CN1028540C - 制造低变应原性苔油的方法 - Google Patents
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Classifications
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- 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
- C11B9/02—Recovery or refining of essential oils from raw materials
- C11B9/022—Refining
Abstract
制造低变应原性苔油的方法,它包括将原材料苔油,一种凝结物或其净油与至少一种在溶液中以单相状态存在的氨基酸反应,并分离除去变应原性不溶物质。
Description
本发明涉及低变应原性苔油(moss oil)更确切地说是有关制备这些低变应原性苔油的方法。
该方法包括除去某些变应原性物质,例如,ethyl hematommate 1,ethyl chorohenmatommate 2,atranorin 3,chloratranorin4,atranol5, chloratranol6,
这此物质存在于大多数苔油中,上述物质的特征在于它们具有醛官能团。
该方法包括将原材料,即未经处理的苔油(一种凝结物或其净油),与至少一种在溶液中以单相状态存在的氨基酸反应,优选的溶液是大体上为醇的溶液,并分离出变应原性不溶物质。
用溶剂萃取地衣得到的苔油(地衣油)具体包括栎扁枝地衣油(Evernia prunastri L.)和树苔藓油(Evernia furfuraceaL.)。
从S.Ohta等人(化学药物通报,28卷,1980年1917页)的工作已知,为了分离出作为席夫碱反应产物的醛类物,可用某些氨基酸钠盐的水溶液处理在水溶液和有机溶液中的醛类物。由于在这种情况下形成了乳化液,并且很难用常规技术防止产生和/或破坏这种乳化液,所以在这种情况下上述分离技术是不适用的。
本发明的新方法克服了由于下面的事实所造成的困难,即初始物料只溶于有机溶剂和氨基酸只溶于水溶液。而且,令人惊奇地发现,这种新方法似乎让人器管感觉不到降低了苔油的品质,换句话说,似乎没有从苔油中除掉任何一种器管可以感觉到的活性化合物。
在本发明的上下文中,苔油中醛1-6的浓度若高于表1所示范围则被认为是变应原性,若低于表1所示的范围则被认为属低变应原性苔油(表1见文后)
合适的工艺参数如下:
氨基酸:优选的氨基酸具有如下通式
其中R1=H,NH2Ⅰ
R2=H,CH3
R3=H,C1-C3-烷基,C1-C3-烷基-氨基,苯基
而且在R1或R3中至少有一个氨基。
优选的氨基酸是天然产生的氨基酸(和各自的同型氨基酸)。并且,优选的氨基酸是其等电点PI在约5.5到约10之间的那些氨基酸,例如赖氨酸,亮氨酸,苯基丙氨酸,还有丙氨酸,甘氨酸,异亮氨酸等。
优选的氨基酸是那些自然界存在的氨基酸。
最好是通过在一种大体上为醇(最好含醇量≥95%)的溶液中操作来达到单相状态,例如诸如甲醇,乙醇,异丙醇等链烷醇溶剂。
水中的氨基酸浓度:宁可浓一些,例如大约30至80%(重量比)。
所用的氨基酸量:每克苔油大约用0.02到0.3克,最好是0.04到0.1克。
当使用的氨基酸以一氢卤化物,例如一氢氯化物(R.HCl)的形式存在时,加入一摩尔当量的碱,例如NaOH或KOH。
pH:在PI所示范围内。
温度:大约20°到80℃,最好是70°到80℃,由此,最好是将原材料苔油的热的有机溶液加到热的氨基酸溶液中。
醇溶液中原材料的合适浓度:
凝结物:占醇的大约5%到40%,最好是大约10%到15%(重量/重量)。
净油:占醇的大约5%到40%,最好是大约10%到15%(重量/重量)。
最后步骤:仅滤去过量的氨基酸和席夫碱。
实施例
引起过敏症的测定:
借助常规的,充分制定的方法确定每一种情况下有无过敏症,即使用豚鼠作MT(最大剂量试验),
使用豚鼠作OET(切开皮肤试验)
使用人作对象作PIPT(重复的局部损伤试验)。
所得的实验数据用来编制表1。
成分1,2,5和6的浓度宜用气相色谱(GC)分析来测定,例如在下列条件下使用内标法:固定相:(聚硅氧烷层)CPSIL5CB;载气:氦气,2毫升/分钟;程序升温:100/270℃/分钟。醛3和4的浓度,宜用高压液相色谱(HPLC)测定,例如,使用外标法,在下列条件下进行:固定相:RP18(反相),粒度7微米;柱子:250×4.6毫米;流动相A:H2O,pH=2.8(H3PO4);流动相B:乙腈;梯度,30分钟80%A到5%A,10分钟5%A;检测器:在260纳米(毫微米)的紫外光波长位置检测。
实施例1
从市售的栎扁枝地衣净油制造低变应原性栎扁枝地衣净油
在一只三颈圆底烧瓶中装入乙醇96°(1.24升)在室温下搅拌加入赖氨酸氢氯化物溶液(6.25克)和溶于10毫升蒸馏水中的一摩尔当量氢氧化钠(1.4克),随后添加溶于乙醇96°(625毫升)中的亮氨酸(6.25克)。在室温下再搅拌30分钟后,加入溶于乙醇96°(625毫升)中的熔化的栎扁枝地衣净油(250克,熔点约70℃)溶液,将全部混合物加热回流一小时。冷却至室温后再搅拌30分钟,将反应混合物于室温用布氏漏斗(在滤纸上)过滤。在水浴上减压蒸去乙醇,水浴温度不得超过65℃。如此制得的低变应原性栎扁枝地衣净油(240克,产率>95%),经分析测试,结果示于表2。(表2见文后)
实施例2
从栎扁枝地衣凝结物制造低变应原性栎扁枝地衣净油
将乙醇96°(900毫升)和熔化的栎扁枝地衣凝结物(150克,熔点约70℃)放入一只三颈圆底烧瓶。将混合物冷至30℃,将赖氨酸氢氯化物(3.75克)溶液用溶于6毫升蒸馏水中的一摩尔当量的氢氧化钾(85%)(1.35克)中和,并和亮氨酸(3.75克)于室温下边搅拌加入烧瓶中。继续搅拌30分钟后,将全部混合物加热回流一小时。冷却至室温后,再搅拌30分钟,将反应混合物冷却至-15℃并用滤纸过滤。在水浴上减压蒸去乙醇,水浴温度不得超过65℃。如此制得的低变应原性栎扁枝地衣净油(110克,产率为凝结物的73%),其分析结果示于表3。(表3见文后)
实施例3
从市售的树苔藓净油制造低变应原性树苔藓净油
除了用“树苔藓净油”代替“栎地衣净油”外,其步骤与实施例1所述的一样。如此制得的树苔藓净油(250克,产率约为市售净油的100%),分析结果示于表4。(表4见文后)
表1
醛 变应原性 低变应原性苔油
苔油中所含% 中所含%
Ethyl hematommate 1 >1 ≤1
Ethyl chlorhematommate 2 >0.05 ≤0.05
Atranorins 3+4 >0.15 ≤0.15
Atranol 5 >0.2 ≤0.2
Chloratranol 6 >0.2 ≤0.2
表2
分析 原材料栎扁枝 处理所得的栎
地衣净油 扁枝地衣净油
Ethyl hematommate 1 3.53 0.90
Ethyl chlorhematommate 2 1.44 <0.05
Atranorins(3+4) 0.30 0.14
Atranol 5 2.83 <0.01
Chloratranol 6 1.40 <0.01
表3
分析 原材料栎扁枝 处理所得的栎
地衣凝结物 扁枝地衣净油
Ethyl hematommate 1 2.40 1.02
Ethyl chlorhematommate 2 0.36 <0.01
Atranorins(3+4) 4.00 0.12
Atranol 5 0.57 <0.01
Chloratranol 6 0.46 <0.20
表4
分析 原材料树苔藓 处理所得的
净油 树苔藓净油
Ethyl hematommate 1 2.26 0.19
Ethyl chlorhematommate 2 0.51 <0.01
Atranorins(3+4) 0.17 0.15
Atranol 5 0.70 <0.01
Chloratranol 6 0.62 <0.13
Claims (7)
2、根据权利要求1的方法,其中反应是在溶液中进行,所述溶液是选自甲醇、乙醇和异丙醇的醇溶液。
3、根据权利要求2的方法,其中醇溶液是乙醇溶液。
4、根据权利要求1的方法,其中所用的氨基酸的等电点在5.5<PI<10的范围内。
5、根据权利要求1或4的方法,其中使用的氨基酸是赖氨酸,亮氨酸或苯基丙氨酸。
6、根据权利要求1或4的方法,其中用的氨基酸是丙氨酸,甘氨酸或异亮氨酸。
7、根据权利要求1或4的方法,其中反应是在70-80℃的温度范围内进行。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP90810468.0 | 1990-06-22 | ||
EP90810468 | 1990-06-22 |
Publications (2)
Publication Number | Publication Date |
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CN1057479A CN1057479A (zh) | 1992-01-01 |
CN1028540C true CN1028540C (zh) | 1995-05-24 |
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CN91104170A Expired - Fee Related CN1028540C (zh) | 1990-06-22 | 1991-06-20 | 制造低变应原性苔油的方法 |
Country Status (8)
Country | Link |
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US (1) | US5118504A (zh) |
EP (1) | EP0468189B1 (zh) |
JP (1) | JPH04226197A (zh) |
CN (1) | CN1028540C (zh) |
DE (1) | DE69106804T2 (zh) |
ES (1) | ES2067092T3 (zh) |
HU (1) | HU206391B (zh) |
RU (1) | RU2092168C1 (zh) |
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DE69307656T2 (de) * | 1992-05-20 | 1997-08-07 | Givaudan Roure Int | Aetherisches oel |
US5510325A (en) * | 1992-05-20 | 1996-04-23 | Givaudan-Roure Corporation | Essential oil |
FR2848111B1 (fr) * | 2002-12-06 | 2005-02-11 | Robertet Sa | Extrait de lichen a teneur reduite en acides resiniques, procede de preparation et utilisations |
US7497947B2 (en) * | 2004-04-14 | 2009-03-03 | Embro Corporation | Devices for water treatment |
FR2953040A1 (fr) * | 2009-11-23 | 2011-05-27 | Nicolas Danila | Dispositif de formulation chimique des parfums a forte concentration d'ingredients naturels sans allergenes a declarer |
EP2753422A1 (en) | 2011-09-07 | 2014-07-16 | Embro Corporation | Use of moss to reduce disinfection by-products in water treated with disinfectants |
US9795809B2 (en) | 2013-12-23 | 2017-10-24 | Embro Corporation | Use of moss to improve dental health |
US20210009921A1 (en) | 2018-03-12 | 2021-01-14 | Université Côte d'Azur | Process for converting atranol and its derivatives into hydrosoluble compounds |
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US4308401A (en) * | 1980-03-13 | 1981-12-29 | Fritzsche Dodge & Olcott Inc. | Halogen containing cyclohexane derivatives, methods of preparation and compositions containing same |
JPS61126013A (ja) * | 1984-11-20 | 1986-06-13 | Kuraray Co Ltd | 香料組成物 |
US4663080A (en) * | 1985-05-21 | 1987-05-05 | Shiseido Company Ltd. | Hypo-allergenic moss oil and production process thereof |
-
1991
- 1991-06-14 ES ES91109767T patent/ES2067092T3/es not_active Expired - Lifetime
- 1991-06-14 DE DE69106804T patent/DE69106804T2/de not_active Expired - Fee Related
- 1991-06-14 EP EP91109767A patent/EP0468189B1/en not_active Expired - Lifetime
- 1991-06-17 HU HU912004A patent/HU206391B/hu not_active IP Right Cessation
- 1991-06-19 US US07/717,622 patent/US5118504A/en not_active Expired - Fee Related
- 1991-06-20 CN CN91104170A patent/CN1028540C/zh not_active Expired - Fee Related
- 1991-06-21 JP JP3150328A patent/JPH04226197A/ja active Pending
- 1991-06-21 RU SU914895619A patent/RU2092168C1/ru active
Also Published As
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---|---|
HUT58785A (en) | 1992-03-30 |
US5118504A (en) | 1992-06-02 |
RU2092168C1 (ru) | 1997-10-10 |
EP0468189A3 (en) | 1992-08-26 |
EP0468189A2 (en) | 1992-01-29 |
EP0468189B1 (en) | 1995-01-18 |
ES2067092T3 (es) | 1995-03-16 |
DE69106804D1 (de) | 1995-03-02 |
JPH04226197A (ja) | 1992-08-14 |
HU206391B (en) | 1992-10-28 |
DE69106804T2 (de) | 1995-08-17 |
CN1057479A (zh) | 1992-01-01 |
HU912004D0 (en) | 1991-12-30 |
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