EP0000257B1 - Dérivés du benzo(c)pyran, leur procédé de préparation et leur utilisation en parfumerie - Google Patents

Dérivés du benzo(c)pyran, leur procédé de préparation et leur utilisation en parfumerie Download PDF

Info

Publication number
EP0000257B1
EP0000257B1 EP78300056A EP78300056A EP0000257B1 EP 0000257 B1 EP0000257 B1 EP 0000257B1 EP 78300056 A EP78300056 A EP 78300056A EP 78300056 A EP78300056 A EP 78300056A EP 0000257 B1 EP0000257 B1 EP 0000257B1
Authority
EP
European Patent Office
Prior art keywords
oil
acid
value
formula
hydrogen atom
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP78300056A
Other languages
German (de)
English (en)
Other versions
EP0000257A1 (fr
Inventor
Richard Clive Cookson
Lorenzo Ferro
Gerald John Ferber
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bush Boake Allen Ltd
Original Assignee
Bush Boake Allen Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bush Boake Allen Ltd filed Critical Bush Boake Allen Ltd
Publication of EP0000257A1 publication Critical patent/EP0000257A1/fr
Application granted granted Critical
Publication of EP0000257B1 publication Critical patent/EP0000257B1/fr
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0069—Heterocyclic compounds
    • C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
    • C11B9/008—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing six atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/38—Unsaturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings
    • C07C47/45—Unsaturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings having unsaturation outside the rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/76—Benzo[c]pyrans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • This invention is concerned with certain novel organic compounds and with perfumery compositions containing the compounds. It has been discovered that these compounds exhibit unique, attractive odours which render them useful in ingredients of perfumery compositions which compositions find use in a wide variety of applications.
  • Such compounds may be individual steroisomers or mixtures of the possible steroisomers of compounds having the above formula.
  • novel compounds of this invention are derivatives of 3,3,7,8-tetramethyl-2-oxabicyclo-(4,4,0)-decane which will hereinafter be referred to for convenience as bigarade-oxides. They may be employed as a major ingredient of these compositions depending upon the desired overall odour required. In general the bigarde-oxides will constitute from 2 to 15, preferably 3 to 7% by weight of the composition.
  • the perfumery compositions of this invention may find use as such or after dilution, but more usually they are added in small proportions to other materials such as space sprays or to soap cosmetic or deodorant compositions or to substrates such as fibre fabric or paper products in order to provide them with agreeable olfactory properties. Such compositions are products of commerce and they may comprise a simple or complex mixture of individual perfumery compounds.
  • our invention provides a compounded perfumery composition
  • a compounded perfumery composition comprising a plurality of odoriferous chemicals together with at least one compound having the formula:- wherein X and m and n are as hereinafter defined.
  • the unique fruity floral odours of the novel bigarade-oxides of our invention find special use in compositions designed for use in various perfumed bath preparations such as bath salts etc.
  • novel perfumery compositions may be compounded according to recognised techniques of the perfumery arts employing known odoriferous perfumery ingredients such as those described in the standard textbooks of the art, e.g. "Soap, Perfumery and Cosmetics” by W.A. Poucher, 8th Edition, published by Chapman and Hall (London) 1974; "Perfume and Flavour Chemicals” by S. Arctander published by the author (Montclair) 1969 "Perfume and Flavour Materials of Natural Origin” also by S. Arctander self-published Elizabeth New Jersey (1960) and "Perfume Technology” by M. Billot and F.V. Wells published by Ellis Horwood Ltd. 1975.
  • odoriferous ingredients which may be blended with the bigarade-oxides in a compounded perfumery composition are the derivatives of 2,6-dimethyl-2-alkoxy octan-7-ol (as claimed in our Dutch Patent Application No. 72.
  • vetivert oil vetiverol
  • vetiveryl acetate guaic wood oil esters of anthranilic acid such as the methyl, N methyl methyl, ethyl, phenyl-ethyl, cinnamyl, linalyl, methyl and geranyl esters, benzyl acetate, lemon oil, dimethyl benzyl carbinol, dimethyl benzyl carbinyl acetate, rose absolute, jasmin absolute, ionones, isononyl acetate, methyl phenyl acetate, styrallyl acetate, B.
  • phenyl ethanol citronellol, citronellal, hydroxy citronellal, geranium oil, geraniol, linalol, nerol, lavandin oil, linalyl acetate, patchouli oil, petitgrain oil, bergamot oil, heliotropin, ethylene rassylate, undecyl aldehyde, cinnamaldehyde, benzyl-salicylate, cinnamyl alcohol, clove bud oil, bay oil, nutmeg oil, pimento berry oil, terpineol, ylang oil, benzyl benzoate, sandal-wood oil, clary sage oil, amyl salicylate, labdanum resin, methyl ionones, dihydro-myrcenol, orange oil, vanillin, ethylvanillin, olibanum resin, musk ambrette, rhodinol, man
  • novel bigarade-oxides are blended with at least two, usually at least five and preferably at least ten of the foregoing ingredients.
  • Preferred compounds for present use are those wherein X represents a methyl group or a hydrogen atom. Most preferably the isomers wherein n and rr l have a value of 1 are used.
  • Particularly preferred odoriferous ingredients for blending with the bigarade-oxides are linalol, linalylacetate, bergamot oil, grapefruit oil, lemon oil, orange oil, petitgrain oil, hexylcinnamic aldehyde, benzylsalicylate, methyl ionones, 2-alkoxy-2,6 dimethyl-octan-7-ols, methylanthranilate, geraniol and nerol and esters thereof, neroli oil, farnesol, nerolidol, eugenol, isoeugenol, patchouli oil, vetiveryl. acetate, cedryl acetate, p-tertiary butyl cyclohexyl acetate and terpineol.
  • the novel bigarade-oxides may conveniently be made by a multi-step synthesis which uses the triene known as allo ocimene as its starting material. Allo acimene is readily available as a product of the thermal isomerisation of ocimene, a triene found as constituent of several essential oils or more usually from the thermal isomerisation of a pinene.
  • the desired intermediate for the production of the novel compounds of the invention is the compound of formula:
  • an unsaturated alcohol as the dienophile in the above reaction, e.g. where X represents a hydrogen atom allyl alcohol can be used.
  • Other dienophiles which yield adducts which can be converted to an alcohol having the above formula may also be employed and the nature of the substituent Y will vary accordingly.
  • acrolein, acrylic acid, acrylate esters and acrylic acid chloride can be employed.
  • an unsaturated aldehyde is employed as the dienophile because of its properties as a dienophile and the ease with which the adduct aldehyde can be converted to the desired alcohol intermediate.
  • acrolein is added to allo-ocimene.
  • the Diels Alder addition can be carried out at elevated temperatures and pressures e.g. 120 to 180°C and 3.51 to 10.53 Kg/cm 2 or at ambient temperatures in the presence of a suitable electrophilic catalyst such as aluminium chloride.
  • a suitable electrophilic catalyst such as aluminium chloride.
  • the Diels-Alder addition of acrolein and allyl alcohol to allo-ocimene has been reported in the Journal of the Chemical Society of Japan Volume 5 (1973 pages 1064 to 1066). This disclosure describes the addition to a mixture of a trans-trans and trans-cis allo-ocimene.
  • the conversion of the aldehyde to the corresponding alcohol may conveniently be achieved using catalytic hydrogenation i.e. heating the aldehyde adduct(s) at an elevated temperature of from 150°C to 170°C under superatmospheric pressure say 12.66 to 14.07 Kg/cm 2 in an atmosphere of hydrogen gas and in the presence of a suitable catalyst.
  • the catalyst employed is copper chromite but other conventional catalysts such as nickel, copper and palladium may be employed.
  • the reduction can be achieved using chemical methods in particular reduction with metal hydrides such as lithium aluminium hydride or sodium borohydride which reagents are normally added to the aldehyde as a solution in ether or water respectively, the reaction proceeding smoothly at ambient temperature.
  • the alcohols may be separated from the mixture of products formed using conventional techniques e.g. fractional distillation or used directly in the next stage in the synthesis.
  • the alcohol thus obtained may be cyclised to the bigarade-oxide by heating preferably under reflux in the presence of a protonic acid catalyst, conveniently an aqueous solution of a mineral acid or phosphoric acid or an organic solution of a sulphonic acid.
  • a protonic acid catalyst conveniently an aqueous solution of a mineral acid or phosphoric acid or an organic solution of a sulphonic acid.
  • the reaction will usually go to completion under reflux with a period of a few hours e.g. 6 to 20 hours.
  • aqueous acid solution is employed as the catalyst.
  • a relatively concentrated solution e.g. 15 to 35% by weight is preferably employed in such a quantity that the volume of the aqueous phase is at least equal to and preferably at least twice the volume of the organic phase.
  • the use of more concentrated acid solutions gives a desirably high yield in a relatively short time e.g. 6 to 10 hours.
  • the oil layer may be separated from the aqueous layer and fractionated to
  • organic solutions of sulphonic acids e.g. para-toluene sulphonic acids in benzene or in an alkyl benzene speeds the reaction and favours the production of these novel compounds wherein n and m have a value of 1.
  • the organic layer is preferably washed with a dilute aqueous solution of a caustic alkali and the bigarade-oxides are then separated by fractional distillation.
  • a compounded perfumery composition was made up as follows (all parts by weight):-

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pyrane Compounds (AREA)

Claims (15)

1. Composé répondant à la formule:
Figure imgb0012
dans laquelle X représente un atome d'hydrogène ou un groupe alkyle comptant 1 à 4 atomes de carbone, m possède une valeur de 0 ou 1, n une valeur de 1 ou 2, n + m = 2 et la ligne en pointillé indique des positions alternatives pour une unité d'insaturation.
2. Composé selon revendication 1, caractérisé en ce que X représente un groupe méthyle.
3. Composé selon la revendication 1, caractérisé en ce que X représente un atome d'hydrogène
4. Composé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que n et m possèdent chacun une valeur de 1.
5. Composition pour parfumerie comprenant une pluralité d'ingrédients odoriférants, caractérisée en qu'elle comprend en outre au moins un composé répondant à la formule:
Figure imgb0013
dans laquelle X représente un atome d'hydrogène ou un groupe alkyle ayant 1 à 4 atomes de carbone, m possède une valeur de 0 ou 1, n une valeur de 1 ou 2, n + m = 2 et la ligne en pointillé indique des positions alternatives pour une unité d'insaturation.
6. Composition selon la revendication 5, caractérisée en ce que X représente un atome d'hydrogène.
7. Composition selon l'une des revendications 5 ou 6, caractérisée en ce que n et m possèdent chacun une valeur de 1.
8. Composition selon l'une quelconque des revendications 5, 6 et 7, caractérisée en ce que la composition comprend en outre un ou plusieurs agents chimiques odoriférants choisis parmi le linalol, l'acétate de linalyle, l'essence de bergamote, l'essence de pamplemousse, l'essence de citron, l'essence d'orange, l'essanec de petitgrain, l'aldéhyde hexylcinnamique, le salicylate de benzyle, les méthyl- ionones, les 2-alcoxy-2,6-diméthyl-octan-ols, l'anthranilate de méthyle, le géraniol et le nérol ainsi que leurs esters, l'essence de néroli, le farnesol nerolidol, l'eugenol, l'isoeugénol, l'essence de patchouli, l'acétate de vétiveryle, l'acétate de cédryle, le cyclohexylacétate de p-tertio-butyle et et le terpineol.
9. Composition selon la revendication 8, caractérisée en ce que les composés répondant à la formule de la revendication 1 représentent 2 à 15% en poids de celle-ci.
10. Composition selon la revendication 9, caractérisée en ce que les composés répondant à la formule de la revendication 1 représentent 3 à 7% en poids de celle-ci.
11. Procédé pour l'obtention d'un composé répondant à la formule:
Figure imgb0014
dans laquelle X représente un atome d'hydrogène ou un groupe alkyle ayant 1 à 4 atomes de carbone, m possède une valeur de 0 ou 1, n une valeur de 1 ou 2, n + m = 2 et la ligne en pointillé indique des positions alternatives pour une unité d'insaturation, caractérisé en ce qu'on cyclise un alcool de formule:
Figure imgb0015
par chauffage en présence d'un acide.
12. Procédé selon la revendication 11, caractérisé en ce que l'acide est l'acide phosphorique.
13. Procédé selon la revendication 12, caractérisé en ce qu'une solution acide aqueuse comprenant 15 à 35% en poids d'acide est utilisée en un volume au moins égal à celui de la phase organique.
14. Procédé selon la revendication 11, caractérisé en ce que l'acide est présent sous la forme d'une solution d'un acide sulfonique dans un solvant organique.
15. Procédé selon la revendication 14, caractérisé en ce que l'acide est l'acide para toluène- sulfonique.
EP78300056A 1977-06-21 1978-06-20 Dérivés du benzo(c)pyran, leur procédé de préparation et leur utilisation en parfumerie Expired EP0000257B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB2586377 1977-06-21
GB2586377 1977-06-21
GB1333878 1978-04-05
GB1333878 1978-04-05

Publications (2)

Publication Number Publication Date
EP0000257A1 EP0000257A1 (fr) 1979-01-10
EP0000257B1 true EP0000257B1 (fr) 1982-02-17

Family

ID=26249725

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78300056A Expired EP0000257B1 (fr) 1977-06-21 1978-06-20 Dérivés du benzo(c)pyran, leur procédé de préparation et leur utilisation en parfumerie

Country Status (6)

Country Link
EP (1) EP0000257B1 (fr)
JP (1) JPS549276A (fr)
AU (1) AU517033B2 (fr)
CA (1) CA1115284A (fr)
DE (1) DE2861629D1 (fr)
GB (1) GB2002358B (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3302000A1 (de) * 1983-01-21 1984-07-26 Danfoss A/S, Nordborg Hydraulisches schieberventil
JPS6174904A (ja) * 1984-09-17 1986-04-17 Daikin Ind Ltd 液圧装置
JP4746684B2 (ja) * 2009-03-24 2011-08-10 有限会社長州電気 伸縮装置

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2483824A (en) * 1947-07-29 1949-10-04 Shell Dev Derivatives of 2, 1-benzopyran

Also Published As

Publication number Publication date
GB2002358B (en) 1982-04-15
DE2861629D1 (en) 1982-03-25
EP0000257A1 (fr) 1979-01-10
GB2002358A (en) 1979-02-21
JPS549276A (en) 1979-01-24
AU3733678A (en) 1980-01-03
CA1115284A (fr) 1981-12-29
AU517033B2 (en) 1981-07-02

Similar Documents

Publication Publication Date Title
US4311617A (en) Perfumery compositions
US3773836A (en) Indanone derivatives and processes for producing same
CN107223120B (zh) 作为新型芳香化学品的1-(7,10,10-三甲基-4-双环[6.2.0]癸基)乙酮
JPWO2018051776A1 (ja) 香料組成物
US4104203A (en) Perfume compositions containing catechol-camphene reaction products
US4100110A (en) Isolongifolene Prins reaction compounds in perfumery
JP3430205B2 (ja) α，β−不飽和ケトン
EP0000257B1 (fr) Dérivés du benzo(c)pyran, leur procédé de préparation et leur utilisation en parfumerie
US4671798A (en) 1,2,3,4,4a,5,8,8a-octahydro-2,2,6,8-tetramethyl-1-naphthalenol, its use as perfuming ingredient and process for making same
JP2012140354A (ja) 新規脂環式アルコール
US3270061A (en) Oxygen-containing dicyclodiene derivatives
US4177170A (en) 3,3,7,8-Tetramethyl-2-oxabicyclo-[4,4,0]-decane derivatives and their use in perfume compositions
US3579550A (en) Oxygenated derivatives of acyclic olefins
US3660489A (en) Novel caranone derivatives perfume compositions containing same and process for their preparation
US5015761A (en) Tricyclo{6.2.1.01,6 }undecanes useful as fragrance chemicals
GB1593181A (en) Carane derivatives and their use in fragrance materials
US3754037A (en) Process for the acetylation of chamigrenes
US3876562A (en) 7,7a-epoxy-5,6,7a-tetrahydro-1,1,2,3,3-pentamethyl 4(3ah)-indanone perfume composition
CA1145774A (fr) Cyclopentanols substitues, methode de preparation et composes les contenant
JPS62169743A (ja) イソプロピル−メチル−ブテノイル−シクロヘキサン誘導体
US4287100A (en) 1,2,3,6-Tetrahydrobenzyl alcohol esters and compositions containing the same
US4818747A (en) Bicyclic aliphatic alcohols and their utilization as perfuming ingredients
US4251398A (en) Cyclohexyl-pentanolides and their use in perfume
US3702343A (en) 2-methyl-2-(tertiary alkyl cyclohexyl) pentan-4-ones and processes
US4643844A (en) Perfume compositions and perfumed articles containing dihydro- and/or tetrahydro-naphthols as fragrance material

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): BE CH DE FR GB NL SE

17P Request for examination filed
DET De: translation of patent claims
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE CH DE FR GB NL SE

REF Corresponds to:

Ref document number: 2861629

Country of ref document: DE

Date of ref document: 19820325

EAL Se: european patent in force in sweden

Ref document number: 78300056.5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19960528

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19960611

Year of fee payment: 19

Ref country code: FR

Payment date: 19960611

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19960626

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19960627

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19960704

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19960812

Year of fee payment: 19

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970620

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19970621

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970630

Ref country code: BE

Effective date: 19970630

BERE Be: lapsed

Owner name: BUSH BOAKE ALLEN LTD

Effective date: 19970630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19980101

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19970620

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980227

EUG Se: european patent has lapsed

Ref document number: 78300056.5

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19980101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980303

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT