Surfactant Surface Active agent (compound)

Surface or Interface : The border between two materials

• extremity thin layer = very small amount (nano world)
• controlled by surface tension (surface free energy)

Determine the looks of materials

some properties

for example Gold

Iron plating Looks Gold
Strong as Iron

Modification of just surface make the material more worthful.

Surfactant
Molecular Structure of Surfactant

Lipophile repulsive
(Alkyl chain) to H2O
strange structure
connected with
no affinity
covalent bond versatile
Hydrophile attractive
function
to H2O
Polarized
group
 Molecular Assembly of Surfactant
(decrease surface tension)

air
Lipophile pushed out surface absorbtion
(Alkyl chain) from H2O
repulsive
to H2O Balance water
aggregation
Hydrophile dissolved in H2O
attractive into H2O
to H2O

Micelle
Hydrophile-Lipophile Balance
HLB
 Surface Properties of Surfactant
Surface tension - concentration Solubility - temperature
of H2O solution of H2O solution

72 mN/m (pure H 2O)

surface tension

solubility

(mol/L)
 cmc
(mN/m)

cmc concentration (mol/L) Kp temperature (°C)

• Critical Micelle Concentration (cmc, mol/L) • Krafft point (Kp, °C)

= minimum concentration of surfactant
Solubility at Kp goes up to cmc
for formation of micelle
• Surface Tension at cmc (cmc, mN/m)
Over cmc, surface tension was kept constant value
 Structural Factor of Gemini
• Alkyl chain length (Lipophilicity)
• Kind of hydrophile (Hydrophilicity)

Lipophile
• Symmetry
Spacer (same or different length of 2 lipophiles)
connecting • Stereochemistry at connecting point
point (syn- /anti- isomer, optical isomer)
Hydrophile
• Spacer length
Gemini • Kind of spacer

Chemical Structure vs. Surface Properties

Relationship
 Synthetic Strategy of Gemini
Strategy 1; Connection of Conventional Strategy 2; Synthetic Block

Lipophile
(spacer)
Functional
group for Hydrophile
connecting

Conventional Gemini Synthetic Gemini

block
• Malonic Gemini • Tartaric Gemini
• Gemsurf®
 Synthetic Strategy for Malonic Gemini
Malonate
H
H H
Base
- CnH2n+1 Br
H CnH2n+1
C C C
EtO C C OEt EtO C C OEt EtO C C OEt
Alkylation
O O O O O O
enolate Malonic ester synthesis
H H
R–Br Br-(CH 2) n-Br
Lipophile Spacer
Malonic Gemini
R R R R R R
hydrolysis decarboxylation
EtO2C C (CH2)n C CO2Et C (CH2)n C HC (CH2)n CH
HO2C CO2H
CO2Et CO2Et CO2H CO2H HO2C CO2H

2/4 Gemini 2/2 Gemini

feature
• No hetero atom at connecting point
• Several length of lipophile and space are available in large scale
 Preparetion of Malonic Gemini
H H i, NaOEt (fresh prepared) H R
in EtOH i, NaH in THF
C C
EtO C C OEt EtO C C OEt
ii, R-Br ii, Br-(CH2)s-Br
O O O O
Diethyl malonate 60-70 % yields

R R R R
aq-KOH in EtOH
EtO2C C (CH2)s C CO2Et C (CH2)n C
CO2H
2/4 Gemini
HO2C
CO2Et CO2Et CO2H CO2H
50-80 % yields > 85 % yields

R R
AcOH, reflux
HC (CH2)n CH 2/2 Gemini
HO2C CO2H
65-95 % yields
R- = CnH2n+1-
 Synthetic Strategy for Tartaric Gemini
Tartaric acid Lipophile
O-Alkylation
RO-
HO OH

HO2C CO2H
Ammonium
–CH2 N Me3 X -
+

Interconversion Carboxylate * *
- +
–CO2 Na
Polyethylene glycol
–CO(OCH2CH2 )n-OH optically
Hydrophile active
Gemini
feature R- = C nH2n+1-
• L-, D-, and meso-Tartaric acid is commercially available.
• Cationic, anionic, and nonionic Gemini were prepared.
 Preparetion of Tartaric Gemini
O O
R-Br, LiOH•H2O
HO C-NMe2 in DMSO at 60°C
RO C-NMe2
HO C-NMe2 ca. 90 % yields RO C-NMe2
O O
Tetramethyltartaramide
CH3Br
LiAlH4 in THF RO CH 2NMe2 in CH3CN RO CH 2N+Me3 cationic
Š
2Br Gemini
RO CH 2NMe2 RO CH 2N+Me3
aq-KOH
BuOH, p-TsOH RO CO2Bu in EtOH RO CO2H anionic
at 120°C
RO CO2Bu RO CO2H Gemini

H-(OCH2CH2)3-OH, p-TsOH RO CO(OCH2CH 2)3-OH

nonionic
at 120°C RO CO(OCH2CH 2)3-OH Gemini
R- = CnH2n+1-
 ®
Synthetic Strategy for Gemsurf
O Esterification O Oxidation O
R-OH / H+ R-O C KMnO4 RŠO C CO2H
O
(– H2O) CO2H
R-O C RŠO C
O O O
Tetrahydrophthalic Gemsurf®
anhydride not isolated
>80% overall yield
R- = C nH2n+1-

feature
• 2 steps and one-pot synthesis
• Unexpensive starting materials and reagents
Large scale Commercially available Gemini
preparation
Relationship between structure / surface properties
Significant factor
• Diastereo-isomerism : Big difference between meso- vs. dl- isomer
• Structural difference near connecting point

Less effective factor

• Optical-isomerism : Few difference between L- vs. D- isomer
• Equal length of 2 lipophile (symmetry)
: Gemsurf with12+12, 14+10, and 16+8 alkyl chains
are almost same properties
• Space length : small differences

Strong influence
of intramolecular lipophile interaction (hydrohobic)