Etherification of darylmethanols and 1-phenylalkan-1-ols over platinum on carbon

Article abstract of DOI:10.2174/157017809789869564

In the presence of platinum on carbon (Pt/C), diarylmethanols and donor substituted 1-phenylalkan-1-ols undergo cross-etherification with primary and secondary alcohols.

Full text of DOI:10.2174/157017809789869564

Letters in Organic Chemistry, 2009, 6, 515-525
515
Etherification of Diarylmethanols and 1-Phenylalkan-1-ols Over Platinum
on Carbon
Thies Thiemann*
Interdisciplinary Graduate School of Engineering Sciences, Kyushu University, 6-1, Kasuga-koh-en, Kasuga-shi,
Fukuoka 816-8580, Japan
Received August 06, 2008: Revised July 21, 2009: Accepted August 24, 2009
Abstract: In the presence of platinum on carbon (Pt/C), diarylmethanols and donor substituted 1-phenylalkan-1-ols
undergo cross-etherification with primary and secondary alcohols.
Keywords: Etherification, platinum on carbon, diarylmethanols, 1-phenylalkan-1-ols.
INTRODUCTION
protracted purification procedures involving metal salt
wastes, the author turned to the use of solid supported metals
as catalysts in etherifications. Recently, the author reported
that 4-alkoxyphenylalkyl carbinols (1) and cinnamyl alkyl
carbinols (3) dimerise in the presence of Pt/C at 135 ºC to
form ethers 2 and 4, respectively (Scheme 1) [8]. Also, (E)-
1,3-diarylprop-2-en-1-ols were found to react with a number
of primary and secondary alcohols [8b]. In the following,
further studies on the cross-etherification of (E)-1,3-
diarylprop-2-en-1-ols are discussed. Furthermore, it is shown
that this Pt/C catalysed cross-etherification can also be
applied to the reaction of diarylmethanols as well as to the
donor-substituted phenylalkanols with primary and
secondary alcohols.
The preparation of ethers is a standard reaction in organic
chemistry. Many of the syntheses of non-symmetric ethers
utilise alcohols as only one of the components of the
reaction, where the other reactant may be a halide [1], an
alkene [2], a triflate [3], tosylate [4] or otherwise activated
ester [5]. Although, there are many examples of
intramolecular reactions of non-symmetric diols leading to
non-symmetric ethers [6], only some preparative methods of
intermolecular reactions of two alcohols to non-symmetric
ethers are known [7]. Many of the latter approaches make
use of the Lewis acidity of metal salts such as, zinc chloride
[7e], magnesium perchlorate [7d] or zirconium tetrachloride
[7g] or of halogens such as of iodine [7h,i]. Others utilise an
R1
R1
RO
R1
O
Pt/C
neat
135 ˚C
RO
OR
OH
2
1
R1
R1
R
R1
O
Pt/C
neat
135 ˚C
R
R
OH
4
3
Scheme 1. Etherification of 4-alkoxyphenyl alkyl carbinols and cinnamyl alkyl carbinols in the presence of Pt/C [8].
in situ activation of one alcohol component under the
conditions of a modified Mitsunobu condensation [7f].
Needless to say that it is necessary in these intermolecular
reactions to suppress the homo-etherification in order that
the cross-etherification between the two different alcohols
becomes the main reaction.
RESULTS AND DISCUSSION
When diarylmethanols 5 are heated at 130 ºC over a long
period of time, a slow dimerisation to the corresponding
bis(diarylmethyl) ethers 6 occurs, a process which does not
complete even after 24h. When a catalytic amount of Pt/C is
added to neat diarylmethanols 5 at 130 ºC, a rapid
etherification ensues which gives products 6 in high yields
(Scheme 2). The same reaction can be found for 1,3-bis(4-
biphenyl)-prop-2-en-1-ol (7), albeit already at lower
temperatures (100 ºC).
In our quest for a cross-etherification process that does
not necessitate added solvents, overly high temperatures or
*Address correspondence to these authors at the Interdisciplinary Graduate
School of Engineering Sciences, Kyushu University, 6-1, Kasuga-koh-en,
Kasuga-shi, Fukuoka 816-8580, Japan; E-mail: thies@cm.kyushu-u.ac.jp
An addition of 10 eq. of a second alcohol, either of a
primary or a secondary alcohol, completely suppresses the
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516 Letters in Organic Chemistry, 2009, Vol. 6, No. 7
Thies Thiemann
MeO
OMe
MeO
OMe
130 ˚C
O
Pt/C
OH
5a
MeO
MeO
OMe
6a
(30 min., 97%)
MeO
130 ˚C
OMe
O
OMe
Pt/C
OH
OMe
5b
6b
OMe
(30 min, 96%)
Scheme 2. Formation of ether dimers from dimethoxyphenyl carbinols over Pt/C.
Pt/C
ROH
+
(10 eq.)
100 ˚C
OH
OR
8
7
9
Scheme 3. Etherification of 1,3-bis(4-biphenyl)-prop-2-en-1-ol over Pt/C.
R1
R1
R
R
+
R2OH
Pt/C
(10 eq.)
neat
130 ˚C
OH
O
R2
8
5
10
Scheme 4.
Table 1. Etherification of 1,3-bis(4-biphenyl)-prop-2-en-1-ol over Pt/C
Alcohol
Alcohol
Product
(R = )
Product
(R = )
OH
(90 min., 85%)
OH
(30 min., 73%)
8d
9d
9a
8a
CH3(CH2)5CH2OH
C7H15 (30 min., 93%)
(2h, 86%)
OH
8b
9b
8e
9e
OH
OH
(30 min., 90%)
CH2CH(CH3)2 (1h, 94%)
9f
8f
8c
9c

Etherification of Diarylmethanols and 1-Phenylalkan-1-ols
Letters in Organic Chemistry, 2009, Vol. 6, No. 7
517
Table 2. Etherification of Diarylcarbinols Over Pt/C
Reactant
Substrate
Product
OH
10a: R = CH3, R1 = 4-CH3,
5c: R = CH3, R1 = 4-CH3
R2 =
(1h, 78%)
8a
OH
10b: R = CH3, R1 = 4-CH3,
R2 =
5c: R = CH3, R1 = 4-CH3
(1h, 82%)
8c
OH
10c: R = CH3, R1 = 4-CH3, R2 =
5c: R = CH3, R1 = 4-CH3
CH2CH(CH3)2
(30 min., 85%)
8f
10d: R = OCH3, R1 = 4-OCH3, R2 =
CH3(CH2)5CH2OH
5a: R = OCH3, R1 = 4-OCH3
C7H15
8b
(30 min., 94%)
10e: R = OCH3, R1 = 4-OCH3, R2 =
OH
5a: R = OCH3, R1 = 4-OCH3
5a: R = OCH3, R1 = 4-OCH3
CH2Ph
(30 min., 91%)
8c
10f: R = OCH3, R1 = 4-OCH3, R2 =
OH
(30 min., 89%)
8d
OH
10g,h: R = OCH3, R1 = 4-OCH3, R2 =
10g: R3 = H: (15 min., 88%)
R3
5a: R = OCH3, R1 = 4-OCH3
R3
8g: R3 = H
8h: R3 = OCH3
10h: R3 = OCH3: (30 min., 74%)
10i: R = OCH3, R1 = 4-OCH3, R2 =
5a: R = OCH3, R1 = 4-OCH3
O
(30 min., 87%)
OH
O
8i
O
10j: R = OCH3, R1 = 4-OCH3, R2 =
5a: R = OCH3, R1 = 4-OCH3
5d: R = OCH3, R1 = H
HO
O
(30 min., 85%)
8j
10k: R = OCH3, R1 = H, R2 = C7H15
CH3(CH2)5CH2OH
8b
(30 min., 75%)
OH
10l: R = OCH3, R1 = H, R2 =
5d: R = OCH3, R1 = H
(3h, 86%)
8a
OH
10m: R = OCH3, R1 = H, R2 = CH2Ph
5d: R = OCH3, R1 = H
(1h, 90%)
8c

518 Letters in Organic Chemistry, 2009, Vol. 6, No. 7
Thies Thiemann
(Table 2). Contd…..
Reactant
Substrate
Product
OH
10n: R = OCH3, R1 = H, R2 =
5d: R = OCH3, R1 = H
(1h, 89%)
8j
OH
10o: R = OCH3, R1 = H, R2 =
5d: R = OCH3, R1 = H
O
(1h, 86%)
O
8k
10p: R = OCH3, R1 = 2-OCH3, R2 =
OH
5b: R = OCH3, R1 = 2-OCH3
CH2Ph
(30 min., 90%)
8c
10q: R = OCH3, R1 = 2-OCH3, R2 =
CH3(CH2)3CH2OH
5b: R = OCH3, R1 = 2-OCH3
5b: R = OCH3, R1 = 2-OCH3
C5H11
8l
(30 min., 94%)
OH
10r: R = OCH3, R1 = 2-OCH3, R2 =
(30 min., 91%)
8k
10s: R = OCH3, R1 = 2-OCH3, R2 =
5b: R = OCH3, R1 = 2-OCH3
O
OH
(30 min., 89%)
O
8i
OH
10t: R = OCH3, R1 = OCH3, R2 =
5b: R = OCH3, R1 = 2-OCH3
(30 min., 81%)
8a
10u: R = H, R1 = H, R2 = C7H15
CH3(CH2)5CH2OH
5d: R = H, R1 =H
5d: R = H, R1 =H
8b
(3h, 25%)
10v: R = H, R1 =H, R2 = C6H5 = Ph
OH
(nr)
8p
homo-etherification and solely products stemming from the
cross-etherification can be found (Schemes 3 and 4, Tables 1
and 2). Again, reactions with diarylmethanols 5 are the best
carried out at 130 ºC (Table 2), while reaction with 1,3-
bis(4-biphenyl)-prop-2-en-1-ol (7) necessitates lower
temperatures (100 ºC) (Table 1).
Reaction proceeds best with electron donor substituted 5,
such as with methyl or methoxy substituted 5. Reaction with
the parent compound 5e proceeds more slowly. The scope of
primary and secondary alcohols is large. Pt driven
isomerisation of olefinic moieties does not take place. Thus,
allyl alcohol (8d) reacts well to give the desired product 9d.
Interestingly, also acid sensitive alcohols such as oxiran-2-
H3CO
OCH3
Pt/C
H3CO
OCH3
+
OCH3
130 ˚C
OH
10v
8q
5a
nr
OCH3
Scheme 5.

Etherification of Diarylmethanols and 1-Phenylalkan-1-ols
Letters in Organic Chemistry, 2009, Vol. 6, No. 7
519
R1
RO
R2
O
R1
+
R2OH
Pt/C
neat
135 ˚C
(10 eq.)
RO
OH
12
8
11
Scheme 6.
ylmethanol (8j) can be reacted with ease. Also, 4-
methoxycinnamyl alcohol (8h), which itself would be
expected to dimerise under the conditions, can be used
successfully as reactant. Indeed, over Pt/C, 4-
methoxycinnamyl alcohol (8h) itself undergoes slow
dimerisation to bis(4-methoxycinnamyl)ether [9], which is
obtained as a separable by-product. Nevertheless, in the
reaction of bis(4-methoxyphenyl)methanol (5a) with 4-
methoxycinnamyl alcohol (8h), the desired product 10h can
be isolated in acceptable yield. When cinnamyl alcohol (8g)
is used and the reaction time shortened to 15 min (at 130 ºC),
only the desired cross-etherification product 10g is formed.
On the other hand, phenols do not react well. Thus, when
phenol (10 eq.) itself is reacted under the conditions with (4-
methoxyphenyl)-phenylcarbinol (5d) at 130 ºC, no cross-
etherification can be observed. Also, the trapping of a
potential diphenylmethyl cation intermediate with electron
rich arenes in a Friedel-Craft type reaction does not occur.
Thus, the reaction of 5a in the presence of 10eq. of anisole
does not yield any tris(p-anisyl)methane (Scheme 5), but
provides exclusively ether 6a.
ether at the same temperatures, indicating that Pt(0) in
aerated diphenyl ether can be oxidised to a higher oxidation
state [14]. In the case of the presence of Pt(II), a reaction
mechanism as detailed by M. M. Abu-Omar et al. and J.
Muzart et al. [11] for Pd(II) can be taken into account. This
involves a Pd-assisted SN reaction of the alcohol, where with
the catalytic system L2PdCl2/AgOTf an SN1 reaction with
intermediate cation formation from the diarylcarbinol
substrate has been formulated [11c].
While the results reported here are from the experiments
carried out with a 5 wt% Pt on carbon as supplied by Wako
Co., also other commercially available samples of Pt on
carbon were tested in the reactions. Of those tested, the only
Pt on carbon that failed to produce any enhancement of
reactivity was found to be Pt/C Degussa type F101 RA/W
(wet). It could also be observed that the etherification of 5a,
a slow reaction in the absence of a catalyst, can be
accelerated significantly even in the presence of platinum
powder (200 mesh). The reaction of 5a with 8c to 10e could
also be carried out successfully with platinum powder, albeit
with longer reaction times (8h, 130 ºC, 80%).
Donor substituted 1-phenylalkan-1-ols 11 can be used
successfully as substrates in the cross-etherication reaction,
catalysed by Pt/C (Scheme 6 and Table 3). In this case, steric
congestion in the substrate such as in the case of 11c leads to
some loss of reactivity, indicating that the reactions proceed
at or near to the surface of the catalyst support (see below).
Here, much longer reaction times are needed (6h vs.
normally 30 min. at 130 ºC).
In conclusion, it could be shown that in the presence of
platinum on carbon (Pt/C), diarylmethanols 5 and donor
substituted 1-phenylalkan-1-ols 11 undergo cross-
etherification with primary and secondary alcohols. Acid-
labile alcohols such as oxiran-2-ylmethanol (8j) and (3-
methyloxetan-3-yl) methanol (8i) are viable substrates for
the reaction.
The actual mechanism of the reaction has not been
ascertained. Reports have appeared of the activation of
oxygen containing substrates with salts of the platinum metal
group, with Pt(II) complexes [10] and Pd(II) salts [11], in
homogeneous reactions. There is some indication in the
present case that the etherification proceeds on or near the
surface of the catalyst. Thus, sterically more exacting
alcohols do not react. tert-Butanol leads to only a small
amount of product and phenylglycidol does not react, while
glycidol itself reacts with ease. It can be believed that Pt (0),
immobilised on the carbon support [12], functions as a weak
Lewis acid catalyst. It is known that alcohols absorb on
platinum [Pt(111)] with an oxygen lone-pair interaction with
platinum of about 42 kJ mol-1 [13]. However, as the above
experiments have been carried out at elevated temperatures
and in the presence of oxygen, it can be known that, the
catalytically active species is not Pt(0), but rather Pt in a
higher oxidation state such as Pt(II). Thus, for other
reactions, the authors have found that Pt, derived from
Pt(PPh3)4, supports transformations in diphenyl ether at
elevated temperatures in the presence of oxygen. These
reactions are not supported by Pt(0) in deaerated diphenyl
EXPERIMENTAL
General
Melting points were measured on a Yanaco microscopic
hotstage and are uncorrected. Infra-red spectra were
measured with JASCO IR-700 and Nippon Denshi JIR-
1
13
AQ2OM machines. H- and
C-NMR spectra were
recorded with a JEOL EX-270 spectrometer. The chemical
shifts were relative to TMS (solvent CDCl3, unless otherwise
noted). Mass spectra were measured with a JMS-01-SG-2
spectrometer (EI, 70 eV). Column chromatography was
carried out on Wakogel 300.
All diarylmethanols were prepared from the
corresponding benzophenones by reduction with NaBH4 in
MeOH. 4,4’-Dimethoxybenophenone (TCI), 2,4’-dimetho-
xybenzophenone (TCI), and 4-methoxybenzophenone (4-
benzoylanisole, TCI) were acquired commercially. 4-
Methoxycinnamyl alcohol (NaBH4, CeCl3, MeOH) was
obtained from 4-methoxycinnamaldehyde (TCI). 1-(4-
Ethoxyphenyl)propan-1-ol and (1-4-octyloxyphenyl)ethanol
were prepared by O-alkylation of phenol (EtI, KOH, DMSO

520 Letters in Organic Chemistry, 2009, Vol. 6, No. 7
Thies Thiemann
Table 3. Etherification of 1-Phenyl-alkan-1-ols Over Pt/C
Substrate
Reactant
Product (Reaction Time/Yield)
H5C2O
H5C2O
CH3(CH2)6CH2OH
8m
12
11a
OH
OR
OH
12a: R = C8H7 (30 min., 88%)
12b: R = CH2Ph (30 min., 86%)
11a
11a
8c
OH
12c: R =
(1h, 84%)
8a
H11C5O
H11C5O
CH3(CH2)6CH2OH
OR
8m
11b
OH
12d: R = C8H17 (30 min., 87%)
12e: R = CH2Ph (30 min., 89%)
OH
11b
8c
H3CO
OH
O
H3CO
8c
OH
11c
12f (6h, 75%)
Br
Br
Br
Ph3P
min. CHCl3
+
Br
OHC
O
O
16
14
(91%)
15
13
B(OH)2
DME, aq. Na2CO3
NaBH4
CeCl3
MeOH
Et2O
OH
O
(88%)
(78%)
17
7
Scheme 7. Preparation of 1,3-bis(biphenyl)prop-2-en-1-one (17) and 1,3-bis(4-biphenyl)-prop-2-en-1-ol (7).
or CH3(CH2)6CH2OH, cetylammonium bromide, 20w% aq.
NaOH), subsequent Friedel-Crafts acylation (acetyl chloride,
propionyl chloride or isobutyroyl chloride, AlCl3, 1,2-
dichloroethane) and reduction with NaBH4 in MeOH or in
MeOH/ether. 1,3-Bis(4-biphenyl)-prop-2-en-1-ol (7) [see
also ref. 15] was prepared by Luche reduction (CeCl3,

Etherification of Diarylmethanols and 1-Phenylalkan-1-ols
Letters in Organic Chemistry, 2009, Vol. 6, No. 7
521
NaBH4, MeOH) [16] from 1,3-bis(4-biphenyl)-prop-2-en-1-
one (17), which itself was synthesised from commercially
available 4-bromobenzaldehyde (13) in two steps, namely by
Wittig Olefination using the stabilised phosphorane 14 [17]
to 15 followed by Suzuki-Miyaura cross coupling reaction
with phenylboronic acid (16) (Scheme 7).
(2C), 127.06 (2C), 127.10 (2C), 127.25 (2C), 127.33, 127.40
(2C), 128.77 (6C), 130.20, 131.48, 135.52, 140.57, 140.59,
140.78, 141.75; MS (EI, 70 eV) m/z (%) = 362 (M+, 22), 344
(100), 181 (42). HRMS Found: 362.1672. Calcd. for
C27H22O: 362.1671. Calcd. for C27H22O: C, 89.47; H, 6.12%.
Found: C, 89.20; H, 6.10%.
Platinum on activated carbon (5 wt%) from Wako Pure
Industries (Lot 167-13911) and platinum powder (200 mesh)
from Kishida Chemicals were acquired commercially.
Procedure B
1,3-Bis(4-biphenyl)-prop-2-en-1-yl heptyl ether (9b). - A
mixture of 7 (300 mg, 0.83 mmol), n-heptanol (960 mg, 8.3
mmol, 10 eq.) and Pt/C (20 mg, 5 wt%, 5.1.10-3 mmol Pt, 0.6
mol%) is kept at 100 ºC for 30 min. Thereafter, the cooled
Procedure A
DL- and meso bis(2-anisyl-4-anisylmethyl)ether (6b). - A
mixture of 5b (550 mg, 2.25 mmol) and Pt/C (50 mg, 5 wt%,
12.7.10-3 mmol Pt, 1.0 mol%) was kept at 130 ºC for 30 min.
Thereafter, the cooled mixture was subjected to a filtration
over silica gel (hexane/ether/CHCl3 2:1:1) to give 9b (528
mg, 96%, DL/meso 55:45) as a colourless oil; IR (neat; A/B)
ꢀ 3000, 2950, 2834, 1611, 1516, 1462, 1439, 1339, 1246,
mixture is subjected to
a filtration over silica gel
(hexane/ether/CHCl3 5:1:1) to give 9b (355 mg, 93%) as a
colourless oil; IR (neat) ꢀ 3028, 2928, 2854, 1601, 1510,
1486, 1459. 1450, 1406, 1378, 1298, 1032, 1006, 968, 839,
762, 697 cm-1; 1H NMR (270 MHz, CDCl3) ꢁ 0.88 (t, 3H, 3J
6.5 Hz), 1.28 (m, 8H), 1.67 (m, 2H), 3.51 (m, 2H, OCH2),
4.96 (d, 1H, 3J 7.0 Hz), 6.37 (dd, 1H, 3J 16.7 Hz, 3J 7.0 Hz),
1
1169, 1113, 1040, 862, 815, 758 cm-1; H NMR (270 MHz,
6.67 (d, 1H, J 16.7 Hz), 7.30 - 7.67 (m, 18H); 13C NMR
3
CDCl3) ꢁ 3.63 (s, 3H, OCH3, A), 3.64 (s, 3H, OCH3, B), 3.75
(67.8 MHz, CDCl3) ꢁ 14.08, 22.62, 26.22, 29.17, 29.95,
31.85, 68.92, 81.41, 126.92 (2C), 127.03 (2C), 127.11 (2C),
127.20 (2C), 127.26 (5C), 127.28, 128.74 (2C), 128.76 (2C),
130.69, 130.78, 135.73, 140.43, 140,54, 140.67 (2C),
140.96; MS (EI, 70 eV) m/z (%) = 460 (M+, 13), 346 (39),
281 (78), 198 (58), 181 (100), 149 (75). HRMS Found:
460.2762. Calcd. for C34H36O: 460.2766. Calcd. for
C34H36O.0.3H2O: C, 87.62; H, 7.91%. Found: C, 87.70; H,
7.83%.
(s, 3H, OCH3, A), 3.76 (s, 3H, OCH3, B), 5.72 (s, 1H, A),
3
5.73 (s, 1H, B), 6.78 (m, 1H, A, B), 6.79 (d, 2H, J 8.6 Hz,
A, B); 6.96 (m, 1H, A, B), 7.24 (d, 2H, 3J 8.6 Hz, A, B), 7.66
(m, 1H, A, B); 13C NMR (67.8 MHz, CDCl3) ꢁ 55.16 (OCH3,
A, B), 55.27 (OCH3, A, B), 73.51 (A), 73.70 (B), 110.46 (A),
110.50 (B), 113.28 (2C, A, B), 120.46 (A, B), 127.17 (B),
127.22 (A), 127.89 (A), 127.97 (B), 128.63 (B, 2C), 128.70
(A, 2C), 131.40 (A), 131.69 (B), 134.76 (B), 135.00 (A),
156.49 (A), 156.72 (B), 158.48 (B), 158.52 (A); MS (EI, 70
eV) m/z (%) = 470 (M+, 2.4), 362 (18), 227 (100), 135 (33),
121 (89). HRMS Found: 470.2094. Calcd. for C30H30O5:
470.2093.
9a - 9f were Prepared According to Procedure B
1,3-Bis(4-biphenyl)-prop-2-en-1-yl cyclopentyl ether
(9a); colourless oil; IR (neat) ꢀ 3024, 2952, 1601, 1514,
1
Bis(bis[4-anisyl]methyl) ether (6a), prepared according
to procedure A: colourless oil; IR (neat) ꢀ 2928, 1612, 1508,
1485, 1450, 1404, 1174, 1092, 970, 838, 758, 696 cm-1; H
NMR (270 MHz, CDCl3) ꢁ 1.75 - 1.79 (m, 8H), 4.11 (m,
1
1456, 1240, 1171, 1030, 826, 751, 701 cm-1; H NMR (270
1H), 5.05 (d, 1H, 3J 7.0 Hz), 6.37 (dd, 1H, 3J 16.5 Hz, 3J 7.0
3
MHz, CDCl3) ꢁ 3.78 (s, 6H, 2 OCH3), 5.28 (s, 2H), 6.84 (d,
2H, 3J 8.9 Hz), 7.24 (d, 2H, 3J 8.9 Hz); 13C NMR (67.8 MHz,
CDCl3) ꢁ 55.26 (4C), 78.91 (2C), 113.72 (8C), 128.45 (2C),
134.82 (4C), 158.84 (4C). MS (EI, 70 eV) m/z (%) = 470
(M+, 2.0), 362 (5.0), 243 (23), 227 (100). HRMS Found:
470.2095. Calcd. for C30H30O5: 470.2093.
Hz), 6.67 (d, 1H, J 16.5 Hz), 7.29 - 7.61 (m, 18H); 13C
NMR (67.8 MHz, CDCl3) ꢁ 23.59, 23.65, 32.53, 32.59,
78.88, 80.09, 126.91 (2C), 127.02 (2C), 127.10 (2C), 127.19
(5C), 127.27, 127.32 (2C), 128.73 (2C), 128.76 (2C),
130.46, 131.16, 135.80, 140.37, 140.41, 140.69, 140.99,
141.01; MS (EI, 70 eV) m/z (%) = 430 (M+, 12) 362 (52),
345 (100), 209 (25), 181 (94), 167 (78), 154 (48), 136 (30).
HRMS Found: 430.2289. Calcd. for C32H30O: 430.2297.
1,3-Bis(4-biphenyl)-prop-2-en-1-ol (7). - At 0 ºC, NaBH4
was added slowly to a mixture of 17 (3.8 g, 10.5 mmol) and
anhydrous cerium trichloride (2.7 g, 11.1 mmol) in methanol
(20 mL) and ether (10 mL); colourless solid. After the
mixture was stirred for 15 min., it was concentrated in vacuo
at ambient temperature. Thereafter, water (40 mL) was
added and the ensuing mixture extracted with chloroform (2
X 30 mL). To the aqueous phase was added ammonium
chloride was added and the mixture was extracted with
chloroform (25 mL). The combined organic phase was dried
over anhydrous MgSO4, concentrated in vacuo, and the
residue was subjected to column chromatography on silica
gel (hexane/ether/CHCl3 1:1:1) to give 7 (3.0 g, 78%); mp.
142 ºC; IR (KBr) ꢀ 3450 (bs, OH), 1486, 1406, 1074, 1004,
963, 824, 759, 694 cm-1; 1H NMR (270 MHz, CDCl3) ꢁ 2.14
1,3-Bis(4-biphenyl)-prop-2-en-1-yl benzyl ether (9c);
colourless solid; mp. 126 ºC; 1H NMR (270 MHz, CDCl3) ꢁ
4.63 (s, 2H, OCH2Ph), 5.08 (d, 1H, 3J 7.0 Hz), 6.41 (dd, 1H,
3
3
3J 15.9 Hz, J 7.0 Hz), 6.70 (d, 1H, J 15.9 Hz), 7.30 - 7.63
(m, 23H); 13C NMR (67.8 MHz, CDCl3) ꢁ 70.21, 81.33,
126.93 (2C), 127.07 (2C), 127.12 (2C), 127.24 (2C), 127.29,
127.35 (2C), 127.44 (2C), 127.59, 127.77 (2C), 128.43 (2C),
128.77 (5C), 130.27, 131.20, 135.63, 138.41, 140.17,
140.55, 140.67, 140.72, 140.91, 147.71; MS (FAB, 3-
nitrobenzyl alcohol) m/z (%) = 452 (M+, 0.7), 345 (4.1).
HRMS Found: 452.2133. Calcd. for C34H28O: 452.2140.
Calcd. for C34H28O.0.1H2O: C, 89.87; H, 6.25%. Found: C,
89.70; H, 6.19%.
3
3
(bs, 1H, OH), 5.45 (d, 1H, J 5.9 Hz), 6.45 (dd, 1H, J 15.4
Hz, 3J 5.9 Hz), 6.76 (d, 1H, 3J 15.4Hz); 7.24 - 7.62 (m, 18H);
13C NMR (67.8 MHz, CDCl3) ꢁ 74.93, 126.79 (2C), 126.91
1,3-Bis(4-biphenyl)-prop-2-en-1-yl allyl ether (9d);
1
colourless oil; H NMR (270 MHz, CDCl3) ꢁ 4.09 (m, 2H),
5.05 (d, 1H, 3J 6.8 Hz), 5.22 (m, 1H), 5.34 (m, 1H), 6.00 (m,

522 Letters in Organic Chemistry, 2009, Vol. 6, No. 7
Thies Thiemann
3
3
3
1H), 6.38 (dd, 1H, J 15.9 Hz, J 7.0 Hz), 6.69 (d, 1H, J
15.9 Hz), 7.29 - 7.63 (m, 18H); 13C NMR (67.8 MHz,
CDCl3) ꢀ 69.35, 81.54, 117.03, 126.93 (2C), 127.05 (2C),
127.11 (2C), 127.22 (2C), 127.27, 127.32 (4C), 127.35 (2C),
128.76 (4C), 130.27, 131.06, 134.83, 135.62, 140.19,
140.53, 140.66, 140.91; IR (neat) ꢁ 3026, 2924, 2852, 1643,
1600, 1511, 1486, 1450, 1407, 1299, 1178, 1074, 1008, 969,
838, 761, 696 cm-1; MS (FAB, 3-nitrobenzyl alcohol) m/z
(%) = 402 (M+, 5.5), 345 (57), 181 (100). HRMS Found:
402.1986. Calcd. for C30H26O: 402.1984
(85). HRMS Found: 302.1665. Calcd. for C22H22O:
302.1671.
Bis(4-tolyl)methyl isobutyl ether (10c); colourless oil; IR
(neat) ꢁ 2929, 1512, 1466, 1177, 1088, 1020, 965, 814, 764,
1
3
697 cm-1; H NMR (270 MHz, CDCl3) ꢀ 0.93 (d, 6H, J 6.5
3
3
Hz, 2 CH3), 1.91 (dsept, 1H, J 6.8 Hz, J 6.5 Hz), 2.31 (s,
3
6H, 2 CH3), 3.19 (d, 2H, J 6.8 Hz), 5.25 (s, 1H), 7.10 (d,
4H, 3J 7.8 Hz), 7.23 (d, 4H, 3J 7.8 Hz); 13C NMR (67.8 MHz,
CDCl3) ꢀ 19.52 (2C), 21.08 (2C), 28.71, 75.83, 83.28,
126.83 (4C), 128.94 (4C), 136.73 (2C), 139.99 (2C); MS
(EI, 70 eV) m/z (%) = 268 (M+, 68), 195 (100), 165 (44), 119
(47). HRMS Found: 268.1828. Calcd. for C19H24O:
268.1827.
1,3-Bis(4-biphenyl)-prop-2-en-1yl cyclohexyl ether (9e);
colourless oil; IR (neat) ꢁ 3026, 2928, 2854, 1650, 1486,
1072, 969, 836, 761, 696 cm-1; H NMR (270 MHz, CDCl3)
1
ꢀ 1.20 - 1.50 (m, 4H), 1.76 (m, 4H), 1.96 (m, 2H), 3.46 (m,
Bis(4-anisyl)methyl heptyl ether (10d); colourless oil; IR
(neat) ꢁ 2966, 2930, 2854, 1610, 1585, 1511, 1463, 1340,
1302, 1250, 1171, 1093, 1076, 827, 757 cm-1; 1H NMR (270
MHz, CDCl3) ꢀ 0.88 (m, 3H), 1.27 (m, 8H), 1.61 (m, 2H),
1H), 5.16 (d, 1H, 3J 6.8 Hz), 6.37 (dd, 1H, 3J 16.2 Hz, 3J 6.8
3
Hz), 6.65 (d, 1H, J 16.2 Hz), 7.27 - 7.60 (m, 18H); 13C
NMR (67.8 MHz, CDCl3) ꢀ 24.21 (2C), 25.85, 32.56 (2C),
74.87, 78.91, 126.89 (2C), 127.01 (2C), 127.07 (2C), 127.16,
127.18 (4C), 127.26 (3C), 128.71 (2C), 128.74 (2C), 130.25,
131.37, 135.81, 140.34 (2C), 140.67, 140.96, 141.22; MS
(FAB, 3-nitrobenzyl alcohol) m/z (%) = 444 (M+, 8.4), 362
(46), 345 (100). HRMS Found: 444.2455. Calcd. for
C33H32O: 444.2453.
3
3.40 (t, 2H, J 6.5 Hz), 3.78 (s, 6H, 2 OCH3), 5.25 (s, 1H),
3
3
6.84 (d, 4H, J 8.6 Hz), 7.23 (d, 4H, J 8.6 Hz); 13C NMR
(67.8 MHz, CDCl3) ꢀ 14.80, 23.34, 26.95, 29.86, 30.62,
32.55, 55.94 (2C, OCH3), 69.74, 83.37, 114.39 (4C), 128.85
(4C), 135.86 (2C), 159.51 (2C); MS (EI, 70 eV) m/z (%) =
342 (M+, 51), 227 (100). HRMS Found: 342.2190. Calcd. for
.
1,3-Bis(4-biphenyl)-prop-2-en-1yl isopropyl ether (9f);
colourless oil; IR (neat) ꢁ3028, 2956, 2868, 1600, 1486,
C22H30O3: 342.2195. Calcd. for C22H30O3 H2O: C, 73.15; H,
8.99. Found: C, 73.35; H, 8.42%.
1
1404, 1076, 1007, 968, 838, 761, 696 cm-1; H NMR (270
Bis(4-anisyl)methyl benzyl ether (10e); colourless oil; IR
(neat) ꢁ2924, 1624, 1505, 1455, 1245, 1172, 1031, 825, 736,
MHz, CDCl3) ꢀ 0.97 (d, 6H, 3J 6.5 Hz, 2 CH3), 1.97 (ddh, 3J
3
6.8 Hz, J 6.8 Hz, 3J 6.5 Hz), 3.23 (dd, 1H, 2J 9.5 Hz, 3J 6.8
1
695 cm-1; H NMR (270 MHz, CDCl3) ꢀ 3.78 (s, 6H, 2
3
3
Hz), 3.34 (dd, 1H, 2J 9.5 Hz, J 6.8 Hz), 4.95 (d, J 6.8 Hz),
3
OCH3), 4.51 (s, 2H), 5.36 (s, 1H), 6.85 (d, 4H, J 8.6 Hz),
3
3
3
6.36 (dd, 1H, J 15.1 Hz, J 6.8 Hz), 6.67 (d, 1H, J 15.1
Hz), 7.30 - 7.61 (m, 18H); 13C NMR (67.8 MHz, CDCl3) ꢀ
19.56 (2C), 31.58, 75.67, 82.44, 126.93 (2C), 127.03 (2C),
127.11 (2C), 127.22 (8C), 127.29, 128.74 (2C), 128.76 (2C),
130.60, 130.87, 140.43, 140.47, 140.69, 140.74, 140.96; MS
(FAB, 3-nitrobenzyl alcohol) m/z (%) = 418 (M+, 22), 361
(20), 345 (53), 239 (37), 181 (100), 167 (51). HRMS Found:
418.2298. Calcd. for C31H30O: 418.2297.
3
7.28 (d, 4H, J 8.6 Hz), 13C NMR (67.8 MHz, CDCl3) ꢀ
55.24 (2C, 2 OCH3), 70.25, 81.55, 113.75 (4C), 127.45,
127.70, 128.33 (4C), 134.58 (2C), 138.58, 158.91 (2C); MS
(EI, 70 eV) m/z (%) = 334 (M+, 14), 243 (31), 227 (100).
HRMS Found: 334.1569. Calcd. for C22H22O3: 334.1569.
.
Calcd. for C22H22O3 0.1H2O: C, 78.46; H, 6.69. Found: C,
78.41; H, 6.61%.
Bis(4-anisyl)methyl allyl ether (10f); colourless oil; IR
(neat) ꢁ2932, 1611, 1507, 1455, 1244, 1169, 1034, 926, 815,
10a - 10u and 12a - 12f were Prepared According to
Procedure B, but the Reactions were Carried Out at 130 ºC
1
772 cm-1; H NMR (270 MHz, CDCl3) ꢀ 3.78 (s, 6H, 2
Bis(4-tolyl)methyl cyclopentyl ether (10a); colourless
oil; IR (neat) ꢁ 2924, 1515, 1453, 1260, 1087, 804, 699 cm-1;
1H NMR (270 MHz, CDCl3) ꢀ 1.47 (m, 2H), 1.73 (m, 6H),
2.31 (s, 6H, 2 CH3), 3.96 (m, 1H), 5.35 (s, 1H), 7.10 (d, 4H,
OCH3), 3.97 (m, 2H), 5.15 - 5.32 (m, 2H), 5.34 (s, 1H), 5.93
3
(m, 1H), 6.85 (d, 4H, 3J 8.6 Hz), 7.25 (d, 4H, J 8.6 Hz); 13C
NMR (67.8 MHz, CDCl3) ꢀ 55.23 (2C, 2 OCH3), 69.46,
81.74, 113.73 (4C), 116.71, 128.20 (4C), 134.67 (2C),
134.97, 158.87 (2C); MS EI, 70 eV) m/z (%) = 284 (M+, 25),
227 (100), 135 (38). HRMS Found: 284.1413. Calcd. for
C18H20O3: 284.1412.
3
3J 8.1 Hz), 7.20 (d, 4H, J 8.1 Hz); 13C NMR (67.8 MHz,
CDCl3) ꢀ 21.10 (2C), 23.60 (2C), 32.41 (2C), 78.87, 80.74,
127.09 (4C), 128.94 (4C), 136.71 (2C), 140.16 (2C); MS
(EI, 70 eV) m/z (%) = 280 (M+, 41), 105 (100), 180 (32), 165
(48), 119 (25). HRMS Found: 280.1832. Calcd. for C20H24O:
280.1827.
Bis(4-anisyl)methyl cinnamyl ether (10g); colourless oil;
1H NMR (270 MHz, CDCl3) ꢀ 3.78 (s, 6H, 2 OCH3), 4.15 (d,
3
3
2H, 3J 5.7 Hz), 5.40 (s, 1H), 6.33 (dt, 1H, J 15.9 Hz, J 5.7
Hz), 6.59 (d, 1H, 3J 15.9 Hz), 6.86 (d, 4H, 3J 8.9 Hz), 7.22 -
7.39 (m, 9H); 13C NMR (67.8 MHz, CDCl3) ꢀ 55.25, 66.13,
81.75, 113.76 (4C), 126.38, 126.46 (2C), 127.57, 128.25
(4C), 128.52 (2C), 132.14, 134.59 (2C), 136.83, 158.89
(2C); MS (EI, 70 eV) m/z (%) 360 (M+, 3.6), 242 (49), 224
(100). HRMS Found: 360.1725. Calcd. for C24H24O3:
360.1725.
Bis(4-tolyl)methyl benzyl ether (10b); colourless oil; IR
(neat) ꢁ 3020, 2922, 2856, 1511, 1451, 1300, 1177, 1068,
813, 764, 733, 636 cm-1; 1H NMR (270 MHz, CDCl3) ꢀ 2.32
(s, 6H, 2 CH3), 4.52 (s, 2H), 5.38 (s, 1H), 7.12 (d, 4H, 3J 8.1
3
Hz), 7.25 (d, 4H, J 8.1 Hz), 7.26 - 7.37 (m, 5H); 13C NMR
(67.8 MHz, CDCl3) ꢀ 21.32 (2C), 70.53, 82.38, 127.23 (4C),
127.64, 127.88 (2C), 128.52 (2C), 129.26 (4C), 137.21 (2C),
138.81, 139.61 (2C); MS (EI, 70 eV) m/z (%) = 302 (M+,
1.9), 211 (100), 195 (97), 181 (25), 165 (33), 119 (51), 91
Bis(4-anisyl)methyl 4-methoxycinnamyl ether (10h);
1
colourless oil; H NMR (270 MHz, CDCl3) ꢀ 3.78 (s, 6H, 2
3
4
OCH3), 3.80 (s, 3H, OCH3), 4.12 (dd, 2H, J 6.2 Hz, J 1.4

Etherification of Diarylmethanols and 1-Phenylalkan-1-ols
Letters in Organic Chemistry, 2009, Vol. 6, No. 7
523
3
3
Hz), 5.40 (s, 1H), 6.19 (dt, 1H, J 14.9 Hz, J 6.2 Hz), 6.51
(dd, 1H, 3J 14.9 Hz, 4J 1.4 Hz), 6.84 (d, 2H, 3J 8.6 Hz), 6.86
(d, 4H, 3J 8.6 Hz), 7.27 (d, 4H, 3J 8.6 Hz), 7.31 (d, 2H, 3J 8.6
Hz); ꢀC (67.8 MHz, CDCl3) 55.24 (2C), 55,26, 69.32, 81.62,
113.75 (4C), 113.95 (2C), 124.11, 127.68 (2C), 128.26 (4C),
129.63, 131.88, 134.68 (2C), 158.88 (2C), 159.29; MS
(FAB, 3-nitrobenzyl alcohol) m/z (%) 391 (MH+, 1.6).
HRMS Found: 391.1904. Calcd. for C25H27O4: 391.1909,
70 eV) m/z (%) = 282 (M+, 21), 197 (100). HRMS Found:
282.1619. Calcd. for C19H22O2: 282.1620.
(4-Anisyl)-phenylmethyl benzyl ether (10m); colourless
oil; IR (neat) ꢁ 3062, 3028, 2932, 2858, 1611, 1585, 1511,
1459, 1302, 1246, 1172, 1093, 1035, 826, 736, 699 cm-1; 1H
NMR (270 MHz, CDCl3) ꢀ 3.78 (s, 3H, OCH3), 4.53 (s, 2H),
5.40 (s, 1H), 6.86 (d, 2H, 3J 8.9 Hz), 7.25 - 7.39 (m, 7H); 13
C
NMR (67.8 MHz, CDCl3) ꢀ 55.24, 70.36, 82.00, 113.79
(2C), 127.00 (2C), 127.32, 127.48, 127.69 (2C), 128.34
(4C), 128.47 (2C), 134.32, 138.49, 142.41, 159.00; MS (EI,
70 eV) m/z (%) = 304 (M+, 17), 213 (59), 197 (100). HRMS
Found: 304.1464. Calcd. for C21H20O2: 304.1463. Calcd. for
1
and bis(4-methoxycinnamyl) ether; colourless solid;[9] H
NMR (270 MHz, CDCl3) ꢀ 3.81 (s, 6H, 2 OCH3), 4.17 (dd,
3
4
3
3
4H, J 5.4 Hz, J 1.4 Hz), 6.20 (dt, 2H, J 15.7 Hz, J 5.4
Hz), 6.57 (dd, 2H, 3J 15.7 Hz, 4J 1.4 Hz), 6.85 (d, 4H, 3J 8.6
3
Hz), 7.32 (d, 4H, J 8.6 Hz); ꢀC (67.8 MHz, CDCl3) 55.27
.
C21H20O2 0.2H2O: C, 81.89; H, 6.67. Found: C, 81.91; H,
(2C, 2 OCH3), 70.83 (2C), 113.97 (4C), 123.82 (2C), 127.68
(4C), 129.53 (2C), 132.28 (2C), 159.30 (2C); MS (EI, 70
eV) m/z (%) 310 (M+, 14), 148 (100). HRMS Found:
310.1566. Calcd. for C20H22O3: 310.1569.
6.61%.
(4-Anisyl)-phenylmethyl but-3-ynyl ether (10n);
colourless oil; IR (neat) ꢁ 3290, 3060, 3028, 3002, 2928,
2866, 2834, 1612, 1585, 1513, 1454, 1248, 1173, 1082,
Bis(4-anisyl)methyl (3-methyloxetan-3-yl)methyl ether
(10i); colourless oil; IR (neat) ꢁ 2988, 2951, 2870, 1610,
1586, 1506, 1459, 1342, 1300, 1084, 1036, 978, 855, 755
cm-1; 1H NMR (270 MHz, CDCl3) ꢀ 1.27 (s, 3H, CH3), 3.47
1
1034, 809, 740, 699, 634 cm-1; H NMR (270 MHz, CDCl3)
ꢀ 1.96 (t, 1H, 4J 2.7 Hz), 2.52 (dt, 2H, 3J 7.0 Hz, 4J 2.7 Hz),
3
3.58 (t, 2H, J 7.0 Hz), 3.78 (s, 3H, OCH3), 5.37 (s, 1H),
6.85 (d, 2H, 3J 8.6 Hz), 7.24 - 7.33 (m, 7H); 13C NMR (67.8
MHz, CDCl3) ꢀ 19.99, 55.24, 66.96, 69.23, 81.40, 83.31,
113.79 (2C), 126.88 (2C), 127.39, 128.34 (4C), 134.17,
142.23, 159.03; MS (EI, 70 eV) m/z (%) = 266 (M+, 29), 238
(15), 197 (100), 189 (50). HRMS Found: 266.1307. Calcd.
2
(s, 2H), 3.79 (s, 6H, 2 OCH3), 4.35 (d, 2H, J 5.9 Hz), 4.53
(d, 2H, 2J 5.9 Hz), 5.28 (s, 1H), 6.85 (d, 4H, 3J 8.6 Hz), 7.23
(d, 4H, J 8.6 Hz); 13C NMR (67.8 MHz, CDCl3) ꢀ 21.11,
3
39.51, 54.77 (2C), 73.47, 79.80 (2C), 82.56, 113.25 (4C),
127.65 (4C), 134.23 (2C), 158.43 (2C); MS (EI, 70 eV) m/z
(%) = 328 (M+, 26), 243 (29), 227 (100), 135 (19). HRMS
Found: 328.1677. Calcd. for C20H24O4: 328.1675.
.
for C18H18O2: 266.1307. Calcd. for C18H18O2 0.4H2O: C,
79.03; H, 6.93. Found: C, 79.00; H, 6.74%.
(4-Anisyl)-phenylmethyl fur-2-yl ether (10o); pale
yellow oil; IR (neat) ꢁ 3112, 3028, 2930, 2836, 1611, 1510,
Bis(4-anisyl)methyl oxiran-2-ylmethyl ether (10j);
colourless oil; IR (neat) ꢁ 2930, 1614, 1509, 1461, 1245,
1
1459, 1246, 1171, 1038, 919, 812, 738, 698 cm-1; H NMR
1
1172, 1088, 917, 880, 829, 755 cm-1; H NMR (270 MHz,
(270 MHz, CDCl3) ꢀ 3.78 (s, 3H, OCH3), 4.46 (s, 2H), 6.28
2
3
CDCl3) ꢀ 2.59 (dd, 1H, J 5.1 Hz, J Hz 2.7 Hz), 2.77 (dd,
(bd, 1H, 3J 3.0 Hz), 6.33 (dd, 1H, 3J 3.0 Hz, 3J 1.9 Hz), 6.85
1H, 2J 5.1 Hz, 3J 4,3 Hz), 3.19 (m, 1H), 3.43 (dd, 1H, 2J 11.3
3
3
(d, 2H, J 8.6 Hz), 7.24 - 7.33 (m, 7H), 7.41 (dd, 1H, J 1.9
Hz, 4J 1.0 Hz); 13C NMR (67.8 MHz, CDCl3) ꢀ 55.24, 62.45,
81.71, 109.30, 110.19, 113.80 (2C), 127.08 (2C), 127.37,
128.34 (2C), 128.57 (2C), 133.93, 142.02, 142.71, 151.92,
159.04; MS (EI, 70 eV) m/z (%) = 294 (M+, 16), 213 (49),
197 (100). HRMS Found: 294.1256. Calcd. for C19H18O3:
294.1256.
2
Hz, 3J 5.7 Hz), 3.68 (dd, 1H, J 11.3 Hz, 3J 3.2 Hz), 3.78 (s,
3
6H, 2 OCH3), 5.37 (s, 1H), 6.85 (d, 4H, J 8.6 Hz), 7.25 (d,
4H, 3J 8.6 Hz); 13C NMR (67.8 MHz, CDCl3) ꢀ 44.44, 50.97,
55.24 (2C), 69.33, 80.05, 113.77 (4C), 128.16 (2C), 128.28
(2C), 134.21, 134.32, 158.96, 158.99; MS (EI, 70 eV) m/z
(%) = 300 (M+, 42), 242 (20), 227 (100), 135 (30). HRMS
Found: 300.1364. Calcd. for C18H20O4: 300.1362.
(2-Anisyl)-(4-anisyl)methyl
benzyl
ether
(10p);
(4-Anisyl)-phenylmethyl heptyl ether (10k); colourless
oil; IR (neat) ꢁ 3060, 3028, 2932, 1612, 1582, 1512, 1453,
1337, 1301, 1246, 1171, 1096, 1036, 829, 782, 725, 698 cm-
1; 1H NMR (270 MHz, CDCl3) ꢀ 0.87 (m, 3H), 1.27 (m, 8H),
colourless oil; IR (neat) ꢁ 3062, 3030, 3002, 2935, 2834,
1610, 1513, 1459, 1243, 1172, 1052, 826, 756, 698 cm-1; 1H
NMR (270 MHz, CDCl3) ꢀ 3.76 (s, 3H, OCH3), 3.77 (s, 3H,
2
2
OCH3), 4.49 (d, 1H, J 11.9 Hz), 4.54 (d, 1H, J 11.9 Hz),
3
1.63 (m, 2H), 3.42 (t, 2H, J 6.5 Hz), 3.78 (s, 3H, OCH3),
3
5.83 (s, 1H), 6.82 (m, 1H), 6.83 (d, 2H, J 8.9 Hz), 6.98 (m,
5.29 (s, 1H), 6.84 (d, 2H, 3J 8.6 Hz), 7.23 - 7.32 (m, 7H); 13
C
1H), 7.19 - 7.37 (m, 8H), 7.57 (m, 1H); 13C NMR (67.8
MHz, CDCl3) ꢀ 55.20, 55.37, 70.56, 76.01, 110.54, 113.51
(2C), 120.77, 126.95, 127.31, 127.65 (2C), 128.21 (3C),
128.43 (2C), 130.92, 134.38, 138.80, 156.63, 158.69; MS
(EI, 70 eV) m/z (%) = 334 (M+, 45), 243 (69), 227 (90), 135
(100), 121 (87), 91 (77). HRMS Found: 334.1572. Calcd. for
C22H22O3: 334.1569.
NMR (67.8 MHz, CDCl3) ꢀ 14.10, 22,69, 26.25, 29.16,
29.92, 31.85, 55.25, 69.16, 83.14, 113.73 (2C), 126.87 (2C),
127.18, 128.28 (4C), 134.98, 142.92, 158.94; MS (EI, 70
eV) m/z (%) = 312 (M+, 43), 197 (100). HRMS Found:
312.2090. Calcd. for C21H28O2: 312.2089.
(4-Anisyl)-phenylmethyl cyclopentyl ether (10l);
colourless oil; IR (neat) ꢁ 2952, 1611, 1509, 1460, 1302,
(2-Anisyl)-(4-anisyl)methyl
pentyl
ether
(10q);
1
1246, 1171, 1034, 810, 732, 698 cm-1; H NMR (270 MHz,
colourless oil; IR (neat) ꢁ 2958, 1612, 1511, 1491, 1459,
CDCl3) ꢀ 1.49 (m, 2H), 1.73 (m, 6H), 3.77 (s, 3H, OCH3),
1244, 1179, 1091, 1032, 818, 754 cm-1; 1H NMR (270 MHz,
3
3.96 (m, 1H), 5.37 (s, 1H), 6.84 (d, 2H, J 8.6 Hz), 7.20 -
3
CDCl3) ꢀ 0.88 (t, 3H, J 7.3 Hz, CH3), 1.32 (m, 4H), 1.63
7.31 (m, 7H); 13C NMR (67.8 MHz, CDCl3) ꢀ 23.56 (2C),
32.35, 32.45, 55.21, 78.92, 80.62, 113.66, 127.07 (4C),
128.20 (2C), 128.44 (2C), 135.12, 143.16, 158.80; MS (EI,
(m, 2H), 3.43 (t, 2H, 3J 6.7 Hz), 3.76 (s, 3H, OCH3), 3.79 (s,
3
3H, OCH3), 5.71 (s, 1H), 6.81 (d, 2H, J 8.9 Hz), 6.82 (m,
3
1H), 6.96 (m, 1H), 7.19 (m, 1H), 7.28 (d, 2H, J 8.9 Hz),

524 Letters in Organic Chemistry, 2009, Vol. 6, No. 7
Thies Thiemann
3
4
3
3
7.49 (dd, 1H, J 7.6 Hz, J 1.6 Hz); 13C NMR (67.8 MHz,
CDCl3) ꢀ 14.03, 22.54, 28.44, 29.65, 55.19, 55.40, 69.16,
110.48, 113.46 (2C), 120.72, 126.79, 128.02, 128.27 (2C),
131.40, 134.88, 156.45, 158.59. MS (EI, 70 eV) m/z (%) =
314 (M+, 59), 243 (50), 227 (100), 135 (37), 121 (58).
HRMS Found: 314.1883. Calcd. for C20H26O3: 314.1882.
6.86 (d, 2H, J 8.6 Hz), 7.23 (d, 2H, J 8.6 Hz); 13C NMR
(67.8 MHz, CDCl3) ꢀ 10.37, 14.07, 14.88, 22.64, 26.22,
29.26, 29.42, 29.91, 31.11, 31.83, 63.37, 68.66, 83.31,
114.13 (2C), 127.81 (2C), 134.98, 158.21; MS (EI, 70 eV)
m/z (%) = 292 (M+, 4.2), 263 (100), 151 (81). HRMS Found:
292.2403. Calcd. for C19H32O2: 292.2402.
.
Calcd. for C20H26O3 0.1H2O: C, 75.96; H, 8.36. Found: C,
75.62; H, 8.30%.
4-Ethoxy-1-(1-benzyloxypropyl)benzene (12b); colour-
less oil; IR (neat) ꢁ 3062, 3028, 2930, 2866, 1612, 1584,
1512, 1454, 1394, 1304, 1244, 1172, 1066, 921, 827, 732,
(2-Anisyl)-(4-anisyl)methyl but-1-ynyl ether (10r);
colourless oil; IR (neat) ꢁ3296, 2928, 1611, 1509, 1491,
1460, 1246, 1178, 1090, 825, 755 cm-1; 1H NMR (270 MHz,
CDCl3) ꢀ 1.95 (m, 1H), 2.51 (m, 2H), 3.58 (m, 2H), 3.76 (s,
3H, OCH3), 3.78 (s, 3H, OCH3), 5.78 (s, 1H), 6.81 (d, 2H, 3J
8.9 Hz), 6.83 (m, 1H), 6.96 (m, 1H), 7.22 (m, 1H), 7.29 (d,
2H, 3J 8.9 Hz), 7.49 (d, 1H, 3J 7.6 Hz); 13C NMR (67.8 MHz,
CDCl3) ꢀ 19.97, 55.20, 55.40, 67.04, 69.13, 76.69, 81.48,
110.50, 113.53 (2C), 120.74, 126.86, 128.29, 128.32 (2C),
130.68, 134.17, 156.54, 158.75; MS (EI, 70 eV) m/z (%) =
296 (M+, 55), 243 (42), 227 (86), 189 (29), 135 (50), 121
(100). HRMS Found: 296.1415. Calcd. for C19H20O3:
296.1412.
697 cm-1; H NMR (270 MHz, CDCl3) ꢀ 0.87 (t, 3H, J 7.3
1
3
3
Hz, CH3), 1.42 (t, 3H, J 7.0 Hz, CH3), 1.67 (m, 1H), 1.87
3
3
3
(m, 1H), 4.04 (q, 2H, J 7.0 Hz), 4.16 (dd, 1H, J 6.5 Hz, J
2
2
6.5 Hz), 4.23 (d, 1H, J 11.9 Hz), 4.43 (d, 1H, J 11.9 Hz),
3
3
6.88 (d, 2H, J 8.6 Hz), 7.20 - 7.32 (m, 5H), 7.23 (d, 2H, J
8.6 Hz); 13C NMR (67.8 MHz, CDCl3) ꢀ 10.38, 14.89, 31.06,
63.40, 70.10, 82.54, 114.28 (2C), 127.35, 127.73 (2C),
128.07 (2C), 128.27 (2C), 134.29, 138.88, 158.41; MS (EI,
70 eV) m/z (%) = 270 (M+, 13), 241 (88), 213 (11), 91 (100).
HRMS Found: 270.1618. Calcd. for C18H22O2: 270.1620.
4-Ethoxy-1-(1-cyclopentyloxypropyl)benzene (12c); col-
ourless oil; IR (neat) ꢁ 2936, 1612, 1511, 1456, 1390, 1341,
1
(2-Anisyl)-(4-anisyl)methyl (3-methyloxetan-3-yl)methyl
ether (10s); colourless oil; IR (neat) ꢁ 2928, 2864, 1613,
1514, 1487, 1468, 1244, 1170, 1086, 1032, 981, 833, 756
1302, 1247, 1173, 1048, 965, 922, 831 cm-1; H NMR (270
MHz, CDCl3) ꢀ 0.87 (t, 3H, 3J 7.3 Hz, CH3), 1.26 - 1.70 (m,
8H), 1.41 (t, 3H, 3J 7.0 Hz, CH3), 3.76 (m, 1H), 4.02 (q, 2H,
3J 7.0 Hz), 4.16 (m, 1H), 6.85 (d, 2H, 3J 8.6 Hz), 7.19 (d, 2H,
3J 8.6 Hz); 13C NMR (67.8 MHz, CDCl3) ꢀ 10.59, 14.91,
23.42 (2C), 31.54, 31.59, 33.14, 63.37, 78.39, 80.91, 114.10
(2C), 127.83 (2C), 135.58, 158.17; MS (EI, 70 eV) m/z (%)
= 248 (M+, 3.8), 219 (29), 163 (38), 151 (100), 107 (19).
HRMS Found: 248.1777. Calcd. for C16H24O2: 248.1776.
cm-1; H NMR (270 MHz, CDCl3) ꢀ 1.35 (s, 3H, CH3), 3.48
1
2
2
(d, 1H, J 8.6 Hz), 3.51 (d, 1H, J 8.6 Hz), 3.76 (s, 3H,
OCH3), 3.79 (s, 3H, OCH3), 4.34 (d, 2H, 2J 5.4 Hz), 4.54 (d,
2H 2J 5.4 Hz), 5.73 (s, 1H), 6.82 (d, 2H, 3J 8.9 Hz), 6.83 (m,
3
1H), 6.96 (m, 1H), 7.26 (m, 1H), 7.28 (d, 2H, J 8.9 Hz),
3
4
7.46 (dd, 1H, J 7.6 Hz, J 1.6 Hz); 13C NMR (67.8 MHz,
CDCl3) ꢀ 21.56, 31.57, 39.56, 55.17, 55.36, 74.11, 80.27
(2C), 80.32, 110.44, 113.48 (2C), 120.72, 126.74, 128.25
(3C), 131.04, 134.37, 156.48, 158.68; MS (EI, 70 eV) m/z
(%) = 328 (M+, 37), 243 (100), 227 (61), 221 (26), 121 (78).
HRMS Found: 328.1678. Calcd. for C20H24O4: 328.1675.
4-Pentoxy-1-(1-octyloxyethyl)benzene (12d); colourless
oil; IR (neat) ꢁ 2928, 2856, 1615, 1512, 1469, 1246, 1173,
1102, 832 cm-1; H NMR (270 MHz, CDCl3) ꢀ 0.87 (t, 3H,
1
3J 6.8 Hz), 0.93 (t, 3H, 3J 6.8 Hz), 1.25 - 1.57 (m, 16H), 1.41
(d, 3H, 3J 6.5 Hz, CH3), 1.78 (m, 2H), 3.25 (t, 2H, 3J 6.8 Hz),
3
3
(2-Anisyl)-(4-anisyl)methyl cyclopentyl ether (10t);
colourless oil; IR (neat) ꢁ 2936, 2836, 1611, 1510, 1489,
1458, 1339, 1246, 1171, 1112, 1030, 986, 813, 754 cm-1; 1H
NMR (270 MHz, CDCl3) ꢀ 5.78 (s, 1H), 1.72 (m, 6H), 1.47
(m, 2H), 3.75 (s, 3H, OCH3), 3.77 (s, 3H, OCH3), 3.93 (m,
1H), 6.80 (d, 2H, 3J 8.9 Hz), 6.81 (m, 1H), 6.95 (m, 1H),
3.94 (t, 2H, J 6.8 Hz), 4.32 (q, 1H, J 6.5 Hz), 6.86 (d, 2H,
3J 8.6 Hz), 7.21 (d, 2H, J 8.6 Hz); 13C NMR (67.8 MHz,
3
CDCl3) ꢀ 14.00, 14.07, 22.46, 22.64, 24.11, 26.19, 28.24,
29.03, 29.25, 29.42, 29.95, 31.82, 67.98, 68.53, 77.38,
114.28 (2C), 127.27 (2C), 136.12, 158.45; MS (EI, 70 eV)
m/z (%) = 320 (M+, 18), 305 (100), 193 (45), 121 (28).
HRMS Found: 320.2714. Calcd. for C21H36O2: 320.2715.
3
3
7.21 (m, 1H), 7.24 (d, 2H, J 8.9 Hz), 7.46 (dd, 1H, J 7.6
Hz, J 1.6 Hz); 13C NMR (67.8 MHz, CDCl3) ꢀ 23.58 (2C),
4
4-Pentoxy-1-(1-benzyloxyethyl)benzene (12e); colour-
less oil; IR (neat) ꢁ 2926, 2858, 1611, 1510, 1244, 1173,
32.38, 32.50, 55.17, 55.36, 74.14, 79.05, 110.39, 113.42
(2C), 120.65, 127.36, 127.99, 128.40 (2C), 131.60, 135.15,
156.63, 158.15; MS (EI, 70 eV) m/z (%) = 312 (M+, 33), 243
(12), 227 (100), 121 (50). HRMS Found: 312.1728. Calcd.
for C20H24O3: 312.1725.
1094, 909, 831, 734, 696 cm-1; H NMR (270 MHz, CDCl3)
1
3
ꢀ 0.93 (t, 3H, J 7.3 Hz, CH3), 1.34 - 1.48 (m, 4H), 1.46 (d,
3
3
3H, J 6.5 Hz, CH3), 1.78 (m, 2H), 3.96 (t, 2H, J 6.8 Hz),
2
2
4.26 (d, 1H, J 11.9 Hz), 4.42 (d, 1H, J 11.9 Hz), 4.44 (t,
Diphenylmethyl heptyl ether (10u) [18]; colourless oil;
IR (neat) ꢁ 3062, 3026, 2924, 2856, 1600, 1492, 1460, 1378,
1303, 1185, 1107, 797, 700, 653, 618 cm-1; MS (EI, 70 eV)
m/z (%) = 282 (M+, 7.5), 243 (31), 213 (42), 167 (100).
HRMS Found: 282.1981. Calcd. for C20H26O: 282.1984.
1H, 3J 6.5 Hz), 6.89 (d, 2H, 3J 8.6 Hz), 7.24 - 7.32 (m, 5H),
3
7.26 (d, 2H, J 8.6 Hz); 13C NMR (67.8 MHz, CDCl3) ꢀ
14.95, 23.41, 25.03, 29.18, 29.96, 68.95, 70.97, 77.65,
115.36 (2C), 128.33, 128.47 (2C), 128.64 (2C), 129.25 (2C),
136.41, 139.72, 159.59; MS (EI, 70 eV) m/z (%) = 298 (M+,
62), 283 (40), 255 (19), 207 (29), 191 (48), 134 (17), 121
(64), 91 (100). HRMS Found: 298.1936. Calcd. for
C20H26O2: 298.1933.
4-Ethoxy-1-(1-octyloxypropyl)benzene (12a); colourless
oil; IR (neat) ꢁ 2930, 2852, 1611, 1510, 1459, 1244, 1173,
1097, 1050, 963, 924, 828 cm-1; 1H NMR (270 MHz, CDCl3)
ꢀ 0.87 (t, 3H, 3J 7.3 Hz, CH3), 0.93 (t, 3H, 3J 6.8 Hz), 1.42 (t,
3H, 3J 7.0 Hz), 1.54 - 1.87 (m, 14H), 3.40 (t, 2H, 3J 6.5 Hz),
3,5-Dimethyl-4-methoxy-1-(1-benzyloxy-2-methylpropyl)
benzene (12f); colourless oil; IR (neat) ꢁ 3032, 2939, 1605,
1510, 1491, 1476, 1460, 1223, 1096, 1020, 881, 848, 735,
3
3
3
4.02 (q, 2H, J 7.0 Hz), 4.16 (dd, 1H, J 6.5 Hz, J 6.5 Hz),

Etherification of Diarylmethanols and 1-Phenylalkan-1-ols
Letters in Organic Chemistry, 2009, Vol. 6, No. 7
525
1
3
698 cm-1; H NMR (270 MHz, CDCl3) ꢀ 0.72 (d, 3H, J 6.7
2007, 17, 1634; (b) Thompson, D. H.; Svendson, C. B.; Di Meglio,
C.; Anderson, V. C. J. Org. Chem., 1994, 59, 2945.
3
Hz, CH3), 1.03 (d, 3H, J 6.7 Hz, CH3), 1.91 (m, 1H), 2.28
(s, 6H, 2 CH3), 3.73 (s, 3H, OCH3), 3.82 (d, 1H, J 7.6 Hz),
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3
2
2
4.19 (d, 1H, J 12.1 Hz), 4.43 (d, 1H, J 12.1 Hz), 6.91 (s,
2H), 7.24 - 7.35 (m, 5H); 13C NMR (67.8 MHz, CDCl3) ꢀ
16.21 (2C), 19.23, 34.84 (2C), 59.64, 70.44, 86.98, 127.24,
127.63 (2C), 127.90 (2C), 128.19 (2C), 130.21 (2C), 136.45,
139.09, 156.19; MS (EI, 70 eV) m/z (%) = 298 (M+, 2.2),
255 (42), 163 (17), 91 (100). HRMS Found: 298.1936.
Calcd. for C20H26O2: 298.1933.
ACKNOWLEDGEMENTS
Part of this work has been carried out within the
framework of a CREST program. Financial support from the
Japan Science and Technology Corporation (JST) is
gratefully acknowledged. The author thanks Ms. Yasuko
Tanaka, Institute of Materials Chemistry and Engineering,
Kyushu University, for the mass and high resolution mass
measurements. The elemental analyses were carried out at
the Centre of Analysis, Kyushu University, Hakozaki
Campus, Fukuoka.
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