Reaction of 5-substituted 2-(3-chloropropanoylamino)benzophenone syn- and anti-oximes with sodium hydroxide

Article abstract of DOI:10.1007/s11176-005-0345-4

Treatment of syn-oximes of 5-substituted 2-(3-chloropropanoylamino)benzophenones with equimolar amount of sodium hydroxide results in formation of syn-oximes of 5-substituted 2-propenoylamino-benzophenones. The corresponding anti isomers under the same co

Full text of DOI:10.1007/s11176-005-0345-4

Russian Journal of General Chemistry, Vol. 75, No. 6, 2005, pp. 915 922. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005,
pp. 969 977.
Original Russian Text Copyright
2005 by Andronati, Simonov, Pavlovskii, Kulikov, Gdanec, Mazepa.
Reaction of 5-Substituted
2-(3-Chloropropanoylamino)benzophenone syn- and anti-Oximes
with Sodium Hydroxide
S. A. Andronati*, Yu. A. Simonov**, V. I. Pavlovskii**,
O. V. Kulikov**, M. Gdanec***, and A. V. Mazepa***
* Institute of Applied Physics, Academy of Sciences of Moldova, Kishinev, Moldova
** Bogatskii Physicochemical Institute, National Academy of Sciences of Ukraine, Odessa, Ukraine
*** Mickiewicz University, Poznan, Poland
Received January 27, 2004
Abstract Treatment of syn-oximes of 5-substituted 2-(3-chloropropanoylamino)benzophenones with
equimolar amount of sodium hydroxide results in formation of syn-oximes of 5-substituted 2-propenoylamino-
benzophenones. The corresponding anti isomers under the same conditions give a mixture of anti-oximes of
5-substituted 2-(propenoylamino)benzophenones and 18-membered 11,22-disubstituted 7,8,18,19-tetrahydro-
dibenzo[d,m][1,10,2,6,11,15]dioxatetraazacyclooctadecine-6,17(5H,16H)-diones.
The chemistry of oxaza macroheterocycles has at-
tracted a wide researchers’ attention [1 8]. Previously
we reported the synthesis and structure of the syn and
anti isomers of 2-(3-chloropropanoylamino)-5-me-
thylbenzophenone (3-chloropropanoyl)oximines, pos-
sible building blocks for 18-membered dibenzodioxa-
tetraaza macrocycles [9]. Proceeding with this re-
search, we synthesized a series of syn and anti
isomers of 3-(chloropropanoyl)oximines of 5-substi-
tuted 2-(3-chloropropanoylamino)benzophenones I V
whose aminolysis gave the corresponding syn and
anti-oximes of 5-substituted 2-(3-chloropropanoyl-
amino)benzophenones VI X. Syn-oximes VI and VII
give syn-oximes XI and XII in almost quantitative
yields, whereas anti-oximes VIII X under the same
conditions form a mixture of competitive , -
dehydrohalogenation and intermolecular O-alkylation
bered 11,22-disubstituted 7,8,18,19-tetrahydrodiben-
zo[d,m][1,10,2,6,11,15]dioxatetraazacyclooctadecine-
6,17(5H,16H)-diones XVI XVIII, respectively (see
Scheme 1).
The yields of compounds XIII XV increase when
stronger bases are used (MeONa, t-BuOK, NaH),
whereas the yields of compounds XVI XVIII much
decrease. Macrocycles XVI XVIII can be synthesized
in an alternative way, via cyclization of compounds
XIII XV under the action of NaOH.
To confirm the structure of compound XII, we
proposed an independent synthesis involving reaction
of 2-amino-5-bromobenzophenone (XIX) with 3-chlo-
ropropanoyl chloride to obtain 5-bromo-2-(3-chloro-
propanoylamino)benzophenone (XX) in 72% yield.
The latter was dehydrochlorinated with NaOH to form
reactions, specifically 5-substituted 2-propenoylamino- 5-bromo-2-(propenoylamino)benzophenone (XXI) that
benzophenone anti-oximes XIII XV and 18-mem-
was converted into syn-oxime XII (Scheme 2).
Scheme 1.
Cl
Cl
O
O
O
CH2
OH
NH
NH
NH
NH3 (aq.)
NaOH
Cl
O
OH
R1
N
R1
N
R1
N
R2
R2
XI, XII
59 93%
R2
O
I, II
VI, VII
96 98%
1070-3632/05/7506-0915 2005 Pleiades Publishing, Inc.

916
ANDRONATI et al.
O
CH2
OH
NH
Cl
O
R1
N
Cl
O
O
R2
43 49%
38 46%
NH
XIII XV
NH
NH3 (aq.)
NaOH
b
a
15 25%
R1
N
NaOH
R1
N
Cl
OH
R2
VIII X
R2
O
O
O
N
R2
III-V
R1
NH
94 97%
R1
N
O
HN
R2
O
XVI XVIII
R1 = Me, R2 = Ph (I, III, VI, VIII, XI, XIII, XVI); R1 = Br, R2 = Ph (II, IV, VII, IX, XII, XIV, XVII); R1 = Br, R2 =
o-ClC6H4 (V, X, XV, XVIII).
1
1
The synthesized compounds all (Table 1) were
characterized by elemental analysis, IR and UV spec-
(3545 cm ), amide N H bond (3395 3400 cm ),
1
amide carbonyl group (1680 1685 cm ), and azo-
troscopy, and mass spectrometry (suggested fragmenta- methine bond (1585 1590 cm ); the respective bands
1
tion patterns were discussed).
of anti isomers VIII X are at 3545 3555, 3245 3270,
1675 1680, and 1595 1605 cm .
1
The IR spectra of syn isomers I and II contain
stretching absorption bands of the NH bond of the free
The IR spectra of syn isomers XI and XII contain
1
1
(3390 3395 cm ) and associated (3330 3355 cm )
stretching absorption bands of the hydroxyl group
1
amido group, ester (1745 1760 cm ) and amide
1
(3545 3550 cm ), amide N H bond (3395 3405,
1
(1685 cm ) carbonyls, and azomethine bond (1575
1
3275 3285 cm ), amide carbonyl group (1680
1
1585 cm ). The respective bands in the spectra of
1
1
1685 cm ), and azomethine bond (1605 cm ); the
anti isomers III V are at 3265 3270, 3225 3235,
respective bands of anti isomers XIII XV are at 3545,
1
1755 1765, 1680 1685, and 1580 1600 cm .
1
3245 3255, 1675 1685, and 1600 1605 cm . Rely-
The IR spectra of syn isomers VI and VII contain
stretching absorption bands of the hydroxy group
ing on data in [9, 10], we can suggest that anti iso-
mers XIII XV have an intramolecular hydrogen bond
Scheme 2.
Cl
O
O
Cl
NH2
O
NH
Cl
72%
O
Br
Br
Ph
Ph
XX
XIX
O
(NH2OH)2 H2SO4,
NaOH
NH
NaOH
36%
XII
85%
O
Br
Ph
XXI
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005

REACTION OF 5-SUBSTITUTED 2-(3-CHLOROPROPANOYLAMINO)BENZOPHENONE
917
Table 1. Yields, melting points, and elemental analyses of the syn and anti isomers of 5-substituted 2-(3-chloropropanoyl-
amino)benzophenone 3-(chloropropanoyl)oximines I V, 5-substituted 2-(3-chloropropanoylamino)benzophenone syn- and
anti-oximes VI X, 5-substituted 2-(propenoylamino)benzophenone syn- and anti-oximes XI XV, and 11,22-disubstituted
7,8,18,19-tetrahydrodibenzo[d,m][1,10,2,6,11,15]dioxatetraazacyclooctadecine-6,17(5H,16H)-diones XVI XVIII
Found, %
H
Calculated, %
M+,
m/z
Comp. no.
Yield, %
mp,
C
Formula
a
C
N
C
H
N
I
II
III
IV
V
VI
VII
VIII
IX
60
36
30
81
62
98
96
97
96
94
59
93
45
43
49
113 115 58.99
126 128 48.31
4.97
3.69
4.91
3.67
3.16
5.46
3.67
5.38
3.68
3.19
5.79
3.78
5.76
3.84
3.21
5.71
3.83
3.22
6.87 C20H20Cl2N2O3
6.00 C19H17BrCl2N2O3
6.89 C20H20Cl2N2O3
5.90 C19H17BrCl2N2O3
5.58 C19H16BrCl3N2O3
8.89 C17H17ClN2O2
7.31 C16H14BrClN2O2
8.87 C17H17ClN2O2
7.37 C16H14BrClN2O2
6.81 C16H13BrCl2N2O2
9.97 C17H16N2O2
8.09 C16H13BrN2O2
9.96 C17H16N2O2
8.14 C16H13BrN2O2
7.40 C16H12BrClN2O2
9.94 C34H32N4O4
58.98 4.95
48.33 3.63
58.98 4.95
48.33 3.63
45.05 3.18
64.46 5.41
50.35 3.70
64.46 5.41
50.35 3.70
46.18 3.15
72.84 5.75
55.67 3.80
72.84 5.75
55.67 3.80
50.62 3.19
72.84 5.75
55.67 3.80
6.88
5.93
6.88
5.93
5.53
8.84
7.34
8.84
7.34
6.73
9.99
8.12
9.99
8.12
7.38
9.99
8.12
7.38
406
470
406
470
504
316
380
316
380
414
280
344
280
344
378
560
688
756
82 87
95 97
58.94
48.35
115 117 45.08
146 148 64.50
133 136 50.39
96 98
64.40
102 104 50.30
183 185 46.20
157 160 72.80
143 146 55.64
164 165 72.80
173 175 55.63
210 215 50.60
X
XI
XII
XIII
XIV
XV
XVI
XVII
XVIII
39 (a), 23 (b) 348 350 72.83
38 (a), 15 (b) 330 335 55.61
46 (a), 25 (b) 327 330 50.64
8.15 C32H26Br2N4O4
7.39 C32H24Br2Cl2N4O4 50.62 3.19
a
The molecular masses determined by mass spectrometry coincide with calculated.
between the amide hydrogen and azomethine nitrogen.
This is evidenced by the long-wave shift of the NH
band with respect to the band of the free NH group in
syn isomers XI and XII. Further evidence is provided
by the fact that the integral intensity of the absorption
18-membered macrocycles XVI XVIII lack bands in
this region.
Earlier we showed that the cyclization of 2-chloro-
acetamidobenzophenone syn-oximes in the presence
of NaOH provides 16-membered dibenzodioxatetraaza
macrocycles [7], and, therewith, the syn configuration
of the C=N O fragment is preserved [8]. With this in
mind, we can admit that 18-membered macrocycles
XVI XVIII, too, preserve the anti configuration of
the starting monopropanoyl derivatives VIII X.
1
bands of the amide N H bond (3250 cm for com-
pound XIV) remains invariable as the solution con-
2
centration is changed from 2.9 10 to 7.25 10 3 M.
With syn isomer XII, the band at 3285 cm 1 is weaker
1
than the free NH band at 3395 cm . The latter ob-
servable suggests suggests that syn isomers XI and
XII contain an intramolecular hydrogen bond that is
cleaved on dilution. The IR spectra of macrocycles
XVI XVIII show stretching absorption bands of the
The mass spectra of the syn (XI, XII) and anti
(XIII XV) isomers are identical to each other. They
contain molecular ion peaks whose intensity depends
on the nature of the 5-substituent. Bromo derivatives
have considerably less stable molecular ions than
methyl derivatives XI and XIII (63%). The main
fragmentation pathway involves simultaneous elimina-
tion of the hydroxy and propenoyl groups to form ions
of the indazole structure. The presence of 5-Br favors
preferential localization of the positive charge on the
propenoyl fragment, as a result of which the base ions
(100%) in the mass spectra of compounds XII and
XIV are at m/z 55. By contrast, methyl (compounds
1
amide NH bond (3255 3275 cm ), amide carbonyl
1
group (1655 1680 cm ), and azomethine bond
1
(1580 1595 cm ). The IR spectra of macrocycles
XVI XVIII suggest a lactam structure of the com-
pounds.
As seen from the above data, syn isomers I, II, VI,
VII, XI, and XII characteristically contain a band at
1
3390 3400 cm , corresponding to the NH bond of a
free amido group, whereas the IR spectra of anti
isomers III V, VIII X, and XIII XV, as well as
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005

918
Table 2. Bond lengths (d) and bond angles ( ) in compound XII and benzene solvate of compound XIV
d, , deg
ANDRONATI et al.
Bond
Angle
XII
solvate XIV
XII
solvate XIV
C1 C6
1.390(4)
1.401(4)
1.490(4)
1.385(4)
1.404(4)
1.345(4)
1.226(3)
1.479(4)
1.299(4)
1.377(4)
1.384(4)
1.374(4)
1.889(3)
1.284(3)
1.478(4)
1.401(3)
1.386(4)
1.394(4)
1.363(5)
1.377(5)
1.373(5)
1.375(4)
1.401(3)
1.424(3)
1.491(3)
1.400(3)
1.405(2)
1.354(2)
1.231(2)
1.486(3)
1.316(3)
1.385(3)
1.382(3)
1.384(3)
1.900(2)
1.287(2)
1.496(2)
1.391(2)
1.392(3)
1.393(3)
1.391(3)
1.392(4)
1.373(4)
1.398(3)
1.358(5)
1.373(5)
1.369(5)
1.369(5)
C6C1C7
118.8(3)
118.2(2)
122.9(2)
119.8(3)
121.1(3)
119.0(2)
128.1(3)
122.4(3)
123.9(3)
113.6(3)
122.9(3)
121.2(3)
118.6(3)
121.3(3)
119.5(2)
119.2(2)
120.3(3)
114.6(2)
119.1(2)
119.1(2)
113.1(2)
118.1(3)
121.4(3)
120.5(3)
120.4(3)
121.0(3)
119.4(3)
120.0(3)
121.1(3)
118.07(17)
117.75(16)
124.17(16)
119.89(17)
120.96(17)
119.12(16)
129.13(17)
123.55(18)
123.43(17)
113.02(17)
122.6(2)
120.67(18)
119.42(18)
121.25(18)
119.42(15)
119.32(14)
120.69(18)
122.78(16)
117.30(16)
119.92(15)
114.40(15)
119.63(18)
120.85(18)
119.50(17)
120.3(2)
C1 C2
C2C1C7
C1 C7
C3C2C1
C2 C3
C3C2N2
C2 N2
C1C2N2
N2 C21
C21 O21
C21 C22
C22 C23
C3 C4
C21N2C2
O21C21N2
O21C21C22
N2C21C22
C23C22C21
C4C3C2
C4 C5
C5 C6
C3C4C5
C5 Br
C6C5C4
C7 N7
C6C5Br
C7 C8
C4C5Br
N7 O71
C8 C13
C8 C9
C5C6C1
N7C7C8
N7C7C1
C9 C10
C10 C11
C11 C12
C12 C13
C2A C3A
C2A C1A
C3A C1A
C1A C3A
C8C7C1
C7N7O71
C13C8C9
C13C8C7
C9C8C7
C10C9C8
C9C10C11
C12C11C10
C11C12C13
C12C13C8
a
a
119.5(2)
120.5(2)
120.2(2)
119.8(2)
a
C
C
2AC3AC1A
a
3A1C1AC2A
119.3(3)
120.9(3)
a
1A
3A
The C
and C
are related as 1
x, 2
y, z.
XI and XIII) effectively stabilizes the indazole frag-
ments whose ions are the most abundant.
5, and indazole 6 ions, of which the latter being
the most abundant.
The molecular ion peaks in the mass spectra of
macrocyclic compounds XVI XVIII decrease in in-
tensity in going from 2,13-dimethyl to 2,13-dibromo
derivatives. The main fragmentation pathway of com-
pounds XVI XVIII is presented in Scheme 3.
We performed a full X-ray analysis of compounds
XII and XIV and obtained a model of structure XVIII.
Selected interatomic distances and bond angles in
structures XII and XIV are listed in Table 2.
The X-ray diffraction analysis gave evidence to
show that compounds XII and XIV the syn and anti
isomers, respectively. Figure 1 presents the molecular
structure of compound XII. The molecular conforma-
tion is stabilized by the intramolecular hydrogen bond
N2 H O71 with the donor acceptor distance of
2.689(4) ; the angle at the H atom is 148(2) , and
the HO71 distance is 1.98(3) . Therewith, a seven-
The primary fragmentation act involves opening of
the macrocycle and elimination of the C3H4NO2 frag-
ment, which is probably associated with cleavage of
the amide and azomethine bond to form the molecular
ion of divenzooxatriaza macrocycle 1. Further frag-
mentation involves formation of benzoxadiazonine
2, benzodiazocine 3, quinazolone 4, benzazete
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005

REACTION OF 5-SUBSTITUTED 2-(3-CHLOROPROPANOYLAMINO)BENZOPHENONE
919
Scheme 3.
+
+
R2
O
R2
O
O
N
O
N
R1
NH
R1
NH
R1
R1
HN
N
O
R2
R2
N
O
H
1
+
H
N
H
O
O
CH
+
N
OH
O
R1
CH2
R1
N
R2
N
R2
2
3
.
R1
C2H4
+
H
H
O
+
N
+
N
N
N
O
N
R1
N
R1
R2
N
R1
R2
R2
R2
7
4
5
6
R1 = Me, Br; R2 = Ph, o-ClC6H4.
membered ring is formed in the molecule. The di-
hedral angle between the fuzed aromatic nucleus and
Br and Ph is 66.2 , which is characteristic of
1,4-benzodiazepines [11, 12]. In the substituent at C2,
there is -electron delocalization, and the N2 C2,
C21 O21, and C22 C23 distances are 1.345, 1.226, and
C23
C22
C21
1.299
(Table 2). Molecules in the crystal form
N2
chains due to the intramolecular hydrogen bond
O71 H O21 [2.629(3) ]. The chains are held to-
gether by van der Waals contacts.
O21
C2
O71
N7
C3
Compound XIV crystallizes as a 2:1 benzene
solvate. The benzene molecule has an intrinsic crysta-
llographic symmetry Ci. Figure 2 presents a fragment
of the structure. The X-ray diffraction data give
evidence to show that the anti isomers have an intra-
molecular hydrogen bond. The presence of the amido
group of E configuration makes possible a strong
intramolecular hydrogen bond N2 H N7 of
2.638(5) with the H N7 distance of 2.00(5) and
the NHN angle of 143(1) . The molecule contains a
pseudo ring that ensures coplanarity of the substi-
tuents and the benzene ring. The molecular conforma-
tion is further stabilized by the C3 H O21 contact
C1
C7
C8
C5
C6
C13
C9
Br
C10
C12
C11
Fig. 1. Molecular structure of 5-bromo-2-(propenoyl-
amino)benzophenone sym-oxime (XII).
with the H O21 distance of 2.26
and the angle at
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005

920
ANDRONATI et al.
C21 N2 1.354(2), C21 C22 1.486(2) ; the length of
the terminal double bond is 1.316(2) ]. The inter-
C11
molecular hydrogen bond O71 H O21 [2.663(5)
]
combines molecules into a chain with a double screw
axis ( x + 2, y + 1/2, z 1/2). The hydrogen bond
has the H O21 distance of 1.83(5) and the angle at
the H atom of 179(1) . The chains are held together
C1A
C2A
C12
C3A
C10
C9
C13
by
interactions. The distance between the anti-
C8
O71
N7
parallel phenyl planes is 3.59 . The interacting
chains form cavities occupied by solvate benzene
molecules. Previously in 1,4-benzodiazepines and
C7
C1
Br
C6
their macrocyclic analogs we observed
or C H
C5
C4
interactions between the base molecules and solvate
aromatic molecules [8, 11], like in [13, 14]. In the
present case we found no such interactions. The
contacts between the base and solvate molecules are
van der Walls in nature. The latter feature renders the
crystals unstable at room temperature.
C2
N2
C3
C22
C21
O21
C23
Figure 3 presents the molecular structure of com-
pound XVIII. The anti configuration of the C=N O
fragment in the macroring is confirmed by the X-ray
diffraction data. This configuration is fixed by two
intramolecular N H N hydrogen bonds. It should
also be noted that the amido group has an E configura-
tion, which maikes the NH hydrogens to point to the
ring cavity, as described in [8].
Fig. 2. Structure of the benzene solvate of 5-bromo-2-
(propenoylamino)benzophenone anti-oxime (XIV).
the H atom of 120 . The dihedral angle between the
fuzed aromatic ring and Br and Ph is 69.9 , like in
compound XII. The interatomic distances are listed
in Table 2. Note the -electron delocalization in the
C2 N2 C21=O21 C22 C23 fragment [C2 N2 1.405(2),
C11
C12
Br1
O7
C7
C10
C5
C13
N6
C8
C4
C9
C3
C32
C31
C36
N2
C33
C34
Cl1
O1
C35
Fig. 3. Molecular structure of compound XVIII.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005

REACTION OF 5-SUBSTITUTED 2-(3-CHLOROPROPANOYLAMINO)BENZOPHENONE
921
EXPERIMENTAL
5-Methyl-2-(3-chloropropanoylamino)benzo-
phenone anti-oxime (VIII). Aqueous ammonia, 5 ml,
was added to a solution of 1.34 g of compound III in
15 ml of freshly distilled dioxane. The suspension that
formed was stirred for 30 min and then poured into
water. A colorless precipitate formed and was washed
with water, dried in air, and recrystallized from a
benzene heptane mixture. Yield 1.01 g (97%),
mp 96 98 C.
The IR spectra were measured on a Specord IR-75
spectrophotometer in CHCl3. The UV spectra were
measured on an SF-56 spectrophotometer in EtOH.
The mass spectra were registered on an MX-1321
instrument with direct sample admission into the ion
source, ionizing energy 70 eV, batch temperature
150 C. The X-ray analysis of compound XII was
performed on a KUMA-4CCD (MoK radiation) from
a shapeless colorless sample with the linear dimen-
sions 0.5 0.5 0.4 mm at 130 K. The sample
strongly fluoresced under X-ray irradiation. Mono-
clinic crystal, space group P21/c1; a 12.615 (3), b
Compounds VI, VII, IX, and X were prepared in
a similar way (Table 1).
5-Bromo-2-(propenoylamino)benzophenone
syn-oxime (XII). A solution of 0.06 g of NaOH in
2 ml of water was added to a solution of 0.568 g of
compound VII in 10 ml of freshly distilled dioxane.
The suspension was stirred for 24 h, the colorless
precipitate that formed was filtered off, washed with
water, and recrystallized from benzene. Yield 0.477 g
(93%), mp 143 146 C.
10.015(2), c 13.973(2)
;
100.40(3) , V 1736.3(7)
3
3, Z 4,
1.470 g cm . Intensities with 516 fra-
mes were rceaglcistered; 0, 90, 180, and 270 ; scann-
ing, step 0.75 ; frame measurement time 8 s. All
intensities were corrected for absorption. A total of
6902 reflections were measured, 2556 of which were
used for solving and refining the structure. The struc-
ture was solved and refined by the SHELX-97 prog-
ram [15] anisotropically for non-hydrogen atoms and
isotropically for hydrogen atoms. The latter were
refined in terms of the solid body model. Final R
factor 0.0352, wR2 0.0894 on 2556 reflections with
Compound XI was prepared in a similar way.
11,22-Dibromo-7,8,18,19-tetrahydrodibenzo-
[d,m][1,10,2,6,11,15]dioxatetraazacyclooctadecine-
6,17(5H,16H)-dione (XVII) and 5-bromo-2-
(propenoylamino)benzophenone anti-oxime (XIV).
a. A solution of 2 g of NaOH in 10 ml of water was
added to a solution of 6.627 g of compound IX in
40 ml of freshly distilled dioxane. The suspension was
stirred for 24 h, the colorless precipitate that formed
was filtered off, washed with water, dried in air, and
washed hot dioxane to obtain 2.23 g (38%) of com-
pound XVII. The mother solution was poured into
water, the precipitate that formed was filtered off,
washed with water, dried in air, and recrystallized
from benzene to obtain 2.58 g (43%) of compound
XIV. Compounds XIII, XV, XVI, and XVIII were
prepared in a similar way (Table 1).
I
2 (I). The X-ray analysis of compound XIV was
performed using a colorless single crystal of prismatic
habitus with the linear dimensions 0.6.0.25.0.25 mm.
The crystal is a benzene solvate and decomposes in
air. For conservation the solvate was cooled to 140 K.
The crystal data were collected and treated as des-
cribed for compound XII. Monoclinic crystal, space
group P21/c1;
13.973(2)
a
12.615 (3),
b
10.015(2),
c
;
100.40(3) , V 1736.3(7) 3, Z 4,
calc
3
1.470 g cm . The experimental data were corrected
for absorption on the basis of -scanning data. A total
of 10341 reflections were measured, 4403 of which
with I
refining. Final R factor 0.0344, wR2 0.0841 on reflec-
tions with I 2 (I). The structure was solved and
2 (I) were used in structure solving and
b. Sodium hydride, 0.418 g, was added to a solu-
tion of 6.627 g of compound IX in 40 ml of dry di-
oxane. The suspension was stirred for 24 h, the color-
less precipitate that formed was filtered off, washed
with water, dried in air, and washed hot dioxane to
obtain 0.84 g (14%) of compound XVII. The mother
solution was poured into water, the precipitate that
formed was filtered off, washed with water, dried in
air, and recrystallized from benzene to obtain 4.02 g
(67%) of compound XIV. In a similar way, com-
pounds XIV and XVII were synthesized with MeONa
and t-BuOK as bases.
refined using the SHELX-97 program package aniso-
tropically for non-hydrogen atoms. The hydrogen
atoms were refined in terms of the solid body model.
Compound XVIII crystallizes as dimers with overlap-
ping diffraction patters. We could determine unit cell
parameters for an individual block. Monoclinic crystal,
a 12.822(3), b 12.236(2), c 19.860
;
100.09(3) ,
3
space group Cc, Z 4, 1.644 g cm . The structure
calc
model was obtained by direct methods using the
SHELX-97 program package and refined isotropically
to R1 0.136.
5-Bromo-2-(3-chloropropanoylamino)benzo-
phenone (XX) was prepared from compound XIX
according to [16].
Compounds I V were synthesized as described
in [9].
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005

922
ANDRONATI et al.
5-Bromo-2-(propenoylamino)benzophenone
and Tkachev, A.V., Mendeleev Commun., 2000, no. 6,
p. 209.
(XXI). A solution of 0.2 g of NaOH in 2 ml of water
was added to a solution of 0.3 g of compound XX in
10 ml of freshly distilled dioxane. The suspension was
stirred for 2 h and poured into water, the yellowish
precipitate was filtered off, dried in air, subjected to
chromatography on silica gel (eluent benzene), and
recrystallized from benzene hexane. Yield 0.097 g
5. Kulikov, O.V., Pavlovskii, V.I., Mazepa, A.V., and
Andronati, S.A., Khim. Geterotsikl. Soedin., 2003,
no. 4, p. 566.
6. Pavlovsky, V.I., Kulikov, O.V., Rusakova, N.V., and
Korovin, Yu.V., Abstracts of Papers, XXVIII Int.
Symp. on Macrocyclic Chemistry, Gdansk, 2003,
p. 197.
1
(36%), mp 86 88 C. IR spectrum (CHCl3), , cm :
3300 (NH), 1675 (NH C=O), 1630 (C=O), 1595
(C=N). UV spectrum (EtOH), max, nm (log ): 249
(4.42), 324 (3.64). Mass spectrum, m/z: 329 [M+].
7. Kulikov, O.V., Andronati, S.A., Pavlovskii, V.I.,
Mazepa, A.V., and Kabanova, T.A., Vestn. Odessk.
Nats. Univ., Ser. Khim., 2000, vol. 5, no. 2, p. 68.
8. Simonov, Yu.A., Suvinska, K., Pavlovskii, V.I., Ku-
likov, O.V., Ganin, E.V., and Andronati, S.A., Dopov.
Nat. Akad. Navuk Ukraini, 2001, no. 6, p. 140.
5-Bromo-2-(propenoylamino)benzophenone
syn-oxime (XII) from compound XXI. A solution of
0.08 g of NaOH in 2 ml of water and 0.149 g of
hydroxylamine sulfate was added to a solution of
0.3 g of compound XXI in 10 ml of ethanol. The
suspension was stirred for 2 h and poured into water,
the colorless precipitate was filtered off, dried in air,
and recrystallized from benzene hexane. Yield
0.267 g (85%).
9. Andronati, S.A., Pavlovskii, V.I., Kulikov, O.V.,
Simonov, Yu.A., and Gdanets, M., Zh. Strukt. Khim.,
2001, vol. 42, no. 5, p. 1035.
10. Pavlovskii, V.I., Kulikov, O.V., Karaseva, T.L., Ka-
banova, T.A., Mazepa, A.V., and Andronati, S.A.,
Ukr. Khim. Zh., 1998, vol. 64, no. 12, p. 123.
11. Andronati, S.A., Andronati, K.S., Neshchadin, D.P.,
Simonov, Yu.A., Kravtsov, V.H., and Lipkovskii, Ya.,
Dopov. Nat. Akad. Navuk Ukraini, 1999, no. 6, p. 149.
Synthesis of macrocycle XVII from compound
XIV. A solution of 0.005 g of NaOH in 2 ml of water
was added to a solution of 0.04 g of compound XIV
in 5 ml of THF. The suspension was stirred for 24 h,
the colorless precipitate that formed was filtered off,
washed with water, dried in air, and washed with hot
THF. Yield 0.006 g (15%).
12. Dvorkin, A.A., Simonov, Yu.A., Bogatskii, A.V.,
Korotenko, T.I., and Andronati, S.A., Dokl. Akad.
Nauk USSR, 1982, no. 4, p. 28.
13. Castellano, R.K., Diederich, F., and Meyer, E.A.,
Angew. Chem., Int. Ed. Engl., 2003, vol. 42, no. 11,
p. 1210.
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005