Inorganic Chemistry
Article
+ H]+, 307 [M + Na]+. Anal. Calcd for C18H40N2: C, 75.98; H, 14.17;
N, 9.85. Found: C, 75.24; H, 13.70; N, 9.48.
Compound L18. Amine 59 (1.05 mmol) was dissolved in anhydrous
THF (10 cm3), and a solution of 3,4-dimethoxybenzenesulfonyl
chloride (1.05 mmol) and triethylamine (3.16 mmol) in anhydrous
THF (10 cm3) was added to the amine solution. A white precipitate
formed immediately on mixing the two solutions. The reaction mixture
was left to stir at room temperature overnight. The precipitate was
filtered and the solvent was removed from the mother liquor to give a
yellow oil, which was purified by column chromatography on silica gel
using 75% EtOAc, 25% n-hexane to afford the desired product as a
Compound L14. Amine 59 (1.76 mmol) was dissolved in anhydrous
THF (10 cm3) under N2, and a solution of 3,4-dimethoxyphenyl
isocyanate (1.76 mmol) dissolved in anhydrous THF (10 cm3) was
added dropwise with stirring at room temperature. The reaction was
stirred at room temperature for 5 h. The solvent was removed to give a
yellow oil, which was purified by column chromatography on silica gel
using 94% EtOAc, 6% MeOH to afford the desired product as a white
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solid. Yield: 76%. H NMR (300 MHz, CDCl3): δ 7.05 (d, 1H, ArH,
yellow oil. Yield: 98%. H NMR (300 MHz, CDCl3): δ 7.49 (dd, 1H,
3JHH = 1.1 Hz), 6.78−6.69 (m, 2H, ArH), 5.59 (br, 1H, NH), 3.84 (s,
ArH, JHH = 2.1, 6.3 Hz), 7.35 (d, 1H, ArH, JHH = 2.1 Hz), 6.64 (d,
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6H, OCH3), 3.27 (q, 2H, CH2, 3JHH = 5.8 Hz), 2.55 (t, 2H, CH2, 3JHH
1H, ArH, JHH = 8.4 Hz), 3.96 (s, 3H, OCH3), 3.95 (s, 3H, OCH3),
3.56 (t, 2H, CH2, JHH = 5.4 Hz), 2.48 (t, 2H, CH2, JHH = 5.4 Hz),
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= 6.0 Hz), 2.40 (t, 4H, CH2, JHH = 8.7 Hz), 1.42−1.17 (m, 24H,
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CH2), 0.86 (t, 6H, CH3, JHH = 7.7 Hz) ppm; 13C NMR: (68 MHz,
2.26 (t, 4H, CH2, JHH = 7.5 Hz), 1.36−1.16 (m, 24H, CH2), 0.91 (t,
6H, CH3, JHH = 7.2 Hz) ppm; 13C NMR: (75 MHz, CDCl3): δ 152,
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CDCl3): δ 157, 149, 146, 132, 114, 112, 107, 56, 56, 54, 39, 32, 29, 29,
27, 27, 23, 14 ppm; MS (ES+): 464 [M + H]+, 484 [M + Na]+; IR
(Nujol, cm−1): 3346 (ν(NH)), 1650 (ν(CO)), 1609 (ν(Ar)); Anal. Calcd
for C27H49N3O3: C, 69.94; H, 10.65; N, 9.06. Found: C, 69.76; H,
10.68; N, 8.77.
149, 131, 121, 110, 110, 56, 56, 54, 52, 40, 32, 30, 29, 27, 27, 23, 14
ppm; MS (ES+): m/z 485 [M + H]+, 507 [M + Na]+; IR (Nujol,
cm−1): 3281 (ν(NH)), 1590 (ν(CO)), 1510 (ν(Ar)); Anal. Calcd for
C26H48N2SO4: C, 64.42; H, 9.98; N, 5.78. Found: C, 64.12; H, 9.93;
N, 5.48.
Compound L15. Amine 59 (1.76 mmol) was dissolved in anhydrous
THF (10 cm3) under N2, and a solution of 3,5-dimethoxyphenyl
isocyanate (1.76 mmol) dissolved in anhydrous THF (10 cm3) was
added dropwise with stirring at room temperature. The reaction was
stirred at room temperature for 5 h. The solvent was removed to give a
yellow oil, which was purified by column chromatography on silica gel
using 94% EtOAc, 6% MeOH to afford the desired product as a white
Methyl 3-(Di-2-ethylhexylamino)propanoate, 6. A solution of di-
2-ethylhexylamine (19.9 mmol) and methyl acrylate (40.0 mmol) in
MeOH (40 cm3) was stirred at room temperature for 24 h. The
solvent was removed using a rotary evaporator and the product was
purified by column chromatography on silica gel using 10% EtOAc,
90% hexane to afford the desired product as a colorless oil. Yield: 67%
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yield. H NMR (250 MHz, CDCl3): δ 3.88 (s, 3H, OCH3), 2.87 (t,
solid. Yield: 97%. H NMR (300 MHz, CDCl3): δ 6.59 (d, 2H, ArH,
3JHH = 2.7 Hz), 6.17 (t, 1H, ArH, 3JHH = 2.7 Hz), 3.77 (s, 6H, OCH3),
2H, NCH2CH2), 2.63 (t, 2H, CH2CO), 2.34 (d, 4H, CHCH2N),
1.35−1.67 (m, 18H, (CH2)3CHCH2), 0.95−1.18 (m, 12H, CH3); 13
C
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3.35 (q, 2H, CH2, JHH = 5.4 Hz), 2.70 (t, 2H, CH2, JHH = 5.4 Hz),
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NMR (68 MHz, CDCl3) ppm: δ 174, 60, 52, 51, 38, 33, 32, 29, 25, 24,
14, 11 ppm; IR (thin film, cm−1): (ν(CH)) 2860−2957, (ν(CO)) 1743,
(ν(CH))1456−1400, (ν(CN)) 1194, (ν(OMe))1033.
2.56 (t, 4H, CH2, JHH = 8.1 Hz), 1.52−1.21 (m, 24H, CH2), 0.88 (t,
6H, CH3, JHH = 8.1 Hz) ppm; 13C NMR: (68 MHz, CDCl3): δ 161,
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141, 98, 96, 55, 54, 39, 32, 30, 29, 28, 27, 26, 23, 14 ppm; MS (ES+):
464 [M + H]+; IR (Nujol, cm−1): 3340 (ν(NH)), 1652 (ν(CO)), 1614
(ν(Ar)); Anal. Calcd for C27H49N3O3: C, 69.94; H, 10.65; N, 9.06.
Found: C, 69.46; H, 10.77; N, 9.02.
Compound L19. Methyl 3-(di-2-ethylhexylamino)propanoate,18
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(13.0 mmol), was dissolved in hexylamine (64.9 mmol) and heated at
85 °C for 24 h. The hexylamine was removed under vacuum and the
residue was purified by column chromatography on silica gel using
50% EtOAc, 50% hexane to afford the desired product as a pale yellow
Compound L16. Amine 59 (1.05 mmol) was dissolved in water (10
cm3) containing NaOH (2.10 mmol). 3,4-Dimethoxylbenzoyl chloride
(1.05 mmol) was dissolved in CH2Cl2 (10 cm3) and added slowly to
the amine solution. The reaction was stirred at room temperature
overnight. The organic layer was separated, dried with MgSO4, and
filtered, and the solvent was removed to give a yellow oil, which was
purified by column chromatography on silica gel using 98% EtOAc, 2%
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oil. Yield: 68%. H NMR (250 MHz, CDCl3): δ 7.85 (t, 1H, NH2),
3.02−3.20 (m, 2H, NHCH2), 2.45 (t, 2H, NCH2), 2.25 (d, 4H,
NCH2), 2.07 (t, 2H, COCH2), 1.30−1.50 (m, 2H, CH2), 0.95−1.30
(m, 24H, CH2,CH), 0.49−0.95 (m, 15H, CH3) ppm; 13C NMR (68
MHz, CDCl3) δ 173, 59, 51, 40, 37, 34, 32, 32, 30, 29, 27, 25, 24, 23,
14, 14, 11 ppm; IR (thin film, cm−1): (ν(NH)) 3290, (ν(CH)) 2957−
2813, (ν(CO)) 1644, (ν(NH))1557, (ν(CH)) 1462−1377.
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MeOH to afford the desired product as a yellow oil. Yield: 85%. H
NMR (300 MHz, CDCl3): δ 7.47 (d, 1H, ArH, JHH = 2.1 Hz), 7.28
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Dimethyl 3,3′-(2-Ethylhexylimino)dipropanoate,18 7. A solution
of 2-ethylhexylamine (19.4 mmol) and methyl acrylate (59.4 mmol) in
MeOH (40 cm3) was stirred at room temperature for 24 h. The
solvent was removed using a rotary evaporator and the product was
purified by column chromatography on silica gel using 10% EtOAc,
90% hexane to afford the desired product as a colorless oil. Yield: 74%.
1H NMR (250 MHz, CDCl3): δ 3.44 (s, 6H, OCH3), 2.54 (t, 4H,
NCH2CH2), 2.22 (t, 4H, CH2CO), 2.00 (d, 2H, CHCH2N), 0.93−
1.24 (m, 9H, CH2,CH), 0.59−0.73 (m, 6H, CH3) ppm; 13C NMR (68
MHz, CDCl3) δ 173, 59, 52, 50, 37, 33, 31, 29, 24, 23, 14, 11 ppm; IR
(thin film, cm−1): (ν(CH)) 2956−2857, (ν(CO)) 1742, (ν(CH)) 1425−
1436, (ν(CN)) 1195, (ν(OMe)) 1042.
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(dd, 1H, ArH, JHH = 2.1, 6.3 Hz), 6.75 (d, 1H, ArH, JHH = 8.4 Hz),
3.94 (s, 3H, OCH3), 3.92 (s, 3H, OCH3), 3.56 (q, 2H, CH2, 3JHH = 5.1
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Hz), 2.64 (t, 2H, CH2, JHH = 5.7 Hz), 2.46 (t, 4H, CH2, JHH = 7.5
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Hz), 1.48−1.25 (m, 24H, CH2), 0.87 (t, 6H, CH3, JHH = 6.9 Hz)
ppm; 13C NMR: (75 MHz, CDCl3): δ 167, 152, 149, 127, 119, 111,
110, 58, 56, 53, 37, 32, 29, 28, 27, 23, 14 ppm; MS (ES+): 449 [M +
H]+, 471 [M + Na]+; IR (Nujol, cm−1): 3337 (ν(NH)), 1637 (ν(CO)),
1604 (ν(Ar)); Anal. Calcd for C27H48N2O3: C, 72.28; H, 10.78; N, 6.24.
Found: C, 71.96; H, 10.88; N, 6.03.
Compound L17. Amine 59 (4.00 mmol) was dissolved in water (40
cm3) containing NaOH (4.40 mmol). 3,5-Dimethoxylbenzoyl chloride
(4.0 mmol) was dissolved in CH2Cl2 (10 cm3) and added slowly to the
amine solution. The reaction was stirred at room temperature
overnight. The organic layer was separated, dried with MgSO4, and
filtered, and the solvent was removed to give a yellow oil, which was
purified by column chromatography on silica gel using 98% EtOAc, 2%
Compound L20. Dimethyl 3,3′(2-ethylhexylimino)dipropanoate 7
(16.6 mmol) was dissolved in hexylamine (133 mmol) and heated at
85 °C for 24 h. The hexylamine was removed under vacuum and the
residue was purified by column chromatography on silica gel using 5%
MeOH, 95% EtOAc to afford the desired product as a pale yellow oil.
Yield: 66%. 1H NMR (250 MHz, CDCl3): δ 7.89−8.03 (br, 2H, NH),
3.08−3.20 (m, 4H, NHCH2), 2.48 (d, 2H, NCH2), 2.81 (t, 4H,
NCH2), 2.37 (t, 4H, COCH2), 1.30−1.48 (m, 4H, CH2), 0.96−1.30
(m, 21H, CH2,CH),0.60−0.96 (m, 12H, CH3) ppm; 13C NMR (68
MHz, CDCl3) δ 173, 59, 53, 40, 37, 33, 32, 31, 30, 29, 27, 25, 24, 23,
14, 14, 11 ppm; IR (thin film, cm−1): (ν(NH)) 3289, (ν(CH)) 2928−
2804, (ν(CO)) 1643, (ν(NH)) 1558, (ν(CH)) 1458−1377.
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MeOH to afford the desired product as a yellow oil. Yield: 81%. H
NMR (300 MHz, CDCl3): δ 6.95 (d, 2H, ArH, 3JHH = 2.7 Hz), 6.57 (t,
1H, ArH, 3JHH = 2.7 Hz), 3.82 (s, 6H, OCH3), 3.51 (q, 2H, CH2, 3JHH
= 5.4 Hz), 2.70 (t, 2H, CH2, 3JHH = 5.4 Hz), 2.50 (t, 4H, CH2, 3JHH
=
8.1 Hz), 1.47−1.24 (m, 24H, CH2), 0.87 (t, 6H, CH3, 3JHH = 6.6 Hz)
ppm; 13C NMR: (75 MHz, CDCl3): δ 167, 161, 137, 107, 105, 103,
55, 54, 52, 37, 32, 30, 29, 27, 27, 23, 14 ppm; MS (ES+): 449 [M +
H]+, 471 [M + Na]+; IR (Nujol, cm−1): 3336 (ν(NH)), 1645 (ν(CO)),
1595 (ν(Ar)); Anal. Calcd for C27H48N2O3: C, 72.28; H, 10.78; N, 6.24.
Found: C, 71.78; H, 10.34; N, 6.11.
Trimethyl 3,3′,3″-Nitrilotripropanoate,18 8. A solution of 35%
aqueous ammonia (21 mmol) and methyl acrylate (168 mmol) in
L
Inorg. Chem. XXXX, XXX, XXX−XXX