Annexes Liste des principaux fragments ioniques

Ali fragments listed bear + 1 charges. To be used in McLafferty's lnterpretative book, and the high-reso­

conjunction with Appendix C. Not ail rnembers of ho­ lution ion data of McLafferty are recornmended as

rnologous and isomeric series are given, The lis! is suppléments. Structural inferences are listed in paren­

meant to be suggestive rather than exhaustive. Ap­ theses.

pendix Il of Hamming and Foster, Table A-7 of

m/z lons- (Structural Inférence) mh Ions- (Structural lnfcrcnce)

0
14 CH,
,I'
,s CH,
58 CH,-C + H, C,H,CHNH,. (CH,),NCH,,
16 0 -,
17 OH CH,

18 H,O, NH, C,H,NHCH,, C,H,S

19 F, H,O 0

26 C�N, C2H2 Il

59 (CH,)2COH, CH,OC,H,, C-OCH, (RCO,CH,),

27 C,H,
NH,C=O + H. .
28 C,H,, CO, N, (air), CH=NH
1
29 C,H,, CHO
CH,
30 CH,NH, (RCH,NH,), NO
CH,OCHCH,, CH,CHCH,OH, C,H,CHOH
31 CH,OH (RCH,OH), OCH,
0
32 0, (air)
/
33 SH. CH,F 60 CH,C, + H. CH,ONO
34 H,S
OH
35 Cl ("Cl at 37)

36 HCI (H "Cl at 38)

?i
39 C1H3
61 CH,C-0 + 2H, CH,CH,SH, CH,SCH,
40 CH,C=N, Ar(aîr)
65 C,H,
41 C,H,, CH,C=N + H,• C,H,NH

42 C,H,. C,H,0 66 O e C,H,, H,S, (RSSR)

43 C,H,. CH,C=O, CH,C=OG, G = R, Ar, NH,,

OR, OH, C,H,N 67 C,H,

68 CH,CH,CH,CsN
H
69 C,H,, CF,, CH,CH=CHC=O,
1

CH,C=O + H (Aldehydcs, McLafferty CH,=C(CH,)C=O

44
Rearrangement), CH,CHNH,, CO,, NH,C=O
70 C,H,.

(RC=ONH,), (CH,),N 71 C,l-1 11, C,H,C=O

0
CH, /
1
72 C,H,C, + H, C,H,CHNH,, (CH,hN=C=O,
CHOH. CH,CH,OH, CH,OCH, (RCH,OCH,),
45
CH,
0
Il
C,H,NHCHCH, and isomers
C-OH, CH,CH-0 + H (CH,CHOHR) 73 Hornologs of 59, (CH,),Si

46 NO,

47 CH,SH (RCH,SH), CH,S

î
74 CH,-C-OCH, + H
48 CH,S + H

49 CH,CI (CH, "Cl al 5 1 )

î ?i
SI CHF,, C,H, 75 C-OC,H, + 2H. C,H,CO + 2H, CH,SC,H,,

53 C,H, (CH,),CSH, (CH,O>,CH, (CH,>,SiOH

54 CH,CH,C=N 76 C,H, (C,H,X, C,H,XY)

SS C,H,. CH,=CHC=O 77 C,H, (C,H,X)

56 C.H, 78 C,H, + H

57 C,H,, C,H,C=O 79 C,H, + 2H, Br ("Brat 81)

"lons inidic.ated as a fragment + ,,H (n • I. 2, 3, , . .) are ions that arise via rcarrangement involving hydrogen transfer.
 A nn�� ,s- (�)

Appendix B (continued)

80 0-CH,,o�
94 0- 0 + H , v C = O
N N
1 1

H CH,
H

CH,SS + H · HD r (H" Br at 82)

[31-c=O
0

81
Q-cH,, C,H,, 6 96 CH,CH,CH,CH,CH,CaaaN

97 C,H,,, [31-cH,
82 CH,CH,CH,CH,Cee,N
s
CCI, (C"Cl"CI at 84, C"CI, at 86

C , H , , , CHCI, (CH"Cl"CI al 85 ). C,H., 98 [31-cH,O + H

83

CH"CI,. at 87), CJ-

85
C,H ,,, C,H,C=O, s 99 C,H,,, C,H,,O. Q
CCIF, (C"CIF, at 87). Q. � 0 0

0
,;P o o o /
100 C,H,C + H. C,H,,CHNH,
C,H,C '" + H . C,H,CHNH l and
-,
86 .... .
rscrners

CH,
0
0
Il

c Il
101 C-OC,H,
87 ,H,CO, hornologs of 73, CH,CH,COCH
0
"Il '
Il
0
102 CH,C-OC,H, + H
0
0
Il
Il
88 CH,-C-OC,H, + H
103 C-OC,H, + 2H C H
C,H,CHONO, . ' ,,$, CH(OC�l,CH,l,
104
0
Il
89 C-OC,H, + 2H, 0-C
105 o-c o,

[C,H,(C=O)G , G - OH , OR, OAr, halogen, NH,]

90 CH,CHONO,, 0-CH

0-CH,CH,, 0-CHC�;

0-CH, (C,H,01,Br), 0-CH

91
106
6CH,
+ H . o- C + 2H,

o-CH,OÇ&OH
(CH,),CI [(CH,),"CI, al 93] ON

107

CH, 0-CH,
92
G- N
-• + H
• C
,H,Br (C,H.'' B r a t 109)
OH

93 CH,Br (CH,"Br al 95 • RCH , B r). C,H,. hr-cH,O

108 V + H, (jl-c=o
r=J OO
ls,,N
_ _ .,)=C=O ' • C,H, (terpènes)
�
CH,
Appendix B (continued)

109
aC=O 127

128
l

HI

mCH,
130
li I ()-C=O

s 1

H
119 CF,CF,,
0

0-r- C-CH,
Co-
CH,.
6- CH,
131
C,F,, 0- Il
CH=CH-C

135 (CH,),Br [(CH,)!'Br at 137]

,l'o. 0

Il

O=��+H
(XC
120 138

C=O
-l'o

121
6- 0 H .
&=, CXN 139 6-c,
NH

C,H., (terpencs) 141 CH,! (RCH,1)

147 (CH,J,Si=O-Si(CH,),
0

I
l 0
122 c.H,C-0 + H, (C,H,CO,R) Il

C=O
149 o:CO + H

123
& F.
oIl

C,H,C-0 + 2H,
c'

0
Il

154

0-0
125 o-s-o
Annexe 6 Liste des principaux fragments neutres (radicalaires ou non)

This list is suggestive rather than comprehensive. It Lafferty are recommended as suppléments. Ali of these

should be used in conjunctlon with Appendix B. Table fragments are lost as neutral species.

5-19 of Hamming and Foster and Table A-5 of Mc-

Molccular

Ion

Minus Fragment Lost Inférence Structure

1 H·

2 2H·

15 CH,·

16 0 (ArNO,. amine oxides, sulfoxidcs); · NH, (carboxamidcs, sulfonamiëes)

17 HO·

18 H,O (alcohols, aldehydcs, ketones)

19 F·
20 HF

26 CH=CH, · CH""'N

27 CH2=CH ·. HC:==N (aromatic nitrites, nitrogcn heterocycles)

28 CH,=CH1• CO, (quinoncs) (HCN + H)

29 CH,CH, •, (ethyl ketones, ArCH,CH,CH,). · CHO

30 NH1CH1 •, CH,O (ArOCH,). NO (ArNO,). C,H,

31 · OCH,(methyl esters), · CH,OH, CH,NH,

32 CH,OH, S

33 HS· (thiols). (· CH, and H10)

34 H,S (thiols)

35 Cl·

36 HCl, 2H,O

37 H,CI (or HCI + H)

38 C,H,. C,N, F,

39 C,H,, HC,N

40 CH,C=CH

41 CH,=CHCH,·

H,

/c,
42 CH,=CHCH,. CH,=C=O. H,C--CH,, NCO, NCNH,

0 0
Il Il

C,H,·(propyl kctones, ArCH,-C,H,). CH,C•(mcthyl ketones, CH,CG, where G =

43
various functional groups), CH,-CH-0 ·, (CH,· and CH,=CH,). HCNO

44 CH,=CHOH. CO, (esters, anhydrides), N,O. CONH,, NHCH,CH,

45 CH,CHOH. CH,CH,O ·(ethyl esters), C01H, CH,CH,NH,

46 (H10 and CH,=CH1), CH,CH,OH, · NO, (ArNO,)

47 CH,S ·

48 CH,SH, SO (sulfoxides), O,

49 ·CH,CI

SI ·CHF,

52 C,H,. C,N,

53 C.H,
54 CH,=CH-CH-CH,

55 CH,=CHCHCH,

56 CH,=CHCH,CH,. CH,CH=CHCH,. 2CO

57 C,H, • (butyl ketoncs), C,H,CO (ethyl ketones, EtC=OG, G = various structural unies)

58 · NCS, (NO + CO), CH,COCH,, C,H,0

Appendix C (continued)

O o 1

I
l .S..
Il

59 CH,Oé -, CH,CNH,. U

60 C,H,OH, CH,=C(OHJ, (acétate esters)'

S·
61 CH,CH,S·, D
62 (H,S and CH,=CH,)

63 ·CH,CH,CI

64 C,H,, S,, SO,

CH,

CH,=C-CH=CH,
68

69 CF,·, C.sH9·

71 C.sH,,·

Il

CH,CH,OC·
73

74 C,H,OH

15 C,H,

76 c.a, es,
77 C,H,, CS,H

78 C,H,. CS,H,. C,H,N

79 B r · , CsH.,N

80 HBr

8S •CCIF,

100 CF,=CF,

119 CF,-CF,·

122 C.H,COOH

127 1 .

128 Hl

•Mcl...affe:rty Rearrangernent.