In situ generated acylimidazolium acetate as an efficient catalyst and acylating agent for the acetylation of alcohols, phenols, and amines at ambient temperature

Article abstract of DOI:10.1016/S1872-2067(12)60660-3

Acylimidazolium acetate was readily prepared in situ from the reaction of imidazole with acetic anhydride and subsequently acted as a catalyst and acylating agent for the efficient acetylation of alcohols, phenols, and amines at ambient temperature.

Full text of DOI:10.1016/S1872-2067(12)60660-3

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Inꢀsituꢀgeneratedꢀacylimidazoliumꢀacetateꢀasꢀanꢀefficientꢀcatalystꢀ
andꢀacylatingꢀagentꢀforꢀtheꢀacetylationꢀofꢀalcohols,ꢀphenols,ꢀandꢀ
aminesꢀatꢀambientꢀtemperatureꢀ
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DepartmentꢀofꢀChemistry,ꢀFacultyꢀofꢀSciences,ꢀPersianꢀGulfꢀUniversity,ꢀBushehrꢀ75169,ꢀIranꢀ
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2.ꢀ ꢀ Experimentalꢀ
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ꢀ
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O
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,'1+ꢁ2-ꢁ #ꢁ!-,$'0+#"TꢁH'2&ꢁ2&'1ꢁ',ꢁ+',"Qꢁ2&#ꢁ.Kꢁ-$ꢁ2&#ꢁ0#ꢂ!2'-,ꢁ
+'6230#ꢁ 5ꢂ1ꢁ "#2#0+',#"ꢁ 3.-,ꢁ !-+.*#2'-,ꢁ -$ꢁ 2&#ꢁ ꢂ!#27*ꢂ2'-,ꢁ
0#ꢂ!2'-,Tꢁ&&#ꢁ0#ꢂ!2'-,ꢁ+#"'3+ꢁ5ꢂ1ꢁ$-3,"ꢁ2-ꢁ #ꢁꢂ!'"'!ꢁ',ꢁꢂ**ꢁ-$ꢁ
ꢁ
ꢁ
O
O
ꢍꢁ
TV
ꢁ
%#ꢂ!2'-,ꢁ !-,"'2'-,1Sꢁ ꢂ!7*'+'"ꢂ8-*'3+ꢁ ꢂ!#2ꢂ2#ꢁ RTRZꢁ ++-*Qꢁ ꢂ*!-&-*ꢁ STRꢁ
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-$ꢁꢂ!#2'!ꢁꢂ!'"ꢁ',ꢁ2&#ꢁ0#ꢂ!2'-,ꢁ+'6230#Qꢁꢂ1ꢁ1&-5,ꢁ',ꢁ-!&#+#ꢁTTꢁ
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4.ꢀ ꢀ Conclusionsꢀ
2'+'8#"ꢁ!-,"'2'-,1Tꢁ$1ꢁ1&-5,ꢁ',ꢁ&ꢂ *#ꢁSꢁꢃ#,20'#1ꢁSTꢅSXꢄQꢁꢂꢁ4ꢂV
0'#27ꢁ -$ꢁ 2&#ꢁ "'$$#0#,2ꢁ .&#,-*1ꢁ #ꢂ0',%ꢁ "'$$#0#,2ꢁ 13 12'23#,21ꢁ
5#0#ꢁ 13!!#11$3**7ꢁ !-,4#02#"ꢁ 2-ꢁ 2&#ꢁ !-00#1.-,"',%ꢁ ꢂ!#2ꢂ2#1ꢁ ',ꢁ
#6!#**#,2ꢁ7'#*"1Tꢁ
$,ꢁ#$$'!'#,2ꢁ.0-2-!-*ꢁ$-0ꢁ2&#ꢁꢂ!#27*ꢂ2'-,ꢁ-$ꢁꢂ*!-&-*1Qꢁ.&#,-*1Qꢁ
ꢂ,"ꢁ ꢂ+',#1ꢁ 5ꢂ1ꢁ $-3,"Tꢁ NVꢂ!7*'+'"ꢂ8-*'3+ꢁ ꢂ!#2ꢂ2#ꢁ '1ꢁ ',20-V
"3!#"ꢁ ꢂ1ꢁ ꢂ,ꢁ #ꢂ1'*7ꢁ .0#.ꢂ0#"ꢁ ꢂ,"ꢁ !&#ꢂ.ꢁ '-,'!ꢁ *'/3'"ꢁ 2&ꢂ2ꢁ .#0V
$-0+1ꢁꢂꢁ!ꢂ2ꢂ*72'!ꢁꢂ!2'4'27Qꢁꢂ,"ꢁ!ꢂ,ꢁ #ꢁ0#V31#"ꢁꢂ2ꢁ*#ꢂ12ꢁSRꢁ2'+#1ꢁ
5'2&ꢁ,-ꢁ- 4'-31ꢁ*-11ꢁ-$ꢁꢂ!2'4'27Tꢁ&&#ꢁꢂ"4ꢂ,2ꢂ%#1ꢁ-$ꢁ-30ꢁ1712#+ꢁ
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ꢂ!7*ꢂ2'-,ꢁ -$ꢁ ꢂ+',#1ꢁ ꢂ2ꢁ ꢂ+ '#,2ꢁ 2#+.#0ꢂ230#Tꢁ 3*#ꢂ1',%*7Qꢁ ꢂ0-V
+ꢂ2'!ꢁ ꢂ+',#1ꢁ !-,2ꢂ',',%ꢁ #*#!20-,ꢁ "-,ꢂ2',%ꢁ -0ꢁ #*#!20-,ꢁ 5'2&V
"0ꢂ5',%ꢁ%0-3.1ꢁ5#0#ꢁ13!!#11$3**7ꢁꢂ!#27*ꢂ2#"ꢁ5'2&',ꢁSꢁ+',TꢁH#ꢁ
ꢂ*1-ꢁ #6ꢂ+',#"ꢁ 2&#ꢁ ꢂ!#27*ꢂ2'-,ꢁ -$ꢁ .0'+ꢂ07ꢁ ꢂ,"ꢁ 1#!-,"ꢂ07ꢁ ꢂ*'V
.&ꢂ2'!ꢁꢂ+',#1ꢁꢃ&ꢂ *#ꢁSQꢁ#,20'#1ꢁTUꢁꢂ,"ꢁTVꢄTꢁQ,$-023,ꢂ2#*7Qꢁ-30ꢁ
ꢂ22#+.21ꢁ2-ꢁꢂ!#27*ꢂ2#ꢁ2&#1#ꢁꢂ+',#1ꢁ5#0#ꢁ3,13!!#11$3*Tꢁ&&#ꢁ$ꢂ'*V
O
O
O
N
NH
HN
N
CH3COO
O
(I)
RXH
CH3COOH
30#ꢁ-$ꢁ2&#ꢁ-.2'+'8#"ꢁ!-,"'2'-,1ꢁ',ꢁ2&#1#ꢁ!ꢂ1#1ꢁ!ꢂ,ꢁ #ꢁ#6.*ꢂ',#"ꢁ
',ꢁ2#0+1ꢁ-$ꢁ2&#ꢁ.K ꢁ4ꢂ*3#ꢁ-$ꢁ2&#ꢁꢂ+',#1Tꢁ*-0ꢁ2&#ꢁ0#ꢂ!2'-,ꢁ2-ꢁ.0-V
ꢂ
!##"ꢁ13!!#11$3**7Qꢁ2&#ꢁꢂ+',#ꢁ,##"1ꢁ2-ꢁ #ꢁꢂ *#ꢁ2-ꢁꢂ22ꢂ!)ꢁ2&#ꢁ!ꢂ0V
-,7*ꢁ!ꢂ0 -,ꢁꢂ2-+ꢁ-$ꢁNVꢂ!7*'+'"ꢂ8-*'3+ꢁꢂ!#2ꢂ2#ꢁꢃIꢄTꢁ'$ꢁ2&#ꢁꢂ*'V
.&ꢂ2'!ꢁꢂ+',#ꢁ'1ꢁ.0-2-,ꢂ2#"ꢁ"30',%ꢁ2&'1ꢁ12#.Qꢁ'2ꢁ5'**ꢁ,-2ꢁ #ꢁꢂ *#ꢁ
2-ꢁ.#0$-0+ꢁꢂ1ꢁꢂꢁ,3!*#-.&'*#Tꢁ
X
O
O
R
O
O
H N
N
CH3COO
2
ꢀ
&&#ꢁ0#31ꢂ '*'27ꢁ-$ꢁꢂꢁ!ꢂ2ꢂ*712ꢁ'1ꢁ-$ꢁ%0#ꢂ2ꢁ'+.-02ꢂ,!#ꢁ$0-+ꢁꢂ,ꢁ
#!-,-+'!ꢂ*ꢁꢂ,"ꢁ#,4'0-,+#,2ꢂ*ꢁ.#01.#!2'4#Tꢁ&&#ꢁ0#31ꢂ '*'27ꢁ-$ꢁ
Schemeꢀ2.ꢀ&&#ꢁ.0-.-1#"ꢁ+#!&ꢂ,'1+ꢁ$-0ꢁꢂ!#27*ꢂ2'-,ꢁ-$ꢁꢂ*!-&-*1Qꢁ.&#V
,-*1Q ꢂ,"ꢁꢂ+',#1T

ꢀ
NajmehꢀNowrouziꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ34ꢀ(2013)ꢀ1787–1790ꢀ
ꢀ
GraphicalꢀAbstractꢀ
Chin.ꢀJ.ꢀCatal.QꢁTRSUQꢁUVSꢁSYZYꢅSY[Rꢁ ꢁ ꢁ "-'SꢁSRTSRSXꢋ-SZYTVTRXYꢃSTꢄXRXXRVU
Inꢀsituꢀgeneratedꢀacylimidazoliumꢀacetateꢀasꢀanꢀefficientꢀcatalystꢀandꢀ
acylatingꢀagentꢀforꢀtheꢀacetylationꢀofꢀalcohols,ꢀphenols,ꢀandꢀaminesꢀatꢀ
ambientꢀtemperatureꢀ
O
H3C
N
ꢁ
NH CH3COO
(8.0 mol%)
)ꢂ(+#&ꢁ)-50-38'#Qꢁ-#7#"#&ꢁZꢂ&0ꢂꢁ$*'8ꢂ"#&ꢁ
X
CH3
R
PersianꢀGulfꢀUniversity,ꢀIranꢀ
RXH
(CH3CO)2O, r.t.
O
NVꢂ!7*'+'"ꢂ8-*'3+ꢁ ꢂ!#2ꢂ2#ꢁ 5ꢂ1ꢁ 13!!#11$3**7ꢁ 31#"ꢁ ꢂ1ꢁ ꢂꢁ 0#ꢂ"'*7ꢁ .0#.ꢂ0ꢂ *#ꢁ
ꢂ,"ꢁ',#6.#,1'4#ꢁ0#!7!*ꢂ *#ꢁ!ꢂ2ꢂ*712ꢁ$-0ꢁ2&#ꢁ#$$'!'#,2ꢁꢂ!#27*ꢂ2'-,ꢁ-$ꢁꢂ*!-&-*1Qꢁ
.&#,-*1Qꢁꢂ,"ꢁꢂ+',#1ꢁꢂ2ꢁꢂ+ '#,2ꢁ2#+.#0ꢂ230#Tꢁ
X = O, NH
R = alkyl, phenyl
SVYRꢁ
!&#ꢂ.,#11Qꢁꢂ4ꢂ'*ꢂ '*'27ꢁꢂ,"ꢁ*-5ꢁ2-6'!'27ꢁ-$ꢁ2&#ꢁ0#ꢂ%#,21ꢁ',ꢁ!-,V
20ꢂ12ꢁ2-ꢁ2&#ꢁ1-+#ꢁ&ꢂ8ꢂ0"-31ꢁ0#ꢂ%#,21ꢁ0#.-02#"ꢁ',ꢁ2&#ꢁ*'2#0ꢂ230#Tꢁ
ꢈSSꢉ 331&.ꢂ*#2&ꢂꢁ3Qꢁꢆꢂ*'2&ꢂ+ ')ꢂꢁ2TꢁApplꢀClayꢀSciQꢁTRSSQꢁWSSꢁVTVꢁ
ꢈSTꢉ -&'0','ꢁ *Qꢁ '+ꢂ,8ꢂ"#&ꢁ #ꢁ KQꢁ 2-31ꢂ8ꢂ"#&ꢁ -ꢁ $ꢁ %Qꢁ 2-&ꢂ++ꢂ".--0Vꢁ
,ꢂ*2-0)ꢁ'Qꢁ$ #"',ꢁ2TꢁChinꢀChemꢀLettQꢁTRSRQꢁTSSꢁSSZYꢁ
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U0"ꢁ#"Tꢁ)#5ꢁꢎ-0)SꢁH'*#7QꢁS[[[ꢁ
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ꢈSXꢉ -!0'4#,ꢁ(ꢁ*ꢁDTꢁChemꢀSocꢀRevQꢁS[ZUQꢁSTSꢁST[ꢁ
ꢈSYꢉ -ꢂ,-ꢁ&Qꢁ+&ꢂ1&'ꢁUQꢁ+0'7ꢂ+ꢂꢁ&TꢁSynthesisQꢁS[[[SꢁSSVSꢁ
ꢈSZꢉ -2#%*'!&ꢁHQꢁK-$*#ꢁ#TꢁAngewꢀChemꢀIntꢀEdꢀEngQꢁS[X[QꢁZSꢁ[ZSꢁ
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ꢈTRꢉ D#"#(1ꢁ(Qꢁ,#,,#22ꢁ)ꢁ-Qꢁꢀ-,,ꢁꢆꢁ2QꢁC'4#0ꢁ-ꢁ&Qꢁ#',%0ꢂ1ꢁ2Qꢁꢆ',ꢁ-Qꢁ+*'4#0ꢁ
3ꢁ$Qꢁ3#2#01-,ꢁ2ꢁ TꢁJꢀOrgꢀChemQꢁS[[UQꢁWZSꢁYTZXꢁ
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