CC BY
20
5. Husain S. S., Nirthanan S., Ruesch D., Solt K., Cheng Q Li G. D., Arevalo E., Olsen R. W., Raines D. E., Forman S. A., Cohen J. B., Miller K. W., "Synthesis of trifluoromethylaryl diazirine and benzophenone derivatives of etomidate that are potent general anesthetics and effective photolabels for probing sites on ligand-gated ion channels", J. Med. Chem., 49 (16) - (2006) - 4818-4825.
6. Venu T. D., Shashikanth S., Khanum S. A., Naveen S., Firdouse A., Sridhar A. M., Prasad J. S., "Synthesis and crystallographic analysis of benzophenone derivatives - The potential anti-inflammatory agents", Bioorganic & Medicinal Chemistry, 15 - (2007) - 3505-3514.
7. Ferris R. G., Hazen R. J., Roberts G. B., Clair M. H. S., Chan J. H., Romines K.R, Freeman G. A., Tidwell J. H., Schaller L. T., Cowan J. R., Short S. A., Weaver K. L., Selleseth D. W., Moniri K. R., Boone L. R., "Antiviral Activity of GW678248, a Novel Benzophenone Nonnucleoside Reverse Transcriptase Inhibitor", Antimicrobial Agents and Chemotherapy, 49 (10) - (2005) - 4046-4051.
8. Manivel P., Roopan S. M., Khan F. N., "Synthesis of o-Substituted Benzophenones by Grignard Reaction of 3-Sub-stituted Isocoumarins", J. Chil. Chem. Soc., 53 (3) - (2008) - 1609-1610.
9. Ashoka S., Chithaiah P., Thipperudaiah K. V., Chandrappa G. T., "Nanostructural zinc oxide hollow spheres: A facile synthesis and catalytic properties", Inorganica Chimica Acta, 363 (13) - (2010) - 3442-3447.
DOI: http://dx.doi.org/10.20534/AJT-16-9.10-104-107
Yuldasheva Mukhabbat Razzoqberdievna, National university of Uzbekistan, the Faculty of Chemistry E-mail: ymuxabbat@bk.ru
Synthesis and analysis of aryl methyl amines
Abstract: Synthesis of alkyl amines derivatives of aromatic hydrocarbons. The structure of the obtained 2,4-de-methylbenzylamine, 2,5- dimethybenzylamine, 2,4,6-threemethyl 3,5-di (N-aminomethyl) nitrobenzene was determined by means of IR spectroscopy and chromato-mass-spectrometry.
Keywords: aromatic hydrocarbons, xylenes, nitro-mesitylene, amidoalkylation, N-hydroxyalkylimide, alkyl amines of aromatic hydrocarbons.
Aromatic compounds and their functional derivatives are the most widen and important class of organic compounds on the base of the chemical transformations of which can be solved the fundamental problems influential ability reflectional reactivity of aromatic substrates and alkylating reagents by using various catalysts.
Continuing systematically investigation of reaction amidoalkylation of aromatic hydrocarbons [1-3], we have studied the amidoalkylation of xylenes and nitro-mezitilena in the presence of proton catalysts, also synthesized aryl alkyl amines.
We investigated synthesis arylalkylimides from ami-dalkyl reaction using from m-xylene which is substitutents of the aromatic ring methyl groups in a consistent orientation and easy reacts with N-hydroxymethylftalimide (N-MFI) by electrophilic substitution. Starting materials for this reaction: m-xylene, N-MFI, cons H2SO4:H3PO4 were taken 6:1:2:1 mol and reaction was continued by string at 120 ° C for four hours. The result of this reaction 1,3-dimethyl-4-(N-phthalimidomethyl)benzene
is obtained in yield 73%. Experimental section contains the IQ-spectrum of compound and H^spectra were obtained 2,29d (6H, 2CH3), 4,6 s (2H, CH2), 6,9d (3H, Ar3H3), 7,75 m (4H, ArR2H4). Subsequent treatment with ^-hydroxoethylphthalimide under the usual reaction conditions afforded substance in 76% yield.
Similarly, the compound of p-xylene's with phthalimidialkyl synthesized as an ordered stages above. The reaction of para- xylene's with N-MFI, H3PO4 and H2SO4 is prolonged for six hours. The result of this reaction 1,4-dimethyl 2-(N-phthalimidomethyl) benzene is obtained in yield 78%.
The reaction of nitrogen mezitilen with N-methylol-phthalimid is carried by one mol out. Phosphoric acid is used as a catalysis. It is defined that in this reaction all substitutents of benzene ring have obtained consistent orientation so that reason it gives a opportunity to make bis-amidalkyle and separate 2,4,6- threemethyl 3,5-di-(N-phthalimidomethyl) nitro benzene by string at 120 ° C in 65% yield.
In it's IR-spectrum the following characterical bands (v, sm-1) were observed: 890 (substituted benzene), 1605 (C-C b ArH), 3030 (=C-H b ArH), 1439 (CH3), 2933 (vsCH2), 1400,1460( SCH2) 2873(vsCH2),
2980(Vas(CH3)- 5
Next experiments associated with hydroxylation of amidoalkyl products of nitromezethylen and m-, p- xy-
lenes with ammonia and NaOH. It is defined that different products can be taken from hydroxylation according to type and quantity of reagents. The hydroxylation reaction of 1,3-dimethyl 4-(N-phthalimidomethyl) benzene is carried out with 25% ammonia water. If ammonia is taken 1:1 mol it would produce arylalkylamine and amide of phthalic acid.
CH3
CH3
O
u /C
NH3, H2O
ch2-n
H3C
ch2-nh2
O
w
HO—C
HO—C // O
// O
When 2,4-demethylbenzylamine is put to chromato-mass-spectra in a condition which we have chosen after 16.001 minutes we can see ions of 2,4- dimethylbenzyl.
H2C
NH4 M/Z = 28
CH M = 107
CH3
ch2^-Nh2
M/Z = 135
In addition, the particular reorientation ofxenon on aromatic nuclear leads to create ammonia ions which can be seen at chromato-mass-spectrometry.
CH3
— Or™'
M/Z = 119
NH2 M = 16
In MS molecules are broken apart and produced narrow piece of ions [128]. Breaking apart ions of 2,4- dimethylbenzyl are illustrated below. First of all, the ions of 3- methylbenzyl are created at 105 M/Z. These ions reorientated like an aromatic compounds
which contain methylen group and produced benzyl ions removing a small amount of methene at 91 M/Z, while the breaking apart higher amount of ethelen compare to benzyl ions amount produces phenyl ions at 77 M/Z.
/ TTCH M=14 M=14
-CH
M/Z = 119
CH2
y
-CH2 M/Z = 105
V \
M/Z = 91
M/Z = 77
It is obvious that the ion of benzyl at 91M/Z produces phenyl ions at 77M/Z.
// \ i + M=14
// \\-i-cH2 ->- K+JI
-CH2
M/Z = 91 M/Z = 77
Generally view of direction of fragmetation in chromato-mass-spectrium is represented below:
3
h2c
+ i~\-CU3
nh4 + \ / .«_
ch m = 107
m/z = 28
ch3
NH2_ m/z = 135
m=14 -ch2
nh2 + m = 16
m/z = 119
ch3 m/z = 105
ch2
m=14 CH2^/ w
m/z = 91
-c2h4
m=28
-ch2 m=14
m/z = 77
In it's IR-spectrum there are following typical bands of absorption (v, sm1): 979, 942 (1,2,4- threesubstituted benzene), 1615, 1599 (C-C b ArH), 3030 (=C-H b ArH), 1717, 3488 (-NH), 2900 (vSCH3), 2951 (v CH,), 1392
2 S3 as 3
(SCH3), 2845 (vSCH2), 1465 (SCH2).
The molecular ions of phthtalic acid which synthesized by hydroxylation of 2,4-dimethylbenzyl amine's are demonstrated after 16,708 minutes at 166 M/Z in mass-spectra.
M=76
+ CO + H2O2„ M/Z=28 M=36
O
.„CpOfH
/X^-O^-H ' % ! _
M/Z=166
M=33
- O-OH
O
C^H
O
M=28^ -CO
C+
M=28 -CO
M/Z=105
M/Z=133
M/Z=77
From this picture you can see fully view of producing ion fragments from the molecular ions.
Hydroxylation of 1,4-dimethyl 2-(N-phthalimi-domethyl) benzene is occurred in the mixture of kalium hydroxyl's with water and ethanol 1:2 molls. After separating water from mixture, remnants are melted in
ch3
h3c
koh, h2o
the methanol. The residue of phthalic acid salt doesn't melt in the methanol. The amine which melted in the methanol can be separated with the help of evaporation method. The hydroxylation afforded 2,5- dimethyben-zylamine in 98% yield:
o
ch3 w
ko—c
h3c
ch2-nh2
ko—c // o
o
In 2,5-dimethybenzylamine's IR-spectrum there are following typical bands of absorption (v, sm1): 958, 802 (1,2,4- threesubstituted benzene), 1600 (C-C b ArH), 3005 (=C-H b ArH), 1708, 3114 (-NH2), 2906 (vSCH3), 2951 (vCH_), 1392 (SCH3), 2845 (vSCH2),
1467 (SCH,).
1,3,5-Threemethyl 2,6-di (N-phthalimidomethyl) nitrobenzene is hydrolysed by 25% ammonia aqua. Hydroxylation process is carried out since boiling temperature of water and 1,3,5-threemethyl 2,6-di (N-phthalimidometh-yl)nitro benzene in 98% yield. Due to ammonia takes excessive amount the arylalklylamine and amide of phthalic acid are produced. The equation of hydrolysis reaction:
no3
The molecular ions of 2,4,6-threemethyl 3,5-di (N-aminomethyl) nitrobenzene demonstrates after 25,802 minutes at 224 M/Z.
+
+
O
+
. no2
no2 2
M/Z=224 M/Z=209 The piece of ions is produced from ordered disintegration of CH2, NH2, and NO2 molecular ions at 209 M/Z.
CH3
i \ + I '
H2N—CH2~ H2N+CH2^^\^CH2
CH3
no2
M/Z=179
M/Z=118
H NO2 M/Z=165
The main part of these ions are produced at 118 M/Z and they also disintegrated more small piece of ions.
h3C_
H2C A
H M/Z=118
M=14^ -CH2
CH3 -CH2
H
H—CJ
-CH
CH3
The general view of reaction
CO
CH3
/ CO
n-ch2-
M/Z=104
KOH, H2O
CH2 M/Z=91 H
CH3
-ONa
CC
ONa
+ H2N-CH2-
M/Z=77
CH3
CH3
Initially, the bond of carbon-nitrogen is broken cause second carbonyl group which is strong positive charged of hydroxyl group connected with carbonyl group. Due and easy attack of hydroxyl group. to breaking C-N bond, redistribution electrons of the
roa
ch3
nch2-f^
ch
oh
ch3
N-CH2t^
c II o
ch3
'OH CH3
-N-CH2-r^' "
ch
o
II
c
-o- ch3
ch3
o
II
c-o-
r^V-^o"
ch3
ch3
o:h
\\>a t 4CH3
u
a. c
^NH-CH
■o.h
ch3
o
u
c-o- _
+ hN-ch2
coh ■■
ch3
//
o
ch3
o
w
c-o-
ch3
c-o- + h2n-ch2-r o I CH3
It is possible synthesis the highest yield of amines by hydroxylation the products of phthalimidoalkylaryl in a base condition.
- If ammonia is taken 1:1 mol (ekvimolar) it would produce arylalkylamine and amide of phthalic acid,
if it takes in an excessive 1:2 mol it would produce arylmethylamine and amide of phthalic acid.
- Hydrolysis of phthalimidoalkylarys with kalium hydroxide produces kalium salt of phthalic acid and arylalkylamines.
O
C
O
o
References:
1. Axmedov Q.N., Okmanov R.Y. Yuldasheva M.R. Benzodioqsan-1,4ni |3-gidroksi- va |3-brometilftalimid bilan amidoalkillash. - 2009. Вестник НУУз - No 3. - С.67-69.
2. Ахмедов К.Н., Юлдашева М.Р., Турсунова М.Р. Взаимодействие изомерных ксилолов с N-бром-метилфталимидом в присутствии каталитических количеств катализаторов. Узб.Хим. Журн. - 2006 - №2. С. 28-32.
3. Axmedov Q.N., Yuldasheva M.R. Mezitilen va psevdokumolning ftalimidoalkil hosilalari sintezi. O'z RFM. -2013. - №4. - C.42-45.
