Organometallics
Article
solution and then extracted with CH Cl (45 mL × 2). The organic
extract was dried and concentrated. The residue was passed through a
flash column, and the eluent was concentrated to give 4 as white solids
reduced products are known compounds, and their spectral analyses
2
2
1
2
are in agreement with the reported data.
Spectral Data of Products. Benzyl Alcohol. H NMR (400 MHz,
CDCl
1
1
(
530 mg, 90%). H NMR (400 MHz, CDCl ): δ 8.95−8.92 (m, 1H,
3
): δ 7.38−7.32 (m, 4H), 7.32−7.25 (m, 1H), 4.67 (s, 2H), 1.95
13
3
Pz-H), 8.26−8.17 (m, 2H, Naph-H), 8.02 (d, J = 8.2 Hz, 1H, Naph-
H), 7.77−7.75 (m, 1H, Pz-H), 7.30 (d, J = 8.2 Hz, 1H, Naph-H),
(br, 1H, OH). C NMR (100 MHz): δ 140.7, 128.4, 127.5, 126.8,
65.3.
13
1
6
1
1
.50−6.47 (m, 1H, Pz-H), 2.78 (s, 3H, CH ). C NMR (100 MHz): δ
p-Methylbenzyl Alcohol. H NMR (400 MHz, CDCl
3
): δ 7.24 (d, J
3
63.7, 154.5, 152.6, 142.8, 139.4, 136.7, 128.0, 122.2, 119.3, 112.5,
= 8.0 Hz, 2H), 7.17 (d, J = 8.0 Hz, 2H), 4.60 (s, 2H), 2.44 (br, 1H),
2
2
.37 (s, 3H). 13C NMR (100 MHz): δ 137.8,137.2, 129.1, 127.0, 64.9,
08.6, 25.6. ESI-HRMS (TOF): m/z calcd for 211.0984 C H N
12
11
4
+
1.0.
(
[M + H] ), found 211.0974.
Preparation of 7-Pyrazolyl-1,8-naphthyridine-2-carboxylic
Acid (1). Dioxane (35 mL) was added to a mixture of 4 (500 mg,
.4 mmol) and SeO (343 mg, 3.1 mmol). The resulting solution was
1
p-Methoxybenzyl Alcohol. H NMR (400 MHz, CDCl ): δ 7.23
3
(d, J = 8.8 Hz, 2H), 6.85 (d, J = 8.8 Hz, 2H), 4.53 (s, 2H), 3.78 (s,
3H), 2.80 (br, 1H). 13C NMR (100 MHz): δ 158.7, 132.9, 128.4,
2
2
1
13.6, 64.6, 55.2.
heated with an oil bath to 70 °C overnight. The reaction mixture was
filtered, and the filtrate was concentrated. The residue was dissolved in
a 0.1 M NaOH aqueous solution. Hydrochloric acid (2 M) was added
slowly until a pale yellow solid precipitated. The solid was collected
1
p-Bromobenzyl Alcohol. H NMR (400 MHz, CDCl ): δ 7.43 (d, J
3
=
8.4 Hz, 2H), 7.15 (d, J = 8.4 Hz, 2H), 4.54 (s, 2H), 3.13 (br, 1H).
13
C NMR (100 MHz): δ 139.6, 131.4, 128.5, 121.3, 64.1.
1
p-Nitrobenzyl Alcohol. H NMR (400 MHz, CDCl ): δ 8.14 (d, J =
and washed with a trace of acetone to give 1 as white solids (340 mg,
3
1
3
1
8
.8 Hz, 2H), 7.48 (d, J = 8.8 Hz, 2H), 4.79 (s, 2H), 2.50 (br, 1H). C
6
0%). H NMR (400 MHz, d -DMSO): δ 8.85 (s, 1H, Pz-H), 8.71 (d,
6
NMR (100 MHz): δ 148.1, 146.9, 12.8, 123.5, 63.9.
J = 8.8 Hz, 1H, Naph-H), 8.66 (d, J = 8.2 Hz, 1H, Naph-H), 8.33 (d, J
Methyl p-(Hydroxymethyl)benzoate. 1H NMR (400 MHz,
=
8.8 Hz, 1H, Naph-H), 8.15 (d, J = 8.2 Hz, 1H, Naph-H), 7.95 (s,
H, Pz-H), 6.70 (s, 1H, Pz-H). 13C NMR (100 MHz): δ 165.8, 153.1,
CDCl ): δ 7.92 (d, J = 8.4 Hz, 2H), 7.33 (d, J = 8.4 Hz, 2H), 4.66
1
1
3
13
(
s, 2H), 3.84 (s, 3H), 3.70 (br, 1H). C NMR (100 MHz): δ 167.1,
52.5, 151.8, 143.3, 140.9, 139.0, 127.7, 122.6, 121.0, 114.3, 109.5. IR
−
1
146.1, 129.6, 128.9, 126.3, 64.3,, 52.0.
(
KBr): 1709 cm (νC O+ ). ESI-HRMS (TOF): m/z calcd for 240.0726
1
1-Phenyl-1-ethanol. H NMR (400 MHz, CDCl ): δ 7.39−7.31
C H N O ([M + H] ), found 240.0726.
3
1
2
9
4
2
(
m, 4H), 7.31−7.24 (m, 1H), 4.86 (q, J = 6.4 Hz, 1H), 2.53 (br, 1H),
1.48 (d, J = 6.4 Hz, 3H). C NMR (100 MHz): δ 145.6, 128.3, 127.3,
Preparation of Complex 5. A mixture of 1 (50 mg, 0.21 mmol)
13
6
and [(η -benzene)RuCl ] (53 mg, 0.11 mmol) in acetonitrile (5 mL)
2
2
1
25.2, 70.3, 25.2. 1
was heated to reflux overnight. Filtration of the reaction mixture gave 5
Cyclohexanol. H NMR (400 MHz, CDCl ): δ 3.63−3.54 (m, 1H),
3
as deep yellow solids (90 mg, 88%), Recrystallization from methanol/
1
1.92−1.82 (m, 3H), 1.76−1.66 (m, 2H), 1.57−1.48 (m, 1H), 1.32−
ether gave 5 as orange crystalline solids. H NMR (400 MHz, d -
6
13
1
.08 (m, 5H). C NMR (100 MHz): δ 70.3, 35.4, 25.4, 24.0.
DMSO): δ 9.40 (m, 1H, Pz-H), 9.20 (m, 1H, Pz-H), 9.10 (d, J = 8.8
Hz, 1H, Naph-H), 8.90 (d, J = 8.2 Hz, 1H, Naph-H), 8.65 (d, J = 8.8
1
m-Hydroxybenzyl Alcohol. H NMR (400 MHz, d -acetone): δ
6
7
.12 (t, J = 7.8 Hz, 1H), 6.87 (s, 1H), 6.80 (d, J = 7.8 Hz, 1H), 6.70
Hz, 1H, Naph-H), 8.49 (d, J = 8.2 Hz, 1H, Naph-H), 7.22 (m, 1H, Pz-
13
H), 6.45 (s, 6H, Bz-H). 13C NMR (100 MHz): δ 165.5, 152.7, 151.7,
(dd, J = 7.8 Hz, J = 2.5 Hz, 1H), 4.56 (s, 2H). C NMR (100 MHz):
δ 157.8, 144.5, 129.7, 118.2, 114.3, 114.0, 64.5.
1
51.2, 149.5, 144.0, 141.0, 133.1, 123.5, 123.5, 113.5, 112.9, 86.3. ESI-
1
p-Cresol. H NMR (400 MHz, CDCl ): δ 7.02 (d, J = 8.4 Hz, 2H),
+
3
HRMS (TOF): m/z calcd for 454.9849 C H ClN O Ru ([5 − Cl] ),
found 454.9853. Anal. Calcd for 5 (C H Cl N O Ru): C, 44.09; H,
13
18
14
4
2
6
1
.72 (d, J = 8.4 Hz, 2H), 2.26 (s, 3H). C NMR (100 MHz): δ 153.3,
18
14
2
4
2
30.0, 129.9, 115.1, 20.4.
2
.88; N, 11.43. Found: C, 43.69; H, 2.57; N, 11.51.
1
o-Cresol. H NMR (400 MHz, CDCl ): δ 7.15−7.04 (m, 2H),
3
Preparation of Complex 6. The procedure for the preparation of
6
3
1
.87−6.81 (m, 1H), 6.76 (d, J = 8.0 Hz, 1H), 4.89 (br, 1H), 2.24 (s,
6
6
(
was similar to that for 5 but with the use of [(η -p-cymene)RuCl ]
13
2
2
H). C NMR (100 MHz): δ 153.7, 131.0, 127.1, 123.7, 120.7, 114.9,
1
55 mg, 80%). H NMR (400 MHz, d -DMSO): δ 9.45−9.39 (m, 1H,
6
5.7.
Pz-H), 9.19−9.15 (m, 1H, Pz-H), 9.11 (d, J = 8.9 Hz, 1H, Naph-H),
1
N,N-Dimethyl-p-toluidine. H NMR (400 MHz, CDCl ): δ 7.04
3
8
8
2
.91 (d, J = 8.3 Hz, 1H, Naph-H), 8.66 (d, J = 8.9 Hz, 1H, Naph-H),
.50 (d, J = 8.3 Hz, 1H, Naph-H), 7.25−7.21 (m, 1H, Pz-H), 6.75 (br,
H, Ar-H), 6.47 (br, 1H, Ar-H), 6.12 (br, 1H, Ar-H), 2.52 (br, 1H, Ar-
(
3
d, J = 8.6 Hz, 2H), 6.67 (d, J = 8.6 Hz, 2H), 2.87 (s, 6H), 2.26 (s,
H). C NMR (100 MHz): δ 148.8, 129.5, 125.5, 113.2, 41.0, 20.2.
Crystallography. Crystals suitable for X-ray determination were
13
13
H), 2.18 (br, 3H, Ar-H), 0.98 (br, 6H, Ar-H). C NMR (100 MHz):
obtained for 5·H O and 6·3CH OH by recrystallization from wet
2
3
1
1
65.5, 152.8, 151.7, 151.1, 149.3, 143.9, 133.2, 129.7, 123.6, 123.5,
13.5, 113.0, 110.4, 100.9, 84.8, 81.8, 79.3, 78.6, 30.4, 21.9, 21.8, 18.7.
methanol. Cell parameters were determined with a Siemens SMART
CCD diffractometer. The structure was solved using the SHELXS-97
1
3
14
ESI-HRMS (TOF): m/z calcd for 511.0472 C H ClN O Ru ([6 −
2
2
22
4
2
program and refined using the SHELXL-97 program by full-matrix
+
2
Cl] ), found 511.0489. Anal. Calcd for 6 (C H Cl N O Ru): C,
2
2
22
2
4
2
least squares on F values. Crystal data of these complexes are given in
4
8.36; H, 4.06; N, 10.25. Found: C, 48.69; H, 3.87; N, 10.51.
the Supporting Information. Other crystallographic data have been
deposited as Supporting Information.
Preparation of Complex 7. The procedure for the preparation of
7
(
was similar to that for 5. Complex 7 was obtained as a yellow solid
1
90%). H NMR (400 MHz, d -DMSO): δ 9.34 (m, 1H, Pz-H), 9.15
6
ASSOCIATED CONTENT
Supporting Information
■
(
m, 1H, Pz-H), 8.95 (d, J = 8.8 Hz, 1H, Naph-H), 8.59 (d, J = 8.2 Hz,
*
S
1
1
H, Naph-H), 8.46 (d, J = 8.8 Hz, 1H, Naph-H), 7.84 (d, J = 8.2 Hz,
A figure giving an ORTEP plot of the cationic part of 6, tables
of crystal data, atomic positional parameters, bond distances
and angles, anisotropic thermal parameters, and calculated
hydrogen atom positions for complexes 5 and 6, and CIF files
H, Naph-H), 7.18 (m, 1H, Pz-H), 6.33 (s, 6H, Bz-H), 2.98 (s, 3H,
13
CH3). C NMR (100 MHz): δ 166.1, 152.7, 150.5, 149.5, 144.4,
39.3, 133.2, 125.1, 120.7, 113.1, 111.2, 86.7, 25.5. ESI-HRMS (TOF):
1
+
m/z calcd for 425.0103 C H ClN Ru ([6 − Cl] ), found 425.0107.
Anal. Calcd for C H Cl N Ru·H O: C, 45.20; H, 3.79; N, 11.71.
18
16
4
18
16
2
4
2
Found: C, 45.56; H, 3.72; N, 11.70.
General Procedure for the Catalytic Reduction. A mixture of
substrate (0.5 mmol), HCOOH (5 mmol), HCOONa (5 mmol), and
AUTHOR INFORMATION
−3
■
complex 5 (7.5 × 10 mmol) in water (5 mL) was stirred at 60 °C for
2
0 h under an N atmosphere. After the reaction, ethyl acetate (5 mL
2
*
×
3) was added to extract the organic products. All organic extracts
were dried and concentrated. The desired product was purified by
chromatography with CH Cl /EtOAc = 30/1−10/1 as eluent. All
Notes
The authors declare no competing financial interest.
2
2
E
dx.doi.org/10.1021/om5003528 | Organometallics XXXX, XXX, XXX−XXX