Cascade reactions of captodative formyl(amino)alkenes with N,O-binucleophiles

Rulev, Alexander Yu.; Ларина, Л. И.; Chuvashev, Yuri A.; Новокшонов, В. В.

doi:10.1070/mc2005v015n03abeh002101

Cited by 5 publications

(2 citation statements)

References 12 publications

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“…In these experiments 4H-1,3,5-dithiazinane (49) (~3%) and 1,2,4-trithiolane 10 (~2%) were detected as side products. It should be noted that in all the experiments the authors did not observe the formation of products from intramolecular cyclization during cyclothiomethylation, although there are examples in the literature [61][62][63][64] of the condensation of 2-amino alcohols with CH 2 O to 1,3-oxazolidines. This is apparently due to the fact that the amino group in the amino alcohols is more nucleophilic than the hydroxyl group and the reaction with CH 2 O and H 2 S takes place in stages, i.e., initially at the NH 2 group with the formation of the dithiazines 51a-c, and subsequent oxymethylation of the obtained N-hydroxyalkyldithiazines by an excess of CH 2 O leads to the corresponding 1,3,5-dithiazinan-5-ylalkoxymethanols 52a-c.…”

Section: Aliphatic Amino Alcohols In Cyclothiomethylation With H 2 S mentioning

confidence: 97%

Cyclothiomethylation of primary amines with formaldehyde and hydrogen sulfide to nitrogen- and sulfur-containing heterocycles (review)

Ахметова

Nadyrgulova

Niatshina

et al. 2009

Chem Heterocycl Comp

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Section: Aliphatic Amino Alcohols In Cyclothiomethylation With H 2 S mentioning

confidence: 97%

Cyclothiomethylation of primary amines with formaldehyde and hydrogen sulfide to nitrogen- and sulfur-containing heterocycles (review)

Ахметова

Nadyrgulova

Niatshina

et al. 2009

Chem Heterocycl Comp

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“…In all cases, no intramolecular cyclization products were detected, though examples of condensation of α-amino alcohols with CH 2 O to 1,3-oxazolidines [16][17][18][19][20] and with epoxyethane to morpholine [20] were reported. Presumably, the reason is that the amino group in amino alcohols is more nucleophilic than the hydroxy group; therefore, the reaction with CH 2 O and H 2 S occurs stepwise.…”

Section: Doi: 101134/s1070428007060218mentioning

confidence: 99%

Thiomethylation of amino alcohols using formaldehyde and hydrogen sulfide

et al. 2007

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Abstract-Three-component condensations of formaldehyde with hydrogen sulfide and hydroxylamine or amino alcohols at a ratio of 3 : 2 : 1 give 47-73% of N-hydroxy(or hydroxyalkyl)-1,3,5-dithiazinanes. The reactions of CH 2 O with H 2 S and hydroxylamine or α-amino alcohols at a ratio of 4 : 3 : 1 involve both amino and hydroxy groups, leading to the corresponding dithiazinanes. 4-Aminobutan-1-ol reacts with CH 2 O and H 2 S under analogous conditions only at the amino group to form 4-(1,3,5-dithiazinan-5-yl)butan-1-ol.Thiomethylation of various amines with formaldehyde and hydrogen sulfide is known to give 1,3,5-dithiazinanes [1][2][3]. With a view to extent the scope of application of this method and elucidate the possibility of using difunctional amino-and hydroxy-containing monomers as substrates, in the present study we examined for the first time reactions of aliphatic amino alcohols with CH 2 O and H 2 S. As initial compounds we selected aqueous ammonia, hydroxylamine, 2-aminoethanol, R-(-)-2-aminobutan-1-ol, 2-amino-3-hydroxypropionic acid (serine), and 4-aminobutan-1-ol. According to [4], hydroxylamine reacts with formaldehyde to give exclusively 1,3,5-trihydroxy-1,3,5-triazine. We have found that three-component condensation of hydroxylamine with CH 2 O and H 2 S at a ratio of 1 : 2 : 1 or 1 : 3 : 2 at 20°C leads to the formation of 1,3,5-dithiazinan-5-ol (I) (Scheme 1). When the amount of the thiomethylating agent (CH 2 O-H 2 S) increases (reactant ratio 1 : 4 : 3), the hydroxy group of the substrate is also involved in the process. At a reactant ratio of 1 : 2 : 1, the yield of compound I is ~31%; also, 5-methyl-1,3,5-dithiazinane (II) is formed as minor product: its fraction does not exceed 1% (Table 1). In the presence of excess CH 2 O and H 2 S (NH 2 OH-H 2 O-H 2 S ratio 1 : 4 : 3), the major product is 1,3,5-dithiazinan-5-yloxymethanol (III, ~56%). In addition, ~3% of 1,3,5-dithiazinane (IV) and ~2% of 1,2,4-trithiolane (V) are formed. Further raising of the amount of CH 2 O-H 2 S to a ratio of (5 : 3) : 1 with respect to hydroxylamine favors preferential formation of alcohol III which is likely to arise from compound I and formaldehyde.

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