878B2 (en) 2008-01-25 2012-01-03 Wacker Chemie Ag Hydrosilylation reactions activated through radiation
US10392479B2 (en) 2014-08-26 2019-08-27 Wacker Chemie Ag Platinum complexes and their use in compounds that can be cross-linked by a hydrosilylation reaction

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
EUR. J. INORG. CHEM., vol. 2015, 2015, pages 226 - 239
LARRY D BOARDMAN ET AL: "195 Pt NMR Study of (n5-Cyclopentadienyl) trialkylplatinum (IV) Complexes", MAGNETIC RESONANCE IN CHEMISTRY, JOHN WILEY , CHICHESTER, GB, vol. 30, no. 6, 1 June 1992 (1992-06-01), pages 481 - 489, XP007901484, ISSN: 0749-1581, DOI: 10.1002/MRC.1260300605 *
ROBINSONSHAW, J. CHEM, SOC., 1965, pages 1529
VEDERNIKOV ANDREI N. ET AL: "Photoinduced activation of arene CH bonds with ([eta]5-cyclopentadienyl)-trimethylplatinum(IV): a possible role of CpPtR2H", MENDELEEV COMMUNICATIONS, vol. 10, no. 1, 1 January 2000 (2000-01-01), GB, pages 20 - 21, XP093273695, ISSN: 0959-9436, Retrieved from the Internet <URL:https://www.mathnet.ru/links/37e14251240ca2f5ec07a1658ebc98dd/mendc4361.pdf> DOI: 10.1070/MC2000v010n01ABEH001168 *

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