Reaction of arylpropargyl aldehydes with 2,3-bis-hydroxylamino-2,3-dimethylbutane: Synthesis of 2-(1-hydroxy-4,4,5,5-tetramethylimidazolidin-2-ylidene)-1-arylethanones

Article abstract of DOI:10.1016/S0040-4020(00)00978-9

Reaction of arylpropargyl aldehydes with 2,3-dihydroxylamino-2,3-dimethylbutane results in the formation of 2-(1-hydroxy-4,4,5,5-tetramethylimidazolidin-2-ylidene)-1-arylethanones in high yields (70-80%). Allowing availability of propargyl aldehydes, this method gives new possibilities for the preparation of 2-(1-hydroxy-4,4,5,5-tetramethylimidazolidin-2-ylidene)-1-arylethanones. (C) 2000 Elsevier Science Ltd.

Full text of DOI:10.1016/S0040-4020(00)00978-9

TETRAHEDRON
Pergamon
Tetrahedron 56 (2000) 10075±10080
Reaction of Arylpropargyl Aldehydes with
2,3-Bis-hydroxylamino-2,3-dimethylbutane: Synthesis of
2-(1-Hydroxy-4,4,5,5-tetramethylimidazolidin-2-ylidene)-1-
arylethanones
Eugene V. Tretyakov,a Alexey V. Tkachev,b,² Tatyana V. Rybalova,b Yurii V. Gatilov,b
David W. Knightc,³ and Sergey F. Vasilevskya,
*
aInstitute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, 630090, Novosibirsk, Russia
bN. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090,
Novosibirsk, Russia
cDepartment of Chemistry, Cardiff University, P.O. Box 912, Cardiff CF10 3TB, UK
Received 20 July 2000; revised 27 September 2000; accepted 12 October 2000
AbstractÐReaction of arylpropargyl aldehydes with 2,3-dihydroxylamino-2,3-dimethylbutane results in the formation of 2-(1-hydroxy-
4,4,5,5-tetramethylimidazolidin-2-ylidene)-1-arylethanones in high yields (70±80%). Allowing availability of propargyl aldehydes, this
method gives new possibilities for the preparation of 2-(1-hydroxy-4,4,5,5-tetramethylimidazolidin-2-ylidene)-1-arylethanones. q 2000
Elsevier Science Ltd. All rights reserved.
Introduction
products of the reaction with arylpropargyl aldehydes1
were 2-(1-hydroxy-4,4,5,5-tetramethylimidazolidin-2-yli-
dene)-1-arylethanones.2
In continuation of our study on possible ways of synthesis
and of the properties of new Ullman's radicals,1 we required
alkynyl derivatives of nitronyl- and iminonitroxides.2 One
of the key steps in the synthesis of spin-labelled 2-imidazo-
line derivatives is the condensation of aldehydes (or their
synthetic equivalents) with 2,3-dihydroxylamino-2,3-di-
methylbutane (introduced as a free base or its acid salt),
leading to formation of the corresponding 1,3-dihydroxy-
4,4,5,5-tetramethylimidazolidines. Ullman reported that
condensation of bis-hydroxylamine with phenylpropargyl
aldehyde yielded the corresponding imidazolidine which
gave the corresponding nitronylnitroxide in an overall
yield of 11% upon treating with an oxidizing agent.2 In
our hands, this procedure led to negative results, necessitat-
ing an extended study of the reaction of propargyl aldehydes
with 2,3-bis-hydroxylamino-2,3-dimethylbutane. We have
found that 1,3-dihydroxy-4,4,5,5-tetramethylimidazolidines
are not formed in the reaction of arylpropargyl aldehydes
with 2,3-dihydroxylamino-2,3-dimethylbutane under the
conditions of the Ullman's synthesis. In fact, the major
Careful review of the literature revealed that the ®rst synthe-
sis of 2-(1-hydroxyimidazolidin-2-ylidene)ethanones was
claimed only very recently in connection with new ideas,
arising in the ®eld of the design of magnetically active
systems on the basis of transition metal complexes with
stable nitroxyls.3 The synthetic scheme includes condensa-
tions of a substituted bis-hydroxylamine with a keto-
aldehyde and provides certain simple compounds,
although the authors state that their synthesis is unaccept-
able for the preparation of complex derivatives due to some
speci®c problems associated with the ketoaldehyde compo-
nent. An alternative way of synthesising such compounds is
by the interaction of the dilithium derivative of 1-hydroxy-
2,4,4,5,5-pentamethylimidazoline with esters of carboxylic
acids.4 Hence, the present formation of 2-(1-hydroxy-
4,4,5,5-tetramethylimidazolidin-2-ylidene)-1-arylethanones
2 by the reaction of propargyl aldehydes with 2,3-
dihydroxylamino-2,3-dimethylbutane seems to be a viable
alternative to the known synthetic methods for the prepara-
tion of these compounds, which are of interest both as a
potential precursor for magneto-active systems as well as
biologically active compounds.
Keywords: hydroxylamine derivatives; propargyl aldehydes; 1-hydroxyimi-
dazolidin-2-ylidenes.
* Corresponding author. Fax: 73832/342350;
e-mail: vasilev@ns.kinetics.nsc.ru
Fax: 173832/344752; e-mail: atkachev@nioch.nsc.ru
²
In this paper, we wish to report the results of our study of
the behaviour of a variety of propargyl aldehydes in such
³
Fax: 101222/874210; e-mail: knightdw@cf.ac.uk
0040±4020/00/$ - see front matter q 2000 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020(00)00978-9

10076
E. V. Tretyakov et al. / Tetrahedron 56 (2000) 10075±10080
Scheme 1.
chemistry and include some discussion of the peculiar
features and possible mechanism of the reaction.
solution was stirred at the temperature mentioned until
disappearance of the starting material (TLC). The total
yields of the reaction products were between 71 and 81%.
We have tested different p-substituted benzene derivatives
1a±e (Scheme 1) and have found that a decrease of the
temperature of the reaction mixture usually results in better
yields and increased purity of the products.
Results and Discussion
Unfortunately, in the original Ullman paper,2 there were
no details of the condensation reaction between phenyl-
propargyl aldehyde and 2,3-dihydroxylamino-2,3-dimethyl-
butane, except for the temperature range (0±808C) and the
solvents used (methanol or benzene). We followed these
conditions but obtained another product. The reactions of
propargyl aldehydes having aromatic substituents with 2,3-
dihydroxylamino-2,3-dimethylbutane were carried out as
follows: 2,3-bis-hydroxylamino-2,3-dimethylbutane was
added to a solution of the propargyl aldehyde 1a±e in
benzene at 58C or in methanol at 2308C and the resulting
The data from combustion analysis and mass spectra of the
reaction products 2a±e formally correspond to the products
of condensation of the propargyl aldehydes with the bis-
hydroxylamine and loss of a molecule of water. However,
1H NMR and 13C NMR spectra, as well as IR data, were not
consistent with the structure of the `Ullman' alkyne deriva-
tives. NMR and IR data of the reaction products showed
that these all belonged to one and the same structural
type, so we performed an X-ray single crystal analysis on
Ê
Figure 1. Molecular structure of compound 2b according to single crystal X-ray analysis. Selected bond lengths (A) and torsional angles (8) are as follows:
C(2)vC(6) 1.409(5), C(6)±C(7) 1.370(5), C(7)vO(7) 1.278(4), C(13)±C(8)±C(7)±C(6) ±6.7(6), C(7)±C(6)±C(2)±N(3) 1.0(6), C(2A)vC(6A) 1.390(5),
C(6A)±C(7A) 1.385(5), C(7A)vO(7A) 1.268(4), C(13A)±C(8A)±C(7A)±C(6A) ±19.2(6), C(7A)±C(6A)±C(2A)±N(3A) 2.0(7).

E. V. Tretyakov et al. / Tetrahedron 56 (2000) 10075±10080
10077
Figure 2. Packing scheme of the molecules 2b and the solvent molecules (ethyl acetate) in the crystalline state according to X-ray crystallography. The ethyl
acetate solvate molecules are in high disorder. The solvate molecules are in high disorder and occupy special positions in throughout cavities.
the simplest phenyl derivative 2b and proved it to belong to
a series of 2-(1-hydroxy-4,4,5,5-tetramethylimidazolidin-2-
ylidene)-1-arylethanones (Fig. 1).
formed in the crystal by the H-bonds O(1)±H¼O(7) (x21,
Ê
y, z) (H¼O(7) 1.64(6) A, O(1)±H¼O(7) 148(5)8) and
Ê
O(1A)±H¼O(7A) (x11, y, z) (H¼O(7A) 1.70(4) A,
O(1A)±H¼O(7A) 176(4)8). Solvent molecules (ethyl
acetate) occupy special positions (0, 0, 0.5) throughout the
cavities (Fig. 2). Parameters of the intramolecular H-bonds
N±H¼O are as follows: N(3)±H¼O(7) (H¼O(7)
2.08(4) A, N(3)±H¼O(7) 126(3)8), N(3A)±H¼O(7A)
Ê
(H¼O(7A) 2.08(4) A, N(3A)±H¼O(7A) 121(3)8).
The crystal structure of the ®rst molecule from the two
crystallographically independent ones is shown in Fig. 1.
The (N)2CvC±C(vO)±Ph fragment is planar within
Ê
Ê
^0.092(3) and ^0.225(3) A, correspondingly, for both
molecules. The envelope-like conformation of the imidazo-
lidine rings can be characterised with C(5) and C(5A) atom
deviations from the plane of the rest of the four atoms by
The 1-hydroxyimidazolidin-2-ylidenel-1-aryl ethanones
2a±e are coloured solids with different tints of yellow,
which are quite stable in the crystalline state but are unstable
in solution, especially in the open air. NMR spectra of all the
compounds 2a±e have more or less broad lines (methyls,
NH, NOH, OvC±CHvN) due to an exchange process. The
lines become narrower upon heating and come to the origi-
nal width on cooling. The exchange might be due to proton
transfer processes and cis-trans-isomerisation, as shown in
Scheme 2.
Ê
0.563(6) and 0.587(7) A. It is worth noting the bond length
equalizing of the CvC±CvO fragment (1.399, 1.378,
Ê
1.273 A, averaged for two molecules, as compared to the
expected mean values5 1.340(13), 1.464(18) and
Ê
1.222(10) A). A search for the fragment (N)2CvC±
C(vO)±C in the Cambridge structural database6 revealed
®ve derivatives of 3-aryl-2-(2-oxoarylethyl)-3H-quinazolin-
4-one having anticonvulsant activity as well as in
2-(benzoylmethylene)-hexahydropyrimidine7
and
2-
(benzoylmethylene)-imidazolidine.8 For all these mole-
cules, the equalising of the bond lengths is also typical,
although in the two later compounds, the formally single
bonds were even shorter than formally double bonds (1.432,
The mechanism of the formation of the condensation
products 2a±e is not clear yet, although the hypothetical
scheme could be described as a two step process (Scheme
1): (1) condensation of the bis-hydroxylamine with the
propargyl aldehydes followed by (2) intramolecular transfer
of the hydroxyl group to the b-carbon of the triple bond.
Ê
1.382, 1.287 and 1.403, 1.384, 1.241 A for the string CvC±
CvO). The pyramidal structure of the N(1) and N(1A)
Ê
atoms (heights of pyramids 0.358(4) and 0.357(4) A) and
the more planar structure of the N(3) and N(3A) atoms
Ê
(heights 0.08(2) and 0.20(2) A) were also features of the
structure. In®nite chains of molecules along the a axis are
As can be seen from the procedure and the yields, the reac-
tion is a very simple route to functionalized 1-hydroxy-2-

10078
E. V. Tretyakov et al. / Tetrahedron 56 (2000) 10075±10080
Scheme 2.
Scheme 3.
imidazolines 2, provided that the corresponding aryl-
propargyl aldehydes are available. There are a number of
methods for the preparation of arylpropargyl aldehydes. In
our hands, the most convenient method is oxidation of the
corresponding arylpropargyl alcohols (prepared from
terminal alkynes or by the method we used) or hydrolysis
of arylpropargyl aldehyde diethyl acetal (precursorsÐ
terminal alkynes). The terminal acetylenes can be easily
synthesised by cross-coupling of organic halides with
trimethylsilylacetylene or 2-methylbut-3-yn-2-ol, followed
by removal of the protecting groups.9
tion. Analytical TLC plates were Silufolw UV-254 (Silpearl
on aluminum foil, Czecho-Slovakia). Silica gel `KSK'
(Russia, 100±200 mech., air dried and activated at 1308C
for 5 h) was used for ®ltration. IR spectra were obtained for
KBr pellets using a Bruker IFS 66 infrared spectrometer.
Melting points were obtained using a Ko¯er melting point
apparatus. Microanalyses were obtained using a Hewlett
Packard 185 analyser and a Carlo Erba 1106 analyser.
Mass spectra were recorded on a Finnigan MAT-8200
instrument using Electron Impact Ionisation technique
(70 eV). For imidazilidines 2a±e, 1H and 13C NMR spectra
were recorded at 1278C using a Bruker DRX-500 spectro-
meter locked to the deuterium resonance of the solvent.
Chemical shifts were calculated relative to solvent signals
used as the internal standards: dH 7.240 ppm and dC
76.900 ppm for CDCl3, dH 7.190 ppm and dC
We prepared arylpropargyl alcohols 3a±e by palladium-
catalysed cross-coupling of aryl iodides with propargyl
alcohol (Scheme 3).10 We have improved the cited method
by using organic solvents in the presence of two equivalents
of piperidine instead of in neat diethylamine. Under these
conditions, aryl iodides react with propargyl alcohol at
30±358C to give arylpropargyl alcohols 3 in high yields
(71±92%). Arylpropargyl aldehydes 1 were then prepared
by oxidation of the corresponding alcohols with pyridinium
chlorochromate similar to the procedure described in ref.11
1
123.500 ppm for Py-d5. The other H NMR spectra were
recorded on a Bruker Avance 300 spectrometer.
(4-Methoxyphenyl)propynal (1a). The compound was
prepared by oxidation of 3a according to Ref. 11
Biphenyl-4-ylpropynal (1c). The compound was
synthesised by the procedure similar to that described in
Ref. 11 Pyridinium chlorochromate (1.20 g, 5.57 mmol)
was added to a stirred solution of 3c (1.05 g, 5.05 mmol)
in dichloromethane (20 ml) at room temperature. The
resulting mixture was stirred for 1.5 h (disappearance of
the starting propargyl alcohol, TLC), then ®ltered
through silica gel. The ®ltrate was concentrated in vacuum
to give compound 1c (0.86 g, 83%) as a yellow solid: mp
78±798C (benzene±hexane 5:1, v/v); IR, nmaxˆ3080,
2179, 1648, 1599, 1480, 1445, 1389, 1263, 1108, 1070,
Thus, the reaction of substituted propargyl aldehydes
with 2,3-dihydroxylamino-2,3-dimethylbutane seems to
be a general synthetic method for the preparation of 2-(1-
hydroxy-4,4,5,5-tetramethylimidazolidin-2-ylidene)-1-aryl-
ethanones 2 and can be used as the ®nal step in the reaction
sequence leading from organic halides via substituted
propargyl aldehydes 1.
Experimental
1
1038, 1019, 1000, 973, 844 cm21; H NMR (CDCl3) d
7.35±7.85 (m, 9H, aromatic H), 9.49 (s, 1H, CHO). Anal.
Calcd for C15H10O: C, 87.36; H, 4.89. Found: C, 87.2; H,
5.0.
All the solvents used were reagent quality. Removal of all
solvents was carried out under reduced pressure and all
commercial reagents were used without additional puri®ca-

E. V. Tretyakov et al. / Tetrahedron 56 (2000) 10075±10080
10079
(4-Bromophenyl)propynal (1d). The compound was
prepared from compound 3d (1.05 g, 4.98 mmol) to give a
yellow viscous oil which was treated with hexane to afford a
solid which was then puri®ed by crystallisation from a
mixture of benzene and hexane to yield the title compound
(0.50 g, 48%) as yellowish crystals with mp 54±558C; lit.:
crude oil;12 IR: nmaxˆ3087, 2199, 1651, 1581, 1474, 1385,
1-Biphenyl-4-yl-2-(1-hydroxy-4,4,5,5-tetramethylimida-
zolidin-2-ylidene)ethanone (2c). Yield 81%. Yellowish
powder with mp 127±1288C (benzene±hexane 5:1, v/v);
IR: nmaxˆ3350, 3090, 2979, 2929, 1597, 1562, 1524,
1484, 1443, 1393, 1295, 1264, 1218, 1168, 1149, 1123,
1
1001, 894, 854; H NMR (CDCl3) d 1.13 (s, 6H, 2 CH3),
1.14 (s, 6H, 2 CH3), 5.60 (s, 1H, CHv), 7.30±7.90 (m, 9H,
aromatic H), 8.9 (br. s, 1H, N±OH); 13C NMR (CDCl3) d
18.01 (imidazolidine-4-C(CH3)2), 23.33 (imidazolidine-5-
C(CH3)2), 60.91 (imidazolidine-C4), 69.25 (imidazolidine-
C5), 78.30 (CHv), 126.57 (aromatic C), 126.93 (aromatic
C), 127.44 (aromatic C),00 128.20 (aromatic C), 128.65
1
1263, 1062, 1009, 980, 821; H NMR (CDCl3) d 7.51 (d,
2H, Jˆ10 Hz, H2 and H6), 7.60 (d, 2H, Jˆ10 Hz, H3 and
H5), 9.56 (s, 1H, CHO).
(4-Nitrophenyl)propynal (1e). The compound was
prepared from compound 3e in 55% yield. Yellow crystals
with mp 122±1238C; {lit.13: mp 123±123.58C}.
0
0
(aromatic C), 137.72 (C1 ), 139.71 (C4 ), 140.22 (C1 ),
164.50 (imidazolidine-C2), 186.00 (CO). Anal. calcd for
C21H24N2O2: C, 74.97; H, 7.19; N, 8.33. Found: C, 74.7;
H, 7.3; N, 8.4. MS, m/z (%): 336.18350 (M1, 75, calcd for
C21H24N2O2 336.18377), 84 (26), 98 (52), 100 (23), 152
(32), 153 (22), 181 (100), 182 (15), 207 (13), 222 (15),
262 (15), 263 (11), 320 (9), 336 (75), 337 (17), 338 (3).
Reaction of propargyl aldehydes with 2,3-bishydroxyl-
amino-2,3-dimethylbutane. General procedure
2,3-Bishydroxylamino-2,3-dimethylbutane14 (0.30 g, 2.03
mmol) was added to a stirred solution of the propargyl alde-
hyde 1a±e (2.03 mmol) in benzene (20 ml) at 58C or in
methanol (20 ml) at 2308C for 10 min. The reaction
mixture was kept at the same temperature for 1±3 h (dis-
appearance of the starting propargyl aldehyde, TLC).
Evaporation of the solvent gave the crude product, which
was puri®ed by ®ltration through silica gel followed by
crystallisation.
1-(4-Bromophenyl)-2-(1-hydroxy-4,4,5,5-tetramethyl-
imidazolidin-2-ylidene)ethanone (2d). Yield 71%.
Yellowish powder with mp 189±1908C (benzene±chloro-
form 10:1, v/v); IR: nmaxˆ3306, 3102, 2972, 2836, 1589,
1567, 1516, 1480, 1451, 1380, 1298, 1266, 1212, 1173,
1149, 1106, 1088, 1068, 1023, 1008, 957, 894, 874, 837;
1H NMR (CDCl3:Py-d5ˆ4:1) d 0.92 (s, 6H, 2 CH3), 0.95 (s,
6H, 2 CH3), 5.51 (s, 1H, CHv), 7.20 (d, 2H, Jˆ9 Hz, H2
and H6), 7.54 (d, 2H, Jˆ9 Hz, H3 and H5), 8.8 (br. s, 1H, N±
OH), 11.1 (br. s, 1H, NH); 13C NMR (CDCl3:Py-d5ˆ4:1) d
17.41 (imidazolidine-4-C(CH3)2), 22.83 (imidazolidine-5-
C(CH3)2), 59.83 (imidazolidine-C4), 68.30 (imidazolidine-
C5), 74.11 (CHv), 123.52 (phenyl-C4), 127.90 (aromatic
C), 130.36 (aromatic C), 139.51 (phenyl-C1), 163.99 (imida-
zolidine-C2), 183.80 (CO). Anal. Calcd for C15H19BrN2O2:
C, 53.11; H, 5.65; Br, 23.55. Found: C, 53.3; H, 5.7; Br,
23.7.
2-(1-Hydroxy-4,4,5,5-tetramethylimidazolidin-2-ylidene)-
1-(4-methoxyphenyl)ethanone (2a). Yield 71%. Yellowish
powder with mp 194±1958C (benzene±chloroform 10:1,
v/v); IR: nmaxˆ3350, 3140, 2985, 2839, 1596, 1573, 1499,
1460, 1391, 1298, 1252, 1218, 1176, 1143, 1112, 1020, 940,
894, 874, 844; 1H NMR (CDCl3:Py-d5ˆ5:2) d 0.83 (s, 6H, 2
CH3), 0.85 (s, 6H, 2 CH3), 3.38 (s, 3H, OCH3), 5.49 (s, 1H,
CHv), 6.52 (d, 2H, Jˆ9 Hz, H2 and H6), 7.60 (d, 2H,
Jˆ9 Hz, H3 and H5), 8.8 (br. s, 1H, N±OH), 10.9 (br. s,
1H, NH); 13C NMR (CDCl3:Py-d5ˆ5:2) d 17.20 (imidazo-
lidine-4-C(CH3)2), 22.68 (imidazolidine-5-C(CH3)2), 54.22
(OCH3), 59.43 (imidazolidine-C4), 67.87 (imidazolidine-
C5), 73.60 (CHv), 112.31 (phenyl-C3 and C5), 127.72
(phenyl-C2 and C6), 133.08 (phenyl-C1), 160.33 (phenyl-
C4), 163.55 (imidazolidine-C2), 184.56 (CO). Anal. Calcd
for C16H22N2O3: C, 66.18; H, 7.64; N, 9.65. Found: C, 66.4;
H, 7.7; N, 9.4.
2-(1-Hydroxy-4,4,5,5-tetramethylimidazolidin-2-ylidene)-
1-(4-nitrophenyl)ethanone (2e). Yield 76%. Yellow
powder with mp 214±214.58C (benzene±chloroform 5:1,
v/v); IR: nmaxˆ3450, 3380, 3108, 2966, 2847, 1589, 1525,
1486, 1463, 1392, 1368, 1344, 1318, 1295, 1265, 1228,
1
1209, 1166, 1146, 1114, 1086, 1024, 897, 853; H NMR
(CDCl3:Py-d5ˆ4:1) d 0.95 (s, 6H, 2 CH3), 0.99 (s, 6H, 2
CH3), 5.56 (s, 1H, CHv), 7.78 (d, 2H, Jˆ10 Hz, H2 and
H6), 7.92 (d, 2H, Jˆ10 Hz, H3 and H5), 8.9 (br. s, 1H, N±
OH), 11.3 (br. s, 1H, NH); 13C NMR (CDCl3:Py-d5ˆ5:2) d
17.46 (imidazolidine-4-C(CH3)2), 22.81 (imidazolidine-5-
C(CH3)2), 60.13 (imidazolidine-C4), 68.61 (imidazolidine-
C5), 75.19 (CHv), 122.57 (phenyl-C3 and C5), 127.04
(phenyl-C2 and C6), 146.42 (phenyl-C1), 147.86 (phenyl-
C4), 164.20 (imidazolidine-C2), 182.14 (CO). Anal. Calcd
for C15H19N3O4: C, 59.01; H, 6.27; N, 13.76. Found: C,
59.2; H, 6.0; N, 13.8. MS, m/z (%): 305.13749 (M1, 100,
calcd for C15H19N3O4 305.13756), 84 (68), 98 (100), 100
(52), 150 (32), 191 (27), 215 (12), 231 (23), 232 (13), 288
(21), 289 (24), 290 (16), 305 (100), 306 (19), 307 (3).
2-(1-Hydroxy-4,4,5,5-tetramethylimidazolidin-2-ylidene)-
1-phenylethanone (2b). Yield 76%. Yellowish powder
with mp 177±1788C (ethyl acetate±hexane 5:1, v/v); IR:
nmaxˆ3360, 3089, 2982, 2811, 1599, 1578, 1522, 1487,
1460, 1394, 1295, 1263, 1217, 1164, 1146, 1121, 1095,
1
1046, 1018, 951, 893, 871; H NMR (CDCl3) d 1.07 (s,
6H, 2 CH3), 1.10 (s, 6H, 2 CH3), 5.58 (s, 1H, CHv),
7.25±7.35 (m, 3H, H2, H4 and H6), 7.70±7.80 (m, 2H, H3
and H5), 8.9 (br. s, 1H, N±OH); 13C NMR (CDCl3) d 17.92
(imidazolidine-4-C(CH3)2),
23.25
(imidazolidine-5-
C(CH3)2), 60.31 (imidazolidine-C4), 69.18 (imidazolidine-
C5), 78.30 (CHv), 126.88 (phenyl-C3 and C5), 127.90
(phenyl-C2 and C6), 129.72 (phenyl-C4), 130.11 (phenyl-
C1), 164.00 (imidazolidine-C2), 187.00 (CO). Anal. Calcd
for C15H20N2O2: C, 69.20; H, 7.74; N, 10.76. Found: C,
69.3; H, 7.9; N, 10.5.
3-(4-Methoxyphenyl)prop-2-yn-1-ol (3a). The compound
was prepared according to the procedure described in
Ref. 10 with some modi®cation. Bis(triphenylphosphine)-
palladium(II) chloride (120 mg, 0.171 mmol) was added to

10080
E. V. Tretyakov et al. / Tetrahedron 56 (2000) 10075±10080
a stirred solution of propargyl alcohol (5.60 g, 0.10 mole),
1-iodo-4-methoxybenzene (23.00 g, 0.0983 mole), piper-
idine (17.0 g, 0.2 mole), and copper iodide (60 mg,
0.32 mmol) in benzene (30 ml) under an argon atmosphere.
The mixture was stirred at 30±358C for 2 h and then ®ltered
through silica gel. The solvent was distilled off and the
residue was chromatographed on a silica gel column
(CHCl3) followed by crystallisation from benzene/hexane
to afford compound 3a (11.78 g, 74%). White powder, mp
61±638C; {lit.11: mp 62.5±64.58C}.
The crystal structure data has been deposited at the
Cambridge Crystallographic Data Centre and allocated the
deposition number CCDC 149659.
Acknowledgements
This work was supported by the Russian Foundation for
Basic Research (grants 98-03-32908a), INTAS (grant #
97-0217), the grant of the Ministry of Education of RF in
the area of fundamental natural sciences (1998±2000), the
Siberian Branch of RAS (grant 2000±12) which are highly
acknowledged by the authors.
3-Biphenyl-4-ylprop-2-yn-1-ol (3b). Yield 88%. Yellow-
ish crystals with mp 88±898C (benzene±hexane 5:1, v/v);
IR: nmaxˆ3287, 2921, 2860, 2225, 1483, 1447, 1404, 1041,
1
1015, 953, 841; H NMR (CDCl3) d 1.71 (br. s, 1H, OH),
4.57 (s, 2H, CH2), 7.32±7.63 (m, 9H, aromatic H). Anal.
Calcd for C15H12O: C, 86.51; H, 5.81. Found: C, 86.4; H,
6.0.
References
3-(4-Bromophenyl)prop-2-yn-1-ol (3d). Yield 92%.
Yellowish crystals with mp 68±698C (benzene±hexane
5:1, v/v); IR: nmaxˆ3276, 2918, 2860, 2237, 1483, 1393,
1. Tretyakov, E. V.; Samoilova, R. I.; Ivanov, Y. V.; Plyusnin, V.
F.; Pashchenko, S. V.; Vasilevsky, S. F. Mendeleev Commun.
1999, 92.
1
1348, 1259, 1238, 1097, 1072, 1027, 951, 823; H NMR
2. Ullman, E. F.; Osiecki, J. H.; Boocock, D. G. B.; Darcy, R.
J. Am. Chem. Soc. 1972, 94, 7049.
(CDCl3) d 1.72 (br. s, 1H, OH), 4.53 (s, 2H, CH2), 7.32
(d, 2H, Jˆ10 Hz, H2 and H6), 7.50 (d, 2H, Jˆ10 Hz, H3
and H5). Anal. Calcd for C9H7BrO: C, 51.22; H, 3.34; Br,
37.86. Found: C, 51.2; H, 3.3; Br, 37.9.
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1699.
3-(4-Nitrophenyl)prop-2-yn-1-ol (3e). Yield 71%. Yellow
crystals with mp 95±968C (benzene); {lit.15: mp 97±988C}.
5. Allen, F. A.; Kennard, O.; Watson, D. G.; Brammer, L.; Orpen,
A. G.; Taylor, R. J. Chem. Soc., Perkin Trans. 2 1987, 12, 1.
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X-Ray crystallographic study of compound 2b
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Using a Bruker P4 diffractometer with graphite mono-
chromated Mo Ka radiation, 5458 independent re¯ections
were measured (u/2u scans with u,258). The crystal
Å
system of compound 2b is triclinic, space group P 1,
Ê
aˆ6.953(2), bˆ15.681(4), cˆ16.542(4) A, aˆ113.40(2),
Ê 3
bˆ95.69(1), gˆ95.07(2)8, Vˆ1630.9(7) A , ?15H20N2O21
1/4(C4H8O2), Mˆ282.36, Zˆ4, Dcˆ1.150 g/cm3, mˆ
0.078 mm21
0.96 mm.
,
F(000)ˆ608, crystal size 0.04£0.17£
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1987, 52, 3662.
The structure was solved by direct methods (shelxs-97) and
re®ned in the anisotropic-isotropic (for atoms H) approxi-
mation using shelxs-97 to wR2ˆ0.2169, Sˆ1.011 for all
re¯ections (Rˆ0.0672 for 2749 F.4s). The hydrogen
atoms were positioned geometrically. Due to high disorder
of the ethyl acetates, solvate molecule we were unable to
interpret the peaks of solvate obtained by differential
synthesis.
12. Heindel, N. D.; Reid, J. R. J. Heterocycl. Chem. 1980, 17,
1087.
13. Manecke, G.; Schenck, H. U. Chem. Ber. 1971, 104, 3395.
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Synthesis 1984, 728.