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Study of the products obtained by treating Glutamic Acid with
Tertiary Butyl Chromate in water
Poonam Singh, Dr.Anita Gupta and Dr.H.O.Pandey
Department of Chemistry, Ranchi University, Ranchi – 834008
---------------------------------------------------------------------------------------------------------------------------------------------------
Abstract :
Di-tert-butyl chromate (TBC) was prepared by dissolving calculated quantity of pure and dry chromium trioxide
(CrO3) in tert-butyl alcohol (TBA). Glutamic acid was treated with TBC in different substrate : oxidant (TBC) molar ratio in water
as solvent. The solid products obtained were isolated, washed, dried, purified and collected as GU11, GU21, GU23. The formulae of
these products have been worked out on the basis of elemental analysis, thermogravimetric studies and FTIR peaks.
Keywords : FTIR, Glutamic acid, Peaks, TBA, TBC, Water
Introduction:
TBC has been used as oxidant by several workers. They have used this oxidant for the oxidation of various types of organic
compounds. In most of these studies, solid complexes of chromium have been obtained. G.D Mishra et.al. 1-11 have used TBC for
oxidizing various organic compounds. In the present work, we have used glutamic acid with TBC in various substrate: oxidant
ratios in water.
Chemical used :
Chromium trioxide (CrO3), TBA, water, Glutamic acid, potassium persulphate (K2S2O8), acetone etc. (Chemical used were all
A.R.Grade.)
Experimental Procedure :
(a) GU 11 (substrate : oxidant :: 1:1 molar ratio) TBC was prepared by dissolving 1 gm of pure and dry CrO3 in 10
ml of TBA. 1.47 gm of glutamic acid was dissolved in water to get substrate solution (SS-1). Exothermic reaction took
place when TBC was added to SS-1 leading to the formation of brown precipitate which turn to brown product when
washed several times with acetone and dried. This was labeled as GU 11.
(b) GU21 (substrate : oxidant :: 1:0.5 molar ratio) : TBC was prepared by dissolving 0.5 gm of pure and dry CrO3 in
10ml of TBA 1.47 gm of glutamic acid was dissolved in water to get substrate solution (SS-2). Exothermic reaction took
place when TBC was added to SS-2 leading to the formation of black precipitate. The product turned into greenish
brown product when washed several times with acetone and dried. This was labeled as GU21.
(c) GU23 (substrate : oxidant :: 1:2 molar ratio) : TBC was prepared by dissolving 0.015 gm of pure and dry CrO3 in
10 ml of TBC. 1.47 gm of glutamic acid was dissolved in water to get substrate solution (SS-3). TBC solution was now
added to SS-3 solution. After 5 minutes it started boiling which showed the highly exothermic nature of the reaction.
The reaction mixture was now left overnight. The solid products obtained thus was washed successively with acetone
and water. The black colour solid was labeled as sample GU 23
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Results and Discussion:
The quantitative analysis of carbon, hydrogen & nitrogen were performed instrumentally. The chromium content was
estimated volumetrically. The proposed formula, percentage composition of the complex was experimentally found as well as
calculated theoretically.
(a) GU 11 : Table 1 shows the comparison of observed and calculated elemental percentage.
Colour - Greyish black
Table I
(COMPOSITION OF GU11)
Element
Observed %
Calculated %
Nitrogen
5.427
4.635
Carbon
23.78
23.84
Hydrogen
14.371
4.304
Chromium
17.33
17.218
Oxygen
49.09
47.68
Empirical Formula :CrNC6H13O9
Proposed Formulation :
CrO[COOH.CH2CH2NH2.CH2CH2COOH]
.4H2O
The FTIR peaks also support the presence of the bonds and groups presents in proposed formula
(Table II).
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Table II
FTIR peak of complex GU11
3549.02
Nature of
Peaks
Broad
3028.24
Broad
1573.91
Sharp
-COO group, Coordinated
COOH group
1442.75
Medium
C-H stretching, C=C
stretching
1408.04
Weak
C=O stretching
1354.03
Sharp
COO- group
1257.59
Sharp
1153.43
Sharp
1091.71
945.12
Weak
O-NO2,Vs(C-O) + S (O-C=O)
V8
C-O of alcohol, COOH,
aldehyde
C-C stretching
Weak
CO coordinated water
879.54
Weak
O-H Rocking (due to water)
802.39
Weak
O-H Rocking (due to water)
763.81
sharp
HCOOH
590.22
424.34
Weak
Cr-O bonding
Weak
Cr-O bonding
Peak at
Group Assignment
Ar-NO2, C-H
stretching
Ar-NO2, C-H stretching
The DTA-TGA curves of the complex GU 11 show the expected loss pattern for the proposed formulation. The two stages of the loss as
supported by DTA curves occur in between 33 0C and 4850C. The 1st loss of 22.548 % (theoretical 24.406 %) corresponds to the escape
four water molecule in the temperature range of 33- 3170C. The second experimental loss of 52.99 % ( theoretical 50.16%) is attributed
two molecules of propanoic acid and amino group leaving
behind the oxide of Cr (Table III,weight loss pattern).
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Table III
WEIGHT LOSS PATTERN
Temperture
Percentage l oss
Wei ght loss pattern
Experi mental Theortical
0
CrO[COOH CH 2 CH2 NH2
CH 2 CH2 COOH]. 4H2O
0
33 C-317 C
22.548
24.406
52.99
50.16
-4H2O
0
0
CrO[COOH CH 2 CH2 NH2
317 C-485 C
CH 2 CH2 COOH]
-[COOH CH 2 CH2 NH2
CH 2 CH2 COOH]
CrO
DTA-TGA curves of complex GU11
TGA
%
DTA
uV
Therm al Analys is Res ult
3 GU11.tadDT A
3 GU11.tadTG A
100.00
150.00
100.00
50.00
50.00
0.00
0.00
0.00
200.00
TGA
%
400.00
600.00
Temp [C]
800.00
1000.00
Therm al Analys is Res ult
3 GU11.tadTG A
100.00
50.00
0.00
0.00
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600.00
Temp [C]
800.00
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DTA
uV
TGA
%
Therm al Analys is Res ult
150.00
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Therm al Analys is Res ult
3 GU11.tadTGA
3 GU11.tadDTA
100.00
100.00
Start
0
33.00x10
C
End
0
1000.00x10
C
Weight Loss
0
-1.844x10
mg
0
-78.301x10
%
0
Start
33.00x10
C
End
0
317.00x10
C
Weight Loss
0
-0.531x10
mg
0
-22.548x10
%
50.00
50.00
Start
0
317.00x10
C
End
0
485.00x10
C
Weight Loss
0
-1.248x10
mg
0
-52.994x10
%
0.00
0.00
0.00
200.00
DTA
uV
400.00
600.00
Temp [C]
800.00
0.00
200.00
400.00
600.00
Temp [C]
800.00
1000.00
Therm al Analys is Res ult
3 GU11.tadDTA
150.00
100.00
50.00
1000.00
Peak
0
406.27x10
C
Onset
0
357.75x10
C
Endset
0
460.23x10
C
Heat
0
69.97x10
J
0
29.71x10
kJ/g
0
Peak
155.02x10
C
Onset
0
99.43x10
C
Endset
0
169.85x10
C
Heat
0
14.06x10
J
0
5.97x10
kJ/g
0.00
0.00
200.00
400.00
600.00
Temp [C]
800.00
1000.00
Results and Discussion :
(b) GU 21 Table 4 shows the comparison of observed and calculated elemental percentage.
Colour - Greyish black
Table IV
(COMPOSITION OF GU21)
Element
Observed %
Calculated %
Nitrogen
7.039
6.36
Carbon
30.57
27.27
Hydrogen
5.362
7.27
Chromium
12.133
11.81
Oxygen
44.896
47.27
Empirical Formula
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: CrNC10H23O13
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Proposed Formula : CrO2 [COOH.CH2
CH2CH2HCHO.HCHO CH2CH2CH2
NH2COOH] 5H2O
The FTIR peaks support the presence of the bonds and groups presents in proposed formula (Table V).
Table V
FTIR peak of complex GU21
Peak at
3035.96
1658.78
Nature of Peaks
Broad
Middle
1573.91
1516.05
Weak
Sharp
1411.89
1354.03
1253.73
Weak
Sharp
Sharp
Group Assignment
Ar-NO2, C-H stretching
C=O stretching (aldehyde),
(-C=C-) Alkene
C=O stretching
-COO group, Coordinated
COOH group
C=O stretching
COO- group
O-NO2,Vs(C-O) + S (O-C=O) V8
1153.43
Sharp
C-O of alcohol, COOH, aldehyde
1087.85
948.98
867.97
806.25
767.67
713.66
540.07
424.34
Weak
Weak
Weak
Weak
sharp
sharp
Weak
Weak
C-C stretching
CO coordinated water
O-H Rocking (due to water)
O-H Rocking (due to water)
HCOOH
HCOOH
Cr-O bonding
Cr-O bonding
The DTA-TGA curves of the complex GU 21 show the expected loss pattern for the proposed formulation. The two stages of the
loss as supported by DTA curves occur in between 1500C 0C and 4850C.The 1st loss of 23.99 % (theoretical 21.06 %)
corresponds to the escape of five water molecules in the temperature range of 150- 2750C. The second experimental loss of
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52.99 %( theoretical 50.16%) is attributed to two molecules of butanoic acid, two molecules of formaldehyde and amino group
leaving behind the oxide of Cr (Table VI,weight loss pattern).
Table VI
WEIGHT LOSS PATTERN
Temperture
Percentage loss
Weight loss pattern
Experimental
0
0
CrO 2[COOH CH 2CH 2CH 2HCHO.HCHO
150 C-275 C
Theortical
23.99
21.26
49.369
57.27
CH 2CH 2CH 2NH 2COOH] 5H2O
-5 H2O
0
0
333 C-500 C
CrO 2[COOH CH 2CH 2CH 2HCHO.HCHO
CH 2CH 2CH 2NH 2COOH]
[COOH CH 2CH 2CH 2HCHO.HCHO
CH 2CH 2CH 2NH 2COOH]
CrO 2
DTA-TGA curves of complex GU21
Therm al Analys is Res ult
DT A
uV
2 GU21.tadDT A
100.00
0.00
0.00
200.00
400.00
600.00
Temp [C]
800.00
1000.00
Therm al Analys is Res ult
TG A
%
2 GU21.tadTG A
100.00
Start
0
150.00x10
C
End
0
275.00x10
C
W eight Loss
0
-0.608x10
mg
0
-23.994x10
%
Start
0
33.00x10
C
End
0
1000.00x10
C
W eight Loss
0
-2.190x10
mg
0
-86.425x10
%
50.00
Start
0
333.00x10
C
End
0
500.00x10
C
W eight Loss
0
-1.251x10
mg
0
-49.369x10
%
0.00
0.00
200.00
400.00
600.00
Temp [C]
800.00
1000.00
Therm al Analys is Res ult
DT A
uV
2 GU21.tadDT A
Peak
0
405.77x10
C
O nset
0
362.21x10
C
Endset
0
458.60x10
C
Heat
0
85.61x10
J
0
33.79x10
kJ/g
100.00
Peak
0
188.15x10
C
O nset
0
178.17x10
C
Endset
0
197.49x10
C
Heat
0
-2.76x10
J
0
-1.09x10
kJ/g
0.00
0.00
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Results and Discussion:
(c) GU23 : Table 7 shows the comparison of observed and calculated elemental percentage.
Colour - Black
Table – VII
COMPOSITION OF GU23
Element
Observed %
Calculated %
Nitrogen
4.247
3.286
Carbon
20.84
22.53
Hydrogen
3.823
5.63
Chromium
12.133
12.20
Empirical Formula
:CrN1C8H17O15
Proposed Formula
:CrO3[COOH CH2
CH2 COOH COOH CH2 CH2NH2COOH] 4H2O
The FTIR peaks support the presence of the bonds and groups presents in proposed formula
(Table VIII).
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Table VIII
FTIR peak of complex GU23
Peak at
3576.02
3016.67
2831.50
Nature of Peaks
Broad
Broad
Broad
Group Assignment
Ar-NO2, C-H stretching
Ar-NO2, C-H stretching
Ar-NO2, C-H stretching
1647.21
Middle
1570.06
Sharp
C=O stretching (aldehyde),
(-C=C-) Alkene
-COO group, Coordinated COOH
group
1446.61
1408.04
1354.03
1149.57
1091.71
945.12
759.95
605.65
Medium
Weak
Sharp
Sharp
Weak
Weak
sharp
Weak
C-H stretching, C=C stretching
C=O stretching
COO- group
C-O of alcohol, COOH, aldehyde
C-C stretching
CO coordinated water
HCOOH
Cr-O bonding
The DTA-TGA curves of the complex GU 23 show the expected loss pattern for the proposed formulation. The two stages of the
loss as supported by DTA curves occur in between 250C 0C and 4700C.The 1st loss of 16.77 % (theoretical 17.118 %)
corresponds to the escape of four water molecules in the temperature range of 25- 3130C. The second experimental loss of
49.678 % ( theoretical 46.062%) is attributed to two molecules of propanoic acid,two molecules of formic acid and an amino
group leaving behind the oxide of Cr (Table IX,weight loss pattern).
Table IX
WEIGHT LOSS PATTERN
Temperture
Percentage loss
Weight loss pattern
Experimental
0
0
25 C-313 C
CrO 3[COOH CH 2 CH2 COOH COOH
CH 2 CH2 NH2 COOH] 4H2O
Theortical
16.77
17.118
49.678
46.062
-4 H2O
0
0
313 C-470 C
CrO 3[COOH CH 2 CH2 COOH COOH
CH 2 CH2 NH2 COOH]
[COOH CH 2 CH2 COOH COOH
CH 2 CH2 NH2 COOH]
CrO 3
DTA-TGA curves of complex GU23
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TGA
%
DTA
uV
Therm al Analys is Res ult
100.00
1-GU23.tad DTA
1-GU23.tad TGA
100.00
50.00
0.00
0.00
0.00
200.00
TGA
%
400.00
600.00
Temp [C]
800.00
1000.00
Therm al Analys is Res ult
100.00
1-GU23.tadTGA
50.00
0.00
0.00
200.00
400.00
600.00
Temp [C]
800.00
1000.00
Therm al Analys is Res ult
DTA
uV
1-GU23.tadDTA
100.00
0.00
0.00
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Therm al Analys is Res ult
TGA
%
1-GU23.tadTGA
100.00
Start
0
25.00x10
C
End
0
313.00x10
C
Weight Loss
0
-0.391x10
mg
0
-16.774x10
%
Start
0
25.00x10
C
End
0
1000.00x10
C
Weight Loss
0
-1.544x10
mg
0
-66.238x10
%
50.00
Start
0
313.00x10
C
End
0
470.00x10
C
Weight Loss
0
-1.158x10
mg
0
-49.678x10
%
0.00
0.00
200.00
400.00
600.00
Temp [C]
800.00
1000.00
Therm al Analys is Res ult
DTA
uV
1-GU23.tadDTA
100.00
Peak
Peak
0
395.44x10
C
Onset
0
343.36x10
C
Endset
0
427.35x10
C
Heat
0
64.11x10
J
0
27.51x10
kJ/g
0
157.65x10
C
0
Onset
106.78x10
C
Endset
0
263.92x10
C
Heat
0
18.24x10
J
0
7.83x10
kJ/g
0.00
0.00
200.00
400.00
600.00
Temp [C]
800.00
1000.00
Conclusion
The reaction conditions in table show that the formation of compounds/ complexes of chromium with glutamic acid is difficult.
The chemical oxidation of glutamic acid under mechanical stirring and microwave condition leads to different product including
nitro derivatives. The degradative oxidation of the substrate takes place when the ratio of oxidant is more as substantiated by
the presence of smaller fragments in case of GU-23. The formation of amino compound in higher ratio of oxidant is supported by
its presence in GU -23 as ligand. This is not observed in other cases where the extent of oxidation is less. Extent of degradative
oxidation increases as the proportion of oxidant is raised, as the lower fragment HCOOH is observed in GU-23. It is also
supported by the fact that some of the complexes like GU-21 & GU-23 is formed with the unoxidised ligand along with other side
products (where the oxidant ratio is less compared to GU-23). Again the solubility of the products in water is more in those
cases when glutamic acid itself is present as ligand. The number of water molecule in the products GU-23 is more whereas it is
less in products GU-11 and GU-21. This may be due to the fact that greater extent of oxidation leads to the formation of smaller
organic moiety and greater number of water molecules.
REFERENCES
1.
2.
3.
4.
5.
6.
G.D. Mishra, (1985). J. Inst. Chem. (Ind.) Pp. 57.
G.D.Mishra, R.Prasad, S.P. Singh and S.Mishra, (1988). J. Inst. Chem. (Ind.) Pp. 60.
G.D.Mishra, H.O.Pandey, and N.N. Mishra, (1990). J. Inst. Chem. (Ind.) 62,37
G.D.Mishra, N.Drivedi, N.N.Mishra, and H.O.Pandey, (1991). J. Inst. Chem. (Ind.)62,67
G.DMishra, S.N.Tiwari, and N.N.Mishra, (1991). J. Inst. Chem. (Ind.)63,217 .
G.D.Mishra, S.N.Tiwari ; N.Dwivedi and M.Alam, (1991). J. Inst. Chem. (Ind.) 63,166
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7. G.D.Mishra, M,Alam, R.Thakur, and N.N.Mishra, (1991). J. Inst. Chem. (Ind.)63,(6)217
8. G.D.Mishra, H.C. Mishra, and L.N.Choubey, (1985).J. Inst. Chem. (Ind.) Soc LX, 521
9. G.D.Mishra, R.K. Singh, and B.H.P. Pingua, (1999). J. Chemtracks, 1:172
10. H.C Mishra, G.Mishra, and L.N. Choubey, (1983).J. Inst. Chem. (Ind.) Soc. Vol. LX
11. G.Mishra, and N.K Tiwari, (2005). J. Chemtracks 7, 163, 168
12. D. Adam, (2003). Nature 421,571
13. C.O. Kappe, Angew, (2004) Chem.Int. Ed. 43,6250
14. F. Freeman, (1986) In Organic Synthesis by oxidation with metal compounds : Mijs. W.J. ; de Jonge, C.R.H.I Eds. Plenum
Press : New York, pp. 68-81
15. Neeraj, A.K. Pandey and G.D. Mishra, (2009) J. Chemtracks 11(2),
16. R.V. Oppenaeur and H.Obermuch, (1949). Assoc.quim. Argent,37,246
ACKNOWLEDGEMENT
I would like to use this auspicious occasion to offer my special thanks and deep sense of gratitude to my supervisor Prof. Dr.
Anita Gupta,Assistant Professor ,SSM college,Ranchi for fruitful discussion, help comments and systematic guidance
throughout the course of investigation.
My acknowledgement are also due to Dr. H.O. Pandey, Head of Department of Chemistry, Ranchi University for inspiration and
humble co-operation.
I am thankful to Dr. S.K.Swain,Research officer and Dr. S.K.Sao,Technical Suprintendent for carring out the instrumental
analysis, FTIR curves obtained by Fourier Transform Infrared Spectrometer and TGA-DTA Thermogravimetric mass BIT
Mesra
I express a deep sense of gratitude to my Husband Shree Arun Sinha,my daughter Ms. Abhigya,my parents, Parents in-laws,
other family members.
Last but not the least, I wish to express my sincere thanks to my subordinate Ms. Sonali for her valuable contribution and cooperation in compiling the thesis. I cannot forget the immense contribution of house assistant, Ms.Shandya and Ms.Bina who
took care of my household work during this period.
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