Chemistry of diazocarbonyl compounds: XVIII. Synthesis and spectral parameters of 1,3-dialkyl- 3-hydroxy-2-diazoketones

Article abstract of DOI:10.1023/B:RUJO.0000034964.50578.fb

Reduction of the carbonyl groups in cyclic and acyclic 2-diazo-1,3- diketones with sodium tetrahydridoborate in aqueous-alcoholic medium, followed by hydrolysis of the reaction mixture over wet silica gel and chromatographic purification on neutral alumin

Full text of DOI:10.1023/B:RUJO.0000034964.50578.fb

Russian Journal of Organic Chemistry, Vol. 40, No. 3, 2004, pp. 316–328. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 3, 2004,
pp. 348–359.
Original Russian Text Copyright © 2004 by Zhdanova, Korneev, Nikolaev.
Chemistry of Diazocarbonyl Compounds:
XVIII.* Synthesis and Spectral Parameters of 1,3-Dialkyl-
3-hydroxy-2-diazoketones
O. V. Zhdanova, S. M. Korneev, and V. A. Nikolaev
St. Petersburg State University, Universitetskii pr. 26, St. Petersburg, 198504 Russia
e-mail: vnikola@VN6646.spb.edu
Received March 15, 2003
Abstract—Reduction of the carbonyl groups in cyclic and acyclic 2-diazo-1,3-diketones with sodium tetra-
hydridoborate in aqueous–alcoholic medium, followed by hydrolysis of the reaction mixture over wet silica gel
and chromatographic purification on neutral aluminum oxide, afforded 1,3-dialkyl-3-hydroxy-2-diazoketones
in 58–87% yield. Bulky substituents at the carbonyl group considerably reduce the efficiency of the process,
and the reduction of cis- and trans-4,6-di-tert-butyl-2-diazocyclohexane-1,3-diones is characterized by low
stereoselectivity (de 40–49%). In the IR spectra of 3-hydroxy-2-diazocyclohexanes, absorption bands
corresponding to stretching vibrations of “free” axial hydroxy groups are located at higher frequencies (by 20–
45 cm–1) than those belonging to equatorial hydroxy groups. These parameters may be useful for
conformational analysis of cyclic hydroxy diazo ketones. Stabilization of the E conformation of acyclic
hydroxy diazo ketones via intramolecular hydrogen bonding is likely to occur only in nonpolar solvents (CCl4,
cyclohexane).
Hydroxy diazo ketones attract much attention due
to diverse synthetic potential of these compounds
which possess three reactive functional groups (C=O,
C=N2, OH) and their utility for target-oriented
synthesis of natural and other compounds, as well as
for studying various theoretical aspects of organic
chemistry [2].
of published data showed that hydroxydiazocarbonyl
compounds are usually synthesized according to the
following approaches (Scheme 1): (a) building up of
a target molecule from two components (synthons),
one of which contains a diazo group, and the other,
a carbonyl group; (b) modification of one carbonyl
group in a diazodicarbonyl compound without
changing the original carbon skeleton.
In order to elucidate stereochemical relations
holding in 1,2-nucleophilic rearrangements of diazo
ketones having different conformations of the CO–CN2
moiety, it was necessary to synthesize a series of
1,3-dialkyl-substituted cyclic and acyclic hydroxy
diazo ketones I. Diazo ketones I were expected to exist
as Z and E isomers with respect to the CO–CN2 bond;
therefore, they could be convenient models for
studying the structure–reactivity relations [3]. Analysis
Scheme 1.
O
N2
+
R'CHO
O
a
b
N2
R
O
OH
N2
H
R
R'
O
R
R'
H
N2
O
O
For a long time [4], method a has been used most
widely. It involves condensation of aldehydes [5] or
ketones [6] with 2-diazocarbonyl compounds in the
absence of a catalyst or by the action of strong bases.
The reaction follows a scheme analogous to aldol
condensation. Most acyclic 3-hydroxy-2-diazocarbonyl
O
OH
H
R'
R
H
R
R'
N2
E Isomer
Z Isomer
* For communication XVII, see [1].
1070-4280/04/4003-0316 © 2004 MAIK “Nauka/Interperiodica”

CHEMISTRY OF DIAZOCARBONYL COMPOUNDS: XVIII.
317
Scheme 2.
ditions for reduction of 1,3-dialkyl-2-diazo-1,3-di-
ketones with a view to obtain the corresponding
3-hydroxy-2-diazoketones [13].
O
O
OH
O
B
X
R1
R2
+
R1
R2
R3
R3
In the present article we describe the synthesis of
cyclic and acyclic 3-hydroxy-2-diazoketones I by
reduction of one carbonyl group in diazo diketones
IIa–IIj with sodium tetrahydridoborate or trihydro-
(trifluoroacetyl)borate (Scheme 3) and discuss some
spectral parameters of compounds I. The conditions
for the synthesis and isolation of 3-hydroxy-2-diazo-
ketones I were optimized using diazodimedone (IIc),
dipropionyldiazomethane (IIi), diazoindandione (IIa)
and dibenzoyldiazomethane (IIg) as substrates. Such
parameters as reactant ratio, solvent, temperature,
reaction time, reducing agent, hydrolysis conditions,
sorbent for chromatographic purification, and some
others were varied (Table 1). As a result, the following
conditions were found to be optimal for the synthesis
of both cyclic and acyclic 3-hydroxy-2-diazoketones I:
N2
N2
R1, R2 = H, Alk, Ar; R3 = OAlk, Alk; X = H, SiMe3, SnBu3,
etc.; B = OH–, BuLi, (i-Pr)2NLi, etc.
compounds having as a rule an alkoxycarbonyl group
(R3 = OAlk) were prepared in this way, and some
cyclic 3-hydroxy-3-alkyl(aryl)-2-diazoketones were
obtained by intramolecular condensation of the diazo
and carbonyl groups [7] (Scheme 2).
Up to now, alternative approach b to building up
3-hydroxy-2-diazocarbonyl fragment was applied very
rarely [8, 9]. An example is the reduction of bicyclic
diazo diketone of the aromatic series (diazoindandi-
one) with sodium tetrahydridoborate, which gave
55% of 2-diazo-3-hydroxyindan-1-one [8]. The same
scheme was later used to prepare acyclic 3-hydroxy-2-
diazoesters (R3 = OAlk) [9] which can be regarded as
alkoxycarbonyl analogs of hydroxy diazo ketones I
(R = Alk); the products were brought into subsequent
transformations without isolation from the reaction
mixture.
(1) Molar reactant ratio diazo diketone II–reducing
agent 1:(0.35–0.8); it is advisable to add sodium tetra-
hydridoborate to the reaction mixture in 2–3 portions;
(2) Reaction time 20–60 min; temperature 2–20°C.
Increase of the reaction time to 3–4 h usually leads to
an appreciable decrease in the yield of hydroxy diazo
ketones I;
(3) Hydrolysis of the reaction mixture should be
performed using neutral silica gel containing 10% of
H2O (0.5–1.0 g of SiO2 per mmole of diazo diketone).
In the synthesis of cyclic hydroxy diazo ketones I,
silica gel can be added directly to the reaction mixture
for 5–6 min, or the mixture can be filtered over
a period of 5–6 min through a layer of silica gel. In
the synthesis of acyclic hydroxy diazo ketones I, it
is better to reduce the time of contact with silica gel to
1–2 min, for these compounds readily undergo further
transformations on silica gel;
Taking into account accessibility of initial 2-diazo-
1,3-diketones [10–12], method b seemed to be the
most promising for the synthesis of 3-hydroxy-2-
diazoketones I. However, our first attempts to apply
the reduction procedure reported in [8] to diazo
diketones having alkyl substituents at the carbonyl
group (unlike diazoindandione) were unsuccessful.
Therefore, we performed a detailed study of the con-
Scheme 3.
N2
N2
(1) NaBH4–EtOH–H2O
(2) SiO2–H2O
O
O
O
OH
(4) The use of methanol [9] or ethanol as solvent
and dilution of the reaction mixture with water [8] con-
siderably reduce the yield of hydroxy diazo ketones I.
H
R
R'
R
R'
Ia–Im
IIa–IIk
Under the above conditions, the reaction mixture
almost always contains an appreciable amount of
unreacted initial diazo diketone II (Table 1, run nos. 3–
14). However, our attempts to raise the conversion by
increasing the amount of reducing agent or reaction
time gave no desired result. When initial diazo
diketone II disappeared from the reaction mixture
(usually, in 5–6 h according to the TLC data), the
yields of hydroxy diazo ketones I were considerably
lower than under standard conditions (20–45 min).
Me
I, II, RR' =
(a),
(b),
(c),
Me
Me
Me
t-Bu
t-Bu
(d),
(e, l),
(j, k),
Me
Me
t-Bu
t-Bu
R = R' = Ph (g), Me (h), Et (i), i-Pr (j), t-Bu (k).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 3 2004

ZHDANOVA et al.
318
Table 1. Reduction of diazo diketones IIa, IIc, IIe, and IIg–IIi with sodium tetrahydridoborate
Reaction conditions
Yield,a %
Run
no.
Comp.
no.
molar ratio
II–NaBH4
reaction
time, h
temperature,
°C
methodb
I
II
1
2
IIa
IIa
IIa
IIa
IIc
IIc
IIc
IIc
IIc
IIc
IIe
IIe
IIe
IIe
IIg
IIg
IIg
IIg
IIi
1:1
0.1
0.25
0.3
0.25
0.25
0.8
0.8
0.8
2
15
3
[8]
a
55
63
75
77
1–2c
30
43
65
39
53
23e
30e
31e
29e
24
41
–
2
2
1:0.5
3
1:0.35
3
a
24
11
26
39
47
41
36
18
68
41
30
29
59f
15f
34f
53f, h
–
4
1:1
3
c
5
1:1
15
3
[8]
a
6
1:1
7
1:(0.5 + 0.3)
1:(0.5 + 0.3)
1:(0.5 + 0.3)
1:1
3
a
ad
8
3
9
3, 20
3
a
10
11
12
13
14
15
16
17
18
19
20
21
0.5
2
c
1:(0.5 + 0.3)
1:(0.5 + 0.3)
1:(2 + 1)
1:(1 + 2)
1:0.5
3
a
24
3, 20
3
a
2.5
20
b
20
3
b
0.3
1.5
1.5
1.5
0.5
0.7
1.0
a
ag
1:(0.5 + 0.3)
1:1
3
3
a
1:1
3
c
–
1:(0.3 + 0.2)
1:(0.5 + 0.2)
1:(0.5 + 0.2)
3
a
49
58
47
IIi
3
a
–
IIi
3
a
–
a
Given are yields of chromatographically pure compounds I and II.
Ethanol was used as solvent with subsequent addition of 15% of water (as a solution of NaBH4). Methods a–c are described in
Experimental.
Yield of 2-diazo-5,5-dimethyl-3-cyclohexenone.
A 20-mmol portion of compound IIc was reduced.
Overall yield of stereoisomers Ie and Il.
Yield of benzoyldiazomethane (IIIg).
The reaction was carried out in THF.
Benzyl alcohol (31%) was isolated in addition to benzoyldiazomethane (IIIg) (53%).
b
c
d
e
f
g
h
Presumably, the transformation of diazo diketones II
into hydroxy diazo compounds I is accompanied by
further reduction of the latter, e.g., to diazoalkane-1,3-
diols which are likely to be unstable (they decompose
during the reaction and/or isolation procedure).
Sodium trihydro(trifluoroacetyl)borate as reducing
agent showed no appreciable advantages with respect
to NaBH4 (Table 1, run nos. 4, 10, 18).
(Table 1, run nos. 3, 4). The reduction of its acyclic
analog, dibenzoyldiazomethane (IIg) was less selective
(Table 1, run nos. 15–18): the major products were
benzoyldiazomethane (IIIg) (run no. 15–17) and
benzyl alcohol (run no. 18). Taking into account that
condensation of diazo ketones with aldehydes and
ketones [4, 5] is a reversible process, we presume that
hydroxy diazo ketone Ig is partially converted into
benzoyldiazomethane IIIg and benzaldehyde which is
then reduced to benzyl alcohol (Scheme 4). Also,
another way of formation of diazo compound IIIg
among the reaction products cannot be ruled out. It
In the reduction of diazoindandione IIa under
optimized conditions, the yield of hydroxy diazo
ketone Ia was greater by a factor of ~1.5 than in
the synthesis according to the known procedure [8]
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 3 2004

CHEMISTRY OF DIAZOCARBONYL COMPOUNDS: XVIII.
319
Scheme 4.
The reduction of epimeric cis- and trans-di-tert-
butyl diazo diketones IIe and IIf with sodium tetra-
hydridoborate gave two pairs of diastereoisomeric
hydroxy diazo ketones Ie/Il and If/Im in a low yield
(Scheme 5; Tables 1, 2). Pure stereoisomers Ie, If, Il,
and Im were isolated by chromatography on neutral
aluminum oxide, and their configuration was deter-
H
O
O
O
O
[H], H2O
H
Ph
Ph
Ph
Ph
N2
N2
IIg
1
mined by H NMR spectroscopy (see below). The
O
ratios of the isomers with axial and equatorial
orientation of the hydroxy group (ax/eq) in pairs Ie/Il
and If/Im differ considerably and are 1:3 and 2.4:1,
respectively. On the whole, these data are quite
consistent with the empirical rules which were drawn
for the reduction of simple cyclohexanones with
sodium tetrahydridoborate [15]: In the reaction with
sterically less hindered cis-diazo diketone IIe, axial
attack on the carbonyl group by the reducing agent is
H
+
PhCHO
Ph
N2
IIIg
involves partial hydrolysis of initial diazo diketone
IIg to benzoyldiazomethane IIIg and benzoic acid
(and then benzyl alcohol), which is typical of aryl-
substituted diazo diketones [14].
Table 2. Yields, decomposition points (or relative densities, or refractive indices), Rf values, and elemental analyses of
hydroxy diazo ketones Ia–If, Ih–Ij, Il, and Im
Found, %
Calculated, %
Comp.
no.
Yield,a Decomposition point,
b
Rf
Formula
%
°C (solvent)
C
–
H
–
N
–
C
–
H
–
N
–
77 (85)
65 (76)
118–119 [8]
–
–
–
Ia
Ib
61–62 (ether)
51.71
51.47
5.77
5.80
19.86
19.79
C6H8N2O2
51.42
57.12
61.20
66.63
66.63
5.75
7.19
8.22
9.59
9.59
19.99
49 (65)
86 (87)
8 (17)
8 (11)
65–66 (ether)
–
–
56.87
56.90
7.26
7.24
17.03
17.03
C8H12N2O2
C10H16N2O2
C14H24N2O2
C14H24N2O2
16.65
14.28
11.10
11.10
Ic
Id
Ie
If
53–54 (hexane–
ether, 6:1)
61.11
61.58
8.37
8.12
14.58
14.53
86–87 (pentane–
ether, 1:1)
0.53
0.43
66.43
66.19
9.56
9.36
10.08
9.98
c
81–82 (pentane–
ether, 1:1)
66.79
66.41
c
9.89
9.49
c
c
c
55
1.5035d
–
–
C5H8N2O2
C7H12N2O2
46.88
53.83
6.29
7.74
21.86
17.94
Ih
Ii
47–58
1.4974d
53.78
53.81
7.23
7.19
1.0576e
c
49–62
23 (50)
18 (26)
1.4857d
1.0005e
–
58.58
58.47
9.05
9.00
C9H16N2O2
C14H24N2O2
C14H24N2O2
58.67
66.63
66.63
8.75
9.59
9.59
15.21
11.10
11.10
Ij
82–83 (hexane–
ether, 1:1)
0.39
0.39
65.91
65.98
9.62
9.47
11.17
10.83
Il
84–85 (hexane–
ether, 1:1)
66.13
65.95
9.55
9.51
10.53
10.76
Im
a
b
c
The optimal yields of hydroxy diazo ketones I are given; in parentheses are given the yields calculated on the reacted diazo diketone II.
Silufol UV-254 plates, hexane–diethyl ether, 1:1.
Hydroxy diazo ketones If and Ih–Ij decomposed to an appreciable extent even during preparation of the analyzer to operation (at 60–
70°C); therefore, satisfactory elemental analyses of these compounds were not obtained.
n2D0.
d240.
d
e
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 3 2004

ZHDANOVA et al.
320
Scheme 5.
IR spectra. Absorption bands due to stretching
N2
N2
vibrations of the C=N2 and C=O groups in the IR
spectra of cyclic (Ib–Id) and acyclic (Ih–Ij) hydroxy
diazo ketones are located in fairly narrow frequency
ranges: ν(C=N2) 2100–2120, 2070–2090 cm–1 and
ν(C=O) 1620–1650, 1630–1650 cm–1 (Table 3, see
Experimental). Comparison of these data with the
corresponding ν(C=N2) and ν(C=O) frequencies for
structurally similar diazo ketones and diazo diketones
(Table 4) shows that introduction of a hydroxy group
into the α-position with respect to the diazo group
leads to an appreciable increase (by 17–20 cm–1) of the
C=N2 stretching vibration frequency. As a rule,
increase in ν(CH2) in the IR spectrum of a diazo com-
pound correlates with increase in its thermal stability
and resistance to acids [10, 16, 17], e.g., as observed in
going from diazo ketones to diazodicarbonyl com-
pounds. However, such a pattern is not typical of
hydroxy diazo ketones I [13], and their stability is
comparable with that of diazo ketones.
O
O
O
OH
NaBH4
t-Bu
Bu-t
t-Bu
Bu-t
IIe (6-cis)
IIf (6-trans)
Ie (4-trans-6-cis), 8%
If (4-trans-6-trans), 18%
N2
O
OH
+
t-Bu
Bu-t
Il (4-cis-6-cis), 23%
IIf (4-cis-6-trans), 8%
likely to occur to give mainly eq-OH isomer Il; trans-
diazo diketone IIf is sterically overcrowded at both
sides of the ring, so that equatorial attack by hydride
ion prevails, and the resulting major stereoisomer If
has equatorial hydroxy group.
The possibility for formation of intramolecular
hydrogen bond in structurally related acyclic hydroxy-
diazocarbonyl compounds has already been discussed
in the literature [20], but no experimental proofs were
given. With the goal of elucidating this problem, we
studied in detail the effect of various parameters
on the IR spectra of cyclic and acyclic diazo com-
pounds I. We have found that the C=O and O–H
stretching vibration frequencies of hydroxy diazo
ketones I strongly depend on the solvent nature,
concentration, and other conditions for recording the
spectra and that the ν(C=N2) frequency almost does
not change. In the IR spectra of cyclic (Ic, Id) and
acyclic (Ii, Ij) hydroxy diazo ketones in nonpolar
solvents (CCl4, cyclohexane), the carbonyl group
generally gives rise to two absorption bands at 1612–
1642 and 1638–1651 cm–1; in the spectra of acyclic
hydroxy diazo ketones Ii and Ij, the positions of these
bands differ only slightly, so that one of these appears
as an inflection on the other (Table 3). Obviously, the
low-frequency component belongs to carbonyl group
involved in hydrogen bond, while the high-frequency
component corresponds to “free” carbonyl group. In
a strong proton-acceptor solvent, such as THF, we
observed bands only from carbonyl groups not
involved in hydrogen bonding, and in film, as well as
in KBr, only those belonging to H-bonded carbonyl
groups are present.
One of a few diazo diketones which failed to react
with sodium tetrahydridoborate under the above
conditions is dipivaloyldiazomethane (IIk). Obviously,
the presence of two bulky tert-butyl substituents at the
carbonyl groups in molecule IIk hamper approach of
the hydride species thereto. An analogous effect of
bulky groups was observed in an attempt to synthesize
dipivaloyldiazomethane (IIk) itself via conventional
diazo transfer reaction [12].
Table 2 gives the optimal yields, decomposition
points, and analytical data of hydroxy diazo ketones I.
Cyclic diazo ketones Ia–If, Il, and Im are relatively
stable light yellow crystalline substances which can be
stored at reduced temperature for a long time without
appreciable decomposition. Acyclic hydroxy diazo
ketones Ih–Ij are viscous oily substances which are
less thermally stable than their cyclic analogs; under
comparable conditions, they undergo appreciable
decomposition in several days. On raising the tempera-
ture to 50–60°C, fast decomposition of compounds
Ih–Ij occurs; therefore, as a rule they cannot be
distilled under a residual pressure of 10–3 to 10–2 mm.
The structure of diazo compounds I was reliably
determined by spectral methods. Unlike diazo ketones
[10, 16, 17] and diazodicarbonyl compounds [18],
physical properties and specific structural features of
3-hydroxy-2-diazoketones were studied very poorly
1
[3]. We examined the IR and H NMR spectra of
Variations observed in the region of hydroxy group
stretching vibrations are similar for hydroxy diazo
ketones Ic, Id and Ii, Ij. In the IR spectra recorded
a series of compounds I (Tables 3–5; Figs. 1, 2) and
drew some conclusions concerning their structure.
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CHEMISTRY OF DIAZOCARBONYL COMPOUNDS: XVIII.
321
Table 3. Principal parameters of the IR spectra of 2-diazo-3-hydroxyketones Ic, Id, Ii, and Ij in different solventsa
ν, cm–1 (absorption, %)
Comp.
no.
Solvent,
concentration, M
ν(C=O)
1618 (52), 1644 (44)
1620 (34), 1647 (52)
1627 (63)
ν(C=N2)
2109 (88)
2108 (88)
2110 (93)
2110 (89)
2106 (75)
2109 (73)
2120 (72)
ν(O–H)
3400 (20), 3595 (5), 3622 (5)
Ic
CCl4, 0.06
CCl4, 0.01
CHCl3, 0.06
CHCl3, 0.01
THF, 0.08
THF, 0.01
KBr
3420 (6), 3598 (10), 3628 (10)
3400 (8), 3590 (10), 3614 (12), 3685 (3)
3590 (10), 3615 (12), 3690 (6)
3400 (33)
1628 (55)
1647 (52)
1648 (49)
3410 (24)
1609 (69)
3455 (39)
Id
Ii
CCl4, 0.06
CCl4, 0.01
CHCl3, 0.06
CHCl3, 0.01
1612 (41), 1638 (39)
1617 (29), 1640 (49)
1623 (51)
2103 (75)
2102 (79)
2106 (82)
2105 (79)
3420 (16), 3595 (1), 3623 (6)
3440 (5), 3602 (1), 3625 (10)
3430 (6), 3615 (12)
1625 (49)
3615 (14), 3690 (5)
C6H12, 0.05
C6H12, 0.005
CCl4, 0.05
CCl4, 0.005
CHCl3, 0.06
CHCl3, 0.01
THF, 0.08
THF, 0.01
Film
1635,b 1650 (60)
2082 (60)
2081 (64)
2087 (86)
2084 (60)
2088 (90)
2090 (88)
2082 (70)
2085 (66)
2093 (54)
3465 (15), 3622 (4)
3470 (14), 3622 (5)
3450 (10), 3620 (8)
3450 (10), 3620 (10)
3610 (8)
1652 (45)
1636,b 1648 (70)
1630,b 1650 (48)
1639 (72)
1640 (67)
3608 (10), 3695 (6)
3410 (20)
1651 (64)
1653 (62)
3400 (14)
1630 (50)
3460 (45)
Ij
CCl4, 0.08
CCl4, 0.01
CHCl3, 0.06
CHCl3, 0.01
Film
1641,b 1650 (48)
1640,b 1651 (46)
1636 (52)
2087 (78)
2085 (70)
2088 (73)
2087 (68)
2088 (65)
3470 (12), 3627 (8)
3475 (10), 3625 (9)
3613 (12)
1638 (44)
3615 (11), 3692 (7)
3440 (44)
1630 (60)
a
Solutions were prepared 30–40 min before recording the spectra.
Inflection.
b
Table 4. Stretching vibration frequencies of the diazo and carbonyl groups in diazo ketones with different structuresa
Cyclic diazo ketones
ν(C=N2), cm–1
2090
Acyclic diazo ketones
ν(C=N2), cm–1
2070
structure
ν(CO), cm–1
structure
ν(CO), cm–1
2-Diazocyclo-
hexanone
4-Diazohexan-
3-one
1640
1645
Ib
2107
2138
1645b
1659
Ii
2090
2120
1650b
1680
IIb
IIi
a
Solutions in CCl4, c = 0.05–0.08 M; the data for diazo ketones IIb and IIi, 2-diazocyclohexanone, and 4-diazohexan-3-one were taken
from [12, 19].
ν(C=O) of the “free” carbonyl group.
b
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ZHDANOVA et al.
322
Table 5. Parameters of the electron absorption spectra of
2-diazo-3-hydroxyketones Ib–Ie, Ii, Ij, and Il
intensity of absorption bands belonging to associated
hydroxy and carbonyl groups (1620, 3400 cm–1) and
increase in the intensity of bands from the free groups.
This means that association in solution is intermole-
cular. In going from concentrated to dilute solutions of
acyclic hydroxy diazo ketones Ii and Ij in CCl4, the
position and intensity of bands due to stretching
vibrations of associated hydroxy and carbonyl groups
change insignificantly (Table 3), indicating formation
of intramolecular hydrogen bonds. However, in weakly
polar chloroform or THF no appreciable differences
between the cyclic and acyclic hydroxy diazo ketones
were observed in the above IR spectral ranges. We can
conclude that intramolecular hydrogen bond in acyclic
hydroxy diazo ketones Ii and Ij is very weak and that
intramolecular stabilization of the E conformation of
these diazo compounds is possible only in nonpolar
solvents (CCl4, cyclohexane).
Electron absorption spectra. Hydroxy diazo
ketones I show in the electron absorption spectra
(Table 5) three bands in the region 220–410 nm. Two
of these (λ 240–285 nm) have comparable intensities,
and the third band at λ 350–410 nm is weaker by
2–3 orders of magnitude. The first two bands strongly
overlap each other, especially in the spectra of cyclic
hydroxy diazo ketones Ib–Id, Ie, and Il in a nonpolar
solvent (hexane); therefore, it is difficult to assign
them to definite electron transitions. By analogy with
other diazocarbonyl compounds [16, 17] and 2-diazo-
1,3-diketones [12], we presume that the bands at
λ 240–285 nm in the spectra of diazo ketones I arise
from π–π* transitions. The blue shift of the third band
in going from a polar solvent to nonpolar, its weak
intensity, and some published data for related diazo-
carbonyl compounds [21] suggest its p–π* origin.
Stereochemistry of cyclic hydroxy diazo ketones
Ib–Id, Ie, If, Il, and Im. The C1 and C2 atoms in
molecules Ib–Id, Ie, If, Il, and Im are sp2-hybridized.
Judging by the shift of the ν(C=N2) and ν(C=O) bands
in the IR spectra (Table 4), the C1–C2 bond therein, as
well as in other diazo ketones [10, 16–18] is charac-
terized by a considerably increased order; therefore,
their structure should resemble that of cyclohexene or
tetrahydronaphthalene. Obviously, the most favorable
ring conformation is half-chair where the substituents
on C4 and C5 are oriented axially and equatorially,
respectively, while those on C3 and C6 are pseudoaxial
(ax') and pseudoequatorial (eq'). According to pub-
lished data [22], the vicinal coupling constants
between 3-H and 4-H in the 1H NMR spectra of 3,4-di-
substituted cyclohexenes and tetrahydronaphthalenes
λ
max, nm (logε)
Comp.
no.
water
ethanola
hexane
248 (3.55),
283 (4.02),
346 (1.76)
–
263 (3.92),
373
Ib
Ic
Id
249 (3.53),
285 (4.03),
348 (1.57)
267 (3.73),
287 (3.94),
370 (1.51)
264 (4.01),
374 (1.50)
253 (3.63),
286 (4.00),
348 (1.66)
–
262 (3.97),
380 (1.32)
b
–
272 (3.98),c
370 (1.52)
264 (4.04),
374 (1.38)
Ie
Ii
241 (3.95),
282 (3.88),
370 (1.56)
–
244 (4.11),
282 (3.26),
406 (1.45)
245 (3.98),
285 (3.83),
373 (1.60)
249 (4.07),
289 (3.68),
390 (1.45)
247 (4.18),
285 (3.30),
408 (1.38)
Ij
Il
b
–
260 (3.92),
280 (3.89),
370 (1.54)
262 (4.01),
372 (1.53)
a
b
c
The spectra of compounds Ie and Il were recorded in 2-propanol.
Compounds Ie and Il are insoluble in H2O.
Unsymmetrical absorption band.
from solutions in nonpolar solvents (CCl4) or con-
centrated solutions in chloroform, absorption bands
from associated (3400–3500 cm–1) and free (3600–
3700 cm–1) hydroxy groups are usually present. The IR
spectra of solutions in THF and pure substances (in
KBr or film) contain absorption bands only from
associated hydroxy groups (Table 3). These findings
suggest that the carbonyl and hydroxy groups in diazo
ketones I are involved in intermolecular hydrogen
bonds. The hydrogen bonds are formed between the
substrate molecules (KBr or film) or between the
substrate and the solvent (THF and CHCl3).
Analysis of the concentration dependence of the IR
spectra in nonpolar solvents (CCl4, cyclohexane)
showed that hydrogen bonds formed by cyclic (Ic, Id)
and acyclic (Ii, Ij) hydroxy diazo ketones have
essentially different characters. The strongest changes
on variation of the concentration are observed in the IR
spectra of cyclic hydroxy diazo ketones Ic and Id.
Reduction of the concentration leads to decrease in the
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CHEMISTRY OF DIAZOCARBONYL COMPOUNDS: XVIII.
323
3
(a)
differ considerably for the cis and trans isomers, J =
3 and 9 Hz, respectively.
1
Figure 1 shows fragments of the H NMR spectra
of compounds Ie, If, Il, and Im in CDCl3 in the δ
range from 4.8 to 5.1 ppm, the same fragments after
addition of a solution of K2CO3 in D2O, vicinal
5.0
5.0
5.0
5.0
(b)
3
coupling constants J3,4, and Newman projections
5.0
5.0
5.0
5.0
along the C3–C4 bond. It is seen that in the molecule of
hydroxy diazo ketone Ie (3J3,4 = 2.3 Hz), the hydroxy
group is located cis with respect to the equatorial tert-
butyl group on C4, i.e., molecule Ie has 4-cis-6-cis
configuration with respect to the hydroxy group. The
second stereoisomer in that pair (compound Il) is
J3–4 = 2.3 Hz
7.0 Hz
2.5 Hz
5.5 Hz
(c)
H
H
H
HO
t-Bu
H
H
H
HO
t-Bu
t-Bu
HO
t-Bu
HO
Ie
H
H
3
characterized by a J3,4 value of 7.0 Hz; therefore, the
Il
If
Im
hydroxy group therein is located trans with respect to
the equatorial tert-butyl group on C4 (4-trans-6-trans
configuration). Likewise, in the diastereoisomer pair
If/Im, the former is characterized by the smaller
1
Fig. 1. Fragments of the H NMR spectra of hydroxy
diazo ketones Ie, If, Il, and Im in the δ range from 4.8
to 5.1 ppm (a) in CDCl3 and (b) after addition of D2O
and (c) Newman projections along the C3–C4 bond.
3
coupling constant J3,4 = 2.5 Hz), and hence it has
4-cis-6-trans configuration, whereas the configuration
of substituents in isomer Im (3J3,4 = 5.5 Hz) is 4-trans-
6-cis with respect to the hydroxy group.
typical of an equimolar mixture of hydroxy diazo
ketones Ie and Il (Fig. 2c). It is obvious that hydroxy
diazo ketone Ic in solution exists as an equilibrium
mixture of two conformers with pseudoaxial and
pseudoequatorial hydroxy groups at a ratio of ~1:1.
Hydroxy ketone Id (Fig. 2e) is likely to exist as
an equilibrium mixture of conformers [ν(OH) 3627
and 3603 cm–1] as well, but the equilibrium is
displaced toward the conformer with equatorial
hydroxy group.
An additional information on the stereochemistry of
cyclic hydroxy diazo ketones I in solution was derived
from the data of IR spectroscopy. It is known that
stretching vibration frequencies of axial and equatorial
hydroxy groups in cyclohexanols differ by 10–15 cm–1,
the higher frequency belonging to the axial hydroxy
group [23]. Diastereoisomeric hydroxy diazo ketones
Ie/Il and If/Im (Fig. 2) showed even greater differ-
ences between stretching vibration frequencies of the
axial and equatorial hydroxy groups, 3620/3575 cm–1
and 3625/3595 cm–1, respectively (∆ν = 30–45 cm–1).
In keeping with published data, stereoisomers Ie and If
[ν(OH) 3620 and 3625 cm–1, respectively] should be
assigned pseudoaxial (ax'), and isomers Il and Im
[ν(OH) 3575 and 3595 cm–1], pseudoequatorial (eq')
orientation of the hydroxy group.
We can conclude that 1H NMR and IR spectroscopy
are useful tools for studying stereochemical structure
of isomeric hydroxy diazo ketones Ie/Il and If/Im,
which provide information on fine details of their
conformational behavior. Both methods successfully
1
supplement each other: parameters of the H NMR
spectra indicate the configuration of substituents, and
the IR spectral data allow us to determine orientation
(axial or equatorial) of the hydroxy group, i.e., to
establish the conformational structure of cyclic
hydroxy diazo ketones I.
To illustrate the potential of vibrational spectros-
copy for conformational analysis of hydroxy diazo
ketones of the cyclohexane series, Fig. 2 shows frag-
ments of the IR spectra of compounds Ic and Id
(Fig. 2d, e) and, for comparison, the corresponding
fragments of the IR spectra of conformationally
homogeneous hydroxy diazo ketones Ie and Il and
their 1:1 mixture (Fig. 2a–c). In the spectrum of Ic
(Fig. 2d) we observed two absorption bands with
approximately equal intensities, which belong to
stretching vibrations of the free hydroxy groups
[ν(OH) 3628 and 3598 cm–1]. An analogous pattern is
Thus, we have developed a preparative procedure
for the synthesis of cyclic and acyclic 3-hydroxy-
2-diazocarbonyl compounds I by reduction of one
carbonyl group in the corresponding 2-diazo-1,3-di-
ketones II with sodium tetrahydridoborate in aqueous–
alcoholic medium, followed by hydrolysis of the reac-
tion mixture over wet neutral silica gel and chromatog-
raphic purification of the products on neutral
aluminum oxide. The presence of bulky substituents at
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ZHDANOVA et al.
324
O
(a)
N2
H
OH
Ie (ax-OH)
O
(b)
N2
OH
H
Il (eq-OH)
(c)
Ie (ax'-OH) + Il (eq'-OH)
O
O
(d)
(e)
H
N2
N2
H
HO
OH
Ic (ax'-OH)
Ic (eq'-OH)
O
O
H
N2
N2
H
HO
OH
Id (ax'-OH)
Id (eq'-OH)
Fig. 2. Fragments of the IR spectra of hydroxy diazo ketones Ic–Ie and Il in the region 3350–3650 cm–1 (solutions in CCl4, c =
0.015 M): (a) compound Ie, (b) compound Il, (c) a 1:1mixture of Ie and Il, (d) compound Ic, and (e) compound Id.
the carbonyl group reduces the efficiency of the
process, and the reduction of stereoisomeric 4,6-di-
tert-butyl-2-diazo-1,3-cyclohexanediones is charac-
terized by low stereoselectivity. The IR absorption
frequencies corresponding to stretching vibrations of
the axial and equatorial hydroxy groups in 3-hydroxy-
2-diazocyclohexanones differ by 30–45 cm–1, and
these parameters can be used for conformational
assignments in the series of cyclic hydroxy diazo
ketones.
methanol, and water were distilled prior to use.
Technical-grade sodium tetrahydridoborate was recrys-
tallized from 1 N NaOH; its purity was checked by
hydrolytic decomposition with subsequent quantitation
of the liberated hydrogen; the purified sample con-
tained more than 98% of the main substance [27].
The reaction mixtures were analyzed by TLC on
silica gel (Silufol UV-254); the hydrolysis was
performed over neutral silica gel L 40–100 µm
(Chemapol, activity grade II), which was preliminarily
freed from Fe3+ ions. Neutral aluminum oxide, 100–
250 µm (Chemapol) was used for column chrom-
atography. Hexane, diethyl ether, and benzene used for
column chromatography were preliminarily dried over
metallic sodium and distilled.
EXPERIMENTAL
Diazo diketones IIa–IIj were prepared from the
corresponding 1,3-diketones and arenesulfonyl azides
via diazo transfer reaction in the presence of anhydrous
potassium fluoride [24] (for compounds IIa–IIc and
IIe–IIg) or triethylamine as catalyst (IId and IIh–IIj)
[25]. Dipivaloyldiazomethane Ik was prepared by
diazotization of the corresponding amine [26]. Ethanol,
The IR spectra were recorded on UR-20 and
Specord 75IR spectrometers. The UV spectra were
measured on SP 8000 Pye Unicam and Perkin–Elmer
M-402 spectrophotometers. The 1H NMR spectra were
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CHEMISTRY OF DIAZOCARBONYL COMPOUNDS: XVIII.
325
obtained on Bruker AM-500 (500 MHz) and Varian
HA-100D/15 (100 MHz) instruments; the 13C NMR
spectra were recorded on a Bruker AM-500 spec-
trometer at 125.76 MHz; CDCl3 was used as solvent
and TMS as internal reference.
ether, 2:1 (0.2 l); hydroxy diazo ketone If, 0.77 g
(18%), diethyl ether (0.4 l). Overall yield of hydroxy
diazo ketones If and Im 1.09g (26%), stereoisomer
ratio 2.4:1.
Reduction of diazo diketones IIa, IIc, and IIg
with sodium trihydrido(trifluoroacetyl)borate.
c. A solution of 2.39 g (21 mmol) of trifluoroacetic
acid in 0.6 ml of water was added under vigorous
stirring to a solution of 0.78 g (21 mmol) of NaBH4 in
1 ml of water, cooled to 0°C. After 2–3 min (when
hydrogen no longer evolved), the resulting solution of
sodium trihydrido(trifluoroacetyl)borate was used in
the reduction.
Reduction of diazo diketones II with sodium
tetrahydridoborate. a. A solution of 5 mmol of
sodium tetrahydridoborate in 8 ml of distilled water
was added dropwise over a period of 3–5 min to
a solution of 10 mmol of diazo diketone II in 50 ml of
ethanol under stirring and cooling with ice water. The
cooling bath was removed, the mixture was stirred for
20 min, and 3 mmol of dry sodium tetrahydridoborate
was added. After 50 min (from the reaction start), the
mixture was filtered through a layer of silica gel (10 g)
on a glass filter, and the sorbent was washed with
methanol (2×10 ml). The solvent was distilled off
under reduced pressure (1–3 mm) to a volume of
10–15 ml, 3 g of aluminum oxide was added, the
mixture was evaporated to dryness, and the residue
was applied to a column charged with 80 g of
aluminum oxide for chromatographic purification.
A freshly prepared solution of 21 mmol of sodium
trihydrido(trifluoroacetyl)borate was added over
a period of 1.5–2 min under stirring to a suspension of
20 mmol of diazo diketone IIa, IIc, or IIg in 10 ml of
ethanol, cooled to 2°C with an ice bath. The mixture
was stirred for 15–120 min until the reaction was
complete (Table 1) and filtered through a 0.5-cm layer
of silica gel, the sorbent was washed with methanol
(3×5 ml), 4 g of Al2O3 was added to the filtrate,
the solvent was distilled off under reduced pressure
(12 mm), and the residue was applied to a column
charged with 10 g of Al2O3. The results are given in
Table 1 (run nos. 4, 10, 18).
Synthesis of stereoisomeric 3-hydroxy-2-diazo-
ketones Ie/Il and If/Im. b. Diazo diketones IIe and IIf
were reduced with 3 equiv of sodium tetrahydrido-
borate, and the reaction mixture was treated as
described in a.
The yields, some physical constants, and elemental
(3r,4c,6c)-4,6-Di-tert-butyl-2-diazo-3-hydroxy-
cyclohexanone (Ie) and (3r,4t,6t)-4,6-di-tert-butyl-2-
diazo-3-hydroxycyclohexanone (Il). Chromatographic
separation of the reaction mixture obtained by reduc-
tion of 2.82 g (6 mmol) of diazo diketone IIe
(according to the general procedure; reaction time 3 h)
gave the following compounds (in the order of
elution): diazo diketone IIe, 1.55 g (55%), hexane–
benzene, 3:1 (0.3 l); hydroxy diazo ketone Ie, 0.22 g
(8%), hexane–diethyl ether, 9:1 (0.3 l), 3:1 (0.2 l);
hydroxy diazo ketone Il, 0.65 g (23%), hexane–diethyl
ether, 1:1 (0.3 l), diethyl ether (0.2 l). Overall yield of
hydroxy diazo ketones Ie and Il 0.87 g (31%),
stereoisomer ratio 1:3.
analyses of diazo ketones I are given in Table 2.
2-Diazo-3-hydroxyindan-1-one (Ia). IR spectrum
(CHCl3, c = 0.05 M), ν, cm–1 (I, %): 900 (8), 920 (9),
1015 (16), 1098 (9), 1165 (10), 1175 (11), 1200 (10),
1250 (11), 1340 (24), 1390 (5), 1605 (11), 1685 (26),
1705 (10), 2095 (46), 3350 br (5), 3545 (6), 3660 (4).
1H NMR spectrum (100 MHz), δ, ppm: 4.36 d (1H,
OH, J = 5.3 Hz), 5.93 d (1H, CHOH, J = 5.5 Hz),
7.46–7.67 m (4H, Harom).
2-Diazo-3-hydroxycyclohexanone (Ib). IR spec-
trum (CCl4, c = 0.06 M), ν, cm–1 (I, %): 872 (10), 938
(20), 958 (14), 1005 (16), 1070 (28), 1115 (12), 1168
(23), 1220 (30), 1228 (31), 1255 (20), 1305 (31), 1335
(54), 1360 (53), 1390 (20), 1420 (14), 1446 (14), 1465
(13), 1620 (58), 1645 (46), 2107 (82), 2865 (11), 2880
(15), 2900 (14), 2930 (20), 2960 (28), 3410 br (22),
3610 (7). 1H NMR spectrum (100 MHz), δ, ppm: 1.60–
2.11 m (4H, 2CH2), 2.18–2.40 m (2H, CH2), 4.86 s
(1H, OH), 4.96 m (1H, CHOH).
(3r,4c,6t)-4,6-Di-tert-butyl-2-diazo-3-hydroxy-
cyclohexanone (If) and (3r,4t,6c)-4,6-di-tert-butyl-2-
diazo-3-hydroxycyclohexanone (Im). Chromatog-
raphic separation of the reaction mixture obtained
by reduction of 4.23 g (9 mmol) of diazo diketone
IIf gave the following compounds (in the order of
elution): diazo diketone IIf, 1.25 g (30%), hexane–
2-Diazo-3-hydroxy-5,5-dimethylcyclohexanone
benzene, 3:1 (0.3 l); hydroxy diazo ketone Im, 0.32 g (Ic). IR spectrum (CCl4, c = 0.06 M), ν, cm–1 (I, %):
(8%), hexane–diethyl ether, 9:1 (0.3 l), hexane–diethyl
988 (18), 999 (17), 1037 (16), 1080 (12), 1138 (12),
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ZHDANOVA et al.
326
1180 (16), 1230 (29), 1280 (30), 1315 (44), 1350 (44),
1363 (43), 1395 (23), 1462 (13), 1478 (15), 1618 (52),
1644 (44), 2109 (88), 2880 (19), 2940 (26), 2968 (38),
3-Diazo-4-hydroxypentan-2-one (Ih). IR spectrum
(CHCl3, c = 0.06 M), ν, cm–1 (I, %): 855 (26), 920
(14), 1000 (11), 1080 (22), 1100 (13), 1200 (10), 1250
(25), 1295 (40), 1355 (24), 1370 (29), 1395 (14), 1620
(51), 2070 (58), 2945 (10), 3410 br (10), 3585 (6).
1H NMR spectrum (100 MHz), δ, ppm: 1.33 d (3H,
CH3COH, J = 7.0 Hz), 2.17 s (3H, CH3C=O), 4.73 s
(1H, OH), 4.78 m (1H, CHOH).
1
3400 br (20), 3595 (5), 3621 (5). H NMR spectrum
(500 MHz), δ, ppm: 1.00 s (3H, CH3); 1.10 s (3H,
CH3); 2.14 s (2H, CH2C=O); 4.39 s (1H, OH); 1.76 q,
1.84 q, and 4.96 m (3H, NCHCHOH; ABX system:
HA 1.60, HB 2.00, HX 4.96; JAB = 13, JAX = 9, JBX = 7.0
Hz). 13C NMR spectrum, δC, ppm: 26.3 (CH3), 30.6
(CCH3), 30.8 (CH3), 45.2 (CH2COH), 50.4 (CH2CO),
63.5 (COH), 71.6 (CH2), 193.8 (C=O).
2-Diazo-3-hydroxy-4,4,6,6-tetramethylcyclo-
hexanone (Id). IR spectrum (CCl4, c = 0.06 M), ν,
cm–1 (I, %): 922 (4), 940 (6), 970 (7), 990 (9), 1008
(16), 1025 (20), 1045 (15), 1058 (15), 1103 (8), 1152
(12), 1179 (21), 1225 (31), 1235 (33), 1279 (33), 1343
(37), 1355 (33), 1390 (39), 1463 (17), 1486 (22), 1612
(41), 1638 (39), 2103 (75), 2878 (21), 2930 (27), 2967
(31), 2983 (29), 3420 br (16), 3595 (2), 3623 (8).
1H NMR spectrum (500 MHz), δ, ppm: 1.06 s, 1.09 s,
1.17 s, and 1.20 s (3H each, CH3); 1.64 q (2H, CH2;
AB system: HA 1.41, HB = 1.87, JAB = 14 Hz); 4.36 s
(1H, OH), 4.44 s (1H, CHOH). 13C NMR spectrum,
δC, ppm: 23.9, 27.0, 29.5, 29.6 (CH3); 35.4 (CHCOH);
41.2 (CHCO), 46.1 (CH2), 63.5 (COH), 70.3 (CH2),
199.9 (C=O).
4-Diazo-5-hydroxyheptan-3-one (Ii). IR spectrum
(CCl4, c = 0.06 M), ν, cm–1 (I, %): 979 (30), 1023 (32),
1059 (32), 1084 (36), 1110 (36), 1235 (42), 1260 (45),
1315 (32), 1334 (31), 1389 (44), 1410 (32), 1472 (32),
1642 (60), 1650 (60), 2087 (81), 2865 (23), 2890 (32),
2950 (39), 2982 (39), 3450 br (10), 3620 (8). 1H NMR
spectrum (500 MHz), δ, ppm: 0.97 d and 1.12 d (6H,
CH3, J = 7,5 Hz), 1.39–1.92 m (2H, CH2OH), 2.52 q
(2H, CH2C=O, J = 7.5 Hz), 4.21 s (1H, OH), 4.66 d
(1H, CHOH, J = 7.0 Hz). 13C NMR spectrum, δC,
ppm: 8.6 and 10.0 (CH3), 27.6 (CHCOH), 31.7
(CHCO), 67.1 (COH), 71.5 (CH2), 195.3 (C=O).
4-Diazo-5-hydroxy-2,6-dimethylheptan-3-one
(Ij). IR spectrum (CCl4, c 0.06 M), ν, cm–1 (I, %): 926
(25), 988 (23), 1042 (37), 1100 (40), 1110 (35), 1162
(24), 1180 (27), 1235 (45), 1256 (48), 1300 (30), 1318
(29), 1335 (9), 1374 (35), 1397 (46), 1462 (28), 1472
(35), 1480 (40), 1641 (70), 1650 (48), 2087 (78), 2885
(36), 2946 (41), 2979 (53), 3470 br (12), 3627 (8).
1H NMR spectrum (500 MHz), δ, ppm: 0.92 d (3H,
CH3, J = 7,0 Hz), 1.06 d (3H, CH3, J = 7.0 Hz), 1.14 d
[6H, (CH3)2CHC=O, J = 7.0 Hz], 1.89 d.sept (1H,
CHCOH, J = 8.0, J = 7.0 Hz), 2.86 sept (1H, CHC=O,
J = 7.0 Hz), 3.95 s (1H, OH), 4.40 d (1H, CHOH,
(3r,4c,6c)-4,6-Di-tert-butyl-2-diazo-3-hydroxy-
cyclohexanone (Ie). IR spectrum (CHCl3, c = 0.06 M),
ν, cm–1 (I, %): 873 (9), 915 (12), 952 (20), 972 (16),
1032 (15), 1062 (19), 1088 (13), 1115 (19), 1164 (15),
1230 (34), 1355 (48), 1383 (45), 1414 (19), 1498 (72),
1645 (44), 2122 (71), 2892 (35), 2932 (32), 2986 (63),
1
3622 (13). H NMR spectrum (100 MHz), δ, ppm:
13
J = 8.0 Hz). C NMR spectrum, δC, ppm: 18.6, 18.7,
1.05 s (9H, t-Bu), 1.10 s (9H, t-Bu), 1.20–2.13 m
(4H, CHCH2CH), 2.38 s (1H, OH), 5.03 d (1H,
CHOH, J = 2.3 Hz).
and 19.0 (CH3); 33.1 (CHCOH); 36.3 (CHCO); 71.2
(COH); 69.7 (CH2); 198.8 (C=O).
(3r,4t,6t)-4,6-Di-tert-butyl-2-diazo-3-hydroxy-
cyclohexanone (Il). IR spectrum (CHCl3, c = 0.05 M),
ν, cm–1 (I, %): 892 (11), 918 (12), 996 (27), 1032 (10),
1108 (10), 1200 (20), 1262 (28), 1312 (22), 1365 (39),
1382 (42), 1410 (20), 1499 (19), 1654 (40), 2119 (76),
(3r,4c,6t)-4,6-Di-tert-butyl-2-diazo-3-hydroxy-
cyclohexanone (If). IR spectrum (CHCl3, c = 0.05 M),
ν, cm–1 (I, %): 928 (14), 952 (12), 1042 (13), 1061
(70), 1093 (31), 1129 (64), 1170 (34), 1210 (30), 1275
(32), 1285 (29), 1300 (24), 1353 (50), 1369 (36), 1386
(48), 1400 (38), 1412 (30), 1465 (26), 1490 (38), 1649
(44), 1668 (46), 2105 (85), 2895 (60), 2958 (62), 2987
(72), 3625 (8). 1H NMR spectrum (100 MHz), δ, ppm:
0.99 s (18H, t-Bu), 1.45–2.15 m (4H, CHCH2CH),
3.13 s (1H, OH), 5.03 d (1H, CHOH, J = 2.5 Hz).
1
2896 (30), 2931 (29), 2986 (57), 3580 (11). H NMR
spectrum (100 MHz), δ, ppm: 1.03 s (9H, t-Bu), 1.06 s
(9H, t-Bu), 1.22–2.15 m (4H, CHCH2CH), 3.68 d
(1H, COH, J = 7.0 Hz), 4.92 d.d (1H, CHOH, J = 7.0,
J = 7.0 Hz).
2-Diazo-3-hydroxy-1,3-diphenylpropanone (Ig).
IR spectrum (CCl4, c = 0.06 M), ν, cm–1 (I, %): 900
(5), 1015 (20), 1180 (16), 1245 (14), 1300 (25), 1330
(35), 1445 (16), 1490 (15), 1570 (20), 1610 (52), 2070
(60), 3010 (7), 3045 (7), 3400 br (10), 3580 (6).
(3r,4t,6c)-4,6-Di-tert-butyl-2-diazo-3-hydroxycy-
clohexanone (Im). IR spectrum (CHCl3, c = 0.05 M),
ν, cm–1 (I, %): 884 (10), 942 (11), 981 (19), 1031 (13),
1045 (12), 1061 (12), 1081 (12), 1120 (15), 1178 (30),
1210 (31), 1252 (34), 1288 (14), 1328 (27), 1343 (32),
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CHEMISTRY OF DIAZOCARBONYL COMPOUNDS: XVIII.
327
Weingarten, P.P.M., Tetrahedron, 1997, vol. 53, p. 2371;
Padwa, A., Kulkarni, Y.S., and Zhang, Z., J. Org. Chem.,
1990, vol. 55, p. 4144; Tsuge, O., Kanemasa, S.,
Suzuki, T., and Matsuda, K., Bull. Chem. Soc. Jpn.,
1986, vol. 59, p. 2851.
1362 (32), 1378 (40), 1410 (21), 1485 (28), 1681 (70),
2115 (87), 2880 (30), 2931 (31), 2975 (60), 3600 (10).
1H NMR spectrum (100 MHz), δ, ppm: 1.01 s (9H,
t-Bu), 1.08 s (9H, t-Bu), 1.51–2.23 m (4H, CHCH2CH),
3.20 s (1H, OH), 4.83 d (1H, CHOH, J = 5.5 Hz).
6. Eistert, B. and Donath, P., Chem. Ber., 1969, vol. 102,
p. 1725; Eistert, B. and Borggrefe, G., Justus Liebigs
Ann. Chem., 1968, vol. 718, p. 142; Miyauchi, K.,
Hori, K., Hirai, T., Takebayashi, M., and Ibata, T., Bull.
Chem. Soc. Jpn., 1981, vol. 54, p. 2142; Nagano, K.,
Chiba, M., and Kim, S.-W., Synthesis, 1983, p. 193;
Ohno, M., Noda, M., Yamomoto, Y., and Eguchi, S.,
J. Org. Chem., 1999, vol. 64, p. 707; Sit, S.-Y., Ehr-
gott, F.J., Gao, J., and Meanwell, N.A., Bioorg. Med.
Chem. Lett., 1996, vol. 6, p. 499.
REFERENCES
1. Nikolaev, V.A., Sieler, J., Nikolaev, Vs.V., Rodina, L.L.,
and Schulze, B., Russ. J. Org. Chem., 2001, vol. 37,
p. 1190.
2. Burger, K., Rudolph, M., Naunhauser, H., and Gold, M.,
Synthesis, 1992, p. 1150; Kocienski, P., Stocks, M.,
Donald, D., Cooper, M., and Manners, A., Tetrahedron
Lett., 1988, vol. 29, p. 4481; Lopez-Herrera, F.J. and
Sarabia-Garsia, F., Tetrahedron, 1997, vol. 53, p. 3325;
Lopez-Herrera, F.J., Valpuesta-Fernandes, M., and
Garsia-Claros, S., Tetrahedron, 1990, vol. 46, p. 7165;
Pellicciari, R.., Natalini, B., Cecchetti, S., and Fringa-
elli, R., J. Chem. Soc., Perkin Trans. 1, 1985, p. 493;
Pellicciari, R., Fringuelli, R., Sisani, E., and Curini, M.,
J. Chem. Soc., Perkin Trans. 1, 1981, p. 2566;
Singh, A.K., Bakshi, R.K., and Corey, E.J., J. Am. Chem.
Soc., 1987, vol. 109, p. 6187; Ye, T. and McKer-
vey, M.A., Tetrahedron, 1992, vol. 48, p. 8007; Col-
lins, J.C., Dilworth, B.M., Garvey, N.T., Kennedy, M.,
McKervey, M.A., and O’Sullivan, M.B., J. Chem. Soc.,
Chem. Commun., 1990, p. 362.
7. Burkoth, T.L., Tetrahedron Lett., 1969, vol. 57, p. 5049;
Snatzke, G., Ehrig, B., and Klein, H., Tetrahedron, 1969,
vol. 25, p. 5601; Padwa, A., Hornbuckle, S.F.,
Zhang, Z., and Zhi, L., J. Org. Chem., 1990, vol. 55,
p. 5297.
8. Severin, T. and Lerche, H., Chem. Ber., 1970, vol. 103,
p. 2148.
9. Davies, H.M.L., Hougland, P.W., and Cantrell, W.R.,
Synth. Commun., 1992, vol. 22, p. 971; Davies, H.M.L.
and Huby, J.S., Tetrahedron Lett., 1992, vol. 33,
p. 6935.
10. Regitz, M. and Maas, G., Diazo Compounds, New York:
Academic, 1986, p. 596.
3. Nikolaev, V.A., Zhdanova, O.V., and Korobitsyna, I.K.,
Zh. Org. Khim., 1981, vol. 17, p. 1775; Nikolaev, V.A.,
Zhdanova, O.V., and Korobitsyna, I.K., Zh. Org. Khim.,
1982, vol. 18, p. 559.
11. Doyle, M.P., McKervey, M.A., and Ye, T., Modern
Catalytic Methods for Organic Synthesis with Diazo
Compounds, New York: Wiley, 1998, p. 9.
12. Korobitsyna, I.K. and Nikolaev, V.A., Zh. Org. Khim.,
4. Biltz, H. and Kramer, E., Justus Liebigs Ann. Chem.,
1924, vol. 436, p. 154; Eistert, B. and Hackmann, E.A.,
Justus Liebigs Ann. Chem., 1962, vol. 657, p. 120;
Wenkert, E. and McPherson, C.A., J. Am. Chem. Soc.,
1972, vol. 94, p. 8084; Woolsey, N.F. and Khalil, M.H.,
J. Org. Chem., 1972, vol. 37, p. 2405; Schoellkopf, U.,
Banhidai, B., Frasnelli, H., Meyer, R., and Beckhaus, H.,
Justus Liebigs Ann. Chem., 1974, p. 1767; Evans, D.A.,
Truesdale, L.K., and Grimm, K.G., J. Org. Chem., 1976,
vol. 42, p. 3335; Disteldorf, W. and Regitz, M., Chem.
Ber., 1976, vol. 109, p. 546.
1976, vol. 12, p. 1244.
13. USSR Inventor's Certificate no. 802269, 1980; Byull.
Izobret., 1981, no. 5; Zhdanova, O.V., Cand. Sci.
(Chem.) Dissertation, Leningrad, 1981; Korneev, S.M.,
Cand. Sci. (Chem.) Dissertation, Leningrad, 1990.
14. Regitz, M. and Liedhegener, A., Chem. Ber., 1966,
vol. 99, p. 3128; Hodson, D., Holt, G., and Wall, D.K.,
J. Chem. Soc. C, 1968, p. 2201; Korneev, S. and
Richter, Ch., Synthesis, 1995, p. 1248.
15. Wigfield, D.C., Tetrahedron, 1979, vol. 35, p. 449.
5. Bagley, M.C., Hind, S.L., and Moody, C.J., Tetrahedron
Lett., 2000, vol. 41, p. 6897; Moody, C.J. and Mor-
fitt, C.N., Synthesis, 1998, p. 1039; Eguchi, Y., Sasaki, F.,
Takashima, Y., Nakajima, M., and Ishikawa, M., Chem.
Pharm. Bull., 1991, vol. 39, p. 759; Holmquist, Ch.R. and
Roskamp, E.J., J. Org. Chem., 1989, vol. 54, p. 3258;
Medvedeva, A.S., Demina, M.M., Borisova, A.I., and
Vyazankin, N.S., J. Organomet. Chem., 1982, vol. 231,
p. 109; Margorskaya, O.I., Medvedeva, A.S., Voron-
kov, M.G., and Vyazankin, N.S., Zh. Obshch. Khim.,
1989, vol. 59, p. 2043; Padwa, A., Sa, M.M., and
16. Korobitsyna, I.K. and Studzinskii, O.P., Usp. Khim.,
1970, vol. 39, p. 1754; Fridman, A.L., Ismagilova, T.S.,
Zalesov, V.S., and Novikov, S.S., Usp. Khim., 1972,
vol. 41, p. 722.
17. Sorriso, S., The chemistry of Diazonium and Diazo
Groups, Patai, S., Ed., New York: Wiley, 1978, vol. 1,
p. 113; Zollinger, H., Diazochemistry II, Weinheim:
VCH, 1995, p. 145.
18. Nikolaev, V.A., Rodina, L.L., and Korobitsyna, I.K.,
Zh. Org. Khim., 1974, vol. 10, p. 1555; Lauer, W.,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 3 2004

ZHDANOVA et al.
Krause, V., Wengenroth, H., and Meier, H., Chem. Ber.,
328
22. Bernath, G., Sohar, P., Lang, K.L., Tornayai, L., and
Kovacs, O.K., Acta Chim. Acad. Sci. Hung., 1970,
vol. 64, p. 81.
1988, vol. 121, p. 465; Nikolaev, V.A., Popik, V.V., and
Korobitsyna, I.K., Zh. Org. Khim., 1991, vol. 27, p. 505.
19. Fahr, E., Chem. Ber., 1959, vol. 92, p. 398; Bassani, R.,
DiFuria, F., and Curci, R., Spectrosc. Lett., 1974, vol. 7,
p. 531.
20. Schoellkopf, U., Banhidai, B., and Frasnelli, H., Justus
Liebigs Ann. Chem., 1974, p. 1767; Tomioka, H.,
Okuno, H., and Izawa, Y., J. Org. Chem., 1980, vol. 45,
p. 5278.
21. Leveson, L.L. and Thomas, C.W., Tetrahedron, 1966,
vol. 22, p. 209; Csizmadia, I.G., Houlden, S.A.,
Meresz, O., and Yates, P., Tetrahedron, 1969, vol. 25,
p. 2121; Sverdlova, O.V., Elektronnye spektry v organi-
cheskoi khimii (Electron Spectra in Organic Chemistry),
Leningrad: Khimiya, 1985, p. 248.
23. Allsop, I.L., Coll, A.R.H., White, D.E., and
Willix, R.L.S., J. Chem. Soc., 1956, p. 4868;
Chiwidoglu, G. and Masschelein, W., Bull. Soc. Chim.
Belg., 1959, vol. 68, p. 484.
24. Popik, V.V., Korneev, S.M., Nikolaev, V.A., and
Korobitsyna, I.K., Synthesis, 1991, p. 195.
25. Regitz, M., Chem. Ber., 1966, vol. 99, p. 3128.
26. Nikolaev, V.A., Frenkh, Yu., and Korobitsyna, I.K.,
Zh. Org. Khim., 1978, vol. 14, p. 1147.
27. Mal’tseva, N.N. and Khain, V.S., Borogidrid natriya
(Sodium Tetrahydridoborate), Moscow: Nauka,
1985, p. 8.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 3 2004