Mass spectra ofN-arylaminosulphonylcarbethoxydiazoacetamides

ORGANIC MASS SPECTROMETRY, VOL. 26, 789-792 (1991)

Mass Spectra of N-Arylaminosulphonylcarbethoxydiazoacetamides Albert T. Lebedevt Organic Chemistry Department, MOSCOW M. V. Lomonosov University, Moscow, 119899, USSR

Vasily A. Bakulev and Mikhail Yu. Kolobov Department of Technology of Organic Compounds, Polytechnic Institute, Sverdlovsk,USSR

The electron impact mass spectra of N-arylaminosulphonylcarbethoxydiazoacetamideswere studied. On the basis of high-resolution mass spectrometric data, mass-analysed ion kinetic energy spectrometry and linked scan experiments a detailed scheme of the fragmentation is proposed. A number of possibilities of charge localization are revealed in the complex decomposition processes of the molecular ions.

spectrometer operating at the same source temperature and electron energy.

INTRODUCTION Continuing our studies on the mass spectrometry of diazo compounds, we have investigated the electron impact (EI) mass spectra of N-arylaminosulphonylcarbet hoxydiazoacetamides 1-5. These compounds are used in the synthesis of 2-aza analogues of the aglycone of the anticancer antibiotic predimine.' In addition, owing to their different functional groups, they may be used widely as precursors of a range of compounds. GI 15+-C-C-C-NHS02NHAr I1

0

I1 11 N2 0

RESULTS AND DISCUSSION The complexity of these compounds makes their fragmentation patterns complicated. However, application of high-resolution mass spectrometry, MIKES and limked scan techniques permitted a detailed scheme of the fragmentation to be established (Scheme 1).

c&c+-C-G-CNH2 I1

0

1-5

I1 I1 N2 0

6

EXPERIMENTAL CzH50-C-C-C-NHS02NHAr

All the compounds studied were prepared at the Polytechnic Institute, Sverdlovsk, USSR, by using a known method.' Their purity was checked by thin-layer chromatography and their structures were confirmed by 'H and 13C NMR spectrometry. The EI mass spectra were determined with Kratos MS30 mass spectrometer operating at 70 eV, with a source maintained at 220 "C.The sample itself was not heated in the direct inlet system in order to minimize thermal decomposition processes. The compositions of all key fragments were confirmed by high-resolution mass spectrometry carried out with the same instrument by manual peak matching. Massanalyzed ion kinetic energy (MIKE) spectra (second field-free region) and B/E and B2/E spectra (first fieldfree region) were determined with a VG ZAB-2F mass

I1

I1

0

0

?ArNHSO,NHCO'

IM-Nd+'

A~NHSOJ

*I:

+. CZHSO-C-C-C-NHNHAr

t:H\\ I1

I1

O

O

~H,O-C-C-NHSO,NHA~

C,H,OSO,N~!

f .

ArC3HO2d*

ATT302N:

C2H50-C-C-NHNHAr

K+. -H: k \

ArC2HON2

-H&N

ArCHN2

t.

ASON*'

kc,.:

C6H4N2

r

0030-493X/91/090789-04 $05.00 0 1991 by John Wiley & Sons, Ltd.

M ~ H ~ OI N Z

/&j/+:,*

I.

s

t Author to whom correspondence should be addressed.

:

ArCHZN:

AKHNO+

P

0

q

Scheme 1

Received 18 January 1991 Revised manuscript received 19 April 1991 Accepted 23 April 1991

A. T. LEBEDEV, V. A. BAKULEV A N D M. Yu. KOLOBOV

790

Table 1. Relative abundances of the common fragments in the mass spectra of diazocompounds 1-5 (% of the total ion current) Ion b

C

d

1.5 0.4 0.3 0.8 0.1

1.9 3.3 1.1 2.6 0.7

1.1 1.3 0.8 1.4 0.4

0.1 0.2

0

P

4

r

S

f

10.1