Plant Derived Flavour and
Fragrance Molecules
Ray Marriott
Biocomposites Centre, Bangor University
Contents

Drivers for plant derived molecules

Legislative framework

Flavour and fragrance product overview

Flavour and Fragrance molecules from plants

Conclusions
Drivers for Plant Derived Molecules
Flavour molecules
 Growth in “Natural” flavourings
 Consumer and retailer pressure

Legislation – EC/1334/2008 (January 2011)

Sustainability
Fragrance molecules

Less emphasis or need for “natural”

Unique properties of plant derived molecules

Cost effective ingredients
Market for Plant Derived Molecules
The worldwide flavours and fragrance ingredient market is worth approximately $7.8
billion (£4.9 billion) in 2011 with an average annual growth rate of 4.5% per year.
“World demand for quality essential oils and their derivatives is likely to see increasing demand in
the coming years, and natural products will continue to remain an important part of the flavours
and fragrances industry”
BCC Research: Report CHM034B
Legislative Framework

Flavouring molecules




EC/1334/2008 – defines “Natural” substances and permitted
methods of preparation
2009/32/EC and 2010/59/EC – defines permitted process
solvents and MRLs
2232/96/EC and amendments – establishes a community list
of flavouring substances
Fragrance molecules


Directive 93/35/EEC and amendments established a list of
cosmetic ingredients (INCI list), section 2 lists perfume and
aromatic raw materials
26 fragrance molecules are considered allergens and
restricted under Cosmetics Directive 2003/15/EC - more may
follow
Production of Natural Flavour Molecules
Renewable raw
materials
Fermentation
Natural sources
Renewable raw
materials
Extraction
(Physical processes)
Fractionation
Enzyme
hydrolysis
Extraction
Fractionation
“White biotechnology”
Extraction
Natural
flavour &
fragrance
molecules
Fractionation
Extraction
Clean
synthesis
Processes compliant with Annex II – EC/1334/2008
Microwave
activation
Renewable raw
materials
Flavour and Fragrance Product Overview

Extracted products





Expressed products


Oleoresins – herbs and spices in particular
Concretes
mostly fragrance applications
Absolutes
Enfluerage – aroma extracted into purified fats & oils
Mostly applied to citrus peel oils
Essential oils


Steam distilled from green or dried plant materials
Often starting materials for aroma molecules
Flavour and Fragrance molecules from plants

F&F molecules are mostly secondary
metabolites and plant chemotype specific

Composition is also subject to climate, location,
harvest date and post harvest processes

Most plant derived molecules are:

Terpenes


Phenolics


Hydrocarbons, alcohols, aldehydes, esters
Alcohols, aldehydes, ethers, esters
Aliphatic esters
Flavour and Fragrance molecules from plants
Most aroma molecules are produced in
specialised structures called trichomes
Lavender
trichomes
Peppermint
trichomes
Terpenes from plants

Most terpenes used in flavour and fragrance formulations
are mono (C=10) or sesquiterpenes (C=15)

Monoterpenes and sesquiterpenes can be acyclic, mono,
bi or very occasionally tricyclic
myrcene
a-farnesene
b-terpinene
camphene
a-bisabolene
tricyclene
g-cadinene
cyperene
Terpene hydrocarbons
= 60%
a-pinene
sabinene
D3-carene
Picea abies
= 60% +
OH
a-pinene
camphene
limonene
terpinen-4-ol
Cupressocyparis leylandii
= 90%
Humulus lupulus
myrcene
caryophyllene
humulene
Terpene alcohols, ketones and aldehydes
60
50
40
menthone
menthol
30
menthyl acetate
L-menthol
menthone
20
menthofuran
10
Mentha piperita
0
30-Oct
30-Sep
50-65%
15-Sep
50-80%
15-Aug
D-carvone
29-Jul
05-Jul
14-Jun
Mentha spicata
L-carvone
Carum carvi
Welsh native Mentha species
piperitone oxide
Mentha x villosa
menthofuran
Mentha aquatica
Linalool from Mentha sp.
Mentha gentilis oil
First fraction
Middle fraction
Residue
Distribution of linalool isomers
Basil
Mentha sp.
Ho leaf
Lavender
Hop
Rose
Geranium
Grapefruit
Lemon
Rosemary
Lilac
Coriander
Jasmine
Enantiomeric distribution (%)
(R)
(S)
100
0
100
0
100
0
96
4
OT=0.7ppb
92
8
60
40
50
50
37
63
32
68
23
77
11
89
10
90
4
96
OT=7.8ppb
Casabianca H, Graff JB, Faugier V, Fleig F, Grenier C (1997) Enantiomeric distribution studies of linalool and linalyl acetate.
A powerful tool for authenticity control of essential oils. HRC J High Res Chrom 21:107-112
Linalool from Coriandrum sativum
Steam
distillation
CO2 extraction
Essential oil
Fractional
distillation
Molecular distillation
Triglycerides
Petroselinic acid
(S)-(+)-linalool
Lauric acid
Adipic acid
Nylon 66
Phenolics from plants
Cinnamaldehyde
(55-75%)
Thymol
(35-55%)
Vanillin
(>95%*)
Carvacrol
(>60%)
Eugenol
(75-90%)
Estragole
(60-75%)
O
methyl salicylate
Anethole
(>75%)
(96-99%)
Plant derived aliphatic esters

Aliphatic esters are much less common than terpenes or
phenolic molecules

Most “natural” esters are produced by enzymatic
esterification of natural alcohols and fatty acids produced
by fermentation (complies with EC/1334/2008)

Aliphatic esters are found mostly in the families
Asteraceae
and Apiaceae
Esters from Chamaemelum nobile L.
60% of English chamomile oil comprises just three esters
2-methyl butyl angelate
Isobutyl angelate
propyl tiglate
Octyl esters – Heracleum species
Heracleum sphondylium
Heracleum mantegazzianum
Composition of hydro-distilled oil
1. octan-1-ol
2. 3-octenyl acetate
3. octyl acetate
4. octyl 2-methyl propanoate
5. octyl butanoate
6. octyl 2-methyl butanoate
7. octyl hexanoate
8. octyl octanoate
3
Heracleum sphondylium
1
6
2
7
4
5
8
3
9. hexyl 2-methyl propanoate
10. hexyl butanoate
11. hexyl 2-methyl butanoate
Heracleum mantegazzianum
10
11
9
2
4
5
6
Multi product streams from Heracleum sp.
Steam
distillation
CO2 extraction
Essential oil
Fractional
distillation
Molecular distillation
Octyl and hexyl
esters
Triglycerides
Psoralens
Petroselinic acid
Polymers
Pharmaceuticals
and drug
precursors
Conclusions

Demand for plant derived F&F molecules is growing

Plants are still an economic source of F&F molecules

A wide range of terpenes, phenolics and aliphatic
compounds can be obtained from UK plants
But!

Crops can often be grown and processed at lower
cost in other parts of the world

UK production needs to be highly efficient and where
possible targeted at multi-product crops
Thank you for your attention!
r.marriott@bangor.ac.uk
Flavouring substances database
http://ec.europa.eu/food/food/chemicalsafety/flavouring/database/dsp_search.cfm
Composition of Heracleum sphondylium scCO2 extract
3
1. octan-1-ol
2. 3-octenyl acetate
3. octyl acetate
4. octyl 2-methyl propanoate
5. octyl butanoate
6. octyl 2-methyl butanoate
7. octyl hexanoate
8. octyl octanoate
7
6
8
1
2
4
5
Psoralens from Heracleum sphondylium
9-[(3,3-Dimethyl-2-oxiranyl)methoxy]-7H-furo[3,2-g]chromen-7-one
8-methoxy psoralen
5-methoxy psoralen
(R)-9-((3,3-Dimethyl-2-oxiranyl)methoxy)-4-methoxyfuro(3,2-g)chromen-7-one
5,8-Diethoxy-2,3-dimethylquinoxaline
8-Isopentenoxy psoralen
nonacosane
b-sitosterol
5,8-dimethoxy psoralen
hentriacontane
hexadecanoic acid
linoleic acid
tetracosanol
nonadecane
octadecanoic acid