RU2551689C1 - Method of obtaining n,n,n-tri[(phenyl(benzyl)sulphanyl)-methyl]amines - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a method of obtaining N,N,N-tri[(phenyl(benzyl)sulphanyl)-methyl]amines (1), which consists in the interaction of phenyl(benzyl)thiols of the general formula R-SH [R is said above] with hexamethylenetetramine with the participation of the catalyst samarium nitrate crystallohydrate, applied on γ-Al₂O₃ Sm(NO₃)₂*6H₂O/γ-Al₂O₃, taken in the stoichiometrical ratio thiol:hexamethylenetetramine 60:10, which is characterised by the fact that the reaction is carried out in the presence of the catalyst samarium nitrate crystallohydrate, applied on γ-Al₂O₃, with the content of the catalyst Sm(NO₃)₂*6H₂O/γ-Al₂O₃ in the reaction mass of 0.03-0.07 wt % relative to hexamethylentetramine in chloroform as the solvent at a temperature of 50-70°C and atmospheric pressure for 3-5 h.

EFFECT: output of N,N,N-tri[(phenyl(benzyl)sulphanyl)-methyl]amines (1) constitutes 91-99%.

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Description

The invention relates to the field of organic chemistry, specifically to a method for producing N, N, N-tri [(phenyl (benzyl) sulfanyl) methyl] amines of the general formula (1):

where R = Ph, Bn

Compounds of formula (1) are promising as new modified crop protection agents against root rot and crop growth enhancing agents (N.B. Troshina, L.G. Yarullina, O.B. Surina, I.V. Maksimov // Cytology T. 48, 2006, No. 6, p. 495-499).

A known method of producing N, N, N-tri [(phenyl (benzyl) sulfanyl) methyl] amines (1) (IE Pollak, GF Grillot. The Thiomethylation of Ammonia. J. Org. Chem., 1967, V.32, No. 9, p. 2891) by the interaction of phenyl (benzyl) thiols with aqueous solutions of formaldehyde (37%) and ammonia in boiling alcohol as a solvent

A significant drawback of the known method is the reaction with the participation of aqueous solutions of gaseous formaldehyde (t. Bale = -19 ° C) and ammonia (t. Bale = -33.34 ° C) in boiling alcohol. Gaseous formalin and ammonia are lacrimators, in addition, during the reaction in a boiling medium, the concentration of the starting reagents changes due to the volatilization of formalin and ammonia.

A known method for producing N, N, N-tri [(phenyl (benzyl) sulfanyl) methyl] amines (1) (G. Dougherty, WH Taylor. Studies in Thiophenol Chemistry. I. A Condensation Reaction between Thiophenols and Condensed Aldehyde-Ammonias. JACS, 1933, V.55, p. 4588) with yields of 95-97% by reaction of phenyl (benzyl) thiols with hexamethylenetetramine in boiling 1,4-dioxane as solvent

A significant disadvantage of this method is the high fire hazard of the process, associated with the need to conduct the reaction at high temperature (> 100 ° C) in boiling dioxane for 24 hours. The use of an ethereal solvent (1,4-dioxane) capable of accumulating peroxide compounds and carrying out the reaction in a boiling medium makes it difficult to produce large scale N, N, N-tri [(phenyl (benzyl) sulfanyl) methyl] amines.

An improved process for the preparation of N, N, N-tri [(phenyl (benzyl) sulfanyl) methyl] amines (1) is proposed.

The essence of the method consists in the interaction of phenyl (benzyl) thiols of the general formula R-SH, where R = C ₆ H ₅ , CH ₂ C ₆ H ₅ , with hexamethylenetetramine involving a samarium nitrate crystalline hydrate catalyst supported on γ-alumina, Sm (NO ₃ ) ₂ * 6H ₂ O / γ-Al ₂ O ₃ , taken in a stoichiometric molar ratio of thiol: hexamethylenetetramine 60:10 when the catalyst content in the reaction mass is Sm (NO ₃ ) ₂ * 6H ₂ O / γ-Al ₂ O ₃ 0.03 -0.07 wt.%, Preferably 0.05 wt.%, Calculated on hexamethylenetetramine in chloroform as solvent at a temperature of 50-70 ° C, preferably 60 ° C and atmospheric pressure for 3-5 hours. The yield of N, N, N-tri [(phenyl (benzyl) sulfanyl) methyl] amines (1) is 91-99%. The reaction proceeds according to the scheme

The target products (1) are formed only with the participation of the corresponding phenyl (benzyl) thiols and hexamethylenetetramine. In the presence of other thiols (e.g., alkyl, hetarylthiols) or other polyamines (e.g., N, N, N, N-tetramethylethanediamine, N, N, N, N-tetramethylpropanediamine), the desired products (1) are not formed. A change in the ratio of the starting reagents in the direction of increasing the content of phenyl (benzyl) thiol with respect to the starting hexamethylenetetramine does not significantly increase the yield of the target product (1).

Reactions were carried out at a temperature of 50-70 ° C. At lower temperatures (e.g. 25 ° C), the reaction rate decreases.

Differences and advantages of the proposed method from the known. In the known method, the reaction takes place in 24 hours in a flammable ether solvent (1,4-dioxane) at a temperature of> 100 ° C to form N, N, N-tri - [(phenyl (benzyl) sulfanyl) methyl] amines (1) s yields 95-97%. In the proposed method, a heterogeneous catalyst Sm (NO ₃ ) ₃ * 6H ₂ ) O / γ-Al ₂ O _{3 is used} , which can be used repeatedly without regeneration. With the participation of a heterogeneous catalyst, the yield of the target products (1) is 91-99%, the reaction time is reduced to 3-5 hours, the reaction temperature is up to 60 ° C, fireproof chloroform is used as a solvent.

The Sm (NO ₃ ) ₂ * 6H ₂ O / γ-Al ₂ O ₃ catalyst is prepared in accordance with the known general principles for the preparation of supported catalysts [N.A. Pakhomov. The scientific basis for the preparation of catalysts: an introduction to theory and practice. Novosibirsk: Publishing House of the SB RAS, 2011, p. 262] by impregnating the γ-Al ₂ O ₃ support with a samarium nitrate solution, followed by drying at 120-130 ° C. The catalyst contains 12.8 wt.% Sm (NO ₃ ) ₂ * 6H ₂ O and 87.2 wt.% Γ-Al ₂ O ₃ .

EXAMPLE 1. 0.66 g (60 mmol) of thiophenol, 0.14 g (10 mmol) of hexamethylenetetramine in 2 ml of chloroform, 0.007 g (0.05 wt.%) Of Sm (NO ₃ ) ₂ * 6H catalyst are placed in a glass reactor mounted on a magnetic stirrer. ₂ O / γ-Al ₂ O ₃ , stirred for 4 hours at a temperature of 60 ° C. N, N, N-tri [(phenylsulfanyl) methyl] amine are isolated from the reaction mass in 95% yield.

Other examples confirming the method are given in table 1.

Table 1 No. p / p Starting thiol The content of Sm (NO ₃ ) ₂ * 6H ₂ O / γ-Al ₂ O ₃ , wt.% Reaction temperature, ° C Reaction time, hour Yield (1),% one Thiophenol 0.05 60 four 95 2 "-" 0.03 60 four 91 3 "-" 0.07 60 four 99 four "-" 0.05 fifty four 94 5 "-" 0.05 70 four 98 6 "-" 0.05 60 5 97 7 "-" 0.05 60 3 93 8 Benzylthiol 0.05 60 four 96

Reactions were carried out at a temperature of 50-70 ° C in chloroform as a solvent.

Spectral characteristics of N, N, N-tri [(phenyl (benzyl) sulfanyl) methyl] amines (1)

N, N, N-tri [(phenylsulfanyl) methyl] amine NMR Spectrum ¹ H δ, ppm: 4.52 s (6H, H ^{2'2′2 ″} ); 7.25-7.45 m (15H, Ar). ¹³ C NMR spectrum, ppm: 59.29 (C ^{2'2′2 ″} ); 127.32 (C ⁷ ); 127.57 (C ^6.8 ); 129.12 (C ^5.9 ); 131.27 (C ⁴ ).

N, N, N-tri [(benzylsulfanyl) methyl] amine NMR Spectrum ¹ H δ, ppm: 3.75 s (6H, H ^{4.4′4 ″} ); 3.98 s (6H, H ^{2'2′2 ″} ); 7.25-7.33 m (15H, Ar). ¹³ C NMR spectrum, ppm: 35.72 (C ^{4.4′4 ″} ); 54.89 (C ^{2'2′2 ″} ); 127.03 (C ⁸ ); 128.56 (C ^7.9 ); 128.92 (C ^6.10 ); 138.49 (C ⁵ ).

Claims (1)

The method of obtaining N, N, N-tri [(phenyl (benzyl) sulfanyl) methyl] amines of the General formula (1)

where R = Ph, Bn
the interaction of phenyl (benzyl) thiols of the general formula R-SH [R = above] with hexamethylenetetramine taken in a stoichiometric ratio of thiol: hexamethylenetetramine 60:10, characterized in that the reaction is carried out in the presence of a samarium nitrate crystalline hydrate catalyst supported on γ-Al ₂ O ₃ , when the catalyst content Sm (NO ₃ ) ₂ * 6H ₂ O / γ-Al ₂ O ₃ in the reaction mass of 0.03-0.07 wt.% With respect to hexamethylenetetramine in chloroform as a solvent at a temperature of 50-70 ° C and atmospheric pressure for 3-5 hours