Synthesis of 4-(ω-X-alkyl)benzonitriles (X = 1,3-dioxan-2-yl, CN, CO2Et) by the reaction of terephthalonitrile dianion with ω-X-alkyl bromides in liquid ammonia

Article abstract of DOI:10.1007/s11172-016-1602-x

The main products of the reaction of terephthalonitrile dianion disodium salt with ω-X-alkyl bromides (2-(2-bromoethyl)-1,3-dioxane, 5-bromovaleronitrile, ethyl 6-bromohexanoate) in liquid ammonia are the corresponding 4-(ω-X-alkyl)benzonitriles. Similar

Full text of DOI:10.1007/s11172-016-1602-x

Russian Chemical Bulletin, International Edition, Vol. 65, No. 10, pp. 2430—2436, October, 2016
2430
Synthesis of 4ꢀ(ωꢀXꢀalkyl)benzonitriles (X = 1,3ꢀdioxanꢀ2ꢀyl, CN, CO2Et)
by the reaction of terephthalonitrile dianion with ωꢀXꢀalkyl bromides in liquid ammonia
R. Yu. Peshkov,a,b Wang Chynyan,b,c E. V. Panteleeva,a,b E. V. Tretyakov,a,b and V. D. Shteingartsa
†
аN. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry,
Siberian Branch of the Russian Academy of Sciences,
9 prosp. Acad. Lavrentiev, 630090 Novosibirsk, Russian Federation.
Fax: +7 (383) 330 9752. Eꢀmail: pantel@nioch.nsc.ru
bNovosibirsk State University,
2 ul. Pirogova, 630090 Novosibirsk, Russian Federation.
cRussianꢀChina Institute of Heilongjiang University,
74 Xuefu Road, 150080 Harbin, China*
The main products of the reaction of terephthalonitrile dianion disodium salt with ωꢀXꢀalkyl
bromides (2ꢀ(2ꢀbromoethyl)ꢀ1,3ꢀdioxane, 5ꢀbromovaleronitrile, ethyl 6ꢀbromohexanoate) in liqꢀ
uid ammonia are the corresponding 4ꢀ(ωꢀXꢀalkyl)benzonitriles. Similar reactions of benzonitrile
radical anion sodium salt lead to ωꢀXꢀalkylbenzenes. In both cases the formation of products is due
to selective ipsoꢀalkylation of anionic forms that indicates the nucleophilic activity of
terephthalonitrile dianion and benzonitrile radical anion in these reactions and the realization of
alkylation via SN2 mechanism.
Key words: terephthalonitrile, benzonitrile, reductive alkylation, alkyl bromides, dianions,
radical anions.
Benzonitriles, containing alkyl or ωꢀfunctionalized
alkyl fragments in paraꢀposition, are traditionally used as
universal structural blocks in fine organic synthesis of
compounds with wide range of practical applications
(liquid crystals,1 pigments,2 macrostructures,3 repelꢀ
lents,4 herbicides,5 sound absorbents,6 oligomer elecꢀ
tron acceptors,7 biologically active compounds and
drugs8). Functionalized benzonitriles are usually obꢀ
tained by Wurtz–Fittig reaction,9 photochemical proꢀ
cesses,10 catalytic11 and electrochemical12 crossꢀcoupꢀ
lings. Despite the prevalence and relatively high effiꢀ
ciency of these methods, their main disadvantages inꢀ
clude the need for preꢀactivation of substrates (in parꢀ
ticular, the introduction of metal and organometallic
substituents), the use of expensive catalysts and ligands
or specific experimental conditions. It is also important to
note that such methods bring about products which can
be contaminated with transition metal compounds.
This requires their special purification prior to their use in
pharmacy.13 In this connection, a synthetic approach usꢀ
ing reductive alkylation of available terephthalonitrile (1)
in liquid ammonia looks attractive. Previously, it was
shown that dianion [1]2–, generated by twoꢀelectron reꢀ
duction of dinitrile 1 with alkali metal in liquid ammonia,
is highly effective synthon of paraꢀcyanophenylation of
alkylꢀ, ωꢀalkenyl halides, and α,ωꢀdibromoalkanes. This
reaction proceeds by the competing mechanisms of nuꢀ
cleophilic substitution (SN2) and electron transfer, folꢀ
lowed by the recombination (ET). On this basis, an uniꢀ
versal access to 4ꢀalkyl (2),14 4ꢀ(ωꢀalkenyl)benzonitriles
(3a—f),15 and α,ωꢀbis(pꢀcyanophenyl)alkanes (4),16
which allows obtaining the products with 40—90% yields
(Scheme 1), was proposed.
The aim of this work is extension of the synꢀ
thetic potential of dianion [1]2– in the production of
ωꢀfunctionalized alkylbenzonitriles. Primary alkyl broꢀ
mides, namely 2ꢀ(2ꢀbromoethyl)ꢀ1,3ꢀdioxane (5a),
5ꢀbromovaleronitrile (5b), and ethyl 6ꢀbromohexanoate
(5c), differing both by the length of alkylene fragment
between bromine atom and functional group and by naꢀ
ture of the functional group, were selected for the invesꢀ
tigation of activity of dianion [1]2– in respect to
ωꢀfunctionalized alkyl halides. The choice of bromides
as alkylation agents is supposed to be optimal as SN2ꢀ
reaction of [1]2– with alkyl chlorides in liquid ammonia
proceeds slower than with alkyl bromides. In the case of
alkyl iodides ET process dominates in the competition
between two mechanisms (SN2 and ET), which leads to
the 2ꢀalkylterephtalonitriles along with 4ꢀalkylꢀ
benzonitriles in the ratio 1/(6—2), respectively (C.f.
Ref. 14a). However, it was difficult to predict before
setting up the experiments that interaction of [1]2– with
alkyl bromides 5a—c would proceed solely by the way of
ipsoꢀalkylation. Really, dianion [1]2– is highly basic and
thus is capable of protonation with relatively acidic
†
Deceased.
* Heilongjiang University, Xuefu Road, 74, Harbin, 150080, China.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2430—2436, October, 2016.
1066ꢀ5285/16/6510ꢀ2430 © 2016 Springer Science+Business Media, Inc.

Terephthalonitrile reductive alkylation
Russ.Chem.Bull., Int.Ed., Vol. 65, No. 10, October, 2016
2431
alkylation of dianion [1]2– were also present. The formaꢀ
tion of these products is possible within ЕТ mechanism.
However, their content was very small: up to 2—3% for
alkylation reagents 5b,c, and up to 6% for bromo acetal
5a. The products of the reductive transformations of funcꢀ
tional groups with the reagents 5a—c were absent. Thus,
the interaction of [1]2– with ωꢀХꢀalkyl bromides 5a—c in
ammonia proceeds predominantly as ipsoꢀalkylation and
results in 4ꢀ(ωꢀХꢀalkyl)benzonitriles 6a—c in reasonꢀ
able yields (see Table 1). Such orientation of the alkylaꢀ
tion is obviously due to dominance nucleophilic compoꢀ
nent of dianion [1]2– reactivity as in the case of unmodiꢀ
fied primary alkyl bromides (compare Ref. 14).
Scheme 1
Scheme 2
2: Alk = nꢀ, iꢀ, sꢀ, tꢀBu; nꢀC5H11, nꢀC8H17, cꢀC6H11; Hal = Cl. Br, I
3
a
b
c
n
1
1
1
R
H
Me
F
3
d
e
f
n
2
3
4
R
H
H
H
4: n = 3, 4, 5
The most probable mechanism of the formation of the
desired products 6a—c is shown in Scheme 3. It is heteroꢀ
lytic (SN2 mechanism) alkylation of the dianion by the site
of maximal electron density14,21 with the formation of
cyclohexadienyl anion [1—Alk]–, which undergoes aroꢀ
matization upon rapid decyanation yielding modified
benzonitriles 6a—c.
The presence of ωꢀХꢀalkylbenzene 7 in noticeable
amounts in the products can be explained as follows.
First, initially formed 4ꢀ(ωꢀXꢀalkyl)benzonitriles 6 can be
αꢀprotons of ester 5b or nitrile 5c, which can afford
benzonitrile.14a,17 In addition, there is a possibility of reꢀ
duction of reactants 5a—c with dianion [1]2– without the
formation of alkylation products (compare Refs 18, 19).
Anyway, the data on the use of such ωꢀmodified alkyl
halides in the Birch reactions of the reductive alkylation
of biphenyl and benzoic acid derivatives20 allowed one to
hope for the positive results.
The dianion [1]2– was generated by reduction of
dinitrile 1 suspension in liquid ammonia with sodium
metal (2.15—2.20 eq) which is more convenient comꢀ
pared to lithium and potassium. It was shown earlier15
that the yields of alkylation products of alkali salt of
dianion [1]2– are weakly dependent on the nature of
the metal (increase by ∼3—5% in the following order
[1]2–[2Li+] < [1]2–[2Na+] < [1]2–[2K+]). An addition to
the suspension of disodium salt of dianion [1]2– in liquid
ammonia of slight excess (1.3 eq) of bromide 5a—c
yielded the mixture of compounds mainly consisting of
expected product, namely corresponding 4ꢀ(ωꢀХꢀalkyl)ꢀ
benzonitrile 6a—c (40—60% according to combined data
Table 1. Reaction of disodium salt of dianion [1]2– with ωꢀХꢀalkyl
bromides 5a—c in liquid ammoniaa
5
X
n
Proꢀ
Yield (%)
ducts
1H NMR
TLCc
and GC/MS
a
b
c
1,3ꢀDioxanꢀ2ꢀyl
CN
2
4
5
6a
7а
6b
7b
6c
7c
42
24
58
23
48
27
36
23
52
18
45
25
1
of H NMR and GC/MS) (Scheme 2, Table 1). Howꢀ
CO2Et
ever, besides compounds 6a—c the corresponding ωꢀХꢀ
alkylbenzene 7a—c (20—30%), alkylation agents 5a—c
(15—20%), and also starting dinitrile 1 (up to 20%) and
some amount of minor unidentified components (total
content <5%) were present in the reaction mixture. Also,
according to GC/MS data the compounds with molecuꢀ
lar ion masses corresponding to the products of orthoꢀ
a Conditions: 2.15—2.20 eq of Na, 1.3 eq. of Br(CH2)nX (5a—c),
NH3 (liquid), –33 °C, 1.5 h.
b Yield is presented according to joint data of 1Н NMR and GC/МS
(by not less than two experiments, deviation of presented value not
more than 5%).
c Separated using preparative TLC.

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Russ.Chem.Bull., Int.Ed., Vol. 65, No. 10, October, 2016
Peshkov et al.
Scheme 3
ment in favor of the route B is the presence of ethyl
cyclopentanecarboxylate (∼5%) among the reaction prodꢀ
ucts in the case of the reagent 5c. Ethyl
cyclopentanecarboxylate is formed, apparently, as the
result of intramolecular cyclization of deprotonated comꢀ
pound 5c.
2ꢀChloroacetonitrile (5d) was involved into the reacꢀ
tion in order to investigate the influence of dianion
[1]2– protonation by alkylation reagent (or by products)
on the synthetic result. In this case, the reaction mixture
1
(according to H NMR and GC/MS data) consisted of
small amount of 4ꢀcyanomethylbenzonitrile23,24 (6d,
11%), 4,4´ꢀdicyanobiphenyl (9, 18%), and starting
dinitrile 1 (46%, Scheme 5). The formation of comꢀ
pound 9 signifies the protonation of dianion [1]2– that
initiates the process of its transformation into benzonitrile
8, followed by crossꢀcoupling25 with dianion [1]2–. The
obtained result indicates that crossꢀcoupling of [1]2– with
nitrile 8 proceeds quicker than reductive alkylation of 8
with chloride 5d, which should lead to phenylacetonitrile.
To confirm the assumption that protonation of dianion
[1]2– is one of the reasons for the formation of ωꢀХꢀ
alkylbenzenes 7a—c, the process of single electron actiꢀ
vation of benzonitrile 8 with sodium in liquid ammonia
followed by inclusion of radical anion of benzonitrile
reduced by dianion [1]2–, as well as by excess alkali metal
to radical anion [6]•–, which upon further processing are
protonated and finally transformed into alkylbenzenes 7
(Scheme 4, route A). This suggestion is rather probable
due to described earlier results of the interaction of dianion
[1]2– with α,ωꢀdibromoalkanes.16 Regardless on the ratio
of the reagents, this reaction yields solely α,ωꢀbis(pꢀ
cyanophenyl)alkanes. That in turn signifies higher reacꢀ
tion rate of [1]2– with initially formed 4ꢀ(ωꢀ
bromoalkyl)benzonitriles than with α,ωꢀdibromoꢀalkanes.
Second, the protonation of dianion [1]2– (by reagents
5a—c, as well as by traces of water in reagents and solꢀ
vents) could take place. This yields benzonitrile (8), folꢀ
lowed by reduction and alkylation leading to alkylbenzenes
7 (compare Ref. 22, see Scheme 4, route B). The arguꢀ
–
[8]• in the reaction with ωꢀХꢀalkyl bromides 5a—c
(Scheme 6, Table 2) was investigated. Previously, such
transformation was performed using nonꢀfunctionalized
alkyl halides as the example. That yielded the correꢀ
sponding alkylbenzenes with sufficiently high yields of
30—50% (it should be taken into account that the radical
anion stoichiometry implies participation of two moles of
this radical anion for the formation of one mole of prodꢀ
Scheme 4
e = [1]2– or Na

Terephthalonitrile reductive alkylation
Russ.Chem.Bull., Int.Ed., Vol. 65, No. 10, October, 2016
2433
Scheme 5
uct).21,22,26 The yields of ωꢀХꢀalkylbenzenes 7a—c reꢀ
mained in the same range of 36—47% according to
1Н NMR and GC/MS (see Table 2) upon using of
functionalized alkyl bromides 5a—c. Besides the prodꢀ
ucts 7a—c, the starting compounds, namely nitrile 8
and alkyl bromides 5a—c, were present in the reaction
products.
In summary, the results obtained allow one to conꢀ
clude that reductive activation of dinitrile 1 with transforꢀ
mation into dianion [1]2–, and also of benzonitrile 8 with
transformation into radical anion [8]•–, followed by treatꢀ
ment with ωꢀfunctionalized alkyl bromides proceeds preꢀ
dominantly
as
ipsoꢀalkylation,
followed
by
decyanation, which leads to the corresponding 4ꢀ(ωꢀXꢀ
alkyl)benzonitriles and 4ꢀ(ωꢀXꢀalkyl)benzenes. The alkyl
bromides with more than one CH2 unit in alkylene bridge
between bromine atom and the functional group should
be used to achieve good yields of the products. Otherwise,
e.g. in the case of 2ꢀchloroacetonitrile the protonation of
dianion [1]2– becomes the main reaction route and the
yields of 4ꢀ(ωꢀXꢀalkyl)benzonitriles are decreased. In genꢀ
eral, the proposed approach can be used as a convenient
and economical method for the synthesis of
α,ωꢀdifunctionalized structural blocks, containing from
one side of the chain cyanophenyl group, opening up
good opportunities for further modification, 27 and from
the other side containing acetal, alkoxycarbonyl or nitrile
function.
Scheme 6
Reaction conditions: Na, NH3 (liquid), ꢀ33 °C, 1.5 h.
Table 2. Reductive alkylation of benzonitrile 8 with
ωꢀХꢀalkyl bromides 5a—ca
Experimental
Alkylation
agent
Yieldb
(mol.%)
1
Н and 13C NMR spectra were registered using Bruker AV 400
5a
5b
5c
7a (38)
7b (36)
7c (47)
and Bruker Avance III 500 spectrometers with ~5% solutions in
CDCl3. Internal standard was residual protonated solvent, the
chemical shifts were represented in the δ scale. The assignment of
signals is made based on the data of heteronuclear correlations
HSQC and HMBC. For uniformity of presentation of spectral data,
the numeration of atoms in structures 6a—c and 7a—c differs from
systematic (Fig. 1). IR spectra were obtained using Vectorꢀ22
spectrometer (Bruker) in thin layer or in KBr. Exact values of the
a Conditions: 1 eq of 8, 0.98 eq of Na, NH3 (liquid),
0.6 eq of Br(CH2)nX (5a—c), –33 °C, 1.5 h.
b Yield according to joint data of 1Н NMR and GLC/
МS (by not less than two experiments, deviation of
presented value not more than 5%).

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Russ.Chem.Bull., Int.Ed., Vol. 65, No. 10, October, 2016
Peshkov et al.
mass of molecular ions are determined using high resolution DFS
massꢀspectrometer. The identification of components by GC/MS
was carried out using Hewlett Packard G1081A. Analytical investiꢀ
gations and registrations of spectra (NMR, IR, MS, and GLC/MS)
were performed by the employees of the MultiꢀAccess Chemical
Service Center SB RAS.
bined ether extract was washed till neutral рН with water, then with
saturated solution of NaCl, dried over MgSO4, and the solvent was
evaporated. The compositions of mixtures and yields of products
were determined according to 1Н NMR (dimethyl terephthalate as
standard) and GLC/MS. Individual compounds were separated by
preparative thin layer chromatography (ТLС) using fixed layer of
absorbent (silica gel 60 PF254 with addition of gypsum, Merck), the
eluent was hexane—Et2O. The result of separation was controlled
visually by exposure of dried plate to UV light. The fractions of
products were washed from the adsorbent by Et2O.
Liquid NH3 was purified by dissolving of metal Na, followed by
distillation into cooled to –70 °C reaction vessel. Metal Na was
cleaned from oxidized surface under the layer of dry hexane.
Terephthalonitrile was purified by sublimation in vacuum (m.p.
222 °C; compare Ref. 28: m.p. 222—223 °C). Benzonitrile was
purified by distillation over P2O5. 2ꢀ(2ꢀBromoethyl)ꢀ1,3ꢀdioxane,
5ꢀbromovaleronitrile, ethyl 6ꢀbromohexanoate, 2ꢀchloroacetonitrile
(Alfa Aesar) were passed through thin layer of silica gel just
before the experiment. Diethyl ether and hexane were purified by
distillation.
4ꢀ[2ꢀ(1,3ꢀDioxanꢀ2ꢀyl)ethyl]benzonitrile (6a), CAS No.
89013ꢀ02ꢀ5, was separated from the reaction mixture of [1]2– and
5a (0.530 g) as colorless solid (182 mg, 0.84 mmol, 36%), m.p.
67.3—67.8 °C (compare Ref. 1i: m.p. 64—65 °C), Rf ≈ 0.15 (hexꢀ
ane—Et2O, 9 : 1, fivefold eluation). IR (KBr), ν/cm–1: 2226 (C≡N).
1H NMR (400.13 MHz) δ Hz): 1.33 (dm, 1 Н, C(5″)H, J = 13.2 Hz);
1.85—1.91 (m, 2 Н, C(2´)H2); 2.00—2.13 (m, Н, C(5″)H); 2.76 (t,
2 Н, C(1´)H2, J = 7.9 Hz); 3.72 (td, 2 Н, C(4″)H, and С(6″)H, J =
12.0 Hz, J = 2.2 Hz); 4.10 (ddm, 2 H, С(4″)Н and C(6″)Н, J = 10.7,
J = 5.2 Hz); 4.48 (t, 1 Н, C(2″)H, J = 5.1 Hz); 7.27 (d, 2 H, С(3)H,
С(5)H, J = 8.2 Hz); 7.54 (d, 2 H, С(2)H, С(6)H, J = 8.2 Hz). 13C
NMR (125.77 MHz) δ: 25.5 (C(5″)); 29.9 (C(1´)); 35.8 (C(2´));
66.7 (C(4″), C(6″)); 100.7 (C(2″)); 109.6 (C(1)); 118.8 (C(CN));
129.0 (С(3), C(5)); 132.0 (C(2), C(6)); 147.3 (C(4)). Massꢀspecꢀ
trum (EI, 70 eV), m/z (Irel (%)): 217 [M]+ (4), 158 (9), 130 (17),
116 (20), 114 (17), 103 (9), 87 (100), 59 (15). Found: m/z 217.1018
[M]+. С13H15NO2. Calculated: M = 217.1097.
Generation of disodium salt of terephthalonitrile dianion ([1]2–
)
and its interaction with ωꢀfunctionalized alkyl halides 5a—d (genꢀ
eral procedure). To the stirred suspension of dinitrile 1 (0.300 g,
2.34 mmol) in liquid NH3 (30—40 mL) in the atmosphere of
evaporating NH3, at temperature –(33—50) °C sodium metal
(2.15—2.20 eq) was added by portions. The obtained blackꢀbrown
suspension of the disodium salt of dianion [1]2– was stirred for
additional 5 min. Then ωꢀXꢀalkyl bromide 5a—d (1.3 eq in respect
to dinitrile 1) was added dropwise and the stirring was continued for
1—1.5 h at –33 °C in the atmosphere of evaporating NH3. Then the
reaction mixture was allowed to contact with air, Et2O (20—30
mL) was added and the stirring was continued until complete evapoꢀ
ration of NH3. Water (30 ml) was added to the residue and the
organic products were extracted with Et2O (3×25 mL). The comꢀ
4ꢀ(4ꢀCyanobutyl)benzonitrile (6b),29 CAS No. 1220102ꢀ01ꢀ1,
was separated from the reaction mixture of [1]2– and 5b (0.432 g) as
colorless oil (0.224 g, 1.22 mmol, 52%), Rf ≈ 0.25 (hexane—Et2O,
Fig. 1. Atom numeration in compounds 6a—c and 7a—c, used for the assignment of NMR spectra.

Terephthalonitrile reductive alkylation
Russ.Chem.Bull., Int.Ed., Vol. 65, No. 10, October, 2016
2435
8 : 2, sevenfold eluation). IR (film), ν/cm–1: 2227 (C≡N), 2247
(C≡N). 1H NMR (500.13 MHz) δ: 1.69—1.72 (m, 2 Н, C(3´)H2);
1.78—1.84 (m, 2Н, C(2´)H2); 2.37 (t, 2 Н, C(4´)H2, J = 7.2 Hz);
2.72 (t, 2 Н, C(1´)H2, J =7.5); 7.28 (d, 2 H, С(3)H, С(5)H, J =
= 8.0 Hz); 7.58 (d, 2 H, С(2)H, С(6)H, J = 8.0 Hz). 13C NMR
(125.77 MHz) δ: 17.9 (C(4´)); 25.7 (C(2´)); 30.6 (C(3´)); 36.0
(C(1´)); 111.0 (C(1)); 119.7 (CCN(1)); 120.1 (CCN(5´)); 130.0
(С(3), C(5)); 133.2 (C(2), C(6)); 147.7 (C(4)). Massꢀspectrum
(EI, 70 eV), m/z (Irel (%)): 184 [M]+ (32), 183 (28), 130 (52), 116
(100), 89 (22). Found: m/z 184.0998 [M]+. С12H12N2. Calcuꢀ
lated: M = 184.1000.
tially benzonitrile 8 (0.3 mL, 3.0 mmol) and sodium metal (0.068 g,
2.96 mmol) were added at temperature –(33—50) °C affording
–
thus darkꢀred solution of benzonitrile radical anion [8]•
.
ωꢀXꢀAlkyl bromide 5a—c (0.6 eq in respect to nitrile 8) was added
to this solution and the stirring was continued for 1.5 h at –33 °C in
the atmosphere of evaporating NH3. Following processing was
performed similarly to described above. The composition of obꢀ
tained in this way reaction mixtures was analyzed by 1Н NMR and
GC/MS methods.
The authors acknowledge the MultiꢀAccess Chemiꢀ
cal Service Center SB RAS for spectral and analytical
measurements. The work was performed with financial
support of Russian Foundation for Basic Research
(Project No 14ꢀ03ꢀ00108) and Federal Agency of Scienꢀ
tific Organizations (Project No 0302ꢀ2016ꢀ0007).
Ethyl 6ꢀ(4ꢀcyanophenyl)hexanоate (6c),30 CAS No. 1888410ꢀ
56ꢀ7, was separated from the reaction mixture of [1]2– and 5c
(0.593 g) as colorless oil (0.258 g, 1.05 mmol, 45%), Rf ≈ 0.42
(hexane—Et2O, 8 : 2, fourfold eluation). IR (film), ν/cm–1: 2227
1
(C≡N), 1732 (C=O). H NMR (400.13 MHz) δ: 1.22 (t, 3 Н,
C(8´)H3, J = 7.2 Hz); 1.33 (quint, 2 Н, C(3´)H2, J = 7.6 Hz);
1.58—1.66 (m, 4 Н, C(2´)H2, C(4´)H2); 2.26 (t, 2 Н, C(5´)H2, J =
= 7.6 Hz); 2.64 (t, 2 Н, C(1´)H2, J = 7.7); 4.09 (q, 2 H, С(7´)Н2,
J = 7.2 Hz); 7.24 (d, 2 H, H(3), H(5), J = 8.2 Hz); 7.53 (d, 2 H,
H(2), H(6), J = 8.2). 13C NMR (125.77 MHz) δ: 14.1 (C(8´));
24.5 (C(3´)); 28.4 (C(4´)); 30.4 (C(2´)); 34.0 (C(5´)); 35.7 (C(1´));
60.1 (C(7´)); 109.5 (C(1)); 118.9 (CCN); 129.0 (С(3), C(5)); 131.9
(C(2), C(6)); 148.0 (C(4)); 173.5 (C(6´)). Massꢀspectrum (EI,
70 eV), m/z (Irel (%)): 245 [M]+ (24), 200 (24), 158 (39), 155 (54),
130 (65), 116 (100), 101 (39), 88 (52). Found: m/z 245.1410 [M]+.
С15H19NO2. Calculated: M = 245.1406.
2ꢀ(2ꢀPhenylethyl)ꢀ1,3ꢀdioxane (7a),31 CAS No. 5663ꢀ30ꢀ9,
was separated from the reaction mixture of [1]2– and 5a (0.530 g) as
colorless oil (103 mg, 0.54 mmol, 23%), Rf ≈ 0.3 (hexane—Et2O,
9 : 1, fivefold eluation). 1H NMR (400.13 MHz) δ: 1.32 (dm, 1 Н,
C(5″)H, J = 13.4 Hz); 1.87—1.92 (m, 2 Н, C(2´)H2); 2.01—2.15
(m, 1 Н, C(5″)H); 2.70 (t, 2 Н, C(1´)H2, J = 7.9 Hz); 3.74 (td, 2 Н,
C(4″)H and С(6″)H, J = 12.0 Hz, J = 2.4 Hz); 4.06—4.12 (m, 2 H,
С(4″)Н and C(6″)Н); 4.49 (t, 1 Н, C(2″)H, J = 5.2 Hz); 7.13—7.18
(m, 3 H, H(2), H(4), H(6)); 7.26 (t, 2 H, H(3), H(5), J = 8.1 Hz).
Massꢀspectrum (EI, 70 eV), m/z (Irel (%)): 192 [M]+ (2), 133 (15),
114 (33), 105 (17), 91 (37), 87 (100), 59 (17).
5ꢀPhenylvaleronitrile (7b),32 CAS No. 7726ꢀ45ꢀ6, was sepaꢀ
rated from the reaction mixture of [1]2– and 5b (0.432 g) as
colorless oil (0.060 g, 0.38 mmol, 16%), Rf ≈ 0.4 (hexane—Et2O,
8 : 2, sevenfold eluation). 1H NMR (400.13 MHz) δ: 1.62—1.70
(m, 2 Н, C(3´)H2); 1.74—1.81 (m, 2 Н, C(2´)H2); 2.33 (t, 2 Н,
C(4´)H2, J = 7.1 Hz); 2.64 (t, 2 Н, C(1´)H2, J = 7.2 Hz); 7.14—
7.20 (m, 3 H, H(2), H(6), H(4)); 7.28 (t, 2 H, H(3), H(5), J =
= 7.0 Hz). Massꢀspectrum (EI, 70 eV), m/z (Irel (%)): 159 [M]+
(24), 158 (20), 91 (100).
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