CN102260146B - Method for preparing hydrogenated hop acid - Google Patents
Method for preparing hydrogenated hop acid Download PDFInfo
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- CN102260146B CN102260146B CN201010189195.0A CN201010189195A CN102260146B CN 102260146 B CN102260146 B CN 102260146B CN 201010189195 A CN201010189195 A CN 201010189195A CN 102260146 B CN102260146 B CN 102260146B
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- humulone
- acid
- hop acid
- isohumulone
- hop
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Abstract
The invention relates to a method for preparing hydrogenated hop acid, in particular to a unique method for preparing the hydrogenated hop acid, including tetrahydro humulone, tetrahydro iso-humulone, hexahydro iso-humulone, or hexahydro lupulone under a hydrogen-free condition. The method has the advantages of simple and safe operation, and good preparation effect.
Description
Technical field
The present invention relates to one and prepare hydrogenated hop acid, comprise the peculiar methods of tetrahydrochysene humulone (claim not only tetrahydrochysene α acid), tetrahydro-iso-humulone (claim tetrahydrochysene different α acid not only), Hexahydroisohumulone (claim six hydrogen different α acid not only) and hexahydrolupulon (but also claiming six hydrogen β acid), more specifically, the present invention relates to a kind of peculiar methods of preparing tetrahydrochysene humulone, tetrahydro-iso-humulone, Hexahydroisohumulone and hexahydrolupulon under no hydrogen condition, this method has easy to operate and safe, prepares effective advantage.
Background technology
Hops or Hops Extract in the process of beer brewing (being called for short hops or hop extract) are added in wort copper provided, humulone composition in hops or hop extract (claims again α acid, as shown in structural formula I below), be isomerizated into isohumulone through chemical reaction and (claim again different α acid or isomery humulone, as shown in formula II below), dissolve in wheat juice, wheat juice becoming beer after yeast fermentation.Isohumulone can be given beer with distinctive bitter taste, suppresses the growth of spoilage microorganisms, strengthens the foam characteristic of beer.Another main component lupulone (claiming again β acid, as shown in formula II I below) of hops or hop extract is insoluble in wheat juice, conventionally can be deposited in wheat grain and abandon it.So lupulone is not almost utilized in brewage.
Structural formula I formula II formula II I
Structural formula IV structural formula V structural formula VI
Structural formula VII structural formula VIII
Wherein, R is sec.-propyl, sec-butyl or isobutyl-.
But isohumulone is unstable to light and day auroral poles in beer, when being loaded on containing the beer of isohumulone, in transparent or green bottle, to be exposed under daylight or under light be to produce a kind of stink that is unfavorable for beer flavor, be called as daylight at beer industry smelly, this is to have produced a kind of new material owing to there is photolysis between the isohumulone composition in beer and naturally occurring sulfide.Find that and the while stable to light still has the reductive derivative of the isohumulone of unique bitter taste.The reductive derivative of the isohumulone using at present has three kinds, be dihydro isohumulone (Rho-isohumulone, as shown in structural formula V), tetrahydro-iso-humulone (as shown in structural formula VI) and Hexahydroisohumulone (as shown in structural formula VII).These three kinds of derivatives not only can not form so-called " daylight is smelly ", and tetrahydro-iso-humulone and Hexahydroisohumulone can also improve the froth stability of beer effectively.For isohumulone, dihydro isohumulone has relatively low bitter taste, and the bitter taste of tetrahydro-iso-humulone is 1.7-2.0 times of isohumulone, and has stronger short bubble and bacteriostatic action.The increase foaming of Hexahydroisohumulone than tetrahydro-iso-humulone slightly a little less than, its bitter taste be isohumulone 1.1-1.3 doubly.In the U.S., the reductive derivative of these isohumulones is as the raw material history of existing more than 20 year of beer production.As one of brewage basic raw material, it can significantly improve anti-Japanese photosensitiveness, the holding property of bubble of beer, can as isohumulone, give beer acerbity and germ resistance simultaneously.In addition, compared with isohumulone, the isohumulone of these hydrogenations has better stability, can extend flavor stability and the shelf-lives of beer.
And another main ingredient lupulone in hops or hop extract does not have bitter taste, but there is the ability that extraordinary anti-bacteria grows.But, because lupulone is insoluble in wheat juice, in Process of Beer Brewing, be waste material substantially, without how many use, if can be apt to add utilization, can improve utilization ratio and the added value of hops or beer medicinal extract.The hydrogenated products hexahydrolupulon (as shown in structural formula VIII) of lupulone not only has extraordinary stability, also has extraordinary antibacterial and anti-oxidant activity.It can be in the product beyond beer, as food, feed, sanitising agent, healthcare products etc.
There are many documents both domestic and external or patent report and made the method for isohumulone and lupulone hydrogenation.For example U.S. Patent number 3,552,975 (1971) disclose a kind of method adds hydrogen by lupulone and is hydrogenated to tetrahydrochysene anaerobic humulone and is oxidized in obtaining tetrahydrochysene humulone (as shown in structural formula IV) in plumbic acid solution through air or oxygen, more changes into tetrahydro-iso-humulone through isomerization.The shortcoming of the method is that oxidation is a lot of when construction cost, and residual poisonous lead compound in product likely.U.S. Patent number 3,923,897 (1975) disclose the another kind of method of preparing tetrahydro-iso-humulone, the method be in organic solvent with various peroxide oxidation tetrahydrochysene anaerobic humulone become after tetrahydrochysene humulone re-isomerization tetrahydro-iso-humulone.The shortcoming of this method is likely to residue in product harmful to food and environment with superoxide and organic solvent.U.S. Patent number 4,644 in 1987,084 disclose a kind of to food and the safer preparation method of environment, only use air, ethanol, water and alkali and acid etc. safety crude substance.The method is from the hop extract of carbon dioxide abstraction, first to separate humulone and two kinds of compositions of isohumulone, and it is described in detail in U.S. Patent number 4,590,296 (1986) and 4,666,731 (1987).Then lupulone hydrogenation in alcoholic solution, filters out palladium powdered carbon catalyzer and adds alkaline aqueous solution and/or inorganic base salts, and logical oxygen or atmospheric oxygen change into tetrahydrochysene humulone, also heating is isomerizated into tetrahydro-iso-humulone simultaneously.China Patent No. 94100149.0 in 1997 discloses one does not need first to separate humulone and lupulone mixture in hop extract, directly humulone and lupulone is changed into tetrahydro-iso-humulone simultaneously.In the method, after hydrogenation, evaporate alcoholic solution, separately add ethane or methylene dichloride and the palladium powdered carbon that stays and air or oxygen are oxidized to tetrahydrochysene humulone in organic solvent, then add alkaline aqueous solution re-isomerization and become tetrahydro-iso-humulone.This method is not only used unsafe organic solvent and is that two-step approach is separately carried out in oxidation and isomerization.U.S. Patent number 5,013 in 1991,571 are disclosed under the existence of noble metal catalyst, with hydrogen, humulone hydrogenation simultaneously and isomery are turned to the method for tetrahydro-iso-humulone, and openly use NaBH
4reductive agent is reduced into tetrahydro-iso-humulone the method for Hexahydroisohumulone.U.S. Patent number 4,918,240 disclose the method for being prepared tetrahydrochysene anaerobic humulone by the lupulone experience step of hydrogenation of purifying.
But foregoing invention method all comprises use, hydrogen carries out hydrogenation.This hydrogenation all must be in anaerobic or without using hydrogen (H under air conditions
2) under specific pressure, through catalyst action, undersaturated double-bond hydrogenation reaction in hop acid is generated to saturated singly-bound, generate tetrahydrochysene humulone (as shown in structural formula IV), tetrahydro-iso-humulone, Hexahydroisohumulone and hexahydrolupulon, under specified pressure, carry out hydrogenation with hydrogen and must have agitator at a high speed and valuable leakproof, explosion-proof retort, and many supporting safety operation facilities, so investment is expensive.
Summary of the invention
The present invention be directed to the problems referred to above proposes.The present invention is a kind of without hydrogen, can under low-temperature atmosphere-pressure, operate, and safe and effective, equipment cost is cheap, the method for all kinds of hydrogenated hop acids of preparation easy and simple to handle.
Therefore, the object of this invention is to provide a kind of method of preparing hydrogenated hop acid, the method comprises the steps:
Make hop acid solution, the formate aqueous solution or formic acid, and noble metal catalyst mixes;
Said mixture is stirred and reacted; And
Acidifying, separation obtain hydrogenated hop acid.This step is specially: after acidifying, leave standstill natural layering, the water that removes lower floor obtains the oil phase on upper strata, and this oil phase is hydrogenated hop acid.
The present invention adopts formic acid (HCOOH) or formate (sodium formiate (HCOO
-na
+), potassium formiate (HCOO
-k
+), calcium formiate ((HCOO
-)
2ca
2+) and ammonium formiate (HCOO
-nH
4 +)) in the aqueous solution, for example, under the effect of noble metal catalyst (palladium carbon catalyst), produce the method for hydrogen ion with the two keys of the C=C on hydrogenated hop acid.
Described hop acid comprises humulone, isohumulone, dihydro isohumulone and lupulone.
Described hop acid solution can be dissolved in the solution that buck forms for hop acid; Described alkali is sodium hydroxide or potassium hydroxide.
Described hop acid solution can be dissolved in the solution that organic solvent forms for hop acid, and described organic solvent can be methyl alcohol, ethanol, propyl alcohol, hexane, pentane, acetone and ether.
The mol ratio of hop acid and formate/formic acid is 1: 1～1: 20; Be preferably 1: 1～1: 10.
Described noble metal catalyst is the powdered carbon containing palladium, platinum or nickel, is preferably the powdered carbon containing palladium, and wherein bullion content is 0.1wt%～20wt%, is preferably 5wt%～10wt%; Catalyst weight is 1%～50% of hop acid weight, is preferably 1%～25%.
The temperature of described reaction is 20 ℃～100 ℃.Be preferably 40 ℃～60 ℃.When higher than room temperature, need heating.Type of heating can adopt any type of heating well known by persons skilled in the art.
The pressure of described reaction is 0.5～10 normal atmosphere, is preferably normal pressure.
The time of described reaction is 0.5～3 hour.
Described formate comprises sodium formiate, potassium formiate, calcium formiate and ammonium formiate.
The hydrogenated hop acid obtaining is tetrahydrochysene humulone, tetrahydro-iso-humulone, Hexahydroisohumulone and hexahydrolupulon.
Described acidifying is to adopt 1～98% sulfuric acid, and carries out at 40～90 ℃.If the temperature in when reaction not in the scope of said temperature, needs reaction system to heat or cooling before acidifying.
This method for hydrogenation is not defined for hydrogenated hop acid, organic compound and organic acid compound containing unsaturated double-bond applicable to other yet.
The invention provides a kind of method that humulone after separating and lupulone is prepared into respectively to tetrahydrochysene humulone, tetrahydro-iso-humulone, Hexahydroisohumulone and hexahydrolupulon from hop extract.
Present method can be carried out under the condition that there is no organic solvent, also can be at single-phase ethanolic soln, or carry out in two phase liquid (being the mixed solution of organic solvent and water).
Not necessarily, the method, before above-mentioned reaction, also comprises the steps:
(1) from hop extract, separate the step of humulone and lupulone; And/or
(2) humulone be isomerizated into for isohumulone and be reduced into the step of dihydro isohumulone;
Step (1) and (2) were all reported to some extent in disclosed patent before many, for example U.S. Patent number 4,590,296 (05/20/1986), U.S. Patent number 4,844,939 (07/04/1989), China Patent No. 941,001,490, U.S. Patent number 4,302,479 (11/24/1981), U.S. Patent number 4,666,731 (05/19/1987), U.S. Patent number 4,002,683, British Patent No. 1,158,697 (07/16/1969), U.S. Patent number 4,234,516 (11/18/1980), be all incorporated herein by reference at this.
Obtain and isolate two compounds with aforesaid method: the one, the hop acid after acidifying, another kind of is the hop acid being dissolved in alkali (sodium hydroxide or the potassium hydroxide) aqueous solution.No matter an important advantage of the present invention is the hop acid of which kind of method generation and can carries out the hydrogenation that does not need hydrogen of uniqueness of the present invention.
When use that aforesaid method obtains when through the hop acid of acidifying, add wherein after organic solvent dissolution, add appropriate formate (sodium formiate, potassium formiate, calcium formiate or ammonium formiate) the aqueous solution or formic acid and noble metal catalyst, stir, and react at the temperature of 20～100 ℃, having reacted after vulcanization acid filters, separate two-phase layer, after evaporation organic solvent layer, can obtain hydrogenated hop acid, described catalyzer is the powdered carbon containing precious metal, wherein precious metal is palladium, platinum and nickel, the content of precious metal is 0.1wt%～20wt%, noble metal catalyst usage quantity is the 1wt%～50wt% of hop acid.Described organic solvent can be methyl alcohol, ethanol, propyl alcohol, hexane, pentane, acetone and ether.
When use that aforesaid method obtains when being dissolved in hop acid in alkali aqueous solution, add wherein appropriate formate (sodium formiate, potassium formiate, calcium formiate or ammonium formiate) or formic acid, and catalyzer, stir, and at the temperature of 20～100 ℃, carry out hydrogenation, having reacted after vulcanization acid filters, separation can obtain the hop acid after hydrogenation, described catalyzer is the powdered carbon containing precious metal, wherein precious metal is palladium, platinum and nickel, the content of precious metal is 0.1wt%～20wt%, 1wt%～50wt% that noble metal catalyst usage quantity is hop acid.
The present invention also provides a kind of and has made containing the organic compound of unsaturated double-bond or the method for organic acid compound hydrogenation, and the method comprises:
Make described organic compound or organic acid compound, the formate aqueous solution or formic acid containing unsaturated double-bond, and noble metal catalyst mixes;
Said mixture is stirred and reacted, and;
Separation obtains described containing the organic compound of unsaturated double-bond or the hydrogenated products of organic acid compound.
Described organic compound or organic acid compound containing unsaturated double-bond comprises humulone, isohumulone, dihydro isohumulone, lupulone, vinylbenzene and linalool etc.
Embodiment
Following examples are only for method of the present invention is described, and do not limit the present invention.
HPLC analysis condition
A. chromatography column: anti-phase liquid phase C-18 permaphase ODS post (4.5 × 100mm);
B. standard substance: ICS-H1 or ICS-T2, ASBC (ASBC);
C. mobile phase ratio: A: B=43: 57 (V/V), wherein A liquid is methyl alcohol, B liquid component: Trisodium Citrate+700ml water+200ml methyl alcohol of the 0.1M of 100ml;
D. sample size: 5 μ l
E. column temperature: room temperature
F. detect wavelength: 254nm
Embodiment 1
To containing adding in 150 milliliters of hexane solutions of 6 grams of isohumulones the aqueous solution containing 6.8 grams of sodium formiates of 150 milliliters and 1.25 grams containing palladium powdered carbon (content of palladium is 5wt%), under normal pressure, be stirred and heated to 60 ℃, after 1 hour, hydrogenation completes, adding sulfuric acid filters, remove lower aqueous solution, evaporation of hexane solution obtain product, separate and detect with UV detector (wavelength 254nm) through HPLC, with standard model (ISC-T2, U.S. ASBC) compare, both retention time are consistent, therefore confirm as tetrahydro-iso-humulone.
Embodiment 2
To the aqueous solution and 1.25 grams of palladium powdered carbons (wherein the content of palladium is 5wt%) containing 6.8 grams of sodium formiates containing adding 150 milliliters in 150 milliliters of KOH aqueous solution of 6 grams of dihydro isohumulones, under normal pressure, be stirred and heated to 60 ℃, after 1 hour, hydrogenation completes, adding sulfuric acid filters, remove lower aqueous solution, obtain oily matter, separate and detect with UV detector through HPLC, with standard model (ICS-H1, U.S. ASBC) compare, both retention time are consistent, therefore confirm as Hexahydroisohumulone.
Embodiment 3
To containing adding 200 milliliters of ethanol, 8 grams of sodium formiates and 1.25 grams of palladium powdered carbons (wherein palladium content 10wt%) in the KOH aqueous solution (30% isohumulone) of 25 grams of isohumulones, under normal pressure, be heated with stirring to 40 ℃, after 1 hour, hydrogenation completes, adding sulfuric acid filters, after evaporating solvent, obtain oily matter, separate and detect with UV detector through HPLC, compare and confirm as tetrahydro-iso-humulone with standard model (ISC-T2, U.S. ASBC).
Embodiment 4
To containing adding 200 milliliters of ethanol, 8 grams of sodium formiates and 1.25 grams of palladium powdered carbons (wherein palladium content 10wt%) in the KOH aqueous solution (30% dihydro isohumulone) of 25 grams of dihydro isohumulones, under normal pressure, be heated with stirring to 40 ℃, after 1 hour, hydrogenation completes, adding sulfuric acid filters, after evaporating solvent, obtain oily matter, separate and detect with UV detector through HPLC, with standard model (ICS-H1, U.S. ASBC) compare, both retention time are consistent, therefore confirm as Hexahydroisohumulone.
Embodiment 5
In 100 milliliters of ethanol containing 6.2 grams of humulones and 7 grams of sodium formiates, add 1.25 grams of palladium powdered carbons (wherein palladium content 10wt%) under normal pressure, to be heated with stirring to 42 ℃, after 2 hours, hydrogenation completes, adding sulfuric acid filters, after ethanol evaporation, obtain oily matter, separate and detect with UV detector through HPLC, with standard model (ISC-T2, U.S. ASBC) to compare, both retention time are consistent, therefore confirm as tetrahydro-iso-humulone.
Embodiment 6
At 5.38 grams of (0.035mol, molecular weight is 154) linalool (linalool) dissolve in 45 milliliters of hexanes, and add 25 ml waters, after stirring, add sodium formiate and 1.0 grams of palladium powdered carbons (wherein palladium content 10%) of 8 grams (0.12mol), under normal pressure, be heated with stirring to 70 ℃, after 2 hours, react, remove by filter palladium powdered carbon, filtrate is poured in separatory funnel, remove lower aqueous solution, upper strata organic solution is removed hexane through distillation (170 ℃), obtain 5 grams of colourless liquids, confirm as Tetrahydrolinalool through GS/MS, molecular weight is 158 (m/z=43, 55, 69, 73, 83, 111, 129, 143), reaction mole yield is 90%.
Claims (5)
1. a method of preparing hydrogenated hop acid, is characterized in that, carries out hydrogenation under no hydrogen condition, and the method comprises the steps:
Make hop acid solution, the formate aqueous solution or formic acid, and noble metal catalyst mixes;
Said mixture is stirred and reacted, and
Acidifying, separation obtain hydrogenated hop acid,
Described formate is sodium formiate, potassium formiate or calcium formiate;
Described hop acid solution is that hop acid is dissolved in the solution that buck forms; Described alkali is sodium hydroxide or potassium hydroxide,
Described hop acid comprises humulone, isohumulone, dihydro isohumulone and lupulone,
Described hydrogenated hop acid is tetrahydrochysene humulone, tetrahydro-iso-humulone, Hexahydroisohumulone and hexahydrolupulon.
2. method according to claim 1, is characterized in that, the mol ratio of described hop acid and formate/formic acid is 1:1～1:20, and described noble metal catalyst weight is 1%～50% of hop acid weight.
3. method according to claim 1, is characterized in that, described noble metal catalyst is the powdered carbon containing palladium, platinum or nickel, and wherein bullion content is 0.1wt%～20wt%.
4. method according to claim 1, is characterized in that, the temperature of described reaction is 20 ℃～100 ℃; The pressure of described reaction is 0.5～10 normal atmosphere; The time of described reaction is 0.5～3 hour.
5. method according to claim 1, is characterized in that, before implementing described method, also comprises the steps:
(1) from hop extract, separate humulone and lupulone; And/or
(2) humulone isomery is turned to isohumulone; And/or be reduced into dihydro isohumulone.
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|---|---|---|---|
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|---|---|---|---|
| CN201010189195.0A CN102260146B (en) | 2010-05-26 | 2010-05-26 | Method for preparing hydrogenated hop acid |
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| CN102260146B true CN102260146B (en) | 2014-06-25 |
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| GB201402471D0 (en) * | 2014-02-12 | 2014-03-26 | Ifast Nv | Method for extraction and dissolution of hop acids in aqueous media |
| CN105732347B (en) * | 2014-12-11 | 2018-09-18 | 北京理博兆禾酒花有限公司 | The method of Solvent-free hydrogenation and hydrogenolysis alpha-acid derivative and the mixture of β acid |
| CN110951559A (en) * | 2019-12-31 | 2020-04-03 | 齐鲁工业大学 | Method for improving beer foam performance by adding tetrahydro or hexahydro isomeric hop extract |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1096509A (en) * | 1994-01-15 | 1994-12-21 | 沈阳佳源国际医疗科技有限公司 | The method for preparing tetrahydro-iso-humulone by hop extract |
| US5523489A (en) * | 1995-02-07 | 1996-06-04 | Miller Brewing Company | Preparation of tetrahydroisohumulones |
-
2010
- 2010-05-26 CN CN201010189195.0A patent/CN102260146B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1096509A (en) * | 1994-01-15 | 1994-12-21 | 沈阳佳源国际医疗科技有限公司 | The method for preparing tetrahydro-iso-humulone by hop extract |
| US5523489A (en) * | 1995-02-07 | 1996-06-04 | Miller Brewing Company | Preparation of tetrahydroisohumulones |
Non-Patent Citations (1)
| Title |
|---|
| Brindaban C. Ranu，et al..Regio- and Stereoselective Hydrogenation of Conjugated Carbonyl Compounds via Palladium Assisted Hydrogen Transfer by Ammonium Formate.《Tetrahedron Letters》.1994,第35卷(第46期),8649-8650. * |
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