CC BY
55
https://doi.org/10.29013/AJT-20-5.6-60-67
Turaeva Khurshida Kamalbaevna, doctoral student
National university of Uzbekistan, the Faculty of Chemistry
E-mail: torayevah@mail.ru Yuldasheva Mukhabbat Razzoqberdievna, Doctor of Chemical Sciences, docent National university of Uzbekistan, the Faculty of Chemistry
E-mail: ymuxabbat@bk.ru
REACTIONS OF NITROMEZITILENE WITH SUBSTITUTED ALKYLMALEINIMIDES
Abstract. Amidoethylation reactions of nitromesitylene with (3-hydroxyethylmaleinimide in the presence of concentrated catalysts of a mixture of concentrated sulfuric acid and phosphoric acid, and with ^-chloroethylmaleinimide in the presence of a small amount of FeCl3x12H2O catalyst were studied. The results showed that amidoalkylation reactions in the presence of Lewis acids were spatially selective, resulting in a single mono- substituted product with high yields. The influence of various factors on the course of the reaction, the yield of the product and their composition was determined. The structure of the synthesized substances was confirmed using physicochemical research methods.
Keywords: Nitromesitylene, (3-hydroxyethylmileinimide (^-GEMI), (3-chlorethylmaleinimide, malein anhydride (MA), FeCl3 x 12H2O.
Introduction. Maleic acid and its derivatives in pling reactions, depending on the conditions select-
the production of polymeric materials [1], various ed. If a maleinimide derivatives are to be used as a
monomers [2], as a binding agent [3], in the produc- sewing agent, reactions involving light and tempera-
tion of various adhesives, as a means of reducing cor- ture. Electrophilic coupling reactions are carried out
rosion and increasing durability in the paint indus- on the double bond for the synthesis of surfactants.
try [4], modifying bitumen [5], aviation technology This, expands the scope of application of maleic acid
[6-7], in medicine as an antiviral and antibacterial derivatives. N-hydroxyalkylmaleinimides are amido-
agent [8-9]. N-Methylolmaleinimide is used in the alkylating reagents and may in turn be starting prod-
amidomethylation of aromatic compounds and in ucts for the synthesis of alkylamines.
the production of surfactants. The products obtained The electrophilic substituted reactions are a
from the amidoalkylation reactions of aromatic com- widely used synthetic method in the aromatic se-
pounds with N-methylolmaleinimide differ from the ries, used in the production ofvarious mono-, di- and
products obtained on the basis of other amidoalkyl- polysubstituted aromatic compounds [10].
ating reagents by the double bond in the maleini- It is known that N-hydroxyalkylamides, N-hy-
mide group, which is used effectively in subsequent droxyalkylimides are among the amidoalkylating re-
syntheses. Reactions leading to double bonding can agents due to their ability to be synthesized under nor-
proceed on the basis of radical or electrophilic cou- mal laboratory conditions, high yield and resistance
to acids. Using these electrophilic reagents, they are possible to synthesize other types of electrophilic reagents, such as haloalkalkylamides, ethers, N, N'-alkyl-ene-bis-amides. The reactivity of N-alkylolimides at room temperature in the presence ofsulfuric acid varies, among which N-alkylolimides have been shown to have high electrophilic properties. We know that intermolecular amidoalkylation reactions are also important, they are possible to synthesize heterocyclic compounds that are difficult to obtain [11].
Results and discussion. This work is devoted to the course of the amidolalkylation reaction on the basis of the new amidoalkylat-ing reagent p-hydroxyethylmaleinimide and P-chloroethylmaleinimide. For the amidoalkylation reaction, p-hydroxyethylmaleinimide was initially selected as the alkylating electrophilic reagent. Based on the literature and taking into account that P-hydroxyethylmaleinimide is the primary alcohol, the amidoalkylation reaction of nitromezitilen was carried out in the presence of a mixture of proton acids, sulfate, phosphoric acid. Despite the fact that the p-hydroxyethylmaleinimide of our choice is the
primary alcohol, the amidoalkylation reactions with it proceed under relatively mild conditions. This is due to the presence of two carbonyl groups in the p-hydroxyethylmaleinimide molecule, or the attraction of the electron cloud density of the functional groups to:
O
8-
HC-
HC-
-
8+ .. C^-CHf* O*H
C8+
CO 8-
The reaction of nitromesitylene with p-hydro-xyethylmaleinimide was studied in the presence of sulfuric, phosphoric acid mixtures. Reagents for the reaction were nitromesitylene: p-GEMI: con.H2SO4/ H3PO4 in soluble benzene in a ratio of1:1 mol, carried out for 3-4 hours.
Analysis of the reaction product by thin-layer chromatography revealed the formation of three new substances on the plate. A 3:1 molar ratio of benzene and acetone were used as the solvent for thin layer chromatography (Figure 1).
1. Reaction product:
a) nitromesitylene,
b) 2,4,6-trimethyl-3- (p-maleinimidoethyl) nitrobenzene, Rf = 0.64
c) 2,4,6-trimethyl-3,5-bis- (p, p'-maleinimidoethyl) nitrobenzene Rf = 0,55
d) ester of p-hydroxyethylmaleinimide Rf = 0.41
2. Nitromesitylene
3. p-hydroxyethylmaleinimide
thin-layer chromatography (TLC) with plates (Pre-coated TLC sheets ALUGAM® Xtra SIL G/ UV254), mobile phase-benzene: acetone 3:1.
Figure 1. Thin layer chromatography analysis
One of these substances are 2, 4, 6-trimethyl-3- midoethyl) nitrobenzene (Rf=0.55), a ester of (p-maleinimidoethyl) nitrobenzene (Rf=0.64), the p-hydroxyethylmaleinimide (Rf=0.41) as an additive others are 2,4,6-trimethyl-3,5-bis-(p, p'-maleini- was confirmed by chromato-mass spectrum (Figure 2).
Results of the analysis of the chromatomass spectrum of the substance obtained from the reaction
of nitromesitylene with (S-GEMI in the device GC-MS
Peak Ret Time Width Area % 1) Solvent benzene, 2) 2,4,6-trimethyl-3,5-bis- (ß, ß'-maleinimidoethyl) nitrobenzene, 3) 2,4,6-trimethyl-3-(ß-maleinimido-ethyl) nitrobenzene, 4) ester of ß-hydroxyethylmaleinimide, 5) nitromesitylene
1 3.082 0.047 19555992 9.68
2 3.792 0.093 41587922 20.03
3 4.756 0.056 64766582 32.05
4 6.862 0.029 13780932 17.66
5 11.119 0.065 40480336 20.58
Figure 2. Results of chromatomass spectrum analysis in GC-MS Formation of fractions of ions of 2,4,6-trimethyl-3,5-bis- (T- maleinimidoethyl) nitrobenzene
m/z=39
p-hydroxyethylmaleinimide is selected as the reagent of amidoalkylation, and forms simple esters, such as primary alcohols. p-hydroxyethylmaleinimides form a simple ether of benzene at a boiling point of 80-85 °C. It is known from the studied literature that the simple esters formed by reagents of amidoalkyl-ation containing the hydroxyl group can also be reagents of amidoalkylation for the reaction. However, simple esters are reagents with low electrophilic ability compared to amidoalkylating alcohols. In order to activate the simple esters formed in amidoalkylation reactions. To increase the reactivity, it is necessary to add an extra amount of catalyst to the reaction
mixture. While part of the extra catalyst is used to decompose the ordinary ether, the other part acts as a catalyst for the amidoalkylation reaction.
However, increasing the catalyst in the reaction requires slightly milder conditions, as the reaction undergoes a polymerization reaction due to the active double bond of the amidoethylation reagent p-hydroxyethylmaleinimide. The reaction resulted in the formation of two new substances -2,4,6-trimethyl-3- ( p-maleinimidoethyl) nitrobenzene, 2,4,6-trimethyl-3,5-bis-(p, p'-maleinimido-ethyl) nitrobenzene are seen.
The reaction equation is as follows:
NO
H3C
COn. H2SO4/H3PO4 -*
Benzene
NO2
O O II
V3' hQN
r O O
no2
O
3
+
3
O
O
2,4,6-trimethyl -3- 2,4,6-trimethyl-3,5-bis-
(P-maleinimidoethyl)nitrobenzene maleinimidoethyl) nitrobenzene
Figure 3. 3D view of the items
C-amidoalkylation reactions of aromatic compounds follow the SEAr2 electrophilic substitution mechanism, such as alkylation and acylation reactions. The reaction mechanism is as follows:
O
// 8
H
H + OSO3H NO2
HsC^ Y CH3 O N02
Subsequent amidoalkylation reactions were performed with-^-chloroethylmaleinimide. For the amidoalkylation reaction of nitromesitylene with N-XEMI in the presence of a catalyst FeCl3x12H2O was carried out at a ratio of 3:1: 2.64x10-4 moles, at 100oC. The reaction revealed that only the mono-substituted product 2-(N-maleinimidoethyl) -1,3,5-trimethyl nitrobenzene was formed with 58% yield, no additional substance was formed. The reaction conditions are given in Table 1.
The reaction equation is as follows:
oh
+
h3<r y ch3
no2
O
o
o
o
2
The reaction mechanism is as follows:
O
N-CH2-CH2-Cl + FeCl3 . 12H2O
S- S+
N-CH2-CH2-Cl----FeCl3 . 12H2O
(I)
Table 1.- Nitromezithylene with P-chloroethylmaleinimide FeCl3x12H2O conditions of amidoalkylation of reaction in the presence of a catalyst
O
O
№ Substrate Mole ratios of reagents substrate: P-ChEMI: cat. Reaction temperature, OC Reaction duration, hours The product formed with ^-chloroethylmaleinimide substrate
% T liquid
1. Nitromesitylene 3:1:2,64x10-4 100 3 58 128-129
2. Nitromesitylene 2:1:2,64x10-4 100 3 55 128-129
3. Nitromesitylene 1:1:2,64x10-4 100 4 50 128-129
It can be seen from the table data that increasing the amount of substrate from 1 to 3 and increasing the reaction time leads to an increase in yield. If the reaction is carried out at a temperature above 100oC, the reaction will lead to resinization ofthe mixture. This is due to the fact that the polymerization is tolerated at
Chromatography obtained during the reaction
„ 1. 2 - (N-maleinimidoethyl) -
1,3,5-trimethyl nitrobenzene
a) nitromesitylene,
b) 2 - (N-maleinimidoethyl) -1,3,5-trimethyl nitrobenzene
2. Nitromesitylene
the expense ofthe active double in maleinimide. When the reaction mixture was examined on the skirt layer chromatography, it was seen that a single new product was formed. No additional reaction was found. A 3:1 molar ratio ofbenzene and acetone was used as the solvent for thin-layer chromatography. (Figure 4)
Chromatography after purification
11. 2-(N-maleinimidoethyl) -1,3,5-trimethyl nitrobenzene Rf = 0.64 2. Nitromesitylene
Figure 4. Thin layer chromatography analysis
The reaction substance was recrystallized in ethyl alcohol and chromatographed again.
IR spectral analysis
Figure 5. IR spectrum of 2-(P-maleinimidoethyl)nitromesitylene
IR spectrum: Infrared Fourier spectrometer "IRTracer-100" (SHIMADZU CORP., Japan 2017) in complete with the prefix broken total internal reflection (NIP) MIRacle-10 c prism diamond/ ZnSe (spectral range on the scale of wave num-bers-4000^400 cm-1; resolution - 4 cm-1, sensitivity signal-to-noise ratio-60,000:1; scanning speed-20 spectra per second).
When we studied the IR spectrum, we found that there were the following absorption lines: deformation and valence oscillations specific to the aromatic ring in the fields 785, 860, 912, 981 and 1633 (cm-1); Deformation and valence oscillations of the HC=CH group in the branches 1219, 1259,
1654 and 2505 (cm deformation and valence oscillations of the methylene groups in the branches 1431 and 2875, 2792 (cm-1), 1633, 1703 (cm-1). in the presence of valence oscillations of the nitrogen-bound carbonyl group. One of the frequencies with an intense appearance was the oscillation of nitro compounds (NO2) in this aromatic ring in the valence symmetric 1259.52 cm-1 regions (Figure 5).
Results of analysis. As a result of electro-philic substituted reaction of nitromesitylene with (3-chloroethylmaleinimide in the presence of iron (III) chloride crystal hydrate mono product with 58% yield 2-(N-maleinimidoethyl)-1,3,5-trimethyl nitrobenzene and p-hydroxyethylmaleinimide in
the presence of sulfate with sulfate as a result, mono with 39,05% yield and bis product with 20,03% yield were formed to form 2,4,6-trimethyl-3,5-bis-(p, (3'-maleinimidoethyl)nitrobenzene. While the dialysis product was formed during the ami-doethylation reaction of nitromezithylene with (3-hydroxyethylmaleinimide, the formation of a mono product was determined by the amidoethyl-ation with (3-chloroethylmaleinimide.
Conclusion and suggestion. Electrophilic substituted reactions in nitromesitylene, which contains one electron acceptor and three electron donor groups in the agreed state, were carried out with derivatives of maleinimide occupied by halogen and
hydroxyl groups. Changes in product yield and composition were determined according to the type of electrophilic reagent obtained for the reaction. It can be concluded that if there are only strong reference electron donor groups in the aromatic ring and the negative charge value in the benzene ring increased, conducting reactions in the presence of strong proton catalysts such as sulfuric acid at low temperatures gives good results. Additionally, if the aromatic ring contains an electron-accepting group, such as a ni-trogroup, which reduces the negative charge value of the ring along with the electron-donor groups, more stringent conditions are required for the reaction to proceed.
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