3.4- dimethoxyphenyl

Appendix - Phenyl acetones by electrolytic oxidation. Process for 3,4-dimethoxyphenyl-acetone preparation. European Patent Application 0247526, Filed 02.12.87 to LARK S.p.a. Milan. 

Ozonolysis, then reduction with Na2S204 at 50°, 57% yield.The 3,4-dimethoxyphenyl derivative was cleaved in 71% yield using these conditions. Ceric ammonium nitrate was reported not to work in this example. 

This azlactone is prepared readily from benzaldehyde according to the procedure given for the azlactone of a-ben-zoylamino-/3-(3,4-dimethoxyphenyl)-acrylic acid (Org. Syn. 13, 8). From 53 g. (0.5 mole) of benzaldehyde, 89.5 g. (0.5 mole) of hippuric acid, 41 g. of fused sodium acetate, and 153 g. of acetic anhydride there is obtained 78-80 g. (62-64 per cent yield) of an almost pure product melting at 165-166° (corr.). This material is sufficiently pure for use in the preparation of phenylalanine. By crystallization from 150 cc. of benzene a product melting at 167-168° (corr.) is obtained. 

Dimethoxyphenyl acetic acid (homoveratric acid) [93-40-3] M 196.2, m 97-99 , pK 4.33. Crystd from water or benzene/ligroin. 

Tetramethoxyisoflavone (5) was the target of the cyclisation reaction of 3,4-dimethoxy-phenol (7) with formyl-(3,4-dimethoxyphenyl)acetic acid (2) in the presence of polyphosphoric acid. 

A synthesis of possible biological significance was effected by Spath and Berger, who ozonised eugenol methyl ether to 3 4-dimethoxyphenyl-acetaldehyde (Villa), which was then condensed with 3 4-dimethoxy-phenylethylamine (Vlllb), and the resulting Schiff s base (IX) treated wit hot 19 per cent, hydrochloric acid, whereby it was transformed into... 

The A-substituted derivatives of 4-oxo-4//-pyrido[l,2-n]pyrimidine-3-carboxamides and -3-acetamides and l,6-dimethyl-4-oxo-1,6,7,8-tetrahy-dro-4//-pyrido[l,2-n]pyrimidine-3-carboxamide were prepared by treatment of the appropriate 3-carboxylic acids and acetic acid, first with an alkyl chloroformate in the presence ofNEt3 in CHCI3 below — 10°C, then with an amine (98ACH515). A-Phenethyl and A-[2-(3,4-dimethoxyphenyl)ethyl] derivatives of 6-methyl-6,7,8,9-tetrahydro-4//-pyrido[l, 2-n]pyrimidine-3-acetamide were obtained in the reaction of 6-methyl-6,7,8,9-tetrahydro-4//-pyrido[l,2-n]pyrimidine-3-acetic acid and phenethylamines in boiling xylene under a H2O separator. Hydrazides of 4-oxo-4//- and 4-oxo-6,7,8,9-tetrahydro-4//-pyrido[l, 2-n]pyrimidine-3-acetic acid were prepared from the appropriate ester with H2NNH2 H2O in EtOH. Heating 4-oxo-4//- and 6-methyl-4-oxo-6,7,8,9-tetrahydro-4//-pyrido[l, 2-n]pyrimidine-3-acetic hydrazides in EtOH in the presence of excess Raney Ni afforded fhe appropriafe 4-oxo-6,7,8,9-fefrahydro-4//-pyrido[l,2-n]pyrimidine-3-acefa-mide. In the case of the 4-oxo-4// derivative, in addition to N-N bond... 

The tautomeric forms 11 and 12, called pyrrolenines, have often been postulated for pyrrole (10), but there is no conclusive evidence for their existence. The report that two isomers exist as the pyrro-lenine forms 13 and 14 (Ar = 3,4-dimethoxyphenyl) must be regarded with considerable doubt. 

Chloro-9,10-dimethoxy-6,7-dihydro-4//-pyrimido[6,1 -a]isoquinolin-4-one was obtained by the cyclization of 7V-[2-(3,4-dimethoxyphenyl)ethyl]barbi-turic acid on the action of boiling POCI3 in 62% yield (98MIP15, 00MIP19,P20). 

A variant on this structure, dioxyline, has much the same activity as the natural product but shows a better therapeutic ratio. Reduction of the oxime (113) from 3,4-dimethoxyphenyl-acetone (112) affords the veratrylamine homolog bearing a methyl group on the amine carbon atom (114). Acylation of this with 4-ethoxy-3-methoxyphenyl acetyl chloride gives the corresponding amide (115). Cyclization by means of phosphorus oxychloride followed by dehydrogenation over palladium yields dioxyline (116). ... 

A mixture of 150 grams of 1-(3, 4 -dimethoxyphenyl)-2-propanone and 70 grams of hydroxylamine hydrochloride in 125 cc of water is stirred while a solution of 51.3 grams of sodium carbonate in 150 cc of water is added over the course of 15 minutes, and while maintaining the reaction mixture at 30°-40°C. The reaction mixture is stirred for an additional two and one-half hour period at room temperature, and is then diluted with an equal volume of water and extracted three times with 300 cc portions of ether. The combined ether extracts are washed with water, dried over anhydrous magnesium sulfate, and the... 

Dimethoxyphenyl)-2-propanone oxime thus prepared boiled at about 165-175°C at 0.6 mm pressure. Analysis showed the presence of 7.23% of nitrogen, compared with the calculated amount of 6.69%. 

A solution of 151 grams of 1-(3, 4 -dimethoxyphenyl)-2-propanone oxime in 200 cc of absolute ethanol is treated with 5 grams of Raney nickel catalyst and ammonia in an autoclave at about 25 atm of pressure and at 75 -100°C. The reduction is complete in about one-half hour and the reaction mixture is filtered and fractionated under reduced pressure to recover the a-methylhomoveratrylamine formed by the reduction. a-Methylhomoveratryl-amine thus prepared boiled at 163°-165°C at 18 mm pressure. 

Chemical Name 1 -(3,4-Dimethoxyphenyl)-4-methyl-5-ethyl-7,8-dimethoxy-5H-2,3-benz-diazepine... 

Chemical Name a-[3-[ [2-(3,4-Dimethoxyphenyl)ethyl] methylamino] propyl] -3,4-dimeth-oxy-a-l 1 -methylethyDbenzeneacetonitrile... 

A solution of 20.7 g (0.1 mmol) of (46 ,56 )-5-amino-2.2-dimethyl-4-phenyl-l,3-dioxane and 19.4 g (0.1 mol) of 3,4-dimethoxyphenyl-2-propanone in 70 mL of CH3OH is warmed to 60 "C and 9 mL of acetic acid is added. After 15 min the mixture is cooled with an ice bath. The precipitated product is filtered off, stirred with 1 L of water for 1 h to dissolve inorganic salts, and again collected by filtration. Drying over NaOH and recrystallization from CH3OH gives the product yield 33.6 g (82%) mp 127 128°C [a] 2 + 85.7 (c = 1, CHC1,). 

S, R, 9uR )-6-(3,4-dimethoxyphenyl)-octal ydro-8-hydmxy-4H-quinolizm-4-one141 yield 81 %... 

A-Acetylhomoveratrylamine2 is prepared by adding 190 ml. of acetic anhydride to a stirred solution of 300 g. (1.80 moles) of /3-(3,4-dimethoxyphenyl)ethylamine [Benzeneethanamine, 3,4-dimethoxy-J (Aldrich Chemical Company, Inc.) in 150 ml. of pyridine at such a rate that the temperature is maintained at 90-95° (ca. 1.5 hours is required). After the solution has been stored at room temperature overnight, the volatile material is evaporated under reduced pressure, and the residue is crystallized from ethyl acetate to give 286-306 g. (78-83%) of acetylated product, m.p. 99-100°. 

Ether, chloromethyl methyl [Methane, chloromethoxy-], 97 Ethylamine, dusoptopyl- [ 2-Propanamme, Af-ethyl-Af-(l-methylethyl)-], 59 Ethylamine, 2-(3,4-dimethoxyphenyl)-[Ben-zeneethanamme, 3,4-dimethoxy-], 5 Ethylene, 1,1-diphenyl- [Benzene, 1,1 -ethenylidenebis-], 32 Ethylene, tetramethyl- [2-Butene, 2,3-dimethyl-], 35... 

Acetic acid, cyano-, ethyl ester 55, 58, 60 Acetic acid, 3,4 dimethoxyphenyl, 55, 45, 46... 

CN (R)-a [[[2- 3,4-dimethoxyphenyl)ethyl]amino]methyl]-4-hydroxybenzenemethanol hydrochloride... 

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