K. Koumoto et al. / Tetrahedron 64 (2008) 168e174
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J¼7.6 Hz, 3H), 1.30 (q, J¼7.3 Hz, 6H), 1.62 (m, 6H), 3.43 (m,
6H), 4.23 (q, J¼7.0 Hz, 2H), 4.38 (s, 2H). Elemental Analysis:
Calculated for C16H34BrNO2$0.2H2O: C, 53.98%; H, 9.76%;
N, 3.93%. Found: C, 53.78%; H, 9.69%; N, 4.06%.
4.1.10. 6-N,N,N-Trimethylammonium-hexanate (3b)
Compound 3b was obtained quantitatively as a white pow-
der in the same way as for the preparation of 2b: FTIR (ATR)
n/cmꢀ1 2954, 1567, 1507, 1490, 1375, 909, 753; H NMR
1
(300 MHz, DMSO-d6) d/ppm 1.22 (m, 2H), 1.43 (m, 2H),
1.62 (m, 2H), 1.76 (t, J¼7.1 Hz, 2H), 3.02 (s, 9H), 3.24 (m,
2H). Elemental Analysis: Calculated for C9H19NO2$0.15H2O:
C, 61.43%; H, 11.08%; N, 7.96%. Found: C, 61.16%; H,
10.79%; N, 7.96%.
4.1.6. 2-(1-Methyl-morpholinium-1-yl)-acetic acid ethyl
ester bromide (7a)
Compound 7a was obtained in 95% yield as a white powder
in the same way as for the preparation of 4a: FTIR (ATR)
n/cmꢀ1 2974, 1731, 1471, 1416, 1226, 1122, 1030, 909; H
1
4.1.11. 2-N,N,N-Triethylammonium-acetate (4b)
NMR (500 MHz, DMSO-d6) d/ppm 1.27 (t, J¼8.8 Hz, 9H),
3.40 (s, 3H), 3.64 (m, 2H), 3.71 (m, 2H), 3.98 (m, 4H), 4.26
(q, J¼8.4 Hz, 2H), 4.72 (s, 2H). Elemental Analysis: Calcu-
lated for C9H18BrNO3$0.1H2O: C, 40.04%; H, 6.81%; N,
5.19%. Found: C, 39.91%; H, 6.81%; N, 5.19%.
Compound 4b was obtained quantitatively as a white pow-
der in the same way as for the preparation of 2b: FTIR (ATR)
n/cmꢀ1 3508, 2992, 1633, 1606, 1479, 1343, 1162, 1015, 984,
1
803, 736; H NMR (500 MHz, DMSO-d6) d/ppm 1.13 (br s,
9H), 3.38 (s, 2H), 3.46 (br s, 6H). Elemental Analysis: Calcu-
lated for C8H17NO2$0.1H2O: C, 59.67%; H, 10.79%; N,
8.70%. Found: C, 59.75%; H, 10.96%; N, 8.80%.
4.1.7. 2-(1-Methyl-piperidinium-1-yl)-acetic acid ethyl ester
bromide (8a)
4.1.12. 2-N,N,N-Tri-n-propylammonium-acetate (5b)
Compound 5b was obtained in 65% yield as a white powder
in the same way as for the preparation of 2b: FTIR (ATR)
n/cmꢀ1 3390, 2973, 1632, 1476, 1337, 1308, 947, 851, 718;
1H NMR (500 MHz, DMSO-d6) d/ppm 0.87 (t, J¼7.0 Hz,
9H), 1.59 (m, 6H), 3.35 (s, 3H), 3.40 (m, 6H), 3.44 (s, 2H).
Elemental Analysis: Calculated for C11H23NO2$0.3H2O: C,
63.91%; H, 11.53%; N, 6.78%. Found: C, 64.05%; H,
11.88%; N, 6.85%.
Compound 8a was obtained in 96% yield as a white powder
in the same way as for the preparation of 4a: FTIR (ATR)
n/cmꢀ1 2945, 1738, 1444, 1214, 1058, 1014, 944, 909, 745;
1H NMR (500 MHz, DMSO-d6) d/ppm 1.23 (t, J¼7.3 Hz,
3H), 1.51 (m, 2H), 1.81 (m, 4H), 3.21 (s, 3H), 3.50 (m, 2H),
3.58 (m, 2H), 4.21 (q, J¼7.2 Hz, 2H), 4.50 (s, 2H). Elemental
Analysis: Calculated for C10H20BrNO2: C, 45.12%; H, 7.57%;
N, 5.26%. Found: C, 45.01%; H, 7.64%; N, 5.26%.
4.1.13. 2-N,N,N-Tri-n-butylammonium-acetate (6b)
Compound 6b was obtained quantitatively as a white pow-
der in the same way as for the preparation of 2b: FTIR (ATR)
n/cmꢀ1 3407, 2956, 2872, 1629, 1472, 1352, 1145, 1307, 867,
712; 1H NMR (300 MHz, DMSO-d6) d/ppm 0.91 (t, J¼7.2 Hz,
9H), 1.26 (m, 6H), 1.54 (m, 6H), 3.33 (s, 2H), 3.41 (m, 6H).
Elemental Analysis: Calculated for C14H29NO2$0.4H2O: C,
67.10%; H, 12.01%; N, 5.59%. Found: C, 66.98%; H,
11.81%; N, 5.67%.
4.1.8. 1,2-Bis{[N,N-dimethyl-N-(acetic acid ethyl ester-1-yl)]-
ammonium-N-yl}ethane dibromide (9a)
To a solution of N,N,N0,N0-tetramethylethylene diamine
(25.0 g) in ethanol (400 mL) cooled to 4 ꢁC was added bromo-
acetic acid (100 mL) and the mixture was stirred at rt for 4
days. Precipitate produced during the reaction was filtered.
The residue was washed by ethanol with ultrasonication and
was dried in vacuo to give 9a (66.6 g, 69%) as a white powder:
FTIR (ATR) n/cmꢀ1 3008, 1745, 1469, 1382, 1241, 1208,
1
1142, 1014, 913, 856, 764; H NMR (500 MHz, DMSO-d6)
4.1.14. 2-(1-Methyl-morpholinium-1-yl)-acetate (7b)
d/ppm 1.28 (t, J¼7.0 Hz, 6H), 3.34 (s, 12H), 4.19 (s, 4H),
4.26 (q, J¼7.2 Hz, 4H), 4.58 (s, 4H). Elemental Analysis: Cal-
culated for C14H30Br2N2O4: C, 37.35%; H, 6.72%; N, 6.22%.
Found: C, 37.37%; H, 6.72%; N, 6.22%.
Compound 7b was obtained quantitatively as a white pow-
der in the same way as for the preparation of 2b: FTIR (ATR)
n/cmꢀ1 2971, 1629, 1367, 1328, 1276, 1117, 1067, 905, 878;
1H NMR (500 MHz, DMSO-d6) d/ppm 3.29 (s, 3H), 3.48 (m,
2H), 3.71 (m, 2H), 3.88 (br s, 4H). Elemental Analysis: Calcu-
lated for C7H13NO3$0.1H2O: C, 52.22%; H, 8.28%; N, 8.70%.
Found: C, 51.95%; H, 8.36%; N, 8.72%.
4.1.9. 4-N,N,N-Trimethylammonium-butylate (2b)
Compound 2a (23.7 g, 0.09 mol) dissolved in water
(20 mL) was passed through ion-exchange chromatography
(Amberite IR-402CL). The eluting solution was evaporate at
45 ꢁC to dryness and the white solid was dried in vacuo using
P2O5 to give 2b (13.2 g, 100%) as a white powder: FTIR
(ATR) n/cmꢀ1 3338, 3037, 2964, 1580, 1488, 1397, 1335,
4.1.15. 2-(1-Methyl-piperidinium-1-yl)-acetate (8b)
Compound 8b was obtained quantitatively as a white pow-
der in the same way as for the preparation of 2b: FTIR (ATR)
n/cmꢀ1 3479, 2943, 1621, 1482, 1370, 1330, 1031, 876, 798;
1H NMR (500 MHz, DMSO-d6) d/ppm 1.50 (m, 2H), 1.74 (br
s, 4H), 3.17 (s, 3H), 3.37 (m, 2H), 3.56 (s, 2H), 3.64 (m, 2H).
Elemental Analysis: Calculated for C8H15NO2$0.1H2O: C,
60.42%; H, 9.65%; N, 8.81%. Found: C, 60.26%; H, 9.45%;
N, 8.85%.
1
968, 932, 762; H NMR (500 MHz, DMSO-d6) d/ppm 1.75
(m, 2H), 1.80 (m, 2H), 3.02 (s, 9H), 3.25 (m, 2H), 3.38 (s,
9H). Elemental Analysis: Calculated for C7H15NO2$0.1H2O:
C, 57.19%; H, 10.44%; N, 9.53%. Found: C, 56.93%; H,
10.44%; N, 9.50%.