Amines tri-n-butylamine

A series of acyclic azophenol-dyed oligoethers 64 (azophenol podand, PoOn n = number of oxygen atoms in the two side arms Fig. 17) also show the com-plexation-coloration with amines in similar manner as described for the azophenol crowns. For example, PoOg (64, n = 2) makes a saltex (Xmax 568 nm) with bulky primary amine, t-BuNH2 in chloroform, whereas it does not with tertiary amine, tri-n-butylamine (Fig. 17). 

Beilstein Handbook Reference) A13-15424 Amine, tributyl- BRN 1698872 CCRIS 4879 EINECS 203-058-7 HSDB 877 N,N-Dibutyl-1-butan-amine Tri-n-butylamine Tributilamina Tributylamine Tris-n-butylamine UN2542 UN3254. Clear liquid mp = -70° bp = 216.5° d O = 0.7770 Xm = 242 nm (e = 1000, CHCI3) slightly soluble in H2O, CCI4, soluble in Me2CO, CeHe, very soluble... 

Synthesis of Amides from Carboxylic Acids/ In the corresponding amidation process (eq 2) there is a requirement for the addition of 1 equiv of a tertiary amine (Tri-n-butylamine) to ensure efficient utilization of the amine component (R R NH). Once again, carboxyl activation is achieved using a 2-halopyridinium salt (2) but, unlike the esterification reaction, amidation is best carried out as a two-step one-pot process. 

Compared with primary and secondary amines, tertiary amines are virtually unreac-tive towards carbenes and it has been demonstrated that they behave as phase-transfer catalysts for the generation of dichlorocarbene from chloroform. For example, tri-n-butylamine and its hydrochloride salt have the same catalytic effect as tetra-n-butylammonium chloride in the generation of dichlorocarbene and its subsequent insertion into the C=C bond of cyclohexene [20]. However, tertiary amines are generally insufficiently basic to deprotonate chloroform and the presence of sodium hydroxide is normally required. The initial reaction of the tertiary amine with chloroform, therefore, appears to be the formation of the A -ylid. This species does not partition between the two phases and cannot be responsible for the insertion reaction of the carbene in the C=C bond. Instead, it has been proposed that it acts as a lipophilic base for the deprotonation of chloroform (Scheme 7.26) to form a dichloromethylammonium ion-pair, which transfers into the organic phase where it decomposes to produce the carbene [21]. 

The reaction of III with two or four equivalents of n-butyllithium resulted in the formation of a new product, N, N-di-n-butyl-terf-butylamine (VI), in yields up to 16% of theory. This previously unknown tertiary amine was identified by infrared and mass spectrometric analyses. A comparison of the mass spectrum of VI with that of the known tri-n-butylamine (Table I) shows thait the same major peaks appear but in quite... 

The authors studied the polymerization of formaldehyde with amines including tertiary amines at —78°C in various solvents (Table 1), and determined the conversion after 15 min reaction time. Tertiary amines are highly reactive initiators for formaldehyde polymerizations even at the level of 10 mole T per mole 1 of formaldehyde. The reactivity of the amine is related to its pXg value but also to the branching of the aliphatic side chains of the substituents on the nitrogen atom. Branched amines, especially when the branching is on the a-carbon atom as in the case of a tertiary butyl group, are less effective initiators than tertiary amines with n-alkyl chains. The pX a of the amine is not the essential feature for an efficient tertiary amine initiator, because pyridine was almost as effective as tri-n-butylamine but quinoline, with a similar pK g as pyridine, is almost inactive (Table 1). 

It is interesting to note that triphenylphosphine is more effective as initiator than tertiary amines. In general it can be stated that the initial rate of formaldehyde polymerization with tri-n-butylamine is proportional to the amine concentration and the initial rate is also proportional to the monomer concentration (Figs. 1 and 2). The temperature dependence of... 

The first three tertiary amines in the aliphatic series were studied by Strecker and Baltes. The authors studied tri-n-butylamine, tri-n-hexylamine, and tri-n-heptyl-amine. Each amine was ozonated at dry ice temperature and treated with picric acid. The tri-n-butylamine oxide picrate readily deposited as crystals on standing. Although the latter two amine oxides formed oily products at first, on long standing in the refrigerator they gave crystals of the amine oxide picrates. The purified amine oxide picrates were analyzed by direct titration with perchloric acid. 

Diaminobutane, DAB (Aldrich), Di-n-Butylamine, DBA (Aldrich), and Tri-n-Butylamine, TBA (Eastman Organic Chemicals), were used as curing agents. Each was distilled under Helium at one atmosphere and sealed. The amine analysis of Critchfield and Johnson (15)was conducted to determine purity. Table I. The purity and the theoretical equivalence were used to determine the weight of amine needed for a given weight of resin. 

No reaction took place with hydrogen peroxide and tri-n-butylamine in the absence of sodium molybdate. The observation that tri-n-butylamine is an effective catalyst led us to evaluate the reaction with a range of structurally different amines. The results are reported in Table 3. 

All the thioethers are liquids at 60°C with the exception of dibenzothiophene. The reactions were performed neat, except dibenzothiophene was reacted in toluene. High yields are obtained. In the absence of sodium molybdenate and tri-n-butylamine the reactions were very slow. There was no evidence for tar formation in the catalysed reactions. The reactions were worked-up by washing with dilute acid. Phase separation was achieved easily. This effectively removed from the product the molybdate (<50 ppm by ion coupled plasma emission spectroscopy) and amine (<0.1% by gas chromatography). 

Tri-n-butylamine is converted to the amine oxide5 with hydrogen peroxide at 90°C, but the amine oxide was not detected (<1% by H-NMR) during the reaction of 1. The amine oxide was not an effective auxiliary for replacement of the amine. A representation of the general reaction is given in Scheme 1. 

Reductions. The combination of trichlorosilane and tertiary amines (tri-n-propylamine, tri-n-butylamine used for the most part) has been used by Benkeser to effect some interesting reductions. Thus polyhalo compounds are reduced cleanly and selectively by this combination 1... 

Dichlorocarbene Dichloronorcarane can be prepared in about 75% yield from cyclohexene, chloroform, and an aqueous solution of sodium hydroxide in the presence of tri-n-butylamine or the hydrochloride as catalyst. Some other tertiary amines or quaternary ammonium salts are equally effective tetra- -butylammonium bromide, N-n-butylpiperidine, N,N-di-n-butylpiperidinium iodide. No primary or secondary amines were found to have this catalytic activity. 

In order to obtain evidence for or against these ideas we have begun an intensive study of the reactions of ozone with a variety of amines. This paper summarizes results from the ozonation of fert-butylamine and of tri-n-butylamine, which furnish evidence for the competitions indicated by Reactions 2, 3, and 4. Additional details will be published elsewhere. 

In the ozonation of tri-n-butylamine at —40°C. with an ozone-nitrogen stream, 1.2 to 1.6 mole equivalents of ozone were absorbed, and the yields of tri-n-butylamine oxide were 53% from chloroform and 6% from pentane solvents. The other products were the side chain oxidation products described by Henbest and Stratford (II). These results eliminate the possibility that the side chain oxidation is an ozone-initiated autoxidation. The mechanism outlined by Reaction 3 explains nicely both the requirement of ozone itself as the oxidizing agent and the solvent effect observed. Solvents such as chloroform would be expected to solvate the ozone-amine adduct (lb) and make the abstraction of the proton in Reaction 3 difficult. Thus, loss of molecular oxygen to give the amine oxide becomes the major reaction (Reaction 2). In pentane solu-... 

Thus after addition of the anhydride and heating, the mixture of amines will be converted to a combination of N-butyl-succinimide, tri-n-butylamine, and the amido salt. The amine may be removed in the forementioned way because neither the salt nor the succinimide is basic. 

After tri-n-butylamine is removed from the mixture, we may use the salt s acidity to isolate it in solution. The succinimide will remain in the organic layer and the primary amine may be produced from it by reacting the imide with hydrazine. Similarly, we may regenerate the secondary amine from the amide by alkaline hydrolysis. 

The water used in this study was double distilled and the amines (N-methyldiethanolamine, tri-n-butylamine, triethylamine, diethylamine, N-diethylmethylamine, dicyclohexylamine and N,N -dimethylaniline) were obtained from the Aldrich Chemical Company Limited, UK as was the monomer 2-hydroxyethylmethacrylate. The monoacrylate water-soluble resin RCP-1784 was supplied by Lankro Chemicals Limited, Eccles, manchester, UK and used as received. 

Since tri-n-butylamine is more basic than triethylamine in the gas phase, we postulate that trimethylamine is less basic than the secondary amines since two longer alkyl groups and hydrogen enrich the electron density at nitrogen more than three methyl groups. Perhaps more interesting is the aqueous basicity ranking of the amines below, which appears to contradict the inductive rationalization of their gas-phase values the tertiary amines are weaker than expected. 

Very similar amines, like tri n butylamine, do not afford the crystalline enriched cis-isomer [847]. Complete transformation is accomphshed in a steady state slurry, meaning a large excess of seed crystalls [850], or when the triethyl amine is slowly removed during crystallization [851]. 

A mixture of phenylacetic acid, benzyl alcohol, and tri-n-butylamine in methylene chloride added under argon to a mixture of l-methyl-2-bromopyridinium iodide and methylene chloride, and refluxed 3 hrs. benzyl phenylacetate. Y 97%. F. e., also with l-methyl-2-chloropyridinium iodide, s. T. Mukaiyama et al., Chem. Lett. 1975, 1045 Bull. Chem. Soc. Japan 50, 1863 (1977) carboxylic acid amides from amines (cf. Synth. Meth. 26, 367) s. ibid. 1975, 1163 3,4-dihydro-2H-pyrido-[1,2-a]pyrimid-2-one as acid scavenger cf. ibid. 1976, 13, 57 lactones from hydroxycarboxylic acids (cf. Synth. Meth. 17, 320) with 2-chloropyridine methio-dide and triethylamine s. ibid. 1976, 49 esters with 2 halogeno-3-ethylbenzothia-zolium salts of ibid. 1976, 267 2-chloro-N-methylbenzothiazolium triflate as condensing agent s. F. Souto-Bachiller, G. S. Bates, and S. Masamune, Chem. Com-mun. 1976, 719. 

Gruzensky and Engel (1959) reported the separation of yttrium and rare earth nitrates with a tertiary amine, 10% by volume of tri-n-butylamine diluted in a ketone, 3-methyl-2-butanone. The maximum extraction was obtained when sufficient amine was present to neutralize the aqueous phase to the point of precipitation. Extraction increased with metal concentration and the separation factors were found to be affected by the concentration of amine. 

However, the addition of sulfur to solvents such as n-butylamine, di-n-butylamine, tri-n-butylamine, triethylamine, morpholine, and ethylenedi-amine yields more highly colored solutions. In these, solvents the relationship between the extinction coefficient, e, and N, the refractive index is not obeyed. Further, two types of behavior are observed. Sulfur in the primary and secondary amines (ii-butylamine, ethylenediamine, di-n-butylamine, and morpholine) dissolves with considerable heat of solution to produce solutions containing numerous ions as measured by a conductance bridge. The following reaction is consistant with these data. 

Spike Solution Mix 250 mL 2-propanol, 250 mL water, 400 mg NaOH, and 2 g tri-n-butylamine. Protect from atmospheric CO2. Weigh out an aliquot of sample containing about 1 meq amine oxide and dissolve in 100 mL 50 50 2-propanol/water (carbonate-free). Add 10.00 mL spike solution. Titrate potentiometrically with 0.1 M HCl, dissolved in water or 2-propanoI. There will be three inflection points. Titrate a 10-mL aliquot of the spike solution separately. There will be two inflection points. Calculation ... 

Nucleotide derivatives. Dry adenosine-5 -phosphoric acid stirred with -carb-ethoxy-a-ethoxyvinyl diethyl phosphate and tri-n-butylamine in abs. dimethyl-formamide until dissolved after 2-3 days, dil. with acetone and the product precipitated with a soln. of anhydrous Nal in acetone Na P -(5 -adenosyl) P -diethyl diphosphate (Y 87 % as the monohydrate) warmed 3 hrs. at 50° in abs. methanol-pyridine, and the product isolated as the NH4-salt NH4 5 -adenosine methyl phosphate (Y 79.2% as the monohydrate).—Pyrophosphoric acid esters react with alcohols, amines, and acids so that the monoester part appears in the product. The adenosine-5 -phosphoric acid group in the intermediate triester is activated and can be easily combined with various nucleophiles. F. e. without isolation of the intermediate s. F. Cramer and R. Witt-mann. B. 9A, 328 (1961) s. a. B. 94, 322 dimethylformamide as phosphorylation catalyst s. B, 94, 989. 

Researchers have been trying to explain how retinal (or retinol) are chromophores in the visual system for more than 40 years with remarkably little success. Dartnall et. al. even claimed that the same retinal-based chromophore accounts for both the broad photopic spectral sensitivity of the eye as well as all three of the color-sensitive photodetectors found in the eye. There may be a problem of semantics related to this claim. In an attempt to synthesize an analog of rhodopsin, they formed a protonated azomethine using retinal and a simple amine, n-butylamine the resulting peak absorption was at 440 nm. It was hoped the material would have a peak near 500 nm (see further discussion below). Its absorption coefficient was not specified in Zollinger. Although this chromophore exhibits apeak in its absorption near that of the S-channel, it does not explain how the chromophores of the other spectral channels are formed. It is an irrelevant compound. 

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