Ind. Eng. Chem. Res. 1994,33, 1062-1066
1062
Amido-Imido1 Tautomerization by Acid-Catalyzed Addition of Nitriles to Undec-10-enoic Acid. 1. Novel Route for Substituted Amidoundecanoic Acids and Their Possible Industrial Utilization Kallappa M. Hosamani'J and Shakunthala K. Hosamanit Department of Chemistry and Department of Mathematics, Janata Shikshana Samiti's (J.S.S.) College, Vidyagiri, Dharwad 580 004, India
Considering the extensive applications of oleochemicals as industrial products, preparation of a series of novel substituted amidoundecanoicacids by the reaction of different nitriles was performed. The specific nitriles fluoroacetonitrile, chloroacetonitrile, bromoacetonitrile, iodoacetonitrile, 6-methoxypropionitrile, p-ethoxypropionitrile, 0-propoxypropionitrile, B-butoxypropionitrile, and ethyl cyanoacetate were added to the double bond of undec-10-enoic acid in the presence of concentrated sulfuric acid followed by hydrolysis. These newly synthesized oleochemicals have been characterized by Fourier transform infrared (FTIR), proton nuclear magnetic resonance ('H NMR), mass spectral (MS), and elemental analyses. Scheme
Introduction During the past decade production and utilization of oil and fat derivatives have grown in size and diversity. These fat-derived chemicals are essential to a variety of industries such as coatings, surfactants, plasticizers, lubricant additives, cosmetics, pharmaceuticals, soaps, detergents, textiles, plastics, and organic pesticides. In the industrial field there has been competition between oleochemicals and petrochemicals. The ever-increasing cost of petrochemicals has diverted the attention of chemists to synthesize new oleochemicals derived from natural oils and fats. The interest in the biological and industrial potentialities of oleochemicalshas resulted in the development of various synthetic procedures for the introduction of a heterocyclic moiety into the hydrocarbon chain. As far as the authors are aware, there are no reports in the literature on the reaction of nitriles with undec-10-enoic acid in strong sulfuric acid medium. Considering the extensive applications of oleochemicals as biological and industrial products, an attempt has been made to synthesize the novel substituted amidoundecanoic acids by the reaction of different nitriles with the double bond of undec-10-enoic acid. However, the reaction of nitriles with the alkenes in strong acid medium yielded the substituted amides has been described by Ritter and Minieri.l Experimental Section Undec-10-enoic acid (99%; Aldrich Chemical Co., Catalogue No. 12,467-2),nitriles (Fluka AG), and sulfuric acid AR (98%, Glaxo Laboratories India Ltd.) were used. The infrared spectra were taken on a Fourier transform infrared (FTIR) Bomem Michelson Series instrument and a Hitachi 270-30 instrument, using KBr pellets. The 'H NMR spectra were recorded from deuterochloroform solution with a Varian T-60 spectrophotometer. The chemical shifts (6) were measured in parts per million (ppm) downfield from internal standard tetramethylsilane
* To whom correspondence should be addressed. + Department of Chemistry. Department of Mathematics.
*
la
CHZ =CH(CH,)&OOH
(i) mcd H&04 (ii) nkrile (RCN) (iii)belwa)'c (iv) hydrolysis
CH3CH(CH2)8COOH
I
NHCR
II
0 (1)
aR = a, -CHzF; b, 4H2CI; c, -CH2Br; d, -CHzI; e, -CH2CH20CH3: 1, -CHzCH2CCH&H3; g, ~ H ~ C H ~ O C H Z C H Z C H ~ ; h, -CH2CH2C€H2CH2CH2CH3; i, -CH2COOCH2CH3.
at 6 = 0. The mass spectra were run on a Finnigan Mat 8230 with Micro PDP 11 Computer instrument. The melting points were recorded on a Thomas-Hoover capillary melting point apparatus. Preparation of (F1uoroacetamido)undecanoicAcid. A homogeneous mixture of 18.4 g (1 mol) of undec-10enoic acid and 17.7 g (3 mol) of fluoroacetonitrile in a dropping funnel was prepared and added in 30 min to 59.4 g (6 mol) of strong sulfuric acid (98% ' ) in a three-necked liter flask fitted with a thermometer and an efficient stirrer. The temperature was maintained below 20 "C by external cooling. After complete addition, the reaction mixture was stirred for 24 h and poured into ice-cold water. The soft syrupy insoluble mass was stirred occassionally and then allowed to stand overnight in dilute acidic medium. The following morning the stirring was continued until the product had hardened to a crumbly wax. The product was washed thoroughly with distilled water and dried. Similarly, different substituted amidoundecanoic acids such as chloro, bromo, iodo, 0-methoxypropion-, ðoxypropion-, @-propoxypropion-,j3-butoxypropion-, and (carbethoxyacetamido)undecanoic acids were prepared using corresponding nitriles and undec-10-enoic acid (Scheme 1). For analytical purposes, the crude compounds were recrystallized from the aqueous alcohol. The uncorrected melting points, yield, and elemental analyses of all the compounds were given in Table 1. Mechanism. In the proposed mechanism it is found that sulfuric acid first adds to the double bond of undec10-enoic acid to form sulfate ester (11, followed by the
0888-5885/94/2633-lO62$04.50/00 1994 American Chemical Society
Ind. Eng. Chem. Res., Vol. 33, No. 4,1994 1063 Table 1
no.
comod Ia Ib
molecular formula
yield, %
mp, OC
carbon, % calcd found
88.0
76-78 59-61 48-50 61-62 53-55 65-67 72-74 89-71 5C-52
59.77 56.12 48.45 42.28 62.72 63.79 64.95 65.65 60.95
86.0 83.0 84.0 80.0 79.0 82.0 88.0 90.0
IC
Id I0 If Ie Ih Ii
reaction of this intermediate with the different nitriles. It may be significant that when the reaction mixture is poured into ice-cold water to isolate the product, an oily material is obtained. The viscous, oily mass (2) requires time to hydrolyze and undergo amido-imido1 tautomerization to the solid amide (3), which is the product actually isolated.
elemental analyses hydrogen, % calcd found
59.62 55.80 48.22 42.12 62.56 63.67 64.71 65.49 60.65
9.20 8.63 7.45 6.50 10.11 10.30 10.48 10.64 9.21
-
CH3
0
I I
11
C-!H-CH
I
RCH
-e
0 11 C--+NH
I
RCH
(CHz)8COOH
I
9.02 8.68 7.32 6.32 9.92 10.20 10.12 10.52 9.09
I
R'CH=CHz
+ H2S04
II
-RCH=C=O
H
O
(3)
I
OH
NHz=CHCH3 m/Z 44
H 'CH(CHz)&HCH3
-e
I
N-CR
I
H
II
+
The McLafferty rearrangement due to the carboxylic acid groups showed the molecular ion peaks at rnlz 60 in all the compounds.
N=CR
I
-
I
R'6HCH3 + -OS03H
N=CR-
CH2(CHz)$OOH
H
- 1
R'CHCH3
I
CH
RCH (1)
R'CHCH3
.
-
CH3
0
I
t
N-CR
5.24 4.92 4.19 3.71 4.78 4.53 4.38 4.16 4.32
H
H
R'CHCH3
I
5.36 5.04 4.35 3.80 4.88 4.65 4.44 4.26 4.44
*ZYl
C2NH=CHCH3 OS03H
nitrogen, % calcd found
II
O
R'CHCH3 hydrolysis
I
N=CR
I
OS03H
(2)
where R' = -(CH2)8COOH.
Results a n d Discussion All the compounds (la-i) showed strong absorption bands a t 3331-3304 and 16261591cm-' for -"stretching and -NH bending rapectively for the presence of secondary amide. The carbonyl stretching at 1707-1702 and 1652-1638 cm-l were observed for saturated aliphatic carboxylic acids and secondary amide carbonyl functional groups, respectively. The infrared spectrum of compound Ii showed a strong absorption band at 1730 cm-' for a ester carbonyl functional group. The lH NMR spectra of all the compounds (Ia-i) exhibited structure-revealing proton signals a t 6 11.5-11.9 (broad singlet, lH, for -COOH, disappeared on D2O addition), 1.3-1.5 (broad multiplet, 14H, for shielded methylene protons, -(CHz)r), and 0.9-1.2 (doublet, 3H, for a terminal -CH3). The molecular ion peaks of straight-chain monocarboxylic acids are weak but usually discernible. However, the molecular ion peaks of all the substituted amidoundecanoic acids were quite distinguishable. The most important characteristic molecular ion peaks at rnlz 44 and 60, due to the McLafferty rearrangements.2 were observed in all the compounds for the secondary amide and monocarboxylic acid functional groups, respectively. The McLafferty rearrangement due to the secondary amide groups showed dominent molecular ion peaks at rnlz 44 in all the compounds.
m'z 60
Besides the McLafferty rearrangement molecular ion peaks, the mass spectrum of each compound resembles the series of hydrocarbon clusters at the interval of 14 mass units. \
\
\
\
0
Data regarding FTIR, lH NMR, and MS of all the compounds (Ia-i) are summarized in Table 2.
Spectral Studies
(F1uoroacetamido)undecanoicAcid (Ia). IR (neat) 3331 cm-I (-NH stretching), 1626 cm-l (-NH bending), 1702cm-' (-C=O stretching of -COOH group), 1642 cm-l (-C=O stretching of secondary amide group); 'H NMR (CDC13) 6 0.89 (d, 3H, terminal -CH3), 1.4 (bs, 12H, chain -(CH2)6-), 1.6 (m, 2H, CH~CHCHT),2.6 (t, BH,-COCHzF), 3.8 (bm, 3H, -CHCH3 + -CH2COOH), 6.3 (bd, lH, -NH, disappeared on D20 addition), 11.8 (bs, l H , -COOH, disappeared on DzO addition). MS rnlz 261 [M+l 244, 216, 202, 188, 174, 160, 146, 132, 118, 104. McLafferty rearrangement molecular ion peaks at mlz 60 and 44 due to carboxylic acid and secondary amide functional groups, respectively.
1064 Ind. Eng. Chem. Res., Vol. 33, No.4,1994 Table 2. Spectral Analyses no.
structures
CH&H(CHA,COOH
I
~HCCH~HPCY
a
infrared v, cm-1 (KBr pellets) 3331 cm-l for >NH stretchingfor Secondary amide; 1626 cm-l for >NH bending for secondary amide; 1702 cm-l for >C=O stretching for saturated aliphatic carboxylic acid; 1642 cm-1 for >C=O stretching for Secondary amide carbonyl 3323 cm-1 for >NH stretching for secondary amide; 1620 cm-1 for >NH bending for secondary amide; 1706 cm-l for >C=O stretching for saturated aliphatic carboxylic acid; 1644 cm-1 for >C=O stretching for secondary amide carbonyl 3326 cm-1 for >NH stretching for secondary amide; 1610 cm-1 for >NH bending for secondary amide; 1704 cm-1 for >C=O stretching for saturated aliphatic carboxylic acid; 1647 cm-l for >C=O stretching for secondary amide carbonyl 3320 cm-1 for >NH stretching for secondary amide; 1615 cm-l for >NH bending for secondary amide; 1707 cm-l for >C=O stretching for saturated aliphatic carboxylic acid; 1644 cm-l for >C=O stretching for secondary amide carbonyl 3316 cm-1 for >NH stretching for secondary amide; 1594 cm-l for >NH bending for secondary amide; 1705 cm-l for >C=O stretching for saturated aliphatic carboxylic acid; 1646 cm-1 for >C=O stretching for secondary amide carbonyl 3314 cm-l for >NH stretching for secondary amide; 1591 cm-l for >NH bending for secondary amide; 1703cm-l for >C=O stretching for saturated aliphatic carboxylic acid; 1638 cm-1 for >C=O stretching for secondary amide carbonyl 3308 cm-l for >NH stretching for secondary amide; 1608 cm-l for >NH bending for secondary amide; 1703cm-1 for >C=O stretching for saturated aliphatic carboxylic acid; 1651 cm-1 for >C=O stretching for secondary amide carbonyl
CI+$H(CH&,COOH
I NHCCH&H@(CH&H3 II
0
(W
3304 cm-1 for >NH stretching for secondary amide; 1602 cm-1 for >NH bending for secondary amide; 1707 cm-l for >C=O stretching for saturated aliphatic carboxylic acid; 1645 cm-l for >C=O stretching for secondary amide carbonyl
nuclear magnetic resonance (1H) 6 values in ppm 11.8 (bs. - . 1H.. COOH. disappeared on DzO addition); 6.3 (bd, lH, >NH, disappeared on D20 addition); 3.8 (bm, 3H, >CHCHs + -CHzCOOH); 2.6 (t, 2H, -COCHzF); 1.6 (m, 2H, -CH&HCHz-); 1.4 (be, 12H, chain -(C&)e-); 0.9 (t, 3H, t-CH3) 11.6 (bs, lH, COOH,disappeared on DzO addition); 6.2 (bd, lH, >NH, disappeared on D20 addition); 4.0 (bm, 3H, >CHCHs + CHzCOOH); 2.3 (t,2H, COCH2Cl-); 1.5 (m, 2H, -CHzCHCHs-); 1.3 (bs, 12H, chain -(cH2)6-); 0.9 (t, 3H, terminal C H S ) 11.7 (bs, lH, COOH,dieappeared on DzO addition); 6.4 (bd, lH, >NH, disappeared on DzO addition); 4.0 (bm, 3H, >CHCHs + -CHzCOOH); 2.1 (t, 2H, COCHZBr); 1.6 (m, 2H, CHZCHCHS-); 1.3 (bs, 12H, chain -(CH&-); 0.9 (t,3H, terminal C H s ) 11.5 (bs, lH, -COOH,disappeared on DzO addition); 6.1 (bd,lH, >NH, disappeared on DzO addition); 4.1 (bm, 3H, >CHCHs + -CHzCOOH); 1.9 (t,2H, -COCHzI); 1.7 (m, 2H, -CHzCHCH3-); 1.4 (bs, 12H, chain -(CH&-); 0.9 (t, 3H, terminal C H s ) 11.7 (bs, lH, C O O H ,disappeared on DzO addition); 6.2 (bd, lH, >NH, disappeared on DzO addition); 4.0 (m, lH, >CHCHs); 3.5 (t, 3H, -0CHs); 2.5 (p, 4H, CHzCHzO-); 1.6 (bm, 2H, -CHzCH(CH+); 1.4 (bs, 14H, chain -(CH&-); 1.0 (d, 3H, terminal C H s ) 11.8(bs, lH, COOH,disappeared on DzO addition); 6.1 (bd, lH, >NH, disappeared on DzO addition); 3.9 (m, 3H, >CHCHs + -0CH2CHa); 2.3 (p, 4H, CHzCHzO-); 1.5 (bs, 16H, chain -(CHz)r); 1.2 (d, 3H, -0CHzCHs); 0.9 (t,3H, terminal C H s ) 11.9 (bs, lH, COOH,disappeared on DzO addition); 6.1 (bd,lH, >NH, disappeared on DzO addition); 3.9 (m, 3H, >CHCHs + -0CHzCH2CHa) ; 2.3 (p, 4H, CHzCHzO-); 1.3 (bs, 18H, chain -(CHz)r + -0CHzCHzCHg); 1.1(d, 3H, terminal CHs) 11.8 (bs, lH, -COOH,disappeared on DzO addition); 6.0 (bd, lH, -NH,disappeared on DzO addition); 4.0 (m, lH, >CH-CHs + -OCHz(CHz)zCHs; 2.4 (D.4H. -CHdXLO-): 1.5 (be, 20H, chain -7CHg)s- + -OCHz(CHz)zCHs); 1.2 (d, 3H, terminal C H s )
maas spectra at m/z 261.244.216. 202, iss, i74, 160,146,132, 118,104,60, and 44
278,261,233, 219, 205,191,177, 163,149,135, 121,60, and 44
322,305,277, 263,249,235, 221,207,193, 179,165,60, and 44
369,352,324, 310,296,282, 268,254,240, 226,212,60, and 44
287,270,242, 228,214,200, 186,172,158, 144,130,60, and 44
301,284,256, 242,228,214, 200,186,172, 158,144,60, and 44
315,298,270, 256,242,228, 214,200,186, 172,158,60, and 44
329,312,284, 270,256,242, 228,214,200, 186,172,60, and 44
Ind. Eng. Chem. Res., Vol. 33, No. 4,1994 1065 Table 2 (Continued) no. 9
structures CH&H(CHdsCOOH
I
NHCCH&OOC&
'd
(Ii)
infrared Y, cm-1 (KBr pellets) 3320 cm-1 for >NH stretching for secondary amide; 1612 cm-l for >NH bending for secondary amide; 1710 for >C-0 stretching for eaturated aliphatic carboxylic acid; 1652 cm-1 for >C=O stretching for secondary amide carbonyl; 1730 cm-l for >C=O Stretching of ester carbonyl group
(Ch1oroacetamido)undecanoicAcid (Ib). IR (neat) 3323 cm-l (-NH stretching), 1620cm-1 (NH bending), 1706 cm-l (-C=O stretching of -COOH group), 1644 cm-' (-C=O stretching of secondary amide group); 'H NMR (CDCl3) 6 0.9 (d, 3H, terminal -CH3), 1.3 (bs, 12H, chain -(CH2)6-), 1.5 (m, 2H, -CH2CHCHs), 2.3 (t, 2H, -COCH2Cl), 4.0 (bm, 3H, -CHCH3 + -CH2COOH), 6.2 (bd, l H , -NH, disappeared on D2O addition), 11.6 (bs, lH, -COOH, disappeared on D2O addition); MS rnlz 278 [M+] 261, 233, 219, 205, 191, 177, 163, 149, 135, 121. McLafferty rearrangement molecular ion peaks at rnlz 60 and 44 due to carboxylic acid and secondary amide functional groups, respectively. (Bromoacetamido)undecanoic Acid (IC). IR (neat) 3326 cm-l (-NH stretching), 1610 cm-l (-NH bending), 1704cm-l (-CEO stretching of -COOH group), 1647 cm-l (-C=O stretching of secondary amide group); lH NMR (CDCl3) 6 0.9 (d, 3H, terminal -CH3), 1.3 (bs, 12H, chain -(CH2)c), 1.6 (m, 2H, -CH&HCH3), 2.1 (t, 2H, -COCH2Br), 4.0 (bm, 3H, -CHCHa + -CH&OOH), 6.4 (bd, lH, -NH, disappeared on D2O addition), 11.7 (bs, l H , -COOH, disappeared on D2O addition); MS rnlz 322 [M+l 305, 277, 263, 249, 235, 221, 207, 193, 179, 165. McLafferty rearrangement molecular ion peaks at m/z 60 and 44 due to carboxylic acid and secondary amide functional groups, respectively. (1odoacetamido)undecanoic Acid (Id). IR (neat) 3320 cm-l (-NH stretching), 1615 cm-l (-NH bending), 1707 cm-l (-C=O stretching of -COOH group) and 1644 cm-1 (-C=O stretching of secondary amide group); 'H NMR (CDCl3) 6 0.9 (d, 3H, terminal -CHA 1.4 (bs, 12H, chain -(CH2)6-), 1.7 (m, 2H, -CH&HCH3), 1.9 (t, 2H, -COCH21), 4.1 (bm, 3H, -CHCH3 + -CH2COOH), 6.1 (bd, l H , -NH, disappeared on D2O addition), 11.5 (bs, l H , -COOH, disappeared on D20 addition); MS rnlz 369 [M+l 352,324,310,296,282,268,254,240,226,212. McLafferty rearrangement molecular ion peaks at rnlz 60 and 44 due to carboxylic acid and secondary amide functional groups, respectively. (8-Methoxypropionamido)undecanoic Acid (Ie). IR (neat) 3316 cm-l (-NH stretching), 1594 cm-l (-NH bending), 1705cm-l (-C=O stretching of a-COOH group), 1646 cm-1 (-C=O stretching of secondary amide group); 1H NMR (CDC13) 6 1.0 (d, 3H, terminal -CH3), 1.4 (bs, 14H, chain -(CH2)7-), 1.6 (bm, 2H, -CH&HCHs), 2.5 (p, 4H, -CH2CH20-), 3.5 (t, 3H, -OCH3), 4.0 (m, lH, -CHCHs), 6.2 (bd, l H , -NH, disappeared on D2O addition), 11.7 (bs, lH, -COOH, disappeared on D2O addition); MS rnlz 287 [M+l 270,242,228,214,200,186, 172,158,144, 130. McLafferty rearrangement molecular ion peaks at m/z 60 and 44 due to carboxylic acid and secondary amide functional groups, respectively. (8-Ethoxypropionamido)undecanoicAcid (If). IR (neat) 3314 cm-l (-NH stretching), 1591 cm-l (-NH
nuclear magnetic resonance (1H) 6 values in ppm 11.8 (bs, lH, -COOH,disappeared on DzO addition); 6.3 (bd, lH, >NH, disappeared on D2O addition); 4.1 (m, lH, >CH-CHs); 3.3 (8,5H, -COOC&); 2.6 (8, 2H, -CHzCOOCzHs); 2.4 (t, 2H, -CHzCOOH); 1.7 (m, 2H, -CHzCHCHs); 1.4 (bs, 12H, chain -(CHz)r); 1.1 (d, 3H, terminal -CHs)
mass spectra at mlz 315,298,270, 256,242, 228, 214,200,186, 172,158,60, and 44
bending), 1703cm-l(-C=O stretching of a -COOH group), 1638 cm-l (-C=O stretching of secondary amide group); 'H NMR (CDCl3) 6 0.9 (d, 3H, terminal -CH3), 1.2 (d, 3H, -OCH2CH3), 1.5 (bs, 16H, chain -(CH2)8-), 2.3 (p, 4H, -CH2CH20-), 3.9 (m, 3H, -CHCH3 -OCH2CH3), 6.1 (bd, lH, -NH, disappeared on D2O addition), 11.8 (bs, l H , -COOH, disappeared on D2O addition); MS rnlz 301 [M+l 284, 256, 242, 228, 214, 200, 186, 172, 158, 144. McLafferty rearrangement molecular ion peaks at mlz 60 and 44 due to carboxylic acid and secondary amide functional groups, respectively. (8-Propoxypropionamido)undecanoicAcid (Ig). IR (neat) 3308 cm-' (-NH stretching), 1608 cm-l (-NH bending), 1703cm-l (-C=O stretching of a -COOH group) and 1651 cm-l (-C=O stretching of a secondary amide group). 'H NMR (CDCl3) 6 1.1(d, 6H, terminal -CH3 -CH3 groups), (bs, 18H, chain-(CH2)8 + -OCH&H2CHs), 2.3 (p, 4H, -CH2CH20-), 3.9 (m, 3H, -CHCH3 + -0CH2CHzCH3),6.1(bd, l H , -NH, disappeared onD2O addition), 11.9 (bs, lH, -COOH, disappeared on D20 addition); MS rnlz 315 [M+l 298,270,256,242,228,214,200,186,172, 158. McLafferty rearrangement molecular ion peaks at mlz 60 and 44 due to carboxylic acid and secondary amide functional groups, respectively. (8-Butoxypropionamido)undecanoicAcid (Ih). IR (neat) 3304 cm-l (-NH stretching), 1602 cm-l (-NH bending), 1707cm-l (-C=O stretching of a-COOH group), 1645 cm-1 (-C=O stretching of secondary amide group); 1H NMR (CDCl3) 6 1.2 (d, 3H, terminal, -CH3), 1.5 (bs, 20H, chain -(CH2)8- + -OCH2(CH2)2CH3), 2.4 (p, 4H, -CH&H20-), 4.0 (m, 3H, -CHCH3 + -OCHz(CHz)&H3), 6.0 (bd, l H , -NH, disappeared on D2O addition), 11.8(bs, l H , -COOH, disappeared on D20 addition); MS mlz 329 [M+l 312, 284, 270, 256, 242, 228, 214, 200, 186, 172. McLafferty rearrangement molecular ion peaks at rnlz 60 and 44 due to carboxylic and secondary amide functional groups, respectively. (Carbethoxyacetamido)undecanoic Acid (Ii). IR (neat) 3320 cm-l (-NH stretching), 1612 cm-1 (-NH bending), 1710cm-l (-C=O stretching of a-COOH group), 1652cm-l (-C=O stretching of a secondary amide group), 1730cm-l (-C=O stretching of ethyl ester group); lH NMR (CDC13) 6 1.1 (d, 3H, terminal -CH3), 1.4 (bs, 12H, chain -(cH2)6-), 1.7 (m, 2H, -CH2CHCH3), 2.4 (t, 2H, -CH2COOH), 2.6 (9, 2H, -CHzCOOCzH5), 3.3 (s, 5H, -COOCfi5), 4.1 (m, lH, -CHCHd, 6.3 (bd, lH, -NH, disappeared on D2O addition), 11.8 (bs, l H , -COOH, disappeared on D20 addition); MS rnlz 315 [M+l 298, 270, 256, 242, 228, 214, 200, 186, 172, 158. McLafferty rearrange-ment molecular ion peaks at rnlz 60 and 44 due
+
+
1066 Ind. Eng. Chem. Res., Vol. 33, No. 4,1994
to carboxylic acid and secondary amide functional groups, respectively.
Literature Cited (1) Ritter, J. J.; Minieri, P. P. Anew reaction of nitriles. I Amides 1948,70,4045from alkenes and mononitriles. J. Am. Chem. SOC. 4048. (2) Silverstein, R. M.; Bassler, G. C.; Morrill, T. C. Mass spectrometry, infrared spectrometry and proton magnetic reso-
nance spectrometry. In Spectrometric Identification of Organic Compounds; John Wiley & Sons: New York, 1981; pp 3-247. Received for review October 22, 1993 Accepted December 16,1993. e Abstract published in Advance ACS Abstracts, January 15, 1994.
