Acetic acid, 3,4-dimethoxy-phenyl

Acetic acid, chloro, tert butyl ester, 55, 94 Acetic acid, cyano-, ethyl ester, 55, 58, 60 Acetic acid, cyano-, methyl ester, 56, 63 Acetic acid, 3,4-dimethoxy-phenyl-, 55,45, 46... 

Substituted-l-Phenyl-2-Nitropropenes. JOC, 18, 1 (1953). 5 g of 2,5-Dimethoxy-4-bromobenzaldehyde, 5 ml of nitroethane (EtN02), and 2 g of ammonium acetate are added to 20 ml of glacial acetic acid. The resulting solution is refluxed for two hours and poured into ice water. If a solid product is obtained it is collected and recrystallized from methanol, ethanol, or acetic acid. If the product is an oil it is separated and crystallized from one of the above. 

Cohare and co-workers reported that aristolactam BU (22) was prepared, following Kupchen s method, by Perkin condensation of 6-bromo-3,4-di-methoxy phenyl acetic acid (119) and o-nitrobenzaldehyde (120) (Scheme 14). The 2-bromo-4,5-dimethoxy-2 -nitro-ds-stilbene-a-carboxylic acid (121) was obtained. The nitro group of 121 was reduced with ferrous sulfate and ammonium hydroxide, and the resulting 2-bromo-4,5-dimethoxy-2 -amino-cw-stilbene-a-carboxylic acid (122) without purification was submitted to the Pschorr phenanthrene synthesis to yield l-bromo-3,4-dimethoxyphen-anthrene-lO-carboxylic acid (123). The phenanthrylamine 124 was prepared from 123 via a Schmidt reaction, and, by treatment with n-butyllithium and CO2, 124, afforded 22 (42). 

The acid-catalyzed cyclization of properly substituted aminoacetaldehyde dialkyl acetals was shown to be a suitable method in the construction of a homo-isopavine (Scheme 39) (132a,172). Treatment of 7V-[l,3-bis(3,4-dimethoxy-phenyl)propyl]aminoacetaldehyde dimethyl acetal (175) with concentrated hydrochloric acid afforded the 7V-norhomoisopavine 176 in 39% yield. This cyclization was also accompanied by some O-demethylation. Product 176 could be readily N-methylated using formaldehyde and sodium borohydride to afford the homoisopavine ( )-177 (772). 

A cold, stirred solution of 1-phenyl-piperazine in tetrahydrofuran was treated all at once with [3-(2-methyl-5,6-dimethoxy)indolyl]glyoxalyl chloride. There was an immediate voluminous precipitate of a white crystalline solid which was removed by filtration. The filtrate was taken to dryness and the residual light brown gum was stirred and shaken with water, ethyl acetate and acetic acid. The mixture was warmed on a steam bath and the resulting solid was collected after cooling in an ice bath thus affording l-[(3-(2-methyl-5,6-dimethoxy)indolyl)glyoxalyl]-4-phenylpiperazine as a near white solid, melting point 163°-174°C. 

A reversed-phase HPLC post-column ion-pair extraction system was developed by Kim and Stewart [71, 72] for the analysis of carboxylic acid drugs and their salts (sodium formate, sodium acetate, 3-bromopropionic acid, 6-aminocaproic acid, 11-bromoundecanoic acid, 1-heptanesulfonic acid, / -n i t rophcny 1 acetic acid, sodium benzoate, sodium salicylate, valproic acid, probenecid, naproxen, ketoprofen, ibuprofen, mefenamic acid, flufenamic acid, and cefuroxime sodium) using a-(3,4-dimethoxy-phenyl)-4,-trimethylammoniummethylcinnamonitrile methosulfate... 

Grams of 4-benzyloxy-3,5-dimethoxy-nitrostyrene are dissolved in 90 cc. of glacial acetic acid and 180 cc. of alcohol and then mixed, while cooling, with 30 grams of zinc dust. After filtering the excess ol zinc dust, the residue is mixed with water and extracted several times with ether. After the ether has been distilled, the residue, consisting of the oxime of the 4-benzyloxy-3,5-dimethoxy-l-phenyl-acetaldehyde. 

Recently 7,8-dimethoxy isochroman-3-one 48 has been synthesised by an interesting route which involves hydroxymethylation of meta-hydroxy phenyl acetic acid in presence of phenylboronic acid. The presence of the latter in the reaction medium specifically brings about hydroxymethylation ortho to the phenolic group... 

The synthesis of unnatural (+)-mesembrine (387) through the asymmetric synthesis of methyl (i )-l-[(3,4-dimethoxy)phenyl]-4-oxocyclohex-2-enyl acetate (390) by cycloaddition of enantiomerically pure vinyl sulfoxide with dichloroketene has been performed 189) (Scheme 43). Vinyl sulfoxide 388 [prepared by conjugate addition of enantiopure acetylenic sulfoxide with (3,4-dimethoxy)phenylcopper] reacted with trichloroacetyl chloride in the presence of freshly prepared zinc-copper couple in THF at 0°C to produce a mixture of mono- and dichloro lactones 389. Reduction of 389 with zinc in acetic acid followed by cyclization and methylation afforded methyl IR-[(3,4-dimethoxy)phenyl]-4-oxocyclohex-2-enyl acetate (390), treatment of which with methylamine brought about amidation and concomitant intramolecular Michael addition to provide 2-oxo-mesembrine (391). Successively, 391 was transformed to (+)-mesembrine (387) in 79% yield (three steps ketalization of an oxo group, reduction of lactam, and deketali-zation)(/S9). 

Phenalenium ring. Trityl perchlorate added to a soln. of l-[a-(3,4-dimethoxy-phenyl)-a-morpholino]benzyl-2-methoxynaphthalene in glacial acetic acid containing 70%-HC104, stirred and heated 1.5 hrs. at 80-90° 6,9,10-trimethoxy-... 

The sulfuric acid (1% w/v) in commercial (Laporte) 36-40%-peracetic acid neutralized by addition to a soln. of Na-acetate in acetic acid, the resulting soln. added dropwise at 40-42° to a stirred soln. of 330 g. 2,5-dimethoxyacetophenone in acetic acid, and stirred overnight at this temp. 245-280 g. 2,5-dimethoxy-phenyl acetate.—This is part of a 3-step prepn. of 2,5-dialkoxyphenols from p-dialkoxybenzenes by Friedel-Crafts ketone synthesis of the respective acetophenones in excess acetyl chloride as solvent, and final hydrolysis of the 2,5-dialkoxyphenyl acetates. F. e. s. C. A. Bartram, D. A. Battye, and G. R. Worthing, Soc. 1963, 4691. 

A wide variety of substituted y-butyrolactones can be prepared directly from olefins and aliphatic carboxylic acids by treatment with manganic acetate. This procedure is illustrated in the preparation of 7-( -OCTYL)-y-BUTYROLACTONE. Methods for the synthesis of chiral molecules are presently the target of intensive investigation. One such general method developed recently is the employment of certain chiral solvents as auxiliary agents in asymmetric synthesis. The preparation of (S.SM+H, 4-BIS(DIMETHYLAMINO)-2,3-DIMETHOXY-BUTANE FROM TARTARIC ACID DIETHYL ESTER provides a detailed procedure for the production of this useful chiral media an example of its utility in the synthesis of (+)-(/ )-l-PHENYL-l-PEN-TANOL from benzaldehyde and butyllithium is provided. 

Concerning bicyclic derivatives, the first 1,2-benzisoxazole, 3-phenyl-l,2-benzisoxazole, was synthesized by treatment of o-nitrobenzophenone oxime with alkali in 1892 <1892CB1498>, and the parent compound was obtained in 1908 <1908ACP47>. In 1881, 5,6-dimethoxy-2,l-benzisoxazole was the first compound of this class to be prepared <1881JPR353>, and in 1882 the unsubstituted system was synthesized by reduction of o-nitrobenzaldehyde with tin in acetic or hydrochloric acid <1882CB2105>. 

To a solution of ( )-a-(3,5-dimethoxy-4-((phenylsulfonyl)oxy)phenyl)-2-amino-4,5-dimethoxycinnamic acid [91 ] (52, 0.92 g, 1.9 mmol) in acetone (150 ml), H2SO4 (0.21 ml, 3.8 mmol, 96%) was added dropwise at 0 C followed by isoamyl nitrite (3.8 mmol, 2 eq.). After 1 h, sodium iodide (1.14 g, 4 eq.) was added in four portions over a 5-h period, the solution was stirred for an additional hour, and enough sodium bisulfite was added to turn the reaction mixture yellow, whereupon it was poured into water (400 ml) and extracted with chloroform (4x50 ml). The organic phases were combined, washed with water (3x100 ml), dried (Na2S04), and evaporated to yield the crude product which was purified by crystallization from ethyl acetate / -hexane to afford 629 mg (71%) of pure 53, m.p. 155.5-158.5 C. 

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