Preparation and characterization of methyl 11-amino-(N-P-toluenesulfonyl)-9-E-octadecenoate and methyl 8-amino-(N-P-toluenesulfonyl)-9-E-octadecenoate

Article abstract of DOI:10.1007/s11746-997-0128-7

Allylic amination of methyl oleate with bis(N-p- toluenesulfonyl) sulfodiimide results in a mixture of methyl 11- amino-(N-p-toluenesulfonyl)-9-E-octadecenoate and methyl 8- amino-(N-p-toluerfesulfonyl)-9-E-octadecenoate in 58% yield. These novel products were isolated and characterized by nuclear magnetic resonance, infrared spectroscopy, mass spectrometry, and melting point. The reaction was analyzed by high- performance liquid chromatography and thin-layer chromatography.

Full text of DOI:10.1007/s11746-997-0128-7

Preparation and Characterization of Methyl
11-Amino-(N-p-toluenesulfonyl)-9-E-octadecenoate
and Methyl 8-Amino-(N-p-toluenesulfonyl)-9-E-octadecenoate
Barry F. Herrona, Marvin O. Bagbya,*, Terry A. Isbellb, Wm. Craig Byrdwellc,
Ron Plattnerd, and David Weisledere
aOil Chemical Research, bNew Crops Research, cFood Quality and Safety Research,
dBioreactive Constituents Research, and eAnalytical Chemical Support, NCAUR, ARS, USDA, Peoria, Illinois 61604
ABSTRACT: Allylic amination of methyl oleate with bis(N-p- toluenesulfonyl) sulfodiimide (1) may react with alkenes to
toluenesulfonyl) sulfodiimide results in a mixture of methyl 11-
amino-(N-p-toluenesulfonyl)-9-E-octadecenoate and methyl 8-
amino-(N-p-toluenesulfonyl)-9-E-octadecenoate in 58% yield.
These novel products were isolated and characterized by nu-
clear magnetic resonance, infrared spectroscopy, mass spec-
trometry, and melting point. The reaction was analyzed by high-
performance liquid chromatography and thin-layer chromatog-
raphy.
form N-(allylic alkenyl) sulfinamidines (4,5). Allylic amina-
tion has been investigated (6–10), but these reactions have
not been applied to fats and oils.
This article reports a one-step synthesis from methyl oleate
to allylic methyl 8- and 11-aminotosylate-9-trans-octade-
cenoates in good yield. This methodology should be applica-
ble to develop fats with an amine functionality in an allylic
position. The work discussed below details the formation of
allylic amines. The clear advantage of this method is that it
furnishes allylic amines in a one-step process (4) and retains
JAOCS 73, 229–234 (1997).
KEY WORDS: Allylic amination, methyl 11-amino-(N-p-
toluenesulfonyl)-9-E-octadecenoate, methyl 8-amino-(N-p- the ester functionality. To facilitate understanding and obser-
toluenesulfonyl)-9-E-octadecenoate, bis(N-p-toluenesulfonyl)
sulfodiimide, methyl oleate.
vation of the reaction process and mechanism, methyl oleate
served as a model substrate. Characterization was done by
using nuclear magnetic resonance (NMR), infrared (IR), and
mass spectrometry (MS). Analysis of the reaction was per-
formed by high-performance liquid chromatography (HPLC)
and thin-layer chromatography (TLC). Olefinic and amine
substitution positions were further identified by gas chro-
matography (GC) and GC–MS analysis of ozonolysis prod-
ucts (11–14) from methyl 11-amino-(N-p-toluenesulfonyl)-9-
E-octadecenoate.
About 13 billion pounds of soybean oil are produced annu-
ally in the United States. While much of this oil is used in
food and feed and about 300 million pounds are used for in-
dustrial products, there is a need to develop additional value-
added products. To meet these needs, our laboratory applies
synthetic organic chemistry techniques to functionalize soy-
bean oil or its fatty acids to produce unique fatty acid materi-
als with varying physical properties. Because reactive sites
within a triacylglycerol molecule are limited to unsaturation
and carboxylate moieties, limited chemical modifications can
be effected to functionalize the triacylglycerol. Although
modifications of the glycerol backbone are possible, fre-
quently it is desirable to maintain the chemical/physical prop-
erties of that moiety. Thus, we directed our attention to the
unsaturated carbon–carbon bond(s) of the acyl group in soy-
bean oil. For this study, we desired to maintain the olefin
functionality within the oil but utilize its unique chemistry to
modify the physical properties of the carbon chain. Extensive
work has been done in the area of allylic halogenation and ox-
idation of fats and oils (1–3), but formation of allylic amines
has received limited attention. It was reported that bis(N-p-
EXPERIMENTAL PROCEDURES
Materials. Methyl oleate (>99%) was purchased from Nu-
Chek-Prep (Elysian, MN). Thionyl chloride (99+%) was ob-
tained from Aldrich Chemical Co. (Milwaukee, WI). p-
Toluenesulfonamide was purchased from Lancaster Synthe-
sis Inc. (Windham, NH). Solvents for chromatography and
extraction were of HPLC quality and were used without fur-
ther purification. The following reaction solvents were dried
(by the methods described) and handled under a nitrogen at-
mosphere: benzene (EM Science, Gibbstown, NJ) was dis-
tilled from CaCl2 (Fisher Scientific, Fair Lawn, NJ), pyridine
(Mallinckrodt Specialty Chemicals Co., Paris, KY) was dis-
tilled from NaOH (Fisher Scientific), dichloromethane (EM
Science) was distilled from CaSO4 (W.A. Hammond Drierite
Co., Xenia, OH), and carbon tetrachloride (J.T. Baker Chemi-
cal Co., Phillipsburg, NJ) was passed through a column of
*To whom correspondence should be addressed at USDA, ARS, NCAUR,
Oil Chemical Research, 1815 North University St., Peoria, IL 61604.
Copyright © 1997 by AOCS Press
229
JAOCS, Vol. 74, no. 3 (1997)

230
B.F. HERRON ET AL.
neutral alumina (Alupharm Chemicals, New Orleans, LA) gel (200–400 mesh, 60Å) purchased from Aldrich Chemical
and stored over 4 Å molecular sieves (Aldrich Chemical Co.). Company, Inc. Samples were eluted with hexane/ethyl acetate
Synthesis of N-sulfinyl-p-toluenesulfonamide (15): A (90:10, vol/vol), and fractions were collected in 10-mL test
250-mL single-necked round-bottom (SNRB) flask and a re- tubes. The fractions were analyzed by TLC on silica gel 60
flux condenser were oven-dried (130°C), then allowed to F254 (25 µm thick on 20 × 20 cm plates) from EM Science and
cool in a desiccator. The flask and condenser were assem- by HPLC. Rf values (TLC) of 0.38 and 0.36 were obtained
bled, and a CaCl2 drying tube was attached atop the con- for methyl 11-amino-(N-p-toluenesulfonyl)-9-E-octade-
denser. The flask was charged with 31.25 g p-toluenesulfon- cenoate and methyl 8-amino-(N-p-toluenesulfonyl)-9-E-oc-
amide and 125 mL benzene as solvent. Thionyl chloride (25 tadecenoate, respectively, when using a hexane/ethyl acetate
g) was added to the reaction mixture. The reaction solution (70:30, vol/vol) solvent system. The isomeric products of
was refluxed for 5 d. After being allowed to cool, the yel- both compounds were resolved by HPLC. A center portion of
lowish solution was filtered to remove precipitates. The sol- each was collected, freed of solvent, and then used for char-
vent was removed in vacuo, and the residue was Kugelrohr- acterization.
distilled (160°C at 20 torr) to obtain 7.7 g of the N-sulfinyl-
p-toluenesulfonamide.
Instrumentation. HPLC analysis was performed on a
Hewlett-Packard 1050 HPLC system (Naperville, IL),
Synthesis of bis(N-p-toluenesulfonyl) sulfodiimide (5). equipped with an autosampler/injector and connected in series
The following operations were performed in a glove bag with with a variable wavelength detector and a Varex evaporative
a nitrogen atmosphere. N-Sulfinyl-p-toluenesulfonamide (7.7 light-scattering detector (Burtonsville, MA). A normal-phase
g) was placed in a dried 25-mL SNRB flask, and then 10 mL econosphere silica column (25 cm × 4.6 mm i.d., 5 µm) from
benzene and 1 mL pyridine were added. The reaction mixture Alltech Associates, Inc. (Deerfield, IL) was used, and all sam-
was stirred overnight, at which point a precipitate had formed. ples were eluted with hexane/ethyl acetate (90:10). Baseline
The solid was collected under vacuum filtration and washed separation of the two isomers was attained, with retention times
with dry carbon tetrachloride. The material was dried under of 15.3 and 19.1 min, respectively.
high vacuum to afford 6.5 g bis(N-p-toluenesulfonyl) sulfodi-
imide. It was found that for best results the sulfodiimide ica, MA), operating at 400 MHz for proton and 100.61 MHz
should be used immediately. for carbon. The instrument used a 5-mm dual, proton/carbon,
Allylic amination of methyl oleate. Continued use of the probe, and samples were dissolved in CDCl3.
NMR data were obtained from a Bruker ARX 400 (Biller-
glove bag and a nitrogen atmosphere is crucial for a successful
The NMR data set for methyl 11-amino-(N-p-toluenesul-
reaction. The bis(N-p-toluenesulfonyl) sulfodiimide (6.5 g) and fonyl)-9-E-octadecenoate is as follows: 1H NMR (400 MHz)
26 mL dry dichloromethane were added to a dried 100-mL δ 7.70 (d, J = 8.2 Hz, 2H), 7.24 (d, J = 8.0 Hz, 2 H), 5.28 (dt,
SNRB flask. Methyl oleate (3.9 g) was added, and the reactants J = 15.3, 6.7 Hz, 1 H), 5.01 (dd, J = 15.3, 7.4 Hz, 1 H), 4.54
were stirred for 3 d. Then, the reaction was quenched with (d, J = 7.8 Hz, 1 H), 3.69–3.64 (m, 1 H), 3.65 (s, 3H), 2.39 (s,
sodium carbonate (6 g) in 45 mL methanol/water (2:1, vol/vol), 3H), 2.28 (t, J = 7.5 Hz, 2 H), 1.79–1.76 (m, 2 H), 1.60–1.57
and the resulting solution was stirred overnight. The mixture (m, 2 H), 1.41–1.16 (m, 20 H) and 0.84 ppm (t, J = 7.0 Hz, 3
was then extracted with diethyl ether/ethyl acetate (1:1, vol/vol). H). 13C NMR (100.61 MHz) δ 174.3, 142.9, 138.6, 132.6,
The organic layer was sequentially washed with water, 4% 129.4, 129.3, 127.2, 56.1, 51.4, 36.0, 34.0, 31.9, 31.7, 29.1,
vol/vol NaOH:brine (1:1), then brine. The organic layer was 29.0, 28.2, 28.7, 25.3, 24.8, 22.6, 21.4, and 14.0 ppm.
dried over anhydrous MgSO4, filtered, and the solvent was re-
The NMR data set for methyl 8-amino-(N-p-toluenesul-
moved in vacuo. The products were purified by flash column fonyl)-9-E-octadecenoate is as follows: 1H NMR (400 MHz)
chromatography with a solvent system of hexane/ethyl acetate δ 7.70 (d, J = 8.2 Hz, 2 H), 7.24 (d, J = 8.1 Hz, 2 H), 5.26 (dt,
(80:20 vol/vol) to obtain 3.57 g of product. Methyl 11-amino- J = 15.3, 6.7 Hz, 1 H), 5.00 (dd, J = 15.3, 7.4 Hz, 1 H), 4.54
(N-p-toluenesulfonyl)-9-E-octadecenoate/m.p. 47.5–48.5°C, (d, J = 7.8 Hz, 1 H), 3.67–3.63 (m, 1 H), 3.64 (s, 3 H), 2.39
eluted off the column first. The methyl 8-amino-(N-p-toluene- (s, 3 H), 2.25 (t, J = 7.5 Hz, 2 H), 1.78–1.75 (m, 2 H),
sulfonyl)-9-E-octadecenoate, m.p. 42.5–43.5°C, eluted second.
1.56–1.53 (m, 2 H), 1.42–1.11 (m, 20 H) and 0.86 ppm (t, J =
Ozonolysis of the allylic aminotosylate ester. Ozonolysis 6.9 Hz, 3 H). 13C NMR (100.61 MHz) δ 174.2, 142.9, 138.3,
was performed as described by Isbell et al. (16). Tosylate 132.8, 129.3, 129.1, 127.2, 56.1, 51.4, 36.0, 34.0, 32.0, 31.8,
ester (3 mg) was dissolved in hexane (4 mL), and the solution 29.4, 29.2, 29.1, 28.9, 28.8, 28.7, 25.2, 24.7, 22.6, 21.4, and
was cooled to −78°C (dry ice/acetone bath). Ozone was 14.1 ppm.
passed through the solution until a faint blue color appeared.
IR spectra were obtained as CCl4 solutions by using a
Triphenylphosphine was added in excess to reduce the Perkin-Elmer 1750 Infrared Fourier Transform Spectrometer
ozonide. The resulting aldehyde and aldehyde-ester mixture (Norwalk, CT). The IR data for both isomers were the same:
was passed through a glass wool plug, then directly injected (NaCl) 3276.8 (m), 2929.6 (s), 2857.3 (s), 1738.0 (s), 1600.6
into the GC and GC–MS for analysis under GC conditions (w), 1499.3 (w),1463.1 (m), 1434.2 (m), τ 1325.7 (m), 1253.4
previously described.
(w), 1202.8 (m), 1159.4 (s), 1094.3 (m), 1047.3 (w), 967.7
Purification. Isolation of products and analytical samples (w), 815.9 (w), 707.4 (w), 664.0 (m), 577.2 (w), and 555.5
were obtained by flash column chromatography with silica cm−1 (w).
JAOCS, Vol. 74, no. 3 (1997)

IMPROVING FUNCTIONAL PROPERTIES OF SOYBEAN OIL
231
Electron ionization (EI) MS data for methyl 11-amino-(N- with methyl oleate (1 equivalent) to form a 1:1 ratio of methyl
p-toluenesulfonyl)-9-E-octadecenoate were accumulated by 11-amino-(N-p-toluenesulfonyl)-9-E-octadecenoate to methyl
direct inlet probe on a Finnigan MAT TSQ 700 (San Jose, 8-amino-(N-p-toluenesulfonyl)-9-E-octadecenoate in 58%
CA). The probe chamber was ramped from 30 to 230°C at yield (Scheme 1). This technique provided a one-step process
6°C/min, and 1 scan/s was collected. Masses and relative to an allylic amine compound.
abundances were as follows: m/z 434.3 (3.1; M − 31, − OMe),
366.2 (100), 334.2 (21.2), 294.2 (12.5), 211.2 (18.0), 155.0 the laboratory with the procedure developed by Hori et al.
(60.0), 137.2 (11.4), 91.1 (65.5), and 55.2 (12.2). (15). Preparation of the reagent requires a moisture-free envi-
The bis(N-p-toluenesulfonyl) sulfodiimide was made in
Electrospray ionization MS data for methyl 11-amino-(N- ronment. Rapid use of the reagent also appeared to be a fac-
p-toluenesulfonyl)-9-E-octadecenoate were obtained on a tor in the success and performance of the allylic amination.
Finnigan MAT SSQ710C Mass Spectrometer with the sam-
Characterization. The proton NMR spectra of the prod-
ple dissolved in hexane/isopropyl alcohol (50:50, vol/vol) ucts clearly showed the appropriate signals to identify these
with ethanolamine (MW = 61) used to produce an ionic compounds. Because of the close similarity of the NMR spec-
adduct. The single peak at m/z 527.5 (M + 62) represents the tra of 11-amino-(N-p-toluenesulfonyl)-9-E-octadecenoate
adduct of methyl 11-amino-(N-p-toluenesulfonyl)-9-E-oc- (Fig. 1) and methyl 8-amino-(N-p-toluenesulfonyl)-9-E-oc-
tadecenoate and the protonated ethanolamine.
tadecenoate (Fig. 2), the following discussion will be limited
EI–MS data for methyl 8-amino-(N-p-toluenesulfonyl)-9- to the NMR spectrum of methyl 8-amino-(N-p-toluenesul-
E-octadecenoate were accumulated by a 70-VSE mass spec- fonyl)-9-E-octadecenoate. The aromatic proton signals of the
trometer at the Mass Spectrometry Laboratory, School of p-toluene group appeared as a doublet of doublets at 7.70 and
Chemical Sciences, University of Illinois. The probe cham-
ber was at 245°C. Mass data collected and relative abun-
dances were as follows: 466.4 (15.1; M + 1), 323.2 (25),
322.2 (100), 310.3 (11.3), 295.3 (42.2), 155.0 (13.9), 91.1
(28.6).
Ozonolysis fragments were analyzed by using a Hewlett-
Packard 5890 Series II GC, equipped with a flame-ionization
detector and an autosampler/injector (Palo Alto, CA). Analy-
sis was conducted on an SP 2330 column, 30 m × 0.25 mm
i.d. (Supelco, Bellefonte, PA) with the following conditions:
column flow rate 1.48 mL/min under a helium head pressure
of 25 psi; split ratio 40:1; ramp program from 50 to 250°C at
5°C/min and held at 250°C for 5 min. Injector and detector
temperatures were set at 250°C.
SCHEME 1
GC–MS data of the ozonolytic reaction mixture were ob-
tained with a Hewlett-Packard 5890A GC, equipped with a
15 m × 0.25 mm i.d. DB-1 column (J & W Scientific, Folsom,
CA) and a Hewlett-Packard 5970 mass selective detector. GC
conditions: helium head pressure 5 psi; split 50:1; injector and
transfer line temperature at 250°C; ramp program 170 to
270°C at 3°C/min. MS conditions: mass range 50 to 550 amu;
electron multiplier 200 volts relative. Mass data collected and
relative abundances for nonan-9-al-1-ate methyl ester were as
follows: m/z 155.2 (10)(M + peak), 143.1 (17), 111.1 (29),
87.1 (72), 83.1 (39), 74.1 (100), 69.1 (19), 67.1 (13), 59.1
(29), 57.1 (15), 55.1 (90).
RESULTS AND DISCUSSION
Synthesis. It was our goal to prepare allylic amines of fatty
acyl esters, including triacylglycerols, and thus increase their
reactivity for possible exploitation in prospective polymer-
ization reactions. To survey the allylic amination process, a
model system was studied with methyl oleate as the substrate.
This reaction provided a mixture of two novel compounds
FIG. 1. 1H nuclear magnetic resonance of methyl 11-amino-(N-p-
with possible elevated reactivity. Specifically, bis(N-p-
toluenesulfonyl) sulfodiimide (1.4 equivalent) was reacted toluenesulfonyl)-9-E-octadecenoate (2).
JAOCS, Vol. 74, no. 3 (1997)

232
B.F. HERRON ET AL.
FIG. 2. 1H nuclear magnetic resonance of methyl 8-amino-(N-p-
toluenesulfonyl)-9-E-octadecenoate (3).
7.24 ppm. The COSY data show that not only there is inter-
action between the aromatic protons but also with the toluene
methyl substituent at 2.39 ppm (Fig. 3).
FIG. 3. COSY spectrum of methyl 8-amino-(N-p-toluenesulfonyl)-9-E-
octadecenoate (3).
At 5.26 ppm, there was a doublet of triplets, which inte-
grates to one proton. The peaks in that spectral region indicate
an olefinic proton, and the peak pattern would suggest the
olefin proton farthest from the nitrogen substituent. The cou-
pling constants were 15.3 and 6.7 Hz. The 15.3 Hz denotes a
trans olefin configuration. The other olefin proton signal ap-
pears at 5.00 ppm as a doublet of doublets with coupling con-
stants of 15.3 and 7.4 Hz and integrates to one proton. This
agrees with the literature report that the carbon–carbon double
bond in allylic amination products is solely E in configuration
(17).
The nitrogen proton peak at 4.54 ppm is a doublet with a
coupling constant of 7.8 Hz. Assignment was confirmed by
peak distortion by the addition of deuterium oxide to the
NMR sample, and the two-dimensional proton/carbon plot in-
dicated that there was no carbon signal related to this proton
(Fig. 4).
There are multiple signals near 3.6 ppm with an integra-
tion of four protons. The singlet at 3.65 ppm is characteristic
of an ester methoxyl group. The multiplet at 3.67–3.63 ppm
is in the appropriate region for a proton attached to a carbon
bearing a heteroatom.
Additional structural connectivity information can be ob-
tained from the COSY data (Fig. 3) where the peak at 5.26
ppm shows correlation with the peak at 5.00 ppm and the
FIG 4. HETCOR spectrum of methyl 8-amino-(N-p-toluenesulfonyl)-9-
E-octadecanoate (3).
multiplet at 1.78–1.75 ppm. In addition, the signal at 5.00 shows that at 2.39 ppm there is another three-proton signal,
ppm has correlation with the signal at 5.26 ppm and a multi- which represents the toluene methyl group. The remaining
plet at 3.67–3.65 ppm. The 4.54 ppm peak (which is the pro- proton spectrum is typical of long-chain fatty acid methyl es-
ton signal from the amine) also has a correlation with the ters, and the proton integration corresponds to the expected
3.67–3.65 ppm multiplet. This information is consistent with number of hydrogens.
the structural configuration shown in Figure 5. The arrows in-
dicate the COSY interactions between protons.
The carbon spectrum shows a carbonyl peak at 174.2 ppm
and peaks at 142.9 and 138.3 ppm, which represent the qua-
Further examination of the proton spectrum in Figure 2 ternary carbons of the aromatic ring. The peaks at 132.8 and
JAOCS, Vol. 74, no. 3 (1997)

IMPROVING FUNCTIONAL PROPERTIES OF SOYBEAN OIL
233
FIG. 6. Fragmentation pattern for methyl 11-amino-(N-p-toluenesul-
fonyl)-9-E-octadecenoate (2).
FIG. 5. Structural assignment.
129.1 ppm are of equal intensity and are in the region typical
for alkenes. The hydrogen–carbon two-dimensional correla-
tion plot gives further proof of the alkene structure with the
132.8 ppm signal of the carbon spectra corresponding to the
5.26 ppm signal of the proton spectra; and the 129.1 ppm
peak of the carbon spectra corresponding to the 5.00 ppm
peak of the proton spectra (Fig. 4). The aromatic 129.3 and
127.2 ppm carbon peaks coincide with the 7.70 and 7.24 ppm
proton peaks. The 56.1 and 51.4 ppm signals represent car-
bon attached to the nitrogen and the methoxy carbon, respec-
tively. The additional 13 peaks found upfield constitute the
remainder of carbons in the compound.
FIG. 7. Fragmentation pattern for methyl 8-amino-(N-p-toluenesul-
fonyl)-9-E-octadecenoate (3).
IR analysis provides additional proof of structure with the (M + 1). Spectra with additional fragmentation were obtained
N-H stretching at 3276.8 cm−1, carbonyl at 1738.0 cm−1, sul- from the electron ionization of the sample (Fig. 7). Major
foxide stretching at 1325.7 cm−1 and 1159.4 cm−1, and S-N fragment pathways are indicated by arrows. The base peak at
stretching at 664.0 cm−1. Confirmation of the trans double m/z 322.2 is the loss of 143.2 amu, representing the loss of
bond appears at 967 cm−1.
C9H15O2 from the methyl ester end of the molecule, and pro-
Electrospray ionization mass-spectral data for methyl 11- vides confirming evidence that the p-toluenesulfonamide
amino-(N-p-toluenesulfonyl)-9-E-octadecenoate were obtained function is located on carbon-8. Fragment ions m/z 310 and
in the form of a single signal with a mass of m/z 527.5 (M + 296 probably represent loss of the p-toluenesulfone and p-
62), corresponding to the ionic adduct of methyl 11-amino-(N- toluenesulfonamide functional groups, respectively. Ions of
p-toluenesulfonyl)-9-E-octadecenoate with ethanolamine that m/z 155 and 91 are common to both regioisomers and repre-
was used as the ion source. Fragmentation data obtained from sent the p-toluenesulfonyl and p-toluene moieties, respec-
the electron ionization of methyl 11-amino-(N-p-toluenesul- tively.
fonyl)-9-E-octadecenoate are shown in Figure 6. The m/z 434.3
Ozonolysis products from methyl 11-amino-(N-p-toluene-
signal is the loss of 31 amu (methoxy group) from the expected sulfonyl)-9-E-octadecenoate and methyl oleate were analyzed
parent molecule, a typical loss with fatty methyl ester fragmen- by GC and GC–MS. There were two distinct chromato-
tation (18). The mass peak of m/z 155, resulting from N-S graphic peaks detected for methyl oleate oxidation. GC and
cleavage, is common with compounds that contain p-toluene- GC–MS identified the peaks as nonanal and methyl 9-alde-
sulfonyl moieties (19). The base peak of m/z 366.2 is the loss hydo-nonanoate. Only methyl 9-aldehydo-nonanoate was
of 99 amu, representing the loss of C7H15 by cleavage between identified from ozonolysis of 11-amino-(N-p-toluenesul-
C11 and C12. The base peak provides evidence that the p- fonyl)-9-E-octadecenoate. This indicated that the double
toluenesulfonamide function is located on carbon-11. Frag- bond 11-amino-(N-p-toluenesulfonyl)-9-E-octadecenoate
mentation of fatty acids with amino groups is known to occur was indeed in the 9,10 carbon position. The expected substi-
adjacent to the amino group (20).
tuted amino-nonanal peak was not observed. Thus, the mass
Mass-spectral data for methyl 8-amino-(N-p-toluenesul- spectra fragmentation data and the ozonolysis products from
fonyl)-9-E-octadecenoate showed a parent peak at m/z 466.4 11-amino-(N-p-toluenesulfonyl)-9-E-octadecenoate indicate
JAOCS, Vol. 74, no. 3 (1997)

234
B.F. HERRON ET AL.
lylic Amination of Olefins and Acetylenes by Imido Selenium
Compounds, Ibid. 53:269–271 (1976).
8. Brimble, M.A., and C.H. Heathcock, Allylic Amination by the
Lewis-Acid-Mediated Ene Reaction of Diethyl Azodicarboxy-
late with Alkenes, J. Org. Chem. 58:5261–5263 (1993).
9. Johannsen, M., and K.A. Jørgensen, Iron-Catalyzed Allylic Am-
ination, Ibid. 59:214–216 (1994).
10. Shea, R.G., J.N. Fitzner, J.E. Fankhauser, A. Spaltenstein, P.A.
Carpino, R.M. Peevey, D.V. Pratt, B.J. Tenge, and P.B. Hop-
kins, Allylic Aelenides in Organic Synthesis: New Methods for
the Synthesis of Allylic Amines, Ibid. 51:5243–5251 (1986).
11. Lorenz, O., and C.R. Parks, Ozonides from Asymmetrical
Olefins. Reaction with Triphenylphosphine, Ibid. 30:1976–1981
(1965).
that the p-toluenesulfonamide group is on carbon-11. Com-
pound 8-amino-(N-p-toluenesulfonyl)-9-E-octadecenoate
was not examined by ozonolysis.
The chromatographic and spectral data confirm that the
compounds made by reacting bis(N-p-toluenesulfonyl) sul-
fodiimide and methyl oleate resulted in the formation of
methyl 11-amino-(N-p-toluenesulfonyl)-9-E-octadecenoate
and methyl 8-amino-(N-p-toluenesulfonyl)-9-E-octade-
cenoate.
ACKNOWLEDGMENTS
12. Benton, F.L., A.A. Kiess, and H.J. Harwood, Ozonolysis as a
Method for Establishing the Positions of Olefinic Linkages, J.
Am. Oil Chem. Soc. 36:457–460 (1959).
13. Privett, O.S., and E.C. Nickell, Studies on the Otonitation of
Methyl Oleate, Ibid. 41:72–77 (1964).
14. Isbell, T.A., and R. Kleiman, Characterization of Estolides Pro-
duced from the Acid-Catalyzed Condensation of Oleic Acid,
Ibid. 71:379–383 (1994).
15. Hori, T., S.P. Singer, and K.B. Sharpless, Allylic Deuteration
and Titration of Olefins with N-Sulfinylsulfonamides, J. Org.
Chem. 43:1456–1459 (1978).
The 70-VSE mass spectrometry data were obtained from the Mass
Spectrometry Laboratory, School of Chemical Sciences, University
of Illinois (Urbana–Champaign, IL), and were purchased in part with
a grant from the Division of Research Resources, National Institutes
of Health (RR 04648).
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