THAT MATKAILU TUUS 20180187123A1 TULDU ( 19) United States (12 ) Patent Application Publication (10 ) Pub. No. : US 2018/ 0187123 A1 CLERY et al. ( 43) Pub . Date : Jul. 5 , 2018 ( 54 ) PERFUME COMPOSITIONS Publication Classification (71 ) Applicant: GIVAUDAN SA , Vernier ( CH ) (51 ) Int. CI. CIIB 9 / 00 (2006 .01 ) (72 ) Inventors : Robin CLERY , Horgen (CH ) ; Sandro ( 52) U . S . CI. DOSSENBACH , Gossau (CH ); CPC ...... CIIB 9 /0092 (2013 . 01 ) ; CIIB 9/ 0096 Dominique LELIEVRE , Kindhausen ( 2013 .01 ) ; CIIB 9 / 008 ( 2013 . 01 ) ; CIIB (CH ) ; Boris SCHILLING , Knonau 9 /0076 ( 2013 . 01 ) ; C11B 9 / 0011 ( 2013 . 01 ) ; ( CH ) CIIB 9 /0053 (2013 . 01 ); CIIB 9 /0034 ( 2013 .01 ) ; C11B 9 / 003 ( 2013 .01 ) ; CIIB (21 ) Appl. No. : 15 /757 , 067 9 /0019 ( 2013 . 01 ) ; CIIB 9 /0061 ( 2013 . 01 ) (22 ) PCT Filed : Sep . 23, 2016 ( 86 ) PCT No .: PCT/ EP2016 / 072698 (57 ) ABSTRACT $ 371 (c )( 1) , A perfume complement comprising one or more compounds ( 2 ) Date : Mar . 2 , 2018 selected from compounds present in the fraction of patchouli oil having a Kovats Retention Index on a DB - 5 column of ( 30 ) Foreign Application Priority Data 1500 or lower and/ or olfactively equivalent perfume ingre Sep . 24 , 2015 (GB ) ...... 1516911 . 3 dients US 2018 /0187123 A1 Jul. 5 , 2018

PERFUME COMPOSITIONS deeper understanding of the chemical constituents respon sible for the finer odour nuances of patchouli oil. FIELD OF THE INVENTION 10008 ]. However, rather than analyzing patchouli oil by conventional GC olfactometry, the applicant carried out [0001 ] This disclosure relates to perfume compositions static head space collection on a sample of patchouli oil, and and perfume ingredients useful therein . subjected the head space , rather than the oil , to GC analysis . The applicant was surprised to find a series of peaks , not BACKGROUND TO THE INVENTION detectable on a standard GC trace of patchouli oil , which [ 0002 ] Patchouli, an essential oil obtained by steam dis corresponded to a series of highly volatile compounds that tillation of the leaves of the patchouli plant (Pogostemon have never been described in patchouli oil to the best cablin ) native to Asia , is a popular fragrance ingredient. The knowledge of the applicant. Furthermore , these compounds , main constituents of the oil are reportedly ß -patchoulene , despite their very high volatility and being present in van a - guaiene , caryophyllene , a - patchoulene, seychellene , ishingly low levels , were found to be significant contributors a -bulnesene , nor- patchoulenol, patchouli alcohol and to some of the odour nuances of patchouli oil. pogostol . Its heavy, distinctive scent has been valued for centuries . SUMMARY OF THE INVENTION [0003 ] There have been many attempts to reproduce the [00091 . The present invention provides in a first aspect a odour of patchouli oil . However, as it is universally regarded perfume complement comprising one or more compounds that the sesquiterpenoid ingredients contained in patchouli selected from compounds present in the fraction of patchouli oil are responsible for the heavy, woody, substantive char oil having a Kovats Retention Index on a DB - 5 column of acteristic odour, perfumers have focused their attention on 1500 or lower and / or olfactively equivalent perfume ingre combinations of terpenes and olfactively similar perfumery dients . ingredients in search of the particular fragrance attributes [0010 ] In another aspect of the invention there is provided observed in patchouli oil . Accordingly , whereas this ortho a fragrance composition comprising said perfume comple dox approach to perfume design mimics the odour of ment. patchouli oil to some extent, it does not quite achieve the [ 0011 ] In yet another aspect of the invention there is oil ' s nuanced hedonic effect. provided a fragrance composition comprising said perfume [ 0004 ] In an alternative approach , advanced fermentation complement and a patchouli extender . techniques have been employed to make synthetic patchouli [0012 ] In another aspect there is provided a method of oils . Sesquiterpene synthases and their use in the preparation adapting , modifying or improving the odour of a fragrance of biosynthetic patchouli oils have been described in WO composition , such as a patchouli extender, said method 2005/ 052163 . An example of such a product , ClearwoodTM comprising the step of adding the perfume complement to (see Technical Disclosure , IP. com Number IPCOM000233341D ), is rich in patchoulol and is reportedly the extender. capable of partially or completely substituting for patchouli [0013 ] In yet another aspect there is provided a consumer oil in various technical and fine perfumery applications . product comprising said perfume complement or said fra While ClearwoodTM is stated to possess all the noble notes grance composition . of fresh patchouli” , it is also stated to be distinguishable from the natural oil “ in particular by its having a less DETAILED DESCRIPTION OF THE pronounced earthy , camphoraceous, spicy and leather char INVENTION acter ” . [0014 ] The invention is based on the surprising discovery [0005 ] Thus, the results of these various endeavours to that a highly volatile fraction of patchouli oil consisting of reconstitute the complex odour of patchouli oil are products compounds having a Kovats Retention Index on a DB - 5 that whilst being somewhat reminiscent of patchouli oil, column of 1500 or lower , which is undetectable on a nevertheless lack its distinctive fragrance characteristics. standard GC trace of the oil , contains one or more ingredi Accordingly , whilst these products cannot truly replace ents that contributes significantly to the odour nuances of patchouli, they can be used to dilute or “ extend ” patchouli patchouli oil. Furthermore, some of these ingredients pos oil , and as such they are hereinafter referred to as “ patchouli sess odours that would not immediately be associated with extenders” . A true synthetic replacement for patchouli oil, the odour of patchouli and as such , they enable perfumers to however, remains elusive . draw on their olfactive equivalents from perfumery ingre [0006 ] There remains a need to provide perfume compo dients that would not conventionally be considered to be sitions (hereinafter “ perfume complements ” ) containing relevant in the context of patchouli . In turn , this enables the ingredients or combinations of ingredients that can be added preparation of perfume complements that are unique , dif to fragrance formulations , such as extenders , to adapt, ferentiating and enable the perfumer to move closer to the improve ormodify them such that their odour more closely true odour of patchouli. resembles the uniquely characteristic odour of patchouli oil. [0015 ] The highly volatile fraction referred to herein [0007 ] If patchouli oil is analyzed by gas chromatography, above can be isolated in a number of ways . Fractional the GC trace reveals the characteristic diverse profile of collection techniques include head space trapping , and frac sesquiterpenoids that are regarded as being responsible for tional distillation techniques under various conditions of its odour and certain other peaks corresponding to com temperature and pressure . pounds that are of no olfactive interest. Therefore , beyond [0016 ] In a particular embodiment of the invention , the confirming the characteristic odour profile of the sesquiter fraction of patchouli oil having a Kovats Retention Index on penoid compounds , conventional GC olfactometry has a DB - 5 column of 1500 or lower can be obtained by trapping proven to be ineffective in helping the perfumer to reach a the head space above a sample of patchouli oil. Thereafter, US 2018 /0187123 A1 Jul. 5 , 2018 the trapped headspace can be analyzed by GC olfactometry n = the number of carbon atoms in the smaller alkane whose and / or GC mass - spectrometry . peak is adjacent to the peak of interest [ 0017 ] Head space trapping and analysis is a technique [ 0025 ] In a particular embodiment of the invention com developed to elucidate the odour compounds present in the pounds present in the fraction of patchouli oil, which may be air surrounding various objects. Usually the objects of present in a trapped head space , and having a Kovats interest are objects that are valued for their highly volatile Retention Index on a DB - 5 column of 1500 or lower, more ingredients surrounding them , such as plants , flowers and particularly 1450 or lower , still more particularly 1400 or foods. lower, still more particularly 1350 or lower , and more [0018 ] In principle , after the head space is analyzed , the particularly still 1300 or lower include , but are not limited scents can then be recreated by perfumers , either by employ to 2 -ethyl furan , 4 - Ethenyl- 2 -methoxyphenol , for example ing the compounds found in the head space , or by substi 4 -VINYL GUAIACOL , ethyl 4 -methylvalerate , (48 ,4aS , tuting them with similarly smelling perfume ingredients on SaR ) - 4 , 8a - Dimethyl- 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 -octahydronaphthalen the perfumer ' s palette . 4a - ol, for example GEOSMIN , 4 - Ethyl- 2 -methoxyphenol , [0019 ] As is known by the person skilled in the art , head for example 4 - ETHYL GUAIACOL , 4 - ethyl phenol, 2 ,6 ,6 space equipment involves a container which surrounds the trimethylcyclohexa - 1, 3 - dienecarbaldehyde, for example sample of interest. Inert gases are passed into the space containing the object or a vacuum is established such that the SAFRANAL , 3 - propyl phenol, iso -butyl methoxy pyrazine , volatile compounds are swept out of the head space and 2 -methoxy - 3 , 6 - dimethyl pyrazine and 1 , 2 , 7 , 7 - tetramethyl captured using a variety of techniques among them cold bicyclo [ 2 . 2 . 1 ]heptan - 2 -ol , for example 2 -METHYL surfaces, solvent traps , and adsorbent materials , with the ISOBORNEOL ( either of the enantiomers , or their mixtures latter techniques capable of longer periods of collection . The in any proportion ) . samples can then be analyzed using techniques such as gas [0026 ] These compounds were not previously known to chromatography -mass spectrometry exist in patchouli oil , and many have odours that would not [0020 ] It was counter- intuitive to use fractional collection be readily associated with the characteristic patchouli odour. in the manner described on patchouli oil, because it is widely For example , ethyl 4 -methylvalerate possesses a very attrac accepted that the important odour contributors are those tive fruity odour that is not at all expected in patchouli . found in the liquid fractions, in particular those having a Furthermore , some of the compounds would not even be Kovats Retention Index above 1500 , and more particularly considered to be useful in perfumery , such as 2 -methyl still , those containing predominately sesquiterpenoids , isoborneol ( either of the enantiomers , or their mixtures in which would be analyzed by GC olfactometry on patchouli any proportion ) , which contributes the earthy odour in dirty oil as such , and not a volatile fraction of patchouli oil, and water. Nevertheless , these compounds, alone or in combi particularly not its head space . nation can form a perfume complement that when added to [0021 ] The Kovats Retention Index as it is known in the patchouli extenders , can elevate the extenders and provide art is defined as the selective retention of perfume ingredi them with more authentic patchouli oil character . ents onto chromatographic columns based on the retention [0027 ] Indeed , the use of 2 -methyl isoborneol (either of volume of the substance with respect to that to a homologous the enantiomers, or their mixtures in any proportion ) in series of n -alkane standards. perfumery is entirely unanticipated and forms another aspect [0022 ] The Kovats Retention Index can be experimentally derived using a DB - 5 column according to techniques well of this invention . known in the art , which do not need further elaboration here . [0028 In a more particular embodiment, the invention In a particular embodiment, an Agilent Technologies 6890 provides the use of 2 -methyl isoborneol ( either of the gas chromatogram with Flame Ionization Detector ( FID ) , or enantiomers , or their mixtures in any proportion ) in a equivalent using a DB - 5 ( 5 % phenyl- methylpolysiloxane ) dilution of 0 . 1 to 1000 ppm in a fragrance composition . column 30 mx0 . 25 mm i . d . , with a 0 .25 micron film thick [0029 ] Although the odour direction of the aforemen ness available from Agilent Technologies . Chromatographic tioned ingredients are very useful as such , or in the context conditions may be 1 mL /min ofhelium carrier with constant of augmenting patchouli extenders , given the fact that some flow programming , a temperature program of 50° C . to 300° of these compounds are not considered as conventional C . at 4° C .min ., detector temperature 350° C ., split injection perfume ingredients , they may not be readily available on at 300° C . the perfumers ' palette . Accordingly, in a perfume comple 10023 ]. Different chromatographic conditions may be ment according to the invention , it may be particularly required to achieve separation of the analytes of interest and desirable to employ olfactively equivalent ingredients in a can be readily adjusted by one skilled in the art. A linear perfume complement, either additive with or as alternatives alkane hydrocarbon standard mix (C8 - C22 available from to , the ingredients found in the volatile fraction , which may Aldrich Chemical Company or equivalent) is injected and be extracted from a head space , with a Kovats Retention the retention time for each component is recorded . The test Index of 1500 or less , recited above . Ingredients that the sample ( appropriately diluted in a suitable solvent) is applicant found to be olfactive equivalents and which may injected under the same conditions, and the retention time be used in perfume complements either additively with or for each component of interest is recorded . The Kovats alternatively to the ingredients referred to above , include but Index under non - isothermal conditions is calculated for each are not limited to 2 , 6 ,6 - trimethylcyclohexa - 1 , 3 - dienecarbal component of interest in the test sample using the equation : dehyde, for example SAFRANAL , 4 , 4 , 8a - trimethyldecahy KI = 100n + 100 [ ( tsubstance - tn ) /( tn + 1 - tn ) ] dronaphthalen -4a -ol , for example METHYL GEOSMIN , ( 3S , 5R , 8S ) - 5 - Isopropenyl - 3 , 8 - dimethyl- 3 ,4 , 5 ,6 , 7 ,8 -hexa Where : hydro - 1 ( 2H ) -azulenone , for example ROTUNDONE or, ( 3S ,5R ,8S ) - 5 - Isopropenyl- 3 , 8 - dimethyl- 3 , 4 , 5 , 6 , 7 , 8 -hexa [0024 ] t = the uncorrected retention time of a peak hydro - 1 ( 2H )- azulenone , for example ROTUNDONE - con substance = the peak of interest taining materials ( for example in the form of Akigala US 2018 /0187123 A1 Jul. 5 , 2018 woodTM ) , 2 - isopropyl- 3 - methoxy pyrazine, or other ( 2 ,6 , 6 - trimethylcyclohexa - 1 , 3 -dien - 1 - yl) but - 2 -en - 1 -one , for olfactively similar pyrazine perfume ingredients , such as example DAMASCENONE , 2 - ( 2 - ( 3 , 3 , 5 - trimethylcyclo 2 -methoxy - 3, 5 dimethylpyrazine , 2 -methoxy -5 ,6 - dimethyl hexyl) acetyl ) cyclopentanone, for example DIONE , 4 - ethyl pyrazine , 2 - isopropyl- 5 -methoxy pyrazine, 2 - isopropyl- 6 octanoic acid , dimethyl sulphide, 2 , 4 -diethoxy -5 -methylpy methoxy pyrazine, 2 - sec -butyl - 3 -methoxy pyrazine or 2 -bu rimidine, for example VETHYMINETM , iso - propyl- 2 tyl - 3 -methoxy pyrazine ; methyl geosmin , rotundone or methyl- 4 - thiazole , pine oil ( in particular Siberian pine oil ) , rotundone - containing materials ( for example in the form of 2 - ( 4 -methylcyclohex - 3 - en - 1 -yl ) propan - 2 -ol , for example Akigalawood® ) , clary sage oil , 3 , 8 , 8 , 11a - tetramethyldo 4 - TERPINEOL , Oct - 1 - en - 3 - 01, for example AMYL VINYL decahydro - 1H -3 ,5a - epoxynaphtho [ 2 , 1 - c ]oxepine , for CARBINOL , 8a , 9 , 9 - Trimethyl- 1 , 2 , 4a , 5 , 6 , 7 , 8 ,8a -octahydro example AMBERKETALTM , 2 - ( 3 , 8 - dimethyl- 1 , 2 , 3 , 4 , 5 , 6 , 7 , 1 ,6 -methanonaphthalen - 1 - ol, for example NOR -PA 8 -octahydroazulen - 5 - yl) propan - 2 - yl acetate , for example TCHOULENOL , 5 - isopropyl- 2 -methylphenol , for example GUAIYL ACETATE , (E ) -1 -( 2 ,6 , 6 - trimethylcyclohexa - 1, 3 CARVACROL , 4 -hydroxy - 3 -methoxybenzaldehyde , for dien - 1 - yl) but - 2 -en - 1 -one , for example DAMASCENONE , example VANILLIN , 4 -allyl - 2 -methoxyphenol , for example 2 -( 2 - ( 3 , 3 , 5 - trimethylcyclohexyl )acetyl ) cyclopentanone , for EUGENOL , 2 -methoxyphenol , for example GUAIACOL , example DIONE , 4 - ethyloctanoic acid , dimethyl sulphide , dihydro 4 - allyl- 2 -methoxyphenol , for example EUGENOL , 2 , 4 - diethoxy - 5 -methylpyrimidine , for example VETHY 3 -hydroxy - 4 , 5 - dimethylfuran - 2 (5H ) -one , for example MINETM , iso -propyl - 2 -methyl - 4 - thiazole, pine oil ( in par CARAMEL LACTONETM 4 - ( 1 - ethoxyvinyl) - 3 , 3 , 5 , 5 -te ticular Siberian pine oil) , 2 - ( 4 -methylcyclohex - 3 - en - 1 - yl) tramethylcyclohexanone , for example KEPHALISTM , fenu propan - 2 - ol, for example 4 - TERPINEOL , oct- 1 - en - 3 - 01, for greek absolute , immortelle absolute , cistus absolute , flouve example AMYL VINYL CARBINOL , 5 - isopropyl- 2 - meth absolute , beeswax absolute , dimethyl trisulphide , ethyl ylphenol , for example CARVACROL , 4 -hydroxy - 3 2 -methylpentanoate , for example MANZANATETM , methoxybenzaldehyde, for example VANILLIN , 4 -allyl - 2 2 -methyl propanoic acid , 3 -methyl butyric acid , 4 -methyl methoxyphenol, for example EUGENOL , octanoic acid and ( Z )- methyl 2 -( 3 -oxo - 2 -( pent - 2 - en - 1 -yl ) 2 -methoxyphenol , for example GUAIACOL , 2 -methoxy -4 cyclopentyl) acetate , for example METHYL EPI JAS propylphenol, for example DIHYDRO EUGENOL , 3 -hy MONATE . droxy - 4 , 5 - dimethylfuran - 2 (5H ) -one , for example CARA [0034 ] These so - called olfactive equivalent ingredients MEL L ACTONE , 4 -( 1 - ethoxyvinyl) - 3, 3 ,5 , 5 would not be considered to be conventional choices for a tetramethylcyclohexanone, for example KEPHALISTM , perfumer given the task of creating an accord with fenugreek absolute , immortelle absolute , cistus absolute , patchouli- like odour. A conventional bottom - up approach flouve absolute , beeswax absolute , (methyltrisulfanyl ) meth for the design of fragrances with patchouli - like odour would ane , for example DIMETHYL TRISULFIDE , ethyl 2 -meth direct the perfumer to concentrate on selecting ingredients ylpentanoate , for example MANZANATETM , 2 -methyl pro from the palette that were woody , heavy , substantive ingre panoic acid , 3 -methyl butyric acid , 4 -methyl octanoic acid , dients in the odour direction of the sesquiterpenoid fraction ( Z ) -methyl 2 - ( 3 - oxo - 2 - ( pent - 2 - en - 1 - yl) cyclopentyl) acetate , of patchouli oil . The discovery of the new fraction of for example METHYL EPI JASMONATE , ingredients in the head space provided the perfumer with [0030 ] In a more particular embodimentof the invention a new reference points from which to select somewhat more perfume complement comprises : unconventional perfumery ingredients . [ 0031] at least one of the ingredients selected from [0035 ] The perfume complements described herein above [0032 ] 2 - ethyl furan , 4 - Ethenyl- 2 -methoxyphenol , for may be further complemented with the addition of one or example 4 - VINYL GUAIACOL , ethyl 4 -methylvalerate , more ingredients selected from the group consisting of ( 45 ,4aS , SAR ) - 4 , 8a - Dimethyl- 1 , 2 , 3 , 4 , 5 ,6 , 7 , 8 - octahy 8 - ( sec -butyl ) - 5 , 6 , 7 , 8 - tetrahydroquinoline , for example BIG dronaphthalen -4a -ol , for example GEOSMIN , 4 - Ethenyl- 2 ARYLTM , carrot seed oil, tea tree oil, 2 , 3 - dimethyl pyrazine , methoxyphenol , for example 4 - ETHYL GUAIACOL , 2 , 5 - dimethyl pyrazine , coffee extract, 5 , 8a - dimethyl - 1 , 3 , 4 , 4 -ethyl phenol, 2 ,6 ,6 -trimethylcyclohexa - 1, 3 -dienecarbal 7 , 8 ,8a -hexahydronaphthalen -4a ( 2H ) - ol, for example dehyde , for example SAFRANAL , 3 -propyl phenol, iso GEOVERTOLTM , ( E ) -4 -methyldec - 3 -en - 5 -ol , for example butyl methoxy pyrazine, 2 -methoxy - 3 , 6 -dimethyl pyrazine UNDECAVERTOLTM , methyl 2 , 4 -dihydroxy - 3 , 6 -dimethyl and 1 , 2 , 7 , 7 - tetramethylbicyclo [ 2 . 2 . 1 ]heptan - 2 -ol , for benzoate , for example EVERNYL , 2 -( 3 - phenylpropyl) pyri example 2 -METHYL ISO BORNEOL , AND at least one of dine , for example CORPS RACINETM , cistus oil , hydrocar the ingredients selected from boresine , suederal or other similar leather accords , 1a , 3 , 3 , [0033 ] 2 - isopropyl - 3 -methoxy pyrazine or other olfac 4 , 6 , 6 -hexamethyl - 1a , 2 , 3 , 4 , 5 , 6 , 7 ,7a -octahydronaphtho [ 2 , 3 tively similar pyrazine perfume ingredients , such as b ]oxirene , for example MOXALONETM , 2 -methoxy - 3, 5 -dimethypyrazine , 2 -methoxy -5 ,6 - dimethyl 2 - isobutylquinoline , for example ISOBUTYL QUINO pyrazine , 2 - isopropyl- 5 -methoxy pyrazine , 2 - isopropyl - 6 LINE , 2 , 3 , 3 - trimethyl- 2 , 3 -dihydro - 1H - inden - 1 - one , for methoxy pyrazine , 2 - sec- butyl - 3 -methoxy pyrazine or 2 -bu example SAFRALEINE , birch tar, cade oil, styrax pyroge tyl- 3 -methoxy pyrazine , 4 , 4 , 8a nated , 2 -methoxy - 4 - methylphenol, for example CREOSOL , trimethyldecahydronaphthalen - 4a -ol , for example cypriol oil, 3 -hydroxy - 2 -methyl - 4H -pyran - 4 -one , for METHYL GEOSMIN , (3S , 5R ,8S )- 5- Isopropenyl- 3 ,8 -dim example MALTOL , 2 - ethyl- 4 -hydroxy - 5 -methylfuran - 3 ethyl- 3 , 4 , 5 , 6 , 7 , 8 - hexahydro - 1 ( 2H ) - azulenone , for example (2H ) - one , for example HOMOFURONOL , 2 -hydroxy - 3 ROTUNDONE or ROTUNDONE - containing materials ( for methylcyclopent - 2 - enone , for example CORYLONE, 2 - ( 4 example in the form of Akigalawood® ), clary sage , Amber Methyl- 1 , 3 - thiazol - 5 -yl ) ethanol, for example ketal, 3 , 8 , 8 , 11a -tetramethyldodecahydro - 1H - 3 ,5a - ep SULPHUROLTM , 2- hydroxy -3 , 4 -dimethyl - 2- cyclopenten oxynaphtho [ 2 , 1 - c ]oxepine , for example AMBERKETALTM , 1 -one , for example METHYL CORYLONE , 4 -allyl - 2 2 - ( 3 , 8 - dimethyl- 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 - octahydroazulen - 5 -yl ) pro methoxyphenyl acetate , for example EUGENYL pan -2 -yl acetate , for example GUAIYL ACETATE , ( E ) -1 ACETATE , ( E ) -2 -methoxy -4 -( prop -1 - en - 1 -yl ) phenol , for US 2018 /0187123 A1 Jul. 5 , 2018

example EUGENOL , 2 -ethoxy -4 -methylphenol , for 2 ,3 -dimethyl pyrazine , 2 , 5 -dimethyl pyrazine , a black example ULTRAVANILTM , ( 1R ,4R ,6R , 10S ) - 4 , 12 , 12 - Trim chocolate accord or a coffee oil obtained by supercriti ethyl- 9 -methylen - 5 - oxatricyclo [ 8 . 2 . 0 . 04 ,6 ] dodecan , for cal carbon dioxide extraction . example CARYOPHYLLENE OXIDE , 1 , 3 , 4 , 5 , 6 , 7 -hexa [0043 ] Group B hydro -. beta ., 1 , 1 , 5 , 5 - pentamethyl - 2H - 2 , 4a -Methanonaph [0044 ] ( i) 2 -methyl 1 , 2 , 7 , 7 - tetramethylbicyclo [ 2 . 2 . 1 ] thalene - 8 - ethanol, for example AMBERMAXTM , (4aR ,5R , heptan - 2 -ol , for example 2 -METHYL ISOBORNEOL 7aS , 9R ) - Octahydro - 2 , 2 , 5 , 8 , 8 ,9a -hexamethyl - 4H -4a , 9 ( either of the enantiomers , or their mixtures in any methanoazuleno [ 5 ,6 - d ) - 1 , 3 - dioxole , for example proportion ), AMBROCENIDETM , 1- ( 2 - tert -butylcyclohexyl ) oxybutan 2 - ol, for example AMBER XTREMTM , tobacco absolute , [0045 ] (ii ) 4 ,4 ,8a -trimethyldecahydronaphthalen -4a - ol , hay absolute , bran absolute, 4 -Methylpentanoic acid , for for example METHYL GEOSMIN , example 4 - methyl valeric acid , isoamyl alcohol, hexanal, [0046 ] ( iii) (48 ,4aS , 8aR ) - 4 , 8a - Dimethyl - 1 , 2 , 3 ,4 , 5 ,6 , 7 , hexanol, ( Z ) -hex - 3 - en - 1 -yl acetate , for example HEX 8 - octahydronaphthalen - 4a - ol, for example GEOSMIN , ENYL - 3 - CIS ACETATE , 2 ,6 ,6 -trimethylbicyclo [ 3 . 1 . 1 ] oct- 1 - en - 3 - ol (oct - 1 - en - 3 - ol, for example AMYL hept- 2 - ene , for example PINENE ALPHA , 6 , 6 - dimethyl- 2 VINYL CARBINOL ), 2 -methyl 1, 2 ,7 , 7 -tetramethylbi methylenebicyclo [ 3 . 1 . 1 ]heptane , for example PINENE cyclo [ 2 . 2 . 1 ]heptan - 2 -ol , for example 2 -METHYL ISO BETA , 4 -methylene - 1 - ( 1 -methylethyl ) bicyclo [ 3 . 1 . 0 ] BORNEOL , and 8a , 9 , 9 - Trimethyl- 1, 2 ,4a ,5 ,6 , 7 ,8 , 8a hexane , for example SABINENE , 7 -methyl - 3 -methyl octahydro - 1 ,6 -methanonaphthalen - 1 -ol , for example eneocta - 1 ,6 - diene , for example MYRCENE , non - 2 - enal, NOR - PATCHOULENOL , 8a , 9 , 9 - Trimethyl- 1, 2 ,4a , 5 , 6 , 7 , 8 ,8a -octahydro - 1 , 6 -metha [0047 ] ( iv ) 5 , 8a - dimethyl- 1 , 3 , 4 , 7 , 8 , 8a - hexahydronaph nonaphthalen - 1 - ol , for example NOR -PATCHOULENOL , thalen - 4a ( 2H ) - ol, for example GEOVERTOL , ( E ) - 4 cis 3 -hexanol , 5 -methyl - 2 -hexanone , for example METHYL methyldec - 3 - en - 5 - ol, for example UNDECAVER ISOAMYL KETONE , 2 -methyl butyric acid , indole , TOLTM , methyl 2 , 4 -dihydroxy - 3 ,6 - dimethylbenzoate , 3 -methyl - 1H - indole , for example SKATOLE , p - cresol, for example EVERNYL and 2 - ( 3 - phenylpropyl) pyri p - cresyl acetate , costus oliffac oil , 6 -methyl - 5 - hepten - 2 - one , dine , for example CORPS RACINETM 2 , 6 , 6 - Trimethyl- 1 - cyclohexene - 1 - carbaldehyde, for [0048 ] Group C example BETA CYCLOCITRAL , ( E ) - 4 - ( 2 ,6 ,6 - trimethylcy [0049 ] (i ) 3 -propyl phenol, clohex - l - en - 1 -yl ) but - 3 - en - 2 - one , for example IONONE BETA , undecan - 2 - one and nonan - 2 -one . [0050 ] ( ii ) 4 - ethyl phenol, [0036 Where trivial names are used to describe useful [0051 ] (iii ) 4 -Ethenyl - 2 -methoxyphenol , for example perfume ingredients hereinabove , the skilled perfumer 4 - VINYL GUAIACOL , 2 , 6 , 6 - trimethylcyclohexa - 1 , 3 would understand that these are commonly used names by dienecarbaldehyde, for example SAFRANAL , 4 - vinyl perfumers . However, the skilled perfumer would also under phenol, 4 - Ethyl- 2 -methoxyphenol , for example stand that these ingredients may also be known by other 4 - ETHYL GUAIACOL , 5 - isopropyl- 2 -methylphenol , trivial synonyms, by CAS registry numbers , or by more for example CARVACROL , 4 - propyl phenol and formal nomenclature , such as IUPAC nomenclature . Fur 3 - ethyl phenol, thermore , the skilled perfumer will be familiar with these [0052 ] (iv ) Cistus oil , hydrocarboresine, suederal or other trivial synonyms, as well as with more formal nomen leather accord ) , la, 3 , 3 , 4 , 6 , 6 -hexamethyl - 1a , 2 , 3 , 4 , 5 , 6 , clature , or at the least, will be aware of standard reference 7 , 7a - octahydronaphtho [ 2 , 3 - b ] oxirene , for example works, such as The Good Scents Company website , or the MOXALONETM , 2 - isobutylquinoline, for example Leffingwell website , which contains a comprehensive list of ISOBUTYL QUINOLINE, 2 ,3 , 3 - trimethyl -2 , 3 -di trivial names , registry numbers and more formal nomencla hydro - 1H - inden - 1 -one , for example SAFRALEINE , ture for the perfume ingredients contained on the perfumer 's birch tar , cade oil , styrax pyrogenated and 2 -methoxy palette . 4 -methylphenol , for example CREOSOL , [ 0037 ] In particular embodiments of the invention , per [0053 ] Group D fume complements comprising more particular combina [ 0054 ] (i ) ( 3S ,5R , 8S ) - 5 - Isopropenyl - 3 , 8 - dimethyl- 3 ,4 , tions of the abovementioned compounds are also provided . 5 , 6 , 7 , 8 -hexahydro - 1 ( 2H ) -azulenone , for example Better to define these combinations , the compounds herein ROTUNDONE ( for example in the form of Akigala above named may be divided into Groups A , B , C , D and E , woodTM ) , clary sage absolute , 3 , 8 , 8 , 11a - tetramethyldo as follows : decahydro -1H -3 ,5a - epoxynaphtho [2 , 1- c ]oxepine , for [ 0038 ] Group A example AMBERKETALTM , [0039 ] ( i) 2 -methoxy -3 ,6 -dimethypyrazine , [ 0055 ] (ii ) 2 - ( 3 , 8 - dimethyl- 1 , 2 , 3 , 4 , 5 ,6 , 7 , 8 -octahydroa [0040 ] ( ii ) 2 - isopropyl- 3 -methoxy pyrazine , 2- isobutyl zulen - 5 - yl) propan - 2 - yl acetate , for example GUAIYL 3 -methoxy pyrazine , ACETATE , ( E ) - 1 - ( 2 , 6 , 6 - trimethylcyclohexa - 1 , 3 - dien [0041 ] (iii ) 2 ,4 - diethoxy - 5 -methylpyrimidine , for 1 - yl) but- 2 - en - 1 -one , for example DAMASCENONE example VETHYMINETM , iso - propyl- 2 -methyl - 4 - thi (Firm ), 2 - (2 - ( 3 , 3, 5 -trimethylcyclohexyl ) acetyl) cyclo azole , Siberian pine oil, 2 - ( 4 -methylcyclohex - 3 - en - 1 pentanone , for example DIONE , yl) propan - 2 -ol , for example 4 - TERPINEOL , [0056 ] ( iii ) 4 -hydroxy - 3 -methoxybenzaldehyde , for 2 -methoxy - 3 , 5 - dimethypyrazine , 2 -methoxy - 5 , 6 -dim example VANILLIN , 4 -allyl - 2 -methoxyphenol , for ethylpyrazine, 2 - isopropyl- 5 -methoxy pyrazine , 2 - iso example EUGENOL , 2 -methoxyphenol , for example propyl -6 -methoxy pyrazine , 2 - sec- butyl - 3 -methoxy GUAIACOL , dihydro 4 -allyl - 2 -methoxyphenol , for pyrazine and 2 -butyl - 3 -methoxy pyrazine, example EUGENOL , 3 -hydroxy - 4 , 5 - dimethylfuran - 2 [0042 ] (iv ) 8 - ( sec -butyl ) - 5 , 6 , 7 , 8 - tetrahydroquinoline , ( 5H ) -one , for example CARAMEL LACTONETM , for example BIGARYLTM , carrot seed oil , tea tree oil , (Giv ), 4 - ( 1 - ethoxyvinyl) - 3 , 3 ,5 , 5 - tetramethylcyclo US 2018 /0187123 A1 Jul. 5 , 2018

hexanone, for example KEPHALIS , fenugreek abso [0072 ] In a further particular embodiment, the compounds lute , immortelle absolute , cistus absolute flouve abso - may be combined to provide perfume complements that lute and beeswax absolute , comprise all of A?i ) , B ( i ) , C ( i ) , D ( i ) and E ( i ) , all of A?ii) , [0057 ] ( iv ) Cypriol oil, 3 -hydroxy - 2 -methyl - 4H -pyran B ( ii ) , ( ii ) , D (ii ) and E (ii ) and at least one compound 4 - one , for example MALTOL , 2 - ethyl- 4 - hydroxy - 5 selected from any one of Groups A ( iii ), B (iii ), C ( iii ), D (iii ) methylfuran - 3 (2H ) - one, for example HOMOFURO and E ( iii) . NOL , 2 - hydroxy - 3 -methylcyclopent - 2 -enone , for [0073 ] In a further particular embodiment, the compounds example CORYLONE , 2 - ( 4 -Methyl - 1 , 3 - thiazol- 5 -yl ) may be combined to provide perfume complements that ethanol , for example SULPHUROLTM 2 -hydroxy - 3 , 4 comprise all of A?i ) , B ( i ) , C ( i ) , D ( i ) and E ( i ) , all of A?ii) , dimethyl- 2 - cyclopenten - 1 - one , for example METHYL B ( ii ) , C ( ii ), D ( ii ) and E ( ii ) and at least one compound CORYLONE , 4 -allyl - 2 -methoxyphenyl acetate , for selected from each of Groups A ( iii ), B ( iii ) , C ( iii ) , D ( iii ) and example EUGENYL ACETATE , iso - 4 - allyl- 2 methoxyphenol, for example EUGENOL , 2 - ethoxy - 4 E ( iii ) . methylphenol, for example ULTRAVANILTM , (1R ,4R , [0074 ] In a further particular embodiment, the compounds 6R , 10S )- 4, 12 , 12 - Trimethyl- 9- methylen -5 -oxatricyclo may be combined to provide perfume complements that 18 . 2 . 0 .04 , 6 ] dodecan , for example comprise all of A?i ), B (i ), C (i ), D ( i) and E (i ) , all of A?ii ), CARYOPHYLLENE OXIDE, 1, 3, 4, 5 ,6 ,7 -hexahydro -. B ( ii) , C ( ii ), D ( ii ) and E (ii ) and all of Groups A ( iii ), B ( iii ), beta . , 1 , 1 , 5 , 5 -pentamethyl - 2H - 2 ,4a -Methanonaphtha C (iii ) , D (iii ) and E ( iii ). lene - 8 - ethanol, for example AMBERMAXTM , (4aR , [0075 ] In a further particular embodiment, the compounds 5R ,7aS ,9R ) - Octahydro - 2 , 2 , 5 , 8 , 8 , 9a -hexamethyl - 4H may be combined to provide perfume complements that 4a , 9 -methanoazuleno [ 5 , 6 - d ] - 1 , 3 - dioxole , for example comprise all of A?i ) , B ( i ) , C ( i ) , D ( i ) and E ( i ) , all of A?ii) , AMBROCENIDETM 1 - ( 2 -tert - butylcyclohexyl) B ( ii ), C ( ii ) , D ( ii ) and E ( ii ) and at least one compound oxybutan - 2 -ol , for example AMBER XTREMTM ( IFF ), selected from any one of Groups A ( iv ) , B ( iv ) , C ( iv ) , D ( iv ) osmanthus accord , tobacco absolute , hay absolute and and E ( iv ). bran absolute , [0076 ] In a further particular embodiment, the compounds [0058 ] Group E may be combined to provide perfume complements that [0059 ] (i ) 4 - ethyloctanoic acid , dimethyl disulphide , comprise all of A?i ) , B ( i ) , C ( i ) , D ( i ) and E ( i ) , all of A?ii) , [0060 ] ( ii ) ethyl 4 -methylvalerate , dimethyl trisulphide , B ( ii ) , C ( ii ) , D ( ii ) and E ( ii ) and at least one compound [0061 ] ( iii ) ethyl 2 -methylpentanoate , for example selected from each of Groups A ( iv ), B ( iv ), C (iv ), D ( iv ) and MANZANATETM , 2 -methylpropanoic acid ( iso E (iv ). butyric ), 3 -methyl butyric acid , 4 -methyloctanoic acid [0077 ] In a further particular embodiment , the compounds and ( Z )- methyl 2 -( 3 -oxo -2 - (pent - 2 -en - 1 -yl ) cyclopen may be combined to provide perfume complements that tyl) acetate , for example METHYL EPI JASMONATE , comprise all of A?i ), B ( i) , C (i ) , D ( i ) and E ( i ) , all of A?ii ) , [0062 ] ( iv ) 4 - methylvaleric acid , isoamyl alcohol, hexa B ( ii ) , C ( ii ) , D ( ii ) and E ( ii ) and all of Groups A ( iv ) , B ( iv ) , nal , hexanol, cis - 3 - hexenyl acetate , alpha -pinene , beta C (iv ), Div ) and E (iv ) . pinene, 4 -methylene - 1 - ( 1 -methylethyl ) bicyclo [ 3 . 1 . 0 ] [0078 ] In a further particular embodiment , the compounds hexane , for example SABINENE, 7 -methyl - 3 may be combined to provide perfume complements that methyleneocta - 1 , 6 -diene , for example MYRCENE , comprise all of A?i ) , B ( i ) , C ( i ) , D ( i ) and E ( i ) , all of A?ii ) , non - 2 - enal, cis 3 -hexenol , 5 -methyl - 2 -hexanone , for example METHYL ISOAMYL KETONE , 2 -methyl B ( ii ), C ( ii) , D ( ii ) and E ( ii ) and at least one compound butyric acid , Castoreum base , indole, 3 -methyl - 1H selected from each of Groups A ( iii ), B ( iii ), C ( iii ), D ( iii ) and indole , for example SKATOLE P -cresol , p - cresyl E ( iii) and A ( iv ), B (iv ) , C ( iv ), D ( iv ) and E ( iv ) . acetate , costus oliffac 6 -methyl - 5 -hepten - 2 -one , 2 ,6 , 6 [00791 . The perfume complements described herein above Trimethyl- 1 - cyclohexene - 1 - carbaldehyde , for example may be used as such to perfume all manner of fragrance BETA CYCLOCITRAL , ( E ) - 4 - ( 2 ,6 , 6 - trimethylcyclo formulations useful in fine or technical perfumery . However, hex -l -en -1 - yl) but- 3 -en -2 -one , for example IONONE the perfume complements are particularly useful when they BETA , undecan - 2 -one and nonan - 2 - one are added to a patchouli extender in order to bring the odour [0063 ] In a particular embodiment, the compounds may be of the extender closer to that of patchouli oil . combined to provide perfume complements in any one of the [ 0080 ] The manner in which the perfume complement is following combinations: added to a fragrance formulation , and in particular a [0064 ] (i ) At least one from Group A through E , patchouli extender, is not particularly critical. Thus , when a 10065 ] ( ii ) At least one each from Group A through E , perfume complement comprises more than one compound , [0066 ] (iii ) At least one of A (i ) , B (i ) , C ( i) , D ( i ) and E (i ) , the compounds may be added to a fragrance formulation , [ 0067 ] (iv ) At least one of A ( ii) , B ( ii ), C ( ii) , D ( ii) and and in particular a patchouli extender, singularly or in any E ( ii ) . combination . [0068 ] In a further particular embodiment, the compounds [0081 Accordingly , in another aspect of the invention may be combined to provide perfume complements that there is provided a method of adapting , modifying or comprise either or both of the following: improving the odour of a fragrance formulation , and in [0069 ] ( i ) All of A ( i) , B ( i) , C ( i) , D ( i ) and E (i ) , particular a patchouli extender, said method comprising the [0070 ] ( ii ) All of A?ii ), B ( ii) , C ( ii ), D ( ii ) and E ( ii ) . step of adding to the formulation a perfume complement [0071 ] In a further particular embodiment, the compounds described herein above . may be combined to provide perfume complements that [0082 ] In a more particular embodiment, in a method of comprise all of A?i) , B ( i ), C ( i ) , D ( i ) and E (i ) and all of A?ii ) , adapting , modifying or improving the odour of a fragrance B (ii ) , C ( ii ), D ( ii ) and E ( ii ). formulation , and in particular a patchouli extender , the US 2018 /0187123 A1 Jul. 5 , 2018

ingredients of the perfume complement are added sequen [0094 ] At least one compound from Groups A (i ) , A ( ii) , tially , separately or simultaneously to the fragrance formu B ( i ) , B ( ii ) , C ( i ) , C ( ii ) , and E ( i) present in the proportion 1 lation . ppm - 100 ppm , and at least compound from group D ( i ) [0083 ] The invention also provides a method of preparing present in the proportion 1000 ppm - 100000 ppm ( 0. 1 % - 10 % a fragrance formulation , comprising the step of adding to a weight percent) , fragrance formulation a perfume complement as herein [0095 ] AND any of the foregoing complements , wherein above defined . [ 0096 ] one or more from groups (iii ) and ( iv ) are present [0084 ] In a more particular embodiment, in a method of from 0 . 1 ppm - 10000 ppm ( 0 .00001 % - 1 % weight percent) , preparing a fragrance formulation , the ingredients of the of the patchouli extender or fragrance formulation . perfume complement are added sequentially , separately or 10097 ] Fragrance formulations , in addition to the perfume simultaneously to a fragrance formulation . complement defined herein above, may contain additional [0085 ] The use of the abovementioned perfume comple perfumery ingredients , carriers and adjuvants commonly ments in combination with patchouli extenders , enables the used in fine perfumery and technical perfumery . preparation of extenders or oils that more closely resemble [0098 ] Many of these additional perfumery and non -per patchouli oil, and that can in many instances, substitute for fumery ingredients are disclosed in reference texts such as the patchouli oil itself . the book by S . Arctander, Perfume and Flavor Chemicals , [ 0086 ] As hereinabove mentioned , there are a number of 1969, Montclair , N . J. , USA , or its more recent versions, or commercially -available patchouli extenders. In addition to in other works of a similar nature, such as thegoodscent the previously -mentioned ClearwoodTM ( ex Firmenich ), company . com and Leffingwell websites, as well as in the other examples include Patchouli Reco 3 ( ex Charabot) , abundant patent literature in the field of perfumery . It is also Patchouli Extender ( ex Ventós ), Patchouli Extender (ex understood that said additional ingredients may also be Indukern ) and Patchouli 2235 , 4184 and DM 0356 ( ex compounds known to release in a controlled manner various Robertet) . types of perfuming compounds , such as perfume precursors [0087 ] In a particular embodiment of the invention , the that are themselves not recognized as perfume ingredients , patchouli extender is the product of advanced fermentation . but which can degrade under the influence of an external 10088 ] In a more particular embodiment, the patchouli stimulus such as light or heat or chemical interaction to extender is formed by the action of a sesquiterpene synthase release a perfumery ingredient. on a suitable terpene precursor substrate. An example of a [ 0099 ] Additional perfumery ingredients include the fol suitable terpene precursor substrate is farnesyl pyrophos lowing non - limiting examples : phate (FPP ) . Sesquiterpene synthases , methods of their [ 0100 ) essential oils and extracts , e . g . castoreum , costus production , as well as their use in the preparation of mix root oil , oak moss absolute , geranium oil , tree moss tures of terpenes , including a patchouli extender, are dis absolute, basil oil , fruit oils such as bergamot oil and closed in WO 2005 /052163 , which is incorporated herein by mandarine oil , myrtle oil , palmarose oil, patchouli oil , reference . petitgrain oil, jasmine oil , rose oil , sandalwood oil , [ 0089 ] In yet another aspect of the present invention , there wormwood oil, lavender oil or ylang -ylang oil, is also provided fragrance formulation comprising a [0101 ] alcohols , e . g . cinnamic alcohol, citronellol, patchouli extender, and a perfume complement as herein 3 -methyl - 5 -( 2 ,2 ,3 - trimethyl -3 -cyclopenten - 1 - yl) -4 above defined . penten - 2 - ol) , for example EBANOLTM - farnesol, geran [ 0090 ] The levels at which the compound or compounds iol, 6 - ethyl- 3 - methyl- 5 ( 6 ) - octen - 1 - ol, for example used in perfume complements may be employed in a fra SUPER MUGUETTM , linalool , menthol , nerol, pheny grance formulation , and in particular a patchouli extender, lethyl alcohol, rhodinol, 5 -( 2 ,2 , 3 - trimethyl- 3 - cyclopen will depend on a variety of factors , including the olfactory tyl) -3 -methylpentan - 2 -ol , for example SANDA nature of the extender or formulation and the olfactory effect LORETM - or 1 - ( 2 , 2 ,6 - trimethylcyclohexyl) hexan - 3 - ol, desired . Thus, the levels of individual compounds will vary for example TIMBEROLTM across a wide range , from as low as 0 .01 ppm or as high as [0102 ] aldehydes and ketones, e. g . 7 -( 3 -methylbutyl ) 10 % by weight based on the total weight of the extender or 1 , 5 -benzodioxepin - 3 - one , for example AZURONETM , fragrance formulation into which they are incorporated . anisaldehyde , 0 - amylcinnamaldehyde, 2 - acetyl- 1 , 2 ,3 , [ 0091] Particular perfume complements and ranges 4 , 5 ,6 , 7 , 8 -octahydro - 1 , 2 , 8 , 8 - tetramethylnaphthalene , include : for example GEORGYWOODTM , hydroxycitronellal, [ 0092] At least one of A (i ) , A ( ii ), B (i ) , B ( ii ) , C (i ) , C ( ii ), 1 - ( 2 , 3 , 8 , 8 -tetramethyl - 1 , 2 , 3 , 4 , 5 ,6 , 7 , 8 -octahydronaph D ( i) , D ( ii ), E ( i ) and E ( ii ), each present in the proportion 0 . 1 thalen - 2 - yl) ethanone , for example ISO E SUPERTM ppm - 100000 ppm ( 0 .00001 to 10 weight percent ) , more ( E ) -3 -methyl cedryl ketone , methylionone , verbenone particularly 0 . 1 ppm - 1000 ppm ( 0 .00001 to 0 . 1 weight or; - 4 - ( 2 , 6 , 6 - trimethylcyclohex - 2 - en - 1 - yl) but- 3 - en - 2 percent ), of the patchouli extender or fragrance formulation . one , for example ISORALDEINETM - 3 - ( 4 - tert- butyl) At least one of A ( i) , A ( ii ), B (i ), B (ii ) , C ( i) , and C ( ii) , each phenyl) - 2 -methylpropanal , for example LILIALTM - 1 present in the range 0 .01 ppm - 100 ppm ( 0 .000001 to 0 .01 ( ( 15 , 8aS )- 1 ,4 , 4 ,6 - tetramethyl- 2 ,3 ,3a , 4 , 5 ,8 -hexahydro weight percent) of the patchouli extender or fragrance 1H - 5 , 8a -methanoazulen - 7 -yl ) ethanone , for example formulation . METHYL CEDRYL KETONE, 1 - (2 , 6 ,6 - trimethyl- 1 [ 0093] At least one compound from Groups A?i ), A ( ii ), cyclohex - 2 - enyl) pent - 1 - en - 3 - one , for example ALPHA B (i ), B (ii ), C ( i) , C ( ii ), and E (i ) is present in the proportion METHYL IONONE , 4 ,6 , 6 - trimethylbicyclo [ 3 . 1 . 1 ] 0 . 1 ppm - 100 ppm , and at least one compound from Groups hept- 3 - en - 2 - one, for example VERBENONE or D (i ), D ( ii ), D (iii ), Div ) is present in the proportion 1000 [0103 ] ethers and acetals , e . g . 3a ,6 ,6 , 9a - tetramethyl- 2 , ppm - 100000 ppm ( 0 . 1 % - 10 % weight percent) of the 4 , 5 , 5a , 7 , 8 , 9 , 9b -octahydro - 1H - benzo [ e ] [ 1 ]benzofuran , patchouli extender or fragrance formulation . for example AMBROX ; TM , geranyl methyl ether, US 2018 /0187123 A1 Jul. 5 , 2018

4 -methyl - 2 - (2 -methylprop -1 -en - 1 -yl ) tetrahydro - 2H absorbents such as carbon or zeolites , cyclic oligosaccha pyran , for example ROSE OXIDE or ( ( 1R , 38 ,6S ) - rel rides and mixtures thereof. They may be dissolved or 2 ' , 2 ', 3 , 7 , 7 - pentamethyl- spiro [bicyclo [ 4 . 1 . 0 ]heptane - 2 , dispersed in a carrier material , such as a fat, or enrobed with 5 '- [ 1 , 3 ] dioxane ], for example SPIRAMBRENETM ), maltose - dextrin , gelatine , gum Arabic and the like . [0104 ] esters and lactones , e . g . benzyl acetate , (1S , 0113 ]. Thus , the disclosure additionally provides a method 6R ,8aR ) - 1, 4 ,4 ,6 - tetramethyloctahydro - 1H -5 ,8a ofmanufacturing a consumer product, comprising the incor methanoazulen - 6 - yl acetate , for example CEDRYL poration of a perfume complement as hereinabove described ACETATE , decalactone , 2 - ( 1 - ( 3 , 3 - dimethylcyclo by admixing the perfume complement to a consumer prod hexyl) ethoxy ) - 2 -methylpropylpropionate , for uct base . example HELVETOLIDETM undecalactone or ( 4 , 8 [ 0114 ] The disclosure additionally provides a method for dimethyl- 2 - propan - 2 - ylidene- 3 , 3a , 4 , 5 , 6 , 8a -hexa improving , enhancing or modifying a consumer product by hydro - 1H -azulen - 6 - yl) acetate, for example VETIV means of the addition thereto of an organoleptically appro ERYL ACETATE , priate amount of a perfume complement as hereinabove [0105 ] macrocycles, e . g . ( Z ) -oxacycloheptadec - 10 described . en - 2 -one , for example AMBRETTOLIDE , 1 , 4 - diox [0115 ] The consumer product in which the perfume acycloheptadecane - 5 , 17 - dione , for example ETH complements may be used may be any such product in YLENE BRASSYLATE or 16 -oxacyclohexadecan which the odour of the perfume complements is desired . 1 - one , for example EXALTOLIDETM , Non -limiting examples include fine perfumery , e . g . perfume [ 0106 The fragrance formulations may also comprise and eau de toilette , fabric care , household products and standard perfumery adjuvants . Adjuvants are ingredients personal care products such as laundry care detergents , rinse that do not influence the olfactive properties of a fragrance conditioner, personal cleansing composition , detergent for formulation , but which can affect its quality in other ways . dishwasher, surface cleaner, laundry products , e . g . softener, Adjuvants may include colourants , pH buffers , preserva bleach , detergent, body -care products , e . g . shampoo , shower tives , anti - oxidants , and the like . Adjuvants may also include gel, air care products and cosmetics , e . g . deodorant, van solvents or diluents and emulsifiers , Suitable solvents ishing cream . include dipropylene glycol (DPG ), isopropyl myristate [ 0116 ] The disclosure is further described with reference ( IPM ) , triethyl citrate ( TEC ), alcohol ( e .g . ethanol) , propyl to the following non -limiting example, which depicts a ene glycol (PG ) , triacetin , diethyl phthalate (DEP ) and specific embodiment. benzyl alcohol. [0107 ] Perfume complements as hereinabove described EXAMPLE may be used in a broad range of fragrance applications , e . g . [0117 ] To a sample of ClearwoodTM patchouli extender ( ex in any field of fine and functional perfumery, such as Firmenich ) was added 10 % by weight of a mixture of the perfumes, air care products , household products, laundry following materials ( the mixture is referred to as “ Formula products , body care products and cosmetics . The comple A ” ): ments can be employed in widely varying amounts , depend ing upon the specific application and on the nature and quantity of other odorant ingredients . The proportion is Formula A % (wt ) typically from 0 .001 to 20 weight percent of the consumer Clary sage abs @ 1 % in DEP product. Cistus abs @ 1 % in DEP (0108 ] In one embodiment, perfume complements of the AKIGALAWOOD TM present invention may be employed in a fabric softener in an 2 -methoxyphenol , for example GUAIACOL @ 0 . 1 % 58%aa5 in DPG amount of from 0 .01 to 5 weight percent. 4 - ethyloctanoic acid @ 0 . 1 % in DPG [0109 ] In another embodiment, perfume complements of 2 -methyl 1, 2 ,7 ,7 -tetramethylbicyclo [ 2 .2 . 1 ]heptan - 2 the present invention may be used in fine perfumery in ol, for example 2 -METHYL ISOBORNEOL @ 1 % in DPG amounts from 0 . 005 to 10 weight percent ( e . g . up to about 2 , 4 - diethoxy - 5 -methylpyrimidine , for example 2 weight percent ) , more preferably between 0 .01 and 5 VETHYMINE TM @ 0 .01 % in DPG weight percent. 2 - isopropyl- 3 -methoxy pyrazine @ 0 .01 % in DPG [ 0110 ] However , these values are given only by way of iso butyric acid @ 0 . 1 % in DPG cistus oil @ 10 % in DEP example , since the experienced perfumer may also achieve 4 - ( 1 - ethoxyyinyl) - 3 , 3 ,5 ,5 -tetramethylcyclohexanone , effects or may create novel accords with lower or higher for example KEPHALIS IM NNNNwAN? concentrations . METHYL GEOSMIN @ 1 % in DPG [0111 ] The perfume complements as hereinabove 3 - propyl phenol @ 0 . 1 % in DPG described may be employed in a consumer product simply by directly mixing the composition with the consumer Total product base ( i. e . the consumer product formulation , less the perfumery component. The base will typically include sur 0118 ] The treated ClearwoodTM , along with an untreated factants , diluents and solvents , bleaches, optical brighteners sample and a sample of patchouli oil were submitted uniden and fluorescent agents , fillers and extenders , pigments , dye tified to a panel oftrained perfumers , who were asked to stuffs and other colouring matters , abrasive materials , deter assess the odour characteristics of the three samples in the gent builders , thickeners and rheology modifiers , used in art following applications : recognised proportions ). [0119 ] Alcoholic solution ( 5 % ) on blotter [0112 ] Alternatively , they may be first entrapped with an [0120 ] Added to shampoo base at 0 . 2 % entrapment material, for example , polymers, capsules , [0121 ] Added to fabric conditioner base at 0 . 2 % sub microcapsules and nanocapsules , liposomes, film formers , sequently used to wash cloth , which was then dried US 2018 /0187123 A1 Jul. 5 , 2018

[0122 ] The findings are shown in the following table . containing materials ( for example in the form of AKIGALAWOODTM ) , 3 , 8 , 8 ,11a - tetramethyldodeca hydro - 1H - 3 , 5a - epoxynaphtho [ 2 , 1 - c ] oxepine , for Application Perfumer comments example AMBERKETALTM , 2 - ( 2 - ( 3 , 3 , 5 - trimethylcy clohexyl )acetyl ) cyclopentanone , for example DIONE , 5 % in Alcoholic solution on blotter and 2 -( 3 ,8 -dimethyl - 1, 2 ,3 , 4, 5 ,6 , 7 ,8 -octahydroazulen Clearwood TM weak , woody . 5 - yl) propan -2 -yl acetate , for example GUAIYL Clearwood TM + Formula A adds earthy and pyrazine ACETATE . character of patchouli Patchouli oil Typical patchouli, soft 24 . A perfume complement according to claim 1 com woody, earthy. prising one or more compounds selected from the group 0 . 2 % In shampoo base consisting of: Clearwood TM weak 2 - ethyl furan , 4 -Ethenyl -2 -methoxyphenol , for example Clearwood TM + Formula A stronger , earthy , smoky 4 - VINYL GUAIACOL , ethyl 4 -methylvalerate (4S , effect 4aS , 8aR ) - 4 , 8a - Dimethyl- 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 - octahy Patchouli oil Strong , powdery effect . dronaphthalen -4a -ol , for example GEOSMIN , 4 - Ethe 0 . 2 % in Fabric Conditioner base . Washed and dried cloth . nyl- 2 -methoxyphenol , for example 4 - ETHYL Clearwood TM Weak woody GUAIACOL , 4 - ethyl phenol, 2 , 6 , 6 - trimethylcyclo Clearwood TM + Formula A more performing , more hexa -1 ,3 -dienecarbaldehyde , for example SAFRA patchouli like . NAL , 3 -propyl phenol, iso -butyl methoxy pyrazine , Patchouli oil Strong , musty , earthy , 2 -methoxy - 3 , 6 - dimethyl pyrazine and 2 -methyl iso medicinal effect . borneol ( either of the enantiomers , or their mixtures in any proportion ) . 1 . A perfume complement comprising one or more com 25 . A perfume complement according to claim 1 com pounds selected from compounds present in the fraction of prising one or more of the compounds selected from the patchouli oil having a Kovats Retention Index on a DB - 5 group consisting of: column of 1500 or lower and /or olfactively equivalent 2 - isopropyl - 3 -methoxy pyrazine, or other olfactively perfume ingredients . similar pyrazine perfume ingredients , such as 2 . A perfume complement according to claim 1 , wherein 2 -methoxy - 3 , 5 - dimethypyrazine , 2 -methoxy - 5 , 6 -dim the compounds have a Kovats Retention Index on a DB - 5 ethylpyrazine, 2 - isopropyl- 5 -methoxy pyrazine , 2 - iso GC column of 1300 or lower, and /or olfactively equivalent propyl- 6 -methoxy pyrazine , 2 -sec - butyl - 3 -methoxy perfume ingredients . pyrazine or 2 -butyl - 3 -methoxy pyrazine, 4 , 4 , 8a -trim 3. (canceled ) ethyldecahydronaphthalen - 4a - ol, for example 4 . (canceled ) METHYL GEOSMIN , ( 3S ,5R , 8S ) - 5 - Isopropenyl- 3 , 8 5 . (canceled ) dimethyl- 3 , 4, 5 ,6 , 7 ,8 -hexahydro - 1 (2H ) -azulenone , for 6 . ( canceled ) example ROTUNDONE or ( 3S ,5R , 8S ) - 5 - Isopropenyl 7 . (canceled ) 3 , 8 - dimethyl - 3 , 4 , 5 , 6 , 7 , 8 -hexahydro - 1 ( 2H ) -azulenone , 8 . ( canceled ) for example ROTUNDONE - containing materials ( for 9 . (canceled ) example in the form of AKIGALAWOODTM ) , clary 10 . (canceled ) sage , 3 , 8 ,8 , 11a -tetramethyldodecahydro - 1H - 3 , 5a - ep 11 . (canceled ) oxynaphtho [ 2 , 1 - c ] oxepine , for example AMBER 12 . ( canceled ) KETALTM , 2 -( 3 ,8 - dimethyl- 1 ,2 , 3 ,4 ,5 , 6 ,7 ,8 -octahy 13 . (canceled ) droazulen -5 - yl) propan - 2 -yl acetate , for example 14 . (canceled ) GUAIYL ACETATE , ( E ) - 1 - ( 2 ,6 , 6 - trimethylcyclohexa 15 . (canceled ) 1, 3 - dien - 1 - yl) but- 2 - en - 1 -one , for example DAMA 16 . (canceled ) SCENONE , 2 -( 2 -( 3 ,3 , 5 -trimethylcyclohexyl )acetyl ) 17 . ( canceled ) cyclopentanone , for example DIONE , 4 - ethyloctanoic 18 . (canceled ) acid , dimethyl sulphide , 2 ,4 -diethoxy - 5 -methylpyrimi 19 . ( canceled ) dine , for example VETHYMINETM , iso - propyl- 2 20 . ( canceled ) methyl- 4 - thiazole , pine oil ( in particular Siberian pine 21. (canceled ) oil) , 2 -( 4 -methylcyclohex -3 -en - 1 -yl ) propan - 2 -ol , for 22 . (canceled ) example 4 - TERPINEOL , oct - 1 - en - 3 - ol, for example 23 . A perfume complement according to claim 1 com AMYL VINYL CARBINOL , 5 - isopropyl- 2 -methyl prising one or more compounds selected from the group phenol, for example CARVACROL , 4 - hydroxy - 3 consisting of: methoxybenzaldehyde , for example VANILLIN , 4 - al 2 -methoxy - 3 , 6 - dimethyl pyrazine , iso -butyl methoxy lyl- 2 -methoxyphenol , for example EUGENOL , pyrazine, 2 -isopropyl - 3 -methoxy pyrazine, 2 -methyl 2 -methoxyphenol , for example GUAIACOL , dihydro iso -borneol ( either of the enantiomers , or their mixtures 4 - allyl- 2 -methoxyphenol , for example EUGENOL , in any proportion ) , 4 ,4 , 8a -trimethyldecahydronaphtha 3 -hydroxy - 4 , 5 - dimethylfuran - 2 (5H ) - one , for example len -4a - ol, for example METHYL GEOSMIN , 4 - ethyl CARAMEL LACTONE , 4 - ( 1 -ethoxyvinyl ) - 3 , 3 , 5 , 5 -te octanoic acid , 3 -propyl phenol, ( 3S ,5R , 8S ) - 5 -Isopro tramethylcyclohexanone , for example KEPHALISTM , penyl- 3, 8 -dimethyl - 3, 4 ,5 ,6 ,7 ,8 -hexahydro - 1( 2H ) fenugreek absolute , immortelle absolute , cistus abso azulenone , for example ROTUNDONE or ( 3S ,5R , 8S ) lute , flouve absolute , beeswax absolute , dimethyl trisul 5 - Isopropenyl - 3 , 8 - dimethyl- 3 , 4 ,5 , 6 , 7 , 8 - hexahydro - 1 phide , manzanate , 2 -methyl propanoic acid , 3 -methyl (2H ) -azulenone , for example ROTUNDONE butyric acid , 4 -methyl octanoic acid and ( Z ) -methyl US 2018 /0187123 A1 Jul. 5 , 2018

2 - ( 3 -oxo - 2 - ( pent- 2 - en - 1 - yl) cyclopentyl ) acetate , for 8 -( sec -butyl ) - 5 ,6 , 7 , 8 - tetrahydroquinoline, for example example METHYL EPI JASMONATE . BIGARYL , carrot seed oil , tea tree oil, 2 , 3 -dimethyl 26 . A perfume complement according to claim 1 com pyrazine , 2 , 5 -dimethyl pyrazine , a black chocolate prising accord , coffee extract , 5 , 8a -dimethyl - 1 , 3 , 4 ,7 , 8 , 8a at least one first ingredient selected from : 2 - ethyl furan , hexahydronaphthalen - 4a (2H )- ol, for example 4 - Ethenyl- 2 -methoxyphenol , for example 4 - VINYL GEOVERTOLTM , ( E ) - 4 -methyldec - 3 -en - 5 -ol , for GUAIACOL , ethyl 4 -methylvalerate , (48 , 4aS ,8aR ) - 4 , example UNDECAVERTOLTM ,methyl 2 , 4 -dihydroxy 8a - Dimethyl- 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 - octahydronaphthalen -4a 3 , 6 -dimethylbenzoate , for example EVERNYL , 2 - ( 3 ol, for example GEOSMIN , 4 - Ethenyl- 2 -methoxyphe phenylpropyl) pyridine , for example CORPS nol, for example 4 -ETHYL GUAIACOL , 4 - ethyl RACINETM , cistus oil , hydrocarboresine , suederal , or phenol, 2 ,6 ,6 - trimethylcyclohexa - 1, 3 -dienecarbalde other similar leather accords, 1a , 3 , 3 , 4 ,6 , 6 -hexamethyl hyde , for example SAFRANAL , 3 - propyl phenol, iso 1a ,2 , 3 ,4 , 5 ,6 ,7 ,7a -octahydronaphtho [ 2 ,3 -b ] oxirene, for butylmethoxy pyrazine , 2 -methoxy - 3, 6 -dimethyl pyra example MOXALONETM , 2 - isobutylquinoline, for zine and 2 -methylisoborneol ; 1 , 2 , 7 ,7 example ISOBUTYL QUINOLINE , 2 , 3 , 3 - trimethyl- 2 , tetramethylbicyclo [ 2 .2 . 1 ]heptan - 2 - ol, for example 3 -dihydro - 1H -inden - 1 -one , for example SAFRA 2 -METHYL ISOBORNEOL ; at least one second ingre LEINE , birch tar , cade oil, styrax pyrogenated , dient selected from : 2 - isopropyl- 3 -methoxy pyrazine, 2 -methoxy - 4 -methylphenol , for example CREOSOL , or other olfactively similar pyrazine perfume ingredi cypriol, 3 -hydroxy - 2 -methyl -4H -pyran - 4 -one , for ents , such as 2 -methoxy - 3 , 5 - dimethypyrazine , example MALTOL , 2 - ethyl- 4 -hydroxy -5 -methylfuran 2 -methoxy - 5 ,6 -dimethylpyrazine , 2 - isopropyl - 5 3 ( 2H )- one , for example HOMOFURONOL , 2 - hy methoxy pyrazine , 2 - isopropyl- 6 -methoxy pyrazine , droxy - 3 -methylcyclopent - 2 - enone , for example 2 -sec -butyl -3 -methoxy pyrazine or 2 -butyl - 3 -methoxy CORYLONE , 2 -( 4 -Methyl - 1 ,3 - thiazol- 5 -yl ) ethanol , pyrazine , 4 , 4 ,8a - trimethyldecahydronaphthalen - 4a - ol, for example SULPHUROLTM , 2 -hydroxy - 3 , 4 -dim for example METHYL GEOSMIN , (3S ,5R ,8S )- 5 - Iso ethyl- 2 -cyclopenten - 1 -one , for example METHYL propenyl - 3 , 8 -dimethyl - 3 , 4 , 5 ,6 , 7 , 8 -hexahydro - 1 (2H ) CORYLONE , 4 -allyl - 2 -methoxyphenyl acetate , for azulenone , for example ROTUNDONE or (3S ,5R ,8S ) example EUGENYL ACETATE , iso - 4 -allyl - 2 5 - Isopropenyl -3 ,8 -dimethyl - 3 ,4 ,5 , 6 ,7 ,8 -hexahydro - 1 methoxyphenol, for example EUGENOL , 2 -ethoxy - 4 (2H ) -azulenone , for example ROTUNDONE methylphenol, for example ULTRAVANIL , ( 1R ,4R , containing materials ( for example in the form of 6R , 10S ) - 4 , 12 , 12 - Trimethyl- 9 -methylen - 5 - oxatricyclo AKIGALAWOODTM ) , clary sage absolute , 3 , 8 , 8 , 11a [8 .2 .0 .04 ,6 ]dodecan , for example tetramethyldodecahydro - 1H - 3 , 5a - epoxynaphtho [ 2 , 1 - c ] CARYOPHYLLENE OXIDE , 1 , 3 , 4 , 5 ,6 , 7 -hexahydro - . oxepine, for example AMBERKETALTM , 2 - ( 3 , 8 - dim beta ., 1 , 1 , 5 ,5 -pentamethyl - 2H - 2 ,4a -Methanonaphtha ethyl- 1 , 2 , 3 ,4 , 5 ,6 , 7 , 8 - octahydroazulen - 5 - yl ) propan - 2 lene - 8 -ethanol , for example AMBERMAXTM , (4aR , yl acetate , for example GUAIYL ACETATE , ( E ) - 1 - ( 2 , 5R , 7aS , 9R ) -Octahydro - 2 , 2 , 5 , 8 , 8 , 9a - hexamethyl- 4H 6 , 6 - trimethylcyclohexa - 1 , 3 - dien - 1 - yl) but - 2 - en - 1 - one , 4a , 9 -methanoazuleno [ 5 , 6 - d ] - 1 ,3 - dioxole, for example for example DAMASCENONE , 2 - ( 2 - ( 3 , 3 , 5 - trimethyl AMBROCENIDETM amber Xtreme, osmanthus cyclohexyl) acetyl) cyclopentanone , for example accord , tobacco absolute , hay absolute , bran absolute , DIONE , 4 - ethyloctanoic acid , dimethyl sulphide, 2 , 4 4 -methyl valeric acid , isoamyl alcohol, hexanal, hexa diethoxy - 5 -methylpyrimidine , for example VETHY nol , hexenyl acetate , 2 ,6 , 6 - trimethylbicyclo [ 3 . 1 . 1 ]hept MINETM , iso - propyl- 2 -methyl - 4 - thiazole , pine oil (in 2 -ene , for example PINENE ALPHA , 6 ,6 -dimethyl - 2 particular Siberian pine oil) , 2 - ( 4 -methylcyclohex - 3 methylenebicyclo [ 3 . 1. 1 ]heptane , for example PINENE en - 1 - yl) propan -2 -ol , for example 4 - TERPINEOL , oct BETA , 4 -methylene - 1 - (1 -methylethyl ) bicyclo [3 .1 . 0 ] 1 -en - 3 -ol , for example AMYL VINYL CARBINOL , hexane, for example SABINENE , 7 -methyl - 3 -methyl 8 , 9, 9 - Trimethyl- 1 , 2 ,4a , 5 ,6 , 7 , 8 , 8a - octahydro - 1, 6 eneocta - 1 , 6 - diene , for example MYRCENE , non - 2 methanonaphthalen - 1 - ol, for example NOR - PA enal, cis 3 -hexanol , methyl isoamyl ketone, 2 -methyl TCHOULENOL , 5 - isopropyl- 2 -methylphenol , for butyric acid , castoreum base , indole, 3 -methyl - 1H example CARVACROL , 4 -hydroxy - 3 -methoxybenzal indole , for example SKATOLE , p - cresol , p -cresyl dehyde , for example VANILLIN , 4 - allyl - 2 -methoxy acetate , costus olifacc, 6 -methyl -5 -hepten -2 - one, 2 , 6 , phenol, for example EUGENOL , 2 -methoxyphenol , for 6 - Trimethyl- 1 - cyclohexene - 1 -carbaldehyde , for example GUAIACOL , dihydro 4 - allyl- 2 -methoxyphe example BETA CYCLOCITRAL , ( E ) - 4 - ( 2 ,6 ,6 - trim nol, for example EUGENOL , 3 -hydroxy - 4 , 5 - dimethyl ethylcyclohex - l -en - 1 -yl ) but -3 -en - 2 -one , for example furan - 2 (5H ) - one , for example CARAMEL LACTONE , IONONE BETA , methyl nonyl ketone and methyl 4 -( 1- ethoxyvinyl )- 3 ,3 , 5 ,5 - tetramethylcyclohexanone , heptyl ketone . for example KEPHALISTM , fenugreek absolute , 28 . A perfume complement comprising at least one Group immortelle absolute , cistus absolute , flouve absolute , A compound and / or at least one Group B , and / or at least one beeswax absolute , dimethyl trisulphide , ethyl 2 -meth Group C , and/ or at least one Group D and /or at least one ylpentanoate , for example MANZANATETM , 2 -methyl Group E compound, wherein propanoic acid , 3 -methyl butyric acid , 4 -methyl Group A octanoic acid and ( Z ) -methyl 2 - ( 3 -oxo - 2 - (pent - 2 - en - 1 ( i) 2 -methoxy - 3 ,6 -dimethypyrazine , yl) cyclopentyl ) acetate , for example METHYL EPI ( ii ) 2 - isopropyl- 3 -methoxy pyrazine, 2 - isobutyl- 3 JASMONATE . methoxy pyrazine , 27 . A perfume complement according to claim 23 com ( iii ) 2 , 4 - diethoxy - 5 -methylpyrimidine , for example prising one or more compounds selected from the group VETHYMINETM iso -propyl - 2 -methyl - 4 - thiazole , consisting of: Siberian pine oil, 2- (4 -methylcyclohex -3 -en -1 - yl) pro US 2018 /0187123 A1 Jul. 5 , 2018 10

pan -2 - ol , for example 4 - TERPINEOL , 2 -methoxy -3 ,5 KEPHALISTM , fenugreek absolute , immortelle abso dimethypyrazine , 2 -methoxy - 5 , 6 -dimethylpyrazine , lute , cistus absolute , flouve absolute and beeswax abso 2 - isopropyl- 5 -methoxy pyrazine, 2 - isopropyl - 6 lute , methoxy pyrazine , 2 - sec - butyl - 3 -methoxy pyrazine ( iv ) Cypriol oil, 3 - hydroxy - 2 -methyl - 4H -pyran - 4 -one , for and 2 - butyl - 3 -methoxy pyrazine, example MALTOL , 2 - ethyl- 4 -hydroxy - 5- methylfuran ( iv ) 8 - ( sec - butyl) - 5 , 6 , 7 ,8 - tetrahydroquinoline , for 3 (2H ) -one , for example HOMOFURONOL , 2 -hy example BIGARYLTM , carrot seed oil , tea tree oil, droxy - 3 -methylcyclopent - 2 - enone , for example 2 , 3 - dimethyl pyrazine , 2 , 5 - dimethyl pyrazine, a black CORYLONE , 2 - ( 4 -Methyl - 1 , 3 - thiazol- 5 - yl) ethanol , chocolate accord or a coffee oil obtained by supercriti for example SULPHUROLTM , 2 -hydroxy - 3 , 4 - dim cal carbon dioxide extraction . ethyl - 2 -cyclopenten - 1 -one , for example METHYL Group B CORYLONE, 4 - allyl - 2 -methoxyphenyl acetate , for (i ) 2 -methyl 1, 2, 7 ,7 - tetramethylbicyclo [ 2. 2. 1 ]heptan - 2 example EUGENYL ACETATE , iso -4 -allyl - 2 ol, for example 2 -METHYL ISOBORNEOL , ( either of methoxyphenol, for example EUGENOL , 2 - ethoxy - 4 the enantiomers , or their mixtures in any proportion ) , methylphenol, for example ULTRAVANILTM , ( 1R ,4R , ( ii ) 4 , 4 ,8a - trimethyldecahydronaphthalen - 4a - ol, for 6R , 10S )- 4, 12 , 12 - Trimethyl- 9 -methylen -5 -oxatricyclo example METHYL GEOSMIN , 18 . 2 .0 .04 , 6 ) dodecan , for example ( iii ) (48 ,4aS , 8aR ) - 4 ,8a - Dimethyl- 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 - octahy CARYOPHYLLENE OXIDE , 1, 3 ,4 ,5 , 6 ,7 -hexahydro -. dronaphthalen - 4a -ol , for example GEOSMIN , oct- 1 beta ., 1 , 1 , 5 , 5 -pentamethyl - 2H - 2 ,4a -Methanonaphtha en - 3 -ol , for example AMYL VINYL CARBINOL , 1 ,2 , lene- 8 - ethanol, for example AMBERMAXTM , ( 4aR , 7 ,7 - tetramethylbicyclo [2 . 2 .1 ]heptan - 2 -ol for example 5R , 7aS , 9R ) - Octahydro - 2 , 2 , 5 , 8 , 8 , 9a -hexamethyl - 4H 2 -METHYL BORNEOL and 8a, 9 ,9 - Trimethyl- 1 ,2 ,4a , 4a , 9 -methanoazuleno [ 5 , 6 - d ] - 1 , 3 - dioxole , for example 5 , 6 , 7 , 8 ,8a -octahydro - 1 , 6 -methanonaphthalen - 1 -ol , for AMBROCENIDETM 1 - ( 2 - tert - butylcyclohexyl ) example NOR -PATCHOULENOL , oxybutan - 2 - ol , for example AMBER XTREMTM , ( iv ) 5 , 8a - dimethyl- 1 , 3 , 4 , 7 , 8 ,8a -hexahydronaphthalen -4a osmanthus accord , tobacco absolute , hay absolute and ( 2H ) - ol, for example GEOVERTOL , ( E ) - 4 -methyldec bran absolute , 3 -en -5 - ol, for example UNDECAVERTOLTM , methyl Group E 2 , 4 - dihydroxy - 3 , 6 - dimethylbenzoate, for example ( i) 4 -ethyloctanoic acid , dimethyl disulphide , EVERNYL and 2 -( 3 -phenylpropyl ) pyridine , for ( ii ) ethyl 4 -methylvalerate , dimethyl trisulphide , example CORPS RACINETM ( iii ) ethyl 2 -methylpentanoate , for example MANZAN Group C ATETM , 2 -methylpropanoic acid , 3 -methyl butyric acid , ( i) 3 -propyl phenol, 4 -methyloctanoic acid and ( Z ) -methyl 2 - ( 3 - oxo - 2 ( ii ) 4 - ethyl phenol, (pent - 2 -en - 1 -yl ) cyclopentyl) acetate , for example METHYL EPI JASMONATE , ( iii ) 4 - Ethenyl- 2 -methoxyphenol , for example 4 - VINYL ( iv ) 4 -methylvaleric acid , isoamyl alcohol, hexanal , hexa GUAIACOL , 2 ,6 , 6 - trimethylcyclohexa - 1 , 3 -dienecarb nol, cis - 3 -hexenyl acetate , alpha -pinene , beta -pinene , aldehyde, for example SAFRANAL , 4 - vinyl phenol, 4 -methylene - 1 - ( 1 -methylethyl ) bicyclo [ 3 . 1 . 0 ]hexane , 4 - , 4 -propyl phenol and 3 - ethyl phenol, for example SABINENE , 7 -methyl - 3 -methyleneocta ( iv ) Cistus oil, hydrocarboresine, suederal ( IFF ) (or leather 1 , 6 - diene , for example MYRCENE , non - 2 -enal , cis accord ), la , 3 , 3 , 4 , 6 , 6 - hexamethyl- 1a , 2 ,3 , 4 , 5 , 6 , 7 ,7a -oc 3 - hexenol, 5 -me -hexan - 2 -one (methyl isoamyl ketone) , tahydronaphtho [ 2 , 3 -b ]oxirene , for example MOX 2 -methyl butyric acid , Castoreum base , indole , ALONETM 2 - isobutylquinoline , for example ISOBU 3 -methyl - 1H - indole , for example SKATOLE p - cresol, TYL QUINOLINE , 2 , 3 , 3 -trimethyl - 2 , 3 - dihydro - 1H p - cresyl acetate , costus oliffac (IFF ) , 6 -me - 5 -hepten - 2 inden - 1 -one , for example SAFRALEINE, birch tar, one , 2 ,6 , 6 - Trimethyl- 1 - cyclohexene - 1 - carbaldehyde, cade oil, styrax pyrogenated and 2 -methoxy -4 -methyl for example BETA CYCLOCITRAL , beta - ionone , phenol, for example CREOSOL , undecan - 2 - one (methyl nonyl ketone ) and nonan - 2 -one Group D (methyl helptyl ketone ) . ( i) ( 3S ,5R ,8S ) - 5 -Isopropenyl - 3 ,8 - dimethyl- 3 ,4 , 5 ,6 ,7 , 8 hexahydro - 1 ( 2H ) - azulenone , for example ROTUN 29 . A perfume complement according to claim 28 com DONE , clary sage absolute , 3 , 8 , 8 , 11a - tetramethyldo prising : decahydro -1H -3 ,5a - epoxynaphtho [ 2, 1 - cJoxepine, for at least one compound from Group A ( i) , at least one example AMBERKETALTM compound from Group B ( i ) , at least one compound (ii ) 2 -( 3 ,8 - dimethyl- 1, 2 ,3 , 4 ,5 ,6 , 7 ,8 -octahydroazulen - 5 from Group C ( i ) , at least one compound from Group yl) propan - 2 -yl acetate , for example GUAIYL D (i ) and at least one compound from Group E ( i ) , ACETATE , ( E ) - 1 - ( 2 ,6 ,6 - trimethylcyclohexa - 1 , 3 -dien or, 1 - yl) but - 2 - en - 1 - one, for example DAMASCENONE , at least one compound from Group A ( ii ) , at least one 2 -( 2 -( 3 ,3 ,5 - trimethylcyclohexyl) acetyl )cyclopen compound from Group B (ii ) , at least one compound tanone, for example DIONE from Group C ( ii ), at least one compound from Group ( iii) 4 -hydroxy - 3 - methoxybenzaldehyde, for example D ( ii ) and at least one compound from Group E ( ii ) . VANILLIN , 4 -allyl - 2 -methoxyphenol , for example 30 . A perfume complement according to claim 28 com EUGENOL , 2 -methoxyphenol , for example GUAIA prising : COL , dihydro 4 - allyl- 2 -methoxyphenol , for example all of A?i ), all of B (i ) , all of C (i ), all of D ( i) and all of E (i ) EUGENOL , 3 -hydroxy - 4, 5 -dimethylfuran -2 (5H ) - one, Or for example CARAMEL LACTONETM , 4 - ( 1 - ethoxyvi all of A?ii ), all of B ( ii ), all of C ( ii ), all of D ( ii) and all of nyl) - 3 ,3 , 5 ,5 - tetramethylcyclohexanone , for example E ( ii ) . US 2018 /0187123 A1 Jul. 5 , 2018

31 . A perfume complement according to claim 28 com 36 . A fragrance formulation according to claim 34 , prising: wherein the patchouli extender is ClearwoodTM . all of A?i ), all of B ( i) , all of C ( i) , all of D ( i) and all of E (i ) , and all of A?ii ) , B ( ii ), C ( ii) , D ( ii ) and E ( ii ) . 37 . A method of adapting , modifying or improving the 32 . A perfume complement according to claim 21 com odour of a fragrance formulation , and in particular a prising : patchouli extender, the method comprising the step of add at least one compound selected from the groups consisting ing to the formulation a perfume complement as defined in of A ( iii ), B ( iii ) , C ( iii ) , D ( iii ) and E ( iii ) and / or claim 1 . at least one compound selected from any one of Groups A ( iv ), B (iv ) , C ( iv ), D ( iv ) and E ( iv ) . 38 . A method according to claim 37, wherein the com 33 . A perfume complement according to claim 12 com pounds contained in the perfume complement are added prising all of A?iv ) , B ( iv ) , C ( iv ) , D ( iv ) and E ( iv ) . separately , sequentially or simultaneously to the fragrance 34 . A fragrance formulation comprising a patchouli formulation . extender and a perfume complement as defined claim 1 . 39 . A consumer product containing a perfume comple 35 . A fragrance formulation according to claim 34 , ment as defined in claim 1. wherein the patchouli extender is prepared by advanced fermentation , preferably by the action of a sesquiterpene 40 . A consumer product containing a fragrance composi synthase on the terpene precursor substrate farnesyl pyro tion as defined in claim 34 . phosphate (FPP ) . * * * * *