70555-95-2

Upstream product

• 118-90-1 ortho-methylbenzoic acid 
• 95280-70-9 2-[(E)-(3,4-dimethoxystyryl)]benzoic acid 
• 27326-44-9 methyl o-vinylbenzoate 
• 71435-93-3 o-<(trimethylsilyl)methyl>benzoic acid 
• 120-14-9 3,4-dimethoxy-benzaldehyde 
• 89-51-0 Homophthalic acid 
• 22073-92-3 3-(3,4-dimethoxyphenyl)-1H-isochromen-1-one 
• 7115-91-5 2-ethoxycarbonylbenzyl bromide 
• 33863-57-9 2-(3',4'-dimethoxybenzoylmethyl)benzoic acid 
• 78752-29-1 o-<(trimethylsilyl)methyl>benzoyl chloride 

Relevant academic research and scientific papers

Reactivity of Anodically Generated 4-Methoxystilbene Cation Radicals: The Influence of Ortho-Substituted Hydroxymethyl, Aminomethyl, and Carboxylic Acid Groups

The effect of ortho′-substituted side chains bearing nucleophilic groups such as CH2OH, CH2NHR, and CO2H on the reactivity of anodically generated 4-methoxy- and 3,4-dimethoxystilbene cation radicals was investigated, and results were compared with those of substrates where the nucleophilic groups such as OH and NHR are directly attached to the aromatic ring. It was found that when ortho′-substituted groups such as CH2OH or CH2NHR are present in the other ring, only direct intramolecular cation-nucleophile reactions occur to give bisbenzopyrans or bisisoquinolines. Crossover products (previously obtained when the ortho′ substituents were OH and NH2) such as the fused benzoxepanes/fused benzoazepanes were not formed. When the ortho′ substituent is COOH, direct intramolecular cation-nucleophile reaction occurs to give the corresponding bis-δ-lactones in high yield. The presence of an additional 3-methoxy substituent resulted in the formation of other fused polycyclic products due to competing aromatic substitution reactions. Reaction pathways leading to the different products and reasons for the difference in behavior shown by the present stilbenes are presented. The results have provided additional insight into the reactivity and behavior of anodically generated stilbene cation radicals.

Synthesis and application of benzyl-TMS derivatives as bench stable benzyl anion equivalents

The regioselective benzylic metalation of toluenes using BuLi/KO tBu/TMP(H) (LiNK metalation conditions) and subsequent transmetalation to Si by reaction with TMSCl provides a general one-pot procedure for the synthesis of substituted benzyltrimethylsilanes. ArCH 2Si(Me)3 derivatives are bench stable reagents yet can serve as benzyl anion equivalents under mild reaction conditions. Following activation with fluoride they can successfully participate in a wide range of additions to both non-enolizable and enolizable carbonyls. In addition, their use in the synthesis of isochromanones and trifluoromethylated amines is illustrated. The broad synthetic scope and mild practical conditions of use for ArCH2Si(Me)3 reagents demonstrate their general potential as benzyl anion equivalents.

Titanocene(III) chloride mediated radical-induced synthesis of 3,4-dihydroisocoumarins: synthesis of (±)-hydrangenol, (±)-phyllodulcin, (±)-macrophyllol and (±)-thunberginol G

A radical-promoted synthesis of 3,4-dihydroisocoumarins has been achieved in moderate to good yields using titanocene(III) chloride (Cp2TiCl) as the radical initiator. The total synthesis of four naturally occurring dihydrocoumarins hydrangenol, phyllodulcin, macrophyllol and thunberginol G has been accomplished using the radical technology. Cp2TiCl was prepared in situ from commercially available titanocene dichloride (Cp2TiCl2) and Zn-dust in THF under argon.

Radical-mediated synthesis of 3,4-dihydroisocoumarins: total synthesis of hydrangenol

A radically promoted synthesis of 3,4-dihydroisocoumarins has been achieved in moderate to good yields using titanocene(III) chloride (Cp2TiCl) as the radical initiator. The total synthesis of (±)-hydrangenol has been completed using this radical technology. Cp2TiCl was prepared in situ from commercially available titanocene dichloride (Cp2TiCl2) and Zn-dust in THF under argon.

Synthesis of 8-desoxythunberginol A and (±)-8-desoxy-3,4- dihydrothunberginol A

A two step synthesis of title isocoumarin isolated from Homalium longifolium and its conversion into corresponding 3,4-dihydroisocoumarin has been described. 3,4-Dimethoxybenzoyl chloride on condensation with homophthalic acid afforded 3-(3′,4′-dimethoxyphenyl)isocoumarin which was demethylated to furnish the 8-desoxythunberginol A, whereas its sequential saponification, reduction and demethylation yielded the (±)-8-desoxy-3,4- dihydrothunberginol A. The synthesized compounds were examined in vitro for antibacterial activity.

Synthesis of 3-aryl- and 3-aryl-3,4-dihydroisocoumarins

The condensation of homophthalic acid 6 with the appropriate acid chlorides 7a-c yield the respective isocoumarins 8a-c, which are converted to keto-acids 9a-c by alkaline hydrolysis. The 3,4-dihydroisocoumarins 12a-c are obtained by reduction of the keto

Reactions of dianions derived from o-toluic acids: Facile synthesis of 3-phenyl-3,4-dihydroisocoumarins and 8-oxotetrahydroprotoberberines

o-Toluic acids have been dideprotonated by treatment with LDA or n-butyllithium in THF at -78 deg C.The obtained dianions heve been reacted with aromatic aldehydes and 3,4-dihydroisoquinolines to get dihydroisocoumarins and 8-oxotetrahydroberberines, respectively.

Facile Generation and Trapping of α-Oxo-o-quinodimethane; a Synthesis of 3-Aryl-3,4-dihydroisocoumarins

Treatment of o-(trimethylsilylmethyl)benzoyl chloride (1) with fluoride ions in the presence of aromatic aldehydes and alkyl fumarates gives 3-aryl-3,4-dihydroisocoumarins (3) and substituted α-tetralones (4), respectively.