Contents

CHAPTER 1: PRODUCTION OF MALONIC ACID ........................................................................................ 2 1.1 1.2 PROCESS BACKGROUND ................................................................................................ 2 IDENTIFICATION OF MALONIC ACID ............................................................................. 3 STRUCTURAL AND DEFINITION OF MALONIC ACID ........................................ 3 PHYSICAL AND CHEMICAL PROPERTIES OF MALONIC ACID ............................................ 4 PHYSICAL AND CHEMICAL PROPERTIES OF WATER, H2O ................................................ 4 PHYSICAL AND CHEMICAL PROPERTIES OF CYANOACETIC ACID..................................... 4 PHYSICAL AND CHEMICAL PROPERTIES OF SODIUM CARBONATE ................................. 4 PHYSICAL AND CHEMICAL PROPERTIES OF SODIUM CYANIDE ....................................... 4 PHYSICAL AND CHEMICAL PROPERTIES OF CHLOROACETIC ACID .................................. 4 PHYSICAL AND CHEMICAL PROPERTIES OF DIETHYL MALONATE ................................... 4 ACETON ........................................................................................................................... 4

1.2.1 1.2.2 1.2.3 1.2.4 1.2.5 1.2.6 1.2.7 1.2.8 1.2.9 1.3

BASIC PROCESS IN MALONIC ACID PRODUCTION ................................................................... 5 HYDROLYSIS OF CYANOACETIC ACID WITH STRONG ACID .............................................. 5 ACID CATALYSED SAPONIFICATION OF MALONIC ESTER (DIETHYL MALONATE) ............ 5 CATALYTIC OXIDATION .................................................................................................... 5

1.3.1 1.3.2 1.3.3

CHAPTER 1: PRODUCTION OF MALONIC ACID

1.1 PROCESS BACKGROUND
INTRODUCTION TO MALONIC ACID
Malonic Acid, Dicarboxymethane, methanedicarboxylic acid, carboxyacetic acid or 1,3-Propanedioic acid with molecular formula C3H4O4 and molecular weight 104.06 g/mole is a white crystalline dicarboxylic acid. Malonic acid melting point is at 133C and its boiling point is at 135C. Malonic acid specific gravity is 1.67 and easily soluble in cold water, alcohol and ether. It can be derived by catalytic oxidizing malic acid or by the hydrolysis of cyanocetic acid with strong acid or by acid catalyzed saponification of malonic ester. Malonic acid itself is rather unstable and has few applications. It's diethyl ester (diethyl malonate) is more important commercially. The ionised form of malonic acid, as well as its esters and salts, are known as malonates. For example, diethyl malonate is malonic acid's ethyl ester. Malonic acid and its esters contain active methylene groups which have relatively acidic alpha-protons due to H atoms adjacent to two carbonyl groups. The reactivity of its methylene group provide the sequence of reactions of alkylation, hydrolysis of the esters and decarboxylation resulting in substituted ketones. The methylene groups in 1,3-dicarboxylic acid utilize the synthesis of barbiturates; a hydrogen atom is removed by sodium ethoxide, and the derivative reacts with an alkyl halide to form a diethyl alkylmalonate. The diethyl dialkylmalonates are converted to barbiturates by reaction with urea. Malonic acid and its esters are characterized by the large number of condensation products. They are important intermediates in syntheses of vitamins B1 and B6, barbiturates, non-steroidal anti-inflammatory agents, other numerous pharmaceuticals, agrochemicals and flavors & fragrances compounds.

1.2 IDENTIFICATION OF MALONIC ACID

1.2.1 STRUCTURAL AND DEFINITION OF MALONIC ACID

Figure 1: Structural formula of Malonic Figure 2: Structural diagram of Malonic Acid Acid. The black spheres are carbons, the whites are hydrogens and the blues are oxygens.

Malonic acid is a carboxylic acid group consisting of three carbon atom, four hydrogen atom and four oxygen atom. The carboxylic acid moiety is considered to be a highly polar organic functional group. This polarity results from the presence of a strongly polarized carbonyl (C=O) group and hydroxyl (O-H) group. Recall that oxygen is a relatively electronegative atom and when covalently bound to carbon and particularly hydrogen, a strong permanent dipole is created. In the case of carboxylic acids, the O-H group is even more strongly polarized than the O-H group of alcohols due to the presence of the adjacent carbonyl moiety.

1.2.2 1.2.3 1.2.4 1.2.5

PHYSICAL AND CHEMICAL PROPERTIES OF MALONIC ACID

PHYSICAL AND CHEMICAL PROPERTIES OF WATER, H2O PHYSICAL AND CHEMICAL PROPERTIES OF CYANOACETIC ACID

1.2.6 1.2.7 1.2.8 1.2.9

PHYSICAL AND CHEMICAL PROPERTIES OF SODIUM CARBONATE PHYSICAL AND CHEMICAL PROPERTIES OF SODIUM CYANIDE PHYSICAL AND CHEMICAL PROPERTIES OF CHLOROACETIC ACID PHYSICAL AND CHEMICAL PROPERTIES OF DIETHYL MALONATE

1.2.10 ACETON

1.3 BASIC PROCESS IN MALONIC ACID PRODUCTION

1.3.1 HYDROLYSIS OF CYANOACETIC ACID WITH STRONG ACID

1.3.2

ACID CATALYSED SAPONIFICATION OF MALONIC ESTER (DIETHYL MALONATE)

1.3.3

CATALYTIC OXIDATION