TERT-BUTYL CHLORIDE
ASPIRIN (ACETYLSALICYLIC ACID)
(CH3)3C-OH + HCl  (CH3)3C-Cl
o-C6H4(COOH)OH + (CH3CO)2O
CH3COOH
In a 250 cm3 separatory funnel place 25 g of anhydrous tert-butyl
alcohol and 85 cm3 of concentrated hydrochloric acid and shake the
mixture from time to time during 20 minutes. After each shaking, loosen
the stopper to relieve any internal pressure. Allow the mixture to stand
for a few minutes until the layers have separated sharply *; draw off and
discard the lower acid layer. Wash the halide with 20 cm 3 of 5% sodium
bicarbonate solution and then with 20 cm3 of water. Dry the preparation
with 5 g of anhydrous calcium chloride. Decant the dried liquid through
a funnel supporting a fluted filter paper into a 100 cm 3 distilling flask,
add 23 chips of porous porcelain and distill. Collect the fraction boiling
at 4951°C. The yield of tert-butyl chloride is 28 g.
*-
the addition of 10 g of anhydrous calcium chloride tends to
concentrate the acid and assists the separation of the chloride; the
yield is slightly improved.
GLASSWARE:
- separatory funnel
- thermometer
- round-bottomed flask
- filter flask
- conical funnel
- distillation water condenser
- filter flask
REAGENTS:
- tert-Butyl alcohol
- ethyl alcohol
- CaCl2
- 5% NaHCO3

o-C6H4(COOH)OCOCH3 +
Place 10 g of dry salicylic acid and 15 g (14 cm 3) of acetic anhydride in
a small conical flask, add 5 drops of concentrated sulphuric acid, and
rotate the flask in order to secure thorough mixing. Warm on a water
bath to about 50-60°C, stirring with the thermometer, for about 15
minutes. Allow the mixture to cool and stir occasionally. Add 150 ml of
water, stir well and filter at the pump. Recrystallise the crude
acetylsalicylic acid from a mixture of equal volumes of acetic acid and
water.
Acetylsalicylic acid decomposes when heated and does not possess a
true, clearly-defined m.p. Decomposition points ranging from 128° to
135° have been recorded. Some decomposition may occur if the
compound is recrystallised from a solvent of high boiling point or if the
boiling period during recrystallisation is unduly prolonged.
GLASSWARE:
- dropping funnel
- thermometer
- two-necked round-bottomed flask
- filter flask
- Bűchner funnel
- reflux condenser
- magnetic stirrer
REAGENTS:
- salicylic acid
- acetic anhydride
- acetic acid
- H2SO4
2,4,6-TRIBROMOANILINE
n-BUTYL ACETATE
C6H5NH2 + 3 Br2  (2,4,6)-C6H2Br3-NH2 + 3 HBr
n-C4H9-OH + (CH3CO)2O  CH3COOC4H9 + CH3COOH
To a solution containing 2.5 g (27 mmol) of aniline and 10 cm 3 of acetic
acid in a 100cm3 conical flask (Erlenmeyer flask) was added drop wise
a solution containing cm3 of bromine and 10 cm3 of acetic acid. The
reaction mixture was stirred and cooled in ice bath. When the reaction
stopped the mixture was added to 30 cm 3 of water in a 100 cm 3 beaker.
The precipitate of 2,4,6-tribromoaniline was collected by vacuum
filtration and allowed to dry in the air. Crystalline tribromoaniline melting
at 119120°C was obtained; yield 8.4-8.8 g (95100%).
Further purification if necessary by recrystallization from ethanol or
methanol.
To 0.5 mol of acetic anhydride add several drops of concentrated
sulphuric acid and then slowly add 0.25 mol of n-butanol stirring the
reaction mixture and keeping the temperature below 30°C (i.e. cooling
the flask i an ice bath). The whole apparatus must be protected against
humidity with a CaCl2 tube. After all the alcohol has been added,
maintain the temperature of 30°C for 45 min and then pour the reaction
mixture into iced water. Separated ester is extracted with ethyl acetate
(3x50 cm3), combined organic extracts are washed with 5% sodium
carbonate solution and dried with anhydrous magnesium sulphate.
During distillation one first removes the solvent and next collects n-butyl
acetate, b.p. 126128°C, yield 85%.
GLASSWARE:
- dropping funnel
- filter flask
- Bűchner funnel
- conical flask
- magnetic stirrer
REAGENTS:
- aniline
- acetic acid
- ethanol
- bromine
GLASSWARE:
- thermometer
- round-bottomed flask
- conical flask
- distillation condenser
- drying tube with CaCl2
- separatory funnel
REAGENTS:
- n-butanol
- acetic anhydride
- 5% NaHCO3
- H2SO4
- MgSO4
CYCLOHEXYL ACETATE
n-PENTYL ACETATE
c-C6H11-OH + (CH3CO)2O  CH3COO-c-C6H11 + CH3COOH
n-C5H11-OH + (CH3CO)2O  CH3COOC5H11 + CH3COOH
To 0.5 mol of acetic anhydride add several drops of concentrated
sulphuric acid and then slowly add 0.25 mol of cyclohexanol stirring the
reaction mixture and keeping the temperature below 30°C (i.e. cooling
the flask i an ice bath). The whole apparatus must be protected against
humidity with a CaCl2 tube. After all the alcohol has been added,
maintain the temperature of 30°C for 45 min and then pour the reaction
mixture into iced water. Separated ester is extracted with ethyl acetate
(3x50 cm3), combined organic extracts are washed with 5% sodium
carbonate solution and dried with anhydrous magnesium sulphate.
During distillation one first removes the solvent and next collects pure
cyclohexyl acetate, b.p. 170172°C, yield 80%.
To 0.5 mol of acetic anhydride add several drops of concentrated
sulphuric acid and then slowly add 0.25 mol of n-pentanol stirring the
reaction mixture and keeping the temperature below 30°C (i.e. cooling
the flask i an ice bath). The whole apparatus must be protected against
humidity with a CaCl2 tube. After all the alcohol has been added,
maintain the temperature of 30°C for 45 min and then pour the reaction
mixture into iced water. Separated ester is extracted with ethyl acetate
(3x50 cm3), combined organic extracts are washed with 5% sodium
carbonate solution and dried with anhydrous magnesium sulphate.
During distillation one first removes the solvent and next collects npentyl acetate, b.p. 141142°C, yield 82%.
GLASSWARE:
- thermometer
- round-bottomed flask
- conical flask
- distillation condenser
- drying tube with CaCl2
- separatory funnel
- two-necked round-bottomed flask
GLASSWARE:
- thermometer
- round-bottomed flask
- conical flask
- distillation condenser
- separatory funnel
- drying tube with CaCl2
- magnetic stirrer
REAGENTS:
- cyclohexanol
- acetic anhydride
- 5% NaHCO3
- ethyl acetate
- MgSO4
- H2SO4
REAGENTS:
- n-pentanol
- H2SO4
- Ethyl acetate
- MgSO4
ISOAMYL ACETATE
PHENYL ACETATE
(CH3)3CHCH2CH2-OH + (CH3CO)2O 
(CH3)3CHCH2CH2-OCOCH3 + CH3COOH
C6H5-O- + (CH3CO)2O  CH3COOC6H5 + CH3COO-
To 0.5 mol of acetic anhydride add several drops of concentrated
sulphuric acid and then slowly add 0.25 mol of 3-methyl-1-butanol
stirring the reaction mixture and keeping the temperature below 30°C
(i.e. cooling the flask i an ice bath). The whole apparatus must be
protected against humidity with a CaCl2 tube. After all the alcohol has
been added, maintain the temperature of 30°C for 45 min and then pour
the reaction mixture into iced water. Separated ester is extracted with
ethyl acetate (3x50 cm3), combined organic extracts are washed with
5% sodium carbonate solution and dried with anhydrous magnesium
sulphate. During distillation one first removes the solvent and next
collects isoamyl acetate, b.p. 141142°C, yield 80%.
GLASSWARE:
- thermometer
- two-necked round-bottomed flask
- conical flask
- distillation condenser
- distillation flask
- magnetic stirrer
- drying tube with CaCl2
- separatory funnel
REAGENTS:
- 3-methyl-1-butanol
- acetic anhydride
- 5% NaHCO3
- H2SO4
- MgSO4
- Ethyl acetate
Cooled solution of sodium salt of phenol, obtained by adding 0.2 mol of
phenol to a solution of 0.3 mol of sodium hydroxide in 50 cm 3 of water,
is added to 200 g of comminuted ice. To obtained the mixture one
quickly adds 0.25 mol of acetic anhydride and stirs the reaction mixture
vigorously for one minute. A colorless layer of phenyl acetate separates
almost immediately upon addition of the anhydride. The product is
separated and washed with a small amount of cold solution of sodium
hydroxide and subsequently with water. Crude ester is distilled to afford
pure phenyl acetate, b.p. 194196°C, yield 95%.
GLASSWARE:
- thermometer
- round-bottomed flask
- conical flask
- distillation condenser
- beaker
- separatory funnel
- magnetic stirrer
REAGENTS:
- phenol
- acetic anhydride
- NaOH
- NaCl
- ice
ACETYLGLYCINE
+ (CH3CO)2O  CH3CO-NH-CH2-COO3.75 g of glycine is dissolved in 15 cm 3 of water, stirred vigorously in a
100 cm3 conical flask and then 10 cm 3 of acetic anhydride is added in
one portion. Stirring is continued for 20 minutes and then the flask is put
in an ice bath or a refrigerator (recommended overnight). Separated
crystals are filtered off under vacuum, washed with cold water and dried
in 100°C. Yield of acetylglycine: 4 g, m.p. 207208°C.
+H
3N-CH2-COO
-
GLASSWARE:
- conical flask
- magnetic stirrer
- filter funnel
- Büchner funnel
- graduated cylinder
REAGENTS:
- glycine
- acetic anhydride
PHTALYLGLYCINE
O
O
O
+ +H3N-CH2-COO- 
O
N
OH
O
O
Phtalic anhydride and glycine are finely ground, mixed well, put into a
crucible or evaporating dish and heated to 150190°C for 15 minutes.
The reaction mixture is then carefully poured into 50 cm 3 of cold water.
Precipitated solid should be crushed and filtered under vacuum.
Obtained product is purified by crystallization from hot water. Yield of
pure product: 3.7 g, m.p. 192193°C.
GLASSWARE:
- conical flask
- reflux condenser
- Büchner funnel
- filter flask
- porcelain mortar
REAGENTS:
- phtalic anhydride
- glycine
PHTALYLACETIC ACID
CYCLOHEXANONE OXIME
O
OH
O
O
+ (CH3CO)2O 
O
O
O
Mixture of 5 g of phtalic anhydride, 12 cm 3 of acetic anhydride and 1 g
of potassium acetate is heated under reflux at 155165°C under CaCl2
for 15 minutes. Next the reaction mixture is poured into an ice-water
mixture. Obtained yellow precipitate is filtered under vacuum and
washed with 15 cm3 of water and then with 10 cm 3 of 50% ethanol. The
product should be dried at 100°C. Yield of crude product: 3 g.
Crystallization from methanol yields yellow needles, m.p. 245246°C.
GLASSWARE:
- round-bottomed flask
- conical flask
- reflux condenser
- filter flask
- Büchner funnel
- drying tube with CaCl2
REAGENTS:
- phtalic anhydride
- acetic anhydride
- potassium acetate
- 50% ethanol in water
O +
H2N OH
N
OH
Dissolve 2.5 g of hydroxyloamine hydrochloride and 4 g of crystallized
sodium acetate in 10 cm 3 of water in a small flask or in a test tube.
Warm the solution to about 40°C and add 2.5 g of cyclohexanone.
Stopper the vessel securely with a cork and shake vigorously for a few
minutes: the oxime soon separates as a crystalline solid. Cool in ice,
filter the crystals at the pump and wash with a little cold water.
Recrystallize from cyclohexane and dry the crystals upon filter paper in
the air. The yield of pure cyclohexanone oxime, m.p. 90°, is 2.5 g.
GLASSWARE:
- round-bottomed flask
- conical flask
- reflux condenser
- filter flask
- Büchner funnel
- stopper
REAGENTS:
- hydroxylamine
- sodium acetate
- cyclohexanone
- cyclohexane
- ice
N-BENZYLIDENEALANINE
BENZALDAZINE
C6H5CHO + H2N-C6H5  C6H5CH=N-C6H5 + H2O
2 C6H5-CHO + H2N-NH2  C6H5-CH=N-N=CH-C6H5 + 2 H2O
To fresh distilled 10.6 g of benzaldehyde in a 50 cm 3 conical flask
(Erlenmeyer flask) 9.4g of aniline was added with stirring. After 15 min.,
18 cm3 of ethanol was added and after 10 min. in room temperature the
mixture was cooled in an ice bath. The reaction mixture was vacuumfiltered using a Büchner funnel. Yield of dry N-benzylideneaniline: 15.2g
(84%), m.p. 52°C.
Into the stirred suspension of 26 g (25 cm 3) of benzaldehyde in 200 cm 3
of H2O hydrazine (0.125 Mol; 10 cm 3 of 40% solution) during 15
minutes was added. The precipitate was filtered off on a Büchner funnel
and recrystallised from ethanol to yield benzaldazine m.p. 91-92OC,
70%.
GLASSWARE:
- conical flask
- filter flask
- Büchner funnel
- magnetic stirrer
- bowl
REAGENTS:
- benzaldehyde
- aniline
- ethanol
- ice
GLASSWARE:
- conical flask
- filter flask
- Büchner funnel
- magnetic stirrer
- round-bottomed flask
REAGENTS:
- benzaldehyde
- hydrazine
- ethanol
- water
HIPPURIC ACID (BENZOYL GLYCINE)
+H
3N-CH2-COO
-
+ C6H5-COCl  C6H5-CO-HN-CH2-COOH
Dissolve 5 g of glycine in 60 cm 3 of 10 per cent. sodium hydroxide
solution contained in a wide-mouthed bottle or in a conical flask. Add
6.2 g (4.0 cm3) of benzoyl chloride in five portions to the solution.
Stopper the vessel and shake vigorously after each addition until all the
chloride has reacted: transfer the solution to a beaker and rinse the
bottle (conical flask) with a distilled water. Place a few grams of crushed
ice in the solution and add concentrated hydrochloric acid slowly and
with stirring until the mixture is acid to Congo red paper. Collect the
resulting crystalline precipitate of hippuric acid (benzoyl aminoacetic
acid), which is contaminated with a little benzoic acid, upon a Büchner
funnel, wash with cold water and drain well. Place the solid in a small
beaker with 20 cm3 of carbon tetrachloride, cover the beaker with a
watch glass and boil the mixture gently for 10 minutes (1). Allow the
mixture to cool slightly, filter by gentle auction, and wash the hippuric
acid on the filter with 3-4 cm3 of carbon tetrachloride. Recrystallise from
boiling water (about 100 cm 3) with the addition of a little decolorizing
carbon if necessary, filter through a hot water funnel and allow to
crystallize. Collect the pure hippuric acid in a Büchner funnel and dry it
in the steam oven. The yield is 5 g, m.p. 187°C.
Note.
(1) The carbon tetrachloride extraction removes any benzoic acid which
may be present.
GLASSWARE:
- round-bottomed flask
- conical flask
- stopper
- filter flask
- Büchner funnel
- beaker
REAGENTS:
- glycine
- benzoyl chloride
- HCl
- NaOH
- carbon tetrachloride
- Congo paper
- ice