Synthesis and properties of N-[2,2-bis(2,4-dihydroxyaryl)ethyl]-N- methylamines and their hydrohalides

Article abstract of DOI:10.1007/s11172-007-0054-8

Condensation of one molecule of α-methylaminoacetaldehyde dimethyl acetal with two molecules of resorcinol or methylresorcinol in hydrohalogen acid solutions led to substituted N-(2,2-diarylethyl)-N-methylamine hydrohalides. Reactions of the corresponding

Full text of DOI:10.1007/s11172-007-0054-8

Russian Chemical Bulletin, International Edition, Vol. 56, No. 2, pp. 330—335, February, 2007
330
Synthesis and properties of Nꢀ[2,2ꢀbis(2,4ꢀdihydroxyaryl)ethyl]ꢀ
Nꢀmethylamines and their hydrohalides
A. R. Burilov,а A. S. Gazizov,a N. I. Kharitonova,a M. A. Pudovik,а
ꢀ
W. D. Habicher,b I. Baier,b and A. I. Konovalova
аA. E. Arbuzov Institute of Organic and Physical Chemistry,
Kazan Research Center, Russian Academy of Sciences,
8 ul. Akad. Arbuzova, 420088 Kazan, Russian Federation.
Fax: +7 (843 2) 75 2253. Eꢀmail: pudovik@iopc.knc.ru
bInstitute of Organic Chemistry, Dresden Technical University,
13 Mommsenstrasse, Dꢀ01062 Dresden, Germany.
Fax: +49 (351) 463 4093
Condensation of one molecule of αꢀmethylaminoacetaldehyde dimethyl acetal with two
molecules of resorcinol or methylresorcinol in hydrohalogen acid solutions led to substituted
Nꢀ(2,2ꢀdiarylethyl)ꢀNꢀmethylamine hydrohalides. Reactions of the corresponding amines with
acetic anhydride, monoꢀ and diisocyanates, and formaldehyde were studied. Conditions for
formation of calixarene from resorcinol and αꢀmethylaminoacetaldehyde dimethyl acetal were
invented.
Key words: resorcinols, acetals, αꢀmethylaminoacetaldehyde, amino phenols, amines,
calix[4]resorcinarene.
Scheme 1
Condensation of resorcinol and its derivatives with
aliphatic and aromatic aldehydes is a principal method
for the synthesis of calix[4]resorcinarenes.1—3 Recently,
we extended the synthetic potentialities of this method by
the use of phosphorylated acetals to obtain calix[4]reꢀ
sorcinarenes bearing phosphorylalkyl substituents at the
lower rim of the molecule.4 Their aminoalkyl analogs are
of particular interest, since the presence of amino groups
can make them serve as key compounds in the synthesis
of new cavitands, carcerands, or nanotubes.
To obtain such structures, we carried out a condensaꢀ
tion of resorcinol (1a) and 2ꢀmethylresorcinol (1b) with
αꢀmethylaminoacetaldehyde dimethyl acetal (2) in hydroꢀ
halogen acid solutions (Scheme 1). Unexpectedly, the
substituted Nꢀ(2,2ꢀdiarylethyl)ꢀNꢀmethylamine hydroꢀ
halides 3a—c, products of the reaction of two molecules
of resorcinol with one molecule of αꢀaminoacetal, were
obtained instead of calixarenes. In order to study the inꢀ
fluence of the conditions on the outcome of the reaction,
we varied the temperature (from 25 to 80 °С) and
the duration of the process (from 4 h to 7 days). Howꢀ
ever, bisꢀresorcinols 3a—c were the only products in all
the cases. Their structures were confirmed by 1H and
13C NMR spectra, and their molecular weights were deꢀ
termined by MALDIꢀTOF massꢀspectrometry.
1: R = H (a), Me (b)
3: R = H, Hal = Cl (a); R = Me, Hal = Cl (b), Br (c)
acetaldehyde or 4ꢀmethoxybenzaldehyde leading to the
compounds of this type, though, the detailed analysis of
the product composition has not been done. In all the
other known cases, reaction of resorcinol with aldehydes
leads to calixarenes. Obviously, the abnormal course of
It should be noted that there is the only documented5
example of the condensation of 2ꢀnitroresorcinol with
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 319—324, February, 2007.
1066ꢀ5285/07/5602ꢀ0330 © 2007 Springer Science+Business Media, Inc.

Nꢀ[2,2ꢀBis(2,4ꢀdihydroxyaryl)ethyl]amines
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 2, February, 2007
331
the reaction (see Ref. 5) can be explained by the effect of
a strong electronꢀwithdrawing nitro group in position 2 of
resorcinol. Thus, the discovered by us aromatic electroꢀ
philic substitution with acetal 2 is a unique one. Resulted
amines of the type 3 can be considered as promising
key intermediates in the synthesis of various organic
and organoelement structures, including spatially orgaꢀ
nized ones.
We also studied the effect of the solvent and acid
nature on the synthetic outcome of the reaction and inꢀ
vestigated some properties of the products obtained. Reꢀ
action of 2ꢀmethylresorcinol (1b) with acetal 2 was carꢀ
ried out in ethanol, water, and in a mixture of ethanol
with water (1 : 1) in the presence of hydrochloric, hydroꢀ
bromic, sulfuric, and trifluoromethanesulfonic acids. It
was shown that the main products of these reactions are
polyphenols of the type 3. The use of the concentrated
hydrohalogen acids gives the highest yields of the target
amines. The yields of these products are much lower, and
the reaction is more complicated in case of sulfuric and
trifluoromethanesulfonic acids.
terizing the two types of nonꢀequivalent trimethylsilyl
groups (δ 0.02 and 0.21). Hydrolysis of compound 5 led to
the free amine 4, spectral characteristics of which were
the same as those of the product obtained using sodium
bicarbonate.
Compounds with amino group of the type 4 and 5 may
be of interest as starting reagents in the synthesis of subꢀ
stances with complexꢀforming and extracting properties,
as well as with properties of polymer stabilizers. In this
connection, some chemical properties of these compounds
were studied. Heating of compound 4 with acetic anꢀ
hydride (ratio 1 : 5) is accompanied by exhaustive acylaꢀ
tion of the amino and hydroxy groups and leads to derivaꢀ
tive 6, readily soluble in organic solvents (Scheme 3).
Scheme 3
Attempted dehydrochlorination of compounds 3 with
aqueous alkali to obtain free amines failed. The use of the
less basic sodium bicarbonate gives free amine 4 from
hydrochloride 3b in only 40% yield (Scheme 2). Apparꢀ
ently, the difficulties with the isolation of free aminoꢀ
phenols involve the ionization of the hydroxy groups in
alkaline media and formation of soluble phenolates. The
tertiary amines also did not yield product 4.
Addition of phenyl isocyanate at compound 4 occurs
on the amino group and gives urea derivative 7 (Scheme 4).
Scheme 2
Scheme 4
It is known that substances with several ligating cenꢀ
ters, able to form chelates, are the most efficient comꢀ
plexꢀforming reagents. In this connection, tethering of
two molecules 4 or 5 by a chainꢀspacer was of undoubted
interest. Hexamethylene and tolylene diisocyanates, easꢀ
ily available and quite active compounds, were chosen as
However, hexamethyldisilazane proved to be a good
dehydrohalogenating agent for salts 3. In fact the prolong
heating of salt 3b in hexamethyldisilazane leads to the
Оꢀsilylated secondary amine 5. The 1H NMR spectrum of
the latter contains two singlets of equal intensity, characꢀ

332
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 2, February, 2007
Burilov et al.
Scheme 5
Scheme 6
the tethering reagents. As a result, dicarbamates 8—10
with free or silylated phenol groups and linkers between
the urea moieties of different flexibility, were obtained
(Scheme 5).
Derivatives 4 and 5 are of particular interest for the
synthesis of calixarenes with the alternating substituents
of various nature at the lower rim of the molecule. The
conventional method using reaction of resorcinols with
aldehydes or acetals is not suitable for calixarenes of this
type. However, they can be accessed by binding of comꢀ
pounds 4 or 5 in reaction with aliphatic and aromatic
aldehydes. There is the only documented synthesis6 of
calixarenes by reaction of dimeric polyphenols of similar
structure with aldehydes. Moreover, the starting polypheꢀ
nol was obtained by a complicated way, namely, by conꢀ
densation of 4ꢀbromoresorcinol with aldehyde and subseꢀ
quent dehalogenation of the product obtained.
We carried out the reaction of polyphenol 3b with
formaldehyde in aqueous acidic medium to obtain calixꢀ
arene 11 with two Nꢀmethylaminomethyl groups at the
lower rim of the molecule (Scheme 6).
As it was shown above, reaction of resorcinol and
methylresorcinol with acetal 2 in ethanol, water or in a
mixture of them in the presence of acids of diverse nature
leads only to the dimeric products, amines 3. Further
investigation of this reaction, including variations of solꢀ
vent—acid combination, allowed us to invent conditions
(dioxane as the solvent, trifluoromethanesulfonic acid as
the acidic agent) providing the formation of calixarenes
12a,b (Scheme 7). Dioxane has been chosen, along with
the other factors, for its high enough boiling point (the
reaction requires rather drastic conditions), as well as for
high solubility of starting compounds in it. The strong
trifluoromethanesulfonic acid is also soluble in dioxane
and readily forms solvates with it. Unfortunately, the data
available now do not allow us to make certain conclusions
about the influence of conditions on the course of the
reaction of resorcinols with αꢀamino acetal 2.

Nꢀ[2,2ꢀBis(2,4ꢀdihydroxyaryl)ethyl]amines
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 2, February, 2007
333
Scheme 7
Nꢀ[2,2ꢀBis(2,4ꢀdihydroxyꢀ3ꢀmethylphenyl)ethyl]ꢀNꢀmethylꢀ
amine hydrochloride (3b). А. The compound was obtained simiꢀ
larly to 3a from 2ꢀmethylresorcinol (1b) (4.38 g, 35.3 mmol),
acetal 2 (2.1 g, 17.7 mmol), water (21 mL), ethanol (16 mL),
and conc. HCl (4.2 mL). The yield was 4.32 g (72%), m.p.
160—163 °С. Found (%): C, 60.37; Н, 6.88; Cl, 10.21; N, 4.07.
C
17H22ClNO4. Calculated (%): C, 60.09; H, 6.53; Cl, 10.43;
N, 4.12. 1H NMR (СD3OD), δ: 2.16 (s, 6 Н, Me); 2.75 (s,
3 Н, NMe); 3.67 (d, 2 Н, NCH2, 3J = 7.90 Hz); 5.01 (t, 1 Н,
CH, 3J = 7.90 Hz); 6.44 (d, 2 Н, H(5) arom., 3J = 8.40 Hz);
3
6.89 (d, 2 Н, H(6) arom., J = 8.40 Hz). 13C NMR (СD3OD),
δ: 8.99 (MeС(3)); 34.05 (СН); 37.19 (NMe); 53.60
(CH2); 108.35 (С(6) arom.); 113.51 (C(5) arom.); 119.83
(C(1) arom.); 126.22 (С(3) arom.); 154.43 (С(2) arom.); 156.27
(С(4) arom.). MS, m/z: 339.5 [M]+. IR, ν/cm–1: 1600 (arom.),
3100—3500 (ОН).
B. The 35% НCl (10 mL) and acetal 2 (1.05 g, 8.82 mmol)
were added sequentially to 2ꢀmethylresorcinol (1b) (2.19 g,
17.6 mmol) under stirring at 5 °С. The reaction mixture was
kept at 20 °С for 2 h. The white crystals of the product formed
were separated, washed with ether and dried in vacuo (2 h,
50 °C, 10 Torr). The yield was 2.51 g (84%), m.p. 160—163 °С.
Nꢀ[2,2ꢀBis(2,4ꢀdihydroxyꢀ3ꢀmethylphenyl)ethyl]ꢀNꢀmethylꢀ
amine hydrobromide (3c). А. The compound was obtained simiꢀ
larly to 3a from 2ꢀmethylresorcinol (1b) (2.19 g, 17.6 mmol),
acetal 2 (1.05 g, 8.82 mmol), water (10 mL), ethanol (10 mL),
and 40% HBr (8.4 mL). The yield was 1.81 g (54%), m.p.
150—153 °С. Found (%): C, 53.35; Н, 5.31; Вr, 21.22; N, 3.71.
С17Н22BrNО4. Calculated (%): C, 53.12; H, 5.73; Вr, 20.83;
N, 3.64. 1H NMR (D2О), δ: 2.02 (s, 6 Н, Me); 2.67 (s, 3 Н,
NMe); 3.56 (d, 2 Н, CH2, 3J = 7.84 Hz); 4.87 (t, 1 Н, СН, 3J =
7.84 Hz); 6.46 (d, 2 Н, H(5) arom., 3J = 8.36 Hz); 6.87 (d, 2 Н,
H(6) arom., 3J = 8.36 Hz).
R = H (1a, 12a), Me (1b, 12b); R´ = CH2N+H2Me•CF3SO3
–
In the conclusion, changing the experimental condiꢀ
tions in the reaction of resorcinols with αꢀmethylaminoꢀ
acetaldehyde dimethyl acetal makes it possible to direct it
toward formation of either linear dimeric or cyclic tetraꢀ
meric products. These substances are of interest as key
intermediates for synthesis of spatially organized strucꢀ
tures of a new type.
Experimental
B. The 40% НВr (10 mL) and acetal 2 (1.05 g, 8.82 mmol)
were added sequentially to 2ꢀmethylresorcinol (1b) (2.19 g,
17.66 mmol) at 5 °С. The mixture was kept at 20 °C for 12 h, the
crystalline product was separated, washed with diethyl ether and
dried in vacuo (2 h, 50 °C, 10 Torr). The yield was 2.95 g (87%),
m.p. 150—153 °С.
Nꢀ[2,2ꢀBis(2,4ꢀdihydroxyꢀ3ꢀmethylphenyl)ethyl]ꢀNꢀmethylꢀ
amine (4). A. An aqueous solution of sodium bicarbonate was
added to a solution of hydrochloride 3b (2.30 g, 7.59 mmol) in
water (5 mL) until the neutral pH value was achieved (litmus).
In 24 h the precipitate formed was filtered off and dried in vacuo
(12 h, 40 °C, 10 Torr). Compound 4 was obtained (0.90 g, 39%)
as amorphous white powder, turning dark upon heating over
250 °C (decomp.). Found (%): C, 67.50; Н, 7.93; N, 4.27.
C17H21NO4. Calculated (%): C, 67.31; H, 7.38; N, 4.62.
1H NMR (DMSOꢀd6, 20 °C), δ: 1.97 (s, 6 Н, Me); 2.28 (s, 3 Н,
NMe); 3.02 (d, 2 Н, СН2, 3J = 4.92 Hz); 4.41 (t, 1 Н, СН, 3J =
4.92 Hz); 6.16 (d, 2 Н, H(5) arom., 3J = 8.20 Hz); 6.43 (d,
2 Н, H(6) arom., 3J = 8.20 Hz). IR, ν/cm–1: 1600 (arom.),
3100—3500 (ОН).
1
H and 13C NMR spectra were recorded on a Bruker
MSLꢀ400 spectrometer (250 (1Н) and 100.62 MHz (13С)), the
chemical shifts were measured relatively to the signals of the
deuterated solvent. IR spectra were recorded on a URꢀ20 specꢀ
trophotometer in the range 400—3600 cm–1 and on a Vector 22
Fourier spectrometer (Bruker) in the range 400—4000 cm–1
(crystal samples were investigated in Nujol mulls or in KBr
pellets). The MALDIꢀTOF massꢀspectra were recorded on a
Finnigan DYNAMO MALDIꢀTOF instrument. Acetal 2 was
purchased from Lancaster.
Nꢀ[2,2ꢀBis(2,4ꢀdihydroxyphenyl)ethyl]ꢀNꢀmethylamine
hydrochloride (3a). A mixture of resorcinol (1a) (3.88 g,
35.3 mmol), acetal 2 (2.1 g, 17.7 mmol), water (21 mL), ethanol
(21 mL), and conc. HCl (4.2 mL) was heated at 70 °С for 10 h.
The solvent was removed, the crystalline precipitate formed was
filtered off, washed with ether and dried in vacuo (2 h, 70 °C,
0.4 Torr). Compound 3a was obtained in a yield of 3.78 g (68%),
m.p. 172—175 °С. Found (%): C, 57.50; Н, 5.93; N, 4.27.
C
15H18ClNO4. Calculated (%): C, 57.79; H, 5.82; N, 4.49.
1H NMR (СD3OD), δ: 2.74 (s, 3 Н, NMe); 3.64 (d, 2 Н,
NCH2, 3J = 7.87 Hz); 4.89 (t, 1 Н, СН, 3J = 7.87 Hz); 6.35 (d,
2 Н, H(5) arom., 3J = 8.53 Hz); 6.45 (s, 2 Н, H(3) arom.); 6.99
(d, 2 Н, H(6) arom., 3J = 8.53 Hz). 13C{1H} NMR (СD3OD), δ:
34.11 (СН); 37.19 (NMe); 53.60 (CH2); 103.82 (С(6) arom.);
108.51 (C(5) arom.); 118.45 (C(1) arom.); 131.13 (С(3) arom.);
156.22 (С(2) arom.); 158.34 (С(4) arom.). MS, m/z: 311.5 [M]+.
IR, ν/cm–1: 1600 (arom.), 3100—3500 (ОН).
B. A mixture of tetrasilyl ether 5 (0.21 g, 0.35 mmol) and
water (10 mL) was refluxed for 1 h, then kept at 20 °С for 5 days.
The precipitate was separated, washed with water and dried
in vacuo (1 h, 60 °C, 0.04 Torr). The yield was 0.08 g (74%),
m.p. >250 °C (decomp.). Found (%): C, 67.66; Н, 7.69; N, 4.31.
C
17H21NO4. Calculated (%): C, 67.31; H, 7.38; N; 4.62.
1H NMR spectrum was identical to that of the sample prepared
by method A.

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Burilov et al.
Nꢀ{2,2ꢀBis[2,4ꢀbis(trimethylsilyloxy)ꢀ3ꢀmethylphenyl]ethyl}ꢀ
1,1,16,16ꢀTetrakis(2,4ꢀdihydroxyꢀ3ꢀmethylphenyl)ꢀ3,14ꢀ
dimethylꢀ3,5,12,14ꢀtetraazahexadecanꢀ4,13ꢀdione (10). A mixꢀ
ture of amine 5 (0.8 g, 1.35 mmol), hexamethylene diisocyanate
(0.11 g, 0.67 mmol), and benzene (10 mL) was refluxed for 15 h.
The solvent was removed to leave the silylated derivative 9 as the
viscous oil. This was diluted with ethanol and kept for 14 days.
The powderꢀlike product formed was filtered off and dried
in vacuo (24 h, 20 °C, 8 Torr). Compound 10 was obtained
(0.27 g, 55%), m.p. 143—144 °С. Found (%): C, 65.03; H, 7.53;
N, 6.81. C42H54N4O10. Calculated (%): C, 65.12; H, 6.98;
Nꢀmethylamine (5). A mixture of hydrochloride 3b (0.6 g,
1.76 mmol) and hexamethyldisilazane (7.65 g, 47.51 mmol) was
kept at 130 °С for 5 h. The excess hexamethyldisilazane was
removed in vacuo (4 h, 80 °C, 0.8 Torr) to leave compound 5
(0.95 g, 90%) as a viscous liquid. Found (%): C, 58.33; H, 8.92;
N, 2.07. C29H53NO4Si4. Calculated (%): C, 58.83; H, 9.02;
N, 2.37. 1H NMR ((CD3)2CO, 20 °C), δ: 0.02, 0.21 (both s,
18 Н each, Me3Si); 2.32 (s, 6 Н, Me); 2.49 (s, 3 Н, NMe); 3.08
(m, 2 Н, СН2); 4.48 (m, 1 Н, СН); 6.18 (m, 2 Н, H(5) arom.);
6.51 (m, 2 Н, H(6) arom.).
1
N, 7.24. H NMR (CD3ОD), δ: 1.34, 1.49 (both m, 4 Н each,
Nꢀ[2,2ꢀBis(2,4ꢀdiacetoxyꢀ3ꢀmethylphenyl)ethyl]ꢀNꢀmethylꢀ
acetamide (6). A mixture of amine 4 (0.5 g, 1.47 mmol), acetic
anhydride (1.5 g, 14.7 mmol), and pyridine (0.1 mL) was kept at
20 °С for 6 h. The volatile components were removed, the resiꢀ
due was dried in vacuo (1 h, 60 °C, 0.4 Torr). Compound 6
(0.61 g, 88%) was obtained, m.p. 200—201 °С. Found (%):
C, 63.50; Н, 6.83; N, 2.27. C27H31NO9. Calculated (%):
C, 63.15; H, 6.08; N, 2.73. 1H NMR ((CD3)2CO), δ: 2.01 (s,
6 Н, Me); 2.35—2.52 (br.s, 15 Н, Ac); 2.71 (s, 3 Н, NMe); 3.91
(m, 2 Н, СН2); 4.87 (m, 1 Н, СН); 6.42 (d, 2 Н, H(5) arom.,
3J = 8.29 Hz); 6.61 (d, 2 Н, H(6) arom., 3J = 8.29 Hz).
Nꢀ[2,2ꢀBis(2,4ꢀdihydroxyꢀ3ꢀmethylphenyl)ethyl]ꢀNꢀmethylꢀ
N´ꢀphenylurea (7). Phenyl isocyanate (0.15 g, 12.6 mmol) was
added to a solution of amine 4 (0.38 g, 12.6 mmol) in acetone
(10 mL) under stirring. The reaction mixture was kept at 20 °C
for 18 h, the precipitate formed was filtered off and dried in vacuo
(2 h, 60 °C, 0.4 Torr). Compound 7 (4.95 g, 93%) was obtained,
m.p. 190—192 °С. Found (%): C, 68.20; Н, 6.89; N, 6.50.
СН2); 2.08 (s, 12 Н, Me); 2.70 (s, 6 Н, NMe); 3.14 (m, 4 Н,
CH2NH); 3.80 (d, 4 Н, CH2NMe, 3J = 7.31 Hz); 6.32 (d, 4 Н,
H(2) arom., 3J = 8.36 Hz); 6.84 (d, 4 Н, H(3) arom., 3J =
8.36 Hz) (the signal of the proton in СНꢀgroup overlaps with the
signal of the solvent (δ 4.79)). IR, ν/cm–1: 1633, 1596 (C=O);
1601 (arom.); 3100—3600 (ОН).
2 , 1 4 ꢀ D i ( m e t h y l a m i n o m e t h y l ) ꢀ 5 , 1 1 , 1 7 , 2 3 ꢀ
tetramethylpentacyclo[19.3.1.13,7.19,13.115,19]octacosaꢀ
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23ꢀdodecaenꢀ
4,6,10,12,16,18,22,24ꢀoctaol dihydrochloride (11). A mixture of
compound 3b (0.36 g, 1.06 mmol), formaldehyde (35% aq.,
1 mL, 11.66 mmol), water (5 mL), and conc. HCl (0.5 mL) was
heated at 100 °С for 8 h. The precipitate formed was filtered off,
washed with acetonitrile and dried in vacuo (12 h, 20 °C, 8 Torr).
Compound 11 (0.28 g, 75%) was obtained, which turns dark on
heating over 290 °C (decomp.). Found (%): C, 61.97; Н, 6.64;
N, 4.31. C36H44Cl2N2O8. Calculated (%): C, 61.45; H, 6.26;
N, 3.98. 1H NMR (D2О), δ: 2.06 (s, 12 Н, Me); 2.70 (s, 6 Н,
NMe); 3.58 (d, 4 Н, СН2, 3J = 7.87 Hz); 4.92 (t, 2 Н, СН, 3J =
7.87 Hz); 6.87 (s, 4 Н, H arom.) (the signal of the protons in
СН2 groups overlaps with the signal of the solvent (δ 4.72)). MS,
m/z: 632 [M – 2 HCl]+.
2 , 8 , 1 4 , 2 0 ꢀ T e t r a ( m e t h y l a m i n o m e t h y l ) p e n t a ꢀ
c y c l o [ 1 9 . 3 . 1 . 1 3 , 7 . 1 9 , 1 3 . 1 1 5 , 1 9 ] o c t a c o s a ꢀ
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23ꢀdodecaenꢀ
4,6,10,12,16,18,22,24ꢀoctaol tetra(hydrotrifluoromethanesulfoꢀ
nate) (12a). A mixture of resorcinol (1a) (3 g, 27.3 mmol),
acetal 2 (3.24 g, 27.3 mmol), trifluoromethanesulfonic acid
(8.18 g, 54.6 mmol), and dioxane (25 mL) was refluxed for 9 h.
The precipitate was separated, washed with dioxane and dried
in vacuo (10 h, 20 °C, 8 Torr). Compound 12a (3.54 g, 41%) was
obtained as amorphous white powder, turning dark upon heatꢀ
ing over 240 °С (decomp.). Found (%): C, 37.09; H, 3.36;
N, 4.08; S, 9.67. C40H48F12N4O20S4. Calculated (%): C, 38.10;
H, 3.84; N, 4.44; S, 10.17. 1H NMR (CD3OD), δ: 2.47 (s, 12 Н,
NMe); 3.45 (d, 8 Н, СН2, 3J = 8.05 Hz); 4.68 (t, 4 Н, СН, 3J =
8.05 Hz); 6.09 (s, 4 Н, Н(4) arom.); 6.72 (s, 4 Н, Н(1) arom.).
13C NMR (D2O), δ: 34.53 (СН); 36.07 (NMe); 53.65 (CH2);
104.58 (С(4) arom.); 119.06 (С(2) arom.); 122.90 (CF3S); 127.24
(С(1) arom.); 154.73 (С(3) arom.). IR, ν/cm–1: 1600 (arom.),
3100—3500 (ОН). MS, m/z: 663 [M – 4 CF3SO2OH]+.
C
24H26N2O5. Calculated (%): C, 68.23; H, 6.20; N, 6.63.
1H NMR ((CD3)2СО), δ: 2.06 (s, 6 Н, Me); 2.84 (s, 3 Н, NMe);
3.80 (d, 2 Н, СН2, 3J = 6.72 Hz); 4.84 (t, 1 Н, СН, 3J =
6.72 Hz); 6.33 (d, 2 Н, H(5) arom., 3J = 8.53 Hz); 6.78 (d, 2 Н,
H(6) arom., 3J = 8.53 Hz); 6.90 (m, 1 Н, Н(15)Ph); 7.19 (m,
2 Н, Н(14)Ph); 7.46 (m, 2 Н, Н(13)Ph). 13C NMR (СD3OD), δ:
9.14, 9.70 (С(7)); 30.61 (С(8)); 38.67 (С(10)); 54.15 (С(9));
107.16 (С(3) arom.); 112.04 (С(5) arom.); 119.16 (С(13) arom.);
120.03 (С(1) arom.); 123.71 (С(15) arom.); 126.49 (С(2) arom.);
129.41 (С(14) arom.); 140.92 (С(12) arom.); 154.92
(С(4) arom.); 155.50 (С(6) arom.); 157.66 (С(11)=О).
N´,N´´´ꢀ(4ꢀMethylꢀ1,3ꢀphenylene)bis{Nꢀ[2,2ꢀbis(2,4ꢀdiꢀ
hydroxyꢀ3ꢀmethylphenyl)ethyl]ꢀNꢀmethylurea} (8). A mixture of
amine 4 (0.61 g, 20.1 mmol), 2,4ꢀdiisocyanatoꢀ1ꢀmethylbenzene
(0.175 g, 10.05 mmol) and acetone (10 mL) was kept at 20 °С for
15 h. The solvent was removed and the product was dried in vacuo
(6 h, 20 °C, 0.04 Torr). Compound 8 was obtained (0.53 g, 83%)
as amorphous white powder, turning dark upon heating over
200 °С (decomp.). Found (%): C, 64.67; Н, 9.12; N, 7.01.
C
43H48N4O10. Calculated (%): C, 65.10; H, 9.02; N, 7.23.
1H NMR ((CD3)2CO), δ: 2.08 (m, 3 Н, Me); 2.11 (m, 12 Н,
Me); 2.95 (m, 6 Н, NMe); 3.89 (m, 4 Н, СН2N); 4.93 (m, 2 Н,
CH); 6.41 (d, 4 Н, H(2) arom., 3J = 8.53 Hz); 6.88 (d, 4 Н,
3
H(3) arom., J = 8.53 Hz); 7.06—7.81 (m, 3 Н, H(13), H(14),
2,8,14,20ꢀTetra(methylaminomethyl)ꢀ5,11,17,23ꢀ
tetramethylpentacyclo[19.3.1.13,7.19,13.115,19]octacosaꢀ
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23ꢀdodecaenꢀ
4,6,10,12,16,18,22,24ꢀoctaol tetra(hydrotrifluoromethanesulfoꢀ
nate) (12b). The compound was obtained similarly to 12a from
2ꢀmethylresorcinol (1b) (1.11 g, 8.97 mmol), acetal 2 (1.07 g,
8.97 mmol), trifluoromethanesulfonic acid (1.41 g, 9.40 mmol),
and dioxane (10 mL). Compound 12b (1.27 g, 43%) was obꢀ
tained as amorphous white powder, turning dark upon heating
H(17)). 13С NMR ((CD3)2CO), δ: 9.18 (С(7)); 13.52 (С(18));
30.35 (С(8)); 36.77 (С(10)); 54.25 (С(9)); 107.21 (С(3) arom.);
112.13 (С(5) arom.); 117.91 (С(17) arom.); 118.47
(С(13) arom.); 120.27 (С(1) arom.); 126.52 (С(14) arom.);
127.47 (С(2) arom.); 130.57 (С(15) arom.); 138.85, 138.91
(С(12), C(16) arom.); 154.98 (С(4) arom.); 155.36 (С(6) arom.);
158.09 (С(11)=О). IR, ν/cm–1: 1627, 1591 (C=O); 1461,
1580 (arom.); 3100—3600 (ОН).

Nꢀ[2,2ꢀBis(2,4ꢀdihydroxyaryl)ethyl]amines
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 2, February, 2007
335
over 260 °С (decomp.). Found (%): C, 43.23; H, 5.78; N, 3.79;
S, 8.96. C44H56F12N4O20S4. Calculated (%): C, 43.45; H, 5.61;
N, 3.90; S, 8.92. 1H NMR (D2O), δ: 2.00 (s, 12 Н, Me); 2.73 (s,
12 Н, NMe); 3.68 (d, 8 Н, CH2,3J = 8.20 Hz); 4.90 (t, 4 Н, СН,
3J = 8.20 Hz); 6.62 (s, 4 Н, H arom.). 13C NMR (D2O), δ:
9.72 (Me); 30.43 (СН); 34.05 (NMe); 53.26 (CH2); 115.83
(С(4) arom.); 118.85 (С(2) arom.); 121.60 (С(1) arom.); 122.48
(CF3S); 151.28 (С(3) arom.). IR, ν/cm–1: 1600 (arom.),
3100—3500 (ОН). MS, m/z: 719 [M – 4 CF3SO2OH]+.
2. J. Vicens and V. Böhmer, Calixarenes: a Versatile Class of
Macrocyclic NMR Compounds, Kluwer Acad. Publ., Dodrecht,
1991, 15.
3. Z. Asfari, V. Böhmer, J. Harrowfield, and J. Vicens, Calixꢀ
arenes, 2001, Kluwer Acad. Publ., Dordrecht—Boston—Lonꢀ
don, 2001.
4. E. V. Popova, Yu. M. Volodin, A. R. Burilov, М. A. Pudovik,
W. D. Habicher, and A. I. Konovalov, Izv. Akad. Nauk, Ser.
Khim., 2002, 1815 [Russ. Chem. Bull., Int. Ed., 2002, 51, 1836].
5. L. M. Tunstad, J. A. Tucker, E. Dalcanale, J. Weiser, J. A.
Bryant, J. C. Sherman, R. C. Helgeson, C. B. Knobler, and
D. J. Cram, J. Org. Chem., 1989, 54, 1305.
References
6. G. Rumboldt, V. Böhmer, B. Botta, and E. F. Paulus, J. Org.
Chem., 1998, 63, 9618.
1. C. D. Gutsche, Calixarenes, The Royal Society of Chemistry,
Cambridge, 1989, 132.
Received November 22, 2006