CN1108644A - 1-苯基-1-氰基-c5-c7烷烃及其制造方法和用途 - Google Patents

1-苯基-1-氰基-c5-c7烷烃及其制造方法和用途 Download PDF

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CN1108644A
CN1108644A CN94118425.0A CN94118425A CN1108644A CN 1108644 A CN1108644 A CN 1108644A CN 94118425 A CN94118425 A CN 94118425A CN 1108644 A CN1108644 A CN 1108644A
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alkane
structural formula
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CN1131852C (zh
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亚瑟·T·利伏斯
梅利·R·海娜
查尔斯·E·J·贝克
凯塞林·E·鲍特维克
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International Flavors and Fragrances Inc
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11BPRODUCING, 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
    • C11B9/00Essential oils; Perfumes
    • C11B9/0061Essential oils; Perfumes compounds containing a six-membered aromatic ring not condensed with another ring
    • C11B9/0065Nitriles
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00Carboxylic acid nitriles
    • C07C255/01Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/33Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring with cyano groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by saturated carbon chains
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00Carboxylic acid nitriles
    • C07C255/01Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/34Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring with cyano groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by unsaturated carbon chains
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00Carboxylic acid nitriles
    • C07C255/01Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/37Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by etherified hydroxy groups

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  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)
  • Cosmetics (AREA)

Abstract

本发明涉及1-苯基-1-氰基C5-C7烷烃,其结构为上式,R1和R2各别代表氢和甲氧基。如果R1是氢,则R2是甲氧基,反之,R1是甲氧基则R2是氢,X代表C3-C5的烷烃直链或烷烃分枝链。此物品用于增强或修正香水成分、香物品、及刮须香水。并叙述制造此1-苯基-1-氰基C5-C7烷烃的过程中以苯甲基氰与醛或酮作用,以钯为催化剂,然后进行氢化作用而得的产品。

Description

本发明涉及1-苯基-1-氰基-C5-C7烷烃,其结构通式为:
R1和R2各别代表氢和甲氧基。如果R1是氢,则R2是甲氧基,反之,R1是甲氧基则R2是氢,X代表C3-C5的直烷烃链或支链烷烃。此物品用于增强或修正香水成分、香物品、及刮须香水。此新颖的合化物,较佳的结构式如下:
Figure 941184250_IMG21
它们是用于加强或增进香水成分,刮须香水及香物品的芳香气。香物品包括但不限于香聚合物,化妆粉,阴离子的、阳离子的、非离子的或两性离子的清洁剂,布料软化剂成分、布料软化剂包括用于烘干机的软化剂。(比如,BOUNCE是由俄亥俄州,辛辛那提市的Procter  &  Gamble公司出品)。
此化合物的结构通式如下:
Figure 941184250_IMG22
以下将涉及本发明的1-苯基-1-氰基-C5-C7烷烃。本发明的1-苯基-1-氰基-C5-C7烷烃,具有赋于、加强或增进花香、玫瑰香、铃兰香、药草香、青草香、水果香、似夙梨香、水杨醛酸酯香、紫苏香、甜香、生橙花香、杏仁香、樱桃香、麝香、香脂香、柏木香、及山艾香偕同甜味、割草香、花香、钤兰香、玫瑰香、水杨酸酯香、茴香脑、香芹酮香、木香等留香,其立时发放的香气为,甜味香、木香、水果香、酒香、割草香、水杨酸酯香、似动物气味、似蜂蜜味、花香、玫瑰香、似松脂香、玫瑰木香。当用于香水成分,刮须香水和其它香物品如肥皂、漂白剂、和任何阴离子的,阳离子的,非离子的,两性离子的清洁剂、布料软化剂等等香物品时,常有清洁的效果。
本发明第一步的制造过程,涉及到以苯甲基氰,其结构式如下:
Figure 941184250_IMG23
和如下结构式的醛类或酮类:
Figure 941184250_IMG24
互相作用。
此处的R3和R4是相同或不同的氢或低级烷烃,其条件是,
R3和R4不是同时为氢,根据下面的反应式:
所得的产物,其结构式如下:
Figure 941184250_IMG26
然后以钯为催化剂,(钯附于碳上)进行氢化作用,其反应式如下:
Figure 941184250_IMG27
如此形成的产品,其结构式如下:
Figure 941184250_IMG28
定名为本发明的1-苯基-1-氰基-C5-C7烷烃的结构通式如下:
Figure 941184250_IMG29
制造本发明的反应式如下:
Figure 941184250_IMG30
此反应进行时,温度保持在35°-90℃之间,以酒精基且无水的碱性金属的氢氧化物为催化剂。所用的酒精可以是甲醇或乙醇。碱性氢氧化物金属可以是氢氧化钾或氢氧化钠。(醛或酮)∶(苯甲基氰的衍生物)的摩尔比例,约为0.5∶1至1∶0.5不等,但摩尔比例以1∶1为宜。(碱性氢氧化物金属)∶(酒精)的摩尔比例,约为每公升含40克至每公升含120克不等。
下面的化合物,其结构式如下:
Figure 941184250_IMG31
与酒精(甲醇或乙醇)的摩尔比例,约为每公升含二摩尔至每公升含六摩尔不等。反应时间约五至三十小时不等。
进行氢化作用的反应式
反应温度约80°-100℃,压力约300-600psig。催化剂以钯附于碳上,钯的含量约占3%-10%不等,但以占5%为宜。
反应结束后,反应总体经过滤并以蒸馏柱分馏。再引述其反应式如下:
Figure 941184250_IMG33
反应到后最时,反应总体加弱酸如醋酸来停止反应,然后用水洗。此反应总体,在进行氢化作用之前,采用蒸馏柱分馏。
以下的表格表明各种成分的不同香性质,其一般结构式如下:
Figure 941184250_IMG34
它在香精上用途很广。
表1
Figure 941184250_IMG35
Figure 941184250_IMG36
本发明的化学物用于下列的柏木香配方:
成分    重量比例
A部分    B部分    C部分
黄葵    40    40    40
麝香酮    60    60    60
香豆素    30    30    30
香柠檬油    150    150    150
柠檬油    100    100    100
甲基紫罗桐    50    50    50
己基肉桂醛    100    100    100
羟基香茅醛    100    100    100
欧薄荷    50    50    50
德州柏木油    85    85    85
维州柏木油    30    30    30
檀香木油(东印度)    40    40    40
丁子香粉    10    10    10
苯乙酸酯    30    30    30
α-苯基-乙醇    40    40    40
β-苯基-乙醇    30    30    30
橡树苔净油    30    30    30
岩兰草油(委内瑞拉)    25    25    25
Figure 941184250_IMG37
62 0 0
Figure 941184250_IMG38
含结构式如下的化合物:
Figure 941184250_IMG39
赋予此柏木香配方以花香、钤兰香、割草香、水杨醛酸酯香、茴香脑香和似香芹酮等留香,并发放出花香、玫瑰香、钤兰香、割草香、水果香、夙梨香、水杨醛酸酯香。根据例子A柏木香配方,可叙述为“是一种柏木芳香物,发散出花香、玫瑰香、钤兰香、割草香、水果香、夙梨香、水杨醛酸酯香并以花香、钤兰香、割草香、水杨醛酸酯香、茴香脑、香芹酮等留香。”
含结构式如下的化合物:
Figure 941184250_IMG40
赋予此柏木香配方以木香、甜味香和杏仁味等留香,并发散出杏仁味和樱桃香。根据例子B柏木香配方,可叙述为“是一种柏木芳香物,以木香、甜味香和杏仁味等留香,并发散出杏仁味和樱桃香。”
含结构式如下的化合物:
Figure 941184250_IMG41
赋予此柏木香配方以割草香、木香、雪茄烟盒香味、水杨醛酸酯香和龙涎香之留香,并发散出割草香和木香。根据例子C柏木香配方,可叙述为“是一种柏木芳香物,有割草香、木香、似雪茄烟盒香味、水杨醛酸酯香盒龙涎香等留香,并发散出割草香和木香。”

Claims (14)

1、将香精加入和增强于一群特选的香精成分,香物品,刮须香水等消费品中,即包括均匀混合而成消费品的步骤,其特征在于,此消费品基本上由香精与至少含一份1-苯基-1-氰基-C5-C7烷烃的混合物,其结构式如下:
Figure 941184250_IMG2
R1,R2各别代表氢与甲氧基,如果R1是氢,则R2是甲氧基,如果R1是甲氧基,则R2就是氢,X代表C3-C5的直链烷烃或分枝链烷烃。
2、如权利要求1所述的程序中的1-苯基-1-氰基-C5-C7烷烃,其特征在于其结构式如下:
Figure 941184250_IMG3
3、如权利要求1所述的程序中的消费品,其特征在于是一种香料混合物。
4、如权利要求1所述的程序中的消费品,其特征在于是一种香物品,此香物品是一种固态或液态的阴离子的,阳离子的,非离子、两性离子的清洁剂。
5、如权利要求1所述的程序中的消费品,其特征在于是一种香物品,同时也是一种香聚合物。
6、一种香的消费品,由一组香成分,香物品,香聚合物及刮须香水组成的,其特征在于它包括一种以消费品为基本,混合香精或至少一份的1-苯基-1-氰基-C5-C7烷烃,其结构式如下:
Figure 941184250_IMG4
此处的R1和R2各代表氢和甲氧基,其条件是,若是R1为甲氧基,则R2为氢,若是R1为氢,则R2为甲氧基;X代表C3-C5烷烃的直链或分枝链。
7、如权利要求6所述的香消费品中,所述的消费品是一种香消费品,其特征在于内含的1-苯基-1-氰基-C5-C7烷烃,此烷烃的结构式如下:
Figure 941184250_IMG5
8、如权利要求6所述的消费品中,所述的消费品是一种刮须香水,其特征在于其组成分为水,酒精和1-苯基-1-氰基-C5-C7烷烃。此烷烃的结构式如下:
Figure 941184250_IMG6
9、如权利要求6所述的香消费品中,其消费品是一种含微细孔洞的聚合物,其特征在于其空隙中以香精填入而组成的,此烷烃聚合物的结构式如下:
Figure 941184250_IMG7
10、1-苯基-1-氰基-C5-C7烷烃是由一群合成物中挑选出来的,其特征在于此化合物群的结构式,分别表示如下:
Figure 941184250_IMG8
11、如权利要求10所述的1-苯基-1-氰基-C5-C7烷烃,其特征在于其结构式如下:
Figure 941184250_IMG9
12、如权利要求10所述的1-苯基-1-氰基-C5-C7烷烃,其特征在于其结构式如下:
Figure 941184250_IMG10
13、如权利要求10所述的1-苯基-1-氰基-C5-C7烷烃,其特征在于其结构式如下:
Figure 941184250_IMG11
14、一种制造1-苯基-1-氰基-C5-C7烷烃的方法,其烷烃的结构式如下:
此处的R1和R2各别为氢和甲氧基,其条件为,若中R1为甲氧基,则R2为氢,若是R1为氢,则R2为甲氧基;X代表C3-C5的直链或分枝链烷烃。
其特征包括(1)实际进行的反应式如下:
即将此结构式
的化合物,与结构式:
的化合物,
温度保持在35°-90℃之间,置于酒精而无水之碱性金属的氢氧化物的存在状况下反应,而形成如下的化合物:
Figure 941184250_IMG16
此处的R3和R4各别代表低级烷基或氢,附带的条件是R3和R4不能同时为氢,以及
(2)将结构式如下的化合物:
Figure 941184250_IMG17
与氢作用时,温度保持在80°-100℃之间,压力保持在300-600psog进行反应。其反应式如下:
Figure 941184250_IMG18
(3)将化合物从反应整体中分离出来,此化合物的结构式如下:
Figure 941184250_IMG19
CN94118425.0A 1994-05-12 1994-12-16 1-苯基-1-氰基-c5-c7烷烃及其用途 Expired - Lifetime CN1131852C (zh)

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US08/241,725 US5389608A (en) 1994-05-12 1994-05-12 1-phenyl-1-cyano-C5 -C7 alkanes, organoleptic uses thereof and process for preparing same

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JP2004528289A (ja) * 2001-01-26 2004-09-16 クエスト・インターナショナル・ビー・ブイ 芳香性化合物
EP1637581B1 (en) 2004-09-16 2008-07-09 Firmenich S.A. Nitrile derivatives as perfuming ingredients
JP5248114B2 (ja) * 2004-12-08 2013-07-31 ジボダン エス エー 有機化合物
GB0518558D0 (en) * 2005-09-12 2005-10-19 Givaudan Sa Improvements in or related to organic compounds
US7390772B2 (en) 2006-05-18 2008-06-24 International Flavor & Fragrances Inc. 1-phenyl-spiro[2.5]octane-1-carbonitrile analogues their use in fragrance formulations

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US2919274A (en) * 1957-09-17 1959-12-29 Sahyun Melville Amidines
NL169613C (nl) * 1975-02-11 1982-08-02 Naarden International Nv Werkwijze ter bereiding van reukstofcomposities respectievelijk geparfumeerde produkten en aldus verkregen geparfumeerde voorwerpen.
RO75279A2 (ro) * 1976-12-31 1980-09-30 Intreprinderea De Medicamente "Terapia",Ro Procedeu de preparare a acizilor cicloalchilfenilacetici
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DE3139358C2 (de) * 1981-10-02 1984-06-07 Dragoco Gerberding & Co Gmbh, 3450 Holzminden Verwendung von 1,1-Di(C↓1↓-C↓6↓-alkyl)-2-phenyl-ethan-Derivaten als Riechstoffe
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US5143899A (en) * 1991-09-13 1992-09-01 International Flavors & Fragrances Inc. Process for preparing phenyl butyronitriles and perfumery use of 2,2-dimethyl-4-phenyl valeronitrile

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CN1131852C (zh) 2003-12-24
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DE69506944D1 (de) 1999-02-11
EP0682010B1 (en) 1998-12-30
US5389608A (en) 1995-02-14

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