SCS Summer School. Fragrance. Marianne Martin. 1

Transcription

1 SCS Summer School Fragrance Marianne Martin 1

2 Aims To inspire your interest in fragrance To encourage an understanding of the chemistry of perfumery To help prepare you for the SCS distance learning diploma examination 2

3 Learner Outcomes by the end of the session learners will be able to: Describe at least one extraction techniques for fragrance ingredients of natural origin Build a perfume molecule Describe the use of at least one synthetic and one natural ingredient in modern perfumery Use a smelling blotter 3

4 What are these botanicals? 4

5 Finding out about: each other and our sense of smell In groups of 3 to 5 people find out: 1. Each other s name/s 2. Any professional work with fragrance 3. Any strong memories related to scent 4. Can you identify all the botanicals on the plate between you? 5. If not describe their odour 6. They all contain essential oils in tiny sacs. You can only see the oil sacs with the naked eye in one of the botanicals. Can you see which one? 5

6 Finding out about: each other and our sense of smell In groups of 3 to 5 people find out: 6. They all contain essential oils in tiny sacs. You can only see the oil sacs with the naked eye in one of the botanicals. Can you see which one? 7. Choose a spokes person to tell the best anecdote or reaction to the botanicals to the whole group 6

7 Lemon Citrus Medica Limonum Citrus fruit Grown in Sicily Essential oil sacs mm diameter Cold extraction techniques 7

8 Cold pressed or expressed oil production 8

9 Lemon Citrus Medica Limonum The odour of the fresh essential oil is mouth wateringly close to the original Citrus oils are prone to oxidation and deteriorate quickly How would you store a citrus oil to improve its shelf life? 9

10 What are these botanicals? 10

11 Rosemary Rosmarinus Officinalis Herb Reputed to aid memory In ancient Greece students would rub rosemary on their foreheads before exams to help them remember 11

12 Rosemary Rosmarinus Officinalis Alpha and beta wave patterns in the brain are affected by rosemary Most people feel more alert but calm when smelling rosemary 12

13 Rosemary Rosmarinus Officinalis Rosemary oil contains camphor Camphor is found in medicated products such as Vick s vapour rub In perfumery we use the term camphoraceous meaning smells camphor like camphor 13

14 Lavender Lavandula Aungstifolia Relaxing for many people Helpful for insomnia In perfumery used both for its floral aspect and its herbaceous aspect Plays a part in the eau de cologne accord and in many male fine fragrances In studies lavender treatment decreased beta waves which indicates drowsiness 14

15 Some academic studies confirming the effects of rosemary oil and lavender EEG activity, alertness, and mood were assessed in 40 adults given 3 minutes of aromatherapy using two aromas, lavender (considered a relaxing odor) or rosemary (considered a stimulating odor). Participants were also given simple math computations before and after the therapy. The lavender group showed increased beta power, suggesting increased drowsiness, they had less depressed mood (POMS) and reported feeling more relaxed and performed the math computations faster and more accurately following aromatherapy. The rosemary group, on the other hand, showed decreased frontal alpha and beta power, suggesting increased alertness. They also had lower state anxiety scores, reported feeling more relaxed and alert and they were only faster, not more accurate, at completing the math computations after the aromatherapy session. (Diego et al, 1998) A study with 140 participants looked at the effects on memory of lavender oil, rosemary oil and no odour (the control group). The rosemary group showed overall improved quality of memory but with an impairment of speed compared to the control. (Moss et al, 2003) Rosemary oil said to have a positive effect on mood, concentration and memory for 10 subjects. (Svoboda et al, 2002) 15

16 Clove Buds Eugenia Caryophyllus Spice Contains 75-80% eugenol What problems might occur in personal care products containing clove oil? eugenol Photographs by Tony Burfield 16

17 Clove Buds Eugenia Caryophyllus Spice Contains 75-80% eugenol Eugenol is one of the commonly reported EU allergens How could the addition of clove oil affect the INCI label of a personal care product? Photographs by Tony Burfield eugenol 17

18 Fragrances including Clove oil Old Spice, Shulton, 1938 Opium, Yves St Laurent,

19 Frankincense or Olibanum resin Boswellia Carterii Frankincense oozes from the stems of a bush and hardens in the sun The bushes grow in arid regions of Yemen and Southern Arabia In ancient times there was an incense trade route Wars were fought over the control of frankincense trade Censer 3 rd century BC Shabwa, Yemen British museum collection 19

20 Photo by Muhammad Al Shanfari 20

21 Frankincense or Olibanum resin Boswellia Carterii Olibanum is processed by steam distillation to make the essential oil Olibanum is also extracted using hydrocarbon solvents to make the resinoid In which products can the sticky resinoids cause problems? 21

22 Fragrances containing Frankincense or Olibanum resin Boswellia Carterii 2MAN Comme des Garçons

23 Benzoin INCI name Botanical name Geographic Origins Botanical part Extract Odour family Styrax Benzoin Styrax Tonkinensis Thailand, Indonesia, Philippines Exudate from tree trunk Resinoid Balsamic 23

24 Balsamic Family Benzoin Balsams are odorous resinous exudates from shrubs found in the desert They are sweet smelling and warm so vanilla is included in the balsamic odour family although it is from a dried bean Balsams and balsamic notes include: Benzoin Myrrh Frankincense or Olibanum in the perfumery trade Opoponax Peru Balsam Tolu Balsam Cistus Labdanum Vanilla Olibanum Myrrh 24 Vanilla

25 Pink Pepper Shinus Molle Relatively new perfumery material (1990s onwards) Extraction method uses liquid CO 2 under high pressure in costly equipment made of 20mm thick stainless steel 25

26 CO 2 Extraction Extraction columns charged with botanical Condenser Evaporator Containing heat exchangers Liquid CO 2 storage tank Sump collecting crude extraction product 26

27 Fragrances including Pink Pepper Pleasures, Estée Lauder,

28 Fragrances including Pink Pepper Prada, Prada, 2004 Gucci Guilty, Guicci, 2012 Tokyo, Kenzo,

29 Fragrances including Pink Pepper Eau des Merveilles, Hermes,

30 Tonka bean Dipteryx odorata The tree that yields tonka beans is from central America especially Venezuala 30

31 Tonka bean Dipteryx odorata Tonka beans contain coumarin 31

32 The first synthetic used in perfumery Coumarin IUPAC name Functional group Occurrence Odour note Perfumery uses Chromen-2-one Lactone Found in nature e.g. Tonka beans Powdery Part of the bottom note accord Blends well with moss, balsamic notes and other lactones Fougère Royale, Houbigant, 1882 contained about 50% of the recently synthesised chemical coumarin 32

33 The First Modern Perfume Fougère Royale, Houbigant, 1882 contained about 50% of the recently synthesised chemical coumarin Fougère means fern in French Ferns have little or no odour Houbigant said in his marketing: If God had created an odour for fern it would be Fougere Royale 33

34 THE FOUGÈRE ACCORD Fougère Houbigant 1882 Paco Rabanne pour homme Paco Rabanne 1973 Drakkar Noir Guy Laroche 1982 Hugo Hugo Boss Brut Shulton 1988 Coolwater Davidoff 2013 Le Beau Male Jean Paul Gaultier 34

35 Variation in Odour Perception Student Odour Recognition Journal entries for Calone a) Watermelon; fresh, sweet; reminds me of a summer picnic with watermelon to eat b) Smells like watermelons and cucumbers; fresh, watery, aquatic feel c) Fresh ozonic; reminds me of sea shore, shells, fish, marine life d) Ocean, salty, fishy; matt, wet; reminds me of a smelly beach, not pleasant 35

36 Influence of Synthetics in 20 th Century Perfumery Calone IUPAC name Functional group Occurrence Odour Family Perfumery uses Trend setter 7-Methylbenzo(1,4)dioxepin-3-one Cyclic diether and ketone Not found in nature Aquatic Fresh ozonic, marine note and water melon. Calone is evident throughout the fragrance profile Calone was patented in 1966 but waited until the 1990s to create a new fashion in fragrance: New West for him, Aramis,

37 Influence of Synthetics in 20 th Century Perfumery and beyond Fragrances containing Calone New West for him Aramis, 1988 Acqua di Giò Giorgio Armani 1996 Boss Pure Hugo Boss 2008 Escape for women Calvin Klein, 1991 L Eau d Issey Issey Miyake 1992 L Eau par Kenzo pour Homme Kenzo

38 Find out about fragrance on the web

39 Fragrance Exam Question 2013 a) Answer all parts: Part 1 State which extraction technique would be used in each of the following scenarios to produce ingredients for the fragrance industry and briefly give your reasons: a) Scenario 1: You are a poor farmer trying to supplement your income with a cash crop. You grow vetivert to create terracing on your land. How would you process the vetivert root with limited capital resources? b) Scenario 2: Jasmin is a delicate flower the odour is destroyed at high temperatures. With fellow farmers and the aid of a fragrance raw material producer you create a cooperative to process jasmin flowers. What extraction method/s would you use to make a product that can be used in alcoholic perfumery? c) Scenario 3: You are a flavour/fragrance raw materials producer. There is a huge demand for natural vanilla flavours. What equipment might you invest in to produce a vanilla extract eligible for natural accreditation by COSMOS or Ecocert? Part 2 Describe in detail the extraction techniques used in scenario 2 above. 2 marks 2 marks 2 marks 9 marks 39

40 Fragrance Exam Question 2013 a) Answer all parts: Part 1 State which extraction technique would be used in each of the following scenarios to produce ingredients for the fragrance industry and briefly give your reasons: a) Scenario 1: You are a poor farmer trying to supplement your income with a cash crop. You grow vetivert to create terracing on your land. How would you process the vetivert root with limited capital resources? 2 marks 40

41 Vetivert oil INCI name Geographic Origins Botanical part Extract Odour family Vetiveria Zizanoides Indonesia, Haiti, Bourbon, India Root Oil Woody Vetivert root Vetivert bundles Vetivert Distillation 41

42 Vetivert oil INCI name Geographic Origins Botanical part Extract Odour family Vetiveria Zizanoides Indonesia, Haiti, Bourbon, India Root Oil Woody Vetivert is a grass above ground with a deep odorous root system Vetivert being planted for terracing Vetivert is used here to help protect the more delicate crop basil 42

43 Water Distillation Distillation is mentioned as early as AD A still with a more efficient condensing system was invented by Arab chemists around 11 th or 12 th century AD Arabic manuscript in the British Library 43

44 Stem Distillation 44

45 Fragrance Exam Question 2013 a) Answer all parts: Part 1 State which extraction technique would be used in each of the following scenarios to produce ingredients for the fragrance industry and briefly give your reasons: b) Scenario 2: Jasmin is a delicate flower the odour is destroyed at high temperatures. With fellow farmers and the aid of a fragrance raw material producer you create a cooperative to process jasmin flowers. What extraction method/s would you use to make a product that can be used in alcoholic perfumery? 2 marks 45

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47 Jasmine Jasminum Officinale Solvent extraction with a hydrocarbon solvent produces jasmine concrete 30 C process temperatures do not destroy the delicate odour Concretes contain waxes and pigments as well as the odorous materials that are not soluble in alcohol Further extraction with alcohol makes the absolute 47

48 Fragrance Exam Question 2013 a) Answer all parts: Part 1 State which extraction technique would be used in each of the following scenarios to produce ingredients for the fragrance industry and briefly give your reasons: c) Scenario 3: You are a flavour/fragrance raw materials producer. There is a huge demand for natural vanilla flavours. What equipment might you invest in to produce a vanilla extract eligible for natural accreditation by COSMOS or Ecocert? 2 marks 48

49 CO 2 Extraction Extraction columns charged with botanical Condenser Evaporator Containing heat exchangers Liquid CO 2 storage tank Sump collecting crude extraction product 49

50 CO 2 Extraction The Process The liquid CO 2 is passed over the botanical in a series of extraction columns The liquid CO 2 laden with extract passes into the evaporator where the CO 2 is allowed to vaporise and removed from the extract The CO 2 is condensed and passed into the storage tank to be used again The extract drains out of the evaporator and is collected Costs The pressures involved to maintain the liquid CO 2 are very high The equipment is made of thick stainless steel Capital costs are high 50

51 CO 2 Extraction Extraction columns containing raw material Condenser Evaporator Containing heat exchangers Liquid CO 2 storage tank Sump collecting crude extraction product 51

52 Below are photographs of some of the botanicals extracted using CO 2 Vanilla Coffee Green tea Pink Pepper 52

53 a) Answer all parts: Fragrance Exam Question 2013 Part 1 State which extraction technique would be used in each of the following scenarios to produce ingredients for the fragrance industry and briefly give your reasons: b) Scenario 2: Jasmin is a delicate flower the odour is destroyed at high temperatures. With fellow farmers and the aid of a fragrance raw material producer you create a cooperative to process jasmin flowers. What extraction method/s would you use to make a product that can be used in alcoholic perfumery? Part 2 Describe in detail the extraction techniques used in scenario 2 above. 2 marks 9 marks 53

54 Solvent extraction Charge the vessel with the botanical in this case rose petals 54

55 This shows the spent rose petals after extraction Also the perforated plates separating the petals allowing the solvent to penetrate 55

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57 Diagram without labels to help with revision: Solvent Extraction 57

58 Solvent Solvent Extraction Extraction 58

59 Solvent Extraction The Process The extraction vessel is charged with the botanical Perforated plates allow for thorough contact between the solvent and the botanical The hydrocarbon solvent is added to the vessel Process temperatures around 30 C are typical After some time the hydrocarbon extract solution is tapped off The solvent is removed from the extract by vacuum distillation The recovered solvent is often reused in future batches The extraction vessel needs to be cleaned removing all the spent charge Steam is used to clean the vessel but is not part of the extraction process 59

60 Solvent Extraction Concrètes The hydrocarbon solvent extracts non-odorous materials from the botanical as well as the odorous materials The non-odorous materials are mainly waxes and colours Concrètes are insoluble in alcohol (ethanol) or water based systems They can be used directly in soap perfumery and non-aqueous balms Concrètes are the starting point for further extraction with ethanol to produce absolutes Absolutes An absolute is made by mixing ethanol with the concrète Tapping off the ethanol solution from the waxes Distilling off the alcohol under vacuum Absolutes are soluble in alcohol (ethanol) but still contain colour 60

61 Comparison of extraction techniques Extract Cold Pressed essential oil from citrus fruit Essential oil by Steam distillation Temp of process Ambient 100 C (lower if vacuum applied) Hydrolysis Sometimes if there is contact with juice (less if dry steam used) Protein degradation stilly odours Contains waxes Contains colour Capital investment for equipment X Low to Medium X Low levels Low (Higher for vacuum and dry steam) Certified Natural by COSMOS Concrete ca 30 C X X High levels Medium X Absolute ca 30 C X X X High levels Medium X CO2 extract Sub critical C typical X X X Medium Very high Super critical 31 C+ X X X Medium Very high 61

62 STABILITY of PERFUME in the PRODUCT BASE 62

63 ACCELERATED PERFUME STABILITY TESTING IN FRAGRANCED END-PRODUCT General Principle: The rate of reaction doubles for every 10 C rise in temperature Thus 24 months 20 C 6 40 C Typical Test Conditions Fridge (3 C) Control Room Temperature (20 C) 6 months 40 C Oven 3 months and 6 months 55 C Oven 1 week UV light (over night) 63

64 ACCELERATED PERFUME STABILITY TESTING IN FRAGRANCED END-PRODUCT CONTROLS Typical Test Conditions Unperfumed control Fridge (3 C) Control Room Temperature (20 C) 6 months 40 C Oven 3 months and 6 months 55 C Oven 1 week UV light (over night) Always include an unperfumed control in accelerated stability testing kept at all the conditions above The unperfumed control base must include all additives for the variant accept the fragrance If problems arise in the unperfumed base they are then not caused by the fragrance The unperfumed control helps in odour assessment 64

65 STABILITY TYPICAL PH FOR VARIOUS PRODUCTS: ph Product base 1 Acid cleaners: Limescale removers 2 3 ACID 4 Anti-perspirant roll-on / Self tanning creams 5 Anti-perspirant deodorants aerosol 5.5 Alcoholic perfumes: Eau de Toilettes etc 6 NEUTRAL 7 Creams / Lotions / Shampoos / Shower gels / Bath foams 8 9 Soaps ALKALINE Low cost soaps / Perm lotions / Depilatories Alkaline cleaners 65

66 STABILITY PERFUME INGREDIENTS AFFECTED by ph of PRODUCT For example: Esters may be affected by ph of product De-esterification to acids and alcohols If the acid involved has an unpleasant odour, such as acetic acid found in vinegar, de-esterification will usually lead to a failed stability test If the acid involved is odourless such as salicylic acid the odour character after de-esterification is often acceptable Sterically hindered esters tend to be more stable 66

67 STABILITY PERFUME INGREDIENTS AFFECTED by ph of PRODUCT What types of personal care products will encourage deesterification reactions? Answer: Aqueous products with acid ph Such as: Antiperspirant deodorant roll-on ph 4 67

68 Terpenes and Terpenoids Isoprene is the building block of essential oil chemistry Monoterpenes can be considered as two isoprene units together head to tail Sequiterpenes can be considered as three isoprene units joined together Isoprene 2-Methylbut-1,3-diene head tail Isoprene unit Isoprene units joining up to make d-limonene Is d-limonene a monoterpene or a sesquiterpene? 68

69 Monoterpenes Strictly speaking monoterpenes are hydrocarbons Hydrophobic Very volatile Easily oxidised to peroxides at double bonds Top notes D-Limonene is the major constituent of citrus oils (99% of orange oil) Pure D-Limonene is very low in odour 69

70 Sequiterpenes Sequi is a Latin prefix which means half as much again Terpenes have 10 carbons and sesquiterpenes 15 Sesquiterpenes are less volatile and contribute to the heart of the fragrance Patchouli oil contains a complex mixture of sesquiterpenes including beta selenine below (and its main constituent patchoulol a sequiterpenoid) Isoprene units (in red) joining up to make beta selenine Beta selenine 70

71 Sequiterpenes Sequi is a Latin prefix which means half as much again Terpenes have 10 carbons and sesquiterpenes 15 Sesquiterpenes are less volatile and contribute to the heart of the fragrance Patchouli oil contains a complex mixture of sesquiterpenes including beta selenine below (and its main constituent patchoulol a sequiterpenoid) 71

72 Aims To inspire your interest in fragrance To encourage an understanding of the chemistry of perfumery To help prepare you for the SCS distance learning diploma examination 72

73 Learner Outcomes by the end of the session learners will be able to: Describe at least one extraction techniques for fragrance ingredients of natural origin Build a perfume molecule Describe the use of at least one synthetic and one natural ingredient in modern perfumery Use a smelling blotter 73

74 Good luck with your studies The average person : takes about 3 million breaths a year Enjoy your sense of smell Thank you 74