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Departamento de Química
Selective alkoxylation of limonene over
Centro de
Química da
Madeira
commercially available clays
Catrinescu, C ª; Castilho, P. C. ª; Fernandes, C a; Breen, C b
ª Centro de Química da Madeira, Chemistry Dept., Madeira University, Campus Universitário da Penteada, 9000-390, Portugal
b Material Research Institute, Sheffield Hallam University, Pond Street, Sheffield S1 1WB, UK
amounts worth extracting, terpinyl alkyl ethers are Acid Activation: clays were treated with HCl at 3 different
usually synthesised through the alkoxylation of concentrations; see Figure 4.
4.
monoterpenes; especially limonene and α-pinene are
monoterpenes; Temperature: reactions performed at 25, 40, 60 and 80º 80ºC
Dresden,, Germany
the most used feedstock molecules1,2 – they are Alcohol / limonene ratio: tested at 1:1 and 2:1. OR
renewable menthane-
menthane-like terpenes available in large Clay / limonene ratio: 100, 200, 300 mg / 0.5 ml limonene
quantities from pine turpentine or as by- by-products Nature of Alcohol:
Alcohol: methanol, ethanol, propanol,
propanol, n-butanol
Green--Sustainable Chemistry , September 10 to 15, 2006 , Dresden
Figure 1: Product distribution of alkoxylation reaction over 4 clays Figure 2: Selectivity of alkoxylation over 4 homoionic forms of a clay Figure 3: Reactivity with 4 linear chain alcohols
100 70 100 90
1st International IUPAC Conference on Green
90 90 80
60
80 80
70
Conversion/Selectivity
Limonene conversion
Product distribution
70 50 70
conversion / selectivity %
60
60 Isomers 60
40
Mono-ether
Conversion 50
50 Di-ether 50 Conversion
Selectivity
Others Selectivity
30 40
40 Limonene 40
30 30 30
20
20 20
20
10
10 10
10
0 0 0
0
SAz SWy SapCa SD Al-SAz Fe-SAz Ni-SAz Na-SAz MeOH EtOH PrOH BuOH
Figure 4: Limonene conversion over 3 acid treated forms of SAz Results discussion
100 The nature of the clay: Limonene reacts readily with dry Nature of the alcohol: Methanol and n-butanol
90 methanol to yield the corresponding methyl terpinyl ether, as gave high limonene conversion and good
80 the main reaction product (good selectivity for all catalysts). selectivity for the mono-
mono-ether. These decreased
Conversio/Selectivity, %
70
Smaller amounts of 1,8,-1,8,-di-
di-methoxy-
methoxy-p-menthanes, isomeric for ethanol and propanol.
propanol. Water contents in the
60
(terpinolene,, α and γ-terpinene,
terpenes (terpinolene terpinene, isoterpinolene),
isoterpinolene), high alcohol, rather than chain length, may be
50
Conversion molecular-
molecular-weight compounds, p- p-cymene and p-menthenes responsible for these findings. t-BuOH failed
Selectivity have also been identified. There is no isomerisation, completely to react with limonene.
40