74254-18-5

Basic information

• Product Name: Benzene, 1-methoxy-3-(1-propenyl)-, (Z)-
• CAS NO: 74254-18-5
• Molecular Formula: C10H12O
• Molecular Weight: 148.205
• Mol File: 74254-18-5.mol

Chemical Properties

• CAS DataBase Reference: Benzene, 1-methoxy-3-(1-propenyl)-, (Z)-(CAS DataBase Reference)
• NIST Chemistry Reference: Benzene, 1-methoxy-3-(1-propenyl)-, (Z)-(74254-18-5)
• EPA Substance Registry System: Benzene, 1-methoxy-3-(1-propenyl)-, (Z)-(74254-18-5)

Safety Data

• Hazardous Substances Data: 74254-18-5(Hazardous Substances Data)

Upstream product

• 88533-69-1 (1RS,2SR)-2-diphenylphosphinoyl-1-(3-methoxyphenyl)propan-1-ol 
• 925-90-6 ethylmagnesium bromide 
• 591-31-1 3-methoxy-benzaldehyde 
• 75-89-8 2,2,2-trifluoroethanol 
• 52956-26-0 (E)-1-methoxy-3-(prop-1-en-1-yl)benzene 
• 52956-27-1 1-(3-methoxyphenyl)propanol 
• 1135821-12-3 ethyl-(2-methoxy-phenyl)-diphenyl-phosphonium; iodide 
• 1135820-79-9 C₂₁H₂₂OP⁽¹⁺⁾*I^(1-) 
• 1135820-52-8 C₂₀H₂₀OP⁽¹⁺⁾*I^(1-) 
• 4736-60-1 ethyltriphenylphosphonium iodide 
• 1530-32-1 ethyltriphenylphosphonium bromide 
• 24743-14-4 1-allyl-3-methoxybenzene 
• 2398-37-0 3-methoxyphenyl bromide 
• 24850-33-7 allyltributylstanane 

Downstream Products

• 52956-26-0 (E)-1-methoxy-3-(prop-1-en-1-yl)benzene 

Relevant articles and documents

Highly Z-Selective Double Bond Transposition in Simple Alkenes and Allylarenes through a Spin-Accelerated Allyl Mechanism

Double-bond transposition in alkenes (isomerization) offers opportunities for the synthesis of bioactive molecules, but requires high selectivity to avoid mixtures of products. Generation of Z-alkenes, which are present in many natural products and pharmaceuticals, is particularly challenging because it is usually less thermodynamically favorable than generation of the E isomers. We report a β-dialdiminate-supported, high-spin cobalt(I) complex that can convert terminal alkenes, including previously recalcitrant allylbenzenes, to Z-2-alkenes with unprecedentedly high regioselectivity and stereoselectivity. Deuterium labeling studies indicate that the catalyst operates through a π-allyl mechanism, which is different from the alkyl mechanism that is followed by other Z-selective catalysts. Computations indicate that the triplet cobalt(I) alkene complex undergoes a spin state change from the resting-state triplet to a singlet in the lowest-energy C-H activation transition state, which leads to the Z product. This suggests that this change in spin state enables the catalyst to differentiate the stereodefining barriers in this system, and more generally that spin-state changes may offer a route toward novel stereocontrol methods for first-row transition metals.

Electrochemistry Broadens the Scope of Flavin Photocatalysis: Photoelectrocatalytic Oxidation of Unactivated Alcohols

Riboflavin-derived photocatalysts have been extensively studied in the context of alcohol oxidation. However, to date, the scope of this catalytic methodology has been limited to benzyl alcohols. In this work, mechanistic understanding of flavin-catalyzed oxidation reactions, in either the absence or presence of thiourea as a cocatalyst, was obtained. The mechanistic insights enabled development of an electrochemically driven photochemical oxidation of primary and secondary aliphatic alcohols using a pair of flavin and dialkylthiourea catalysts. Electrochemistry makes it possible to avoid using O2 and an oxidant and generating H2O2 as a byproduct, both of which oxidatively degrade thiourea under the reaction conditions. This modification unlocks a new mechanistic pathway in which the oxidation of unactivated alcohols is achieved by thiyl radical mediated hydrogen-atom abstraction.

Engineering P450 Peroxygenase to Catalyze Highly Enantioselective Epoxidation of cis-β-Methylstyrenes

P450 119 peroxygenase and its site-directed mutants are discovered to catalyze the enantioselective epoxidation of methyl-substituted styrenes. Two new site-directed P450 119 mutants, namely T213Y and T213M, which were designed to improve the enantioselectivity and activity for the epoxidation of styrene and its methyl substituted derivatives, were studied. The T213M mutant is found to be the first engineered P450 peroxygenase that shows highly enantioselective epoxidation of cis-β-methylstyrenes, with up to 91 % ee. Molecular modeling studies provide insights into the different catalytic activity of the T213M mutant and the T213Y mutant in the epoxidation of cis-β-methylstyrene. The results of the calculations also contribute to a better understanding of the substrate specificity and configuration control for the regio- and stereoselective peroxygenation catalyzed by the T213M mutant.

A facile and convenient sequential homobimetallic catalytic approach towards β-methylstyrenes. A one-pot Stille cross-coupling/isomerization strategy

An efficient one-pot synthetic approach towards β-methylstyrenes is reported. The transformation, based on sequential homobimetallic catalysis, involves a Stille cross-coupling reaction between aryl halides and allyltributylstannane, followed by an in situ palladium-catalyzed conjugative isomerization. The reaction was optimized, and the best results were obtained with 10 mol% Pd(PPh3)2Cl2, 8.0 equiv. LiCl, and 0.5 equiv. PPh3 in diglyme at 130 °C for 12 h. It was demonstrated that the reaction tolerates a wide variety of functional groups. This journal is the Partner Organisations 2014.

Efficient double bond migration of allylbenzenes catalyzed by Pd(OAc) 2-HFIP system with unique substituent effect

A novel catalyst system of Pd(OAc)2-HFIP induces double-bond migration of allylbenzenes under mild conditions with low catalytic loading to afford 1-propenylbenzenes. The reaction shows a unique substituent effect that is highly dependent on the distance of substituents from the allylic moiety. Thus, the reactivity of substrates bearing a methyl group is ordered in para > meta > ortho, whereas it is entirely reversed as ortho > meta > para for methoxy and chloro substituents.

Role of the methoxy group in product formation via TiCl 4 promoted 4-phenyldioxolane isomerizations

The product distribution obtained from the TiCl 4 initiated intramolecular isomerizations of 4-methoxyphenyl-and trimethoxyphenyldioxolanes at -78 °C, -30 °C and 0 °C provided insights into the important regiochemical role played by these groups in such Mukaiyama-type rearrangements through their resonance effects on the aryl ring of the dioxolanes. ARKAT USA, Inc.

Stereoselective Wittig olefination reactions employing a novel ortho-P-aryl alkoxide effect

Non-stabilized ortho-P-alkoxy-substituted ylides react with aromatic and aliphatic aldehydes providing (E)-olefins with high stereocontrol, also allowing easy phosphine oxide removal in certain cases.

Methoxy-substituted stilbenes, styrenes, and 1-arylpropenes: Photophysical properties and photoadditions of alcohols

The photochemistry of trans-stilbene and four methoxy-substituted stilbene derivatives has been investigated in a variety of solvents. The fluorescence of all five trans isomers was quenched by 2,2,2-trifluoroethanol (TFE). Upon irradiation of the five substrates in TFE, the products derived from photoaddition of the solvent were detected. Nuclear magnetic resonance spectroscopy of the products formed by irradiation in TFE-OD indicated that the proton and nucleophile are attached to two adjacent atoms of the original alkene double bond. Irradiation of the corresponding methoxy-substituted styrenes and trans-1-arylpropenes in TFE produced the analogous solvent adducts. The photoaddition of TFE proceeded with the general order of reactivity: styre > trans-1-arylpropenes > trans-stilbenes. Transient carbocation intermediates were observed following laser flash photolysis of the stilbenes in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP). The results are consistent with a mechanism that involves photoprotonation of the substrates by TFE or HFIP, followed by nucleophilic trapping of short-lived carbocation intermediates. Compared to the other stilbene derivatives, trans-3,5-dimethoxystilbene displayed a large quantum yield of fluorescence and a low quantum yield of trans-cis isomerization in polar organic solvents. The unique photophysical properties of trans-3,5-dimethoxystilbene are attributed to formation of a highly polarized charge-transfer excited state (μe = 13.2 D).

Photoinduced nucleophilic addition of ammonia and alkylamines to methoxy-substituted styrene derivatives

The photoamination of trans-1-arylpropenes (aryl = 2-methoxyphenyl), (1), 3-methoxyphenyl (2) 3,4-dimethoxyphenyl (3), and 4-methoxyphenyl (4) with NH3, i-PrNH2, and t-BuNH2 (RNH2), in the presence of p-dicyanobenzene (p-DCB) gave 2-alkylamino-1 arylpropanes (9) and/or 2-alkylamino-1-aryl-1-(4-cyanophenyl)propanes (10). The photoaminations of 1,2-dihydro-7-methoxynaphthalenes (6-8) with RNH2 in the presence of p-DCB gave mainly 2-alkylamino-1-(4-cyanophenyl)-6-methoxy-1,2,3,4-tetrahydronaphthalene s (13). The photoamination of trans-1-(3,5-dimethoxyphenyl)propene (5) with i-PrNH2 occurred at aromatic ring to give trans-1-(2-isopropylamino-3,5-dimethoxyphenyl)propene (11). The photoaminations of 1-4 and 6-8 with NH3 in the presence of m-dicyanobenzene gave the aminated products without incorporation of cyanophenyl group. Furthermore, the addition of 1,3,5-triphenylbenzene and m-terphenyl for these reactions improved the yields of the photoaminated products.

The Stereocontrolled Horner-Wittig Reaction: Synthesis of Disubstituted Alkenes

Addition of the lithium derivatives of phosphine oxides Ph2P(O)CH2R1 to aldehydes gives erythro adducts (11) with good stereoselectivity.Reduction of α-diphenylphosphinoyl ketones (12) gives threo adducts (11) with even better stereoselectivity.Purification by flash chromatography and/or crystallisation followed by elimination of Ph2PO2 gives pure Z- or E-alkenes with high material conversion.Explanations are offered for the stereoselectivities, conditions defined for full stereochemical control, and guidelines suggested for approaches to a given alkene.