14003-77-1

Upstream product

• 7429-37-0 trans-1,2-dibromocyclohexane 
• 139-02-6 sodium phenoxide 
• 822-67-3 Cyclohex-2-enol 
• 108-95-2 phenol 
• 1521-51-3 rac-3-bromocyclohexene 
• 1165952-91-9 cyclohexa-1,3-diene 
• 76644-52-5 rac-3-acetoxycyclohexene 
• 5614-35-7 3-phenoxycyclohexene 

Downstream Products

• 13524-79-3 1,2,3,4,4a,9b-hexahydrodibenzo[b,d]furan 
• 13130-19-3 1,2,3,4-tetrahydrodibenzo[b,d]furan 
• 56821-94-4 (4aS,9bS)-1,2,4a,9b-Tetrahydro-dibenzofuran 
• 13524-72-6 1-(2-hydroxyphenyl)cyclohexene 
• 27124-70-5 1-(cyclohex-2-enyl)-2-methoxybenzene 
• 59457-19-1 (2-cyclohex-2-enyl-phenoxy)-acetic acid 

Relevant academic research and scientific papers

Gold catalysis: Experimental mechanistic insights into the anellation of phenols with 1,3-dienes Dedicated to Prof. Hubert Schmidbaur on the occasion of his 80th birthday.

An intermediate of the anellation reaction of phenols and 1,3-dienes could be detected, isolated and characterized as the hydroarylation product. The other conceivable intermediate, the hydroaryloxylation product, was prepared via Pd-catalysis and converted under the conditions of the gold catalysis, too. Under exactly the same conditions a very fast Claisen rearrangement took place delivering the formal hydroarylation product as well. After this fast intermolecular formation of the intermediate (formed either directly via the hydroarylation pathway or via a hydroaryloxylation/Claisen rearrangement sequence) the subsequent intramolecular reaction leading to the product turned out to be significantly slower. The major product is the cis-diastereomer (cis-3/trans-3 = 12:1).

Rearrangements of Cycloalkenyl Aryl Ethers

Rearrangement reactions of cycloalkenyl phenol and naphthyl ethers and the acid-catalyzed cyclization of the resulting product were investigated. Claisen rearrangement afforded 2-substituted phenol and naphthol derivatives. Combined Claisen and Cope rearrangement resulted in the formation of 4-substituted phenol and naphthol derivatives. In the case of cycloocthylphenyl ether the consecutive Claisen and Cope rearrangements were followed by an alkyl migration. The mechanism of this novel rearrangement reaction is also discussed.

Synthesis and inhibitory evaluation of cyclohexen-2-yl- and cyclohexyl-substituted phenols and quinones to endothelial cell and cancer cells

Alkylation of phenols with 1,3-cyclohexadiene (1) has been conducted and a series of cyclohexen-2-yl- and cyclohexyl-substituted phenols and quinones were screened against the proliferation of HUVEC and cancer cells. Phenol type as well as the size and occupied position of the substitute are important for the alkylating reaction and the inhibitory activity and selectivity of a compound. 2,5-Di(cyclohexen-2-yl)benzene-1,4-diol (25) bearing two cyclohexen-2-yl groups and 2-tert-butyl-5-(cyclohexen-2-yl)benzene-1,4-diol (30) bearing cyclohexen-2-yl and tert-butyl groups exhibited good selectivity against HUVEC proliferation (IC50s of 2.0 and 1.4?μM, respectively) with relatively low toxicity to ccc-HPF-1.

Calcium-catalyzed friedel-crafts alkylation at room temperature

Chemical Equatation Representation A novel calcium catalyst was found to efficiently functionalize electron-rich arenes with secondary and tertiary benzylic, propargylic, and allylic alcohols under very mild reaction conditions. The new catalyst system significantly enlarges the scope of the reaction, which was previously limited except for the few examples with secondary benzylic alcohols.

Photogeneration of o-Quinone Methides from o-Cycloalkenylphenols

6-Alkylidenecyclohexa-2,4-dienones (o-quinone methides II) have been generated by photolysis of 2-(2′-cycloalkenyl)phenols 1 and trapped by methanol to give the ring-opened products 2. The best results have been obtained with the cyclohexenyl derivatives 1a, 1e, and 1f. In the case of the cyclopentenyl derivative 1b, photoproduct 2b was not observed, whereas only small amounts of 2c and 2d were formed from the seven- and eight-membered ring analogues 1c and 1d. Thus, ring size appears to be a key factor in the formation of o-quinone methides. This experimental result has been rationalized by means of density-functional theory (DFT) calculations. On the other hand, phenol substitution also appears to play a role in the process. Thus, electron-withdrawing groups such as CF3 (1f) accelerate the reaction, whereas the opposite is true for electron-donating groups such as OCH 3 (1e). This is explained by an excited-state intramolecular proton transfer (ESIPT) mechanism, as the above results are consistent with the excited-state acidities of the different phenols. The lack of reactivity in the case of ketone 1g, where the intersystem crossing quantum yield is close to unity, allows us to rule out a mechanism involving the triplet state.

Molybdenum(II)-catalyzed allylation of electron-rich aromatics and heteroaromatics

The stable, readily available molybdenum(II) complexes [Mo(CO)4Br2]2 (B) and Mo(CO)3(MeCN)2-(SnCl3)Cl (C) have been found to catalyze C-C bond- forming allylic substitution with electronrich aromatics (e.g., 15 + PhOMe → 62) and heteroaromatics (e.g., 15 + 36 → 88) as nucleophiles under mild conditions (room temperature, 30 min-3 h). Remarkable is the para-selectivity for anisole, whereas phenol tends to favor ortho-substitution in certain instances. Mechanistic and stereochemical experiments are indicative of Lewis-acid catalysis rather than a metal template-controlled process.

Hydroalkylation of Phenol to Cyclohexylphenyl in the Presence of Pd-Al2O3 and NaCl-AlCl3 under Hydrogen Pressure

The hydroalkylation of phenol (1) in the presence of palladium catalyst and fused salt (NaCl-AlCl3) under hydrogen pressure was carried out.By using 1percent Pd-Al2O3 (1g) and the fused salt (1:1 mol ratio, 6g), 4-cyclohexyphenol (6) was obtained selectively from 1 (30g) in a yield of 31.9 percent at 120 deg C for 4.5 h.Cyclohexylphenols were formed by way of 2-cyclohexen-1-ol and 1.Keywords-hydroalkylation; palladium catalyst; fused salt; phenol; 2-cyclohexylphenol; 4-cyclohexylphenol; 2-cyclohexylcyclohexanone

REACTION OF PHENOL WITH 1,3-CYCLOHEXADIENE IN THE PRESENCE OF ALUMINUM PHENOLATE

The controlled synthesis of 2- and 2,6-di(2-cyclohexenyl)phenols was realized by the cycloalkenylation of phenol with 1,3-cyclohexadiene in the presence of aluminum phenolate.Alkenylation is accompanied by intramolecular cyclization of the cyclohexenylphe