Search PubMed⌕ Search

SEARCH · Search PubMed

Results for “Butylamines”

Search indexed PubMed citations on genomics, clinical trials, systematic reviews and public health. Explore titles, authors and supplied subject terms, then open the PubMed record.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 109 records · Page 6Linked to original sources
PubMed2005

New 6-butylamino-6-deoxycellulose and 6-deoxy-6-pyridiniumcellulose derivatives with highest regioselectivity and completeness of reaction.

This paper investigates the nucleophilic substitution (S(N)) reactions of tosylcellulose with butylamine and pyridine, respectively. The S(N) reactions of tosylcellulose 1 (DS(Total) 2.02; DS(C-6) 1.0) with butylamine carried out at 25, 50, 75 and 100 degrees C in both dimethyl sulfoxide (DMSO) and pure butylamine showed that the regioselectivity of substitution at C-6 of cellulose is temperature dependent: the highest regioselectivity at C-6 can be reached at 25 and 50 degrees C; substitution at C-2 also occurred at 75 and 100 degrees C. The substitution speed in pure butylamine is greater than that in the presence of DMSO. A complete and regioselective substitution at C-6 with a DS of 1.0 was obtained under the conditions of 50 degrees C, 40 h in butylamine. The substitution reactions of 1 with pyridine carried out at 25, 50, 75 and 100 degrees C for 24h in DMSO did not occur. In contrast to this the S(N) reactions done in pure pyridine showed that a temperature- and steric-dependent, regioselective substitution took place at C-6 at temperatures from 25 to 145 degrees C. The highest regioselectivity and completeness at C-6 can be obtained at 100 degrees C for 90 h, whereas at 145 degrees C substitution also occurs at C-2. The results were proved by 1H NMR and 13C NMR spectroscopy.

Butylamines↗
PubMed1987

Alpha-proton abstraction and carbanion formation in the mechanism of action of lysyl oxidase.

Tetranitromethane (TNM) was employed as an electrophilic reagent to probe for the lysyl oxidase-catalyzed processing of n-butylamine to an intermediate carbanion during the oxidation of this amine to n-butyraldehyde according to a prior description of the use of TNM to trap enzyme-generated carbanion intermediates (Christen, P. and Riordan, J. F. (1968) Biochemistry 7, 1531-1538). The addition of n-butylamine to assay mixtures containing lysyl oxidase and TNM markedly increased the background rate of nitroform release. The Km for n-butylamine was essentially the same whether determined from the rate of lysyl oxidase-catalyzed nitroform release or from the rate of n-butyraldehyde production in the absence of TNM, the latter assessed by measurements of the rate of H2O2 formation. The initial rate of substrate- and enzyme-dependent nitroform production was linearly related to functional active site content. These data are consistent with the enzyme-dependent abstraction of an alpha-proton from the substrate to form an intermediate enzyme-bound carbanion. Kinetic analyses of the oxidation of n-butylamine and 1,1-dideutero-n-butylamine by lysyl oxidase revealed kinetic isotope effects on Vmax and Vmax/Km parameters, consistent with a rate-contributing alpha-proton abstraction step. These and other available data are incorporated into a proposal for the mechanism of action of this enzyme.

Amino Acid Oxidoreductases↗
PubMed1976

Interaction between proteins and detergents which contain a hydrocarbon chain longer than 16 carbon atoms. III. Competitive inhibition of trypsin by cetyldimethylbenzylammonium chloride.

Tryptic activity was competitively inhibited by cationic detergents which contain a cetyl group or longer hydrocarbon chains. Since the cetyl group is much longer than the side chains of lysine or arginine residues of substrates for trypsin, the nature of inhibition by cetyldimethylbenzylammonium chloride was examined using Na-benzoyl-L-arginine-p-nitroanilide as substrate and compared to that by butylamine. The inhibition by cetyldimethylbenzylammonium chloride occurred instantaneously and was completely reversible. The inhibitory effect of cetyldimethylbenzylammonium chloride was strongly dependent on both pH and salt concentration, contrasting with inhibition by butylamine which was relatively indifferent to these changes. The Ki value of cetyldimethylbenzylammonium chloride at pH 7.5 and 25 degrees C was calculated to be 2.0 +/- 0.3 mM, which is equal to that of butylamine within experimental errors. The standard entropy change of binding of cetyldimethylbenzylammonium chloride (44 +/- 2 cal/mol/degree) was much larger than for butylamine, indicating the formation of an efficient hydrophobic bond between the cetyl group and the enzyme.

Binding Sites↗
PubMed1996

Cross-reactivity between a penicillin and a cephalosporin with the same side chain.

BACKGROUND: The cross-reactivity between penicillins and cephalosporins can be influenced by different factors, which are not all well known. The chemical structure of the side chain may contribute to the cross-reactivity. OBJECTIVE: The study was carried out in allergic subjects who are selectively responsive to amoxicillin to determine allergenic cross-reactivity with a cephalosporin containing a side chain identical to that of amoxicillin, cefadroxil, and one containing a different side chain, cefamandole. METHODS: Allergic subjects with a selective response to amoxicillin were chosen according to the following criteria: history of an immediate allergic reaction to amoxicillin, negative skin test responses to benzylpenicilloyl and minor determinant mixture of benzylpenicillin, negative RAST response to benzylpenicilloyl, and good tolerance to benzylpenicillin and phenoxymethyl penicillin challenges. In addition, subjects had to have a positive skin test response to amoxicillin and/or positive RAST response to amoxicilloyl or, if these test results were negative, a positive challenge test response to amoxicillin. In vivo cross-reactivity to cefadroxil was assessed by giving oral cefadroxil at increasing doses from 5 to 500 mg. In vitro cross-reactivity was determined by RAST inhibition studies with amoxicilloyl RAST disks and the following monomeric conjugates in the fluid phase: amoxicillin-butylamine, cefadroxil-butylamine, and the side chain para-hydroxy-phenylglycine. Tolerance to cefamandole was determined by giving 100 mg and then 500 mg parenterally. RESULTS: Twenty-one patients with a selective response to amoxicillin were included in the study. Eight subjects (38%) had a positive response to cefadroxil, and none reacted to cefamandole. In vitro RAST inhibition studies indicated that cefadroxil-butylamine monomers cross-reacted with amoxicillin butylamine and the side chain contributed relevantly to the inhibition. CONCLUSIONS: These results indicate that the percentage of cross-reactivity between penicillins and cephalosporins with an identical side chain is high and that this critical part of the molecule seems to be an important contributor to these results. The value is higher than previously reported data from similar studies of non-side-chain-related cephalosporins.

Adolescent↗
PubMed2006

Involvement of a putative [Fe-S]-cluster-binding protein in the biogenesis of quinohemoprotein amine dehydrogenase.

Quinohemoprotein amine dehydrogenase (QHNDH) of Paracoccus denitrificans contains a peptidyl quinone cofactor, cysteine tryptophylquinone, as well as intrapeptidyl thioether cross-links between Cys and Asp/Glu residues within the smallestgamma-subunit of the alphabetagamma heterotrimeric protein. A putative [Fe-S]-cluster-binding protein (ORF2 protein) encoded between the structural genes for the alpha- and gamma-subunits of QHNDH in the n-butylamine-utilizing operon likely belongs to a Radical SAM (S-Ado-Met) superfamily that includes many proteins involved in vitamin biosynthesis and enzyme activation. In this study the role of ORF2 protein in the biogenesis of QHNDH has been explored. Although the wild-type strain of Paracoccus denitrificans produced an active, mature enzyme upon induction with n-butylamine, a mutant strain in which the ORF2 gene had been mostly deleted, neither grew in the n-butylamine medium nor showed QHNDH activity. When the mutant strain was transformed with an expression plasmid for the ORF2 protein, n-butylamine-dependent bacterial growth and QHNDH activity were restored. Site-specific mutations in the putative [Fe-S]-cluster or SAM binding motifs in the ORF2 protein failed to support bacterial growth. The alpha- and beta-subunits were both detected in the periplasm of the mutant strain, whereas the gamma-subunit polypeptide was accumulated in the cytoplasm and stained negatively for redox-cycling quinone staining. Matrix-assisted laser desorption ionization time-of-flight mass spectrometric analysis revealed that the gamma-subunit isolated from the mutant strain had not undergone posttranslational modification. These results unequivocally show that the putative [Fe-S]-cluster- and SAM-binding ORF2 protein is necessary for the posttranslational processing of gamma-subunit, most likely participating in the formation of the intrapeptidyl thioether cross-links.

Amino Acid Sequence↗
PubMed2000

Effect of common food preservatives on mycelial growth and spore germination of Fusarium oxysporum.

The growth and spore germination inhibition of Fusarium oxysporum f.sp. radicis-cucumerinum by the common food additives: acetic acid, formic acid potassium sorbate, propionic acid, sorbic acid, and the fungistatic agent sec-butylamine was examined in vitro. The inhibitory efficacy of these chemicals decreased in the following order: sorbic acid, potassium sorbate, propionic acid, acetic acid, sec-butylamine and formic acid. At pH 6.4, the ED50 value for mycelium growth was: 976 ppm for sorbic acid, 1292 ppm for potassium sorbate, 2435 ppm for propionic acid, 3805 ppm for acetic acid, 3962 ppm for sec butylamine and 4668 ppm for formic acid. The ED50 value for spore germination was: 225 ppm for potassium sorbate, 1201 ppm for sorbic acid, 1402 ppm for propionic acid, 1600 ppm for sec-butylamine, 1957 ppm for acetic acid and 2485 ppm for formic acid.

Dose-Response Relationship, Drug↗
PubMed1997

[Study on ion chromatography (IC) for the low-molecular weight amines].

In this paper the retention behaviors of low-molecular weight amines (methylamine, dimethylamine, trimethylamine, ethylamine, propylamine sec-butylamine, n-butylamine, ethanolamine, diethanolamine, triethanolamine) on Ionpac CS12 column were for the first time studied with modern ion chromatograph. The column is usually used for routine analysis of inorganic cations and it strongly retains these organic amines. So they are difficult to be eluted by dilute aqueous HCl alone. The addition of acetonitrile (ACN) as a modifier can improve the peak shape and resolution. Influences of concentrations (ACN & HCl) on separation and detection were investigated separately and the chromatographic conditions were optimized. Aqueous solution of 20 mmol/L HCl containing 1% or 5% ACN (5% for higher molecular weight amines) was used as the eluant with a flow rate of 1.0 mL/min to optimize the column efficiency. In addition to methylamine, ethanolamine and diethanolamine, all other amines can well be separated from each other. According to the structure they may be divided into three classes: (a) methylamine, dimethylamine and trimethylamine; (b) diethanolamine and triethanolamine; (c) ethylamine, propylamine, sec-butylamine and n-butylamine. The three classes of mixtures were separately injected into the IC system and resolutions being obtained by the developed method were: (a) 1.25 and 1.52; (b) 1.20; (c) 2.45, 2.05 and 2.10 respectively. The new method is characterized by rapidity, convenience, sensitivity and simultaneous determination of some inorganic cations. It was separately used for determination of diethanolamine, triethanolamine, NH4+ in explosive samples and of Na+, K+, MgZ+, Ca2+ in water supply with satisfactory results. The retention mechanism of amines on CS12 column and effect of organic modifier were also preliminarily explored.

Biogenic Amines↗
PubMed2000

Do amines react with protonated peptides in the gas phase via transacylation reactions to induce peptide bond cleavage?

The proposal that protonated peptides react with NH(3) in the gas phase via transacylation reactions (Tabet et al., Spectros. Int. J. 5: 253 1987) has been investigated by studying the reactions of the fixed charge derivatives [RC(O)NMe(2)CH(2)CO(2)H](+) (R=Me and Ph) with pyridine and triethylamine and the reactions of protonated glycine oligomers and leucine enkenphalin with butylamine. Under the near thermal conditions of the quadrupole ion trap, both the fixed charge derivatives as well as the protonated peptides react with the amines via either proton transfer or proton bound dimer formation. Collision induced dissociation of protonated peptides in the presence of butylamine yields b(n) and y(n) sequence ions as well as [b(n) + BuNH(2)](+) and [y(n) + BuNH(2)](+) ions. MS(3) experiments reveal that a major route to these [b(n) + BuNH(2)](+) and [y(n) + BuNH(2)](+) ions involves ion-molecule reactions between the b(n) and y(n) sequence ions and butylamine. MS(4) experiments, carried out to determine the nature of the [b(n) + BuNH(2)](+) ions, reveal that they correspond to a mixture of hydrogen bonded (i.e. proton bound dimer) and covalent amide bond structures.

Acylation↗
PubMed1989

Biotransformation of terodiline. V. Stereoselectivity in hydroxylation by human liver microsomes.

The stereoselective hydroxylation of N-tert-butyl-4,4-diphenyl-2-butylamine (Terodiline) was studied in human liver microsomes. Formation of the two main metabolites, N-tert-butyl-4(4-hydroxyphenyl)-4-phenyl-2-butylamine (II) and N-(2-hydroxymethyl-2-propyl)-4,4-diphenyl-2-butylamine (VI), was found to be stereoselective. R-Terodiline was preferentially transformed by phenolic hydroxylation to the 2R,4S-II and 2R,4R-II forms with a pronounced selectivity for the former. The formation rate ratio 2R,4S-II/2R,4R-II was about 6, obtained from two liver preparations. S-Terodiline was mainly hydroxylated to the alcohol 2S-VI although phenolic hydroxylation to the 2S,4S-II and 2S,4R-II also occurred, yielding about equal amounts of the two phenols.

Adult↗
PubMed1992

Kinetic evidence for the existence of an unstable intermediate in the trinitrophenylation-induced rhodanese inactivation reaction.

1. Rhodanese inactivation by 2,4,6-trinitrobenzenesulphonate, in the presence of n-butylamine in the reaction medium, has been studied by a kinetic analysis of the data, based on the assumption that enzyme inactivation is brought about by direct reaction of this with the modifying agent. 2. Initial reaction rates for rhodanese activity loss were determined by a mathematical analysis of the first three recorded values of rhodanese residual activity. 3. It was found that fractional rhodanese activity values, at infinite reaction time with 2,4,6-trinitrobenzenesulphonate (end-point values), were significantly lower than the values calculated on the assumption of rhodanese inactivation being entirely due to direct trinitrophenylation of enzyme protein. 4. Also, initial enzyme inactivation values were higher in the presence, rather than in the absence, of n-butylamine. 5. These results indicate that 2,4,6-trinitrobenzenesulphonate-induced rhodanese inactivation, in the presence of n-butylamine in the reaction medium, is due to the generation of a highly reactive, unstable intermediate, probably a free radical species.

Animals↗
PubMed2004

Application of colorimetric indicators and thermo-hand method to determine base permeation through chemical protective gloves.

The aim of this study was to assess the use of colorimetric indicator pads and the thermo-hand method for detection of inorganic/organic base permeation of chemical protective gloves under simulated in-use conditions. Breakthrough times for four types of gloves were determined based on the color change of pads and ranged from 3 to 10 min for butylamine, from 4 min to >4 hours for diisopropylamine, from 6 min to >4 hours for triethylamine, and >4 hours for sodium hydroxide. Quantification was performed for butylamine, diisopropylamine, and triethylamine by gas chromatography following solvent desorption. These chemicals exhibited >99% adsorption on the pads at spiking levels of 1.08-1.11:g for each base. The recovery for the system was calculated for each chemical, with results ranging from 50-74% (RSD < or = 5%) for these bases over the spiking range 0.22-1.11 microg. The quantitative mass of the bases on the pads at the time of breakthrough detection ranged from 118-121, 117-120, and 109-116 microg/cm2 for butylamine, diisopropylamine, and triethylamine, respectively. The thermo-hand test method and base indicators together should find utility in detecting, collecting, and quantitatively analyzing base permeation samples under simulated in-use conditions.

Butylamines↗
PubMed1989

An analysis of Trichinella pseudospiralis excretions and study of their effect on striated muscles of mouse.

The causes of changes observed after infection of muscles with Trichinella pseudospiralis larvae were studied. The changes are not only regressive, but also proliferative (activation and mitosis of satellite cells and formation of new myotubes). By means of high-performance liquid chromatography (HPLC) and an original method it was found that T. pseudospiralis larvae excrete into their environment among others a great amount of n-butylamine. A direct application of n-butylamine into the gluteal muscle of mouse supported the assumption that this amine is one of the factors causing the changes in muscles induced by T. pseudospiralis infection. The application of n-butylamine into the muscle resulted in regressive and regenerative changes similar to that observed in case of T. pseudospiralis infection.

Animals↗
PubMed2004

A general study of [(eta5-Cp')2Ti(eta2-Me3SiC2SiMe3)]-catalyzed hydroamination of terminal alkynes: regioselective formation of Markovnikov and anti-Markovnikov products and mechanistic explanation (Cp'=C5H5, C5H4Et, C5Me5).

A general study of the regioselective hydroamination of terminal alkynes in the presence of [(eta5-Cp)2Ti(eta2-Me3SiC2SiMe3)] (1), [(eta5-CpEt)2Ti(eta2-Me3SiC2SiMe3)] (CpEt=ethylcyclopentadienyl) (2), and [(eta5-Cp*)2Ti(eta2-Me3SiC2SiMe3)] (Cp*=pentamethylcyclopentadienyl) (3) is presented. While aliphatic amines give mainly the anti-Markovnikov products, anilines and aryl hydrazines yield the Markovnikov isomer as main products. Interestingly, using aliphatic amines such as n-butylamine and benzylamine the different catalysts lead to a significant change in the observed regioselectivity. Here, for the first time a highly selective switch from the Markovnikov to the anti-Markovnikov product is observed simply by changing the catalyst. Detailed theoretical calculations for the reaction of propyne with different substituted anilines and tert-butylamine in the presence of [(eta5-C5H5)Ti(=NR)(NHR)] (R=4-C6H4X; X=H, F, Cl, CH3, 2,6-dimethylphenyl) reveal that the experimentally observed regioselectivity is determined by the relative stability of the corresponding pi-complexes 10. While electrostatic stabilization favors the Markovnikov performance for aniline, the steric repulsive destabilization disfavors the Markovnikov performance for tert-butylamine.

Journal Article↗
PubMed2006

The effect of acidic and basic additives on the enantioseparation of basic drugs using polysaccharide-based chiral stationary phases.

The enantioseparation of nine commercially available basic drugs was achieved on polysaccharide-based chiral stationary phases with the acidic additive ethanesulfonic acid and the basic additive butylamine. Seven different commercially available CSPs were used for the study (AD, AS, OD, OJ, OG, OB, and OC). Mobile phase additives have been proven to be essential in obtaining satisfactory enantio-resolution in terms of both efficiency and selectivity. Significantly improved selectivities were obtained for the basic probe drugs with the acidic additive, ethanesulfonic acid, rather than the basic additive, butylamine. This is best seen with Chiralpak AS CSP. No enantioseparation for the nine drugs was observed when butylamine was used as an additive; however, satisfactory enantioseparation for the nine drugs was achieved using ethanesulfonic acid. Higher column efficiencies were observed with the acidic additive, especially when isopropanol was used as a modifier. Higher sensitivity was also achieved with ethanesulfonic acid because of the significantly lower background at the UV detection wavelength. The acidic additive was demonstrated to be superior to the basic additive for the enantioseparation of basic drugs using seven different polysaccharide-based CSPs. These results are counterintuitive to the common "rule of thumb" in enantioseparation that states acidic additives work best for acidic analytes and basic additives work best for basic analytes. The beneficial effects of acidic additive in enantioseparations observed in this study could significantly improve the applicability of polysaccharide-based CSPs for the enantioseparation of basic analytes.

2-Propanol↗
PubMed1991

Indirect determination of isocyanates by gas chromatography.

A gas chromatographic method was developed to determine the purity of synthesized isocyanate monomers, specifically isocyanatoacrylates, and to determine the isocyanate content of synthesized polymers and prepolymers. The method is a modification of an ASTM procedure in which an isocyanate is allowed to react with excess di-n-butylamine. In the ASTM method, the amount of isocyanate present is calculated indirectly from the amount of unreacted di-n-butylamine, determined by back titration with standard hydrochloric acid. Determination of the excess di-n-butylamine by the gas chromatographic method developed has the advantages of providing better precision and requiring less sample than the titrimetric method. The two methods were compared using phenyl isocyanate as a model test compound. A synthesized monomer, methyl alpha-isocyanatoacrylate, was also analyzed, for comparison by both methods.

Chromatography, Gas↗
PubMed2003

Optical sensor for amine vapors based on dimer-monomer equilibrium of indium(III) octaethylporphyrin in a polymeric film.

A novel transduction chemistry for the development of a polymer film-based optical sensor that responds reversibly to gas-phase amine species at sub-ppm levels is described. The sensor is based on the equilibrium of a indium(III) octaethylporphyrin hydroxide ion-bridged dimer species with corresponding monomeric porphyrins within a thin poly(vinyl chloride) film as a function of the level of volatile amine in the surrounding gas phase. The presence of amines causes the dimeric species to be converted to monomer via the ligation of the amine with the In(III) center of the porphyrin structure. This yields a significant change in the visible absorption spectrum of the film, with a decrease in the intensity of the Soret band corresponding to the dimer (lambdamax = 390 nm) and a concomitant increase in the Soret band for the monomer lambdamax = 406-408 nm). Response to different amines is based on their relative partition coefficient into the polymer film and their strength of axial ligation reactions, with a selectivity pattern of 1-butylamine > 1-propylamine > pyridine > triethylamine > ethylamine > methylamine > diethylamine > tert-butylamine > ammonia. It is further shown that a significant concentration of dimeric species within the polymer film can only be achieved if appropriate amounts of lipophilic anionic sites are also incorporated into the polymer in the form of a tetraphenylborate derivative and the resulting film is equilibrated briefly with water prior to gas-phase measurements. With optimized film compositions, 1-butylamine can be detected in the gas phase to levels approaching 0.1 ppm, while less lipophilic ammonia can be monitored down to 10 ppm, with fully reversible responses to each species. A simple mathematical model for the response of the amine sensor is presented and shown to predict the optical behavior observed.

Amines↗
PubMed2002

The effect of ligand charge on the coordination geometry of an Fe(III)ion: five- and six-coordinate Fe(III) complexes of tris(2-benzimidazolylmethyl)amine.

By using the tripodal tetradentate ligand tris(2-benzimidazolylmethyl)amine (H(3)ntb), which can have several charge states depending on the number of secondary amine protons, mononuclear octahedral and dinuclear trigonal bipyramidal Fe(III) complexes were prepared. The reaction of mononuclear octahedral [Fe(III)(H(3)ntb)Cl(2)]ClO(4), 1, with 3 equiv of sec-butylamine in methanol led to the formation of mononuclear cis-dimethoxo octahedral Fe(III)(H(2)ntb)(OMe)(2), 2. One equivalent of the sec-butylamine was used to generate the monoanionic H(2)ntb(-) ligand where one of the three amines in the benzimidazolyl groups was deprotonated. The remaining 2 equiv were used to generate two methoxides that were coordinated to the octahedral Fe(III) ion in a cis fashion as demonstrated by the chlorides in 1. Reaction of 1 with excess (7 equiv) sec-butylamine generated the doubly deprotonated dianionic Hntb(2-) that stabilized the dinuclear mu-oxo Fe(III)(2)O(Hntb)(2), 3, adopting a five-coordinate trigonal bipyramidal geometry. The magnetic data for 3 are consistent with the antiferromagnetically coupled Fe(III) (S = 5/2) sites with the coupling constant J = -127 cm(-1).

Journal Article↗
PubMed1996

Imido Complexes Derived from the Reactions of Niobium and Tantalum Pentachlorides with Primary Amines: Relevance to the Chemical Vapor Deposition of Metal Nitride Films.

Reactions of niobium and tantalum pentachlorides with tert-butylamine (>/=6 equiv) in benzene afford the dimeric imido complexes [NbCl(2)(N(t)Bu)(NH(t)Bu)(NH(2)(t)Bu)](2) (90%) and [TaCl(2)(N(t)Bu)(NH(t)Bu)(NH(2)(t)Bu)](2) (79%). The niobium complex exists as two isomers in solution, while the tantalum complex is composed of three major isomers and at least two minor isomers. Analogous treatments with isopropylamine (>/=7 equiv) give the monomeric complexes NbCl(2)(N(i)Pr)(NH(i)Pr)(NH(2)(i)Pr)(2) (84%) and TaCl(2)(N(i)Pr)(NH(i)Pr)(NH(2)(i)Pr)(2) (84%). The monomeric complexes are unaffected by treatment with excess isopropylamine, while the dimeric complexes are cleaved to the monomers MCl(2)(N(t)Bu)(NH(t)Bu)(NH(2)(t)Bu)(2) upon addition of excess tert-butylamine in chloroform solution. Treatment of niobium and tantalum pentachlorides with 2,6-diisopropylaniline affords insoluble precipitates of [NH(3)(2,6-(CH(CH(3))(2))(2)C(6)H(3))](2)[NbCl(5)(N(2,6-(CH(CH(3))(2))(2)C(6)H(3)))] (100%) and [NH(3)(2,6-(CH(CH(3))(2))(2)C(6)H(3))](2)[TaCl(5)(N(2,6-(CH(CH(3))(2))(2)C(6)H(3)))] (100%), which react with 4-tert-butylpyridine to afford the soluble complexes [4-t-C(4)H(9)C(5)H(4)NH](2)[NbCl(5)(N(2,6-(CH(CH(3))(2))(2)C(6)H(3)))] (45%) and [4-t-C(4)H(9)C(5)H(4)NH](2)[TaCl(5)(N(2,6-(CH(CH(3))(2))(2)C(6)H(3)))] (44%). Sublimation of [NbCl(2)(N(t)Bu)(NH(t)Bu)(NH(2)(t)Bu)](2), MCl(2)(N(i)Pr)(NH(i)Pr)(NH(2)(i)Pr)(2), and [NH(3)(2,6-(CH(CH(3))(2))(2)C(6)H(3))](2)[MCl(5)(N(2,6-(CH(CH(3))(2))(2)C(6)H(3)))] leads to decomposition to give [MCl(3)(NR)(NH(2)R)](2) as sublimates (32-49%), leaving complexes of the proposed formulation MCl(NR)(2) as nonvolatile residues. By contrast, [TaCl(2)(N(t)Bu)(NH(t)Bu)(NH(2)(t)Bu)](2) sublimes without chemical reaction. Analysis of the organic products obtained from thermal decomposition of [NbCl(2)(N(t)Bu)(NH(t)Bu)(NH(2)(t)Bu)](2) showed isobutylene and tert-butylamine in a 2.2:1 ratio. Mass spectra of [NbCl(2)(N(t)Bu)(NH(t)Bu)(NH(2)(t)Bu)](2), [TaCl(2)(N(t)Bu)(NH(t)Bu)(NH(2)(t)Bu)](2), and [NbCl(3)(N(i)Pr)(NH(2)(i)Pr)](2) showed the presence of dimeric imido complexes, monomeric imido complexes, and nitrido complexes, implying that such species are important gas phase species in CVD processes utilizing these molecular precursors. The crystal structures of [4-t-C(4)H(9)C(5)H(4)NH](2)[NbCl(5)(N(2,6-(CH(CH(3))(2))(2)C(6)H(3)))], [NbCl(3)(N(i)Pr)(NH(2)(i)Pr)](2), [NbCl(3)(N(2,6-(CH(CH(3))(2))(2)C(6)H(3)))(NH(2)(2,6-(CH(CH(3))(2))(2)C(6)H(3)))](2), and [TaCl(3)(N(2,6-(CH(CH(3))(2))(2)C(6)H(3)))(NH(2)(2,6-(CH(CH(3))(2))(2)C(6)H(3)))](2) were determined. [4-t-C(4)H(9)C(5)H(4)NH](2)[NbCl(5)(N(2,6-(CH(CH(3))(2))(2)C(6)H(3)))] crystallizes in the space group P2(1)/c with a = 12.448(3) Å, b = 10.363(3) Å, c = 28.228(3) Å, beta = 94.92(1) degrees, V = 3628(5) Å(3), and Z = 4. [NbCl(3)(N(i)Pr)(NH(2)(i)Pr)](2) crystallizes in the space group P2(1)/c with a = 9.586(4) Å, b = 12.385(4) Å, c = 11.695(4) Å, beta = 112.89(2) degrees, V = 1279.0(6) Å(3), and Z = 2. [NbCl(3)(N(2,6-(CH(CH(3))(2))(2)C(6)H(3)))(NH(2)(2,6-(CH(CH(3))(2))(2)C(6)H(3)))](2) crystallizes in the space group P2(1)/n with a = 10.285(3) Å, b = 11.208(3) Å, c = 23.867(6) Å, beta = 97.53 degrees, V = 2727(1) Å(3), and Z = 2. [TaCl(3)(N(2,6-(CH(CH(3))(2))(2)C(6)H(3)))(NH(2)(2,6-(CH(CH(3))(2))(2)C(6)H(3)))](2) crystallizes in the space group P2(1)/n with a = 10.273(1) Å, b = 11.241(2) Å, c = 23.929(7) Å, beta = 97.69(2) degrees, V = 2695(2) Å(3), and Z = 2. These findings are discussed in the context of niobium and tantalum nitride film depositions from molecular precursors.

Journal Article↗