M-Propylamine

Problem 18.4 Does M-propylamine or 1-propanol have the higher boiling point ... 

If the reaction temperature is kept at — 70°C (or lower), a secondary amine other than the two mentioned above affords the diaminochloro-cyclopropenium salt in the following yield (%) dimethylamine 10, diethylamine 56, di-M-propylamine 56, di-f-propylamine 69. 

Conjugate addition of strong nucleophiles to the >C=N—C=C< moiety, followed by ring opening of the resulting saturated 5(4H)-oxazolone. Thus, 57 reacts with simple or peptidic amino acid esters [Eq. (31)]. Similarly, 62 gives 63 in methanolic M-propylamine, and... 

The volume of ether added should be sufficient to precipitate most of the tri-m-propylamine hydrochloride in solution. The checkers diluted to a total volume of about 1 I. to precipitate the salt more efficiently. 

The NMR spectra of the interaction of 9-BBN with two series of amines with regular increasing steric requirements are studied (1) for the role of strain as a factor, (2) for the stability of addition compounds formed, and (3) for their exchange with an amine. One set of a Py bases includes Py and 2-methyl-, 2-ethyl, 2-isopropyl-, and 2-ferfbutylpyridine the second set is aliphatic amines such as M-propylamine, isopropylamine, diethylamine, diisopropylamine, and triethylamine, which are of increasing steric requirements and are examined for their interaction with 9-BBN. Quinuclidine (QN), a base with relatively low steric requirements, is compared with triethylamine, a base with very large steric requirements. 

Tri-n-propylamine [102-69-2] M 143.3, b 156.5 , d 0.757, n 1.419, pK 10.66. Dried with KOH and fractionally distd. Also refluxed with toluene-p-sulfonyl chloride and with KOH, then fractionally distd. The distillate, after addn of 2% phenyl isocyanate, was redistd and the residue fractionally distd from sodium. [Takahashi et al. J Org Chem 52 2666 1987.]... 

Hexane-free LDA was prepared by the dropwise addition of n-BuLi in hexane (leq, 2.4m) to a stirred solution of di-isopropylamine (1.5eq.) in hexane (ca. 2m) at 0°C. After complete addition, the viscous mixture was stirred for a further lOmin, after which time the hexane and excess di-iso-propylamine were removed under reduced pressure at 0°C. The resulting white solid was redissolved in sufficient THF at 0 °C to give an approximately 0.3 M solution. 

A variety of cleavage conditions have been reported for the release of amines from a solid support. Triazene linker 52 prepared from Merrifield resin in three steps was used for the solid-phase synthesis of aliphatic amines (Scheme 22) [61]. The triazenes were stable to basic conditions and the amino products were released in high yields upon treatment with mild acids. Alternatively, base labile linker 53 synthesized from a-bromo-p-toluic acid in two steps was used to anchor amino functions (Scheme 23) [62]. Cleavage was accomplished by oxidation of the thioether to the sulfone with m-chloroperbenzoic acid followed by 13-elimination with a 10% solution of NH4OH in 2,2,2-trifluoroethanol. A linker based on l-(4,4 -dimethyl-2,6-dioxocyclohexylidene)ethyl (Dde) primary amine protecting group was developed for attaching amino functions (Scheme 24) [65]. Linker 54 was stable to both acidic and basic conditions and the final products were cleaved from the resin by treatment with hydrazine or transamination with ra-propylamine. 

Nevertheless, the results observed for the reactions of o- and p-11 uoronitrobenzenes with propylamines demonstrate that (a) the dichotomy is not only observed when comparing primary with secondary amines (b) the origin is not due to primary steric effects (c) when there is no artho-n. m group the decrease in rate for the bulky amine is greater (d) the diminution in rate is due to an inhibition effect in the base-catalysed decomposition. 

Diazirines are the cyclic isomers of the alphatic diazo compounds. Both the diaziridines and the diazirines are starting materials for the synthesis of alkyl hydrazines. 3,3-Pentamethyl-enediaziridine can be hydrolyzed quantitatively to hydrazine. Methylamine may be substituted for ammonia in the procedure resulting in l-methyl-3,3-pentamethylenediaziridine (m.p. 35-36°, yield 62% of theoretical) and then methyl hydrazine. Use of ethylenediamine leads to ethylene bis-hydrazine via a bifunctional diaziridine (m.p. 143-144°, yield 48% of theoretical). Ammonia can also be replaced by w-propylamine or cydo-hexylamine cyclohexanone by acetone. 

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. ... 

Condensation of /3-phenylpropionamides with arylaldehydes, and then cyclization to l-aryl-2-benzazepin-3-ones (Pictet-Spengler reaction) is successful in PPA. The reaction fails, however, with aliphatic aldehydes. An analogous condensation between /3-(m-hydroxyphenyl)propylamine and then cyclization in hot butanol yields l-aryltetrahydro-2//-... 

Table II lists first-order rate constants, corrected for hydrolysis of ester in buffer alone. Propylamine served as a reference amine in its presence k (in min-1) for aminolysis decreased progressively from 0.98 x 10-2 to 0.51 x 10-2 to 0.05 x 10-2 as the length of the acyl group increased from 2 to 12 carbons (see Table II). The sharp drop for nitrophenyl laurate may be the result of micelle formation23 even at concentrations of 6x 10-6 M...

Figure 15. Open tubular liquid chromatography of amine-NBD derivatives using on-column fluorescence detection. Peaks correspond from left to right to ethylamine, n-propylamine, n-butylamine, cyclohexylamine, and n-hexylamine. Conditions 20-p.m X 8.3-m column with C-18 bonded phase 20% acetonitrile and 80% water (v/v) mobile phase at a linear velocity of 0.50 cm/s on-column injection of 5 nL. (Reproduced from reference 59. Copyright 1984 American Chemical Society.)...

Apples, pears Homogenized, extraction with chloroform, 0.1 M HC1, neutralized Na2C03, extraction chloroform HPTLC NH2 plates deriva-tized with propylamine, Supelco LC 18 Chloroform-cyclohexane-methanol (6.0 1 0.1), methanol-phosphate buffer (pH 6.6) (56 44) UV 285 nm UV 280 nm 48... 

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