Organic Chemistry - Group 5 - Functional Group (2)

National University – HCMC International University

SHOOL OF BIOTECHNOLOGY SUBJECT: ORGANIC CHEMISTRY LECTURER: PH.D HOÀNG LÊ SƠN

List of students: NGUYỄN HẢI ĐĂNG PHẠM VŨ ANH NGUYỄN THỊ PHƯƠNG THÙY VÕ TƯỜNG KHANH NGUYỄN HỮU LỘC  

BTUN08001 BTUN08004 BTUN08032 BTUN08048 BTIU08147

General Content: INTRODUCTION CLASSIFICATION 6 IMPORTANT GROUPS IN CHEMISTRY OF LIFE INTERMOLECULAR FORCES PHYSICAL PROPERTIES REFERENCES

WHAT ARE FUNCTIONAL GROUPS?  In organic chemistry, functional groups are specific groups of atoms within molecules that are responsible for the characteristic chemical and physical reactions of those molecule.  Functional groups define the structure of a family of compounds and determine its properties.

CLASSIFICATION: TWO TYPES OF CLASSIFICATION

Classification based on hetaroatoms Classification based on the bond

a.Hydrocarbon

Classification based on hetaroatoms

b.Groups containing halogen c.Groups containing oxygen d.Groups containing nitrogen e.Groups containing phosphorus and sulfur

 Classification based on the bond: a.σ bonds (single bond) b.π bonds

6 IMPORTANT GROUPS IN LIFE OF CHEMISTRY Hydroxyl group Carbonyl group

Carboxyl group

Amine group

Suflhydryl group Phosphate group

A. Hydroxyl group: Definition: A functional group which has one oxygen atom bonded to one hydrogen atom is called hydroxyl group.

-R-O-H (where R is any “alkyl” group)

Name Of Compound:

-Alcohols (their specific names usually end in -ol) -Example: ethanol (ethyl alcohol)

Physical Properties: -Boiling point: higher than alkanes (E.g: ethanol 78oC , ethane -162oC) -Hydrophilic (water loving) -Methanol, ethanol, propanol  soluble in water -Butanol  moderately soluble in water -Alcohols which containing 5 or more carbon atoms  effectively insoluble in water

-Most of the common alcohols are colorless liquids at room temperature. Ethanol, methanol, and isopropyl alcohols are free-flowing liquids. -The higher alcohols-those containing 4 to 10 carbon atoms- are vicous (oily). -Some of the highly branched alcohols and many alcohols containing 12 or more carbon atoms are solids.

Chemical Properties: 1/ Undergo oxidation -> aldehydes, ketones, carboxylic acid:

2/ Dehydrates -> ankenes:

3/ React to form ester compound:

4/ Undergo Nucleophilic substitution:

Classification of purified water: +Distilled water (water that has virtually all of its impurities removed through distillation.) +Double-distilled water +Demineralized water (water that has its mineral ions remove)

Health effects of water - Water is needed to detoxify the kidneys and the liver -Magnesium, calcium, fluoride, and other nutrients in water can help to protect against nutritional deficiency -If our body has a lack of water we will become constipated - Your skin will look and be healthier -You'll have less headaches and/or dizzy spells -Safe water (safe for drinking and bathing) could prevent 1.4 million child deaths from diarrhea each year

Application: -Methanol can be used as an alcohol fuel -Ethanol can be used as: beverage, alcohol fuel, solvent in medical drugs, perfumes and vanilla, ethanol based-soap -Alcohol gels have become common as hand sanitizers

B. CARBONYL GROUP: Definition: -A carbonyl group is a functional group composed of a carbon atom doublebonded to an oxygen atom. -Oxygen is more electronegative than carbon, and thus pulls electron density away from carbon to increase the bond's polarrity. Name of compound:

Aldehydes and Ketons.

CLASSIFICATION:

ALDEHYDE: Physical Properties: -HCHO, CH3CHO is gas, they have strong smell, dissolve in water. -Aldehyde has more than 3C is liquid but slightly than water. -HCHO (35%-40%) is called A solution of Fomalin . -Aldehydes have at least one carbon attached to the carbonyl group.

KETONES

Physical Properties: -Ketones have two organic groups attached to the carbonyl group -The carbonyl group is polar as a consequence of the fact that the electronegative of the oxygen center is greater than that for carbonyl carbon. -Ketones are nucleophilic at oxygen and electrophilic at carbon.

Chemical properties: ALDEHYDE: 1.React with H2: R-CHO + H2 --> R-CH2OH. 2. React with NaHSO3: R-CHO + NaHSO3 --> R-CHOH SO3Na 3. React with HCN: R-CHO + HCN --> R-CHOH CN We see that: +1 -1 C + 2e --> C Aldehyde is oxidizable.

KETONES: 1.React with H2: R-CO-R’ + H2 --> R-CHOH-R’ (Alcohol)

2. React with HCN: R-CO-R’ + HCN --> R-COH-R’ CN

ALDEHYDE:  Oxidation-reduction reaction: The main reaction of Aldehyde is Tollens’ mirror silver test: R-CHO + 2[Ag(NH3)2]OH --> 2Ag + 3NH3 + H2O

RCOONH4+

 Benedict’s reaction (Cu(OH)2): RCHO + 2Cu(OH)2 --> RCOOH + Cu2O + 2H2O HCHO + 4Cu(OH)2 --> CO2 + 2Cu2O + 5H2O

 Bromine water reaction: R-CHO + Br2 + H2O --> R-COOH + 2HBr

KETONES:  React with Br2: CH3-CO-CH3 + Br2 --> CH3-CO-CH2Br + HBr

DO NOT MAKE Br2 LOOSE ITS COLOR

Biological Function:

GLUCOSE (C6H12O6)

-Glucose is a carbohydrate, and is the most important simple sugar

in human metabolism. Glucose is called a simple sugar or a monosaccharide because it is one of the smallest units which has the characteristics of this class of carbohydrates.

-Glucose, also known as - grape sugar, blood sugar, or corn sugar. -The normal concentration of glucose in the blood is about 0.1%, but it becomes much higher in persons suffering from diabetes.

-The living cell uses it as a source of energy and metabolic intermediate. -In animals and fungi, glucose is the result of the breakdown of glycogen -In plants the breakdown substrate is starch. -When oxidized in the body in the process called metabolism, glucose degrades to carbon dioxide, water -Energy from glucose is obtained from the oxidation reaction C6H12O6 + 6O2 --> 6CO2 + 6H2O

Application: -Aldehydes: HCHO: used to produce plastic, dye, pharmaceutical product, medicine. -HCHO 37% - 40% is Fomalin, used to embalm a corpse. -CH3CHO: used to produce D.D.T (one kind of insecticide). -Ketones : used to synthetize organic compound, polime, clorofom, iodofom

C. Carboxyl group:

Definition: -Carboxyl group is chemical functional groups with one carbon, one hydrogen, and two oxygen atoms (COOH), usually written -COOH or -CO2H .

-EX : acetic acid ( CH 3 COOH )

THE IUPAC NAME OF A CARBOXYLIC ACID IS DERIVED FROM THAT OF THE LONGEST CARBON CHAIN THAT CONTAINS THE CARBOXYL GROUP BY DROPPING THE FINAL -E FROM THE NAME OF THE PARENT ALKANE AND ADDING THE SUFFIX -OIC FOLLOWED BY THE WORD “ACID.” THE CHAIN IS NUMBERED BEGINNING WITH THE CARBON OF THECARBOXYL GROUP.

Common name

IUPAC name

Chemical formula

Formic Acid

Methanoic Acid

HCOOH

Acetic Acid

Ethanoic Acid

CH3COOH

Propionic Acid

Propanoic Acid

CH3CH2COOH

Butyric Acid

Butanoic Acid

CH3(CH2)2COOH

Valeric Acid

Pentanoic Acid

CH3(CH2)3COOH

Caproic Acid

Hexanoic Acid

CH3(CH2)4COOH

Enanthic Acid

Heptanoic Acid

CH3(CH2)5COOH

Caprylic Acid

Octanoic Acid

CH3(CH2)6COOH

Pelargonic Acid

Nonanoic Acid

CH3(CH2)7COOH

Physical Properties: Boiling point and melting point : -Boiling point is the temperature at which vapor pressure saturated liquid surface by atmospheric pressure . -There are two factors that affect the boiling temperature and melting point is the molecular weight organic compounds and Hydrogen bond of this compounds . Ex : acetic acid have boiling point at 118°C Formic acid have boiling point at 100,8 °C (213,3 °F) . Melting point g/mole Formula Boiling point Propanoic Acid

C3H6O2

Melting point C4H8O2

-21 °C (252 141 °C (414 74,08 g/mol K) K) -7,9 °C (265,1 K)

163,5 °C (436,5 K)

88,1051 g/mol

Chemical Properties: Stability of the acid : In the homologous organic acids , stability of acid decrease with the increasing molecular weight: H-COOH > CH3-COOH > CH3-CH2-COOH Axit fomic Axit axetic React with metal : Ex: CH3COOH + Mg React with basic : Ex : HCOOH

+ NaOH

Axit propionic

 CH3COOMg + H2

 HCOONa +H2O

React with salt: Ex: CH3COOH + CaCO3  (CHCOO)2Ca + CO2 + H2O React with alcohols to give ester : Ex: CH3COOH + C2H5OH  CH3COOC2H5 + H2O

Haloenation

Ring substitution in aromatic acids

Biological -A form of Vitamin C is called ascorbic acid and is a carboxylic acid function: -Carboxylic acids that have very long, unbranched chains of 12-24 carbon atoms attached to them are called fatty acids , they are important in the formation of fat in the body . -Lactic acid is generated in muscles of the body as the individual cells metabolize sugar and do work. A buildup of lactic acid, caused by overexertion, is responsible for the fatigue one feels in the muscles by such short-term use.

Application: -Carboxyl group used to produce chemical compounds . -Many carboxylic acids are present in the foods and drinks we ingest, like malic acid (found in apples), tartaric acid (grape juice), and oxalic acid (spinach and some parts of the rhubarb plant) -Carboxylic acids are also very important industrially. Perhaps one of the most important industrial applications of compounds with carboxyl groups is the use of fatty acids--carboxyl groups attached to long carbon chains--making soaps, detergents, and shampoos . Carboxylic acids are also important in the manufacture of greases, crayons, and plastics .

D. Amine Group: Definition:

-Amines are organic compounds which are composed from ammonia by replacing one, two or three of the hydrogen atoms on an ammonia molecule by alkyl or aryl group.

Classification: Primary amines:

Secondary amines:

Tertiary amines:

Name Of Compound:

AMINE

Physical -Primary andProperties: secondary amines can form hydrogen bonds to each other and water. Tertiary cannot form hydrogen bonds to each other but can form hydrogen bonds to water.

-The boiling point: in the isomers of amine, the boiling point of primary amines is highest and tertiary amines is lowest.

-Amines are soluble in water.

-All of the amines have stench odor.

Chemical Properties:

Basicity: Amines are organic derivatives of ammonia, so basic properties of amines like ammonia. NH3 + H2O ↔ NH4+ + HORNH2 + H2O ↔ RNH3+ + HOAmines react with acid (1):

Ammonium salts react with bases: CH3NH3Cl + NaOH → CH3NH2 + NaCl + H2O C6H5NH3Cl + NaOH → C6H5NH2 + NaCl + H2O Halogenation C6H5NH2 + 3Br2 → C6H5NH2(Br)3 + 3HBr Sulphurization C6H5NH2 + HOSO3H → H2N-C6H5-SO3H + H2O

Amines react with nitrous acid: Primary amine: R-NH2 + HO-NO → R-OH + N2↑ + H2O (alcohol) Secondary amine: (2)

-Tertiary amine does not react with nitrous acid

Biological Function: -Linear chains of amino acid build block of proteins

Application: -Many drugs are designed to mimic with the action of natural amine neurotransmitters. Ex: glucosamine is a building block of proteoglycans which are essentially protein molecules.

5.Sulfhydryl Group: Definition: - Sulfhydryl or Thiol is a functional group consisting one sulfur atom bonded to one hydrogen atom.

Name of compounds:

-The name of compounds containing sulfhydryl groups are formed by adding the prefix “- thiol”.

Physical Properties: Odor : -The odor of thiols is often strong and repulsive, particularly for those of low molecular weight . -However, not all thiols have unpleasant odors. -Ex : Propanethiol (C3H7SH) is found in freshly sliced onion

Boiling Points & Solubility: -Thiols show little association by hydrogen bonding , with both water molecules and among themselves .

-Hence, they have lower boiling point and are less solube in water and other polar solvent than alcohols of similar molecular weight. They boil at considerably lower temperatures:  H2O..........100 CH3OH…..64.7 C2H5OH….78.3

H2S……….-61 CH3SH…….7.6 C2H5SH……34.7

• Chemical propeties: S-alkylation Thiols, or more particularly their conjugate bases, are readily alkylated to give thioethers: RSH + R'Br + base → RSR' + [Hbase]Br Acidity The sulfur atom of a thiol is quite nucleophilic, rather more so than the oxygen atom of an alcohol. The group and its corresponding anion are readily oxidized by reagents such as bromine to give an organic disulfide (R-S-S-R). 2R-SH + Br2 R-S-S-R + 2HBr

Redox: -Thiols, especially in the presence of base, are readily oxidized by reagents such as iodine to give an organic disulfide (R-S-S-R). -2 R-SH + Br2 → R-S-S-R + 2 HBr Oxidation by more powerful reagents such as sodium hypochlorite or hydrogen peroxide yields sulfonic acids (RSO3H).

-R-SH + 3H2O2 → RSO3H + 3H2O Thiols participate in thiol-disulfide exchange: -RS-SR + 2 R'SH → 2 RSH + R'S-SR' This reaction is especially important in nature.

Biological Function: Cysteine (Cys) -As the functional group of the amino acid cysteine, the thiol group plays an important role in biology: amino acid. -When the thiol groups of two cysteine residues (as in monomers or constituent units) are brought near each other in the course of protein folding, an oxidation reaction can generate a cystine unit with a disulfide bond (-S-S-). -A physical manifestation of cysteinecystine equilibrium is provided by hair straightening technologies.

-Sulfhydryl groups in the active site of an enzyme can form noncovalent bonds with the enzyme's substrate as well, contributing to catalytic activity. -Active site cysteine residues are the functional unit in cysteine proteases. -Cysteine residues may also react with heavy metal ions because of the high affinity between the soft sulfide and the soft metal.

Application: -Enzyme Ficin (EC 3.4.22.3) , a thiol protease, presents in the latex of some fig species (genus Ficus, family Moraceae) From the latex of this fig, we have received the preparation of ficin and determined some factors which effect on the activity of this enzyme such as pH, temperature , substracts.

6. PHOSPHATE GROUP:

Definition: (PO43- ) - An anion formed by dissociation of H3PO4 - Structure: one central phosphorous atom attached with four oxygen atoms in a tetrahedral arrangement.

Name of compound: -Organic Phosphate -Eg: Name of some compounds:

Physical Properties: -PO4 3-general mass: 94.973 g/mol -For example: ATP  Formula : C10 H16 P3O13 N5  Molar mass : 507.181 g/mol  Highly soluble in water  Quite stable in solutions between pH 6.8–7.4 but is rapidly hydrolysed at extreme pH  Best stored as an anhydrous salt.

Chemical Properties: - The phosphate ion is derived from phosphoric acid by electrolytic dissociation reaction in 3 steps: H3PO4

H+ + H2PO4_

H2PO4_

H+ + HPO4

2_

HPO4

H+ + PO4

3_

2_

Why phosphate group show the characteristic of an acid? -Because the oxygen atom with double bond and phosphorous atom are electron withdrawal .

-We can use H3PO4 to make some examples.

-H3PO4 is an average acid, it can make the reaction with base, salt of weaker acid.

React with Base: H3PO4 + NaOH = NaH2PO4 + H2O

(the ratio of this reaction : 1:1) H3PO4 + NaOH = NaHPO4 + H2O (the ratio of this reaction: 1:2) H3PO4 + NaOH = Na3PO4 + H2O (the ratio of this reaction: 1:3) React with Salt of weaker acid: 2H3PO4 + 3CaCO3 = Ca3(PO4)2 + 3 H2O + 3CO2

Biological Function: -Phosphate can be found in ATP, ADP, and AMP, and can be released by the hydrolysis of ATP or ADP.

What is ATP?

-An energy – rich molecule in all cells especially in

muscle cell.

-In cell biology, ATP play an important role as a coenzyme

in energy transfer.

Application: - Phosphate is a component to build the phospholipids in lipid bilayer.

Function of lipid bilayer: -A barrier between the transport inside and outside the cell. -Polar molecules and ions are transported across cell membranes encapsulated within molecules called ionophores. -Phosphate in the cell has 2 main functions in biology: Storage energy and Signaling.

Intermolecular Forces: Definition: -All matter is held together by force. The force between atoms within a molecule is a chemical or intramolecular force. The force between molecules is a physical or intermolecular force.

CLASSIFICATION: • • • •

Dipole-dipole interaction Hydrogen bonding London forces Ion-dipole forces

LONDON DISPERSION FORCES -The weakest of the imtermolecular forces. -London forces are the attractive forces that cause nonpolar substances to condense to liquids and to freeze into solids when the temperature is lowered sufficiently

ION-DIPOLE -An ion-dipole force is an attractive force that results from the electrostatic attraction between an ion and a neutral molecule that has a dipole. -A positive ion (cation) attracts the partially negative end of a neutral polar molecule. -A negative ion (anion) attracts the partially positive end of a neutral polar molecule

Dipole-dipole interaction • Dipole-dipole interactions are the forces that occur between permanent dipoles of two polar molecules. • Dipole-dipole forces exist when molecules are neutral polar (the partial positive charge on one molecule is attracted with the partial negative charge on another molecule)

Hydrogen bonding: -Hydrogen bond is interaction between a hydrogen atom bonded to N, O, F with a nonbonding electron pairs on an N, O, F atom on another molecule

Comparison between intermolecular forces and intramolecular forces : Intramolecular forces which are existed within molecules and influence on chemical properties. Covalent bonds that join atoms together in molecules. The ionic bonds that join ions together in ionic compounds The metallic bonds found in solid metals.

Intermolecular forces which are existed between moleculars and influence on physical properties. Intermolecular forces hold together most organic compounds to each other

Ionic

Covalent

Metallic

Intermolecular

Bond strength

Strong

Very strong

Variable

Weak

Hardness

Moderate to high Very hard, brittle Low to moderate; Crystal soft and somewhat plastic ductile, malleable

Electrical conductivity

Conducts by ion Insulators in solids Good conductors; Insulators in both solid and liquid states transport, but only and liquid states conducts by when liquid or electron transport dissociated

Melting point

Moderate to high Low

Solubility

Soluble in polar solvents

Very low solubility Insoluble except Soluble in organic solvents in acids or alkalis by chemical reaction

Examples

Most minerals

Diamond, oxygen, Cu, Ag, Au, other Organic compounds hydrogen, organic metals molecules

Comparison table of the propertiesstrength, of subtances with intermolecular generally forces and intramolecular forces: (1) moderate

Generally high

Low

PHYSICAL PROPERTIES: Melting Point: -The temperature that can change the solid to liquid by the application of heat. -In melting, the energy is needed for overcoming the attractive forces in crystalline solid. - The characteristic of melting point is figure and indentify pure compounds , elements.

- The higher in melting point, the stronger of intermolecular force.

- When the covalent molecules have the same weight, the melting point depends upon the identify of the functional group.

-If the compounds have the same functional group, the higher melting point is depended on its symmetry. -Symmetry is used to determine the melting point of compounds, having the same functional group and similar molecular weights, but very different shapes.

Boiling point: - The temperature at which the transition from liquid to the gaseous phase occurs in the pure substance at fixed pressure. - Boiling point needs energy to overcome the attractive forces in liquid state. - Similar to melting point, the stronger of intermolecular forces, the higher melting point.

-Consider the examples below which illustrate the effect of size and polarizability on boiling points.

SOLUBILITY: Definition: Solubility is the property of a solid , liquid , or gaseous chemical substance called solute to dissolve in a liquid solvent to form a homogeneous solution . The solubility of one substance in another is determined by the balance of intermolecular forces between the solvent and solute, and the entropy change that accompanies the solvation.

In dissolving a compound, the energy needed to break up the interactions between the molecules or ions of the solute comes from new interactions between the solute and the solvent.

polar dissolves polar nonpolar dissolves nonpolar likes dissolves like

ex : a very polar ( hydrophilic ) solute such as urea is very soluble in highly polar water, less soluble in fairly polar methanol , and practically insoluble in non-polar solvents such as benzene. In contrast, a non-polar or lipophilic solute such as naphthalene is insoluble in water, fairly soluble in methanol, and highly soluble in non-polar benzene.

-An organic compound is water soluble only if it contains one polar functional group capable of hydrogen bonding with the solvent for every five C atoms it contains .To dissolve an ionic compound, the strong ion-ion interactions must be replaced by many weaker ion dipole interactions.

•REFERENCE: PHOSPHATE:

•http://wapedia.mobi/en/Organophosphate •http://en.wikipedia.org/wiki/File:Trisodium_phosphate_3D.jpg •http://en.wikipedia.org/wiki/File:0-phosphate-3D-balls.png •http://www.chemdrug.com/databases/dataimg/7/62657.png •http://fiehnlab.ucdavis.edu/Metabolite-Library-2007/124.png •http://www.ecplaza.net/search/0s1nf20sell/tripotassium_phosphate.html •http://www.ecplaza.net/search/0s1nf20sell/tripotassium_phosphate.html •http://vi.wikipedia.org/wiki/Adenosine_triphosphate

1.kentsimmons.uwinnipeg.ca/cm1504/atp.htm 2.http://static.howstuffworks.com/gif/rd/chemical-elements-of-fertilizers0.jpg PHYSICALPROPERITES:

•http://en.wikipedia.org/wiki/Melting_point •http://en.wikipedia.org/wiki/Boiling_point •http://chemistry.uca.edu/faculty/manion/2401/2401res/chap3.pdf

CARBOXYL GROUP: •http://www.bookrags.com/research/carboxyl-group-woc/ •http://www.tutorvista.com/content/chemistry/chemistry-iv/oxygen-ii/acidity.php •http://www.cem.msu.edu/~reusch/VirtualText/crbacid1.htm HYDROXYL GROUP:

1.(1) http://en.wikipedia.org/wiki/Hydroxyl 2.(2) http://upload.wikimedia.org/wikipedia/commons/thumb/8/88/Hydroxyl3D.png/200px-Hydrox (3)http://www.britannica.com/EBchecked/topic/13366/alcohol (4)http://en.wikipedia.org/wiki/Alcohol (5)http://www.ncbi.nlm.nih.gov/pubmed/31434 SULHYDRYT GROUP: http://en.wikipedia.org/wiki/Sulfhydryl_group http://www.arkema-inc.com/index.cfm?pag=123

AMINES:

1. http://en.wikibooks.org/wiki/Organic_Chemistry/Amines#Properties •http://dl.clackamas.cc.or.us/ch106-05/nomencla.htm •http://en.wikibooks.org/wiki/Organic_Chemistry/Amines#Properties •http://wapedia.mobi/en/Amine •http://bhptemp.mypcat.com/mihirkanani/pcat-gifs/products-small/quinine-sulphate_106781

INTERMOLECULAR FORCES: http://en.wikipedia.org/wiki/Intermolecular_force http://www.chem.purdue.edu/gchelp/liquids/iondip.html http://en.wikipedia.org/wiki/Hydrogen_bond http://www.webchem.net/notes/chemical_bonding/dipoled http://en.wikipedia.org/wiki/Van_der_Waals_force corvallis.k12.or.us/cvhs/kirscha/Exploring Intermolecular Forces...