Cyanoethyl amines

Ammonium thiocyanate, 0479 Azidoacetonitrile, 0714 2,2/-Azobis(2,4-dimethylvaleronitrile), 3668 Azoisobutyronitrile, 3011 2,2/-Azoisovaleronitrile, 3345 Bis(acrylonitrile)nickel(0), 2312 Bis(2-cyanoethyl)amine, 2397... 

Benzyl bromide, Molecular sieve, 2735 Benzyl chloride, Catalytic impurities, 2738 1,2-Bis(chloromethyl)benzene, 2946 Bis(2-cyanoethyl)amine, 2397 Bis(trimethylsilyl) peroxomonosulfate, 2602 Borane -tetrahydrofuran, 0138 Butylmagnesium chloride, 1641 Calcium acetylide, Methanol, 0585 Calcium chloride, 3923 Cerium, Water, 3961... 

Alanine has been prepared by the catalytic reduction of cyanoacetic esters 1 or salts 2 by heating acrylonitrile,3 /3-amino-propionitrile,4 iw-(/3-cyanoethyl)-amine,5 /3-hydroxypropionitrile, /3-alkoxypropionitriles,7 u.s-(/3-cyanocthyl) ether,8 or bis-(fi-cyano-ethyl) sulfide 8 with aqueous ammonia at 150-225° by the hydrolysis of /3-aminopropionitrile with concentrated hydrochloric acid and subsequent removal of the acid with anion exchange resins.9 The method as described above has been published.10 Additional references to methods of preparation are given in connection with a procedure for the making of /3-alanine from suc-cinimide through the action of potassium hypobromite.11... 

Aminopropionitrile and bis-(fi-cyanoethyl)-amine have been made by the addition of anhydrous 2-3 or aqueous4 ammonia to acrylonitrile. 

Preparation of Secondary Aliphatic Nitramines. A solution of / ,/ -bis(cyanoethyl)amine (10.0 grams, 0.08 mole) in 60 ml. of methylene chloride was cooled to —30°C., and 5.3 grams (0.04 mole) of nitronium tetrafluoroborate was added over a 10-minute period. The mixture was stirred for 1 hour at 0°C., then 4 hours at room temperature. The hydro-fluoroboric acid salt of / ,/ -bis (cyanoethyl) amine, 8.3 grams, 99% yield,... 

SYNS BBCE BIS-(2-CYANOETHYL)A VnNE NJSI-BIS(2-CYANOETHYL)AMINE 2-CYANO-N-(2-CYANO-ETHYL)ETHANAMINE DI(2-CIANOETIL)AMMINA (ITALIAN) 2,2 -DICYANODIETHYLAMINE DI-(2-CYANOETHYL)AMINE IDPN 3,3 -I flNOBIS-PROPANENITRILE L aNO-, -DIPROPIONITRILE P,p-L aNODIPROPIONITRILE P,P -IMINODIPROPIO-NITRILE 3,3 -IMINODIPROPIONITRILE 2341 I.S. USAF A-8564... 

DICYANOETHAN E see SNEOOO DI-(2-CYANOETHYL)AMINE see BIQ500 DICYANOGEN see COOOOO DICYANOMETHANE see MAO250... 

The addition of ammonia to acrylonitrile gives /S-aminopropionitrile and fczs-(/S-cyanoethyl)-amine. The former is hydrolyzed directly to /S-amino-propionic acid (90%) by barium hydroxide, " and the latter may also be converted through the intermediate phthalimide to the same amino acid (6S)%). A variation of this procedure involves condensation of phthalimide and acrylonitrile to /S-phthalimidopropionitrile, Both amino and carboxyl groups are formed during the subsequent hydrolysis by hydrochloric acid. The free /S-alanine (75%) is liberated from the hydrochloride by lithium hydroxide. ... 

Arecoline is prepared from bis(2-cyanoethyl)amine (174) which is a by-product of the alanine synthesis [125] (Scheme 23). 

Bachman and Barker247 cyclized bis-(2-cyanoethyl)amine in a simple reaction, obtaining a 70% yield of 4-iminopiperidine-3-carbonitrile ... 

Dioxan (400 ml), distilled over sodium, is placed in a three-necked flask fitted with a gas inlet tube, a reflux condenser carrying a calcium chloride tube, and an efficient stirrer. Naphthalene (25 g), sodium (2 g), and bis-(2-cyanoethyl)amine (50 g) are added and the air is replaced by nitrogen. The mixture is heated, with stirring, on a water-bath for several hours, then poured whilst hot into benzene (11), in which the cyclic compound is insoluble. After recrystallization from ethanol, the 4-iminopiperidine-3-carbonitrile melts at 187-188° with decomposition. 

It was shown [108] that the nitration of aromatic amines proceeds differently depending on their basicity. Amines of moderate to low basicity, such as bis(2-cyanoethyl)amine (pATa = 5.25J, bis(2,2,2-trinitroethyI)-amine (p/ a = 0.05) are nitrated by NO2 BF4 to the corresponding N-nitramines in acetonitrile or ethyl acetate in yields of 87-98%. The nitration of highly basic dialkylamines (pK = 8.70-11.15) is accompanied by the partial reduction of NO2 BF4 to nitrosonium tetrafluoroborate and the formation of nitrosamines, The content of nitrosamine in the reaction mixture increases with increase of the reaction temperature. Nitronium hexafluorosilicate proved to be a milder nitrating agent its application makes it possible to reduce greatly the formation of nitroso- derivatives. 

Multldentate amine complexes. In a more general study, Drago et al. (11,12) were able to attach bis(cyanoethyl)amine to iodomethylated polystyrene (Equation 2). Reduction affords the bound dipropylene-triamlne system. 

As an alternative to the two-step approach, mesoporous silica with organic moieties covalently linked to their internal surface could be obtained in a single-step cocondensation of siloxane and organosiloxane precursors using similar supramolecular templating techniques as those for the synthesis of pure silica. Successful one-step syntheses of MCM-41 silicas modified with alkyl, phenyl, vinyl. cyanoethyL amine, thiol, and propylsulfonic acid moieties were reported in the literature.Similar preparations were extended to MCM-48 silica and to meso-... 

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