liNTRODUCTION OBJECTIVES AND INVESTIGATIONS...
Transcript of liNTRODUCTION OBJECTIVES AND INVESTIGATIONS...
3 SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACALIXARENE SYNTHESIS
ABSTRACT
liNTRODUCTION
2 OBJECTIVES AND INVESTIGATIONS
3 EXPERIMENTAL
3.1 SYNTHESIS AND CHARACTERIZATION
3.1.1 CAux[n]ARENES (CnAs, n=4-8) 2n
3.1.1.1 p-tert-BUTYLCALIX[ 4 )ARENE
3.1.1.2 p-tert-BUTYLCALIX[5)ARENE
3.1.1.3 p-tert-BUTYLCALIX[6]ARENE
3.1.1.4 p-tert-BUTYLCALIX[7]ARENE
3.1.1.5 p-tert-BUTYLCALIX[8]ARENE
3.1.2 2-CHLOROALKYL-ETHERS OF CALJX(n]ARENES 3n
3.1.3 2-CHLOROALKYL-(p-tert-BUTYL)PHENYL ETHER 6
3.1.4 CAux[n]ARENE-(p-tert-BUTYL)PHENYL 1,2-DIETHERS 4n
3.1.5 CALIX(n]ARENE-THIACALIX(n)ARENE PSEUDO DIMERS Sn
3.1.6 HALO-DE-ALKOXYLATION OF Sn
3.1.7 A BRIEF DISCUSSION ON CONFORMATIONAL PREFERENCES OF Sn
4 CONCLUSION
REFERENCES
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SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACALIXARENE SYNTHESIS
Abstract
The trend in supramolecular chemistry till date has been the synthesis of novel receptors
and subsequent exploration of their possible applications. As evident from literature, the
number of publications concerning the synthesis {not derivatization) of thiacalixarenes has
reached a plateau. Present chapter demonstrates a simple and versatile approach for the
synthesis of various thiacalixarene homologs, and hence, we hope, may rejuvenate the
chemistry of this exciting class of supramolecules. The modularity of the strategy permits
its adaptation to produce variety of other supramolecular assemblies like carcerands and a
plethora of other heteracalixarenes.
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SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACAUXARENE SYNTHESIS
liNTRODUCTION
Heteracalixarenes (HCnAs, n=4-8 represents number of phenyl units in the macrocycle,
(Figure 3.1), the hetero-atom bridged metacyclophens, have earned significant interest in
the last decade by virtue of their structural similarities with calixarenes 2n (CnAs), but with
much superior complexing abilities.l1·3l The main hurdle in the evolution of
heteracalixarene chemistry is their synthesis, especially, of higher HCnAs, which are not
easily accessible generally.l4l In this chapter, we demonstrate an intuitive strategy to
synthesize various thiacalixarene homologs ln (TCnAs-sulfur bridged heteracalixarenes),
via respective calixarene templates.
Since the first practicable synthesis of TCnAs,l5l
there has been very few successful reports on the
subject.IG-11) Previously (Chapter 2}, we have
investigated microwave assisted reactions,
yielding ls-s in minor yields.l12l No reports for
synthesis of ls-s (especially for ls and l1) in substantial yields are available so far. To
understand the problem on hand in its correct perspective, it would be appropriate to
briefly review the chemistry of thiacalixarene synthesis. As has been reported earlier, the
template effect is not so pronounced in the case of TCnA synthesis, as compared to CnAs.
l1-3,5l In case of CnA synthesis, the number of aromatic units in the product macrocycle
depends largely on the template ion used as base catalyst.l13lln the presence of NaOH, the
predominant product is 24, while, if KOH is used, the product is a mixture of 26 and 2s.
Further, odd member CnAs (2s, 27) are achievable as byproducts in synthetically useful
yields, which is not the case with TCnAs, where such products are generally obtained in
trace amounts. The reason being, stringent thermodynamic requirements for the
cyclization of acyclic oligo-phenolsulfide intermediates whose fate depends upon their
thermodynamic stability, and hence end up as 14-the most thermodynamically stable
product amongst all TCnAs.l5l This was further evident from our recent investigations
(Chapter 2) of thiacalixarene synthesis protocoJ.14•12l Though significant success was
achieved in the synthesis of higher TCnAs (ls-s), the optimized methods required much
more rigorous maintenance of reaction conditions, and thus not viable for large scale
synthesis.
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SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACALIXARENE SYNTHESIS
2 OBJECTIVES AND INVESTIGATION
One way to prepare higher TCnAs in good yields is to search for better templates {a partly
successful approach).l6-11l However, a more appropriate approach would be, to pre
organize individual phenol units according to required geometry and then add sulfur
bridges between them, thereby removing the possibility of uncontrollable oligomerization
completely. Pre-organizing many phenol units may seem a daunting task at first, which
may not be possible practically except via templation or better true complexation.
However, if the phenol units are restricted to move within certain limits, it may essentially
serve the same purpose. In practice, the restriction was imposed upon the phenol units by
anchoring them covalently on fixed scaffolds, namely, calixarenes, and thus, were brought
into a state of pre-organization.
!~,,:·, ~~rq~:;~%{;
. ~v1~'t;l!WJ:i;f¥l
~,~~t{:~~-~e,~i~~~~sr~~~l1~~~~i5~ It was also required by this strategy tHat; after anchoring the pHenol units to the calixarene
scaffold, the calix should retain/acquire a cone conformation, otherwise, cyclization {via
complete sulfurization) to form a macrocycle would be impossible. Two pathways were
employed to anchor phenol units on a calixarene scaffold {Scheme 3.1). The first approach
was to append an ethylchloride chain on 2n {Route A-by reacting with 1-chloro-2-
bromoethane) and react p-tert-butylphenol with the available chloride of 3n. While
successful in case of 4 and partly for 2s, the approach failed to secure the cone
conformation in case of higher CnAs {26-s) due to small size of appended chain, which was
unable to restrict the flip-flop motion of the calix-framework,113l and hence a mixture of
conformers was obtained, separable only through tedious column chromatography. The
second approach was to utilize template effect of CnAs towards alkali metal ions and
directly attach pre-formatted Ph-0-Et- chains on CnAs {Route B-by reaction with 6). This
approach was greatly successful on a wide range for 24-7, and partly for 2s. Beyond 28, the
cavity size becomes too large and hence, the restriction of the flip-flop motion of the
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SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACALIXARENE SYNTHESIS
calixarene-framework becomes too tough to accomplish.
Having pre-organized the phenol units, the next step would be to add sulfur bridges
between the appended phenol units. However, the traditional 'elemental su/fur-NaOH
heating' method would not work satisfactorily in this case, reason being, the sulfurization
process involves a keto intermediate,14l which in turn requires a free phenolic -OH, not
available in 4n. Indeed, direct sulfurization of 4n with this approach yielded a very small
amount of completely sulfurized products Sn, along with a diverse consortium of mono
sulfurized to poly sulfurized products, as detected by UPLC-MS analysis of the reaction
mixture after completion of the reaction. Though 5n were detected in the reaction
mixture, it was not possible to isolate them, and hence a better method was required for
sulfurization. An already known sulfurization technique is the one using SCh, which was
coincidently used for the first synthesis of 14 in a step-wise manner.114l In present case,
sulfurization of 4n with SCb gave excellent results in all the cases, and CnA-TCnA pseudo
dimers 5n were obtained in good yields. Compound 54 has already been prepared by
reacting tetra-((2-tosyl}-ethyl}ether of calix[4]arene with thiacalix[4]arene. Conformational
preferences of various 54 derivatives and their comparative study with bis(calix[4]arenes}
has also been reported.l15l The 1HNMR spectra of all variants 54-s showed similar
unrestrained structuresJl&-zo)
The final step to achieve the TCnA derivatives was exhaustive halo-de-alkoxylation121l of 5n
in aqueous ethanol using lil, to cleave the ether linkages between two macrocycles (1n &
2n}, followed by their chromatographic separation or fractional crystallization (based on
differential solubility}. As can be inferred from the data listed in Table 3.1, all TCnA variants
have been achieved in very decent yields, and though being a multi-step synthesis,
satisfactory overall yields promise its application on relatively larger scales. Further, the
CnA templates may be recuperated with high overall% recovery ranging from ca. 60-75%.
Present strategy, viz. pre-organization of individual aromatic units with the help of other
a~~,Wi:t~t~~rj~t~~~~r~g!~\"~~~~{~r~~~~,~t~::~~i~~~l"g:~~,~~E!~~~~~,~::: ·.7c''
similar assembly and subsequent cyclization to produce pseudo dimers, is modular in a
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SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACALIXARENE SYNTHESIS
sense that it can be applied to synthesize other supramolecular assemblies of calix family
in numerous ways. A complimentary approach has been successfully demonstrated by
Gale et. al.,l22,23) whereby, to manifest calix[4/S]pyrroles, four/five ketone functions
{bridging units) were appended to the calix[4/S]arene scaffold and pyrroles {aromatic
units) were inserted afterwards. For instance, the strategy can be extended {a) to prepare
various heteracalixarenes, with hetero-atom bridges other than sulfur, by employing
different reagents for cyclization of appended phenol units {b) to synthesize TCnA
derivatives with various p-substitutions {for which cyclization is not possible via direct
sulfurization), as long as they are sufficiently activating to permit m-substitution. It may be
noticed that 5 possesses a carcerand type structure, and thus, this approach can be
employed to produce some more exciting carcerands as well.
It may be noticed here that some of the calix[n]arene templates {especially the odd
numbered homologs) are themselves not very easy to prepare {and thus expensive),
therefore it is highly desirable to recover the unreacted/partially reacted templates. In this
regard, two strategies can be employed. That is, either to recover the unreacted fraction at
the end of each step and hydrolyze them appropriately, or collect unreacted fractions of all
steps and proceed with the hydrolysis. Both the strategies were tested and gave equally
satisfactory results, however, from practical view point the latter strategy is beneficial. In
practice, all the residual fractions {including solid residues, washings, mother liquor of
crystallization etc.) were collected and evaporated to dryness under vacuum. The solid/
semi-solid residue obtained was then washed/triturated with hexane and evaporated to
dryness to give solid powder. The powder was washed with warm aq. ethanol {10%, v/v) to
remove inorganic salts. The final residue was then subjected to alkaline hydrolysis with aq.
NaOH/KOH {2M) or halo-de-alkoxy/ation under reflux conditions followed by usual work
up. The purification was carried out by crystallization or column chromatography. For the
sake of obtaining a clear picture of quantitative recovery, the results of recovery {%) of
calix[S]arene for all individual steps {in a complete reaction cycle) have been summarized
in Table 3.2 as a representative example. Overall % recovery of 2s is ca. 70% in this case.
Similarly, the % recovery ranges from ca. 60-75% for different homologs, which is very
good for a four step reaction. % Recoveries are calculated on the basis of initial amount of
2s derivative reacted in each step.
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SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACALIXARENE SYNTHESIS
3 EXPERIMENTAL
All the reagents used were of AR grade, procured from Sigma-Aldrich. The reagents were
used without further purification. The solvents were dried appropriately wherever
required. Melting points were taken in a single capillary tube using Toshniwal melting point
apparatus and are uncorrected. EA was carried out on Heraeus CarloEbra 1108 elemental
analyzer. NMR spectra were recorded on Bruker DPX-400 AVANCE in CDCh with
tetramethylsilane as internal standard. Liquid chromatography was conducted on Waters
Acquity UPLC system (Milford, MA, USA) with Waters analytical column, type UPLC BEH Cts
reversed phase (lOOmm long and 2.1mm internal diameter with 1.7Sj..lm particle size)
maintained at 40°C, mobile phase composition was methanoi:O.Ol% acetic acid (90:10, v/
v). Waters Oasis HlB solid phase extraction cartridges (30j..lm) were used for extraction.
Mass measurements were done on Waters, ·Quattro Premier XE (Milford, MA, USA),
equipped with electrospray ionization and operating in positive ionization mode.
3.1 SYNTHESIS AND CHARACTERIZATION
3.1.1 CAux[n]ARENES (CnAs, n=4-8) 2n
Calix[n]arenes were prepared by established procedures (Scheme 3.2).124-25)
3.1.1.1 p-tert-BUTYLCALIX[ 4 ]ARENE
lOg (66mmol) of p-tert-butylphenol was mixed with
lOml of 3N NaOH and 9. 7g of 37% formaldehyde
solution. The mixture was heated at 50-SSOC for 4-Sh and
then at 110-120°C for 2h to give a yellow solid. This was
stirred with lOOml of lN HCI for lh to neutralize the P;~~~~ ' /i:f'Jt?:;{b'(~~";,..,; ~o,-.;:;.,~:~)i_
2 ~·· n>
base, and the solid was removed by filtration, washed ~~i~-q~~~:~t4~~~~';
with water, and dried in an oven at 110-120°C for 30min. This material was mixed with 70g
of diphenyl ether and heated to 210-220°( for 2h. The reaction mixture was cooled,
treated with 150ml of ethyl acetate, and filtered to yield 5.47g of a white solid. This
material was treated with 75ml of toluene, heated at reflux for 30min, and filtered hot to
remove insoluble higher oligomers. Upon cooling, the toluene solution deposited crystals
which were recrystallized from toluene to give 2.75g (25%) of p-tert-butylcalix[4]arene.
3.1.1.2 p-tert-BUTYLCALIX[S]ARENE
A mixture of 22.50g (lSOmmol) of p-tert-butylphenol, lS.Og (37.5mmol) of paraformal
dehyde, 4.50g (40mmol) of potassium tert-butoxide, and 300ml of tetraline was stirred
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SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACALIXARENE SYNTHESIS
mechanically for 6h at 55°( in a 1l three-necked round-bottomed flask equipped with a
Dean-Stark trap. The temperature was then raised to 150°C and maintained for 6h, with
mechanical stirring. The product mixture was cooled to room temperature, and 900ml of
CHCI3 was added. The insoluble polymer that precipitated was removed by filtration after
2h. The CHCh solution was washed sequentially with 300ml of a 5% aqueous NaOH
solution, 300ml of 5% HCI, and 300ml of water and dried (anhydrous Na2S04) for 24h. The
solution was then concentrated under reduced pressure {1mm Hg). The residue was
triturated with 150ml of absolute ethanol at 40°C. The ethanol solution was found to
contain five components by TLC (silica). After the solution was allowed to stand for 48h at
0°C, 4.3g of a solid product precipitated from the ethanol solution. Thin-layer
chromatography revealed that the solid was a mixture of two compounds. Column
chromatography of the crude product, which was soluble in the hot iso-propyl alcohol,
with 100g of silica gel, afforded 2.06g of pure p-tert-butylcalix[5]arene, yield 6.1%.
3.1.1.3 p-tert-BUTYLCALIX[6]ARENE
A slurry of 10.0g (0.066 mol) of p-tert-butylphenol, 4.0g {133mmol) of paraformaldehyde,
and 6ml of 5N RbOH in 100ml of xylene was refluxed in an inert atmosphere with efficient
stirring for 4h in a 500ml flask equipped with a Dean and Stark collector. The cooled
reaction mixture was filtered, and the solid obtained was suspended in 300ml of CHCb,
and shaken with 100ml of 1N HCI. The organic layer was separated, washed with water,
dried over anhydrous Na2S04, and concentrated to 100ml. Addition of methanol caused
the precipitation of a solid, which was removed by filtration to give 7.85g (73%) colorless
product. Recrystallization from CHCI3 produced a white solid with the melting point of
380-381°(.
3.1.1.4 p-tert-BUTYLCALIX(7]ARENE
A 1-l three-necked round-bottomed flask equipped with a mechanical stirrer, condenser,
and Dean-Stark trap was charged with 180g (1.20mol) of p-tert-butylphenol, 72g (2.40mol)
of paraformaldehyde, 600ml of 1,4-dioxane, and 13.50g (240mmol) of KOH dissolved in
6ml of water. The heterogeneous mixture was refluxed under a nitrogen atmosphere for
30h, with efficient mechanical stirring. After the mixture was cooled to room temperature
and 30ml of 8M HCI was added, the solvents were removed under reduced pressure. The
crude product was then triturated successively, with 600ml of water (12h) and 1l of
methanol (6h), dissolved in 1.1l of CHCb, and dried over anhydrous Na2S03, for 24h. After
addition of 450ml of methanol, the solution was allowed to remain at ooc for 24h,
resulting in the crystallization of white solid, removed by filtration. The filtrate was
62
SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACALIXARENE SYNTHESIS
concentrated under reduced pressure to 1.3l and 450ml of methanol then added. Further
crystallization at ooc for 24h furnished an additional white substance, removed by
filtration. The filtrate was concentrated, diluted with methanol, and allowed to crystallize
in the same manner for additional two times. Purification of these combined fractions by
column chromatography (two times) with silica afforded G.llg {3.7%} of p-tert-butylcalix
[7]arene, MP 248-2Src.
3.1.1.5 p-tert-BUTYLCALIX(8]ARENE
A slurry of 27.8g {0.18mol) p-tert-butylphenol, 9.0g {0.30mol) paraformaldehyde, and
0.4ml 10N KOH in 150ml of xylene was refluxed in an inert atmosphere with efficient
stirring for 4h in a SOOml flask equipped with a Dean-Stark water collector. After 30min all
of the solid had gone into solution, and after 1h a white precipitate began to separate. The
reaction mixture was refluxed for 4h, cooled, and filtered. The solid product was washed,
in succession with 100ml portions of toluene, ether, acetone and water and was then
dried and recrystallized from CHCI3 to afford 20.4g (64%) of the p-tert-butylcalix[B]arene as
colorless, glistening needles:MP 411-412°C.
3.1.2 2-CHLOROALKYL-ETHERS OF CALIX(n)ARENES 3n
2n (2Smmol) was suspended in dry acetone
(SOOml) containing anhydrous alkali carbonate
(nx3.75mmol) and 1,2-chlorobromo-ethane
(nxSOmmol). The mixture was heated under
reflux for 6-14h. After cooling, the solid resi
due was filtered and extracted thrice with di
chloromethane. The combined filtrates were evaporated under vacuum to remove. From
the solid residue containing the mixture of conformational isomers, the cone isomer 3n
was separated by fractional crystallization from ethanol-chloroform (4:1, v/v) solution
(Scheme 3.3). Yields are summarized in Table 3.3.
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SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACALIXARENE SYNTHESIS
34:Colorless prisms (from CHCI3) MP >3oo·c, MS m/z 900 (M+1), 1HNMR (300 MHz, CDCh):6 1.19 (s,
36H,But), 6.41 (s, 8H, Ar-H), 3.24 & 4.66 (d, 8H, ArCH2Ar, j=12.6), 4.35 & 4.18 (t, OCH2CHzCI), 13CNMR (75 MHz, CDCh):6 31.6 (But), 32.6 (ArCHzAr), 43.1 (CHzCI), 75.0 (OCHz), 135.9, 143.1, 160.7 (Ar), EA Calc. for
CszHGs04CI4 (C:69.48, H:7.62), Found (C:69.40, H:7.59).
lHNMR Data for 34
8 7
4.40
1 rl ... \1)
0 0
6
BCNMR Data for 3 ..
r- r-iO\O'IoOM
0 MlOII')O'\U') \1) ~MMNN rl ..................... ..-t
I I y \ I
I I I 170 150 130
4.30 ppm
\1)
U) .., \1) ...
"' rl
4.20
rl rl rl
5 4 ppm
0
U)
r-
1
... "'
3
3.25
2
I
"' rl
0 0
"'
110 90 80 70 60 50 40 30 20 10 ppm
0
0
Current Data Parameters NAME Octll 2006 EXPNO 11 PROCNO
F2 - Acquisition Parameters Oat• 20061013 TiMe 2. 31 IN STRUM spect PROBHD 5 .. PABBO BB-
PULPROG ~q30
TD 32168 SOLVENT CDC13 NS 3200 DS SWH 10330.578 Hz
riDERS 0.366732 Hz
AQ 1. 5900832 RG 179 DW 48.400 DE 6. 00 TE 299.8 K
Dl 1. 00000000 TDO
CHANNEL fl --------NUCl 1H
Pl 10.65 PL1 0.00 dB
SFOl 300.1330875 MHZ
F2 - Processnq Paraaeters sr 32768 SF 300.1300000 MHZ
NOW EM
SSB 0 LB 0. 30 Hz
GB 0 PC 1. 00
Current Data Paraaeters NAME Oct13 2006 EXPNO 23 PROCNO 1
F2 ... Acquisition Para•eters Date 20061013 Time 3.37 IN STRUM
PROBHD PULPROG TD SOLVENT NS DS SWH FIDERS AQ
RG DW DE TE D1 dll DELTA TDO
NUCl P1 PL1 SFOl
spect 5 •• PABBO BB-
19PCJ30 32768 CDC13
3000
29761.904 Hz 0. 8979536 Hz
0. !>969723 210
16.800 6.00
299.8 K 2. 00000000 0. 03000000 1. 89999998
1
CHANNEL fl .............. .. 13C
7. 80 0.00 dB
75.7703643 MHZ
•••••••• CHANNEL f2 --------CPDPRG2 waltzl6 NUC2 1H PCPD2 80.00 PL12 11. so dB PL13 11. so dB
PL2 0.00 dB
SF02 300.1320005 MHZ
F2 - Processng Parameters SI 32168 SF 15.7518790 MHZ
WDW EM SSB 0 LB 1. 00 Hz
GB 0 PC 1. 40
64
SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACALIXARENE SYNTHESIS
3s:MP >300"C, MS m/z 1125 (M+1), 1HNMR (300 MHz, CDCh) 6 1.18 (s, 36H,Bu1), 6.49 (s, 8H, Ar-H), 3.66 &
5.58 (d, 8H, ArCH2Ar, j=12.5), 4.37 & 4.14 (t, OCH2CH2CI), 13CNMR (75 MHz, CDCh) 6 31.1 (Bu1), 32.7 (ArCH2Ar), 43.1 (CH2CI), 74.8 (OCH2), 135.9, 143.3, 159.9 (Ar), EA Calc. for <=GsHssOsCis (C:69.48, H:7.62),
Found (C:69.35, H:7.56).
lHNMR Data for 3s
Current Data ParaMeters NAME Octl3 2006 EXPNO ,.
... ... co PROCNO 1 M ..... ..... ... F2 - Acquisition Para111eters
Date 20061013 -co
~ Jlk_ "' Time 2.57
A _a IN STRUM spect PROBHD 5 mm PABBO 88-
PULPROG zg30 TO 32768
/ SOLVENT CDC13
5.6 4.4 4.1 3.7 NS 3200
ppm OS 4 SWH 10330.578 Hz
FIDERS 0.355582 Hz
AQ 1. 7233946
I I I RG 180
_r ow 48.400
DE 6.00 TE 300.0 K
"' Dl 1. 00000000 ... TOO
"' CHANNEL fl --------... ... NUCl lH M .....
Pl 10.65 co ... "' PLl o.oo dB
"' "' f l ~ 1
SFOl 300.1330875 MKZ
J; !! T' F2 - Processng Parameters 0 ... ..... 51 32768 0 0 "' "' 0 0 SF 300.1300000 MKz
N "' wow EM
SSB 0
LB 0.30 Hz
GB 8 7 6 5 4 3 2 0 PC 1.00
ppm
13CNMR Data for 3s Current Data Paraaeters
"' C""''0\0'\0M NAME Octll 2006 co ......tNr"'-...-tr-41""1
"' MLOIIlO\LO EXPNO 25
"' o::rMP\NN ... MLON...-t....t..-1 PROCNO ..... .... r-4 .-1..-t r-t ... ~MMMMM
I I y \ I I '-.'-.!::::,.,"+-" F2 - Acquisition Para•etera Data 20061013 -Time 3 .sa IN STRUM spect PROBHD 5 •• PABBO BB-
PULPROG ZC}pg30
TD 32768
SOLVENT CDC13 NS 3000 OS 4 SWH 29761.904 Hz
FIDERS 0.9032895 Hz
AQ 0.6134749
RG 209 OW 16.800 DE 6.00 TE 299.9 K
Dl 2. 00000000
dll 0. 03000000 DELTA 1. 89999998
TOO 1
CHANNEL fl --------NOCl 13C Pl 1.80 PLl 0 .oo dB
SFOl 15.1703643 MHZ
CHANNEL f 2 •••••••• CPDPRG2 waltzl6 NUC2 lH PCPD2 80.00 PL12 17. so dB
PL13 11. so dB
PL2 o. 00 dB
SF02 300. 1320005 MHZ
F2 - Processng Parameters SI 32768 SF 75.7578790 MHZ
NOW EM SSB 0 LB 1.00 Hz GB 0
170 150 130 110 90 80 70 60 50 40 30 20 10 0 PC 1. 40
ppm
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SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACALIXARENE SYNTHESIS
3.1.3 2-CHLOROALKYL-(p-tert-BUTYL)PHENYL ETHER 6
p-tert-Butylphenol (100mmol) was suspended
in dry acetone (SOOml) containing a 1.5 fold
excess of anhydrous KzC03 (150mmol) and two
fold excess of 1,2-chlorobromoethane (200
mmol). The mixture was heated under reflux
for 4 h. After cooling, the solid residue was ~~11f~Y?*~~1;: ~~ert~~~~t
filtered and extracted with dichloromethane three times. The combined filtrates were
evaporated under vacuum to remove solvents. The solid residue was crystallized from
CHCI3, Yield 89% (Scheme 3.4).
6:1HNMR (300 MHz, CDCh):6 7.50 (s, 2H, Ar-H), 6.92 (s, 2H, Ar-H, j=7.50), 1.34 (s, 9H, t-Bu), 4.23 (s, 2H,
OCH2), 4.12 (s, 2H, CH2CI, j=7.70), 13CNMR (75 MHz, CDCh):6 31.3, 34.2 (But), 125.4, 114. 7, 142.9, 156.6 (Ar),
75.2 (OCH2), 43.1) (CH2CI) I ESI MS:m/z 214 (M+1), EA Calc. for c12H170CI (C:67.76, H:8.06), Found (C:67.69, H
8.09).
lHNMR Spectrum of 6
6.95 4.25 4.15 ppm
I I }( ....
0 N ~ ., "' ...
f f u I I !! 0 ": 00\
N N N..,
8 7 6 5 4 3 2 ppm
3.1.4 CAux[n]ARENE-(p-tert-BUTYL)PHENYL 1,2-DJETHERS 4n
... ....
...
N
"' 00
1
Current Data Paraaeters NAME Octl2 2006
EXPNO 8
PROCNO 1
F2 - Acquisition Para•eters Date_ 20061012 Ti111e 3. 31 INSTRUM spect PROBHO 5 mm PABBO BB-
PULPROG !:930
TO 32168 SOLVENT CDC13 NS 3200 OS • SKH 10330.578 •• FIDERS 0.369452 .. AQ 1. 6342901 sec RG 183
•• 48.400 usee DE 6. 00 usee TE 300.2 • 01 1. 00000000 sec TOO 1
•••••••• CHANNEL fl •••••••• NUCl lH Pl 10.65 usee PLl 0.00 dB SFOl 300.1330875 MH~
F2 - Processnq Parameters Sl 32768 SF 300.1300000 MHZ WOW EM SSB 0 LB 0.30 Hz GB D
0 PC 1. 00
Route A:A mixture of 3n (2Smmol) and p-tert-butylphenol (nxSOmmol) was suspended in
dry acetone (SOOmL) containing anhydrous alkali carbonate (nx37.Smmol). The mixture
was heated under reflux for 10-24h. After cooling, the solid residue was filtered and
washed with CHzCh (SOmL) three times. The combined filtrates were evaporated under
vacuum to remove solvents. The product was crystallized from chloroform (Scheme 3.5).
66
BCNMR Spectrum of 6
"' a. ..; N
"' ... .... .... I I
I I I I I
170 150
I
...... "'"' "'"' .... .... y
I I
130
01:1&~
Ai¥h .. ~ >: .
. . '
r-r-...... ........ ........ y
I I I
110
SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACALIXARENE SYNTHESIS
Current Data Para•eter.s NAME Oct:l2 2006
N r-fNP'lM(I") EXPNO 13 ...; M"=r'.-tr-f.-t PROCHO 1 r- VMMMM
I I ........~ F2 - Acquisition Parameter., Date 20061002 -Ti•e 4 .11 INSTRUH spect PROBHD 5 •• PABBO BB-
POLPROG zgpCJ30
TD 32168
SOLVENT CDC13
NS 3000
DS SWR 29761.904 Hz
FIDERS 0.9197351 Hz
•o 0.6253191
RG 208 DW 16.800 usee
DE 6. 00 usee
TE 300.1 • Dl 2. 00000000 ... dll 0. 03000000 ... DELTA 1. 8!U99998 ... TOO 1
.................. CHANNEL f1 --------NUCl 13C
P1 1. 80 usee PL1 0. 00 dB
SFOl 75.7703643 MHZ
................ CHANNEL f2 --------CPDPRG2 waltzl6 NUC2 1R
PCPD2 80.00 use<: PL12 17. so dB
PLll 17. so dB
PL2 0.00 dB
SF02 300.1320005 MRz
F2 - Procesang Parameters SI 32768 SF 75.7578790 ""' wow EM
SSB LB 1.00 ••
I I I I I I GB 0
90 80 70 60 50 40 30 20 10 0 PC 1.40
ppm
(SOOml) containing anhydrous alkali carbonate (nx38mmol) and heated under reflux for
10-24h. After cooling, the solid residue was filtered and CH2Ch soluble fraction was
separated by extraction, cone conformer 4n was obtained by crystallization from CHCh.
67
SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACALIXARENE SYNTHESIS
44 :Yield 82%. 1HNMR (300 MHz, CDCJ3):8 7.10, 7.50 (s, 8H, Ar-H), 0.82, 0.85, 1.33 (s, 72H, t-Bu), 6.32, 6.96 (s,
8H, Ar-H), 4.35, 5.43(m, 16H, OCH2CH20, j=7.7), 3.24, 4.66 (d, 16H, ArCH2Ar, j=12.5}, 13CNMR (75 MHz,
CDCJ3):8 30.8, 31.8, 34.1, 36.5 (Bu1), 133.6, 135.8, 144.2, 161.5 (Ar), 72.1, 75.0 (OCH2CH20), 31.9 (ArCH2Ar),
MS:m/z 1353 (M+1), EA Calc. for C92H12oOs (C:81.61, H:8.93), Found (C:81.61, H:8.80).
tHNMR Spectrum of 44
,., ... U")
U") ,.,
... Jl
,......-( ....... ' -r--r--r--"1---r""'•' ..... 'T'I -r--r---r>' .....,..,....., ...,........,..1""""""T 7.7 7.0 5.5 4.7
ppm
J I _r I
8
U")
r-
I 0
"' "' d !"! "''"' ON
7
N ,., "'
CX)
"'
6
U")
l ! "'
t3CNMR Spectrum of 44
...-4...-tqtqti.I')U")lf"'lOC""'MMM \0\0"''"'::'MMMMMMMM
v~~)-7d~
5
"'
U") ,.,
1 l ~ ! 0 "' .....
4 ppm
4. 4 3.3
... N
~ 0
0.-<
U"'IN r-r-
\ I
I
3 2
,., "' CX)
;
N 0
"'
I.C)qoqt<Q'...-4.-1000 MMMMMMMMM
~v~
170 150 130 110 90 80 70 60 50 40 30 20 10 ppm
Current Data ParaMeters NAME Nov02 2006
EXPNO
PROCNO
F2 - Acquisition Parameters Date 20061102 Time 10.37 INSTRUM spect PROBHD 5 mm PABBO BB-
PULPROG
TO
SOLVENT NS
OS
SWH
FI DERS AQ RG ow DE
TE
01 TOO
<l930 32768 CDC13
3200
10330.578 Hz 0.349935 Hz
1. 5293553 180
48.400 usee 6.00 usee
299.9 K 1.00000000
CHANNEL fl ••••••••
NUCl lH Pl 10.65 usee PLl 0.00 dB SFOl 300.1330875 Mflz
F2 - Processng Parameters SI 32768 SF 300.1300000 MHz wow
••• LB GB
EM
0 0. 30 Hz
Q PC 1. 00
0
Current Data Para•eters NAME Nov04 2006 EXPNO
PROCNO
F2 - Acquisition Para•eters Date 20061104 TiJie- 10.31 INSTRUM spect PROBHD 5 IDIA PA880 88-
PULPROG TO
SOLVENT NS
OS
SWH
FIDERS AO RG OM
DE
TE
01 dll DELTA
TOO
NUCl P1 PL1 SFOl
CPDPRG2 NUC2 PCPD2 PL12 PL13 PL2 SF02
zgpg30 32768 CDC13
3000
29761.904 Hz 0.8980452 Hz 0.5954638 sec
210 16.800
6.00 usee 299.9 K
2. 00000000 0.03000000 1.89999998
CHANNEL fl •••••••• 13C
7.80 0. 00 dB
75.7103643 MHZ
CHANNEL f2 --------waltzl6
1H 80.00 11.50 dB 11.50 dB
0.00 dB 300.1320005 MHZ
F2 - Processng Parameters SI 32768 SF 75.1578790 MHZ
wow EM SSB 0 LB 1. 00 Hz
GB 0 PC 1. 40
68
SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACALIXARENE SYNTHESIS
45:Yield 78%. 1HNMR (300 MHz, CDCI3):& 7.10, 7.68 (s, 8H, Ar-H), 0.82, 0.87, 1.32 (s, 72H, t-Bu), 6.33, 6.71 (s,
8H, Ar-H), 4.37, 5.33(m, 16H, OCH2CHzO, j=7.7), 3.66, 5.58 (d, 16H, ArCH2Ar, j=12.6), 13CNMR (75 MHz,
CDCh):& 30.5, 31.1, 34.0, 35.9 (Bu1), 133.2, 135.7, 144.3, 159.9 (Ar), 71.9, 75.6 (OCHzCH20), 32.1 (ArCH2Ar),
M5:m/z 1693 (M+1), EA Calc. for CmH1so01o (C:81.61, H:8.93), Found (C:81.52, H:8.79).
1HNMR Spectrum of 4s
....--.',......,....... ~ .........--.-.- ,.._,_r-..',.......-r--<' ~ 7.7 7.1 6.7 5.6 5.3 4.4 3.7
.r .r I I Jl
0)
"' 0 ....
i f
,., ,., "'
0)
,., ,.,
f l !'! 0 0\
ppm
I f
.... ,.,
! 0\
"' "'
r 0
.... ....
N ,.,
N 0\
,., 0
0) 0\
Current Data Paraaetera NAME Nov02 2006
EXPNO PROCNO
F2 - Acquisition Paraaeters Date_ 20061102 'riae 10.56 INSTRVH #pect PROBHD S am PABBO 88-
PULPROG TO SOLVENT HS
OS
SWH
FIDERS AO kG ow DE TE 01 TOO
zg30 32168 CDC13
3200
• 10330.578 Hz
0. 340753 Hz 1.5174056 sec
181 48.400 usee
6.00 uaec 300.1 K
1. 00000000 sec 1
•••••••• CHANNEL f 1 •••••••• NUCl lH. Pl 10.65 usee PLl 0.00 dB SFOl 300.1330815 MHZ
F2 - Processnq Para•eters St 32768 SF 300.1300000 MHZ MDV
sse Le Ge
EM 0
8 7 6 5 4 ppm
3 2 I
1 0 PC
0. 30 Hz 0
1.00
13(NMR Spectrum of 4s
0\ 0\
0\ 0\ U")U") ........ y
C"')Mf"'"r""-t"-\DNNN('I
~<QOU")ll'}lt)LOMMMM
.;roqoMMMP'lMMM"'l ,...,...,...,...,...,...r-tr-tr-t .... y Vr.J.J d, J....l
I I I I I I I I I I I I I I
170 150 130 110
"'"' .., .... .... ....
II
0'1000.-tr-11/li.Oil')
LO.;r.;r...,.Nr-tOOO MMMMMMMMM
~\~
I I I I I I I I I I I I I I I I I I I I I
90 80 70 60 50 40 30 20 10 0 ppm
Current Data Paraaetera NAME Nov04 2006 EXPNO 4 PROCNO
F2 - Acquisition Para•etera Date_ 20061104 Time 10.11 INSTRUH spect PROBHD 5 •na PABBO 88-PULPROG Z«Jpg30 TO 321'68 SOLVENT CDC13 NS 3000 OS 4
s•a 29761.904 Hz FlDERS 0.9177,83 Hz AO 0. 6060S32 sec RG 208 DW 16.800 usee a£ 6.00 usee TE 300.1 K Dl 2. 00000000 sec dll 0.03000000 sec DELTA 1.89999998 .uc TOO 1
•••••••• CHANNEL t.l •••••••• NUC1 l3C Pl 7,80 u•ec PLl 0.00 dB SFOl 75.7703643 MHZ
•••••••• CBAHH.EL 12 •••••••• CPDPRG2 NUC2 PCPD2 PL12 PL13 PL2 SF02
walttl6
1R 80.00 usee 11.50 dB 11.50 dB o.oo dl!l
300.1320005 MHZ
F2 - Processng Parameters SI 32768 SF wow sse LB
G.e PC
75.7518790 MHZ EM
0 1. 00 Hz
0 1.40
69
SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACALIXARENE SYNTHESIS
46:Yield 70%. 1HNMR (300 MHz, CDCh):5 7.10, 7.56 (s, 8H, Ar-H), 0.90, 0.93, 1.33 (s, 72H, t-Bu), 6.37, 6.88 (s,
8H, Ar-H), 4.25, 5.41(m, 16H, OCH2CH20, j=7.7), 4.03, 5.44 (d, 16H, ArCH2Ar, j=12.6), 13CNMR (75 MHz,
CDCh):5 30.9, 31.6, 34.8, 37.0 (But), 134.8, 135.8, 144.8, 161.4 (Ar), 72.0, 77.2 (OCH2CH20), 32.2 (ArCH2Ar),
MS:m/z 2032 (M+1), EA Calc. for C13aH1ao012 (C:81.61, H:8.93), Found (C:81.55, H:8.95).
lHNMR Spectrum of 4&
M .... "' M ... "' "'
"' OA ~~k "' .... 00
__;(A_ XA_ _.; / ' I .. '
7.1 6.9 ppm
..r JJ I J r-..,
"' .... ... "' oa> "' "'
.... ., ~ jf I
I :!:1 "' '! 0 0 0 "' 0
......... M
8 7 6 5
13(NMR Spectrum of 4&
........
170
CDOOCDCOOO\DCDCOOOCD
"Q'~tt)ti)U")I/)OQ'"Q'"Q'OQ' qto;;J"P"'MMMMMMM ...-tt-tr-tr-tr-t"""r-t""".-f..-t y "J.-,) .J J J .1 .J
150 130 110
5.4
!..J
"' "' ... M
! 1 !'3 "'0
........
4 ppm
"'0 r- "' r- r-
1 I
I
,...__
~
"' .... "' 0
"' 0\
3 2 1
OOOQ)C:ON\D0\0\0'\
90 80 70 60 50 40 30 20 10 ppm
0
0
Current Data Parameters NAME Nov02 2006
EXPNO 12
PROCNO 1
F2 - Acquisition Paraaeters Date 20061102 -Til'le 11.31 IN STRUM spect PROBHD 5 mm PABBO 88-
PULPROG zgJO TO 32768 SOLVENT CDC13
NS 3200 OS • SWR 10330.578 .. FIDERS 0.352843 •• AO 1.5234126 RG 179 ow 48.400 DE 6. 00 usee TE 299.8 • 01 1. 00000000 TOO 1
CHANNEL fl ···= ...... N\JCl '" Pl 10.65 PLl 0.00 dB
SFOl 300.1330815 HH•
F2 - Proceasng Parameters 51 32768
SF 300.1300000 HH<
wow EM
SSB 0
LB 0. 30 •• GB 0 PC 1. 00
Current Data Para•eters NAME Nov04 2006 EXPNO 9
PROCNO
F2 - Acquisition Paraaeters Date_ 20061104 Time 11.01 INSTRUH speet PROBHD 5 mm PAB80 88-
PULPROG Z9P930 TO 32168 SOLVENT CDC13 NS 3000 OS • ••• 29761.904 .. F IDERS 0.9123079 .. AQ 0.5863124 RG 20. DW 16.800 usee D£ 6. 00
T£ 300.1 K
Dl 2.00000000 dll 0. 03000000 DELTA 1. 89999998 TOO
CHANNEL fl --------NUCl 13C Pl 1. 80 usee
PLl 0.00 dB SFOl 15-.7103643 MH•
CHANNEL f2 --------CPDPRG2 waltz16 NUC2 lH PCPD2 80.00 usee
PL12 11.50 dB
PL13 11. so dB
PL2 0. 00 dB
SF02 300.132000~ ""' F2 Sl
- Pcocessng Parameters 32768
SF NOW SSB LB GB PC
75.1578790 MHZ.
EM
0 1.00 Hz
0 1. 40
70
SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACALIXARENE SYNTHESIS
47:Yield 59%. lHNMR (300 MHz, CDCh):b 7.15, 7.69 (s, 8H, Ar-H), 0.90, 1.02, 1.32 (s, 72H, t-Bu), 6.43, 6.99 (s,
8H, Ar-H), 4.25, 5.53(m, 16H, OCHzCHzO, j=7.7), 3.78, 5.64 (d, 16H, ArCH2Ar, j=12.5), 13CNMR (75 MHz,
CDCh):b 30.8, 32.0, 34.5, 36.2 (Bu1), 135.1, 135.6, 146.6, 160.7 (Ar), 73.3, 76.1 (OCHzCHzO), 32.3 (ArCHzAr),
MS:m/z 2370 (M+1), EA Calc. for C161H210014 (C:81.61, H:8.93), Found (C:81.49, H:8.81).
1HNMR Spectrum of 47
M U') "' N
N M
["""r--,-_,~............,~~~T--
8.0
"' 0
N
8
1.1
U'>N o .....
"'"" 1
f M ...
Q)
"' M
6
1.0
_jl
M U')
"""' 0"'
N M
ppm
5
13(NMR Spectrum of 47
r-r- \0\0\01.0\D\0.-4.-I.-tr-1
00 \DIDLOLOLOLOLOLOLOLO
"'"' 'lll''lll'MMPlMMMMM .......... ....-lr-lr-f....-l ..... l""fr-lr-1.-t...-4
y y 'l,d J J I J J
110 150 130 110
5.5
/_r
"' N
N
"' M
"' 0
N
4 ppm
..... ..,
.,.., r- ....
\ I
I
90 80 10 ppm
3.8
0
""'' Q) . "'"' r-..... Q) Q)
3 2 1
NLOLOLOMOCOCOCO
\O'IIl''lll'-=:I'"NNOOO Mr")Mt"lMMr")MM
~v~
60 50 40 30 20
0
10 0
Current Data Parameters NAME Nov02 2006
EXPNO PROCHO
18
F2 - Acquisition Parameters Date 20061102 -Time 11.47
IN STRUM spect
PROBHD 5 ... PABBO BB-
PULPROG Z930 TD 32768
SOLVENT CDC13
NS 3200
DS 4 SHH 10330.578 Hz
FIDER.S 0.350982 Hz
•o 1.4499934 RG 178 DH 48.400 usee:
DE 6.00 TE 299.8 • 01 1.00000000 TOO 1
CHANNEL fl --------NUCl 18
Pl 10.65 usee: PL1 0.00 dB
SFOl 300.1330875 MHz
F2 - Processng Paraaeters SI 32768
SF 300.1300000 MHz
WOW EM
SSB 0
LB 0. 30 Hz
GB
PC 1. 00
Curren~ Data Para•eters NAME Nov04 2006 EXPNO 13
PROCNO
F2 - Acquisition Para•eters Date 20061104 Tiae 12.11 IN STRUM spect PROBHD 5 •• PABBO BB-
PULPROG %9P930 TD 32768 SOLVENT CDC13
NS 3000 DS SWH 29761.904 Hz
FIDERS 0.9145464 Rz
AQ 0. 5849659 RG 208
DW 16.800 DE 6.00 usee TE 300.1 K
01 2. 00000000 dll 0.03000000 DELTA 1. 89999998 TOO
............. CHANNEL fl --------NUCl 13C
P1 1.80
PL1 o.oo dB
SFOl 75.7703643 MHz
CHANNEL f2 •••••••• CPDPRG2 valtzl6 NUC2 1H
PCPD2 80.00 PL12 11. so dB
PL13 17. so dB
PL2 0. 00 dB
SF02 300.I32000S MHZ
F2 - Proce.ssng Parameters SI 32768 SF 75.7518790 HHz wow EM
SSB 0 LB 1. 00 Hz
GB 0 PC 1.40
71
SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACALIXARENE SYNTHESIS
4a:Yield 37%. 1HNMR (300 MHz, CDCI3):& 7.18, 7.76 (s, 8H, Ar-H), 0.89, 1.10, 1.32 (s, 72H, t-Bu), 6.51, 7.01 (s,
8H, Ar-H), 4.25, 5.55(m, 16H, OCH2CH20, j=7.7), 3.80, 5.64 (d, 16H, ArCH2Ar, j=12.5), 13CNMR (75 MHz,
CDCh):& 30.9, 31.9, 34.4, 36.3 (Bu1), 134.9, 135.8, 146.3, 160.8 (Ar), 73.1, 76.0 (OCH2CH20), 32.4 (ArCH2Ar),
MS:m/z 2709 (M+1), EA Calc. for C184H24o016 (C:81.61, H:8.93), Found (C:81.50, H:8.87).
lHNMR Spectrum of 4a
( ~ .......-------...........,.... 8.0 7.2 7.0
_[ _r[ J _jf ..... "' "' "' "'
"' .... "' .... 0
"' "'"' "' U'IM 0 .-.o "' 0"'
N Nqo .... NM
8 7 6 5
13CNMR Spectrum of 4a
"'"' MMOOOOQ)000\0\0'10\
"'"' \0\DtOLOtOLO...rqo.qo.qo
"'"' .qo.qoMMMMMMMM ........ ........................ r-t.-tl"""fr-4.-t ....
y y 'Jrd J J d ,.J..J
170 150 130 110
5.6 ppm
I _j
"' N
0
N "' "' 0
.... N
4 ppm
o.-.
"'M .... .... \ I
I I
90 80 70 ppm
I' 4.2
3
60
3.8
2
N ....
.... 0'1 r.:J:i I,Q
. "'"' .... .... "'"'
1
P'}~.q'<q'<q'0\0\0'10\
\Dqo'QO.qoNI"""fOOO MMMMMMMMM
~v~
50 40 30 20
0
10 0
current Data Parameters NAME Nov02 2006 EXPNO 23 PROCNO
F2 - Acquisition Paraaeters Date 20061102 Time 12.09 INSTRUM PROBRD
POLPROG
TD SOLVENT NS
DS SWR
FIDERS AQ
RG
DW
DE
TE
01
TDO
Smm spect
PABBO BB-Z930
32768 CDC13
3200
• 10330.578 0.361149
1. 6234983 181
48.400 6.00
300.2 1. 00000000
I
•• ••
K
CHANNEL fl •••••••• NUCl 1H P1 10.65 PLl 0.00 dB SFOl 300.1330875 MRz
F2 - Processng Para•eters Sl 32768 SF 300.1300000 ""' WDW •• SSB 0
LB 0. 30 "' GB
PC 1.00
Current Da~a Paraaeters NAHE Nov04 2006 EXPHO 18 PROCNO
F2 - Acquisition ParaMeters Date 20061104 Ti•e 12.51 INSTRUK spect PROBHD 5 •• PABBO 88-
PULPROG Z9P930 TO 32768 SOLVENT CDC13 NS 3000 OS • s•• 29761.904 .. riDERS 0. 9235188 •• AQ 0.59-15372 RG 210
DN u.aoo DE 6. 00 TE 300.0 • Dl 2. 00000000 dll 0.03000000 DELTA 1. 89999998 TOO I
•••••-•• CHANNEL fl --------NIJCl 13C
PI 1. 80 PLI 0. 00 dB
SFOl 15.7703643 ••• CHANNEL f2 ••••••••
CPDPRG2 waltz16 NUC2 IH
PCPD2 80.00 PL12 17. so •• PL13 17. so dB
PL2 0.00 dB
SF02 300. 1320005 ••• F2 - Processng Paramet.ers Sl 32768 SF 75. 7!:178790 ••• wow EM SSB 0 LB 1.00 •• GB 0 PC 1. 40
72
SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACAUXARENE SYNTHESIS
3.1.5 CALIX(n)ARENE-THIACALIX(n)ARENE PSEUDO DIMERS 5n
Method C:A mixture of 4 (2Smmol), elemental sulfur Ss (SOmmol), and MOH (2Smmol) in
super-dry diphenyl ether (100ml) was stirred for 15min, heated gradually to 160°C over a
period of 1h and kept at this temperature for further 3h. The temperature was again raised
to 230°C over a period of 3h and maintained for further 3h. The resulting reaction mixture
was cooled to ambient temperature and analyzed by UPLC-MS. 1ml of reaction mixture
was sampled after every 30min, loaded on solid phase extraction cartridge and washed
with acetonitrile (1mlx2) to selectively remove decomposition residues. The products
were then eluted with methanol (1mlx3) and SOjlL of the elute was injected for analysis of
product mixture. No isolable quantity of 5 was achieved in any case (Scheme 3.6) .
.
~ g J ~~:~).
.
.
.
.
'
:~:-; ".9
'
#~ <"
... ~··
.. ~ ~:: ) ••• ···.&\VlJf'
0< :1, . 11.: .. \••i' (::.:.~-
.. ,,,.
Method D:To a solution of 4 (10mmol) in dry CH2Ch (100ml) was added SCh (nx40mmol in
CH2Cb) and stirred for 2h at 0°C. The reaction mixture was refluxed for 2h and allowed to
cool to ambient temperature spontaneously. The excess of SChwas destroyed with careful
addition of iced water with continuous stirring. The organic layer was separated and
evaporated to dryness with aid of vacuum. The residue obtained was washed with
acetone, ethanol and chloroform:ethylacetate (1:1, v/v) mixture to obtain respective
products 5n. The products were recrystallized in CH2Cb.
~,~t
\~~:~t! >350•>
:---~.t;;','i4V'
~.I>· 221~
~.~!~ 2581+ 'i~Rr%'i•
>~5Qfi ,-_{.~-~
C:748Q.
~t~i,. ~i~~;
~~i 2~;49:; t:.:~~ j· ·,
73
SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACALIXARENE SYNTHESIS
54:Yield 62%. 1HNMR (300 MHz, CDC!s):& 7.12, 7.66 (s, 8H, Ar-H), 0.82, 0.85, 1.33 (s, 72H, t-Bu), 6.49, 6.94 (s,
8H, Ar-H), 4.35, 5.43(m, 16H, OCHzCHzO, j=7.7), 3.24, 4.66 (d, 16H, ArCH 2Ar, j=12.7), 13CNMR (75 MHz,
CDC!s):l> 30.9, 31.8, 33.5, 34.3 (Bu1), 134.2, 135.4, 144.3, 160.9 (Ar), 72.6, 74.0 (OCH2CH20), 31.9 (ArCH2Ar),
EA Calc. for C92H1120a54 (C:74.96, H:7.66, 5:8.70), Found (C:75.01, H:7.60, 5:8.66).
lHNMR Spectrum of 54
M
"' M ..,. M M
"' ..,.
JA_AA_hRhA ' ' I .
7.7 7.1 5.4 4.3 ppm
f fJ J I ..,.
"' M
"' ..,. ..,.
"' "' "' "' "'
M M 0 "' "' 0 0 0 "' "' 0
8 7 6 5
13CNMR Spectrum of 54
170
"' en 00
"'"' .......... y
o:;ro:;rLOI.OLOLOo:;r~"'t'"'t' o:;r...,MMMMMMMM ......tMMMr-tMMr-lr-lr-1 Y'Ja.d.JddJ.J
150 130 110
II "' "'
M 0
"' M
..,.
"' "' .....
4 ppm
I
M 0
0\0
.,.N
\I
3
"' ..,.
"' 0
"'
2 1
~MMMM...-tOOO MMMMMMMMM
~~
90 80 70 60 50 40 30 20 10 ppm
0
0
Current Data Paraaeters NAME Novll 2006 EXPNO 9 PROCNO
F2 - Acquisition Para•eters Date 20061111 Time 10.44 IN STRUM spect PROBHD 5 mm PABBO BB-PULPROG zq30 TD 32768 SOLVENT CDCll NS 3200 DS SWH 10330.518 Hz
F IDERS 0.351194 Hz
AQ 1. 5151749 RG 180 DW 48.400 DE 6.00 TE 300.0 K
Dl 1. 00000000 TDO
CHANNEL f1 --------NUCl lH Pl 10.65 PLl 0.00 dB
SFOl 300.1330875 MHZ
F2 - Processng Parameters SI 32768 SF 300.1300000 MHz
WDW EM SSB 0 LB 0.30 Hz
GB 0 PC 1.00
Current Data Paraaeters NAME Novll 2006 EXPNO 2 PROCNO
F2 - Acquisition Paraaeters Date_ 20061112 Time 10.17 IN STRUM spect PROBHD 5 mm PABBO 88-PULPROG zgpg30 TD 32768 SOLVENT CDC13 NS 3000 DS SWH 29761.904 Hz
FIOERS 0.9184965 Hz
AQ 0.6134259 ••c RG 208 DW 16.800 DE 6.00 TE 300.0 K Dl 2. 00000000 dll 0.03000000 DELTA 1. 89999998 TDO
CHANNEL f1 --------NUCl 13C Pl 1. so PLl 0.00 dB SFOl 75.7703643 MHz
CHANNEL f2 --------CPDPRG2 walt1:16 NUC2 lH PCPD2 80.00 PL12 17.50 dB PL13 17.50 dB PL2 0. 00 dB SF02 300.1320005 MHz
F2 SI
- Processnq Parameters 32768
SF WDW SSB LB GB PC
75.7578790 HHz EM
0 1. 00 Hz
0 1.40
74
SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACALIXARENE SYNTHESIS
55:Yield 58%. 1HNMR (300 MHz, CDCh):5 7.10, 7.48 (s, 8H, Ar-H), 0.82, 0.87, 1.30 (s, 72H, t-Bu), 6.49, 6.69 (s,
8H, Ar-H), 4.37, 5.33(m, 16H, OCH2CH20, j=7.7), 3.66, 5.58 (d, 16H, ArCH2Ar, j=12.6), 13CNMR (75 MHz,
CDCh):5 29.8, 31.1, 35.0, 35.9 (Bu1), 133.6, 135.0, 144.1, 158.7 (Ar), 71.1, 73.6 (OCH2CH20), 31.7 (ArCH2Ar),
EA Calc. for CmH14001oSs (C:74.96, H:7.66, S:8.70), Found (C:74.85, H:7.63, S:8.76).
lHNMR Spectrum of Ss
M M
"'
rM
0 M
00 C>
)A_~~ "' ... .-< "'
___jQ __KA__ _ft / ..,_,... ,...__,.....
7.5 7.1 5.6
II f f m
"' "' 0
M M om 0 0 om
.-<0
8 7 6
13CNMR Spectrum of Ss
170
r- roo 00
"'"' .-< .-<
y
150 130
ppm
_r/ M M
"'
... "' 0 m
5
110
5.3 4.4
I _[ ..... M
"' M m 0
4 ppm
"'.-<
M C> r-r-
1 I
I
~ 3.7
3
... "' m 0
00 m
2
cnooor--nc»coco lt")l/')PJ'lPJ'lr-lr-10\0\0\ MMMMMMNNN
~v~
90 80 70 60 50 40 30 20 10 ppm
0
0
Current Data Parameters NAME Novll 2006 EXPNO 12
PROCNO
F2 - Acquisition Parameters Date 20061111 Time 11.17 IN STRUM spect PROBHD 5 mm PABBO BB-PULPROG zq30 TD 32768 SOLVENT CDC!)
NS 3200 DS SWH 10330.578 Hz
FIDERS 0.351814 Hz
AQ 1.7168524 RG 183 DW 48.400 DE 6.00 TE 300.1 K
D1 1. 00000000 TDO
CHANNEL fl --------NUCl 1H
P1 10.65 PL1 0. 00 dB
SFOl 300.1330&75 MHz
F2 - P.rocessng Para•eters Sl 32768 SF 300.1300000 MHZ
WDW EM
SSB 0 LB 0. 30 Hz
GB 0 PC 1.00
Current. D.at:a Paraaet:ers NAME Novl2 2006 EXPNO 5 PROCNO
F2 - Acquisition Para•eters Date_ 20061112 Time 10.46 IN STRUM PROBHD
PULPROG
TD SOLVENT NS DS ... FIDERS
AO RG
DW DE TE D1 dll DELTA TDO
NUCl P1 PL1
SFOl
CPDPRG2 NUC2 PCPD2 PL12 PL13 PL2 SF02
spect 5 •• PABBO BB-
zqpq30 32768 CDC13
3000
29761.904 Rz
0.8979497 Hz
0.5923531 209
16.800 6.00
300.1 • 2. 00000000 0. 03000000 1.89999998
1
CHANNEL f1 ••••••••
1JC 7. 80 0. 00 dB
75.1703643 MHz
CHANNEL f2 --------wa1tz16
lH 80.00 11.50 dB 11.50 dB
0.00 dB 300.1320005 MHz
F2 - P:cocessng Parameters S1 32168 SF 75.7578790 HHz wow EM SSB 0 LB 1. 00 Hz GB 0 PC 1.40
75
SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACAUXARENE SYNTHESIS
56:Yield 57%. 1HNMR (300 MHz, CDCb):~ 7.10, 7.56 (s, 8H, Ar-H), 0.90, 0.93, 1.31 (s, 72H, t-Bu), 6.47, 6.88 {s,
8H, Ar-H), 4.25, 5.41{m, 16H, OCH2CH20, j=7.7), 4.03, 5.44 (d, 16H, ArCHzAr, j=12.6), 13CNMR (75 MHz,
CDCb):~ 30.5, 31.6, 33.7, 35.0 (Bu1), 134.4, 135.9, 143.6, 161.1 (Ar), 73.0, 78.2 (OCH2CH20), 31.9 (ArCH2Ar),
EA Calc. for C13sHt6s012S6 (C:74.96, H:7.66, 5:8.70), Found (C:74.91, H:7.59, 5:8.68).
IHNMR Spectrum of 56
8
7.1
_[ _[ J J
N 0
co co
o"'
M"' "' 0"' "'
.-<0 0
7 6
t3CNMR Spectrum of 56
I I I 170 150 130
J .... ~
"'
.... 0
M
5.4 ppm
5
I 110
4.3
If "' N
"' ... "'0
I
4 ppm
90
4.2
N 0
M r- r-
1 I
I
I 80 70
3
ppm
4.0
2
I 60 50 40
.... M
~
"' co
30
M 0
"'
1 0
20 10 0
current Data Paraaeters NAME Novll 2006 EXPNO PROCNO
15
F2 - Acquisition Parameters Date 20061111 TiMe 12.45 !NSTRUM PROBHD POLPROG
TD SOLVENT NS DS SWH
FIDERS
•o RG DW DE TE D1 TDO
NUCl
P1
PL1
spect S mm PABBO BB-
ZC)30
32768 CDC13
3200
10330.578 Hz
0.360142 Hz 1.5381499
178 48.400
6. 00 300.2 K
1. 00000000 1
CHANNEL fl •••••s•• 18
10.65 u:sec 0. 00 dB
SFOl 300.1330875 MHz
F2 - Processng Parameters SI 32768 SF 300.1300000 MHz
WDN EM
SSB 0
LB 0.30 Hz
GB PC 1. 00
Current Data Para•eters NAME Nov12 2006 EXPNO PROCNO
F2 - Acquisition Paraaetera Date 20061112 -Tl•e 11.21 IN STRUM spect PROBHD s mm PABBO BB-
PULPROG zgpg30 TD 32768 SOLVENT CDC13 NS 3000 DS SOH 29161.904 Hz
FIDERS 0.9073924 Hz
AO 0.5990628 RG 209 DW 16.800 DE 6.00 TE 300.0 K
D1 2.00000000 .. c dll 0.03000000 soc DELTA 1.89999998 TDO 1
CHANNEL f1 ................ NUCl 13C P1 1. 80 usee PL1 0.00 dB
SFOl 75.1703643 MHz
CHANNEL f2 --------CPDPRG2 walt2:16 NUC2 1H PCPD2 80.00 usee PL12 11. !10 dB PL13 11. so dB
PL2 0.00 dB SF02 300.1320005 MHZ
F2 - Pcocessng Parameters SI 32768 SF 15. 7!»78190 MHZ WDW EM SSB 0 LB 1. 00 Hz GB 0 PC 1.40
76
SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACALIXARENE SYNTHESIS
S1:Yield 54%. 1HNMR (300 MHz, CDCh):8 7.18, 7.68 (s, 8H, Ar-H), 0.90, 1.02, 1.32 (s, 72H, t-Bu), 6.51, 6.97 {s,
8H, Ar-H), 4.25, 5.53{m, 16H, OCH2CH20, j=7.7), .3.78, 5.64 (d, 16H, ArCH2Ar, j=12.4}, 13CNMR (75 MHz,
CDCh):8 30.9, 32.0, 35.2, 36.6 (Bu1}, 135.0, 135.9, 147.5, 160.8 (Ar), 74.4, 76.1 (OCH2CH20), 33.0 (ArCH2Ar),
EA Calc. for C161H19601~1 (C:74.96, H:7.66, S:8.70), Found (C:74.90, H:7.61, S:8.73}.
1HNMR Spectrum of 57
.., "' "' N
"' N ...
JL _A_ __al _l_ JL ---,----.-.' I ~ I
7.7 7.2 5.7 5.6
I If J Jf ,.... .... ... "' "' "'
00 ..;
"' "' "'
~~ ~ ~ ,....
~ "' r-o "' ....... 0 00 0\ 00\
N N N NM
8 7 6
13CNMR Spectrum of 57
00 00
00
"'"' ........ y
lf)lf'I0\0\0\0'10000
f'f"""I.OI.ll&Oillll")lf'III'II.O -.:r"'I'MPlMMP')MMM ...-l.....t.....t...-1-tr-fr-f.-tr-t.-1
Y'~.J.J•J.J
I 5.5
ppm
5
I 170
I 150
I 130 110
. . I .... I 4.3 4.2 3.8 3.7 (
I _[ "' N
.... 00
1 ,....
1 T I .... ( N "' 0\.-<0
"' 0 •00 ,.... ... N "'"'"' -r
4 3 2 1 ppm
"'"" \7
II I I I
90 80 70 60 50 40 30 20 10 ppm
0
I 0
Cun:ent Data Para•eters N!o-ME Novll 2006 EXPNO 20 PROCNO 1
F2 - Acquisition Para•eters Date 20061111 -Tiae 1.28 INSTRUM apeet PROBHD 5 •m PABBO 88-
PULPROG zq30 TD 32768 SOLVENT CDC13 NS 3200 DS 4 SWH 10330.578 Hz
FI DERS 0.359879 Hz AQ 1. 454182 RG 180 DW 48.400 DE 6. 00 TE 299.8 • 01 1. 00000000 TOO 1
CHANNEL fl --------NUCl 1H Pl 10.65 PL1 0 .oo dB
SFOl 300.1330875 MRz
F2 - Proceasnq Par•meters SI 32768 SF 300. 1300000 MHz
wow EM SSB 0 LB 0.30 Hz
GB 0 PC 1.00
Current Data Para•eters NAME Nov12 2006 EXPNO PROCNO
12
F2 - Acquisition Para•eter• Date 20061112 -Ti•e 12.07 IN STRUM spect PROBHD 5 •• PABlO BB-PULPROG &9P930 TD 32768 SOLVENT CDCl) NS 3000 DS SWH 29761.904 Rz FIDERS 0.9142965 Hz AQ 0.5915273 RG 210 DW 16.800 DE 6. 00 usee TE 299.9 • Dl 2. 00000000 dii 0. 03000000 DELTA 1. 89999998 TOO
CHANNEL f1 --------NUCl 13C Pl 1.80 PLI 0.00 dB SFOl 75.7703643 MHZ
CHANNEL .. --------CPDPilG2 walt&16 tlUC2 IR PCPD2 80.00 uaec PL12 11.50 dB PLll 17.50 dB PL2 0.00 dB SF02 300.1320005 MHZ
F2 - P.rocessng; Parameter• SI 32768 SF 75.7578790 MHZ WON EM SSB 0 LB 1. 00 Hz GB 0 PC 1.40
77
SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACALIXARENE SYNTHESIS
Sa:Yield 32%. 1HNMR (300 MHz, CDCh):l> 7.18, 7.76 (s, 8H, Ar-H), 0.89, 1.10, 1.32 (s, 72H, t-Bu), 6.50, 7.01 (s,
8H, Ar-H), 4.25, 5.55(m, 16H, OCH2CH20, j=7.7), 3.80, 5.64 (d, 16H, ArCH2Ar, j=12.5), 13CNMR (75 MHz,
CDCh):l> 30.8, 31.9, 35.2, 36.5 (Bu1), 134.8, 135.7, 147.4, 158.9 (Ar), 74.6, 77.0 (OCH2CH20), 33.0 (ArCH2Ar),
EA Calc. for C184Hm016Ss (C:74.96, H:7.66, S:8.70), Found (C:74.89, H:7.60, S:8.67).
1HNMR Spectrum of Sa
8
I
"' 0
JJ .... 0
0\0 00
NN
7
J 0
"'
"' "' ....
7.1
6
Jf "' "' "'
"' .... 00\
N..,
5.6 ppm
5
13CNMR Spectrum of Sa
170
"'"' Q) Q)
"' "' ........ y
l"""r"'-IJ')lt11J")lt)<o;f'~"''f'<o;f'
'OIP<o:t'MMMMMMMM ............... .-f .......................... .....
y~.JJJL.J
I 150 130 110
5.5
I _[ "' N
N
"' .... "' 0
N
4 ppm
0\0
,... .... ,...,... \1
I
..--.-.---4.2 3. 8
3
00\
.... "' "' Q) . "'"' ,... .... Q) Q)
2 1
l()NNNOO'\CX>C:OCXI
I.Dl()U")l()M ..... OOO MMMMMMMf"''M
~\~
I I I I I I 90 80 70 60 50 40 30 20 10
ppm
0
0
current Data Para•et.er:s NAME Novll 2006 EXPNO 24 PROCNO
F2 - Acquisition Para••tera Date 20061111 -Tirne 1. 49 INSTP.UM spec:t PROBHD 5 •m PABBO 88-
PULPROG zglO TD 32768 SOLVENT CDCll NS 3200 DS • SWR 10130.578 Hz FIDERS 0.340611 Hz AQ 1. 5134257 ... RG 181
DW 48.400 usee D£ '· 00
usee
T£ 300.2 • D1 1. 00000000 ... TDO
CHANNEL f1 --------NUCl 18
P1 10.65 usee PLl o.oo dB
SFOl 300.1330175 MR•
F2 - Proc•11snq Parameters 51 32768 SF 300.1300000 MH•
WDW EM SSB 0 LB 0. 30 Hz GB 0 PC 1.00
Current. Data Para•etera NAME Nov12 2006 EXPNO l8
PROCNO
F2 - Acquisition Para•eters Date 20061112 -Time 12.55 INSTRUH spect PROBHD 5 •• PABBO 88-PULPROG &qpC)30 TD 32768 SOLVENT CDC13
NS 3000 DS • SWB 29161.904 .. FIDERS 0.9014S59 .. AQ 0.5814326 ... RG 208 DW 16.800 usee DE 6.00 us•c TE 300.1 • 01 2. 00000000 ... dll 0. 03000000 ... DELTA 1. 89999998 ... TDO
CHANNEL t1 --------HUCI 13C PI 1. 80 usee PL1 o. 00 dB SFOl 75.7703Ei43 MHZ
•••••••• CHANNEL l2 •••••••• CPDPRG2 wdtzl6 NUC2 PCPD2 PL12 PL13 PL2 SF02
F2 -51 SF WOW
SSB LB GB PC
1R 80.00 17.50 17.50 o. 00
300.132000S
ProeessnC) Parameters 32168
75.7578190 EM
l. 00 0
1. 40
dB dB dB M ..
MH&
••
78
SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACAUXARENE SYNTHESIS
3.1.6 HALO-DE-ALKOXVLATION OF 5n
:~~:::::nal::h:~::. :::::,::o:~u::o:~:~~:: ~. '.f .. £.:, .. :~.:.".··· ".".~.·'.' and added with nxSOml Lil solution {4M in 50% aq. . -1 ,_, :· )i
~-~·~·.· ~), ~- .... ·,}~;,,
alcohol, v/v). The reaction mixture was brought to ~"''~)~;: al
::.":1::::::::~::::::::~~ :ti::i:~~::: :::~~ ~.~.-.·.~.!' .•... :.,i~l The reaction mixture was acidified with lOOml 1M L'i· ·. HCI and the products were recovered by filtration, · ·~:v
~!i~:~;~0~~~~:~~~~!,:~~~·· followed by drying to yield solid residue. The residue
was dissolved in SOml chloroform, filtered and chromatographed on silica gel {200mesh,
lOOmm length, 15mm diameter column) using hexane:chloroform {1:1-2, v/v) mobile
phase {Scheme 3.7).
Characterization data of all calixarene derivatives 24-8 have already been published,124•25l
where as characterization data of 14-s derivatives have already been recorded in previous
chapter and hence not repeated here.
3.1.7 A BRIEF DISCUSSION ON CONFORMATIONAL PREFERENCES OF 5n
The structure of pseudo dimers {calix-thiacalix tubes) 5n was confirmed by 1H & BCNMR,
and ESI-mass spectral data. The 1HNMR spectra of all 5n homologs were well resolved. For
instance, in case of 56, the 1HNMR spectrum contains four singlets in the aromatic region
{6.47, 6.88, 7.10, 7.56), two pairs of multiplets of ethylene -QCHzCHzD- protons {4.25,
4.82, 5.05, 5.41), two doublets from bridging methylene group -ArCH2Ar- protons {4.03 &
5.44), and also a set of singlets from tert-butyl groups {0.90, 0.93}. 13CNMR spectra contain
eight sets of closely spaced aromatic signals {two in each set) in aromatic region, four
signals of -OCHzCHzO- carbons, and four signals from p-tert-butyl substituents of the upper
rim. The results of 1H & BCNMR measurements are in very good agreement with existing
literature, especially with the results of extensive study of structural preferences {of calix-,
thiacalix-, and hybrid calix-thiacalix tubes, i.e. symmetric and asymmetric/pseudo dimers)
carried out by Kovalev et a/.1151 throug 1HNMR spectroscopy {tube 54 has already been
reported by Kovalev eta/.)
Now let us examine the NMR Spectra. The double set of all NMR signals, especially in the
aromatic region, indicates that both calix frameworks {calix and thiacalix) of pseudo dimers
56 contain two types of aromatic rings, suggesting Czv symmetry. Further, it is known that
79
SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACAUXARENE SYNTHESIS
C6A and TC6A possess near C2v symmetry in their crystal structure with a single
conformation, but when solvated, they exhibit two different conformers (flattened/
pinched cone - C2v and cone CGv) at lower temperature (as is evident from their NMR
spectra). At higher temperature, in solution, they undergo rapid pinched cone - cone -
pinched cone inter conversion, effectively giving averaged signals. A similar pattern of
apparent asymmetry in present compounds (pseudo dimers) can be envisaged due to
conformational properties of constituent calixarene fragments themselves, which form the
tube (pseudo dimer). A more comprehensive discussion on the conformational
preferences of calix[4]arene-thiacalix[4]arene tubes (and other symmetric tubes) can be
availed by referring to the work of Kovalev et a/.115) where as the work of Beer et a/.116-20)
may be of particular interest for study of conformational analysis of bis(calix[4]arene)
tubes and their various derivatives (accomplished with the aid of NMR spectroscopy as
well as X-ray diffraction analysis). The latter have also studied the metal complexation and
accompanying structural changes for the bis-calix tubes.
5 CONCLUSION
In the present chapter, we have demonstrated a simple and versatile approach for the
synthesis of various thiacalixarene homologs. The modularity of the strategy permits its
adaptation to produce variety of other supramolecular assemblies like carcerands and a
plethora of other heteracalixarenes. Further, the carcerand like intermediates (pseudo
dimers) achieved in this fashion have dimensions of nano scale, and are excellent
examples of supramolecular nano-tubes, which may be further explored in future course
to fulfill variety of purposes already described in nano-sciences.
80
------------------------------------ ---- -
SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACAUXARENE SYNTHESIS
REFERENCES
1. Z. Asfari, V. Bohmer, J. Harrowfield, J. Vicens, in Calixarenes 2001, Kluwer
Academic, Dordrecht, 2001.
2. N. Morohashi, F. Narumi, N. lki, T. Hattori, S. Miyano, Chern. Rev. 2006, 106, 5291.
3. P. Lhotak, Eur. J. Org. Chern. 2004, 1675.
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Kamiyama, S. Miyano, Tetrahedron Lett. 1997, 38, 3971.
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8. S. Shokova, V. Tafeenko, V. Kovalev, Tetrahedron Lett. 2002, 43, 5153.
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Lett.2003,44,8093.
10. Y. Kondo, K. Endo, N. lki, S. Miyano, F. Hamada, J. Incl. Phenom. Macrocycl. Chern.
2005, 52, 45.
11. Y. Kondo, F. Hamada, J. Incl. Phenom. Macrocycl. Chern. 2007, 58, 123.
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13. J. Lang, J. Vagherova, J. Czernec, P. Lhotak, Supremo/. Chern. 2006, 18, 371.
14. T. Sone, Y. Ohba, K. Moriya, H. Kumada, K. Ito, Tetrahedron 1997, 53, 10689.
15. E. Khomich, M. Kashapov, I Vatsuro, E. Shokova, B. Kovalev, Russ. J. Org. Chern.
2007, 43, 192.
16. P. Schmitt, P. Beer, G. Michael, P. Sheen, Angew. Chern., Int. Ed. 1997, 36, 1840.
17. S. Matthews, P. Schmitt, V. Felix, M. Drew, P. Beer, J. Am. Chern. Soc. 2002, 124,
1341.
18. S. Matthews, V. Felix, M. Drew, P. Beer, Org. Biomol. Chern. 2003, 1, 1232.
19. P. Webber, P. Beer, G. Chen, V. Felix, M. Drew, J. Am. Chern. Soc. 2003,125, 5774.
20. S. Matthews, N. Rees, V. Felix, M. Drew, P. Beer, lnorg. Chern. 2003,42,729.
21. J. March, in March's Advanced Organic Chemistry, ed. M. Smith, John Wiley & Sons
Inc., New York, 5th edn. 2001, 519.
22. P. Gale, J. Sessler, V. Lynch, P. Sansom, Tetrahedron Lett. 1996, 37, 7881.
81
-------------------------- -~-- -- -
SYNTHESIS II-INDIRECT APPROACHES TOWARDS THIACALIXARENE SYNTHESIS
23. P. Gale, J. Genge, V. Kral, M. McKervey, J. Sessler, A. Walker, Tetrahedron Lett. 1997,
38,8443.
24. C. D. Gutsche, in Calixarenes, Monographs in_ Supramolecular Chemistry, J. F.
Stoddart, Ed., The Royal Society of Chemistry, Cambridge and london, 1989.
25. C. D. Gutsche, in Calixarenes Revisited, Monographs in Supramolecular Chemistry,
Cambridge, 1998.
82