Reactions of 3,3,3-trichloro(trifluoro)-1-nitropropenes with 2-morpholinoalk-1-enes

Article abstract of DOI:10.1007/s11172-011-0020-3

The reaction of 3,3,3-trichloro(trifluoro)-1-nitropropenes with 2-morpholinoalk-1-enes affords the nitroalkylated Z-enamines whose subsequent hydrolysis results in 2-trihalomethyl-1-nitroalkan-4-ones.

Full text of DOI:10.1007/s11172-011-0020-3

Russian Chemical Bulletin, International Edition, Vol. 60, No. 1, pp. 143—147, January, 2011
143
Reactions of 3,3,3ꢀtrichloro(trifluoro)ꢀ1ꢀnitropropenes
with 2ꢀmorpholinoalkꢀ1ꢀenes
V. Yu. Korotaev,a A. Yu. Barkov,a P. A. Slepukhin,b and V. Ya. Sosnovskikha
aA. M. Gorky Ural State University,
51 prosp. Lenina, 620083 Ekaterinburg, Russian Federation.
Fax: +7 (343) 261 5978. Eꢀmail: Vyacheslav.Sosnovskikh@usu.ru
bI. Ya. Postovsky Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences,
20 ul. S. Kovalevskoi, 620041 Ekaterinburg, Russian Federation
The reaction of 3,3,3ꢀtrichloro(trifluoro)ꢀ1ꢀnitropropenes with 2ꢀmorpholinoalkꢀ1ꢀenes
affords the nitroalkylated Zꢀenamines whose subsequent hydrolysis results in 2ꢀtrihalomethylꢀ
1ꢀnitroalkanꢀ4ꢀones.
Key words: 3,3,3ꢀtrihaloꢀ1ꢀnitropropenes, enamines, Michael reaction, nitro compounds,
fluorine organic compounds, Xꢀray diffraction study.
Due to high electrophilicity of the double bond, 3,3,3ꢀtriꢀ
chloro(trifluoro)ꢀ1ꢀnitropropenes find ever increasing apꢀ
plication as CCl3ꢀ and CF3ꢀcontaining synthons for the
preparation of polyfunctional compounds in both the reacꢀ
tions with nucleophilic reagents1—5 and the cycloaddition
reactions.6—11 Recently,12 we have described an example
of a tandem [4+2]/[3+2] cycloaddition where these nitroꢀ
alkenes acted as the heterodiene and dipolarophile in the
reaction with 2,3ꢀdihydrofuran. The data on the reactions
of polyhaloalkylated nitroolefins with enamines are very
limited. It is only known that the reaction of 3,3,3ꢀtrifluoꢀ
roꢀ1ꢀnitropropene with ethyl 3ꢀmorpholinocrotonate afꢀ
fords the cyclobutane derivative as a result of [2+2] carboꢀ
cyclization13 and the reactions of polyfluoroalkylated
nitroalkenes with enamines of cycloalkanones and acetoꢀ
phenone afford βꢀpolyfluoroalkyl γꢀnitro ketones.14 In the
present work, we studied the features of the reactions of
3,3,3ꢀtrichloro and 3,3,3ꢀtrifluoroꢀ1ꢀnitropropenes (1a,b)
with 2ꢀmorpholinoalkꢀ1ꢀenes (morpholine enamines of
pinacoline and acetophenone) in polar (dichloromethane)
and nonꢀpolar (benzene) solvents under the conditions of
the kinetic control.
CF3ꢀnitroalkene 1b, the yield of compound 3b increases
to 87% if the reaction is performed without solvent for 0.5 h.
The formation of compounds 3 proceeds as the Michael
addition through the betaine intermediate А, which, unꢀ
der these conditions, does not undergo intramolecular
cyclization into cyclobutane or cyclic nitronate (1,2ꢀoxꢀ
azine Nꢀoxide). Such reaction pathway would be expected
Scheme 1
Results and Discussion
It was established that the reaction of nitroalkenes 1a,b
with 3,3ꢀdimethylꢀ2ꢀmorpholinobutꢀ1ꢀene (2), which is
prepared from pinacoline and morpholine, in dichloroꢀ
methane for 3 days (1a) or 2 h (1b) at room tempearature
affords nitroalkylated enamines 3a,b in yields of 68 and
72%, respectively, which are hydrolyzed almost quantitaꢀ
tively into γꢀnitro ketones 4a,b upon treatment with dilute
HCl in ethanol (Scheme 1). In the case of more reactive
X = Cl (a), F (b)
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 137—140, January, 2011.
1066ꢀ5285/11/6001ꢀ143 © 2011 Springer Science+Business Media, Inc.

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Korotaev et al.
based on the known data15—20 on the reactions of enamꢀ
ines with the nonꢀhalogenated analogs of nitroalkenes 1.
Compounds 3b and 4b have been prepared earlier21 from
enamine 2 and 2ꢀdiazoꢀ3,3,3ꢀtrifluoroꢀ1ꢀnitropropane;
however, the configuration of the double bond in 3b was
not established.
Scheme 2
Xꢀray diffraction study of the sample of 3a showed that
its double bond has the Zꢀconfiguration (Fig. 1). This
conclusion can be expanded to the fluorinated analog 3b,
1
since the H NMR spectra of compounds 3a,b in CDCl3
are very similar and characterized by the close chemiꢀ
cal shifts of the protons of the aliphatic chain (taking
into account the large deshielding effect of the trichloꢀ
romethyl group compared to the trifluoromethyl one) and
the presence of the AMX spin system with the spinꢀspin
coupling constants JA,M = 11.4—11.8 Hz, JA,X = 9.0 Hz,
and JM,X = 3.8—5.1 Hz.
reaction mixture, obtained γꢀnitro ketones 8a,b in yields
of 77—87% (Scheme 3). The intermediate nitroalkylated
enamines have not been isolated in this case due to their
easy hydrolysis by the atmospheric moisture. The disꢀ
tinctive feature of the 1H NMR spectra of γꢀnitro ketones
4a,b and 8a,b, among which 4a and 8a were prepared
for the first time, is a significant difference in the valꢀ
ues of constans for the geminal methylene protons at
the C=O group (2J = 18.2—18.6 Hz) and nitro group
(2J = 13.6—14.2 Hz).
The replacement of dichloromethane for nonꢀpolar
benzene or hexane in the case of compound 1b does not
result in new products, while, in the case of compound 1a,
the reaction proceeds mainly as [4+2] cycloaddition to
afford a mixture of 1,2ꢀoxazine Nꢀoxide 5 (84%), cycloꢀ
butane 6 (8%), and enamine 3a (8%) (1H NMR spectral
data) (Scheme 2). When the resulting mixture was treated
with an aqueous solution of acetic acid for 6 h, enamine 3a
formed in a yield of 68%. We failed to isolate oxazine 5 in
the pure form due to easy ring opening to form compound
3a. The bulky trichloromethyl group occupies the equatoꢀ
rial cisꢀposition in oxazine 5 in relation to the equatorial
tertꢀbutyl group, which is indicated by the large spinꢀspin
coupling constans for the protons of the CН2 group with
the axial H(4) atom (3J = 10.5 Hz and 3J = 7.5 Hz).
It is known that the reactions of enamine 7 derived
from morpholine and acetophenone with 2ꢀdiazoꢀ3,3,3ꢀ
trifluoroꢀ1ꢀnitropropane (C6H6, ~20 °C, 1 h)21 and niꢀ
troalkene 1b (CH2Cl2, ~20 °C, 2 h)14 afford γꢀnitro ketone
8b. We performed the reaction of nitro alkenes 1a,b with
enamine 7 in benzene and, after acid hydrolysis of the
Scheme 3
X = Cl (a), F (b)
The synthetic value of the carbonyl and nitro groups is
wellꢀknown; therefore, the γꢀnitro ketones desribed in the
present work are of definite interest as substrates for subꢀ
sequent syntheses based on them, in particular, for the
preparation of γꢀnitro and γꢀamino βꢀtrihalomethylalꢀ
kanols. Our preliminary results on reduction of nitro
ketone 4b with sodium borohydride and lithium alumiꢀ
num hydride showed that the former reaction is chemoꢀ
selective (only the carbonyl group is reduced, the raꢀ
tio of diastereomers 9 is 1 : 1, and the yield is 83%),
and the latter is diastereoselective (both functional groups
are reduced, the ratio of diastereomers 10 isolated in the
form of hydrochlorides is 1 : 10, and the yield is 47%)
(Scheme 4).
C(1)
Cl(2)
C(2)
C(4)
C(7)
C(6)
C(9)
C(8)
C(3)
O(2)
Cl(3)
C(5)
Cl(1)
N(2)
N(1)
C(10)
C(13)
C(12)
Thus, the reactions of 3,3,3ꢀtrichloro(trifluoro)ꢀ1ꢀ
nitropropenes with 2ꢀmorpholinoalkꢀ1ꢀenes afford nitroꢀ
alkylated Zꢀenamines and βꢀtrihalomethylꢀγꢀnitroketones,
which are of interest for the synthesis of polyfunctional
CCl3ꢀ and CF3ꢀcontaining compounds.
O(3)
C(11)
O(1)
Fig. 1. Molecular structure of compound 3a.

4ꢀMorpholinoꢀ1ꢀnitroꢀ2ꢀtrihalomethylalkꢀ3ꢀenes
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 1, January, 2011
145
Scheme 4
2,2ꢀDimethylꢀ6ꢀnitroꢀ5ꢀtrichloromethylhexanꢀ3ꢀone (4a).
A mixture of enamine 3a (0.36 g, 1.0 mmol), 0.1 M HCl (2 mL),
and ethanol (2 mL) was stirred for 4 h at 50 °C, cooled to ~20 °C,
extracted with dichloromethane (3×2 mL), and dried with
Na2SO4. After removal of the solvent, a lightꢀyellow oil of
the title compound was obtained. The yield was 0.26 g (88%).
Found (%): C, 37.04; H, 4.75; N, 4.97. C9H14Cl3NO3. Calculatꢀ
ed (%): C, 37.20; H, 4.86; N, 4.82. IR, ν/cm–1: 1711, 1563,
1377, 1355. 1H NMR (CDCl3), δ: 1.21 (s, 9 H, But); 2.96
(dd, 1 H, H(4a), J = 18.6 Hz, J = 8.1 Hz); 3.36 (dd, 1 H, H(4b),
J = 18.6 Hz, J = 3.3 Hz); 4.16 (dddd, 1 H, H(5), J = 8.1 Hz,
J = 5.9 Hz, J = 4.7 Hz, J = 3.3 Hz); 4.52 (dd, 1 H, H(6a),
J = 13.8 Hz, J = 5.9 Hz); 4.92 (dd, 1 H, H(6b), J = 13.8 Hz,
J = 4.7 Hz).
2,2ꢀDimethylꢀ6ꢀnitroꢀ5ꢀtrifluoromethylhexanꢀ2ꢀone (4b) was
prepared analogously. The yield was 91%, b.p. 90—91 °C (2 Torr)
(cf. Ref. 21: b.p 90—91 °C (2 Torr)). IR, ν/cm–1: 1712, 1566,
1380, 1339. 1H NMR (CDCl3), δ: 1.19 (s, 9 H, But); 2.85
(dd, 1 H, H(4a), J = 18.5 Hz, J = 8.6 Hz); 2.97 (dd, 1 H, H(4b),
J = 18.5 Hz, J = 4.4 Hz); 3.64—3.76 (m, 1 H, H(5)); 4.52
(dd, 1 H, H(6a), J = 13.6 Hz, J = 5.1 Hz); 4.63 (dd, 1 H, H(6b),
J = 13.6 Hz, J = 6.3 Hz). 19F NMR (CDCl3), δ: 91.9 (d, CF3,
J = 8.0 Hz).
Reaction of nitro alkene 1a with 3,3ꢀdimethylꢀ2ꢀmorpholiꢀ
nobutꢀ1ꢀene (2). To a solution of enamine 2 (1.69 g, 10.0 mmol)
in dry benzene (5 mL), a solution of nitro alkene 1a (1.90 g,
10.0 mmol) in dry benzene (5 mL) was added dropwise with
stirring over 15 min. The resulting mixture was stirred for 30 min
at ~20 °C and the precipitate that formed was filtered off and
washed with pentane. A mixture (1.97 g, 55%) of products 3a, 5,
and 6 in a ratio of 8 : 84 : 8 was obtained as a white powder,
m.p. 119—120 °C. Found (%): C, 43.27; H, 5.94; N, 7.97.
C13H21Cl3N2O3. Calculated (%): C, 43.41; H, 5.88; N, 7.79.
IR, ν/cm–1: 1624, 1560, 1454, 1369, 1354, 1243, 1111. When
this mixture was treated with aqueous acetic acid for 6 h, enamꢀ
ine 3a was obtained in a yield of 68%.
6ꢀtertꢀButylꢀ6ꢀmorpholinoꢀ4ꢀtrichloromethylꢀ5,6ꢀdihydroꢀ
4Hꢀ1,2ꢀoxazineꢀ2ꢀoxide (5) was prepared as a mixture with comꢀ
pounds 3a (8%) and 6 (8%) and was not isolated in the pure form
due to its instability. 1H NMR (500 MHz, C6D6), δ: 0.81 (s, 9 H,
But); 2.12 (dd, 1 H, H(5a), J = 14.5 Hz, J = 10.5 Hz); 2.24 (dd, 1 H,
H(5b), J = 14.5 Hz, J = 7.5 Hz); 2.46—2.54 (m, 2 H, N(CHH)2);
2.83—2.90 (m, 2 H, N(CHH)2); 3.27 (ddd, 1 H, H(4), J = 10.5 Hz,
J = 7.5 Hz, J = 3.2 Hz); 3.26—3.33 (m, 4 H, O(CH2)2); 6.44
(d, 1 H, H(3), J = 3.2 Hz). 13C NMR (126 MHz, C6D6), δ: 26.1,
26.8, 43.1, 48.4, 54.2, 67.4, 68.2, 100.9, 106.5.
Experimental
IR spectra were recorded on a Perkin—Elmer Spectrum
BXꢀII instrument in KBr pellets. 1Н, 19F, and 13C NMR spectra
were recorded on Bruker DRXꢀ400 (400, 376, and 100 MHz,
respectively) and Bruker Avance II (500 MHz) spectrometers in
CDCl3 and C6D6 using Me4Si and C6F6 as internal standards.
Nitro alkenes 1a,b (see Refs 1 and 22), as well as enamines 2
and 7 (see Refs 23 and 24) were prepared according to known
procedures.
(Z)ꢀ2,2ꢀDimethylꢀ3ꢀmorpholinoꢀ6ꢀnitroꢀ5ꢀtrichloromethylꢀ
hexꢀ3ꢀene (3a). To a solution of enamine 2 (1.69 g, 10.0 mmol)
in dry dichloromethane (2 mL), a solution of nitro alkene 1a
(1.90 g, 10.0 mmol) in dry dichloromethane (5 mL) was added
dropwise with stirring over 15 min. The mixture was stirred for
three days at ~20 °C, the solvent was evaporated, and the residue
was recrystallized from pentane to give enamine 3a in a yield of
2.43 g (68%), m.p. 79—80 °C. Found (%): C, 43.38; H, 5.94;
N, 7.76. C13H21Cl3N2O3. Calculated (%): C, 43.41; H, 5.88;
N, 7.79. IR, ν/cm–1: 1645, 1561, 1377, 1353. 1H NMR (CDCl3),
δ: 1.16 (s, 9 H, But); 2.84—2.93 (m, 2 H, N(CHH)2); 3.00—3.08
(m, 2 H, N(CHH)2); 3.70 (br.s, 4 H, O(CH2)2); 4.46 (dd, 1 H,
H(6a), J = 11.4 Hz, J = 9.0 Hz); 4.86 (td, 1 H, H(5), J = 9.4 Hz,
J = 3.8 Hz); 5.06 (dd, 1 H, H(6b), J = 11.4 Hz, J = 3.8 Hz); 5.40
(d, 1 H, H(4), J = 9.8 Hz). 1H NMR (C6D6), δ: 0.97 (s, 9 H,
But); 2.65—2.80 (m, 4 H, N(CH2)2); 3.52—3.64 (m, 4 H,
O(CH2)2); 3.86 (dd, 1 H, H(6a), J = 11.4 Hz, J = 9.0 Hz); 4.44
(dd, 1 H, H(6b), J = 11.4 Hz, J = 3.9 Hz); 4.82 (td, 1 H, H(5),
J = 9.3 Hz, J = 3.9 Hz); 5.22 (d, 1 H, H(4), J = 9.7 Hz).
13C NMR (C6D6), δ: 30.4 (C(1)), 40.4 (C(2)), 52.5 (NCH2),
56.6 (C(6)), 67.7 (OCH2), 78.0 (C(5)), 99.9 (CCl3), 116.3 (C(4)),
164.9 (C(3)).
(Z)ꢀ2,2ꢀDimethylꢀ3ꢀmorpholinoꢀ6ꢀnitroꢀ5ꢀtrifluoromethylꢀ
hexꢀ3ꢀene (3b) was prepared from enamine 2 and nitro alkene 1b
according to the procedure described for compound 3a (the duꢀ
ration of stirring was 2 h and the yield was 72%); if the reaction is
performed without solvent for 0.5 h, the yield was 87%, m.p.
98—99 °C (cf. Ref. 21: m.p. 98—99 °C). IR, ν/cm–1: 1653, 1562,
1383, 1351. 1H NMR (CDCl3), δ: 1.12 (s, 9 H, But); 2.95 (t, 4 H,
N(CH2)2, J = 4.4 Hz); 3.70 (t, 4 H, O(CH2)2, J = 4.4 Hz); 4.36
(dd, 1 H, H(6a), J = 11.8 Hz, J = 9.0 Hz); 4.45—4.57 (m, 1 H,
H(5)); 4.71 (dd, 1 H, H(6b), J = 11.8 Hz, J = 5.1 Hz); 5.19
(d, 1 H, H(4), J = 10.1 Hz). 19F NMR (CDCl3), δ: 92.1 (d, CF3,
J = 8.2 Hz).
1ꢀtertꢀButylꢀ1ꢀmorpholinoꢀ2ꢀnitroꢀ3ꢀtrichloromethylcycloꢀ
1
butane (6) was detected by H NMR spectroscopy in a mixture
with compounds 3a (8%) and 5 (84%). 1H NMR (500 MHz,
C6D6), δ: 1.77 (ddd, 1 H, H(4a), J = 12.8 Hz, J = 10.2 Hz,
J = 0.8 Hz); 1.84 (dd, 1 H, H(4b), J = 12.8 Hz, J = 9.0 Hz);
2.55—2.65 (m, 4 H, N(CH2)2); 3.42—3.46 (m, 4 H, O(CH2)2);
4.05 (dt, 1 H, H(3), J = 10.2 Hz, J = 9.0 Hz); 5.10 (dd, 1 H,
H(2), J = 9.0 Hz, J = 0.6 Hz).
4ꢀNitroꢀ1ꢀphenylꢀ3ꢀtrichloromethylbutanꢀ1ꢀone (8a). To
a solution of enamine 7 (1.89 g, 10.0 mmol) in dry benzene
(5 mL), a solution of nitro alkene 1a (1.90 g, 10.0 mmol) in dry
benzene (5 mL) was added dropwise with stirring over 15 min.
The resulting mixture was stirred for 30 min at ~20 °C, the solꢀ
vent was removed under reduced pressure, and 0.1 M HCl
(10 mL) was added to the residue. The resulting mixture was

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Korotaev et al.
stirred for 30 min at ~20 °C, extracted with dichloromethane
(3×3 mL), and the extract was dried with Na2SO4. After removal
of the solvent, the residue was recrystallized from hexane. The
yield was 2.39 g (77%), m.p. 68—69 °C. Found (%): C, 42.53;
H, 3.36; N, 4.49. C11H10Cl3NO3. Calculated (%): C, 42.54;
H, 3.25; N, 4.51. IR, ν/cm–1: 1685, 1597, 1581, 1552, 1375,
1354. 1H NMR (CDCl3), δ: 3.44 (dd, 1 H, H(2a), J = 18.2 Hz,
J = 8.5 Hz); 3.87 (dd, 1 H, H(2b), J = 18.2 Hz, J = 3.4 Hz); 4.40
(dtd, 1 H, H(3), J = 8.5 Hz, J = 5.1 Hz, J = 3.4 Hz); 4.64
(dd, 1 H, H(4a), J = 14.2 Hz, J = 5.3 Hz); 4.98 (dd, 1 H, H(4b),
J = 14.2 Hz, J = 4.9 Hz); 7.52 (t, 2 H, H(3´), H(5´), J = 7.6 Hz);
7.64 (tt, 1 H, H(4´), J = 7.4 Hz, J = 1.2 Hz); 8.00 (d, 2 H, H(2´),
H(6´), J = 8.0 Hz).
4ꢀNitroꢀ1ꢀphenylꢀ3ꢀtrifluoromethylbutanꢀ1ꢀone (8b) was preꢀ
pared according to the procedure described for compound 8a in
a yield of 87%, m.p. 59—60 °C (from pentane) (cf. Ref. 21: m.p.
60—61 °C). IR, ν/cm–1: 1680, 1598, 1581, 1551, 1387, 1347.
1H NMR (CDCl3), δ: 3.35 (dd, 1 H, H(2a), J = 18.4 Hz,
J = 9.2 Hz); 3.47 (dd, 1 H, H(2b), J = 18.4 Hz, J = 4.0 Hz);
3.87—4.00 (m, 1 H, H(3)); 4.64 (dd, 1 H, H(4a), J = 13.8 Hz,
J = 4.7 Hz); 4.72 (dd, 1 H, H(4b), J = 13.8 Hz, J = 6.6 Hz);
7.52 (t, 2 H, H(3´), H(5´), J = 7.7 Hz); 7.64 (tt, 1 H, H(4´),
J = 7.4 Hz, J = 1.2 Hz); 7.97 (d, 2 H, H(2´), H(6´), J = 8.0 Hz).
19F NMR (CDCl3), δ: 90.9 (d, CF3, J = 8.7 Hz).
6,6,6ꢀTrifluoroꢀ2,2ꢀdimethylꢀ5ꢀnitromethylhexanꢀ3ꢀol (9).
To a solution of nitro ketone 4b (2.41 g, 10.0 mmol) in ethanol
(5 mL), NaBH4 (0.19 g, 5.0 mmol) was added with stirring porꢀ
tionwise over 5 min. The resulting mixture was stirred for 3 h at
~20 °C, 0.1 M HCl (6 mL) was added, and the mixture was
extracted with dichloromethane (3×4 mL). The extract was dried
with Na2SO4. After removal of the solvent, the residue was disꢀ
tilled in vacuo. The yield was 2.02 g (83%), b.p. 117—119 °C
(2 Torr). Found (%): C, 44.47; H, 6.81; N, 5.71. C9H16F3NO3.
Calculated (%): C, 44.44; H, 6.63; N, 5.76. 1H NMR (CDCl3),
δ: 0.91 (s, 9 H, But); 1.41 (ddd, 1 H, CHH, J = 14.6 Hz,
J = 10.8 Hz, J = 7.6 Hz); 1.68—1.76 (m, 1 H, CH); 1.95 (ddt,
1 H, CHH, J = 14.6 Hz, J = 5.0 Hz, J = 1.8 Hz); 3.30—3.52
(m, 2 H, CHCF3, OH); 4.56 (dd, 1 H, CHHNO2, J = 14.2 Hz,
J = 4.8 Hz); 4.81 (dd, 1 H, CHHNO2, J = 14.2 Hz, J = 5.3 Hz)
(52%); 0.92 (s, 9 H, But); 1.68—1.76 (m, 2 H, CHH, CH); 1.80
(ddd, 1 H, CHH, J = 14.6 Hz, J = 10.8 Hz, J = 3.5 Hz);
3.30—3.52 (m, 2 H, CHCF3, OH); 4.60 (dd, 1 H, CHHNO2,
J = 14.0 Hz, J = 7.0 Hz); 4.66 (dd, 1 H, CHHNO2, J = 14.0 Hz,
J = 6.8 Hz) (48%). 19F NMR (CDCl3), δ: 91.0 (d, CF3,
J = 9.0 Hz) (52%); 90.6 (d, CF3, J = 8.7 Hz) (48%).
N, 5.61. 1H NMR (DMSOꢀd6), δ: 1.53 (ddd, 1 H, CHH,
J = 14.8 Hz, J = 10.8 Hz, J = 4.4 Hz); 1.75 (ddd, 1 H, CHH,
J = 14.8 Hz, J = 7.1 Hz, J = 1.8 Hz); 2.88—2.98 (m, 1 H,
CHCF3); 3.03 (dd, 1 H, CHHN, J = 13.3 Hz, J = 6.5 Hz); 3.08
(dd, 1 H, CHHN, J = 13.3 Hz, J = 6.0 Hz); 3.17 (d, 1 H, CH,
J = 10.2 Hz); 7.50—9.00 (br.s, 4 H, OH, NH3+). 19F NMR
(DMSOꢀd6), δ: 93.9 (d, CF3, J = 9.4 Hz) (91%); 93.8 (d, CF3,
J = 9.5 Hz) (9%).
Xꢀray diffraction study of compound 3a was performed on
a
Xcalibur
3
automatic singleꢀcrystal diffractometer
(Т = 150(2) K, MoꢀKα radiation, graphite monochromator, ω/2θ
scanning in the region of 2θ < 56.5°). Crystallographic data:
a = 26.518(3) Å, b = 7.9003(5) Å, c = 18.2210(12) Å, α = γ = 90°,
3
β = 114.574(8)°, V = 3471.6(5) Å , space group C2/c, monoclinꢀ
ic crystal system, Z = 8, C13H21Cl3N2O3, dcalc = 1.376 g cm–3
.
The intensities of 5798 reflections were measured, among which
4178 were independent (Rint = 0.0264). The structure was solved
by the direct method using the SHELXSꢀ97 program.25 The
refinement of structural parameters was performed by the leastꢀ
squares method in the anisotropic isotropic (for the H atoms)
approximation using the SHELXLꢀ97 software system.25 The
positions of the Н atoms were calculated geometrically (the
riding model). The final values of the divergence factors were
wR2 = 0.2535, R1 = 0.0580 for 3170 reflections with I > 2σ
(S = 1.013). The peaks of maximum and minimum residual denꢀ
sities were 0.798 and –0.362 е Å–3, respectively. The details for
Xꢀray diffraction study are deposited in the Cambridge Crystalꢀ
lographic Data Centre (CCDC 785766).
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5ꢀAminomethylꢀ6,6,6ꢀtrifluoroꢀ2,2ꢀdimethylhexanꢀ3ꢀol hydroꢀ
chloride (10). To a suspension of LiAlH4 (1.52 g, 40 mmol) in dry
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Received August 16, 2010