622-97-9

Basic information

• Product Name: 4-Methylstyrene
• Synonyms: P-VINYLTOLUENE;p-Methylphenylene;P-METHYLSTYRENE;PARA-METHYLSTYRENE;VINYLTOLUENE;METHYLSTYRENE;4-METHYLSTYRENE;4-Methylphenylene
• CAS NO: 622-97-9
• Molecular Formula: C₉H₁₀
• Molecular Weight: 118.18
• EINECS: 210-762-8
• Product Categories: Imidazoles
• Mol File: 622-97-9.mol
• Article Data: 261

Chemical Properties

• Melting Point: -34 °C
• Boiling Point: 170-175 °C(lit.)
• Flash Point: 114 °F
• Appearance: Clear colorless to light yellow/Liquid
• Density: 0.897 g/mL at 25 °C(lit.)
• Vapor Pressure: <1 mm Hg ( 20 °C)
• Refractive Index: n20/D 1.542(lit.)
• Storage Temp.: 2-8°C
• Solubility: 0.089g/l
• Explosive Limit: 1.1-5.2%(V)
• Water Solubility: Miscible with benzene. slightly miscible with water.
• BRN: 1209317
• CAS DataBase Reference: 4-Methylstyrene(CAS DataBase Reference)
• NIST Chemistry Reference: 4-Methylstyrene(622-97-9)
• EPA Substance Registry System: 4-Methylstyrene(622-97-9)

Safety Data

• Hazard Codes: Xn
• Statements: 10-36/37/38-65
• Safety Statements: 26-36-62
• RIDADR: UN 2618 3/PG 3
• WGK Germany: 3
• RTECS: WL5076000
• TSCA: Yes
• HazardClass: 3
• PackingGroup: III
• Hazardous Substances Data: 622-97-9(Hazardous Substances Data)

Usage

Chemical Properties

CLEAR COLOURLESS TO LIGHT YELLOW LIQUID

Uses

4-Methylstyrene is used as a monomer for polyesters and in plastics production. It is also used as an intermediate in paint and coating additives. Further, it is used with other vinyltoluene isomers (3-vinyltoluene) as monomers for the preparation of poly(vinyltoluene). In addition to this, it is employed as a bi- ligand in the preparation of cationic, two-coordinate triphenylphosphine-gold(I)-pi complexes. Further, it is involved in Heck coupling reactions with chlorobenzene.

General Description

A clear colorless liquid with an aromatic odor. Flash point 129°F. Usually shipped with an inhibitor such as tert-butyl catechol added May polymerize if contaminated or subjected to heat. If polymerization takes place inside a closed container, the container may rupture violently. Vapors irritate the mucous membranes. Less dense than water and insoluble in water. Hence floats on water. Density is 7.6 lb / gal. Used in making plastics, especially as a monomer for polyesters.

Air & Water Reactions

Flammable. Insoluble in water.

Reactivity Profile

4-Methylstyrene may react vigorously with strong oxidizing agents. May react exothermically with reducing agents to release hydrogen gas. In the presence of various catalysts (such as acids) or initiators, may undergo exothermic addition polymerization reactions. May undergo autoxidation upon exposure to the air to form peroxides. These peroxides and polyperoxides are usually extremely unstable and liable to detonation. The peroxidation of butadiene has been involved in several serious industrial accidents.

Health Hazard

Inhalation or contact with material may irritate or burn skin and eyes. Fire may produce irritating, corrosive and/or toxic gases. Vapors may cause dizziness or suffocation. Runoff from fire control or dilution water may cause pollution.

Purification Methods

Purify it as the above styrenes and add a small amount of antioxidant if it is to be stored. It has UV in EtOH at max 285nm (log 3.07), and in EtOH + HCl 295nm (log 2.84) and 252nm (log 4.23). [Schwartzman & Carson J Am Chem Soc 78 322 1956, Joy & Orchin J Am Chem Soc 81 305 1959, Buck et al. J Chem Soc 23771949, Beilstein 5 IV 1369.]

InChI:InChI=1/C9H10/c1-3-9-6-4-8(2)5-7-9/h3-7H,1H2,2H3

Synthetic route

4-methylcinnamic acid (1866-39-3) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
With methyl tributylammonium chloride; sodium hydroxide at 150℃; for 5h;	99.1%
With hydrogen bromide Behandeln des Reaktionsprodukts mit Soda;
With ferulic acid decarboxylase from Saccharomyces cerevisiae In aq. phosphate buffer; dimethyl sulfoxide at 25℃; pH=7.4; Kinetics; Enzymatic reaction;

vinyl acetate (108-05-4) + para-bromotoluene (106-38-7) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
Stage #1: para-bromotoluene With magnesium; lithium chloride In tetrahydrofuran at 0 - 20℃; for 2h; Schlenk technique; Inert atmosphere; Stage #2: vinyl acetate With iron(III) chloride In tetrahydrofuran at 0℃; for 3h; Schlenk technique; Inert atmosphere;	99%
Stage #1: para-bromotoluene With magnesium; lithium chloride In tetrahydrofuran at 20℃; for 2h; Inert atmosphere; Stage #2: vinyl acetate With iron(III) chloride; N,N,N,N,-tetramethylethylenediamine In tetrahydrofuran at 0 - 20℃; for 4h;	99%
With [2,2]bipyridinyl; tetrabutylammonium tetrafluoroborate; cobalt(II) bromide In pyridine; acetonitrile at 20℃; Electrolysis;	53%
Stage #1: para-bromotoluene With magnesium; lithium chloride In tetrahydrofuran at 0 - 20℃; for 2h; Inert atmosphere; Stage #2: vinyl acetate With iron(III) chloride In tetrahydrofuran at 0℃; for 2h; Inert atmosphere;	49%

4-n-methylphenylacetylene (766-97-2) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
With sodium dodecylbenzenesulfonate; hydrogen; palladium diacetate In water at 25℃; under 760.051 Torr; for 0.75h;	99%
With piperazine; NiO doped titania In methanol at 20℃; for 3h; Inert atmosphere; Sealed tube; UV-irradiation;	97%
With hydrogen In ethanol at 100℃; under 4500.45 Torr; for 24h; chemoselective reaction;	93%

vinyl methanesulfonate (63918-53-6) + 4-methylphenylboronic acid (5720-05-8) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
With sodium tetrachloropalladate(II); cataCXium F sulf; potassium carbonate In water at 100℃; for 16h; Suzuki Miyaura coupling; Inert atmosphere;	99%

vinyl 4-methylbenzenesulfonate (83813-73-4) + 4-methylphenylboronic acid (5720-05-8) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
With sodium tetrachloropalladate(II); cataCXium F sulf; potassium carbonate In water at 100℃; for 16h; Suzuki Miyaura coupling; Inert atmosphere;	99%

4-Methylbenzyl alcohol (589-18-4) + Methyl phenyl sulfone (3112-85-4) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
With sodium hydride In mineral oil at 135℃; for 10h; Inert atmosphere; Schlenk technique;	99%

para-bromotoluene (106-38-7) + tri-n-butyl(vinyl)tin (7486-35-3) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
With palladium diacetate; N,N′-bis(2,6-diisopropylphenyl)imidazol-2-ylidene hydrochloride; tetrabutyl ammonium fluoride In tetrahydrofuran; 1,4-dioxane at 80℃; for 48h;	98%
With Pd/Fe3O4; cesium fluoride In 1,4-dioxane at 100℃; for 24h; Stille Cross Coupling;	75%

(vinyl)trimethoxylsilane (2768-02-7) + 4-tolyl iodide (624-31-7) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
With 1-butyl-3-methyl-3H-imidazol-1-ium fluoride In acetonitrile at 70℃; Hiyama Coupling; Inert atmosphere;	98%
With sodium hydroxide In water at 100℃; for 10h; Hiyama Coupling;	75%

4-n-methylphenylacetylene (766-97-2) → 1-ethenyl-4-methylbenzene (622-97-9) + 4-methylethylbenzene (622-96-8)

Conditions	Yield
With hydrogen In hexane at 40℃; under 760.051 Torr; for 3h;	A 96% B 4%
With hydrogen; platinum nanoparticles In methanol at 90℃; under 10343.2 Torr; for 4.5h; Title compound not separated from byproducts.;	A 88 % Spectr. B 12 % Spectr.
With hydrogen In hexane under 760.051 Torr; chemoselective reaction;

1-(chloroethynyl)-4-methylbenzene (33491-04-2) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
Stage #1: 1-(chloroethynyl)-4-methylbenzene With titanium(IV) isopropylate; isopropylmagnesium bromide In diethyl ether at -50℃; Metallation; Stage #2: With hydrogenchloride; water Hydrolysis;	95%

Methyltriphenylphosphonium bromide (1779-49-3) + 4-methyl-benzaldehyde (104-87-0) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
Stage #1: Methyltriphenylphosphonium bromide With n-butyllithium In tetrahydrofuran at 0℃; for 0.5h; Inert atmosphere; Stage #2: 4-methyl-benzaldehyde In tetrahydrofuran at 20℃; Inert atmosphere;	95%
With potassium carbonate In 1,4-dioxane for 16h; Reflux;	92%
With 1,8-diazabicyclo[5.4.0]undec-7-ene In toluene for 16h; Wittig reaction; Heating;	81%

tetravinylsilane (1112-55-6) + 4-tolyl iodide (624-31-7) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
With potassium fluoride; Pd (3 wt%)/C In N,N-dimethyl-formamide at 130℃; under 1500.15 Torr; for 3h; Reagent/catalyst; Time; Hiyama Coupling; Inert atmosphere;	95%

formaldehyd (50-00-0) + 4-Methylbenzyl alcohol (589-18-4) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
Stage #1: 4-Methylbenzyl alcohol With triethylphosphine hydrobromide at 100℃; for 0.166667h; Microwave irradiation; Stage #2: formaldehyd With potassium carbonate In water at 100℃; for 0.0833333h; Microwave irradiation;	95%

p-allyltoluene (3333-13-9) + ethene (74-85-1) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
With Hoveyda-Grubbs catalyst second generation; di-μ-bromobis-(tritert-butylphosphine)dipalladium(I) In tetrahydrofuran at 60℃; under 7500.75 Torr; for 16h; Autoclave;	94%

para-bromotoluene (106-38-7) + vinyl magnesium bromide (1826-67-1) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
With C17H36ClN6NiP2(1+)*Cl(1-) In tetrahydrofuran for 6h; Kumada Cross-Coupling; Inert atmosphere;	94%

para-bromotoluene (106-38-7) + potassium vinyltrifluoroborate → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
With C17H36ClN6NiP2(1+)*Cl(1-); potassium tert-butylate In toluene at 120℃; for 16h; Suzuki-Miyaura Coupling; Inert atmosphere;	93%
With caesium carbonate; triphenylphosphine; palladium dichloride In tetrahydrofuran; water at 85℃; for 7h; Suzuki-Miyaura reaction;	79%

4-tolyl iodide (624-31-7) + vinyl magnesium bromide (1826-67-1) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
Stage #1: vinyl magnesium bromide With indium(III) chloride In tetrahydrofuran; hexane at -78 - 20℃; Stage #2: 4-tolyl iodide With tetrakis(triphenylphosphine) palladium(0); carbon monoxide In tetrahydrofuran; hexane at 60℃; for 1h;	92%
Stage #1: vinyl magnesium bromide With indium(III) chloride In tetrahydrofuran at -78 - 20℃; Stage #2: 4-tolyl iodide; bis-triphenylphosphine-palladium(II) chloride In tetrahydrofuran for 0.5h; Heating; Further stages.;	89%
Stage #1: vinyl magnesium bromide With indium(III) chloride In tetrahydrofuran Stage #2: 4-tolyl iodide With tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran Heating;	68%

1-(1,2-dibromoethyl)-4-methylbenzene (33458-08-1) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
With indium; niobium pentachloride In tetrahydrofuran at 20℃; for 0.166667h; Sonication; chemoselective reaction;	92%
With 1,1'-bis(trimethylsilyl)-1,1',4,4'-tetrahydro-4,4'-bipyridylidene In acetonitrile at 20℃; for 2h; Inert atmosphere;	92%
With diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate; sodium carbonate In dimethyl sulfoxide at 20℃; for 1.5h; Inert atmosphere; Irradiation;	86%

2-(4-methylphenyl)oxirane (13107-39-6) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
With carbon monoxide In tetrahydrofuran; water at 110℃; under 6840.46 Torr; for 2h; Autoclave; chemoselective reaction;	90%
With sodium iodide; tin(ll) chloride In ethanol for 0.0833333h; Reflux; Green chemistry;	90%
With hydrogen; triethyl phosphite In isopropyl alcohol at 100℃; under 4500.45 Torr; for 12h; Glovebox; chemoselective reaction;	89%

CH3C6H4CH(CH3)OH (536-50-5) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
With aluminum (III) chloride; triphenylphosphine In nitromethane at 80℃; for 2h;	89%
With potassium pyrosulfate bei der Destillation;
at 120℃; for 0.25h; Microwave irradiation; Ionic liquid;

4-tolyl iodide (624-31-7) + ethenyltrimethylsilane (754-05-2) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
With bis(η3-allyl-μ-chloropalladium(II)); tris(diethylamino)sulfonium difluorotrimethylsiliconate In tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide at 50℃; for 2h;	89%
With potassium fluoride; Pd (0.87 wt%)/MgO In N,N-dimethyl-formamide at 130℃; under 1500.15 Torr; for 7h; Time; Reagent/catalyst; Hiyama Coupling; Inert atmosphere;	78%
With TEA; palladium diacetate; triphenylphosphine In N,N-dimethyl-formamide at 85℃; for 24h;	51 % Chromat.

4-tolyl iodide (624-31-7) + trivinyl indium (75076-64-1) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
With bis-triphenylphosphine-palladium(II) chloride In tetrahydrofuran for 0.5h; Heating;	89%

4-Methylbenzyl chloride (104-82-5) + Chloromethyltrimethylsilane (2344-80-1) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
Stage #1: 4-Methylbenzyl chloride With polymer bound α-sulfonyl monocarbanions In tetrahydrofuran; N,N-dimethyl-formamide at 80℃; solid-phase synthesis; Stage #2: Chloromethyltrimethylsilane With Lithium dimsyl In tetrahydrofuran at 20℃; Stage #3: With tetrabutyl ammonium fluoride In tetrahydrofuran at 20℃;	89%

4-tolyl iodide (624-31-7) + tri-n-butyl(vinyl)tin (7486-35-3) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
layered double hydroxide-supported nanoplatinum In 1-methyl-pyrrolidin-2-one at 100℃; for 8h; Stille coupling reaction;	88%
With palladium; N,N-dimethyl-formamide In 1-methyl-pyrrolidin-2-one at 120℃; for 15h;	65%

4-methylphenyl tosylate (3899-96-5) + vinyl magnesium bromide (1826-67-1) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
With C17H36ClN6NiP2(1+)*Cl(1-) In tetrahydrofuran for 6h; Kumada Cross-Coupling; Inert atmosphere;	87%

ethene (74-85-1) + para-bromotoluene (106-38-7) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
With 10H-phenothiazine; bis(μ-chloro)bis{(2-(1-(hydroxyimino)methyl)phenyl-C1,N)palladium(II)}; potassium acetate In N,N-dimethyl acetamide at 105℃; under 1551.49 Torr; for 24h; Heck-Mizoroki reaction; Inert atmosphere;	86%
With 1-ethyl-piperidine; 1,8-diazabicyclo[5.4.0]undec-7-ene; PdCl2{P(OC6H5)3}2 In carbon dioxide at 130℃; under 7600 Torr; for 18h; Mizoroki-Heck reaction;
With tributyl-amine; potassium carbonate; palladium In N,N-dimethyl-formamide at 150℃; under 7757.43 Torr; for 1h; Heck reaction; microwave irradiation;
With palladium diacetate; triethylamine; tris-(o-tolyl)phosphine In acetonitrile at 60℃; under 3345.86 Torr; Heck Reaction; Sealed tube;

dimethylsulfone (67-71-0) + 4-Methylbenzyl alcohol (589-18-4) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
With platinum on carbon; potassium tert-butylate; hydrogen In toluene under 1875.19 Torr; for 10h; Inert atmosphere; Reflux;	86%

4-methylbenzenediazonium tetrafluoroborate (459-44-9) + potassium vinyltrifluoroborate → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
With 1-butyl-3-methylimidazolium Tetrafluoroborate; azapalladacycle catalyst In methanol at 20℃; for 0.166667h;	83%
azamacrocyclic palladium(0) In 1,4-dioxane at 20℃; for 3.5h; Suzuki-Miyaura cross-coupling;	36%

4-tolyl iodide (624-31-7) + 4,4,6-trimethyl-2-vinyl-1,3,2-dioxaborinane (4627-10-5) → 1-ethenyl-4-methylbenzene (622-97-9)

Conditions	Yield
With silver(l) oxide; tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran at 67℃; for 24h; Suzuki-Miyaura reaction;	83%

1-ethenyl-4-methylbenzene (622-97-9) → 2-(4-methylphenyl)oxirane (13107-39-6)

Conditions	Yield
With tert.-butylhydroperoxide; C15H12ClMoN3O7 In methanol; dichloromethane for 1h; Reagent/catalyst;	100%
With tert.-butylhydroperoxide; cis-[MoO2(N'-(3-ethoxy-2-hydroxybenzylidene)-2-methoxybenzohydrazide-2H)(OH2)] In methanol; dichloromethane for 1h; Catalytic behavior; Reflux;	100%
With tert.-butylhydroperoxide; C22H22Br4N6O7S2V2 In methanol; dichloromethane for 1h;	100%

1-ethenyl-4-methylbenzene (622-97-9) → 4-methylethylbenzene (622-96-8)

Conditions	Yield
With C28H18Co(1-)*K(1+)*2C4H10O2; hydrogen In toluene at 20℃; under 1500.15 Torr; for 3h; Reagent/catalyst; Time; chemoselective reaction;	100%
With hydrogen In ethanol at 20℃; under 760.051 Torr; for 0.833333h; Green chemistry;	99%
With hydrazine hydrate In tetrahydrofuran at 20℃; for 24h; Irradiation;	99%

1-ethenyl-4-methylbenzene (622-97-9) → 1-(1,2-dibromoethyl)-4-methylbenzene (33458-08-1)

Conditions	Yield
With bromine In chloroform at 0℃; Inert atmosphere;	100%
With bromine In chloroform at 0 - 20℃; for 1h; Inert atmosphere;	100%
With [bis(acetoxy)iodo]benzene; potassium bromide In dichloromethane; water at 20℃; for 0.25h;	98%

triethylsilane (617-86-7) + 1-ethenyl-4-methylbenzene (622-97-9) → (E)-1-(p-methylphenyl)-2-(triethylsilyl)ethylene (75476-54-9)

Conditions	Yield
dodecacarbonyl-triangulo-triruthenium In benzene at 80℃; for 5h;	100%
With dimanganese decacarbonyl; N,N-bis(diphenylphosphino)isopropylamine at 140℃; for 24h; Sealed tube;	82%
With norborn-2-ene; chloro(1,5-cyclooctadiene)rhodium(I) dimer; triphenylphosphine In tetrahydrofuran at 100℃; for 2h; Schlenk technique; Inert atmosphere; Sealed tube;	82%

Trichloromethanesulfonyl chloride (2547-61-7) + 1-ethenyl-4-methylbenzene (622-97-9) → 1,1,1,3-tetrachloro-3-(4-methylphenyl)propane (86862-25-1)

Conditions	Yield
Ru2Cl4((+)-diop)3 In benzene at 100℃;	100%
dichlorotris(triphenylphosphine)ruthenium(II) In benzene at 100℃; for 24h;	55%

1-ethenyl-4-methylbenzene (622-97-9) → 2-bromo-1-(p-tolyl)ethanol (60655-81-4)

Conditions	Yield
With N-Bromosuccinimide; water In acetonitrile at 20℃;	100%
With potassium bromate; sulfuric acid; water; potassium bromide In dimethyl sulfoxide at 70 - 80℃; for 0.5h;	97%
With sodium periodate; sulfuric acid; lithium bromide In water; acetonitrile at 25℃; pH=6.12;	95%

1-ethenyl-4-methylbenzene (622-97-9) + triphenylphosphine (603-35-0) → <β-(4-methyl)styryl>triphenylphosphonium perchlorate

Conditions	Yield
With LutClO4; potassium carbonate In dichloromethane electrolysis (20 mA; current density; 1 mA/cm-2);	100%

1-ethenyl-4-methylbenzene (622-97-9) → (E)-4,4'-dimethylstilbene (18869-29-9)

Conditions	Yield
tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride In dichloromethane for 2h; Heating;	100%
With 3-butyl-1-methyl-1H-imidazol-3-ium hexafluorophosphate; Grubbs-type ruthenium at 20℃; for 4h;	89%
With tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride In methanol; dichloromethane; water at 45℃; for 8.5h; Ionic liquid; Inert atmosphere; Catalyst solution in CH2Cl2/BMIM incapsulated within polydimethylsiloxane thimble;	76%

1-ethenyl-4-methylbenzene (622-97-9) → 4-methyl-benzaldehyde (104-87-0)

Conditions	Yield
With sodium periodate; C31H29Br2N3Ru*CH2Cl2 In water; ethyl acetate; acetonitrile at 25℃; for 0.5h; Inert atmosphere; Schlenk technique;	100%
With tert.-butylhydroperoxide; manganese(II,III) oxide In acetonitrile at 70℃; for 3h;	98%
With iron(III) trifluoromethanesulfonate; 2-((4R,5R)-1-((4-(tert-butyl)phenyl)sulfonyl)-4,5-diphenylimidazolidin-2-yl)-6-((4R,5R)-1-((4-(tert-butyl)phenyl)sulfonyl)-4,5-diphenylimidazolidin-2-yl)pyridine; oxygen In 1,2-dichloro-ethane at 70℃; under 760.051 Torr; for 6h; Reagent/catalyst; Solvent; Green chemistry; chemoselective reaction;	96%

1-ethenyl-4-methylbenzene (622-97-9) → oligo(4-methylstyrene), Mw = 2456, Mn = 1501, isotactic fraction 85%; monomer(s): 4-methylstyrene

Conditions	Yield
[Ni(η3-CH2C(Me)CH2)(κ1P-PPh2CH2CH=CH2)][BAr'4] In 1,2-dichloro-ethane at 25℃; for 22h;	100%

1-ethenyl-4-methylbenzene (622-97-9) + [Pd(CH3)(carbonyl)(1,4-diisopropyl-1,4-diaza-1,3-butadiene)](1+)[B(3,5-(CF3)2C6H3)4](1-) (208589-78-0) → CH3C6H4CHCH2COCH3Pd(CH3)2CHNCHCHNCH(CH3)2(1+)*B[C6H3(CF3)2]4(1-)=CH3C6H4CHCH2COCH3Pd(CH3)2CHNCHCHNCH(CH3)2B[C6H3(CF3)2]4 (208589-81-5)

Conditions	Yield
In chloroform-d1 addn. of p-methylstyrene to complex soln. at -10°C, gentle heating to 20°C;	100%
In chloroform addn. of p-methylstyrene to complex soln. at -10°C, gentle heating to 20°C;	100%
In dichloromethane (N2); addn. of p-methylstyrene to a soln. of palladium complex in CH2Cl2at -15°C, slow warming to 25°C; addn. of hexane, washing with hexane, drying in vac.; elem. anal.;	96%

1-ethenyl-4-methylbenzene (622-97-9) + 2-hydroxy-2-methylpropanenitrile (75-86-5) → (+/-)-2-(4'-methylphenyl)-propionitrile (75920-45-5)

Conditions	Yield
With 3-[bis-(4-methoxy-phenyl)-phosphanyl]-2H-isoquinolin-1-one; N-{6-[bis-(4-methoxy-phenyl)-phosphanyl]-pyridin-2-yl}-2,2-dimethyl-propionamide; bis(1,5-cyclooctadiene)nickel (0) In toluene at 35℃; for 25h; Inert atmosphere; regioselective reaction;	100%

1-ethenyl-4-methylbenzene (622-97-9) + C19H16O3 → 2-phenyl-5-(p-tolyl)-2,3,4,5-tetrahydronaphtho[1,2-b:4,3,-b’]difuran

Conditions	Yield
With 1,1,1,3',3',3'-hexafluoro-propanol; Pentafluorobenzoic acid In dichloromethane at 20℃; for 1h; regioselective reaction;	100%

1-oxothiolane (1600-44-8) + 1-ethenyl-4-methylbenzene (622-97-9) + trifluoromethylsulfonic anhydride (358-23-6) → (E)-1-(4-methylstyryl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate

Conditions	Yield
In dichloromethane at -40 - 20℃; Inert atmosphere;	100%

1-ethenyl-4-methylbenzene (622-97-9) + pyridin-2-yl sulfenyl chloride (59089-57-5) → 3-(4-methylphenyl)-2H,3H-thiazolo[3,2-]pyridin-4-ium chloride

Conditions	Yield
Stage #1: pyridin-2-yl sulfenyl chloride With sulfuryl dichloride In dichloromethane at 20℃; for 0.166667h; Stage #2: 1-ethenyl-4-methylbenzene In dichloromethane at 20℃; for 20h; regioselective reaction;	100%

1-ethenyl-4-methylbenzene (622-97-9) + 2-pyridineselenenyl chloride (82998-10-5) → 3-(4-methylphenyl)-2H,3H-selenazolo[3,2-]pyridin-4-ium chloride

Conditions	Yield
Stage #1: 2-pyridineselenenyl chloride With bromine In chloroform at 20℃; for 0.333333h; Stage #2: 1-ethenyl-4-methylbenzene In chloroform at 20℃; for 6h; Reflux; regioselective reaction;	100%

1-ethenyl-4-methylbenzene (622-97-9) + [N-(p-tolylsulfonyl)imino]phenyliodinane (55962-05-5) → N-tosyl-2-(p-tolyl)aziridine (97401-87-1)

Conditions	Yield
With [CuI(tris[(tetramethylguanidino)-phenyl]amine)][PF6] In acetonitrile for 2h; Inert atmosphere; Molecular sieve;	99%
With [PhB{CH2P(p-CF3Ph)2}3]Cu(PPh3) In dichloromethane at 20℃; for 5h; Inert atmosphere; Schlenk technique;	97%
With iodine In water at 20℃; for 10h; Green chemistry;	91%

1-ethenyl-4-methylbenzene (622-97-9) + phenylboronic acid (98-80-6) → E-1-methyl-4-styryl-benzene (4714-21-0, 130059-91-5, 130059-95-9, 1657-45-0, 1860-17-9)

Conditions	Yield
With palladium diacetate; acetic anhydride; 2,3-dicyano-5,6-dichloro-p-benzoquinone In acetic acid at 90℃; for 27h; Heck reaction;	99%
With [2,2]bipyridinyl; methanesulfonic acid; palladium(II) trifluoroacetate In N,N-dimethyl-formamide at 100℃; for 24h; Schlenk technique;	92%
With C38H36Cl2Fe2N2Pd2; oxygen In N,N-dimethyl-formamide at 50℃; for 3h; Heck reaction;	87%
With N-Bromosuccinimide; palladium diacetate In toluene at 20℃; for 12h; Heck Reaction; Inert atmosphere; Schlenk technique;	70%
With palladium diacetate; sodium acetate In acetic acid at 25℃; for 20h;	99 % Chromat.

1-ethenyl-4-methylbenzene (622-97-9) + ethene (74-85-1) → 1-methyl-4-(1-methyl-2-propenyl)benzene (97664-18-1)

Conditions	Yield
With 2-benzyloxymethylphenyldiphenylphosphine; bi(allylnickel bromide); sodium tetrakis[(3,5-di-trifluoromethyl)phenyl]borate In dichloromethane at 23℃; under 760.051 Torr; for 11h; Schlenk technique;	99%
With hexakis(acetonitrile)nickel(II) tetrafluoroborate; diethylaluminium chloride; triphenylphosphine In dichloromethane; toluene at 20℃; under 7500.6 Torr; for 1h; hydrovinylation;	84%
With 2; diethylaluminium chloride; triphenylphosphine In dichloromethane; toluene under 7500.6 Torr; for 0.5h; Yield given;
With silver trifluoromethanesulfonate; triphenylphosphine; bi(allylnickel bromide) In dichloromethane at -55℃; under 760 Torr; for 2h;
With C33H63ClOP2Ru; silver trifluoromethanesulfonate In dichloromethane for 6h; Inert atmosphere;

1-ethenyl-4-methylbenzene (622-97-9) + 2-carbonyl-3-butenenitrile (60556-87-8) → 3,4-dihydro-2-(4-methylphenyl)-2H-pyran-6-carbonitrile

Conditions	Yield
In acetonitrile at 81℃; for 24h; hetero-Diels-Alder cycloaddition;	99%

1-ethenyl-4-methylbenzene (622-97-9) + 2,3-dimethyl-2,3-butane diol (76-09-5) → (R)-pinacol (1-(p-methylphenyl)ethyl) boronate (257298-94-5)

Conditions	Yield
Stage #1: 1-ethenyl-4-methylbenzene With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; (R)-2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl; benzo[1,3,2]dioxaborole In 1,2-dimethoxyethane at -66 - -65℃; for 7h; hydroboration; Stage #2: 2,3-dimethyl-2,3-butane diol In 1,2-dimethoxyethane at -66 - 20℃; Substitution;	99%
Stage #1: 1-ethenyl-4-methylbenzene With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; (R)-2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl; benzo[1,3,2]dioxaborole In 1,2-dimethoxyethane at -68℃; for 7h; Inert atmosphere; Stage #2: 2,3-dimethyl-2,3-butane diol In 1,2-dimethoxyethane at -68 - 20℃; optical yield given as %ee;	65%

1-ethenyl-4-methylbenzene (622-97-9) + 4-nitrobenzaldehdye (555-16-8) → 3-chloro-1-(4-nitro-phenyl)-3-p-tolyl-propan-1-ol

Conditions	Yield
Stage #1: 1-ethenyl-4-methylbenzene; 4-nitrobenzaldehdye With phenylborondichloride In dichloromethane at 25℃; for 6h; Stage #2: With water	99%

1-ethenyl-4-methylbenzene (622-97-9) + 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane (25015-63-8) → 2-(2-(4-methylphenyl)ethyl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane

Conditions	Yield
With bis(1,5-cyclooctadiene)diiridium(I) dichloride; 1,2-bis-(diphenylphosphino)ethane In dichloromethane at 20℃; for 24h;	99%
With bis(1,5-cyclooctadiene)diiridium(I) dichloride; 1,4-di(diphenylphosphino)-butane In tetrahydrofuran at 20℃; for 24h;	95%
With bis(diphenylphosphino)butane; bis(1,5-cyclooctadiene)diiridium(I) dichloride In tetrahydrofuran under N2; pinacol borane was reacted with ligand in THF at room temp. for 24 h in the presence of Ir-complex and bis(diphenylphosphino)butane; chromy.;	95%

1-ethenyl-4-methylbenzene (622-97-9) + iodobenzene (591-50-4) → 4-methylstilbene (4714-21-0)

Conditions	Yield
With potassium phosphate tribasic trihydrate In N,N-dimethyl-formamide at 120℃; for 2h; Heck Reaction;	99%
With potassium carbonate In N,N-dimethyl-formamide at 50℃; for 0.133333h; Catalytic behavior; Heck Reaction; Sonication; Green chemistry;	97%
With triethylamine In water; acetonitrile at 60℃; for 2h; Heck Reaction;	97%

1-ethenyl-4-methylbenzene (622-97-9) + [(CH3CNC6H4OCH3)2Pd(CH3)(CO)](1+)*B(C6H3(CF3)2)4(1-)=[(CH3CNC6H4OCH3)2Pd(CH3)(CO)][B(C6H3(CF3)2)4] → [(CH3CNC6H4OCH3)2Pd(CH3C6H4CHCH2COCH3)](1+)*B(C6H3(CF3)2)4(1-)=[(CH3CNC6H4OCH3)2Pd(CH3C6H4CHCH2COCH3)][B(C6H3(CF3)2)4]

Conditions	Yield
In not given	99%

1-ethenyl-4-methylbenzene (622-97-9) + [(CH3CNC6H3(CH3)2)2Pd(CH3)(CO)](1+)*B(C6H3(CF3)2)4(1-)=[(CH3CNC6H3(CH3)2)2Pd(CH3)(CO)][B(C6H3(CF3)2)4] → [(C10H12N)2Pd(CH3C6H4CHCH2COCH3)](1+)*B(C6H3(CF3)2)4(1-)=[(C10H12N)2Pd(CH3C6H4CHCH2COCH3)][B(C6H3(CF3)2)4]

Conditions	Yield
In not given	99%

1-ethenyl-4-methylbenzene (622-97-9) + t-butyl diazoacetate (35059-50-8) → tert-butyl (1R*,2S*)-2-(4-methylphenyl)cyclopropane-1-carboxylate

Conditions	Yield
With C67H51IrN2O2 In tetrahydrofuran at -78℃; for 24.1667h; optical yield given as %ee; enantioselective reaction;	99%

Upstream product

• 67-56-1 methanol 
• 32327-68-7 p-methyl-2-phenylethyl chloride 
• 159755-12-1 1-(1-bromoethyl)-4-methylbenzene 
• 109-87-5 Dimethoxymethane 
• 106-42-3 para-xylene 
• 2768-02-7 (vinyl)trimethoxylsilane 
• 624-31-7 4-tolyl iodide 
• 124-38-9 carbon dioxide 
• 99-87-6 4-methylisopropylbenzene 
• 530-45-0 1,1-di(4-methylphenyl)ethane 
• 74-85-1 ethene 
• 106-38-7 para-bromotoluene 
• 7486-35-3 tri-n-butyl(vinyl)tin 
• 98-59-9 p-toluenesulfonyl chloride 

Downstream Products

• 20821-95-8 5-(4-methylphenyl)-3-phenyl-4,5-dihydroisoxazole 
• 96-09-3 styrene oxide 
• 13107-39-6 2-(4-methylphenyl)oxirane 
• 122445-12-9 10methyl-4-(3-methylpentyl)benzene 
• 128752-86-3 diethyl <2-(p-methylphenyl)ethyl>malonate 
• 86862-25-1 1,1,1,3-tetrachloro-3-(4-methylphenyl)propane 
• 5216-32-0 cis-1,2-dichloro-1,2-diphenylethene 
• 75476-54-9 (E)-1-(p-methylphenyl)-2-(triethylsilyl)ethylene 
• 83739-60-0 1-(2-bromo-1-methoxyethyl)-4-methylbenzene 
• 105028-82-8 (2-Iodo-2-p-tolyl-ethyl)-carbamic acid methyl ester 
• 80621-73-4 4-methyl-1-(1,2-dimethoxyethyl)benzene 
• 80621-74-5 C₂₀H₂₆O₂ 
• 84508-58-7 2-Bromo-1,1-dimethoxy-1-(4-methylphenyl)ethane 
• 121687-98-7 3-p-Tolyl-2,3-dihydro-naphtho[1,2-b][1,4]dioxine 

Relevant articles and documents

Photoredox Catalyzed Sulfonylation of Multisubstituted Allenes with Ru(bpy)3Cl2 or Rhodamine B

A highly regio- and stereoselective sulfonylation of allenes was developed that provided direct access to α, β-substituted unsaturated sulfone. By means of visible-light photoredox catalysis, the free radicals produced by p-toluenesulfonic acid reacted with multisubstituted allenes to obtain Markovnikov-type vinyl sulfones with Ru(bpy)3Cl2 or Rhodamine B as photocatalyst. The yield of this reaction could reach up to 91%. A series of unsaturated sulfones would be used for further transformation to some valuable compounds.

Controlling the Lewis Acidity and Polymerizing Effectively Prevent Frustrated Lewis Pairs from Deactivation in the Hydrogenation of Terminal Alkynes

Two strategies were reported to prevent the deactivation of Frustrated Lewis pairs (FLPs) in the hydrogenation of terminal alkynes: reducing the Lewis acidity and polymerizing the Lewis acid. A polymeric Lewis acid (P-BPh3) with high stability was designed and synthesized. Excellent conversion (up to 99%) and selectivity can be achieved in the hydrogenation of terminal alkynes catalyzed by P-BPh3. This catalytic system works quite well for different substrates. In addition, the P-BPh3 can be easily recycled.

Phenylacetylene semihydrogenation over a palladium pyrazolate hydrogen-bonded network

The palladium azolate/carboxylate network (Pd-dmpzc) catalyses the selective hydrogenation of phenylacetylene to styrene in water. Under optimised conditions, at a Pd:NaBH4 ratio of 1:100 at 40 °C, Pd-dmpzc provided much better results than Pd(OAc)2 or PdCl2(CH3CN)2. Analysis of the recovered catalyst revealed the presence of different Pd2+ species and Pd0 NPs which contributed in the catalytic reaction.