An Unknown Aldehyde or Ketone You will receive a sample of a pure aldehyde or ketone chosen from the list of possible

unknowns given later in the handout. You will: Determine the atmospheric boiling point of the unknown; Obtain (or receive a copy of) the infrared spectrum of the unknown; Receive a copy of the H NMR spectrum of the unknown; Prepare a solid derivative of the unknown and determine its melting point; and Identify the unknown by interpreting the information collected. Boiling Point Determination Place about 0.5 mL of the unknown in a dry 10- 75-mm test tube and add several boiling chips. Clamp the tube upright with the bottom resting in a small heating mantle. Suspend a thermometer (200 C scale) inside the tube so that the bulb is about 1-1.5 cm above the surface of the liquid and not touching the walls of the tube. Heat the sample to reflux (= boiling without evaporation). The boiling point is the temperature at which the hot vapors condense on the thermometer bulb and walls of the tube. If the heat input is raised, the temperature will not rise. Be sure to record an estimate of the uncertainty in the boiling point. Since the bp is the temperature at which the vapor pressure of the liquid equals the atmospheric pressure, the experimental boiling point will vary with altitude and weather. As a result, the observed boiling point is most likely to fall below the true 1 atmosphere boiling point. Spectroscopic Analysis It is difficult to tell an aldehyde from a ketone by IR spectroscopy, but the presence of an aldehyde is very obvious by H NMR. Consult a table of chemical shifts to find the ppm value for the RCHO signal. IR spectroscopy indicates if the compound is aromatic (contains benzene rings) or aliphatic (contains sp3 and sp2 hybridized atoms only). The IR spectrum also shows if the aromatic ring is monosubstituted, ortho-, meta-, or para-disubstituted. Check up on the frequencies for these peaks in the tables in the chapter on infrared spectroscopy. A methyl ketone or CH3CO-R has distinctive peaks in both the H NMR and IR spectrum. Look these up. Preliminary Identification Based upon the boiling point, IR, and NMR spectroscopy, some of the unknowns on the list of suspects can be immediately eliminated as possibilities for your unknown. Determine from the list which remains whether it is most appropriate to make only the semicarbazone derivative or only the 2,4-dinitrophenylhaydrazone. Usually, you should not need to make both derivatives. Final Identification Use the melting point of the dry solid derivative of the unknown and the other information to assign a unique identification to the unknown aldehyde or ketone. It should be possible to narrow down the list of suspects to a single unknown. If not, what are the two most likely suspects? Why can the data at hand not differentiate between them? Take care to consider the relative reliability of the data: that is, which information has the largest uncertainty?

Unknown Aldehyde or Ketone Page 1 of 3

Working Safely The unknowns are not highly toxic unless ingested in significant amounts. Avoid prolonged skin contact with the unknown and keep your fingers out of eyes, ears, nose, and mouth. Wash your hands after handling the unknown. Waste aldehyde or ketone should be placed in the container provided for disposal. Possible Unknowns and the Melting Points of the Solid Derivatives* Compound Boiling Point mp Semicarbazone mp 2,4-Dinitrophenylhydrazone 2-butanone 80 135 117 2-pentanone 102 110 143 3-pentanone 102 139 156 hexanal 128 106 104 cyclopentanone 131 205 142 4-heptanone 145 133 75 3-heptanone 148 102 100 2-heptanone 151 127 89 heptanal 153 109 108 cyclohexanone 155 166 162 octanal 171 98 106, 96 2-octanone 173 123 58 benzaldehyde 179 222 237 salicyladehyde 196 231 252 * data taken mostly from CRC Handbook of Tables for Identification of Organic Compounds, 3rd ed., Rappoport, Z., editor, CRC Press, Cleveland OH, 1967. Preparation of Semicarbazones
O H2N C NHNH3 Cl + CH3CO2 Na H2N O C NHNH2

+ NaCl + CH3CO2H

semicarbazide hydrochloride

semicarbazide

O H2N C NHNH2 + R

O C R'

C R'

NNH

C NH2

+ H2O

aldehyde or ketone

Dissolve 1 millimole (= 0.001 mole) of the unknown in 1 mL 95% ethanol in a reaction tube or 10- x 75-mm test tube. Add 1.25 mL 1 M aqueous semicarbazide hydrochloride [avoid skin contact: possible mutagen; wash hands] followed by 1 mL 1.5 M aqueous sodium acetate. Mix the liquids thoroughly. If and only if two liquid layers form, add 95% ethanol dropwise while shaking the tube to just obtain a clear single phase. [Sometimes you get really lucky and a solid forms right away: this is usually the product! No extra alcohol needed thenjust continue with procedure.] Heat the tube in a 60-70 water bath for about 10 minutes, and then cool the mixture to room temperature, and then in an ice bath. If no crystals have formed on cooling in ice, add a few drops of water to the tube and scratch the inside wall of the tube under the liquid surface with a
Unknown Aldehyde or Ketone Page 2 of 3

semicarbazone

glass rod. Collect the solid by suction filtration on filter paper in a Hirsch funnel, wash the crystals with several mL cold water, and then dry the solid on filter paper. If the melting point is not definitive, the solid may need to be recrystallized from 95% ethanol. Place the filtrate from the synthesis in the waste container provided. Preparation of 2,4-Dinitrophenylhydrazones
NHNH2 NO2 O2N + O R C R' aldehyde or ketone R C N NH R' O2N NO2 + H2O

2,4-dinitrophenylhydrazine

2,4-dinitrophenylhydrazone

Wear gloves! Dissolve 0.5 millimoles (= 0.0005 moles) of the carbonyl compound in 1 mL 95% ethanol in a 10-mL Erlenmeyer flask. Add 4 mL of the prepared 0.1 M 2,4-dinitrophenylhydrazine reagent (possible carcinogen, stains fingers, contains acid) and swirl to mix to the solutions. IF a solid does not form at room temperature, warm the mixture on the hot plate until the alcohol just starts to boil, and then remove it to cool on the bench. Complete cooling in an ice bath. Collect the solid on filter paper in a Hirsch funnel by suction filtration, and rinse the solid well with water. Discard the filtrate in the waste bottle provided. Be sure you have emptied the filter flask before doing the next step! Rinse the solid with 1 mL 5% aqueous NaHCO3 solution followed by 5 mL water. This removes any leftover acid in the reagent. This filtrate can be flushed down the sink in there is no solid present. Dry the derivative on filter paper before taking its melting point. If necessary, recrystallize the solid from 95% ethanol.

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