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Chemical Structure| 3375-31-3

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Hwang, Dong-Jin ; Yang, Chuanhe ; Wang, Yinan ; Kelso, Hannah ; Pochampally, Satyanarayana ; Pfeffer, Lawrence M , et al.

Abstract: Background/Objectives: Human glioblastoma (GBM) is the most aggressive brain cancer in adults and a highly treatment-refractory malignancy. The overall prognosis for the GBM is extremely poor, with a median survival of 12–14 months after initial diagnosis. Many GBM patients initially respond to the DNA alkylating agent temozolomide (TMZ), but patients often become therapy-resistant, and tumors recur. We previously reported that treatment with PFI-3, which is a small molecule inhibitor of the bromodomain of the BRG1 subunit of the SW1/SNF chromatin remodeling complex, enhanced the sensitivity of GBM cells to TMZ in vitro and in vivo GBM animal models. Our general objective was to perform an SAR study of new diphenyl PFI-3 analogs. Methods: New structural analogs of PFI-3 were developed, synthesized, and tested for their ability to enhance TMZ-induced GBM cell death by ELISA. Results: Following on the enhanced activity of compounds 2a and 2b, new diphenyl PFI-3 analogs with specific structural adjustments were made to better understand the structural requirements to optimize function. Additionally, several new structurally different candidates (e.g., 4a, 4b, and 5) showed much better efficacy in sensitizing GBM cells to TMZ-induced GBM cell death. Conclusions: Four series of PFI-3 analogs (2, 3, 4, and 5) were designed, synthesized, and tested for the ability to sensitize GBM cells to TMZ-induced cell death. Series 2 optimized the A-ring and R-isomer chirality. Series 3 used a 5-membered linker with weak activity. Series 4’s di-phenyl urea compounds showed better bromodomain inhibition. Series 5’s methoxyphenyl-B-ring analogs were exceptionally strong inhibitors.

Keywords: bromodomain ; glioblastoma (GBM) ; therapeutic enhancing drug (TED) ; anti-GBM activity ; structure-activity relationship (SAR) ; PFI-3 analog ; temozolomide (TMZ)

Purchased from AmBeed: ; ; ;

Meador, William E ; Saucier, Matthew A ; Tucker, Max R ; Kruse, Nicholas A ; Mobley, Alexander J ; Brower, Connor R , et al.

Abstract: Shortwave infrared (SWIR, 1000-1700 nm) and extended SWIR (ESWIR, 1700-2700 nm) absorbing materials are valuable for applications including fluorescence based biological imaging, photodetectors, and light emitting diodes. Currently, ESWIR absorbing materials are largely dominated by inorganic semiconductors which are often costly both in raw materials and manufacturing processes used to produce them. The development of ESWIR absorbing organic molecules is thus of interest due to the tunability, solution processability, and low cost of organic materials compared to their inorganic counterparts. Herein, through the combination of heterocyclic indolizine donors and an antiaromatic fluorene core, a series of organic chromophores with absorption maxima ranging from 1470-2088 nm (0.84-0.59 eV) and absorption onsets ranging from 1693-2596 nm (0.73-0.48 eV) are designed and synthesized. The photophysical and electrochemical properties of these chromophores, referred to as FluIndz herein, are described via absorption spectroscopy in 17 solvents, cyclic voltammetry, solution photostability, and transient absorption spectroscopy. Molecular orbital energies, predicted electronic transitions, and antiaromaticity are compared to higher energy absorbing chromophores using density functional theory. The presence of thermally accessible diradical states is demonstrated using density functional theory and EPR spectroscopy, while XRD crystallography confirms structural connectivity and existence as a single molecule. Overall, the FluIndz chromophore scaffold exhibits a rational means to access organic chromophores with extremely narrow optical gaps.

Purchased from AmBeed: ; ; ;

Diana M. Soto-Martínez ; Garrett D. Clements ; John E. Díaza, Joy Becher ; Robert C. Reynoldsb, Christina Ochsenbauer ; Timothy S. Snowden ;

Abstract: The von Hippel-Lindau (VHL) protein serves as the substrate recognition subunit of the multi-subunit Cullin-2 RING E3 ubiquitin ligase (CRL2VHL), which regulates intracellular concentrations of hypoxia inducible factors (HIFs) through a ubiquitin proteasome system (UPS) cascade. Strategic recruitment of CRL2VHL by bi- or trifunctional targeted protein degraders (e.g., PROTACs®) offers the prospect of promoting aberrant polyubiquitination and ensuing proteasomal degradation of disease-related proteins. Non-peptidic, L-hydroxyproline-bearing VHL ligands such as VH032 (1) and its chiral benzylic amine analog Me-VH032 (2), are functional components of targeted protein degraders commonly employed for this purpose. Herein, we compare two approaches for the preparation of 1 and 2 primarily highlighting performance differences between Pd(OAc)2 and Pd-PEPPSI-IPr for the key C–H arylation of 4-methylthiazole. Results from this comparison prompted the development of a unified, five-step route for the preparation of either VH032 (1) or Me-VH032 (2) in multigram quantities, resulting in yields of 56% and 61% for 1 and 2, respectively. Application of N-Boc-L-4-hydroxyproline rather than N-tert-butoxycarbonyl to shield the benzylic amine during the coupling step enhances step economy. Additionally, we identified previously undisclosed minor byproducts generated during arylation steps along with observations from amine deprotection and amidation reaction steps that may prove helpful not only for the preparation of 1 and 2, but for other VHL recruiting ligands, as well.

Purchased from AmBeed: ; ; ; ; ; ; 3959-07-7

Zhumin Zhang ; Jordan L. Chasteen ; Bradley D. Smith ;

Abstract: The chemosensor literature contains many reports of fluorescence sensing using polyaromatic hydrocarbon fluorophores such as pyrene, , or polyaryl(ethynylene), where the fluorophore is excited with ultraviolet light (<400 nm) and emits in the visible region of 400–500 nm. There is a need for general methods that convert these “turn-on” hydrocarbon fluorescent sensors into ratiometric sensing paradigms. One simple strategy is to mix the responsive hydrocarbon sensor with a second non-responsive dye that is excited by ultraviolet light but emits at a distinctly longer wavelength and thus acts as a reference signal. Five new cyanine dye cassettes were created by covalently attaching a pyrene, , or biphenyl(ethynylene) component as the ultraviolet-absorbing energy donor directly to the pentamethine chain of a deep-red cyanine (Cy5) energy acceptor. Fluorescence emission studies showed that these Cy5-cassettes exhibited large pseudo-Stokes shifts and high through-bond energy transfer efficiencies upon excitation with ultraviolet light. Practical potential was demonstrated with two examples of ratiometric fluorescence sensing using a single ultraviolet excitation wavelength. One example mixed a Cy5-cassette with a pyrene-based fluorescent indicator that responded to changes in Cu2+ concentration, and the other example mixed a Cy5-cassette with the fluorescent pH sensing dye, .

William E. Meador ; Timothy A. Lewis ; Abdul K. Shaik ; Kalpani Hirunika Wijesinghe ; Boqian Yang ; Amala Dass , et al.

Abstract: Fluorescence-based biological imaging in the shortwave infrared (SWIR, 1000–1700 nm) is an attractive replacement for modern in vivo imaging techniques currently employed in both medical and research settings. Xanthene-based fluorophores containing heterocycle donors have recently emerged as a way to access deep SWIR emitting fluorophores. A concern for xanthene-based SWIR fluorophores though is chemical stability toward ambient nucleophiles due to the high electrophilicity of the cationic fluorophore core. Herein, a series of SWIR emitting silicon-rosindolizine (SiRos) fluorophores with emission maxima >1300 nm (up to 1550 nm) are synthesized. The SiRos fluorophore photophysical properties and chemical stability toward nucleophiles are examined through systematic derivatization of the silicon-core alkyl groups, indolizine donor substitution, and the use of o-tolyl or o-xylyl groups appended to the fluorophore core. The dyes are studied via absorption spectroscopy, steady-state emission spectroscopy, solution-based cyclic voltammetry, time-dependent density functional theory (TD-DFT) computational analysis, X-ray diffraction crystallography, and relative chemical stability over time. Optimal chemical stability is observed via the incorporation of the 2-ethylhexyl silicon substituent and the o-xylyl group to protect the core of the fluorophore.

Purchased from AmBeed: ; ; ; ; ;

Qing Yun Li ; Leigh Anna Hunt ; Kalpani Hirunika Wijesinghe ; Christine Curiac ; Ashley Williams ; Amala Dass , et al.

Abstract: Strong photoinduced oxidants are important to organic synthesis and solar energy conversion, to chemical fuels or electric. For these applications, visible light absorption is important to solar energy conversion and long-lived excited states are needed to drive catalysis. With respect to these desirable qualities, a series of five 5,6-dicyano[2,1,3]benzothiadiazole (DCBT) dyes are examined as organic chromophores that can serve as strong photooxidants in catalytic systems. The series utilizes a DCBT core with aryl groups on the periphery with varying electron donation strengths relative to the core. The dyes are studied via both steady-state and transient absorption and emission studies. Additionally, computational analysis, voltammetry, crystallography, and absorption spectroelectrochemistry are also used to better understand the behavior of these dyes. Ultimately, a strong photooxidant is arrived at with an exceptionally long excited state lifetime for an organic chromophore of 16 µs. The long-lived excited state photosensitizer is well-suited for use in catalysis, and visible light driven photosensitized water oxidation is demonstrated using a water-soluble photosensitizer.

Purchased from AmBeed: ; ; ; ; ; ; ; ; ; ; ; 51364-51-3 ; 538-75-0 ; 584-08-7 ; 1122-91-4 ; 123-30-8 ; 108-88-3 ; 109-77-3 ; 64-19-7 ; 603-35-0

Campbell, Allea ; Alsudairy, Ziad ; Dun, Chaochao ; Akram, Fazli ; Smith-Petty, Kayla ; Ambus, Abrianna , et al.

Abstract: Covalent organic framework (COF)-supported palladium catalysts have garnered enormous attention for cross-coupling reactions. However, the limited linkage types in COF hosts and their suboptimal catalytic performance have hindered their widespread implementation. Herein, we present the first study immobilizing palladium acetate onto a dioxin-linked COF (Pd/COF-318) through a facile solution impregnation approach. By virtue of its permanent porosity, accessible Pd sites arranged in periodic skeletons, and framework robustness, the resultant Pd/COF-318 exhibits exceptionally high activity and broad substrate scope for the Suzuki-Miyaura coupling reaction between aryl bromides and arylboronic acids at room temperature within an hour, rendering it among the most effective Pd/COF catalysts for Suzuki-Miyaura coupling reactions to date. Moreover, Pd/COF-318 demonstrates excellent recyclability, retaining high activity over five cycles without significant deactivation. The leaching test confirms the heterogeneity of the catalyst. This work uncovers the vast potential of dioxin-linked COFs as catalyst supports for highly active, selective, and durable organometallic catalysis.

Keywords: covalent organic framework (COF) ; dioxin-linked COF ; Pd(II) immobilization ; Suzuki-Miyaura coupling

Purchased from AmBeed: ; ; ; ; ;

Alternative Products

Product Details of Palladium (II) acetate

CAS No. :3375-31-3
Formula : C4H6O4Pd
M.W : 224.51
SMILES Code : CC([O-])=O.CC([O-])=O.[Pd+2]
MDL No. :MFCD00012453
InChI Key :YJVFFLUZDVXJQI-UHFFFAOYSA-L
Pubchem ID :167845

Safety of Palladium (II) acetate

GHS Pictogram:
Signal Word:Danger
Hazard Statements:H302-H315-H318-H335-H410
Precautionary Statements:P261-P264-P270-P271-P280-P302+P352-P304+P340-P305+P351+P338-P310-P330-P362+P364-P403+P233-P501
Class:9
UN#:3077
Packing Group:

Application In Synthesis of Palladium (II) acetate

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 3375-31-3 ]

[ 3375-31-3 ] Synthesis Path-Downstream   1~27

  • 1
  • [ 1001-26-9 ]
  • [ 19472-74-3 ]
  • [ 3375-31-3 ]
  • [ 2622-14-2 ]
  • 3-(ethoxy-hydroxy-methylene)-3H-indene-1-carbonitrile, sodium salt [ No CAS ]
YieldReaction ConditionsOperation in experiment
With sodium chloride; sodium t-butanolate; In 1,2-dimethoxyethane; Example 5 3-(ETHOXY-HYDROXY-METHYLENE)-3H-INDENE-1-CARBONITRILE, SODIUM SALT A solution of tricyclohexylphosphine (21.5 mg, 0.0770 mmol) in ethylene glycol dimethyl ether (10 mL) under nitrogen was charged with palladium (II) acetate (11.5 mg, 0.0510 mmol). The reaction was stirred at room temperature until the solution was homogenous (approx. 15 minutes), cooled to 0° C. and charged with sodium tert-butoxide (2.53 g, 25.5 mmol). After 5 minutes a solution of 2-bromo-phenylacetonitrile (1.32 mL, 10.2 mmol) and ethyl-3-ethoxyacrylate (1.47 mL, 10.2 mmol) in ethylene glycol dimethyl ether (10 ml) was added dropwise over 10 minutes. Upon complete addition, the reaction was warmed to room temperature then heated to 85° C. for 1 hour. The reaction was cooled to room temperature then diluted with ethyl acetate (50 mL) and poured into aqueous potassium dihydrogen phosphate (0.25 M, 50 mL), pH=7. The aqueous layer was saturated by addition of sodium chloride as solid and the organic layer separated and washed with aqueous saturated sodium chloride (1*50 mL), dried over anhydrous sodium sulfate, filtered and concentrated in vacuo affording 3-(ethoxy-hydroxy-methylene)-3H-indene-1-carbonitrile, sodium salt, as a dark brown oil (1.74 g, 84percent) which solidifies on standing. 1H NMR (400 MHz, CD3CN) delta8.04 (d, 1H, J=6.0), 7.58 (s, 1H), 7.43 (d, 1H, J=6.0), 6.98-6.91 (m, 2H), 4.25 (q, 2H, J=7.2), 1.35 (t, 3H, J=7.2); 13C NMR (100 MHz, CD3CN) delta166.7, 135.5, 132.3, 131.3, 122.8, 120.5, 119.0, 118.4, 117.7, 103.3, 79.2, 58.2, 14.6; IR (ATR, neat) 2176, 1597, 1465, 1257, 1195,1068, 1029, 754 cm-1.
  • 2
  • [ 1001-26-9 ]
  • [ 51655-39-1 ]
  • [ 3375-31-3 ]
  • [ 2622-14-2 ]
  • [ 474024-32-3 ]
YieldReaction ConditionsOperation in experiment
With sodium chloride; sodium t-butanolate; In 1,2-dimethoxyethane; Example 7 3-(ETHOXY-HYDROXY-METHYLENE)-5,6-DIMETHOXY-3H-INDENE-1-CARBONITRILE, SODIUM SALT A solution of tricyclohexylphosphine (82.0 mg, 0.293 mmol) in ethylene glycol dimethyl ether (10 mL) under nitrogen was charged with palladium (II) acetate (43.7 mg, 0.195 mmol). The reaction was stirred at room temperature until the solution was homogeneous (approx. 15 minutes) and stirred an additional 5 minutes before cooling to 0° C. and charging with sodium tert-butoxide (996 mg, 9.75 mmol). After 5 minutes a solution of 2-bromo-4,5-dimethoxyphenylacetonitrile (1.00 g, 3.90 mmol) and ethyl-3-ethoxyacrylate (0.564 ml, 3.90 mmol) in ethylene glycol dimethyl ether (5 ml) was added dropwise over 10 minutes. Upon complete addition the reaction mixture was warmed to room temperature and then heated to 85° C. for 16 hours. The reaction was cooled to room temperature then diluted with methyl tert-butyl ether (50 mL) and poured into aqueous potassium dihydrogenphosphate (0.25 M, 100 mL). The aqueous layer was separated and solid sodium chloride was added to the aqueous layer until saturated. The aqueous layer was extracted with ethyl acetate (1*125 mL) and this organic layer was washed with aqueous saturated sodium chloride 12*35 ml), dried over sodium sulfate, filtered and concentrated in vacuo affording 3-(ethoxy-hydroxy-methylene)-5,6-dimethoxy-3H-indene-1-carbonitrile, sodium salt, as a dark brown oil (906 mg, 3.3 mmol, 85 percent) which crystallized on standing. 1H NMR (400 MHz, d4-MeOH) delta7.64 (s, 1H), 7.46 (s, 1H), 6.99 (s, 1H), 4.56 (q, 2H, J=7.1), 3.86 (s, 6H), 1.38 (t, 3H, J=7.05); 13C NMR (100 MHz,d4-MeOH) delta167.8, 145.0, 144.5, 130.2, 129.4, 126.4, 123.3, 112.5, 104.0, 102.6, 100.7, 79.0, 58.4, 55.6, 14.1; IR (ATR, neat) 3499, 2164, 1629, 1482, 1449, 1282, 1207, 1157, 1124, 1076, 845, 769 cm-1.
  • 3
  • [ 123-91-1 ]
  • [ 6165-68-0 ]
  • [ 4565-31-5 ]
  • aq. NaCl [ No CAS ]
  • [ 3375-31-3 ]
  • [ 497-19-8 ]
  • [ 3779-27-9 ]
YieldReaction ConditionsOperation in experiment
In water; ethyl acetate; Step B 5-(Thien-2-yl)-thiophene-2-carboxaldehyde To a solution of thien-2-ylboronic acid (0.939 g, 7.34 mmol) and Na2 CO3 (2.40 g, 22.6 mmol) in water (75 mL) is added p-dioxane (75 mL). This mixture is treated sequentially with 5-carboxy-2-thiophenecarboxaldehyde (1.43 g, 7.48 mmol) and palladium (II) acetate (151 mg, 0.673 mmol) and allowed to stir at ambient temperature for 16 hours. The solvent is evaporated in vacuo. To the residue is added EtOAc (400 mL) and water (300 mL). The aqueous layer is acidified to pH 1 with 1.0N aq. HCl. The aqueous layer is extracted with EtOAc (2*200 mL). The organic extracts are combined, washing with brine (200 mL), 5percent aq. Na2 S2 O3 (200 mL), sat. aq. NaCl (200 mL), drying (Na2 SO4), and the solvent evaporation in vacuo affords the title compound.
  • 4
  • [ 180307-56-6 ]
  • {4-[6-bromo-1-(4-fluoro-benzyl)-1H-indazol-3-yl]-piperidin-1-yl}-acetic acid tert-butyl ester [ No CAS ]
  • [ 3375-31-3 ]
  • [ 6163-58-2 ]
  • [ 180307-57-7 ]
YieldReaction ConditionsOperation in experiment
With sodium hydrogencarbonate; triethylamine; lithium chloride; In N,N-dimethyl-formamide; (x) 4-{2-[3-(1-tert-Butoxycarbonylmethyl-piperidin-4-yl)-1-(4-fluoro-benzyl)-1H-indazol-6-yl]-(E)-vinyl}-piperidine-1-carboxylic acid tert-butyl ester A stirred mixture of {4-[6-bromo-1-(4-fluoro-benzyl)-1H-indazol-3-yl]-piperidin-1-yl}-acetic acid tert-butyl ester (286 mg, 0.57 mmol), <strong>[180307-56-6]4-vinyl-piperidine-1-carboxylic acid tert-butyl ester</strong> (120 mg, 0.57 mmol), lithium chloride (24 mg, 0.57 mmol), triethylamine (0.24 ml, 1.71 mmol), palladium (II) acetate (8 mg 0.03 mmol), tri-o-tolylphosphine (35 mg, 0.11 mmol), and DMF (5 ml) was heated at 105 (oil-bath temperature) under nitrogen for 18 h. When cool, the mixture was evaporated in vacuo, treated with aqueous saturated sodium bicarbonate (20 ml), and extracted with ethyl acetate (2*20 ml). The combined, dried (Na2 SO4) organic extracts were evaporated, and the residue purified by flash chromatography over silica gel (Merck 9385). Elution with ethyl acetate --cyclohexane (1:2) afforded impure fractions and pure fractions (I). The impure fractions were purified by flash chromatography over silica gel (Merck-9385) eluding with ethyl acetate--cyclohexane (gradient 1:4 to 1:2) to give pure fractions (II). The pure fractions (I) and (II) were combined to give the title compound as a pale yellow oil (195 mg).
  • 5
  • [ 3032-81-3 ]
  • [ 3375-31-3 ]
  • [ 115-19-5 ]
  • 1-(3,5-dichlorophenyl)-3-methyl-1-butyn-3-ol [ No CAS ]
YieldReaction ConditionsOperation in experiment
With hydrogenchloride; triethylamine; triphenylphosphine; EXAMPLE 31 1-(3,5-Dichlorophenyl)-3-methyl-1-butyn-3-ol A mixture of 25.5 g (0.094 mole) of <strong>[3032-81-3]3,5-dichloroiodobenzene</strong>, 550 ml dry triethylamine, 12 g (0.14 mole) of 2-methyl-2-hydroxy-3-butyne, 0.42 g (0.0019 mole) palladium (II) acetate, and 1 g (0.0038 mole) of triphenylphosphine was heated to reflux under nitrogen for four hours. The resulting mixture was cooled, diluted with ether and washed with two 500-ml portions of 3N hydrochloric acid. The ether layer was separated, dried over anhydrous magnesium sulfate, and evaporated in vacuo to yield the crude product as an oily residue. The purified product was obtained by distillation to yield 7.95 g, bp 115°-125° C./0.0001 mm.
With hydrogenchloride; triethylamine; triphenylphosphine; EXAMPLE A 1-(3,5-Dichlorophenyl)-3-methyl-1-butyn-3-ol A mixture of 25.5 g (0.094 mole) of <strong>[3032-81-3]3,5-dichloroiodobenzene</strong>, 550 ml dry triethylamine, 12 g (0.14 mole) of 2-methyl-2-hydroxy-3-butyne, 0.42 g (0.0019 mole) palladium (II) acetate, and 1 g (0.0038 mole) of triphenylphosphine was heated to reflux under nitrogen for four hours. The resulting mixture was cooled, diluted with ether and washed with two 500-ml portions of 3N hydrochloric acid. The ether layer was separated, dried over anhydrous magnesium sulfate, and evaporated in vacuo to yield the crude product as an oily residue. The purified product was obtained by distillation to yield 7.95 g, bp 115°-125° C./0.0001 mm.
With hydrogenchloride; triethylamine; triphenylphosphine; EXAMPLE 26 1-(3,5-Dichlorophenyl)-3-methyl-1-butyn-3-ol A mixture of 25.5 g (0.094 mole) of <strong>[3032-81-3]3,5-dichloroiodobenzene</strong>, 550 ml dry triethylamine, 12 g (0.14 mole) of 2-methyl-2-hydroxy-3-butyne, 0.42 g (0.0019 mole) palladium (II) acetate, and 1 g (0.0038 mole) of triphenylphosphine was heated to reflux under nitrogen for four hours. The resulting mixture was cooled, diluted with ether and washed with two 500-ml portions of 3N hydrochloric acid. The ether layer was separated, dried over anhydrous magnesium sulfate, and evaporated in vacuo to yield the crude product as an oily residue. The purified product was obtained by distillation to yield 7.95 g, bp 115°-125° C./0.0001 mm.
  • 6
  • 1-1'-bis(diphenyphosphino)ferrocene [ No CAS ]
  • [ 10365-98-7 ]
  • [ 3375-31-3 ]
  • [ 145369-29-5 ]
  • 6-(3-Methoxyphenyl)-2-naphthalenecarbonitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
With caesium carbonate; In ethyl acetate; N,N-dimethyl-formamide; EXAMPLE 47A 6-(3-Methoxyphenyl)-2-naphthalenecarbonitrile A solution of Example 28B (300 mg, 1 mmol), palladium (II) acetate (22 mg, 0.1 mmol) and 1-1'-bis(diphenyphosphino)ferrocene (111 mg, 0.2 mmol) was stirred in DMF (3 mL) for 15 min, treated with Cs2CO3 (813 mg, 2.5 mmol) and 3-methoxyphenylboronic acid (228 mg, 1.5 mmol), stirred for 20 min at 80 C., cooled, treated with pH 7 buffer (10 mL) and extracted with diethyl ether. The ether extracts were dried (MgSO4), concentrated and purified on silica gel with 10% ethyl acetate/hexane to provide 140 mg of the title compound as a white solid. MS (DCI/NH3) m/e 277 (M+NH4)+.
With caesium carbonate; In ethyl acetate; N,N-dimethyl-formamide; EXAMPLE 47A 6-(3-Methoxyphenyl)-2-naphthalenecarbonitrile A solution of Example 28B (300 mg, 1 mmol), palladium (II) acetate (22 mg, 0.1 mmol) and 1-1'-bis(diphenyphosphino)ferrocene (111 mg, 0.2 mmol) was stirred in DMF (3 mL) for 15 min, treated with Cs2CO3 (813 mg, 2.5 mmol) and 3-methoxyphenylboronic acid (228 mg, 1.5 mmol), stirred for 20 min at 80 C., cooled, treated with pH 7 buffer (10 mL) and extracted with diethyl ether. The ether extracts were dried (MgSO4), concentrated and purified on silica gel with 10% ethyl acetate/haexane to provide 140 mg of the title compound as a white solid. MS (DCI/NH3) m/e 277 (M+NH4)+.
  • 7
  • potassium phosphate [ No CAS ]
  • [ 3375-31-3 ]
  • [ 224311-51-7 ]
  • [ 328918-90-7 ]
  • [ 108-95-2 ]
  • [ 403612-06-6 ]
YieldReaction ConditionsOperation in experiment
With nitrogen; In toluene; EXAMPLE 16 2-Methyl-2-(4-{2-[5-methyl-2-(4-phenoxy-phenyl)-oxazol-4-yl]-ethoxy}-phenoxy)-propionic Acid A mixture of 2-(4-{2-[2-(4-bromo-phenyl)-5-methyl-oxazol-4-yl]-ethoxy}-phenoxy)-2-methyl-propionic Acid Ethyl Ester (0.30 g, 0.614 mmol), potassium phosphate (0.26 g, 1.22 mmol), 2-(di-tert-butylphosphino)biphenyl (0.014 g, 0.0469 mmol) and phenol (0.069 g, 0.733 mmol) in toluene (6 mL) was degassed three times by successive application of vacuum to the reaction vessel followed by nitrogen purge. Palladium (II) acetate (0.007 g, 0.0312 mmol) was added to the reaction and the mixture heated to reflux under nitrogen for 3 h. The reaction was cooled to room temperature, diluted with Et2O, and extracted with water then 1 N NaOH (10 mL). The organic layer was dried (MgSO4) and the solvent removed in vacuo to give 0.316 g of crude 2-methyl-2-(4-{2-[5-methyl-2-(4-phenoxy-phenyl)-oxazol-4-yl]-ethoxy}-phenoxy)-propionic acid ethyl ester MS (ES+) Calc'd for C30H31NO6: Found m/e 502.3 (M+1, 100percent).
  • 8
  • [ 109-01-3 ]
  • 8-chloro-2-[3-(4-phenyl-3,6-dihydro-1 (2H)-pyridinyl)propyl]-4(3H)-quinazolinone [ No CAS ]
  • [ 3375-31-3 ]
  • [ 224311-51-7 ]
  • [ 437999-29-6 ]
YieldReaction ConditionsOperation in experiment
In tetrahydrofuran; methanol; dichloromethane; toluene; EXAMPLE 15 A mixture of 8-chloro-2-[3-(4-phenyl-3,6-dihydro-1 (2H)-pyridinyl)propyl]-4(3H)-quinazolinone (50 mg), 1-methylpiperazine (19.8 mg), palladium (II) acetate (2.96 mg), 2-(di-t-butylphosphino)biphenyl (7.86 mg), sodium t-butoxide (23 mg) in toluene (0.4 ml and tetrahydrofuran (0.2 ml) was stirred at 80° C. under nitrogen atmosphere overnight. The mixture was cooled, diluted with water and extracted with dichloromethane twice. The combined extracts were dried over magnesium sulfate and concentrated. The residue was purified by preparative thin layer chromatography on silica gel using 10percent methanol in dichloromethane to give the 8-(4-methyl-1-piperazinyl)-2-[3-(4-phenyl-3,6-dihydro-1(2H)-pyridinyl)propyl]-4(3H)-quinazolinone. Mass (APCI): 444.3 (M++H)
  • 9
  • [ 4052-88-4 ]
  • [ 15184-96-0 ]
  • [ 3375-31-3 ]
  • (C6H3(CH3)CH2N(CH3)2PdOOCCH3)2 [ No CAS ]
  • {Pd(OCOCH3)(C7H5NO2N(CH3)2)}2 [ No CAS ]
  • 10
  • [ 2622-63-1 ]
  • [ 3375-31-3 ]
  • [ 64-19-7 ]
  • [ 180182-47-2 ]
  • 11
  • [ 3375-31-3 ]
  • [ 402822-72-4 ]
  • 2Pd(2+)*2CH2C6H4C6H4P(C6H5)2(1-)*2O2CCH3(1-)*(C2H5)2O=[Pd(CH2C6H4C6H4P(C6H5)2)(O2CCH3)]2*(C2H5)2O [ No CAS ]
  • 12
  • [ 97239-80-0 ]
  • [ 696-63-9 ]
  • [ 3375-31-3 ]
  • [ 1154043-13-6 ]
  • 13
  • [ 16413-71-1 ]
  • [ 3375-31-3 ]
  • C30H34N2O4Pd2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
In dichloromethane; [00613] In order to get any useful information about palladium-mediated C-F bond formation process, isolation of Pd(IV)-F complex was attempted. Hoping to get crystalline compound, the dimethyl(naphthalenylmethyl)amine palladium complex was synthesized with tetrapyrazoylborate.
  • 14
  • [ 3375-31-3 ]
  • [ 224311-51-7 ]
  • acetato(2'-di-tert-butylphosphino-1,1'-biphenyl-2-yl)palladium(II) [ No CAS ]
  • 15
  • 5-(2-bromobenzyl)-5,6-dihydrophenanthridine [ No CAS ]
  • [ 3375-31-3 ]
  • [ 5350-41-4 ]
  • 8H,9H-8a-Azabenzo[fg]naphthacene [ No CAS ]
YieldReaction ConditionsOperation in experiment
81% With potassium carbonate; Example 5 8H,9H-8a-Azabenzo[fg]naphthacene 55.3 g (158 mmol) of 5-(2-bromobenzyl)-5,6-dihydrophenanthridine are dissolved in 500 ml of dimethylformamide under protective-gas atmosphere. 17.3 g (75 mmol) of benzyltrimethylammonium bromide and 31.28 g (226 mmol) of potassium carbonate are added to this solution. 5.08 g (22 mmol) of Pd(OAC)2 is subsequently added under protective gas, and the mixture is stirred at 120° C. for 9 h. After this time, the reaction mixture is cooled to room temperature and extracted with dichloromethane. The combined organic phases are dried over Na2SO4 and evaporated. The residue is recrystallised from n-heptane. The yield is 34 g (81percent).
  • 16
  • [ 1417885-96-1 ]
  • [ 3375-31-3 ]
  • [ 131274-22-1 ]
  • [ 454185-98-9 ]
  • methyl 2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl)acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
Example 33 Preparation of methyl 2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl)acetate (C17) In a 200 mL flask, 3-bromo-1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazole (3.45 g, 11.2 mmol), and methyl 2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)acetate (3.71 g, 13.4 mmol) were diluted with dioxane (45 mL) and water (11 mL). This solution was sparged with nitrogen gas for 10 minutes. Then tri-tert-butylphosphonium tetrafluoroborate (0.325 g, 1.12 mmol), diacetoxypalladium (0.126 g, 0.560 mmol) and cesium fluoride (3.40 g, 22.4 mmol) were added as solids. The flask was sealed and evacuated with vacuum and purged with nitrogen gas. The reaction was warmed to an internal temperature of 60° C. and stirred for 18 hours. The reaction was poured into a brine solution and extracted with ethyl acetate (3*50 mL). The combined organics were dried over magnesium sulfate, filtered, and concentrated. The resulting residue was purified by flash chromatography using 0-10percent ethyl acetate/hexanes as eluent to afford the title compound as an off white solid (3.45 g, 82percent): 1H NMR (400 MHz, DMSO-d6) delta 9.41 (s, 1H), 8.11-8.04 (m, 4H), 7.63 (ddt, J=7.9, 2.1, 1.1 Hz, 2H), 7.48-7.36 (m, 2H), 3.77 (s, 2H), 3.64 (s, 3H); 19F NMR (376 MHz, DMSO-d6) delta -57.02; ESIMS m/z 378 ([M+H]+)
  • 17
  • [ 67-66-3 ]
  • [ 3375-31-3 ]
  • [ 538-58-9 ]
  • [ 52522-40-4 ]
  • 18
  • [ 402-69-7 ]
  • [ 3375-31-3 ]
  • C12H6F2N2O4Pd [ No CAS ]
  • 19
  • [ 67-56-1 ]
  • [ 3375-31-3 ]
  • [ 33332-28-4 ]
  • [ 118853-60-4 ]
YieldReaction ConditionsOperation in experiment
80% With 1,1'-bis-(diphenylphosphino)ferrocene; triethylamine; at 85℃; under 7600.51 Torr; for 5h;Large scale; A solution of 6-chloro-2-pyrazinamine (4 kg, 31 mol, 1.00 equiv), Et3N (4.7 kg,46.5 mol, 1.50 equiv), Pd(OAc)2 (139 g, 0.62mo1, 0.02 equiv), dppf (343 g, 0.62 mol, 0.02equiv) in methanol (60 L) was placed in a 100 L pressure tank reactor(10 atm).The resulting solution was allowed to react for 5 h while maintaining the temperature at 85°C. The reaction progress was monitored by TLC (DCM: MeOH = 20: 1) until the starting material was consumed completely, and cooled to room temperature. The resulting mixture was concentrated under vacuum. The residue was washed with water 50 L. Thefilter was collected and dried. The product (3.8 kg, purity = 95 percent, 80 percent yield)obtained as a pale brown solid.1H-NIVIR (300 MHz, DMSO-d6) : 8.27(1H, s), 8.06(1H, s), 6.87(2H, b), 3.84(3H, s). LC-MS: m / z = 154(M+H) +.
  • 20
  • [ 621-38-5 ]
  • [ 3375-31-3 ]
  • [ 76-05-1 ]
  • C20H14Br2F6N2O6Pd2 [ No CAS ]
  • 21
  • strontium nitrate [ No CAS ]
  • [ 98-05-5 ]
  • [ 1643-19-2 ]
  • [ 3375-31-3 ]
  • [ 6106-41-8 ]
  • (C16H36N)3Na[SrPd12O6(OH)3(PhAsO3)6(C5H9O2)3]·0.5C5H9O2Na·22H2O [ No CAS ]
  • 22
  • strontium nitrate [ No CAS ]
  • [ 98-05-5 ]
  • [ 3375-31-3 ]
  • [ 6106-41-8 ]
  • Na4[SrPd12O6(OH)3(PhAsO3)6(C5H9O2)3]·C5H9O2Na·21H2O [ No CAS ]
  • 23
  • [ 3375-31-3 ]
  • [ 117408-98-7 ]
  • 2C2H3O2(1-)*Pd(2+)*C12H16N2O [ No CAS ]
  • 24
  • [ 99368-66-8 ]
  • [ 3375-31-3 ]
  • [ 98-16-8 ]
  • [ 529-20-4 ]
  • C42H26F12N6O6Pd2 [ No CAS ]
  • 25
  • [ 3375-31-3 ]
  • [ 81-07-2 ]
  • [ 607-01-2 ]
  • [ 1192-62-7 ]
YieldReaction ConditionsOperation in experiment
66% General procedure: Complexes 4, 6, 8 and 10-12 were prepared by the following method. SacH (0.5mmol, 91.6mg) in water (5mL) was added to a solution of Pd(OAc)2 (0.25mmol, 56.1mg) in MeCN (10mL) and the solution was stirred for 30min at rt. Then, the corresponding phosphine (0.5mmol) in MeOH (10mL) was added to this solution and the resulting solutions were refluxed over a day. Complexes 2, 5 and 9 were synthesized using the same procedure, but the SacH/phosphine ratio was 2:1. In the case of 9, DMSO (10mL) was added to the reaction medium to dissolve the solid particles. The powders of these complexes were obtained after removal of the solvents using a rotary evaporator.
  • 26
  • [ 3375-31-3 ]
  • [ 22112-83-0 ]
  • (meso‐tetrakis[4‐(methoxycarbonyl)phenyl]porphyrinato)palladium(II) [ No CAS ]
  • 27
  • [ 1336-21-6 ]
  • [ 1761-56-4 ]
  • [ 3375-31-3 ]
  • C13H12N2O2Pd [ No CAS ]
 

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