6
A.V. Teodorovi ´c et al. / Journal of Molecular Structure xxx (2014) xxx–xxx
The synthesis of 7-tridecanol was performed by reduction of
-tridecanone with LiAlH in dry Et O.
All of acetoxydecanes and acetoxytridecanes were prepared
UV-photolytic oxidative LTA decarboxylation of tetradecanoic acid in
benzene (B)
7
4
2
In a stirred suspension of 4.434 g (10 mmol) of LTA and 2.284 g
3
from corresponding alcohols by the reaction with acetic anhydride
in pyridine (the yields were 90–97%). Acetoxyalkanes were puri-
fied by preparative GC and their purity was checked by analytical
(10 mmol) of tetradecanoic acid in 210 cm of benzene slow
stream of purified Ar was introduced for 30 min at room tempera-
ture and in the absence of light. Mixture was irradiated with UV-
lamp (high pressure Hg-lamp Q81, at 100 V) at room temperature
until completion (i.e. until disappearance of tetravalent lead which
was monitored by potassium iodide/starch paper tracks) and then
1
13
GC and characterized by IR, H and C NMR spectra.
Lead(IV) acetate (Sigma Aldrich) was recrystallized twice from
glacial acetic acid containing 3% acetic anhydride, sucked dry in a
Büchner funnel, and dried in a vacuum desiccators over potassium
hydroxide.
3
worked up. After completion of the reaction, 200 cm of diethyl
ether was added and mixture was filtered. The filtrate was washed
Preparative GC: Varian Aerograph 920 gas chromatograph; the
column consisted of CW20M; hydrogen was used as a carrier gas
at inlet pressure of 0.18 MPa. Analytical gas chromatography
with water, diluted HCl (1:1), aqueous Na
2 3
CO (5%) and water.
After drying (CaSO ), the solvents were removed under reduced
4
pressure and the products in the residue were analyzed by analyt-
ical gas chromatography and separated by preparative gas chroma-
tography. The results of all runs are given in Tables 1, 3 and 4.
(
GC): Varian Model 3400 gas chromatograph and Perkin–Elmer
F-11 gas chromatograph equipped with a flame ionization detector
was used to measure the retention characteristics. Hydrogen was
used as a carrier gas at different inlet pressure. The conditions
for the separation of acetoxydecanes: 100 m capillary glass column
packed with Carbowax 20M (CW20M), at 140 °C under 0.25 MPa
H ; decenes: 100 m capillary glass column packed with O-4-n-
2
pentyloxybenzoyl oxime (PBO) liquid crystal in chloroform [21];
tridecene and tridecane: 100 m capillary glass column packed with
Thermal oxidative LTA decarboxylation of tetradecanoic acid in acid as
solvent (C)
The mixture of 11.42 g (50 mmol) of tetradecanoic acid and
4.43 g (10 mmol) of LTA was heated to the rate and slow stream
of purified Ar was introduced for 10 min in the absence of light.
Mixture was heated (120 ± 2 °C) and stirred for 24 h. After comple-
3
PBO liquid crystal, at 82 °C under 0.18 MPa H
1
2
; acetoxytridecanes:
00 m capillary glass column packed with CW20M, at 57 °C under
.25 MPa H
IR spectra: Perkin–Elmer FTIR spectrophotometer model Spec-
trum One.
NMR spectra: Varian Gemini 2000 NMR spectrometer at
00 MHz. Samples are analyzed as CDCl solution using tetrameth-
ylsilane (TMS) as internal standard.
tion of the reaction, to the cooled solution 50 cm of diethyl ether
3
and 50 cm of water were added. Ether layer was removed and
0
2
.
2 3 4
washed with aqueous Na CO (5%) and brine. After drying (CaSO ),
the solvents were removed under reduced pressure and the prod-
ucts in the residue were analyzed by analytical gas chromatogra-
phy and separated by preparative gas chromatography. The
results of all runs are given in Table 1.
2
3
GCMS analysis: the gas chromatograph (Varian Gas-
Chromatograph Model 340, column packed with CW20M) was
connected via an open split interface and a fused silica capillary
Deamination of 1-aminodecane using amyl nitrite (Control reaction)
Solution of 0.787 g (5 mmol) of 1-aminodecane, 0.300 g
(5 mmol) of glacial acetic acid and 0.644 g (5.5 mmol) of amyl
3
(
at 250 °C) to the ion source of a Finnigan MAT 8230 spectrom-
nitrite in benzene (10 cm ) was heated to reflux for 4 h. Reaction
eter; EIMS: ion source, 170 °C, 70 eV.
mixture was then cooled to r.t., diluted with diethyl ether
3
3
Reaction mixtures were first fractionated by preparative gas
chromatography. Every fraction was analyzed by analytical gas
chromatography and GCMS analysis. Reaction product (acetates,
alkenes, phenylalkanes, etc.) were known compounds and were
characterized and identified on the basis of the spectral data
and/or by comparison with authentic samples synthesized by
independent routes.
(30 cm ) and washed with saturated NaHCO
3
(4 Â 15 cm ), dilute
3
3
solution of sulfuric acid (2 Â 15 cm ), water (5 Â 25 cm ) and dried
over anhydrous magnesium sulfate. After removing of solvent, by
distillation under atmospheric pressure (over Vigreux column
length 30 cm), mixture was fractionated by preparative GC (ace-
tates and decenes). Each fraction was further analyzed by analytical
GC (general remarks). The results of all runs are given in Table 2.
Thermal oxidative LTA decarboxylation of tetradecanoic acid in
benzene (A)
The thermal LTA decarboxylation in benzene was performed
as described previously [22]. Mixture of 4.434 g (10 mmol) of
MC simulation
The program for simulation was developed in Fortran 90 pack-
age. This packet enables generation of the numbers uniformly dis-
tributed between 0 and 1 by using an intrinsic function called
RANDOM_NUMBER (gamma). The optional name ‘‘gamma’’ is
defined by the user and takes the value between 0 and 1. It can
be used as probability that some process (reaction) may appear.
The algorithm for simulation of reaction was explained in follow-
ing steps:
3
LTA and 2.284 g (10 mmol) of tetradecanoic acid in 60 cm of
benzene was used in thermal reactions. Before starting the
oxidative decomposition slow stream of purified Ar was intro-
duced into stirred mixture of acid and LTA in benzene for
3
0 min at room temperature and in the absence of light. The
oxygen-free mixture resulting from the above described proce-
dure [22] was stirred and heated under reflux (without light pro-
tection) until completion (i.e. until disappearance of tetravalent
lead which was monitored by potassium iodide/starch paper
tracks) and then worked up.
1. According to Scheme 3 and 4 the set of all transition probabili-
ties for all intermediates pij was sampled. The values of all pij
are between 0 and 1. The number of all elements in reaction
is A
2. The simulation was started from element 1a and the number of
that element is A = 1.
i
= 0.
After completion of the LTA oxidation, the mixture was cooled,
treated with 50 cm3 of diethyl ether and filtered. The filtrate was
1
washed with water, diluted HCl (1:1), aqueous Na
2
CO
3
(5%) and
3. By using intrinsic function RANDOM_NUMBER (gamma), the
water. After drying (CaSO ), the solvents were removed under
4
probability of formation any element from 1a is given.
reduced pressure and the products in the residue were analyzed
by analytical gas chromatography and separated by preparative
gas chromatography. The results of all runs are given in Tables 1,
4. It was assumed that the element k was created from 1a if the
k
condition
R
j=1
p
1a,j
6 c was satisfied.
k k
5. When element k is created, then is A = A + 1 and the step 4
3
and 4.
was applied for element k.
Teodorovi?, Aleksandar V.
