Fifth International Electronic Conference on Synthetic Organic Chemistry (ECSOC-5), http://www.mdpi.org/ecsoc-5.htm, 1-30
September 2001

[D0008]

Mass Spectra of Some 4- and 5-Substituted Derivatives of Benzoselenadiazoles

Ján Leško1*, Viktor Milata2 and Marcel Schultz2

1Central Laboratory, Faculty of Chemical Technology, Slovak University of Technology, SK-812 37
Bratislava, Radlinského 9, Slovak Republic. E-mail: lesko@chelin.chtf.stuba.sk
2Department of Organic Chemistry, Faculty of Chemical Technology, Slovak University of Technology,
SK-812 37 Bratislava, Radlinského 9, Slovak Republic. E-mail: vmilata@cvt.stuba.sk, (http://www.chtf.stuba.sk/KATEDRY/koch/milata/viktor.htm), schultzmarcel@hotmail.com

Received: 27 July 2001 / Uploaded 7 August 2001

Abstract: Electron impact mass spectra of variety of eight 4-substituted and eight 5-substituted benzoselenadiazoles are presented and their spectral fragmentations are discussed. New mass spectra containing selenium in heterocyclic azole atom containing ring.

Keywords: Selenium, 2,1,3-benzselenadiazole, aminoethylenes, aminomethylene compounds, enamine.

Introduction

Although the mass spectra of heterocyclic oxygen and sulphur compounds have been intensively investigated [1], limited data are available in the literature on the mass spectra of benzoselenadiazoles [2, 3]. We have prepared new compounds of some 4- and 5-substituted derivatives of benzoselenadiazoles and in order to prove their structures we used mass spectrometry and 1H a 13C NMR spectroscopy.
 

Results and Discussion

The structural formulae of the compound studied in the present paper are shown in Table 1.
 
 






Table 1. 2,1,3-benzoselenadiazol-4-/or 5-ylaminoethylenes.
 
4-subst.
5-subst.
X
Y
1
9
COCH3
COCH3
2
10
COOCH3
COOCH3
3
11
COOC2H5
COOC2H5
4
12
COOC(CH3)2OCO
5
13
CN
COOCH3
6
14
CN
COOC2H5
7
15
COCH3
COOCH3
8
16
COCH3
COOC2H5

 
 
 
 
 

The relative abundances of the mass spectra 1 – 16 are given in Table 2. In the electron ionization mass spectra all of the studied compounds are observed the corresponding molecular ions, where the abundance ratio of the isotopes of selenenium is characteristic [4].
 
 
 
 

Table 2. EI mass spectra of 4- and 5-substituted derivatives of benzoselenadiazolesa,b.

No m/z (%)

1 309 M+. (27), 307 (14), 268 (12), 266 (62), 264 (31), 263 (12), 262 (11), 224 (12), 112 (11), 43 (100).

2 341 M+. (35), 309 (80), 307 (40), 282 (70), 250 (35), 249 (46), 143 (53),103 (36), 59 (57), 53 (100).

3 369 M+. (50), 323 (92), 321 (48), 296 (100), 294 (49), 249 (32), 223 (58), 221 (28), 143 (93), 53 (51).

4 353 M+. (8), 295 (29), 225 (18) ,223 (94), 221 (47), 143 (100), 116 (15),103 (17), 53 (52),43 (76).

5 308 M+. (82), 306 (42), 276 (36), 249 (61), 248 (100), 246 (55), 168 (57), 103 (50), 76 (45), 52 (54).

6 322 M+. (64), 320 (32), 276 (31), 249 (62), 248 (100), 247 (31), 246 (47),168 (31), 103 (28), 52 (35),

7 325 M+. (20), 293 (16), 282 (62), 280 (31), 250 (34), 248 (18), 223 (17), 143 (46), 53 (35), 43 (100).

8 339 M+. (41), 296 (100), 294 (59), 293 (54), 265 (44), 250 (71), 248 (37) 223 (32), 143 (80), 53 (53).

9 309 M+. (77), 307 (36), 266 (28), 252 (42), 250 (28), 224 (27), 172 (20), 143 (27), 112 (100), 70 (26).

10 341 M+. (78), 339 (39), 309 (100), 307 (50), 250 (51), 157 (50), 143 (32), 103 (36), 59 (66).

11 369 M+. (71), 367 (35), 323 (100), 321 (49), 267 (42), 250 (50), 223 (44),170 (28), 143 (68), 103 (28).

12 353 M+. (11), 295 (36), 251 (27), 250 (59), 248 (32), 223 (33), 143 (100), 76 (23), 53 (50), 43 (99).

13 308 M+. (95), 306 (46), 276 (54), 249 (71), 248 (42), 169 (69), 168 (100),103 (76), 76 (65), 52 (63).

14 322 M+. (93), 320 (45), 276 (66), 249 (95), 247 (49), 169 (100),168 (95), 103 (72), 76 (65), 52 (92).

15 325 M+. (51), 323 (26), 293 (35), 291 (18), 265 (69), 263 (34), 250 (35),248 (19), 143 (33), 43 (100).

16 339 M+. (44), 337 (21), 293 (36), 291 (17), 265 (71), 263 (35), 250 (35), 248 (17), 143 (32), 43 (100).

aTen the most abundant ions in the mass spectra are presented.

bM+. for the most abundant isotope 80Se.
 
 
 
 

The most abundant isotopes are 80Se (49,7 %) and 78Se (23,6 %). The main fragmentation pathways depend on the presence of substituents X and Y. The fragmentation of M+. with Y = COOCH3 or COOC2H5 substituents include the elimination ofCH3OH or C2H5OH to produce [M – CH3OH]+. or [M – C2H5OH]+. species, which further lose CO, and if X = CN, then the subsequent decomposition is the elimination of Se (general fragmentation scheme 1). The elimination of the radicals .COOCH3 and .COOC2H5 from M+. show a rise in abundant fragment ions in most cases, too. There are some differences between 4- a 5-substituted isomers as, for example, the fragment ion [M - .COOC2H5]+ , m/z 296 is 100 % in 6, unlike in 11, it is only 5 %. This fact can serve for distinguishing the 4- and 5-substituted isomers, respectively.
 
 

General fragmentation scheme 1





 The presence of X = COCH3 group in the molecules show a rise in fragment ions [M - .COCH3]+ with different relative abundance. If the second substituent Y = COOCH3 or COOC2H5, then the subsequent decomposition of the ion [M - COCH3]+. is the elimination of the molecule methanol or ethanol respectively. In 1 and 7, the fragment [COCH3]+, m/z 43 itself represents the base peak. If both X = Y = COCH3, the peak at m/z 112 represents the fragment ion with a probable structure [(CH3CO)2 C = CH2]+. This species is formed by b-cleavage to the aromatic ring with the hydrogen rearrangement, as it was described previously [5]. Fragment ion at m/z 112 represents the base peak in 9 (5-substituted) while in 1 (4-substituted) it is only 11 %.

Some important fragmentation scheme of the compounds 1 - 16 are presented:


 
 


 
 


 
 


 
 


 
 


 
 


 
 
 
 
 
 

Conclusion
 
 

We decided to publish the mass spectra of the new prepared selenium containing compounds as well as their fragmentation behaviour under electron impact.
 
 
 
 

Experimental
 
 

The EI mass spectra (low resolution) were recorded on a MS 902 S (A.E.I. – Kratos, Manchester) mass spectrometer using a direct probe heated to suitable temperature. The ionizing energy was maintained at 70 eV and the electron current was 100 m A. The temperature of the ion source was kept at 200°C. The metastable transitions were recorded in the second field free region.

The compounds studied in the present paper were synthesised at the Department of Organic Chemistry and the publication is under preparation (6), these results are published in (7).
 
 
 
 

References and Notes
 
 

  1. Porter, Q. N. Mass Spectrometry of Heterocyclic Compounds, 2nd Ed.; Wiley: New York, 1985.
  2. Pedersen, Ch. L.; Moller J. Acta Chem. Scand. 1975, B 29, 483.
  3. Arshadi, M. R. Org. Mass Spectrom. 1978, 13, 379.
  4. Mills, I.; Cvitaš, T.; Homann, K.; Kallay, N.; Kuchitsu, K. IUPAC, Quantities, Units and Symbols in Physical Chemistry;Black Sci. Publ.: Oxford, 1988.
  5. Milata , V.; Ilavský, D.; Goljer, I.; Leško, J.; Henry-Basch, E.; Barry, J. Bull. Soc. Chim. Fr. 1996, 133, 897.
  6. Milata, V.; Schultz, M.; Duddeck, H.; Prónayová, N.; Leško, J. (prepared for the press).
  7. Leško J.; Milata V.; Schultz M. Molecules2000, 5, 937.