A convenient synthesis of novel 20-, 23-, and 26-membered macrocyclic oxathiadibenzo- and oxathiadinaphthalenocrown ethers, part 1

Article abstract of DOI:10.1515/znb-2005-0813

A series of novel oxathiadibenzo- and oxathiadinaphthalenocrown ethers 1-18 have been successfully synthesized in good yield and in a simple way. They were characterized by NMR, mass spectroscopy and elemental analysis.

Full text of DOI:10.1515/znb-2005-0813

A Convenient Synthesis of Novel 20-, 23-, and 26-Membered Macrocyclic
Oxathiadibenzo- and Oxathiadinaphthalenocrown Ethers, Part 1
Muhammad Ashram
Chemistry Department, College of Science, Mutah University, Mutah, Al-Karak, Jordan
Reprint requests to Dr. Muhammad Ashram. E-mail: ashram 1961@yahoo.com
Z. Naturforsch. 60b, 891 – 900 (2005); received March 7, 2005
A series of novel oxathiadibenzo- and oxathiadinaphthalenocrown ethers 1 – 18 have been suc-
cessfully synthesized in good yield and in a simple way. They were characterized by NMR, mass
spectroscopy and elemental analysis.
Key words: Fullerenes, Macromolecules, Crown Ethers, Oxathiacrown Ethers
Introduction
might be capable to include fullerenes, we undertook
a program to synthesize new series of large ring size
and deep cavity of crown ethers namely oxathiadiben-
zocrown ethers (1 – 4, 9, 10, 13, 14, 17) and oxathiad-
inaphthalenocrown ethers (5 – 8, 11, 12, 15, 16, 18) in
order to evaluate, in future studies, their potential as
suitable new supramolecular hosts for fullerenes.
It has been shown that molecules of large ring size,
deep cavity and presence of multiple π-π van der
Waals interactions between the electron-rich aromatic
ring(s) and the electron-poor fullerenes are of inter-
est in host-guest fullerene chemistry [4]. Therefore, we
believe that the above crowns and in particular the ones
that contain naphthalene units, could be attractive can-
didates as receptors for C60 or / and C70.
Fullerenes appeared as third generation of carbon
clusters after graphite and diamond [1]. Several meth-
ods have been developed and applied for the separation
of specific size and/or isomers of fullerenes from mix-
tures [2].
The supramolecular (i. e., non-covalent or ionic)
complexation of fullerenes with a variety of macro-
molecule hosts is a subject of extensive ongoing inter-
est [3 – 15]. It has been shown that dibenzo-24-crown-8
forms an inclusion complex with C60 in preference to
C70 [16] while azacrown ethers form a complex with
C70 in preference to C60 [17].
As part of our ongoing research towards developing
and designing new supramolecules [5, 18, 19] that
Scheme 1.
c
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892
M. Ashram · Macrocyclic Oxathiadibenzo- and Oxathiadinaphthalenocrown Ethers
Scheme 2.
Results and Discussion
synthesizing the macrocycles was successful as shown
in Schemes 2, 3 and 4. As shown in Scheme 2, re-
The first synthetic approach investigated towards
thiacrown ethers 1 – 4, 13 and 14 is outlined in
Scheme 1.
The ditosylates 19 and 20 were envisioned as be-
ing suitable precursors to condense with ethane 1,2-
dithiol, bis(2-mercaptoethyl)sulfideor bis(2-mercapto-
ethyl)ether. However all attempts to synthesize the
above crown ethers via this route failed, affording only
resinous products. Fortunately, an alternative route for
action of two equivalents of aldehyde 21 or ester
22 with one equivalent of ethane1,2-dithiol or bis(2-
mercaptoethyl)sulfide in presence of anhydrous potas-
sium carbonate in refluxing anhydrous acetonitrile for
24 h afforded the compounds 23 – 26 in quantitative
yield. Reduction of dialdehydes 23 or 24 with NaBH4
in methanol and diesters 25 or 26 with LiAlH4 in
tetrahydrofuran followed by chlorination with freshly
distilled thionyl chloride in dry benzene at room tem-
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M. Ashram · Macrocyclic Oxathiadibenzo- and Oxathiadinaphthalenocrown Ethers
893
Scheme 3.
perature produced dichlorides 31 – 34 as key precur- General procedure for the synthesis of dialdehydes 23, 24
and 35
sors in very good yield. The syntheses of crown ethers
1 – 8 and 9 – 12 were accomplished by reaction of
dichlorides 31 – 34 with corresponding aliphatic thi-
ols (Scheme 3). Several attempts of final cyclization
of precursors 31 or 32 with an appropriate thiol in
presence of potassium hydroxide and ethanol/benzene
mixture failed to give the expected macrocycles 1, 2,
3 or 4. However, replacement of the ethanol/benzene
solvent mixture by acetonitrile in presence of potas-
sium carbonate at reflux temperature afforded the de-
sired macrocycles 1 – 12 in very good yield. The syn-
In a 100 ml one-necked flask equipped with a magnetic
stirrer bar and a reflux condenser, o-(2-bromoethoxy)benz-
aldehyde 21 (2.0 g, 8.7 mmol), dithiol (4.35 mmol) and an-
hydrous K2CO3 (1.81 g, 13.1 mmol) were mixed with an-
hydrous CH3CN (50 ml). The mixture was refluxed for 24 h
and then allowed to cool to room temperature. The mixture
was filtered and the solid was washed with CHCl3. The com-
bined filtrate was evaporated to dryness to obtain the desired
dialdehydes in nearly quantitative yield.
thetic procedure for crown ethers 13– 18 is the same as 1,14-Diformyl-1,2;13,14-dibenzo-3,12-dioxa-6,9-dithia-
tetradeca-1,13-diene (23)
for crowns 1 – 12 except the use of dichlorides 39 and
40 as key precursors (Scheme 4).
Pale yellow solid. Yield 1.65 g (97%). An analytical sam-
ple was purified by TLC using ethyl acetate/hexane (2:3) as
Experimental Section
◦
eluent. – M. p. 93 – 94 C. – 1H NMR: δ = 2.90 (s, 4 H,
Melting points are uncorrected. 1H NMR and 13C NMR
spectra were recorded on a 200 MHz and 50 MHz NMR
spectrometers, respectively. Unless otherwise noted, sam-
ples were dissolved in CDCl3 using TMS as internal stan-
dard. All reagents were of analytical grade and used with-
out further purification. Chromatographic separations were
carried out on thin layer chromatography (TLC) using silica
gel GF254 (Fluka) or column chromatography using silica
gel columns (60 – 120 mesh, CDH). All reactions were car-
ried out under dry nitrogen. Ditosylates 19 and 20 and o-(2-
bromoethoxy)benzaldehyde 21 were prepared according to
the literature procedures [20].
SCH2CH2S), 3.02 (t, J = 6 Hz, 4 H, SCH2CH2O), 4.22 (t,
J = 6 Hz, 4 H, SCH2CH2O), 6.90 – 7.06 (m, 4 H), 7.52 (t,
J = 3 Hz, 2 H), 7.80 (d, J = 4 Hz, 2 H), 10.48 (s, 2 H,
CHO). – 13C NMR: δ = 30.1, 33.0, 68.6, 113.0, 121.4,
125.0, 128.8, 135.6, 160.6, 189.5 (C=O). – +APCI MS: m/z
[M+1]+ calcd. for C20H22S2O4: 391.1; found 391.2 (25%).
1,17-Diformyl-1,2;16,17-dibenzo-3,15-dioxa-6,9,12-trithia-
heptadeca-1,16-diene (24)
Pale yellow solid. Yield 1.88 g (95%). An analytical sam-
ple was purified by TLC using ethyl acetate/hexane (2:3) as
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894
M. Ashram · Macrocyclic Oxathiadibenzo- and Oxathiadinaphthalenocrown Ethers
Scheme 4.
◦
eluent. – M. p. 71 – 72 C. – 1H NMR: δ = 2.82 (br, 8 H, 1,17-Diformyl-1,2;16,17-dibenzo-3,9,15-trioxa-6,12-dithia-
SCH2CH2SCH2CH2S), 3.04 (t, J = 6 Hz, 4 H, SCH2CH2O), heptadeca-1,16-diene (35)
4.28 (t, J = 6 Hz, 4 H, SCH2CH2O), 6.92 – 7.10 (m, 4 H),
7.55 (t, J = 4 Hz, 2 H), 7.84 (d, J = 4 Hz, 2 H), 10.50 (s,
2 H, CHO). – 13C NMR: δ = 30.0, 32.4, 32.6, 68.2, 112.5,
121.1, 125.2, 128.5, 135.4, 160.1, 189.4 (C=O). – +APCI
MS: m/z [M+1]+ calcd. for C22H26S3O4: 451.1; found
451.2 (65%).
The crude product was purified by column chromatog-
raphy using ethyl acetate/hexane (2:3) as eluent to give a
pale yellow oil. Yield 1.87 g (98%). – H NMR: δ = 2.79
(t, J = 4 Hz, 4 H, OCH2CH2SCH2CH2OAr), 3.02 (t, J =
4 Hz, 4 H, OCH2CH2SCH2CH2OAr), 3.68 (t, J = 4 Hz,
1
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M. Ashram · Macrocyclic Oxathiadibenzo- and Oxathiadinaphthalenocrown Ethers
895
4 H, OCH2CH2SCH2CH2OAr), 4.20 (t, J = 4 Hz, 4 H, Synthesis of methyl 3-(2-bromoethoxy)-2-naphthoate (22)
OCH2CH2SCH2CH2OAr), 6.92 – 7.05 (m, 4 H), 7.50 (t, J =
In a 250 ml one-necked flask equipped with a mag-
4 Hz, 2 H), 7.83 (d, J = 4 Hz, 2 H), 10.48 (s, 2 H, CHO). –
netic stirrer bar and a reflux condenser, methyl 3-hydroxy-
13C NMR: δ = 31.0, 32.1, 69.1, 71.0, 112.6, 121.0, 124.5,
2-naphthoate (10.1 g, 0.05 mol), 1,2-dibromoethane (93.1 g,
128.5, 136.1, 160.6, 189.6 (C=O). – +APCI MS: m/z [M+1]+
0.5 mol) and anhydrous K2CO3 (13.8 g, 0.1 mol) were mixed
calcd. for C22H26S2O5: 435.1; found 435.1 (80%).
with anhydrous CH3CN (500 ml). The mixture was refluxed
for 2 days and then cooled to room temperature, filtered and
the solid was washed with CH3CN. The filtrate was evapo-
General procedure for the synthesis of diols 27, 28 and 37
rated to dryness under reduced pressure. The crude product
was purified by column chromatography on silica gel using
ethyl acetate/hexane (1:4) as eluent to give 22 as a pale yel-
low oil 12.8 g (83%). – 1H NMR: δ = 3.75 (t, J = 6 Hz,
2 H, OCH2CH2Br), 3.99 (s, 3 H, OCH3), 4.46 (t, J = 6 Hz,
2 H, OCH2CH2Br), 7.20 (s, 1 H), 7.41 (t, J = 4 Hz, 1 H),
7.52 (t, J = 4 Hz, 1 H), 7.71 (d, J = 4 Hz, 1 H), 7.82 (d,
J = 4 Hz, 1 H), 8.32 (s, 1 H). – 13C NMR: δ = 28.6, 52.2,
69.0, 109.0, 122.1, 125.0, 127.5, 127.9, 128.0, 128.8, 133.0,
135.9, 154.0, 166.6 (C=O). – +APCI MS: m/z [M+1]+ calcd.
for C14H13BrO3: 309.0; found 309.0 (M+, 100%).
To a solution of dialdehyde (4.44 mmol) in THF (50 ml)
at room temperature was added NaBH4 (0.68 g, 17.8 mmol).
After 10 min the reaction was quenched by adding 5 ml of
cold water followed by aqueous 5% HCl until the solution
becomes acidic to pH paper. The mixture was extracted with
diethyl ether (50 ml). The organic layer was dried over anhy-
drous MgSO4 and then evaporated to afford the diols in high
yield.
1,16-Dihydroxy-2,3;14,15-dibenzo-4,13-dioxa-7,10-dithia-
hexadeca-2,14-diene (27)
Pale yellow semi-solid. Yield 1.76 g (98%). – 1H NMR:
δ = 2.84 (s, 4 H, SCH2CH2S), 2.89 (s, 2 H, OH), 2.98 (t, J =
4 Hz, 4 H, SCH2CH2O), 4.21 (t, J = 4 Hz, 4 H, SCH2CH2O),
4.69 (s, 4 H, ArCH2), 6.82 (d, J = 4 Hz, 2 H), 6.92 (t, J =
4 Hz, 2 H), 7.25 (m, 4 H). – 13C NMR: δ = 31.9, 32.2, 62.2,
67.0, 111.3, 121.2, 128.9, 129.0, 130.0, 156.8. – +APCI MS:
m/z [M+1]+ calcd. for C20H26S2O4: 395.13; found 377.1
(M+-OH, 100%).
General procedure for the synthesis of diesters 25, 26 and 36
In a 250 ml one-necked flask equipped with a mag-
netic stirrer bar and a reflux condenser, methyl 3-(2-
bromoethoxy)-2-naphthoate 22 (3.1 g, 10.0 mmol), di-
thiol [HS(CH2CH2S)nH, n = 1, 2, or (HSCH2CH2)2O]
(5.0 mmol) and anhydrous K2CO3 (10.0 mmol) were mixed
with anhydrous CH3CN (150 ml). The mixture was refluxed
for 24 h and then allowed to cool to room temperature. The
mixture was filtered and the solid was washed with CH3CN.
The combined filtrate was evaporated to dryness to obtain the
desired diesters in nearly quantitative yield.
1,19-Dihydroxy-2,3;17,18-dibenzo-4,16-dioxa-7,10,13-tri-
thianonadeca-2,17-diene (28)
The crude product was washed with benzene to give a
colorless solid. Yield 1.8 g (94%). – M. p. 75 – 76.5 C. –
1,14-Di-(methoxycarbonyl)-1,2;13,14-dinaphthaleno-3,12-
dioxa-6,9-dithiatetradeca-1,13-diene (25)
◦
1H NMR: δ = 2.81 (br, 8 H, SCH2CH2SCH2CH2S), 2.98
(t, J = 4 Hz, 4 H, SCH2CH2O), 4.21 (t, J = 4 Hz, 4 H,
SCH2CH2O), 4.69 (s, 4 H, Ar-CH2), 6.88 (d, J = 4 Hz,
2 H), 6.97 (t, J = 4 Hz, 2 H), 7.18 – 7.33 (br, 4 H). –
13C NMR: δ = 31.5, 32.1, 32.2, 61.9, 66.5, 111.1, 121.0,
128.4, 128.5, 129.0, 156.1. – +APCI MS: m/z [M+1]+ calcd.
for C22H30S3O4: 455.13; found 437.2 (M+-OH, 100%).
The crude product was washed with diethyl ether to
give a pale yellow solid. Yield 2.7 g (98%). – M. p. 108 –
109.5 ◦C. – 1H NMR: δ = 2.99 (s, 4 H, SCH2CH2S), 3.06 (t,
J = 5 Hz, 4 H, SCH2CH2OAr), 3.92 (s, 6 H, OCH3), 4.31
(t, J = 5 Hz, 4 H, SCH2CH2OAr), 7.20 (s, 2 H), 7.39 (t,
J = 4 Hz, 2 H), 7.51 (t, J = 4 Hz, 2 H), 7.70 (d, J = 4 Hz,
2 H), 7.81 (d, J = 5 Hz, 2 H), 8.30 (s, 2 H). – 13C NMR:
δ = 31.0, 32.0, 52.5, 69.1, 108.4, 121.6, 124.9, 127.5, 127.7,
128.5, 128.6, 133.0, 136.0, 154.9, 166.5. – +APCI MS: m/z
[M+1]+ calcd. for C30H30S2O6: 551.15; found 349 (M+-
C12H9O3, 21%).
1,19-Dihydroxy-2,3;17,18-dibenzo-4,10,16-trioxa-7,13-di-
thianonadeca-2,17-diene (37)
Colorless oil. Yield 1.9 g (97%). – 1H NMR: δ = 2.78
(t, J = 6 Hz, 4 H, OCH2CH2SCH2CH2OAr), 3.0 (t, J =
6 Hz, 4 H, OCH2CH2SCH2CH2OAr), 3.66 (t, J = 6 Hz,
4 H, OCH2CH2SCH2CH2OAr), 4.21 (t, J = 6 Hz, 4 H,
OCH2CH2SCH2CH2OAr), 4.69 (s, 4 H, ArCH2), 6.85 (d,
J = 4 Hz, 2 H), 6.95 (t, J = 4 Hz, 2 H), 7.19 – 7.31 (m, 4 H). –
1,17-Di-(methoxycarbonyl)-1,2;16,17-dinaphthaleno-3,15-
dioxa-6,9,12-trithiaheptadeca-1,16-diene (26)
The crude product was purified by column chromatogta-
13C NMR: δ = 31.9, 32.0, 62.1, 67.0, 71.0, 111.0, 120.8, phy using ethyl acetate/hexane (3:7) as eluent to give a color-
128.6, 129.0, 129.5, 156.4. – +APCI MS: m/z [M+1]+ calcd. less solid. Yield 2.51 g (81%). – M. p. 80 – 81 ◦C. – 1H NMR:
for C22H30S2O5: 439.15; found 421.2 (M+-OH, 100%).
δ = 2.88 (br, 8 H, SCH2CH2SCH2CH2S), 3.05 (t, J = 4 Hz,
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M. Ashram · Macrocyclic Oxathiadibenzo- and Oxathiadinaphthalenocrown Ethers
4 H, SCH2CH2OAr), 3.93 (s, 6 H, OCH3) 4.30 (t, J = 5 Hz, 8 H, SCH2CH2SCH2CH2S), 2.71 (t, J = 3 Hz, 4 H,
4 H, SCH2CH2OAr), 7.18 (s, 2 H), 7.37 (t, J = 5 Hz, 2 H), SCH2CH2OAr), 4.05 (t, J = 3 Hz, 4 H, SCH2CH2OAr),
7.50 (t, J = 5 Hz, 2 H), 7.57 (d, J = 5 Hz, 2 H), 7.80 (d, 4.41 (d, J = 2 Hz, 4 H, ArCH2), 5.02 (br, 2 H, OH), 7.08
J = 6 Hz, 2 H), 8.30 (s, 2 H). – 13C NMR: δ = 30.9, 32.1, (s, 2 H), 7.10 – 7.22 (m, 4 H), 7.53 – 7.61 (m, 4 H), 7.65
32.3, 52.2, 68.8, 108.0, 121.5, 124.6, 126.2, 127.5, 127.9, (s, 2 H). – 13C NMR [D6]-DMSO: δ = 31.0, 32.5, 32.6,
128.0, 132.5, 136.0, 154.5, 166.5 (C=O). – +APCI MS: m/z 58.9, 68.2, 106.2, 124.1, 125.6, 126.0, 126.9, 128.0, 128.9,
[M+1]+ calcd. for C32H34S3O6: 611.15; found 409.1 (M+- 132.7, 133.5, 154.4. – +APCI MS: m/z [M+1]+ calcd. for
C12H9O3,100%).
C30H34S3O4: 555.16; found 537.1 (M+- OH, 100%).
1,17-Di-(methoxycarbonyl)-1,2;16,17-dinaphthaleno-3,9,
15-trioxa-6,12-dithiaheptadeca-1,16-diene (36)
1,19-Dihydroxy-2,3;17,18-dinaphthaleno-4,10,16-trioxa-
7,13-dithianonadeca-2,17-diene (38)
Golden oil. Yield 2.88 g (98%). – 1H NMR: δ = 2.87
(t, J = 4 Hz, 4 H, OCH2CH2SCH2CH2OAr), 3.04 (t, J =
3 Hz, 4 H, OCH2CH2SCH2CH2OAr), 3.70 (t, J = 4 Hz,
4 H, OCH2CH2SCH2CH2OAr), 3.95 (s, 6 H, OCH3), 4.30
(t, J = 4 Hz, 4 H, OCH2CH2SCH2CH2OAr), 7.20 (s, 2 H),
7.39 (t, J = 3 Hz, 2 H), 7.54 (t, J = 3 Hz, 2 H), 7.71 (d,
J = 4 Hz, 2 H), 7.80 (d, J = 4 Hz, 2 H), 8.29 (s, 2 H). –
13C NMR: δ = 31.5, 32.1, 52.1, 69.0, 71.0, 108.0, 122.0,
124.9, 126.6, 127.8, 128.2, 128.5, 132.8, 135.9, 154.3, 166.8
(C=O). – +APCI MS: m/z [M+1]+ calcd. for C32H34S2O7:
595.17; found 393.1 (M+-C12H9O3, 100%).
Colorless solid. Yield 2.18 g (91%). – M. p. 103 –
104 ◦C. – 1H NMR [D6]-DMSO: δ = 2.89 (t, J =
4
Hz, 4 H, OCH2CH2SCH2CH2OAr), 3.10 (t, J =
4 Hz, 4 H, OCH2CH2SCH2CH2OAr), 3.71 (t, J = 4 Hz,
4 H, OCH2CH2SCH2CH2OAr), 4.35 (t, J = 3 Hz, 4 H,
OCH2CH2SCH2CH2OAr), 4.76 (d, J = 2 Hz, 4 H, ArCH2),
5.34 (t, J = 2 Hz, 2 H, OH), 7.39 (s, 2 H), 7.41 – 7.56 (m,
4 H), 7.85 – 7.92 (m, 4 H), 7.96 (s, 2 H). – 13C NMR [D6]-
DMSO: δ = 31.3, 31.8, 59.0, 68.6, 70.1, 106.5, 124.5, 126.0,
126.7, 127.1, 128.0, 129.0, 132.9, 133.8, 154.8. – +APCI
MS: m/z [M+1]+ calcd. for C30H34S2O5: 539.18; found
521.2 (M+- OH, 100%).
General procedure for the synthesis of diols 29, 30 and 38
General procedure for the synthesis of dichlorides 31 – 34
and 39 – 40
To a suspension of LiAlH4 (0.34 g, 8.9 mmol) in an-
hydrous THF (100 ml) was added a solution of diester
(4.45 mmol) in anhydrous THF (50 ml) at room tempera-
ture. The reaction mixture was stirred for 5 – 10 min and
then was quenched by adding the mixture into wet diethyl
ether (250 ml) at 0 ◦C. The mixture was then acidified with
aqueous 5% HCl. The organic layer was separated and the
aqueous layer was extracted with diethyl ether (100 ml). The
combined organic layers were dried over anhydrous MgSO4
and evaporated to give the product.
To a solution of diol (1.08 mmol) in anhydrous ben-
zene (150 ml) was added freshly distilled SOCl2 (0.24 ml,
3.2 mmol). The reaction mixture was stirred at room temper-
ature for 0.5 – 1.5 h and then was quenched by adding 20 ml
of cold water. The organic layer was washed with water until
the aqueous layer was neutral to pH paper. The organic layer
was dried over anhydrous MgSO4 and evaporated to give the
product.
1,16-Dihydroxy-2,3;14,15-dinaphthaleno-4,13-dioxa-7,10-
dithiahexadeca-2,14-diene (29)
1,16-Dichloro-2,3;14,15-dibenzo-4,13-dioxa-7,10-dithia-
hexadeca-2,14-diene (31)
Pale yellow solid. Yield 2.0 g (91%). – M. p. 139 –
140 ◦C. – 1H NMR [D6]-acetone: δ = 2.99 (s, 4 H,
SCH2CH2S), 3.11 (t, J = 3 Hz, 4 H, SCH2CH2OAr), 4.20 (t,
J = 2 Hz, 2 H, OH), 4.34 (t, J = 4 Hz, 4 H, SCH2CH2OAr),
4.58 (d, J = 2 Hz, 4 H, ArCH2), 7.29 (s, 2 H), 7.30 – 7.48
(m, 6 H), 7.80 (t, J = 3 Hz, 2 H), 7.92 (s, 2 H). – 13C NMR
[D6]-acetone: δ = 33.6, 31.6, 60.1, 68.9, 106.5, 124.5, 125.0,
126.6, 127.5, 128.4, 128.8, 132.4, 133.1, 155.0. – +APCI
MS: m/z [M+1]+ calcd. for C28H30S2O4: 495.16; found
477.2 (M+- OH, 100%).
Colorless solid. Yield 0.38 g (81%). – M. p. 91 – 92 ◦C. –
1H NMR: δ = 2.89 (s, 4 H, SCH2CH2S), 3.00 (t, J = 3 Hz,
4 H, SCH2CH2OAr), 4.20 (t, J = 4 Hz, 4 H, SCH2CH2OAr),
4.66 (s, 4 H, ArCH2), 6.85 – 7.00 (m, 6 H), 7.35 (t, J = 3 Hz,
2 H). – 13C NMR: δ = 31.5, 33.1, 41.5, 68.5, 112.1, 121.1,
126.0, 130.5, 131.0, 156.0. – +APCI MS: m/z [M+1]+ calcd.
for C20H24S2O2Cl2: 431.06; found 395.1 (M+-Cl, 100%).
1,19-Dichloro-2,3;17,18-dibenzo-4,16-dioxa-7,10,13-tri-
thianonadeca-2,17-diene (32)
1,19-Dihydroxy-2,3;17,18-dinaphthaleno-4,16-dioxa-7,10,
13-trithianonadeca-2,17-diene (30)
The crude product was washed with diethyl ether to give
a pale yellow solid. Yield 0.39 g (74%). – M. p. 54 – 55 ◦C. –
Colorless solid. Yield 2.4 g (98%). – M. p. 142 – 1H NMR: δ = 2.81 (br, 8H, SCH2CH2SCH2CH2S), 2.98
143 ◦C.
–
1H NMR [D6]-DMSO: δ = 2.60 (br, (t, J = 3 Hz, 4 H, SCH2CH2OAr), 4.20 (t, J = 3 Hz, 4 H,
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M. Ashram · Macrocyclic Oxathiadibenzo- and Oxathiadinaphthalenocrown Ethers
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SCH2CH2OAr), 4.65 (s, 4 H, ArCH2), 6.86 – 7.10 (m, 4 H), 4 Hz, 4 H, OCH2CH2SCH2CH2OAr), 3.62 (t, J = 4 Hz,
7.28 – 7.40 (m, 4 H). – 13C NMR: δ = 31.7, 32.4, 33.0, 42.0, 4 H, OCH2CH2SCH2CH2OAr), 4.35 (t, J = 3 Hz, 4 H,
68.5, 112.0, 121.2, 126.1, 130.0, 130.6, 157.0. – +APCI MS: OCH2CH2SCH2CH2OAr), 4.88 (s, 4 H, ArCH2), 7.40 (s,
m/z [M+1]+ calcd. for C22H28S3O2Cl2: 491.06; found 455.1 2 H), 7.33 – 7.51 (m, 4 H), 7.79 – 7.87 (m, 4 H), 7.96
(M+-Cl, 100%).
(s, 2 H). – 13C NMR [D6]-DMSO: δ = 31.2, 31.9, 42.7,
68.8, 71.0, 107.8, 124.8, 127.0, 127.4, 127.8, 128.2, 128.4,
131.0, 135.0, 154.5. – +APCI MS: m/z [M+1]+ calcd. for
C30H32S2O3Cl2: 575.12; found 538.2 (M+- Cl, 100%).
1,16-Dichloro-2,3;14,15-dinaphthaleno-4,13-dioxa-7,10-
dithiahexadeca-2,14-diene (33)
Pale yellow solid. Yield 0.43 g (75%). – M. p. 104 –
General procedure for the synthesis of the crown ethers
1 – 18
◦
105 C. – 1H NMR: δ = 2.99 (s, 4 H, SCH2CH2S), 3.08
(t, J = 3 Hz, 4 H, SCH2CH2OAr), 4.34 (t, J = 3 Hz, 4 H,
SCH2CH2OAr), 4.79 (s, 4 H, ArCH2), 7.14 (s, 2 H), 7.30 –
7.50 (m, 4 H), 7.66 – 7.78 (m, 4 H), 7.82 (s, 2 H). – 13C NMR:
δ = 31.1, 32.9, 42.1, 68.6, 105.8, 124.1, 126.5, 127.0, 128.0,
130.1, 131.0, 132.7, 133.3, 154.9. – +APCI MS: m/z [M+1]+
calcd. for C28H28S2O2Cl2: 531.1; found 495.0 (M+- Cl,
100%).
Macrocycles 1 – 18 were synthesized under high dilution
employing in modified form cyclization procedure of Buter
and Kellogg [21]. In a 250 ml three-necked flsask equipped
with a magnetic stirrer bar and a reflux condenser and a gas
line to maintain a nitrogen atmosphere, anhydrous K2CO3
(0.54 g, 3.9 mmol) was suspended in anhydrous CH3CN
(150 ml). To this well-stirred solution at reflux temperature
was added a solution containing dithiol [HS(CH2CH2S)nH,
n = 1, 2 or (HSCH2CH2)2O] (1.3 mmol) and dichloride
31−34, 39, 40 (1.3 mmol) in anhydrous CH3CN (50 ml or
3 ml of DMF + 47 ml of CH3CN in the case of dichloride
33, 34 and 40) was added drop wise over a period of 10 –
12 h. The reaction mixture was further refluxed with stirring
for another 12 h. The reaction mixture was filtered and the
filtrate was evaporated. The residue was dissolved in CHCl3
(100 ml) and washed with H2O. The organic layer was dried
over anhydrous MgSO4 and then evaporated. The purifica-
tion was carried out as indicated by the entries below for the
separate compounds.
1,19-Dichloro-2,3;17,18-dinaphthaleno-4,16-dioxa-7,10,
13-trithianonadeca-2,17-diene (34)
Pale yellow solid. Yield 0.46
g (73%). – M. p.
94 – 95 ◦C. – 1H NMR [D6]-DMSO: δ = 2.62 (br,
8 H, SCH2CH2SCH2CH2S), 2.80 (t, J = 3 Hz, 4 H,
SCH2CH2OAr), 4.08 (t, J = 3 Hz, 4 H, SCH2CH2OAr),
4.61 (s, 4 H, ArCH2), 7.18 (s, 2 H), 7.08 – 7.28 (m, 4 H),
7.55 – 7.62 (m, 4 H), 7.74 (s, 2 H). – 13C NMR [D6]-DMSO:
δ = 31.0, 32.2, 32.6, 42.9, 68.9, 107.5, 124.9, 127.1, 127.5,
127.8, 128.2, 128.6, 130.9, 134.8, 154.2. – +APCI MS:
m/z [M+1]+ calcd. for C30H32S3O2Cl2: 591.1; found 556.1
(M+- Cl, 46%).
2,3;10,11-Dibenzo-1,12-dioxa-5,8,15,18-tetrathiacyclo-
eicosane-2,10-diene (1)
1,19-Dichloro-2,3;17,18-dibenzo-4,10,16-trioxa-7,13-di-
thianonadeca-2,17-diene (39)
The crude product was purified by column chromatogra-
phy using ethyl acetate/hexane (1.5:8.5) as eluent to give 1
as a colorless solid. Yield 0.31 g (53%). – M. p. 78 – 79 ◦C. –
1H NMR: δ = 2.77 (s, 4 H, SCH2CH2S), 2.98 (s, 4 H,
SCH2CH2S), 3.10 (t, J = 3 Hz, 4 H, SCH2CH2O), 3.80 (s,
4 H, ArCH2), 4.21 (t, J = 3 Hz, 4 H, SCH2CH2O), 6.85 (d,
J = 4 Hz, 2 H), 6.95 (t, J = 3 Hz, 2 H), 7.18 – 7.30 (m, 4 H). –
13C NMR: δ = 30.6, 31.5, 32.0, 33.2, 69.0, 112.0, 121.6,
127.2, 128.6, 130.6, 156.4. – +APCI MS: m/z [M+1]+ calcd.
for C22H28S4O2: 453.09; found 453.2 (100%). – Analysis
for C22H28S4O2: calcd. C 58.37, H 6.23, S 28.33; found
C 58.29, H 6.20, S 28.39.
The crude product was purified by column chromato-
graphy using ethyl acetate/hexane (1:4) to give a color-
less oil. Yield 0.36 g (71%). – 1H NMR: δ = 2.84 (t,
J = 3 Hz, 4 H, OCH2CH2SCH2CH2OAr), 3.00 (t, J =
4 Hz, 4 H, OCH2CH2SCH2CH2OAr), 3.70 (t, J = 3 Hz,
4 H, OCH2CH2SCH2CH2OAr), 4.21 (t, J = 4 Hz, 4 H,
OCH2CH2SCH2CH2OAr), 4.75 (s, 4 H, ArCH2), 6.89 (d,
J = 3 Hz, 2 H), 6.96 (t, J = 3 Hz, 2 H), 7.29 (d, J = 2 Hz,
2 H) 7.37 (t, J = 2 Hz, 2 H). – 13C NMR: δ = 31.0, 31.5,
41.2, 68.0, 70.1, 111.5, 120.1, 129.5, 130.0, 156.4. – +APCI
MS: m/z [M+1]+ calcd. for C22H28S2O3Cl2: 476.09; found
476.1 (M+, 80%).
2,3;13,14-Dibenzo-1,15-dioxa-5,8,11,18,21-pentathiacyclo-
1,19-Dichloro-2,3;17,18-dinaphthaleno-4,10,16-trioxa-7,
tricosane-2,13-diene (2)
13-dithianonadeca-2,17-diene (40)
Colorless solid. Yield 0.42 g (67%). – M. p. 61 –
The crude product was purified by TLC using ethyl ac-
62 ◦C. – 1H NMR [D6]-DMSO: δ = 2.85 (t, J = etate/hexane (1:4) as eluent to give 2 as a colorless solid.
4
Hz,
4
H, OCH2CH2SCH2CH2OAr), 3.02 (t, J = Yield 0.26 g (39%). – M. p. 105 – 106 ◦C. – 1H NMR:
Unauthenticated
Download Date | 6/27/17 6:49 AM

898
M. Ashram · Macrocyclic Oxathiadibenzo- and Oxathiadinaphthalenocrown Ethers
δ = 2.67 (br, 8 H, SCH2CH2SCH2CH2S), 2.94 (s, 4 H, 553.13; found 553.0 (100%). – Analysis for C30H32S4O2:
SCH2CH2S), 3.05 (t, J = 4 Hz, 4 H, SCH2CH2O), 3.82 (s, calcd. C 65.18, H 5.83, S 23.20; found C 65.11, H 5.76,
4 H, ArCH2 ), 4.20 (t, J = 4 Hz, 4 H, SCH2CH2O), 6.86 (d, S 23.10.
J = 3 Hz, 2 H), 6.95 (t, J = 3 Hz, 2 H), 7.16 – 7.32 (m, 4 H). –
2,3;13,14-Dinaphthaleno-1,15-dioxa-5,8,11,18,21-penta-
thiacyclotricosane-2,13-diene (6)
13C NMR: δ = 30.0, 32.0, 32.1, 33.2, 33.4, 68.3, 111.6,
121.5, 127.0, 128.3, 131.0, 156.1. – +APCI MS: m/z [M+1]+
calcd. for C24H32S5O2: 513.1; found 513.2 (100%). – Anal-
ysis for C24H32S5O2: calcd. C 56.21, H 6.29, S 31.26; found
C 56.11, H 6.21, S 31.19.
The crude product was washed with benzene to give 6 as a
pale brown solid. Yield 0.48 g (61%). – M. p. 145 – 146 ◦C. –
1H NMR: δ = 2.75 (br, 8 H, SCH2CH2SCH2CH2S), 3.00
(s, 4 H, SCH2CH2S), 3.11 (t, J = 3 Hz, 4 H, SCH2CH2O),
3.94 (s, 4 H, ArCH2 ), 4.31 (t, J = 3 Hz, 4 H, SCH2CH2O),
7.13 (s, 2 H), 7.31 – 7.48 (m, 4 H), 7.68 – 7.74 (m, 4 H), 7.78
(s, 2 H). – 13C NMR: δ = 30.2, 31.3, 32.0, 32.2, 33.5, 68.5,
106.3, 124.1, 125.2, 125.4, 127.3, 128.6, 128.8, 129.6, 133.8,
154.6. – +APCI MS: m/z [M+1]+ calcd. for C32H36S5O2:
613.13, found 613.2 (100%). – Analysis for C32H36S5O2:
calcd. C 62.71, H 6.09, S 26.15; found C 62.80, H 5.88,
S 26.21.
2,3;10,11-Dibenzo-1,12-dioxa-5,8,15,18,21-pentathiacyclo-
tricosane-2,10-diene (3)
The crude product was purified by TLC using ethyl ac-
etate/hexane (1:4) as eluent to give 3 as a colorless solid.
Yield 0.29 g (44%). – M. p. 85 – 86 ◦C. – 1H NMR: δ = 2.75
(s, 4 H, SCH2CH2S), 2.92 (br, 8 H, SCH2CH2SCH2CH2S),
3.00 (t, J = 3 Hz, 4 H, SCH2CH2O), 3.79 (s, 4 H, ArCH2),
4.19 (t, J = 3 Hz, 4 H, SCH2CH2O), 6.88 (d, J = 3 Hz,
2 H), 6.94 (t, J = 3 Hz, 2 H), 7.18 – 7.28 (m, 4 H). –
2,3;10,11-Dinaphthaleno-1,12-dioxa-5,8,15,18,21-penta-
13C NMR: δ = 30.5, 31.5, 31.8, 32.9, 33.2, 69.0, 112.0, thiacyclotricosane-2,10-diene (7)
121.3, 127.8, 129.0, 131.0, 156.5. – +APCI MS: m/z [M+1]+
The crude product was purified by column chromatogra-
calcd. for C24H32S5O2: 513.1; found 513.2 (100%). – Anal-
ysis for C24H32S5O2: calcd. C 56.21, H 6.29, S 31.26; found:
C 56.27, H 6.35, S 31.32.
phy using CHCl3 as eluent to give ◦7 as a colorless solid. Yield
0.49 g (63%). – M. p. 136 – 138 C. – 1H NMR: δ = 2.79
(s, 4 H, SCH2CH2S), 2.92 (br, 8 H, SCH2CH2SCH2CH2S),
3.02 (t, J = 3 Hz, 4 H, SCH2CH2O), 3.90 (s, 4 H, ArCH2),
4.29 (t, J = 3 Hz, 4 H, SCH2CH2O), 7.08 (s, 2 H), 7.18 – 7.45
(m, 4 H), 7.61 – 7.71 (m, 6 H). – 13C NMR: δ = 31.0, 31.4,
32.0, 32.9, 33.1, 68.8, 106.8, 124.0, 126.2, 126.6, 127.5,
128.8, 129.0, 129.2, 134.0, 154.8. – +APCI MS: m/z [M+1]+
calcd. for C32H36S5O2: 613.13; found 613.0 (100%). – Anal-
ysis for C32H36S5O2: calcd. C 62.71, H 5.92, S 26.15; found
C 62.67, H 5.81, S 26.09.
2,3;13,14-Dibenzo-1,15-dioxa-5,8,11,18,21,24-hexathia-
cyclohexacosane-2,13-diene (4)
The crude product was washed with diethyl ether
to give
(39%).
4
as
a
pale yellow solid. Yield 0.29
g
–
M. p. 103 – 104.5 ◦C.
–
1H NMR: δ =
2.69 (br, 8 H, SCH2CH2SCH2CH2S), 2.88 (br, 8 H,
SCH2CH2SCH2CH2S), 3.00 (t, J = 3 Hz, 4 H, SCH2CH2O),
3.79 (s, 4 H, ArCH2), 4.20 (t, J = 3 Hz, 4 H, SCH2CH2O),
6.83 (d, J = 2 Hz, 2 H), 6.94 (t, J = 3 Hz, 2 H), 7.15 –
7.30 (m, 4 H). – 13C NMR: δ = 30.1, 31.4, 32.0, 32.2, 32.6,
33.0, 68.8, 112.0, 121.3, 127.5, 128.5, 130.6, 157.0. – +APCI
MS: m/z [M+1]+ calcd. for C26H36S6O2: 573.1; found 573.2
(100%). – Analysis for C26H36S6O2: calcd. C 54.51, H 6.33,
S 33.57; found C 54.41, H 6.26, S 33.48.
2,3;13,14-Dinaphthaleno-1,15-dioxa-5,8,11,18,21,24-hexa-
thiacyclohexacosane-2,13-diene (8)
The crude product was washed with benzene to give 8 as
a colorless solid. Yield 0.56 g (64%). – M. p. 156 – 158 ◦C. –
1H NMR: δ = 2.74 (br, 8 H, SCH2CH2SCH2CH2S), 2.91
(br, 8 H, SCH2CH2SCH2CH2S), 3.08 (t, J = 3 Hz, 4 H,
SCH2CH2O), 3.92 (s, 4 H, ArCH2), 4.30 (t, J = 3 Hz, 4 H,
SCH2CH2O), 7.11 (s, 2 H), 7.32 – 7.48 (m, 4 H), 7.63 –
7.75 (m, 6 H). – 13C NMR: δ = 30.8, 31.4, 32.1, 32.2,
32.5, 33.1, 68.8, 106.8, 124.0, 126.2, 126.4, 127.6, 128.5,
128.7, 129.6, 133.7, 154.2. – +APCI MS: m/z [M+1]+ calcd.
for C34H40S6O2: 673.13, found 673.0 (100%). – Analysis
for C34H40S6O2: calcd. C 60.68, H 5.99, S 28.58; found
C 60.77, H 6.11, S 28.45.
2,3;10,11-Dinaphthaleno-1,12-dioxa-5,8,15,18-tetrathia-
cycloeicosane-2,10-diene (5)
The crude product was washed with diethyl ether to give
5 as ◦a pale yellow solid. Yield 0.34 g (48%). – M. p. 135 –
136 C. – 1H NMR: δ = 2.85 (s, 4 H, SCH2CH2S), 3.05
(s, 4 H, SCH2CH2S), 3.08 (t, J = 3 Hz, 4 H, SCH2CH2O),
3.96 (s, 4 H, ArCH2), 4.35 (t, J = 3 Hz, 4 H, SCH2CH2O),
7.10 (s, 2 H), 7.30 – 7.45 (m, 4 H), 7.60 – 7.72 (m, 4 H),
7.74 (s, 2 H). – 13C NMR: δ = 31.5, 31.8, 32.8, 33.5, 69.0,
106.9, 124.2, 126.5, 126.8, 127.8, 128.7, 129.0, 129.9, 133.9,
2,3;13,14-Dibenzo-1,8,15-trioxa-5,11,18,21-tetrathiacyclo-
tricosane-2,13-diene (9)
The crude product was washed with benzene to give
155.0. – +APCI MS: m/z [M+1]+ calcd. for C30H32S4O2: 9 as a colorless solid. Yield 0.30 g (47%). – M. p.
Unauthenticated
Download Date | 6/27/17 6:49 AM

M. Ashram · Macrocyclic Oxathiadibenzo- and Oxathiadinaphthalenocrown Ethers
899
83 – 84 ◦C. – 1H NMR: δ = 2.70 (t, J = 3 Hz, 4 H, J = 4 Hz, 4 H, OCH2CH2SCH2CH2OAr), 2.91 (br,
OCH2CH2SCH2CH2OAr), 2.98 (s, 4 H, SCH2CH2S), 3.05 8 H, SCH2CH2SCH2CH2S), 3.08 (t, J = 3 Hz, 4 H,
(t, J = 3 Hz, 4 H, OCH2CH2SCH2CH2OAr), 3.64 (t, J = OCH2CH2SCH2CH2OAr), 3.68 (t, J = 4 Hz,
4 H,
4 Hz, 4 H, OCH2CH2SCH2CH2OAr), 3.81 (s, 4 H, ArCH2 OCH2CH2SCH2CH2OAr), 3.99 (s, 4 H, ArCH2), 4.31
), 4.20 (t, J = 3 Hz, 4 H, OCH2CH2SCH2CH2OA), 6.86 (d, (t, J = 3 Hz, 4 H, OCH2CH2SCH2CH2OAr), 7.12 (s,
J = 4 Hz, 2 H), 6.92 (t, J = 4 Hz, 2 H), 7.14 – 7.30 (m, 4 H). – 2 H), 7.29 – 7.48 (m, 4 H), 7.70 (br, 4 H), 7.72 (s, 2 H). –
13C NMR: δ = 30.5, 31.2, 31.5, 33.4, 68.6, 70.6, 112.1, 13C NMR: δ = 31.0, 31.2, 32.8, 33.0, 68.9, 70.8, 106.9,
121.3, 127.6, 128.8, 130.9, 156.2. – +APCI MS: m/z [M+1]+ 124.0, 126.2, 126.5, 127.6, 128.9, 129.3, 154.3. – +APCI
calcd. for C24H32S4O3: 497.12, found 497.2 (100%). – Anal- MS: m/z [M+1]+ calcd. for C34H40S5O3: 657.16; found
ysis for C24H32S4O3: calcd. C 58.03, H 6.49, S 25.82; found 657.2 (100%). Analysis for C34H40S5O3: calcd. C 62.16,
C 58.12, H 6.40, S 25.91.
H 6.14, S 24.40; found C 62.28, H 6.17, S 24.51.
2,3;10,11-Dibenzo-1,12,18-trioxa-5,8,15,21-tetrathiacyclo-
tricosane-2,10-diene (13)
2,3;13,14-Dibenzo-1,8,15-trioxa-5,11,18,21,24-pentathia-
cyclohexacosane-2,13-diene (10)
The crude product was purified by TLC using ethyl
acetate/hexane (1:4) as eluent to give 13 as pale yel-
low solid. Yield 0.25 g (38%). – M. p. 74 – 75 ◦C. –
1H NMR: δ = 2.71 (s, 4 H, SCH2CH2S), 2.88 (t, J =
3 Hz, 4 H, OCH2CH2SCH2CH2OAr), 3.02 (t, J = 3 Hz,
4 H, OCH2CH2SCH2CH2OAr), 3.75 (t, J = 3 Hz, 4 H,
OCH2CH2SCH2CH2OAr), 3.78 (s, 4 H, ArCH2), 4.18 (t,
J = 3 Hz, 4 H, OCH2CH2SCH2CH2OAr), 6.82 (d, J = 4 Hz,
2 H), 6.91 (t, J = 4 Hz, 2 H), 7.12 – 7.25 (m, 4 H). –
13C NMR: δ = 30.0, 31.4, 31.6, 31.9, 68.8, 71.5, 112.0,
121.0, 127.4, 128.5, 131.0, 156.2. – +APCI MS: m/z [M+1]+
calcd. for C24H32S4O3: 497.12; found 497.2 (100%). – Anal-
ysis for C24H32S4O3: calcd. C 58.03, H 6.49, S 25.82; found
C 58.15, H 6.56, S 25.93.
The crude product was purified by TLC using ethyl ac-
etate/hexane (1:4) as eluent to give 10 as a pale yellow
◦
solid. Yield 0.48 g (66%). – M. p. 72 – 73 C. – 1H NMR:
δ = 2.70 (t, J = 4 Hz, 4 H, OCH2CH2SCH2CH2OAr),
2.90 (br, 8 H, SCH2CH2SCH2CH2S), 3.09 (t, J = 3 Hz,
4 H, OCH2CH2SCH2CH2OAr), 3.62 (t, J = 4 Hz, 4 H,
OCH2CH2SCH2CH2OAr), 3.82 (s, 4 H, ArCH2), 4.22 (t,
J = 3 Hz, 4 H, OCH2CH2SCH2CH2OAr), 6.85 (d, J = 3 Hz,
2 H), 6.92 (t, J = 3 Hz, 2 H), 7.12 – 7.28 (m, 4 H). –
13C NMR: δ = 31.0, 31.2, 31.8, 32.5, 33.0, 68.9, 70.5, 112.0,
121.0, 127.5, 128.1, 130.5, 157.0. – +APCI MS: m/z [M+1]+
calcd. for C26H36S5O3: 557.13; found 557.2 (100%). – Anal-
ysis for C26H36S5O3: calcd. C 56.08, H 6.52, S 28.79; found
C 56.20, H 6.61, S 28.91.
2,3;13,14-Dibenzo-1,15,21-trioxa-5,8,11,18,24-pentathia-
cyclohexacosane-2,13-diene (14)
2,3;13,14-Dinaphthaleno-1,8,15-trioxa-5,11,18,21-tetra-
thiacyclotricosane-2,13-diene (11)
The crude product was purified by TLC using ethyl
acetate/hexane (1:4) as eluent to give 14◦as pale yellow
solid. Yield 0.27 g (37%). – M. p. 68 – 69 C. – 1H NMR:
δ = 2.64 (br, 8 H, SCH2CH2SCH2CH2S), 2.85 (t, J =
3 Hz, 4 H, OCH2CH2SCH2CH2OAr), 3.20 (t, J = 3 Hz,
4 H, OCH2CH2SCH2CH2OAr), 3.71 (t, J = 4 Hz, 4 H,
OCH2CH2SCH2CH2OAr), 3.81 (s, 4 H, ArCH2), 4.16 (t,
J = 3 Hz, 4 H, OCH2CH2SCH2CH2OAr), 6.82 (d, J =
2 Hz, 2 H), 6.92 (t, J = 2 Hz, 2 H), 7.12 – 7.29 (m, 4H). –
13C NMR: δ = 30.0, 31.9, 32.0, 32.2, 32.3, 68.1, 71.2, 111.8,
121.2, 127.5, 128.6, 130.9, 156.0. – +APCI MS: m/z [M+1]+
calcd. for C26H36S5O3: 557.13; found 557.2 (100%). – Anal-
ysis for C26H36S5O3: calcd. C 56.08, H 6.52, S 28.79; found
C 56.15, H 6.59, S 28.87.
The crude product was washed with diethyl ether to
give 11 as pale yellow solid. Yield 0.43 g (55%). – M. p.
◦
152 – 153.5 C. – 1H NMR: δ = 2.75 (t, J = 3 Hz, 4 H,
OCH2CH2SCH2CH2OAr), 3.00 (s, 4 H, SCH2CH2S), 3.11
(t, J = 3 Hz, 4 H, OCH2CH2SCH2CH2OAr), 3.64 (t, J =
4 Hz, 4 H, OCH2CH2SCH2CH2OAr), 3.96 (s, 4 H, ArCH2),
4.30 (t, J = 4 Hz, 4 H, OCH2CH2SCH2CH2OAr), 7.10
(s, 2 H), 7.46 – 7.52 (m, 4 H), 7.68 (br, 4 H), 7.70 (s,
2 H). – 13C NMR: δ = 30.9, 31.2, 32.6, 33.0, 68.5, 70.5
107.0, 123.8, 126.1, 126.3, 127.2, 128.6, 128.7, 128.9, 133.7,
154.6. – +APCI MS: m/z [M+1]+ calcd. for C32H36S4O3:
597.15; found 597.2 (100%). – Analysis for C32H36S4O3:
calcd. C 64.39, H 6.08, S 21.49; found C 64.31, H 6.17,
S 21.61.
2,3;10,11-Dinaphthaleno-1,12,18-trioxa-5,8,15,21-tetra-
thiacyclotricosane-2,10-diene (15)
2,3;13,14-Dinaphthaleno-1,8,15-trioxa-5,11,18,21,24-
pentathiacyclohexacosane-2,13-diene (12)
The crude product was washed with benzene to give 15
as a pale yellow solid. Yield 0.53 g (68%). – M. p. 115 –
The crude product was washed with diethyl 116 ◦C. – 1H NMR: δ = 2.78 (s, 4 H, SCH2CH2S), 2.90 (t,
ether to give 12 as a colorless solid. Yield 0.61 g J = 3 Hz, 4 H, OCH2CH2SCH2CH2OAr), 3.10 (t, J = 3 Hz,
(72%). – M. p. 98 – 99.5 ◦C. – 1H NMR: δ = 2.75 (t, 4 H, OCH2CH2SCH2CH2OAr), 3.79 (t, J = 3 Hz, 4 H,
Unauthenticated
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900
M. Ashram · Macrocyclic Oxathiadibenzo- and Oxathiadinaphthalenocrown Ethers
OCH2CH2SCH2CH2OAr), 3.91 (s, 4 H, ArCH2), 4.30 (t, Yield 0.27 g (38%). – M. p. 54 – 55 ◦C. – 1H NMR: δ = 2.69
J = 4 Hz, 4 H, OCH2CH2SCH2CH2OAr), 7.08 (s, 2 H), (t, J = 3 Hz, 4 H), 2.90 (t, J = 3 Hz, 4 H), 3.01 (t, J = 3 Hz,
7.28 – 7.45 (m, 4 H), 7.62 – 7.75 (br, 6 H). – 13C NMR: δ = 4 H), 3.61 (t, J = 3 Hz, 4 H), 3.72 (t, J = 4 Hz, 4 H), 3.81
31.0, 31.2, 32.0, 68.9, 71.4 106.6, 124.0, 126.0, 126.3, 127.5, (s, 4 H, ArCH2), 4.18 (t, J = 3 Hz, 4 H), 6.81 (d, J = 2 Hz,
128.9, 129.0, 129.8, 133.9, 154.4. – +APCI MS: m/z [M+1]+ 2 H), 6.90 (t, J = 2 Hz, 2 H), 7.18 (d, J = 2 Hz, 2 H), 7.23
calcd. for C32H36S4O3: 597.15; found 597.1 (100%). – Anal- (t, J = 2 Hz, 2 H). – 13C NMR: δ = 31.2, 32.0, 32.9, 33.0,
ysis for C32H36S4O3: calcd. C 64.39, H 5.99, S 21.49; found 69.9, 71.5, 72.3, 113.0, 122.4, 128.8, 129.5, 130.6, 157.7. –
C 64.46, H 6.01, S 21.57.
+APCI MS: m/z [M+1]+ calcd. for C26H36S4O4: 541.13;
found 541.2 (100%). – Analysis for C26H36S4O4: calcd.
C 57.74, H 6.71, S 23.71; found C 57.65, H 6.66, S 23.63.
2,3;13,14-Dinaphthaleno-1,15,21-trioxa-5,8,11,18,24-
pentathiacyclohexacosane-2,13-diene (16)
2,3;13,14-dinaphthaleno-1,8,15,21-tetraoxa-5,11,18,24-
The crude product was washed with benzene to give 16 as
a colorless solid. Yield 0.37 g (43%). – M. p. 133 – 135 ◦C. –
1H NMR: δ = 2.69 (br, 8 H, SCH2CH2SCH2CH2S), 2.89 (t,
J = 3 Hz, 4 H, OCH2CH2SCH2CH2OAr), 3.09 (t, J = 3 Hz,
4 H, OCH2CH2SCH2CH2OAr), 3.72 (t, J = 3 Hz, 4 H,
OCH2CH2SCH2CH2OAr), 3.90 (s, 4 H, ArCH2), 4.29 (t,
J = 3 Hz, 4 H, OCH2CH2SCH2CH2OAr), 7.10 (s, 2 H),
7.28 – 7.42 (m, 4 H), 7.69 (br, 6 H). – 13C NMR: δ = 30.8,
31.8, 32.1, 68.1, 71.4, 106.5, 124.0, 126.5, 126.6, 127.5,
128.8, 128.9, 129.7, 133.9, 154.5. – +APCI MS: m/z [M+1]+
calcd. for C34H40S5O3: 657.16; found 657.2 (100%). – Anal-
ysis for C34H40S5O3: calcd. C 62.16, H 6.14, S 24.40; found
C 62.11, H 6.09, S 24.48.
tetrathiacyclohexacosane-2,13-diene (18)
The crude product was washed with diethyl ether to give
18 as a pale yellow solid. Yield 0.63 g (76%). – M. p. 79 –
◦
80 C. – 1H NMR: δ = 2.72 (t, J = 3 Hz, 4 H), 2.90 (t,
J = 3 Hz, 4 H), 3.09 (t, J = 3 Hz, 4 H), 3.60 (t, J = 3 Hz,
4 H), 3.75 (t, J = 4 Hz, 4 H), 3.94 (s, 4 H, ArCH2), 4.29
(t, J = 3 Hz, 4 H), 7.09 (s, 2 H), 7.25 – 7.42 (m, 4 H),
7.66 (br, 6 H). – 13C NMR: δ = 31.0, 31.1, 31.3, 32.0,
68.8, 70.9, 71.2, 116.9, 124.0, 126.1, 126.5, 127.5, 128.6,
128.8, 129.5, 133.8, 154.9. – +APCI MS: m/z [M+1]+ calcd.
for C34H40S4O4: 641.18; found 641.2 (100%). – Analysis
for C34H40S4O4: calcd. C 63.72, H 6.29, S 20.01; found
C 63.80, H 6.23, S 20.11.
2,3;13,14-Dibenzo-1,8,15,21-tetraoxa-5,11,18,24-tetrathia-
cyclohexacosane-2,13-diene (17)
Acknowledgement
I thank Ms. Linda Winsor at Memorial University of New-
foundland, Canada for recording the mass spectra reported
The crude product was purified by TLC using ethyl ac-
etate/hexane (1:4) as eluent to give 17 as pale yellow solid. herein.
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