Hydroacetoxylation of olefins with acetic acid genetated in situ from vinyl acetate in the presence of ruthenium complexes

Article abstract of DOI:10.1134/S1070428011020011

Ruthenium complexes catalyze the decomposition of vinyl acetate releasing the acetic acid and its subsequent addition to linear and cyclic olefins.

Full text of DOI:10.1134/S1070428011020011

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 2, pp. 155160. Pleiades Publishing, Ltd., 2011.
Original Russian Text  R.I. Khusnutdinov, N.A. Shchadneva, L.F. Khisamova, U.M. Dzhemilev, 2011, published in Zhurnal Organicheskoi Khimii, 2011,
Vol. 47, No. 2, pp. 167172.
Hydroacetoxylation of Olefins with Acetic Acid
Genetated in situ from Vinyl Acetate
in the Presence of Ruthenium Complexes
R. I. Khusnutdinov, N. A. Shchadneva, L. F. Khisamova, and U. M. Dzhemilev
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, Ufa, 450075 Russia
e-mail: ink@anrb.ru
Received May 4, 2010
Abstract—Ruthenium complexes catalyze the decomposition of vinyl acetate releasing the acetic acid and its
subsequent addition to linear and cyclic olefins.
DOI: 10.1134/S1070428011020011
Ru(OH)Cl3
Acetates of palladium, thallium, lead, and mercury are
known to catalyze the acetic acid addition to olefins [1–3].
The reaction requires severe conditions, it is carried out
in excessAcOH, and often provides a mixture of products
[1–3]. We recently found that rhodium compounds, in
particular, Wilkinson’s complex Rh(PPh3)3Cl, catalyzed
the decomposition of vinyl acetate with the liberation
of acetic acid and the subsequent addition of AcOH to
a multiple bond [4]. This conjugate reaction occurs the
best with the series of olefins of the norbornene structure
containing a double bond activated by the “-strain”.
Yet our attempt to extend this reaction to nonactivated
-olefins and simple cycloolefins was unsuccessful. As
showed further research, efficient catalysts of the vinyl ac-
etate decomposition followed by the addition ofAcOH to
nonactivated olefins proved to be ruthenium complexes,
among which the most active were Ru(PPh3)2Cl2 and
Ru(OH)Cl3. However in contrast to rhodium compounds
the reactions involving the ruthenium catalysts require
more stringent conditions: 140–180°C, 2–8 h.
CH3CH(OAc)2
+
OAc
CH2Cl2,
140°C, 5 h
I
The complex Ru(PPh3)2Cl2 catalyzes the similar re-
action, but since the Ru(OH)Cl3 is more available it has
been used in the majority of the experiments. The best
solvents are dichloromethane and chloroform. In benzene,
toluene, ether solvents (ethyl ether, THF, dioxane) and
without solvent the reaction failed to proceed.
The monitoring by GLC and titration showed that in
the presence of Ru(OH)Cl3 at 160°C the vinyl acetate
gradually decomposed with the liberation of acetic acid
that accumulated in the reaction mixture but was not con-
sumed. For instance, the content of AcOH after 1 h was
6.9, after 2 h, 8.8, after 3 h, 16.4, after 4h, 16.7 mg ml−1.
The content of the ethylidene diacetate in the reaction
mixture to the end of the run did not exceed 1–2%. In
CH2Cl2 the vinyl acetate underwent complex transfor-
mations. For inatance, after 1 h of heating the reaction
mixture the content of AcOH reached 9.1 mg ml−1, and
it was consumed in the course of the process (after 2 h,
6.0, after 3 h, 5.9 mg ml−1). The yield of the ethylidene
diacetate, the product of AcOH addition to vinyl acetate,
after 3 h attained 80%. Further heating is undesirable,
for the reaction is reversible, and after 4 h the content of
AcOH in the presence of CH2Cl2 is 10.6 mg ml−1. The
atalysts are used in the amount no more than 1 mol%. The
increase in the catalyst concentration led to the formation
Vinyl acetate (I) proper in the presence of Ru(OH)Cl3
at 140°C within 5 h (or at 160°C in 3 h) in 80% yield was
converted into ethylidene diacetate, namely, the acetic
acid evolved in the course of the reaction from the vinyl
acetate added to its double bond. The other product of the
vinyl acetate decomposition, acetylene, under the action
of the catalyst afforded benzene that did not virtually
affect the reaction course being an additional solvent.
155

KHUSNUTDINOV et al.
156
cyclopentyl acetate (VIII) was 97%, the yield of cyclodo-
decyl acetate (XI) was below 10%.
in the reaction mixture of macromolecular compounds.
In the preceding study [4] we carried out a preliminary
activation of the catalysts by their heating in CH2Cl2 or
CHCl3 at 200°C, and then used the activated catalyst for
the hydroacetoxylation at lower temperature (80–100°C).
This trick was inefficient with ruthenium since the reac-
tion proceeded with a notable rate only at the elevated
temperature.
OAc
I
Ru(OH)Cl3, CH2Cl2,
180°C, 3 h
(CH2)n
VIII_XI
(CH2)n
The composition of the reaction mixture obtained by
heating cyclododecyl acetate (XI) at 180°C over 3 h in
the presence of 1 mol% of Ru(OH)Cl3 was close in the
composition to the reaction product obtained by the reac-
tion of cyclododecene with vinyl acetate under similar
conditions, demonstrating the reversibility of the reaction.
The reaction with vinyl acetate catalyzed with Ru(OH)
Cl3 fairly efficiently occurred with nonactivated -olefins
and cycloolefins: The addition of AcOH to these sub-
strates was faster than to the vinyl acetate as showed the
total absence of the ethylidene diacetate in the reaction
mixture.
The norbornene possessing an activated double
bond reacted with vinyl acetate under milder conditions
(140°C, 2 h). The reaction proceeded stereoselectively
giving norbornyl-exo-2-acetate (XII) in 92% yield. The
structure of acetate XII was unambiguously proved by
the 13C NMR spectrum and by comparison with the
sample formerly obtained in the presence of rhodium
complex [4].
In the case of -olefins the yields of the alkyl acetate
depends on the length of the alkyl group in the olefin mol-
ecule. Thus while the yields of 2-hexyl (II) and 2-heptyl
(III) acetates obtained in the reaction of vinyl acetate with
1-hexene and 1-heptene reached 98 and 95% respectively,
the yield of 2-octadecyl acetate (V) did not exceed 8%.
OAc
I
R
I
Ru(OH)Cl3,
R
OAc
II_V
CH2Cl2,
Ru(OH)Cl3, CH2Cl2,
XII
180°C, 2 h
140°C, 2 h
The styrene behaves peculiarly in this reaction. Its
reaction products with vinyl acetate in the presence of
Ru(OH)Cl3 are three compounds: (1E)-1,3-diphenylbut-
1-ene (XIIIa), 2- and 1-acetoxy-1,3-diphenylbutanes
(XIIIb and XIIIc) in the ratio 6 : 5 : 1 (Scheme 2). The
structure of esters XIIIb and XIIIc suggests that in the
case of styrene the olefin undergoes catalytic dimerization
before the hydroacetoxylation. The yield and the compo-
sition of the reaction products was established by isolation
of the target compounds by column chromatography,
by analyses with GC-MS method and preparative GLC
R = Bu (II), C5H11 (III), C10H21 (IV) C16H33 (V).
The hydroacetoxylation proceeded fairly cleanly with
allylcyclohexane and allylbenzene (Scheme 1).
The similar dependence of the product yield on the
length of the hydrocarbon chain was conserved also in
the cycloolefins series. For instance, when the yield of
Scheme 1.
I
OAc
Scheme 2.
VI
Ru(OH)Cl3
CH3
I
180°C, 3 h,
CH2Cl2
Ph
Ph
Ph
180°C, 1 h
CH3
XIIIa
I
OAc
Ph
Ph
+
+
Ph
Ph
OAc
VII
OAc CH3
n = 1 (VIII), 2 (IX), 4 (X), 8 (XI).
XIIIb
XIIIc
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HYDROACETOXYLATION OF OLEFINS WITH ACETIC ACID
157
Scheme 3.
using an internal reference (cyclohexyl acetate) with the
correction of peaks area. The structure of the linear olefin
XIIIa was confirmed by the 13C NMR spectrum and by
comparison with an authentic sample [5].
I,
AcO
Ru(OH)Cl3
CH2Cl2,
OAc
180°C, 2 h
The cycloocta-1,5-diene in this process reacted ex-
clusively at one double bond to form 5-acetoxycyclooct-
1-ene (XIVa), i.e., the addition of AcOH to the diene
occurred without the transannular rearrangement char-
acteristic of this compound [6].
XVIIa
OAc
XVIIb
progress was monitored by GLC.
OAc
I
The ruthenium catalysts proved to be more efficient
for performing the reaction in question also in the series
of electron-deficient olefins. This advantage is well seen
by the example of the proper vinyl acetate that at heat-
ing in typical conditions is selectively converted into
ethylidene diacetate.
Ru(OH)Cl3, CH2Cl2,
180°C, 1 h
XIV
2-Pentene reacted with the vinyl acetate giving 2- and
3-pentyl acetates (XVa, XVb) in the ratio 1 : 10 C and
the overall yield 90%. The reaction proceeded at 140°C
over 3 h. Because of the similar boiling points of acetates
XVa and XVb we determined their yields and the ratio by
GLC and GC-MS methods by comparison with authentic
esters obtained from 2- and 3-pentanols. The structure of
acetates XVa and XVb was proved by 13C NMR spectra.
In particular, the presence of signals of double intensity
at 9.29 (C1,5) and 26.55 ppm (C2,4) is characteristic of
3-pentyl acetate XVb having a symmetric structure. In its
turn, the spectrum of 2-pentyl acetate contains 7 signals
of carbon atoms (see EXPERIMENTAL).
The regioselectivity of the addition of AcOH gener-
ated from the vinyl acetate is also observed with acrylo-
nitrile which in 75% yield is converted into 2-acetoxy-
propionitrile (XVIII).
OAc
I
CN
CN
XVIII
Ru(OH)Cl3, CH2Cl2,
160°C, 3 h
The direction of the reaction of vinyl ethers with the
vinyl acetate depends on their structure. For instance,
the addition of AcOH to vinyl butyl ether results in the
formation of 1-butoxyethyl acetate (XIX) in 85% yield.
The hydroacetoxylation of 2-hexene requires more se-
vere conditions (170°C, 3 h), the conversion of the initial
olefin does not exceed 60%, and the reaction provides a
mixture of two regioisomers: 2- (II) and 3-hexyl acetate
(XVI) in the ratio 3 : 2.
The vinyl phenyl ether under similar conditions was
converted into phenyl acetate (XX).
I
I,
Ph OAc
XX
O Ph
OAc
Ru(OH)Cl3, CH2Cl2,
160°C, 3 h
Ru(OH)Cl3
II
+
CH2Cl2,
XVI
170°C, 3 h
The behavior in the studied reaction of electron-
deficient allyl monomers depends on the nature of the
substituent. Thus, the allylamine and the allyltrimethyl-
silane in the reaction with the vinyl acetate even under
the mild conditions (120°C, 1 h) were converted into
polymeric products. The allyl acetate and methyl acetate
were recovered from the reaction mixture intact, and
the methyl acrylate and methyl methacrylate suffered
polymerization.
The 2,5-dimethylhexa-1,5-diene with two 1,1-disub-
stituted double bond added the acetic acid to both double
bonds at the use of the 4-fold excess of vinyl acetate,
but the yield of the diacetate XVIIa did not exceed 40%
(Scheme 3). The attempt to increase the yield of com-
pound XVIIa by prolonged heating failed, and even after
3 h of heating the reaction mixture contained monoacetate
XVIIb. Besides we found in the reaction mixture acetic
acid and the initial 2,5-dimethylhexa-1,5-diene, appar-
ently due to the reversibility of the process. The reaction
While the allyl alcohols in the chosen reaction condi-
tions underwent a fast polymerization, the but-3-en-1-ol
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KHUSNUTDINOV et al.
158
2-Hexyl acetate (II). Yield 98%, bp 80–81°C
(40 mm Hg). IR spectrum, , cm–1: 1740 (C=O). 13C
NMR spectrum, , ppm: 14.03 (C6), 20.08 (C1), 21.27
(CH3), 22.69 (C5), 27.81 (C4), 35.80 (C3), 71.22 (C2),
170.79 (C=O). Found, %: C 67.31; H 9.75. C8H16O2.
Calculated, %: C 67.57; H 9.93.
was selectively acetylated at the hydroxy group, and the
double bond remained untouched.
I
OAc
OH
Ru(OH)Cl3, CH2Cl2,
140°C, 3 h
XXI
2-Heptyl acetate (III). Yield 95%, bp 83–84°C
(13 mm Hg). IR spectrum , cm–1: 1740 (C=O). 13C NMR
spectrum, , ppm: 13.95 (C7), 19.95 (C1), 21.29(CH3),
22.54 (C6), 26.90 (C4), 31.65 (C5), 35.80 (C3), 72.42
(C2), 170.38 (C=O).
The structure of compounds synthesized was es-
tablished from the spectral data, the comparison with
authentic samples and the published data.
EXPERIMENTAL
2-Dodecyl acetate (IV). Yield 22%, bp 144–145°C
13
(13 mm Hg). C NMR spectrum, , ppm: 14.09 (C12),
19.91 (C1), 21.29 (CH3), 22.70 (C11), 25.42 (C4), 27.55
(C5), 28.01 (C6), 28.13 (C7), 28.36 (C8), 29.21 (C9), 31.35
(C10), 36.13 (C3), 71.85 (C2), 170.38 (C=O).
The purity od obtained compounds was checked and
the composition of the reaction products was analyzed
by GLC on a chromatograph Chrom-5, flame-ionization
detector, columns 1.2 and 3 m long, diameter 3 mm; sta-
tionary phase 5% of SE-30 on Chromaton N-AW-HMDS
(0.125–0.160 mm), carrier gas helium (50 ml/min), oven
temperature 50–220°C.
IR spectra in the range 550–3600 cm–1 were recorded
on a spectrophotometer Bruker Vertex 70V from pellets
with KBr or mulls in mineral oil. 1H and 13C NMR spectra
were registered on a spectrometer Bruker Avance-400 at
operating frequencies 400.13 and 100.62 MHz in CDCl3,
chemical shifts were measured with respect to TMS. Mass
spectra were measured on a GC-MS instrument Shimadzu
QP-2010 Plus, capillary column Supelko PTE-5 (30
m0.35 mm). Elemental composition was determined
on an analyzer Carlo Erba-1106.
2-Octadecyl acetate (V). Yield 8%. IR spectrum ,
cm–1: 1740 (C=O), 1200 (C–O–C). 13C NMR spectrum,
, ppm: 14.10 (C18), 19.91 (C1), 21.29 (CH3), 22.68 (C17),
25.39 (C4), 27.55 (C5), 27.74 (C6–9), 28.01 (C10), 28.12
(C11), 28.35 (C12), 28.90 (C13), 28.99 (C14,C15), 31.91
(C16), 35.93 (C3), 71.04 (C2), 170.38 (C=O). Found, %:
C 76.79; H 12.91. C20H40O2. Calculated, %: C 76.86;
H 12.90.
1-Methyl-2-cyclohexylethyl acetate (VI). Yield
50%, bp 94–95°C (12 mm Hg). 13C NMR spectrum,
, ppm: 20.44 (C1), 21.32 (CH3), 25.99 (C6, C8), 26.84
(C7), 33.05 (C5, C9), 37.52 (C4), 43.44 (C3), 72.49 (C2),
170.45 (C=O). Found, %: C 71.48; H 10.83. C11H20O2.
Calculated, %: C 71.69; H 10.94.
Hydroacetoxylation of olefins applying vinyl ac-
etate. Into a stainless-steel pressure microreactor of 17 ml
capacity was charged under argon 0.1 mol of catalyst
Ru(OH)Cl3, 10 mmol of olefin, 15 mmol of vinyl acetate,
and 2 ml of dichloromethane. The reactor was hermeti-
cally closed. The reaction was carried out at constant
stirring over 1–3 h at 140–180°C (depending on the
structure of the initial olefin). On completing the reaction
the reactor was cooled to room temperature and opened.
The reaction mixture was filtered through a bed ofAl2O3
(eluent hexane–ether, 1:1), the solvent was distilled off,
the residue was distilled in a vacuum.
1-Methyl-2-phenylethyl acetate (VII). Yield 66%,
bp 98–99°C (6 mm Hg). 13C NMR spectrum, , ppm:
20.96 (CH3), 21.33 (C1), 42.31 (C3), 71.67 (C2), 127.66
(C7), 129.51 (C5, C9), 129.77 (C6, C8), 137.67 (C4), 170.80
(C=O). Found, %: C 73.96; H 7.78. C11H14O2. Calculated,
%: C 74.12; H 7.92.
Cyclopentyl acetate (VIII). Yield 97%, bp 70–71°C
(40 mm Hg) (bp 153–154°C [8]). IR spectrum, , cm–1:
1738 (C=O), 1200 (C–O–C). 13C NMR spectrum, , ppm:
21.08 (CH3), 23.63 (C3, C4), 32.70 (C2, C5), 76.51 (C1),
169.25 (C=O).
Cyclohexyl acetate (IX). Yield 98%, bp 82–83°C
(40 mm Hg) (bp 172–174°C [8]). 13C NMR spectrum,
, ppm: 21.02 (CH3), 24.25 (C3, C5), 25.95 (C4), 32.19
(C2, C6), 72.11 (C1), 169.20 (C=O). Mass spectrum, m/z
(Irel, %): [M]+ absent, 100 (2), 99 (2), 83 (4), 82 (48), 81
(4), 67 (35), 61 (3), 58 (4), 55 (10), 54 (9), 43 (100), 42
(5), 41 (10), 39 (8).
Ethylidene 2,2'-diacetate. Yield 80%, bp 90°C
(20 mm Hg) {bp 69°C (17 mm Hg) [7]}. IR spectrum,
, cm–1: 1760 (C=O). 13C NMR spectrum, , ppm: 19.20
(CH3), 20.76 (CH3), 88.24 (CH), 168.55 (C=O). Found,
%: C 49.12; H 6.75. C6H10O4. Calculated, %: C 49.31;
H 6.90.
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HYDROACETOXYLATION OF OLEFINS WITH ACETIC ACID
159
Cyclooctyl acetate (X). Yield 58%, bp 110–112°C
(20 mm Hg) {bp 98–100°C (13 mm Hg) [8]}. 13C NMR
spectrum, , ppm: 21.29 (CH3), 22.89 (C3, C7), 25.38 (C5),
27.04 (C4, C6), 34.52 (C2, C8), 74.92 (C1), 170.23 (C=O).
Found, %: C 70.24; H 10.47. C10H18O2. Calculated, %:
C 70.54; H 10.65.
13C NMR spectrum, , ppm: 15.19 (C5), 18.44 (C4), 19.10
(C1), 20.84 (CH3), 37.87 (C3), 74.61 (C2), 170.38 (C=O).
3-Pentyl acetate (XVb). Yield 80%, bp 130.5–131°C
{bp 130–131°C (10 mm Hg) [10]}. 13C NMR spectrum,
, ppm: 9.29 (C1, C5), 20.99 (CH3), 26.55 (C2, C4),
76.63 (C3), 176.24 (C=O). Found, %: C 64.41; H 10.72.
C7H14O2. Calculated, %: C 64.57; H 10.84.
Cyclododecyl acetate (XI). Yield 9.6%, bp 97–98°C
(2 mm Hg) {bp 145–147°C (13 mm Hg) [8]}. IR spec-
trum, , cm–1: 1745 (C=O). 13C NMR spectrum, , ppm:
21.18 (CH3), 25.76 (C3, C11), 27.55 (C4, C10), 27.74 (C5,
C6, C7, C8, C9), 37.20 (C2, C12), 73.55 (C1), 170.55 (C=O).
Found, %: C 73.95; H 11.45. C14H26O2. Calculated, %:
C 74.19; H 11.56.
3-Hexyl acetate (XVI). Yield 25%, bp 75–76°C
(30 mm Hg). 13C NMR spectrum, , ppm: 10.11 (C1),
14.30 (C6), 19.29 (C5), 21.16 (CH3), 30.58 (C2), 39.47
(C4), 72.54 (C3), 172.15 (C=O). Found, %: C 67.41;
H 9.69. C8H16O2. Calculated, %: C 67.57; H 9.93.
2,5-Diacetoxy-2,5-dimethylhexane (XVII). Yield
40%. Compound XVII was isolated by column chro-
matography (eluent hexane–ether, 1:1). 13C NMR spec-
trum, , ppm: 21.56 (CH3), 23.56 (C1, 6–8), 38.70 (C3,5),
81.01 (C2,4), 175.67 (C=O). Found, %: C 62.12; H 9.54.
C12H22O4. Calculated, %: C 62.58; H 9.63.
Norbornyl exo-2-acetate (XII). Yield 92%, bp 60–
60.5°C (8 mm Hg) {bp 64–66°C (10 mm Hg) [9]}.
1H NMR spectrum, , ppm: 1.30–1.90 m (4H, H3,H5,
H6, H7), 2.18  (CH3), 2.45 s (2H, H1, H4), 4.75 s (H2).
13C NMR spectrum, , ppm: 20.94(C9), 24.40 (C6), 28.33
(C5), 35.37 (C7), 35.52 (C4), 39.70 (C3), 41.68 (C1), 77.50
(C2), 170.91 (C8).
5-Acetoxy-2,5-dimethylhex-1-ene (XVIIb). Yield
20%, bp 80–81°C (12 mm Hg). 13C NMR spectrum, ,
ppm: 14.04 (C1,7), 21.58 (CH3), 23.56 (C6,8), 31.64 (C4),
81.09 (C5), 128.08 (C3), 132.25 (C2), 175.64 (C=O).
Found, %: C 70.35; H 10.48. C10H18O2. Calculated, %:
C 70.54; H 10.65.
(E)-1,3-Diphenylbut-1-ene (XIII). Yield 50%.
1H NMR spectrum, , ppm: 1.87 d (3H, CH3), 4.05 q (1H,
CH), 6.78 m (1H, =CH), 6.80 d (1H, =CH). 13C NMR
spectrum, , ppm: 21.51 (CH3), 42.71 (C3-butene), 127.41
(C1-butene), 135.78 (C2-butene); aromatic: 125.31 (C16),
125.94 (C14), 126.79 (C6,10), 127.28 (C12), 127.57 (C8),
127.90 (C13,15), 128.08 (C7,9), 135.69 (C5), 143.20 (C11).
Found, %: C 92.09; H 7.91. C16H16. Calculated, %:
C 92.25; H 7.75.
2-Acetoxypropionitrile (XVIII). Yield 75%, bp 89°C
(30 mm Hg). 13C NMR spectrum , ppm: 20.92 (CH3),
21.94 (C1), 61.45 (C2), 117.52 (CN), 169.45 (C=O).
Found, %: C 52.89; H 6.05; N 12.15. C5H7NO2. Calcu-
lated, %: C 53.08; H 6.23; N 12.38.
1- and 2-Acetoxy-1,3-diphenylbutanes XIIIb and
XIIIc were isolated as a mixture by column chromatog-
raphy (eluent hexane–ether, 1:1). 13C NMR spectrum, ,
ppm (XIIIb): 22.88 (CH3), 23.08 (C4), 41.95 (C3), 44.44
(C2), 64.19 (C1), 170.57 (C=O); aromatic: 125.94 (C14),
126.30 (C7,9), 127.70 (C13,15), 128.07 (C8), 128.62 (C6),
129.88 (C12,16), 130.54 (C10), 141.24 (C5), 147.71 (C11);
(XIIIc): 15.13 (C4), 20.74 (CH3), 39.10 (C1), 42.41 (C3),
65.95 (C2), 170.97 (C=O); aromatic: 120.16 (C12,16),
127.41 (C8), 128.47 (C13–15), 129.15 (C6,7,9,10), 139.03
(C5), 144.73 (C11). Found, %: C 80.24; H 7.45. C18H20O2.
Calculated, %: C 80.56; H 7.51.
1-Butoxyethyl acetate (XIX). Yield 85%, bp 70–
71°C (20 mm Hg). 13C NMR spectrum, , ppm: 13.59
(C4), 18.18 (C3), 19.90 (C6), 20.55 (CH3), 30.43 (C2),
63.99 (C1), 82.92 (C5), 170.82 (C=O). Found, %: C 59.75;
H 9.89. C8H16O3. Calculated, %: C 59.97; H 10.06.
Phenyl acetate (XX). Yield 80%, bp 80°C (10 mm Hg)
(bp 196°C [11]). 13C NMR spectrum, , ppm: 20.87
(CH3), 121.43 (C2,6), 125.32 (C4), 128.90 (C3,5), 150.93
(C1), 169.38 (C=O).
1-Acetoxybut-3-ene (XXI). Yield 90%, bp 125–
126°C. 13C NMR spectrum, , ppm: 20.46 (CH3), 32.82
(C2), 63.19 (C1), 116.81 (C4), 133.80 (C3), 170.65 (C=O).
Found, %: C 62.89; H 8.75. C6H10O2. Calculated, %:
C 62.13; H 8.83.
4-Acetoxycyclooct-1-ene (XIV). Yield 81%, bp
63–64°C (1 mm Hg) 13C NMR spectrum, , ppm: 21.16
(CH3), 24.70 (C2), 25.42 (C6), 27.36 (C7), 29.47 (C5),
33.95 (C3), 75.44 (C4), 129.44 (C1), 129.95(C8), 170.15
(C=O). Found, %: C 71.12; H 9.43. C10H16O2. Calculated,
%: C 71.39; H 9.58.
ACKNOWLEDGMENTS
2-Pentyl acetate (XVa). Yield 9%, bp 130–131°C.
The study was carried out under the financial support
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