New anthracenyl-substituted phosphonates: Synthesis and utility

Article abstract of DOI:10.1055/s-2007-965947

Chlorination of α-hydroxyphosphonate anthracen-9-yl(5,5-dimethyl-2- oxo-2λ⁵-1,3,2-dioxaphosphinan-2-yl)methanol (11) using thionyl chloride unexpectedly yields 10-(5,5-dimethyl-2-oxo-2λ⁵-1,3, 2-dioxaphosphinan-2-ylmethylene)anthracen

Full text of DOI:10.1055/s-2007-965947

PAPER
893
New Anthracenyl-Substituted Phosphonates: Synthesis and Utility
A
nthracenyl-Subst
.
itute
d
Phosp
C
honates . Kumara Swamy,* Venu Srinivas, K. V. P. Pavan Kumar, K. Praveen Kumar
School of Chemistry, University of Hyderabad, Hyderabad 500046, India
Fax +91(40)23012460; E-mail: kckssc@uohyd.ernet.in
Received 26 October 2006; revised 6 December 2006
and co-workers.7 One of the other ways by which the an-
thracenyl group can be introduced is by using the Horner–
Wadsworth–Emmons (HWE) reaction via a suitable
phosphonate and an aldehyde. The anthracenyl moiety
Abstract: Chlorination of a-hydroxyphosphonate anthracen-9-
yl(5,5-dimethyl-2-oxo-2l5-1,3,2-dioxaphosphinan-2-yl)methanol
(11) using thionyl chloride unexpectedly yields 10-(5,5-dimethyl-2-
oxo-2l5-1,3,2-dioxaphosphinan-2-ylmethylene)anthracen-9(10H)-
one (13), 2-(10-chloroanthracen-9-ylmethyl)-5,5-dimethyl-2l5- may be present in either of the two, but to our knowledge,
1,3,2-dioxaphosphinan-2-one (14), and 10-(5,5-dimethyl-2-oxo-
2l5-1,3,2-dioxaphosphinan-2-ylmethylene)-9,10-dihydroanthra-
cen-9-ol (15) in addition to 2-[anthracen-9-yl(chloro)methyl]-5,5-
dimethyl-2l5-1,3,2-dioxaphosphinan-2-one (12). The reaction of 2-
chloro-5,5-dimethyl-1,3,2-dioxaphosphinane (5) with 9-anthralde-
hyde leads to 2-chloro-1,1-dimethylethyl hydrogen 10-(5,5-dimeth-
yl-2-oxo-2l5-1,3,2-dioxaphosphinan-2-ylmethylene)-4a,9,9a,10-
tetrahydroanthracen-9-ylphosphonate (20) in addition to 12. Bromi-
nation of 11 with phosphorus tribromide affords the 10-bromoan-
thracen-9-yl product, 2-(10-bromoanthracen-9-ylmethyl)-5,5-
dimethyl-2l5-1,3,2-dioxaphosphinan-2-one (22). Reaction of 12
with 4-chloro- or 4-nitrobenzaldehyde in the presence of sodium
phosphonates with anthracenyl residue are too few in
number.8
In our earlier work on the synthesis of phosphonates, we
derivatized Pudovik products of the type aryl(5,5-dimeth-
yl-2-oxo-2l5-1,3,2-dioxaphosphinan-2-yl)methanol or
used the straightforward reaction of a P–Cl precursor with
a suitable aldehyde [Scheme 1, (a) and (b)].9 Other syn-
thetically viable routes to analogous phosphonates in-
clude those shown in Scheme 1, (c) and (d).10,11 When we
tried to utilize the routes shown in Scheme 1 (a) and (b)
hydride affords the products, 9-(2-arylvinyl)anthracenes 23 and 24 for phosphonates with an anthraldehyde residue, the reac-
in an uncommon Horner–Wadsworth–Emmons-type reaction.
Compound 22 underwent the normal Horner–Wadsworth–Emmons
reaction with benzaldehydes or ferrocenecarbaldehyde to afford
Horner–Wadsworth–Emmons reaction of [anthracen-9-
disubstituted alkenes. One of these alkenes, (E)-9-bromo-10-[2-(4-
bromophenyl)vinyl]anthracene (26), undergoes Sonogashira cou-
tions led to several rather unexpected products and this is
what we describe in this paper. Additionally, the expected
yl(chloro)methyl]phosphonates takes place with the elim-
ination of chlorine rather than of hydrogen, which is not
normal.12 The Horner–Wadsworth–Emmons products
that contain a bromoaryl group undergo Sonogashira cou-
pling readily to afford multiply connected unsaturated
systems with an anthracene residue. These results, which
add to the utility of the phosphonates thus synthesized, are
also described herein.
pling with terminal alkynes to afford the conjugated alkynes (E)-9-
bromo-10-[2-(4-ethynylphenyl)vinyl]anthracenes 30–32 in moder-
ate yields. X-ray crystal structures of 12–15, 20, 23 and (E)-9-bro-
mo-10-[2-(4-methoxyphenyl)vinyl]anthracene (27) have been
determined.
Key words: phosphonates, arenes, halogenation, Horner–Wads-
worth–Emmons reaction, cross-coupling
SOX2 (X = Cl, Br)
or PI3
O
O
O
O
O
O
P
Anthracene and its derivatives are of immense interest in
materials chemistry as organic semiconductors1 and pho-
toswitches.2 Many of these compounds are highly fluores-
cent and thermochromic or photochromic.3 They can also
act as light-induced electron donors or acceptors and can
undergo photodimerization.4 Their applications in optical,
electronic, or magnetic switches incorporated in poly-
mers, films, or crystals are quite often based on this pho-
todimerization property. Because of effective blocking on
one side, the carbenes with carbon attached to C9 of an-
thracene are quite stable in the triplet form.5 Anthracene-
based compounds are also useful for probing DNA cleav-
age and related studies on biological systems.6 In view of
these applications, we are interested in systems possessing
the anthracenyl residue. Several interesting epoxy-an-
thracene derivatives have recently been prepared by Celik
P
CH-Ar
X
CH-Ar
OH
(a)
(b)
2 [X = Cl], 3 [X = Br], 4 [X = I]
1
O
O
O
O
O
neat, ∆
P
P
Cl
+ ArCHO
CH-Ar
Cl
5
2
(i) LiHDMS, THF, Me3SiCl
(ii) NFBS or (CCl3)2
or (BrCl2C)2 or I2
O
EtO
EtO
P
O
EtO
EtO
CHAr
X
P
(iii) LiOH, H2O, THF
CH2Ar
(c)
7 [X = F, Cl, Br, I]
6
O
O
PPh3, DDQ, MX
R
R
P(OEt)2
P(OEt)2
MX = n-Bu4NBr, n-Bu4NI, NaN3
(d)
X
OH
9 [X = Br, I, N3]
8
SYNTHESIS 2007, No. 6, pp 0893–0901
x
x
.
x
x
.2
0
0
7
Advanced online publication: 20.02.2007
DOI: 10.1055/s-2007-965947; Art ID: P12806SS
Scheme 1
© Georg Thieme Verlag Stuttgart · New York

894
K. C. Kumara Swamy et al.
PAPER
The simple reaction of a-hydroxyphosphonate 11, derived
from the Pudovik reaction between the phosphonate 10
and 9-anthraldehyde, with thionyl chloride gives four dis-
tinct products 12–15 (Scheme 2) that can be separated by
column chromatography. The same products are observed
when 1:1 or higher stoichiometry is used (31P NMR evi-
dence), but for better yields, a higher stoichiometry is re-
quired and hence used. Although the expected a-
chlorophosphonate 12 is the major product, the remaining
products 13–15 can be identified from their 31P NMR
spectra with the chloro compounds 12 and 14 exhibiting
well-separated signals. The structures were confirmed by
X-ray crystallography (Figure 1). It can be noted that 14
is an isomer of 12, while the hydroxy compound 15 is an
isomer of the precursor 11.
Formation of the a-chlorophosphonate 12 could occur by
the normal attack of chloride on the carbon a to phospho-
rus while that of 14 occurs by attack at C10 of the an-
thracene ring (Scheme 3) via an intermediate of type I.
Thus the liberated HCl appears to be involved in the for-
mation of 12 and 14. This is also corroborated by our ear-
lier results in which the a-hydroxyphosphonates 16 and
17 derived from furfuraldehyde and cinnamaldehyde led
to unexpected chlorophosphonates 18 and 19
(Scheme 4).9c In the later steps, the stabilized carbocation
at C10 (II) may be involved and may undergo attack by
the anion (or water during work-up).
Figure 1 Structures of 12, 13, 14, and 15. The bond parameters are
normal. Hydrogen bond data for 15 (D-H···A): O4–H···O(3A) 0.82 Å,
1.89 Å, 2.701(2) Å, 170.2°.
–
probably by the migration of the ClSO2 anion to C10 and
subsequent hydrolysis and proton shift.
Interestingly, in the other route involving direct reaction
of 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphinane (5)
with 9-anthraldehyde, a number of products are also
formed among which compound 12 and the bisphospho-
nate 20 (Scheme 5, Figure 2) are the major components
that can be readily isolated. For compound 20, apart from
the two signals in the 31P NMR, the PCH (saturated) pro-
ton appears as a doublet at d = 4.48 with an unusually
large coupling [2JP-H = 30.0 Hz] while the PCH= proton
appears at d 6.03 [2JP-H = 12.0 Hz]. The molecule is
dimeric via hydrogen bonding through O5–H···O6¢.
Formation of 13 requires oxidation of 11 or 14, probably
during work-up. Although compound 15 is an isomer of
11, on passing the latter through a silica gel column (hex-
ane) isomerization did not take place. Thus 15 would have
been formed during the reaction with thionyl chloride,
O
O
H
O
P
HO
O
O
O
O
H
Et3N, toluene
r.t.
P
+
10
11
O
O
O
O
O
Cl
P
P
O
+
+
O
12 63% (δP = 12.4)
13 7% (δP = 9.6)
SOCl2, CH2Cl2
0 °C
r.t
11
O
O
O
O
O
P
P
O
+
H
OH
Cl
14 5% (δP = 20.3)
15 15% (δP = 11.4)
Scheme 2
Synthesis 2007, No. 6, 893–901 © Thieme Stuttgart · New York

PAPER
Anthracenyl-Substituted Phosphonates
895
O
O
O
O
O
O
O
P
P
S
O
Cl
rearrangement (?)
9
9
11
14
15
+
(i) hydrolysis
H Cl
+
10
10
(ii) proton shift
H
OH or Cl
II
I
(b) other possible pathways to 15
(a) possible intermediates in the formation of 12, 14 and 15
Scheme 3
SOCl2,
CH2Cl2
The formation of 20 is unexpected, but probably occurs by
further reaction of 5 with the chlorophosphonate 12
formed in the reaction. Opening of the ring at P2 [cf.
Figure 2, Scheme 6], is not due to hydrolysis, but because
of the attack of a chloride on the saturated OCH2 carbon;
this chloride anion must have come after the attack of 5 on
12 and subsequent dearomatization of the central ring of
the anthracene system. The colorless nature of 20 (12 is
yellow) is also consistent with the loss of aromatization at
the anthracene central ring. Hydrolysis at the P(2)–Cl cen-
ter probably occurs during the final stages (most likely
during work-up); the X-ray crystal structure of 20 also
confirms the presence of a hydrogen bonded P–OH group
as shown in Figure 2. As regards the cleavage of the 1,3,2-
dioxaphosphinane ring at P2, we had earlier observed a
similar phenomenon when 5 was treated with 2,2-dimeth-
ylpropane-1,3-diol/N-chlorodiisopropylamine, which led
to 2-(3-chloro-2,2-dimethylpropyl)-1,3,2-dioxaphosphi-
nan-2-one (21) (Figure 3);13 other examples of similar
cleavage also exist in the literature.14 Finally, although ac-
tivation of 10-position of the anthracenyl system is known
in a few cases,15 isolation of a compound like 20 could
open up a new way of forming bisphosphonates.
O
O
O
O
O
O
P
P
Cl
O
O
OH
16
18
O
SOCl2,
CH2Cl2
Ph
Cl
O
Ph
O
O
P
P
O
O
OH
17
19
Scheme 4
O
H
O
neat
.
.
P
+
Cl
O
5 (1.5 equiv)
O
P
O
O
O
12 +
P
OH
Cl
30%
H
O
20 35% (δP = 11.2, 24.1)
Cl
O
O
O
Scheme 5
P
O
21
Figure 3
Unlike the case of chlorination, when compound 11 was
brominated with phosphorus tribromide, only one phos-
phonate 22, the bromo analogue of 14, is obtained in very
high yields. Here, 1:1 stoichiometry works well and addi-
tional phosphorus tribromide improves the yields margin-
ally. The isolation of the product is also much easier. This
observation is significant since it allows the preparation of
a large number of alkyne–anthracenyl–alkene conjugates
using first the Horner–Wadsworth–Emmons reaction of
22 with aldehydes and then coupling the products with
alkynes under Sonogashira conditions (vide infra). A spe-
cies of type V is a possible intermediate in the formation
of 22 (Figure 4).
Figure 2 A diagram showing the molecular structure of 20·CH2Cl2.
Solvent is not shown. Selected bond parameters (Å): P1–O1 1.569(2),
P1–O2 1.583(2), P1–O3 1.456(2), P1–C15 1.775(2), P2–O4 1.563(1),
P2–O5 1.536(1), P2–O6 1.497(1), P2–C10 1.815(2). Hydrogen bon-
ded D-H, H···A, D···A, and D-H···A parameters: O5–H(O5)···O6¢
0.69(4), 1.86(4), 2.548(2) Å, 175(4)°.
Synthesis 2007, No. 6, 893–901 © Thieme Stuttgart · New York

896
K. C. Kumara Swamy et al.
PAPER
O
O
O
O
O
O
O
O
1
P
P
P
+
H
Cl
H
O
H
H2O
20
– HCl
H
H
12
O
O
P
P
Cl
Cl
2
O
O
O
.
.
P
Cl
Cl
O
Cl
5
III
IV
Scheme 6
O
O
O
O
O
O
O
O
O
O
O
Br
Br
P
P
H
P
P
O
Cl
P
O
H
9
NaH
H+Br–
– NaCl
10
VI
12
Br
22 80% (δP = 20.3)
V
Scheme 8
Figure 4
The corresponding reaction with 10-bromoanthracen-9-
ylmethylphosphonate 22 gave the alkenes 25–28 smooth-
ly; the ferrocenyl alkene 29 was also readily prepared
(Scheme 9). The location of bromine at C10 of anthracene
ring in 22 was confirmed by the X-ray crystal structure of
its Horner–Wadsworth–Emmons product 27 [Figure 5
(b)]. It may be noted that a specific route for anthracenyl-
substituted alkenes specifically involving a 4,4¢-dimethyl-
2,2¢-bipyridyl ligand by the dehydration of the precursor
alcohol has recently been reported.6b Our route offers a
general entry to a large number of alkenes containing the
anthracenyl residue.
Interestingly, compound 12 undergoes a Horner–Wad-
sworth–Emmons-type reaction readily with aromatic al-
dehydes in the presence of sodium hydride as a base to
afford alkenes 23 and 24 that contain the anthracenyl res-
idue, but with the chlorine is missing and its position tak-
en up by a hydrogen (Scheme 7).9c,14 The yields were only
moderate here and clearly other products with Rf values
close to the isolated products were present.16,17 At the mo-
ment we do not have a rationale for the unusual chlorine
removal from 12 to yield 23 and 24, except to note that we
confirmed the structures of 12 (vide supra) and 23
[Figure 5 (a)] by X-ray crystallography also. It is possible
that during the reaction, a part of the sodium hydride is
utilized to convert the -CH(Cl) phosphonate 12 into -CH2
phosphonate VI (Scheme 8) and a part is further utilized
to form the carbanion from VI prior to the reaction with
the aldehyde. However, in a blank reaction of 12 with so-
dium hydride we could not identify the species VI.
O
O
P
O
R
CHO
NaH, THF, 0 °C
R
Br
22
H
O
O
O
Br
R
P
Cl
CHO
H
25 R = H 70%
26 R = Br 80%
27 R = OMe 66%
28 R = NO2 58%
NaH, THF, 0 °C
12
H
O
R
Fe
H
H
O
Br
23 R = NO2 50%
24 R = Cl 48%
H
Scheme 7
29 65%
Scheme 9
Synthesis 2007, No. 6, 893–901 © Thieme Stuttgart · New York

PAPER
Anthracenyl-Substituted Phosphonates
897
hyde with 5 leads not just to the expected a-chlorophos-
phonate 12, but also to the bis-substituted phosphonate 20.
The utility of phosphonates 12 and 22 in the Horner–
Wadsworth–Emmons reaction has been demonstrated.
The bromoarene products from Horner–Wadsworth–
Emmons reaction were later used in the Sonogashira cou-
pling with alkynes, demonstrating the versatility of the in-
termediates thus synthesized.
Figure 5 Structures of compounds 23 and 27
All reactions were carried out under dry N2 unless otherwise indi-
cated. Chemicals were procured from Aldrich or local manufactur-
ers and were purified when required.19 Anhyd, oxygen free solvents
were prepared according to standard procedures. IR spectra were re-
corded on a JASCO FTIR 5300 spectrophotometer. The NMR spec-
tra were recorded in CDCl3 on a Bruker 200 or a 400 MHz NMR
spectrometer at 25 °C. Elemental analyses were carried out on a
Perkin-Elmer 240C CHN analyzer. MS spectra were recorded using
GCMS-QP2010 and LCMS-2010A instruments.
As discussed, we are interested in anthracenyl compounds
with extended conjugation. In this context, we treated alk-
ene 26 with the phenylacetylene, 2-methylbut-3-yn-2-ol,
or oct-1-yne under Sonogashira conditions18 and obtained
the coupled products 30–32 in respectable yields
(Scheme 10). As is common with most palladium-cata-
lyzed reactions, the presence of a hydroxy group does not
pose any problem (cf. 31). In the reaction using phenyl-
acetylene we isolated only the monocoupled product 30,
while the reaction of oct-1-yne afforded both the mono-
32 and the biscoupled 33 products, although the yield of
the latter was low. We have not made attempts to maxi-
X-ray crystal data were collected on a Bruker AXS SMART diffrac-
tometer using Mo-Ka (l = 0.71073 Å) radiation. The structures
were solved and refined by standard methods.20 All non-hydrogen
atoms were refined anisotropically. Compound 20·CH2Cl2 con-
tained a disordered CH2Cl2 molecule (not shown in Figure 2). The
quality of data was only moderate for 13 and 23, but was sufficient
mize the yields, but the results clearly demonstrate the enough to allow us to be certain about the structure. For hydrogen
atoms bonded to carbon, a riding model was used. CIF files were de-
utility of the bromoanthracenyl-substituted alkenes pre-
posited at Cambridge Database (CCDC 613031–613037). Copies of
pared in this work.
the data can be obtained, free of charge, on application to CCDC, 12
Union Road, Cambridge, CB2 1EZ, UK [fax: +44(1223)336033 or
e-mail: deposit@ccdc.cam.ac.uk].
H
R
H
Br
Anthracen-9-yl(5,5-dimethyl-2-oxo-2l5-1,3,2-dioxaphosphi-
nan-2-yl)methanol (11)
Br
PdCl2(PPh3)2, CuI
Et3N, dioxane
H
To a stirred soln of 10 (5.12 g, 34 mmol) in anhyd toluene (70 mL)
was added Et3N (2.4 mL, 17 mmol) and 9-anthraldehyde (7.22 g, 35
mmol) under N2 and the mixture stirred at r.t. for 3 h. The yellow
colored solid formed was filtered, washed with toluene (20 mL),
and evacuated to yield 11, which was recrystallized (CH2Cl2–tolu-
ene, 1:1); yield: 10.14 g (84%); mp 166–168 °C. Solubility was too
low to obtain a satisfactory 13C NMR spectrum.
26
H
R
Br
H
30 R = Ph 50%
31 R = C(OH)Me2 46%
32 R = n-C6H13 48%
IR (KBr): 3287, 1464, 1248, 1198, 1082 cm–1.
1H NMR (200 MHz, DMSO-d6): d = 0.34, 0.97 (2 s, 6 H, 2 CH3),
3.03, 3.27 (2 dd → t, J = 8.8, 8.8 Hz, 2 H, OCHAHB of one set), 3.52
(br s, 1 H, OH), 3.71, 3.82 (2 dd → t, J = 8.8, 8.8 Hz, 2 H, OCHAHB
of second set), 6.68 (d, 1 H, JP-H = 14.6 Hz, PCH), 7.48–8.15 (m, 9
H, ArH). The four OCHAHB protons showed up separately in this
compound.
H
n-C6H13
31P NMR (80 MHz, DMSO-d6): d = 16.9.
n-C6H13
H
Anal. Calcd for C20H21O4P: C, 67.41; H, 5.94. Found: C, 67.45; H,
6.10.
33 10%
Reaction of 11 with Thionyl Chloride; Isolation of 12–15
To an ice-cold soln of 11 (4.24 g, 11.8 mmol) in CH2Cl2 (50 mL)
was added SOCl2 (3.3 mL, 47 mmol) dropwise. The mixture was
stirred at r.t. for 4 h, quenched with cold H2O (40 mL), and extracted
with CH2Cl2 (3 × 20 mL). The combined organic layers were
Scheme 10
Thus, the naive reaction of thionyl chloride with a-hy-
droxyphosphonate 11, derived from 9-anthraldehyde,
leads to four distinct products that include (i) the expected washed with H2O (3 × 30 mL) and sat. brine (40 mL), dried (anhyd
a-chlorophosphonate 12, (ii) the C10 oxo product 13, (iii)
C10 chloro product 14, which is an isomer of 12, and (iv)
Na2SO4), and concentrated to give a solid. This was subjected to
column chromatography (silica gel, EtOAc–hexane) to give 12–15;
compound 12 was separated using 20% EtOAc–hexane, 13 using
the C10 hydroxy product 15, which is an isomer of 11.
30% EtOAc–hexane, 14 using 35% EtOAc–hexane, and 15 using
Even the atom-precise addition reaction of 9-anthralde-
40% EtOAc–hexane.
Synthesis 2007, No. 6, 893–901 © Thieme Stuttgart · New York

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K. C. Kumara Swamy et al.
PAPER
2-[Anthracen-9-yl(chloro)methyl]-5,5-dimethyl-2l5-1,3,2-di-
oxaphosphinan-2-one (12)
Recrystallized (CH2Cl2–hexane, 4 + 1 mL); yield: 2.81 g (63%); mp
150–152 °C.
13C NMR (100 MHz, CDCl3): d = 20.6, 21.9 (2 s, 2 CH3), 32.4 (d,
JP-C = 6.0 Hz, CMe2), 69.7, 76.3, 76.4 (2 d, JP-C = 6.0 Hz each, 2
OCH2), 110.1 (d, JP-C = 180.0 Hz, PC), 124.6, 125.4, 126.0, 127.6,
128.4, 129.3, 129.4, 130.0, 130.8, 132.0, 138.0, 139.0, 153.5 (d,
JP-C = 5.3 Hz).
IR (KBr): 2968, 2895, 1670, 1473, 1275, 1059, 1006, 829, 783, 731
cm–1.
31P NMR (80 MHz, CDCl3): d = 11.4.
1H NMR (400 MHz, CDCl3): d = 0.92, 1.06 (2 s, 6 H, 2 CH3), 3.66–
4.27 (m, 4 H, 2 OCH2), 6.74 (d, JP-H = 20.0 Hz, 1 H, PCH), 7.47–
9.00 (m, 9 H, ArH).
13C NMR (100 MHz, CDCl3): d = 21.2, 21.5 (2 s, 2 CH3), 32.6 (d,
JP-C = 7.0 Hz, CMe2), 48.3 (d, JP-C = 159.5 Hz, PCHCl), 77.0, 77.2
(2 d, JP-C = 8.0 Hz, 2 OCH2), 122.1, 124.1, 124.8, 125.5, 126.2,
127.0, 127.2, 127.7, 129.1, 129.9, 130.4, 130.5, 130.8, 130.9, 131.3,
131.9.
Anal. Calcd for C20H21O4P: C, 67.41; H, 5.94. Found: C, 67.46; H,
5.94.
2-[Anthracen-9-yl(chloro)methyl]-5,5-dimethyl-2l5-1,3,2-di-
oxaphosphinan-2-one (12) and 2-Chloro-1,1-dimethylethyl
Hydrogen 10-(5,5-Dimethyl-2-oxo-2l5-1,3,2-dioxaphosphinan-
2-ylmethylene)-4a,9,9a,10-tetrahydroanthracen-9-ylphospho-
nate (20)
A mixture of 5 (1.35 g, 8.0 mmol) and 9-anthraldehyde (1.40 g, 6.9
mmol) was stirred at 80 °C for 2 d. The 31P NMR spectrum of the
crude mixture showed peaks at d = 11.2, 11.9, 12.3, 24.2, 35.7, 35.8.
Excess of aldehyde was removed by passing the mixture through a
short column (silica gel, EtOAc–hexane). Compounds correspond-
ing to two spots (TLC) with Rf values lower than that of the alde-
hyde were collected and crystallized (CH2Cl2–hexane). The
compounds 12 (higher Rf, yellow crystals) and 20 (lower Rf, white
crystals) were separated readily by hand-picking to give 12 (0.89 g,
35%) and 20 (1.07 g, 30%).
31P NMR (162 MHz, CDCl3): d = 12.4.
Anal. Calcd for C20H20ClO3P: C, 64.26; H, 5.34. Found: C, 64.42;
H, 5.34.
10-(5,5-Dimethyl-2-oxo-2l5-1,3,2-dioxaphosphinan-2-ylmethyl-
ene)anthracen-9(10H)-one (13)
Recrystallized (CH2Cl2–hexane, 4 + 1 mL); yield: 0.31 g (7%); mp
200–202 °C.
IR (KBr): 1665, 1263, 1055, 1001, 775 cm–1.
1H NMR (400 MHz, CDCl3): d = 0.76, 1.21 (2 s, 6 H, 2 CH3), 3.62–
3.83 (m, 4 H, 2 OCH2), 6.43 (d, JP-H = 11.1 Hz, 1 H, PCH), 7.61–
8.57 (m, 8 H, ArH).
2-Chloro-1,1-dimethylethyl Hydrogen 10-(5,5-Dimethyl-2-oxo-
2l5-1,3,2-dioxaphosphinan-2-ylmethylene)-4a,9,9a,10-tetrahy-
droanthracen-9-ylphosphonate (20)
Mp 196–198 °C; X-ray structural analysis was performed on this
sample.
IR (KBr): 3059, 2974, 1601, 1572, 1476, 1271, 976 cm–1.
13C NMR (100 MHz, CDCl3): d = 20.6, 21.7 (2 s, 2 CH3), 32.5 (d,
JP-C = 6.1 Hz, CMe2), 76.5, 76.6 (2 s, 2 OCH2), 115.4 (d, JP-C
=
179.5 Hz, PC), 124.2, 126.9, 127.2, 129.3, 130.0, 130.8, 131.0,
131.3, 132.6, 133.4, 134.6, 139.0, 139.3, 149.6 (d, JP-C = 4.8,
PC=C), 184.3 (s, C=O).
31P NMR (80 MHz, CDCl3): d = 9.6.
1H NMR (400 MHz, CDCl3): d = 0.81, 0.85, 0.91, 1.26 (4 s, 12 H,
4 CH3), 3.13–3.29 (m, 4 H, 2 OCH2), 3.80–4.05 (m, 4 H, 2 OCH2),
4.48 (d, JP-H = 29.0 Hz, 1 H, PCH), 6.03 (d, JP-H = 11.7 Hz, 1 H,
PCH=C), 7.17–8.13 (m, 8 H, ArH), 9.3 (br s, 1 H, OH).
13C NMR (100 MHz, CDCl3): d = 20.2, 22.1, 22.2, 22.3 (4 s,
4 CH3), 32.3 (d, JP-C = 6.1 Hz, CMe2), 36.7 (d, JP-C = 7.1 Hz, CMe2),
46.7 (d, JP-C = 135.0 Hz, PCH), 51.1 (s, CH2Cl), 69.6 (d, JP-C = 7.8
Hz, OCH2), 75.6, 76.7 (2 d, JP-C = 5.8 Hz each, 2 OCH2), 110.2 (d,
JP-C = 178.4 Hz, PCH), 125.0, 127.2, 128.1, 128.2, 128.3, 128.4,
128.5, 128.6, 129.0, 129.1, 129.6, 129.7, 131.2, 131.3, 132.4, 132.5,
137.8, 138.1, 152.5 (all aromatic C).
Anal. Calcd for C20H19O4P: C, 67.80; H, 5.37. Found: C, 67.83; H,
5.40.
2-(10-Chloroanthracen-9-ylmethyl)-5,5-dimethyl-2l5-1,3,2-di-
oxaphosphinan-2-one (14)
Recrystallized (benzene, 5 mL); yield: 0.22 g (5%); mp 176–178
°C.
IR (KBr): 2966, 1669, 1521, 1474, 1278, 1006, 987, 833, 785, 733
cm–1.
31P NMR (80 MHz, CDCl3): d = 11.2, 24.2.
1H NMR (400 MHz, CDCl3): d = 0.45, 0.84 (2 s, 6 H, 2 CH3), 3.26–
3.32 (m, 2 H, OCHAHB), 4.02–4.07 (m, 2 H, OCHAHB), 4.38 (d,
JP-H = 22.8 Hz, 2 H, PCH), 7.64–8.63 (m, 8 H, ArH).
13C NMR (100 MHz, CDCl3): d = 21.0, 21.2 (2 s, 2 CH3), 26.8 (d,
JP-C = 137.5 Hz, PC), 32.3 (s, CMe2), 75.1, 75.2 (2 s, 2 OCH2),
121.4, 121.8, 125.0, 125.1, 125.6, 126.4, 126.5, 128.1, 128.5, 128.6,
130.7.
2-(10-Bromoanthracen-9-ylmethyl)-5,5-dimethyl-2l5-1,3,2-di-
oxaphosphinan-2-one (22)
To a soln of 11 (5.00 g, 14.0 mmol) in CH2Cl2 (80 mL) maintained
at 0 °C was added PBr3 (1.6 mL, 16.8 mmol) dropwise under N2
over a period of 15 min and the reaction was maintained at 0 °C for
a further 0.5 h. The mixture was stirred at r.t. for 12 h and then
quenched by the addition of ice-cold H2O, extracted with CH2Cl2,
washed with H2O (3 × 20 mL), dried (anhyd Na2SO4), and the sol-
vent was removed to give the bromophosphonate with ~95% purity.
The yield could be marginally improved by using a higher stoi-
chiometry 11/PBr3 (1:2); yield: 4.7 g (80%); mp 168–170 °C.
31P NMR (80 MHz, CDCl3): d = 20.3.
Anal. Calcd for C20H20ClO3P: C, 64.26; H, 5.34. Found: C, 64.38;
H, 5.34.
IR (KBr): 2928, 1732 (w), 1473, 1259, 1061, 1007, 985, 748 cm–1.
10-(5,5-Dimethyl-2-oxo-2l5-1,3,2-dioxaphosphinan-2-ylmethyl-
ene)-9,10-dihydroanthracen-9-ol (15)
Recrystallized (MeCN–CH2Cl2, 4 + 1 mL); yield: 0.70 g (15%); mp
208–210 °C.
1H NMR (400 MHz, CDCl3): d = 0.44, 0.83 (2 s, 6 H, 2 CH3), 3.29,
4.04 (dd each, 4 H, 2 OCH2), 4.37 (d, JP-H = 14.8 Hz, 2 H, PCH2),
7.51–8.64 (m, 8 H, ArH).
13C NMR (50 MHz, CDCl3): d = 21.1, 21.3 (2 s, 2 CH3), 27.1 (d,
JP-C = 137.0 Hz, PCH2), 32.3 (d, JP-C = 6.0 Hz, CMe2), 75.3 (d,
JP-C = 7.5 Hz, 2 OCH2), 124.1, 124.8, 125.2, 126.5, 127.0, 128.7,
129.1, 130.4, 131.1, 131.2 (all aromatic C).
IR (KBr): 3362, 3065, 2961, 1597, 1562, 1263, 1060, 1008, 825
cm–1.
1H NMR (400 MHz, CDCl3): d = 0.77, 1.21 (2 s, 6 H, 2 CH3), 2.70
(br s, 1 H, OH), 3.67–3.80 (m, 4 H, 2 OCH2), 5.60 (s, 1 H, CHOH),
6.10 (d, JP-H = 13.8 Hz, 1 H, PCH), 7.38–8.25 (m, 8 H, ArH).
Synthesis 2007, No. 6, 893–901 © Thieme Stuttgart · New York

PAPER
Anthracenyl-Substituted Phosphonates
899
31P NMR (80 MHz, CDCl3): d = 20.3.
9-Bromo-10-[2-(4-bromophenyl)vinyl]anthracene (26)
Yield: 0.45 g (80%); mp 206–208 °C.
Anal. Calcd for C20H20BrO3P: C, 57.29; H, 4.81. Found: C, 57.24;
H, 4.80.
LC-MS: m/z = 419, 421 [M]+ (79,81Br).
IR (KBr): 1487, 1435, 1337, 1071, 1005, 972, 949, 903, 837, 799,
775, 752, 737 cm–1.
1H NMR (400 MHz, CDCl3): d = 6.84 (d, J = 16.0 Hz, 1 H, Ar-
CH=), 7.47–8.61 (m, 13 H, ArH, ArCH=CH).
13C NMR (50 MHz, CDCl3): d = 122.1, 122.9, 125.4, 125.8, 126.4,
127.1, 128.1, 128.2, 128.8, 130.4, 132.0, 133.2, 135.9, 136.8.
9-[2-(4-Nitrophenyl)vinyl]anthracene (23) and 9-[2-(4-Chloro-
phenyl)vinyl]anthracene (24); General Procedure
To a suspension of NaH (0.18 g, 7.6 mmol) in THF (30 mL), the
phosphonate 12 (0.71 g, 1.9 mmol) was added at 0 °C and the mix-
ture stirred for 30 min. Then aldehyde (1.9 mmol) was added and
the mixture stirred at r.t. for 10 h. It was then quenched by addition
of ice-cold H2O (20 mL) and extracted with Et2O (3 × 20 mL). The
combined organic layers were washed with H2O and sat. brine and
dried (Na2SO4). The solvent was evaporated to afford a red solid,
which was purified by column chromatography (hexane).
Anal. Calcd for C22H14Br2: C, 60.31; H, 3.22. Found: C, 60.44; H,
3.21.
9-Bromo-10-[2-(4-methoxyphenyl)vinyl]anthracene (27)
Yield: 0.33 g (66%); mp 160–162 °C; this compound was recrystal-
lized (CHCl3–hexane, 2 + 0.5 mL) for X-ray crystal structure deter-
mination.
IR (KBr): 1603, 1508, 1441, 1250, 1173, 1028, 748 cm–1.
1H NMR (400 MHz, CDCl3): d = 3.89 (s, 3 H, CH3), 6.84 (d,
J = 16.4 Hz, 1 H, PhCH=), 7.0–8.6 (m, 13 H, ArH, PhCH=CH).
13C NMR (50 MHz, CDCl3): d = 55.5, 114.3, 122.2, 122.6, 125.2,
125.4, 125.5, 126.2, 126.8, 127.0, 127.8, 127.9, 128.1, 128.7, 129.9,
130.4, 130.6, 134.1, 136.7, 137.4, 159.6, 159.8.
9-[2-(4-Nitrophenyl)vinyl]anthracene (23)
Yield: 0.30 g (50%); mp 184–186 °C; this was recrystallized
(CH2Cl2–hexane, 4 + 1 mL) for X-ray crystal structure analysis.
IR (KBr): 2924, 1674, 1591, 1516 1338, 736 cm–1.
1H NMR (200 MHz, CDCl3): d = 6.98–8.56 (m, 15 H, ArH,
ArCH=).
13C NMR (50 MHz, CDCl3): d = 124.3, 125.4, 125.5, 126.0, 126.8,
127.1, 127.3, 127.5, 129.0, 129.7, 130.0, 131.5, 134.1, 135.1, 143.6.
Anal. Calcd for C23H17BrO: C, 70.96; H, 4.40. Found: C, 70.98; H,
4.40.
Anal. Calcd for C22H15NO2: C, 81.21; H, 4.65; N, 4.30. Found: C,
81.21; H, 4.68; N, 4.37.
LC-MS: m/z = 325 [M]+.
9-Bromo-10-[2-(4-nitrophenyl)vinyl]anthracene (28)
Yield: 0.30 g (58%); mp 196–198 °C.
IR (KBr): 1591, 1514, 1339, 1262, 1105, 1017, 885, 850, 802, 734
cm–1.
1H NMR (400 MHz, CDCl3): d = 7.05 (d, J = 16.0 Hz, 1 H,
PhCH=), 7.50–8.50 (m, 13 H, ArH, PhCH=CH).
13C NMR (50 MHz, CDCl3): d = 124.3, 125.4, 125.5, 126.0, 126.2,
127.1, 127.4, 128.5, 128.9, 129.7, 129.9, 131.3, 131.5, 135.1, 143.6.
9-[2-(4-Chlorophenyl)vinyl]anthracene (24)
Yield: 0.27 g (48%); mp 160–162 °C; the sample contained ca 2%
of another Horner–Wadsworth–Emmons product and hence the
CHN analysis was not recorded.
IR (KBr): 3030, 1620, 1487, 1086, 731 cm–1.
1H NMR (400 MHz, CDCl3): d = 6.82 (d, J = 16.0 Hz, 1 H,
CHC6H4-4-Cl), 7.39–7.74 (m, 8 H, anthryl-H), 7.81 (d, J = 16.0 Hz,
1 H, ArCH=CHC6H4-4-Cl), 8.28 (d, J = 8.8 Hz, 2 H, anthryl-H),
8.38 (s, 1 H), 8.52 (d, J = 8.8 Hz, 2 H, anthryl-H).
13C NMR (50 MHz, CDCl3): d = 125.1, 125.8, 126.3, 126.7, 127.8,
128.6, 129.0, 130.1, 132.2, 133.9, 135.5, 136.0, 136.7.
Anal. Calcd for C22H14BrNO2: C, 65.36; H, 3.50; N, 3.46. Found: C,
65.38; H, 3.56; N, 3.56.
[2-(10-Bromoanthracen-9-yl)vinyl]ferrocene (29)
Yield: 0.39 g (65%); mp 166–168 °C.
IR (KBr): 1616, 1437, 1327, 1254, 1105, 1044, 999, 955, 903, 822,
799, 766, 748 cm–1.
LC-MS: m/z = 315 [M]+.
1H NMR (400 MHz, CDCl3): d = 4.30, 4.40, 4.63 (3 s, 9 H, ferroce-
nyl-H), 6.67 (d, J = 16.0 Hz, 1 H, FeC5H5CH=), 7.41–8.60 (m, 9 H,
ArH, -CH=CH-).
13C NMR (50 MHz, CDCl3): d = 67.2, 69.4 (ferrocenyl-C), 83.2
[C(ferrocenyl)CH=CH], 121.5, 122.0, 125.5, 126.2, 126.7, 127.0,
128.2, 128.8, 130.5, 134.4, 136.5.
9-(2-Arylvinyl)-10-bromoanthracenes 25–29; General Proce-
dure
To a suspension of NaH (0.14 g, 60% suspension, 5.72 mmol) in
THF (20 mL) stirred at 0 °C was added 10-bromophosphonate 22
(0.54 g, 1.28 mmol) in one portion. The mixture stirred for 30 min,
the aldehyde (1.28 mmol) was added, and the contents were brought
to r.t. and stirred for 12 h. Then crushed ice was added, the product
extracted with Et2O and chromatographed (silica gel, hexanes) to
afford the alkenes 25–29.
Anal. Calcd for C26H19BrFe: C, 66.84; H, 4.10. Found: C, 66.92; H,
4.07.
LC-MS: m/z = 467, 469 [M]+ (79,81Br).
9-Bromo-10-styrylanthracene (25)
Yield: 0.32 g (70%); mp 154–156 °C.
IR (KBr): 1435, 1339, 1254, 963, 903, 748 cm–1.
1H NMR (400 MHz, CDCl3): d = 6.91 (d, J = 16.4 Hz, 1 H,
PhCH=), 6.95–8.61 (m, 14 H, ArH, PhCH=CH).
9-Bromo-10-{2-[4-(phenylethynyl)phenyl]vinyl}anthracenes
(30); Typical Procedure
To previously evacuated mixture of 26 (0.30 g, 0.68 mmol),
PdCl2(PPh3)2 (2 mol%), and CuI (4 mol%) in anhyd dioxane (3
mL), Et3N (0.57 mL, 4.09 mmol) was added followed by slow ad-
dition of phenylacetylene (0.23 mL, 2.05 mmol) in anhyd dioxane
(1 mL) over a period of 40 min. When the addition was complete,
the mixture was heated at 80 °C for 12 h and then solvent removed
in vacuo. The residue was purified by column chromatography
(hexane–EtOAc) to give 30; yield: 0.16 g (50%); mp 110–112 °C.
13C NMR (50 MHz, CDCl3): d = 122.7, 124.6, 125.2, 125.7, 126.1,
126.6, 127.7, 128.2, 129.0, 130.4, 130.5, 133.7, 137.1, 138.0.
Anal. Calcd for C22H15Br: C, 73.55; H, 4.21. Found: C, 73.67; H,
4.26.
LC-MS: m/z = 359, 361 [M]+ (79,81Br).
Synthesis 2007, No. 6, 893–901 © Thieme Stuttgart · New York

900
K. C. Kumara Swamy et al.
PAPER
IR (KBr): 1694, 1483, 1435, 1381, 1271, 1159, 1069, 1007, 953,
847, 795, 760 cm–1.
1H NMR (400 MHz, CDCl3): d = 6.84 (d, J = 16.6 Hz, 1 H,
ArCH=), 7.36–8.76 (m, 18 H, PhC≡C, ArH, ArCH=CH).
13C NMR (100 MHz, CDCl3): d = 86.6, 101.3, 117.4, 122.0, 123.7,
125.5, 125.9, 126.3, 126.4, 127.3, 128,1, 128.2, 128.6, 129.4, 131.7,
132.0, 132.1, 132.4, 133.7, 136.1, 136.6, 137.3.
References
(1) (a) Kim, Y.-H.; Shin, D.-C.; Kim, S.-H.; Ko, C.-H.; Yu, H.-
S.; Chae, Y.-S.; Kwon, S.-K. Adv. Mater. 2001, 13, 1690.
(b) Ito, K.; Suzuki, T.; Sakamoto, Y.; Kubota, D.; Inoue, Y.;
Sato, F.; Tokito, S. Angew. Chem. Int. Ed. 2003, 42, 1159.
(c) Ando, S.; Nishda, J.-i.; Fujiwara, E.; Tada, H.; Inoue, Y.;
Tokito, S.; Yamashita, Y. Chem. Mater. 2005, 17, 1261.
(d) Sasaki, H.; Wakayama, Y.; Chikyow, T.; Barrena, E.;
Dosch, H.; Kobayashi, K. Appl. Phys. Lett. 2006, 88,
081907. (e) Cui, W.; Zhang, X.; Jiang, X.; Tian, H.; Yan, D.;
Geng, Y.; Jing, X.; Wang, F. Org. Lett. 2006, 8, 785.
(2) Photoswitches: (a) Schafer, C.; Mattay, J. Photochem.
Photobiol. Sci. 2004, 3, 331. Switch: (b) Callan, J. F.; De
Silva, A. P.; McClenaghan, N. D. Chem. Commun. 2004,
2048. OLED, DFT calculations: (c) Raghunath, P.; Reddy,
M. A.; Gouri, C.; Bhanuprakash, K.; Jayathirtha Rao, V. J.
Phys. Chem. A 2006, 110, 1152.
Anal. Calcd for C30H19Br: C, 78.44; H, 4.17. Found: C, 78.51; H,
4.12.
LC-MS: m/z = 459, 461 [M]+ (79,81Br).
4-{4-[2-(10-Bromoanthracen-9-yl)vinyl]phenyl}-2-methylbut-
3-yn-2-ol (31)
Yield: 0.14 g (46%); mp 134–136 °C.
IR (KBr): 3455, 1671, 1593, 1487, 1441, 1283, 1069, 808, 754
cm–1.
(3) Bailey, D.; Williams, V. E. Chem. Commun. 2005, 2569.
(4) (a) Becker, H. D. Chem. Rev. 1993, 93, 145. (b) Laurent, H.
B.; Castellan, A.; Desvergne, J.-P.; Lapouyade, R. Chem.
Soc. Rev. 2000, 29, 43. (c) Ihmels, H.; Leusser, D.; Pfeiffer,
M.; Stalke, D. Tetrahedron 2000, 56, 6867. (d) Jones, S.;
Atherton, J. C. C. Tetrahedron: Asymmetry 2001, 12, 1117.
(e) Atherton, J. C. C.; Jones, S. Tetrahedron Lett. 2002, 43,
9097. Diels–Alder reaction: (f) Bawa, R. A.; Jones, S.
Tetrahedron 2004, 60, 2765. (g) Atherton, J. C. C.; Jones, S.
Tetrahedron 2003, 59, 9039. (h) Horiguchi, M.; Ito, Y. J.
Org. Chem. 2006, 71, 3608.
1H NMR (400 MHz, CDCl3): d = 1.88 [s, 6 H, C(CH3)2], 6.84 (d,
J = 16.6 Hz, 1 H, ArCH=), 7.36–8.76 (m, 13 H, PhC≡C, ArH, Ar-
CH=CH).
13C NMR (100 MHz, CDCl3): d = 31.6, 31.9, 66.3, 79.1, 105.8,
116.8, 122.0, 125.2, 125.4, 125.5, 125.8, 126.3, 126.5, 127.1, 128.1,
128.2, 129.2, 130.4.
Anal. Calcd for C27H21BrO: C, 73.48; H, 4.80. Found: C, 73.38; H,
4.86.
LC-MS: m/z = 423, 425 [M – 16]+ (79,81Br).
(5) Iwamoto, E.; Hirai, K.; Tomioka, H. J. Am. Chem. Soc.
9-Bromo-10-[2-(4-oct-1-ynylphenyl)vinyl]anthracene (32)
Yield: 0.15 g (48%); mp 96–98 °C.
IR (KBr): 1483, 1379, 1071, 1007, 965, 801, 752 cm–1.
1H NMR (400 MHz, CDCl3): d = 0.93–2.80 (m, 13 H, aliphatic-H),
6.90 (d, J = 16.0 Hz, 1 H, ArCH=), 7.49–8.66 (m, 13 H, ArH,
ArCH=CH).
13C NMR (100 MHz, CDCl3): d = 14.1, 19.6, 20.3, 22.6, 28.8, 31.5,
80.6, 102.8, 118.8, 119.1, 121.9, 125.0, 125.7, 126.0, 126.2, 126.5,
127.0, 127.5, 128.1, 129.4, 130.5, 132.0, 132.4, 133.5, 136.2, 136.4,
137.5.
2003, 125, 14664.
(6) DNA cleavage, anthracene derivatives: (a) Tan, W. B.;
Bhambhani, A.; Duff, M. R.; Rodger, A.; Kumar, C. V.
Photochem. Photobiol. 2006, 82, 20. (b) Ghosh, T.; Maiya,
B. G.; Samanta, A.; Shukla, A. D.; Jose, D. A.; Kumar, D.
K.; Das, A. J. Biol. Inorg. Chem. 2005, 10, 496.
(c) Marques, F.; Paulo, A.; Campello, M. P.; Lacerda, S.;
Vitor, R. F.; Gano, L.; Delgado, R.; Santos, I. Radiat. Prot.
Dosim. 2005, 116, 601.
(7) Cakmak, O.; Erenler, R.; Tutar, A.; Celik, N. J. Org. Chem.
2006, 71, 1795.
(8) Reports in which such anthracenyl compounds are utilized
for two photon cross-sections: (a) Yang, W. J.; Kim, C. H.;
Jeong, M.-Y.; Lee, S. K.; Piao, M. J.; Jeon, S.-J.; Cho, B. R.
Chem. Mater. 2004, 16, 2783. Phosphonate: (b)Lee, S. K.;
Yang, W. J.; Choi, J. J.; Kim, C. H.; Jeon, S.-J.; Cho, B. R.
Org. Lett. 2005, 7, 323.
(9) (a) Kumaraswamy, S.; Selvi, R. S.; Kumara Swamy, K. C.
Synthesis 1997, 207. (b) Praveen Kumar, K.; Muthiah, C.;
Kumaraswamy, S.; Kumara Swamy, K. C. Tetrahedron Lett.
2001, 42, 3219. (c) Muthiah, C.; Praveen Kumar, K.; Aruna
Mani, C.; Kumara Swamy, K. C. J. Org. Chem. 2000, 65,
3733.
Anal. Calcd for C30H27Br: C, 77.08; H, 5.82. Found: C, 77.12; H,
5.81.
LC-MS: m/z = 467, 469 [M]+ (79,81Br).
9-Oct-1-ynyl-10-[2-(4-oct-1-ynylphenyl)vinyl]anthracene (33)
Yield: 0.03 g (10%); mp 116–118 °C.
IR (KBr): 1483, 1379, 1071, 1007, 965, 801, 752 cm–1.
1H NMR (400 MHz, CDCl3): d = 0.94–2.81 (m, 26 H, aliphatic-H),
6.92 (d, J = 16.0 Hz, 1 H, ArCH=), 7.48–8.66 (m, 13 H, ArH,
ArCH=CH).
13C NMR (100 MHz, CDCl3): d = 14.1, 19.6, 20.2, 22.6, 28.2, 28.6,
28.8, 29.1, 30.2, 31.4, 31.8, 80.6, 91.7, 102.7, 118.5, 123.2, 123.7,
124.8, 124.9, 125.2, 125.6, 125.9, 126.3, 126.4, 126.5, 126.8, 127.4,
129.4, 132.0, 132.4, 132.8, 136.3, 137.1.
(10) Iorga, B.; Eymery, F.; Savignac, P. Tetrahedron 1999, 55,
2671.
(11) Firouzabadi, H.; Iranpoor, N.; Sobhani, S. Tetrahedron
2004, 60, 203.
LC-MS: m/z = 497 [M]+.
(12) In normal Horner–Wadsworth–Emmons reactions,
hydrogen is eliminated by the base to produce the carbanion,
which then reacts with the aldehyde.
(13) Said, M. A.; Kumara Swamy, K. C.; Chandra Mohan, K.;
Venkata Lakshmi, N. Tetrahedron 1994, 50, 6989.
(14) Shokol, V. A.; Kozhushko, B. N. Russ. Chem. Rev. 1985, 54,
98.
(15) Duan, S.; Turk, J.; Speigle, J.; Corbin, J.; Masnovi, J.; Baker,
R. J. J. Org. Chem. 2000, 65, 3005.
Acknowledgment
We thank CSIR (New Delhi) for financial support, DST (New De-
lhi) for Single Crystal X-ray diffractometer facility at the University
of Hyderabad, and UGC (New Delhi) for equipment under UPE and
CAS programs. V.S. and K.V.P.K. thank CSIR for fellowships.
(16) There is a possibility that compound 12 and its anion react
with each other in a disproportionation-like reaction to form
Synthesis 2007, No. 6, 893–901 © Thieme Stuttgart · New York

PAPER
a low equilibrium concentration of the corresponding a,a-
Anthracenyl-Substituted Phosphonates
901
8.37 (d with virtual coupling, 4 H, anthryl-H), 8.42 (s, 1 H,
anthryl-H). Product b: d = 6.74–6.82 (m, 2 H, olefinic-H),
7.25–7.66 (m, 11 H, phenyl-H, anthryl-H, olefinic-H), 8.38
(d, J = 8.8 Hz, 2 H, anthryl-H), 8.58 (d, J = 8.8 Hz, 2 H,
anthryl-H)].
dichlorophosphonate plus the nonchlorinated phosphonate
anion. The latter presumably reacts much faster with the
aldehyde than does the anion of compound 12. However, the
dichlorophosphonate could not be detected in the crude
product mixture [31P/1H NMR]. In the normal reaction, the
C–Cl moiety is retained: see: (a) Kumaraswamy, S.;
Kumara Swamy, K. C. Tetrahedron Lett. 1997, 38, 2183.
(b) Muthiah, C.; Praveen Kumar, K.; Kumaraswamy, S.;
Kumara Swamy, K. C. Tetrahedron 1998, 54, 14315.
(17) We have also observed two butadiene products of very close
TLC Rf values from the reaction of 12 with using
(18) (a) Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron
Lett. 1975, 16, 4467. (b) Negishi, E.; Anastasia, L. Chem.
Rev. 2003, 103, 1979.
(19) Perrin, D. D.; Armarego, W. L. F.; Perrin, D. R. Purification
of Laboratory Chemicals; Pergamon: Oxford, 1986.
(20) A program for crystal structure solution and refinement:
(a) Sheldrick, G. M. SHELX-97; University of Göttingen:
Germany, 1997. (b) Sheldrick, G. M. SADABS, Siemens
Area Detector Absorption Correction; University of
Göttingen: Germany, 1996. (c) Sheldrick, G. M.
SHELXTLNT Crystal Structure Analysis Package, Version
5.10; Bruker Analytical X-ray System: WI, 1999.
cinnamaldehyde. One of these contains hydrogen at the C10
(product a) and the second one (product b) does not [1H
NMR (400 MHz, CDCl3): product a: d = 6.75 (d, J = 16.0
Hz, 1 H, olefinic-H), 6.84 (dd, J = 10.8, 16.0 Hz, 1 H,
olefinic-H), 7.25–7.58 (m, 11 H, phenyl-H, anthryl-H), 8.03,
Synthesis 2007, No. 6, 893–901 © Thieme Stuttgart · New York