Synthesis of fluorescent aminophosphonates by green chemistry procedures

Article abstract of DOI:10.1080/10426507.2017.1308934

Fluorescent aminophosphonates were obtained using optimized conditions of the microwave-stimulated Kabachnik-Fields reaction. Unfortunately, in the case of more demanding, bulky amines and aldehydes this reaction failed to give the desired products.

Full text of DOI:10.1080/10426507.2017.1308934

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
Synthesis of Fluorescent Aminophosphonates by
Green Chemistry Procedures
Anna Kuśnierz & Ewa Chmielewska
To cite this article: Anna Kuśnierz & Ewa Chmielewska (2017): Synthesis of Fluorescent
Aminophosphonates by Green Chemistry Procedures, Phosphorus, Sulfur, and Silicon and the
Related Elements, DOI: 10.1080/10426507.2017.1308934
To link to this article: http://dx.doi.org/10.1080/10426507.2017.1308934
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SYNTHESIS OF FLUORESCENT AMINOPHOSPHONATES BY GREEN CHEMISTRY
PROCEDURES
Anna Kuśnierz and Ewa Chmielewska*
Department of Bioorganic Chemistry, Faculty of Chemistry, Wrocław University of Science and
Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland
CONTACT ewa.chmielewska@pwr.edu.pl
This paper is dedicated to the memory of Prof. Harry R. Hudson.
ABSTRACT
Fluorescent aminophosphonates were obtained using optimized conditions of the microwave-
stimulated Kabachnik-Fields reaction. Unfortunately, in the case of more demanding, bulky
amines and aldehydes this reaction failed to give the desired products.
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KEYWORDS
Aminophosphonates, Kabachnik-Fields reaction, fluorescence, microvawe-assisted synthesis,
nanoparticles
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INTRODUCTION
α-Aminophosphonates are compounds that contain N-C-P structural fragment.1 Over recent years
they have attracted substantial attention, mainly due to their interesting biological properties,
with some of them being already commercialized.1,2,3,4,5 Some papers report their fluorescent
properties along with their synthesis.6,7,8,9,10 These studies are stimulated by their possible use in
constructing fluorescent probes for in-cell profiling activities of some enzymes11,12,13 or by that
their libraries may serve for building up diagnostic tools.6 This assumption results from the fact
that aminophosphonates are effective inhibitors of proteases and phosphatases1,2,14,15,16 and that
their fluorescence may change upon binding to these proteins.
In this paper we have studied the efficiency of some green chemistry procedures for the
preparation of some model fluorescent aminophosphonates. Additionally, their fluorescent
properties were evaluated.
RESULTS AND DISCUSSION
Kabachnik-Fields reaction (also called phospha-Mannich reaction) is one of the oldest
and perhaps the most commonly used for preparation of aminophosphonates.17,18,19 Its variant of
choice is the use of, the described recently, microwave assisted synthesis.20,21,22,23 We have used
this procedure to optimize the reaction conditions for the reaction of 2-aminoanthracene with
benzaldehyde and diethyl phosphite (Scheme 1), which provided compound 1.
2-Aminoanthracene is practically insoluble in most of the organic solvents and therefore the
reaction was carried out in two phase system consisting of solvent and solid non-soluble
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reagents. Out of three solvents used acetonitrile appeared to be of choice (Table 1), while the
molar ratio of substrates (anthracene:benzaldehyde:phosphite) was set at 1:1:1.2. Quite
unexpectedly, the yield of reaction was dependent not only on the time of reaction under
microwave stimulation but also on the time of completing of the process at room temperature
31
(Table 1). If the crude product was examined by P NMR just after reaction with microwaves
the lack of product was observed (entry 3). When analyzing this product after a week, 76% of
yield of aminophosphonate was seen (entry 4). Prolonged storage of the reaction mixture at room
temperature up to two weeks indicated quantitative reaction (entry 6). For comparison, reaction
carried out by omitting microwave step and preliminary by heating the reagents in acetonitrile at
100°C and left for a week at room temperature provided the desired product 1 in 20% yield.
These results clearly show that application of microwaves is beneficial as it was demonstrated
earlier. Increase in the temperature of microwave stimulation to 135°C appeared to be
disadvantageous (entries 8 and 9). It is worth to note that application of 100°C resulted in
pressure of 1 barr and 300 Watts of initial power, which stabilize at 200 W, whereas for 135°C
pressure reached 3 barrs with power of 100W.
Thus, the optimal reaction conditions were set as follows: reaction in acetonitrile under
microwave stimulation at 100°C for 20 min followed by two weeks at room temperature. These
conditions were unsuccessfully applied when trying to react 2-aminoanthracene with more
demanding, bulky substrates such as 2-methylbenzaldehyde and 1-naphtalenecarbaldehyde. The
application of other amines also gave quite unsatisfactory results. Among 1-aminoanthracene, 5-
aminofluorescein, 6-aminofluorescein, 5-amino-1,10-phenanthroline, 1-naphtylamine, 2-
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naphtylamine and 1-naphtylmethylamine we succeeded in obtaining only the products of the last
two amines, namely compounds 2 and 3, (Scheme 2) in satisfactory yield.
The obtained aminophosphonates 1, 2 and 3 were then converted into corresponding acids by
standard reaction with bromotrimethylsilane followed by methanolysis (see representative
example in Scheme 3).24
Fluorescence spectra (emission and excitation) of compounds 1-8 dissolved in dimethyl
sulfoxide (5 mM) were determined in the range of 360-750 nm, using excitation wavelengths
fixed at 366 nm respectively. As expected the highest fluorescence (although still moderate) was
observed in the case of N-anthracyl derivatives 1 and 4, which emitted around at 510 and 730
nm, with ester exhibiting stronger fluorescence (Figure 1). In this case strong quenching of
starting amine fluorescence by these compounds was observed. When comparing with DMSO
ester 1 shows slight hypsochromic effect versus DMSO (720 nm), while acid slightly
batochromic at 390 nm.
In the second approach we have used two, available from previous studies,25 magnetic
nanoparticles functionalized with aminophosphonic acids as catalysts of solventless reaction of
equimolar quantities of benzylamine, benzaldehyde and diethyl phosphite (Scheme 4). Reaction
carried out in 100°C for 11 hours, gave around 80% of yield of isolated product 726 regardless of
presence (78% in the case of catalyst 1 and 81% for catalyst 2) or absence (87% of yield) of the
catalyst. When using microwaves (100°C, 15 min) instead of simple heating the obtained yields
declined to 15%. It shows limited usefulness of our magnetic nanoparticles as catalysts for
preparation of aminophosphonates. For reactions carried out in a microwave (without magnetic
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nanoparticles) in 100°C for 15 minutes, the yield of isolated product 7 was 37%. The best yields
have been obtained for reactions without magnetic nanoparticles carried out in 130°C for 15
minutes. This conditions allowed to obtain the product with 86% yields. The same yield was
obtained in a reaction carried out in a microwave at 100°C for 1hour. The extension of time does
not result in increased the yield in reaction.
CONCLUSIONS
Our studies indicate some usefulness of green Kabachnik-Fields approach for the preparation of
fluorescent aminophosphonates. Our studies have also shown that this popular reaction is limited
to rather simple substrates lacking steric bulkiness.
EXPERIMENTAL
All solvents and reagents were purchased from commercial suppliers, were of analytical
grade and used without further purification. Unless otherwise specified, solvents were removed
1
31
13
with a rotary evaporator. The H, P and C NMR spectroscopic experiments were performed
on a Bruker Advance II Ultrashied Plus 600.58 MHz (1H) i 243.12 MHz (31P{1H}) and 151.02
MHz (13C) and on a Bruker Ultrashield operating at 400.13 MHz (1H) i 161.98 MHz (31P{1H}).
Measurements were made in CDCl3 (99.8 at. %D) and DMSOd6 (99.8 at. %D) solutions at 300
K, which was supplied by ARMAR AG (Dottingen, Switzerland). Chemical shifts are reported in
ppm relative to TMS and 85% H3PO4, used as external standards, while coupling constants are
reported in Hz.
Melting points were determined on an SRS Melting Point Apparatus OptiMelt MPA 100 and are
reported without correction. Mass spectra were recorded at the Faculty of Chemistry, Wroclaw
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University of Science and Technology using a Waters LCT Premier XE mass spectrometer
(method of ionization ESI). Reactions were monitored by thin-layer chromatography (TLC)
carried out on 0.25 mm silica gel plates with a fluorescent label (silica gel 60F254, Merck
Poland, Warsaw, Poland) and the components were visualized by the following methods: UV
light absorbance, and/or incubation with iodine. Microwave reactions were conducted in
microwave synthesizer Biotage Initiator + SP Wave (Biotage, Uppsala, Sweden).
A typical fluorescence emissions spectrum between 360 and 750 nm (slit 10 nm) for selected
aminophosphonates esters dissolved in dimethyl sulfoxide (DMSO) was determined using
excitation wavelengths fixed at 366 nm (slit width, 10 nm). Generally, strong quenching of
DMSO fluorescence by these compounds was observed. Also fluorescence excitation
measurements (between 350 and 750 nm) have been performed by fixing the detection
wavelengths at 400 nm (slit width, 10 nm). Spectrofluorometric measurements were performed
using 5 mM DMSO solutions of aminophosphonates at 25°C using Spectra Max Gemini XPS
(Molecular Devices, Sunnyvale, USA) Fluorescence Microplate Reader and SofMax Pro 7.0
programme. Measurement was performed in 96 well plate format working at two wavelengths:
1
excitation at 366 nm and emission at 400 nm. The Supplemental Materials contains sample H,
13C and 31P NMR spectra of products 1 -- 6 (Figures S 1 -- S 17).
Optimized general synthetic procedure
The mixture of 2-aminoanthracene (0.50 g, 2.5 mmol), benzaldehyde (0.26 mL, 2.5 mmol) and
diethyl phosphite (0.39 mL, 3.0 mmol) in acetonitrile (4 mL) was placed for 20 min at 100C in
a microwave synthesizer (Biotage Initiator + SP Wave). After cooling to room temperature it
was left at room temperature for two weeks to complete the reaction. After removal of volatile
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components of the reaction crude yellow-greenish oil was obtained. It was then washed with
hexane (35 mL). The desired compound 1 was obtained as beige solid (100% of yield).
Diethyl (N-anthrac-2-ylamino)benzylphosphonate (1)
1
Mp. 149-152°C; 31P NMR (243.12 MHz, CDCl3, ppm): δ = 22.54; H NMR (600.58 MHz,
CDCl3, ppm): δ = 1.17 & 1.33 (each: 3H, t, J = 7.05 Hz, OCH2CH3), 3.72-3.76 & 3.98-4.02
(each: 1H, m, POCH2), 4.14-4.23 (2H, m, POCH2), 4.99 (1H, d, J = 23.9 Hz, CHP), 6.76 (1H, d,
J = 2.06 Hz, Ar), 7.08 (1H, dd, J = 9.04 Hz, Ar), 7.31-7.35 (2H, m, Ar), 7.38-7.42 (3H, m, Ar),
7.59-7.61 (2H, m, Ar), 7.84 (2H, m, Ar), 7.91 (1H, d, J = 8.21 Hz, Ar), 8.02 (1H, s, Ar), 8.24
(1H, s, Ar); 13C NMR (151.02 MHz, CDCl3, ppm): δ = 16.23 (d, J = 5.7 Hz, CH3), 16.47 (d, J =
5.8 Hz, CH3), 56.05 (d, J = 150.0 Hz, CHP), 63.35 (d, J = 6.99 Hz, OCH2), 63.48 (d, J = 6.97
Hz, OCH2), 103.86, 120.19, 123.0, 123.82, 125.33, 126.10, 127.40, 127.62, 127.85 (d, J = 5.5
Hz), 128.10 (d, J = 3.2 Hz), 128.20, 128.73 (d, J = 2.55 Hz), 129.52, 129.74, 129.77, 132.39,
133.04, 135.54 (d, J = 2.8 Hz), 143.02, 143.11; HRMS (TOF MS ESI): [M+H]+ Calcd. for
C25H26NO3P: 420.1729 found: 420.1730.
Diethyl (N-napht-2-ylamino)benzylphosphonate (2)
Yield 58%; beige solid melting at 105-107°C (lit. 104-105C27,28,29; 31P NMR (243.12 MHz,
CDCl3, ppm): δ = 23.73; 1H NMR (600.58 MHz, CDCl3, ppm): δ = 1.16 & 1.32 (each: 3H, t, J =
7.1 Hz, OCH2CH3), 3.71-3.75 & 3.98-4.00 (each: 1H, m, POCH2), 4.10-4.21 (2H, m, POCH2),
4.93 (1H, d, J = 24.1 Hz, CHP), 6.74 (1H, d, J = 2.2 Hz, Ar), 7.01 (1H, dd, J = 8.8 Hz, Ar), 7.19-
7.22 (1H, m, Ar), 7.23-7.31 (1H, m, Ar), 7.32-7.34 (1H, m, Ar), 7.37 (2H, t, J = 7.7 Hz, Ar), 7.52
(1H, d, J = 8.24 Hz, Ar), 7.54-7.56 (2H, m, Ar), 7.64-7.67 (2H, m, Ar); 13C NMR (151.02 MHz,
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CDCl3, ppm): δ = 16.25 (d, J = 5.8 Hz, CH3), 16.48 (d, J = 5.8 Hz, CH3), 56.10 (d, J = 150.7 Hz,
CHP), 63.40 (t, J = 7.5 Hz, OCH2), 106.47, 118.15, 122.49, 126.12, 126.32, 127.60, 127.90 (d, J
= 5.6 Hz), 128.04, 128.06, 128.68, 128.70, 129.06, 134.79, 135.72, 135.74, 143.99 (d, J =
14.46Hz); HRMS (TOF MS ESI): [M+H]+ Calcd. for C21H24NO3P: 370.1572 found: 370.1570.
Diethyl (N-napht-1-ylmethylamino)benzylphosphonate (3)
Yield 62%; dense yellow oil; 31P NMR (243.12 MHz, CDCl3, ppm): δ = 24.34; 1H NMR (600.58
MHz, CDCl3, ppm): δ = 1.09 & 1.21 (each: 3H, t, J = 7.1 Hz, OCH2CH3), 3.75-3.75 & 3.92-3.96
(each: 1H, m, POCH2), 4.02-4.06 (m, 2H, OCH2CH3), 4.01&4.30 (2H, AB system, J1 = 13.2 Hz,
CH2NH), 4.11 (1H, d, J = 20.4Hz, CHP), 7.36-7.38 (2H, m, Ar), 7.41-7.45 (3H, m, Ar), 7.50-
13
7.52 (4H, Ar), 7.80 (1H, d, J = 8.1 Hz, Ar), 7.87-7.89 (1H, m, Ar),8.11-8.13 (1H, m. Ar); C
NMR (151.02 MHz, CDCl3, ppm): δ = 16.19 (d, J = 5.9 Hz, CH3), 16.39 (d, J = 6.0 Hz, CH3),
49.18 & 49.31 (each: s, CH2NH), 60.03 (d, J = 153.7 Hz, CHP), 62.80 (d, J = 6.9 Hz, OCH2),
63.15 (d, J = 7.0 Hz, OCH2), 124.04, 125.27, 125.68, 125.95, 126.67, 128.06, 128.07, 128.10,
128.59, 128.62 (d, J = 7.0 Hz), 128.79 (d, J = 6.1 Hz), 131.96, 133.92, 134.73, 135.76, 135.78;
HRMS (TOF MS ESI): [M+H]+ Calcd. for C22H26NO3P: 384.1684 found: 384.1680.
Diethyl (N-phenylamino)benzylphosphonate (7)30
The mixture of benzylamine (0.5 g, 4.66 mmol), benzaldehyde (0.48 mL, 4.66 mmol) and diethyl
phosphite (0.72 mL, 5.5 mmol) and functionalized nanoparticle (cat. 1 or cat. 2) (35 mg) were
heated and simultaneously stirred at a temperature of 110°C on a heating plate (100°C in the
reaction medium) of a Radley’s Carousel apparatus for 11 hours. The resulting oil was dissolved
in chloroform in the presence of a catalyst and were separated with a magnet outside
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(decantation). The resulting product was washed with chloroform and dry under vacuum (78% -
cat. 1 or 81% - cat. 2). If the reaction was carried out without catalyst (87%), the resulting oil
was dissolved in chloroform (100 mL) and purified by washing with water (100 mL), saturated
sodium chloride solution (100 mL) and again with water (100 mL). The solution was dried over
anhydrous MgSO4, and the solvent was evaporated under vacuum.
Yield 87%; yellow oil; 31P NMR (243.12 MHz, CDCl3, ppm): δ = 23.51; 1H NMR (600.58 MHz,
CDCl3, ppm): δ = 1.16 (3H, t, J = 6.01 Hz, POCH2CH3) 1.30 (3H, t, J = 6.01 Hz, POCH2CH3)
3.58&3.84 (2H, AB system, J1 = 18.02 Hz, CH2N) 3.91-3.94 (2H, m, POCH2CH3) 4.05 (H, d, J
13
= 24.02 Hz, CHP) 4.07-4.14 (2H, m, POCH2CH3), 7.28-7.46 (10H, m, Ar); C NMR (151.02
MHz, CDCl3, ppm): δ = 16.36 (dd, J1 = 6.02, J2 = 30.20 Hz), 51.23 (d, J = 16.61 Hz), 59.61 (d, J
= 154.04 Hz, CHP) 62.97, 127.14, 127.92, 127.94, 128.37, 128.29, 128.49, 128.50, 128.68,
128.73, 128.82, 128.99, 129.02. HRMS (ES+TOF) m/z: [M+H]+ Calcd. for C18H24NO3P
334.1572, found 334.1570.
Synthesis of acids -- representative procedure
Diethyl (N-anthrac-2-ylamino)benzylphosphonate (1) (0.40 g, 1 mmol) was dissolved on dry
dichloromethane (100 mL). Reaction was carried out under nitrogen and it was started by
addition of bromotrimethylsilane (1 mL) followed by stirring for 24 h at room temperature. Then
volatile components of reaction mixture were evaporated off and oily residue dissolved in
methanol (100 mL) and stirred at room temperature for next 24 h. Then the solvents were
evaporated and resulting brown solid was washed with water (36mL) and chloroform (36 mL)
yielding brownish solid of compound 4 with 48% of yield.
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(N-Anthrac-2-ylamino)benzylphosphonic acid (4)
Mp. 160-164°C; 31P NMR (243.12 MHz, CDCl3, ppm): 18.50; 1H NMR (400.13 MHz, DMSOd6,
ppm): δ = 4.81 (1H, d, J = 24.6 Hz, CHP), 6.52-6.69 (1H, m, Ar), 6.95-7.01 (1H, m, Ar), 7.19-
7.20 (1H, m, Ar), 7.28-7.37 (3H, m, Ar), 7.55 (2H, d, J = 7.60 Hz, Ar), 7.76-7.95 (3H, m, Ar),
13
8.05-8.11 (1H, m, Ar), 8.24-8.68 (2H, m, Ar); C NMR (151.02 MHz, DMSOd6, ppm): 56.30
(d, J = 145.6 Hz, CHP), 121.43, 121.89, 122.17, 122.64, 123.82, 124.28, 125.67, 125.91, 126.09,
126.47, 127.28 (d, J = 8.8 Hz), 127.73, 128.30, 128.48, 128.60, 128.69, 128.70 (d, J = 4.52 Hz),
129.08 (d, J = 17.4 Hz), 129.81, 132.35 (d, J = 10.8 Hz); HRMS (TOF MS ESI): [M+H]+ Calcd.
for C22H18NO3P: 362.0946 found: 362.0946.
(N-Napht-1-ylamino)benzylphosphonic acid (5)
Yield 86%, white solid, mp. 193-197°C; 31P NMR (161.98 MHz, DMSOd6, ppm): δ = 18.72; 1H
NMR (600.58 MHz, DMSOd6, ppm): δ = 4.80 (1H, d, J = 24.1 Hz, CHP), 6.73 (1H, d, J = 2.0
Hz, Ar), 7.01-7.10 (1H, m, Ar), 7.19 (1H, td, J = 7.2 Hz, Ar), 7.23-7.27 (2H, m, Ar), 7.29 (2H, t,
J = 7.6 Hz, Ar), 7.44 (1H, d, J = 8.2 Hz, Ar), 7.54 (2H, d, J = 7.8 Hz, Ar), 7.58 (1H, d, J = 8.9
13
Hz, Ar), 7.61 (1H, d, J = 8.0 Hz, Ar); C NMR (151.02 MHz, DMSOd6, ppm): 55.75 (d, J =
146.3 Hz, CP), 104.28, 118.85, 121.38, 125.49, 125.89, 126.71, 127.29, 127.78, 127.77, 128.16,
128.19, 128.22, 134.61, 138.31, 145.41, 145.51; HRMS (TOF MS ESI): [M+H]+ Calcd. for
C17H16NO3P: 312.0789 found: 312.0780.
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(N-Napht-1-ylmethylamino)benzylphosphonate (6)
Yield 42%, white solid, mp. 129-131°C; 31P NMR (243.12 MHz, DMSOd6, ppm): δ = 14.43; 1H
NMR (600.58 MHz, DMSOd6, ppm): δ = 2.35 (1H, d, J = 22.8Hz, CHP), 2.44&2.66 (2H, AB
system, J = 13.77 Hz, CH2NH), 5.30 (3H, br s, Ar), 5.35 (2H, br s, Ar), 5.40-5.42 (1H, m, Ar),
5.45 (2H, t, J = 6.4 Hz, Ar), 5.49 (1H, d, J = 6.7 Hz, Ar), 5.71 (1H, d, J = 7.7 Hz, Ar), 5.86 (2H,
13
t, J = 8.2 Hz, Ar); C NMR (151.02 MHz, DMSOd63, ppm): 47.07 & 47.17 (each; s, CH2NH),
62.40 (d, J = 132.8 Hz, CHP), 121.38, 123.93, 124.05, 124.19, 124.22, 124.46, 125.71, 125.91,
126.73, 127.02, 127.05, 129.31, 131.42, 133.48, 139.19, 139.22; HRMS (TOF MS ESI):
[M+H]+ Calcd. for C18H18NO3P: 326.0946 found: 326.0937.
(N-phenylamino)benzylphosphonate (8)31
Diethyl (N-phenylamino)benzylphosphonate 7 (0.03 mol) was dissolved in 20 mL of 6 N
hydrochloric acid and heating in 90°C for 12 h. After cooling, the volatile components were
removed using a rotary evaporator, and the resulting oil was dissolved in a minimal amount of
hot water, decoloured with activated charcoal and purified by crystallization from a hot water.
Yiel 93%, white solid, mp. 235-236°C (lit. 235-236°C 26); 31P NMR (161.98 MHz, D2O+NaOD,
ppm): δ = 16.90; 1H NMR (600.58 MHz, D2O+NaOD, ppm): δ = 3.44&3.56 (2H, AB system, J1
= 18.02 Hz, CH2N) 3.64 (1H, d, J = 18.02 Hz, CHP) 7.20-7.37 (10H, m, Ar); 13C NMR (151.02
MHz, ppm): δ = 51.43 (d, J = 13.53 Hz), 63.11 (d, J = 133.60 Hz, CHP), 126.39, 126.41, 127.21,
128.02, 128.03, 128.61, 128.64, 128.73, 128.77, 129.11 (d, J = 5.06 Hz), 139.42, 140.52 (d, J =
4.82 Hz). HRMS (ESI-TOF) m/z: [M-H]+ Calcd. for C14H16NO3P 276.0789, found 276.0793.
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Acknowledgements
The work was financed by a statutory activity subsidy from the Polish Ministry of Science and
Higher Education for the Faculty of Chemistry of Wrocław University of Science and
Technology and Wrocław Center of Biotechnology, program The Leading National Research
Center Program (KNOW) for years 2014-2018.
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Table 1. Optimization of the conditions of Kabachnik-Fields reaction
Entry Molar ration Temp.
of substrates
Solvent
Reaction time
Yield by 31P
NMR
microwave
room temp.
week
1
2
3
4
5
6
7
8
9
1:1:1.2
1:1:1.2
1:1:1.2
1:1:1.2
1:1:1.5
1:1:1.2
1:1:1.2
1:1:1.2
1:1:1.2
100°C
100°C
methanol
benzene
20 min.
20 min.
20 min.
20 min.
20 min.
20 min.
30 min.
20 min.
40 min.
34%
53%
week
100°C acetonitrile
100°C acetonitrile
100°C acetonitrile
100°C acetonitrile
100°C acetonitrile
135°C acetonitrile
130°C acetonitrile
-
no reaction
76%
week
week
60%
two weeks
two weeks
two weeks
two weeks
100%
100%
99%
94%
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Figure 1. Emission fluorescence spectra of (N-anthracylamino)bezylphosphonates versus
athracylamine and DMSO
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O
H
NH2
N
P(O)(OEt)2
H
HP(O)(OEt)2
+
+
1
Scheme 1. Reaction of 2-aminoanthracene with benzaldehyde and diethyl phosphite
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H
H
N
P(O)(OEt)2
N
P(O)(OEt)2
2
3
Scheme 2. Products of reaction of naphtylamines with benzaldehyde and diethyl phosphite
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H
H
N
P(O)(OH)2
N
P(O)(OEt)2
1./ Me3SiBr
2./ CH3OH
4
1
H
H
N
P(O)(OH)2
N
P(O)(OH)2
5
6
Scheme 3. An example: conversion of fluorescent aminophosphonate 1 into an acid 4 and the
structures of three remained products 5 and 6
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Scheme 4. Kabachnik-Fields reaction catalyzed by nanoparticles
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