전단원 요약정리

전단원 요약정리

Soonchunhyang University

Department of Chemical Engineering Prof. Jungkyun Im

순천향대 나노화학공학과

임 정 균 교수

생유기화학

(Bioorganic Chemistry)

Free-Radical Chain-Growth Polymerization

In CH₂ CH X

In CH₂ CH X Initiation:

Propagation: In CH₂ CH X

CH₂ CHX

In CH₂CH CH₂ CH

X X

CH₂ CHX

etc.

Termination: HC X

+ CH

X (radical coupling) HC

X CH X

C H₂ HC

X

+ CH X

CH₂

disproportionation

CH₂ + CH X C

X

CH

Chain Transfer (Hydrogen Abstraction)

HC X

+ C

X H

C H₂

X

+ C

X Synthetic Polymer

Cationic Chain-Growth Polymerization

and so on R⁺ + H₂C CH

X

CH₂

R CH

X +

C H₂ CH

X

Anionic Chain-Growth Polymerization

and so on R^– + H₂C CH

X

CH₂

R CH

X

–

C H₂ CH

X

Step-Growth Polymerization (illustrated for polyesters)

HO C O

C O

OH

O H₂ –

HO O C

O

C O

OH from diol from diacid

(two units) +

HO OH

HO O C

O

C O

OH

HO C O

C O

OH or

HO OH

four units three units

Synthetic Polymer

Saponification of a Triglyceride

C

H₂ O C R O

C

H O C R O

C

H₂ O C R O

+ 3 NaOH

C H₂ O

C

H O

C H₂ O

+ 3 Na⁺ O C R O

–

H H H

Hydrogenation of a Triglyceride (Hardening)

C

H₂ O C O

C

H O C

O

C

H₂ O C O

CH₂

( )_nCH CH CH( ₂)_mCH₃

CH₂

( )_nCH CH CH( ₂)_mCH₃

CH₂

( )_nCH CH CH( ₂)_mCH₃

H₂ 3 Ni, heat

C

H₂ O C O

C

H O C

O

C

H₂ O C O

CH₂

( )_nCH₂CH₂(CH₂)_mCH₃

CH₂

( )_nCH₂CH₂(CH₂)_mCH₃

CH₂

( )_nCH₂CH₂(CH₂)_mCH₃

Lipid and detergent

Hydrogenolysis of a Triglyceride

H₂ 6

zinc chromite C

H₂ O C O

C

H O C

O

C

H₂ O C O

R

R

R

C H₂ O

C

H O

C H₂ O

+ HOH₂C R H

H H

1.

Know the meaning of: triglyceride, fatty acid, fat, oil, hardening of a vegetable oil, hydrogenolysis, soap, saponification.

Know the structures and common names of the acids listed in Table 15.1.

Given the name of a glyceride, write its structure.

4.

Given the name or structure of a carboxylic acid, write the formula for the corresponding glyceride.

요점 사항 Lipid and detergent

CH₂ HO

CH OH CH

CH CH

CH O HO

O

H OH

acyclic (aldehyde)

CH₂ HO

CH O CH

CH CH CH HO

O

H OH

cyclic (hemiacetal) OH

anomeric carbon

CH O CHOH) CH₂OH

( _n

aldose

H₂O Br₂,

or

Ag⁺or Cu²⁺

CO CHOH) CH₂OH

( _n

aldonic acid

2H

CH O CHOH) CH₂OH

( _n

aldose

HNO₃ CO CHOH)

( _n

aldaric acid

2H

CO₂H Acyclic ad Cyclic Equilibration

Oxidaton

polysaccharide

oligosaccharide

monosaccharide

Hydrolysis

Carbohydrate

Reduction

CH O CHOH) CH₂OH

( _n

aldose

H₂, catalyst

or CHOH)

CH₂OH

( _n

alditol NaBH₄

CH₂OH

Esterification and Etherification

Ac₂O OH

H OH

H H

OH H

HO OH₂C H

O

Ac = CH₃C O

OAc

H OAc

H H

H AcO

OH₂C Ac

O OAc

OH

H OH

H H

OH H

HO OH₂C H

O NaOH,(CH₃)₂SO₄

or CH₃ I, Ag₂O

O

H O

H H

O H OH₂C

O CH₃O

CH₃

CH₃

CH₃ CH₃

Formation of Glycosides

OH

H OH

H H

OH H

HO OH₂C H

O

H⁺ ROH

OH

H OH

H H

OR H

HO OH₂C H

O

+ H₂O

Carbohydrate

H

C CO₂H NH₃ + R

HO^–

H⁺

H C CO₂ NH₃ +

R ^–

HO^–

H⁺

H C CO₂ NH₂

R ^–

dipolar ion

H C CO₂ NH₃

R ^–

+

+ R'OH + H⁺

H

C CO₂ R' NH₃ +

R + H₂O

O H₂ H

C CO₂ NH3

R ^–

+

+ R' C Cl O

HO^– 2

C R'

O NH H C CO₂

R ^–

+ 2 + Cl^– Dissociation of Amino Acids

Esterification

Acylation

Ninhydrin Reaction

N O

O OH

OH +

H C CO₂ NH₃

R ^–

+ 2

O

O

O

O

+ RCHO + CO₂ + 3H₂O + H⁺

–

Amino acid, peptide, protein

H

C CO₂ NH₂

R H

base

H

C CO₂ NH

R H

NO₂

NO₂

+ F^– F

NO₂

NO₂

+

N C S + H₂N H C R

C O

N H

N H

C S

N H

C R H

C O

N

H H₂O

HCl

S

O N

NH

C H

R

+ H₂N

= peptide chain Sanger’s Reagent

Edman Degradation

Amino acid, peptide, protein

(CH₃)₃CO C O O

C O

OC(CH₃)₃ + H₃N R C H

1

CO₂^– base

di- t -butyl dicarbonate

(CH₃)₃CO C O

NH R C H

1

CO₂^–

BOC or P

P NH

R C H

1

CO2

– + Cl CH2

뺺l^–

P NH

R C H

1

C O

O CH₂

= polymer

(CH₃)₃CO C O

NH R C H

1

C O

O CH₂

HCl

CH₃CO₂H

N H₂

R C H

1

C O

O CH₂ + CO₂ + (CH₃)₂C CH₂ Peptide Synthesis

a. N-protection:

b. Polymer attachment:

c. Deprotection (removal of the protecting group):

Amino acid, peptide, protein

H O

H H

O

O P O

O

–O

N

H

Base H₂O enzyme

H O

O

N

H

Base

H O

H O

O

N

H

Base H₂O

H

HO^– O

P O

–O

–

nucleotide

DNA segment

H O

H O

N

H

Base HO

nucleoside

H H O

H O

H HO

2-deoxy-D-ribose H O

+ HN-Base

H₂O H⁺

heterocyclic base

Hydrolysis of Nucleic Acids

Nucleic acid

1. Know the meaning of: nucleic acid, nucleotide, nucleoside.

2. Know the structures of: cytosine, thymine, adenine, guanine, uracil, 2-deoxy-D-ribose, D-ribose.

3. Know the meaning of: DNA, RNA, N-glycoside, pyrimidine base, purine base.

4. Given the name, draw the structure of a specific nucleoside.

5. Write an equation for the hydrolysis of a specific nucleoside by aqueous acid. Write the steps in the reaction mechanism.

6. Given the name, draw the structure of a specific nucleotide.

7. Write an equation for the hydrolysis of a specific nucleotide by aqueous base.

8. Draw the structure of an N-glycoside and an O-glycoside.

9. Given the name or abbreviation for a DNA or RNA nucleotide or nucleoside, draw its structure.

10. Draw the primary structure of a segment of an RNA or DNA chain.

11. Explain why only pyrimidine-purine base pairing is permissible in the double helix structure.

12. Describe the main features of the secondary structure of DNA.

13. Explain, with the aid of structures, the role of hydrogen bonding in nucleic acid structures.

14. Describe the main features of DNA replication.

15. Given the base sequence in one strand of a DNA molecule, write the base sequence in the other strand, or in the derived mRNA. Conversely, given a base sequence for mRNA, write the base sequence in one strand of the corresponding DNA.

16. Given a synthetic polyribonucleotide and the peptide sequence in the resulting polypeptide, deduce the codons for the amino acids.

17. Describe the main features of protein biosynthesis.

18. Explain the different functions of messenger, ribosomal, and transfer RNA.

19. Know the meaning of: codon, anticodon, genetic code, transcription, polymerase chain reaction.

요점 사항