VALIDATION SHEETSTUDENTS,

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

PREFACEAssalamualaikum 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

ACETONE 2

TABLE OF CONTENT

VALIDATION SHEET......................................................................................................1

PREFACE.......................................................................................................................2

TABLE OF CONTENT.....................................................................................................3

LIST OF TABLE.............................................................................................................. 6

TABLE OF FIGURE.........................................................................................................7

LIST OF ATTACHMENT..................................................................................................8

INTRODUCTION............................................................................................................9

PHYSICAL PROPERTIES OF ACETONE..........................................................................12

CHEMICAL PROPERTIES OF ACETONE........................................................................16

1) Basic Properties of Ketones............................................................................16

2) Addition to Carbonyl Group...........................................................................18

3) Addition of Hydrogen Cyanide.......................................................................24

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

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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

Industry Scale.........................................................................................................39

Laboratory Scale.....................................................................................................43

Biochemistry scale..................................................................................................46

ACETONE EXISTENCE IN NATURE...............................................................................56

UTILITY OF ACETONE..................................................................................................59

Acetone as a Solvent..............................................................................................59

Cleaner and Degreaser...........................................................................................61

Nail varnish remover..............................................................................................61

Paint remover.........................................................................................................62

Nail extension.........................................................................................................63

HAZARD AND SAFETY WARNING FOR ACETONE........................................................65

Emergency Overview..............................................................................................65

Potential Health Effects..........................................................................................65

First Aid Measures..................................................................................................66

Fire Fighting Measures...........................................................................................67

Handling and Storage.............................................................................................68

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Exposure Controls/Personal Protection.................................................................68

Stability and Reactivity...........................................................................................69

ACETONE IN NEWS.....................................................................................................71

Introduction about Diabetes..................................................................................71

Laboratory Diagnosis..............................................................................................73

Metabolic Disorders from Diabetes Mellitus:.........................................................73

REFERENCES...............................................................................................................77

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LIST OF TABLE

Table 1 . Physical Properties of Acetone....................................................................15

Table 2 . Physical properties of isopropyl alcohol......................................................42

Table 3 . Inoculation of the bacteria..........................................................................50

Table 4 . Result of the inoculation.............................................................................50

Table 5 . Inoculation for related inoculation..............................................................54

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TABLE OF FIGUREFigure 1 . Acetone........................................................................................................9

Figure 2 . Condense structure of acetone..................................................................12

Figure 3 . Structure and Dimension for Acetone Molecule........................................12

Figure 4 . Ball-and-stick Model for Acetone Molecule...............................................12

Figure 5 . Space-Filling Model for Acetone Molecule.................................................13

Figure 6 . Curve relating the two glycerol. to one flask, continuos curves, puryvic acid

was added at the commencement of and curve during fermentation........53

Figure 8 . Atmosphere of our earth............................................................................56

Figure 9 . Acetone as a solvent..................................................................................60

Figure 10 . Acetone as cleaner and degreaser...........................................................61

Figure 11 . Acetone as Nail polish remover................................................................62

Figure 12 . Acetone as Paint Remover.......................................................................63

Figure 13 . Acetone as Nail extension........................................................................63

Figure 14 . Metabolic Disorders of Uncontrolled DIabetes Mellitus..........................74

Figure 15 . Acetone in human breath........................................................................74

ACETONE 7

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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INTRODUCTION

Figure 1 . Acetone

Acetone, also known as propanone, dimethyl ketone, 2-propanone, 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 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

ACETONE 9

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.

ACETONE 11

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)

ACETONE 13

Density 0.7925 g/cm3

Melting point −94.9 °C, 178 K, -139 °F

Boiling point 56.53 °C, 330 K, 134 °F

Solubility in water miscible

Acidity (pKa) 24.2

Refractive index (nD) 1.35900 (20 °C)

Viscosity 0.3075 cP

STRUCTURE

Molecular shape trigonal planar at C=O

Dipole moment 2.91 DHAZARDS

MSDS External MSDS

EU classification F

XiR-phrases R11, R36, R66, R67

S-phrases (S2), S9, S16, S26

NFPA 704310

Flash point −17 °CAutoignitiontemperature

465 °C

Explosive limits 4.0–57.0

Threshold Limit Value 500 ppm (TWA), 750 ppm (STEL)

LD50 >2000 mg/kg, oral (rat)

SUPPLEMENTARY DATA PAGE

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Structure and Properties n, εr, etc.

Thermodynamicdata

Phase behaviourSolid, liquid, gas

Spectral data UV, IR, NMR, MSTable 1 . Physical Properties of Acetone

ACETONE 15

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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

ACETONE 16

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.

ACETONE 17

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

ACETONE 18

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.

ACETONE 19

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:

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

ACETONE 20

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 carbonyl compound has carbocation character. The electron-

deficient carbon is 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

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:

ACETONE 21

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

Addition is less favorable when groups are present that donate

electrons by resonance to the carbonyl carbon

ACETONE 22

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:

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

ACETONE 23

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 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:

ACETONE 24

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 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 low-molecular weight

ketones is another characteristics carbonyl-addition reaction

ACETONE 25

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

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

ACETONE

Na-hydroxypropanesulfonate

26

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 separated by filtration and washed with ether to remove

contaminating substance. Treatment of the 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

ACETONE 27

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,

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

ACETONE 28

weak acid such as ammonium chloride), which is added in a separates step to the

reaction mixture.

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.

ACETONE 29

Hydride ion from LiAlH4 or NaBH4 is the nucleophile, and the proton is delivered

from acid added in a separate step (in the case of LiAlH4 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 isolated and

identified by its appearance and melting point; both bromoform and chloroform are

liquids at ordinary temperature.

ACETONE 31

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

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

ACETONE 32

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

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

ACETONE 33

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

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

ACETONE 34

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.

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.

ACETONE 35

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 carbon-carbon bond formation.

11) Test for aldehydes and ketones and differentiation between them

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

ACETONE 36

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 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 SO2.

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

ACETONE 37

yellow to pink or reddish violet. Ketones, in which the addition of bisulfite proceed

to a smaller extent, do not restore the color.

ACETONE 38

Capture 4

CHEMICAL PREPARATION OF ACETONE

Industry ScaleThere 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 :

Results from the oxidation of the first reactor contain Cumene hydroperoxide

9-12%, 15-20% in the second reactor, 24-29% in the 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

ACETONE 39

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:

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 can be run well using a catalyst such as that used in

isopropyl alcohol dehydrogenation process.

ACETONE 40

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:

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 85-90%.

Hot gas out of the reactor consisting of isopropyl alcohol, acetone, and

hydrogen is passed scrubber, to separate the 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:

ACETONE 41

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, 2-propanol, 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

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:

a. Acetone is heated under reflux with successive quantities of potassium

permanganate until the violet colour is persisting. It’s then dried with

ACETONE 42

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 (-

80C). The crystals are filtered off and quickly transferred to dry distilling flask

connected to an efficient conceder and to a receiver cooled in ice. Upon gentle

warming, the acetone distills rapidly.

Laboratory ScaleAcetone 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

ACETONE 43

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

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

ACETONE 44

REACTION OF CaCO3

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

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

ACETONE

CH3.COO

CH3.COO

CH3

CH3

45

Biochemistry ScaleThis 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 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).

ACETONE

CH3C

CH3

CH3

CH3

CH3

46

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

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

ACETONE 47

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 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 H20 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 per cent of CuSO 4

ACETONE 48

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 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

ACETONE 49

converted with equal rapidity into some other characteristic product, most probably

ethyl alcohol.

Table 3 . Inoculation of the bacteria

Table 4 . Result of the inoculation

ACETONE 50

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 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.

ACETONE 51

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 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 52

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 53

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 54

most probably ethyl alcohol. This conclusion is supported by the form of the ethyl

alcohol curve in Fig. 1.

ACETONE 55

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

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

ACETONE 56

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 2-methyl-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 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 non-enzymatically 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

ACETONE 57

with bacterio-plankton, so the net question, whether marine bacteria is a significant source of leucine

ACETONE 58

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 59

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.

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.

ACETONE 60

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 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.

ACETONE 61

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 62

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

ACETONE 63

you 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 64

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 damage and is a medical emergency. Other

symptoms are expected to parallel inhalation.

ACETONE 65

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 below hips to prevent aspiration into

lungs. Never give anything by mouth to an unconscious person. Call a physician

immediately.

ACETONE 66

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 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.

ACETONE 67

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 well-ventilated 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.

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

ACETONE 68

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 full-face piece positive-pressure, air-supplied respirator. WARNING : air-purifying

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

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:

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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

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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 the polytriad:

polyuria (excessive urination), polydypsia (excessive thirst), and polyphagia

(excessive hunger).

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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 low-sugar 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 types do not necessarily correspond to the ages

suggested although most incidences of Type I occur before the age of 20.

Laboratory Diagnosis

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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 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

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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

Figure 14 . Acetone in human breath

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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 (beta-hydroxybutyric

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.

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

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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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