JPS6015627B2 - Production method of α-tocopherol - Google Patents
Production method of α-tocopherolInfo
- Publication number
- JPS6015627B2 JPS6015627B2 JP747376A JP747376A JPS6015627B2 JP S6015627 B2 JPS6015627 B2 JP S6015627B2 JP 747376 A JP747376 A JP 747376A JP 747376 A JP747376 A JP 747376A JP S6015627 B2 JPS6015627 B2 JP S6015627B2
- Authority
- JP
- Japan
- Prior art keywords
- tocopherol
- yield
- purity
- solvent
- reaction
- 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.)
- Expired
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 description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229940087168 alpha tocopherol Drugs 0.000 title claims 3
- 229960000984 tocofersolan Drugs 0.000 title claims 3
- 239000002076 α-tocopherol Substances 0.000 title claims 3
- 235000004835 α-tocopherol Nutrition 0.000 title claims 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- KEVYVLWNCKMXJX-ZCNNSNEGSA-N Isophytol Natural products CC(C)CCC[C@H](C)CCC[C@@H](C)CCC[C@@](C)(O)C=C KEVYVLWNCKMXJX-ZCNNSNEGSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000011592 zinc chloride Substances 0.000 claims description 9
- 235000005074 zinc chloride Nutrition 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 239000001707 (E,7R,11R)-3,7,11,15-tetramethylhexadec-2-en-1-ol Substances 0.000 claims description 4
- BLUHKGOSFDHHGX-UHFFFAOYSA-N Phytol Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C=CO BLUHKGOSFDHHGX-UHFFFAOYSA-N 0.000 claims description 4
- HNZBNQYXWOLKBA-UHFFFAOYSA-N Tetrahydrofarnesol Natural products CC(C)CCCC(C)CCCC(C)=CCO HNZBNQYXWOLKBA-UHFFFAOYSA-N 0.000 claims description 4
- BOTWFXYSPFMFNR-OALUTQOASA-N all-rac-phytol Natural products CC(C)CCC[C@H](C)CCC[C@H](C)CCCC(C)=CCO BOTWFXYSPFMFNR-OALUTQOASA-N 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 4
- BOTWFXYSPFMFNR-PYDDKJGSSA-N phytol Chemical compound CC(C)CCC[C@@H](C)CCC[C@@H](C)CCC\C(C)=C\CO BOTWFXYSPFMFNR-PYDDKJGSSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 238000003763 carbonization Methods 0.000 claims 1
- 239000007809 chemical reaction catalyst Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229960001295 tocopherol Drugs 0.000 description 23
- 239000011732 tocopherol Substances 0.000 description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 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 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229930003799 tocopherol Natural products 0.000 description 7
- 235000010384 tocopherol Nutrition 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000000199 molecular distillation Methods 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ZAKOWWREFLAJOT-CEFNRUSXSA-N D-alpha-tocopherylacetate Chemical group CC(=O)OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C ZAKOWWREFLAJOT-CEFNRUSXSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- -1 and ligroin Natural products 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- ZAKOWWREFLAJOT-UHFFFAOYSA-N d-alpha-Tocopheryl acetate Natural products CC(=O)OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C ZAKOWWREFLAJOT-UHFFFAOYSA-N 0.000 description 2
- FOYKKGHVWRFIBD-UHFFFAOYSA-N gamma-tocopherol acetate Natural products CC(=O)OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 FOYKKGHVWRFIBD-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- AVGAIPMGSIOHFZ-UHFFFAOYSA-N dichloromethane;2-propan-2-yloxypropane Chemical compound ClCCl.CC(C)OC(C)C AVGAIPMGSIOHFZ-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 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 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001189 phytyl group Chemical group [H]C([*])([H])/C([H])=C(C([H])([H])[H])/C([H])([H])C([H])([H])C([H])([H])[C@@](C([H])([H])[H])([H])C([H])([H])C([H])([H])C([H])([H])[C@@](C([H])([H])[H])([H])C([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Pyrane Compounds (AREA)
Description
【発明の詳細な説明】
本発明は、Ｑ−トコフェロールの製造法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing Q-tocopherol.
さらに詳しくは、２・３・５ートリメチルー１・４ーハ
イドロキノンと、フイトール及び／又はィソフイトール
とを、塩化亜鉛を触媒として縮合せしめてＱートコフヱ
ロールを製造する方法に関するものである。従来、Ｑー
トコフェロールの製造法として、２・３・５−トリメチ
ルー１・４ーハイドロキノンとフイトール及び／又はィ
ソフィトールを縮合せしめるに際し、塩化亜鉛を結合剤
として使用し、リグロイン、テトラリン、ベンゼン、ト
ルェン、キシレンなどの脂肪族あるいは芳香族炭化水素
系溶媒中で加熱還流する方法が知られている。しかし、
これら従来方法では加熱還流と云う苛酷な反応条件が必
須であるため、往々にして副反応が生じ、フィチルダィ
マー等の高沸点化合物が創生する。これら高潔点化合物
は蒸留による精製操作では除去困難で、ガスクロマトグ
ラフ上あるいは薄層クロマトグラフ上これら高沸点化合
物の狭雑のない純度の高いＱ−トコフェロールを得るた
めには、縮合反応生成物の蒸留精製操作における蟹出範
囲を厳密にコントロールしなければならず、目的物Ｑ−
トコフェロール収率低下の大きい原因となっている。本
発明者等は、従来のＱートコフェロール製造法の上託せ
る欠点を解除して高純度のＱートコフェロールを収率よ
く製造すべく研究し、本発明の方法によって所期の目的
が蓮せられる事を確認した。More specifically, the present invention relates to a method for producing Q tocopherol by condensing 2,3,5-trimethyl-1,4-hydroquinone with phytol and/or isophytol using zinc chloride as a catalyst. Conventionally, as a method for producing Q tocopherol, zinc chloride is used as a binder when condensing 2,3,5-trimethyl-1,4-hydroquinone with phytol and/or isophytol, and ligroin, tetralin, benzene, toluene, A method of heating under reflux in an aliphatic or aromatic hydrocarbon solvent such as xylene is known. but,
Since these conventional methods require severe reaction conditions such as heating under reflux, side reactions often occur and high-boiling compounds such as phytyl dimer are created. These high-point compounds are difficult to remove by purification by distillation, and in order to obtain highly pure Q-tocopherol without the contamination of these high-boiling point compounds on gas chromatography or thin layer chromatography, it is necessary to distill the condensation reaction product. It is necessary to strictly control the extraction range during refining operations, and the target product Q-
This is a major cause of a decrease in tocopherol yield. The present inventors have conducted research to eliminate the drawbacks of conventional Q-tocopherol production methods and produce high-purity Q-tocopherol in good yield, and have achieved the intended purpose by the method of the present invention. I confirmed that it is possible.
本発明の方法は２・３・５−トリメチルー１・４ーハイ
ドロキノンとフイトール及び／又はイソフイトールとを
塩化亜鉛を触媒として縮合反応せしめてＱートコフェロ
ールを製造するに際して、反応溶媒として低級脂肪族ハ
ロゲン化炭化水素系溶媒と低級脂肪族エーテル系溶媒と
の混合溶媒を使用してはートコフェロールを製造する事
からなる。The method of the present invention involves the condensation reaction of 2,3,5-trimethyl-1,4-hydroquinone with phytol and/or isophytol using zinc chloride as a catalyst to produce Q tocopherol, in which lower aliphatic halogenation is used as a reaction solvent. Tocopherol is produced using a mixed solvent of a hydrocarbon solvent and a lower aliphatic ether solvent.
本発明の方法において使用される低級脂肪族ハロゲン化
炭化水素系溶媒としては、例えばジクロルメタン、クロ
ロホルム、四塩化炭素、エチレンジクロラィド等を挙げ
る事ができる。低級脂肪族エーテル系溶媒としては、例
えばジメチルェーテル、ジエチルエーテル、エチルメチ
ルエーナル、ジプロピルエーテル、ジイソプロピルエー
ナル、ジーｎーブチルェーテルを挙げる事ができる。上
記溶媒において、ジクロルメタンーイソブロピルェーテ
ル混合溶媒の使用が特に好ましい結果を与えた。本発明
の方法の利点は、縮合反応を行なうに際して加熱還流を
行なう必要のない事で、そのため従釆法の欠点である高
沸点化合物の創生が殆どなく、縮合生成物を常法に従っ
て分子蒸留した場合、純度９７％以上〔ナショナル ホ
ーミュラリー（ＮａｔｊｏＭＩＦｏ側ｕｌａｒｙ）第１
４登第７斑〜７６２頁記載のガスクロマト法によるビタ
ミンＥ定量法に従って測定した。Examples of the lower aliphatic halogenated hydrocarbon solvent used in the method of the present invention include dichloromethane, chloroform, carbon tetrachloride, and ethylene dichloride. Examples of lower aliphatic ether solvents include dimethyl ether, diethyl ether, ethyl methyl ether, dipropyl ether, diisopropyl ether, and di-n-butyl ether. Among the above solvents, the use of a dichloromethane-isopropylether mixed solvent gave particularly favorable results. The advantage of the method of the present invention is that there is no need to heat reflux when carrying out the condensation reaction, so there is almost no generation of high-boiling compounds, which is a drawback of the conventional method, and the condensation product is subjected to molecular distillation using a conventional method. If the purity is 97% or more [National Homulary (NatjoMIFo side ulary) 1st
It was measured according to the vitamin E quantitative method using the gas chromatography method described on page 762 of No. 4, No. 7.
以下同じ〕のＱートコフェロールが８８％以上の収率で
得られると云う高結果をもたらした。また従来法に比較
して高沸点化合物の狭雑が少ない事は、ガスクロマトグ
ラフ上あるいは薄層クロマトグラフ上にても確認された
。以上より本発明は、従来法に比してより高純度のＱー
トコフェロールを、より高収率で提供する事をその目的
とするものとする。The same results hereinafter] were obtained in a yield of 88% or more. It was also confirmed on a gas chromatograph or thin layer chromatograph that the concentration of high boiling point compounds was less than in the conventional method. From the above, it is an object of the present invention to provide Q tocopherol with higher purity and higher yield than conventional methods.
次に実施例および比較例により本発明を説明する。Next, the present invention will be explained with reference to Examples and Comparative Examples.
なお目的物Ｑートコフェロールの純度は前記したナショ
ナル ホーミュラリー第１４坂記載のガスクロマト法に
従って測定した。実施例 １
２・３・５−トリメチルー１・４−ハイドロキノン７．
８夕（０．０５モル）、無水塩化亜鉛６．８夕０．０５
モル）をジクロルメタン２０の‘、ジイソプロピルエー
テル５の‘の混合溶媒に加え、更に氷酢酸１叫を加えた
のち、室温にて櫨梓下にィソフィトール（純度９５％）
１５．６夕（０．０５モル）を３時間を要して滴下し、
滴下終了後、更に３０分間同一条件下で縄拝した。The purity of the target substance Q tocopherol was measured according to the gas chromatography method described in National Homulary No. 14, mentioned above. Example 1 2,3,5-trimethyl-1,4-hydroquinone7.
8 mol (0.05 mol), anhydrous zinc chloride 6.8 mol 0.05
After adding 1 mol of dichloromethane and 5 mol of diisopropyl ether to a mixed solvent of 1 mol of dichloromethane and 5 mol of diisopropyl ether, add isophytol (purity 95%) at room temperature.
15.6 moles (0.05 mol) was added dropwise over 3 hours,
After the dropping was completed, the rope was bowed under the same conditions for an additional 30 minutes.
反応終了後、溶媒を減圧留去して得られる赤褐色油状物
をｎ−へキサン１５０泌に溶解し、水、２％水酸化ナト
リウ水溶液、飽和食塩水にて順次洗修し、苦硝で乾燥し
たのち、溶媒を減圧蟹去した。赤燈色油状物質（粗Ｑー
トコフェロール）２２．１夕を得た。収率９９％（ィソ
フイトールを基として）純度 ９５％
この赤燈色油状物質を分子蒸留に附して無色油状物質（
精製Ｑートコフヱロール）１８．９夕を得た。After the reaction, the solvent was distilled off under reduced pressure, and the resulting reddish brown oil was dissolved in 150% n-hexane, washed successively with water, 2% aqueous sodium hydroxide, and saturated brine, and dried with bitter salt. Thereafter, the solvent was removed under reduced pressure. 22.1 hours of a red light oil (crude Q-tocopherol) was obtained. Yield 99% (based on isophytol) purity 95% This reddish oil is subjected to molecular distillation to produce a colorless oil (
Purified Q-tocopherol) 18.9 hours was obtained.
収率８８％純度 ９９％
実施例 ２
２・３・５ートリメチル−１・４ーハイドロキノン７．
８夕、イソフイトール１５６夕、糠水塩化亜鉛５．６夕
、氷酢酸１の‘をジクロルメタン２０泌、ジェチルェー
テル３の‘の浪合溶媒を使用し、実施例１に従って反応
処理した。Yield 88% Purity 99% Example 2 2,3,5-trimethyl-1,4-hydroquinone7.
After 8 days, reaction treatment was carried out according to Example 1 using a mixture of 156 times of isophytol, 5.6 times of bran water zinc chloride, 1 part of glacial acetic acid, 20 parts of dichloromethane, and 3 parts of diethyl ether.
粗Ｑ−トコフェロール：赤燈色油状物質
収量 ２１．９夕（収率９８％）
純度 ９３％
精製Ｑ−トコフェロール：無色油状物質
収量 １８１夕（収率滋％）
純度 ９８％
実施例 ３
２・３・５−トリメチルー１・４−ハイドロキノン７．
８夕、ィソフィトール１５．６夕、無水塩化亜鉛６．８
夕、氷酢酸１の‘をヱチレンジクロラィド２０泌、ジイ
ソプロピルェーテル５の‘の混合溶媒を使用し実施例１
に従って反応処理した。Crude Q-tocopherol: Reddish oily substance Yield: 21.9 hours (yield: 98%) Purity: 93% Purified Q-tocopherol: Colorless oily substance: Yield: 181 hours (yield: 98%) Purity: 98% Example 3 2-3・5-trimethyl-1,4-hydroquinone 7.
8 evenings, isophytol 15.6 evenings, anhydrous zinc chloride 6.8 evenings
In the evening, Example 1 was prepared using a mixed solvent of 1 part of glacial acetic acid, 20 parts of ethylene dichloride, and 5 parts of diisopropyl ether.
The reaction was carried out according to the following.
粗Ｑ−トコフェロール：赤燈色油状物質
収量 ２２．２夕（収率９９％）
純度 ９２％
精製Ｑートコフヱロール：無色油状物質
収量 １８．８夕（収率８４％）
純度 聡％
実施例 ４
２・３・５−トリメチル−１・４ーハイドロキノン７．
８２、ィソフィトール１５．６夕、無水塩化亜鉛５．６
夕、氷酢酸１泌を１・１・１ートリクロルェタン２０舷
、ジーｎーブチルェーテル３の‘の混合溶媒を使用し、
実施例１に従って反応処理した。Crude Q-tocopherol: Reddish oily substance Yield 22.2 hours (yield 99%) Purity 92% Purified Q-tocopherol: Colorless oily substance Yield 18.8 hours (yield 84%) Purity Satoshi% Example 4 2. 3,5-trimethyl-1,4-hydroquinone7.
82, isophytol 15.6%, anhydrous zinc chloride 5.6%
In the evening, using a mixed solvent of 1 part of glacial acetic acid, 20 parts of 1,1,1-trichloroethane, and 3 parts of di-butyl ether,
The reaction was carried out according to Example 1.
粗Ｑ−トコフェロール：赤燈色油状物質収量 ２１．８
夕（収率職％）
純度 ９４％
精製Ｑートコフェロール：無色油状物質
収量 １８．５夕（収率８６％）
純度 斑％
実施例 ５
２・３・５−トリメチルー１・４ーハイドロキノン１１
４夕（０．７モル）、イソフイトール２３４夕（０．７
５モル）、無水塩化亜鉛１０５夕、氷酢酸１５の‘を１
・１ージク０ルエタン３００のと、ジイソプロピルェー
テル７５叫の混合溶媒を使用し、実施例１に従って反応
処理した。Crude Q-tocopherol: Red light oil yield 21.8
Purity (yield %) Purity 94% Purified Q-tocopherol: colorless oil Yield 18.5 (yield 86%) Purity Spot % Example 5 2,3,5-trimethyl-1,4-hydroquinone 11
4 moles (0.7 mol), isophytol 234 moles (0.7 mol)
5 moles), 105 parts of anhydrous zinc chloride, 1 part of glacial acetic acid
- A reaction treatment was carried out according to Example 1 using a mixed solvent of 300 parts of 1-dichloroethane and 75 parts of diisopropyl ether.
粗ｑ−トコフェロール：赤燈色油状物質
収量 ３３２夕（収率９９．４％）
純度 ９４％
この粗Ｑートコフェロール３３２のこ無水酢酸１９３夕
、酢酸ナトリウム滋夕、亜鉛末２．４夕、トルェン２５
０心を加え２時間燈拝下に加熱還流し、反応終了後、反
応液を放冷、次いで氷水１〆中に注ぎ入れ、有機溶媒層
を分取し、水洗、芝硝にて乾燥したのち、溶媒を減圧留
去した。Crude q-tocopherol: reddish oily substance Yield: 332 ml (yield 99.4%) Purity: 94% This crude q-tocopherol: 332 ml, acetic anhydride: 193 ml, sodium acetate, zinc powder: 2.4 ml, toluene 25
Add zero core, heat under reflux for 2 hours under light, and after the reaction is complete, the reaction solution is left to cool, then poured into ice water. The organic solvent layer is separated, washed with water, and dried with Shiba Glass. , the solvent was distilled off under reduced pressure.
殆ど無色の油状物質はートコフェリル アセテート３６
４夕を得た。収率９９．５％これを分子蒸留して精製Ｑ
ートコフェリル アセテート３２０夕を得た。The almost colorless oily substance is tocopheryl acetate 36
I got 4 nights. Yield 99.5% This was purified by molecular distillation Q
Tocopheryl acetate 320mg was obtained.
本品の純度は聡２％であつた。比較例 １
実施例１においてジイソブロピルェーテルを使用しない
他は同様の操作を行ない、精製Ｑ−トコフェロールを得
た。The purity of this product was 2% Satoshi. Comparative Example 1 Purified Q-tocopherol was obtained by carrying out the same operation as in Example 1 except that diisopropylether was not used.
黄赤色油状物質 ２０．８夕（収率９３％）純度 ７８
％比較例 ２
実施例１においてジィソプロピルェーテル２５の‘だけ
を使用して、ジクロルメタンを使用しない他は同様の操
作を行ない、精製Ｑ−トコフヱロールを得た。Yellow-red oil 20.8 min (yield 93%) Purity 78
% Comparative Example 2 Purified Q-tocopherol was obtained by carrying out the same operation as in Example 1 except that only diisopropyl ether 25' was used and dichloromethane was not used.
黄色油状物質 ２０．２夕（収率９１％）純度 ６２％Yellow oil 20.2 hours (yield 91%) Purity 62%
Claims (1)
と、フイトール及び／又はイソフイトールとを、塩化亜
鉛を触媒として縮合反応せしめてα−トコフエロールを
製造するに際して、反応触媒として低級脂肪族ハロゲン
化炭化水素系溶媒と低級脂肪族エーテル系溶媒との混合
溶媒を使用する事を特徴とする、α−トコフエロールの
製造法。1 When producing α-tocopherol by condensation reaction of 2,3,5-trimethyl-1,4-hydroquinone and phytol and/or isophytol using zinc chloride as a catalyst, lower aliphatic halogenated carbonization is used as a reaction catalyst. A method for producing α-tocopherol, characterized by using a mixed solvent of a hydrogen solvent and a lower aliphatic ether solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP747376A JPS6015627B2 (en) | 1976-01-28 | 1976-01-28 | Production method of α-tocopherol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP747376A JPS6015627B2 (en) | 1976-01-28 | 1976-01-28 | Production method of α-tocopherol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5291865A JPS5291865A (en) | 1977-08-02 |
| JPS6015627B2 true JPS6015627B2 (en) | 1985-04-20 |
Family
ID=11666746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP747376A Expired JPS6015627B2 (en) | 1976-01-28 | 1976-01-28 | Production method of α-tocopherol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6015627B2 (en) |
-
1976
- 1976-01-28 JP JP747376A patent/JPS6015627B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5291865A (en) | 1977-08-02 |
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