Synthesis of new functionalized hydroxy- and aminomethylphosphinates with indan moieties

Article abstract of DOI:10.1002/hc.21419

The convenient synthesis of new functionalized organophosphorus acids and their derivatives containing indan moieties was developed. The regioselective radical addition of bis(trimethylsiloxy)phosphine to indene proceeds to give rise to 2-indanylphosphoni

Full text of DOI:10.1002/hc.21419

Received: 1 August 2017
DOI: 10.1002/hc.21419
Revised: 18 April 2018
|
|
R E S E A R C H A R T I C L E
Synthesis of new functionalized hydroxy- and
aminomethylphosphinates with indan moieties
Andrey A. Prishchenko
Ludmila I. Livantsova
Mikhail V. Livantsov
Valery S. Petrosyan
Olga P. Novikova
|
|
|
|
Department of Chemistry, M.V. Lomonosov
Moscow State University, Moscow, Russia
Abstract
The convenient synthesis of new functionalized organophosphorus acids and their
derivatives containing indan moieties was developed. The regioselective radical ad-
dition of bis(trimethylsiloxy)phosphine to indene proceeds to give rise to
2-indanylphosphonite as key compound for preparation of above acids with bicyclic
substituents. Azobis(isobutyronitrile) (AIBN) in the conditions of its thermolysis
was used as effective initiator of the addition reaction. The further treatment of or-
ganophosphorus acids trimethylsilyl esters with the methanolic sodium methoxide
solution resulted in the water-soluble sodium salts of the corresponding acids.
Correspondence
Andrey A. Prishchenko, Department of
Chemistry, M.V. Lomonosov Moscow State
University, Moscow, Russia.
Email: aprishchenko@yandex.ru
Funding information
Russian Foundation for Basic Research,
Grant/Award Number: 17-03-00169
1
INTRODUCTION
|
2
RESULTS AND DISCUSSION
|
Functionalized hydroxy- and aminomethylphosphonates
(phosphinates) and their derivatives are the promising or-
ganophosphorus biomimetics of natural hydroxy and amino
acids and widely used as effective multidentate ligands and
biologically active substances with multifactor activity. It
should be noted that the functionalized organophosphorus
acids with aryl, heterocyclic, and bicyclic moieties are of
particular interest among these substances.[1-4] Earlier, we
described original methods for the synthesis of aminometh-
ylenebisphosphonic acid derivatives[5], as well as new aryl-
substituted methylphosphonic and methylenediphosphonic
acids and their derivatives[6a] using trimethylsilyl esters of
trivalent phosphorus acids as highly reactive synthons. In the
present work, convenient methods for the synthesis of func-
tionalized amino- and hydroxymethylphosphinic acids and
their derivatives, including bicyclic moieties of indan as well
as aromatic and heterocyclic substitutents, are proposed via
highly reactive bis(trimethylsiloxy)phosphine. Preliminary
brief data on the synthesis of organophosphorus derivatives
of indan were published by us earlier (cf. [6b-e]). In this arti-
cle, we are reporting detailed synthesis of 32 new compounds
with important moieties of heterocycles and amino acids, in-
In the present work, we accomplished radical addition of
bis(trimethylsiloxy)phosphine to indene. It has been estab-
lished that the radical addition of bis(trimethylsiloxy)phos-
phine to indene proceeds regioselectively to give phosphonite
1 as new key synthon in high yield. Azobis(isobutyronitrile)
was used as a reaction initiator under the conditions of its
thermolysis (100-120°C; Scheme 1).
Phosphonite 1 was successfully used by us for pre-
paring the derivatives of new functionalized aminometh-
ylphosphinic acids, including bicyclic indan moieties.
Thus, phosphonite 1 readily reacts with aminomethylat-
ing reagents such as aminals, N-chloromethylamides, and
N-ethoxymethyl-N,N-bis(trimethylsilyl)amine to form
phosphinates 2 in good yields, the reaction conditions
being determined by the reactivity of the aminomethylating
reagent (cf.[7]). Various aminals interact with phosphonite
1 only under heating in the presence of zinc chloride as
a catalyst, but the highly reactive N-chloromethylamides
react already at 10°C. Phosphonite 1 reacts with N-
ethoxymethyl-N,N-bis(trimethylsilyl)amine at 20-120°C,
and chlorotrimethylsilane and zinc chloride are also used
as catalysts (Scheme 2).
1
cluding their full characterization via complete H, 13C, and
The interaction of phosphonite 1 with sulfur is a conve-
nient method for the synthesis of thiophosphonate 3, and the
31P NMR data.
|
Heteroatom Chemistry. 2018;e21419.
https://doi.org/10.1002/hc.21419
wileyonlinelibrary.com/journal/hc
© 2018 Wiley Periodicals, Inc.
1 of 9

2 of 9
PRISHCHENKO Et al.
|
addition of phosphonite 1 via its POSi moiety to the carbonyl
group of various aldehydes proceeds under mild conditions
and leads to substituted trimethylsiloxymethylphosphinate
4, including aromatic and heterocyclic moieties along with
indan group (Scheme 3).
The reaction of phosphonite 1 with trimethylsilyl acry-
late proceeds as a 1,4-addition to the conjugated system of
acrylate with the formation of ketene acetal 5a as an interme-
diate, the further interaction of intermediate 5a with diethyl
phosphite results in phosphinate 5 containing a propionic
acid group (cf.[8]), (Scheme 4). It should be noted that dieth-
ylphosphite smoothly removes only one trimethylsilyl group
of ketene acetal 5a, and this method can be used for further
synthetic purposes.
31P NMR spectra where the data for the major isomer are
presented first.
3
CONCLUSIONS
|
Summarizing, we have developed convenient methods for
the synthesis of new derivatives of functionalized amino-and
hydroxymethylphosphinic acids, including bicyclic moieties
of indan as well as aromatic and heterocyclic substituents,
based on readily available starting materials such as indene
and trimethylsilyl esters of trivalent phosphorus acids. The
resulting compounds are convenient synthons for the prepa-
ration of various functionalized organophosphorus com-
pounds and are of interest as biologically active substances
with various properties and promising polydentate ligands.
The treatment of phosphonite 1, phosphinates 2,4,5, and
thiophosphonate 3 with dilute solutions of sodium methoxide in
methanol gives stable water-soluble sodium salts of correspond-
ing phosphonous 6, thiophosphonic 8, and phosphinic 7,9,10
acids (Scheme 5). Salts 6-10 are colorless hygroscopic crystals.
The structures of organophosphorus acids and their de-
rivatives 1-10 with indan moieties were confirmed by the
1H, 13C, 31P NMR spectra where the characteristic signals of
corresponding moieties were observed. The numbers of the
4
EXPERIMENTAL
|
The H, 13C, and 31P NMR spectra were registered on a
Bruker Avance-400 spectrometer (400, 100, and 162 MHz,
respectively) against TMS as internal standard (1H and 13C)
and 85% H3PO4 in D2O as external standard (31P). All reac-
tions were carried out under dry argon in anhydrous sol-
vents. The starting esters of organophosphorus acids were
prepared as described.[8,9] Sodium salts 6-10 are decom-
posed above 100°C and do not have clear melting points.
1
carbon atoms used for the description of the H, 13C NMR
1
spectra for compounds 1,24,5 in the experimental section
are shown in the schemes (see Schemes 1-4). According to
the NMR spectral data, the compounds with asymmetrical
atoms and various amide moieties are the mixtures of ste-
1
reoisomers, and their ratio was determined by the H and
4.1
Bis(trimethylsilyl) 2,3-dihydro-1H-
|
2
3
inden-2-ylphosphonite (1)
a
1
(Me3SiO)2P
(Me3SiO)2PH +
A mixture of bis(trimethylsiloxy)phosphine (48 g 0.23 mol),
1H indene (21 g, 0.18 mol) and azobis(isobutyronitrile) (0.2 g,
0.0012 mol) was heated to 100°C. Then, the temperature of
the reaction mixture was gradually raised to 120°C over the
1
SCHEME 1 Reagents and conditions: (a) AIBN, 100-120°C
2
3
OSiMe3
OSiMe3
P
1
b
a
P
1
C4H2NR2
- Me3SiCl
- Me3SiNR2
CH2NR2
O
O
2a-d
2e-i
5
6
5
6
5
6
COC7H3
7 (c),
7
(b),
N
O (d), N(Me)CHO (e), N
(f),
N
N
R2N = NMe2 (a),
C5H2C6H3
O
5
6
7(g),
7
(h), N(COOEt)C5H2COOEt (i).
N
N
6
5
8
O
9
SCHEME 2 Reagents and conditions:
(a) (R2N)2CH2, ZnCl2, 110-130°C;
(b) R2NCH2Cl, CH2Cl2, 10°C, (c)
(Me3Si)2NCH2OEt, CH2Cl2, Me3SiCl,
ZnCl2, 20-120°C
OSiMe3
c
1
P
CH2N(SiMe3)2
-Me3SiOEt
O
2j

PRISHCHENKO Et al.
3 of 9
|
2
3
OSiMe3
a
b
1
P(OSiMe3)2
S
1
P
C4H(OSiMe3)X
O
3
4a-c
(c).
(b),
X = Ph (a),
SCHEME 3 Reagents and conditions:
N
O
(a) S, C6H6, 80°C; (b) XCHO, CH2Cl2, 10°C
2
3
OSiMe3
P
a
OSiMe3
C4H2C5H2COOSiMe3
b
1
1
SCHEME 4 Reagents and conditions:
(a) CH2=CHCOOSiMe3, Et2O, 20°C; (b)
(EtO)2P(O)H, Et2O, 40°C
P
CH2CH=C(OSiMe3)2
- (EtO)2POSiMe3
O
O
5a
5
ONa
a
1
P
- n MeOSiMe3
H
O
6
ONa
a
2a-j
P
- n MeOSiMe3
CH2NR2
O
7a-j
O
(c),
N
(g),
O (d), N(Me)CHO (e), N(Et)Ac (f),
(b),
N
N
N
R2N = NMe2 (a),
N
(h), N(COOEt)CH2COOEt (i), NH2 (j).
O
a
P(ONa)2
S
3
- n MeOSiMe3
8
ONa
P
a
4a-c
- n MeOSiMe3
CH(OH)X
O
9a-c
(c).
(b),
X = Ph (a),
N
O
ONa
a
5
P
- n MeOSiMe3
CH2CH2COONa
SCHEME 5 Reagents and conditions:
O
10
(a) n MeONa (n = 1,2), MeOH, Et2O, 10°C
course of 1 hr. After that the reaction mixture was distilled
in a vacuum to obtain 49 g of phosphonite I, yield 83%, bp
126°C (1 mm Hg). 1H NMR (CDCl3, 400 MHz), δ, ppm: 0.21
(s, 18H, 2 Me3Si), 2.31 (d, 1H, 2JPH = 3.6 Hz, 3JHH = 8.8 Hz,
C1H), 2.90-3.05 (m, 4H, 2 C2H2), 7.08-7.20 (m, 4H, 4 CArH).
31P NMR (CDCl3, 162 MHz), δ, ppm: 155.6 (s). Anal. Calcd
for C15H27O2PSi2. C 55.18; H 8.33. Found: C 55.02; H 8.17.
4.2
Trimethylsilyl 2,3-dihydro-1H-inden-2-
|
yl(N,N-dimethylaminomethyl)phosphinate (2a)
3
13C NMR (CDCl3, 100 MHz), δ, ppm: 1.3 (d, JPC = 4.6 Hz,
Me3Si), 32.0 (d, 2JPC = 19.7 Hz, C2), 46.3 (d, 1JPC = 20.3 Hz,
C1), 124.2 (s, CAr), 126.0 (s, CAr), 143.1 (d, 3JPC = 5.6 Hz, C3).
A
mixture of phosphonite
1
(6.5 g, 0.02 mol),
bis(dimethylamino)methane (2.2 g, 0.022 mol), and zinc

4 of 9
PRISHCHENKO Et al.
|
chloride (0.1 g, 0.0007 mol) was heated at 110-130°C
for 1.5 hr and then distilled to obtain 4.6 g of phosphinate
CArH). 13C NMR (CDCl3, 100 MHz), δ, ppm: 0.6 (s, Me3Si),
32.3 and 32.8 (s, C2), 36.3 (d, JPC = 97.9 Hz, C1), 54.9
1
1
2a, yield 74%, bp 141°C (1 mm Hg). H NMR (CDCl3,
(d,3JPC = 8.7 Hz, C5), 56.1 (d, 1JPC = 111.3 Hz, C4), 66.1 (s,
3
400 MHz), δ, ppm: 0.34 (s, 9H, Me3Si), 2.45 (s, 6H,
C6), 123.6 (s, CAr), 125.8 (s, CAr), 141.1(d, JPC = 6.5 Hz,
Me2N), 2.12 and 2.75 (C4HAHBN, 2H, JPHA = 10.8 Hz,
C3) and 141.2 (d,3JPC = 8.0 Hz, C3). 31P NMR (CDCl3,
162 MHz), δ, ppm: 41.2 (s). Anal. Calcd for C17H28NO3PSi.
C 57.77; H 7.98. Found: C 57.68; H 7.89.
2
2JPHB = 8.4 Hz, JHAHB = 14.8 Hz, HA and HB), 2.85-2.95
2
(m, 1H, C1H), 3.10-3.40 (m, 4H, C2H2), 7.20-7.30 (m, 4H,
4 CArH). 13C NMR (CDCl3, 100 MHz), δ, ppm: 0.1 (s,
Me3Si), 31.6 (s, C2), 32.2 (s, C2), 35.5 (d, JPC = 97.9 Hz,
1
4.6
Trimethylsilyl 2,3-dihydro-1H-
C1), 46.5 (d,3JPC = 9.7 Hz, C5), 46.6 (d, 3JPC = 10.5 Hz, C5),
|
inden-2-yl(N-methyl-N-formylaminomethyl)
56.7 (d,1JPC = 112.1 Hz, C4), 123.0 (s, CAr), 125.2 (s, CAr),
phosphinate (2e)
140.7 (d, 3JPC = 9.1 Hz, C3), 140.5 (d,3JPC = 9.1 Hz, C3). 31
P
NMR (CDCl3, 162 MHz), δ, ppm: 41.6 (s). Anal. Calcd for
C15H26NO2PSi. C 57.85; H 8.41. Found: C 57.68; H 8.29.
Phosphinates 2b-d were obtained similarly.
To a solution of phosphonite 1 (5.4 g, 0.017 mol) in meth-
ylene chloride (10 mL), a solution of N-chloromethyl-
N-methylformamide (1.8 g, 0.017 mol) in methylene
chloride (5 mL) was added dropwise with stirring at 10°C.
The solvent was then removed, and the residue was distilled
in a vacuum to obtain 3.8 g of phosphinate 2e, yield 70%, bp
187°C (1 mm Hg). The first isomer, 75%. 1H NMR (CDCl3,
400 MHz), δ, ppm: −0.05 (s, 9H, Me3Si), 2.36-2.48 (m,
1H, C1H), 2.82-3.00 (m, 4H, 2 C2H2), 2.87 (s, 3H, MeN),
3.18-3.68 (m, 2H, C4H2), 6.80-6.92 (m, 4H, 4 CArH), 7.78
(s, 1H, CHO). 13C NMR (CDCl3, 100 MHz), δ, ppm: 0.6 (s,
Me3Si), 31.8 (s, C2), 32.80 (s, C2), 35.3 (s, MeN), 36.1 (d,
1JPC = 96.7 Hz, C1), 42.5 (d, 1JPC = 101.0 Hz, C4), 123.6 (s,
4.3
Trimethylsilyl 2,3-dihydro-1H-inden-2-
|
yl(piperidin-1-ylmethyl)phosphinate (2b)
Yield 78%, bp 169°C (1 mm Hg), mp 61°C. 1H NMR
(CDCl3, 400 MHz), δ, ppm: 0.13 (s, 9H, Me3Si), 1.40-1.43
(m, 6H, 2 C6H2, C7H2), 2.30-2.60 (m, 4H, 2 C2H2), 2.68-2.85
(m, 2H, C1H2), 2.95-3.20 (m, 6H, C4H2, 2 C5H2), 7.00-7.10
(m, 4H, 4 CArH). 13C NMR (CDCl3, 100 MHz), δ, ppm: 1.0
(s, Me3Si), 23.6 (s, C7), 25.8 (s, 2 C6), 32.7 and 33.4 (s, C2),
36.7 (d, JPC = 98.0 Hz, C1), 56.4 (d, JPC = 9.8 Hz, C5),
57.3 (d, 1JPC = 113.8 Hz, C4), 123.0 (s, CAr), 126.2 (s, CAr),
141.6 (d, 3JPC = 9.9 Hz, C3), 141.8 (d, 3JPC = 9.8 Hz, C3). 31P
NMR (CDCl3, 162 MHz), δ, ppm: 42.4 (s). Anal. Calcd for
C18H30NO2PSi. C 61.51; H 8.60. Found: C 61.26; H 8.52.
2 CAr), 125.9 (s, 2 CAr), 140.8 (d, JPC = 8.9 Hz, C3), 140.9
1
3
3
3
(d, JPC = 8.6 Hz, C3), 161.7 (s, CO). 31P NMR (CDCl3,
1
162 MHz), δ, ppm: 38.8 (s). The second isomer, 25%. H
NMR (CDCl3, 400 MHz), δ, ppm: -0.05 (s, 9H, Me3Si), 2.36-
2.48 (m, 1H, C1H), 2.82-3.00 (m, 4H, 2 C2H2), 2.77 (s, 3H,
MeN), 3.18-3.68 (m, 2H, C4H2), 6.80-6.92 (m, 4H, 4 CArH),
7.72 (s, 1H, CHO). 13C NMR (CDCl3, 100 MHz), δ, ppm: 0.6
(s, Me3Si), 32.0 (s, C2), 32.5 (s, C2), 35.3 (s, MeN), 35.9 (d,
4.4
Trimethylsilyl 2,3-dihydro-1H-inden-2-
|
yl(azepan-1-ylmethyl)phosphinate (2c)
1
1JPC = 96.1 Hz, C1), 46.9 (d, JPC = 99.5 Hz, C4), 123.6 (s,
Yield 80%, bp 191°C (1 mm Hg), mp 48°C. 1H NMR
(CDCl3, 400 MHz), δ, ppm: 0.17 (s, 9H, Me3Si), 1.40-1.60
(m, 8H, 2 C6H2, 2 C7H2), 2.60-2.90 (m, 6H, C1H2, 2 C2H2),
3.00-3.30 (m, 6H, C4H2, 2 C5H2), 7.00-7.20 (m, 4H, 4 CArH).
13C NMR (CDCl3, 100 MHz), δ, ppm: 1.2 (s, Me3Si), 26.8
(s, C7), 28.1 (s, 2 C6), 32.8 (s, C2), 33.4 (s, C2), 36.6 (d,
2 CAr), 125.9 (s, 2 CAr), 140.3 (d, JPC = 8.8 Hz, C3), 140.5
3
3
(d, JPC = 8.4 Hz, C3), 162.1 (s, CO). 31P NMR (CDCl3,
162 MHz), δ, ppm: 38.3 (s). Anal. Calcd for C15H24NO3PSi.
C 55.36; H 7.43. Found: C 55.23; H 7.35.
Phosphinates 2f-j were obtained similarly.
1JPC = 97.8.0 Hz, C1), 56.5 (d, JPC = 113.8 Hz, C4) 57.6
1
4.7
Trimethylsilyl 2,3-dihydro-1H-inden-
(d, JPC = 7.8 Hz, C5), 124.2 (s, 2 CAr), 126.3 (s, 2 CAr),
3
|
2-yl(N-ethyl-N-acetylaminomethyl)phosphinate
141.8 (d, 3JPC = 9.7 Hz, C3),142.0 (d, 3JPC = 9.8 Hz, C3). 31
P
(2f)
NMR (CDCl3, 162 MHz), δ, ppm: 43.2 (s). Anal. Calcd for
C19H32NO2PSi. C 62.43; H 8.82. Found: C 62.28; H 8.75.
Yield 73%, bp 187°C (1 mm Hg). 1H NMR (CDCl3,
400 MHz), δ, ppm: 0.15 (s, 9H, Me3Si), 0.84 (t, 3H,
3JHH = 7.2 Hz, C6H3), 1.76 (s, 3H, C7H3), 2.32-2.41 (m, 1H,
C1H), 2.74-2.98 (m, 4H, 2 C2H2), 3.10-3.36 (m, 3H, C4HB,
4.5
Trimethylsilyl 2,3-dihydro-1H-inden-2-
|
yl(morpholin-4-ylmethyl)phosphinate (2d)
C5H2), 3.71 (dd, 2H, JHAHB = 15.2 Hz, JPHA = 5.6 Hz,
C4HB), 6.70-6.85 (m, 4H, 4 CArH). 13C NMR (CDCl3,
100 MHz), δ, ppm: 0.4 (s, Me3Si), 12.2 (s, C6), 20.1 (s, C7),
2
2
Yield 81%, bp 175°C (1 mm Hg), mp 55°C. 1H NMR
(CDCl3, 400 MHz), δ, ppm: −0.01 (s, 9H, Me3Si), 2.20-2.45
(m, 4H, 2 C2H2), 2.52-2.60 (m, 1H, C1H), 2.80-3.10 (m, 6H,
C4H2, 2 C5H2), 3.36 (s, 4H, 2 C6H2), 6.84-6.94 (m, 4H, 4
31.6 (s, C7), 32.9 (s, C2), 36.1 (d, JPC = 95.5, C1), 42.1 (d,
1
1JPC = 102.0 Hz, C4), 43.2 (s, 2 C5), 123.4 (s, 2 CAr), 125.7 (s,

PRISHCHENKO Et al.
5 of 9
|
2 CAr), 140.8 (d, 3JPC = 9.1 Hz, C3), 140.9 (d,3JPC = 9.9 Hz,
C3), 169.0 (s, CO). 31P NMR (CDCl3, 162 MHz), δ, ppm:
39.9 (s). Anal. Calcd for C17H28NO3PSi. C 57.77; H 7.98.
Found: C 57.52; H 7.90.
140.7 (d, JPC = 8.7 Hz, C3), 155.0 (d, JPC = 3.0 Hz, C7),
3
3
168.1 (s, CO). 31P NMR (CDCl3, 162 MHz), δ, ppm: 39.6
1
(s). The second isomer, 30%. H NMR (CDCl3, 400 MHz),
δ, ppm: 0.23 (s, 9H, Me3Si), 1.16-1.30 (m, 6H, 2 CH3), 2.35-
2.50 (m, 1H, C1H), 2.70-2.90 (m, 4H, 2 C2H2), 3.20-3.68 (m,
2H, C4H2), 3.65-3.75 (m, 4H, 2 CH2O), 4.02 (s, 2H, C5H2),
6.85-6.95 (m, 4H, 4 CArH). 13C NMR (CDCl3, 100 MHz), δ,
ppm: 0.01 (s, Me3Si), 13.1 (s, 2 Me), 31.3 (s, C2), 31.4 (s, C2),
4.8
Trimethylsilyl 2,3-dihydro-1H-inden-
|
2-yl[(2-oxopyrrolidin-1-yl)methyl]phosphinate
(2g)
35.2 (d, JPC = 94.9 Hz, C1), 44.4 (d, JPC = 102.8 Hz, C4),
1
1
Yield 76%, bp 186°C (1 mm Hg). 1H NMR (CDCl3,
400 MHz), δ, ppm: −0.12 (s, 9H, Me3Si), 1.55-1.70 (m, 2H,
C6H2), 1.90-2.00 (m, 2H, C7H2), 2.38-2.39 (m, 1H, C1H),
2.75-2.92 (m, 6H, 2 C2H2, C5H2), 3.00-3.44 (m, 2H, C4H2),
6.74-6.85 (m, 4H, 4 CArH). 13C NMR (CDCl3, 100 MHz),
δ, ppm: 0.38 (s, Me3Si), 17.1 (s, C6), 29.3 (s, C7), 31.6
47.8 (s, C(5)), 61.0 (s, CH2O), 123.3 (s, CAr), 125.6 (s, CAr),
140.2 (d, JPC = 8.7 Hz, C3), 140.3 (d, JPC = 8.7 Hz, C3),
154.6 (s, C7), 168.1 (s, CO). 31P NMR (CDCl3, 162 MHz),
δ, ppm: 39.1 (s). Anal. Calcd for C20H32NO6PSi. C 54.40; H
7.31. Found: C 54.15; H 7.22.
3
3
(s, C2), 32.5 (s, C2), 35.7 (d, JPC = 95.9 Hz, C1), 41.1 (d,
1
4.11
Trimethylsilyl 2,3-dihydro-1H-inden-
1JPC = 104.4 Hz, C4), 47.6 (s, C5), 123.4 (s, 2CAr), 125.7 (s, 2
CAr), 140.6 (d, 3JPC = 7.2, C3), 140.6 (d, 3JPC = 7.2 Hz, C3),
140.7 (d, 3JPC = 9.1 Hz, C3), 173.8 (s, CO). 31P NMR (CDCl3,
162 MHz), δ, ppm: 39.1 (s). Anal. Calcd for C17H26NO3PSi.
C 58.10; H 7.46. Found: C 57.98; H 7.28.
|
2-yl[N,N-bis(trimethylsilyl)aminomethyl]
phosphinate (2j)
Yield 74%, bp 171°C (1 mm Hg). The first isomer, 65%.
1H NMR (CDCl3, 400 MHz), δ, ppm: -0.35-0.02 (m, 27H,
Me3Si), 2.30-2.45 (m, 1H, C4HB), 2.55-2.65 (m, 1H, C1H),
2.85-3.05 (m, 5H, C4HA, 2 C2H2). 13C NMR (CDCl3,
100 MHz), δ, ppm: -1.0 (s, Me3SiO), 0.68 (s, Me3SiN),
33.0 (s, C2), 33.6 (s, C2), 34.8 (d, 1JPC = 94.1 Hz, C1), 39.7
(d, 1JPC = 103.3 Hz, C4), 123.6 (s, 2 CAr), 125.9 (s, 2 CAr),
141.3 (d, 3JPC = 10.5 Hz, C3). 31P NMR (CDCl3, 162 MHz),
δ, ppm: 44.0 (s). The second isomer, 35%. 1H NMR (CDCl3,
400 MHz), δ, ppm: -0.35-0.02 (m, 27H, Me3Si), 2.30-2.45
(m, 1H, C4HB), 2.55-2.65 (m, 1H, C1H), 2.85-3.05 (m, 5H,
C4HA, 2 C2H2). 13C NMR (CDCl3, 100 MHz), δ, ppm: -0.9
(s, Me3SiO), 1.8 (s, Me3SiN), 32.7 (s, C2), 33.2 (s, C2),
35.0 (d, 1JPC = 93.8 Hz, C1), 43.0 (d, 1JPC = 103.0 Hz, C4),
4.9
Trimethylsilyl 2,3-dihydro-1H-inden-2-
|
yl[(2-oxoazepan-1-yl)methyl]phosphinate (2h)
Yield 72%, bp 205°C (1 mm Hg), mp 72°C. 1H NMR
(CDCl3, 400 MHz), δ, ppm: 0.53 (s, 9H, Me3Si), 1.25-1.55
(m, 6H, C6H2, C7H2, C8H2), 2.20-2.30 (m, 2H, C9H2), 2.35-
2.50 (m, 1H, C1H), 2.85-3.15 (m, 4H, 2 C2H2), 3.25-3.50
(m, 4H, C4H2, C5H2), 6.82-7.15 (m, 4H, 4 CArH). 13C NMR
(CDCl3, 100 MHz), δ, ppm: -0.24 (s, Me3Si), 22.0 (s, C7),
22.6 (s, C8), 27.2 (s, C6), 28.4 (s, C9), 31.1 (s, C2), 32.1 (s,
1
1
C2), 35.3 (d, JPC = 95.7 Hz, C1), 45.1 (d, JPC = 103.2 Hz,
C4), 49.3 (s, C5), 122.8 (s, 2 CAr), 125.0 (s, 2 CAr), 140.2
(d, 3JPC = 9.3 Hz, C3), 140.4 (d, 3JPC = 9.3 Hz, C3), 175.0 (s,
CO). 31P NMR (CDCl3, 162 MHz), δ, ppm: 39.4 (s). Anal.
Calcd for C19H30NO3PSi. C 60.13; H 7.97. Found: C 60.01;
H 7.88.
3
123.6 (s, 2 CAr), 126.0 (s, 2 CAr), 141.8 (d, JPC = 5.1 Hz,
C3). 31P NMR (CDCl3, 162 MHz), δ, ppm: 41.3 (s). Anal.
Calcd for C19H38NO2PSi3. C 53.35; H 8.95.Found: C 53.20;
H 8.87.
4.12
Bis(trimethylsilyl) 2,3-dihydro-1H-
|
4.10
Trimethylsilyl 2,3-dihydro-
inden-2-ylthiophosphonate (3)
|
1H-inden-2-yl[N-ethoxycarbonyl-N-
(ethoxycarbonylmethyl)aminomethyl]
phosphinate (2i)
To a solution of phosphonite 1 (4 g, 0.012 mol) in benzene
(10 mL) of sulfur (0.4 g, 0.013 mol) was added. After exo-
thermic reaction had been complete, the mixture was heated
for 15 min on a water bath and cooled. Excess sulfur was
filtered off, the solvent was removed, and the residue was
distilled in a vacuum to obtain 4 g (91%) of thiophosphonate
Yield 78%, bp 200°C (1 mm Hg). The first isomer, 70%. 1H
NMR (CDCl3, 400 MHz), δ, ppm: 0.19 (s, 9H, Me3Si), 1.16-
1.30 (m, 6H, 2 CH3), 2.35-2.50 (m, 1H, C1H), 2.70-2.90 (m,
4H, 2 C2H2), 3.20-3.68 (m, 2H, C4H2), 3.65-3.75 (m, 4H, 2
CH2O), 3.91 (s, 2H, C5H2), 6.85-6.95 (m, 4H, 4 CArH). 13C
NMR (CDCl3, 100 MHz), δ, ppm: 0.01 (s, Me3Si), 13.5 (s, 2
1
3, bp 142°C (1 mm Hg). H NMR (CDCl3, 400 MHz), δ,
ppm: 0.34 (s, 18H, 2 Me3Si), 2.75-2.90 (m, 1H, C1H), 3.10-
3.40 (m, 4H, 2 C2H2), 7.10-7.25 (m, 4H, 4 CArH). 13C NMR
(CDCl3, 100 MHz), δ, ppm: 1.1 (s, Me3Si), 34.3 (s, C2), 44.8
(d, 1JPC = 117.7 Hz, C1), 124.0 (s, CAr), 126.2 (s, CAr), 141.5
Me), 32.4 (s, C2), 32.5 (s, C2), 35.1 (d, JPC = 95.9 Hz, C1),
1
44.8 (d, JPC = 105.0 Hz, C4), 48.0 (s, C5), 59.8 (s, CH2O),
1
3
3
123.2 (s, CAr), 125.5 (s, CAr), 140.5 (d, JPC = 8.7 Hz, C3),
(d, JPC = 10.6 Hz, C3). 31P NMR (CDCl3, 162 MHz), δ,

6 of 9
PRISHCHENKO Et al.
|
ppm: 75.1 (s). Anal. Calcd for C15H27O2PSSi2. C 50.24; H
7.59. Found: C 50.03; H 7.50.
(s, Me3Si), 32.8 (s, C2), 33.1 (s, C2), 37.4 (d, 1JPC = 97.4 Hz,
C1), 67.8 (d, 1JPC = 118.6 Hz, C4H), 109.0 (s, CFur), 110.2 (s,
CFur), 123.5 (s, CAr), 126.2 (s, CAr), 141.0 (d, 3JPC = 8.9 Hz,
C3), 141.1 (d, JPC = 8.9 Hz, C3), 141.9 (s, CFurHO). 150.0
3
4.13
Trimethylsilyl 2,3-dihydro-1H-
(s, CFurO). 31P NMR (CDCl3, 162 MHz), δ, ppm: 36.7 (s).
Anal. Calcd for C20H31O4PSi2. C 56.84; H 7.39. Found: C
56.73; H 7.23.
|
inden-2-yl[phenyl(trimethylsiloxy)methyl]
phosphinate (4a)
To a solution of phosphonite 1 (4 g, 0.012 mol) in meth-
ylene chloride (10 mL), a solution of benzaldehyde (1.2 g,
0.011 mol) in methylene chloride (5 mL) was added drop-
wise with stirring at 10°C. The solvent was then removed,
and the residue was distilled in a vacuum to obtain 4 g of
phosphinate 4a, yield 83%, bp 182°C (1 mm Hg), mp 92°C.
The first isomer, 60%. 1H NMR (CDCl3, 400 MHz), δ, ppm:):
0.04 (s, 9H, Me3Si), 0.08 (s, 9H, Me3Si), 2.75-2.95 (m, 1H,
C1H), 3.05-3.40 (m, 4H, 2 C2H2), 4.91 (d, 1H, 2JPH = 9.6 Hz,
C4H), 7.10-7.55 (m, 9H, 4 CArH, C6H5). 13C NMR (CDCl3,
100 MHz), δ, ppm:): 0.17 (s, Me3Si), 1.07 (s, Me3Si), 32.9
4.15
Trimethylsilyl 2,3-dihydro-1H-inden-
|
2-yl[pyridin-3-yl(trimethylsiloxy)methyl]
phosphinate (4c)
Yield 83%, bp 188°C (1 mm Hg), mp 83°C. The first isomer, 65
%. 1H NMR (CDCl3, 400 MHz), δ, ppm: 0.05 (s, 18H, Me3Si),
2.50-2.65 (m, 1H, C1H), 2.70-3.00 (m, 4H, 2 C2H2), 4.68 (d,
1H, 2JPH = 9.2 Hz, C4H), 6.70-6.95 (m, 4H, 4 CArH), 7.15-8.60
(m, 4H, 4 CPyH). 13C NMR (CDCl3, 100 MHz), δ, ppm: 0.2
(s, 2 Me3Si), 31.1 (s, C2), 31.4 (s, C2), 37.3 (d, 1JPC = 98.1 Hz,
(s, C2), 33.4 (s, C2), 34.7 (d, JPC = 95.4 Hz, C1), 74.1 (d,
C1), 70.7 (d, JPC = 114.4 Hz, C4H), 123.6 (s, CAr), 125.8 (s,
1
1
1JPC = 114.9 Hz, C4H), 124.4 (s, CAr), 126.5 (s, CAr), 127.3
(s, CPh), 127.8 (s, CPh), 128.1 (s, CPh), 137.2 (s, CPh), 142.0
(d, 3JPC = 9.3 Hz, C3), 142.1 (d, 3JPC = 8.2 Hz, C3). 31P NMR
(CDCl3, 162 MHz), δ, ppm: 40.5 (s).The second isomer, 40%.
1H NMR (CDCl3, 400 MHz), δ, ppm: 0.02 (s, 9H, Me3Si),
0.09 (s, 9H, Me3Si), 2.75-2.95 (m, 1H, C1H), 3.05-3.40 (m,
4H, 2 C2H2), 5.03 (d, 1H, 2JPH = 7.6 Hz, C4H), 7.10-7.55 (m,
9H, 4 CArH, C6H5). 13C NMR (CDCl3, 100 MHz), δ, ppm:
0.96 (s, Me3Si), 1.99 (s, Me3Si), 33.7 (s, C2), 34.1 (s, C2),
35.2 (d, 1JPC = 96.3 Hz, C1), 74.0 (d, 1JPC = 115.3 Hz, C4H),
141.8 (d, 3JPC = 9.2 Hz, C3), 142.0 (d, 3JPC = 9.3 Hz, C3). 31P
NMR (CDCl3, 162 MHz), δ, ppm: 39.4 (s). Anal. Calcd for
C22H33O3PSi2. C 61.08; H 7.69. Found: C 60.92; H 7.55.
CAr), 132.3 (s, CPy), 140.4 (d, JPC = 9.0 Hz, C3), 140.5 (d,
3
3JPC = 11.0 Hz, C3), 140.6 (d, JPC = 8.6 Hz, CPy), 147.7 (d,
3
3JPC = 4.4 Hz,CPy),153.8(s,CPy).31PNMR(CDCl3,162 MHz),
1
δ, ppm: 38.8 (s). The second isomer, 35%. H NMR (CDCl3,
400 MHz), δ, ppm: −0.19 (s, 9H, Me3Si), −0.02 (s, 9H, Me3Si),
2.25-2.40 (m, 1H, C1H), 2.70-3.00 (m, 4H, 2 C2H2), 4.79 (d,
1H, 2JPH = 7.2 Hz, C4H), 6.70-6.95 (m, 4H, 4 CArH), 7.15-8.60
(m, 4H, 4 CPyH). 13C NMR (CDCl3, 100 MHz), δ, ppm: -0.7
(s, Me3Si), -0.6 (s, Me3Si), 32.1 (s, C(2)), 32.5 (s, C(2)), 34.2
(d, 1JPC = 96.6 Hz, C1), 71.2 (d, 1JPC = 112.5 Hz, C4H), 123.5
(s, CAr), 126.0 (s, CAr), 132.6 (s, CPy), 140.8 (d, 3JPC = 9.3 Hz,
C3), 140.9 (d, 3JPC = 9.0 Hz, C3), 141.0 (d, 3JPC = 8.0 Hz, CPy),
147.8 (d, 3JPC = 5.4 Hz, CPy), 151.0 (s, CPy). 31P NMR (CDCl3,
162 MHz), δ, ppm: 39.5 (s). Anal. Calcd for C21H32NO3PSi2. C
58.17; H 7.44. Found: C 58.01; H 7.30.
4.14
Trimethylsilyl 2,3-dihydro-1H-
|
inden-2-yl[fur-2-yl(trimethylsiloxy)methyl]
phosphinate (4b)
4.16
Trimethylsilyl 2,3-dihydro-1H-
|
inden-2-yl[2-(trimethylsiloxycarbonyl)ethyl]
phosphinate (5)
Yield 82%, bp 169°C (1 mm Hg). The first isomer, 60 %.
1H NMR (CDCl3, 400 MHz), δ, ppm: -0.11 (s, 9H, Me3Si),
-0.10 (s, 9H, Me3Si), 2.60-2.75 (m, 1H, C1H), 2.85-3.15
A solution of trimethylsilyl acrylate (3.1 g, 0.02 mol) in
methylene chloride (5 mL) was added dropwise with stirring
to a solution of phosphonite 1 (6.5 g, 0.02 mol) in methylene
chloride (15 mL). The mixture was kept for 2 hr with stirring,
then diethyl phosphite (4.1 g, 0.03 mol) was added to the
mixture. The solvent was removed, and the residue was dis-
tilled to obtain 6.7 g of phosphinate 5, yield 84%, bp 178°C
(1 mm Hg). 1H NMR (CDCl3, 400 MHz), δ, ppm: 0.02 (s, 9H,
Me3Si), 0.10 (s, 9H, Me3Si), 1.70-1.85 (m, 1H, C1H), 2.30-
2.45 (m, 2H, C4H2), 2.85-3.00 (m, 6H, 2 C2H2, C5H2), 6.85-
7.00 (m, 4H, 4 CArH). 13C NMR (CDCl3, 100 MHz), δ, ppm:
-0.9 (s, Me3Si), 0.04 (s, Me3Si), 23.1 (d, 1JPC = 93.0 Hz, C4),
27.6 (d, 2JPC = 2.0 Hz, C5),32.3 (s, C2), 32.8 (s, C2), 123.7 (s,
2CAr), 126.1 (s, 2CAr), 140.9 (s, C3), 171.9 (d,3JPC = 15.3 Hz,
2
(m, 4H, 2 C2H2), 4.79 (d, 1H, JPH = 10.0 Hz, C4H), 6.17-
6.37 (m, 2H, 2 CFurH), 7.52 (s, 2H, 2 CFurHO). 13C NMR
(CDCl3, 100 MHz), δ, ppm: 0.83 (s, Me3Si), 0.47 (s, Me3Si),
1
32.3 (s, C(2)), 32.8 (s, C(2)), 35.0 (d, JPC = 96.7 Hz, C1),
1
66.9 (d, JPC = 119.8 Hz, C4H), 109.7 (s, CFur), 110.4 (s,
CFur), 123.6 (s, CAr), 125.9 (s, CAr), 141.3 (d, 3JPC = 10.6 Hz,
3
C3), 141.4 (d, JPC = 11.3 Hz, CFurHO), 149.8 (s, CFurO).
31P NMR (CDCl3, 162 MHz), δ, ppm: 37.4 (s). The second
1
isomer, 40%. H NMR (CDCl3, 400 MHz), δ, ppm: 0.02 (s,
9H, Me3Si), -0.07 (s, 9H, Me3Si), 2.35-2.50 (m, 1H, C1H),
2
2.85-3.15 (m, 4H, 2 C2H2), 4.82 (d, 1H, JPH = 10.8 Hz,
C4H), 6.17-6.37 (m, 2H, 2 CFurH), 7.51 (s, 2H, 2 CFurHO).
13C NMR (CDCl3, 100 MHz), δ, ppm: 0.36 (s, Me3Si), 0.62

PRISHCHENKO Et al.
7 of 9
|
C6). 31P NMR (CDCl3, 162 MHz), δ, ppm: 45.4 (s). Anal.
Calcd for C18H31O4PSi2. C 54.24; H 7.84. Found: C 54.03;
H 7.74.
C2H2), 2.90-3.00 (m, 6H, C4H2, 2 C5H2), 7.00-7.15 (m, 4H, 4
CArH). 13C NMR (D2O, (CD3)2SO, 100 MHz), δ, ppm: 22.5
(s, 2 C7), 27.8 (s, 2 C6), 34.5 (s, C2), 38.7 (d, 1JPC = 97.1 Hz,
C1), 57.7 (d, JPC = 102.4 Hz, C4), 58.0 (d, JPC = 5.1 Hz, 2
C5), 125.4 (s, 2 CAr), 127.2 (s, 2 CAr), 144.4 (d, 3JPC = 9.7 Hz,
C3). 31P NMR (D2O, (CD3)2SO, 162 MHz), δ, ppm: 36.0 (s).
Anal. Calcd for C16H23NNaO2P. C 60.94; H 7.35. Found: C
60.80; H 7.39.
1
3
4.17
Sodium 2,3-dihydro-1H-inden-2-
|
ylphosphonite (6)
A solution of phosphonite 1 (4.9 g, 0.015 mol) in diethyl
ether (5 mL) was added with stirring at 10°C to a solution of
sodium methylate (0.81 g, 0.015 mol) in methanol (20 mL).
The resulting mixture was refluxed, the solvent was removed,
and the residue was kept in a vacuum (1 mm Hg) for 1 hr to
obtain 3 g of salt 10a, yield 97%. 1H NMR (D2O, 400 MHz),
δ, ppm: 2.35-2.50 (m, 1H, C1H), 2.90-3.15 (m, 4H, 2 C2H2),
6.83 (dd, 1JPH = 500.7, 3JHH 2.2 Hz, PH), 7.10-7.25 (m, 4H, 4
CArH). 13C NMR (D2O, 100 MHz), δ, ppm: 32.2 (s, C2), 38.8
(d, 1JPC = 94.5 Hz, C1), 124.6 (s, CAr), 126.7 (s, CAr), 142.7
4.21
Sodium 2,3-dihydro-1H-inden-2-
|
yl(morpholin-4-ylmethyl)phosphinate (7d)
1
Yield 95 %. H NMR (D2O, 400 MHz), δ, ppm: 2.50-2.60
(m, 4H, 2 C2H2), 2.70-2.75 (m, 1H, C1H), 3.00-3.10 (m, 6H,
C4H2, 2 C5H2), 3.64 (s, 4H, 2 C6H2), 7.10-7.21 (m, 4H, 4
CArH). 13C NMR (D2O, 100 MHz), δ, ppm: 34.2 (s, C2), 38.9
(d, 1JPC = 96.7 Hz, C1), 55.7 (d,3JPC = 4.5 Hz, 2 C5), 58.2 (d,
1JPC = 110.5 Hz, C4), 66.5 (s, 2C6), 125.0 (s, 2CAr), 126.9
3
(d, JPC = 9.1 Hz, C3). 31P NMR (D2O, 162 MHz), δ, ppm:
1
3
32.8 (d, JPH = 500.7 Hz). Anal. Calcd for C9H10NaO2P. C
(s, 2CAr), 144.1 (d, JPC = 10.1 Hz, C3). 31P NMR (D2O,
52.95; H 4.94. Found: C 52.68; H 5.03.
162 MHz), δ, ppm: 31.7 (s). Anal. Calcd for C14H19NNaO3P.
Salts 7-10 were obtained analogously.
C 55.45; H 6.31. Found: C 55.29; H 6.28.
4.18
Sodium 2,3-dihydro-1H-inden-2-
4.22
Sodium 2,3-dihydro-1H-inden-2-yl(N-
|
|
yl(N,N-dimethylaminomethyl)phosphinate (7a)
methyl-N-formylaminomethyl)phosphinate (7e)
1
Yield 95%. H NMR (D2O, 400 MHz), δ, ppm: 2.35 (s, 6H,
Yield 95%. The first isomer, 55%.1H NMR (D2O,
400 MHz), δ, ppm: 2.30-2.50 (m, 1H, C1H), 2.90-3.00 (m,
4H, 2 C2H2), 3.10 (s, 3H, MeN), 3.29-3.50 (m, 2H, C4H2),
7.10-7.25 (m, 4H, 4 CArH), 7.71 (s, CHO). 13C NMR (D2O,
100 MHz), δ, ppm: 33.1 (s, C2), 36.7 (s, MeN), 37.2 (d,
1JPC = 96.4 Hz, C1), 43.7 (d, 1JPC = 94.2 Hz, C4), 124.6 (s,
2CAr), 126.7 (s, 2CAr), 142.7 (d, 3JPC = 9.3 Hz, C3), 165.4
(s, CO). 31P NMR (D2O, 162 MHz), δ, ppm: 35.9 (s). The
Me2N), 2.55-2.70 (m, 2H, C1H, C4HA), 3.00-3.15 (m, 5H,
C2H2, C4HB), 7.10-7.30 (m, 4H, 4 CArH). 13C NMR (D2O,
100 MHz), δ, ppm: 33.1 (s, C2), 37.7 (d, 1JPC = 96.6 Hz, C1),
46.8 (d, 3JPC = 4.2 Hz, Me2N), 57.5 (d, 1JPC = 99.1 Hz, C4),
124.6 (s, CAr), 126.6 (s, CAr), 142.9 (d, JPC = 9.9 Hz, C3).
3
31P NMR (D2O, 162 MHz), δ, ppm: 37.8 (s). Anal. Calcd for
C12H17NNaO2P. C 55.17; H 6.54. Found: C 54.94; H 6.65.
1
second isomer, 55%. H NMR (D2O, 400 MHz), δ, ppm:
2.30-2.50 (m, 1H, C1H), 2.90-3.00 (m, 4H, 2 C2H2), 3.05
(s, 6H, Me2N), 3.20-3.50 (m, 2H, C4H2), 7.10-7.25 (m,
4H, 4 CArH), 7.91 (s, CHO). 13C NMR (D2O, 100 MHz), δ,
ppm: 33.1 (s, C2), 36.6 (s, MeN), 37.7 (d, 1JPC = 97.6 Hz,
4.19
Sodium 2,3-dihydro-1H-inden-2-
|
yl(piperidin-1-ylmethyl)phosphinate (7b)
1
Yield 94 %. H NMR (D2O, (CD3)2SO, 400 MHz), δ, ppm:
1.30-1.50 (m, 6H, 2 C6H2, C7H2), 2.50-2.65 (m, 5H, C1H, 2
C2H2), 2.95-3.20 (m, 6H, C4H2, 2 C5H2), 7.10-7.20 (m, 4H, 4
CArH). 13C NMR (D2O, (CD3)2SO, 100 MHz), δ, ppm: 22.4
C1), 43.5 (d, JPC = 94.4 Hz, C4), 124.5 (s, 2CAr), 126.6
1
(s, 2CAr), 142.4 (d, JPC = 8.6 Hz, C3),164.5 (s, CO).
3
31P NMR (D2O, 162 MHz), δ, ppm:36.3 (s). Anal. Calcd
for C12H15NNaO3P. C 52.37; H 5.49. Found: C 52.02; H
5.57.
(s, C7), 24.6 (s, 2 C6), 33.8 (s, C2), 38.6 (d, JPC = 97.0 Hz,
1
C1), 56.9 (d, JPC = 9.2 Hz, C5), 57.8 (d, JPC = 112.3 Hz,
3
1
C4), 122.0 (s, CAr), 125.4 (s, CAr), 142.7 (d, JPC = 10.0 Hz,
3
C3). 31P NMR (D2O, (CD3)2SO, 162 MHz), δ, ppm: 31.9 (s).
Anal. Calcd for C15H21NNaO2P. C 59.80; H 7.03. Found: C
59.69; H 7.07.
4.23
Sodium 2,3-dihydro-1H-inden-2-yl(N-
|
ethyl-N-acetylaminomethyl)phosphinate (7f)
Yield 96%. The first isomer, 70 %. 1H NMR (D2O, (CD3)2SO,
400 MHz), δ, ppm: 1.03 (t, 3H, 3JHH = 6.4 Hz, C6H3), 1.97
(s, 3H, C7H3), 2.18-2.38 (m, 1H, C1H), 2.80-3.10 (m, 4H, 2
C2H2), 3.37 (d, 2H, 2JPH = 9.6 Hz, C4H2), 6.95-7.25 (m, 4H,
4 CArH). 13C NMR (D2O, (CD3)2SO, 100 MHz), δ, ppm: 13.4
4.20
Sodium 2,3-dihydro-1H-inden-2-
|
yl(azepan-1-ylmethyl)phosphinate (7c)
1
Yield 96 %. H NMR (D2O, (CD3)2SO, 400 MHz), δ, ppm:
1.40-1.60 (m, 8H, 2 C6H2, 2 C7H2), 2.45-2.65 (m, 5H, C1H, 2
(s, C6), 21.5 (s, C7), 34.2 (s, C2), 37.7 (d, JPC = 96.8 Hz,
1

8 of 9
PRISHCHENKO Et al.
|
C1), 39.1 (d, JPC = 101.7 Hz, C4), 44.8 (s, C5), 125.2 (s,
42.6 (d, 1JPC = 102.3 Hz, C4), 47.1 (s, C5), 60.2 (s, CH2O),
124.0 (s, CAr), 125.9 (s, CAr), 140.1 (d, 3JPC = 8.9 Hz, C3),
154.9 (s, C7), 167.8 (s, C6). 31P NMR (D2O, (CD3)2SO,
162 MHz), δ, ppm: 31.7 (s). The second isomer, 40%.
1H NMR (D2O, (CD3)2SO, 400 MHz), δ, ppm: 1.40-1.60
(m, 6H, 2 CH3), 2.36-2.40 (m, 1H, C1H), 2.84-3.05 (m,
1
CAr), 127.1 (s, CAr), 144.2 (d, JPC = 9.9 Hz, C3), 171.5 (s,
3
CO). 31P NMR (D2O, (CD3)2SO, 162 MHz), δ, ppm: 33.5
1
(s). The second isomer, 30%. H NMR (D2O, (CD3)2SO,
400 MHz), δ, ppm: 0.93 (t, 3H, JHH = 6.6 Hz, C6H3),
3
2.05 (s, 3H, C7H3), 2.18-2.38 (m, 1H, C1H), 2.80-3.05 (m,
4H, 2 C2H2), 3.49 (d, 2H, JPH = 6.8 Hz, C4H2), 6.95-7.25
4H, 2 C2H2), 3.49 (d, 2H, JPH = 7.2 Hz, C4H2), 4.2 (s,
2
2
(m, 4H, 4 CArH). 13C NMR (D2O, (CD3)2SO, 100 MHz),
2H, C5H2), 6.95-7.20 (m, 4H, 4 CArH). 13C NMR (D2O,
(CD3)2SO, 100 MHz), δ, ppm: 12.9 (s, 2 Me), 30.9 (s, C2),
35.0 (d, 1JPC = 95.2 Hz, C1), 42.1 (d, 1JPC = 101.3 Hz, C4),
46.9 (s, C5), 61.5 (s, CH2O), 123.8 (s, CAr), 125.1 (s, CAr),
δ, ppm: 12.7 (s, C6), 22.7 (s, C7), 33.5 (s, C2), 36.9 (d,
1JPC = 96.4 Hz, C1), 40.4 (d, JPC = 100.4 Hz, C4), 42.4 (s,
1
C5), 125.3 (s, CAr), 127.2 (s, CAr), 143.9 (d, JPC = 8.0 Hz,
3
C3), 172.6 (s, CO). 31P NMR (D2O, (CD3)2SO, 162 MHz),
δ, ppm: 31.0 (s). Anal. Calcd for C14H19NNaO3P. C 55.45;
H 6.31. Found: C 55.32; H 6.35.
139.7 (d, JPC = 8.9 Hz, C3), 154.2 (s, C7), 167.8 (s, C6).
3
31P NMR (D2O, (CD3)2SO, 162 MHz), δ, ppm: 31.1 (s).
Anal. Calcd for C17H23NNaO6P. C 52.18; H 5.92. Found:
C 52.02; H 5.98.
4.24
Sodium 2,3-dihydro-1H-inden-2-yl[(2-
|
oxopyrrolidin-1-yl)methyl]phosphinate (7g)
4.27
Sodium 2,3-dihydro-1H-inden-2-
|
yl(aminomethyl)phosphinate (7j)
Yield 95%. 1H NMR (D2O, (CD3)2SO, 400 MHz), δ, ppm: 1.85-
1.90 (m, 2H, C6H2), 2.17-2.22 (m, 2H, C7H2), 2.24-2.32 (m, 1H,
C1H), 2.85-2.98 (m, 4H, 2 C2H2), 3.23 (d, 2H, 2JPH = 9.2 Hz,
C4H2), 3.50-3.56 (m, 2H, 2 C5H2), 7.01-7.14 (m, 4H, 4 CArH).
13C NMR (D2O, (CD3)2SO, 100 MHz), δ, ppm: 18.2 (s, C(6)),
31.2 (s, C(7)), 34.0 (s, C(2)), 38.9 (d, 1JPC = 94.8 Hz, C1), 43.5
1HNMR(D2O, 400 MHz), δ, ppm:2.72(d, 2H, 2JPH = 8.7 Hz,
C4H2), 2.90-3.00 (m, 1H, C1H), 3.10-3.25 (m, 4H, 2 C2H2),
7.10-7.25 (m, 4H, 4 CArH). 13C NMR (D2O, 100 MHz),
δ, ppm: 30.5 (s, C2), 35.4 (d, JPC = 96.3 Hz, C1), 52.7 (d,
1
1JPC = 97.8 Hz, C4), 124.2 (s, CAr), 126.4 (s, 2CAr), 140.8 (d,
3JPC = 9.8 Hz, C3). 31P NMR (D2O, 162 MHz), δ, ppm: 39.2
(s). Anal. Calcd for C10H13NNaO2P. C 51.51; H 5.62.Found:
51.39; H, 5.54.
1
(d, JPC = 94.1 Hz, C4),49.3 (s, C5), 124.9 (s, CAr), 126.8 (s,
CAr), 144.7 (d, 3JPC = 10.2 Hz, C3). 31P NMR (D2O, (CD3)2SO,
162 MHz), δ, ppm: 30.7 (s). Anal. Calcd for C14H17NNaO3P. C
55.82; H 5.69. Found: C 55.68; H 5.74.
4.28
Disodium 2,3-dihydro-1H-inden-2-
|
4.25
Sodium 2,3-dihydro-1H-inden-2-yl[(2-
ylthiophosphonate (8)
|
oxoazepan-1-yl)methyl]phosphinate (7h)
1
Yield 97%. H NMR (D2O, 400 MHz), δ, ppm: 2.65-2.75
Yield 96%.1H NMR (D2O, (CD3)2SO, 400 MHz), δ, ppm: 1.22-
1.45 (m, 6H, C6H2, C7H2, C8H2), 2.15-2.20 (m, 2H, C9H2), 2.32-
2.45 (m, 1H, C1H), 2.75-3.05 (m, 4H, 2 C2H2), 3.30-3.45 (m,
4H, C4H2, C5H2), 6.80-7.10 (m, 4H, 4 CArH). 13C NMR (D2O,
(CD3)2SO, 100 MHz), δ, ppm: 20.2 (s, C7), 21.9 (s, C8), 26.9 (s,
C6), 28.0 (s, C9), 31.8 (s, C2), 35.8 (d, 1JPC = 96.8 Hz, C1), 44.5
(m, 1H, C1H), 3.60-3.80 (m, 4H, 2 C2H2), 7.09-7.25 (m,
4H, 4 CArH). 13C NMR (D2O, 100 MHz), δ, ppm: 35.3 (d,
2JPC = 6.4 Hz, C2), 45.4 (d, JPC = 105.9 Hz, C1), 124.5
1
(s, CAr), 126.3 (s, CAr), 143.7 (d, JPC = 11.4 Hz, C3).
3
31P NMR (D2O, 162 MHz), δ, ppm: 61.8 (s). Anal. Calcd
for C9H9Na2O2PS. C 41.87; H 3.51. Found: C 41.71; H
3.56.
1
(d, JPC = 99.5 Hz, C4), 47.5 (s, C5), 123.5 (s, CAr), 125.2 (s,
CAr), 142.6 (d, 3JPC = 10.1 Hz, C3). 31P NMR (D2O, (CD3)2SO,
162 MHz), δ, ppm: 31.8 (s). Anal. Calcd for C16H21NNaO3P. C
58.36; H 6.43. Found: C 58.18; H 6.39.
4.29
Sodium 2,3-dihydro-1H-inden-2-
|
yl[hydroxy(phenyl)methyl]phosphinate (9a)
1
Yield 96%. H NMR ((CD3)2SO, 400 MHz), δ, ppm: 2.10-
4.26
Sodium 2,3-dihydro-1H-inden-2-yl
2.60 (m, 1H, C1H), 2.72-3.18 (m, 4H, 2 C2H2), 4.75 (d, 1H,
|
[N-ethoxycarbonyl-N-(ethoxycarbonylmethyl)
2JPH = 13.2 Hz, C4H), 6.90-7.25 (m, 9H, 4 CArH, C6H5). 13
C
aminomethyl]phosphinate (7i)
NMR ((CD3)21SO, 100 MHz), δ, ppm: 33.6 (s, C2), 33.9 (s,
Yield 94%. The first isomer, 60%. 1H NMR (D2O, (CD3)2SO,
400 MHz), δ, ppm: 1.40-1.60 (m, 6H, 2 CH3), 2.36-2.40
(m, 1H, C1H), 2.84-3.05 (m, 4H, 2 C2H2), 3.31 (д, 2H,
2JPH = 8.4 Hz, C4H2), 4.12 (s, 2H, C5H2), 6.95-7.20 (m, 4H,
4 CArH). 13C NMR (D2O, (CD3)2SO, 100 MHz), δ, ppm:
C2), 35.9 (d, JPC = 96.1 Hz, C1), 73.6 (d, JPC = 97.3 Hz,
1
C4), 123.8 (s, CAr), 125.6 (s, CAr), 126.6 (s, CPh), 127.2 (s,
CPh), 142.0 (s, CPh), 143.4 (d, JPC = 4.0 Hz, C3), 143.5 (d,
3
3JPC = 4.0 Hz, C3). 31P NMR ((CD3)2SO, 162 MHz), δ, ppm:
34.8 (s). Anal. Calcd for C16H16NaO3P. C 61.94; H 5.20.
Found: C 61.72; H 5.26.
12.9 (s, 2 Me), 32.3 (s, C2), 36.4 (d, JPC = 96.5 Hz, C1),
1

PRISHCHENKO Et al.
9 of 9
|
ACKNOWLEDGMENTS
4.30
Sodium 2,3-dihydro-1H-inden-2-
|
yl[hydroxy(fur-2-yl)methyl]phosphinate (9b)
We thank the Russian Foundation for Basic Research for fi-
nancial support (grant number 17-03-00169).
1
Yield 97%. H NMR ((CD3)2SO, 400 MHz), δ, ppm: 2.25-
2.40 (m, 1H, C1H), 2.70-3.20 (m, 4H, 2 C2H2), 4.65 (d,
2
1H, JPH = 10.0 Hz, C4H), 6.29 (s, 1H, CFurH), 6.34 (s, 1H,
ORCID
CFurH), 7.01-7.07 (m, 5H, C6H5), 7.49 (s, 1H, CFurHO). 13C
Andrey A. Prishchenko
org/0000-0002-1302-5317
http://orcid.
NMR ((CD3)2SO, 100 MHz), δ, ppm: 33.5 (s, C2), 33.4 (s,
C2), 36.8 (d, JPC = 97.3 Hz, C1), 65.8 (d, JPC = 110.0 Hz,
1
1
C4), 106.9 (s, CFurH), 110.2 (s, CFurH), 123.8 (s, CAr), 125.7
(s, CAr), 141.5 (s, CFurHO), 143.4 (d, JPC = 10.1 Hz, C3),
3
REFERENCES
154.9 (s, CFurO). 31P NMR ((CD3)2SO, 162 MHz), δ, ppm:
33.1 (s). Anal. Calcd for C14H14NaO4P. C 56.01; H 4.70.
Found: C 55.89; H 4.66.
[1] O. I. Kolodiazhnyi, Russ. Chem. Rev. 2006, 75, 227.
[2] V. P. Kukhar, H. R. Hudson, Aminophosphonic and
Aminophosphinic Acids. Chemistry and Biological Activity,
Wiley, New York, New York 2000, 634.
[3] S. C. Fields, Tetrahedron 1999, 55, 12237.
4.31
Sodium 2,3-dihydro-1H-inden-2-
|
[4] F. H. Ebetino, Phosphorus, Sulfur Silicon Relat. Elem. 1999, 144-
146, 9.
[5] A. A. Prishchenko, M. V. Livantsov, O. P. Novikova, L. I.
Livantsova, G. M. Averochkin, V. S. Petrosyan, Heteroat. Chem.
2015, 26, 405.
yl[hydroxy(pyridin-3-yl)methyl]phosphinate
(9c)
1
Yield 95%. H NMR ((CD3)2SO, 400 MHz), δ, ppm: 2.32-
2.55 (m, 1H, C1H), 2.70-3.10 (m, 4H, 2 C2H2), 4.75 (d, 1H,
2JPH = 12.0 Hz, C4H), 6.90-7.10 (m, 4H, 4 CArH), 7.20-8.67
(m, 4H, 4 CPyH). 13C NMR ((CD3)2SO, 100 MHz), δ, ppm:
[6] a) A. A. Prishchenko, M. V. Livantsov, O. P. Novikova, L. I.
Livantsova, V. S. Petrosyan, Heteroat. Chem. 2016, 27, 381. b) A.
A. Prishchenko, M. V. Livantsov, O. P. Novikova, L. I. Livantsova,
Y. N. Koval’, E. V. Grigor’ev, Russ. J. Gen. Chem. 2003, 73,
1658. c) A. A. Prishchenko, M. V. Livantsov, O. P. Novikova,
L. I. Livantsova, V. S. Petrosyan, Heteroat. Chem. 2008, 19,
345. d) A. A. Prishchenko, M. V. Livantsov, O. P. Novikova, L.
I. Livantsova, V. S. Petrosyan, Heteroat. Chem. 2008, 19, 352.
e) A. A. Prishchenko, M. V. Livantsov, O. P. Novikova, L. I.
Livantsova, V. S. Petrosyan, Heteroat. Chem. 2008, 19, 418.
[7] A. A. Prishchenko, M. V. Livantsov, V. S. Petrosyan, Russ. J. Gen.
Chem. 1994, 64, 1316(in Russian) .
33.5 (s, C2), 39.9 (s, C2), 35.7 (d, JPC = 95.8 Hz, C1), 70.5
1
(d, 1JPC = 108.7 Hz, C4), 122.5 (s, CPy), 134.1 (s, CPy), 137.2
(s, CPy), 143.2 (s, C3), 143.3 (s, C3), 146.9 (s, CPy), 146.1
(s, CPy). 31P NMR ((CD3)2SO, 162 MHz), δ, ppm: 34.5 (s).
Anal. Calcd for C15H15NNaO3P. C 57.88; H 4.86. Found: C
57.73; H 4.91.
4.32
Disodium 2,3-dihydro-1H-inden-2-
|
[8] V. D. Romanenko, M. V. Shevchuk, V. P. Kukhar, Current. Org.
Chem. 2011, 15, 2774.
yl(2-carboxyethyl)phosphinate (10)
Yield 95%. 1H NMR (D2O, (CD3)2SO, 400 MHz), δ, ppm: 1.50-
1.65 (m, 1H, C1H), 2.15-2.40 (m, 2H, C4H2), 2.80-3.00 (m, 6H,
2 C2H2, C5H2), 6.00-7.15 (m, 4H, 4 CArH). 13C NMR (D2O,
[9] L. Wozniak, J. Chojnowski, Tetrahedron 1989, 45, 2465.
(CD3)2SO, 100 MHz), δ, ppm: 26.3 (d, JPC = 89.8 Hz, C4),
1
How to cite this article: Prishchenko AA, Livantsov
MV, Novikova OP, Livantsova LI, Petrosyan VS.
Synthesis of new functionalized hydroxy- and
aminomethylphosphinates with indan moieties.
Heteroatom Chem. 2018;e21419.
30.9 (d, 2JPC = 6.1 Hz, C5), 33.7 (d, 1JPC = 98.1 Hz, C1), 34.1 (s,
C2), 125.0 (s, 2 CAr), 126.9 (s, 2 CAr), 143.9 (d, 3JPC = 9.8 Hz,
C3), 180.2 (d,3JPC = 15.7 Hz, C6). 31P NMR (D2O, (CD3)2SO,
162 MHz), δ, ppm: 39.1 (s). Anal. Calcd for . C12H13Na2O4P. C
48.34; H 4.39. Found: C 48.26; H 4.44.
https://doi.org/10.1002/hc.21419