Catalytic synthesis of 1,3-propylenediamines

Article abstract of DOI:10.1134/S1070428011020035

The hydrogenation on Raney nickel of 3-alkenyl-substituted pyrazolines and also of 3-methyl-5-(2-furyl)-1H-pyrazoline and 3,3′-bipyrazoline afforded substituted 1,3-diaminobutanes, 1,3-diaminopentanes, 1,3-diaminohexane, and 1,3,4,6-tetraaminohexane. Under the same conditions from 3-acetyl-4-(2-furyl)- 1H-pyrazoline 3-amino-2-methyl-4-(2-furyl)pyrrolidine was obtained.

Full text of DOI:10.1134/S1070428011020035

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 2, pp. 168172. Pleiades Publishing, Ltd., 2011.
Original Russian Text  K.V. Yakovlev, D.V. Petrov, V.A. Dokichev, Yu.V. Tomilov, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 2,
pp. 180184.
Catalytic Synthesis of 1,3-Propylenediamines
a
a
a
b
K. V. Yakovlev , D. V. Petrov , V. A. Dokichev , and Yu. V. Tomilov
aInstitute of Organic Chemistry, Ufa Scientific Center, Russian Academy of Sciences,
Ufa, 450054 Russia
e-mail: dokichev@anrb.ru
Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow
b
Received February 17, 2010
Abstract—The hydrogenation on Raney nickel of 3-alkenyl-substituted pyrazolines and also of 3-methyl-5-
(
1
2-furyl)-1H-pyrazoline and 3,3'-bipyrazoline afforded substituted 1,3-diaminobutanes, 1,3-diaminopentanes,
,3-diaminohexane, and 1,3,4,6-tetraaminohexane. Under the same conditions from 3-acetyl-4-(2-furyl)-1H-
pyrazoline 3-amino-2-methyl-4-(2-furyl)pyrrolidine was obtained.
DOI: 10.1134/S1070428011020035
Polymethylene polyamines are found in all living 1-amino-2-pyrrolidone were obtained [12].
cells, they are involved in many important biological
In the present study aiming at the synthesis of new
processes and possess a wide range of physiological
compounds of this series, in particular, of 1,3-propyl-
activity ( tuberculocidal, immunodepressant, antitumor
enediamines of linear structure the hydrogenation was
etc.) [1–3]. Recent research showed that the polyamine
investigated of 3-vinyl- (Ia), cis-3-[(1E)-prop-1-en-1-
yl]- (Ib), 3-isopropenyl-4,5-dihydro-3H-pyrazole (Ic),
-isopropenyl-3-methyl-4,5-dihydro-3H-pyrazole (Id),
-methyl-5-(2-furyl)-4,5-dihydro-1H-pyrazole (II),
-acetyl-4-(2-furyl)-4,5-dihydro-1H-pyrazole (III), and
,4',5,5'-tetrahydro-3H,3'H-3,3'-bipyrazole (IV).
derivatives based on spermidine and spermine exhibit
high activity against Alzheimer’s disease, cystic fibro-
3
3
3
4
sis, and also of various tumors and cancer cells [4–7].
,3-Propylenediamine fragment are included into the
1
structure of many drugs used in the treatment of the
central nervous system [e.g., antidepressant imipramine
The hydrogenation was carried out in a steel rotating
(tofranil)] [3]. The modification of the terminal fragments
pressure reactor in methanol over Raney nickel at 100°C
and the hydrogen pressure 10–13 MPa over 6 h. Under
the chosen conditions pyrazolines Ia–Id with various
vinyl substituents in the position 3 cleanly converted
into the corresponding 1,3-propylenediamines Va–Vd
in 87–99% yields. In none of performed experiments
the formation of side products was detected originating
from the characteristic of 3-vinylpyrazolines catalytic or
thermal dediazotization of the pyrazoline ring [13–15].
of poly-β-aminoesters with the help of 1,3-diaminopen-
tane improved the biophysical properties of biodegradable
polymeric nanoparticles formed as a result of the selfas-
sembling of the DNAplasmids, and of the hydrolytically
degradable poly-β-aminoesters favoring the effective
function of the nonviral gene transfer to the embryonic
human cells (hESCs) [8].
One convenient method of preparation of 1,3-propyl-
enediamines consists in the hydrogenation over Raney Ni
under hydrogen pressure of alkyl- and aryl-substituted
pyrazolines [9–11]. By this procedure only 1,3-propyl-
enediamines with branched hydrocarbon chain were
prepared [9–11]. As known, the hydrogenation direction
depends also on the character of the substituent in the
initial pyrazoline. For instance, the 1-benzyl-3,5,5-
trimethylpyrazoline was converted into toluene, and from
methyl 1H-pyrazoline-3-carboxylates derivatives of 3- or
R2
R2
R1
R1
Ni/Ra, H2
R3
R3
N
N
H N NH2
2
_
_
Ia Id
Va Vd
1
2
3
1
2
3
1
R = R = R = H (a); R = R = H, R = Me (b); R =
3
2
1
2
3
R = H, R = Me (c); R = R = Me, R = H (d).
1
68

CATALYTIC SYNTHESIS OF 1,3-PROPYLENEDIAMINES
Scheme 1.
169
The hydrogenation of 3-methyl-5-(2-furyl)-4,5-
dihydro-1H-pyrazole (II) containing a furan substituent
in the position 5 of the heterocycle proceeded both at the
pyrazoline fragment and the C=C bonds of furan ring.
We isolated from the reaction mixture 1,3-diamino-1-(2-
furyl)butane (VI) and 1,3-diamino-1-(2-tetrahydrofuryl)
butane (VII) in 9 and 68% yield respectively. 1,3-Diami-
nobutane (VII) was present as a mixture of diastereomers
COMe
COMe
NH2
Ni/Ra, H
2
N
NH
NH2
O
O
III
A
NH2
1
3
in the ratio 1 : 1.5 (according to C NMR data).
Ni/Ra, H2
NH
O
VIII
N
NH2
O
O
HN
II
H N
2
VI
The composition and structure of compounds obtained
1
13
was proved by mass, IR, H and C NMR spectra. For
instance, the presence in the IR spectra of the absorption
+
NH2
O
–1
H N
VII
bands of NH groups in the region 3115–3356 cm
2
2
confirmed the formation of the amine fragment. In the
1
H NMR spectra the proton signals of NH and NH
2
Under the chosen conditions the only product of the
catalytic reduction of 3-acetyl-4-(2-furyl)-4,5-dihydro-
groups appear as broadened singlets in the region 1.25–
Scheme 2.
1
H-pyrazole (III) was 3-amino-2-methyl-4-(2-furyl)
pyrrolodine (VIII) obtained in 84% yield due to the
intramolecular condensation of diamine A (Scheme 1).
NH2
+
O
The structure of compound VIII was proved by
m/z 122.06
1
NMR and mass spectra. In the H NMR spectrum the
.
_
NH CH2_CH
_
proton signal of the methyl group gives rise to a doublet
3
+
+
.
.
at 1.26 ppm, and signals of NH and NH groups appear
2
NH2
as a broad singlet at 1.72 ppm. The proton signals of the
_NH3
O
O
2
3
pyrrolodine ring at the atoms C and C are observed as
a multiplet (2.76–2.90 ppm) and a doublet of doublets
HN
HN
3
3
m/z 149.09
VIII, m/z 166.11
(
3.31 ppm), J 9.9 and J 10.2 Hz. The characteristic
3
'
4'
5'
2'
_
NH CH2_CH3
_
signals of the atoms C , C , C , C of the furan ring ap-
pear in the C NMR spectrum at 104.99, 110.00, 141.53,
2
13
+
.
1
55.74 ppm respectively.
NH
The mass spectrum of compound VIII contained
O
m/z 121.07
the molecular ion peak, m/z 166.1103. The intensity of
the molecular ion peaks of all synthesized 1,3-propyl-
enediamines was very low (<0.1%). The interpretation
of the mass spectrum of heterocycle VIII underlain by
the concept of charge and unpaired electron localiza-
tion showed that the characteristic diagnostic fragments
+
.
+
CH2
.
.
_
_
NH
O
O
H N
2
NH2
m/z 110.06
m/z 94.04
formed by elimination of NH and the decomposition of
3
the nitrogen heterocycle.
N
NH2
H N
2
N
The reduction of 4,4',5,5'-tetrahydro-3H,3'H-3,3'-bi-
pyrazole (IV) gave 1,3,4,6-tetraaminohexane (IX) in 99%
yield as a difficultly separable diastereomeric mixture in
Ni/Ra, H
2
N N
H N NH2
2
13
the ratio 1 : 1.2 (according to C NMR data) (Scheme 2).
IV
IX
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 2 2011

170
YAKOVLEV et al.
3
+
2
.51 ppm. The signals of atoms C (49.40–54.47 ppm)
41 (25). M 110.1466. C H N . M 110.1571.
6 10 2
in the 13C NMR spectra of 1,3-propylenediamines are
located downfield as compared with the signals of atom
General procedure of pyrazolines hydrogenation.
In a steel rotating pressure reactor (V 100 cm ) was
3
1
C (39.56–42.39 ppm).
charged the pyrazoline solution in 20 ml of MeOH, Raney
nickel prepared from 0.16 g of nickel-aluminum alloy, and
the reaction mixture was maintained for 6 h at 100°C and
hydrogen pressure 10–13 MPa. The catalyst was filtered
off, the solvent was distilled off at a reduced pressure.
Therefore the catalytic hydrogenation of vinyl-
substituted pyrazolines with hydrogen in the presence of
Raney nickel makes it possible to obtain the corresponding
1
,3-diamines which at the presence of a keto group in the
molecule immediately transform into pyrrolodines.
1
,3-Diaminopentane (Va). From 1 g (0.01 mol) of
pyrazoline Ia was obtained 0.89 g (87%) of diamine
Va. IR spectrum, ν, cm : 3334–3257, 2958–2873,
EXPERIMENTAL
–
1
1
1
575–1436, 1319 (NH ). H (NMR spectrum CDCl ), δ,
2
3
1
13
H and C NMR spectra were registered on a spec-
trometer Bruker AM-300 (300.13 and 75.47 MHz re-
2
4
ppm: 0.87 t (3H, Me, J 7.3 Hz), 1.18–1.58 m (4H, H , H ),
.64 br.s (4H, NH ), 2.68 m (1H, H ), 2.82 m (2H, H ).
3
1
1
13
2
spectively), internal reference Me Si. IR spectra were re-
4
C NMR spectrum (CDCl ), δ, ppm: 10.11 (Me), 30.87
3
corded on spectrophotometers UR-20 and Specord M-80
from thin films. Mass spectra were obtained on a liquid
chromato-mass spectrometer Shimadzu LCMS-2010EV
in the chemical ionization mode at the atmospheric
pressure, and on a high resolution GC-MS instrument
Thermo Finnigan MAT 95 XP at the ionizing electrons
energy 70 eV (ionizing chamber temperature 250°C, direct
sample admission at 50–270°C, heating rate 10 deg/min).
4
2
1
3
(
(
C ), 39.21 (C ), 40.06 (C ), 50.89 (C ). Mass spectrum
+
Chemical ionization): m/z 103 [M + H] . Mass spectrum,
m/z (I , %): 85 (54) [M – NH ] , 73 (11) [M – Et] , 72
+
+
rel
3
+
(
69) [M – NH – CH ] , 58 (100) [M – NH – CH –
2 2 2 2
+
+
CH ] , 56 (68), 44 (84) [NH CH CH ] , 41 (27), 32 (99),
9 (83). M 102.0933. C H N . M 102.1781.
5 14 2
2
2
2
2
+
2
The physicochemical constants of 1,3-diaminopentane
Va coincided with the published data [19].
,3-Diaminohexane (Vb). From 1 g (0.009 mol) of
pyrazoline Ib was obtained 1.03 g (99%) of diamine Vb.
Initial compounds Ia, Ic,Id, II–IV were prepared by
procedures [13, 14, 16–18].
1
Raney nickel. To a mixture of 160 mg of powdery
nickel-aluminum alloy (50/50) in 6 ml of water was added
within 20–25 min 4.0 g (0.1 mol) of NaOH. The mixture
was heated at 40–45°C till total end of gas evolution. The
Raney nickel was washed with distilled water till neutral
washings, the with MeOH (5×5–6 ml).
–1
IR spectrum, ν, cm : 3356–3196, 2956–2872, 1600,
1
1
450, 1379, 1035 (NH ). H NMR spectrum (CDCl ),
2
3
δ, ppm: 0.88 t (3H, Me, J 5.7 Hz), 1.18–1.52 m, (6H,
H2,4,5), 1.71 br.s (4H, NH ), 2.58–2.86 m (3H, H1,3).
2
1
3
C NMR spectrum (CDCl ), δ, ppm: 13.83 (Me), 18.88
3
5
4
2
1
3
(C ), 38.84 (C ), 40.23 (C ), 40.49 (C ), 49.40 (C ).
Mass spectrum (Chemical ionization): m/z 117 [M +
3
-Isopropenyl-4,5-dihydro-3H-pyrazole (Ic). To
+
+
H] . Mass spectrum: m/z (I , %): 99 (17) [M – NH ] ,
7
8 g (0.48 mol) of isoprene was added 243 ml of ether so-
lution of diazomethane prepared from 24.3 g (0.236 mol)
of N-methyl-N-nitrosourea, and the mixture was left for
8 h in the dark at room temperature. The solvent was
removed at a reduced pressure. The residue was distilled
rel
3
+
+
8
(
[
6 (9) [M – NH – CH ] , 84 (12) [M – NH – Me] , 73
2 2 3
10) [M – Pr] , 72 (42) [M – NH – CH – CH ] , 70 (13)
M – NH – Et] , 56 (36), 44 (98), 42 (13). M 116.0953.
+
+
2 2 2
+
+
4
3
C H N . M 116.2047.
6
16
2
in a vacuum. Yield 12.43 g (64%), light-yellow oily fluid,
bp 40°C (1 kPa). IR spectrum, ν, cm : 2974, 1649 (C=C),
1,3-Diamino-4-methylpentane (Vc). From 1 g
–1
(0.009 mol) of pyrazoline Ic was obtained 0.99 g (95%)
1
–1
1
(
548 (N=N), 1456, 1375, 1278, 898. H NMR spectrum
of diamine Vc. IR spectrum, ν, cm : 3358–3197, 2936–
4
1
CDCl ), δ, ppm: 1.19–1.31 m (1H, H ), 1.65 br.s (3H,
Me), 1.65–1.74 m (1H, H ), 4.10–4.20 m (1H, H ), 4.47–
.51 m (1H, H ), 4.74 t (1H, H , J 8.7 Hz), 4.84 br.s (1H,
H ), 4.86 br.s (1H, H ). C NMR spectrum (CDCl ),
δ, ppm: 19.02 (Me), 21.21 (C ), 75.34 (C ), 91.46 (C ),
11.85 (C ), 141.50 (C ). Mass spectrum (Chemical
ionization): m/z 111 [M + H] . Mass spectrum, m/z (I ,
): 82 (25) [M – N ] , 81 (13), 67 (100), 65 (12), 53 (14),
2870, 1597, 1465, 1384, 1367, 1041, 848 (NH ). H NMR
3
2
4
5
spectrum (CDCl ), δ, ppm: 0.77 d (3H, Me, J 6.8 Hz),
3
5
1'
4
4
0.81 d (3H, Me, J 6.8 Hz), 1.15–1.35 m (1H, H ), 1.37–
1.57 m (2H, H ), 1.7 br.s (4H, NH ), 2.41–2.55 m (1H,
H ), 2.65–2.87 m (2H, H ). C NMR spectrum (CDCl ),
3
δ, ppm: 16.60 (Me), 16.68 (Me), 33.50 (C ), 37.64 (C ),
39.56 (C ), 54.47 (C ). Mass spectrum (Chemical ioniza-
tion): m/z 117 [M + H] . Mass spectrum, m/z (I , %):
2'
2' 13
2
3
2
4
5
3
3
1
13
2
'
1'
4
2
1
+
1
3
rel
+
+
%
2
rel
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 2 2011

CATALYTIC SYNTHESIS OF 1,3-PROPYLENEDIAMINES
171
+
+
2
3
1
5'
3'
2'
4'
9
[
4
9 (17) [M – NH ] , 84 (12) [M – NH – Me] , 73 (10)
3 3
(C ), 45.26 (C ), 54.04 (C ), 67.64 (C ), 83.99 (C ); main
+
+
M – i-Pr] , 72 (42) [M – NH – CH – CH ] , 56 (24),
4 (100). M 116.0943. C H N . M 116.2047.
diastereomer: 24.54 (Me), 25.62 (C ), 28.16 (C ), 43.41
2
2
2
+
2
3
1
5'
2'
(C ), 45.66 (C ), 52.33 (C ), 68.02 (C ), 83.21 (C ). Mass
6
16
2
+
spectrum (Chemical ionization): m/z 159 [M + H] . Mass
spectrum, m/z (I , %): 141 (1) [M – NH ] , 115 (3) [M –
NH2=CHCH3] , 100 (3) [M – NH2=CHCH3 – Me] , 87
1
,3-Diamino-3,4-dimethylpentane (Vd). From
g (0.008 mol) of pyrazoline Id was obtained 1.04 g
99%) of diamine Vd. IR spectrum, ν, cm : 3340–3163,
026–2816, 1598, 1452, 1384, 1375, 1039, 906 (NH2).
+
1
(
3
1
rel
3
+
+
–
1
+
(
25) [M – O=CHCH CH(CH )NH ] , 70 (7), 44 (100).
2
3
2
+
M 158.2265. C H N O. M 158.2414.
8
18
2
H NMR spectrum (CDCl ), δ, ppm: 0.83 d (3H, Me,
3
3
-Amino-2-methyl-4-(2-furyl)pyrrolodine (VIII).
J 6.9 Hz), 0.84 d (3H, Me, J 6.9 Hz), 0.95 s (3H, 5-Me),
2
4
From 513 mg (0.0028 mol) of pyrazoline III in the pres-
ence of Ni-Ra prepared from 0.08 g of nickel-aluminum
alloy was obtained 389 mg (84%) of pyrrolodine VIII.
IR spectrum, ν, cm : 3354–3115, 2962–2873, 1589,
1509, 1452, 1375, 1010, 734 (NH ). H NMR spectrum
(CDCl ), δ, ppm: 1.26 d (3H, Me, J 6.0 Hz), 1.72 br.s
3
(3H, NH , NH), 2.76–2.90 m (2H, H , H ), 3.01 m (1H,
H ), 3.16 d.d (1H, H , J 7.4, J 11.3 Hz), 3.31 d.d (1H,
H , J 9.9, J 10.2 Hz), 6.08 d (1H, H , J 2.7 Hz), 6.29 t
1
.48 t (2H, H , J 7.9 Hz), 1.50 m (1H, H ), 2.50 br.s
1
1
(
4H, NH ), 2.72 t (1H, H , J 7.5 Hz), 2.73 t (1H, H ,
2
1
3
J 7.9 Hz). C NMR spectrum (CDCl ), δ, ppm: 16.46
3
–
1
5
4
2
(
Me), 16.89 (Me), 24.03 (C ), 36.79 (C ), 36.95 (C ),
1
1
3
42.39 (C ), 53.08 (C ). Mass spectrum (Chemical ioniza-
2
+
tion): m/z 131 [M + H] . Mass spectrum, m/z (I , %):
rel
5
4
+
+
113 (2) [M – NH ] , 98 (2) [M – NH – Me] , 87 (25)
2
3
3
2
5
+
+
[
M – i-Pr] , 86 (34) [M – NH – CH – CH ] , 70 (17),
2 2 2
3
3'
+
5
8 (100), 44 (12), 43 (13), 41 (9), 29 (29). M 130.1465.
4
'
5'
(
1H, H , J 1.8, J 2.7 Hz), 7.33 d (1H, H , J 1.8 Hz).
C H N . M 130.2313.
7
18
2
1
3
C NMR spectrum (CDCl ), δ, ppm: 18.54 (Me), 49.10
3
2
Hydrogenation of 3-methyl-5-(2-furyl)-4,5-
dihydro-1H-pyrazole (II). From 1 g (0.007 mol) of
pyrazoline II in the presence of Ni-Ra prepared from
5
4
3
3'
(
1
(
C ), 50.23 (C ), 62.13 (C ), 65.13 (C ), 104.99 (C ),
4
'
5'
2'
10.00 (C ), 141.53 (C ), 155.74 (C ). Mass spectrum
Chemical ionization): m/z 167 [M + H] . Mass spectrum,
m/z (I , %): 166 (16) [M] , 149 (46) [M – NH ] , 121
11), 110 (24) [C H NO] , 94 (70) [C H O] , 80 (10), 57
7 8 6 6
+
0
.16 g of nickel-aluminum alloy was obtained 0.81 g of
a mixture of compounds VI and VII in the yields 9 and
8% respectively.
,3-Diamino-1-(2-furyl)butane (VI). IR spectrum,
+
+
rel
3
+
+
(
(
6
+
+
100) [C H N] , 56 (25), 44 (10), 39 (6). M 166.1103.
3
7
1
C H N O. Calculated M 166.2203.
9
14
2
–
1
ν, cm : 3354–3277, 2928–2868, 1589, 1064, 921
1
,3,4,6-Tetraaminohexane (IX). From 1 g (0.007 mol)
of pyrazoline IV in the presence of Ni-Ra, prepared from
.22 g of nickel-aluminum alloy was obtained 1.02 g
99%) of tetraamine IX as a mixture of two diastereomers
in the ratio 1 : 1.2 differing in the position of signals in
1
(
NH ). H NMR spectrum (CDCl ), δ, ppm: 1.19 d (3H,
2
3
Me, J 6.2 Hz), 1.43 br.s (4H, NH ), 1.8–2.0 m (2H,
2
0
(
2
3
1
H ), 2.72–2.80 m (1H, H ), 4.03 t (1H, H , J 7.7 Hz),
.13 m (1H, H ), 6.33 m (1H, H ), 7.35 m (1H, H ).
C NMR spectrum (CDCl ), δ, ppm: 24.92 (Me), 45.98
C ), 45.05 (C ), 50.66 (C ), 103.69 (C ), 109.73 (C )
40.95 (C ), 159.15 (C ). Mass spectrum (Chemical
ionization): m/z 155 [M + H] . M 154.2095. C H N O.
3
'
4'
5'
6
1
3
3
13
–1
the C NMR spectrum. IR spectrum, ν, cm : 3356–3275,
2
3
1
3'
4'
(
1
1
2
(
926–2868, 1585, 1480, 921 (NH ). H NMR spectrum
CDCl ), δ, ppm: 1.25–1.80 m (12H, NH , H ), 2.70–
3.00 m (6H, H
2
5
'
2'
2,5
3
2
+
+
1,3,4,6 13
8
14
2
). C NMR spectrum (CDCl ), δ,
3
M 154.2096.
,3-Diamino-1-(2-tetrahydrofuryl)butane (VII).
A mixture of two diastereomers in the ratio 1:1.5 differ-
2
1
ppm, minor diastereomer: 37.54 (C ), 39.26 (C ), 39.41
1
b
3
2
1
(C ) 54.28 (C ); main diastereomer: 35.48 (C ), 39.41
1
3
(C ), 53.59 (C ). Mass spectrum (XAND): m/z 147 [M +
1
3
H]+. C H N . Calculated M 146.2341.
ing in the position of signals in the C NMR spectrum.
6
18
4
–
1
IR spectrum, ν, cm : 3354–3277, 2928–2868, 1589,
1
ACKNOWLEDGMENTS
1
1
1
2
(
3
064, 921 (NH ). H NMR spectrum (CDCl ), δ, ppm:
2
3
3
',4'
.19 d (6H, Me, J 6.2 Hz), 1.20–1.80 m (8H, H ),
2
The study was carried out under the financial support
of the Presidium of the Russian Academy of Sciences
(program “Development of preparation methods for
chemical substances and creation of new materials” from
the direction “Development of the methodology of the
organic synthesis and creation of compounds with valu-
.43 br.s (8H, NH ), 1.88 d.d (4H, H , J 6.0, J 6.4 Hz),
2
3
.61–2.74 m (1H, H , minor diastereomer), 2.91–3.05 m
1H, H , main diastereomer), 3.05–3.16 m (2H, H ),
.52–3.61 m (1H, H , minor diastereomer), 3.62–3.91 m
5H, H2',5'). C NMR spectrum (CDCl ), δ, ppm, minor
3
1
5
'
13
(
3
3
'
4'
diastereomer: 24.14 (Me), 25.90 (C ), 28.16 (C ), 43.55
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