Facile synthesis of mono and dibenzo N,N-disubstituted diaza 18-crown-6 derivatives

Article abstract of DOI:10.1002/jhet.5570380142

This study represents a facile synthesis of building blocks (1-3) of crown ethers and amine precoursers (4a-d). The study also involves synthesis of mono and dibenzo N,N-disubstituted diaza 18-crown-6 derivatives with high yield without chromatographic pu

Full text of DOI:10.1002/jhet.5570380142

Jan-Feb 2001
Facile Synthesis of Mono and Dibenzo
281
N,N'-Disubstituted Diaza 18-Crown-6 Derivatives
Giray Topal [a], Nadir Demirel [b], Mahmut Tog˘rul [b],
Yılmaz Turgut [b] and Halil Hos¸gören* [b]
[a] University of Dicle, Faculty of Education, Department of Chemistry
[b] University of Dicle, Faculty of Science, Department of Chemistry
21280 Diyarbakır, Turkey
Received June 22, 2000
This study represents a facile synthesis of building blocks (1-3) of crown ethers and amine precoursers
(4a-d). The study also involves synthesis of mono and dibenzo N,N'-disubstituted diaza 18-crown-6
derivatives with high yield without chromatographic purification and high vacuum distillation. The complex
ability of host the ethers was evaluated in terms of structural modification.
J. Heterocyclic Chem., 38, 281 (2001).
Introduction.
crown ethers. The advanteges of benzo- substitution
include potentially ease of synthesis, increased solubility
of host compounds in organic solvents, and simpler nmr
spectra of the host macrocycles and their complexes [7].
In general, complexes formed with saturated crown
ethers are more soluble and stable in aliphatic solvent
than are those formed with aromatic crown ethers. On
the other hand, the presence, in the crown compounds,
of aromatic nuclei carries with it certain advantages.
For example, complex formation with aromatic crowns
can be followed commercial using ultra-violet
spectrophotometers [8].
The remarkable ability of crown ethers, such as
18-crown-6, to form complexes with alkali metal cations
and a wide range of other cations including primary alkyl-
ammonium cations, was discovered by Pedersen [1]. This
observation has been studied by several groups [2], and
crown ethers have been designed and synthesised that
show high chiral selectivity in complexe formation [3] and
also in the catalysis of chemical reactions [4].
It has been shown [5,6] that benzo-derivatives of crown
ethers have an ability to form complexes with primary
alkylammonium salts that are similar to that of the parent

282
G. Topal, N. Demirel, M. Tog˘rul,Y. Turgut and H. Hos¸gören
Vol. 38
It is known that the most stable complex is formed with
reaction of 3 with four different aryl and alkyl amine in the
presence of sodium carbonate (Na CO ) as base in a Dean-
Stark apparatus to remove water formed at 100-110 °C in
a cation which fits well into the molecule cavity of a given
ligand, whereas a stable complex is not formed if the ion is
too large or to small to lie in the cavity. Hence in order to
investigate the effect of benzo substitution on complex
formation of diaza crown ethers with alkali metal and
primary alkyl-aryl ammonium cations five different
crown ethers with various lipophilic character were
synthesized.
2
3
good yield.
Cyclization of 2 with 4a-c in refluxing acetonitrile
(CH CN) gave macrocycles 5a-c in yields of 75%, 73%
3
and 72% respectively. An interesting result was obtained
in the synthesis of 5a-c. Although sodium perchlorate
(NaClO ) was added to the reaction medium to promote
4
cyclization, the product analysis revealed that macrocycles
existed as free ligand, no complexation was observed.
Cyclization of 2 with an appropriate diamine in refluxing
Result and Discussion.
The versatile building blocks of crown ethers (1-3) and
amine precursours (4a-d) were prepared as shown in
scheme-1 and scheme-2 respectively. The advantage of our
procedure, in synthesis of 1, compared with those in
litaratüre is summarized as follows; it is a single step
reaction of catechol with ethelene oxide at mild
temperature in high yield. Sutherland and co-workers
synthesised 1 using more than one step with a low overall
yield. Another method is recorded in a patent [8].
Synthesis of diamine (4a-d) was accomplished by the
xylene or CH CN gave macrocycles 6a-b in yields of 74%
3
and 76% respectively.
Macrocycles 6a-b were isolated as NaClO and barium
4
perchlorate (Ba(ClO ) ) complexes respectively. This
4 2
result showed that benzo substitution on diaza crown
ethers enhances selectivity. On the other hand dibenzo
substitution, due to steric hindrence of the benzene units
on the ring, diminished the selectivity of crown ethers on
alkali metals.

Jan-Feb 2001
Mono and Dibenzo N,N'-Disubstituted Diaza 18-Crown-6 Derivatives
283
EXPERIMENTAL
Anal. Calcd. for: C H Cl O C, 51.08; H, 5.14. Found: C,
10 12 2 2
51.64; H, 5.06.
1,2-Bis-[2-(N-Hexylamino)ethoxy]benzene (4a).
General Information.
1,2-Bis-(2-chloroethoxy)benzene (8.62 g, 36.68 mmol),
1
The H nmr spectra were obtained at 400 MHz on a BRUKER
sodium carbonate (Na CO ) (15.55 g, 146.7 mmol) and
2
3
DPX-400 High Perpormance Digital FT-NMR in deuterio-
chloroform (CDCl ) with TMS as the internal standard. The
nmr spectra were obtained at 100 MHz on a BRUKER DPX-400
High Perpormance Digital FT-NMR. The elemental analyses
were obtained with CARLO-ERBA 1108 Model. Infrared
hexylamine (29.69 g, 293.44 mmol) was stirred at 100-110 °C
under dry nitrogen with a Dean-Stark apparatus to remove water
from the reaction medium. The benzene extract was dried
13
C
3
(Na CO ) and evaporated. The product distilled to give 9.64 g
2
3
(72.2 %) bp 181-182 °C at 0.1 mm-Hg; ir: ν 3335, 3274, 3063,
Spectra were obtained on
a MIDAC-FTIR Model
3036, 2927, 2894, 1593, 1502, 1454, 1377, 1328, 1255, 1120,
1700 Spectrophotometer. Melting points were obtained on a
GALLENKAMP Model apparatus with open capillaries. All
chemicals were reagent grade unless otherwise stated.
-1
1
1112, 1042, 933, 741 cm ; H nmr (CDCl ): δ 0.89 (t, J 6.87
3
Hz, 6H); 1.28-1.38 (m, 12H); 1.52 (p, J 7.21 Hz, 4H); 1.8
(bs, 2H); 2.67 (t, J 7.29 Hz, 4H); 3.01 (t, J 5.31 Hz, 4H); 4.11
13
(t, J 5.32 Hz, 4H); 6.90-6.94 (m, 4H); C nmr (CDCl ): δ 14.2,
1,2-Bis-(2-hydroxy ethoxy)benzene (1).
3
22.9, 27.3, 30.5, 32.1, 49.2, 50.2, 69.3, 115.1, 121.8, 149.5.
Catechol (11.0 g, 100 mmol) and diethylamine hydrochloride
(as catalyst) were cooled to -80 °C in a sealed container. Ethylene
Oxide (9.8 ml, 200 mmol) was added to the mixture at the same
temperature, and the mixture was kept at 30-35 °C for 10 days.
The product distilled under reduced pressure for further purifica-
tion to give 18.81 g (95 %) of 1, mp 81-83 °C. (Lit. [7]: mp 93-94
°C) ir: ν 3495, 3396, 3314, 3082, 3068, 2957, 2939, 2926, 1594,
1510, 1454, 1426, 1320, 1248, 1213, 1112, 1089, 1070, 1042
Anal. Calcd. for: C H N O •2HCl: C, 60.39; H, 9.68; N,
6.40. Found:C, 60.6; H, 9.57; N, 6.47.
22 40
2 2
1,2-Bis-[2-(N-Octylamino)ethoxy]benzene (4b).
This compound was prepared using a method similar to that
used for the 1,2-bis-[2-(N-hexylamino)ethoxy]benzene (4a),
from 1,2-bis-(2-chloroethoxy)benzene (7.62 g, 32.42 mmol),
Na CO (13.74 g, 129.7 mmol) and octylamine (33.52 g,
2
3
-1
1
cm ; H nmr (CDCl ): δ 3.63 (bs, 2H); 3.93 (t, J 4.27 Hz, 4H);
259.7 mmol). The product yield was 56%, (7.64 g) bp 190-192
3
13
4.12 (t, J 4.32 Hz, 4H); 6.95 (s , 4H); C nmr (CDCl ): δ 61.4,
°C at 0.1 mmHg; ir: ν 3316, 3064, 3033, 2921, 2848, 1587,
3
-1
1
71.8, 115.3, 122.4, 149.3.
1501, 1447, 1250, 1124, 1040, 737cm ; H nmr (CDCl ): δ
3
Anal. Calcd. for: C
60.42; H,7.43.
H O : C, 60.59; H, 7.12. Found: C,
0.89 (t, J 6.86 Hz, 6H); 1.29-1.32(m, 20H); 1.52 (p, J 7.15 Hz,
4H); 1.8 (bs, 2H); 2.68 (t, J 7.3 Hz, 4H); 3.02 (t, J 5.31 Hz,
4H); 4.12 (t, J 5.31 Hz, 4H); 6.91-6.95 (m, 4H); C nmr
10 14 4
13
1,2-Bis-(2-p-tolylsulphonylethoxy)benzene (2).
(CDCl ): δ 14.4, 23.0, 27.8, 29.6, 29.9, 32.2, 49.4, 50.3, 69.4,
3
115.2, 122.0, 149.5.
Anal. Calcd. for: C H N O •2HCl: C, 63.26; H, 10.21; N,
5.67. Found: C, 63.58; H, 10.69; N, 5.63.
1,2 Bis-(2-hydroxyethoxy)benzene (26.73 g, 135 mmol) was
dissolved in pyridine (110 ml ) at -10 °C. p-Toluene sulphonyl
chloride (51.43, 270 mmol) was added to the mixture over
three hours and then stirred at -10 °C for four hours. The mixture
was kept overnight at 4 °C. The product crystallised from
methanol to give 65.48 g (96%) of 2, mp. 95-95.5 °C. (Lit. [7]:
mp 95.5-97 °C, Lit.[8]: mp 95-96 °C) ir: ν 3093, 3070, 3046,
2938, 2877, 1601, 1501, 1454, 1355, 1253, 1224, 1170, 1123,
26 48
2 2
1,2-Bis-[2-(N-Benzylamino)ethoxy]benzene (4c).
This compound was prepared using a method similar to that used
for 1,2-bis-[2-(N-Hexylamino)ethoxy]benzene (4a), from 1,2-bis-
(2-chloroethoxy)benzene (8.62 g, 36.68 mmol), Na CO (15.55 g,
146.7 mmol) and benzylamine (31.44 g, 292.2 mmol). The product
yield was 70% (9.65 g), bp 200-202 °C at 0.1 mmHg; ir: ν 3318,
3067, 3029, 2928, 2874, 2836, 1643, 1589, 1496, 1458, 1249, 1218,
1118, 1041, 910, 740, 694 cm ; H nmr (CDCl ): δ 2.10 (bs, 2H);
3.03 (t, J 5.25 Hz, 4H); 3.86 (s , 4H); 4.15 (t, J 5.23 Hz, 4H); 6.95
(s, 4H); 7.32-7.38 (m, 10 H); C nmr (CDCl ): δ 48.7, 54.1, 69.7,
115.4, 122.2, 127.4, 128.6, 128.9, 140.9, 149.7.
2
3
-1
1
1100, 1062, 1015, 921, 811, 773 cm ; H nmr (CDCl ): δ 2.46
3
(s, 6H); 4.18 (t, J 4.83 Hz, 4H); 4.34 (t, J 4.85 Hz, 4H); 6.82-6.94
13
(dq, 4H); 7.34-7.83 (dd , 8H); C nmr (CDCl ): δ 22.0, 67.8,
3
-1
1
3
68.8, 116.8, 123.1, 128.3, 130.3, 133.3, 145.4, 148.9.
Anal. Calcd. for: C
H O S : C, 56.9; H, 5.2; S, 12.65.
24 26 8 2
13
3
Found: C, 57.2; H, 5.3; S, 12.60.
.
1,2-Bis-(2-chloroethoxy)benzene (3).
Anal. Calcd. for: C H N O 2HCl: C, 64.14; H, 6.73; N,
24 28
2 2
6.23. Found: C, 64.06; H, 6.74; N, 6.160.
A solution of 1,2-bis-(2-hydroxyethoxy)benzene (16.43 g,
83 mmol) and pyridine (13.38 g , 170 mmol ) in absolute benzene
1,2-Bis-[2-(N-dodecylamino)ethoxy]benzene (4d).
(200 ml) was stirred at 80 °C. Thionyl chloride (SOCl ) (20.15 g,
2
This compound was prepared using a method similar to that
used for the 1,2-bis-[2-(N-hexylamino)ethoxy]benzene (4a),
from 1,2-bis-(2-chloroethoxy)benzene (8.62 g, 36.68 mmol),
170 mmol) was added to the solution dropwise in three hours and
then left for 18 hours. The mixture was cooled to the room
temperature and 10 ml concentrated hydrochloric acid (HCl) and
10 ml water was added. The resulting organic phase was washed
twice with water. The benzene extract was dried with potassium
carbonate (K CO ) and evaporated. The product crystallised
Na CO (15.55 g, 146.7 mmol) and dodecylamine (54.28 g,
2
3
293.44 mmol). The product was 10.7 g (70%), bp 220-222 °C at
0.1 mmHg; ir: ν 3326, 3076, 3057, 2960, 2913, 2852, 1582,
-1
1496, 1473, 1442, 1270, 1255, 1208, 1115, 1038, 835, 733 cm ;
2
3
1
from methanol to give 17.55 g (90%) of 3, mp 55-56 °C; ir: ν
H (CDCl ): δ 0.90 (t, J 6.69 Hz, 6H); 1.28-1.33 (m, 40H); 1.58
3
3072, 3018, 2963, 2917, 2869, 1593, 1456, 1422,1257, 1196,
(bs, 2H); 2.71 (t, J 7.33 Hz, 4H); 2.90 (t, J 5.02 Hz, 4H); 4.09
-1
1
13
1126, 769, 746, 666 cm ; H nmr (CDCl ): δ 3.76 (t, J 5.86 Hz,
(t, J 5.02 Hz, 4H); 6.78-7.00 (m, 4H); C nmr (CDCl ): δ 14.5,
3
3
13
4H); 4.21(t, J 5.86 Hz, 4H); 6.91 (s, 4H); C nmr (CDCl ):
23.1, 27.6, 29.7, 29.9, 29.9, 29.9(5), 29.9(9), 30.0, 30.0, 32.3,
48.7, 49.8, 72.1, 117.7, 119.9, 150.7.
3
δ 42.7, 70.4, 116.9, 123.1, 149.2.

284
G. Topal, N. Demirel, M. Tog˘rul,Y. Turgut and H. Hos¸gören
Vol. 38
Anal. Calcd. for: C H N O •2HCl: C, 67.40; H, 10.98; N,
4.62. Found: C, 67.81; H, 11.23; N, 4.23.
1,10-didodecyl-4,7-dioxa-1,10-diazadecane (23.23 g, 48.0 mmol)
was added simultaneously. The mixture was stirred at 80 °C for 36
34 64
2 2
hours. The THF-CH CN extract was dried and evaporated and the
3
N,N'-Dihexyl-7,16-diaza-1,4,10,13-tetraoxa-2,3,11,12-dibenzo-
cyclooctadeca-2,11-diene (5a).
residue crystallised from ethyl acetate to give the NaClO •H O
4
2
complex of N,N'-didodecyl-7,16-diaza-1,4,10,13-tetraoxa-2,3-
benzocyclooctadec-2-ene mp 71-72 °C. The free ligand was
recovered by passing the complex through a column on basic
alumina (Al O ) to give 22.94 g (74%), mp 43-45 °C; ir: ν 3311,
To the mixture of Na CO (20 g, 188.6 mmol) and sodium
2
3
perchlorate monohydrate (NaClO •H O) (6.74 g, 48.0 mmol) in
4
2
tetrahydrofuran-acetonitrile (THF-CH CN) (800 ml) 1,2-bis-
3
2
3
(2-p-tolylsulphonylethoxy)benzene (8.67 g, 17.14 mmol) and
1,2-bis-[2-(N-hexylamino)ethoxy]benzene (6.24 g, 17.14 mmol)
was added simultaneously. The mixture was stirred at 80 °C for
3186, 3114, 2955, 2918, 2851, 2804, 1586, 1505,1472, 1253, 1121,
-1
1
1087, 758, 716, 625 cm ; H nmr (CDCl ): δ 0.86 (t, J 6.71 Hz,
3
6H); 6.89-7.02 (m, 8H); 3.65 (s, 4H); 4.16 (t, J 4.69Hz, 4H); 2.87
(t, J 4.59 Hz, 4H); 2.72 (t, J 4.53 Hz, 4H); 2.56 (t, J 8.01 Hz, 4H);
36 hours. The THF-CH CN extract was evaporated to give a
3
white solid. The product crystallised from ether-ethyl acetate to
4.16 (t, J 4.69 Hz, 4H); 3.60 (t, J 4.66 Hz, 4H); 1.10-1.45 (m, 42H);
give 8.33 g (75%) mp 130-131 °C; ir: ν 3063, 2954, 2925, 2854,
13
C nmr (CDCl ): δ 14.0, 22.7, 24.8, 27.5, 29.3, 29.6, 29.7, 31.9,
3
-1 1
2799, 1594, 1112, 1049, 1022 cm ; H nmr (CDCl ): δ 6.86-6.90
3
52.3, 52.4, 53.8, 64.8, 66.3, 68.8, 113.6, 122.0, 147.0.
(m, 8H); 4.09 (t, J 6.23 Hz, 8H); 3.29 (t, J 6.23 Hz, 8H); 2.63 (t, J
Anal. Calcd. for: C
H N O •NaClO •H O: C, 62.40; H,
40 74 2 4 4 2
7Hz, 4H); 0.49-1.50 (m, 4H); 1.33-1.35 (m, 12H) 0.92 (t, J 6.64
9.69; N, 3.64. Found: C, 62.70; H,10.70; N, 3.56.
Anal. Calcd. for: C H N O ; C, 74.25; H, 12.64; N, 4.33.
13
Hz,6H); C nmr (CDCl ): δ 6.28, 24.88, 29.31, 30.31, 34.06,
3
40 74
2 4
56.03, 56.59, 69.24, 114.31, 122.80, 150.91.
Found: C, 74.57; H,12.76; N, 4.28.
Anal. Calcd. for: C
H N O : C,72.96; H, 9.57; N, 5.32.
32 50 2 4
N,N'-Dibenzyl-7,16-diaza-1,4,10,13-tetraoxa-2,3-benzo-
cyclooctadec-2-ene (6b).
Found: C, 72.71; H, 9.76; N, 5.10.
N,N'-Dioctyl-7,16-diaza-1,4,10,13-tetraoxa-2,3,11,12-dibenzo-
cyclooctadeca-2,11-diene (5b).
To a mixture of n-tripropylamine ( 8.1 g , 56.5 mmol) in xylene
(200 ml) 1,2-bis-(2-p-tolylsulphonylethoxy)benzene (5.7 g,
11.3 mmol) and 1,10-dibenzyl-4,7-dioxa-1,10-diazadecan (3.7 g,
11.3 mmol) was added simultaneously. The mixture was stirred at
110 °C for 16 hours. The mixture was then cooled to the room
temperature, was washed with hot methanol to remove unreacted
amine and tosylate. The xylene was then evaporated and the product
This compound was prepared using a method similar to that
used for N,N'-dihexyl-7,16-diaza-1,4,10,13-tetraoxa-2,3,11,12-
dibenzocyclooctadeca-2,11-diene (6a), from 1,2-bis-(2-p-tolyl-
sulphonylethoxy)benzene (6.02 g, 12 mmol),1,2-bis-[2-(N-
Octylamino)ethoxy]benzene (5 g, 12 mmol), Na CO (5 g,
2
3
47 mmol) and NaClO .H O (1.67 g, 12 mmol). The product was
4
2
was dissolved in ethanol and equimolar Ba(ClO ) in ethanol was
4 2
crystallised from CH CN to give 5.1 g (73%) mp 135.5-137 °C;
3
added to the solution. After crystallisation, the product was filtered
and washed twice with methanol to give 7.1 g (76%) of the
ir: ν 3063, 2919, 2848, 1595, 1505, 1469, 1454, 1337, 1256,
-1 1
1229, 1122, 1046, 1022, 775, 735 cm ; H nmr (CDCl ): δ 0.91
3
Ba(ClO ) complex of N,N'-dibenzyl-7,16-diaza-1,4,10,13-
4 2
(t, J 6.76 Hz, 6H); 6.84-6.90 (m, 8H); 4.09 (t, J 6.21 Hz, 8H);
3.29 (t, J 6.21 Hz, 8H); 2.63 (t, J 7.49 Hz, 4H); 1.51 (bs, 4H);
tetraoxa-2,3-benzocyclooctadec-2-ene mp 300 °C dec; ir: ν 3438,
3085, 3061, 3029, 2952, 2887, 2860, 1594, 1505,1458, 11364,
13
1.32 (s, 20H); C nmr (CDCl ): δ 14.5, 23.1, 27.8, 28.5, 29.7,
-1 1
3
1245, 1193, 1121, 1049, 731, 634 cm ; H nmr (DMSO-d ): δ 2.79
6
30.0, 32.3, 54.2, 54.7, 67.4, 112.4, 121.0, 149.1.
(t, J 5.80 Hz, 2H); 2.96 (t, J 5.80 Hz, 2H); 3.54 (t, J 5.80 Hz, 2H);
Anal. Calcd. for: C H N O : C, 74.22; H, 9.96; N, 4.81.
4.02 (t, J 5.81 Hz, 2H); 3.69 (s, 4H); 3.46 (s, 4H); 6.81-7.34
36 58
2 4
13
Found: C, 74.30; H, 10.44; N, 4.55.
(m, 14 H); C nmr (DMSO-d ): δ 53.4, 54.2, 59.4, 68.2, 70.1, 70.8,
6
114.4, 121.7, 127.6, 128.9, 129.4, 140.4, 149.3.
N,N'-Dibenzyl-7,16-diaza-1,4,10,13-tetraoxa-2,3,11,12-dibenzo-
cyclooctadeca-2,11-diene (5c).
Anal. Calcd. for:C H N O •Ba(ClO ) : C, 43.58; H, 4.60;
30 38
2
4
4 2
N, 3.39. Found: C, 43.27; H,4.82; N, 3.64.
This compound was prepared using a method similar to that used
for N,N'-dihexyl-7,16-diaza-1,4,10,13-tetraoxa-2,3,11,12-dibenzo-
cyclooctadeca-2,11-diene (6a), from 1,2-bis-(2-p-tolylsulphonyl-
ethoxy)benzene (7.63 g,15 mmol) 1,2-bis-[2-(N-benzyl-
REFERENCES AND NOTES
[1] C. J. Pedersen, J. Am. Chem. Soc., 89, 7017 (1967).
[2a] D. J. Cram, R. C. Helgeson, R. Sausa, J. M. Timko,
Newcomb, P. Moreau, F. De Jong, G. W. Gokel, D. H. Hoffman, L. A.
Domeier, S. C. Peacock, K. Madan and L. Kaplan, Pure Appl. Chem., 43,
327 (1975); [b] Gokel and H. D. Durst, Synthesis., 168 (1976).
[3a] R. C. Helgeson, J. M. Timko, P. Moreau, S. C. Peacock, J. M.
Mayer and D. J. Cram, J. Am. Chem. Soc., 96, 6762 (1974); [b] G.
Dotsevi, Y. Sogah, and D. J. Cram, J. Am. Chem. Soc., 98, 3040 (1976).
[4] Y. Chao and D. J. Cram, J. Am. Chem. Soc., 98, 1015 (1976).
[5] J. M. Timko, R. C. Helgeson, M. Newcomb, G. W. Gokel and
D. J. Cram, J. Am. Chem. Soc., 96, 7097 (1974).
[6a] F. De Jong, D. N. Reinhoudt, C. J. Smit and R. Huis,
Tetrahedron Letters., 4783, (1976); [b] F. De Jong, D. N. Reinhoudt,
R.Huis, Tetrahedron Letters., 3985, (1977).
[7] Leslie C. Hodgkinson and Ian O. Sutherland, J. Chem. Soc.
Perkin Trans 1., 1908, (1979).
amino)ethoxy]benzene (5.67 g, 15 mmol), Na CO (6.4 g,
2
3
60 mmol) and NaClO •H O (2.12 g, 15 mmol). The product was
4
2
crystallised from CH CN to give 6.28 g (72%) mp 178-180 °C (Lit.
3
[8]: m 176 °C); ir: ν 3061, 3027, 2976, 2909, 2860, 1595, 1513,
-1
1467, 1447, 1377, 1334, 1255, 1229, 1120, 1039, 1022, 777, cm
;
1
H nmr (CDCl ) δ 3.34 (t, J 6.1 Hz, 8H); 4.12 (t, J 6.1 Hz, 8H),
Ph CH2-3.85 (s, 8H); 6.81-7.43 (m, 18H); C nmr (CDCl ): δ 55.8,
3
13
3
60.9, 69.3, 114.3, 122.8, 129.3, 131.0, 142.0, 150.9.
Anal. Calcd. for: C H N O : C, 75.80; H, 7.06; N, 5.20.
34 38
2 4
Found: C, 75.56; H, 7.42; N, 5.46.
N,N'-Didodecyl-7,16-diaza-1,4,10,13-tetraoxa-2,3-benzo-
cyclooctadec-2-ene (6a).
To the mixture of Na CO (20 g, 188.6 mmol) and NaClO .H O
2
3
4
2
(6.74 g, 48.0 mmol) in THF-CH CN (800 ml) 1,2-bis-(2-p-tolyl-
sulphonylethoxy)benzene (24.27 g, 48.0 mmol) and
[8] C. J. Pedersen and M. H. Bromels, U.S. Patent., 3 847 949,
(1974).
3