Phenyl dimethylamine

The Step 4 product (0.8 mmol) dissolved in 2 ml THF was treated with 1ml 1M LiOH, then refluxed 1 hour, cooled, and treated with 1 ml 1M HC1. The mixture was concentrated and the residue (0.145 mmol) dissolved in 1ml DMF. The solution was treated with 3-(dimethoxyphosphoryloxy)-l,2,3-benzotriazine (0.18 mmol) followed by [3-(l-aminoethyl)-phenyl]-dimethylamine (0.145 mmol) dissolved in 0.5 ml DMF containing 81 jxl triethylamine. The solution was stirred 8 hours at 25°C, then filtered, and applied directly to a preparatory HPLC column (C18, 10-100% methyl alcohol/water/0.1% trifluoroacetic acid) for purification. The residue was then dissolved in 3 ml methyl alcohol and applied to a SAX column having hydroxide as the counter ion. The product was eluted with 10 ml methyl alcohol and isolated. 

Diphenylthiirene 1-oxide reacts with hydroxylamine to give the oxime of benzyl phenyl ketone (79JA390). The reaction probably occurs by addition to the carbon-carbon double bond followed by loss of sulfur monoxide (Scheme 80). Dimethylamine adds to the double bond of 2,3-diphenylthiirene 1,1-dioxide with loss of sulfur dioxide (Scheme 81) (75JOC3189). Azide ion gives seven products, one of which involves cleavage of the carbon-carbon bond of an intermediate cycloadduct (Scheme 81) (80JOC2604). 

Phenyl diazonium ion, PhN2, reacts with nucleophiles in several ways. Water displaces N2 to give phenol, while dimethylamine adds to the terminal N. 

Experimental observations indicate that electron-rich aromatic nucleophiles, such as phenoxide, add to phenyl diazonium ion in the same way as dimethylamine. 

Condensation of ethyl acetoacetate with phenyl hydrazine gives the pyrazolone, 58. Methylation by means of methyl iodide affords the prototype of this series, antipyrine (59). Reaction of that compound with nitrous acid gives the product of substitution at the only available position, the nitroso derivative (60) reduction affords another antiinflammatory agent, aminopyrine (61). Reductive alkylation of 61 with acetone in the presence of hydrogen and platinum gives isopyrine (62). Acylation of 61 with the acid chloride from nicotinic acid affords nifenazone (63). Acylation of 61 with 2-chloropropionyl chloride gives the amide, 64 displacement of the halogen with dimethylamine leads to aminopropylon (65). ... 

A suspension of 45 g 3-phenoxycarbonyloxy-1 -methyl-7-chloro-5-pheny -1,3-dihydro-2H-1,4-benzodiazepin-2-one in 450 ml methanol is treated with stirring, with 43 ml of a solution of dimethylamine in methanol (containlng31 gdimethylamine in 100 ml). Stirring ismaintained at 20°C to 25°C during 5 hours. The reaction mixture is filtered, and the filtrate is diluted with 450 ml water. The precipitate thus formed, is 3-(N,N-dimethylcarbamoyloxy)-1-methy -7-chloro-5-phenyl-1,3-dihydro-2H-1,4-benzodiazepin-2-one, which is collected on a filter, dried and recrystallized from ethyl acetate, and has a melting point of 173°C to 174°C. 

By way of graphical example of the various algebraic and geometrical concepts that are introduced in this chapter, we will make use of a measurement table adapted from Walczak etal.[ ]. Table 31.2 describes 23 substituted chalcones in terms of eight chromatographic retention times. Chalcone molecules are constituted of two phenyl rings joined by a chain of three-carbon atoms which carries a double bond and a ketone function. Substitutions have been made on each of the phenyl rings at the para-positions with respect to the chain. The substituents are CFj, F, H, methyl, ethyl, i-propyl, t-butyl, methoxy, dimethylamine, phenyl and NO2. Not all combinations two-by-two of these substituents are represented in the... 

The first step of a free radical aromatic substitution, the formation of the a-com-plex, is also an addition step. The o,m,p-product ratio therefore also responds to steric effects. This is shown for the free radical phenylation and dimethylamination of toluene and r.-butylbenzene in Table 8. The larger the substituent on the aromatic system and the bulkier the attacking radical, the more p-substitution product is obtained at the expense of o-substitution. In the phenylation reaction the yield of m-product also increases in contrast to the dimethylamination reaction. The substitution pattern of this latter reaction is, in addition to the steric effect, governed heavily by polar effects because a radical cation is the attacking species113. ... 

If trivalent phosphoms compounds are to be treated as electron-deficient species, then reactions of oxadiazoles with some Lewis acids should be reported here. 2-Phenyl-l,3,4-oxadiazole reacting with phosphoms trichloride in pyridine solution in the presence of triethylamine at low temperature furnished the respective dichlorophosphine and chlorophosphine, which were trapped by dimethylamine to give the corresponding amides. 2-Phenyl-l,3,4-oxadiazole also interacts over 24 h with the less reactive chlorodiphenylphosphine and dichlorophenylphosphine at room temperature to give phosphines (Scheme 14) <1999CHE1117>. These reactions of oxadiazoles resemble the behavior of 1-alkylimidazoles toward trivalent phosphorus derivatives. 

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>. 

Ein weiteres, auch in bezug auf die Stereochemie gut untersuchtes Beispiel dieser Art ist die Reaktion von 3-Acetoxy-3-aryl-3-(3-pyridyl)-propenen mit Dimethylamin unter Palla-dium(ll)-Katalyse, die zu (Z/ -Gemischen von l-Aryl-3-dimethylamino-l-(3-py-ridinyl)-propenen fuhren, z.B. zu (Z)- + (E)-l-(4-Brom-phenyl)-3-dimethylamino-l-(3-pyridyl)-propen im Verhaltnis 1,2 1. Die gleichen Produkte, jedoch in anderem (Zj Ey-Verhaltnis, erhalt man unter den gleichen Reaktionsbedingungen auch aus den iso-meren 3-Acetoxy-1 -aryl-1 -(3-pyridyl)-propenen3 ... 

By the extension of the above-mentioned stereoselective asymmetric addition of alkylithiums to other organolithium reagents such as lithium salts of methyl phenyl sulfide, 2-methylthiazoline, trialkylsilylacetylene, N-nitroso-dimethylamine, and acetonitrile, chiral oxiranes (95) U1), thiiranes (96) nl), acetylenic alcohols (98) 112), and amino alcohols (97) U1) were readily obtained. 

The procedure given above is an adaptation of the methylation method first used by Sommelet and Ferrand3 and developed more fully by Clarke, Gillespie, and Weisshaus.2 /3-Phenylethyldi-methylamine has been prepared from /9-phenylethylamine by alkylation with dimethyl sulfate 4 by the reaction of fi-phenyl-ethylamine and of N-methyl- S-phenylethylamine with formaldehyde 6 by catalytic reduction of phenylacetonitrile in the presence of dimethylamine 3 by the reaction of dimethylamine with /3-phenylethyl chloride 7 8 9 and with /3-phenylethyl bromide 9 and by the reaction of phenylacetaldehyde with dimethylamine.10... 

AMINES. An amine is a derivative of NH3 in which there is a replacement for one or more of the H atoms of Nil, by an alkyl group, such as -CH3 (methyl) or -C2H5 (ethyl) or by an aryl group, such as (>, H (phenyl) or i ll (naphthyl). Mixed amines contain at least one alkyl and one aryl group as exemplified by methylphenylamine CH3 Nnij O.H . When one, two, and three H atoms arc thus replaced, the resulting amines ate known as primary, secondary, and tertiary, icspectively. Thus, methylamine, CH3NH2, is a primary amine dimethylamine, iCHj) NH, is a secondary amine and trimethylamine. (CHs N. is a tertiary amine. Secondary amines sometimes are called imines tertiary amines, nitriles. 

The electrophilic properties of substituted 6//-l,3-thiazine-6-ones (208) in solution also shows reactivity at C-2 in acidic conditions and at C-6 in basic conditions. The regioselective reaction of 4-ethoxycarbonyl-2-phenyl-6//-l,3-thiazine-6-one with dimethylamine leads, after ring opening and reclosure, to two diasteriomeric 5-dimethylcarboxamido-4-ethoxy-carbonyl-2-phenyl-A2-thiazolines 209 and 210, whose structures were confirmed by X-ray diffraction studies on 210 (Scheme 84) (88BSF897). Com-... 

---