4-Aminophenyl diphenylphosphinite (APDPP) as a heterogeneous and acid scavenger reagent for thiocyantion or isothiocyanation of alcohols and protected alcohols

Article abstract of DOI:10.1080/10426500802417950

4-Aminophenyl diphenylphosphinite (APDPP) as a heterogeneous phosphinite reagent is used for the efficient conversion of alcohols, trimethylsilyl- and tetrahydropyranyl ethers, α-hydroxy phosphonates, and - trimethylsilyloxyphosphonates to their corresponding thiocyanates or isothiocyanates in the presence of Br₂ and NH₄SCN.

Full text of DOI:10.1080/10426500802417950

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4-Aminophenyl
Diphenylphosphinite (APDPP)
as a Heterogeneous and
Acid Scavenger Reagent
for Thiocyantion or
Isothiocyanation of Alcohols
and Protected Alcohols
Nasser Iranpoor a , Habib Firouzabadi a & Mohammad
Gholinejad a
a Chemistry Department, College of Sciences, Shiraz
University, Shiraz, Iran
Published online: 22 Jul 2009.
To cite this article: Nasser Iranpoor , Habib Firouzabadi & Mohammad Gholinejad
(2009): 4-Aminophenyl Diphenylphosphinite (APDPP) as a Heterogeneous and Acid
Scavenger Reagent for Thiocyantion or Isothiocyanation of Alcohols and Protected
Alcohols, Phosphorus, Sulfur, and Silicon and the Related Elements, 184:8, 2010-2019
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Phosphorus, Sulfur, and Silicon, 184:2010–2019, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500802417950
4-Aminophenyl Diphenylphosphinite (APDPP)
as a Heterogeneous and Acid Scavenger Reagent
for Thiocyantion or Isothiocyanation of Alcohols
and Protected Alcohols
Nasser Iranpoor, Habib Firouzabadi,
and Mohammad Gholinejad
Chemistry Department, College of Sciences, Shiraz University, Shiraz,
Iran
4-Aminophenyl diphenylphosphinite (APDPP) as a heterogeneous phosphinite
reagent is used for the efficient conversion of alcohols, trimethylsilyl- and tetrahy-
dropyranyl ethers, α-hydroxy phosphonates, and α-trimethylsilyloxyphosphonates
to their corresponding thiocyanates or isothiocyanates in the presence of Br and
2
NH SCN.
4
Keywords Alcohol; 4-aminophenyl diphenylphosphinite; isothiocyanate; tetrahydropy-
ranyl ether; thiocyanate; trimethylsilyl ether
INTRODUCTION
Conversion of alcohols to alkyl halides and alkyl thiocyanates or
isothiocyanates by the use of phosphines has been widely studied.1–6
Apart from these reactions, the use of in situ generated PPh3(SCN)2
for this transformation is also reported.7,8 In these reactions, the
separation of the soluble phosphine oxide byproduct is tedious and
time-consuming work. Some attempts to solve this problem, such
as the use of polymer supported phosphines,9–12 phosphines tagged
crown ethers,13 (p-dimethyl aminophenyl)-diphenylphosphine (DAP-
DP),14 1,2-bis(diphenylphosphineo)ethane,15 4-diphenyl phosphinyl
benzoic acid 2-trimethylsilanyl ether ester (DPPBE),16 and perfluori-
nated phosphines17 are reported in the literature. Polymer supported
Received 16 April 2008; accepted 18 August 2008.
We are grateful to Shiraz University Research Council for the partial support of this
work and for a grant from Organization of Management and Programming of Iran.
Address correspondence to Nasser Iranpoor and Habib Firouzabadi, Chemistry De-
partment, College of Sciences, Shiraz University, Shiraz 71454, Iran. E-mail: iran-
poor@chem.susc.ac.ir; firouzabadi@chem.susc.ac.ir
2010

Thiocyanation of Alcohols and Protected Alcohols
2011
FIGURE 1 The structure of APDPP.
phosphines are the most widely used heterogeneous reagents for re-
placement of triphenylphosphine in organic synthesis. We have also
recently prepared and applied (SiO2)nPCl3−n, (Silphos) as an inor-
ganic, silica-based, polymeric phosphorane reagent in different organic
transformations.18-19 However, apart from their costs, the polymeric
reagents usually have the problems of lower efficiency compared to
the monomeric ones and also difficulty of scaling-up the reactions. In
this article, we report the use of 4-aminophenyl diphenylphosphinite
(APDPP) (Figure 1) as a heterogeneous and acid scavenger reagent
for the conversion of alcohols, and trimethylsilyl and tetrahydropy-
ranyl ethers to their corresponding thiocyanates or isothiocyanates
in the presence of molecular bromine and NH4SCN in acetonitrile
at room temperature (Scheme 1). α-Hydroxyphosphonates and α-
trimethylsilyloxyphosphonates were also successfully subjected to this
transformation (Scheme 2).
SCHEME 1
SCHEME 2

2012
N. Iranpoor et al.
RESULTS AND DISCUSSION
There are different reagent systems reported in the literature for
the preparation of thiocyanates as important and valuable sulfur-
containing compounds.20–24 Most of the reported methods involve the
use of homogeneous phosphorous-containing reagents and usually suf-
fer from the tedious work-up procedure and isolation of the produced
byproduct phosphorous oxide compounds. Recently, we have introduced
4-aminophenphyl diphenylphosphinite (APDPP) as a heterogeneous
phosphinite reagent for the conversion of alcohols and protected al-
cohols to their corresponding halides in the presence of molecular halo-
gens or N-halosuccinimides.25
Now we report on the applicability of this heterogeneous phos-
phorane (APDPP) for the efficient conversion of hydroxyl function-
ality and its trimethylsilyl and tetrahydropyranyl derivatives to
thiocyanate or isothiocyanate functionalities in the presence of Br2
and NH4SCN. Optimization of the reaction conditions showed that
the stoichiometric ratio of 1:1.6:1.6:3.2 for the mixture of benzyl
alcohol/APDPP/Br2/NH4SCN in CH3CN at room temperature is suit-
able for conversion of benzyl alcohol to its corresponding thiocyanate.
These reaction conditions were then applied for the conversion of struc-
turally different alcohols and α-hydroxyphosphinates to their thio-
cyanates or isothiocyanates. The results of this study are shown in
Table I.
The suggested mechanism is similar to that which has been proposed
for Ph3P (Scheme 3).7,8
SCHEME 3

Thiocyanation of Alcohols and Protected Alcohols
2013
APDPP/Br2, NH4SCN
ROH−−−−−−−−−−−−−−→ RSCN and/orRNCS
MeCN, r.t
TABLE I Conversion of Alcohols and α-Hydroxyphosphinates into
Thiocyanates or Isothiocyanatesa,b
Time
(h)
Ratio of
RSCN/RNCS
Isolated
yield %
Entry
R
1
2
3
4
5
6
7
8
Benzyl
1
0.75
5
1
3
3
8
5
100/0
92/8
94
82
80
90
p-methoxybenzyl
p-nitrobenzyl
1-phenyl-3-propyl
2-octyl
1,1-diphenylmethyl
1-adamantyl
100/0
100/0
54/46
0/100
15/85
85/15
89 (as mixture)
90
85 ( as mixture)
63
benzyl- HPO(OEt)
C
2
|
9
p-methoxybenzyl- HPO(OEt)
5
80/20
60
C
2
|
aOptimized ratio of ROH/APDPP/Br2/NH4SCN is 1:1.6:1.6:3.2.
bAll the products are known compounds and identified by comparison of their
spectral data with those prepared according to the literature.6–9,28,29
The conversion of alcohols into thiocyanates or isothiocyates could
occur through the reaction between APDPP (I) with molecular bromine
to produce APDPP+Br/Br− (II), followed by the reaction with NH4SCN
to produce the reactive heterogeneous APDPP+SCN/SCN− (III) as the
thiocyataing agent. Attack of alcohol to the positively charged phospho-
nium ion in APDPP+SCN/SCN− (III) makes the hydroxyl functionality
a good leaving group in which its nucleophilic substitution with thio-
cyanate or isothiocyanate ions produces the product. In support of this
mechanism, the precipitated ammonium thiocyanate salt of the corre-
sponding phosphinate ester (IV) was easily isolated by filtration and
washed with water to remove its contaminated ammonium bromide.
After drying in vacuum oven, its IR spectrum as KBr disk showed the
ammonium group as a broad strong band centered at 3105 cm−1. The
absorption bands for SCN and P O groups also appear as strong bands
at 2056 and 1400 cm−1, respectively. The formation of (IV) shows the
acid scavenger nature of this phosphinite reagent.
We then examined the possibility of this transformation for
trimethylsilyl and also THP ethers. The optimized stoichiometric ratios
of ROSiMe3/APDPP/Br2/NH4SCN and ROTHP/APDPP/Br2/NH4SCN
were found to be 1:1.2:1.2:2.4 and 1:2:2:4, respectively, in CH3CN
at room temperature. These optimized ratios were employed for the

2014
N. Iranpoor et al.
APDPP/Br2, NH4SCN
ROY−−−−−−−−−−−−−−−→ RSCN and/or RNCS
MeCN, r.t
TABLE II Conversion of Trimethylsilyl Ethers,
α-Trimethylsilyloxyphosphonates, and Tetrahydropyranyl Ethers
into Thiocyanates and Isothiocynatesa,b
RSCN/
RNCS
Isolated
yield (%)
Entry
R
Y
Time
1
2
3
4
benzyl
SiMe3
SiMe3
SiMe3
SiMe3
immediately
immediately
5 min
100/0
92/8
100/0
52/48
92
86
90
p-methoxybenzyl
o-nitrobenzyl
2-octyl
5 min
89 (as a
mixture)
90
5
6
7
8
9
1,1-diphenylmethyl
benzyl
1-phenyl-3-propyl
1,1-diphenylmethyl
SiMe3
THP
THP
THP
SiMe3
5 min
7 h
8 h
24 h
45 min
0/100
100/0
100/0
0/100
92/8
83
80
70
85
benzyl- HPO(OEt)
C
2
|
10
11
p-methoxybenzyl -CHPO(OEt)2
SiMe3
SiMe3
30 min
1 h
88/12
94/6
77
80
|
p-chlorobenzyl- HPO(OEt)
C
2
|
aThe molar ratio of ROTHP/APDPP/Br2/NH4SCN is 1:2:2:4 and α-trimethylsilyloxy-
phosphonates or ROSiMe3/APDPP/Br2/NH4SCN is 1:1.2:1.2:2.4.
bAll the products are known compounds and identified by comparison of their
spectral data with those prepared according to the literature.6–9,28
conversion of trimethylsilyl ethers, tetrahydrpyranyl ethers, and also
α-trimethylsilyloxyphosphinate to their corresponding thiocyanates or
isothiocyanates in good to high yields. The results of this study are
shown in Table II.
The formation of thiocyanates or isothiocyanates in these reactions is
a structure-dependent reaction that has been previously observed by us
and the other groups.5–7 It has been observed that increasing the steric
hindrance of the substrate increases the formation of isothiocyates. The
results of Tables I and II show that the reaction of primary alcohols
produces thiocyanates as the sole product along with trace formation
of isothiocyanates as the minor products (0–8%). For 2-octanol as a
secondary alcohol, both thiocyanate and isothiocyanate were obtained
in nearly equal amounts. Also, benzhydrol as a bulky alcohol gave its
isothiocyanate as the sole product of the reaction. For 1-adamananol
as a tertiary alcohol, its corresponding isothiocyanate and thiocyanate
were produced with the ratio 85:15.

Thiocyanation of Alcohols and Protected Alcohols
2015
APDPP/Br2, NH4SCN
ROY−−−−−−−−−−−−−−−→ RSCN and/or RNCS
MeCN, r.t
TABLE III Selective Reaction of Trimethyl Silyl Ethers in the
Presence of Hydroxyl Compounds
Entry
1
Binary mixture
benzyl
R
Time (min)
1
GC yields (%)a
H
0
100
0
100
0
100
10
90
5
95
5
SiMe3
H
SiMe3
H
SiMe3
H
SiMe3
H
2
3
4
5
6
p-methoxybenzyl
1
5
o-nitrobenzyl
2-octyl
5
1,1-diphenylmethyl
5
SiMe3
H
SiMe3
benzyl- HPO(OEt)
C
45
2
|
95
aThe yield was determined by GC analysis using internal standard.
We have also observed that with APDPP/Br2/NH4SCN, the conver-
sion of trimethylsilyl ethers to their thiocyanates or isothiocyanates is
a highly selective reaction in the presence of their alcohols. We have
shown this selectivity by a series of competitive reactions in binary
mixtures as summarized in Table III.
The reason for the higher reactivity of trimethylsilyl ethers com-
pared to alcohols is not clear to us. However, we may suggest that the
more pronounced H-bonding interaction between alcohol molecules and
the amino group of APDPP(III) makes them less reactive compared to
silyl ethers in this transformation.
EXPERIMENTAL
Chemicals were either prepared in our laboratory or obtained from
Fluka (Switzerland) and Merck chemical companies. Infrared spectra
were recorded on a Perkin-Elmer 781 spectrometer. Nuclear magnetic
resonance spectra were recorded on an Avance DPX-250 MHz spec-
trometer. GC analyses were recorded on a Shimadzu GC-14A.
Typical Procedure for the Conversion of Benzyl Alcohol
to Benzyl Thiocyanate by APDPP/Br2/NH4SCN
To a flask containing a stirring mixture of APDPP (0.46 g, 1.6 mmol) and
Br2 (0.08 mL, 1.6 mmol), NH4SCN (0.24 g, 3.2 mmol) in dry CH3CN

2016
N. Iranpoor et al.
(7 mL) was added at room temperature and stirred for 2 h until all
bromine was consumed. Then benzyl alcohol (0.1 mL, 1 mmol) was
added to this mixture. TLC monitoring or GC analysis showed the
completion of the reaction after 1 h. The reaction mixture was filtered
to remove the produced heterogeneous phosphinate ester and ammo-
nium bromide. The solvent was then evaporated, and the residue was
washed with 25 mL of diethyl ether. Diethyl ether was then evaporated
and for further purification, the product was chromatographed on a col-
umn of silica-gel using n-hexane-ethyl acetate (5:1) as eluent. Benzyl
thiocyanate was obtained in 94% yield (0.14 g), mp = 38–39◦C (Lit.8,
1
mp 39–40◦C), H NMR (CDCl3/TMS): δ = 4.25 (2H, s), 7.21–7.31 (5H,
m); 13C NMR (CDCl3/TMS): δ = 134.8, 129.5, 129.4, 129.3, 112.4, 38.7.
This reaction was also successfully scaled up to 8 folds. Isolated yield
for the scaled up reaction was found to be 91%.
Typical Procedure for the Conversion of Benzyl Trimethylsilyl
Ether to Benzylthiocyanate by APDPP/Br2/NH4SCN
NH4SCN (0.18 g, 2.4 mmol) was added to a flask containing APDPP
(0.35 g, 1.2 mmol) and Br2 (0.06 ml, 1.2 mmol) in CH3CN (7 mL) at room
temperature. After 2 h, the orange color of bromine changed to pale
yellow or disappeared. To this reaction mixture, benzyltrimethylsilyl
ether (0.18 g, 1 mmol) was added at room temperature. GC analysis
or TLC monitoring showed the completion of the reaction after 1 min.
For isolation of the produced phosphinite ester byproduct, the mixture
was filtered. After evaporation of the solvent, the residue was washed
with diethyl ether (25 mL). The crude product was chromatographed
on a column of silica-gel using n-hexane-ethyl acetate (5:1) as eluent.
The corresponding thiocyanate was obtained in 92% yields (0.13 g). The
product was identified by comparison with a known sample.8
Typical Procedure for the Conversion of
Benzyltetrahydropyranyl Ether to Benzylthiocyanate by
APDPP/Br2/NH4SCN
To a flask containing a stirring mixture of APDPP (2 mmol, 0.58 g)
and Br2 (2 mmol, 0.1 ml) in CH3CN (7 mL), NH4SCN (0.3 g, 4 mmol)
was added at room temperature. After 2 h, benzyltetrahydropyranyl
ether (0.18 g, 1 mmol) was added to the reaction mixture. TLC and GC
analysis of the reaction showed the completion of the reaction after 7
h. The reaction mixture was filtrated to remove the produced phosphi-
nate ester. After evaporation of the solvent, the residue was washed
with 25 mL of diethyl ether. In order to purify the obtained product, it

Thiocyanation of Alcohols and Protected Alcohols
2017
was passed through a short column of silica-gel using n-hexane-ethyl
acetate (5:1) as eluent. Benzyl thiocyanate was obtained in 83% yield
(0.12 g).
Typical Procedure for the Conversion of Diethyl
α-Hydroxybenzylphosphinate to Diethyl
α-Thiocyanatobenzylphosphinate Using APDPP/Br2/NH4SCN
To a flask containing APDPP (0.46 g, 1.6 mmol) and Br2 (0.1 ml,
2 mmol) in CH3CN (7 mL), NH4SCN (0.24 g, 3.2 mmol) was added
at room temperature and stirred for 2 h. To this reaction mixture, di-
ethyl α-hydroxybenzylphosphinate (0.244 g, 1 mmol) was added. TLC
and GC analysis showed the completion of reaction after 5 h. The mix-
ture was filtered, and after evaporation of solvent, the residue was
washed with diethyl ether (25 mL). After evaporation, the residue was
chromatographed over a short column of silica-gel (2 cm thick) using
n-hexane-ethyl acetate as an eluent. α-Thiocyanatobenzylphosphinate
was obtained in 63% yield, 0.18 g. The product was identified by com-
parison of its spectral data with the literature.6a
Typical Procedure for the Conversion of Diethyl
α-Trimethylsilyloxyphosphonates to Diethyl
α-Thiocyanobenzylphosphinate by APDPP/Br2/NH4SCN
To a flask containing a stirring mixture of APDPP (0.35 g, 1.2 mmol)
and Br2 (0.06 g, 1.2 mmol) in CH3CN (7 mL), NH4SCN (0.18 g, 2.4
mmol) was added at room temperature and stirred for 2 h. Then α-
trimethylsilyloxyphosphonates (0.31 g, 1 mmol) was added to this re-
action mixture. TLC and GC analysis of the reaction showed the com-
pletion of the reaction after 45 min. The reaction mixture was then
filtered. After evaporation of the solvent, the residue was washed with
25 mL of diethyl ether. For further purification, the residue was chro-
matographed on a column of silica-gel using n-hexane-ethyl acetate
(5:2) as eluent. α-Thiocyanobenzylphosphinate was obtained in 85%
yield (0.24 g) and identified by comparison with a known sample.6a 1
H
NMR (CDCl3/TMS): δ (ppm) = 1.12 (t, 3 H, 3JHH= 7.15 Hz, OCH2CH3),
1.40 (t, 3 H, 3JHH= 7.15 Hz, OCH2CH3), 3.85–3.96 (m, 1 H, OCH2CH3),
4.09–4.23 (m, 1 H, OCH2CH3), 4.33–4.42 (m, 2 H, OCH2CH3), 4.65
(d, 1 H, 2JPH= 17.8 Hz, CH), 7.47–7.60 (m, 5 H, C6H5). 13C NMR
(CDCl3/TMS): δ(ppm) = 16.34 (d, 3JCP= 5.7 Hz, OCH2CH3), 16.47 (d,
3JCP= 5.7 Hz, OCH2CH3), 47.83 (d, 1JCP= 148.1 Hz, CH), 64.07 (d,
2JCP= 7 Hz, OCH2CH3), 64.69 (d, 2JCP= 7 Hz, OCH2CH3), 114.54

2018
N. Iranpoor et al.
(SCN), 130.08–130.43, 133.01 (C6H5). 31P NMR (CDCl3): δ‘(ppm) =
17.17.
Diethyl α-Thiocyanato-4-methoxybenzylphosphonate
1H NMR (CDCl3/TMS): δ = 1.34 (t, 3 H, 3JHH= 7.15 Hz, OCH2CH3),
1.56 (t, 3 H, 3JHH= 7.15 Hz, OCH2CH3), 3.98 (s, 3 H, 4-OCH3), 4.09–
4.39 (m, 4 H, OCH2CH3), 4.62 (d, 1 H, 2JPH= 17.6 Hz, CH), 7.03 (d,
2 H, 3JHH= 8.6 Hz, C6H4), 7.45 (d, 2 H, 3JHH= 8.6 Hz, C6H4). 13C
NMR (CDCl3/TMS): δ = 16.64 (d, 3JCP= 5.6 Hz, OCH2CH3), 16.83 (d,
3JCP= 5.6 Hz, OCH2CH3), 47.64 (d, 1JCP= 146.8 Hz, CH), 56.70 (4-
OCH3), 64.38 (d, 2JCP= 7.15 Hz, OCH2CH3), 64.82 (d, 2JCP= 7.15 Hz,
OCH2CH3), 114.63 (SCN), 115.11, 129.18, 131.11, 160.78 (C6H4). 31P
NMR (CDCl3): δ(ppm) = 17.43.
Diethyl α-Thiocyanato-4-chlorobenzylphosphonate
1H NMR (CDCl3/TMS): δ= 1.37 (t, 3 H, 3JHH= 7.15 Hz, OCH2CH3),
1.49 (t, 3 H, 3JHH= 7.15 Hz, OCH2CH3), 3.91–4.06 (m, 1 H,OCH2CH3),
4.12–4.22 (m, 1 H, OCH2CH3), 4.28–4.39 (m, 2 H,OCH2CH3), 4.71 (d, 1
H, 2JPH= 18.3 Hz, CH), 7.39 (d, 2 H, 2JHH= 8.6 Hz, C6H4), 7.78 (d, 2 H,
2JHH= 8.6 Hz, C6H4).13C NMR (CDCl3/TMS): δ= 16.66 (d, 3JCP= 5.6 Hz,
OCH2CH3), 16.91 (d, 3JCP= 5.6 Hz, OCH2CH3), 47.54 (d, 1JCP= 145.1
Hz, CH), 64.52 (d, 2JCP= 7.15 Hz, OCH2CH3), 65.11 (d, 2JCP= 7.15 Hz,
OCH2CH3), 114.01 (SCN), 130.1, 131.21, 131.45, 136.04 (C6H4). 31P
NMR (CDCl3): δ(ppm) = 16.58.
p-MeO-PhCH2SCN: 1H NMR (CDCl3/TMS): δ = 3.2 (3H, s), 3.9 (2H,
s), 6.88–7.26 (4H, m); 13C NMR (CDCl3/TMS): δ = 159.5, 132.8, 127.5,
115.9, 111.2, 55.3, 38.8.
PhCH2CH2CH2SCN: 1H NMR (CDCl3/TMS): δ= 2.0 (2 H, q), 2.7 (2
H, t), 2.9 (2 H, t), 7.1–7.5 (5 H, m);13C NMR (CDCl3/TMS): δ= 140.3,
129.1, 128.9, 126.8, 112.6, 34.2, 32.5, 31.6.
1
CH3(CH2)5CH(SCN)CH3: H NMR (CDCl3/TMS): δ= 0.8 (3 H, t),
0.75 (2 H, m), 0.95 (3 H, d), 1.1 (6 H, m), 1.7 (2 H, q), 2.5 (1 H, m);13C
NMR (CDCl3/TMS): δ= 111.9, 46.1, 37.3, 32.0, 29.1, 27.3, 22.9, 22.3,
14.4.
Ph2CHNCS: mp = 56–58◦C, (Lit.26, mp 57–58◦C); 1H NMR
(CDCl3/TMS): δ= 6.98 (1 H, s), 6.98-7.38 (10 H, m).13C NMR
(CDCl3/TMS): δ= 150.0, 139.6, 129.3, 128.7, 127.9, 65.0.
1
p-NO2-PhCH2SCN: mp = 87–88◦C, (Lit.,27 mp 85–86◦C); H NMR
(CDCl3/TMS): δ= 4.22 (2 H, S), 7.52 (2 H, m), 8.23(2 H, m);13C NMR
(CDCl3/TMS): δ= 146.4, 140.1, 128.3, 122.7, 109.3, 35.32.

Thiocyanation of Alcohols and Protected Alcohols
2019
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