Solid-phase reactions of alkanedicarboxylic acids with the Pb(OAc) 4-NH4Cl system

Article abstract of DOI:10.1070/MC2003v013n06ABEH001815

The title reactions of HOOC(CH₂)_nCOOH acids afford α,ω-dichloroalkanes (n = 3, 4, 6) and lactones (n = 3, 4) as the main products.

Full text of DOI:10.1070/MC2003v013n06ABEH001815

, 2003, 13(6), 264–265
Solid-phase reactions of alkanedicarboxylic acids with the Pb(OAc)4–NH4Cl system
Gennady I. Nikishin,a Lyubov L. Sokova,a Viktor D. Makhaevb and Nadezhda I. Kapustina*a
a N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russian Federation.
Fax: +7 095 135 5328; e-mail: nika@ioc.ac.ru
b Institute of Problems of Chemical Physics, Russian Academy of Sciences, 142432 Chernogolovka, Moscow Region,
Russian Federation
10.1070/MC2003v013n06ABEH001815
The title reactions of HOOC(CH2)nCOOH acids afford α,ω-dichloroalkanes (n = 3, 4, 6) and lactones (n = 3, 4) as the main
products.
In the last decade, the solid-phase and solvent-free reactions
of organic compounds have attracted considerable attention.
Interest in these reactions arises from ecological and eco-
nomical factors, as well as from the fact that some solid-phase
reactions are highly regioselective and stereoselective.1–3
We studied reactions with lead tetraacetate, which is widely
used as an oxidising reagent in organic chemistry. We oxidised
alkan-1-ols and 1-alkylcycloalkanols with lead tetraacetate and
lead tetraacetate–metal halide systems4,5 and found unexpected
results. Thus, the mechanism of the solid-phase oxidation of
alkan-1-ols is different from that in a liquid phase.4
PbIVOAc/PbIIOAc
OH
OPbIV/PbII
Cl
Cl
2
2
– AcOH
O
O
4b
5
– PbIVCl/PbIICl
O
O
3b
Scheme 2
Here, we report on the solid-phase reactions of Pb(OAc)4,
viz., the oxidative decarboxylation of alkanedicarboxylic acids,
such as glutaric, adipic, and suberic acids 1a–c. We found that
the solid-phase reactions of acids 1a–c with the Pb(OAc)4–
NH4Cl system gave rise to α,ω-dichloroalkanes 2a–c, lactones
3a,b, and ω-chloro acids 4b,c (Scheme 1).†
†
Procedures for the reactions of alkanedicarboxylic acids with the
Pb(OAc)4–NH4Cl system.
(a) Without mechanical activation (method A). A mixture of an acid,
Pb(OAc)4 and NH4Cl was thoroughly stirred in a bottle (5–10 min) and
kept at room temperature until the reaction was complete [complete
conversion of Pb(OAc)4]. The reaction products were extracted (CHCl3,
diethyl ether), and their yields were determined by GLC using an internal
standard. The conversion of Pb(OAc)4 was determined iodometrically.9
The reaction products were isolated by column chromatography (silica
gel, 40/100 mesh; heptane–ethyl acetate, 3:7). The structures of the
A combination of Pb(OAc)4 with NH4Cl was used as an
oxidising reagent. The solid-phase reactions were carried out in
two modes (with and without mechanical activation in a vibra-
tion mill). The results are given in Table 1, together with the
results of the reactions of acids 1a–c and 4b with the Pb(OAc)4–
NH4Cl system in an acetic acid solution (at 80 °C) for com-
parison. Note that the liquid-phase decarboxylation of carboxylic
acids with Pb(OAc)4 and the chlorodecarboxylation with the
Pb(OAc)4–LiCl system have been studied in considerable detail.6
As for alkanedicarboxylic acids, it is only known that the
reactions of glutaric and adipic acids with Pb(OAc)4 and I2 in
CCl4 solutions under UV irradiation at 77 °C afforded 1,3-di-
iodopropane (12%) and 1,4-diiodobutane (33%), respectively.7
Under the reaction conditions, acids 1a–c were transformed
into γ-butyrolactone 3a, δ-valerolactone 3b, and 1,6-dichloro-
hexane 2c, respectively, in high yields either in a solid phase
with mechanical activation or in a liquid phase. The solid-
phase reactions, which were not mechanically activated, pro-
ceeded less selectively. Thus, the reactions of acids 1b,c gave
predominantly dichloroalkanes 2b,c along with chloro acids
4b,c in a ratio of ~3–4:1. The reaction of acid 1a produced
1,3-dichloropropane 2a and γ-butyrolactone 3a in a ratio of ~1:2.
In a liquid phase, lactone 3b was derived from chloro acid 4b
through the formation of lead salt Cl(CH2)4COOPbIV/PbII 5, as
evidenced by the results of runs 7, 8 and 15 (Table 1) (Scheme 2).†
The solid-phase reaction of chloro acid 4b without mecha-
nical activation gave 1,4-dichlorobutane 2b rather than lactone
reaction products were confirmed by H and 13C NMR (200 MHz) and
IR spectroscopy (NaCl) and GC–MS (70 eV), as well as by comparison
with authentic samples.
1
(b) With mechanical activation (method B). The reaction mixture
(total weight of 1–2 g) was mechanically activated at room temperature
using a vibration mill with a vibration frequency of 12 Hz and an
amplitude of 11 mm in a sealed steel reactor with a volume of ~80 cm3.
In the reactions, steel balls 12.3 mm in diameter with a total weight of
~150 g were used for activation. The duration of mechanical treatment
was 4 h. Then, the reaction mixture was treated according to the above
procedure.
(c) In a solution in AcOH (method C). The reaction mixture of 1a–c or
4b, Pb(OAc)4 and NH4Cl in AcOH (10 ml) was heated with vigorous
stirring at 80 °C until the complete conversion of lead. Then, an excess
of AcOH was distilled off, and the residue was treated as described
above.
1
For 2a: H NMR (CDCl3) d: 2.15–2.36 (m, 2H, CH2), 3.72 (t, 4H,
J 6.0 Hz). 13C NMR (CDCl3) d: 34.81 (CH2), 41.43 (CH2Cl).
1
For 2b: H NMR (CDCl3) d: 1.91–1.98 (m, 4H, CH2), 3.59 (t, 4H,
CH2Cl, J 6.0 Hz). 13C NMR (CDCl3) d: 29.61 (CH2), 44.11 (CH2Cl).
1
For 2c: H NMR (CDCl3) d: 1.43–1.51 (m, 4H, CH2), 1.73–1.82 (m,
4H, CH2), 3.54 (t, 4H, CH2Cl, J 6.3 Hz). 13C NMR (CDCl3) d: 21.01
(CH2), 32.32 (CH2), 44.85 (CH2Cl).
1
For 3a: H NMR (CDCl3) d: 2.13–2.28 (m, 2H, CH2), 2.43 (t, 2H,
J 7.9 Hz), 4.30 (t, 2H, CH2, J 7.0 Hz). 13C NMR (CDCl3) d: 21.91,
27.54, 68.37 (CH2), 177.68 (C=O). IR (NaCl, n/cm–1): 1772 (C=O).
HO
OH
Pb(OAc)4–NH4Cl
n
1
O
O
For 3b: H NMR (CDCl3) d: 1.79–1.83 (m, 4H, CH2), 2.56 (t, 2H,
CH2, J 6.4 Hz), 4.36 (t, 2H, CH2, J 5.4 Hz). 13C NMR (CDCl3) d: 19.00,
22.23, 29.80, 69.56 (CH2), 171.87 (C=O). IR (NaCl, n/cm–1): 1712
(C=O).
1a c
–
OH
n
Cl
n
1
Cl
Cl
For 4b: H NMR (CDCl3) d: 1.79–1.82 (m, 4H, CH2), 2.40 (t, 2H,
n
O
O
O
CH2COOH, J 6.5 Hz), 3.55 (t, 2H, CH2Cl, J 5.7 Hz). 13C NMR (CDCl3)
d: 21.79, 31.55, 33.08 (CH2), 44.28 (CH2Cl), 179.03 (C=O). IR (NaCl,
n/cm–1): 1704 (C=O). MS, m/z: 137 [M + H]+.
2a–c
3a,b
4b,c
a n = 1
b n = 2
c n = 4
1
For 4c: H NMR (CDCl3) d: 1.81–1.91 (m, 8H, CH2), 2.42 (t, 2H,
CH2COOH, J 6.6 Hz), 3.60 (t, 2H, CH2Cl, J 5.8 Hz). 13C NMR (CDCl3)
d: 20.12, 20.65, 21.81, 31.72, 33.43 (CH2), 44.31 (CH2Cl), 179.21
(C=O). IR (NaCl, n/cm–1): 1707 (C=O). MS, m/z: 165 [M + H]+.
Scheme 1
– 264 –

, 2003, 13(6), 264–265
Therefore, the solid-phase reactions of alkanedicarboxylic
acids 1a–c with the Pb(OAc)4–NH4Cl system with or without
mechanical activation and the liquid-phase reactions provide a
new approach to γ-butyro- and δ-valerolactones and 1,5- and
1,7-dichlorolalkanes, which can find use in preparative chemistry.
Table 1 Compositions and yields of the reaction products of alkane-
dicarboxylic acids 1a–c and chloro acid 4b with the Pb(OAc)4–NH4Cl
system.a
Products and yields/mmol
Reaction
Reaction
time/h
Run
Acid
conditionsb
2
3
4
This work was supported by the Russian Foundation for
Basic Research (grant no. 02-03-32810a) and the Federal
Programme on Support of Leading Scientific Schools (project
no. 2121.2003.3).
1
2
3
1a
A
B
C
48
4
0.3
0.27
+
–
0.49
0.93
0.83
–
–
–
4
5
6
7
8
1b
A
A
B
C
C
48
72c
4
0.3
0.15
0.41
0.62
0.05
–
–
–
0.65
0.90
0.40
0.14
0.17
0.20
–
References
1 F. Toda, Acc. Chem. Res., 1995, 28, 480.
–
0.47
2 B. A. Lorsbach and M. J. Kurth, Chem. Rev., 1999, 99, 1549.
3 K. Tanaka and F. Toda, Chem. Rev., 2000, 100, 1025.
4 N. I. Kapustina, L. L. Sokova, V. D. Makhaev, A. P. Borisov and G. I.
Nikishin, Izv. Akad. Nauk, Ser. Khim., 2000, 1870 (Russ. Chem. Bull.,
Int. Ed., 2000, 49, 1842).
5 N. I. Kapustina, L. L. Sokova, V. D. Makhaev, L. A. Petrova and G. I.
Nikishin, Izv. Akad. Nauk, Ser. Khim., 1999, 2104 (Russ. Chem. Bull.,
1999, 48, 2080).
9
10
11
12
1c
A
A
B
C
96
96c
4
0.44
0.60
0.92
0.79
–
–
–
–
0.11
0.13
–
0.3
–
13
14
15
4b
A
B
C
48d
4
0.3d
0.41
–
–
–
0.92
0.88
–
–
–
6 R. A. Sheldon and J. K. Kochi, Organic Reactions, J. Wiley and Sons,
Inc., New York–London–Sydney–Toronto, 1972, vol. 19, p. 279.
7 D. H. R. Barton and E. P. Serebryakov, Proc. Chem. Soc., 1962, 309.
8 L. Fieser and M. Fieser, Reagents for Organic Synthesis, J. Wiley,
New York–London–Sydney, 1968.
aAcid, 1 mmol; Pb(OAc)4, 2 mmol; NH4Cl, 4 mmol; conversion of Pb(OAc)4,
~ 100%. A, solid-phase reaction without mechanical activation. B, solid-
b
phase reaction with mechanical activation. C, reaction in a solution in AcOH
c
d
(10 ml), 80 °C. Pb(OAc)4, 3 mmol; NH4Cl, 6 mmol. Pb(OAc)4, 1 mmol;
NH4Cl, 2 mmol.
3b (run 13). In this case, lactonization is hindered because
two rigidly fixed reaction centres in salt 5 are far apart. The
mechanical treatment of salt 5 in a vibration mill led to the
cyclization to lactone 3b with high selectivity, apparently, due
to the formation of defects in the crystal lattice (run 14).
Received: 30th June 2003; Com. 03/2141
– 265 –