Post on 20-Feb-2018
7/24/2019 BBR 26703 ana,ena,keton.pdf
1/69
Bab 2:MENULIS STRUKTUR KIMIA ORGANIK
Hatijah BasriUniv.Tun Hussein Onn Malaysia
7/24/2019 BBR 26703 ana,ena,keton.pdf
2/69
Objektif
Mengenalpasti jeniskumpulan berfungsi sebatian
Melukis struktur kimiasebatian organik mengikut
kumpulan berfungsi
7/24/2019 BBR 26703 ana,ena,keton.pdf
3/69
Overview Struktur Kimia Organik
Kumpulan-kumpulan berfungsi dalam kimia organik:
Alkana (alkane) dan Alkil halida (alkyl halide)
Alkena (alkene) dan Alkuna (alkyne)
Alkohol dan eter
Sebatian karbonil
-Aldehid dan keton
- Asid Karboksilik dan ester
7/24/2019 BBR 26703 ana,ena,keton.pdf
4/69
Sebatian organik (Sebatian karbon)
Definisi:Kimia Organik ialah kajian kimia sebatianyang mengandungi karbondan hidrogen.
Apakah keistimewaan karbon? Hampir 90 % bahanyang digunakan/berada oleh/dalam badan kitamengandungi karbon.
Aplikasi kimia organik
Perubatan Industri Petroleum
Industri Tekstil
Metaboolisme Manusia Plastik dan polimer
Petrokimia Sains Genetik.
7/24/2019 BBR 26703 ana,ena,keton.pdf
5/69
*Sebatian Organik kegunaan dalamaplikasi perubatan
Sulfonamide-asas bagibeberapa drugs, agenantimikrob sintetik
anthracyclines, banyak digunakansebagai penawar kanser sejak 1960s
Xopenex
(levalbuterolHCl)InhalationSolution
Antihypercholesterolemiccompounds lovastatinand simvastatin arewidely used in medicinefor the lowering of levelsof blood cholesterol
steroid - moleculesthat are critical forkeeping the bodyrunning smoothly
http://localhost/var/www/apps/conversion/tmp/scratch_1//patentimages.storage.googleapis.com/WO2002072566A1/imgf000003_0001.png7/24/2019 BBR 26703 ana,ena,keton.pdf
6/69
Beberapa produk kimia organik
DNA
Minyak pati
Ubatan
Bahan Aktif Farmaseutikal
Materials
Petrol
Pigmen
7/24/2019 BBR 26703 ana,ena,keton.pdf
7/69
Ciri utama Sebatian Organik
Mudah terbakar dan mudah terurai kepada gas(jika tidak mengandungi gabungan logamdalam struktur).
Amnya, tbls kimia bagi sebat organik adalahperlahan.
Sebahagian sebatian organik mungkinmengandungi komponen halogen (less
flammable)
yang tinggi e.g. (X = F, Cl, Br, I,).
**How many H atom can bind to C atom?
7/24/2019 BBR 26703 ana,ena,keton.pdf
8/69
Kumpulan Berfungsi
Kumpulan Berfungsi:atom atau kumpulanatom dalam molekul yang menunjukkan setciri fizikal dan/atau kimia tertentu
Kumpulan berfungsi penting untuk 3 sebab;1. unit-unit ini membahagi sebatian-sebatian
organik kepada kelas-kelas.
2. Unit ini merupakan tapak bagi bermulanya tblaskimia.
3. Asas bagi penamaan sebatian organik.
7/24/2019 BBR 26703 ana,ena,keton.pdf
9/69
Penamaan (Nomenclature): RingkasanKump Berfungsi Bermula .. Berakhir.. Bilangan C
Alkana Met ana 1
Alkena Et ena 2
Alkuna Prop una 3
Alkohol But ol 4
Aldehid Pent .al 5
Keton Heks on 6
Asid Karboksilik Hept asidoik 7
Ester Oct R. oat 8Alkil Halida Non il halida 9
Eter Dec R.. R.. eter 10
Aromatik
7/24/2019 BBR 26703 ana,ena,keton.pdf
10/69
Beberapa contoh:
Lukis dan namakan hidrokarbon berikut :(a) alkohol, 5 atom C
(b) keton, 3 atom C
(c) Asid Karboksilik, 7 atom C
Beri nama sebatian mengikut IUPAC :(a) CH3CH2COH
(b) CH3CH2COCH3(c) CH2=C(CH3)CH3(d) CH3CH2COOCH3(e)
7/24/2019 BBR 26703 ana,ena,keton.pdf
11/69
Alkana, CnH2n+2
7/24/2019 BBR 26703 ana,ena,keton.pdf
12/69
Isomerism
In chemistry, isomers are compounds with thesame molecular formulabut different structural
formulas.[1]Isomers do not necessarily share
similar properties, unless they also have the
same functional groups. There are manydifferent classes of isomers, like stereoisomers,
enantiomers, geometrical isomers, etc. (see
chart below). There are two main forms of
isomerism: structural isomerismand
stereoisomerism
N l & K i
http://en.wikipedia.org/wiki/Chemistryhttp://en.wikipedia.org/wiki/Molecular_formulahttp://en.wikipedia.org/wiki/Structural_formulahttp://en.wikipedia.org/wiki/Structural_formulahttp://en.wikipedia.org/wiki/Isomer#cite_note-1http://en.wikipedia.org/wiki/Functional_grouphttp://en.wikipedia.org/wiki/Structural_isomerismhttp://en.wikipedia.org/wiki/Stereoisomerismhttp://en.wikipedia.org/wiki/Stereoisomerismhttp://en.wikipedia.org/wiki/Structural_isomerismhttp://en.wikipedia.org/wiki/Functional_grouphttp://en.wikipedia.org/wiki/Isomer#cite_note-1http://en.wikipedia.org/wiki/Structural_formulahttp://en.wikipedia.org/wiki/Structural_formulahttp://en.wikipedia.org/wiki/Molecular_formulahttp://en.wikipedia.org/wiki/Chemistry7/24/2019 BBR 26703 ana,ena,keton.pdf
13/69
Nomenclature & Keisomeran
Alkanes
ButanaISOMERS
2-metil propana
Pentana
ISOMERS2-metil butana
2,2-dimetil propana
Heksana
ISOMERS
Heptana
ISOMERS
7/24/2019 BBR 26703 ana,ena,keton.pdf
14/69
Nomenclature (Penamaan) & Keisomeran
Isomer Struktur:
Sebatian dengan sifat fizikal dan kimia berbeza tetapi formulamolekul yang sama.
Stereoisomer
Sebatian2 dengan formula molekul sama tetapi susunanatom yang berbeza.Berbeza antara satu sama lain pada orientasi kumpulandalam molekul.Stereoisomer teringkas ialah isomer cisdan trans.Butena, C4H8, wujud dalam isomer cisdan trans.
7/24/2019 BBR 26703 ana,ena,keton.pdf
15/69
Namakan 2 sebatian ini dannyatakan jika keduanya adalahisomer antara satu sama lain.
Bagaimana dengan menamakan
sebatian alkana siklik?
siklopentana
siklobutana
7/24/2019 BBR 26703 ana,ena,keton.pdf
16/69
cis-3,4-dimetil-3-heptena
C=C
CH3
H3C
CH3CH2CH2CH2CH3
trans-1,2-dikloro-1-butena
C=C
HCl
CH3CH
2
Cl
7/24/2019 BBR 26703 ana,ena,keton.pdf
17/69
Alkena, CnH2n
7/24/2019 BBR 26703 ana,ena,keton.pdf
18/69
Ciri utama molekul alkena ialah ikatan dubel.
Ik terdiri drp 1 ik. kovalen (sigma) dan 1 ik. (pi).
Sebat mengandungi ik. Dubel dikatakan tidak tepu
(unsaturated)kerana boleh bertbls dengan hidrogendengan kehadiran mangkin.
Sebatian yang dihasilkan ialah sebatian tepu
(saturated) / tidak mengandungi ik. berbilang (multiple).
Sifat fizik: hampir sama dengan alkana i.e. wujud
sebagai gas pada suhu bilik.Isomer alkena mempunyai takat didih hampir sama
(sukar dipisah).
Ciri Alkena:
7/24/2019 BBR 26703 ana,ena,keton.pdf
19/69
Alkene Nomenclature
The rules for alkenes are similar to those used for alkanes. The following rules
summarize alkene nomenclature.
1. Identify the longest continuous chain of carbon atoms that contains the carbon-
carbon double bond.
2. The parent name of the alkene comes from the IUPAC name for the alkane with
the same number of carbon atoms, except the -aneending is changed to -enetosignify the presence of a double bond. For example, if the longest continuous chain
of carbon atoms containing a double bond has five carbon atoms, the compound is a
pentene.
3. Number the carbon atoms of the longest continuous chain, starting at the endclosest to the double bond. Thus, is numbered from right to left, placing the double
bond between the second and third carbon atoms of the chain. (Numbering the
chain from left to right incorrectly places the double bond between the third and
fourth carbons of the chain.)
7/24/2019 BBR 26703 ana,ena,keton.pdf
20/69
The position of the double bond is indicated by placing the
lower of the pair of numbers assigned to the double-bonded
carbon atoms in front of the name of the alkene. Thus, the
compound shown in rule 2 is 2-pentene.
The location and name of any substituent molecule or groupis indicated. For example, is 5-chloro-2-hexene.
Finally, if the correct three-dimensional relationship is
known about the groups attached to the double-bondedcarbons, the cisor transconformation label may be assigned.
Thus, the complete name of the compound in rule 4 (shown
differently here)
Alkene Nomenclature
cis-5-chloro-2-hexene
7/24/2019 BBR 26703 ana,ena,keton.pdf
21/69
Alkene Reactions
Oxidation
Electrophilic Addition rxn
Halogenation
Hydrohalogenation
Hydration (Direct water addition)
Hydrogenation
7/24/2019 BBR 26703 ana,ena,keton.pdf
22/69
Alkene Reactions
Oxidation
(purple) (brown)
*Baeyer Test
Cleavage reaction (further oxidation)
* any water-soluble compound that produces this color change when added
to cold potassium permanganate must possess double or triple bonds.
7/24/2019 BBR 26703 ana,ena,keton.pdf
23/69
**Markonikovs Rule: The halide component of HX bonds preferentially at the more
highly substituted carbon, whereas the hydrogen prefers the carbon which already
contains more hydrogens.
+
Hydrohalogenation/Alkyl halide addition
7/24/2019 BBR 26703 ana,ena,keton.pdf
24/69
Alkynes, CnH2n-2
7/24/2019 BBR 26703 ana,ena,keton.pdf
25/69
Physical Properties of Alkynes
The physical properties of alkynes are very similar to those of
the alkenes. Alkynes are generally nonpolar molecules with little solubility in
polar solvents, such as water.
Solubility in nonpolar solvents, such as ether and acetone, is
extensive.
Like the alkanes and alkenes, alkynes of four or fewer carbon
atoms tend to be gases.
Name: ?
Answer: 5-chloro-2-hexyne
7/24/2019 BBR 26703 ana,ena,keton.pdf
26/69
The principal reaction of the alkynes is addition across the
triple bond to form alkanes.These addition reactions are analogous to those of the
alkenes.
Hydrogenation
Alkyne Addition Reactions
Name the end product of 5-methyl-3-heptynes
after hydrogenation process
A: 3-methylheptane
7/24/2019 BBR 26703 ana,ena,keton.pdf
27/69
Halogenation
Hydrohalogenation
**Markonikovs Rule: The halide component of HX bonds preferentially at the more
highly substituted carbon, whereas the hydrogen prefers the carbon which already
contains more hydrogens.
Alkyne Addition Reactions
7/24/2019 BBR 26703 ana,ena,keton.pdf
28/69
Alkyne Reactions
Combustion?
C6 combustion?
7/24/2019 BBR 26703 ana,ena,keton.pdf
29/69
Preparation of Alkynes
Deydrohalogenation/Dihaloalkane elimination
Dehalogenation
7/24/2019 BBR 26703 ana,ena,keton.pdf
30/69
Mechanism dihaloalkane elimination
7/24/2019 BBR 26703 ana,ena,keton.pdf
31/69
Preparation of Alkynes
Substitution
* acetylene
Acidity of alkynes
7/24/2019 BBR 26703 ana,ena,keton.pdf
32/69
From alkene
Preparation of Alkynes
7/24/2019 BBR 26703 ana,ena,keton.pdf
33/69
Exercise:
Question 1: What are the major products of the
following reactions: a.) 1,2-Dibromopentane with sodium amide in liquid
ammonia
b.) 1-Pentene first with Br2and chloromethane,
followed by sodium ethoxide (Na+-O-CH2CH3)
Question 2: What would be good starting molecules
for the synthesis of the following molecules:
7/24/2019 BBR 26703 ana,ena,keton.pdf
34/69
Cont..
Question 3: Use a 6 carbon diene to synthesize a
6 carbon molecule with 2 terminal alkynes.
7/24/2019 BBR 26703 ana,ena,keton.pdf
35/69
Reactions Summary (Alkenes)
Type Reaction
Addition of Halogen, X2 >C=C< + X2 >CH(X)-CH(X)< (X= Cl, Br)
Addition of Polar reagents >C=C< + H-OH >CH(H)-CH(OH)C=C< + H-X >CH(H)-CH(X)< (X = Cl, Br, F, I)
Hydroboration-Oxidation RCH2=CH2 (BH3) (RCH2=CH2)3B (H2O2/OH-)
RCH2CH2OH
Addition of Hydrogen >C=C< + H2 (Pd, Pt or Ni) >CH(H)-CH(H)C=CH-CH=C< + X2 >CH(X)-CH(X)-C=CH +>CH(X)-CH=CH-C(X)C=CH-CH=C< + HX >CH-CH(X)-C=CH + >CH-
CH=CH-C(X) 50 mL)
Ethanol/ethyl alcohol/grain alcohol
The acohol of alcoholic beverages; the fermentation of honey, grain, or
fruit juices to yield beers and wines was probably the first chemicalreaction to be discovered; metabolized in the body to produce
acetaldehyde
Isopropyl alcohol/2-propanol
Rubbing alcohol is 70%isopropyl alcohol and 30% water
7/24/2019 BBR 26703 ana,ena,keton.pdf
48/69
Alcohols are classified as primary (1), secondary
(2), or tertiary (3) according to how many carbongroups are attached to the carbon bearing the OH
group:
R-CH2-OH primary (1)R-CH(R)-OH secondary (2)
R-C(R)(R)-OH tertiary (3)
The number of hydrogens on the carbon bearing the
OH group does affect some chemical properties.
Classification of Alcohols
7/24/2019 BBR 26703 ana,ena,keton.pdf
49/69
Some properties of alcohol
Polar solventdue to hydrogen bonding
Since the OH group makes alcohols polar, they will
mix with polar solvents like water as long as the
carbon chain is fairly short.*The longer the carbon chain,the less soluble the alcohol is.
Because alcohols hydrogen bond to each other,
theyhave higher boiling points than alkanes of the
same molecular weight. *The boiling point of alcohols
increases as the molecules become larger.e.g. bp: phenol (181.7 C); toluene (110.6 C)
S ti f th O
7/24/2019 BBR 26703 ana,ena,keton.pdf
50/69
Some properties of ether
Ethers are relatively stable and unreactive in many respect; some react slowly with
air to produceperoxides(contain O-O).The peroxides from low MW ethers such as diiso-propyl ether and tetrahydrofuran
are explosiveand extremely dangerous.
Ethers boiling point(bp) are somewhat higherthan bp of comparable alkane. E.g.
B.p.(C): CH3-O-CH3(-25) ; CH3CH2CH3(-45)
O
Acidic cleavage:
Claisen Rearrangement
Reaction of ether
O-CH2-CH=CH2Claisen rearrangement
250 C
OHCH2-CH=CH2
HBr,H2O
Reflux
O-CH2-CH3 OH
+ CH3CH2Br
7/24/2019 BBR 26703 ana,ena,keton.pdf
51/69
Reaction of Alcohols
Dehydration of Alcohols to Produce Alkenes
CH3CH2CH(OH)CH3 CH3CH=CHCH3+ H2O
(+CH3CH2CH=CH2)
Metal salt (Alkoxide) formation:Alcohols are only slightlyweaker acids than water, with a Kavalue of approximately
11016. The reaction of ethanol with sodium metal (a base)
produces sodium ethoxide and hydrogen gas. This reaction is
identical to the reaction of sodium metal with water.
H2SO4, 180 C
Reaction of Alcohols
7/24/2019 BBR 26703 ana,ena,keton.pdf
52/69
Alkyl Halide formation
Dehydration of alcohols to produce ethers
R-OH + R-OH R OR + H2O
Oxidation of alcohols
*R-OH RH-C=O R-C=O-OH
*1 : Aldehyde; 2 : ketone
Reaction of Alcohols
H2SO4, 140 C
KMnO4 KMnO4
R ti f Al h l
7/24/2019 BBR 26703 ana,ena,keton.pdf
53/69
Substitution, Lucas Reagent (ZnCl2)
CH3CH2OH + HCl CH3CH2Cl + H2O
alcohol + hydrogen halide alkyl halide + water (ZnCl2)
This reaction with the Lucas Reagent (ZnCl2) is a qualitative test
for the different types of alcohols because the rate of the reaction
differs greatly for a primary, secondary and tertiary alcohol.
The difference in rates is due to the solubility of the resulting
alkyl halides
Tertiary Alcohol turns cloudy immediately (the alkyl halide is not
soluble in water and precipitates out)
Secondary Alcohol turns cloudy after 5 minutes
Primary Alcohol takes much longer than 5 minutes to turn cloudy
Reaction of Alcohols
Alcohols preparation
7/24/2019 BBR 26703 ana,ena,keton.pdf
54/69
Preparation from.. Reaction
Reduction of Carbonyl Compounds R-C=O ([H]) R-CH-OH; [H] = reducing
agent e.g. LiAlH4, NaBH4
*R-C=O-H R-CH-OH (1)
R-C=O-R R-CHR-OH (2)
Reduction of carboxylic Acids and Esters R-C=OOH or R-C=OOR R-CH-OH
(not as rapid as carbonyl compounds)
Reaction of carbonyl compounds with
Grignard Reagents
RC=O R-CH2OH + HOMgX
p p
1. LiAlH4, ether
2. H3O+
1. NaBH4,ethanol
2. H3O+
1. NaBH4,ethanol
2. H3O+
1. RMgX, ether
2. H3O+
7/24/2019 BBR 26703 ana,ena,keton.pdf
55/69
Aldehydes and Ketones-Carbonyl compounds
N l
7/24/2019 BBR 26703 ana,ena,keton.pdf
56/69
Nomenclature
Formula Common name/systematic name
HCHO Formaldehyde/Methanal
CH3CHO Acetaldehyde/Ethanal
CH3CH2CHO Propionaldehyde/Propanal
CH3CH2CH2CHO Butyraldehyde/Butanal
CH3CH2CH2CH2CHO Valeraldehyde/Pentanal
CH2=CHCHO Acrolein/Propenal
Benzaldehyde/BenzenecarbaldehydeCHO
N l t
7/24/2019 BBR 26703 ana,ena,keton.pdf
57/69
Nomenclature
Formula Common name/systematic name
CH3C=OCH3 Dimethyl ketone(acetone)/Propanon
CH3CH2C=OCH2CH3 Diethyl ketone/3-Pentanone
Benzophenone/Diphenyl ketone
C=O
7/24/2019 BBR 26703 ana,ena,keton.pdf
58/69
Aldehydes and Ketones
contain a carbonyl (C=O)
groupC HO
CH3 - C- H
O
CH3 -C-CH3
O
C
O
Functionalgroup
Acetaldehyde(an aldehyde)
Acetone(a ketone)
Functionalgroup
Reaction of Aldehyde and Ketones
7/24/2019 BBR 26703 ana,ena,keton.pdf
59/69
Reaction of Aldehyde and Ketones
Oxidation: RCH=O RC=O-OH
Addition of Grignard reagents:
CrO3,H3O+
Acetone, 0 C
*Aldehydes are readily oxidized to yield carboxylic acids but ketones are
generally inert towards oxidation.
e.g. CH3(CH2)4CH=O CH3(CH2)4C=O-OH
CrO3,H3O+
Acetone, 0 C
RC=ORR-MgX, Ether
H3O+
RRRC-OH
Reaction of Aldehyde and Ketones
7/24/2019 BBR 26703 ana,ena,keton.pdf
60/69
Reaction of Aldehyde and Ketones
Reduction: RCR=O RCH-OH
Tollens Test
*In a Tollens test, Ag+
is reduced to Ag0
, leaving inside surface of the flaskcoated with a reflective silver mirror.
* Only aldehyde (ketone will not) response in Tollens test.
:H-
From NaBH4
CHOHCN
CN-C-OH
CHO HO-C=OAg2O
NH4OH, H2O, EtOH+ Ag
7/24/2019 BBR 26703 ana,ena,keton.pdf
61/69
Carboxycylic Acid and Esters-Carbonyl compounds
N l t
7/24/2019 BBR 26703 ana,ena,keton.pdf
62/69
Nomenclature
Formula Common name/systematic
nameHCOOH Formic acid/Methanoic acid
CH3COOH Acetic acid/Ethanoic acid
CH3CH2COOH Propanoic acid
CH3CH2CH2COOH Butanoic acid
CH3CH2CH2CH2COOH Pentanoic acid
CH2=CHCHO Acrolein/Propenal
Benzoic acidCOOH
7/24/2019 BBR 26703 ana,ena,keton.pdf
63/69
Carboxylic Acids
contain a carboxyl (-COOH) group
C O
O
H CH3
-C-O-H
O
CH3
COOH CH3
CO2
H
: ::
:
or or
Acetic acid
(a carboxylic acid)
Functionalgroup
7/24/2019 BBR 26703 ana,ena,keton.pdf
64/69
Carboxylic Esters
Ester:a derivative of a carboxylic acidin which the carboxyl hydrogen is
replaced by a carbon group
C O
O
Functionalgroup
CH3 -C-O-CH2 -CH3
Ethyl acetate
(an ester)
:
:
: :O
7/24/2019 BBR 26703 ana,ena,keton.pdf
65/69
Carboxylic Amide
Carboxylic amide, commonly referred to as anamide: a derivative of a carboxylic acid inwhich the -OH of the -COOH group is replacedby an amine
the six atoms of the amide functional group
lie in a plane with bond angles of
approximately 120
CH3 -C-N-H
H
Acetamide(a 1 amid e)
O
C N
O
Functionalgroup
7/24/2019 BBR 26703 ana,ena,keton.pdf
66/69
For most carboxylic acids, Kais approximately 10-5; e.g.
acetic acid, Ka= 1.76 10-5.
Although much weaker than mineral acids, carboxylic acid
are much stronger acids than alcohols
Acid carboxylic preparation
Oxidation of Primary Alcohol
CH3(CH2)8-OH CH3(CH2)8C(OH)=O
Oxidation of a substituted alkylbenzene with KMnO4orNa2Cr2O7; benzoic acid is formed
CrO3
H3O+
CH3 KMnO4
H2O,95 C
COOHNO2 NO2
7/24/2019 BBR 26703 ana,ena,keton.pdf
67/69
Amines
contain an amino group; an sp3-hybridized
nitrogen bonded to one, two, or three carbonatoms
an amine may by 1, 2, or 3
C H3 N H
H
C H3 N H
C H3
C H3 N C H3
C H3
Methylamine(a 1 amine)
Dimethylamine(a 2 amine)
Trimethylamine(a 3 amine)
: : :
7/24/2019 BBR 26703 ana,ena,keton.pdf
68/69
Summary
For each functional groups discussed (alkane alkenes
7/24/2019 BBR 26703 ana,ena,keton.pdf
69/69
For each functional groups discussed (alkane, alkenes,
alkynes, alcoholðer, aldehyde&ketone, acid
carboxylic & ester); please look into their
Nomenclature, try the most difficult one, Also look into
naming some common aromatic, amine and amide
compounds.
Special reactions such oxidation/reduction; memorizereagents involved.
The most discussed method of preparation, the
reagents and expected outcome
Special test to differentiate certain carbonyl
compounds or between alkanes, alkenes and alkynes