Electron-transfer reduction of selected alcohols with alkalide K-, K+(15-crown-5)2 via organometallic intermediates

Article abstract of DOI:10.1016/j.jorganchem.2004.04.026

The course of the reaction of alkalide K^-, K⁺ (15-crown-5)₂ 1 with selected alcohols depends on the kind of alcohol and the mode of substrate delivery. In the case of methanol, potassium methoxide formed initially undergoes destructfion at the excess of 1. It results in potassium oxide and methylpotassium. The latter opens the crown ether ring giving potassium tetraethylene glycoxide vinyl ether and methane. A similar course of the process is observed for propanol. Potassium glycidoxide is the main product formed in the reaction of 1 with glycidol. Its oxirane ring is opened at the excess of 1. Organopotassium alkoxides, i.e., potassium potassiomethoxide and dipotassium potassiopropane-1,2-dioxide are intermediate products of this reaction. They react then with the crown ether. Potassium methoxide, potassium enolate of acetaldehyde, dipotassium propane-1, 2-dioxide and potassium tetraethylene glycoxide vinyl ether are the final products of this process.

Full text of DOI:10.1016/j.jorganchem.2004.04.026

Journal of Organometallic Chemistry 689 (2004) 2361–2367
www.elsevier.com/locate/jorganchem
Electron-transfer reduction of selected alcohols with alkalide
Kꢀ, Kþ(15-crown-5)2 via organometallic intermediates
a
a,
b
Zbigniew Grobelny , Andrzej Stolarzewicz *, Adalbert Maercker ,
c
d
e
Stanisław Krompiec , Janusz Kasperczyk , Jozef Rzepa , Holger Frey
f
ꢀ
a
Institute of Materials Science, University of Silesia, Bankowa 12, 40-007 Katowice, Poland
b
Institut f€ur Organische Chemie, Universit€at Siegen, 57068 Siegen, Germany
Department of Analytical and General Chemistry, Silesian University of Technology, 44-101 Gliwice, Poland
c
d
Chair of Molecular Biology, Biochemistry and Biopharmacy, Medical University of Silesia, 41-200 Sosnowiec, Poland
e
Institute of Chemistry, University of Silesia, 40-007 Katowice, Poland
Institut f€ur Organische Chemie, Johannes-Gutenberg-Universit€at, 55099 Mainz, Germany
f
Received 4 February 2004; accepted 21 April 2004
Abstract
The course of the reaction of alkalide Kꢀ, Kþ(15-crown-5)2 1 with selected alcohols depends on the kind of alcohol and the mode
of substrate delivery. In the case of methanol, potassium methoxide formed initially undergoes destruction at the excess of 1. It
results in potassium oxide and methylpotassium. The latter opens the crown ether ring giving potassium tetraethylene glycoxide
vinyl ether and methane. A similar course of the process is observed for propanol. Potassium glycidoxide is the main product formed
in the reaction of 1 with glycidol. Its oxirane ring is opened at the excess of 1. Organopotassium alkoxides, i.e., potassium po-
tassiomethoxide and dipotassium potassiopropane-1,2-dioxide are intermediate products of this reaction. They react then with the
crown ether. Potassium methoxide, potassium enolate of acetaldehyde, dipotassium propane-1,2-dioxide and potassium tetraeth-
ylene glycoxide vinyl ether are the final products of this process.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Methanol; Glycidol; Propanol; Alkalide; Potassium anions; Electron-transfer reduction; Organopotassium intermediates
1. Introduction
literature. This work describes for the first time the
study in such area. Methanol, propanol, glycidol and
Kꢀ, Kþ(15-crown-5)2 1 in tetrahydrofuran solution
were selected for this study.
Alkalides, Mꢀ, MþC, are salts containing alkali metal
anions and cations complexed by a ligand, e.g., crown
ether [1–4]. They are known as two-electron-transfer
species [5], used in the reactions with alkenes [6–9], al-
kines [10], alkyl halides [11,12], silyl halides [13], ketones
[14,15], esters [16–20], and ethers [12,20–28]. Organo-
metallic compounds were intermediate products in those
systems. They underwent various fast reactions, for ex-
ample with crown ether applied for the preparation of
alkalide [29].
Methanol and propanol are simple alcohols. Glycidol
possesses two functional groups, i.e., the oxirane ring
and the hydroxyl group. Thus, it can take part in two
kinds of reaction [30]. For example, the oxirane ring is
opened in the presence of alkoxides [31–33]. Cleavage
occurs exclusively in the b-position, i.e., between oxygen
and the CH2 group. This mechanism of the ring opening
has been also reported for the reaction of chiral glycidol
with thiols under basic condition [34]. A similar mech-
anism is assumed for the reaction of (R)- or (S)-glycidol
with phenols in the presence of triethylamine in absolute
ethanol or sodium hydroxide in water [35]. On the other
hand, the O–H bond is cleaved in reactions of glycidol
with vinyl ethers [36]. The appropriate glycidyl ethers
Data concerning the behaviour of alcohols in the
presence of alkalides were till now not presented in the
* Corresponding author. Tel.: +48-32-359-14-21; fax: +48-32-259-69-
29.
E-mail address: astolarzewicz@silesianet.pl (A. Stolarzewicz).
0022-328X/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.04.026

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Z. Grobelny et al. / Journal of Organometallic Chemistry 689 (2004) 2361–2367
are formed in this case. The oxirane ring does not take
part in this process. A similar phenomenon was recently
described in [37]. Glycidol reacted with potassium hy-
dride exclusively as a typical alcohol, giving potassium
glycidoxide and hydrogen. This means that the activity
of one of the groups present in the glycidol molecule
results in the inactivity of another. Further examples
supporting this rule are given in [30].
The products obtained in the reaction of 1 with the
excess of propanol included hydrogen and potassium
propoxide. At the excess of 1 the latter decomposed to
potassium oxide and propylpotassium, which opened
the crown ether ring giving propane and 7. It means that
methanol and propanol react in the same manner with
the alkalide.
A similar phenomenon was previously described for
allylic and benzylic alcohols and their silylated deriva-
tives [38]. It was found that alkoxides obtained in the
reaction of these alcohols with butyllithium could be
cleaved even with a less reactive lithium powder when
using of 4,40-di-tert-butylbiphenyl (DTBB) in a catalytic
amount. That resulted in appropriate alkyllithium
compounds, which reacted with different electrophiles.
Crown ether was not applied in such a system.
The excess of glycidol in relation to 1 was used in the
second series of experiments. Hydrogen evolution was
observed during the reaction. The process was stopped
by the addition of benzyl bromide to identify volatile
benzyl derivatives of non-volatile reaction products.
Two compounds were detected in the reaction mixture
after benzylation, i.e., benzyl glycidyl ether (19%) and 2-
benzyloxy-1-propanol (3%). This shows that potassium
glycidoxide and potassium 1-hydroxypropane-2-oxide
were the original products of the reaction. The experi-
ments were repeated several times with very similar
product distribution. Only these two benzylated potas-
sium alkoxides and hydrogen were obtained each time.
Various reaction mechanisms were taken into ac-
count to explain these results. The most probable is that
the process starts with the electron transfer from Kꢀ of 1
to the glycidol molecule. K° and the radical anion 9 are
formed in this reaction (Scheme 3). The unstable 9 can
decompose to the radical anion 10 due to the oxirane
ring opening in the b-position. Then, K° transfers the
second electron to 10 giving the organopotassium
compound 11. It reacts with another glycidol molecule,
2. Results and discussion
An excess of methanol in relation to 1 was used in the
first series of experiments. The blue solution of 1 became
colorless when it was dropped into methanol. Potassium
anions of 1 vanished at this moment [4]. Hydrogen
evolution was observed at the same time. The reaction
mixture was quenched by the addition of benzyl bro-
mide. Only one product was detected in the system after
its benzylation, i.e., benzyl methyl ether (in 25% yield).
In a separate experiment methanol was dropped into
a solution of 1 until the reaction mixture became col-
orless, i.e., until Kꢀ was decayed. It means that potas-
sium anions were still at the excess in relation to
methanol except for the moment of discoloration. The
evolution of hydrogen and methane took place in this
case. Tetraethylene glycol benzyl vinyl ether was found
in the reaction mixture after its quenching with benzyl
bromide.
Basing on these results a following mechanism of the
process is proposed. The electron-transfer reduction of
methanol with 1 leads to the formation of hydrogen and
two kinds of potassium methoxide molecules, 3 and 30
(Scheme 1). However, at the excess of 1 the alkoxide is
then destroyed to methylpotassium 6 and potassium
oxide. 6 reacts immediately with crown ether giving
methane and potassium tetraethylene glycoxide vinyl
ether 7 (Scheme 2).
−
.
K , K+ + CH3OH
−
Ko
+
CH3O
H
, K+
1
2
CH3OH
−
.
+
−
, K+
+
−
CH3O , K + ½ H2
CH3O
H
½ H2 + CH3O , K
3’
2’
3
BnBr
CH3OBn
4
where: K+ denotes K+(15-crown-5); the second crown ether molecule was omitted.
Scheme 1.

Z. Grobelny et al. / Journal of Organometallic Chemistry 689 (2004) 2361–2367
2363
−Ko
−
.
K− , K+ + CH3O−, K+
3 or 3’
Ko
+
CH3 O−, K+
, K+
1
5
K2O + · CH3 + 2 (15-crown-5)
Ko
H2O
O
15-crown-5
O−, K+
O
O
2 KOH
CH3K
CH4
+
O
6
7
BnBr
O
OBn
O
O
O
8
Scheme 2.
Scheme 3.
causing its deprotonation, giving potassium 1-hydroxy-
propane-2-oxide 12 and potassium glycidoxide 130. On
the other hand, hydrogen evolves during the decompo-
sition of 9 to potassium glycidoxide 13. The latter
possesses a counter ion complexed by two crown ether
molecules. However, K° can also react with glycidol.
This leads to the formation of 130 and hydrogen. Thus,
three kinds of alkoxides are formed in the process, i.e.,

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Z. Grobelny et al. / Journal of Organometallic Chemistry 689 (2004) 2361–2367
12, 13, and 130, although only two benzylated prod-
ucts, i.e., 2-benzyloxy-1-propanol 14 and benzyl glycidyl
ether 15 are obtained after benzylation of the reaction
mixture.
This means that the system found differs from those
known until now [30–37]. Both the oxirane ring and the
O-H bond are cleaved in glycidol by Kꢀ. The rule pre-
sented in the literature that the activity of one of these
groups is connected with the inactivity of another is not
valid in the studied system.
In further experiments the reaction of glycidol was
conducted in reverse. Glycidol was dropped into a so-
lution of 1 until the reaction mixture became colorless.
In this case the benzylated reaction products included
benzyl methyl ether (in 12% yield), benzyl vinyl ether
(15%), 1,2-dibenzyloxypropane (26%), and tetraethylene
glycol benzyl vinyl ether (15%). Benzyl glycidyl ether,
i.e., the benzylated product of potassium glycidoxide
was not observed. This means that additional reactions
occur in the system containing an excess of 1. Kꢀ
transfers one electron to 13 or 130, giving K° and the
radical anion 16 (Scheme 4). The oxirane ring of 16 is
then opened in the b-position. The radical anion 17
formed may react in two ways. In the first path, it de-
composes to the radical anion of formaldehyde 18 [27]
and the enolate anion of acetaldehyde 19, which are
stabilized by resonance. Then, K° transfers the next
electron to 18 giving potassium potassiomethoxide 21. It
opens the crown ether ring. This in turn results in po-
tassium tetraethylene glycoxide vinyl ether 7 and po-
tassium methoxide 30, similar as described in [27]. In the
second path the electron is transferred from K° to 17.
−
O-, K+
O-, K+
K-, K+
+
, K+
˚
+ K
O
O
13 or 13'
1
16
O-, K+
O-, K+
17
K˚
CH2O-
-CH2O , K+
O-, K+
K
O-, K+
O-, K+
+
19
18
20
BnBr
K
˚
OBn
O-, K+
O
K
O-, K+
O-, K+
O
23
+
21
22
O-, K+
O
O
O
7
O-, K+
CH3O-, K+
+
O
BnBr
O
3'
O
O
O
7
OBn
OBn
+
24
8
OBn
BnBr
O
O
O
OBn
O
O
CH3OBn +
8
4
O
Scheme 4.

Z. Grobelny et al. / Journal of Organometallic Chemistry 689 (2004) 2361–2367
2365
Organopotassium glycoxide 20 formed attacks then
crown ether. 7 and dipotassium propane-1,2-dioxide 22
are the final products of the process. However, 1 can
also react with 12. It results in the formation of 22 and
hydrogen. Thus, at the excess of 1 further reactions took
place with the participation of potassium anions. Initial
products were destroyed and some new compounds were
observed in the reaction mixture. 4, 8, 23, and 24 are
their benzylated derivatives found after benzylation.
The processes presented in Schemes 1–4 are very fast,
similarly as it has been found in earlier works [22–28].
Organopotassium compounds are formed at the excess
of 1. However, their benzylated derivatives were not
detected in the reaction mixture. It means that they
underwent further reactions before benzylation, in spite
of the fact that the quenching agent was used immedi-
ately after mixing of reagents.
This is another example found by us that organopo-
tassium compounds easily open the crown ether ring
giving unsaturated alkoxide containing four CH2CH2O
groups. It seems that this reaction might be applied as a
method helpful for checking the presence of short-lived
organometallic intermediates in the reaction mixture,
i.e., for their qualitative analysis. However, some limi-
tations on this method should be taken into account in
this case. The negative result of the experiment, i.e., the
absence of the expected alkoxide, cannot be a proof that
the studied reaction occurs without the participation of
organometallic intermediates [29].
700 quadrupole detector. Diethylene glycol dimethyl
ether was used as an internal standard for yield mea-
surements. Gaseous reaction products were searched for
by GC with a 2.4-m stainless steel column packed with
Al2O3, 0.02–0.03 mm, deactivated with 5% K2CO3 in an
INCO 505 gas chromatograph equipped with a flame
1
ionization detector. H and 13C NMR spectra were re-
corded at 20 °C on a Varian VXR-300 multinuclear
spectrometer at the 1H resonance frequency of 300
MHz, and at the 13C resonance frequency of 75 MHz.
Deuterated acetone was used as the solvent. Chemical
shifts were referenced to tetramethylsilane (TMS) serv-
ing as an internal standard.
Glycidol (Merck) was distilled at 61 °C/15 mm Hg.
Tetrahydrofuran (POCH) was boiled over CuCl to de-
compose peroxides and then over CaH2 for 10 h; finally
it was distilled at 66 °C. The fraction obtained was dried
over metallic potassium for 20 h and redistilled prior to
use. Methanol and propanol were distilled twice. 15-
Crown-5 (Aldrich) was dried under vacuum at 50 °C for
8 h. Potassium (Fluka) was purified in boiling tetrahy-
drofuran and then distilled under high vacuum.
4.1. 2-Benzyloxy-1-propanol and 1-benzyloxy-2-propanol
A mixture of 0.3 mol 1,2-propanediol, 0.1 mol benzyl
chloride, 50% NaOH (60 mL), 0.005 mol tetrabuty-
lammonium hydrogensulfate, and benzene (60 mL) was
stirred intensely at 70–80 °C on a water bath for 3 h.
Subsequently cooled water (100 mL) and hexane (100
mL) was added to the mixture. The layers were sepa-
rated, the organic layer was washed three times with
water (50 mL) and dried with anhydrous MgSO4. After
removing hexane and benzene on a rotatory evaporator
the residue was distilled under reduced pressure. A
mixture of 2-benzyloxy-1-propanol and 1-benzyloxy-2-
propanol was finally obtained in 82% yield (40:60).
B.p. ¼ 130–131 °C/3 mm Hg. The attempt to separate
the mixture was unsuccessful. 1H NMR spectra were
analyzed by a simulation study, using NMR software
MestRe-C 2.3a (Unidade de Resonancia Magnetica,
Universidade de Santiago de Compostela, La Coruna,
Spain).
3. Conclusions
The mechanism of the reaction of 1 with selected al-
cohols depends on the mode of substrate delivery. De-
protonation of alcohol occurs at its excess. It leads to
the appropriate alkoxide, which is decomposed at the
excess of 1. Potassium oxide and short-lived organopo-
tassium intermediates are formed in the case of simple
alcohols, e.g., methanol or propanol. The organopo-
tassium compounds react then with crown ether giving
potassium tetraethylene glycoxide vinyl ether.
The course of the reaction of 1 with potassium gly-
cidoxide differs from that with simple alkoxides. The
oxirane ring opening occurs in such a case and potas-
sium oxide is not formed. However, the oxirane ring of
glycidol is opened also at its excess resulting in orga-
nopotassium alkoxide. The latter reacts with the next
glycidol molecule and does not with crown ether.
4.1.1. 2-Benzyloxy-1-propanol (14)
1H NMR (CDCl3): d ¼ 7:30 ꢀ 7:35 (m, 5 H, Ph); 4.61
(s, 2 H, CH2); 3.75 (m, 1 H, CHðMÞ; JAM ¼ 6:0 Hz,
4. Experimental
JBM ¼ 4:8 Hz, JMX ¼ 6:3 Hz); 3.55 (q, 1H, CHðAÞ
JAB ¼ 10; 2 Hz, JAM ¼ 6:0 Hz); 3.45 (q, 1 H, CHðBÞ
JAB ¼ 10:2 Hz, JBM ¼ 4:8 Hz); 1.20 (d, 3 H, CHðXÞ
;
;
;
GC–MS analyses of liquids were run on a 30-m fused
silica capillary column DB-5 in a Varian 3300 gas
chromatograph equipped with a Finnigan MAT SSQ
JMX ¼ 6:3 Hz). Mass spectrum (m=e): 166 [Mþ, 1]; 107
(25); 91 (100); 79 (6); 77 (6); 75 (8); 65 (22); 51 (1).

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Z. Grobelny et al. / Journal of Organometallic Chemistry 689 (2004) 2361–2367
4.1.2. 1-Benzyloxy-2-propanol
(CH); 73.23 (CH2–Ph); 71.03 (CH2–Ph); 17.25 (CH3).
13C NMR spectrum was earlier presented in [41]. Mass
spectrum (m=e): 256 [Mþ, 1]; 165 (36); 107 (18); 91 (100);
79 (6); 65 (13); 39 (2).
GC–MS and NMR spectra of benzyl glycidyl ether
[26], benzyl methyl ether [27], benzyl propyl ether [27],
and tetraethylene glycol benzyl vinyl ether [12] have
been reported previously.
1H NMR (CDCl3): d ¼ 7:30 ꢀ 7:35 (m, 5 H, Ph); 4.55
(s, 2 H, CH2); 3.97 (m, 1 H, CHðMÞ; JAM ¼ 3:0 Hz,
JBM ¼ 7:5 Hz, JMX ¼ 6:3 Hz); 3.42 (q, 1 H, CHðAÞ
JAB ¼ 8:5 Hz, JAM ¼ 3:0 Hz); 3.26 (q, 1 H, CHðBÞ
JAB ¼ 8:5 Hz, JBM ¼ 7:5 Hz); 1.12 (d, 3 H, CHðXÞ
;
;
;
4.4. General procedure
JMX ¼ 6:3 Hz). Mass spectrum (m=e): 165 [Mþ, 30]; 107
Preparation of Kꢀ, Kþ(15-crown-5)2 1 tetrahydrofu-
ran solution was performed at ambient temperature in an
apparatus presented in [12]. Potassium (about 1.5 g) was
distilled into a reactor under a high vacuum. Then, 0.2 M
15-crown-5 solution in tetrahydrofuran (10 mL) was
dropped on the metal mirror. After 25 min of ultrasonic
mixing a deep blue 0.1 M solution of 1 was obtained. The
solution was finally filtered through a glass frit.
The reaction was conducted in a 50 mL reactor
thermostatted at 25 °C. In one series of experiments 0.1
M solution of 1 (10 mL) was gradually introduced into
the reactor filled with 0.5 M of selected alcohol in tet-
rahydrofuran (10 mL) while mixing. In the other ex-
periments the blue potassium solution was titrated with
0.1 M alcohol solution until discoloration of the reac-
tion mixture. Benzyl bromide (10% excess in relation to
potassium ions) was used as the quenching agent to
transform non-volatile reaction products into the vola-
tile compounds. Then, water (2 mL) was added to the
reaction mixture obtained at the excess of 1. The basicity
of the water phase was found in the system with meth-
anol or propanol, which indicated the presence of po-
tassium hydroxide. The products obtained were
identified matching their mass spectra, retention times,
as well as NMR spectra.
(32); 91 (100); 79 (6); 77 (5); 65 (18); 51 (1).
4.2. Benzyl vinyl ether (23)
A mixture of 0.01 mol 2-bromoethylbenzyl ether, 0.01
mol 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and tet-
rahydrofuran (10 mL) was stirred intensely at 60 °C for
8 h. Subsequently cooled pentane (10 mL) was added
and the mixture was left at 0 °C overnight. The salt
precipitate was filtered and washed with 10 mL of tet-
rahydrofuran and pentane mixture (1:1). Volatile frac-
tions were removed by distillation and benzyl vinyl ether
was obtained in practically quantitative yield (purity
>99%; GC). B.p. ¼ 50–51 °C/16 mm Hg. Mass spectrum
(m=e): 134 [Mþ, 4]; 116 (7); 105 (11); 91 (100); 77 (7); 65
(30); 51 (9); 39 (11). 1H and 13C NMR spectra (in
CDCl3) have been already presented in [39,40].
4.3. 1,2-Dibenzyloxypropane (24)
A mixture of 0.1 mol 1,2-propanediol, 0.22 mol
benzyl chloride, 50% NaOH (60 mL), 0.007 mol tetra-
butylammonium hydrogensulfate, and benzene (60 mL)
was stirred intensely at 70–80 °C on a water bath for 3 h.
Subsequently cooled water (100 mL) and hexane (100
mL) was added. The layers were separated, the organic
layer washed three times with water (50 mL) and dried
with anhydrous MgSO4. After removal of hexane and
benzene the residue was distilled under reduced pressure.
1,2-Dibenzyloxypropane was finally obtained in 62%
yield (purity >97%; GC). B.p. ¼ 170–171 °C/2 mm Hg.
Acknowledgements
The authors are indebted to Dr. K. Skutil for the
analysis of gaseous compounds with the GC technique.
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