Reactions of 2,4-diaryl 1,3,2,4-dithiadiphosphetane- 2,4-disulfides with resorcinol and 1,3-bis(2-hydroxyethoxy) benzene

Article abstract of DOI:10.1080/17415993.2011.613120

Novel bisaryldithiophosphonic acids were obtained by the reactions of 2,4-diaryl 1,3,2,4-dithiadiphosphetane-2,4-disulfides with resorcinol and 1,3-bis(2-hydroxyethoxy)benzene. [image omitted].

Full text of DOI:10.1080/17415993.2011.613120

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Reactions of 2,4-diaryl 1,3,2,4-
dithiadiphosphetane- 2,4-disulfides
with resorcinol and 1,3-bis(2-
hydroxyethoxy) benzene
Ilyas S. Nizamov a b , Yevgeniy N. Nikitin b , Lyubov A. Almetkina
b , Gulnaz R. Sabirzyanova b , Alexander R. Burilov a & Michail A.
Pudovik a
a AE Arbuzov Institute of Organic and Physical Chemistry , 420088
Kazan, Arbuzov Street, 8, Russia
b Kazan (Volga Region) Federal University , 420008 Kazan,
Kremlyovskaya Street, 18, Russia
Published online: 31 Aug 2011.
To cite this article: Ilyas S. Nizamov , Yevgeniy N. Nikitin , Lyubov A. Almetkina , Gulnaz R.
Sabirzyanova , Alexander R. Burilov & Michail A. Pudovik (2011) Reactions of 2,4-diaryl 1,3,2,4-
dithiadiphosphetane- 2,4-disulfides with resorcinol and 1,3-bis(2-hydroxyethoxy) benzene, Journal
of Sulfur Chemistry, 32:5, 413-417, DOI: 10.1080/17415993.2011.613120
To link to this article: http://dx.doi.org/10.1080/17415993.2011.613120
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Journal of Sulfur Chemistry
Vol. 32, No. 5, October 2011, 413–417
Reactions of 2,4-diaryl 1,3,2,4-dithiadiphosphetane-
2,4-disulfides with resorcinol and 1,3-bis(2-hydroxyethoxy)
benzene
Ilyas S. Nizamova,b*, Yevgeniy N. Nikitinb, Lyubov A. Almetkinab, Gulnaz R. Sabirzyanovab,
Alexander R. Burilova and Michail A. Pudovika
aAE Arbuzov Institute of Organic and Physical Chemistry, 420088 Kazan, Arbuzov Street, 8, Russia; bKazan
(Volga Region) Federal University, 420008 Kazan, Kremlyovskaya Street, 18, Russia
(Received 4 July 2011; final version received 2 August 2011)
Novel bisaryldithiophosphonic acids were obtained by the reactions of 2,4-diaryl 1,3,2,4-
dithiadiphosphetane-2,4-disulfides with resorcinol and 1,3-bis(2-hydroxyethoxy)benzene.
HO
OH
HO
O
OH
O
S
P
S
P
S
P
S
P
Ar
2
Ar
Ar
S
Ar
Ar
S
O
S
S
4
O
O
O
O
O
P
P
SH
HS
SH
HS
Ar
1a,b
5a,b
3a,b
(a)
(b)
Ar = HO
O
Keywords: 2,4-diaryl1,3,2,4-dithiadiphosphetane-2,4-disulfides;resorcinol;1,3-bis(2-hydroxyethoxy)benzene;
bisaryldithiophosphonic acids
1. Introduction
Tetracoordinated organophosphorus thioacids, as well as their esters and salts, have a wide
range of applications as lubricant additives, antioxidants, extractives, complexing agents, pes-
ticides, etc. (1, 2). Bisdithiophosphonic acids are new types of tetracoordinated phosphorus
thioacids bearing two dithiophosphoryl groups. 2,4-Dimethyl 1,3,2,4-dithiadiphosphetane-2,4-
disulfide has been reported to react with alkylene glycols in 1:1 molar ratio in diethyl ether
suspension at room temperature to give bisalkyldithiophosphonic acids (3). We have previously
prepared bisaryldithiophosphonic acids in the reactions of 2,4-diaryl 1,3,2,4-dithiadiphosphetane-
*Corresponding author. Email: isnizamov@mail.ru
ISSN 1741-5993 print/ISSN 1741-6000 online
© 2011 Taylor & Francis
http://dx.doi.org/10.1080/17415993.2011.613120
http://www.tandfonline.com

414 I.S. Nizamov et al.
2,4-disulfides with alkylene glycols such as 1,4-butandiol and triethylene glycol (4–7). We now
extendthisapproachtohydroxyphenolssuchasresorcinoland1,3-bis(2-hydroxyethoxy)benzene.
2. Results and discussion
The reaction of Lawesson-like reagents with compounds containing a pair of hydroxyl groups
has been described (8). Lawesson’s reagent has been reported to react with catechol to form 2-(4-
methoxyphenyl)-1,3,2λ5-benzodioxaphosphole-2-thione, whereas with ethane-1,2-diols and 4,5-
dihydro-1,3,2λ5-dioxaphosphole-2-thione together with 2,4-bis(4-methoxyphenyl)-6,7-dihydro-
1,5,3,2λ5, 4λ5-dioxathiadiphosphepine-2,4-dithione are obtained (8). The reaction of 2,4-
diferrocenyl 1,3,2,4-dithiadiphosphetane-2,4-disulfide with catechol or 3,5-di-tert-butylcatechol
occurs in boiling toluene, resulting in the formation of 1,3,2λ5-dioxaphosphole-2-thione deriva-
tives (9). Thus, no bisaryldithiophosphonic acids were obtained in pure form in the reactions with
catechols. Compounds isolated in previous studies (8, 9) seem to be secondary products. We have
proposed that these reactions proceed via the intermediate formation of thermally unstable ini-
− − − −
tial products containing the S P O X O P S fragment (where X = alkylene, arylene), which
then decompose leading to the final products. To avoid the formation of secondary products,
we have determined the optimal conditions for the formation of bisaryldithiophosphonic acids
in the reactions with hydroxyphenols. We have chosen resorcinol as a homolog of catechol as
a substrate for thiophosphorylation. It should be noted that the chemical behavior of resorcinol
and 1,3,2,4-dithiadiphosphetane-2,4-disulfides has not been reported. The reactions of 2,4-diaryl
1,3,2,4-dithiadiphosphetane-2,4-disulfides 1a and b with resorcinol 2 in benzene at room tem-
perature over 10 days (for 1a) or at 60 ◦C over 2 h (for 1b) have brought about the formation of
O,Oꢀ-(benzene-1,3-diyl)-1,3-bis(aryldithiophosphonic) acids 3a and b (Scheme 1).
To avoid the formation of oligomers, we have carried out these reactions (Scheme 1) under large
dilutions. Compounds 3a and b are white crystalline solids. While bands of strong intensity for
the hydroxyl groups in the region ν 3380 cm−1 in the IR spectra of 3a and b are absent, they reveal
the characteristic bands for S H bonds ν 2538–2352 cm−1. However, hydroxyl groups of the aryl
−
substituent remained attached to 3a and revealed a sharp band of medium intensity at ν 3618 cm−1
.
The 31P NMR spectra of 3a and b in benzene solutions show singlets in the range of δP = 88.1 and
87.9 ppm, respectively. These signals are typical for dithiophosphonic acids (10). In spite of 3a
and b containing two stereogenic centers at the phosphorus atoms, we observed only one singlet
in their experimental 31P NMR spectra. This phenomenon might be explained by a prototropic
−
rearrangement in the S P S heteroatom triad. Alternatively, the two chiral phosphorus atoms are
perhaps too far apart and the 31P peaks for the two diastereomers are accidentally equivalent. The
1H NMR spectrum of 3a in CDCl3 solution exhibits two high-intensity singlets at δ = 1.47 and
1.50 ppm for the methyl protons of the 3,5-di-tert-butyl-4-hydroxyphenyl groups [(CH3)3C, Ar]
in the ratio of ∼ 1 : 1, indicating the formation of 3a as a mixture of diastereoisomers. A mass
peak at m/e 711 in the electron impact (EI) mass spectrum of 3a is due to its molecular ion [M]+
(calculated molecular mass M of 3a is 711.0). A mass peak at m/e 639 observed in the MALDI
S
P
S
P
S
Ar
S
HO
S
S
OH
Ar
Ar
O
O
P
P
+
Ar
SH
HS
1a,b
2
3a,b
(a)
(b)
Ar = HO
O
Scheme 1. The reaction of 2,4-diaryl 1,3,2,4-dithiadiphosphetane-2,4-disulfides with resorcinol.

Journal of Sulfur Chemistry 415
S
S
P
Ar
S
S
S
S
Ar
Ar
HO
O
OH
(a)
P
O
O
O
O
O
P
+
P
Ar
SH
HS
1a,b
4
5a,b
(b)
Ar = HO
O
Scheme 2. The reaction of 2,4-diaryl 1,3,2,4-dithiadiphosphetane-2,4-disulfides with 1,3-bis
(2-hydroxyethoxy)benzene.
TOF mass spectrum of 3b is attributable to the molecular ion [M + H]+ (calculated molecular
mass M of 3b is 638.7).
The formation of products of similar structure could be expected using the 2-hydroxyethoxyl
derivative of resorcinol. It should be noted that 1,3-bis(2-hydroxyethoxy)benzene 4 contains
aliphatic hydroxyl groups in contrast to the aromatic ones found in resorcinol 2. It is of
considerable interest to compare the reactivity of hydroxyl compounds 2 and 4 toward 1,3,2,4-
dithiadiphosphetane-2,4-disulfides. We have found that 4 reacts with dithiadiphosphetanes 1a and
b at room temperature to give O,Oꢀ-benzene-1,3-bis[ethoxy-2-(aryldithiophosphonic)] acids 5a
and b (Scheme 2).
The reactions of 1a and b with 4 were performed under large dilutions in benzene similar
to the procedure used for 2. The formation of 5b containing the 4-phenoxyphenyl substituents
occurred within 2 h, whereas the reaction of dithiadiphosphetane 1b with resorcinol 2 proceeded
for 8 h to form thioacid 3b with the same 4-phenoxyphenyl groups. Moreover, the products 3a
and b in the reactions of resorcinol 2 were prepared in yields of 67–85%. In contrast, the yields
of 5a and b in the reactions of 2-hydroxyethoxyl derivative 4 were increased to 91%. Thus, we
have shown that 4 is more reactive than 2 toward 1a and b. The 31P NMR spectra of 5a and
b in benzene solutions revealed singlets at δP = 89.0 and 87.6 ppm, respectively. The 1H NMR
spectrum of 5a in CDCl3 solution showed characteristic resonances due to the presence of the
OCH2CH2O fragment attached to the phosphorus atom. The OCH2CH2OP protons appeared as a
triplet in the region of δ = 4.27 ppm with 3JHH = 5.2 Hz in 5a.A doublet of triplets observed in the
region of δ = 4.57 ppm has been assigned to the methylene protons (the OCH2CH2OP fragment)
attached to the phosphorus atom via the oxygen with 3JHH = 5.2 and 3JPH = 0.14.3 Hz. The EI
mass spectrum of 5b exhibited a mass peak at m/e 727 for its molecular ion [M]+. The MALDI
TOF mass spectrum of 5a exhibited a mass peak at m/e 821.8 for the ion [M + Na]+ (calculated
molecular mass M of 5a is 799.1).
3. Conclusions
The reactions of 2,4-diaryl 1,3,2,4-dithiadiphosphetane-2,4-disulfides with resorcinol and 1,3-
bis(2-hydroxyethoxy)benzene are of interest from the point of view of organothiophosphorus
chemistry as they lead to new bisaryldithiophosphonic acids that may serve as the initial
compounds on the way to some derivatives with potential biological activity.
4. Experimental
The IR spectra were obtained in KBr pellets, suspended in vaseline oil or as a liquid film, with
1
a Bruker Vector-22 infrared spectrophotometer. The H NMR spectra were taken on a Bruker

416 I.S. Nizamov et al.
Avance-600 spectrometer (600 MHz) in CDCl3. The 31P NMR spectra were recorded with a
Bruker Avance-400 (161.9 MHz) instrument in C6H6 with 85% H3PO4 as an external reference.
Massspectra(EI, 70 eV)weredeterminedonaDFSThermoElectronCorporationchromato-mass-
spectrometer (sample directly introduced). Mass spectra MALDI TOF were run on an Ultrafex
Bruker (UV laser, 337 nm).
4.1. O,Oꢀ-(Benzene-1,3-diyl)-1,3-bis(3,5-di-tert-butyl-4-hydroxyphenyldithiophosphonic)
acid 3a
Resorcinol 2 (0.11 g, 1.0 mmol) was added portionwise under dry argon under stirring at 20 ◦C
to the suspension of 0.6 g (1.0 mmol) of dithiadiphosphetane 1a in 15 ml of anhydrous benzene,
and stirring was continued for 8 h. The mixture was filtered and the filtrate was evaporated at
reduced pressure (0.5 mm Hg) at 40 ◦C for 1 h and then in vacuum (0.02 mm Hg) to give the
residue that was solidified when stored. The yield of 3a was 0.6 g (85%), mp 80–81 ◦C. Anal.
found: C, 57.32; H, 6.44; P, 8.63; S, 16.23. C34H48O4P2S4 requires C, 57.44; H, 6.81; P, 8.71;
S, 16.04%. IR (KBr pellet, νmax, cm−1): 3618 (H O, Ar), 3085 ( C H, Ar), 2959, 2913, 2913,
− −
−
−
−
−
2872 (CH3), 2538 (S H, free), 2437 (S H, bonded), 1594, 1478 (C C, Ar), 1429 (CH3), 1364
1
−
−
−
(CH3), 1111, 1119 [(P)O C], 973 (O C), 660 (P S), 595 (P S). H NMR: δH 1.47 and 1.50
−
[two s, 36H, (CH3)3C, Ar], 2.59 (m, 2H, PSH), 5.03 (m, 2H, HO Ar), 6.41 and 6.43 (two d, 1H,
2-C6HO2P, 4JHH = 2.2 Hz), 6.67 and 6.71 (two d, 1H, 5-C6HO2P, 3JHH = 8.3 Hz), 7.07 and 7.13
(two d, 2H, 4,6-C6HO2P, 3JHH = 8.3 Hz), 7.83 and 7.92 (two d, 4H, 2,6-C6H2P, 3JPH = 15.9 Hz).
MS (EI) m/e (Irel): 711 [M]+. (5). 31P NMR, δP: 88.1.
4.2. O,Oꢀ-(Benzene-1,3-diyl)-1,3-bis(4-phenoxyphenyldithiophosphonic) acid 3b
Product 3b (0.8 g, 67%) was obtained similarly from 1.0 g (1.9 mmol) of dithiadiphosphetane 1b
and (0.21 g, 1.9 mmol) resorcinol 2, mp 46–48 ◦C.Anal. found: C, 56.20; H, 3.91; P, 9.40; S, 20.46.
C30H24O4P2S4 requires C, 56.41; H, 3.79; P, 9.70; S, 20.08. IR (νmax, cm−1): 3064, 3030 ( C H,
− −
−
−
−
−
−
Ar), 2352 (S H), 1584, 1488 (C C, Ar), 1122 [(P)O C], 930 (O C), 695 (P S), 520 (P S).
1H NMR: δH 1.19 (m, 2H, PSH), 6.94 (two d, 4H, 3,5-C6H2O, 3JHH = 7.4 Hz), 7.02 (two d, 4H,
3,5-C6H2P, 3JHH = 7.9 Hz), 7.18 (two d, 2H, 4-C6HO, 3JHH = 7.4 Hz and 3JHH = 7.4 Hz), 7.34
(dd, 4H, 2,6-C6H2O, 3JHH = 7.4 Hz), 7.83 (dd, 4H, 2,6-C6H2P, 3JHH = 7.9 and 3JPH = 13.4 Hz).
MS (MALDI TOF, matrix – 1,8,9-trihydroxyanthracene) m/e: 639 [M + H]+. 31P NMR, δP: 87.9.
4.3. O,Oꢀ-Benzene-1,3-bis[ethoxy-2-(3,5-di-tert-butyl-4-hydroxyphenyldithiophosphonic)]
acid 5a
Product 5a (0.8 g, 91%) was obtained similarly from 0.66 g (1.1 mmol) of dithiadiphosphetane
1a and 4 (0.22 g, 1.1 mmol), mp 63–64 ◦C. Anal. Found: C, 57.10; H, 7.49; P, 7.42; S, 15.88.
C38H56O6P2S4 requires C, 57.12; H, 7.06; P, 7.75; S, 16.05. IR (KBr pellet, νmax, cm−1): 3619
−
− −
−
(H O, Ar), 3009 ( C H, AR), 2959, 2912, 2871 (CH3, CH2), 2364, 2350 (S H), 1590, 1492
1
−
−
−
−
3
(C C, AR), 1430 (CH3), 1364 (CH3), 1043 [(P)O C], 956 (O C), 656 (P S), 507 (P S). H
NMR, δH: 1.46 [s, 36H, (CH3)3C, Ar], 3.00 (m, 2H, PSH), 4.27 (t, 4H, OCH2CH2OP, JHH
=
5.2 Hz); 4.57 (dt, 4H, OCH2CH2OP, 3JHH = 5.2 and 3JPH = 14.3 Hz); 5.65 (m, 2H, HO Ar), 6.53
(m, 3H, 4,5,6-C6H3O2), 7.18 (m, 1H, 2-C6HO2), 7.83 (d, 4H, 2,6-C6H2P, 3JPH = 16.4 Hz). MS
(MALDI TOF, matrix – 1,8,9-trihydroxyanthracene) m/e: 821.8 [M + Na]+, 782 [M − HO]+,
−
767.8 [M − S] , 750 [M S HO] . 31P NMR, δP: 89.0.
+
+
− −

Journal of Sulfur Chemistry 417
4.4. O,Oꢀ-Benzene-1,3-bis[ethoxy-2-(4-phenoxyphenyldithiophosphonic)] acid 5b
Product 5b (1.0 g, 91%) was obtained similarly from 1.0 g (1.5 mmol) of dithiadiphosphetane 1b
and 4 (0.3 g, 1.5 mmol) as a paste.Anal. found: C, 56.36; H, 4.58; P, 8.64; S, 17.35. C36H32O6P2S4
requires C, 56.18; H, 4.44; P, 8.52; S, 17.65. IR (liquid film, νmax, cm−1): 3066, 3036 ( C H,
− −
−
−
−
Ar), 2941, 2815 (CH2), 2528 (S H, free), 2443 (S H, bonded), 1585, 1490 (C C, Ar); 1041
1
−
−
−
[(P)O C], 957 (O C), 686 (P S), 530 (P S). H NMR, δH: 3.00 (m, 2H, PSH); 4.27 (t, 4H,
OCH2CH2OP, 3JHH = 4.6 Hz); 4.58 (dt, 4H, OCH2CH2OP, 3JHH = 4.6 and 3JPH = 15.2 Hz), 7.04
(m, 4H, 3,5-C6H2O; 4H, 3,5-C6H2P), 7.21 (two d, 2H, 4-C6HO, 3JHH = 7.4 Hz), 7.40 (dd, 4H,
2,6-C6H2O, 3JHH = 7.8 Hz), 7.98 (dd, 4H, 2,6-C6H2P, 3JHH = 8.3 and 3JPH = 14.8 Hz). MS (EI)
m/e (Irel): 727 [M]+ (5). MS (MALDI TOF, matrix – the solution of sulfur in toluene) m/e: 727.5
[M + H]+, 695.4 [M – S]+. 31P NMR, δP: 87.6.
Acknowledgements
The study was performed with the financial support of the Russian Foundation for Basic Researches (Grant No. 11-03-
00264-a).
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