[go: up one dir, main page]

CN1041434C - 采用龙脑烯腈作香料 - Google Patents

采用龙脑烯腈作香料 Download PDF

Info

Publication number
CN1041434C
CN1041434C CN88104903A CN88104903A CN1041434C CN 1041434 C CN1041434 C CN 1041434C CN 88104903 A CN88104903 A CN 88104903A CN 88104903 A CN88104903 A CN 88104903A CN 1041434 C CN1041434 C CN 1041434C
Authority
CN
China
Prior art keywords
nitrile
campholenic
oil
composition
pure
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 - Fee Related
Application number
CN88104903A
Other languages
English (en)
Other versions
CN1032188A (zh
Inventor
欧内斯特·约西姆·伯伦克
柯劳司·赫尔曼·卡皮尔
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.)
Symrise AG
Original Assignee
Draggo Gerberding and Co
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 Draggo Gerberding and Co filed Critical Draggo Gerberding and Co
Publication of CN1032188A publication Critical patent/CN1032188A/zh
Application granted granted Critical
Publication of CN1041434C publication Critical patent/CN1041434C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • 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
    • C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
    • C11B9/003—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing less than six carbon atoms

Landscapes

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

Abstract

已发现式A的α-龙脑烯腈和式B的γ-龙脑烯腈可出人意料地用作香料，特别是用作香料混合物的成分而使化妆品或工业消费品散发出香味，其中两种腈或单独使用或与添加剂混合使用。

Description

采用龙脑烯腈作香料
带龙脑烯骨架的人物在自然界中以醚油成分存在，如刺梅油中的α-龙脑烯醛2(A.F.Thomas.Helv.Chim.Acta，55,815(1972))。α-龙脑烯醛具有新鲜松香味。
龙脑烯醛2的某些长链衍生物具有木质-动物质类气味特点，相当于某些东印度檀香油的特点(Ubersicht in：E.-J.Brucke und E.Klein“Chemistrg of Sandalwood Fragrance”，in“FragranceChemistry”(Editor E.Theimer)，Academic Press，NewYork，1982，S.424-426))。
Figure C8810490300031
一般来说，对合成香料的需求是持续不断的，所制合成香料要适宜且具有相同质量，长期贮存过程中即使与其它物质接触时仍可保持稳定并具有所希望的嗅觉特征，即令人愉快和尽可能接近天然品并具有足够强度的芳香味特点，而且能够有利地影响化妆品或工业用品的香味。现已发现，式A的α-龙脑烯腈和式B的7-龙脑烯腈可完全满足这一要求，因为这些化合物可制得，为极其稳定的化合物，具有非常独特的气味特点并且扩香力极强，而这正是在许多方面极为有用的香料的特点。这些化合物因其气味特点而适于制成独创的化妆品，甚至作为极不相同香味特点的油性化妆品的成分。由于其化学稳定性，特别是耐酸性高，还使其特别适于使浸浊性相当强的基质(洗涤剂，家用清洁剂等)散发出香味。
Figure C8810490300041
     A：Δ3(2)；R1＝H，R2＝-R3＝R4＝CH3
     B：Δ1(2)；R1＝R2＝R3＝CH3，R4＝H
因此，本发明涉及式A的α-龙脑烯腈(下称4)以及式B的7-龙脑烯腈(下称6)作为香料或作为香料混合物的成分而使化妆品或工业消费品散发出香味的应用。其中，式A和B还包括龙脑烯腈的立体异构体，如蛇形线所示。根据本发明，A和B两种腈可以纯态或混合态得到应用。
对应于龙脑烯醛2的腈A已于1883年由V.Meger通过氯代甲烷对樟脑肟的作用而得到；但当时并不清楚这种产物的结构(V.Meger，Ber.Dt.Chem.Ges.16，2981(1883))。F.Tiemann成功地阐明并提出式A的结构(F.Tiemann，Ber.Dt.Chem.Ges.29，3006(1896))；在同一著作中作者还说明了用稀硫酸作用于樟脑肟而制得A的方法。此外，热解或光解有时也能生成腈A(T.Sato和H.Obase，Tetrahedron Lett.1967，(633-36)。另一方面，A还可用樟脑肟通过五氧化二磷(M.Nazir et al.，Pakistan J.Sci.Ind.Res.10(1)13-16(1967)或浓盐酸(N.G.Kozlov和T.Pekh，Zh.Org.Khim.1982，18(5)，1118-9))的作用而制得。在樟脑亚胺热解或光解混合物中有时也有A存在(L.J.Winters，J.F.Fisher和E.R.Ryan，Tetrahedron Letters 1971，129-132)。
α-龙脑烯腈A的嗅觉特点在文献中没有任何报道，而且文献中也根本没有说明7-龙脑烯腈B。
在作所气味鉴定时，与鸢尾根提取物比较起来，纯α-龙脑烯腈A具有扩香力强的香豆提取物和柑桔皮果香味，而纯7-龙脑烯腈B则是扩香力强的浓郁鲜木质味并具有枯茗附属特点。两种龙脑烯腈均可强化香料油的主要特点和扩香力。
龙脑烯腈A和B的香味效果是新颖独特的，不仅是纯态，而且呈混合态时也如此。此外，这些香味效果是出人意料的，一方面明显不同于已知龙脑烯衍生物的嗅觉特征，另一方面又决不可能根据其它已知腈的香型特征而预知，而且相当强的金属油脂附属特点对已知带柠檬主要特点的脂族腈如癸腈，十三烯-2-腈，香茅腈或牻牛儿腈来说是典型的，但是不希望出现，而腈A和B却不具有这些特点。因此，这方面的一般经验也表明，不允许根据已知香料的嗅觉特征而强制性地给结构相似的化合物作出结论，因为不管是味觉机理，还是化学结构对味觉的影响，都已作过深入的研究，而且还不可能依此而按常识预见到，已知香料的组成改变是否就一定意味着嗅觉特征的改变并且还不可能评价这种变化的好坏。
为制得腈A和B，可采取各种不同的方式，其中有两种反应途径已证明是特别适宜的，即：
1.按以下流程I将龙脑烯醛2肟化，然后脱水：
Figure C8810490300051
从α-龙脑烯醛2，α-环氧蒎烷的重排产物出发，即可用常规方法得到相应的肟3并可用乙酸酐脱水而得纯α-龙脑烯腈4(A)。
2.按以下流程II重排樟脑肟5。
Figure C8810490300061
用樟脑以普通方法得到的肟5再按Tiemann法用稀硫酸进行转化，其中先生成α-龙脑稀腈4和7-龙脑烯腈6的混合物。经过硫酸数小时的作用，可使α-龙脑烯腈基本上完全转化成7-龙脑烯腈。因此，首次出现纯7-龙脑烯腈6(B)。
根据所采用的反应途径的不同，可从旋光或非旋光离析物出发而选择性地将两种腈A和B制成旋光或非旋光产物，并且根据本发明不仅可用纯立体异构体，而且可用其混合物以及外消旋物。
用以下实施例详述本发明，但并不限制本发明。实施例1具有甜草特点的香料油
                             a        b橙油                             180g     180g乙酸异冰片酯                     300g     300g环枯蓬酸酯                       5g       5g香柠檬油                         100g     100g迷迭香油，土耳其产               30g      30g蒿油                             10g      10gBase Bigaradia 18*)              15g      15gApfelbase*)                      10g      10g二甲基-四氢苯甲醛                5g       5g乙酸苯乙烯酯                     20g      20g己基肉桂醛，α                                       100g     100g老鹳草油Bourbon，合成品          10g      10g苯基乙基醇                       30g      30g香茅醇                           100g     100gYlanat(对-叔丁基环己基乙酸酯)    30g      30gLignofix*)(乙酰基雪松烯)         30g      30g广藿香油                         20g      20gStemone(Givaudan)                5g       5g格蓬香树脂                       10g      10gMoschus Ambrette                 20g      20g环戊癸交酯                        20g     20gα-龙脑烯腈                               30g二丙二醇                          30g      -
                              1080g   1080g
*)DRAGOCO特定产品
香料油a具有甜草特点。
组合物b不含气味中性的二丙二醇，而含约3％α-龙脑烯腈，其味浓，新鲜并且显示出令人快悦的果味香型，特别适于泡沫浴。
实施例2
具有浓郁木质香特点的香料油
                                a        bEvernylR                          5g       5gBrahmanolR(DRAGOCO)               5g       5g丁子香酚甲基醚                     5g       5gDecatoneR(Givaudan)10％于DPG中    5g       5gGalaxolideR(IFF)                  20g      20g肉豆油                           20g      20gLilialR                           30g      30gSauge Claree Resinoid              35g      35gEichenmoos提取物，新鲜的南斯拉夫产(50％于DPG中)          50g      50g异丁基喹啉(10％于DPG中)          50g      50gMoschus Keton                    60g      60g丁子香酚                         80g      80g乙酸里哪基酯                     100g     100g杂熏衣草油                       100g     100g香柠檬油(无furocumarin)          100g     100gLignofix(DRAGOCO)                290g     290g二丙二醇                         45g      -7-龙脑烯腈                       -        45g
                             1000g    1000g
组合物a具有浓郁的木香味，而在向组合物b加有7龙脑烯腈的情况下，则发现具有极希望得到的甜草香特点(似Lavendel)以及显著的留香性。
实施例3
具有酸涩特点的香料油
                              a       b香柠檬油                          100g    100gCedernblatterol                   150g    150g洋艾油                            30g     30g迷迭香油，土耳其产                45g     45g穗熏衣草油，西班牙产             20g     20gMuskatellersalbeiol              10g     10g薄荷油，巴西产                   5g      5g苯基乙基醇                       100g    100g香茅醇                           30g     30g苯基醚                           10g     10g老鹳草油Bourbon                  5g      5g里哪醇                           50g     50g乙酸里哪酯                       60g     60g甲基紫罗兰酮，7                  50g     50gYlanat(4-叔丁基环己基乙酸酯)     50g     50g萜品醇，纯                       100g    100g茴香醛                           50g     50gLignofix*)(乙酰基雪松烯)         100g    100g水杨酸苄酯                       70g     70g依兰-依兰油，合成品              30g     30g格蓬提取物                       5g      5gCumarin                          50g     50g环戊癸交酯                       30g     30g二丙二醇                         40g     -7-龙脑烯腈                       -       40g
                             1240g   1240g*)DRAGOCO特定产品香料油a具有酸涩草复合香味。
组合物b含约3％ 7-龙脑烯腈，味浓，显草香特点并且具有新摘茶叶味特色。
实施例4
花香型香料油
                          a         bBrahmanolR                   20g       20g香茅醇                        50g       50g苯基乙基醚                    175g      175g吲哚                          4g        4g异丁子香粉                    6g        6g乙酸苄酯                      30g       30g里哪醇                        40g       40g萜品醇，纯                    240g      240gMuguetalkohol*)(2，2-二甲基-3-苯基丙醇)      200g      200gZimtalkohol                   40g       40g乙酸香茅酯                    20g       10g对羟基苄基丙酮*)              15g       15gBuccoxime*)(1.5-二甲基-8-肟基-二环-3，2，1-辛烷)       70g       70g二丙二醇                      90g       87gα-龙脑烯腈(A)                -         2g7-龙脑烯腈(B)                 -         1g
                        1000g     1000g
*)DRAGOCO特定产品
组合物a味浓，略显花香特点，似Maiglockchem，带热带果香附属特点。若加少量化合物A和B(组合物b)则显示出另一种气味特点，似令人快悦的“白花”香，带“素心兰”香型。
实施例5
下表表明α-龙脑烯腈在各种基质(同样适用于7-龙脑烯腈)中具有极高的稳定性。在进行鉴定的3个等级中，几乎全是“很好(SG)”只有一次“好(G)”，而没有出现“不好(NG)”。
                      气味稳定性
        试验基质    剂量(％)     1月室温   1月40℃     3月室温    3月40℃  气味效果(盖住基质时的扩香力)
  纯酸性    (H3PO4)纯碱性皂，白带TAED的全洗涤剂液态全洗涤剂柔软剂泡沫浴洗发剂气溶胶-抗汗剂喷剂防晒油/水-乳液     0.50.51.00.20.30.23.00.54.01.00.3     SGSGSGSGSGSGSGSGSGSGSG     SGSGSGSGSGSGSGSGSGSGSG     SGSGSGSGSGSGSGSGSGSGSG     GSGSGSGSGSGSGSGSGSGSG     强强强很强强很强很强很强强强很强
稳定性：SG＝很好(特点不变化)
        G＝好(特点变化小，合格)
        NG＝不好(特点变化，不合格)

Claims (1)

1.α-和/或γ-龙脑烯腈作为香料或香料混合物的成分而使化妆品或工业消费品散发出香味的应用。
CN88104903A 1987-08-07 1988-08-06 采用龙脑烯腈作香料 Expired - Fee Related CN1041434C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP3726418.4 1987-08-07
DE19873726418 DE3726418A1 (de) 1987-08-07 1987-08-07 Verwendung von campholennitrilen als riechstoff

Publications (2)

Publication Number Publication Date
CN1032188A CN1032188A (zh) 1989-04-05
CN1041434C true CN1041434C (zh) 1998-12-30

Family

ID=6333347

Family Applications (1)

Application Number Title Priority Date Filing Date
CN88104903A Expired - Fee Related CN1041434C (zh) 1987-08-07 1988-08-06 采用龙脑烯腈作香料

Country Status (7)

Country Link
US (1) US4912088A (zh)
EP (1) EP0302816B1 (zh)
JP (1) JPH0633395B2 (zh)
CN (1) CN1041434C (zh)
AT (1) ATE79896T1 (zh)
DE (2) DE3726418A1 (zh)
ES (1) ES2042793T3 (zh)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4111902A1 (de) * 1991-04-12 1992-10-15 Haarmann & Reimer Gmbh Cyclopentyl-cyanomethyl-cyclopentene, verfahren zu ihrer herstellung und ihre verwendung als riechstoffe
PL2094650T3 (pl) * 2006-12-08 2012-06-29 V Mane Fils Zastosowanie pochodnych kamfolenowych jako składników zapachowych w przemyśle perfumeryjnym i środków aromatyzujących
FR2950342B1 (fr) * 2009-09-18 2011-09-02 Mane Fils V Nouveaux aldehydes et nitriles issus de l'isophorone, ainsi que leur utilisation en parfumerie
GB201521758D0 (en) 2015-12-10 2016-01-27 Givaudan Sa Organic compounds

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2053199A (en) * 1979-05-09 1981-02-04 Polak S Frutal Work Bv Novel nitriles and their use as perfume chemicals

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3981891A (en) * 1972-01-18 1976-09-21 Societe Anonyme Roure Bertrand Dupont Cyclopentanone derivatives, odoriferous compositions containing them and process of preparation thereof
CA1118450A (en) * 1978-03-20 1982-02-16 Willem Lenselink Menthane nitriles
US4490284A (en) * 1982-09-29 1984-12-25 Dragoco Gerberding & Co. Gmbh 1,1-Di(C1 -C6 -alkyl)-2-phenyl-ethane derivatives as perfuming ingredients

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2053199A (en) * 1979-05-09 1981-02-04 Polak S Frutal Work Bv Novel nitriles and their use as perfume chemicals

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CA101:91245B 1984.1.1 Bardyshev,等 *
CA101:91245B 1984.1.1 Bardyshev,等;CA102:24837D 1985.1.1 Kozlov N.G等;CA77:48644E 1972.1.1 Pirisino,Geroeamo等 *
CA102:24837D 1985.1.1 Kozlov N.G等 *
CA77:48644E 1972.1.1 Pirisino,Geroeamo等 *

Also Published As

Publication number Publication date
US4912088A (en) 1990-03-27
CN1032188A (zh) 1989-04-05
JPH01113496A (ja) 1989-05-02
JPH0633395B2 (ja) 1994-05-02
DE3726418A1 (de) 1989-02-16
ES2042793T3 (es) 1993-12-16
DE3874047D1 (de) 1992-10-01
ATE79896T1 (de) 1992-09-15
EP0302816B1 (de) 1992-08-26
EP0302816A2 (de) 1989-02-08
EP0302816A3 (en) 1989-11-02

Similar Documents

Publication Publication Date Title
EP0056109B1 (fr) Utilisation de 2,6,6-triméthyl-cyclohex-2-ène-1-yl-carboxylate de méthyle à titre d'ingrédient parfumant
CN113025426B (zh) 作为加香成分的新戊酸1-异丙氧基-1-氧代丙-2-基酯
EP0482385B1 (fr) (2E,4Z,7Z)-Décatriénoate d'éthyle et son utilisation à titre d'ingrédient parfumant ou aromatisant
CN1041434C (zh) 采用龙脑烯腈作香料
JP2610309B2 (ja) 新規香料
JP3793591B2 (ja) 着香物質および／またはフレーバ付与物質としてのテルペン誘導体
US4144199A (en) Safranic acid ester perfume compositions
US4036774A (en) Fragrant soap compositions containing alpha-substituted acetaldehyde and ketone
DE2008254A1 (de) Geruchs- und Geschmaeksstoffe
US6509312B1 (en) Aliphatic esters and their utilization as perfuming ingredients
EP1229032A2 (en) 1,3-oxathianes as perfuming and flavouring ingredients
US6723313B2 (en) 2-,5-,6-,7-,8-substituted oct-2-en-4-ones
US5569660A (en) Utilization of an alkyl-substituted pyridine as a perfuming ingredient
DE69803429T2 (de) Von 3-Isopropenyl-1,2-dimethyl-1-cyclopentanol abgeleitete Nitrile und Aldehyde und ihre Verwendung in der Parfümerie
JP2002080886A (ja) ニトリルの混合物を含む芳香組成物
JP5399376B2 (ja) 付香成分としての４−ドデセン誘導体
SU786913A3 (ru) Композици душистых веществ парфюмерного назначени
JP3759670B2 (ja) 賦香組成物、香粧品ならびに賦香組成物または香粧品の匂い特性を付与するか、改善するか、強調するかまたは変更する方法
EP2079436B1 (en) Alpha, beta, unsaturated nitriles as fragrances
US4428870A (en) Perfume composition containing phenylethynyl carbinols
JP2727253B2 (ja) ２，６―ジメチル―５―ヘプテン―４―オリド
JPH0352517B2 (zh)
EP2928995B1 (en) Odorants of the violet type
CA1061097A (en) Cycloaliphatic unsaturated esters as flavour and odour agents
WO2005026092A1 (en) 4-methyldec-4-en-3-ol and fragrance composition

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C15 Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993)
OR01 Other related matters
C56 Change in the name or address of the patentee

Owner name: HIMMERLISY JIONT LIABILITY CO.,LTD.

Free format text: FORMER NAME OR ADDRESS: DRAGOCO GERBERDING + CO. GMBH

CP01 Change in the name or title of a patent holder

Patentee after: Symrise Gmbh & Co Kg

Patentee before: Dragoco Gerberding & Co. GmbH

C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee