DE1617009A1 - Fragrances - Google Patents

Description

- on, κ. assmann

OH. R, KOSNIMMMKK DIPt * -PMVS. R,

1M9NOHINI,

Ar / i8 1890 I 1 96070

FLAVORS AHD WMMKOES HO ·, Iw tork, Fragrances

There is a significant need in the perfumery industry on subs dance with a holy scent note «the suBin & est something constant 1st. Materials are particularly desirable the one hols-like fragrance old a warrior-like fragrance unite. Such hol-like, fight-like fragrance batteries find versatile use in the manufacture of fragrance modifications and manufacture ParfumKusaanietteetsungen · A limited Lots of such materials are available from natural sources, but the natural materials vary widely in quality subject, expensive and limited (and often critical short term) available. .

The present invention relates to new compositions and Components, as well as new procedures and advanced steps, their Features are described below as an example

0098 87/1631 _ba d

and the proposed embodiments of the invention affect.

lure said respective s the new erfindungegeoÄßen cyclic materials 1, 5f S-Trlmethyl-IJ-oxabicyolo / iO, 1 »0] trideca-4,8-diene and its hydrogenated" cyclislerte and redusierte DeriYate including 1 ₉ S9- ^ i * etkylcyclododec «-4,8 ~ dittt-2 ~ one and cyclized Srinethyleyclododeeatrien and EpoxyderlYate des oyollaorten Xriaethyloyolododeeatriene · The process according to the invention basically concerns the conversion of 1.5 _; 9-Irimethyl-cycle4odeeatrlen Kit, an epoxidation agent and if necessary a cyclization agent, both agents can be used. Under certain conditions, the treatment leads to a serious epoxy derivative, and under other conditions a ketone material is obtained as the main product · The substances produced in this way can be further treated as * .B. through hydrogenation or editing » from other useless new materials. »,

These new cyclic materials are the following: I _f 5t9 * -0yolododeeatriea-1 _v 5f9-derived from the general Poreel I.

BATH

003887/1531

in the C ^ - γ _Λ - CHj the

HO - 0 - OH ·, HgG · »0 - 091«, or Q - O -OH,

means and the dashed

represent; the oyclized

O ^ * Gg - CH. the Oroppiertsng HO - 0 HC - C - CH. tmS means the Speaqrprodvkte der ofei «« a cy-

elized derivatives, wean 6 ^ - C _m - OH «the Owippiemog

HC »C - OH, means.

The compounds of the öbi £ $ t & fforael I are made dusch λ) ütaeetsung tob 1, $, 9-Cyelod «9deo« trien-1 _t 5.9 alt of an organic pencerbonic acid ttmter uae β freeing conditions in Öegecvairt; A mlimllsohen rain in the formation ^ τ © η 1,5,9-Irieethyl-15 * oxmbioyclo [10,1,0] tridee & «4, a-diene, old an organic percai?

€ 09887/1631 ^mp

Ton 1y5 _i 9-Iriaethyläodeea-5 _f 9- & ien-2-one, and / or

b) Cyclization of 1,5,9 ~ ^ rinttliyl-13-oxabicyclo [iC, 1 _t O] trideca-4,6-diene or of 1 _v 5 ₍ 9- ^ rttiethylo7clododeofitrien <-1 _f 5f9 with a

Proton donor cyclization agent,

and if necessary, one or more of the following Terfabrens-8 tnfens

o) catalytic © reduction of the products of stages a) and b), ms Reduce one or more unsaturation hindrances or Gen Ιο before making from it,

d) Reduction of the 1,5,9-? riÄethyl-.13-oacabicyolo [10 _i 1 _i O] trideca-4 _f 8 "'diena with an alkaline ketal hydride with formation of 1> 5, S-trimethyloyolododeee / -4 _v 8-diene-> 1-ol _f

e) Epoxidation of the cyclized products formed in step o) with a percarboxylic acid in the presence of an alkaline reagent.

The new materials mentioned here can be used in a large number of Stole from finished perfume sets and components for ready «Barefoot UsaMieneetsungen to be installed. £ e was found that the new materials according to the invention go on and on described in more detail below, have a persistent fragrance, which you are particularly suitable after only familiarization with Pa? - Foot shaving sets in which a starry wood-like scent note is needed.

BATH ORIGINAL

00S887 / 1S31

One of the main materials "files obtained by YergendÄ · invention is 1,5" 9-tri "etbylri5- ^ imtIoyclo [1O ₉ I ₉ O] trideoa-4,6-diene (in the following course al * * Bicyolo- < J-12 "beeeiohnet). Due Bicyclo-C-12 is manufactured by Behft & älsaa« του 1,3,9-iriaethylcyclododeoatrien (read follow & den aaoa al « ^e Oyolo ^ -C-12" b »- aeiohnot) alt an organieeheii Peroftrbofisttar · In Segtiamrt an alkaline Ree ^ geas. Oieee Utaeetettnf should be carried out under certain conditions, that * every greater * YASseziMng · fttr the action cach-Uill «igt. '

Sin another main hangover 1 * 1 _f ä «8 dttrcb d * e

according to ancestors, iet oyoliaiertee! frisethylcyclod ode ca tr ion, la following «tioh as" oyclisiertee 0yolo-O-12 *

endorsed. A cyclized Bleyolo-0-12 could also be obtained according to the present invention. From the following description it will emerge that the oiled materials are useful perfume- and fragrance-modifying substances and products for the manufacture of other arfanous and dnftaodilizing subotanses.

The erf indungegesäßen oyclieierten Katerialien can be obtained by treating the cyclo-C-1 2 or Bloyclo-Katerials ■ it einesQ Frotonendonator or mttum Blektronenekjteptor. Although the Re & ktionßEöohanißffliua has not yet been fully clarified, it is currently assumed that the ^ rotonevdonator is a

0O9SS7 / 1831

forms "in which one of the Jtappelblndungeii contains a proton or a positive charge and that this charge is there and matter! responsive pike. Examples of solohe Frotonendonmt'orwtterialien are sulfuric acid and various PhoephorsMuren eineobliefilion dilute orthophosphoric ₉ konsentrlerter phosphoric acid and phosphorus earlier & acids such as Pyro - and polyphosphoric acids. A precautionary cyolizing agent is 85% phosphoric acid. Boron trifluoride .1st esenfalle eia srAmoasAres C ^ elizing agent. Unless otherwise stated, see all 1 e.ile »quantities, percentages and proportions based on weight,

The present invention is also defined by the attached ⁽ Zeiolmiangen, in which Figures 1 and 2 infrared

represent öba © rptiom iiaaMR spectra of the oyelieievten BIcyolo-O-12;

FIG. 3 gives an infrared absorption spectrum of ojolislertea Cyclo-C-12 again? and Figure 4 shows an infrared absorbency peel & sfa from epoiy-cyoli-

constituted oyoIo-C-12.

Cyclo ~ C "12 is used iss aUgeaeinen available in purities of 90 £ and above, and it may in this Fora" In carrying out the S _r f indung is allgeBelnen is jedooh bevorsugt, clean the material on virtually 100 f> Hein unit shown below. Such purification is easily effected by fractional distillation.

. . . ■ 'BAD ORiGiNAL

009817/1811

At the 2> ore "s eriindungsecaafien Yerfa & sene ale Xposc ^ ierunge & ittel eleventh organic Pexeaxbonsttiaze used Ik al 1 & can mean, jefi © organic alipbatlsene or aromti-

see Peroarbonefture with 1 to about 10 carbon atoms

Success inventions are invested in. Arose, ti «cfc * Peroar-

bonsMuren like Perbeiuioeslliastf «Pesphtteleettre w & Oh3.Qff |» erbeBSoe «- eä ^ ren and« liphatleolia Tete * .t / how0na9A like wttneoheniweisrtexweise beia

used, lime beroxsiggt Terweafiete ergaaleeb »represents Pereesigsliase äar. la is in the sl% is @ £ s ^ practically 1 fetch of the oxgafdeolien Perattrare tux Each fetch of the en treating C ^ olo- € -> 1i sm

Ue good JLuebutteii am Bioyole-® * »11 en - # κ @ & βϊιοα ₉ 9 © Ht®; © i® al» kmlißckes Reaeens anweeeafi aein. Ba da "" sf i @ äf ^ gig "ai $ e Heaktionegenieoh pnti ^ tiseh anhydrous _t is% mter of the Ansfiru @ k * all" lieohee reagent ^{9 used here,} a material is rare that there is leaktionegeaisoh in wles ^ igea Heoius alkaline brook wlir4e. line large Tielaahl voa Balsen a stficken baee bit an aelwleiieren acid «Soinn ft & - dissen Sweck are used. Sin bHBToxsugtee pH <»Icontrolliesendee material represents twaasorfrelea l & tritBBacetat.

The treatment ύολ Cyclo-C-12 ait «inem

is Törsugewaiee durohfef @ hrt in an "" inert EeaktlonstrMger.

- '.: ■■. ^: './ """. - BADOBIGINAL

QOSiST / Vf ti

Am such a re & ktionträger let wHaoohonawerterwelse a sungeaittel for the components of the Re & ktionagemieohee or oine Liquid in which the components of the Reaktlonegenlschee easily dlsperglerbar elad. The carrier serves dtisu, a longer contact the coaponents of the Rsaktionagesischee safely share the bus and the ! facilitate temperature control and also the UiRsetinmg see TerlAngasaen. 2u suitable carriers at the DurchftThruiag dea inventions? experienced8 include chlorinated soles ^ asscretof « fe like Ghlorofora and SetrAChlorkarbonstoff »aronatleche Materia.» Lien like Beasol and toluene and oxygen-containing solvents vle Biätfcjrlftther. lin beTorsugter 9r8ger at the practical Durohitthrung the invention let Hethylenohlorld.

The epoxidation can be carried out internally via a teaperatural laboratory, depending on the particular Eonsentratlen of the Reaktlonepe, rtiier ₉ the outer surface of the Reaktlonegef & ß and other TerfQgs «£« a · equipment and the like · In a low separator "rejection is not taken into account Long sesJctloneseity whereas with a too high feasperature the tUwetmag uaemeBeoht soiaMll “At too high sea temperatures the RMktloasfssehwimdiglceit become so strong that it leads over Iznloslom. Bs is therefore wtinsohsnswert "the Spoxydlerungsreaktion v« i ^ Ses ermturen 1 "range τοη about -15 ⁰ C to 5O etva ⁰ O 4" whMitthr "ii ·

BAD LOCAL

-OOIIIf / ilti.

The time required for the spoxydation reaction varies in inverse proportion to the temperature and should be sufficient to ensure a high level of sensitivity. It is reaction conveniently controlled by introducing d "e Cyclo-C-12 and optionally the Slower in ei" Raaktiomsgef & ß, which Rait MischTorriohtungen and WMmetföertraguagevorriehtungen is equipped, and anßchlieSenÄ "langeeiM addition of the required amount of Epozydierungeaittel they · ReaktionsBaase can nötigenfallo ici geutineohten \ The temperature must be maintained after the admissibility of the reaction adLttel has been given until the temperature is complete.

In allgsEseinen a Seaperaturbereioh of about -15 ⁰ O to about 3O ° E over a period of about 2 τοη bi »5 hours for the addition of per carboxylic acid needed. The pressure can be carried out at sub-atmospheric or tiberata-atmospheric pressure, but if sub-atmospheric pressure is used, it should not be so low that boiling or substantial yerda consumption of deaers or any of the reaction partners takes place. UmeetBung is preferably carried out at Iteoephäreadruck. If the reaction is sensitive to the presence of water, it should not be carried out in a very humid atmosphere, although it is not necessary to do so. If desired, the unsetting can be carried out under an inert atmosphere such as nitrogen, argon or the like.

00S8l? / 1S3t

- ίο -

When the Bpoaqräieru & gsreaktion is practical, it will she finished by adding Waster. There »Vaseer is in there · Organic KatorIaI braided and removed from it, being the distance aa loiohtesten duroh decanting the organic layer can be made from the previous layer.

The Reaktlonsproduktgesiieeh can "be ereinigt by adding a reducing agent" dee to any traces SpoXsrdierungcaittelB su inactivating · Zvtk example, the organic layer of v ftrige & äSsmag a reagent such as sleen & 3Bonlttfiaulfat be treated old Veit. The reaction product is generally further deacidified, for example with a väfirigen Eatrlueibicarbonatlueung, vm remove all traces of acidic materials see below. The ®iujcle> -0-12 is obtained from the reaction mixture by distillation after washing and decanting the organic sehloht.

The reaction product is a clear liquid an intense and constant HolahAaber-Buft · Se has one Boiling point from 106 to 10θ ° 0 at 1.0 m Bg and a | °. « 1.5046 to 1.5055. The XR, SCR and Maeaenspcktren stianen ttbereln old spanked nöglion geoetrical isomers, einsehlleSlloh one of the following structures

BAD ORfGiNAL

009817/1131

- it -

Bicjolo C-12 derivatives are manufactured and treated with it WeBseretoif in the present «ines Hjdrier! Cate% eatore vie Sicke !, Palladium, platinum «Bhodius or dsrea Sfclsen» Prevailed lly— dri ^ Jattalyetitoren elnft Salladii »and daeesii Salse vie Pmlladiuechlorid.

If the Dihyarcbicyclo- € ~ 1S report is desired, the β Haterial Bit will be a hol tfaenerst @ £ f h ^ Mz ^ & Tk, The f etrahjdroiraterial can be obtained by TerveBänztg tos 2 or sislsr Molen Vaoeezv at off. Bo is open iohtl i _P d «S Genieohe of the Bieyclo-0-12 lind Sihydroaaterlale or the dihydro- lind $ et? .Ahydroderivate by taviating the Meage at ¥ &8" er * toff up to eu 2 mol hergeeteil "can earth. The hydrogenation can be carried out at pressures of about 14.1 atii200 pslg), over & tasoaph & risohe pressures in the order of Ton7.03atti (.100 pslg) are prevented, since the unset * img goes faster and more quickly under eolehen pressure conditions.

bath

To carry out the hydrogenation, the catalyst can be used directly in the BioyolO-O-12 can be introduced and the Geaieoh can then Treated with hydrogen · It is preferred that an inert reaction carrier be the Bicyolo-C-12 in the hydrogenation process is sugeaiseht. So are s.B. lower alkynols want »* ti te Reaction carrier and ethanol is more slow to react.

The temperature used can range from 81% to over 10O ⁰ O and it is kept at 80 to 10O ⁰ O torso. At low temperatures, the Vaeserstoff is only absorbed slowly while lying at temperatures "ear riel higher than 100 ⁰ C, the reaction proceeds so that calibration sohnell * s problems give rise to their control.

The hydrogenated Bioyelo-C-12 is isolated from the reaction chemistry by filtration, did not remove the catalyst solids and by a subsequent distillation, did one if necessary to remove used frlgersubstanfi. Sa will advised against such a distillation to remove the carrier liquid under Yakwa durohBUfdhren. If desired, can the hydrogenated material can be further purified by fractionated Distillation.

The hydrogenation of Bicyolo-0-12 with a KoI of hydrogen leads to dihydro compounds including 1,5,9-triaethyl-15-exabicyclo (iO _t 1, O] trideo & -4-0n, this compound is a colorless oil with eicco bolB-like air scent, a boiling point of - 009887/1831.

72 ⁰ CI »·! 0.2 si Hg UBd «according to aj °« 1.5021 · 8pekfcrftiaftttr * i «ibut« ett latten recognize that the Holefeulazgevient was 222 and the failure of the connection follows:

Λ • ■

If t Get What β era toff bet hydrogenation Tezwendet wtrden, ^ F9? RiBieth3rl "13-oxfibioyolo [OK _r 1.0] t ^ ideo" n is 1 obtained. Since »Katerlal represents a colorless oil old holsBänliolier Aabex & uftnote, similar to the dee Bioyolo-C-12, old eiatA boiling point of 72 ⁰ O at 0.2 approx% and ng * 1.4975. Mass spectroscopy, which reveals a molecular weight of 224, confirms the structure shown *

/ V ν

009 8 87/1 ^ 31

The cyclization of Cyoio-0-12 or Bicjolo-O-12 is Yorsugsweiss durohgeffifert in the presence of a Reaktionstragers _t wünsehens · werterweiee of such, in which the ReaJctionspartner 18s Iioh or are readily dispergierhar. As examples of very valuable solvents, there may be mentioned so-called dissolving agents and subetitated arcofctlach · LisvagKlttel such · bensol, toluene, xylene and chlorobensol, aliphatic ·> oil contains a number of chlorinated solvents and toluene the bsrorsugtea frigersitlwtanssn ds.r

The cyclization of the Oyelo-0-12 is carried out by Tarei-Bohen in any order of the carrier toffee, the cyclization age and the Cyclo-C-12, the cyclization temperature can be as low as the temperature or slightly lower, for example 2S ⁰ O, to see below 300 ⁰ O rich, although in many Vienna obere.Temperaturgrensen of 20O ⁰ O or wfinsohenswert among which are · The lower Zeopera doors führea su very long reaction was th * is berorsugt so Dafi "higher" 2emperAtur "& su use what rom Terwendeten Oyolisiertangsmittel and Realction Triger depends · Semperaturen as the upper end of the Bervlohe can read Vebenrealctions, which are faster than the desired

I am another imctor who sets the Oyoli beer temperature is the end or balance point of the calculation trigger. You reaction can go through with lower or upper atmospheric pressures

BATH

009887 / TS31

leads are and ataosphirleeher Srnek lot usually at the most convenient and comfortable and wise! and the use of a generator at RttokfluAtasperaturtn lent lends a Sespemtorkontrol · So kaaaen sor Oyolleieruns clay Cyclo-C-12 SeapertttoreB tob 25 it 50O ⁰ O TerveBdet do, although an upper "SeBneratazerfease tobohens vohens vohens 200 °. Dloeo CyelleiesangeremlctioB is sireelallliceten at --etapcraturen ron 100 Me 130 ° 0 dtsse ^. In these tepporaturcn, 15 kinates can be carried out for about 10 hours, whereby the actual BeelrttlonenBelt tor Oyclieierung adfifi the kind dueeSge finished product cycle is canceled,

tta Bicyclo-0-12 su cy ole ile, is / "in the Oesieeh from ffrB £ ern and Cyclieierunsemlttel hor ^ e and the Bloyolo-C-12 is then added within about 2 to about β hours" with the XeB ^ eiratttT i * lMol * M »*? tervoiae la Bereion tob 30 to 40 ⁰ O is kept * Sin more preferred ceraturation levels on the duration of the Oyellierunsereaktion are about 32 to 35 ⁰ O. The er. The required reactivity is tared, among other things, inversely proportional to the temperature. If the admission sn sohBell takes place tmd the temperature is eebr high, ice water degradation flee Bioyolo-C-12 can occur

■ = ■ ■ ■■ "■ -." .- .. ■ - BAD OBIGlNAl

0098877

■ ■ - 16 -

It takes an unusually long time to complete the Urneet exercise . * It is therefore preferred to use this setting under conditions to carry out that 4 to 6 stages are essentially necessary, us to roll the üraeetming su.

After the decomposition reaction is complete, it becomes water tnigesetst, ura wash the organic material bu that is then decanted. The reaction product can be subjected to one or more further washing operations and is then treated with an alkalizing agent, s.B. with oinera strong alkali such as sodium hydroxide or the Salt of a strong base and a weak acid such as Hatriuahii & rbonat, to remove all further traces of AoIditat see below ο

If the cyelization reaction is complete and the reaction has been neutralized and washed, the product is purified further, for example by distillation or exifaction. For example, it has been found that fractional distillation is particularly satisfactory for cleaning deodorant products. If a still higher purity is desired, the product can be purified by preparative chromatography technology

BATH

009887/1 631

Brinduogegemäßoe cyolized cyclo-0 »12 kstsfi waiter are treated with a Snoxydieriaigealttel wbüsx formation of the epoxy derivatives. The Bpoxydarivaie τοη eyolleiertea Oyele-0-12 are produced in practically the same way as the Bieyclo-0-12 from "de" Oyolo-O-12.

For the distilled eyclieated Bioyolo <-C ~ 12 it is not useful for Parftiaeriesv / corner "the material is to be used, as a constant boiling mixture forms, as was found only by Gao-PlÜBoigkeits-Chrroatographical analyzes , 5,9-Irimetliyi-13-oxabicyclo [10,1,0] tridöCß-4,8-diene el © a clear liquid gevo & n & n with a boiling point of 95 to 100 ⁰ C fcei 0.4 use Hg, »| ⁰ · 1 * 5040 to 1.5101, the infrared

(IR) is shown in JPigar 1 * xmd the nuclear-magnetioehe ResonanBapektrua (HSR) ia figor 2. FIG. 2 is the inflection level at about 5.3 ppci, Biagra & n is reproduced in a reinforced format above the complete reproduction. The IR-Spekirraa was obtained with a Böcktaan spectral plaotoaater model IR 4 under the specified conditions and the 9SR-Spe3etrisa on eiseci Tarian Ifcdell Λ 6 © with the specified parameters.

The cyolyzed Gyclo ~ G-12 did see p. in one flood of fractions » which boil at 106 to 12ß ° G at 1.0 to 1.5 iaa Hg »

009887/1031

where the low-boiling fractional have a Breofc & ngsiaäex p μ f, §045 * which is enough for di «feffharaiedesftea fsaktion tii 1.5104. VaOh more? Befcatodlungf w tee oyolieierte material en epocytosed, sets da · oyelieievt · oyoXo-G-12 a © liquid Aar aii izftktioBMi, Ai · b «i tone 120. bit 134 ° 0 at 1.6 to 1 _e 3 hi Hf« i « there.

J rtlobt Tön 1 "4948 for the ai" dri ^ 8i "a" aAea share to see below

1.4982 for the hofcereiedeaaeii share · · Sae oyolieierte Ojclo-0-12 woist && S in Figure 3 roped Inf ^ axot-Absorptioneepek «· and the Bposcy-eyolisleri © OyoIo-0-12 has the infrared shown in Pi-4 Abeorptienespectrcs. The IR spectra of FIGS. 5 and 4 are cooled under the specified conditions. Bas Eposy-c ^ elislerte Cjolo-0-12 has a. inten * iTon aiigenelieen l & olsArtigen «rad Jtampt erigen öeruch on the bedding pleasure iet · Se can be stated that the combination ran oyelisiertea 2ioyolo» 0-> 12 nad Ipozy-oyolieierte «öyclo-0-12 results in a Boftaat« r £ al, which indicates an intense initial grade of consistency.

Bas alcohol Serimt τοη Biejrol <H3 ~ 12 is duroh treatment of the Sleyoltnaterials sit a »reducing agent with the formation of the Alcohol ^ produced. Water and oxygen should be used with this tfasetsung will be excluded and it will be advised that Reaction in @ in @ r inert Ataoephär® such as Stiokstof ^, argon or the like., Durolieuführöß. It is particularly preferred that

BATH

009887/1631

tftasetsung enter eiaer Sohtttssehicht τοη tsoeknettasi nitrogen through

Inconsistent reducing agents in the manufacture of alcohols are represented by LlttoiaBÄluainiuefaydrid. 91 The reaction is carried out in the presence of a substance which is a solvent for the reducing agent. Venn LithiumalUBinluBhydrid aid Eeduktionemittel used materials such as "Digly & e * (OiKthylenglylcoldiaethjl & Tiser) never Losu & gaaittel Torvendet be and 7e-tran7drofuran is suitable for the process particular, tetrahydrofuran is AUOH nutelioh m® in controlling Beaktion" since the fund in Rfiokflnetetq ^ erature dee j & mssigsslitele held verden Isann,

The reduction is known to be increased at sex temperatures of 60 to 200 ⁰ O dTB. The Xeevogeaittel tfSs the conditions ■ in general the upper feg ^ eratnrgrensen, where the uasetsttng d ^ can be carried out roughly. At Sempera-

tures under the area, the reduction is unsatisfactory. Ttbera'teoa ^ hSrisohe pressure «can aage be applied to increase the boiling point of the reading device or pergierBittels and to allow the operation for some readings.

.- ■: - ■, .. -_ ■■ ■■■■■■■■■ '■; ' ' BATH

0 0 98 87/1 $ 31

The tent required for the reduction is usually sufficient from 2 to 10 hours

When the alcohol has been formed by the reduction, it becomes clear see below the Reakilensmaose slow water re-set and the alkalicchsn Materials are then made by adding a suitable acid like igssaere neutralized, the alcohol formed is out the Reaktiocasaoee old a suitable solutionmalttel vie diethyl ether removed.

-Dan αesIsch from geosetrlsohen Zeoaeren of ifSfS-TrlKethylcyclwlodeca-i ^ Q-dien-i-ol represents a clear «VIfIe-, blbidity with a boiling point of 115 to 118 ° C at 0 _t 1 bsb Hg and n | ° - 1.5134 to 1.5143. This alcohol caused a necessary haul-like tetiver deficiency. * Blue Eoaponente of this G em hole β can be represented by the following structure * © ».el:

OH

The orf isdvngsgenäSe KetonisosierengeBleoh can after a Uo oetEung can be made similar to that let «dl»

009887/1631

BATH

Formation of the Epoxyäsdet WiXd ₉ except dftfi das

or pS-lamtrolllerecde means of the Petcarbonsltare ve £ gelae-> »En will. The same ile & ctloneaditen, leßperfttvizren "Brooke" ad iüerte! Fr & Gör «earths used for the Setoniiers division, wi © them above Jn Zuc & E & enhfing »it 3ioyelo-G-12 cc ^ egnbec» ind · Das Koton-RsoktiocBprcdiiktgeTiieöb vixd bit water and an »aqueous Reducing agents ge ^ aeehen, τη eegebeae & fialle Torgende not ^ Bgso et »to Perea ^ onsütir · m sereetien · Die nach de« Vaechcn bis bus Keutraliiäi against Xao3dnae inherited organic * Layer is velcuusaeatilliert, - tni gsgtlieneni & lXs vor & miaftene i & erto Renktionsΐΐ'ίίgor mi removed ^ s · BeMsdliiiig dee products a »it ο ine «atkalifjohBii smock like KöSri ^ eti latritoebieaslso & at kas & nr <gevaRät be safe in the 2a & t £ erm «ag joder xestliohen acid Bus parts.

The profit oct if it is fractionally distilled, with 1.5> 9-trimethyloyclofiodecß-5 "9" ^ len "2 * -oa hurry a little liquid he" fealtsn vird old a boiling point tone 123 The 13t ° Ö bal.S "$ 'seD% uud B ^ "1.5050" to. 1.5057 "Bas material lsaim durol? the following structure? foraol

η--

■ -. ■ '. '- BAD ORfGIMAL

0 9887 / 1B31

The inventive new Gyolododee & the & derivmt · «iod do particularly well? Vertfen & OBG As SuftaamterielifB, ice scent Kodifllfttionea & teri & lien uM τοη ans * Production SarfuasMsaaaeneetsuageju They are special for Parfnaeriesweek "well suited t wnn a holsaxtigss Aroem cewtineotit vizd. Bim eyelleiarte Bloyolo-O "12 lot of beetmfltre Beaerkeneweart because of its bitter, holsftirligen Inutpfenrligeii 2hiftes ₉ and the Bposqr ^ eyollsiert Bieyelo-O-IS because of its intense helse.-like scent tea. The Bieyolo-0-12 and the AlkoHol! " Often a part το «hols-like Aabertyp herostellen» kSmien the invented tfftteriftllen old ti el · »species tob Ihiftaateriallert are coablnated» like »with the Syp Toa flowers» Moaohus »OewUrs, Aldehyd, Oriental borrowed and Farn Coss (esio-soss) · The new- erf indungsgtnKfien Mtoteriftlie & kSanen Anoh old usual $ ftr £ uasttaftteen koablnierl be "oil as" it nmturlio & s, Bjnthetisoaen Olen _t Istern, Aldeb7den _f Xetonen "alcohols" IAC "tone, £ Usnngsaitt" lii _t 2> f ixatlren, ispergi _l ezBittelit _> Snxlgiezait y surface smokers, A «cosoltreÜmitteln va & the like.

is open to the fact that the oyolized Xfttori & lien, the Al- \

kohel end the ketcm wilnschtenifelle are hydrogenated kunnea, the Büaydre »or Setxaaydroderitsame herenstellett _r as above in Siieaaenbeng with the Heratelltsng the dihydro- and Setmbydroivate of. Bloyo.lo-0-12 was even beoobriebeis »

BAD ORJGlWAL

009887/1631

The following examples are very rare Tent is carried out backwards, without si «äö

Beiapi ·! 1

from

Bin aeaiseb «us 3 1 waseerirelöw ÜÄtöjliiaohloriä» S20 «(10 mol) vaeser-freeB Iatriw» eetat and1020 g (5 Sol) oyclodod »oe-1 _e 5,9-trJ. * N vixt Ib« i &
dft · with «inoB stirrer _t « la «« IhtaMmt «nal ei» «Sz®pftriefet« r let. SU g «xtüsrt · RaektleüWMa ■ · irlad mxsi O ⁰ O brought uai at ditser« «parntai ¹ 3 Sttm &« fi fabelten, «iteead 1005 β (5.5 mol) 40 £ ig * r P« r «8Sie» * Rrc mgtgebem «« χββιι. It is held at 0 to 5 ^{0 for} a further period.

You orgenische 3 chi oht is daaa bit 2 1 Yaaeer getfaeebea, xm die DeaetauBg ebsubreofim, uad decaatiert · you oi ^ gaaleoae layer vixd with an equal Tollmen one? 5 £ igea «Sirigea L0 * nng yon SisenaBaoaitiaBulphat geMaeoaea» vm possibly · voxtea & «a · remove remaining perishables. You osgaaleoae layer is then deceated. Bit of a gee & ttSgtea «Hfirigea Χββαη« το »Iatriwbiearbonat treated and distilled, whereby 944 g 1» 5 _f 9-Srlaethyl-13 ~ o3abloyole [10.1 _v 0] trideGa * 4 ₉ 8-diea are obtained.

This material is a clear liquid. Bit one intense holsfihnllohen Ambexduft · Is has a boiling point of

OO9807 / T631

106 to 1ΟΘ ° 0 at 1.0 η H «, n | ° - 1 ₉ 5046 to 1.5075. Bie IS-hbA iai "M" p "grpiilaeban Irgebnlas · eiaA In an overdrive old d" described. Structure.

Similar results are obtained, which are called "tfben * oeelure, Ohlor ~, Stoaaeiseaalose HoA 2" ri ^ tttool8iär "i instead of the above mentioned 7 · νΑώατ ·" rrnnmeäkt .

Be game S.

«» 12

An Oeeiech & «s 500 β Bioyülo-ö-12 mcfc Example 1 xmd 25 g Pallad iuftchlorld is diluted 500 g anhydrous ittenol and 1 mol hydrogen is introduced into the reaction and at 100 ° 0 and 7.03 etü (100 p * l «) adsorbed. The solid Zfetalysatoraftterial is removed by filtration and the liquid obtained is vaSniuadistilled, to remove the ethanol eu.

Xs is 1,5,9 ^ ri3Be-lliyl-'15-onbioyolo [10, f, 0] trideem-4-en τοη in an amount of 475 g · erbalten Bieaes a colorless oil MOIE asked telargewioat of 222 _f a boiling point of 72 ⁰ E at 0.2 na Hg and n | ° m 1.5021.

BAD OFHGlNAL

009887 / $ 3t

Example 3

Bas BleyGlo-0-12 gene & S Example 1, the whole kethole of Example 2 4 is hydrogenated, if it was Tßllstiadig en hydrogenate, the filtration siir Satfessauag des Itital ^ setore WiA after Bntfevsnoe dee itMnol «vie la, example 2 ertibt the Tzttictieaienmg 4SO g 1 _for 5.9 tinyl "Fe III! '' -13 - '' ^ le7oio [1O _v 1 _v O} tridet" n "a fAzfeloeee Cl with eiaes SieSepuskt

72 ⁰ O at 0.2 aa% ιΐΒά al ⁰ - 1.4975. BIe

keitie ücijättlgiiüg m & die Keeeeiy ^ pektroekople soaps a holocular cattle troa 224.

Beiepiol 4

Oyollolertas Bioyele-0 ~ 12

Sin QealBoh ans 960 g 85 ^ ig @ r? & Oaplioä? 8ämfe usiS 480 g Beasol is placed in the reaction vessel & I smokt » umm with eisiem Itihre ?, auokfluflkonäeiieator» fhexaoaete? isa £ sbeopftsie & ter is fitted. Sas Ööaiocä vlTd on eiae 2? «Öipfisatux r && brought about 34 ° O vied then at 32 to 35 ° C» wfibr «Bä 957 g of the sown example t produced Bioyolo-0-12 i & nerli & lb ▼ on 1 to 2 times were added.

Bach 6-stundiges daiaerndefii stirring at 32 to 35 ⁰ O is given the Reaktionsitasee ac 'inta equal volume of water. The organic layer becomes delmutiex-fc and old a saturated one

■. _ - - ''. - .. ■ .. ■ "'. BATHROOM 0R1S5MÄL

009887/1631

vti? i £ en Lueiisg tos ItetsitisMe & rbo & at geufteehen until ei · against neutrel reacts, and dam «nf one SO os> * (£ 4 rope-) distilled.

Ee throw sth &? 5O g of a constant boiling eeaieo & ee d ··

ateri & l *, as ttöE ^ A d «s-91« eiges & eite-0li £ Qafttoexa is bestirnt ,, o ^ »lt« ii · Sited · K * t * rl & I b * i a ftnge & elK «n bolsAitigöii laapfesttVti ^ eK IHift, eiaeii Ton 32 him 36 ⁰ CU # i 1 _t 1 äs Hg _s 1 ^ - 1 ₉ 5O4O l "ie 1, Iafr" red- ^ bf? OrptioKii! G |! * 3e ^ njß is in ligwt 1 onfi dft "in Vignr 2 ascended.

Example 5

Sin Gesisoh "ras 19 g SitMiaBäluainiiiaSi ^ SRM tsni §00 el dxOfuxan wixd gebzaeht in a Eealttiemigeflt ei, d 's with a" stirrer, Bttokfl »£ ök: oafieneator waae Sropftriehter" is nsceetattet, aaoMu "by @ ei% S kit dry nitrogen "A mixture of 5t g 1, § _e ^ -TrlÄ" tiiyi-13-ox "bicyoloi ίθ, 1 _ff O] triaeoa-4 ₉ 8-dien and 100 el Set3tt & jdr <ifGirttii is dtn flask & w of the dropping triohter wäbrtnft 2 Stiasden stigefifgt, vtitr · ^ das Φ «like oh with leiohtea RflekflisS gelielteia visd« 3) * j§ Brnitsea wixd d «nn another 6 hours continued» by Amm Qemlaoh at EüekfluS en balten.

BAD ORJGtNAL

009887/1631

D ·· B «ürtioa ^ eelech

and «it 52 g Waeetr lASgaea Tör« »t * t. 5Ö wH 52 * 1 * «l« * il * Isnr ·

WcsAen Äeaa godca Vom * m & de * Reakt £ oiseg # Bl8®M

«Ad tee Qeiieöh wisÄ old an« 4

Der BlätthylätTi »r wisfi

tli3rloyelödoa «Gtt <» 4, S * -aie & ~ 1 ~ el Al «« is »lüLsa?« Flfleii i «k« it erfcftltea verftea, «it ei & oi Si # fi © pesftt Tom 115 him HB ⁹ O is 0,1 at Hg »b | ° - 1.5154 to 1.5145. Di · fcmMe & fttieelit »» · - eonsaeverte ielg «n _t d * 9 which is lat« riiil ei »tertilM« Alfeofeol.

A öemisoh ouch 632 g of 1,5 ^ ^ F ^ -IriaetiiyioyöleÄödeini I -iriett tmd 1800 si Methylenöhlöyia wi2d 4a iron XelV "t" iBeefftlist "d" r eiaift SUibxev, ϊϊι®2 "αββΐ * Γ _# fiuolcfXoStoaleasatos aad faecupftriohter ausgtstatt · * Is »Dee £« nisei & visu At & t «if» door of about O ⁰ C gives & oht vst & Bit 605 «40 | (ie« v inn «ztiftll» from 5 etaMsa ^ dusetet, «oo« i δ «« CNesieeli xsnttf stir at 0 to 5 ⁰ O g «b * l%« tt wisd. Da « Mhsmk viid further © 5 Sttmden fortgeeetat, MoMft al«? eree8ig «8: iir« s «gAl> 1i« «aAet let.

same bit Bea & tioneaasse throws daira with einea / 7eltaM & one wMrigea BieenejaofiieBStiffttlSaiteg gewaeolifii, va itieltt-O ^ geeetste Pereeeigeiure eu »eretCrea. The organic Sehloht is then washed against Xeolostw until the end of the VentrmlitXt and the money is removed by TeJaxta & eetlllation. The final product is made using a 90 ce (5 foot) faatal rotating column distilled

In this way 106 g of 1 _> 5 »9-5friae1; hyleyolododece-5f9-dien-2-one are obtained as clear fliesigkoit» with one you »

Tone 128 to 131 ⁰ C at 2.6 nta Hg and n ^ ° - 1 ₉ 50 50 to

1.5057.

Example 7 Qyollelertes OyοIp-O-12

In a 1! Reaction flask fitted with a stirrer, ter, Rtiökflufikondensator and Heisaaniel equipped. Itt, 250 g of fiensol »250 g of Polyphoephorefture and 250 g of Sifiethyloyclododeeatrien brought in. The cash register is stirred and 8 Heated under reflux for hours. The Keaktionssasee part Then calibrate an organic phase and a phase in ßwsi Phassnt v & firlg-acidic phase. The organic phase is decanted the aqueous-acidic phase becomes Bit Qlnea Voltaeca Bensol

009887/1831 ^BAD

The bensol layer is washed with 3 volumes of saturated solution and dried over calcium sulfate and filtered vaoA. The Sensol is recovered and the product is distilled. The resulting product provides a laonraag-ISOH is having a boiling range 106-128 ⁰ O at 1.0 to 1.5 "Hg and a van ng range 1.5045 to 1.5104. The infrared spectra

this material is shown in FIG. Example 8

1000 BJl of ethylene chloride (CH ₂ Ol ₂ ), 180 g of anhydrous jiatrito acetate and 238 according to Example 7 are prepared in a 5 l flask, which is attached to a Hührer, Shezsdieter _{y RückHuss condenser and dropping funnel.} leveled Cyolo-C-12 introduced. In addition, it is ^{cooled to 0} ° O and stirred for three hours, during which 284 g of acetic acid are added to the acidic solution.

When the addition of the pere acidic acid is complete, the stirring is continued for 5 hours at a temperature of 0 to 5 °. The E & aktionßisaeee irinS & mm About! Teoht are left. For about 12 hours the re & ktionssasse is under-booed on Perozard salary. 1 1 Yasser is added to the reaction caese and the mass is then stirred and passed over into a 3ohe meter.

0Q9887 / 1S31

1617Q09

Bi * organic SoMoht vlsä separated usfi washed bit t Tolwen vaerlgea fatrimohlorid, 2 ToIumb 10 £ lgea Bisei HiQBSUlAIt (? EüH ₄ (80 ₄ ) ₂ ), sweiiea old 2 Toltaen g «eltti« tea BSatricabiocarbonat uodMtobloridbatridea. You Eeaktionsis & eae is dAim practiced Maenesitaeulfe / fe e ^^^ olmet ^ »1 filtered and the solubility wivA isolated at 50 ° 0 at 10 aa Hg. The gross weight of the epexyflated ProAaktee is 256 ff.

Dae product virs fi & na distilled vobei epoxyoyolisiertes 0jol> -.! 0-12 ale a ffliiesigkeit exbftltea is bit a Siedebereiob ron ISO to 134 ⁰ O at 1.6 to 5 SB Bfc, and a * ⁰ "Sereiöh tos 1 ₉ 494β bie 1 , 4922 · Bas IS-8pektniB is reproduced in 4, Pss Material 2sat iron intensive- "nholesertigen wa & kaspferartlge" Soft *

Example p

A iterft & siieeisaenBdtsiiiig vird doroh 7eznisohen the following ingredients Sm given Ternältnis made!

Bentendtello gile Bergasotei 150 Orangenfil (Florida) 75

2 lemon oil (Celifornie), O.P. . 15th

. - BAD GTmiM

00988771631

Oylated Bicy © lo-0-t2 according to Example 4
Bog «nol, Ü.SP

ⁿ Lyml * (Srfiroaq ^ iieftliylpeiityl earboxaldeoya)

StyraXlyl acetate
Hang © xtr »
Potltgrnin Sl
P »techwli dark

, rereiBigt (bulked)

20 50 10

50 5

4 25

Example 10

Blae

in «3 en

Beieplel 9

Alcohol Toa Bloyolo-C-IZ ges & B Example 5

50

these two väßrigea ethanol

daim »1t, chilled we & filtered _s tas oln

tlegest® 11 tea making K81ni3Chwasser · The two like this

09 81? Π S3 .BADOWQ »3AL

• shared Iölülaotwasser show «In Sitroearoem on da · naon tends to have a lilac-like Aaber and Kasgpfer-like scent,

This Ctrundsusaaraeiaeetstingen köimen aöoh rerweadtt verden _s in soap or other Seilettenaftikel as lotions, Aeroeolspraye and the like. Jhxft old su Terflelien. The derivatives obtained according to the present invention are used as shown in the following example.

Example 11 The following ParfDmBUsaaaonsetsuns is hezgeetellti Beatand parts quantity (g) Oasela abeolut 60 Methyl ionone 60 Jasmine extra 80

“Erollöl, bigarad. 60

Patechuliei 60

Vanillin 60

Yiolot 60

Epoacy-cyclized Qyclo-QM

according to Setepiel 8 60

Lemon oil 80

120

BATH

C 0 9 8 8? / 1 S 3 1

TS17 & 09

Beetanateile I gorteetgimg) LaveodelÖl, fraßsösieoh ettfiee orange oil

1000

The above Gaialeoh was checked tmd it «nsde seAmdeB, that ee elnea high Qrad of rich tmfl bestttodlgeif new hols-like, ejaberSlislioher Qtiftlitat.

9887/1631 ^BÄD ° ""

Claims (1)

Eetentanspraohe 1, use as Sarfta or Jtaft - »- rerleilieade0 material of the general bondage l-N QH * OH, Hg - 0 - - 0 «- H or α -« β - «- CHL bathes and the dashed lines represent Sinfkoh- or Soppel-indentmgen; trad der cycliel @ rt © n derivatives _v wenii 9 '' 3 * ^{ie the} grouping E - p ~ - O - OH ^ or BO »0» OH- represents, and the £ poxy products of the ot »ijge & ejolieierte Beri ^ ate ^ if 0 ^ - γ — OR * represents the grouping W «6 - OB ^ and τοη eichen the above compounds · 2. Application according to Claim 1, characterized in that the ip ^ fHCjolododeoaderivat t _f 5.9-9riaieth3rl [10.1 _e 0] trideea ~ 4,3-diene is used. BATH 009887 / 1S 31 1617003 - 55 -. 3 · Use according to claim 1, characterized in that dafi al · iV ^ iS-Oyelododecaderivat 1 »5,9-ΤτΐΕΐβίΐϊ ^ 1-13-τθ» 6, Μθ2Τθ1ο 1, Ojtridee-4-en is used, 4. Use according to claim 1, characterized in that as 1.5 f 9-Cy elododecader ivat 1.5 »9-triaethyl-13-osa" bIoyclo [10, 1 _r O] trldecane Terwoadet vird » 5. Use according to claim 1, daduroh gekexmaelolmet »that as 1 "5" g-Cyolododecader! Tat cyolie lertes 1.5 " ShTt iaiethyl-13-oxabylcyclo [10,1,0] tridGca-4,8-di.en with a boiling point of 95 to 10O ⁰ O on ■■ '■.' at 0.4 bo Ή &, ng ^υ «1 _f 5040 to 1.5101 and dta in FIG. 6. Use according to Claim 1, which is known as 1r5, S-CyclododecaderiTÄt © yclieierter 1,5, trien-1,5,9 with eisea 8iedeb © reioh τό »106 to 128 ⁰ O at 1.0 to 1 , 5 m Hg and -des in? Igur 3 inclined infrared absorption spectrum is used. . 7. Yervendung according to claim 1, characterized in that as 1 »5ί 9-Cyolododecöderivat Epoay-cryclisiert« «1.5, S-EriBethylcycle dodecatrien-1,5,9 rait a Boiler« I from 120 to 134 ⁰ C at 1 _r 6 Ijis 1,3 © κ Hg and the infrared shown in Figure 4 « is used. 009387/1031 BA & - 36 - 8. Utilization & aeh claim 1, characterized in that as 1.5 _t 9-Oy «n.oÄodeeÄaeri * at 1.5» 9-Ϊ riftethyloyolododecft-5 · 9-dien-2-one is used * 9 · yerweadung according to lnapruoh 1, fladttreh f «3c * imseiohn9t that tv 5« d-Cyelodedeoaderivat 1, 5 , 9- ^ t? Ii » ^< öiyIoyolc4od« CG-4,8-dltn-1-ol is used. 10. 1,5,9-Oyclo <3cHlecatri * ö "1 _? 5, SD« riTftt »der ? orael S "\ in the -CH, - f - OH «, or c— C — CH ^ and the dashed lines linearly or represent double bonds; the orolieierte derivatives, if Ϊ *. Or CH- the groupings. Hd - ^^ C-— CH. or flC «« o-— CH «° l ^e ^ il * ι \ j means; and the spoxy products of the above oylated derivatives, Cl · - C? Hj the grouping HG a Q — OH. means, BATH ORIGINAL 003087/1831 ■ "■■■: ■■■ -57> · ;; -; 11 «1,5,9- £ rmethyX-13-OTÄ]> iGycl © [10, 1 * O] trideoa-4, G-diene. 12. iV5 »9-Iriiiethyl-15-e3Ät> tey © loC 10, 1, 13. 1 * 519- $ rlaethyl-13-O3Hit> loyoleC 10, 1 _t 0] tr4 & «oatt · 4,8-dlen nlt einea Sie ^ eptmJtt of 95 Me 100 ° Ö at 0,4 η Hg ₉ * ⁰ 1,5040 bit I ₉ SiOi ₉ uafi «5 <* a eat Pi ^ er 1 gesel ^ tea In £ S "Red and the one in Tigta? 2 geacistess 15. Cyolielertefl I ^. ^ IriaethyloyolododecÄtTitn-, 5.9 a boiling range τοη 106 to 128 ° Ö t> ei ^ I ₉ O to 1.5 ras Hg and the one shown in Figure $ 16. Epoxy-ojoliolerteß 1, SiS-Trlasthylcycloöodeöfttriea-i, 5.9 with a boiling range of 120 to 154 ⁰ O at 1.6 to 1.5 tm Hg and the in ligur 4 gases Igten infrared absorption spectrum. 009 8 87/1831 bei, ll & Bg 1 dough SfeOl gtgea 001, Abl "Btaai" * br * lt · 500 op · WM * öifsÄ) Ϊilterbaafiweit · 4 op · Spektnat-Terstir- mg 4 fief. ? «Ld 0.1 g tasig 10 250 sto. PtgTAJ If ifaöl BAD OR] 009887/1631 Blank page