Active methylene compounds

The hydrogens in methane practically do not exhibit acidic character. However when two of the hydrogens are replaced
by electron withdrawing groups, the rest of the hydrogens become acidic in nature. The electron withdrawing groups
present on both sides attract the electron towards themselves and thus weaken the –CH bond of methylene. Thus
hydrogen atom can dissociate to give a stable anion. This same phenomena applies to EAA, the two hydrogen atoms
bonded to methylene group become acidic and reactive due to two electron withdrawing functional groups i.e. acetyl
and ester attached o methylene carbon.
Thus methylene group attached to two electron withdrawing functional groups is termed as reactive methylene group

1. ACTIVE METHYLENE COMPOUNDS GUIDED BY, Prof . LOKNATH RAI PRESENTED BY, SHRYLI K S 3 rd SEMISTER YUVARAJA’S COLLEGE (AUTONOMOUS) 03/09/2018 03/09/2018 ACTIVE METHYLENE COMPOUNDS 1

2. CONTENTS Introduction Active Methylene Compounds Preparation Physical Properties Chemical Properties Synthetic Uses Conclusion References Acknowledgement 03/09/2018 ACTIVE METHYLENE COMPOUNDS 2

3. INTRODUCTION 03/09/2018 ACTIVE METHYLENE COMPOUNDS 3 Compound 1: Methylene Compound

4. ACTIVE METHYLENE COMPOUNDS 03/09/2018 ACTIVE METHYLENE COMPOUNDS 4 Compound 2: Ethyl Acetoacetate Compound 3: Diethyl Malonate

5. PREPARATION 03/09/2018 ACTIVE METHYLENE COMPOUNDS 5 Reaction 1: Preparation of Ethyl Acetoacetate. Reaction 2: Preparation of Diethyl Malonate.

6. PHYSICAL PROPERTIES Colorless. Pleasant Smelling. Neutral to Litmus. Sparingly soluble in Water Freely soluble in Alcohol and Ether. High Boiling Point. 03/09/2018 ACTIVE METHYLENE COMPOUNDS 6

7. CHEMICAL PROPERTIES Acidity of Methylene Hydrogen. Salt Formation Alkylation Acid Hydrolysis Ketonic Hydrolysis 03/09/2018 ACTIVE METHYLENE COMPOUNDS 7

8. ACIDITY OF METHYLENE HYDROGENS 03/09/2018 ACTIVE METHYLENE COMPOUNDS 8 Reaction 3: Acidity of Methylene Hydrogen in Ethyl Acetoacetate. Reaction 4: Acidity of Methylene Hydrogen in Diethyl Malonate.

9. STABILITY INDUCTIVE EFFECT RESONANCE 03/09/2018 9 Inductive Effect in Ethyl Acetoacetate Resonance in Ethyl Acetoacetate Resonance in Diethyl Malonate

10. SALT FORMATION 03/09/2018 ACTIVE METHYLENE COMPOUNDS 10 Reaction 5: Salt Formation in Ethyl Acetoacetate. Reaction 6: Salt Formation in Diethyl Malonate.

11. ALKYLATION 03/09/2018 ACTIVE METHYLENE COMPOUNDS 11 Reaction 7: Alkylation of Ethyl Acetoacetate. Reaction 8 : Alkylation of Diethyl Malonate.

12. ACID HYDROLYSIS 03/09/2018 ACTIVE METHYLENE COMPOUNDS 12 Reaction 10: Acid Hydrolysis of Diethyl M alonate. Reaction 9 : Acid Hydrolysis of Ethyl Acetoacetate.

13. KETONIC HYDROLYSIS 03/09/2018 ACTIVE METHYLENE COMPOUNDS 13 Reaction 11: K etonic Hydrolysis of Ethyl Acetoacetate.

14. SYNTHESIS OF ALKYLACETIC ACIDS 03/09/2018 ACTIVE METHYLENE COMPOUNDS 14 Reaction 12: Synthesis of Alkylacetic Acid using Ethyl Acetoacetate. Reaction 13: Synthesis of Alkylacetic Acid using Diethyl Malonate.

15. SYNTHESIS OF DIALKYLACETIC ACID 03/09/2018 ACTIVE METHYLENE COMPOUNDS 15 Reaction 14: Synthesis of Dialkylacetic Acid using Ethyl Acetoacetate . Reaction 15: Synthesis of Dialkylacetic Acid using Diethyl Malonate.

16. SYNTHESIS OF SUCCINIC ACID 03/09/2018 ACTIVE METHYLENE COMPOUNDS 16 Reaction 16: Synthesis of Succinic Acid using Ethyl Acetoacetate. Reaction 17: Synthesis of Succinic Acid using Diethyl Malonate.

17. SYNTHESIS OF ADIPIC ACID 03/09/2018 ACTIVE METHYLENE COMPOUNDS 17 Reaction 19: Synthesis of Adipic Acid using E thyl Acetoacetate. Reaction 20: Synthesis of Adipic Acid using Diethyl Malonate.

18. SYNTHESIS OF KETO ACIDS 03/09/2018 ACTIVE METHYLENE COMPOUNDS 18 Reaction 21: Synthesis of K eto Acids using Diethyl Malonate.

19. SYNTHESIS OF α , β - UNSATURATED ACIDS 03/09/2018 ACTIVE METHYLENE COMPOUNDS 19 Reaction 23: Synthesis of using Diethyl Malonate.   Reaction 22: Synthesis of using E thyl Acetoacetate.  

20. SYNTHESIS OF METHYL KETONES 03/09/2018 ACTIVE METHYLENE COMPOUNDS 20 Reaction 24: Synthesis of Methyl Ketones using Ethyl Acetoacetate .

21. SYNTHESIS OF DIKETONES 03/09/2018 ACTIVE METHYLENE COMPOUNDS 21 Reaction 25: Synthesis of Diketones using Ethyl Acetoacetate.

22. SYNTHESIS OF ACETONYL ACETONE 03/09/2018 ACTIVE METHYLENE COMPOUNDS 22 Reaction 26: Synthesis of Acetonyl Acetone using Ethyl Acetoacetate.

23. SYNTHESIS OF 4- METHYL URACIL 03/09/2018 ACTIVE METHYLENE COMPOUNDS 23 Reaction 27: Synthesis of 4- Methyl Uracil using Ethyl Acetoacetate.

24. SYNTHESIS OF BARBITURIC ACID 03/09/2018 ACTIVE METHYLENE COMPOUNDS 24 Reaction 28: Synthesis of Higher Barbituric Acid using Diethyl Malonate.

25. SYNTHESIS OF ANTIPYRINE 03/09/2018 ACTIVE METHYLENE COMPOUNDS 25 Reaction 29: Synthesis of Antipyrine using Ethyl Acetoacetate.

26. SYNTHESIS OF α - AMINO ACIDS 03/09/2018 ACTIVE METHYLENE COMPOUNDS 26 Reaction 30: Synthesis of Higher α - Amino Acids using Diethyl Malonate.

27. CONCLUSION 03/09/2018 ACTIVE METHYLENE COMPOUNDS 27 Fig 1: Products derived from, Alkyl and Dialkyl Acetic Acid, Succinic Acid, Adipic Acid, Crotonoic Acid, methyl Ketones, Diketones , Barbituric Acid, Antipyrine & Glycin .

28. REFERENCES 03/09/2018 ACTIVE METHYLENE COMPOUNDS 28 Arun Bahl , B. S Bahl , A Textbook of Organic Chemistry. 11 th Edition. 1971. S Chand & Company LTD Publications, Ghaziabad, Delhi, Shahibabad industrial Area, 201005. 916 pages. L G Wade, Jr., Maya Shankar Simgh , Organic Chemistry, 6 th Edition, 2008. Prentic Hall PTR, Dorling Kindersly (India) Pvt. Ltd, licenses of Pearson Education in South Asia. 1320 pages. Wtodzimerz U, Ketarzyna J, Katarzyna W, Andrzej G, Properties and Application of Diketones And their Derivatives, CHEMIK 2011, 65, 273-282 Redha I. Al- Byati , Iyad S. Hameed & Mustafa K. Toema , 2011. Synthesis of New Heterolytic Compounds Derived From 4- Amino Antipyrine . College of Science- Mustansiriyah University & College of Education- Tikrit University. 7 pages. Dr. Vimal Rah, 2007. Organic Synthesis via enolates . Lecturer, Dep. Of Chemistry. S.G.T.B Khalsa College, Delhi. 31 pages. Kenneth E Hamlin, Jr & Walter H Hartung , 1942. The Synthesis of α - Amino Acids From Substituted Acetoacetic Esters. Research Laboratory, School of Pharmacy, University of Maryland, Baltimore. 10 pages. http://www.chem.ucalgary.ca/courses/350/Carey5th/Ch21/ch21-1-2.html https:// chem.libretexts.org/Reference/Organic_Chemistry_Glossary/Active_Methylene_Compound https:// pubs.acs.org/doi/abs/10.1021/jo01279a029 http://www.ochempal.org/index.php/alphabetical/a-b/active-methylene-compound /

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30. ACKNOWLEDGEMENT 03/09/2018 ACTIVE METHYLENE COMPOUNDS 30 I express my sincere gratitude to my guide, Dr. Loknath Rai for his guidance throughout the preparation of my seminar. I also thank D r. Soumya P T for helping me with this seminar. I thank the department of Molecular Biology for providing me this opportunity to present my seminar. Thank you all for your patience.

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