JPS62209071A - Production of alpha-tocopherol - Google Patents
Production of alpha-tocopherolInfo
- Publication number
- JPS62209071A JPS62209071A JP5140786A JP5140786A JPS62209071A JP S62209071 A JPS62209071 A JP S62209071A JP 5140786 A JP5140786 A JP 5140786A JP 5140786 A JP5140786 A JP 5140786A JP S62209071 A JPS62209071 A JP S62209071A
- Authority
- JP
- Japan
- Prior art keywords
- tocopherol
- formaldehyde
- organic acid
- polymer
- present
- 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.)
- Pending
Links
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 title claims abstract description 76
- 235000004835 α-tocopherol Nutrition 0.000 title claims abstract description 38
- 229940087168 alpha tocopherol Drugs 0.000 title claims abstract description 33
- 229960000984 tocofersolan Drugs 0.000 title claims abstract description 33
- 239000002076 α-tocopherol Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011732 tocopherol Substances 0.000 claims abstract description 21
- 229930003799 tocopherol Natural products 0.000 claims abstract description 18
- GZIFEOYASATJEH-VHFRWLAGSA-N δ-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 GZIFEOYASATJEH-VHFRWLAGSA-N 0.000 claims abstract description 14
- GZIFEOYASATJEH-UHFFFAOYSA-N D-delta tocopherol Natural products OC1=CC(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 GZIFEOYASATJEH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000010389 delta-tocopherol Nutrition 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 239000002446 δ-tocopherol Substances 0.000 claims abstract description 7
- -1 organic acid ammonium salt Chemical class 0.000 claims abstract description 6
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 11
- 235000019149 tocopherols Nutrition 0.000 claims description 7
- QUEDXNHFTDJVIY-UHFFFAOYSA-N γ-tocopherol Chemical class OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-UHFFFAOYSA-N 0.000 claims description 7
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 abstract description 29
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 abstract description 16
- 229960001295 tocopherol Drugs 0.000 abstract description 14
- 235000010384 tocopherol Nutrition 0.000 abstract description 11
- WGVKWNUPNGFDFJ-DQCZWYHMSA-N β-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C WGVKWNUPNGFDFJ-DQCZWYHMSA-N 0.000 abstract description 11
- 239000000047 product Substances 0.000 abstract description 9
- 235000010382 gamma-tocopherol Nutrition 0.000 abstract description 7
- 239000002478 γ-tocopherol Substances 0.000 abstract description 7
- QUEDXNHFTDJVIY-DQCZWYHMSA-N γ-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-DQCZWYHMSA-N 0.000 abstract description 7
- 229930040373 Paraformaldehyde Natural products 0.000 abstract description 6
- 239000007795 chemical reaction product Substances 0.000 abstract description 6
- 229920002866 paraformaldehyde Polymers 0.000 abstract description 6
- 235000007680 β-tocopherol Nutrition 0.000 abstract description 6
- 239000011590 β-tocopherol Substances 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium on carbon Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 3
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- KWIPUXXIFQQMKN-UHFFFAOYSA-N 2-azaniumyl-3-(4-cyanophenyl)propanoate Chemical compound OC(=O)C(N)CC1=CC=C(C#N)C=C1 KWIPUXXIFQQMKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229940090948 ammonium benzoate Drugs 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 2
- 239000011343 solid material Substances 0.000 abstract 1
- WGVKWNUPNGFDFJ-UHFFFAOYSA-N β-tocopherol group Chemical group CC1(OC2=C(C=C(C(=C2CC1)C)O)C)CCCC(CCCC(CCCC(C)C)C)C WGVKWNUPNGFDFJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 229930003427 Vitamin E Natural products 0.000 description 9
- 229940046009 vitamin E Drugs 0.000 description 9
- 235000019165 vitamin E Nutrition 0.000 description 9
- 239000011709 vitamin E Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000004071 biological effect Effects 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 5
- 239000005695 Ammonium acetate Substances 0.000 description 5
- 235000019257 ammonium acetate Nutrition 0.000 description 5
- 229940043376 ammonium acetate Drugs 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 150000003772 α-tocopherols Chemical class 0.000 description 5
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229940066595 beta tocopherol Drugs 0.000 description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- VZWXIQHBIQLMPN-UHFFFAOYSA-N chromane Chemical class C1=CC=C2CCCOC2=C1 VZWXIQHBIQLMPN-UHFFFAOYSA-N 0.000 description 2
- 239000000039 congener Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000007265 chloromethylation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003611 tocopherol derivatives Chemical class 0.000 description 1
- ZJVTYKZWDWVIFD-UHFFFAOYSA-N zinc;hydrochloride Chemical compound Cl.[Zn] ZJVTYKZWDWVIFD-UHFFFAOYSA-N 0.000 description 1
- 125000001020 α-tocopherol group Chemical group 0.000 description 1
Landscapes
- Pyrane Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明はα−トコフェロールの新規な製造方法に関する
ものである。さらに詳しくいえば、β−１γ−１及びδ
−のトコフェロールの少なくとも１′ｍを含有するトコ
フェロール類を原料とし、高度のビタミンＥ生物活性を
育するα−トコフェロールを収率よく製造する方法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel method for producing α-tocopherol. More specifically, β-1γ-1 and δ
The present invention relates to a method for producing α-tocopherol with high yield, which exhibits a high degree of vitamin E biological activity, using tocopherols containing at least 1'm of tocopherol as a raw material.
従来の技術
天然にはα−１β−１ｒ−及びδ−などのトコフェロー
ル同族体が存在することは知られており、これらはいず
れも、一般式
で示される構造の２−メチル−（４’、 ８’、 １２
’ −トリメチル−トリデシル）−６−クロマノールを
基本骨格とするものである。BACKGROUND ART It is known that tocopherol analogues such as α-1β-1r- and δ- exist in nature, and all of these are 2-methyl-(4', 8', 12
The basic skeleton is '-trimethyl-tridecyl)-6-chromanol.
前記一般式（１）におけるＲ１、Ｒ２及びＲ３はそれぞ
れ水素原子又はメチル基であり、各トコフェロールは次
に示すようなＲ１，Ｒ２及びＲ３を有している。R1, R2 and R3 in the general formula (1) are each a hydrogen atom or a methyl group, and each tocopherol has R1, R2 and R3 as shown below.
これから分かるように、α−トコフェロールは５．７．
８−トリメチルドコールであり、β−１γ−１δ−など
の非α−トコフェロール類はα一体のメチル基の１個又
は２個が水素原子に置換されている化合物である。As you can see, α-tocopherol is 5.7.
Non-α-tocopherols such as 8-trimethyldochol and β-1γ-1δ- are compounds in which one or two of the methyl groups of the α-unit are substituted with hydrogen atoms.
これらのトコフェロール類は特に植物油中に豊富に含有
されており、２ないし３種の同族体が混在している場合
が多い。トコフェロール同族体のビタミンＥ生物活性は
同族体間で著しく異なっておす、α−トコフェロールが
最も高いビタミンＥ活性を有することが知られている。These tocopherols are particularly abundantly contained in vegetable oils, and two or three types of homologs are often mixed together. It is known that the vitamin E bioactivity of tocopherol congeners varies significantly between congeners, with alpha-tocopherol having the highest vitamin E activity.
ところが、植物油中に含有されるトコフェロール類の中
では、α−トコフェロールの含’；ｉ率が一般に低く１
例えば大豆油トコフェロール中のトコフェロールＰＩ
ｉ 体の含有率は、α−トコフェロール１０％１ γ−
トコフェロール６０チ、δ−トコフェロール３０％であ
る。However, among the tocopherols contained in vegetable oils, the content of α-tocopherol is generally low.
For example, tocopherol PI in soybean oil tocopherol
The content of i form is α-tocopherol 10%1 γ-
It contains 60% tocopherol and 30% δ-tocopherol.
したがって、天然に豊富に存在するこれら非α−トコフ
ェロール類のタロマン核ニメチル基ヲ１個ないし２個導
入することによシ、ビタミンＥ活性の高いα−トコフェ
ロールを得ることは極めて有意義なことである。Therefore, it is extremely meaningful to obtain α-tocopherol with high vitamin E activity by introducing one or two talomanic nuclear dimethyl groups of these naturally abundant non-α-tocopherols. .
従来、ビタミンＥ生物活性の低い非α−トコフェロール
類ヲα−トコフェロールに転換する方法としては１次に
示す３ａｌの方法が知られている。Conventionally, as a method for converting non-α-tocopherols with low vitamin E biological activity into α-tocopherol, the 3al method shown below is known.
まず第１の方法は、触媒の存在下に、非α−トコフェロ
ールのクロマン核にヒドロキシメチル基を導入したのち
、これを還元してメチル基に転換する方法であυ、例え
ばホウ酸の存在下にホルムアルデヒドを反応させ、得ら
れた生成物を亜鉛−塩酸によシ還元してα−トコフェロ
ールを得る方法（特公昭４２−６３４９号公報）、ある
いはリン酸の存在下にホルムアルデヒドを高温高圧下で
反応させてα−トコフェロールを得る方法（特公昭５８
−１７１９２号公報）などが提案されている。The first method is to introduce a hydroxymethyl group into the chroman nucleus of non-α-tocopherol in the presence of a catalyst, and then convert it into a methyl group by reducing it. For example, in the presence of boric acid. A method of reacting formaldehyde with formaldehyde and reducing the resulting product with zinc-hydrochloric acid to obtain α-tocopherol (Japanese Patent Publication No. 42-6349), or a method of reacting formaldehyde in the presence of phosphoric acid at high temperature and high pressure. Method for obtaining α-tocopherol by reaction (Special Publication No. 1983)
-17192), etc. have been proposed.
しかしながら、前者の方法においては、製品の純度及び
収率は満足しうるものではなく、その上還元に亜鉛を用
いているので、廃水処理にも問題があり、また、後者の
方法においては、同様に廃水処理に問題があるとともに
、高温高圧反応のため、装置上の制約が免れないという
問題もある。However, in the former method, the purity and yield of the product are not satisfactory, and since zinc is used for reduction, there are problems in wastewater treatment, and in the latter method, the same In addition to problems with wastewater treatment, there is also the problem of equipment limitations due to high temperature and high pressure reactions.
第２の方法は、非α−トコフェロールのクロマン核にク
ロロメチル基を導入したのち、還元する方法で２例えば
クロロメチル化に塩化水素ガスを、還元に亜鉛を用いる
方法が提案されている（特開昭５６−６８６７８号公報
）。しかしながら、この方法においても装置及び廃水処
理の問題は避けられない。The second method involves introducing a chloromethyl group into the chroman nucleus of non-α-tocopherol and then reducing it.2 For example, a method has been proposed in which hydrogen chloride gas is used for chloromethylation and zinc is used for reduction (especially Publication No. 56-68678). However, even with this method, problems with equipment and wastewater treatment are unavoidable.
第３の方法は酢酸溶媒中で、ヘキサメチレンテトラミン
を反応させてホルミル化し、次いでホルミル基を接触還
元してメチル基に転換する方法である。しかしながら、
この方法においては１通常溶媒及び酸触媒として大量の
酢酸を使用しなければならず、かつα−トコフェロール
への転化率及び収率が極めて低いという問題がある。The third method is to react hexamethylenetetramine in an acetic acid solvent to formylate it, and then convert the formyl group into a methyl group by catalytic reduction. however,
In this method, a large amount of acetic acid must be used as a solvent and an acid catalyst, and the conversion rate and yield to α-tocopherol are extremely low.
この改良法として、少量の有機酸存在下にヘキサメチレ
ンテトラミンと反応させ、次いで接触還元する方法が提
案されている（特開昭５３−１１０６９号公報）。しか
しながら、この方法においては、従来の方法に比べて酸
の使用量は少ないものの、α−トコフェロールへの転化
率や選択率に関しては必ずしも満足しうるものではない
。As an improved method of this, a method has been proposed in which reaction is performed with hexamethylenetetramine in the presence of a small amount of organic acid, followed by catalytic reduction (Japanese Patent Laid-Open No. 11069/1983). However, in this method, although the amount of acid used is smaller than in conventional methods, the conversion rate and selectivity to α-tocopherol are not necessarily satisfactory.
発明が解決しようとする問題点
本発明の目的は、このような従来の方法が肩する問題を
解決し、ビタミンＥ生物活性の低い非α−トコフェロー
ル類に１個ないし２個のメチル基を導入して、該非α−
トコフェロール類を高度なビタミンＥ生物活性ヲ有する
α−トコフェロールに高収率で転換する新規な方法を提
供することにある。Problems to be Solved by the Invention The purpose of the present invention is to solve the problems faced by the conventional methods, and to introduce one or two methyl groups into non-α-tocopherols with low biological activity of vitamin E. Then, the non-α-
The object of the present invention is to provide a new method for converting tocopherols into α-tocopherol, which has a high degree of vitamin E biological activity, in high yield.
問題点を解決するための手段
本発明者らは、前記目的全達成するために鋭意検討を重
ねた結果、有機酸アンモニウム塩の存在下に、 非α−
トコフェロール類とホルムアルデヒド又はその重合体と
を反応させ、得られた反応生成物を接触還元することに
よシ、その目的を達成しうろことを見出し、この知見に
基づいて本発明を完成するに至った。Means for Solving the Problems In order to achieve all of the above objects, the inventors of the present invention have made extensive studies to achieve all of the above objectives.
The inventors discovered that the object could be achieved by reacting tocopherols with formaldehyde or a polymer thereof and catalytically reducing the resulting reaction product, and based on this knowledge, they completed the present invention. Ta.
すなわち、本発明は、有機酸アンモニウム塩の存在下ニ
おいて、β−１γ−及びδ−トコフェロールの少なくと
も１種を含有するトコフェロール類をホルムアルデヒド
又はその重合体と反応させ、次いで接触還元することを
特徴とするα−トコフェロールの製造方法を提供するも
のである。That is, the present invention involves reacting tocopherols containing at least one of β-1γ- and δ-tocopherol with formaldehyde or a polymer thereof in the presence of an organic acid ammonium salt, and then catalytic reduction. The present invention provides a method for producing α-tocopherol.
本発明方法において１例えば酢酸アンモニウム存在下に
、ｒ−トコフェロールとバラホルムアルデヒドとを反応
させて得られる生成物は、５−ヒドロキシメチル−７，
８−ジメチルトコール及び５−アミノメチル−７，８−
ジメテルトコールであシ。In the method of the present invention, for example, the product obtained by reacting r-tocopherol and paraformaldehyde in the presence of ammonium acetate is 5-hydroxymethyl-7,
8-dimethyltocol and 5-aminomethyl-7,8-
Dimetertocol.
これらのヒドロキシメチル基及びアミノメチル基は接触
還元により容易にメチル基に転換され、５゜７．８−ト
リメチルドコールすなわちα−トコフェロールとなる。These hydroxymethyl groups and aminomethyl groups are easily converted into methyl groups by catalytic reduction, resulting in 5°7.8-trimethyldocol, ie, α-tocopherol.
本発明方法によれば、β−及びγ−トコフェロールは１
回の操作で容易にメチル化されα−トコフェロールとな
る。−万δ−トコフエロールハ１回の操作でほとんど定
量的にβ−トコフェロールとなるので、同一操作を繰り
返すことによりα−トコフェロールとすることができる
。According to the method of the present invention, β- and γ-tocopherol are
It is easily methylated to α-tocopherol in one step. Since -10,000 δ-tocopherol can be converted into β-tocopherol almost quantitatively in one operation, it can be converted into α-tocopherol by repeating the same operation.
本発明方法において用いられる原料の非α−トコフェロ
ール類は、いずれの同族体単独又は混合物でよく、また
、純度の如何にかかわらず使用できる。天然においては
、非α−トコフェロール類はα−トコフェロールと共存
する場合が多いが、本発明においてはα−トコフェロー
ルの共存はなんら反応の妨げにはならない。したがって
、植物油から得られる粗製混合物の状態であっても、出
発原料として使用可能である。The raw material non-α-tocopherols used in the method of the present invention may be any homologue alone or a mixture thereof, and may be used regardless of its purity. In nature, non-α-tocopherols often coexist with α-tocopherol, but in the present invention, the coexistence of α-tocopherol does not hinder the reaction in any way. Therefore, even in the form of a crude mixture obtained from vegetable oils, it can be used as a starting material.
本発明方法において用いる有機酸アンモニウム塩として
は、ギ酸アンモニウム、酢酸アンモニウム、安息香酸ア
ンモニウムなどが挙げられる。これらのＭ機酸アンモニ
ウムは、原料の非α−トコフェロール１モルに対し％
１〜２モルの範囲で用いるのが好ましい。Examples of the organic acid ammonium salt used in the method of the present invention include ammonium formate, ammonium acetate, ammonium benzoate, and the like. These M organic acid ammonium are
It is preferable to use it in a range of 1 to 2 moles.
一万、ホルムアルデヒド又はその重合体としては、特に
バラホルムアルデヒドが好適であシ、その使用量は、該
非α−トコフェロール１モルに対し、好ましくは２〜１
０モルの範囲で選ばれる。As the formaldehyde or its polymer, paraformaldehyde is particularly suitable, and the amount used is preferably 2 to 1 mol per mol of the non-α-tocopherol.
It is selected within the range of 0 mol.
本発明方法においては、該非α−トコフェロール類とホ
ルムアルデヒド又はその重合体との反応は溶媒中で行う
のが好ましい。この溶媒としては例ｔｉｌトルエン、ベ
ンゼン、シクロヘキサンなどの炭化水素類、イソプロピ
ルエーテルやブチルエーテルなどのエーテル類を用いる
ことができる。In the method of the present invention, the reaction between the non-α-tocopherol and formaldehyde or its polymer is preferably carried out in a solvent. As this solvent, for example, hydrocarbons such as toluene, benzene, and cyclohexane, and ethers such as isopropyl ether and butyl ether can be used.
また、この反応は１通常８０〜１３０℃の範囲の温度に
おいて行われる。Further, this reaction is usually carried out at a temperature in the range of 80 to 130°C.
本発明方法においては、前記の反応により得られた生成
物をさらに接触還元するが、この接触還元操作は、該反
応生成物中の固形物を除去したものについて施すことが
好ましく、初気圧としては１０〜２０に９／ｄ程度の低
圧で十分であり、また。In the method of the present invention, the product obtained by the above reaction is further catalytically reduced, but this catalytic reduction operation is preferably performed on the reaction product from which solids have been removed, and the initial pressure is A low pressure of about 10 to 20 to 9/d is sufficient.
触媒としては、ニッケル系、パラジウム系、白金系など
の通常の接触還元に慣用されている触媒を用いることが
できるが、これらの中でパラジウム−炭素触媒が好適で
ある。反応温度は通常９０〜１３０℃の範囲で選ばれ、
反応時間は２〜４時間程度で十分である。また、この接
触還元は１通常溶媒中で行われるので、前記の固形物除
去後の溶媒を含む反応生成物をそのまま接触還元しても
よいし、また、必要に応じ該反応生成物中の溶媒を留去
後、これに別の溶媒を加えて接触還元してもよい。As the catalyst, nickel-based, palladium-based, platinum-based catalysts that are commonly used in normal catalytic reduction can be used, and among these, a palladium-carbon catalyst is preferred. The reaction temperature is usually selected in the range of 90 to 130°C,
A reaction time of about 2 to 4 hours is sufficient. In addition, since this catalytic reduction is usually carried out in a solvent, the reaction product containing the solvent after solid matter removal may be catalytically reduced as it is, or if necessary, the solvent in the reaction product may be After distilling off, another solvent may be added to carry out catalytic reduction.
発明の効果
本発明方法は、Ｔ４機酸アンモニウム塩の存在下ニ非α
−トコフヱロールとバラホルムアルデヒドなどとを反応
させ、得られた生成物を接触還元してα−トコフェロー
ルを製造する方法であって。Effects of the Invention The method of the present invention provides a method for treating non-α in the presence of T4 organic acid ammonium salt.
- A method for producing α-tocopherol by reacting tocopherol with paraformaldehyde or the like and subjecting the obtained product to catalytic reduction.
この方法によると温和な反応条件でビタミンＥ生物活性
の低い非α−トコフェロールから収率よく高度なビタミ
ンＥ生物活性全Ｍするα−トコフェロールを得ることが
できる。According to this method, it is possible to obtain α-tocopherol having a high total M vitamin E biological activity in good yield from a non-α-tocopherol having a low vitamin E biological activity under mild reaction conditions.
実施例 次に実施例により本発明全さらに詳細に説明する。Example Next, the present invention will be explained in more detail with reference to Examples.
実施例１
γ−トコフェロール（γ−トコフェロール９０．２チ、
β−トコフェロール２．８％、ｉトコフェロール９３％
）１０２をトルエン１００ｍＡに溶解し、これにパラホ
ルムアルデヒド３．（１，酢酸アンモニウム１．０１を
添加し、３時間還流下にかきまぜたのち、反応液をろ過
して固形物を除き、減圧下にトルエンを留去する。得ら
れた生成物’１ｌＯＯｄのエタノールに溶解し、これに
１０％パラジウム−炭素０．５２を添加して、オートク
レーブ中で水素初圧２０Ｋｐ／ｄとし、１１０〜１２０
℃で２時間接触還元する。次いで反応液よりパラジウム
−炭素をろ別し、ろ液を減圧下に濃縮して黄色油１０．
１Ｆを得た。このものを高速液体クロマトグラフィーに
より分析した結果、α−トコフェロールのＭｌｔは８８
％であり、収率は９２．５％であった。Example 1 γ-tocopherol (γ-tocopherol 90.2%,
β-tocopherol 2.8%, i-tocopherol 93%
) 102 was dissolved in 100 mA of toluene, and paraformaldehyde 3. (1. After adding 1.01 g of ammonium acetate and stirring under reflux for 3 hours, the reaction solution is filtered to remove solids, and toluene is distilled off under reduced pressure. The resulting product is 1 lOOd of ethanol. 10% palladium-carbon 0.52 was added thereto, the initial pressure of hydrogen was adjusted to 20 Kp/d in an autoclave, and the pressure was increased to 110-120 Kp/d.
Catalytic reduction for 2 hours at °C. Next, palladium-carbon was filtered off from the reaction solution, and the filtrate was concentrated under reduced pressure to give a yellow oil of 10.
Obtained 1F. As a result of analyzing this product by high performance liquid chromatography, the Mlt of α-tocopherol was 88.
%, and the yield was 92.5%.
実施例２
酢酸アンモニウムの代りにギ酸アンモニウム１．２２を
用い、他は実施例１と同様に処理して、α−トコフェロ
ール７８．６％１ γ−トコフェロール４．５％の黄色
油１０．１９を得た。Example 2 Using 1.22% ammonium formate instead of ammonium acetate, and otherwise treating in the same manner as in Example 1, a yellow oil containing 78.6% α-tocopherol and 4.5% γ-tocopherol 10.19% was obtained. Obtained.
実施例３
大豆油粗トコフェロール（α−トコフェロール６．１％
１β−トコフェロール１．１％、γ−トコフェロール３
７．７％、δ−トコフェロール１６．３％。Example 3 Soybean oil crude tocopherol (α-tocopherol 6.1%
1β-tocopherol 1.1%, γ-tocopherol 3
7.7%, δ-tocopherol 16.3%.
その他３８．８％）２０７をトルエン１００−に溶解し
、これにパラホルムアルデヒドａ、ｓｒ、酢酸アンモニ
ウム１．２２を添加して３時間、還流下にかきまぜたの
ち１反応液を濾過して固形物を除去し、減圧下にトルエ
ンを留去する。得られた生成物は実施例１と同様に還元
して、黄色油１９．８ ｆ （α−トコフェロール４３
．６％、β−トコフェロール１６．０％、その他４１．
４％）を得た。この黄色油に同一の操作を繰り返してα
−トコフェロール５８．０％、その他４１．４％の黄色
油１９．７９を得た。Other 38.8%) 207 was dissolved in toluene 100-, paraformaldehyde a, sr, and ammonium acetate 1.22 were added thereto, and the mixture was stirred under reflux for 3 hours.The reaction solution was filtered to obtain a solid. is removed and toluene is distilled off under reduced pressure. The obtained product was reduced in the same manner as in Example 1 to give a yellow oil of 19.8 f (α-tocopherol 43
．． 6%, β-tocopherol 16.0%, others 41.
4%). Repeat the same operation on this yellow oil and α
- A yellow oil of 19.79% was obtained, containing 58.0% of tocopherol and 41.4% of others.
Claims (1)
−及びδ−トコフェロールの少なくとも１種を含有する
トコフェロール類をホルムアルデヒド又はその重合体と
反応させ、次いで接触還元することを特徴とするα−ト
コフェロールの製造方法。1 In the presence of organic acid ammonium salt, β-, γ
A method for producing α-tocopherol, which comprises reacting tocopherols containing at least one of - and δ-tocopherol with formaldehyde or a polymer thereof, followed by catalytic reduction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5140786A JPS62209071A (en) | 1986-03-11 | 1986-03-11 | Production of alpha-tocopherol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5140786A JPS62209071A (en) | 1986-03-11 | 1986-03-11 | Production of alpha-tocopherol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62209071A true JPS62209071A (en) | 1987-09-14 |
Family
ID=12886081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5140786A Pending JPS62209071A (en) | 1986-03-11 | 1986-03-11 | Production of alpha-tocopherol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62209071A (en) |
-
1986
- 1986-03-11 JP JP5140786A patent/JPS62209071A/en active Pending
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