Acylation studies with Meldrum's acid

Article abstract of DOI:10.1080/00397910500180469

Meldrum's acid (1) on bisacylation with succinyl chloride afforded a neutral diketo product (2); however, the dimer enolic products (3) with acidic nature resulted in glutaryl and adipyl dichlorides. Monoacylation of (1) with acetyl chloride gave acidic 5-acetyl Meldrum's acid (4) in enol form. Copyright Taylor & Francis, Inc.

Full text of DOI:10.1080/00397910500180469

This article was downloaded by: [Fordham University]
On: 18 November 2012, At: 23:52
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954
Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH,
UK
Synthetic Communications: An
International Journal for Rapid
Communication of Synthetic
Organic Chemistry
Publication details, including instructions for
authors and subscription information:
http://www.tandfonline.com/loi/lsyc20
Acylation Studies with
Meldrum's Acid
P. P. Mahulikar a & R. B. Mane b
a School of Chemical Sciences, North Maharashtra
University, Jalgaon, India
b Department of Chemistry, Shivaji University,
Kolhapur, India
Version of record first published: 18 Aug 2006.
To cite this article: P. P. Mahulikar & R. B. Mane (2005): Acylation Studies with
Meldrum's Acid, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 35:16, 2139-2141
To link to this article: http://dx.doi.org/10.1080/00397910500180469
PLEASE SCROLL DOWN FOR ARTICLE
Full terms and conditions of use: http://www.tandfonline.com/page/terms-
and-conditions
This article may be used for research, teaching, and private study purposes.
Any substantial or systematic reproduction, redistribution, reselling, loan,
sub-licensing, systematic supply, or distribution in any form to anyone is
expressly forbidden.
The publisher does not give any warranty express or implied or make any
representation that the contents will be complete or accurate or up to
date. The accuracy of any instructions, formulae, and drug doses should be

independently verified with primary sources. The publisher shall not be liable
for any loss, actions, claims, proceedings, demand, or costs or damages
whatsoever or howsoever caused arising directly or indirectly in connection
with or arising out of the use of this material.

Synthetic Communicationsw, 35: 2139–2141, 2005
Copyright # Taylor & Francis, Inc.
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910500180469
Acylation Studies with Meldrum’s Acid
P. P. Mahulikar
School of Chemical Sciences, North Maharashtra University,
Jalgaon, India
R. B. Mane
Department of Chemistry, Shivaji University, Kolhapur, India
Abstract: Meldrum’s acid (1) on bisacylation with succinyl chloride afforded a neutral
diketo product (2); however, the dimer enolic products (3) with acidic nature resulted in
glutaryl and adipyl dichlorides. Monoacylation of (1) with acetyl chloride gave acidic
5-acetyl Meldrum’s acid (4) in enol form.
Keywords: Meldrum’s acid, acylation
Meldrum’s acid (1) (2,2-dimethyl-1,3-dioxane-4,6-dione; isopropylidene
malonate) has attracted considerable attention from synthetic organic
chemists.[1–4] Meldrum’s acid exhibits an overwhelming propensity to
undergo bis-alkylation reaction with alkyl halides. Our interest was to
study[5–10] bis-acylation of Meldrum’s acid with dichlorides of succunic,
glutaric, and adipic acids. The bis-acylation was observed with succinyl
dichloride to give the diketo derivative (2). However, glutaryl and adipyl
dichlorides with Meldrum’s acid and pyridine as a base afforded the
dimeric product, in which two molecules of Meldrum’s acid reacted with
one mol of acid dichloride.
Received in India February 5, 2005
Presented at the National Symposium on Newer Concepts in Organic Synthesis,
1998, Aurangabad, India, [Abstract: 1.29].
This paper is dedicated to Prof. M. M. Salunkhe, Vice-Chancellor, Shivaji
University, Kolhapur–416 004 (Former Director, Institute of Science, Mumbai
400 032) India.
Address correspondence to P. P. Mahulikar, School of Chemical Sciences, North
Maharashtra University, Jalgaon 425 001, India. E-mail: mahulikarpp@rediffmail.com
2139

2140
P. P. Mahulikar and R. B. Mane
In conclusion, cyclic bis-acylation of Meldrum’s acid was restricted to
succinic acid dichloride. With higher homologues such as glutaryl and
adipyl dichlorides, a dimeric product was formed (Scheme 1).
SUCCINYL MELDRUM’S ACID (2)
Pyridine (0.02 M) was added dropwise to a solution of Meldrum’s acid (1)
(0.01 M) in 10 ml of dry CH2Cl2. After 15 min the reaction mixture was
cooled to 08C and succinyl dichloride (0.011 M) in 5 ml of CH2Cl2 was
added. After stirring for 6 h at rt, the contents were poured into 30 ml of
water and extracted with CH2Cl2. The organic extract was successively
washed with water twice, dil. HCl, water, NaHCO3 solution, and brine and
dried over anhydrous Na2SO4 and by fused CaCl2. The removal of solvent
gave crude product, which was recrystallized from chloroform–light
petroleum ether to give succinyl Meldrum’s acid (2), 87%, mp 2208C dec.
1H NMR (90 MHz, CDCl3): d 1.80 (s, 6H, gem-dimethyl), 2.61 (s, 4 H,
CH2CH2), IR (KBr, cm21): 1720, 1710. Anal. calcd. for C10H10O6: C,
53.01%, H, 4.53%. Found: C, 53.09%, H, 4.42%.
ACYLATION OF MELDRUM’S ACID WITH GLUTARYL
AND ADIPYL CHLORIDES (3)
The reaction of glutaryl/adipyl dichlorides[11,12] (0.011 M) with Meldrum’s
acid (1) (0.01 M) was carried out as described. The crude product was
recrystallized from chloroform–light petroleum ether to afford 3 (40–42%).
Scheme 1. Acylation of Meldrum’s acid.

Acylation Studies with Meldrum’s Acid
2141
1
(3a, mp 858C) H NMR, (90 MHz, CDCl3): d1.77 (s, 12 H, 2 gem-
dimethyl), 2.02 (m, 2 H, CH2, middle), 3.19 (m, 4 H, 2CH2), 15.01 (bs, 2 H,
2 OH); IR (KBr, cm21): 3450–3115, 1775, 1730, 1700, 1645. Anal. calcd. for
C17H20O10: C, 53.12%, H, 5.20%. Found: C, 53.17%, H, 5.16%.
(3b, mp 978C) 1H NMR (90 MHz, CDCl3): d 1.64 (m, 4 H, 2 CH2), 1.80
(s, 12 H, 2 gem-dimethyl), 2.82 (m, 4 H, 2 CH2), 15.00 (bs, 2 H, 2 OH). IR
(KBr, cm21): 3450–3115, 1778, 1730, 1704, 1642. Anal. calcd. for
C18H22O10: C, 54.27%, H, 5.52%. Found: C, 54.19%, H, 5.58%.
ACKNOWLEDGMENT
We thank the University Grants Commission, New Delhi, India, for financial
assistance.
REFERENCES
1. Meldrum, A. N. J. Chem. Soc. 1908, 93, 598.
2. McNab, H. Chem. Soc. Rev. 1978, 7, 345.
3. Chen, B. C. Heterocycles 1991, 32 (3), 529.
4. Davidson, D.; Bernhard, S. A. J. Amer. Chem. Soc. 1948, 70, 3426.
5. Oikawa, Y.; Sugano, K.; Yonemitsuo, O. J. Org. Chem. 1978, 43, 2087.
6. Oikawa, Y.; Yoshioka, T.; Sugano, K.; Yonemitsuo, O. Org. Synth. 1985, 63, 198.
7. Kumbhar (alias Mahulikar), P. P.; Salunkhe, M. M.; Mane, R. B. Indian J. Chem.
1991, 30B, 891.
8. Kumbhar (alias Mahulikar), P. P. Application of Meldrum’s acid in Organic
Synthesis, Ph.D. thesis, Shivaji University: Kolhapur, India, 1993.
9. Hase, T. A.; Salonen, K. Synth. Commun. 1980, 10, 221.
10. Obaza, J.; Smith, F. X. Synth. Commun. 1982, 12, 19.
11. Vogel, A. I. Textbook of Practical Organic Chemistry, 4th edn.; ELBS: Longman,
Harlow, Essex, UK, 1978.
12. a) Fuson, R. C.; Walker, J. T. Org. Synth. Coll., Vol. II, 1943, 169, Ed. Blatt, A. H.,
John Wiley & Sons, NY; b) Guha, P. C.; Sankaran, D. K. Org. Synth. Coll., Vol.
III, 1955, 623, Ed-in-Chief Horning, E. C., John Wiley & Sons, NY.