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A Facile Route to ConvertAcetylacetone into Other β-Diketones with Acyl ChloridesPromoted by SamariumTriiodideWenying Hao a , Yongmin Zhang a , Taokai Ying a &Pin Lu aa Department of Chemistry , Hangzhou University ,Hangzhou, 310028, P.R. ChinaPublished online: 23 Aug 2006.

To cite this article: Wenying Hao , Yongmin Zhang , Taokai Ying & Pin Lu (1996) AFacile Route to Convert Acetylacetone into Other β-Diketones with Acyl ChloridesPromoted by Samarium Triiodide, Synthetic Communications: An International Journalfor Rapid Communication of Synthetic Organic Chemistry, 26:12, 2421-2427, DOI:10.1080/00397919608004552

To link to this article: http://dx.doi.org/10.1080/00397919608004552

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SYNTHETIC COMMUNICATIONS, 26(12), 2421-2427 (1996)

A FACILE ROUTE TO CONVERT ACETYLACETONE INTO OTHER P-DIKETONES WITH ACYL CHLORIDES

PROMOTED BY SAMARIUM TRIIODIDE

Wenying Hao, Yongmin Zhang ' , Taokai Ying and Pin Lu

Department of Chemistry, Hangzhou University Hangzhou 310028, P. R. China

ABSTRACT: Reaction of acetylacetone with acyl chlorides in the presence of SmI3 gave Pdiketones RCOCH2COCH3 ( I or RCOCHzCOR ( I[ ) in good yields under mild and neutral conditions.

Recently, lanthanide compounds, in particular samarium diio- dide , have been of great interest as versatile reagents in organic syn- thesis'. At the same time, much attention has been devoted to the ap- plication of samarium ( IlI ) compoudns'. For example, we have re- ported that, promoted by Sm13, a-haloketones can react with aldehy- des to give a,fkunsaturated ketones3, Sasai reported that l-hyloro-2- heptanone is able to react with benzaldehyde to form a-chloro-Phy- droxy ketones catalyzed by Sm (HMDS)34, in the presence of Sm

* To whom mrrapondcnce should be addressed

242 1

Copyright 0 1996 by Marcel Dekker, Inc.

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2422 HA0 ET AL.

At-5C

No. Major Product Yield(%)

(OTF)3,benzylamine can add to ethyl crotonate to form pamino es- t e r ~ ~ ; Mori reported that mediated by SmI2 or SmI3, a-haloketones

may react with a-ketocarboxylates and a-diketones to give a-hydroxy- y-ketocarboxylates and 2-hydroxy-1 , 4-diketones respectively6. Very recently, we have found that samarium triiodide promoted the reac- tion of ebromoacetophenone with acyl chloride'. Now we wish to re- port that Sm13, which is considered as a hard Lewis acid, can pro- mote the reaction of acetylacetone with acyl chlorides to give new p diketones. The reaction is shown in the scheme and the results are summarized in table 1.

We found that the temperature has an important influence on the reaction. When the reaction is carried out at -5°C ,the major product is I and the yields are good(75-83%) , whereas at 70°C , the major

At 70%

No. Major Product Yield (%)

Scheme 0 0 0 0

II II 0 0 0 II II U II U

CHs++Hz+*Hs + R<--CI CHs*--CHz+R f R--C--CHz+R

la C ~ H ~ C O C H Z C O C H ~ 75

2a p-IC6H4COCH~COCH3 83

3a P-CH~OC~HICOCHZCOCH~ 82

4a CH~(CHZ) ,OCOCH~COCH~ 78

5a m-CICsH4COCH2COCH3 81

6a p-CH3C6H4C0CHzCOCH3 81

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SAMARIUM "RIIODIDE 2423

product is I[ and the yields are 73-78%. But when the reaction is carried out at room temperature, I and I[ are both formed in a ratio of 3 : 2 and each of the yields is low, even after extended reaction times. Furthermore , we studied the analogous reaction of benzoylace- tone with benzyl chloride at 70%, and dibenzoylmethane was ob- tained as we expected.

According to the report of Hauser', a possible reaction niecha- nism is as follows:

o 0 I I

R - C - C I +Smls R - C ' f[CLSmlr]- + -

:OS!?ll, 0 : 0 - S m1, 0 I I I - I

0 0 II I

CHs-C+Hz--C--CHa +Smh -[ C H s + C H - C - C t l a m H a - - C < t l - C - - C l I , ] 0

C-R I

I

, \

0 I 1 0

C-R I I R

c==o I c c I

CHs, A /CHI

I 41 - C H s CH C H a - HfO

__c

\ / \ / c c 0 0

OH 0

/ \ I T

I ! $Ii/

T h e SmI? plays a double role in the reaction. It assists in ioniza- tion of the acyl chloride, and converts the acetylacetone into a samari- um derivative of the enolate. Then acyliuni ion react with the carban- ion of the enolate to afford a product containing three acyl group 011

one carbon'. T h e most strongly acidic" of these acyl groups is then cleaved" and the corresponding Bdiketone is obtained.

It is known that usual methods to form P-diketone, such as Claisen condensations of esters with ketones in the presence of

NaOC2H5 as catalyst are limited to the condensations of alkyl acetates

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2424 HA0 ET AL.

with methyl ketones to give Bdiketones of the structrue R-CO-CH2- CO-CH3. Our present reaction could bc used for the convcrsion of these types of Pdiketones into others of the structure R-CO-CH2-CO- R' under mild and neutral conditions. This makes it a good method for preparation of a number of B diketones which are not available by direct ester condensation". Experimental

' H-NMR spectra were recorded in CCll ,CDCb or DMSO on a JEOL PMX 6Osi spectrometer using T M S as internal standard. IR spectra were obtained on a PE-683 spectrometer. Melting points are uncorrected. The solvents were predried according to standard proce- dures before use. The reactions were performed in a Schlenk type glass apparatus and under a nitrogen atmosphere. General procedure.

A mixture of powdered samarium (0. 30g, 2mmol) and iodine (0. 75g93mmol) in dry acetonitrile (20ml) was stirred at room tem- peratures until the samarium disappeared. To the resulting brown yel- low suspension of SmI3 was added a mixture of acetylacetone (Zmmol,-5"C/ lmmol, 70'C) and acyl chloride (Zmmol) and the resulting mixture was stirred for 3h at -5'C or 70°C. It was then treated with dilute hydrochloric acid and extracted with ether. The combined organic layers were washed with aqueous sodium thiosul- fate , dried over magnesium sulfate, and evaporated. The crude prod- uct was purified by column chromatography (silica gel, CHzClz: petroleum ether = 1 : 1 as eluant). The spectral and analytical data of the products are as follows:

Benzoylacetone ( l a ) :mp 57-58'C

5H ) IR(KBr , cm-',u> : 1620,1705 Dibenzoylmethane ( lb ) :mp 72-73'C 'H-NMR(CCI4,TMS):7. 40-8.03(m,lOH),6.73,16.70(~,2H)

'H-NMR(CC14,TMS): 1.93(~,3H)95.93(~,2H),7- 20-7.79(d,

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SAMARIUM TRIIODLDE 2425

IR(KBr,cm-',u): 1646,1730 p-Iodobenzoylacetone(2a) :mp 116-117°C ' H -NMR (CC14,TMS) : 2. 07(s, 3H), 7. 40-7. 80(m, 4H), 5. 97, 15.93(s,2H) IR(KBr,cm-',u):1691,1766 Di ( p - 1odobenzoyl)methane ( 2b) : m p 175 - 176 'C 'H--NMR(DMSO,TMS):~.~~(S,~H),~.~~-~.~~(~,~H) IR (KBr ,cm-', u) : 1707,1782 p-Anisoylacetone (3a) :mp 52-53°C H-NMR(CC14,TMS) :Z. 03(~,3H),3. 73(~,3H) ,6.70-6.83(d, 2H),7.70-7.83(d,2H),5.93,16.26(~,2H) IR(KBr,cm-',u): 1643,1725 Di(p-Anisoy1)methane (3b) : mp 105- 106 "C ' H -NMR(CC14 ,TMS) : 3. 73(s 6H) 6. 70-6.83(d 4H) 7.70- 7.83(d 94H) 6.52, 17.12(~,2H) IR(KBr ,cm-' ,u> : 1652,1731 ~auroylacetone(4a) :mp 31 -32°C 'H -NMR(CC14,TMS):0. 83-1. 33(m,21H),2. 08-2. 36(t,

IR(KBr ,cm-' ,u> : 1728,1746 m - Chlorobenzoylacet one (5a) : mp 4 4 - 4 5 OC lH-NMR(CCi4,TMS) :2. 06(~,3H),7.23-7.73(m,8H) ,5. 97, 15. 80(s,2H) IR(KBr,cm-',u):1680,1724 Di (m -Chlorobenzoyl)methane (5b) : mp 135 - 136 "C ' H-NMR(CDC13,TMS) :6.76(s,2H) ,7.30-7.93(m,8H) IR(KBr ,cm-' ,u) : 1683,1725 p - T oluoylace t one ( 6a 1 : oil

2H),5.27,15.26(~,2H)

'H-NMR(CC14,TMS):Z. 03(~,3H),2.30(~,3H),7.03-7- 15(d, 2H),7.57-7. 70(d92H),5. 97,16. 06(s,2H) IR(cm-',u):1694,1738 Di ( p -Toluoyl ) me thane ( 6 b ) : mp 1 1 7 - 1 18 "C 'H-NMR(CCl4,TMS) :2.36(~,6H) ,6.73(~,2H),7. 13-7.27(d,

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HA0 ET AL. 2426

4H) ,7.80-7.93(d,4H) IR(KBr,cm-’,u):1690,1745 Acknowl egment

China for financial support. References

We are grateful to the National Natural Science Foundation of

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SAMARIUM TRIIODIDE 2427

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