The synthesis of new 1,3-oxazolidines and 1,3-oxazinanes containing (η6-arene)tricarbonylchromium group based on condensation between aldehydes and amino alcohols

Article abstract of DOI:10.1007/s11172-018-2153-0

The condensation reactions of β- and γ-amino alcohols containing phenyl or (η⁶-arene) tricarbonylchromium substituent with formaldehyde, acetaldehyde, benzaldehyde, and (η⁶-benzaldehyde)tricarbonylchromium were studied. The resulting 1,3-oxazolidine and 1,3-oxazinane products were isolated in a pure form and identified by different physicochemical methods. The effect of (η⁶-arene)tricarbonylchromium moiety on the reaction process was demonstrated.

Full text of DOI:10.1007/s11172-018-2153-0

Russian Chemical Bulletin, International Edition, Vol. 67, No. 5, pp. 884—892, May, 2018
884
The synthesis of new 1,3-oxazolidines and 1,3-oxazinanes
containing (η6-arene)tricarbonylchromium group
based on condensation between aldehydes and amino alcohols
A. N. Artemov,a E. V. Sazonova,a N. A. Krylova,a E. A. Zvereva,a N. A. Pechen,a G. K. Fukin,b
A. V. Cherkasov,b V. I. Faerman,a and N. Yu. Grishinaa
aN. I. Lobachevsky State University of Nizhny Novgorod,
Build. 5, 23 prosp. Gagarina, 603950 Nizhny Novgorod, Russian Federation.
Fax: +7 (831) 465 8162. E-mail: zarovkinan@mail.ru
bG. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences,
49 ul. Tropinina, 603137 Nizhny Novgorod, Russian Federation.
Fax: +7 (831) 462 7497. E-mail: gera@iomc.ras.ru
The condensation reactions of β- and γ-amino alcohols containing phenyl or (η6-arene)
tricarbonylchromium substituent with formaldehyde, acetaldehyde, benzaldehyde, and
(η6-benzaldehyde)tricarbonylchromium were studied. The resulting 1,3-oxazolidine and
1,3-oxazinane products were isolated in a pure form and identified by different physicochemi-
cal methods. The effect of (η6-arene)tricarbonylchromium moiety on the reaction process was
demonstrated.
Key words: (η6-arene)tricarbonylchromium complexes, heterocyclic compounds, 1,3-ox-
azolidines, 1,3-oxazinanes, amino alcohols, aldehydes, condensation.
Scheme 1
In recent times, a research area related to obtaining of
complexes of transition metals with natural and biologic-
ally active compounds and other advanced products of fine
organic synthesis is extensively developed. Opportunities
for their practical applications as unique catalysts, organic
semiconductors, linker compounds, and also materials for
nonlinear optics are being explored.1,2 To continue stud-
ies on the synthesis of heterocyclic compounds containing
tricarbonylmetal groups,3—8 we report in the present work on
new 1,3-oxazolidines and 1,3-oxazinanes with (η6-arene)-
tricarbonylchromium moieties.
Results and Discussion
The condensation of carbonyl compounds with amino
alcohols is the most common and widely used method to
assemble heterocycles containing β-positioned nitrogen
and oxygen atoms.9,10 Thus, we aimed to obtain the above
mentioned heterocycles by the condensation of aldehydes
1a—d with β- (2a—d) or γ-amino alcohols (3a,b), wherein
one or both reactants contained (arene)tricarbonylchro-
mium moiety (Scheme 1). Reactions of β-amino alcohols
led to 1,3-oxazolidines 4a—i, while in case of γ-amino
alcohols 1,3-oxazinanes 5a—c were formed.
The selected aldehydes were formaldehyde (1a) (as
paraformaldehyde), acetaldehyde (1b), benzaldehyde (1c),
and (η6-benzaldehyde)tricarbonylchromium (1d).
The following compounds were used as amino alcohols:
1: R = H (a); Me (b); Ph (c); (OC)3CrPh (d)
2: R´ = Ph, R´´ = H (a), Me (b); R´ = (OC)3CrPh, R´´ = H (c), Me (d)
3: R´ = Ph (a), (OC)3CrPh (b)
Compound
R
Н
Me
Ph
H
Me
Н
Me
Н
R´
Ph
Ph
Ph
Ph
R´´
H
H
4a
4b
4c
4d
4e
4f
4g
4h
4i
H
Me
Me
H
Ph
(OC)3CrPh
(OC)3CrPh
(OC)3CrPh
(OC)3CrPh
Ph
H
Me
Me
—
—
—
Me
H
5a
5b
5c
Ph
H
Ph
(OC)3CrPh
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 0884—0892, May, 2018.
1066-5285/18/6705-0884 © 2018 Springer Science+Business Media, Inc.

1,3-Oxazacycloalkanes with (arene)Cr(CO)3 group
Russ. Chem. Bull., Int. Ed., Vol. 67, No. 5, May, 2018
885
2-(N-phenylamino)ethanol (2a), 1-(N-phenylamino)-
propan-2-ol (2b), their tricarbonylchromium complexes
(compounds 2c and 2d, respectively), 3-(N-phenylamino)-
propan-1-ol (3a), and its tricarbonylchromium complex 3b.
Tricarbonylchromium complexes 2c, 2d, and 3b were
synthesized according to the Rausch11 method via a ther-
mal reaction of the corresponding arene with (triammine)
(tricarbonyl)chromium (Scheme 2).
Similarly to amino alcohol 2a, 1-(N-phenylamino)-
propan-2-ol (2b) did not react with (η6-benzaldehyde)-
tricarbonylchromium (1d), but underwent condensation
with aldehydes not containing the tricarbonylchromium
moiety. Its reaction with formaldehyde (1a) provided in-
dividual product 4d,13 while a nonseparable mixture (1 : 1)
of the two diastereomers (cis- and trans-4e) was formed
in the case of acetaldehyde (1b).
Scheme 2
The next stage of this work was to investigate the con-
densation reactions of chromium-containing amino alco-
hols 2c,d with aldehydes 1a—d (see Scheme 1). All
1,3-oxazolidines obtained in these reactions were isolated
pure by column chromatography with subsequent recrys-
tallization and identified by HPLC, UV-Vis, IR, and
1H-NMR spectroscopy, and mass spectrometry. The reac-
tion conditions and some characteristics of the products
are shown in Table 2.
R = CH2OH (2a,c); CH(Me)OH (2b,d); (CH2)2OH (3a,b)
Reagents and conditions: (NH3)3Cr(CO)3, dioxane, 120 °С.
Complexes 2c, 2d, and 3b were obtained for the first
time as yellow-brown oils oxidizable in air. Their HPLC
chromatograms contained only one peak (Table 1). In the
IR spectra of compounds 2c, 2d, and 3b, absorption bands
characteristic of amino alcohols and also intense bands of
valence vibrations of CO bonds in tricarbonylchromium
moieties within 1853—1952 cm–1 range were present (see
Table 1). Their mass spectra contained the expected mo-
lecular (see Table 1) and also fragment ions (see Exper-
imental).
The nature of substituents in reacting molecules has
a great influence on the yield of products and the outcome
of the condensation.12 Thus, the reactions of 2-(N-phen-
ylamino)ethanol (2a) with formaldehyde (1a), acetalde-
hyde (1b), and benzaldehyde (1c) successfully proceed to
give the corresponding disubstituted 1,3-oxazolidines13,14
(compounds 4a—c, see Scheme 1), while the reaction of
amino alcohol 2a with (η6-benzaldehyde)tricarbonyl-
chromium (1d) in toluene at 120 °C did not provide the
expected heterocyclic product. Most likely, the introduc-
tion of bulky Cr(CO)3 group into the benzaldehyde mol-
ecule was crucial to increase the steric hindrance affecting
the possibility of condensation reaction.
The reaction of η6-[(2-hydroxyethylamino)benzene]
tricarbonylchromium (2c) with an excess of paraform-
aldehyde (1a) in toluene after 4 h at 120 °C resulted in two
products, which were separated by column chromatography.
The first one (the yield of 35%) was the expected 1,3-ox-
azolidine 4f. The second product had a mass number of
315 for the molecular ion according to the mass spectrum.
Its 1H NMR spectrum contained signals from four meth-
ylene groups of the heterocyclic ring and a phenyltricar-
bonylchromium group. The acquired data allowed one to
identify this substance as η6-[(hexahydro-1,3,5-dioxaze-
pin-5-yl)benzene]tricarbonylchromium (6) (Scheme 3).
Structure 6 was confirmed by the X-ray diffraction of
single crystal (Fig. 1 and Table 3). Molecule 6 is based on
a seven-membered heteroatomic cycle, which includes one
nitrogen and two oxygen atoms. The lengths of N(1)—C (10)
C(6)
O(4)
C(11)
C(5)
C(4)
C(7)
C(10)
O(5)
C(12)
O(1)
C(2)
C(8)
C(1)
Table 1. Some characteristics of arenetricarbonylchromium-
containing amino alcohols 2c, 2d, and 3b
Cr(1)
C(9)
N(1)
C(13)
Amino HPLC,
alcohol τ/min
Yield
(%)
IR,
MS
EI, 70 eV,
m/z (Irel (%))
C(3)
O(3)
ν(С≡О)/cm–1
(KBr)
O(2)
2c
2d
3b
4.9
5.1
5.0
54
65
33
1949, 1853
1952, 1853
1947, 1861
273 [М]+ (65)
287 [М]+ (20)
287 [M]+ (2)1
Fig. 1. Molecular structure of η6-[(hexahydro-1,3,5-dioxazepin-
5-yl)benzene]tricarbonylchromium (6). Thermal ellipsoids are
given at 30% probability. Hydrogen atoms are omitted.

886
Russ. Chem. Bull., Int. Ed., Vol. 67, No. 5, May, 2018
Artemov et al.
Table 2. Reactions of aldehydes 1a—d with amino alcohols 2c, 2d, and 3a,b and some characteristics of 1,3-oxazolidines
4f—i and 1,3-oxazinanes 5a—ca
Aldehyde
Amino
alcohol
Product
(%)
τ/hb
Yieldc
M.p./°С
IR (KBr),
MS EI
ν(С≡О)/cm–1 (70 eV), m/z (Irel (%))
1a
1b
1c
1d
1a
1b
2c
2c
2c
2c
2d
2d
4f
4
6
6
6
6
6
35
31
—
—
30
18
53
61
28
—
—
22
127—128
70—71
—
1957, 1883
285 [M]+ (7)1
299 [M]+ (10)
—
4g
1948, 1882
d
—
—
—
d
—
—
1947, 1852
1938, 1855
1935, 1849
—
—
4h
cis-4i
trans-4i
5а
131—132
84—85
105—106
Oil
299 [M]+ (2)1
313 [M]+ (2)1
313 [M]+ (5) 1
163 [M]+ (64)
239 [M]+ (22)
—
1a
1с
1d
1с
1a
3а
3а
3а
3b
3b
2
4
4
4
5b
23—24
—
—
—
d
—
—
d
—
—
—
5c
1.5
114—115
1948, 1848
299 [M]+ (52)
a The reaction was carried out at 120 °С in all the cases.
b τ is reaction duration.
c Yield was calculated after isolation and purification of compounds.
d The desired products were not formed.
Scheme 3
and N(1)—C(13) bonds were 1.444(3) and 1.470(3) Å,
respectively. The hybridization of N(1) atom was close
to sp2: the C (4)—N(1)—C (10), C (4)—N(1)—C (13),
and C (10)—N (1)—C (13) angles were 120.2(2), 120.1(2),
and 118.9(2)°, respectively. The O—C distances belong to
a narrow range of values, 1.409(3)—1.426(3) Å. The
C(12)—C(13) bond length was 1.520(3) Å. The carbonyl
groups of Cr(CO)3 moiety had the eclipsed orientation
relative to the phenyl ring. The Cr—Carene and Cr—(CО)
distances remained in the intervals of 2.206(2)—2.327(2)
and 1.831(2)—1.842(2) Å, respectively (see Table 3). The
C—Cr—C angles in the tricarbonylchromium moiety are
close to 90° (87.66(9)—89.82(9)°).
The formation of byproduct 6 in that reaction may be
explained by taking into account the stepwise mechanism
of the condensation (see Scheme 3): the product of the
addition of the amino alcohol to the carbonyl group of
formaldehyde could either undergo an elimination of the
water molecule providing 1,3-oxazolidine 4f or participate
in a competitive reaction with the next molecule of form-
Table 3. Selected bond lengths (d) and angles (ω) in complex 6
Bond
d/Å
Bond
d/Å
Angle
ω/deg
N(1)—C(10)
N(1)—C(13)
C(12)—C(13)
O(5)—C(12)
O(5)—C(11)
O(4)—C(11)
O(4)—C(10)
Сr(1)—C(4)
Сr(1)—C(5)
Сr(1)—C(6)
Сr(1)—C(7)
Сr(1)—C(8)
1.444(3)
1.470(3)
1.520(3)
1.423(3)
1.409(3)
1.415(3)
1.426(3)
2.327(2)
2.245(2)
2.206(2)
2.235(2)
2.222(2)
Сr(1)—C(9)
Сr(1)—C(1)
Сr(1)—C(2)
Сr(1)—C(3)
C(4)—C(9)
C(4)—C(5)
C(5)—C(6)
C(6)—C(7)
C(7)—C(8)
C(8)—C(9)
2.257(2)
1.831(2)
1.842(2)
1.837(2)
1.423(3)
1.424(3)
1.408(3)
1.413(3)
1.405(3)
1.410(3)
C(4)—N(1)—C(10)
C(4)—N(1)—C(13)
C(10)—N(1)—C(13)
N(1)—C(10)—O(4)
C(11)—O(4)—C(10)
O(4)—C(11)—O(5)
C(11)—O(5)—C(12)
O(5)—C(12)—C(13)
N(1)—C(13)—C(12)
C(3)—Cr(1)—C(1)
C(3)—Cr(1)—C(2)
C(1)—Cr(1)—C(2)
120.2(2)
120.1(2)
118.9(2)
112.3(2)
112.3(2)
113.5(2)
114.0(2)
112.3(2)
112.3(2)
88.04(9)
89.82(9)
87.66(9)

1,3-Oxazacycloalkanes with (arene)Cr(CO)3 group
Russ. Chem. Bull., Int. Ed., Vol. 67, No. 5, May, 2018
887
aldehyde producing seven-membered product 6 via de-
hydration.
C(5)
C(7)
C(4)
C(10)
O(4)
N(1)
The reaction of compound 2c with acetaldehyde (1b)
in toluene at 120 °C after 6 h provided the expected
η6-[(2-methyl-1,3-oxazolidin-3-yl)benzene]tricarbonyl-
chromium (4g) in the yield of 31%. Its IR spectrum con-
tained intense bands corresponding to the vibrations of
CO in the tricarbonylchromium moiety. In the mass spec-
trum of complex 4g, the expected molecular ion (see Table 2)
and characteristic fragment ions were observed (see
Experimental). Its 1H NMR spectrum contained a doublet
at 1.40 ppm from the methyl substituent interacting
with the proton at the C(2)H moiety, multiplets from
protons of the heterocyclic ring at 3.34—3.45, 3.46—3.58,
3.98—4.11, 4.11—4.23 and 4.97—5.09 ppm, respectively,
and also signals from the phenyltricarbonylchromium
moiety (4.97—5.83 ppm).
Numerous attempts of carrying out the reactions of
chromium-containing amino alcohol 2c with benzalde-
hyde (1c) or its complex 1d were unsuccessful apparently
due to steric reasons. However, the reaction between
η6-{[(2-hydroxyprop-1-yl)amino]benzene}tricarbonyl-
chromium (2d) and paraformaldehyde (1a) provided the
desired 1,3-oxazolidine (4h). It was also possible to con-
dense amino alcohol 2d with acetaldehyde (1b), which
afforded two diastereomers, cis- and trans-4i, in the ratio
of 1 : 3.
C(6)
C(9)
C(8)
Cr(1)
O(2)
C(12)
C(11)
C(13)
C(2)
C(1)
C(3)
O(3)
O(1)
Fig. 2. Molecular structure of η6-[(5-methyl-1,3-oxazolidin-3-yl)-
benzene]tricarbonylchromium (4h). Thermal ellipsoids are given
at 30% probability. Hydrogen atoms are omitted.
the oxazolidine cycle in the molecule of 4h was disordered
at two positions and had an envelope conformation.
The oxygen atom deviated from the CNCC plane by
0.34—0.58(2) Å. The lengths of N—C and O—C bonds
in the heterocyclic ring were in the intervals of 1.462(2)—
1.467(2) Å and 1.389(3)—1.45(2) Å, respectively. The
C(11)—C(13) distance was close to that in alkanes and
equal to 1.505(4) Å. Same as in case of compound 6, the
carbonyl groups of Cr(CO)3 moiety had the eclipsed
orientation relative to the phenyl ring. The Cr—Carene
and Cr—(CО) distances were 2.203(2)—2.353(2) and
1.824(2)—1.842(2) Å, respectively (see Table 4).
Six-membered 1,3-oxazinanes 5a—c were prepared in
a similar way from γ-amino alcohols 3a,b and aldehydes
1a, 1c, and 1d (see Scheme 1). The reaction conditions
and some characteristics of the products are shown in Table 2.
Thus, boiling of 3-(N-phenylamino)propan-1-ol (3a)
with paraformaldehyde (1a) in toluene (for 2 h) provided
3-phenyl-1,3-oxazinane (5a) in the yield of 61%.
2,3-Diphenyl-1,3-oxazinane (5b) was similarly obtained
from amino alcohol 3a and benzaldehyde (1c) after 4 h in
a significantly lower yield (28%). Thus, the condensation
rate was noticeably decreased from formaldehyde to benz-
aldehyde. Attempts of carrying out the reactions between
amino alcohol 3a and (η6-benzaldehyde)tricarbonylchro-
Complexes 4h, cis-, and trans-4i were bright yellow
crystals with sharp melting points, while physicochemical
methods of analysis confirmed the purity and structure of
these compounds (see Table 2 and Experimental). Com-
pound 4h was also characterized by X-ray diffraction of
single crystal (Fig. 2 and Table 4). According to these data,
Table 4. Selected bond lengths (d) and angles (ω) in complex 4h
Bond
d/Å
Bond
d/Å
Angle
ω/deg
Cr(1)—C(4)
Cr(1)—C(5)
Cr(1)—C(6)
Cr(1)—C(7)
Cr(1)—C(8)
Cr(1)—C(9)
Cr(1)—C(1)
Cr(1)—C(2)
Cr(1)—C(3)
C(4)—C(9)
C(4)—C(5)
2.257(2)
2.208(2)
2.221(2)
2.203(2)
2.262(2)
2.353(2)
1.838(2)
1.824(2)
1.842(2)
1.421(2)
1.412(2)
C(5)—C(6)
C(6)—C(7)
C(7)—C(8)
C(8)—C(9)
N(1)—C(10)
N(1)—C(12)
C(11)—C(12)
O(4)—C(11)
C(10)—O(4)
C(11)—C(13)
1.405(3)
1.408(2)
1.403(2)
1.426(3)
1.467(2)
1.462(2)
1.542(3)
1.445(3)
1.389(3)
1.505(4)
C(9)—N(1)—C(10)
C(9)—N(1)—C(12)
C(12)—N(1)—C(10)
O(4)—C(10)—N(1)
C(10)—O(4)—C(11)
O(4)—C(11)—C(12)
N(1)—C(12)—C(11)
C(3)—Cr(1)—C(1)
C(3)—Cr(1)—C(2)
C(1)—Cr(1)—C(2)
121.9(2)
123.4(2)
109.1(2)
105.2(2)
103.2(2)
104.4(2)
100.1(2)
90.97(8)
85.97(7)
89.34(8)

888
Russ. Chem. Bull., Int. Ed., Vol. 67, No. 5, May, 2018
Artemov et al.
mium (1d) and also between chromium-containing amino
alcohol 3b and aldehyde 1c were unsuccessful apparently
due to steric reasons.
C(5)
C(7)
C(4)
C(10)
C(6)
O(2)
N(1)
(η6-Arene)tricarbonylchromium derivative of 1,3-ox-
azinane 5c was obtained via reaction of η6-{[(3-hydr-
oxyprop-1-yl)amino]benzene}tricarbonylchromium (3b)
with paraformaldehyde (1a). Product 5c was a yellow
crystalline solid with a melting point of 114—115 °C. The
absorption maximum in its UV-Vis spectrum at 318 nm
and the intense bands in the region of valence vibrations
of carbonyl at 1848 and 1948 cm–1 in the IR spectrum of
compound 5c confirmed the presence of the tricarbonyl-
chromium moiety in its structure. The mass spectrum of
1,3-oxazinane 5c contained the expected molecular ion
O(4)
C(9)
C(8)
Cr(1)
C(2)
C(13)
C(11)
C(1)
C(12)
C(3)
O(3)
O(1)
Fig. 3. Molecular structure of η6-[(1,3-oxazinan-3-yl)benzene]-
tricarbonylchromium (5c). Thermal ellipsoids are given at 30%
probability. Hydrogen atoms are omitted.
1
with a mass number of 299. The H NMR spectrum of
complex 5c contained a quintet from the C(5)H2 moiety
in the high field at 1.79 ppm, signals from the C(4)H2 and
C(6)H2 moieties at 3.50 and 3.85 ppm, a signal from the
methylene group between the two heteroatoms at 4.82 ppm,
and signals from the aromatic ring coordinated with the
chromium atom in the interval of 5.12—5.78 ppm.
and were in the range of 108.9(2)—111.3(2)° (see Table 5).
The Cr—Carene distances in 5c were close to those in
compounds 6 and 4h and remained in the interval of
2.193(2)—2.389(2) Å, which is typical of arenetricarbon-
ylchromium complexes.15 Same as in case of compounds
6 and 4h, the angles in Cr(CO)3 moiety of 5c were close
to 90° (see Table 5). The Cr(CO)3 moiety was located on
the side of oxazinane ring with respect to the C(4)—C(9)
plane of aromatic cycle.
To conclude, arenetricarbonylchromium-containing
amino alcohols were obtained for the first time and applied
for the synthesis of a number of representatives of new
classes of (η6-arene)tricarbonylchromium derivatives of
1,3-oxazolidines and 1,3-oxazinanes. The (η6-phenyl)
tricarbonylchromium derivatives of amino alcohols were
very sensitive to increasing of the size of substituents in
the carbonyl compound, thus affecting the condensation
that proceeded easily only with the simplest aliphatic alde-
hydes (formaldehyde and acetaldehyde).
The molecular structure of obtained heterocyclic
compound 5c was confirmed by the X-ray diffraction of
single crystal (Fig. 3 and Table 5). According to the X-ray
diffraction data, the oxazinane ring in compound 5c was
disordered at two positions similar to the oxazolidine
cycle in 4h. The heterocycle was having the chair confor-
mation at each of the positions, however, with different
orientations. At the first position, the O(4), C(10), C(12),
and C(13) atoms belong to the same plane (the average
deviation of the atoms from the plane did not exceed
0.03(2) Å), while the N(1) and C(11) atoms were shifted
in different directions relative to the plane by 0.69(2) and
0.65(2) Å, respectively. At the other position, the N(1)
and C(10)—C(12) atoms were almost in the same plane
(the average deviation of the atoms from the plane was
0.11(2) Å), while the O(4) and C(13) atoms deviated by
0.66(2) and 0.31(2) Å, respectively. The O—C bond lengths
in the oxazolidine ring were 1.42(2)—1.452(3) Å, and the
N—C distances were 1.442(2)—1.460(2) Å. The angles
inside the heterocyclic ring were close to tetrahedral ones
Experimental
The solvents were distilled over sodium metal at atmospheric
pressure. Ethyl acetate was dried over calcium chloride and distilled.16
The commercial paraformaldehyde and acetaldehyde from Sigma-
Table 5. Selected bond lengths (d) and angles (ω) in compound 5c
Bond
d/Å
Bond
d/Å
Angle
ω/deg
Cr(1)—C(4)
Cr(1)—C(5)
Cr(1)—C(6)
Cr(1)—C(7)
Cr(1)—C(8)
Cr(1)—C(9)
Cr(1)—C(1)
Cr(1)—C(2)
Cr(1)—C(3)
O(4)—C(11)
O(4)—C(10)
2.246(2)
2.193(2)
2.215(2)
2.202(2)
2.261(2)
2.389(2)
1.820(2)
1.829(2)
1.820(2)
1.452(3)
1.426(2)
N(1)—C(13)
N(1)—C(10)
C(11)—C(12)
C(12)—C(13)
C(4)—C(9)
C(4)—C(5)
C(5)—C(6)
C(6)—C(7)
C(7)—C(8)
C(8)—C(9)
1.460(2)
1.451(9)
1.527(9)
1.523(2)
1.423(2)
1.399(2)
1.407(2)
1.397(2)
1.416(2)
1.416(2)
C(9)—N(1)—C(10)
C(9)—N(1)—C(13)
C(10)—N(1)—C(13)
O(4)—C(10)—N(1)
O(4)—C(11)—C(12)
C(10)—O(4)—C(11)
C(11)—C(12)—C(13)
N(1)—C(13)—C(12)
C(3)—Cr(1)—C(1)
C(3)—Cr(1)—C(2)
C(1)—Cr(1)—C(2)
121.2(2)
122.8(2)
109.7(2)
111.0(2)
111.3(2)
108.9(2)
109.3(2)
109.6(2)
88.51(8)
86.15(7)
87.63(8)

1,3-Oxazacycloalkanes with (arene)Cr(CO)3 group
Russ. Chem. Bull., Int. Ed., Vol. 67, No. 5, May, 2018
889
Aldrich were used. Benzaldehyde (1c) was purified by distillation
under reduced pressure. (η6-Benzaldehyde)tricarbonylchromium
was prepared according to the known procedure.17 2-(N-Phenyl-
amino)ethanol (2a), 1-(N-phenylamino)propan-2-ol (2b), and
3-(N-phenylamino)propan-1-ol (3a) were synthesized by aryla-
tion of the corresponding amino alcohols with iodobenzene in
the presence of copper(I) chloride according to the published
procedure.18 (Triammine)(tricarbonyl)chromium (NH3)3Cr(CO)3
was prepared according to the reported method.11
toluene (20 mL) were placed into a 30 mL glass tube. The tube
was deaerated in liquid nitrogen and sealed in vacuo, then
heated in the oil bath at 120 °C. The tube was cooled down to
room temperature and opened; the reaction mixture was con-
centrated in vacuo. The reaction products were isolated from the
residue using column chromatography.
2,5-Dimethyl-3-phenyl-1,3-oxazolidine (4e), cis- and trans-
isomers (1 : 1), was obtained according to the general procedure
from amino alcohol (2b) (0.500 g, 3.3 mmol) and acetaldehyde
(1b) (0.410 g, 9.3 mmol); the reaction duration was 6 h; the elu-
ent was hexane—ethyl acetate (2 : 1). The yield was 58%, color-
less viscous oil. HPLC: two peaks, τ = 8.9 and 9.1 min. UV-Vis
(MeCN, H2O), λ/nm: 202, 247, 434. MS (EI, 70 eV), m/z (Irel (%)):
177 [M]+ (30), 162 [M – Me]+ (25), 134 [M – CH2СHMe – H]+
(100), 104 [M – MeCHOCH(Me) – H]+ (45), 91 [M –
– MeCHOCH(Me)CH2]+ (20), 77 [M – MeCHOCH(Me)CH2N]+
(30). 1H NMR (acetone-d6, 400 MHz), δ: 1.30—1.41 (m, 12 H,
Me); 2.83, 3.14 (both t, 1 H each, NCH2CH, J = 8.6 Hz); 3.55
(dd, 1 H, NCH2CH, J = 8.6 Hz and J = 5.9 Hz); 3.64 (dd, 1 H,
NCH2CH, J = 8.2 Hz and J = 5.9 Hz); 4.04—4.17, 4.45—4.56
(both m, 1 H each, CH2CHO); 5.19 (q, 1 H, NCHO, J = 5.1 Hz);
5.26 (q, 1 H, NCHO, J = 5.5 Hz); 6.58 (t, 4 H, m-HPh, J = 9.4 Hz);
6.63—6.73 (m, 2 H, p-HPh); 7.14—7.23 (m, 4 H, o-HPh).
Compounds 4f and 6 were obtained according to the general
procedure from amino alcohol 2c (0.140 g, 2.0 mmol) and para-
formaldehyde 1a (0.550 g). The reaction duration was 4 h; the
eluent was hexane—ethyl acetate (3 : 1). Isolated crystalline
products 4f and 6 were recrystallized from the hexane—ethyl
acetate mixture (4 : 1) and dried in vacuo.
The condensation products were isolated and purified by
column chromatography using Acros silica gel (0.035—0.070 mm)
under argon, eluent was hexane—ethyl acetate. HPLC was carried
out on a Knauer Smartline 5000 chromatograph equipped with
a S 2600 UV diode matrix detector, a Diasfer-110-C16 column,
5 μm, 4.6×250 mm, the eluent was a mixture of acetonitrile—
water (84 : 16) at the rate of eluent flow of 0.7 mL min–1
;
UV spectra of eluates were recorded in the 200—500 nm range.
IR spectra were recorded on an Infralyum FT-801 spectrometer
in the range of 450—4000 cm–1 in KBr pellets. 1H NMR spectra
were recorded on an Agilent DD2 NMR 400NB spectrometer
(400 MHz) in acetone-d6. Mass spectrometric investigations were
performed for m/z range of 70—500 Da with temperature pro-
gramming from 50 to 450 °C at heating rate of 100 deg min–1
.
Synthesis of arenetricarbonylchromium-containing amino al-
cohols 2c, 2d, and 3b (general procedure). N-Phenylamino alco-
hol (2a, 2b, or 3a) (30.0 mmol), (triammine)(tricarbonyl)
chromium (6.1 g, 32.6 mmol), and dioxane (50 mL) were placed
in a previously deaerated and then filled with argon two-necked
flask equipped with a reflux condenser and a gas burette with
dibutyl phthalate. The reaction mixture was heated in the oil bath
at 120 °C until evolution of ammonia (2.1 L) stopped, then the
flask was cooled and filled with argon. The resulting reaction
mixture was filtered through Al2O3 layer on a Schott filter under
argon flow. The solvent was removed in vacuo. The product was
obtained as a viscous oily liquid with yellow-brown color.
η6-[(2-Hydroxyethylamino)benzene]tricarbonylchromium (2c).
The yield was 54%, oil. HPLC: single peak, τ = 4.9 min. UV-Vis
(MeCN, H2O), λ/nm: 219, 314, 434. IR (KBr), ν/cm–1: 3402
(ν(О—H, N—H)); 3098 (ν(С—HAr)); 2936, 2875 (ν(С—H));
1949, 1853 (ν(С≡О)); 1633, 1555 (ν(СAr—СAr)); 758, 681, 633
(ω(С—HAr)). MS (EI, 70 eV), m/z (Irel (%)): 273 [M]+ (65), 217
[M – 2 СО]+ (16), 189 [M – 3 СО]+ (90), 143 [M – 3 CO –
– CH2CH2OH – H]+ (100), 137 [M – Cr(CO)3]+ (14), 52 [Cr]+ (4).
η6-{[(2-Hydroxyprop-1-yl)amino]benzene}tricarbonylchrom-
ium (2d). The yield was 65%, oil. HPLC: single peak, τ = 5.1 min.
η6-[(1,3-Oxazolidin-3-yl)benzene]tricarbonylchromium (4f).
The yield was 35%, yellow crystals, m.p. 127—128 °C. HPLC:
single peak, τ = 6.0 min. UV-Vis (MeCN, H2O), λ/nm: 219, 318,
435. IR (KBr), ν/cm–1: 3082 (ν(CAr—H)); 2902, 2857 (ν(C—H));
1957, 1883 (ν(C≡O)); 1607, 1553 (ν(CAr—CAr)); 810, 775, 682,
671 (ω(CAr—H)). MS (EI, 70 eV), m/z (Irel (%)): 285 [M]+ (7),
229 [M – 2 CO]+ (3), 201 [M – 3 CO]+ (100), 171 [M – 3 CO –
– CH2O]+ (65), 105 [M – Cr(CO)3 – CH2CH2O]+ (50), 52
[Cr]+ (87). 1H NMR (acetone-d6, 400 MHz), δ: 3.40 (t, 2 H,
NCH2CH2, J = 6.3 Hz); 4.13 (t, 2 H, OCH2CH2, J = 6.3 Hz);
4.79 (s, 2 H, NCH2O); 4.99 (d, 2 H, o-HPh, J = 6.7 Hz); 5.06
(t, 1 H, p-HPh, J = 6.3 Hz); 5.83 (t, 2 H, m-HPh, J = 6.3 Hz).
η6-[(Hexahydro-1,3,5-dioxazepin-5-yl)benzene]tricarbon-
ylchromium (6). The yield was 30%, yellow crystals, m.p.
111—112 °C. HPLC: single peak, τ = 6.7 min. UV-Vis (MeCN,
H2O), λ/nm: 218, 318, 434. IR (KBr), ν/cm–1: 3013 (ν(CAr—H));
2865 (ν(C—H)); 1938, 1846 (ν(C≡O)); 1631, 1607, 1541 (ν(CAr—CAr));
846, 756, 676, 633 (ω(CAr—H)). MS (EI, 70 eV), m/z (Irel (%)):
315 [M]+ (10), 231 [M – 3 CO]+ (8), 201 [M – 3 CO – CH2O]+
(80), 171 [M – 3 CO – CH2OCH2O]+ (50), 149 [M – Cr(CO)3
– CH2O]+ (90), 143 [M – 3 CO – CH2CH2OCH2OCH2]+ (55),
105 [M – Cr(CO)3 – CH2OCH2OCH2]+ (100), 52 [Cr]+ (83).
1H NMR (acetone-d6, 400 MHz), δ: 3.55, 3.98 (both t, 2 H each,
NСH2СH2, OСH2СH2, J = 5.1 Hz); 4.83, 4.97 (both s, 2 H each,
NCH2O, OCH2O); 5.10 (t, 1 H, p-HPh, J = 6.3 Hz); 5.38 (d, 2 H,
o-HPh, J = 7.0 Hz); 5.81 (t, 2 H, m-HPh, J = 7.0 Hz).
UV-Vis (MeCN, H2O), λ/nm: 216, 317, 434. IR (KBr), ν/cm–1
:
3458, 3295 (ν(О—H, N—H)); 3106 (ν(С—HAr)); 2953, 2872
(ν(С—H)); 1952, 1853 (ν(С≡О)); 1633, 1555 (ν(СAr—СAr)); 784,
691 (ω(С—HAr)). MS (EI, 70 eV), m/z (Irel (%)): 287 [M]+ (20),
231 [M – 2 СО]+ (15), 203 [M – 3 СО]+ (80), 143 [M – 3 CO –
– CH2CH(Me)OH – H]+ (100), [Cr]+ (10).
η6-{[(3-Hydroxyprop-1-yl)amino]benzene}tricarbonylchrom-
ium (3b). The yield was 33%, oil. HPLC: single peak, τ = 5.0 min.
UV-Vis (MeCN, H2O), λ/nm: 219, 314, 434. IR (KBr), ν/cm–1
:
3383 (ν(О—H, N—H)); 3052, 3024 (ν(С—HAr)); 2937, 2877
(ν(С—Н)); 1947, 1861 (ν(С≡О)); 1602, 1557, 1504 (ν(СAr—СAr));
752, 694, 635 (ω(С—HAr)). MS (EI, 70 eV), m/z (Irel (%)): 287
[M]+ (2), 203 [M – 3 CO]+ (10), 151 [M – Cr(CO)3] + (35), 106
η6-[(2-Methyl-1,3-oxazolidin-3-yl)benzene]tricarbonylchrom-
ium (4g) was obtained according to the general procedure from
amino alcohol 2c (0.140 g, 0.5 mmol) and acetaldehyde (1b)
(0.550 g, 12.5 mmol). The reaction duration was 6 h; the eluent
was hexane—ethyl acetate (3 : 1). The product was recrystallized
from hexane—ethyl acetate mixture (6 : 1) and dried in vacuo.
The yield was 31%, yellow crystals, m.p. 70—71 °C. HPLC:
[M – Cr(CO)3 – (CH2)2OH]+ (100), 77 [M – Cr(CO)3
–
– NH(CH2)3OH]+ (12), 52 [Cr]+ (56).
Condensation of aldehydes with amino alcohols in the sealed
glass tube (general procedure). Amino alcohol, aldehyde, and

890
Russ. Chem. Bull., Int. Ed., Vol. 67, No. 5, May, 2018
Artemov et al.
single peak, τ = 7.3 min. UV-Vis (MeCN, H2O), λ/nm: 218, 312,
435. IR (KBr), ν/cm–1: 3088 (ν(CAr—H)); 2851, 2926 (ν(C—H));
1948, 1882 (ν(C≡O)); 1603 (ν(CAr—CAr)); 815, 667, 632 (ω(CAr—H)).
MS (EI, 70 eV), m/z (Irel (%)): 299 [M]+ (10), 243 [M – 2 CO]+
(10), 215 [M – 3 CO]+ (48), 185 [M – 3 CO – CH2O]+ (100),
171 [M – 3 CO – CH2CH2O]+ (10), 143 [M – 3 CO –
– CH2CH2OCHMe]+ (28), 77 [M – Cr(CO)3 – CH2CH2OCH-
(Me)N]+ (10), [Cr]+ (11). 1H NMR (acetone-d6, 400 MHz), δ:
1.40 (d, 3 H, Me, J = 5.1 Hz); 3.34—3.45, 3.46—3.58, 3.98—4.11,
4.11—4.23 (all m, 1 H each, NCH2, NCH2, OCH2, OCH2);
aldehyde (1b) (1.7600 g, 40.0 mmol). The reaction duration was
6 h; the eluent was hexane—ethyl acetate (4 : 1). The isomers
were separated by column chromatography on silica gel using the
mixture of hexane—ethyl acetate as the eluent. The cis-isomer
cis-4i was eluted first, while the trans-isomer trans-4i was the
second one. The pure isomers were recrystallized from hexane—
ethyl acetate mixture (6 : 1) and dried in vacuo.
cis-η6-[(2,5-Dimethyl-1,3-oxazolidin-3-yl)benzene]tricarbon-
ylchromium (cis-4i). The yield was 18%, yellow crystals, m.p.
84—85 °С. HPLC: single peak, τ = 8.4 min. UV-Vis (MeCN,
H2O), λ/nm: 219, 317, 432. IR (KBr), ν/cm–1: 3052 (ν(CAr—H));
2894 (ν(C—H)); 1938, 1855 (ν(C≡O)); 1546 (ν(CAr—CAr)); 789,
669 (ω(СAr—H)). MS (EI, 70 eV), m/z (Irel (%)): 313 [M]+ (2),
257 [M – 2 CO]+ (2), 229 [M – 3 CO]+ (25), 185 [M – 3 CO –
– MeCHO]+ (100), 143 [M – 3 CO – MeCHOCH(Me)CH2]+
(38), 77 [M – Cr(CO)3 – MeCHOCH(Me)CH2N]+ (12), 52
[Cr]+ (22). 1H NMR (acetone-d6, 400 MHz), δ: 1.32 (d, 3 H,
Me, J = 5.9 Hz); 1.39 (d, 3 H, Me, J = 5.5 Hz); 2.84—2.88 (m,
1 H, CH2); 3.63 (dd, 1 H, CH2, J = 8.6 Hz and J = 5.5 Hz);
4.45—4.54 (m, 1 H, CH2СHMe); 4.98 (d, 2 H, o-HPh, J = 7.0 Hz);
5.04 (t, 1 H, p-HPh, J = 6.3 Hz); 5.25 (q, 1 H, NCH(Me)O,
J = 5.5 Hz); 5.80—5.83 (t, 2 H, m-HPh, J = 6.3 Hz).
4.97—5.09 (m, 3 H, CHMe, m-HPh); 5.15 (dd, 1 H, p-HPh
J = 10.2 Hz and J = 4.7 Hz); 5.83 (t, 2 H, o-HPh, J = 5.5 Hz).
,
η6-[(5-Methyl-1,3-oxazolidin-3-yl)benzene]tricarbonylchrom-
ium (4h) was obtained according to the general procedure from
amino alcohol 2d (0.170 g, 0.6 mmol) and paraformaldehyde (1a)
(0.580 g). The reaction duration was 6 h; the eluent was
hexane—ethyl acetate (4 : 1). The product was recrystallized
from hexane—ethyl acetate mixture (4 : 1) and dried in vacuo.
The yield was 30%, yellow crystals, m.p. 131—132 °С. HPLC:
single peak, τ = 7.3 min. UV-Vis (MeCN, H2O), λ/nm: 219, 316,
432. IR (KBr), ν/cm–1: 3048 (ν(CAr—H)); 2995 (ν(C—H));
1947, 1852 (ν(C≡O)); 1552 (ν(CAr—CAr)); 825, 674 (ω(CAr—H)).
MS (EI, 70 eV), m/z (Irel (%)): 299 [M]+ (2), 243 [M – 2 CO]+
(4), 215 [M – 3 CO]+ (20), 171 [M – 3 CO – MeCHO]+ (100),
143 [M – 3 CO – CH2CH(Me)OCH2]+ (23), [Cr]+ (29). 1H NMR
(acetone-d6, 400 MHz), δ: 1.35 (d, 3 H, Me, J = 5.9 Hz); 2.93
(t, 1 H, NCH2CH, J = 8.2 Hz); 3.53 (dd, 1 H, NCH2CH, J = 8.2 Hz
and J = 6.3 Hz); 4.31 (hex, 1 H, CH, J = 6.3 Hz); 4.72 (d, 1 H,
NCH2O, J = 2.4 Hz); 4.89—5.00 (m, 3 H, NCH2O, o-HPh);
5.04 (t, 1 H, p-HPh, J = 5.9 Hz); 5.82 (t, 2 H, m-HPh, J = 5.9 Hz).
Isomers of complex 4i were obtained according to the general
procedure from amino alcohol 2d (1.200 g, 4.2 mmol) and acet-
trans-η6-[(2,5-Dimethyl-1,3-oxazolidin-3-yl)benzene]tricarb-
onylchromium (trans-4i). The yield was 53%, m.p. 105—106 °С.
HPLC: single peak, τ = 7.8 min. UV-Vis (MeCN, H2O), λ/nm:
219, 317, 431. IR (KBr), ν/cm–1: 3040 (ν(CAr—H)); 2921, 2852
(ν(C—H)); 1935, 1849 (ν(C≡O)); 1630, 1547 (ν(CAr—CAr)); 679,
799 (ω(СAr—H)). MS (EI, 70 eV), m/z (Irel (%)): 313 [M]+ (5),
257 [M – 2 CO]+ (5), 229 [M – 3 CO]+ (30), 185 [M – 3 CO –
– MeCHO]+ (100), 143 [M – 3 CO – MeCHOCH(Me)CH2]+
(31), 77 [M – Cr(CO)3 – MeCHOCH(Me)CH2N]+ (12), 52
[Cr]+ (30). 1H NMR (acetone-d6, 400 MHz), δ: 1.33 (d, 3 H,
Table 6. Crystallographic data, parameters used in the X-ray diffraction experiments and refinements for
complexes 6, 4h, and 5c
Parameter
6
4h
5c
Formula
C
13H13CrNO5
C13H13CrNO4
299.24
Pna21
16.3065(5)
7.4539(2)
10.1594(3)
90
C13H13CrNO4
299.24
Molecular weight
Space group
a/Å
315.24
–
P1
P21/n
7.5793(6)
8.5955(6)
10.6299(8)
7.2925(6)
10.6982(9)
15.9011(13)
90
102.2830(10)
90
1212.15(17)
b/Å
c/Å
α/deg
97.1450(11)
101.3102(11)
104.7299(11)
645.57(8)
4
β/deg
90
90
γ/deg
V/Å3
1234.84(6)
4
1.610
0.935
2.30—35.62
Z 2
dcalc/mg mm–3
1.622
0.905
1.640
0.953
2.32—35.62
μ/mm–1
Scan range, θ/deg
Number of reflections
measured
1.99—28.70
6841
3010
0.0163
0.999
0.0397
0.1012
23477
5479
0.0240
1.002
0.0265
0.0646
0.37/–0.53
22432
4739
0.0435
1.066
0.0491
0.1104
0.65/–0.94
independent with I > 2σ(I)
Rint
GOOF (F2)
R1 (I > 2σ(I))
ωR2 (all data)
Residual electron density
(max/min)/е Å–3
0.60/–0.30

1,3-Oxazacycloalkanes with (arene)Cr(CO)3 group
Russ. Chem. Bull., Int. Ed., Vol. 67, No. 5, May, 2018
891
Me, J = 5.9 Hz); 1.44 (d, 3 H, Me, J = 4.7 Hz); 3.02—3.13
(m, 1 H, CH2); 3.31 (d, 1 H, CH2, J = 5.5 Hz); 3.55—3.62 (m, 1 H,
CH2СHMe); 4.10—4.20 (m, 1 H, NCH(Me)O); 4.93 (d, 1 H,
o-HPh, J = 7.0 Hz); 5.00—5.11 (m, 2 H, o-HPh, p-HPh); 5.84
(t, 2 H, m-HPh, J = 7.0 Hz).
3.85 (t, 2 H, OCH2CH2, J = 5.5 Hz); 4.82 (s, 2 H, NCH2O);
5.12 (t, 1 H, p-HPh, J = 6.3 Hz); 5.40 (d, 2 H, o-HPh, J = 6.7 Hz);
5.78 (t, 2 H, m-HPh, J = 6.3 Hz).
X-ray analysis. Crystals for the X-ray diffraction studies were
obtained via crystallization from the hexane—ethyl acetate mix-
tures of 4 : 1 (6, 5c) and 6 : 1 (4h). The intensities of reflections
were measured using Bruker Smart Apex (6) and Bruker D8 Quest
(4h, 5c) diffractometers (Mo-Kα-radiation, λ = 0.71073 Å,
ω-scanning, T = 100 K). The integration of experimental intens-
ity arrays and taking into account the absorption were performed
using SMART, APEX2,19 and SADABS20 software packages.
The structures were solved by a direct method and refined by the
full-matrix least squares method on F2hkl with anisotropic ther-
mal parameters for all the non-hydrogen atoms. Hydrogen atoms
were placed in geometrically calculated positions and refined
using a riding model. The calculations were performed using the
SHELX21 software package.
Table 6 shows the crystallographic data for compounds 6, 4h,
and 5c and parameters used in the X-ray diffraction experiments.
The structures were deposited in the Cambridge Crystallographic
Data Centre with the following CCDCs: 1579170 (6), 1579168
(4h), and 1579169 (5c); they are available online at ccdc.cam.
ac.uk/structures.
3-Phenyl-1,3-oxazinane (5a) was obtained according to the
general procedure from amino alcohol 3a (3.00 g, 19.9 mmol)
and paraformaldehyde (1a) (2.460 g). The reaction duration was
2 h; the eluent was hexane—ethyl acetate (4 : 1). The yield was
61%, oil. HPLC: single peak, τ = 6.5 min. UV-Vis (MeCN, H2O),
λ/nm: 202, 247, 282. IR (KBr), ν/cm–1: 3038, 3070 (ν(СAr—H));
2952, 2858 (ν(С—H)); 1599 (ν(СAr—СAr)); 835, 737, 694
(ω(СAr—H)). MS (EI, 70 eV), m/z (Irel (%)): 163 [M]+ (64), 162
[M – H]+ (87), 134 [M – (CH2)2 – H]+ (30), 120 [M – (CH2)3 –
– H]+ (13), 105 [M – O(CH2)3]+ (100), 104 [M – O(CH2)3 – H]+
(71), 91 [M – CH2O(CH2)3]+ (9), 77 [M – NCH2O(CH2)3]+
(27). 1H NMR (acetone-d6, 400 MHz), δ: 1.36 (quint, 2 H,
CH2CH2CH2, J = 5.5 Hz); 3.56 (t, 2 H, NCH2CH2, J = 5.5 Hz);
3.89 (t, 2 H, NCH2CH2, J = 5.5 Hz); 4.90 (s, 2 H, NCH2O);
6.88 (t, 1 H, p-HPh, J = 7.4 Hz); 7.09 (d, 2 H, o-HPh, J = 8.2 Hz);
7.28 (t, 2 H, m-HPh, J = 8.2 Hz).
2,3-Diphenyl-1,3-oxazinane (5b). Benzaldehyde (1c) (2.440 g,
23.0 mmol), 3-(N-phenylamino)propan-1-ol (3a) (3.410 g,
22.6 mmol), and toluene (35 mL) were placed into a round-
bottomed one-necked flask equipped with a Dean—Stark trap.
The reaction mixture was heated in the oil bath at 120 °С for
4 h, then cooled down to room temperature, and concentrated
in vacuo. The reaction product 5b was isolated from the residue
by column chromatography (eluent was hexane—ethyl acetate,
4 : 1), recrystallized from hexane—ethyl acetate mixture (4 : 1)
and dried in vacuo. The yield was 28%, m.p. 23—24 °С. HPLC:
single peak, τ = 12.2 min. UV-Vis (MeCN, H2O), λ/nm: 205,
248. IR (KBr), ν/cm–1: 3058, 3032 (ν(С—HAr)); 2950, 2922,
2850 (ν(С—H)); 1598 (ν(СAr—СAr)); 757, 730, 698 (ω(С—HAr)).
MS (EI, 70 eV), m/z (Irel (%)): 239 [M]+ (22), 181 [M –
– O(CH2)3]+ (20), 162 [M – Ph]+ (47), 132 [M – PhCHO – H]
(25), 105 [M – PhCHO(CH2)2]+ (100), 104 [M – PhCHO(CH2)2
– H]+ (72), 91 [M – PhCHO(CH2)3] (13), 77 [M – PhCHO-
(CH2)3N]+ (25). 1H NMR (acetone-d6, 400 MHz), δ: 1.55—1.69,
1.69—1.82, 3.49—3.60, 3.81—3.96, 3.61—3.71, 4.00—4.16 (all m,
1 H each, CH2CH2CH2, CH2CH2CH2, NCH2, NCH2, OCH2,
OCH2); 6.02 (s, 1 H, CHPh); 6.84 (t, 1 H, p-HPhN, J = 7.0 Hz);
7.08—7.21 (m, 4 H, o,m-HPhN); 7.25 (t, 1 H, p-HPh, J = 7.0 Hz);
7.33 (t, 2 H, m-HPh, J = 7.0 Hz); 7.48 (d, 2 H, o-HPh, J = 7.4 Hz).
η6-[(1,3-Oxazinan-3-yl)benzene]tricarbonylchromium (5c)
was obtained according to the general procedure from amino
alcohol 3b (2.530 g, 8.8 mmol), paraformaldehyde (1a) (1.720 g),
and toluene (35 mL) in a 50 mL glass tube. The reaction duration
was 1.5 h; the eluent was hexane—ethyl acetate (2 : 1). The
product 5c was recrystallized from hexane—ethyl acetate mixture
(4 : 1) and dried in vacuo. The yield was 22%, m.p. 114—115 °С.
HPLC: single peak, τ = 6.6 min. UV-Vis (MeCN, H2O), λ/nm:
219, 318, 436. IR (KBr), ν/cm–1: 3113 (ν(СAr—H); 2919, 2854
(ν(С—H)); 1948, 1848 (ν(С≡О)); 1613, 1540 (ν(СAr—СAr)); 677,
630 (ω(СAr—H)). MS (EI, 70 eV), m/z (Irel (%)): 299 [M]+ (52),
243 [M – 2 CO]+ (29), 215 [M – 3 CO]+ (76), 187 [M – 3 CO –
– (CH2)2] + (32), 171 [M – 3 CO – (CH2)3 – 2 H] + (28), 157
[M – 3 CO – (CH2)3O] + (86), 121 [M – Cr(CO)3 – (CH2)3] +
(12), 120 [M – Cr(CO)3 – (CH2)3 – H]+ (100), 52 [Cr]+ (14).
1H NMR (acetone-d6, 400 MHz), δ: 1.79 (quint, 2 H,
CH2CH2CH2, J = 5.5 Hz); 3.50 (t, 2 H, NCH2CH2, J = 5.5 Hz);
The authors are grateful to Yu. A. Gracheva and E. S.
Shchegravina, the graduate students at Department of
Chemistry of N. I. Lobachevsky State University of Nizhny
Novgorod, for the registration of 1H NMR spectra.
This work was financially supported by the Council
on Grants of the President of the Russian Federation
(Program for state support for leading scientific schools
and young scientists, Project No. MK-1142.2017.3).
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Received November 28, 2017;
in revised form January 29, 2018;
accepted February 22, 2018