4- Methoxy- benzyl methyl

OS 85] ]R 33] ]P 65] By means of HPLC analysis, it could be shown that all three types of products were formed during reaction in the micro reactor [69]. For a typical experiment, the main fraction was composed of 4-mefhoxybenzaldehyde dimethylacetal, the second largest fraction consisted of the aldehyde and 4-methoxy-benzyl methyl ether was generated in a smaller amoimt. 

M p-methoxy-benzyl-methyl ketone (l-p-methoxy-phenyl-2-propanone) (or analog), 20 g NH Cl, 225 ml methanol saturated with NHj, 25 ml NH OH and shake with 1-3 atmospheres Hj until uptake ceases. Filter, wash precipitate with methanol or acidify with HCl and dry, evaporate in vacuum to get p-methoxy-amphetamine or analog. 

The cleavage proceeds by initial reduction of the nitro groups followed by acid-catalyzed cleavage. The DNB group can be cleaved in the presence of allyl, benzyl, tetrahydropyranyl, methoxy ethoxy methyl, methoxymethyl, silyl, trityl, and ketal protective groups. 

Quinoxalin-2-ones are in tautomeric equilibrium with 2-hydroxy-quinoxalines, but physical measurements indicate that both in solution and in the solid state they exist as cyclic amides rather than as hydroxy compounds. Thus quinoxalin-2-one and its A -methyl derivative show practically identical ultraviolet absorption and are bases of similar strength. In contrast, the ultraviolet spectra of quinoxalin-2-one and its 0-methyl derivative (2-methoxyquinoxaIine) are dissimilar. The methoxy compound is also a significantly stronger base (Table II). Similar relationships also exist between the ultraviolet absorption and ionization properties of 3-methylquinoxalin-2-one and its N- and 0-methyl derivatives. The infrared spectrum of 3- (p-methoxy-benzyl)quinoxalin-2-one (77) in methylene chloride shows bands at 3375 and 1565 cm" which are absent in the spectrum of the deuterated... 

Ortho (1,1-Azido methyl anisole), liq, bp 118° at 14mm of Hg. Prepd from a mixt of N-Nitroso-N-(2-methoxy-benzyl)-hydrazine and dil sulfuric acid by steam distn (Ref 1). Explodes when heated quickly (Ref 1) ... 

Manche Ather werden ahnlich den Alkoholen auch von Mischungen aus Lithiumala-nat/Aluminiumchlorid angegriffen. So laBt sich z.B. Bis-[4-methoxy-benzyl]-ather durch Lithiumalanat/2 Aluminiumchlorid in 83%iger Ausbeute zu 4-Methoxy-1-methyl-benzol reduzieren3. Dibenzylather wird dagegen nicht reduziert. Zur Reduktion mit Lithiumalanat/Titan(IV)-chlorid4 bzw. Natrium-bis-[2-methoxy-athoxy]-dihydrido-alu-minat5 s.Lit. 

Benzyl-(4-chlor-benzyliden)- 664 Bis-[fluoracetyl]- 239 Bis-[2-fluor-athyl]- 239 (Bis-[4-methoxy-phenyl]-methyl)- 377 Bis-[2-methyl-propyl]- 358 Bis-[2-phenyl-2-cyan-vinyl]- 58 tert.-Butyl-(hydroxy-tert.-butyl)-... 

M m-methoxy-toluene (or analog), 30 ml HCI, 30 ml benzene cool to 0° and with cooling and stirring saturate with HCI. Add 0.15 M formaldehyde and then more HCI for fifteen minutes. Stir at room temperature for two hours and dry, evaporate in vacuum the benzene layer to get about 30% 2-methyl-4-methoxy-benzyl-CI (or analog). 0.5 M (l), 0.8 M NaCn, 5 g Nal or K1 in 250 ml dry acetone stir and boil twenty hours. Filter, wash precipitate with 100 ml acetone and dissolve precipitate with 75 ml benzene. Wash with 100 ml water and dry, evaporate in vacuum to get about 80% yield 2-methyl-4-methoxy-benzyl-CN (II). 0.1 M (ID in 60 ml 10N NH3 in methanol 4 g Ni-Cr20 and shake in autoclave at 70-100 atmospheres H2 and 120° to get about 80% yield of the phenethylamine. 

The stereospecific C-alkylation of a range of benzylic ketones, such as tetralones, 2-phenylcyclohexanones and cycloheptanones, and 2-phenyl-y-lactones, has also been described [8]. For example, Af-(4-trifiuoromethylbenzyl)cinchonidinium bromide catalyses the reaction of 1,5-dibromopentane with 7-methoxy-l-methyl-2-tetralone to yield the (R)-l-(5-bromopentyl) derivative (75% yield with 60% ee). 

In an extension of this work, Schnider and his colleagues condensed the salt (36) with the Grignard reagent from p-methoxy-benzyl chloride. The product (40), on reduction (41) and cyclizar-tion, affords the methoxylated morphinan (41). Removal of the methyl ether affords the narcotic analgesic racemorphan (43). ... 

OCH3 7-(4-Metho.xy-phenyl)-2-methyl-... 45 6-(4-Methoxy-benzyl)-7-( 4-methoxy-phenyl)-2-methyl-... 35... 

Mit 1-Amino-propan erhalt man analog das 13-Methyl-9-propylamirw-2,3,IQ-trimethoxy-5,6-dihydro-(dibenzo aig]chinolizinium)-chlorid mit Pyrrolidin und einigen anderen Ami-nen verlauft die Reaktion anders. N-Methyl-papaverinium-jodid laBt sich mil 2-Amino-ethanol, wie oben beschrieben, unter Austausch nur einer Methoxy-Gruppe in l-(3,4-Dimethoxy-benzyl)-6-(2-hydroxy-ethylamino)-7-methoxy-2-methyl-isochmolinium-jodid (90%) uberfiihren1. 

J. Cl 0 ch2-O (nicht isoliert)r Na[BH4J/CH30II/H20 0°, 1 h 5-Benzyloxy-4-(4-benzyl- oxy-phenyl)-6-methoxy- 2-methyl-l,2,3,4-hexa- hydro-isochinolin (rac-Di-O-benzyl- latifin) 51. r 1... 

Benzyloxy-l-( 4-benzyloxy-3-methoxy-benzyl) -6-methoxy-2- (4-methyl-benzolsulfonyl)-... 

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