LXXII.—Methylation by means of formaldehyde. Part I. The mechanism of the interaction of formaldehyde and ammonium chloride; the preparation of methylamine and of dimethylamine

Werner, Emil Alphonse

doi:10.1039/ct9171100844

Cited by 22 publications

(13 citation statements)

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“…At temperatures higher than 100 °C, an equimolar solution of formaldehyde and ammonia may also lead in a few hours to the formation of amine compounds, such as methylamine (CH 3 NH 2 ), dimethylamine (CH 3 ) 2 NH and trimethylamine (CH 3 )3N ( Jones and Wheatley, 1918;Werner, 1917 ). Noted that this reaction also leads to the formation of amino acids in acid hydrolysis conditions ( Fox and Windsor, 1970;Hulett et al, 1971 ) and in alkaline hydrolysis conditions with the presence of glycolaldehyde ( Kebukawa et al, 2017 ).…”

Section: Formation Of a Diverse Suite Of New Soluble Compoundsmentioning

confidence: 99%

Evolution of interstellar organic compounds under asteroidal hydrothermal conditions

Vinogradoff

Bernard

Guillou

et al. 2018

Icarus

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International audienceCarbonaceous chondrites (CC) contain a diversity of organic compounds. No definitive evidence for a genetic relationship between these complex organic molecules and the simple organic molecules detected in the interstellar medium (ISM) has yet been reported. One of the many difficulties arises from the transformations of organic compounds during accretion and hydrothermal alteration on asteroids. Here, we report results of hydrothermal alteration experiments conducted on a common constituent of interstellar ice analogs, Hexamethylenetetramine (HMT – C 6 H 12 N 4). We submitted HMT to asteroidal hydrothermal conditions at 150 °C, for various durations (up to 31 days) and under alkaline pH. Organic products were characterized by gas chromatography mass spectrometry, infrared spectroscopy and synchrotron-based X-ray absorption near edge structure spectroscopy. Results show that, within a few days, HMT has evolved into (1) a very diverse suite of soluble compounds dominated by N-bearing aromatic compounds (> 150 species after 31 days), including for instance formamide, pyridine, pyrrole and their polymers (2) an aromatic and N-rich insoluble material that forms after only 7 days of experiment and then remains stable through time. The reaction pathways leading to the soluble compounds likely include HMT dissociation, formose and Maillard-type reactions, e.g. reactions of sugar derivatives with amines. The present study demonstrates that, if interstellar organic compounds such as HMT had been accreted by chondrite parent bodies, they would have undergone chemical transformations during hydrothermal alteration, potentially leading to the formation of high molecular weight insoluble organic molecules. Some of the diversity of soluble and insoluble organic compounds found in CC may thus result from asteroidal hydrothermal alteration

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Section: Formation Of a Diverse Suite Of New Soluble Compoundsmentioning

confidence: 99%

Evolution of interstellar organic compounds under asteroidal hydrothermal conditions

Vinogradoff

Bernard

Guillou

et al. 2018

Icarus

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“…Eschweiler (18) has already treated a n u m b e r of amines with formalin to obtain the corresponding N-methyl derivatives. Werner (19) has also investigated t h e methylated products of ammonia with formalin a n d proposed a n criamine theory f o r the mechanism of the Eschweiler reaction. Considering the fact that the t r e a t m e n t of If with formalin under a variety of conditions, even in basic media, afforded the N-methyl derivative (VIIa), it is assumed that the N-methylol would be reduced to Vlla by attack of a hydride anion d u e to formaldehyde in the absence of a n y trace of formic acid.…”

Section: \ IImentioning

confidence: 99%

Mannich and eschweiler‐clarke reaction of 1‐benzyl‐1,2,3,4‐tetrahydroisoquinolines. Studies on the syntheses of heterocyclic compounds. Part CCCXVIII

Kametani

Noguchi

Saito

1969

Journal of Heterocyclic Chem

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Modified Mannich reactions of a number of 1‐benzyl‐1,2,3,4‐tetrahydroisoquinolines (Ia‐Ie) were attempted to afford the corresponding protoberberine derivatives (IIa‐IIe) in good yield. Treatment of both If and Ig with formalin under a variety of Mannich or Eschweiler‐Clarke conditions did not give the expected protoberberine derivatives IIf and IIg, but afforded the N‐methyl derivatives (VIIa) and (VIIb), respectively.

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“…Diethylamine-ad,. DCI was prepared by the method reported by Werner (23). Acetaldehyde-ad, (Merck Sharp and Dohme, I g) was added to a solution of ammonium chloride-d4 (Merck Sharp and Dohme) in D 2 0 (1 g, ND,CI in 4 ml D20).…”

Section: Ma Rerialsmentioning

confidence: 99%

Hydrolysis of Sulfamoyl Chlorides. II. Hydrogen Participation in the Hydrolysis of Diethyl and Methylethylsulfamoyl Chlorides

Ko¹,

Robertson²

1972

Can. J. Chem.

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Diethylsulfamoyl chloride (2) hydrolyzes eight times faster than dimethylsulfamoyl chloride (1). In 2 the secondary deuterium isotope effect was found to be about 2, hence hydrogen participation is important in the hydrolysis of this compound. The temperature coefficient of the enthalpy of activation ( A c t ) is exceptional (-39 cal mol-' deg-') for a reaction presumably following an SNI mechanism. The kinetic solvent isotope effect was normal for such a mechanism. The corresponding value of AC: for the hydrolysis of piperidylsulfamoyl chloride (4) was about the same as found for 2 while the value for the methylethyl isomer (3) was -66 cal deg-' mol-', an intermediate value supporting an explanation based on solvent exclusion. Experiments in mixed solvents support the hypothesis that solvent reorganization is the major factor in determining the value of AC: for 2 but not for 4.Le chlorure de dii.thylsulfamoyle (2) hydrolyse huit fois plus vite que le chlorure de dimCthylsulfamoyle (1). Dans 2, l'effet isotopique secondaire du deuterium est trouve a peu prts egal a 2, par suite la participation de I'hydrogtne est importante dans I'hydrolyse de ce composC. Le coefficient de temptrature de l'enthalpie d'activation (AC:) est exceptionnel (-39 cal mol-' deg-') pour une reaction suivant probablement un mecanisme SN1. L'effet isotopique cinetique du solvant ttait normal pour un tel mtcanisme. La valeur correspondante de AC: pour I'hydrolyse du chlorure de pipi.ridylsulfamoyle (4) a ttC environ la meme que celle trouvte pour 2 tandis que la valeur de I'isomere methyltthyl (3) etait de -66 cal deg-' mol-', valeur intermediaire ktayant une explication fondke sur I'exclusion de solvant. Des exptriences dans des solvants melanges ttayent I'hypothtse que la reorganisation du solvant est le facteur principal dans la determination de la valeur de AC: pour 2 mais non pas pour 4.

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LXXII.—Methylation by means of formaldehyde. Part I. The mechanism of the interaction of formaldehyde and ammonium chloride; the preparation of methylamine and of dimethylamine

Cited by 22 publications

References 0 publications

Evolution of interstellar organic compounds under asteroidal hydrothermal conditions

Evolution of interstellar organic compounds under asteroidal hydrothermal conditions

Mannich and eschweiler‐clarke reaction of 1‐benzyl‐1,2,3,4‐tetrahydroisoquinolines. Studies on the syntheses of heterocyclic compounds. Part CCCXVIII

Hydrolysis of Sulfamoyl Chlorides. II. Hydrogen Participation in the Hydrolysis of Diethyl and Methylethylsulfamoyl Chlorides

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