Methyl phenyl amines

OCN3 H3C6 MgBr 14 ( 4-Methoxy-phenyl)-methyl-phenyl-amin 80... 

Auch die Reaktion von Azido-benzol und seinen Methyl-, Chlor- und Nitro-Derivaten mit Methyl-benzolen in Gegenwart von Bortrifluorid fuhrt in den meisten Fallen zu Gemischen von aromatischen Aminen, wobei man z.B. aus 4-Azido-l-methyl-benzol und 1,3-Dimethyl-benzol als Hauptprodukt (2,4-Dimethyl-phenyl)-(4-methyl-phenyl)-amin (67%) neben 4-Methyi-N-(3-methyl-benzyl)-anilin (7,5%) und 4-Methyl-anilin (5%) erhalt, aus l-Azido-4-methyl-benzol und Mesitylen jedoch (4- (Methyl-phenyl)-(2,4,6-trime-thyl-phenyl)-amin (55%) neben nur wenig 2,4,6-Trimethyl-anilin (1%)2. 

Man erhalt auf diese Weise z. B. Bis-[4-methyl-phenyl]-amin, (4-Methoxy-phenyl)-(4-methyl-phenyl)-amin bzw. (4-Chlor-phenyl)-(4-methyl-phenyl)-amin. 

Methylnonylthiuronium Pi crate A69-L Methyl phenyl amines. See under Amino-toluenes A265... 

Mono-methyl aniline, CeHsNH(CHa), or methyl phenyl amine,... 

P.15) Benzenamine, A-methyl-, N-methylaniline methyl (phenyl) amine [100-61-8]... 

Deall lation. Chloroformates such as vinyl chloroformates (40) are used to dealkylate tertiary amines. Chloroformates are superior to the typical Von Braun reagent, cyanogen bromide, because of increased selectivity producing cleaner products. Other chloroformates such as aHyl, methyl, phenyl, and trichloroethyl have also been used in dealkylation reactions. Although the dealkylation reaction using chloroformates is mostiy carried out on tertiary amines, dealkylation of oxygen or sulfur centers, ie, ethers or thioethers, can also be achieved. a-Chloroethyl chloroformate [50893-53-3] (ACE-Cl) (41,42) is superior to all previously used chloroformates for the dealkylation reaction. ACE-Cl has the advantage that the conditions requked for ACE... 

In the course of this study, the authors determined /Lvalues for dibenzyl, methyl phenyl, methyl p-nitrophenyl, di-p-tolyl, di-isopropyl and tetramethylene sulphoxides and for diethyl, dipropyl and dibutyl sulphites. The /Lscales are applied to the various reactions or the spectral measurements. The /Lscales have been divided into either family-dependent (FD) types, which means two or more compounds can share the same /Lscale, family-independent (FI) types. Consequently, a variety of /Lscales are now available for various families of the bases, including 29 aldehydes and ketones, 17 carboxylic amides and ureas, 14 carboxylic acids esters, 4 acyl halides, 5 nitriles, 10 ethers, 16 phosphine oxides, 12 sulphinyl compounds, 15 pyridines and pyrimidines, 16 sp3 hybridized amines and 10 alcohols. The enthalpies of formation of the hydrogen bond of 4-fluorophenol with both sulphoxides and phosphine oxides and related derivatives fit the empirical equation 18, where the standard deviation is y = 0.983. Several averaged scales are shown in Table 1588. 

A variety of ligands were used to hydrogenate 73a, 74a-b, 75a-b, and 76a with moderate results. Steric interactions were magnified and that may explain why nearly all of the substrates in Scheme 15 give less than optimal results. A-methyl-A-phenyl-amine derived enamines 74a and 75a were resistant to hydrogenation where the analogous A-methyl-W-benzyl-amine-based enamines were completely converted with SimplePHOX ligand 77 with moderate enantioselectivity. 

Reaction of 4-chloro-6-fluoropyrido[3,4- pyrimidine 59 with [3-methyl-4-(pyridin-3-yloxy)phenyl]amine 60, followed by coupling the formed amine 61 with (3-azabicyclo[3.1.0]hex-6-yl)carbamic acid fi r7-butyl ester, afforded the substituted derivative 62 <2002EPP1249451>. Compound 59 was also reacted with 3-bromoaniline to give the 4-anilino derivative 63 that upon treatment with either methyl- or dimethylamine gave the corresponding 4,6-diamino derivatives 64 (Scheme 2) <1997W09726259, 1995W09519774>. 

Die intramolekulare Amin-Addition bei 1-Aryl-l-[2-(methylamino-methyl)-phenyl]-l-al-kenen unter Bildung von 1,2,3,4-Tetrahydro-isochinolinen wird durch Kaliumhy-droxid katalysiert2. 

Auch kern-substituierte Phenylierungs-Reagenzien konnen verwendet werden. So erhalt man z.B. aus Anilin mit Diacetoxy-tris-[4-methyl-phenyl]-bismut (4-Methyl-phenyl)-phe-nyl-amin in 98% Ausbeute1. 

Unter UV-Bestrahlung erhalt man aus 2-Azido-l-methyl- bzw. 4-Azido-l-methyl-benzol und Mesitylen (2-Methyl-phenyl)-(2,4,6-trimethyl-phenyl) - und (4-Methyl-phenyl)-(2, 4,6-trimetkyl-phenyl)-amin in 59%- bzw. 84%iger Ausbeute3 ... 

Diethyl(trifluoromethyl)amine (19) and [difluoro(phenyl)methyl](dimethyl)amine (21) are synthesized from the corresponding diethylformamide (18) and N, /V-dimethylbenzamide (20), respectively. The fluorination is achieved with sulfur tetrafluoride in the presence of potassium fluoride at 150l,C.36... 

Diethyl(trifluoromethyl)amine (19 14.1 g, 0.1 mol) was added dropwise to i-PrOH (22 6g, 0.1 mol) at 40CC with stirring, an exothermic reaction occurred and the mixture was brought to reflux. Once the addition was complete the mixture was stirred for a further 15 min. The volatile 2-fluoropropane (23) which evolved during the course of the reaction was condensed into a cold trap at — 78°C yield 4.6 g (74%). An identical yield was obtained when the same procedure was performed with [difluoro(phenyl)-methyl](dimethyl)amine (21) instead of 19. 

Tetranitro-3 methylnitramino-di phenyl-amine, also called in Beil N-Nitro-N-methyl-N -[2-nitro-phenyl)-2,4.6 trinitropbenylendia-min-( 1.3), 0JN-CiH4.NH-C6H(N0a)J-N(N02).CHs. Yel crysts (from AcOH), mp 200°(dec). Was prepd by treating 2,4,6-tr ini tro-3-me th y Ini tramino-diphenylamine with HNO,(d 1.49) at RT. Its expl props were not examined... 

In the second method (Scheme 26) a 3-oxo ester is synthesized from an acid chloride and 2,2-dimethyl-l,3-dioxane-4,6-dione. Then, reductive amination of the 3-oxo ester with a-methyl(phenyl)methylamine provides a 3-amino- 3-alkyl propionic acid ester. This compound is then converted into the corresponding aldehyde, which is condensed with an eno-late to afford the final product. A representative synthetic procedure of this method is given in detail. 

Amine Bis-[2-fluoro-ethyl]-(3-methyl-phenyl)- ElOa, 576 (OTos - F)... 

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