Synthesis of N-(2-hydroxyphenyl)-1,8-naphthalimide and its derivatization at the hydroxy group

Article abstract of DOI:10.1007/s11172-011-0080-4

The reaction of 1,8-naphthalic anhydride with 2-aminophenol afforded N-(2-hydroxyphenyl)-1,8-naphthalimide, which was then derivatized at the hydroxy group.

Full text of DOI:10.1007/s11172-011-0080-4

Russian Chemical Bulletin, International Edition, Vol. 60, No. 3, pp. 512—520, March, 2011
512
Synthesis of Nꢀ(2ꢀhydroxyphenyl)ꢀ1,8ꢀnaphthalimide
and its derivatization at the hydroxy group
I. I. Ponomarev, M. Yu. Zharinova, Z. S. Klemenkova, P. V. Petrovskii, and Z. A. Starikova
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5085. Eꢀmail: firebird@ineos.ac.ru
The reaction of 1,8ꢀnaphthalic anhydride with 2ꢀaminophenol afforded Nꢀ(2ꢀhydroxyꢀ
phenyl)ꢀ1,8ꢀnaphthalimide, which was then derivatized at the hydroxy group.
Key words: Nꢀ(2ꢀhydroxyphenyl)ꢀ1,8ꢀnaphthalimide, alkylation, phenols, [2+3]ꢀcycloꢀ
addition, 1,2,3ꢀtriazoles, polynaphthalimides.
NꢀArylꢀ1,8ꢀnaphthalimides may be of interest as comꢀ
The synthesis of PNI can be performed in dipolar aproꢀ
pounds modeling the structure of the repeating units of
the corresponding polynaphthalimides (PNI) based on
1,4,5,8ꢀnapthalenetetracarboxylic acid dianhydride and
aromatic diamines. The data obtained in investigations of
the synthesis of model functional naphthalimides and their
chemical modifications are useful for the estimation of the
optimal conditions for the polycondensation followed by
polymerꢀanalogous reactions of the target PNI. These
polymers are characterized by high oxidative and thermal
stability and good film formation and, in the presence of
ionogenic groups, show promise as membranes in lowꢀ
temperature fuel cells.1 Studies of the threeꢀdimensional
structures of model naphthalimide molecules provide inꢀ
formation on the threeꢀdimensional structures of the reꢀ
peating units in PNI. In addition, Nꢀarylꢀ1,8ꢀnaphthalꢀ
imides have fluorescence properties and can emit radiaꢀ
tion in the UV region due to which they are of interest as
fluorescent dyes.2
In the present study, we investigated the possibility of
derivatization of Nꢀ(2ꢀhydroxyphenyl)ꢀ1,8ꢀnaphthalimide
(1) with sulfoꢀ and carboxyꢀsubstituted alkyl and aryl moiꢀ
eties. Earlier, compound 1 (see Ref. 3) and some its anaꢀ
logs2 have been synthesized by heating the starting anꢀ
hydride and the corresponding primary amine in pyridine
in the presence of zinc acetate and 4 Å molecular sieves.
Evidently, the aboveꢀdescribed method is unsuitable for
the synthesis of PNI because the latter are insoluble in
pyridine. In addition, the fact that the final products were
isolated from the reaction mixture by chromatography inꢀ
dicates that side reactions occur.
tic solvents, but, as a rule, PNI are insoluble in these
solvents. However, earlier it has been found that the presꢀ
ence of certain substituents, in particular, the hydroxy
group (that is present in the starting amine as well) in PNI
can substantially improve the solubility of the polymers,
and in this case the synthesis can be carried out in dipolar
aprotic solvents.4
Hence, we chose Nꢀ(2ꢀhydroxyphenyl)ꢀ1,8ꢀnaphthalꢀ
imide (1) as the model compound for PNI with hydroxy
groups, the conditions of its synthesis being similar to the
conditions of the polymer synthesis (dipolar aprotic
solvents, heating, and the catalysis by a carboxylic
acid—organic base system, in the absence of which highꢀ
molecularꢀweight PNI cannot be synthesized).1,4
In the present study, we found that imide 1 can be synꢀ
thesized in quantitative yield by the reaction of 1,8ꢀnaphthꢀ
alenedicarboxylic acid anhydride (2) with 2ꢀaminophenol
(3) in DMF upon heating (60—120 °C) in the presence of
benzoic acid and triethylamine as the catalysts (Scheme 1).
Scheme 1
Certain naphthalimides and PNI can be easily preꢀ
pared by performing the reactions in phenols in the presꢀ
ence of a carboxylic acid and an organic base as the cataꢀ
lysts.4 However, a serious drawback of this method is that it
requires the use of toxic and aggressive phenols as solvents.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 501—509, March, 2011.
1066ꢀ5285/11/6003ꢀ512 © 2011 Springer Science+Business Media, Inc.

Nꢀ(2ꢀHydroxyphenyl)ꢀ1,8ꢀnaphthalimide
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 3, March, 2011
513
The alkylation of the hydroxy group in compound 1
was also performed in DMF. Initially, the phenoxide was
generated with the use of the deprotonating agent (NaH,
K2CO3, or ButOK) and then an alkylating agent was adꢀ
ded. The alkylation was most efficient when phenoxide
was generated with the use of sodium hydride.
1,3ꢀPropane sultone and sodium 3ꢀbromopropaneꢀ
sulfonate were chosen for the introduction of the alkylꢀ
sulfo group (Scheme 2).
C(21)
C(20)
C(19)
C(15)
C(16)
O(3)
C(14)
C(13)
C(17)
The modification occurred in high yield when these
reagents were taken in a slight excess, no advantages of
a particular reagent being observed.
C(18)
N(1)
O(2)
C(4)
C(5)
The introduction of functional arenes into molecule 1
was performed in two steps (Scheme 3). Initially, comꢀ
pound 1 was alkylated with propargyl bromide. Then the
[2+3]ꢀcycloaddition at the triple bond of propargyl
ether 5 (Huisgen reaction) was performed in the presence
of CuI.5 The structure of product 5 was completely
confirmed by 1H NMR and Fourierꢀtransform infrared
spectroscopy, elemental analysis, and Xꢀray diffracꢀ
tion (Fig. 1).
O(1)
C(1)
C(2)
C(12)
C(6)
C(3)
C(9)
C(11)
C(7)
C(8)
C(10)
Aryl azides 6—8 used in the cycloaddition were synꢀ
thesized in quantitative yields from the corresponding
anilines by the diazotization followed by the treatment of
the diazonium salt with sodium azide. Then azides 6—8
(after recrystallization or immediately in the reaction mixꢀ
ture) were mixed with a solution of propargyl derivative 5
in DMSO and the catalysts (see Scheme 3).
The 1,3ꢀdipolar addition of alkyne 5 to azides 6—8
readily occurs upon heating to 80 °C and the addition of
D,Lꢀproline (in the absence of the latter, the reaction does
not proceed). It should be noted that triethylamine does
not facilitate this reaction.
Fig. 1. Molecular structure of compound 5.
On passing to polymerꢀanalogous reactions, IR moniꢀ
toring becomes a convenient tool since the sampling reꢀ
quires a short time. The reactions with propargyl bromide
and then with the certain azide are accomapnied by subꢀ
stantial changes in the arrangement and the shape of bands
in the IR spectra in the range of 3700—1500 cm–1
The structure of phosphonate 9 was confirmed by Xꢀray
diffraction (Fig. 2).
Carboxy groups of enhanced acidity were introduced
into model naphthalimide 1 with the use of ethyl bromoꢀ
difluoroacetate (Scheme 4).
It appeared that the reaction of compound 1 with ethyl
bromodifluoroacetate reaction was not completed. The
19F NMR data indicate that the alkylating agent is conꢀ
sumed in side reactions. It remains unclear why the reacꢀ
.
The azido group gives an intense absorption band in
the IR spectra in the region of 2000—2400 cm–1,6 due to
which (in combination with 1H NMR spectroscopy) azide
transformations can be easily monitored. In the case of
azides, which were synthesized in the present study, the
azide group is manifested at 2100—2120 cm–1
.
Scheme 2
B is a base.

514
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 3, March, 2011
Ponomarev et al.
Scheme 3
tion of phenoxide 1a with ethyl bromodifluoroacetate ocꢀ
curred only during the first day in spite of the presence of
1a in the reaction mixture for several days and the addition
of an excess of the base for the more complete deprotonaꢀ
tion of the hydroxy group.
To optimize the procedure for the synthesis, the ratio
of the reagents and the reaction temperature were varied.
We found that the temperature has only a slight effect on
the outcome of the reaction in the range of 2—80 °C alꢀ
though the heating results in an increase in the fraction of
byꢀproducts. The additional purification of ethyl bromodiꢀ
fluoroacetate by distillation does not raise the yield.
A change in the ratio of the reacting components showed
that the addition of an excess of ethyl bromodifluoroaceꢀ
tate results in a substantial increase in the yield of the
target product (from 25 to 70% in the case of 2 and 4 equiv.
of the reagent, respectively).
Due to a substantial difference in the positions of the
signals for the fluorine atoms of the starting ethyl bromoꢀ
difluoroacetate and product 12 (δ –62.19 and –75.53,
respectively, in DMSOꢀd6), the course of the reaction can
be roughly monitored by 19F NMR spectroscopy. Howevꢀ
er, 19F NMR spectroscopy provides only the qualitative
monitoring of the reaction because the starting compound
1 does not contain fluorine atoms and the ratio of the
integrated intensities of the signals not always corresponds
to the actual conversion of 1.
Scheme 4

Nꢀ(2ꢀHydroxyphenyl)ꢀ1,8ꢀnaphthalimide
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 3, March, 2011
515
C(116)
C(117)
O(14)
C(118)
C(115)
C(114)
C(113)
C(119)
C(120)
O(16)
N(11)
C(11)
C(12)
C(121)
N(12)
C(16)
C(15)
C(17)
N(14)
C(127)
C(132)
O(15)
C(13)
C(19)
C(126)
C(128)
C(122)
C(125)
C(14)
C(112)
C(18)
C(110)
N(13)
C(131)
O(11)
C(123)
O(12)
P(1)
C(124)
C(111)
O(13)
C(129)
C(130)
Fig. 2. Molecular structure of compound 9. One of two crystallographically independent molecules is shown.
Based on the Xꢀray diffraction study of substitution
products 5, 9, and 12, certain conclusions were made about
the spatial arrangement of the Nꢀarylꢀ1,8ꢀnaphthalimides
molecules containing ortho substituents in the phenyl ring
and about their crystal packing.
In all molecules, the Nꢀarylꢀ1,8ꢀnaphthalimide moiꢀ
eties have similar structures (Figs 1—3). Thus, the triꢀ
cyclic system is planar, and the phenyl ring is twisted
about the C—N bond by 108.9 (5), 95.3° (9), 103.2, and
102.3° (in two independent molecules of 12). The C—N
bond length is 1.438(2), 1.440(1), 1.441(3), and 1.450(3)
Å in 5, 9, and two independent molecules of 12, respecꢀ
tively. This is consistent with the data published in the
literature.7 The deviation of the oxygen atom bound to the
phenyl ring is small (0.01—0.09 Å). The average C(Ph)—O
bond length is 1.365 Å.
An increase in the degree of branching of the Oꢀsubꢀ
stituent (12 > 5 > 9) has an effect only on the angle of
rotation of the phenyl ring with respect to the tricyclic
system. The bond lengths and bond angles in all these
molecules have standard values.
The molecular packing in the crystal structures of 5,
9, and 12 is determined by π—π stacking interactions
between the aromatic rings and is complicated with
an increase in the number of aromatic rings in the moleꢀ
cule (5, 9 → 12). In the structure of 5, two molecules
are linked together by the π—π stacking interaction
only between the tricyclic moieties (the distance beꢀ
tween the planes d = 3.35 Å) to form intermolecular dimers
(Fig. 4).
O(4)
F(1)
C(20)
C(21)
C(19)
C(17)
C(18)
O(5)
F(2)
C(22)
C(16)
C(15)
O(3)
C(13)
O(1)
C(1)
N(1)
C(14)
C(2)
C(3)
C(4)
C(12)
C(10)
O(2)
C(11)
C(5)
C(6)
C(7)
C(9)
C(8)
Fig. 3. Molecular structure of compound 12.
In the structure of 12, the π—π stacking interacꢀ
tion is also observed between the tricyclic moieties, reꢀ

516
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 3, March, 2011
Ponomarev et al.
Fig. 4. Crystal packing of compound 5.
Fig. 5. Crystal packing of compound 12.

Nꢀ(2ꢀHydroxyphenyl)ꢀ1,8ꢀnaphthalimide
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 3, March, 2011
517
sulting in stacks of the molecules (Fig. 5) running along
the a axis (the distances between the planes d = 3.40
and 3.57 Å).
crystal structure is composed of there are double layers
(parallel to the ab plane and separated by the O=P(OEt)2
substituents) (Fig. 6).
In molecule 9, the phenyltriazole moiety is orthogonal
to the Nꢀphenyl ring but is parallel to the tricyclic moiety
(the dihedral angle between the planes is 4.0о). As a result,
there are π—π stacking interactions between all aromatic
moieties (the interplanar distances are 3.4—3.5 Å). The
To sum up, we studied the conditions of the alkylation
of the hydroxy group in compound 1. Based on the results
of the study, the corresponding polymerꢀanalogous reacꢀ
tions of poly(2ꢀhydroxyphenyl)naphthalimides can be simꢀ
ilarly investigated.
Fig. 6. Crystal packing of compound 9.

518
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 3, March, 2011
Ponomarev et al.
Nꢀ(2ꢀPropargyloxyphenyl)ꢀ1,8ꢀnaphthalimide (5). Potassium
tertꢀbutoxide (0.123g, 1.1 mmol) was added to a solution of comꢀ
pound 1 (0.289 g, 1 mmol) in DMF (2 mL), and then propargyl
bromide (0.131 g, 1.1 mmol) was added dropwise. The synthesis
was carried out at ∼20 °C for 8 h (TLC monitoring). Then water
was added to the mixture. The precipitate that formed was filꢀ
tered off, washed with water until neutral pH, dried, recrystalꢀ
lized from an ethanol—acetone mixture, and dried in vacuo at
Experimental
The melting points were determined on a Boetius hotꢀstage
apparatus and are uncorrected. The 1H, 31P, and 19F NMR specꢀ
tra were recorded on Bruker AMXꢀ400 (400.13 MHz), Bruker
Avanceꢀ400 (161.98 MHz), and Bruker AVꢀ300 (282.40 MHz)
instruments in DMSOꢀd6. The chemical shifts δ were calculated
based on the residual signals for protons of the deuterated solꢀ
1
60 °C. The yield was 0.32 g (75%), m.p. 173—176 °C. H NMR
vent as the internal standard (1H) and 85% H3PO4
CFCl3
19F) as the external standards. The assignments in the
NMR spectra are the authors' opinion.
The IR absorption spectra of samples were recorded on
a MagmaꢀIR 750 Nicolet Fourierꢀtransform infrared spectroꢀ
meter in the 4000—400 cm–1 region.
The course of the reactions was monitored and the purity of
the reaction products was checked by TLC on Silufol UVꢀ254
plates using ethanol—toluene (3 : 1, v/v) (A) and ethyl aceꢀ
tate—toluene (1 : 5, v/v) (B) mixtures as the eluents.
(
31P) and
(400 MHz), δ: 3.52 (t, 1 H, CCH, 3JH—H = 4.1 Hz); 4.78 (d, 2 H,
OCH2, 4JH—H = 4.1 Hz); 7.15 (t, 1 H, oꢀC6H4, 3JH—H = 7.6 Hz);
(
3
7.30 (d, 1 H, oꢀC6H4, JH—H = 7.6 Hz); 7.40 (d, 1 H, oꢀC6H4,
3
3JH—H = 7.5 Hz); 7.3 (t, 1 H, oꢀC6H4, JH—H = 7.3 Hz); 7.92
(t, 2 H, C(3)H, C(6)H, 3JH—H = 7.4 Hz); 8.52 (d, 2 H, C(4)H,
CH(5), 3JH—H = 7.6 Hz); 8.53 (d, 2 H, C(2)H, C(7)H, 3JH—H
=
= 8.3 Hz). IR (KBr), ν/cm–1: 3235 (C≡CH); 1710, 1668 (C=O);
1237 (ArOCH2). Found (%): C, 77.00; H, 3.99; N, 4.33.
C21H13NO3. Calculated (%): C, 77.05; H, 4.00; N, 4.28.
Nꢀ(2ꢀHydroxyphenyl)ꢀ1,8ꢀnaphthalimide (1). Dimethylformꢀ
amide (6 mL) and triethylamine (0.455 g, 4.5 mmol) were added
to a mixture of 1,8ꢀnaphthalenedicarboxylic acid anhydride 2
(1.784 g, 9 mmol), oꢀaminophenol 3 (1.03 g, 9.5 mmol), and
benzoic acid (0.549 g, 4.5 mmol). The synthesis was carried out
with stirring at 70 °C for 12 h. In the course of the reaction, the
reactants first dissolved and then the product precipitated.
The course of the reaction was monitored by TLC (system B,
Rf = 0.7). The precipitate that formed was filtered off, washed
with acetone, and dried in vacuo at 140 °C. The yield was 2.4 g
(90%), m.p. 328—331 °C. 1H NMR (400 MHz), δ: 6.94 (t, 1 H,
Diethyl 4ꢀazidobenzylphosphonate (6). Diethyl 4ꢀaminoꢀ
benzylphosphonate (Acros Organics) was subjected to diazotizaꢀ
tion according to the procedure described8 for toluidine. Then
an equivalent amount of a 30% aqueous sodium azide solution
was added to the aqueous solution of the diazonium salt cooled
to 0 °C in such a way as to maintain the temperature below 5 °C.
The mother liquor over the oil that formed was removed by
decantation. The oil was dried in vacuo over P2O5. The reaction
occurred quantitatively. 1H NMR (400 MHz), δ: 1.17 (t, 6 H,
3
2
Me, JH—H = 7.1 Hz); 3.23 (d, 2 H, CH2P, JH—P = 21.5 Hz);
3
3.95 (dq, 4 H, MeCH2, JH—H
=
3JH—P =7.3 Hz); 7.04—7.12
(m, 2 H, C6H4); 7.28—7.36 (m, 2 H, C6H4). 31P NMR, δ: 26.47
(s, CH2P). Found (%): C, 49.02; H, 6.01; N, 15.65; P, 11.52.
C11H16N3O3P. Calculated (%): C, 49.07; H, 5.99; N, 15.61;
P, 11.50.
3
3
oꢀC6H4, JH—H = 7.6 Hz); 7.00 (d, 1 H, oꢀC6H4, JH—H
=
= 8.2 Hz); 7.25 (d, 1 H, 3JH—H = 7.8 Hz); 7.30 (d, 1 H, oꢀC6H4,
3JH—H = 7.7 Hz); 7.90 (t, 2 H, H(3)C, H(6)C, 3JH—H = 7.7 Hz);
8.50 (d, 4 H, H(2)C, H(4)C, H(5)C, H(7)C, 3JH—H = 7.2 Hz);
9.69 (br.s, 1 H, HO). IR (KBr), ν/cm–1: 3301 (OH); 1703, 1650
(C=O). Found (%): C, 74.77; H, 3.79; N, 4.84. C18H11NO3.
Calculated (%): C, 74.73; H, 3.83; N, 4.84.
Sodium 3ꢀazidobenzenesulfonate (7). The diazonium salt was
synthesized from methanilic acid according to the procedure
described earlier8 for sulfanilic acid. Then an equivalent amount
of a 30% aqueous sodium azide solution was added to the aqueꢀ
ous solution of the diazonium salt cooled to 5 °C in such a way as
to maintain the temperature below 12 °C. The precipitate of the
azide that formed was filtered off and dried. The reaction ocꢀ
curred quantitatively. 1H NMR (400 MHz), δ: 7.04—7.09
(m, 1 H, C(4)H); 7.27—7.31 (m, 1 H, C(2)H); 7.38 (t, 1 H,
C(5)H, 3JH—H = 7.6 Hz); 7.42 (d, 1 H, C(6)H, 3JH—H = 7.6 Hz).
IR (KBr), ν/cm–1: 2107 (N3); 1213, 1175, 1047 (SO3–). Found (%):
C, 32.55; H, 1.80; N, 19.03; S, 14.47. C6H4N3NaO3S. Calcuꢀ
lated (%): C, 32.58; H, 1.82; N, 19.00; Na, 10.39; S, 14.50.
Sodium 4,4´ꢀdiazidodiphenylꢀ2,2´ꢀdisulfonate (8). The diꢀ
azonium salt was synthesized from 4,4´ꢀdiaminodiphenylꢀ2,2´ꢀ
disulfonic acid according to a known procedure.8 Then an equivꢀ
alent amount of a 30% aqueous sodium azide solution was added
to the aqueous solution of the diazonium salt cooled to 10 °C in
such a way as to maintain the temperature below 20 °C. The
reaction occurred quantitatively. The reaction mixture was conꢀ
centrated to dryness, and the residue was recrystallized from an
isopropanol—water mixture. 1H NMR (400 MHz), δ: 6.93—7.00
(m, 2 H, C(5)H, C(5´)H); 7.31—7.38 (m, 2 H, C(6)H, C(6´)H);
7.56 (s, 2 H, C(3)H, C(3´)H). IR (KBr), ν/cm–1: 2116 (N3);
1233, 1205, 1043, 1032 (SO3–). Found (%): C, 32.70; H, 1.38;
N, 19.00; S, 14.54. C12H6N6Na2O6S2. Calculated (%): C, 32.73;
H, 1.37; N, 19.09; S, 14.56.
Sodium or potassium salt of Nꢀ[2ꢀ(3ꢀsulfopropoxy)phenyl]ꢀ
1,8ꢀnaphthalimide (4). Potassium carbonate (0.173 g, 1.25 mmol)
or potassium tertꢀbutoxide (0.123 g, 1.1 mmol) was added to
a solution of compound 1 (0.289 g, 1 mmol) in DMF (2 mL).
After 30 min, propane sultone (0.134 g, 1.1 mmol) was added.
The reaction was carried out at ∼20 °C for 8 h. The course of the
reaction was monitored by TLC (system A, Rf = 0.4). After comꢀ
pletion of the reaction, the mixture was diluted with water. The
precipitate that formed upon cooling was filtered off, dried, and
recrystallized from water. The yield was 0.35 g (78%) and 0.31 g
(69%) in the reactions with the use of potassium carbonate and
potassium tertꢀbutoxide, respectively.
The synthesis with the use of sodium hydride (0.042 g,
1.05 mmol) as the base in THF was carried out in a similar way at
50 °C. The yield was 0.239 g (60%), m.p. > 300 °C (decomp.).
1H NMR (400 MHz), δ: 1.70—1.85 (m, 2 H, CH2CH2CH2);
2.22—2.40 (m, 2 H, CH2SO3); 3.98—4.13 (m, 2 H, OCH2); 7.07
3
(t, 1 H, oꢀC6H4, JH—H = 6.9 Hz); 7.20 (d, 1 H, oꢀC6H4,
3
3JH—H = 7.9 Hz); 7.35 (d, 1 H, oꢀC6H4, JH—H = 6.9 Hz); 7.44
(t, 1 H, oꢀC6H4, 3JH—H = 6.8 Hz); 7.92 (t, 2 H, C(3)H, C(6)H,
3JH—H = 7.4 Hz); 8.53 (d, 4 H, C(2)H, C(4)H, C(5)H, C(7)H,
3JH—H = 7.0 Hz). Found (%): C, 56.16; H, 3.56; N, 3.15;
S, 7.18. C21H16KNO6S. Calculated (%): C, 56.11; H, 3.59;
N, 3.12; S, 7.13.

Nꢀ(2ꢀHydroxyphenyl)ꢀ1,8ꢀnaphthalimide
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 3, March, 2011
519
Diethyl 4ꢀ[5ꢀ(2ꢀnaphthalimidophenoxymethyl)ꢀ1Hꢀ1,2,3ꢀtriꢀ
azolꢀ1ꢀyl]benzylphosphonate (9). An ethanolic solution of azide
6 (0.23 g, 1 mmol), copper(I) iodide (0.01 g), sodium ascorbate
(0.01 g), and D,Lꢀproline (0.01 g) were added to a suspension of
compound 5 (0.271 g, 0.829 mmol) in a 1 : 1 ethanol—water
mixture (4 mL). The reaction was carried out at 80 °C (TLC
monitoring). After completion of the reaction, the precipitate
that formed was filtered off, dried, and recrystallized from aceꢀ
tone. The yield was 70%, m.p. > 300 °C (decomp.). 1H NMR
(300 MHz), δ: 1.19 (t, 6 H, Me, 3JH—H = 7.0 Hz); 3.33 (d, 2 H,
itate that formed was filtered off, dried, and recrystallized from
an acetone—water mixture. The yield was 0.4 g (80%), m.p.
> 300 °C (decomp.). 1H NMR (400 MHz), δ: 5.27 (s, 2 H,
CH2); 7.11—7.19 (m, 1 H, C6H4); 7.39 (d, 1 H, C6H4, 3J = 7.6 Hz);
7.47—7.57 (m, 3 H, C6H4); 7.62 (d, 1 H, C6H4, 3J = 7.9 Hz);
7.70 (d, 1 H, C6H4, 3J =7.5 Hz); 7.90 (t, 2 H, C(3)H, C(6)H,
3J = 7.7 Hz); 7.99 (s, 1 H, mꢀC6H4); 8.50 (d, 2 H, C(4)H, C(5)H,
3J = 8.2 Hz); 8.52 (d, 2 H, C(2)H, C(7)H, 3J = 7.2 Hz); 8.57
(s, 1 H, HC het.). Found (%): C, 59.09; H, 3.13; N, 10.20;
S, 5.82. C27H17N4NaO6S. Calculated (%): C, 59.12; H, 3.12;
N, 10.21; S, 5.85.
2
3
CH2P, JH—P = 21.8 Hz); 3.95 (dq, 4 H, MeCH2, JH—H
=
=
3JH—P = 7.3 Hz); 5.26 (s, 2 H, CH2O); 7.10—7.20 (m, 1 H,
Disodium 4,4´ꢀbis[5ꢀ(2ꢀnaphthalimidophenoxymethyl)ꢀ1Hꢀ
1,2,3ꢀtriazolꢀ1ꢀyl]diphenylꢀ2,2´ꢀdisulfonate (11). An equivalent
amount of an aqueous solution of azide 8 was added to a solution
of compound 5 (0.33 g, 1 mmol) in DMSO (3 mL). Then
copper(I) iodide (0.01 g), sodium ascorbate (0.01 g), and D,Lꢀ
proline (0.01 g) were added as the catalytic system. The reaction
was carried out at 80 °C (TLC monitoring). After completion of
the reaction, the precipitate that formed was filtered off, dried,
and recrystallized from an acetone—water mixture (1 : 1). The
yield was 0.55 g (75%), m.p. > 300 °C (decomp.). 1H NMR
(400 MHz), δ: 5.29 (m, 4 H, CH2); 7.11—7.19 (m, 2 H,
oꢀC6H4); 7.40 (d, 2 H, oꢀC6H4, 3JH—H = 7.9 Hz); 7.46 (d, 2 H,
C6H4); 7.35—7.52 (m, 5 H, C6H4); 7.63 (d, 2 H, C6H4, 3JH—H
=
3
= 8.2 Hz); 7.87 (t, 2 H, C(3)H, C(6)H, JH—H = 7.7 Hz); 8.49
(d, 4 H, C(2)H, C(4)H, C(5)H, C(7)H, 3JH—H = 7.8 Hz); 8.52
(s, 1 H, HC het.). 31P NMR, δ: 26.13 (s, CH2P). Found (%):
C, 63.88; H, 4.66; N, 9.63; P, 5.29. C31H27N4O6P. Calculated (%):
C, 63.91; H, 4.67; N, 9.62; P, 5.32.
Sodium 3ꢀ[5ꢀ(2ꢀnaphthalimidophenoxymethyl)ꢀ1Hꢀ1,2,3ꢀtriꢀ
azolꢀ1ꢀyl]benzenesulfonate (10). 3ꢀAzidobenzenesulfonic acid 7
(0.223 g, 1 mmol) was added to a solution of compound 5 (0.3 g,
0.917 mmol) in DMSO (3 mL). Then copper(I) iodide (0.01 g),
sodium ascorbate (0.01 g), and D,Lꢀproline (0.01 g) were added
as the catalytic system. The reaction was carried out at 80 °C
(TLC monitoring). After completion of the reaction, the precipꢀ
3
H(6)C, JH—H = 7.8 Hz); 7.48—7.55 (m, 4 H, oꢀC6H4); 7.62
(d, 2 H, C(5)H, 3JH—H = 8.0 Hz); 7.87—7.98 (m, 4 H, C10H6); 8.28
Table 1. Crystallographic characteristics and refinement statistics for compounds 5, 9, and 12
Compound
5
9
12
Molecular formula
Molecular weight
C21H13NO3
327.32
C32H29N4O6
C22H15F2NO5
411.35
596.56
Space group
Pꢀ1
Pna21
Pꢀ1
Т/K
a/Å
b/Å
c/Å
α/deg
β/deg
100
100
17.123(1)
9.4125(6)
35.270(2)
90.0
90.0
90.0
5684.4(6)
8
295
8.4541(7)
8.8692(8)
11.0406(6)
102.354(2)
104.074(2)
93.840(2)
778.18(11)
2
8.4013(5)
9.3718(6)
11.9756(7)
78.657(1)
84.324(1)
89.963(1)
919.78(10)
2
γ/deg
V/Å3
Z
dcalc/g cm–3
Crystal color, habit
Crystal dimensions/mm
Diffractometer
μ/cm–1
1.397
1.394
1.485
Colorless plate
0.65×0.45×0.30
«Bruker Apex II CCD»
0.94
Colorless plate
0.55×0.40×0.25
«Bruker Apex II CCD»
1.51
Colorless plate
0.45×0.30×0.20
«Bruker Apex II CCD»
1.19
Scan mode
φ/ω
2θmax/deg
Total number of reflections
56.0
6798
54.0
56927
60.0
11964
Number of independent
3727 (0.0169)
12298 (0.0541)
5311 (0.0203)
reflections (Rint
)
R1 (based on F for reflections with I > 2σ(I))
(number of reflections)
0.0381 (3190)
0.0452 (10752)
0.0438 (3427)
wR2 (based on F2 for all reflections)
Number of refined parameters
0.1081
226
0.338/–0.239
0.1045
775
0.825/–0.445
0.0973
272
0.208/–0.205
Residual electron density/e•Å–3
,
ρ
max/ρ
min
GOOF
F(000)
1.017
340
1.015
2496
1.018
424

520
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 3, March, 2011
Ponomarev et al.
(s, 2 H, C(3)H); 8.47—8.54 (m, 8 H, C10H6); 8.55 (s, 2 H,
HC het.). Found (%): C, 59.20; H, 2.97; N, 10.26; S, 5.80.
tron density maps and refined based on F 2 with anisotropic
hkl
displacement parameters. All hydrogen atoms were positioned
geometrically and refined using the riding model with U(H) =
= nU(C), where U(C) are the equivalent thermal parameters of
the carbon atoms to which the corresponding H atoms are bonded,
n = 1.5 for CH groups and 1.2 for CH2 and CH3 groups.
All calculations were carried out with the use of the SHELXTL
PLUS 5 program package.9
The atomic coordinates, bond lengths, bond angles, and therꢀ
mal parameters were deposited with the Cambridge Crystalloꢀ
graphic Data Centre (CCDC 770667ꢀ9) and can be obtained,
free of charge, on application to (www.ccdc.cam.uk/conts/
retrieving.html; CCDC, 12 Union Road, Cambridge CB2 1EZ;
fax: +44 1223 335 033; or deposit@ccdc.cam.ac.uk).
C
54H32N8Na2O12S2. Calculated (%): C, 59.23; H, 2.95; N, 10.23;
S, 5.86.
Nꢀ[2ꢀ(1,1ꢀDifluoroꢀ2ꢀethoxyꢀ2ꢀoxoethoxy)phenyl]ꢀ1,8ꢀ
naphthalimide (12). Potassium tertꢀbutoxide (0.123 g, 1.1 mmol)
was added to a solution of compound 1 (0.289 g, 1 mmol) in
DMF (2 mL). After a while, ethyl bromodifluoroacetate (0.406 g,
2 mmol) was added dropwise. The reaction mixture turned brown
and a substance began to precipitate. According to the TLC
data, two products formed. The reaction was carried out at 50 °C
for 3 days. According to the TLC data, the reaction was not
brought to completion. The reaction mixture was poured into
cold water. The precipitate that formed was filtered off and reꢀ
crystallized. According to the TLC and 1H NMR data, the preꢀ
cipitate consisted of product 12 and the starting compound 1 in
a ratio of 2 : 1.
We thank E. I. Goryunov for help in the interpretation
of the NMR spectra.
The reaction in the presence of potassium carbonate (0.18 g,
1.3 mmol) was carried out in a similar way at 50 °C. After the
addition of water, a white precipitate formed. The precipitate
was filtered off. Then an ethanol—acetone mixture was added to
the precipitate, and the residue that remained undissolved was
filtered off. According to the TLC data, this residue is the startꢀ
ing imide 1. The precipitate that formed from the solvent mixꢀ
References
1. G. I. Timofeeva, I. I. Ponomarev, A. R. Khokhlov, R. Merꢀ
cier, B. Sillion, Synthesis and Investigation of New Water
Soluble Sulfonated RigidꢀRod PolyꢀNaphthoyleneimide, Macꢀ
romol. Symp., 1996, 106, 345.
2. H. Cao, V. Chang, R. Hernandez, M. D. Heagy, J. Org.
Chem., 2005, 70, 4929.
3. S. Nishizaki, Nippon Kagaku Zasshi, 1965, 86, 696; Chem.
Abstr., 1966, 64, 3321.
4. I. I. Ponomarev, Dr. Sc. (Chem.) Thesis, A. N. Nesmeyanov
Institute of Organoelement Compounds, Russian Academy
of Sciences, Moscow, 1991 (in Russian).
5. F. SantoyoꢀGonzalez, F. HernandezꢀMateo, Heterocycl.
Chem., 2007, 7, 133.
6. D. Brown, A. Floyd, M. Sainsbury, Spectroscopy of Organic
Molecules, John Wiley, New York, 1988.
7. A. Yu. Kovalevskii, I. I. Ponomarev, M. Yu. Antipin, I. G.
Ermolenko, O. V. Shishkin, Izv. Akad. Nauk, Ser. Khim.,
2000, 168 [Russ. Chem. Bull., Int. Ed., 2000, 49, 70].
8. H. E. FiersꢀDavid, L. Blangey, Grundlegende Operationen
der Farbenchemie, SpringerꢀVerlag, Wien, 1952, 402 pp.
9. G. M. Sheldrick, SHELXTL Ver.5.0, Software Referense
Manual, Siemens Industrial Automation, Inc., Madison,
1995.
1
ture was filtered off and dried. According to the H NMR data,
the precipitate consisted of product 12 and the starting comꢀ
pound 1 in a ratio of 1 : 2. IR of the mixture, ν/cm–1: 3305 (OH);
1706, 1669 (C=O); 1240—1100 (CF2, ArOCH2).
The reaction with the use of 4 equiv. of ethyl bromodifluoroꢀ
acetate afforded 0.33 g of the precipitate. According to the
1H NMR data, the precipitate consisted of product 12 and the
starting compound 1 in a ratio of 4 : 1.
Product 12 was separated from an admixture of the starting
compound by recrystallization from an acetone—water mixture.
The yield was 0.16 g (50%), m.p. >300 °C (decomp.). 1H NMR
(400 MHz), δ: 0.50 (t, 3 H, Me, 3JH—H = 7.1 Hz); 3.86 (dq, 2 H,
CH2, 3JH—H = 7.1 Hz); 7.49—7.57 (m, 2 H, oꢀC6H4); 7.58—7.67
(m, 2 H, oꢀC6H4); 7.94 (t, 2 H, C(3)H, C(6)H, 3JH—H = 7.8 Hz);
3
8.55 (d, 2 H, C(4)H, C(5)H, JH—H = 7.2 Hz); 8.53 (d, 2 H,
C(2)H, C(7)H, 3JH—H = 8.3 Hz). 19F NMR, δ: –75.53 (s, CF3).
Found (%): C, 64.20; H, 3.66; F, 9.27; N, 3.39. C22H15F2NO5.
Calculated (%): C, 64.24; H, 3.68; F, 9.24; N, 3.41.
Xꢀray diffraction study. Single crystals of the compounds were
obtained by crystallization from acetone (5 and 9) or an ethyl
acetate—ethanol mixture (12). The Xꢀray data collection and
structure refinement statistics are given in Table 1. Absorption
corrections were not applied. The structures solved by direct
methods. All nonhydrogen atoms were located in difference elecꢀ
Received May 25, 2010;
in revised form February 25, 2011