Goals: 1. To learn some common properties of alcohols and phenols. 2. To distinguish phenols from the three types of alcohols by chemical tests. Concepts: Alcohols are organic compounds containing an -OH functional group bonded to a carbon atom. There are three classes (types) of alcohols: primary secondary and tertiary as sho!n belo!.
"rimary alcohol: #CH 2 -OH the $#% an al&yl group and the 'OH are attached to a primary carbon atom a carbon bonded to one other carbon atom (highlighted). H C OH R H H C OH H 3 C H # primary carbon (econdary alcohol: # 2 CH-OH the 2 $#% al&yl groups and the -OH are attached to a secondary carbon atom a carbon attached to t!o other carbon atoms from the 2 $#%()H*-) H C OH R R H C OH H 3 C H 3 C # # secondary carbon Tertiary alcohol: # * C-OH the * $#% al&yl groups and the 'OH are attached to a tertiary carbon atom (highlighted) a carbon attached to three other carbon atoms from the * $#% ()H*-) R C OH R R CH 3 C OH H 3 C H 3 C # # tertiary carbon # The +nternational ,nion of "ure and Applied )hemistry (+,"A)) method of nomenclature for alcohols use the ending ol . )hange the $e% ending of an al&ane to ol (i.e. methane to ol methanol ethane to ol ethanol). 1 Physical Properties of Alcohols: 1. Alcohols are colorless at room temperature. 2. Alcohols form hydrogen bonds !ith !ater. H O H O H R *. Alcohols form intermolecular hydrogen bonds (!ith itself). This causes alcohols to ha-e higher boiling points than hydrocarbon of similar molecular mass. R O H O H R .. Alcohols !ith / or less carbon atoms are soluble in !ater. Chemical Properties of Alcohols: 1. O0idation of alcohols by strong o0idants such as 12)r2O2 in H2(O. is possible but differs depending on the degree of alcohol. 30amples a b and c belo! sho! ho! a primary secondary and tertiary alcohol respecti-ely respond to treatment of o0idants. +f a reaction has occurred using 12)r2O2 in H2(O. there is a color change from orange to green. a) 1 2 Cr 2 O 2 4 45 R C H O )r 4* 4 #)H 2 OH primary alcohol aldehyde green6blue orange
R C H O R C OH O 7urther o0idation of carbo0ylic acid )H * )H 2 OH 4 )r 45 )r 4* green6blue orange 4 H 3 C C H O an aldehyde further o0idation H 3 C C OH O a carbo0ylic acid a primary alcohol 2 b) 1 2 Cr 2 O 2 4 45 R C R O )r 4* 4 # 2 )HOH secondary alcohol &etone green6blue orange 4 )r 45 )r 4* green6blue orange 4 H 3 C C CH 3 O a &etone 8O further o0idation OH C H 3 C H CH 3 a secondary alcohol c) Tertiary alcohol: #*)OH 4 12)r2O2 8O O9+:AT+O8
4 )r 45 orange OH C H 3 C CH 3 CH 3 a tertiary alcohol 8o reaction (still orange) 2. ;ucas Test: This test is for lo! molecular !eight alcohols and it distinguishes the rates of reaction of alcohols !ith the ;ucas reagent (H)l and <n)l2). "ositi-e indicator of the reaction is the formation of a !ater insoluble al&yl chloride as cloudiness or a precipitate. The formation of an al&yl chloride !ith tertiary alcohol is -ery rapid follo!ed by the secondary alcohol that may ta&e from / to 2= minutes to form -isible cloudiness. "rimary alcohols do not react !ith ;ucas reagent or it may sho! -ery little result in a -ery long time. * o alcohol: #*)OH 4 H)l (<n)l2) #*)l (al&yl chloride) 4 H2O >ery 7ast (insoluble6cloudiness)
4 CH 3 C H 3 C CH 3 OH * o alcohol H)l <n)l 2 CH 3 C H 3 C CH 3 Cl 4 H 2 O al&yl chloride (insoluble-cloudiness)
4 CH 3 C H 3 C H OH 2 o alcohol H)l <n)l 2 CH 3 C H 3 C H Cl 4 H 2 O al&yl chloride (insoluble-cloudiness) slo! 1 o alcohol: #)H2OH 4 H)l (<n)l2) 8o reaction6-ery -ery slo!
4 H C H 3 C H OH 1 o alcohol H)l <n)l 2 no reaction (no cloudiness) Phenols: "henolic compounds ha-e a ben@ene ring !ith the 'OH group attached to the ben@ene ring carbon atom. The simplest compound is phenol ()5H/OH) or OH . "henols are considered -ery !ea& acids. They ha-e different physical and chemical properties from alcohols. They neither undergo o0idation nor react !ith the ;ucas reagent. Ho!e-er phenols react !ith 7e)l* to form a para-phenol-7e comple0 (!hich has a purple color). 4 7e 4* OH (orange) OH Fe para phenol comple0 (purple) Materials: 5 medium si@e test tubes ethanol (ethyl alcohol) 2-propanol (isopropyl alcohol) tertiary butyl alcohol (2-methyl-2-propanol) phenol cyclohe0anol 2A 12)r2O2 in H2(O. (o0idant) H)l '<n)l2 (;ucas reagent) 2= A phenol 1A 7e)l* pH paper stirring rod and an un&no!n Wear safety goggles and dispose of chemicals in proper containers. Procedures: . o all parts of this experiment in the fume hood. 1. (olubility in Bater: "lace 2= drops of each alcohol phenol and an un&no!n in 5 separate test tubes in a test tube rac& labeling each test tube. Add 2 m; of distilled !ater to each test tube. +f the substance is soluble (miscible) in !ater there !ill be no separate layers. +f it is insoluble (immiscible) a cloudy mi0ture or layers !ill form. #ecord your obser-ation in the table belo!. 2. Acidity: To each test tube in step 1 dip a stirring rod and touch it to the pH paper. )ompare the color of the paper !ith the chart on the container to chec& the pH of the solution. Bash and dry the stirring rod before dipping it to the ne0t test tube. #ecord your obser-ations in the table belo!. *. O0idation of alcohols: )lean / test tubes !ith soap and !ater and dry the test tube !ith a paper to!el. ;abel each test tube and place them on a test tube rac&. "lace / drops of the alcohols phenol and an un&no!n in each test tube. Add * drops of the o0idant (12)r2O2-H2(O.) to each test tube. Obser-e if there is a change in color from orange to green6blue for the alcohols. #emember that only the primary and secondary alcohols undergo o0idation. The positi-e indicator is a change from orange to green6blue in 1-2 minutes. )olor change to any other color but green6blue is a negati-e reaction. #ecord your obser-ations. .. 7erric )hloride Test for "henolic compounds: )lean / test tubes !ith soap and !ater and dry the test tube !ith a paper to!el. ;abel each test tube and place them on a test tube rac&. "lace / drops of the alcohols phenol and an un&no!n in each test tube. Add * drops of 1A 7e)l* to each test tube. The positi-e indicator is the purple color of the phenol-7e comple0. Any color other than purple is negati-e. Obser-ation (heet for "rocedures 1-. 8ame of substance (olubility in !ater Acidity )olor change (orange to green6blue) #eaction product (aldehyde &etone 7e-comple0) Type of alcohol phenol n6a ethanol 2-propanol cyclohe0anol t-butyl alcohol / Cour un&no!n /. ;ucas% #eagent Test: Deasure 2 m; of the ;ucas reagent into fi-e labeled test tubes on a test tube rac&. Add / drops of each of the follo!ing to each test tube: ethyl alcohol 2- propanol cyclohe0anol t-butyl alcohol and deioni@ed !ater as a control. Di0 reagents !ell using a stirring rod. Bash and dry your stirring rod after each use. Obser-e and record formation of an insoluble product (cloudiness) the positi-e indicator that a reaction has ta&en place at different times. Alcohols Type of alcohols (1 o 2 o * o ) 1 minute (cloudy) * minutes (cloudy) / minutes (cloudy) 1= minutes (cloudy) 1/ minutes (cloudy) 3thanol 2-propanol )yclohe0anol t-butyl alcohol (2-methyl-2- propanol) your un&no!n !ater ,se the results of the tests for alcohol and phenol to identify your un&no!n. Ei-e reasons !hy you belie-e your un&no!n is FFFFFFF. Gustify your ans!er. 5 !uestions: 1. (ince all alcohols form hydrogen bond !ith !ater does this mean all alcohols are soluble (miscible) in !aterH BhyH 2. Brite the structure for each of the follo!ing alcohol identify !hat type of alcohol (its degree) and !rite the reaction product !ith an o0idant 12)r2O2-H2(O.. +f no reaction occurs !rite 8#. 2 * a) 2-pentanol b) 1-methyl-cyclopentanol c) 1-he0anol d) 2-methyl-2-butanol e) methylphenol *. Brite the structure for each of the follo!ing alcohols identify !hat type of alcohol (its degree) and !rite the reaction product !ith the ;ucas reagent. +f no reaction !rite 8#. . / a) 2-pentanol b) 1-methyl-cyclopentanol c) 1-he0anol d) 2-methyl-2-butanol e) methylphenol .. +f you add 12)r2O2 in H2(O. to a test tube !ith an un&no!n alcohol in it and the solution stays orange !hat can you conclude about the alcoholH 2 I