Practical preparation of diphenylmethyl ethers from 2-diphenylmethoxypyridine using catalytic iron(III) chloride

Article abstract of DOI:10.1039/c9ob01093a

A novel facile synthetic method for producing diphenylmethyl (DPM) ethers from 2-diphenylmethoxypyridine was developed. A variety of DPM ethers was successfully achieved with high yield via treatment of alcohols with 2-diphenylmethoxypyridine in the presence of catalytic FeCl₃. The procedure is a practical and efficient synthetic procedure to protect various alcohols, and it can be applied to prepare bioactive compounds.

Full text of DOI:10.1039/c9ob01093a

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Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
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DOI: 10.1039/C9OB01093A
ARTICLE
Practical Preparation of Diphenylmethyl Ethers from 2-
Diphenylmethoxypyridine using Catalytic Iron (Ⅲ) Chloride
Van Hieu Tran,a,b Minh Thanh Laa,b and Hee-Kwon Kim*a,b
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
A novel facile synthetic method for producing diphenylmethyl (DPM) ethers from 2-diphenylmethoxypyridine was
developed. A variety of DPM ethers was successfully achieved with high yield via treatment of alcohols with 2-
diphenylmethoxypyridine in the presence of catalytic FeCl3. The procedure is a practical and efficient synthetic procedure
to protect various alcohols, and it can be applied to prepare bioactive compounds.
diphenylmethyl trichloroacetimidate for preparation of DPM
ethers.18 However, the reaction of trichloroacetimidate with alcohols
for DPM ether preparation requires high temperatures (such as the
high reflux temperature of toluene, 110 °C) and long reaction times
(e.g., 24 h). In addition, this reaction may produce side products by
rearrangement of the DPM-protected amine, leading to efficiency
concerns.
Introduction
Protection and deprotection methods are widely used in many
organic syntheses. Various protecting groups have been employed
for multistep synthesis of natural products or bioactive compounds,
and useful protecting groups have been developed. Diphenylmethyl
(DPM) groups are commonly used to protect hydroxyl groups. These
products are known as benzhydryl ethers and were first used for
protection of thiols.1 DPM groups have been widely used because
deprotection of the DPM group can be readily achieved under mild
conditions. For example, a hydrogenation procedure has been used
for removal of DPM groups from protected ethers.2 Acidic reaction
conditions such as aqueous HCl in THF, trifluoroacetic acid in
CH2Cl2, TiCl4, or electrolytic reduction are also useful for
deprotection of DPM groups.3-7 In addition to protection of hydroxyl
groups in multistep synthesis, DPM ethers have been employed as
effective bulky motifs for several chiral-selective reactions and for
preparation of biologically active compounds such as H3 receptor
antagonist and therapeutic agents for cocaine dependence.8-12
Several methods have been developed to form DPM ethers due to
their importance in organic synthesis. It was reported that
transformations of alcohol to the corresponding DPM ether were
achieved by treatment of alcohol with benzhydrol under acidic
conditions (scheme 1).13-14 However, such reactions have employed
harsh conditions such as use of strong acids or large amounts of acid,
which may affect several sensitive functional groups. Reactions
using tri-diphenylmethyl phosphate, diphenylmethyl diphenyl
phosphate, and diphenyldiazo methane to produce DPM ethers were
also developed.15-17 However, the synthetic procedure for alkyl
phosphates was expensive. In addition, diazo compounds are
unstable, and careful treatment is required due to their toxicity.
Other non–diazo-mediated methods have been developed for
DPM etherification. In particular, Chisholm’s group introduced O-
In addition, several metal-based catalysts have been used to
synthesize ethers from benzydrol, namely NbCl5 (niobium(V)
chloride), and PdCl2 (palladium chloride).19-20 However, these
catalysts are expensive, and the use of benzydrol could lead to self-
etherification to produce the byproduct bis(diphenylmethyl) ether.
Thus, it is desirable to find new efficient reaction procedure using
more suitable catalysts that are effective and inexpensive.
2-O-Substituted pyridines have recently been employed for
synthesis of ethers.21 Dudley and colleagues reported that 2-
benzyloxy-1-methylpyridinium salt, a reaction intermediate, could
be a useful benzyl transfer agent for preparation of benzyl ethers.21
However, formation of ethers using the synthetic method took one
day and required two reaction steps. In addition, reaction conditions
to produce benzyl ethers required high temperatures. Even though
the 2-benzyloxy-1-methylpyridine-mediated reaction showed a
weakness for etherification, we assumed that this approach could be
applied to other reactions, including synthesis of DPM ethers.
Previous work
R
Ph
O
H+
H
+
+
R OH
R OH
Ph
Ph
O
Ph
Ph
Ph
R
Ph
O
N
Ph
N
This work
a.Address here Department of Nuclear Medicine, Molecular Imaging & Therapeutic
Medicine Research Center, Chonbuk National University Medical School and
Hospital, Jeonju, 54907, Republic of Korea
R
Ph
3 mol% FeCl3
O
b.Research Institute of Clinical Medicine of Chonbuk National University-Biomedical
Research Institute of Chonbuk National University Hospital, Jeonju, 54907,
Republic of Korea
R OH
+
Ph
O
N
Ph
Ph
Scheme 1 Synthesis of diphenylmethyl ethers
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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Organic & Biomolecular Chemistry
Page 2 of 8
ARTICLE
Journal Name
We hypothesized that highly efficient reactions to form DPM ethers
Our initial screening study suggests that the reaction result was
could be discovered with reaction of 2-diphenyloxy-1- significantly affected by catalyst type, as shown inVTieawbAlreticl1e.OnOlinuer
DOI: 10.1039/C9OB01093A
methylpyridine and alcohols in the presence of a novel catalyst. To result indicated that the use of bases including K2CO3 and DBU or
the best of our knowledge, there is no synthetic method to convert 2- Lewis acids such as BF3∙OEt2, ZnCl2, and BiCl3 could not yield the
diphenylmethoxypyridine to DPM ethers via application of metal- desired product (Table 1). Reactions using CuCl2, MnCl2, and ZrCl4
based catalysts. Herein, we describe a novel practical synthetic produced the desired DPM esters with very low yields (less than
method using catalytic metal-based reagents to prepare DPM ethers 10%). Addition of SnCl4 and AlCl3 to the reaction resulted in
from 2-diphenylmethoxypyridine.
increased yields of the target product. However, the results were still
unsatisfactory. Finally, the reaction experiment with FeCl3 was
examined to prepare DPM ether, and the transformation yield of
benzyl alcohol to the DPM ether was significantly increased to 94%,
suggesting that FeCl3 is the most effective known catalyst for DPM
etherification.
Next, solvents were screened for DPM etherification. The
screening study suggested that DCE was an effective reaction
solvent (Table 2) for the reaction using 3 mol% of FeCl3, providing a
corresponding DPM ether with 94% yield. We also tried to decrease
the catalyst loading to develop a green chemical protocol. Thus,
various amounts of FeCl3 catalyst were used in the reaction to form
DPM ethers. As shown in Table 2, the amount of catalyst loading
could be reduced to 1 mol% to afford a DPM ether product with
satisfactory reaction yield.
Results and discussion
Cl
N
KOH
R
R
OH
3
Ph
Ph
O
3 mol% FeCl3
18-Crown-6
Ph
OH
Ph
O
N
Ph
Ph
DCE
toluene
4
2
1
Scheme 2 Novel synthetic strategy of diphenylmethyl ethers
2-Diphenylmethoxypyridine (compound 2), a starting material,
was easily synthesized via reaction of diphenylmethyl alcohol with
2-chloropyridine, potassium, and 18-crown-6 according to our
previous method, as shown in Scheme 2.22
We assumed that a catalytic reagent such as a Lewis acid would
be good choice in DPM etherification. In the initial study, benzyl
alcohol was employed as a substrate for the reaction with 2-
diphenylmethoxypyridine. Etherification reactions of benzyl alcohol
were performed in the presence of 1.5 equiv. of 2-
diphenylmethoxypyridine, 1.0 equiv. of benzyl alcohol, and 0.03
equiv. of various reagents at 70 °C for 10 h, and the conversion
yields from alcohols to the corresponding ethers were evaluated.
Table 2 Screening of solvent for in situ etherificationa
Ph
Ph
FeCl3
+
Ph
OH
O
Ph
Ph
Ph
O
N
Solvent, 10 h
4
2
3
Entry
Catalyst
(equiv.)
Solvent
THF
Yieldb
(%)
43
Table
1
Screening of catalyst for DPM etherificationa
1
FeCl3 (0.03)
FeCl3 (0.03)
FeCl3 (0.03)
FeCl3 (0.03)
FeCl3 (0.03)
FeCl3 (0.2)
Ph
Ph
Catalyst
2
MeCN
Dioxane
Toluene
DCE
45
50
71
94
95
95
94
74
87
63
+
Ph
OH
O
Ph
Ph
Ph
O
N
DCE, 10h
4
2
3
3
Entry
Catalyst
Temp.
Yieldb
(%)
4
1
2
K2CO3
DBU
70 °C
70 °C
70 °C
70 °C
70 °C
70 °C
70 °C
70 °C
70 °C
70 °C
70 °C
70 °C
NRc
NRc
NRc
NRc
NRc
3
5
6
DCE
3
BF3∙OEt2
ZnCl2
BiCl3
7
FeCl3 (0.1)
DCE
4
8
FeCl3 (0.05)
FeCl3 (0.01)
FeCl3 (0.01)
FeCl3 (0.005)
DCE
5
9
DCE
6
CuCl2
MnCl2
ZrCl4
10c
11d
DCE
7
2
DCE
8
5
a Reaction conditions: compound 2 (1.5 mmol), alcohol (1.0 mmol),
solvent (2 mL), 70oC, 10 h
9
AlCl3
SnCl4
FeCl3
None
52
b Isolated yield after purification via flash column chromatography
c Reaction conducted for 24 h
10
11
12
53
d Reaction conducted for 40 h
94
Using this result, the scope of this reaction for the synthesis of
DPM ethers was evaluated using different types of alcohols (Table
3). Aliphatic primary alcohols were readily converted into the
corresponding DPM ethers in high yields (Table 3, entries 2-4).
Unsaturated alcohols such as allyl alcohol and propargyl alcohol
were also reacted with 2-diphenylmethoxypyridine in the presence of
NRc
a Reaction conditions: compound 2 (1.5 mmol), alcohol (1.0 mmol),
catalyst (0.03 mmol), DCE (2 mL), 70 oC, 10 h
b Isolated yield after purification via flash column chromatography
c No reaction
2 | J. Name., 2012, 00, 1-3
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ARTICLE
Table 3 Scope of DPM etherification using various alcoholsa
catalytic FeCl3, and the desired DPM esters were obVtaieiwneAdrticilne O9n3li%ne
and 92% yields respectively (Table 3, entries 5-6).
DOI: 10.1039/C9OB01093A
Next, secondary and tertiary alcohols were investigated to
investigate steric effects on reaction yields (Table 3, entries 7–10).
Reactions of isopropanol, a secondary alcohol, provided the target in
86% yield. When tert-butyl alcohol, which has a greater steric effect,
was treated with 2-diphenylmethoxypyridine under the same
conditions, the synthetic yield of the DPM ether was 84%.
Cyclohexanol was also used as an alicyclic substrate to examine the
scope of this reaction protocol; the target DPM ether was prepared
with 87% yield. Besides, benzhydrol containing two aromatic rings
Ph
Ph
O
N
2
Ph
3 mol% FeCl3
R
OH
R
O
Ph
DCE, 70 oC, 10h
3
4
Entry
Alcohol
Product
Yieldb
(%)
Ph
readily
reacted
with
with
2-diphenylmethoxypyridine.
OH
OH
1
3a
4a
94
O
O
Ph
Bromopropanol, diols, and 3-(benzyloxy)propan-1-ol were also
tested to show more functional group tolerance, and the reactions
successfully yield the corresponding DPM ethers (Table 3, entries
11–14). Development of efficient procedures to convert phenol to its
DPM ether is valuable because achieving good synthetic results
using existing procedures for this reaction can be difficult.20 Thus,
phenol was investigated for this reaction, and was etherified using 2-
diphenylmethoxypyridine with 90% yield. Additionally, reactions of
phenols with electron-donating and electron-withdrawing groups
gave the target DPM ethers in high yields ranging from 85% to 95%
(Table 3, entries 15–18). This result suggested that usage of catalytic
amounts of FeCl3 could produce the desired DPM ethers from a
variety of aromatic alcohols with satisfactory yield. N-Cbz–protected
amino alcohol was also examined to assess functional group
tolerance; the target DPM ether 4n was readily obtained in 91%
yield (Table 3, entry 19).
Ph
4b
4c
94
93
2
3
3b
3c
Ph
Ph
OH
O
Ph
Ph
89
93
4
5
4d
4e
OH
3d
3e
3f
O
Ph
Ph
OH
OH
O
O
Ph
Ph
92
6
4f
Ph
Ph
OH
4g
4h
86
87
7
8
3g
3h
O
Ph
Ph
Table 4 Scope of DPM etherification using various diphenyl
OH
methanolsa
O
Ph
Ph
R2
R3
OH
OH
9
3i
3j
4i
4j
84
90
O
Ph
O
N
R1
O
Ph Ph
O
5
10
Ph
Ph
3 mol% FeCl3
R1 OH
Ph
DCE, 70 oC, 10h
R3
R2
92
85
78
11
12
4k
4l
Br
OH
3k
3
6
Br
O
O
Ph
Ph
O
O
O
HO
OH
3l
HO
Ph
Ph
NO2
Cl
OH
Ph
O
13
4m
3m
6c, 90%
6b, 94%
6a, 95%
HO
HO
Ph
O
O
O
14
15
93
90
BnO
OH
3n
3o
4n
4o
BnO
O
Ph
Ph
F
F
Cl
Cl
Ph
O
OH
Ph
Ph
6e, 96%
6d, 91%
6f, 95%
H3CO
Cl
O
O
O
H3CO
OH
91
16
4p
4q
4r
3p
O
NO2
Cl
Ph
95
85
91
Cl
OH
17
18
3q
3r
6i, 91%
6g, 91%
6h, 90%
O
Ph
Ph
O2N
O
O
O
O2N
OH
O
Ph
Ph
F
F
Cl
Cl
4s
Ph
19
3s
CbzHN
OH
CbzHN
O
6j, 90%
6k, 96%
6l, 95%
a Reaction conditions: alcohol (1.0 mmol), compound 2 (1.5 mmol),
FeCl3 (0.03 mmol), DCE (2 mL), 70°C for 10 h
a
Reaction conditions: alcohol (1.0 mmol), compound 2 (1.5 mmol),
FeCl3 (0.03 mmol), DCE (2 mL), 70 °C for 10 h
b Isolated yield after purification via flash column chromatography
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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ARTICLE
Different structures of diphenyl methyl ether scaffold were also
Journal Name
A proposed reaction mechanism for this DPM esterification is
View Article Online
found in commercially available drugs or bioactive compounds,
including dopamine reuptake inhibitor and dopamine transporter
inhibitors.12, 23 Thus, to demonstrate the utility of FeCl3-catalyzed
DPM etherification, this procedure was applied to conversion of
diverse substituted 2-diphenylmethoxypyridines bearing mono-/di-
substitions to substituted diphenylmethyl ethers, as shown in Table 4.
First, mono-substituted 2-diphenylmethoxypyridine was used to
prepare a series of diphenylmethyl ethers. Alcohols such as butyl
alcohol and allyl alcohol readily reacted with mono-substituted 2-
shown in Scheme 5. 2-DiphenylmethoxypyDriOdIi:n1e0.2103is9/aCc9tOivBa0te10d9b3Ay
coordination of FeCl3 with nitrogen atom to generate a FeCl3-2-
diphenylmethoxypyridine complex intermediate, which undergoes
intermolecular nucleophilic attack by alcohol to give the DPM ether
product. Then, FeCl3 was given back to the reaction and
continuously catalyze DPM ether reaction.
Besides, deprotection reaction of DPM ether was performed
(Table 5). Several reagents (10 mol%) was tested for DPM
deprotection of compound 4n at room temperature for 12 h. When
compound 4n was treated with FeCl3 and MnCl2, target product was
not prepared. However, reaction of compound 4n with AlCl3 and
ZrCl4 yielded the corresponding product with 44% and 78% yields,
respectively. The result indicated that employment of FeCl3 did not
influence on the deprotection of DPM ether, suggesting that it was
useful to prepare DPM ether, and ZrCl4 is an effective catalytic
reagent to remove DPM group from DPM ethers.
diphenylmethoxypyridine-bearing,
electron-donating
groups
(methyl-) and electron-withdrawing groups (nitro-, and chloro-)
under the optimal reaction conditions, yielding the desired
diphenylmethyl ether products in high yields (Table 4, 6a-6c, and
6g-6i). In addition, di-substituted 2-diphenylmethoxypyridine was
employed for treatment of alcohols, and bis(4-methylphenyl)methyl
ethers and bis(4-halophenyl)methyl ethers were successfully
obtained in high yields. These results indicate that the novel
synthetic method using FeCl3 can be used to prepare various
biologically active compounds.
Table 5 DPM deprotection study with catalysts
Ph
Reagent
(10 mol%)
Next, scale-up DPM etherification was conducted (Scheme 3). In
the gram-scale reaction of benzyl alcohol, DPM ether was
successfully obtained from the same reaction conditions: reaction of
benzyl alcohol (3a) (100.0 mmol, 10.8 g) with 2-
diphenylmethoxypyridine (2) afforded the target ether product (4a)
in 88% yield via optimized reaction conditions. Thus, this reaction
method is effective and scalable.
BnO
O
Ph
BnO
OH
rt, 12 h
4n
3n
Reagents
FeCl3
No reaction
MnCl2
No reaction
AlCl3
44%
ZrCl3
78%
(10 mol%)
Ph
Conclusions
Ph
FeCl3 (3 mol%)
DCE, 70 oC, 10 h
O
N
Ph
2
In conclusion, a novel and efficient synthetic method for DPM
etherification of various alcohols was developed. A novel
synthetic protocol of DPM ethers is valuable to protect alcohols
and to prepare bioactive compounds because many drugs
contain diphenylmethyl ether moieties. Here, we described the
Ph
OH
O
Ph
Ph
4a
3a
100.0 mmol, 10.8 g
24.11 g, 88%
Scheme 3 Gram-scale reaction of benzyl alcohol (3a) with 2-
diphenylmethoxypyridine (2).
FeCl3-catalyzed
reaction
of
alcohols
with
2-
diphenylmethoxypyridine to yield DPM ethers in high yield.
The novel method is practical and highly efficient in producing
DPM ethers, and it is a promising approach for preparation of
bioactive compounds such as drugs.
Besides, 1-butanethiol, another nucleophile, was employed for
this reaction, and it was found that the conversion yield was 91%
under the same reaction condition (Scheme 4).
Ph
Ph
FeCl3 (3 mol%)
+
SH
Experimental
General methods
S
Ph
Ph
O
N
DCE, 70 oC, 10 h
7
2
8 (91%)
Scheme
4
Reaction of
1-butanethiol (7) with 2-
Reactions were performed in a well-dried flask under argon
atmosphere unless noted otherwise. Solvents used as reaction
media were dried over pre-dried molecular sieves (4 Å ) in a
microwave oven. Solvents for extraction and chromatography
were reagent grade and used as received. Column
chromatography was performed with silica gel 60 (70−230
diphenylmethoxypyridine (2).
O
N
1
mesh) using a mixture of DCM/hexane as eluent. H and 13C
2
O
N
NMR spectra were, respectively, recorded on a 400 MHz (1H
NMR), 100 MHz (13C NMR) spectrometer in deuterated
chloroform (CDCl3) with tetramethylsilane(TMS) as an internal
reference. Data are reported as (ap = apparent, s = singlet, d =
doublet, t = triplet, q = quartet, m = multiplet, br = broad;
coupling constant(s) in Hz, integration). High-resolution mass
spectroscopy was performed using a magnetic sector analyzer.
9
FeCl3
OH
FeCl3
R
3
HO
N
R
HO
N
O
1
All of the new compounds were identified by H and 13C NMR,
FeCl3
4
and high resolution mass spectroscopy. The identity of the
known compounds was established by the comparison of their
1H and 13C NMR peaks with the authentic values.
Scheme
5
Proposed etherification mechanism using 2-
diphenylmethoxypyridine with FeCl3.
Procedure
for
the
preparation
of
2-
4 | J. Name., 2012, 00, 1-3
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Journal Name
diphenylmethoxypyridinium (2)
ARTICLE
7.31 – 7.28 (m, 2H), 6.07 – 5.97 (m, 1H), 5.47 (s, 1H), 5.38 –
Benzydrol (3.0 g, 16.2 mmol), followed by 2-chloropyridine 5.33 (m, 1H), 5.26 – 5.22 (m, 1H), 4.07 –D4O.I0:510(.1d0t3,V9Jie/Cw=9A5Ort.iBc6l0e1HO0nz9l,i3nAJe
(1.9 mL, 19.5 mmol), and toluene (40 ml) were added = 1.6 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 142.22 (2C),
sequentially to the round bottom flask. Potassium hydroxide 134.79, 128.40 (4C), 127.44 (2C), 127.02 (4C), 116.91, 82.63,
(3.66g, 65.13 mmol) was ground in a mortar in pestle and then 69.07; HRMS (ESI) m/z (M+H)+ calcd for C16H17O = 225.1279,
added to the reaction flask, followed by 18-crown-6 (0.21 g, found 225.1280.
0.81 mmol). The reaction mixture was heated at 110 °C) for 2h. ((Prop-2-ynyloxy)methylene)dibenzene (4f). Colorless liquid
1
After cooling to room temperature, the reaction mixture was (0.204 g, 92 %); H NMR (400 MHz, CDCl3) δ 7.42 - 7.31 (m,
diluted with ethyl acetate (2 x 50 mL), washed with water (80 10H), 7.52 (s, 1H), 4.20 (d, J = 2.4 Hz, 2H), 2.49 (t, J = 2.4 Hz,
mL), followed by brine (80 mL). The organic layer was dried 1H); 13C NMR (100 MHz, CDCl3) δ 141.17 (2C), 128.46 (4C),
thoroughly over anhydrous sodium sulfate, and concentrated in 127.71 (2C), 127.30 (4C), 81.67, 79.76, 74.61, 55.81; HRMS
vacuo. Column chromatography of the residue (1:2 (ESI) m/z (M+H)+ calcd for C16H15O = 223.1123, found
dichloromethane/ hexane) yielded the product
(3.65 g, 93%). m.p. 59 - 61°C; H NMR (600 MHz, CDCl3) δ (isopropoxymethylene)dibenzene (4g). Colorless liquid (0.194
8.14 – 8.12 (dd, J = 5.0 Hz, J = 1.5 Hz, 1H), 7.58 (ddd, J = 8.0 g, 86%); H NMR (400 MHz, CDCl3) δ 7.41 – 7.33 (m, 8H),
2 as a white solid 223.1125.
1
1
Hz, J = 7.0, Hz, J = 1.5 Hz, 1H), 7.46 (d, J = 6.5 Hz, 4H), 7.33 7.29 – 7.25 (m, 2H), 5.53 (s, 1H), 3.74 – 3.68 (m, 1H), 1,27 (d,
(t, J = 7.0 Hz, 4H), 7.29 (s, 1H), 7.25 – 7.23 (m, 2H), 6.88 (d, J J = 6.4 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 143.00 (2C),
= 7.0 Hz, 1H), 6.82 (ddd, J = 6.5 Hz, J = 5.5, Hz, J = 1 Hz, 1H); 128.32 (4C), 127.26 (2C), 127.11 (4C), 80,47, 69.11, 22.28
13C NMR (100 MHz, CDCl3) δ 162.9, 146.9, 141.6, 138.7, (2C); HRMS (ESI) m/z (M+H)+ calcd for C16H19O = 227.1436,
128.4, 127.5, 127.3, 117.0, 111.6, 77,5; HRMS (ESI) m/z found 227.1438.
(M+H)+ calcd for C18H16NO = 262.1232, found 262.1237.
(Cyclohexyloxymethylene)dibenzene (4h). Colorless liquid
(0.208 g, 87%); H NMR (400 MHz, CDCl3) δ 7.40 – 7.27 (m,
1
10H), 5.59 (s, 1H), 3.43 – 3.38 (m, 1H), 1,98 – 1.95 (m, 2H),
1.80 - 1.78 (m, 2H), 1.54 – 1.45 (m ,3H), 1.30 -1.20 (m, 3H);
General procedure of the synthesis of diphenylmethoxyl
ethers (4a-4s) & (6a-6l)
To a solution of benzyl alcohol (0.108 g. 1.00 mmol) and 2- 13C NMR (100 MHz, CDCl3) δ 143.17 (2C), 128.29 (4C),
diphenylmethoxypyridine (0.39 g, 1.50 mmol) in DCE (2 mL) 127.20 (2C), 127.15 (4C), 79,97, 75.05, 32.41 (2C), 25.89,
FeCl3 (0.0048 g. 0.03 mmol) was added. The mixture was 24.15 (2C); HRMS (ESI) m/z (M+H)+ calcd for C19H23O =
stirred at 70 °C for 10h. The reaction mixture was extracted 267.1749, found 267.1751.
with ethyl acetate (2 x 10 mL), and then washed with water (10
(tert-butoxymethylene)dibenzene (4i). Colorless liquid (0.218
1
mL), followed by brine (10 mL). The organic layer was dried g, 84%); H NMR (400 MHz, CDCl3) δ 7.39 – 7.31 (m, 8H),
over anhydrous sodium sulfate and concentrated under reduced 7.28 – 7.23 (m, 2H), 5.63 (s, 1H), 1.27 (s, 1H); 13C NMR (100
pressure. The resulting residue was then purified by flash MHz, CDCl3) δ 145.13 (2C), 128.14 (4C), 126.94 (2C), 126.76
column chromatography on silica gel with hexane-CH2Cl2 as (4C), 75.75, 75.00, 28.79 (3C); HRMS (ESI) m/z (M+H)+ calcd
eluent to afford the desired product 4a as a colorless liquid for C17H21O = 241.1592, found 241.1593.
(0.260 g, 94%).
Oxybis(methanetriyl)tetrabenzene (4j). White solid (0.315g,
(Benzyloxymethylene)dibenzene (4a). Colorless liquid (0.260 90%). m.p. 108 -110.0°C; 1H NMR (400 MHz, CDCl3) δ 7.41 – 7.38
1
g, 94%); H NMR (400 MHz, CDCl3) δ 7.46 – 7.31 (m, 15H), (m, 8H), 7.36 – 7.33 (m, 8H), 7.30 – 7.25 (m, 4H), 5.43 (s, 2H); 13C
5.51 (s, 1H), 4.62 (s, 2H); 13C NMR (100 MHz, CDCl3) δ NMR (100 MHz, CDCl3) δ 142.22 (4C), 128.41 (8C), 127.45 (4C),
142.67, 138.43, 128.45 (4C), 128.41 (2C), 127.75 (2C), 127.57, 127.28 (8C), 80.00 (2C); HRMS (ESI) m/z (M+H)+ calcd for
127.51 (2C), 127.17 (4C), 82.51, 70.53; HRMS (ESI) m/z C26H23O = 351.1749, found 351.1751.
(M+H)+ calcd for C20H19O = 275.1436, found 275.1438.
((3-bromopropoxy)methylene)dibenzene (4k). Colorless oil
1
Butoxymethylene)dibenzene (4b). Colorless oil (0.225 g, (0.28 g, 92%). H NMR (400 MHz, CDCl3) δ 7.39 – 7.33 (m, 8H),
1
94%); H NMR (400 MHz, CDCl3) δ 7.38 – 7.26 (m, 10H), 7.31 – 7.26 (m, 2H), 5.39 (s, 1H), 3.61 (t, J = 5.6 Hz, 4H), 2.23 –
5.35 (s, 1H), 3.48 (t, J = 6.8 Hz, 2H), 1.69 – 1.62 (m, 2H), 1.49 2.17 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 142.15 (2C), 128.41
– 1.42 (m, 2H), 0.93 (t, J = 7.2 Hz, 2H); 13C NMR (100 MHz, (4C), 127.50 (2C), 126.94 (4C), 83.88, 68.49, 33.10, 30.82; HRMS
CDCl3) δ 142.66 (2C), 128.31 (4C), 127.29 (2C), 126.96 (4C), (ESI) m/z (M+H)+ calcd for C16H18BrO = 305.0541, found 305.0545.
83.57, 68.95, 32.01, 19.48, 13.96; HRMS (ESI) m/z (M+H)+ 3-(benzhydryloxy)propan-1-ol (4l). Colorless oil (0.21g, 85%).
calcd for C17H21O = 241.1592, found 241.1594.
1H NMR (400 MHz, CDCl3) δ 7.34 – 7.29 (m, 8H), 7.25 – 7.22
(Heptyloxymethylene)dibenzene (4c). Colorless liquid (0.262 (m, 2H), 5.35 (s, 1H), 3.79 (t, J = 5.6 Hz, 2H), 3.64 (t, J = 6.0
g, 93%);1H NMR (400 MHz, CDCl3) δ 7.41 – 7.33 (m, 8H), Hz, 2H), 2.10 (s, 1H), 1.92 – 1.86 (m, 2H); 13C NMR (100
7.31 – 7.25 (m, 2H), 5.36 (s, 1H), 3.48 (t, J = 6.4 Hz, 2H), 1.71 MHz, CDCl3) δ 142.02 (2C), 128.48 (4C), 127.56 (2C), 126.85
– 1.65 (m, 2H), 1.43 – 1.37 (m, 2H), 1.32 – 1.28 (m, 6H), 0.91 (4C), 84.19, 68.16, 61.96, 32.32; HRMS (ESI) m/z (M+H)+
(t, J = 6.8 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 142.67 (2C), calcd for C16H19O2 = 243.1385, found 243.1389.
128.38 (4C), 128.32 (2C), 127.29 (4C), 83.59, 69.27, 31.86,
29.92, 29.18, 26.25, 22.66, 14.12; HRMS (ESI) m/z (M+H)+ Colorless oil (0.24g, 78%). 1H NMR (400 MHz, CDCl3) δ 7.38
calcd for C20H27O = 283.2062, found 283.2065. – 7.32 (m, 8H), 7.30 – 7.24 (m, 2H), 5.34 (s, 1H), 3.49 (d, J =
(4-(benzhydryloxymethyl)cyclohexyl)methanol
(4m).
((Cyclopropylmethoxy)methylene)dibenzene (4d). Yellowish 6.0 Hz, 2H), 3.31 (d, J = 6.4 Hz, 2H), 1.95 – 1.92 (m, 2H), 1.86
1
liquid (0.211 g, 89%); H NMR (400 MHz, CDCl3) δ 7.42 - – 1.83 (m, 2H), 1.69 – 1.64 (m, 1H), 1.49 – 1.44 (m, 1H), 1.40
7.27 (m, 10H), 5.47 (s, 1H), 5.46 (s, 1H), 3.37 (d, J = 6.8 Hz, (s, 1H), 1.08 – 0.95 (m, 4H); 13C NMR (100 MHz, CDCl3) δ
2H), 1.20 - 1.16 (m, 1H), 0.58 - 0.56 (m, 2H), 0.25 - 0.22 (m, 142.66 (2C), 128.32 (4C), 127.31 (2C), 126.94 (4C), 83.67,
2H); 13C NMR (100 MHz, CDCl3) δ 142.47 (2C), 128.37 (4C), 74.79, 68.72, 40.65, 38.45, 29.47 (2C), 28.97 (2C); HRMS (ESI)
127.36 (2C), 127.05 (4C), 83.12, 73.66, 10.78, 3.13 (2C); m/z (M+H)+ calcd for C21H27O2 = 311.2011, found 311.2014.
HRMS (ESI) m/z (M+H)+ calcd for C17H19O = 239.1436, found
((3-(benzyloxy)propoxy)methylene)dibenzene
(4n).
239.1437.
Yellowish oil (0.31g, 93%). 1H NMR (400 MHz, CDCl3) δ 7.40
(Allyloxymethylene)dibenzene (4e). Colorless liquid (0.208 g, - 7.38 (m, 15H), 5.39 (s, 1H), 4.54 (s, 2H), 3.68 (t, J = 6.4 Hz,
93% yield); 1H NMR (400 MHz, CDCl3) δ 7.42 – 7.34 (m, 8H), 2H), 3.63 (t, J = 6.4 Hz, 2H), 2.05 - 1.99 (m, 2H); 13C NMR
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(100 MHz, CDCl3) δ 142.50 (2C), 138.56, 128.37 (6C), 127.68, CDCl3) δ 150.21, 147.08, 141.14, 128.72 (2C), 128.05, 127.41
View Article Online
127.53, 127.34 (2C), 126.99 (4C), 83.73, 73.27, 67.48, 66.06, (2C), 127.03 (2C), 123.62 (2C), 82.72, 69.16, 31.90, 19.45,
DOI: 10.1039/C9OB01093A
30.34; HRMS (ESI) m/z (M+H)+ calcd for C23H25O2
333.1855, found 333.1852.
=
13.94; HRMS (ESI) m/z (M+H)+ calcd for C17H20NO3
286.1443, found 286.1447.
=
(Phenoxymethylene)dibenzene (4o). White solid (0.234 g, 4,4'-(butoxymethylene)bis(methylbenzene) (6d). Colorless
90%); m.p. 53-54 °C; 1H NMR (400 MHz, CDCl3) δ 7.48 - 7.39 liquid (0.243 g, 91%); 1H NMR (400 MHz, CDCl3) δ 7.25 (d, J
(m, 4H), 7.38 - 7.36 (m, 4H), 7.32 - 7.25 (m, 4H), 7.01- 6.99 (m, = 8.4 Hz, 4H), 7.14 (d, J = 8.0 Hz, 4H), 5.29 (s, 1H), 3.45 (t, J
3H), 6.26 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 158.13, = 6.4 Hz, 2H), 2.33 (s, 6H), 1.66 – 1.62 (m, 2H), 1.50 – 1.41 (m,
141.31 (2C), 129.37 (2C), 128.61 (4C), 127.74 (2C), 126.92 2H), 0.92 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ
(4C), 121.00, 116.13 (2C), 81.70; HRMS (ESI) m/z (M+H)+ 139.92 (2C), 136.79 (2C), 128.99 (4C), 126.85 (4C), 83.26,
calcd for C19H17O = 261.1279, found 261.1280.
68.83, 32.05, 21.13 (2C), 19.51, 14.01; HRMS (ESI) m/z
1-(benzhydryloxy)-4-methoxybenzene (4p). White solid (M+H)+ calcd for C19H25O = 269.1905, found 269.1908.
1
(0.263 g, 91%); m.p. 58-60°C; H NMR (400 MHz, CDCl3) δ 4,4'-(butoxymethylene)bis(fluorobenzene) (6e). Colorless
1
7.46 – 7.44 (m, 4H), 7.39 – 7.35 (m, 4H), 7.32 – 7.30 (m, 2H), liquid (0.264 g, 96%); H NMR (400 MHz, CDCl3) δ 7.32 -
6.93 – 6.90 (m, 2H), 6.80 - 6.78 (m, 2H) 6.14 (s, 1H), 3.75 (s, 7.29 (m, 4H), 7.05 – 7.01 (m, 4H), 5.32 (s, 1H), 3.45 (t, J = 6.4
3H); 13C NMR (100 MHz, CDCl3) δ 153.99, 152.26, 141.51 Hz, 2H), 1.66 – 1.61 (m, 2H), 1.46 – 1.41 (m, 2H), 0.94 (t, J =
(2C), 128.56 (4C), 127.69 (2C), 126.94 (4C), 117.28 (2C), 7.6 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 163.32, 160.88,
114.51 (2C), 82.64, 55.64; HRMS (ESI) m/z (M+H)+ calcd for 138.24, 138.22, 128.55, 128.47, 115.35, 115.14, 82.19, 68.92,
C20H19O2 = 291.1385, found 291.1387.
31.93, 19.47, 13.94; HRMS (ESI) m/z (M+H)+ calcd for
1-(benzhydryloxy)-4-chlorobenzene(4q). White solid (0.279 g, C17H19F2O = 277.1404, found 277.1405.
95%); m.p. 62-64°C; 1H NMR (400 MHz, CDCl3) δ 7.45 - 7.43 4,4'-(butoxymethylene)bis(chlorobenzene) (6f). Colorless
1
(m, 4H), 7.40 – 7.36 (m, 4H), 7.33 – 7.28 (m, 2H), 7.20 (dd, J = liquid (0.293 g, 95%); H NMR (400 MHz, CDCl3) δ 7.33 -
8.8 Hz, J = 2.4 Hz, 2H), 6.92 (dd, J = 8.8 Hz, J = 2.2 Hz, 2H), 7.26 (m, 8H), 5.28 (s, 1H), 3.44 (t, J = 6.4 Hz, 2H), 1.66 – 1.21
6.20 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 156.65, 140.83 (m, 2H), 1.46 – 1.41 (m, 2H), 0.94 (t, J = 7.2 Hz, 3H); 13C
(2C), 129.27 (2C), 128.69 (4C), 127.91 (2C), 126.86 (4C), NMR (100 MHz, CDCl3) δ 140.75 (2C), 133.28 (2C), 128.60
125.91, 117.45 (2C); HRMS (ESI) m/z (M+H)+ calcd for (4C), 128.22 (4C), 82.18, 69.03, 31.90, 19.46, 13.94; HRMS
C19H16ClO = 295,0890, found 295.0893.
(ESI) m/z (M+H)+ calcd for C17H19Cl2O = 309.0813, found
1-(benzhydryloxy)-4-nitrobenzene (4r). White solid (0.259 g, 309.0812.
85%); m.p. 68-70°C; 1H NMR (400 MHz, CDCl3) δ 8.17 – 8.15 1-(allyloxy(phenyl)methyl)-4-methylbenzene (6g). Colorless
1
(dd, J =7.2 Hz, J = 2.4 Hz, 2H), 7.43 – 7.39 (m, 10H), 7.05 – liquid (0.216 g, 91%); H NMR (400 MHz, CDCl3) δ 7.40 -
7.03 (dd, J =7.2 Hz, J = 2.4 Hz, 2H), 6.34 (s, 1H); 13C NMR 7.34 (m, 4H), 7.28 - 7.27 (m, 3H), 7.17 - 7.15 (m, 2H), 6.06 -
(100 MHz, CDCl3) δ 162.96, 141.61, 139.83 (2C), 128.88 (4C), 5.96 (m, 1H), 5.44 (s, 1H), 5.37 - 5.32 (dq, J = 16.8 Hz, J = 1.6
128.30 (2C), 126.77 (4C), 125.82 (2C), 115.95 (2C), 82.49; Hz, 1H), 5.25 - 5.21 (dq, J = 10.8 Hz, J = 1.2 Hz, 1H), 4.05 -
HRMS (ESI) m/z (M+H)+ calcd for C19H16NO3 = 306.1130, 4.03 (dt, J = 5.2 Hz, J = 1.6 Hz, 2H), 2.36 (s, 3H); 13C NMR
found 306.1132.
(100 MHz, CDCl3) δ 142.44, 139.23, 137.11, 134.87, 129.11,
Benzyl 5-(benzhydryloxy)pentylcarbamate (4s). Yellowish 128.37, 127.33, 127.00, 126.92, 116.84, 82.46, 69.63, 21.16;
1
liquid (0.366 g, 91%); H NMR (400 MHz, CDCl3) δ 7.39 – HRMS (ESI) m/z (M+H)+ calcd for C17H19O = 239.1436, found
7.26 (m, 15H), 5.35 (s, 1H), 5.12 (s, 2H), 4.78 (s, 1H), 3.48 (t, J 239.1438.
= 6.4 Hz, 2H), 3.24 – 3.19 (m, 2H), 1.71 – 1.66 (m, 2H), 1.55 – 1-(allyloxy(phenyl)methyl)-4-chlorobenzene (6h). Colorless
1
1.43 (m, 4H); 13C NMR (100 MHz, CDCl3) δ 156.36, 142.51 liquid (0.232 g, 90 %); H NMR (400 MHz, CDCl3) δ 7.37 -
(2C), 136.66 (2C), 128.52 (2C), 128.37(4C), 128.13, 128.09, 7.28 (m, 9H), 6.03 - 5.96 (m, 1H), 5.43 (s, 1H), 5.36 - 5.31 (dq,
127.88, 127.37 (2C), 126.94 (4C), 83.67, 68.85, 66.60, 41.04, J = 17.2 Hz, J = 1.6 Hz, 1H), 5.25 - 5.21 (dq, J = 10.4 Hz, J =
29.77, 29.52, 23.58; HRMS (ESI) m/z (M+H)+ calcd for 1.2 Hz, 1H), 4.05 - 4.03 (m, 2H); 13C NMR (100 MHz, CDCl3)
C26H30NO3 = 404.2224, found 404.2225.
δ 141.69, 140.83, 134.55, 133.15, 128.55, 128.53, 128.33,
1-(butoxy(phenyl)methyl)-4-methylbenzene (6a). Colorless 127.70, 126.97, 117.13, 81.88, 69.71; HRMS (ESI) m/z
1
liquid (0.241 g, 95%); H NMR (400 MHz, CDCl3) δ 7.40 – (M+H)+ calcd for C16H16ClO = 259.0890, found 259.0892.
7.34 (m, 4H), 7.28 – 7.26 (m, 3H), 7.17 – 7.15 (m, 2H), 5.35 (s, 1-(allyloxy(phenyl)methyl)-4-nitrobenzene (6i). Yellowish
1
1H), 3.48 (t, J = 6.4 Hz, 2H), 2.35 (s, 3H), 1.67-1.65 (m, 2H), liquid (0.244 g, 91%); H NMR (400 MHz, CDCl3) δ 8.19 -
1.52 -1.45 (m, 2H), 0.95 (t, J = 7.6 Hz, 3H); 13C NMR (100 8.16 (m, 2H), 7.57 - 7.54 (m, 2H), 7.38 - 7.28 (m, 5H), 6.01 -
MHz, CDCl3)
δ 142.89, 139.70, 136.94, 129.04 (2C), 5.92 (m, 1H), 5.50 (s, 1H), 5.34 - 5.29 (dq, J = 17.2 Hz, J = 1.6
128.31(2C), 83.42, 68.89, 66.60, 32.04, 21.15, 19.52, 14.01; Hz, 1H), 5.26 - 5.22 (dq, J = 10.4 Hz, J = 1.2 Hz, 1H), 4.08 -
HRMS (ESI) m/z (M+H)+ calcd for C18H23O = 255.1749, found 3.97 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 149.77, 147.15,
255.1752.
140.65, 134.17, 128.80, 128.22, 127.45, 127.15, 123.66, 117.49,
1-(butoxy(phenyl)methyl)-4-chlorobenzene (6b). Colorless 81.67, 69.83; HRMS (ESI) m/z (M+H)+ calcd for C16H16NO3 =
1
liquid (0.258 g, 94%); H NMR (400 MHz, CDCl3) δ 7.37 – 270.1130, found 270.1135.
7.27 (m, 9H), 5.33 (s, 1H), 3.49 – 3.44 (m, 2H), 1.67 - 1.64 (m, 4,4'-(allyloxymethylene)bis(methylbenzene) (6j). Colorless
2H), 1.47 -1.42 (m, 2H), 0.94 (t, J = 7.2 Hz, 3H); 13C NMR liquid (0.226 g, 90%); 1H NMR (400 MHz, CDCl3) δ 7.27 (d, J
(100 MHz, CDCl3) δ 142.89, 139.70, 136.94, 129.04 (2C), = 8.0 Hz, 4H), 7.17 (d, J = 8.0 Hz, 4H), 6.05 – 5.96 (m, 2H),
128.31(2C), 83.42, 68.89, 66.60, 32.04, 21.15, 19.52, 14.01; 5.41 (s, 1H), 5.36 – 5.31 (dq, J = 17.2 Hz, J = 1.6 Hz, 1H), 5.24
HRMS (ESI) m/z (M+H)+ calcd for C17H20ClO = 275.1203, – 5.21 (dq, J = 10.4 Hz, J = 2.0 Hz, 1H), 4.04 – 4.02 (dt, J = 5.2
found 275.1204.
Hz, J = 1.2 Hz, 2H), 2.35 (s, 6H); 13C NMR (100 MHz, CDCl3)
1-(butoxy(phenyl)methyl)-4-nitrobenzene (6c). Yellowish δ 139.47 (2C), 136.96 (2C), 134.96, 129.05(4C), 126.92(4C),
1
liquid (0.256 g, 90%); H NMR (400 MHz, CDCl3) δ 8.18 – 116.73, 82.32, 69.57, 21.14 (2C); HRMS (ESI) m/z (M+H)+
8.15 (m, 2H), 7.54 – 7.52 (m, 2H), 7.34 – 7.28 (m, 5H), 5.40 (s, calcd for C18H21O = 253.1592, found 253.1593.
1H), 3.50 – 3.41 (m, 2H), 1.66 - 1.61 (m, 2H), 1.46 -1.40 (m, 4,4'-(allyloxymethylene)bis(fluorobenzene) (6k). Colorless
1
2H), 0.96 – 0.86 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, liquid (0.249 g, 96%); H NMR (400 MHz, CDCl3) δ 7.32 -
6 | J. Name., 2012, 00, 1-3
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ARTICLE
7.26 (m, 4H), 7.04 - 6.99 (m, 4H), 5.99 - 5.91 (m, 1H), 5.39 (s, 14. M. T. Thornton, L. C. Henderson, Org. PrepV.iePwrAortciceledO. nIlninte.
2013, 45, 395-420.
1H), 5.32 - 5.27 (dq, J = 17.2 Hz, J = 1.2 Hz, 1H), 5.23 - 5.19
(dq, J = 10.4 Hz, J = 1.6 Hz, 1H), 3.99 - 3.97 (dt, J = 5.6 Hz, J
= 1.6 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 163.39, 160.95,
137.80 (2C), 137.77 (2C), 134.46, 128.64 (2C), 128.56 (2C),
117.34, 115.44, 115.22, 81.18, 69.66; HRMS (ESI) m/z
(M+H)+ calcd for C16H15F2O = 261.1091, found 261.1095.
4,4'-(allyloxymethylene)bis(chlorobenzene) (6l). Colorless
DOI: 10.1039/C9OB01093A
15. L. Lapatsanis. Tetrahedron. Lett. 1978, 19, 3943-3944.
16. D. Best, S. F. Jenkinson, S. D. Rule, R. Higham, T. B.
Mercer, R. J. Newell. Tetrahedron. Lett. 2008, 49, 2196-
2199.
17. M. Kolovos, C. Froussios. Tetrahedron. Lett. 1984, 25
,
3909-3912.
1
18. K. T. Howard, B. C. Duffy, M. R. Linaburg, J. D. Chisholm.
Org. Biomol. Chem. 2016, 14, 1623-1628.
19. J. S. Yadav, D. C. Bhunia, K. K. Vamshi, P. Srihari.
Tetrahedron. Lett. 2007, 48, 8306-8310.
20. Y. Bikard Y, J. M. Weibel, C. Sirlin, L. Dupuis, J. P.
Loeffler, P. Pale. Tetrahedron. Lett. 2007, 48, 8895-8899.
21. K. W. C. Poon, G. B. Dudley. J. Org. Chem. 2006, 71
liquid (0.278 g, 95%); H NMR (400 MHz, CDCl3) δ 7.34 -
7.28 (m, 8H), 6.00 - 5.92 (m, 1H), 5.39 (s, 1H), 5.35 - 5.29 (dq,
J = 18.4 Hz, J = 2.0 Hz, 1H), 5.26 - 5.22 (dq, J = 10.4 Hz, J =
1.6 Hz, 1H), 4.02 - 4.00 (dt, J = 5.2 Hz, J = 1.2 Hz, 2H); 13C
NMR (100 MHz, CDCl3) δ 140.31 (2C), 134.32 (2C), 133.44,
128.68 (4C), 128.30 (4C), 117.34, 81.15, 69.73; HRMS (ESI)
m/z (M+H)+ calcd for C16H15Cl2O = 293.0500, found 293.0501.
,
3923-3927.
1
Benzhydryl(butyl)sulfane (8). Colorless oil (0.23g, 91%). H
22. M. T. La, H.-K. Kim. Tetrahedron. Lett. 2018, 59, 1855-
1859.
23. S. H. Ingwersen, S. Snel, T. G. K. Mant, D. Edwards. J.
NMR (400 MHz, CDCl3) δ 7.44 - 7.41 (m, 4H), 7.33 - 7.28 (m,
4H), 7.25 - 7.20 (m, 2H), 5.15 (s, 1H), 2.39 (t, J = 7.2 Hz, 2H),
1.58 - 1.51 (m, 2H), 1.41 - 1.32 (m, 2H), 0.86 (t, J = 7.2 Hz,
3H); 13C NMR (100 MHz, CDCl3) δ 141.62 (2C), 128.50 (4C),
128.29 (4C), 127.07 (2C), 54.16, 32.02, 31.14, 22.01, 13.68;
HRMS (ESI) m/z (M+H)+ calcd for C17H21S = 257.1364, found
257.1365.
Pharm. Sci. 1993, 82, 1164-1166.
Conflicts of interest
There are no conflicts to declare
Acknowledgements
This research was supported by Basic Science Research
Program through the National Research Foundation of Korea
(NRF)
funded
by
the
Ministry
of
Education
(2018R1D1A1B07047572). Tran Van Hieu was supported by
the BK21 Plus program in the Chonbuk National University
Medical School.
Notes and references
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Organic & Biomolecular Chemistry
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DOI: 10.1039/C9OB01093A
Highly efficient synthesis of diphenylmethyl Ethers from alcohols and 2-diphenylmethoxypyridine
in the presence of iron chloride has been developed.