Ph.D., Ziyadullaev O.E., prof. Turabdjanov S.M.

masters Juraev R.S., Lecturer Abdurakhmanovа S.S.

Tashkent Chemical Technological Institute, Uzbekistan

SYNTHESIS OF AROMATIC ACETYLENE ALCOHOLS OF THE METHODS GRINYARA-IOTSICHA

Reacting with phenylacetylen (FA) croton aldehyde and near ketones in the presence of organomagnesium compounds synthesized aromatic acetylenic alcohols (AAA).

Organometallic compound first synthesized by E. Franklin. M. Barbe is shifted synthesized organometallic compounds [1, 2]. French scientist B. Grinyar reaction of alkyl halides with anhydrous magnesium metal powder mixed synthesized organometallic compounds (reagent Grinyara) and developed the conditions of their application to various organic syntheses. New stable compounds by reaction with alkynes reagent Grinyara synthesized J. Iotsich [3, 4].

The high reactivity of C≡C- and C-H bonds in alkynyl makes them participants in the diverse reactions that form the basis of section synthetic organic and industrial chemistry [5, 8].

AAA thanks to important applications are used on a large scale in various industries, including the oil and gas industry as bio inhibitory products biological corrosion of metal equipment, as ion exchangers for the purification of hazardous waste and production of oil and gas [6], as an additive stability at low for aviation fuel temperatures [7], in paint factories in the light industry, agriculture, medicine and electrical engineering for various purposes.

In reaction Grinyara- Iotsicha using croton aldehyde and ketones (acetone, methylethylketone, methylisopropylketone, pinokaline and acetophenone) FA by their interaction with the organomagnesium compound synthesized in the following respective compounds AAA- 1-phenyl-3-methylbutyn-1-ol-3 (I) 1-phenyl-3-methylpentin-1-ol-3 (II) 1-phenyl-3,4-dimethylpentyn-1-ol-3 (III), 1-phenyl-3,4,4-trimethylpentyn-1-ol-3 (IV) 1,3-diphenylbutyn-1-ol-3 (V) and 1-phenylgekcyn-4-in-1-ol-3 (VI). The scheme of the reaction has been offered as following

here: R= ‒CH_3, R'= ‒CH₃; R= ‒CH₃, R'= ‒C₂H₅; R= ‒CH_3, R'= izo ‒C₃H₇, R= ‒CH₃,

R'= ‒C(СH₃)₃; R= ‒CH₃, R'= ‒С₆H₃, R= ‒H, R'= ‒СH=CH‒CH₃.

Synthesis process AAA method Grinyara- Iotsicha conducted at a temperature range -5-10 °C in the presence of solvents diethyl ether (DEE) and tetrahydrofuran (THF). The starting materials were taken in equimolar amounts. The results are shown in the table.

Table

Influence of the nature and duration of the reaction solvents on the yield of AAS (temperature 0 ° -5, starting materials in an equimolar ratio)

ААA	Products, %
	solvent DEE		solvent THF
	ААA	intermediate and auxiliary connections	ААA	intermediate and auxiliary connections
Duration of reaction, 2 hour
I	75,0	18,3	87,4	6,5
II	68,4	23,4	83,5	10,2
III	56,4	29,5	74,5	15,3
IV	53,0	34,7	69,3	18,4
V	50,0	39,6	66,0	21,0
VI	64,3	26,4	79,0	14,1
Duration of reaction, 4 hour
I	78,6	13,2	89,6	4,5
II	71,8	17,4	85,0	7,6
III	60,6	21,6	75,2	13,0
IV	55,9	25,0	71,0	15,5
V	54,7	28,0	68,7	18,2
VI	68,0	20,0	81,2	12,2
Duration of reaction, 6 hour
I	67,3	24,8	82,2	11,4
II	62,4	27,0	77,6	17,0
III	52,4	37,0	69,5	18,4
IV	45,2	41,6	63,2	21,0
V	42,7	44,0	57,3	23,7
VI	58,6	35,6	70,6	17,4

The table shows that when using THF as solvent, increasing the reaction time from 2 to 4 hours, an increase yield. However, with increasing duration of synthesis up to 6 hours, a sharp fall of efficiency AAA exit.

The table shows that when the reaction is carried out in solvents DEE and THF in AAA is formed with a high yield. For example, with a reaction time 4 hours temperature -5- 0 ^oC in a solvent DEE, yield AAA: I- 78,8; II- 71,8; III- 60,6; IV- 55,9; V- 54,7 and VI- 68,0%, and in case of replacement solvent THF respectively 89,6; 85,0; 75,2; 71,0; 68,7 and 82,2%. Comparing the reaction results in different solvents shows that the average selectivity output y THF solvent by 13,0% more than the DEE. This reaction is due to the greater polarity of THF molecule compared to DEE.

The reaction carried out in THF, AAA negligible amount of by-products and intermediates. Solubility Iotsicha reagent in THF solution is very high; it creates a comfortable environment for the last phase of collision with aldehydes and ketones. Halogen AAA salt formed during the reaction is hydrolyzed, THF serves as a catalyst and, disaggregated electron pairs in its molecule solvation salts promote conversion AAA. THF relatively low solubility in water than DEE forms with water an unstable tetramethylglycol in weakly acidic medium and forms tetrametilenhlorgidrin acid as a byproduct. This reduces the amount of alkoxides formed by reacting a basic salt AAA and provides the basis for the synthesis of alcohols in high yield.

To explore possible areas of application of the synthesized compounds was studied their microbiological activity against the biological corrosion of pipelines of the oil industry in the laboratory together with the staff of the Institute of Microbiology, Academy of Sciences of Uzbekistan [9, 10].

AAA obtained possess microbiological activity, among the compounds studied V, I and II have active antibacterial properties against bacteria Pseudomonas, Arthrobacter chroococcum, Micrococcus album, Micrococcus sulfurous, Desulfovibrio vulgaris, Acinetobacter sp; Rhodococcus eruthropolis, Rhodococcus luteus, Rhodococcus terrae, Basillus sp. isolated from samples of oil field pipelines.

The optimal conditions for the synthesis of AAA: equimolar ratio of the starting materials; temperature -5- 0 ^oC, the solvent THF, the reaction time of 4 hours. In this case it has been determined that very maximum yield of product is I synthesized AAA – I- 89,6; II- 85,0; III- 75,2; IV- 71,0; V- 68,7 and VI- 81.2%.

Literature:

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2. Nesmeyanov A.N., Nesmeyanov N.A. Beginning of the organic chemistry. M.: 1969. Vol.1. 381 p.

3. Agronomov A.E. Selected chapters of organic chemistry. M.: Chemistry, 1990. pp. 264-287.

4. Temnikova T.I. The course of theoretical bases of organic chemistry. L. 1962. pp. 414-423.

5. Temkin O.N. Acetylene chemistry "acetylene tree" in organic chemistry XXI century // Soros Educational Journal. 2001. T.7. №6. pp. 32-41.

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7. Ziyadullaev O.E., Mirhamitova D.H., Nurmanov S.E. Synthesis of 1-Phenyl-3,4-dimethylpentyn-1-ol-3 and its vinyl ether // Journal Reports of the Academy of Sciences of Uzbekistan. 2012. №3. pp. 40-45.

8. Shchelkunov S.A., Sivolobova A.O., Mataeva S.O., Minbaev D.B., Muldahmedov Z.M. Grinyara reacting the 2-methyl-4-chlorobut-3-yn-2-ol in environments substituting diethyl ether// Journal of Organic Chemistry. 2001. №1. pp. 17-37.

9. Ziyadullaev O.E. Synthesis and technological of aromatic acetylenic alcohols, their vinyl ethers on the base of phenylacetylene: des. cand. chem. sc. Tashkent. 2011. p. 213.

10. Ziyadullayev O.E. Mahatova G.B. Synthesis of aromatic acetylenic alcohols ORT Publishing-Аpplied Sciences in Europe: tendencies of contemporary development, Stuttgart, Germany, 2014. pp. 415-417.