H-Propylamine

It is not an exaggeration to state that Brosch and Kirmse s contribution to the same reaction, but 34 years later (1991), was a sensation. At that time, theory and experiment (Ford and Scribner, 1983) indicated that the dediazoniation of 1-alkanediazonium ions is endothermic in the gas phase. Therefore, Brosch and Kirmse considered it as rather unlikely that racemates are really formed in such significant amounts as found by Streitwieser and Schaeffer for [l- H]butylamine (31%) and 2-methyl[l- H]propylamine (72%). 

Isothiazole itself (283), Rx = Rj = Rj - H, is converted to thiazole in 7% yield, in propylamine as solvent using a low-pressure mercury lamp (642). 

The Tcrom ester is prepared from the cesium salt of an N-protected amino acid by reaction with 2-(trifluoromethyl)-6-chromylmethyl bromide (DMF, 25°, 4 h, 53-89% yield). Cleavage of the Tcrom group is effected by brief treatment with n-propylamine (2 min, 25°, 96% yield). It is stable to HCl/dioxane, used to cleave a BOC group. ... 

A template synthesis employing Ni(OAc)2, 2,5-dihydroxy-2,5-dimethyl-1,4-dithiane, and 3,3 -iminobis(propylamine) gave the water-soluble five-coordinate complex [Ni(495)], the crystal structure of which shows trigonal bipyramidal coordination of Ni11 with the central amine and terminal thiolates in plane and the two imino nitrogens in axial positions. Solvatochromism of the complex is interpreted in terms of S" H bonding, which may be of relevance to the catalytic cycle in hydrogenases.1341... 

Reduction of 3-benzyl-8-chloro-4-oxo-4//-pyrido[l,2- ]pyrimidine-2-carboxylate <2004W004/064741> and 2-methyl-4-oxo-4//-pyrido[l,2-tf]pyrimidine-3-carboxylate <2003T4123> with DIBAL-H afforded 2- and 3-formyl derivatives, respectively. Reduction of /V-(4-fluorobenzyl)-3-hydroxy-8-[methoxy(methyl)amino]-4-oxo-6,7,8,9-tetra-hydro-4//-pyrido[l,2- ]pyrimidine-2-carboxamide with Zn-dust in aqueous AcOH afforded the 8-methylamino derivative, which was acylated with AcOH in the presence of Hiinig s base, HOBt, and l-(3-dimethylaminopro-pyl)-3-ethylcarbodiimide-HCl <2004W004/058756>. 3-(Perhydropyrido[l,2- ]pyrimidin-2-yl)propylamine was obtained by catalytic hydrogenation of 2-(perhydropyrido[l,2- ]pyrimidin-2-yl)propionitrile over a Pt02 catalyst <2003FRP1275647>. 

Reactions that involve significant bond formation in the ratedetermining step are in general expected to exhibit large and negative volumes of activation. This was for instance found for a series of cyclometallation reactions of benzylidenebenzylamines, -anilines, and -propylamine with palladium acetate in toluene and acetic acid solution (171, 172). The cyclometallated compounds are formed via C-H electrophilic bond activation to produce different types of metalla-... 

The triplet reaction of 2-nitrodibenzo[fc,primary amines (n-propylamine and benzylamine) was studied110 in polar and apolar solvents. In polar solvents, the irradiation results in the formation of two isomeric compounds, (alky-lamino)hydroxynitrodiphenyl ether andiV-(alkylamino)-2-nitrophenoxazine (equation 54). In apolar solvents, only the nitrophenoxazine is obtained. In polar solvents, the exciplex formed between the 2-n i trodi benzol h,e [ 1,4]dioxin triplet state and amines dissociates to the solvated radical ions, from which the diphenyl ether arises. 1-Nitrodibenzo[fr,e][l,4]dioxin is stable even on prolonged irradiation. 

Besides the increased reactivity, formation of species like 6a may also produce a change in the rate-determing step in substitutions of ortho-derivatives when compared with the para-isomers. For example, it has been recently demonstrated that the formation of 1 (L = F R1 = n-C H7, i-C3H7 R2 = H) is rate-limiting in the reaction of n-propylamine and isopropylamine with o-fluoronitrobenzene in toluene, while it is the decomposition of the corresponding zwitterionic intermediate that is rate-determining in the same reactions... 

A variety of alkyl amines B, including 1-propylamine, ethylene diamine, 1,3-diaminopropane, and (7 )-l-amino-2-propanol have been used as reactants. The guest exchange kinetic results are reported in Table 13. The presence of more than one reacting [/3-CD-H-A] structure is observed with A = DOPA and penicillamine. The results have been rationalized in terms of specific interactions in the relevant inclusion complexes which determine their structure and relative stability. 

AIPO4-5 molecular sieve (BET surface area, 299 m g ) used in this study was prepared by the method of Wilson et al. [1j. VjOg/AIPO -S samples were prepared by impregnating with aqueous solutions of ammonium vanadate after removing templating agent in the AIPO -S by calcining at 530°C. The samples were dried at 110 C for 24 h then calcined in air at 550°C for 2 h. VAPO -S was prepared from gel mixture of phosphoric acid, pseudoboehmite, vanadium pentoxide, tri-propylamine and water (1.3 PrjN x AljOj PjOj 40 HjO) by crystallization at 165°C for 3 - 7 days [7. ... 

Ha/Moutmori[lonit-(3-Trimethylsilyl-propylamin)-Pd-Komplex/C2 H5 0 H Normaldruck 20 25° 5 lOmin 3-Nitro-anilin 99 2... 

Like the oxa method for naming ethers (Problem 14.61), the aza method is used for amines. Di-n-propylamine, CH3CH2CH2NHCH2CH2CH3, is 4-azaheptane and piperidine is azacyclohexane. The four H s of NH can be replaced to give a quaternary (4°) tetraalkyl (tetraaryl) ammonium... 

Several further experimental results lend support to the mechanisms postulated to explain the formation of the photoproducts. Thus irradiation of thiophene and substituted thiophenes in the presence of -propylamine leads to pyrroles, presumably via cyclopro-penylthiocarbonyl, or Dewar thiophene, intermediates (75T785). An extremely interesting development is the isolation of l,2,3,4-tetrakis(trifluoromethyl)-5-thiabicyclo[2.1.0]pent-2-ene, or perfluoro(tetramethyl Dewar thiophene) (2) by vapor-phase irradiation of perfluorotetramethylthiophene (81ACR76) the yield is about 58%. The half-life of thermal rearomatization of (2) at 160 °C is 5.1 h. The fluxional behaviour of the Dewar thiophene... 

H-Propanol and ri-propyl acetate account for about 70% of the U.S. propionaldehyde derivative market. These compounds are used principally in flexographic and gravure inks which require volatile solvents to prevent smearing and ink accumulation on the printing presses. Some propanol is also converted into n-propylamines which aie important pesticide intermediates. -Propanol is also employed as a precursor for glycol ethers. 

Kempter and co-workers prepared benzodiazocines 134 (R = R1 = H R2 = H, Me) from 135 (R = H, Me) by reduction and subsequent cyclo-condensation with the appropriate carbonyl compound (75MI7 87ZC36). For example, these workers condensed 3-(o-aminophenyl)propylamine with either phosgene or alkyl chloroformate to obtain 134 (R = R1 = R2 = H, X = O). Reaction of the same diamine (77MI5 87ZC36) and substituted derivatives (77MI5) with carbon disulfide afforded thio-... 

R)-a-incthylbcnzylairnne (R)-a-( 1 -naphthyl)ethy lamine (R)-a-phenyl-l-propylamine (R)-n orepi n ep h ri n c (R)-2-aminobutane... 

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