Ethers isoquinoline

Table 20. Glass transition temperatures or poly(arylene ether isoquinoline)s...

Diphenylamine Ethylamine 2-Ethylhexyl chloride Hydroquinone monomethyl ether Isoquinoline... 

Dimethylamine Dimethyl formamide Dimethylolpropionic acid 2,2-Dimethylpropanol Diphenylamine Ethylene chlorohydrin Hydrogen cyanide Hydroquinone monomethyl ether Isoquinoline Methyl isocyanate Nonanoic acid Phenolsulfonic acid Phosphorus oxychloride Pyrrole Quinaldine Sodium nitrate Stannic chloride Strontium salicylate Thioglycolic acid o-Xylene 2,3-Xylenol 2,3-Xylidine pharmaceutical mfg., orals Candelilla (Euphorbia cerifera) wax Cholecalciferol Ergocalciferol pharmaceutical mfg., parenterals Cholecalciferol Ergocalciferol pharmaceutical processing Chlorotrifluoromethane pharmaceutical prods. 

Hay has reported the synthesis of poly(aryl ether ketones) containing o-dibenzoylbenzene moieties by the polymerization of 1,2-bis(4-fluorobenzoyl) benzene with various bisphenolates in DM AC (32). Transformation of the o-dibenzoyl(benzene) moiety in the polymer chain to a heterocycle by cyclization with small molecules was developed as a means of increasing the pol5mer chain stiffness and solvent resistance. It was demonstrated that reaction of the polymer with hydrazine monohydrate in the presence of a mild acid in chlorobenzene converted the poly(aryl ether ketone) to a poly(aryl ether phthalazine), a new class of heterocyclic-containing polyether (Scheme V) (33). Likewise, reaction of the polymer with benzylamine in a basic medium led to amorphous, thermally stable poly(aryl ether isoquinolines) (Scheme V) (34). Another example of the use of the o-benzoyl cyclization strategy is the intramolecular ring closure of poly(aryl ketones) containing 2,2 -dibenzoylbiphenyl units to form poly(aryl ether phenanthrenes) (35-37). 

The poly(ether ketone)s can be converted to poly(ether phthalazine)s 21 or poly(ether isoquinoline)s 22 by reaction with hydrazine and benzylamine, respectively. This conversion results in polymers in which there is considerable straightening of the polymer chains and this results in substantial increases in the glass transition temperatures (30 - 40 °C), in the solution viscosities, and in the apparent molecular weights as measured by GPC using polystyrene standards. 

The poly(ether phthalazine)s and poly(ether isoquinoline)s synthesized to date are amorphous materials, soluble in solvents such as chloroform at room temperature and they can be cast into tough, transparent, pale yellow, flexible films. 

Poly(aryl ether isoquinoline)S chromatography Poly( 1 -butene oxide), see Poly(oxy(ethylethylene) Chloroform SEC, p-styragel 3004... 

Pellotine and Anhalonidine. The A -acetyl derivative of mezcaline (I NHj— NHAc), on treatment with phosphoric oxide, yields 6 7 8-trimethoxy-l-methyl-3 4-dihydrowoquinoline (picrate, m.p. 181-2°), which, on successive catalytic hydrogenation and treatment with methyl sulphate, yields 6 7 8-trimethoxy-l 2-dimethyl-l 2 3 4-tetrahydro-isoquinoline identical with 0-methylpellotine (picrate, m.p. 167-8°), whence it appears that pellotine must be a dimethyl ether of 6 7 8-trihydroxy-1 2-dimethyl-l 2 3 4-tetrahydrowoquinoline. Pellotine and anhalonidine on complete methylation yield the same product, and as anahalonidine is a secondary base and differs from pellotine by containing —CHj less, it must be a dimethyl ether of 6 7 8-trihydroxy-l-methyl-1 2 3 4-tetrahydrowoquinoline, and pellotine should be A -methyl-anahalonidine. 

In methanol, isoquinoline and the ester gave the benzo[fif]indolizine [(121), cf. Section II,D,3] while in ether the labile adduct, tetra-methyl llbH-benzo[a]quinolizine-l,2,3,4-tetracarboxylate (122) was obtained. The labile adduct is much less easily isoraerized than the 9-methyl-9aH-quinolizines derived from pyridines (Section III,F,1) but with boiling xylene or, better, with sulfuric-acetic acids the cor-... 

To a solution of 50 grams of 6,7-dimethoxy-3-methyl-T(4 -ethoxy-3 -methoxybenzyl)-dihy-droisoquinoline base in 200 ml of dry benzene are added 150 ml of decalin, and the mixture is distilled until its temperature reaches 180°C. 1.5 grams of 5% palladium on carbon are then added. The mixture is stirred under reflux for about 6 hours to dehydrogenate the dihydroisoquinoline. On cooling, the reaction mixture is diluted with petroleum ether and the precipitated 6,7-dimethoxy-3-methyl-1-(3 -methoxy-4 -ethoxybenzyl)-isoquinoline is filtered off and recrystallized from dilute ethanol. 

Synthesis in m-cresol. The dianhydride (1.35 mmol) is added to a stirred solution of 1.35 mmol of die diamine in die appropriate amount of m-cresol containing 6 drops of isoquinoline under N2 at room temperature. After 3 h, it is heated to reflux (ca. 200° C) and maintained at that temperature for 3 h. During this time, the water of imidization is distilled from die reaction mixture along with 1 to 3 mL of m-cresol. The m-cresol is continually replaced to keep the total volume of the solution constant. After die solution is allowed to cool to room temperature, it is diluted witii 20 mL of m-cresol and then slowly added to 1 L of vigorously stirred 95% ethanol. The precipitated polymer is collected by filtration, washed witii ethanol and ether and dried under reduced pressure at 125°C for 24 h. 

Sulfuric acid 96% (technical quality) and diethyl ether (technical quality) were purchased from Bie Bemtsen A/S, Sandbaekvej 7, DK-2610 Roedovre, Denmark and used without further purification. Isoquinoline (97%) and potassium nitrate (99%) were purchased from Aldrich Chemical Company, Inc. and used without further purification. 

Thioxo-2,3-dihydro[l, 2,4]triazino[6,5-c]isoquinolin-6-one 189 was obtained (75ZOR2407) by the cyclization of the 3-thiosemicarbazone 188 with alkali. Compound 188 was prepared by the reaction of 3-anilino-1,4-dihydro- 1,4-isoquinolinedione 187 or the ether 186 with thiosemicarbazide. Compound 187 was obtained by reaction of the ether 186 in benzene with aniline. The ether 186 was obtained from the alkylation of 179 (R = H) via its silver salt 185. 

The synthesis of 3-aryltetrahydroisoquinolines was accomplished by electrophilic aromatic substitution of polysubstituted phenols and phenyl ethers with Lewis acid-generated tosyliminium ions of 2-tosyl-3-methoxytetrahydroisoquinoline derivatives <00SL801>. In addition isoquinoline was reported to react with N-tosylated (R)- or (S)-amino acid fluorides to afford optically active dihydroimidazoisoquinolinones. The reaction proceeds via acylation followed by attack of the tosylamino group at Cl of the intermediate 2-tosylaminoacylisoquinolinium salt <00TL5479>. 

The Delft synthesis makes use of an acid-catalyzed ring closure - in fact an intramolecular aromatic alkylation - of a l-(3,5-dihydroxy-4-methoxybenzyl) isoquinoline derivative that is prepared starting from (natural) gallic acid. One of the hydroxyl groups is removed via a Pd/ C hydrogenation of the benzyl ether. Other catalytic steps play an important role some steps were improved recently [27]. The crucial step in the Rice synthesis makes use of a l-(2-bromo-5-hydroxy-4-methoxybenzyl)isoquinoline derivative that is also cyclized in an acid-catalyzed ring closure to the morphinan skeleton, followed by catalytic removal of the bromo substituent (Scheme 5.8). 

The thermal ring closure of 1-isoquinolinylaminomethylenemalonates (1058) by heating in diphenyl ether at 235-260°C for 5-15 min gave pyrim-ido[2,l-a]isoquinoline-3-carboxylates (1059) in 67-83% yields [78USP-4127720 84JAP(K) 172472]. 

The ethyl radical directly attacks the heteroaromatic base, while the acetaldehyde acts as a source of acetyl radical. Photochemical oxy-alkylation has also been tried with ethers. The reaction has been successfully carried out with pyridines, quinolines, isoquinolines,cinno-lines, and quinoxalines. Particularly good yields were obtained with caffeine (16) (Scheme 14). ... 

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