L-bromo-7-methoxy

Benzene, bromo, 55, 51 Benzene, 1 -bromo4-chloro, 55, 51 Benzene, 4-bromo-l,2-dimethyl-, 55, 51 Benzene, l-bromo-4-fluoio-, 55, 51 Benzene, l-bromo-4-methoxy-, 55, 51 Benzene, 1-bromo-3-methyl-, 55, 51 Benzene, l-bromo-4-methyl- [Toluene, 4-bromo-], 55, 49... 

The reaction of 1-alkoxynaphtalenes with copper (II) bromide in benzene produced a mixture of 4-bromo-1-alkoxynaphtalenes and 4,4 -dialkoxy-l,l -binaphtyls. For instance, the reaction of 1-methoxynaphtalene 4 with copper(II) bromide in refluxing benzene for 2 h. gave a mixture of 4-bromo-1-methoxy-naphtalene 5 (47 %) and 4,4 -dimethoxy-l,l -binaphtyl 6 (45 %). In contrast, in similar reaction using alumina-supported copper(II) bromide at 30°C, only dimerization occurred and no brominated compounds were obtained. 

Bromo-l-phthalimidopentane 3 was obtained in 72-82 g yield by refluxing 92 g of 1,4-dibromopentane 1, 55.5 g of potassium phthalimide 2, and 200 mL dry acetone on a steam bath for 30 h. Compound 3 (30 g) and 42 g 6-methoxy-8-aminoquinoline 4 refluxed at 130-135 °C for 6 h, extracted with benzene to separate insoluble 6-methoxy-8-aminoquinoline hydrobromide, the residue from evaporation of the benzene was refluxed with stirring with 100 mL of an alcoholic solution of 6 g hydrazine hydrate for 4 h, the solution was concentrated, made acidic to Congo red with 8 N hydrochloric acid, filtered, and washed with boiling water. The combined filtrate and washings was concentrated, made alkaline, extracted with benzene, and distilled in vacuo to give 20.5 g primaquine 6, which was treated with 19 mL 85% phosphoric acid in absolute ethanol, formed 42.5% primaquine diphosphate. 

Primaquine Primaquine, 8-[(4-amino-l-methylbutyryl)amino]-6-methoxyquinoline (37.1.2.4), is made from 6-methoxy-8-nitroquinoline (37.1.2.1), which is synthesized in a Skraup reaction from 4-methoxy-2-nitroaniline and glycerol in the presence of sulfuric acid. The nitro group in this compound is reduced to make 6-methoxy-8-aminoquinoline (37.1.2.2). Alkylating the amino group with 4-bromo-l-phthalimidopentane gives 8-[(4-phthalimido-l-methylbutyryl)amino]-6-methoxyquinoline (37.1.2.3), the hydrazi-nolysis of which removes the phthalimide protection, giving primaqnine [28,29]. 

Benzaldehyde, 4-ethoxy-3-methoxy-, 56, 44 Benzaldehyde, 4-ethoxy-3-methoxy-, ethylene acetal, 56, 44 Benzaldehyde, 4-isopropyl-, 55,10 Benz[e ] anthracene, 58, 15, 16 BENZENAMINE, 4-bromo-Ar, V-dimcthyl-3-(tnfluoromethyl)-, 55, 20 Benzene, bromo-, 55,51 Benzene, 1 bromo-4-chloro-,55, 51 Benzene, 4-bromo-l, 2-dimethyl, 55, 51 Benzene, l-bromo-4-fluoro-, 55, 51 Benzene, 1 -bromo-4-methoxy-, 55,51 Benzene, l-bromo-3-methyl-, 55, 51 Benzene, 4-(cr/-buty 1-1-ethyl, 55, 10 Benzene, chemical hazard warning, 58, 168 Benzene, chloro-,56, 86 Benzene, l-ethyl-4-isopropyl-, 55, 10... 

The bromine group in 4-bromo-5-methoxy-2-trifluoromethyl-l,10-phenanthroline has been replaced by lithium with w-butyllithium and the lithio derivative reacted with pyridine 2-aldehyde.215... 

Bromo-3,4-dimethyl-l-methoxy-carbonyl- 151 Bieyclo 3.3.0Joct-2-ene... 

Bis-[chloromcthyl]-2, 2 -dichloro- 646 2-Bis-[4-methoxy-phenyl]- 1699 2-Bis-[4-methyl-phenyl]- 1699 l -Bis-[trimethylsilyl]- 1691 (Bis-[triphenylphosphan]-chloro-nickelo)-2,2,2, 2 -tetramethyl- 225 3 (or 3,3 )-Bis-[trimethylsilyl]-2,2 -dichloro- 2710 Bromo- 1443 Bromo-l-methoxy- 1508 Bromo-1-methoxy- 1508 Bromo-1-methyl- 1271 Bromo-1-methyl- 1271, 2699 Chloro- 946 Chloro-l-cyano- 558 Chloro-1, 2-dimethyl- 550 Chloro-2,2(or 2,3)-dimethyl- 558, 559 Chloro-3-ethyl-2-methyl- 558 Chloro-l-methyl- 2699 Chloro-2-methyl- 551 Chloro-2,2,2 -trimethyl- 558 Chloro-2,2,3,3-tetramethyl- 558, 559 ( 1 -Cyclopentenyl)-1 -methoxy- 1889 2 -Dibromo-2,2-dichloro-l-methyl- 2194, 2 -Dibromo-l,r-dimethyl- 2700 (2,2-Dibromo-cthcnyl)-2-phcnyl- 1792, 2-Dibromo-l-methyl- 1271 (Dibromomethylen)-l-methyl- 2302, 2-Dibromo-l-methyl-3-methylen- 2302, 2 -Di-tcrt.-butyl-2,2 -dimethyl-3,3.3, 3 -tetra-bromo- 2413... 

Several other examples of stereoselective synthesis of polycyclic ketones, via carbonylative [2 + 2 + 1] cycloaddition of organopalladium compounds derived from norbornene and norbor-nadiene, have been reported53,54,121. These reactions are useful in the synthesis of cyclopen-tanoid compounds, such as dihydrojasmone54 The nickel-catalyzed version of this method was used in a total synthesis of methylenomycin B55 and in the stereoselective synthesis of bicy-clo[3.3.0]oct-l-en-3-one derivatives56. Thus, (E)- or (Z)-9-bromo-l-methoxy-7-nonen-2-yne (5), upon intramolecular carbonylative cyclization promoted by tetracarbonyl nickel, afford the same stereoisomer of methyl 1,2,4,5.6,6a-hexahydro-3-methoxymethyl-2-oxo-l-pentaleneac-etate (6) in 43-50% yield with a relative trans configuration of the H-l and H-6a protons. 

A solution of 0.84 mL (64 mmol) of tetracarbonylnickel in 4 mL of hexane is added dropwise to a solution of ( )- or (Z)-9-bromo-l-methoxy-7-nonen-2-yne (5) in 15 mL of CH,OH and the reaction mixture is kept at 15 rC for 10 h. Then the temperature is raised to 40 C for 1 h. Elimination of excess tetracarbonylnickel is carried out by flushing with N2 (caution ) while the temperature is kept at 40%. After solvent evaporation, the residue is partitioned between CH2C12 and H20. The Organic layer is dried and evaporated to give a crude product (700 mg) which is purified by Hash chromatography (EtOAc/hexane 1 1) yield 0.38 g (50%) H-l and H-6a have relative trans geometry (determined by nmr 37H-].H-6a = 3.1 Hz). 

The first synthesis for methyl (Z)-2-methoxy-6-hexadecenoate was reported by Soderquist et al. [35]. The idea behind the construction of the a-methoxy functionality was the addition of a carboxy synthon to the corresponding aldehyde, in this case 5- pentadecenal, followed by methylation of the hydroxy group. This synthesis started with the Suzuki-Miyaura cross coupling of 4-bromo-l-butyl-9-borabicyclononane with (Z)-l-bromo-l-undecene, prepared as shown in Fig. (11). 

The Doebner-von Miller reaction was used as a method of choice for the synthesis of several biological active quinoline compounds. The anti-malarial drug primaquine, which acts against the hepatic stage of plasmodia infection, was synthesized by a Skraup reaction fi om 4-methoxy-2-nitroaniline and glyceron in the presence of sulfiiric acid. The nitro group was then reduced and alkylated with 4-bromo-l-phthalimidopentane to provide the protected primaquine, which was deprotected by using hydrazine. ... 

C17H2 3Br02, (6aRS,9RS,1OaRS)-4-Bromo-1-methoxy-6,6,9-trimethyl-6a,7,8,9,10,10a-hexahydro-6H-dibenzo[b,d]pyran, 46B, 329 Cl7H23N208RbS, 4-Nitrobenzo-l,4,7,10,13,16-hexaoxacyclooctadecane rubidium thiocyanate, 44B, 299... 

Preparations from the stem bark of the Indian curry-leaf tree, Murraya koenigii Spreng. (Rutaceae) are used externally to cure skin eruptions. Extraction of the stem bark yielded three compounds, two of which appear to be carbazole derivatives, while the third is as yet of unknown character. Murraj anine, C14H11NO2 (mp 168°) was shown by examination of its spectra and reactions, and by conversion into 3-methylcarbazole and 1-methoxycarbazole, to be either 6-formyl-l-methoxycarbazole or 3-formyl-1-methoxycarbazole (IV), probably the latter (19). This conclusion has now" been confirmed by an unambiguous synthesis (30). 4-Bromo-o-anisidine was converted bj diazotization followed by reduction with stannous chloride into 4-bromo-2-methoxy-])henylh drazine (V). Condensation of V w ith cyclohexanone and cj cli-... 

Like its lithium analogue, sodium cyclopentadienylide gives, with quaternary pyridinium salts, pyridone methides of the type (85)The same and related reagents yield analogous products by reaction with 2- and 4-bromo-l-alkylpyridinium salts , with 4-methoxy- or 4-phenoxy-1-alkylpyridinium salts . ... 

Acetophenone, methyl-/7-tolyl ketone p-chloroacetophenone, /7-bromoaceto-phenone, methyl -anisyl ketone, 2,4-di-methoxyacetophenone,2-methyl-4-metho-xyacetophenone, 5-methyl-2-methoxyace-tophenone, acetocumene, 2,5-trimethyl-acetophenone, 0-, m-, p-hydroxyaceto-phenone, 2,4-dihydroxyacetophenone, 3-methoxy-4-hydroxyacetophenone, o-nitroacetophenone, m-nitroacetopheno-ne, /7-nitroacetophenone, o-, m-, /7-ami-noacetophenone, 2-aceto-l -naphthoxy-acetic acid, 2-aceto-4-bromo-l-naphtho-xyacetic acid... 

Nucleophilic Substitution Reactions. Many of the transformations reali2ed through Michael additions to quiaones can also be achieved usiag nucleophilic substitution chemistry. In some iastances the stereoselectivity can be markedly improved ia this fashion (100), eg, ia the reaction of ben2enethiol with esters (R = CH C O) and ethers (R = 3) 1,4-naphthoquiaones. 2-Bromo-5-acetyloxy-l,4-naphthoquiQone [77189-69-6J, R = Br, yields 75% of 2-thiophenyl-5-acetyloxy-l,4-naphthoquinone [71700-93-1], R = SC H. 3-Bromo-5-methoxy-1,4-naphthoquinone [69833-10-9], R = Br, yields 82% of 3-thiophenyl-5-methoxy-l,4-naphthoquinone [112740-62-2] R = SC H. ... 

When large groups, such as phenyl, bromo, ethoxycarbonyl or nitro are attached at position 3, the principal products are l-alkylcinnolin-4(l/f)-ones. Cyanoethylation and acetylation of cinnolin-4(l/f)-one takes place exclusively at N-1. Phthalazin-l(2/f)-ones give 2-substituted derivatives on alkylation and acylation. Alkylation of 4-hydroxyphthala2in-l(2/f)-one with an equimolar amount of primary halide in the presence of a base leads to 2-alkyl-4-hydroxyphthalazin-l(2/f)-one and further alkylation results in the formation of 4-alkoxy-2-alkylphthalazinone. Methylation of 4-hydroxy-2-methyl-phthalazinone with dimethyl sulfate in aqueous alkali gives a mixture of 4-methoxy-2-methylphthalazin-l(2/f)-one and 2,3-dimethylphthalazine-l,4(2//,3//)-dione, whereas methylation of 4-methoxyphthalazin-l(2/f)-one under similar conditions affords only 4-methoxy-2-methylphthalazinone. 

Itazigrel (137) is an antithrombotic compound because of its inhibition of platelet aggregation induced by collagen. It is synthe.sizcd froin l-bromo-l-(4-methoxy)benzoyl-4-methoxytol-uene (135) by reaction in the usual way with triflucffothioacetamide (136) to give itazigrel 471. 

An elegant extension of these intramolecular acylnitrene-induced ring expansions has been used for the synthesis of cyclopent[h]azepines.2 2-Haloindan-l-yl azidoformates 14 (X = Cl, Br), when subjected to pyrolysis at 300 °C in a hot tube packed with calcium oxide and copper turnings, produce cyclopent[6]azepine (15), as a dark turquoise oil, in excellent yield. Lesser yields (30 and 50%, respectively) of the 4-bromo and 3-methoxy derivatives can be similarly obtained. 

Bromo-6,7,8,9-tetrahydro-l//-3-benzazepin-2-amine(6) with thiocyanate ion undergoes substitution of bromide to give the thiocyanatotetrahydro-l//-3-benzazepine 7.105 Attempts to replace bromide by azide ion failed, as did diazotization of the amine group with sodium nitrite in 6 M sulfuric acid. Oddly, treatment of the aminobromo compound with sodium borohydride in methanol results not in reduction, but in methoxy-debromination to give the 2-methoxy derivative which, on the basis of HNMR spectral data, is best represented as the 2-imino tautomer 8. 

Activating groups at the 5-position led to high yields when bromination took place in chloroform or acetic acid. Products obtained were the 4-bromo derivatives of 5-amino- (90%), 5-hydroxy- (95%), and 5-methoxy-benzisothiazole (40%). Use of the bromine-sulfuric acid-silver sulfate system raised the yield of the last-named product to 87% [80JCR(S)197], 7-Amino-4-chloro-l,2-benzisothiazole was brominated in the 6-position [71JCS(C)3994],... 

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