Preparation and reaction of quinolinyl (or pyridinyl)phosphonium salts with base and pivalaldehyde

Article abstract of DOI:10.3987/COM-11-12154

α- and γ-Heteroaryltriphenylphosphonium iodides were prepared by reaction of the corresponding heteroaryl iodides with triphenylphosphine. Reaction of β-heteroaryl iodides with triphenylphosphine in the presence of a palladium catalyst gave β-heteroaryltriphenylphosphonium iodides. Elimination of the heteroaryl group was achieved by treating the heteroaryltriphenylphosphonium iodides with a base. Further, the heteroaryl group was trapped with pivalaldehyde to introduce a pivaloyl substituent onto the heteroaromatic ring.

Full text of DOI:10.3987/COM-11-12154

HETEROCYCLES, Vol. 83, No. 4, 2011
837
HETEROCYCLES, Vol. 83, No. 4, 2011, pp. 837 - 847. © The Japan Institute of Heterocyclic Chemistry
Received, 25th January, 2011, Accepted, 21st February, 2011, Published online, 28th February, 2011
DOI: 10.3987/COM-11-12154
PREPARATION AND REACTION OF QUINOLINYL (OR
PYRIDINYL)PHOSPHONIUM SALTS WITH BASE AND
PIVALALDEHYDE
Minami Shimada, Osamu Sugimoto,* Akihiro Sato, and Ken-ichi Tanji
Laboratory of Organic Chemistry, School of Food and Nutritional Sciences
University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-8526, Japan
osamu@u-shizuoka-ken.ac.jp
Abstract – - and -Heteroaryltriphenylphosphonium iodides were prepared by
reaction of the corresponding heteroaryl iodides with triphenylphosphine.
Reaction of -heteroaryl iodides with triphenylphosphine in the presence of a
palladium catalyst gave -heteroaryltriphenylphosphonium iodides. Elimination
of
the
heteroaryl
group
was
achieved
by
treating
the
heteroaryltriphenylphosphonium iodides with a base. Further, the heteroaryl group
was trapped with pivalaldehyde to introduce a pivaloyl substituent onto the
heteroaromatic ring.
INTRODUCTION
There are many reactions that take advantage of the high affinity between phosphorus and oxygen.
Alkenes are prepared via reaction of carbonyl compounds with phosphonium ylides (Wittig reaction)1 or
phosphonate carbanions (Horner-Wadsworth-Emmons reaction).2 Carboxylic acids and sulfonic acids can
be converted into the corresponding acyl chlorides and sulfonyl chlorides using phosphorus
oxychloride,3,4
phosphorus
pentachloride,5
triphenylphosphine-carbon
tetrachloride6
or
triphenylphosphine-N-chlorosuccinimide.7 Phosphorus oxyhalides, triphenylphosphine-N-halosuccinimi-
des and triphenylphosphine-trichloroisocyanuric acid are used for halogenation of
hydroxyheteroaromatics.8,9 We have reported in
a
preliminary communication10 that
heteroaryltriphenylphosphonium iodides prepared from triphenylphosphine and heteroaryl iodides react
with protonic solvents such as water and ethanol in the presence of base to eliminate the heteroaryl group
(A). We have now applied this reaction to carbon-carbon bond formation (B) and report our results in this
paper (Scheme 1).

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HETEROCYCLES, Vol. 83, No. 4, 2011
protonic solvents
Het
H
E
Het PPh3 I
bases
A
electrophiles (E+)
Het
B
Scheme 1
RESULTS AND DISCUSSION
Initially, quinolinyltriphenylphosphonium iodides (1-3) were prepared by two routes, Method A and
Method B, as shown in Scheme 2.
PPh3
R
N
I
I
Method A
PPh3
110 °C
1 (85%)
3 (91%)
PPh3
I
PPh3
I
R
N
R
N
R
N
1 (4-PPh3I, R = Cl)
2 (3-PPh3I, R = H)
3 (2-PPh3I, R = H)
PdI
PPh3, Pd2(dba)3
xylene, reflux
2 (95%)
Method B
R
N
Scheme 2
Method A is a simple addition-elimination reaction between triphenylphosphine and organic halides, but
requires the halide to be reactive towards nucleophiles, while Method B is a palladium catalyzed cross
coupling reaction11 between triphenylphosphine and organic halides that does not require reactivity
towards nucleophiles. Method A12 can be applied to the reaction of 2-iodo- and 4-iodoquinoline
derivatives since it is known that the positions  or  to the ring nitrogen in nitrogen-containing
heteroaromatics are reactive with nucleophiles.13 For example, reaction of 7-chloro-4-iodoquinoline with
triphenylphosphine at 110 °C gave the disired phosphonium iodide 1 in 85% yield. Similarly, reaction of
2-iodoquinoline with triphenylphosphine at 110 °C afforded 3 in 91% yield. In contrast, reaction of
3-iodoquinoline with triphenylphosphine does not proceed under these conditions because the position 
to the ring nitrogen in nitrogen-containing heteroaromatics is inert to nucleophiles. However,

HETEROCYCLES, Vol. 83, No. 4, 2011
839
3-iodoquinoline can be converted to the phosphonium salt using Method B. Reaction of 3-iodoquinoline
with triphenylphosphine in xylene in the presence of catalytic amount of
a
tris(dibenzylideneacetone)dipalladium gave the phosphonium salt, 2 in 95% yield.
Method A can also be used to prepare pyridinyl derivatives since the -position of the pyridine ring is
reactive with nucleophiles.13 Preparation of 2-pyridinyltriphenylphosphonium iodides 4 and 5 was carried
out by reaction of triphenylphosphine with 2-iodopyridine and 2,5-diiodopyridine at 140 °C in 66% and
79% yields, respectively (Scheme 3).
Scheme 3
Next, preparation of 2-pyridinyltriphenylphosphonium trifluoromethanesulfonate (6) by using
2-(trifluoromethanesulfonyloxy)pyridine as a substrate instead of 2-iodopyridine was examined (Table 1).
First, reaction of the substrate with triphenylphosphine by Method A was attempted because the
trifluoromethanesulfonyloxy group is regarded as a good leaving group.14,15 The product 6 was not
obtained, however, even when the reaction was run at 120-130 °C for 0.5 h (Entry 1). Preparation of 6
using the palladium catalyzed coupling reaction was then carried out. A mixture of the substrate,
triphenylphosphine, and tetrakis(triphenylphosphine)palladium was heated at 130 °C for 0.5 h to
gratifyingly afford 6 in 87% yield (Entry 2).
Table 1
PPh3, Pd(PPh3)4 (presence or absence)
OSO2CF3
condition
N
OSO2CF3
N
PPh3
6
Entry
Pd(PPh3)4
none
Condition
120-130 °C, 0.5 h
130 °C, 0.5 h
Yield of 6 (%)
1
2
0
0.3 mol%
87
The reactivity of the quinolinyltriphenylphosphonium iodides (1-3) was then evaluated by treating them
with several reagents (Table 2). Reaction of 1 with water or ethanol was unsuccessful (Entries 1, 2). On

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HETEROCYCLES, Vol. 83, No. 4, 2011
the other hand, reaction of 1 with basic solvents such as aqueous sodium hydroxide (Entry 3) and
ethanol-triethylamine (Entry 4) gave the desired quinoline in 82% and 87% yields, respectively.
Moreover, the quinoline was obtained in good yield even though an aprotic solvent,
N,N-dimethylformamide containing triethylamine was used (Entry 5). This result suggests that a
quinolinyl anion abstracts a proton even from an aprotic compound because of its instability at high
temperature. Generation of quinolines by reaction of 2 and 3 with ethanol-triethylamine (Entries 6, 7)
proceeded in a manner similar to that in Entry 4.
Table 2
I
reagent
PPh3
H+ (derived from solvent)
R
N
R
N
1 (4-PPh3I, R = Cl)
2 (3-PPh3I, R = H)
3 (2-PPh3I, R = H)
Entry
Substrate
Reagent
H2O
Condition
reflux, 5 h
reflux, 0.5 h
reflux, 1 h
reflux, 1 h
120 °C, 1.5 h
reflux, 1 h
reflux, 1 h
Yield (%)
1
2
3
4
5
6
7
1
1
1
1
1
2
3
trace
0
EtOH
0.5 N NaOH
EtOH, Et3N
DMF, Et3N
EtOH, Et3N
EtOH, Et3N
82
87
67
87
73
Functionalization of the quinoline substrates was next examined. Reaction of 3 with base in the presence
of pivalaldehyde was carried out to introduce the pivaloyl substituent at the -position of the quinoline
ring (Table 3). This reaction was conducted at room temperature because the generated quinolinyl anion
would be unstable at higher temperatures. To avoid generation of quinoline, either no or an aprotic
solvent was used. The combination of triethylamine in tetrahydrofuran afforded the product,
2,2-dimethyl-1-(2-quinolinyl)-1-propanol in 39% yield along with 23% of revovered quinoline (Entry 1).
When strong bases such as sodium hydroxide (Entry 2), sodium oxide (Entries 3-5), and potassium
hydroxide (Entries 6-8) were used, product yields were slightly improved, but recovered quinoline was
still isolated as a byproduct. Interestingly, elimination of the quinolinyl group occurs selectively to react
with pivalaldehyde or a proton source, but elimination of the phenyl group followed by trapping with
pivalaldehyde does not occur.

HETEROCYCLES, Vol. 83, No. 4, 2011
841
Table 3
Yields (%)
tBuCHO
Entry
Base
Solvent
Condition
(eq)
6
Product
Quinoline
1
2
3
4
5
6
7
8
Et3N (2.0 eq)
NaOH (2.0 eq)
Na2O (2.0 eq)
Na2O (1.0 eq)
Na2O (1.0 eq)
KOH (2.0 eq)
KOH (2.0 eq)
KOH (1.3 eq)
THF
THF
rt, 24 h
rt, 24 h
rt, 24 h
rt, 24 h
rt, 22 h
rt, 24 h
rt, 24 h
rt, 17 h
39
48
50
44
60
46
61
32
23
48
24
37
31
19
33
19
6
6
THF
6
benzene
none
28
6
THF
6
benzene
none
28
Treatment of 2 with base in the presence of pivalaldehyde was then carried out to compare its reactivity
with that of 3 (Table 4).
Table 4
tBuCHO
Yields (%)
Entry
Base
Solvent
Condition
(eq)
6
Product
Quinoline
1
2
3
4
5
KOH (2.0 eq)
KOH (2.0 eq)
KOH (4.1 eq)
Na2O (1.1 eq)
tBuOK (1.0 eq)
benzene
THF
rt, 24 h
rt, 22 h
rt, 29 h
rt, 21 h
rt, 44 h
29
25
41
0
67
56
36
24
27
6
28
28
28
none
none
none
13
A mixture of 2, potassium hydroxide, and pivalaldehyde in a solvent (benzene, THF, and no solvent) was
stirred at room temperature to give 2,2-dimethyl-1-(3-quinolinyl)-1-propanol in 29%, 25%, and 41%
yields with quinoline in 67%, 56%, and 36% yields, respectively (Entries 1-3). As compared with the
results in Table 3, the yield of the desired product was lower and that of quinoline higher. In addition, the
use of sodium oxide and potassium t-butoxide as base afforded the product in poor yields (Entries 4, 5).

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HETEROCYCLES, Vol. 83, No. 4, 2011
Next, the reaction of 1 with base in the presence of pivalaldehyde at room temperature was explored
(Table 5). In this case, elimination of the 7-chloroquinolinyl group proceeded smoothly to give high total
yields of the desired product and 7-chloroquinoline (Entries 2-4, 62-90%), but the eliminated
7-chloroquinolinyl group was preferentially trapped by a proton rather than pivalaldehyde.
Table 5
tBuCHO
Yields (%)
7-chloroquinoline
Entry
Base
Solvent
Condition
(eq)
28
6
Product
1
2
3
4
Na2O (1.0 eq)
KOH (2.0 eq)
KOH (4.0 eq)
KOH (2.0 eq)
none
benzene
CH2Cl2
THF
rt, 16.5 h
rt, 24 h
rt, 24 h
rt, 24 h
0
16
0
44
74
63
49
10
6
13
Figure 1 shows the speculated stabilities of quinoline carbanions generated from 2-, 3-, and
4-quinolinyltriphenylphosphonium salts and bases. It is reasonable that a carbanion at the -position of
quinoline (-carbanion) is more stable than the -carbanion, and the -carbanion is more stable than the
-carbanion since the ring nitrogen has a strong inductive effect (“I effect”) for stabilization of nearby
carbanions. Unstable carbanions such as the -carbanion immediately trap a proton from other reagents.
Figure 1
From the results shown above, it is estimated that carbanions at the -position of pyridines, by reaction of
2-pyridinyltriphenylphosphonium salts with base, will trap pivalaldehyde to form
2,2-dimethyl-1-(2-pyridinyl)-1-propanols. As shown in Table 6, 2-pyridinyltriphenylphosphonium iodide

HETEROCYCLES, Vol. 83, No. 4, 2011
843
(4), (5-iodo-2-pyridinyl)triphenylphosphonium iodide (5) and 2-pyridinyltriphenylphosphonium
trifluoromethanesulfonate (6) were used as substrates to test this hypothesis. As expected, carbon-carbon
bond formation proceeded to give the products in moderate to good yields. It was found that both triflates
and iodides are effective in this transformation.
Table 6
R
R
base,tBuCHO, solvent
X
N
PPh3
N
OH
4 (R = H, X = I)
5 (R = I, X = I)
6 (R = H, X = OSO2CF3)
tBuCHO
Entry
Substrate
Base
Solvent
Condition
Yield (%)
(eq)
6
1
2
4
4
4
4
5
5
5
5
6
6
6
KOH (2.0 eq)
KOH (2.0 eq)
KOH (7.0 eq)
Na2O (1.0 eq)
KOH (2.0 eq)
KOH (2.1 eq)
KOH (7.0 eq)
Na2O (1.0 eq)
KOH (2.0 eq)
KOH (2.0 eq)
KOH (7.0 eq)
benzene
THF
rt, 24 h
rt,22 h
rt, 19 h
rt, 24 h
rt, 24 h
rt, 22 h
rt, 23 h
rt, 24 h
rt, 24 h
rt, 24 h
rt, 24 h
67
38
6
3
28
28
6
none
61
4
none
74
5
benzene
THF
44 (23*)
36 (26*)
53 (12*)
52 (25*)
41
6
6
7
28
28
6
none
8
none
9
THF
10
11
6
benzene
none
50
28
62
* : Yields of 3-iodopyridine
In summary, we have demonstrated that heteroaryltriphenylphosphonium salts react in the presence of
base to eliminate the heteroaryl group, which can then be trapped with an aldehyde or proton.
Furthermore, the reactivity of the eliminated heteroaryl group with pivalaldehyde varies depending on the
position of the carbanion in the heteroaromatic ring.
EXPERIMENTAL
1
All melting points were not corrected. H-NMR spectra were measured with an Hitachi R-90H
spectrometer (90 MHz) using tetramethylsilane as an internal standard.
Preparation of 7-chloro-4-quinolinyltriphenylphosphonium iodide (1) (Scheme 2): A mixture of

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HETEROCYCLES, Vol. 83, No. 4, 2011
7-chloro-4-iodoquinoline (5790 mg, 20.0 mmol) and triphenylphosphine (5246 mg, 20.0 mmol) was
dissolved in CH2Cl2 (50 mL). The CH2Cl2 was then removed under atmospheric pressure and the residue
heated at 110 °C for 1 h followed by recrystallization from EtOH to give 1 (9362 mg, 85%).
1
1: Yellow prisms. Mp 257-265 °C. H-NMR (DMSO-d6) ppm: 7.28-8.13 (18H, m, C3,C5,C6, and
triphenyl-H), 8.42 (1H, brs, C8-H), 9.28 (1H, t, J=4.3 Hz, C2-H). Anal. Calcd for C27H20ClINP: C, 58.77;
H, 3.65; N, 2.54. Found: C, 58.50; H, 3.86; N, 2.33.
Preparation of 3-quinolinyltriphenylphosphonium iodide (2) (Scheme 2): A mixture of 3-iodoquinoline
(3840 mg, 15.1 mmol), tris(dibenzylideneacetone)dipalladium (140 mg, 0.153 mmol), triphenylphosphine
(3944 mg, 15.0 mmol) and xylene (10 mL) was heated to reflux for 16 h. The reaction mixture was then
washed with AcOEt and the residual solids dried under reduced pressure to give 2 (7400 mg, 95%).
2: Slightly yellow solids (recryst. from AcOEt-EtOH). Mp 234-235 °C. 1H-NMR (CDCl3) ppm: 7.56-8.12
(17H, m, C6,C7, and triphenyl-H), 8.21 (1H, d, J=8.1 Hz, C5-H), 8.43 (1H, d, J=7.7 Hz, C8-H), 8.87 (1H,
dd, J=4.5 Hz, 2.3 Hz, C4-H), 9.09 (1H, dd, J=14.7 Hz, 2.1 Hz, C2-H). Anal. Calcd for C27H21INP: C,
62.68; H, 4.09; N, 2.71. Found: C, 62.52; H, 4.21; N, 2.76.
Preparation of 2-quinolinyltriphenylphosphonium iodide (3) (Scheme 2): A mixture of 2-iodoquinoline
(3460 mg, 13.6 mmol) and triphenylphosphine (3559 mg, 13.6 mmol) was heated at 110 °C for 1 h 40
min. The reaction mixture was then washed with AcOEt and the residual powder dried under reduced
pressure to give 3 (6377 mg, 91%).
3: Milky white powder. Mp 213-214 °C. 1H-NMR (CDCl3) ppm: 7.57-8.30 (20H, m, C3,C5,C6,C7,C8, and
triphenyl-H), 8.85 (1H, dd, J=8.6 Hz, 5.5 Hz, C4-H). Anal. Calcd for C27H21INP·0.5H2O: C, 61.61; H,
4.21; N, 2.66. Found: C, 61.60; H, 4.63; N, 2.51.
Preparation of 2-pyridinyltriphenylphosphonium iodide (4) (Scheme 3): A mixture of 2-iodopyridine
(4100 mg, 20.0 mmol) and triphenylphosphine (5246 mg, 20.0 mmol) was heated at 140 °C for 3 h. The
reaction mixture was cooled and washed with AcOEt (30 mL) to give 4 (6129 mg, 66%).
4: Slight yellow powder. Mp 287.6 °C (lit.,16 289-292 °C). 1H-NMR (DMSO-d6) ppm: 7.46-8.40 (18H, m,
C3,C4,C5, and phenyl-H), 9.07 (1H, d, J=4.4 Hz, C6-H).
Preparation of (5-iodo-2-pyridinyl)triphenylphosphonium iodide (5) (Scheme 3): A mixture of
2,5-diiodopyridine (6628 mg, 20.0 mmol) and triphenylphosphine (5258 mg, 20.0 mmol) was heated at
140 °C for 5 h. The reaction mixture was cooled and washed with AcOEt (20 mL) and the residue
recrystallized from EtOH to give 5 (9319 mg, 79%).
1
5: Yellow prisms. Mp 243.4 °C. H-NMR (DMSO-d6) ppm: 7.49-8.19 (16H, m, C3 and phenyl-H),
8.48-8.75 (1H, m, C4-H), 9.32 (1H, s, C6-H). Anal. Calcd for C23H18I2NP: C, 46.57; H, 3.06; N, 2.36.
Found: C, 46.45; H, 3.07; N, 2.52.

HETEROCYCLES, Vol. 83, No. 4, 2011
845
Preparation of 2-pyridinyltriphenylphosphonium trifluoromethanesulfonate (6) (Table 1): A mixture of
2-trifluoromethanesulfonyloxypyridine (3177 mg, 14.0 mmol), triphenylphosphine (3668 mg, 14.0 mmol)
and tetrakis(triphenylphosphine)palladium (51 mg, 0.0441 mmol) in CH2Cl2 (10 mL) was stirred and
CH2Cl2 was then removed. The residual mixture was heated at 130 °C for 30 min. The reaction mixture
was then cooled and washed with Et2O (20 mL). The crude solids were purified by silica gel column
chromatography (eluted with hexane-AcOEt (5:1)) to give 6 (5985 mg, 87%).
1
6: White powder. Mp 251.8-253.4 °C (lit.,16 256-259 °C). H-NMR (CDCl3) ppm: 7.48-8.03 (17H, m,
C4,C5, and phenyl-H), 8.14 (1H, m, C3-H), 8.99 (1H, d, J=4.9 Hz, C6-H).
Reaction of 1 with 0.5 N NaOH solution (Table 2, Entry 3): A mixture of 1 (552 mg, 1.00 mmol) in 0.5 N
aqueous NaOH (20 mL) was heated to reflux for 1 h. The reaction mixture was then neutralized and
extracted with AcOEt. The organic layer was concentrated and purified by silica gel column
chromatography (eluted with hexane-AcOEt (3:1)) to give 7-chloroquinoline (135 mg, 82%).
1
7-Chloroquinoline: Colorless liquids. MS 163 (M+). H-NMR (CDCl3) ppm: 7.28-7.62 (2H, m, C3 and
C6-H), 7.76 (1H, d, J=8.7 Hz, C5-H), 7.96-8.28 (2H, m, C4 and C8-H), 8.91 (1H, dd, J=4.1 Hz, 1.4 Hz,
C2-H).
Reaction of 1 with EtOH and triethylamine (Table 2, Entry 4): A mixture of 1 (552 mg, 1.00 mmol),
EtOH (10 mL) and triethylamine (3 mL) was heated to reflux for 1 h. After EtOH and triethylamine were
removed under reduced pressure, the residue was purified by silica gel column chromatography (eluted
with hexane-AcOEt (3:1)) to give 7-chloroquinoline (143 mg, 87%).
Reaction of 1 with N,N-dimethylformamide and triethylamine (Table 2, Entry 5): A mixture of 1 (552 mg,
1.00 mmol), N,N-dimethylformamide (2 mL) and triethylamine (2 mL) was heated at 120 °C for 1.5 h.
The reaction mixture was then purified by silica gel column chromatography (eluted with hexane-AcOEt
(2:1)) to give 7-chloroquinoline (109 mg, 67%).
Reaction of 2 with EtOH and triethylamine (Table 2, Entry 6): A mixture of 2 (517 mg, 1.00 mmol),
EtOH (10 mL) and triethylamine (3 mL) was heated to reflux for 1 h. After EtOH and triethylamine were
removed under reduced pressure, the residue was purified by silica gel column chromatography (eluted
with hexane-AcOEt (1:1)) to give quinoline (112 mg, 87%).
1
Quinoline: Colorless liquids. H-NMR (CDCl3) ppm: 7.39 (1H, dd, J=8.3 Hz, 4.2 Hz, C3-H), 7.48-7.93
(3H, m, C5, C6, and C7-H), 7.96-8.31 (2H, m, C4 and C8-H), 8.92 (1H, dd, J=4.2 Hz, 1.5 Hz, C2-H).
Reaction of 3 with EtOH and triethylamine (Table 2, Entry 7): A mixture of 3 (523 mg, 1.01 mmol),
EtOH (10 mL) and triethylamine (3 mL) was heated to reflux for 1 h. After EtOH and triethylamine were
removed under reduced pressure, the residue was purified by silica gel column chromatography (eluted
with hexane-AcOEt (1:1)) to give quinoline (95 mg, 73%).

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HETEROCYCLES, Vol. 83, No. 4, 2011
Reaction of heteroaryltriphenylphosphonium salts with base in the presence of pivalaldehyde (General
procedure for Table 3-6): A mixture of heteroaryltriphenylphosphonium salts, pivalaldehyde, base, and
solvent (if applicable) was stirred at room temperature. Water was then added to the reaction mixture and
the suspension neutralized with 1 N HCl solution. The suspension was extracted with AcOEt. After the
organic layer was concentrated, the residue was purified by silica gel column chromatography to give the
pure compounds.
2,2-Dimethyl-1-(2-quinolinyl)-1-propanol: White solids. Mp 77.7 °C (lit.,17 73-75 °C). 1H-NMR (CDCl3)
ppm: 0.98 (9H, s, tBu), 4.52 (1H, d, J=5.8 Hz, CHOH), 4.78 (1H, d, J=5.8 Hz, CHOH), 7.32 (1H, d, J=8.4
Hz, C3-H), 7.40-7.98 (3H, m, C5, C6, and C7-H), 8.08 (2H, d, J=8.4 Hz, C4 and C8-H).
1
2,2-Dimethyl-1-(3-quinolinyl)-1-propanol: Pale yellow needles. Mp 177.4 °C. H-NMR (CDCl3) ppm:
0.98 (9H, s, tBu), 2.29 (1H, brs, CHOH), 4.61 (1H, s, CHOH), 7.38-7.91 (3H, m, C5, C6, and C7-H), 8.06
(2H, brs, C4 and C8-H), 8.83 (1H, d, J=1.9 Hz, C2-H). Anal. Calcd for C14H17NO: C, 78.10; H, 7.96; N,
6.51. Found: C, 78.06; H, 8.04; N, 6.66.
2,2-Dimethyl-1-(7-chloro-4-quinolinyl)-1-propanol: Yellow solids. Mp 160.2 °C. 1H-NMR (CDCl3) ppm:
0.97 (9H, s, tBu), 2.54 (1H, brs, CHOH), 5.26 (1H, s, CHOH), 7.30-7.65 (2H, m, C3 and C6-H), 7.92-8.16
(2H, m, C4 and C8-H), 8.83 (1H, d, J=4.6 Hz, C2-H). Anal. Calcd for C14H16ClNO: C, 67.33; H, 6.46; N,
5.61. Found: C, 67.43; H, 6.53; N, 5.76.
1
2,2-Dimethyl-1-(2-pyridinyl)-1-propanol: Yellow solids. Mp 54.1-55.2 °C (lit.,18 53-57 °C). H-NMR
t
(CDCl3) ppm: 0.92 (9H, s, Bu), 4.06-4.52 (2H, br, CHOH), 7.08-7.31 (2H, m, C3 and C5-H), 7.63 (1H,
ddd, J=7.6 Hz, 7.6 Hz, 1.8 Hz, C4-H), 8.55 (1H, dd, J=4.7 Hz, 1.8 Hz, C6-H).
1
2,2-Dimethyl-1-(5-iodo-2-pyridinyl)-1-propanol: Colorless prisms. Mp 77.5-78.5 °C. H-NMR (CDCl3)
ppm: 0.91 (9H, s, tBu), 3.81 (1H, d, J=7.3 Hz, CHOH), 4.31 (1H, d, J=7.3 Hz, CHOH), 7.02 (1H, d, J=8.2
Hz, C3-H), 7.93 (1H, dd, J=8.2 Hz, 1.9 Hz, C4-H), 8.76 (1H, d, J=1.9 Hz, C6-H).
1
3-Iodopyridine: Yellow solids. Mp 53.8 °C (lit.,19 52.3-53.0 °C). H-NMR (CDCl3) ppm: 7.09 (1H, dd,
J=8.1 Hz, 4.6 Hz, C3-H), 8.00 (1H, ddd, J=8.1 Hz, 1.5 Hz, 1.1 Hz, C4-H), 8.55 (1H, dd, J=4.6 Hz, 1.1 Hz,
C2-H), 8.84 (1H, d, J=1.5 Hz, C6-H).
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