72667-90-4

Upstream product

• 917-64-6 methyl magnesium iodide 
• 1201-38-3 2',5'-dimethoxyacetophenone 
• 25245-34-5 1-bromo-2,5-dimethoxybenzene 
• 67-64-1 acetone 
• 2785-98-0 2,5-dimethoxybenzoic acid 
• 150-78-7 1,4-dimethoxybezene 
• 62890-98-6 2,5-dimethoxyphenylmagnesium bromide 
• 2150-40-5 methyl 2,5-dimethoxybenzoate 
• 74-88-4 methyl iodide 

Downstream Products

• 96826-23-2 C₂₀H₂₆O₄ 
• 53581-82-1 2,5-dimethoxy-4-(2-propyl)benzaldehyde 
• 189766-10-7 (S)S-1,4-dimethoxy-2-isopropyl-5-p-tolylsulfinylbenzene 
• 189766-17-4 (SS)-2-isopropyl-5-(p-tolylsulfinyl)-1,4-benzoquinone 
• 4132-71-2 2-Isopropyl-1,4-dimethoxybenzene 
• 96826-39-0 C₂₂H₃₀O₄ 
• 72667-91-5 2-propenyl-1,4-dimethoxybenzene 

Relevant academic research and scientific papers

Expeditious and practical synthesis of tertiary alcohols from esters enabled by highly polarized organometallic compounds under aerobic conditions in Deep Eutectic Solvents or bulk water

An efficient protocol was developed for the synthesis of tertiary alcohols via nucleophilic addition of organometallic compounds of s-block elements (Grignard and organolithium reagents) to esters performed in the biodegradable choline chloride/urea eutectic mixture or in water. This approach displays a broad substrate scope, with the addition reaction proceeding quickly (20 s reaction time) and cleanly, at ambient temperature and under air, straightforwardly furnishing the expected tertiary alcohols in yields of up to 98%. The practicability of the method is exemplified by the sustainable synthesis of some representative S-trityl-L-cysteine derivatives, which are a potent class of Eg5 inhibitors, also via telescoped one-pot processes.

High-capacity organic cathode active materials of 2,2′-bis-p-benzoquinone derivatives for rechargeable batteries

Rechargeable batteries using organic cathode materials are expected to afford high mass energy densities since these materials can undergo multiple electron redox reactions per molecule. Although the batteries using benzoquinone (BQ) derivatives as organic cathode active materials exhibited high theoretical capacity, their practical capacities and cycle retention were far from satisfactory. To overcome these problems, dimeric BQ derivatives based on the 2,2′-bis-p-benzoquinone (BBQ) framework were synthesized, and the charge-discharge behaviour of the prepared cells using BBQs as the cathode active materials was investigated. BBQ-based cells exhibited excellent performance compared to those based on BQ monomers. For example, the BBQ cell afforded a high initial capacity of 358 A h kg-1 (more than twice that of current lithium-ion batteries that use LiCoO2 as the cathode active material) and a high cycle retention of 198 A h kg-1 at 50 cycles. Electrochemical measurements and density functional theory (DFT) calculations indicated that three electron-redox reactions generally occur in BBQ derivatives, although (OMe)2-BBQ appeared to undergo a four-electron redox reaction.

Spectral properties and absolute rate constants for β-scission of ring-substituted cumyloxyl radicals. A laser flash photolysis study

A laser flash photolysis study of the spectral properties and β-scission reactions of a series of ring-substituted cumyloxyl radicals has been carried out. All cumyloxyl radicals display a broad absorption band in the visible region of the spectrum, which decays on the microsecond time scale, leading to a strong increase in absorption in the UV region of the spectrum, which is attributed to the corresponding acetophenone formed after β-scission of the cumyloxyl radicals. The position of the visible absorption band is red-shifted by the presence of electron-donating ring substituents, while a blue-shift is observed in the presence of electron-withdrawing ring substituents, suggesting that + R ring substituents promote charge separation in the excited cumyloxyl radical through stabilization of the partial positive charge on the aromatic ring of an incipient radical zwitterion. Along this line, an excellent Hammett-type correlation between the experimentally measured energies at the visible absorption maxima of the cumyloxyl radicals and σ+ substituent constants is obtained. A red-shift is also observed on going from MeCN to MeCN/H2O for all cumyloxyl radicals, pointing toward a specific effect of water. The ring substitution does not influence to a significant extent the rate constants for β-scission of the cumyloxyl radicals, which varies between 7.1 × 105 and 1.1 × 106 s-1, a result that suggests that cumyloxyl radical β-scission is not governed by the stability of the resulting acetophenone. Finally, κβ increases on going from MeCN to the more polar MeCN/H2O 1:1 for all cumyloxyl radicals, an observation that reflects the increased stabilization of the transition state for β-scission through increased solvation of the incipient acetophenone product.

Structural effects on the OH--promoted fragmentation of methoxy-substituted 1-arylalkanol radical cations in aqueous solution: The role of oxygen acidity

A kinetic and product study of the OH--induced decay in H2O of the radical cations generated from some di- and tri-methoxy-substituted 1-arylalkanols (ArCH(OH)R·+) and 2- and 3-(3,4-dimethoxyphenyl) alkanols has been carried out by using pulse- and γ-radiolysis techniques. In the 1-arylalkanol system, the radical cation 3,4-(MeO)2C6H3CH2OH ·+ decay at a rate more than two orders of magnitude higher than that of its methyl ether; this indicates the key role of the side-chain OH group in the decay process (oxygen acidity). However, quite a large deuterium kinetic isotope effect (3.7) is present for this radical cation compared with its α-dideuterated counterpart. A mechanism is suggested in which a fast OH deprotonation leads to a radical zwitterion which then undergoes a rate-determining 1,2-H shift, coupled to a side-chain-to-ring intramolecular electron transfer (ET) step. This concept also attributes an important role to the energy barrier for this ET, which should depend on the stability of the positive charge in the ring and, hence, on the number and position of methoxy groups. On a similar experimental basis, the same mechanism is suggested for 2,5-(MeO)2C6H3CH2OH ·+ as for 3,4-(MeO)2C6H3CH2OH ·+, in which some contribution from direct C-H deprotonation (carbon acidity) is possible. In fact, the latter process dominates the decay of the trimethoxylated system 2,4,5-(MeO)3C6H2CH2OH ·+, which, accordingly, reacts with OH- at the same rate as that of its methyl ether. Thus, a shift from oxygen to carbon acidity is observed as the positive charge is increasingly stabilized in the ring; this is attributed to a corresponding increase in the energy barrier for the intramolecular ET. When R = tBu, the OH--promoted decay of the radical cation ArCH(OH)R·+ leads to products of C-C bond cleavage. With both Ar = 3,4- and 2,5-dimethoxyphenyl the reactivity is three orders of magnitude higher than that of the corresponding cumyl alcohol radical cations; this suggests a mechanism in which a key role is played by the oxygen acidity as well as by the strength of the scissile C-C bond: a radical zwitterion is formed which undergoes a rate-determining C-C bond cleavage, coupled with the intramolecular ET. Finally, oxygen acidity also determines the reactivity of the radical cations of 2-(3,4-dimethoxyphenyl)ethanol and 3-(3,4-dimethoxyphenyl)propanol. In the former the decay involves C-C bond cleavage, in the latter it leads to 3-(3,4-dimethoxyphenyl) propanal. In both cases no products of C-H deprotonation were observed. Possible mechanisms, again involving the initial formation of a radical zwitterion, are discussed.

ortho-Directed metallation in the regiocontrolled synthesis of enantiopure 2- and/or 3-substituted (S)S (p-tolylsulfinyl)-1,4-benzoquinones

Enantiomerically pure (S)S-(p-tolylsulfinyl)-1,4-benzoquinones with alkyl and methoxy substituents at C-2 and/or C-3 are synthesized by CAN oxidation of adequately substituted (S)S-(p-tolylsulfinyl)-1,4-dimethoxyaromatic precursors 2 or 3. These compounds were obtained by ortho-directed metallation or bromo-metal exchange from the corresponding p-methoxyanisoles in a highly regiocontrolled manner.

Ring-substituted 1,1,2,2-tetraalkylated 1,2-bis(hydroxyphenyl)ethanes. 4. Synthesis, estrogen receptor binding affinity, and evaluation of antiestrogenic and mammary tumor inhibiting activity of symmetrically disubstituted 1,1,2,2-tetramethyl-1,2-bis(hydroxyphenyl)ethanes

The syntheses of symmetrically 2,2'-disubstituted derivatives of 1,1,2,2-tetramethyl-1,2bis(4-hydroxyphenyl)ethane (1) are and of 5,5'-, and 6,6'-disubstituted derivatives of 1,1,2,2-tetramethyl-1,2-bis(3-hydroxyphenyl)ethane (6) are described (1 and 6 are strong antiestrogens with mammary tumor inhibiting activity exhibiting only slight estrogenic properties): (2,2'-substituents) F (2), Cl (3), OCH3 (4), CH3 (5); (5,5'-substituents) Cl (7); (6,6'-substituents) F (8), Cl (9), OCH3 (10), CH3 (11). The synthesis of 1-11 was accomplished by reductive coupling of the corresponding 2-phenyl-2-propanols with TiCl3 and LiAlH4. The binding affinity of the compounds to the calf uterine estrogen receptor was measured relative to that of [3H]estradiol by a competitive binding assay. With the exception of 7 and 10 all other compounds showed relative binding affinity (RBA) values between 0.5 and 6.4% that of estradiol, 2 (RBA value 6.4), and 8 and 9 (4.0 and 3.5), exceeding those of the corresponding unsubstituted 1 and 6 (3.6 and 3.0). Compounds exhibiting RBA values of >2.5% were evaluated in the mouse uterine weight test. The substituted derivatives showed an increase in uterotrophic and a decrease in antiuterotrophic activity compared to 1 and 6. Compound 2 showed a strong, dose-dependent inhibition on the DMBA-induced hormone-dependent mammary tumor of the SD-rat, exceeding that of the parent compound 1. At a dose of 5 mg/kg per day, 2 reduced total tumor area by 47% and caused a complete remission in 74% of the tumors.

SUBSTITUTED 7,7',8,8'-TETRACYANOQUINODIMETHANES. I. METHODS OF SYNTHESIS OF SUBSTITUTED 7,7',8,8'-TETRACYANOQUINODIMETHANES

The synthesis of 2-methyl-, 2,5-dimethyl-, and 2-isopropyl-7,7'-8,8'-tetracyanoquinodimethanes was realized from 2-methyl-, 2,5-dimethyl-, and 2-isopropyl-1,4-cyclohexanediones.These cyclic diketones are obtained with good yields by the Birch reduction of 2-chloromethyl-, 2,5-dichloromethyl-, and 2-isopropyl-1,4-dimethoxybenzenes.

Phenylalkylamines with potential psychotherapeutic utility. 2. Nuclear substituted 2-amino-1-phenylbutanes

A series of 2-amino-1-(4-substituted-2,5-dimethoxyphenyl)butanes was prepared as analogues of (R)-2-amino-1-(2,5-dimethoxy-4-methylphenyl)butane (1a). 1-(2,5-Dimethoxyphenyl)-2-(N-phthalimido)butane (7) was utilized as a synthetic intermediate common to many of the target compounds. Animal data are presented indicating that most of these analogues have low hallucinogenic potential. Selected compounds were compared with 1a in an avoidance-response acquisition model which differentiates between 1a and the human hallucinogens DOM (2a) and DOET (2b). Structure-activity relationships of these analogues are discussed.