Synthesis of vanadyl acetylacetonate – Protocol C
V2 O 5 2H 2SO 4 C 2 H 6 O 4(Hacac) 2 Na 2 CO 3 2VO(acac) 2 2 Na 2SO 4 C 2 H 4 O 5H 2 O 2CO 2
Reaction. Place 2.5 mL distilled water in a 25 mL round-bottomed flask and slowly add 2.5 mL (46
mmol) of concentrated sulphuric acid (about 229% excess). Then add 6 mL (103 mmol) of ethanol
(about 1395% excess) followed by 1.25 g (7 mmol) vanadium pentoxide. Attach a water cooled
condenser and reflux this mixture for about 1.5 hours using a heating mantle. Cool the mixture and
filter using a small plug of glass wool, discarding any solid residue. Add 3 mL (29 mmol) of
acetylacetone (about 6% excess) dropwise to the filtrate with stirring. Neutralize the mixture by
adding it carefully to a solution of 10 g (94 mmol) of anhydrous sodium carbonate (about 586%
excess) in 75 mL of distilled water, contained in a 250 mL beaker, while stirring the mixture. Cool
the resulting mixture in an ice bath for 15 minutes.
Isolation. Suction filter the resulting mixture. Wash the dark green product with two portions of 5
mL of cold distilled water. Dry under vacuum for 15 minutes, then dry in a vacuum desiccator over
anhydrous calcium chloride.
Purification. Not prescribed.
Safety. See hazards associated with the reagents in Table 1.
Greenness Assessment. The evaluation was performed using the Green Star (GS) and the results are
shown in Figure 1.
REACTION ISOLATION GLOBAL
P1 P1 P1
P12 P2 P12 P2
P12 P5
P10 P3 P10 P3
P9 P5 P9 P5
P10 P6
P8 P6 P8 P6
P7 P7 P7
GSAI = 40.00 GSAI = 25.00 GSAI = 35.00
Figure 1. Greenness assessment (GS) for the synthesis of vanadyl acetylacetonate
Construction of the GS
V2 O 5 2H 2SO 4 C 2 H 6 O 4(Hacac) 2 Na 2 CO 3 2VO(acac) 2 2 Na 2SO 4 C 2 H 4 O 5H 2 O 2CO 2
Table 1 presents the hazards and scores associated with the substances involved and Table 2 presents
the scores used to construct the green stars.
Table 1. Hazards for the synthesis of vanadyl acetylacetonate, protocol C
Step Score: hazards to...
Substances involved Hazard code
R I Pu HH E P
Stoichiometric reagents
Acetylacetonec (CAS 123-54-6) H226, H302 2 1 2
Ethanolb (CAS 64-17-5) H225 1 1 3
Sodium carbonate (CAS 497-19-8) H319 2 1 1
Sulphuric acid (CAS 7664-93-9) H314 3 1 1
H302, H332, H335, H341,
Vanadium pentoxide (CAS 1314-62-1) 3 3 1
H361, H372, H411
Auxiliary substances
Solvents
Watera,b - 1 1 1
Product
Vanadyl acetylacetonate (3153-26-2) H302, H315, H319, H335 2 1 1
Waste
Carbon dioxide H280 1 1 2
H224, H302, H317, H319,
Ethanal 3 1 3
H335, H351
Ethanol b H225 1 1 3
Sodium carbonate (aqueous solution) - 1 1 1
Sodium sulphate (aqueous solution) - 1 1 1
Sulphuric acid (dilute solution) - 1 1 1
Vanadyl sulphate hydrate H302 2 1 2
Watera,b - 1 1 1
R – Reaction; I – Isolation; Pu – Purification; HH – Human Health; E – Environment; P – Physical
a Renewable; b Degradable to innocuous products; c Degradable
Table 2. Scores used to construct the green star for the synthesis of vanadyl acetylacetonate,
protocol C
Reaction Isolation Global
Green Chemistry
Principle
s Explanation s Explanation s Explanation
P1 Vanadyl sulphate
2 1 Ethanal, H351 1 Ethanal, H351
Prevention hydrate, H302
Excess of reagents > Excess of reagents >
P2
1 10%, formation of by- NA 1 10%, formation of by-
Atom Economy
products products
Vanadium pentoxide, Vanadium pentoxide,
P3
H341, H361, H372, H341, H361, H372,
Less hazardous 1 NA 1
H411, sulphuric acid, H411, sulphuric acid,
chemical synthesis
H314, ethanal, H351 H314, ethanal, H351
P5
Safer solvents and 3 Water 3 Water 3 Water
auxiliary substances
P6
Increase energy 2 0 ºC ≤ T ≤ 100 ºC 2 0 ºC ≤ T ≤ 100 ºC 2 0 ºC ≤ T ≤ 100 ºC
efficiency
P7
Substances not Substances not Substances not
Use renewable 1 1 1
renewable renewable renewable
feedstocks
P8
3 One stage NA 3 One stage
Reduce derivatives
P9
3 Without catalysts NA 3 Without catalysts
Catalysts
P10 Substances not Substances not Substances not
1 1 1
Design for degradation degradable degradable degradable
Vanadium pentoxide, Vanadium pentoxide,
P12 H341, H361, H372, H341, H361, H372,
Safer chemistry for 1 sulphuric acid, H314, 1 Ethanal, H224 1 sulphuric acid, H314,
accident prevention ethanal, H224, ethanal, H224,
ethanol, H225 ethanol, H225
s – Score; NA – Not applicable
References
Glidewell, C.; “Metal Acetylacetonate Complexes: Preparation and Characterization” in Woollins, J., Ed.; Inorganic
Experiments, 2nd ed., Wiley-VCH, Weinheim, 2003; Exp. 3.16.
