Sulfur&PhosphorusCompounds.ppt untuk perkimiawian

Ilmu kimia

1. MEDC 527 Fall 2008 1
OrganoSulfur Compounds
Sulfur (S)
S and O :: atomically similar
Sulfur also intimately involved in biological processes
Sulfur forms two bonds in a manner similar to O
But sulfur may form more because of the presence of d-orbitals, e.g.,
–S(O)– and –S(O
2
)–

2. MEDC 527 Fall 2008 2
HSH HOH
RSH ROH
RSR' ROR'
RSSR' ROOR'
R
S
OH
R
O
OH
R
S
SH
R
O
OH
RS
R
R
RO
R
R
Hydrogen sulfide water
Thioalcohol (mercaptans)
Thioethers(sulfides)
Disulfides
Thioacids
Dithioacids
Sulfonium ion Oxonium ion++
OrganoSulfur Compounds
RS
O
R'
RS
O
R'
O
RS
O
OH
RS
O
OH
O
ROS
O
OH
O
Sulfoxides (OS = +4)
Sulfones (OS = +6)
Sulfinic Acids (OS = +4)
SulfonicAcids (OS = +6)
Sulfates (OS = +6)
Sulfur compounds that have an O analog … without O analog

3. MEDC 527 Fall 2008 3
OrganoSulfur Compounds
S
S
Indene 1-thiaindene
Cyclohexane Thiocyclohexane
Nomenclature
Thiols: CH
3
SH methane thiol or methylmercaptan or mercaptomethane
PhSH benzene thiol or phenylmercaptan or mercapto benzene
Sulfoxides and Sulfones CH
3
S(O)CH
2
CH
3
methyl ethyl sulfoxide
CH
3S(O
2)CH
2CH
3 methyl ethyl sulfone

4. MEDC 527 Fall 2008 4
OrganoSulfur Compounds
+
H
3
NCH(COO
-
)CH
2
CH
2
CONHCH(CH
2
SH)CONHCH
2
COO
-
or
+
H
3
NCH(COO
-
)CH
2
CH
2
CO-CYS-GLY
• Common and Important Sulfur Compounds
— Glutathione
Involved in a variety of detoxification, transport and metabolic
processes
Substrate for peroxidase reactions
Maintains balance of sulfhydryl groups (-SH of Cys) in proteins
O
H
HH
OHOH
O
N
N
N
N
NH
2
PPO
O
O
O
O
CH
3
CH
3
OH
O
N
H
N
O
H
SH
Coenzyme A (CoASH)
— Coenzyme A
Plays a major role in the biosynthesis and metabolism of a
number of important molecules, including fatty acids

5. MEDC 527 Fall 2008 5
OrganoSulfur Compounds
O
H
HH
OHOH
S
N
N
N
N
NH
2
CH
3
NH
2
HOOC
SAM
++
• Common and Important Sulfur Compounds
— S-Adenosylmethionine
— Heparin, Heparan Sulfate, Chondroitin Sulfate …
Glycosaminoglycans have numerous physiological roles
Plays a major role in the methyl
transfer reactions, e.g. onto
phenolic groups or DNA …
O
OH
OH
O
COO
O
O
CH
2
OH
NHSO
3
OH
O
O
CH
2
OSO
3
NHCOCH
3
OH
O
OH
OH
O
COO
O
O
CH
2
OSO
3
NHSO
3
OH
O
OSO
3
OH
O
COO
O
O
CH
2
OSO
3
NHSO
3
OH
_
_
_
_
_
_
_
_ _
_

6. MEDC 527 Fall 2008 6
Heterocycles Containing Sulfur
 Basic Ring Systems
N
S
S
S
T e t r a h y d r o t h i o p h e n e
(t h i o la n e)
T h io p h e n e
(T h i o l e)
1 , 3-t h i a z o l e
S
N N
N
CH
3
CH
3
S
N N
N
CH
3
CH
3
methapyrilene
N
S
N
NH
O
NH
2
OMe
S
O
COOH
ceftizoxime
S
N
NH
2
S
OO
NH
2
thiazolsulfone
 Examples in Drugs
(Antihistamine) (Antibiotic) (Antimalarial)

7. MEDC 527 Fall 2008 7
OrganoPhosphorus Compounds
Phosphorus (P)
N and P :: atomically similar
Phosphorus is an important part of most important biological
materials, DNA, RNA, ATP, …
Phosphorus forms three bonds like N
But P may form more because of d-orbitals

8. MEDC 527 Fall 2008 8
OrganoPhosphorus Compounds
R
P
R
R
R
P
R
R
R
N
R
R
R
N
R
R
H C l
H C l
..
..
++
++
C l
C l
--
--
R
P
R
R
R
P
R
R
CH
3
R
N
R
R
R
N
R
R
CH
3
CH
3
I
CH
3
I
..
..
++
++
I
I
--
--
R
P
R
R
R
P
R
R
R
N
R
R
R
N
R
R
H
2
O
2
H
2
O
2
..
..
O
O
Comparison of reactions of P and N
….in acidification …. in quaternary salt formation ….in oxidation
•Differences
•Maximum # bonds with N = 4; it is 5 or 6 with P depending on the number of d-
orbitals involved
•P does not form many unsaturated compounds because of poor p-p overlap, e.g, no –
P=P- known (diazo are known); nor are phosphorus analogs of nitriles or amides
•Few unsaturated P compounds known, nearly all have P=O (double bond with
oxygen)
•P does not give stable aromatic compounds, e.g., no phosphorus analog of pyrrole or
pyridine is known
•Similarities

9. MEDC 527 Fall 2008 9
OrganoPhosphorus Compounds
Phosphate buffer
OHPOH
OH
O
OHPO
OH
O
OHPO
O
O
OPO
O
O
pK
A
=2.15 pK
A
=7.20 pK
A
=12.38
--
--
-- --
--
--
N
N
N
N
O
OCH
2
H
HH
OH
O
PO
O
O
O
C
H
2
H
HH
OH
O
NH
N
O
O
-
Adenine
Uracil
1’
2’
3’
4’
5’
1’
3’
5’
N
N
N
N
O
OCH
2
H
HH
OH
O
PO
O
O
O
C
H
2
H
HH
OH
O
NH
N
O
O
--
Adenine
Uracil
1’
2’
3’
4’
5’
1’
3’
5’
RNA
N
N
N
N
O
C
H
2
H
HH
OHOH
OPO
O
O
P
O
O
OP
O
O
O
--
-- -- --
ATP