Synthesis and reactivity of 3-(1-hydroxy-3-buten-1-yl)chromone

Article abstract of DOI:10.3184/030823408X314437

Zn-induced allylation of chromone-3-carbaldehyde 1 produces 3-(1-hydroxy-3-butene-1-yl)chromone 2, which gives back 1 on treatment with formalin under acidic conditions, and reacts differently towards nitrogenous nucleophiles.

Full text of DOI:10.3184/030823408X314437

208 RESEARCH PAPER
APRIL, 208–211
JOURNAL OF CHEMICAL RESEARCH 2008
Synthesis and reactivity of 3-(1-hydroxy-3-buten-1-yl)chromone
Partha Karmakar, Tarun Ghosh, Debasish Chakrabarty, Sourav Maiti and
Chandrakanta Bandyopadhyay*
Department of Chemistry, R. K. Mission Vivekananda Centenary College, Rahara, Kolkata 700 118, West Bengal, India
Zn-induced allylation of chromone-3-carbaldehyde 1 produces 3-(1-hydroxy-3-butene-1-yl)chromone 2, which gives
back 1 on treatment with formalin under acidic conditions, and reacts differently towards nitrogenous nucleophiles.
Keywords: allylation, oxonia-Cope rearrangement, 3-formylchromone, Schiff bases, 1-benzopyrans
Prins reaction on homoallyl alcohol has drawn much attention
in recent years as it provides an easy route for the synthesis of
tetrahydropyran rings, which are widely distributed in many
complex natural products.1 4-Substituted tetrahydropyran
moieties have been synthesied from the reaction of homoallylic
alcohol and aldehyde in the presence of Brønsted or Lewis
acid, HCl or HBr,2-4 InCl35,6 and In(OTf)3.7,8 Acetals involving
the homoallyl alcohol in place of a mixture of aldehyde and
homoallyl alcohol can produce tetrahydropyran in the presence
of TiCl4 or SnBr4.9 Recently, one-pot Prins-Ritter reaction
on homoallyl alcohol has been carried out in the presence of
CeCl3 catalyst.10 Alkenes react with formaldehyde in presence
of H2SO4 in AcOH to produce 1,3-diacetoxy compounds.11
In an attempt to synthesise a tetrahydropyran ring linked at
the 3-position of a chromone ring, Barbier allylation and then
thePrinsreactionwereemployedonchromone-3-carbaldehyde
1.12 The synthesis of 3-(1-hydroxy-3-buten-1-yl)chromone 2
and some of its reactions are reported in this paper.
A few cases of allyl transfer reaction have been reported.13-19
Pyrolysis of a β–hydroxyolefin produces the carbonyl
compound and alkene.20 To verify the possibility of thermal
rearrangement, compound 2 was heated neat at 150°C for 4 h,
but no change was observed. Again, no aldehyde 1 was
detected from the reaction mixture obtained by heating 2 under
reflux for 6 h in AcOH containing a trace of concentrated
H2SO4. Considering the involvement of formaldehyde, a
plausible mechanism is considered based on 2-oxonia Cope
rearrangement. In this, a [3,3]-sigmatropic shift on 3 produces
4, which on hydrolysis gives 1 (Scheme 2).
Considering the overall process to be a case of allylation
and deallylation on the formyl function of 1, we tried to utilise
this chemistry as a protection and deprotection of aldehyde
function in 1. It has been reported that acetalation of 1 is
not adequate protection for the aldehyde function towards
nitrogenous nucleophiles.21
Treatment of 2 with NH2OH in ethanol produces 5,
1
which appeared from H NMR as a mixture of the syn and
Results and discussion
anti dioximes. It resembles the product obtained from the
reaction of hydroxylamine with chromone 6 (Scheme 3),22
but compound 5a could not be isolated in pure form from the
reaction mixture of 2a and NH2OH.
The reaction may proceed by initial attack of NH2OH at the
C-2 position of the chromone moiety of 2 to produce 7, which
tautomerises to the monooxime 8 (Scheme 3). Base-induced
retro-aldol type C–C bond cleavage followed by oximation or
oximation followed by base-induced C–C bond cleavage leads
to 5 as a mixture of syn and anti dioximes. Formation of 5
A mixture of aldehyde 1 (1 equiv.), allyl bromide (1.5 equiv.)
and Zn dust (4 equiv.) in THF containing saturated aqueous
NH4Cl was stirred for 12 h. After the usual work-up and
chromatographic separation compound 2 was isolated in
moderate yields (Scheme 1). In order to synthesise the
dihydropyran, homoallylic alcohol 2 was heated with formalin
under reflux in acetic acid containing a trace of H2SO4.
Surprisingly, and somewhat disappointingly, the compound
isolated after work up was found to be 1 (Scheme 1).
O
O
Ha
a
Hn
Hm
R
R
CHO
Hb
b
H
OH
O
O
Hx
2
1
For 1-15 a: R = H
b: R = Me
Reagents: a, allyl bromide / Zn / NH4Cl, THF-H2O
b, CH2O / H2SO4, AcOH
c: R = Cl
Scheme 1
O
O
O
O
CH2O/H+
R
R
R
O
O
O
O
O
3
4
CH2
H
2
H2O
1 + CH3CH=CH2
1 + HOCH2CH2CH=CH2
Scheme 2
* Correspondent. E-mail: kantachandra@rediffmail.com
PAPER: 08/5008

JOURNAL OF CHEMICAL RESEARCH 2008 209
OH
O
O
2 + NH2OH
H
R
R
NOH
N
OH
6
5
NH2OH
OH
H
R
R
HO
O
H
NHOH
R
H
O
NOH
OH
OH
O
O
NOH
8
7
Scheme 3
from 2 may also be considered to proceed via the intermediate
formation of chromone 6. To confirm the feasibility of the
formation of 6 from 2, it was heated in EtOH containing 2
equiv. of pyridine for 6 h, but no change was observed.
However, when the same experiment was performed using
piperidine (2 equiv.) in place of pyridine, chromone 6 was
produced as the only isolable product (Scheme 4). Formation
of chromone 6 from 2 may be rationalised by considering a
Michael-type addition of piperidine to the C2-C3 bond of the
chromone ring of 2 to form 9. Intramolecular proton transfer
followed by the expulsion of 3-butenal (10) and piperidine
from 9 lead to the formation of 6. Regarding the function of
piperidine as a catalyst here, it was found that a lesser amount
of piperidine (0.5 equiv.) failed to complete the reaction even
after 10 h of heating. This may be due to interaction of the
piperidine with 3-butenal. Compound 2 failed to react with
o-phenylenediamine or p-toluidine when heated in ethanol for
20 h or 12 h, respectively.
Reaction of 2 with ethylenediamine (11) produces the Schiff
base 12, rather than a diazepine derivative bearing the
homoallylic alcohol moiety. It has been reported23 that the
chromone 6 reacts with ethylenediamine to form 2,3-dihydro-
5-(2-hydroxyphenyl)-1,4-diazepine. Hence the possibility
of formation of 6 as an intermediate en route to 12 can be
ruled out. Formation of 12 may be rationalised by considering
the initial attack of an amino function of ethylenediamine at
the C-2 position of the pyran ring of 2 followed by the pyran
ring opening to form 13 (Scheme 5). The second amino
function of ethylenediamine attacks the β–position of the αβ–
unsaturated ketone moiety of 13 resulting in the imidazolidine
14. Subsequent expulsions of butenal and imidazoline lead
to the formation of o-hydroxyacetophenone 15, which
reacts with ethylenediamine to form the diimine 12. Indeed,
o-hydroxyacetophenone reacts with ethylenediamine in EtOH
readily to form 12 (R = H) in excellent yield. The sequence
of elimination of the butenal and imidazoline moieties in 14
could not be ascertained.
N
O
O
H
O
+
2
+
6
+
CHO
R
N
H
N
H
10
9
Scheme 4
OH
OH
HO
NH2
11
2 +
N
N
O
R
R
R
NH2
11
CH3
CH3
CH3
15
12
- imidazoline
H
O
R
R
R
HO
- 10
H
N
H
N
H
N
OH
O
OH
O
OH
O
HN
N
H2N
H
14
13
Scheme 5
PAPER: 08/5008

210ꢀ JOURNALꢀOFꢀCHEMICALꢀRESEARCHꢀ2008
1-(5-Chloro-2-hydroxyphenyl)propane-1,3-dione 1,3-dioxime (5c):ꢀ
White fine crystalline compound (105 mg, 92%); m.p. 168–170°C. IR:
νmaxꢀ3279,ꢀ2888,ꢀ1640,ꢀ1595,ꢀ1485ꢀcm-1. NMR: δHꢀ(DMSO-d6)ꢀ(syn:ꢀ
anti 5:ꢀ3)ꢀ3.68ꢀ(2ꢀH,ꢀd,ꢀJꢀ=ꢀ4.9ꢀHz,ꢀCH2ꢀa),ꢀ3.74ꢀ(2ꢀH,ꢀd,ꢀJꢀ=ꢀ4.9ꢀHz,ꢀ
CH2ꢀs),ꢀ6.66ꢀ(1ꢀH,ꢀt,ꢀJꢀ=ꢀ4.9ꢀHz,ꢀCH=Nꢀs),ꢀ6.90ꢀ(2ꢀH,ꢀd,ꢀJꢀ=ꢀ8.6ꢀHz,ꢀ
3'-Hꢀsꢀ+ꢀa),ꢀ7.27ꢀ(2ꢀH,ꢀdd,ꢀJꢀ=ꢀ8.6,ꢀ2.1ꢀHz,ꢀ4'-Hꢀsꢀ+ꢀa),ꢀ7.39ꢀ(1ꢀH,ꢀd,ꢀ
Jꢀ=ꢀ2.1ꢀHz,ꢀ6'-Hꢀs),ꢀ7.42ꢀ(1ꢀH,ꢀd,ꢀJꢀ=ꢀ2.1ꢀHz,ꢀ6'-Hꢀa),ꢀ7.49ꢀ(1ꢀH,ꢀt,ꢀ
Jꢀ=ꢀ4.9ꢀHz,ꢀCH=Nꢀa),ꢀ10.69ꢀ(1ꢀH,ꢀs,ꢀexchangeable,ꢀC3-OHꢀa),ꢀ11.10ꢀ
(1ꢀH,ꢀs,ꢀexchangeable,ꢀC3-OHꢀs),ꢀ11.18ꢀ(1ꢀH,ꢀs,ꢀexchangeable,ꢀC1-OHꢀ
s),ꢀ11.28ꢀ(1ꢀH,ꢀs,ꢀexchangeable,ꢀC1-OHꢀa),ꢀ11.85ꢀ(1ꢀH,ꢀs,ꢀexchange-
able,ꢀC2'-OHꢀs)ꢀandꢀ11.87ꢀ(1ꢀH,ꢀs,ꢀexchangeable,ꢀC2’-OHꢀa).ꢀAnal.ꢀ
calcd.ꢀforꢀC9H9ClN2O3:ꢀC,ꢀ47.28;ꢀH,ꢀ3.97;ꢀN,ꢀ12.25.ꢀFound:ꢀC,ꢀ47.05;ꢀ
H,ꢀ3.85;ꢀN,ꢀ12.01.
Inꢀ conclusion,ꢀ weꢀ haveꢀ studiedꢀ anꢀ allylation-deallylationꢀ
reactionꢀ ofꢀ theꢀ chromoneꢀ aldehydesꢀ 1ꢀ andꢀ alsoꢀ theꢀ retro-
aldolꢀreactionꢀofꢀtheꢀhomoallylꢀalcoholsꢀ2ꢀinducedꢀbyꢀsomeꢀ
nitrogenousꢀnucleophiles.
Experimental
IRꢀspectraꢀwereꢀrecordedꢀinꢀKBrꢀonꢀaꢀBeckmannꢀIRꢀ20Aꢀinstrument,ꢀ
1HꢀNMRꢀspectraꢀinꢀCDCl3ꢀonꢀaꢀBrukerꢀ300ꢀMHzꢀspectrometer,ꢀmassꢀ
spectraꢀonꢀanꢀQtofꢀMicroꢀYAꢀ263ꢀinstrumentꢀandꢀelementalꢀanalysesꢀ
onꢀaꢀPerkinꢀElmerꢀ240Cꢀelementalꢀanalyser.ꢀLightꢀpetroleumꢀrefersꢀtoꢀ
theꢀfractionꢀwithꢀdistillationꢀrangeꢀ60-80°C.
Allylation of chromone-3-carbaldehydeꢀ(1):ꢀgeneral procedure
Theꢀaldehydeꢀ1ꢀ(10ꢀmmol),ꢀZnꢀdustꢀ(2.5ꢀg,ꢀ40ꢀmmol),ꢀallylꢀbromideꢀ
(1.8ꢀg,ꢀ15ꢀmmol)ꢀwasꢀstirredꢀinꢀTHFꢀ(100ꢀml)ꢀcontainingꢀsaturatedꢀ
aqueousꢀNH4Clꢀ(2ꢀml)ꢀforꢀ12ꢀhꢀatꢀroomꢀtemperature.ꢀTheꢀreactionꢀ
mixture was then filtered, the solvent was removed from the filtrate
underꢀ reducedꢀ pressure,ꢀ andꢀ ice-waterꢀ (50ꢀ g)ꢀ wasꢀ addedꢀ toꢀ theꢀ
concentrate.ꢀAnꢀoilyꢀmassꢀseparatedꢀandꢀwasꢀextractedꢀwithꢀCHCl3.ꢀ
Theꢀ organicꢀ layerꢀ wasꢀ washedꢀ withꢀ brine,ꢀ driedꢀ overꢀ Na2SO4ꢀ andꢀ
chromatographedꢀonꢀsilicaꢀgelꢀ(100–200).ꢀCompoundꢀ2 wasꢀobtainedꢀ
fromꢀtheꢀcolumnꢀusingꢀbenzeneꢀasꢀeluent.
Treatment ofꢀ2ꢀwith piperidine: formation of chromonesꢀ6
Theꢀchromoneꢀ2 (1ꢀmmol)ꢀandꢀpiperidineꢀ(170ꢀmg,ꢀ2ꢀmmol)ꢀwereꢀ
heated under reflux in ethanol (15 ml) for 6 h. The reaction mixture
wasꢀ concentratedꢀ underꢀ reducedꢀ pressure.ꢀ Ice-waterꢀ (25ꢀ g)ꢀ wasꢀ
addedꢀtoꢀtheꢀconcentrate.ꢀTheꢀoilyꢀmassꢀseparatedꢀwasꢀextractedꢀwithꢀ
CHCl3,ꢀwashedꢀwithꢀwater,ꢀdriedꢀoverꢀNa2SO4ꢀandꢀchromatographedꢀ
overꢀsilicaꢀgelꢀ(100–200).ꢀCompoundꢀ6ꢀwasꢀisolatedꢀusingꢀbenzeneꢀasꢀ
eluent.ꢀTheꢀcompoundsꢀwereꢀidenticalꢀinꢀallꢀrespectsꢀwithꢀauthenticꢀ
samples.
6-Methylchromoneꢀ(6b):ꢀYieldꢀ90ꢀmgꢀ(56%),ꢀm.p.ꢀ92–94°C;ꢀ(lit.25ꢀ
m.p.ꢀ93°C).
3-(1-Hydroxybut-3-en-1-yl)chromoneꢀ (2a):24ꢀ Faintlyꢀ yellowꢀ oilꢀ
(1.20 g, 56%). IR: νmaxꢀ3320,ꢀ2900,ꢀ1650,ꢀ1605,ꢀ1470ꢀcm-1.ꢀNMR:ꢀ
δHꢀ2.50-2.60ꢀ(1ꢀH,ꢀm,ꢀHm),ꢀ2.69–2.77ꢀ(1ꢀH,ꢀm,ꢀHn),ꢀ3.38ꢀ(1ꢀH,ꢀbrs,ꢀ
exchangeable,ꢀOH),ꢀ4.77ꢀ(1ꢀH,ꢀt,ꢀJꢀ=ꢀ6.4ꢀHz,ꢀCHOH),ꢀ5.13–5.18ꢀ(2ꢀH,ꢀ
m,ꢀHaꢀ+ꢀHb),ꢀ5.80–5.91ꢀ(1ꢀH,ꢀm,ꢀHx),ꢀ7.39–7.48ꢀ(2ꢀH,ꢀm,ꢀ6-H,ꢀ8-H),ꢀ
7.66–7.71ꢀ(1ꢀH,ꢀm,ꢀ7-H),ꢀ7.94ꢀ(1H,ꢀs,ꢀ2-H)ꢀandꢀ8.21ꢀ(1ꢀH,ꢀdd,ꢀJꢀ=ꢀ7.9,ꢀ
1.5ꢀHz,ꢀ5-H).
3-(1-Hydroxybut-3-en-1-yl)-6-methylchromoneꢀ(2b):ꢀLightꢀyellowꢀ
crystalline solid (1.40 g, 61%); m.p. 68–70°C. IR: νmaxꢀ3399,ꢀ2917,ꢀ
1638,ꢀ1605,ꢀ1484ꢀcm-1; δHꢀ2.45ꢀ(3ꢀH,ꢀs,ꢀCH3),ꢀ2.50–2.60ꢀ(1ꢀH,ꢀm,ꢀHm),ꢀ
2.67–2.75ꢀ(1ꢀH,ꢀm,ꢀHn),ꢀ3.40ꢀ(1ꢀH,ꢀbr,ꢀs,ꢀexchangeable,ꢀOH),ꢀ4.72ꢀ
(1ꢀH,ꢀt,ꢀJꢀ=ꢀ5.5ꢀHz,ꢀCHOH),ꢀ5.12–5.17ꢀ(2ꢀH,ꢀm,ꢀHaꢀ+ꢀHb),ꢀ5.79–5.92ꢀ
(1ꢀH,ꢀm,ꢀHx),ꢀ7.36ꢀ(1ꢀH,ꢀd, Jꢀ=ꢀ8.6ꢀHz,ꢀ8-H),ꢀ7.48ꢀ(1ꢀH,ꢀdd,ꢀJꢀ=ꢀ8.6,ꢀ2.2ꢀ
Hz,ꢀ7-H),ꢀ7.90ꢀ(1ꢀH,ꢀs,ꢀ2-H)ꢀandꢀ8.00ꢀ(1ꢀH,ꢀd,ꢀJꢀ=ꢀ2.2ꢀHz,ꢀ5-H).ꢀAnal.ꢀ
calcd.ꢀforꢀC14H14O3:ꢀC,ꢀ73.03;ꢀH,ꢀ6.13.ꢀFound:ꢀC,ꢀ72.84;ꢀH,ꢀ5.90%.
6-Chloro-3-(1-hydroxybut-3-en-1-yl)chromoneꢀ(2c):ꢀLightꢀyellowꢀ
crystalline solid (1.50 g, 60%); m.p. 84–86°C. IR: νmax/cm-1ꢀ3319,ꢀ
2918, 1641, 1604, 1464; δHꢀ2.46–2.55ꢀ(1ꢀH,ꢀm,ꢀHm),ꢀ2.68–2.76ꢀ(1ꢀ
H,ꢀm,ꢀHn),ꢀ3.22ꢀ(1ꢀH,ꢀbrs,ꢀexchangeable,ꢀOH),ꢀ4.79ꢀ(1ꢀH,ꢀt,ꢀJꢀ=ꢀ5.8ꢀ
Hz,ꢀCHOH),ꢀ5.13–5.17ꢀ(2ꢀH,ꢀm,ꢀHaꢀ+ꢀHb),ꢀ5.79–5.92ꢀ(1ꢀH,ꢀm,ꢀHx),ꢀ
7.43ꢀ(1ꢀH,ꢀd, Jꢀ=ꢀ8.8ꢀHz,ꢀ8-H),ꢀ7.61ꢀ(1ꢀH,ꢀdd,ꢀJꢀ=ꢀ8.8,ꢀ2.3ꢀHz,ꢀ7-H),ꢀ
7.96ꢀ(1ꢀH,ꢀs,ꢀ2-H)ꢀandꢀ8.15ꢀ(1ꢀH,ꢀd,ꢀJꢀ=ꢀ2.3ꢀHz,ꢀ5-H);ꢀAnal.ꢀcalcd.ꢀforꢀ
C13H11ClO3:ꢀC,ꢀ62.29;ꢀH,ꢀ4.42.ꢀFound:ꢀC,ꢀ61.72;ꢀH,ꢀ4.25%.
6-Chlorochromoneꢀ (6c):ꢀYieldꢀ 100ꢀ mgꢀ (55%),ꢀ m.p.ꢀ 138–140°C;ꢀ
(lit.25ꢀm.p.ꢀ140°C).
Action of ethylenediamine withꢀ2:ꢀformation of bisiminesꢀ12
Aꢀ mixtureꢀ ofꢀ homoallylicꢀ alcoholꢀ 2ꢀ (1ꢀ mmol),ꢀ ethylenediamineꢀ
(180 mg, 3 mmol) in EtOH (15 ml) was heated under reflux forꢀ
5ꢀh.ꢀSolventꢀwasꢀremovedꢀfromꢀtheꢀreactionꢀmixtureꢀunderꢀreducedꢀ
pressureꢀ andꢀ coldꢀ waterꢀ (15ꢀ ml)ꢀ wasꢀ addedꢀ toꢀ theꢀ concentrate.ꢀ
Theꢀ resultantꢀ semisolidꢀ massꢀ wasꢀ extractedꢀ withꢀ benzene,ꢀ washedꢀ
withꢀwaterꢀandꢀdriedꢀoverꢀNa2SO4.ꢀOnꢀconcentrationꢀitꢀaffordedꢀ12ꢀasꢀ
aꢀyellowꢀcrystallineꢀsolid.
N,N'-bis[1-(2-hydroxyphenyl)ethylidene]ethylenediamineꢀ (12a):ꢀ
Yield (80 mg, 54%); m.p. 188–190°C. IR: νmaxꢀ3450,ꢀ2960,ꢀ1615,ꢀ
1500ꢀcm-1. δHꢀ2.39ꢀ(6ꢀH,ꢀs,ꢀ2ꢀ×ꢀCH3),ꢀ3.98ꢀ(4ꢀH,ꢀs,ꢀ2ꢀ×ꢀCH2),ꢀ6.76–
6.82ꢀ(2ꢀH,ꢀm,ꢀ2ꢀ×ꢀ5-H),ꢀ6.92ꢀ(2ꢀH,ꢀdd,ꢀJꢀ=ꢀ8.3,ꢀ0.9ꢀHz,ꢀ2ꢀ×ꢀ3-H),ꢀ
7.25–7.30ꢀ(2ꢀH,ꢀm,ꢀ2ꢀ×ꢀ4-H),ꢀ7.52ꢀ(2ꢀH,ꢀdd,ꢀJꢀ=ꢀ8.0,ꢀ1.2ꢀHz,ꢀ2ꢀ×ꢀ6-H)ꢀ
andꢀ15.84ꢀ(2ꢀH,ꢀbrs,ꢀexchangeable,ꢀ2ꢀ×ꢀOH);ꢀMS:ꢀm/zꢀ297ꢀ(Mꢀ+ꢀH+).
N,N'-bis[1-(5-Chloro-2-hydroxyphenyl)ethylidene]ethylenediamineꢀ
(12c): Yield (120 mg, 66%); m.p. 236–238°C. IR: νmaxꢀ3447,ꢀ2910,ꢀ
1615,ꢀ1492ꢀcm-1. δHꢀ2.38ꢀ(6ꢀH,ꢀs,ꢀ2ꢀ×ꢀCH3),ꢀ4.00ꢀ(4ꢀH,ꢀs,ꢀ2ꢀ×ꢀCH2),ꢀ
6.88ꢀ(2ꢀH,ꢀd,ꢀJꢀ=ꢀ9.0ꢀHz,ꢀ2ꢀ×ꢀ3-H),ꢀ7.23ꢀ(2ꢀH,ꢀdd,ꢀJꢀ=ꢀ9.0,ꢀ0.9ꢀHz,ꢀ
2ꢀ×ꢀ4-H),ꢀ7.50ꢀ(2ꢀH,ꢀd,ꢀJꢀ=ꢀ0.9ꢀHz,ꢀ2ꢀ×ꢀ6-H)ꢀandꢀ15.76ꢀ(2ꢀH,ꢀbrs,ꢀ
exchangeable,ꢀ2ꢀ×ꢀOH).
Reaction of the hydroxybutenyl chromoneꢀ2ꢀwith formaldehyde
Theꢀchromoneꢀ2ꢀ(2ꢀmmol),ꢀ37%ꢀaqueousꢀformaldehydeꢀ(1ꢀml)ꢀandꢀ
concentratedꢀ H2SO4ꢀ (threeꢀ drops)ꢀ inꢀ AcOHꢀ (10ꢀ ml)ꢀ wereꢀ heatedꢀ
under reflux for 2 h. The reaction mixture was concentrated under
reducedꢀpressure.ꢀIce-waterꢀ(15ꢀg)ꢀwasꢀthenꢀaddedꢀtoꢀtheꢀconcentrateꢀ
to afford a solid mass. This was filtered off, washed with water, dried
inꢀairꢀandꢀcrystallisedꢀfromꢀbenzene-lightꢀpetroleumꢀtoꢀaffordꢀ1ꢀasꢀaꢀ
whiteꢀcrystallineꢀsolid.ꢀCompoundsꢀ1aꢀ(210ꢀmg,ꢀ60%),ꢀ1bꢀ(300ꢀmg,ꢀ
80%)ꢀ andꢀ 1c (340ꢀ mg,ꢀ 81%)ꢀ wereꢀ identicalꢀ inꢀ allꢀ respectsꢀ withꢀ
authenticꢀsamples.
Compoundsꢀ 12a, cꢀ areꢀ identicalꢀ inꢀ allꢀ respectꢀ (m.p,ꢀ m.m.pꢀ andꢀ
superimposableꢀ IR)ꢀ withꢀ theꢀ samplesꢀ preparedꢀ fromꢀ appropriateꢀ
hydroxyacetophenonesꢀ15ꢀandꢀethylenediamine.
WeꢀgratefullyꢀacknowledgeꢀC.ꢀS.ꢀI.ꢀR.,ꢀNewꢀDelhiꢀ[Projectꢀ
no. 01(2206)/07/EMR-II] for financial assistance; IICB and
IACS, Jadavpur for spectral analysis and finally the college
authorityꢀforꢀprovidingꢀresearchꢀfacilities.
Received 20 December 2007; accepted 10 April 2008
Paper 07/5008 doi: 10.3184/030823408X314437
Reaction of chromoneꢀ2ꢀwith hydroxylamine; formation of dioximesꢀ5
Compoundꢀ 2ꢀ (0.5ꢀ mmol),ꢀ hydroxylamineꢀ hydrochlorideꢀ (140ꢀ mg,ꢀ
2ꢀmmol)ꢀandꢀsodiumꢀacetateꢀ(330ꢀmg,ꢀ4ꢀmmol)ꢀinꢀEtOHꢀ(25ꢀml)ꢀwereꢀ
heated under reflux for 4 h. Solvent was then removed under reduced
pressureꢀtoꢀleaveꢀaꢀwhiteꢀsolid.ꢀIce-waterꢀ(10ꢀg)ꢀwasꢀadded,ꢀstirredꢀforꢀ
10 min and filtered. The residue was washed with water, dried in air
andꢀrecrystallisedꢀfromꢀCHCl3/MeOHꢀtoꢀgiveꢀtheꢀdioximeꢀ5ꢀasꢀwhiteꢀ
fine crystalline solid.
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