Supplementary information
Hydroamination reaction of dialkyl esters of 2-buthenedioic acids with polyetheramines
under catalytic and non-catalytic conditions
Emília Tálas, Gábor P. Szíjjártó, András Tompos*
Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences,
Hungarian Academy of Sciences, 1117 Budapest, Magyar Tudósok körútja 2, Hungary
*
Corresponding author, Tel.: +36 1 3826 501, email: tompos.andras@ttk.mta.hu, address: H-1519 Budapest,
P.O.Box 286, Hungary (András Tompos)
Product analysis
As the amine reactants (Jeffamine D-230 and Jeffamine D-400) are mixtures of
oligomers with average molar weights of 230 and 400 respectively, depending on the number
of the -CH(CH3)-CH2-O- units (x) the following molecular weights of the individual
components are expected (Table 1).
Table S1. The molecular weights of the individual components expected in the Jeffamines and
in their addition products
x
FW
FWproduct
FWproduct
Jeffamine
Jeffamine-dibutyl
Jeffamine-dibutyl
individual
maleate 1:1 (asymmetric) maleate1:2 (symmetric)
components
addition product
addition product
individual components
individual components
1
132
360
588
2
190
418
646
3
248
476
704
4
306
534
762
5
364
592
820
6
422
650
878
7
480
708
936
8
538
766
994
9
596
824
1052
10
654
882
1110
As can be seen from ESI mass spectrum of Jeffamine D-230 (Fig. S1), the x values are
2, 3, 4, 5 and 6. Besides the molecular ions of [M+H]+, the double charged ones [M+2H]2+
also appeared. The most intense signal was given at x = 3. The highest x value was 6 which
gave a valid signal in about a thousand-fold dilution. The Jeffamine D-400 showed similar
ESI mass spectra (Fig. S2) with the major component of x = 6. The starting amines did not
contain ESI-MS detectable pollutants the same as the unsaturated di-esters (Figs. S3-S4).
Fig S1. ESI mass spectrum of Jeffamine D-230 starting material.
Jeffamine D-230 [M+H]+ ,
Jeffamine D-230 [M+2H]2+
2
Fig. S2. ESI mass spectrum of Jeffamine D-400 starting material.
Jeffamine D-400 [M+H]+ ,
Jeffamine D-400 [M+2H]2+
Fig. S3. ESI mass spectrum of diethyl maleate starting material
Fig. S4. ESI mass spectrum of dibutyl maleate starting material
3
According to the difficulties connected to the isolation, (i.e. (i) both reactants (reactant
mixtures indeed) and products (product mixture indeed) are viscous liquids with high
molecular weights and high boiling points, (ii) Jeffamines and the desired products have no
chromophore group, consequently the UV detection ordinarily used for column
chromatographic methods cannot be applied) the reaction mixtures obtained after 1 week
reaction time were analyzed as products mixtures. The ESI mass spectrum of the products
mixture obtained from the reaction of Jeffamine D-230 and dibutyl maleate (Figure 5A)
shows that starting amines were not present in detectable amount. Molecular ions of by
products such as products of ring closure, amide formations and polymerization also did not
appear in detectable amount. Only molecular ions of the mixture of the symmetric addition
product containing ester groups on both ends (main components) and molecular ions of the
mixture of asymmetric addition product containing ester groups on one end appeared in the
form of [M+H]+, [M+2H]2+and [M+Na]+(shown in Figure 5C). However quantitative data for
the ratio of symmetric and asymmetric adducts cannot be obtained based on ESI mass spectra
because the ionization efficiency is significantly higher for primary amines than for secondary
amines resulting in much higher intensity for the asymmetric addition products than for the
symmetric ones in case of equal concentrations. In order to prove this statement, 1% (Figures
5B) and 10 % (Figure 5C) Jeffamine D-230 (primary diamines) was added into the above
product mixture. As can be seen the relatively small amount of primary diamines gave higher
intensities than the secondary diamines. The following order can be written for the estimated
the ionization efficiency:
starting material > asymmetric addition product > symmetric addition product
ESI mass spectrum of Jeffamine D-400 and dibutyl maleate reaction mixture after 1
week reaction time shows a similar picture (Figure 6).
The structural units characteristic for 1H NMR of the starting materials and that of the
products are depicted in Figure 7. 1H NMR spectra of the product mixture (top) from the
reaction between Jeffamine D-230 and dibutyl maleate (stoichiometric ratio of the starting
materials=1:2, reaction time=1 week), the Jeffamine D-230 starting material (bottom) and the
assignments are presented in Figure 8. The same spectra for Jeffamine D-400 (bottom) and for
its product mixture (top) are given in Figure 9. The 1H-13C HSQC spectra are shown in Figure
10 (reaction mixture of Jeffamine D-230) and Figure11 (reaction mixture of Jeffamine D400). The presence of the saturated ester parts of the product mixtures can be seen in the
HSQC spectra. The three new HSQC peaks (H~3.8 ppm, C~55 ppm, characteristic for CH
groups, adjacent to N and C=O; H~2.9 ppm, C~51 ppm, characteristic for CH adjacent to
N; H~2.7 ppm,C~38 ppm characteristic for CH2 group , adjacent to C=O) are in agreement
with the proposed structure. The complete 1H, 13C resonance assignment could not be
performed because the samples are mixtures of compounds with different number of ether
units. The 1H NMR spectra show the presence of fumarate olefinic proton (at ~6.8 ppm) in the
product mixtures. This observation can be explained by the formation of the asymmetric
products in accordance with the ESI-MS results
Figure 12 shows the situation when dibutyl maleate was added in to the CDCl3
solution of Jeffamine D-230. The sign of the double bond of fumarate appeared immediately.
4
Fig. S5. ESI mass spectra obtained in methanol solution
A: Jeffamine D-230 and dibuthyl maleate reaction mixture after 1 week reaction time,
B: A+1% Jeffamine D-230
C: A+10% Jeffamine D-230
Assignments of the mass spectrum: Jeffamine D-230 starting material [M+H]+,
asymmetric addition products [M+H]+, symmetric addition products [M+H]+,
symmetric addition products [M+Na]+
5
Fig. S6. ESI mass spectra of Jeffamine D-400 and dibutyl maleate reaction mixture after 1
week of reaction time
Assignments of the mass spectrum:
asymmetric adition products [M+H]+,
symmetric addition products [M+H]+,
symmetric addition products [M+Na]+
6
Fig. S7. Characteristic structural units of the Jeffamine starting materials and the symmetric addition product
Fig. S8.
(bottom) 1H NMR spectrum of Jeffamine D-230 in CDCl3, measured at 400 MHz.
(top) 1H NMR spectrum of the product of reaction between Jeffamine D-230 and dibutyl malete (1:2) after 1 week
(measured in CDCl3 solution at 400 MHz)
Fig. S9.
(bottom) 1H NMR spectrum of Jeffamine D-400 in CDCl3, measured at 400 MHz.
(top) 1H NMR spectrum of the product of reaction between Jeffamine D-400 and dibutyl maleate (1:2) after 1 week
(measured in CDCl3 solution at 400 MHz)
9
Fig. S10.
H – 13C HSQC spectrum of the product of reaction between Jeffamine D-230 and dibutyl maleate (1:2) after 1 week
(measured in CDCl3 solution at 400 MHz)
1
10
Fig. S11.
H – 13C HSQC spectrum of the product of reaction between Jeffamine D-400 and dibutyl maleate (1:2) after 1 week
(measured in CDCl3 solution at 400 MHz)
1
11
Fig. S12.
(bottom) 1H NMR spectrum of Jeffamine D-230 in CDCl3 measured at 400 MHz.
(middle) 1H NMR spectrum of Jeffamine D-230 and dibutyl maleate added into CDCl3 solution measured at 400MHz
(top) 1H NMR spectrum of Jeffamine D-230, dibutyl maleate and dibutyl fumarate added into CDCl3 solution measured at
400 MHz.
12