Analysis of amine compounds by capillary gas chromatography using ammonia–helium carrier gas

The use of 10%, 1%, and 0.1% ammonia in helium as carrier gas was investigated as a means of improving poor chromatographic peak shape often associated with low level determinations of amine compounds using thin film capillary columns. The 1% ammonia in helium was found suitable for improving the peak shape of sterically unhindered amine compounds, such as urethane and certain aliphatic primary amines, during gas chromatographic analysis on thin film columns. There was a negligible effect on the peak tailing arising on thick film columns. The 0.1% ammonia in helium was suitable, but not as efficient as the 1% ammonia in helium, in eliminating the peak tailing associated with low level analysis of amine compounds. The signal-to-noise (S/N) ratio improved from < 1 using helium carrier gas to 20–25 (for certain test amine compounds) using 1% ammonia in carrier gas. The 10% ammonia in helium carrier gas had an effect on the chromatographic performance similar to that of the 1% ammonia in helium, but the baseline level was very high and this mixture was not used in further studies.     

Effect of ammonia carrier gas on the response of the flame ionization detector

The effect of using ammonia as a carrier gas on the response of the flame ionization detector (FID) has been investigated. It was found that the FID response, calculated as the effective carbon number (ECN), increased for all the compounds studied when ammonia, rather than helium, was used. The change was 0–0. 9 carbon atom for hydrocarbons, one carbon atom for alcohols and diphenyl ether, and 0.4–1 carbon atom for phenols and ketones. The increase in ECN was larger for amines (0. 8–5 carbon atoms), but these numbers also reflected an improvement in chromatographic performance as a result of reduced adsorption on the column. The largest change in signal-to-noise ratio, a six-fold increase, was obtained for octyl-amine; ratios for hexyl methyl ketone, diisobutyl ketone, dihexyl-amine, dibutylamine, and N-methyloctylamine increased by a factor of 2–3 when ammonia was used as carrier gas. To determine the extent to which the effect on detector response was solely attributable to ammonia, a mixture of 5 % ammonia in nitrogen was used as detector make-up gas with helium as carrier gas. Under these conditions the noise in the FID increased but for most of the compounds studied the signal-to-noise ratio also increased.     

The “Borrowing Hydrogen Strategy” by Supported Ruthenium Hydroxide Catalysts: Synthetic Scope of Symmetrically and Unsymmetrically Substituted Amines

The N‐alkylation of ammonia (or its surrogates, such as urea, NH₄HCO₃, and (NH₄)₂CO₃) and amines with alcohols, including primary and secondary alcohols, was efficiently promoted under anaerobic conditions by the easily prepared and inexpensive supported ruthenium hydroxide catalyst Ru(OH)_x/TiO₂. Various types of symmetrically and unsymmetrically substituted “tertiary” amines could be synthesized by the N‐alkylation of ammonia (or its surrogates) and amines with “primary” alcohols. On the other hand, the N‐alkylation of ammonia surrogates (i.e., urea and NH₄HCO₃) with “secondary” alcohols selectively produced the corresponding symmetrically substituted “secondary” amines, even in the presence of excess amounts of alcohols, which is likely due to the steric hindrance of the secondary alcohols and/or secondary amines produced. Under aerobic conditions, nitriles could be synthesized directly from alcohols and ammonia surrogates. The observed catalysis for the present N‐alkylation reactions was intrinsically heterogeneous, and the retrieved catalyst could be reused without any significant loss of catalytic performance. The present catalytic transformation would proceed through consecutive N‐alkylation reactions, in which alcohols act as alkylating reagents. On the basis of deuterium‐labeling experiments, the formation of the ruthenium dihydride species is suggested during the N‐alkylation reactions.     

Retention of organic compounds in capillary gas chromatography using humid carrier gases

The influence of humid carrier gases (nitrogen and carbon dioxide) on the retention of polar compounds in a capillary column with polypropylcyanophenylsiloxane stationary liquid phase OV-225 was studied. It is noted that when humid carbon dioxide is used as the carrier gas, the retention of primary amines sharply increases. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1129–1131, June, 1999.     

Interactions of copper tetra-tert-butylphthalocyanine with nitrogen- and sulfur-containing compounds in solutions

Interactions of ammonia, aliphatic amines, hydrogen sulfide, and sulfur dioxide with copper tetra-tert-butylphthalocyanine (CuPc) in squalane were studied by spectrophotometry and gas liquid chromatography in the CuPc concentration range of 1·10^–3—5·10^–2 mol L^–1. The sorption properties of the CuPc—squalane stationary liquid phases (SLPs) are governed by the physicochemical nature of the CuPc nanoaggregates in solution. The -type nanoaggregates exhibit particularly high activity to hydrogen sulfide; the activities to primary and secondary amines are also high.     

Amination of [60]fullerene by ammonia and by primary and secondary aliphatic amines--preparation of amino[60]fullerene peroxides

Ammonia and aliphatic amines react readily in the oxygen-rich regions of the Cs symmetric fullerene peroxides C60(O)(OOtBu)4 (1) and C60(OH)(Br)(OOtBu)4 (2 c). Michael addition-type hydroamination of the 1,4-diene moiety on the central skew-pentagon was observed when 1 was treated with ammonia or with nonbulky primary amines, while sterically demanding primary amines opened the epoxy moiety to form vicinal aminohydroxy fullerene compounds with the amino group on the central pentagon. In 2 c the bromo group was replaced under similar conditions by ammonia and primary amines. Cyclic secondary amines showed different reaction patterns, forming hydrogenation products or aminoketal-fullerenes when treated with 1 and 2 c, respectively. Single-electron transfer (SET) is the key step in all the proposed mechanisms. The compounds were characterized by their spectroscopic data, and in addition, three single-crystal X-ray structures were obtained.     

Microwave-assisted synthesis of primary amine HX salts from halides and 7 M ammonia in methanol

The atom economical synthesis of hydrogen halide salts of primary amines, directly from the corresponding halides, avoids the production of significant amounts of secondary amine side products, and requires only evaporation of the solvent to access the products in yields generally greater than 90%. The procedure uses microwave irradiation in 7 M ammonia in methanol (Aldrich) at 130 °C from 0.5 to 2.5 h and works on a variety of alkyl halides, as well as mesylates and tosylates. Benzylamines are obtained from benzyl halides without significant amounts of the secondary amine side products that result without microwave heating. Direct isolation of even highly volatile primary amines as their hydrogen halide salts makes the method ideal for use in parallel synthesis.     

Determination of primary and secondary amines in foodstuffs using gas chromatography and chemiluminescence detection with a modified thermal energy analyser

A simple method is described for the determination of primary and secondary amines in foodstuffs by gas chromatography with a modified thermal energy analyser, operated in the nitrogen mode. Food samples were subjected to mineral oil vacuum distillation and the isolated amines were derivatized with benzenesulphonyl chloride to form the corresponding sulphonamides, which were fractionated to yield primary and secondary amine derivatives using a modified Hinsberg procedure. The detection limit for individual amines using a 10-g food sample was 10 micrograms/kg (ppb) and recoveries were in excess of 80%.     

Transformations ofmyo-inositol hexa-O-nitrate under the action of amines

Reactions ofmyo-inositiol hexa-O-nitrate with ammonia and primary amines yield tetrahydroxy-1,4-benzoquinone derivatives,viz., its tetraammonium salt and its diimines, respectively. Reactions with secondary and tertiary amines give salts of rhodizonic acid, which are converted into salts of croconic acid under certain conditions. The reactions with secondary amines involve intermediate formation of radical species, which were dectected by ESR spectroscopy. A scheme for the chemical transformations ofmyo-inositol hexa-O-nitrate under the action of amines was proposed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2962–2967, December, 1996.     

Synthesis and Insecticidal Efficacy of Novel Bis Quinazolinone Derivatives

A novel bis benzoxazin‐4‐one derivative has been synthesized and utilized to construct a new series of bis quinazolin‐4(3H)‐one derivatives via the reactions with different nitrogen nucleophiles namely, primary amines (ammonia, ethanolamine, and 4‐aminoantipyrine), secondary amines (morpholine and piperidine), diamine (o‐phenylenediamine), hydrazine hydrate, and hydroxylamine. The insecticidal efficacy of newly synthesized compounds was also studied. The structural features of the synthesized compounds were assigned by spectral analysis.     

Ionic liquids as silica deactivating agents in gas chromatography for direct analysis of primary amines in water

Analysis of primary amines in aqueous samples remains a challenging analytical issue. The preferred approach by gas chromatography is hampered by interactions of free silanol groups with the highly reactive amine groups, resulting in inconsistent measurements. Here, we report a method for direct analysis of aliphatic amines and diamines in aqueous samples by gas chromatography (GC) with silanol deactivation using ionic liquids (ILs). ILs including trihexyl(tetradecyl)phosphonium bis 2,4,4-(trimethylpentyl)phosphinate (Cyphos IL-104), 1-methyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide [pmim][Tf(2)N] and N″-ethyl-N,N,N',N'-tetramethylguanidinium tris(pentafluoroethyl)trifluorophosphate [etmg][FAP] were tested as deactivating media for the GC liner. Solutions of these ILs in methanol were injected in the system prior to the analysis of primary amines. Butane-1,4-diamine (putrescine, BDA) was used as a reference amine. The best results were obtained using the imidazolium IL [pmim][Tf(2)N]. With this deactivator, excellent reproducibility of the analysis was achieved, and the detection limit of BDA was as low as 1mM. The applicability of the method was proven for the analysis of two different primary amines (C4-C5) and pentane-1,5-diamine.     

Ring Opening of N‐Sulfonyl Aziridines by Amines in Silica‐Water

Ring opening reactions of N‐sulfonyl aziridines by primary and secondary amines in silica gel (SG)‐water system were achieved, which provided a mild, practical and environmentally benign method to synthesize mono‐ and bis‐sulfonyl substituted amines. When primary and secondary amines were used in excess, they reacted with N‐sulfonyl aziridines smoothly at room temperature, mainly affording 1:1 ring opening products. Reactions of primary amines with 2 equiv. of aziridines produced 2:1 ring opening products. Some 1:1 products can be cyclized with CS₂ to synthesize N‐sulfonyl cyclothioureas also in water.     

Quantitative analysis of ethylenediamine in plasma by capillary column gas chromatography

A specific and sensitive method for the determination of ethylenediamine in human plasma is described. The aqueous sample is treated with m-toluoyl chloride, yielding the N,N′-bis(m-toluoyl) derivative of the diamine, which is extracted into dichloromethane and quantitated after “on column” methylation by capillary gas liquid chromatography with alkali flame ionization detection. The corresponding derivative of putrescine serves as internal standard. The assay is reproducible and calibration curves are linear over the concentration range 0.05 to 10 μg · ml^?1. The lower detection limit is about 10 ng · ml^?1. The structures of the compounds of interest eluting from the capillary column are examined by gas liquid chromatography/mass spectrometry. The assay has been applied to the analysis of ethylenediamine in plasma following the administration of aminophylline and ethylenediamine in a cross-over study to patients with bronchopulmonary diseases. The method also proves suitable for measuring other primary and secondary amines and diamines in aqueous solutions by gas liquid chromatography.     

Development of a General Non‐Noble Metal Catalyst for the Benign Amination of Alcohols with Amines and Ammonia

The N‐alkylation of amines or ammonia with alcohols is a valuable route for the synthesis of N‐alkyl amines. However, as a potentially clean and economic choice for N‐alkyl amine synthesis, non‐noble metal catalysts with high activity and good selectivity are rarely reported. Normally, they are severely limited due to low activity and poor generality. Herein, a simple NiCuFeO_x catalyst was designed and prepared for the N‐alkylation of ammonia or amines with alcohol or primary amines. N‐alkyl amines with various structures were successfully synthesized in moderate to excellent yields in the absence of organic ligands and bases. Typically, primary amines could be efficiently transformed into secondary amines and N‐heterocyclic compounds, and secondary amines could be N‐alkylated to synthesize tertiary amines. Note that primary and secondary amines could be produced through a one‐pot reaction of ammonia and alcohols. In addition to excellent catalytic performance, the catalyst itself possesses outstanding superiority, that is, it is air and moisture stable. Moreover, the magnetic property of this catalyst makes it easily separable from the reaction mixture and it could be recovered and reused for several runs without obvious deactivation.     

Pt-Sn/γ-Al2O3-catalyzed highly efficient direct synthesis of secondary and tertiary amines and imines

Versatile syntheses of secondary and tertiary amines by highly efficient direct N‐alkylation of primary and secondary amines with alcohols or by deaminative self‐coupling of primary amines have been successfully realized by means of a heterogeneous bimetallic Pt–Sn/γ‐Al₂O₃ catalyst (0.5 wt % Pt, Pt/Sn molar ratio=1:3) through a borrowing‐hydrogen strategy. In the presence of oxygen, imines were also efficiently prepared from the tandem reactions of amines with alcohols or between two primary amines. The proposed mechanism reveals that an alcohol or amine substrate is initially dehydrogenated to an aldehyde/ketone or NH‐imine with concomitant formation of a [PtSn] hydride. Condensation of the aldehyde/ketone species or deamination of the NH‐imine intermediate with another molecule of amine forms an N‐substituted imine which is then reduced to a new amine product by the in‐situ generated [PtSn] hydride under a nitrogen atmosphere or remains unchanged as the final product under an oxygen atmosphere. The Pt–Sn/γ‐Al₂O₃ catalyst can be easily recycled without Pt metal leaching and has exhibited very high catalytic activity toward a wide range of amine and alcohol substrates, which suggests potential for application in the direct production of secondary and tertiary amines and N‐substituted imines.     

Light‐Activated Sensitive Probes for Amine Detection

Our new, simple, and accurate colorimetric method is based on diarylethenes (DAEs) for the rapid detection of a wide range of primary and secondary amines. The probes consist of aldehyde‐ or ketone‐substituted diarylethenes, which undergo an amine‐induced decoloration reaction, selectively to give the ring‐closed isomer. Thus, these probes can be activated at the desired moment by light irradiation, with a sensitivity that allows the detection of amines at concentrations as low as 10⁻⁶ m in solution. In addition, the practical immobilization of DAEs on paper makes it possible to detect biogenic amines, such as cadaverine, in the gas phase above a threshold of 12 ppbv within 30 seconds.     

气相色谱-质谱法同时测定塑料食品接触材料中25种芳香族伯胺的迁移量

采用固相萃取前处理技术,结合气相色谱-质谱法对食品接触材料中25种芳香族伯胺的迁移量进行了同时测定。样品中25种目标物分别用蒸馏水和30 g/L醋酸浸出后,用氨水调节浸泡液至pH 8～10,经固相萃取小柱富集净化,再用体积比为1:1的叔丁基甲醚和乙醇混合液洗脱定容后用气相色谱-质谱仪测定。不同芳香族伯胺的检出限略有差异,在0.4～2.0 μg/kg的范围内。加标水平在10 μg/kg时,除2,4-二氨基苯甲醚在酸性模拟物中的回收率较低外,其他芳香族伯胺的回收率均在51.6%～118.4%之间,相对标准偏差(n=7)为0.5%～9.8%。同时探讨了不同实验条件如叔丁基甲醚和乙醇的体积比、pH值等条件对25种芳香族伯胺回收率的影响。结果表明,该方法准确、稳定,完全满足欧盟指令No 10/2011对食品接触塑料材料及制品中芳香族伯胺特定迁移量的限量要求,可用于食品接触材料中芳香族伯胺的实际检验。     

配体交换气相色谱法分离低级脂肪胺

本文报道了以焦磷酸钛(TiPP)作固定相,含氨和水汽的高纯氮气为载气,用配体交换气相色谱法分离脂肪胺混合物的工作。研究了气相配体浓度、固定相的离子形式、柱温等诸因素对保留和分离的影响,探讨了胺的保留机理。     

Influence of the carrier gas on retention factors of gaseous hydrocarbons on polytrimethylsilylpropyne using capillary gas chromatography

The retention factor and height equivalent of a theoretical plate for gaseous hydrocarbons C₁—C₄ were studied on capillary columns with the layer of the new polymeric adsorbent polytrimethylsilylpropyne (PTMSP) as functions of the nature and pressure of the carrier gas. The retention factor k increases in the series helium < nitrogen < carbon dioxide. The k values depend linearly on the average pressure of the carrier gas in a capillary column with the adsorption PTMSP layer.     

Multialkylation of aqueous ammonia with alcohols catalyzed by water-soluble Cp*Ir-ammine complexes

Novel water-soluble Cp*Ir-ammine complexes have been synthesized, and a new and highly atom-economical system for the synthesis of organic amines using aqueous ammonia as a nitrogen source has been developed. With a water-soluble and air-stable Cp*Ir-ammine catalyst, [Cp*Ir(NH(3))(3)][I](2), a variety of tertiary and secondary amines were synthesized by the multialkylation of aqueous ammonia with theoretical equivalents of primary and secondary alcohols. The catalyst could be recycled by a facile procedure maintaining high activity. A one-flask synthesis of quinolizidine starting with 1,5,9-nonanetriol was also demonstrated. This new catalytic system would provide a practical and environmentally benign methodology for the synthesis of various organic amines.