The use of BrCCl3-PPh3 in Appel type transformations to esters, O-acyloximes, amides, and acid anhydrides

Article abstract of DOI:10.1016/j.crci.2016.04.004

Esters, acyloximes, amides and acid anhydrides have been prepared from the respective carboxylic acids, oximes, amines and alcohols by the use of the reagent combination BrCCl₃-PPh₃. The reactions obviate the handling acyl halides or more aggressive reagents PCl₃, POCl₃, or SOCl₂. Furthermore, the environmentally hazardous CCl₄ used in Appel-type reactions is replaced with BrCCl₃, a reagent of less environmental concern.

Full text of DOI:10.1016/j.crci.2016.04.004

C. R. Chimie xxx (2016) 1e12
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Full paper/Memoire
The use of BrCCl3-PPh3 in Appel type transformations to
esters, O-acyloximes, amides, and acid anhydrides
Mariam Al-Azani a, Mazen al-Sulaibi a, Nuha al Soom a, Yosef Al Jasem b,
,
*
Bernhard Bugenhagen c, Bassam Al Hindawi a, Thies Thiemann a
a Department of Chemistry, United Arab Emirates University, Al Ain, Abu Dhabi, United Arab Emirates
b Department of Chemical Engineering, United Arab Emirates University, Al Ain, Abu Dhabi, United Arab Emirates
c Institute for Inorganic and Applied Chemistry, University of Hamburg, Martin-Luther-King-Platz 6, D-20146, Hamburg, Germany
a r t i c l e i n f o
a b s t r a c t
Article history:
Esters, acyloximes, amides and acid anhydrides have been prepared from the respective
carboxylic acids, oximes, amines and alcohols by the use of the reagent combination
BrCCl3-PPh3. The reactions obviate the handling acyl halides or more aggressive reagents
PCl3, POCl3, or SOCl2. Furthermore, the environmentally hazardous CCl4 used in Appel-type
reactions is replaced with BrCCl3, a reagent of less environmental concern.
Received 12 January 2016
Accepted 4 April 2016
Available online xxxx
Keywords:
ꢀ
© 2016 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.
Appel reaction
Bromotrichlorocarbon
Amidation
Esterification
Acid anhydrides
O-acyloximes
1. Introduction
[4] with nitriles, in esterification and amidation reactions
[5] and in the preparation of dichlorovinyl derivatives from
In laboratories where the working environment does
not allow the preparation and purification of acid halides
and the handling of reagents such as PCl3, PCl5, SOCl2, or
POCl3, a larger number of possible synthetic methodologies
of carboxylic acids to the respective anhydrides, amides,
and esters are inapplicable. It is in these cases that the use
of Appel-type reagents to prepare acyl halides in situ pre-
sents itself, where the acyl halides are reacted further with
carboxylates, amines, alcohols or oximes.
The versatile combination of triphenylphosphine (PPh3)
and tetrachlorocarbon (CCl4) is the original Appel reagent,
which can be used in a larger number of transformations
[1]. Originally utilized in the reaction of alkanols with
chloroalkanes [1,2], PPh3-CCl4 has been shown to be
effective in the reaction of carboxamides [3] and aldoximes
the corresponding aldehydes and ketones [6]. Additionally,
phosphoric acid derivatives can be transformed to respec-
tive amides and phosphoric anhydrides. However, CCl4 is
known to be an extremely hepatotoxic substance. Also,
because of its long life-span in the atmosphere once
released (as it does not oxidize or photodegrade in the
troposphere), its involvement in the deterioration of the
stratospheric ozone layer has been noted [7]. Furthermore,
due to the provisions of the Montreal protocol and its
subsequent amendments on substances that deplete the
ozone layer, CCl4 has been replaced for many applications.
Thus, CCl4 is used no longer as a solvent for chemical re-
actions, and scientists have started looking for substitutes.
In Appel-type reactions, CBr4 instead of CCl4 has been used,
but it is expensive. In more recent times, the exchange of
CCl4 for BrCCl3 has been investigated to some degree. The
latter reagent is preferred over CCl4 since it is of less
environmental concern, is not listed as an ozone depletor
* Corresponding author.
E-mail address: thies@uaeu.ac.ae (T. Thiemann).
http://dx.doi.org/10.1016/j.crci.2016.04.004
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1631-0748/© 2016 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.
Please cite this article in press as: M. Al-Azani, et al., The use of BrCCl3-PPh3 in Appel type transformations to esters, O-acy-
loximes, amides, and acid anhydrides, Comptes Rendus Chimie (2016), http://dx.doi.org/10.1016/j.crci.2016.04.004

2
M. Al-Azani et al. / C. R. Chimie xxx (2016) 1e12
and because its higher polarity does not reach the strato-
sphere so easily. Therefore, there is less concern about its
photolysis in the stratosphere [8]. The employment of
PPh3-BrCCl3 in amidation reactions [9], in the reaction of
aldehydes with dihalovinyl compounds [10] and of aldox-
imes and amides to nitriles [11] has been published already.
In this paper, the use of BrCCl3-PPh3 in Appel type trans-
formations of acids to esters and anhydrides and of keto
oximes to acyloximes is discussed.
see that the use of BrCCl3/PPh3 in the reaction of cinnamic
acids led exclusively to the corresponding cinnamides and
not to 1,4-addition adducts as side products (Scheme 1).
Only in some cases of the reaction of alkoxycinnamic acids
under these conditions can a small amount of the corre-
sponding (E)-1-bromo-2-(4-alkoxyphenyl)ethene be iso-
lated as
a
side-product, regardless of the added
nucleophile. A typical example is given in the trans-
formation of 4d to 5g, where a small amount of (E)-1-
bromo-2-(4-methoxyphenyl)ethene (6) is produced,
(Scheme 1).
2. Results and discussion
Next, we investigated whether the reagent combination
BrCCl3/PPh3 could be used in the reaction of carboxylic
acids with acid anhydrides. When benzoic acid was treated
with BrCCl3/PPh3 in refluxing CH2Cl2, it was realized that
acyl halides were formed, where from this reaction benzoyl
chloride could be isolated in pure form after flash chro-
matography. Having established the formation of acyl
The authors' initial interest in the use of Appel-type
transformations of acids to their derivatives stemmed
from the need to prepare cinnamides from alkylami-
doalkylquinone derivatives [12]. Although the use of
BrCCl3/PPh3 had been documented in the conversion of
carboxylic acids to carboxamides [13], we were gratified to
i. PPh3/CBrCl3
CH2Cl2
ii. PhCH2NH2 (2a)
CH3(CH2)14CO2H
CH3(CH2)14CONCH2Ph
1
3a (89%)
O
i. PPh3/CBrCl3
CH2Cl2
ii. R2NH2 (2)
O
OH
NHR
2a: R = CH Ph
2b: R = n-C H
R
R
5a: R1 = H; R2 = CH2Ph (92%)
5b: R1 = 3-Cl; R2 = CH2Ph (93%)
5c: R1 = H; R2 = n-C8H17 (88%)
4a: R1 = H
4b: R1 = 3-Cl
O
i. PPh3/CBrCl3
CH2Cl2
ii. R2R3NH (2)
O
OH
NR R
2c: R R = -(CH ) -
2d: R R = -(CH ) -
2e: R = R = 2-ethyhexyl
R
R
4a: R1 = H
4c: R1 = 2,5-di-OCH3
5d: R1 = H; R2-R3 = -(CH2)5- (84%)
5e: R1 = H; R2-R3 = -(CH2)4- (80%)
5f: R1 = 2,5-di-OCH3; R2 = R3 = 2-
ethyhexyl (60%)
O
O
i. PPh3/CBrCl3
CH2Cl2
NHCH Ph
OH
ii. PhCH2NH2 (2a)
5g (83%)
Br
H CO
H CO
4d
+
H CO
6 (10%)
Scheme 1. Amidation of cinnamic acids with PPh3-CBrCl3 as a reagent.
Please cite this article in press as: M. Al-Azani, et al., The use of BrCCl3-PPh3 in Appel type transformations to esters, O-acy-
loximes, amides, and acid anhydrides, Comptes Rendus Chimie (2016), http://dx.doi.org/10.1016/j.crci.2016.04.004

M. Al-Azani et al. / C. R. Chimie xxx (2016) 1e12
3
halides in this transformation, the reaction of the acyl ha-
lides in situ with carboxylates as nucleophiles was war-
ranted. Previously, carboxylic acid anhydrides have been
prepared from the respective carboxylic acids by using re-
agents that are both activating and dehydrating such as
phosphorus pentoxide [12], carbodiimides [13], isocyanates
[14], imidazolinium chlorides [15], phosgene [16] tri-
chlorotrifluoroacetone [17] and triphosgene [18]. Also,
carboxylic acids can be transformed into an activated acyl
species first, which subsequently is further reacted with an
equivalent of the carboxylic acid or the carboxylate to
furnish the acid anhydride. Examples of this are the acti-
vation with 2,4-dichloro-1,3,5-triazine [19] or the ZnCl2-
catalysed reaction of 2-acyl-4,5-dichloropyridazin-3(2H)-
ones [20]. Most frequently, however, acid chlorides are
used to prepare acid anhydrides. In these cases the acid
chlorides can be prepared separately, isolated, and subse-
quently reacted with the carboxylic acid or its anion under
various conditions [21].
an equivalent of either dry triethylamine or 1,8-
diazabicycloundec-7-ene (DBU), leads to the correspond-
ing acid anhydrides in good yield (Scheme 2). The products
were obtained from the reaction mixtures by rapid column
chromatography.
From the above results, it was deemed likely that car-
boxylic esters should also be accessible through the same
strategy, by changing the nucleophile to an alcohol, adding
the alcohol after the activation of the acid and/or its in situ
transformation to the acyl halide. This indeed proved to be
the case as is seen from Scheme 3. The authors preferred
venting the hydrogen halide produced as a side product, by
submitting the reaction vessel intermittently to vacuum
rather than adding a tertiary amine base to the reaction
solution. The alkyl carboxylates were produced in accept-
able yield and the process can be seen as a viable alterna-
tive to other known esterification methods, when used at
the laboratory scale.
Finally, the authors investigated whether this general
strategy of using BrCCl3/PPh3 in the activation of carboxylic
acids would give access to acyl oximes as well. Recently,
acyl oxime derivatives have attracted considerable
We found that the reaction of carboxylic acids with
BrCCl3/PPh3 in refluxing CH2Cl2 and the subsequent addi-
tion of a further equivalent of carboxylic acid, followed by
O
CO2H
PPh3/CBrCl3
Et3N, CH2Cl2
O
CO2H
7a
8a (97%)
O
PPh3/CBrCl3
Et3N, CH2Cl2
O
O
CO2H
2
7b
8b (63%)
O
O
PPh3/CBrCl3
Et3N, CH2Cl2
CO2H
O
R
R
R
7c: R = H
7d: R = 4-Br
8c: R = H (78%)
8d: R = 4-Br (79%)
O
O
CO2H PPh3/CBrCl3
O
Et3N, CH2Cl2
R
R
R
4a: R = H
4b: R = 3-Cl
4c: R = 2,5-di-OCH3
4e: R = 3,4-di-OCH3
9a: R = H (71%)
9b: R = 3-Cl (73%)
9c: R = 2,5-di-OCH3 (76%)
9d: R = 3,4-di-OCH3 (72%)
Scheme 2. Preparation of anhydrides with PPh3-CBrCl3 as a reagent.
Please cite this article in press as: M. Al-Azani, et al., The use of BrCCl3-PPh3 in Appel type transformations to esters, O-acy-
loximes, amides, and acid anhydrides, Comptes Rendus Chimie (2016), http://dx.doi.org/10.1016/j.crci.2016.04.004

4
M. Al-Azani et al. / C. R. Chimie xxx (2016) 1e12
CO2R
PPh3/CBrCl3
CH2Cl2
CO2H
ROH
O2N
O2N
10a: R = Et
11a: R = Et (87%)
11b: R = i-Prop (85%)
O
10b: R = i-Prop
7e
C
CO2H
PPh3/CBrCl3
CH2Cl2
O
OH
Cl
Cl
10c
11c (89%)
7f
CO2-n-C7H15
PPh3/CBrCl3
CH2Cl2
CO2H
n-C7H15OH
Cl
Cl
10d
O
11d (89%)
7g
O
PPh3/CBrCl3
CH2Cl2
CO2H
H
OH
R
H
H
H
4d: 4-OCH3
4e: 3,4-di-OCH3
H
H
H3CO
11e: 4-OCH3 (68%)
11f: 3,4-di-OCH3 (76%)
R
H3CO
10e
Scheme 3. Esterification using PPh3/BrCCl3.
attention in medicinal research due to their antiphytoviral,
antitumor, antibacterial, and fungicidal bioactivities. A
larger number of studies on their synthesis and biological
activities have been reported [22]. Some acyl oximes have
been found to cleave DNA in a process that is triggered by
UV light [23]. The weak NeO bond of the acyl oximes is
cleaved selectively to generate the iminyl and carboxy
radicals which can then cause the cleavage of the DNA. In
our research on cancer-active estrone based molecules, we
were interested to prepare O-cinnamoyl estrone-17-oximes
such as 13a. Within this context, we succeeded to react
estrone-17-oxime 12a with the substituted cinnamic acid
4e in the presence of BrCCl3/PPh3 (Scheme 4). This
methodology was found to be quite general to react oximes
and acids with O-acyl oximes (Scheme 5).
Finally, in order to assess the typical molecular struc-
tural parameters of aromatic O-acyl oximes, the crystal
structure of 2,5-dimethoxyacetophenone oxime 4-
nitrobenzoate 13g was studied. The crystallization was
carried out in a mixture of CH2Cl2/diethyl ether/hexane (1/
1/1ev/v/v) at room temperature, where 13g was isolated as
clear light yellow plates. 13g was crystallized in the
monoclinic space group P21/C with unit cell parameters:
a ¼ 17.1206 (6), b ¼ 8.17107 (19), c ¼ 11.6431 (3) Å,
b
¼
102.779 (3)ꢀ (Table 1). Selected bond distances and angles
are listed in Table 2. The molecular structure of 2,5-
O
N
O
PPh3/CBrCl3
CH2Cl2
H3CO
H3CO
CO2H
H
OH
N
H
H
H
4e
H
H
H3CO
13a
H3CO
12a
(76%)
OCH3
H3CO
Scheme 4. Preparation of a N-cinnamoylestrone-17-oxime.
Please cite this article in press as: M. Al-Azani, et al., The use of BrCCl3-PPh3 in Appel type transformations to esters, O-acy-
loximes, amides, and acid anhydrides, Comptes Rendus Chimie (2016), http://dx.doi.org/10.1016/j.crci.2016.04.004

M. Al-Azani et al. / C. R. Chimie xxx (2016) 1e12
5
CO2H
O
PPh3/CBrCl3
N
R
CH2Cl2
4a
OH
N
O
CO2H
7c
12b
13b: R = (E)-CH=CH-Ph (82%)
13c: R = Ph (80%)
O
R
CO2H
PPh3/CBrCl3
CH2Cl2
N
O2N
O
OH
N
7c
4e
O2N
CO2H
13d: R = Ph (77%)
12c
13e: R = (E)-CH=CH-Ph-p-OMe (80%)
H3CO
Br
+
6
H3CO
(12%)
O
R
N
PPh3/CBrCl3
CH2Cl2
O
H3CO
H3CO
CO2H
OH
N
H3CO
H3CO
4d
13f: R = (E)-CH=CH-Ph-(3,4)-di-OMe
(73%)
12d
O
R
OCH3
N
PPh3/CBrCl3
CH2Cl2
O2N
O
OH
OCH3
N
CO2H
OCH3
7e
OCH3
12e
13g: R = Ph-p-NO2 (72%)
Scheme 5. O-acylation of oximes with PPh3/BrCCl3 as the reagent.
dimethoxyacetophenone oxime 4-nitrobenzoate (13g) is
shown in Fig.1. In the oxime ester moiety, the bond-lengths
of C15]N1 and C17]O4 are 1.288 (2) Å and 1.1977 (19) Å,
respectively, which is characteristic of double-bonds. The
values of the C17eO3 and N1eO3 bonds are 1.3538 (19) Å
and 1.4520 (16) Å, respectively, indicating a single-bond-
character. These bond-lengths are in the expected range
The nitro-group is slightly tilted with respect to the ar-
omatic ring C7eC12 (torsion-angle: C11eC10eN2eO5 ¼ 4.5
(2) ꢀ). The methoxy-groups on the aromatic ring (C1eC6)
show
a
significant difference in torsion angles
(C4eC5eO1eC13 ¼ 175.2 (1) ꢀ) and C1eC2eO2eC14 of
155.5(2) ꢀ). This can be explained with packing-effects. The
average two planes of the aromatic rings (non-hydrogen
atoms) form an angle of 26.17 (2) ꢀ between each other. This
is mainly due to torsions in the bonds O3eN1 and C15eC1
and a further indication of a localized double-bond between
of oxime-esters [24].
ꢀ
The bond angles of C15eN1eO3 ¼ 108.16 (12)
,
ꢀ
C17eO3eN1 ¼ 112.40 (11) are typical for linear oxime-
esters [24].
C15 and N1 in contrast to an extended p-system.
Please cite this article in press as: M. Al-Azani, et al., The use of BrCCl3-PPh3 in Appel type transformations to esters, O-acy-
loximes, amides, and acid anhydrides, Comptes Rendus Chimie (2016), http://dx.doi.org/10.1016/j.crci.2016.04.004

6
M. Al-Azani et al. / C. R. Chimie xxx (2016) 1e12
Table 1
anhydrides are obtained, when the acids upon activation
Crystallographic data and structure refinement details.
with PPh3-BrCCl3 are reacted with a further equivalent of
acid in the presence of a tertiary amine. An X-ray crystal
structural analysis of acyloxime 13g was carried out. It is
envisaged that Appel-type reactions as the ones shown
here will gain further importance with the advancement of
strategies towards the recycling of the by-product triphe-
nylphosphine oxide to triphenylphosphine [25].
CCDC deposit number
Chemical formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal size (mm)
Crystal system
Space group
a (Å)
1001765
17H16N2O6
344.32
100
0.71073
0.75 0.33 0.10
Monoclinic
P21/C
17.1206 (6)
8.17107 (19)
11.6431 (3)
102.779 (3)
1588.45 (8)
4
1.440
720
0.111
3.1e27.5
ꢁ19 ꢂ h ꢂ 21;
ꢁ6 ꢂ k ꢂ 10;
ꢁ15 ꢂ l ꢂ 14
7139
C
4. Experimental
b (Å)
c (Å)
(ꢀ)
4.1. General
b
V (Å3)
Z
Melting points were measured on a Stuart SMP 10
melting point apparatus and are uncorrected. Infrared
spectra were measured with a Thermo/Nicolet Nexus 470
FTIR ESP Spectrometer. 1H and 13C NMR spectra were
recorded with a Varian 400 NMR (1H at 395.7 MHz, 13C at
100.5 MHz) and a Varian 200 MHz NMR spectrometer (1H
at 200.0 MHz, 13C at 50.3 MHz). The chemical shifts are
relative to TMS (solvent CDCl3, unless otherwise noted).
Mass spectra were measured with a JMS-01-SG-2 spec-
trometer. CHN-analysis was performed on a LECO TruSpec
Micro instrument. Column chromatography was carried
out on a silica gel (60 A, 230e400 mesh, Sigma-Aldrich).
Analytical thin layer chromatography (TLC) was carried out
on silica on TLC Alu foils from Fluka (with fluorescent in-
Dc (g/cm3)
F (000)
Absorption coeff. (mmꢁ1
)
q
range (ꢀ)
Index ranges
Reflections collected
Independent reflections
Observed reflections
3515 [Rint ¼ 0.026]
2726
Data/restraints/parameters
3515/0/229
1.059
0.0444, 0.0971
0.0624, 0.1091
0.28, ꢁ0.28
Goodness-of-fit on F2
R, wR indices [I > 2
s
(ꢀ)]
R, wR indices (all data)
Largest diff. peak and hole (e Åꢁ3
)
dicator at
l
¼ 254 nm). Triethylamine was dried over solid
KOH and distilled. 1,8-Diazabicycloundec-7-ene (DBU) was
stored over solid KOH. The oximes 12 were prepared by the
reaction of the ketones with ammonium hydrochloride
(4 mol eq.) in a solvent mixture of ethanol and water [26].
3-Arylacrylic acids 4bee and 7b were prepared by a one-
pot Wittig olefination e hydrolysis reaction of the respec-
tive benzaldehydes and 9-anthranylcarbaldehyde with
ethoxycarbonylmethylidenetriphenylphosphorane [27].
Table 2
Selected bond lengths (Å) and angles (ꢀ).
Bond lengths
C(2)eO(2)
C(5)eO(1)
C(10)eN(2)
C(13e(1)
C(14)eO(2)
C(15)eN(1)
1.3714 (19)
1.3747 (19)
1.477 (2)
C(17)eO(3)
C(17)eO(4)
O(3)eN(1)
O(5)eN(2)
O(6)eN(2)
1.3538 (19)
1.1977 (19)
1.4520 (16)
1.2298 (18)
1.2253 (17)
1.428 (2)
1.4348 (19)
1.288 (2)
Bond angles
C(5)eO(1)eC(13)
C(2)eO(2)eC(14)
C(15)eN(1)eO(3)
C(17)eO(3)eN(1)
117.20 (13)
117.03 (13)
108.16 (12)
112.40 (11)
O(5)eN(2)eO(6)
N(1)eC(15)eC(1)
O(3)eC(17)eO(4)
123.79 (14)
113.67 (13)
125.03 (15)
4.2. General procedure for the preparation of cinnamides
4.2.1. N,N-Bis(2-ethylhexyl) 3-(1,4-dimethoxyphen-2-yl)
propenoic acid amide (5f)
To a solution of PPh3 (980 mg, 3.74 mmol) in dry CH2Cl2
(12 mL) BrCCl3 (1.50 g, 7.66 mmol) was added. The resulting
mixture was stirred at rt for 30 min, during which it turned
reddish-brown. Thereafter, 2,5-dimethoxycinnamic acid
(4c, 700 mg, 3.37 mmol) was added, and the mixture was
heated under reflux for 45 min. Thereafter, di(2-ethylhexyl)
amine (1.62 g, 6.71 mmol) was added dropwise via a sy-
ringe, where the ensuing reaction is exothermic. The re-
action mixture was stirred at reflux for 14 h. Then, the
cooled mixture was concentrated in vacuo, and the residue
was subjected directly to column chromatography on a
silica gel to give 5f (875 mg, 2.03 mmol, 60%) as a colorless
oil; nmax neat/cmꢁ1) 2961, 2877, 1660, 1622, 1506, 1489,
1047, 772; dH (400 MHz, CDCl3) 1.00 (16H, m),1.48 (20H, m),
1.69e1.79 (2H, m), 3.28e3.43 (4H, m), 3.77 (3H, s, OCH3),
3.81 (3H, s, OCH3), 6.82 (1H, d, 3J ¼ 8.8 Hz), 6.84 (1H, d,
3J ¼ 8.8 Hz), 7.00 (1H, s), 7.02 (1H, d, 3J ¼ 15.6 Hz), 7.86 (1H,
d, 3J ¼ 15.6 Hz); dC (67.8 MHz, CDCl3, DEPT) 10.7 (CH3), 10.8
(CH3), 14.0 (CH3), 14.1 (CH3), 23.1 (CH2, 2C), 23.7 (CH2), 24.0
(CH2), 28.7 (CH2), 28.8 (CH2), 30.5 (CH2), 30.7 (CH2), 37.6
The molecules of 13g are arranged in two stacks, prop-
agating along the b-axis. Molecules in each stack are related
by C-glide operation and are linked to each other through
C14eH14A…O5 hydrogen bonding (Fig. 2). Along the c-
axis, neighbored stacks are linked by C8eH8…O4,
C16eH16C…O4 and C16eH16B…O6 hydrogen bonds
(Table 3).
Symmetry codes of molecules showing the labeled in-
teractions are shown in Fig. 2: i: ꢁx, ꢁ1/2 þ y, 1/2 ꢁ z; ii: ꢁx,
1 ꢁ y, ꢁz; iii: x, 1.5 ꢁ y, ꢁ1/2 þ z; iv: 1 ꢁ x, 1/2 þ y, 1/2 ꢁ z; v:
1 ꢁ x, 1 ꢁ y, 1 ꢁ z.
3. Conclusion
In a modified Appel-type reaction, cinnamic and ben-
zoic acids have been reacted with amines, alcohols, and
oximes, using the relatively environmentally friendly re-
agent combination PPh3-BrCCl3. It was also shown that
Please cite this article in press as: M. Al-Azani, et al., The use of BrCCl3-PPh3 in Appel type transformations to esters, O-acy-
loximes, amides, and acid anhydrides, Comptes Rendus Chimie (2016), http://dx.doi.org/10.1016/j.crci.2016.04.004

M. Al-Azani et al. / C. R. Chimie xxx (2016) 1e12
7
Fig. 1. Molecular structure of 2,5-dimethoxyacetophenone oxime 4-nitrobenzoate (13g) with the atomic numbering scheme. Displacement ellipsoids are drawn
at the 50% probability level.
Fig. 2. Aview of intermolecular interactions between adjacent molecules 13g that lead to the 3D network (colored molecules have the same orientation and layout).
(CH), 40.0 (CH), 50.7 (CH2), 52.0 (CH2), 55.7 (OCH3), 56.0
(CH3), 112.3 (CH), 114.4 (CH), 115.4 (CH), 119.6 (CH), 125.2
4.2.2. N-Benzylpalmitamide (3a)
As colorless needles, mp 98 ꢀC (Lit. mp 95 ꢀC [28]); IR
(KBr) nmax: 3305 (NH), 2918, 2848, 1639, 1549, 1457, 733,
(Cquat), 137.5 (CH), 152.8 (Cquat), 153.4 (Cquat), 167.3 (Cquat
CO).
,
696 cmꢁ1; 1H NMR (400 MHz, CDCl3)
d
: 0.81 (t, 3J ¼ 6.8 Hz,
Please cite this article in press as: M. Al-Azani, et al., The use of BrCCl3-PPh3 in Appel type transformations to esters, O-acy-
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8
M. Al-Azani et al. / C. R. Chimie xxx (2016) 1e12
Table 3
CH), 128.7 (2C, CH), 129.4 (CH), 135.5 (Cquat), 142.1 (CH),
165.3 (Cquat, CO).
Hydrogen bonds for 13g (Å and ꢀ ).
DeH…A
DeH
H…A
D…A
DeH…A
4.2.7. N-Pyrrolidinyl cinnamide (5e)
C3eH3…O1#1
0.950
0.950
0.980
0.980
0.980
2.496 (1)
2.516 (1)
2.599 (1)
2.601 (1)
2.501 (1)
3.375 (2)
3.317 (2)
3.141 (2)
3.330 (2)
3.177 (2)
153.9 (1)
142.1 (1)
115.0 (1)
131.3 (1)
125.9 (1)
Pale yellow solid; mp 99 ꢀC (mp 93e94 ꢀC [33]); nmax
(KBr/cmꢁ1) 3060, 2968, 2873, 1652, 1600, 1452, 1433, 986,
865, 761, 706, 681, 568, 547, 487; dH (400 MHz, CDCl3)
1.84e2.01 (4H, m), 3.56e3.63 (4H, m), 6.71 (1H, d,
3J ¼ 15.6 Hz), 7.30e7.37 (3H, m), 7.50e7.53 (2H, m), 7.68
(1H, d, 3J ¼ 15.6 Hz); dC (100.5 MHz, CDCl3) 24.3 (CH2), 26.1
(CH2), 46.1 (CH2), 46.6 (CH2), 118.8 (CH), 127.8 (2C, CH),
128.7 (2C, CH), 129.5 (CH), 135.3 (Cquat), 141.7 (CH), 164.7
(Cquat, CO).
C8eH8…O4#2
C14eH14A…O5#1
C16eH16B…O6#1
C16eH16C…O4#2
Symmetry codes: #1: x, 1.5 ꢁ y, ꢁ1/2 þ z; #2: ꢁx, 1 ꢁ y, ꢁz.
3H, CH3), 1.16e1.26 (m, 14H), 1.57 (m, 2H), 2.14 (t,
3J ¼ 7.6 Hz, 2H), 4.37 (d, 3J ¼ 8.0 Hz, 2H), 5.64 (b, NH, 1H),
7.19e7.29 (m, 5H); 13C NMR (100.5 MHz, CDCl3)
d: 14.1, 22.7,
25.8, 29.3, 29.4, 29.5, 31.9, 36.8, 43.6, 127.5, 127.8 (2C), 128.7
(2C), 138.4, 173.0 (CO); MS (EI, 70 eV) m/e (%) ¼ 345 (Mþ),
149 (100).
4.2.8. N-Benzyl 4-methoxycinnamide (5g) [34]
Colorless needles; mp 145e146 ꢀC; nmax (KBr/cmꢁ1
)
3282 (s, NH), 3030, 2929, 2834, 1644, 1605, 1528, 1252,
1217, 1174, 1028, 972, 825, 752, 699; dH (400 MHz, CDCl3)
3.81 (3H, s, OCH3), 4.54 (2H, d, 3J ¼ 5.6 Hz), 6.11 (1H, m),
6.86 (2H, d, 3J ¼ 8.4 Hz), 7.26e7.34 (5H, m), 7.42 (2H, d,
3J ¼ 8.5 Hz), 7.62 (1H, d, 3J ¼ 15.6 Hz); dC (100.5 MHz, CDCl3)
43.8, 55.3 (OCH3), 114.2 (2C), 118.0, 127.4, 127.5, 127.9 (2C),
128.7 (2C), 129.4 (2C), 138.2, 141.0, 160.9, 166.2 (CO).
4.2.3. N-Benzyl cinnamide (5a)
Colorless needles, mp 107 ꢀC (Lit. mp 106e108 ꢀC [29]);
IR (KBr) nmax: 3280 (br s, NH), 3080, 2921, 1654, 1614, 1541,
1450, 1348, 1230, 1213, 979, 751, 696 cmꢁ1; 1H NMR (CDCl3,
400 MHz)
d
: 4.56 (d, 3J ¼ 5.6 Hz, 2H), 6.06 (br s, NH, 1H),
6.42 (d, 3J ¼ 16.0 Hz, 1H), 7.25e7.30 (m, 3H), 7.47e7.48 (m,
2H), 7.66 (d, 3J ¼ 16.0 Hz, 1H); 13C NMR (100.5 MHz, CDCl3)
4.3. General procedure for the preparation of carboxylic acid
anhydrides
d
: 43.8 (ꢁ), 120.4 (CH), 127.6 (CH), 127.8 (2C, CH), 127.9 (2C,
CH), 128.7 (2C, CH), 128.8 (2C, CH), 129.7 (CH), 134.7 (Cquat),
138.1 (Cquat), 141.4 (CH), 165.8 (Cquat, CO); MS (EI, 70 eV) m/e
(%) ¼ 237 (Mþ).
4.3.1. Cinnamic anhydride (9a)
To
a
solution of triphenylphosphine (910 mg,
3.47 mmol) in dry dichloromethane (10 mL) bromotri-
chloromethane (710 mg, 3.58 mmol) was added, and the
resulting mixture was stirred at a rate for 30 min to give a
reddish-brownish solution. Thereafter, cinnamic acid (4a,
451 mg, 3.05 mmol) was added, and the resulting mixture
was held at reflux for 5 h. Thereafter, cinnamic acid
(451 mg, 3.05 mmol) and subsequently triethylamine
(310 mg, 3.05 mmol) were added, and the reaction mixture
was held at reflux for 8 h. Then, the cooled solution was
concentrated in vacuo, and the concentrate was subjected
to rapid column chromatography on a silica gel [CH2Cl2-
hexane 2:1] to give cinnamic anhydride (9a, 605 mg, 71%)
as colorless crystals; mp 139e140 ꢀC (mp 138 ꢀC [35]); IR
(KBr) nmax: 3060, 3027, 1767, 1701, 1632, 1450, 1305, 1270,
1228,1201,1074, 960, 858, 761, 690, 676, 551 cmꢁ1; 1H NMR
4.2.4. N-Benzyl 3-chlorocinnamide (5b)
Colorless needles; mp 112 ꢀC [Lit. mp 108e109 ꢀC [30]);
nmax (KBr/cmꢁ1) 3295, 3058, 2927, 1652, 1616, 1538, 1424,
1331, 1228, 1079, 1035, 969, 858, 787, 696, 664; dH
(400 MHz, CDCl3) 4.57 (2H, d, 3J ¼ 5.6 Hz), 5.97 (1H, b, NH),
6.40 (1H, d, 3J ¼ 15.6 Hz), 7.27e7.37 (8H, m), 7.48 (1H, s),
7.61 (1H, d, 3J ¼ 15.6 Hz); dC (100.5 MHz, CDCl3) 43.9, 121.7,
126.2, 127.4, 127.7, 127.9, 128.8, 129.6, 130.1, 134.8, 136.6,
137.9, 140.0, 165.2 (CO).
4.2.5. N-Octyl cinnamide (5c) [31]
Colorless solid; IR (KBr) nmax: 3285, 3063, 2954, 2926,
2853, 1668, 1653, 1548, 1476, 1460, 1333, 1224, 993, 869,
768, 721 cmꢁ1 1H NMR (CDCl3, 400 MHz)
; d: 0.86 (t,
3J ¼ 6.8 Hz, 3H), 1.26e1.30 (m, 10H), 1.54 (m, 2H), 3.36 (dt,
3J ¼ 6.0 Hz, 3J ¼ 6.0 Hz, 2H), 6.38 (d, 3J ¼ 15.6 Hz, 1H),
7.33e7.35 (m, 3H), 7.47e7.49 (m, 2H), 7.61 (d, 3J ¼ 15.6 Hz,
(CDCl3, 400 MHz)
d
: 6.53 (d, 3J ¼ 16.0 Hz, 2H), 7.43e7.45 (m,
6H), 7.57e7.59 (m, 4H), 7.86 (d, 3J ¼ 16.0 Hz, 2H); 13C NMR
(CDCl3, 100.5 MHz) d: 116.7 (2C, CH), 128.6 (4C, CH), 129.1
1H); 13C NMR (CDCl3, 100.5 MHz)
d
: 14.1 (CH3), 22.6 (ꢁ),
(4C, CH), 131.3 (2C, CH), 133.7 (2C, Cquat), 148.7 (2C, CH),
162.5 (2C, Cquat, CO).
27.0 (ꢁ), 29.2 (ꢁ), 29.3 (ꢁ), 29.7 (ꢁ), 31.8 (ꢁ), 39.8 (ꢁ),
120.7 (CH), 127.7 (2C, CH), 128.8 (2C, CH), 129.6 (CH), 134.8
(Cquat), 140.8 (CH), 165.9 (Cquat, CO); MS (EI, 70 eV) m/e
(%) ¼ 233 (Mþ).
4.3.2. Phthalic anhydride (8a)
Colorless solid; mp 130 ꢀC (Lit. 130e131 ꢀC [36]); IR
(KBr) nmax: 1851, 1762, 1598, 1469, 1258, 1108, 907, 713,
4.2.6. N-Piperidinyl cinnamide (5d)
533 cmꢁ1; 1H NMR (400 MHz, CDCl3)
d: 7.90e7.92 (m, 2H),
8.02e8.04 (m, 2H); 13C NMR (CDCl3, 100.5 MHz) 125.7 (2C,
CH), 131.3 (2C, Cquat), 136.0 (2C, CH), 162.8 (Cquat, CO); MS
(EI, 70 eV) m/e (%) ¼ 148 (Mþ, 20), 104 (100).
ꢀ
ꢀ
Colorless solid; mp 123 C (mp 122 C [32]); nmax (KBr/
cmꢁ1) 3078, 3027, 2933, 2849, 1645, 1588, 1458, 1442, 1281,
1249, 1223, 1018, 992, 764; dH (400 MHz, CDCl3) 1.57e1.70
(6H, m), 3.61 (4H, br s), 6.89 (2H, d, 3J ¼ 15.2 Hz), 7.30e7.50
(3H, m), 7.48e7.52 (2H, m), 7.62 (2H, d, 3J ¼ 15.2 Hz); dC
(100.5 MHz, CDCl3) 24.6 (CH2), 25.8 (br s, CH2), 26.6 (br s,
CH2), 43.3 (br s, CH2), 47.1 (br s, CH2), 117.7 (CH), 127.7 (2C,
4.3.3. Anthranyl-9-acrylic anhydride (8b)
As an orange solid; mp 216e218 ꢀC (Lit. 216e218 ꢀC
[37]); IR (KBr) nmax: 3052, 1760, 1706, 1123, 935, 913, 744,
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M. Al-Azani et al. / C. R. Chimie xxx (2016) 1e12
9
702 cmꢁ1; 1H NMR (CDCl3, 400 MHz)
d
6.63 (d, 3J ¼ 16.0 Hz,
7.10 (s, 2H), 7.19 (d, 3J ¼ 8.4 Hz, 2H), 7.81 (d, 3J ¼ 15.6 Hz,
2H), 7.50e7.59 (m, 8H), 8.04 (dm, 3J ¼ 8.0 Hz, 4H), 8.29 (dm,
2H); 13C NMR (CDCl3, 50.3 MHz)
d: 55.9 (2C, 2 OCH3), 56.0
3J ¼ 7.6 Hz, 4H), 8.51 (s, 2H), 8.93 (d, 3J ¼ 16.0 Hz, 2H); 13
C
(2C, 2 OCH3), 109.9 (2C, CH), 111.1 (2C, CH), 114.4 (2C, Cquat),
123.6 (2C, CH), 126.8 (2C, CH), 148.5 (2C, CH), 149.3 (2C,
NMR (CDCl3, 100.5 MHz) d: 124.9 (4C, CH), 125.4 (4C, Cquat),
125.5 (4C, CH), 126.9 (4C, CH), 128.1 (2C, Cquat), 129.0 (4C,
CH), 129.3 (2C, CH), 129.5 (4C, Cquat), 131.2 (2C, CH), 146.4
(2C, CH), 162.0 (2C, Cquat, CO). Anal. Calcd for C34H22O3
(478.54): C, 85.34%; H, 4.63%. Found: C, 85.25%; H, 4.73%.
C
C
quat), 152.0 (2C, Cquat), 162.9 (2C, Cquat, CO). Anal. Calcd for
22H22O7 (398.41): C, 66.32%; H, 5.57%. Found: C, 66.02%; H,
5.62%.
4.4. General procedure for the preparation of esters
4.3.4. Benzoic anhydride (8c)
Slowly crystallizing, colorless solid; mp 41 ꢀC (Lit. 42 ꢀC
[21a]); IR (neat) nmax: 3065, 3010, 1786, 1724, 1599, 1491,
1452, 1315, 1213, 1173, 1040, 1018, 995, 873, 778, 701,
4.4.1. Ethyl 4-nitrobenzoate (11a)
To
a
solution of triphenylphosphine (910 mg,
3.47 mmol) in dry dichloromethane (20 mL) bromotri-
chloromethane (710 mg, 3.58 mmol) was added, and the
resulting mixture was stirred at a rate for 30 min to give a
reddish-brownish solution. 4-Nitrobenzoic acid (509 mg,
3.04 mmol) was added and the solution was stirred at
reflux for 1 h. Thereafter, dry ethanol (0.50 mL, 400 mg,
8.7 mmol) was added dropwise via a syringe. The resulting
mixture was stirred at reflux for 12 h. Thereafter, it was
cooled and subjected directly to column chromatography
on a silica gel (ether/CHCl3/hexane 1:1:3) tꢀo give 11a
(515 mg, 87%) as colorless crystals; mp 56e59 C; IR (KBr)
nmax: 3120, 3057, 2990, 1716, 1607, 1526, 1351, 1279, 1103,
615 cmꢁ1; 1H NMR (CDCl3, 400 MHz)
d: 7.50e7.54 (m, 4H),
7.65e7.69 (m, 2H), 8.14e8.17 (m, 4H); 13C NMR (CDCl3,
100.5 MHz) 128.8 (2C), 128.9 (4C), 130.6 (4C), 134.6 (2C),
162.4 (2C, Cquat, CO); MS (EI, 70 eV) m/e (%) ¼ 226 (Mþ, 5),
105 (100).
4.3.5. 4-Bromobenzoic anhydride (8d)
Colorless solid; mp 221e224 ꢀC [Lit. mp 217e218 ꢀC
[38a], 225 ꢀC [38b]; IR (KBr) nmax: 1786, 1721, 1586, 1480,
1396, 1226, 1173, 1067, 1004, 824, 826, 793, 738, 676,
625 cmꢁ1
;
1H NMR (CDCl3, 400 MHz) 7.68 (d, 3J ¼ 8.8 Hz,
2H), 8.00 (d, 3J ¼ 8.8 Hz, 2H); 13C NMR (CDCl3, 100.5 MHz)
127.5 (2C, Cquat), 130.2 (2C, Cquat), 131.9 (4C, CH), 132.4 (4C,
CH), 161.4 (2C, Cquat, CO); MS (EI, 70 eV) m/e (%) ¼ 340 (Mþ),
338 (Mþ), 185, 183.
871, 841, 787, 714, 505 cmꢁ1; 1H NMR (CDCl3, 400 MHz)
d:
1.41 (t, 3J ¼ 7.2 Hz, 3H), 4.42 (q, 3J ¼ 7.2 Hz, 2H, OCH2), 8.19
(d, 3J ¼ 9.2 Hz, 2H), 8.26 (d, 3J ¼ 9.2 Hz, 2H); 13C NMR
(CDCl3, 100.5 MHz) d: 14.2 (CH3), 62.0 (OCH2), 123.5 (2C,
CH), 130.6 (2C, CH), 135.8 (Cquat), 150.4 (Cquat), 164.7 (Cquat
,
4.3.6. 3-Chlorocinnamic anhydride (9b)
CO). Anal. Calcd for C9H9NO4 (195.17): C, 55.39%; H, 4.65%;
N, 7.18%. Found: C, 55.53%; H, 4.69%; N, 7.10%.
Silvery shiny needles, mp 117e118 ꢀC; IR (KBr) nmax
:
3079, 1758, 1709, 1629, 1134, 940, 784, 665 cmꢁ1 1H NMR
;
(CDCl3, 400 MHz)
d
: 6.52 (d, 3J ¼ 16.0 Hz, 2H), 7.35e7.46 (m,
4.4.2. Isopropyl 4-nitrobenzoate (11bꢀ)
6H), 7.57 (s, 2H), 7.78 (d, 3J ¼ 16.0 Hz, 2H); 13C NMR (CDCl3,
Colorless crystals; mp 110e112 C; IR (neat) nmax: 3112,
3081, 3076, 2987, 2939, 2880, 1713, 1525, 1282, 1100, 1011,
100.5 MHz) d: 118.0 (2C, CH), 126.8 (2C, CH), 128.2 (2C, CH),
130.4 (2C, CH), 131.2 (2C, CH), 135.2 (2C, Cquat), 135.4 (2C,
quat), 147.1 (2C, CH), 161.9 (2C, Cquat, CO). Anal. Calcd for
918, 875, 841, 788, 718 cmꢁ1; 1H NMR (CDCl3, 400 MHz)
d:
C
1.38 (d, 3J ¼ 6.4 Hz, 6H, 2 CH3), 5.27 (hept., 3J ¼ 6.4 Hz, 1H),
C18H12Cl2O3 (347.19) C, 62.27%; H, 3.48%. Found: C, 62.43%;
H, 3.57%.
8.18 (d, 3J ¼ 9.2 Hz, 2H), 8.25 (d, 3J ¼ 9.2 Hz, 2H); 13C NMR
(CDCl3, 100.5 MHz) d: 21.8 (2C, 2 CH3), 69.7 (OCH), 123.4
(2C, CH), 130.6 (2C, CH), 136.2 (Cquat), 150.4 (Cquat), 164.2
(Cquat, CO). Anal. Calcd for C10H11NO4 (209.20): C, 57.41%; H,
5.30%; N, 6.70%. Found: C, 57.33%; H, 5.45%; N, 6.68%.
4.3.7. Bis(2,5-dimethoxycinnamic) anhydride (9c)
Pale yellow solid; mp 103e105 ꢀC; IR (KBr) nmax: 3078,
3008, 2947, 2912, 1837, 1714, 1704, 1625, 1579, 1498, 1458,
1428, 1322, 1290, 1255, 1206, 1086, 1049, 1018, 985, 947,
4.4.3. Benzyl 3-chlorobenzoate (11c) [39]
866, 805, 719, 669 cmꢁ1; 1H NMR (CDCl3, 400 MHz)
d: 3.80
Colorless oil; nmax (neat/cmꢁ1) 3067, 3034, 2954, 2888,
1723, 1575, 1278, 1254, 1126, 1073, 747, 696; dH
(400 MHz, CDCl3) 5.36 (2H, s, OCH2), 7.35e7.45 (6H, m),
7.52 (1H, d, 3J ¼ 8.0 Hz), 7.95 (1H, d, 3J ¼ 8.0 Hz), 8.04
(1H, s); dC (100.5 MHz, CDCl3) 67.1 (OCH2), 127.8 (CH),
128.3 (2C, CH), 128.4 (2C, CH), 128.7 (CH), 129.7 (CH),
129.8 (CH), 131.8 (Cquat), 133.1 (CH), 134.5 (Cquat), 135.6
(Cquat), 165.2 (Cquat, CO).
(s, 6H, 2 OCH3), 3.86 (s, 6H, 2 OCH3), 6.60 (d, 3J ¼ 16.0 Hz,
2H), 6.87 (d, 3J ¼ 8.8 Hz, 2H), 6.96 (dd, 3J ¼ 8.8 Hz,
4J ¼ 2.8 Hz, 2H), 7.06 (d, 4J ¼ 2.8 Hz, 2H), 8.12 (d,
3J ¼ 16.0 Hz, 2H); 13C NMR (CDCl3, 100.5 MHz) 55.8 (2C, 2
OCH3), 56.1 (2C, 2 OCH3),112.5 (2C, CH),113.6 (2C, CH),117.5
(2C, CH), 118.3 (2C, CH), 123.2 (2C, Cquat), 143.8 (2C, CH),
153.3 (2C, Cquat), 153.5 (2C, Cquat), 163.2 (2C, Cquat, CO). Anal.
Calcd for C22H22O7 (398.41): C, 66.32%; H, 5.57%. Found: C,
66.74%; H, 5.62%.
4.4.4. Heptyl 2-chlorobenzoate (11d) [40]
Colorless oil; nmax (neat/cmꢁ1) 2956, 2929, 2857, 1732,
1593, 1469, 1436, 1292, 1250, 1118, 1051, 747; dH (400 MHz,
CDCl3) 0.88 (3H, t, 3J ¼ 7.0 Hz, CH3), 1.26e1.58 (8H, m),
1.72e1.77 (2H, m), 4.32 (2H, t, 3J ¼ 6.4 Hz, OCH2), 7.28e7.45
(3H, m), 7.79 (1H, dd, 3J ¼ 7.6 Hz, 4J ¼ 2.0 Hz); dC
(100.5 MHz, CDCl3) 14.1 (CH3), 22.6 (CH2), 26.0 (CH2), 28.6
(CH2), 28.9 (CH2), 31.7 (CH2), 65.7 (OCH2), 126.5 (CH), 130.5
4.3.8. Bis(3,4-dimethoxycinnamic) anhydride (9d)
Pale yellow solid; mp 177e179 ꢀC; IR (KBr) nmax: 3119,
3072, 2995, 2993, 2960, 2931, 2835, 1756, 1716, 1627, 1598,
1581, 1513, 1461, 1425, 1270, 1163, 1444, 1084, 1023, 1001,
869, 815 cmꢁ1; 1H NMR (CDCl3, 200 MHz)
d: 3.95 (s, 12H, 4
OCH3), 6.41 (d, 3J ¼ 15.6 Hz, 2H), 6.91 (d, 3J ¼ 8.4 Hz, 2H),
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10
M. Al-Azani et al. / C. R. Chimie xxx (2016) 1e12
(Cquat), 130.9 (CH),131.3 (CH), 132.3 (CH), 133.6 (Cquat), 165.9
(Cquat, CO).
55.3 (OCH3), 104.0 (CH), 114.7 (2C, CH), 127.3 (2C, CH), 128.7
(Cquat), 136.5 (CH), 159.6 (Cquat) and 13e (826 mg, 80%) as a
pale yellow solid; mp 130e133 ꢀC; IR (KBr) nmax: 1754,1624,
1602, 1573, 1524, 1513, 1351, 1309, 1286, 1249, 1178, 1102,
4.4.5. 3-O-Methylestra-1,3,5(10)-trien-17b-yl 4-(E)-
methoxycinnamate (11e)
1026, 981, 921, 825, 735 cmꢁ1; 1H NMR (400 MHz, CDCl3)
d:
As a colorless solid, mp 126e128 ꢀC; IR (KBr/cmꢁ1
)
nmax
:
2.50 (s, 3H, CH3), 3.84 (s, 3H, OCH3), 6.46 (d, 3J ¼ 16.0 Hz,
2919, 2866, 2836, 1701, 1636, 1604, 1575, 1512, 1497, 1323,
1H), 6.92 (d, 3J ¼ 8.8 Hz, 2H), 7.53 (d, 3J ¼ 8.8 Hz, 2H), 7.60
1257, 1205, 1172, 1033, 984, 967, 828, 812; 1H NMR
(dd, J ¼ 8.0 Hz, 3J ¼ 8.0 Hz, 1H), 7.82 (d, 3J ¼ 16.0 Hz, 1H),
3
(400 MHz, CDCl3)
d: 0.90 (3H, s, CH3), 1.25e2.31 (13H, m),
8.20 (dm, 3J ¼ 8.0 Hz, 1H), 8.29 (dm, 3J ¼ 8.0 Hz, 1H), 8.56
2.85e2.87 (2H, m), 3.77 (3H, s, OCH3), 3.83 (3H, s, OCH3),
4.82 (1H, dd, 3J ¼ 9.2 Hz, 3J ¼ 8.0 Hz), 6.32 (1H, d,
3J ¼ 16.0 Hz), 6.63 (1H, d, 4J ¼ 2.8 Hz), 6.70 (1H, dd,
3J ¼ 8.8 Hz, 4J ¼ 2.8 Hz), 6.90 (2H, d, 3J ¼ 8.8 Hz), 7.20 (1H, d,
3J ¼ 8.4 Hz), 7.48 (2H, d, 3J ¼ 8.8 Hz), 7.62 (1H, d,
(dd, 4J ¼ 2.0 Hz, 4J ¼ 1.6 Hz, 1H); 13C NMR (100.5 MHz,
CDCl3) d: 14.4 (CH3), 55.4 (OCH3), 112.4 (CH), 114.4 (2C, CH),
122.1 (CH), 125.1 (CH), 126.9 (Cquat), 129.7 (CH), 130.1 (2C,
CH), 132.9 (CH), 136.8 (Cquat), 146.5 (CH), 148.4 (Cquat), 160.5
(Cquat), 161.8 (Cquat), 164.6 (Cquat). Anal. Calcd for
C18H16N2O5 (340.33): C, 63.63; H, 4.85; N, 8.19%. Found: C,
63.89; H, 4.87; N, 7.96%.
3J ¼ 16.0 Hz); 13C NMR (100.5 MHz, CDCl3)
d
: 12.2, 23.3,
26.2, 27.2, 27.7, 29.8, 37.0, 38.6, 43.2, 43.8, 49.8, 55.2 (OCH3),
55.4 (OCH3), 82.6 (OCH), 111.5 (CH), 113.8 (CH), 114.3 (2C,
CH), 116.1 (CH), 126.4 (CH), 127.2 (Cquat), 129.7 (2C, CH),
132.5 (Cquat), 137.9 (Cquat), 144.0 (CH), 157.4 (Cquat), 161.3
(Cquat), 167.4 (Cquat, CO). Anal. Calcd for C29H34O4. (446.58):
C, 78.00%; H, 7.67%. Found: C, 78.14%; H, 7.44%.
4.5.2. 3-O-Methyl estra-1-3,5(10)-trien-17-one-17-oxime N-
3,4-(E)-dimethoxycinnamate (13a)
As a colorless solid, mp 152e154 ꢀC (isopropanol/diethyl
ether); IR (KBr/cmꢁ1
) nmax 3061, 2930, 2864, 2837, 1734,
1627, 1597, 1513, 1465, 1420, 1307, 1266, 1236, 1162, 1124,
4.4.6. 3-O-Methylestra-1,3,5(10)-trien-17b-yl 3,4-(E)-
1021, 979, 863, 816 cmꢁ1; 1H NMR (CDCl3, 400 MHz, CDCl3)
dimethoxycinnamate (11f)
d
: 0.83e2.91 (m, 15H), 1.05 (s, 3H, CH3), 2.91 (s, 3H, OCH3),
As a colorless solid, mp 162e165 ꢀC; nmax (KBr/cmꢁ1
)
3.77 (s, 3H, OCH3), 3.92 (s, 3H, OCH3), 6.37 (d, 3J ¼ 16.0 Hz,
1H), 6.63 (d, 4J ¼ 2.8 Hz, 1H), 6.71 (dd, 3J ¼ 8.8 Hz,
4J ¼ 2.8 Hz,1H), 6.87 (d, 3J ¼ 8.4 Hz,1H), 7.06 (d, 4J ¼ 2.0 Hz),
7.13 (dd, 3J ¼ 8.4 Hz, 4J ¼ 2.0 Hz,1H), 7.21 (d, 3J ¼ 8.8 Hz,1H),
3010, 2953, 2863, 2843, 2805, 2698, 1612, 1596, 1510, 1445,
1417, 1294, 1257, 1155, 1139, 1024, 848, 812, 782, 616, 570;
dH (400 MHz, CDCl3) 0.90 (3H, s, CH3), 2.84e2.88 (2H, m),
1.25e2.31 (13H, m), 3.77 (3H, s, OCH3), 3.91 (3H, s, OCH3),
3.92 (3H, s, OCH3), 4.83 (1H, dd, 3J ¼ 8.0, 3J ¼ 7.6 Hz, OCH),
6.32 (1H, d, 3J ¼ 16.0 Hz), 6.63 (1H, d, 4J ¼ 2.8 Hz), 6.70
(1H, dd, 3J ¼ 8.4 Hz, 4J ¼ 2.8 Hz), 6.86 (1H, d, 3J ¼ 8.4 Hz),
7.05 (1H, d, 4J ¼ 2.0 Hz), 7.10 (1H, dd, 3J ¼ 8.4 Hz,
4J ¼ 2.0 Hz), 7.20 (1H, d, 3J ¼ 8.4 Hz), 7.61 (1H, d,
3J ¼ 16.0 Hz); dC (100.5 MHz, CDCl3) 12.2, 23.3, 26.2, 27.2,
27.7, 29.8, 37.0, 38.6, 43.2, 43.8, 49.8, 55.2 (OCH3), 55.9
(OCH3), 56.0 (OCH3), 82.7 (OCH), 109.5, 111.0, 111.5, 113.8,
116.2, 122.6, 126.4, 127.5, 132.5, 137.9, 144.3, 149.2 (Cquat),
151.0 (Cquat), 157.4 (Cquat), 167.3 (Cquat, CO). Found: C,
75.76%; H, 7.32%. Calcd. for C30H36O5. (476.60): C, 75.60%;
H, 7.61%.
7.71 (d, 3J ¼ 16.0 Hz, 1H); 13C NMR (CDCl3, 100.5 MHz)
d:
17.1, 22.9, 26.1, 27.2, 27.3, 29.6, 33.7, 38.2, 43.8, 45.5, 52.8,
55.2 (OCH3), 55.9 (OCH3), 56.0 (OCH3), 109.7, 111.0, 111.5,
113.8, 113.9, 122.7, 126.4, 127.4, 132.1, 137.6, 145.4, 149.2,
151.2, 157.5, 165.1, 178.7 (Cquat, CO). Found: C, 73.69%; H,
7.37%; N, 2.73%. Calcd. for C30H35NO5 (489.60): C, 73.59%; H,
7.21%; N, 2.86%.
4.5.3. Fluoren-9-one oxime benzoate (13b)
As a yellow solid, mp 180e183 ꢀC; IR (KBr) nmax: 1743,
1597, 1449, 1319, 1248, 1178, 1091, 1081, 1064, 1026, 975,
889, 785, 731, 711, 644 cmꢁ1; 1H NMR (CDCl3, 400 MHz)
d:
7.30e7.69 (m, 9H), 8.01 (d, 3J ¼ 7.6 Hz, 1H), 8.21 (d,
3J ¼ 7.2 Hz, 2H), 8.29 (d, 3J ¼ 7.6 Hz, 1H); 13C NMR (CDCl3,
4.5. General procedure for the preparation of O-acyloximes
100.5 MHz) d: 120.1 (CH), 120.4 (CH), 123.6 (CH),128.5 (CH),
128.6 (CH), 128.8 (2C, CH), 128.9 (Cquat), 129.9 (3C, CH),
130.1 (Cquat), 131.7 (CH), 132.6 (CH), 133.6 (CH), 134.5 (Cquat),
141.1 (Cquat), 142.8 (Cquat), 159.1 (Cquat), 164.2 (Cquat). Anal.
Calcd for C20H13NO2. (299.32) 0.2H2O: C, 79.30%; H, 4.46%,
N 4.62%. Found: C, 79.26%; H, 4.34%; N, 4.64%.
4.5.1. 3-Nitroacetophenone oxime 4-methoxycinnamate (13e)
To
a
solution of triphenylphosphine (910 mg,
3.47 mmol) in dry dichloromethane (10 mL) bromotri-
chloromethane (710 mg, 3.58 mmol) was added, and the
resulting mixture was stirred at a rate for 30 min to give a
reddish-brownish solution. Then, 4-methoxycinnamic acid
(4d, 542 mg, 3.04 mmol) was added, and the mixture was
stirred at reflux for 45 min. Thereafter, 3-
nitroacetophenone oxime (12c, 545 mg, 3.03 mmol) was
added, and the mixture was stirred at reflux for another
12 h. Column chromatography on a silica gel (CH2Cl2) gave
(E)-1-bromo-2-(4-methoxyphenyl)ethene (6, 77 mg, 12%)
[41] as a colorless solid; mp 52e56 ꢀC (Lit. mp 58e59 ꢀC
[42]); nmax (KBr/cmꢁ1) 2958, 2837, 1607, 1512, 1256, 1028,
950, 927, 836, 777, 526; dH (400 MHz, CDCl3) 6.60 (1H, d,
3J ¼ 14.0 Hz), 6.84 (2H, d, 3J ¼ 8.4 Hz), 7.03 (1H, d,
3J ¼ 14.0 Hz), 7.22 (2H, d, 3J ¼ 8.4 Hz); dC (100.5 MHz, CDCl3)
4.5.4. Fluoren-9-one oxime cinnamate (13c)
As a pale yellow solid; mp 126e128 ꢀC; IR (KBr) nmax
:
3029, 1746, 1634, 1449, 1308, 1116, 951, 788, 761, 733,
646 cmꢁ1; 1H NMR (CDCl3, 400 MHz)
d
: 6.74 (d, 3J ¼ 16.0 Hz,
1H), 7.28e7.66 (m, 11H), 7.97 (md, 1H), 7.98 (d, 3J ¼ 16.0 Hz,
1H), 8.31 (md, 1H); 13C NMR (CDCl3, 100.5 MHz)
d: 114.9
(CH), 120.1 (CH), 120.3 (CH), 123.5 (CH), 128.4 (3C, CH),
128.5 (CH), 129.0 (2C, CH), 130.1 (CH), 130.2 (Cquat), 130.9
(CH), 131.7 (CH), 132.6 (CH), 134.1 (Cquat), 134.5 (Cquat), 141.2
(Cquat), 142.6 (Cquat), 147.3 (CH), 158.4 (Cquat), 164.6 (Cquat
,
CO). Anal. Calcd for C22H15NO2 (325.36): C, 81.21%; H,
4.65%; N, 4.30%. Found: C, 81.49%; H, 4.70%; N, 4.36%.
Please cite this article in press as: M. Al-Azani, et al., The use of BrCCl3-PPh3 in Appel type transformations to esters, O-acy-
loximes, amides, and acid anhydrides, Comptes Rendus Chimie (2016), http://dx.doi.org/10.1016/j.crci.2016.04.004

M. Al-Azani et al. / C. R. Chimie xxx (2016) 1e12
11
4.5.5. 3-Nitroacetophenone oxime benzoate (13d)
Acknowledgements
Ms. M. Al Azani thanks the UAEU for a PhD scholarship.
References
As a colorless solid, mp 139e141 ꢀC; IR (KBr) nmax: 1746,
1530, 1349, 1246, 1057, 1021, 931, 776, 738, 707, 676,
670 cmꢁ1 1H NMR (400 MHz, CDCl3)
; d: 2.59 (s, 3H, CH3),
7.49e7.53 (m, 2H), 7.61e7.63 (m, 2H), 8.13 (d, 3J ¼ 7.6 Hz,
2H), 8.26 (d, 3J ¼ 7.6 Hz, 1H), 8.32 (dd, 3J ¼ 7.6 Hz,
4J ¼ 1.2 Hz, 1H), 8.61 (s, 1H); 13C NMR (100.5 MHz, CDCl3)
d:
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14.6 (CH3), 122.1 (CH), 125.3 (CH), 128.7 (2C, CH), 129.7 (3C,
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C15H12N2O4. (284.27): C, 63.38%; H, 4.25%, N 9.85%. Found:
C, 63.36%; H, 4.27%; N, 9.88%.
4.5.6. 6-Methoxy-1-tetralone oxime 3,4-dimethoxycinnamate
(13f)
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:
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; d: 1.89 (m, 2H),
2.75 (dd, 3J ¼ 6.0 Hz, 3J ¼ 6.0 Hz, 2H), 2.92 (dd, 3J ¼ 6.0 Hz,
3J ¼ 6.0 Hz, 2H), 3.81 (s, 3H, OCH3), 3.92 (s, 6H, 2 OCH3),
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d: 21.4 (CH2), 25.6
(CH2), 29.9 (CH2), 55.3 (OCH3), 55.9 (OCH3), 56.0 (OCH3),
109.7 (CH), 111.0 (CH), 113.0 (2C, CH), 113.6 (Cquat), 121.7
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,
4.5.7. 2,5-Dimethoxyacetophenone oxime 4-nitrobenzoate
(13g)
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2992, 2969, 2937, 2836, 1741, 1606, 1527, 1499, 1468, 1410,
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ꢁ
ꢁ
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loximes, amides, and acid anhydrides, Comptes Rendus Chimie (2016), http://dx.doi.org/10.1016/j.crci.2016.04.004

12
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Please cite this article in press as: M. Al-Azani, et al., The use of BrCCl3-PPh3 in Appel type transformations to esters, O-acy-
loximes, amides, and acid anhydrides, Comptes Rendus Chimie (2016), http://dx.doi.org/10.1016/j.crci.2016.04.004