Dimethyl benzylamine

Elimination of hydrogen bromide from bromohexadienes with dimethyl-benzylamine, 41, 50 Enamines, 41, 65 uses of, 41, 66... 

Caution. Tetrahydrofuran is extremely flammable and forms explosive peroxides only fresh, peroxide-free material should be used. N, N-dimethyl-benzylamine causes skin and eye burns and is harmful if inhaled or absorbed through the skin. It should be manipulated in a well-ventilated fume hood protective gloves and goggles should be worn. 

In the same way, some others dipolar aprotic solvents are inconsistent with the use of complex bases. Thus dimethyl formamide is rapidly destroyed and condensation of Ph—CH2—Cl leads to a substantial amount of N,N-dimethyl benzylamine. N-Methyl pyrrolidone and, of course, dimethyl sulfoxyde react very easily with complex bases. Pyridine turns brown very rapidly. 

The solid benzylic bromide (for 1 and 2) or chloride (for 3) (2.00 mmol) in an evacuated 50-mL flask was exposed to dimethylamine gas from a lecture bottle (1 bar) at room temperature overnight. The quantitatively obtained A,N-dimethyl-benzylamines were obtained in pure form after condensation of the excess gas to a trap at 77 K for recovery, washing with water, and drying in a vacuum. 

The reactions of iV,A-dimethyl benzylamine [176] and benzylalcohol [177] with butyllithium and butyllithium TMEDA, respectively, result in specific ortho-lithiation, and are typical examples of the coordination only mechanism [1]. The benzylamine forms a complex with butyllithium, experimentally this is visible by a modest, but significant and promptly occurring heating effect when the amine is quickly added to the solution of butyllithium. Addition of benzylalcohol to two equivalents of BuLi TMEDA results also in the formation of a complex, viz. PhCH2OLi BuLi (analogous to the aggregates from alkali alkoxides and BuLi, e. g. 

AI3-26794 Araldite accelerator 062 BDMA Benz-enemethanamine, N,N-dimethyl- Benzyl-N,N-dimethyl-amine Benzylamine, N,N-dimethyl- Benzyldimethyl-amine N-Benzyldimethylamine N-Benzyl-N,N-dimethyl-amine CCRIS 6693 Dabco B-16 Dimethyl-benzylamine N,N-Dimethylbenzylamine N,N-Dimethyl-N-benzylamine N,N-Dimethylbenzenemethanamine EINECS 203-149-1 NSC 5342 Pentamin BDMA N-(Phenylmethyl)dimethylamine Sumine 2016 UN2619. Amine-based catalyst for flexible slabstock PU foam. Used as a polyurethane catalyst and an epoxy curing agent. Liquid mp = -75° bp = 181° d° = 0.915 7.m = 252, 268, 265 nm (cyclohexane) slightly soluble in H2O, freely soluble in EtOH, Et20 LD50 (rat orl) = 265 mg/kg. Air Products Chemicals Inc. Pentagon Chems. Ltd. -... 

Hauser et al. [1] investigated the metallation of JV.JV-dimethyl benzylamine with a number of strong bases. Whereas BuLi and BuNa gave either exclusively the O-metallated or a-metallated derivative, the reaction with PhLi, PhNa, and PhK led directly to the a-metallated product. A similar result is obtained when treating the amine with BuLi t-BuOK (= BuK ) in a mixture of THF and hexane [2]. The dark-red solution thus obtained reacts very smoothly with alkyl halides even at very low temperatures. In fact, the reaction with methyl iodide may be carried out like a titration using the characteristic colour as indicator. 

Rollman and co-workers have reported a study on Rh elution from polymer supports where the Rh was anchored to porous macroreticular polymer supports based on polystyrene cross-linked through divinylbenzene or ethyleneglycoldimethacrylate via dibutylphenylphosphine or AW-dimethyl-benzylamine groups. When a flow reactor at 85-100 °C and 5-10 MPa H2/CO was used Rh concentrations of 0.2-17 x 10 M were observed in the effluent. Increasing metal loadings, CO pressure, or the polarity of the solvent caused a corresponding increase in Rh loss while increasing temperature decreased metal loss. If these results are representative of the... 

Fig. 8 a-b. Conversion (a) of model epoxy compounds with phenol at 120 °C in presence of 1% catalyst, a Cycloaliphatic epoxy compounds LIX and LX (b) Glycidyl derivatives XVIII and XVII (see Table 14). b 1 - LIX, no catalyst 2 - LIX, oxalic acid 3 - LIX, lV,Ar-dimethyl-benzylamine 4 - LIX, ZnCl2 5 - LX, no catalyst 6 - LX, oxalic acid 7 LX, N,AT-dimethyl-benzylamine 8 - LX, ZnCl2. (b) 1 - XVIII, no catalyst 2 - XVIII, oxalic acid 3 - XVIII, N,1S -dimethylbenzylamine 4 - XVIII, ZnCl2 5 - XVII, no catalyst 6 - XVII, oxalic acid 7 -XVII, NjTST-dimethylbenzylamine 8 - XVII, ZnCl2... 

Most experimental studies have supported the nondissociative mechanism (a) for this reaction,but one study reported the following results the polyphos-phoric acid (PPA)-catalyzed Beckmann rearrangement of pinacolone oxime produced N-f-butylacetamide, while the PPA-catalyzed rearrangement of 2-methyl-2-phenylpropiophenone oxime produced N-benzoyl-a, -dimethyl-benzylamine and benzamide. Carrying out the rearrangement on a mixture of pinacolone oxime and 2-methyl-2-phenylpropiophenone oxime produced the products expected from each reactant, plus Af-f-butylbenzamide and N-acetyl-a,a-dimethylbenzylamine. 

Furans represent an important class of electron-rich heterocycles which are useful intermediates in synthetic chemistry and are broadly found as structural motifs of many natural products and pharmaceutically important substances [333]. Since furans are generally less nucleophilic than indoles and pyrroles, their catalytic enantioselective Friedel-Crafts-type conjugate addition has been much less developed so far. Very recently Harada et al. have developed a catalytic system able to achieve good enantioselectivities in the Friedel-Crafts alkylation of electron-rich furans with acychc a,p-unsaturated ketones [334]. As depicted in Scheme 2.117, a//o-threonine-derived oxazaborolidinone 190 (10 mol%) in the presence of V,V-dimethyl benzylamine (10 mol%) as cocatalyst in ether at -40°C, is an efficient catalytic system for the reaction affording the corresponding functionalized furans with good yields and enantioselectivities. 

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