130059-91-5

Basic information

• Product Name: 1-Methyl-4-((Z)-styryl)-benzene
• CAS NO: 130059-91-5
• Molecular Weight: 194.276
• Mol File: 130059-91-5.mol
• Article Data: 525

Chemical Properties

• CAS DataBase Reference: 1-Methyl-4-((Z)-styryl)-benzene(CAS DataBase Reference)
• NIST Chemistry Reference: 1-Methyl-4-((Z)-styryl)-benzene(130059-91-5)
• EPA Substance Registry System: 1-Methyl-4-((Z)-styryl)-benzene(130059-91-5)

Safety Data

• Hazardous Substances Data: 130059-91-5(Hazardous Substances Data)

Upstream product

• 100-42-5 styrene 
• 60126-95-6 p-tolylazoxy p-tolyl sulphone 
• 10557-67-2 N-nitroso-p-methyl-acetanilide 
• 33604-67-0 (4-methylphenyl)azo 4-methylphenyl sulfone 
• 60126-94-5 phenylazoxy p-tolyl sulphone 
• 106-38-7 para-bromotoluene 
• 624-31-7 4-tolyl iodide 
• 1923-01-9 trimethyl(1-phenylvinyl)silane 
• 459-44-9 4-methylbenzenediazonium tetrafluoroborate 
• 19319-11-0 (Z)-1-phenyl-2-(trimethylsilyl)ethylene 
• 30818-48-5 benzyl 4-methylbenzyl sulphoxide 
• 622-97-9 1-ethenyl-4-methylbenzene 
• 591-50-4 iodobenzene 
• 26272-72-0 1-(phenylsulfonyl)-2-p-tolyldiazene 

Downstream Products

• 135733-73-2 (+/-)-erythro-α,α'-dibromo-4-methyl-bibenzyl 
• 135733-75-4 1-((1R,2R)-1,2-Dibromo-2-phenyl-ethyl)-4-methyl-benzene 
• 76583-56-7 1-(3,5-Diphenyl-4-p-tolyl-1H-pyrrol-2-yl)-isoquinoline 
• 76583-55-6 1-(4,5-Diphenyl-3-p-tolyl-1H-pyrrol-2-yl)-isoquinoline 
• 104-87-0 4-methyl-benzaldehyde 
• 100-52-7 benzaldehyde 
• 832-71-3 3-methylphenathrene 
• 2431-00-7 p-methylbenzil 
• 22440-35-3 trans-2-(4-methylbenzenyl)-3-phenyl-oxirane 
• 1657-45-0 trans-4-methylstilbene radical cation 
• 298710-76-6 (4-styrylbenzyl)phosphonic acid diethyl ester 

Relevant articles and documents

Nickel nanoparticles supported on diphenylphosphinated poly(vinyl alcohol-co-ethylene) as a new heterogeneous and recyclable catalyst for Mizoroki–Heck reactions

Nickel nanoparticles (NiNPs) supported on diphenylphosphinated poly(vinyl alcohol-co-ethylene) (DPP-PVA-co-PE) were synthesised by first reacting poly(vinyl alcohol-co-ethylene) with chlorodiphenylphosphine (ClPPh2) under basic conditions and then treating the product with Ni(OAc)2 followed by reduction with NaBH4. (DPP-PVA-co-PE)-NiNPs, a new metallised polymer, was then shown to efficiently catalyse Mizoroki–Heck reactions of aryl iodides, bromides or activated chlorides with olefins such as styrene and n-butyl acrylate in dimethylformamide. In contrast with other polymer-supported catalysts, the main advantage of this method is the low cost of the catalyst due to the simple synthetic route using easily obtained materials and good recoverability. Transmission electron microscopy and X-ray diffraction measurements were used to show the high metal dispersion and small sizes of Ni nanoparticle on the surface of the modified polymer. DPP-PVA-co-PE-NiNPs could be recycled several times.

Three phase microemulsion/sol-gel system for aqueous C-C coupling of hydrophobic substrates

Heck, Stille, Suzuki and three-component coupling reactions with hydrophobic substrates have been carried out in water. The substrates are initially transformed by a general procedure into a microemulsion, which consists of nearly 90% water with the aid of sodium dodecyl sulfate and either PrOH or BuOH. The surfactant carries the molecules of the substrates to Pd(OAc)2 entrapped within a hydrophobicitized silica sol-gel matrix where the coupling between the substrates is assumed to take place. The products are then returned by the surfactant into the microemulsion from which it can be released. The immobilized palladium catalyst is leach proof and recyclable. It can be used in various coupling processes at least six times without loss of activity. Experiments with D2O have revealed that the water does not take part in the coupling process, but it has an effect on the pore size of the sol-gel matrix, which hosts the palladium catalyst. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Palladium-EDTA and palladium-EdteH4 catalyzed Heck coupling reactions in pure water

Palladium-catalyzed Heck coupling reactions of styrene with bromoarene derivatives are carried out under aerobic conditions in water using water-soluble N;N;N ′ ;N ′ -tetrakis(2-hydroxyethyl)ethylenediamine (EdteH4) and ethylenediaminetetraacetic acid dis

Bimetallic nano alloy architecture on a special polymer: Ni or Cu merged with Pd for the promotion of the Mizoroki–Heck reaction and the Suzuki–Miyaura coupling

Abstract: Novel Ni-Pd and Cu-Pd bimetallic nano alloys was designed and heterogenized on the highly robust ABPBI [poly(2,5-benzimidazole)] polymer in high yields using NaBH4 as reducing agent. These were versatile ligand free catalysts for the Mizoroki–Heck reaction and Suzuki–Miyaura coupling. The bimetallic Ni-Pd-ABPBI catalyst for the Mizoroki–Heck reaction of 4-iodo anisole could be recycled 5 times with high yields. Aryl bromides could also be activated for the Mizoroki–Heck reaction using Cu-Pd-ABPBI NP catalysts, with moderate yields. Graphic abstract: Synopsis Novel bimetallic Ni-Pd and Cu-Pd nano alloys, heterogenized on the robust ABPBI [poly(2,5-benzimidazole)] polymer using NaBH4 as reducing agent, is described. These were versatile ligand free, noble metal conservative catalysts, for the Mizoroki–Heck reaction and the Suzuki–Miyaura coupling. Aryl bromides were activated for the Mizoroki–Heck reaction using the Cu-Pd-ABPBI catalyst.[Figure not available: see fulltext.]

Removal of benzotriazole moiety from 2-[2-aryl-2-(benzotriazol-1- yl)ethyl]tetrahydro-2H-pyrans and 2-[2-aryl-2-(benzotriazol-1-yl)ethyl]-5- (methyl)tetrahydrofurans using lithium naphthalene radical anion

In order to see the effects of non-bonding electrons in oxygen atoms on the cleavage of a bond between N-1 of the benzotriazole moiety and the a- carbon atom bonded to N-1 by lithium (6a) and sodium naphthalenides (6b), 2- [2-aryl-2-(benzotriazol-1-yl)ethyl]tetrahydro-2H-pyrans (4), and 2-[2-aryl- 2-(benzotriazol-1-yl)ethyl]-5-(methyl)tetrahydrofurans (5), and 1- (benzotriazol-1-yl)-1,2-diphenylethane (7) were prepared. The reactions of 4 with 6a in THF at room temperature gave 2-(2-arylethyl)tetrahydro-2H-pyrans (12) in 45 to 62 % yields along with benzotriazole and naphthalene. In addition, 2-(benzoylethyl)tetrahydro-2H-pyran (15) (12 %) was obtained only from the reaction of 2-[2(benzotriazol-1-yl)-2-(phenyl)ethyl]tetrahydro-2H- pyran. Similarly, the reactions of 5 with 6a under the same conditions afforded 2-(2-arylethyl)-5-(methyl)tetrahydrofurans (30) in 59 to 77 % yields along with the foregoing byproducts. Interestingly, the reaction of 7 with 6a under the same conditions gave deoxybenzoin (24) in 41% yield along with the foregoing byproducts. The results suggest that 6a acts as a single electron- transfer agent in the reactions of 4 and 5, and a base in the reaction ofT. It is envisaged that for the former, Li+ participates in the formation of a six-membered cyclic intermediate so that cleavage of a-C-N-1 bond is facilitated to give eventually 12 and 22, whereas for the latter, 6a abstracts a proton from a-C bonded to N-1 to generate a carbanion 19, which extrudes a nitrogen molecule to generate a new phenyl carbanion 20. Protonation leading to mono iminobenzoin 21, followed by hydrolysis gives 15. The formation of 24 can be explained based on the same mechanism as for the latter reaction.

Unconventional Pd nanoparticles' growth induced by a competitive effect between temperature-dependent coordination and reduction of grafted amino ligands for Heck reaction

A useful and interesting unconventional phenomenon of Pd nanoparticle formation, i.e., significantly inhibited particle growth at elevated temperatures, has been observed for the first time by growing Pd nanoparticles on a type of nonreactor, amino group-functionalized hollow mesoporous silica nanoparticles (amino-HMSNs). Such an unconventional effect is evidenced to be a competitive result between temperature-dependent coordination and reduction action of amino groups on the shell of HMSNs based on a series of experiments of probing the coordination and reduction capability of the amino groups to a Pd precursor K2PdCl6. A possible mechanism has been proposed to demonstrate and clarify the unconventional growth of Pd nanoparticles on the shell of amino-HMSNs. The as-synthesized Pd nanoparticles on the amino-HMSNs, therefore, show a tunable temperature-dependent small size range (a finding of unconventional particle growth effect may offer a novel protocol for particle size modulation during materials design and fabrication.

Ruthenium-Catalyzed Heck-Type Olefination and Suzuki Coupling Reactions: Studies on the Nature of Catalytic Species

Ruthenium-catalyzed Heck olefination and Suzuki cross coupling reactions have been developed. When starting with a ruthenium complex [RuCl 2(p-cymene)]2 as a homogeneous catalyst precursor, induction periods were observed and ruthenium colloids of zero oxidation state were generated under catalytic conditions. Isolated ruthenium colloids carried out the olefination, implying that active catalytic species are ruthenium nanoclusters. To support this hypothesis, ruthenium nanoparticles stabilized with dodecylamine were independently prepared via a hydride reduction procedure, and their catalytic activity was subsequently examined. Olefination of iodobenzene with ethyl acrylate was efficiently catalyzed by the ruthenium nanoparticles under the same conditions, which could be also reused for the next runs. In poisoning experiments, the conversion of the olefination was completely inhibited in the presence of mercury, thus supporting our assumption on the nature of catalytic species. No residual ruthenium was detected from the filtrate at the end of the reaction. On the basis of the postulation, a heterogeneous catalyst system of ruthenium supported on alumina was consequently developed for the Heck olefination and Suzuki cross coupling reactions for the first time. It turned out that substrate scope and selectivity were significantly improved with the external ligand-free catalyst even under milder reaction conditions when compared to results with the homogeneous precatalyst. It was also observed that the immobilized ruthenium catalyst was recovered and reused up to several runs with consistent efficiency. Especially in the Suzuki couplings, the reactions could be efficiently carried out with as low as 1 molpercent of the supported catalyst over a wide range of substrates and were scaled up to a few grams without any practical problems, giving coupled products with high purity by a simple workup procedure.

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Aqueous-phase, palladium-catalyzed cross-coupling of aryl bromides under mild conditions, using water-soluble, sterically demanding alkylphosphines

Sterically demanding, water-soluble alkylphosphines have been used in combination with various palladium salts in Suzuki, Sonogashira, and Heck couplings of aryl bromides under mild conditions in aqueous solvents. The tert-butyl-substituted ligands 2-(di-tert-butylphosphino)ethyltrimethylammonium chloride (t-Bu-Amphos) and 4-(di-tert-butylphosphino)-N,N-dimethylpiperidinium chloride (t-Bu-Pip-phos) in combination with palladium(II) salts were found to give catalysts that were significantly more active than catalysts derived from tri(3-sulfonatophenyl)phosphine trisodium (TPPTS). Suzuki couplings of unactivated aryl bromides occurred efficiently at room temperature in water/acetonitrile and water/toluene biphasic mixtures or in neat water. Notably, Suzuki couplings of hydrophilic aryl bromides gave high yields without using organic solvents for the reaction or purification. This methodology has been applied to a highly efficient synthesis of diflunisal. The catalyst derived from t-Bu-Amphos was recycled three times in Suzuki couplings in water/toluene before catalyst activity began to significantly drop. The average yield of four cycles was >80% per cycle. Heck and Sonogashira couplings were carried out under mild conditions (50 and 80°C, respectively) with unactivated aryl bromides to give coupled products in high yield.

Mizoroki-Heck carbon-carbon cross-coupling reactions by water-soluble palladium (II) complexes in neat water

Water-soluble palladium complexes were synthesized, characterized, tested as (pre)catalyst for Mizoroki-Heck carbon-carbon cross-coupling reactions in water. Cross-coupling of aryl iodides and bromides with methyl and ethyl acrylates was achieved at 140 °

Palladium-catalyzed Heck reaction of aryl bromides in aqueous media using tris(N-heterocyclic carbene) ligands

A highly effective, easy to handle and environmentally benign process for palladium-mediated Heck reaction was developed. The in situ prepared three-component system composed of palladium(II) acetate, a tris(azolinium) bromide and potassium tert-butoxide,

Palladium (II) complexes with the unsymmetrical H-spirophosphorane ligand HP(OCMe2CMe2O)(OCH2CMe2NH): Synthesis, structural and catalytic studies

We have investigated the reactivity of the unsymmetrical H-spirophosphorane (HSP) ligand HP(OCMe2CMe2O)(OCH2CMe 2NH) 1 towards different palladium(II) precursors and synthesised the mononuclear complexes [PdCls

Triarylantimony dicarboxylates as pseudo-halides for palladium-catalyzed cross-coupling reaction with arylboronic acids and triarylbismuthanes without any base

The reaction of triarylantimony diacetates (6) with organoboron reagents (9) in the presence of Pd(PPh3)4 led to the formation of cross-coupling products, biaryls (10, 12 and 14-17), in moderate to excellent yields under mild conditions without any base. Similar reaction of 6 with triarylbismuthanes (18) also gave the corresponding cross-coupling products. Single crystal X-ray analysis of tri(p-tolyl)antimony diacetate (6b) and tris(p-trifluoromethylphenyl)antimony diacetate (6e) revealed the geometry of both central antimony atoms being intermediate between trigonal bipyramidal and pentagonal bipyramidal arrangement with intramolecular coordination between the antimony and two carbonyl oxygen atoms with cis orientation.

Immobilized palladium on surface-modified Fe3O 4/SiO2 nanoparticles: As a magnetically separable and stable recyclable high-performance catalyst for Suzuki and Heck cross-coupling reactions

A palladium-based catalyst (Fe3O4/SiO 2/HPG-OPPh2-PNP) supported on chlorodiphenylphosphine- functionalized magnetic nanoparticles was successfully prepared from Fe 3O4/SiO2 with sequential attachment of glycerol and chlorodiphenylphosphine, followed by treatment of an ethanolic solution of palladium chloride with hydrazine. The as-prepared catalyst was characterized by ICP-AES, FTIR, XRD, SEM, and TEM. The Fe3O4/SiO 2/HPG-OPPh2-PNP was found as a magnetically separable and highly active catalyst for Suzuki coupling reactions of aryl iodides, bromides, and chlorides as well as Heck reactions of aryl iodides and bromides. Under appropriate conditions, all reactions afforded the desired products in moderate to excellent yields. Moreover, this catalyst can be easily recovered by using a magnetic field and directly reused for at least six cycles without significant loss of its activity.

Use of tetrahydropyrimidinium salts for highly efficient palladium-catalyzed cross-coupling reactions of aryl bromides and chlorides

New, sterically demanding 1,3-dialkyl-3,4,5,6-tetrahydropyrimidinium salts (2) as NHC precursors have been synthesized and characterized. These salts, in combination with palladium acetate, provided active catalysts for the cross-coupling of aryl chloride

Heterobimetallic Pd/Mn and Pd/Co complexes as efficient and stereoselective catalysts for sequential Cu-free Sonogashira coupling–alkyne semi-hydrogenation reactions

A series of heterobimetallic PdII/MII complexes (MII = Mn, Co) were synthesised and tested as precatalysts for sequential Sonogashira coupling–alkyne semi-hydrogenation reactions to form Z-aryl alkenes. The carbometalated heterobimetallic PdII/CoII complex CoPdL3′ demonstrated an apparent cooperative effect compared to the corresponding monometallic counterparts. This compound was identified as a potent single-molecule catalyst for the one-pot Cu-free Sonogashira coupling of aryl bromides with terminal alkynes followed by chemo- and stereoselective semi-hydrogenation of the alkyne intermediate using NH3·BH3 as a hydrogen source. Furthermore, different aromatic substrates have been tested to show the generality of the reaction for the synthesis of Z-alkenes, including biologically active combretastatin A-4. In addition, the homogeneous nature of the catalytically active species was demonstrated.

A Solid-Phase Assisted Flow Approach to In Situ Wittig-Type Olefination Coupling

Described herein is the development of a continuous flow, solid-phase triphenylphosphine (PS-PPh3) assisted protocol to facilitate the in situ coupling of reciprocal pairs of halogen and carbonyl functionalised molecular pairs by a Wittig olefination within 15 mins. The protocol entails injecting a single solution (1 : 1 CHCl3 : EtOH) containing the halogenated and carbonyl-based substrates into a continuously flowing stream of CHCl3 : EtOH (1 : 1), passed through a fixed bed of K2CO3 and PS-PPh3. With advancement to the previous PS-PPh3 coupling procedures, the method employs a traditional polystyrene-based immobilisation matrix, the substrate scope of the protocol extended to substituted ketones, secondary alkyl chlorides, and an unprotected maleimide scaffold.