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Mass Spectros
Mass Spectros
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bromine vinyl chloride methylene chloride
spectra show that Cl is also composed of two isotopes, more abundant with
mass 35Da, & minor isotope 37Da.The isotopic composition of Cl & Br is : Cl:
75.77% 35Cl & 24.23% 37Cl ; Br: 50.50% 79Br & 49.50% 81Br. Presence of Cl or
Br in a molecule or ion is easily detected by noticing the intensity ratios of ions
differing by 2Da. In case of CH2Cl2,molecular ion consists of three peaks at m/z
=84, 86 & 88Da & their diminishing intensities may be calculated from natural
abundances given above. Loss of Cl atom gives two isotopic fragment ions at
m/z=49 & 51Da, clearly incorporating a single Cl atom. F2& I2 are mono isotopic
, having masses of 19Da & 127Da respectively. Presence of halogen atoms in a
molecule or fragment ion does not change odd-even mass rules given above.
Fragmentation ; The fragmentation pattern of the spectra beside the
determination of the molar weight of an unknown compound also suitable to
give structural information, especially in combination with the calculation of
the degree of unsaturation from the molecular formula (when available). Neutral
fragments frequently lost are carbon monoxide, ethylene, water,ammonia,
and hydrogen sulfide.
fragmentations arise from:
•homolysis processes. An example is the cleavage of C-C next to a heteroatom
butylpentanoate
The loss of a methyl radical generates the base peak at m/z=95 Da. The
m/z=81 & 67 ions are smaller homologues of this ion (14 mass units less).
Cyclohexene compounds undergo a retro-Diel-Alder rearrangement to give
diene and alkene fragments. The charge may reside on either fragment, with
the larger usually predominating. In this case both ions are relatively strong
(m/z=54 & 56).
4,4-dimethylcyclohexene
Molecular formula and index of Hydrogen deficiency (IHD) ; There is no
simple way of predicting how many isomers a given molecular formula will
yield, (it can range from one to many). Structures are different if they cannot
be superimposed upon one another. Keep in mind that there is rotation about
all single bonds not involved in a ring, but not about double bonds. Because all
of the formulas that you will be dealing with are based on the C atom, it may be
useful to review the ways that C can bond to itself and to other atoms. We will
limit ourselves, for now, to the C atom with four bonds. Below are the possible
combinations of C having a total of four bonds.
In a hydrocarbon where all the C atoms have only single bonds & no rings are
involved, the compound would have the maximum number of H atoms. If any of
the bonds are replaced with double or triple bonds, or if rings are involved,
there would be a “deficiency” of H atoms. By calculating the index of hydrogen
deficiency (IHD), we can tell from the molecular formula whether& how many
multiple bonds & rings are involved. IHD is also called Degree of Unstaturation.
This will help cut down the possibilities one has to consider in trying to come up
with all the isomers of a given formula. Here is a summary of how the index of
hydrogen deficiency (IHD) works.A double bond and ring each counts as one
IHD.A triple bond counts as two IHD.
Hydrocarbons (CxHy): IHD = (2x + 2 - y)/2 (where x and y stand for # of C and
H respectively.)
Example 1 ; IHD for C2H4 is (2(2) + 2 - 4)/2 = 1
This means it can have either one double bond or one ring. It cannot have a
triple bond. Since you cannot form a ring with only two C’s, it must have a
double bond.
Example 2 ; IHD for C4H6 is (2(4) + 2 - 6)/2 = 2
This means it can have either one double bond and a ring such as or two
double bonds such as CH2=CH−CH=CH2 or CH2=C=CH−CH3 or two
rings , or one triple bond, such as CH3C≡CCH3.
Compounds Containing Elements Other than C and H
•O and S atoms do not affect the IHD.
•Halogens (F, Cl, Br, I) are treated like H atoms (CH2Cl2 has the same IHD as
CH4).
•For each N, add one to the number of C and one to the number H (CH5N is
treated as C2H6. CH4N2O is treated as C3H6 by adding 2 to # of C & 2 to # of H).
•Do not forget that when double bonds & rings are involved, geometric
isomers are possible.
Index of Hydrogen Deficiency (IHD) — a Way to Get Useful Information
from a Molecular Formula ; A fairly simple calculation based on the molecular
formula of a molecule gives information about total number of pi bonds &/or
rings that are present in molecule. The method can't tell the difference between
pi bonds & rings; it only gives the total. It involves noting number of hydrogens
in the molecular formula, & comparing that number with the number that would
be present in an acyclic saturated hydrocarbon having the same number of C-
atoms. Consider the following series of molecules, all having 5 carbon atoms:
molecular general
name structure formula formula
pentane CH3 CH2 CH2 CH2 CH3 C5H1 2 Cn H2n+2 (acyclic alkane)
Therefore,C10H16 has a total of 3 pi bonds &/or rings. You can't tell how many of
each.
Calculating IHD for molecules containing O, N. or halogens
The presence of heteroatoms in a molecule may or may not make a difference
in how one calculates Hsat. Consider first the effect of oxygen. Ethane is C2H6,
ethanol is C2H6O and dimethyl ether is also C2H6O. Notice that the presence of
oxygen has no effect on the number of H's found in the molecules. Now
consider ethylamine (CH3CH2-NH2 = C2H7N) or dimethylamine (CH3-NH-CH3 =
C2H7N). Notice that the presence of one N increases the number of hydrogens
by 1. Finally, consider chloroethane (CH3CH2-Cl = C2H5Cl). Notice that the
presence of one halogen reduced the number of hydrogens by 1. In all of these
cases, the molecules are saturated and contain no rings.
In summary, the presence of oxygen has no effect on the calculation of Hsat,
but it must be reduced by 1 for each halogen present, and increased by 1 for
each nitrogen. The formula for calculating Hsat for the general case is then given
as follows, where X is the number of halogens in the molecule, and N is the
number of nitrogens. Hsat = (2C + 2) – X + N . As an exercise, calculate IHD for
C7H10ClN3O3. If you have done it correctly, you will find that IHD = 4, which
means a total of 4 rings and/or pi bonds. Any rings may or may not contain the
N or O, and pi bonds may be between two carbons (C=C, CC), carbon and
oxygen (C=O), carbon and nitrogen (C=N, CN), two nitrogens (N=N), or
nitrogen and oxygen (N=O). You can't tell from the IHD alone.
Practice problems
Calculate the IHD for each of the following and see whether it corresponds to
the structure shown.
a) b) CH3CHCHCH2CHCH2
d)
c)
e) CH3C≡CCOCH3
Answers
a) IHD = 3 ; b) IHD = 2 ; c) IHD = 5 ; d) IHD = 1 ; e) IHD = 3
Q1; An organic compound (A) is composed of carbon, hydrogen and nitrogen,
with carbon constituting over 60% of the mass. It shows a molecular ion at
m/z=112 amu in the mass spectrum.
1. Write a plausible Molecular Formula for compound A: C6 H12 N2
2. How many Rings + Double Bonds must be present in compound A? (2
rings and/or double bonds)
Q2;Another compound, B, composed only of carbon, hydrogen and oxygen,
also shows a molecular ion at m/z=112 amu.
3. Write a plausible Molecular Formula for compound B, assuming it has three
double bonds and no rings. C6H8O2
Q3;Compound C is composed only of carbon, hydrogen and oxygen, and
shows a molecular ion at m/z=180 amu. Carbon accounts for 60% of the
molecular mass.
4. Write a plausible Molecular Formula for compound C. C H O
5. How many Rings + Double Bonds must be present in compound C?
C9 H8 O4; This is Aspirin ; 6 rings and/or double bonds
Fragmentation Patterns of Different Organic Compounds ; The
fragmentation of molecular ions into an assortment of fragment ions is a mixed
blessing. The nature of fragments often provides a clue to molecular structure,
but if molecular ion has a lifetime of less than a few microseconds it will not
survive long enough to be observed. Without molecular ion peak as reference,
the difficulty of interpreting a mass spectrum increases markedly. Most organic
compounds give mass spectra that include a molecular ion. Among simple
organic compounds, most stable molecular ions are those from aromatic rings,
other conjugated pi-electron systems & cycloalkanes. Alcohols, ethers & highly
branched alkanes generally show greatest tendency toward fragmentation.
Fragmentation Patterns of Aliphatic Hydrocarbons The mass spectrum of
dodecane (on next page) illustrates the behavior of an unbranched alkane.
Since there are no heteroatoms in this molecule, there are no non-bonding
valence shell electrons. So, the
radical cation character of the
molecular ion (m/z = 170) is
delocalized over all the covalent
bonds. Fragmentation of C-C
bonds occurs because they are
usually weaker than C-H bonds &
this produces mixture of alkyl
radicals & alkyl carbocations. The
positive charge commonly resides on smaller fragment, so one see a
homologous series of hexyl (m/z=85), pentyl (m/z = 71), butyl (m/z = 57), propyl
(m/z =43), ethyl (m/z =29) & methyl (m/z=15) cations. These are accompanied
by set of corresponding alkenyl carbocations (e.g. m/z =55,41 & 27) formed by
loss of 2H. All significant fragment ions in this spectrum are even-electron
ions.In most alkane spectra propyl & butyl ions are most abundant.
The mass apectra of three different saturated hydrocarbons are displayed
below. Two are isomeric hexanes & third is cyclohexane. Comments regarding
the fragmentation patterns are presented in the box to the right of each
spectrum. Ions are sometimes characterized by loss of a specific neutral
fragment from the molecular ion,e.g. a M-15 ion is identified as loss of a methyl
group. Odd-electron ions, including the molecular ion, are colored orange when
marked. Even-electron ions are colored magenta. The three examples are
hydrocarbons having no functional groups are;
Hexane shows same fragmentation pattern as other unbranched alkanes.
Thus, alkyl carbocations at m/z=15, 29, 43 & 57 Da provide the dominant peaks
in the spectrum. The m/z=57 butyl cation (M-29) is the base peak, and the
m/z=43 and 29 ions are also abundant. Chain branching influences the
fragmentation of isomeric hexane. The molecular ion at m/z=86 is weaker than
that for hexane itself & M-15 ion at m/z=71 is stronger. The m/z=57 ion is
almost absent . An isopropyl cation (m/z=43) is very strong,& corresponding
propene radical-cation at m/z=42 (colored orange), produced by loss of
propane, gives the base peak. Molecular ion at m/z=84 is stronger than acyclic
compounds. The base peak at m/z=56 is produced by loss of ethene, so it is an
odd-electron ion (colored orange). The alkenyl cations at m/z=41 & 27 are
stronger than alkyl cations (m/z=43 & 29). The loss of methyl (m/z=69), & a
small m/z=15 ion obviously require some hydrogen rearrangements.
The MS of a typical hydrocarbon, n-decane is shown below.
The molecular ion is seen as a small peak at m/z = 142. C10H22 = (10 x 12) +
(22 x 1) = 142 g/mol Notice the series ions detected that correspond to
fragments that differ by 14 mass units, formed by the cleavage of the bonds
between the different -CH2- units
Toluene example ;The mass spectrum for toluene has around 30 signals.
Several peaks can be rationalized in this fragmentation pattern.
The presence of a functional group, particularly one having a heteroatom Y
with non-bonding valence electrons (Y = N, O, S, X etc.), can dramatically alter
the fragmentation pattern of a compound. This influence is thought to occur
because of a "localization" of the radical cation component of the molecular ion
on heteroatom. After all, it is easier to remove (ionize) a non-bonding electron
than one that is part of a covalent bond. By localizing the reactive moiety,
certain fragmentation processes will be favored. These are summarized in the
following diagram, where the green shaded box at top displays examples of
such "localized“molecular ions. The first two fragmentation paths lead to even-
electron ions, & elimination (path #3) gives an odd-electron ion. Note the use of
different curved
arrows to show
single electron
shifts compared
with electron pair
shifts.The charge
distributions
shown above are
common, but for
each cleavage
process the
charge may
sometimes be carried by the other (neutral) species, & both fragment ions are
observed. Of the three cleavage reactions described. here, alpha-cleavage is
generally favored for N-,O-,& S-compounds. Indeed, in the previously displayed
spectra of 4-methyl-3-pentene-2-one & N,N-diethylmethylamine major
fragment ions come from α-cleavages.
Pentanal displays a set of ions with alkyl chain (
m/z =57, 43, 41, 29 & 27). The molecular ion at
m/z=86 is very weak, as is M-1 ion at m/z =85
(aldehydes show fragment ions involving loss of
groups attached to carbonyl function). Thus, m/z
= 29 ion is probably due to both ethyl & HCO
cations. Odd-electron rearrangement ions are
observed at m/z=58 (possibly loss of CO) & 44
(rearrangement involving loss of propene).
The molecular ion at m/z=86 is more abundant
than aldehyde spectrum. Loss of carbonyl
substituents by alpha-fragmentation include: loss
of methyl (M-15 at m/z=71) & loss of a propyl
radical (M-43 at m/z=43). These comprise the
most prominent fragment ions.
The molecular ion at m/z=86 is about as strong
as in 2-pentanone. Because of the symmetry,
ethyl groups are only carbonyl substituents that
can be lost by an alpha-fragmentation. The
strongest fragment ions are found at m/z=57 loss
of an ethyl group) and m/z=29 (an ethyl cation).
The molecular ion in mass spectrum of
ethyl acetate is weak. The base peak results
from an alpha-fragmentation of ethoxyl radical
to give an m/z=43 ion. Alpha-cleavage to an
M-15 ion is very weak. The loss of water to
generate odd-electron ion at m/z=70 is
curious. Small CH3 & C2H5 ions are found at
m/z=15 & 29.
The isomeric ester, methyl propanoate, has
a more abundant molecular ion than ethyl
acetate. The alpha fragmentation of methoxyl
radical generates strong m/z=57 ion. Alpha-
fragmentation of ethyl group leads to both m/z
= 59 & 29. A smaller methyl peak is also seen.
The stability of dimethylformamide (DMF)
is evident in the abundance of its molecular
ion (m/z=73), which is also the base peak. A
small M-15 peak is observed, but the second
most abundant ion is loss of HCO by an
alpha-cleavage (m/z=44). Other ions at
m/z=42, 30 & 28 are probably derived from
the m/z=44 ion.
In 1-pentanol there are two significant odd-
electron fragment ions, one at m/z=70 (loss of
water), & other at m/z=42 (loss of water and
ethene). The fragment ion at m/z=55 is due to
a methyl radical loss from m/z=70 ion. The
m/z=31 ion may be a protonated formaldehyde
ion, formed by alpha-fragmentation.
3-Pentanol shows three significant
fragment ions. Alpha-fragmentation (loss of an
ethyl radical) forms the m/z=59 base peak.
Loss of water from this gives a m/z=41
fragment, and loss of ethene from m/z=59
gives a m/z=31 fragment.
The molecular ion (m/z=90) is strong, &
the presence of sulfur is indicated by a larger
than usual M+2 (m/z=92) peak. This is true for
m/z=75 & 47 peaks as well. Loss of methyl &
ethyl radicals generate ions at m/z=75 & 61.
The odd-electron rearrangement ion at m/z=62
results from loss of ethene. m/z=47 may be
formed from m/z=62 by loss of methyl radical.
The MS of benzyl alcohol is shown below
The molecular ion is seen at m/z = 108. Note the small peaks at 109 and 110
which correspond to the presence of small amounts of 13C in the sample
(which has about 1% natural abundance).
Fragmentation via loss of 17 (-OH) gives a common fragment seen for alkyl
benzenes at m/z = 91. Loss of 31 (-CH2OH) from the molecular ion gives 77
corresponding to the phenyl cation.
The mass spectrum of1-aminopentane is
simple, thanks to the directive influence of
nitrogen. Alpha-fragmentation generates the
m/z=30 even-electron cation, which is the only
significant fragment ion. The molecular ion
(m/z=87) is rather weak.
The mass spectrum of 3-aminopentane
is only slightly more complex than is isomer
above. The molecular ion is very weak, and
alpha-fragmentation again provides the base
peak (m/z=58). Loss of ammonia from this ion
generates the m/z=41 ion.
The cyclic 20 amine, piperidine, has a
complex mass spectrum. The molecular ion at
m/z=85 is relatively strong. Alpha-fragmentation
of H-gives the M-1 base peak. Because of the
ring, alpha-fragmentation of a C-group does not
result in a change of mass. This ring-opened
cation-radical may then lose ethyl radical or
ethene to give respectively m/z=56 & 57 ions.
Loss of an allyl radical from ring-opened
molecular ion would produce the m/z=44 ion.
Mass Spectrum