Allyl-substituted macrocyclic crown formazans: Promising precursors for polymer-supported macrocycles

Article abstract of DOI:10.1055/s-2001-15233

The bisphenol 1 was obtained by reacting the amine hydrochloride 11 with cyanoacetic acid in aqueous sodium hydroxide solution. Thermal rearrangement of 1,5-bis(allyloxyphenyl)formazan (7) failed to give 1. Alkylation of the bis phenol 1 with 1,3-dibromopropane in basic solution under high dilution conditions gave the corresponding allyl-substituted macrocyclic formazan 2a in a very low yield. On the other hand, diazotization of the new bis amine hydrochloride 3a,b with NaNO₂ in hydrochloric acid followed by coupling with the appropriate active methylene compounds furnished the corresponding macrocyclic formazans 2a-d. Compounds 3a,b were obtained by first reacting the K-salt of 12 with the appropriate dihalides to give the corresponding bis acetamides 13 and 14, respectively. Subsequent acid hydrolysis of the latter afforded 3a,b in good yield.

Full text of DOI:10.1055/s-2001-15233

PAPER
1331
Allyl-Substituted Macrocyclic Crown Formazans: Promising Precursors for
Polymer-Supported Macrocycles
A
llyl-Substitute
d
M
s
a
crocyc
l
h
ic Crow
n
Fo
r
rmazansaf A. Abbas,* Ahmed H. M. Elwahy
Department of Chemistry, Faculty of Science, Cairo University, Giza, A. R. Egypt
Fax (00202)5727556; E-mail: ashraf@chem-sci.cairo.eun.eg
Received 27 February 2001; revised 22 March 2001
Abstract: The bisphenol 1 was obtained by reacting the amine hy-
drochloride 11 with cyanoacetic acid in aqueous sodium hydroxide
solution. Thermal rearrangement of 1,5-bis(allyloxyphenyl)forma-
zan (7) failed to give 1. Alkylation of the bis phenol 1 with 1,3-di-
bromopropane in basic solution under high dilution conditions gave
the corresponding allyl-substituted macrocyclic formazan 2a in a
very low yield. On the other hand, diazotization of the new bis
amine hydrochloride 3a,b with NaNO2 in hydrochloric acid fol-
lowed by coupling with the appropriate active methylene com-
pounds furnished the corresponding macrocyclic formazans 2a d.
Compounds 3a,b were obtained by first reacting the K-salt of 12
with the appropriate dihalides to give the corresponding bis aceta-
mides 13 and 14, respectively. Subsequent acid hydrolysis of the
latter afforded 3a,b in good yield.
Key words: alkylation, thermal rearrangement, diazotization, cou-
pling, macrocyclic formazans
Figure
The chemistry and diverse applications of formazans have
been the subject of a large number of reviews that have
been cited previously.1 Moreover, there is recent growing
interest in the synthesis of macrocyclic crown formazans2
due to their useful applications in selective metal
extraction3–6 and determination.7–16 Such applications de-
pend mainly on the cavity size of the macrocyclic crown
formazans as well as on the substituents in the macrocy-
cle. In this respect, we recently reported the synthesis of
some macrocyclic formazans I (Figure) and studied their
evaluation in spectrophotometric determination of lithium
as well as carriers in cesium ion selective electrode.1,17–21
The use of such compounds on a large scale for industrial
purposes is inhibited by their expense. A potentially use-
ful way around this problem lies in attracting the com-
plexing agent to the polymeric backbone and then
facilitating its retrieval. In the last decades, large numbers
of both soluble and insoluble polymers containing crown
compounds have been developed and have been the sub-
ject of many reviews.22–27 In connection with this finding
and in continuation of our interest in the chemistry and ap-
plication of formazans, we report here on the synthesis of
the first macrocyclic formazans with allyl moiety, which
can be subsequently utilized as promising monomers for
the synthesis of polymer-supported macrocycles.
Scheme 1
Synthesis 2001, No. 9, 29 06 2001. Article Identifier:
1437-210X,E;2001,0,09,1331,1336,ftx,en;Z02001SS.pdf.
© Georg Thieme Verlag Stuttgart · New York
ISSN 0039-7881
We planned to construct the allyl-substituted macrocyclic
formazans 2 by two strategies as shown in Scheme 1. In
the first strategy, we studied the formation of 2 by reacting

1332
A. A. Abbas, A. H. M. Elwahy
PAPER
Scheme 2
the corresponding 1,5-bis(3-allyl-2-hydroxy)formazan 1 for 2 hours furnished 55% of 10. Compound 11 was alter-
with the appropriate dihalo compound in basic solution natively obtained in 75% yield upon treatment of 2-aceta-
under high dilution conditions. The second strategy de- mido-6-allylphenol (12)28 with ethanolic solution
pends firstly on the formation of the bisamine hydrochlo- containing hydrochloric acid. Tiffany28 reported the syn-
rides 3 followed by diazotization with NaNO2 in thesis of 12 in 50% yield by heating 2-allyloxyacetami-
hydrochloric acid and subsequent coupling with the ap- dophenol (5) at 190°C in N,N-dimethylaniline. It is
propriate active methylene compounds.
noteworthy to mention here that repeating the above reac-
tion under the same condition described by Tiffany gave
only 20% of 12.
Two routes were attempted to synthesize the new allyl-
substituted formazans 1 as outlined in Schemes 2, 3. In
the first route (Scheme 2), our attention focused on the The bisphenol 1 was then reacted with 1,3-dibromopro-
synthesis of 1,5-bis(2-allyloxy)formazan 7, which should pane in ethanolic solution containing sodium ethoxide un-
then undergo thermal rearrangement to give 1. Unfortu- der high dilution conditions. The 1H NMR spectrum of the
nately, heating 7 in an oil bath at 180°C for 2 hours did not reaction products indicated the presence of the macrocy-
lead to the formation of 1. Instead, the reaction gave an clic formazan 2a together with other reaction products
oily residue that could not be easily handled nor character- whose structures could not be determined so far. The for-
ized. Compound 7 was obtained in 65% yield by diazoti- mation of 2a was also supported by the presence of the
zation of the corresponding 2-allyloxyaniline correct molecular ion peak in the mass spectrum. After
hydrochloride, and subsequent coupling with cyanoacetic successive purifications on preparative TLC, a pure sam-
acid in aqueous sodium hydroxide solution. The latter was ple of 2a was isolated in only 2.5% yield. Repeated at-
obtained from 2-acetamidophenol (4) by first alkylation tempts to enhance the yield of 2a by performing the
with allyl bromide to give 5 followed by hydrolysis with alkylation reaction under different basic conditions were
ethanolic solution containing hydrochloric acid.28 In the also unsuccessful.
second route (Scheme 3), the 6-allyl-2-aminophenol 11
was chosen as the precursor for 1 (R = CN) via initial dia-
zotization with NaNO2 in hydrochloric acid followed by
coupling with cyanoacetic acid in aqueous sodium hy-
droxide solution. Compound 11 was obtained in 70%
yield by reacting N-(3-allyl-2-hydroxyphenyl)phthalim-
ide (10) with hydrazine hydrate in ethanolic solution con-
In anticipation of the low yield of the macrocyclic forma-
zan 2a, we applied the second strategy as outlined in
Scheme 4. Thus, reaction of the K-salt of 1228 with 1,3-di-
bromopropane or , -dibromo-o-xylene in DMF afford-
ed 65% and 68%, respectively, of the corresponding
bis(acetamido) ethers 13 and 14. The latter underwent
acid hydrolysis upon treatment with ethanolic solution
containing hydrochloric acid to give 70% and 72%, re-
spectively, of the corresponding bis amine hydrochlorides
taining hydrochloric acid. The latter was obtained from
N-(2-hydroxyphenyl)phthalimide (8)29 by first alkylation
with allyl bromide to give 70% of 9. Subsequent thermal
3a,b. Diazotization of 3a,b with NaNO2 in hydrochloric
rearrangement of 9 upon heating in an oil bath at 180°C
acid followed by coupling with cyanoacetic acid in pyri-
Synthesis 2001, No. 9, 1331–1336 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Allyl-Substituted Macrocyclic Crown Formazans
1333
Scheme 3
with a Varian GEMINI 200 spectrometer (200 MHz, 1H NMR) for
compounds 2a–d, 9, 10, 13 and 14 or with a Brucker WM-300 in-
strument (for compounds 1 and 7). Mass spectra were recorded on
a GCMS-QP 1000 EX or a Varian 311A instrument. Elemental
analyses were carried out at the Microanalytical Centre, Cairo Uni-
versity. 1,3-Dibromopropane and , -dibromo-o-xylene were used
as purchased from Aldrich.
dine containing CuSO4 yielded 35% and 30%, respective-
ly, of the corresponding macrocylic formazans 2a,b.
Moreover, the macrocylic formazans 2c,d substituted
with phenyl group in the formazyl carbon were obtained
in 10% and 7% yields, respectively, by diazotization of
3a,b with NaNO2 in hydrochloric acid followed by cou-
pling with phenylpyruvic acid in aqueous sodium hydrox-
ide solution.
Formazans 1, 7 and Macrocyclic Formazans 2a,b;
General Procedure
A solution of the appropriate amine hydrochloride 6, 11 (2 mmol)
or diamine dihydrochloride 3a, b (1 mmol) in H2O (5 mL) and con-
cd HCl (3 mL) was diazotized at –5°C with a solution of NaNO2
(0.23 g in 5 mL water) during 30 min. Stirring was continued for 1
h at –5°C, and then the reaction mixture was added dropwise with
stirring to a solution containing cyanoacetic acid (1 mmol) [in H2O
(10 mL) containing NaOH (1.2 g ) for compounds 1 and 7 or in py-
ridine (150 mL), CuSO4 5H2O (0.5 g) and H2O (20 mL) for com-
pounds 2a,b] over 1 h. The reaction mixture was kept in the freezer
overnight. The solid, which precipitated by adding concd HCl, was
collected and crystallized from the proper solvent (for 1 and 7) or
purified on preparative TLC using silica gel (60 F254) [CH2Cl2 pe-
troleum ether (40 60), 2:1] (for 2a,b).
In conclusion, we have prepared the first macrocyclic for-
mazans with allyl substituents in the macrocycles. Further
studies on the attachment of the new macrocycles to a
polymeric backbone are now in progress and will be de-
scribed in due course. Although our first strategy for con-
striction of 2 did not yield considerable amount of the
product, this method led to the formation of the new allyl-
substituted formazans 1 and 7, which should also be good
precursors for the synthesis of new polymeric formazans
of expected useful applications.
All mps are uncorrected. IR spectra (KBr) were recorded on a Per-
kin Elmer 1430 spectrophotometer. NMR spectra were measured
Synthesis 2001, No. 9, 1331–1336 ISSN 0039-7881 © Thieme Stuttgart · New York

1334
A. A. Abbas, A. H. M. Elwahy
PAPER
Scheme 4
3-Cyano-1,5-bis(3-allyl-2-hydroxyphenyl)formazan (1)
Application of the general procedure (using 11) gave crude 1, which
was crystallized from toluene as deep red crystals. Yield: 60%; mp
175°C.
1,13-Diallyl-16,17-dihydro-5H,15H-dibenzo[b,i][1,11,4,5,7,8]di-
oxatetraazacyclotetradecine-7-carbonitrile (2a)
(a) Application of the general procedure (using 3a) gave deep red
crystals of 2a. Yield: 35%; Rf = 0.89; mp 195 196°C.
1
IR: = 3352.1 (OH), 2233.4 (CN) 1639 (C=C), 1245, 1065 (N=N)
cm .
1H NMR (CDCl3): = 3.47 (d, 4H, J = 6.4 Hz, CH2-CH=CH2), 5.18
(d, 2H, Jcis = 11.4 Hz, CH=CH2), 5.19 (d, 2H, Jtrans = 16.2 Hz,
CH=CH2), 5.97 6.06 (m, 2H, CH=CH2), 6.94 7.56 (m, 6H, Ar-
H), 8.70 (br s, 2H, OH), 14.62 (s, 1H, NH).
IR: = 2225 (CN), 1641 (C=C), 1255, 1047 (N=N) cm .
1
1H NMR (CDCl3): = 2.26 (quintet, 2H, J = 4.6 Hz, OCH2CH2),
3.48 (d, 4H, J = 6.6 Hz, CH2-CH=CH2), 4.17 (t, 4H, J = 5.0 Hz,
OCH2), 5.09 5.20 (m, 4H, CH=CH2), 5.89 6.09 (m, 2H,
CH=CH2), 7.14 7.79 (m, 6H, Ar-H), 15.15 (s, 1H, NH).
MS: m/z (%) = 401 (M+, 27), 360 (56), 255 (12), 227 (25), 105
13C NMR (CDCl3): = 114.3 (CN), 116.8, 121.1, 128.6, 131.5, 136
(100).
(Ar-CH, CH=CH), 133.2, 136.3, 147.9 (Ar-C, C=N).
MS: m/z (%) = 361 (M+, 12), 360 (58), 198 (52.5), 104 (100), 76
Anal. Calcd for C23H23N5O2 (401.46): C, 68.81; H, 5.77; N, 17.44.
Found: C, 68.90; H, 5.70; N, 17.75.
(55).
(b) To a solution of 1 (5 mmol) in ethanolic solution of sodium
ethoxide [prepared from Na (2.30 g, 10 mmol) and absolute EtOH
(100 mL)] was added 1,3-dibromopropane (5 mmol). The reaction
mixture was removed in vacuo and the remaining material was pu-
rified as in method (a) to give 2.5% of 2a.
Anal. Calcd for C20H19N5O2 (361.40): C, 66.47; H, 5.30; N, 19.38.
Found: C, 66.31; H, 5.31; N, 19.40.
1,5-Bis(2-allyloxyphenyl)-3-cyanoformazan (7)
Application of the general procedure (using 6) gave crude 7, which
was crystallized from MeOH as deep red crystals. Yield: 65%; mp
85°C.
7,19-Diallyl-5,21-dihydro-11H-tribenzo[b,i,m][1,11,4,5,7,8]dioxa-
tetraazacyclopentadecine-13-carbonitrile (2b)
Application of the general procedure (using 3a) gave deep red crys-
tals of 2b. Yield: 30%; Rf = 0.89; mp 255 257°C.
1
IR: = 2225.7 (CN), 1642 (C=C), 1240, 1050 (N=N) cm .
1H NMR (CDCl3): = 4.69 (d, 4H, J = 4.9 Hz, OCH2), 5.30 (d, 2H,
cis = 10.6 Hz, CH=CH2), 5.44 (d, 2H, Jtrans = 17.3 Hz, CH=CH2),
5.99 6.09 (m, 2H, CH=CH2), 6.97 7.79 (m, 8H, Ar-H), 12.99 (s,
1
IR: = 2225 (CN), 1639 (C=C), 1261, 1065 (N=N) cm .
J
1H NMR (CDCl3): = 3.60 (d, J = 6.4 Hz, 4H, CH2-CH=CH2),
5.11 5.21 (m, 8H, OCH2, CH=CH2), 5.99 6.18 (m, 2H,
CH=CH2), 7.16 7.74 (m, 10H, Ar-H), 14.96 (s, 1H, NH).
MS: m/z (%) = 464 (M+, 12), 423 (14), 359 (13), 251 (25), 161 (22),
104 (100).
1H, NH).
13C NMR (CDCl3): = 70.2 (CH2), 115 (CN), 114, 116.7, 117.9,
121.8, 129.9, 132.9 (Ar-CH, CH=CH), 126.8, 136.7, 151.9 (Ar-C,
C=N).
MS: m/z (%) = 361 (M+, 28), 320 (18.3), 213 (26), 161 (41.6), 105
(100).
Anal. Calcd for C28H25N5O2 (463.53): C, 72.55; H, 5.44; N, 15.11.
Found: C, 72.65; H, 5.30; N, 14.99.
Anal. Calcd for C20H19N5O2 (361.40): C, 66.47; H, 5.30; N, 19.38.
Found: C, 66.40; H, 5.25; N, 19.42.
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Allyl-Substituted Macrocyclic Crown Formazans
1335
Macrocyclic Formazans 2c,d
H2O, and crystallized from EtOH to give colorless crystals of 13 and
14, respectively.
A solution of the appropriate diamine dihydrochloride 3a,b (1
mmol) in H2O (5 mL) and concd HCl (3 mL) was diazotized at –5°C
with a solution of NaNO2 (0.23 g in 5 mL H2O) during 30 min. Stir-
ring was continued for 1 h at –5°C, and the mixture was added drop-
wise with stirring to a solution containing phenylpyruvic acid [in
H2O (10 mL) containing NaOH (1.2 g)] over 1 h. The reaction mix-
ture was then kept in the freezer overnight. The solid that precipitat-
ed was collected and purified on preparative TLC using silica gel
(60 F254) [CH2Cl2 petroleum ether (40 60), 1:2].
Compound 13
Yield: 65%; mp 154°C.
IR: = 3352.1 (NH), 1693 (CO), 1645 (C=C), 1245, 1076 (N=N)
1
cm .
1H NMR (CDCl3): = 1.99 (s, 6H, COCH3), 2.23 (quintet, 2H,
J = 5.6 Hz, OCH2CH2), 3.45 (d, 4H, J = 6.4 Hz, CH2-CH=CH2),
4.22 (t, 4H, J = 5.4 Hz, OCH2), 5.04 5.15 (m, 4H, CH=CH2), 5.85
6.05 (m, 2H, CH=CH2), 6.90 8.30 (m, 6H, Ar-H), 8.57 (br s, 2H,
NH).
1,13-Diallyl-16,17-dihydro-5H,15H-7-phenyldibenzo-[b,i]-
[1,11,4,5,7,8]dioxatetraazacyclotetradecine (2c)
Prepared from 3a.
Anal. Calcd for C25H30N2O4 (422.52): C, 71.07; H, 7.16; N, 6.63.
Found: C, 70.90; H, 7.25; N, 6.77.
Deep red crystals; yield: 10%; Rf = 0.58; mp 140 142°C.
Compound 14
1
IR: = 1640 (C=C), 1267, 1050 (N=N) cm .
Yield: 68%; mp 138 140°C.
1H NMR (CDCl3): = 2.29 (quintet, 2H, J = 5 Hz, OCH2CH2), 3.52
(d, 4H, J = 6.6 Hz, CH2-CH=CH2), 4.23 (t, 4H, J = 5.2 Hz, OCH2),
5.16 (d, 2H, Jcis = 9.2 Hz, CH2=CH), 5.20 (d, 2H, Jtrans = 16.0 Hz,
CH=CH2), 5.92 6.15 (m, 2H, CH=CH2), 7.13 8.22 (m, 11H, Ar-
H), 15.13 (s, 1H, NH).
1H NMR (CDCl3): = 2.15 (s, 6H, COCH3), 3.81 (d, 4H, J = 6.2 Hz,
CH2-CH=CH2), 5.36 5.47 (m, 8H, CH=CH2, OCH2), 6.18 6.40
(m, 2H, CH=CH2), 7.24 8.47 (m, 10H, Ar-H), 8.32 (br s, 2H, NH).
Anal. Calcd for C30H32N2O4 (484.59): C, 74.36; H, 6.66; N, 5.78.
Found: C, 74.10; H, 6.50; N, 6.00.
MS: m/z (%) = 453 (M++1, 82), 250 (37), 160 (85), 91 (100).
Anal. Calcd for C28H28N4O2 (452.55): C, 74.31; H, 6.24; N, 12.38.
Found: C, 74.50; H, 6.33; N, 12.44.
N-(2-Allyloxyphenyl)phthalimide (9)
To a solution of 829 (5 mmol) in ethanolic sodium ethoxide solution
[prepared from Na (1.15 g, 5 mmol) and absolute EtOH (30 mL)]
was added allyl bromide (5 mmol). The reaction mixture was heated
under reflux for 4 h, the solvent was removed in vacuo, and the re-
maining precipitate was collected, washed with H2O, and crystal-
lized from EtOH as colorless crystals.
7,19-Diallyl-5,21-dihydro-11H-13-phenyltribenzo[b,i,m]-
[1,11,4,5,7,8]dioxatetraazacyclopentadecine-13-carbonitrile (2d)
Prepared from 3b.
Deep red crystals; yield: 7%; Rf = 0.67; mp 154 156°C.
1
IR: = 1642 (C=C), 1261, 1054 (N=N) cm .
Yield: 70%; mp 117°C.
1H NMR (CDCl3): = 3.62 (d, 4H, J = 6.2 Hz, CH2-CH=CH2),
5.10 5.29 (m, 8H, OCH2, CH=CH2), 6.00 6.20 (m, 2H,
CH=CH2), 7.19 8.22 (m, 15H, Ar-H), 15.08 (s, 1H, NH).
IR: = 1705, 1770 (C=O), 1640 (C=C) cm–1.
1H NMR (CDCl3): = 4.56 (d, 2H, Jcis = 6.4 Hz, CH2-CH=CH2),
5.14 (d, 1H, J = 10.6 Hz, CH=CH2), 5.25 (d, 1H, Jtrans = 17.4 Hz,
CH=CH2), 5.83 6.0 (m, 1H, CH=CH2), 7.08 7.97 (m, 8H, Ar-H).
MS: m/z (%) = 515 (M+, 42), 410 (22), 250 (100), 91 (100).
Anal. Calcd for C33H30N4O2 (514.62): C, 77.02; H, 5.88; N, 10.89.
Found: C, 76.95, H, 5.92; N, 10.59.
Anal. Calcd for C17H13NO3 (279.29): C, 73.11; H, 4.69; N, 5.02.
Found: C, 72.99; H, 4.75; N, 4.90.
Bis(2-aminophenoxy)ether Dihydrochlorides 3a,b; General
Procedure
N-(3-Allyl-2-hydroxyphenyl)phthalimide (10)
Compound 9 (5 mmol) was heated in an oil bath at 180 190°C for
2 h. The remaining materials upon cooling were triturated with
EtOH, collected, and crystallized from EtOH to give 10 as colorless
crystals.
To a solution of 13 (or 14) (10 mmol) in absolute EtOH (20 mL) was
added concd HCl (16 mL). The reaction mixture was heated under
reflux for 1 h and the solvent was removed in vacuo. The remaining
solid was collected and crystallized from EtOH Et2O to give pale
yellow crystals of 3a (or 3b).
Yield: 55%; mp 168 170°C.
IR: = 3343 (OH), 1703, 1774 (C=O), 1641 (C=C) cm–1.
1,3-Bis(6-allyl-2-aminophenoxy)propane Dihydrochloride (3a)
Colorless crystals; yield: 70%; mp 232 234°C.
1H NMR (CDCl3): = 3.48 (d, 2H, J = 6.4 Hz, CH2-CH=CH2), 5.15
(d, 1H, Jcis = 10.6 Hz, CH=CH2), 5.19 (d, 1H, Jtrans = 18.0 Hz,
CH=CH2), 5.92 6.15 (m, 1H, CH=CH2), 6.98 7.96 (m, 7H, Ar-
H).
Anal. Calcd for C21H28Cl2N2O2 (411.37): C, 61.31; H, 6.86; N, 6.81;
Cl, 17.24. Found: C, 61.50; H, 6.50; N, 6.50; Cl, 16.99.
Anal. Calcd for C17H13NO3 (279.29): C, 73.11; H, 4.69; N, 5.02.
Found: C, 73.29; H, 4.76; N, 5.23.
1,2-Bis(6-allyl-2-aminophenoxymethyl)benzene Dihydrochloride
(3b)
Colorless crystals; yield: 72%; mp 240 242°C.
6-Allyl-2-aminophenol Hydrochloride (11)
(a) To a solution of 10 (10 mmol) in EtOH (20 mL) was added hy-
drazine hydrate (15 mmol) and HCl (2 mL). The reaction mixture
was heated under reflux for 30 min. The solid obtained was collect-
ed by filtration. The filtrate was concentrated by rotary evaporator
(approx. 10 mL) and then kept in the freezer overnight. The solid
obtained was collected and crystallized from EtOH as colorless
crystals.
Anal. Calcd for C26H30Cl2N2O2 (473.44): C, 65.96; H, 6.39; N, 5.92;
Cl, 14.98. Found: C, 66.21; H, 6.44; N, 6.20; Cl, 14.77.
1,3-Bis(2-acetamido-6-allylphenoxy)propane (13) and 1,2-
Bis(2-acetamido-6-allyl-phenoxymethyl)benzene (14); General
Procedure
To a solution of the potassium salt of 121 (20 mmol) in DMF was
added 1,3-dibromopropane or , -dibromo-o-xylene (10 mmol).
The reaction mixture was heated under reflux for 15 min. The sol-
vent was removed in vacuo, the remaining residue was washed with
Yield: 70%; mp 215 217°C.
Synthesis 2001, No. 9, 1331–1336 ISSN 0039-7881 © Thieme Stuttgart · New York

1336
A. A. Abbas, A. H. M. Elwahy
PAPER
Anal. Calcd for C9H12ClNO (185.65): C, 58.23; H, 6.51; N, 7.54;
Cl, 19.10. Found: C, 58.50; H, 5.76; N, 7.70; Cl, 18.91.
(12) Attiyat, A. S.; Ibrahim, Y. A.; Christain, G. D. Microchem.
J. 1988, 37, 122.
(13) (a) Sitnikova, R. V.; Krylova, A. N.; Zelichenok, S. L.;
Dziomko, V. M.; Ostrovskaya, V. M.; Zhukova, T. E.;
Tolmacheva, E. I. Zh. Anal. Khim. 1982, 37, 611. (b)Chem.
Abstr. 1982, 97, 174017.
(b) To a solution of 12 (10 mmol) in EtOH (20 mL) was added HCl
(2 mL), the reaction mixture was heated under reflux for 1 h. The
solvent was removed in vacuo and the remaining material was col-
lected and crystallized as in method (a), yield: 75%.
(14) Christain, G. D. Lithium 1990, 3, 181.
(15) (a) Ostrovskaya, V. M.; Sitnikova, I. G.; Ryabokobylko, Yu.
S.; Dziomko, V. M.; Sitnikova, R. V.; Avrutskii, Ya. G.;
Neduva, A. A.; Misionzhnik, E. Yu. Otkrytiya, Izobret.
1989, 185. (b) Chem. Abstr. 1989, 111, 224523.
(16) (a) Kravchenko, M. S.; Ostrovskaya, V. M.; Fumarova, M.
Sh. Vysokochist. Veshchestva 1990, 152. (b) Chem. Abstr.
1991, 114, 239405.
(17) Ibrahim, Y. A.; Elwahy, A. H. M.; Abbas, A. A. Heteroat.
Chem. 1996, 7, 215.
(18) Abbas, A. A. Tetrahedron 1998, 54, 12421.
(19) Ibrahim, Y. A.; Elwahy, A. H. M.; Barsum, N. B.; Abbas, A.
A.; Kella, S. K. Talanta 1998, 47, 1199.
(20) Ibrahim, Y. A.; Barsum, N. B.; Elwahy, A. H. M.; Kella, S.
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