Ethyl amines, 2-bromo

The synthesis of quinapril begins with formation of the AT-carboxyalkyl alanine intermediate 26 (Scheme 10.6) (Hoefle and Klutchko, 1982 Kaltenbronn et al., 1983 Klutchko et al., 1986). Displacement of ethyl-2-bromo-4-phenylbutanoate (24) by (S)-alanyl-tert-butyl ester provided the secondary amine as a diastereomeric mixture. Deprotection of this mixture allowed for the selective recrystalhzation of the undesired (/ ,S)-isomer, and isolation of the desired (6,6)-isomer 26 from the mother liquor. 

Macrocycle LXXXVIII was prepared (13) in an 8% yield from the reaction of the disodium salt of ethane-1,2-dithiol with di(2-bromo-ethyl)amine in ethanol at high dilution, and it was found to complex with Ni(II) and Co(II) ions when these were added as salts. A macrocycle containing the same donor atoms (LXXXIX) has been obtained in the form of complexes (87) by the template reactions of l,2-bis(2-aminophenylthio)ethane and 1,4-bis (2-formylphenyl)-1,4-dithiabutane with Ni(II) and Co(II) perchlorates. Iron, cobalt, nickel, and zinc as their M(II) perchlorates have been used as templates in the formation of XC (55, 133). 

The Reformatsky reaction between 2-allylcycZohexanone and ethyl a-bromo-/3-phenylpropionate yielded the acid [l], which on cyclization gave two acids, one of which was the expected 13-allyl-derivative [li]. The other acid did not react with bromine and was allotted the structure [l 11 ] on Curtius degradation it afforded the amine [liii]. The acid [in] was recovered mainly unchanged after heating with spongy palladium at 310° C. for one hour [21]. 

Despite the large numbers of water-soluble monomers that can be polymerized by ATRP, several problems remain to be solved. For example, Brittain et al. [217] have shown that the aqueous polymerization of 45 (DMA), catalyzed by CuBr/L (L= HMTETA, tris[2-(dimethylamino)ethyl]amine (Meg-TREN) and 1,4,8,11-tetra-methyl-1,4,8,11-tetraazacyclotetradecane (Me4Cyclam)) is not controlled because of the slow but irreversible decomposition of the bromo-terminated end-group of the dormant chains. Aqueous polymerization of acryhc [199] and styrenic monomers [203] also appears to be difficult to control, as imphed by the rarity of known examples. 

Bordwell et a/.354 358 have made an extensive study of the rearrangement reactions brought about by nucleophilic attack on a range of substituted halogenobenzo[b]thiophene-1,1-dioxides. 3-Chloromethyl- and 2-bromo-3-methylbenzo[b]thiophene-l,1-dioxide each give the same product with piperidine, the structure of which (Ref. 2, p. 358) has now been amended to 84 (R1 = R2 = H). With piperidine, 2-bromo-3-ethyl- and 2-ethyl-3-bromo-benzo[/>]thiophene-l,1-dioxides give amines 82a and 82b, respectively.354... 

Another route converted ethyl co-bromocaproate (ethyl 6-bromohexanoate, 1.148) to ethyl 7-bromo-8-oxo-nonanoate, 1.149. The bromide was displaced by phthal-imide and later unmasked to an amine. The ketone moiety in 1.149 was converted to... 

Under the protection of nitrogen, the substrate 2-bromo-6-methyl phenol (30.0 g, 160 mmol) and diisopropyl ethyl amine (82.9 mL, 480 mmol) were added to 0 °C dichloromethane (600 mL). Under the stirring condition, MOMCl (18.1 g, 240 mmol) was added, heated to room temperature, and reacted for 3 h. TLC showed that the reaction was completed. 1 N diluted hydrochloric acid (200 mL) was slowly added drop wise at 0 °C to adjust pH = 7. Dichloromethane (200 mL) was added to the system. The aqueous phase was extracted with dichloromethane (3 X 200 mL). The organic phases were combined, washed with saturated brine (200 mL), dried over anhydrous sodium sulfate, and hltered. The hltrate was concentrated under reduced pressure. The resulting crude product was separated and purihed by hash column chromatography (PE/EA = 100 1) to give 32 g colorless liquid Rf— 0.80, PE/EA = 10 1), 89 % yield. 

C3 6H3i,Br2N20i2 CsHgO, 1-( 4-Bromo-2,6-dimethylphenyl)-2- (4-bromo-2,6-dimethylphenyl)imino-1,2-dihydro-3,4,5,5,6,7-hexacarbomethoxy-5h-1-pyrindine (acetone solvate), 37B, 144 CagHaeNiiOa 2 H2O, Tris[ (2-methyl-8-guinolyloxy)ethyl]amine dihydrate, 46B, 267... 

Fig. 2. Structures of live pH sensors (upper) and PET principle of sensors off-on (bottom). 1 N-(l-bromo-2-naphthylmetliyl) diethanolamine 2 iV-(l-bromo-2-naphthylmethyl)bis(2-chloro-ethyl)amine 3 iV-(l-bromo-2-naphthylmethyl)bis(2-bromoethyl)amine 4 Al-(l-bromo-2-naph-thylmethyl)bis(2-iodoethyl)amine 5 A/, Af -bis(l-bromo-2-naphthylmethyl)diaza-18-crown-6.

Purine, 6-bromo-9-/3-D-(2,3,5-tri-0-acetyl)ribofuranosyl-synthesis, 5, 598 Purine, 6-carboxy-reactions, 5, 549 Purine, 8-carboxy-reactions, 5, 549 Purine, 2-chloro-reactions, 5, 561 synthesis, 5, 597 Purine, 6-chloro-alkylation, 5, 529 glycosylation, 5, 529 oxidation, 5, 539 3-oxides reactions, 5, 554 synthesis, 5, 595 reactions, 5, 561, 595 with ammonia, 5, 562 with fluorides, 5, 563 with trimethylamine, 5, 562 9- -D-ribofuranoside synthesis, 5, 560 synthesis, 5, 597, 598 Purine, 8-chloro-amination, 5, 542 Purine, 6-chloro-8-ethoxy-synthesis, 5, 591 Purine, 6-chloro-9-ethyl-dipole moment, 5, 522 Purine, 6-chloro-2-fluoro-riboside... 

The chemistry of indium metal is the subject of current investigation, especially since the reactions induced by it can be performed in aqueous solution.15 The selective reductions of ethyl 4-nitrobenzoate (entry 1), 2-nitrobenzyl alcohol (entry 2), l-bromo-4-nitrobenzene (entry 3), 4-nitrocinnamyl alcohol (entry 4), 4-nitrobenzonitrile (entry 5), 4-nitrobenzamide (entry 6), 4-nitroanisole (entry 7), and 2-nitrofluorenone (entry 8) with indium metal in the presence of ammonium chloride using aqueous ethanol were performed and the corresponding amines were produced in good yield. These results indicate a useful selectivity in the reduction procedure. For example, ester, nitrile, bromo, amide, benzylic ketone, benzylic alcohol, aromatic ether, and unsaturated bonds remained unaffected during this transformation. Many of the previous methods produce a mixture of compounds. Other metals like zinc, tin, and iron usually require acid-catalysts for the activation process, with resultant problems of waste disposal. 

A variety of cleavage conditions have been reported for the release of amines from a solid support. Triazene linker 52 prepared from Merrifield resin in three steps was used for the solid-phase synthesis of aliphatic amines (Scheme 22) [61]. The triazenes were stable to basic conditions and the amino products were released in high yields upon treatment with mild acids. Alternatively, base labile linker 53 synthesized from a-bromo-p-toluic acid in two steps was used to anchor amino functions (Scheme 23) [62]. Cleavage was accomplished by oxidation of the thioether to the sulfone with m-chloroperbenzoic acid followed by 13-elimination with a 10% solution of NH4OH in 2,2,2-trifluoroethanol. A linker based on l-(4,4 -dimethyl-2,6-dioxocyclohexylidene)ethyl (Dde) primary amine protecting group was developed for attaching amino functions (Scheme 24) [65]. Linker 54 was stable to both acidic and basic conditions and the final products were cleaved from the resin by treatment with hydrazine or transamination with ra-propylamine. 

Serine has been prepared by the Strecker method from glycol-aldehyde 1 and from ethoxyacetaldehyde,2 3 by the condensation of ethyl formate with ethyl hippurate followed by reduction and hydrolysis,4 5 from the reaction product of chloromethyl ether with ethyl sodium phthalimidomalonate,6 and by amination of a-bromo-/3-methoxypropionic acid with subsequent demethyla-tion.7... 

The Curtius rearrangement provides a route to carbamates of a-amino sulfonamides (Scheme 25). 108 Reaction of the ethyl ester of an a-bromo acid 52 with Na2S03 yielded the sodium salt of the corresponding sulfonic acid 53. Treatment of 53 with PQ5 afforded the sulfonyl chloride 54 which on reaction with an amine gave the sulfonamide 55. The latter... 

Amine Bis-[trifluoromethyl]-(2-bromo-2-fluoro-ethyl)- EI0b2. 06 (Educt)... 

Gomberg and Pemert4 recommended the use of the sodium diazotates for the preparation of biaryls from aniline and from p-toluidine and the normal diazo method for negatively substituted amines such as the bromo- and nitro-anilines. Grieve and Hey 7 found little difference in the yields of biaryls obtained by the two procedures when they coupled diazotized aniline with six different components benzene, toluene, m-xylene, chlorobenzene, nitrobenzene, and ethyl benzoate. Where it is applicable, this modification offers the advantage that the dropwise addition of alkali is eliminated. 

Note. Only a one-pot indirect aminolysis has been reported. 3-Bromo-5-ethyl-l,6-naphthyridin-2( l//)-one (19) gave 3-bromo-5-ethyl-l,6-naphthyridin-2-amine (20) (POCl3, reflux, 16 h crude chloro compound NH3/EtOH, 100°C, sealed, 16 h 92% analogs likewise).590... 

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