Method for production of o-(n-butyl)-o-(2-ethyl-n-hexyl)-dithiophosphoric acid 1-(n,n-dimethylaminomethyl)-benzotriazole salt

FIELD: organic chemistry, in particular new lubricating oil additive.

SUBSTANCE: 1-(N,N-dimethylaminomethyl)-benzotriazole is brought into reaction with equimolar amount of O-(n-butyl)-O-(2-ethyl-n-hexyl)-dithiophosphoric acid at 80-100°C for 2-4 h. Yield of finished product is 92-100 %.

EFFECT: corrosion-resistant additive with antioxidative, high antiscoring properties, compatible with base oil.

1 cl, 1 ex, 2 tbl

 

The present invention relates to the field of synthesis of additives to lubricating oils, in particular, to a method for producing 1-(N,N-dimethylaminomethyl)-benzotryazolyl salt of O-(n-butyl)-O-(2-ethyl-n-hexyl)-dithiophosphoric acid of General formula (1), perspective as ashless additives to oils.

The specified connection formula (1) can be used as additives with enhanced extreme-pressure, anti-wear properties, high thermal and oxidative stability.

The known method [U.S. Pat. U.S. No. 4519928, CL 10 M 1/32, 1985] receiving lubricant additives of the General formula (2) alkylation of benzotriazole. The additive is injected in the amount of 1 wt.% in the lubricating oil to provide anti-oxidation and anti-corrosion properties.

where R is hydrogen or hydrocarbon With1-C12radical, R1and R2- C1-C4-alkyl, R3- C1-C12-alkyl.

In a known manner there can be obtained 1-(N,N-dimethylaminomethyl)-benzotryazolyl salt of O-(n-butyl)-O-(2-ethyl-n-hexyl)-dithiophosphoric acid (1).

The known method [A.m.kuliev “Chemistry and technology of additives to oils and fuels. M.: Chemistry, 1985, str] get ash additives DF-11 (zinc salt of O-(n-butyl)-O-(2-ethyl-n-hexyl)-dithiophosphoric the acid of General formula (3), interaction paternostro phosphorus with isobutyl and isooctyl alcohols at 100-120°to dialkyldithiophosphoric acid, which is neutralized with 20°With zinc oxide.

The known method does not allow to obtain 1-(N,N-dimethylaminomethyl)-benzotryazolyl salt of O-(n-butyl)-O-(2-ethyl-n-hexyl)-dithiophosphoric acid (1). Furthermore, the way ash additive DF-11 has good antiwear and antioxidant properties, but the lack of extreme-pressure properties.

The purpose of the invention - creation method of producing ashless lubricant additives, operating at high pressures, in particular, additives for oils with improved extreme pressure properties.

The essence of the method lies in the interaction equimolar quantities of 1-(N,N-dimethylaminomethyl)-benzotriazole with O-(n-butyl)-O-(2-ethyl-n-hexyl)-dithiophosphoric acid at a temperature of 80-100°C, preferably 90°C for 2-4 hours, preferably 3 hours Produced 1-(N,N-dimethylaminomethyl)-benzotryazolyl salt of O-(n-butyl)-O-(2-ethyl-n-hexyl)-dithiophosphoric acid (1) with the release of 92-100%.

Target product (1) is formed only with the participation aminomethylpropanol benzotriazole and O-(n-butyl)-O-(2-ethyl-n-hexyl)-dithiophosphoric acid. In the presence of other aminomethylated who's products (for example, aminomethylpyridine phenol or 1,2,4-triazole), other derivatives dithiophosphoric acid (for example, diarylethylene acid) of the target product (1) is not formed. Changing the ratio of initial reagents in the direction of increase or decrease of one of the components reduces the yield of the target product (1). The reaction was performed using toluene as solvent. In other solvents (e.g., aliphatic) decreases the yield of the target product(1).

The proposed method has the following advantages:

The method allows to obtain high yields ashless additive to lubricating oils of General formula (1), the synthesis of which is not described in literature.

The method is illustrated by the following examples:

EXAMPLE 1. In thermostated glass reactor fitted with mechanical stirrer, reflux condenser and a gas-feeding tube at room temperature (20-21° (C) the temperature in the nitrogen atmosphere is placed 100 mmol 1-(N,N-dimethylaminomethyl)benzotriazole and 100 mmol of O-(n-butyl)-O-(2-ethyl-n-hexyl)-dithiophosphoric acid in 30 ml of toluene, with stirring, heated to 90°and incubated for 3 hours, produce 1-(N,N-dimethylaminomethyl)benzotryazolyl Sol O-(n-butyl)-O-(2-ethyl-n-hexyl)-dithiophosphoric acid (1) with a yield of 97%.

The spectral characteristics of 1-(N,N-dimethylaminomethyl)-benzotryazolyl salt of O-(n-butyl)-O-(2-the Teal-n-hexyl)-dithiophosphoric acid (1):

IR range (νcm-1): 565 (P=S), 665 (P=S), 740, 950, (P-O), 990 (R-O-C), 1150 (R-O), 1295 (C-O), 1450. An NMR spectrum1N (δppm, CDCl3TMS): 0.88, 0.98 (m, N, 3H), 1.28 (m, N, CH2), 1.82-2.06 (m, 1H, CH), 2.68, 2.80 (s, 6N, CH3), 3.68-4.16 (m, 4H, CH2O), 5.63 (s, 2H, NCH2N), 7.75-8.08 (s, 4H, CH=CH). An NMR spectrum13With (δ, ppm): 14.08 (1), 19.03 (2), At 34.96 (3), 68.75 d (4,2Jcf=7.6 Hz), 14.06 (C5), 22.94 (6), 28.83 (7), 29.98 (8), At 39.77 (C9,3Jpc=7.6 Hz), 72.77 (10,2JRS=7.6 Hz), 23.32 (11), 10.90 (12), 41.54 (13With14), 71.26 (15), 133.22 (C16), 108.93 (17), 129.17 (18), 125.14 (19), 120.73 (20), 145.61 (21). Found, %: C, 54.21; H, 8.01; S, 13.22; N, 12.24. C21H39S2PN4O2. Calculated, %: C, 53.16; H, 8.23; S, 13.50, H, 6.54; N, 11.82; Oh, 6.75.

Other examples of the method are given in table 1.

td align="center"> 90
Table 1
№ p/pThe reaction temperature, °Reaction time, hoursOutput (1), %
1.90397
2.1003100
3.80392
4.4100
5.90295

The reaction was carried out at equimolar the ratio of initial reagents in toluene solution.

Additive (1)obtained according to examples 1-5 was dissolved in industrial oil AND 100A in the amount of 3 wt.% and compared its properties with known additive DF-11 (table 2).

As follows from table 2, obtained in accordance with the invention, 1-(N,N-dimethylaminomethyl)-benzotryazolyl salt of O-(n-butyl)-O-(2-ethyl-n-hexyl)-dithiophosphoric acid has in comparison with the known additive DF-11 (zinc salt of O-(n-butyl)-O-(2-ethyl-n-hexyl)-dithiophosphoric acid) the best anti-wear properties, good compatibility with the base oil. In addition, they retain such performance properties of the additive DF-11, as anti-oxidant and anti-corrosion, consequently, are suitable additives to obtain oils of class TM-5 in accordance with TGL 21160. Additive DF-11 allows you to get the gear oil before class performance TM-3.

The way to obtain 1-(N,N-dimethylaminomethyl)-benzotryazolyl salt of O-(n-butyl)-O-(2-ethyl-n-hexyl)-dithiophosphoric acid formula

as an additive for lubricating oils which, namely, that 1-(N,N-dimethylaminomethyl)-benzotriazol subjected to interaction with equimolar number of O-(2-ethyl-n-hexyl)-dithiophosphoric acid in the environment of toluene at a temperature of 80-100°C for 2-4 hours



 

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