- Method for synthesizing aminoacetonitrile hydrochloride from hydrocyanic acid
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The invention relates to the technical field of organic chemical synthesis. The method comprises the following steps: reacting hydrocyanic acid with formaldehyde to obtain a hydroxyacetonitrile aqueous solution, reacting hydroxyacetonitrile with ammonia to obtain an aminoacetonitrile aqueous solution, reacting aminoacetonitrile with hydrogen chloride, and concentrating, crystallizing, filtering and drying the obtained feed liquid to obtain aminoacetonitrile hydrochloride. The method provided by the invention is simple in technological process and mild in reaction condition, high-temperature and high-pressure operation is not involved, and used equipment is conventional equipment; except hydrocyanic acid, other raw materials are easy to obtain, and the raw material cost is low; waste waterand waste gas are small in amount and can be used indiscriminately, and only a small amount of ammonium chloride is generated; the product quality is good, and the appearance and content are higher than those of a sodium cyanide process.
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Paragraph 0030; 0034; 0038; 0042; 0046; 0050; 0054; 0058
(2020/08/18)
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- Facile Access to 1,4-Disubstituted Pyrrolo[1,2- a ]pyrazines from α-Aminoacetonitriles
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An efficient and practical synthetic protocol for the synthesis of 1,4-disubstituted pyrrolo[1,2- a ]pyrazine derivatives is described that originates from α-substituted pyrroloacetonitriles which, in turn, are readily available from aryl and alkyl aldehydes. The α-pyrroloacetonitriles were subjected to a Friedel-Crafts acylation with methyl chlorooxoacetate followed by reduction of the nitrile group under Pd-catalyzed hydrogenation conditions and finally aromatization with DDQ leading to the desired pyrrolo[1,2- a ]pyrazine derivatives. This method was generalized and successfully applied to various aryl, heteroaryl, and alkyl substrates. The developed protocol provides direct and convenient access to 1,4-disubstituted ring systems in moderate to good overall yields (51-68percent) without the need for purification of the intermediates. Further functionalization via the stepwise halogenation (bromination, iodination) and nitration was also demonstrated. In addition, the potential of the ester functionality for elaboration was demonstrated by manipulating into heterocyclic ring systems, exemplified by conversion into benzoxazole derivatives.
- Basha, Mushkin,Belema, Makonen,Dhar, T. G. Murali,Gupta, Anuradha,Gupta, Arun Kumar,Indasi, Gopi Kumar,Karmakar, Ananta,Mathur, Arvind,Meanwell, Nicholas A.,Ramalingam, Sridharan,Rampulla, Richard
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supporting information
p. 441 - 449
(2020/01/23)
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- THIOPHENE DERIVATIVES FOR THE TREATMENT OF DISORDERS CAUSED BY IGE
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Thiophene derivatives of formula (I) and a pharmaceutically acceptable salt thereof are provided. These compounds have utility for the treatment or prevention of disorders caused by IgE, such as allergy, type 1 hypersensitivity or familiar sinus inflammation.
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Page/Page column 186
(2020/01/11)
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- New synthesis method of orotic acid
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The invention belongs to the field of organic chemistry and discloses a new synthesis method of orotic acid, comprising the following steps: S1: enabling glycolonitrile and ammonia wate to react, thusobtaining a reaction system a in which a product is aminoacetonitrile A; S2: enabling aminoacetonitrile A and cyanate to react, thus obtaining a reaction system b in which a product is cyanomethylurea B; S3: performing condensation-rearrangement on cyanomethylurea B and glyoxylic acid in an alkaline solution to obtain orotic acid I. The method has the advantages of safe operation, low cost, lesspollution from three wastes, total reaction yield of 80% or above, and easy industrialization.
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Paragraph 0019; 0035-0036; 0040-0041; 0045-0046
(2019/01/13)
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- Corresponding amine nitrile and method of manufacturing thereof
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The invention relates to a manufacturing method of nitrile. Compared with the prior art, the manufacturing method has the characteristics of significantly reduced using amount of an ammonia source, low environmental pressure, low energy consumption, low production cost, high purity and yield of a nitrile product and the like, and nitrile with a more complex structure can be obtained. The invention also relates to a method for manufacturing corresponding amine from nitrile.
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Paragraph 0153; 0154; 0155; 0160; 0161
(2018/05/07)
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- Prebiotic selection and assembly of proteinogenic amino acids and natural nucleotides from complex mixtures
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A central problem for the prebiotic synthesis of biological amino acids and nucleotides is to avoid the concomitant synthesis of undesired or irrelevant by-products. Additionally, multistep pathways require mechanisms that enable the sequential addition of reactants and purification of intermediates that are consistent with reasonable geochemical scenarios. Here, we show that 2-aminothiazole reacts selectively with two- and three-carbon sugars (glycolaldehyde and glyceraldehyde, respectively), which results in their accumulation and purification as stable crystalline aminals. This permits ribonucleotide synthesis, even from complex sugar mixtures. Remarkably, aminal formation also overcomes the thermodynamically favoured isomerization of glyceraldehyde into dihydroxyacetone because only the aminal of glyceraldehyde separates from the equilibrating mixture. Finally, we show that aminal formation provides a novel pathway to amino acids that avoids the synthesis of the non-proteinogenic α,α-disubstituted analogues. The common physicochemical mechanism that controls the proteinogenic amino acid and ribonucleotide assembly from prebiotic mixtures suggests that these essential classes of metabolite had a unified chemical origin.
- Islam, Saidul,Bu?ar, Dejan-Kre?imir,Powner, Matthew W.
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p. 584 - 589
(2017/05/31)
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- Hydrogen Liberation from Gaseous 2-Bora-1,3-diazacycloalkanium Cations
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Evidence is presented for cyclization to yield 2-bora-1,3-diazacycloalkanium cations in the gas phase. While the neutral compounds in solution and solid phase are known to possess an acyclic structure (as revealed by X-ray diffraction), the gaseous cations (from which borohydride BH4- ion has been expelled) have a cyclic structure, as revealed by InfraRed Multiple Photon Dissociation (IRMPD) spectroscopy and collisionally activated decomposition (CAD). The IRMPD decomposition of the monocyclic ions proceeds principally via H2 expulsion, although CAD experiments show additional pathways. Pyrolyses of solid monomeric salts and small oligomers produce higher polymers that are consistent with H2 expulsion as the major pathway. Deuterium labeling experiments show that scrambling occurs prior to IRMPD or CAD decomposition in the gas phase.
- Bendo, Jay-Ar,Martens, Jonathan,Berden, Giel,Oomens, Jos,Morton, Thomas Hellman
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p. 7910 - 7916
(2017/10/27)
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- Synthesis of aldehydic ribonucleotide and amino acid precursors by photoredox chemistry
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Light work: UV irradiation of a system formed by adding copper(I) cyanide to an aqueous solution of glycolonitrile, sodium phosphate, and hydrogen sulfide efficiently generates aldehyde precursors to the building blocks of RNA and proteins. Copyright
- Ritson, Dougal J.,Sutherland, John D.
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supporting information
p. 5845 - 5847
(2013/07/11)
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- METHOD FOR PRODUCING AMINONITRILES
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The invention relates to a process for preparing an amino nitrile mixture comprising aminoacetonitrile (AAN) and from 5 to 70% by weight of iminodiacetonitrile (IDAN), which comprises heating crude AAN which is largely free of formaldehyde cyanohydrin (FACH-free) at a temperature of from 50 to 150° C.
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Page/Page column 3
(2010/02/17)
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- PRODUCTION METHOD FOR ETHYLENEAMINE MIXTURES
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The invention relates to a process for preparing an ethylene amine mixture, which comprises hydrogenating an amino nitrile mixture comprising at least two α-amino nitriles in an amount of at least 5% by weight in each case in the presence of a catalyst and, if appropriate, a solvent.
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Page/Page column 10
(2010/05/13)
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- Design and synthesis of dipeptidyl nitriles as potent, selective, and reversible inhibitors of cathepsin C
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A series of dipeptide nitriles with a thienyl alanine in P2 were identified as potent and selective cathepsin C inhibitors. Incorporation of a substituted cyclopropyl moiety in P1 effectively protects these derivatives against hydrolase activity in whole blood.
- Guay, Daniel,Beaulieu, Christian,Jagadeeswar Reddy,Zamboni, Robert,Methot, Nathalie,Rubin, Joel,Ethier, Diane,David Percival
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scheme or table
p. 5392 - 5396
(2010/05/02)
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- 2-ARYLTHIAZOLE DERIVATIVES AS CXCR3 RECEPTOR MODULATORS
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The invention encompasses compounds of Formula I or pharmaceutically acceptable salts thereof, which are modulators of the CXCR3 chemokine receptor function useful for the treatment or prevention of pathogenic inflammatory processes, autoimmune diseases or graft rejection processes. Methods of use and pharmaceutical compositions are also encompassed.
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Page/Page column 56
(2010/11/28)
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- Primary amides as selective inhibitors of cathepsin K
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The nitrile warhead used in a series of cathepsin K inhibitors can be replaced by a less electrophilic primary amide. The accompanying loss of potency can be partially recovered by introducing a substituent α to the amide. The potency gain resulting from this addition is not achieved with the nitrile derivatives due to a different geometry of the cysteine adduct in the enzyme active site. This study led to the identification of the primary amide 2g, which is an inhibitory substrate, with an IC50 of 10 nM against cathepsin K and excellent selectivity versus the other cathepsins.
- Leger, Serge,Bayly, Christopher I.,Black, W. Cameron,Desmarais, Sylvie,Falgueyret, Jean-Pierre,Masse, Frederic,Percival, M. David,Truchon, Jean-Francois
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p. 4328 - 4332
(2008/02/10)
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- SUBSTITUTED QUINAZOLINE DERIVATIVES AND THEIR USE AS INHIBITORS
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The use of a compound of formula (I) 1 or a salt, ester or amide thereof; where X is O, or S, S(O) or S(O)2, or NR6 where R6 is hydrogen or C1-6 alkyl,; R5 is an optionally substituted 5-membered heteroaromatic ring, R1, R2 ,R3, R4 are independently selected from various specified moieties, in the preparation of a medicament for use in the inhibition of aurora 2 kinase. Certain compounds are novel and these, together with pharmaceutical compositions containing them are also described and claimed
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- Kinetics of reversible carbon deprotonation of 2-nitroethanol and 2-nitro-1,3-propanediol by hydroxide ion, water, amines, and carboxylate ions. A normal br?nsted α despite an imbalanced transition state
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Rates of reversible carbon deprotonation of 2-nitroethanol (2) and 2-nitro-1,3-propanediol (3) by hydroxide ion, water, amines, and carboxylate ions and pKa values for the ionization at carbon (pKaCH) and oxygen (pKaOH) and ionization of the aci-forms (pKaNOH) were determined in aqueous solution at 25 °C. The pKaCH values for 2 and 3 are 8.60 and 7.68, respectively, as compared to 10.22 for CH3NO2. The acidifying effect of the CH2OH groups is attributed to a combination of inductive electron withdrawal and hyperconjugative stabilization of the respective nitronate ions, possibly coupled with intramolecular hydrogen bonding stabilization of this ion. The higher acidity of 2-nitroethanol compared to nitromethane is reflected in higher rates of proton transfer from 2-nitroethanol, implying a "normal" Br?nsted α between 0 and 1. This contrasts with the negative α value based on the reaction of OH- with nitromethane, nitroethane, and 2-nitropropane (Kresge, A. J. Can. J. Chem. 1974, 52, 1897). Reasons why a normal α value is observed in the current system are discussed.
- Bernasconi, Claude F.,Panda, Markandeswar,Stronach, Michael W.
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p. 9206 - 9212
(2007/10/03)
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- EQUILIBRIUM OF α-AMINOACETONITRILE FORMATION FROM FORMALDEHYDE, HYDROGEN CYANIDE AND AMMONIA IN AQUEOUS SOLUTION: INDUSTRIAL AND PREBIOTIC SIGNIFICANCE
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The equilibrium constant, Kan(H2CO), for the formation of α-aminoacetonitrile from formaldehyde, ammonia and hydrogen cyanide was evaluated at 25 deg C.A first estimation of Kan(H2CO) was obtained from extrathermodynamic relationships of the type log K' vs Σ?*.The final value was then obtained from a comparison of the experimental and calculated pH dependences of α-hydroxy- and α-aminoacetonitrile concentrations.From these results, it appears that, after equilibrium, the ratio between the concentrations of the two precursors glycine and hydroxyethanoic acid, is a linear function of the concentration of free ammonia, i.e. /=21 at 25 deg C.
- Moutou, G.,Taillades, J.,Benefice-Malouet, S.,Commeyras, A.,Messina, G.,Mansani, R.
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p. 721 - 730
(2007/10/02)
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- Highly Sterically hindered Carbon Acids: The Intrinsic Reactivity of 5,5',5''-Trimethyl- and 3,3',3'',5,5',5''-Hexamethyl-2,2',2'',4,4',4''-Hexanitrotriphenylmethanes
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Rate constants (kpB,kpBH) for the reversible deprotonation of 5,5',5''-trimethyl- and 3,3',3'',5,5',5''-hexamethyl-2,2',2'',4,4',4''-hexanitrotriphenylmethanes (2 and 3) by primary aliphatic amines, piperidine and morpholine as well as by phenoxide anions and hydroxide anion have been measured in H2O-Me2SO (20:80) at 25 deg C.Comparison of the results obtained with those for 2,2',2'',4,4',4''-hexanitrotriphenylmethane (1a) shows that the introduction of methyl groups in positions adjacent to the nitro groups decreases markedly the thermodynamic acidity of theexocyclic CH group: ΔpK2a1a = 1.68; ΔpK3a1a = 6.48.It is suggested that these decreases are very likely the reflection of a twisting of the nitro groups out of their attached aromatic planes and therefore of a reduced resonance stabilization of the conjugated carbanions C-2 and C-3.Other important steric effects are operating in the ionization of 2 and 3.These arise from the accumulation of ortho-nitro groups in the triphenylmethane system which makes the approach of the base reagents from the exocyclic carbon of 2 and 3 very difficult.The finding of extremely low intrinsic reactivities for 2 and 3 and the observation of a much greater catalytic efficiency of primary amines than of secondary amines in assisting the proton transfers are the two most striking manifestations of these F-strain effects.
- Terrier, Francois,Xiao, Lan,Farrell, Patrick G.,Moskowitz, Danielle
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p. 1259 - 1263
(2007/10/02)
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- Kinetics of Amine Addition to Benzylidenemalonodialdehyde in 50percent Me2SO-50percent water
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The kinetics of the reaction of benzylidenemalonodialdehyde with piperidine, morpholine, n-butylamine, 2-methoxyethylamine, glycinamide, glycine ethyl ester, cyanomethylamine, and semicarbazide have been determined in 50percent aqueous Me2SO at 20 deg C.The reaction leads to a zwitterionic adduct, PhCH(RR'NH(1+))C(CHO)2(1-) (TA(+/-)), that is in fast acid-base equilibrium with the anionic adduct, PhCH(RR'N)C(CHO)2(1-) (TA(1-)).With strongly basic amines at high pH there is also attack of the amine on one of the carbonyl groups, which acts as a rapid preequilibrium.Rate constants for the formation of TA(+/-) (k1) and its reverse (k-1), as well as equilibrium constants (K1 = k1/k-1) and the pKa of TA(+/-) were determined for all the amines.Intrinsic rate constants (k0 = k1 = k-1 when K1 = 1) were calculated.The intrinsic rate constants are lower than those for amine addition to benzylidene Meldrum's acid.This is consistent with the greater role played by resonance in stabilizing TA(+/-) derived from benzylidenemalonodialdehyde.However, k0 for piperidine/morpholine addition to benzylidenemalonodialdehyde is much higher than for the reaction of benzylideneacetylacetone with the same amines, indicating that the rate-depressing effect of intramolecular hydrogen bonding in TA(+/-) derived from benzylidenemalonodialdehyde is much smaller than that in TA(+/-) derived from benzylideneacetylacetone.Even though semicarbazide is an α-effect nucleophile, no enhancement of k1 was observed, but K1, estimated on the basis of a structure-reactivity relationship, is larger than expected based on the pKa of the amine.This result is attributed to a low νnucn value.
- Bernasconi, Claude F.,Stronach, Michael W.
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p. 1993 - 2001
(2007/10/02)
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- Kinetics of Amine Addition to Benzylidene-1,3-indandione and Other Vinylic β-Diketones. Effect of Cyclic Structure and Steric Strain on Intrinsic Rate Constants
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The kinetics of the reactions of benzylidene-1,3-indandione (4) with piperidine, morpholine, n-butylamine, 2-methoxyethylamine, glycinamide, and cyanomethylamine and the reactions of benzylidene-3,5-heptanedione (5), benzylidene-2,6-dimethyl-3,5-heptanedione (6), and benzylidenedibenzoylmethane (7) with piperidine and morpholine have been measured in 50% Me2SO-50% water (v/v) at 20 °C and 0.5 M ionic strength. The reactions lead, in all cases, to the reversible formation of the zwitterionic adduct PhCH(RR′NH+)C(COX)2- (TA±) that is in fast equilibrium with its anion PhCH(RR′N)C-(COX)2-(TA-). Rate constants for nucleophilic addition (k1) and its reverse (k-1) as well as the pKa, of TA± were determined for all reactions. The intrinsic rate constant (k0 = k1 = k-1 when K1 = 1) for amine addition to 4 is abnormally high, whereas k0 for the reactions of 5-7 are abnormally low and similar to k0 in magnitude for amine addition to benzylideneacetylacetone reported previously. The terms "abnormally high" and "abnormally low" refer to positive and negative deviations, respectively, from a plot of log k0 for amine addition to a series of electrophilic olefins of the type PhCH=CYY′ vs log k0 for deprotonation of carbon acids of the type CH2YY′. The high k0 for the reaction of 4 is attributed to its cyclic structure, which assures that the π-overlap required for the stabilization of the adduct is strongly developed in the transition state. The low k0 values for the reactions of 5-7 arise from intramolecular hydrogen bonding, which is strong in TA± but poorly developed in the transition state, and from steric strain in the adduct, which is strongly developed in the transition state. All these effects can be viewed as manifestations of the principle of nonperfect synchronization (PNS).
- Bernasconi, Claude F.,Stronach, Michael W.
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p. 2222 - 2227
(2007/10/02)
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- Novel amide derivatives, processes for production thereof, and agricultural-horticultural fungicide containing them
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An amide derivative represented by the following general formula (I) STR1 wherein one of X and Y represents a sulfur atom and the other represents a carbon atom, Z represents a nitrile or thioamide group, each of R1 and R2 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a halomethyl group or a phenyl group, and R3 represents an alkenyl group having 2 to 6 carbon atoms, a haloalkenyl group having 2 to 4 carbon atoms, a furyl group, a thienyl group, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an alkynyloxy group having 3 to 5 carbon atoms, an alkynylthio group having 3 to 5 carbon atoms, a pyrazolyl group, or an unsubstituted or halo-substituted phenyl group; processes for producing the amide derivative; an agricultural-horicultural fungicide comprising the amide derivative as an active ingredient; and to an agricultural-horicultural fungicidal composition comprising the amide derivative of general formula (I) as an active ingredient.
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- Photochemical Formation of Methylamine and Ethylenediamine from Gas Mixtures of Methane, Ammonia, and Water
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The photolysis of mixtures of CH4, NH3, and H2O with a low-pressure mercury lamp led to the formation of considerable amounts of methylamine and ethylenediamine with oxygen-containing compounds, ethane, and hydrogen.CH2NH2 radicals formed during photolysis were detected by ESR applying a spin trap technique, and it was suggested that the coupling of the radicals leads to the formation of ethylenediamine.
- Ogura, Kotaro,Migita, Catharina T.,Yamada, Tooru
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p. 1563 - 1566
(2007/10/02)
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- The Ammonolysis of Trichloroethylene to Glycine
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Glycine was obtained by the ammonolysis of trichloroethylene with aqueous ammonia. Various alkalines, such as alkaline metal hydroxides, carbonates, and hydrogencarbonates, accelerated the reaction; the yield of glycine was 40-70percent after a 4 h reaction at 180 deg C. Our results on the effect of alkalines indicate that ammonolysis proceeded sequentially via the formation of aminoacetonitrile. A good yield of the intermediate compound, aminoacetonitrile, was obtained by heating trichloroethylene at 70 deg C with anhydrous ammonia under reaction conditions.
- Inoue, Masami,Enomoto, Saburo
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