Acetone

VALIDATION SHEET STUDENTS,

SITI AISYAH

CITRA METYA OKTIANISA

NIS 08.54.06319

NIS 08.54.06140

PARENTS,

SUBJECT TEACHER,

RUSMAN, S.Si, M.Si NIP 19781113 200502 1 1 001

ACETONE 1

PREFACE Assalamualaikum Wr. Wb.

Thankful to Allah SWT, because without Allah’s helps, we cannot finish this paper, there is ACETONE. This module made base on the information from various media. This module contained by acetone with its properties and preparation, completed with the illustration from figures that served and selected in such a manner so it will help to understand the subject. All of this made in order to make the readers think further and find out more complete information. We hope, this paper will give you a lot of benefits to understand about acetone and especially to our regard teacher. All of mistakes are absolutely caused of us as ordinary students. Hopes this module will give us a lot of benefits. Amin.

Wassalamualaikum. Wr. Wb.

Bogor, May 2009

Citra Meyta Oktianisa & Siti Aisyah

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TABLE OF CONTENT VALIDATION SHEET.....................................................................................1 PREFACE.....................................................................................................2 TABLE OF CONTENT....................................................................................3 LIST OF TABLE.............................................................................................5 TABLE OF FIGURE........................................................................................6 LIST OF ATTACHMENT.................................................................................7 ...................................................................................................................7 INTRODUCTION...........................................................................................8 PHYSICAL PROPERTIES OF ACETONE.........................................................11 CHEMICAL PROPERTIES OF ACETONE........................................................15 1)Basic Properties of Ketones................................................................15 2)Addition to Carbonyl Group................................................................17 3)Addition of Hydrogen Cyanide............................................................23 4)Bisulfite Addition Compound..............................................................25 5)Reduction of Carbonyl Compounds to Alcohol....................................27 6)The Haloform Reaction.......................................................................30 7)Addition of Haloform to Carbonyl Compounds....................................32 8)The Pinacol Reduction........................................................................32 9)Imine Formation with Primary Amines................................................33 10)Reactions of ketones with Grignard Reagents..................................34 11)Test for aldehydes and ketones and differentiation between them..36 CHEMICAL PREPARATION OF ACETONE.....................................................39

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Industry Scale .......................................................................................39 Laboratory Scale....................................................................................44 Biochemistry Scale................................................................................46 ACETONE EXISTENCE IN NATURE..............................................................58 UTILITY OF ACETONE.................................................................................61 Acetone as a Solvent.............................................................................61 Cleaner and Degreaser..........................................................................63 Nail varnish remover.............................................................................63 Paint remover .......................................................................................64 Nail extension........................................................................................65 HAZARD AND SAFETY WARNING FOR ACETONE........................................67 First Aid Measures.................................................................................68 Fire Fighting Measures...........................................................................69 Handling and Storage............................................................................70 Exposure Controls/Personal Protection..................................................71 Stability and Reactivity..........................................................................72 ACETONE IN NEWS....................................................................................73 Introduction about Diabetes..................................................................73 Laboratory Diagnosis.............................................................................75 Metabolic Disorders from Diabetes Mellitus:..........................................75 REFERENCES ............................................................................................79

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LIST OF TABLE Table 1 . Physical Properties of Acetone...................................................14 Table 2 . Physical properties of isopropyl alcohol.....................................42 Table 3 . Inoculation of the bacteria..........................................................51 Table 4 . Result of the inoculation.............................................................52 Table 5 . Inoculation for related inoculation..............................................56

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TABLE OF FIGURE Figure 1 . Acetone.......................................................................................8 Figure 2 . Condense structure of acetone.................................................11 Figure 3 . Structure and Dimension for Acetone Molecule........................11 Figure 4 . Ball-and-stick Model for Acetone Molecule................................11 Figure 5 . Space-Filling Model for Acetone Molecule.................................12 Figure 6 . Curve relating the two glycerol. to one flask, continuos curves, puryvic acid was added at the commencement of and curve during fermentation.............................................................................................55 Figure 7 . Atmosphere of our earth...........................................................58 Figure 8 . Acetone as a solvent.................................................................62 Figure 9 . Acetone as cleaner and degreaser............................................63 Figure 10 . Acetone as Nail polish remover...............................................64 Figure 11 . Acetone as Paint Remover......................................................65 Figure 12 . Acetone as Nail extension.......................................................65 Figure 13 . Metabolic Disorders of Uncontrolled DIabetes Mellitus...........76 Figure 14 . Acetone in human breath.......................................................77

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LIST OF ATTACHMENT 9 Organic Chemistry Module by Rusman, S.Si., M.Si.

dkk (page 115) 9 General Organic and Biochemistry by McGraw-Hill

(page 758-807) 9 Pengantar Ke Kimia Organik Hayati by Penerbit ITB 9 Kimia Organik by Fessenden & Fessenden (page 1-

63) 9 Principle of Organic Chemistry (page 249-281) 9 Pengantar ke Kimia Organik by Herman Busser (page

91-93) 9 Source from www.medterms.com 9 Source from www.smallstuff-digest.com 9 Source from www.elmhurst.edu 9 Printout of pdf from www.jbc.org (page 1-8)

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Capture 1 INTRODUCTION

Figure 1 . Acetone

Acetone, also known as propanone, dimethyl ketone, 2propanone, propane-2-on, dimetilformaldehida, and β-ketopropana, is a liquid compound that is colorless and highly flammable. He is the simplest ketone. Acetone soluble in various comparisons with water, ethanol, diethyl ether, etc. He himself is also an important solvent. Acetone is used to make plastics, fibers, pharmaceuticals, and chemical compounds other. In addition to the industry manufactured, acetone can also be found in nature, including the human body in small womb. Acetone is also known as dimethyl ketone or propanone are important compounds of aliphatic ketones. First acetone produced by dry distillation of calcium acetate, fermentation carbohydrates

ACETONE 8

into acetone, butyl and athyl-alcohol that replaces in the year 1920. It undergoes reform process in 1950 and 1960 the process dehydrogenation 2-propanol and cumene oxidation into phenol and acetone. A long with propene oxidation process, this method produces more than 95% acetone produces in the world. Acetone requirement in Indonesia always increase but there is no Indonesian company have to producing acetone in industry scale until today. To meet domestic demand, Indonesia brought acetone from other countries such as: United States, The Netherlands, China, Korean, Japan, and Singapore. Indonesia had imported acetone as 10.999 tons in 2002, 12.785 tons in 2003, 13.401 tons in 2004, 12.251 tons in 2005, and 14.203 tons in 2006 Most simple aldehydes and ketones are liquids. However, formaldehyde and acetone are gas with boiling point for acetone is 56.530C and that is near with room temperature. Ketones are polar molecules because of the C=O bond dipole

Because of their polarity, ketones has higher boiling point than alkenes or alkanes with similar molecular weights and shapes. But since ketones are not hydrogen-bond donors, their boiling point are considerably lower than those of the corresponding alcohols.

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Ketones with four fewer carbons have considerably solubility in water because they can accept hydrogen bonds from water at the carbonyl oxygen.

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Capture 2 PHYSICAL PROPERTIES OF ACETONE

Figure 2 . Condense structure of acetone

Figure 3 . Structure and Dimension for Acetone Molecule

Figure 4 . Ball-and-stick Model for Acetone Molecule

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Figure 5 . Space-Filling Model for Acetone Molecule

IUPAC NAME PROPANONE

OTHER NAMES β-ketopropane, dimethyl ketone, dimethylformaldehyde, DMK, propanone, 2-propanone, propan-2-one

IDENTIFIER CAS NUMBER

67-64-1

PubChem

180

ChemSpider

175

EC-number

200-662-2

RTECS number

AL31500000

InChi key

CSCPPACGZOOCGX-UHFFFAOYAF

PROPERTIES Molecular formula

C3H6O

Molar mass

58.08 g mol−1

Appearance

Colorless liquid (white snow-like form when solid)

Density

0.7925 g/cm3

Melting point

−94.9 °C, 178 K, -139 °F

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Boiling point

56.53 °C, 330 K, 134 °F

Solubility in water

miscible

Acidity (pKa) Refractive index (nD)

24.2

Viscosity

0.3075 cP

1.35900 (20 °C)

STRUCTURE Molecular shape

trigonal planar at C=O

Dipole moment HAZARDS

2.91 D

MSDS

External MSDS

EU classification

F

R-phrases

Xi R11, R36, R66, R67

S-phrases

(S2), S9, S16, S26

NFPA 704

Flash point Autoignition temperature Explosive limits Threshold Limit Value LD50

3 1 0 −17 °C 465 °C 4.0–57.0 500 ppm (TWA), 750 ppm (STEL) >2000 mg/kg, oral (rat)

SUPPLEMENTARY DATA PAGE Structure and

n, εr, etc.

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Properties Thermodynamic data Spectral data

Phase behaviour Solid, liquid, gas UV, IR, NMR, MS

Table 1 . Physical Properties of Acetone

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Capture 3 CHEMICAL PROPERTIES OF ACETONE

1)Basic Properties of Ketones The basicity of the carbonyl group that is conferred upon it by the unshared oxygen electrons is manifested by its ready protonation by strong acid and its coordination with Lewis acids :

The basicity of carbonyl compound can be greatly increase if the positive charge of the resulting conjugate acid is delocalized by resonance; that is, if a number of contributing structure of comparable energy can be written. Acetones are weakly basic and reacts at the carbonyl oxygen with protons or Lewis acid

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As figure above, the protonated form of an acetone is resonance stabilized. The resonance structure on the right shows that the protonated carbonyl compound has carbocation character. In fact, we shall find in some cases that the conjugate acids of ketones undergo typical carbocation reactions. Closely related to pronated acetone are alpha-alkoxycarbocation : cartions in which the acidic is replaced by an alkyl group.

Such ion is considerably more stable than ordinary alkyl cations. For example, a secondary alpha-alkoxycarbocation is about 40 kcal/mol more stables in the gas phase than an ordinary secondary carbocation

These ions owe their stabilities to the resonance interaction of the electrom-deficient carbon with the neighboring oxygen. This resonance effect far outweighs the electron-attacking inductive effect of the oxygen, which, by itself, would destabilize the carbocation. Ketones, especially acetone, in solution are considerably less basic than alcohols. In other words, their conjugate acids are more acidic than those of alcohol.

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Since protonated ketones are resonance stabilized and protonated alcohols are not, we might have expected the protonated carbonyl compound to be more stable relative to their conjugate bases and therefore less acidic. As the pKa values above, this is not the case. The relative acidity of protonated alcohols and carbonyl compounds has been found to be yet another example of a solvent effect. In the as phase, ketone is indeed more basic than alcohols. One reason for the greater basicity of alcohols in solution that protonated alcohols have more O-H protons to participate in hydrogen bonding to solvent than do protonated ketone.

2)Addition to Carbonyl Group a.

Mechanisms

of

carbonyl-addition

reactions Carbonyl-addition reactions occur by two general types of the mechanisms.

The

first

general

mechanism

occurs

under

basic

conditions. In this mechanism, a nucleophile attach the carbonyl group at the carbonyl carbon, and the carbonyl oxygen becomes negatively charged. In cyanohydrin formation, for example, the cyanide ion, formed by ionization of HCN, is the nucleophile

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The negatively charged oxygen—essentially an alkoxide ion—is a relatively strong base, and its protonated by either water or HCN to complete the addition:

The mechanism, called nucleophilic addition, has no analogy in the reactions of ordinary alkenes. The pathway occurs with aldehydes and ketones because, in the transition state, negative charge is placed on oxygen, an electronegative atom. The same reaction on an alkene would place negative charge on a relatively electropositive carbon atom.

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Attack by the nucleophile occurs on the carbon of the carbonyl group rather than the oxygen for the same reason: negative charge is placed on the more electronegative atm— oxygen. Among the reactions we have studied, the closest analogy to nucleophile carbonyl addition is nuclephilic ring opening of epoxides. Both mechanisms involve attack a nuclephilic at carbon, giving a negativey charge oxygen:

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An orbital picture of nucleophilic addition, along with the geometry of nucleophilic attack on the carbonyl group, is shown in fig. 19.8. when a nucleophilic attack a carbonyl group, it attacks the π-bond from above or below the plane of the molecule, “pushing” an electron pair onto the carbonyl oxygen. The second mechanism for carbonyl addition occurs under acidic conditions, and is closely analogous to electrophilic addition

to

alkenes.

Acid-catalyzed

hydration

of

carbonyl

compounds is an example of this mechanism. The carbonyl group is first protonated an acid in solution.

The

protonated

character.

The

carbonyl

compound

electron-deficient

carbon

has is

carbocation attacked

by

anucleophile, in this case water, which then loses a proton, completing the addition. The particular mechanism is very much like that for the hydration of alkene. Notice that under basic conditions, the nucleophile is usually a fairly strong base, and the acid that protonates the negative oxygen is usually a weak acid—in many cases the conjugate acid of the nucleophile. Under basic conditions strong acids are not available to complete the protonation, nor are they necessary, since the alkoxide is a fairly strong base. Conversely, under acidic conditions, the carbonyl is protonated by a relatively strong acid, and the nucleophile is usually a fairly weak base. Under acidic conditions, strong bases are not available, nor are

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they necessary, since a protonated carbonyl compound is very electrophilic—it is, after all, a carbocation. In the fact, sometimes beginning students are tempted to write mechanisms involving strong acids and strong bases at the same time:

Mechanisms such as this are extremely rare, because high concentrations of H3O+ (a strong acid) and OH- (a strong base) cannot axist at the same time in solution. The appropriate nucleophile for the second equation is water, not hydroxide, because under acidic aqueous conditions, water usually acts as the base. b.

Equilibrium

in

Carbonyl-Addition

reactions Hydration and cyanohydrin formation have in common the fact that they are reversible. (Not all carbonyl additions are reversible.) cyanohydrin formation, for example, favors the product in the case of aldehydes and methyl ketones, but not aromatic ketones. Hydration occurs more extensively with aldehydes than with ketones. What is the reason for these effects? • Addition is more favorable for aldehydes than for ketones • Electronegative groups near the carbonyl carbon make carbonyl addition more favorable

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• Addition is less favorable when groups are present that donate electrons by resonance to the carbonyl carbon

Each of these effects is understandable in terms of the relative stabilities of aldehydes and ketones. The stability of the carbonyl compound relative to the addition product governs the ΔG0 for addition. This point is illustrated in figure below. The conclusion from the figure is that added stability in the carbonyl compound increases the energy change (ΔG0), and

hence

decreases

the

equilibrium

constant,

for

formation of an addition product. What stabilize carbonyl compounds? One way to answer this question is to consider the resonance structure of the carbonyl group:

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The structure on the right, although not as important a contributor as the one on the left, reflects the polarity of the carbonyl group, and has the characteristics of a carbocation. Therefore anything that stabilizes carbocations also tends to stabilize carbonyl compounds. Since alkyl groups stabilize carbocations, ketones are more stable than aldehydes (R=H). We can see the stability reflected in the relative heats of formation of aldehydes and ketone. ACETONE with ΔHf0= - 52.0 kcal/mol, is 6.1 kcal/mol more stable than its isomer propionaldehyde which has ΔHf0=-45.9 kcal/mol. Since alkyl groups stabilize carbonyl compounds, the equilibria for additions to ketones are less favorable than those for additions to aldehydes (trend1). Formaldehyde, with two hydrogen and no alkyl groups bound to the

carbonyl,

has

a

very

large

equilibrium

constant

for

hydrations. Electronegative

groups

such

as

halogens

destabilize

carbocations by an inductive effect, and also destabilize carbonyl compounds. Thus, halogens make the equilibria for addition more favorable (trend 2). In fact, chloral hydrate (known in medicine as a hypnotic) is a stable crystalline compound.

3)Addition of Hydrogen Cyanide The addition of hydrogen cyanides to ketones (especially acetone) is a less general reaction than the addition to aldehydes, since it is a slower

ACETONE 23

reaction, frequently with a less favorable equilibrium and is influenced by structural factor. However, simple ketones, such as acetone, add HCN readily to form the corresponding cyanohydrins.

Chyanohydrin are usefull synthetic intermediates since they can be hydrolyzed (usually with HCl/H2O) to alpha hydroxy acid:

The product of HCN addition is termed a cyanohydrin. Cyanohydrins constitute a special class of nitriles (organic cyanides). Notice that the preparation of cyanohydrins is another method of forming carbon-carbon bonds.

All carbonyl-addition reactions show a complementarity between the plarity of the addition reagent and the polarity of the carbonyl group. Thus, the electropositive end of the addition reagent (the proton) adds to the electronegative end of the carbonyl group (the oxygen), and the

ACETONE 24

electronegative

end

of

the

reagent

(-OH

or

–CN)

adds

to

the

electropositive end of the carbonyl group (the carbonyl carbon)

The generalization is analogous to the marnovnikov rule for alkenes addition

4)Bisulfite Addition Compound The addition of sodium bisulfite to aldehydes and to the lowmolecular weight ketones is another characteristics carbonyladdition reaction

Na-hydroxypropanesulfonate

The product of this reaction is commonly called a “bisulfite addition compound”. It is a salt, and if an attempt is made to convert it into the corresponding acid by treatment with a mineral acid, the aldehydes is regenerated and SO2 is evolved. This result illustrates the reversible character of the addition reaction. The bisulfite reaction follows the basic pattern of the addition reaction generalized in (3). The bisulfite ion

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Has a plethora of available electrons pairs, and it would be difficult to decide a priori whether the attack proceeded to form an oxygen-carbon or sulfur-carbon bond:

Indeed, it was found necessary to carry out a detailed study of the constitution of the bisulfite addition compounds to establish that it is actually a carbon-sulfur bond that is formed, and that the reaction proceed (with acetone in the following example) by attack of the unshared electron pair of the sulfur atom

The addition of sodium bisulfite is a very useful means of isolating aldehydes from mixture. The bisulfite addition compound (a sodium salt) frequently separates as a crystalline solid, especially when the concentrated (40%) sodium bisulfite is used, and can be

ACETONE 26

separated

by

contaminating

filtration

and

washed

with

substance. Treatment of

ether

the

to

remove

purified

addition

compound with dilute acid or alkali regenerates the aldehyde, which can then be separated by extraction or distillation.

5)Reduction of Carbonyl Compounds to Alcohol The addition of hydrogen to the carbonyl double bond leads to the formation of primary alcohols from aldehydes and secondary alcohols from ketones. Lithium aluminum hydride, sodium borohydride, and NaBH4 are useful for reduction of carbonyl groups of aldehydes and ketones and not those of acid derivatives. Lithium aluminum hydride, on the other hand, reduces acids and acid derivatives as well as aldehydes and ketones. Aldehydes and ketone are reduced to alcohols with either lithium aluminum hydride, LiAlH4, or sodium borohydride, NaBH4. These reaction result in the net addition of the elements of H2 across the C=O bond Lithium aluminum hydride, this reagent, one of the most useful reducing agents in organic chemistry, serves generally as a source of H-, the hydride ion. This is reasonable because hydrogen is more electronegative than aluminum (table 1.1). Thus, the Al-H bonds of the –AlH4, ion carry a substantial fraction of the negative charge. In other words,

ACETONE 27

The hydride ion n LiAlH4, is very basic. For example, LiAlH4 reacts violently with water, and therefore must be used in dry solvents such as anhydrous ether and THF.

Like many good bases, the hydride ion in LiAlH4 is a good nucleopile. The reaction of LiAlH4 with aldehydes and ketones involves the nucleophile attack of hydride (delivered from –AlH4) on the carbonyl carbon. A lithium ion coordinated to the carbonyl oxygen acts as a Lewis-acid catalyst

The aloxide salt (which actually exist as a complec with the Lewis acid AlH3 or other trivalent-aluminum species present in solution) is converted by protonation into the alcohol product. The proton source in water (or an aqueous solution of a weak acid such as ammonium chloride), which is added in a separates step to the reaction mixture.

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As the stoichiometries, all four hydrides of LiAlH4 are active, although we shall not consider here the detailed mechanism for reduction by hydride equivalents beyond the first. The reaction of sodium borohydride with aldehydes and ketones is conceptually similar to that LiAlH4. The sodium ion, however, does not coordinate to the carbonyl oxygen as well as the lithium ion does. For the reason, NaBH4 reductions are carried out in protic solvents, such as alcohols. Hydrogen bonding between the alcohol solvent and the carbonyl group serves as a weak acid catalyst that active the carbonyl group. NaBH4 reacts only slowly with alcohols, and even be used in water if the solution is not acidic.

All four hydride equivalents of NaBH4 are active in the reduction. Because LiAlH4 and NaBH4 are hydride donors, reductions by these and related reagents are generally refereed to as hydride reductions. The important mechanism point about these reactions is that they further examples of nucleophilic addition. Hydride ion from LiAlH4 or NaBH4 is the nucleophile, and the proton is delivered

ACETONE 29

from acid added in a separate step (in the case of LiAlH 4 reductions) or solvent (in the case of NaBH4 reductions).

6)The Haloform Reaction Ketones that contain the grouping –COCH3, such as acetone, react with alkaline solutions of bromine, chlorine, and iodine (i.e., with sodium hypobromite, hypochlorite, and hypoiodite) to furnish the corresponding haloform (bromoform, CHBr3, etc) and the salt of the acid RCOOH (from RCOCH3) :

This reactions, called the haloform reaction, proceeds in two stages : the first (using NaOCl as the example) is the halogenation of the –COCH3 group to –COCCl3; the second is the cleavage of the resulting RCOCCl3 by the hydroxide in the alkaline solution :

ACETONE 30

The nucleophilic attack of OH- on the carbonyl carbon atom is aided by the strong inductive withdrawal of electrons by the three chlorine atoms of the _CCl3 group. This inductive reduction of electron density on the carbon atom of –CCl3 also permits its dissociation as the negative (:CCl3)-ion. The process is completed by the protonation of :CCl3- (which is a very strong base), to give CHCl3. In the case of the equation above, the reaction is complete to the right because in the alkaline solution the ionization of the acid CH3CH2COOH is complete to give CH3CH2COO-, to which carbonyl addition does not occur. The haloform reaction is carried out by adding a solution of sodium hypochloride or hypobromite to the methyl ketone, or by adding iodine (dissolve in aqueous potassium iodide) to a solution of the ketone in aqueous or methanolic alkali. For diagnostic (as contrasted with preparative) purposes iodine is commonly used because iodoform is a crystalline yellow solid which can be readily

ACETONE 31

isolated and identified by its appearance and melting point; both bromoform and chloroform are liquids at ordinary temperature.

7)Addition of Haloform to Carbonyl Compounds It can be anticipated from the last equation that CHCl3 in the presence of a base should be capable of adding to a carbonyl group. This is indeed the case :

The addition of bromoform gives the corresponding tribromo compound “brometone”. These trihalo-t-butyl alcohols are used in medicine as hypnotics and sedatives; they are similar in structure and action to chloral hydrate, Cl3C.CH(OH)2, a much-used hypnotic drug. This addition of chloroform or bromoform to the carbonyl group is, of course, smply anther of the class of addition reactions that proceed by nucleophilic attack upon the carbonyl carbon atom :

8)The Pinacol Reduction

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The reaction of acetone with magnesium (which has been activated by amalgamation with mercury by treatment with mercuric chloride) yields a solid magnesium derivative which is decomposed by hydrolysis into a magnesium salt (of the acid used for the hydrolysis) and pinacol

The “pinacol reduction” is one-electron reduction (per molecule of ketone), and proceeds by the acceptance of the two electrons of magnesium by two molecules of acetone, followed by pairing of the lone electron to form a carbon-carbon bond :

9)Imine Formation with Primary Amines A primary amine is an organic derivative of ammonia in which only one ammonia hydrogen is replaced by an alkyl or aryl group. An imine is a nitrogen analog of an aldehyde or ketone in which the C=O group is replaced by a C=N-R group

ACETONE 33

Imine are prepared by the reaction of aldehyde or ketones with primary amine

Formation of imines is reversible, and generally takes place with acid r base catayses, or with heat. Imine formation is typically driven to completion by precipitation of the imine, removal of water, or both. The mechanism of imine formation begins as a nucleophilic addition to the carbonyl group. In this case, the nucleophilic is an amine. In the first step od the mechanis, the amine reacts with the aldehyde or ketone to give an unstable addition compound called a carbinolamine. The mechanism of the addition is analogous to the mechanism of other reversible additions attack of the nucleophile on the carbonyl carbon, followed by proton transfers to and from solvent

10) Reactions of ketones with Grignard Reagents

ACETONE 34

Addition of Grignard reagents to ketones is an ether solvent, followed by protonolysis, gives alcohols. This is the most single application of the Grignard reagent in organic chemistry

The reaction of Grignard reagents with ketones is another example of carbonyl addition. In this reaction, the magnesium of the Grignard reagent, a Lewis acid, coordinated with the carbonyl oxygen.

This

coordination,

much

like

protonation

in

more

conventional acid-catalyzed additions, increases the positive charge on the carbonyl carbon. The carbon group of the Grignard reagent attacks the carbonyl carbon recall that this group is a strong base that behaves much like a carbanion

The product of this addition, a brommagnesium alkoxide, is eesentially the magnesium salt of an alcohol. Addition of dilute acid to the reaction mixture gives an alcohol.

ACETONE 35

Because of the great basicity of the Grignard reagent, this addition, like hydride reductions, is not reversible, and works wth just about any aldehyde or ketone. The reactions of organolithium and sodium acetylide reagents with aldehydes and ketones are fundamentally similar to the Grignard reaction,

The reaction of Grignard and related reagents with ketones is important not only because it can be used to convert ketones into alcohold, but also because it is an excellent method of carboncarbon bond formation.

11)Test for aldehydes and differentiation between them

ketones

and

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The addition of bisulfite and HCN is not a property of aldehydes only, but of certain kinds of ketones (e.g., R-COCH3) as well. Thus, the classification of an unknown carbonyl compound as an aldehyde cannot safely be based solely upon the observation that it forms a cyanohydrin or a bisulfite addition compound. On the other hand, a carbonyl compound that does not react in either of these ways is probably not an aldehyde. The clearest distinction between aldehydes and ketones lies in the ease with which aldehydes can be oxidized to acids with certain reagents, and the stability of ketones to these reagents. Two oxidizing agents that are commonly used for this purpose are Tollen’s reagent and Fehling’s solution or the very similar Benedict’s reagent). Tollen’s reagent is an ammoniacal solution of the silver ion-ammonia complex; it is readily reduced by easily oxidized compounds with the formation of metallic silver (as a black precipitate or silver mirror) :

The criterion of a positive test is the appearance of metallic silver: the organic products of the oxidation are usually not demonstrated as the test is ordinarily performed. Fehling’s solution and Benedict’s reagent are both cupric complexes, and a readily oxidized compound will redce cupric ion to the cuprous state, with the formation of an orange to red precipitate of cuprous oxide (Cu2O) Neither tollen’s reagent nor Fehling’s solution is specific for aldehydes, since other easily oxidized compounds will also ve

ACETONE 37

positive tests. But if the question is one of distinguishing between simple aldehydes and ketones, only aldehydes will give positive tests, ketone will not. Based on the fact, the sugar fructose will reduce Fehling’s solution and Tollen’s reagent. Fructose is ahydroxy ketone, containing the grouping (gambar); and it is found that Fehling’s solution will also oxidize other compounds with this structure. For example, acetoin, CH3COCHOHCH3, will give a positive Fehling’s test. Simple dialkyl ketones, however, will not. Aldehydes can also be recognized by their ability to react with Schiff’s reagent. This reagent is formed by adding sulfur dioxide to a

solution

of

a

magenta

dye

called

“fuchsine”,

with

the

decolorization of the dye as a result of the addition to it of SO 2. The greater reactivity of aldehydes in the addition of bisulfite ion (which is a hydrated for of SO2) allows the aldehyde to abstract SO2 from the dye, restoring the color. A positive test is the change of color of the reagent from colorless or pale yellow to pink or reddish violet. Ketones, in which the addition of bisulfite proceed to a smaller extent, do not restore the color.

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Capture 4 CHEMICAL PREPARATION OF ACETONE

Industry Scale There are several kinds of manufacturing processes commercially acetone, include:

Process Cumene Hydroperoxide Cumene

initially

oxidized

to

Cumene

Hydroperoxide

at

atmospheric air or oxygen-rich are in one or several oxidation. Temperature used is between 80 ° C - 130 ° C with 6 atm, and with the addition of Na2CO3. The oxidation process is generally run in 3 or 4 series reactor installed. Reaction : C 6 H 5 CH (CH 3 ) 2 → C 6 H 5 (CH 3 ) 2 → C 6 H 5 OH → C 3 H 6 O

Results from the oxidation of the first reactor contain Cumene hydroperoxide 9-12%, 15-20% in the second reactor, 24-29% in the

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third reactor, and 32-39% in the next reactor. Then the fourth reactor product concentration that evaporated until hydroperoxide cumnene be 75-85%. Then with the addition of acid will occur cumene hydroperoxide cleavage reaction into a mixture that consists of Phenol, acetone, and various other products such as chumylphenols,

acetophenone,

dimethyl

phenylcarbinol,

metylstyrene, and hydroxyacetone. The mixture then neutralized by the addition of sodium phenoxide or other bases or with other ion exchangers. Then separated and the crude mixture of acetone obtained by distillation. To obtained the desired purity necessary addition of one or more columns distillation. If you used columns, the first column to separates or impurity likes Propionaldehyde and Acetaldehyde. While the second column to separate the functions of weight consisting mostly of water. Acetone obtained as a result of the second tower (Kirk & Othmer, 1991).

Propylene Oxidation Process Propylene oxidation process becomes acetone can take at a temperature of 1450C and pressure of 10 atm with the help of bismuth catalyst on alumina phaspomolibdat. In this process consists of reaction products and propanoldehyde acetone. Reaction: CH 2 = CHCH 3 +

1 O2 → C 3 H 6 O + C 3 H 6 O 2

The oxidation process of making isopropyl alcohol acetone in this process, isopropyl alcohol mixed with air and used as bait reactor operating at a temperature of 2000C-8000C. The reaction

ACETONE 40

can be run well using a catalyst such as that used in isopropyl alcohol dehydrogenation process. CH 3CHOHCH

3

+

1 O2 → H 2 O + C 3 H 6 O 2

This reaction is very exothermic (43rd kcal/mol) at 250C and for temperature control was needed very carefully to prevent the resulting decline on yield. To get a good conversion reactor can be designed to direct the desired results. The process is rarely used when compared wth te dehydrogenation process (Kirk & Othmer, 1983).

Isopropyl alcohol dehydrogenation process Another process which is very important to produce acetone is a catalytic dehydrogenation reaction which is endothermic. Reaction:

C 3 H 8 O + 66.5 kJ

mol

( pada 3720 C ) → C 3 H 6 O + H 2

In this process evaporated with isopropyl alcohol and heated in a vaporizer HE by using steam and then inserted into the multi tubular fixed bed reactor. There are a number of catalyst that can be used in this process is a combination of zic oxide, zirconium oxide, a combination copper chromium oxide, copper, silicon oxide. This reactor operating conditions is 1.5-3 atm and temperature is 4000C-6000C. With this conversion process can reach 75-98% and the yield can reach 8590%. Hot gas out of the reactor consisting of isopropyl alcohol, acetone, and hydrogen is passed scrubber, to separate the

ACETONE 41

insoluble gas (H2) with acetone, isopropyl alcohol, and water. Results from the scrubber is distilled, acetone taken as a result of the mixture while isopropyl alcohol and water as a result of bottom. The results are distilled down again for isopropyl alcohol recovery is taken as result of that later in the recycle to the reactor (Kirk & Othmer, 1983). Isopropyl alcohol dehydrogenation process is selected because it has the following reasons: a.

Isopropyl alcohol dehydrogenation process does not

require O2 separation unit of the air before being fed into the reactor b.

With the amount of isopropyl alcohol the same, the

conversion of greater dehydrogenation process so that the results acetone is more available. c.

In the oxidation process of corrosion problems that can

disrupt the process, while at dehydrogenation process, it can be reduced. One of the most important material in the preparation of acetone is isopropyl alcohol. It has other name, such as isopropanol, 2propanol, dimethyl carbynol, etc. Physical properties of isopropyl alcohol Molecular formula C3H7OH Molecular Weight 60.10 g/mol Appearance Colorless liquid Boiing point 83.2 0C Freezing Point -88.5 0C Refractive index 1.3772 Viscosity 2.4 cP Density 0.7854 g/cm3 Specific Gravity 0.7864 Table 2 . Physical properties of isopropyl alcohol

ACETONE 42

Although major impurities in commercial grades of acetone or methanol, acetic acid, and water, the analytical reagent generally contains less than 0,1 % of the organic impurities although the water content may be as high as 1%. Commercial acetone may be purified in several ways: Acetone is heated under reflux with successive quantities

a.

of potassium permanganate until the violet colour is persisting. It’s

then

dried

with

anhydrous

potassium

carbonate

or

anhydrous calcium sulphate (anhydrous of calcium chloride should not be used as some chemical combination occurs) filtered from the desiccant and fractionated; precautions are exclude moisture. b.

To 700 ml of acetone (b.p. : 56-570C), contained in a

littler bottle, a solution of 3 g of silver nitrate in 20 ml of water added, followed by 20 ml of 1 M NaOH, and the mixture is shaken for about 10 minutes. The mixture is then filtered, dried with anhydrous calcium sulphate and distilled. c.

When only a relatively small quantity of pure dry

acetones required, it may be purified through the bisulphate complex: the la tter is decomposed with sodium carbonate solution dried over anhydrous calcium sulphate and distilled. A more

convenint

procedure

is

to

make

use

of

addition

compound with sodium iodide, which decomposes on gentle heating and it’s particularly well adapted for the preparation of pure acetone. 100 grams of finely powdered sodium iodide are dissolved under reflux in 440 g of boiling commercial acetone, and the solution is cooled in a mixture of ice and salt (-8 0C). The crystals are filtered off and quickly transferred to dry distilling flask connected to an efficient conceder and to a

ACETONE 43

receiver cooled in ice. Upon gentle warming, the acetone distills rapidly.

Laboratory Scale Acetone is produced directly or indirectly from propene. Most commonly, in the cumenen process, benzene is alkylated with propene and the resulting cumene (isopropyl benzene) is oxidized to give phenol and acetone C 6 H 5 CH (CH 3 ) 2 + O2 → C 6 H 5 OH + OC (CH 3 ) 2

This

conversion

entails

the

intermediacy

of

cumene

hydroperoxide C6H5C(OOH)(CH3)2. Acetone is also produced by the direct oxidation of propene with a Pd (II) or Cu (II) catalyst, akin to the Wacker process.

Oxidation of Secondary Alcohol

For this reaction, the secondary alcohol is oxidized. Oxidizing agent can be K2Cr2O7 in acid condition or KmnO4 in acid condition.

Catalitic Dehydrogenation of Secondary Alcohols

ACETONE 44

In this case, a catalyst is added. For this reaction, the catalyst is Cu metal in temperature is 300oC.

Ozonolysis of Alkenes

By alkaline hydrolysis of gen-dihalides

REACTION OF CaCO3 If calcium or sodium salt from distilled and dried fat acid, ketone will be formed

ACETONE 45

CH3.CO

CH3

O CH3.CO

CH3

O

Acetyl halide and grignard reagent Acetyl halide reacts with grignard reagent will form ketone.

Nitrile reaction Nitrile reacts with grignard reagent will form addition reaction and if the resulted is oxidized, it will form ketone

CH3 C

CH3

CH3

CH3

CH3

Biochemistry Scale This is it, the biochemistry of acetone formation from sugars by Bacillus acetoethylicum Acetone is found among the products of two distinct types of bacteriological fermentation. Anaerobic bacilli of the amyloback

ACETONE 46

type produce acetone and butyl alcohol from a large series of sugars, and the characteristic acid products are butyric and acetic acids. A second group of bacilli produce acetone and ethyl alcohol from sugars, and the volatile acids produced are acetic acid anti formic acid. The first member of this group to be described was Bacills macerans by Schardinger (I), and the second was isolated, described, and named by Northrop, Ishe, and Senior (2) Bacillus acetoethylicunz. The two species differ in only one important characteristic; namely, Bacillus acetoethylicum alone is able to ferment galactose and lcvulose in a medium containing ammonium salts as the source of nitrogen. The investigation of this type of fermentation was continued by Arzberger, Peterson, and Fred (3, 4), and mention will be made later of several important points established by these workers. Neuberg and his associstes have discussed the method by which acetone is produced by bacterial action, and they are of the opinion that the following scheme holds for both the amylobacter and maccrans types of fermentation (5). Northrop in his original paper reported that the neutral products of the fermentation of several sugars were 5 to 10 percent acetone and 12 to 25 percent ethyl alcohol, whereas, there was no acetone produced from glycerol, but the yield of ethyl alcohol rose to 40 per cent. An attempt has been made to study further these fermentations, to account for the difference in the products, and to utilize the experimental evidence obtained in formulating a biochemical scheme for this organism.

EXPERIMENTAL

ACETONE 47

The parent culture used in this investigation was obtained by the courtesy of the American Museum of Natural History, New York. Stock cultures have been maintained for several years by periodic transfers in a medium containing maize meal and 1 per cent CaC03. For the purpose of these experiments active cultures were obtained in the following manner. Agar plate cultures grown aerobically were prepared from an active maize culture. Individual colonies were transferred to two types of liquid media, one containing 3 per cent maltose and the other 3 per cent glycerol in a stock solution of mineral salts, calcium carbonate, and peptone. For several weeks the organism was kept active in these two media in order to rule out from our glycerol experiments any changes due to an initial transfer of the bacillus from a medium containing sugar. Both types of media support active fermentations.

Experiment I A preliminary qualitative examination was made of the products obtained by the fermentation of gIucose, maltose, and glycerol. Two points of theoretical significance were established. Previous reports contain very little information regarding the nature of the gas which is evolved. Northrop does not mention the subject, and in the experiments of Arzberger, Peterson, and Fred the gas was estimated quantitatively as CO2. That H, is evolved in sugar and glycerol fermentations can be shown by collecting samples of gas, removing the CO2 by means of NaOH, and exploding the residue with air. This is in accordance with the facts relating to similar bacteriological fermentations. The second point of importance is that traces of pyruvic acid are present at various times in fermenting media containing

ACETONE 48

glycerol or glucose. This was first indicated satisfactorily during an examination

of

old

test-tube

cultures,

using

the

method

recommended by Simon and Piaux (6) and Quastel (7). To a small volume of culture add 2 cc. of H 20 and supersaturate with solid (NH4)2SO4 in the cold. Add a crystalof sodiumnitroprusside and 2 cc. of NH40H. Shake and allow standing at room temperature. A blue colour gradually develops, and in dilute solutions of pyruvic acid its intensity is proportional to the concentration of the acid. The test is essentially Rothera’s test for acetone, and when this substance is present in the medium it is impossible to establish the presence of traces of pyruvic acid in the mixture owing to the purple color which develops. This difficulty can be overcome in the following manner. A sample of the culture to be tested is heated for 5 minutes at 50°C and 20 mm. of pressure. A little capryl alcohol is added to prevent foaming. Acetone distills over without decomposition of any pyruvic acid which may be present. The test outlined above can be then applied to the residue. The blue color obtained varies from a greenish blue to a pure indigo, according to the amount of pyruvic acid in solution, and for this reason difficulty was encountered when attempts were made to estimate pyruvic acid by these of a standard solution and the calorimeter. A method has been devised, however, which has given satisfactory results in experiments during which the utilization of pyruvic acid by the bacillus was followed. The following standardized conditions are necessary. To 4 cc. of distilled H20 add 1 cc. of the culture and excess of (NH4)2SO4 crystals. Run in from a pipette 2 cc. of a 1 per cent solution of sodium nitroprusside, freshly prepared, and 1 cc. of NH4OH. Allow to stand for 10 minutes, and shake at intervals. Compare the color which develops with a series of test-tubes containing from 1 to 20

ACETONE 49

per cent of CuSO4 in H20 by means of a block comparator. These tubes must be previously standardized in terms of pyruvic acid. In this way concentrations of pyruvic acid from zero to 0.2 per cent can be measured. The remaining products found in our preliminary experiments were those which have been identified by previous workers.

Experiment 2 In order to study more completely the occurrence of pyruvic acid in the fermentation, and its relation to acetone formation, the following experiment was performed. Three series of test-tubes containing maltose, glucose, and glycerol respectively in 3 per cent concentration were prepared, and inoculated. The basis of these media was a mineral salt solution containing also 0.5 per cent of peptone and 1 per cent of CaC03. The glycerol tubes were inoculated from stock glycerol cultures in an active condition, and the sugar-containing tubes from maltose cultures. They were incubated at 38oC, and at intervals a tube of each type was examined qualitatively for acetone and pyruvic acid. Observations regarding

gas

evolution

were

also

made.

The

results

are

summarized in Table I. In the tubes containing sugar pyruvic acid was present during the first half of the fermentation period. Later the free acid disappeared, and acetone accumulated. The maltose tubes were more active than the glucose ones, but the amount of pyruvic acid which could be detected was by far the greater in the glucose medium. In the glycerol fermentation a trace of pyruvic acid was present on the 5th day and more definite amounts on the 21st day of incubation. The loss of acetone in all the tubes was due to

ACETONE 50

evaporation. There appeared to be two possible explanations for the almost complete absence of pyruvic acid and acetone in the products of the glycerol fermentation: (n) the organism only produces the acid from glycerol with difficulty, and pyruvic acid being the intermediate in acetone formation, little of the latter takes place; and (b) pyruvic acid is formed readily from glycerol, but it is converted with equal rapidity into some other characteristic product, most probably ethyl alcohol.

Table 3 . Inoculation of the bacteria

ACETONE 51

Table 4 . Result of the inoculation

EXPERIMENTAL 3 During our preliminary experiment.s in which B. ncetoethylicum was grown for about twenty generations in a glycerol medium it was always possible to detect. acetone in the products by qualitative methods. To obt.ain more definite information regarding the time and extent of this formation the following experiment was performed. Two flasks containing 1,500 cc. of 3 per cent maltose and 3 per cent glycerol medium respectively were prepared, and sterilized in the usual way. Each contained an equal amount, of filter paper, cut into thin strips. The flasks were inoculated with 200 cc. of an active culture in the same type of medium. Samples of 100 cc. were withdrawn at intervals under sterile conditions, and distilled. Quantitative measurements of acetone and

ACETONE 52

ethyl alcohol were made, acetone by the Mcssinger method and ethyl alcohol by oxidation with potassium dichromate and sulfuric acid, followed hy a titration of the excess dichromate with potassium thiosulfat. Tt is unnecessary to describe the methods of procedure in detail. These observations were continued until both fermentations had finished. and the results are given in Table II. This experiment was performed three times. This experiment indicates that during the glycerol fermentation there is a small amount of acetone formed during the second half of the fermentation period. Samples of culture after the 8th day gave a definite purple color when Rothera’s test for acetone was made, showing that the quantitative measurements obtained by the iodoform method were not due ‘to the ethyl alcohol. At no time during this experiment was it possible to detect pyruvic acid in either flask. These fermentations were more active than test-tube cultures, and these observations suggest that the occurrence of free pyruvic acid is determined not only by the nature of the substrate but also by the activity of individual fermentations.

EXPERIMENTAL 4 Acting on the hypothesis, that in the last experiment no acetone was formed in the early stages of the glycerol fermentation owing to the absence of pyruvic acid in the product. Several experiments of the following general type were performed. To one flask containing 1,500 cc. of glycerol medium were prepared and sterilized. ‘1’0 one flask was added just previous to its inoculation 100 cc. of H20 containing 4 gm. of pyruvic acid (Eastman Kodak Company), neutralized with NaOH. The solution of pyruvate had

ACETONE 53

been sterilized by passage through a Barkefeld filter. Both flasks were inoculated with 200 CC. of an active culture in glycerol medium. It intervals during the period of incubation quantitative measurements of pyruvic acid, acetone, and ethyl alcohol were made. On the 2nd clay we observed that almost the whole of the pgruvic arid had been utilized by the organism, and that already acetone had been produced. By the 4th day all the pyrliric acid had been destroyed, and the acetone content of the medium showed an increase of 200 per cent. Ethyl alcohol formation and gas production were also more rapid in the flask which contained pyruvic acid. On the 8th day of incubation a second quantity of pyruvic acid, 3 gm.. was neutralize and sterilized. The solution contained 3 gm of glycerol and was made up to 100 cc. This was added to the flask which had received the first batch. The effect on the general appearance of the fermentation was very pronounced. Gas production was greatly stimulated, and the surface of the medium was covered with filter paper and calcium carbonate. The pyruvic acid was again rapidly utilized, and the effects on the rates of formation of ethyl alcohol and acetone are indicated in Table III and Fig. 1.

ACETONE 54

Figure 6 . Curve relating the two glycerol. to one flask, continuos curves, puryvic acid was added at the commencement of and curve during fermentation

The information obtained by these experiments justifies several important conclusions. In the first place it is clear that Bacillus acetoethylicum utilizes very rapidly any free pyruvic acid in a glycerol medium. This results in the formation of acetone earlier and larger in amount than in the control flask. The two processes do not coincide in time, but about half of the acetone formation takes place after pyruvic acid has disappeared from the medium. These facts suggest that in the formation of acetone from pyruvic acid there are intermediates formed which accumulate.

ACETONE 55

Table 5 . Inoculation for related inoculation

The actual yield of acetone from the pyruvic acid is not equal to that required by the scheme:

From the amount of pyruvic acid added to the flask in this experiment we should expect to obtain 0.180 gm. of acetone per 100 CC., which with the amount formed in the control flask equals 0.205 gm. Roughly one-half of this amount was obtained, and it is clear that from the pyruvic acid some other derivative is obtained,

ACETONE 56

most probably ethyl alcohol. This conclusion is supported by the form of the ethyl alcohol curve in Fig. 1.

ACETONE 57

Capture 5 ACETONE EXISTENCE IN NATURE

It is known that the biosphere issued a large number of volatile organic compounds into the atmosphere such as methane, isoprene, and monoter-pen removed from terrestrial source in large numbers (millions of metric tons) per year globally and has a significant effect on atmospheric chemistry and global climate. Sea is a significant source of light hydrocarbons including ethane, ethylene, propane, and propylene. Mostly, all of that hydrocarbon compounds are produced by phytoplankton.

Figure 7 . Atmosphere of our earth

ACETONE 58

Currently there is an increasing tendency to determine the role of acetone in the chemistry of the atmosphere and determine the natural source of acetone. It is found in the upper troposphere and lower stratosphere in large numbers and may be contributor to the formation of single hydrogen radicals. Some of the acetone found in the atmosphere as a result of photochemical reactions of natural hydrocarbons, direct emissions from biological sources may also be an important source of acetone. Atmospheric oxidation of various biogenic hydrocarbons such as 2methyl-3-butene-2-ol and various monoterpenes also contribute to secondary production of acetone. There are several biological source of acetone which had been known. Among them are well characterized, which includes the enzymatic decarboxylation of acetone acetate in certain bacteria and non-enzymatic decarboxylation of acetone acetate in animals. Bacteria that have been known to produce acetone is a variety of anaerobic bacteria, including clostridium acetobutylicum to produce acetone which is used commercially. Other bacteria are aerobic bactera that produce small amounts of acetone as a metabolic by product, for example, are some strains of Streptococcus cremois and Streptococcus lactis when grown in skim milk. Strains brevibacterium linens producing some volatile carbonyl compounds including acetone when cultured in a solution of casein; formation of acetone will be stimulated by amino acids include aspartic acid, glutamic acid, and leucine. In addition to bacteria that have been mentioned above, bacteria have been isolated from seawater by Nemecek-Marshall and his group from the University of Colorado namely Vibrio sp., is also able to produce acetone as the main product when cultured in media containing L-leucine. Acetone is the main product in the culture-marine Vibrio. Leucine degradation have been detected in a small portion of bacteria, like Pseudomonas aeruginosa using leucine catabolic path similar to the luecine catabolic path in animal tissues, in which

ACETONE 59

leucine and will be converted into acetyl coenzyme into a acetone acetate. In animal tissues, is considered as the amino acid leucine that is ketogenik because acetone acetate will further degrade nonenzymatically to produce acetone. However, that remains a question and still need further proof is whether marine-Vibrio produce acetone in situ. Or whether the acetone fund in sea water with bacterio-plankton, so the net question, whether marine bacteria is a significant source of leucine

ACETONE 60

Capture 6 UTILITY OF ACETONE

Aceton is miscible with water (soluble in all proportions). The water solubility of ketones along a homologous series diminishes rapidly as molecular weight increases. Acetone and 2-butanone is especially valued as solvent because they dissolve not only water, but also a wide variety of organic compounds. These solvents have sufficient low boiling points that they can be easily separated from other less volatile compounds. Acetone, with a dielectric constant of 20.7, is a polar solvent, and is often used as a solvent or co-solvent for nucleophilic substitution reactions Acetone, the simplest ketone, is produced industrially by the dehydrogenation of isopropyl alcohol and, to a smaller extent, by a special fermentation process starting with starch or molasses. Acetone is a very important industrial chemical. It is a valuable solvent in the preparation of lacquers and other coating.

Acetone as a Solvent

ACETONE 61

Figure 8 . Acetone as a solvent

Acetone is the strongest and fastest evaporating solvent around. Excellent for dissolving two-part epoxies before set up, for cleaning fiberglass repair tools and for thinning fiberglass resin. Acetone will easily remove sticky residue on glass and porcelain left by stickers and labels, and will clean lacquer tools well. As acetone is highly volatile, is will not work as a thinner for most oil paints and coatings. Mixing with water dilutes strength and slows evaporation rate. Acetone is used in auto body shops and boatyards, for auto body repair, fiberglass hull repair and other epoxy or fiberglass projects. Acetone is a good solvent that is a component of some paints and varnishes, as well as for most plastics and synthetic fibers. It is ideal for thinning fiberglass resin, cleaning fiberglass tools and dissolving two-part epoxies and superglue before hardening. Acetone can also dissolve many plastics, including those used in Nalgene bottles made of polystyrene, polycarbonate and some types of polypropylene.

ACETONE 62

Many millions of kilograms of acetone are consumed in the production of the solvents methyl isobutyl alcohol and methyl isobutyl ketone. These products arise to give diacetone alcohol. 2(CH 3 ) 2 CO → (CH 3 ) 2 C (OH )CH 2 C (O )CH 3

Acetone is used as a solvent by the pharmaceutical industry and as a denaturize agent in denaturated alcohol. Acetone is also present as an excipient in some pharmaceutical products. Acetone is too strong for use as a coating solvent. It will attack plastics, synthetic fabrics etc. It’s none photochemical reactive. Acetone is a colorless liquid with a mildly pungent odor.

Cleaner and Degreaser

Figure 9 . Acetone as cleaner and degreaser

Acetone is a heavy-duty degreaser, it is useful in the preparation of metal prior to painting; it also thins polyester resins, vinyl and adhesives.

Nail varnish remover

ACETONE 63

Acetone is often the primary component in cleaning agents such as nail polish remover. Acetone is a component of superglue remover and it easily removes residues from glass and porcelain.

Figure 10 . Acetone as Nail polish remover

Nail polish is easily removed with nail polish remover, which is basically an organic solvent but may also include oils, scents and coloring. Nail polish remover packages may include individual felt pads soaked in remover, a bottle of liquid remover that can be used with a cotton ball, and even containers filled with foam and remover that can be used by inserting a finger into the container and twisting until the polish comes off. The base solvent in nail polish remover is usually acetone or ethyl acetate. Acetonitrile has been used, but is more toxic: two cases have been reported of accidental poisoning of young children by acetonitrile-based nail polish remover, one of which was fatal. Acetonitrile has been banned in cosmetics (including nail polish removers) in the European Economic Area since 17 March 2000.

Paint remover ACETONE 64

Figure 11 . Acetone as Paint Remover

It can be used as an artistic agent; when rubbed on the back of a laser print or photocopy placed face-down on another surface and burnished firmly, the toner of the image is allowed to transfer to the destination surface.

Nail extension

Figure 12 . Acetone as Nail extension

If you wish to remove your nail extensions do not pick them off this will cause damage to your natural nails, its best to book an appointment with your nail technician to have them removed or if you wish to do this yourself then you should soak them in acetone. You can keep your extensions for as long as you wish however you

ACETONE 65

do need to have maintenance on them regularly to keep them in the best shape, this will usually need to be done every 2 or 3 weeks.

ACETONE 66

Capture 7 HAZARD AND SAFETY WARNING FOR ACETONE Emergency Overview DANGER! EXTREMELY FLAMMABLE LIQUID AND VAPOR. VAPOR MAY CAUSE FLASH FIRE. HARMFUL IF SWALLOWED OR INHALED. CAUSES IRRITATION TO SKIN, EYES AND RESPIRATORY TRACT. AFFECTS CENTRAL NERVOUS SYSTEM.

Potential Health Effects Inhalations Inhalation of vapors irritates the respiratory tract. May cause coughing, dizziness, dullness, and headache. Higher concentrations can produce central nervous system depression, narcosis, and unconsciousness. Ingestion: Swallowing small amounts is not likely to produce harmful effects. Ingestion of larger amounts may produce abdominal pain, nausea and vomiting. Aspiration into lungs can produce severe lung

ACETONE 67

damage and is a medical emergency. Other symptoms are expected to parallel inhalation. Skin Contact: Irritating due toe defatting action on skin. Causes redness, pain, drying, and cracking of the skin. Eye Contact: Vapors are irritating to the eyes. Splashes may cause severe irritation, with stinging, tearing, redness and pain. Chronic Exposure: Prolonged or repeated skin contact may produce severe irritation

or

dermatitis.

Aggraviation of Pre-existing conditions Use of alcoholic beverages toxic effects. Exposure may increase the toxic protentian of chlorinated hydrocarbons, such as chloroform, trichloroethane

First Aid Measures Inhalation Remove to fresh air. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical attention. Ingestion Aspiration

hazard.

If

swallowed,

vomiting

may

occur

spontaneously, but DO NOT INDUCE. If vomiting occurs, keep head

ACETONE 68

below hips to prevent aspiration into lungs. Never give anything by mouth to an unconscious person. Call a physician immediately. Skin Contact Immediately flush skin with plenty of water for at least 15 minutes. Remove contaminated clothing and shoes. Get medical attention. Wash clothing before reuse. Thoroughly clean shoes before reuse. Eye Contact Immediately flush eyes with plenty of water for at least 15 minutes, lifting upper and lower eyelids occasionally. Get medical attention.

Fire Fighting Measures Fire Flash point : -20oC (-4F) CC Autoignition temperature : 465oC (869 F) Flammable limits in air % by volume : Lel : 2,5; uel : 12,8 Extremely flammable liquid and vapor ! vapor may cause flash fire Explosion Above flash point, vapor-air mixture are explosive within flammable limits noted above. Vapors can flow along surfaces to

ACETONE 69

distant ignition source and flash back. Contact with string oxidizer may cause fire. Sealed containers may rupture when heated. This material may produce a floating fire hazard. Sensitive to static discharge. Fire Extinguishing Media Dry chemical, alcohol foam or carbon dioxide. Water may be ineffective. Water spray may be used to keep fire exposed containers cool, dilute spills to nonflammable mixtures, protect personnel attempting to stop leak and disperse vapors. Special information In the event of a fore, wear full protective clothing, such as breathing apparatus with full face piece operated in the pressure deman or other positive pressure mode.

Handling and Storage Protect against physical damage. Store in a cool, dry wellventilated location, away from any area where the fire hazard may be a cute. Outside or detached stroge s preferred. Separate from incompatibles. Containers should be bonded and grounded for transfers to avoid static sparks. Storage and use areas should be NO SMOKING AREA. Use non-sparking type tools and equipment, including explosion proof ventilation. Containers of this material may be hazardous when empty since they retain product residues (vapors, liquid); observe all warning and precautions listed for the product.

ACETONE 70

Exposure Controls/Personal Protection Ventilation system A system of local and/or general exhaust is recommended to keep employee exposures below the airborne exposure limits. Local exhaust ventilation is generally preferred because it can control the emissions of the contaminant at its source, preventing dispersion of it into the general work area. Personal respirators If the exposure limit is exceeded and engineering controls are not feasible, a half-face organic vapor respirator may be worn up to ten times the exposure limit, or the maximum use concentration specified by the appropriate regulatory agency or respirator supplier, whichever is lowest. A full face-piece organic vapor respirator may be worn up to 50 times the exposure limit, or the maximum use concentration specified by the appropriate regulatory agency or respirator supplier, whichever is lowest. For emergencies or instances where the exposure levels are not known, use a fullface piece positive-pressure, air-supplied respirator. WARNING : airpurifying respirators do not protect workers in oxygen-deficient atmospheres

Skin Protection Wear impervious protective clothing, including boots, gloves, lab coat, apron or coveralls, as appropriate, to prevent skin contact. Eye contact

ACETONE 71

Use chemical safety goggles and/or a full face shield where splashing is possible. Maintain eye wash fountain and quick-drench facilities in work area.

Stability and Reactivity Stability Stable under ordinary conditions of use and storage. Hazardous Decomposition Products: Carbon dioxide and carbon monoxide may form when heated to decomposition. Hazardous Polymerization: Will not occur. Incompatibilities: Concentrated

nitric

and

sulfuric

acid

mixtures,

oxidizing

materials, chloroform, alkalis, chlorine compounds, acids, potassium t-butoxide. Conditions to Avoid: Heat, flames, ignition sources and incompatibles

ACETONE 72

Capture 8 ACETONE IN NEWS

“Ketonuria” Ketonuria is a condition in which abnormally high amounts of ketone bodies (a byproduct of the breakdown of cells) are present in the urine. "Ketonuria" is derived from the Greek words "keton" (acetone) and

"ouron"

(urine).

Related

words

include

"ketogenesis"

(production of ketone bodies), "ketosis" or "ketonemia" (the presence of ketone bodies in the blood) and "ketotic" (adjective describing conditions involving ketone bodies). One of ketonuria cases is DIABETES

Introduction about Diabetes Diabetes, because of its frequency, is probably the most important metabolic disease. It affects every cell in the body and the biochemical processes of carbohydrate, lipid, and protein metabolism. The term diabetes came from Greek words meaning "siphon" or "run through". In medicine, it signifies the

excretion

of an excessive urine volume. Diabetes is characterized by

ACETONE 73

the

polytriad:

polyuria

(excessive

urination),

polydypsia

(excessive thirst), and polyphagia (excessive hunger). There are several types of diabetes indicated by qualifying terms: 1) Diabetes Insipidus - ("lacks flavor") Diabetes

Insipidus

Is

a

relatively

rare

chronic

disease

characterized by the excretion of large quantities of dilute urine but free from sugar and other abnormal constituents. The pituitary gland fails to produce the hormone vasopressin which controls reabsorption of water from the kidneys. 2) Renal Diabetes Renal Diabetes is a benign form of glucosuria due to a lowsugar threshold in the kidneys. Blood glucose levels are normal but the kidney fails to reabsorb the normal amount of glucose back into the blood. Glucose above the threshold is excreted in the urine. 3) Diabetes Mellitus (Latin for sweet) Diabetes Mellitus is the most familiar type of diabetes and most of the time is referred to as "diabetes" without the qualifier. The fundamental cause of diabetes mellitus is a low level or complete lack of the hormone insulin from the pancreas. From a practical standpoint, there are two types of diabetes mellitus: Type I - where the pancreas secretes no insulin, and Type II where there is some insulin available from the pancreas. The

ACETONE 74

types do not necessarily correspond to the ages suggested although most incidences of Type I occur before the age of 20.

Laboratory Diagnosis The laboratory diagnosis of diabetes depends on finding glucose in the urine (glucosuria), however the appearance of glucosuria may result from a variety of causes. In diabetes mellitus, glucose appears in the urine because a hyperglycemia condition exists in the blood. Therefore, the glucose concentration should also be measured in the blood. Glucosuria can occur temporarily from emotional

stress

or

pain,

hyperthyroidism,

alimentary

hyperglycemia, and meningitis. Apparently, the kidney acts as a safety valve against the excessive accumulation of glucose in the blood. If the glucose level becomes too high, then the renal threshold in the kidneys may be exceeded. The renal threshold is a concentration level above which all glucose is not reabsorbed in the blood, but the excess above the threshold concentration remains in the urine. A threshold is analogous to a dam and only when the water level becomes too high, does the water spill over the dam. Many other substances in the blood have their own threshold levels and when the threshold is exceeded, the substance appears in the urine.

Metabolic Disorders from Diabetes Mellitus: Normally, more than 80% of the energy produced by the body is derived from the combustion of carbohydrates. If carbohydrate metabolism is severely limited, the cell begins to oxidize fat

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reserves for energy. In addition, proteins are degraded to amino acids which in turn are converted to glucose. If excessive fat metabolism occurs in conjunction with inadequate carbohydrate metabolism, there are inadequate amounts of oxaloacetic acid with which to react with acetyl CoA from the fatty acid spiral. An excess of acetyl CoA leads to a build up of ketone bodies leading to ketosis and since ketone bodies are also acids, this leads to a condition known as acidosis. Severe acidosis, if not counteracted, can result in coma and death. A diabetic coma is accompanied by labored breathing, a dry parched mouth and tongue, acetone on the breath, a rapid pulse, low blood pressure and often vomiting.The metabolic disorders associated with diabetes mellitus are summarized in the graphic on the below.

Figure 13 . Metabolic Disorders of Uncontrolled DIabetes Mellitus

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Figure 14 . Acetone in human breath

In Another relatively easy laboratory test can be made for ketone bodies in the urine. The condition is known as acetonuria from the acetone present. Ketones bodies result in diabetes mellitus for the very same reasons as given for starvation. Ketone bodies are not normally found in urine nor are they present with the other types of diabetes listed. Ketone bodies are present in various amounts depending upon the severity of the diabetes mellitus. Ketone bodies consist chemically of three substances (betahydroxybutyric acid, acetoacetic acid, and acetone). When ketone bodies are released, they enter the bloodstream, acidify the blood, and are eventually excreted mostly in urine. (One type of ketone body exits via the lungs.) Without treatment, glucose and ketone bodies may build to dangerous levels in the blood. Stress and illness can increase the risk of glucose and ketone buildup. When glucose and ketone bodies build to very high levels, the following conditions then exist: •

Hyperglycemia: too much sugar in the blood.

•

Ketoacidosis: too many ketone bodies in the blood.

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•

Ketonuria: accumulation of ketone bodies in the urine. When ketone is excreted, sodium is excreted along with it. Ironically, ketonuria is a desired effect of a special "ketogenic

diet" used to prevent or reduce the number of seizures in people with epilepsy (seizure disorders). Some physicians use this diet when conventional medications fail to control seizures or when the side effects of medications become intolerable. The ketogenic diet, which is high in fats and low in protein and carbohydrates, mimics starvation and raises the level of ketone bodies in the blood. The ketone bodies can prevent or decrease the incidence of many types of seizures, including myoclonic (spastic) and atonic (drop) seizures. They may also limit other types of seizures, including so-called staring spells. Why ketone bodies may inhibit such seizures is not known. The ketogenic diet is very strict and must be closely managed under a physician's supervision. Only a limited number of medical centers are equipped and trained to prescribe it.

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REFERENCES

Rusman, S.Si, M.Si., dkk. 2009. Organic Chemistry Module. Bogor : SMAKBo Denningston, K. J., Topping Joseph J. 2004. General Organic and Biochemistry. Fifth edition. USA : McGraw-Hill Wilbraham, Antony C., dkk. 1992. Pengantar Ke Kimia Organik Hayati. Bandung : Penerbit ITB Geissman, T. A. 1962. Principles of Organic Chemistry. USA : W. H. Freeman and Company Busser, Herman. 1960. Pengantar Ke Kimia Organik. Bandung : Tjikapundung Fessenden & Fessenden. 1986. Kimia Organik. Edisi ke-3 jilid 2. Jakarta : Penerbit Erlangga http://www.jtbaker.com/msds/englishhtml/a0446.htm http://www.unclespot.com/disclaimer.html

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http://dow-answer.custhelp.com/cgibin/dow_answer.cfg/php/enduser/std_adp.php? p_faqid=3810&p_created=1124387309&p_topview=1 http://smallstuff-digest.com/cgi-bin/archives.cgi? category=cat_safety http://www.medterms.com/script/main/art.asp?articlekey=12478 http://www.elmhurst.edu/~chm/vchembook/624diabetes.html http://www.ncbi.nlm.nih.gov/pubmed/9235526 http://en.wikipedia.org/wiki/Diabetes_mellitus http://en.wikipedia.org/wiki/acetone http://www.ncbi.nlm.nih.gov/pmc/articles/PMC371996/ http://www.jbc.org/content/261/9/3952.full.pdf http://wiki.answers.com/Q/What_is_acetone_used_for http://images.google.co.id/imglanding?q=metabolism%20human %20acetone%20diabetes %20melitus&imgurl=http://dentalmumbai.com/images/badbreathhalitosis.jpg&imgrefurl=http://dentalmumbai.com/bad_breath. htm&usg=__NCvPITD0LDWgWLyz5UfagGlsag=&h=200&w=191&sz=14&hl=id&um=1&itbs=1 &tbnid=ayrgyfjfVU0ncM:&tbnh=104&tbnw=99&prev=/image s%3Fq%3Dmetabolism%2Bhuman%2Bacetone%2Bdiabetes %2Bmelitus%26um%3D1%26hl%3Did%26sa%3DX%26tbs %3Disch:1&um=1&sa=X&tbs=isch:1&start=13#tbnid=ayrgyf jfVU0ncM&start=17

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http://images.google.co.id/imglanding?q=metabolism%20human %20acetone%20diabetes %20melitus&imgurl=http://www.liveingoodhealth.info/wpcontent/uploads/cc/Diabetes_mellitus76.jpg&imgrefurl=http:// www.liveingoodhealth.info/article/the-difference-betweenethanol-andtrifluoroethanol/&usg=__GrNp6dyMdBsg6OrDa_d0oISrx8Y=&h =208&w=261&sz=59&hl=id&um=1&itbs=1&tbnid=j4Sm9wb zIXwP_M:&tbnh=89&tbnw=112&prev=/images%3Fq %3Dmetabolism%2Bhuman%2Bacetone%2Bdiabetes %2Bmelitus%26um%3D1%26hl%3Did%26sa%3DX%26tbs %3Disch:1&um=1&sa=X&tbs=isch:1&start=15#tbnid=j4Sm9 wbzIXwP_M&start=19 http://www.jbc.org/content/64/1/41.full.pdf

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