ꢀ´
Parık et al.
4138 Organometallics, Vol. 29, No. 18, 2010
(15 mL). An ethereal solution of dimethylamine (1 M, 12 mL) was
slowly added at 0 ꢀC, and the resulting suspension was stirred for
24 h at room temperature. The evaporation of solvents afforded the
crude product, which was purified by chromatography on silica
(EtOAc-hexane, 2:1). Yield: 0.60 g (93%) of a yellow oil. 1H NMR
(CDCl3, 300 MHz): δ 2.29 (s, 3H, Ph-CH3), 2.77 (s, 3H, N-CH3),
3.10 (s, 3H, N-CH3), 3.88 (s, 3H, O-CH3), 7.21 (d, J = 7.9 Hz, 1H,
Ph-H), 7.84 (m, 2H, Ph-H). 13C NMR (CDCl3, 75 MHz): δ 18.7
(Ph-CH3), 34.4(N-CH3), 38.1(N-CH3), 52.1(O-CH3), 125.9, 127.2,
130.3, 131.4, 134.4 (C-Ph), 141.1 (C-Ph), 166.5 (CdO), 170.4
(CdO). IR: ν 2951, 2929, 1723, 1639, 1510, 1437, 1407, 1395,
1300, 1288, 1258, 1220, 1198, 1110, 1067, 778 cm-1. HR-MS (ES):
calcd for C12H16NO3 222.1130; found 222.1149.
Pentacarbonyl[(N,N-dimethylamino)(3-carboxyphenyl)carbene]-
chromium(0) (2b). The same method as that used for the prepara-
tion of 2a starting from pentacarbonyl[(N,N-dimethylamino)(3-
methoxycarbonylphenyl)carbene]chromium(0) (1b) (377 mg; 0.98
mmol) afforded a yellow solid of the product (308 mg; 85%).
Mp > 110 ꢀC (dec). 1H NMR (CDCl3, 300 MHz): δ 3.08 (s, 3H,
N-CH3), 4.03 (s, 3H, N-CH3), 6.97 (d, J = 8.2 Hz, 1H, Ar-H), 7.45
(s, 1H, Ar-H), 7.51 (t, J = 8.0 Hz, 1H, Ar-H), 7.92 (d, J = 8.2 Hz,
1H, Ar-H). 13C NMR (CDCl3, 75 MHz): δ 47.3 (CH3), 52.4
(CH3), 121.1 (Ar-CH), 124.5 (Ar-CH), 127.5 (Ar-CH), 129.9
(Ar-CH), 131.9 (Ar-Cq), 153.4 (Ar-Cq), 167.9 (CO2H), 218.0
(CO), 224.8 (CO), 265.1 CdCr). IR (CHCl3): ν 2055, 1976, 1992
cm-1. Anal. Calcd (%) for C15H11CrNO7: C 48.79, H 3.00, N 3.79.
Found: C 48.65, H 3.27, N 3.65.
N,N-Dimethylisophthalamic Acid Methyl Ester. This com-
pound was prepared by a reaction of 3-chlorocarbonylbenzoic
acid methyl ester with dimethylamine in diethyl ether. 1H NMR
(CDCl3, 300 MHz): δ 2.99 (bs, 3H, N-CH3), 3.11 (bs, 3H,
N-CH3), 3.92 (s, 3H, OCH3), 7.49 (t, J = 8.2 Hz, 1H, Ar-H),
7.62 (d, J = 7.6 Hz, Ar-H), 8.06 (m, 2H, Ar-H). 13C NMR
(CDCl3, 75 MHz,): δ 35.2 (N-CH3), 39.4 (N-CH3), 52.1
(O-CH3), 128.0 (Ar-CH), 128.5 (Ar-CH), 130.1 (Ar-Cq), 130.4
(Ar-CH), 131.4 (Ar-CH), 136.5 (Ar-Cq), 166.2 (CO), 170.4
(CO). HR-MS: calcd for C11H13NO3 207.0895; found 207.0894.
Pentacarbonyl[(N,N-dimethylamino)(3-methoxycarbonylphenyl)-
carbene]chromium(0) (1b). To a suspension of chromium hexa-
carbonyl (2.2 g, 10 mmol) in THF (50 mL) was added at -78 ꢀC via
a syringe a solution of sodium naphthalenide prepared from sodium
(0.6 g, 26 mmol) and naphthalene (3.4 g, 26.5 mmol) in THF
(50 mL). The reaction mixture was then allowed to warm to 0 ꢀC,
stirred at this temperature for 30 min, and cooled to -78 ꢀC, and
3-methoxycarbonyl-N,N-dimethylbenzamide (1.45 g, 7 mmol) in
THF (5 mL) was added via a syringe. The solution was allowed to
warm to 0 ꢀC, stirred for 30 min at 0 ꢀC, and then cooled to -78 ꢀC,
and trimethylchlorosilane (2.5 mL, 20 mmol) was added via a
syringe. The solution was stirred at -78 ꢀC for 30 min, and then the
cooling bath was removed. The mixture was stirred for an addi-
tional 1 h without cooling, and neutral alumina (8 g) was added.
THF was removed under reduced pressure, and the residue was
dried under high vacuum to remove all solvents. Hexane (15 mL)
was then added, and the suspension formed was transferred to the
top of a column filled with silica gel (60 g). Naphthalene was eluted
with hexane, and further elution with hexane-dichloromethane
General Procedure for the Preparation of Amido Acids 3a-d.
Esteramide (0.5 mmol) and potassium hydroxide (56 mg,
1 mmol) were dissolved in a mixture of CH3OH (1 mL) and
water (0.5 mL), and the mixture was stirred and heated to 50 ꢀC
for 1 h. The methanol was then evaporated in a vacuum, the
residue was acidified by several drops of concentrated hydro-
chloric acid, extracted with dichloromethane (2Â 1 mL), and
dried over Na2SO4, and the solvent was evaporated.
N,N-Dimethylterephthalamic Acid (3a). Yield: 83%. 1H NMR
(CDCl3, 300 MHz): δ 2.98 (s, 3H, CH3), 3.16 (s, 3H, CH3), 7.51
(d, J = 8.2 Hz, 2H, Ar-H), 8.13 (d, J = 8.2 Hz, 2H, Ar-H), 10.05
(bs, 1H, CO2H), in accordance with ref 20. 13C NMR (CDCl3, 75
MHz): δ 35.5 (CH3), 39.5 (CH3), 127.0 (Ar-CH), 130.1 (Ar-CH),
130.4 (Ar-Cq), 140.9 (Ar-Cq), 170.3 (CO), 170.6 (CO).
N,N-Dimethylisophthalamic Acid (3b). Yield: 47%. Mp:
102-103 ꢀC (acetone). 1H NMR (CDCl3, 300 MHz): δ 2.99 (s,
3H, N-CH3), 3.14 (s, 3H, N-CH3), 7.50 (t, J = 7.6 Hz, 1H,
Ar-H), 7.67 (d, J = 7.6 Hz, 1H, Ar-H), 8.11 (d, J = 7.6 Hz, 1H,
Ar-H), 8.13 (s, 1H, Ar-H). 13C NMR (CDCl3, 75 MHz): δ 35.5
(CH3), 39.6 (CH3), 128.6 (Ar-CH), 128.7 (Ar-CH), 129.9
(Ar-Cq), 131.2 (Ar-CH), 132.1 (Ar-CH), 136.3 (Ar-Cq), 170.0
(CO), 170.7 (CO). IR: ν 2961, 2929, 1739, 1708, 1614, 1596,
1573, 1453, 1412, 1401, 1300, 1277, 1258, 1205, 742 cm-1. HR-
MS: calcd for C10H11NO3 193.0739; found 193.0734.
3,N,N-Trimethylterephthalamic Acid (3c). Yield: 89%. Mp:
200-202 ꢀC. 1H NMR (CDCl3, 300 MHz): δ 2.34 (s, 3H, CH3),
2.83 (s, 3H, N-CH3), 3.16 (s, 3H, N-CH3), 7.27 (d, J = 8.0 Hz,
1H, Ar-H), 7.95 (m, 2H, Ar-H), 10.55 (bs, 1H, CO2H). 13C
NMR (CDCl3, 75 MHz): δ 18.8 (CH3), 34.6 (N-CH3), 38.3
(N-CH3), 126.0 (Ar-CH), 127.8 (Ar-CH), 129.9 (Ar-Cq), 132.0
(Ar-CH), 134.5 (Ar-Cq), 141.4 (Ar-Cq), 170.69 (CO), 170.75
(CO). IR: ν 2926 (m), 2801 (m), 2586 (m), 1705 (s), 1614 (s), 1587
(s), 1515 (m), 1485 (m), 1416 (s), 1399 (s), 1276 (s), 1257 (s), 1223
(s), 1196 (s), 1114 (m), 1069 (m), 962 (w), 856 (w), 780 (m), 746
(m), 704 (w), 660 (m). Anal. Calcd (%) for C11H13NO3: C 63.76,
H 6.32, N 6.76. Found: C 64.20, H 6.19, N 6.72.
1
mixture (2:1) gave a product as a yellow oil (0.377 g, 14%). H
NMR (CDCl3, 300 MHz,): δ 3.06 (s, 3H, N-CH3), 3.92 (s, 3H,
O-CH3), 4.02 (s, 3H, N-CH3), 6.92 (d, J = 7.6 Hz, 1H, Ar-H), 7.39
(s, 1H, Ar-H), 7.48 (t, J = 7.6 Hz, 1H, Ar-H), 7.87 (d, J = 7.6 Hz,
1H, Ar-H). 13C NMR (CDCl3, 75 MHz): δ 46.2 (CH3), 51.4 (CH3),
52.3 (CH3), 120.0 (Ar-CH), 123.4 (Ar-CH), 127.0 (Ar-CH), 128.9
(Ar-CH), 130.5 (Ar-Cq), 152.40 (Ar-Cq), 166.5 (CO2), 216.9 (CO),
223.5 (CO), 274.2 (CdCr). IR (CHCl3): ν 2058, 1978, 1992 cm-1
.
Anal. Calcd (%) for C16H13CrNO7: C 50.14, H 3.42, N 3.65.
Found: C 50.48, H 3.62, N 3.27.
4,N,N-Trimethylisophthalamic Acid (3d). Yield: 85%. Mp:
155-157 ꢀC. 1H NMR (CDCl3, 300 MHz): δ 2.36 (s, 3H,
CH3), 2.85 (s, 3H, N-CH3), 3.16 (s, 3H, N-CH3), 7.30 (d, J =
7.7 Hz, 1H, Ar-H), 7.90 (s, 1H, Ar-H), 7.96 (d, J = 7.7 Hz, 1H,
Ar-H), 9.50 (bs, 1H, CO2H). 13C NMR (CDCl3, 75 MHz): δ 19.4
(CH3), 34.8 (N-CH3), 38.6 (N-CH3), 127.4 (Ar-Cq), 127.6
(Ar-CH), 130.3 (Ar-CH), 130.6 (Ar-CH), 136.6 (Ar-Cq), 140.5
(Ar-Cq), 170.3 (CO), 170.4 (CO). IR: ν 2923, 1716, 1597, 1399,
1286, 1248, 1214, 1129, 1118, 765 cm-1. HR-MS: calcd for
C11H13NO3 207.0895; found 207.0891.
Pentacarbonyl[(N,N-dimethylamino)(4-carboxyphenyl)carbene]-
chromium(0) (2a). Pentacarbonyl[(N,N-dimethylamino)(4-methoxy-
carbonylphenyl)carbene]chromium(0) (1b) (200 mg; 0.52
mmol), powdered KOH (112 mg; 2 mmol), water (5 mL), THF
(5 mL), and methanol (2 mL) were stirred under argon at 50 ꢀC for
5 h (starting compound quantitatively disappeared during that
time). Volatile solvents were then evaporated in a vacuum, and
nonacidic impurities were extracted with CH2Cl2. The pH of the
mixture was adjusted to 1-2 with diluted H3PO4, and the product
was extracted with diethyl ether. Extracts were dried over Na2SO4
and evaporated to afford a product as a yellow solid (180 mg;
92%), which decomposes without melting. 1H NMR (DMSO-d6,
300 MHz): δ 3.03 (s, 3H, N-CH3), 3.94 (s, 3H, N-CH3), 6.87 (d,
J = 8.4 Hz, 2H, Ar-H), 7.97 (d, J = 8.1 Hz, 2H, Ar-H), 12.94 (bs,
1H, COOH). 13C NMR (DMSO-d6, 75 MHz): δ 47.4, 52.3, 120.3,
128.8, 130.8, 156.7, 167.8, 217.9, 224.8, 265.1. IR (CHCl3): ν 2056,
Acknowledgment. This project was supported by the
Research Centre “The Structure and Synthetic Applica-
tions of Transition Metal Complexes-LC06070” of the
Ministry of Education, Youth and Sports of the Czech
Republic and by the MSM6046137301 and the MSM-
0021627501 research projects of the same Ministry.
1976, 1932 cm-1. Anal. Calcd (%) for C15H11CrNO7 0.5H2O: C
ꢁ
(20) Pytela, O.; Kulhanek, J. Collect. Czech. Chem. Commun. 2002,
67, 596.
3
47.62, H 3.17, N 3.70. Found: C 47.58, H 3.53, N 3.46.