TW442487B - Benzodifurantriones, a process for their preparation, compounds prepared therefrom and their preparation processes - Google Patents
Benzodifurantriones, a process for their preparation, compounds prepared therefrom and their preparation processes Download PDFInfo
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經濟部中央標準局員工消f合作社印製 A6 B6 五、發明説明(1 ) 本發明係闞於苯并二呋哺三麵與彼等之互變異構形式、 一種彼等之製備方法、中間物酸氣化物、苯并二呋喃酮之 製備方法、中間物苯并呋哺_及一種笨并呋哺酮之製備方 法0 根據本發明之第一項特性》有提供化學式(1):Printed by the staff of the Central Bureau of Standards, Ministry of Economic Affairs, A6, B6. Cooperatives. 5. Description of the invention (1) The present invention is a tautomeric form of benzodifuran and their tautomers, a method for their preparation, and an intermediate. Method for preparing acid gas, benzodifuranone, intermediate benzofuran and a method for preparing benzofuranone 0 According to the first characteristic of the present invention, the chemical formula (1) is provided:
化學式[1] 之苯并二呋喃三酮I 其中: W係未經取代或經取代之芳基。 w之遘合之取代基之簧例係烷基;烯基;烷氧基;烷氧 基烷基:烷氧基烷氧基;烷基羰基;烷氧基羰基;烷氧基 羰基烷氧基;烷氧基烷氧基羰基烷氧基;烷基羰基伸氧基 烷氧基;氰基烷基;氰基烷氧基;羥基烷基;羥基烷氧基 :鹵素基烷基,特別地氟基-、氯基-或溴基烷基;鹵素 基烷氧基,特別地氟基-、氯基-或溴基烷氧基;烷基硫 基;芳基硫基;芳基伸氧基;烷基磺醯基;芳基磺醯基; 鹵素基,特別地氣基或溴基;羥基;氰基;硝基;胺基; 垸基胺基;二烷基胺基;環烷基胺基:烷基羰基胺基;芳 基羰基胺基;烷基磺醯基胺基;芳基磺釀基胺基;環烷基 本纸張尺度逋用中國國家標準(CNS) f 4規格(210X 297公釐丨 .....................................................................................裝.............. 訂 .............線 (請先閃讀背面之;±意事項再塡寫本頁) 442487 A6 B6 五、發明説明(2 ) :及被-CN 、-C1 、-F、-Br 、-OH 、-C00C ι-4-烷基、 -COOCi-4-烷基OCi-4-烷基、-苯基、-OCOC:-*-烷基取 代之烷基胺基與二烷基胺基;以及較佳地在此等基中之烷 基或烷氧基包含自1至8個碳原子,特別地自1至4個碳 原子;烯基包含自2至6個碳原子|特別地自2至4個碳 原子;芳基係笨基或萘基及環烷基包含自3至8個碳原子 *更佳地自4至6個碳原子而特別地6個碳原子。每届烷 基、烷氧基或烯基可分別地係直鏈或支鍵烷基或烷氧基。 W較佳地係萘基或笨基,更佳地化學式:Benzodifurantrione I of the formula [1] wherein: W is an unsubstituted or substituted aryl group. Examples of the combined substituents of w are alkyl; alkenyl; alkoxy; alkoxyalkyl: alkoxyalkoxy; alkylcarbonyl; alkoxycarbonyl; alkoxycarbonylalkoxy ; Alkoxyalkoxycarbonylalkoxy; alkylcarbonyl alkoxyalkoxy; cyanoalkyl; cyanoalkoxy; hydroxyalkyl; hydroxyalkoxy: haloalkyl, especially fluorine -Yl, chloro- or bromoalkyl; haloalkoxy, especially fluoro-, chloro- or bromoalkoxy; alkylthio; arylthio; aryloxy; alkyl Sulfofluorenyl; arylsulfofluorenyl; halogen, especially gas or bromo; hydroxyl; cyano; nitro; amine; fluorenylamino; dialkylamino; cycloalkylamino: Alkylcarbonylamino group; arylcarbonylamino group; alkylsulfonylamino group; arylsulfonylamino group; cycloalkyl This paper is in accordance with Chinese National Standard (CNS) f 4 (210X 297mm)丨 ................................................. ................................................. Order ............. line (please read the back of the page first; ± notes before writing this page) 442 487 A6 B6 V. Description of the invention (2): and -CN, -C1, -F, -Br, -OH, -C00C-4-alkyl, -COOCi-4-alkylOCi-4-alkyl , -Phenyl, -OCOC:-*-alkyl substituted alkylamino and dialkylamino groups; and preferably alkyl or alkoxy groups in these groups contain from 1 to 8 carbon atoms , Especially from 1 to 4 carbon atoms; alkenyl contains from 2 to 6 carbon atoms | especially from 2 to 4 carbon atoms; aryl-based benzyl or naphthyl and cycloalkyl contains from 3 to 8 Carbon atoms * more preferably from 4 to 6 carbon atoms and especially 6 carbon atoms. Each alkyl, alkoxy or alkenyl group can be a straight or branched alkyl or alkoxy group, respectively. Preferably it is naphthyl or benzyl, more preferably its chemical formula:
經濟部中央標準局員工消費合作社印製 之一涸基, 其中: 環A係未經取代或被自1至5個基取代。 環A之較佳取代基係選自Ci-4-烷基、Ci-4-烷氧基、 羥基、Cx-4-烷氧基-烷氧基羰基“-4-烷氧基、胺 基、-烷基胺基與(Ci-4-皖基)2胺基及其組合物。 環A較佳地係未纆取代或係被自1至3個基取代。在1 俚取代基存在於環A中之情況下此取代基較佳地偽在4 -位 置中,在2涸取代基存在於環A之情況下此等取代基較佳 地係在3-與4-位置中* Μ及在3個取代基存在於瑁A之情 況中此等取代基較桂地係在3-、4-與5-位置中。 -4- 本紙張尺度逋用中國國家標準(CNS)甲4規格(210x297公釐) ...............................................................................裝......................訂.............線 請先別讀背面之,注意事項再塡寫夂頁) 442487 A6 B6 五、發明説明(3 ) 化學式(1)之苯并二呋喃三酮可以多棰互變異構形式存 在*例如K由化學式(1A)與(1B):One of the bases printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, where: Ring A is unsubstituted or replaced by 1 to 5 bases. Preferred substituents for ring A are selected from Ci-4-alkyl, Ci-4-alkoxy, hydroxyl, Cx-4-alkoxy-alkoxycarbonyl "-4-alkoxy, amine, -Alkylamino and (Ci-4-Anil) 2amino and combinations thereof. Ring A is preferably unsubstituted or substituted with from 1 to 3 groups. Substituents are present in the ring at 1 俚In the case of A, this substituent is preferably pseudo in the 4-position, and in the case where a 2 'substituent is present in ring A, these substituents are preferably in the 3- and 4-positions * M and in In the case where 3 substituents are present in 瑁 A, these substituents are in the 3-, 4-, and 5-positions than Guidi. -4- This paper size uses the Chinese National Standard (CNS) A4 size (210x297) (Mm) ............................... ................................................................. ..... Order ............. Please do not read the back of the line first, and then write the title page for precautions) 442487 A6 B6 V. Description of the invention (3) of the chemical formula (1) Benzodifurantriones can exist in the polyfluorene tautomeric form * For example, K is represented by the chemical formulas (1A) and (1B):
化學式[1A] 化學式[1B] 代表之形式,及計盪由化學式(1)代表之结構包括所有互 變異構形式。 根據本發明之另一項特徴,係提供一棰製備式U)之苯 并二呋喃三醣之方法,係經由式(2)化合物: 先-"讀背面之,注意事項再填窩本頁) 裝The formula represented by Chemical Formula [1A], and the structure represented by Chemical Formula (1) includes all tautomeric forms. According to another feature of the present invention, a method for preparing a benzodifuran triose of formula U) is provided by using a compound of formula (2):-Read the "back", and then note the page ) Loaded
0H0H
經濟部t央標準局員工消费合作社印製 化學式[2] 與式(3)化合物之反« :Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. The inverse of the compound of formula [2] and formula (3) «:
化學式[3] 本紙張尺度遴用十國a家樣準(CNS)甲4現格1.210X297公釐) 442487 A6 B6 五、發明説明(4 ) 其中: V係如上文定義;及 每個X與X1分別地係鹵素基;烷基;-OH ; -HH2; -HH烷基與-Η (烷基)2。 由X與X1代表之鹵素基較佳地係- Cl 、-Br或-1,及更 佳地-Cl 、-Br 。由X與X1代表之-0烷基較佳地係 -OCi-e-烷基,更佳地-OCi-u-烷基及特別地-0CH3或 -〇C2H5。由X與X1代表之-NH烷基較佳地偽-NHCi-e-烷基 及更佳地-MHCx-4-烷基。由X與X1代表之-H (烷基)2較佳 地係-N (Ci-e-烷基>2及更佳地-N (Ci-4-烷基)2。 X及X1較佳地係-C1或-Br 。 視使用之反應條件而定,化學式(2)之化合物與化學式 (3)之化合物之反應可K 一個或兩倨階段發生。 在一種兩個階段反應中,首先將化學式(2)之一種化合 物與化學式(3)之一棰化合物反應K生成化學式(4):Chemical formula [3] This paper uses 10 national standards (CNS) A4 (1.210X297mm) 442487 A6 B6 V. Description of the invention (4) Where: V is as defined above; and each X and X1 is a halogen group; alkyl; -OH; -HH2; -HH alkyl and -fluorene (alkyl) 2. The halogen group represented by X and X1 is preferably -Cl, -Br or -1, and more preferably -Cl, -Br. The -0 alkyl group represented by X and X1 is preferably -OCi-e-alkyl group, more preferably -OCi-u-alkyl group and particularly -0CH3 or -OC2H5. The -NH alkyl represented by X and X1 is preferably pseudo-NHCi-e-alkyl and more preferably -MHCx-4-alkyl. -H (alkyl) 2 represented by X and X1 is preferably -N (Ci-e-alkyl) 2 and more preferably -N (Ci-4-alkyl) 2. X and X1 are preferred The ground system is -C1 or -Br. Depending on the reaction conditions used, the reaction of the compound of the formula (2) and the compound of the formula (3) can occur in one or two stages. In a two-stage reaction, first, A compound of chemical formula (2) reacts with a hydrazone compound of chemical formula (3) to form chemical formula (4):
化學式[4] 裝......................訂....................線 I.請先閃讀背面之.注意事項再填寫本頁) 經濟部t夬標準局員工消费合作社印製 之〜種化合物* 其中: 本纸張尺度適用中國國家標準(CSS)甲4規格(210x297公釐) 442487 -濟部中央標準局貝工消费合作社印製 A6 ____B6_ 五、發明説明(5 ) W與X係如上文定義。 此棰反應之第一個階段較佳地係在一棰觸媒之存在下進 行。觸媒較佳地係一種非-親核之鐮•更佳地一種第三级 胺及特別地三乙胺、吡啶、2 -二甲胺基吡啶、4 -二甲胺基 吡啶或二甲基甲醯胺。觸媒較佳地偽以化學式(2)之化合 物之0.1至5.0%重Μ比存在。 稱若霈要,可經由視情況於降低之壓力下之蒸謅以除去 反應介質而分離化學式(4>之化合物•或者可不進一步處 理即在反應之第二個階段中使用反應琨合物。 在第二個睹段中*可於一種非-親核之鐮之存在下·將 化學式U)之化合物環化成化學式(1)之笨并二呋喃三酮 ,非-親核之鹼較佳地係第三鈒胺諸如三乙胺、三丙胺、 三丁胺、Ν,Ν-二異丙基乙胺、二氮基二環辛烷或吡啶,一 種第四级箝化合物諸如Ν -乙基吡啶,一棰驗金羼碳酸鹽諸 如碳酸鉀、一種亞碩諸如二甲亞碾,或者一種鐮金屬烷氧 化物諸如第三丁氧化鉀。 非-親核之驗對化學式(4)之化合钧之比例較佳地係自 2:1至10:1,更佳地自2:1至5:1及特別地自2:1至3:1 〇 可將一棰酸结合劑加入方法之第二階段中,遘合之酸结 合劑係無楗之碳酸馥、碳酸氫鹽、氧化物及酗酸鹽諸如納 、钾或鈣碳酸鹽,納或鉀碳酸氫篇,鎂、钙或鉍氧化物或 者_酸砰。 在一種軍一階段反懕中,於一棰非-親核之鐮之存在下 -7- ί請先況讀背面之江意事項再填寫本頁) .裝 ^w 線 强疋度國固家標準(CNS)甲4規格丨210x297公釐.1 442487 A6 B6 五、發明説明(6 ) 及視情況於一種酸结合劑之存在下,化學式(2)之一種化 合物與化學式(3)之一種化合物反應。通合之非-親核之 鹼及酸結合劑係Μ上敘述者。在一種單一陏段反應中,非 -親核之鹹對化學式(1)之化合物之比例較佳地係自1:1 至10:1,更佳地自1:1至5:1及特別地自1:1至3:1 。在 一種酸結合劑與一種非-親核之《[兵同使用之情況下,结 合劑與鹼對化學式(2)之化合物之合計至少3莫耳當量偽 需要的。 本發明之單一或兩個階段反應可經由在一種液體介霣中 加熱反應物而進行•較佳地一種侑性液體介質•更佳地在 一種乾燥惰性液體介質中及特別地在一種脂族烴中諸如己 烷*或一種芳族烴諸如苯、甲笨或二甲苯,或者一種鹵化 脂族烴諸如二氯甲烷、氛彷或二氛乙烷*或者一種鹵化芳 族烴諸如氯苯或1,2-二氯笨,或者一種醚諸如二甘醇、二 甲醚、二乙醚或四氫呋喃,或者一種酯諸如醋酸乙酯或一 種醣胺諸如二甲基甲醸胺或一棰嗣諸如丙酮。 本方法之單一或闱饀階段反應較佳地搽於自20勺至180 υ,更佳地於自30t:至12〇υ ·特別地於自4〇υ至80Χ:之 溫度及啻用地於使用之液體介質之画流溫度下進行。 ©濟部中央標準局員工消费合作社印製 ί請先"讀背面之&意事項再填寫本頁} 化學式(1)之笨并二呋喃三嗣可纆由將反應混合物冷卻 與倒入水中、随後蒸皤Μ除去液體介質及經由例如遇濾之 自剌餘含水物質中分離產品,而分離出。 化學式(4)之化合物之瑁化成化學式(1)之苯并二呋喃 三_,亦可於夫里得夸夫特之條件下進行,此種情況下在 -8- 夂紙張尺度適用f國國家標準丨CNS)甲4规格丨210x297公釐丨 442487 A6 B6 五、發明説明(7 ) 一種路κ士酸諸如氯化鋁、氛化鐮(m )、Μ化鋅或三類化 晒之存在下於一種乾燥憤性液體介質中較佳地在一種脂族 烴諸如己烷、一種芳族烴諸如甲苯或二甲笨、一種鹵化腊 族烴諸如二氛甲垸或二氯乙烷或者一種鹵化芳族烴諸如氛 笨如1,2 -二氣苯中加熱酸氛化物。此種環化作用較佳地係 於自20^0至12〇υ之通度及習用於使用之液體介質之回流 溫度下進行。產品可經由將反應混合物冷卻及倒入冰與水 之混合物中、阚後分離及蒸發液賵介質而分離出。 化學式(2)之化合物可如在英固專利2068402Α中敘述, 經由氫輥或苯二酚與一種經光學地取代之苯’乙酵酸於高溫 度下在一種酸阑媒之存在下之反應、》後將反應混合物倒 入水中及經由過滹收集沈澱之產品而製備。 化學式(4)之化合物係新穎的及於是此形成本發明之另 一項特性,有提供化學式(4): 〇Chemical formula [4] Loading ............ Ordering ............ Line I Please flash read the back. Please note before filling out this page) ~ Compounds printed by the Consumers' Cooperatives of the Ministry of Economic Affairs and the Standards Bureau * Among them: This paper size is applicable to China National Standard (CSS) A4 (210x297) (%) 442487-Printed by A6 ____B6_, Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (5) W and X are as defined above. The first stage of this reaction is preferably performed in the presence of a catalyst. The catalyst is preferably a non-nucleophilic sickle. More preferably a tertiary amine and especially triethylamine, pyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine or dimethyl Formamidine. The catalyst is preferably present in a ratio of 0.1 to 5.0% by weight to the compound of the chemical formula (2). It is said that if necessary, the compound of the formula (4>) can be separated by removing the reaction medium by distillation under reduced pressure as appropriate, or the reaction complex can be used in the second stage of the reaction without further processing. In the second paragraph, it can be cyclized in the presence of a non-nucleophilic sickle. The compound of formula U) is cyclized into a benzodifuran trione of formula (1). The non-nucleophilic base is preferably Tertiary amines such as triethylamine, tripropylamine, tributylamine, N, N-diisopropylethylamine, diazabicyclooctane or pyridine, a fourth-order clamp compound such as N-ethylpyridine, A test gold carbonate such as potassium carbonate, an asusol such as dimethyl arylene, or a sickle metal alkoxide such as third potassium butoxide. The ratio of the non-nucleophilic test to the chemical compound (4) is preferably from 2: 1 to 10: 1, more preferably from 2: 1 to 5: 1 and particularly from 2: 1 to 3: 10. A monoacid binding agent may be added to the second stage of the method. The combined acid binding agent is free of rhenium carbonate, bicarbonate, oxides, and acid salts such as sodium, potassium, or calcium carbonate. Or potassium bicarbonate articles, magnesium, calcium or bismuth oxide or _ acid bang. In the first phase of military counterattack, in the presence of a non-nuclear prokaryosis, -7- ί Please read the Jiang Yi matters on the back before filling out this page). Install ^ w 线 强强 疋 度 国 固 家Standard (CNS) A4 specifications 丨 210x297 mm.1 442487 A6 B6 V. Description of the invention (6) and optionally a compound of the chemical formula (2) and a compound of the chemical formula (3) in the presence of an acid binder reaction. General non-nucleophilic bases and acid binders are described above. In a single hydrazone reaction, the ratio of non-nucleophilic salt to the compound of formula (1) is preferably from 1: 1 to 10: 1, more preferably from 1: 1 to 5: 1 and especially From 1: 1 to 3: 1. In the case where an acid-binding agent and a non-nucleophilic compound are used together, a total of at least 3 molar equivalents of the compound and the base to the compound of formula (2) is required. The single or two-stage reaction of the present invention can be carried out by heating the reactants in a liquid medium. Preferably, an alkaline liquid medium. More preferably in a dry inert liquid medium and especially in an aliphatic hydrocarbon. Such as hexane * or an aromatic hydrocarbon such as benzene, methylbenzene or xylene, or a halogenated aliphatic hydrocarbon such as dichloromethane, ammonium or dioxane *, or a halogenated aromatic hydrocarbon such as chlorobenzene or 1, 2-Dichlorobenzyl, or an ether such as diethylene glycol, dimethyl ether, diethyl ether or tetrahydrofuran, or an ester such as ethyl acetate or a sugar amine such as dimethylformamide or a hydrazone such as acetone. The single-stage or 闱 饀 -stage reaction of the method is preferably carried out from 20 scoops to 180 υ, more preferably from 30 t: to 12 〇 · particularly at temperatures from 4 〇 to 80 ×: The liquid medium is drawn at a drawing temperature. © Printed by the Employees' Cooperative of the Central Bureau of Standards of the People's Republic of China. Please read " read the & remarks on the back and fill in this page first. Then, the liquid medium is distilled off to remove the liquid medium, and the product is separated from the remaining water-containing material through, for example, filtration, and then separated. The chemical conversion of the compound of the chemical formula (4) into the benzodifuran tri_ of the chemical formula (1) can also be performed under the conditions of Fridquaft. In this case, the country of -8- 夂 paper is applicable to the country of f Standard 丨 CNS) A4 specifications 丨 210x297 mm 丨 442487 A6 B6 V. Description of the invention (7) A kind of road kappa acid such as aluminum chloride, atmospheric sickle (m), zinc zinc or three types of chemical exposure In a dry, irritating liquid medium, preferably in an aliphatic hydrocarbon such as hexane, an aromatic hydrocarbon such as toluene or dimethylbenzene, a halogenated wax hydrocarbon such as diazaformamidine or dichloroethane, or a halogenated aromatic Groups of hydrocarbons such as benzene, such as 1,2-digas benzene, are heated by acid odorants. This cyclization is preferably performed at a degree of flow from 20 ^ 0 to 12〇υ and the reflux temperature of the liquid medium customarily used. The product can be separated by cooling and pouring the reaction mixture into a mixture of ice and water, separating it afterwards and evaporating the liquid medium. The compound of the chemical formula (2) can be reacted via an hydrogen roller or hydroquinone with an optically substituted benzene 'acetic acid at a high temperature in the presence of an acid eliminator, as described in Ingu Patent 20684402A, After that, the reaction mixture was poured into water and the precipitated product was collected by filtration. The compound of formula (4) is novel and thus forms another characteristic of the present invention, which provides formula (4): 〇
化學式[4] 裝...........…:4--------------……線 一請先閃讀背面之ΐί意事項再填寫本頁~ 經濟部中央標準局員工消f合作社印製 之一種化合物, 其中: W及X偽如上文定義。 根據本發明之另一項特激*係提供一種製備式彳^洽物 本纸張尺度適用中1國家橒準ί CNS)甲4規格(210 X 297公釐) 442487 A6 B6 五、發明説明(8 ) 之方法: 〇Chemical formula [4] Pack .................: 4 --------------...... Please read the notice on the back of the line before filling in this page ~ A compound printed by a cooperative of employees of the Central Standards Bureau of the Ministry of Economic Affairs, where: W and X are as defined above. According to another special excitement of the present invention, a preparation method is provided. The paper size is applicable in 1 country. CNS) A4 specification (210 X 297 mm) 442487 A6 B6 5. Description of the invention ( 8) Method: 〇
化學式[5] 係經由式(1)之笨并二呋哺三嗣與式(6)化合物之反應: 丫The chemical formula [5] is via the reaction of benzodifuranthine and hydrazone with the compound of the formula (6):
化學式[6] 經濟郎t央標準局員工消費合作社印製Chemical formula [6] Printed by Jiro Lang t Central Standard Bureau employee consumer cooperative
其中: 環B係未烴取代,除了基Y Μ外者,或者被一届或兩届 另外之基取代; Ϊ係一個富含電子之活化基;及 W係如上文定義。 環Β之取代基之實钶係以上為W所敘述者。於環Β被一 0另外之基取代之情況下*此取代基較佳地係在3-位置中 ,即鄰接於基Υ :於瓖Β被兩個另外之基取代之情況下· 此等取代基較佳係在3-及5-位置中*即皆鄹接於基Υ 。 由Υ代表之富含電子活化基較佳係-OR '-HRR1 、-SR -10- 本紙張尺度逋用中1 a家標準ICNS)f 4规格(210x297公踅丨 ............................................................................裝:.......................可.................線 (請先^讀背面Λ注意事項再塡寫本頁j 44248 7 經濟部中央標準局員工消費合作社印製 A6 B6 五、發明說明(9 ) 、-HHCOR2及-HHSOaR2,其中每僩R及R1分別地係-H或-$基 '環烷基、芳基或芳烷基•每涸基可視情況被取代, 从及R3涤-烷基、環烷基、芳基或芳烷基,每涸基可視情 況被取代;或者於Y係-HR R1之情況下,R及Ϊ?1連同彼等 連结之Η原子形成一雜環基、諸如一個H-六氫吡啶基或一 個嗎福啉基ί或者於Υ係- NRR1之情況下* R或R1之一傾 連同Y連结之環B之碳原子及環B上相鄰之碳原子形成一 個雙環基,諸如與環B之一涸四氳唼啉基 (tetrahydroquinolinyl)或吲跺基。在由 R 、R1 或 R2 代表 之基係經取代之情況下,較佳之取代基之實例係羥基、氮 基、溴基、硝基、氰基及(^烷氧基。 由R 、IT或Rz代表之烷基較佳地係烷基及更佳地 烷基•由R 、Ri或R2代表之芳基較佳地係苯基· Μ 及由R 'R1或R2代表之芳烷基較佳地係芳基-Ci-*-烷基及 更佳地苄基。每個烷基可係直鍵或支鐽烷基。 此方法可娌由在一棰酸縮合劑之存在下·視情況在一種 液體介質中加熱反應物而進行。酸縮合劑較佳地係一捶無 機酸•更佳地一種確酸諸如疏酸•或者一棰有機酸,更佳 地—種烷烴羧酸諸如乙酸或丙酸或者一種烷基-或芳基磺 酸諸如甲磺酸、甲笨磺酸或十二烷基笨磺酸/液《介質較 佳地係一種惰性有機液鸦,更佳地一種芳族烴諸如甲笨或 二甲苯,或者一種鹵化芳族烴諸如氛笨或1,2-二氯笨,或 者係任何上述之酸縮合劑•或者係一種或一種K上縮合爾 及/或一種或一棰K上液體介質之一種姐合物。 -11- 本紙張尺度適用中國國家搮準iCNS)甲4规格(210X 297公釐) …… ............. .............:.·.......................裝......................訂.....................線 ί請先*'4讀背面之,·ί£意事項再填寫本頁} 442487 A6 _B6 五、發明説明(l〇 ) 方法較佳地係於自5〇υ至180X;及更佳地於7〇υ至16〇υ 之溫度、Μ及於一種適合之液體介質存在之情況下、習用 地於回流下進行。 其中Υ係-0Η或其中Α帶有一個羥基之化學式(5>之化 合物•可與例如烷化劑、豳化劑或磺醸化劑進一步反應, K分別製造0烷基、0豳基及〇磺醯基衍生物。 根據本發明之另一項特戡*係提P —種製備式(5)化合 物之方法•係經由式(7)之笨并呋喃嗣:Among them: Ring B is unsubstituted hydrocarbon, except for the group Y M, or substituted by one or two other groups; Ϊ is an electron-rich activating group; and W is as defined above. The substituents of ring B are as described above. In the case where ring B is substituted with a 0 additional group * This substituent is preferably in the 3-position, ie adjacent to the group Υ: In the case where 瓖 Β is replaced with two other groups The radicals are preferably in the 3- and 5-positions *, that is, both are attached to the radical. The electron-rich activation group represented by Υ is preferably -OR '-HRR1, -SR -10- 1 paper standard ICNS) f 4 specifications (210x297) ............ ........................................ ......... install: ............ may ... ............ line (please ^ read the notice on the back Λ before writing this page j 44248 7 printed by A6 B6 of the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (9), -HHCOR2 and -HHSOaR2, where each R and R1 are -H or-$ 'cycloalkyl, aryl, or aralkyl, respectively. Each fluorenyl group may be substituted according to the circumstances, and R3 is poly-alkyl, ring Alkyl, aryl, or aralkyl, each of which may be optionally substituted; or in the case of Y-HR R1, R and Ϊ? 1 together with their attached fluorene atoms form a heterocyclic group, such as a H-hexahydropyridyl or a morpholinyl, or in the case of actinide-NRR1 * one of R or R1 is taken together with the carbon atom of ring B connected to Y and the adjacent carbon atom on ring B to form one A bicyclic group, such as tetrahydroquinolinyl or indioyl with one of the rings B. In R, R1 or In the case where the group represented by R2 is substituted, examples of preferred substituents are hydroxy, nitrogen, bromo, nitro, cyano, and (^ alkoxy. The alkyl represented by R, IT, or Rz is preferred Geoalkyl and better alkyl • Aryl represented by R, Ri or R2 is preferably phenyl · M and aralkyl represented by R'R1 or R2 is preferably aryl-Ci- * -Alkyl group and better benzyl group. Each alkyl group can be a straight bond or a branched alkyl group. This method can be performed by heating the reactants in a liquid medium in the presence of a monoacid condensing agent, as appropriate. The acid condensing agent is preferably an inorganic acid • more preferably an acid such as oleic acid • or an organic acid, more preferably—an alkanecarboxylic acid such as acetic acid or propionic acid or an alkyl-or An aryl sulfonic acid such as methanesulfonic acid, methanesulfonic acid or dodecylbenzylsulfonic acid / liquid; the medium is preferably an inert organic liquid, more preferably an aromatic hydrocarbon such as methylbenzene or xylene, or A halogenated aromatic hydrocarbon such as Benzene or 1,2-Dichlorobenzyl, or any of the above-mentioned acid condensing agents, or one or more K-condensers and / or one A sister compound of a liquid medium on K. -11- This paper size is applicable to China National Standard iCNS) A4 specification (210X 297 mm) .................. ............: .............. install ... ........... Order .............. line 请 Please read the first * '4 on the back, · 意 £ Fill out this page} 442487 A6 _B6 V. Description of the invention (10) The method is preferably from 50o to 180X; and more preferably from 70o to 160o, and a suitable liquid In the presence of a medium, the conventional site is performed under reflux. Compounds of the formula (5) in which 化学 is -0 & or wherein A bears a hydroxyl group can be further reacted with, for example, an alkylating agent, an alkylating agent or a sulfonating agent, and K produces an alkyl group, an alkyl group, and an alkyl group, respectively. Sulfonyl derivatives. According to another feature of the present invention * is the extraction of P—a method for preparing compounds of formula (5). • Via benzofuran hydrazone of formula (7):
(請先閃讀背面之„注意事項再4寫本II 0R3(Please flash down the „Cautions on the back side before writing 4 copies II 0R3
0 化學式[7] 經濟部中央標準局員工消费合作社印製 與式(6)化合物之反懕 其中: W 、環B及Y係如上文定義; R3 偽-H、-COR2 、-S02R2,其中R2偽如上文定義;Μ 及 R4 係-C00R2,其中R2係如上文定義;-C0NRR 1 ,其中 R及R1係如上文定義;-C00H或其鐮金羼、鐮土金 羼或銨鹽;或者-C0X2 ,其中X2係鹵素基。 於由R4代表之基係-C00H之金靥鼸之情況下,鹺金羼 較佳地係鋰、納或鉀,更佳地納或鉀,於R4係-C00H之晚 **12- 本紙張尺度適用中國國家標準(CNS)甲4规格(210x297公釐) 442487 經濟部中央標準局員工消費合作杜印製 Α6 Β6 五、發明説明(.11 ) 土金屬鹽之情況下*鹼土金羼較佳地係鎂或鈣,於R4係 -COOH之銨鹽之情況下·銨可係或者其中烷基包含自 1至10個碳原子之一種經單-、二-、三或四烷基取代之 銨。在基-C0X2中由X2代表之鹵素較佳地係溴基或氯基* 更佳地氯基。 此方法可纆由視情況在一種酸縮合劑之存在下及視情況 在一種液體介質之存在下*加熱反應物而進行。酸縮合劑 較佳地係一種無機酸•更佳地一種碥酸諸如硫或者一 種有楗酸,更佳地一種烷烴羧酸諸如乙酸或丙酸或者一種 烷基-或芳基磺酸諸如甲磺酸、甲笨磺酸或十二烷基苯硝 酸。液體介質較佳地係一種惰性有機液體,更佳地一種芳 族烴諸如甲苯或二甲笨*或者一種鹵化芳族烴諸如氯笨或 1,2-二氛苯,或者係任何上述之酸縮合劑*或者係一種或 一種以上縮合劑及/或一種或一種Μ上液S3介質之一種姐 合物。 方法較佳地係於自5〇υ至180TC及更佳地於70t:至16〇υ 之溫度、Κ及於一種逋合之液體介宵存在之情況下、習用 地於回流下進行。 化學式(5)之化合物可經由任何習用之方法而自反應混 合物中分離,例如經由反應琨合物之邁濾。化學式(5)之 化合物可經由任何習用之方法而纯化,諸如用一種遘合之 液體諸如甲醇或水洗滌*或者經由自—種遘合之有機液應 (諸如一種酵例如甲酵、乙酵、丙酵、2-甲氧基乙酵,一 種醯胺例如二甲基甲醸胺•或者一棰鹵化芳烴例如氯-或 -13- 本纸張尺度適用中國國家標準(CNS)甲4规格(210X297公釐)0 Chemical formula [7] Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs and the compound of formula (6) where: W, ring B and Y are as defined above; R3 pseudo-H, -COR2, -S02R2, where R2 As defined above; M and R4 are -C00R2, where R2 is as defined above; -C0NRR 1, where R and R1 are as defined above; -C00H or its sickle tincture, sickle tincture or ammonium salt; or- C0X2, where X2 is a halogen group. In the case of the base-C00H gold tincture represented by R4, the gold tincture is preferably lithium, sodium or potassium, more preferably sodium or potassium, at night of R4-C00H ** 12- this paper Standards are applicable to China National Standard (CNS) A4 specifications (210x297 mm) 442487 Consumption cooperation by employees of the Central Bureau of Standards of the Ministry of Economic Affairs Du printed A6 B6 V. Description of the invention (.11) In the case of earth metal salts * Alkaline earth gold is better Terrestrial Magnesium or Calcium, in the case of R4-series-COOH ammonium salts. Ammonium may be or ammonium substituted with mono-, di-, tri- or tetraalkyl-based ammonium. . The halogen represented by X2 in the group -COX2 is preferably a bromo group or a chloro group *, more preferably a chloro group. This method can be carried out by optionally heating the reactants in the presence of an acid condensing agent and optionally in the presence of a liquid medium. The acid condensing agent is preferably an inorganic acid. More preferably, an acid such as sulfur or an organic acid, more preferably an alkanecarboxylic acid such as acetic acid or propionic acid or an alkyl- or arylsulfonic acid such as methanesulfonic acid. Acid, methanesulfonic acid or dodecylbenzene nitric acid. The liquid medium is preferably an inert organic liquid, more preferably an aromatic hydrocarbon such as toluene or dimethylbenzyl * or a halogenated aromatic hydrocarbon such as chlorobenzyl or 1,2-dibenzobenzene, or any of the above acid condensations Agent * is a sister compound of one or more condensing agents and / or one or one M S3 medium. The method is preferably performed at a temperature from 50 to 180 TC and more preferably from 70 t: to 16 υ, K and in the presence of a mixed liquid medium, conventionally under reflux. The compound of formula (5) can be isolated from the reaction mixture by any conventional method, for example, by filtration through a reaction mixture. The compound of formula (5) can be purified by any conventional method, such as washing with a compounded liquid such as methanol or water *, or from a compounded organic liquid (such as a leaven such as formazan, acetonitrile, Propionate, 2-methoxyacetic acid, a kind of ammonium such as dimethylformamide • or a halogenated aromatic hydrocarbon such as chlorine- or -13- (Mm)
....................... ............. ……:… ............t........................玎...................^ ί請先'"讀背面之,注意事項再填寫太頁J j 2 4· 210 9 3 9 5號專利申請案 中文説明書修正頁(8 3年1 2月 7'f _<ίΒ 本 vbl- ^ v> 五、發明説明(12 ) —氣苯)中之结晶 根據本發明之另一項持遨* ί糸提供式(7 )化合物: OR3............. ............. ......: ............ ..t .............. 玎 ................... ^ ί Please First, 'read the back of the page, and pay attention to the matter before filling in the page of J j 2 4 · 210 9 3 9 No. 5 Chinese Patent Application Specification Correction Page (83 years 1 February 7'f _ < ίΒ 本 vbl- ^ v > V. Crystallization in (12)-Gas benzene) According to another aspect of the present invention, a compound of formula (7) is provided: OR3
0 經濟部中央標準局員工消費合作杜印製 化學式[7] 其中: y 、R3及R4係如上文定義= 根撺本發明之考一項特性,有提供一搏經由將化學式 (1 )之一種化合物與Z Η反應而製简化學式ί 7 j之一榷化合 物之方法,其中Z係-0 Η 、- ϋ R 2 ' - H R R 1或X 2,其中R 、 R 1、R 2 & X 2係如上文定義。 此方法可羿由視情況在一種液體介質之存在下,混合反 應物而進行。適合之液體介質可除水或任何上述之惰性有 機液體。化學式(1 )之化合物與水之反應,即於Ζ係-0 Η 之情況下,可在一棰鹼性溶液中進行。適合之鹼性溶液包 括鹸金屬氫氧化物或氫氧化鞍(諸如氫氧化納或氫氧化鉀 )之水溶液或鹼金騙碳酸謅(諸如碳酸納或碳酸鉀)之水溶 液 方法較佳地係於自0 t至1 0 (TC >更佳地於目1 〇 _;C至6 0 :C 及特別地自1 0 _t至6 (TC之溫度下進行。 化學式(7 _!之化合物可經由任何習用之方法而自反應温 -14- 本紙張尺度適用中國國家揉隼(CNS } A4規格(210X297公釐) * 813.10,000 ---------^------'订------'^ (請先閲讀背面之注意事項再填寫本頁) 4 48^^2 1 09 39 5號專利申請案 中文說明書修正頁U8年9月) A7 B7 修正補充 五、發明説明( 合物中分離*例如羥由反應混合物之過濾= 化學式⑴、⑷及⑺之化合物作為多種有楗化合物之製備 之中間钧涤有甩的,待定言之在染料、農樂化學品及醫藥 品之製造中作為中間物使用。化學式(5)之化合物可作為 染料使用·特定言之合成纺織材料諸如聚酯之著色。 本發明藉下列茛例而進一步舉例說明。 蜇例1 經濟部中央標隼局肩工消費合作社印裝 max <請先閲讀背面之注意事項再填寫本頁) 將草醯氛(2.6份)及4 -二甲胺基吡啶(0.1份)加入5 -羥 -2 -嗣-3-笨-2,3 -二氫笨并呋喃(4.52份)在乾烽二氯甲烷 (5 0份)中之懸浮液中。將混合物攪拌及於回流下加熱經過 約6小時,直到氯化氫氣體之釋出停止為止。將混合物冷卻 至20 t及滴狀地將三乙胺(5份)在乾烽二氯甲烷(25份)中 之溶液於搅拌下、在5分鐘內加入。於將混合物冷卻及倒 入水(100份)中與將2莫耳濃度氫氯酸(20份)加入之前*回 流經過另外之3小時。經由蒸餾除去二氯甲烷,Μ留下產 品如懸浮在水中之一種棕色結晶固體。經由過漶收集產品 、及將其乾燥,Κ產生7-苯-7-氫-2, 3, 6-三網-笨并[1:2 -1),4:5-1)|]二呋喃(5.3份,94.6%)。經由自乙腈中之再结 晶而純化產品(在二甲基甲醯胺中λ max =552納眾’ =35,000) ° 經纯化之產物量(重量計):2.7份 產率:43¾ 熔點:220-222 1C 结構分析得到: 15 本紙張尺度適用中國國家標隼(CNS > A4規格(2ίΟΧ297公釐〉 442487 第3 2 1 Ο 9 3 9 5號專利申請荼 中文說明書修正頁(δδ年9月) 五、發明説明( 修正 各 ί-月 Η 補充 88. 9. 10 Α7 Β70 Consumption cooperation between employees of the Central Bureau of Standards of the Ministry of Economic Affairs, printed chemical formula [7] where: y, R3, and R4 are as defined above = according to a feature of the present invention, there is a way to provide chemical formula (1) A method for preparing a compound of simplified formula Γ 7 j by reacting a compound with Z Η, wherein Z is -0 Η,-ϋ R 2 ′-HRR 1 or X 2, wherein R, R 1, R 2 & X 2 It is as defined above. This method can be performed by mixing the reactants in the presence of a liquid medium, as appropriate. Suitable liquid media may be water or any of the above inert organic liquids. The reaction of the compound of the chemical formula (1) with water, that is, in the case of Z series-0 ,, can be carried out in a 棰 alkaline solution. Suitable alkaline solutions include aqueous solutions of rhenium metal hydroxides or saddle hydroxides (such as sodium hydroxide or potassium hydroxide) or aqueous solutions of alkali gold rhenium carbonate (such as sodium carbonate or potassium carbonate). The method is preferably based on 0 t to 10 (TC > more preferably in head 1 〇_; C to 60: C and particularly from 10 _t to 6 (TC). Compounds of the chemical formula (7 _! Can be passed through any Self-reaction temperature in customary methods -14- This paper size applies to the Chinese national standard (CNS) A4 (210X297 mm) * 813.10,000 --------- ^ ------ 'Order ------ '^ (Please read the notes on the back before filling in this page) 4 48 ^^ 2 1 09 39 Revised page of the Chinese specification for Patent Application No. 5 September U8) A7 B7 Amendment Supplement V. Invention Explanation (Separation in the compound * For example, hydroxyl is filtered by the reaction mixture = compounds of formula ⑴, ⑷ and ⑺ are used as intermediates for the preparation of various fluorene compounds. There are dyes, agrochemicals and medicines to be specified. It is used as an intermediate in the manufacture of products. The compound of chemical formula (5) can be used as a dye. Specifically, synthetic textile materials such as The color of the ester. The present invention is further illustrated by the following examples. 蜇 Example 1 Printed by the Central Government Bureau of the Ministry of Economic Affairs, shoulder worker consumer cooperative, max < please read the notes on the back before filling this page) 2.6 parts) and 4-dimethylaminopyridine (0.1 parts) were added with 5-hydroxy-2 -fluorene-3-benzyl-2,3-dihydrobenzfuran (4.52 parts) in dry dichloromethane (50 0 Parts) in the suspension. The mixture was stirred and heated under reflux for about 6 hours until the release of hydrogen chloride gas stopped. The mixture was cooled to 20 t and triethylamine (5 parts) was dried in the form of drops.溶液 The solution in dichloromethane (25 parts) was added with stirring within 5 minutes. Before the mixture was cooled and poured into water (100 parts) and 2 moles of hydrochloric acid (20 parts) was added * Reflux was passed for another 3 hours. The dichloromethane was removed by distillation, leaving the product as a brown crystalline solid suspended in water. The product was collected by drying and dried to produce 7-benzene-7-hydrogen-2 , 3, 6-trinet-benzo [1: 2 -1), 4: 5-1) |] difuran (5.3 parts, 94.6%). Reconstructed from acetonitrile Crystal purified product (λ max = 552 nm in dimethylformamide) = 35,000) Purified product amount (by weight): 2.7 parts yield: 43¾ Melting point: 220-222 1C Structure analysis yields: 15 This paper size applies to the Chinese national standard (CNS > A4 size (2ίΟχ297mm) 442487 No. 3 2 1 Ο 9 3 9 No. 5 Chinese Patent Application Specification Revised Page (δδ September September) V. Description of the Invention (Revised Each ί-month Η Supplement 88. 9. 10 Α7 Β7
〇 (請先聞讀背面之注意事項再填寫本頁)〇 (Please read the notes on the back before filling in this page)
NMR PP ffl , de -DMS0: 6.80, 雙 波 峰, j = 7Hz , 2H , 7.22, 三 波 峰, j 二 7HZ , 1H, 7.40, 三 波 峰, j =7 Hz , 2H , 7.80, 雙 波 峰, j = 7Hz , 2H , 微 分析 id: 果:X C68 . 3 , Η 2.8 ,而C 1 β Η ί s〇 s要求 C 58 質譜分析 於m/2 280下測得 AJL. 从實例1之方法 經濟部中央標準局員工消費合作社印製 氯 瞌 草 將 及 份 啶 吡 基 胺 甲 羥 -- 5 Λ 加 份 5 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) 8 2 1 0 9 3 9 5號專利申請案 由々說明軎feTF苜年9月)A7 B7NMR PP ffl, de -DMS0: 6.80, double peak, j = 7Hz, 2H, 7.22, triple peak, j 7HZ, 1H, 7.40, triple peak, j = 7 Hz, 2H, 7.80, double peak, j = 7Hz , 2H, microanalysis id: Fruit: X C68. 3, Η 2.8, and C 1 β Η s s requires C 58 mass spectrometry to measure AJL at m / 2 280. Method from Example 1 Central Standard of Ministry of Economics Printed by the Consumer Cooperative of the Bureau of the People's Republic of China and Chlorpyrimidine and Pyridylamine Methyl Hydroxide-5 Λ Plus 5 copies This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 8 2 1 0 9 3 9 Patent application No. 5 is explained by 々feTF (September) (A7) B7
44248J 五、發明说明() -2 -丽- 3- (4 -甲氧基笨基)-2,3-二氫苯并呋喃(2.56份)在 二氛甲烷(25份)中之懸浮液中。 產品7-U -甲氧基笨基)-7-氫-2,3,6-三_ -笨并(1:2- 1>14:5-1)。二呋喃(3.26份;105%)。纆由研磨成粉末及用 二氣甲烷洗滌而純化◊在二甲基甲韓胺中,純化產物 (1.28份,41%)λ max 552 納米、ε max 28,680。質譜測 定顯示符合結構於310之分子難子。 芦Μ 3 以茛例2之方法。 將5-羥-2-酮-3 - (4-乙氧基拜·基)-2,3-二氣笨并呋喃 (2.7份)反應,Κ產生產品7-(4-乙氧基苯基)-7-氫-2,3, ...-· 6-三氧-苯并(1:2-1>,4:5-1)’)二呋喃.(3,25份;100%).。 在二甲基甲醯胺中纯化之i品_ (1 . 23份;38% ) λ aax 56 2納米、e max 3 1 , 429。質譜測定顯示符合结構於324 冬分子離子。 啻制4 Μ實例2之方法。 將5-羥- 2-_-3-(4-丙氧基苯基)-2,3-二氫苯并呋喃 (2.δ4份)反應,Μ產生產品7-(4-丙氧基苯基)-卜氫 3,6-三嗣-苯并(1:2-1),4:5-1),)二呋喃(3.53份;104%)。 在二甲基甲醯胺中純化之產品(1_40份,41%)λ max t 562納米、ε max 25,623。質譜測定顯示苻合结構於338 之分子離子。 - g例 以實例2之方法。 將草醯氛(3.9份)及2-二甲胺基吡啶(0.1份)加人5~徑 16 - 本紙張尺度適用中囡國家螵準(CNS ) A4说格(210X297公釐) ---------^-----^—1τ--------,ii (請先閱讀背*之注意事碩再填寫本頁) 經44248J V. Description of the invention () -2 -Li- 3- (4-methoxybenzyl) -2,3-dihydrobenzofuran (2.56 parts) in suspension in dichloromethane (25 parts) . Product 7-U -methoxybenzyl) -7-hydro-2,3,6-tri-benzyl (1: 2-1-> 14: 5-1). Difuran (3.26 parts; 105%). ◊ Purified by grinding into powder and washing with digas methane. 二 In dimethylmethanamine, the purified product (1.28 parts, 41%) λ max 552 nm, ε max 28,680. Mass spectrometry showed molecular dipoles with structure 310. LuM 3 was prepared in the same manner as in Example 2. Reacting 5-hydroxy-2-one-3-(4-ethoxybylyl) -2,3-digas benzofuran (2.7 parts) to produce the product 7- (4-ethoxyphenyl ) -7-Hydrogen-2,3, ...- · 6-trioxo-benzo (1: 2-1 >, 4: 5-1) ') Difuran. (3,25 parts; 100%) .. Product i purified in dimethylformamide (1.23 parts; 38%) λ aax 56 2 nm, e max 3 1, 429. Mass spectrometry showed molecular structures consistent with 324 winter molecular ions. Method for making 4M Example 2. The 5-hydroxy-2--2--3- (4-propoxyphenyl) -2,3-dihydrobenzofuran (2.δ4 parts) is reacted to produce the product 7- (4-propoxybenzene Phenyl) -hydrogen 3,6-trifluorene-benzo (1: 2-1), 4: 5-1),) difuran (3.53 parts; 104%). The product purified in dimethylformamide (1-40 parts, 41%) λ max t 562 nm, ε max 25,623. Mass spectrometry showed molecular ions with a coupled structure at 338. -g Example Take the method of Example 2. Add grass flavor (3.9 parts) and 2-dimethylaminopyridine (0.1 parts) to 5 ~ 16 16-This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) --- ------ ^ ----- ^ — 1τ --------, ii (Please read the note of the back * before filling in this page)
中 央 標 準 局 Ά 工 消 费 合 作 杜 印 X 44248? 82109395號專利申明票 中寸銳明軎條ΤΗ頁(85年9月丄Α7 Β7 修正補充 五、發明説明() -2-詷- 3-(4-丁氧基苯基)-2,3-二氫笨并块喃(3.49份)在 二氛甲烷(75份)中之懸浮液中。 產品7-( 4-丁氧基苯基)-7_氫-2 ,3,6-三嗣-笨并(1:2-b,4:5-b·)二呋喃(11.35份;107.5%)。 在二甲基甲醯胺中纯化之產品(3,60份,36%)λ max 561 納米、ε max 35,159’ 分析 C,68.2; Η,4.5; C20H1606要求“68.2;Η,4·5%。質譜滴定法顯不’付合结 構之於3 5 2之分子之離子與碎體15 當例6 Μ實例2之方法。 將5-羥-2-嗣- 3-(4-異丙氧p苯基)-2,3-二显苯并咲喃 (2.84份)反應,Μ產生產品7-(4-異丙氧基笨基)-7-氫_2, 3,6-三嗣-笨并(l:2*b,4:5-b,)二呋喃(3.72 份;110%) s -在二甲基甲_胺中純化之產品Π·55份,46%)λΜχ 561納芾、ε max 29,583。質.譜測定顯示苻合结構於338之 分子離子。 g俐7 以賁例2之方法。 將草醯氯(0.65份)及2-二甲胺基吡啶(〇.〇5份)加人5-徑 -2*·銅_3-(4 -甲基笨基)_2,3_二氫笨并呋喃(1.2份)在一氯 經濟部中央標準局I工消費合作社印掣 (請先閱讀背面之注意事項再填寫本頁) 甲烷(15份)中之恝浮液中。 __ 產品7-(4 -甲基苯基)-7 -氫3,6 -三嗣-苯并U:2-b’ 4:5-b,)二呋喃(1.7份;115%)。 在二甲基甲醵胺中純化之產品A max 555 . 6納來、ε 本紙張尺度適用中國國家榡準(CNS ) Α4規格(2!ΟΧ297公釐) 4 42 48f 82109395號專利申請荼 中寸為昍書條TF苜(85年A7 B7The Central Bureau of Standards, Industrial and Consumer Cooperation, Du Yin X 44248? 82109395 Patent Declaration Ticket, sharp sharp strips, Η ((September 1985 丄 Α7 Β7 Amendment Supplement V. Description of the invention () 詷 3- 3- 3- (4 -Butoxyphenyl) -2,3-dihydrobenzyl sulfan (3.49 parts) in suspension in dichloromethane (75 parts). Product 7- (4-butoxyphenyl) -7 _Hydrogen-2,3,6-trifluorene-benzyl (1: 2-b, 4: 5-b ·) difuran (11.35 parts; 107.5%). The product purified in dimethylformamide ( 3,60 parts, 36%) λ max 561 nm, ε max 35,159 'Analytical C, 68.2; Η, 4.5; C20H1606 requires "68.2; Η, 4.5%. Mass spectrometry method does not show that the structure of the compound is in the range of 3 5 The ions and fragments of the molecule of 2 are shown in Example 6 and the method of Example 2. The 5-hydroxy-2-fluorene 3- (4-isopropoxy pphenyl) -2,3-dibenzobenzopyran (2.84 parts) reaction, M produced the product 7- (4-isopropoxybenzyl) -7-hydro_2, 3,6-trifluorene-benzyl (l: 2 * b, 4: 5-b, ) Difuran (3.72 parts; 110%) s-product purified in dimethylmethylamine (55 parts, 46%) λMχ 561 nanometer, ε max 29,583. Quality. Spectral measurement shows that the coupled structure is at 338 Molecule G Li7 The method of Example 2 was added to chlorchloride (0.65 parts) and 2-dimethylaminopyridine (0.05 parts) to 5-diameter-2 * · copper_3- (4 -Methylbenzyl) _2,3_dihydrobenzylfuran (1.2 parts) Printed by the I Industrial Consumer Cooperative of the Central Standards Bureau of the Ministry of Chlorine Economics (please read the precautions on the back before filling this page) Methane (15 parts ) In the hydrazone solution. __ Product 7- (4-methylphenyl) -7-hydrogen 3,6-trifluorene-benzo U: 2-b '4: 5-b,) difuran (1.7 115%). The product purified in dimethylformamide A max 555.6 Nr., Ε This paper size is applicable to China National Standard (CNS) A4 (2! 〇297297 mm) 4 42 48f 82109395 No. of patent applications for TF alfalfa (85 years A7 B7)
經濟部中央標準局員工消費合作社印製 五、發明説明() — max 29, 2 08 (0. 75份,51% )。質譜測定法顯示,符合结構 之於294之分子之離子與晬體。1Η及13Cnmr·皆苻合结構。 音Μ 8 以簧例2之方法。 將5-羥-2-嗣- 3-(3-甲基苯基)-2,3-二氫苯并呋喃(2.4 份)反應,以產生產品7-(3-甲基苯基)-7-氫-2, 3, 6-三酮 -苯并(l:2-b,4:5-bf)二呋喃(2.8份;95%)。 在二甲基甲醯胺中純化之產品.λ max 554納米_、e max 34,000。質譜測定法顯示,符"合結構之於294 ·之分子之離 子與碎體。1 Η及1 3 C n m r皆符合结構。 富俐Q - 以實例2之方法。 將5-羥-2-嗣- 3-(3,4-二甲氧基苯基)-2,3-二氫笨并呋 蝻(2. 86份)反應,K產生產品7-(3,4-二甲氧基笨基)-7-氫-2, 3 , 6-三銅-笨并(1 :2-b, 4: 5-b ·)二呋喃(2 . 7份;80 % )。 鈍化之產品係一種混合物,質譜測定法顯示,苻合所笳 要结構之於340之分子之難子。 音例1 0 从實例2之方法。 . 將草鹺溴(3.3份)及2 -二甲胺^吡啶(0 . 1 2 5份)加入5 -羥 -2-嗣-3-苯-2,3-二氫苯并呋喃X5.65份)在二氢甲烷(50份 )中之懸浮液中。 產品於纯化之後-,係與在實鈣1中獲得者完全相同。 -13 - 本紙張尺度適用中困國家橾孪(CNS ) A4規格(2IOX297公釐) 士 民------ -- T____ - . i (請先閲讀背面之注意事項再填寫本頁) 442487 A6 B6 烴濟部t央標準局員工消费合作社印製 五、發明説明(17 ) g拥1 ΐ 將草醢Μ (17.5份)及吡啶(0.5份)加入5-羥-2-酮-3-苯 -2,3-二氫苯并呋喃(22.6份)在二氛甲烷(200份)中之懸浮 液中。於6小時回流之後,將氯-酮-醋酸2-酮-3-苯-2,3 -二氫-苯并呋喃-5-基醮分離出·及將酚(9,9份)加入,Μ 及將混合物回流18小時。溶劑之除去,產生粗產品草酸 (2-酮-3-笨-2,3-二氫-笨并呋喃-5-基)_苯基酯(33.3份 ;89% )。在甲酵中之研磨成粉末及自乙酸乙酯中之再结 晶產生一棰纯產品。分析C,70.4; H,3,7: C22H1306要求 C,70.8; Η,3.59έ。熔點 1341C · Μ及 13Cn»r產生符合結構 之光繒。 在二氛甲烷中陲後與三乙胺之環化及純化*產生與茛例 1中獲得者完全相同之產品。 如實例11反應而製備之氛-麵__酸2-酮-3-苯-2,3-二氫 -苯并呋喃-5-基酯與對-硝基酚在甲笨中、於回流下之反 應,於纯化之後產生草酸(4-硝基-苯基)酷(2-酮-3-苯-2,3-二氩-苯并呋喃-5-基)酯(33%產率)。分析C, 63.5; Η·3.3; H,3,5; C22H13N08要求 C,63.0; N,3.3% 。質譜测定法顯示於419之一種分子之離子。 在二氛甲烷中隨後與三乙胺之環化及純化*產生與實例 1中獲得者完全相同之產品。 啻例1 3 如實例11反應而製備之氯-酸2-酮-3-苯-2,3-二氣 -19- 本紙張尺度適用t國1家標準(CNS;策4«咚丨210父297公釐) --------------------------------------------------------------------------------裝......................訂....................線 <請先閉讀背面之,注意事項再填寫本頁一 44248 7 A6 ____B6 五、發明説明(18 ) ••苯并呋哺-5-基酯與2,6-二甲基酚在甲苯中、於回流下之 反應,於纯化之後產生草酸(2,6-二甲基-苯基)酯(2-嗣 -3-苯-2 ,3-二氫-苯并呋喃-5-基)酯(38%產率}。分析 C.70.6; H,4,l; C24H1806 要求 C.71.8; Η·4.2%。質繒测 定法顯示於402之一種分子之雛子。 在二氛甲烷中随後與三乙胺之瑁化及純化,產生與賁例 1中獲得者完全相同之產品。 g捆1 4 Μ艙二-(?-醢-3-芏-2·:;-二镢笼夹晡-5-氬)睡夕脚楢〇 方法A : 經濟部中央標準总員工消費合作杜印製 (請先:4讀背面、'-注意事項再塡寫本頁) 於氮大氣下,將5-羥-2-酮-3-苯-2,3-二氳苯并呋喃 (23份)及草醣氯(65份)加入二氯甲烷(1990份)中。將二甲 基甲缠胺(7.3份)在二氯甲烷(133份)中之溶液於30分鐘 内滴狀地加入。將溶液加热至回流經過21小時,然後冷卻 至周圍溫度。將另外之草醢氯(65份)加人·随後將另外之 在二氯甲烷(133份)中之二甲基甲醢胺(7.3份)加入。再 加熱溶液至回流經過24小時。於冷卻至周園溫度之後,用 水(500份)洗嫌反應混合物及於真空下蒸餵溶劑。用甲醇 將棕色似焦油之殘渣漿液化,產生如一種灰白色固體之草 酸二(2-酮-3-苯-2,3-二氫笨并呋喃-5-伸氧)酯(132份)。 純化之產品之In mi·、13Cn nr 、質量及紅外線光譜係符合 结構。 方法B : -20- 本紙張尺度適用申國國家標準(as I π 4遢格ί 210χ 297公釐) 4 42 48 7 A6 B6 五、發明説明(19 ) (請先¾讀背面之,注意事項再填窝本頁) 於氮大氣下,將5-羥-2-嗣-3-笨-2,3-二氫笨并呋喃 (464份)、草豳氯(305份〉、甲笨(347份)及2-二甲胺基 吡啶(7份)加入二氯甲烷(10600份)中。加熱懸浮液至回 流溫度烴過2.5小時。於冷卻至周圍溫度之後’將另外之 在二氱甲烷(5300份)中、包含三乙胺(202份)之5-羥-2-嗣 -3 -笨-2,3 -二氫苯并呋哺(464份)於1小時内加入,及將 紫色之溶液於周圍溫度下攫拌過夜。於用冷水洗滌之後, 於真空下蒸餾溶劑,Μ產生一種紫色固體(1120份自_ 酸乙酯之再結晶產生草酸二- (2-酮-3-苯-2,3-二氫苯并呋 喃-5-伸氧)酷(559份)*此物質係與由方法Α製備之樣本 完全相同。 實例L5· 7-笼-7-值醢-茉井M:2-h.4:5-b'l二眹晡之郸 備° 將草酸二- (2-嗣-3-笨- 2,3-二氫苯并呋喃-5-伸氧)酯 (60份)溶解於二甲基乙醯胺(470份)、甲苯(44份)、三乙 胺(20份)及49份之2-二甲胺基吡啶在二氯甲烷中之1%重 量:膜積溶液中。於80 1C加熱溶液2小時。將甲磺酸 (19份)加入冷卻之反應混合物中*及除去揮發物(75^0/ 1. 0毫米汞柱)。將生成之暗紅色焦油(107份)溶解於二 氛甲烷(1325份)中、用水洗滌、分雛及自有櫬相中除去溶 經濟部t央標準局貝工消费合作社印製 品 I 1 /IV 粗辑 生固 產色 以紅 ,暗 劑種 油 份 并 笨 - 嗣 三 生 產 晶 結-7完 之苯本 中7-樣 酯之之 乙備喃 酸製呋 酷 Α 二 自法 J 。方b' H 雷 份由:5 4 與 4 氫 同 相 全 本紙張尺度適用中國國家標準(CNS.i ® 4蝌格(210x 297公釐丨 442487 A6 B6 經濟部中央標準局員工消费合作社印製 五、發明説明(20 ) 經由氣賭與液體廇析術及1Ηη·Γ)。 窗捆1 fi 重秘二-(7-鹂-3-(2.5-二甲某笼某)-2.3-二氩笼并!》矣_ 袖氬)酯之製備。 i ΐ R-H-2 -碥-3-(2.5-二甲某笼某1-2.3-二氲笼井味 晡。 使用Μ製備2,5-二甲基笨乙酵酸之方法係類似於由利布 索瑪(Riebsoaer)及霣文(Irvine)敘述者(有機合成文集 (Org.Synth., Co 11.)第三卷•第32 7頁)。如此,將於對-二甲苯(38份)中之嗣基丙二酸(oxonalonate)乙醋(25份) 在0-5t於氮大氣下播拌,同時於20分鐘内將無水氣化鍚 (46份)加入。經由另外之對-二甲苯(43份)之加入而維持 混合物流勖•及容許其加熱至周圍溫度。於3小時攒拌之 後*在冰與10莫耳澹度氫氛酸之混合物上驟冷混合物,及 將其萃取入二乙醚中9用水洗滌分離之有機相、於疏酸鎂 之上乾燥、遇濾及於降低之壓力下蒸發溶劑。然後於真空 下蒸餾粗棕色油(31份)· Μ產生(2,5-二甲基苯基 >-羥丙 二酸二乙酿(26份)。Hriar、13Cn·!·與質膳及微最分析皆 符合结構。 將(2,5-二甲基笨基 羥丙二酸二乙_之樣本(21份)與 氫氧化鉀(21份)在水(84份)中之溶液於981C反應5小時。 於冷卻至周圔溫度後•用二乙醚洗嫌反應混合物、及用 10莫耳濃度氫氛酸酸化。於加熱至98t經遇另外之2小時 之後,將經冷卻之物質萃取入二乙醚中。於硫酸鎂之上乾 -22-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention () — max 29, 2 08 (0.75 copies, 51%). Mass spectrometry showed ions and carcasses of 294 molecules that conformed to the structure. 1Η and 13Cnmr · are all coupled structures. The tone M 8 is the same as that of the spring example 2. 5-hydroxy-2-fluorene- 3- (3-methylphenyl) -2,3-dihydrobenzofuran (2.4 parts) was reacted to give the product 7- (3-methylphenyl) -7 -Hydrogen-2, 3, 6-trione-benzo (l: 2-b, 4: 5-bf) difuran (2.8 parts; 95%). Product purified in dimethylformamide. Λ max 554 nm, e max 34,000. Mass spectrometry showed that the ions and fragments of the molecule with a structure of 294 · were in combination. 1 Η and 1 3 C n m r all conform to the structure. Fu Li Q-Take the method of Example 2. Reaction of 5-hydroxy-2-hydrazine 3- (3,4-dimethoxyphenyl) -2,3-dihydrobenzfurfuramidine (2.86 parts), K yielded product 7- (3, 4-dimethoxybenzyl) -7-hydro-2, 3, 6-tricopper-benz (1: 2-b, 4: 5-b ·) difuran (2.7 parts; 80%) . The passivated product is a mixture, and mass spectrometry shows that the difficult structure of the 340 molecule is combined with the desired structure. Example 1 0 The method from Example 2. . Add grass bromide (3.3 parts) and 2-dimethylamine ^ pyridine (0.1 125 parts) to 5-hydroxy-2-hydrazine-3-benzene-2,3-dihydrobenzofuran X5.65. Parts) in suspension in dihydromethane (50 parts). After purification-the product was exactly the same as obtained in Calcium 1. -13-This paper size applies to the CNS A4 specification (2IOX297 mm) Shimin -------- T____-. I (Please read the notes on the back before filling this page) 442487 A6 B6 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Hydrocarbons. 5. Description of the invention (17) g holds 1 ΐ Add grasshopper (17.5 parts) and pyridine (0.5 parts) to 5-hydroxy-2-one-3-benzene -2,3-Dihydrobenzofuran (22.6 parts) in a suspension in dichloromethane (200 parts). After refluxing for 6 hours, chloro-keto-acetic acid 2-keto-3-benzene-2,3-dihydro-benzofuran-5-ylfluorene was isolated and phenol (9,9 parts) was added, M And the mixture was refluxed for 18 hours. Removal of the solvent gave the crude product oxalic acid (2-keto-3-benzyl-2,3-dihydro-benzylfuran-5-yl) -phenyl ester (33.3 parts; 89%). Milling in formazan to powder and recrystallization from ethyl acetate produces a pure product. Analysis C, 70.4; H, 3,7: C22H1306 requires C, 70.8; Η, 3.59. Melting points 1341C · M and 13Cn »r produce photoluminescence conforming to the structure. Cyclization and purification with triethylamine after tritium in dichloromethane produces the same product as obtained in buttercup example 1. The atmosphere-face__acid 2-keto-3-benzene-2,3-dihydro-benzofuran-5-yl ester prepared with the reaction of Example 11 and p-nitrophenol in methylbenzyl under reflux After the reaction, (4-nitro-phenyl) oxa (2-keto-3-benzene-2,3-diargon-benzofuran-5-yl) oxalate was obtained after purification (33% yield). Analysis C, 63.5; Η · 3.3; H, 3, 5; C22H13N08 requires C, 63.0; N, 3.3%. Mass spectrometry showed a molecular ion at 419. Subsequent cyclization and purification with triethylamine in dichloromethane * yielded exactly the same product as obtained in Example 1.啻 Example 1 3 Chloro-acid 2-keto-3-benzene-2,3-digas-19 prepared according to the reaction in Example 11- This paper is applicable to 1 national standard (CNS; policy 4 «咚 丨 210 parent 297 mm) ---------------------------------------------- ---------------------------------- install ............... ....... Order ............ line < Please close the back of the page first, pay attention to matters before filling in this page one 44248 7 A6 ____B6 five Explanation of the invention (18) • The reaction of benzofuran-5-yl ester and 2,6-dimethylphenol in toluene under reflux, after purification, oxalic acid (2,6-dimethyl- Phenyl) ester (2-fluoren-3-benzene-2,3-dihydro-benzofuran-5-yl) ester (38% yield). Analysis C.70.6; H, 4, l; C24H1806 Requirement C .71.8; Η · 4.2%. The mass spectrometry method showed a brood of a molecule of 402. Subsequent dehydration and purification with triethylamine in dichloromethane produced the same product as that obtained in Example 1. G bundle 1 4 Μ cabin two-(?-醢 -3- 芏 -2 ·:;-two 镢 cage clip 晡 -5-argon) sleeping 夕 foot method 〇 Method A: Central Ministry of Economic Affairs Central Staff Consumption Cooperation Du Printed (please read: 4 read the back, '-Cautions before transcribing Page) In a nitrogen atmosphere, add 5-hydroxy-2-one-3-benzene-2,3-difluorenylbenzofuran (23 parts) and xylitol chloride (65 parts) to dichloromethane (1990 parts). A solution of dimethylformamide (7.3 parts) in dichloromethane (133 parts) was added dropwise over 30 minutes. The solution was heated to reflux for 21 hours and then cooled to ambient temperature. Grasshopper chlorine (65 parts) was added. Then another dimethylformamide (7.3 parts) in dichloromethane (133 parts) was added. The solution was heated again to reflux for 24 hours. Cooled to week After the temperature, the reaction mixture was washed with water (500 parts) and the solvent was evaporated under vacuum. The brown tar-like residue slurry was liquefied with methanol to produce bis (2-keto-3-benzene-2) oxalate as an off-white solid. , 3-Dihydrobenzylfuran-5-ethanoxy) ester (132 parts). In mi ·, 13Cn nr, quality and infrared spectrum of the purified product are in accordance with the structure. Method B: -20- National Standards (as I π 4 遢 格 210 x 297 mm) 4 42 48 7 A6 B6 V. Description of the Invention (19) (Please read the back first, note that Please fill in this page again.) Under a nitrogen atmosphere, 5-hydroxy-2-hydrazine-3-benzyl-2,3-dihydrobenzylfuran (464 parts), chlorchlor (305 parts), and methylbenzyl ( 347 parts) and 2-dimethylaminopyridine (7 parts) were added to dichloromethane (10600 parts). The suspension was heated to reflux temperature over 2.5 hours. After cooling to ambient temperature ', add another 5-hydroxy-2-hydrazone-3 -benzyl-2,3-dihydrobenzofurone in dioxane (5300 parts) containing triethylamine (202 parts) Add (464 parts) over 1 hour, and stir the purple solution at ambient temperature overnight. After washing with cold water, the solvent was distilled under vacuum to produce a purple solid (1120 parts from the recrystallization of ethyl acetate to produce di- (2-keto-3-benzene-2,3-dihydrobenzofuran) -5-Extended oxygen) Cool (559 parts) * This substance is exactly the same as the sample prepared by method A. Example L5 · 7-cage-7-value 醢 -Mojing M: 2-h.4: 5-b 'l Dioxin's Preparation ° Dissolve di- (2-fluoren-3-benzyl-2,3-dihydrobenzofuran-5-exoxy) ester (60 parts) in dimethylacetamide (470 parts), toluene (44 parts), triethylamine (20 parts) and 49 parts of 1% by weight of 2-dimethylaminopyridine in dichloromethane: in a membrane solution. The solution was heated at 80 1C 2 Hours. Methanesulfonic acid (19 parts) was added to the cooled reaction mixture * and volatiles (75 ^ 0/1. 0 mm Hg) were removed. The resulting dark red tar (107 parts) was dissolved in dichloromethane ( 1,325 parts), washed with water, separated chicks, and own phase. Removed from the Ministry of Economic Affairs, Central Bureau of Standards, Shellfish Consumer Cooperative Co., Ltd. Printed Products I 1 / IV. The rough solid color is red, and the dark oil is not stupid. -Thirty-three production of 7-like esters in benzene by crystallisation-7 Furfuryl A from acetopyranic acid A two-method J. Fang b 'H thunder from: 5 4 and 4 Hydrogen in-phase full paper size Applicable to Chinese national standards (CNS.i ® 4 grid (210x 297 mm 丨442487 A6 B6 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (20) Through air gambling and liquid decantation and 1Ηη · Γ). 2.5-Dimethyl Cage) -2.3-Diargon Combo! "! _ Sleeve Argon) Ester Preparation. I ΐ RH-2-碥 -3- (2.5-Dimethyl Cage 1-2.3-Dipyridine Nangjing miso. The method for preparing 2,5-dimethylbenzyl acetic acid using M is similar to that described by Riebsoaer and Irvine (Org. Synth., Co. 11.) Volume III • Page 32 7). In this way, oxonalonate ethyl acetate (25 parts) in p-xylene (38 parts) will be broadcast under nitrogen atmosphere at 0-5t Stir while adding anhydrous vaporized mash (46 parts) over 20 minutes. Maintain the flow of the mixture by adding additional p-xylene (43 parts) and allow it to heat to ambient temperature. Stir for 3 hours After * on ice with 10 The mixture was quenched on a mixture of otohydroxamic acid, and extracted into diethyl ether. The separated organic phase was washed with water, dried over magnesium sulfate, filtered and the solvent was evaporated under reduced pressure. Crude brown oil (31 parts) was distilled under vacuum to produce (2,5-dimethylphenyl) -hydroxymalonate diethyl alcohol (26 parts). Hriar, 13Cn ·! · Are in accordance with the structure and texture analysis. A sample of (2,5-dimethylbenzylhydroxymalonate) (21 parts) and a solution of potassium hydroxide (21 parts) in water (84 parts) were reacted at 981C for 5 hours. After cooling to After the temperature is reached, the reaction mixture is washed with diethyl ether and acidified with 10 mol hydrogen peroxide. After heating to 98t for another 2 hours, the cooled material is extracted into diethyl ether. In magnesium sulfate Above the dry
夂紙張尺度適用中國國家橾準丨CM)咬4扣ni〇x297公釐J ................. ........................… .........裝......................、玎.................線 (請先闕讀背面·-注意事項再塡寫本頁) 442487 A6 B6 經濟邾中央樣準局員工消费合作社印製 五、發明説明(21 ) 燦經分離之有機相,過濾及於降低之®力下蒸發溶劑。於 靜置之後,粗琥珀色油U5份)固化。自甲苯中之再結晶產 生2,5-二甲基苯乙醇酸(7份)。Inrar、13CnBr·及質_皆符 合結構。 經由在英國專利2068402A中敘述之方法,將2, 5-二甲基 笨乙醇酸(65份)與氫餛(33份)及98%硫酸(32份)和甲笨 U40份)反應,K產生5-羥-2-酮-3-(2,5-二甲基笨基)-2,3-二氫笨并咲喃(33份),烴由结晶及層析術分離此種物 質。純化產品之In ·γ光譜符合结構。 m首除二- (2.5 -二甲某笼某)-2.3丄二氣笼并 P#晡-S -柚氩)酷。 將5-羥-2-醣- 3-(2,5-二甲基笨基)-2,3-二氫笨并呋哺 (2.54份)、草醢氛(0.64份)及0.37份之2-二甲胺基吡啶在 二氯甲烷中之10%重量:重量溶液加入二氯甲烷(53份)中 。於氮大氣下,加热懸浮液至回流溫度經過26小時。將另 外之草醯氛(0.2份)加入。於回流溫度下6 2小時之後•將 溶液冷郤至周園溫度、用水洗滌及經由蒸餾除去溶劑,K 產生一棰粗製、似玻璃之產品(3.6份)。自釀酸乙醅中之 再结晶產生草酸二- (2-嗣- 3-(2,5-二甲基笨基)-2,3-二氫 苯并呋喃-5-伸氧)酯(1.17份)。inmr光譜符合结構。 奮锎1 7 -二田甚呆某)-7-¾ - 2U -三麵-¾ # Γ1 :2-h. 4:5-^1二咕晡之餺椹。 將草酸二- (2-鼷- 3-(2,5-二甲基笨基)-2,3-二氫笨并呋 -23- 本紙張尺度適用中囷國家標準(CNS〗浓4馒格f 210x297公釐} ................ .......................................................裝..........i . !.訂..............線 (請先¾讀背面之注意事項再蜞寫本頁j 42487 經濟部t央標準局員工消费合作社印製 A6 B6 五、發明説明(22 ) 喃-5-伸氧)酯(〇_8份)及三乙胺(〇·26份)加入二甲基乙豳 胺(18.7份)中。加熱溶液至701C經過1小時°經由蒸餾 (70 =0/0. 2毫米汞柱)除去揮發物。Μ負離子偵檢方式使 用IonSpray lc/ms分析產品油(0.96份)’此分析顯不主要 成分具有質量/霣子(a/e)= 307 (完全相等於308之分子 量)及碎體模式,符合7-(2,5-二甲基笨基)-7-氫-2,3, 6-三酮-笨并[l:2-b,4:5-b']二呋喃。 窗例1 8 於將2-乙基苯胺(1.3扮)加人之前,將7-笨-7-氫-2, 3,6-三酮-苯并[1:2-1>,4:5-^^]二呋哺(2.8份)於播拌下 加入冰醋酸(45份)與硫酸(1.25份)之混合物中*及於回流 下加熱90小時。將反應混合物冷卻與倒人水(1〇〇份)中、 及經由過濾收集沈載之固體、用水洗滌直到不含酸為止、 Μ及於40X:乾煉,以產生3-笨-7-(4-胺-3-乙基苯基)-2, 6-二嗣_2,6-二氫笨并-[1:2-1),4:5-1)’:1二呋哺(35%>。 窨例1 9 將7-苯-7-氫-2,3,6-三嗣-苯并[1:2-1>,4:5-1)’]二呋喃 (2_8份)加入1,2-二氣苯(20份甲苯磺酸(1,9份)與 酚(1份)之琨合物中,及於冷卻至周圍溫度之前*於140 -150t加熱混合物2 1/2小時。以過《收集生成之晶體固 體,及用1,2-二氣苯、甲酵、水與再用甲酵洗滌,Μ及乾 堍,Μ產生3-笨-7-U-羥基笨基卜2,6-二醑-2,6-二氫苯 并-[l:2-b, 4:5-b']二呋喃(69.4%)。 g ffl 20 ------------------------------------- --------------......................t......................’玎.................綠 ί請先其讀背面"注意事項再填寫本頁) -24 _ 紙乐尺度適用令國國家橒準(CNS;甲4蜆略f 210χ 297公 44248 7 A6 B6 經濟部中央標準局員工消费合作社印製 五、發明説明(23 ) 於將2-乙基苯胺<1.3份)加人之前,將7-苯-7-S-2, 3.6- 三_-笨并(1:2-1),4:5-1)’)二呋喃(2.8份)於攪拌下 加入冰酷酸(47.5份)與硫酸(2.5份)之混合物中,及於回 流下加熱90小時。將反應混合物冷卻與倒入水(100份)中 、及經由遇濾收集沈澱之固體、用水洗滌直到不含酸為止 、以及於40*0乾煉,K產生3-(4-胺-3-乙基苯基)-7-笨- 2.6- 二酮-2,6-二氫笨并(1:2-1),4:5-1)')二呋喃(3.8份; 10 0%)。於纯化之後在二甲基甲騸胺中λΒ3Χ 63 5納米 、e max 38,543。 苷例2 1 將 7-苯-7-S-2,3.6-三嗣-苯并(l:2-b,4:5-b'> 二呋喃 (2.8份)與N:N-二乙基苯胺(2·25份)在鄰-二氛苯(1〇份) 中、於回流下反應5小時。於冷卻及用甲酵稀釋之後*及 烴由過滅分離,以產生3-(4-Ν:Ν-二乙胺基苯基)-7-苯_ 2.6- 二嗣-二氫苯并(1:2外,4:5-1)|)二呋喃(1.95份; 47.5% )。於純化之後,在二甲基甲醢胺中λ nax 672納 米、e *ax 38.559。分析 C,74.7; Η,5,1; Ν,3·1; C26H21N04 要求 C,75.9; Η,5,1; Ν,3.4%。質譜測定法顯 示,符合结構之於411之分子之離子與碎饅。w m ?.?. 以實例20之方法。 將7-苯-7-氫_2,3,6-三酮-笨并(1:2-1),4:5-1)')二呋喃 (2,8份)與2-乙基6-甲基笨胺(1.5份)反應,以產生3-(3 -甲-4-胺-5-乙基笨基)-7-笨-2,6-二酮-2,6-二氳笨并 -25- 本紙張尺度逋用中國囷家標準ICNS)1? 4«格1210X297公釐) ί請先另請背面之迮意事項再填寫本頁) 裝夂 The paper size is applicable to China's national standards. CM) Bite 4 buckle ni × 297mm J ................... .............................................. ............. line (please read the back first--notes before you write this page) 442487 A6 B6 Printed by the Consumers' Cooperatives of the Central Bureau of Economics and Prospects V. Invention Description (21 ) The separated organic phase is filtered and the solvent is evaporated under reduced pressure. After standing, the crude amber oil (U5 parts) solidified. Recrystallization from toluene yielded 2,5-dimethylphenylglycolic acid (7 parts). Inrar, 13CnBr, and qualitatively all conform to the structure. By the method described in British Patent 20684402A, 2,5-dimethylbenzylic acid (65 parts) is reacted with hydrogen hydrazone (33 parts) and 98% sulfuric acid (32 parts) and methylbenzyl U40 parts), and K is produced. 5-hydroxy-2-one-3- (2,5-dimethylbenzyl) -2,3-dihydrobenzylpyran (33 parts), hydrocarbons were separated by crystallization and chromatography. The In · γ spectrum of the purified product conformed to the structure. Divide the first two-(2.5-two in one cage and one in the cage) -2.3 丄 two air cages and P # 晡 -S-grapefruit argon) cool. Add 5-hydroxy-2-sugar 3- (2,5-dimethylbenzyl) -2,3-dihydrobenzfurfurone (2.54 parts), grass grass flavor (0.64 parts) and 0.37 parts of 2 -10% by weight of dimethylaminopyridine in dichloromethane: a weight solution is added to dichloromethane (53 parts). Under a nitrogen atmosphere, the suspension was heated to reflux temperature for 26 hours. Add another grass fragrance (0.2 parts). After 6 2 hours at reflux temperature • The solution was cooled to ambient temperature, washed with water, and the solvent was removed by distillation. K produced a stack of crude, glass-like product (3.6 parts). Re-crystallization from acetoacetic acid to produce di- (2-fluorene-3- (2,5-dimethylbenzyl) -2,3-dihydrobenzofuran-5-ethanoxy) oxalate (1.17 Copies). The inmr spectrum fits the structure. Fenyu 1 7-Ertian is so dumb) -7-¾-2U-三 面 -¾ # Γ1: 2-h. 4: 5- ^ 1 The two gurgles. Di- (2- 鼷-3- (2,5-dimethylbenzyl) -2,3-dihydrobenzfurfur-23- This paper is applicable to the National Standard of China (CNS) Concentration 4 馒f 210x297 mm) ............... ................ Installing ......... i.!. Order ... ...... line (please read the precautions on the back before writing this page j 42487 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A6 B6 V. Description of the invention (22) -5--5-oxygenation) Esters (0-8 parts) and triethylamine (0.26 parts) were added to dimethylacetamide (18.7 parts). The solution was heated to 701C over 1 hour through distillation (70 = 0 / 0.2 mm Hg Column) to remove volatiles. M negative ion detection method uses IonSpray lc / ms to analyze the product oil (0.96 parts) 'This analysis shows that the main component has mass / sprout (a / e) = 307 (exactly equal to the molecular weight of 308) And fragmentary mode, consistent with 7- (2,5-dimethylbenzyl) -7-hydro-2,3, 6-trione-benzyl [l: 2-b, 4: 5-b '] di Furan Window Example 1 Before adding 2-ethylaniline (1.3), add 7-benzyl-7-hydro-2, 3,6-trione-benzo [1: 2-1 >, 4 : 5-^^] Difuran (2.8 servings) in Add the mixture of glacial acetic acid (45 parts) and sulfuric acid (1.25 parts) under stirring and heat under reflux for 90 hours. The reaction mixture is cooled and poured into water (100 parts) and collected by filtration. Solid, washed with water until acid-free, and at 40X: dry-milled to yield 3-benz-7- (4-amine-3-ethylphenyl) -2, 6-difluorene_2,6- Dihydrobenzyl- [1: 2-1), 4: 5-1) ': 1 Difuran (35%). Example 1 9 7-Benzene-7-hydrogen-2,3,6- Trifluorene-benzo [1: 2-1 >, 4: 5-1) '] difuran (2-8 parts) was added with 1,2-digasbenzene (20 parts toluenesulfonic acid (1,9 parts) and phenol ( 1 part) of the admixture, and before cooling to ambient temperature *, heat the mixture at 140-150t for 2 1/2 hours. Collect the crystal solids produced, and use 1,2-digas benzene and formazan , Water, and then washed with formazan, M and dried, M produces 3-benz-7-U-hydroxybenzyl 2,6-difluorene-2,6-dihydrobenzo- [l: 2-b , 4: 5-b '] difuran (69.4%). G ffl 20 -------------------------------- ----- --------------...... t ........ .............. '玎 ...... Please read it on the back " Note (Please fill in this page again for the matters needing attention) -24 _ Paper music scales apply national standards (CNS; A4 strategy f 210χ 297 public 44248 7 7 A6 B6 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ) Before adding 2-ethylaniline < 1.3 parts), add 7-benzene-7-S-2, 3.6-tri-benz (1: 2-1), 4: 5-1) ' ) Difuran (2.8 parts) was added to a mixture of citric acid (47.5 parts) and sulfuric acid (2.5 parts) with stirring, and heated under reflux for 90 hours. The reaction mixture was cooled and poured into water (100 parts), and the precipitated solid was collected by filtration, washed with water until acid-free, and dried at 40 * 0. K yielded 3- (4-amine-3- Ethylphenyl) -7-benzyl-2.6-dione-2,6-dihydrobenzyl (1: 2-1), 4: 5-1) ') difuran (3.8 parts; 100%). After purification, λB3X 63 5 nm, e max 38,543 in dimethylformamide. Glycoside example 2 1 7-benzene-7-S-2,3.6-trifluorene-benzo (l: 2-b, 4: 5-b '> difuran (2.8 parts) and N: N-diethyl Aniline (2.25 parts) was reacted in o-diazabenzene (10 parts) under reflux for 5 hours. After cooling and diluting with formazan * and the hydrocarbons were separated by extinction to produce 3- (4 -N: N-diethylaminophenyl) -7-benzene-2.6-difluorene-dihydrobenzo (except 1: 2, 4: 5-1) |) difuran (1.95 parts; 47.5%). After purification, λ nax 672 nm, e * ax 38.559 in dimethylformamide. Analysis C, 74.7; 4.7,5,1; Ν, 3 · 1; C26H21N04 requires C, 75.9; Η, 5,1; Ν, 3.4%. Mass spectrometry showed that the ions and fragments of 411 molecules conformed to the structure. w m?.?. Take the method of Example 20. 7-benzene-7-hydro-2,3,6-trione-benz (1: 2-1), 4: 5-1) ') difuran (2,8 parts) and 2-ethyl 6 -Methylbenzylamine (1.5 parts) is reacted to produce 3- (3-methyl-4-amine-5-ethylbenzyl) -7-benzyl-2,6-dione-2,6-dibenzylbenzyl And 25- This paper uses the Chinese standard ICNS) 1? 4 «Grid 1210X297 mm) Please fill in this page with the intention on the back)
:tT 44248 7 A6 B6 經濟邾中央楳準扃貝工消費合作社印製 五、發明說明(24 ) (l:2-b,4:5-bM二呋哺(3.45份:87%)。於纯化之後,在 二甲基甲豳胺中λιη3χ 640納米、e aax 30.462。質譜瀾 定法顯示,符合结構之於397之分子之雕子與碎體。 g Μ K實例20之方法。 將 7-笨-7-S-2.3.6-三醑-苯并(l:2-b,4:5-b,)二呋哺 (0.28份)與N-苄基-鄰-甲苯胺(0.25份)反應•以產生 3-(3-甲-4-N-笨甲醵基胺基苯基)-7-笨-2,6-二嗣-2,6-二 氫笨并(l:2-b,4:5-b·)二呋喃<0.16份)。於純化之後,在 二甲基甲醣胺中λ nax 644.4纳米、έ·3χ 42,0 92。分析 C,77.2; H,4.6; H,3.0; C30H21N04 要求 C.78.4; Η,4.6; N,3.0%。質譜測定法顯示,符合结構之於459之 分子之雄子與碎體° •S m? A Μ實例20之方法。 將7-苯-7-氫-2,3,6-三阑-苯并(1;2-1>,4:5-1)1)二咲喃 (1. 4份)與Ν -乙基笨胺(〇 · ? 4份)反應,Κ產生3 - (4 - Ν -乙 基胺基苯基)-7-笨-2,6-二蹰-2,6-二 S 苯并(l:2-b, 4:5-b·)二呋喃(1.45份;76%)。於純化之後’在二甲基甲醢 胺中 XBase 648 納米、e nax 31,365。 g拥25 Μ實例20之方法。 將 7-苯-7-厘 _2,3,6-三_ -苯并(l:2-b,4:5-b·)二呋喃 (0.28份)與郾甲笨酚(0.15份)反應,以產生3-(3-甲-4-理 -26- 本紙張尺度適用中國國家揉準(CNS)虫4規格(210X297公釐) (請先閃讀背面之注意事項再塡寫本頁) _ * 1 44248 7 經濟部中央標準局員工消費合作社印製 A6 _B6 五、發明説明(25 ) 基苯基)-7-苯-2,6-二酮-2,6-二氫笨并(l:2-b, 4:5-b')二 呋喃(0.27份;73%)。在二甲基甲醢胺中Amax 523.6納 米、emax 39,148。 啻例2β 以實例20之方法。 將7-笨-7-氫-2,3,6-三_-笨并(1:2-1).4:5-1)')二呋喃 (0.28份)與對甲笨酚(0.15份)反應,Μ產生3-(2-羥-5-甲 基苯基)-7-苯-2,6-二_-2,6-二氫苯并(1:2-1>,4:5-1)')二 呋喃(0.15份)。λ max 441.6 納米(寛波峰)。(:,73.6; H,3.8; C23H1405 要求 C,74.6; H,3.8% 。質譜測定法顬 示》符合结構之於37 0之分子之離子。1Hoinr光譜符合结 播。 n m 27 κ霣例20之方法。 將7-苯-7-氫-2,3,6-三嗣-苯并(1:2-1^4:5-1)’)二呋喃 (2.8份)與甲氧基苯(1.5份)反應,Κ產生3-U-甲氧基笨 基)-7-笨-2,6-二嗣-2,6-二氫苯并(1:2-卜,4:5-1>’)二呋喃 (1,48份;40%)。在二甲基甲睡胺中λ «ax 501納米、ε aax 35,530° 窨捆Μ 以實例20之方法。 將7-苯-7-氫-2,3,6-三醑-苯并(1:2-1),4:5-1^)二呋喃 (2. 8份)與丙氧基苯(1.5份)反應* Κ產生3-(4-丙氧基笨 基)-7-笨- 2,6-二酮,2,6-二氫苯并(1:2-1),4:5-1>’)二呋梅 -27- 夂纸張又度適用中國固家標.〖CNS)®4規洛(21〇父297公釐) ί請先問讀背面之注意事項再塡寫本頁) 裝 、vs .線. 44248 7 A6 B6: tT 44248 7 A6 B6 Printed by the Economic, Central, and Quasi-Peugeot Consumer Cooperatives V. Description of the Invention (24) (l: 2-b, 4: 5-bM difurfur (3.45 parts: 87%). Purified After that, in dimethylformamide, λιη3χ 640 nm, e aax 30.462. Mass spectrometry method shows that the structure of the molecule and the fragment of the 397 molecule are in accordance with the method. MG Example 20 method. 7- 笨- 7-S-2.3.6-Trifluorene-benzo (l: 2-b, 4: 5-b,) difuran (0.28 parts) reacts with N-benzyl-o-toluidine (0.25 parts) • To produce 3- (3-methyl-4-N-benzylmethylaminoaminophenyl) -7-benzyl-2,6-difluorene-2,6-dihydrobenzyl (l: 2-b, 4 : 5-b ·) difuran < 0.16 parts). After purification, λ nax was 644.4 nm, and 3 × 42,0 92 in dimethylmethosamine. Analysis C, 77.2; H, 4.6; H, 3.0; C30H21N04 requires C. 78.4; Η, 4.6; N, 3.0%. Mass spectrometry showed that the structure of males and fragments of molecules of 459 conformed to the method of Example 20 of Sm? AM. 7-Benzene-7-hydrogen-2,3,6-tril-benzo (1; 2-1 >, 4: 5-1) 1) dipyran (1.4 parts) and N-ethyl Reaction of benzylamine (4. 4 parts), K produced 3-(4-N-ethylaminophenyl) -7-benzyl-2,6-difluorene-2,6-diS benzo (l: 2-b, 4: 5-b ·) difuran (1.45 parts; 76%). After purification 'XBase 648 nm, e nax 31,365 in dimethylformamide. g. Method of 25 M Example 20. 7-Benzene-7-Crystal_2,3,6-tri_-benzo (l: 2-b, 4: 5-b ·) difuran (0.28 parts) was reacted with benphenol (0.15 parts) In order to produce 3- (3- 甲 -4- 理 -26-, this paper size is applicable to the Chinese National Standard (CNS) Worm 4 specifications (210X297 mm) (please read the precautions on the back before writing this page) _ * 1 44248 7 A6 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs _B6 V. Description of the invention (25) phenylphenyl) -7-benzene-2,6-dione-2,6-dihydrobenzyl (l : 2-b, 4: 5-b ') difuran (0.27 parts; 73%). In dimethylformamide, Amax is 523.6 nm and emax is 39,148.啻 Example 2β The method of Example 20 was used. 7-benz-7-hydro-2,3,6-tri_-benz (1: 2-1) .4: 5-1) ') difuran (0.28 parts) and p-methylbenzol (0.15 parts) ) Reaction, M produces 3- (2-hydroxy-5-methylphenyl) -7-benzene-2,6-di-2,6-dihydrobenzo (1: 2-1 >, 4: 5 -1) ') Difuran (0.15 parts). λ max 441.6 nm (寛 peak). (:, 73.6; H, 3.8; C23H1405 requires C, 74.6; H, 3.8%. Mass spectrometry method shows "Ions conforming to the structure of a molecule of 37 0. 1 Hoinr spectrum meets the broadcast. Nm 27 κ Example 20 of Method: 7-benzene-7-hydro-2,3,6-trifluorene-benzo (1: 2-1 ^ 4: 5-1) ') difuran (2.8 parts) and methoxybenzene (1.5 Parts) reaction, K produces 3-U-methoxybenzyl) -7-benzyl-2,6-difluorene-2,6-dihydrobenzo (1: 2-Bu, 4: 5-1 > ' ) Difuran (1,48 parts; 40%). [Lambda] ax 501 nm, [epsilon] ax 35,530 [deg.] In dimethyl mesidine. The method of Example 20 was used. 7-benzene-7-hydro-2,3,6-trifluorene-benzo (1: 2-1), 4: 5-1 ^) difuran (2.8 parts) and propoxybenzene (1.5 Parts) reaction * K produces 3- (4-propoxybenzyl) -7-benzyl-2,6-dione, 2,6-dihydrobenzo (1: 2-1), 4: 5-1 > ') Difuran-27- 夂 Paper is again applicable to China Gujia standard. 〖CNS) ® 4 gauge Luo (21〇 father 297 mm) ί Please read the precautions on the back before writing this page) Installation, vs. Cable. 44248 7 A6 B6
五、發明説明(26 ) 經濟部中央標準局兵工消费合作社印製 (1.91份;48%)。在二甲基甲醯胺中Amax 505納米、emax 45,100〇C,74.6; H,4.3%; C25H1805 要求 C,75.4; Η,4.5% 。質譜測定法顯示,符合结構之於398之分子之 離子與碎體。音锎 筠某茧某)-2.6-二 g-2.fi-二氩茉 #Μ 二肽晡之脚備 1>將7-苯-7-11-笨并二呋喃-2,3,6-三酮(2.8份)溶解 於過量之稀氫氧化納中,K產生一種灃黃色溶液。經由濃 氫氛酸之加入而酸化溶液* Μ產生一棰幾乎無色之固體沈 溅,經由過濾收集此沈狼及用水洗滌,然後於真空中、於 無水氯化鈣之上乾嫌。以生產(5-羥-2-酮-3-苯-2,3-二氫 笨并呋喃-6-基)-酮-醋酸(2.55份>。 ii)將(5-羥-2-阑-3-苯-2,3-二氫苯并呋喃-6-基_ -醋酸(0.75份)加人1,2-二氛笨(10份)、對-甲苯磺酸 (0.5份)及酚(0.3份)之混合物中*於冷卻之前加熱反應 混合物至回流娌遇2小時,Μ及藉薄層層析術、對照作為 參比物質之標題化合物真實樣本、檢測樣本。 將整個反應混合物溶解於(1〇〇份)二甲基甲醸胺中、以 二甲基甲醢胺適當地稀釋、及浦量於582納米之光學密度 。經由與參比樣本之已知莫耳消光係數比較,3 -笨-Τα-羥 基苯基 )-2,6-二嗣 -2,6-二氫苯并-[l:2-b,4:5-b'] 二呋哺之產率係67%。 -28- 本纸張尺度適用中國國家橒準(CXS ) π 4规格(210X 297公釐) f琦先Μ讀背面之a意事項再磷寫本頁} .裝 4 4^487 θ Μ 第'3 2丨0 9 3 9 5號專利申請案 中文説明書修正頁U 3年1 2月 五、發明説明(27 Α7Γ# 正 B十本年A 3 —|^4^-T - 式 方 之 相 9 2 例網 賁三 a\ 6 Μύ, 自 氬 I -~ - 基 ί本 其上 氧 丙V. Description of the invention (26) Printed by the Military Industry Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (1.91 copies; 48%). In dimethylformamide, Amax is 505 nm, emax is 45,100 ° C, 74.6; H, 4.3%; C25H1805 requires C, 75.4; Η, 4.5%. Mass spectrometry showed that the ions and fragments of the 398 molecule conformed to the structure.锎 筠 锎 筠 some cocoon) -2.6-di g-2.fi-diargon #M dipeptide 晡 晡 1 > 7-benzene-7-11-benzodifuran-2,3,6- The triketone (2.8 parts) was dissolved in an excess of dilute sodium hydroxide, and K produced a yellowish yellow solution. The solution was acidified by the addition of concentrated hydrogen acid. M produced a pile of almost colorless solid splashes, which were collected by filtration, washed with water, and then dried under vacuum on anhydrous calcium chloride. In order to produce (5-hydroxy-2-one-3-benzene-2,3-dihydrobenzfuran-6-yl) -one-acetic acid (2.55 parts >. ii) -3-Benzene-2,3-dihydrobenzofuran-6-yl_-acetic acid (0.75 parts) with 1,2-diazepine (10 parts), p-toluenesulfonic acid (0.5 parts) and phenol (0.3 parts) of the mixture * The reaction mixture was heated to reflux for 2 hours before cooling, and the true sample and test sample of the title compound were used as reference materials by thin layer chromatography and control. The entire reaction mixture was dissolved in (100 parts) of dimethylformamide, appropriately diluted with dimethylformamide, and an optical density of 582 nm. By comparison with the known Moire extinction coefficient of the reference sample, 3 -Benzyl-Tα-hydroxyphenyl) -2,6-difluorene-2,6-dihydrobenzo- [l: 2-b, 4: 5-b '] The yield of difuran is 67%. -28- The size of this paper is applicable to China National Standard (CXS) π 4 specification (210X 297 mm). F Qi first read the meaning on the back and write this page}. 4 4 ^ 487 θ Μ 3 2 丨 0 9 3 9 No. 5 Patent Application Chinese Specification Revision Page U 3 years 1 February 5 、 Invention Description (27 Α7Γ # 正 B 十 本年 A 3 — | ^ 4 ^ -T-Formula Phase Phase 9 2 cases of net 贲 三 a \ 6 Μύ, since argon I-~-radical
Ti 并 笨Ti is dumb
1D I 溝 製 始 開 喃 呋 革- ¾ 苺 4 b I 5 4 b I 2 1L 并 苯分 氬.7一 二 4 I—L - 4 ΰ Λ 二, 5 2 ®示 二顯 13-法 定 1 基譜 苯冒: 1 氧喃 丙呋 2 - 子 離 之ρ;ιί 子窗 % 3')基 7--b苯 自:5基 ,4,氧 式-b丙 方:2異 之(1-W并 相笨 9 2 例 實 與 基 苯 基 氧 丙 異 0 基 三¾ (5-Μ 3’挥 4 氫 氫 I 3 二 -7備 製 r-J . - 始網 開二 喃B-呋2, - ΰ (请先閲讀背面之注意事項再填寫本頁) 苯泮(1 : 2 - b , 4 : 5 - b ')二呋喃:質_測定法顯示,於4 1 4之 分子之離子Ρ Λ1D I Furan Furan-¾ Berry 4 b I 5 4 b I 2 1L acene argon. 7 1 2 4 I—L-4 ΰ Λ 2, 5 2 ® shows the second display 13-legal 1 base Spectral benzene risk: 1 oxpropran 2-ionic ion ρ; ιί sub-window% 3 ') group 7--b benzene from: 5 group, 4, oxo-b propyl side: 2 different (1-W Benzene oxypropyl isopropyl group ¾ (5-M 3 'volatilized 4 hydrogen hydrogen I 3 di-7 prepared rJ.-Start network open difuran B-furan 2,-ΰ (Please read the precautions on the back before filling this page) Benzene (1: 2-b, 4: 5-b ') Difuran: Quantitative_assay shows that the ion of the molecule P 4 Λ Λ
ILJCiiL Μ與莨洌2 0相丨从之方式‘自7 -笨-7 -霞-2 , 3 , ΰ -三銅-笨 并(1 : 2 - b , 4 : 5,b ’)二眹喃開始,製蔺3 - ( 4 H -二乙肢朞 茏基)-7 -苯-2 , 6 -二銅-2,6 -二氫笨并(1 : 2 - b , 4 : 5 - b ‘)二呋 喃。質譜測定法顯不,f ΐ 4丨1 2L分子Z離子 經濟部中央標準局員工消費合作社印製 9 2 本紙張尺度適用中國國家搮準(CNS) Α4規格(210Χ2Μ公釐) 83.3. 10,000The phase of ILJCiiL Μ and 相 2 0 丨 from the way 'Si 7 -ben-7 -Xia-2, 3, ΰ -three copper-benzyl (1: 2-b, 4: 5, b') Initially, the production of pyrene 3-(4 H -diethionyl fluorenyl) -7 -benzene-2, 6 -dicopper-2,6 -dihydrobenzo (1: 2-b, 4: 5-b ′ ) Difuran. Mass spectrometry shows no, f ΐ 4 丨 1 2L molecule Z ion Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 9 2 This paper size applies to China National Standard (CNS) Α4 (210 × 2M mm) 83.3. 10,000
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GB939301422A GB9301422D0 (en) | 1993-01-25 | 1993-01-25 | Process and compounds |
GB939322826A GB9322826D0 (en) | 1992-11-25 | 1993-11-05 | Compound |
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