AMINES

Exercise 1:

Give structures for the following nitroarenes:`

(i) 2, 4 dinitrotoluene

(ii) 3,4, 6 trinitrotoluene

(iii) 3,4 dimethyl 1,2 dinitrobenzene

(iv) TNT

Exercise 2:

Why NO2- ion behaves as an ambident nucleophilie

Exercise 3: Although trimethylamine and n- propylamine have the same molecular weight, the former boils at a lower temperature (276 K) than the latter (322K) Explain

Exercise 4:

How will you prepare ethylamine from acetaldehyde?

Exercise 5: Amino group in ethylamine (CH3CH2NH2) is basic but not in acetamide (CH3CONH2) or acetanilide (C6H5NHCOCH3) why?

Exercise 6: What is the role of conc. H2SO4 in the nitration of benzene with a mixture of conc. HNO3 and conc. H2SO4?

Exercise 7:

Convert n butylamine from propene in 3 steps.

Exercise 8: Name the products and write chemical reactions when following compounds are hydrolysed.

(a) CH3CH2CN with dil. HCl

(b) CH3CN with H2O2 (alkaline)

(c) C2H5NO2 with dil. HCl

Exercise 9:

What is Baker Mullikens Test?

Exercise 10: (i) Give the structure of A (C3H9N) such that if it reacts with benzene sulphonyl chloride to form a solid insoluble in alkali.

(ii) Name the compounds that are formed by heating [(CH3)3NC2H5]+ OH + and[(CH3)4N] OH

SOLUTIONS

Exercise 2:

It can attack from two sites either from oxygen or from nitrogen.

Exercise 3:

n-propyl amine form H-bonding hence has higher boiling point.

Reproduction Exercise 4: CH3CHO + NH2OH > CH3CH = NOH > CH3 CH2NH2

Exercise 5: In acetamide or acetanilide electron withdrawing group (CH3CO) decrease the electron density on nitrogen hence decrease the basicity of compound.

Exercise 6:

H2SO4 works as acid and protonates HNO3 to produce NO2+ ion.

Exercise 7:

Exercise 8:

(a) CH3CH2CN + 2H2O Propanoic acid

> CH3CH2COOH + NH3

OH (b) CH 3CN + H2O H2 O 2 > CH3CONH2 Ethanamide

dil. HCl (c) C2H5NO2 + H2O > CH3COOH + NH2OH

Exercise 9. Hydroxylamine on warming with ammonical silver nitrate solution (Tollen s reagent) gets oxidized to nitroso compound and reduces Tollen s reagent to metallic silver. This reaction is a test for nitro compounds and is known as Baker Milliken s test.

LiAlH4 / ether CH3CH2 NO2 > CH3CH2NH2 1o amine

Exercise 10: (i) CH3CH2NHCH3 (ii) (CH3)3N.C2H4 and (CH3)3N.CH3OH respectively.

Carbohydrate

Exercise 1:

Explain the terms anomers and epimers taking example from carbohydrate chemistry. - and - glucose present in the equilibrium mixture having

Exercise 2: Calculate the percentage composition of rotation of +52.7. Exercise 3:

Write the structure of alanine or CH3CH(NH2)COOH as it would exist in strongly basic solution.

Exercise 4: Write eqilibria showing the amphoteric behaviour of a water solution of glycine. All monoaminomonocarboxylic acids are slightly acidic. Exercise 5: How can lysine and glycine be separated from each other? The isoelectric points are pH 9.6 for lysine and pH 5.97 for glycine? Exercise 6: An electric current is passed through an aqueous solution of mixture of alanine (isoelectric point 6.0), glutamic acid (3.2) and arganine (10.7) buffered at pH= 6. What is the fate of the three acid?

Exercise 7:

Identify A, B, C..

Exercise 8. If one strand of a DNA has the sequence -AATCGTAGGCAC-.What is the sequence of complementary strand.

Exercise 9. Match items in list I with those in the list II form the combinations shown

List I (i) Pepsin (ii) Nucleic acid (iii) Ascorbic acid (iv) Testosterone

List II (A) Genetic material (B) Digestive enzyme (C) Antibiotic (D) Sex hormone (E) Vitamin

Exercise 10.

Two samples of DNA, A and B have melting temperatures 320 and 330 K respectively. can you draw

any conclusion from these data regarding their base content ?

Answers

Exercise 1: Epimers are those isomers which differ in configuration about a single chiral (asymmetric) centre in molecules containing more than one chiral centre. For example, glucose and mannose (both aldohexoses) are epimers to each other as they differ in the configuration of only C2. Anomers are epimers in which the chiral site was formely a carbonyl carbon. Thus - and - methyl glucosides are anomers to each other. Similarly, - and - methyl fructosides are also anomers.

Exercise 2: Let a and b the mole fraction of a - and b - glucose respectively at equilibrium. Then a+b=1 (i) However, we know that the specific rations of a - and b - glucose are +112 and +19 respectively. Thus if the specific rotation of the equilibrium mixture is +52. 7. Then at equilibrium

112a + 19b = 52.7 (ii) From equation (i), b = 1 a Putting the value of b in equation (ii) 112a + 19 (1 a) = 52.7 On solving a = 0.362 or 36.2% b = 0.638 or 63.8%

Exercise 3

Since the solution is acidic the reaction to the right is favoured hence the anion predominates.

Exercise 5: An aqueous solution of the mixture is placed between two electrodes. The pH is adjusted to either 9.6 or 5.97, and an electric current is passed. At pH 9.6 lysine does not migrate, while anionic glycine migrates to the anode, where it is colloide. At pH=5.97, glycine does not migrate while cationic lysine migrates to the cathode. Exercise 6: At pH 6 glutamic acid is present as an anion and migrates to the anode. Arganine is present as a cation and migrates to the cathode. Alanine is dipolar ion remains uniformlly distributed in solution. Exercise 7:

Exercise 8.

TTAGCATCCGTG

Exercise 9. pepsin is a diagestic enzyme, nucleic acid is genetic material, ascorbic acid is vitamin C and testosterone is sex hormone. Exercise 10. C.G base pair has 3 hydrogen bonds and AT base pair has two H bonds, therefore, CG base pair is more stable than AT base pair. Since sample B has higher melting point than sample A, therefore sample B has higher CG content as compared to sample A

PHENOLS 1.Which is the stronger acid in each of the following pair? Explain your reasoning. (a) Phenol or p-hydroxybenzaldehyde Solution (a) The best approach when comparing the acidities of different phenols is to assess opportunities for stabilization of negative charge in their anions. Electron delocalization in the anion of p-hydroxybenzaldehyde is very effective because of conjugation with the formyl group. A formyl substituent, like a nitro group, is strongly electron-withdrawing and acidstrengthening, especially when ortho or para to the hydroxyl group. p-Hydroxybenzaldehyde, with a Ka of 2.4 108, is a stronger acid than phenol question 2 Write chemical equations expressing each of the following: (a) Preparation of o-nitrophenyl acetate by sulfuric acid catalysis of the reaction between a phenol and a carboxylic acid anhydride Solution: (a) The problem specifies that an acid anhydride be used; therefore, use acetic anhydride to prepare the acetate ester of o-nitrophenol Q3.

.In the following reaction identify the product in each case.

(a) 3-Benzyl-2,6-dimethylphenol treated with bromine in chloroform. Sol: 3-Benzyl-4-bromo-2,6-dim ethylphenol (isolated in 100% yield)
Q4.Why o-nitrophenol has lower boiling point than its m and para counterpart? Sol: Chelation Q5. Synthesise Benzene from I)catechol and 2)picric acid? Sol1) Use H2S2O7 and then NaOH fusion. 2)Cl2, Hno3.. Q6.Why does aq NaHCO3 dissolves RCOOH but not phenol? Sol:Acid base equilibria lie towards weak acid and weak base. Q7.What is the effect of electron withdrawing group on Phenol? SOL:Disperse negative charge and stabilize phenoxide ion. Q8.Which is more acidic Alcohol or phenol? Sol: Phenol due to resonance. Q9. how to prepare Phenol from chlorobenzene? Sol: NaOH, BENZYNE formation. Q10;How will you prepare phenol from cumene? Sol: O2 and Acid.

AMINO ACIDS

1.

The Strecker synthesis of amino acids involves treating aldehydes with a mixture of NH 4Cl and KCN followed by hydrolysis. The first step involves a nucleophilic attack by NH 3. a. If ethanal is the starting material, what is the structure of the compound formed after ethanal reacts with the NH 4Cl/KCN mixture? Write mechanisms for the reactions which lead to the formation of this compound.

b.

2.

Amino acid analysis of angiotensin II, a blood-pressure-regulating hormone in blood plasma, shows the composition: Arg, Asp, His, Ile, Phe, Pro,Tyr, Val. An N-terminal analysis using the Sanger or Edman methods shows that the N-terminal residue is aspartic acid. Using carboxypeptidase, the C-terminal residue is found to be phenylalanine. Partial hydrolysis of angiotensin II with dilute HCl yields the following fragments: Ile, Tyr, Val Arg, Asp, Val Phe, Pro His, Ile, Pro Arg, Tyr, Val Propose a structure for angiotensin II.

Asp-Arg-Val-Tyr-Ile-His-Pro-Phe

3.

Betaine, C5H11O2N, occurs in beet sugar molasses. It is a water-soluble solid that melts with decomposition at 300C. It is unaffected by base but reacts with HCl to form a crystalline product, C5H12O2NCl. It can be made in either of two ways: treatment of glycine with methyl iodide, or treatment of chloroacetic acid with trimethylamine. Draw a structure for betaine that accounts for its properties.

4.

A hexapeptide with the composition Arg, Gly, Leu and 3 Pro residues is found to have proline at both the Cand N- terminal positions. Partial hydrolysis gives the following peptides: Gly-Pro-Arg, Arg-Pro, and Pro-LeuGly. What is the structure of the hexapeptide?

Pro-Leu-Gly-Pro-Arg-Pro

5.

The isoelectric point of alanine is 6.0. Draw the structure of its predominant form when present in a buffer of pH 7.0.

6.

Of the 20 L-amino acid structures presented in this course, only cysteine has an R configuration. Why?

NH2 has 1st priority then CH2SH as S has higher atomic number than O 7. A mixture of the following three peptides , Gly-Lys, Gly-Asp, and Gly-Ala, is spotted on a strip of paper which is moistened by an aqueous buffer solution of pH 6.0. The left side of the paper is attached to the positive electrodes in an electrophoresis experiment (and the right to the negative electrode). After applying a potential and allowing a time period, one spot is near the positive electrode, another is close to the negative electrode and the other hasnt moved. Locate each peptide.

Principal forms at pH 6:

Lysine alanine aspartic acid Gly-Lys moves to negative electrode, Gly-Ala doesnt move, Gly-Asp moves to positive electrode

8.

Propose a synthesis of phenylalanine from benzene.

Q. 9 Explain Gabriel Pthalamide synthesis for the preparation of GLYCINE?

SOL:

10: What are Essential and non essential Amino acids? Sol: Essential Amino acids must be supplied to our diet as are not synthesized in body while non essential amino acids are synthesised in our body.