CN100366596C - Process for producing 2-(l-menthoxy)ethanol compound - Google Patents

Process for producing 2-(l-menthoxy)ethanol compound Download PDF

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Publication number
CN100366596C
CN100366596C CNB2004800078636A CN200480007863A CN100366596C CN 100366596 C CN100366596 C CN 100366596C CN B2004800078636 A CNB2004800078636 A CN B2004800078636A CN 200480007863 A CN200480007863 A CN 200480007863A CN 100366596 C CN100366596 C CN 100366596C
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oxygen base
menthol
compound
peppermint oxygen
preparation
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CN1764622A (en
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足立谦一郎
石田贤哉
松田洋幸
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Takasago International Corp
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Takasago Perfumery Industry Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/02—Preparation of ethers from oxiranes
    • C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/18—Ethers having an ether-oxygen atom bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C43/196—Ethers having an ether-oxygen atom bound to a carbon atom of a ring other than a six-membered aromatic ring containing hydroxy or O-metal groups
    • 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
    • C07C2601/14—The ring being saturated

Abstract

A process by which a 2-(L-menthoxy)ethanol compound which can enable foods or beverages, cigarettes, cosmetics, etc. to give a refreshing cool feeling can be produced from inexpensive materials through a simple step at low cost. The process, which is for producing a 2-(L-menthoxy)ethanol compound represented by the general formula (1) (wherein R represents hydrogen, alkyl, or 1-hydroxyalkyl), comprises reacting L-menthol with a 1,2-epoxyalkane in the presence of a catalyst comprising a Lewis acid.

Description

The preparation method of 2-(L-peppermint oxygen base) alcohol compound
Technical field
The present invention relates to the preparation method of 2-(L-peppermint oxygen base) alcohol compound.More particularly, the invention provides a kind of by the simple process step, and at lower cost preparation have and can make diet product, tobacco, makeup etc. have the method for 2-(the L-peppermint oxygen base) alcohol compound of ice-cold effect and salubrious sensation.
Background technology
Known have a multiple material that can produce ice-cold sensation (creeping chill) or salubrious sensation (refrigerant sense) (below be generically and collectively referred to as " ice-cold salubrious sense ") at people's skin and mucous membrane, particularly oral cavity, nasal cavity, throat, eye.The example of representative substances is a peppermint main body of oil L-menthol, and it is widely used among chewing gum, toothpaste, the shampoo etc.Although the L-menthol has the ice-cold salubrious sensation of intensive, its effect can not continue for a long time, and usually owing to its intensive mint type fragrance has limited its purposes and consumption.
Therefore, based on the purpose of improving persistence and fragrance, continually developing compound with the ice-cold salubrious sense effect that is similar to the L-menthol always.As this compounds, the 3-replacement-right-menthane compounds that for example has that can enumerate (is consulted the spy and is opened clear 47-16647 communique; The spy opens clear 47-16449 communique; And English Patent GB 1,315,626 specification sheetss), N-replacement-right-menthane-3-Carbox amide (consult the spy and open clear 47-16648 communique), right-menthane glycols compound (consult the spy and open clear 47-16650 communique), 3-(L-peppermint oxygen base)-1, the 2-propylene glycol (is consulted the spy and is opened clear 61-48813 communique, and U.S. Pat P 4,459,425 specification sheets), (2S)-3-{ (1R, 2S, 5R)-[5-methyl-2-(1-methylethyl) cyclohexyl] oxygen base }-1,2-propylene glycol (consult the spy and open flat 7-82200 communique), (1 ' R, 2 ' S, 5 ' R)-3-L-peppermint oxygen base alkane-1-alcohol compound (consult the spy and open 2001-294546 communique specification sheets) etc.Because these compounds do not have the intensive mint smell as the L-menthol, and the ice-cold sustainable long time of salubrious sense effect, thereby are very useful.
In above-claimed cpd, the spy opens the (1 ' R that is put down in writing in the 2001-294546 communique, 2 ' S, 5 ' R) though-3-L-peppermint oxygen base alkane-1-alcohol compound has good ice-cold salubrious sense effect, up to now can't be with easy and inexpensive method preparation.Open the 2001-294546 communique according to the spy, this compound be by use lithium aluminium hydride also the method for the ether compound that obtains of reason L-menthol and Mono Chloro Acetic Acid prepare, formality is loaded down with trivial details and cost is high.
Summary of the invention
The object of the present invention is to provide and a kind ofly can use cheap raw material, by simple technology and can prepare at lower cost have good ice-cold dose and salubrious agent function, belong to (1 ' R, 2 ' S, 5 ' R)-2-(the L-peppermint oxygen base) ethanol of 3-L-peppermint oxygen base alkane-1-alcohol compound and the method for its similar compound.
The present inventor has carried out research repeatedly for achieving the above object.Found that: if use Lewis acid to make L-menthol and 1 as catalyzer, the reaction of 2-epoxy alkane, need cautious sodium hydride etc. in the time of then can need not to use expensive raw material, expensive catalysts and processing, more need not through complicated step, pass through single step reaction, extremely simply and at lower cost prepare described target compound 2-(L-peppermint oxygen base) alcohol compound, and finished the present invention based on this understanding.
That is, the present invention is: the preparation method of (1) 2-(L-peppermint oxygen base) alcohol compound is characterized in that: in the presence of the catalyzer that Lewis acid is formed, make the represented L-menthol of following general formula (I):
With following general formula (II) represented 1,2-epoxy alkane compounds reaction,
(in the formula, R represents hydrogen atom, alkyl or 1-hydroxyalkyl),
Prepare the represented 2-of following general formula (III) (L-peppermint oxygen base) alcohol compound:
Figure C20048000786300061
(in the formula, R represents group same as described above).
And the present invention also comprises:
(2) as above-mentioned (1) described preparation method, the wherein said catalyzer of being made up of Lewis acid is for being selected from one or two or more kinds the compound in aluminum chloride, zinc chloride, zinc bromide, iron(ic) chloride (III) and the boron trifluoride diethyl ether title complex; And
(3) as above-mentioned (1) or (2) described preparation method, the wherein said catalyzer of being made up of Lewis acid is a kind of in aluminum chloride and the zinc chloride or two kinds;
(4) as each described preparation method of above-mentioned (1)～(3), wherein said 1,2-epoxy alkane compounds is an oxyethane.
Preferred forms of the present invention
Below, the present invention will be described in detail.
As mentioned above, the present invention use cheap L-menthol and above-mentioned general formula (II) represented 1,2-epoxy alkane compounds (hereinafter referred to as " 1; 2-epoxy alkane compounds (II) ") is produced the represented 2-of above-mentioned general formula (III) (L-peppermint oxygen base) alcohol compound (hereinafter referred to as " 2-(L-peppermint oxygen base) alcohol compound (III) ") as starting compound by single step reaction.
L-menthol as starting compound is a known compound, and another starting compound 1,2-epoxy alkane compounds (II) can use commercially available product, also can use by ordinary method synthetic compound.
In above-mentioned general formula (II) and general formula (III), R represents hydrogen atom, alkyl or 1-hydroxyalkyl.
When R is alkyl, can be any one of straight chained alkyl or branched-chain alkyl, preferred carbonatoms be 1～5 straight or branched alkyl.Be the specific examples of 1～5 alkyl as preferred carbonatoms, that can enumerate has methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, a tert-pentyl etc.
In addition, when R is the 1-hydroxyalkyl, can be the 1-hydroxyalkyl of straight chain, perhaps also can be the 1-hydroxyalkyl of side chain.At this moment, the preferred carbonatoms of R is the 1-hydroxyalkyl of 1～5 straight or branched.The specific examples of preferred 1-hydroxyalkyl can be enumerated methylol, 1-hydroxyethyl, 1-hydroxyl n-propyl, 1-hydroxyl-1-methylethyl, 1-hydroxyl normal-butyl and 1-hydroxyl n-pentyl etc.
L-menthol and 1, the usage ratio of 2-epoxy alkane compounds (II) are the L-menthol with respect to 1mol, preferred 0.1～5.0mol, more preferably 1 of 0.5～2.5mol, 2-epoxy alkane compounds (II).When both usage ratio is outside above-mentioned scope, be difficult to successfully generate target compound 2-(L-peppermint oxygen base) alcohol compound (III).
Lewis acid as catalyzer can be any Lewis acid, wherein, because one or two or more kinds in (anhydrous) aluminum chloride, (anhydrous) zinc chloride, zinc bromide, iron(ic) chloride (III) and the boron trifluoride diethyl ether title complex can obtain target compound 2-(L-peppermint oxygen base) alcohol compound (III) with highly selective and high yield, so preferably use.Wherein, consider from the selectivity and the productive rate of target compound 2-(L-peppermint oxygen base) alcohol compound (III) of reaction, more preferably use separately (anhydrous) aluminum chloride and (anhydrous) zinc chloride any one or both are mixed use.
Lewis acidic usage quantity is starting compound (matrix) the L-menthol with respect to 1mol, preferred 0.01～3.0mol, more preferably 0.1～1.0mol.If the not enough above-mentioned 0.01mol of lewis acidic usage quantity, then be difficult to successfully generate target compound 2-(L-peppermint oxygen base) alcohol compound (III), on the other hand, promptly usage quantity can not improve productive rate and transformation efficiency above 1.0mol, is uneconomic therefore.
From reaction steadily carry out consider with aspect such as operability, preferably in organic solvent, carry out L-menthol and 1, the reaction of 2-epoxy alkane compounds (II).The kind of organic solvent there is no special qualification, and that can enumerate has for example varsols such as hexane, heptane, toluene; Halogenated hydrocarbon solvents such as methylene dichloride; Ether solvents such as tetrahydrofuran (THF), dioxane, diethyl ether, Di Iso Propyl Ether, methyl tertiary butyl ether, glycol dimethyl ether.The preferred varsols such as hexane, pentane, toluene that use are considered in aspects such as operability during wherein, from price and aftertreatment.
Usually at-50 ℃～100 ℃, preferably under-30 ℃～40 ℃ temperature, make L-menthol and 1,2-epoxy alkane compounds (II) reaction 0.5～15 hour, preferred 1.0～5.0 hours, can pass through single step reaction, extremely simple and highly selective obtains target compound 2-(L-peppermint oxygen base) alcohol compound (III).
Can adopt one or two or more kinds the method in the process for purification commonly used such as various chromatograms, distillation, recrystallization that 2-(the L-peppermint oxygen base) alcohol compound (III) that so obtains is made with extra care.
And the full text of Japanese patent application (special hope) 2003-111597 specification sheets described content is included among this specification sheets.
Embodiment
Below, by enumerating embodiment the present invention is carried out specific description, but the present invention is not limited to following example.
Embodiment 1: use Aluminum chloride anhydrous to prepare 2-(L-peppermint oxygen base) ethanol
(1) in the four-hole boiling flask of 1000ml, add 100.0g (641mmol) L-menthol and 42.7g (320mmol) Aluminum chloride anhydrous, behind nitrogen replacement, in ice-cooled, add 500ml toluene and begin stirring.The temperature of confirming reaction solution drops to after about 5 ℃, adds 57g oxyethane, and keeping the liquid temperature simultaneously is 5～10 ℃.Charging is at room temperature further stirred and was finished reaction in 1 hour after finishing.
(2) then, cool off reaction solution once more and remain on below 20 ℃, 10% hydrochloric acid with 150ml washs simultaneously.Then, wash with saturated sodium bicarbonate water of 50ml and 100ml saturated aqueous common salt successively, remove moisture content, under reduced pressure, reclaim solvent, obtain rough 2-(L-peppermint oxygen base) ethanol 123.1g with sodium sulfate.It is carried out Wei Geluo distillation (PVC グ ロ one steams and stays) (Vigoureux distillation), reclaim unreacted raw material and separation and purification target compound, obtain 2-(L-peppermint oxygen base) ethanol 60.8g (theoretical yield based on the L-menthol is 47.4%), and reclaim unreacted L-menthol 45.7g.
Comparative example 1: use sodium hydride to prepare 2-(L-peppermint oxygen base) ethanol
With respect to the L-menthol of 1mol, use the sodium hydride of 1.1mol, the liquid temperature during reaction is about 95 ℃, and the total overall reaction time is 1.0 hours, and other conditions the same with embodiment 1 makes L-menthol and reacting ethylene oxide, prepares 2-(L-peppermint oxygen base) ethanol.
The result of embodiment 1 and comparative example 1 is as shown in table 1 below, comprising transformation efficiency, 2-(L-peppermint oxygen base) alcoholic acid selectivity and 2-(the L-peppermint oxygen base) ethanol yield of L-menthol.
Table 1
Catalyzer (reaction reagent) Temperature of reaction (℃) Reaction times (hr) Transformation efficiency (%) Selectivity (%) Productive rate (%)
Kind Usage quantity 1)
Embodiment 1 Anhydrous AlCl 3 0.5mol 5～10 2.0 54.5 88.6 47.4
Comparative example 1 NaH 1.1mol 95 1.0 68.8 61.6 42.4
1) with respect to the usage quantity of 1molL-menthol
By the result of last table 1 as can be known, compare with the embodiment 1 that uses the lewis acid catalyst Aluminum chloride anhydrous, in the comparative example 1 that uses the basic catalyst sodium hydride, the necessary usage quantity of catalyzer is more, and target product 2-(L-peppermint oxygen base) alcoholic acid selectivity and productive rate are lower.
Embodiment 2: use various lewis acid catalysts to prepare 2-(L-peppermint oxygen base) ethanol
L-menthol with respect to 1mol, use 0.2mol lewis acid catalyst as shown in table 2 below respectively, adopt temperature of reaction and reaction times as shown in table 2, other conditions are the same with embodiment 1, make L-menthol and reacting ethylene oxide, preparation 2-(L-peppermint oxygen base) ethanol.Its result is as shown in table 2 below, and transformation efficiency, selectivity and productive rate have the implication identical with table 1.
Table 2
Experiment numbers Catalyzer (reaction reagent) Temperature of reaction (℃) Reaction times (hr) Transformation efficiency (%) Selectivity (%) Productive rate (%)
Kind Usage quantity 1)
1 Anhydrous AlCl 3 0.2mol 40 2.0 38.8 86.2 33.5
2 ZnCl 2 0.2mol 40 3.0 27.4 91.2 25.0
3 BF 3·OEt 2 0.2mol 40 2.0 49.7 48.7 24.2
1) with respect to the usage quantity of 1molL-menthol
By the result of last table 2 as can be known, under the situation of the catalyzer that uses Aluminum chloride anhydrous and zinc chloride to form as Lewis acid, can highly selective and high yield obtain target product 2-(L-peppermint oxygen base) ethanol.
Industrial applicibility
2-(L-peppermint oxygen base) alcohol compound (III) has good ice-cold effect and salubrious effect, but owing to be not suitable for the preparation method of practical application, not yet be widely used up to now, by method of the present invention, can use MENTHOL and 1, the cheap compound that this class of 2-epoxyalkane compounds (II) is commonly used is as raw material, by the technique of single step reaction, simply and at low cost prepare 2-(L-peppermint oxygen base) alcohol compound (III) with high productivity.
Join in the extensive stocks such as various diet product, cosmetics, tobacco by 2-(the L-peppermint oxygen base) alcohol compound with the present invention's preparation, enable to have gentle fragrance and lasting good coolness and salubrious sense, thereby can improve the value of these commodity.

Claims (4)

1.2-the preparation method of (L-peppermint oxygen base) alcohol compound is characterized in that: in the presence of the catalyzer that Lewis acid is formed, make the represented L-menthol of following general formula (I):
Figure C2004800078630002C1
With following general formula (II) represented 1,2-epoxy alkane compounds reaction,
In the formula, R represents hydrogen atom, alkyl or 1-hydroxyalkyl,
Prepare the represented 2-of following general formula (III) (L-peppermint oxygen base) alcohol compound:
Figure C2004800078630002C3
In the formula, R represents group same as described above.
2. preparation method as claimed in claim 1, the wherein said catalyzer of being made up of Lewis acid is for being selected from one or two or more kinds compound of aluminum chloride, zinc chloride, zinc bromide, iron(ic) chloride (III) and boron trifluoride diethyl ether title complex.
3. preparation method as claimed in claim 1 or 2, the wherein said catalyzer of being made up of Lewis acid is a kind of in aluminum chloride and the zinc chloride or two kinds.
4. as each described preparation method of claim 1～3, wherein said 1,2-epoxy alkane compounds is an oxyethane.
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JP5863019B2 (en) * 2011-10-27 2016-02-16 高砂香料工業株式会社 Method for producing 3-mentoxypropanol, and cooling agent composition
CN102964223A (en) * 2012-11-13 2013-03-13 宁波杭州湾新区珠峰企业管理服务有限公司 Preparation method of propylene glycol monomethyl ether
CN106146536B (en) * 2015-04-25 2019-07-26 山东新时代药业有限公司 A kind of preparation method of everolimus
CN104876944B (en) * 2015-05-13 2017-11-10 普济生物科技（台州）有限公司 A kind of preparation method of everolimus

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001294546A (en) * 2000-02-28 2001-10-23 Takasago Internatl Corp (1'r,2's,5'r)3-1-menthoxyalkan-1-ol cold-sensing agent
JP2002128720A (en) * 2000-10-23 2002-05-09 Takasago Internatl Corp Method for producing 3-1-menthoxypropane-1,2-diol
JP2002322111A (en) * 2001-04-23 2002-11-08 Takasago Internatl Corp Method for producing 3-1-menthoxypropane-1,2-diol

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001294546A (en) * 2000-02-28 2001-10-23 Takasago Internatl Corp (1'r,2's,5'r)3-1-menthoxyalkan-1-ol cold-sensing agent
JP2002128720A (en) * 2000-10-23 2002-05-09 Takasago Internatl Corp Method for producing 3-1-menthoxypropane-1,2-diol
JP2002322111A (en) * 2001-04-23 2002-11-08 Takasago Internatl Corp Method for producing 3-1-menthoxypropane-1,2-diol

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