CHAPTER

11

Anhydrides
Phthalic Anhydride Maleic Anhydride References Figure Figure 11-1 209 (206) Tables Table Table Table Table 11-1 11-2 11-3 11-4 210 210 211 212 (205) (206) (207) (207) 206 207 208

*Numbers in parentheses indicate in-text page reference.

Carboxylic acid anhydrides exhibit symmetrical and asymmetric (C=O) 2 stretching vibration [rip (C=O) 2 and Vop (C=O)2], respectively. Open chain saturated aliphatic anhydrides exhibit rip (C=O) 2 in the range 1815-1825 cm -1 and Vop (C=O) 2 in the range 1745-1755 cm -1. The rip (C=O) 2 mode has stronger IR band intensity than Vop (C--O) 2. Conjugation lowers both modes. The strong band in the range 1770-1780cm -1 is assigned to rip (C=O)2, and the weaker IR band in the region 1715-1725 cm -1 is assigned to Vop (C=O)2. In the case of unconjugated 5membered ring anhydrides the IR bands occurring in the range 1845-1870 cm -1 have relatively weak intensity and the IR bands in the range 1775-1800 cm -1 have strong intensity. These bands are assigned as rip (C--O)2 and Vop (C=O)2, respectively. Conjugated 5-membered anhydrides exhibit the weak IR band in the range 1850-1860cm -1 and the strong IR band in the region 1760-1780 cm -1, which are assigned to rip (C=O) 2 and Vop (C=O)2, respectively (1,2). It was found helpful in the discussions of the v(C=O) 2 modes of anhydrides to give letters and numbers to classify each type. For example, an open chain anhydride such as acetic is labeled (OC), succinic anhydride whose cyclic structure includes a 5-membered saturated ring (5SR), glutaric anhydride whose cyclic structure include a 6-membered saturated ring (6SR), maleic and phthalic anhydrides whose cyclic structures include a 5-membered unsaturated ring (5UR), naphthalic anhydride whose cyclic structure includes a 6-membered unsaturated ring (6UR), and 2,2-biphenyldicarboxylic anhydride whose cyclic structure includes a 7-membered unsaturated ring (7UR), (3). Table 11.1 lists IR vapor phase and Raman data in the neat phase for anhydrides. 205

206

Anhydrides

Ring strain and conjugation play a role in the v(C=O) 2 modes for anhydrides. The frequency separation between Yip (C--O)2 and Vop (C=O) 2 together with their band intensity ratio also can be used to classify anhydrides. The inductive effect also affects the v(C=O) 2 modes for OC anhydrides. For example, Vip (C=O) 2 decreases in the order 1830, 1825, 1824, and 1822 cm -1 and Vop (C=O) 2 decrease in the order 1775, 1769, 1761, and 1759 cm -1 for acetic, propionic, isobutyric and 2-ethylbutyric anhydrides, respectively. Moreover, when the inductive effect causes electrons to be withdrawn from the (C=O)2 bonds such as in the case of trifluoroacetic anhydride, rip (C=O)2 and Vop (C=O) 2 occur at the relatively high frequencies of 1881 and 1817, respectively (3). Table 11.2 lists Raman data and assignments for carboxylic acid anhydrides. In the Raman, the rip (C=O) 2 mode is always more intense than Vop (C=O)2. The OCU compounds exhibit rip (C=O) 2 and Vop (C=O) 2 in the range 1771-1788cm -1 and 1715-1725cm -1, respectively, and occur at lower frequency than the OC anhydrides due to the effects of conjugation of the C=O and C=C groups.

PHTHALIC

ANHYDRIDE

Figure 11.1 shows the IR spectra of phthalic anhydride in the region 2000-1600cm -1. The spectrum on the left is that for a saturated solution of phthalic anhydride in CC14 solution, the center spectrum is that for a saturated solution of phthalic anhydride in a 23.1% vol. CHC13/CC14 solution, and the spectrum on the right is that for a saturated solution of phthalic anhydride in CHC13 solution. All spectra were recorded using 0.2-mm KBr cells. The spectrum is more intense in going from left to right due to the increased solubility in CHC13. What is important in this case is to note that the 1789 cm -1 band is more intense than the 1776 cm -1 band in CC14 solution, in 23.1% vol. in CHC13/CC14 solution the two bands have equal intensity, and in CHC13 solution the 1775cm -1 band has more intensity than the 1788cm -1 band. Whereas phthalic anhydride is a planar molecule with C2v symmetry, changes in the band intensity ratio can not be attributed to the presence of rotational conformers because solvent techniques are also used to determine which bands in each set of band results from which rotational conformer. In the case of phthalic anhydride, the doublet near 1789cm -1 and 1776cm -1 is the result of Vop (C=O) 2 in Fermi resonance with a combination tone. It is common practice (but not correct) to assign as the fundamental the band in the doublet with the most intensity; in this case it is Vop (C=O) 2. The dilemma in this situation is apparent in the middle spectrum where both bands have equal intensity and only one Vop (C=O) 2 mode. The answer is that both bands are in Fermi resonance, and each band is a mixture of Vop ( C - O ) 2 and the combination tone. After correction for Fermi resonance, Vop (C--O) 2 shows a steady decrease in frequency in CC14 solution (1784.6cm -1) to (1779.4cm -1) in CHC13 solution. This is a decrease of 5.2 cm -1 for Vop (C=O) 2 going from CC14 to CHC13 solution, and this is reasonable from study of the other carbonyl-containing compounds included in this book. It is important to note that Yip (C=O)2 decreased only 3 c m -1 in going from CC14 solution (1856cm -1) to (1853 cm -1) in CHC13 solution. The behavior of Vop (C--O)2 and Vop (C=O) 2 in solvents such as CC14 and CHC13 will be discussed in Volume 2 of the book. The general decrease in frequency of Vop (C=O)2 and Yip C=O2 is attributed to the field effect of the solvent. Hydrogen bonding

Variables in Data Interpretation

207

between the C13CH protons and the two carbonyl groups plays a role in lowering both v(C=O)2 frequencies compared to where they occur in CC14 solution. The lowest rip (C--O)2, Vop (C=O)2 and CT frequencies for phthalic anhydride are observed for solutions in dimethyl sulfoxide. These are 1850cm -1, 1788 crn -1, and 1772cm -1, respectively. After correction for ER. the unperturbed Vop (C=O)2 is determined to be 1780.5 and CT at 1788.9 cm -1 (4).

MALEIC

ANHYDRIDE

Vibrational assignments have been made for maleic anhydride (5). The combination tone (560cm -1, B, q-1235 cm -1, A, = 1795cm -1, B,) was ruled out as the possibility of being in Fermi resonance with Vop (C--O)2, because it was noted that there is a strong dependence of the band intensity ratio on the nature of the solvent while the frequencies remain practically constant (6). Phthalic anhydride reported on in the preceding showed the same phenomena, but Vop (C=O) 2 was shown to be in Fermi resonance. Table 11.3 lists IR data for maleic anhydride in n-C6H14/CHC13, CHC13/CC14, and nC6H14/CCI4 mole % solutions. Maleic anhydride is of the type 5UR (3). The v(C--O) 2 frequencies for the 5% UR structure might be expected to be lower than those for 5SR structure due to conjugation of the C - C group with the two C = O groups. However, the ring strain is more in the case of maleic anhydrate than in the case of succinic anhydride, as the C = C bond distance is less than the C - C bond distance. Therefore, the two opposing effects essentially cancel each other in the case of maleic anhydride. Maleic anhydride is a planar structure with C2v symmetry. The Yip (C--O)2 mode belongs to the A 1 symmetry species while Vop (C=O) 2 belongs to the B1 symmetry species. Therefore, Vop (C--O) 2 can only be in Fermi resonance with a combination tone belonging to the B1 symmetry species. It can not be in Fermi resonance with an overtone because any overtone is assigned to the A 1 symmetry species. A study of Table 11.3 shows that two bands occur in the range 1770 and 1793 cm -1 in each of the solvent systems, and in all cases the higher frequency band has more intensity than the lower frequency band. As in the case of phthalic anhydride, the Vop (C=O) 2 mode is in Fermi resonance with the B1 combination tone. The experimental data has been corrected for Fermi resonance, and unperturbed Vop (C--O) is determined to be between 1789.8 and 1790cm -1 in n-C6H14 solution, 1787.1-1787.5cm -1 in CC14 solution, 17851785.4cm -1 in CHC13 solution, and 1778.9cm -1 in 60.19mol % (CH3)2SO/CC14. These Vop (C=O) 2 frequencies decrease in the order of increasing polarity of the solvent, and also decrease in frequency as the reaction field of the solvent is increased. Table 11.4 lists the in-phase and out-of-phase (C=O) 2 stretching vibrations for hexahydrophthalic, tetrachlorophthalic, tetrabromophthalic, dichloromaleic (7), phthalic (4), and maleic anhydrides in different physical phases (6). In all cases the Vop (C=O) 2 modes have been corrected for Fermi resonance. These data show that both Vip (C=O)2 and Vop (C=O) 2 decrease progressively in the order: vapor, and C6H14, CC14, CHC13 and (CH3)2SO solution phases. In all cases the Vop (C=O) 2 mode decreases more in frequency in each solvent pair than does the Yip (C=O) 2 mode. In the case of styrene-maleic anhydride copolymer, the anhydride has a 5SR structure, and in CH2C12 solution Yip (C--O)2 and Vop ( C - O ) occur at 1856.6 and 1779.7 cm -1, respectively, and

208

Anhydrides

in CHC13 solution at 1856.5 and 1778cm -1, respectively. In this case, rip(C--O) 2 decreases 0.1 cm -1, and Vop ( C - O ) decreases 1 cm -1, a factor of 10 (7); this type of frequency difference was noted in the study of the other anhydride in different solvent systems.

REFERENCES
1. Dauben, W. S. and Epstein, W. W. (1959). J. Org. Chem., 24, 1595. 2. Bellamy, L. J., Connelly, B. J., Phillpots, A. R., and Williams, A. L. (1960). Z. Elecktrochem., 64, 563. 3. Nyquist, R. A. (1984). The Interpretation of Vapor-phase Infrared Spectra: Group Frequency Data, Vol. 1, Philadelphia: Sadtler Research Laboratories, Division of Bio-Rad. 4. Nyquist, R. A. (1989). Appl. Spectrosc., 43, 1374. 5. Mirone, P. and Chiorboli, P. (1962). Spectrochim. Acta, 18, 1425. 6. Nyquist, R. A. (1990). Appl. Spectrosc., 44, 438. 7. Nyquist, R. A. (1990). Appl. Spectrosc., 44, 783. 8. Schrader, B. (1989). Raman/Infrared Atlas of Organic Compounds, 2nd edition, Germany, VCH.

Variables in Data Interpretation

t~

209

tt~

eo ..J

_r
.O ~ O A

t~

,z2

7
O

eq

r ,x2

"X~

t~ 9,-~ O

:~06
0

210
TABLE 11.1 IR vapor-phase data and Raman data in the neat phase for anhydrides

Anhydrides

Anhydride type OC OCU 5SR 6SR 5UR 6UR 7UR [Raman data]

sym.(C=O) 2 str. cm -1 1822-1830 [1771-1788] 1861-1880 1820-1830 1855-1880 1802 1800

asym.(C=O) 2 str. cm -1 1759-1775 [1715-1725] 1802-1812 1782-1790 1785-1813 1768 1772

(A)sym.(C=O) 2 str. (A)asym.(C=O) 2 str. 0.96-1.31 0.11-0.23 0.35-0.51 0.07-0.35 0.72 0.66

Frequency separation crn -1 55-63 [39-581 59-72 36-40 51-85 34 28

TABLE 11.2

Raman data and assignments for carboxylic anhydrides ip(C=O)2 cm- 1 1853(3) 1788(3) 1782(3) 1771 (27,p) 1771(32) 1841(6) 1812(7,p) 1813(7,p) 1877(28,p) 1834(2) 1780(18) 1840(45) op(C=O) 2 cm- 1 1782(0) 1730(2) 1725(2) 1732 (vwk) 1715(13) 1770(1) 1743(3,p) 1751(3,p) 1810(9,p) 1729(1) 1755(vwk) 1760(37) Frequency separation cm -1 71 58 57 39 56 71 69 62 67 105 25 80
C--C str.

Anhydride Allylsuccinic Acrylic Me thacrylic Crotonic* Benzoic* Citraconic Propionic* Butyric* Trifluoroacetic* 4-Cyclohexene1,2-dicarboxylic* Glutaric* Phthalic * Reference 8.

Type 5SR OCU OCU OCU OCU 5UR OC OC OC 5SR 6SR 5UR

cm -1 1644(8) 1630(9) 1639(9) 1648(80,p) 1652(3)

Ring breathing cm-1

1629(3)

1005(44)

Variables in Data Interpretation

0
9

211

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,~

,-"~ 0

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cJ o

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i

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ce~ c 4 0 0

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9

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212
Anhydrides
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