RU2235093C1 - 4,6-bis-(nonyloxycarbonylmethylamino)-1,3,5-triazine 2- trimethylammonium chloride as surface-active substance - Google Patents

Abstract

FIELD: organic chemistry, surfactants.

SUBSTANCE: invention relates to derivatives of 1,3,5-triazine, namely, to 4,6-(bis-(nonyloxycarbonylmethylamino)-1,3,5-triazine 2-trimethylammonium chloride of the formula:

that is used as a surface-active substance.

EFFECT: valuable properties of compound.

2 cl, 1 tbl, 4 ex

Description

The invention relates to organic chemistry and chemistry of surface-active substances (surfactants), specifically to a new, substituted 1,3,5-triazine - 2-trimethylammonium chloride-4,6-bis (nonyloxycarbonylmethylamino) -1,3,5-triazine structure

as a cationic surfactant type.

As you know, the chemistry of surfactants is booming. This is due not only to the level of sanitary-hygienic preparation of the population, but also to the need to develop new, effective, non-toxic and non-allergenic compounds that can reduce the surface tension of liquids and have good cleaning properties even in hard water. The last condition is best suited for the cationic type of surfactants, the assortment of which, unfortunately, is very limited. The development of new cationic surfactants is a crucial task.

Known 2-allylamino-4,6-bis (ethyloxycarbonylamino) -1,3,5-triazine structure

which is used as an effective modifier-hardener of epoxy oligomers in anhydride curing compositions [US Pat. RF №2187505 / S.N.Mikhailichenko, A.A. Chesnyuk, L.D. Konyushkin, V.N. Zaplishny. 2-Allylamino-4,6-bis (ethoxycarboxylatomethylamino) -1,3,5-triazine as an effective modifier-hardener of epoxy oligomers in anhydride curing compositions. Bull. Invent., 2002, No. 23] - (prototype in structure).

Its use as a surfactant is unknown.

Also known cetrimethylammonium chloride (CMAC) structure

HMAC is obtained by the known quaternization reaction of dimethylaminohexadecyl methyl chloride according to Hoffmann and is used as a cationic surfactant (surfactant) [Surfactants and compositions: Handbook / Ed. M.Yu. Pletnev. - M .: OOO “Firm Klavel”, 2002, 768 p.]. TsMAH is successfully used as a surfactant and conditioning additive in the composition of rinses and balms - (prototype for use).

The disadvantage of using CMAC is the relatively low ability to reduce the surface tension of aqueous solutions, as well as the high acidity of its solutions.

The technical solution to the problem is to increase the ability to reduce the surface tension of aqueous solutions, reduce the acidity of solutions and expand the range of surfactants used.

The objective is achieved by obtaining a new derivative of a series of 1,3,5-triazine - 2-trimethylammonium chloride-4,6-bis (nonyloxycarbonylmethylamino) -1,3,5-triazine (TNCT) structure

which can be used as an effective cationic type of surfactant.

The novelty of the claimed proposal is seen in the fact that a new derivative of 2-substituted 1,3,5-triazines is proposed as a surfactant, which allows to reduce the surface tension of aqueous solutions. The compound is characterized by high surface activity even at high (1 · 10 ^-1 wt.%) Dilutions, which dramatically reduces the flow rate on the DW and improves the environmental situation.

At the same time, the claimed TNCT is obtained by a known method, the interaction of 2-chloro-4,6-bis (nonyloxycarbonylmethylamino) -1,3,5-triazine with dry, gaseous trimethylamine in a mixture of benzene: ether at a temperature of 20-25 ° C [A.A .Chesnyuk, S.M. Mykhaylichenko, V.S. Zavodnov and V.N. Zaplichny. CGS, 2002, No. 2, p .97-203]. The starting 2-chloro-4,6-bis (nonyloxycarbonylmethylamino) -1,3,5-triazine is prepared by a known method by the reaction of cyanurichloride with p-toluenesulfate-neonyloxycarbonylmethylamine (1: 2 mol) in solution, in acetone, in the presence of an equimolar amount of sodium bicarbonate [ V.N. Zapishny, I.A. Asaturian, G.M. Poghosyan. Synthesis of 2-piperidyl-4,6-diglycyl-8-triazine diallyl esters. Arm Chem. J., 1976, v. 29, No. 12, p. 1065-1067].

Used cyanuric chloride immediately before use is purified by crystallization from CCl ₄ , and the solvents are fractionated and dried by known methods [A. Gordon, R. Ford. Companion chemist. M.: Mir, 1976, 541 pp.].

To compare the surface activity using the known surfactant cetrimethylammonium chloride (CMAC) - a prototype for use.

Examples of the execution of the proposed proposal are presented below.

Example 1. 2-Chloro-4,6-bis (nonyloxycarbonylmethylamino) -1,3,5-triazine (KhNAT). A mixture of 1.5 g (0.02 mol) of aminoacetic acid, 3.47 g (0.02 mol) of nonanol-1 and 3.8 g (0.02 mol) of p-toluenesulfonic acid in 25 ml of benzene is boiled with a Dean nozzle - Start and reflux until the visual separation of the water in the nozzle stops. The mixture is boiled for another 3 hours, benzene is distilled off to half the volume, and the residue is distilled off to dryness in a water-jet vacuum in a water bath. Obtain 3.5 g (91%) of p-toluenesulfate of nonyl glycine ester (TSH) in the form of a white color, amorphous and highly hygroscopic substances with so pl. 25-27 ° C.

Found,%: C 58.11; H 8.58; N 3.52; C ₁₈ H ₃₁ NSO ₅ .

Calculated,%: C 57.88; H 8.37; N, 3.75.

IR, ν, cm ^-1 : 3430-3300 ear. from. (-NH $\genfrac{}{}{0ex}{}{\text{+}}{\text{3}}$ ); 1720 cf. (C = O); 1630, 1595, 1500 cf. (C = C, C = N - cont. And cyanurate cycle.); 1140.1100, 1015 cf. (C-O-C).

PMR, δ, ppm (group): 7.55-7.65 (2H d. Σ H ² + H $\genfrac{}{}{0ex}{}{\text{6}}{\text{hair dryer}}$ ) J = 8.3; 6.83-7.01 (2H d. Σ H ³ + H $\genfrac{}{}{0ex}{}{\text{6}}{\text{hair dryer}}$ ) J = 8.3; 5.05 (3H s. NH $\genfrac{}{}{0ex}{}{\text{+}}{\text{3}}$ ); 4.04-4.29 (12H m. - (CH ₂ ) _6- ); 3.96-4.01 (2H t. OCH ₂ ); 3.88-3.92 (2H m. NH $\genfrac{}{}{0ex}{}{\text{+}}{\text{3}}$ H ₂ ); 2.35 (3H, s. CH _sAr ); 1.62-1.74 (2H m, CH ₂ CH ₃ ); 0.72-0.88 (3H t, CH ₂ CH ₃ ) J = 6.8.

To a solution of 0.86 g (0.0047 mol) of cyanuric chloride in 15 ml of acetone, 3.5 g (0.0094 mol) of the obtained TSH are added and with stirring at a temperature of 5-7 ° C, 1.56 g (0) are added in small portions. , 0186 mol) sodium bicarbonate. The reaction mixture is stirred for another 1 hour at the same temperature, 2 hours at 20 and 12 hours at 40 ° C. The mixture was evaporated to dryness in a water-jet vacuum, the residue was washed thoroughly with water and purified by crystallization from alcohol with activated carbon. After drying, 2.0 g (83%) of 2-chloro-4,6-bis (nonyloxycarbonylmethylamino) -1,3,5-triazine (KhNAT) is obtained in the form of a white crystalline solid with a melting point of 121-123 ° C.

Found,%: C 58.70; H, 8.81; N, 13.48. C ₂₅ H ₄₄ N ₅ O ₄ Cl.

Calculated,%: C 58.39; H, 8.62; N, 13.62.

IR, ν, cm ^-1 (group): 3230, 3070 cf. (NH); 1735 s. (C = O); 1570, 1550 cf. (C = C, C = N - cont. And cyanurate cycle.); 1120.1065 cf. (C-O-C).

PMR, δ, ppm (group): 7.54-7.99 (2H, broad s., NH); 3.99-4.00 (4H m. OCH ₂ ); 3.82-3.96 (4H m. NCH ₂ ); 1.55-1.64 (4H q, CH ₂ CH ₃ ) J = 6.0; 1.16-1.40 (24H m, CH ₂ CH ₂ CH ₂ ); 0.83-0.92 (6H t, CH ₃ ) J = 6.0.

Like ion (mass spectroscopically) 514.

Example 2. 2-Chloro-4,6-bis (nonyloxycarbonylmethylamino) -1,3,5-triazine (KhNAT). Under conditions similar to example 1, from the same amounts of cyanuric chloride, TSH and soda, with the only difference being that soda was added at 6-8 ° C, and stirring was continued for 3 hours at 25 and 10 hours at 45 ° C, 2.1 g (87%) 2-chloro-4,6-bis (nonyloxycarbonylmethylamino) -1,3,5-triazine (KhNAT) as a white crystalline substance with a melting point of 121-123 ° C.

Found,%: C 58.70; H, 8.81; N, 13.48. C ₂₅ H ₄₄ N ₅ O ₄ Cl.

Calculated,%: C 58.39; H, 8.62; N, 13.62.

IR, ν, cm ^-1 (group): 3230.3070 cf. (NH); 1735 s. (C = O); 1570, 1550 cf. (СО, C = N - res. And cyanurate cycle.); 1120.1065 cf. (C-O-C).

PMR, δ, ppm (group): 7.54-7.99 (2H, broad s., NH); 3.99-4.00 (4H m. OCH ₂ ); 3.82-3.96 (4H m. NCH ₂ ); 1.55-1.64 (4H q, CH ₂ CH ₃ ) J = 6.0; 1.16-1.40 (24H m, CH ₂ CH ₂ CH ₂ ); 0.83-0.92 (6H t, CH ₃ ) J = 6.0.

Like ion (mass spectroscopically) 514.

Example 3. 2-Trimethylammonium chloride-4,6-bis (nonyloxycarbonylmethylamino) -1,3,5-triazine (TNT). Through a solution of 2.0 g (0.0039 mol) of KhNAT in 20 ml of a mixture of absolute benzene and ether (1: 1 by volume), with stirring and a temperature of 20 ° С, dry trimethylamine is bubbled in a weak stream of nitrogen for 4 hours. a copious precipitate is filtered off, washed with dry benzene (2 × 10 ml) and dried. Obtain 1.8 g (89.6%) of the target TNCT in the form of a white crystalline powder with so pl. 133-145 ° C.

Found,%: C 58.49; H, 9.11; N, 14.78. C ₂₈ H ₅₃ N ₆ O ₄ Cl.

Calculated,%: C 58.66; H, 9.31; N, 14.66.

IR, ν, cm ^-1 (group): 3090, 3060 cf. (NH); 1739 p. (C = O); 1595, 1530 cf. (C = C, C = N - cont. And cyanurate cycle.); 1220 cf. (NMe ₃ ); 1065, 1030 cf. (C-O-C).

PMR, δ, ppm (group): 7.55-8.99 (2H, broad s., NH); 4.00-4.10 (4H m. OCH ₃ ); 3.85-3.97 (4H m. NCH ₂ ); 3.25 (9H s. Nme ₃ ); 1.57-1.65 (4H q, CH ₃ CH ₂ ) J = 6.0; 1.20-1.40 (24H m, CH ₂ CH ₂ CH ₂ ); 0.85-0.93 (6H t, CH ₃ ) J = 6.0.

Like ion (mass spectroscopically) 573.

Example 4. 2-Trimethylammonium chloride-4,6-bis (nonyloxy-carbonylmethylamino) -1,3,5-triazine (TNT). Under conditions similar to example 3, from 2.0 g (0.0039 mol) of KhNAT and dry trimethylamine with the only difference that bubbling is continued for 3.5 hours at 15 ° C, 1.87 g (93%) of TNCT are obtained as white crystalline powder with so pl. 133-145 ° C.

Found,%: C 58.49; H, 9.11; N, 14.78. C ₂₈ H ₅₃ N ₆ O ₄ Cl.

Calculated,%: C 58.66; H, 9.31; N, 14.66.

IR, v, cm ^-1 (group): 3090.3060 cf. (NH); 1739 p. (C = O); 1595, 1530 cf. (СО, C = N - cont. And cyanurate cycle.); 1220 cf. (NMe ₃ ); 1065.1030 cf. (C-O-C).

PMR, δ, ppm (group): 7.55-8.99 (2H, broad s., NH); 4.00-4.10 (4H m. OCH ₂ ); 3.85-3.97 (4H m, NCH ₂ ); 3.25 (9H s. NMe ₃ ); 1.57-1.65 (4H q, CH ₂ CH ₃ ) J = 6.0; 1.20-1.40 (24H m, CH ₂ CH ₂ CH ₂ ); 0.85-0.93 (6H t, CH ₃ ) J = 6.0.

Like ion (mass spectroscopically) 573.

The synthesized TNTC is used as the cationic type of surfactant.

While preparing their aqueous solutions with a concentration of 0.1-10.0 wt.% And measure the value of surface tension (σ, n / m) according to the well-known method of Rebinder [A. Schwartz and J. Perry. Surfactants. M .: Publishing. IL, 1953, p. 263]. For comparison, an aqueous solution of cetrimethylammonium chloride (CMAC) of the appropriate concentration is used. As a control, use the option with water that does not contain any additives. The data obtained (according to the results of three measurements) were averaged, and the arithmetic mean values were used for further calculations. Surface activity in% of control was determined by the formula

σ = a-in _i / in _i · 100%,

where a and in _i are the values of σ of the control and experimental examples, respectively. The results are tabulated.

As can be seen from the data in this table, the use of the proposed TNTC as a surfactant leads to the following results.

In the case of TNTC, its use as a cationic type of surfactant in a concentration of 0.01-10.0 wt.% Reduces the value of σ in comparison with the control by 40.7-261.5% (19.6-50.5 instead of 71.0 n / m), while the use of the known cetrimethylammonium chloride reduces this indicator in comparison with the control only by 28.1-213% (22.6-55.4 instead of 71.0 n / m).

In addition, it turned out that the acid properties of the proposed surfactant in comparison with the known decreased by 1.62 units. pH (pH value of a 1% solution of 4.92 for TNTC, instead of pH 3.3 for a 1% solution of known CMAC).

Thus, the use of the claimed TNTC as a cationic type of surfactant can significantly reduce the surface tension of their aqueous solutions, as well as reduce the acidity of the solutions, which is very important from the point of view of subsequent practical use, since the solutions are characterized by high surface activity even at high ( 1 · 10 ^-1 wt.%) Dilutions and low acidity, which reduces the consumption of DW and improves the ecological situation.

Claims (1)

2-Trimethylammonium chloride-4,6-bis (nonyloxycarbonylmethylamino) -1,3,5-triazine structure

as an effective cationic type of surfactant.