Alkylative amination aldehydes

Sodium (metal). Used as a fine wire or as chips, for more completely drying ethers, saturated hydrocarbons and aromatic hydrocarbons which have been partially dried (for example with calcium chloride or magnesium sulfate). Unsuitable for acids, alcohols, alkyl halides, aldehydes, ketones, amines and esters. Reacts violently if water is present and can cause a fire with highly flammable liquids. 

Among the polymeric stabilizers may be listed poly-condensed polymers based on alkyl phenols, aldehydes, and ketones of the aliphatic series, where = 1 - 8 and R,R means alkyl [24], Na, K, Ca phenolates of poly-condensed polymers [25], and also products of epichlor-ide with one or more aliphatic amines C3—C30 [26]. 

Aldehydes hydric alcohols. and secondary alkyl amines... 

Unsymmetrical secondary aliphatic amines have been prepared by reaction of alkyl halides with benzylidene amines and subsequent hydrolysis 814 by reaction of alkyl halides with alkyl amines 5 by reduction of amine-aldehyde adducts 8-8 and by dealkylation of tertiary amines with dibenzoyl peroxide. ... 

Another type of N-alkylation was achieved by the [IrCl(cod)]2-catalyzed reductive alkylation of secondary amine with aldehyde and silane (Equation 10.29) [53], For example, the treatment of dibutylamine 117 with butyraldehyde 118 and EtsSiH 119 (a 1 1 1 molar ratio amine, aldehyde and silane) or polymethyUiydrosiloxane (PMHS) in 1,4-dioxane at 75 °C under the influence of a catalytic amount of [lrCl(cod)]2, gave tributylamine 120. 

The N-alkylation of amines with alcohols [63] can also be carried out with Ir catalysts through a similar domino sequence reaction. In this case, the aldehyde/ketone resulting from oxidation is condensed with an amine to the corresponding imine, which is hydrogenated to the alkylated amine [63]. By way of example, the reaction of benzyl alcohol with aniline in toluene afforded benzylaniline in a 88% isolated yield by using catalytic amounts of [ lr(/z-Cl)Cp Cl 2]/K2C03. 

ALKYLATIONS OF ALDEHYDES via REACTION OF THE MACNESIOEN AMINE SALT OF AN ALDEHYDE 2,2-DIMETHYL-3-PHENYLPROPIONALDEHYDE... 

The lower members of the homologous series of 1. Alcohols 2. Aldehydes 3. Ketones 4. Acids 5. Esters 6. Phenols 7. Anhydrides 8. Amines 9. Nitriles 10. Polyhydroxy phenols 1. Polybasic acids and hydro-oxy acids. 2. Glycols, poly-hydric alcohols, polyhydroxy aldehydes and ketones (sugars) 3. Some amides, ammo acids, di-and polyamino compounds, amino alcohols 4. Sulphonic acids 5. Sulphinic acids 6. Salts 1. Acids 2. Phenols 3. Imides 4. Some primary and secondary nitro compounds oximes 5. Mercaptans and thiophenols 6. Sulphonic acids, sulphinic acids, sulphuric acids, and sul-phonamides 7. Some diketones and (3-keto esters 1. Primary amines 2. Secondary aliphatic and aryl-alkyl amines 3. Aliphatic and some aryl-alkyl tertiary amines 4. Hydrazines 1. Unsaturated hydrocarbons 2. Some poly-alkylated aromatic hydrocarbons 3. Alcohols 4. Aldehydes 5. Ketones 6. Esters 7. Anhydrides 8. Ethers and acetals 9. Lactones 10. Acyl halides 1. Saturated aliphatic hydrocarbons Cyclic paraffin hydrocarbons 3. Aromatic hydrocarbons 4. Halogen derivatives of 1, 2 and 3 5. Diaryl ethers 1. Nitro compounds (tertiary) 2. Amides and derivatives of aldehydes and ketones 3. Nitriles 4. Negatively substituted amines 5. Nitroso, azo, hy-drazo, and other intermediate reduction products of nitro com-pounds 6. Sulphones, sul-phonamides of secondary amines, sulphides, sulphates and other Sulphur compounds... 

Direct catalytic intermolecular a-allylic alkylation of aldehydes and cyclic ketones has been achieved using a one-pot combination of a transition metal catalyst, Pd(PPh3)4, and an organocatalyst a secondary amine which facilitates enamine catalysis.300... 

A less common approach to 2,5-diketopiperazine was reported by Marcaccini et al. [79] who used a Ugi-4CR between amines, aldehydes, isocyanides, and chloroacetic acid to get adducts 140. Treatment of 140 with ethanolic potassium hydroxide led to an intramolecular amide N-alkylation reaction, giving 2,5-diketopiperazines 141... 

This method is effective for aldehydes bearing a or /1-alkyl substituents and alkyl zincs other than Et2Zn. It is noteworthy that only negligible alkylation of aldehyde (< 2%) is observed under these conditions. The produced amines can be further elaborated to optically enriched acylated amines with high efficiency and without any detectable loss of enantiopurity (Scheme 9.25). 

Polyurethanes (PU) The odor of many polyurethanes is caused by fishy smelling low molecular weight amines, mostly methylamines like trimethylamine, degradation products of the amine catalysts used during production. In some cases after evaporation of the fishy smelling amines, other odor qualities remain. One noticeable odor of PU samples was earthy, nutty, which can often be attributed to substituted pyrazines, formed by condensation of two a-aminoketones, subsequent oxidation or alkylation by aldehydes. One example is 2-ethyl-3,5-dimethylpyrazine (Mayer and Breuer, 2006). 

Amines will also react as nucleophiles with a wide range of electrophiles including alkyl halides, aldehydes, ketones, and acid chlorides. 

Alcohols and aldehydes are also suitable materials for the creation of an alkyl amine. In addition to the aforementioned formation of alkyl chloride as an intermediate, alcohols can be directly converted to amines under hydrogenation conditions in the presence of ammonia while aldehydes are prereacted to form imine followed by hydrogenation [13]. Selectivity of the primary amine with these techniques is difficult and this process is more typically utilized for the preparation of tertiary amines where the reaction can be driven to completion. In certain cases, alcohols and aldehydes provide structural elements which are not attainable from natural sources. An example is the formation of a hydrogenated tallow 2-ethyl hexyl amine. The amine is prepared as shown below in eqn 6.1.8 using a hydrogenated tallow amine reacted with 2-ethyl hexanal [14, 15] ... 

Similarly, (V-ethyl-l-naphthylamine was prepared in 88% yield, and (V-ethyl-, N-bu-tyl- and (V-benzyl-2-naphthylamine, and (V-ethyl- and (V-butyl-/ -toluidine were prepared in 50-64% yields.34 In the alkylation of / -toluidine and / -anisidine with butyraldehyde, N,N-dibutyl derivatives were also produced in 19 and 25% yields, respectively. The Emerson-Waters procedure was also applied to the reductive alkylation of 2-phenylpropylamines and 2-phenylisopropylamines with C1-C3 aldehydes (amine aldehyde ratio = 1 3).35 With higher aldehydes the monosubstituted products were isolated in good yields (in 48-94% yields with acetaldehyde), while with formaldehyde (V.N-dimethyl derivatives were obtained in 51-85% yields. 

The reductive alkylation with aldehydes to prepare Al-n-alkylarylamines generally leads to a mixture of /V,/V-dialkyl- and A-alkylarylamines, and the yields of alkylated amines are often poor with aldehydes other than formaldehyde (see eq. 6.12). 

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