Di-n-hexylamine

Phenyl-3-oxopropanoic acid (25 mmol) and EtjN (87.5 mmol) were dissolved in THF (150 ml) and cooled to —40°C. Ethyl chloroformate (27.5 mmol) was added dropwise to this solution and then the reaction mixture was stirred for 30 min at —20°C. Di-n-hexylamine (27.5 mmol) was added to the suspension and it was stirred at room temperature for an additional hour. The reaction mixture was diluted with water (100 ml) and extracted with ether (400 ml). The extract was washed with aq. 5% HCl (100 ml) and brine (2 X 100 ml) and dried over NajSO. The crude amide was obtained by removal of the solvent in vacuo and phenylhydrazine (25 mmol) was added. The mixture was heated to 100°C for 30 min. The residue was held in vacuo to remove the water formed and then powdered ZnCl2 (125 mmol) was added. The mixture was heated at 170"C with manual stirring for 5 min. The cooled residue was dissolved in acetone (100 ml) and diluted with ether (500 ml). Water (100 ml) was added. The organic layer was separated and washed successively with 5% aq. HCl (100 ml) and brine (2 x 100 ml) and dried over NajSO. The solvent was removed in vacuo, and the residue was recrystallized from EtOAc-hexane. The yield was 79%. 

Amines. Primary amines, RNHj, where R is alkyl, arylalkyl, or cycloalkyl, when boiled with Raney nickel (no Hj) are converted into the secondary amine (80% yield) and some tertiary amine (10%). n-Hexylamine —> di-n-hexylamine (70%) and tri-n-hexylamine (9%). The reaction is considered to involve dehydrogenation to the aldimine followed by addition of the starting amine, elimination of ammonia, and hydrogenation. 

Di-n-hexylamine added at 90 to a soln. of N-cyclohexylthiophthalimide in heptane, and stirred 6 hrs. -> N-cyclohexylthiodi-n-hexylamine. Y 96%. K. Boustany, Chimia 24, 396 (1970) different reaction with prim, amines cf. Tetrah. Let. 1970, 4983. 

Preparation of Poly(n-butylamino)(di-n-hexylamino)phosphazene Linear (NPCl2)n that is soluble in THF or benzene was prepared with solution polymerization of (NPCl2)3. Also, poly(n-butylamino)(di-n-hexylamino)phosphazene was prepared by the reaction (NPCl2)n, di-n-hexylamine, and n-butylamine using triethylamine in THF at room temperature and bubbling dry nitrogen gas. After the reaction was over, triethylamine hydrochloride was removed by filtration. When the filtrate was added to ethanol, white colored polymer was precipitated. The polymer was dissolved in THF, and then the solution was added to ethanol. This purification procedure of the polymer was repeated several times. 

Analogous products are obtained if 2-fury lmethylamine, di-n-propylamine, or -(1,5-dimethyl)hexylamine are used instead of NH3, with yields of 67, 88 and 84%, respectively. 

DIISOPROPYLAMINE DI-n-PROPYLAMINE n-HEXYLAMINE TRIETHYLAMINE 6-AMINOHEXANOL DIISOPROPANOLAMINE TRIETHANOLAMINE N-AMINOETHYL PIPERAZINE TRIETHYL PHOSPHATE HEXAMETHYLENEDIAMINE HEXAMETHYL PHOSPHORAHIDE TRIETHYLENE TETRAMINE HEXAMETHYLDISILOXANE... 

Fig. 7. Conversion-time curves for polymerization of NCA s (0.224 mole l l) with amines (0.015 mole l-1) at 25 C in iV.iV-dimethylformamide. O y-Ethyl-L-glutamate NCA-di-isopropylamme A y-Ethyl-L-glutamate NCA-n-hexyl-amine Q Sarcosine NCA-di-isopropylaraine Sarcosine NCA-n-hexylamine. (Reprinted from paper by C, H. Bamford, and H. Block Polyamino Acids, Polypeptides and Proteins, p, 65, Wisconsin University Press 1962 (Fig. 7)3...

The effect of /3-methyl groups was investigated only for the cis-a-arylsulphonyl-j3-bromo- or /3-chloro-ethylenes. The 2-4- to 3-9-fold rate decrease with MeO- ion, as well as the 1-3- to 3-2-fold decrease for /3-bromo-a-p-nitrobenzenesulphonylethylene-di-n-butylamine and cyclo-hexylamine reactions, may point to a contribution of the elimination-addition route with these nucleophiles. When the elimination becomes more difficult, either for thep-methyl derivative or with a chlorine leaving group, a j8-methyl group decreases the substitution rate 20- to 84-fold with the same amines. With PhS- ion, for which other substitution routes are less probable, the rate retardation is higher (322- to 3100-fold). 

Fig. 2. Conversion—time curves for polymerization of NCAs (0.224 mole 1 ) initiated by amines at 25°C in i i,AT-dimethylformamide solution, o 7-ethyl-L-glutamate NCA/di-isopropylamine, sarcosine NCA/n-hexylamine, 7-ethyl-L-glutamate NCA/n-hexylamine, Dsareosine NCA/di-isopropylamine. Bamford and Block [22],...

Dosing of the olefin feed with ammonia or other amines during the break-in period produces a rapid, though temporary, increase in activity. Steady-state activity is temporarily increased 200-500% by injecting n-butylamine, hexylamine, aniline, or di-n-butylamine into the feed. Amines with no N-H bonds, e.g., pyridine or triethylamine, inhibit the metathesis reaction. Pretreatment of the catalyst with ammonia before contact with olefin leaves the catalyst relatively inactive for metathesis reactions. In contrast, treating fully broken-in catalysts with pure ammonia at 430-450° C, or continuous addition of ammonia to the olefin feed, increases metathesis activity. Takahashi investigated the effects of ammonia, carbon tetrachloride,and 60 volatile compounds, including hydrocarbons and com-... 

Caspary (1968a) indicated the usefulness of low temperature for the identification of materials having room-temperature spectra which are similar to each other (e.g., -hexyl bromide and n-heptyl bromide -butylamine and n-hexylamine and sebacic acid di-n-butyl ester and azelaic acid di- -butyl ester [Fig. 3.16]). He compared other compounds at room temperature and low temperature, such as various ketones (19686) and aldehydes (1965). These substances, all of which are liquids at room temperature, show many differences at the low temperature. 

Ce2H77Ni9Zn, Zinc phthalocyanine - n-hexylamine, 37B, 286 Ca4H52Mn2N2oO, M Oxo-bis(phthalocyanatopyridinemanganese(III)) di-pyridinate, 32B, 238... 

The procedure is illustrative of a general method of ethylating amines, wherein one reacts the amine with ethylene using an alkali-metal salt of the amine as catalyst.2 Di- -butylamine and -hexylamine have been thus ethylated at 130-160°, aniline, o-toluidine, and N-methylaniline at 240-275°. In general, higher olefins add to amines only sluggishly.2... 

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