RU2529512C2 - Method of producing 1,8-{bis[(pent-2,4-dion-3-yl)methylsulphanyl]}-3,6-dioxaoctane and 4,4'-{bis[(pent-2,4-dion-3-yl)methylsulphanyl]}-diphenyl oxide - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to organic chemistry, particularly a method of producing 1,8-{bis[(pent-2,4-dion-3-yl)methylsulphanyl]}-3,6-dioxaoctane (1a) and 4,4'-{bis[(pent-2,4-dion-3-yl)methylsulphanyl]}-diphenyl oxide (1b) of general formula (1):

where (1a)

(1b)

characterised by that formaldehyde (37%) reacts with α,ω-dithiol HS-X-SH, where X=(CH)₂O(CH)₂O(CH)₂; n-C₆H₄-O-C₆H₄-n, and acetylacetone in the presence of a Al₂O₃/SiO₂ catalyst, with molar ratio acetylacetone:CH₂O:α,ω-dithiol:Al₂O₃/SiO₂=2:2:1:(0.03-0.07), at room temperature (about 20°C) and atmospheric pressure for 5-7 hours in a chloroform-ethanol solvent mixture (1:1, by volume).

EFFECT: method of producing 1,8-{bis[(pent-2,4-dion-3-yl)methylsulphanyl]}-3,6-dioxaoctane (1a) and 4,4'-{bis[(pent-2,4-dion-3-yl)methylsulphanyl]}-diphenyl oxide (1b), which can be used as selective sorbents, extractants and complexing agents.

1 tbl, 1 ex

Description

The invention relates to the field of organic chemistry, in particular to a method for producing 1,8- {bis [(pent-2,4-dion-3-yl) methylsulfanyl]} - 3,6-dioxoctane (1a) and 4,4′- {bis [(pent-2,4-dion-3-yl) methylsulfanyl]} - diphenyl oxide (1b) of the general formula (1):

;

Where

;

Similar O, S-containing compounds can be used as selective sorbents, extractants and complexing agents [I.V. Svistunova, E.V. Fedorenko. α-Substituted boron difluoride acetylacetonates. Zhokh, 2008, v. 78, No. 8, pp. 1280-1288].

There is a method for producing an α-substituted pent-2,4-dione [N. Lego. Synthesis of arylacetones from aryl halides and acetylacetonate. Chemistry Letters, 1982, p.597-600], in particular the preparation of aryldiacetones (2) by the reaction of aryl halides with sodium and potassium acetylacetonates in the presence of an equimolar amount of copper halides in dimethyl phthalate (DMF) at 100 ° C according to the scheme:

M = Na, K

R = H, 2-CH ₃ , 4- CH ₃ , 4-CH ₃ O, 3-CH ₃ CO, 3-PhCO, 4-NO ₂

X = Br, I

Y = Cl, Br, I

In a known manner, 1,8- {bis [(pent-2,4-dion-3-yl) methylsulfanyl]} - 3,6-dioxaoctane (1a) and 4,4 ′ - {bis [(pent- 2,4-dion-3-yl) methylsulfanyl]} - diphenyl oxide (1b) by the general formula (1).

A known method of producing bis - {(N, N′-dimethyl amino) methylsulfanyl} -3,6-dioxoctane, bis - {(N, N′-dimethylamino) methylsulfanyl} diphenyl oxide and bis (N, N′-dimethylamino) methylsulfanyl} -alkanes (3) [PPKhayrullina, B.F. Akmanov, T.V. Tyumkina, R.V. Kunakova, A.G. Ibrahimov. N, N, N ′, N′-tetramethylmethanediamine is an effective reagent for aminomethylation of thiols. ZhORKh, 2012, v. 48, No. 2, pp. 189-193], by the aminomethylation of α, ω-dithiols with bisamine in the presence of a catalytic amount of SmCl ₃ · 6H ₂ O or FeCl ₃ · 6H ₂ O at a reaction temperature of 60 ° C within 1.5 hours with a yield of 80-94% according to the scheme:

;

;

;

;

The known method does not lead to the production of 1,8- {bis [(pent-2,4-dion-3-yl) methylsulfanyl]} - 3,6-dioxoctane (1a) and 4.4 ′ - {bis [(pent- 2,4-dion-3-yl) methylsulfanyl]} - diphenyl oxide (1b) of the general formula (1).

The closest prototype is the method [Y. Suzuki, M. Shimawaki, E. Miyazaki, I. Osaka, K. Takimiya. Quinoidal oligothiophenes with (acyl) cyanomethylene termini: synthesis, characterization, properties, and solution processed n-channel organic field-effect transistors. Chemistry of Materials, 2011, vol. 23, No. 3, p.795-804] to obtain a bis- (pent-2,4-dion-3-yl) -substituted compound (4) by reacting bis- (2,2-thien-5,5-diyl) diacetonitrile with acetyl chloride in the presence of NaH according to the scheme:

In a known manner, 1,8- {bis [(pent-2,4-dion-3-yl) methylsulfanyl]} - 3,6-dioxaoctane (1a) and 4,4 ′ - {bis [(pent- 2,4-dion-3-yl) methylsulfanyl]} - diphenyl oxide (1b), information about which is not available in the literature.

A selective method is proposed for producing 1,8- {bis [(pent-2,4-dion-3-yl) methylsulfanyl]} - 3,6-dioxoctane and 4.4 ′ - {bis [(pent-2,4-dion -3-yl) methylsulfanyl]} - diphenyl oxide of the formula (1).

The essence of the method consists in the interaction of formaldehyde (37%) with α, ω-dithiol HS-X-SH, where X = (CH) ₂ O (CH) ₂ O (CH) ₂ ; n-C ₆ H ₄ -O-C ₆ H ₄ -n, and acetylacetone in the presence of a catalyst A1 ₂ O ₃ / SiO ₂ , with a molar ratio of acetylacetone: CH ₂ O: α, ω-dithiol: Al ₂ O ₃ / SiO ₂ = 2: 2: 1: (0.03-0.07), preferably 2: 2: 1: 0.05, in a solvent CHCl ₃ : C ₂ H ₅ OH (vol. 1: 1), at room temperature (~ 20 ° C) and atmospheric pressure for 5-7 hours, preferably 6 hours. Yield 1,8- {bis [(pent-2,4-dion-3-yl) methylsulfanyl]} - 3,6-dioxoctane and 4,4′- {bis [(pent-2,4-dion-3-yl) methylsulfanyl]} - diphenyl oxide of the general formula (1) is 71-94%. The reaction proceeds according to the scheme:

;

Where

;

1,8- {Bis [(pent-2,4-dion-3-yl) methylsulfanyl]} - 3,6-dioxaoctane (1a) and 4.4 ′ - {bis [(pent-2,4-dion- 3-yl) methylsulfanyl]} - diphenyl oxide (1b) are formed only with the participation of formaldehyde corresponding to α, ω-dithiol and acetylacetone, taken in a stoichiometric ratio of 2: 1: 2. With a different ratio of the starting reagents, the selectivity of the reaction decreases. In the presence of other aldehydes (e.g., alkyl-, aryl-substituted aldehydes), other 1,3-dicarbonyl compounds (e.g., malonic acid dimethyl ether, acetoacetic ether), the desired products are not formed by the general formula (1). Without a catalyst, the reaction does not go.

Carrying out this reaction in the presence of an Al ₂ O ₃ / SiO ₂ catalyst of more than 7 mol% does not lead to a significant increase in the yield of the target product (1). The use of catalyst Al ₂ O ₃ / SiO ₂ less than 3 mol.% Reduces the yield (1). Reactions were carried out at room temperature (~ 20 ° C). At temperatures above 20 ° C (for example, 60 ° C), energy consumption increases, and at temperatures below 20 ° C (for example, -10 ° C), the reaction rate decreases. The experiments were carried out in a solvent mixture of chloroform-ethanol (1: 1 vol.), Because in this mixture, the starting reagents and target products dissolve well (1).

Significant differences of the proposed method

In the proposed method, commercially available acetylacetone, formaldehyde, α, ω-dithiols are used as starting reagents, and a mesoporous amorphous aluminosilicate catalyst with atomic ratio Si: Al = 40: 1 obtained by the method [ V.A. Veklov, B.I. Kutepov, PPTalipova, N.G. Grigorieva, U.M. Dzhemilev, V.A. Drozdov. A method of obtaining a mesoporous amorphous mixed elementosilicates. 2011. No. 2420455. Bull. No. 16]. The method allows to obtain 1,8- {bis [(pent-2,4-dion-3-yl) methylsulfanyl]} - 3,6-dioxaoctane (1a) and 4.4 ′ - {bis [(pent-2,4 -dion-3-yl) methylsulfanyl]} - diphenyl oxide (1b) by the general formula (1). In the known method, hard-to-reach bis (2,2-thien-5,5-diyl) diacetonitrile with acetyl chloride is used as starting reagents, and pyrophoric sodium hydride is used as a catalyst. In a known manner, 1,8- {bis [(pent-2,4-dion-3-yl) methylsulfanyl]} - 3,6-dioxaoctane (1a) and 4,4 ′ - {bis [(pent- 2,4-dion-3-yl) methylsulfanyl]} - diphenyl oxide (16) by the general formula (1).

The method is illustrated by the following examples.

Example 1: 1.47 ml (20 mmol) of formaldehyde (37% aqueous solution), 1.63 ml (10 mmol) of 3,6-dioxo are placed in a Schlenk vessel mounted on a magnetic stirrer in an argon atmosphere at room temperature (~ 20 ° C) -1,8-octanedithiol and stirred for 30 minutes, add 1.5 ml of CHCl ₃ and 1.5 ml of C ₂ H ₅ OH, 2.06 ml (20 mmol) of acetylacetone and 0.081 g (0.05 mmol) of Al ₂ O ₃ / SiO ₂ , mix at ~ 20 ° C for 6 hours. 1.8- {bis [(pent-2,4-dion-3-yl) methylsulfanyl]} -3,6-dioxoctane is isolated from the reaction mass in 86% yield.

Other examples confirming the method are given in the table.

No. p / p Starting α, ω-dithiol The ratio of acetylacetone: formaldehyde: α, ω-dithiol: Al ₂ O ₃ / SiO ₂ , mmol Reaction time, h Yield (1),% one 3,6-dioxo-1,8-octanedithiol 2: 2: 1: 0.05 6 86 2 "-" 2: 2: 1: 0.07 6 94 3 "-" 2: 2: 1: 0.03 6 71 four "-" 2: 2: 1: 0.05 5 79 5 "-" 2: 2: 1: 0.05 7 89 6 4,4′-Dimercaptodiphenyl oxide 2: 2: 1: 0.05 6 91

All experiments were carried out in a solvent mixture of chloroform-ethanol (1: 1, vol.) At room temperature (~ 20 ° C).

Spectral characteristics of compounds (1a, b)

1,8- {Bis [(pent-2,4-dion-3-yl) methylsulfanyl]} - 3,6-dioxaoctane (1a)

The oil is light orange in color. R _f = 0.61 (eluent C6H ₁₄ -EtOAc, 1: 4) IR spectrum (ν, cm ^-1 ): 716 (CS), 1022 (С-О), 1110 (COC), 1418 (СН ₂ -), 1599, 1699 (C = O).

¹ H NMR Spectrum (δ, ppm, J, Hz): 2.24 (s, 12H, CH ₃ (21.24, 25.25)); 2.70 (t, 4H, CH ₂ (2.9), J = 6.4); 3.52 (d, 4H, CH ₂ (11.15), J = 5.6); 3.64 (d, 4H, CH ₂ (5.6), J = 3.2); 3.67 (t, 4H, CH ₂ (3.8), J = 6.6).

¹³ C NMR Spectrum (δ, ppm): 22.87 (C-21.24.24.25.26); 29.46 (C-11.15); 30.89 (C-2.9); 70.32 (C-3.8); 71.01 and 106.6 (enol form) (C-12, 16); 71.60 (C-5.6); 192.13 (S-13, 17, 19, 22).

Mass spectrum, m / z: 429 [M + Na] ⁺ . Found (%): C, 51.71; H, 8.13; S, 14.59. C ₁₈ H ₃₀ O ₆ S ₂ . M _theory. = 406. Calculated (%): C, 53.18; H, 7.44; S, 15.77.

4,4 ′ - {Bis [(pent-2,4-dion-3-yl) methylsulfanyl]} - diphenyl oxide (1b)

Orange oil. R _f = 0.54 (eluent C ₆ H ₁₄ -EtOAc, 1: 4) IR spectrum (ν, cm ^-1 ): 714 (CS), 1012 (С-О), 1238 (Ar-O-Ar), 1416 (CH ₂ -), 1485 and 1555 (Ar), 1581 and 1697 (C = O), 3410 (OH).

¹ H NMR Spectrum (δ, ppm, J, Hz): 2.16 (s, 12H, CH ₃ (21, 27, 30, 31)); 3.76 (s, 4H, CH ₂ (8, 23)); 3.85 (t, 2H, CH (9.24), J = 6.8); 6.92, 7.30, 7.40, 7.50 (m, 8H, CH _Ar ).

¹³ C NMR spectrum (δ, ppm): 22.87 (C-21, 27, 30, 31); 34.58 (C-8, 23); 69.15 (C-9, 24); 119.58, 128.93, 134.32, 156.64 (C _Ar ); 192.44 (S-10, 19, 25, 28).

Mass spectrum, m / z: 481 [M + Na] ⁺ . Found (%): C, 61.60; H, 5.56; S, 14.84. C ₂₄ H ₂₆ O ₅ S ₂ . M _theory. = 458. Calculated (%): C, 62.86; H, 5.71; S, 13.98.

Claims (1)

The method of obtaining 1,8- {bis [(pent-2,4-dion-3-yl) methylsulfanyl]} - 3,6-dioxoctane (1a) and 4.4 ′ - {bis [(pent-2,4- dion-3-yl) methylsulfanyl]} - diphenyl oxide (1b) of the general formula (1):

Where

;

characterized in that formaldehyde (37%) is reacted with α, ω-dithiol HS-X-SH, where X = (CH) ₂ O (CH) ₂ O (CH) ₂ ; n-C ₆ H ₄ -OC ₆ H ₄ -n, and acetylacetone in the presence of an Al ₂ O ₃ / SiO ₂ catalyst, with a molar ratio of acetylacetone: CH ₂ O: α, ω-dithiol: Al ₂ O ₃ / SiO ₂ = 2: 2: 1: (0.03-0.07), at room temperature (~ 20 ° C) and atmospheric pressure for 5-7 hours in a solvent mixture of chloroform-ethanol (volume. 1: 1).