You are on page 1of 8

CHEM 31.

1 FINALS REVIEWER 24 October 2018 Expected results:


Post-Lab Discussion Ethanol: N/A
Experiment 10: Aldehydes and Ketones Formalin: silver mirror
: Reactions involving aldehydes and ketones Acetone: colorless solution
: Standard confirmatory test for the presence of Benzaldehyde: silver mirror (after heating)
aldehydes and ketones Schiff’s Test
INTRODUCTION Reagent: leucofuchsin
: Carbonyl group is a polar group Test for aldehydes
C=O, C is the carbonyl carbon Positive result: formation of violet colored
: Carbonyl oxygen atom allows molecules of solution
aldehydes and ketones to form strong Negative result: pink solution
hydrogen bonds to molecules of water but it Reaction
cannot have strong hydrogen bonds between Ethanol: N/A
their molecules Formalin: indigo soln/ppt
: aldehydes are always terminal Acetone: light pink soln
: ketones are always internal Benzaldehyde: indigo soln/ppt
Nucleophilic addition to the carbon-oxygen Benedict’s Test
double bond Reagent: CuSO4, citrate, NaHCO3
: nawawalan ng saturation o nawawalan ng Test for aliphatic aldehydes
double bond Does not give a positive result for
: occurs via 2 ways aromatic aldehydes
(1) Attack of a strong Nu- 1* Positive result: formation of brick red ppt
(2) Acid catalyst + weak Nu- 2* which is Cu2O
Catalyst will protonate oxygen then the Negative result: blue soln because of
Nucleophile will attack free Cu2+
Carbonyl carbon: trigonal planar, susceptible to Reaction: redox reaction
attack both front and back side Ethanol: N/A
: highly reactive Formalin: brick red ppt
: partial positive charge; oxygen has the partial Acetone: blue sol’n
negative charge Benzaldehyde: blue sol’n
OBJECTIVE: to examine the reactivities of Fehling’s Test
various aldehydes and ketones Reagent: cupric tartrate complex ion
2,4-DNPH Test Test for aldehydes
test for aldehydes and ketones Related to benedict’s test
reagent: 2,4-dinitrophenyl hydrazine Positive result: formation of a brick red
positive result: formation of yellow to ppt (CU2O)
orange precipitate Negative result: blue soln
negative result: orange to red solution Iodoform Test
reaction mechanism – acid catalyzed Based on the production of iodoform
nucleophilic addition (CHI3)
Ethanol - negative Reagent: NaOH, KI, I2
Acetone – positive – yellow orange ppt Hypoiodite (IO-) is formed and acts as an
Benzaldehyde – positive – yellow orange ppt oxidizing agent (weak)
Formalin – positive N/A – be/cause it doesn’t Test for methyl ketones and 2-alkanols
have another R group Positive result: formation of bright yellow
Tollens’ Test ppt
Reagent: [Ag(NH3)2]NO3 or Negative result: yellow solution
ammoniacal silver nitrate Needs only one carbon
Test for aldehudes Ethanol: bright yellow ppt
Positive result: formation of silver mirror Formalin: N/A
Negative result: coloreless solution Acetone: bright yellow ppt
Reaction: redox reaction Benzaldehyde: N/A
Effect of Acid Concentration on Hydrazine Epimers: are carbohydrates that differ in
Formation configuration on only 1 stereogenic center
If the acid concentration is too love the : allose and altorse, carbon2
reaction occurs slower : allose OH at the right, altrose OH at left
o 0.02M CH3COOH : glucose and mannose, carbon 2
If the acid concentration is too high, the : glucose OH at right (right left right right)
reaction would not happen and mannose OH at left
o 0.05M HCl : glucose and galactose, carbon 4
o acid-base reaction with : glucose OH at right, galactose OH at
hydrazine left
Reaction is pH dependent
Rate of reaction: 0.5M HCl < 0.02M Mutarotation: monosaccharides are reducing
CH3COOH < 0.02 M HCl sugars because of the presence of hemiacetal
Differentiate the following cpds group
Heptanal and heptanol: any tests for : mutarotation stops when a glycosidic bond to
aldehydes the carbonyl carbon is formed
: schiff’s test, purple sol’n, heptanal Hemiacetal carbon: carbon atom
p-ethylbenzaldehyde and ethanol attached to 2 oxygen atoms and has
: Schiff’s, purple sol’n, p-ethylbenzaldehyde an OH group attached to it
3-pentanone and 3-pentanol Anomeric carbon: carbonyl carbon
: 2,4-DNPH, yellow to orange ppt, 3-pentanone capable of having alpha and Beta
o-chlorobenzaldehyde and 3-benzylpropanal configuration
: Benedict’s, brick red, 3-benzylpropanal : goes through open-chain form then, ring
4-methyl-3-pentanone and 3-methyl-2- closing
pentanone For aldohexoses – glucopyranose
: iodoform test, yellow ppt, 3-methyl-2- For ketohexoses – fructofuranose
pentanone (methyl ketone) Tip: look at OH
hexanone and hexanal Alpha – one up one down OH
: Schiff’s, purple soln, hexanal Beta – both up OH and CH2OH group
Oligosaccharides
Experiment 11: Carbohydrates : 2-10 monosaccharides
Carbohydrates: broad class of : bond between them is a glycosidic bond
polyhydroxylated aldehydes and ketones : glycosidic bond = alkoxy group of one sugar
: OH group and carbonyl carbon unit attaches itself to the anomeric carbon
: CH2O, CnH2nOn : sucrose, maltose, lactose
Classification : sucrose (non-reducing) = glucose and
- Simple sugars: monosaccharides fructose, alpha 1-2 glycosidic bond
- Complex sugars: disaccharides, : alpha because pababa si oxygen
oligosaccharides, and polysaccharides : maltose (reducing) = alpha 1,4-glycosidic
Fischer Projection bond
Haworth Projection : lactose (reducing) = beta 1,4-glycosidic bond
Chair Conformation Polysaccharides
: more than 10 monosaccharide units
Monosaccharides : starch – a polymer of a-D-glucose
: may be classified as either aldoses or ketoses : yields a mixture of water-soluble
: glucose - aldohexose amylose and amylopectin upon hydrolysis
: fructose – 6 carbon ketohexose : amylose – linear
Ketoses: dihydroxyacetone : amylopectin – branched alpha 1,6
Ketopentose: ribolose Cellulose: polymer of B-D-glucose
Family trees of Ketose and Aldose : principal structural component of
Aldose plants
: partial hydrolysis cellobiose,
complete hydrolysis D-glucose
QUALITATIVE TESTS FOR CARBOHYDRATES FORMATION OF OSAZONE
Based on the production of furfural and Based on the reactivity of the aldehyde and
furfural derivative potential aldehyde group
Based on the reactivity of the aldehyde Reagent: phenylhydrazine, HCl + heat 20 min
or potential aldehyde group (i.e. : identify monosaccharides and reducing
hemiacetal) disaccharides
Phenolic compounds react with these in : positive: yellow to yellow-orange ppt
acid to give colored ppt = positive : negative: red soln
Molisch’s Test Osazone formation
Reagent: a-Naphtol, H2SO4 : monosaccharides that are epimeric at C-2
: all carbs will yield positive result (in free or give the same osazone
combined form) : phenylhydrazine targets C1 and C2
: positive result: red violet/ purple ring at the : disaccharides with a free anomeric carbon
interface gives a positive result
Molisch Test Expected results
Glucose – purple interface Glucose yellow-orange ppt
Sucrose – purple interface Maltose yellow-orange ppt
Starch – purple interface Fructose yellow-orange ppt
Bial’s Test Sucrose – red soln
Reagent: Orcinol, HCl, FeCl3 + heat (30-45min)
: differentiate pentoses from hexoses HYDROLYSIS OF OLIGOSACCHARIDES AND
: pentoses: blue green solution - ribose POLYSACCHARIDES
: hexoses: yellow – brown solution - glucose In the presence of acid disaccharides can be
Seliwanoff’s Test hydrolyzed back into its monosaccharide units
Reagent: resorcinol, H2SO4 + heat (15 min) Sucrose
: differentiate ketoses from aldoses : reagent: HCl + heat, 10% NaOH, benedict’s
: positive (ketoses): bright red solution reagent
: negative (aldoses): pink solution unhydrolyzed: blue solution
Rate: fructose > sucrose > glucose hydrolyzed: brick red ppt
Glucose – pink solution Starch
Fructose – red solution : components 20-30% amylose linear a1 4 and
Sucrose – pink solution 70-80% amylopectin branched a1 4 and
OXIDATION OF ALDEHYDES a1 6
Benedict’s Test : amylose: soluble in water, amylopectin:
: test for reducing sugars insoluble in water
: positive result: brick-red ppt : kapag nawala ang helix structure ni starch,
: negative result: blue solution nawawala yung blue complex and forms a
: rate: glucose > fructose > maltose > sucrose > yellow solution
starch Amylodextrin
Barfoed’s Test : short-chained amylose produced from
Reagent: cupric acetate, acetic acid + heat debranching amylopectin
(10 min) : I2 in KI: wine red
: differentiate reducing monosaccharides from : benedict’s test: green
reducing disaccharides : polysaccharides take longer because they
: positive (monosaccharides): brick red ppt) have more glycosidic bonds to break
: negative (reducing disaccharides): blue
solution benedict’s test – I2 in KI test
: limitation – heat the sample for too long, unhydrolyzed sucrose – blue soln – n/a
possibility of hydrolysis hy sucrose – brick red ppt – n/a
positive: flucose, fructose unhy starch – blue soln - blue-violet soln
negative: maltose hy starch – brick red ppt - yellow soln
How can you say that it’s a reducing sugar?
You have a hemiacetal
Experiment 12: Hydroxamic Test: General test for esters
Carboxylic Acid and Derivatives Procedure: EtOAc or ether + alcoholic NH2OH
Reactivity in HCl hear alcoholic HCl +FeCl3
Basicity Trend : basis is the production of hydroxamic acid
NR2 amide > RO- (ester) > OH- carboxylic positive result: purple or magenta colored
acid > RCOO- anhydrided > Cl- acyl solution; presence of esters
halide Why alcoholic solutions?
Use of alcoholic solutions: ensures miscibility of
Reactivity esters with reagents
Acyl halide > anhydride > carboxylic acid > Addition of alcoholic HCl before FeCl3-
ester > amide We need our pH to be slightly more acidic to
prevent the formation of Fe(OH)3 precipitate
RESULTS AND DISCUSSIONS Hydrolysis of Acid Derivatives
Solubility of NaHCO3 All carboxylic acid derivatives form
Solvent: 5% NaHCO3 carboxylic acid (or carboxylate) when
Observation: miscibility and efferevescence hydrolyzed
Reactions : * Hyrdolysis reaction can either be base-
Test for Acetic Acid or acid-catalyzed
Reagents: NaOH + CH3COOH + FeCl3 Base catalyzed –> carboxylate ion
Addition of CH3COOH is controlled until Acid catalyzed –> carboxylic acid
solution is slightly acidic BASE CATALYZED
Observation: formation of red-colored sol’n Ester
If basic, false positive -> FeOH3 Ethyl acetate + NaOH reflux + HCl
Reaction: * Observation: production of sour smell
Test for Benzoic Acid (formation of acetic acid)
Benzoic Acid + heat + NH4OH until slightly basic Anhydride
boil of xs NH3 FeCl3 Water + acetic anhydride litmus
Observation: formation of flesh-colored ppt Observation: blue litmus paper turns to red
Reaction: * Solution is acidic
Boil bc we don’t want NH3 giving false positive Amide
Formation of Esters Benzamide + NaOH heat blue litmus
General Observation: production of Observation: production of pungent odor;
fruity odor vapors turn red litmus paper to blue
Reaction pathways Production of ammonia will symbolize
Carboxylic acids and amides not reactive hydrolyzed benzamide
enough to synthesize an ester requires a ACID CATALYZED
catalyst Ester
Acyl halides and anhydrides ester synthesis Observation: production of sour smell
does not require catalysts NOT all acid-catalyzed hydrolysis of ester
From caraboxylic acid (catalyst required) produces a sour smell
CH3COOH + EtOH + H2SO4 (catalyst) heat Amide
(warm) Observation: no pungent odor (NH4+ is
Observation: production of “plastic balloon produced instead of NH3)
smell”
From Acyl Halide (no catalyst required) Base ang mas maganda for hydrolysis of ester:
Benzoyl Chloride + EtOH because of the carboxylate ion intermediate,
Observation: wintergreen-like or medicinal-like irreversible. Acid catalyzed is reversible
smell reaction. Hindi siya magrereact via nucleophilic
Mas maganda kasi hindi harsh yung conditions acyl substitution
to react
Acyl chloride to ester is more favored rather Test Ch3COOH miscible with effervescene
than from ester to acyl chloride C6H5Cooh partial solubility ; bubble form on the
solids
Test for acetic acid – NaOH and FeCl3 – red Synthesis of Esters
colored solution Reflux (45-60min) Cool to Room Temp
Test for benzoic acid – NH4OH – flesh-colored Why are these steps necessary? We reflux to
ppt prevent volatilization of ester product
Frormation of esters – carboxylic acid – plastic Transfer to sep funnel + saturated NaCl
balloon smell ethyl acetate Salting out to enhance layer separation
Acyl halide – wintergreen-like smell benzoyl organic layer + NaHCO3 + anhydrous
Hydroxamic test – positive for esters – purple or Na2SO4
magents colored solution Separation of layer
Organic layer:
Hydrolysis of acid derivation + NaHCO3 (s) used the effervescence as an
Anhydride – blue to red indicator of the acid-base neutralization
Esters – sour smell after addition of HCl + anhydrous Na2SO4 until it no longer
Amide – evolution of pungent odor (production aggregates as drying agent? Why didn’t we
of NH3), red litmus paper turns to blue use CaCl2? Para matanggal yung alcohol
product inside the organic layer. CaCl2
Experiment 13: Nucleophilic Acyl Substitution: removes ester
The Synthesis of Esters Simple Distillation
Esters: carboxylic acid derivatives Recap
R-COOR or Ar-COOR Give at least 3 ways to prevent decrease
Known for its aroma and flavor - Add alcohol in excess
Either natural or synthetic; commonly - Use absolute alcohol
found in fruits - Use of more activated carboxylic acid
Synthesis; acid catalyzed reactions of derivatives such as anhydrides and acyl
RCOOH and ROH chlorides
ROH serves as the nucleophile - Use of H2SO4 instead of other acids –
Minimize the H2O introduced, use excess concentrated to prevent introduction of
amount of one reactant in the synthesis water and acts as a dehydrating agent
Le Chatelier’s Principle - Use of solid NaHCO3 instead of
Xs ROH – forward reaction, shift to right aquaeous NaHCO3
Minimize H2O – shift to the right - Use of Na2SO4 instead of CaCl2
Leaving group is H2O
Methodology Experiment 14: Saponification: Herbal Soap
ROH + RCOOH RBF with boiling chips + Making
conc. H2SO4 Saponification: formation of soaps
Reaction of ROH and RCOOH : hydrolysis of ester linkages in a fat or oil
Alcohol (xs reactant) and carboxylic acid sample forming glycerol and fatty acid salts
(limiting reactant (soap)
Why should alcohol be in xs? Le : makes use of hydrolyzing agent aka lye
Chatelier’s Principle (NaOH or KOH, strong base)
What are other way that will favor : NaOH solid soaps, KOH liquid soaps
formation of esters? Minimize : Only additives: coloring powder, essential /
introduction of H2O in the reaction fragrance oil, herbal extracts
More reactive carboxylic acid Saponification is irreversible
derivatice. Use acyl halides or Tracing: indication that the process is
anhydrides as starting reagents than around 90% complete and the lye will
RCOOH. Use absolute ROH (ethanol). no longer separate form the oil
+ concentrated H2SO4 Soap is cured for 5-6 weeks for the
acid catalyst – to protonate carboxylic acid to NaOH to be completely consumed
make it more reactive Hot Process vs. Cold Process
Why was H2SO4 used instead of any other HOT
acid? Because it is also a dehydrating agent : ends as soon as cooking is finished
: since lye is used up already, any additives : product carboxylate salt
added will not be affected by the base : application soap making
: “rough” appearance bc of heat and form Transesterification
bubbles as it heats and cools : Reagents: triglyceride, NaOH, ROH
COLD : Nu: RO-
: takes 24-36 hours : product esters
: adding additives may react with the base : application biodiesel production
: less dense and smoother in texture Experiment 15: Hinsberg’s Method for
STAGES OF HOT PROCESS Characterizing Amines
Separation – separation of solids from Amines: contain an amine group
liquids, occasionally stirred : relatively weak bases due to lone pair on N
Coming together and rinsing – stirred : can be classified as 1, 2, 3.
vigorously to release hot air Characterization of 1,2,3
“Mashed potato” like consistency – look Reagent: benzenesulfonyl chloride
less bubbly and greasier; pH should be
around 8-10
saponification
: process of soap making: combination of fats
or oils with a lye solution
: saponification value, the amount of lye sulfonamides: products of benzenesulfonyl
needed for a certain kind of oil chloride and amines
: qualities of soap : density is greater than water
hardness / softness Hinsberg’s method: based on solubility of
amount of lather sulfonamide products
harshness / mildness Primary Amines: produce acidic sulfonamides
: these qualities are determined by types of fats when reacted with benzenesulfonyl chloride
/ oils used Acidic sulfonamide soluble in NaOH, insoluble
solubility of soap in water in acid
: the sodium salts of long chain carboxylic : white ppt
acids (soaps) are almost completely miscible in Secondary Amines: produce non-acidic
water sulfonamide
: micelle formation : insoluble in aquaeous NaOH layer formation
hydrophobic tail and hydrophilic head : layer formation in NaOH, and dense liquid
: soap allows water to remove normally- residue in HCl
insoluble matter by emulsification Tertiary Amines: it does not react with the
hydrophobic part traps the dirt, hydrophilic benzenesulfonyl chloride
part is soluble in H2O : no sulfonamide formed; layer separation dure
Synthetic detergents to polarity difference
: with sulfates or sulfonates as their polar groups : Addition of HCl reacts with tertiary amine to
: offer an advantage over soaps as they can form quarternary ammonium salt
function in hard water (i.e. watercontaining : solubility observed is due to acid-base
Ca2+, Mg2+, Fe2+, and Fe3+) ion rich commonly, reaction of tertiary amine with HCl
Ca2+ and Mg2+ mahirap magbula Expected results
: water-softening soap additive Aniline - sulfonamide is dissolved –
… compounds that bind with metal cations to white/cream ppt
prevent precipitation with soap Diethylamine – dense, organic residue (layer of
: NaHCO3 Borax (sodium borate or sodium globule containing sulfonamide – layer
tetraborate), EDTA compounds, citric acid formation
: sodium lauryl sulfate Triethlyamine – layer formation (upper layer is
Saponification vs. Transeseterification just the tertiary amine) – miscible
Saponification Primary – secondary – tertiary
: reagent: triglyceride, NaOH, H2O B.S.Cl Soluble – insoluble – NVR
: Nu: OH- HCl Insoluble – NVR – soluble
Limitation: amphiprotic amine (i.e. amines Experiment 16:
containing acidic and basic properties) Synthesis of 1-phenylazo-2-naphthol (Sudan 1)
Example: N-methylaminobenzoic acid Objectives:
: rxn false positive To synthesize a red-orange azo dye
Other methods of characterization called SUDAN I or 1-phenylazo-2-
NITROUS ACID TEST: Liebermann nitroso test naphthol using the two-pot synthesis
Reagent: Nitrous acid (HO-N=O) To purify the synthesized dye using
: reacts will all classes of amines, and recrystallization
differentiates them based on the products To utilize ingrain dyeing to color cotton
Primary Amines: evolution of N2 (g) fabric using the synthesized dye
Aromatic primary amines: yield orange or red Aniline + 12 M HCl + d.H2O -> phenyldiazonium
precipitate, stability of diazonium salt is solution
resonance stabilized Cool to below 5C –NaNO2 – ice bath
Secondary Amines: yellow organic layer (low B-naphthol + 5% aq. NaOH – ice bath -> B-
MW) or low melting soids (for aromatic amines naphthoxide solution
of higher aliphatic amines)
Tertiary amines: no reaction; except for tertiary Crude Sudan I + unreacted phenyldiaoznium +
alkylamins which form green para-nitroso B-naphthoxide + water
derivatives Filtrate – discard
CYCLIC IMIDE FORMATION Residue – recrystallize in ethanol pure Sudan
1 and 2 amines react with cyclic I. melting point 132C
anhydrides to form crystalline amides
3 amines do not react Ingrain dyeing dyed slight fade
REACTION WITH ISOCYANATES MAIN REACTION
1 and 2 amines react with isocyanates Diazotization and coupling reaction
to form crystalline substituted urea EAS – electrophilic aromatic substitution
3 amines do not react
Preparation of B-naphthoxide ion
B-naphthol + OH - resonance-stabilized
napthoxide ion
Addition of NaOH enhances electron
donating capability of hydroxyl group
Do not let the solution get too acidic
urea If acidic env’t, protonate, leaving you
CONVERSION TO AMIDE with a carbocation that is susceptible to
3 amines do not produce amides forming other side products
PICRATE SALTS OR MOLECULAR COMPLEXES Preparation of phenyldiazonium ion
addition of 2,4,6-trinitrophenol (diazotization)
precipitates with distinct melting points Primary aromatic amines
CHLOROANIL TEST Only formed in strongly acidic solutions
amines dissolved in dioxane produces with sodium nitrite
colored adducts when mixed with High pH will cause side reactions
chloroanil (2,3,5,6-tetrachloro-p- Coupling reaction: electrophilic aromatic
benzoquinone) substitution
Electrophile: phenyldiazonium ion
Attachment ortho or para? Number of
resonance structures intermediates o-7, p-6. O-
4 intermediates remained aromaticity, p-2
remained aromaticity

Properties of dyes
: dyes are colored compounds
chromophore: whole extended conjugated : lysochrome – dye used for biochemical
system; color-bearer, responsible for light staining of triglycerides, fatty acids, lipoproteins
absorption : generally, they are considered carcinogenic
auxochrome: parts of the molecule that compounds
increase/decrease the wavelength absorbed DETERMINATION OF AMINE AND COUPLING
by the whole molecule COMPONENT OF AN AZO DYE
TYPES OF DYEING : identify precursors of azo dyes
Direct dying: simply putting together the fabric 1 locate azo group (N=N)
and dye moleculres 2 look at the fxl groups attached to the
: similar IMFA between dye and fabric aromatic rings, identify wheter they EWG or EDG
Mordant dyeing: involves use of a mordant 3 mark areas susceptible to EAS in each
(glue) that reacts with both the fxl groups of the aromatic ring
dye and fabric, making them stick together 4 the markings that coincide with the azo group
: most mordants are heavy metal salts; limited then that is the coupling component and the
application dure to increasing toxicity other is the amine component
: example: chromium 5. If, on the other hand, the markings coincide
Disperse dying: dye simply being dispered on with –N=N- group on both aromatic rings, then
the fabric as it is the coupling components is the ring that is more
: for hydrophobic synthetic fiber (acetate rayon activated toward EAS.
and polyester)
Ingrain dyeing: synthesize the dye within the
fabric
: employed when dye and cloth do not have
very similar IMFAs
: cotton is very polar, and Sudan I is non-polar
: dyes used for ingrain dyeing are usually to big
to be able to anchor to the cloth itself

Properties fastness and levelness


Fastness: retentiveness of the cloth for the dye
Levelness: uniformity of the color on the fabric

Property Direct Dying Ingrain Dying


Synthesis and Dye is Dye is
Staining synthesized synthesized
before after staining
staining
IMFA Similar IMFA IMFA
between dye between dye
and fabric and fabrics is
not very
similar
Attachment Dye is not Dye
of dye to usually big molecule is
fabric and is too large and
attached to is trapped
fabric via inside grains
IMFA of fabric

Application of Sudan Dyes


: mainly used for coloring solvents, oils, waxes,
petrol, shoe, and floor polishes (hydrophobic
interactions)