Synthesis of new conjugated diynes containing carbamate groups, and study of their properties

Article abstract of DOI:10.1023/A:1020326818084

Carbamates of monoacetylene and diacetylene series were synthesized and characterized. A catalytic system CuI-pyrrolidine was applied for the first time to a synthesis of symmetrical diacetylenes by oxidative dimerization of terminal acetylenes. The compa

Full text of DOI:10.1023/A:1020326818084

Russian Journal of Organic Chemistry, Vol. 38, No. 6, 2002, pp. 775 787. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 6, 2002,
pp. 817 829.
Original Russian Text Copyright
2002 by Vyazmin, Berezina, Remizova, Domnin, Gleiter.
Synthesis of New Conjugated Diynes Containing Carbamate
Groups, and Study of Their Properties
S. Yu. Vyazmin1, S. E. Berezina1, L. A. Remizova1,
I. N. Domnin1, and R. Gleiter2
1Research Institute of Chemistry of St. Petersburg State University, St. Petersburg, 198504 Russia
2R. Gleiter. Organisch-Chemisches Institut der Universitat Heidelberg, D-69120 Heidelberg, Germany
Received December 10, 2001
Abstract Carbamates of monoacetylene and diacetylene series were synthesized and characterized.
A catalytic system CuI-pyrrolidine was applied for the first time to a synthesis of symmetrical
diacetylenes by oxidative dimerization of terminal acetylenes. The comparative activity of diynes
obtained was studied in the photoinitiated solid-phase topochemical polymerization. Diyne
carbamates undergoing thermal polymerization were obtained for the first time.
Functionally-substituted diacetylenes are interest-
ing both from theoretical and practical viewpoints,
and therefore they are the object of versatile inter-
disciplinary studies [1]. Diacetylene moiety is
encountered in many natural compounds [2], and syn-
thetic antibiotics containing endiyne structure exhibit
pronounced anticancer activity [3]. The compounds
have found wide use in fine and general organic syn-
thesis [4, 5]. The studies in this field got a new
momentum from the discovery of Wegner of solid-
phase topochemical polymerization of these com-
pounds initiated by UV and -radiation, and some-
times by just heating [6]. Polyacetylenes generated by
this process possess unidimensional totally conjugated
backbone with mainly enyne (seldom butatriene)
crystal structure [7].
The unique feature of the reaction is the possibility
to obtain a single crystal of polymer from a single
crystal of monomer. The polyacetylenes are more and
more applied as chromatic element in biosensors
[8 10]. They are especially promising materials for
non-linear optics since they possess the largest values
of non-linear optical susceptibility of the third order
3
( ) among all known organic compounds [11, 12].
The polymerizability of initial monomeric diynes
and polymerization rate essentially depend on the
specificity of molecular packing in crystals [13].
The usually applied criteria are taken from crystallo-
graphy: d1, the distance between the neighboring
molecules in a stack, and 1, the angle between the
axis through the system of triple carbon-carbon bonds,
and the axis through the centers of the ordinary
1070-4280/01/3806-775$27.00 2002 MAIK Nauka/Interperiodica

776
VYAZMIN et al.
carbon-carbon bonds that are located between the
triple bonds. Instead of d1 parameter S1 is often used.
The synthesis of diacetylene arylcarbamates can be
effected along two ways. The first one involves a
synthesis of monoacetylene terminal arylcarbamates
followed by their oxidative dimerization into the
target products. The second way includes reaction of
diacetylene glycols with aryl isocyanates. The dis-
advantage of the latter procedure consists in the
possibility of side reaction affording cyclic ether by
intermolecular dehydration of two molecules of di-
acetylene glycol effected by aryl isocyanate. For
instance, in reaction of dodeca-5,7-diyne-1,12-diol
with phenyl isocyanate alongside diacetylene
carbamate were obtained carbanilide and a cyclic
diacetylene ether formed as a result of dehydration of
the initial diacetylene glycol with phenyl isocyanate
[14]. Therefore we chose the first method.
The values d1 4.9 , 3.4
S1 4.0
,
45
are the best, for in this case the reacting carbon1atoms
are approached to a required distance, and trans-1,4-
polyaddition occurs. However in a general case
the prediction of diacetylene molecule packing in a
crystal cannot be performed basing on its structural
formula.
The target of this study was establishing of relation
between the structure and activity in solid-phase topo-
chemical polymerization of diynes with arylcarbamate
groups capable of forming hydrogen bonds in the
neighboring stacks and thus of approaching them in
space. The other factors affecting the polymerization
are the number of methylene groups between the
system of the triple bonds and arylcarbamate groups,
and the character of substituent in the arylcarbamate
group which by its donor or acceptor properties can
influence the strength of the hydrogen bond.
The reaction of monoacetylene alcohols and aryl
isocyanates gave rise to monoacetylene carbamates
Ia l.
X= H (a, d, h, j, k), MeO (b, e), NO2 (c, f), Me2N (g, i); n = 2 (a c), 3 (d g), 6 (h, i), 7 (j), 9 (k).
Compound Il was prepared by reaction of 10-unde-
cyn-1-ol with tosyl isocyanate along the following
scheme:
were the first to use in the synthesis of symmetrical
diynes a catalytic system CuI-pyrrolidine that was
formerly successfully applied to preparation of un-
symmetrical diynes [17]. It is known from published
data that in oxidative dimerization of the terminal
acetylenes the choice of a base plays a crucial role
[18], and here are important both the basicity and the
sterical accessibility of the nitrogen for the interaction
with copper salts. Pyrrolidine is a strong base (pka
11.1) [19], and it has been applied both as a catalyst
and a solvent, and oxidation has been effected by air
oxygen.
Isocyanates are known to be supersensitive to
moisture forming with water the corresponding N,N -
diarylcarbamides. The monoacetylene carbamates
were isolated by preparative TLC. The spectral data
confirming the structure of compounds Ia l obtained
are presented in Table 1, and physical constants and
elemental analyses in Table 2.
Diyne carbamates IIa k were prepared by oxid-
ative dimerization of monoacetylene carbamates Ia k.
The oxidative dimerization process of terminal
acetylenes has several modifications [15, 16]. We
X = H (a, d, h, j, k), MeO (b, e), NO2 (c, f), Me2N
(g, i); n = 2 (a c), 3 (d g), 6 (h, i), 7 (j), 9 (k).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002

SYNTHESIS OF NEW CONJUGATED DIYNES
777
1
Table 1. IR, H and 13C NMR spectra of monoacetylene carbamates Ia l
1a
Compd.
no.
IR spectrum, , cm
1H NMR spectrum, , ppmb
13C NMR spectrum, , ppmb
Ia
Ib
Ic
3445s(NH), 3340s(C CH), 2.06 t (1H, C CH), 2.61 t.d (2H, 19.74 (C CCH2), 63.30 (OCH2), 70.40
2110 w (C C), 1720 v.s C CCH2), 4.28 t (2H, OCH2), 6.80 (C CH), 80.67 (C CH), 119.14 (o-C
(C=O), 1600 s (C arom- br.s (1H, NH), 7.09 m (1H, p-H arom), 124.00 (p-C arom), 129.48
C arom), 1520 s ( NH) arom), 7.40 m (4H, m, o-H arom) (m-C arom), 138.10 (i-C arom),
153.54 (C=O)
3445 s (NH), 3320 s (C
2.05 t (1H, C CH), 2.60 t.d (2H, 19.75 (C CCH2), 55.90 (OCH3), 63.22
CH), 2110w C C), 1720 v.s C CCH2), 3.80 s (3H, OCH3), 4.27 t (CH2O), 70.33 (C CH), 80.72 (C CH),
(C=O), 1600 s (C arom-C (2H, OCH2), 6.70 br.s (1H, NH), 114.67 (m-C arom), 121.18 (o-C
arom), 1510 s ( NH)
6.69 m (2H, m-H arom), 7.29 m (2H, arom), 131.13 (i-C arom), 153.92
o-H arom) (C=O), 156.48 (p-C arom)
3270s(NH), 3390s(C CH), 2.07 t (1H, C CH), 2.62 t.d (2H, 19.07 (C CCH2), 63.51 (CH2O), 70.93
3060 s (C arom H), 2950 s C CCH2), 4.27 t (2H, OCH2), 7.80 m (C CH), 80.59 (C CCH2), 118.16
(Csp3 H), 2930 s (Csp3 H), (2H, o-H arom), 8.21 m (2H, m-H (o-C arom), 125.22 (m-C arom),
2110 w (C C), 1730 v.s arom), 9.40 br.s (1H, NH)
(C=O), 1600 c (C arom-C
142.95 (i-C arom), 146.02 (p-C
arom), 153.38 (C=O)
arom), 1555 v.s ( NO2),
as
1510 s ( NH), 1330 v.s (
s
NO2)
Id
Ie
3280s (NH), 3305s(C CH), 1.90 qn (2H, CH2CH2CH2), 2.07 t (1H, 15.57 (C CCH2), 28.24 (CH2CH2CH2),
3040s(C arom H), 2960s C CH), 2.34 t.d (2H, C CCH2), 4.29 t 64.11 (CH2O), 69.55 (C CH), 83.45
(Csp3 H), 2930 c (Csp3 H), (2H, OCH2), 6.90 br.s (1H, NH), 7.05 (C CH), 119.17 (o-C arom), 123.84
2110 w (C C), 1700 v.s t (1H, p-H arom), 7.28 t (2H, m-H (p-C arom), 129.43 (m-C arom),
(C=O), 1600 s (C arom-C arom), 7.38 d (2H, o-H arom)
138.31 (i-C arom), 153.98 (C=O)
arom), 1545 s ( NH)
3270s(NH), 3310s(C CH), 1.89 qn (2H, CH2CH2CH2), 2.01 t (1H, 15.56 (C CCH2), 28.28 (CH2CH2CH2),
3040 s (C arom H), 2960 s C CH), 2.32 t.d (2H, C CCH2), 3.79 s 55.88 (OCH3), 64.02 (CH2O), 69.50
(Csp3 H), 2940 s (Csp3 H), (3H, OCH3), 4.25 t (2H, OCH2), 6.79 (C CH), 83.51 (C CH), 114.64 (m-C
2860 s (Csp3 H), 2110 w br.s (1H, NH), 6.85 d (2H, m-H arom), 121.17 (o-C arom), 131.35
(C C), 1700 v.s (C=O), arom), 7.28 d (2H, o-H arom)
1600 s (C arom-C arom),
(i-C arom), 154.37 (C=O), 156.38
(p-C arom)
1535 s ( NH)
If
3285s(NH), 3380s(C CH), 1.89 qn (2H, CH2CH2CH2), 2.06 t 14.91 (C CCH2), 28.13 (CH2CH2CH2),
3040 s (C arom H), 2960 s (1H, C CH), 2.32 t.d (2H, C CCH2), 64.12 (CH2O), 70.02 (C CH), 83.23
(Csp3 H), 2930s(Csp3 H), 2110 4.28 t (2H, OCH2), 7.75 d (2H, o-H (C CH), 118.06 (o-C arom), 125.22
w (C C), 1730 v.s (C=O), arom), 8.29 d (2H, m-H arom), 9.30 (m-C arom), 142.85 (i-C arom),
1600 s (C arom-C arom), br.s (1H, NH)
145.97 (p-C arom), 154.57 (C=O)
1555v.s ( NO2), 1510 s (
as
NH), 1330 v.s ( NO2)
s
Ig
3440s (NH), 3310s(C CH), 1.91 qn(2H, CH2CH2CH2), 2.01 t (1H, 15.61 (C CCH2), 28.34 (CH2CH2CH2),
2110 w (C C), 1720 v.s C CH), 2.33 t.d (2H, C CCH2), 2.92 s 41.47 (CH3), 63.91 (CH2O), 69.35
(C=O), 1580 s (C arom-C (6H, CH3), 4.25 t (2H, OCH2), 6.41 (C CH), 83.56 (C CH), 113.81 (m-C
arom), 1510 s ( NH)
br.s (1H, NH), 6.75 d (2H, m-H arom), 121.43 (o-C arom), 128.00
arom), 7.21 d (2H, o-H arom)
(i-C arom), 148.10 (p-C arom),
154.36 (C=O)
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778
VYAZMIN et al.
Table 1. (Contd.)
1a
Compd.
no.
IR spectrum, , cm
1H NMR spectrum, , ppmb
13C NMR spectrum, , ppmb
Ih
3440s(NH), 3315s(C CH), 1.4 1.6 m (6H, CH2), 1.70 qn(2H, CH2), 18.72 (C CCH2), 25.80, 28.19, 28.71,
2120 w (C C), 1710 v.s 1.97 t (1H, C CH), 2.21 t. d (2H, 29.20 (CH2), 65.65 (CH2O), 68.74
(C=O), 1600 s (C arom-C C CCH2), 4.18 t (2H, OCH2), 6.79 (C CH), 84.91 (C CH), 119.09 (o-C
arom), 1510 s ( NH)
br.s (1H, NH), 7.07 t (1H, p-H arom), 123.74 (p-C arom), 129.42
arom), 7.31 t (2H, m-H arom), 7.39 d (m-C arom), 138.40 (i-C arom),
(2H, o-H arom)
154.16 (C=O)
Ii
3440s(NH), 3310s(C CH), 1.4 1.6 m (6H, CH2), 1.70 qn(2H, CH2), 18.72 (C CCH2), 25.82, 28.22, 28.73,
2110 w (C C), 1720 v.s 1.98 t (1H, C CH), 2.21 t.d (2H, 29.26, (CH2), 41.48 (CH3), 65.45
(C=O), 1580 s (C arom-C C CCH2), 2.93 s(6H, CH3), 4.15 t (2H, (CH2O), 68.65 (C CH), 84.93 (C CH),
arom), 1510 s ( NH)
OCH2), 6.40 br.s (1H, NH), 6.72 d 113.80 (m-C arom), 121.39 (o-C
(2H, m-H arom), 7.21 d (2H, o-H arom), 127.97 (i-C arom), 148.12
arom)
3450s(NH), 3320s(C CH), 1.3 1.8 m (10H, CH2), 1.96 t (1H, 18.76 (C CCH2), 26.14, 28.74, 28.97,
2120 w (C C), 1720 v.s (C CH), 2.21 t.d (2H, C CCH2), 4.19 t 29.1, 31.10 (CH2), 65.72 (CH2O),
(C=O), 1600 s (C arom-C (2H, OCH2), 6.67 br.s (1H, NH), 68.59 (C CH), 85.03 (C CH), 119.05
arom), 1510 s ( NH) 7.08 t (1H, p-H), 7.31 t (2H, m-H (o-C arom), 123.74 (p-C arom), 129.43
(p-C arom), 154.38 (C=O)
Ij
Ik
Il
arom), 7.39 d (2H, o-H arom)
(m-C arom), 138.37 (i-C arom),
154.07 (C=O)
3450s(NH), 3320s(C CH), 1.2 1.8 m (14H, CH2), 1.96 t (1H, 18.79 (C CCH2), 26.24, 28.85, 29.10,
2120 w (C C), 1720 v.s C CH), 2.21 t.d (2H, C CCH2), 4.19 t 29.33, 29.40, 29.60, 29.76 (CH2),
(C=O), 1600 s (C arom-C (2H, OCH2), 6.69 br.s (1H, NH), 7.08 65.79 (CH2O), 68.52 (C CH), 85.16
arom), 1510 s ( NH) t (1H, p-H arom), 7.31 t (2H, m-H (C CH), 119.03 (o-C arom), 123.72
arom), 7.39 d (2H, o-H arom)
(p-C arom), 129.43 (m-C arom),
138.40 (i-C arom), 154.11 (C=O)
3470s(NH), 3290s(C CH), 1.19 1.45 m (10H, CH2), 1.45 1.62 m 18.20 (C CCH2), 21.51, 25.37, 28.24,
2120 w (C C), 1735 v.s (4H, CH2), 1.96 t (1H, C CH), 2.18 t.d 28.49, 28.79, 28.87, 29.10 (CH2),
(C=O), 1590 s (C arom-C (2H, C CCH2), 2.46 s (3H, CH3), 4.06 t 67.02 (CH3), 67.99 (CH2O), 76.47
arom), 1340 v.s ( SO2), (2H, OCH2), 7.28 br.s (1H, NH), 7.32 (C CH), 84.56 (C CH), 128.19 (m-
1150 v.s ( SO2) as
d (2H, m-H arom), 7.92 d (2H, o-H C arom), 129.41 (o-C arom), 135.49
s
arom)
(p-C arom), 144.81 (i-C arom),
150.51 (C=O)
a
IR spectra of compounds Ia, b, g l were recorded in CHCl3, those of compounds Ic f from KBr pellets.
1H and 13C NMR spectra of compounds Ic, f were registered in acetone-d6, of the other compounds in CDCl3.
b
Table 2. Yields, melting points, and elemental analyses of monoacetylene carbamates Ia k
Found, %
Calculated, %
H
Compd. Yield,
mp,
oC
Formula
no.
%
C
H
N
C
N
Ia
Ib
Ic
Id
Ie
If
Ig
Ih
Ii
79
61
50
50
71
47
44
43
67
50
81
40
52 53
84 86
118 120
45 47
46 48
93 94
103 105
46 48
70 72
48 49
44 46
70 72
70.04
65.78
56.32
70.90
67.25
58.07
68.24
73.25
70.94
74.30
75.11
62.17
5.79
6.37
4.36
6.57
6.48
5.06
7.37
7.66
8.45
8.07
9.03
7.45
7.33
6.19
11.94
6.93
5.92
11.03
11.42
5.86
9.86
5.50
5.08
3.91
C11H11NO2
C12H13NO3
C11H10N2O4
C12H13NO2
C13H15NO3
C12H12N2O4
C14H18N2O2
C15H19NO2
C17H24N2O2
C16H21NO2
C18H25NO2
C19H27NO4S
69.83
65.74
56.41
70.92
66.94
58.06
68.27
73.42
70.80
74.10
75.22
62.44
5.86
6.44
4.30
6.45
6.48
4.87
7.37
7.80
8.39
8.16
8.77
7.45
7.40
6.39
11.96
6.89
6.00
11.29
11.37
5.71
9.71
5.40
4.87
3.83
Ij
Ik
Il
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002

SYNTHESIS OF NEW CONJUGATED DIYNES
The reaction was completed within 15 20 min and
779
furnished the desired compounds in high yield. The
products were isolated from the reaction mixture as
follows. First the reaction mixture was quenched with
saturated aqueous solution of NH4Cl and extracted
with tetrahydrofuran. The diacetylene compound after
removing THF contained pyrrolidine as an impurity.
Further purification was carried out by two proce-
dures: by chromatography and by treating the diacet-
ylene on glass frit filter with diluted hydrochloric
acid. The attempts to separate this mixture by pre-
parative thin-layer chromatography were inefficient
for diynes easily polymerized on the sorbent hamper-
ing the elution. This fact resulted in a relatively low
yield (48%) of compound IIa. The washing of diynes
with 15% aqueous HCl was more successful. We also
demonstrated that this method provided excellent
results also in dimerization of terminal acetylene
alcohols. We attempted to carry out the dimerization
of terminal acetylenes by classical method with
Glaser Hay catalyst (complex of CuCl with tetra-
methylethylenediamine) and oxygen flow through the
reaction mixture for several hours to effect oxidation.
However this attempt failed even at equimolar
amounts of the catalyst and terminal acetylene.
We cannot yet rationalize the different behavior
pattern of acetylene and diacetylene diols in reaction
with tosyl isocyanate.
We carried out estimation of the strength of inter-
molecular hydrogen bond in solid compound IId. To
this end the IR spectra of the compound were
registered from a sample pelleted with KBr and from
solutions in CH2Cl2 of 1% and 0.5% concentration.
Therewith the absorption band of the stretching vibra-
tions of the N H bond appeared in the first case at
1
3333 cm whereas in both solutions this band was
1
observed at 3430 cm . The formation enthalpy of the
hydrogen bond may be calculated by a formula
from [24].
H = 1.3 ( )1/2,
where H is formation enthalpy of the hydrogen bond
1
(kJ mol ),
is the frequency difference for the
in diluted solution and in
stretching vibrations
the solid state respectively (cm ). Our calculation
gave the value 12.8 kJ mol . It should be noted
NH
1
We tried to prepare from compound Il the
corresponding diyne by oxidative dimerization on
1
however that the formation enthalpy value for a
hydrogen bond is considered to be appropriate if the
catalytic
systems
CuI pyrrolidine,
CuI
i-Pr2NH Pd(PPh3)2Cl2 I2 [20], and also by Hay [21,
22] and Eglintone methods [23]. At the use of two
former systems strong tarring occurred, and after
using Glase Hay or Eglintone procedures the initial
tosyl carbamate Il remained intact and was recovered
from the reaction mixture. In special runs compound
Il was stirred with equimolar amounts of CuI disper-
sion both in pyrrolidine and dichloromethane solu-
tion, and the initial tosyl carbamate did not suffer any
changes. The reaction of 10,12-docosadiyne-1,22-diol
and tosyl isocyanate provided a complex mixture of
products, and we failed to isolate from the mixture
the desired diyne.
1
is larger than 100 cm [25]; in our case this value
1
amounted to 93 cm .
The spectral data supporting the structure of com-
pounds IIa k obtained are listed in Table 3, physical
constants and elemental analyses in Table 4.
The final stage of this study involved investigation
of photoinitiated polymerization of diyne carbamates
IIa k in the solid phase under UV light with various
wavelength [26].
It is known from published data that whereas the
activation energy of thermal polymerization amounts
1
to 80 105 kJ mol , the corresponding value for
Yet the reaction of 2-butyne-1,4-diol with tosyl
isocyanate under conditions used in the synthesis of
monoacetylene carbamates Ia l afforded product III;
its structure and composition was proved by spectral
data and elemental analysis.
1
photopolymerization reaches only 10 kJ mol [27].
To the polymerization kinetics correspond two types
of curves: with a long induction time and with none
[28, 29].
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002

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VYAZMIN et al.
1
Table 3. IR, H and 13C NMR spectra of diacetylene carbamates IIa k
1a
Compd.
no.
IR spectrum, , cm
1H NMR spectrum, , ppmb
13C NMR spectrum, , ppmb
IIa
3445s(NH), 1740v.s (C=O), 2.68 t (4H, C CCH2), 4.21 t (4H, OCH2), 19.91 (C CCH2), 62.44 (OCH2), 66.49
1600 s (C arom-C arom), 7.01 t (2H, p-H arom), 7.30 t (4H, (C CC C), 74.74 (CH2C C), 118.71
1520 s ( NH)
m-H arom), 7.60 d (4H, o-H arom), (o-C arom), 123.06 (p-C arom),
8.79 br.s (2H, NH)
129.13 (m-C arom), 139.58 (i-C
arom), 153.58 (C=O)
IIb
3450s(NH), 1720 v.s (C=O), 2.69 t (4H, C CCH2), 3.79 s(6H, 19.57 (C CCH2), 55.14 (OCH3), 62.32
1600 s (C arom-C arom), OCH3), 4.21 t (4H, OCH2), 6.87 d (4H, (OCH2), 68.02 (C CC C), 74.48
1520 s ( NH)
m-H arom), 7.49 d (4H, o-H arom), (CH2C C), 114.29 (m-C arom),
8.61 br.s (2H, NH)
121.15 (o-C arom), 131.38 (i-C
arom), 154.37 (C=O), 156.38 (p-C
arom)
IIc
3330s(NH), 3060s(C arom 2.77 t (4H, C CCH2), 4.21 t (4H, OCH2), 19.77 (C CCH2), 63.10 (OCH2), 66.20
H), 3040s(C arom H), 2960 7.82 d (4H, o-H arom), 8.22 d (4H, (C CC C), 74.42 (CH2C C), 118.22
s (Csp3 H), 2850s(Csp3 H), m-H arom), 9.50 br.s (2H, NH) (o- C arom), 1125.25 (m-C arom),
1740 v.s (C=O), 1600s(C
arom-C arom), 1555 v.s
142.42 (i-C arom), 146.02 (p- C
arom), 153.50 (C=O)
(
NO2), 1520s( NH), 1330
as
v.s ( NO2)
s
IId
IIe
3330s(NH), 3050s(C arom 1.89 qn (4H, CH2CH2 CH2), 2.40 t (4H, 15.68 (C CCH2), 28.10 (CH2CH2CH2),
H), 3040s(C arom H), 2950s C CCH2), 4.20 t (4H, OCH2), 7.00 t 63.31 (CH2O), 66.02 (C CC C), 76.80
(Csp3 H), 2840s(Csp3 H), 1700 (2H, p-H arom), 7.27 t (4H, m-H (C CCH2), 118.64 (o-C arom), 122.91
v.s (C=O), 1600s(C arom-
C arom), 1535 s ( NH)
arom), 8.55 d (4H, o-H arom), 8.67 (p-C arom), 129.10 (m-C arom),
br.s (2H, NH) 139.74 (i-C arom), 153.85 (C=O)
3300s(NH), 3040s(C arom 1.89 qn (4H, CH2CH2 CH2), 2.41 t (4H, 14.93 (C CCH2), 27.39 (CH2CH2CH2),
H), 2960s(Csp H), 2930s C CCH2),3.79 s(6H, OCH3), 4.18 t 54.38 (OCH3), 62.42 (CH2O), 65.24
3
(Csp3 H), 2830s(Csp3 H), 1700 (4H, OCH2), 6.67 d (4H, m-H arom), (C CC C), 76.06 (C CCH2), 113.51
v.s (C=O), 1600 s (C arom- 7.47 d (4H, o-H arom), 8.48 br.s (m-C arom), 119.53 (o-C arom),
C arom), 1515 © ( NH)
(2H, NH)
132.00 (i-C arom), 153.29 (C=O),
156.16 (p-C arom)
IIf
3300 s (NH), 3040 s (C arom 1.89 qn (4H, CH2CH2 CH2), 2.42 t (4H, 15.65 (C CCH2), 27.89 (CH2CH2CH2),
H), 2930 ©(Csp3 H), 2860 c C CCH2), 4.25 t (4H, OCH2), 7.89 d 62.42 (CH2O), 66.04 (C CC C), 76.72
(Csp3 H), 1740 v.s (C=O), (4H, o-H arom), 8.21 d (4H, m-H (C CCH2), 118.12 (o-C arom), 119.53
1600 c (C arom-C arom), arom), 9.28 br.s (2H, NH)
1555 v.s ( NO2), 1510 ©
(m-C arom), 142.89 (i-C arom),
145.98 (p-C arom), 153.56 (C=O)
as
(
NH), 1330 v.s ( NO2)
s
IIg 3300s(NH), 3040s(C arom 1.89 qn (4H, CH2CH2 CH2), 2.42 t (4H, 16.49 (C CCH2), 28.23 (CH2CH2CH2),
H), 2960s(Csp H), 2850s C CCH2), 2.92 s(12H, NMe2), 4.22 t 41.42 (CH3), 63.93 (CH2O), 66.27
(Csp3 H), 1690 v.s (C=O), (4H, OCH2), 6.42 br.s (2H, NH), 6.72 (C CC C), 113.74 (m-C arom), 121.74
3
1610s(C arom-C arom),
1515 s ( NH)
d (4H, m-H arom), 7.21 d (4H, o-H (o-C arom), 128.02 (i-C arom),
arom) 148.10 (p-C arom), 154.32 (C=O)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002

SYNTHESIS OF NEW CONJUGATED DIYNES
781
Table 3. (Contd.)
1a
Compd.
no.
IR spectrum, , cm
1H NMR spectrum, , ppmb
13C NMR spectrum, , ppmb
IIh 3480s(NH), 1750 v.s (C=O), 1.31 1.75 m (16H, CH2), 2.28 t (4H, 19.52 (C CCH2), 25.81, 28.53, 28.81,
1600s(C arom-C arom),
1505 s ( NH)
C CCH2), 4.20 t (4H, OCH2), 6.68 29.17 (CH2), 65.64 (CH2O), 65.84
br.s (2H, NH), 7.08 t (2H, p-H arom), (C CC C), 119.05 (o-C arom), 123.76
7.31 t (4H, m-H arom), 7.39 d (4H, (p-C arom), 129.44 (m-C arom),
o-H arom)
138.36 (i-C arom), 154.07 (C=O)
IIi 3440s(NH), 1720 v.s (C=O), 1.35 1.75 m (16H, CH2), 2.37 t (4H, 19.52 (C CCH2), 25.83, 28.56, 28.85,
1580s(C arom-C arom),
1510 © ( NH)
C CCH2), 2.91 s(12H, CH3), 4.15 t 29.24 (CH2), 41.46 (CH3), 65.45
(4H, OCH2), 6.42 br.s (2H, NH), 6.72 (CH2O), 65.81 (C CC C), 113.78 (m-C
d (4H, m-H arom), 7.21 d (4H, o-H arom), 121.39 (o-C arom), 128.01
arom)
(i-C arom), 148.10 (p-C arom),
154.36 (C=O)
IIj 3440s(NH), 1720 v.s (C=O), 1.3 1.75 m (20H, CH2), 2.28 t (4H, 19.52 (C CCH2), 26.13, 28.59, 29.08,
1600s(C arom-C arom),
1510 s ( NH)
C CCH2), 4.18 t (4H, OCH2), 6.65 29.26, 30.10 (CH2), 65.70 (CH2O),
br.s (2H, NH), 7.08 t (2H, p-H 68.36 (C CC C), 119.06 (o-C arom),
arom), 7.30 t (4H, m-H arom), 7.41 d 123.73 (p-C arom), 129.42 (m-C
(4H, o-H arom)
arom), 138.39 (i-C arom), 154.09
(C=O)
IIk 3450s(NH), 1730 v.s (C=O), 1.2 1.8 m (28H, CH2), 2.26 t (4H, 19.60 (C CCH2), 26.24, 28.70, 29.18,
1600s(C arom-C arom),
1510 s ( NH)
C CCH2), 4.18 t (4H, OCH2), 6.67 29.33, 29.59, 29.73, 30.11 (CH2),
br.s (2H, NH), 7.07 t (2H, p-H 65.79 (CH2O), 68.35 (C CC C),
arom), 7.29 t (4H, m-H arom), 7.41 119.03 (o-C arom), 123.72 (p-C
d (4H, o- H arom)
arom), 129.43 (m-C arom), 138.40
(i-C arom), 154.12 (C=O)
a
IR spectra of compounds IIa, b, h k were taken in CHCl3, of compounds IIc g in KBr pellets.
1H and 13C NMR spectra of compounds IIa f were recorded in acetone-d6, of the other substances in CDCl3.
b
Table 4. Yields, melting points, and elemental analyses of diacetylene carbamates IIa k
Found, %
Calculated, %
H
Compd. Yield,
mp,
oC
Formula
no.
%
C
H
N
C
N
IIa
IIb
IIc
IId
IIe
IIf
IIg
IIh
IIi
48
77
90
77
78
90
80
70
76
73
89
152 154
70.35
66.15
56.65
71.27
67.46
58.42
68.48
73.75
71.16
74.03
75.43
5.67
5.67
3.96
5.91
6.22
4.32
6.92
7.43
7.92
7.78
8.44
7.08
6.49
12.21
6.84
6.11
11.32
11.41
5.72
9.71
5.53
4.75
C22H20N2O4
C24H24N2O6
C22H18N4O8
C24H24N2O4
C26H28N2O6
C24H22N4O8
C28H34N4O4
C30H36N2O4
C34H46N4O4
C32H40N2O4
C36H48N2O4
70.20
66.05
56.66
71.27
67.23
58.30
68.55
73.74
71.05
74.39
75.49
5.36
5.54
3.89
5.98
6.08
4.48
6.99
7.43
8.07
7.80
8.45
7.44
6.42
12.01
6.93
6.03
11.33
11.42
5.73
9.75
5.42
4.89
a
a
107 109
129 131
142 144
167 169
127 129
160 162
118 120
96 98
IIj
IIk
a
Compounds IIa, b undergo solid-phase topochemical polymerization before they are heated to melting points.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002

782
VYAZMIN et al.
The data in Table 5 also show that the activity of
diyne carbamates in polymerization depends on the
wavelength of the radiation. At the use of the mercury
lamp of medium pressure PRK-400 with a Pyrex
glass filter the samples are irradiated with light in the
range of 360 370 nm wavelength. The diyne
carbamates have no absorption bands in this spectral
range (see figure and Table 6), and therefore no
polymerization occurs.
When the same lamp is used without the Pyrex
filter, about 16% of the radiation power correspond
to the region with a maximum at 254 nm [31] that
apparently ensures the activity of diyne aryl-
carbamates in the solid-phase polymerization. Note
however that monomer conversion in this case
constitutes about a half of that obtained under irradia-
tion with a lamp BUV-15 with the main wavelength
Typical UV spectrum of diyne carbamates IIa k.
Since the penetrability of the far UV radiation
(180 300 nm) is low, the polymerization was carried
out in a water dispersion of crushed diyne crystals
under stirring. The process is heat-releasing , and
therefore water played the role of heat-transfer agent.
The irradiation period and wavelength of the UV light
were important parameters for the polymerization
process.
254 nm. Diyne p-nitrophenylcarbamates virtual-
max
ly did not polymerize within the experiment period
under UV irradiation with the above sources. How-
ever at prolonged (within several tens of hours)
standing in diffused daylight a polymerization was
observed that apparently should be described with
kinetic curves with a long induction period. Although
these compounds absorb light at 360 370 nm the
intensity is not sufficient for fast polymerization, or
the energy of the triplet excited state of the nitro-
phenylcarbamate group is lower than that of diacetyl-
ene group and therefore the energy transfer to the
diacetylene fragment becomes impossible.
The results of photoinitiated solid-phase poly-
merization of compounds IIa k are presented in
Table 5. The data suggest the following conclusions.
In the series of phenylcarbamates with an odd number
of methylene groups (n = 3, 7, 9) the activity in
polymerization grew with chain elongation. The same
effect is observed with phenylcarbamates with an
even number of methylene groups (n = 2, 6), and the
compounds with the even number of methylene
groups were more active, than those with the odd
number (carbamates with two and six CH2 groups
were more active than their respective analogs with
three and seven CH2 groups). The increase in activity
of diyne carbamates with growing number of methyl-
ene groups suggested the following hypothesis. It is
known that diacetylene molecules located in stacks as
bars are synchronously rotating in the course of
polymerization without displacement of the mass
centers. Since these carbamate molecules are fixed at
the ends with the hydrogen bonds this rotation
requires internal freedom that is just provided by
methylene groups playing the role of spacers. With
growing number of methylene groups the degree of
freedom also increases resulting in higher polymeriz-
ation degree. The separation of the diyne carbamates
in two groups may be only due to the different
crystallographic packing. Interestingly enough that in
the literature was described the polymerization of
diyne phenylcarbamates with n = 4, 5, 6 under -ir-
radiation (60 Mrad) where the diyne phenylcarbamate
with 5 methylene groups was inactive, and the com-
pounds with 4 and 6 methylene groups furnished
polymer in 95 and 70% yield respectively [30].
In a series of diyne carbamates with para-substitu-
ents in the benzene ring (NO2, H, CH30, Me2N) the
lowest polymerization activity was observed in
p-nitrophenylcarbamates IIb and IIe. The activity
considerably grew in going to phenylcarbamates and
further to p-methoxycarbamate IIb and IIf. On the
contrary, the introduction of a p-dimethylamino
group (compounds IIg and IIi) resulted in decreased
activity in photopolymerization.
More detailed interpretation of the results obtained
requires data on the packing of molecules of these
compounds in the unit cells of their crystals.
As reported in the literature [32], the diyne
carbamate are not capable of thermal polymerization.
The results of this study invalidate this statement.
Two among eleven previously unknown diyne
carbamates we synthesized were active in thermal
polymerization: 3,5-octadiyne-1,8-diyl bis[n-(4-meth-
oxyphenyl)carbamate] (IIb), and 3,5-octadiyne-1,8-
diyl bis[n-(4-nitrophenyl)carbamate] (IIc). Diyne IIb
changed from colorless to dark-red even at
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002

SYNTHESIS OF NEW CONJUGATED DIYNES
783
Table 5. Degree of diyne carbamate IIa k conversion at UV irradiation from different sources (%)a
Lamp BUV-15
run no. 1 run no. 2
Lamp PRK-400 without filter
Compd.
no.
Color of polymer IVa k
run no. 1
run no. 2
IIa
IIb
IIc
IId
IIe
IIf
IIg
IIh
IIi
25
80
0
17
28
0
26
82
0
17
27
0
Orange
Dark-red
41
0
8
14
0
42
0
9
13
0
Blue
Blue
9
8
Light-violet
Light-red
Dark-red
Blue
48
28
31
57
50
27
34
55
IIj
IIk
27
28
Blue
a
The degree of conversion is given to the nearest percent.
Table 6. UV spectra of diyne carbamates IIa k depending on substituent X in phenyl ringa
1, nm
1, nm
2, nm
2, nm
260, nm
370, nm
360
min
max
min
ma
250
X
[log
l mol cm ]
1,
[log
l mol cm ]
1,
[log
l mol cm ]
2,
[log
l mol cm ]
2,
[log ,
l mol cm ]
[log ,
l mol cm ]
min
ma
min
ma
1
1
1
1
1
1
1
1
1
1
1
1
H
214 (3.84)
235 (4.48)
273 (3.27)
250 (3.44)
254 (3.16)
260 (3.13)
250 (4.26)
254 (3.96)
260 (3.01)
250 (3.46)
254 (3.37)
260 (3.46)
250 (4.29)
254 (4.37)
260 (4.49)
360 ( )
366 ( )
370 ( )
360 ( )
366 ( )
MeO
NO2
215 (3.79)
210 (4.17)
230 (3.82)
240 (4.52)
219 (4.25)
266 (4.54)
264 (2.81)
255 (3.37)
297 (2.50)
289 (3.49)
319 (4.41)
312 (3.54)
370 ( )
360 (3.71)
366 (3.53)
370 (3.36)
360 ( )
366 ( )
370 ( )
Me2N
a
Average values in homologous series.
storage in a refrigerator. The attempt to measure the
melting points of these carbamates led to polymeriz-
ation, and melting started over 190 200 C with
decomposition (with charring and gas evolution).
enyne structure. As known from the literature, the
absorption bands of triple bonds in the spectra of the
initial diacetylenes are situated in the region of higher
frequencies. The monomers possess a strong band
1
C C at 2260 cm , and polymers have two strong
The structure of polydiacetylenes IVb, IVc, and
IVi was proved by Raman spectroscopy. In the
spectra of these compounds were present the absorp-
tion bands of conjugated double bonds at 1475 (IVb),
1
bands C C at 2100 cm , and a C=C band at
1
1500 cm [33].
EXPERIMENTAL
1
1480 (IVc), 1500 (IVi) cm , and of conjugated triple
1
bonds at 2100 cm (in all the three compounds).
IR spectra were recorded from 3% solutions in
CHCl3 on spectrophotometer Specord 75IR, from
0.5% and 1% solutions in CH2Cl2 and from KBr
These data exclude the presence of a butatriene struc-
ture and reveal formation of polydiacetylenes of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002

784
VYAZMIN et al.
pellets on Fourier spectrometer Bruker IFS-88. The
Raman spectra were measured on Ramalog-5 instru-
ment equipped with an argon laser ( 488 nm). UV
spectra were taken in CH3CN on spectrophotometer
(15 mmol) of 3-butyn-1-ol, 3.075 g (18.75 mmol) of
4-nitrophenyl isocyanate, 75 mg of dibutyltin bis(2-
ethylhexanoate), 2 drops of Et3N, and 45 ml of
anhydrous THF. The 4-nitrophenyl isocyanate was
added by small portions.
1
Specord M40 UV-Vis. H and 13C NMR spectra were
registered on spectrometer Bruker DPX-300 at 300
and 75 MHz respectively, solvents CDCl3 and
(CD3)2CO, internal reference TMS. Mass spectra
were obtained on GC-MS instrument MKh-1330,
ionizing electrons energy 70 eV. TLC analyses were
carried out on Silufol UV-254 plates, development
under UV-irradiation or with potassium permanganate
solution. The preparative TLC was performed on
Silpearl silica gel, spots were visualized under UV
irradiation. The topochemical solid-phase polymeriz-
ation was carried out under UV radiation of mercury
4-Pentyn-1-yl N-phenylcarbamate (Id) was
prepared similarly to compound Ia from 0.84 g
(10 mmol) of 4-pentyn-1-ol, 1.49 g (12.5 mmol) of
phenyl isocyanate, 50 mg of dibutyltin bis(2-ethyl-
hexanoate), 1 drop of Et3N, and 30 ml of anhydrous
THF.
4-Pentyn-1-yl N-(4-methoxyphenyl)carbamate
(Ie) was prepared similarly to compound Ia from
0.84g (10mmol) of 4-pentyn-1-ol, 1.86g (12.5mmol)
of 4-methoxyphenyl isocyanate, 50 mg of dibutyltin
bis(2-ethylhexanoate), 1 drop of Et3N, and 30 ml of
anhydrous THF.
lamps of low pressure BUV-15 (
medium pressure PRK-400 (
without a Pyrex glass filter. max
254 nm) and of
366 nm) with and
max
4-Pentyn-1-yl N-(4-nitrophenyl)carbamate (If)
was prepared similarly to compound Ia from 0.84 g
(10 mmol) of 4-pentyn-1-ol, 2.05 g (12.5 mmol) of
4-nitrophenyl isocyanate, 50 mg of dibutyltin bis(2-
ethylhexanoate), 1 drop of Et3N, and 30 ml of
anhydrous THF. The 4-nitrophenyl isocyanate was
added by small portions.
The initial acetylene alcohols were prepared by the
following procedures. 3-Butyn-1-ol was obtained
from lithium acetylide and oxirane [34]. 4-Pentyn-1-
ol was synthesized by reaction of tetrahudrofurfuryl
chloride with sodium amide in liquid ammonia [35].
The synthesis of 6-octyn-1-ol was analogous to [36]
and included four stages starting with 1,6-hexanediol.
7-Nonyn-1-ol was prepared by alkylating propargyl
alcohol followed by isomerization into a terminal
acetylene alcohol [37, 38]. The four-stage synthesis
of 10-undecenyn-1-ol proceeded from 10-udecenoic
acid [39 41].
4-Pentyn-1-yl N-(4-dimethylaminophenyl)
carbamate(Ig). To a solution of 0.155 g (1.85 mmol)
of 4-pentyn-1-ol dried with molecular sieves, 10 mg
of dibutyltin bis(2-ethylhexanoate), and 1 drop of
Et3N in 10 ml of anhydrous THF was added dropwise
at stirring 0.32 g (2 mmol) of phenyl isocyanate. The
completion of reaction could not be determined by
TLC following the consumption of the initial alcohol,
for the alcohol and carbamate had the same Rf value.
The reaction mixture was stirred for 2 h, the solvent
was distilled off in a vacuum, and the residue was
subjected to preparative TLC on silica gel (eluent
hexane ether, 5: 7). The target product was eluted
from silica gel with THF and dried on MgSO4.
3-Butyn-1-yl N-phenylcarbamate (Ia). To a solu-
tion of 1.4 g (20 mmol) of 3-butyn-1-ol, 100 mg of
dibutyltin bis(2-ethylhexanoate), and 2 drops of Et3N
in 60 ml of anhydrous THF was added dropwise at
stirring 2.98 g (25 mmol) of phenyl isocyanate. Then
the reaction mixture was stirred for 1 h (TLC
monitoring). After total consumption of the initial
3-butyn-1-ol the solvent was distilled off in a vacuum,
and the residue was subjected to preparative TLC on
silica gel (eluent hexane ether, 1: 1). The reaction
product was eluted from silica gel with THF, and the
solution was dried on MgSO4.
7-Octyn-1-yl N-phenylcarbamate (Ih) was pre-
pared in the same way as compound Ia from 0.42 g
(3.3 mmol) of 7-octyl-1-ol dried with molecular
sieves, 0.43 g (3.63 mmol) of phenyl isocyanate,
15 mg of dibutyltin bis(2-ethylhexanoate), 1 drop of
Et3N, and 10 ml of anhydrous THF.
3-Butyn-1-yl N-(4-methoxyphenyl)carbamate
(Ib) was prepared similarly to compound Ia from
1.05 g (15 mmol) of 3-butyn-1-ol, 2.8 g (18.75mmol)
of 4-methoxyphenyl isocyanate, 75 mg of dibutyltin
bis(2-ethylhexanoate), 2 drops of Et3N, and 45 ml of
anhydrous THF.
7-Octyn-1-yl N-(4-dimethylaminophenyl)-
carbamate (Ii) was prepared in the same way as com-
pound Ig from 0.19 g (1.5 mmol) of 7-octyl-1-ol
dried with molecular sieves, 0.27 g (1.65 mmol) of
4-dimethylaminophenyl isocyanate, 8 mg of dibutyltin
bis(2-ethylhexanoate), 1 drop of Et3N, and 10 ml of
anhydrous THF.
3-Butyn-1-yl N-(4-nitrophenyl)carbamate (Ic)
was prepared similarly to compound Ia from 1.05 g
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002

SYNTHESIS OF NEW CONJUGATED DIYNES
785
8-Nonyn-1-yl N-phenylcarbamate (Ij) was pre-
pared in the same way as compound Ia from 0.42 g
(3 mmol) of 8-nonyl-1-ol, 0.445 g (3.75 mmol) of
phenyl isocyanate, 15 mg of dibutyltin bis(2-ethyl-
hexanoate), 1 drop of Et3N, and 10 ml of anhydrous
THF.
dried on MgSO4. UV spectrum (CH3CN), max, nm
(log ): 235 (4.79), 273 (3.28) fine structure.
3,5-Octadiyne-1,8-diyl bis-N-(4-methoxyphenyl)-
carbamate (IIb). In 1.5 ml of pyrrolidine was dis-
solved 0.22 g (1 mmol) of carbamate Ib and 19 mg
(0.1 mmol) of CuI. The reaction mixture was stirred
at room temperature for 15 min. Then the reaction
mixture was quenched with saturated aqueous NH4Cl
(5 ml), and extracted with THF (3 10 ml). After
THF was distilled off in a vacuum, the residue was
washed with 15% water solution of HCl and then
with water till neutral washings. UV spectrum
(CH3CN), max, nm (log ): 240 (4.51), 289 (3.49).
10-Undecyn-1-yl N-phenylcarbamate (Ik) was
prepared in the same way as compound Ia from
0.84 g (5mmol) of 10-undecyl-1-ol, 0.715 g (6mmol)
of phenyl isocyanate, 25 mg of dibutyltin bis(2-ethyl-
hexanoate), 2 drops of Et3N, and 15 ml of anhydrous
THF.
10-Undecyn-1-yl N-(4-methylphenyl)carbamate
(Il) was prepared in the same way as compound Ia
from 0.84 g (5 mmol) of 10-undecyl-1-ol, 0.76 g
(5 mmol) of tosyl isocyanate, 25 mg of dibutyltin
bis(2-ethylhexanoate), 2 drops of Et3N, and 5 ml of
3,5-Octadiyne-1,8-diyl
bis-N-(4-nitrophenyl)-
carbamate (IIc) was prepared analogously to com-
pound IIb from 0.235 g (1 mmol) of carbamate Ic,
19 mg (0.1 mmol) of CuI, and 1.5 ml of pyrrolidine.
UV spectrum (CH3CN), max, nm (log ): 218 (4.23),
318 (4.38).
anhydrous THF. Mass spectrum, m/z (Irel, %): 365
.
(0.5) [M]+ , 302 (1.3) [M SO2+1]+ ., 301 (5.8)
.
[M SO2]+ , 216 (7.8) [TsNHC(OH)2]+ , 210 (1.3)
4,6-Decadiyne-1,10-diyl bis-N-phenylcarbamate
(IId) was prepared analogously to compound IIb
from 0.406 g (2 mmol) of carbamate Id, 38 mg
(0.2 mmol) of CuI, and 2 ml of pyrrolidine. UV spec-
trum (CH3CN), max, nm (log ): 235 (4.54), 273
(3.15) fine structure.
[NHC(O)O(CH2)9C CH]+ , 199(0.4)[TsNHC=OH]+ ,
.
198 (1.3) [TsNHC=O]+ , 197 (3.8) [TsN=C=O]+ ,
+
+
156 (2.9) [p-CH3C6H4S(O)OH] , 155 (53) [Ts] , 152
+
.
+
(1.0)[CH3(CH2)8C CH] , 151(3.4) [(CH2)9C CH] ,
.
150 (6.6) [CH2=CH(CH2)7C CH]+ , 135 (4.2), 122
.
+
+
(0.8) [CH3(CH2)6C CH] ,
(7.0) [(CH2)7C CH] ,
120 (7.6) [CH2= CH(CH2)5C CH] , 110 (3.1)
4, 6-Decadiyne-1, 10-diyl bis-N-(4-methoxy-
phenyl)carbamate (IIe) was prepared analogously to
compound IIb from 0.23 g (1 mmol) of carbamate
Ie, 19 mg (0.1 mmol) of CuI, and 1.5 ml of pyrroli-
dine. UV spectrum (CH3CN), max, nm (log ): 241
(4.54), 289 (3.49).
121
.
+
.
+
+
[CH3(CH2)5C CH] , 109 (10) [(CH2)6C CH] , 108
.
+
(78)
[CH2= CH(CH2)4C CH] ,
107
(18)
+
+
[CH2= CHCH(CH2)3C CH] , 91 (100) [CH3C6H5] ,
.
82 (32) [CH3(CH2)3C CH]+ , 81 (14) [(CH2)4C
.
CH]+ , 80 (26) [CH2=CH(CH2)2C CH]+ , 69 (26)
4,6-Decadiyne-1,10-diyl bis-N-(4-nitrophenyl)-
carbamate (IIf) was prepared analogously to com-
pound IIb from 0.25 g (1 mmol) of carbamate Id,
19 mg (0.1 mmol) of CuI, and 1.5 ml of pyrrolidine.
+
.
+
[CH3(CH2)2C= CH2] , 68 (37) [CH3(CH2)2C CH] ,
67 (5) [(CH2)3C CH]+ , 66 (26) [CH2=CHCH2C
.
CH]+ , 55 (32) [CH3CH2C= CH2]+ , 54 (18)
.
[CH3CH2C CH]+ , 41 (55) [CH3C= CH2]+ , 39 (18)
UV spectrum (CH3CN),
(4.26), 320 (4.43).
max, nm (log ): 219
[CH2C CH]+ .
4, 6-Decadiyne-1, 10-diyl bis-N-(4-dimethyl-
aminophenyl)carbamate (IIg). In 1 ml of pyrroli-
dine was dissolved 0.07 g (0.28 mmol) of carbamate
Ig and 5 mg (0.028 mmol) of CuI. The reaction mix-
ture was stirred for 40 min at room temperature (TLC
monitoring). The reaction mixture was quenched with
saturated water solution of NH4Cl (2 ml), and the
product was extracted into THF (3 5 ml). THF was
partially removed in a vacuum, and the product was
precipitated by 10-fold amount of water (20 ml),
filtered off, and washed with water. UV spectrum
(CH3CN), max, nm (log ): 266 (4.57), 311 (3.63).
3,5-Octadiyne-1,8-diyl bis-N-phenylcarbamate
(IIa). In 3 ml of pyrrolidine was dissolved 0.45 g
(2.28 mmol) of carbamate Ia and 44 mg (0.23 mmol)
of CuI. The reaction mixture was stirred at room
temperature for 20 min. At this moment TLC test
showed no initial compound in the reaction mixture.
Then the reaction mixture was quenched with saturat-
ed aqueous NH4Cl (5 ml), and extracted with THF
(3 10 ml). THF was distilled off in a vacuum, the
reaction product was isolated by preparative TLC on
silica gel (eluent ether THF, 10: 1). The target
product was washed from silica gel with THF and
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002

786
VYAZMIN et al.
15 mg (0.078 mmol) of CuI, and 1.5 ml of pyrroli-
7, 9-Hexadecadiyne-1, 16-diyl bis-N-phenyl-
dine. UV spectrum (CH3CN), max, nm (log ): 235
(4.41), 273 (3.40) fine structure.
carbamate (IIh) was prepared analogously to com-
pound IIg from 0.245 g (1 mmol) of carbamate Ih,
19 mg (0.1 mmol) of CuI, and 1.5 ml of pyrrolidine.
UV spectrum (CH3CN), max, nm (log ): 235 (4.18),
273 (3.36) fine structure.
10, 12-Docosadiyne-1, 22-diyl bis-N-phenyl-
carbamate (IIk) was prepared analogously to com-
pound IIg from 0.287 g (1 mmol) of carbamate Ik,
19 mg (0.1 mmol) of CuI, and 1.5 ml of pyrrolidine.
UV spectrum (CH3CN), max, nm (log ): 235 (4.47),
273 (3.18) fine structure.
7,9-Hexadecadiyne-1,16-diyl bis-N-(4-dimethyl-
aminophenyl)carbamate (IIi) was prepared ana-
logously to compound IIg from 0.288 g (1 mmol) of
carbamate Ii, 19 mg (0.1 mmol) of CuI, and 1.5 ml
of pyrrolidine. UV spectrum (CH3CN), max, nm
(log ): 266 (4.52), 312 (3.45).
2-Butyne-1,4-diyl bis[N,N -di(4-methylphenyl-
sulfonyl)]carbamate (III) was prepared in the same
way as compound Il from 172 mg (2 mmol) of 2-
butyne-1,4-diole, 0.556 ml (4 mmol) of tosyl iso-
cyanate, 10 mg of dibutyltin bis(2-ethylhexanoate),
2 drops of Et3N, and 5 ml of anhydrous THF. Yield
130 mg (23%), mp 166 168 C (with decomposition).
8, 10-Octadecadiyne-1,18-diyl bis-N-phenyl-
carbamate (IIj) was prepared analogously to com-
pound IIg from 0.2 g (0.77 mmol) of carbamate Ij,
1H NMR spectrum (CD3COCD3), , ppm: 2.43 s
(6H, CH3), 4.71 s (4H, CH2O), 7.42 d (4H, m-H
arom), 7.89 d (4H, o-H arom). 13C NMR spectrum
(CD3COCD3), , ppm: 21. 03 (CH3), 53. 62
(CH2O) 81.16 (C C), 128.47 (m-C arom), 129.96
(o-C arom), 136.92 (p-C arom), 145.24 (i-C arom),
150.64 (C=O). Found, %: C 49.96; H 4.36; N 5.76.
C20H20N2O8S2. Calculated, %: C 49.99; H 4.20; N
5.83.
without a Pyrex glass filter. Under the latter condi-
tions was performed only polymerization of com-
pounds IIb f, k.
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