Synthesis and characterization of novel chiral (1R,2R)-1,2-Bis[5- (aminomethylphospinic acid)-1,3,4-thiadiazol-2-YL]ethane-1,2-diols

Article abstract of DOI:10.1080/10426507.2011.636412

(1R,2R)-1,2-bis[5-(arylideneamino)-1,3,4-thiadiazol-2-yl]ethane-1,2-diol (2a-d) were synthesized by using appropriate aldehydes and (1R,2R)-1,2-bis(5- amino-1,3,4-thiadiazol-2-yl)ethane-1,2-diol (1) as a starting compound. Then, the phosphinic acid component (3a-d) were obtained from (2a-d) and hypophosporus acid. In addition, the structures of the novel chiral compounds (2a-d) and (3a-d) were confirmed by elemental analyses, IR, ¹H-NMR, ¹³C-NMR, and ³¹P-NMR spectra. ¹H NMR and ¹³C NMR spectra for 1, 2a, and 3a (Figures S1-S6) are available online in the Supplemental Materials. Copyright Taylor and Francis Group, LLC 2012.

Full text of DOI:10.1080/10426507.2011.636412

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Phosphorus, Sulfur, and Silicon and the
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Synthesis and Characterization
of Novel Chiral (1R,2R)-1,2-Bis[5-
(Aminomethylphospinic Acid)-1,3,4-
Thiadiazol-2-YL]Ethane-1,2-Diols
P. Koparir a , M. Karaarslan b , C. Orek c & M. Koparir c
a Department of Chemistry, Forensic Medicine, Malatya, Turkey
b Department of Chemistry, Aksaray Universty, Aksaray, Turkey
c Department of Chemistry, Firat University, Elazig, Turkey
Accepted author version posted online: 04 Jan 2012.Published
online: 30 May 2012.
To cite this article: P. Koparir , M. Karaarslan , C. Orek & M. Koparir (2012) Synthesis and
Characterization of Novel Chiral (1R,2R)-1,2-Bis[5-(Aminomethylphospinic Acid)-1,3,4-Thiadiazol-2-
YL]Ethane-1,2-Diols, Phosphorus, Sulfur, and Silicon and the Related Elements, 187:7, 864-870, DOI:
10.1080/10426507.2011.636412
To link to this article: http://dx.doi.org/10.1080/10426507.2011.636412
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Phosphorus, Sulfur, and Silicon, 187:864–870, 2012
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2011.636412
SYNTHESIS AND CHARACTERIZATION OF NOVEL
CHIRAL (1R,2R)-1,2-BIS[5-(AMINOMETHYLPHOSPINIC
ACID)-1,3,4-THIADIAZOL-2-YL]ETHANE-1,2-DIOLS
P. Koparir,1 M. Karaarslan,2 C. Orek,3 and M. Koparir3
1Department of Chemistry, Forensic Medicine, Malatya, Turkey
2Department of Chemistry, Aksaray Universty, Aksaray, Turkey
3Department of Chemistry, Firat University, Elazig, Turkey
GRAPHICAL ABSTRACT
N
N
HO
H
N
N
N
HO
H
N
R1-CHO
N
N
H2
N
R1
N
S
N
H2
S
S
N
HO
S
H
R1
O
H
H
1
R1: a) 2-hydroxynaphthalen- 1-yl b) 4-nitrophenyl
2a-d
c) 4-methoxyphenyl
d) 4-chlorophenyl
H3PO2
O
P
N
N
HO
H
N
HO
N
N
H
R1
H
H
R1
S
N
H
S
P
OH
HO
H
O
3a-d
Abstract (1R,2R)-1,2-bis[5-(arylideneamino)-1,3,4-thiadiazol-2-yl]ethane-1,2-diol (2a–d)
were synthesized by using appropriate aldehydes and (1R,2R)-1,2-bis(5-amino-1,3,4-
thiadiazol-2-yl)ethane-1,2-diol (1) as a starting compound. Then, the phosphinic acid
component (3a–d) were obtained from (2a–d) and hypophosporus acid. In addition, the
structures of the novel chiral compounds (2a–d) and (3a–d) were confirmed by elemental
analyses, IR, 1H-NMR, 13C-NMR, and 31P-NMR spectra.
1H NMR and 13C NMR spectra for 1, 2a, and 3a (Figures S1–S6) are available online in the
Supplemental Materials.
Keywords 1,3,4-Thiadiazole; aminophosphinic acid; tartaric acid; ethane-1,2-diol
INTRODUCTION
Phosphinic acids are of growing importance in understanding and modulating bio-
logical processes.1 In recent years, the synthesis of α-substituted phosphoryl derivatives
(phosphonic and phosphinic acids) has attracted significant attention, due to their biologi-
cal activities with broad application as enzyme inhibitors, antimetabolites, and antibiotics.2
Received 29 September 2011; accepted 26 October 2011.
This work was supported by Grant no. FF.11.17 of the Research Fund of Firat University (FUBAP).
Address correspondence to Pelin Koparir, Department of Chemistry, Forensic Medicine, TR-44000, Malatya,
Turkey. E-mail: pelin.kutulay@adalet.gov.tr
864

SYNTHESIS AND CHARACTERIZATION OF NOVEL CHIRAL
865
Among functionalized phosphinic acids, α-aminoalkylphosphinic derivatives have poten-
tial biological properties, such as antibacterial,2 herbicidal,3 and fungicidal activities.4 1-
aminoalkylphosphinic acids, the phosphinic acid analogs of 1-amino carboxylic acids, are
an important class of compounds that exhibit a variety of interesting and useful properties.5
In addition, the structure of the phosphinic functional group mimics the transition
state of peptide hydrolysis, and the symmetric nature of the phosphinic acid derivatives is
expected to be of benefit in their binding to the homodimer of HIV-protease having C2-axis
symmetry.5
Proteolytic enzymes, responsible for cleavage of an amide bond in peptide substrates,
are involved in variety of physiological and pathological processes, thus representing a
group of the most attractive targets for drug design and development.6,7 The discovery of
highly potent and selective inhibitors of proteases, able to discriminate between different
members of the same family of proteases, remains a continuous challenge. A phosphinic
moiety ( PO2−CH2 ) is considered to mimic the high-energy tetrahedral transition state
of peptide bond hydrolysis and due to this ability phosphinate pseudopeptides attract
considerable interest providing a wide range of potent inactivators of proteolitic enzymes,
particularly metalloproteases.8–10
The 1,3,4-thiadiazole ring is associated with diverse biological activities probably by
virtue of incorporating a toxophoric N C S linkage, the importance of which has been
well stressed in many pesticides.11–14 Various 2-amino/substituted-amino-1,3,4-thiadiazoles
and their Schiff bases have recently received significant importance because of their diverse
biological properties.15 Enantiomerically pure 1,2-diols are valuable intermediates in the
organic synthesis of biologically active compounds and natural products.16 They are readily
transformed into chiral epoxides,17 aziridines, and amino alcohols.18 Moreover, the 1,2-diol
functionality is found in a number of synthetic and pharmaceutical intermediates.19
Compounds that have optical activity can change to another compound that has op-
tical activity without breaking of covalent bonds, which is connected with asymmetric
carbon atoms. In this change, the configuration stays unchanged. So, our synthesized com-
pound configuration is the same as that of our starting compound (the reactions are shown
in Scheme 1). However, this reaction mechanism shows that the stereochemistry of the
products is unchanged, and the synthesized compound 2a–d and 3a–d are enantiomerically
pure.
N
N
HO
H
N
N
N
HO
H
N
R1-CHO
N
N
H2
N
R1
N
S
N
H2
S
S
N
HO
S
H
R1
HO
H
1
2a-d
R1: a) 2-hydroxynaphthalen- 1-yl b) 4-nitrophenyl
c) 4-methoxyphenyl d) 4-chlorophenyl
H3PO2
O
N
O
H
N
H
N
HO
P
N
N
H
R1
H
H
R1
S
NH
S
O
P
OH
H
H
O
3a-d
Scheme 1

866
P. KOPARIR ET AL.
In the present paper, we have investigated the preparation and characterization of
various 1,3,4-thiadiazole containing Schiff bases (2a–d) and aminophosphinic acid (3a–d)
derivatives of novel chiral compounds.
In light of the studies conducted on the synthetic chemistry of phosphinic acids during
last 15 years, we have also partly contributed to this progress by developing a new chiral
aminophosphinic acid synthesis.
RESULTS AND DISCUSSION
Chemistry
The reactions for the synthesis of 1–3, are shown in Scheme 1. (1R,2R)-1,2-bis(5-
amino-1,3,4-thiadiazol-2-yl)ethane-1,2-diol (1) was synthesized by treating thiosemicar-
bazide with the (2R,3R)-(+)-tartaric acid according to the published procedure.20–23
The amine (1), on treatment with aromatic aldehydes, furnished Schiff bases of thiadi-
azoles (2a–d), which, on reaction with hypophosphorus acid in the presence of acetonitrile
yielded (1R,2R)-1,2-bis[5-(aminomethylphospinic acid)-1,3,4-thiadiazol-2-yl]ethane-1,2-
diol (3a–d).
Natural chiral compounds (from the chiral pool) often offer an alternative to the syn-
thesis of enantiomerically pure products. (2R,3R)-(+)-tartaric acid is one chiral carboxylic
acid isolated from natural sources. In this study, we aimed to synthesized (1R,2R)-1,2-
bis(5-amino-1,3,4-thiadiazol-2-yl)ethane-1,2-diol (1) by using (2R,3R)-(+)-tartaric acid
as starting compound. In the light of above observations, we have selected 1 as the start-
ing compound, which were synthesized according to the literature procedure published
previously.20–23
The sulfuric acid was used as catalyst in the preparation of 2a–d. In generally, the
preparation of arylidene compounds containing heterocyclic structure is used sulfuric acid
as catalyst.22 This type of compounds is used due to low the steric effects of sulfuric acid
as catalyst.
We thought, it worthwhile to synthesize a new series of Schiff bases (2a–d) and
aminophosphinic acids (3a–d) having a 1,3,4-thiadiazole moiety with the objective of
obtaining new biologically active compounds.
Finally, we have also partly contributed to this progress by obtaining chiral Schiff
bases and chiral aminophosphinic acid derivatives, which involve 1,3,4-thiadiazole groups.
In the IR spectrum of 2a–d, 3a–d the most characteristic absorptions are at 3405–3501
cm−1 (OH), 3269–3301 cm−1 (NH), 1625–1630 cm−1 (N CH), 1601–1613 cm−1 (C N),
1252–1259cm−1 (P O), 989–1112 cm−1 (P O), and 2314–2402 cm−1 (P H). In the
1H-NMR spectra, characteristic signals due to the NH protons appeared at 5.44–5.49.
The signals due to the (N CH) protons appeared at 8.05–8.11 and those arising from the
(PH) protons appeared at 5.09–5.12. The signals due to the (CH–P) protons appeared at
4.76–4.79. The signals due to the aromatic protons appeared as multiples at 6.95–8.37.
31P-NMR spectrum of the product (3a–d) exhibited peaks 28.3–28.4 and compares well
with the value reported previously 15.3–28.3.24 The data for all compounds are given in
the experimental section. Spectra for 1 (Figures S1 and S2), 2a (Figures S3 and S4), and
3a (Figures S5 and S6) can be found in the Supplemental Materials available online.
The yield of 2b was high. The reason for this could be the lack of conjugation between
n-electrons on nitrogen atoms with the aromatic ring in intermediate compounds of 2b.

SYNTHESIS AND CHARACTERIZATION OF NOVEL CHIRAL
867
On the other hand, yields of 2a, 2c, and 2d were more moderate, because of an effective
conjugation they have with the aromatic ring in intermediate compounds of 2a, 2c, and 2d.
EXPERIMENTAL
Melting points were determined on a Thomas Hoover melting point apparatus and
use uncorrected, but checked by differential scanning calorimeter (DSC). Specific rotations
were recorded on a POLS-1 high-sensitivity polarimeter, with a fixed sodium lamp of
wavelength 589 nm. The IR spectra were measured with Perkin–Elmer Spectrum One
FTIR spectrophotometer. The 1H, 13C, and 31P spectra were taken on Bruker AC-300 and
1
Bruker AC-400 NMR spectrometer operating at 400 MHz for H, 100 MHz for 13C, and
161.9 MHz for 31P NMR. Compounds were dissolved in CDCl3, D2O and chemical shifts
were referenced to DSS, TMS, (1H and 13C NMR) and 85% H3PO4 (31P NMR). Elemental
analyses were performed on a LECO-CHNS-938. Starting chemicals were obtained from
Merck or Aldrich.
Synthesis of (1R,2R)-1,2-Bis(5-Amino-1,3,4-Thiadiazol-2-yl)Ethane-
1,2-Diol (1)
The synthesis of 1 was carried out accor◦ding to a method given in the literature.20
White solid, yield 77%, m.p. 138–139 C. IR (KBr, cm−1) υ: 3413 ( OH), 3195
( NH2) 1621 ( C N), 980 ( C S C) cm−1. 1H NMR (400 MHz, D2O, δ, ppm): 4.16
(s, 2H, 2 × CH), 4.65 (s, 6H, HDO form 2 × NH2 and 2 × OH). 13C NMR (100 MHz,
CDCl3, TMS, δ, ppm): 178.6, 165.0, 74.0. Elemental analysis: C6H8N6O2S2 Calculated:
C, 27.69; H, 3.10; N, 32.29. Found: C, 27.63; H, 3.09; N, 32.18. [α]D −173◦ (c 4, water).
20
General Procedure for the Synthesis of (1R,2R)-1,2-Bis[5-
(Arylideneamino)-1,3,4-Thiadiazol-2-yl]Ethane-1,2-Diol (2a–d)
A mixture of (1R,2R)-1,2-bis(5-amino-1,3,4-thiadiazol-2-yl)ethane-1,2-diol (1)
(10 mmol) and aromatic aldehydes (20 mmol) were added to of ethanol- chloroform (7:3)
(100 mL). Then a few drops of concentrated sulfuric acid were added as a catalyst and the
solution was refluxed for 12 h. The solvent was removed under reduced pressure and the
residue was recrystallized from ethanol to give 2a–d.
(1R,2R)-1,2-Bis(5-{[(2-Hydroxynaphthalen-1-yl)Methylidene]Amino}-
1,3,4-Thiadiazol-2-yl)Ethane-1,2-Diol (2a)
Shining white solid, yield 51%, m.p. 156–157 ◦C. IR (KBr, cm−1) υ: 3450 ( OH),
1628 ( HC N), 1607 ( C N) cm−1. 1H NMR (400 MHz, CDCl3, δ, ppm): 6.68 (d, 2H,
2 × CH OH, J = 10.14), 6.89–6.98 (br, 4H, OH), 7.22 (d, 2H, J1,2 = 8.05, H-1, H-1ꢁ),
7.55–7.74 (m, 4H, H-4, H-4ꢁ; H-5, H-5ꢁ), 8.02 (d, 2H, J2,1 = 10.53, H-2, H-2ꢁ), 8.07 (br,
2H, 2 × N CH), 8.18 (dd, 2H, J6,5 = 7.80, J6,4 = 1.17, H-6, H-6ꢁ), 8.37 (dd, 2H, J3,4
=
6.63, J3,5 = 1.17, H-3, H-3ꢁ). 13C NMR (100 MHz, CDCl3, TMS, δ, ppm): 175.6, 165.1,
153.4, 149.3, 130.9, 127.8, 127.4, 127.0, 120.4, 115.9, 113.5, 73.9. Elemental analysis:
C28H20N6O4S2 Calculated: C, 59.14; H, 3.55; N, 14.78. Found: C, 59.09; H, 3.49; N,
14.77. [α]D −3.907◦ (c 1, ethanol).
20

868
P. KOPARIR ET AL.
(1R,2R)-1,2-Bis(5-{[(4-Nitrophenyl)Methylidene]Amino}-1,3,4-
Thiadiazol-2-yl)Ethane-1,2Diol (2b)
Shining white solid, yield 80%, m.p. 196–197 ◦C. IR (KBr, cm−1) υ: 3460 ( OH),
1630 ( HC N), 1602 ( C N) cm−1. 1H NMR (400 MHz, CDCl3, δ, ppm): 6.67 (d, 2H,
2 × CH OH), 6.88–6.96 (br, 2H, OH), 7.47–8.17 (m, 10H, Ar H and 2 × N CH). 13
C
NMR (100 MHz, CDCl3, TMS, δ, ppm): 175.4, 173.4, 169.4, 168.2, 153.6, 140.6, 131.6,
125.4, 125.5, 73.8. Elemental analysis: C20H14N8O6S2 Calculated: C, 45.62; H, 2.68; N,
21.28. Found: C, 45.59; H, 2.65; N, 21.30. [α]D −5.852◦ (c 1, ethanol).
20
(1R,2R)-1,2-Bis(5-{[(4-Methoxyphenyl)Methylidene]Amino}-1,3,4-
Thiadiazol-2-yl)Ethane-1,2-Diol (2c)
◦
White solid, yield 49%, m.p. 211–210 C. IR (KBr, cm−1) υ: 3475 ( OH), 1625
( HC N), 1611 ( C N) cm−1. 1H NMR (400 MHz, CDCl3, δ, ppm): 3.80 (s, 6H, 2 ×
OCH3), 6.66 (d, 2H, 2 × CH OH), 6.82–6.86 (br, 2H, 2 × OH), 6.91–7.37 (m, 8H, Ar H),
8.05 (br, 2H, 2 × N CH). 13C NMR (100 MHz, CDCl3, TMS, δ, ppm): 174.9, 173.4,
169.4, 168.1, 164.6, 132.4, 127.9, 113.1, 73.8, 56.4. Elemental analysis: C22H20N6O4S2
Calculated: C, 53.20; H, 4.06; N, 16.92. Found: C, 53.17; H, 4.01; N, 17.00. [α]D −5.462◦
20
(c 1, ethanol).
(1R,2R)-1,2-Bis(5-{[(4-Chlorophenyl)Methylidene]Amino}-1,3,4-
Thiadiazol-2-yl)Ethane-1,2-Diol (2d)
◦
Shine white, solid yield 60%, m.p. 224–225 C. IR (KBr, cm−1) υ: 3501 ( OH),
1627 ( HC N), 1602 ( C N) cm−1. 1H NMR (400 MHz, CDCl3, δ, ppm): 6.66 (d, 2H,
2 × CH OH), 6.83–6.85 (br, 2H, 2 × OH), 7.02–7.29 (m, 8H, Ar H), 8.11 (br, 2H, 2 ×
N CH) 13C NMR (100 MHz, CDCl3, TMS, δ, ppm): 174.8, 173.4, 169.3, 168.0, 164.6,
132.4, 127.8, 112.1, 73.6. Elemental analysis C20H14Cl2N6O2S2 Calculated: C, 47.53; H,
2.79; N,16.63. Found: C, 46.99; H, 2.80; N,16.59. [α]D −5.662◦ (c 1, ethanol).
20
General Procedure for the Synthesis of (1R,2R)-1,2-Bis[5-
(Aminomethylphospinic Acid)-1,3,4-Thiadiazol-2-yl]Ethane-1,2-Diol (3a–d)
Schiff base 2a–d (5 mmol) was dissolved in acetonitrile (10 mL) and H3PO2
(10 mmol), and the mixture was refluxed for 5 h, then stirred at room temperature for
24 h. The formed precipitate was collected by filtration, which was then dissolved in 0.1
M NaOH. The solution was filtrated and acidified to precipitate the product, which was
collected by filtration.
[({5-[(1R,2R)-1,2-Dihydroxy-2-(5-{[(2-Hydroxynaphthalen-1-yl)
(Hydroxyphosphonoyl) Methyl]Amino}-1,3,4-Thiadiazol-2-yl)Ethyl].-1,3,4-
Thiadiazol-2-yl}Amino)(2-Hydroxynaphthalen-1-yl)Methyl]phosphinic
acid (3a)
◦
White solid, yield 57%, m.p. 337–338 C. IR (KBr, cm−1) υ: 3495 ( OH), 3299
( NH), 2389 ( P H), 1607 ( C N), 1254 ( P O), 1081 ( P O) cm−1. H NMR
1
(400 MHz, CDCl3, δ, ppm): 4.76 (d, 2H, 2 × CHP), 5.10 (d, 2H, 2 × PH), 5.45 (br, 2H, 2

SYNTHESIS AND CHARACTERIZATION OF NOVEL CHIRAL
869
× NH), 6.67 (d, 2H, 2 × CHOH), 6.88–6.98 (br, 4H, OH), 7.21 (d, 2H, J1,2 = 8.05, H-1,
H-1ꢁ), 7.56–7.74 (m, 4H, H-4, H-4ꢁ; H-5, H-5ꢁ), 8.02 (d, 2H, J2,1 = 10.53, H-2, H-2ꢁ), 8.18
(dd, 2H, J6,5 = 7.80, J6,4 = 1.17, H-6, H-6ꢁ), 8.36 (dd, 2H, J3,4 = 6.63, J3,5 = 1.17, H-3,
H-3ꢁ), 8.81 (br, 2H, 2 × POH). 13C NMR (CDCl3, TMS, δ, ppm): 175.6, 167.0, 165.0,
159.8, 153.4, 136.1, 130.9, 127.8, 127.4, 127.0, 120.3, 101.9, 73.9. 31 P NMR (161,9 MHz,
CDCl3, δ, ppm): 28.4; Elemental analysis C28H26N6O8P2S2 Calculated: C, 48.00; H, 3.74;
N, 12.00. Found: C, 47.98; H, 3.75; N, 12.07. [α]D −4.907◦ (c 1, ethanol).
20
[({5-[(1R,2R)-1,2-Dihydroxy-2-(5-{[(Hydroxyphosphonoyl)(4-
Nitrophenyl)Methyl]Amino}-1,3,4-Thiadiazol-2-yl)Ethyl]-1,3,4-
Thiadiazol-2-yl}Amino)(4-Nitrophenyl)Methyl]Phosphinic
Acid (3b)
White solid, yield 82%, m.p. 321–322◦C. IR (KBr, cm−1) υ: 3465 ( OH), 3301
1
( NH), 2402 ( P H), 1613 ( C N), 1258 ( P O), 1112 ( P O) cm−1. H NMR
(400 MHz, CDCl3, δ, ppm): 4.78 (d, 2H, 2 × CHP), 5.12 (d, 2H, 2 × PH), 5.49 (br,
2H, 2 × NH), 6.65 (d, 2H, 2 × CHOH), 6.89–6.96 (br, 2H, 2 × OH), 7.46–8.11 (m, 8H,
Ar H), 8.79 (br, 2H, 2 × POH) 13C NMR (CDCl3, TMS, δ, ppm): 174.0, 167.1, 165.8,
164.0, 150.1, 140.2, 131.2, 124.5, 72.9. 31 P NMR (CDCl3, TMS, δ, ppm): 28.4; Elemental
analysis C20H20N8O10P2S2 Calculated: C, 36.48; H, 3.06; N, 17.02. Found: C, 36.44; H,
3.01; N, 16.98. [α]D −6.523◦ (c 1, ethanol).
20
[({5-[(1R,2R)-1,2-Dihydroxy-2-(5-{[(Hydroxyphosphonoyl)(4-
Methoxyphenyl)Methyl]Amino}-1,3,4-Thiadiazol-2-yl)Ethyl]-1,3,4-
Thiadiazol-2-yl}Amino)(4-Methoxyphenyl)Methyl]Phosphinic
Acid (3c)
White solid, yield 51%, m.p. 331–332◦C. IR (KBr, cm−1) υ: 3501 ( OH), 3272
( NH), 2314 ( P H), 1602 ( C N), 1252 ( P O), 989 ( P O) cm−1. 1H NMR (400
MHz, CDCl3, δ, ppm): 3,79 (s, 6H, 2 × OCH3), 4.77 (d, 2H, 2 × CHP), 5.09 (d, 2H,
2 × PH), 5.44 (br, 2H, 2 × NH), 6.67 (d, 2H, 2 × CHOH), 6.88–6.95 (br, 2H, 2 × OH),
7.01–7.16 (m, 8H, Ar H), 8.83 (br, 2H, 2 × POH) 13C NMR (CDCl3, TMS, δ, ppm):
31
174.9, 165.9, 163.5, 160.8, 130.4, 129.0, 116.0, 72.9, 56.5. P NMR (CDCl3, TMS, δ,
ppm): 28.3; Elemental analysis C22H26N6O8P2S2 Calculated: C, 42.04; H, 4.17; N, 13.37.
Found: C, 41.96; H, 4.21; N, 13.07. [α]D −6.702◦ (c 1, ethanol).
20
[({5-[(1R,2R)-1,2-Dihydroxy-2-(5-{[(Hydroxyphosphonoyl)(4-
Chloroyphenyl)Methyl]Amino}-1,3,4-Thiadiazol-2-yl)Ethyl]-1,3,4-
Thiadiazol-2-yl}Amino)(4-Chlorophenyl)Methyl]Phosphinic
Acid (3d)
◦
White solid, yield 59%, m.p. 356–357 C. IR (KBr, cm−1) υ: 3405 ( OH), 3269
( NH), 2369 ( P H), 1601 ( C N), 1259 ( P O), 1077 ( P O) cm−1. 1H NMR (400
MHz, CDCl3, δ, ppm): 4.79 (d, 2H, 2 × CHP), 5.11 (d, 2H, 2 × PH), 5.47 (br, 2H, 2 × NH),
6.68 (d, 2H, 2 × CHOH), 6.88–6.98 (br, 2H, 2 × OH), 7.08–7.27 (m, 8H, Ar H), 8.81
(br, 2H, 2 × POH). 13C NMR (CDCl3, TMS, δ, ppm): 173.9, 165.8, 164.0, 139.0, 139.4,
31
136.0, 134.0, 129.7, 72.5. P NMR (CDCl3, TMS, δ, ppm): 28.4; Elemental analysis

870
P. KOPARIR ET AL.
C20H20Cl2N6O6P2S2 Calculated: C, 37.69; H, 3.16; N, 13.18. Found: C, 37.58; H, 3.15; N,
13.20. [α]D −6.572◦ (c 1, ethanol).
20
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