A.

TITTLE OF EXPPERIMENT
Synthetic of Cyclohexanone
B. THE OBJECTIVE OF EXPERIMENT
At the end of the experiment student are expected
1. Skilled in the secondary alcohol oxidation cyclic
2. Can understant the cyclic secondary alcohol oxidation reaction
C. REVIEW OF LITERATURE
Functional groups are common and specific arrangements of atoms that
impart predictable reactivity and properties to a molecule. Even though there are
millions of organic compounds, you may be relieved to know that we can readily
understand much about whole families of compounds simply by learning about
the properties of the common functional groups. For example, all alcohols contain
an OH (hydroxyl) functional group attached to a saturated carbon bearing nothing
else but carbon or hydrogen. Alcohols as simple as ethanol in alcoholic beverages
and as complex as ethinyl estradiol in birth control pills have this structural unit
in common. All aldehydes have a C(O) (carbonyl) group with one bond to a
hydrogen and the other to one or more carbons, such asin benzaldehyde (from
almonds). All ketones include a carbonyl group bonded by its carbon to one or
more other carbons on each side, as in the natural oil menthone, found in
geraniums and spearmint. Hydrocarbons are compounds that contain only carbon
and hydrogen atoms. The hydrocarbons family also incildes alkanes, alkenes,
alkynes, and aromatic compounds. compounds such as the alkanes, whose
molecules contain only single bonds, are referred to as saturated compounds
because these compounds contain the maximum number of hydrogen atoms that
the carbon compound can possess. Compounds with multiple bonds, such as
alkenes, alkynes, and aromatic hydrocarbons, are called unsaturated compounds
because they possess fewer than the maximum number of hydrogen atoms, and
they are capable of reacting with hydrogen under the proper conditions
(Solomons, 2011: 53-54).
Alkenes, sometimes called olefi ns, are hydrocarbons that contain a
carbon–carbon double bond, CPC, and alkynes are hydro carbons that contain a
carbon–carbon triple bond, CqC. Alkenes occur abundantly in nature, but alkynes
are much less common. Ethylene, for instance, is a plant hormone that induces
ripening in fruit, and pinene is the major component of turpentine. ldehydes and
ketones undergo a nucleophilic addition reaction with water to yield the
corresponding carbonyl hydrates, sometimes called geminal (gem) diols from the
Latin geminus, meaning “twin.” The reaction is reversible, and the gem diol
product can eliminate water to regenerate a ketone or aldehyde. The position of
the equilibrium between hydrate and aldehyde/ketone depends on the structure of
the carbonyl compound. The equilibrium strongly favors the carbonyl compound
in most cases, with the hydrate favored only for a few simple aldehydes. An
aqueous solution of acetone, for instance, consists of about 0.1% hydrate and
99.9% ketone, whereas an aqueous solution of formaldehyde (CH 2O) consists of
99.9% hydrate and 0.1% aldehyde. The nucleophilic addition of water to
aldehydes and ketones is slow in pure water but is catalyzed by both base and
acid. The base-catalyzed addition reaction takes place by the mechanism shown
previously, with the negatively charged hydroxide ion as the nucleophile and in
the water catalyzed is equation as the proton source in the final step (Murry, 2011:
78 and 305).
Ketones contain a polar carbonyl group (carbon–oxygen double bond),
which has a partially negative oxygen atom and a partially positive carbon atom.
Because the electronegative oxygen atom forms hydrogen bonds with water
molecules, aldehydes and ketones with one to four carbons are very soluble.
However, aldehydes and ketones with five or more carbon atoms are not soluble
because longer hydrocarbon chains, which are nonpolar, diminish the solubility
effect of the polar carbonyl group. Earlier in this chapter, we saw that primary
alcohols can oxidize to aldehydes. However, aldehydes are easily oxidized further
to carboxylic acids. In contrast, ketones produced by the oxidation of secondary
alcohols do not with because ketones is the other undergo further oxidation
(Timberlake, 2012: 430-431).
Perhaps the most valuable reaction of alcohols is their oxidation to yield
carbonyl compounds—the opposite of the reduction of carbonyl compounds to
give alcohols. Primary alcohols yield aldehydes or carboxylic acids, and
secondary alcohols yield ketones, but tertiary alcohols don’t normally react with
oxidizing agents. Primary alcohols are oxidized either to aldehydes or to
carboxylic acids, depending on the reagent used. Older methods were often based
on Cr(VI) reagents, such as CrO3 or Na2Cr2O7 , but the most common current
choice for preparing an aldehyde from a primary alcohol in the laboratory is to use
a periodinane, which contains an iodine atom in the ?5 oxidation state. This
reagen Secondary alcohols are oxidized to produce ketones. For a sensitive or
costly alcohol, a periodinane is often used. For a large-scale oxidation, however,
an inexpensive reagent such as CrO3 or Na2 Cr2O7 in aqueous acetic acidis more
economicalt is too expensive for large scale use in industry, however (Murry,
2011: 271-272).
The reaction is an elimination and is favored at higher temperatures. The
most commonly used acids in the laboratory are Brønsted acids—proton donors
such as sulfuric acid and phosphoric acid. Lewis acids such as alumina ( Al 2O3)
are often used in industrial, gas-phase dehydrations. Organic synthesis is the
process of building organic molecules from simpler precursors. Syntheses of
organic compounds are carried out for many reasons. Chemists who develop new
drugs carry out organic syntheses in order to discover molecules with structural
attributes that enhance certain medicinal effects or reduce undesired side effects.
Crixivan, whose structure is shown below, was designed by small-scale synthesis
in a research laboratory and then quickly moved to large-scale synthesis after its
approval as a drug. In other situations, organic synthesis may be needed to test a
hypothesis about a reaction mechanism or about how a certain organism
metabolizes a compound (Solomons, 2011: 297 and 317).
The initial product of conjugate addition is a resonance-stabilized enolate
ion, which typically undergoes protonation on the carbon to give a saturated
aldehyde or ketone product. Conjugate addition occurs because the
electronegative oxygen atom of the unsaturated carbonyl compound withdraws
electrons from th carbon thereby making it more electron-poor and more
electrophilic than a typicalalkene C=C bond. Aldehydes and ketones are among
the most important of all compounds, both in the chemical industry and in
biological chemistry. ketones are usually protected by converting them into
acetals. Acetals, like other ethers, are stable to bases, reducing agents, and various
nucleophiles, but they can be cleaved by treatment with acid. Thus, you can
selectively reduce the ester group in a keto ester by converting the keto group into
an acetal, reducing the ester with LiAlH 4 in ether, and removing the acetal
protecting group by treatment with aqueous acid. Aldehydes are easily oxidized to
yield carboxylic acids, RCHO n RCO2H, but ketones are unreactive toward
oxidation. This reactivity difference is a consequence of structure: aldehydes have
a CHO proton that can be removed during oxidation, but ketones do not (Murry,
2011: 299, 308-312).
The general synthetic strategy employed to prepare the chalcone
derivatives (3a-h) was based on Claisen Schmidt condensation, which was
reported previously. The structures of all the 8 chalcone derivatives (3a-h)
synthesized in this research were established on the basis of IR, 1 H-NMR, and 13
C-NMR spectral data. The synthesized chalcones derivatives (3a-h) were
submitted to the Michael addition reaction. A series of 8 chalcone-1,5-diketones
(5a-h) was prepared by base catalyzed addition of cyclohexanone to chalcones
(3a-h) under solvent-free phase transfer catalyst condition. It is observed that the
Michael-type addition of cyclohexanone to chalcone derivatives (3a-h) can be
easily carried out and gives product 5 in satisfactory yield. However, the position
of substituents affects the reaction yields. While the high yields were achieved in
m- and p-substituted 5a, c, d, g, h, the low yields were observed to o-substituted
5b, e, and f as seen in Table 1. It is assumed that the low yields could be attributed
to the steric hindrance of o-substituents (Ceylan, 2008: 55-56).
The selectivity is mainly to cyclohexanol in the 325-400 K temperature
range for all catalysts in the hydrogenation reaction of cyclohexanone. It was
reported for cyclohexene hydrogenation on Pt(111) that only cyclohexane was
formed in the reaction at the 300–400 K temperature range. Alloyed Sn does not
appreciably modify the Pt(111) selectivity. It has an effect on the reaction rate
where, at low temperature, increasing the amount of tin increases the reaction rate.
This increase in rate is attributed to a favorable modification of the nature of the
active metallic sites and reaction orders are comparable to those observed for
liquid phase hydrogenation of cyclohexanone over Pt/SiO2, the order with respect
to the hydrogenation reaction 1,4 cyclohaxananion acetophenon (Olivas, 2004:
285-292).
D. APPARATUS AND MATERIAL
1. Apparatus
a. Beaker 1000 mL 1 unit
b. Beaker 250 mL 1 unit
c. Beaker 100 mL 1 unit
d. Measuring Glass 100 mL 1 unit
e. Measuring Glass 10 mL 1 unit
f. Separation Funnel 500 mL 1 unit
g. Destillation Flask 500 mL 1 unit
h. Erlenmeyer 250 mL 1 unit
i. Thermometer 110oC 1 unit
j. Drop Pipette 1 unit
k. Stir rod 2 units
l. Cooling bar 1 unit
m. Condensor 1 unit
n. Funnel 1 unit
o. Spray bottle 1 unit
p. Spatula 1 unit
q. Cork stopper 1 unit
r. Smooth rag 1 unit
s. Coarse rag 1 unit
t. Stative 1 unit
u. Clamp 1 unit
v. Hot plate 1 unit
2. Chemicals
a. Potassium bichromate (K2Cr2O7)
 b. Sulfuric acid concentrated (ASAM SULFAT)
c. Aquadest (H2O)
d. Ice (H2O)
e. Cyclohexanol (C6H11OH)
f. Magnecium oxide anhydrate (MgO)
g. Salt of sodium chloride (NaCl)
h. Aluminium foil (Al2O3)
i. Petroleum ether
j. Filter paper
E. WORK PROCEDURES
1. Diluted 20.5 gr in 100 ml of water in beaker glass 250 ml
2. Added with carefully 10 ml of sulfuric acid concentrated.
3. Added Cyclohexanol in round flask and enter some of boiling stone.
4. Into a round flask add little by little solution of potassium bikromate, observe
and temperature will increase.
5. If temperature start 55℃ cooled with water and save the temperature between
50-60 ℃. Then cooled in air may be half hour.
6. Do distillation the solution and add before 100 ml of water until get destilate
50 mL.
7. Saturated the solution with NaCl and separate with separate funnel.
8. Layer extracted with 12 ml of petroleum ether. Combined this extract with
cyclohexanon layer.
9. Dried with MgO anhydrate, then filter the solution into measuring glass.
F. OBSERVATION RESULT
No. Activity Result
1. Weight of K2Cr2O7 20,6 gr of K2Cr2O7
2. Dissolve with 100 ml of H2O 100 ml of K2Cr2O7 solution
changed into red solution
3. add asam sulfat The mixture was changed into
red brown solution
4.
Add on destillation flask The mixture was red brown
 5. Destillated mixture solution Temperature is 55oC and the
color is black
6. K2Cr2O7 + concentrated asam sulfat Destillated solution was
+ cyclohexanol +100 mL H2O and obtained and the color was
do destilation of the solution changed from red brown to
yellow
7. Add NaCl 13 gram into destillated The mixture solution still
mixture solution yellow
8. Add petroleum eter -There was 3 layers
-The up layer was yellow
-The second layer was
transparant
-The bottom layers was yellow

G. DATA ANALYSIS
If known : Mass of Potassium dichromate = 20,5 gram
Mass of cyclohexanol = 10 gram
Mr K2Cr2O7 =294 gram/mol
Mr C6H11OH =100 gram/mol
` Density of K2Cr2O7 = 0,95gram/ml
Volume of C6H11OH = 10 ml
Volume of K2Cr2O7 = 10 mL
Asked : % rendemen = .... ?
gram 10 gram
¿ = =0,1 mol
Solution : n C6H11OH Mr gram
10 0
mol
gram 20,5 gram
¿ = =0,06 mol
n K2Cr2O7 Mr gram
294
mol

C6H11OH + K2Cr2O7 C6H10 + H2O

Initial : 0,1mol 0,06 mol - -
React : 0,06mol 0,06 mol 0,06 mol 0,06 mol
Eq : 0,04mol - 0,06 mol 0,06 mol
Mass of C6H10 (theory) = mol C6H10 x Mr C6H10
= 0,06Mol x 112 gram/Mol
= 6,72 gram
Mass of C6H10 (practicum) = ρ C6H10 X Volume C6H10
= 0,949 gram/ml x 4ml
= 3,796 gram
massofpractic
% Rendement = ×100 %
massoftheory
3,796 gram
= × 100 %
6,72 gram
= 0,564 X 100 %
= 56,4 %
H. DISCUSSION
Sikloheksanon merupakan senyawa organik yang dapat dibuat melalui
oksidasi sikloheksanol menjadi sikloheksanon. Pada percobaan ini pembuatan
sikloheksanon dilakukan dengan mengoksidasi alkohol sekunder siklik menjadi
keton siklik. Kondisi optimum reaksi reduksi dan oksidasi ini adalah pada
temperatur 55-600C (Solomon, 2011: 318).
Tujuan dari percobaan ini adalah agar mahasiswa terampil dalam
melakukan oksidasi alkohol sekunder siklik dan dapat memahami reaksi oksidasi
alkohol sekunder siklik. Oksidasi sikloheksanol menjadi sikloheksanon
menggunakan kalium bikromat sebagai zat oksidator dalam suasana asam. Saat
kalium bikromat dilarutkan dengan air, maka kalium bikromat akan terurai
menjadi ion-ion kalium bikromat yang akan bereaksi dengan ion H+ dan
menghasilkan larutan berwarna jingga. Pelarutan ini dilakukan dengan pemanasan
agar kalium bikromat dapat larut dengan cepat dan sempurna. Larutan kalium
bikromat kemudian ditambahkan dengan asam sulfat menghasilkan larutan
berwarna merah dan suhu larutan menjadi panas sehingga reaksi ini bersifat
eksotermik (perpindahan energi panas dari larutan ke lingkungan). Setelah
penambahan asam sulfat, larutan didiamkan hingga suhunya mencapai 300 C. Hal
ini bertujuan agar pada saat penambahan sikloheksanol tidak menghasilkan panas
yang terlalu tinggi. Asam sulfat berfungsi untuk mempercepat reaksi tetapi tidak
ikut bereaksi, asam sulfat tidak hanya sebagai katalis namun dalam reaksi ini asam
sulfat bereaksi dengan sikolheksanol yang merupakan alkohol dan pemberi
suasana asam. Larutan kemudian ditambahkan sikloheksanol. Sikloheksanol
berfungsi sebagai bahan baku dalam pembuatan sikloheksanon yang akan
mengalami oksidasi. Pencampuran antara sikloheksanol dan larutan kalium
bikromat dilakukan dengan mengocok labu erlenmeyer agar campuran tersebut
bercampur secara sempurna dan menghasilkan larutan berwarna hitam dengan
suhu larutan yang tinggi (panas). Kenaikan suhu ini terjadi karena reaksi oksidasi
sikloheksanol menjadi keton merupakan reaksi eksoterm (perpindahan energi
panas dari sistem ke lingkungan).
Selanjutnya campuran tersebut ditutup dalam labu destilasi bertutup
aluminium foil agar tidak meletup dan agar suhunya tidak melebihi 50 ℃. Jika
suhunya kurang dari 50 ℃ maka campuran didinginkan dengan air es, jika
suhunya melebih 60 ℃ maka sikloheksanon akan rusak karna alkohol hanya dapat
bereaksi pada suhu 55-60 ℃. Jika suhu campuran telah konstan, maka campuran
didestilasi yang berfungsi untuk memisahkan larutan ke dalam masing-masing
komponennya, dalam hal ini untuk memisahkan sikloheksanon dari komponen-
komponen seperti senyawa-senyawa lainnya agar diperoleh sikloheksanon yang
murni.
Adapun prinsip dasar destilasi yaitu pemisahan suatu larutan berdasakan
perbedaan titik didihnya, dan prinsip kerjanya ialah pemanasan, penguapan, dan
pengembunan. Tujuan dari destilasi ialah untuk memurnikan sikloheksanon yang
mengandung zat pengotor yang berasal dari hasil reaksi oksidasi. Setelah
diperoleh destilat sebanyak 4 mL, 4 mL tersebut dimasukkan kedalam corong
pisah, dimana corong pisa bertujuan untuk ekstraksi. Ekstraksi adalah suatu proses
pemisahan campuran berdasarkan perbedaan sifat kepolaran dan perbedaan massa
jenis antara dua senyawa. Campuran diekstraksi agar memperoleh senyawa
sikloheksanon. Ekstraksi pelarut menyebabkan campuran memisah. Hal ini
disebabkan karena sikloheksanon bersifat semipolar dan cenderung nonpolar
sedangkan air bersifat polar. Lapisan sikloheksanon berada pada bagian atas
karena massa jenis sikloheksanon lebih kecil daripada air. Massa jenis
sikloheksanon adalah 0,95 gr/mL sedangkan massa jenis air adalah 1 gr/mL.
Selanjutnya lapisan air diekstraksi dengan petroleum eter kemudian
dimasukkan ke dalam corong pisah sehingga terbentuk tiga lapisan. Lapisan atas
berwarna kuning, lapisan tengah bening dan lapisan bawah berwarna kuning,
berwarna kuning menunjukkan skloheksanon sedangkan bening mengandung
petroleum eter dan air. Hal ini dapat terjadi karena suhu sebelum didestilasi
mengalami penurunan, sehingga pembentukan sikloheksanon yang tidak
sempurna dan pada saat pemisahan menggunakan corong pisah terdapat sedikit
kesalahan karena kurangnya konsep dan keterbatasan waktu yang dimiliki
sehingga praktikan tidak dapat melanjutkan percobaan. Petroleum eter dan air
dapat bercampur karena sifat kepolaran yang sama. Petroleum eter berfungsi
untuk memisahkan sikloheksanon dengan air. Akan tetapi, hasil percobaan tidak
sesuai dengan teori. Berdasarkan teori dari Timberlake (2012: 430-431), hasil
yang terbentuk ada dua lapisan yaitu pada lapisan atas adalah sikloheksanon dan
lapisan bawah adalah air dan petroleum eter.
Campuran kemudian dijenuhkan dengan menggunakan garam NaCl
sedikit demi sedikit sehingga tidak lewat jenuh, adapun fungsi penjenuhan dengan
NaCl yaitu untuk memisahkan yang masih bercampur dengan sikloheksanon, agar
sikloheksanon yang terbentuk keluar dari lapisan air. Selanjutnya, lapisan air
diekstraksi menggunakan petroleum eter yang berfungsi untuk mengikat
sikloheksanon yang masih terikat dalam air. Setelah itu, lapisan air dibuang dan
lapisan sikloheksanon dicampur dengan lapisan sikloheksanon yang telah
dijenuhkan kemudian ditambahkan magnesium sulfat anhidrat yang berfungsi
untuk mengikat sisa-sisa air. Adapun reaksinya yaitu:
MgSO4 + xH2O → MgSO4 + xH2O
Kemudian untuk memperoleh sikloheksanon yang murni maka campuran
disaring dengan menggunakan kertas saring untuk memisahkan sikloheksanon
dengan MgO dengan hasil yang diperoleh berwarna putih. Percobaan ini
menghasilkan sikloheksanon yang sebanyak 4 ml dan rendaman hasilnya yaitu
56,4% dimana pada 100% larutan terdapat 56,4,9% sikloheksanon. Adapun
reaksinya:

K2Cr2O7 + 2H2O H2Cr2O7 + 2KOH

H2Cr2O7 + 2KOH + H2SO4 2CrO3 + K2SO4 + 3H2O

H OH O

[O] + H2 O
H2Cr2O7

OH
O OH O
OH OH
OH-
+ O=Cr + O=Cr
H
OH OH

O
OH O
OH
O Cr
O
O Cr O
OH OH-
H OH + Cr OH + H2O
OH

OH O

6 + K2Cr2O7 + 4H2SO4 6 + Cr2(SO4)3 + 7 H2O + H2SO4

I. CONCLUSION AND SUGGESTION

1. Conclusion
a. oxidation of secondary alcohol cyclic do with react cyclohexanol with
k2cr2o7 and asam sulfat produce cyclohexanone (ketone compound).
b. Oxdation can occur because there is a oxidation agent of Cr 2O7 in acidic
state from asam sulfat and the preparation of cyclohexanone we do
purification technique like, distillation, separate funnel unsaturated and
dry.
2. Suggestion
 For apprrentice should be diciplined, should be on time to come in
laboratory, dont be noise when practicum occur and always coordination with
their friends.

BIBLIOGRAPHY

Ceylan, Musatafa and Hayreddin Gezegen. 2008. Preparation of 1,5 Diketones by

Addition of Cyclohexanone to Chalcones under Solvent-free Phase
Transfer Catalyst Condition. Turk J Chem. 32(1): 55-61

Murry, John Mc. 2011. Fundamental of Organic Chemistry. USA: Changnge

Learning, PP: 78-312

Olivas, A., Dmitri, I, Jerdev., Bruce E. Koel. 2004. Hydrogentaion of

Cyclohexanone on PT-Sn Surface Alloys. Journal Catalysis. 222(1): 285-
292

Solomons, T, W, Graham and Craig B Fryhile. 2011. Organic Chemstry Tenth

Edition. USA: Petra Recter, PP: 53-317

Timbarlake. 2012. Chemistry Seventh Edition. USA: Prantice Hall, PP: 430-431
 ANSWER OF QUESTION

1. How to explain that reaction above is oxidation reaction?

Answer:
From the reaction can see that secondary alcohol cyclic add oxygen and
produce compound that bond with oxygen this reaction i called oxidation.
2. Why temprature can’t more than 600C?
Answer:
It is because the optimum reaction is between 50-60 0C. If more than it not
cyclohexanone that will form.
3. From procedur in top, explain three separation technique in organic
compounds
Answer:
a. Distillation is purification/ separation technique of liquid compound based
on different of boiling point
 b. Separated funnel is separate technique of component that not homogency
because of different polarand density
c. Filter separate technique based oin the size of compound that want
separate

RATIFICATION PAGE

Complete report of advance basic chemistry experiment entitled

“Synthetic of Cyclohexanone“, that arranged by :
name : Radiatul Awalia Amir
id : 1713441007
class : ICP of Chemistry Education
group : III (Three)
after checked by ssistant and assistant coordinator, so this report was accepted.

Makassar, May 2018

Coordinator assistant Assistant

Imranah, S.Pd A. Cici Kurnia Abidin, S.Si

Known by,
Lecturer of Responsibility

Hardin, S.Si., S.Pd., M.Pd

NIP. 19870807 2015 04 1 004