Bromoacetyl reactions

Chromone, 2-amino-3-chloro-synthesis, 3, 713 diacetate, 3, 714 Chromone, 3-aroyl-photochemistry, 3, 695 Chromone, 2-benzhydryl-3-benzoyl-photoenolization, 3, 695 Chromone, 3-benzoyl-2-benzyl-photoenolization, 3, 695 Chromone, 3-benzoyl-2-methyl-synthesis, 3, 823 Chromone, 2-benzyl-in photochromic processes, 1, 387 Chromone, 3-benzyl-photolysis, 3, 695 Chromone, 3-bromo-synthesis, 3, 828 Chromone, 3-bromoacetyl-ring opening, 3, 713 Chromone, 3-bromo-2-methyl-reactions... 

Chloro-2,3,4,4fl,5,6-hexahydro-l //-pyrazino[l, 2-fl]quinolin-2-one (407) was prepared when 6-chloro-2-[A -(2-bromoacetyl),-A -(rerf-butoxycarbonyl) aminomethyl]-l,2,3,4-tetrahydroquinoline (406) was first treated with TFA, then the evaporated reaction mixture was heated in DMF in the presence of powdered K2CO3 (96USP5576319). 

Bromoacetyl fluoride, 46, 6 Bromobenzene, reaction with potassium f-butoxide, 46, 89... 

The reaction of methyl 2-[benzyl(bromoacetyl)amino]benzoate with ammonia yields the benzo-diazepinedione 32.209... 

On the other hand, refluxing 9 in formic acid for 5 h afforded the N-formyl derivative 11 in high yield. Acetylation of 9 by refluxing in acetic acid, afforded acetic acid N -(2-(7-hydroxy-2-oxo-2H-chromen-4-yl)-acetyl)-hydrazide 12 in good yield. Compound 13 was also obtained by refluxing 9 with 3-(2-bromoacetyl)-4-hydroxy-2H-chromen-2-one in ethanol. Reaction of compound 9 with phenyl isothiocyanate in ethanol at room temperature gave 4-phenyl-1 - (7-hydroxy-2-oxo-2 H-chromen-4-acetyl- )thiosemicarbazide 14. 

Pyranopyrroloimidazoles have been prepared stereospecifically by an intramolecular 1,3-dipolar cycloaddition reaction. Either enantiomer of the imidazoline derivative 176 (the -enantiomer is shown) may react with the bromoacetyl-containing acrylate dipolarophile 177, in the presence of l,8-diazabicyclo[5.4.0]undec-7-ene (DBU), to give the diastereomerically pure tricyclic product 178 in moderate yield (Equation 15). This reaction involves quaternization of the imidazole N, reaction of the quaternary salt with base to give the 1,3-dipole, which can then react, intramolecularly and stereospecifically, with the tethered dipolarophile <1997TL1647>. 

Thiazolonaphthyridinium salts 331 can be produced either by bromination of the 2-alkenylpyridine precursor, or by thermal cyclization of the 2-(bromoacetyl)pyridine (Scheme 81) <1997CL1203>, and reaction of the pyrano-pyrimidine 332 with o-aminothiophenol gives the benzothiazole-fused pyridopyrimidinedione 333 (Equation 118) <2003JCCS887>. 

Although the primary utility of active halogen compounds is to modify sulfhydryl groups in proteins or other molecules, the reaction is not totally specific. Iodoacetyl (and bromoacetyl) derivatives can react with a number of functional groups within proteins the sulfhydryl group of cysteine, both imidazolyl side chain nitrogens of histidine, the thioether of methionine, and... 

A frequently used strategy to couple peptides to the surface of liposomes consists in the use hydrophobic/amphipathic anchors that are functionalized with maleimide or bromoacetyl groups, i.e., thiol-reactive functions, which give by reaction with HS-peptides very stable thioether linkages. These functions are conveniently introduced into hydrophobic anchors such as phospholipids, e.g., PE (9,10), the adjuvant PamsCAG (11) or cholesterol... 

Scheme 19 Segment Synthesis by Reaction of a Peptide Thioacid with a Bromoacetyl Peptidel1001...

Haloacetyl Method The haloacetyl method uses supports that contain lodoacetyl or bromoacetyl groups for the immobilization of ligands through sulfhydryl residues. These supports are usually prepared via the reaction of an amine-containing material with iodoacetic or bromoacetic acid in the presence of ethyldimethylaminopropyl carbodii-mide (EDC) at pH 4 to 5. EDC reacts with the carboxylic acid in iodo- or bromoacetic acid... 

Protection of the secondary alcohol as the corresponding methoxy methyl (MOM) ether, followed by removal of the Boc group with ZnBr2 in dichloromethane and acylation of the incipient secondary amine with bromoacetyl bromide in the presence of K2CO3 afforded the bromoacetamide 114 in 86% yield from 113. Treatment of 114 with methanolic ammonia afforded the corresponding glycinamide which was directly subjected to cyclization in the presence of NaH in toluene/HMPA to afford the bicyclic compound 115 in 79% overall yield from 114. Next, a one-pot double carbomethoxylation reaction was performed by the sequencial addition of n-BuLi in THF followed by addition of methylchloroformate, that carbomethoxylated the amide nitrogen atom. Subsequent addition of four equiv of methyl chloroformate followed by the addition of 5 equiv of LiN(TMS)2 afforded 116 as a mixture of diastereomers in 93% yield that were taken on directly without separation. 

Thorpe-Ziegler synthesis of 3-aminoindoles with additional functional groups was used as part of the synthesis of condensed indoles [e.g., azepines (94) were obtained from 3-amino-2-benzoylindoles (93) (91JHC379) (Scheme 24)]. In these cases the nature of the substituent R is important for a smooth reaction (Ac < Bz < 2-N02-benzoyl, but no reaction when R = H). With 2-chloro-3-(/V-bromoacetyl-/V-methylamino)pyridine and o-benzoylaminobenzonitriles (95), the condensed pyridodiazepinones 97 and 99 (95H753) were obtained via intermediates 96 and 3-aminoindoles intermediate (via 98) 3-aminoindoles followed by substitution of the 2-chloro substituent by the resulting 3-amino group (Scheme 25). 

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