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Negative ion chemical ionization mass spectrometry of some isocyanates

Osamu Suzuki 1 and Hans Brandenberger Department of Forensic Chemistry, University of Zfirich, Ziirichbergstrasse 8, CH-8028 Zfirich, Switzerland Negativionen-Massenspektrometrie mit chemischer Ionisierung von einigen lsocyanaten Zusammenfassung. Die Negativionen-Massenspektren yon 3 aliphatischen und 4 aromatischen Isocyanaten wurden mittels chemischer Ionisation bei tiefem Quellendruck aufgenommen, und zwar mit den Reagensgasen CH4, CO2 und N20. Alle Verbindungen lieferten intensive Anionen mit m/z 42. Mit CH4 erhielten wir die quasi-molekularen Anionen M + 1 f/Jr aliphatische sowie M + 1 uud M - 1 ffir aromatische Isocyanate. Das Reagens N20 ergab die anionischen Substitutionsprodukte M + 15 und M + 30. Sowohl CO2 als auch N20 fiihrten mit aromatischen Isocyanaten zur Bildung von M - 12 Anionen. Versuche mit ~3CO2 und mit C~8Oz als Reagensgase zeigten, dal3 die Anionen M 12 und M + 15 den Ionen [ M - C O + O]- und [ M - H + O]entsprechen. Summary. Negative ion mass spectra for 3 aliphatic and 4 aromatic isocyanates have been obtained by low pressure chemical ionization, using CH4, CO2 and N20 as reagent gases. All compounds furnished intense anions at m/z 42. With CH4, quasi-molecular anions were observed at m/z M + 1 for aliphatic and m/z M + 1 and M - 1 for aromatic isocyanates. With N20, anionic substitution products at m/z M + 15 and M + 30 were observed, and with CO2 and N20, peaks at m/z M - 12 could be detected for all aromatic isocyanates. Studies with 13CO2 and Ct802 as reagent gases showed that the anions at m/z M - 1 2 and M + 15 correspond to [ M - CO + O]- and [ M - H + O]-, respectively.
also briefly studied using two isotopically labeled reagent gases.

CO 2 as

Experimental
Phenyl isocyanate, l-naphthylisocyanate, toluene 2,4diisocyanate, propyl isocyanate, butyl isocyanate and cyclohexyl isocyanate were obtained from Fluka AG, Buchs, Switzerland; diphenylmethane 4,4'-diisocyanate from Merck, Darmstadt, West Germany; and carbon- t 3C_dioxide and carbon dioxide-1802 from Merck Sharp & Dohme, Canada Limited, Montreal, Canada. Except for diphenylmethane 4,4'-diisocyanate, all isocyanates were dissolved in n-hexane. Diphenylmethane 4,4'-diisocyanate was dissolved in benzene. About 1 gl of the solution containing 1 - 5 gg of the compounds was injected into the port of the gas chromatograph (GC). The instrument used was an LKB 2091 GC-MS combination unit, modified for CI MS as described by Ryhage [2]. For work in the negative CI mode, the polarities of the magnetic current, accelerating voltage and repeller voltage were reversed [3]. GC conditions and retention times of the respective compounds were as follows. Phenyl isocyanate: 1.5 m x 2 ram, 3% OV-17 on Chromosorb G-HP, 150~ retention time (RT) 1.5 min; 1-naphthylisocyanate: 0.5 m x 2 ram, 3% SE-30 on Chromosorb G-HP, 150~ RT 2.9 min; toluene 2,4-diisocyanate: 0.5 m x 2 ram, 3~ SE30, 150 ~C, RT 1.6 min; diphenylmethane 4,4'-diisocyanate: 0 . 5 m x 2 m m , 3% OV-17, 250~ RT 2.3rain; propyl isocyanate: 1.5 m x 2 ram, 3% OV-17, 80~ RT 1.8 rain; butyl isocyanate: 1 . 5 m x 2 m m , 3% OV-17, 80~ RT 1.6 min; and cyclohexyl isocyanate: 1.5 m x 2 ram, 3% OV17, 150~ RT 1.3 rain. Injection temperature was about 20~ higher than the column temperature, and helium flow rate was 10 ml/min. Negative CI mass spectra were recorded with CH~, CO2 and N20 as reagent gases, at a chamber pressure of about 1 x 10 -2 Torr except with C1802. Other negative CI MS conditions were: accelerating voltage, 3,5 kV; total electron emmission, 500 gA; electron energy, 250eV; separator temperatures, 225 ~C; and ion source temperature, 260 ~C. Positive EI mass spectra were run at 70 eV.

Introduction
Isocyanates are extensively used in the production of flexible and rigid foams, polyurethane paints and adhesives. Thus a large number of industrial workers are exposed to isocyanates, which are known to irritate the respiratory tract and very often cause asthma-like symptoms. Although mass spectrometry (MS) of isocyanates by positive electron impact (EI) has been reported [1], negative ion chemical ionization (CI) MS of these compounds remains to be explored. The present paper deals with negative CI mass spectra of seven isocyanates commonly used in industry. The mechanisms of formation of some anions were
Present address: Department of Legal Medicine, Hamamatsu

Results and discussion


Negative CI mass spectra of isocyanates

University School of Medicine, Hamamatsu 431-31, Japan Offprint requests to: H. Brandenberger
Fresenius Z Anal Chem (1987) 326:228-231 9 Springer-Verlag 1987

The negative CI mass spectra of the seven isocyanates, together with their positive E1 spectra for comparison, are

Orilinalarieil~#

'~176 5~
%

70 eV

[M-28]*

#;
II, ,

Mr

119

64
, ..... . s'o ' ' 1~o ' . . 40 . . .
/z

100 CATIONEI t% 70 e"v" 50

Mr 174

TOLUENE 2,4-OIISOCYANATE

145

M,~

100fl'2AN'O-+120 oH.OI ,. 1,
Ill,..IlL

'

2~o

o,

,LL Jll,. ., J.,,,.. i ..,I ...... iJl...... ,.... i I ,

,,IL .....
. . . .

50

11~0

"~ 'i~ ,~!?""


1~o . . . .

r
2~o '

m/z

% 5O

ANION
CI CH, CH3

N,C=O N-C,O 102 [M-l]- [M+1]173 175


, I..I.; "r'" ' "1';~o "' ' .[.I. '"' 2~0 i , m/z

50

NmC=O

122

o, " Jo

....

~o ' '"

' ,~o . . . .

40

,j, ,

rn/z

Oi

. . . . . . . . . . . . . . . .

510 ~ 1001 % 50 42 ANION OI CO=

'

'

' 1~0

'~176 A?SNco, f'" ,I~~],o "i I~pl-I IM+,=-13,,


50 10!f ANION % C.~ N20 5 100 [M'281.12]. 91 [M+15]134
[M+30]" . . . . . . . .

102 J li 2 .,.... I., .,, ,. t b........ II........... . . . . I~o . . . . I.I,,.


I~O h44

[M-12]162 . ,
' '

150

200

m/z

C, ....
510

I..
, "i 2~0 '

m/z

% 5

CI N20 104

119

[M-2]" [M-28]" 172 1146 I [M+151l, IMq2]-II 189 162

[[
L

[M+30]~

I I..

.!o.7

149

i .i.

"so "'

'

' ,,~o'

,Io . . . .

2~o"

, m/z

510

,,,, J

,I........ ,.,.. J,L.


i i

100

J,l,., i

LJ.....i ,

1~0

..... ,

I,

'

~?

2/o

mlz

Fig. 1. Positive E1 and negative CI (CH4, CO2 and N 2 0 as reagent gases) mass spectra of phenyl isocyanate. Anion spectra below m/z 45 with N20 were not recorded owing to the interference of anions from the reagent gas

Fig. 3. Positive EI and negative CI mass spectra of toluene 2,4-

diisocyanate

100f7 ATON'TEJ50114 1.M'141L: 1"NYL--Y' EIev"" O


o, .,L. h. ,

,ll,

..J,,.

.,.

hn.

510 . . . .

1~0 '

'"'

., ' 1~0 . . . .

200

m/z

so

/
'

0,..,.
................ 50 . . . . ~0 . . . .

,,~ ~4o/
,1[

%,,_ ["'1~....... 1, ...... ~0 . . . .

0 i' I

2(J0

m/z

I i!fNONNo --.__-~ o~'o . . . . ~AOo ' ' ' ' .0~o"' '

2kOo "rn'z

,4o ;~o

=;
CI

l[~+~o]m,z
mass spectra

" '" ' s ''


and

+ l,~od~,
negative

k.+ ,.I.,.~i+o

Fig. 2. Positive EI
naphthylisocyanate

of 1-

presented in Figs. 1 - 7. We have used three different reagents, viz. CH4, CO2 and N 2 0 , in the negative CI mode, because these gases often give different spectra by different reaction mechanisms. With CH4, electron attachment dominates, while N20 yields O- and [NO]-, which ionize

substrate molecules by the exchange of negative charge; CO2 is capable of reacting by either electron attachment or charge exchange [4]. The different reagent gases yielded different negative ion spectra (Figs. 1 - 7 ) . For all aromatic isocyanates (Figs. 1 - 4), the positive EI spectra showed molecular cations which constituted the base peaks, while negative CI spectra with CH4 as reagent gas gave quasi-molecular peaks at both m/z M + 1 and m/z M-~ 1. The M + 1 peaks are formed by the addition of H generated in the ion source from CH4 [4]. Peaks at m/z M - 2 (loss of 2H) appeared in some spectra of aromatic isocyanates with the reagent N20 (Figs. 2 - 4 ) . Peaks at m/z M - J 2 were observed for all spectra of aromatic isocyanates with COz and NzO (Figs. 1 - 4 ) . Anions at m/z M + 15 were detected in the spectrum of phenyl isocyanate with COz (Fig. 1) and also in all spectra of aromatic isocyanates with N20 (Figs. 1 - 4 ) . Peaks at m/z M + 30 were also detected with N20; they were clearly visible for the diisocyanates (Figs. 3 and 4), but very small for the monoisocyanates (Figs. I and 2). Anions at m/z M - 2 8 (loss of CO) were commonly observed in all spectra of aromatic isocyanates with N20 as reagent gas. The spectra of aliphatic compounds, viz. propyl and butyl isocyanates (Figs. 5 and 6), were quite different from those of the aromatic compounds. Positive EI spectra of both aliphatic isocyanates gave quasi-molecular peaks at m/z M-I, and fragment peaks at m/z 56, probably due to a cleavage in e-position to the nitrogen atom. In the spectra with CH4, anions at m/z M + 1 appeared, but those at m/z M - 1 found for the aromatic isocyanates showed up only weakly. The spectra taken with CO2 and N20 showed peaks at m/z 72 (Figs. 5 and 6), which probably correspond to [56 + 0]-. Cyclohexyl isocyanate (Fig. 7) gave a small molecular cation in the positive EI mode and a quasi-molecular anion
229

100

r
CATION
E!

%/ 50

~ ~o

70 eV

208 221

o. ~
' 510 .

J~_J_,L, ........ ,L., ,.,L


. . . 11~0 ' ' '

!
' W" 2 , ,

,,,
, ,

2~0` '

I
'

'

'

'

mlz

ANION CZ CH,

Cl

J 510` . . . . . . 1. . ANION CI CO=

. _ ~... L. .. ' 1~o '

I .....,

'~o

'

2~o

.lb '~+'"

'

z m/z

1!f
%/ El

148

i,0
L

[M-12]"

, ~o , ,

,, ,~;,

~.,

,~o ,_~ ~,. ,%..,

.,L

:~ ~o ,~ . . . .

,~

"~'oN CI
N20 1i

2Z0"l1222

I ~'0`(M+~sl265
t [M+3Q]"

o0roN Ii
70 eV

~0 .

. . .

1(~0.

. . .

I~0 .

. . .

i 'M'12]-" i T '~)0. . . . 2~0


% 41 43

PROPYLISOCYANATE
Mr 85

1~176
56 50 100 %t 50

Fig, 4 Positive EI and negative CT mass spectra of diphenylmethane 4,4'-diisocyanate


CATION 70 eV

BUTYLISOCYANATE
Mr 99

501

42

[M.1] 84 I'

[M-l]* 7O
,= ...... d .

o/'

,,fl ....... b"10

Ih

1'00

, m/z

o'

5'o

. ..h.

'

Ti
, I ~ 1"0(]

rnlz

10or AN,ON =/ | CI

50

=il
I
ANION

I}'2
56 50
i i ,,,

CH3"CH2"CH;oN=C=O [M +1186 I ,

2 ANION C'f CH, [M+1]100

o' % 50

,1, ,

I '

100

,,

, ,

m/z

o' %

i,l..

5~0

''

100

mlz

CI COs

412ANIONco=CI

, 1,72,,

72

5~

CH..=-CI-I='-CI~- =C=O CI~..-N

0.

~f
I 5D

J,

~~
,,, '

,,,

. '

. '

100"

1'

mlz

'

s'o
ANIONN~oCI [2

"I'II

100

;**'"

_mlz

ANIONN2oCI

0,i[

56

~o

.~l.l.h

16o

=m/z

....

Jo

.L..

,,I

m/z

Fig. 5. Positive ET and negative CI mass spectra ofpropyl isocyanate

Fig. 6. Positive EI and negative CT mass spectra of butyl isocyanate

at m/z M + 1 with CH4 as reagent gas. In the spectrum with NzO, some peaks below m/z 100 and a small addition product at m/z M + 15 were observed. Strong peaks at m/z 42 (NCO) were noted in almost all spectra taken with CH4 and CO2 as reagent gases (Figs. 1 7), suggesting that this peak can be used to screen the isocyanate group. In our trials, the peak at m/z 42 is not shown in the spectra with N20, since we did not record the 230

spectra below m/z 45 owing to the interference of the reagent gas anions.

Sensitivity of negative CI MS
The sensitivity of negative CI MS for isocyanates was checked by monitoring the total ion currents. It varied according to the nature of the compound and the reagent

100 % 50

CATIONEI 70 eV 41

67

82

97

1!i}- A
" 4

CO= I X 10~Torr

~0Mi12][M'201-1
90

,~IENYL I$OCYANATE Mr119

125
c,
100 % 50 [M+II" Oi t'" c'l CN,

M+

, Ih ....

I .

.... I, . . . .

'1

,1.

150

II1/Z

C=

f
.

1M+151-

91

114 1~0 . . . . "2~0


m/z

........ ]l . . . . . . . Lh. . . . . . . . . . . . . .

510 . . . .
,.,o.,o+

1(~0 . . . .

CYCLOI'~E L ISOCu X~f


Mr 1~5

i 50

N-C=O
9091

go
CI ~N=C=O

'

10o 107

,],

126

- m/z

I .

5 i~

,...+

4"41 ...... " II

1~0

'

L ,.. '

+l.
' '

i I''

' ' I 200

m/z

'1+ 150'

~'

100[ 50

CO: 42 ANION

O,
% 5

........ 5i0
CI ANION

i 59 ,,, l J

... ;.

.;..... , .,.I .... J..~ 1~0 196

ph

150

m/z

,ool
,,,

91

107
[M+151"

o, "i I' ,' , i' ,' 11~ 'i' 1,3,4, I " ' ;- ,
50 100 150 2/0

.~1

mix

N=O 50

50
[M+151-

.......

I. . . . . . .

,l.,

....

14~1
I

[M-28Y [M-10191 109 90 107


' so;

[M+171,!~,

t0g

m/z

Fig. 7. Positive EI and negative CI mass spectra of cyclohexyl isocyanate gas used. With our instrument, the intensity of the total ion current in the negative CI mode was about 1 0 - 5 0 % of that in positive EI mode. The sensitivity of negative CI MS for aromatic isocyanates is somewhat better than for aliphatic isocyanates.
Studies with

0,

,,,,'v

~,'1ooi"d'1~,..;

+~o" ,

't'"

, "2~0 ~

~l~

Fig. 8 A - D . Negative CI mass spectra of phenyl isocyanate with CO2, 13CO2 and C18Oz as reagent gases. The spectra with 13CO2 and C1802 were measured at 1 x 10 -z and 3 x 10 -3 Torr, respectively. The reference spectrum with unlabeled C O / a t 3 x 10-3 Torr is also given. A - D see text

13CO2and Ca802

as reagent gases

To investigate the mechanisms of the formation of some anions in the spectra with CO2, we replaced the t2CO2 by laC-labeled and by 180-labeled CO2. The results are presented in Fig. 8 for phenyl isocyanate. The spectra were recorded at I x 10 -2 Torr with tsCO2 and at 3 x 10 -3 Torr with C1802, due to the low pressure in the C~802 bottle we had obtained. Therefore, a control spectrum with COz at 3 x 10- 3 Tort is also presented in Fig. 8 C. Some quantitative differences in the patterns could be noted by comparing the spectra taken at different pressures. At 3 x 10 -3 Torr (Fig. 8C), the peak at m/z 42 became the base peak and the M-12 peak was much smaller than at 1 x 10 -2 Torr (Fig. 8 A). With 13CO2, the spectrum remained unchanged (Fig. 8B), but with CtSOz, the M-12 and M + 15 anions, observed with normal COz, shifted to m/z M - 1 0 and M + 1 7 , respectively (Fig. 8D), This proves that these

anions contain single oxygen atoms derived from the reagent gas. We can therefore conclude that the M - 1 2 and M + 15 anions correspond to [ M - C O + O]-, and [ M - H + O]-, respectively. The experiment with C18Oz was also carried out with butyl isocyanate. The peak at m/z 72 shifted to m/z 74 (spectra not shown), supporting the view that this anion is formed by addition of O - to the product at m/z 56.

References

1. Ruth JM, Philippe RJ (1966) Anal Chem 38:720 2. Ryhage R (1976) Anal Chem 48:1829 3. Brandenberger H, Ryhage R (1978) In: Frigerio A (ed) Recent developments in mass spectrometry in biochemistry and medicine, vol. 1. Plenum, New York, p 327 4. Brandenberger H (1980) In: Frigerio A0 McGamish M (eds) Recent developments in mass spectrometry in biochemistry and medicine, vol. 6. Elsevier, Amsterdam, p 391
Received March 13, 1986

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