JPS647062B2 - - Google Patents
Info
- Publication number
- JPS647062B2 JPS647062B2 JP57076368A JP7636882A JPS647062B2 JP S647062 B2 JPS647062 B2 JP S647062B2 JP 57076368 A JP57076368 A JP 57076368A JP 7636882 A JP7636882 A JP 7636882A JP S647062 B2 JPS647062 B2 JP S647062B2
- Authority
- JP
- Japan
- Prior art keywords
- allyl
- cyclodextrin
- formula
- groups
- group
- 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
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 13
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 9
- WGHKKEJHRMUKDK-UHFFFAOYSA-N cyclohexa-2,5-dien-1-one Chemical class O=C1C=CCC=C1 WGHKKEJHRMUKDK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229920000858 Cyclodextrin Polymers 0.000 claims description 6
- -1 allyl halide Chemical class 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 150000002989 phenols Chemical class 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- BPRYUXCVCCNUFE-UHFFFAOYSA-N 2,4,6-trimethylphenol Chemical compound CC1=CC(C)=C(O)C(C)=C1 BPRYUXCVCCNUFE-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical class [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 3
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 3
- 229940043377 alpha-cyclodextrin Drugs 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- 229920001353 Dextrin Polymers 0.000 description 2
- 239000004375 Dextrin Substances 0.000 description 2
- ULGZDMOVFRHVEP-RWJQBGPGSA-N Erythromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=O)[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 ULGZDMOVFRHVEP-RWJQBGPGSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000019425 dextrin Nutrition 0.000 description 2
- IILMKSDECSXASD-UHFFFAOYSA-N 2,4,6-trimethylcyclohexa-2,5-dien-1-one Chemical compound CC1C=C(C)C(=O)C(C)=C1 IILMKSDECSXASD-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical group CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- PMDCZENCAXMSOU-UHFFFAOYSA-N N-ethylacetamide Chemical group CCNC(C)=O PMDCZENCAXMSOU-UHFFFAOYSA-N 0.000 description 1
- ZMZINYUKVRMNTG-UHFFFAOYSA-N acetic acid;formic acid Chemical compound OC=O.CC(O)=O ZMZINYUKVRMNTG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229940097362 cyclodextrins Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229960003276 erythromycin Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- KERBAAIBDHEFDD-UHFFFAOYSA-N n-ethylformamide Chemical group CCNC=O KERBAAIBDHEFDD-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-AZXPZELESA-N n-methylacetamide Chemical group C[15NH]C(C)=O OHLUUHNLEMFGTQ-AZXPZELESA-N 0.000 description 1
- ATHHXGZTWNVVOU-VQEHIDDOSA-N n-methylformamide Chemical group CN[13CH]=O ATHHXGZTWNVVOU-VQEHIDDOSA-N 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は、一般式〔１〕
〔式中Ａ，Ｂ，Ｃ，Ｄ，Ｅは水素又は低級アル
キル基である。但し、Ａは水素であることはな
い。〕
で表されるパラ位置換フエノール誘導体に対して
ハロゲン化アリル誘導体を反応させるに当り、一
級水酸基をすべてＮ−アルキルホルムアミド基又
はＮ−アルキルアセトアミド基で置換したシクロ
デキストリンを触媒として用いることにより、一
般式〔２〕
〔式中Ａ，Ｂ，Ｃ，Ｄ，Ｅは〔１〕式と同じ。
但し、Ａは水素であることはない。Ｒは置換又は
非置換アリル基である。〕
で表される４位のアリル化された２，５−シクロ
ヘキサジエノン誘導体を高収率及び高選択的に製
造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to general formula [1] [In the formula, A, B, C, D, and E are hydrogen or lower alkyl groups. However, A is never hydrogen. ] In reacting the allyl halide derivative with the para-substituted phenol derivative represented by, by using as a catalyst a cyclodextrin in which all primary hydroxyl groups are substituted with N-alkylformamide groups or N-alkylacetamido groups, General formula [2] [In the formula, A, B, C, D, and E are the same as in formula [1].
However, A is never hydrogen. R is a substituted or unsubstituted allyl group. ] It is related with the method of manufacturing the 4-position allylated 2,5-cyclohexadienone derivative represented by these with high yield and high selectivity.
４位にアリル基を有する２，５−シクロヘキサ
ジエノン粒導体は、２個のＣ−Ｃ二重結合とカル
ボニル基が共役しているために反応性に富み、ま
た分子内で環化するのに適した位置にアリル基が
あるために、生理活性物質その他の有用な物質の
合成原料となる重要な化合物である。たとえば、
Journal of American Chemical Society、第
100巻、1978年発行、第4618頁に記載されている
ように、化合物〔３〕
を出発原料として抗生物質エリスロマイシンが合
成できる。 The 2,5-cyclohexadienone particle conductor having an allyl group at the 4-position has high reactivity because the two C-C double bonds and the carbonyl group are conjugated, and it is also difficult to cyclize within the molecule. Because it has an allyl group in a suitable position, it is an important compound that can be used as a raw material for the synthesis of physiologically active substances and other useful substances. for example,
Journal of American Chemical Society, Vol.
As described in Volume 100, published in 1978, page 4618, compound [3] The antibiotic erythromycin can be synthesized using this as a starting material.
従来、４位にアリル基を有する２，５−シクロ
ヘキサジエノン誘導体は、まず、芳香族溶媒中で
ナトリウムメトキシドとパラ位置換フエノール類
の１：１混合物にハロゲン化アリルを作用させて
６位がアリル化された２，５−シクロヘキサジエ
ノン誘導体〔４〕
〔式中Ａ，Ｂ，Ｃ，Ｄ，Ｅは水素、置換および
非置換アルキル基、アリル基、アルコキシル基、
またはアリール基、Ｒは置換あるいは非置換アリ
ル基。但し、Ａは水素であることはない。〕を合
成し、つぎに、これをメタノール塩酸中で反応さ
せてアリル基を６位に転移せしめるという２段階
の反応で合成されていた。しかしながら、この方
法は、特に第１段階目の反応物〔３〕の分離精製
が固難であること、および多量の有機溶媒を使用
するなどの欠点を有する。 Conventionally, 2,5-cyclohexadienone derivatives having an allyl group at the 4-position were prepared by first treating a 1:1 mixture of sodium methoxide and a para-substituted phenol with an allyl halide in an aromatic solvent to form an allyl group at the 6-position. allylated 2,5-cyclohexadienone derivative [4] [In the formula, A, B, C, D, and E are hydrogen, substituted and unsubstituted alkyl groups, allyl groups, alkoxyl groups,
or an aryl group; R is a substituted or unsubstituted allyl group; However, A is never hydrogen. ], and then reacted in methanol-hydrochloric acid to transfer the allyl group to the 6-position. However, this method has drawbacks such as difficulty in separating and purifying the reactant [3], particularly in the first step, and the use of a large amount of organic solvent.
本発明は、環状オリゴ糖であるシクロデキスト
リン（以下、非修飾デキストリンと記す）の一級
水酸基をＮ−アルキルホルムアミド基またはＮ−
アルキルアセトアミド基により置換して得られる
シクロデキストリン（以下、修飾デキストリンと
記す）を触媒として使用することにより、パラ位
置換フエノール類とハロゲン化アリルとの、水溶
液中の１段階の反応により、目的生成物である
２，５−シクロヘキサジエノン誘導体〔２〕を高
収率および高選択的に合成することを可能とする
ものである。 The present invention provides a method for converting the primary hydroxyl group of cyclodextrin (hereinafter referred to as unmodified dextrin), which is a cyclic oligosaccharide, to an N-alkylformamide group or an N-
By using a cyclodextrin obtained by substitution with an alkyl acetamide group (hereinafter referred to as modified dextrin) as a catalyst, a one-step reaction between a para-substituted phenol and an allyl halide in an aqueous solution produces the desired product. This makes it possible to synthesize the 2,5-cyclohexadienone derivative [2] in high yield and with high selectivity.
すなわち、本発明者らは、パラ位置換フエノー
ル誘導体と水酸化ナトリウムまたは水酸化カリウ
ムの水溶液に上記の修飾シクロデキストリンを加
え、溶解せしめた後にハロゲン化アリルを滴下す
ることにより、２，５−シクロヘキサジエノン誘
導体を高収率および高選択性で合成することに成
功した。実施例１に示すとおり、本発明における
目的物〔２〕の収率は85％であり、選択率は100
％である。これに対し、比較例１に示すように、
非修飾シクロデキストリンを触媒とする場合の目
的物〔２〕の収率および選択率は、それぞれ48％
および53％である。また、比較例２に示すとおり
修飾シクロデキストリンおよび非修飾シクロデキ
ストリンのいずれも触媒として用いない場合に
は、〔２〕の収率および選択率は、それぞれ24％
および25％である。 That is, the present inventors added the above-mentioned modified cyclodextrin to an aqueous solution of a para-substituted phenol derivative and sodium hydroxide or potassium hydroxide, dissolved it, and then added the allyl halide dropwise to obtain 2,5-cyclohextrin. We succeeded in synthesizing sadienone derivatives in high yield and selectivity. As shown in Example 1, the yield of the target product [2] in the present invention was 85%, and the selectivity was 100%.
%. On the other hand, as shown in Comparative Example 1,
When unmodified cyclodextrin is used as a catalyst, the yield and selectivity of the target product [2] are 48%, respectively.
and 53%. Furthermore, as shown in Comparative Example 2, when neither modified cyclodextrin nor unmodified cyclodextrin is used as a catalyst, the yield and selectivity of [2] are 24%, respectively.
and 25%.
本発明で言うＮ−アルキルホルムアミド基と
は、例えば、Ｎ−メチルホルムアミド基、Ｎ−エ
チルホルムアミド基などである。また、Ｎ−アル
キルアセトアミド基とは、例えば、Ｎ−メチルア
セトアミド基、Ｎ−エチルアセトアミド基などで
ある。 The N-alkylformamide group referred to in the present invention includes, for example, N-methylformamide group and N-ethylformamide group. Further, the N-alkylacetamide group includes, for example, an N-methylacetamide group and an N-ethylacetamide group.
本発明で用いる修飾シクロデキストリンは、例
えば、Journal of American Chemical
Society、第102巻、1980年発行、第762頁に記載
された方法により合成することができる。すなわ
ち、α−シクロデキストリン、あるいは、β−シ
クロデキストリンをトシルクロリドと反応させ
て、その一級水酸基をすべてトシル化した後、ア
ルキルアミンおよびギ酸−酢酸混合無水物あるい
は無水酢酸と順次反応させて目的物を得る。 The modified cyclodextrin used in the present invention is, for example, published in the Journal of American Chemical
It can be synthesized by the method described in Society, Vol. 102, published in 1980, p. 762. That is, α-cyclodextrin or β-cyclodextrin is reacted with tosyl chloride to tosylate all of its primary hydroxyl groups, and then reacted sequentially with an alkylamine and formic acid-acetic acid mixed anhydride or acetic anhydride to obtain the desired product. get.
修飾シクロデキストリンは反応中に変化せず、
反応後そのまま再使用が可能である。エーテル抽
出により２，５−シクロヘキサジエノン誘導体を
分離後、反応系を酸性にすると溶解度の減少のた
めに修飾シクロデキストリンが沈澱する。この簡
便な方法で修飾シクロデキストリンの８〜９割は
回収され、回収された修飾シクロデキストリンは
完全に再使用にたえる。 Modified cyclodextrins do not change during the reaction,
It can be reused as is after the reaction. After separating the 2,5-cyclohexadienone derivative by ether extraction, when the reaction system is made acidic, the modified cyclodextrin precipitates due to decreased solubility. With this simple method, 80 to 90% of the modified cyclodextrin can be recovered, and the recovered modified cyclodextrin can be completely reused.
つぎに、本発明を具体的に実施例を挙げて説明
するが、これにより本発明を制限するものではな
い。 Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.
実施例 １
Journal of American Chemical Society、第
102巻、1980年発行、第762頁に記載された方法に
より、α−シクロデキストリン（半井化学薬品株
式会社製、特級試薬）の一級水酸基をすべてＮ−
メチルホルムアミド化した。この修飾シクロデキ
ストリン８ｇと0.20ｇの２，４，６−トリメチル
フエノール（東京化成株式会社製、特級試薬）を
50mlの１％水酸化ナトリウム水溶液に溶かし、室
温で0.9ｇの臭化アリル（東京化成工業株式会社
製、特級試薬）を滴下しつつ24時間反応せしめ
る。反応後、反応液を50mlのエチルエーテルで５
回抽出し、エチルエーテル層を乾燥した。このよ
うにして0.22ｇの生成物を得、1H−NMR測定を
行なつた結果、この生成物はすべて２，４，６−
トリメチル−４−アリル−２，５−シクロヘキサ
ジエノンであつた。すなわち、目的物の収率およ
び選択率はそれぞれ85％および100％であつた。Example 1 Journal of American Chemical Society, Vol.
By the method described in Volume 102, published in 1980, page 762, all the primary hydroxyl groups of α-cyclodextrin (manufactured by Hanui Chemical Co., Ltd., special grade reagent) were converted to N-
Methylformamidated. 8 g of this modified cyclodextrin and 0.20 g of 2,4,6-trimethylphenol (manufactured by Tokyo Kasei Co., Ltd., special grade reagent) were added.
Dissolve in 50 ml of 1% aqueous sodium hydroxide solution, and react at room temperature for 24 hours while adding dropwise 0.9 g of allyl bromide (manufactured by Tokyo Chemical Industry Co., Ltd., special grade reagent). After the reaction, dilute the reaction solution with 50 ml of ethyl ether.
It was extracted twice and the ethyl ether layer was dried. In this way, 0.22 g of product was obtained, and as a result of 1 H-NMR measurement, all of this product was 2,4,6-
It was trimethyl-4-allyl-2,5-cyclohexadienone. That is, the yield and selectivity of the target product were 85% and 100%, respectively.
比較例 １
0.20ｇの２，４，６−トリメチルフエノール
（東京化成工業株式会社製、特級試薬）と7.5ｇの
α−シクロデキストリン（半井化学薬品株式会社
製、特級試薬）を50mlの１％水酸化ナトリウム水
溶液に溶かし、室温で0.9ｇの臭化アリル（東京
化成工業株式会社製、特級試薬）を滴下しつつ24
時間反応せしめる。反応後、反応液を50mlのエー
テルで５回抽出し、エーテル層を乾燥した。この
ようにして0.18ｇの生成物を得、1H−NMR測定
を行なつた結果、この生成物の53％は２，４，６
−トリメチル−４−アリル−２，５−シクロヘキ
サジエノンであり、２，４，６−トリメチル−６
−アリル−２，５−シクロヘキサジエノンおよび
２，４，６−トリメチルフエニル−アリルエーテ
ルはそれぞれ26％、21％であつた。すなわち、目
的物の収率および選択率はそれぞれ48％および53
％であつた。Comparative Example 1 0.20 g of 2,4,6-trimethylphenol (manufactured by Tokyo Chemical Industry Co., Ltd., special grade reagent) and 7.5 g of α-cyclodextrin (manufactured by Hanui Chemical Co., Ltd., special grade reagent) were mixed with 50 ml of 1% water. Dissolved in an aqueous sodium oxide solution, and dropwise added 0.9 g of allyl bromide (manufactured by Tokyo Kasei Kogyo Co., Ltd., special grade reagent) at room temperature.
Let time react. After the reaction, the reaction solution was extracted five times with 50 ml of ether, and the ether layer was dried. In this way, 0.18 g of a product was obtained, and as a result of 1 H-NMR measurement, 53% of this product was 2,4,6
-trimethyl-4-allyl-2,5-cyclohexadienone, and 2,4,6-trimethyl-6
-Allyl-2,5-cyclohexadienone and 2,4,6-trimethylphenyl-allyl ether were 26% and 21%, respectively. That is, the yield and selectivity of the target product are 48% and 53%, respectively.
It was %.
比較例 ２
0.20ｇの２，４，６−トリメチルフエノール
（東京化成工業株式会社製、特級試薬）を50mlの
１％水酸化ナトリウム水溶液に溶かし、室温で
0.9ｇの臭化アリル（（東京化成工業株式会社製、
特級試薬）を滴下しつつ24時間反応せしめる。反
応後、反応液を50mlのエーテルで５回抽出し、エ
ーテル層を乾燥した。このようにして0.19ｇの生
成物を得、1H−NMR測定を行なつた結果、この
生成物の25％は２，４，６−トリメチル−２，５
−シクロヘキサジエノンであり、２，４，６−ト
リメチル−６−アリル−２，４−シクロヘキサジ
エノンおよび２，４，６−トリメチルフエニル−
アリルエーテルはそれぞれ50％および25％であつ
た。すなわち、目的物の収率および選択率はそれ
ぞれ24％および25％であつた。Comparative Example 2 Dissolve 0.20 g of 2,4,6-trimethylphenol (manufactured by Tokyo Kasei Kogyo Co., Ltd., special grade reagent) in 50 ml of 1% aqueous sodium hydroxide solution, and dissolve at room temperature.
0.9 g of allyl bromide (manufactured by Tokyo Kasei Kogyo Co., Ltd.,
React for 24 hours while dropping special grade reagent). After the reaction, the reaction solution was extracted five times with 50 ml of ether, and the ether layer was dried. In this way, 0.19 g of a product was obtained, and as a result of 1 H-NMR measurement, 25% of this product was 2,4,6-trimethyl-2,5
-cyclohexadienone, 2,4,6-trimethyl-6-allyl-2,4-cyclohexadienone and 2,4,6-trimethylphenyl-
Allyl ether was 50% and 25% respectively. That is, the yield and selectivity of the target product were 24% and 25%, respectively.
Claims (1)
キル基である。但し、Ａは水素であることはな
い。〕 で表されるパラ位置換フエノール誘導体に対して
ハロゲン化アリル誘導体を反応させるに当り、一
級水酸基をすべてＮ−アルキルホルムアミド基又
はＮ−アルキルアセトアミド基で置換したシクロ
デキストリンを触媒として用いることにより、一
般式〔２〕 〔式中Ａ，Ｂ，Ｃ，Ｄ，Ｅは〔１〕式と同じ。
但し、Ａは水素であることはない。Ｒは置換又は
非置換アリル基である。〕 で表わされる４位のアリル化された２，５−シク
ロヘキサジエノン誘導体を高収率及び高選択的に
製造する方法。[Claims] 1 General formula [1] [In the formula, A, B, C, D, and E are hydrogen or lower alkyl groups. However, A is never hydrogen. ] In reacting the allyl halide derivative with the para-substituted phenol derivative represented by, by using as a catalyst a cyclodextrin in which all primary hydroxyl groups are substituted with N-alkylformamide groups or N-alkylacetamido groups, General formula [2] [In the formula, A, B, C, D, and E are the same as in formula [1].
However, A is never hydrogen. R is a substituted or unsubstituted allyl group. ] A method for producing an allylated 2,5-cyclohexadienone derivative at the 4-position with high yield and high selectivity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57076368A JPS58194835A (en) | 1982-05-07 | 1982-05-07 | Synthesis of 4-allyl-2,5-cyclohexadienone derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57076368A JPS58194835A (en) | 1982-05-07 | 1982-05-07 | Synthesis of 4-allyl-2,5-cyclohexadienone derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58194835A JPS58194835A (en) | 1983-11-12 |
| JPS647062B2 true JPS647062B2 (en) | 1989-02-07 |
Family
ID=13603397
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57076368A Granted JPS58194835A (en) | 1982-05-07 | 1982-05-07 | Synthesis of 4-allyl-2,5-cyclohexadienone derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58194835A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04100762A (en) * | 1990-08-17 | 1992-04-02 | Mk Seiko Co Ltd | Car washer |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3575127D1 (en) * | 1984-02-14 | 1990-02-08 | Hirai Hidefumi | MANUFACTURE OF SUBSTITUTED UNSATURED SIX-PIECE RING CONNECTIONS FROM PHENOLA COMBINATIONS. |
| ATE197594T1 (en) * | 1994-12-20 | 2000-12-15 | Kimberly Clark Co | IMPROVED, CHANGEABLE COMPOSITION |
-
1982
- 1982-05-07 JP JP57076368A patent/JPS58194835A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04100762A (en) * | 1990-08-17 | 1992-04-02 | Mk Seiko Co Ltd | Car washer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58194835A (en) | 1983-11-12 |
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