JPS5829736A - Synthesis of 4-allyl-2,5-cyclohexadienone derivative - Google Patents
Synthesis of 4-allyl-2,5-cyclohexadienone derivativeInfo
- Publication number
- JPS5829736A JPS5829736A JP56127077A JP12707781A JPS5829736A JP S5829736 A JPS5829736 A JP S5829736A JP 56127077 A JP56127077 A JP 56127077A JP 12707781 A JP12707781 A JP 12707781A JP S5829736 A JPS5829736 A JP S5829736A
- Authority
- JP
- Japan
- Prior art keywords
- allyl
- cyclodextrin
- para
- derivative
- substituted
- 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
- 238000003786 synthesis reaction Methods 0.000 title abstract description 3
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920000858 Cyclodextrin Polymers 0.000 abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 12
- 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 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- -1 allyl halide Chemical class 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 150000002989 phenols Chemical class 0.000 abstract description 5
- 239000000243 solution Substances 0.000 abstract description 5
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 abstract description 4
- 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 abstract description 4
- 229940043377 alpha-cyclodextrin Drugs 0.000 abstract description 4
- 239000007864 aqueous solution Chemical class 0.000 abstract description 4
- 239000001116 FEMA 4028 Substances 0.000 abstract description 3
- 125000003545 alkoxy group Chemical group 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 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 abstract description 3
- 235000011175 beta-cyclodextrine Nutrition 0.000 abstract description 3
- 229960004853 betadex Drugs 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000013543 active substance Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- WGHKKEJHRMUKDK-UHFFFAOYSA-N cyclohexa-2,5-dien-1-one Chemical class O=C1C=CCC=C1 WGHKKEJHRMUKDK-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical class [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 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 group [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 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
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-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
- 239000002244 precipitate Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000007039 two-step reaction Methods 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は４位に置換あるいは非置換アリル基を有スζ２
，５−’／クロー・キサジェノン誘導体〔１〕〔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〕を選択的に製造す
る方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides an allyl group having a substituted or unsubstituted allyl group at the 4-position.
,5-'/Clo-xagenone derivative [1] [in the formula A
, B, C, D, E are hydrogen, substituted and unsubstituted alkyl groups, allyl groups, alkoxyl groups, or aryl groups, and R is a substituted or unsubstituted allyl group].
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、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、−！、だ分子内で環化す
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。A 2,5-cyclohexadienone derivative having an allyl group at the 4-position has high reactivity because two C-C double bonds and a carbonyl group are conjugated, and -! Because it has an allyl group in a position suitable for cyclization within the molecule, 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 Ｃｈｅｍｉ
ｃａｌ ５ｏｃｉｅｔｙ、第１００巻、 １９７８年
発行、第４６１８頁に記載されているように、化合物〔
２〕
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。Journal of American Chemi
Cal 5ociety, Vol. 100, Published in 1978, p.
2] can be used as a starting material to synthesize the antibiotic erythromycin.
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ェノール類の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、４
−シクロへキサジェノン誘導体〔３〕
〔３〕
〔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〕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〕の分離精製が困難であること、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 phenol substituted at the para-position with an allyl halide in an aromatic solvent. is allylated 2,4
-Cyclohexagenone derivative [3] [3] [wherein A, B, C, D, and E are hydrogen, substituted and unsubstituted alkyl groups, allyl groups, alkoxyl groups, or aryl groups, R is substituted or unsubstituted allyl The allyl group was synthesized in a two-step reaction, in which the allyl group was synthesized 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 reactant [3], particularly in the first stage, 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を触
媒として使用することによシ、パラ位置換フェノール類
とハロゲン化アリルとの、水溶液中の１段階の反応によ
シ、目的生成物である２、５−シクロへキサジェノン誘
導体〔１〕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 uses cyclodextrin, which is a cyclic oligosaccharide, as a catalyst to produce the desired product 2 through a one-step reaction of para-substituted phenols and allyl halides in an aqueous solution. , 5-cyclohexagenone derivative [1] can be synthesized in high yield and with high selectivity.
すなわち２本発明者らは、パラ位置換フェノール誘導体
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および２に示す通り２本発明におけ
る目的物〔１〕の収率は５０〜６０チであり１選択率は
４０〜５５チである。これに対し、比較例１に示すよう
に、シクロデキストリンを用いない反応における〔１〕
の収率は１５〜２５チであり２選択率は１８〜２８チで
ある。Namely, the present inventors added cyclodextrin to an aqueous solution of a para-substituted phenol derivative and sodium hydroxide or potassium hydroxide, dissolved it, and then added dropwise allyl halide to produce a 2,5-cyclohexadienone derivative. were successfully synthesized in high yield and selectivity. As shown in Examples 1 and 2, the yield of the target product [1] in the present invention is 50 to 60%, and the selectivity is 40 to 55%. In contrast, as shown in Comparative Example 1, [1] in the reaction without using cyclodextrin
The yield is 15-25 and the 2 selectivity is 18-28.
シクロデキストリンとしては、α−シクロデキストリン
とβ−シクロデキストリンのいずれも用いｂことができ
る。As the cyclodextrin, both α-cyclodextrin and β-cyclodextrin can be used.
シクロデキストリンは反応中に変化せず２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。Cyclodextrin does not change during the reaction and can be reused as is after two reactions. After separation of the 2,5-cyclohexadienone derivative by ether extraction.
反応系を酸性にすると溶解度の減少のためにシクロデキ
ストリンが沈澱する。この簡便な方法でシクロデキスト
リンの７〜８割は回収され９回収されたシクロデキスト
リンは完全に再使用にたえるａつぎに本発明を具体的に
実施例をあげて説明するが、これにより本発明を制限す
るものではない。When the reaction system is made acidic, cyclodextrin precipitates due to decreased solubility. With this simple method, 70 to 80% of the cyclodextrin is recovered, and the recovered cyclodextrin can be completely reused.Next, the present invention will be specifically explained with examples. It does not limit the invention.
実施例１
０．２０ｇの２．４．６−）リメチルフェノール（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。Example 1 0.20 g of 2.4.6-)limethylphenol (manufactured by Tokyo Chemical Industry Co., Ltd., special grade reagent) and 7.5 g of α-cyclodextrin (manufactured by Hanui Chemical Co., Ltd.).
特級試薬）を５０ｍＡ！の１チ水酸化ナトリウム水溶液
に溶かし、室温で０．９９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２反応液を５０ｍ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ｏ、 ｉ ｓ
ＩＩの生成物を得、 Ｈ−ＮＭＲ測定を行なった結
果、この生成物の５３チは２，４゜６−ドリメチルー４
−アリル−２，５−シクロヘキサジエノンであり、
２，４．６−ドリメチルー６−アリルー２，４−シクロ
ヘキサジエノンおよび２．４．６−トリメチルフェニル
−アリルエーテルはそれぞれ２６％、２１％であった。special grade reagent) at 50mA! The solution was dissolved in an aqueous solution of sodium hydroxide, and reacted at room temperature for 24 hours while adding 0.99 allyl bromide (special grade reagent, manufactured by Tokyo Kasei Kogyo Co., Ltd.) dropwise. After the reaction, the two reaction solutions were extracted five times with 50 m of ether, and the ether layer was dried. In this way o, is
As a result of obtaining the product II and performing H-NMR measurement, it was found that 53 molecules of this product were 2,4°6-drimethyl-4
-allyl-2,5-cyclohexadienone,
2,4.6-dolimethyl-6-allyl-2,4-cyclohexadienone and 2,4.6-trimethylphenyl-allyl ether were 26% and 21%, respectively.
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チであった。That is, the yield and selectivity of the target product were each 48%.
and 53 chi.
実施例２
実施例１と同様の操作により、７．５ｇのα−シクロデ
キストリンの代わりに７．５ｇのβ−シクロデキストリ
ン（半井化学薬品株式会社製、特級試薬）を使用し、
０．２０．！ｉ’の生成物を得た。Ｈ−ＮＭＲ測定に
より、この生成物の４１チは２，４．６−ドリメチルニ
２，５−シクロヘキサジエノンであり。Example 2 By the same operation as in Example 1, 7.5 g of β-cyclodextrin (manufactured by Hanui Chemical Co., Ltd., special grade reagent) was used instead of 7.5 g of α-cyclodextrin,
0.20. ! The product i' was obtained. According to H-NMR measurement, 41% of this product was 2,4.6-drimethyldi-2,5-cyclohexadienone.
２、４．６− ）サメチル−６−アリル−２，４−−シ
、クロヘキサジエノンおよび２．４．６− ）リメチル
フェニルーアリルエーテルはそれぞれ３４チおよび２８
チであった。すなわち２、目的物の収率および選択率は
いずれも４１％であった。2,4.6-) samethyl-6-allyl-2,4-cy,chlorhexadienone and 2.4.6-)limethylphenyl-allyl ether are 34 and 28, respectively.
It was Chi. That is, 2. The yield and selectivity of the target product were both 41%.
比較例１
０、２０９の２．４．６− ）リメチルフェノール（東
京化成工業株式会社製、特級試薬）を５０ｍ１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１反応液を５０ ｍ
ｌ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０．１９９の生成物を得。Comparative Example 1 0, 209, 2.4.6-) Limethylphenol (manufactured by Tokyo Kasei Kogyo Co., Ltd., special grade reagent) was dissolved in 50 ml of 1% aqueous sodium hydroxide solution, and 0.9 g of allyl bromide ( A special grade reagent manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the mixture for 24 hours. After reaction, transfer one reaction solution to 50 m
The extract was extracted 5 times with 1 liter of ether, and the ether layer was dried. A product of 0.199 was thus obtained.
’Ｈ−ＮＭＲ測定を行なった結果、この生成物の２５チ
は２，４．６−１リメチル−２，５−シクロヘキサジェ
ノ／であシ、 ２，４．６−）ジメチル−６−アリル
−２，４−シクロヘキサジエノンおよび２．４．６−
トリメチルフェニル−アリルエーテルはそれぞれ５０チ
および２５チであった。すなわち、目的物の収率および
選択率はそれぞれ２４チおよび２５チであった。As a result of 'H-NMR measurement, 25% of this product was 2,4.6-1-dimethyl-2,5-cyclohexageno/dehyde, 2,4.6-)dimethyl-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.
特許出願人 平井英史Patent applicant Hidefumi Hirai
Claims (1)
ル誘導体を反応させるにあたシ、ンクロデキストリンを
触媒として用いることにより、４位のアリル化された２
、５−シクロへキサジェノン誘導体を高収率および高選
択的に製造する方法When reacting the phenol derivative substituted at the 4-position with the allyl derivative substituted at the 4-position, nclodextrin is used as a catalyst.
, a method for producing 5-cyclohexagenone derivatives in high yield and with high selectivity
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56127077A JPS5829736A (en) | 1981-08-13 | 1981-08-13 | Synthesis of 4-allyl-2,5-cyclohexadienone derivative |
| EP82900665A EP0073837B1 (en) | 1981-03-09 | 1982-03-09 | Process for selectively producing para-substituted derivatives of phenols |
| DE8282900665T DE3274104D1 (en) | 1981-03-09 | 1982-03-09 | Process for selectively producing para-substituted derivatives of phenols |
| EP19840112783 EP0158709B1 (en) | 1981-03-09 | 1982-03-09 | A process for producing a para-substituted phenol derivative |
| DE8484112783T DE3276858D1 (en) | 1981-03-09 | 1982-03-09 | A process for producing a para-substituted phenol derivative |
| PCT/JP1982/000066 WO1982003073A1 (en) | 1981-03-09 | 1982-03-09 | Process for introducing substituent to p-position of phenols |
| US06/530,158 US4523031A (en) | 1981-08-11 | 1983-09-07 | Process for producing a para-substituted phenol derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56127077A JPS5829736A (en) | 1981-08-13 | 1981-08-13 | Synthesis of 4-allyl-2,5-cyclohexadienone derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5829736A true JPS5829736A (en) | 1983-02-22 |
| JPH0134212B2 JPH0134212B2 (en) | 1989-07-18 |
Family
ID=14951000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56127077A Granted JPS5829736A (en) | 1981-03-09 | 1981-08-13 | Synthesis of 4-allyl-2,5-cyclohexadienone derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5829736A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007055225A (en) * | 2005-07-29 | 2007-03-08 | Asami Seisakusho:Kk | Curing method for concrete, mold for concrete and curing apparatus for concrete product |
-
1981
- 1981-08-13 JP JP56127077A patent/JPS5829736A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007055225A (en) * | 2005-07-29 | 2007-03-08 | Asami Seisakusho:Kk | Curing method for concrete, mold for concrete and curing apparatus for concrete product |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0134212B2 (en) | 1989-07-18 |
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