Synthesis and condensation reactions of the boron difluoride complex with 3-acetyl-4-hydroxy-1-methyl-2-quinolone

Article abstract of DOI:10.1007/s11172-008-0229-y

A reaction of 3-acetyl-4-hydroxy-1-methyl-2-quinolone with boron trifluoride etherate gave its boron difluoride complex. Condensation of this complex with various carbonyl compounds afforded new 2-quinolone derivatives (polymethine and styryl dyes) that i

Full text of DOI:10.1007/s11172-008-0229-y

Russian Chemical Bulletin, International Edition, Vol. 57, No. 8, pp. 1734—1739, August, 2008
1734
Synthesis and condensation reactions of the boron difluoride complex
with 3ꢀacetylꢀ4ꢀhydroxyꢀ1ꢀmethylꢀ2ꢀquinolone
A. V. Manaev,a I. N. Okhrimenko,a K. A. Lyssenko,b and V. F. Traven´a
aD. I. Mendeleev University of Chemical Technology of Russia,
3 Miusskaya pl., 125047 Moscow, Russian Federation.
Fax: +7 (495) 609 2964. Eꢀmail: traven@muctr.edu.ru
bA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
A reaction of 3ꢀacetylꢀ4ꢀhydroxyꢀ1ꢀmethylꢀ2ꢀquinolone with boron trifluoride etherate
gave its boron difluoride complex. Condensation of this complex with various carbonyl comꢀ
pounds afforded new 2ꢀquinolone derivatives (polymethine and styryl dyes) that intensely
absorb in the visible region of the spectrum and show effective fluorescence.
Key words: quinolones, boron complexes, dyes, aldol condensation, fluorescence, crystal
structure.
Complex formation with boron compounds substanꢀ
Scheme 1
tially increases the reactivity of the methyl group of the
acetyl fragment in vicꢀacyl(hydroxy)coumarins.1,2 Such
complexes easily undergo condensation with carbonyl
compounds and their derivatives in acetic anhydride and
in a mixture of acetic and sulfuric acids. The resulting
products are usually dyes with intense absorption at long
wavelengths and effective fluorescence.3,4
In the present work, we studied the synthetic scope of
similar boron difluoride complexes based on 2ꢀquinolone
derivatives. The quinolone series was represented by
3ꢀacetylꢀ4ꢀhydroxyꢀ1ꢀmethylꢀ2ꢀquinolone, a known
intermediate in the synthesis of potential bactericides
and fungicides.5—8
F(2)
F(1)
B(1)
Results and Discussion
O(1)
O(2)
Reactions of boron trifluoride etherate with 3ꢀacetylꢀ
4ꢀhydroxyꢀ1ꢀmethylꢀ2ꢀquinolone (1) in benzene gave its
boron difluoride chelate complex 2 (Scheme 1).*
The structure of complex 2 was confirmed by 1H NMR
spectroscopy, mass spectrometry, elemental analysis, and
Xꢀray diffraction analysis (Fig. 1).
C(1)
C(7)
C(6)
C(10)
C(11)
C(2)
C(8)
C(9)
1
In the H NMR spectrum of chelate 2, the signal for
the methyl protons of the acetyl fragment is shifted
downfield by 0.5 ppm relative to the starting free hydroxy
compound 1. Therefore, the methyl protons in chelate 2
are more acid and allow condensation reactions with carꢀ
bonyl compounds. In control experiments, the starting
C(5)
C(3)
O(3)
C(4)
C(12)
* In Schemes 1—5, the protons are numbered for signal assignꢀ
ment in the H NMR spectra.
Fig. 1. General view of compound 2.
1
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1701—1706, August, 2008.
1066ꢀ5285/08/5708ꢀ1734 © 2008 Springer Science+Business Media, Inc.

Dioxaborinoquinolones
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 8, August, 2008
1735
C(12)
O(1A)
F(1A)
O(3)
B(1A) F(2A)
C(9)
N(1)
C(2A)
C(1A)
C(11)
C(10)
O(2A)
C(4)
C(7A)
C(5)
C(8)
C(6A)
C(5A)
a
C(3)
C(10A)
C(6)
C(8A)
C(2)
C(7)
O(1)
C(4A)
B(1)
C(1)
N(1A)
O(2)
F(2)
C(11A)
C(9A)
O(3A)
C(12A)
F(1)
c
0b
Fig. 2. Stacking interaction between the molecules in crystal
structure 2.
quinolone 1 proved to be inert under the conditions
of both baseꢀ and acidꢀcatalyzed condensation.
According to Xꢀray diffraction data, introduction of
the boron difluoride fragment into compound 1 substanꢀ
tially equalizes the bond lengths. The bond lengths charꢀ
acteristic of a sixꢀmembered boron heterocycle suggest a
conjugation in the fragment O—C=C—C=O (Table 1).
The observed equalization of the C—C and C—O bonds
is due to the formation of a donorꢀacceptor B...O bond
and a considerable degree of πꢀdelocalization. The
C(7)—O(1), C(7)—C(8), C(8)—C(10), and C(10)—O(2)
bond lengths are 1.309(2), 1.398(2), 1.426(2), and 1.283(2) Å,
respectively. The B—O bond lengths in the complex
are close (1.480 and 1.502 Å), with slight elongation of
the B(1)—O(2) bond. The molecule is planar because the
meanꢀsquare deviation of the atoms from its plane
does not exceed 0.01 Å (except for the F and H atoms).
In the crystal, the molecules are packed in piles aligned
with the crystallographic axis b. The piles are stabilized by
Fig. 3. Molecular packing in crystal structure 2.
sufficiently strong stacking interactions (Fig. 2). The
distance between the planes of the molecules is 3.32 Å.
The shortest C...C contacts are C(5)...C(7A) (3.398(2) Å),
C(1)...C(9A) (3.402(2) Å), and C(3)...C(10A) (3.346(2) Å).
These piles are united into a threeꢀdimensional frameꢀ
work through a number of shortened contacts C—H...O,
the shortest contact being H(2)...O(3) (2.25 Å, the angle
CHO is 155°) (Fig. 3).
Complex 2 reacts with various carbonyl compounds
under mild conditions to give the corresponding conꢀ
densation products at the methyl group. For instance, a
reaction of two moles of compound 2 with triethyl
orthoformate in the presence of triethylamine yielded
Table 1. Selected bond lengths (d) and angles (ω) in boron complex 2 from Xꢀray diffraction data
Bond
d/Å
Parameter
Value
Angle
ω/deg
F(1)—B(1)
F(2)—B(1)
B(1)—O(1)
B(1)—O(2)
N(1)—C(5)
N(1)—C(9)
N(1)—C(12)
O(1)—C(7)
O(2)—C(10)
O(3)—C(9)
C(6)—C(7)
C(7)—C(8)
C(8)—C(9)
C(8)—C(10)
1.360(3)
1.367(3)
1.480(2)
1.502(3)
1.390(2)
1.396(2)
1.471(2)
1.309(2)
1.283(2)
1.227(2)
1.438(2)
1.398(2)
1.463(3)
1.426(2)
Bond
C(10)—C(11)
Angle
d/Å
1.487(3)
ω/deg
F(1)—B(1)—O(2)
F(2)—B(1)—O(2)
O(1)—B(1)—O(2)
O(1)—C(7)—C(8)
C(7)—C(8)—C(9)
C(10)—C(8)—C(9)
O(3)—C(9)—N(1)
N(1)—C(9)—C(8)
O(3)—C(9)—C(8)
O(2)—(10)—C(8)
O(2)—C(10)—C(11)
C(8)—C(10)—C(11)
108.01(17)
108.27(17)
110.06 (16)
122.75(16)
120.82(15)
121.12(16)
120.05(17)
116.51(15)
123.44(16)
120.16(16)
114.82(16)
125.01(17)
C(5)—N(1)—C(9)
C(5)—N(1)—C(12)
C(9)—N(1)—C(12)
C(7)—O(1)—B(1)
C(10)—O(2)—B(1)
F(1)—B(1)—F(2)
O(1)—C(7)—C(6)
C(8)—C(7)—C(6)
C(7)—C(8)—C(10)
F(1)—B(1)—O(1)
F(2)—B(1)—O(1)
123.19(15)
119.63(15)
117.18(15)
123.16(15)
125.66(15)
111.40(17)
116.85(15)
120.40(16)
118.06(16)
109.65(17)
109.41(18)

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Russ.Chem.Bull., Int.Ed., Vol. 57, No. 8, August, 2008
Manaev et al.
Scheme 2
Scheme 3
F
F
B
O
O
HC(O)NMe2
Me
Ac2O
N
O
Me
2
F
F
B
O
O
1
4
6
2
3
N(Me)2
5
N
O
Me
4
symmetric polymethine dye 3 (Scheme 2). In acetoniꢀ
trile, compound 3 absorbs at 581 nm with a high molar
absorption coefficient and shows noticeable fluorescence.
A reaction of complex 2 with DMF gave enamine 4
(Scheme 3), which can serve as a valuable synthon for
transformations of the 2ꢀquinolone fragment.
Condensation of various aromatic and heterocyclic
aldehydes with complex 2 afforded boronꢀcontaining styryl
dyes 5a—g, which are characterized by high molar
absorption coefficients in the longꢀwavelength region
and exhibit considerable fluorescence in solutions
(Scheme 4). Hydrolysis of compounds 5a—f yielded new
Scheme 4
F
F
F
F
B
B
O
O
O
O
OH
O
O
1) H2O, EtOH,
Na2CO3
1
4
1
4
6
6
2
3
2
3
Me
R
R
RCHO
2) HCl
5
5
Ac2O/AcOH,
H2SO4
N
O
N
O
N
Me
Me
Me
2
5a—g
6a—f
8
7
O
7
8
9
7
8
9
7
8
Me
R =
Me
,
,
10
10
9
N
,
S
Me
N
O
O
Me
Me
Me
Me
a
c
d
b
8
9
Me
Me
8
7
11
8
O
7
10
10
9
12
10
7
MeO
11
11
O
N
9
S
,
,
N
Me
Me
N
H
e
f
g

Dioxaborinoquinolones
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 8, August, 2008
1737
Table 2. Elemental analysis data and the band positions in the
electronic absorption spectra of compounds 2—4, 5a—g, and
6a—f
Experimental
1H NMR spectra were recorded on a Bruker WPꢀ200ꢀSY
instrument (200 MHz) in DMSOꢀd6 and CDCl3 with Me4Si
as the internal standard. Electronic absorption spectra were
recorded on a Specord UVꢀVIS spectrometer in acetonitrile.
Mass spectra were recorded on a PE SCIEX API165 spectroꢀ
meter (ELSD UV254) (ionizing voltage 80 eV, emitter temperaꢀ
ture 250 °C, evaporator temperature 240 °C).
Comꢀ
pound
Molecular
formula
Found
Calculated
UVꢀVis,
(%)
λ
max/nm
–
4
С
H
N
(ε•10
)
2
C12H10BF2NO3
С31Н33B2F4N3O6
С15Н15BF2N2O3
С21Н19BF2N2O3
С20Н16BF2NO4
C21H18BF2NO5
С19Н17BF2N2O3S
С21Н19BF2N2O4S
С25Н23BF2N2O3
С26H21BF2N2O5
С21Н20N2O3
54.34 3.79 5.31
54.38 3.80 5.29
57.91 5.09 6.44
394
(2.11)
581
Xꢀray diffraction analysis of compound 2 (C12H10BF2NO3,
M = 265.02) was carried out on a Smart 1000 CCD automatic
threeꢀcircle diffractometer. At 120 K, the crystals are monoꢀ
clinic: a = 10.2838(10) Å, b = 6.7343(6) Å, c = 16.2397(15) Å,
3
58.03 5.15 6.53 (14.92)
4
56.19 4.61 8.68
56.25 4.69 8.5
63.59 4.86 7.02
63.66 4.83 7.07
62.63 4.22 3.56
62.69 4.21 3.66
60.97 4.36 3.43
61.05 4.39 3.39
56.64 4.34 6.92
56.74 4.26 6.96
56.64 4.28 6.27
56.78 4.31 6.31
66.93 5.12 6.24
66.98 5.17 6.25
63.69 4.33 5.69
63.70 4.32 5.71
72.53 5.68 7.98
72.42 5.75 8.05
71.67 5.07 4.16
71.63 5.11 4.18
68.96 5.17 3.90
69.03 5.24 3.83
64.38 5.11 7.83
64.39 5.12 7.90
63.56 4.99 7.13
63.62 5.08 7.07
74.87 5.98 7.04
74.98 6.04 7.00
375
(3.31)
570
(7.32)
462
(6.12)
490
(4.45)
594
(4.96)
585
(5.21)
592
(8.24)
512
(2.39)
525
(5.84)
398
(3.65)
423
(2.02)
550
(2.96)
535
3
β = 92.476(6)°, V = 1123.62(18) Å , dcalc = 1.567 g cm–1, space
5a
5b
5c
5d
5e
5f
5g
6a
6b
6c
6d
6e
6f
group P21/n, Z = 4. The intensities of 11 683 reflections were
measured on an automatic diffractometer at 120 K (MoꢀKα
radiation, graphite monochromator, ωꢀscan mode, 2θmax = 58°);
2982 observed reflections (Rint = 0.0383) were used in further
calculations. The structure was solved by the direct method and
refined by the fullꢀmatrix leastꢀsquares method in the anisotroꢀ
picꢀisotropic approximation on F2. The hydrogen atoms were
located from electronꢀdensity difference maps and refined
isotropically. Final residuals are wR2 = 0.1447 (GOOF = 1.016)
for all reflections (R1 = 0.0566 for 1747 reflections with
I > 2σ(I)). All calculations were performed with the SHELXTL PLUS
program package.
3ꢀAcetylꢀ4ꢀdifluoroboryloxyꢀ1ꢀmethylꢀ2ꢀquinolone (2).
A threeꢀneck flask fitted with a stirrer, a dropping funnel, and a
reflux condenser with a drying calciumꢀchloride tube was
charged with 3ꢀacetylꢀ4ꢀhydroxyꢀ1ꢀmethylꢀ2ꢀquinolone (1)7
(21.7 g, 0.1 mol). Compound 1 was dissolved in a minimum
amount of dry benzene (200 mL). The mixture was refluxed to
complete homogenization. Then BF3•Et2O (15.62 g, 0.11 mol)
was added dropwise and the reaction mixture was refluxed for
1 h. The precipitate that formed was filtered off, washed with
benzene, and dried in air. Yield 22.8 g (86%), m.p. 226—227 °C.
1H NMR (DMSOꢀd6), δ: 2.72 (s, 3 H, Me); 3.55 (s, 3 H, MeN);
7.31 (t, 1 H, H(3)); 7.51 (d, 1 H, H(4), J = 8.8 Hz); 7.79 (t, 1 H,
H(2)); 8.08 (d, 1 H, H(1), J = 8.4 Hz). MS, m/z (Irel (%)): 265 (85).
Triethylammonium 1,5ꢀbis(4ꢀdifluoroboryloxyꢀ1ꢀmethylꢀ
2ꢀoxoꢀ1,2ꢀdihydroquinolinꢀ3ꢀyl)ꢀ5ꢀoxopentaꢀ1,3ꢀdienꢀ1ꢀolate
(3). Triethyl orthoformate (0.15 g, 1 mmol) and triethylamine
(0.28 mL, 2 mmol) were added to a solution of boron complex 2
(0.53 g, 2 mmol) in acetic anhydride (5 mL). The reaction
mixture was heated at 60 °C for 30 min and cooled. After 4 h, the
precipitate of the dye was filtered off. The filter cake was washed
with hexane (10 mL) and recrystallized from acetic acid. The
yield of compound 3 was 0.54 g (83%), m.p. 284—285 °C. 1H NMR
(DMSOꢀd6), δ: 1.18 (t, 9 H, Me3); 3.10 (q, 6 H, (—CH2—)3);
3.62 (s, 6 H, MeN); 7.33 (t, 2 H, H(3), H(9), J = 6.2 Hz); 7.54
(d, 2 H, H(4), H(8), J = 8.8 Hz); 7.76—7.85 (m, 4 H, H(2),
H(10), H(5), H(7)); 8.13 (d, 2 H, H(1), H(11), J = 6.6 Hz);
8.90 (t, 1 H, H(6), J = 6.2 Hz). MS, m/z (Irel (%)): 541 (70).
4ꢀDifluoroboryloxyꢀ3ꢀ[3ꢀdimethylaminopropꢀ2Eꢀenoyl]ꢀ
1ꢀmethylꢀ2ꢀquinolone (4). Dimethylformamide (0.15 mL, 2 mmol)
was added dropwise to a solution of compound 2 (0.53 g, 2 mmol)
in acetic anhydride (5 mL). The reaction mixture was heated at
90 °C for 30 min. On cooling, ethanol (2.5 mL) was added,
which was accompanied by spontaneous heating of the reaction
mixture. On cooling, the precipitate that formed was filtered
off and recrystallized from ethyl acetate. The yield of compound
4 was 0.25 g (76%), m.p. 297—298 °C. 1H NMR (DMSOꢀd6),
С20Н17NO4
C21H19NO5
С19Н18N2O3S
С21Н20N2O4S
С25Н24N2O3
(3.87)
530
(5.72)
4ꢀhydroxyꢀ2ꢀquinolone derivatives 6a—f, which fluoresce
in both solutions and the solid state.
The structures of compounds 6 were proved by
1H NMR spectroscopy. The lowꢀfield region (δ 7.30—9.00)
1
of their H NMR spectra shows, apart from the signals
for the aromatic protons, doublets for the vinyl protons
with a coupling constant of 12—15 Hz. Such a constant
suggests the transꢀconfiguration of these compounds. The
spectra of compounds 6a—f also contain a signal for
the OH proton at δ 17—19. The mass spectra of all the
compounds obtained show molecular ion peaks with
intensities of 40—100%.
The electronic absorption spectra of compounds 5a—g
and 6a—f exhibit a narrow intense band (Table 2). In the
spectra of the hydrolysis products, the absorption band
experiences a hypsochromic shift by 50—60 nm relative
to the peak for the boron chelates. On the whole, both the
dyes and their complexes absorb in nearly the same specꢀ
tral regions as similar coumarinꢀbased dyes.3

1738
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 8, August, 2008
Manaev et al.
δ: 3.40 (s, 6 H, Me); 3.61 (s, 3 H, MeN); 7.34 (t, 1 H, H(3));
7.55 (d, 1 H, H(4)); 7.74 (m, 2 H, H(1), H(6)); 8.11 (m, 1 H,
H(2), J = 8.4 Hz); 8.53 (d, 1 H, H(5), J = 12.0 Hz). MS, m/z
(Irel (%)): 320 (100).
Condensation of boron complex 2 with aldehydes (general
procedure). A. A solution of an aldehyde (4 mmol) in acetic
anhydride (2 mL) was added at 60 °C to a solution of boron
difluoride complex 2 (1.06 g, 4 mmol) in acetic anhydride (10 mL).
The reaction mixture was heated at 90 °C for 30 min. On cooling,
the precipitate that formed was filtered off. The filter cake was
washed with acetic acid and recrystallized from acetic acid to
give compounds 5a,d—g.
B. A solution of an aldehyde (4 mmol) in acetic acid (2 mL)
and conc. H2SO4 (0.5 mL) were added at 60 °C to a solution
of boron difluoride complex 2 (1.06 g, 4 mmol) in acetic acid
(6 mL). The reaction mixture was heated at 90 °C for 30 min.
On cooling, the precipitate that formed was filtered off. The
filter cake was washed with acetic acid and recrystallized from
acetic acid to give compounds 5b,c.
4ꢀDifluoroboryloxyꢀ3ꢀ[3ꢀ(4ꢀmethoxycarbonylꢀ5ꢀmethylꢀ
3ꢀphenylpyrrolꢀ2ꢀyl)propꢀ2Eꢀenoyl]ꢀ1ꢀmethylꢀ2ꢀquinolone (5g).
1
Yield 59% (A), m.p. >350 °C (decomp.). H NMR (CDCl3), δ:
2.72 (s, 3 H, Me); 3.46 (s, 3 H, MeO); 3.62 (s, 3 H, MeN); 7.21
(m, 2 H, H(3), H(4)); 7.38 (m, 5 H, H(7), H(8), H(9), H(10),
H(11)); 7.58 (d, 1 H, H(6), J = 14.8 Hz); 7.71 (t, 1 H, H(2)); 8.26
(d, 1 H, H(1), J = 8.8 Hz); 8.48 (d, 1 H, H(5), J = 14.8 Hz);
8.69 (s, 1 H, NH). MS, m/z (Irel (%)): 490 (90).
Hydrolysis of boron difluoride complexes 5a—f (general proꢀ
cedure). An appropriate boron difluoride complex 5a—f (3 mmol)
was dissolved in aqueous 60% ethanol (10 mL). Anhydrous
Na2CO3 (1.59 g, 15 mmol) was added and the reaction mixture
was refluxed for 1—5 h. The course of the reaction was moniꢀ
tored by TLC. The heating was continued until the starting
boron difluoride complex was completely consumed. On cooling,
the resulting solution was filtered and acidified to pH 6.5—7.
The precipitate that formed was filtered off, washed with water,
and recrystallized from propanꢀ2ꢀol.
3ꢀ[3ꢀ(4ꢀDimethylaminophenyl)propꢀ2Eꢀenoyl]ꢀ4ꢀhydroxyꢀ
1ꢀmethylꢀ2ꢀquinolone (6a). Yield 67%, m.p. 206—207 °C. 1H NMR
(DMSOꢀd6), δ: 3.04 (s, 6 H, NMe2); 3.59 (s, 3 H, MeN); 6.78
(d, 2 H, H(8), H(9), J = 8.8 Hz); 7.31 (t, 1 H, H(3)); 7.49—7.62
(m, 3 H, H(4), H(7), H(10); 7.75 (t, 1 H, H(2)); 7.94 (d, 1 H, H(6),
J = 15.2 Hz); 8.12 (d, 1 H, H(1), J = 8.3 Hz); 8.44 (d, 1 H, H(5),
J = 15.2 Hz), 14.4 (s, 1 H, OH). MS, m/z (Irel (%)): 348 (65).
4ꢀHydroxyꢀ3ꢀ[3ꢀ(4ꢀmethoxyphenyl)propꢀ2Eꢀenoyl]ꢀ1ꢀmethylꢀ
2ꢀquinolone (6b). Yield 71%, m.p. 195—196 °C. 1H NMR
(DMSOꢀd6), δ: 3.51 (s, 3 H, MeN); 3.80 (s, 3 H, MeO); 6.98 (d,
2 H, H(8), H(9), J = 8.7 Hz); 7.18 (t, 1 H, H(3)); 7.38 (d, 1 H, H(4),
J = 8.7 Hz); 7.59—7.69 (m, 4 H, H(2), H(6), H(7), H(10));
8.07—8.21 (m, 2 H, H(1), H(5)). MS, m/z (Irel (%)): 335 (100).
3ꢀ[3ꢀ(2,4ꢀDimethoxyphenyl)propꢀ2Eꢀenoyl]ꢀ4ꢀhydroxyꢀ
1ꢀmethylꢀ2ꢀquinolone (6c). Yield 83%, m.p. 146—147 °C. 1H NMR
(CDCl3), δ: 3.22 (t, 3 H, MeO); 3.59 (s, 3 H, MeN); 3.72 (s,
3 H, MeO); 6.38—6.51 (m, 2 H, H(8), H(9)); 7.18—7.29 (m,
2 H, H(3), H(4)); 7.62—7.78 (m, 2 H, H(2), H(7)); 8.16 (d,
1 H, H(6), J = 15.2 Hz); 8.25—8.32 (m, 2 H, H(1), H(5)); 17.98
(s, 1 H, OH). MS, m/z (Irel (%)): 365 (80).
3ꢀ[3ꢀ(5ꢀDimethylaminoꢀ2ꢀthienyl)propꢀ2Eꢀenoyl]ꢀ
4ꢀhydroxyꢀ1ꢀmethylꢀ2ꢀquinolone (6d). Yield 72%, m.p. 221—222 °C.
1H NMR (DMSOꢀd6), δ: 3.14 (s, 6 H, NMe2); 3.56 (s, 3 H,
MeN); 6.19 (d, 1 H, H(8), J = 4.6 Hz); 7.31 (d, 1 H, H(4),
J = 8.8 Hz); 7.46—8.15 (m, 5 H, H(1), H(2), H(3), H(6),
H(7)); 8.33 (d, 1 H, H(5), J = 13.4 Hz); 13.83 (s, 1 H, OH).
MS, m/z (Irel (%)): 354 (65).
4ꢀHydroxyꢀ1ꢀmethylꢀ3ꢀ[3ꢀ(5ꢀmorpholinoꢀ2ꢀthienyl)ꢀ
propꢀ2Eꢀenoyl]ꢀ2ꢀquinolone (6e). Yield 80%, m.p. 214—215 °C.
1H NMR (DMSOꢀd6), δ: 1.84 (m, 4 H, H(10), H(11)); 3.26
(m, 4 H, H(9), H(12)); 3.48 (s, 3 H, MeN); 6.64 (d, 1 H, H(8),
J = 2.8 Hz), 7.06 (t, 1 H, H(3)); 7.31—7.56 (m, 3 H, H(2),
H(4), H(7)); 7.73 (d, 1 H, H(6), J = 15.2 Hz); 7.95 (d, 1 H,
H(1), J = 8.8 Hz); 8.08 (d, 1 H, H(5), J = 15.2 Hz). MS, m/z
(Irel (%)): 396 (70).
4ꢀDifluoroboryloxyꢀ3ꢀ[3ꢀ(4ꢀdimethylaminophenyl)propꢀ
2Eꢀenoyl]ꢀ1ꢀmethylꢀ2ꢀquinolone (5a). Yield 84% (method A),
m.p. 300—301 °C. 1H NMR (DMSOꢀd6), δ: 3.18 (s, 6 H, NMe2);
3.63 (s, 3 H, MeN); 6.91 (d, 2 H, H(8), H(9), J = 9.2 Hz); 7.37
(t, 1 H, H(3)); 7.59 (d, 1 H, H(4), J = 8.8 Hz); 7.79—7.87 (m,
3 H, H(2), H(7), H(10)); 8.17 (d, 1 H, H(1), J = 8.3 Hz); 8.40
(d, 1 H, H(6), J = 14.8 Hz); 8.53 (d, 1 H, H(5), J = 14.8 Hz).
MS, m/z (Irel (%)): 396 (65).
4ꢀDifluoroboryloxyꢀ3ꢀ[3ꢀ(4ꢀmethoxyphenyl)propꢀ2Eꢀenoyl]ꢀ
1ꢀmethylꢀ2ꢀquinolone (5b). Yield 78% (B), m.p. 275—276 °C.
1H NMR (DMSOꢀd6), δ: 3.63 (s, 3 H, MeN); 3.89 (s, 3 H,
MeO); 7.14 (d, 2 H, H(8), H(9), J = 8.8 Hz); 7.48—7.62 (m, 3
H, H(2), H(3), H(4)); 7.83 (d, 1 H, H(6), J = 14.6 Hz), 7.89 (d,
2 H, H(7), H(10), J = 8.8 Hz), 8.31 (d, 1 H, H(1)), 8.65 (d, 1 H,
H(5), J = 14.6 Hz). MS, m/z (Irel (%)): 383 (70).
4ꢀDifluoroboryloxyꢀ3ꢀ[3ꢀ(2,4ꢀdimethoxyphenyl)propꢀ2Eꢀ
enoyl]ꢀ1ꢀmethylꢀ2ꢀquinolone (5c). Yield 63% (B), m.p. 273—274 °C.
1H NMR (CDCl3), δ: 3.26 (t, 3 H, MeO); 3.65 (m, 6 H, MeN,
MeO); 6.43 (s, 1 H, H(9)); 6.54 (d, 1 H, H(8), J = 9.0 Hz);
7.20—7.37 (m, 3 H, H(2), H(3), H(4)); 7.69—7.85 (m, 2 H,
H(1), H(7)); 8.40 (d, 1 H, H(6), J = 14.8 Hz); 8.51 (d, 1 H,
H(5), J = 14.8 Hz). MS, m/z (Irel (%)): 413 (90).
4ꢀDifluoroboryloxyꢀ3ꢀ[3ꢀ(5ꢀdimethylaminoꢀ2ꢀthienyl)propꢀ2Eꢀ
enoyl]ꢀ1ꢀmethylꢀ2ꢀquinolone (5d). Yield 80% (A), m.p. 312—313 °C.
1H NMR (DMSOꢀd6), δ: 3.39 (s, 6 H, NMe2); 3.62 (s, 3 H,
MeN); 6.86 (d, 1 H, H(8), J = 5.1 Hz); 7.34 (t, 1 H, H(3)); 7.55
(d, 1 H, H(4), J = 8.3 Hz); 7.71—7.77 (m, 2 H, H(2), H(6));
8.02—8.11 (m, 2 H, H(1), H(7)); 8.33 (d, 1 H, H(5), J = 12.9 Hz).
MS, m/z (Irel (%)): 402 (100).
4ꢀDifluoroboryloxyꢀ1ꢀmethylꢀ3ꢀ[3ꢀ(5ꢀmorpholinoꢀ2ꢀthienyl)ꢀ
propꢀ2Eꢀenoyl]ꢀ2ꢀquinolone (5e). Yield 67% (A), m.p. 292—293 °C.
1H NMR (DMSOꢀd6), δ: 1.92 (m, 4 H, H(10), H(11)); 3.41
(m, 4 H, H(9), H(12)); 3.60 (s, 3 H, MeN); 6.96 (d, 1 H, H(8),
J = 4.2 Hz); 7.29 (t, 1 H, H(3)); 7.47—7.51 (m, 2 H, H(4),
H(6)); 7.71 (t, 1 H, H(2)); 8.03—8.21 (m, 3 H, H(1), H(5),
H(7)). MS, m/z (Irel (%)): 444 (85).
4ꢀDifluoroboryloxyꢀ1ꢀmethylꢀ3ꢀ[4ꢀ(1,3,3ꢀtrimethylꢀ
2,3ꢀdihydroꢀindolꢀ2ꢀylidene)butꢀ2ꢀenoyl]ꢀ2ꢀquinolone (5f). Yield
76% (A), m.p. 316—317 °C. The 1H NMR spectrum of
compound 5f was not recorded because of its low solubility.
MS, m/z (Irel (%)): 448 (65).
4ꢀHydroxyꢀ1ꢀmethylꢀ3ꢀ[4ꢀ(1,3,3ꢀtrimethylꢀ2,3ꢀdihydroꢀ
indolꢀ2ꢀylidene)butꢀ2ꢀenoyl]ꢀ2ꢀquinolone (6f). Yield 69%, m.p.
224—225 °C. 1H NMR (DMSOꢀd6), δ: 1.66 (s, 6 H, Me2); 3.68
(s, 3 H, MeN); 3.72 (s, 3 H, MeN); 6.57 (d, 1 H, H(7), J = 14.8 Hz);
7.28—7.84 (m, 8 H, H(1), H(3), H(4), H(5), H(8), H(9), H(10),
H(11)); 8.10 (t, 1 H, H(2)); 8.64 (t, 1 H, H(6)); 11.99 (s, 1 H,
OH). MS, m/z (Irel (%)): 400 (60).

Dioxaborinoquinolones
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 8, August, 2008
1739
4. V. F. Traven, T. A. Chibisova, A. V. Manaev, Dyes Pigments,
2003, 58, 41.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 07ꢀ03ꢀ00936).
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Received May 29, 2007;
in revised form March 26, 2008