Experiment 8B

Experiment 8B
Qualitative Analysis II
Introduction
Qualitative analysis of an unknown organic compound is an indispensible tool in experimental organic chemistry. This method is done in order to determine the possible structures of an unknown sample. The different functional groups present in an organic compound are identified by reacting the sample with different reagents that react that gives a visible result. It is an indispensable tool in experimental organic chemistry as well as other fields such as the study of natural products and biochemistry.
Sodium Metal
Results
Sample
n-butyl alcohol Sec-butyl alcohol Tert-butyl alcohol Structure/Formula of compound responsible for visible results H2 H2
Visible Result
Evolution of gas
Evolution of gas
Evolution of gas
H2
Tests for Alcohols
Sodium Metal
Type of Reaction: Acid-Base Reaction General Formula:
Tests for Alcohols
Sodium Metal
Mechanism
bubbles
sodium alkoxide
Tests for Alcohols
Sodium Metal
Complications
Dealing with sodium metal can be exciting. Make sure that all samples are dry before proceeding with test.
Tests for Alcohols
Sodium Metal
1. What property of alcohol is demonstrated in the reaction with Na metal? What is the formula of the gas liberated?
The alcohol exhibits acidic property in the reaction with Na metal. The hydrogen atom is replaced by Na producing H2 shown in the reaction: 2 ROH + 2 Na 2 RO()Na(+) + H2
(http://www2.uni-siegen.de/~pci/versuche/english/v44-1-1.html)
Tests for Alcohols
Sodium Metal
2. Dry test tube should be used in the reaction between the alcohols and Na metal. Why?
A dry test tube should be used because Na metal is highly reactive with water and may ignite violently due to the H2 gas produced
(http://www2.uni-siegen.de/~pci/versuche/english/v44-1-1.html)
Tests for Alcohols
Lucas Reagent (HCl/ZnCl2)

Results
Sample Visible Result
Structure/Formula of compound responsible for visible results

None
n-butyl Sec-butyl alcohol Tert-butyl alcohol
No layer Formation of layers Formation of layers
(CH3)2CHCl + H2O
(CH3)3CCl + H2O
Tests for Alcohols

Type of Reaction: Nucleophilic Substitution Substrate: Attacking Agent: Cl General Formula:
Tests for Alcohols

Mechanism (SN1 for 2 and 3 ROH)
insoluble layer Tests for Alcohols

Mechanism (SN2 for 1 ROH)
insoluble layer
Tests for Alcohols

ZnCl2 is a Lewis acid that complexes strongly with the lone-pairs oxygen. This weakens the CO bond and creates a better leaving group.
ZnCl2 also enhances the reactivity of the HCI by polar coordination.
Tests for Alcohols

Complications The test applies only to those alcohols soluble in the reagent (monofunctional alcohols lower than hexyl and some polyfunctional alcohols).
Tests for Alcohols

3. Why is the Lucas test not used for alcohols containing more than eight carbon atoms?
The Lucas test applies only to alcohols soluble in Lucas reagent (monofunctional alcohols with less than 6 carbons and some polyfunctional alcohols). Long chains of carbon makes the compound nonpolar and the OH group less functional. This results to the insolubility of the alcohol in the reagent, rendering the test ineffective.
Tests for Alcohols

4. Explain why the order of reactivity of the alcohols toward Lucas reagent is 3>2>1?
The reaction of alcohols with Lucas reagent is a nucleophilic substitution reaction. In an S-n1 reaction, the rate determining step is the carbocation. The carbocation is most stable in a tertiary alcohol and is therefore formed faster than a secondary and a primary carbocation. (Solomons and Fryhle)
Tests for Alcohols
Potassium Dichromate
Results
Structure/Formula of compound responsible for visible results Cr3+
n-butyl
Blue-green soln
Sec-butyl Tert-butyl
Blue-green Yellow-orange
Cr3+ Cr2O72Tests for Alcohols
Type of Reaction: Reduction-Oxidation General Formula:
Tests for Alcohols
Mechanism
Tests for Alcohols
Mechanism
Tests for Alcohols
Mechanism
elimination
chromate ester
green (due to chromium ion, Cr3+)
Tests for Alcohols
For 1 ROH, RCHO products are further oxidized to form RCOOH
Tests for Alcohols
Tertiary alcohols do not react because there will not be any b-hydrogens to eliminate.
Tests for Alcohols
Complications Aldehydes, which also give a positive test, are better characterized in other ways. The color usually develops in 5 - 15 seconds. Enols may give a positive test. Phenols give a dark colored solution which is not blue-green like a positive test.
Tests for Alcohols
5. Illustrate with equations the reactions of the following alcohols with Potassium Dichromate solution:
Proof that dichromate is a strong oxidizing reagent in an acidic soln (0 = 1.33 V) (0 = 0.13 V)
n-butylalcohol
CH3CH2CH2CH2OH + Cr2O7 2CH3CH2CH2COOH
CH3CH2CH2CHO + [O]
sec-butylalcohol
CH3CH2CH(OH)CH3 + Cr2O7 2-
CH3CH2COCH3 + H2O
tert-butylalcohol
(CH3)3COH + Cr2O7 2- no reaction
Tests for Alcohols
Ferric Chloride
Results
Sample Visible Result Structure/Formula of compound responsible for visible results Fe(OAr)3 Fe(OAr)3 Fe(OAr)3 Fe(OAr)3
Tests for Phenols
Phenol Catechol Resorcinol a-naphthol
Brown-black Brownish Brownish green Purple solution
Ferric Chloride
Type of Reaction: Complexation General Formula:
Tests for Phenols
Ferric Chloride
Mechanism
blue to violet color
Tests for Phenols
Ferric Chloride
Complications
Not all phenols or enols give positive results. Most oximes, hydroxamic acids, and sulfinic acids give a positive test. Bulky groups on the benzene ring, especially in the ortho position, may cause the experiment to show a negative result. Activating groups attached to the ring decreases the wavelength caused by less electron excitation, thus causing a different color of positive result.
Tests for Phenols
Bromine Water
Mechanism
Sample Visible Result Structure/Formula of compound responsible for visible results 2,4,6-tribromophenol
Phenol Catechol
Light brown Dark solution
Bromination of benzene ring Tribromoresorcinol

2,4-dibromo-1-naphthol
Tests for Phenols
Resorcinol
a-naphthol
Yellow with precipitate

Dark cloudy solution
Bromine Water
Type of Reaction: Electrophilic Substitution Substrate: ArOH Attacking Agent: Br+ brown to black solution General Formula:
yellow Br color is removed
Tests for Phenols
Bromine Water
Mechanism
Tests for Phenols
Bromine Water
The aromatic ring is activated by the hydroxy group, therefore, it can react by electrophilic addition
Tests for Phenols
Bromine Water
Complications Mercaptans react readily. HBr is generated, but will not be observed since the reagent is aqueous.
Tests for Phenols
Millons (Hg(NO3)2 in H2O)

Results
Sample Visible Result Structure/Formula of compound responsible for visible results Hg complex with phenols Hg complex with phenols
Phenol Catechol
Dark upper layer, light bottom

Dark solution
Resorcinol a-naphthol
Dark purple Greenish yellow
Hg complex with phenols Hg complex with phenols

Tests for Phenols

Type of Reaction: Electrophilic Addition and Complexation Substrate: Ar-OH and tyrosine Attacking Agent: Hg(NO3)2 General Formula:
Tests for Phenols

Mechanism
1. Nitration of aromatic ring 2. Complexation with mercuric ion
Produces: red complexes and ppt
Tests for Phenols

6. What functional group is responsible for the observed result in Millons test?
Phenol interacts with nitric acid, nitrated phenol reacts with mercury and mercury salts are formed. This reaction accounts for the observed positive result in Millons test.
Tests for Phenols
2,4-dinitrophenylhydrazine
Results
Sample Formaladehyde Acetaldehyde Visible Result Yellow ppt Orange, brown(heated) Structure/Formula of compound responsible for visible results 2,4-dinitrophenylhydrazone 2,4-dinitrophenylhydrazone
Acetone
Benzaldehyde
Orange ppt
Orange ppt
2,4-dinitrophenylhydrazone
2,4-dinitrophenylhydrazone
Tests for Aldehydes and Ketones
Type of Reaction: Nucleophilic Addition Substrate: Attacking Agent:
General Formula:
Mechanism
Mechanism
yellow to red ppt
Complications Some ketones give oils which will not solidify. Some allylic alcohols are oxidized by the reagent to aldehydes and give a positive test.
7. Why is it disadvantageous to use a strong acid catalyst in the reaction of aldehyde or ketone with 2,4-DNPH?
The use of a strong acid reverses the sequence of the reaction. Instead of the nucleophilic attacking the substrate followed by the electrophile, in the presence of a strong acid, the weaker ucleophile attacks the carbon to stabilize the forming hemiacetal. Water abstracts the H+ of the hemiacetal. Hemiacetals are less stable and will form acetals which do not show the visible changes expected of the test.
8. Show the mechanism for the reaction of acetaldehyde with the following reagents:
a. 2,4 DNPH
a. 2,4 DNPH
Bisulfite
Mechanism
Structure/Formula of compound responsible for visible results H2CH(OH)SO3- Na+
Formaldehyde
Ppt formation
Acetaldehyde
Acetone Benzaldehyde
Ppt formation
No Ppt Ppt formation
H3C(OH) SO3- Na+

H3CC(OH)SO3- Na+ (C6H6)CH(OH)SO3- Na+
Bisulfite
Type of Reaction: Nucleophilic Addition Substrate: Attacking Agent: General Formula:
Bisulfite
Mechanism
insoluble
Bisulfite
Complications Aryl methyl ketones form the precipitate slowly or not at all. Addition complex stable only in neutral solution.
Bisulfite
b. NaHSO3
Schiffs Test (Fuschine in NaHSO

Results
solution)
Formaldehyde Acetaldehyde Acetone Benzaldehyde
Purple Red-purple No change purple

solution)
Type of Reaction: Nucleophilic Addition and Elimination Substrate:
Attacking Agent: Schiffs Reagent General Formula:

Schiffs Reagent (fuchsia/pink)
solution)
(bis-N-sulfinic acid of p-rosaline hydrochloride) aka fuchsin-aldehyde reagent or Leucosulfonic acid

Mechanism
solution)

Product: Quinoid Dye (purple/magenta)
solution)

Complications
solution)
In this test the reagent should not be heated, and the solution tested should not be alkaline. When the test is used on an unknown, a simultaneous test on a known aldehyde and a known ketone should be performed for comparison.
solution)
9. Why is the Schiffs test considered a general test for aldehydes?

Differentiation of aldehydes from ketones becomes the main purpose of using Schiffs test since it cannot distinguish one kind of aldehyde from another.
Tollens Test (Ag(NH3)2OH)

Results
Sample Visible Result Structure/Formula of compound responsible for visible results Ag Ag None
Formaladehyde Acetaldehyde Acetone
Silver mirror Silver mirror Clear
Benzaldehyde
Silver mirror
Ag

Type of Reaction: Reduction-Oxidation Reducing Agent: Oxidizing Agent: Ag(NH3)2+ General Formula:

Mechanism
silver mirror

Complications
The test tube must be clean and free of oil if a silver mirror is to be observed. Easily oxidized compounds give a positive test. For example: aromatic amine, some phenols, a-alkoxy and a-dialkylaminoketones.

10.What test will you use to differentiate each of the following pairs? Give also the visible result.
Acetaldehyde and acetone
Schiffs reagent: acetaldehyde purple solution; acetone no reaction Tollens test: acetaldehyde silver mirror; acetone no reaction

10.What test will you use to differentiate each of the following pairs? Give also the visible result.
Acetaldehyde and bezaldehyde
Acetaldehyde and benzaldehyde can be distinguished from each other using the Bisulfite test since it is also an indication whether the sample is an aliphatic aldehyde or an aromatic aldehyde. Aldehyde will react faster than benzaldehyde because an aromatic ring makes the compound more electron-rich, making the compound less susceptible to nucleophilic attack. Both will form a red precipitate due to cuprous oxide.
Iodoform Test (NaOH/I2KI)

Results
Structure/Formula of compound responsible for visible results None
Formaladehyde
None
Acetaldehyde
Acetone Benzaldehyde
Yellow Ppt
Yellow Ppt None
CHI3
CHI3 None

Type of Reaction: Nucleophilic Addition + Substitution
addition substitution
Substrate:
I+
Attacking Agent: General Formula:
OH-

Mechanism: Secondary alcohols/ethanol with an adjacent methyl group are oxidized to methyl ketones/ethanal by iodine bleach.

Mechanism (Nucleophilic Addition Part)

Mechanism (Nucleophilic Substitution Part)
yellow ppt

Complications Test will not be positive if the R group is a diortho substituted aryl group.

11.What structural feature in a compound is required for a positive iodoform test? Will ethanol give a positive iodoform test? Why or why not?
Ketones and alcohols with a methyl group directly adjacent to a carbonyl group or a carbon atom bearing a hydroxyl group react with an alkaline solution of iodine to produce a yellow solid, iodoform. Ethanol will give a positive result because it can be oxidized to an aldehyde with a methyl group attached to a carbonyl group.

12.Show the mechanisms for the iodoform using acetaldehyde as the test sample:
Fehlings Test [Cu(C4H4O6)2]4 Results


Cu2O
Formaladehyde
Brick Red Precipitate
Acetaldehyde
Acetone

None
Cu2O
No rxn
Benzaldehyde
Cu2O
Fehlings Test [Cu(C4H4O6)2]4 Type of Reaction: Reduction-Oxidation Reducing Agent: (reducing sugar) Oxidizing Agent: [Cu(C4H4O6)2]4 General Formula:
Fehlings Test [Cu(C4H4O6)2]4 Fehlings Reagent: Sodium tartrate, NaOH and CuSO4 forming a copper-tartrate complex
Fehlings Test [Cu(C4H4O6)2]4 Mechanism
Fehlings Test [Cu(C4H4O6)2]4 Mechanism
brick red ppt
Fehlings Test [Cu(C4H4O6)2]4 Complications None.
Molisch (a-naphthol in ethanol)

Results
Test Samples Visible Result Structure Formula of Compound Responsible for the Visible Result
Glucose
1% Sucrose Maltose
Violet Ring
Violet Ring Violet Ring
1% Boiled Starch
Violet Ring

Type of Reaction: Nucleophilic Substitution Substrate: furfural or hydroxymethylfurfural Attacking Agent: a-naphthol General Formula:

Mechanism
Dehydration of Hexose Sugar by H2SO4 (elimination)

Mechanism
Dehydration of Pentose Sugar by H2SO4 (elimination)

Mechanism

Mechanism

Mechanism
violet
Benedicts Test [Cu3(citrate)2]

Results
Sample Visible Result Structure/Formula of compound responsible for visible results Cu2O Cu2O Cu2O No rxn
Glucose Maltose
Brick Red Precipitate Brick Red Precipitate
Sucrose
Boiled starch
No change

Type of Reaction: Reduction-Oxidation Reducing Agent: (reducing sugar) Oxidizing Agent: Cu3(citrate)2 General Formula:

Benedicts Reagent: Sodium citrate, CuSO4 and NaHCO3 forming copper-citrate

Mechanism

Mechanism
brick red ppt

Complications
Not general for simple aldehydes and ketones. Hydrazine derivatives give a positive test.
Hinsberg (benzenesulfonyl chloride)

Results

C6H5SO2NRH C6H5SO2NR2 R3NHCl C6H5SO2NRH C6H5SO2NRH
Tests for Amines
Methylamine Dimethylamine Trimethylamine Aniline n-methylamine
ppt in acid ppt in base/acid ppt in base ppt in baseacid ppt in acid

Type of Reaction: Nucleophilic Substitution Substrate: Attacking Agent: General Formula:
Tests for Amines

Mechanism (1 amines)
water soluble
water insoluble
Tests for Amines

water insoluble
Tests for Amines

water insoluble
Tests for Amines

water soluble
Tests for Amines

Complications
Amphoteric compounds give erroneous results. Some sodium salts of benzenesulfonamides of primary amines are insoluble in the Hinsberg solution and may appear to be secondary amines. Some tertiary amine hydrochloride salts are insoluble in dilute HCl and water and may also appear to be secondary amines.
Tests for Amines
Esterification
Results
Structure/Formula of compound responsible for visible results methyl 2hydroxybenzoate
Salicylic acid
Colorless with wintergreen odor
Tests for Carboxylic Acid + Derivatives
Esterification
Esterification
Mechanism
ester with odor
Esterification
Complications
None.
Hydrolysis of Benzamide
Results

ammonia
Benzamide
Red to blue litmus Pungent odor
Type of Reaction: Nucleophilic Substitution Substrate: Attacking Agent: OH General Formula:
Mechanism
basic and pungent
Complications
none
Hydrolysis of Ester
Results
Sample
Visible Result
Ethylacetate
Loss of Sweet Odor
Acetic acid and Ethanol
Hydrolysis of Ester
Hydrolysis of Ester
Mechanism
Hydrolysis of Ester
Complications
none
Hydrolysis of Anhydride
Results
Acetic anhydride
Acidic
Acetic acid
Type of Reaction: Nucleophilic Substitution Substrate: Attacking Agent: HOH General Formula:
Mechanism
Complications
Higher aliphatic anhydrides and aromatic anhydrides are not readily hydrolyzed with water and thus may not give a positive test.
Hydroxamic Acid Test

(hydroxylamine hydrochloride)
Results
Sample Visible Result Burgundy or magenta color Red to violet color Structure/Formula of compound responsible for visible results
Ethylacetate
Benzamide
Hydroxamate complexes
Acetic anhydride
Burgundy or magenta color

Burgundy or magenta color
Benzoylchloride

hydroxamic acid

Formation of Hydroxylamine
KOH is added to consume the HCl, so that the reaction will not proceed backward

(hydroxylamine hydrochloride) Mechanism for Anhydrides

(hydroxylamine hydrochloride) Mechanism for Acyl Halides

Mechanism for Esters

(hydroxylamine hydrochloride) Mechanism for Amides

Ferric Hydroxamate Complex Formation
red/violet/burgundy/magenta color
The solution is acidified by HCl to prevent the excess base from reacting with FeCl3 (a Lewis Acid)

(hydroxylamine hydrochloride) Complications
Some acids will give a positive test. Primary and secondary nitro compounds, imides, some amides, most nitriles, and aldehydes (with no ahydrogens give a positive test. Some sterically hindered amides fail to react.
Last Guide Question!

13. A colorless liquid has a bp 199-201C and burns with a smoky flame. The sodium fusion test proved negative for the presence of halogens, nitrogen and sulfur. It was not soluble in water, 5% aqueous sodium hydroxide, or 5% hydrochloric acid. However, it dissolved in sulfuric acid with evolution of heat. It did not give a precipitate with 2,4-DNPH solution and did not decolorize bromine-methylene chloride solution. The unknown liquid did give a positive hydroxamate test and was found to have a saponification equivalent of 136. Identify the unknown liquid.
Smoky flame indicates that the compound is aromatic. It tested negative for 2,4-DNPH, telling us that it is neither an aldehyde nor a ketone. Negative tests for bromine in methylene chloride solution also indicates that it is neither an alcohol nor a phenol. A positive test for hydroxamate test tells us that it is an acid derivative, which can undergo saponificationtherefore it is an ester. Finally, an aromatic ester with a boiling point range of 199201oC is methyl benzoate.
References
http://chemed.chem.purdue.edu/genchem/topicreview/bp /ch9/active.php http://www.biologie.uni-hamburg.de/bonline/library/newton/Chy251_253/Lectures/Oxidation_of _Alcohols/Oxidation.html http://homepages.ius.edu/DSPURLOc/c122/ket.htm http://www.curvedarrowpress.com/partd/tollens.html http://web.pdx.edu/~wamserc/C335W99/Fans.htm http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/ amine1.htm http://www.demochem.de/p30_Z_mol-e.htm
References
Hornback, J.M. (2006). Organic Chemistry. 2nd Ed. Belmont, CA: Thomas Brooks/Cole. Shriner, R.L. (2004). Systematic Identification of Organic Compounds. NJ: John Wiley and Sons Inc. Vogel, A.I. (1989). Vogels Textbook of Practical Organic Chemistry 5th Ed. UK: Longman Group.

Experiment 8B

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Experiment 8B

Tests for Alcohols

Tests for Alcohols

Tests for Alcohols

Tests for Alcohols

Lucas Reagent (HCl/ZnCl2)

Structure/Formula of compound responsible for visible results

n-butyl Sec-butyl alcohol Tert-butyl alcohol

No layer Formation of layers Formation of layers

Lucas Reagent (HCl/ZnCl2)

Tests for Alcohols

Lucas Reagent (HCl/ZnCl2)

insoluble layer Tests for Alcohols

Lucas Reagent (HCl/ZnCl2)

Tests for Alcohols

Lucas Reagent (HCl/ZnCl2)

ZnCl2 also enhances the reactivity of the HCI by polar coordination.

Tests for Alcohols

Lucas Reagent (HCl/ZnCl2)

Tests for Alcohols

Lucas Reagent (HCl/ZnCl2)

Tests for Alcohols

Lucas Reagent (HCl/ZnCl2)

Tests for Alcohols

Cr3+ Cr2O72Tests for Alcohols

Tests for Alcohols

Tests for Alcohols

Tests for Alcohols

green (due to chromium ion, Cr3+)

Tests for Alcohols

Tests for Alcohols

Tests for Alcohols

Tests for Alcohols

CH3CH2CH2CH2OH + Cr2O7 2CH3CH2CH2COOH

Phenol Catechol Resorcinol a-naphthol

Brown-black Brownish Brownish green Purple solution

Tests for Phenols

blue to violet color

Tests for Phenols

Light brown Dark solution

Bromination of benzene ring Tribromoresorcinol

Yellow with precipitate

yellow Br color is removed

Tests for Phenols

Tests for Phenols

Tests for Phenols

Tests for Phenols

Millons (Hg(NO3)2 in H2O)

Dark upper layer, light bottom

Dark purple Greenish yellow

Hg complex with phenols Hg complex with phenols

Millons (Hg(NO3)2 in H2O)

Tests for Phenols

Millons (Hg(NO3)2 in H2O)

Produces: red complexes and ppt

Tests for Phenols

Millons (Hg(NO3)2 in H2O)

Tests for Phenols

Tests for Aldehydes and Ketones

Tests for Aldehydes and Ketones

yellow to red ppt

Tests for Aldehydes and Ketones

Tests for Aldehydes and Ketones