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European	Journal	of	Chemistry	3	(3)	(2012)	314‐315	

European	Journal	of	Chemistry	
ISSN	2153‐2249	(Print)	/	ISSN	2153‐2257	(Online)		2012	EURJCHEM	

DOI:10.5155/eurjchem.3.3.314‐315.641	

	
	

	

	

European	Journal	of	Chemistry	
Journal	homepage:	www.eurjchem.com	

	 	 	

Selective	iodination	of	2‐acetyl‐1‐naphthol	using	iodine	and	iodic	acid		
under	solvent‐free	grinding	technique 

Sainath	Zangadea,*,	Shyam	Mokleb,	Avinash	Shindeb	and	Yeshwant	Vibhuteb	

a	Department	of	Chemistry,	Madhavrao	Patil	Mahavidyalaya,	Palam,	Prabhani,	Maharashtra,	431720,	India	
b	Laboratory	of	Organic	Synthesis,	Department	of	Studies	in	Chemistry,	Yeshwant	Mahavidyalaya,	Nanded,	Maharashtra,	431602,	India	

*Corresponding	author	at:	Department	of	Chemistry,	Madhavrao	Patil	Mahavidyalaya,	Palam,	Prabhani,	Maharashtra,	431720,	India.		
Tel.:	+91.982.2939699;	fax:	+91.246.2253726.	E‐mail	address:	drsbz@rediffmail.com		(S.	Zangade).	

	
	

	 	

	 	 	
ARTICLE	INFORMATION	 	 ABSTRACT
Received:	27	May	2012	
Received	in	revised	form:	02	June	2012	
Accepted:	02	June	2012	
Online:	30	September	2012	

KEYWORDS	

	 Selective	electrophilic	 iodination	of	2‐acetyl‐1‐naphthol	was	achieved	using	 iodine	and	 iodic
acid	in	combination	with	grinding	at	room	temperature	under	solvent‐free	conditions	to	yield
1‐(1‐hydroxy‐4‐iodo‐naphthalen‐2‐yl)‐ethanone.	Grinding	mode	of	 reactions	has	 not	 only	 of
interest	from	economical	point	of	view,	in	many	cases	they	also	offer	considerable	advantages
in	terms	of	yield,	mild	reaction		conditions,	selectivity	and	simplicity	of	reaction	procedure.	

Iodine	
Iodic	acid	
Solvent‐free	
Grinding	technique	
Selective	iodination	
2‐Acetyl‐1‐naphthol	

	
1.	Introduction	
	

Aromatic	 iodo	 compounds	 are	 valuable	 and	 versatile	
synthetic	 intermediates	 in	 organic	 chemistry	 [1].	 They	 are	
useful	for	the	preparation	of	organometallic	reagents,	and	some	
are	potential	intermediates	for	the	synthesis	of	pharmaceutical	
and	bioactive	materials	[2,3].	They	are	also	 important	and	the	
most	 reactive	 intermediates	 for	 various	 cross‐coupling	
reactions	and	especially	useful	for	formation	of	carbon‐carbon	
and	 carbon‐heteroatom	 bonds	 [4].	 Recently	 the	 reagents	
reported	 for	 iodination	 of	 arenes	 include,	 iodine‐nitrogen	
dioxide	 [5],	 iodine	 F‐TEDA‐[1‐chloromethyl‐4‐fluoro‐1,4‐
diazoniabicyclo	 [2,2,2]	 octane‐bis‐(tetrafluoroborate)]	 [6],	 bis‐
N‐iodosuccinimide	 [7],	 trichloroisocyanuric	 acid‐I2‐Wet	 SiO2	
[8],	 mercury(II)‐oxide‐iodine	 [9],	 iodine‐monochloride	 [10],	
bis(pyridine)iodonium(I),	tetrafluoroborate	CF3SO3H	[11],	NIS‐
CF3SO3H	 [12],	 iodine	 silver	 sulfate	 [13],	 iodine‐mercury	 salts	
[14]	 and	 NaOCl‐NaI	 [15].	 However,	 most	 of	 these	 methods	
suffer	 from	major	drawbacks	 such	 as	use	of	harsh	 conditions,	
toxic	 heavy‐metal	 catalysts,	 non‐slectivity	 and	 longer	 reaction	
times.	Use	of	iodine	in	combination	with	iodic	acid	found	to	be	
an	 efficient	 iodinating	 agent	 for	 iodination	 for	 aromatic	
compounds.	 In	view	of	 these	observations	we	report	here	 the	
selective	 iodination	 of	 2‐acetyl‐1‐naphthol	 (bicyclic	 arene)	
using	 iodine	 and	 iodic	 acid	 under	 solvent‐free	 environment	
using	grinding	technique	(Scheme	1).	
	
2.	Experimental	
	
2.1.	Instrumentation	
	

Melting	point	was	determined	in	an	open	capillary	tube	and	
is	 uncorrected.	 IR	 spectra	 were	 recorded	 in	 KBr	 pellets	 on	 a	
Shimadzu	 FT‐IR	 spectrometer.	 1H	 and	 13C	 NMR	 spectra	 were	

obtained	 in	DMSO‐d6	 on	Avance	300	MHz	 spectrometer	using	
TMS	as	an	internal	standard.	The	mass	spectra	were	recorded	
on	EI‐Shimadzu‐GC‐MS	spectrometer.	Elemental	analyses	were	
performed	 on	 a	 Carlo	 Erba	 106	 Perkin‐Elmer	 model	 240	
analyzer.	
	
2.2.	Synthesis	
	

Mixture	 of	 2‐acetyl‐1‐naphthol	 (50	 mmol),	 iodine	 (20	
mmol),	 taken	 in	open	mortar	and	grind	with	pestle	 for	2	min.	
To	 this	 reaction	 mixture	 saturated	 solution	 of	 iodic	 acid	 (10	
mmol)	 was	 added	 and	 grinding	 was	 continued	 up	 to	
disappearance	 of	 reactant	 spot	 on	 thin	 layer	 chromatography	
(TLC).	 After	 completion	 of	 grinding	 saturated	 solution	 of	
Na2S2O3	 (10	 mL)	 was	 added	 to	 remove	 excess	 of	 iodine	 to	
obtained	 solid	 product.	 Resultant	 solid	 product	 was	 filtered	
through	 simple	 büchner	 funnel,	 washed	 with	 cold	 water	 and	
crystallized	 from	 ethanol	 to	 yield	 1‐(1‐hydroxy‐4‐iodo‐
naphthalen‐2‐yl)‐ethanone	 (Scheme	 1).	 The	 purity	 of	
compound	was	checked	by	TLC,	using	hexane/	ethyl	acetate	as	
the	mobile	phase.	

1‐(1‐Hydroxy‐4‐iodo‐naphthalen‐2‐yl)‐ethanone:	 Color:	
Light	 greenish.	 Yield:	 94%.	M.p.:	 156	 oC.	 FT‐IR	 (KBr,	 ν,	 cm‐1):	
3070,	1726,	1622,	1583,	1494,	1442,	1411,	1232,	831,	759.	1H	
NMR	(300	MHZ,	DMSO‐d6,	δ,	ppm):	14.0	(s,	1H,	OH),	8.2	(s,	1H,	
Ar‐H),	8.4‐7.2	(m,	4H,	Ar‐H),	2.7	(s,	3H,	CH3).	13C	NMR	(75	MHz	
DMSO‐d6,	 δ,	 ppm):	 196.24	 (C	 of	 C=O),	 156.35	 (C	 of	 Ar‐OH),	
137.63	 (C	 of	 Ar‐C),	 135.37	 (C	 of	 Ar‐C),	 132.73	 (C	 of	 Ar‐C),	
131.86	 (C	 of	 Ar‐C),	 129.70	 (C	 of	 Ar‐C),	 127.48	 (C	 of	 Ar‐C),	
124.58	(C	of	Ar‐C),	120.14	(C	of	Ar‐C),	93.89	(C	of	Ar‐I),	24.17	
(C	of	CH3).	MS	(EI,	m/z	(%)):	312	(M+,	100),	297	(60),	294	(20),	
269	(10),	241	(20),	186	(5),	167	(10),	142	(20),	128	(40),	114	
(65),	 74	 (20),	 63	 (30).	 Anal.	 calcd.	 for	 C12H9O2I:	 C,	 46.15;	 H,	
2.88.	Found:	C,	45.18;	H,	2.86	%.	



Zangade	et	al.	/	European	Journal	of	Chemistry	3	(3)	(2012)	314‐315	 315	
 

	

	
	

Scheme	1
	
	
3.	Result	and	discussion	
	

In	continuation	of	earlier	research	work	[16‐19],	we	report	
here	 in	 a	 simple,	 rapid,	 efficient	 and	 environmentally	 benign	
solvent‐free	iodination	of	2‐acetyl‐1‐naphthol	using	iodine	and	
iodic	 acid	 in	 combination	with	grinding	 at	 room	 temperature.	
The	iodination	occur	selectively	at	electron	rich	centre	i.e.	para‐
position	 to	 ‐OH	 group.	 The	 corresponding	 product	 1‐(1‐
hydroxy‐4‐iodo‐naphthalen‐2‐yl)‐ethanone	 obtained	 in	 94%	
yield.	 In	 grindstone	 technique,	 reaction	 occurs	 through	
generation	of	local	heat	by	grinding	of	crystals	of	substrate	and	
reagent.	Reactions	are	initiated	by	grinding,	with	the	transfer	of	
very	 small	 amount	 of	 energy	 through	 friction.	 Such	 reactions	
are	 simple	 to	handle,	 reduce	pollution,	 comparatively	 cheaper	
to	 operate	 and	 may	 regarded	 as	 more	 economical	 and	
ecologically	 favorable	 procedure	 in	 chemistry	 [20].	 Obtained	
iodo	 product	 established	 on	 the	 basis	 of	 spectral	
characterization,	 IR,	 1H	 NMR,	 13C	 NMR,	 MS,	 and	 elemental	
analysis.	
	
4.	Conclusion	
	

In	 summary,	 we	 have	 described	 selective	 iodination	 of							
2‐acetyl‐1‐naphthol	using	 iodine	and	iodic	acid	under	solvent‐
free	grindstone	technique.		

	
Acknowledgements	
	

The	 authors	 gratefully	 acknowledge	 University	 Grant	
Commission	 (UGC)	 New	Delhi	 for	 sanctioning	major	 research	
grant	 (No.	 38‐267/2009).	 The	 authors	 are	 also	 thankful	 to	
Principal,	 Yeshwant	 Mahavidyalaya,	 Nanded,	 for	 providing	
laboratory	 facilities	 and	 Director	 Indian	 Institute	 of	 Chemical	
Technology	 (IICT),	 Hyderabad,	 for	 providing	 necessary	
instrumental	facilities.		
	
References	
	
[1]. Diederich,	 F.;	 Stang,	 P.	 J.	 Metal‐Catalyzed	 Cross	 Coupling	 Reactions;	

Wiley‐VCH:	Weinheim,	Germany,	1998.		
[2]. Seevers,	R.	H.;	Counsell,	R.	Chem.	Rev.	1982,	82,	575‐590.		
[3]. Alonso,	F.;	Beletskaya,	I.	P.;	Yus,	M.	Chem.	Rev.	2002,	102,	4009‐4092.		
[4]. Olivera,	R.;	San	Martin,	R.;	Dominguez,	E.	Tetrahedron	Lett.	2000,	41,	

4357‐4360.		
[5]. Noda,	Y.;	Kashima,	M.	Tetrahedron	Lett.	1997,	38,	6225‐6228.		
[6]. Zupan,	M.;	Iskra,	J.;	Stavber,	S.	Tetahedron	Lett.	1997,	38,	6305‐6306.		
[7]. Carreno,	 M.	 C.;	 Ruano,	 J.	 G.;	 Sanz,	 G.;	 Toledo,	 M.	 A.;	 Urbano,	 A.	

Tetrahedron	Lett.	1996,	37,	4081‐4084.		
[8]. Akhlaghinia,	B.;	Rahmani,	M.	Turk.	J.	Chem.	2009,	33,	67‐72.		
[9]. Orito,	K.;	Hatakeyama,	T.;	Takeo,	M.	Synthesis	1995,	1273‐1277.		
[10]. Hubig,	S.	M.;	Jung,	W.;	Kochi,	J.	K.	J.	Org.	Chem.	1994,	59,	6233‐6244.		
[11]. Barluenga,	 J.;	 Gonzalez,	 J.	 M.;	 Garcia‐Martin,	 M.	 A.;	 Campos,	 P.	 J.;	

Asensia,	G.	J.	Org.	Chem.	1993,	58,	2058‐2060.		
[12]. Olah,	G.	A.;	Wang,	D.;	Sandford,	G.;	Prakash,	G.	K.	S.	J.	Org.	Chem.	1993,	

58,	3194‐3195.		
[13]. Sy,	W.	W.	Tetrahedron	Lett.	1993,	34,	6223‐6224.		
[14]. Bachki,	A.;	Foubelo,	F.;	Yus,	M.	Tetrahedron	1994,	50,	5139‐5146.		
[15]. Edgar,	K.	J.;	Falling,	S.	N.	J.	Org.	Chem.	1990,	55,	5287‐5291.		
[16]. Zangade,	 S.;	 Mokle,	 S.;	 Chavan,	 S.;	 Vibhute,	 Y.	 Orbital	 Elec.	 J.	 Chem.	

2011,	3,	144‐149.		
[17]. Zangade,	S.;	Shinde,	A.;	Patil,	A.;	Vibhute,	Y.	Eur.	J.	Chem.	2012,	3,	208‐

210.		

[18]. Zangade,	S.;	Shinde,	A.;	Vibhute,	A.;	Vibhute,	Y.	Pak.	 J.	Chem.	2012,	2,	
18‐23.		

[19]. Shinde,	A.	T.;	Zangade,	S.	B.;	Chavan,	S.	B.;	Vibhute,	A.	Y.;	Nalwar,	Y.	S.;	
Vibhute,	Y.	B.	Synth.	Commun.	2010,	40,	3506‐3513.		

[20]. Bose,	A.	K.;	Pednekar,	S.;	Ganguly,	S.	N.;	Chakraborty,	G.;	Manhas,	M.	S.	
Tetrahedron	Lett.	2004,	45,	8351‐8353.