JPS5984857A - Manufacture of 9-(3-methylimino-1-propenyl)-anthracene - Google Patents
Manufacture of 9-(3-methylimino-1-propenyl)-anthraceneInfo
- Publication number
- JPS5984857A JPS5984857A JP58171437A JP17143783A JPS5984857A JP S5984857 A JPS5984857 A JP S5984857A JP 58171437 A JP58171437 A JP 58171437A JP 17143783 A JP17143783 A JP 17143783A JP S5984857 A JPS5984857 A JP S5984857A
- Authority
- JP
- Japan
- Prior art keywords
- methylimino
- anthracene
- propenyl
- formula
- manufacture
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/38—Unsaturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings
- C07C47/44—Unsaturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings polycyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/24—Anthracenes; Hydrogenated anthracenes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
本りｔｓ １ｊｌＪは式
％式％
で表わされる化合物をメチルアミンと反応させることか
ら成る、式
で表わされる９−（６−メチルイミノ−１−プロペニル
）−アントラセンの製法にｂＡ”ｆル。DETAILED DESCRIPTION OF THE INVENTION This paper ts 1jlJ describes a process for the preparation of 9-(6-methylimino-1-propenyl)-anthracene represented by the formula %, which comprises reacting a compound represented by the formula % with methylamine. bA”f le.
本発明の化合物は価値ある化合物脣に系学的に活性な化
合物例えは向精神系的に活性な化合ｑｓ９−（ｒ−７ミ
ノプロビルＪ−９，１０−ジヒドロ−９，１０−エタノ
ーフントラセン（米国！侍８「第３，３９９．２ ［Ｊ
１号明細曹に記載）藪埴用の中間生成物である。この
活性１ヒ合物は、例えは本明細’４ＭＫ記載の方法によ
って作られた納規１ヒ会物ケ、エチレンと反応させ、式
０Ｈ＝ＯＨ−ＯＲ＝ＮＯＨ３
で表わされる化合物を得、そして生成した化合物を次に
水素ｌｊ刀１１することにより製造することができる。The compounds of the present invention are valuable compounds as well as systematically active compounds, such as the psychoactively active compound qs9-(r-7minoprovir J-9,10-dihydro-9,10-ethanolophuntracene( USA! Samurai 8 “No. 3,399.2 [J
(described in Specification No. 1) This is an intermediate product for Yabutani. This active compound is reacted with ethylene, for example, by the method described in the specification '4MK, to obtain a compound of the formula 0H=OH-OR=NOH3, and The resulting compound can then be produced by hydrogenation.
式（Ｕ）で表わされる出発物質は、式
で表わされる化合物なアセタール化し、そし−Ｃｍられ
たアセタール化化合物をエチニルエーテルまたはエチニ
ルエステル例工ばビニルエーテルまたはビニルエステル
と反応させ、そし【生成する縮分生成物を酸水ｆｔ４液
で分解することにより得ることができる。The starting material of formula (U) is obtained by acetalizing a compound of formula, reacting the acetalized compound with -Cm with an ethynyl ether or ethynyl ester, such as a vinyl ether or vinyl ester, and It can be obtained by decomposing the fraction product with ft4 acid water.
ル；下本発明をその実施例につい【さらに具体的に説明
する。Below, the present invention will be described in more detail with reference to its embodiments.
例 １
６−（９−アンスリル）−アクロレイン１１．６ｇと３
３％エタノール性メチルアミン９．１１との無水エタノ
ールｆＪＱｍｅ中の混合物ｖ２０分間かぎまぜながら徐
徐に４０゛υＫ ７Ｊ［Ｉ熱する。このαγ明な褐負色
浴液を０℃に冷却すると暗黄色の結晶が分離する。これ
をろ別し、イソゾロパノール１５ｍ１および酢酸エチル
５ｒｎｅからｌ＊ ａ；ｙ晶する。こうして構造式
％式％
で表わされる９−（６−メチルイミノ−１−プロペニル
ノーアントラセンが線片１２２．５〜１２４．５ （、
！の黄色側状体として得られる。Example 1 6-(9-anthril)-acrolein 11.6g and 3
Heat the mixture in absolute ethanol fJQme with 3% ethanolic methylamine 9.11 v slowly to 40°υK 7J [I] with stirring for 20 minutes. When this αγ bright brown-negative bath liquid is cooled to 0° C., dark yellow crystals are separated. This is filtered and crystallized from 15 ml of isozolopanol and 5 rne of ethyl acetate. In this way, 9-(6-methylimino-1-propenylnoanthracene represented by the structural formula % formula % has a wire segment of 122.5 to 124.5 (,
! Obtained as yellow lateral bodies.
出発物質はυ下のようＫし′Ｃ得られる。The starting material is converted to K'C as shown below.
オルトぎ酸トリエチルエステル１３７．１．ＦＫＥ？、
−ジエチルエーテラートＱ、ｆ３ｍｌを添加し、仄にか
きまぜながらアントラセン−９−７′ルデヒド１６４．
８ 、ＳＦを少量宛添加する。生成するＡ色ベーストを
４０〜４５“υに加熱すると、粘稠な４＃ｉ５亦色溶液
が徐徐に生成する。２時間後にフラスコの内容物を冷却
し始め、同時にエチルビニルエーテル６３．４．９を反
応混合物の温度が２０℃を越えないような速度で滴加す
る。２時間後にイソゾロパノール１６１ ｍｌおよび２
規定塩ｆＲ２４ｍｌを添加し、混合物を還流しながら８
時間力ｏＭする。約１〜２時間後に生成物は比軟的急速
に析出し始める。混合物を５“Ｃに冷却し、微細な濃い
黄色の結晶をろ別スる。これを各８（Ｊｍｌのイソプロ
パツールで２ｔｍａ沖し、ｆ３（Ｊａｇの水で１回抗浄
し、史に８０ｍ１のイソゾロパノールで洗沖し、こうし
て得た構造式
で表わされる６−（９−アンスリル）−７クロレイｙ
？ ８ Ｕ ｍｍ Ｈｇ ／ ８０ ”（３で＾空中で
Ｍ）ｋが一定になるまで１２時間乾燥する。この物質は
黄金色であり、１７２〜１７４′υで融解し、クロロホ
ルム−酢酸エチルから１回再結晶した後に１７４〜１７
５℃で融解する。収量は１７１．？（＠ｉ＃廠の９２％
）である。Orthoformic acid triethyl ester 137.1. FKE? ,
-Add 3 ml of diethyl etherate Q, and stir gently while anthracene-9-7'rudehyde 164.
8. Add a small amount of SF. When the resulting A color base is heated to 40-45"υ, a viscous 4#i5+ color solution is gradually formed. After 2 hours, the contents of the flask begin to cool and at the same time ethyl vinyl ether 63.4.9 are added dropwise at such a rate that the temperature of the reaction mixture does not exceed 20° C. After 2 hours, 161 ml of isozolopanol and 2
24 ml of normal salt fR was added and the mixture was refluxed for 8 hours.
Time power oM. After about 1-2 hours the product begins to precipitate out rapidly. The mixture was cooled to 5"C and the fine dark yellow crystals were filtered out. Each of these was washed with 8 (Jml) isopropanol for 2 tma, washed once with F3 (Jag) of water, and washed with water. 6-(9-anthryl)-7chlorei expressed by the structural formula obtained by washing with 80 m1 of isozolopanol
? Dry for 12 hours to a constant k of 8 U mm Hg/80" (3^M in air). The material is golden yellow, melts at 172-174'υ, and is washed once from chloroform-ethyl acetate. 174-17 after recrystallization
Melt at 5°C. The yield is 171. ? (92% of @i#廠
).
参考例１
トルエン１５ＱｉＪ中の？−（６−メチルイミノ−１−
プロペニル）−アントラセン１２．２５．？＝にオート
クレーブ中でｉ ｓ ｏ ”ｃに加熱する。熱エチレン
の注入により８０気圧に加圧し、反応編合′甥を８０気
圧の圧力および１８υ゛υのｍ［Ｋ ２０時間おく。混
合物を冷却し、共窒中で浦発させる。Reference example 1 In toluene 15QiJ? -(6-methylimino-1-
propenyl)-anthracene 12.25. ? Pressurize to 80 atm by injection of hot ethylene and leave the reaction mixture at a pressure of 80 atm and m[K of 18 υ゛υ for 20 hours. Cool the mixture. Then, it is released in a co-nitrogen tank.
こうして構造式
で表わされる粗製の９−（３−メチルイミノ−１−プロ
ペニル）−９，１０−ゾヒドローソ、１〇−エタノーア
ントラセンが褐色の無理形物質として得られる。In this way, crude 9-(3-methylimino-1-propenyl)-9,10-zohydroso, 10-ethanoanthracene represented by the structural formula is obtained as a brown irrational substance.
試料をメタノールから結晶させ、そして再結晶させる。The sample is crystallized from methanol and recrystallized.
この無色の結晶は融点１２８〜１２９′υをもつ。The colorless crystals have a melting point of 128-129'υ.
参考例２
参考例１に記載の融麿１２８〜１２９ ”Ｃの？−（３
−メチルイミノ−１−プロペニルフーソ。Reference Example 2 Yumaro 128-129”C?-(3
-Methylimino-1-propenylfuso.
１０−ジヒドロ−９，１０−ニタノーフントラセン５．
４６１を水添用オートクレーブ中で、う不一・ニッケル
１．Ｕ 、？ （！たは１υチパラジウム炭０．３ ｐ
）の存在下におい【、１００“Ｃおよびｉｕ。10-dihydro-9,10-nitanophantracene5.
461 in a hydrogenation autoclave, nickel 1. U,? (! or 1υ palladium charcoal 0.3 p
) in the presence of [, 100"C and iu.
気圧（ケ゛−ジ圧）の水素圧で、梢製アルコールＩＯ，
Ｕ＋＋＋ｅ中で１０時間水素絵加する。６１却後に触媒
をろ別し、ｋｊ剤な真空中で半分まで＃貿する。Atmospheric pressure (cage pressure) hydrogen pressure, Kozue alcohol IO,
Add hydrogen for 10 hours in U+++e. 6. After cooling, the catalyst is filtered and transferred to half in a vacuum.
次にこの溶液に編化水素の酢酸エチル中の２規定溶融を
この溶液が弱酸性反応を示すまでｇＮ加する。Next, gN of a 2N melt of hydrogen formation in ethyl acetate is added to this solution until the solution exhibits a weakly acidic reaction.
こうして４１４ｍ式
で衣わさ１する融点２４１〜２４３℃の９−（３−メチ
ルアミノプロピル）−９，１０−ジヒドロ−９，１０−
エタノ−アントラセン塩酸塩が晶出する。イソプロパツ
ールから再結晶すると１融点２４６〜２４４°′Ｃの無
色の結晶が得られる。In this way, 9-(3-methylaminopropyl)-9,10-dihydro-9,10- with a melting point of 241 to 243°C is prepared using the 414m formula.
Ethano-anthracene hydrochloride crystallizes out. Recrystallization from isopropanol gives colorless crystals with a melting point of 246-244°C.
Claims (1)
から成る、式 で戒ねされる９−（６−メチルイミノ−１−プロペニル
）−フントラ七ンの製法。[Claims] A process for the preparation of 9-(6-methylimino-1-propenyl)-huntra7ine, which is defined by the formula, and which comprises reacting the compound of the formula 1 with methylamine.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH2576/71 | 1971-02-23 | ||
| CH257671A CH552548A (en) | 1971-02-23 | 1971-02-23 | 9-(3-oxo-1-propenyl)-9,10-dihydro-9,10-ethenoanthracenes - - inters for psychotropic drugs |
| CH667/72 | 1972-01-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5984857A true JPS5984857A (en) | 1984-05-16 |
| JPS6121943B2 JPS6121943B2 (en) | 1986-05-29 |
Family
ID=4236901
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56088325A Expired JPS5915892B2 (en) | 1971-02-23 | 1981-06-10 | 3-(9-Anthryl)-Production method of acrolein |
| JP58171438A Expired JPS6014016B2 (en) | 1971-02-23 | 1983-09-19 | Process for producing 9-(3-methylamino-1-propenyl)-anthracene |
| JP58171437A Granted JPS5984857A (en) | 1971-02-23 | 1983-09-19 | Manufacture of 9-(3-methylimino-1-propenyl)-anthracene |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56088325A Expired JPS5915892B2 (en) | 1971-02-23 | 1981-06-10 | 3-(9-Anthryl)-Production method of acrolein |
| JP58171438A Expired JPS6014016B2 (en) | 1971-02-23 | 1983-09-19 | Process for producing 9-(3-methylamino-1-propenyl)-anthracene |
Country Status (2)
| Country | Link |
|---|---|
| JP (3) | JPS5915892B2 (en) |
| CH (2) | CH544732A (en) |
-
1971
- 1971-02-23 CH CH871773A patent/CH544732A/en not_active IP Right Cessation
- 1971-02-23 CH CH257671A patent/CH552548A/en not_active IP Right Cessation
-
1981
- 1981-06-10 JP JP56088325A patent/JPS5915892B2/en not_active Expired
-
1983
- 1983-09-19 JP JP58171438A patent/JPS6014016B2/en not_active Expired
- 1983-09-19 JP JP58171437A patent/JPS5984857A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| CH552548A (en) | 1974-08-15 |
| JPS6014016B2 (en) | 1985-04-11 |
| CH544732A (en) | 1974-01-15 |
| JPS5915892B2 (en) | 1984-04-12 |
| JPS6121943B2 (en) | 1986-05-29 |
| JPS57126439A (en) | 1982-08-06 |
| JPS5980639A (en) | 1984-05-10 |
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