SU1198074A1 - Acetylene ethoxydioxolans-1,3 as reagents for coal flotation and method of producing same - Google Patents

Abstract

1. Acetyl ethoxydioxolanes-1, 3 of general formula 1 СНз сf. € H, I C — R CH, c — I o he / and OCzHs: where R is methyl, ethyl, propyl, isobutyl. SU. .. 1198074 B 5/28

Description

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The invention relates to organic chemistry, in particular to a new method of producing new compounds (acetylene toxydioxolanes), which are used as flotation agents in the coal industry.

The purpose of the invention is to increase the flotation properties in the range of acetylene 1,3-dioxolia.

PRI me R 1. 4,4,5-Trimethyl-2ethoxy-5- (3-methyl-3-hydroxy-1-butinsh1) 1, 3-dioxolane.

but. The reaction mixture, consisting of 10.85 g (0.058 g-mol), 2,5,6-trimethyl-3-heptin-2, 5,6-triol, 8.6 g (0.058 g-mol) of ethyl ortho-ester and 0.3 g (0.0024 g-mol) of benzoic acid are placed in a Klisen flask equipped with a thermometer and a downward cooler. Then the mixture is heated at the bath temperature, while the ethyl alcohol formed is distilled from the reaction zone. The reaction is stopped with the onset of carbon dioxide emission (recorded by turbidity of barite water), the formation of which indicates the beginning of the decomposition of the target product.

Next, the reaction mixture is cooled, diluted with absolute ether and neutralized with potash. The precipitate was filtered off, and 8.91 g (72% yield) of 4,4,5-trimethyl-2-ethoxy-5 (3-methyl-3-hydroxy-t-butynyl) -1,3-dioxolane was distilled from the filtrate by distillation. with bp 113-116 C / 3 mmHg p 1.4635, d O, 9789. Purity according to GY (X 99.5%.

Found,%: C 64,16; H 9.39.

 ,

Calculated,%: C 64.46; H 9.09.

IR spectrum: stretching vibrations (-C-5C-) in the region of 2220 cm, stretching vibrations (OH-groups) in the region

l /

3400 cm

strong absorption in the region of 1200-950, characteristic of the orthoformyl group.

b. According to the method of example 1a, heated to 155 ° C out of 10.85 g (0.058 g-mol) of 2,5,6-trimethyl-3heptin-2, 5,6-tri-ol, 8.6 g (0.058 g-mol) of ethyl ortomonyl 8.4 g (63% yield) of 4,4,5-trimethyl-2-ethoxy-5 (3-methyl-3-hydroxy-1- butynyl) -1,3, -dioxolane with so kip. PZ-Pb C /

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/ 3 mmHg, nj4,4635, 9787. Purity on GLC 99.3%.

EXAMPLE 2: 4 5-Dimethyl-4ethyl-2-ethoxy-5- (3-methyl-3-hydroxy-15 butynyl) -1,3-dioxolane.

According to the method of example 1a, when heated to from 30 g (0.15 g-mol) 2,5,6-trimethyl-3-octin-2,5,6-triol, 23 g (0.15 g-mol) of ethyl ortho formic ester and 0.96 g (0.0078 gmol) of benzoic acid get 20 g (yield 60%) of 4,6-dimesh1-4-ethyl2-ethoxy-5- (3-methyl-3-hydroxy-1-butynyl) -1, 3-dioxolane with so Kip. 125 s / 15/6 mmHg, p 1,4692, d 0,9654. Purity on GLC 99%.

Found,%: C 65.30; H 9.06. Garden Hj4 0.

Calculated,%: C 65.62; H 8.36. 20 IR spectrum: stretching vibrations () in the region 2120, stretching vibrations (OH groups) in the region of 3400 cm, deformation and stretching vibrations of the ortho-formyl group 25 in the region of 1200-950 cm.

Froze 4,5-Dimethyl-4-propyl 2-ethoxy-5- (3-methyl-3-hydroxy-1-butynyl) -1, 3-dioxolane.

Similar to the method of example ta from 5.35 g (0.025 g-mol) 2,5,6-trimtyyl-3-nonin-2, 5,6-triol, 3.7 g (0.025 g mol) of ethyl ortramyl ether and 0, 16 g (0.0013 g-mol) of benzoic acid get 4.41 g (yield 66.6%) of the desired 4,5-dimethyl 5 4-P1: oshsh-2-ethoxy-5- (3-methyl-3- hydroxy-butynyl) -1,3-dioxolane with a bp. 140-142s / 5 mmHg, and 1.4689, df 0.9904, GLC purity 99.5%.

Found,%: C 66.46; H 9.51;

SooN, 0 ".

Calculated,%: G 66.66; And 9.63.

IR spectrum: stretching vibrations (-CsC-) in the region of 2220 cm, stretching vibrations (OH groups) in the range of 3400, deformation and stretching vibrations of the ortho-formyl group in the range of 1200-950 cm.

Example 4. 4,5-DimetsI-4Iso-bytesI-2-ethoxy-5- (3-metsI-3-ok50 Si-1-butynyl) -1,3-dioxolane.

According to the method of example 1a of 11.4 g (0.05 g-mol) 2,5,6,8-tetramethyl-Znonine-2, 5,6-triol, 7.4 g (0.05 gmol) of ethyl ortoformate 55 of ether and 0.34 g (0.0027 g-mol) of benzoic acid, 7.8 g (yield 55%) of 4,5-dimethyl-4-iso-butyl 2-ETOXI-5- (3-metsh-3-hydroxy) are obtained. -1-buty31

Nile) -1,3-dioxolane with so kip. 135С / / 4 mmHg,, 4650,, 9798. GLC purity 99.6%. Found,%: C 67.38; H 9.94. .

From “6 HjjO.

Calculated% C, 67.64; H 9.85.

IR spectrum: stretching vibrations (-CeC-) in the range of 2270, stretching vibrations (OH-groups) in the range of 3450 cm, deformation and stretching vibrations of the ortho-formyl group in the range of 1200-950 cm.

The preferred temperature range is 100-110 s. . Carrying out the process at a higher temperature () than does not lead to an increase in the yield of acetylene ethoxydioxolanes as compared with the yields obtained under optimal conditions, and therefore it is impractical to raise the temperature so as not to increase the power consumption. At a lower temperature, for example 85-90 s, the yield of the target products decreases (a large return of the original product). .

The effect of temperature on the yield of the target product (under the conditions of Example 1) follows:

Temperature The yield of the target process

. 100

72 63 155 85-90

45

In tab. Table 1 shows the results of experiments carried out under the conditions of Example 1, with different ratios of components and reaction.

From tab. 2 that if the catalyst (benzoic acid) is taken in smaller quantities (0.0014 g-mol), the yield of the target product falls from 72 to 47%. The increase in the amount of catalyst (0.0040 g-mol) is not advisable, since does not affect the yield of the target products (you

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the stroke remains within the same range (70%), thereby not being economically justified.

The data of the comparative tests show that the optimal technical5 economic performance of the coal fines flotation process is achieved already at a consumption of 100 g of the proposed reagent per 1 ton of coal, while to obtain similar results in the flotation of the T-66 reagent used at the concentration plant (a mixture of two atomic alcohols dioxane and pyran series), its consumption should be not less than 1000 g / t, i.e. 10 times.

The study of the flotation properties of reagents was carried out according to the method of flotation of coal sludge with the individual use of compounds of formula (1).

Test method. 100 g of coal is soaked in 1000 ml of water and floated at room temperature in a laboratory pneumatic type machine. Flotation was carried out on coal slurry TSOF Karagandinsk.

The results of the comparative tests of the flotation activity of the above-acetylenic ethoxy-

, Q dioxolan-1,3 are given in table. 2

Comparative test data show that all acetylenic ethoxydioxolanes-1,3 of formula 1 exhibit flotation activity. As can be seen from the table. 2, the best results were obtained when used as a collector of ethoxydioxolane-1, 3, with ethyl radical. The latter makes it possible to increase the efficiency of coal flotation in comparison with the known T-66 reagent, the concentrate yield increases by 4.75%, its ash content decreases by 1.64%, and the ash content of waste increases by 12.77%.

Compounds of formula 1 with R-CHj,

Cin able to reduce the floi ash content

to concentrate by 2.7-4% and raise

the ash content of the waste is 1.5-6, -4%, which confirms the high flotation activity of these compounds.

Claims (2)

1. Acetylene ethoxydioxolanes - 1,3 of the general formula 1 € Н, СН ₃ СН ₃ ι ¹ 1 „ CH, -C-CSc-C - CR ³ I II he oo s / \ and OS ₂ H ₅ where R is methyl, ethyl, propyl, isobutyl, as reagents for coal flotation. 2. A method of producing acetylene ethoxydioxolanes-1,3 common ^{ly 1} CH, CH, I I sn, -s-s ^ s-s - I he i o \ ^ζ / \ n form — sn, I C-R I about 0C ₂ H ₅ where R is methyl, ethyl, propyl, isobutyl, the corresponding corresponding triol of general formula P: I'm that CH ₃ SI, CH, II ³ I ³ s-C-C = C-C-CH 1 I he where R has the indicated react) with an equimolar amount of triethyl ester of orthoformic acid in the presence of benzoic acid as a catalyst at 100-110 ° C and a molar ratio of reactants and catalyst 1: 1. (0,041-0,052), respectively.