Organic Chemistry for Cosmetic Chemists

Organic Chemistry for Cosmetic Chemists
Tony O’Lenick Thomas O’Lenick, PhD October 2015

Organic Chemistry Organic Chemistry however has profound effects upon our formulations. This becomes clear when a formulator tries to substitute one raw material for another. Armed with only INCI names this can be a best a frustration or at worst a complete failure. Why is this the case?

Organic Chemistry Why is this the case?
Many of our raw materials come from different raw material bases and despite common names are not identical. Many manufacturers use different processes to make their products. These differing processes result in different % conversion, by products and un-reacted raw materials. Many manufacturers use processing aides, and other additives.

Back the the Basics Before we dive into Organic chemistry or more commonly called O-Chem we need the basics First off

Back the the Basics How do we draw Chemical Structures
Hydrocarbons- All Carbon and Hydrogens Alkanes Alkenes Alkynes Cyclic Aromatic Compounds CH3CH2CH3

Organic Chemistry Structures and Naming

Hydrocarbon Hydrocarbons are organic compounds that are composed of carbon and hydrogen. To start the naming process we need to start with the simplest form. Compounds with all single Carbon-Carbon bonds. Hydrocarbons are named by identification of the longest continuous carbon chain. They are named by the number of carbons in that chain followed the suffix “-ane”

Hydrocarbons Now come the memorization part… The prefixes… Number
of Carbons Name Molecular Formula Structural Formula 1 Methane CH4 - 2 Ethane C2H6 CH3CH3 3 Propane C3H8 CH3CH2CH3 4 Butane C4H10 CH3(CH2)2CH3 5 Pentane C5H12 CH3(CH2)3CH3 6 Hexane C6H14 CH3(CH2)4CH3 7 Heptane C7H16 CH3(CH2)5CH3 8 Octane C8H18 CH3(CH2)6CH3 9 Nonane C9H20 CH3(CH2)7CH3 10 Decane C10H22 CH3(CH2)8CH3 Now come the memorization part… The prefixes…

Isomers What are isomers? Example
When you have two or more chemical structures that have the same molecular formula but different structures. Example How many Isomers of pentane (C5H12) can you draw? 1 Pentane 2 2-Methyl Butane 3 2,2-Dimethyl Propane

Branching? When a carbon chain is handing off of the carbon chain but is not part of the primary carbon chain, you name the number of carbons, but add a –yl at the end. 4-Ethyl 3-Methyl Heptane 3-Methyl 4-Propyl Octane 3-Methyl Heptane Heptane

Cyclic Alkanes CycloPentane Pentane C5H10 What about?
2 1 3 CycloPentane Pentane 5 4 C5H10 No it is not an isomer. It has 2 fewer hydrogens. Cyclic compounds have the same type naming but the word Cyclo-

Alkenes What about hydrocarbons with Double Bonds?

Hydrocarbons Alkenes are:
Compounds with at least one Carbon-Carbon double bond. Name them the same way you name alkanes, except: You have to identify where the double bond is Drop the –ane and replace it with –ene. Number of Carbons Name Molecular Formula Structural Formula 2 Ethene C2H4 CH2=CH2 3 Propene C3H6 CH3CH=CH2

Alkenes trans 2-Pentene Pentene 2-Pentene Pentane cis 2-Pentene

Cyclic –enes? 3-Methyl cyclopentene CycloPentane CycloPentene

Alkynes Alkynes are: Name them the same way you name alkanes, except:
Compounds with at least one Carbon-Carbon triple bond. Name them the same way you name alkanes, except: You have to identify where the double bond is Drop the –ane and replace it with –yne. Number of Carbons Name Molecular Formula Structural Formula 2 Ethyne C2H2 CHCH 3 Propyne C3H6 CH3CCH

Alkynes No Cis and Trans There are a limited number of cyclics.
Pentyne 2-Pentyne Pentane No Cis and Trans There are a limited number of cyclics.

Alkenes to Alkanes Hydrogenation involves hydrogen gas and a metal

Conjugation Conjugation as we have seen, leads to stability and if the conditions are correct, aromatic compounds. There is another added benefit that we see a lot in cosmetic chemistry….Absorption Before we discuss how conjugation, lets briefly discuss absorption in organic molecules.

Resonance Lets review Alkenes Now we have a diene.
When dienes are on adjacent carbons, they can have resonance with each other. + −

So….what does that really mean?
Aromatic Compounds Aromatic Compounds, also known as arenes or aromatics, are chemical compounds that contain conjugated planar ring systems with delocalized π electron clouds instead of discrete alternating single and double bonds. Typical aromatic compounds are benzene and toluene. They should satisfy Hückel’s rule.1 So….what does that really mean? 1.

Aromatic Compounds http://en.wikipedia.org/wiki/Ouroboros

Benzene

Absorption of Organic Molecules
Absorption can provide information about organic materials. There are 2 important absorptions Infrared UV-Vis Tells us what kind of bonds are involved.

Conjugation’s effect on Absorption
UV light has just the right amount of energy to cause an electronic transition. It is the energy gap that determines what wavelength is absorbed.

HOMO and LUMO π* π* π π O H3C CH3 O H3C CH CH2

Organic Filters s Avobenzone Homosalate Octocrylene

Not just for drinking anymore…
Alcohol Not just for drinking anymore…

Alcohol Alcohols are named by the functional hydoxyl group.
Alcohols can be branched or linear. Oxygen prefers to have 2 bonds, so they are classified according to what they are connected to.

Alcohols Primary CH3CH2OH Secondary CH3CH(CH3)OH Tertiary (CH3)3COH OH
1 2 1 OH 3 2 OH 1

The original nitrogen…
Amines The original nitrogen…

Amines Amines are named based on this functional group.
-NHx Nitrogen likes to make 3 bonds They are named based on how many non-hydrogen atoms are bonded to the Nitrogen. CH3 + CH3NH2 CH3 NH CH3 CH3 N CH3 H Primary Amine Secondary Amine Tertiary Amine

Ethers Ethers are named based on this functional group.
R1-O-R2 Oxygen likes to have 2 bonds, so ethers are typically non- reactive They are named by their alkyl chains. CH3 O CH3 CH3 O CH2CH3 Dimethyl ether Methyl Ethyl ether

Carbonyl Group The gateway drug…

Carbonyl Group There is a large subsection of functional groups that are based on the Carbonyl group. The carbonyl groups is R2C=O The functional group is then based on what R is. The Carbon in the Carbonyl is reactive and is very important in Organic synthesis.

Aldehyde Aldehyde is conforms to the following structure.
They are named by their parent alkyl chain, but drop the –e and replace it with –al. O H O O H H CH3 H Methanal (Formaldehyde) Ethanal

Ketones A ketone where the R group(s) are carbons.
They are named by their parent alkyl chain, but drop the –e and replace it with –one. O R2 R1 O O H3C CH3 CH3CH2CH2 CH2CH3 Dimethyl Keytone (Acetone) 3-Hexanone

Carboxylic Acid An Acid is a carboxyl with a C(O)OH.
They are named by their parent alkyl chain, but drop the –e and replace it with –ic acid O R2 OH O O H3C OH CH3CH2CH2 OH Ethanoic Acid (Acetic Acid) Hexonic acid

Esters An Ester is a carboxyl with a C(O)OR.
They are named by their parent alkyl chain with the carbonyl, but drop the –e and replace it with –oate O R2 OR1 O O OCH2CH3 CH3CH2CH2 H3C OCH3 Methyl Ethanoate (Methyl Acetate) Ethyl Butanoate

Anhydrides Anhydrides are compounds that have the following structure.
They are named by their parent alkyl chain with the carbonyl, but drop the –e and replace it with –oic anhydride O O R2 O R1 O O O CH3CH2CH2 O H3C O CH3 O CH2CH3 Ethanoic Anhydride Butanoic Propanoic anhydride

Epoxides, Alkyl Halides and Acyl Halides
Epoxides (oxarines) are 3 membered rings. O H2C CH2 Alkyl Halides CH3CH2-X X = Cl, Br, F, ect. Acyl Halides O R2 X X = Cl, Br, F, ect.

Practice makes perfect…
Problems Practice makes perfect…

Examples Identify the functional group(s): 1 2 3 4 5 6

Some Synthesis Concepts
Umpolung Is a rather obscure German word, it means “Group Reversal”. One of the most dramatic uses of this concept can be seen in the making of esters. Lets do an example…. Lets Draw Stearyl Oleate & Oleyl Stearate

Umpolung Sometimes Cause confusion in using this concept
Lack of availability of technical data; Multiple methods of naming; Different raw materials Cause confusion in using this concept

Melting Point, °C: 42

CAS Melting Point, °C: 43

Analogues and Homologues
A very important concept that one needs to understand the difference between an analogous series and a homologous series Analogous series are those that differ only in the functional group present. So, for example, sodium laureth-2-sulfate and sodium laureth-2-phosphate are two analogues. Their common raw material is lauryl alcohol with two moles of ethylene oxide.

Analogues The substantial difference in properties between these analogues is due only to the different functional groups. Changes within a analogous series generally result in profound differences, including compatibility with other ingredients.

Homologues If one varies the carbon chain in the group, a series of homologues is prepared. Such a homologous pair is sodium lauryl (C12) sulfate and sodium behenyl (C22) sulfate. The differences in the properties of these two surfactants are due to the differing number of carbon atoms in the molecule. Changes within a homologous series generally result in different melt points, foam, viscosity and conditioning effects It is often advantageous to take into account such differences as these in order to select a chemistry that will give the desired property. The process becomes even more complicated when one considers modifications that change both functionality and carbon chain distribution.

Raw Materials

Raw Materials There are many different “chemicals” out there to make products from. Several components go into picking the correct starting materials. Cost Availability Purity Origins of Materials Natural Oils (Triglycerides) Petroleum (Crude Oil) Minerals (Quatz) Methyl Esters Ethylene Propylene Silicon Fatty Alcohols Alpha Olefins Chlorosilanes Fatty Amines Silicone Glycerin Organofunctional

Natural Oils Triglycerides
Petroleum-based Alkanolamide Methyl Ester Acids Alkanes, Alkenes & Alkynes Ether Phosphate Alcohol Ether Sulfate Phosphate Ethoxylates Ether Sulfosuccinate Sulfate Sulfosuccinate Guerbet Alcohols Ether Ester Ether Carboylate Esters Phosphates Sulfates

Natural Oils Triglycerides
Petroleum-based Alkanolamide Methyl Ester Acids Alkanes, Alkenes & Alkynes Alkanolamide Ethoxylated Amines Imidazoline Alcohol Fatty Amine Aminosulfosuccanate Sulfobetaine Amphoterics Phophobetane Betaines Betaines Quats Amphoteric

Triglycerides The oil of nature…

Triglycerides Triglycerides are key raw materials
Triglycerides are the fatty tri-ester of glycerin. O O R O O R1 O R2 O

Triglyceride Typically there are 3 classes of Triglycerides
Why is this important? Class I Products Rich in Components below C18 Class II Products Rich in Unsaturated Components Class III Products Rich in Components with Chain Lengths Higher than C18

Class I Oils

Coconut Oil Source: Coconut oil is the most abundant processed natural oil. Comes from the seeds of the cocs nucifera plant. Is the major source of Lauric Acid (C12) Component Concentration (% wt) C8 8.0 C10 7.0 C12 48.0 C14 19.0 C16 C18 3.0 C18:1 5.0 C18:2 2.0

Class II Oils Unsaturated C18 Triglycerides

Soybean Oil Source: Comes from the soybean glycerin max. Component
Concentration (% wt) C8 - C10 C12 C14 C16 7.0 C18 4.0 C18:1 29.0 C18:2 54.0 C18:3 5.0

Class III Oils

Meadowfoam Oil Source:
Derived from the herbaceous winter plant (limnanthes alba). Component Concentration (% wt) C20:1 (n = 5) 63.0 C20:2 (n = 5.13) 12.0 C22:1 (n = 5) 3.0 C22.1 (n = 13) C22.2 (n = 5.13) 10.0

Carbon-Carbon Bonds? Double bonds or unsaturation tends to:
Turn dark when heated Go rancid over time

Methyl Esters OH O HO OH O R O O R1 O O + 3 CH3OH R2 OCH3 3 x R2 O Methyl esters are made by the reaction of a triglyceride with methanol in the presence of a catalyst. Commercial manufacturing of methyl esters is accomplished by using a continuous hydrogenolysis process. The Methyl ester is separated from the glycerin and distilled to produce narrow fraction products useful as ram materials for the preparation of surfactant products.

Reactions And let the fun begin…

Organic Chemistry There are many reactions involved in organic chemistry…. Instead of memorizing name reaction after name reaction, it is much simpler to breakdown the reactions into simple steps or trends. With the understanding of these trends, we can understand the reaction without memorizing a bunch of reactions.

Reactions Rule number 1 when we start looking at reactions is
ALWAYS PUSH ELECTRONS!!! Reactions always go from atoms with high electron content to electron deficient atoms. The atoms with high electron content are called Nucleophilies. Electron deficient atoms are called electophiles

Typical Nucleophilies
Lone Pair Electrons: O , N, S, Cl, Br, I π-bonds

Nucleophilic Substitution
WE now know what nucleophilic means…

Subsitution Reactions
What is a “Subsitution Reaction”? Simply put a Subsitution reaction is replacing one group with another, or subsituting one group for another. There are 2 basic Subsitution reactions: SN1 SN2 Can be used to make Amids, Esters, Quats, ECT..

Neclophillic Subsitution Reaction SN1
SN1 Reactions are a two step reaction. They are called SN1 because the rate of the reaction is based on the carbocation. rate= k[+] 3o > 2o NO 1o Step 1 Rate Limiting Material Mixture of R and S

Neclophillic Subsitution Reaction SN2
SN2 Reactions are a One step reaction. They are called SN2 because the rate of the reaction is based on the carbocation. rate= k[Starting Material][Nuc] 1o > 2o Typically no 3o Product inversion (R  S)

Elimination Reactions
They go hand and hand with the SNs…

Elimination Reactions
Elimination reactions are just like the SN reactions, except you get a double bond instead of a substitution. Consider the reaction. CH2 CH3 H3C OH H -OH -Br H CH2 H CH2 CH3 H3C + -OH H3C Br CH2 CH3 H3C CH3

E1 Mechanism -OCH3 + -Cl +

Elimination -OCH3 + -Cl

E2 Mechanism

Cl -OCH3 + E1 Cl -OCH3 + E2

Esterification

Esters Esters are an important class of compounds made by nuclephilic substitution. Esters are a diverse class of compounds that have a variety of functional attributes useful to the cosmetic chemist. The functionality is determined by the structure. The ester reaction in simple form.

Neclophillic Subsitution Reaction @ SP2
+ HOR2 + HOH R1 HO OR2 R1 O O + + HOR3 HOR2 R1 OR3 OR2 R1

Esters Reactants Products Structurally,
Acid & Base – High Acid Value & Hydroxyl value. Saponification value is low. Products Acid Value and Hydroxyl value are low Saponification value is High Structurally, Direct esterification Transesterification

Esters Esters can be described by the process used to make them.

Direct Esterification
This Ester is made from an Acid and Alcohol. O OCH2CH3 O CH3(CH2)3 + CH3CH2OH + HOH CH3(CH2)3 HO HO + Isopropyl Palmitate Palmitic Acid Isopropyl Alcohol

Trans-Esterification
This type of ester is made from by reacting an Ester and Alcohol. You always get a mixture of Esters but can separate with packed column. O OCH2CH3 O CH3(CH2)3 + CH3CH2OH + CH3OH CH3(CH2)3 OCH3

This Ester is made from an Triglyceride and Alcohol. CH2OH CH3(CH2)10C(O)OCH | | CHOH CH3(CH2)10C(O)OCH + 3 CH3(CH2)11OH -> CH3(CH2)10C(O)O(CH2)11CH | | CH2OH CH3(CH2)10C(O)OCH2 Triglyceride Alcohol Ester Glycerin

Triglyceride and Alcohol. Esters may also be prepared by the reaction of a triglyceride with a fatty alcohol, releasing glycerin. Glycerin is often removed by allowing it to settle from the ester and decantation. This reaction is generally conducted using acid or metal catalyst.

Question How would an ester made from an acid, in the direct process differ from the same ester made by transesterification using either methyl ester or triglyceride?

Types of Esters The structure of Esters fall into three categories: 1. Simple 2. Complex 3. Polyesters

Simple Ester O CH3(CH2)3 OR1 This type of ester is made from a mono-acid and mono- Alcohol Consider OCH3 O CH3(CH2)8 Name? IUPAC ? INCI?

Simple Ester Raw Materials? Find the weak spot of the molecule
OCH3 O CH3(CH2)8 Raw Materials? Find the weak spot of the molecule Break the molecule and see what it is O CH3(CH2)8 OH OCH3 HOCH3

Complex Esters Complex Esters are made from:
Mono Acids & Poly Alcohols Poly Acids / Mono Alcohols

Complex Esters CH2O | O-CH2-C-CH3 CH3 CH2OH | HO-CH2-C-CH3 CH3 CH2OH |
Neopentyl glycol (NPG) You can have a mono-ester or a di-ester

Complex Esters Trimethylol propane (TMP) 3 hydroxyl groups CH2OH |
CH2OH | HO-CH2-C-CH2CH3

Complex Esters Glycerin 3 hydroxyl groups CH2-OH | CH-OH

Complex Esters Pentaerythritol (PE) 4 hydroxyl groups CH2OH |
CH2OH | HO-CH2-C-CH2-OH

Complex Esters Di-Pentaerythritol (DPE) 6 hydroxyl groups CH2OH CH2OH
CH2OH CH2OH | | HO-CH2-C-CH2-OCH2-C-CH2OH

An Example CH2O OCH2-C-CH2O CH2O Name? Why is the name Laurate? O
(CH2)10CH3 O CH2O CH3(CH2)10 O (CH2)10CH3 O OCH2-C-CH2O (CH2)10CH3 O CH2O Name? Pentaetyrthritol tetralaurate Why is the name Laurate?

Another Example CH2O OCH2-C-CH2OH CH2O Name? O (CH2)10CH3 O CH3(CH2)10
Pentaetyrthritol trilaurate

Question Now for the real question…..
How would you expect the two to function differently in formulations? (CH2)10CH3 O (CH2)10CH3 O CH2O CH3(CH2)10 O CH3(CH2)10 O (CH2)10CH3 O CH2O OCH2-C-CH2OH OCH2-C-CH2O (CH2)10CH3 O (CH2)10CH3 O CH2O CH2O

Problem Lets make 200 g of Lauryl Stearate
O(CH2)11CH3 O CH3(CH2)16 Determine the Formula of the reactants Stearic Acid CH3(CH2)16COOH Lauryl Alcohol CH3(CH2)11OH

Problem O O(CH2)11CH3 O CH3(CH2)16 + HO-(CH2)11CH3 CH3(CH2)16 HO
Write a Balanced Equation O O(CH2)11CH3 O CH3(CH2)16 + HO-(CH2)11CH3 + HOH CH3(CH2)16 HO

Problem Determine MW Reactants Stearic Acid CH3(CH2)16COOH C18H36O2
= 284 Lauryl Alcohol CH3(CH2)11OH C12H24O C12*12 = H24 1*24 = O 1*16= 16 = 184

Problem Determine Mole Ratio and % Material MW MR MCH % Grams
Stearic Acid Lauryl Alcohol Total In theory there will 3.8% Water generated and 96.2 % Ester at 100% Rxn

Amide Amides are an important class of compounds made by nuclephilic substitution. Amides are a diverse class of compounds that have a variety of functional attributes useful to the cosmetic chemist. Alkanolamides are a diverse class of compounds, used commonly in personal care to alter the salt curve of formulation and provide a thickening effect to the formulation The functionality is determined by the structure. The Amide reaction in simple form.

Direct Amidation This Amide is made from an Acid and Amine. O NHCH2CH3
+ CH3CH2NH2 + HOH CH3(CH2)3 HO Reactants Acid Value & Alkali Value are HIGH Products Acid Value & Alkali Value are LOW Saponification Value- Increases

Amide Types Structurally amides fall into two categories based upon alkanolamine type: Monohydroxy -amines (monoethanolamine, monoisopropanolamine) Dihydroxyamines (diethanolamine, diisopropanolamine) There are no amides based upon tertiary amines. Additionally, within each category amides can be classified by the fatty raw materials and can be: Saturated Unsaturated Branched Guerbet

Amide from Methyl Esters
Methyl ester is reacted with ethanolamines, releasing methanol. The use of the methyl ester for amid synthesis offers the most flexibility in obtaining pure carbon numbers in the product. Methyl esters can be fractionated easily and almost any carbon number methyl ester can be used to make unique products. Methanol is removed by distillation leaving behind the amid. This reaction is generally conducted using base catalyst. Methanol, a flammable liquid, must be efficiently removed to obtain a high purity product. Air must be excluded to prevent color formation.

Direct Amidation This Amide made from an Ester and Amine. O NHCH2CH3 O
+ CH3CH2NH2 + HOCH3 CH3(CH2)10 OCH3 Methyl Laurate Ethylamine N-Ethyl Lauramide Methanol

Specifications Amine Value – Amine value is a measure of the unreacted amine content. It will drop as the reaction proceeds. GLC- The ratio of carbon distribution of the amid can be determined by GLC. The distribution is critical to performance. Color – This is a good indication of the way in which the product was made. Darker colors generally indicate that the product was exposed to more heat and consequently may have more oxidation. FTIR – This instrumental method is a great method to develop a fingerprint for the product. The availability of analytical programs to look at numerical comparisons to a standard pre-approved lot offers the chemist a unique method of verifying batch-to-batch variability. Melt point – The melting temperature is an important property to check % Glycerin – Even in instances where there is an acid value, it is critical to check glycerin content to determine is the acid was added to a product made by reaction of a triglyceride.

Lactams Are molecules that are cyclic amides O O NH + HOH H2N HO

Amide from Fatty Acids O NHCH2CH3 O CH3(CH2)10 + CH3CH2NH2 + HOH CH3(CH2)10 HO Fatty Acid is reacted with an ethylamine, releasing water. Water is removed by distillation leaving behind the amid. This reaction is generally conducted without catalyst. . Water must be efficiently removed to obtain a high purity product. Air must be excluded to prevent color formation.

Amide from Fatty Acids Specifications
Acid Value – Acid value measures added acid. Acid reacts with amine to form amid. In cases of esters made by transesterification, there will be no acid value, unless the acid is post added, that is added after the making of the product. Amine Value – Amine value is a measure of the unreacted amine content. It will drop as the reaction proceeds. GLC- The ratio of carbon distribution of the amid can be determined by GLC. The distribution is critical to performance. Color – This is a good indication of the way in which the product was made. Darker colors generally indicate that the product was exposed to more heat and consequently may have more oxidation. FTIR – This instrumental method is a great method to develop a fingerprint for the product. The availability of analytical programs to look at numerical comparisons to a standard pre-approved lot offers the chemist a unique method of verifying batch-to-batch variability.

Amide from Triglycerides
A triglyceride is reacted with an alkanolamine, releasing glycerin. Glycerin is not removed and is left in the product in which it is soluble. This reaction is generally conducted using a base catalyst.

Specifications Acid Value – Acid value measures added acid. Acid reacts with amine to form amide. In cases of esters made by transesterification, there will be no acid value, unless the acid is post added, that is added after the making of the product. Amine Value – Amine value is a measure of the unreacted amine content. It will drop as the reaction proceeds. GLC- The ratio of carbon distribution of the amid can be determined by GLC. The distribution is critical to performance. Oolor – This is a good indication of the way in which the product was made. Darker colors generally indicate that the product was exposed to more heat and consequently may have more oxidation. FTIR – This instrumental method is a great method to develop a fingerprint for the product. The availability of analytical programs to look at numerical comparisons to a standard pre- approved lot offers the chemist a unique method of verifying batch-to-batch variability. Melt point – The melting temperature is an important property to check. % Glycerin – Even in instances where there is an acid value, it is critical to check glycerin content to determine is the acid was added to a product made by reaction of a triglyceride.

Problem Lets Make 200 g of Lauramide DEA
NH(CH2)2OH O CH3(CH2)10 Determine the Formula of the Reactants Lauric Acid CH3(CH2)10COOH Diethanolamine N-(CH2CH2-OH)2

Problem O NH(CH2CH2OH)2 O CH3(CH2)3 + (HOCH2CH2)2NH2 CH3(CH2)10 HO
Write a Balanced Equation O NH(CH2CH2OH)2 O CH3(CH2)3 + (HOCH2CH2)2NH2 + HOH CH3(CH2)10 HO

Problem Determine Emp Formula Lauric Acid CH3(CH2)10COOH C12H24O2
Diethanolamine N-(CH2CH2-OH) C4H10N

Problem Determine MW Reactants Lauric Acid CH3(CH2)10COOH C12H24O2
= 200 Diethanolamine N-(CH2CH2-OH) C4H10O2N C12*4 = H10 1*10 = N 1*14= 14 = 104 O2*16 = 32

Lauric Acid DEA Total There will theoretically be 5.9 % water generated and 94.1% Amide, if there is 100% reaction

Carboxylates Soap from Methyl Ester
Methyl Esters are saponified by reaction with KOH. The methanol produced is generally distilled from the product. O O- O CH3(CH2)10 + KOH + HOCH3 CH3(CH2)10 OCH3 K+ Potassium Laurate

Carboxylates Soap from Methyl Ester
Methyl Esters are saponified by reaction with KOH. The methanol produced is generally distilled from the product. O O- O CH3(CH2)10 + KOH + CH3OH CH3(CH2)10 OCH3 K+ Potassium Laurate

Carboxylates Soap from Triglycerides
This reaction is used to produce the so-called glycerin soaps. The reaction produces three moles of soap and one mole of glycerin. The glycerin stays in the soap and alters hardness of the soap giving the characteristic glycerin soap feel.

Soap Specifications Acid Value – Acid value measures added acid. Acid reacts with base to form soap. In cases of esters made by transesterification, there will be no acid value, unless the acid is post added, that is added after the making of the product Alkali Value – Alkali value is a measure of the unreacted base content, added to saponify the oil. It will drop as the reaction proceeds. Color – This is a good indication of the way in which the product was made. Darker colors generally indicate that the product was exposed to more heat and consequently may have more oxidation. FTIR – This instrumental method is a great method to develop a fingerprint for the product. The availability of analytical programs to look at numerical comparisons to a standard pre-approved lot offers the chemist a unique method of verifying batch-to-batch variability. Melt point – The melting temperature is an important property to check % Glycerin – Even in instances where there is an acid value, it is critical to check glycerin content to determine is the acid was added to a product made by reaction of a triglyceride.

Carboxylates from Fatty Alcohols
Sodium mono-chloroacetate is reacted with fatty alcohol or fatty alcohol ethoxylate in the presence of sodium methylate catalyst. Chloride ion is produced, which forms sodium chloride. Sodium chloride, a crystalline solid, is filtered off.

Carboxylates Fatty Alcohol

Carboxylates Fatty Alcohol
Category Specification INCI Name Trideceth-7 Carboxylic acid Appearance Clear Amber Liquid Color, Gardner 3 Max Acid Value 45.0 – 52.0 % Solids 90.0 – 92.0 pH (1 % DI water) 3.0 – 4.0 Solubility (DI water) Cloudy, translucent NaCl 1.0 % Max

Betaines Amido betaines are prepared by the reaction of sodium mono chloroacetate with an amido tertiary amine. Sodium chloride is produced.

Problem Make 200 grams of a 35% active Lauramido propylbetaine

Problem Next Determine Formula of Reactants
Lauramidopropyl dimethylamine C17H36ON2 Sodium monochloroacetate C2H2O2Na Cl

Problem Determine MW Reactants Lauramidopropyl dimethylamine C17H36ON2
= 268 Sodium monochloroacetate C2H2O2Na Cl C2*12 = H2 *1= 2 O2*16=32 Na 23*1 Cl 36*1=36 =117

Lauryl DMAPA Sodium monochloroacetate Total

Problem Adjust for water (60% water) Material MW MR MCH % Grams
Lauryl DMAPA Sodium monochloroacetate Total Material % % Lauryl DMAPA * Sodium monochloroacetate * Water Total

Problem Adjust for water (60% water) Material MW MR MCH % Grams
Lauryl DMAPAS Sodium monochloroacetate Total Material % % Lauryl DMAPA * Sodium monochloroacetate * Water Total % NaCl is 4.2% for 40% Active

Amino Propionates These products are a type of amphoteric surfactant that are capable of existing in a cationic, anionic and zwitterionic form depending upon pH. This separates them from betaines, which are amphoteric surfactants that cannot exist in the anionic form. The products are made by the reaction of a primary amine with two moles of acrylic acid in aqueous solution. Additionally, unlike betaines these products do not have salt produced during the reaction and consequently are salt free.

Amino Propionates

Quats Quats, or more formally, quaternary compounds are tetra-substituted ammonium compounds. The generic formula is as follows; R2 | R1-N+-R M- R1 is generally alkyl or alkylamido. R2 most often is methyl, or hydroxy ethyl. R3 is commonly methyl, ethyl, or benzyl. The exact nature of the “R” groups dictates performance. The M is a counter-ion needed for charge balance and is generally either Cl, or CH3SO4.

Chloride Quat Quaternary compounds, or simply quats are cationic compounds. This class of materials find a wide range of applications, including conditioning of hair and skin and germicidal compounds. The reaction is one in which a tertiary amine is reacted with an organic chlorine containing compound for example benzyl chloride to produce a quat liberation inorganic chloride ion.

Chloride Quat

Chloride Quat Germicidal Quats include: Benzalkonium chloride
Cetyl trimethylammonium bromide Cetylpyridunium chloride Cetylpyridinium chloride Benzethonium chloride

Sarcosinates Sarcosinate surfactants are mild, biodegradable anionic surfactants derived from fatty acyl chlorides and sarcosine. These compounds features lather building and resistance to sebum delathering in cleaners, polymers, industrial chemicals, petroleum and lubricant products. Sarcosinates are used as a foaming and cleansing agent for shampoo, shaving foams and foam washes and is soap bars to take advantage of the excellent lather and skin feel contribution.

Sarcosinates

Electrophilic Substitution

Electrophilic Substitution Sulfonation
SO3,prepared by the burning of sulfur, is reacted with fatty alcohol giving the fatty sulfate sauer ester, which is neutralized in a subsequent step water by hydroxide ion, most commonly with sodium as the counter ion. Potassium ammonium and even lithium salts have been prepared.

Electrophilic Substitution Sulfonation

Special Requirements SO3 is a very reactive corrosive and noxious material. Commonly SO3 is made by burning sulfur just prior to sulfation. The use of SO3 in making products is not recommended since very specialized reactors and handling equipment are needed.

Electrophilic Substitution Sulfonation (CSA)
Chlorosulfonic acid, a liquid, is reacted with fatty alcohol giving the fatty sulfate sauer ester, and unlike the SO3 version HCl. The HCl is removed via vacuum and reacted with water to make aqueous HCl. To the extent the HCl is not removed the product has NaCl after neutralization.

Electrophilic Substitution Sulfonation (CSA)

Special Requirements Chlorosulfonic acid (CAS), while easier to handle than SO3 is likewise a very reactive corrosive and noxious material. If it comes in contact with water it liberates HCl gas. It can cause a fire in contact with celluosics. The use of CSA in making products needs to be conducted under very specific anhydrous conditions, and the resulting HCl gas needs to be removed and disposed of properly. Consequently, very specialized reactors and handling equipment are needed.

Cyclo-addition reactions
Round and round we go…

Cyclo-addition reactions
There are a set of rules called the Woodward Hoffmann Rules Essentially they determined that the pathway of concerted pericyclic reactions were determined by the symmetry properties of the orbitals that were directly involved. Reactions involving 4n + 2 electrons will be thermogenically allowed (heat) 4n electrons will be photogenically allowed

Diels-Alder Reaction This reaction is a reaction involving a Diene (4 electrons) and a Dienophile (2 electrons) All you need is heat!

Diels-Alder Reaction

Diels-Alder Reaction What are the starting materials?

2 + 2 clycoaddition These types of reactions are photochemically allowed. All you need is hν light. R1 R1 + R2 R2

Dimer Acid Dimer acid describes a reaction mixture that is composed of a series of substituted cyclohexene-dicarboxylic acids formed by the Diels-Alder reaction. The reaction requires a dienophile and a diene. The mixture of products is a consequence of the various isomers that can occur with the reaction. Commercially, the product is made using tall oil fatty acid, derived from pine trees. This material has roughly the proper stiochometric ratio of diene ( linoleyl) to dienophile (oleyl).

Dimer Acid

Click Chemistry New and improved…

Click Chemistry “Click Chemistry” is a concept pioneered by Barry Sharpless, seeks to define the “ideal” chemical reaction. Give High Chemical Yields Produce few or no toxic byproducts Be stereospecific Produce products that are physiologically stable Have simple reaction conditions.

Click Chemistry Click chemistry is a reaction involving an azide N3 and a Alkyene. Cu(I)

Click Chemistry O N3 O NaN3 Cl N3 O OH N O OH

Ring Opening Alkoxylation
Lower molecular weight epoxides (oxiranes) such as ethylene oxide, propylene oxide and butylene oxide are capable of reacting with hydroxyl generally under base catalysis, causing a ring opening and an addition of oxyalkylene group Reaction with ethylene oxide adds polyoxyethylene groups, with propylene oxide adds polyoxypropylene groups and with butylene oxide adds polyoxybutylene groups. All these groups and mixtures thereof bring new solubility properties to the compounds to which they are added. The resulting compound likewise contains a hydroxyl group so a variety number of moles of oxide can be added. Lower molecular weight oxiranes are very reactive and the safe and efficient utilization of these materials require rigorous chemical engineering, advanced materials handling technology and innovative catalyst technology

Ring Opening Ring opening reaction is a reaction where a ring is open or broken. Ethoxylation Propoxylation Carboxylation (anhydrides)

Alkoxylation Ethoxylation is the reaction of an alcohol with ethylene oxide, producing a R-O-(CH2CH2O)xH Propoxylation is the reaction of an alcohol with propylene oxide, producing a R-O-(CH2CHO)xH | CH3

Ring Closing Reactions

How about a molecule that has an Alcohol and acid?
If a molecule has two reactive groups on it, it can form cyclics. The reactive groups have to be the correct number of carbons apart. 6 > 5 > 7 O O 5 3 O 6 HOH 1 HO HO 4 2 Lactone

Lactams Description: The preparation of lactams from ether amine and butryolactone actually occurs in two distinct steps. The first is ring opening of the butryolactone by nucleophilic attack of the carbonyl by the ether amine. The second is ring closure, making water and a cyclic amid, commonly called a lactam. Are molecules that are cyclic amides O O NH HOH H2N HO Lactam

Lactams

Imidazoline Description: Amino ethyl ethanol amine (AEEA) is reacted with a fatty acid to produce an amide with a free amino group. Subsequently, the ring is closed at high temperature producing a second mole of water.

Note: The first reaction (amid formation) occurs at about 180oC. The second occurs as the temperature is increased to 200oC. Efficient removal of water is necessary to obtain a high purity (90%+) product.

Sorbitan Esters Sorbitol, a hexose sugar, is cyclized by dehydration to form the 1:4 sorbitan structure. Esterification occurs mainly at the side-chain OH group, but some occurs at the ring OH's. Sorbitan esters are products made the reaction of sorbitol and fatty acids. Sorbitol is generally provided as a 70% solution in water. The reaction actually includes three distinct steps. They are (1) removal of water, (2) cyclization of linear sorbitol to make sorbitan and (3) esterification of the sorbitan with a fatty acid. Many modern techniques make the product in one batch running the first step in the presence of all the raw materials, then cyclizing and esterifying in tandem

Sorbitan Esters

Alkylpolyglucoside Description: Alkylpolyglucoside or APGs have been known for many years. If fact in 1893, the German chemist Emil Fischer combined fatty alcohols and glucose obtained from coconut or palm kernel oil and corn for the first time in However, it took almost one hundred years, to commercialize these products

Alkylpolyglucoside

Why is ring closing a problem?
If a molecule has two reactive groups on it, it can form 4 1 2 3 5 6 O + O - O O

Carbon-Carbon Bond Formation
How do we form carbon-carbon bonds…

Tutomerization Tautomers are isomers that interconvert by a chemical reaction called Tautomerization.

Why is this reaction important?
Everything we have done so far has dealt with the formation of Carbon-R bonds, but what about Carbon-Carbon bonds? The most common why to do this involves an Enol What is a Enol? - O O R R H Base Enol

Enol Reactions Enol reacted with an acid Enol with an Ester O O - O O
+ + H2O R OH R R O - OR1 + HOR1 +

Enol Reactions Enol with Aldehyde O O - O + + H2O R H R

Aldol Condensation

Guerbet Reaction ( an Aldol Condensation)
Under the proper conditions, linear alcohols can be oxidized to aldehydes, undergo an aldol condensation and produce Guerbet alcohols. The class of materials has been known for many years. Guerbet alcohols are regio-specific beta branched oils that are liquid to very low temperatures. They are super-fatting agents and are used to make a variety of esters.

Guerbet Reaction ( an Aldol Condensation)

Amine Oxidation

Amine Oxides An amine oxide, also known as amine-N-oxide and N-oxide, is a chemical compound that contains the functional group R3N+-O− (sometimes written as R3N=O or R3N→O). In the conventional formula assigned to the amine oxides R3N→O, the link uniting the nitrogen and oxygen atoms is a semipolar bond. The term amine oxide applies only to oxides of tertiary amines including nitrogen-containing aromatic compounds like pyridine. A tertiary amine is reacted with 35% peroxide in aqueous solution. The product is an amine oxide.

Amine Oxides

Amine Oxides -Typical Specifications
Appearance Provides a general indication of heat history and product quality Amine Oxide Active Measures purity pH (10% Sol.) Measures pH an important indication of product ionic nature. Free Peroxide Measures unreacted H2O2 and consequently % reaction. Free Amine Measures unreacted amine and consequently % reaction. Color (APHA) Provides a general indication of heat history and product quality.

Reduction Perhaps one of the most important and commonly overlooked reaction class is a group of related reactions called reduction. Within the class are several key reaction types, hydrogenation, hydrogenolysis and reduction. The commonality is the fact that hydrogen is reacted with various organic materials in the presence of a catalyst and most often a solvent. As will become clear the choice of organic material, solvent and catalyst has a profound impact on the product obtained.

Group Specific (Hydrogenolysis)

Hydrogenolysis Hydrogenolysis is a process in which hydrogen, in the presence of a suitable metal catalyst reacts with an organic compound breaking it into two molecules that are in low oxidation state ( for example a ethyl ester to two alcohols).

Group Specific Hydrogenolysis
This reaction allows for the reduction of the methyl ester while keeling the vinyl group in tact. The process relies upon specific catalysts developed to have this specificity. This reaction is used to make commercial oleyl alcohol and related materials.

Group Specific Hydrogenolysis

Polymers

What are Polymers? Polymers are macromolecules
Poly = Many -mer = Parts Typically Polymers can be: Natural Synthetic

Brief History “Polymer” was first used by Berzelius in 1833. In 1839, Charles Goodyear discovered vulcanization, by combining natural rubber with sulfur and hearting it to 270 °C The first truly synthetic polymer used on a commercial scale was phenol-formaldehyde resin by Baekeland, “bakelite”. In 1920, Staudinger: Polymers are high molecular weight molecules. (Nobel Prize in 1953) The Prevailing Theory: Polymers were aggregates of small molecules. “Drop the idea of large molecules. Organic molecules with a molecular weight higher than 500 do not exist” -Advice given to Hermann Staudinger

Polymer chemistry Polymer chemistry is organic chemistry on a much larger scale. It involves the reaction of molecules or monomers with at least two reactive sites. Free radical chemistry involves double bonds. When the molecular weight of polymers is increased, the mechanical and chemical properties of the polymers will drastically change.

Nylon 6,6 Wallace Carothers invented Nylon 6,6.
1940 Nylon hit the streets

Nylon Rope Trick The polymerization is so quick that when the two materials come into contact, they instantly form a polymer.

New Terms Structural Unit or Monomer Unit: The monomer or the residue from the monomer. Repeat unit: the unit enclosed in the brackets. Homo Polymer: Polymer formed by one monomer. Hetero polymers or copolymers: Contain more than one atom type in the bracket unit. Degree of Polymerization (DP or Xn): The total number of structural units in the polymer chain. Polydispersity (PDI): Polymer are polydisperse meaning they have many different polymer chain lengths.

Polymer Nomenclature PolyX Based on the Monomer:
If “X” is a single word, the name of the polymer is is written out directly PolyX If “X” consists of two or more words, parentheses should be used. Poly(vinyl chloride) (PVC) is made by the polymerization of vinyl chloride CH2=CHCl

Polymer Nomenclature Based on polymer Structure
The most common method for condensation polymers since the polymer contains different functional groups than the monomer. Common Functional Groups…. Polyesters Polyamides

Polycarbonate Polyurethane

Definitions Thermoplastic: Polymers that are not cross-linked can melt and flow, can dissolve. Step growth polymers: They are called step growth because the monomer adds on either chain end. Molecular weight builds slowly, high molecular weight only at high conversion. Chain Growth Polymers: New monomers add to the chain end only. Every reaction adds to the molecular weight.

MW Difference Chain and Step Growth
Chain growth

Molecular Weight 10,000 lbs 1 lbs Since this is polymer chemistry, we will consider a very realistic, everyday example to explore Molecular weight……

Mn Mn = 2,000

Molecular Weight

Polydispersity (PDI) So how can we tell which molecular weight do we use? Both Mn & Mw have value, but how do we apply them to a polymer sample? In Polymer science it is common to use the ratio of the weight average to the number average as a measure of the breadth of the distribution rather than the moments and this ratio is called the polydispersity.

Molecular Weight First we have to understand a basic principle in polymer chemistry Hydrodynamic volume of a polymer in solution

GPC This technique is an INDIRECT method for determining molecular weight It is based off of comparing the Hydrodynamic Volume of your polymer in solution to the Hydrodynamic Volume of a series of Polymers of known size and distribution (Standard). The polymer is dispersed into a solvent and passed though a column, based on the size of the polymer, the elusion time will be different

Molecular Weight

GPC It is important to note that:
If you take 3 polystyrene samples of the exact same MW, but have different polymer structure (branched, linear, comb-like) they can elute at DIFFERENT TIMES!!! Also, if you have have 2 polymers of the exact same MW, one Polystyrene and the other one PMMA. They can elute at DIFFERENT TIMES!!!! Luckily for us Benoit and co-workers came up with a Universal Calibration Curve. Based on: The product of Intrinsic Viscosity & MW was directly proportional to Hydrodynamic Volume.

Tm and Tg Polymeric materials are characterized by two major types of transition temperatures- The crystalline melting temperature (Tm) and the glass transition temperature (Tg) Tm : the melting temperature, just like a traditional small molecule. Tg : The temperature at which the amorphous domain of a polymer take on the characteristic properties of the glassy state = brittle, stiffness and rigidity.

Free Radical Polymerization
There are several steps involved in the polymerization process. Initiation Propagation Termination

Polymerization Most commonly BPO is used to polymerize Styrene . x 2

Polymerization . . n +

Chain Growth Polymerization
This type of polymerization happens by a series of steps, most commonly a series of reactions. Common Ester is formed when an acid is reacted with an alcohol, but what about a diacid and diol? O O + HOCH2CH2CH2OH HO R1 HO O O H H R1 OCH2CH2CH2O O n

Common Step Growth Polyurethane Nylon

Controlled Living Polymerization

Controlled “Living” polymerization
There are a few techniques that can produce polymers with a PDI close to 1. Atom Transfer Radical Polymerization (ATRP) Reversible Addition-Fragmentation Chain Transfer (RAFT) There are some problems with the Controlled living, but these two are promising for the cosmetic world.

ATRP + CuCl + Ligand + CuCl2 + Ligand . . . + ( )n . + . .
O Cl + CuCl + Ligand O R1 . + CuCl2 + Ligand R1 O R1 . O R1 . O + O R1 . O O R1 . O ( )n Cl + O R1 + CuCl + Ligand Cl O R1 . + CuCl2 + Ligand

Synthesis DEGMMA to MAPMA: 100 : 5 GPC CuBr/HMTETA used as catalyst
DMF as a solvent Polymer was purified by: Percipitation in hexanes Passed through a short neutral aluminum oxide/silica gel column GPC Mn = 43,000 g/mol PDI = 1.13

RAFT . . . . + Z = Ph R = C(CH3)2CN H3C CH3 C N S Z I R S Z I R C N

RAFT Macromolecules 2008, 41,

Organic Chemistry for Cosmetic Chemist
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Organic Chemistry for Cosmetic Chemist

Organic Chemistry for Cosmetic Chemists

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