Amines related to 2,5-dimethoxyphenethylamine. II.
Baltzly, Richard; Buck, Johannes S.
Journal of the American Chemical Society (1940), 62 164-7.
CODEN: JACSAT ISSN: 0002-7863. Journal language unavailable. CAN 34:10439 AN 1940:10439 CAPLUS
Abstract
2,5-(MeO)2C6H3CHO and BrCH2CO2Et, condensed by the Reformatski.crn.i method, give 80% of Et beta-(2,5-dimethoxyphenyl)hydracrylate, yellow, b1 164-7°; the hydrazide, m. 161.5.degree. (all m. ps. cor.); the Curtius rearrangement yields 5-(2,5-dimethoxyphenyl)-2-oxazolidone, m. 107°, cleavage of which by cold, concd. HCl gives beta-(2,5-dimethoxyphenyl)-beta-hydroxyethylamine-HCl, m. 158.5.degree.; this and the other salts may be crystd. from abs. EtOH by addn. of Et2O or AcOEt or both;
the amine also results by reduction of 2,5-dimethoxyphenacylamine-HBr, yellow, m. 195° (decompn.), which is prepd. by condensation of 2,5-(MeO)2C6H3COCH2Br (I) and hexamethylenetetramine and hydrolysis with HBr. I and PhCH2NHMe in Et2O give 2,5-dimethoxyphenacylmethylbenzylamine (II), whose HCl salt, m. 167.5.degree.; reduction with PtO2 and H in EtOH gives beta-(2,5-dimethoxyphenyl)-beta-hydroxyethylmethylamine-HCl, m. 151.5.degree.. II with MeMgI, followed by catalytic reduction, yields beta-(2,5-dimethoxyphenyl)-beta-hydroxypropylmethylamine, whose HCl salt m. 158-9°.
2,5-(MeO)2C6H3Ac and BrCH2CO2Et, condensed with Zn-Cu alloy, yield after sapon. beta-methyl-beta-(2,5-dimethoxyphenyl)hydracrylic acid, m. 121-2.degree.; the hydrazide, m. 112°, results in 27% yield from the crude washed (but not distd). ester; unsatisfactory results were obtained with the distd. ester or that prepd. from the acid, due to the tendency of the compds. to dehydrate when distd. or subjected to acids; Curtius rearrangement yields 5-methyl-5-(2,5-dimethoxyphenyl)-2-oxazolidone, m. 159°; cold concd. HCl gives b-(2,5-dimethoxyphenyl)-beta-hydroxypropylamine-HCl, m. 174°.
Bromohydroquinone di-Me ether, converted into the Grignard reagent and reacted with Me2NCH2CN, the base liberated with NH3, extd. with Et2O and treated with EtOH-HCl, gives 2,5-dimethoxyphenacyldimethylamine-HCl (III), m. 171° (decompn.), catalytic reduction of which yields beta-(2,5-dimethoxyphenyl)-beta-hydroxyethyldimethylamine-HCl, m. 155°; its methochloride, m. 185-6°.
The free base from III and MeMgI give beta-(2,5-dimethoxyphenyl)-beta-hydroxypropyldimethylamine-HCl, m. 176.5.degree.; methochloride, m. 213.5.degree..
alpha-Isonitroso-2,5-dimethoxypropiophenone, pale yellow, m. 97-8°, was prepd. by Hartung's method (Patent US1989093 (http://l2.espacenet.com/dips/viewer?PN=US1989093&CY=gb&LG=en&DB=EPD)
, C. A. 29, 1941.7); catalytic reduction yields beta-(2,5-dimethoxyphenyl)-beta-hydroxyisopropylamine-HCl, m. 175-6° (decompn.).
The alpha-Br deriv. of 2,5-(MeO)2C6H3COEt with excess of MeNH2 in Et2O gives 2,5-dimethoxy-alpha-methylaminopropiophenone (IV), whose HCl salt, m. 172-3° (decompn.); catalytic reduction yields beta-(2,5-dimethoxyphenyl)-beta-hydroxyisopropylmethylamine, whose HCl salt (V) m. 170°.
The alpha-dimethylamino analog of IV m. 154-6° (decompn.); that of V m. 198° (decompn.); the methochloride of the latter m. 221-3° (decompn.). It is assumed that the hydroxyisopropylamine group has the ephedrine, rather than the pseudoephedrine, configuration; the relatively high m. ps. and the methods of prepn. support this view.
Since the OCR of Adobe Acrobat can't handle low resolution scans of old scientific journals as well as a human, here are the original PDFs on Rhodium's site for whomever is interested.
https://www.thevespiary.org/rhodium/Rhodium/pdf/archive/merbst/Amines%20related%20to%202-5-dimethoxyphenethylamine%201.pdf (https://www.thevespiary.org/rhodium/Rhodium/pdf/archive/merbst/Amines%20related%20to%202-5-dimethoxyphenethylamine%201.pdf)
https://www.thevespiary.org/rhodium/Rhodium/pdf/archive/merbst/Amines%20related%20to%202-5-dimethoxyphenethylamine%202.pdf (https://www.thevespiary.org/rhodium/Rhodium/pdf/archive/merbst/Amines%20related%20to%202-5-dimethoxyphenethylamine%202.pdf)
https://www.thevespiary.org/rhodium/Rhodium/pdf/archive/merbst/Amines%20related%20to%202-5-dimethoxyphenethylamine%203.pdf (https://www.thevespiary.org/rhodium/Rhodium/pdf/archive/merbst/Amines%20related%20to%202-5-dimethoxyphenethylamine%203.pdf)
https://www.thevespiary.org/rhodium/Rhodium/pdf/archive/merbst/Amines%20related%20to%202-5-dimethoxyphenethylamine%204.pdf (https://www.thevespiary.org/rhodium/Rhodium/pdf/archive/merbst/Amines%20related%20to%202-5-dimethoxyphenethylamine%204.pdf)
https://www.thevespiary.org/rhodium/Rhodium/pdf/archive/merbst/Amines%20related%20to%202-5-dimethoxyphenethylamine%205.pdf (https://www.thevespiary.org/rhodium/Rhodium/pdf/archive/merbst/Amines%20related%20to%202-5-dimethoxyphenethylamine%205.pdf)
For anyone interested in OCRing old journals using Acrobat Reader, just upgrade to version 6.01 then click the down arrow to the right of the "T with a dashed square around it" on the second row of the toolbar. Choose the "Column Select Tool" and then drag a square around the text you would like to capture, then right click Copy and paste it into a text document. Then spend the time to go through the text document and correct the OCR errors or else it will look like the above post :-[ .
Hydroxy- and Dihydroxyphenylethylmethylamines and Their Ethers
Johannes S. Buck
J. Am. Chem. Soc. 54, 3661-3665 (1932) (https://www.thevespiary.org/rhodium/Rhodium/pdf/2ch.phenylpropionamide.pdf)
(https://www.thevespiary.org/rhodium/Rhodium/pdf/2ch.phenylpropionamide.pdf)