Dimethyl-phenyl-amine

K N-Dimethy Ion Mine N,N-Dimethyl phenyl-amine or N,N-Dimethylaminobenzene,... 

Molecular rotors with a dual emission band, such as DMABN or A/,A/-dimethyl-[4-(2-pyrimidin-4-yl-vinyl)-phenyl]-amine (DMA-2,4 38, Fig. 13) [64], allow to use the ratio between LE and TICT emission to eliminate instrument- and experiment-dependent factors analogous to (10). One example is the measurement of pH with the TICT probe p-A,A-dimethylaminobenzoic acid 39 [69]. The use of such an intensity ratio requires calibration with solvent gradients, and influences of solvent polarity may cause solvatochromic shifts and adversely influence the calibration. Probes with dual emission bands often have points in their emission spectra that are independent from the solvent properties, analogous to isosbestic points in absorption spectra. Emission at these wavelengths can be used as an internal calibration reference. 

It is supposed that the nickel enolate intermediate 157 reacts with electrophiles rather than with protons. The successful use of trimethylsilyl-sub-stituted amines (Scheme 57) permits a new carbon-carbon bond to be formed between 157 and electrophiles such as benzaldehyde and ethyl acrylate. The adduct 158 is obtained stereoselectively only by mixing nickel tetracarbonyl, the gem-dibromocyclopropane 150, dimethyl (trimethylsilyl) amine, and an electrophile [82]. gem-Functionalization on a cyclopropane ring carbon atom is attained in this four-component coupling reaction. Phenyl trimethyl silylsulfide serves as an excellent nucleophile to yield the thiol ester, which is in sharp contrast to the formation of a complicated product mixture starting from thiols instead of the silylsulfide [81]. (Scheme 58)... 

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. 

SYNTHESIS OF [l-(2,4-DIMETHYL-PHENYL)-ETHYL]-(4-METHOXY-PHENYL)-AMINE... 

Dimethyl-phenyl)-eth-( )-ylidene]-phenyl-amine (51.0 mg, 0.20 mmol)... 

N,N-Dimethyl-xeny amine or N,N-Dimethyl-p-bipheny(amine. See N,N-DimethyIaminobi-phenyl in this Vol, pD1308-R... 

Hexonltro-3,3 -dimethyl-dlphenylamine or Bis(3-methyl-2,4,6-tri-nitro-phenyl)-amine, [CHJ.C4H(NOJ)3]2NH, bm tables (from ale), mp 60°. Can be prepd by warming 4,6-dinitro-3,3 -dimethyl-diphenyl amine with nitric acid(d 1.5) on a water bath. Its expl props were not investigated... 

Moreover, the formation of enoxy-silanes via silylation of ketones127 by means of N-methyl-N-TMS-acetamide (1 72) in presence of sodium trimethylsilanolate (173) was reported in 1969 and since then, the use of silylating reagents in presence of a catalyst has found wide appreciation and growing utilization as shown in recent papers128-132 (Scheme 27). Diacetyl (181) can be converted by trifluoromethylsul-fonic acid-TMS-ester (182) into 2,3-bis(trimethylsiloxy)-l, 3-butadiene (7treatment with ethyl TMS acetate (7 5)/tetrakis(n-butyl)amine fluoride l-trimethylsiloxy-2-methyl-styrene (i<56)130. Cyclohexanone reacts with the combination dimethyl-TMS-amine (18 7)/p-toluenesulfonic acid to 1-trimethylsiloxy-l-cyclohexene (iSS)131. Similarly, acetylacetone plus phenyl-triethylsilyl-sulfide (189) afford 2-triethylsiloxy-2-pentene-4-one (790)132. ... 

Amin Dimethyl-phenyl- -imin E16a, 1043 (N-Deprotinier.)... 

N-(2,3-Dimethyl-phenyl)- -methylester E4, 466 (SM -> SR) N-(l-Methyl-2-phenyl-ethyl)- (Salze) E4, 461 (CS2 + Amin)... 

Sulfimid S,S-Dimethyl-N (2,3-dimethyl-phenyl)- Ell, 905 (R2SO + Amin)... 

Dimethyl-propyl-amin Dicthyl-(2-phenyl-ethyl)-amin Benzyl-dime thyl-amin Dimethyl-(4-methoxy-benzyl)-amin Bcnz°L ... 

Asymmetric palladium(0)-catalysed substitution of racemic allylic substrates with malonate and benzylamine as nucleophiles were performed using new enantiopure cyclic (3-iminophosphine ligands namely (2,6-dimethyl-phenyl)-( 1 -phenyl-2, 3,3a, 8a-tetrahydro- 1H-1 -phospha-cyclopenta[-a]inden-8-ylidene)-amines 1 (RP)... 

SYNTHESIS OF (2,6-DIMETHYL-PHENYL)-(l-PHENYL-2,3,3a,8a-TETRAHYDRO-lH-l-PHOSPHA-CYCLOPENTA[a]INDEN-8-YLIDENE)-AMINES 1RP... 

Amsberry and Borchardt have applied Cain s cascade concept to prepare lipophilic polypeptide prodrugs. The amine functionality of the polypeptide is coupled to 2 -acylated derivatives of 3-(2, 5 -dihydroxy-4, 6 -dimethyl-phenyl)-3,3-dimethylpropionic acid (Fig. 33.23). Under simulated physiological conditions the parent amine is regenerated in a two-step process enzymatic hydrolysis... 

By oxidation of the labeled products [28 and 29 or 30ab] to labeled benzoic and substituted benzoic acids followed by assay of these purified acids for carbon-14, the relative migratory abilities of the Ar groups with respect to phenyl were determined. Thus in the dehydration, with phosphorus pentoxide in xylene, of a series of carbinols (27, X = OH), the following migratory aptitudes (Ar Ph) were determined p-xenyl, 1-3 m-tolyl, 1-6 p-i-propylphenyl, l-8 3,4-dimethyl-phenyl, 1-9 p-tolyl, 2-0 p-ethylphenyl, 2-2 p-t-butylphenyl, 3-2 and p-anisyl, 21-2. Burr (1953) demonstrated the p-tolyl phenyl migration ratio to be 2-5 during the solvolysis of 2-phenyl-2- p-tolylethyl-l-i C tosylate (27, Ar = p-tolyl, X = tosyl). In a series of deaminations of the primary amines (27, X = NH ) and 31 (Ar = p-tolyl and o-tolyl) the p-tolyl phenyl (1 2), p-biphenyl phenyl (1 0) p-anisyl phenyl... 

The novel concept of elaboration of unactivated olefins by nucleophiles has been reported. Nucleophilic attack is initiated by reaction of the olefin with dimethyl(tnethylthio)sulphonium fluoroborate (4) and, in conjunction with nitrogen nucleophiles, a high degree of regiocontrol is observed in an azasul-phenylation reaction (Scheme 7), the products of which not only permit an overall olefin amination, but also an oxazoline synthesis, a m-hydroxyamination, and an aziridine synthesis. The analogous selenium reagent, dimethyl(phenyl-seleno)sulphonium fluoroborate, p-phenylselenates a variety of anilines in moderate yield. ... 

Abel and Dunster have reported that dimethyl(trimethylstannyl)amine, on treatment with phenyl isothiocyanate, yields the trimethylstannyl-thiourea (301). On the other hand, Matsuda and his co-workers found that the related reaction of N-trimethylsilyl(diphenylmethylene)amines with isothiocyanates affords equilibrium mixtures of the two rapidly interconvertible tautomeric compounds (302) and (303). ... 

Two closely related indoles fused to an additional saturated ring have been described as CNS agents. The first of these is obtained in straightforward manner by Fischer indole condensation of functionalized cyclohexanone 0 with phenyl hydrazine (19). The product, cyclindole (21) shows antidepressant activity. The fluorinated analogue flucindole (26) can be prepared by the same scheme. An alternate route starting from a somewhat more readily available intermediate involves as the first step Fischer condensation of substituted phenyl hydrazine with 4-hydroxycyclohexanone (23). The resulting alcohol (24) is then converted to its tosylate (25). Displacement by means of dimethyl amine leads to the antipsychotic agent flucindole (26). ... 

Of this product, 4.5 g in 30 cc of dry isopropyl alcohol are refluxed for 16 hours with 2.5 g of (3-chloroethyl dimethyl amine. The solution is cooled and filtered clear from the solid by-product. The solvent is removed under reduced pressure on the steam bath and the residue is washed with anhydrous ether. It is dissolved in ethyl acetate from which it crystallizes. It is the hydrochloride of (3-(dimethylamino)ethyl ester of 2-phenyl-2-( 1-hy-droxycyclopentyl) ethanoic acid, melting at 134° to 136°C. 

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