JPH0470295B2 - - Google Patents
Info
- Publication number
- JPH0470295B2 JPH0470295B2 JP25555186A JP25555186A JPH0470295B2 JP H0470295 B2 JPH0470295 B2 JP H0470295B2 JP 25555186 A JP25555186 A JP 25555186A JP 25555186 A JP25555186 A JP 25555186A JP H0470295 B2 JPH0470295 B2 JP H0470295B2
- Authority
- JP
- Japan
- Prior art keywords
- tetramethoxynaphthalene
- methyl
- formyl
- shikonin
- butene
- 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
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 8
- FBYIJIHPWCXRHH-UHFFFAOYSA-N 1,4,5,8-tetramethoxynaphthalene-2-carbaldehyde Chemical compound O=CC1=CC(OC)=C2C(OC)=CC=C(OC)C2=C1OC FBYIJIHPWCXRHH-UHFFFAOYSA-N 0.000 claims description 7
- GTFBEJZJLDKOHE-UHFFFAOYSA-N 4-methyl-1-(1,4,5,8-tetramethoxynaphthalen-2-yl)pent-4-en-1-ol Chemical compound COc1ccc(OC)c2c(OC)c(cc(OC)c12)C(O)CCC(C)=C GTFBEJZJLDKOHE-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- NEZONWMXZKDMKF-JTQLQIEISA-N Alkannin Chemical compound C1=CC(O)=C2C(=O)C([C@@H](O)CC=C(C)C)=CC(=O)C2=C1O NEZONWMXZKDMKF-JTQLQIEISA-N 0.000 description 8
- 241001071917 Lithospermum Species 0.000 description 8
- UNNKKUDWEASWDN-UHFFFAOYSA-N alkannin Natural products CC(=CCC(O)c1cc(O)c2C(=O)C=CC(=O)c2c1O)C UNNKKUDWEASWDN-UHFFFAOYSA-N 0.000 description 8
- LGMPVUDVTHHFDR-UHFFFAOYSA-N 4-chloro-2-methylbut-1-ene Chemical compound CC(=C)CCCl LGMPVUDVTHHFDR-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- LQQKULWAVYAOBB-UHFFFAOYSA-N 1,2,3,4-tetramethoxynaphthalene Chemical compound C1=CC=CC2=C(OC)C(OC)=C(OC)C(OC)=C21 LQQKULWAVYAOBB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- -1 (4-pentenyl)-1,4,5,8-tetramethoxynaphthalene Chemical compound 0.000 description 1
- SWNROPPWBFHVCS-UHFFFAOYSA-N 1,4,5,8-tetramethoxynaphthalene Chemical compound C1=CC(OC)=C2C(OC)=CC=C(OC)C2=C1OC SWNROPPWBFHVCS-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 206010020649 Hyperkeratosis Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002260 anti-inflammatory agent Substances 0.000 description 1
- 229940121363 anti-inflammatory agent Drugs 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- SLUNEGLMXGHOLY-UHFFFAOYSA-N benzene;hexane Chemical compound CCCCCC.C1=CC=CC=C1 SLUNEGLMXGHOLY-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012136 culture method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 241000411851 herbal medicine Species 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000001047 purple dye Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000006257 total synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、シコニンの合成中間体である２−
（１−ヒドロキシ−４−メチル−４−ペンテニル）
−１，４，５，８−テトラメトキシナフタレンと
その製造法に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention provides 2-
(1-hydroxy-4-methyl-4-pentenyl)
-1,4,5,8-tetramethoxynaphthalene and its manufacturing method.
（従来の技術）
日本、中国、朝鮮半島に産する紫根の主成分で
あるシコニンおよびそのエステルは古代からの有
名な漢方薬で、皮膚消炎剤、抗腫瘍剤、抗菌剤と
して勝れた効果を有するのみならず、古代紫染染
料としても、つとに貴重品とされてきた。しかる
にその資源としては自然植生の紫草の根を探すの
みであつたから、年々枯渇の一途をたどり、現在
では専ら中国からの輸入に依存しているのであ
る。これらの理由から、近時カルス培養法による
製造も開始されたが極めて高価である。(Prior art) Shikonin, the main component of purple root found in Japan, China, and the Korean Peninsula, and its esters are famous Chinese herbal medicines from ancient times, and have excellent effects as skin anti-inflammatory agents, antitumor agents, and antibacterial agents. It was also considered a valuable item as an ancient purple dye. However, since the only resource available for this was to search for the purple roots of natural vegetation, it has been depleted year by year, and is currently dependent solely on imports from China. For these reasons, production by a callus culture method has recently been started, but it is extremely expensive.
本発明者等は曩にシコニン製造法を特開昭59−
175449号に、またシコニン合成中間体の製造法を
特開昭61−204153号として提案した。これら提案
した方法は、２−ホルミル−１，４，５，８−テ
トラメトキシナフタレンを原料として途中４工程
を経て化成した２−（1′−アセトキシ−4′−オキ
シ−4′−メチルペンチル）−５，８−ジアセトキ
シ−１，４−ナフトキノンより出発する合成法で
あり、かかる出発原料の製造工程を大幅に短縮し
全工程の合理化を図る必要があつた。 The present inventors first published a method for producing shikonin in Japanese Unexamined Patent Application Publication No. 59-1989.
175449, and also proposed a method for producing a shikonin synthetic intermediate as JP-A-61-204153. In these proposed methods, 2-(1'-acetoxy-4'-oxy-4'-methylpentyl) was chemically synthesized from 2-formyl-1,4,5,8-tetramethoxynaphthalene through four intermediate steps. This is a synthetic method starting from -5,8-diacetoxy-1,4-naphthoquinone, and it was necessary to significantly shorten the manufacturing process for this starting material and streamline the entire process.
（この発明が解決しようとする問題点）
シコニンの合成は(2)式に示すシコニンの化学構
造のうち、Ａ部分とＢ部分とに分けてそれぞれを
作り、その合体によつて構成するのが普通であ
る。しかしながら、Ｂ部分には化学的に極めて活
性な炭素二重結合が含まれているために、従来の
合成化学的知識を以てしてはＡ部分と結合させる
ことが困難であつた。このために本発明者らがそ
の全合成法を開発する以前にはシコニンの化学合
成は成功しなかつたのである（J.Chem.Soc.、
Chem.Commun.、1983、987）。(Problems to be Solved by this Invention) Shikonin is synthesized by separating the A part and B part of the chemical structure of shikonin shown in formula (2), and then combining them. It's normal. However, since part B contains a chemically extremely active carbon double bond, it has been difficult to bond it to part A using conventional synthetic chemistry knowledge. For this reason, the chemical synthesis of shikonin had not been successful before the inventors developed its total synthesis method (J.Chem.Soc.
Chem.Commun., 1983, 987).
そこで本発明は、別途出願の１，４，５，８−
テトラメトキシナフタレン製造法の結果物である
２−ホルミル誘導体から、工業的に実施容易な、
工程の短縮されたシコニン製造法を提供すること
を目的とするものである。 Therefore, the present invention is based on the separately filed application Nos. 1, 4, 5, 8-
From the 2-formyl derivative that is the result of the tetramethoxynaphthalene production method, it is possible to obtain
The purpose of the present invention is to provide a method for producing shikonin with a shortened process.
（問題点を解決するための手段）
上記目的は、２−ホルミル−１，４，５，８−
テトラメトキシナフタレンに４−クロロ−２−メ
チル−１−ブテンのグリニヤール化合物を反応さ
せることを特徴とする化学構造式、
で表される２−（１−ヒドロシキ−４−メチル−
４−ペンテニル）−１，４，５，８−テトラメト
キシナフタレンの製造法によつて達成される。(Means for solving the problem) The above purpose is to
A chemical structural formula characterized by reacting a Grignard compound of 4-chloro-2-methyl-1-butene with tetramethoxynaphthalene, 2-(1-hydroxy-4-methyl-
This is achieved by a method for producing (4-pentenyl)-1,4,5,8-tetramethoxynaphthalene.
上記(1)式で表される化合物は新規物質である。 The compound represented by the above formula (1) is a new substance.
本発明方法に適用される原料物質である２−ホ
ルミル−１，４，５，８−テトラメトキシナフタ
レンは式、
で表され先に本発明者らが新規化合物として合成
したもので（J.Chem.Soc.、Chem.Commun.、
1983、987）、今一つの原料４−クロロ−２−メチ
ル−１−ブテンは市販の３−メチル−３−ブテン
−１−オールから容易に化成することができる。 2-formyl-1,4,5,8-tetramethoxynaphthalene, which is a raw material applied to the method of the present invention, has the formula: It is expressed by the present inventors and was previously synthesized as a new compound (J.Chem.Soc., Chem.Commun.,
1983, 987), another raw material, 4-chloro-2-methyl-1-butene, can be easily synthesized from commercially available 3-methyl-3-buten-1-ol.
本発明化合物は、上記４−クロロ−２−メチル
−１−ブテンにエーテル中で常法によりマグネシ
ウムを作用させてグリニヤール化合物となし、上
記２−ホルミル−１，４，５，８−テトラメトキ
シナフタレンのテトラヒドロフランなどの溶媒溶
液を加え、室温下に反応させ、塩析後、常法によ
りクロロホルムなどで抽出・精製することによつ
て取得することができる。 The compound of the present invention is obtained by reacting magnesium with the above 4-chloro-2-methyl-1-butene in ether by a conventional method to obtain a Grignard compound, and the above-mentioned 2-formyl-1,4,5,8-tetramethoxynaphthalene It can be obtained by adding a solvent solution such as tetrahydrofuran, reacting at room temperature, salting out, and extracting and purifying with chloroform or the like in a conventional manner.
次に実施例を挙げて本発明の内容をさらに詳細
に説明する。 Next, the content of the present invention will be explained in more detail by giving examples.
実施例 １
２−ホルミル−１，４，５，８−テトラメトキ
シナフタレンの製法（原料物質３）
１，４，５，８−テトラメトキシナフタレン
6.0ｇ（25ｍmol）をクロロホルム50mlに溶かし、
塩化ホスホリル19.0ｇ（125ｍmol）とＮ，Ｎ−
ジメチルホルムアミド9.0ｇ（125ｍmol）を滴下
する。のち反応系を６時間還流下に加熱する。氷
水中に注ぎ分解したのちクロロホルムで抽出し
た。抽出液を常法により水洗、乾燥したのち、ク
ロロホルムを蒸発させると結晶が残る。ヘキサン
−ベンゼン混合液で再結晶して精製し、6.72ｇ
（99％）の収率で２−ホルミル−１，４，５，８
−テトラメトキシナフタレンの黄色結晶を得た。
融点は124〜125.5℃である。標準試料と混融して
確認した。Example 1 Method for producing 2-formyl-1,4,5,8-tetramethoxynaphthalene (raw material 3) 1,4,5,8-tetramethoxynaphthalene
Dissolve 6.0g (25mmol) in 50ml of chloroform,
Phosphoryl chloride 19.0g (125mmol) and N,N-
9.0 g (125 mmol) of dimethylformamide is added dropwise. The reaction system is then heated under reflux for 6 hours. After decomposition by pouring into ice water, the mixture was extracted with chloroform. After the extract is washed with water and dried in a conventional manner, the chloroform is evaporated to leave crystals. Purified by recrystallization with hexane-benzene mixture, 6.72g
2-formyl-1,4,5,8 with a yield of (99%)
- Yellow crystals of tetramethoxynaphthalene were obtained.
The melting point is 124-125.5°C. Confirmed by mixing with standard sample.
実施例 ２
４−クロロ−２−メチル−１−ブテン（原料物
質）の製法
３−メチル−３−ブテン−１−オール102ｇ
（1.18mol）をピリジン103ｇ（1.30mol）に溶か
し、−５℃に冷却して塩化チオニル155ｇ
（1.30mol）を−５〜＋３℃で３時間で滴下する。
なお０℃で６時間かきまぜて反応を続け、のち室
温で一夜放置する。200mlの水を加えて水蒸気蒸
留する。食塩で塩析して有機物層を分かち、塩化
カルシウムで乾燥する。分別蒸留すると21.4ｇ
（20％）のイソプレン（bp34.5℃）が留出したの
ち、４−クロロ−２−メチル−１−ブテン24.5ｇ
（20％）、bp102.5℃（文献値102℃、W.Kirmse、
M.Kapps、R.B、Hager、Chem、Ber.、1966
99、2855）が得られる。Example 2 Method for producing 4-chloro-2-methyl-1-butene (raw material) 102 g of 3-methyl-3-buten-1-ol
(1.18 mol) was dissolved in 103 g (1.30 mol) of pyridine, cooled to -5℃, and 155 g of thionyl chloride was added.
(1.30 mol) was added dropwise over 3 hours at -5 to +3°C.
The reaction was continued by stirring at 0°C for 6 hours, and then left overnight at room temperature. Add 200ml of water and steam distill. Salt out with common salt to separate the organic layer, and dry with calcium chloride. 21.4g when fractionally distilled
(20%) of isoprene (bp34.5℃) was distilled out, and 24.5g of 4-chloro-2-methyl-1-butene
(20%), bp102.5℃ (literature value 102℃, W.Kirmse,
M.Kapps, R.B., Hager, Chem, Ber., 1966
99, 2855) is obtained.
実施例 ３
２−（１−ヒドロキシ−４−メチル−４−ペン
テニル）−１，４，５，８−テトラメトキシナ
フタレン(1)の製法
４−クロロ−２−メチル−１−ブテン1.04ｇ
（0.01mol）を２mlのエーテルと10mlのテトラヒ
ドロフランで覆つたマグネシウム0.244ｇ
（0.01mol）に滴下し、グリニヤール溶液をつく
る。２−ホルミル−１，４，５，８−テトラメト
キシナフタレン(3)0.77ｇ（2.8ｍmol）をテトラヒ
ドロフラン５mlに溶かした溶液を０℃でかきまぜ
ながら滴下し、さらに室温で１時間反応させる。
のち塩化アンモニウム水溶液を加えて分解し、ク
ロロホルムで抽出する。抽出液を常法により炭酸
水素ナトリウム水、食塩水で洗浄し、無水硫酸ナ
トリウムで乾燥し、溶媒を除くと油状の生成物(1)
0.96ｇ（95％）が得られる。要すればシリカゲ
ル、もしくはアルミナゲルのカラムクロマトグラ
フイーでクロロホルムを用いて精製する。以下に
示す分析によつて化合物(1)であることが確認され
た。Example 3 Process for producing 2-(1-hydroxy-4-methyl-4-pentenyl)-1,4,5,8-tetramethoxynaphthalene (1) 1.04 g of 4-chloro-2-methyl-1-butene
0.244 g of magnesium (0.01 mol) covered with 2 ml of ether and 10 ml of tetrahydrofuran
(0.01mol) to make a Grignard solution. A solution of 0.77 g (2.8 mmol) of 2-formyl-1,4,5,8-tetramethoxynaphthalene (3) dissolved in 5 ml of tetrahydrofuran was added dropwise with stirring at 0° C., and the mixture was further reacted at room temperature for 1 hour.
Afterwards, ammonium chloride aqueous solution is added to decompose, and the mixture is extracted with chloroform. The extract was washed with aqueous sodium bicarbonate and brine in a conventional manner, dried over anhydrous sodium sulfate, and when the solvent was removed, an oily product (1) was obtained.
0.96g (95%) is obtained. If necessary, purify by silica gel or alumina gel column chromatography using chloroform. It was confirmed to be compound (1) by the analysis shown below.
赤外分析3480（OH）、1645（Ｃ＝Ｃ）、880cm-1（
Ｃ＝CH2）。Infrared analysis 3480 (OH), 1645 (C=C), 880 cm -1 (
C= CH2 ).
NMR分析（CDCl3）δ1.75（ｓ、3H、CH3）、1.8
〜2.4（ｍ、5H、２×CH2とOH）、4.74（ｍ、
2H、Ｃ＝CH2）、5.22（ｔ、1H、Ｊ＝６、４
Hz、−ＣＨ（OH）−）、6.81（ｓ、2H、ArH）、
6.98（ｓ、1H、ArH）。NMR analysis (CDCl 3 ) δ1.75 (s, 3H, CH 3 ), 1.8
~2.4 (m, 5H, 2 x CH2 and OH), 4.74 (m,
2H, C=CH 2 ), 5.22 (t, 1H, J=6, 4
Hz, -C H (OH) -), 6.81 (s, 2H, ArH),
6.98 (s, 1H, ArH).
マススペクトル分析MSm／e346（M+）、328（M+
−H2O）、313、258、243、234。Mass spectrum analysis MSm/e346 (M + ), 328 (M +
−H2O ), 313, 258, 243, 234.
元素分析 C20O26H5としての
計算値 Ｃ、69.34：Ｈ、7.56％
分析値 Ｃ、68.84：Ｈ、7.54％
赤外分析図、NMR分析図、マススペクトル分
析図をそれぞれ第１〜３図に示す。Elemental analysis Calculated value as C 20 O 26 H 5 C, 69.34: H, 7.56% Analytical value C, 68.84: H, 7.54% Infrared analysis chart, NMR analysis chart, and mass spectrum analysis chart are shown in Figures 1 to 3, respectively. Shown below.
（発明の効果）
本発明によりシコニンの合成法における工程が
著しく短縮され、合理化が達成される。その工程
を反応式で示せば次の通りである。(Effects of the Invention) According to the present invention, the steps in the shikonin synthesis method are significantly shortened and rationalization is achieved. The process is shown in the following reaction formula.
（特開昭61−204153号の方法）（特開昭59−
175449号の方法） (method of JP-A-61-204153) (JP-A-59-
175449 method)
第１図〜第３図は、本発明新規化合物について
のそれぞれ赤外分析図、NMR分析図およびマス
スペクトル分析図である。
FIGS. 1 to 3 are an infrared analysis diagram, an NMR analysis diagram, and a mass spectrum analysis diagram, respectively, for the novel compound of the present invention.
Claims (1)
４−ペンテニル）−１，４，５，８−テトラメト
キシナフタレン。 ２ ２−ホルミル−１，４，５，８−テトラメト
キシナフタレンに４−クロロ−２−メチル−１−
ブテンのグリニヤール化合物を反応させることを
特徴とする化学構造式、 で表される２−（１−ヒドロキシ−４−メチル−
４−ペンテニル）−１，４，５，８−テトラメト
キシナフタレンの製造法。[Claims] 1. Chemical structural formula, 2-(1-hydroxy-4-methyl-
4-pentenyl)-1,4,5,8-tetramethoxynaphthalene. 2 2-formyl-1,4,5,8-tetramethoxynaphthalene with 4-chloro-2-methyl-1-
A chemical structural formula characterized by reacting a Grignard compound of butene, 2-(1-hydroxy-4-methyl-
4-Pentenyl)-1,4,5,8-tetramethoxynaphthalene production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25555186A JPS63112531A (en) | 1986-10-29 | 1986-10-29 | 2-(1-hydroxy-4-methyl-4-pentenyl)-1,4,5,8-tetramethoxy-n aphthalene and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25555186A JPS63112531A (en) | 1986-10-29 | 1986-10-29 | 2-(1-hydroxy-4-methyl-4-pentenyl)-1,4,5,8-tetramethoxy-n aphthalene and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63112531A JPS63112531A (en) | 1988-05-17 |
| JPH0470295B2 true JPH0470295B2 (en) | 1992-11-10 |
Family
ID=17280294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25555186A Granted JPS63112531A (en) | 1986-10-29 | 1986-10-29 | 2-(1-hydroxy-4-methyl-4-pentenyl)-1,4,5,8-tetramethoxy-n aphthalene and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63112531A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100336792C (en) * | 2005-04-21 | 2007-09-12 | 上海交通大学 | Total synthesis method for preparing receme alkannin |
| CN105642127B (en) * | 2016-01-13 | 2018-01-05 | 厦门理工学院 | A kind of preparation method of anthraquinone functionalization polyvinylidene fluoride (PVDF) ultrafiltration membrane |
-
1986
- 1986-10-29 JP JP25555186A patent/JPS63112531A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63112531A (en) | 1988-05-17 |
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