Amines acetaldehydes

SYNS ACETALDEHYDE, AMINE SALT ALDEHYDE AMMONIA 1-AMINOETHANOL a-AMINOETHYL ALCOHOL ETHANOL, l-AAnNO-(8CI,9CI)... 

Activated acyl donors such as vinyl esters, halogenated methyl or ethyl ester, oxime esters or carboxylic acid anhydrides are often preferred for acylation of alcohols. With vinyl esters, acylation is in general fast and quantitative, as the equilibrium is driven by the release of vinyl alcohol, which will spontaneously tautomerize to volatile acetaldehyde. Amine nucleophiles will typically react spontaneously with these acyl donors, which hence cannot be used for resolution of amines. Vinyl acetate and ethyl acetate are common reagents (and often also solvents) for enzymatic kinetic resolution of alcohols and amines, respectively [9],... 

ISOCIANATO de METILO (Spanish) (624-83-9) Forms explosive mixture with air (flash point 0°F/- 18°C). Reacts slowly with water violently with warm water or steam, forming carbon dioxide and heat. Decomposes above 100°F/38 C. Violent reaction with acetaldehyde, amines, alcohols, acids, alkalis, strong oxidizers. Unless inhibited, can produce unstable peroxides contact with iron, tin, copper, or salts of these elements, or with certain catalysts such as triphenylarsenic oxide, triethylphosphine, or tributyltin oxide, or elevated temperatures may cause polymerization. Incompatible with glycols, amides, ammonia, caprolactam. Attacks some plastics, rubber, or coatings. The uninhibited monomer vapor may block vents and confined spaces by forming a solid polymer material. 

Other fairly recent commercial products, poly(vinyl amine) and poly(vinyl amine vinyl alcohol), have addressed the need for primary amines and their selective reactivity. Prior efforts to synthesize poly(vinyl amine) have been limited because of the difficulty hydrolyzing the intermediate polymers. The current product is prepared from /V-ethenylformamide (20) formed from the reaction of acetaldehyde and formamide. The vinyl amide is polymerized with a free-radical initiator, then hydrolyzed (eq. 7). 

Reactions with Ammonia and Amines. Acetaldehyde readily adds ammonia to form acetaldehyde—ammonia. Diethyl amine [109-87-7] is obtained when acetaldehyde is added to a saturated aqueous or alcohoHc solution of ammonia and the mixture is heated to 50—75°C in the presence of a nickel catalyst and hydrogen at 1.2 MPa (12 atm). Pyridine [110-86-1] and pyridine derivatives are made from paraldehyde and aqueous ammonia in the presence of a catalyst at elevated temperatures (62) acetaldehyde may also be used but the yields of pyridine are generally lower than when paraldehyde is the starting material. The vapor-phase reaction of formaldehyde, acetaldehyde, and ammonia at 360°C over oxide catalyst was studied a 49% yield of pyridine and picolines was obtained using an activated siHca—alumina catalyst (63). Brown polymers result when acetaldehyde reacts with ammonia or amines at a pH of 6—7 and temperature of 3—25°C (64). Primary amines and acetaldehyde condense to give Schiff bases CH2CH=NR. The Schiff base reverts to the starting materials in the presence of acids. 

Primary aromatic amines react with aldehydes to form Schiff bases. Schiff bases formed from the reaction of lower aUphatic aldehydes, such as formaldehyde and acetaldehyde, with primary aromatic amines are often unstable and polymerize readily. Aniline reacts with formaldehyde in aqueous acid solutions to yield mixtures of a crystalline trimer of the Schiff base, methylenedianilines, and polymers. Reaction of aniline hydrochloride and formaldehyde also yields polymeric products and under certain conditions, the predominant product is 4,4 -methylenedianiline [101 -77-9] (26), an important intermediate for 4,4 -methylenebis(phenyhsocyanate) [101-68-8], or MDI (see Amines, aromatic amines, l thylenedianiline). 

Grouping Acetone Ethane Ethyl-acetate Acetylene Ethyl amine Ethylene Acetaldehyde Ethyl glycol Crude oil Ethyl-ether Carbon disulphide Ethyl Nitrite... 

A test for secondary amines (e.g. proline) is the Chloranil test (1 drop of a 2% acetaldehyde solution in DMF, followed by one drop of a 2% solution of p-chloranil in DMF, leave for 5 mins). A positive test gives blue stained beads. 

Tetrahydroharman, m.p. 179-80°, has been prepared by a number of workers by a modification of this reaction, viz., by the interaction of tryptamine (3-)5-aminoethylindole) with acetaldehyde or paraldehyde and Hahn et al. have obtained a series of derivatives of tetrahydronorharman by the use of other aldehydes and a-ketonic acids under biological conditions of pH and temperature, while Asahina and Osada, by the action of aromatic acid chlorides on the same amine, have prepared a series of amides from which the corresponding substituted dihydronorharmans have been made by effecting ring closure with phosphorus pentoxide in xylene solution. 

In contrast to Wittig and Mayer s results (40), ethylidenebisdimethyl-amine (1,1-bisdimethylaminoethane) has been prepared, albeit by a very different method [AsN(CH3)2 plus acetaldehyde in ether see Section VII], and found to be distillable with only slight decomposition (J9). 

A reagent more reactive than tris(dimethylamino)arsine employed by Weingarten and White 39) was tetrakis(dimethylamino)titanium (145). With this compound it was possible to prepare N,N-dimethyl(l-isopropyl-2-methylpropcnyl)amine (147) from diisopropyl ketone. Weingarten and White 39) have suggested a possible mechanism for this reaction (see p. 88). If benzaldehyde 39,111), formaldehyde 111), or acetaldehyde 39) is used, the corresponding gem diamine or aminal (143) is formed. 

Experimental evidence, obtained in protonation (3,6), acylation (1,4), and alkylation (1,4,7-9) reactions, always indicates a concurrence between electrophilic attack on the nitrogen atom and the -carbon atom in the enamine. Concerning the nucleophilic reactivity of the j3-carbon atom in enamines, Opitz and Griesinger (10) observed, in a study of salt formation, the following series of reactivities of the amine and carbonyl components pyrrolidine and hexamethylene imine s> piperidine > morpholine > cthyl-butylamine cyclopentanone s> cycloheptanone cyclooctanone > cyclohexanone monosubstituted acetaldehyde > disubstituted acetaldehyde. 

Because of self-condensation under the conditions of the alkylation reaction, enamines derived from acetaldehyde or monosubstituted acetaldehydes cannot usually be alkylated 28) except when there is a bulky secondary amine used to produce the enamine 32a). In these cases C alkylation takes place in good yield. 

The Maunich reaction of a ketone, an amine, and an aldehyde is one of the few three-component reactions in organic chemistry. Cyclohexanone, for example, reads with dimethylamine and acetaldehyde to yield an amino ketone. The reaction takes place in two steps, both of which are typical carbonyl-group reactions. 

Auxiliary-controlled Streeker syntheses have so far only been carried out with amines serving as the chiral components. In the first asymmetric Streeker synthesis a solution of sodium cyanide, ( — )-(S)-a-methylbeuzylamine and its hydrochloride in water was mixed with a methanolie solution of acetaldehyde and stirred for five days. Hydrolysis of the resulting amino nitrile and subsequent hydrogenolysis furnished L-alanine with 90% optical purity 38-39-85. 

A very elegant approach has been developed by Kanerva et al. DKR of N-hetrocyclic a-amino esters is achieved using CAL-A [54]. Racemization occurs when acetaldehyde is released in situ from the acyl donor. In this case aldehyde-catalyzed racemization of the product cannot occur (Figure 4.28). This is one of the few examples reported for DKR of secondary amines (For a recent example see the above text and Ref. [38]). 

Secondary amines react at room temperature with acetaldehyde and p-chloranil according to the following scheme to yield intensely blue-colored dialkylaminovinylquinone derivatives [2] ... 

The blue derivatives formed with the reagent by alkaloids remain stable for at least one day and usually much longer (cover the chromatogram with a glass plate) [2, 6, 7]. The shade of color produced can be affected by fluorescence indicators incorporated in the silica gel layer [7]. Tertiary amine alkaloids do not react at room temperature with the acetaldehyde-containing reagent [2]. 

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