CHAPTER

Aliphatic Amines
NH 2 Stretching Frequencies for Aliphatic Amines NH 2 Wag Frequencies for Aliphatic Amines NH 2 Bending for Alkylamines Raman Data for Primary Amines Chemical Reactions of Alkylamines Containing NH 2 or NH Groups Secondary Aliphatic Amines References Tables Table 8-1 Table 8-2 147 (144) 148 (145) 143 144 145 145 145 146 146

*Numbers in parentheses indicate in-text page reference.

In the discussion of aliphatic amines it is necessary to coin symbols for each type of amine, and this was established in Reference (1). The symbols P, S, and T are used first to denote primary, secondary, and tertiary amines (NH 2, NH, and N), respectively. The symbols P', S', and T' are used second to denote the structure of the alkyl portion of the amine [RCH2-, (R)2CH, and (R)3C] for the primary, secondary, and tertiary, respectively. For example, dimethylamine would be denoted as SP~Pt, disopropylamine as SS~S t, methylamine as PP', and tert-butylamine as PT t.

N H 2 S T R E T C H I N G F R E Q U E N C I E S FOR ALIPHATIC A M I N E S
In the vapor phase, vasym. NH 2 and vsym. NH 2 have weak IR band intensity, and often the vasym. NH 2 mode is not observed. The vasym. NH 2 mode is assigned in the region 34043422 cm -1 and vsym. NH 2 in the region 3340-3361 cm -1. In most cases, vsym. NH 2 has more intensity than vasym. NH 2 (1). However, the situation is reversed in the 2-alkoxyethylamine series, but is normal in the 3alkoxypropylamine series. Thus, this intensity reversal results from weak intramolecular hydrogen bonding between an N - H proton and the free pair of electrons on the 2-alkoxy oxygen atom. 143

144

Aliphatic Amines

Primary aliphatic amines with PS' structure exhibit vsym. NH 2 in the region ~ 3 3 3 0 3340cm -1, and this IR band is weak. When observed, vasym. NH 2 is assigned in the region ~3400-3422 c m - 1 . Primary aliphatic amines with PT' structure exhibit vsym. NH 2 in the region 3322-3335 cm -1, and vasym. NH 2 when observed in the region 3395-3400 cm -1. Both IR bands are weak. In summary, the v N H 2 frequency progressing in the order PP', PS', and PT' is shown here (1)"
Structure R - CH 2 - N H 2 (R-)CH-NH 2 ( R - ) C ( - N H 2) HO-CH 2-CH 2-NH 2 HO-CH 2-CHCH 3-NH 2 HO-CH2-C(CH3 ) 2 - N H 2 vasym. NH 2 cm -1 3404-3422 ~3400-3422 3395-3400 3465 3414 3400 vsym. NH 2 cm -1 3340-3361 3330-3340 3322-3335 3342 3348 3335 Type PP' PS' PT' PP' PS' PT'

NH 2 WAG

FREQUENCIES

FOR ALIPHATIC

AMINES

Table 8.1 lists IR vapor-phase data and assignments for primary alkylamines. The compounds with PP' structure exhibit a strong relatively broad band in the region 764-780cm -1. The absorbance (A)ratios: (A) [NH 2 wag]/(A) [vsym. CH 2] and (A) [NH 2 wag]/(A)[CH 2 bend] show that the values decrease progressing in the order C 2 to C19. This presumably indicates that (A) for NH 2 wag is relatively constant, and that (A) for vsym. CH 2 and (A) for CH 2 bend increase as the number of (CH2) n increases. Correlations such as these are valuable in spectrastructure identification of unknown aliphatic amines. The cycloalkyamines with the structure PS' exhibit NH 2 wag in the region 755-785 c m - 1 , and with the exception of cyclohexylamine increase in frequency as the cycloalkyl ring increases in size from C 3 to C 8. The absorbance (A) ratios for NH 2 wag/vsym. CH 2 and NH 2 wag/CH 2 bend also decrease in value as the number of CH 2 groups increase from 3 to 8. The NH 2 wag for alkylamines is also affected by the structure of the alkyl group. For example, PP', PS', and PT' exhibit NH 2 wag in the regions 760-780cm -1, 779-799cm -1, and 800813 c m - 1 , respectively. In addition, a weak band assigned to v C - N is also affected by the nature of the alkyl group. For example, v C - N for PP', PS', and PT' occur in the regions 10431085cm -1, 1111-1170cm -1, and 1185-1265cm -1, respectively. Both NH 2 wag and v C - N increase in frequency with increased branching on the 0~-carbon atom of the alkyl group. As already noted here, vsym. NH 2 decreased in frequency with increased branching on the alkyl 0~carbon atom. The apparent reason for the decrease in frequency of vsym. NH 2 is that with increased branching on the 0~-carbon atom more electrons are released to the C - N group (inductive affect). This causes the N atom to become more basic; consequently, the NH 2 bonds are weakened causing the v N H 2 modes to vibrate at lower frequencies. Also, the inductive effect increases in the order P', S', and T', and this causes the C - N bond strength to increase in the same order. Consequently, v C - N increases in frequency as the strength of the hydrogen bond increases. In addition, the NH 2 wag increases in frequency in the order P', S', and T'. This is because it takes more energy for the two relatively charged NH 2 protons to wag about the relatively negative free pair of electrons in the C - N plane as the protons and the nitrogen atom have increasingly relative opposite electrical charges. A similar explanation was presented for the v O H , v C - O , OH torsion for alkanols (see Chapter 6).

Variables in Data Interpretation

145

NH 2 BENDING

FOR ALKYLAMINES

The NH 2 bending mode for the alkylamines with ppt structure occurs in the region 15991629 cm -1, with PSt in the region 1612-1621 cm -1, and with PT t in the region 1610-1616 cm -1, and has weak to weak-medium IR band intensity in the vapor phase. Therefore, the NH 2 bending mode frequencies are not useful for distinguishing between alkylamines with PPt, PS t, and PT t structures. In the liquid it is assigned in the region 1590-1627 cm -1 with medium intensity (3). In contrast, NH 2 bend for arylamines (anilines) occurs at higher frequency with strong IR band intensity (3). (See the next chapter.)

RAMAN

DATA FOR

PRIMARY

AMINES

Table 8.2 lists Raman data and assignments for the neat phase for primary amines. In the neat phase, vasym. NH 2 and vsym. NH 2 occur in the region 3 3 6 7 - 3 3 7 9 c m -1 and 3307-3322 c m -1, respectively. In all cases, the vsym. NH 2 mode has more relative band intensity than the vasym. NH 2 modes as indicated by the number in parenthesis (2). It is interesting to compare the vasym. NH 2 and vsym. NH 2 frequencies obtained for butylamine (1-aminobutane) in the vapor and liquid phases: vasym. NH 2 (3411 cm -1, vap. and 3376 cm -1, liq.) and vsym. NH 2 (3345 cm -1, vap. and 3322 cm -1, liquid). This comparison shows that vasym. NH 2 and vsym. NH 2 occur at lower frequency in the liquid phase by 35 and 23 c m - 1, respectively. Two of the examples given in Table 8.2 contain a 4-aminocyclohexyl group, and both exhibit a very strong Raman band at 784 c m -1, which is assigned to the cyclohexyl breathing mode.

CHEMICAL

REACTIONS

OF ALKYLAMINES

CONTAINING

NH 2 OR NH GROUPS This section is brought to the reader's attention for matters of safety and because it can cause confusion when interpreting spectral data. From experience it has been noted that heat generated from the chemical reaction of aliphatic primary or secondary amines with CS 2 can cause the entire content of the volumetric flask to blow out of its mouth. This can cause an injury, or possibly a fire, because CS2 has a low flashpoint. These chemical reactions occur as follows:

II
2R-NH2+CS2-> R-N-C-S" N*H3-R

I
H
S

II
2(R-)2NH + CS2 -~ (R-)2N-C-S" +NH(-R)2

146

Aliphatic Amines

As well, if exposed to air for a period of time these same alkylamines can undergo comparable reactions with CO 2 (replace CS 2 with CO2). In addition, alkylamines can react slowly with solvents such as CC14, CHC13, and CH2C12, and this can cause problems in specifically identifying the original sample.

SECONDARY

ALIPHATIC

AMINES

The N - H stretching band for compounds of form (R--)2NH is weak, and is not readily detected in compounds whose IR spectra have been recorded in the vapor phase (1). However, N - H wag has strong IR band intensity with half bandwidths varying between 50 and 100 cm -1 and occurs in the region 6 8 6 - 7 5 0 c m -1 in the vapor phase. Thus, it occurs at lower frequency than NH 2 wag. In the liquid, the weak IR band occurs in the region 3320-3280 cm -1 and in dilute solution in the region 3310-3360 cm -1 (3). Dialkylamines with SPIP I structure exhibit NH wag in the region 699-715 cm -1, with SPISt structure near "-,686 cm -1. These data suggest that NH wag decreases in frequency in the order SS~S~, SPaSI, and SPIP t, which is the opposite order for the primary alkylamines (see the preceding materials here). In the dialkyl amine series with SP'P ~ structure a band assigned as v N ( - C ) 2 occurs in the region 1132-1151 cm -1 (1).

REFERENCES 1. Nyquist, R. A. (1984). The Interpretation of Vapor-Phase Infrared Spectra: Group Frequency Data, Philadelphia: Sadtler Research Laboratories, Division of Bio-Rad Laboratories, Inc. 2. Raman Data from the Sadtler Research Laboratories, Philadelphia: Division of Bio-Rad Laboratories, Inc. 3. Lin-Vien, D., Colthup, N. B., Fateley, W. G., and Grasselli, J. G. (1991). The Handbook of Infrared and Raman Characteristic Frequencies of Organic Molecules, San Diego: Academic Press.

Variables in Data Interpretation TABLE 8.1 IR vapor-phase data and assignments for primary amines (A) INH2 wag] (A)[s.CH 2 str.l

14 7

Amine Methyl Ethyl Propyl Butyl Heptyl Octyl Nonyl Decyl Undecyl Tridecyl Tetradecyl Pentadecyl Octadecyl Nonadecyl

a.CH 3 str. 2960 (0.640)

a.CH 2 str.

s.CH 3 str. 2898 (0.600) 2922 (0.940)

s.CH 2 str.

CH 2 bend

s.CH 3 bend

NH 2 wag 778 (0.784) 772 (1.087) 764 (0.630) 779 (0.664) 770 (0.248) 771 (0.190) 775 (0.189) 780 (0.120) 775 (0.131) 775 (0.050) 770 (0.060) 770 (0.040) 775 (0.035) 775 (0.044) 755 (1.230) 779 (0.223) 770 (0.170) 784 (0.151) 785 (0.060)

(A)[NH2 wag] (A)[CH 2 bend]

2970 (0.700) 2970 (0.462) 2970 (0.460) 2970 (0.290) 2970 (0.410)

2970 (0.040)

2965 (1.240) 2978 (1.230) 2940 (1.250) 2940 (1.250) 2930 (1.250) 2930 (1.250) 2935 (1.250) 2935 (1.210) 2935 (1.250) 2938 (1.250) 2930 (1.250) 2935 (1.250) 2930 (1.250) 3100 (0.220) 2968 (1.250) 2935 (1.250) 2930 (1.250) 2932 (1.150)

2870 (0.640) 2880 (0.679) 2880 (0.621) 2868 (0.510) 2964 (0.510) 2864 (0.530) 2864 (0.380) 2864 (0.570) 2864 (0.310) 2864 (0.310) 2860 (0.310) 2962 (0.310) 2860 (0.400) 3010 (0.250) 2884 (0.420) 2864 (0.420) 2860 (0.320) 2868 (0.199)

1456 (0.164) 1465 (0.135) 1465 (0.120) 1468 (0.130) 1465 (0.091) 1466 (0.100) 1466 (0.080) 1465 (0.100) 1460 (0.050) 1460 (0.058) 1460 (0.059) 1465 (0.045) 1460 (0.089) 1455 (0.140) 1459 (0.061) 1458 (0.130) 1460 (0.100) 1459 (0.069)

1398 (0.280) 1387 (0.129) 1387 (0.111) 1377 (0.080) 1385 (0.050) 1388 (0.066) 1385 (0.035) 1385 (0.050) 1389 (0.020) 1385 (0.050) 1385 (0.011) 1385 (0.005) 1385 (0.005)

1.69 0.93 1.07 0.49 0.37 0.36 0.32 0.23 O.16 0.19 0.13 0.11 0.11

6.63 4.67 5.53 1.9 2.09

1.89

1.51 1.11
1.01

1.11 0.68 0.77 0.49

Cyclopropyl Cyclopentyl

4.03 0.53 0.41 0.47 0.31

8.79 3.66 1.42 1.51 0.87

Cycloheptyl Cyclooctyl

148
TABLE 8.2 Raman data and assignments for primary amines bis-(4-Aminocyclohexyl) methane Hexamethylene diamine 3367(1) 3307(3) 2-Aminoethyl methyl ether 3379(1) 3322(3) 2985(5) 2950(6) 3-Methoxypropyl amine 3377(2) 3319(5) 2929(7) 2868(4) 2826(6) 2811(5) 2755(3) 1450(9)

Aliphatic Amines

1-Aminobutane 3376(1) 3322(3) 2963(5) 2938(7)

Ethoxyethyl amine 3379(1) 3322(3) 2977(5) 2934(9) 2870(5)

4,4'-bis(pAmino-cyclohexyl) methane 3367(0) 3312(1) 2931(2)

Assignment a.NH 2 s.NH 2 a.CH 3 str. a.CH 2 str. a.CH 2 str. s.CH 2 str. s.CH 2 str. C.T. C.T. NH 2 bend CH2 bend Ring breathing

3311(1)

2899(1)

2875(4)

2853(2) 2797(2) 1444(7) 1441(5) 784(9) 1459(6) 1640(1) 1440(9)

2823(4) 2723(2) 1597(1) 1453(9)

2846(3)

1441(5) 784(9)