The Chemistry of Fragrances...The Chemistry of Fragrances Perfumes and More 28 March 2019 1. Brief...

The Chemistry of FragrancesPerfumes and More

28 March 2019


28 March 2019

1. Brief History


28 March 2019

1. Brief History2. Nobel Prize (2004)


28 March 2019

1. Brief History2. Nobel Prize (2004)3. Catalytic Preparation of Fragrances


28 March 2019

1. Brief History2. Nobel Prize (2004)3. Catalytic Preparation of Fragrances4. Industrial Organometallic Processes


28 March 2019

1. Brief History2. Nobel Prize (2004)3. Catalytic Preparation of Fragrances4. Industrial Organometallic Processes5. Toxicology Outline


28 March 2019

1. Brief History2. Nobel Prize (2004)3. Catalytic Preparation of Fragrances4. Industrial Organometallic Processes5. Toxicology Outline6. Review of Flavor & Fragrance (2018)

Fortineau, A.-D., Chemistry Perfumes Your Daily Life. J. Chem. Educ. 2004, 81 (1), 45.

Brief History of Fragrances

• <1850: only the wealthiest could afford fragrances and perfumes

• <1900: Perfumes were made of entirely natural materials

• 2019: over 3000 fragrance ingredients are available to consumers (>90% chemically synthesized)

• Expected in everything from household cleaners to shampoo to processed food and more!



• Use of fragranced materials dates back thousands of years

• “Perfume” comes from Latin per fume meaning “through smoke” as in the burning of incense

• Egyptians pressed, boiled, dried, powdered, macerated in fat, and even distilled

• The early Crusades spread perfumes to Middle Age Europe

• Alchemy turned into chemistry in the 19th century, and fragrance was at the forefront

• 1882: Paul Parquet created Fougere Royale from synthetic coumarin, oakmoss, geranium, and bergamont



• Traditional discovery and development of new synthetic chemicals were based on the analysis of natural sources:• Plants (lavender, jasmine)• Fruits (lemon, orange)• Animal (musk, ambergris)

• Three main methods for acquiring





Expression





Steam Distillation





Solvent Extraction



• Chanel No5 was the first commercial perfume to use synthetic materials

• Synthetic materials are:• Cheaper• Less prone to degradation



• Much like medicinal chemistry, derivatives are explored after natural detection

Gautschi, M.; Bajgrowicz, Ja. A.; Kraft, P. Flavours and Fragrances 2001, 55, 379-387

Development of Types of Odors

Musk



Woody



‘Prodrug’ equivalence in perfumes

.

2004 Nobel Prize in Medicine & Physiology

Linda B. Buck Richard Axel

Howard Hughes Medical Institute Columbia University College of Physicians and Surgeons

Howard Hughes Medical Institute Fred Hutchinson Cancer Research Center

Buck, L. B., Unraveling the Sense of Smell (Nobel Lecture). Angew. Chem. Int. Ed. 2005, 44 (38), 6128-6140.


Two main questions:• How do mammals detect so many different environmental chemicals?• How does the brain translate those chemicals into diverse odor

perception and behaviors?





Humans can sense 10,000 to 100,000 chemicals (small, volatile)






G-protein coupled receptors (GPCR) were discovered to be responsible for odor detection







Odor receptors seem to be randomly distributed







Odor receptors seem to be randomly distributed

Different odorants can all trigger one type ofreceptor neuron

Axel, R., Scents and Sensibility: A Molecular Logic of Olfactory Perception (Nobel Lecture). Angew. Chem. Int. Ed. 2005, 44 (38), 6110-6127.




Why study smell?



Why study smell?It’s a primal sense




Can we study smell?




Can we study smell?It’s difficult to understand, but ithas tangible pieces(molecules &receptors)





What questionsshould be asked?






How do we smell?How does the brain learnand interpret these signals?







• 1300 odor receptors in a mouse







• 1300 odor receptors in a mouse• 500 in a human








• C. elegans have 302 neurons of which 16

are dedicated to odorrepresenting a 1000

odorant receptorgenes








• C. elegans have 302 neurons of which 16

are dedicated to odorrepresenting a 1000

odorant receptorgenes

Gene coding isclearly important

for odorrecognition


2004 Nobel Prize in Medicine & PhysiologyMapping brains/neurons when exposed to odors in mice & fruit flies


2004 Nobel Prize in Medicine & PhysiologyMapping brains/neurons when exposed to odors in mice & fruit flies

Clear relationship but get stuck at “ghost in the machine”

Chapuis, C.; Jacoby, D., Catalysis in the preparation of fragrances and flavours. Applied Catalysis A: General 2001, 221 (1), 93-117.

Catalytic Preparation of FragrancesCatalytic Hydrogenations


Catalytic Preparation of Fragrances


Catalytic Preparation of FragrancesCatalytic Hydride Reduction


Catalytic Preparation of FragrancesCatalytic Dehydrogenation


Catalytic Preparation of FragrancesCatalytic C–C bond formation


Catalytic Preparation of FragrancesCatalytic C–O bond formation/cleavage

Beller, M.; Blaser, H.-U. Organometallics as Catalysts in the Fine Chemical Industry; 2012.

Synthesis of Fragrances with Organometallic ChemistryAldehydes are extremely common in synthetic perfumes


Aldehydes are extremely common in synthetic perfumes

Synthesis of Fragrances with Organometallic Chemistry

Beller, M.; Blaser, H.-U. Organometallics as Catalysts in the Fine Chemical Industry; 2012.Bovo, S.; Scrivanti, A.; Bertoldini, M.; Beghetto, V.; Matteoli, U., A New Enantioselective Catalytic Route to Florhydral®. Synthesis 2008, 16, 2547–2550.



Beller, M.; Blaser, H.-U. Organometallics as Catalysts in the Fine Chemical Industry; 2012.da Silva, J. G.; Vieira, C. G.; dos Santos, E. N.; Gusevskaya, E. V., Hydroformylation of endocyclic double bonds in para-menthenic terpenes under mild conditions. Applied Catalysis A: General 2009, 365 (2), 231-236.




Hydrogenation with Ruthenium Yields Synthetic Analogs


Beller, M.; Blaser, H.-U. Organometallics as Catalysts in the Fine Chemical Industry; 2012.Christian C, Gautier A, Blanc P-A (1995) Eur. Pat. Appl. EP 643958 A2 (Firmenich SA)



Beller, M.; Blaser, H.-U. Organometallics as Catalysts in the Fine Chemical Industry; 2012.Chapuis C (2004) Chem Biodivers 1:980-102



Beller, M.; Blaser, H.-U. Organometallics as Catalysts in the Fine Chemical Industry; 2012.Schulte-Elte K-H, Pamingle H, Vial C (1998) Eur. Pat. Appl. EP 882697 A1 (Firmenich SA)



Criteria 2 Document

Toxicology

©2019 Research Institute for Fragrance Materials

Toxicology


Toxicology


#3

Exposure

Threshold

#4

Data

Generation

#2

Read-

Across Data

#1

Data

Methods

Toxicology


How to analyze 3000 fragrance materials?

Toxicology


Fragrances

Acids Alcohols Esters Aldehydes KetonesNitrogen

containingOxygen

containingSulfur

containingHydrocarbons

UnsaturatedSaturated

Vinyl Vinylene Aromatic a,b unsaturated Heterocyclic

ConjugatedCyclic Straight chain Branched

Spiro Bicyclo Macrocyclic

Cyclic Straight chain Branched

# C, LogKow # C, LogKow

Clustering based on extended fragment

Extended fragment

Functional group

Clustering based on functional group

Toxicology


How to analyze 3000 fragrance materials?

Toxicology


Alpha alkylsubstituted

Alpha aryl substituted

Hetero aromatic

Alkyl substituted aromaticBeta alkyl

substituted

Alpha alkyl substituted

hetero aromatic

Rea

ctiv

ity

Similar

Dissimilar

Cinnamaldehyde

o-MethoxyCinnamaldehyde

p-MethoxyCinnamaldehyde

Toxicology


http://fragrancematerialsafetyresource.elsevier.com

http://fragrancematerialsafetyresource.elsevier.com/

.

• Emotional Response• Analytical Testing• Medicinal Testing• Botany• Flavor/Scent Delivery Systems• Physical Response (biology)• Categorization Methods for Data• Physical Properties

Some Topics Not Covered

Anesthetic and fear



Tsutsui, Y.; Mizuno, J.; Sunada, K., Does the aroma of a patient’s preferred dental topical anaesthetic affect anxiety,

fear, and autonomic nervous system activity prior to dental local anaesthesia? A randomized trial. Flavour Fragrance

J. 2018, 33 (6), 405-410.

Hamakawa, M.; Okamoto, T., The effect of different emotional states on olfactory perception: A preliminary study. Flavour

Fragrance J. 2018, 33 (6), 420-427.



Tsutsui, Y.; Mizuno, J.; Sunada, K., Does the aroma of a patient’s preferred dental topical anaesthetic affect anxiety, fear, and

autonomic nervous system activity prior to dental local anaesthesia? A randomized trial. Flavour Fragrance J. 2018, 33 (6),

405-410.

Hamakawa, M.; Okamoto, T., The effect of different emotional states on olfactory perception: A preliminary study.

Flavour Fragrance J. 2018, 33 (6), 420-427.

Emotional states

.



Lee, S. M.; Cho, A. R.; Yoo, S.-H.; Kim, Y.-S., Effects of maltodextrins with different dextrose-equivalent values. Flavour

Fragrance J. 2018, 33 (2), 153-159.

Apriceno, A.; Girelli, A. M.; Scuto, F. R.; Tarola, A. M., Determination of furanic compounds and acidity for Italian honey quality.


Texier–Bonniot, T.; Berdagué, P.; Robins, R. J.; Remaud, G.; Lesot, P., Analytical contribution of deuterium 2D-NMR in oriented media

to 2H/1H isotopic characterization: the case of vanillin. Flavour Fragrance J. 2018, 33 (3), 217-229.

Analyzing biodegradation

.



Lee, S. M.; Cho, A. R.; Yoo, S.-H.; Kim, Y.-S., Effects of maltodextrins with different dextrose-equivalent values. Flavour Fragrance J.

2018, 33 (2), 153-159.

Apriceno, A.; Girelli, A. M.; Scuto, F. R.; Tarola, A. M., Determination of furanic compounds and acidity for Italian honey

quality. Flavour Fragrance J. 2018, 33 (6), 411-419.

Texier–Bonniot, T.; Berdagué, P.; Robins, R. J.; Remaud, G.; Lesot, P., Analytical contribution of deuterium 2D-NMR in oriented media

to 2H/1H isotopic characterization: the case of vanillin. Flavour Fragrance J. 2018, 33 (3), 217-229.

Quality testing

.



Lee, S. M.; Cho, A. R.; Yoo, S.-H.; Kim, Y.-S., Effects of maltodextrins with different dextrose-equivalent values. Flavour Fragrance J.

2018, 33 (2), 153-159.

Apriceno, A.; Girelli, A. M.; Scuto, F. R.; Tarola, A. M., Determination of furanic compounds and acidity for Italian honey quality.


Texier–Bonniot, T.; Berdagué, P.; Robins, R. J.; Remaud, G.; Lesot, P., Analytical contribution of deuterium 2D-NMR in

oriented media to 2H/1H isotopic characterization: the case of vanillin. Flavour Fragrance J. 2018, 33 (3), 217-229.

2D-NMR probing technique

.



Taiti, C.; Costa, C.; Figorilli, S.; Billi, M.; Caparrotta, S.; Comparini, D.; Mancuso, S., Volatome analysis approach for the

taxonomic classification of tree exudate collection using Proton Transfer Reaction Time of Flight Mass Spectrometry. Flavour

Fragrance J. 2018, 33 (3), 245-262.

Belhassen, E.; Bressanello, D.; Merle, P.; Raynaud, E.; Bicchi, C.; Chaintreau, A.; Cordero, C., Routine quantification of 54 allergens in

fragrances using comprehensive two-dimensional gas chromatography-quadrupole mass spectrometry with dual parallel secondary

columns. Part I: Method development. Flavour Fragrance J. 2018, 33 (1), 63-74.

Plant classification technique

.



Taiti, C.; Costa, C.; Figorilli, S.; Billi, M.; Caparrotta, S.; Comparini, D.; Mancuso, S., Volatome analysis approach for the taxonomic

classification of tree exudate collection using Proton Transfer Reaction Time of Flight Mass Spectrometry. Flavour Fragrance J. 2018,

33 (3), 245-262.

Belhassen, E.; Bressanello, D.; Merle, P.; Raynaud, E.; Bicchi, C.; Chaintreau, A.; Cordero, C., Routine quantification of 54

allergens in fragrances using comprehensive two-dimensional gas chromatography-quadrupole mass spectrometry with dual

parallel secondary columns. Part I: Method development. Flavour Fragrance J. 2018, 33 (1), 63-74.

Allergen detection

.



Jentzsch, P. V.; Gualpa, F.; Ramos, L. A.; Ciobotă, V., Adulteration of clove essential oil: Detection using a handheld Raman

spectrometer. Flavour Fragrance J. 2018, 33 (2), 184-190.

Purity testing

.



Trytek, M.; Paduch, R.; Pięt, M.; Kozieł, A.; Kandefer-Szerszeń, M.; Szajnecki, Ł.; Gromada, A., Biological activity of

oxygenated pinene derivatives on human colon normal and carcinoma cells. Flavour Fragrance J. 2018, 33 (6), 428-437.

Nagai, K.; Horii, Y.; Fujisaki, Y.; Fuyuki, R.; Misonou, Y., Effects of olfactory stimulation with scents of grapefruit and

lavender essential oils on the skeletal muscle sympathetic nerve and muscle blood flow in rats. Flavour Fragrance J. 2018,

33 (2), 135-143.

Satou, T.; Hayakawa, M.; Goto, Y.; Masuo, Y.; Koike, K., Anxiolytic-like effects of essential oil from Thymus vulgaris was

increased during stress. Flavour Fragrance J. 2018, 33 (2), 191-195.

Cancer treatment

.






lavender essential oils on the skeletal muscle sympathetic nerve and muscle blood flow in rats. Flavour Fragrance J. 2018, 33 (2),

135-143.

Satou, T.; Hayakawa, M.; Goto, Y.; Masuo, Y.; Koike, K., Anxiolytic-like effects of essential oil from Thymus vulgaris was

increased during stress. Flavour Fragrance J. 2018, 33 (2), 191-195.

Blood flow

.






lavender essential oils on the skeletal muscle sympathetic nerve and muscle blood flow in rats. Flavour Fragrance J. 2018,

33 (2), 135-143.

Satou, T.; Hayakawa, M.; Goto, Y.; Masuo, Y.; Koike, K., Anxiolytic-like effects of essential oil from Thymus vulgaris

was increased during stress. Flavour Fragrance J. 2018, 33 (2), 191-195.

Stress reduction

.



Satou, T.; Hanashima, Y.; Mizutani, I.; Koike, K., The effect of inhalation of essential oil from Rosmarinus officinalis

on scopolamine-induced Alzheimer's type dementia model mice. Flavour Fragrance J. 2018, 33 (3), 230-234.

Ambrosch, S.; Duliban, C.; Heger, H.; Moser, E.; Laistler, E.; Windischberger, C.; Heuberger, E., Effects of 1,8-Cineole and

(–)-Linalool on Functional Brain Activation in a Working Memory Task. Flavour Fragrance J. 2018, 33 (3), 235-244.

Natsch, A.; Kern, S.; Corbi, E.; Pérès, C.; Nägelin, M.; Leijs, H.; van Strien, M.; Calandra, M. J.; Wang, Y., Interlaboratory

evaluation of methods to quantify skin-sensitizing hydroperoxides of limonene and linalool (II): Analysis in cosmetic bases.


Alzheimer’s treatment

.



Satou, T.; Hanashima, Y.; Mizutani, I.; Koike, K., The effect of inhalation of essential oil from Rosmarinus officinalis on

scopolamine-induced Alzheimer's type dementia model mice. Flavour Fragrance J. 2018, 33 (3), 230-234.

Ambrosch, S.; Duliban, C.; Heger, H.; Moser, E.; Laistler, E.; Windischberger, C.; Heuberger, E., Effects of 1,8-Cineole and (–)-

Linalool on Functional Brain Activation in a Working Memory Task. Flavour Fragrance J. 2018, 33 (3), 235-244.

Natsch, A.; Kern, S.; Corbi, E.; Pérès, C.; Nägelin, M.; Leijs, H.; van Strien, M.; Calandra, M. J.; Wang, Y., Interlaboratory

evaluation of methods to quantify skin-sensitizing hydroperoxides of limonene and linalool (II): Analysis in cosmetic bases.


Brain activity

.



Satou, T.; Hanashima, Y.; Mizutani, I.; Koike, K., The effect of inhalation of essential oil from Rosmarinus officinalis on

scopolamine-induced Alzheimer's type dementia model mice. Flavour Fragrance J. 2018, 33 (3), 230-234.

Ambrosch, S.; Duliban, C.; Heger, H.; Moser, E.; Laistler, E.; Windischberger, C.; Heuberger, E., Effects of 1,8-Cineole and

(–)-Linalool on Functional Brain Activation in a Working Memory Task. Flavour Fragrance J. 2018, 33 (3), 235-244.

Natsch, A.; Kern, S.; Corbi, E.; Pérès, C.; Nägelin, M.; Leijs, H.; van Strien, M.; Calandra, M. J.; Wang, Y.,

Interlaboratory evaluation of methods to quantify skin-sensitizing hydroperoxides of limonene and linalool (II):

Analysis in cosmetic bases. Flavour Fragrance J. 2018, 33 (4), 322-330.

Cosmetic damages

.



Swathy, J. S.; Mishra, P.; Thomas, J.; Mukherjee, A.; Chandrasekaran, N., Nanometric neem oil emulsification

through microfluidization, and its therapeutic potential against Aeromonas culicicola infection in Cyprinus carpio.


Antibacterial effects

.



Yi, Q.-y.; Yi, S.-w.; Qin, T.-f.; Li, C.-y., Using RAPD and ISSR Molecular Markers to Analyze the Genetic Diversity of

Rose scented Pelargonium Populations. Flavour Fragrance J. 2018, 33 (1), 75-81.

Genetic testing

.



Starkenmann, C.; Niclass, Y.; Beaussoubre, P.; Zimmermann, J.; Cayeux, I.; Chappuis, C. J.-F.; Fieber, W., Use of

fecal and sawdust biochar as a new perfume delivery system. Flavour Fragrance J. 2018, 33 (1), 82-90.

Song, J.; Chen, H., Preparation of aroma microcapsules with sodium alginate and tetradecylallyldimethylammonium

bromide (TADAB) and its potential applications in cosmetics. Flavour Fragrance J. 2018, 33 (2), 160-165.

Fecal & Sawdust biochar for perfume delivery

.



Starkenmann, C.; Niclass, Y.; Beaussoubre, P.; Zimmermann, J.; Cayeux, I.; Chappuis, C. J.-F.; Fieber, W., Use of fecal and

sawdust biochar as a new perfume delivery system. Flavour Fragrance J. 2018, 33 (1), 82-90.

Song, J.; Chen, H., Preparation of aroma microcapsules with sodium alginate and tetradecylallyldimethylammonium

bromide (TADAB) and its potential applications in cosmetics. Flavour Fragrance J. 2018, 33 (2), 160-165.

Alginate microcapsules

.



Mohammadi, N.; Ehsani, M. R.; Bakhoda, H., Development of caffeine-encapsulated alginate-based matrix combined

with different natural biopolymers, and evaluation of release in simulated mouth conditions. Flavour Fragrance J.

2018, 33 (5), 357-366.

Horváth, B.; Pál, S.; Széchenyi, A., Preparation and in vitro diffusion study of essential oil Pickering emulsions stabilized by

silica nanoparticles. Flavour Fragrance J. 2018, 33 (6), 385-396.

Alginate encapsulation

.



Mohammadi, N.; Ehsani, M. R.; Bakhoda, H., Development of caffeine-encapsulated alginate-based matrix combined with

different natural biopolymers, and evaluation of release in simulated mouth conditions. Flavour Fragrance J. 2018, 33 (5),

357-366.

Horváth, B.; Pál, S.; Széchenyi, A., Preparation and in vitro diffusion study of essential oil Pickering emulsions

stabilized by silica nanoparticles. Flavour Fragrance J. 2018, 33 (6), 385-396.

Nanoparticle stabilization

.

• Emotional Response• Analytical Testing• Medicinal Testing• Botany• Flavor/Scent Delivery Systems*• Physical Response (biology)• Categorization Methods for Data• Physical Properties


Chappuis, C. J.-F.; Huber, R.; Niclass, Y.; Starkenmann, C., Simulating latrine conditions to assess perfume

performance against malodour. Flavour Fragrance J. 2018, 33 (4), 313-321.

Latrine models

.



Romagny, S.; Coureaud, G.; Thomas-Danguin, T., Key odorants or key associations? Insights into elemental and

configural odour processing. Flavour Fragrance J. 2018, 33 (1), 97-105.

Bastiaan-Net, S.; van den Berg-Somhorst, D. B. P. M.; Ariëns, R. M. C.; Paques, M.; Mes, J. J., A novel functional screening

assay to monitor sweet taste receptor activation in vitro. Flavour Fragrance J. 2018, 33 (2), 173-183.

Odor and mental connections

.



Romagny, S.; Coureaud, G.; Thomas-Danguin, T., Key odorants or key associations? Insights into elemental and configural

odour processing. Flavour Fragrance J. 2018, 33 (1), 97-105.

Bastiaan-Net, S.; van den Berg-Somhorst, D. B. P. M.; Ariëns, R. M. C.; Paques, M.; Mes, J. J., A novel functional

screening assay to monitor sweet taste receptor activation in vitro. Flavour Fragrance J. 2018, 33 (2), 173-183.

Monitoring sweet receptors

.



Cicchetti, E.; Vasseur, C., Critical comparison of selected olfactometric methods for the determination of impact

odorants. Proposal of a new representation of olfactometric results. Flavour Fragrance J. 2018, 33 (2), 144-152.

Argument for bubble plots

.



Larcinese-Hafner, V.; Tchakalova, V., Co-surfactant, co-solvent, and hydrotropic properties of some common cooling

agents. Flavour Fragrance J. 2018, 33 (4), 303-312.

Barzegar, H.; Mehrnia, M. A.; Nasehi, B.; Alipour, M., Fabrication of peppermint essential oil nanoemulsions by

spontaneous method: Effect of preparing conditions on droplet size. Flavour Fragrance J. 2018, 33 (5), 351-356.

Surfactant properties of cooling agents

.



Larcinese-Hafner, V.; Tchakalova, V., Co-surfactant, co-solvent, and hydrotropic properties of some common cooling agents.


Barzegar, H.; Mehrnia, M. A.; Nasehi, B.; Alipour, M., Fabrication of peppermint essential oil nanoemulsions by

spontaneous method: Effect of preparing conditions on droplet size. Flavour Fragrance J. 2018, 33 (5), 351-356.

Nanoemulsions

Dai, Y.; Liu, Y.; Sun, B.; Yang, S.; Tian, H., Enantioselective syntheses and sensory properties of 2‐Alken‐4‐olides. Flavour Fragrance J. 2018, 33 (2), 166-172.

Enantioselective Syntheses and Sensory Properties of 2-Alken-4-olides

Dai, Y.; Liu, Y.; Sun, B.; Yang, S.; Tian, H., Enantioselective syntheses and sensory properties of 2‐Alken‐4‐olides. Flavour Fragrance J. 2018, 33 (2), 166-172..


Sharplessasymmetricdihydroxylation



Sensory panel test:5 healthy, non-smoking judges

2 male, 3 femaleAges 23 to 29





Retention Times





Amount neededfor detection

Tromelin, A.; Chabanet, C.; Audouze, K.; Koensgen, F.; Guichard, E., Multivariate statistical analysis of a large odorants database aimed at revealing similarities and links between odorants and odors. Flavour Fragrance J. 2018, 33 (1), 106-126.

Multivariate statistical analysis of a large odorants database aimed at revealing similarities and links

between odorants and odors

• Break up odors into “subjective” categories• 150 odor notes• 1000-2000 odorants

• Use self-organizing maps (SOMs) to relate odor with structure via Artificial Neural Network (ANN)

• Draw 3777 odorants from Flavor-Base (a large library of compounds)

• Retain 3571 after removing compounds activating retronasal stimuli

• Remove any descriptors with <5 related compounds• Kept ones like “fruity,” “floral”• Removed 63 odorants

• Used AI to split odorants into similarity “trees”; cut trees at 3 dimensions deep




“Green Split”




• “Rose” can be related to “honey,” “metallic,” “geranium”• “Honey” and “geranium” never exist in an odor description

together• “Rose-honey” and “rose-geranium-metallic” are different

odors related to the perception of the flowers called “roses”

Ding, R.; Li, Y.; Liu, Y.; Sun, B.; Yang, S.; Tian, H., Synthesis of butenolides by reactions of 3-alkenoic acids with diphenyl sulfoxide/oxalyl chloride. Flavour Fragrance J. 2018, 33 (6), 397-404.Stamatopoulos, P.; Frérot, E.; Tempère, S.; Pons, A.; Darriet, P., Identification of a New Lactone Contributing to Overripe Orange Aroma in Bordeaux Dessert Wines via Perceptual InteractionPhenomena. J. Agric. Food. Chem. 2014, 62 (12), 2469-2478.Rajkumar, G.; Shanmugam, S.; Galvâo, M. d. S.; Dutra Sandes, R. D.; Leite Neta, M. T. S.; Narain, N.; Mujumdar, A. S., Comparative evaluation of physical properties and volatiles profile of cabbages subjected to hot air and freeze drying. LWT 2017, 80, 501-509.Shu, N.; Shen, H., Aroma‐impact compounds in Lysimachia foenum‐graecum extracts. Flavour Fragrance J. 2009, 24 (1), 1-6.

Synthesis of butenolides by reactions of 3‐alkenoic acids with diphenyl sulfoxide/oxalyl chloride

Ding, R.; Li, Y.; Liu, Y.; Sun, B.; Yang, S.; Tian, H., Synthesis of butenolides by reactions of 3-alkenoic acids with diphenyl sulfoxide/oxalyl chloride. Flavour Fragrance J. 2018, 33 (6), 397-404.

Synthesis of butenolides by reactions of 3‐alkenoic acids with diphenyl sulfoxide/oxalyl chloride

González, C. G.; Mustafa, N. R.; Wilson, E. G.; Verpoorte, R.; Choi, Y. H., Application of natural deep eutectic solvents for the “green”extraction of vanillin from vanilla pods. FlavourFragrance J. 2018, 33 (1), 91-96.

Application of natural deep eutectic solvents for the “green” extraction of vanillin from vanilla pods

• 2000 to 3000 tons vanilla produced every year

• <1% of vanillin in the flavor market is from vanilla

• Most extracted with aqueous ethanol (50% v/v)• Leaves potentially undesirable ethanol (up to 35% v/v)• Only non-toxic option

• Natural deep eutectic solvents (NADES) might be an option

• Ionic liquids could be useful, but they are highly toxic

• Some natural liquid mixtures have been shown to be ionic• Organic acids/bases• Could explain biological phenomena

• Unlike lipids or water, can dissolve taxol, rutin, etc.

González, C. G.; Mustafa, N. R.; Wilson, E. G.; Verpoorte, R.; Choi, Y. H., Application of natural deep eutectic solvents for the “green”extraction of vanillin from vanilla pods. FlavourFragrance J. 2018, 33 (1), 91-96.

Application of natural deep eutectic solvents for the “green” extraction of vanillin from vanilla pods

Chai, K.; Xu, Z.; Zheng, L.; Zhou, L.; Tong, Z.; Ji, H., Facile separation of cinnamyl acetate and cinnamaldehyde based on host–guest complexation with β-cyclodextrin. Flavour Fragrance J. 2018, 33 (4), 285-293.

Facile separation of cinnamyl acetate and cinnamaldehyde based on host–guest complexation

with β‐cyclodextrin

• Flavoring agent

• BP: 265 °C

• Fragrance agent• Antifungal activity• BP: 248 °C




• Guest-Host technique for separation

• β-cyclodextrin (CD) showed good affinity for CAc in past reports



with β‐cyclodextrinUsing ROESY (Rotating frame Overhause Effect Spectroscopy) to probe

1H-1H coupling through space

Aromatic CAcProtons





Aromatic CAProtons





Aromatic CAProtons

Both show Ph-ringdeep in β-CD




Similar new peaks suggest complexes are isostructural

Chiang, N.; Ho, C. T.; Munafo Jr, J. P., Identification of key aroma compounds in raw and roasted lily bulbs (Bai He). Flavour Fragrance J. 2018, 33 (4), 294-302.http://www.ingenieria-analitica.com/downloads/dl/file/id/1226/product/95/presentacion_sniffers.pdf

Identification of key aroma compounds in raw and roasted lily bulbs (Bai He)

• Lily bulbs (‘Bai He’) are a popular ingredient in Chinese cooking

• Little is known about the odorants responsible for their distinct aroma

• Solvation followed by gas chromatography-olfactometry (GC/O) were used to identify new aroma-active compounds



• They dilute each identified compound and rate how dilute they can still smell it; this gives a flavor dilution (FD) factor• Dilute 1:1 , 1:2, …, 1:1024

• Raw: 25 odorants detected in the FD range from 1 to 1024• Roasted: 42 odorants detected in the FD range from 1 to 1024

Odorants with FD > 63 in Raw Lily Bulbs



Odorants with FD > 63 in Roasted Lily Bulbs

Chen, S.; Xu, Y.; Qian, M. C., Comparison of the aromatic profile of traditional and modern types of Huang Jiu (Chinese rice wine) by aroma extract dilution analysis and chemical analysis. Flavour Fragrance J. 2018, 33 (3), 263-271.

Comparison of the aromatic profile of traditional and modern types of Huang Jiu (Chinese rice wine) by

aroma extract dilution analysis and chemical analysis

• “Pure” microorganism fermentation changes aroma profile

• Huang Jiu is a good study• 60% is from traditional techniques

• Open pottery jars• 30 to 90 days• 3 years of aging

• 40% is from modern techniques • Fermentation tanks• 20 to 30 days• 1 year of aging

• Tested with GC-O and GC-MS


Comparison of the aromatic profile of traditional and modern types of Huang Jiu (Chinese rice wine) by

aroma extract dilution analysis and chemical analysis

Kost, B.; Matysiak, S.; Kula, J.; Bonikowski, R., Synthesis of thiophene derivatives with long-lasting citrusy type odour. Flavour Fragrance J. 2018, 33 (4), 279-284.

Synthesis of thiophene derivatives with long-lasting citrusy type odour

Kost, B.; Matysiak, S.; Kula, J.; Bonikowski, R., Synthesis of thiophene derivatives with long-lasting citrusy type odour. Flavour Fragrance J. 2018, 33 (4), 279-284.

Synthesis of thiophene derivatives with long-lasting citrusy type odour

Determined by a 6-person panel


Chemistry Careers in Fragrance

Firmenich(Geneva)

IFF(Mid-Atlantic)

Givaudan(Vernier)

Symrise(Holzminden)

Takasago(Tokyo)

Frutarom(Haifa)

Sensient(Milwaukee)

Robertet(Nice)

T Hasegawa(Tokyo)

Huabao(Hong Kong)

The Chemistry of Fragrances...The Chemistry of Fragrances Perfumes and More 28 March 2019 1. Brief...

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