TW442487B - Benzodifurantriones, a process for their preparation, compounds prepared therefrom and their preparation processes - Google Patents

Abstract

Benzodifurantriones of formula (1): in which W is unsubstituted or substituted aryl, a process for their preparation via dioxo intermediates and processes for their conversion into benzodifuranone dyes and compounds of formula (7): are provided wherein R3 is -H, -COR2, -SO2R2- which R2 is alkyl, cycloalkyl, aryl or aralkyl and R4 is -COOR2, -CONRR1 in which R and R1 each independently is -H, alkyl, cycloalkyl, aryl or aralkyl; -COOH or the alkali metal, alkaline earth metal or ammonium salts thereof; or -COX2- which X2 is halo.

Description

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:

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:

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):

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

0H

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) «:

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):

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

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

The chemical formula [5] is via the reaction of benzodifuranthine and hydrazone with the compound of the formula (6):

Chemical formula [6] Printed by Jiro Lang t Central Standard Bureau employee consumer cooperative

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):

(Please flash down the „Cautions on the back side before writing 4 copies II 0R3

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 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 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 (Please read the notes on the back before filling in this page)

NMR 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 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)

The 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)

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 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 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

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 is dumb

1D 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

The 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

Claims (2)

442487 τ! Ί · *! fy: '] ^ jy Patent Supplement No. 82109395 Chinese Application (June 89) Example 4 Analytical data of compound 1. Melting point: 256 ° C (obtained by DSC analysis) 2. Mass spectrum data : (Electron impact: positive) M + at m / s338 3. High pressure liquid chromatography (HPLC): (reverse phase ion-pair eluent) 9.259 ° 4. Microanalysis: Actual values are% C 67.25,% H4.04, C19H1405 The theoretical value is% C 67.46 «% H4.14 5. UV / visible light is 562 nm (ε_ is 34, (M8) (in DMF) 6. 'HNMR 15 ! 5 U • T1i'PE,. \ S CK \ WK〇BO4734SUP DOC 442487 Chemical shift 5 / ppn ^ CDCl3 Integration result coupling specified group 7.75 2H double wave H2 or H3 7.0 2H double wave H3 or H2 6.75 2H single wave H1 4.0 2H three-wave peak och2 3.4 1H broad H4 / OH 1.82 2H six-wave sin ch2 1.05 3H three-wave ch3 7. 13C NMR 15 15 U: \ TYPE \ WCK. \\ TCCVB347} ^ SUP DOC -2 44248 7 Chemical shift 6 / ppm at CDC13 Coupling carbon atom type designation group 169 s fourth order C9 164 s fourth order Cl 160 s fourth order C4 154 s four Class C14 150 s Class C8 144 s Class IV Cl 138 s Class C2 130 d CH C12 123 s Class Cll 120 s Class C3 117 s Class IV CIO 115 d CH C13 97 d CH C6 96 d CH C5 70 t ch2 C15 23 t ch2 C16 11 q ch2 C17 L T'l Pt WCK AVKC'B'J4? 34SijP DOC " 442 4 8? Article 821093? 5 諕 Patent application inspection = document application (November) ABC0 humiliated 89 2 V "charge 0-" <-6. Type of patent application scope The formula [U and its formula I: V is the group of the following chemical formula: Or wherein: ring A is unsubstituted or substituted by 1 to 5 selected from Ci-α-fluorenyl and CX-4 -fluorenyl and combinations thereof Group substitution: 2 .—Method of making benzodiazepine 3 1Ϊ of formula (1): (Please read the precautions on the back before filling out this page) T, -β Ministry of Economy _ 央 橾 准 局Employee consumer cooperative printing Chemical formula [1] Profitable type (2) Hua Hejun: The standard of this paper is applicable to Chinese National Standard (CNS) A4 Washing (21〇 乂 297 mm) A8 B8 C8 D8 6. Application scope of patents OH The chemical formula [2] reacts with the compound of formula (3 1: (Please read the precautions on the back before filling this page) Chemical ^ [3] where: y is a group of the following chemical formula: Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs: Ring A is unsubstituted or substituted with 1 to 5 groups selected from Ci-4-alkyl and Ci-4-fluoroxy and combinations thereof; and X and X 1 are each dihalide: 拫 According to the method in the scope of patent application, the reaction is based on the non-silver paper method, applicable to China National Standards (CNS) A4 (2! OX297 mm) ) ^ AO A Q. 1 A8 B8 Cfi D8 6. The scope of patent application is carried out in the presence of nuclear base: 4. The method according to item 2 of the scope of patent application • The reaction island is in the presence of non-nucleophilic base and acid binder Carry on. 5. — Method for making benzodifuran and succinimide of the formula (1): (Please read the precautions on the back before filling this page) Include the following steps: a) Make the compound of formula (2): 0H 0 Chemical formula Printed by the Consumer Cooperative of the Central Government Bureau of the Ministry of Economy Reaction with the compound of formula (3): Chemical formula [3] 〇 Chemical formula The paper method is fully applicable to Chinese National Standard (CNS) A4 (21 × 29? Mm) 々, the scope of patent application Μ generating formula (4 > (Please read the notes on the back before filling this page) Chemical formula [4] b) The cyclized compound (4) compound K produces benzodifuran tri copper of formula (1), where: W is a group of the following chemical formula: Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, where: Ring A polyester is unsubstituted or substituted with 1 to 5 groups selected from -alkyl a C i -4 -fluorenyloxy and combinations thereof: 6. According to The method of applying for the fifth item of patent scope, wherein step a) is performed in the presence of a non-silver nucleobase > The paper scale is applicable to China National Standard (CNS) A4 (210X 297 mm) 44248 7 A8 B8 C8 D8 VI. Patent Application Range 7. The method according to item 5 of the patent application range, wherein step a > is carried out in the presence of a non-nucleophilic base and an acid binding agent. 8. The method according to item 5 of the scope of patent application, wherein step b) is performed in the presence of a non-nucleophilic base or in the presence of Louise: 9 .— a compound of formula (_ 4): 〇 Chemical formula [4] where: V is a group of the formula: (Please read the notes on the back before filling out this page) -'Fill in this I * νδ Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. Among them: Ring A except for unsubstituted or 1 to 5 is selected from C i 4 -fluorenyl and C i 4 -fluorenyloxy and combinations thereof; and X is a dental group. 1 0, —A method for preparing compound of formula (5): I -5-This paper size is applicable to Chinese National Standard (CNS) A4 (210 > < 297 mm) 442487 8 8 8 8 ABCD VI. Application Patent scope: or -C 0 X 2, where X 2 is a polyester halide. Printed by the Order of the Ministry of Economic Affairs of the Central Bureau of Standardization, Shellfish Consumer Cooperatives (please read the precautions on the back, and then fill out this page) i / t,-Oral paper size is applicable to Chinese National Standards (CNS) A4 this grid (210X297) (Centi) 4 48 ^^ 2 1 09 39 No. 5 Patent Application Chinese Specification Correction Page U8 Sep. 8) A7 B7 Amendment Supplement V. Description of the Invention (Separation in the compound * For example, the filtration of the hydroxyl group by the reaction mixture = chemical formula ⑴, ⑷ Compounds of hydrazone are used as intermediates in the preparation of various hydrazone compounds. To be stated, they are used as intermediates in the manufacture of dyes, agricultural chemicals and pharmaceuticals. Compounds of formula (5) can be used as dyes · Specifically speaking, the color of synthetic textile materials such as polyester. 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 of the shoulder labor consumer cooperative max < please read the precautions on the back before (Fill in this page) Grass grass (2.6 parts) and 4-dimethylaminopyridine (0.1 parts) are added to 5-hydroxy-2 -fluorene-3-benzyl-2,3-dihydrobenzfuran (4.52 parts) In dried methylene chloride (50 parts) In suspension. The mixture was stirred and heated under reflux for about 6 hours until the evolution of hydrogen chloride gas ceased. The mixture was cooled to 20 t and a solution of triethylamine (5 parts) in dry dichloromethane (25 parts) was added dropwise over 5 minutes with stirring. The mixture was refluxed for an additional 3 hours before it was cooled and poured into water (100 parts) and 2 moles of hydrochloric acid (20 parts) was added. The dichloromethane was removed by distillation and M left the product as a brown crystalline solid suspended in water. The product was collected via perylene and dried, and K produced 7-benzene-7-hydro-2, 3, 6-trinet-benzy [1: 2 -1), 4: 5-1) |] difuran (5.3 copies, 94.6%). The product was purified by recrystallization from acetonitrile (λ max = 552 nm in dimethylformamide) = 35,000) Purified product amount (by weight): 2.7 parts yield: 43¾ Melting point: 220- 222 1C structural analysis results: 15 This paper size is applicable to Chinese national standard (CNS > A4 size (2ί〇 × 297mm) 442487 No. 3 2 1 Ο 9 3 9 5 Chinese Patent Application Revised Page (δδ September) V. Description of the invention (amend each ί-month Η supplement 88. 9. 10 Α7 Β7 〇 (Please read the notes on the back before filling in this page) NMR PP ffl, de -DMS0: 6.80, double peak, j = 7Hz, 2H, 7.22, three peak, j 2 7HZ, 1H, 7.40, three peak, j = 7 Hz, 2H, 7.80, double peaks, j = 7Hz, 2H, microanalysis id: Fruit: X C68. 3, Η 2.8, and C 1 β Η s s requires C 58 mass spectrometry analysis at m / 2 AJL was measured at 280. From the method of Example 1, printed chlorpyrifos and pyridylamine methylol by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs-5 Λ plus 5 This paper size applies to Chinese National Standards (CNS) A4 specification (210X 297 mm) 8 2 1 0 9 3 9 Patent application No. 5 explained by 々feTF april September) A7 B7 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 out this page) X 44248? No. 82109395 Patent declaration ticket In sharp sharp note page (September 1985 A7 B7 Amendment Supplement V. Description of the invention () -2- 詷-3- (4-butoxyphenyl) -2 , 3-Dihydrobenzyl sulfan (3.49 parts) in a suspension in dichloromethane (75 parts). Product 7- (4-butoxyphenyl) -7-hydro-2,3,6- Tripyridine- (1: 2-b, 4: 5-b ·) difuran (11.35 parts; 107.5%). Product purified in dimethylformamide (3,60 parts, 36%) λ max 561 nm, ε max 35,159 'Analyze C, 68.2; Η, 4.5; C20H1606 requires "68.2; ·, 4.5%. Mass spectrometry shows no ions and fragments of molecules with a structure of 3 5 2 15 When the method of Example 6M Example 2. Reacting 5-hydroxy-2-hydrazine 3- (4-isopropoxy pphenyl) -2,3-dihexylbenzopyran (2.84 parts), The product 7- (4-isopropoxybenzyl) -7-hydro_2, 3,6-trifluorene-benz (l: 2 * b, 4: 5-b,) difuran (3.72 parts; 110%) s-purified product in dimethylmethylamine (55 parts, 46%) λMχ 561 nanometers, ε max 29,583. Mass spectrometric analysis showed that the molecular structure of the coupled structure was 338. gli 7 Take the method of Example 2. Add 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 Cooperative Consumer Cooperative of the Central Standards Bureau of the Ministry of Chlorine Economics (please read the precautions on the back before filling this page) Floating in methane (15 parts) In the liquid. __ Product 7- (4-methylphenyl) -7-hydrogen 3,6-trifluorene-benzo U: 2-b '4: 5-b,) difuran (1.7 parts; 115%) The product purified in dimethylformamide A max 555.6 nanometers, ε This paper size is applicable to China National Standard (CNS) A4 specification (2! 〇 × 297 mm) 4 42 48f 82109395 Inch Note TF Clover (85 A7 B7 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 is applicable to the middle and poor countries (CNS) A4 size (2IOX297mm) Shimin ---------T____-. I (Please read the precautions on the back before filling this page) " 442 4 8? No. 821093? 5 申请 Patent application inspection = document application for special perimeter rashes (November 89) ABC0 shame 89 2 V "charge 0--" <-VI. Types of Patent Application Range ί 1) Benzobifurantriamidine The formula [U and its formula I: V is the group of the following chemical formula: Or wherein: ring A is unsubstituted or substituted by 1 to 5 selected from Ci-α-fluorenyl and CX-4 -fluorenyl and combinations thereof Group substitution: 2 .—Method of making benzodiazepine 3 1Ϊ of formula (1): (Please read the precautions on the back before filling out this page) T, -β Ministry of Economy _ 央 橾 准 局Employee consumer cooperative printing Chemical formula [1] Profitable type (2) Hua Hejun: The paper scale is applicable to the Chinese National Standard (CNS) A4 wash case (21〇 乂 297 mm)