JPS6219546A - Purification of n-borneol - Google Patents
Purification of n-borneolInfo
- Publication number
- JPS6219546A JPS6219546A JP60156021A JP15602185A JPS6219546A JP S6219546 A JPS6219546 A JP S6219546A JP 60156021 A JP60156021 A JP 60156021A JP 15602185 A JP15602185 A JP 15602185A JP S6219546 A JPS6219546 A JP S6219546A
- Authority
- JP
- Japan
- Prior art keywords
- borneol
- isoborneol
- reaction
- solid acid
- crude
- 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.)
- Granted
Links
- 229940116229 borneol Drugs 0.000 title claims abstract description 94
- 238000000746 purification Methods 0.000 title description 3
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 claims abstract description 69
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 claims abstract description 69
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims abstract description 68
- CRPUJAZIXJMDBK-UHFFFAOYSA-N camphene Chemical compound C1CC2C(=C)C(C)(C)C1C2 CRPUJAZIXJMDBK-UHFFFAOYSA-N 0.000 claims abstract description 40
- DTGKSKDOIYIVQL-MRTMQBJTSA-N Isoborneol Natural products C1C[C@@]2(C)[C@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-MRTMQBJTSA-N 0.000 claims abstract description 35
- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 239000011973 solid acid Substances 0.000 claims abstract description 30
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 22
- PXRCIOIWVGAZEP-UHFFFAOYSA-N Primaeres Camphenhydrat Natural products C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 claims abstract description 20
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229930006739 camphene Natural products 0.000 claims abstract description 20
- ZYPYEBYNXWUCEA-UHFFFAOYSA-N camphenilone Natural products C1CC2C(=O)C(C)(C)C1C2 ZYPYEBYNXWUCEA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000004821 distillation Methods 0.000 claims abstract description 11
- 238000009835 boiling Methods 0.000 claims abstract description 9
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 14
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 claims 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 abstract description 12
- 230000018044 dehydration Effects 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 27
- 239000007795 chemical reaction product Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 238000000926 separation method Methods 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- -1 phthalate ester Chemical class 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 4
- 239000004927 clay Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000723346 Cinnamomum camphora Species 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229930008380 camphor Natural products 0.000 description 2
- 229960000846 camphor Drugs 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- CFJYNSNXFXLKNS-UHFFFAOYSA-N p-menthane Chemical compound CC(C)C1CCC(C)CC1 CFJYNSNXFXLKNS-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000341 volatile oil Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000123611 Dipterocarpaceae Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000218641 Pinaceae Species 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 235000017339 Pinus palustris Nutrition 0.000 description 1
- 241000204936 Pinus palustris Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- QUSSPXNPULRXKG-UHFFFAOYSA-N galleon Natural products O1C(=CC=2)C(OC)=CC=2CCCCC(=O)CCC2=CC=C(O)C1=C2 QUSSPXNPULRXKG-UHFFFAOYSA-N 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000171 lavandula angustifolia l. flower oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229930004008 p-menthane Natural products 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010668 rosemary oil Substances 0.000 description 1
- 229940058206 rosemary oil Drugs 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はｎ−ボルネオールの精製法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for purifying n-borneol.
更に詳しくは、不純物としてイソボルネオールを含有す
る粗ボルネオールを不活性媒体中に溶解し、固体酸化合
物の存在下、液相にてイソボルネオールを脱水してカン
フエンとなし、これを分離することによって高純度のｎ
−ボルネオールを得るｎ−ボルネオールの精製法に関す
る。More specifically, crude borneol containing isoborneol as an impurity is dissolved in an inert medium, the isoborneol is dehydrated to camphene in the liquid phase in the presence of a solid acid compound, and this is separated to form high-density borneol. Purity n
-Regarding a method for purifying n-borneol to obtain borneol.
ｎ−ボルネオールは、天然にフタバガキ科のドリオバラ
ノプス アロマチイカ（Ｄｒｙｏｂａｌａｎｏｐｓａｒ
ｏｎ＋ａｔｉｃａ ） 、ディ カンフォラ（Ｄ、ｃａ
ｍｐｈｏｒａ）、ディ ロンギファラ（Ｄ、１ｏｎｇｉ
ｆｏｌｉａ） 、マツ科のアビニス コンカラー（Ａｂ
ｉｅｓ ｃｏｎｃｏｌｏｒ） 、ピナス パラストリス
（Ｐｉｎｕｓ ｐａｌｕｓｔｒｉｓ ）などの精油中、
あるいはラベンダー油、ローズマリー油、スパイク油中
などに存在し、主として香粧用として広く使用されてい
る化合物であるが、その産地が限定されるのみならず、
生産量も変動する。N-borneol is naturally derived from Dryobalanopsar, a member of the Dipterocarpaceae family.
on+atica), di canfora (D, ca
mphora), di longifara (D, 1ongi
folia), Abinis concolor (Ab) of the Pinaceae family
ies concolor), in essential oils such as Pinus palustris,
It is also a compound that exists in lavender oil, rosemary oil, spike oil, etc., and is widely used mainly for cosmetics, but its production area is not only limited, but also
Production volume also fluctuates.
従ってｎ−ボルネオールは、一般には樟脳の還元、ある
いはα−ピネンと有機酸との反応により合成する方法の
ほか、種々の合成法により製造されている。Therefore, n-borneol is generally produced by reduction of camphor or reaction of α-pinene with an organic acid, as well as various synthetic methods.
かかる合成法によって得られる粗ボルネオールは、必ず
イソボルネオールを含有しており、通常、その含有量は
２５重量％以上である。Crude borneol obtained by such a synthesis method always contains isoborneol, and the content is usually 25% by weight or more.
従来、例えば香粧用として使用される場合には、上記の
如き粗ボルネオールであっても特に問題とはならず、高
純度のｎ−ボルネオールは必要とされなかった。Conventionally, when used for cosmetics, for example, crude borneol as described above did not pose a particular problem, and high purity n-borneol was not required.
しかしながら、近年、ｎ−ボルネオールを工業用原料と
して使用する用途が見出され、例えば重合用上ツマ−の
アルコール成分として使用する場合には、不純物の非常
に少ない、例えば純度が９５重量％以上の高純度のｎ−
ボルネオールが必要とされる。However, in recent years, applications have been found for using n-borneol as an industrial raw material. For example, when using n-borneol as an alcohol component for polymerization, it is necessary to use n-borneol with very few impurities, for example, with a purity of 95% by weight or more. High purity n-
Borneol is required.
従来、不純物としてイソボルネオールを含有する粗ボル
ネオールを精製する方法としては、例えば■溶剤に対す
る溶解度の差を利用して再結晶を繰り返す方法、あるい
は■ベンゼン中に粗ボルネオールを溶解し、これに塩化
亜鉛あるいはｐ−）ルエンスルホン酸を加えて加温し、
イソボルネオールをカンフエンとなし、残ったｎ−ボル
ネオールをフタル酸エステルとして再結晶後鹸化して、
ｎ−ボルネオールとする方法などが知られている。Conventionally, methods for purifying crude borneol containing isoborneol as an impurity include: (1) repeating recrystallization by taking advantage of the difference in solubility in solvents, or (2) dissolving crude borneol in benzene and adding zinc chloride to it. Alternatively, add p-)luenesulfonic acid and heat,
Isoborneol is converted into camphene, the remaining n-borneol is recrystallized as a phthalate ester, and then saponified.
A method of converting it into n-borneol is known.
しかしながら、■再結晶を繰り返す方法は、含有するイ
ソボルネオールの量が多い場合には、ｎ−ボルネオール
の回収率が大きく低下し、好ましい方法ではない。However, the method (1) of repeating recrystallization is not a preferred method because the recovery rate of n-borneol decreases significantly when the amount of isoborneol contained is large.
また、■塩化亜鉛あるいはｐ−）ルエンスルホン酸を触
媒として用い、イソボルネオールをカンフエンへ反応さ
せる方法は、該触媒による反応装置の腐蝕が大きいため
、耐蝕性の良好な高級材質を使用する必要があり、また
該触媒を分離するため繁雑な水洗工程を必要とするほか
、強酸性であるため、イソボルネオールの残存率を低く
しようとすると、目的物であるｎ−ボルネオールも脱水
されるという欠点を有し、何れも好ましい方法ではない
。In addition, in the method of reacting isoborneol to camphene using zinc chloride or p-)luenesulfonic acid as a catalyst, the reaction equipment caused by the catalyst is highly corroded, so it is necessary to use high-grade materials with good corrosion resistance. Moreover, in addition to requiring a complicated water washing process to separate the catalyst, it is also strongly acidic, so if you try to reduce the residual rate of isoborneol, the target product, n-borneol, will also be dehydrated. Both methods are not preferred.
本発明は、かかる従来の技術的課題を背景になされたも
ので、粗ボルネオールからイソボルネオールの含有量が
掻めて少ない高純度のｎ−ボルネオールを得ることを目
的とする。The present invention was made against the background of such conventional technical problems, and an object of the present invention is to obtain high-purity n-borneol containing significantly less isoborneol from crude borneol.
本発明者らは、前記従来技術の有する欠点を克服すべく
鋭意検討した結果、シリカ・アルミナ、活性白土、ゼオ
ライトなどの固体酸化合物を触媒とし、粗ボルネオール
を、不活性媒体中で加熱することによって、ｎ−ボルネ
オールは殆ど変化せず、インボルネオールのみ脱水反応
することを見出し、本発明に到達したものである。As a result of intensive studies to overcome the drawbacks of the above-mentioned conventional techniques, the present inventors discovered that crude borneol is heated in an inert medium using a solid acid compound such as silica/alumina, activated clay, or zeolite as a catalyst. They found that n-borneol hardly changes and only inborneol undergoes a dehydration reaction, and the present invention was achieved based on this finding.
即ち、本発明は、粗ボルネオール中に含有されるイソボ
ルネオールを脱水してカンフエンに誘導し、これを分離
することによって高純度ｎ−ボルネオールを得るに際し
、粗ボルネオールを不活性媒体中に溶解し、触媒として
の固体酸化合物の存在下、液相を維持する条件下に６０
〜１６０℃にてイソボルネオールの脱水反応を行うこと
を特徴とするｎ−ボルネオールの精製法である。That is, the present invention dehydrates isoborneol contained in crude borneol to induce camphene and separates it to obtain high purity n-borneol, which involves dissolving the crude borneol in an inert medium, 60 in the presence of a solid acid compound as a catalyst and under conditions that maintain a liquid phase.
This is a method for purifying n-borneol, which is characterized by carrying out a dehydration reaction of isoborneol at a temperature of ~160°C.
まず、本発明において適用される粗ボルネオールとは、
例えば前記したように天然の精油から分離したもの、ま
たは酒精溶液において金属ナトリウムにより樟脳を還元
して得られるｎ−ボルネオールと少量のイソボルネオー
ルとの混合物、更にはα−ピネンと有機酸との反応によ
り合成されたものなどである。First, crude borneol applied in the present invention is
For example, as mentioned above, it is separated from natural essential oils, or a mixture of n-borneol and a small amount of isoborneol obtained by reducing camphor with metallic sodium in an alcoholic solution, or a reaction between α-pinene and an organic acid. These include those synthesized by
また、本発明において使用される不活性媒体としては、
ヘキサン、ヘプタンなどの脂肪族炭化水素、ベンゼン、
トルエン、キシレン、ｐ−サイメンなどの芳香族炭化水
素、シクロヘキサン、ビナン、ｐ−メンタンなどの脂環
族炭化水素、ジオキサン、ジエチルセルフルプなどのエ
ーテル類などが挙げられるが、溶解性、経済性の点から
、好ましくは芳香族炭化水素が用いられ、特に好ましく
はカンフエンの沸点（約１６０℃）より高い沸点、好ま
しくは１６５℃以上の沸点を有するもの、例えばｐ−サ
イメン（沸点１７７℃）が用いられる。In addition, the inert medium used in the present invention includes:
Aliphatic hydrocarbons such as hexane and heptane, benzene,
Examples include aromatic hydrocarbons such as toluene, xylene, and p-cymene, alicyclic hydrocarbons such as cyclohexane, vinylane, and p-menthane, and ethers such as dioxane and diethyl cellulph. For this reason, aromatic hydrocarbons are preferably used, particularly those having a boiling point higher than the boiling point of camphene (approximately 160°C), preferably 165°C or higher, such as p-cymene (boiling point 177°C). It will be done.
カンフエンより沸点が低い不活性媒体を使用した場合、
例えば粗ボルネオール中のイソボルネオールの含有量が
多いと、カンフエンの溶液中の濃度が高くなり、１回の
晶析では高純度のｎ−ボルネオールを得ることができず
、再結晶を繰り返す必要があることもある。If an inert medium with a boiling point lower than camphuene is used,
For example, if the content of isoborneol in crude borneol is high, the concentration of camphene in the solution will be high, and high purity n-borneol cannot be obtained in one crystallization, and recrystallization must be repeated. Sometimes.
前記不活性媒体の使用量はミ使用する媒体の種類によっ
て異なるが、本質的には反応温度においてｎ−ボルネオ
ールが溶解するに充分な量であればよく特に制限はない
が、一般にはｎ−ボルネオール１００重量部に対し、２
０〜１，０００重量部、好ましくは５０〜３００重量部
である。The amount of the inert medium used varies depending on the type of medium used, but essentially there is no particular restriction as long as the amount is sufficient to dissolve n-borneol at the reaction temperature, but in general, n-borneol is used. 2 for 100 parts by weight
The amount is 0 to 1,000 parts by weight, preferably 50 to 300 parts by weight.
本発明において脱水触媒として用いられる固体酸化合物
としては、シリカ、アルミナ、シリカ・アルミナ、白土
、ゼオライトなど天然に産出する種々の化合物のほか、
合成品も挙げられる。Solid acid compounds used as dehydration catalysts in the present invention include various naturally occurring compounds such as silica, alumina, silica/alumina, clay, and zeolite.
Synthetic products may also be mentioned.
一般に固体酸化合物としては、気相反応にて脱水能力が
ある化合物であれば有効であるが、好ましくは酸強度Ｈ
８の値が−８，２以上、＋３．３以下、特に好ましくは
酸強度Ｈｏの値が−５，６以上、＋１．５以下の化合物
が使用される。In general, solid acid compounds are effective if they have the ability to dehydrate in a gas phase reaction, but preferably they have an acid strength of H
A compound having an acid strength Ho value of -8.2 or more and +3.3 or less, particularly preferably a compound having an acid strength Ho value of -5.6 or more and +1.5 or less is used.
酸強度Ｈａの値が＋３．３よりも大きい固体酸化合物を
用いた場合、例えば１２０℃にて８時間反応してもイソ
ボルネオールは２０％程度の反応率にしかならないので
好ましくなく、一方酸強度Ｈｏの値が−８，２よりも小
さい固体酸化合物を用いた場合には、イソボルネオール
の脱水反応が充分終了しないうちにｎ−ボルネオールの
副反応が起こることもあるので好ましくない。If a solid acid compound with an acid strength Ha value higher than +3.3 is used, for example, even if the reaction is carried out at 120°C for 8 hours, the reaction rate of isoborneol will only be about 20%, which is not preferable. When a solid acid compound having a Ho value of less than -8.2 is used, it is not preferable because a side reaction of n-borneol may occur before the dehydration reaction of isoborneol is sufficiently completed.
使用する固体酸化合物の形状は、粉末状、粒子状、ペレ
ット状など如何なる形状でもよく、反応面からは表面積
の多い粉末状が好ましく、反応形式によっては触媒分離
が不要となるペレット状が好ましい場合もあり、特に限
定されるものではない。The shape of the solid acid compound used may be any shape such as powder, particulate, or pellet. From the viewpoint of reaction, a powder with a large surface area is preferable, and depending on the reaction type, a pellet may be preferable since catalyst separation is not necessary. There are some, but there are no particular limitations.
本発明において、固体酸化合物の使用量は、粗ボルネオ
ール中のイソボルネオールの含有量および反応条件など
によって異なるが、通常、粗ボルネオールに対し０．１
〜５０重量％、好ましくは０、２〜２０重量％、特に好
ましくは０．５〜１０重量％である。In the present invention, the amount of the solid acid compound used varies depending on the isoborneol content in the crude borneol and the reaction conditions, but is usually 0.1% relative to the crude borneol.
~50% by weight, preferably 0.2-20% by weight, particularly preferably 0.5-10% by weight.
触媒となる固体酸化合物の使用量が、粗ボルネオールに
対して０．１重量％未満と少ない場合には、イソボルネ
オールの脱水反応が遅すぎて好ましくなく、一方５０重
量％より多い場合は触媒である固体酸化合物ののコスト
が高くなり好ましくない。If the amount of the solid acid compound used as a catalyst is less than 0.1% by weight based on crude borneol, the dehydration reaction of isoborneol will be too slow, which is undesirable. On the other hand, if it is more than 50% by weight, the catalyst will This is not preferable because the cost of some solid acid compounds increases.
本発明における脱水反応は、液相下に実施され、該反応
温度は、使用する固体酸化合物の種類および量ならびに
不活性媒体の種類によって異なるが、通常、６０℃〜１
６０℃、好ましくは８０〜１５０°Ｃで実施される。The dehydration reaction in the present invention is carried out in a liquid phase, and the reaction temperature varies depending on the type and amount of the solid acid compound used and the type of inert medium, but is usually 60°C to 1°C.
It is carried out at 60°C, preferably 80-150°C.
反応温度が６０℃未満の場合には反応速度が遅すぎ、一
方反応温度１６０℃より高い場合には目的物であるｎ−
ボルネオールの脱水反応が顕著となるので好ましくない
。If the reaction temperature is less than 60°C, the reaction rate is too slow, while if the reaction temperature is higher than 160°C, the target product n-
This is not preferable because the dehydration reaction of borneol becomes significant.
本発明における脱水反応の時間は特に制限はなく、使用
する固体酸化合物の種類および量、反応温度ならびに反
応形式などによって異なるが、操作性および経済性の点
より、通常、０．０５〜２０時間、好ましくは０．５〜
１０時間で実施される。The time for the dehydration reaction in the present invention is not particularly limited and varies depending on the type and amount of solid acid compound used, reaction temperature, reaction format, etc., but from the viewpoint of operability and economic efficiency, it is usually 0.05 to 20 hours. , preferably 0.5~
It will be carried out in 10 hours.
本発明の脱水反応を実施するに際し、その反応の形式は
バッチ反応、連続反応、いずれ′でも良く、また反応器
形式も攪拌槽、充填塔などのほか、如何な゛る形式でも
よい。When carrying out the dehydration reaction of the present invention, the reaction format may be batch reaction or continuous reaction, and the reactor format may be of any type, such as a stirred tank or a packed column.
例えば、粒状の固体酸化合物を使用する場合には、充填
塔形式が好ましく用いられ、所定の温度下に所定の滞留
時間でボルネオールの溶液を流通させるのみで反応を行
わしめることが可能であり、後記する固体酸化合物を分
離する工程が不要となる利点がある。For example, when using a granular solid acid compound, a packed column format is preferably used, and the reaction can be carried out simply by passing a solution of borneol at a predetermined temperature for a predetermined residence time. There is an advantage that the step of separating the solid acid compound, which will be described later, is not necessary.
また、本発明の脱水反応は、通常、大気下もしくは窒素
気流下、常圧下で実施される。Further, the dehydration reaction of the present invention is usually carried out in the atmosphere or in a nitrogen stream under normal pressure.
以上のように、本発明は、（１）粗ボルネオールを不活
性媒体中に溶解し、固体酸化合物の存在下、６０〜１６
０℃にてイソボルネオールを脱水反応する工程よりなり
、これにより得られる反応生成液は、ｎ−ボルネオール
、カンフエン、使用された不活性媒体および固体酸化合
物を主成分とするが、ｎ−ボルネオールを有効に分離、
回収するためには、本発明に更に（ＩＩ）固体酸化合物
を分離する工程、（ＩＩＩ）カンフエンを蒸留などの手
段により分離する工程、（ｒＶ）冷却あるいは不活性媒
体の留去によりｎ−ボルネオールを晶析する工程、およ
び（Ｖ）ｎ−ボルネオールを分離回収する工程の４工程
を付加し、合計５工程より構成するとよい。As described above, the present invention provides (1) dissolving crude borneol in an inert medium and dissolving the crude borneol in the presence of a solid acid compound at 60 to 16
It consists of a step of dehydrating isoborneol at 0°C, and the resulting reaction product liquid contains n-borneol, camphene, the inert medium used, and a solid acid compound as main components, but does not contain n-borneol. effective separation,
In order to recover, the present invention further includes (II) a step of separating the solid acid compound, (III) a step of separating camphene by means such as distillation, and (rV) cooling or distillation of an inert medium to remove n-borneol. It is preferable to add four steps: a step of crystallizing , and a step of separating and recovering (V) n-borneol, to constitute a total of five steps.
ここで、（ＩＩ）固体酸化合物分離工程では、反応生成
液を、例えば通常の圧減器、葉状濾過器、回転濾過器な
どの濾過手段を用いて濾過、分離するものである０本工
程は、場合により（ＩＩＩ）カンフエン分離工程の後に
実施してもよい。Here, in the solid acid compound separation step (II), the reaction product liquid is filtered and separated using a filtration means such as an ordinary pressure reducer, leaf filter, rotary filter, etc. , may optionally be carried out after the camphuene separation step (III).
また、（ＩＩＩ）カンフエン分離工程は、生成するカン
フエンの量および使用する不活性媒体によってその実施
態様が異なる。Furthermore, the embodiment of the camphuene separation step (III) differs depending on the amount of camphuene produced and the inert medium used.
例えばカンフエンの生成量が１０重量％程度と比較的少
なく、かつカンフエンよりも沸点の高い不活性媒体を使
用した場合には、反応中に生成するカンフエンの大半が
実質的に反応系から留去する場合もあるので、該（ＩＩ
Ｉ）カンフエン分離工程を省略することが可能であるが
、通常はカンフエンの生成量が２５重量％程度と多いの
で、カンフエンよりも沸点の高い不活性媒体を使用し、
本工程においてカンフエンを蒸留にて分離する。For example, if the amount of camphuene produced is relatively small, about 10% by weight, and an inert medium with a boiling point higher than that of camphuene is used, most of the camphuene produced during the reaction will be substantially distilled off from the reaction system. In some cases, the corresponding (II
I) It is possible to omit the camphuene separation step, but since the amount of camphuene produced is usually as high as about 25% by weight, an inert medium with a boiling point higher than that of camphuene is used,
In this step, camphuene is separated by distillation.
この場合の蒸留条件は、例えば常圧蒸留の場合には塔頂
温度１５７〜１６０℃、還流比１〜５程度で実施され、
また減圧蒸留の場合には塔頂圧力３０〜１００Ｔｏｒｒ
、塔頂温度６６〜９６℃、還流比１〜５程度の条件下で
実施される。The distillation conditions in this case are, for example, in the case of atmospheric distillation, the tower top temperature is 157 to 160 ° C., and the reflux ratio is about 1 to 5.
In addition, in the case of vacuum distillation, the tower top pressure is 30 to 100 Torr.
The reaction is carried out under conditions of a tower top temperature of 66 to 96°C and a reflux ratio of about 1 to 5.
かくて（ｎ）固体酸分離工程および（Ｉ［［）カンフエ
ン分離工程を経た反応生成液は、実質的にｎ−ボルネオ
ールと不活性媒体とよりなるので、（ＩＶ） ｆｌ−ボ
ルネオール晶析工程において、反応生成液中から該ｎ−
ボルネオールを晶析させ、分離する。ｎ−ボルネオール
は、ｄ一体およびｌ一体の融点が約２０８℃、ｄｌ一体
の融点が約２０４℃であり、いずれも不活性媒体に較べ
て高融点を有するので、例えば■反応生成液を２０〜４
０℃に冷却するか、■１０〜３００Ｔｏｒｒの減圧下で
不活性媒体をｎ−ボルネオール／不活性媒体（重量比）
＝５０／１００、好ましべは７０／１００、更に好まし
くは１００／１００程度になるまで留去し、次いで常温
において晶析するか、■前記■および■の手段を組み合
わせて晶析すれば、ｎ−ボルネオールが結晶として析出
される。Thus, the reaction product liquid after passing through the (n) solid acid separation step and the (I , the n-
The borneol is crystallized and separated. N-borneol has a melting point of about 208°C for d and l, and about 204°C for dl, both of which have higher melting points than an inert medium. 4
Cool to 0°C or mix n-borneol/inert medium (weight ratio) under reduced pressure of 10 to 300 Torr.
= 50/100, preferably the stamens are 70/100, more preferably about 100/100, and then crystallized at room temperature, or by combining the methods of (2) and (2) above, n-borneol is precipitated as crystals.
このように、（ｒＶ）ｎ−ボルネオール分離工程で晶析
された該ｎ−ボルネオールの結晶を回収するには、前記
（ｎ）固体酸化合物分離工程で使用されたと同様の通常
の濾過手段を用いればよい。In this way, in order to recover the crystals of n-borneol crystallized in the (rV) n-borneol separation step, the same ordinary filtration means as used in the solid acid compound separation step (n) above can be used. Bye.
なお、更に高純度のｎ−ボルネオールを得るためには、
かくて分離、回収されたｎ−ポルネールの結晶を、例え
ば更に不活性媒体に溶解し、前記（ＩＶ）晶析、（Ｖ）
分離を数回繰り返して精製することもできる。In addition, in order to obtain even higher purity n-borneol,
The thus separated and recovered n-pornaire crystals are further dissolved in an inert medium, for example, and subjected to the above (IV) crystallization and (V)
Purification can also be achieved by repeating the separation several times.
本発明は、粗ボルネオールの精製に際し、脱水触媒とし
て固体酸化合物を用いることによりｎ −ボルネオール
は殆ど変化させることなく、イソボルネオールのみを脱
水反応させ、高純度のｎ−ボルネオールを得るものであ
る。The present invention uses a solid acid compound as a dehydration catalyst during purification of crude borneol to cause only isoborneol to undergo a dehydration reaction without substantially changing n-borneol, thereby obtaining highly pure n-borneol.
以下、実施例を挙げて本発明を更に詳しく説明するが、
本発明は特許請求の範囲を越えない限りこれらの実施例
に限定されるものではない。Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these embodiments unless it goes beyond the scope of the claims.
なお、実施例中、特に断らない限り、部および％は、重
量基準である。In the examples, unless otherwise specified, parts and percentages are based on weight.
実施例１
還流冷却器、温度計を備えたｔｏｏｏ容量部の撹拌槽に
、粗ボルネオール（ｎ−ボルネオール６９．８％、イソ
ボルネオール２５，１％、その他の成分５．１％よりな
る）２００部、ｐ−サイメン２００部、および粉末状シ
リカ・アルミナ（日揮化学■製、Ｎ−６３３Ｌ、酸強度
＋１．５〜−３．０）４部を仕込み、１２０℃の温度に
て５時間攪拌した。Example 1 200 parts of crude borneol (consisting of 69.8% n-borneol, 25.1% isoborneol, and 5.1% other components) was placed in a stirring tank of too much volume equipped with a reflux condenser and a thermometer. , 200 parts of p-Cymene, and 4 parts of powdered silica/alumina (manufactured by JGC Chemical Corporation, N-633L, acid strength +1.5 to -3.0) were charged and stirred at a temperature of 120° C. for 5 hours.
反応生成液をサンプリングし、ガスクロマトグラフィー
で分析した結果、粗ボルネオールを基準としてｎ−ボル
ネオール６９．６％、イソボルネオール０． ２％、カ
ンフエン２２．６％、ジボルニルエーテル（ｎ−ボルネ
オールの脱水物）１．２％、その他の成分６．４％であ
った。The reaction product liquid was sampled and analyzed by gas chromatography, which revealed that n-borneol was 69.6% and isoborneol was 0.9% based on crude borneol. 2%, camphene 22.6%, dibornyl ether (n-borneol dehydrate) 1.2%, and other components 6.4%.
この反応生成液より９０℃にて加圧濾過機を用いてシリ
カ・アルミナを濾過、分離した後、塔頂圧カフ０Ｔｏｒ
ｒ、塔頂温度８７℃の減圧下に精留し、カンフエン４３
部を含む留出液５０部を分離回収した。After filtering and separating silica and alumina from this reaction product liquid using a pressure filter at 90°C, the top pressure cuff was adjusted to 0 Torr.
r, rectified under reduced pressure at a tower top temperature of 87°C to produce camphene 43
50 parts of distillate containing 50 parts were separated and collected.
蒸留残査を３０℃に冷却して、ｎ−ボルネオールを析出
させ、これを加圧濾過機を用いて濾過し結晶９１部を分
離回収した。The distillation residue was cooled to 30° C. to precipitate n-borneol, which was filtered using a pressure filter to separate and collect 91 parts of crystals.
得られた結晶は、ｎ−ボルネオールの純度が９８．２％
であり、またこの中にはイソボルネオールが０．１％含
有されていた。The purity of n-borneol in the obtained crystals was 98.2%.
This contained 0.1% isoborneol.
実施例２〜６
実施例１において、不活性媒体の使用量、固体酸化合物
の種類およびその使用量ならびに反応温度および反応時
間を第１表の如く変えた以外は、実施例１と同様に脱水
反応を行った。Examples 2 to 6 Dehydration was carried out in the same manner as in Example 1, except that the amount of inert medium used, the type and amount of solid acid compound used, and the reaction temperature and reaction time were changed as shown in Table 1. The reaction was carried out.
脱水反応後の反応生成液の組成を第１表に示した。Table 1 shows the composition of the reaction product solution after the dehydration reaction.
得られた反応生成液より固体酸化合物を分離し、カンフ
エンおよび不活性媒体がｐ−サイメンの場合は該ｐ−サ
イメンの一部を実施例１に準じて蒸留により回収した後
、冷却、晶析し、実施例１と同様に高純度のｎ−ボルネ
オールを得た。The solid acid compound is separated from the resulting reaction product liquid, and if camphuene and the inert medium are p-cymene, a part of the p-cymene is recovered by distillation according to Example 1, followed by cooling and crystallization. Then, in the same manner as in Example 1, high purity n-borneol was obtained.
使用した固体酸化合物は、以下の通りである。The solid acid compounds used are as follows.
セカード 品用企業■製、商品名；Ｋｗ酸強度＋１．５
〜−３．０
活性白土 水沢化学側製、ガレオンアースＨ酸強度−３
，０〜−５，６
（以下余白）
比較例１
実施例３において、反応温度を１７０℃とした以外は、
実施例１と全く同様に脱水反応を行った。Manufactured by SEKADO Supplier Company ■, product name: Kw acid strength +1.5
~-3.0 Activated clay, manufactured by Mizusawa Chemical, Galleon Earth H acid strength -3
,0 to -5,6 (blank below) Comparative Example 1 In Example 3, except that the reaction temperature was 170°C,
The dehydration reaction was carried out in exactly the same manner as in Example 1.
脱水反応後の反応生成液の組成を第１表に併せて示す。The composition of the reaction product solution after the dehydration reaction is also shown in Table 1.
比較例２
実施例１において、反応温度を５０℃とした以外は、実
施例１と全く同様に脱水反応を行った。Comparative Example 2 A dehydration reaction was carried out in exactly the same manner as in Example 1, except that the reaction temperature was 50°C.
脱水反応後の反応生成液の組成を第１表に併せて示す。The composition of the reaction product solution after the dehydration reaction is also shown in Table 1.
実施例７
実施例１と同様な反応装置に、粗ボルネオール（ｎ−ボ
ルネオール６９．８％、イソボルネオール２５．１％、
その他の成分５．１％よりなる）２００部、トルエン２
００部および粉末状シリカ・アルミナ（日揮化学■製、
Ｎ６３３Ｌ）５部を仕込み、１１０℃にて５時間攪拌し
た。Example 7 Crude borneol (n-borneol 69.8%, isoborneol 25.1%,
(consisting of 5.1% of other ingredients) 200 parts, toluene 2
00 parts and powdered silica/alumina (manufactured by JGC Chemical ■,
5 parts of N633L) were added and stirred at 110°C for 5 hours.
反応生成液をガスクロマトグラフィーにより分析したと
ころ、カンフエン２５．４％、イソボルネオール０．３
％、ｎ−ボルネオール６９．５％、ジボルニルエーテル
０．４％、その他の成分４．４％であった。Analysis of the reaction product liquid by gas chromatography revealed that camphene was 25.4% and isoborneol was 0.3%.
%, n-borneol 69.5%, dibornyl ether 0.4%, and other components 4.4%.
この反応生成液よりシリカ・アルミナを加圧濾過機を用
いて濾過、分離した後、塔頂温度１１０〜１２０℃の常
圧蒸留により、主としてトルエンを含有する留分１３０
部を回収した。After filtering and separating silica and alumina from this reaction product liquid using a pressure filter, a fraction 130 containing mainly toluene is distilled by atmospheric distillation at a tower top temperature of 110 to 120°C.
Part was collected.
得られた蒸留残査を２５℃まで冷却し、ｎ−ボルネオー
ルを析出させ、これを分離して、結晶１０３部を得た。The obtained distillation residue was cooled to 25° C. to precipitate n-borneol, which was separated to obtain 103 parts of crystals.
この結晶は、ｎ−ボルネオール純度９６．３％で、カン
フエン２．９％、イソボルネオール０．１％を含有して
いた。The crystals had an n-borneol purity of 96.3% and contained 2.9% camphene and 0.1% isoborneol.
実施例８〜９
実施例４および実施例６において、不活性媒体をトルエ
ンに変えた以外は実施例４．６と同様にして脱水反応を
行った。Examples 8 to 9 In Examples 4 and 6, the dehydration reaction was carried out in the same manner as in Example 4.6 except that the inert medium was changed to toluene.
反応生成液の組成は、実施例４および６と殆ど同様であ
った。The composition of the reaction product liquid was almost the same as in Examples 4 and 6.
即ち、実施例８の場合の反応生成液の組成は、粗ボルネ
オールを基準としてｎ−ボルネオール６９．２％、イソ
ボルネオール１．７％、カンフエン２４．１％、ジボル
ニルエーテルＯ％、その他の成分５６０％であり、また
実施例９の場合の反応生成液の組成は、粗ボルネオール
を基準としてｎ−ボルネオール６８．３％、イソボルネ
オール１．５％、カンフエン２４．０％、ジポルニルエ
ーテル１．４％、その他の成分４．８％であった。That is, the composition of the reaction product liquid in Example 8 was based on crude borneol: 69.2% n-borneol, 1.7% isoborneol, 24.1% camphene, 0% dibornyl ether, and other components. 560%, and the composition of the reaction product liquid in Example 9 was 68.3% n-borneol, 1.5% isoborneol, 24.0% camphene, 1 dipornyl ether, based on crude borneol. .4%, and other components 4.8%.
比較例３〜４
実施例１と同様な反応装置に、実施例１または実施例７
で使用された前記粗ボルネオール２００部、トルエン５
００部およびｐ−）ルエンスルホン酸１０部または塩化
亜鉛４０部を仕込み、１１０℃にて２時間攪拌した。Comparative Examples 3-4 Example 1 or Example 7 was added to the same reaction apparatus as Example 1.
200 parts of the crude borneol used in
00 parts and 10 parts of p-)luenesulfonic acid or 40 parts of zinc chloride were added, and the mixture was stirred at 110°C for 2 hours.
反応後の生成液の組成を第１表に併せて示す。The composition of the product solution after the reaction is also shown in Table 1.
実施例１０
実施例７において、固体酸化合物として、ゼオライト（
東洋曹達■製、ＴＳＺ−３３０、酸強度−３，０〜−５
，６）４部を用い、反応時間を１時間とした以外は、実
施例７と同様に脱水反応を行った。Example 10 In Example 7, zeolite (
Manufactured by Toyo Soda ■, TSZ-330, acid strength -3.0 to -5
, 6) was used, and the dehydration reaction was carried out in the same manner as in Example 7, except that the reaction time was 1 hour.
反応生成液をガスクロマトグラフィーにより分析したと
ころ、その組成は、ｎ−ボルネオール６８．０％、イソ
ボルネオール０．８％、カンフエン２６．０％、その他
の成分５．２％であった。When the reaction product liquid was analyzed by gas chromatography, its composition was 68.0% n-borneol, 0.8% isoborneol, 26.0% camphene, and 5.2% other components.
実施例１１
実施例１と同様な反応装置に、ボルネオール（ｎ−ボル
ネオール９３．７％、イソボルネオール１．８％、カン
フエン２．１％、その他の成分２．４％よりなる）２０
０部、トルエン２００部、ゼオライト（東洋曹達■製、
ＴＳＺ−３３０）２部を仕込み、１１０℃にて２時間攪
拌した。Example 11 In a reactor similar to Example 1, 20 borneol (consisting of 93.7% n-borneol, 1.8% isoborneol, 2.1% camphene, and 2.4% other components) was added.
0 parts, toluene 200 parts, zeolite (manufactured by Toyo Soda ■,
TSZ-330) was added thereto, and the mixture was stirred at 110°C for 2 hours.
この反応生成液より約１００℃の温度下でゼオライトを
濾過、分離した後、冷却し２５℃にて結晶を析出させ、
これより濾過、分離することにより、結晶１５７部を得
た。After filtering and separating the zeolite from this reaction product liquid at a temperature of about 100°C, it is cooled and crystals are precipitated at 25°C.
By filtration and separation, 157 parts of crystals were obtained.
得られた結晶は、ｎ−ボルネオール純度９９．１％で、
イソボルネオール０．１％を含有していた。The obtained crystals had n-borneol purity of 99.1%,
It contained 0.1% isoborneol.
本発明に従えば、前記の如き従来技術に見られる触媒に
よる装置の腐食は全くなく、また触媒除去のための繁雑
な水洗工程も必要とせず、極めて安価に高純度ｎ−ボル
ネオールを得ることができる。According to the present invention, there is no corrosion of the equipment due to the catalyst as seen in the prior art, and there is no need for a complicated water washing process to remove the catalyst, making it possible to obtain highly pure n-borneol at an extremely low cost. can.
また、本発明の更なる利点は、水洗工程を必要としない
ため、溶媒（不活性媒体）の使用量を少なくすることが
でき、触媒（固体酸化合物）を分離し、カンフエンを除
去した後、単に冷却するのみで高純度のｎ−ボルネオー
ルを晶出させることができる点にある。A further advantage of the present invention is that since no water washing step is required, the amount of solvent (inert medium) used can be reduced, and after separating the catalyst (solid acid compound) and removing camphuene, The advantage is that high purity n-borneol can be crystallized simply by cooling.
Claims (4)
を脱水してカンフェンに誘導し、これを分離することに
よって高純度ｎ−ボルネオールを得るに際し、粗ボルネ
オールを不活性媒体中に溶解し、触媒としての固体酸化
合物の存在下、液相を維持する条件下に６０〜１６０℃
にてイソボルネオールの脱水反応を行うことを特徴とす
るｎ−ボルネオールの精製法。(1) When obtaining high-purity n-borneol by dehydrating isoborneol contained in crude borneol and guiding it to camphene and separating it, crude borneol is dissolved in an inert medium and used as a catalyst. 60-160°C under conditions that maintain a liquid phase in the presence of a solid acid compound
1. A method for purifying n-borneol, which comprises carrying out a dehydration reaction of isoborneol.
請求の範囲第１項記載のｎ−ボルネオールの精製法。(2) The method for purifying n-borneol according to claim 1, wherein camphene produced is separated by distillation.
である特許請求範囲第１項記載のｎ−ボルネオールの精
製法。(3) The method for purifying n-borneol according to claim 1, wherein the inert medium has a boiling point of 165° C. or higher at normal pressure.
＋３．３以下である特許請求の範囲第１項記載のｎ−ボ
ルネオールの精製法。(4) The acid strength H_o of the solid acid compound is -8.2 or more,
The method for purifying n-borneol according to claim 1, wherein the n-borneol content is +3.3 or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60156021A JPS6219546A (en) | 1985-07-17 | 1985-07-17 | Purification of n-borneol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60156021A JPS6219546A (en) | 1985-07-17 | 1985-07-17 | Purification of n-borneol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6219546A true JPS6219546A (en) | 1987-01-28 |
| JPS6238344B2 JPS6238344B2 (en) | 1987-08-17 |
Family
ID=15618578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60156021A Granted JPS6219546A (en) | 1985-07-17 | 1985-07-17 | Purification of n-borneol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6219546A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1070164C (en) * | 1996-01-02 | 2001-08-29 | 唐松柏 | Pinene esterifying and saponifying process synthesizing borneol and composite boron-titanium based catalyst |
| CN1100745C (en) * | 1998-03-15 | 2003-02-05 | 唐松柏 | Three-type high-purity synthetic borneols and economic making method for getting from crude product |
| CN101723807B (en) | 2009-12-14 | 2012-10-24 | 上海应用技术学院 | Preparation method of borneol |
| CN102942452A (en) * | 2011-12-14 | 2013-02-27 | 江西普正制药有限公司 | Preparation method of natural borneol |
| CN103739448A (en) * | 2014-02-01 | 2014-04-23 | 闻永举 | Method for preparing high-purity borneol from camphor, camphor reduction product and borneol |
| CN110698317A (en) * | 2019-09-11 | 2020-01-17 | 云南林缘香料有限公司 | Method for extracting high-purity camphene from light components of by-products in borneol synthesis production |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755527B (en) * | 2014-02-01 | 2016-07-13 | 闻永举 | The method being prepared high-purity borneol by Lauraceae extract or Herba Blumeae Balsamiferae extract |
| WO2016119270A1 (en) * | 2015-01-31 | 2016-08-04 | 闻永举 | Method of preparing high-purity borneol from camphor, camphor reduction product, and borneo camphor |
-
1985
- 1985-07-17 JP JP60156021A patent/JPS6219546A/en active Granted
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1070164C (en) * | 1996-01-02 | 2001-08-29 | 唐松柏 | Pinene esterifying and saponifying process synthesizing borneol and composite boron-titanium based catalyst |
| CN1100745C (en) * | 1998-03-15 | 2003-02-05 | 唐松柏 | Three-type high-purity synthetic borneols and economic making method for getting from crude product |
| CN101723807B (en) | 2009-12-14 | 2012-10-24 | 上海应用技术学院 | Preparation method of borneol |
| CN102942452A (en) * | 2011-12-14 | 2013-02-27 | 江西普正制药有限公司 | Preparation method of natural borneol |
| CN103739448A (en) * | 2014-02-01 | 2014-04-23 | 闻永举 | Method for preparing high-purity borneol from camphor, camphor reduction product and borneol |
| CN110698317A (en) * | 2019-09-11 | 2020-01-17 | 云南林缘香料有限公司 | Method for extracting high-purity camphene from light components of by-products in borneol synthesis production |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6238344B2 (en) | 1987-08-17 |
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