Reactions of heterocycles with thiophosgene. Part IV. β,4-Dichloro-2-isothiocyanatocinnamaldehyde, a product from 4,7-Dichloroquinoline

Abstract

c=s(conj. CHO), and the n.m.r. spectra showed the aldehyde proton signal as a doublet ( J 4 Hz) at T ca. 0.1 coupled to the vinyl proton (d, J 4 Hz) at 7 ca. 3.2.2-Aminopyridine yielded the expected product (17) together with 4,7-dichloroquinoline. P-Aminoethanol

Total synthesis of (+)‐vinblastine: Control of the stereochemistry at C18′

“…The indole unit 25 was derived from 7‐mesyloxyquinoline ( 36 ) utilizing a novel indole synthesis developed in our laboratory (Scheme ) 19. Quinoline ring opening with thiophosgene,20 followed by addition of malonate into the resulting isothiocyanate 37 delivered thioanilide 38 . Radical cyclization of 38 smoothly proceeded to furnish an indole, which underwent a decarboxylative Mannich reaction to convert the malonate moiety into an acrylate moiety, resulting in the production of indole unit 25 .…”

Recent Advances in the Synthesis of Thienoquinolines (Quinoline‐fused heterocycle)

“…The compound 1 underwent intermolecular dealkylation with methyl‐ether by sodium ethanethiolate, resulted in 7‐Chloro‐4‐methoxy‐thieno[2,3‐ b ]quinoline‐2‐carboxylate 2 in moderate yields [12] . (Scheme 1) Afterwards, they functionalized the 4‐methoxy‐group of compound 2 with 2‐diethylaminoethylamine by nucleophilic displacement to afford amino‐amide derivative 3 , further addition of hydrazine in benzene alcohol to provide hydrazine‐derivative 4 .…”

“…For instance, in 1970s, Hull and co-workers have reported an efficient synthesis of varied heterocyclics, including thieno [b] quinolines via intramolecular alkylation with methyl chloroacetate using 7-chloro-1,2-dihydro-4-methoxy-2-thioxoquinoline-3carbaldehyde as a starting precursor. [12] Almost simultaneously, In 1976, Shanmugam and co-worker described the synthesis of thieno[b]quinolines via hydrobromination using a similar substrate by the Hull group. [13] In addition, they reported thieno [b] quinolines from other substrates using 2-chloro-3-vinylquinolines, and 3-vinylquinoline-2(1H)-ones in good to excellent yields.…”

“…There are sizeable effects have been made for the synthesis of thienoquinoline by various research groups. For instance, in 1970s, Hull and co‐workers have reported an efficient synthesis of varied heterocyclics, including thieno[b]quinolines via intramolecular alkylation with methyl chloroacetate using 7‐chloro‐1,2‐dihydro‐4‐methoxy‐2‐thioxoquinoline‐3‐carbaldehyde as a starting precursor [12] . Almost simultaneously, In 1976, Shanmugam and co‐worker described the synthesis of thieno[ b ]quinolines via hydrobromination using a similar substrate by the Hull group [13] .…”

Studies toward the Synthesis of Lepadiformine A

“…■ EXPERIMENTAL SECTION 7-Chloro-4-methoxyquinoline (10). 29 Sodium metal (2.38 g, 103 mmol) was slowly added to methanol (50 mL) at −30 °C with stirring. The reaction was stirred at room temperature for 18 h. A solution of 4,7-dichloroquinoline (4.04 g, 20.4 mmol) in 5 mL of methanol was added to the sodium methoxide solution, and the mixture was heated to reflux for 24 h. The excess methanol was removed via distillation or rotary evaporation.…”