Diethyl -amine

Figure 7 shows a fit of the UNIQUAC equation to the iso-baric data of Nakanishi et al. (1967) for the methanol-diethyl-amine system this system also exhibits strong negative deviations from Raoult s law. The UNIQUAC equation correctly re-... 

DIETHYL AMINE 240-418 -2 9626E 0l -3 2272E 03 -2.1227E-02 8.0047E 00 0 ... 

DIETHYL AMINE -1.3600EA03 3.2979EA04 -9.5371E-02 2.A382EA02... 

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. 

V-trimethyl silyl diethyl-amine [996-50-9] TMSDEA (CH3)3SiNH(C3H3)3... 

V-Trimethyl silyl diethyl amine (TMSDEA) is a stroagly basic silylatiag reageat and is particulady usehil for derivatiziag low molecular weight acids. The reaction by-product, diethylamine, is volatile enough to be easily removed from the reaction medium. 

The methods of preparation of ferrocene have been reviewed by Pauson and by Fischer. Ferrocene has been made by the reaction of ferric chloride with cyclopentadienylmagnesium bromide, by the direct thermal reaction of cyclopentadiene with iron metal, by the direct interaction of cyclopentadiene with iron carbonyl, by the reaction of ferrous chloride with cyclopentadiene in the presence of organic bases such as diethyl-amine, by the reaction of ferrous chloride with sodium cyclo-[lentadienide in liquid ammonia, and from cyclopentadiene and... 

Disulfiram may be made by the reaction of diethyl amine with carbon disulfide in the presence of sodium hydroxide. The (CjHjljNCSSNa intermediate is oxidatively coupled using hydrogen peroxide to give disulfiram. 

One mole of the chloracetyl xylidide thus prepared and 2.5 to 3 mols diethyl amine are dissolved in 1,000 ml dry benzene. The mixture is refluxed for 4 to 5 hours. The separated diethyl amine hydrochloride is filtered off. The benzene solution is shaken out two times with 3N hydrochloric acid, the first time with 800 ml and the second time with 400 ml acid. To the combined acid extracts is added an approximately 30% solution of sodium hydroxide until the precipitate does not increase. 

Mixtures of 3//-azepines are also formed from l,2-dimethyl-4-nitrobenzene, which in diethyl-amine yields A,./V-diethyl-5,6-dimethyl-3//-a7cpin-2-amine (9%) and AfN-diethyl-4,5-dimeth-yl-3f/-azcpin-2-aminc (22% oxalate mp 119-120°C).66 Likewise, 2,4-dimethyl-l-nitrobenzene furnishes a mixture of /V.A-diethyl-5,7-dimethyl-3//-azepin-2-amine (7% oxalate mp 140-141UC) and /V,A-diethyl-3,5-dimethyl-3//-azepin-2-amine (2% oxalate mp 85-86 C). The symmetrically substituted l,3-dimethyl-5-nitrobenzene, as expected, yields only (V.tV-diethyl-4,6-dimethyl-3//-azepin-2-amine (46% bp 96 99 (2/1.3 Torr). 

Figure 14.9 Vapor-liquid equilibrium data and calculated values for the diethyl-amine-water system. Calculations were done using parameters from simplified CLS estimation [reprinted from Computers Chemical Engineering with permission from Elsevier Science],...

Ethyl Propane-a,a,y,y-tetracarboxylate.—To a mixture of 1600 g. (10 moles, 1510 cc.) of ethyl malonate (Note 1) and 400 g. of 40 per cent formalin (5.3 moles) in a 5-I. round-bottom flask, cooled to 50 by immersion in ice, is added 25 g. (35 cc.) of diethyl-amine. The mixture is then allowed to come to room temperature and remain for fifteen hours, after which the flask is heated under a reflux condenser on a boiling water bath for six hours. The aqueous layer is then separated, and the residue is distilled under reduced pressure (Note 2) from a 3-I. special Claisen flask (Org. Syn. 1,40). The ester distils at i9o-2oo°/i2 mm.(2io-2i5°/2o mm.) The yield (Note 3) is 1000 g. (61 per cent of the theoretical amount). 

The dieneamine, however, maintains the normal (2+4) mode of diene reactivity followed by elimination of diethyl amine, thus yielding 2,7-diphenyl tropone (364). 

Thermochemical data from the compilation of Stull et at., 1969. Entropy values are based on a 1 M standard state. The asterisk denotes symmetry-corrected quantities. Symmetry numbers were chosen as follows 18 for the n-alkanes, cis-3-hexene, dibuthyl sulphide, diethyl ether, and diethyl amine 2n for the cycloalkanes and 2 for all of the remaining ring compounds 3 for the alkanols, alkanethiols and alkyl amines 9 for the methyl alkyl sulphides... 

The selectivity in favor of the desired monobenzylated product was found to be >99% and the immobilized Pt02 was found to be 4-5 times more active than the commercial Adams catalysts. In solution or in immobilized form, the PtOz colloid is effective in the hydrogenation of carbonyl compounds or of olefins. Recently, the heterogeneous catalytic amination of aryl bromides by immobilized Pd(0) particles has been reported [163], Secondary amines such as piperidine and diethyl amine are used in the amination of aryl bromides and the reaction proceeds with good turnover numbers and regio-control. The catalysts can be reused repeatedly without loss of activity or selectivity after filtration from the reaction mixture. 

It is also common and correct to name amines with each alkyl branch listed as an attachment before the suffix -amine. In this system of nomenclature, the molecules in Figure 1.16 are ethylamine, methyl ethyl amine, and methyl diethyl amine. Several other methods of naming amines exist, but they will not be covered in this course. 

Solvent effects have been investigated in isatin (193) hydrolysis. Results from ethanol-water and acetonitrile-water mixtures revealed that for alkaline hydrolysis log k was correlated with the reciprocal of the dielectric constant. A tetrahedral intermediate (194) is involved, which breaks down to yield the ring-opened amino acid (195). A comparison has been made of the lability of isatin (193) towards diethyl-amine and hydroxide ion, the latter showing the greater effect. ... 

Water and methanol react in specially favourable systems only. Amines are much more effective as became clear at the beginning of the investigations by the possibility of photoamination in amine/ water and amine/methanol mixtures. Interestingly, nitroanisoles, like other aromatic nitro-compounds, when irradiated in pure diethyl-amine give only reduction products (Barltrop and Bunce, 1968). 

As it may be a useful comparison, it is asked what is the enthalpy change for the formal, simple insertion of an oxygen atom in the NH bond of an amine (W-hydroxylation) For ammonia, the change to hydroxylamine is only +4 kJ moH . The exothermicity of the comparable change for the primary methyl amine is —27.2 kJmoH (g) and for the secondary diethyl amine it is —49.3 kJmoH . 

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