NEW REACTIONS AND DERIVATIVES OF UREA SYNTHESIS OF TRIAZINES<sup>1</sup>

Paquin, Alfred Max

doi:10.1021/jo01154a001

Cited by 11 publications

(14 citation statements)

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“…The N-methylene derivative of a primary amine [10] may be used in place of the latter. Ethylenediamine and ethanolamine have been used [3][4][5] as bifunctional amines in a three-component condensation and ethanolamine and N,N-dimethylethylenediamine [7] in the condensation with DMU. In all four cases the expected 5-substituted 1,3,5-triazinan-2-one cyclic Mannich bases were obtained.…”

mentioning

confidence: 99%

Unexpected Formation of a Tricycle in the Reaction of 1,3-Bis(Hydroxymethyl)Urea with Propane-1,3-Diamine*

Hamoud

Рамш

Певзнер

et al. 2014

Chem Heterocycl Comp

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By contrast with the aminomethylation of thiourea by formaldehyde and primary amines to form 5-substituted 1,3,5-triazinane-2-thiones (see studies [1,2] and references therein) the aminomethylation of urea has not attracted so much work [3-10], the most recent being published in 1991. Because of the possibility of different condensations involving urea and formaldehyde [11,12] cyclic urea Mannich bases are better obtained not by a three-component condensation of urea, formaldehyde, and the corresponding primary amine [3-5, 7] but rather using 1,3-dimethylolurea (DMU) (1) [13], prepared from urea and formaldehyde, which then condenses with a suitable primary amine [7,8] or by condensing urea with the previously prepared dimethylol derivative of a primary amine with or without isolation of the indicated intermediate product [9]. The N-methylene derivative of a primary amine [10] may be used in place of the latter. Ethylenediamine and ethanolamine have been used [3][4][5] as bifunctional amines in a three-component condensation and ethanolamine and N,N-dimethylethylenediamine [7] in the condensation with DMU. In all four cases the expected 5-substituted 1,3,5-triazinan-2-one cyclic Mannich bases were obtained.

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mentioning

confidence: 99%

Unexpected Formation of a Tricycle in the Reaction of 1,3-Bis(Hydroxymethyl)Urea with Propane-1,3-Diamine*

Hamoud

Рамш

Певзнер

et al. 2014

Chem Heterocycl Comp

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“…In contrast, urea reacts with up to three units of formaldehyde per molecule under similar conditions (Becher [8] and others [4,[9][10][11][12] ). Because of the fact that 1,3-dimethylurea reacts only with one molecule of formaldehyde, the formation of polymeric chains is not possible, but a single condensation takes place.…”

Section: Similarities Differences and Limitations Of The Model Systemmentioning

confidence: 93%

Investigation of the reaction of 1,3‐dimethylurea with formaldehyde by quantitative on‐line NMR spectroscopy: a model for the urea–formaldehyde system

Steinhof

Scherr

Hasse

2015

Magnetic Reson in Chemistry

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Quantitative on-line NMR spectroscopy is applied to study equilibria and reaction kinetics of the reaction of formaldehyde with 1,3-dimethylurea. This reaction system serves as a model system for the much more complex but industrially relevant urea-formaldehyde system. The aim is to study individual reactions and intermediates. The 1,3-dimethylurea-formaldehyde system undergoes only four reactions and, unlike urea-formaldehyde, does not form polymers. The following reactions are studied in detail: (1) the hydroxymethylation, (2) the formation of hemiformals of the hydroxymethylated intermediate, and (3) two condensation reactions of which the first leads to methylene bridges, the other to ether bridges. NMR spectroscopic chemical shift data of the reacting species are provided for the (1) H, (13) C, and (15) N domains. Equilibrium data of reactions (1), (2), and (3) are determined by quantitative (1) H and (13) C NMR spectroscopy at molar ratios of formaldehyde to 1,3-dimethylurea between 1:2 and 16:1 at a pH value of 8.5. Reaction kinetic experiments using an NMR spectrometer coupled to a batch reactor led to a reaction kinetic model parametrized with true species concentrations. The model takes into account reactions (1), (2), and (3). It describes the reaction system well for molar ratios of 1:1, 2:1, and 4:1, temperatures of 303 to 333K, and pH values from 5.0 to 9.5. Dilution experiments with a micro mixer coupled to the NMR spectrometer are conducted to estimate the time to equilibrium of reaction (2) of which the time constant is significantly lower than those of reactions (1) and (3). Copyright © 2015 John Wiley & Sons, Ltd.

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“…The mixture was then heated for 1.5 h under reflux, and the precipitate was filtered off from the hot mixture and dried under reduced pressure. Yield 7.21 g (69%), mp 195-200°C (from H 2 O); published data: mp 208-210°C [3], 209-210°C [4,14].…”

Section: Nn′-bis(hydroxymethyl)thiourea (2)mentioning

confidence: 99%

“…However, only a few data are available on three-component condensations of thiourea (1) with formaldehyde and simplest aliphatic diamines. Paquin [3,4] reported on the reactions of thiourea with formaldehyde and ethylenediamine at molar ratios of 1 : 2 : 1 and 2 : 4 : 1, which afforded 5-(2-aminoethyl)-1,3,5-triazinane-2-thione and 5,5′-(ethane-1,2-diyl)bis(1,3,5-triazinane-2-thione), respectively. Neither three-component condensations of thiourea (1) with formaldehyde and propane-1,3-diamine or butane-1,4-diamine nor two-component condensations of N,N′-bis(hydroxymethyl)thiourea (2) with ethane-1,2-, propane-1,3-, and butane-1,4-diamines were studied previously.…”

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confidence: 99%

Reaction of thiourea with formaldehyde and simplest aliphatic diamines

et al. 2016

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N,N′-Bis(hydroxymethyl)thiourea reacted with propane-1,3-diamine at a molar ratio of 2 : 1 to give 5,5′-propane-1,3-diylbis(1,3,5-triazinane-2-thione), whereas 1, 3,5,7,11,13,15,17-octaazatricyclo[15.3.1.1 7,11 ]docosane-4,14-dithione was obtained in the reaction with equimolar amounts of the reactants. Tricyclic product was also formed in the three-component condensation of thiourea with formaldehyde and propane-1,3-diamine at a ratio of 1 : 3 : 1. The reactions of N,N′-bis(hydroxymethyl)thiourea with ethane-1,2-diamine (2 : 1) and of thiourea with formaldehyde and butane-1,4-diamine (1 : 2 : 1) afforded 5,5′-(ethane-1,2-diyl)bis(1,3,5-triazinane-2-thione) and 5,5′-(butane-1,4-diyl)bis(1,3,5-triazinane-2-thione), respectively.

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NEW REACTIONS AND DERIVATIVES OF UREA SYNTHESIS OF TRIAZINES¹

Cited by 11 publications

References 0 publications

Unexpected Formation of a Tricycle in the Reaction of 1,3-Bis(Hydroxymethyl)Urea with Propane-1,3-Diamine*

Unexpected Formation of a Tricycle in the Reaction of 1,3-Bis(Hydroxymethyl)Urea with Propane-1,3-Diamine*

Investigation of the reaction of 1,3‐dimethylurea with formaldehyde by quantitative on‐line NMR spectroscopy: a model for the urea–formaldehyde system

Reaction of thiourea with formaldehyde and simplest aliphatic diamines

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NEW REACTIONS AND DERIVATIVES OF UREA SYNTHESIS OF TRIAZINES1

Cited by 11 publications

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Unexpected Formation of a Tricycle in the Reaction of 1,3-Bis(Hydroxymethyl)Urea with Propane-1,3-Diamine*

Unexpected Formation of a Tricycle in the Reaction of 1,3-Bis(Hydroxymethyl)Urea with Propane-1,3-Diamine*

Investigation of the reaction of 1,3‐dimethylurea with formaldehyde by quantitative on‐line NMR spectroscopy: a model for the urea–formaldehyde system

Reaction of thiourea with formaldehyde and simplest aliphatic diamines

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NEW REACTIONS AND DERIVATIVES OF UREA SYNTHESIS OF TRIAZINES¹