CC BY
8
https://doi.org/10.29013/AJT-22-3.4-100-109
Kholikulov B. N..,
Tashkent Chemical-Technological Institute Tashkent Uzbekistan
Makhsumov A. G.,
Tashkent Chemical-Technological Institute Tashkent Uzbekistan
Umrzokov A. T Department of Chemical Technologyy Navoi State Mining Institute, Uzbekistan
Ziyadullayev A.E
Tashkent Chemical-Technological Institute Tashkent Uzbekistan
SYNTHESES AND TECHNOLOGY OF 2-BROMO-SUBSTITUTED BIS-CARBAMATE DERIVATIVES, PROPERTIES AND THEIR APPLICATION.
Abstract. The article studied the synthesis of N, N'-hexamethylenebis[(2-bromophenoxy)-carba-mate], The products of N, N'-dichloro substitution, N, N'-dinitroso substitution, N, N'-disodium substitution and N, N'-dibenzyl substitution were studied N, N'-hexamethylenebis[(2-bromophenoxy-carbamate] formed during the synthesis. Reaction centers and the reaction mechanism involved in the synthesis of these substances have also been proposed. proved by IR spectroscopy.The process used organic solvents and catalysts.The reaction yield was from 90.6% to 93.3%.The biological activity of the obtained substances was studied and compared with the Roslin preparation.
Keywords: 2-bromo-substituted bis-carbamates, N, N'-hexamethylenebis[(2-bromophenoxy)-carbamate], N, N'-dichloride, N, N'-dinitroso, N, N'-disodium, N, N'-dibenzyl.
Introduction. Today, the modern search for the and also, as anti-aging of vulcanization of rubbers,
chemistry and properties of bis-carbamate com- the creation of a solvation theory intensification of
pounds that are currently intensively developing are the processes of dyeing and printing fabrics from
attracting the attention of many researchers, both in natural and chemical fibers in liquid ammonia and
Uzbekistan and abroad [1-4]. This is connected, on organic solvents[5-8]. In addition, the study of the
the one hand, with the rich possibilities of phenyl, regularities of solid-phase fixation of dyes from tex-
carbamate, halogen, polyhydrocarbon groups in tile materials, the creation of the theoretical foun-
the molecules of organic compounds, and, on the dations for the use of bio-catalytic systems for the
other hand, with the properties of the most organic processes of enrichment of tequistyle materials, the
compounds, valuable for practical use, bromophe- plasma-chemical activation of fibers that form poly-
nyl groups, as well as bis-carbamate bonds. Many mers, the use ofhigh-frequency fields and microwave
examples are written when the introduction of radiation in chemical-and-chemical production is of
halogen- and phenyl-carbamate bonds leads to the great importance [9-12].
appearance of various kinds of gamma - possessing This is explained by the high reactivity of the
biological, pharmacological activity, the ability to highly diverse functional group to complex forma-
inhibit the corrosion of metals, coatings, stabilizers tion. It was necessary to determine high-precision
for halogen-containing polymers, impregnations, unique optimal methods for the introduction of bis-
carbamate groups into the indicated types of compounds and to study the dependence of the reactions used due to the mobile proton at N-H substituting functional groups. As a result, a new, previously poorly studied and represented by only the simplest examples, a region of derivatives of two bromophe-nyl-containing bis-carbamates appeared [13-17].
Metods and materials. 1. Synthesis of N, N'-hexamethylene bis [(2-bromophenoxy)-carba-mate]. Into a three-necked flask, equipped with a reverse actuator with a calcium chloride tube, mechanical stirrer, thermometer and dropping funnel, placed 17.3 g (0.1 mol) of 2-bromophenol in 50 ml of DMF, 25 ml triethylamine, and while stirring, 8.5 ml (0.05 mol) of HMDI was added dropwise from a dropping funnel. The reaction continued for 4-5 hours at a temperature of 28-49 °C. The precipitate was filtered off, washed with distilled water 2-3 times, and dried at room temperature. Appearance white-grayish powdery product. Yield 23.83g (92.4% of theoretical): T.melt. =107-108°C; Rf =0.75; Mm=513.8. The individuality of the obtained product was checked by TLC on a fixed layer (Al2O3) II degree of purity in the system: (C6H6: CH3COOC2H5: 4); Found,%: C 46,59; H 4,17; N5,41; Br 30,88 Calculated for C20H22Br2N2O4,% C46,71; H 4,28; N5,45; Br 31,10:
2. Preparation of N, N'-dichloro-N, N'-hexa-methylene bis [(2-bromophenoxy)-carbamate]. Into a three-necked flask, equipped with a reverse actuator with a chlorine tube, automixer and thermometer, 5.14 g (0.01 mol) of N, N'-hexamethylene bis [(2-bromophenoxy)-carbamate], 60 ml carbon tetrachloride, 27.0 g of wet alumina and 4.8 g of calcium hypochlorite was added dropwise at 37 °C for 4 hours. Then the reaction mass was left for 33 hours. The precipitate that formed was filtered off and washed with ether. Received 5.28 g (90.6% of theoretical); T.melt.=89-90 °C; Rf=0.73; Mm=582.8; Found,%: C 41.04; H 3.33; N4.79; CI 12.07; Br 27.14 Calculated for C20H20Br2Cl2N2O4,%: C41.18; H 3.43; N4.80; Cl 12.18; Br 27.26
3. Obtaining N, N'-dinitroso-N, N'-hexa-meth-ylene bis [(2-bromophenoxy) -carbamate]. To a suspension of the composition 5.14 g (0.01 mol) of N, N'-hexamethylene bis [(2-bromophenoxy)-car-bamate], 70 ml of 98% formic acid with stirring and cooling to 0-5 °C in portions over 1 hour was added 0.13 mol of NaNO2, then stirring at the same temperature, the reaction was continued for 1 hour. TLC analysis of the reaction mixture every 6-10 minutes. The formed precipitate was filtered off, washed with 50 ml of ice water, and dried in air at room temperature. For methods (A-D), the filtrate was extracted with ethyl acetate (2 x 50 ml), washed with ice water and 5% aqueous soda solution, dried with magnesium sulfate and evaporated to dryness. For all methods (A-D), precipitates and residues after evaporation of the extracts were combined. The obtained N, N'-dinitroso compounds-N, N'-hexamethylene bis [(2-bromophenoxy)-carbamate] were determined by Rf, washed off with acetone sorbent. The solvent was evaporated to dryness at room temperature in a desiccator vacuum. The N, N'-dinitroso derivative of N, N'-hexamethylene bis [(2-bromophenoxy)-carbamate] was recrystallized from hexane and ethyl acetate. Product (3) yield -5.32 g (93.3% of theoretical); Rf=0.71; Mm=571.8; T.melt.=330 °C (decomposition). Found,%: C 41.82; H 3.36; N9.66; Br 27.97; Calculated for CHn N4BrO6,%: C41.97;
' 20 20 4 2 6' '
H 3.49; N9.79; Br 27.94.
4. N, N'-dibenzyl-N, N'-hexamethylene bis [(2-bromophenoxy) -carbamate]. In a three-necked flask equipped with a return flow with a calcium chloride tube, with an auto mixer and a thermometer, 5.38 g (0.01 mol) of N, N'-disodium-N, N'-hexamethylene bis [(2-bromophenoxy)-carbamate], 40 ml dry benzene. 2.4 ma (0.02 mol) of benzyl iodide was added dropwise while changing slowly. The mixture was then stirred for 13 hours while heating in a boiling water bath. After cooling, 25 ml of water was added, the precipitate was separated and recrystallized with 50% alcohol. Product yield (5) - 6.33 r (91.4% from theoretical); T.melt.=168-169 °C;
Rf=0.76; MM=693.8; Found,%: C 58.69; H 4.83;
N3.89; Br 22.89; Calculated for C34H34Br2N2O//o: C58.80; H 4.90; N4.03; Br 23.03.
N, N'-diisopropyl-N, N'-hexamethylene bis [(2-bromophenoxy)-carbamate] Obtained similarly by the above-described method. Interactive compounds (IV) (CH3)2CHJ and CHJ connections received (6) and (7) with outputs 90,2/ and 87.3;
OH + O=C=N
O
-C-N O H
Results and discussion: New derivatives of N, N'-hexamethylene bis [(2-bromophenoxy)-carba-mates] were obtained by the interaction of ortho-bromophenol with hexamethylene diisocyanate. Selective, energy-saving, waste-free technological synthesis was carried out according to the scheme:
N=C=O+ HO
+DMFA +Et3N
N-C-H O
O
The reaction is carried out in a medium of dimeth-ylformamide and triethylamine at room temperature for 4 hours. It should be noted that derivatives of N, N-
hexamethylene bis [(2-bromophenoxy)-carbamates] were obtained in a rather high yield. Physicochemical parameters of compounds (1) are given in (table 1).
Table 1. - Physicochemical parameters of compounds (1)
1
^^^^Structural formula Names Out-put,% Xmelt., ^ Rf Grossformula Element. Analysis,% М м
Calcul. Find.
N Br N Br
(c^j)—O—C—C—O—(C^j) -\ OH HO )— Br Br 92.4 107108 0.75 5.45 31.1 5.41 30.88 513.8
High density, selectivity and easy mobility of the
electron cloud group —N = C = 0 cause its high reactivity. The product yield was 92.4%. As expected, the products were obtained with good yields by the mechanism of the AN reaction. The physicochemical characteristics of bis-carbamate derivatives are apparently due to the high density and easy mobility of
the electron cloud conjugated (-N = C — o) group, which leads to an increase in the positive charge on the carbon atom of the isocyanate group, facilitating the attack of this atom by the nucleophilic agent, this is the answer to the question of whether this occurs
by increasing the positive charge on the carbon atom or by stabilizing the transition state. However, in our case, -OH hydroxyl group, having a free pair, attacks the electrophilic center in the isocyanate molecule with the formation of an intermediate product which then rearranges into the final reaction product.
On the basis of our proposals and literature data, the probable mechanism of the interaction of 2-bro-mophenol with hexamethylene diisocyanate can be represented by the following scheme:
© © 0 + :0=C=N
© © © Br N=C=0: +
O—H
I I I I
0=C—N
O—C—N II I O H
(C)
H-0
N-C=0
N-C—O I II H O
One of the starting reagents was purified using 4.5: 1.0).To prove the structure of N, N'-polymeth-preparative thin-layer chromatography on Al2O3 in ylene bis-[(2-bromophenoxy)-carbamate], the the system (HCOOH: CH3COCH3: CHCl3=0.5: method of IR spectroscopy was used (Table 2).
Table 2.- IR - spectra of compounds (1)
1
IR- spectra, v, sm-1
Structural formula —N— H q- —N-C—O— H O —C— O AAA -CH2- ^CH2
/C^^)—O—C—N^^/XV'AN— C—O— A—A II 1 1 II \aa/ -\ OH HO )- Br Br 3394 771-726 1284 1690 721-767 29382942 3.35
To study the reactivity with respect to N-H reaction centers, N, N'-hexamethylene-bis-[(2-bromophenoxy)-carbamate], we carried out rare reactions: N, N'-dinitrosisation, N, N'-dichlorination, N, N'-dimetallization and N, N'-dialkylation.
Chemical transformations of N, N'-poly-methylene bis[(2-bromophenoxy)-carbamate]. Obtaining N, N'-dichlorinated compounds (1). Derivatives of N, N'-polymethylene-bis[(2-bromophenoxy)-carbamate] (1) are the most valu-
able raw material for the further synthesis of various biologically active compounds used in engineering, agriculture, and also have a high reaction center of the N-H group for carrying out reactions of nucleo-philic and electrophilic substitutions. We have developed an efficient, affordable, cheap, stable and environmentally friendly method for carrying out the N, N'-dichlorination of a bis-carbamate derivative with calcium hypochlorite on wet alumina.
-O—C-N O H
N-C—O H O
Br
nCa(OCl2)2)
Al2O3 '
O—C—N O Cl
N—C—O-Cl O
Br
Table 3.- Physicochemical characteristics of compounds (2)
Compound 2 Structural formula~"^^^ Out put,% T.melt °C Rf Gross formula Element. Analysis^ M M
Cal cul. Find.
N Cl N Cl
(c^f/—O—C—N^AA\—C—O—(f^)) -\ O Cl Cl O /— Br Br 90.6 89-90 0.75 C20H20Br2Cl2N2O4 4.8 12.1 4.7 12.07 582.8
Outlet conections (2) - 90.6%. T.melt= 89-90 °C; polymethylene -(CH2) n-chain react with nitrosose. As
Physicochemical parameters are given on the table 3. a result of the reaction of N, N'-dinitrosidation, N, N'-
Preparation of N, N'-dinitroso derivatives of hexamethylene-bis[(2-bromophenoxy)-carbamate]
compounds (1): The reactions of N, N'-dinitrosida- (1) with NaNO2 (in excess) in 98% HCOOH at a
tion ofcompounds (1) are comparatively little studied temperature of0-50C, N, N'-dinitroso-substituted (3)
in the world literature. According to the literature and with a yield 93.3%.N, N'-dinitrosisation proceeds by
our own research, nitrogen atoms associated with the the mechanism of electrophilic damage (SE).
O—C-N O H
N-C—O H O
NaNO2/HCOOH ->■
t=0-50c
O—C—N O N O
E'
N—C—O N O O
The attacking agent is nitrosonium ion - N Since nitrous acid, which is the most common nitrosating agent, which exists in free form, sodium nitrite and a strong acid were used for the process (HCOOH). The resulting nitrous acid, attaching a proton, generates an ion - NO : HNO2 + H+ -<->-
© ©
H2NO2 -NO + H2O
NaNO2 + HCOOH
© ©
©
H2NO2
N, N'-dinitrosation is carried out while cooling the reaction mixture: an increase in temperature is undesirable, since this reduces the yield of the target product, and sometimes affects the direction.
N, N'-dinitroso compounds are identified by absorption bands N—N=O group.
A stripe in the area 1500-1420 sm-1 for
N—N=O group(table 4).
H2NO2
N— + HCOONa + H2O
Table 4. - IR - spectra of compounds (3)
Connection name IR - spectra, v, sm 1
-CH2- \ N—C—O- / Il O q- \ N-N=O C-Br —C— O AAA
<A^z—O—C-N^AA^-C—O—(C^î) V—y il 1 1 il V-v -\ ON NO /- Br II II Br Br O O Br 2920 1621 771-736 1500-1420 654 1690 768-732
3
In addition to spectral data, the structure of tion of N, N'-dinitroso-N, N'-hexamethylene bis
N, N'-dinitroso compounds was additionally con- [(2-bromophenoxy)-carbamate] with aqueous solu-
firmed by a chemical method, i.e. by reaction of N, tions of ammonia with cyclohexylamine gave mono-
N'-dinitrosoation products with amines. The reac- and 1,3-disubstituted carbamates [26-27].
O—C—N O N O
- 2
N-C—O
I II NO
II
O
O
-C-N O H
Thus, the resulting compounds once again prove that the nitrogen atoms bound to the poly-methylene chain are subjected to nitrosation at N, N'-dinitrosidation of -N, N'-hexamethylene-bis [(2-bromophenoxy)-carbamate].
+ 2
NH2
HOH
+ HO
OH
2N2!
O—C-N II I ON II
O
N
I
N
II
O
-C—O
II
O
These conclusions are in good agreement with the literature data [26-27]. Physicochemical parameters of the compound (1) on table 5.
Table 5.- Physicochemical characteristics of compounds (3)
+
Structural formula Out-put% Xmelt Rf Gross formula Element analysis,% М м
Calcul. Find
N N
—O—C—N^^^^^N—C—O— -( ON NO )- Br O O Br 93.3 330 0.71 C2oH2oN4Br2Q6 9.79 9.66 571.8
Preparation of N, N'-dibenzyloyl-substitut-ed bromo-carbamate derivatives of compounds (1). Dibenzylation at N-H groups in bis-carbamates (1) with benzyl iodides is of undoubted interest for establishing the reactivity of compounds (1). Ben-
zylation reactions were carried out, the interaction of N, N'-disodium derivatives of N, N'-hexamethylene with benzyl iodide in anhydrous benzene at a temperature of 35-48 °C and benzyl iodide was added dropwise with stirring for 4.5 hours.
-2NaJ
The occurrence of the benzylation reaction exclusively at the N, N'-nitrogen atom is explained, apparently, by the relatively easy dissociation of sodium from this atom after the presence of neighboring car-bonyl groups. The connection (5) yield was ~91.4%.
(4)
Table 6.- Physicochemical characteristics of compounds (5)
Out-put% T.melt °C Rf Gross formula Element. analysis,% M M
Calcul Find
N N
(C^))—O—c—N^^/AXv/AN—C—O— -( O CH2 H2C O )- Br 1 1 Br ô Ô 91.4 168-169 0.76 C34H34Br2N204 4.03 3.89 693.8
Physicochemical characteristics of the drug (5), given on the table 6.
Similarly, according to the method described above: N, N'-diisopropyl- N, N'-hexamethylene bis [(2-bromophenoxy) -carbamate] in 90.2% yield, T.melt.=111-112 °C and N, N'-dimethyl- N, N'-hexamethylene bis [(2-bromophenoxy) -carbamate] was obtained using the above-described method with a yield of 87.7%; T.melt.=97-98 °C.
Regulating activity of compounds: For the growth of the stimulating medium of compounds N, N'-hexamethyl bis [(2-bromophenoxy) -carbamate], tests in the laboratory of plant chemistry of the Academy of Sciences of the Republic of Uzbekistan in laboratory conditions, biot cultural services served vegetable and cotton seeds. In the experiments, cucumbers of the "Uzbekistan-740" variety, tomatoes of the "Temp" variety and medium-staple cotton of the "6524" variety were used. The preparations were dissolved in DMF and the method of
pre-sowing seed soaking was used for 18-20 hours; 0.01; 0.001; 0.0001 and 0.00001%. Repetition of experiments 4th fold. Accounting for measuring the length of the stem and root in 10-day-old cotton seedlings. It was accepted that all drugs tend to stimulate muscle growth, both in vegetables and cotton. Primary screening was carried out according to the method of Yu. V. Rakitin. This method allows you to quickly determine the degree of physiological activity of new chemical compounds, which reveals the stimulation or inhibition of the germination of plant seeds, as well as by changing the length of the roots and the length of the stem part. The preparations were tested for seed locks in solutions of different concentrations, followed by germination in Petri dishes. Control seeds were soaked in distilled water. Each series of experiments is accompanied by control. The control variants and the culture medium of the experiments are fixed 3.5, 7 and 10 days after inoculation (table 7).
Table 7.- Effect of preparation 1 on seed germination and growth cotton seedlings "S-6524"
^^^^^^^ Experiments Drug ^^^^^^^ Concent-ration,% Germination, °C Cotton
Root growth,% Stem growth,%
Control-water b/0 100.0 100.0 100.0
—O—C-N^^/ANv/\-C—O—(c^j) -( OH HO y- Br Br 0.1 100.0 114.3 106.3
0.01 87.0 93 92
0.001 91.0 109 96
0.0001 97.4 156.3 139.6
0.00001 95.1 117.6 121.5
Roslyn - (famous) 0.75-1.0 96 103.3 102.7
The study of the studied drug on the growth-stimulating activity of cotton shows, that the drug contributed to the germination of seeds and the development of the seedling system. Thus, the preparation of (l) N, N'-hexamethylene bis [(2-bromophenoxy)-carbamate] -when using 0.0001% and 0.00001% accelerated the growth of the root and stem of seeds above the control (table 7).
It was found that when soaking tomato seeds, the compounds (l) in total: N, N'-hexamethylene bis
[(2-bromophenoxy)-carbamate]:0,1;0,01;0,001% (7,500 times dilution) helped to increase their germination, most efficient germination improved environment improved by drug study ( 1 ), outstripping control by 56%. The best effect of stimulation of the roots of roots and stems of tomato seedlings was obtained by us when the seeds were soaked in a solution with the preparation ( 1 ), the stimulation of root growth was 77%, and the stem part 49% compared to control (table 8).
Table 8.- Effect of preparation 1 on seed germination and growth of tomato seedlings "TEMP"
Experiments Drug (1) Concent ration,% Germination, seed 2,3,5 day,% Tomato
Root growth,% Stem growth,%
Control-H20 b/0 55.0 100.0 100.0
(f^t)—O—O—(c^j) —( OH HO /— Br Br 0.1 60.0 129.2 136.3
0.01 57.0 148.6 139.7
0.001 59.0 153.4 144.5
0.0001 60.0 177 149.2
0.00001 57.0 138.7 125.6
Roslyn - (famous) 0.75-1.0 56.0 107.4 104.5
Study of the drug (l) for growth stimulation of activity on cucumber seeds of minor effects. The growth impulse is mainly observed in the stem of the seedlings. The drug (l) N, N'-hexamethylene bis [(2-bromophenoxy)-carbamate] - at a concen-
tration of 41.4% increased control, and also, respectively, compared with the control (table 9).
The effect of preparation 1 on seed germination and growth of seedlings of cucumbers variety "Uz-bekistan-740".
Table 9.
Experiments Drug (1) Concentration^ Germination across 5 days,% Cucumbers
Seed growth,% Stem growth,%
Control-H20 b/0 85.0 100.0 100.0
(c^))—O C C O—(f^) -( OH HO /— Br Br 0.1 88.0 117.0 109.3
0.01 90.0 118.0 117.5
0.001 90.0 136.4 139.6
0.0001 88.0 139.7 141.7
0.00001 85.0 118.6 114.3
Roslyn - (famous) 0.75-1.0 85.0 103.4 102.7
Thus, the drug(l) at a concentration of: (0.1; 0.01; 0.001%) is the most effective growth-stimulating drug for vegetables and cotton in laboratory
conditions and further more in-depth study in the field is recommended.
Conclusion: When studying the synthesis, properties and use of bromo-substituted biscarbamate
derivatives, the reaction was carried out at room temperature for 4 hours in the presence of dimeth-ylformamide and triethylamine. In the process, it was observed that derivatives of the starting material, N, N-hexamethylene-bis[(2-bromophenoxy-carbamates]), were formed in much higher yields. In this case, the high density, selectivity and easy mobility of the group electron cloud were based on its high reactivity. To study the reactivity with N-H
reactive centers, N, N'-hexamethylene-bis-[(2-bro-mophenoxy-carbamate], N, N'-dinitation, N, N'-dichlorination, N, N'-dimetallization, N, N' Reactions - dialkylations were carried out and analyzed, and the yield was 92.4%.The biological activity of the obtained compounds was studied, the drug at a concentration (0.1; 0.01; 0.001%) was tested in the laboratory and recommended as the most effective drug for the growth of vegetable and cotton crops.
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