TW474811B - Novel thiazolyl benzofuran derivatives having activities as leukotriene and srs-a antagonists or inhibitors and the pharmaceutical composition thereof - Google Patents

Abstract

This invention relates to novel thiazolyl benzofuran derivatives of formula (I), wherein R1 is C1-6 alkyl, L is single bond or C1-6 alkylene optionally substituted with aryl, oxo or hydroxy, and Q is a heterocyclic group optionally substituted with one or more suitable substituent (s); or C1-6 alkoxy substituted with phenyl which is substituted with one or more suitable substituent (s) and at least one of which is C-1-6 alkoxy optionally substituted with cyano, protected carboxy, carboxy, C1-6 alkylene, a heterocyclic group optionally substituted with oxo, or amidino optionally substituted with hydroxy or C1-6 alkoxy, or its salt, which possess activities as leukotriene and SRS-A antagonists or inhibitors.

Description

811 V. Description of the invention (1) u '... B: jVU Θ ft Field of invention. D〆 > > (The present invention is related to novel compounds and their pharmaceutically acceptable salts. Especially, it has leukoenoids and allergies. Novel Blazolyl Benzofuran Derivatives and Their Permissible Salts of Slow Reactant (hereinafter referred to as SES-A) Antagonists or Inhibitors 9 Preparation Method 9 Pharmaceutical Compositions and Methods for Preventing Allergies and Inflammation of Human or Animal Background Several K-oxazolylbenzofuran derivatives 9 are known, for example, in He te Γ 0 cyc 1. Ch em • 9 1 6 9 9 7 (1 97 9) 9 Ch e ica 1 A bstract, 7 〇, 1 1 6 3 0 b and 9 0, 1 52 0 6 2 t »and EPN 0. 5 28 3 37 〇 Description of the invention The object of the present invention is to provide leukotrienes and SRS-A antagonists or inhibitors. Derivatives of active oxazolyl benzofuran And its pharmaceutically acceptable salt. Another hundred of the present invention is to provide a method for producing the derivative and its salt. Another giant of the present invention is to provide the Pi azolyl benzofuran derivative and its pharmaceutically acceptable salt. Ingredients of peony composition. Another huge aspect of the present invention is to provide a treatment method using the Iff azolyl benzofuran derivative and its pharmaceutical derivatives to prevent allergies or inflammations 9 especially to prevent asthma 9 psoriasis hepatitis bronchitis 9 gastritis 9 Esophagitis 9 Pancreatitis, Arthritis 9 Medical Inflammation »Inflammatory Abdominal Disorder 5 Shock (such as septic shock, anaphylactic shock, etc.), Arteriosclerosis, Myocardial infarction, Cerebral vasospasm, Ranitis 9 Conjunctivitis & Eczema 9 Hemostatic encephalopathy 9 Chronic obstructive pulmonary disease t Cerebral edema i Adult respiratory distress syndrome > Neonatal pulmonary hypertension 9 Ch r 〇h η's disease, dermatitis (such as ectopic dermatitis, etc.) & gt Rheumatism 9 Stomach Ulcers 9 Peptic ulcers 9 Gout, etc. The giant substance of the present invention, Plazobenzfurfuran-3-an derivative or its salt is novel and 474811 A7 B7. 5. Description of the invention (2) can be represented by the following formula (2) :

In the formula, R 1 is a low alkyl group, L is a single bond or a low alkylene group which may be substituted with an aryl group, oxygen or a hydroxyl group, and Q is a heterocyclic group which may have one or more appropriate substituents; or a low alkoxy group is substituted with Aryl and one or more suitable substituents and at least one is a lower alkoxy group which may be substituted with a fluorenyl group, a protected carboxyl group, a carboxyl group, a low alkylene group, may be substituted with an oxygen heterocyclic group, or may be substituted with a hydroxyl group or lower Formamyl, an alkane group. A preferred form of the formula (I) is a compound of the following formula (II). (Please read the notes on the back before filling this page)

In the printed format of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs-A1-A 2 -A 3-(a) -CR2 = CR 3 -X-, (b) -N = N-NR4-or (c) -NR5 -N = N-, X is S, 0 or NR 6, and R 2, R 3, R 4, RS & R 6 are each hydrogen or a suitable substituent. In addition, R 2 and R 3 and the attached fluorene atom may have more than one suitable Substituent-½ Tsa feft β Among the compounds of formula (II), the following compounds are particularly preferred, where R2 and R3 are each hydrogen or a substituent selected from the following, such as fluorenyl; carboxyl; protected carboxyl; Aryl; and can be substituted with fluorenyl, carboxyl, protected -4-This paper size applies Chinese National Standard (CNS) A4 (210X 297 mm) 474811 A7 B7 V. Description of the invention (3) Carboxyl, Heterocyclyl or cyano-lower alkyl, R4 is hydrogen or a lower alkyl that can be substituted with aryl, this aryl can be substituted with carboxyl or protected carboxyl, and R5 and R6 are the same as β4. The second preferred form in formula (I) is a compound of formula (III):

In the formula, Y is CR1Q or N, and R7, R8, R9, and R10 are each hydrogen or a suitable substituent. In addition, when R7 and R8 are connected to a nearby sulfon atom, an aromatic ring which may have more than one appropriate substituent is formed. Among the compounds of the formula (III), the following compounds are preferred, in which R7 and R8 are connected to each other to form a ring, and R7 and R8 have the following structure: -CR11, CR12-CR13 = CR14-, employees of the Central Standards Bureau of the Ministry of Economic Affairs Printed by a consumer cooperative (please read the precautions on the back before filling out this page) R9 is hydrogen; cyano; aldehyde; carboxyl; protected carboxyl; heterocyclic group; can be substituted with fluorenyl, carboxyl or protected carboxyl Alkyl; or lower alkenyl with carboxyl or protected carboxyl, βω is the same as R 9 and R11, R12, R03 and RM are each hydrogen or the substituent is selected from fluorenyl; carboxyl; protected carboxyl; halogen; Nitro; Amine; Hydroxyl; Low-cycloalkane; This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 474811 A7 B7 V. Description of the invention (4) Low alkyl and can be replaced with halogen, Hydroxy, fluorenyl, carboxyl or protected carboxyl; and lower alkoxy may be substituted with fluorenyl, heterocyclyl, fluorenyl, carboxyl, protected carboxyl, low alkylene, or may be substituted with halogen, fluorenyl, Carboxyl or protected aryl. Among such compounds of formula (III), the following are particularly preferred: wherein Y is N, R 9 is a heterocyclic group, and one of R 11, I 12, R 13 and RW is a lower alkoxy group and the other is hydrogen. The third preferred form of the compound of formula (I) is as follows, where L is a single bond, and Q is a lower alkanoyl group substituted with an aryl group, wherein the aryl group is substituted with one or more of the same or different alkoxy groups. Substituted by carboxyl, protected carboxyl, fluorenyl, cyano, and low alkylene, may be substituted by heterocyclic group of gas, or may be substituted by methylamino group of hydroxy or lower alkyl group. Among such compounds of formula (I), the following compounds are particularly preferred, in which Q is a lower alkoxy group substituted with an aryl group, wherein an aryl group is substituted with a lower alkoxy group, and a lower alkoxy group is substituted with a carboxyl group. The object (I) or a salt thereof can be produced by the following production method. Manufacturing Method 1 (Please read the notes on the back before filling this page)

-6-This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) 474811 A7 B7 V. Description of the invention (rΜΑ2_

L --C --NH '(V) (VI) or its salt -ili-i-R2

Method 3

I 4-l-z2 (VII)

I-N-T or its salt 馎 Method 4 (VIII) or its salt

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

-L-Q1 off

L-Q2 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, 15 Η-Ν;, 16 Γ \

(IX) or its reactive derivative or salt thereof

L-Q3 Responsive derivative or its salt The paper size applies the Chinese National Standard (CNS) A4 specification (2l0'i297_mm) 474811 A7 B7 V. Description of the invention (b Preparation method

RJ (1-4) or its salt

-► R

L-Q, (1-5) or its salt

RJ 〇, N ι | .. I y I -l-L-Q6 (1-6), S ^

N

S ^

LQ- (Please read the notes on the back before filling this page) or its salt method 8 p ^ QL-〇- (1-7) or its salt production method 9 (1-7) or its salt- < Λΐ / s Mi It n

-L-Q * 1 R ”Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs n

l-q1〇 debenzyl

-N

RJ TV9 (1-9) or its salt The paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm) 474811 A7 B7 V. Description of the invention (7 Quefa 10

• Q 10 r17-z3 (X) g a • ίΑΙ Jl-Ιιί N || | τ ~ 1-11) -nil

-L -Q or its salt Production method 11 or its salt

Ο -N

L-Q (1-8) 8 R18-24 (XI) or its salt or its production method 1 2 Π

(Please read the notes on the back before filling this page) Ο -Ν

L-Q (1-13) 13 Dragon r] — Ο

L-Q 14 or its Han-^ Ai > JXS Law 13 (1-14) or its Han -SAl-£ Πΐ Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

S "

Lx-Q (1-15) or its salt

-L ^ -Q This paper size applies to Chinese National Standard (CNS) A4 specification (2 丨 OX297 mm) 474811 A7 B7 V. Description of the invention (

-N

L-Q15 formazan (1-17)

L ~ * Q 16 砟 其 锞 JIB production method 15 (1-18; or its salt

L-Q 16 (IP-18) oxidation

L-Q 17 (Please read the notes on the back before filling this page) or its salt (1-19) or its salt

r \ -N

L-Q 17 esterification (1-19)

(1-20) or its reactive derivative at a carboxyl group or a salt thereof 17

L-Q 17 (1-19) or its salts

Liang Qihan-Λ 3S Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

l-q19 10- 474811 A7 B7 V. Description of Invention (9) Method 18

L-Q20 (1-22)

L-Q 21

Tellurium-τΛ SOLI method 19 -N (1-23) or Lu Hanxi, SB.

L-Q 21

ch2 (COOR ^ J (1-23) or its salt 20

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

χ-〇22 Decarboxylation (1 ~ 24)

L-Q 23 (1-25) or its han -CAi IlTl manufacturing method 2 1 Tellurium han-¾¾ 7s sn Printed by the staff consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

L-QJ: I-18]

L-Q 24 (1-26) or its j > s mx irK fm -11 This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) 474811 A7 B7 V. Description of the invention (, ◊)

, 25 (1-27) h2n-oh (XIII) or its salt or its salt 靱 法 2 3

L-Q26

L-Q 26 z5-coor! (XIV) (1-28) or its salt

27

0H (1-30), 30

-0H (XV)

3_ ^ 28 (1-31) or its salt • τΛ / s ftlt or its salt form --------- Refer to this text ----- 1T ------ 0 (Please read first Note on the back, please fill out this page again) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs R1 to R14, L, Q, X and Y are defined as above, R 15 is hydrogen or low alkyl, R16 is hydrogen, low alkyl , Arylsulfonyl, amine or heterocyclic group, and R 15 and R 16 together with the connected sulfonic atom to form a heterocyclic group containing more than one heteroatom, R 17 is a lower alkyl group which may be substituted with a carboxyl group, and a protected carboxyl group, Or aryl group can be substituted with halogen, carboxyl or protected carboxyl, -1 2- (continued on page 14) This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 474811 A7 B7 Central Standard of the Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperatives V. Description of the Invention (^) 1 1 R 3 3 is a low alkyl group which may be substituted with an aryl group substituted with a carboxyl group or a protected carboxyl group 1 1 group 9 1 1 β 3C) is a low alkyl group (substituted To aryl, where aryl is substituted with more than one /-· —S please 1 first 1 same or different alkanoyl groups, which can be substituted with carboxyl, protected carboxyl, see ik 1 group »cyano, low alkyl, can be substituted with heterocyclic group, or can be substituted with 1 or 1 methyl group with hydroxyl or low alkyl group 0 Note 1 IR, t is low alkyl, Boxing item 1 | Q 1 is a heterocyclic group substituted with one or more appropriate substituents, and at least-one is refilled. F is page Nw> 1 I (1) protected carboxyl group, 1 1 (2) lower alkyl substituted with Substituted by a protected carboxyl or aryl group to be protected by a 1 1 carboxyl group, or substituted by a protected carboxyl or aryl group to be substituted by a protected carboxyl group or an aryl group to be protected by a 1 carboxyl group; or 1 I lower alkoxy group substituted by an aryl group Group, where the aryl group is substituted with one or more appropriate substituted groups and at least--値 is substituted with a lower alkane group to be protected carboxyl group, 1 1 Q 2 is substituted with a heterocyclic group and substituted with one or more suitable substituents, and at least 1 锢• 1 is 1 (1) carboxyl 9 1 1 (2) low alkyl substituted with carboxy or aryl substituted with carboxy, or 1 I (3) low alkoxy substituted with carboxy or aryl substituted with carboxy; or 1 1 Low alkane substituted with aromatic Where aryl is substituted with more than one appropriate 1 1 substituted group and at least-one is low alkoxy substituted with carboxyl, 1 IQ 3 is heterocyclic group substituted with one or more suitable substituents, and at least one 1 1- 1 4-1 I (continued from the 1st chant) 1 1 This paper size is applicable to the Chinese National Standard (CNS) A4 size (210X 297 mm) 474811 A7 B7 V. The description of the invention (Η) is (1) carbamoyl Can be substituted with more than one lower alkyl, arylsulfonyl, amine or heterocyclic group, (2) Carboxamidine substituted with difluorenyl substituent, and it forms a heterocyclic ring containing more than one heteroatom with the connected nitrogen atom (3) lower alkyl substituted with carbamate or aryl substituted with carbamate, where carbamate is defined as (1) and (2) above, or (4) low alkoxy substituted Substituted by carbamoyl group or aryl group, wherein carbamoyl group is defined as (1) and (2) above; or substituted by alkane group with aryl group, where aryl group is substituted with more than one appropriate Substituents and at least one of them are substituted with carbamoyl, wherein carbamoyl is defined as (1) and (2) above, Q4 is hetero Substituted with one or more suitable substituents, and at least one is lower alkyl substituted with halogen, Q5 is heterocyclyl substituted with more than one appropriate substituent, and at least one fluorene is substituted with low alkyl, and Q 6 is hetero The cyclic group is substituted with more than one appropriate substituent, and at least one is (1) Carbamate, printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) (2) Low alkyl Group substitution with carbamate or aryl group with carbamate group, or (3) low alkoxy substitution with carbamate group or aryl group with carbamate group; or low alkanoyl group with aryl group, Among them, the aryl substitution is more than one appropriately -1 5- This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) 474811 A7 B7 V. Description of the invention (as small as M 0 Q is substituted by methyl benzylamine to Substitute alkoxylans as low as one and the base substitution is appropriate to 1 to replace the base ring heterocycle or the radical 氡 to replace the radical aryl or cyano to replace, the radical alkane cyano is lower or lower気 Substitute for aryl or cyano The low aeroalkane is appropriate to substitute 1 for the basic aryl in which the basic aryl is substituted for the basic alkane as low as and the 8-based Q is substituted for the cyano to replace the basic alkane as low as the basic It is appropriate to use 1 to replace the base ring heterocycle or oxazole four to replace the aryl aromatic or oxazole four to replace, and the carbazolidine four low or oxazole four to replace the aryl or oxazole four to Substitute low alkane for low acetylene. Use 1 to replace the basic aryl in aryl aryl for low alkane (please read the precautions on the back before filling this page).

The radical two is the radical Q9iT. The radical four is substituted by the radical alkane as low as 値 1 as few as 1 and the radical substitution is appropriate. One is substituted by the heterocyclic radical 1 as low as the radical substitution is appropriate. Substitute 1 for the base ring and 10 for the basic hydroxyl printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. The number of base hydroxyl groups is as low as 1 and the base is appropriately substituted with 1 for the base ring and 11 for halogen. Or the carboxy group is protected by a carboxyl group, and the carboxy group is protected by a carboxyl group. The base group or the alkyl group is low, and the number of base groups is as low as 1 and the base group is appropriately substituted by one: ring-hetero is 12.  Application of Chinese National Standard (CNS) A4 specification (210 X 297 mm) for this paper size 474811 Printed by A7 B7, Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (《M (1) Tetrazolyl substituted with low alkyl Group, which may be substituted with a carboxyl group or an aryl group substituted with a protected hydroxy group, (2) a lower alkyl group substituted with a tetrazolyl group, which may substitute an alkoxy group substituted with a carboxyl group or a protected group with an aryl group; or an aryl group With a lower alkyl tetrazolyl group, this lower alkyl group may be substituted with a carboxyl group or an aryl group substituted with a protected carboxyl group, or (3) a lower alkanoyl group may be substituted with a lower alkyl group substituted with a lower alkyl group, and this lower alkyl group may Substitute aryl group substituted with carboxyl group or protected carboxyl group; or aryl group substituted tetrazolyl group substituted with lower alkyl group, this lower alkyl group can replace aryl group substituted with carboxyl group or protected carboxyl group, Q 13 is heterocyclic group substituted with One or more suitable substituents, and at least one is nitro, Q 14 is a heterocyclic group substituted with one or more suitable substituents, and at least one is an amine group, Q 15 is a heterocyclic group substituted with one or more suitable substituents, Q 16 is Heterocyclyl substituted with more than one suitable substituent, and at least one A methyl group, Q 17 is a heterocyclic group substituted with one or more suitable substituents, and at least one is a carboxyl group, Q 18 is a heterocyclic group substituted with one or more suitable substituents, and at least one is a protected carboxyl group, and Q 19 is a heterocyclic group The cyclic group is substituted with more than one suitable substituent, and at least one is methylol, Q20 is a heterocyclic group substituted with more than one suitable substituent, and at least one -1 7-(Please read the precautions on the back before filling this page ) This paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) 474811 Printed by A7 B7, Central Consumers ’Cooperative of the Ministry of Economic Affairs. 5. Description of the invention (Ό is a low alkyl group substituted with a hydroxyl group, and Q21 is a heterocyclic ring. Group is substituted with one or more suitable substituents, and at least one is lower alkyl substituted with halogen, Q22 is heterocyclic group substituted with one or more appropriate substituents, and at least one is lower alkyl substituted with -CH (C001U) 2, Q 23 is a heterocyclyl substituted with one or more suitable substituents, and at least one is a lower alkyl substituted with -CH2 COOR ^, Q 24 is a heterocyclyl substituted with one or more suitable substituents, and at least one is vinyl substituted with a carboxyl , Q 25 A lower alkoxy group is substituted with an aryl group, wherein the aryl group has been substituted with one or more appropriate substituents, and at least one of them is a low alkoxy group substituted with a cyano group, and Q26 is a low alkoxy group substituted with an aryl group, wherein the aryl group has Substitute with more than one suitable substituent, and at least one fluorene is a lower alkanoyl group substituted with a methyl group substituted by a hydroxyl group, Q 27 is a low alkoxy group substituted with an aryl group, wherein the aryl group has been substituted with one or more appropriate substituents, And at least one is substituted with a low alkoxy group such as 1,2, 4-P and other oxazolidin-5-one-3-yl group, Q28 is substituted with a low alkanoyl group and substituted with an aryl group, wherein the aryl group is substituted with one or more of the same Or different alkanoyl groups, which can be substituted with carboxyl, protected carboxyl, fluorenyl, cyano, lower alkylene, heterocyclic with oxygen, or formyl with hydroxy or lower alkoxy , L 1 is a low alkylene group substituted with a gas, L 2 is a low alkylene group substituted with a hydroxy group, L 3 is a single bond, and Z1, Z2, Z3, 24, and 25 are each a radical. * 1 8-(Please read the notes on the back before filling out this page) This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 474811 Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Explanation (· 7) In this text, suitable examples of various definitions included in the present invention are detailed as follows. Unless otherwise specified, "low" means C i-e. The term "appropriate substituent" refers to a fluorenyl group; a carboxyl group, a protected carboxyl group; a cyano group; a halogen; a nitro group; an amine group; a fluorenylamino group; a lower alkylsulfonylamino group; a lower alkylsulfonylamino group; a hydroxyl group; Alkylthio; lower alkylsulfinyl; lower alkylsulfinyl; aminesulfinyl; aryl; heteroaryl; lower alkenyl which can be substituted with amidino, carboxyl or protected carboxyl; lower cycloalkane ; Low alkyl which can be substituted with fluorenyl, carboxyl, protected carboxyl, halogen, hydroxy, low alkylene, cyano, heterocyclyl or aryl which can be substituted with fluorenyl, carboxyl or protected carboxyl; low Alkyl radicals can be substituted with cyano, fluorenyl, carboxyl, protected carboxyl, lower alkylene, heterocyclic radicals can be replaced with oxygen, formamyl radicals can be replaced with hydroxyl or lower alkyl radicals, or aryl radicals It can be substituted with halogen, fluorenyl, carboxyl or protected carboxyl; etc. "Appropriate" lower alkyl "and" lower alkylamino "," lower alkylthio "," lower alkylsulfinyl "and A suitable "low alkyl moiety" in "low alkylsulfonyl" may be a straight or branched Cl-6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, Butyl, tert-butyl, pentyl, hexyl and the like, which is suitably Ci - 4 lower alkyl such as methyl, ethyl, propyl, butyl, isobutyl or tert-butyl. Appropriate "lower alkylene" may be straight or branched (: 1 to 6 lower alkylene, such as methylene, ethylidene, trimethylene, propylidene, tetramethylene, pentamethylene Group, hexamethylene, ethylidene, ethylene, propylene. Suitable "lower alkenyl J may be straight or branched C2-6 alkenyl such as -1 9-(Please read the back Note: Please fill in this page again.) This paper size applies to the national standard of China (CNS) A4 (210X297 mm) 474811 A7 B7 5. Description of the invention (β) Vinyl, low ethyl, propenyl, butenyl, Isobutenyl, etc. β Suitable "aryl" and "arylsulfonyl" in arylsulfonyl may be phenyl, triphenyl, tolyl, xylyl, tricyl, isopropylbenzyl , Di (third butyl) phenyl, etc., which is preferably phenyl or tolyl. Suitable "halogen j may be fluorine, ammonia, bromine or iodine, among which fluorine, chlorine or bromine is suitable. Suitable" low alkyl "Gasyl" can be straight chain or branched (: 1-e alkane, such as methoxy, ethyl, propyl, isopropyl, isobutyl, butoxy, pentyl, etc. ,among them Is a methoxy group. A suitable "heterocyclic group" may be a saturated or unsaturated, monocyclic or polycyclic heterocyclic group containing one or more heteroatoms selected from N, S and 0, and is preferably a heterocyclic group containing N Atoms, such as (1) Unsaturated 1 to 4 N 3 to 7 members (preferably 5 to 6 members) heteromonocyclic groups, such as pyrrolyl, pyrrolyl, oxazolyl, pyrazolyl, pyridyl, pyrimidine Base, pyridyl, trityl, such as 4H-1,2,4-triazolyl, 1H-1, 2,3-triazolyl, 2H-1,2,3-triazolyl Etc.), tetrazolyl, (1H-tetrazolyl, 2H-tetrazolyl, etc.); printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) (2) Including 1 to 4N saturated 3 to 7 members (preferably 5 to 6 members) heteromonocyclic groups, such as pyrrolidinyl, oxazolyl, piperidinyl, piperazinyl, etc .; (3) containing 1 to 5 N Saturated fused heterocyclic groups, such as indino, isoindolyl, indoxy, benzimidazolyl, oxalinyl, isoxolinyl, indazolyl, benzotriazole, tetrazole [Tetrazol [1,5-b] Tara well group, etc.] etc .; -20- This paper size applies to China National Standard (CNS) A4 specifications (210X2 97mm) 474811 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description ('9) (4) Unsaturated 3-7 members (preferably 5-6 members) with a single heterocyclic ring base , Such as pyranyl, furanyl, etc .; (5) Unsaturated 3 to 7 members (preferably 5 to 6 members) containing 1 to 2 S, heteromonocyclic groups, such as fluorenyl, etc .; (6) containing 1 to 2 / 0 and 1 ~ 3 · N unsaturated 3 ~ 7 members (preferably 5 ~ 6 members) heteromonocyclic group, such as oxazolyl, isoxazolyl, oxadiazolyl (such as 1, 2, 4- Duck diamidinyl, oxadiazolyl such as 1,2,4-U, 1,3,4-oxadiazolyl, 1,2,5-oxadiazolyl, etc.); etc. (Ή contains 1 to 2 Unsaturated 0 to 1 to 3 N 3 to 7 members (preferably 5 to 6 members) heteromonocyclic groups, such as morpholinyl, etc .; (8) containing 1 to 2 0 and 1 to 3 N Saturated fused ring groups such as benzazolyl, benzazolyl, etc .; (9) Unsaturated 3-7 members containing 1 ~ 2S and 1 ~ 3 値 N (preferably 5-6 members) ) Heteromonocyclic groups, such as blind oxazolyl, blind oxazolyl (such as 1,2,4-oxadiazolyl, 1,3,4-carbadiazolyl, 1,2,5-oxadiazolyl, etc. (2) Saturated with 3 ~ 7 members (preferably 5) containing 1 ~ 2_S and 1 ~ 3 N 6 members) heteromonocyclic groups, such as thiomorpholinyl, oxazolyl, etc .; (11) unsaturated fused heterocyclic groups containing 1 to 2 S and 1 to 3 N, such as phenylhydrazyl The above-mentioned "heterocyclic group" may be substituted with a suitable substitution such as a lower alkyl group, a cyclolower alkyl group, and the like, such as 4-methylpiperidinyl, 4-cyclohexylpiperidinyl, and the like. Among the above, preferred heterocyclic groups containing Q and Q1 to Q28 are as described in (1), (3) or (9) above, and the most preferable one is tetrazolyl, indyl, dahenyl or oxazolyl;- 2 1-(Please read the precautions on the back before filling this page) This paper size applies to Chinese National Standard (CNS) A4 specification (2 丨 0'〆297 mm) 474811 A7 B7 V. Description of the invention (-) R Including The basic ring hetero is better than 14 R to 9 R and 7 or 4 is the best), and the best (2 is the middle and the upper is as follows, the ring nitrogen is better than Lian '' phase base and _16 τί Four best is best and 30 β 0 A radical containing two oxazoles is better or better than basic and azole; Is the four bases morpholino or best? ) Group (1 piperidine, the upper group such as pyridine can be in its J-based amine group fluorenyl alkane or lower group Γ 0 and group J aryl group, the amino group 醯 醯 Γ group is lipid and J can be The base part Γ is based on methylamine or can be acidified. Its carboxyl group is derived from methylamino alkane carboxyl to protect its content. It can be a hexyl group or an arylmethyl group. Armour The substituents are suitably acetyl, propyl, ethyl, phosphonium, ammonium, ammonium, etc., and the amine group is derived from s ^ S 草 _ * f « ® ϋ 心 代 丁丁 (¾ take the grass care and protect the M-based ring to replace it as you can (please read the precautions on the back before filling out this page) Acetylmethylamine, Ethylamine, Ethylenediamine * U, fW, M, the base amine S1Silfis Benzene or methyl 7 N-); to the '5 and other 5 groups to form a methyl form with amidoamine i) substituted N- -SK,-Dimethylpyridine dipyridine is taken as a substitution of 4-(Upper N subprotons are printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs and printed with piperidyl 1-hexyl, cyclic 4 carbonyl, and pyridyl carbonyl. Radical I t 1 ± ΙΑ such as tf-,-.  The alkyl piperidinyl lower methyl ring 4- or, the alkyl carbonyl carbonyl low trap is substituted with a carbonyl group and the pyridylcarbonyl phenoline carbonyl group is substituted with a corkyl group containing a keto group 7 Isyl quinoline? The base is substituted with a base such as a benzyl group such as a low-fat group, the base is substituted with a base when the nitrate is substituted with a base based on a naphthyl aquatane, and the base is a base with a base of 4 School M ^ 0 0 ^ Zn II * This isIfi such as package {Keji uses ethylphenoxymethyl paper standard to apply Chinese National Standard (CNS) A4 specifications (210X297 mm) 474811 Printed by A7, Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs B7__V. Description of the invention (Η) 醯 Base, etc.). A suitable "protected carboxyl group" may be a conventionally protected carboxyl group that is allowed by pharmaceuticals, such as an esterified carboxyl group. A specific example of the carboxyl portion of the esterified carboxyl group is a low alkyl group (such as methyl, ethyl, propyl, and tertiary). Butyl, etc.), which can be substituted with substituted or unsubstituted aryl groups (such as benzyl, 4-methylbenzyl, 2,4,6-tribenzyl, etc.) and the like. Suitable "cyclo-lower alkyl" and "cyclo-lower alkyl" in "low-cycloalkane" may be C3-6 cycloalkyl, such as cyclopropyl, cyclopentyl, cyclohexyl and the like. Appropriate "free radicals" may be halogen [such as fluorine, chlorine, bromine, iodine], arylsulfonyl [such as tricresyloxy, ethylsulfonyloxy, etc.], oxyphosphonium salts [+ such as-0- PPh3 Etc.], among which halogen is preferred. The appropriate pharmaceutically acceptable salts of the target substance (I) are customary and contain metal salts, such as alkali gold tincture salts (such as sodium salt, potassium salt, etc.) and alkaline earth metal salts (such as calcium salt, magnesium salt, etc.), amine salts, organic Alkali salts (such as trimethylamine salt, triethylamine salt, triethylamine salt, pyrimidine salt, picolin salt, dicyclohexylamine salt, Ν, Ν'-dibenzyl ethylenediamine salt, etc.), organic Acid salt, anti acid salt (such as 2 acid salt, trifluoroacetate, maleic acid salt, tartrate, fumaric acid salt, mesylate, benzenesulfonate, formate, toluene Sulfonate, etc.), inorganic acid salts (such as hydrochloride, hydrobromide, hydroiodate, sulfate, phosphate, etc.), and salts of amino acids (such as spermine, aspartic acid, Glutamic acid, etc.) and so on. Compounds of formula (I) may contain more than one asymmetric center and may therefore have opposite palm bodies or diastereomers. In addition, some alkenyl-containing compounds of formula (I) may have cis-2 3- (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) Α4 size (210X 297 mm) ) 474811 A7 B7 5. Description of the invention (p) or trans isomer. The invention may contain mixtures or individual isomers thereof. Compounds of formula (I) may contain tautomers and the present invention may contain mixtures or individual isomers thereof. The compound of formula (I) and its salt may be in the form of a solvate, which is also within the scope of the present invention. The hydrate is preferably hydrate and ethoxide. The present invention also contains isotopic sacrifice derivatives of compounds of formula (I) for biological research. The manufacturing method of the object (I) is detailed below. Production method 1 The object (I) or a salt thereof can be prepared by subjecting a compound (IV) or a salt thereof to a cyclization reaction. The reaction is suitable for the presence of a dehydrating agent [such as acetic anhydride] or a base such as gold test [such as lithium, sodium, potassium, etc.], alkaline earth metal [such as calcium, magnesium, etc.], gold test [hydrogen] [such as Naim], pound Earth metal arsenic hydride [such as hydrazone, etc.], alkali metal arsenic oxide [such as sodium formazan, sodium ethane gas, potassium third butoxide, etc.], alkaline earth aurantium hydride [such as magnesium formate, Magnesium ethoxylate, etc.], Trialkylamines [Trimethylamine, Triethylamine, etc.], Picolin, 1,5-Diacylbicyclo [4. 3. 0] non-5-ene, 1,4-diazine bicyclic [2. 2. 2] octane, 1,8-diazine bicyclic [5. 4. 0] eleven-7-ene and the like. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling out this page) The reaction is generally performed in conventional solvents, such as dioxane, tetrahydrofuran, pyridine, aromatic hydrocarbons (such as benzene, toluene, Xylene, etc.] or other organic solvents that have no adverse effect on the reaction. The reaction temperature is not fixed, and it is generally carried out under cooling to heating. Method 2-2 4-This paper size applies to Chinese National Standard (CNS) A4 specifications (210X297 mm) 474811 A7 B7 V. Description of the invention (> The object (II-1) or its salt can be prepared by reacting the compound (V) or its salt with the compound (VI) or its salt. General reaction In conventional solvents, such as alcohols [such as methanol, ethanol, propanol, isopropanol, etc.], aromatic hydrocarbons [such as benzene, toluene, xylene, etc.], ethyl acetate, acetonitrile, diUI alkane, chloroform, dichloromethane, N, N -dimethylformamide, or other organic solvents that do not adversely affect the reaction. The reaction temperature is fixed, and it is generally carried out under cooling to heating. Process 3 Compound (III) or a salt thereof can make the compound (VII) or its salt and compound (V III) or a salt thereof. The reaction is generally carried out in the presence of an inorganic or organic base. A suitable inorganic may contain alkali metals (such as sodium, potassium, etc.), alkali metal hydrides (such as NaOH, KOH, etc.), alkali gold tincture. Osmates (such as sodium hydrogen osmate, potassium osmate, etc.), osmium metal master salts (such as sodium sulfonate, etc.), earth metal master salts (such as calcium carbonate, etc.), and metal hydrides (such as NaH, etc.) etc. Appropriate organic test may contain tri-lower alkylamines (such as triethylamine, N, N-diisopropylethylamine, etc.), alkyl magnesium bromide (such as methyl magnesium bromide, ethyl bromide)纟 ϋ, etc.), lithium alkyl (such as methyl lithium, butyl lithium, etc.), lithium diisopropylamidide, lithium hexamethyl disilazide, etc. "Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read first Note on the reverse side, please fill in this page again) The reaction is generally performed in conventional solvents, such as water, alcohols (such as methanol, ethanol, isopropanol, etc.), tetrahydrofuran, dioxane, toluene, dichloromethane, chloroform, Ν, Ν- Dimethylmethanamine or other organic solvents or their mixtures that do not adversely affect the reaction. The reaction temperature is not critical and is generally lower than Cool down to warm up. -25- This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 474811 A7 B7 V. Description of the invention (Method 4 Object (1-2) or its order) Compound (1-1) or its salt is obtained by deesterification reaction. This reaction is usually carried out by conventional methods such as hydrolysis, reduction, etc. The hydrolysis is preferably carried out in the presence of an age or an acid containing a Lewis acid. A suitable base contains an inorganic base And organic tests, such as alkali metals [such as lithium, sodium, potassium, etc.], alkaline earth metal tincture [such as magnesium, calcium, etc.], its hydroxide or sulfonate or double sulfonate, trioxaneamine [such as trimethylamine, Triethylamine, diethylisopropylamine, etc.], picolin, 1,5-diazine bicyclo [4. 3. 0] non-5-ene, 1,4-diazine bicyclic [2. 2. 2] octane, 1,8-diazine bicyclo [5 · 4.  0] eleven -7-ene and the like. Suitable acids may include organic acids [such as formic acid, acetic acid, propionic acid, triacetic acid, trifluoroacetic acid, etc.] and inorganic acids [such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, etc.] and Lewis acids [such as three Boron bromide, etc.]. The reaction is generally carried out under water, alcohol (such as methanol, ethanol, etc.), xylene, diethanol monomethyl ester, digas methane, tetrahydrofuran, a mixed solution thereof, or other organic matter which does not adversely affect the reaction. The reaction temperature is not critical, and it is generally carried out under cooling to back temperature. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) This reduction reaction is particularly suitable for removing 4-nitrobenzyl, 2-iodoethyl, 2, 2, 2- Ester group of trigas ethyl. The reduction method used to remove the reaction may include chemical reduction and catalytic reduction. The reduction is performed by a conventional method including chemical reduction and catalytic reduction. A suitable reducing agent for chemical reduction is a combination of metals (such as tin, iron zinc, etc.) or gold tincture compounds (such as chromium chloride, acetic acid, etc.) with organic or inorganic-2 6- This paper applies Chinese national standards (CNS ) A4 specification (210 × 297 mm) 474811 A7 B7 V. Description of the invention (acids (such as formic acid, acetic acid, propionic acid, trifluoroacetic acid, p-toluenesulfonic acid, hydrochloric acid, hydrobromic acid, etc.) Suitable for catalyst reduction Catalysts are customary, such as platinum catalysts (such as platinum plate, sponge platinum, platinum black, platinum oxide, etc.), and rake catalysts (such as sponge rake, rake black, gasification handle, rake / shuttle, gelatinous platinum, Rake Hydroxide / Sulfur, Rake / Barium Sulfate, Rake / Sulfuric Acid, etc.], Nickel catalysts [such as reduced nickel, nickel oxide, Ruanlai nickel, etc.], Cobalt catalysts (such as reduced cobalt, Ruanlai cobalt, etc.), Iron contacts Catalysts [such as reduced iron, Ruan Lai Tie, etc.], copper catalysts (such as reduced copper, Ruan Lai Cu, Woolman copper, etc.), etc. β This catalyst can be reacted in the presence of hydrogen or such as formic acid, ammonium formate, cyclohexene The reduction reaction is generally carried out in a solvent that does not adversely affect the reaction. Water, alcohol [such as methanol, ethanol, propanol, etc.], N, N-dimethylformamide, or a mixture thereof. Therefore, when the acid used in the chemical reaction of the hydration is a liquid, it can also be used as a solvent. The suitable solvent for the catalyst reduction reaction may be a sulphuric solvent, and other conventional solvents, such as diethyl ether, dioxane, tetrahydrofuran, etc. or a mixture thereof. The reaction temperature is not fixed and is generally carried out under cooling to heating. Preparation method 5 Economy Printed by the Ministry of Standards and Staff ’s Consumer Cooperatives (Please read the notes on the back before filling out this page) Compound (1-3) or its salt can make compound (1-2) or its carboxyl reactive derivative or its salt and The compound (IX) or its amine-reactive derivative or a salt thereof is prepared. The amine-based appropriate reaction derivative of the compound (IX) may contain Schiff ’s fluorene obtained from the compound (IX) and a carbonyl compound such as an aldehyde, ketone, or the like. -Type imine or its tautomeric diamine isomer; composed of compound (IX) and such as Ν, Ο -bis (trimethylsilane-21-this paper size applies to Chinese National Standard (CNS) A4 specification (210 × 297 mm) ) 474811 A7 B7 V. Description of the invention (> 〇 ) Silane derivatives obtained from silylating agents such as acetamide, N-trimethylsilylacetamide. Suitable reaction derivatives of compound (1-2) may contain fluorenyl chloride, anhydride, activated fluoramine, activated ester, etc. Appropriate The anhydride may be a symmetric anhydride or a mixed anhydride with an acid such as a substituted phosphoric acid (such as dialkyl phosphoric acid, phenyl phosphoric acid, diphenyl phosphoric acid, dibenzyl phosphoric acid, halogenated phosphoric acid, etc.), dialkyl phosphorous acid, sulfuric acid, thiosulfuric acid, Alkane sulfonic acid, (such as methanesulfonic acid, ethanesulfonic acid, etc.), alkane sulfonic acid, aliphatic carboxylic acid (such as pivalic acid, valeric acid, isovaleric acid, etc.), etc. Properly activated sulfonamide can be oxazolidine , 4-substituted imidazolamide, dimethylpyrazolamide, triazolamide, tetrazolidine, etc. Suitable activated esters are dimethylimide methyl esters ((ch3) 2n = ch-], vinyl esters, Propynyl ester, 4-nitrophenyl ester, 2,4-dinitrophenyl ester, trichlorophenyl ester, pentachlorophenyl ester, pentafluorophenyl ester, mesylate, phenylthioester, p-nitrophenylthioester, Carboxymethylthioester, pyranyl ester, pyridyl ester, 8-quinololine thioester, and N-hydroxy compounds (such as N, N-dimethylhydroxylamine, 1-hydroxy-2H-pyridone, N-hydroxy-butane Diamidine , N-Hydroxyphthalimide, N-Hydroxybenzotriazole, etc.] activated esters and the like. These reactive derivatives can be arbitrarily selected depending on the kind of the compound (1-2) to be used. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). If the compound (I-2) reacts in free form or its salt, it should be reacted in the presence of the following condensing agent; Carbodiimides [eg N, H'-dicyclohexyl sulfonated diimine, N-cyclohexyl-N '-(4-diethylaminocyclohexyl) sulfonated diimine, N-ethyl- N '-(3 -dimethylaminopropyl) sulfonated diimine or its hydrochloride], diphenylphosphine hydrazide, diphenylsulfenyl chloride, diethylsulfonyl cyanide, bis (-2 8-Ben Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 474811 A7 B7 V. Description of the invention (Clever) Chlorazine // imidazolium B5 1 3-oxazolimidylcarbonyloxyethyl. Carbonyloxyethyl J τ * Η I group, etc. Cyanide Chloride Polytriline 0 Hydrodipyridine Amine. Low-line three-way, lower salt in acid storage sulfonium is not as good as metallurgical base or available in the machine, etc. should be morpholinotransmorphane low 0 ^ 0 soluble «methyl hydrogen ^ Xi Jia Yu} 'two general grade N- Monoalcohol N should be propane, antiisoform, gas 0 Propane water such as alkanediol glycol alcohol, ethane, methanol chloroform, such as t benzyl 0, Ying Liang should not oppose it or its amine / 4 «When the temperature is increased, the temperature is increased until it is colder than 0. The lower solution is mixed strictly without temperature or the warming agent should be dissolved by the reaction method. The gas is 5-compounded. Chemical compound can be cyanide, belongs to I—, gold and other potassium-containing compounds can be compounded and reacted. Anti-metallic compounds such as C, etc. can be combined with copper 0 to T-cyanide (please first (Please read the notes on the back and fill in this page again.) Store the media when it is in contact with it. It should be transferred. Instead, use the alkali in the iodine e agent Gold Ad such as Xi 3, etc. 3, etc. * \ 7 化, C miscellaneous i Γ, d Na A: Iodine alcohol such as product, t commercial water product 4 Ruhua 46, etc. Alcohol ethyl alcohol as printed by the staff consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs There should be no reaction. Add to the solution or mix it under the liquid, and add it to the amine temperature. Add one or two times to the base, and N agent, N, dissolved, it has no «degree, ring Pyridoxine reaction? Pyridine anti-method, non-chemical compound can be salted or 7 I 0 (water derived demethylpyridine salt obtained from I, its paper size applies to Chinese National Standards (CNS) A4 specification (210X297 mm) 474811 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of invention (μ) The dehydration reaction can be dehydration of carbamoyl group to hydrazone based on customary methods, and appropriate dehydrating agents can be phosphorus compounds (Such as phosphorus pentoxide, phosphorus pentachloride, thorium oxychloride, pyrocatechin tri-gasification dish, etc.); sub-horizontal chloride; or triaryl groups (such as triphenylsulfonium, etc.) and atmosphere simulation Or tetragasification of carbon. The reaction is generally carried out in conventional solvents, such as water, alcohols (such as methanol, ethanol, isopropanol, etc.), tetrahydrofuran, dioxane, toluene, digasmethane, atmospheric imitation, Ν, Ν -dimethyl Methylformamide or other organic solvents or their mixtures that do not adversely affect the reaction The reaction temperature is not fixed and is generally carried out under cooling to warming. Preparation method 8 The target compound (1-8) or its salt can be obtained by reacting the compound (1-7) or its salt with an azide compound. Appropriate stack Nitrogen compounds may contain rhenium osmium azide [such as beta sodium sulfide, beta potassium osmide, etc.], alkaline earth metal osmium nitride [such as calcium azide, etc.], aluminum azide, hydrogen azide, azide Trimethyltin, etc. The reaction is generally carried out in, for example, tetrahydrofuran, dioxane, N, N-dimethylformamide or other organic solvents which do not adversely affect the reaction. The reaction temperature is indeterminate and is generally carried out under heating to heating. Method 9 The compound (I-1D) or a salt thereof can be prepared by removing the benzyl group of the compound (1-9) or a salt thereof. Removal of benzyl is generally performed by a conventional method that can remove benzyloxy as a hydroxyl group, and the applicable agent can be boron tribromide; a combination of trifluoroacetic acid and a sulfur compound (such as thiomethoxybenzene, 1,2-ethanedione Thiols, etc.); Lewis acid (such as -30- (Please read the notes on the back before filling in this page) This paper size applies to Chinese National Standard (CNS) A4 specification (210 × 297 mm) 474811 A7 B7 V. Description of the invention (Β) in combination with Louis 鹸 (such as ethylene glycol, etc.); trimethylsilyl iodine; etc. The removal of benzyl is generally carried out using a catalyst and a catalyst reduction reaction of hydrogen or a hydrogen donor. Appropriate catalysts used in catalyst reduction reactions are customary, such as sodium catalysts (such as platinum black, lead sulfonate, platinum gaseous compounds, etc.), rake catalysts (such as black, sulfonate, rake gaseous compounds, etc.), etc. β Appropriate The hydrogen donating agent may be cyclohexene, cyclohexadiene, ammonia formate, hydrazine, etc. The reaction is generally carried out in water, alcohols [such as methanol, ethanol, isopropanol, etc.], tetrahydrofuran, diII, etc., toluene, digas methane. , Aeroform, Ν, Ν-dimethylformamide, or other non-defective reactions The reaction is carried out in an organic solvent of alum or a mixed solution thereof. The reaction temperature is not strictly determined and is generally carried out under cooling to warming. Production method 10 Compound (1-11) or a salt thereof can make compound (I-1ϋ) or a salt and compound thereof (X) or a salt thereof. The reaction can be imitated by the method 3, so the reaction conditions (such as solvent, reaction temperature, etc.) can be referred to the method 3. Preparation method 11 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs ( Please read the precautions on the back before filling this page) The target (1-12) or its salt can be prepared by reacting the compound (1-8) or its salt with the compound (XI) or its salt. Under the test, such as the gold hurricane (such as sodium, potassium, etc.), alkaline earth metal rhenium (such as magnesium, calcium, etc.), its hydride or hydrogenation or sulfonate or disulfonate. It is carried out under customary solvents without adverse effects, such as -3 1-This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 474811 A7 B7 V. Description of the invention (v) Water, dioxane, alcohol) such as Methanol, ethyl acetate, etc.), acetonitrile, tetrahydrofuran, Ν, Ν- 二Methylformamide, acetone, 2-butanone, or a mixture thereof. Therefore, when the compound (X I) is in a liquid, it can also be used as a solvent. The reaction temperature is not critical and is generally carried out under cooling to heating. In the reaction, the compound (1-12) can be substituted at the 1 or / and 2 position with R 18 β according to the reaction conditions. This is also within the scope of the present invention. Production method 12 The compound (1-14) or a salt thereof can be obtained by reducing the compound (1-13) or a salt thereof. The reduction is performed by a conventional method including chemical reduction and catalytic reduction. Suitable reducing agents for chemical reduction are a combination of metals (such as tin, iron zinc, etc.) or metal compounds (such as chromium chloride, chromium acetate, etc.) and organic or inorganic acids (such as formic acid, acetic acid, propionic acid, trifluoroacetic acid, etc.). P-toluenesulfonic acid, hydrochloric acid, hydrobromic acid, etc.). Appropriate catalysts for catalyst reduction are users, such as platinum catalysts (such as platinum plate, platinum black, platinum oxide, etc.), and rake catalysts (such as rake black, oxide rake, and Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs). Printed (Please read the precautions on the back before filling in this page) Rake / Sulfur, etc.], Nickel catalysts [such as reduced thorium, nickel oxide, Ruan Laixi, etc.], Ming catalysts [such as reduced cobalt, Ruanlai cobalt Etc.], iron catalysts [such as reduced iron, Ruan Lai copper, etc.], copper catalysts [such as reduced copper, Ruan Lai copper, Woolman copper-etc.] and so on. The reduction reaction is generally carried out in a conventional solvent which does not adversely affect the reaction, such as water, an alcohol [such as methanol, ethanol, propanol, etc.], N, N-dimethylformamide or a mixture thereof. Therefore, when the acid used in the above chemical reduction reaction is a liquid, it can also be used as a solvent. In addition, the catalyst reduction reaction is suitable -32- The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 474811 A7 B7 V. Description of the invention (V) The solvent used can be the above solvents, and other conventional solvents, Such as diethyl ether, dioxane, tetrahydrofuran, etc. or a mixture thereof. The reaction temperature is not strictly determined and is generally carried out under cooling to warming. Preparation method 13 Compound (1-16) or a salt thereof can be prepared by reacting compound (1-15) or a salt thereof with a reducing agent. An appropriate reducing agent can be Aluminium hydride (such as lithium aluminum hydride, lithium lithium hydride), borohydride (such as sodium borohydride, etc.), aluminum alkoxide (such as isopropyl aluminum oxide, etc.) and so on. The reaction is preferably carried out in the presence of water, alcohols (such as methanol, ethanol, isopropanol, etc.), aerosol, ether, dioxane, or other organic solvents or their mixtures that do not adversely affect the reaction. The reaction temperature is not critical and is generally carried out under cooling to heating. Production method 14 Compound (1-18) or a salt thereof can be prepared by reacting compound (1-17) or a salt thereof with a formate. A suitable formylating agent may be Ν, Μ-dimethylformamide; (CH3) 2 Ν + = CHC1.  Cl2 Ρ02_ (Vilsmeier reagent prepared by the reaction of Ν, Ν -dimethylformamide with atmospheric phosphorus, phosgene, etc.); printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back first) (Fill in this page again.) When the formazan is Ν, Ν -dimethylformamide, the reaction should be in the presence of a base such as a low alkyl metal (such as n-butyllithium, ethylmagnesium bromide, etc.). get on. The reaction is generally carried out in an alkane such as diU, tetrahydrofuran, N, N-dimethylformamidine, methane, imitation, or other organic solvents or mixed solvents which do not adversely affect the reaction. -33- The size of this paper is applicable to Chinese National Standard (CNS) A4 (2 丨 0 × 297mm) 474811 A7 B7 V. Description of the invention (^) The reaction temperature is not fixed and is generally carried out under cooling to heating. Production method 15 Compound (1-19) or a salt thereof can be prepared by gasifying compound (1-18) or a salt thereof. The gasification reaction is generally performed by a user who can oxidize methylformyl to a carboxyl group. A suitable oxidizing agent may be an oxyacid such as periodate (such as sodium periodate, potassium periodide, etc.), and a peroxy acid such as benzyl peroxide. Acids (such as peroxybenzic acid, isogas peroxybenzic acid, etc.), potassium permanganate, chromic acid, sodium pervaporate, etc. The reaction is generally used in conventional solvents such as water, alcohols (such as methanol, ethanol, propanol, etc.), tetrahydrofuran, alkane such as diH, digas methane, diazaethane, aeroform, N, N-dimethylformamide, N , N-dimethylacetamide, or other organic solvents or their mixtures that do not adversely affect the reaction. Among solvents, a hydrophilic solvent may be used in combination with water. The reaction temperature is not fixed and is generally carried out under cooling to heating. Production method 16 The compound (I-2Q) or a salt thereof can be prepared by reacting a compound (1-19) or a reaction derivative of a carboxyl group thereof or a salt thereof with a hydroxy compound. The carboxyl-reactive derivative of compound (1-19) may be a halogen (such as tritium gas, terbium bromide, etc.). Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back before filling this page). Suitable hydroxy compounds can be alcohols (such as methanol, ethanol, propanol, benzyl alcohol, etc.), phenol, resorcin, etc. The reaction is generally carried out in a conventional solvent such as diethyl ether, tetrahydrofuran, dioxane or other organic solvents which do not adversely affect the reaction, or a mixture thereof. Therefore, when the above hydroxy compound is in a liquid, it can also be used as a solvent. -3 4-This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) 474811 A7 B7 5. Description of the invention (W) The reaction temperature is not fixed and is generally carried out under cooling to heating. When the compound (1-19) is used in the form of a free acid, the reaction is preferably performed in the presence of an inorganic acid or a condensing agent. A suitable inorganic acid may be exemplified by the above-mentioned production method 4 and a suitable condensing agent may be exemplified by the above-mentioned production method 5. Production method 17 The compound (1-21) or a salt thereof can be obtained by reacting the compound (1-19) or a salt thereof with a reducing agent. Suitable reducing agents may be aluminum hydrides (such as aluminum hydride, lithium hydride aluminum tributoxide, etc.), borohydrides (such as borane-dimethylmethylene sulfide complex, sodium borohydride, etc.), Aluminum alkoxide (such as aluminum isopropylate, etc.) and so on. The reaction is preferably carried out in the presence of water, alcohols (such as methanol, ethanol, isopropanol, etc.), chloroform, diethyl ether, dioxane, or other organic solvents or their mixtures that do not adversely affect the reaction. The reaction temperature is not critical and is generally carried out under cooling to heating. Production method 18 Compound (1-23) or a salt thereof can be obtained by compound (1-22) or a salt thereof. Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). The halogenation reaction is generally performed using conventional halogenating agents, such as halogens (such as chlorine, bromine, etc.), and phosphorus trihalides (such as three Phosphor bromide, phosphorus trichloride, etc.), phosphorus pentahalide (such as phosphorus pentachloride, phosphorus pentabromide, etc.), phosphorus oxychloride (such as phosphorus trichloride, phosphorus trichloride, etc.); grasshopper _ ( (Such as grass chlor chloride, grass chloro bromide, etc.), sulfolazone (such as sulfonium atmosphere, etc.), pyridinium bromide hydrobromide, etc. The reaction is generally in solvents such as water, alcohols (such as methanol, ethanol, isopropanol, etc.) -35- This paper size applies to Chinese National Standard (CNS) A4 specifications (210 × 297 mm) 474811 A7 B7 V. Description of the invention (M), benzene , Dioxane, N, N-dimethylformamide, tetrahydrofuran, methane dioxane, dioxane, chloroform, ether, or other organic solvents or their mixtures which do not adversely affect the reaction. The reaction temperature is not critical and is generally carried out under cooling to warming. Production method 19 The compound (1-24) or a salt thereof can be obtained by reacting the compound (1-23) or a salt thereof with a malonic acid derivative (XII). The reaction is generally carried out in the presence of an inorganic or organic hafnium such as the production method 3. The reaction is generally used in conventional solvents, such as water, alcohols (such as methanol, ethanol, isopropanol, etc.), tetrahydrofuran, dioxane, toluene, N, N-dimethylformamide, or other organic solvents that do not adversely affect the reaction. Or mixed solution. The reaction temperature is not critical and is generally carried out under cooling to warming. Production method 20 The compound (1-25) or a salt thereof can be prepared by decarboxylating the compound (1-24) or a salt thereof. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) This reaction contains deesterification and acid-catalyzed decarboxylation. This deesterification reaction is preferably performed in the presence of an inorganic base as exemplified in Production Method 3. The acid used in the acid-catalyzed carboxylation reaction may be an inorganic or organic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, and the like. The reaction is generally carried out in conventional solvents such as water, alcohols (such as methanol, ethanol, isopropanol, etc.), tetrahydrofuran, dimer, toluene, xylene, dichloromethane, aerobic, N, N-dimethylformamidine Amines or other organic solvents or their mixtures that do not adversely affect the reaction. -36- This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 474811 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (from) The reaction temperature is not rigorous and is generally cooled to Under heating. Production method 2 1 Compound (1-26) or a salt thereof can be obtained by reacting compound (1-18) or a salt thereof with malonic acid. The reaction is generally carried out in the presence of organic bases such as ammonia, primary or secondary amines (e.g. methylamine, dimethylamine, piperidine, etc.), pyridine, picolin, and the like. Process 2 2 Compound (1-28) or a salt thereof can be obtained by reacting compound (1-27) or a salt thereof with hydroxylamine or a salt. The reaction can be carried out according to Example 11 or a similar method. Process 2 3 Compound (1-29) or a salt thereof can be obtained by reacting compound (1-28) or a salt thereof with compound (XIV) or a salt thereof. The reaction can be carried out according to Example 119 or a similar method. Production method 2 4 The compound (1-31) or a salt thereof can be prepared by condensing the compound (I-3Q) or a salt thereof with the compound (X V) or a salt thereof. This reaction can be performed according to the Mi tunobu reaction or a salt-like method thereof. This reaction is suitable for the presence of di-lower alkyl azodicarboxylate (such as diethyl azodicarboxylate) and trialkyl or triarylphosphonium (such as triphenylphosphine). The reaction is generally carried out in a conventional solvent, such as tetrahydrofuran, dioxane, toluene, methylene chloride, aerobic, Ν, Ν-dimethylformamide, or other organic solvents which do not adversely affect the reaction, or a mixture thereof. The reaction temperature is not fixed and is generally carried out under cooling to warming. -3 7-(Please read the notes on the back before filling in this page) The paper size applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 474811 A7 B7 5. Description of the invention (μ) The target compound can be used if necessary According to customary usage, the isolation is purified from the reaction solution and converted into the target salt. Suitable salts of the compounds (I), (I-1) to (I-3 1), (I I), (I I-1), and (I I I) to (XV) can be exemplified as the compound (I). The target compound (I) or a pharmaceutically acceptable salt thereof has potent activity as a leukotriene and SRS-A antagonist or inhibitor, and can be used to prevent allergies or inflammation in humans or animals, especially to prevent asthma, psoriasis, hepatitis, and branches. Tracheitis, gastritis, esophagitis, pancreatitis, arthritis, nephritis, inflammatory abdominal disease, shock (such as septic shock, anaphylactic shock, etc.), animal sclerosis, myocardial infarction, cerebral vasospasm, rickets, conjunctivitis, Eczema, hemostatic encephalopathy, chronic obstructive pulmonary disease, cerebral edema, adult snoring distress syndrome, neonatal pulmonary hypertension ^ Chrohn's disease, dermatitis (such as ectopic dermatitis, etc.), rheumatism, gastric ulcer , Peptic ulcer, gout, etc. To illustrate the usefulness of the object (I), the pharmacological data of the representative compound (I) are shown below. 3 H-Leuko triptin D4 receptor binding (i) Test method (a) Membrane preparation Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (Please read the precautions on the back before filling this page) Human tissue lymphoma cells U937 Polytorn (Kinematica) was homogenized in 5mHTris-HCl (PH7_5), and the tissue pieces were removed by centrifugation (100OXg, 10 minutes). The supernatant was centrifuged (3600 Q X g, 20 minutes), and the obtained particles were resuspended in a buffer solution (5ibH Tris-HCl (pH 7. 5), homogenize with a Teflon homogenizer and centrifuge (3 6 QQ 0 X g, 20 minutes), the obtained particles are used as the rough film part, stored at -7 (TC for future use. -38- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 474811 A7 B7 V. Description of the invention (β) (b) 3 Η-leukotriene D4 combined with the preparation membrane The frozen crude membrane part is thawed and suspended in the culture medium 1 (1QbH Tris -HC 1 ρ Η 7 · 5, 1 0 b HC a C 1 2, 1 0 is Μ M g C 1 2,5 B Μ Cysteine, 51! 1! 1 Glycine). Combined with the analysis, the 311-leukotriene 04 (0. 31 ^) and drug and membrane prepared with 100 / il (100 / ^ g protein / tube) incubate at 25 ° C for 30 minutes in medium 1 with a final dissolution volume of 500; ul) e immediately vacuum filtered through Whatnan GF / B filter to »1 ice-cold buffer (10nH Tris-HCl PH7. 5) Wash 3 times to achieve receptor binding from free 3 Η-leukotriene D4. The binding in the presence of lyuM leukotriene D4 is non-specific binding. The radioactivity remaining in the dishwasher was measured by a liquid flash meter (Packerd TRI-CARB 4530). (ii) Test results --------- Clothing-(Please read the precautions on the back before filling this page) Order the test compound printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (Example No.) IC50 ( nM) 2 1 < 5 22-2 < 5 22-16 < 5 2 2-23 < 5 22-24 < 5 22-27 < 5 28-3 < 5 34-3 < 5 34-5 < 5 34-8 < 5 34-10 < 5 34-11 < 5 105-1 < 5 This paper size is in accordance with Chinese National Standard (CNS) A4 specifications (ίΐϋ_97 mm) 474811 A7 B7 V. Description of the invention (4) When used for treatment, the compound (I) and its pharmaceutically acceptable salt of the invention may be used as an active ingredient And blends such as organic or inorganic solid, semi-solid or liquid excipients suitable for oral, parenteral or topical application, such as capsules, tablets, tablets, tablets, suppositories, solutions, lotions, inhalants, Ophthalmic preparations, lotions, suspensions, emulsions, ointments, gels, etc. β may further contain adjuvants, stabilizers, wetting or emulsifying agents, buffering agents and other conventional additives if necessary. The dose of Compound (I) varies depending on the age and physical condition of the patient. The average single dose is about 0.1, 1, 10, 50, 100, 250, 500 and 1000 mg. Compound (I) is effective for the above diseases. Generally, each person administers 0.1 to about 100 mg per day. The abbreviation used is as follows: (Please read the precautions on the back before filling this page) Mee: = methyl printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Et: = ethyl η P r:: propyl i P r: = isopropyl η B u = butyl t Bu: = third butyl c P en = cyclopentyl B z 1 = benzyl B zh = Dityl Tet: = 1H -tetrazol-5 -yl Ph: = phenyl The following production examples and examples illustrate the invention. -4 0-This paper size is in accordance with Chinese National Standard (CNS) A4 (210X 297 mm) 474811 A7 B7 V. Description of the invention Preparation Example 1 Mixed 3 -Methylmethyl-5-methyl B indole ( 0.50g) hydroxylamine hydrochloride (0.44g) and sodium acetate (0.52 g) in acetic acid (5 m 1), stirred for 2 hours, then added acetic anhydride (2.5 m 1), the reaction flow was 0. 5 hours. After cooling, the reaction mixture was poured into ice water and extracted with ethyl acetate. The insoluble matter was filtered off, and the filtrate was washed with water and brine, dried over magnesium sulfate, and concentrated under reduced pressure. After silica gel column chromatography, the solution was dissolved in ethyl acetate and a gaseous M solution, and the filtrate containing the target substance was collected and concentrated under reduced pressure to obtain 3-methyl-5-methylindole (109 mg). IR (Nujol): 3250, 2200, 1520 cm'1 NMR (CDC13, δ): 2.48 (3Η, s), 7.15 (1H, d, J = 8.4Hz), 7.37 (1H, d, J = 8.4Hz) , 7.56 (1H, s), 7.69 (1H, d, J = 2.9Hz), 8.79 (1H, br s) MASS: 157 (M + H) + H12_ The following compounds were prepared in the same manner as in Preparation Example 1. (Please read the notes on the back before filling this page)

Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs-41- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 474811 A7 B7 V. Description of the invention (〇) Preparation example R12 R13 R14 Physical properties 2- 1 Cl Η H IR (Nujol): 3250, 2200, 1520 cm-1 NMR (CDC13, δ): 7.30 (1H, dd, J = 8.7, 1.9Hz), 7.41 (1H, d, J = 8.7Hz) / 7.70 — 7.80 (2Hr m), 8.77 (1H, br s) MASS: 176 (M +) 2-2 F Η H IR (Nujol): 3250, 2200, 1170 cm-1 NMR (DMSO-dg, δ) : 7.15 (1H, ddd, J = 9.2, 9.1, 1.9Hz), 7.42 (1H, dd, J = 9.2, 2.5Hz), 7.58 (1H, dd, J = 9.1, 4.5Hz), 8.32 (1H, s ), 12.31 (1H, br-s) MASS: 161 (M + H) + 2-3 K Cl H IR (Nujol): 3250, 2210, 1170 cm'1 NMR (DMSO-dg, δ): Ί.26 (1H, dd, J = 8.5, 1.9Hz), 7.63 (1H, d, J = 1.9Hz), 7.66 (1H, d, J = 8.5Hz), 8.31 (1H, s), 12.31 (1H, br s ) MASS: 176 (M) + Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Preparation Example 3 Add 4-Tertiary Butylhydrazine Hydrochloride (5.0) Aqueous sodium hydrogen acid solution, the mixture was extracted with ethyl acetate, and dried over magnesium sulfate. Evaporated under reduced pressure to give 4-phenyl-butoxy third well (4. 2g). The resulting product was azeotropically stirred under reflux with benzene (70 ml) of ethyl pyruvate (3.2 g) for 2 hours. After cooling, benzene solution of p-toluenesulfonic acid (-4 2-This paper is in accordance with Chinese National Standard (CNS) A4 Specifications (210X297 mm) 474811 A7 B7 V. Description of the invention (4i) 70ml), azeotropically stirred at reflux for 2 hours. After cooling, the reaction mixture was collected by filtration and concentrated under reduced pressure. The residue was separated into aqueous sodium hydrogen sulfonate and ethyl acetate. The ethyl acetate layer was washed with water and brine, dried over magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography, and then dissolved in a mixed solution of ethyl acetate and n-hexane. The solutions containing the target substance were combined and concentrated under reduced pressure to obtain ethyl 5-tert-butylindole-2-carboxylate (4.00 g).

mp: 109-11CTC IR (Nujol): 3230, 1690, 1530, 1520, 1460, 1320, 1250 cm'1 NMR (CDC13, δ): 1.41 (9Η, s), 1.45 (3H, t, J = 7.1Hz ), 4.40 (2H, q, J = 7.1Hz), 7.18 (1H, m), 7.24-7.45 (2H, m), 7.65 (1H, d, J = 0.8Hz), 8.94 (1H, br s) MASS : 246 (M + H) + Preparation Example 4 A solution of ethyl 5 -third butylindole-2-carboxylate (3.0 g) and IN NaOH was added to tetrahydrofuran (2 0 m 1) and methanol (1 0 m 1), and the mixture was stirred at 40 ° C. for 5 hours. Remove the solution. The resulting aqueous solution was acidified with dilute hydrochloric acid. The precipitate was collected by filtration, and washed with water to obtain 5-tert-butylindole-2-carboxylic acid (2.47 g). IR (Nujol): 3350, 3100, 1660, 1520, 1460, 1320, * 1250 cm-1 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) NMR (CDCI3, δ ): 1.41 (9Η, s), 7.04 (1H, d, J = 2.0Hz), 7.30-7.40 (2H, m), 7.58 (1H, s), 11.56 (1H, s), 12.80 (1H, br s ) MASS: 218 (M + H) + Preparation Example 5 Mixed 5-third butylindin-2-carboxylic acid (2.3 g) and copper powder (0.46 g)-4 3-this paper The scale is applicable to the national standard (CNS) A4 specification (2I0X297 mm) 474811 A7 B7 V. Description of the invention (Heart) Sunnyline (20 m 1) liquid. Stir at 2 2 0 -C for 1 hour. After cooling, the mixed solution was separated into dilute hydrochloric acid and diethyl ether. The diethyl ether layer was washed with dilute hydrochloric acid 3 times, sodium hydrogen sulfonate and brine, dried with sulfuric acid, and distilled under reduced pressure to obtain 5-third butylindole B (2 1 0 g) 0 IR (Nujol): 3400, 1720, 1575, 1470, 1415, 1360, 1315 cm-1 NMR (CDCI3 / δ): 1.39 (9Η, s), 6.49-6.52 (1H, m), 7 · 14 — 7 · 17 (1H, ία), 7 · 24_7 · 34 (2H, m), 7.64 (1H, s), 8.02 (1Η, br s) MASS: 174 (M + H) + 馎Backlog fi

Under ice cooling, sulfosyl isocyanate (1 ml) was added dropwise to a suspension of 5 -tributylindole (2.1 g) in acetonitrile (15 m 1) over 10 minutes. After stirring at the same temperature for 1 hour, a solution of N, N-dimethylformamide (1 m 1) in acetonitrile (20 in 1) was added and stirred at 50 for 1 hour. The reaction mixture was poured into ice-water and extracted with ethyl acetate. The solution was washed with brine, dried over magnesium sulfate, and evaporated under reduced pressure. The obtained residue was subjected to silica gel column chromatography, and the mixture was separated with ethyl acetate and n-hexane. Indine (1.2Dg). mp: 185-187 ° C IR (Nujol): 3250, 2200, 1520 cm'1

Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs of the People's Republic of China (Please read the notes on the back before filling this page) NMR (CDC13 / δ): 1.49 (9H, s), 7.42 (2H, s), 7.71 (1H, d, J = 3.0Hz), 7.74 (1H, d, J = 0.7Hz), 8.88 (1H, br s) MASS: 199 (M + H) + Preparation Example 7 The following compounds were modeled as suitable wormworm compounds in Preparation Example 6 be made of. -4 4-This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) 474811 A7 B7 V. Description of the invention (^)

Preparation example r12 r13 r14 Physical properties, 7-1 iPr Η H mp: 160-161 ° C IR (Nujol): 3250, 2200, 1520, 1460, 1420, 1380, 1240 cm-1 NHR (CDC13, δ): 1.32 (6H, d, J = 7.0Hz), 3.05 (1H, sept, J = 7.0Hz), 7.22 (1H, dd, J = 1.6, 8.6Hz), 7.40 (1H, d, J = 8.6Hz), 7.61 (1H, d, J = 0.8Hz), 7.70 (1H, d, J = 1.8Hz), 8.67 (1H, br s) MASS: 185 (M + H) + 7-2 KH Me mp: 175-176 ° C IR (Nujol): 3250, 2200, 1525, 1460, 1440, 1380, 1340, 1330, 1230 cm-1 ^ NMR (DMS0-d6, δ): 2.51 (3H, s), 7.06-7.18 (2H, m ), 7.46 (1H, d, J = 7.1Hz), 8.26 (1H, d, J = 3.1Hz), 12.22 (1H, br s) MASS: 157 (M + H) + -------- -^^ 衣 — (Please read the notes on the back before filling this page)

-4I Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs —45— This paper is in accordance with the Chinese National Standard (CNS) A4 (210X297 mm) 474811 A7 B7, Invention Description (material) 51 Preparation Example r12 r13 r14 Physical Properties

7-3 H Me Η mp: 149-150 ° C IR (Nujol): 3250, 2200, 1530, 1500, 1450, 1410, 1360 cm-1 NMR (DMSO-dg, δ): 2.42 (3H, s), 7.07 (1H, dd, J = 1.0, 8.1Hz), 7.34 (1H, d, J = 1.0Hz), 7.52 (1H, d, J = 8.1Hz), 8.16 (1H, d, J = 2.8Hz), 12.05 (1H, br s) MASS: 157 (M + H) +

7-4 CF3 Η H mp: 163-1640C IR (Nujol): 3200, 2210, 1620, 1600, 1510, 1450, 1430, 1370, 1355, 1340. cm-1 NMR (CDC13, δ): 7.59 (2H, s), 7.86 (1H, d, J = 3.0Hz), 8.09 (1H, s), 9.06 (1H, br s) MASS: 210, 211, 212

7-5 OBzl Η H mp: 158-163 ° C IR (Nujol): 3200, 2200, 1620, 158 0 cm-** NMR (DMSO-dg, δ): 5.16 (2H, s), 6.99 (1H , dd, J = 2.6, 8.8Hz), 7.18 (1H, d, J = 2.6Hz), 7.32- Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) 7.51 ( 6H, m), 8.17 (1H, d, J = 3.0Hz), 12.07 (1H, br s) MASS: 249 (M + H) +, -46 ~ This paper size applies to China National Standard (CNS) A4 specifications ( 210X297 mm) ^ 811 A7 B7 V. Description of the invention (〇) Preparation example R12 R13 R14 Physical properties (Please read the precautions on the back before filling this page)

7 ~ 6 K OMe H mp: 189-190 ° C IR (Nujol): 3250, 3100, 2200, 1630, 1580, 1530 cm-1 NMR (DMS0-d6, δ): 3.80 (3H, s), 6.88 ( 1H, dd, J = 2.2, 8.9Hz), 7.02 (1H, d, J = 2.2Hz), 7.50 (1H, d, J = 8.9Hz), 8.10 (1H, d, J = 2.9Hz), 11.97 ( 1H, br s) ____MASS: 173 (M + H) + _ Production "Example 8 Mix 5-benzyloxy-2-nitrophenylacetic acid (4.0Og), concentrated sulfuric acid (0.6ml) and isopropanol ( 4ϋι »1) Stir to reflux for 1 day. The solution was evaporated and redissolved in ethyl acetate. Wash sequentially with sodium bicarbonate water, water and brine, and dry with magnesium sulfate. Concentrated under reduced pressure to give 5-benzylamino-2-nitrophenylisopropyl acetate (4.20g) e

mp: 143.0-147.8 ° C IR (Nujol): 1740, 1620, 1600, 1510 cm-1 NMR (CDC13, δ): 1.23 (6H, d, J = 6.9Hz), 3.96 (2H, s), 5.00 ( 1H, sept, J = 6.9Hz), 5.13 (2H, s), 6.87 (1H, printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, J = 2.8Hz), 6.96 (1H, dd, J = 9.〇 , 2.8Hz), 7.34-7.43 (5H, m), 8.18 (1H, d, J = 2.8Hz), 13.68 (1H, br s) MASS: 330 (M + H) +, 288, 270 ^ Preparation Example 9 Mix 5-benzylamino-2-nitrophenyl isopropyl acetate (4.2 g), ammonium gas (0.42 g) and iron powder (4.2 g) in a mixture of ethanol (20 μβ1) and water (10 ml) , -4 7- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 474811 A7 B7 V. Description of the invention (4) Stir at 8 (TC for 1.2 hours. After cooling, filter the reaction The solution was concentrated under reduced pressure. The layers were separated into water and ethyl acetate, and the organic layer was washed with brine, dried over magnesium sulfate, and evaporated under reduced pressure to give 2-amino-5-benzyloxyphenyl isopropyl acetate (3.9 g). Preparation Example 10 A solution of potassium acetate (1.34g), 2-amino-5-benzyloxyphenyl isopropyl acetate (3.9g) and acetic anhydride (4.0g) in benzene (40ml) was mixed at 8D ° C. Stir 3D points. Drop within 15 minutes Add isovaleronitrile (2.3 g) and stir at the same temperature for 4 hours. After cooling, insoluble matter is filtered off, and the filtrate is concentrated under reduced pressure. Redissolve in isopropanol (3Qml) containing concentrated sulfuric acid (0.5 m 1) , Stir for 3 hours at 8 G ° C. Cool to room temperature, filter the crystals, and wash with isopropyl ether to give 5-benzyloxy-1 问 -wen-3 -carboxylic acid isopropyl ester 2.4 g. IR (Nujol): 1740, 1620, 1600, 1510 cm-1 NMR (DMSO-dg, δ): 1.35 (6Η, d, J = 6.9Hz), 5.18 (2H, s), 5.20 (1H, sept, J = 6.9Hz), 7.17 (1H, dd, J = 2.4, 9.0Hz), 7.32-7.50 (1H, m), 7.58 (1H, d, J = 9.0Hz), 13.77 (1H, br s) MASS: 311 ( M + H) +, 269 Preparation Example 11 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). Ethyl-3-(3 i -dimethylaminopropyl) carbonylation Diimine (5 · 8 7 011) was added under cooling with 4 -isopropylbenzene trap hydrochloride (5.0 g), acetic acid (1.8 4 m 1), triethylamine (3.73ml) and 1- A solution of hydroxybenzitriazole hydrate (40.4 mg) in dichloromethane (50 ml) was stirred at room temperature overnight. The solvent was distilled off, and the layers were diluted with dilute hydrochloric acid and ethyl acetate. Washed with saline The organic layer was dried over magnesium sulfate and concentrated under reduced pressure. Silica gel column chromatography, the dichloromethane and methanol mixed solution were separated, the filtrate of the target compound was collected, and concentrated under reduced pressure to give 1-ethylamyl-2- (4-isopropylphenyl)- Well (3.00g). This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 474811 A7 B7 V. Description of invention (〇)

mp: 118.7-119.7 ° C IR (Nujol): 3350-3000, 1650 cm 1 NMR (CDC13, δ): 1.20 and 1.22 (6H, d, J = 6.9Hz), 2.05 and 2.11 (3H, s), 2.83 (1H, sept, J = 6.9Hz), 5.74 and 6.10 (6H, br s), 6.69-7.40 (5Hf m) MASS: 193 (M + H) + E_JTj @ U_2_ Suspension 1-Ethyl- 2-( 4 -cumyl) hydrazone (2.95g), hydroxylamine hydrochloride (3.49g), and sodium sulfate (14.32g) in water (50ml) containing 1N hydrochloric acid water (15.6 m 1), heated to 1 0 Q ° C. To the homogeneous reaction mixture, chloral (3.04g) was added dropwise, and the mixture was heated to 100 ° C for 10 minutes. At room temperature, half of the solvent was distilled off and extracted with ethyl acetate. The organic layer was washed with water, brine, dried over magnesium sulfate, and concentrated under reduced pressure. Silica gel column chromatography, dissolving in a mixture of methane and methanol. The target compound layer was collected and concentrated under reduced pressure to obtain 2.89 g of N-acetamido-4-isopropyl-isonitrosoethylanilide.

mp: 113.5-115.5 ° C IR (Nujol): 3600-2500 cm-1 NMR (CDC13, δ): 1.20 (6Η, d, J = 6.9Hz), 1.96 (3Η, s), 2.87 (1H, br s ), 7.10-7.40 (4H, m), 7.50 and 8.04 (1H, br s), 9.08 and 10.03 (1H, br s) MASS: 264 (M + H) + Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ( (Please read the precautions on the reverse side before filling out this page) Preparation Example 1 Add N-acetamido-4-isopropyl-isonitrosoacetanilide (1.87 g) in batches at 55 ° C Concentrated sulfuric acid, heated to 85 ° C, reacted for 15 minutes, after cooling, water (2 E) g) was added, and the suspension was flowed for 3.5 hours. The precipitate was filtered off. Washing with water and a mixture of isopropyl ether and digas methane gave 5-isopropyl-1-indene 11¾-3-carboxylic acid. -49- This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) 474811 A7 B7 V. Description of the invention (4〇

mp: > 230 ° C IR (Nujol): 3400-2300, 1700 cm-1 NMR (CDC13, δ): 1.26 (6Η, d, J = 6.9Hz), 3.04 (1H, sept, J = 6.9Hz) , 7.36 (1H, d, J = 8.7Hz), 7.57 (1H, d, J = 8.7Hz), 7.89 (1H, s), 13.68 (1H, br s) MASS: 205 (M + H) + elemental analysis ： C11H12N2 Calculated value: C 64.69, H 5.92, N 13.72 Measured value: C 64.46, H 5.99, N 13.62 Preparation Example 1 4 Mixed 5 -isopropyl-1H -ind_-3 -carboxylic acid (1.44g) and concentrated Sulfuric acid (2 drops) in methanol (20 m 1) was stirred at reflux for 1 day, the solvent was distilled off, and then dissolved in ethyl acetate. The ethyl acetate extract was sequentially washed with sodium bicarbonate water, water and brine, dried over magnesium sulfate, and concentrated under reduced pressure to give methyl 5-isopropyl-1H-Hindole-3-carboxylate (1.39g) e.

mp: 143.0-147.8 ° C IR (Nujol): 3400-3000, 1720 cm-1 NMR (CDCI3, δ): 1.34 (6H, d, J = 6.9Hz), 3.09 (1H, sept, J = 6.9Hz) , 3.07 (3H, s), 7.38 (1H, dd, J = 8.7, 1.6Hz), 7.66 (1H, d, J = 8.7Hz), 8.03 (1H, d, J = 1.6Hz), 13.68 (1H, br s) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) MASS: 219 (M + H) + Preparation Example 1 5 The following compounds were obtained by simulating Preparation Example 14. 1H-indolin-3-carboxylic acid benzyl ester The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) 474811 A7 B7 V. Description of the invention (49) IR (Nujol): 3230, 1680, 1585 , 1450 cm-1 NMR (CDC13, δ): 5.54 (2Η, s), 7.25-7.50 (7H, m), 7.72 (1H, d, J = 8.4Hz), 8.17 (1H, d, J = 8.4Hz ) Preparation Example 1 6 3 -methylamidoindo-5-carboxylic acid (3.47g), hydroxylamine hydrochloride (1.97g) and sodium acetate (2.41 g) in acetic acid (3 0 in 1) After stirring for 12 hours, acetic anhydride (15 m 1) was added and the reaction was refluxed for 5 hours. After cooling, the mixture was filtered and evaporated under reduced pressure. After adding methanol, the mixture was evaporated under reduced pressure. Sulfinous sulfonium gas (8 m 1) and a small amount of N, N-dimethylformamide were added to the residual digas methane (20 ml). After stirring at room temperature for 2 hours, the mixture was evaporated under reduced pressure. Treat with methanol and concentrate under reduced pressure. The layers were separated into sodium bisulfate water and ethyl acetate. The ethyl acetate layer was washed with brine, dried over magnesium sulfate, evaporated under reduced pressure, and subjected to silica gel column chromatography. The mixed solution of ethyl acetate and aerosol was dissolved. The target compound was collected, and concentrated under reduced pressure to obtain 3-aminoindolido-5 -carboxylic acid methyl ester (2.87 g). IR (Nujol): 3250, 2200, 1720, 1690, 1620, 1520 cm-1 NMR (CDCI3, δ): 3.89 (3Η, s), 7.66 (1H, d, J = 8.6Hz), 7.90 (1H, dd , J = 8.6, 1.6Hz), 8.26 (1H, d, J = 1.6Hz), 8.42 (1H, s), 12.60 (1H, br s) MASS: 200 (M) +, 169, 141 Preparation example 1 7 Yin Juju, a consumer cooperative of employees of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Mix 4 -Third-Butyl-2- (5-methylmethylphenylfuran-2-yl) Bfazole ( 1.83 g) and tetrahydrofuran (10 ml) of triethyllinacetate (1.53 ml) and N, N-dimethylformamide (10 inl) were stirred under ice-cooling. After a few minutes, potassium tert-butoxide was added and stirred at the same temperature for 1 hour. The resulting mixture was poured into ice-water and extracted with ethyl acetate. The organic layer was washed with brine, dried over magnesium sulfate, and decompressed -5 1-This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) 474811 A7 B7 V. Description of the invention (p) Concentrated to obtain a slurry, which is passed through silicone gel Column chromatography, dissolving with a mixture of n-hexane and ethyl acetate. The target compound was collected, and concentrated under reduced pressure to obtain ethyl (E) -3- [2- (4-tributylbutylcarbazol-2-yl) phenylarfuran-5-yl] acrylate (0-68 g). IR (Nujol): 1705, 1625, 1580, 1500, 1280 cm-1 NMR (CDC13, δ): 1.35 (3Η, t, J = 7.1Hz), 1.41 (9H, s), 4.28 (2H, q, J = 7.1Hz), 6.45 (1H, d, J = 16.0Hz), 7.00 (1H, s), 7.34 (1H, s), 7.54 (2H, s), 7.78 (1H, d, J = 16.0Hz), 7.77 (1H, s) MASS: 356 (M + H) + Preparation Example 1 8 (E) -3- [2- (4-Third-Butylazolidin-2-yl) -Benzofuran-5-yl ] A solution of ethyl acrylate (0.65 g) in tetrahydrofuran (lOffll) was hydrogenated with 10% Pd-C (0.1 g) at room temperature under atmospheric pressure. The catalyst was filtered off, and concentrated under reduced pressure to obtain ethyl 3- [2- (4-tert-butyltriazol-2-yl) benzofuran-5-yl] propanoate (0.65g) o IR (Neat): 1725, 1630, 1585, 1500, 1400 cm-1 NMR (CDC13, δ): 1.23 (3Η, t, J = 6.8Hz), 1.41 (9Η, s), 2.66 (2H, t, J = 7.8Hz), 3.04 (2H, t, J = 7.8Hz), 4.13 (2H, q, J = 6.8Hz), 7.00 (1H, s), 7.23 (1H, dd, printed by the staff consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please first Read the notes on the back and fill in this page) J = 1.4, 8.0Hz), 7.30-7.55 (2H, m), 7.75 (1H, d, J = 1.4Hz) MASS: 358 (M + H) + Preparation M. ... li Lithium aluminum hydride (. 14 g) is added with 3-[2-(4 -tert-butylcarbazol-2-yl) phenylphosphofuran-5-yl] propionate (0.65 g) Tetrahydrofuran in a blunt gas chamber-5 2-This paper is in accordance with Chinese National Standard (CNS) M specifications (210X 297 mm) 474811 A 7 B7 V. Description of the invention (β) A mixed solution is formed at temperature, stirred for 2 hours, added water, filtered The precipitate was removed, and the mixture was extracted with ethyl acetate. The organic layer was washed with brine, dried over magnesium sulfate, and concentrated under reduced pressure to give 3- [2- (4-tert-butyltriazol-2-yl) benzofuran-5-yl] propyl Alcohol (〇.42g) 0 IR (Nujol): 3250, 3100, 1500, 1460 cm-1 NMR (CDC13, δ): 1.41 (9Η, s), 1.80-2.05 (2H, m), 2.81 (2H, t, J = 7.4Hz), 3.69 (2H, t, J = 6.2Hz), 6.96 (1H, s), 7.17 (1H, dd, J = 1.8 and 8.4Hz), 7.28 (1H, s), 7.42 (1H, d, J = 1.8Hz) , 7.44 (1H, d, J = 8.4Hz) MASS: 316 (M + H) + mixed 3- [2- (4 -Third-butyloxazosin-2-yl) phenylsulfan-5-yl] Propanol (0.40 g) and methane (5 ml), sulphur tritium gas (0.4 ml), were stirred at reflux for 5 hours. After cooling to room temperature, the solution was concentrated under reduced pressure, and the layers were partitioned between sodium bicarbonate and ethyl acetate. The organic layer was washed with brine, dried over magnesium sulfate, and decompressed to give 4-tert-butyl-2- [5- (3 -Gaspropyl) benzofuran-2-yl] Plazole (D 28g) 0 IR (Neat): 1585, 1500, 1460 cm-1 NMR (CDC13, δ): 1.41 (9Η, s), 2.06-2.20 (2H, m), 2.88 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) (2H, t, J = 7.4Hz) / 3.54 (2H, t, J = 6.4 Hz), 6.97 (1H, s), 7.16 (1H, dd, J = 2.2, 8.4Hz), 7.27 (1H, s), 7.43 (1H, d, J = 2.2Hz), 7.45 (1H, d, J = 8.4Hz) MASS: 334 (M + H) + table salt (0.47g) added 4-third butyl-2- (5-methyl phenyl benzofuran-53-this paper size applies Chinese national standards (CNS ) A4 size (210X297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 474811 A7 _B7__ V. Description of the invention (η) -2-yl) azole (0.41g), sodium hydrogen phosphate 12 hydrate (0.23g) And 2-methyl-2-butane (0.69 ml) in water (3rol), tetrahydrofuran (7.5 ml) and a third butanol (12.6 m 1) were mixed. After 4 hours, sodium hydrogen sulfide was added. It was extracted with ethyl acetate, and the organic layer was washed with brine, dried over magnesium sulfate, and concentrated under reduced pressure, dissolved in 1 N-N a 0 Η, treated with sulfonate, and diluted with hydrochloric acid. The precipitate was collected and washed with water to give 2- (4-tert-butyltriazol-2-yl) benzofuran-5-carboxylic acid (0.38 g). IR (Nujol): 2500-2700, 1680, 1610, 1585 οπΓ1 NMR (DMS0-d6, δ): 1.37 (9Η, s), 7.53 (1H, s), 7.65 (1H, s), 7.80 (1H, d , J = 8.7Hz), 8.00 (1H, dd, J = 1.7 and 8.7Hz), 8.37 (1H, d, J = 1.7Hz) MASS: 302 (M + H) + will be 2- (4-the third one The mixed solution of oxyzolidazol-2-yl) phenylbenzofuran-5-carboxylic acid (5.0 g) and sulfinyl nitrogen (12.1) 111> in tetrahydrofuran (501011) was stirred at 50 ° for 2 hours. After cooling to room temperature, the precipitate was collected by filtration, and washed with isopropyl ether to obtain 2- (4-tert-butyl Ptazol-2-yl) benzofuran-5-carbonyl chloride hydrochloride (5.57 g) e IR (Nujol). : 2500-2200, 1830, 1790, 1770, 1740, 1600, 1585, 1560 cm-1 Preparation Example 2 3 Tetrahydrofuran (10 ml) of 5-benzylindoline (0.50 g) at room temperature and 2-3 atmospheres Hydrogenated with 10% Pd-C (0.1 g). The catalyst was filtered off, and the filtrate was concentrated under reduced pressure. Ethyl 4-bromobutyrate (0.475 m 1), potassium sulfonate (0.4 4 3 g) and methyl ethyl ketone were added to the mixture and stirred under reflux for 1 day. The solvent was removed, and the target substance was collected by silica gel column chromatography, ethyl acetate and toluene mixed solution. 4-This paper size is applicable to China National Standards (CNS) M specifications (2 丨 0X W7 mm) I order ~ (Please (Please read the notes on the back before filling this page) 474811 A7 _B7__ 5. Description of the invention (Η) layer, concentrated under reduced pressure to obtain ethyl 4-[(5-indolinyl) oxy] butyrate (() .398) . IR (Neat): 3400, 1720, 1620, 1580, 1470, 1455, 1420 cm-1 NMR (CDC13, δ): 1.26 (3Η, t, J = 7.1Hz), 2.13 (2H, quint, J = 7.3Hz ), 2.55 (2H, t, J = 7.3Hz), 4.04 (2H, t, J = 7.3Hz), 4.15 (2H, q, J = 7.1H ?;), 6.4Ί--6.47 (1H, m) , 6.84 (1H, dd, J = 2.4, 8.8Hz), 7.09 (1H, d, J = 2.4Hz), 7.15-7.17 (1H, m), 7.27 (1H, d, J-8.8Hz), 8.02 ( 1H, br s) MASS: 287 (M + H) +, 115 mixed 5-ethylammonyl-2-hydroxybenzaldehyde (1.68g), 2-bromomethyl-4-tert-butyl Stazole, 5 carbonic acid Potassium (1.24 g) and potassium iodide (0.59 g) in N, N-dimethylformamide (1 0 π 1) were stirred at room temperature for 5 hours. The mixture was added to ice water and extracted with ethyl acetate. The organic layer was washed with brine, dried over magnesium sulfate, and concentrated under reduced pressure. The obtained slurry was mixed with xylene of acetic anhydride under reflux for 1 day. After cooling to room temperature, the resulting slurry was subjected to silica gel column chromatography, and the mixed solution of toluene and ethyl acetate was dissolved. The target compound layer was collected and decompressed to obtain 4-tert-butyl-2- (5-ethylfluorenylbenzofuran-2-yl) Pfazole (1.83 g). IR (Nujol): 1680, 1600, 1500 cm-1 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) NMR (CDC13, δ): 1.41 (9Η, s), 2.68 (3Η, s), 7.02. (1Η, s), 7.41 (1H, d, J = 0.8Hz), 7.59 (1H, d, J = 8.6Hz), 8.01 (1H, dd, J = 1.8 and 8.6 Hz), 8.27 (1H, d, J = 1.8Hz) MASS: 300 (M + H) + -55- This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 474811 A7 _ __B7_ V. Description of the Invention (Materials) Preparation of J1 Example 25 (Please read the precautions on the back before filling this page) Blind at 2- (4-Third-butyl-2- (5-Ethylphenylbenzofuran-2-yl) A solution of oxazole (0.6 g) in methane (5 ml) was added dropwise to a solution of copper (II) bromide (0.89 g) in ethyl acetate (7bU) at reflux for 20 minutes. Stir at reflux for 9 hours and cool To room temperature, add water, neutralize with sodium hydrogen sulfonate, filter off insoluble matter, extract with ethyl acetate, wash with brine, dry over magnesium sulfate, and concentrate under reduced pressure. Silica gel column chromatography, mixed with toluene and ethyl acetate Dissolve. Collect the target and decompress it to give 4-tert-butyl-2- [5-bromoethylfluorenyl)骈 furan-2-yl] azole (0.45 g) 〇IR (Nujol): 3100, 1685, 1605, 1500, 1430 cm-1 NKR (CDC13, δ): 1.42 (9Η, s), 4.52 (2Η, s), 7.04 (1Η, s), 7.43 (1H, s), 7.63 (1H, d, J = 8.7Hz), 8.02 (1H, dd, J = 1.7, 8.7Hz), 8.30 (1H, (d, J = 1.7Hz) MASS: 380 (M + H) +, 378 (M + H) + Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, Miao Yin, dropwise add methyl magnesium bromide (1 M) Tetrahydrofuran (2.6 ml) into a solution of 4-tert-butyl-2- (5-formylbenzofuran-2-yl) oxazole (3.0 g) in tetrahydrofuran (30 ml). Isothermal After stirring for 15 minutes, it was poured into ice water, neutralized with dilute hydrochloric acid, extracted with ethyl acetate, washed with water and brine, dried over magnesium sulfate, and evaporated under reduced pressure. After silica gel column chromatography, the mixed solution of n-hexane and ethyl acetate was dissolved. The target solution was decompressed to give 4-tert-butyl-2- [5- (1-hydroxyethyl) benzopyranfuran-2-yl) conazole (2.04 g). IR (Nujol): 3500-3000 NMR (CDC13, δ): 1.41 (9H, s >, 1.56 (3H, d, J = 6.4Hz), 5.01 (1H, q, J = 6.4Hz), 6.98 (1H, s), 7.31 (1H, s), 7.36 (1H, dd, J = 8.6, 1.7Hz), 7.51 (1H, d, J = 8.6Hz), 7.62 (1H, d, J = 1.7Hz) MASS: 302 (M + H) + This paper size applies the Chinese National Standard (CNS) A4 specification (doWh mm) _ 474811 A7 B7 V. Description of the invention (Jiang) Preparation Example 27 The following compounds were prepared by simulating Preparation Example 26.

Preparation Example R19 Physical properties 27-1 Et IR (Nujol): 3500-3000 cm-1 NMR (CDC13, δ): 0.93 (3H, t, J = 7.0Hz), 1.42 (9H, s), 1.81 ( 2H, quint, J = 7.0Hz), 4.70 (1H, t, J = 7.0Hz), 6.98 (1H, s), -7.33 (1H, dd, J = 8.5, I.6Hz), 7.34 (1H, s ), 7.51 (1H, d, J = 8.5Hz), 7.59 (1H, d, J = 1.6Hz) MASS: 316 (M + H) + '27-2 Ph IR (Nujol): 3500-3000 cm-1 NMR (CDC13, δ): i.41 (9H, s), 5.96 (1H, s), 6.97 (1H, s), 7.25-7.50 (8H, m), 7.65 (1H, d, J = 1.6Hz) MASS: 364 (M + H) + Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs (Please read the precautions on the back before filling out this page) 馎 Example 28 Mixed 2- (4-Third-Butyl-2- [ 5- (1-Hydroxyethyl) benzofuran-2-yl) conazole (1.5 g) and 1,2-digasethane (35 ml) of sulfenyl chloride (0.44 ml) were stirred under reflux for 2 hours. After cooling, adjust the pΗ value to 7 with sodium hydrogen sulfonate, separate the organic layer, wash with brine, dry with magnesium sulfate, and evaporate under reduced pressure to obtain 2- (4-第 -57-) This paper size applies Chinese national standards (CNS ) A4 specification (210X297 mm) 474811 A7 B7 V. Description of the invention (r0 tributyl-2- [5- (1-chloroethyl) benzopyranfuran-2-yl) P azole (1.31 g). IR (Nujol): 1300 cm-1 NMR (CDCI3, δ): 1.41 (9Η, s), 1.92 (3Η, d, J = 6.8Hz), 5.24 (1H, q, J = 6.8Hz), 6.99 (1H, s), 7.31 (1H, s), 7.42 (1H, dd, J = 8.6, 1.8Hz), 7.53 (1H, d, J = 8.6Hz), 7.65 (1H, d, J = 1.8Hz) MASS: 320 (M + H) + Preparation Example 2 9 The following compounds were prepared by following Preparation Example 2 8 in the following manner.

^ —— N

tB, R19 Preparation example R19 Physical properties 29-1 Et IR (Nujol): 1250 cm-1 NMR (CDCI3, δ): 1.02 (3Η, t, J-7.2H-), 2.19 (2Η, quint, J = 7.2 Hz), 4.90 (1H, t, J = 7.2Hz), 6.98 (1H, s), printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) 7.29 (1H, s ), 7.37 (1H, dd, J = 8.6, 1.8Hz), 7.52 (1H, d, J = 8.6Hz), 7.61 (1H, d, J = 1.8Hz) MASS: 334 (M + H) + 29- 2 Ph NMR (CDCI3, δ): 1.55 (9H, s), 6.25 (1H, s), 7.08-7.50 (9H, m), 7.73 (1H, s) MASS: 378 (M + H) + -58- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 474811 A7 B7 V. Description of the invention (β) M Preparation Example 30 Mixed 2-hydroxy-3-methylaminobenzaldehyde (3.04g), 2- Ethyl bromopropionate (5.85g) and dimethyl fiH (20iBl) of potassium sulfonate (4.14g) were stirred at 70 ° C for 5 hours. Diluted with water, neutralized with IN hydrochloric acid, extracted with ethyl acetate, separated the organic layer, washed with brine, dried over magnesium sulfate, and concentrated. The crude product (6.93g) was subjected to silica gel column (60g) chromatography, n-hexane and toluene (6: 1 ~ 5: 1) Dissolved to give 2- (2-methylamino-6-methoxyphenoxy) -ethyl propionate (5.25g). IR (Film): 1735, 1685, 1580 cm'1 NMR (CDC13, δ): 1.23 (3Η, t, J = 7Hz), 1.64 (3H, d, J = 7Hz), 3.88 (3H, s), 4.13 (2H, q, J = 7Hz), 5.05 (1H, dd, J = 7Hz), 7.14 (2H, m), 7.47 (1H, m), 10.61 (1H, s) Preparation Example 3 1 The following compounds were used in the preparation examples Made by 30. (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs-59- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 474811 A7 B7 V. Description of the invention (Β)

R ^, r22 O ^^ COOR20 OHC

Preparation example r20 r21 r22 r23 r24 Physical properties 31-1

Me Me

H o Me H ((S) -isomer) [a] E5 = -45.43. (C = 1.0, CHC13) IR (Film): 1740, 1685, 1250 cm-1 NMR (CDC13, δ): 1.64 (3H, d, J = 6.9Hz), 3.72 (3H, s), 3.88 (3H, s), 5.05 (1H, q, J = 6.9Hz), 7.12 (2H, d, J = 4.6Hz), 7.44 (1H, t, J = 4.6Hz), 10.60 (1H, s) MASS: 239 (M + H) + (Please read the notes on the back before filling this page)

31-2 Bzh nPr H 〇Me H Printed by 31-3 Me Et IR (Film): 1740, 1686, 1580 cm-1 NMR (CDC13, δ): 0.94 (3H, t, J = 7Hz), 1.3-1.6 (2H, m), 2.0 (2H, m), 3.63 (3H, s), 5.17 (1H, t, J = 6Hz), 6.88 (1H, s), 7.0-7.4 ( 13H, m), 10.58 (1H, s) H OMe H IR (Film): 1742, 1690, 1585 cm ~ -NMR (CDCI3, δ): 1.10 (3ΙΓ, t, J = 7Hz), 2.04 (2H, m ), 3.69 (3H, s), 3.86 (3H, s), 5.00 (1H, t, J = 6Hz), 7.1 (2H, m), _7.4 (1H, m), 10.63 < 1H, s) _60_ This paper size is in accordance with Chinese National Standard (CNS) A4 (210X 297 mm) 474811 A7 B7 V. Description of the invention (β Preparation example r20 r21 r22 r23 r24 Physical properties 31-4

Et Me Me OMe H IR (Film): 1730, 1685, 1580 cm-1 NMR (CDC13, δ): 1.34 (3H, t, J = 7Hz) / 1.59 (6H, s), 3.78 (3H, s), 4.28 (2H, q, J = 7Hz), 7.0-7.2 (2H, m), 7.43 (1H, m), 10.48 (1H, s)

31-5 tBu Η H OMe H NMR (CDC13, δ): 1.46 (9H, s), 3.89 (3H, s), 4.72 (2H, s), 7.11-7.16 (2H, m), 7.4-7.5 (1H , m), 10.65 (1H, s) (Please read the precautions on the back before filling this page)

31-6 Me H Me OMe H ((R)-isomer) fa] ^ 5 = + 44.39 ° (c = 0.9, CHCI3) IR (Film): 1740, 1680, 1580, 1470 cm-1 NMR (CDC13 , δ): 1.64 (3H, d, J = 6.9Hz), 3.72 (3H, s), 3.88 (3H, s), 5.05 (1H, q, J = 6.9Hz), 7.09-7.18 (2H, m) , 7.40-7.49 (1H, m), 10.60 (1H, s) MASS: 239 (M + H) + 31-7 Bzh nPr Η H 〇Me IR (Film): 1750, 1732, 1675, 1600, 1496 cm- 1 NHR (CDC13, δ): 0.96 (3H, t, J = 7Hz), 1.55 (2H, m), 2.0 (2H, m), 3.58 (3H, s), 4.81 (1H, dd, J = 5.2, 7.2Hz), S.13 (1H, d, J = 2.2Hz), 6.52 ΠΗ, dd, J = 2.2, 8.8Hz), 6.92 (1H, s), 7.1-7.37 (10H, m), 7.82 (1H , d, J = 8.8Hz), 10.43 (1H, _s) ________ -61- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 474811 A7 B7 V. Description of the invention (k) (Please read the notes on the back before filling this page) Mix 2,4-dihydroxybenzaldehyde (6. 12g), potassium hydroxide (3.0g), and potassium iodide (2.0g) into Ν, Ν-dimethyl Formamidine (60ml). Ethyl 4-bromobutyrate (8.65 g) was added, and the mixture was stirred overnight at room temperature. Poured into dilute hydrochloric acid, extracted with ethyl acetate, washed the organic layer with brine, dried over magnesium sulfate, and concentrated. The crude product was subjected to silica gel column chromatography and toluene. And ethyl acetate (20: 1) was mixed and separated to obtain 3.8 g of ethyl 4- (4-methylamidino-3-hydroxyphenylamino) butyrate, as an oil. IR (Neat): 1720, 1625, 1575 cm-1 NMR (CDC13, δ): 1.26 (3Η, d, J = 7.1Hz), 2.13 (2H, m), 2.51 (2H, t, J = 7Hz), 4.07 (2H, t, J = 6Hz), 4.15 (2H, q, J = 7.1Hz), 6.41 (1H, d, J = 2.2Hz), 6.52 (1H, dd, J = 2.2, 8.6Hz), 7.42 (1H, d, J = 8.6Hz), 9.71 (1H, s), 11.46 (1H, s) Preparation Examples The following compounds were obtained as in Preparation Example 32.

OH 0HCvJ \ ^^^ 0-τ-〇Η2—hY-COOEt Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs This paper is printed in accordance with Chinese National Standard (CNS) A4 (2 丨 0 '乂 297 mm) 474811 A7 B7 V. Description of the invention (p) Preparation example η Physical properties (please read the precautions on the back before filling this page) 33-1 4 IR (Nujol): 1725, 1660, 1640, 1615, 1570, 1500, 1460, 1415 cm-1 NMR (CDC13, δ): 1.26 (3Η, t, J = 7.0Hz), 1.80-1.85 (4H, m), 2.35-2.42 (2H, m), 4.00- 4.08 (2H, m), 4.14 (2H, q, J = 7.0Hz), 6.41 (1H, d, J = 2.2Hz), 6.52 (2H, dd, J = 2.2, 8.6Hz), 7.42 (1H, d, J = 8.6Hz), 9.71 (1H, s), 11.47 (1H, s) MASS: 267 (M + K) + 33-2 5 NMR (CDC13, δ): 1.26 (3H, t, J = 7.0Hz), I. 42- 1.95 (6H, m), 2.28-2.37 (2H, m), 4.00- 4.19 (4H, m), 6.40 (1H, d, J = 2.2Hz), 6.53 (1H, dd, J = 2.2, 8.6Hz) , 7.42 (1H, d, J = 8.6Hz), 9.71 (1H, s), II. 47 (1H, s) MASS: 281 (M + H) + Preparation example 34 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 0 β Ν 卞 卞 5glN group 4, s (3 释 2 狎, mixed acid and water, and 2 f Λ at 6f • WM, 7 / IV 5 gi Benzene two-compartment acid, pentamene 1) bromine 0! 0 I 2 2 / V, διg) sub 44 methyl 2 di Γ \ The layer machine has separated extract ethyl acetate and neutral acid to obtain concentrated and dry 0 acid 4g ο Sulfur. 8, / V Washed ester water methyl salt benzene edible acid, acid-based gas benzoic acid Benzene methyl paper This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 474811 A7 B7 V. Description of the invention U >) IR (Film): 1740, 1682, 1590 cm-1 NMR (CDC13, δ): 0.96 (3Η, t, J = 7.7Hz), 1.52 (2H, m), 2.03 (2H, m), 4.86 ( 1H, dt, J = 2, 8Hz), 6.68 (1H, d, J = 8Hz), 6.91 (1H, s), 7.0-7.4 (12H, m), 7.85 (1H, dd, J = 2, 8Hz) , 10.59 (1H, s) Preparation Example 35 The following compound was obtained by simulating Preparation Example 34. (Please read the notes on the back before filling this page)

Printed by the Consumers' Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs I-64- This paper size applies to the Chinese National Standard (CNS) A4 (210X: 297 mm) 474811 A7 B7 V. Description of the invention (H)

O ’, COOR 20

R2! R22 OHC

twenty four

R (Please read the precautions on the back before filling out this page) Printed Preparation Example r2〇r21 r22 r24 by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economy 35-1 Bzh nPr H —CKCH2) " 3COOEt IR (Nujol): 1750, 1730, 1675, 1600, 1575, 1500, 1430 cm-1 NMR (CDC13, δ): 0.96 (3H, t, J = 7.3Hz), 1.26 (3H, t, J = 7.2Hz), 1.43-1.60 (2H, m), 1.93-2.13 (4H, m), 2.46 (2H, t, J = 7.2Hz), 3.61-3.90 (2H, m), 4.15 (2H, q, J = 7.2Hz), 4.81 ( 1Ή, dd, J = 5.2, 7.2Hz), 6.12 (1H, d, J = 2.2Hz), 6.50 (1H, dd, J = 1.4, 8.7Hz), 6.S4 (1H, s), 7.10-7.33 (10H, m), 7.82 (1H, d, J = 8.7Hz), 10.42 (1H, s) * 65 — This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 474811 A7 B7 V. Invention Explanation (μ) Preparation example r2〇r21 r22 r24 Physical properties 35-2 Bzh nPr H -CKCH2 ^ 4COOEt IR (Nujol): 1750, 1730, 1670, 16ϋϋ, 1570, 1490 cm-1 NHR (CDC13, δ): 0.95 (3H, t, J = 7.8Hz), 1.26 (3H, t, J = 7.0Hz), 1.50-1.60 (2H, m), 1.60-1.80 (4H, m), 2.00-2.20 (2H, m), 2.30-2.50 (2H, m), 3.60-3.90 (2H, m), 4.12 (2H, q, J = 7.0Hz), 4.75-4 .85 (1H, m), 6.11 (1H, s), 6.50-6.66 (1H, m), 6.90 (1H, s), 7.10-7.40 (10H, m), 7.85 (1H, d, J = 8.7Hz ), 10.42 _ (1H, s) _ 35-3 Bzh nPr H -0-fCH2f5COOEt IR (Nujol): 1750, 1730, 1675, 1600, 1585, 1490 cm-** NMR (CDCI3, δ): 0.95 ( 3H, t, J = 7.4Hz), 1.26 (3H, t, J = 7.1Hz), 1.40-1.80 (8H, m), 1.90-2.20 (2H, m), 2.28-2.36 (2H, m), 3.60 -3.80 (2H, m), 4.09-4.20 (2H, m), 4.81 • (1H, t, J = 7.0Hz), 6.12 (1H, s), printed by the shoulder workers' consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please Read the precautions on the back before filling this page) 6.52 (IK, d, J = 9.0Hz), 6.91 (1H, s), 7.10-7.35 (10H, m), 7.82 (1H, d, J = 8.8Hz) , 10.42 (1H, s) -66 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (; 210X297 mm) 474811 A7 B7 V. Description of the invention (k) Preparation example R20 R21 R22 R24 Physical properties 35-4 Bzl KH -0-fCH2f3COOEt IR (Nujol): 1750, 1730, 1670, 1600, 1540 cm_l NMR (CDC13, δ): 1.26 (3H, t, J = 7.2Hz), 2.10 (2H, quint, J = 7.4Hz), 2.49 (2H, t, J = 7.4Hz), 3.99 (2H, t, J = 7.4Hz), 4.15 (2H, q, J = 7.2Hz), 4.76 (2H, s), 5.25 (2H, s), 6.28 (1H, d, J = 2Hz), 6.59 (1H, dd, J = 2, 8.4Hz), 7.35 (5H, s), 7.82 (1H, d, J = 8.4Hz), 10.37 (1H , s) MASS: 40Γ (M + K) + 35-5 Me Et H -〇 < CH2) " 3COOEt IR (Nujol): 1750, 1730, 1675, 1600, 1580, 1540, 1440, 1400 cm-1 NMR (CDCI3, δ): 1.10 (3H, t, J = 7.4Hz), 1.26 (3H, t, J = 7.2Hz), 2.00-2.17 (4H, m), 2.50 (2H, t, J = 7.4Hz ), 3.77 (3H, s), 4.04 (2H, t, J = 6.2Hz), 4.15 (2H, q, J = 7.2Hz), printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the back first) Please fill in this page again for notes) 4.69 (1H, t, J = 6.0Hz), 6.28 (1H, d, J = 2.0Hz), 6.55 (1H, dd, J = 2.0, 8.9Hz), 7.83 (1H, d, J = 8.9Hz), 10.41 (1H, d, J = 0.7Hz) MASS: 353 (M + H) + 35-6 Et Me Me H · IR (Film): 1730, 1680, 1660, 1595 cnC1 NMR (CDC13, δ): 1.23 (3H, t, J = 7Hz), 1.69 (6H, s), 4.24 (2H, q, J = 7Hz), 6.78 (1H, d, J = 8Hz), 7.02 (1H, t, J = 7.5Hz), 7.45 (1H, dt, J = 2, 7 · 5Ηζ), 7.85 (1H, dd, J = 2, 8Hz), __10.52 (1H, s) _ paper size Applicable to China #_ 准 (CNS) A4 specification (210X297 mm) '474811 A7 B7 V. Description of invention (w) Preparation example R2 0 R21 R22 · !? 24 Physical properties 35-7 3zh n3u Η H IR (Film): 1750, 1685, 1595 cm-1 NMR (CDCI3, δ): 0.87 (3H, t, J = 7.7Hz), 1.4 ( 4H, m), 2.07 (2H, m), 4.85 (1H, t, J = 6Hz), 6.68 (1H, d, J = 8Hz), 6.92 (1H, s), 7.0-7.4 (12H, m), 7.85 (1H, dd, J = 2, 8Hz), 10-59 (1H, s) 35-8 Et -iCH2f3 H IR (Film): 1725, 1685, 1595 cm-1 ------- ----- (Please read the notes on the back before filling this page) 35-9 Me Et Η H IR (Film): 1745, 1685, 1598 cm'1 NMR (CDC13, δ): 1.06 (3H, t, J = 7.7Hz), 2.08 (2H, dt, J = 6, 7Hz), 3.76 (3H, s), 4.74 (1H, t, J = 6Hz), 6.81 (1H, d, J = 8Hz), 7.06 (1H, t, J = 8Hz), 7.51 (1H, t, J = 8Hz), 7.87 _ (1H, dd, J = 2, 8Hz), 10.59 (1H, s) Order staff consumption of the Central Standards Bureau of the Ministry of Economic Affairs Cooperative society printed the following Preparation Example 34 to obtain the following compounds. 4- (4-methylfluorenyl-3-methylphenoxy) butyric acid ethyl ester IR (Neat): 1730, 1670, 1600, 1575, 1500, 1460, 1430, 1390 cm-1 NMR (CDC13, δ) : 1.26 (3Η, t, J = 7.2Hz), 2.14 (2Η, quint, J = 7.2Hz), 3.90 (3H, s), 4.15 (2H, q, J = 7.2Hz), 4.10 (2H, q, J = 7.2Hz), 6.45 (1H, d, 'J = 2.2Hz), 6.53 (1H, dd, J = 2.2, 8.6Hz), 7.79 UH, d, J = 8.6Kz), 10.28 (1H, s) This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 474811 A7 B7 5. Description of the invention (β) Preparation Example 37 The third butyl bromoacetate (1_958), 2,5-dihydroxy Benzaldehyde (1.38 舀) was dissolved in dimethylideneϋϋ (15ml), potassium sulfonate (2.07g) was added, and the mixture was stirred at room temperature for 2 hours. Water was added thereto, and the mixture was extracted with 1N hydrochloric acid, extracted with ethyl acetate, and the organic layer was washed with brine. After drying over magnesium sulfate and concentrating, the crude product was chromatographed on a silica gel column (40 g), and the mixed solution of toluene and ethyl acetate (9: 1) was dissolved away.

The first eluate gave 2,5-bis (third butane carbonylmethoxy) benzaldehyde (0.588). mp: 89-90 ° C IR (Nujol): 1740, 1680 cm-1 NMR (CDC13, δ): 1.47 (9H, s), 1-49 (9H, s), 4.51 (2H, s), 4.60 ( 2H, s), 6.83 (1H, d, J = 9Hz), 7.17 (1H, dd, ~ J = 3, 9Hz), 7.27 (1H, d, J = 3Hz) The second eluate is 2- (third Butanecarbonylmethoxy) -5 -hydroxybenzaldehyde (1.60g). NMR (CDCI3, δ): 1.49 (9Η, s), 4.61 (2H, s), 6.56 (1H, br S), 6.75 (1H , d, J = 9Hz), 7.03 (1H, dd, J = 2.5, 9Hz), 7.26 (1H, d, J = 3Hz), 10.46 (1H, s) Printed (Please read the notes on the back before filling this page) Ethyl 4-bromobutyrate (1.48g) and 2- (Third-butanecarbonylmethyl) -5-hydroxybenzaldehyde (1.28g) Soluble in methyl ethyl ketone (201111). After adding potassium sulfonate powder (1.05 g), stir in an oil bath at 100 ° C for 7 hours. It was concentrated, diluted with water, extracted with ethyl acetate, and the organic layer was washed with brine and dried over magnesium sulfate. After concentration, the crude product was chromatographed on a silica gel column (35g), and toluene and ethyl acetate (19: 1 ~ 4: 1) were dissolved to give 4- (4-tert-butoxycarbonylmethyl-3-methylbenzylphenoxy Base)-Ethyl butyrate 0.55 g, oily β -69- This paper size applies Chinese National Standard (CNS) A4 specification (2 丨 0X 297 mm) 474811 A7 B7 V. Description of the invention (w) IR (Nujol): 1730, 1675 cm-1 NMR (CDCI3 / δ): 1.25 (3H, d, J = 7Hz), 1.47 (9H, s), (Please read the precautions on the back before filling this page) 2.01 ( 2H, m), 2.50 (2H, t, J = 7Hz), 4.00 (2H, t, J = 6Hz >, 4.15 (2H, q, J = 7Hz), 4.60 (2H, s), 6.81 (1H, d , J = 3Hz), 7.09 (1H, dd, J = 3, 9Hz), 7.33 (1H, d, J = 3Hz), 10.53 (1H, s) -Methoxyphenoxy) ethyl propionate (2.60g), tetrahydrofuran-water (9: 1) solution, add sodium borohydride (185ml), stir at same temperature for 2 hours, add dilute hydrochloric acid (1 N, 5ml) ). Stir for 1 hour. Dilute with water, extract with ethyl acetate, separate the organic layer from brine, and dry over magnesium sulfate. After concentration, the crude product is chromatographed on a silica gel column (29g), and the toluene and ethyl acetate (7: 1) are mixed and separated. Get 2- ( Ethyl 2-hydroxymethyl-6-methoxyphenoxy) propionate (1.85 g). IR (Film): 3420, 1730, 1585 cm-1 NMR (CDCI3, δ): 1.25 (3Η, t, J = 7Hz), 1.60 (3Η, d, J = 7Hz), 3.59 (1H, dd, J = 5, 8.4Hz), 3.83 (3H, s), 4.2 (2H, q, J = 7Hz), 4.53 ( 1H, dd, J = 8.4, 12.2Hz), 4.89 (1H, dd, J = 5.0, 12.2Hz), 5.11 (1H, q, J = 7Hz), 6.82-7.06 (3H, in) Central Bureau of Standards, Ministry of Economic Affairs There are 9 3 cases printed by the employees' consumer cooperatives in the list of prepared imitation papers, which are applicable to China National Standard (CNS) A4 specifications (210 > < 297 mm) 474811 A7 B7 V. Description of the invention (w) R21 \ ^ R22 ct ^ coor20

Preparation example r20r21r22r23r24 Physical properties 40-1 Me Me H OMe Η [α] §5 = -57.69 ° (c = 0.93, CHCI3) IR (Film): 3600-3000, 1730, 1265 cm-: ((S) -iso Structure) NMR (CDC13, δ): 1.60 (3H, d, J = 6.9Hz), 3.73 (3H, s), 3.83 (3H, s), 3.38 (1H, dd, J = 5.1, 8.4Hz), 4.55 (1H, dd, J = 5.1, 8.4Hz), 4.89 (1H, dd, J = 5.1, 12.2Hz), 5.12 (1H, q, J = 6.9Hz), 6.83-7.06 (3H, m) (Please (Please read the notes on the back before filling out this page) 40-2 Bzh nPr H OMe H IR (Film): 3400, 1730, 1582 cm * 1 NMR (CDC13, δ): 0.93 (3H, t, J = 7Hz), 1.50 (2H, m), 2.0 (2H, m), 3.68 (3H, s), 4.47 (1H, d, J = 12Hz), 4.84 (1H, d, J = 12Hz), 5.30 (1H, t, J = 6Hz), β. 8-7.0 (3H, m), 7.2-7.3 (10H, m) 40-3 Me Et H OMe H IR (Film): 3410, 1735, 1585 cm'1 NMR (CDCI3, δ): 1.08 (3H, t, J = 7.6Hz), 2.0 (2H, m), 3.70 (3H, s), 3.82 (3H, s), 4.51 (1H, dT J = 12.1Hz), 4.95 (IK, d, J = 12.1Hz), 5.73 (1H, t, J = 6Hz), 6.82-7.26 (3H, m) This paper size applies to China National Standard (CNS) A4 specifications ( 21〇X297 mm) -71- 474811 A7 B7 V. Description of the invention (π) Preparation example r20r21r22r23r24 Physical properties. 40-4 Et Me Me OMe H IR (Film): 3400, 1720, 1582 cm-1 NMR (CDC13, δ): 1.34 (3H, t, J = 7Hz), 1.50 (6H, t, J = 7Hz), 2.60 (1H, br s), 3.74 (3H, s), 4.28 (2H, q, J = 7Hz >, 4.65 (2H, s), 6.8 -7.1 (3H, m) 40-5 tBu Η H OMe H IR (Film): 3400, 1725, 1585 cm'1 NMR (CDCI3, δ): 1.48 (9H, s), 3.85 (3H, s), 4.68 (2H, s), 4.70 (2H, s), 4.2 (1H, br s), 6.8-7.1 (3H, ra) 40-6 Me H Me OMe H l'a) ^ 5 = + 52.43 ° (c = 1.05, CHC13) IR (Film): 3300-3000, 1730, 1580, ((R) -isomer) 1480 cirT1 NMR (CDCI3, δ): 1.60 (3H, d, J = 6.9Hz), 3.74 (3H , s), 3.83 (3K, s), 4.54 (1H, d, J = 12.2Hz), 4.88 (1H, d, J = 12.2Hz), 5.12 (1H, d, J = 6.9Hz), 6.85 (1H , dd, J = 2.0, ___ 7.8Hz), 6.88-7.06 (2H, m) 40-7 Bzh nPr Η H OMe IR (Film): 3400, 1734, 1610, 1588, 1500 cm- · *-Central Ministry of Economic Affairs Printed by the Consumer Bureau of Standards Bureau (please read the notes on the back before filling this page) NMR (CDC13, δ): 0.95 (3H, t, J = 7Hz), 1.47 (2H, m), 1.97 (2H, m ), 2.72 (1H, dd, J = 4 .1, 8.4Hz), 3.63 (3H, s), 4.47 (1H, dd, J = 8.2, 12.0Hz), 4.79 (1H, dd, J = 4.1, -12.0Hz), 4.87 (1H, t, J = 6.2Hz), 6.29 (1H, d, J = 2.2Hz), 6.46 (1H, dd, J = 2.2, 8.2Hz), 6.88 (1H, s), _________ 7-1-7.3 (11H, m) _- 72- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 474811 A7 B7 V. Description of the invention (7 ') Ice-cold 2- (2-methylphenoxy) valeric acid diphenyl methyl ester (8.Og) tetrahydrofuran-water (9: 1, 80ml), sodium borohydride (380mg) was added, and the mixture was stirred at the same temperature for 2 hours, and 1N hydrochloric acid (20 m 1) was added, and stirred for 1 hour. It was diluted with water, extracted with ethyl acetate, and the organic layer was separated, washed with brine, and dried over magnesium sulfate. After concentration, the crude product was purified on a silica gel column (29g), and toluene and ethyl acetate (9: 1 mixed solution were separated to give 2- [2- (hydroxymethyl) phenoxy] valeric acid diphenyl methyl ester (6.81g). 〇IR (Film) 3420, 1730, 1600, 1585 cm-1 NMR (CDC13, δ): 0.94 (3H, t, J = 7Hz), 1.5 (2H, m), 2.0 (2H, m), 2.53 (1H, br s), 4.54 (1H, d, J = 12.4Hz), 4.86 (1H, d, J = 12.4Hz), 4.9 (1H, m), 6.70 (1H, d, J = 8Hz), 6.88 (1H, s), 6: 96 (1H, d, J = 8Hz), 7.1-7.4 (12H, m) Preparation Example A2 Following Preparation Example 4 1 the following compounds were obtained. (Please read the precautions on the back before filling in this (Page 21)

R 22 20 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs

R

R 24

'COOR -73- This paper size applies to China National Standard (CNS) A4 specification (210 × 297 mm) 474811

Preparation example R20 R21 R22 R24 R25

42-1 Bzh nPr H -OfCH2f3COOEt H IR (Nujol): 3400, 1750, 1730, 1610, 1585, 1500 cm-1 NMR (CDC13 / δ): 0.95 (3H, t, J = 7.4Hz), 1.26 (3H , t, J = 7.1Hz), 1.29-1.60 (2H, m), 1.90-2.10 (4H, m), 2.44 (2H, t, J = 7.4Hz), 2.70 (1H, dd, J = 4.6 , 8.4Hz >, 3.70-3.92 (2H, m), 4.14 (2H, q, J = 7.4Hz), 4.43 (1H, d, J = 8.4Hz), 4.49 (1H, d, J = 8.4Hz), 4.74-4.90 (2H, m), 6.28 (1H, d, J = 2-2Hz), 6.43 (1H, dd, J = 2.2, 8.4Hz), 6.89 (1H, s), 7.11-7.36 (10H, m )

42-2 Bzh nPr H -CHCH2y4COOEt H IR (Nujol): 3400, 1740, 1725, 1610, 1585, 1500, 1450 cm-1 NHR (CDC13, δ): 0.95 (3H, t, J = 7.4Hz), economic Printed by the Ministry of Standards and Labor ’s Consumer Cooperatives (please read the precautions on the back before filling this page) 1.26 (3H, t, J = 7.1Hz), 1.44-1.54 (2H, m), 1.71-1.75 (4H, m), 1.93-2.04 (2H, m), 2.31-2.38 (2H, m), 2.76-2.80 (1H, ία), 3.65-3.85 (2H, m), 4.13 (2H, q, J = 7.1Hz) , 4.4-4.51 (1H, m), 4.76-4.90 (2H, m), 6.28 (1H, d, J = 2.2Hz), 6.43 (1H, dd, J = 2.2, 8.6Hz), 6.68 (1H, s ), _ 7.11-7.34 (10H, m) -74- This paper size is applicable to Chinese National Standard (CNS) A4 (210X 297 mm) 474811 A7 B7 V. Description of the invention (^) Preparation examples r20 r21 r22 r24 r25

42-3 Bzh nPr H -0-fCH2f 5COOEt H IR (Nujol): 3400, 1740, 1730, 1610, 1585, 1500 cm-1 NMR (CDC13 / δ): 0.95 (3H, t, J = 7.4Hz >, 1.26 (3H, t, J = 7.1Hz), 1.4-1.8 (8H, m), 1.9-2.1 (2H, m), 2.32 (2H, t, J = 7.4Hz), 2.7-2.8 (1H, m) , 3.66-3.80 (2H, m), 4.13 (2H, q, J = 7.1Hz), 4.40-4.51 (1H, m), 4.75-4.90 (2H, m), 6.29 (1H, d, J = 2.2Hz ), 6.44 (1H, dd, J = 2.2, 8.2Hz), 6.68 (1H, s), 7.11-7.32 (10H, m)

42-4 Bzl Η H -O (CH7f3C00Et H -IR (Nujol): 3400, 1720, 1610, 1590, 15 0 0 era -1 NMR (CDC13, δ): 1.26 (3H, t, J = 7.2Hz), 2.08 (2H, quint, J = 7.4Hz), 2.49 (2H, t, J = 7.4Hz), 3.95 (2H, t, J = 7.4Hz), 4.14 (2H, q, J = 7.2Hz), 4.64 ( 2H, s), 4.72 (2H, s), 5.22 (2H, s), 6.36 (1H, d, J = 2.2Hz >, 6.48 (1H, dd, J = 2.2, 8.2Hz), 7.18 (1H, d , J = 8.2Hz), 7.36 (5H, s)

42-5 Me Et K -0-fCH2f 3COOEt H IR (Nujol): 3400, 1725, 1610, 1585, printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) 1500, 1430 cnT1 NMR (CDC13, δ): 1.09 (3H, t, J = 7.4Hz), 1.26 (3H, t, J = 7.2Hz), 2.00-2.17 (.4H, m), 2.49 (2H, t, J = 7.4Hz), 3.04 (1H, br s), 3.74 (3H, s), 3.96 (2H, t, J = 6.0Hz), 4.14 (2H, q, J = 7.4Hz), 4.43 (1H, d, J = 10.8Hz), 4.75 (1H, t, J = 6.0Hz), 4.85 (1H, d, J = 10.8Hz), 6.36 (1H, d, J = 2.2Hz), 6.46 (1H, dd, J = 2.2, 8.2Hz), 7.18 (1H, d, J = 8.2Hz)

This paper size applies to China National Standard (CNS) A4 (210 x 297 mm)-7S 474811 Μ _____ · _B7 V. Description of invention (μ) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, printed by the Bayer Consumer Cooperative, R20 R21 R22 R24 R25 42-6 St He Me Η H IR (Film): 3400, 1720, 1598 cm-1 NMR (CDC13, δ): 1.22 (3H, t, J = »7Hz), 1.65 (6H, s), 4.22 ( 2H, d, J = 7Hz), 4.66 (2H, s), 6.73 (1H, dd, J = l, 8Hz), 6.96 _ (1H, nt), 7.16 (1H, m), 7.30 (1H, m) 42-7 Bzh nBu Η IR H IR (Film): 3400, 1730, 1600, 1585 cm'1 NMR (CDCI3, δ): 0 · 87 (3H, t, J = 7Hz), 1.4 (4H, m), 2.0 (2H, m), 2.72. (1H, br s), 4.54 (1H, d, J = 12.4H2), 4.85 (1H, d, J = 12.4Hz), 4.9 (1H, m), 6.70 (1H, d, J = 8Hz) / 6.95 (1H, s), 6.96 (1H, d, J = 8Hz), 7.1-7.4 (12H, m) 42-8 Et -fCH2 ^ 3 Η H NMR (CDC13, δ): 1.11 (3H, t, J = 7Hz), 1.98-2.1 (2H, m), 2.45-2.85 (5H, m), 4.15 (2H, q, J = 7Hz), 4.71 (2H, d, J = 6.3Hz), 6.44 (1H, d, J = 8Hz), 6.93 _ (1H, m) r 7.14 (1H, m), 7.29 (1H, m) 42-9 Me Et Η IR H IR (Film): 3400, 1730, 1600, 1590 cm_l NMR (CDCI3, δ): 1.10 (3K, t, J = 7H z), 2.04 (2H, m), 3.76 (3H, s), 4.52 (1H, d, J = 12Hz), 4.79 (1H, t, J = 6Hz), 4.92 (1H, d, J = 12Hz), 6.77 (1H, d, J = 9Hz), _ 6.96 (1H, m), 7.1-7.3 (2H, m) ------ IT ------ φ. (Please read the precautions on the back first (Fill in this page again) -76- This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 474811 A7 B7

Imprint by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (〆) Preparation example r20 R21 r22 r24 r25 42-10 tBu Η Η H -〇-fCH2f3C〇Et IR (Nujol): 3400, 1720 cm-1 MMR (CDCI3, δ): 1.26 (3H, d, J = 7Hz), 1.47 (9H, s), 2.08 (2H, m), 2.50 (2H, t, J = 7Hz), 2.86 (1H, br s), 3.96 (2H, t, J = 6Hz), 4.14 (2H, q, J = 7Hz), 4.51 (2H, s), 4.67 (2H, s), 6.7 (2H, m), 6.8 _ (1H, ra) _ 42-11 tBu Η Η H -〇-CH2-COOtBt IR (Nujol): 3430, 1745 cm-1 NMR (CDCI3, δ): 1.47 (9H, s), 1.48 (9H, s), 3.45 ( 1H, t, J = 7Hz), 4.62 (2H, s), 4.54 (2H, s), 4.67 (2H, d, J = 7Hz), 6.7-6.9 (3H, m) Preparation Example 43 The following compounds. 4- (4-Hydroxymethyl-3-methoxyphenoxy) butyric acid ethyl ester IR (Neat): 3400, 1720, 1605, 1585, 1500, 1460, 1420 cm " NMR (CDC13, δ): 1.26 ( 3Η, t, J = 7.2Hz), 2.03-2.17 (3H, m), 2.51 (2H, t, J = 7.3Hz), 3.84 (3H, s), 4.00 (2H, t, J = 6.1Hz >, 4.15 (2H, q, J = 7.1Hz), 4.60 (2H, d, ^ .3Hz) / 6.41 (1H, d / J = 2.3Hz), 6.43-6.50 (2H, rn), 7.14 (1H, d, J = 8.0Hz) Trifluoromethanesulfonium (D. 7 4 m 1) was added dropwise to the ice-cold 2-(5-hydroxy-phenylsulfanylfuran-2-yl) -4 -tert-butyltriazole (l. Og), Ν, Ν -dimethylamino-77- This paper size applies to China National Standard (CNS) A4 (210X 297 mm) ml I Is! Nn ...... nn-.. .....,? T (Please read the precautions on the back before filling out this page) 474811 A7 B7 V. Description of the invention (#) Pyridine (671 ^) and 2,6-lantidin (0.521111, 4.39111111〇1 ) Was dried at a temperature below 10 ° C and mixed with dichloromethane (10m 1), and stirred at room temperature for 2 hours. The reaction mixture was washed with dilute hydrochloric acid, dried over magnesium sulfate, evaporated under reduced pressure, silica gel column chromatography, and n-hexane-ethyl acetate. Ester (4: 1) dissociates to give 2- (4-tert-butyltriazole- 2-yl) benzene Furan-5-yltrifluoromethanesulfonate 1.39 g, colorless oil. IR (Neat): 3100, 2950, 1615, 1585, 1500, 1460, 1430 cm-1 NMR (CDC13 / δ): 1.41 (9Η, s ), 7.04 (1H, s), 7.24 (1H, dd, J = 2.4 and 7.9Hz), 7.35 (1H, d, J = 0.8Hz), 7.54 (1H, d, J = 2.4Hz), 7.58 (1H , d, J = 7.9Hz) MASS: 406 (M + H) + Preparation Example 4 5 Blowing monoxide at room temperature into 2- (4-tert-butylifazol-2-yl) triflate Phenylfuran-5-ester (6.Og), terbium acetate (99.7®g), 1,3-bis (diphenylphosphino) propane (183mg, 0.44mmol) and triethylamine (4.13ml) in methanol ( 15 ml) and N, N-dimethylformamide (30 ml) were mixed for 1 hour. Heat to 7 Q ° C and stir under a gasified carbon bubble for 3 hours. It was filtered through a C e 1 ite bed, washed with ethyl acetate, and the filtrate and washing liquid were collected, concentrated under reduced pressure, and subjected to silica gel column chromatography. The ethyl acetate-n-hexane was used to isolate 2- (4-tert-butyltriazole-2). -Yl) Benzofuran-5-carboxylic acid methyl ester as a colorless powder (3.92 g). IR (Nujol): 3200, 1720, 1610 cm-1 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) NMR (CDCI3, δ): 1.42 (9Η, s), 3.95 (3Η, s), 7.02 (1H, s), 7.39 (1H, s), 7.57 (1H, d, J = 8.7Hz), 8.09 (1H, dd, J = 1.7 and 8.7Hz), 8.36 (1H , d, J = 1.7Hz) MASS: 316 (M + H) + Example 1 Mixed Crude 4 -Third-Butyl-2- [5- (Thiamine Methyl) Benzamurol 7 8-Paper Standards are applicable to China National Standard (CNS) A4 specifications (210X297 mm) 474811 Printed bags A7 B7 of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (W) Nan-2-yl] conazole (0.73g) and 4- A solution of ethyl acetate (0.92 g) in ethyl acetate (30 m 1) was stirred and refluxed for 18 hours. After cooling, pour sodium hydrogen sulfonate, extract with ethyl acetate, wash the organic layer with brine, dry over magnesium sulfate, and concentrate under reduced pressure. Column chromatography with silica gel, ethyl acetate dissolves, collect the solution containing the target, and decompress. 4-tert-butyl-2- {5-{[4- (ethoxycarbonylmethyl) blazol-2-yl] methyl} benzofluoran-2-yl] -azole (0.61 g) is obtained. IR (Film): 3130, 1740, 1630, 1590, 1520, 1500 cm-1 NMR (CDC13, δ): 1.28 (3Η, t, J = 7.1Hz), 1.41 (9Η, s), 3.82 (2H, d , J = 0.6Hz), 4.20 (2H, q, J = 7.1Hz), 4.41 (2H, s), 6.98 (1H, s), 7.06 (1H, t, J = 0.6Hz), 7.28 (1H, dd, J = 8.5, 1.8Hz), 7.30 (1H, d, J = 0.9Hz), 7.50 (1H, d, J = 8.5Hz >, 7.56 (1H, dd, J = 1.8, 0.9Hz) MASS: 440 (M +), 425, 368, 270, 254 Example 2 Soluble 4 -Third-Butyl-2- [5- (thiaminemethyl) benzylfuran-2-yl] pyrazole (740mg) and 3- Bromo-4-gas-4-phenylbutyric acid (600mg) in ethyl acetate (8.0ml), heated to reflux for 13.5 hours. After cooling, the precipitate was collected by filtration, washed with ethyl acetate, dissolved in ethyl acetate, and hydrogen peroxide. It was washed with sodium water and brine, dried over magnesium sulfate, and concentrated under reduced pressure to obtain a mixed solution, and passed through a silica gel column. Chromatography, gas imitation, methanol and ethyl acetate mixed solution (20: 1: 1 ~ 20: 1: 2) were dissolved, and the layer containing the target substance was collected and decompressed to obtain 4 -third butyl-2-{5- [(5-carboxymethyl-4-phenylblazol-2-yl)) benzofuran-2-yl] pyrazole (72 mg). mp: 174-180 IR (Nujol): 1710, 1500, 1223, 1182 cm-1 NMR (DMSO-dg, δ): 1.36 (9H, s), 3.48 (2H, s), 4.44 (2H, s), 7.35-7.75 (10H, m) MASS: 488 (M +), 444 ----— This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling in this Page) 474811 A7 B7 V. Explanation of the invention (outside) Example Η Mixing 4 -Third-butyl-2-[5-(cyanomethyl) phenylsulfanfuran-2-yl] itazole (1.31g) and thioethylhydrazone 4N of amine-1,4-dioxane hydrochloride (4ml) and chloroform, stirred at reflux for 30 minutes, removed the solvent at the same temperature, washed with water to obtain crude 4-tert-butyl-2- [5- (thiamine methylamine) Fluorenylmethyl) benzofuran-2-yl] ifazole (1.23g) NMR (DMSO-dg, δ): 1.36 (9%, s), 3.93 (2H, s), 7.41 (1H, dd, J = 8.5, 1.8Hz), 7.47 (1H, s), 7.53 (1H, d, J = 0.9Hz), 7.58 (1H, d, J = 8.5Hz), 7.65 (1H, dd, J = 1.8, 0.9 Hz) Mixing crude 4-tert-butyl-2- [5- (thiaminemethyl) phenylbenzofuran-2-yl] Utazole (1.23g) and ethyl bromopropionate (0.86g) Ν, Ν-dimethylformamide (14 m 1), and stirred at 50 ° C for 9 hours. Poured into sodium hydrogen sulfonate, extracted with ethyl acetate, washed with brine, dried over magnesium sulfate, and concentrated under reduced pressure. The resulting precipitate was washed with isopropyl ether to give 4-tert-butyl-2- {5- {[4- (ethyl Carboxyl) carbazol-2-yl] methyl} benzofuran-2-yl} blazol (0.793). IR (Nujol): 3100, 1720, 1590, 1500 cm-1 NMR (DMSO-dg, δ): 1.30 (3Η, t, J = 7.1Hz), 1.36 (9H, printed by the staff consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (Please read the notes on the back before filling this page) s), 4.29 (2H, q, J = 7.1Hz), 4.50 (2H, s), 7.40 (1H, dd, J = 8.6, 1.7Hz), 7.49 (1H, s), 7.53 (1H, d, J = 0.7Hz) / 7.69 (1H, d, J = 8.6Hz), 7.70 (1H, dd, J = 1.7, 0.7Hz), 8.40 (1H, s) MASS: 426 (M +), 255 M 4 The compound of formula 3 was obtained as in Example 3. -8 0-This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 474811 A7 B7 V. Description of the invention (π) 4-Third-butyl-2- {5- {[4- (Gas (Methyl) benzozol-2-yl] methyl} benzofuran-2-yl} brazole IR (Film): 3140, 1590, 1500 cm-1 NMR (CDCI3, δ): 1.41 (9Η, s), 4.41 (2H, s), 4.69 (2H, s), 6.98 (1H, s >, 7.17 (1H, s), 7.28 (1H, br d, J = 8.4Hz), 7.31 (1H, br s) , 7.51 (1H, d, J = 8.4Hz), 7.56 (1H, br s) MASS: 402 (M +), 301, 270, 254 Example 5 Mixed 4-tert-butyl-2- {5- {(4 -(Ethoxycarbonyl) triazol-2-yl] methyl} benzopyrfuran-2-yl) triazole (0.79g) and NaOH (0.17g) in water (2 m 1) and methanol (6 m 1) Stir at reflux for 3 hours. After cooling, concentrated under reduced pressure, dissolved in water, neutralized with dilute hydrochloric acid, extracted with ethyl acetate, washed the organic layer with brine, dried over sulfuric acid IM, concentrated under reduced pressure, and washed with a small amount of ethyl acetate to obtain 4-tert-butyl-2 -{5-[(4-Carboxy Pf-2-yl) methyl] phenylarfuran-2-yl) carbazole (0.69 g).

mp: 227-230 ° C IR (Nujol): 3120, 2600, 1680, 1590, 1490 cm-1 NMR (DMS〇-d6, δ): 1.36 (9H, s), 4.48 (2H, s), 7.40 Economy Printed by the Consumer Standards Cooperative of the Ministry of Standards of the People's Republic of China (Please read the notes on the back before filling this page) (1H, dd, J = 8.6, 1.7Hz), 7.49 (1H, s), 7.53 (1H, d, J = 0.7Hz), 7.69 (1H, d, J = 8.6Hz), 7.70 (1H, dd, J = l.7, 0.7Hz), 8.32 (1H, s) MASS: 398 (M +) / 255 cases 5 gives the following compounds. 1) 4-Third-butyl-2- {5-{[4- (carboxymethyl) azol-2-yl] methyl} benzopyranfuran-2-yl) carbazole-8 1-paper size Applicable to China National Standard (CNS) A4 specification (2 丨 0'〆297 mm) 474811 A7 B7 V. Description of the invention (and) IR (Nujol): 3140, 2700, 2600, 1730, 1590, 1530, 1500 cm-- * · NMR (CDC13, δ): 1.41 (9Η, s), 3.87 (2Η, d, J = 0.8Hz), 4.43 (2H, s), 6.99 (1H, s), 7.03 (1H, t, J = 0.8Hz), 7.27 (1H, dd, J = 8.5, 1.5Hz), 7.31 (1H, d, J = 0.9Hz), 7.51 (1H, d, J = 8.5Hz), 7.55 (1H, dd, J = l.8, 0.9Hz) MASS (m / z): 412 (M +), 368, 270, 254 2) 5- [2- (4 -Third-butyl-pyrazol-2-yl) benzofuran -5-yl] -10-carboxybenzyl) -1H-tetrazole. NMR (CDC13, δ): 1.40 (9Η, s), 6.16 (2H, s), 6.93 (1H, d, J = 7.2Hz), 7.02 (1H, s), 7.34 (1H, s), 7.41-7.62 (4H, m), 7.85 (1H, br s), 8.18 (1H, dd, J = 7.7, 1.4Hz) MASS (m / z): 459 (M +), 325, 297, 282, 267 Example 7 Ministry of Economic Affairs Printed by the Consumer Standards Cooperative of the Central Bureau of Standards (please read the precautions on the back before filling out this page) Mixed 5- [2- (4 -Third-butylcarbazol-2-yl) benzofuran-5-yl]- A mixture of 2- [2- (ethoxycarboxy) benzyl] -2H-tetrazole (2.04 g) and 5N NaOH water (1-5 ml) in methanol (20 ml) and tetrahydrofuran (15 ml) was stirred at room temperature for 1 day. It was concentrated under reduced pressure, dissolved in methanol (2 ml), and left to stand without precipitation. The precipitate was collected by filtration, and washed with ethyl acetate to obtain 5- [2-U-tert-butylblazol-2-yl) benzofuran- Sodium salt of 5-yl] -2- (2-carboxybenzyl) -2H-tetrazole (1.28 g). -8 2-This paper size is in accordance with Chinese National Standard (CNS) A4 (2I0X 297 mm) 474811 A7 B7_ 5. Description of the invention (")

mp: 150-151 ° C IR (Nujol): 1610, 1590, 1570, 1530, 1500 cm-1 NMR (DMS0-d6, δ): 1.37 (9H, s), 6.52 (2H, s), 6.79 (1H , dd, J = 6.8, 2.0Hz), 7.19-7.29 (2H, m), 7.53 (1H, s), 7.65 (1H, br s), 7.82 (1H, dd, J = 6.8, 1.7Hz), 7.87 (1H, d, J = 8.6Hz), 8.10 (1H, dd, J = 8.6, 1.7Hz), 8.45 (1H, br d, J = 1.7Hz) MASS (m / z): 282, 267 Example 8 Simulation Example 7 gave a compound of the following formula. 5- [2- (4-Third-butyltriazol-2-yl) benzylfuran-5-yl] -10-carboxybenzyl) -1H-tetrazole sodium salt. IR (Nujol): 1610, 1590, 1560, 1500 cm-1 NMR (DMS0-d6, δ): 1.39 (9Η, s), 6.28 (2Η, br m), 6.62 (1H, m), 7.18-7.29 ( 2H, m), 7.53 (1H, s), 7.60 (1H, s), 7.77 (1H, dd, J = 8.7, 1.8Hz), 7.87 (1H, d, J = 8.7Hz), 7.87 (1H, m ), 8.21 (1H, br d, J = 1.8Hz) MASS (m / z): 282, 267 Example 9 4-Third-Butyl-2- {5-[(4-Carboxyrazol-2-yl) Methyl] benzylfuran-2-yl} pyrazole (0.20g), 2-methylbenzenesulfonamide (0.10g), 4-printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the note on the back first) Please fill in this page again) dimethylaminopyridine (0.12g), and 1- (3-dimethylaminopropyl) -3-ethylcarbonyldiimine hydrochloride (0.19g) -dimethyl A solution of methylformamide (6 ml), stirred at room temperature for 2 days, poured into ice water, extracted with ethyl acetate, washed the organic layer with brine, dried over magnesium sulfate, concentrated under reduced pressure, and subjected to silica gel column chromatography, ethyl acetate Dissolve, collect the solution of the target, recrystallize from ether, and filter -83- This paper is in accordance with China National Standard (CNS) A4 (210X297 mm) 474811 A7 B7 5. Description of the invention (a) 4-tert-butyl -2- { 5-{{4- [N- (2-methylbenzenesulfonyl) amine methylamidino] Ufazole-2-yl) methyl} benzofluoran-2-yl} pyrazole (0.18 g) 0

mp: 201-203 ° C IR (Nujol): 1550, 1500 cm 1 NMR (DMS〇-d6, δ): 1.36 (9H, s), 2.55 (3H, s), 4.41 (2H, s), 7.14- 7.38 (4H, m), 7.48 (1H, s), 7.50 (1H, d / J = 0.7HZ), 7.63-7.67 (2H, m), 7.84 (1H, s), 7.87 (1H, dd, J = 7.3, 1.5 Hz) Example 1 0 Mixed 4-Third-Butyl-2- {5- {[4- (chloromethyl) blazol-2-yl] methyl} benzofuran-2-yl) -azole (0.46 g), sodium cyanide (0.22 g) and potassium iodide (0.19 g) in methanol (10 in 1), and stirred under reflux for 2 1 hour. After cooling, it was poured into ice water, extracted with ethyl acetate, the organic layer was washed with brine, dried over magnesium sulfate, and concentrated under reduced pressure to obtain a slurry, which was subjected to silica gel column chromatography, and the ethyl acetate and toluene (1: 20) solution was dissolved. The target was collected and decompressed to give 4-tert-butyl-2-{5-([4-(cyanomethyl) _azole-2-yl] methyl] benzopyran-2-yl} carbazole (0.19 g) IR (Nujol): 3100, 2250, 1590, 1530, 1500 cm-1 NMR (CDC13, δ): 1.41 (9Η, s), 3.89 (2Η, d, J = 1.0Hz), Central Standard of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperative (please read the precautions on the back before filling out this page) 4.39 (2H, s), 6.99 (1H, s), 7.18 (1H, t, J = 1.0Hz), 7.27 (1H, dd , J = 8.4, 1.9Hz), 7.31 (1H, d, J = 0.9Hz), 7.52 (1H, d, J = 8.4Hz), 7.55 (1H, dd, J = l.9, 0.9Hz) MASS ( m / z): 393 (M +), 254 to 8 4 _ This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 474811 A7 B7_ V. Description of the invention (h)

®ULL Mixed 4 -Third-Butyl-2-{5-{[4- (Methyl) azol-2-yl] methyl} benzofuran-2-yl} PIazole (0 · 1 9 g) , Sodium azide (0.43 g) and N, N-dimethylformamide (3nl) of gasified ammonium (0.36 g), stirred at 120 ° C for 3 days, after cooling, poured into ice water The organic layer was extracted with ethyl acetate, washed with brine, dried over magnesium sulfate, and decompressed to obtain a slurry. The silica gel column chromatography was performed sequentially with a mixture of chloroform and methanol (50: 1), followed by a gaseous solution and methanol (1 0: 1). Dissolve. The target was collected and decompressed to give 5- {2- {[2- (4-tert-butyltriazol-2-yl) phenylarfuran-5-yl] methyl) carazol-4-ylmethyl} -1H-tetrazole (0.12 g). IR (Nujol): 2740, 1500 cm-1 NMR (CDCI3, δ): 1.41 (9H, s), 4.40 (2H, s), 4.44 (2H, s) f 6.99 (1H, s) 7 7.09 (1H, s), 7.24 (1H, br d, J = 8.5HZ), 7.28 (1H, s), 7.50 (1H, d, J = 8.5Hz), 7.51 (1H, br s) MASS: 436 (M +), 254 Example 1 2 A compound of the following formula was obtained as in Example 11. 5- [2- (4-Third-Butyltriazol-2-yl) phenylarfuran-5-yl] -1H-tetrazole. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) IR (Nujol): 2700, 1620, 1600, 1570, 1500 cm'1 NMR (CDCI3, δ): 1.38 (9Η , s), 7.54 (1H, s), 7.71 (1H, d, J = 1.0Hz), 7.95 (1H, d, J = 8.7Hz), 8.08 (1H, dd, J = 8.7, 1.7Hz) , 8.45 (1H, dd, J = 1.7, 1.0Hz) MASS: 325 (M +), 297, 282, 267 -85- This paper size applies to China National Standard (CNS) A4 (21 OX 297 mm) 474811 A7 B7 V. Description of the invention (deduction) Example 1 3 Mixed 5- [2- (4-Third-Butylbrazol-2-yl) benzopyranfuran-5-yl] -1H-tetrazole (1.55g), 2 -Ethyl iodomethyl benzyl acid (1.67g), and 2-butane (15ml) solution of potassium succinate (1.8Dg), stirred at reflux for 5 hours, after β cooling, poured into water, extracted with ethyl acetate, organic The layer was washed with brine, dried over magnesium sulfate, concentrated under reduced pressure, and subjected to silica gel column chromatography. Toluene and ethyl acetate were separated. Collect the target substance and decompress it to give 5- [2- (4-Third-butyl_azol-2-yl) benzopyranfuran-5-yl] -2- [2- (ethanecarbonyl) benzyl] -2H-tetrazole (2.05g) and 5- [2- (4-tert-butyltriazol-2-yl) benzofuran-5-yl] -1- [2- (ethoxycarboxy) benzyl Yl] -1H-tetrazolium (0-24g) 0 5- [2- (4-Third-butyl-pyrazol-2-yl) benzopyranfuran-5-yl] -2- [2- (ethane carbonyl ) Benzyl] -2H-tetrazole IR (Film): 3140, 1770, 1720, 1620, 1600, 1580, 1530, 1500 cm-1 NMR (CDC13, δ): 1.42 (9H, s), 1.43 (3H , t, J = 7.1Hz), 4.43 (2H, q, J = 7.1Hz), 6.35 (2H, s), 6.98 (1H, br d, J = 7Hz), 7.01 (1H, s), 7.2 (1H , m), 7.40 (1H, d, J = 0.9Hz), 7.46 (1H, m), 7.63 (1H, d, J = 8.6Hz), 8.10 (1H, br d, J = 7Hz), 8.16 (1H , dd, J = 8.6, 1.7Hz), printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs (please read the precautions on the back before filling this page) 8.43 (1H, dd, J = 1.7, 0.9Hz) MASS ( m / z): 487 (M +), 430, 414, 386, 353, 325, 310, 282, 267 5- [2- (4 -Third-butyl-blazol-2-yl) benzofuran-5- Yl] -1- [2- (ethoxycarbonyl) benzyl] -1H-tetrazole-8 6- This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm). Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 474811 A7 _B7__ V. Description of the Invention (Jiang) IR (Film): 3120, 1730, 1710, 1600, 1580, 1530, 1500 NMR (CDC13, δ): 1.38 (3Η, t, J = 7.1Hz), 1.41 (9Η, s), 4.33 (2H, q, J = 7.1Hz), 6.18 (2H, s), 6.83 (1H, br d, J = 6.2Hz), 7.03 (1H, s), 7.2 (1H, m), 7.34 (1H, d / J = 0.7Hz), 7.48 (1H, m), 7.55 (1H, dd, J = 8.6, 1.7Hz), 7.62 (1H, d, J = 8.6Hz), 7.83 (1H, dd, J = 1.7, 0.7Hz), 8.14 (1H, brd, J = 7.5Hz) MASS (m / z): 487 (M +), 458, 414, 386, 353, 324, 310, 287, 267 Example 1 4 Mixed with 4-tert-butyl-2- [5- (chloromethyl) phenylhydrazone-2 -Yl] carbazole (0.30 g), indolin-3 -benzyl acetate (0.25 g), Na 0 Η (0.24 g) and a small amount of hexadecyltrimethyl chloride Dichloromethane (10ml) of ammonium, stir at reflux for 3 hours, add water, neutralize with dilute hydrochloric acid, concentrate under reduced pressure, silica gel column chromatography, dissolve the mixed gas of methane and methanol, collect the target, and reduce the pressure to give 1- ([2 -(4-tert-butyltriazol-2-yl) benzofuran-5-yl Methyl) indol flowers P 3 - acetic acid (0 · 1 8 g). mp: 111-115 ° C (dec.) IR (Nujol): 2500-2700, 1710, 1610 cm-1 NMR (CDCI3, δ): 1.39 (9H, s), 3.77 (2H, s), 5.28 (2H , s), 6.95 (1H, s), 7.04-7.29 (7H, m), 7.40 (1H, d, J = 8.5Hz), 7.61 (1H, d, J = 7.2Hz) MASS: 444 (M) + , 400, 270 Add Na H (60% oil, 30 mg) to 3-cyano-6-methylindane II at room temperature. 7-This paper size is applicable to Chinese National Standard (CNS) A4 specifications. (210X297 mm) Order Aw. (Please read the precautions on the back before filling this page) 474811 A7 _B7_ V. Description of the invention (u) (73mg) in Ν, Ν -dimethylformamide (2ml) solution. After 30 minutes, 4-tert-butyl-2- [5- (chloromethyl) benzopyranfuran-2-yl] azolazole (150 mg) and a small amount of KI were added. Stir for 3 hours, add ice water, acidify with dilute hydrochloric acid, extract with ethyl acetate, wash the organic layer with brine, dry with magnesium sulfate, and decompress to obtain a slurry. After silica gel column chromatography, dissolve the toluene and ethyl acetate mixtures, collect the The target compound is decompressed to give 4-tert-butyl-2- {5-[(3-cyano-6-methylindohdo-1-yl) methyl] phenylsulfan-2-yl] pyrazole (0.2g).

mp: 103-105 ° C IR (Nujol): 2200, 1530, 1450, 1350 cm-1 NMR (CDC13, δ): 1.40 (9H, s), 2.75 (3H, s), 5.39 (2H, s), 6.99 (1H, s), 7.09-7.19 (3H, m), 7.27 (1H, d, J = 0.9Hz), 7.37 (1H, d, J = 1.4Hz), 7.52 (1H, d, J = 8.5Hz ), 7.56 (1H, s), 7.66 (1H, d, J = 8.2Hz) MASS: 426 (M + H) + Example 1 fi The compound of formula 15 was obtained as in Example 15. (Please read the notes on the back before filling in this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 8 8 _ This paper size applies to China National Standard (CNS) A4 (210X297 mm) 474811 A7 B7 V. Invention Explanation (π)

16-1 Me Η H CH IR (Nujol): 2200 cm-1 NMR (DMSO-dg, δ): 1.34 (9H, s), 2.40 (3H, s), 5.60 (2H, s), 7.12 (1H, d, J = 7.9Hz), 7.35 (1H, d, J = 8.2Hz), 7.44-7.69 (6H, m), 8.46 (1H, s) MASS: 426 (M + H) +

H Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs

H Me CH mp: 50-56 ° C IR (Nujol): 2200 cm'1 NMR (CDC13, δ): 1.40 (9H, s), 2.56 (3H, s), 5.69 (2H, s), 6.94-7.03 (2H, in), 7.00 (1H, s), 7.12 (1H, d, J = l.lHz), 7.17 (1H, d, J = 7.8Hz), 7.23 (1H, d, J = 0.9Hz), 7.50 (1H, d, J = 8.5Hz), 7.58 (1H, s), 7.65 (1H, d, J = 7.8Hz) MASS: 426 (M + H) + This paper size applies to Chinese National Standard (CNS) Μ Specifications (2 丨 〇'〆297mm) -89- 474811 A7 B7 V. Description of the invention (〇) Example R12 r13 r14 y Physical data 16-3 iPr Η H CH IR (Neat): 2950, 2200, 1530, 1480 , 1440, 1390, 1350 cm-1 NMR (CDC13, δ): 1.30 (6H, d, J = 7.0Hz), 1.40 (9H, s), 3.04 (1H, hept, J = 7.0Hz), 5.40 (2H , s), 6.99 (1H, s), 7.13 (1H, dd, J = 1.8, 9.4Hz), 7.18 (1H, dd, J = 1.6, 8.2Hz), 7.26-7.32 (2H, m), 7.39 ( 1H, s), 7.51 (1H, d, J = 8.4Hz), 7.60 (1H, s), 7.62 (1H, s) 'MASS: 454 (M + H) + 16-4 tBu Η H CH IR (Neat ): 2200, 1530, 1480, 1440, 1390, 1355 cm-1 NMR (CDC13, δ): 1.39 (9H, s), 1.40 (9H, s), 5.40 (2H, s), 6.99 (1H, s) , 7.14 (1H, dd, J = 1.9, 8.6Hz), 7.27-7.41 (4H, m), 7.51 (1H, d, economy Printed by the Central Consumer Standards Cooperative of the Ministry of Justice (please read the precautions on the back before filling this page) J = 8.6Hz), 7.61 (1H, s), 7.60 (1H, d, J = l.lHz) MASS: 468 (M + H) + -90 This paper size applies Chinese National Standard (CNS) A4 specification (210X297mm) 474811 A7 B7 V. Description of the invention () Example R12 r13 r14 γ Physical data 16-5

CF 3 Η Η CH mp: 101-102 ° C IR (Nujol): 2210, 1460, 1375, 1320 cm " -1 NMR (CDC13, δ): 1.40 (9H, s), 5.47 (2H, s. ), 7.00 (1H, s), 7.13 (1H, dd, J = 1.9, 8.6Hz), 7.29 (1H, d, J = 0.8Hz), 7.40 (1H, d, J = 1.2Hz), 7.50 -7.58 (3H, ^ m), 7.75 (1H, s), 8.10 (1H, s) MASS: 480 (M + H) + (Please read the precautions on the back before filling this page) 16-6

F

Η H

CH -1 IR (Nujol): 2200, 1190 cm NMR (CDCI3, δ): 1.42 (9H, s), 5.42 (2H, s), 7.01 (1H, s), 7.01-7.15 (2H, m), 7.30 (1H, dd, J = 9.0, 4.2Hz), 7.40-7.55 (4H, m), 7.67 (1H, s) MASS: 430 (M + H) + 16-7

Cl Consumer Co-operation of Central Bureau of Standards, Ministry of Economic Affairs_PRINT 印 H CH IR (Nujol): 3150, 2230, 1530, 1500, 1490 cnT1 NMR (CDC13, δ): 1.40 (9H, s), 5.41 (2H, s ), 7.00 (1H, s), 7.10 (1H, dd, J = 1.9, 8.5Hz), 7.18-7.32 (3H, m), 7.38 (1H, d, J = 1.2Hz), 7.52 ( 1H, d, J = 8.5Hz) f 7.64 (1H, s), 7.76 (1H, d, J = 1.7Hz) MASS: 445 (M +), 270 This paper size applies to China National Standard (CNS) A4 (21〇'〆297mm) • 91 · 474811 A7 B7 V. Description of the invention (~) Example r12 r13 r14 γ Physical data 16-8 Η Cl H CH IR (Nujol): 2230, 1610, 1535, 1500, 1350 cm-1 NMR (CDC13, δ): 1.40 (9H, s), 5.37 (2H, s), 7.00 (1H, s), 7.11 (1H, dd, J = 1.9, 8.5Hz), 7.24-7.29 (2H, m), 7.39 (2H, d, J = 1.9Hz), 7.52 (1H, d, J = 8.5Hz), 7.61 (1H, s), 7.68 (1H, d, J = 8.4Hz) MASS: 445 (M +), 270 16-9 N〇2 Η H CH IR (Nujol): 2230, 1620, 1515, 1340 cm-1 Standards of the Ministry of Economic Affairs% Printed by employee consumer cooperatives (please read the precautions on the back before Fill out this page) NMR (CDC13, δ): 1.40 (9H, s), 5.50 (2H, s >, 7.10 (1 H, s), 7.14 (1H, dd, J = 1.9, 8.5Hz), 7.28 (1H, d, J = 0.9Hz), 7.42 (1H, d, J = 1.3Hz), 7.49 (1H, d, J = 9.2Hz >, 7.55 (1H, d, J = 8.5Hz), 7.80 (1H, s), 8.20 (1H, d, J = 9.2, 2.2Hz), 8.72 (1H, d, J = 2.2Hz) MASS : 456 (M +), 426, 270, 255 -92- The paper size is applicable to Chinese National Standard (CNS) A4 (2 丨 〇'〆297mm) 474811 A7 B7 V. Description of Invention (妗) Central Standard of the Ministry of Economic Affairs Examples of printed bags for employees' cooperatives in the Bureau R12 R13 R14 Y Physical data 16-10 COOMe Η H CH IR (Nujol): 2200, 1710, 1615, 1530, 1500 cm-1 NMR (DMS0-d6, δ): 1.35 (9H, s), 3.57 (3H, s), 5.68 (2H, s), 7.39 (1H, dd, J = 1.6, 8 6Hz), 7.46 (1H, s), 7.49 (1H, s), 7.66- 7.75 (2H , m), 7.81 (1H, d, J = 8.6Hz), 7.87-7.94 (1H, m), 8.26 (1H, s), 8.71 (1H, s) MASS: 469 (M +), 438, 286, 270 16-11 Η OMe H CH mp: 175-17.6 ° C-IR (Nujol): 2200, 1625, 1530, 1495 cm-1 NMR (CDC13, δ): 1.40 (9H, s), 3.80 (3H, s) , 5.37 (2H, s), 6.80 (1H, d, J = 2.2Hz), 6.95 (1H, dd, 2, 8, 8Hz), 6.99 (1H, s), 7.13 (1H, dd, J = 1.8, 8.5Hz), 7.27 (1H, s), 7.38 (1H, s), 7.52 (1H, d , J = 8.5Hz), 7.53 (1H, s), 7.65 (1H, d, J = 8.8Hz) MASS: 442 (M + H) + -93- (Please read the precautions on the back before filling this page) This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 474811 A7 B7 V. Description of invention (W) Example R12 R13 R14 Y Physical data (Please read the precautions on the back before filling this page) 16-12 OBzl Η H CH IR (Nujol): 2200, 1220 cm-1 NMR (CDC13, δ): 1.40 (9H, s), 5.12 (2H, s), 5.39 (2H, s), 6.99 (1H, s), 7.01 (1H, dd, J = 2.3, 9.0Hz), 7.09-7.53 (11H, m), 7.59 (1H, s) MASS: 518 (M + H) + 16-13 Me Η IR N IR (Nujol): 2200 cm'1 NMR (CDC13, δ): 1.40 (9H, s), 2.48 (3H, s), 5.71 (2H, s), 6.98 (1H, s), 7.19-7.30 (3H, m), 7.36 ( 1H, d, J = 8.7Hz), 7.46-7.50 (2H, m), 7.61 (1H, s) MASS: 427 (M + H) + Example 1 7 NaH (60% oil, 0 15 g) N, N-dimethylformamide (5ffll) solution of human ind P # -2-methylcarboxylate (0.56 g). After 30 minutes, add 4- Printing by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. The third base is methyl chloride. The slurry of the material solution is collected and reduced, and the pressure is reduced. The drying solution is dry-mixed with magnesium ester acid, acetic acid, ethyl acetate, and water benzene salt. The layering machine column has a gum base-5 -furan.骈 Phenyl-2 azole) o pt7g group 8 butyl (0 triester methylene 4 acid T carboxy 2 I [2 _ {时 二 I 1 2 ： 得}) condensed indented paper This paper applies the Chinese national standard (CNS) A4 specifications (2! 0 × 297 mm) printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 474811 A7 B7 V. Description of invention (%) mp; 108-109eC (from diisopropyl ether) IR (Nujol): 1710, 1610, 1590, 1515 cm-1 NMR (CDC13, δ): 1.39 (9H, s), 3.87 (3H, s), 5.93 (2H, s), 6.94 (1H, s), 7.08 (1H, dd, J = 1.8, 8.5 Hz), 7-12-7.43 (7H / m), 7.72 (1H, d, J = 8.0Hz) MASS: 444 (M) +, 286, 270, 254 Example 1 8 will 1- ((2- (4 -Third butyl carbazol-2-yl) benzylfuran-5-yl] methyl) B-Methyl-2-carboxylate (0.86g), Na0H (0.77g) in water (10 m 1) and ethanol (2 Q m 1) were mixed and refluxed for 2 hours. The solvent was removed, dissolved in water, and diluted with hydrochloric acid. To P Η 3. The precipitate was collected by filtration and dried under vacuum to obtain 1-{[2- (4-tert-butyltriazole-2-yl) phenylbenzofuran-5-yl] methyl) indodol-2-carboxylic acid (Q. 8 0 g). mp: 160 ° C (dec.) IR (Nujol): 2500-2700, 1690, 1515, 1500 cm-1 NMR (CDC13, δ): 1.38 (9H, s), 4.0 (1H, br s), 5.92 ( 2H, s), 6.94 (1H, s), 7.08 (1H, dd, J = 1.8, 8.5Hz) 7.13-7.41 (6H, m), 7.54 (1H, s), 7.73 (1H, d, J = 8.〇Hz) MASS: 430 (M > +, 386, 270, 255 丄 Mixed 1-{[2- (4 -Third-butyltriazol-2-yl) phenylarfuran-5-yl] forma Group) benzene (10 m 1) ft of 11-2-carboxylic acid (0.46 g) and sulfenylsulfonium gas (0.16 ml) was refluxed for 2 hours. After cooling, it was concentrated, treated with concentrated ammonia water, taken from acetic acid S 6 _, the organic layer was washed with brine, dried over magnesium sulfate, and steamed to give 1-{[2-U -third butyl azole- 2 -yl) benzofuran 5_yl] methyl) indocin-2-Centamidine (0.40g).

叩: 151-151.5 ° C IR (Nujol): 3350, 3150, 1630, 1600 cm-1 NMR (CDCI3, δ): 1.39 (9H, s), 5.80-6.00 (2H, br s), 5.94 ( 2H, s >, 6.94 (1H, s), 7.10-7.34 (6H, m), 7.40 (1H, d, J = 8.0Hz), 7.68 (1H, d, J = 7.8Hz) MASS: 429 (h +) , 411, 385, 270 -9 5-Applicable to this paper size) 8 size 4 (21〇 × 297 mm) " -------- · clothing ------, 1T ----- 1 # (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 474811 A7 B7 V. Description of the invention (9Γ) m 1) adding N, N -dimethylformamide (0 -8 6 m 1), after 10 minutes, adding 1-{[2-(4 -tert-butyloxazole-2 -yl) Benzofuran-5 -yl] methyl} indiodol-2 -carboxamide (0.43 g) in N, N-dimethylformamide (5 in 1) solution. After stirring at room temperature for several minutes, sodium bicarbonate water was added. The precipitate was collected by filtration, washed with water, and air-dried to give 4-tert-butyl-2-{5--[(2-cyanoindiodo-1 -yl) methyl] benzopyranfuran-2-yl} thiazole (0.43 g ) 0 IR (Nujol): 2200, 1600, 1500 cm-1 NMR (CDC13, δ): 1.39 (9Η, s), 5.58 (2Η, s), 6.97 (1H, s), 7.13-7.40 (7H, m ), 7.47 (1H, d, J = 8.5Hz), 7.68 (1H, d, J = 8.0Hz) MASS: 411 (M +), 296, 270, 255 M 2 1 Mixed 4 -Third butyl-2- {5-[(3 -Cyano-6-methylindiodol-butyl) methyl] benzofuran-2-yl] thiazole (0.19 g), sodium azide (0.32 g ), Gasified ammonium (0.30 g) of N, N-dimethylformamide (2 in 1) and stirred at 120 ° C for 7 2 hours. Cool to room temperature, pour into ice water, acidify with dilute hydrochloric acid, collect the precipitate by filtration, and air-dry. After silica gel column chromatography, dichloromethane and methanol mixed solution dissolve. Pyridoxazol-2-yl) benzylfuran-5 -yl] methyl) -6-methylindole II-do-3 -yl}-1 fluorene -tetrazole (0.04 g)

mp: 240-245 ° C IR (Nujol): 2500-2700, 1620, 1600, 1490, 1450, 1410 cm-1 NMR (DMSO-dg, δ): 1.34 (9H, s), 2.44 (3H, s) , 5.64 (2H, s), 7.10 (1H, d, J = 8.4Hz), 7.36 (1H, dd, J = 1.7, 8.5Hz), 7.47 (1H, s), 7.51 (1H, d, J = 1.7 Hz), 7.51 (1H, s), 7.63 (1H, s), 7.69 (1H, d, J = 8.5Hz), 8.12 (1H, d, J = 8.4Hz), 8.14 (1H, s) MASS: 469 (M + H) + Example 22 Following Example 21 The following compound was prepared. -9 6-This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297mm) I ------- • Cloth ------ 1T ------ Φ (Please read the back first Please note this page before filling in this page) 474811 A7 B7 V. Description of the invention (today r

example

2 1 R

4 IX R

Y 22-1 Me Η H CH IR (Nujol): 3500-2500 cm-1 NMR (DMSO-dg, δ): 1.34 (9H, s), 2.45 (3H, s), 5.65 (2H, s), 7.12 (1H, d, J = 8.3Hz), 7.35 (1H, d, J = 8.6Hz), 7.47-7.71 (5H, m), 8.05 (1H, s), 8.18 (1H, s) MASS: 469 (M + H) + H 2-2 2 Printed H Me CH mp: 165-185 ° C (dec.) IR (Nujol): 3300, 2500-3000, 1610, 1590, 1500, 1450, 1360 cm-1 NMR (CDC13, δ): 1.41 (9H, s), 2.49 (3H, s), 5.52 (2H, s), 6.83-7.12 (5H, m), 6.95 (1H, s), 7.22 (1H, d, J = 8.6Hz), 7.89 (1H, s), 8.17 (1H, d, J = 8.0Hz) MASS: 469 (M + H) + Element analysis: c26h24n6os-i / 4ch2ci2: Calculated value : C 64.37, H 5.04, N 17.16 Measured value: C 64.23, H 5.12, N 17.21 -97- This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) --------- • Clothing ------? 1 ------ 9 (Please read the precautions on the back before filling this page) 474811 A7 B7 V. Description of the invention (%)

Example R12 R13 R14 Y

22-3 iPr Η H CH

mp: 153-159 ° C IR (Nujol): 3400, 2700, 1620, 1600, 1490, 1400 cm-1 NMR (DMSO-dg, δ): 1.28 (6H, d, J = 7.0Hz), 1.34 (9H , s), 3.03 (1H, hept, J = 7.0Hz), 5.65 (2H, s), 7.19 (1H, dd, J = 2.2, 8.5Hz), 7.37 (1H, dd, J = 2.1, 8.6Hz) , 7.47 (1H, s), 7.51 (1H, s), 7.59 (1H, d, J = 8.5Hz), 7.66 (1H, d, J = 2.2Hz), 7.68 (1H, d, J = 8.6 Hz), 8.10 (1H, s), 8.21 (1H, s) MASS: 497 (M + H) + Elemental analysis: ^ 28 ^ 2 9 ^ ζ〇3 · Η2〇 · Calculated value: C 66.04, Η 5_82, N 16.50 Found: C 65.97, H 6.18, N 15.85

22-4 tBu Η H CH mp: 162-169eC IR (Nujol): 3300, 2700-2500, 1620, 1600, 1460, 1380 cm-1 NMR (DMS0-d6, δ): 1.34 (9H, s) f 1.36 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page) (9Η, s >, 5.65 (2Η, s), 7.37 (2Η, dd, J = 2.2, 8.9Hz), 7.47 (1H, s), 7.51 (1H, s), 7.59 (1H, d, J = 8.9Hz), 7.60 (1H, d, J = 1.8Hz), 7.68 (1H, d, J = 8.9Hz), 8.20 (1H, s), 8.24 (1H, d, J = 1.8Hz) MASS: 511 (M + H) + This paper size applies the national standard of China (CNS) A4 (210X297 mm) 98- 474811 Ministry of Economic Affairs Printed by the Consumer Standards of the Central Bureau of Standards A 7 B7 V. Description of Invention (W) Example R12 R13 R14 Y 22-5 CF3 Η H CH mp: 190-200 ° C IR (Nujol): 3300, 2500-2700, 1630, 1600, 1490, 1460, 1410, 1380, 1340 cm-1 NMR (DMSO-dg, δ): 1.34 (9H, s), 5.78 (2H, s) f 7.39 (1H, dd, J = 2.2, 8.6Hz) , 7.48 (1H, s), 7.52 (1H, s), 7.62 (1H, dd, J = 1.8, 8.4Hz), 7.69 (1H, s), 7.71 (1H, d, J = 8.4Hz), 7.96 ( 1H, d, J = 8.6Hz), 8.42 (1H, s), 8.62 (1H, s) MASS: 523 (M + H) + Element analysis: C26H 21F3N6os'H2 °: Calculated: C 57.80, H 4.29, N 15.55 Found: C 58.34, H 4.58, N 14.96 22-6 FH. H CH IR (Nujol): 3600-3000, 1180 cm-1 NMR (DMSO -dg, δ): 1.34 (9H, s), 5.69 (2H, s), 7.17 (1H, t, J = 9.3Hz >, 7.38 (1H, d, J = 8.6Hz), 7.47 (1H, s) , 7.51 (1H, s), 7.67-7.77 (3H, m), 7.93 (1H, d, J = 9.7Hz), 8.31 (1H, s) MASS: 473 (M + H) + (Please read the Please fill in this page again for the matters needing attention) -99- This paper size applies to Chinese National Standard (CNS) A4 specification (21 OX 297 mm) 474811 A7 B7 V. Description of invention (shirt)

Example R12 R13 R14 Y

22-7 Cl Η H CH (Please read the notes on the back before filling this page) mp: 238 ° C (dec.) IR (Nujol): 3300-3500, 3100, 1630, 1600, 1500, 1410 cm'1 NMR (DMS0-d6 / δ): 1.35 (9H, s), 5.71 (2H, s), 7.30-7.40 (2H, m), 7.47 (1H, s), 7.51 (1H, s), 7.67 ( 1H, s), 7.70 (1H, d, J = 9.5Hz), 7.76 (1H, d, J = 8.8Hz), 8.27 (1H, d, J = 2.0Hz), 8.32 (1H, s) _MASS: 488 (M +), 455, 270, 255

22-8 H Cl H CH mp: 245 ° C (dec.) IR (Nujol): '2500-3000, 1625, 1600, .1500 cm-1 NMR (DMSO-dg, δ): 1.36 (9H, s) , 5.69 (2H, s), 7.30 (1H, dd, J = l-8, 8.5Hz), 7.38 (1H, dd, J = l.8, 8.5Hz), 7.47 (1H, s), 7.53 (1H , s >, 7.69 (1H, s), 7.71 (1H, d, J = 8.5Hz), 7.89 (1H, d, J = 1.8Hz), 8.25 (1H, d, J = 8.5Hz), 8.25 (1H , s) MASS: 488 (M +), 455, 270, 255 Printed by the Central Standard of the Ministry of Economic Affairs

This paper size is applicable to Chinese National Standard (CNS) A4 (2! 0X297 mm) 474811 A7, B7 V. Description of Invention (W) Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs R12 R13 R14 Y 22-9 Ν〇 2 Η Η CH mp: 162 ° C (dec.) IR (Nujol): 3300-3000, 1630, 1600, 1510, 1410, 1430 cm-1 NMR (DMSO-dg, δ): 1.46 (9H, s), 5.79 (2H, s), 7.42 (1H, dd, J = 1.6, 8.6Hz), 7.46 (1H, s), 7.51 (1H, s), 7.70-7.74 (2H, m), 7.96 (1H, d, J = 9.2Hz), 8.19 (1H, dd, J = 2.3, 9.2Hz), 8.47 (1H, s), 9.18 (1H, d, J = 2.3Hz) MASS: 500 (M + H) + 22-10 COOMe Η H CH mp: 218 ° C (dec.) IR (Nujol): 3200, 2500-2700, 1710, 1650, 1630, 1600, 1500, 1400, 1390 cm-1 NMR (DMSO-dg, δ): 1.40 (9H, s >, 3.90 (3H, s), 5.74 (2H, s), 7.39 (1H, dd, J = 1.8, 8.5Hz), 7.47 (1H, s), 7.51 (1H, s ), 7.68 (1H, s), 7.70 (1H, d, J = 8.5Hz), 7.83 (1H, d, J = 8.7Hz), 7.91 (1H, dd, J = 1.5, 8.7Hz), 8.32 (1H , s), 8.98 (1H, s) MASS: 511 (MH) + (Please read the precautions on the back before filling this page) -101- This paper size applies to China National Standard (CNS) A_4 specifications 210X 297 mm) 474811 A7 ___ B7 V. Description of the invention (⑽) Printing example of the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs R12 R13 R14 Y 22-11 H OMe H CH mp: 239-242eC IR (Nujol): 3200, 2500-2700, 1620, 1600, 1590, 1460 cm-1 NMR (DMSO-dg, δ): 1.34 (9H, s), 3.82 (3H, s), 5.64 (2H, s >, 6.92 (1H, dd, J = 2.2, 8.6Hz), 7.27 (1H, d, J = 2.2Hz), 7.39 (1H, dd, J = 1.8, 9.0Hz), 7.47 (1H, s), 7.53 (1H, s), 7.68 ( 1H, s), 7.69 (1H, d, J = 8.6Hz), 8.07 (1H, s >, 8.11 (1H, d, J = 9.0Hz) MASS: 485 (M + H) + Elemental analysis C26H24N6 ° 2S ' H2 °: Calculated: C 62.13, H 5.21, N 16.72 Real side: C 62.30, H 5.28, N 16.43 22-12 OiPr Η H CH IR (Nujol): 3100-2500, 1200 cm-1 NMR (DMSO- dg, δ): 1.30 (6H, d, J = 6.0Hz), 1.34 (9H, s), 4.63 (1H, hept, J = 6.0Hz), 5.63 (2H, s), 6.90 (1H, dd, J = 8.9, 2.4Hz), 7.37 (1H, dd, J = 8.5, 1.8Hz), 7.47 (1H, s), 7.51 (1H, s), 7.56 (1H, d, J = 8.5Hz), 7.66 (1H , s), 7.69 (1H, d, J = 8.9Hz), 7.72 (1H, d, J = 2.4Hz), 8.19 (1H, s) MASS: 513 (M + H) + (Please read the note on the back first (Fill in this page again) Paper size is applicable to Chinese National Standard (CNS) A4 (210X 297 mm) -102- 474811 A7 __ · _ B7 V. Description of Invention (W) Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs R12 R13 R14 Y 22- 13 O-cPen Η H CH IR (Nujol): 3600-2500, 1200 cm-1 NMR (CDC13, δ): 1.39 (9H, s), 1.40- 2.00 (8H, m), 4.82 (1H, br s) , 5.23 (2H, s >, 6.88 (1H, dd, J = 8.9, 2.3Hz), 6.99 (1H, s), 7.01 (1H, d, J = 8.5Hz), 7.07 (1H, s), 7.18- 7.30 (3H, m), 7.79 (1H, d, J = 2.3Hz), 7.86 (1H, s) MASS: 539 (M + H) + 22-14 OMe Η H CH mp: 166-170 ° C (dec .) IR (Nujol): 3300, 2500-2700, 1630, 1610, 1480, 1460, 1380, 1220 cm-1 NMR (DMSO-d6, δ): 1.34 (9H, s), 3.83 (3H, s), 5.64 (2H, s), 6.92 (1H, dd, J = 2.4, 9.0Hz), 7.36 (1H, br d, J = 8.5Hz), 7.47 (1H, s), 7.51 (1H, s), 7.59 (1H, d, J = 9.0Hz), 7.60-7.72 (3H, m), 8.19 (1H, s) MASS: 485 (M + H) +, 286 22-15 OH Η H CH mp: 242 ° C (dec-) IR (Nujol): 3600-3000 cm-*-NMR (DMSO-dg, δ): 1.34 (9H, s), 3.35 (1H, br s >, 5.59 (2H, s), 6.78 ( 1H, dd, J = 2.2, 8.8Hz), 7.36 (1Ή, d, J = 8.5Hz), 7.46 (1H, s), 7.47 (1H, d, J = 8.8Hz), 7.50 (1H, s), 7.65 (1H, d, J = 2.2Hz), 7.69 ( 1H, d, J = 8.5Hz) (Please read the notes on the back before filling in this page) This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) —103— 474811 A7 B7, Invention Description ( 1.3)-Example R12 r13 r14 γ

22-16 -〇CH2-Tet Η H CH (Please read the notes on the back before filling this page)

mp: 192-196 ° C IR (Nujol): 3700-3000, 1250 cm-1 NMR (DMS0-d6, δ): 1.34 (9H, s), 5.04 (2H, br s), 5.28 (2H, s) , 5.62 (2H, s), 6.99 (1H, dd, J = 2.4, 8.9Hz), 7.36 (1H, dd, J = l.7, 8.5Hz), 7.47 (1H, s), 7.50 (1H, s ), 7.58 (1H, d, J = 8.9Hz), 7.65 (1H, s), 7.68 (1H, d, J = 8.5Hz >, 7.88 (1H, d, J = 2.4Hz), 8.19 (1H , ____ sj _._

22-17 -0CH2C00Me Η H CH

mp: 137-139eC IR (Nujol): 3300-1750, 1630, 1610, 1470, 1380 cm-1 NMR (DMSO-dg, δ): 1.34 (9H, s), 3.72 (3H, s >, 4.85 (2H , s), 5.65 (2H, s), 6.98 (1H, dd, J = 9.0, 2.5Hz >, 7.34 (1H, dd, J = 1.8, 8.5Hz), 7.47 (1H, s), 7.51 ( 1H, d, J = 0.8Hz), 7.61 (1H, d, J = 9.0Hz), 7.63-7.71 (3H, m), 8.23 (1H, s) ____ MASS: 542 (M +), 528, 499, 270 Under the Ministry of Standards and Standards, printed by consumer cooperatives 104. The paper size is suitable for U National Standards (CNS) A · 4 specifications [21 (} > < 297 public directors) Example) R12 R13 R14 Υ 22-18 -OC (Me) 2C00Et Η H CH mp: 136.8-137.8 ° C IR (Nujol): 3200-2300, 1720 cm'1 NMR (CDC13, δ): 1.32 (3H, t , J = 7.12Hz), 1.39 (9H, s), 1.57 (6H, s), 4.30 (2H, q, J = 7.12Hz), 5.22 (2H, s), 6.86 (1H, dd, J = 2.2, 8.9Hz), 6.98 (1H, s), 7.01 (1H, dd, J = 1.8, 8.5Hz), 7.11 (1H, s), 7.12 (1H, d, J = 8.9Hz), 7.23-7.27 (2H, m), 7.81-7.84 (2H, m) MASS: 585 (M + H) + 22-19 -0CH2C (Me) 2COOMe Η H CH mp: 160 ° C (dec.) IR (Nujol): 3200-2300, 1720 cm-1 NMR (DM SO-dg, δ): 1.28 (6H, s), 1.34 (9H, s), 3.62 (3H, s), 4.05 (2H, s), 5.64 (2H, s), 6.90 (1H, dd, J = 2.3, 9.0Hz), 7.34 (1H, d, J = 8.5Hz), 7.47 (1H, s), 7.50 (1H, s), 7.57 (1H, d, J = 9.0Hz), 7.62-7.71 (3H, m), 8.20 (1H, s) MASS: 585 (M + H) + (Please read the notes on the back before filling this page) Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy — 105 — This paper size applies to China Standard (CNS) A4 specification (21 OX 297 mm) 474811 A7 B7 V. Examples of invention r12 r13 r14 γ 22-20 Η Η Me CMe mp: 225-228 ° C (dec.) IR (Nujol): 2600, 1620, 1600, 1500 cm-1 NMR (DMS0-d6 / δ): 1.34 (9H, s), 2.74 (3H, s), 5.70 (2H, s), 7.13-7.25 (3H, m), 7.42 (1H, br s), 7.46 (1H, s), 7.47 (1H, d, J = 0.6Hz), 7.60-7.68 (1H, m), 7.66 (1H, d, J = 8.5Hz), 7.9 -8.02 (1H, m) MASS: 469 (M + H) +, 307, 270

22-21 Η Η H CH mp: 143-145 ° C (dec.) IR (Nujol): 3400, 3120, 1625, 1600, 15 0 0 cm-1 NMR (DMSO-dg, δ): 1.34 (9H, s), 5.69 (2H, s), 7.26-7.31 (2H, m), 7.38 (1H, dd, J = 1.8, 8.5Hz), 7.47 (1H, s), 7.51 (1H, s), 7.67 -7.71 (3H, m), 8.23-8.27 (1H, m), 8.25 (1H, s) MASS: 455 (M + H) +, 427, 412, 270

22-22 Η Η Η N Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) IR (Nujol): 3300-3000, 1590, 1490 cm-1 NMR (DMSO-dg , δ): 1.34 (9H, s), 5.91 (2H, s), 7.29-7.40 (2H, m), 7.46 (1H, s), 7.51 (1H, s), 7.46-7.54 (1H, m) , 7.63-7.68 (2H, m), 7.88 (1H, d, J = 8.6Hz) / 8.35 (1H, d, J = 8.1Hz) _MASS: 456 (M + H) +, 413_ -106- This paper size Applicable to China National Standard (CNS) A4 specification (210X 297 mm) 474811 A7 B7 V. Description of invention (td)

Example R12 R13 R14 Y

22-23 OMe Η Η N mp: 140-145 ° C (dec.) IR (Nujol): 3300, 3100, 1625, 1600, 1500 cm-1 NMR (DMSO-dg, δ): 1.34 (9H, s) , 3.88 (3H, s), 5.92 (2H, s), 7.21 (1H, dd, J = 2.3, 9.2Hz), 7.36 (1H, d, J = 8.6Hz), 7.46 (1H, s), 7.50 ( 1H, s), 7.60-7.70 (3H, m), 7.86 (1H, d, J = 9.2Hz) MASS: 486 (M + H) +, 460, 270 Elemental analysis: C25H23N7〇2S-l / 2H2〇:

Calculated 倌: C 60.71, H 4.89, N 19.84 Found: C 60.75, H 4.99, N 18.94 22-24 -OH Η IR N IR (Nujol): 3300-3000, 2500-2700, 1590 cm-1 NMR (DMSO -dg, δ): 1.34 (9H, s), 5.88 (2H, s), 7.07 (1H, dd, J = 2.3, 9.0Hz), 7.35 (1H, dd, J = l.8, central standard of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperative (please read the notes on the back before filling this page) (8.5Hz), 7.47 (1H, s), 7.51 (1H, s), 7.61-7.69 (3H, m), 7.75 (1H , d, J = 9.0Hz), 9.65 (1H, s) MASS: 472 (M + H) + — 107— This paper size is applicable to Chinese National Standard (CNS) A4 grid (210X 297 mm) 474811 A7 • B7 V. Description of the invention (Ά)

Example R12 R13 R14 Y

22-25 -0CH2C00Et Η Η N

mp: 120-121 ° C IR (Nujol): 3500, 3100, 2500-2700, 1750, 1730, 1605, 1500 cm-1 NMR (DMSO-dg, δ): 1.24 (3H, t, J = 7.1Hz) , 1.34 (9H, s), 4.20 (2H, q, J = 7.1Hz), 4.90 (2H, s), 5.93 (2H, s), 7.28 (1H, dd, J = 2.4, 9.1Hz), 7.36 ( 1H, d, J = 2.4Hz), 7.47 (1H, s), 7.51 (1H, s), 7.60- 7.69 (3H, m), 7.89 (1H, d, J = 9.2Hz) MASS: 558 (M + H) + Elemental analysis: C28H27N7 ° 4S-1 * 2H2 °: Calculated values: C 58.06, H 5.12, N 16.93

Found: C 58.04, H 4.96, N 16.74 22-26 iPr Η Η 'N mp: 132.5 ° C (dec.) IR (Nujol): 3600-2300 cm- ^ NMR (DMS0-d6, δ): 1.29 ( 6H, d, J = 6.9Hz), 3.10 (1H, hept, J = 6.9Hz), 5.93 (2H, s), 7.37 (1H, printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the note on the back first) Please fill in this page again) dd, 3 = 1.1, 8.6Hz), 7.46 (1H, s), 7.49 (1H, d, J = 8.8Hz), 7.51 (1H, s), 7.65 (1H, s), 7.67 (1H, d, J = 8.6Hz), 7.86 (1H, d, J = 8.8Hz >., 8.14 (1H, s > MASS: 498 (M + H) +) This paper size applies to China National Standard (CNS) A4 Specifications (210X297 mm) 474811 A7 B7 V. Description of the invention

Example R12 R13 R14 Y

22-27 Me Η Η N (Please read the notes on the back before filling this page) mp: 134 ° C (dec.) IR (Nujol): 3600-3000 cm-1 NMR (CDC13 ,. δ): 1.41 ( 9H, s), 1.72 (3H, s), 5.57 (2H, s), 6.94-7.02 (3H, m), 7.13 (1H, s), 7.22-7.26 (3H, m), 7.36 (1H, d, J = 8.7Hz), 8.17 (1H, br s) MASS: 470 (M + H) +

22-28 H -COOMe H CH

mp: 143.0-147.8eC IR (Nujol): 3300, 3100, 2500-2700, 1715, 1630, 1600, 1500, 1235 cm-1 NMR (DMSO-dg, δ): 1.34 (9H, s), 3.87 (3H , s), 5.81 (2H, s), 7.37 (1H, dd, J = l. 9, 8.5Hz) ', 7.47 (1H, s), 7.52 (1H, s), 7.65 (1H, s), 7.71 (1H, d, J = 8.5Hz), 7.89 (1H, dd, J = 1.4, 8.4Hz), 8.33 (1H, br s), 8.35 (1H, d, J = 8.4Hz), 8.43 (1H, s > MASS: 531 (M + H) + Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs -109 This paper size is applicable to Chinese National Standard (CNS) A4 (210X 297 mm) 474811 A7 B7 V. Description of the invention (> 4) Example R12 R13 Rl4 Y 22-29 Η fCH2f4COOEt Η CH IR (Nujol): 3300, 3100, 2500-2700, (Please read the precautions on the back before filling this page) 1735, 1630, 1605, 1500, 1250 cm -1 NMR (DMSO-dg, δ): 1.13 (3H, t, J = 7.1Hz), 1.34 (9H, s), 1.40-1.70 (4H, m), 2.67 (2H, t, J = 7.1Hz) , 2.60-2.75 (2H, m), 4.01 (2H, q, J = 7.1Hz), 5.65 (2H, s), 7.11 (1H, d, J = 8.3Hz), 7.35 (1H, d, J = 8.5 Hz), 7.47 (1H, s), 7.51 (2H, s), 7.66 (1H, br s), 7.68 (1H, d, J = 8.5Hz), 8.13 (1H, d, J = 8.5Hz), 8.15 (1H, s) MASS: 53d (M + H) +

22-30 -CH2〇H Η H CH mp: 196-198eC (dec.) IR (Nujol): 3300-3100, 2500-2700, 1630, 1605, 1500, 1250 cm-1 NMR (DMSO-dg, δ) : 1.41 (9H, s), 4.61 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (2H, s), 5.17 (1H, br s), 5.66 (2H, s), 7.25 (1H, d, J = 8.4Hz ), 7.35 (1H, d, J = 8.6Hz), 7.47 (1H, s), 7.51 (1H, s), 7.65-7.70 (3H, n〇, 8.13 (1H, d, J = 8.5Hz), 8.15 (1H, s) MASS: 485 (M + H) +, 440 -110— This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 474811 A7 B7 V. Description of the invention (w) Example r12 r13 r14 γ

22-31 -fCH2 > 2c〇〇H Η H CH mp: 217 ° C (dec.) IR (Nujol): 3300-3100, 2500-2700, 1700, 1620, 1600, 1250 cm-1 NMR (DMSO-dg , δ): 1.34 (9H, s), 2.52-2.60 (2H, m), 2.90-3.00 (2H, m), 5.64 (2H, s), 7.17 (1H, d, J = 8.5Hz), 7.37 ( 1H, d, J = 8.5Hz), 7.47 (1H, s), 7.51 (1H, s), 7.60 (1H, d, J = 8.5Hz), 7.66 (1H, s), 7.68 (1H, d, * J = 8.6Hz), 8.08 (1H, S), 8.20 (1H, s) ____ MASS: 527 (M + H) +

22-32 Η H -OCH2COOMe CH mp: 217eC (dec.) IR (Nujol): 3100, 2500-2700, 1760, 1625, 1600, 1580, 1500, 1450, 1290, 1200, 1180, 1100 cnT1 NMR (DMSOg / δ): 1.34 (9H, s), 3.33 (3H, s), 4.98 (2H, s >, 5.95 (2H, s) f 6.83 (1H, s, J = 7.7Hz), 7.15 (1H, t, J = 7.7Hz), 7.38 (1H, dd, printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) J = l.7, 8.6Hz), 7.46 (1H, s), 7.49 (1H, d, J = 0.7Hz), 7.65 (1H, d, J = 8.6Hz), 7.66 (1H, dd, J = 0.7, 1.7Hz), 7.86 (1H, d , J = 7.5Hz), 8.17 (1H, s). _ MASS: 543 (M + H) '286 -111- This paper size applies to Chinese national standards (CNS > A4 size (210X 297 mm) 474811 A7 B7 V. Description of the invention (^) m 2 3 At room temperature, Na (油) (60 oil, 0.81 g) was added to 5-benzyloxyindole 11 -3 -acetic acid (2.5 g) of N, N. -A solution of dimethylformamide (40 ml). After 30 minutes, 4-tert-butyl-2- [5- (chloromethyl) benzofuran-2-yl] oxazole (2.71 g ), Continue stirring for 4 hours, poured into ice water, acidified with dilute hydrochloric acid, collected the precipitate by filtration, and subjected to silica gel column chromatography. The mixed solution of methane and methanol was dissolved, the target substance was collected, concentrated under reduced pressure, and the residue recrystallized from ethanol water was collected by filtration, and washed with ethanol water to obtain 5-benzyloxy-1-{[2- (4 -third butyl ifazole- 2 -yl) phenylbenzofuran-5 -yl] methyl} indodol-3 -acetic acid (4.15 g). IR (Nujol): 2500-2700, 1700, 1480 cirT1 NMR (CDC13, δ): 1.40 (9Η, s), 3.78 (2H, s), 5.08 (2H, s), -5.31 (2H, s), 6.91 (1H, dd, J = l.8, 8. · 9Ηζ), 6.96 (1H, s), 7.06-7.47 (12H, m) MASS: 551 (M + H) +, 286 Example 24 Mixed 5-benzylamino-l- {[2- (4-tert-butylifazol-2-yl ) Phenylfuran-5-yl] methyl) Indole 3-3-acetic acid (3.0g), 10% Pd-C (0.6g) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Please fill in this page again), a mixture of ammonium formate (2.Og) in ethanol (60ml) and water (6ml), stir and reflux for 18 hours, filter off the crystals, concentrate under reduced pressure, and dissolve in 10% HC 1 methanol ( 2 0 Q m 1) mixed liquid and placed in the refrigerator for 2 days. Concentrated under reduced pressure, layered sodium hydrogen sulfonate and ethyl acetate, washed the organic layer with brine, dried over magnesium sulfate, and reduced to give 1-{[2- (4-tert-butyloxazol-2-yl) Benzofuran- 5-yl] methyl) -5 -hydroxyindole-3 -acetic acid methyl ester (1.76 g). -1 1 2-This paper size is in accordance with Chinese National Standard (CNS) A4 (2! 0X297 mm) 474811 A7 B7 5. Description of the invention (" 〇 IR (Neat): 3300, 1720, 1610, 1580, 1360 cm -1 NMR (CDC13, δ): 1.40 (9Η, s), 3.69 (3Η, s), 3.71 (2Η, s), 5.29 (2H, s), 6.76 (1H, dd, J = 0.5, 8.8Hz) , 6.98 (1H, s), 7.02 (1H, d, J = 0.5Hz), 7.06-7.12 (3H, m), 7.25-7.33 (2H, m), 7.43 (1H, d, J = 8.5Hz) MASS : 475 (M + H) + Example 25 Mixed 1-{[2- (4 -Third-butylcarazol-2-yl) benzofuran-5-yl] methyl) -5 -hydroxyindole B- 3-methyl acetate (0.35 g), ethyl 5-bromovalerate

Ester (0.22 2m 1) and potassium arsenate (0.31 g) in butyrate (5 m 1), stirred at 80 ° C for 18 hours, filtered off the insolubles, and concentrated under reduced pressure. The obtained slurry was subjected to silica gel column chromatography, and the mixed solution of ethyl acetate and n-hexane was separated. The target substance was collected and decompressed to obtain. The crystal was recrystallized from n-hexane and collected by filtration. Tributylbenzozol-2-yl) benzofuran-5-yl] methyl} -5- (4-ethoxycarbonylbutoxy) indol-3 methyl acetate (0 2 3 g). Ί-R (Nujol): 1725, 1610, 1585, 1460, 1360 cm-1 NMR (CDC13, δ): 1.25 (3Η, t, J = 7.1Hz), 1.40 (9H, s), 1.81-1.88 (4H , m), 2.35-2.39 (2H, m), 3.71 (3H, s), 3.75 (2H, s), 4.00-4.05 (2H, m), 4.13 (2H, q, J = 7.1Hz), 5.33 ( 2H, s), 6.83 (1H, dd, J = 2.3, 8.8Hz), 6.97 (1H, s), 7.06 (1H, d, J = 2.3Hz), 7.05- 7.11 (2H, m), 7.11 (1H , s), 7.15 (1H, d, J = 8.8Hz >, printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) 7.34 (1H, s), 7.45 (1H, d, J = 8.5Hz) MASS: 603 (M + H) + Example 26 The following compound was prepared as in Example 25. -113- This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm) 474811 A7 B7 V. Description of the invention () tBu

NMR (CDC13, δ): 1.30 (3H, t, J = 7.1Hz), 1.40 (9H, s), 1.51 (6H, s), 4.28 (2H, q, J = 7.1Hz), 5.38 (2H, s ), 6.95 (1H, dd, J = 2.2, 9.0Hz), 7.00 _ (1H, s), 7.13 (1H, dd, J = 1.8, 8.5Hz), 7.21-7.28 (3H, m), 7.40 (1H , s), 7.52 (1H, d, J = 8.5Hz), 7.58 (1H, s) MASS: 542 (M + H) + (Please read the notes on the back before filling this page) H2 Central Bureau of Standards, Ministry of Economic Affairs Negative mp: 95-98 ° C IR (Nujol): 2250, 1738, 1500 cm-1 NMR (DMSO-dg, δ): 1.35 (9H, s), 1.22 (3H, t, J = 7.1Hz), 4.18 (2H, q, J = 7.1Hz), 4.92 (2H, s), 5.90 (2H, s), 7.29 (1H, dd, J = 2.3, 7.9Hz), 7.31 (1H, s), 7.38 (lH, dd, J = 1.7, 8.6Hz), 7.48 (1H, s), 7.52 (1H, s), 7.67 (1H, d, J = 8.6Hz), 7.70 (1H, s) , 7.98 (1H, d, J = 10.0Hz) MASS: 515 (M + H) + This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -114- 474811 A7 _B7__ 5. Description of the invention Ο Example 27 Mixed 1-{[2- (4-Third-butyl Pfazol-2-yl) phenylarfuran-5-yl] methyl) -5- (4-ethyloxobutoxy) ind B-methyl-3-acetate (0.2g) and IN NaOH (1.66ml) in Hydrofuran (2ml) and methanol (1ml) were mixed, and the mixture was stirred at room temperature for 4 hours, the solvent was removed, the aqueous layer was acidified with dilute hydrochloric acid, and the precipitate was collected by filtration. -2-yl) phenylbenzofuran-5-yl] synyl) -5- (4-carboxybutoxy) indodol-3-acetic acid (0.15g). IR (Nujol): 3300, 2700-2500, 1690, 1610 cm_1 NMR (DMSO-d6, δ): 1.34 (9H, s), 1.6-1.8 (4H, m), 2.28 (2H, t, J = 6.7Hz), 3.63 (2H, s), 3.9- 3.95 (2H, m), 5.43 (2H, s), 6.75 (1H, dd, J = 2.2, 8.8Hz), 7.02 (1H, d, J = 2.2Hz), 7.26 (1H, dd, J = l. 7, 8.5Hz), 7.30 (1H, d, J = 8.8Hz), 7.34 (1H, s), 7.47 (1H, s), 7.49 (1H, s), 7.57 (1H, br s), 7.63 (1H, d, J = 8.5Hz), 12.0 (2H, br s) MASS: 561 (M + H) + Example 27 gave the following compound. tBu -115- This paper size applies to China National Standard (CNS) A4 (210X 297mm) I -------------- 1T ------ (Please read the (Please fill in this page again)

Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 474811 A7 B7, Invention Description (M) Example D Υ Physical data

28-1 -C (Me) 2- CH mp: 206-215 ° C IR (Nujol): 3600-2300, 1710, 1250 cm-1 NMR (DMSO-dg, δ): 1.35 (9H, s), 1.51 (6H, s), 5.63 (2H, s), 6.90 (1H, dd, J = 2.3, 8.9Hz), 7.38 (1H, d, J = 8.5Hz), 7.47 (1H, s), 7.51 (1H, s), 7.58 (1H, d, J = 8.9H2), 7.67 (1H, s), 7.69 (1H, d, J = 8.5Hz), 7.79 (1H, d, J = 2.3Hz), 8.16 (1H, s) MASS: 557 (M + H) +

28-2 '-CH2C (Me) 2- CH mp: > 230 ° C IR (Nujol): 3400-3000, 1730, 3200-2300, 1260 cm " 1 NMR (DMSO-dg, δ): 1.26 (6H , s), 1.34 (9H, s), 4.02 (2H, s), 5.64 (2H, s >, 6.90 (1H, dd, J = 2.3, 9.0Hz), 7.35 (1H, d, J = 8.5Hz > , 7.47 (1H, s), 7.50 (1H, s), 7.57 (1H, d, J = 9.0Hz), 7.62-7.72 (3H, m), 8.21 (1H, s) Staff Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Printed (please read the precautions on the back before filling this page) MASS: 571 (M + H) + -116- This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 474811 A7 __ B7 Description of the Invention (K) Printed Case D by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economics Υ Physical data 28-3 -CH2- CH mp: 228-230 ° C IR (Nujol): 3350, 3100, 1790, 1765, 1630, 1600 , 1490 cm-1 NMR (DMS0-d6, δ): 1.34 (9H, s), 4.73 (2H, s), 5.65 (2H, s), 6.96 (1H, dd, J = 2.5, 9.0Hz), 7.36 (1H, d, J = 8.5Hz), 7.47 (1H, s), 7.51 (1H, s), 7.60 (1H, d, J = 9.0Hz), 7.65-7.74 (3H, m), 8.21 (1H, s) 28-4 -CH2- N mp: 180-185 ° C (dec.) IR (Nujol): 3300, 2500-2700, 1720, 1620, 1590, 1500 cm-1 NMR (DHSO-dg, δ): 1.34 (9H, s), 4.80 (2H, s), 5.93 (2H, s), 7.26 (1H, dd, J = 2.3, 9 · 1Ηζ), 7.30 (1H, dd, J = 1.9, 8.6Hz), 7.47 (1H, s), 7.51 (1H, s), 7.61 (1H, d, J = 2.3Hz), 7.61 (1H, s), 7.66 (1H, d, J = 8.6Hz), 7.88 (1H, d, J = 9.1Hz) MASS: 530 (M + H) + Elemental analysis: C26H23N7〇4S-3H2〇: Calculated value · c 53.51, H 5.01, N 16.80 Measured value: C 53.49, Η 4.56, N 16-54 (Please read the precautions on the back before filling in this page) This paper size applies to China National Standard (CNS) A4 (2IOX297 mm) -117- 474811 A7 B7__ V. Description of the invention (m0 Example 29 mixed 1-([2- (4 -Third-butyloxazosin-2-yl> phenylsulfan-5-yl] methyl) -5 -hydroxyindole II -3-methyl acetate (0.474 g), benzyl 4-bromobutyrate (0.34 g), potassium carbonate (0.19 g), Ν, Ν -dimethylformamide (5oil) mixed solution And stirred at 5 Q ° C for 8 hours. Cooled to room temperature, added ice water, extracted with ethyl acetate, washed the organic layer with brine, dried over magnesium sulfate, concentrated under reduced pressure, and subjected to silica gel column chromatography. The ethyl acetate was separated. The target substance was collected and decompressed to give 5- [3 -(Benzylcarbonyl) propanyl] -l- {[2- (4-tertiary-butyl ifazol-2-yl) phenylsulfan-5-yl] methyl) indine-3-acetic acid methyl ester (0.36 g) 〇 (Please read the precautions on the back before filling this page)

IR (Neat): 3100, 2950, 1725, 1615, 1575, 1480 cm- 1 NHR (CDC1 3, δ): 1.40 (9H, s), 2.08-2.21 (2H, m), 2.60 (2H, t , J = 7.3Hz), 3.70 (3H, s), 3.74 (2H, s), 4.05 (2H, t / J = 6.0Hz), 5.13 (2H, s), 5.32 (2H, s), 6.80 (1H , dd, J = 2.3, 8 .8Hz), 6.96 (1H, s), 7.05 (1H / d, J ~ 2. 3Hz), 7.05-7. 11 (3H / m), 7. 31-7.35 (7H , m) r 7.45 (1H, d, J = 8.5Hz) MASS: 651 (M + H) + This paper size applies to China National Standard (CNS) A4 size (210X 297 mm) 474811 Employees of the Central Standards Bureau of the Ministry of Economic Affairs Cooperative printed A 7 ____B7 V. Description of the invention (⑺) m r9 r12 Physical data 30-1 -CH2COOMe -0CH2C00Bzl IR (Neat): 1730, 1580, 1480 cm_1 NMR (CDC13, δ): 1.40 (9H, s), 3.69 (3H, s), 3.70 (2H, s), 4.71 (2H, s), 5.25 (2H, s), 5.33 (2H, s), 6.90 (1H, dd, J = 0.5, 8.8Hz) , 6.97 (1H, s), 7.05-7.09 (2H, m), 7.12 (1H, s), 7.17 (1H, d, J = 8.9Hz), 7.24 (1H, s), 7.29-7.36 (6H, m ), 7.46 (1H, d, J = 8.5Hz) MASS: 623 (M + H) + 30-2 -CN -OCH2CN IR (Nujol): 2200, 1230 cm-1 NMR (CDCI3, δ): .1.40 ( 9H, s), '4.83 (2H, s), 5.41 (2 H, s), 7.00 (1H, s), 7.01 (1H, dd, J = 8.9, 2.5Hz), 7,12 (1H, dd, J = 8.5, 1.9Hz), 7.18-7.34 (3H, m) , 7.39 (1H, s), 7.52 (1H, d, J = 8.5Hz), 7.65 (1H, s) MASS: 466 (M +), 270 30-3 -CN -0CH2C00Me IR (Nujol): 2200, 1740, 1220 cm-1 NMR (CDCI3, δ): 1.40 (9H, s), 4.70 (3H, s), 5.39 (3H, s), 7.00 (1H, s >, 7.02 (1H, dd, J = 2.4, 8.9 Hz), 7.12 (1H, dd, J = 1.8, 8.4Hz), 7-14 (1H, id, J = 2.4Hz), 7.27 (1H, s), 7.29 (1H, d, J = 8.9Hz), 7.39 (1H, d, J = 1.8Hz), 7.52 (1H, d, J = 8.4Hz), 7.60 (1H, s) MASS: 499 (M +), 270 (Please read the precautions on the back before filling this page ) This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) —119— 474811 A7 B7 V. Description of the invention (Example R-

R 12 physical data 30-4 -CH2COOMe -0Cn2

IR (Nujol): 1720, 1615, 1580, 1480, 1440, 1360 cm_r 〇〇Me NMR (CDC13, δ): 1.41 (9H, s), 3.69 (3H, s), 3.7-1 (? \\, 5 ), 5.15 (2H, s), 5.34 (2H, s), 6.92 (1H, dd, J = 2.5, 8.7Hz) f 6.97-7.17 (4H, m), 7.30 (1H, s), 7.36 (1H, s), 7.39-7.56 (3H, m), 7.68 (1H, d, J = 7.7Hz), 7.94-8.04 (2H, m), 8.16 (1H, s) MASS: 623 (M + H) + (Please Please read the notes on the back before filling this page) The Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs of the People's Republic of China printed 5- [3- (benzyloxycarbonyl) propanyl] -Bu {[2- (4-Third-butylthiazole A mixture of 2--2-yl) phenylbenzofuran-5-yl] methyl) indan-3-acetic acid methyl ester in tetrahydrofuran (2ml) and methanol (2ml) was hydrogenated under reduced pressure at room temperature under 10% Pd_C (60 ng). The crystals were filtered off and concentrated under reduced pressure to give 1-[[2-(4-tert-butyltriazol-2-yl) phenylarfuran-5-yl] methyl} -5- (3-carboxypropanyl ) Indole-3-methyl acetate (0.16 g). IR (Nujol): 2700, 1725, 1715, 1490 cm-1 NMR (CDCI3, δ): 1.40 (9Η, s), 2.13 (2Η, quint, J = 7.0 Hz), 2.61 (2H, t, J = 7.0Hz), 3.70 (3H, s), 3.74 (2H, s), 4.06 (2H, t, J = 7.0Hz), 5.31 (2H, s), 6.82 < 1H, dd, J = 2.2, 8.9 Hz), 6.97 (1H, s), 7.06-7.17 (4H, m), 7.29 (1H, s), 7.34 (1H, s), 7.45 (1H, d, J = 8.5Hz) MASS: 561 (M + H) + 12 0- This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm). Printed bags for employees' cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 474811 A7 _B7__ V. Description of the invention (M) Example 3 2 Example 31 The following compounds were obtained. 1-{[2- (4-Third-butyltriazol-2-yl) phenylarfuran-5-yl] methyl} -5-(carboxypropanyl) indole-3 -methyl acetate. IR (Nujol): 1735, 1580, 1485 cm-1 NMR (CDC13, δ): 1.40 (9Η, s >, 3.70 (3Η, s), 3.74 (2Η, s), 4.71 (2H, s), 4.8- 5.0 (1H, br s), 5.33 (2H, s), 6.90 (lH, dd, J = 2.4,8.9Hz), 6.97 (lH, s), 7.10- 7.20 (4H, m), 7.30 (1H, s ), 7.34 (1H, s), 7.45 (1H, d, J = 8.5Hz) MASS: 533 (M + H) +

Example M Mixed l- {[2- (4-Third-Butyl Blazol-2-yl) phenylarfuran-5-yl] methyl) -5- (carboxypropoxy) indodol-3 -acetic acid 145 mg of methyl ester, 24.4 mg of dimethylamine hydrochloride and 1H-hydroxybenzitriazole hydrate 4Q. 4iag in dichloromethane 2 m 1, and ethyl-3-(3 '-dimethylaminepropyl) tritiated Diimine 46.5 mg was stirred at room temperature for 2 hours, the solvent was removed, and the residue was partitioned between sodium bisulfate and ethyl acetate. The organic layer was washed with brine, dried over magnesium sulfate, concentrated under reduced pressure, and subjected to silica gel column chromatography (n-hexane-ethyl acetate). The fractions containing the target substance were combined and concentrated under reduced pressure to obtain 1- {[2- (4-tert-butylcarbazol-2-yl) phenylarfuran-5-yl] methyl} -5- (N, N -Dimethylamine formamylmethoxy) indino-3-methyl acetate 0.16 g. IR (Neat): 1730, 1650, 1575, 1480, 1340 cm-1 NMR (CDCI3, δ): 1.40 (9Η, s), 2.89 (3H, s), 3.11 (3H, s), 3.72 (2H, s ), 3.75 (2H, s), 4.72 (2H, s), 5.33 (2H, s), 6.90 (1H, dd, J = 2.4, 9.0Hz), 6.97 (1H, s), 7.08-7.25 (5H, m), 7.35 (1H, s), 7.46 (1H, d, -12 1- This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) ------------ ----, 1τΑν ~ (Please read the precautions on the back before filling this page) 474811 A7 B7 V. Description of the invention (J = 8.5Hz) MASS: 560 (M + H) ft 3 A. Example 3 3 obtained The following compounds

(Please read the notes on the back before filling out this page) 4 3 Printed by the Consumer Cooperatives of the Central Standards Bureau, Ministry of Economic Affairs, CH mp: > 200 ° C (dec.) IR (Nujol): 3500, 2300, 1670 cm- NMR (DMS〇-d6, δ): 1.34 (9H, s), 4.48 (2H, s), 5.64 (2H, s), 7.00 (1H, dd, J = 2.4, 8.9Hz >, 7.36 (1H, dd, J = l.7, 8.5Hz), 7.38 (lH, br s), 7.47 (1H, S), 7.51 (1H, s), 7.58 (1H, br s), 7.62-7.65 (2H, m), 7.68 (1H, d, J = 8.6Hz), 7.75 (1H, d, J = 2.4Hz), 8.19 (1H, s) MASS: 528 (M + H Bu-122- This paper size is applicable to China National Standard (CNS) A4 Specification (210 '乂 297 mm) 474811 A7 B7 V. Description of the Invention (^) -M < ^ ί6 物理 Physical Data 34-2 Methylamine CH mp: 179 ° C (dec.) IR (Nujol): 3500-3100, 1660 cm-1 NMR (DMSO-dg, δ): 1.34 (9H, s), 2.67 (3H, d, J = 4.6Hz), 4.52 (2H, s), 5.65 (2H , s), 7.01 (1H, dd, J = 2.4, 9.0Hz), 7.36 (1H, d, J = 8.5Hz), 7.48 (1H, s), 7.51 (1H, s), 7.59-7.71 (3H, m), 7.77 (1H, d, J = 2.3Hz), 8.09 (1H, br s), 8.21 (1H, s) MASS: 542 (M + H) +

34-3 1-pyrrolidinyl CH mp:> 230 ° C IR (Nujol): 3500-2300, 1615, 1190 cm_l NMR (DMSO-dg, δ): 1.34 (9H, s), 1.75-2.00 (4H , m), 3.55 (2H, t, J = 6.6Hz), 4.74 (2H, s), printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) 5.64 (2H, s), 6.95 (1H, dd, J = 2.4Hz, 8.9Hz), 7.35 (1H, dd, 3 = 1.1, 8.5Hz), 7.47 (1H, s), 7.51 (1H, s), 7.58 (1H, d, J = 8.9Hz), 7.63-7.70 (3H, m), 8.18 (1H, s) MASS: 582 (M + H) + ** 123— This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 (Mm) 474811 A7 B7 V. Description of the invention (^) Example Υ Physical data

R

34-4 piperidinyl io mp z > 2000 ° C IR (Nujol): 3200-2200, 1620, 1250 cnfl NMR (DMS0-d6 / δ): 1.34 (9H, s), 1.45 (2H, br s), 1.62 (4H, br s), 3.44 (4H, br s), 4.82 (2H, s), 5.64 (2H, s), 6.95 (1H, dd, J = 2.4, 8.9Hz), 7.35 ( 1H, dd, J = 1.7, 8.5Hz), 7.47 (1H, s), 7.51 (1H, s), 7.58 (1H, d, J = 8.9Hz), 7.63-7.70 (3H, m), 8.19 (1H , s) MASS: 596 (M + H) +

34-5 Mothyl CH mp: > 230 ° C IR (Nujol): 3500-2500, 1620, 1250 cm-1 NMR (DMSO-dg, δ): 1.34 (9H, s), 3.30-3.80 (4H , br s), 4.86 (2H, s), 5.64 (2H, s), 6.96 (1H, dd, J = 2.4, 8.9Ηζ), 7.36 (1H, dd, J = l.8, 8.5Hz), 7.34 (1H, s), 7.38 (1H, s), 7.47-7.71 (4H, m), 8.18 (1H, s) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling in this Page) MASS: 598 (M + H) + -124- This paper size is applicable to Chinese National Standard (CNS) A4 (210X 297 mm) 474811 Μ B7 V. Description of the invention (^ Example n < r ^

Y Physical Data 34-6 4 -thiomorpholinyl

CH mp: > 230 ° C IR (Nujol): 3500-2500, 1620 cm-1 NMR (DMS0-d6, δ): 1.34 (9H, s), 2.73 (2H, s), 3.74 (4H, s) , 5.65 (2H, s), J = 2.4, 8.9Hz), J = 1.7, 8.9Hz), 7.51 (1H, s), 2.89 (2Uf s), 4.85 (2H, s), 6.96 (1H, dd, 7.36 (1H, dd, 7.48 (1H, s), ^ .57-7.71 (4H, m), 8.20 (1H, s) MASS: 614 (M + H) + (Please read the notes on the back before filling in this Page) 34-7 4-methylpiperidin-1-yl, printed by the Consumer Cooperatives of the Central Standards Bureau, Ministry of Economic Affairs, CH mp: 232 ° C (dec.) IR (Nujol): 3600-2300, 1620, 1250 cm-1 NMR (DMSO-dg, δ): 1.34 (9H, s), 2.26 (3H, s), 2.35 (4H, br s), 3.50 (4H, br s), 4.84 (2H, s), 5.62 (2H, s), 6.92 (1H, dd, J = 2.4, 8.9Hz), 7.34 (1H, dd, J = 1.7, 8.5Hz), 7.47 (1H, s), 7.50 (1H, s), 7.55 (1H, d , J = 8.9Hz), 7.62-7.72 (3H, m), 8.16 (1H, s) MASS: 611 (M + H) + .125. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ) 474811 M B7 V. Description of the invention (W) Example Y Physical data R 34-8 CH mp: 206.7 ° C (dec.) IR (Nujol): 3500-2300, 1620, 1-1-cm 1250 cm_1 NMR ( DMS〇-d6, δ): 1 .18 (6H, br s), 1.34 (9H, s), 1.59 (1H, br s), 1.73 (4H, br s), 2.50 (2H, br s >, 2.62 (2H, br s), 3.48 ( 4H, br s), 4.83 (2H, s), 5.63 (2H, s), 6.94 (1H, dd, J = 2.4, 8.9Hz >, 7.35 (1H, dd, J = l.7, 8.5Hz ), 7.46 (1H, s), 7.50 (1H, s), 7.57 (1H, d, " j = 8.9Hz) / 7.63-7.71 (3H, m), 8.17 (1H, s) MASS: 679 (M + H) + (Please read the notes on the back before filling this page)

, TT 34_9 4 -Methylpiperon_-1 -Printed by the Consumers' Cooperative of the Central Standards Bureau, Ministry of Economics, based on amines CH mp: 179.1C (dec.) IR (Nujol): 3650-2500, 1660, 1270 cm-1 NMR (DMS〇-d6, δ): 1.34 (9H, s), 2.24 (3H, s), 2.85 (4H, br s), 3.47 (4H, br s), 4.47 and 4.91 (2H, sx 2), 5.62 (2H, s), 6.98 (1H, m), 7.35 (1H, d, J = 8.5Hz), 7.47 (1H, s), 7.50 (1H, s), 7.51-7.75 (4H, m), 8.16 (1H, d, J = 8.5Hz) > 8.82 and 9.24 (1H, br sx 2) MASS: 626 (M + H) + This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm)- 126 · 474811 A7 B7 V. Description of the invention (M) 133 cases of Y physical data-N ^ r16

34-10 ^ N mp: > 250 ° C Amine IR (Nujol): 3450, 3200 (br), 2500-2700, 1660, 1590, 1500 cm'1 NMR (DMSO-dg, δ): 1,34 (9H, s), 4.53 (2H, s), 5.89 (2H, s >, 7.26 (1H, dd, J = 2.4, 9.1Hz), 7.35 (1H, d, J = 8.9Hz), 7.42 (1H, br s), 7.46 (1H, s), 7.50 (1H, s), 7.64 (2H, s), 7.64-7.71 (2H, m), 7.84 (1H, d, J = 9.1Hz) MASS: 529 (M + H) +, 504 34-11 N mp: 180-190 ° C (dec.) Methylamino IR (Nujol): 3300, 2500-2700, 1650, 1600, 1500 cm-1 NMR (DMS〇-d6, δ): 2.68 (3H, d, printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) J = 4.7Hz), 4.58 (2H, s)., 5.93 (2H, s), 7.31 (1H, dd, J = 2.4, 9.1Hz), 7.30-7.35 (1H, m), 7.47 (1H, s), 7.51 (1H, s), 7.65 (1H, s), 7.68 (1H , m), 7.69 (1H, br s), 7.90 (1H, d, J = 9.1Hz), 8.05-8.15 (1H, m) MASS: 543 (M + H) + Elemental analysis C27H26N8〇3S.l / 2H2 〇: Calculated value: C 58.79, H 4.93, N 20.31 Real side value: C 58.73, H 5.08, N 19.36 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -127- 474811 V. Invention Ming (14 Printing Example of Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economics-N < r16 Y Physical Data 34-12 N mp: 152-164 ° C (dec.) — Dimethylamine IR (Nujol) • 3300, 2500- 2700, 1630, 1600, 1500 cm-1 NMR (DMS0-d6, δ): 1.34 (9H, s), 2.87 (3H, s), 3.06 (3H, s), 4.93 (2H, s), 5.93 (2H, s), 7.26 (1H, dd, J = 2.3, 9.1Hz), 7.36 (1H, d, J = 8.5Hz), 7.47 (1H, s), 7.51 (1H, s), 7.60- 7.70 ( 3H, m), 7.87 (1H, d, J = 9.1Hz) MASS: 557 (M + H) + 34-13 4 -thiomorinyl N IR (Nujol): 3300, 1620, '2500-2700, 1500 cm_l NMR (DMSO- d6, δ): 1.34 (9H, s), 2.5-2 .80 (4H, m), 2.70-2.80 (4H, m), 4.96 (2H, s), 5.93 (2H, s) / 7.27 (1H, dd, J = 2.3, 9.1Hz), 7 .36 (1H, dd, J = 1.9, 8.6Hz), 7 .47 (1H, s), 7.51 (1H, s), 7.60- 7.70 (3H, s), 7.88 (1H, d, J = 9.1Hz) MASS: 615, 616 -128- (Continued on page 128) (Please read the precautions on the back before filling this page) Applicable to China National Standard (CNS) A4 specification (210X 297 mm) 474811 A7 B7 V. Description of the invention ('such as) ΆΑ5. Add mesylmethane (0.13ml) at -40 ° C, add 3 -hydroxy-2, 2-dimethylpropanoate to 20 minutes A gas mixture of methane (0.13 g) and triethylamine (0.28 ml). After 1 hour, warm to room temperature, concentrate under reduced pressure, separate the layers with aqueous sodium hydrogen sulfonate and ethyl acetate, wash the ethyl acetate layer with brine, dry over magnesium sulfate, and distill under reduced pressure to give the corresponding mesylate (0. 21g). Mixed 1- {[2- (4-Third-Butyl Blazol-2-yl) Benzylfuran-5-yl] methyl} -5-hydroxyindolin-3 -carbonitrile (0.35 g) N, N-dimethylformamide (5 si 1) of the mesylate (0.21 g) and potassium sulfonate (0.23 g), stirred at 100 ° C for 2 0 hours. After cooling, pour into water, acidify with dilute hydrochloric acid, collect the precipitate by filtration, wash with water, and separate by silica gel column chromatography, ethyl acetate and toluene mixed solution, collect the target, and concentrate under reduced pressure to give 1- {[2- (4-第Tributyltriazol-2-yl) benzofluoran-5-yl] methyl} -5- (2-methylamino-2-methylpropoxy) B? L Udo-3 -carbonitrile (0.18 g). IR (Nujol): 2200, 1725 cm-1 NMR (CDCI3 / δ): 1.34 (6Η, s), 1.40 (9H, s), 3.70 (3H, s), 4.02 (2H, s), 5.39 ( 2H, s), 6.91 (1H, d, J = 9.0Hz), 6.99 (1H, s), 7.10 (1H, d, J = 8.5Hz), 7.18-7.26 (3H, m), 7.37 (1H, s ), 7.51 (1H, d, J = 8.5Hz >, 7.59 (1H, s > Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) MASS: 542 (M + H ) + —— An example 36 Add trifluoroacetic acid (10 m 1) to 4 -third butyl-2-{5-[(3 -amino-5 -benzyloxin-1 -yl) methyl Phenyl] benzofuran-2-yl} carbazole (0.54g), m-cresol (0.28ml), thiomethoxybenzene (0.28ml) and ethylenedi] 28-A (continued from page * 128) This paper The scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 474811 A7 B7 _ V. Description of the invention (W) Thiol (0.5 6 in 1) mixed solution. Stir for 4 hours and pour into water (1 0 0 m 1), neutralize with sodium hydrogen sulfonate, extract with ethyl acetate, wash the organic layer with water and brine in sequence, dry with magnesium sulfate, concentrate under reduced pressure, and use silica gel column chromatography to dissolve the mixed solution of toluene and ethyl acetate. Collect The target substance was concentrated under reduced pressure to obtain 4-tert-butyl-2- {5-[(3-cyano-5-hydroxyindin-phenyl) methyl] benzopyranfuran-2-yl} carbazole (3 0 5 mg) 0 IR (Nujol): 3350-2800, 2200 cm-1 NMR (DMS〇-d6, δ): 1.35 (9H, s), 5.54 (2H, s), 6.78 (1H, dd, J = 2.2, 8.9Hz), 6.92 (1H, d, J = 2.2Hz), 7.36 (1H, dd, J = l.8, 8.5Hz), 7.47 (1H, s), 7.48 (1H, d, J = 8.5 Hz), 7.50 (1H, s), 7.65 (1H, s), 7.66 (1H, d, J = 8.9Hz), 8.37 (1H, s), 9.32 (1H, br s) MASS: 428 (M + H ) + Example 37 Mixed 4-tert-butyl-2- {5-[(3-cyano-5-hydroxyindole-l-yl) methyl] benzofluoran-2-yl} ifazole (158mg) , N, N-dimethylformamide (1.5ml) solution of methyl iodide (0.1ml) and sodium sulfonate (1.5g), stirred at room temperature for 3 days, diluted with brine, extracted with ethyl acetate, and salt The organic layer was washed with water, dried with sulfuric acid IM, and decompressed to obtain 4-tributyl-2- {5-[(3- ) Cyano-5 -methylaminoindiodo-1 -yl) methyl] benzopyranfuran-2-yl} thiazole. IR (Neat): 2230, 1620, 1530, 1490, 1460, 1380, 1230 cm_l NMR (CDC13, δ): 1.40 (9Η, s), 3.87 (3H, s), 5.39 '(2H, s), 6.93 ( 1H, dd, J = 2.4, 9.0Hz), 6.99 (1H, s), 7.12 (1H, dd, J = 1.9, 8.5Hz), 7.19 (1H, d, J = 2.4Hz), 7.25 (1H, d , J = 9.0Hz), 7.26 (1H, br s), 7.39 (1H, d, J = 1.9Hz), 7.51 (1H, d, J = 8.5Hz), 7.59 (1H, s) MASS: 441 (M + ), 270, 255 -129- This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 474811 A7 B7 V. Description of the invention (> 〇 例 · Ί8 Example 37 gives the following compound. 卜 { [2-(4 -Third-butyl _ _-2 -yl) phenyl hydrazone-5 -yl] formyl

Group) -5 -methylaminoindino-3 -carbonitrile mp: 100-102 ° C IR (Nujol): 2210, 1500 cm-1 NMR (DMSO-dg, δ): 1.35 (9H, s), 3.85 (3H, s), 5.89 (2H, s), 7.20-7.26 (2H, m), 7.38 (1H, dd, J = l.9, 8.6Hz), 7.48 (1H, s), 7.52 (1H, s), 7.67 (1H, s, J = 8.6Hz), 7.70 (1H, s), 7.95 (1H, d, J = 9.5Hz) MASS: 443 (M + H) + Example 39 Mixing [2- (4 -Third-butyl carbazol-2-yl) benzofuran-5 -yl] methyl) -5- (carboxymethoxy) B-H-D-3-yl) -1H-tetrazole (60 mg) And 1,1'-carbonyldioxazole (60 mg) in digas methane (2 ml) and stirred at room temperature for 5 hours, followed by the sequential addition of dimethylamine hydrochloride (16.5 mg) and triethylamine (0.5 ml). Stir for 18 hours. It was concentrated under reduced pressure, acidified with dilute hydrochloric acid, extracted with ethyl acetate, washed with brine, dried over sulfuric acid, concentrated under reduced pressure, and subjected to silica gel column chromatography, and the mixed solution of chloroform, ethyl acetate and methanol was dissolved. Collect the object, printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). The reduction is 5-{1-{[2-(4 -Third butyl carbazole-2 -Yl) phenylbenzofuran-5-yl] methyl) -5- (N, N -dimethylamine formamidinemethyl) indil-3 -yl} -1Η-tetrazole (30. lmg) . -13 0- This paper size applies Chinese National Standard (CNS) A4 (210X 297 mm) 474811 A7 B7 V. Description of Invention (W) mp: 258 ° C (dec.) IR (Nujol): 3100, 2700- 2500, 1630, 1620, 1500, 1490, 1390, 1345, 1320, 1300, 1260, 1240, 1210 cm-1 NMR (DMS0-d6, δ): 1.34 (9H, s), 2.86 (3H, s), 3.05 (3H, s), 4.82 (2H, s), 5.64 (2H, s), 6.96 (1H, dd, J = 2.6, 9.0Hz), 7.36 (1H, d, J = 8.5Hz), 7.47 (1H, s), 7.51 (1H, s), 7.59 (1H, d, J = 9.0Hz), 7.6Ί-7.70 (3H, m), 8.20 (1H, s) 3 examples

5 6 (Please read the notes on the back before filling out this page) The paper size printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 474811 A7 B7 V. Description of the invention (W) M -N < ^ 6 Physical data 40-1 Amine mp: 181-186 ° C (dec.) IR (Nujol): 3500, 3300, 1670, 1630, 1600, 1510, 1260, 1220 cm_l NMR ( DMSO-dg, δ): 1.34 (9H, s), 1.41 (6H, s), 5.64 (2H, s), 6.97 (1H, dd, J = 2.3, 8.9Hz), 7.30 (1H, br s), 7.38 (1H, dd, J = 1.7, 8.5Hz), 7.47 (1H, s), 7.52 (1H, s), 7.56 (1H, br s), 7.61 (1H, d, J = 8.9Hz), 7.68 (1H, s), 7.70 (1H, d, 'J = 8.5Hz), 7.84 (1H, d, J = 2.3Hz), 8.19 (1H, s) MASS: 556 (M + H) +, 309 ( Please read the notes on the back before filling out this page.) Amine 2 I ο 4 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs mp: 227 C (dec.) IR (Nujol): 3400, 2500-2700, 1640, 1630, 1610, 1550, 1480, 1460, 1410, 1380 cm-1 NMR (DMSO-dg, δ): 1.35 (9H, s), 1.39 (6H, s), 2.69 (3H, d, J = 4.8Hz) , 5.42 (2H, s), 6.94 (1H, dd, J = 2.3, 8.9Hz), 7.39 (1H, dd, J = 1.7, 8.5Hz), 7.48 (1H, s), 7.52 (1H, s), 7.61 (1H, d, J = 8.9Hz), 7.68 (1H, s), 7.70 (1H, d, J = 8.5 Hz), 7.84 (1H, d, J = 2.3Hz), 8.13 (1H, d, J = 4.8Hz), 8.20 (1H, s) MASS: 570 (M + H) +, 309 —132— Paper size Applicable to China National Standard (CNS) A4 specification (210X 297mm) 474811 A7 B7 V. Description of the invention (…) I? 丄 0 Physical data 40-3 Dimethylamine IR (Nujol): 3300, 2500-2700, 1630 , 1600, 1150, 1120 cm-1 NMR (CDC13, δ): 1.39 (9H, s), 1.61 (6H, s), 3.06 (3H, s), 3.06 (3H, s), 5.27 (2H, s) , 6.82 (1H, dd, J = 2.3, 8.9Hz), 6.97 (1H, s), 7.07 (1H, dd, J = 1.7, 0.7Hz), 7.14 (1H, d, J = 8.7Hz), 7.18 ( 1H, d, J = 8.9Hz), 7.27-7.36 (2H, m), 7.80 (1H, d, J = 2.3Hz), 7.96 (1H, s) MASS: 584 (M + H) + mixed 5- { l- {[2- (4- (trimethyltriazol-2-yl) phenylhydrazine-5-yl] methyl} -5- (carboxymethylamino) indiodol-3-yl} -1H -Tetrazolium (12.2.4 mg), 2-Tosylsulfazone (43.7 mg), 1-Ethyl-3-(3 _-2 printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please Read the notes on the back before filling out this Page) Methylaminopropyl) sulfodiimide hydrochloride (61.4mg) and dimethylaminopyridine (50.Omg) of N, N-dimethylformamidine (1.5ml) at room temperature Stir for 3 days, pour into water, acidify with dilute hydrochloric acid, collect the precipitate by filtration, wash with water, dissolve in NaOH water, acidify with dilute hydrochloric acid, filter the precipitate with filtration, and wash with water to obtain [2- (4-tert-butyltriazole-2-yl ) Benzylfuran-5-yl] methyl} -5- [N- (2-Tosylsulfonyl) aminomethanemethoxy] indodol-3 -yl}-1 H -tetrazole (1 3 5.7 mg) 〇-1 3 3-This paper size is applicable to Chinese National Standard (CNS) A4 (210X 297 mm) 474811 A7 B7 V. Description of the invention (· ") mp: 156-166. . IR (Nujol): 3500-3000, 2500-2700, 1730, 1630, 1605, 1480, 1460, 1380, 1350, 1200, 1160, 1130 cm-1 NMR (DMSO-dg, δ): 1.34 (9Η, s) , 2.57 (3Η, s), 4.74 (2H, s), 5.64 (2H, s), 6.89 (1H, dd, J = 9.0, 2.4Hz), 7.27-7.34 (3H, m), 7.46-7.70 (8H , m >, 7.95 (L [l, d, J = 6.8Hz), 8.20 (1H, s) MASS: 682 (M + H) +, 270 Example 42 mixed 4-tert-butyl-2- [5- (Gas methyl) benzofuran-2-yl] pyrazole (0.36 g), indole-3 -carboxylic acid benzyl ester (0.3 Q g), and potassium arsenate (0.33 g) The methyl ethyl ketone (2flml) solution was stirred and refluxed for 7 hours. Cool to room temperature, filter the mixture, and concentrate the filtrate under reduced pressure. The slurry was subjected to silica gel column chromatography, and the mixture of n-hexane and ethyl acetate was separated. The target substance was collected and concentrated under reduced pressure to give 1 -[[2- (4-Third-butylcarbazol-2-yl) phenylsulfan-5-yl] methyl} -1H-N 丨 azole-3 -carboxylic acid benzyl ester (0.40 g) and 2 -{[2- (4 -Third-butyl-Petazol-2-yl) phenylarfuran-5 -yl] methyl}-2 pyrene-indazole-3 -carboxylic acid pyrester (0.1 2 g ). 1- {[2- (4 -Third-Butyl Blazol-2-yl) benzopyranfuran-5-yl] methyl}-1 hydrazone-benzazole-3-benzyl carboxylate IR ( Neat): 1710, 1610, 1585, 1500, 1475 cm-1 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (Please read the precautions on the back before filling this page) NMR (CDC13, δ): 1.40 (9Η, s ), 5.34 (2H, s), 5.80 (2H, s), 6.96 (1H, s), 7.20-7.56 (12H, m), 8.18 (1H, d, J = 8.0Hz) MASS: 522 (M + H ) + 2- {[2- (4-Third-Butyl Blazol-2-yl) Benzylfuran-5-yl] methyl} -2H-H 丨 azole-3-carboxylic acid benzyl-1 3 4 -This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) 474811 A7 B7 V. Description of the invention ("^" IR (Neat): 1700, 1585, 1500, 1475 cm-1 NMR (CDC13, δ) : 1.40 (9H, s), 5.45 (2H, s), 6.20 (2H, s), 6.9.6 (1H, s), 7.21-7.46 (10H, m), 7.59 (1H, s), 7.83 (1H , d, J-8.5HZ), 7.98 (1H, d, J = 8.1Hz) MASS: 522 (M + H) + Example 43 The following compound was obtained as in Example 42. 1) 5-Benzylamino-l- {[2- (4-Third-Butyl Blazol-2-yl) Benzylfuran-5-yl] methyl) -1H-H3 Isopropyl ester IR (Neat): 1700, 1490 cm-1 NMR (CDC13, δ): 1.40 (9Η, s), 1.47 (2Η, d, J = 6.3Hz), 5.13 (2H, s), 5.42 (1H , hept, J = 6.3Hz), 5.76 (2H, s), 6.97 (1H, s), 7.08 (1H, dd, J = 2.4, 8.9Hz), 7.18-7.48 (10H, m), 7.66 (1H, d, J = 2.0Hz) MASS: 580 (M + H) + 2) 1_ {〔2- (4 -Third-Butyltriazol-2-yl) phenylarfuran-5-yl] methyl) -5 -Isopropylazole-3-carboxylic acid methyl ester

mp: 126.2-127.4 ° C IR (Nujol): 1710 cm-1 NMR (CDCI3, δ): 1.30 (6H, d, J = 6.9Hz), 1.39 (7H, s), Staff Consumer Cooperative of Central Bureau of Standards, Ministry of Economic Affairs Printed (Please read the notes on the back before filling this page) 3.06 (1H, hept, J = 6.9Hz), 4.06 (3H, s), 5.77 (2H, s), 6.97 (1H, s), 7.21- 7.29 (4H, m), 7.46 (1H, d, J = 8.4Hz), 7.49 (1H, s), 8.07 (1H, s) MASS: 488 (M + H) + mixed 1- ((2- (4 -Third butyl Pfazol-2-yl) benzofuran-5-yl] -135- This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) 474811 A7 _ ^ _ B7_ V. Description of the invention (^) Methyl) -1H-B benzazole-3-carboxylic acid benzyl ester (0.35g), sodium methoxide (0-lg) and formamidine (4ml) in tetrahydrofuran (2ml) were stirred at 100 ° C for 2 hours. Cool to room temperature, concentrate under reduced pressure, add water, collect the precipitate by filtration, and wash with n-hexane and isopropyl ether to obtain 1-([2- (4-tert-butyltriazol-2-yl) benzofuran-5-yl ] Methyl}-1 fluorene-indazole-3 -carboxamide (0.22 g). IR (Nujol): 3450, 3250, 3150, 3100, 1670, 1600, 1500, 1495 cm-1 NMR (DMS0 -d6, δ): 1.34 (9Η, s), 5.85 (2H, s), 7.20- 7.50 (6H, m), 7.63-7.75 (3H, m), 7.83 (1H, d, J = 8.5Hz), 8.10 (1H, d, J = 8.1Hz) MASS: 431 (M + H) + The same compound as in Example 4 4 was obtained. 1) 5-benzylamino-1- ([2- (4-tert-butylbenzene) Azol-2-yl) benzofuran-5 -yl] methyl}-1 fluorene -indazol-3 -carboxamide

mp: 152-155eC IR (Nujol): 3450, 3150, 1670, 1590, 1480 cm-1 NMR (DMS0-d6, δ): 1.34 (9H, s), 5.14 (2H, s), 5.81 (2H, s ), 7.18 (1H, dd, J = 2.3, 9.1Hz), 7.30-7.50 (10H, m), 7.60-7.70 (3H, m), 7.75 (1H, d, J = 9.1Hz) MASS: 537 (H + H) + Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs (please read the precautions on the back before filling out this page) 2) l- {〔2- (4 -Third butyl acezol-2-yl ) Benzylfuran-5-yl] methyl}-5 -isopropyl-1 Η-丨 azole-3 -carboxamide

mp: 123.3-130.0 ° C IR (Nujol): 3500-2500, 1670 cm-1 NMR (DMS〇-d6, δ): 1.24 (6H, d, J = 6.9Hz), 1.34 (9H, s), 3.03 (1H, hept, J = 6.9Hz), 5.81 (2H, s), 7.33-7.39 (3H, m), 7.47 (1H, s), 7.50 (1H, s), 7.63-7-76 (4H, m ), 8.01 (1H, s) MASS: 473 (M + H) + This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 474811 A7 B7 V. Description of invention (K) 3) 2- {〔 2- (4-Third-butylcarbazol-2-yl) phenylsulfan-5-yl] methyl}-2 fluorene-PWazole-3 -carboxamidine

Nip: 201-202eC IR (Nujol): 3450, 3100, 1680, 1605, 1500, 1460, 1380, 1350 cm-1 NMR (DMSO-dg, δ): 1.33 (9H, s), 6.07 (2H, s ), 7.18- 7.40 (3H, m), 7.47 (1H, s), 7.51 (1H, s), 7.63-7.77 (3H, m), 7.86 (1H, d, J = 9.0Hz), 8.00 (2H, br s) MASS: 431 (M + H) + eg. 4 6 5-Isooxy-1- {[2- (4 -Third-Butyl Blind-2-yl) Phenylfuran- 5-yl] methyl} -1H-B3Iazole-3-carboxamidine (0.122 g) was added to a 1M solution of boron tribromide in digas methane (0.57 ml) and stirred at room temperature for 1.5 hours. Concentrated under reduced pressure, layered with sodium carbonate water and ethyl acetate, separated the organic layer, dried over magnesium sulfate, and decompressed to give 1- {[2- (4-tert-butyltriazol-2-yl) phenylbenzofuran- 5-yl] methyl) -5-hydroxy-1H-B3azol-3-carboxamide (0.08 g).

mp: 221-223 ° C IR (Nujol): 3300, 3150, 1655, 1610, 1600 cm ^ NMR (DHSO-dg, δ): 1.34 (9H, s), 5.76 (2H, s), 6.95 Central Ministry of Economic Affairs Printed by the Consumer Bureau of Standards Bureau (please read the notes on the back before filling this page) (1H, dd, J = 2.3, 9.2Hz), 7.29 (1H, br s), 7.34 (1H, dd, 8.6Hz) , 7.47 (1H, s), 7.51 (1H, s), 7.49 (1H, d, J = 2.3Hz), 7.60-7.68 (4H, m), 9.40 (1H, s) MASS: 447 (M + H) + Example 47 The following compound was obtained as in Example 17. -1 3 7-This paper size applies Chinese National Standard (CNS) A4 (210X 297 mm) 474811 A7 B7 V. Description of the invention (M) 1) 2-methyl- l- {[2- (4-第TributylBtazole-2-yl) phenylbenzofuran-5 -yl] methyl} indodol-3 -yl) -3-carboxylic acid ethyl ester IR (Nujol): 1690, 1545, 1500 cm-1 NMR (CDC13, δ): 1.39 (9Η, s), 1.47 (3Η, t, J = 7.1Hz), 2.76 (3H, s), 4.43 (2H, q, J = 7.1Hz), 5.45 (2H, s) , 6.96 (1H, s), 7.00 (1H, dd, J-2.0, G.5Hz), 7.17 7.31 (5H, m), 7.45 (1H, d, J = 8.4Hz), 8.17-8.21 (1H, m ) MASS: 472 (M +), 270 (base) 2) l- {[2- (4-Third-Butylbrazol-2-yl) phenylarfuran-5-yl] methyl) indodol-3 -Methyl carboxylate IR (Neat): 1690, 1530, 1500 cm-1 NMR (CDC13, δ): 1.40 (9Η, s), 3.91 (3H, s), 5.41 (2H, s), 6.96 (1H, s), 7.14 (1H, dd, J = 1.9, 8.5Hz), 7.20 (1H, d, J = 7.2Hz), 7.24-7.39 (5H, m), 7.48 (1H, d, J = 8.5Hz), 7.86 (1H, s), 8.18-8.24 (1H, m) MASS: 444 (M +), 367, 327, 312, 270 3) 2- {l- {[2- (4-tert-butyl azole)- 2-yl) phenylbenzofuran-5-yl] methyl} indin-3-yl) methyl 2-methylpropionate IR (N eat): 3100, 1730, 1610, 1590 cm-1 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back before filling this page) NMR (CDCI3, δ): 1.40 (9Η, s), 1.69 (6Η, s), 3.65 (3H, s), 5.37 (2H, s), 6.97 (1H, s), 7.02 (1H, s), 7.08- 7.20 (3H, m), 7.27-7.30 (2H, m), 7.36 (1H, d, J = 1.0Hz), 7.48 (1H, d, J = 8.5Hz), 7.65-7.69 (1H, m) MASS: 486 (M +), 427, 270 (base) Example 48 Example 18 gave the following compound. -1 38- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 474811 A7 B7 V. Description of the invention (^) B t

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

COOH example R1Q Physical data 48-1 Me mp: 227-229 ° C (dec.) IR (Nujol): 3110, 2600, 1650, 1535 cm-1 NMR (CDC13, δ): 1.39 (9H, s), 2.81 (3H, s), 5.47 (2H, s), 6.94 (1H, s), 7.02 (1H, dd, J = 2.0, 8.5Hz), 7.18-7.33 (5H, m), 7.46 (1H, d, J = 8.5Hz), 8.3-8.34 (1H, m) MASS: 444 (M +), 270 (base) 48-2 H mp: 230-235oC (dec.) IR (Nujol): 2600, 1695, 1665, 1540, 1500 cm'1 NMR (DMSO-dg, 5): 1.34 (9H, s), 5.62 (2H, s), 7.18-7.22 (2H, m), 7.39 (1H, d, J = 10.0Hz), 7.46 ( 1H, s), 7.50 (1H, s), 7.58-7.69 (3H, m), 8.02-8.06 (1H, m), 8.30 (1H, s), 12.08 (1H, br s) Central Standards of the Ministry of Economic Affairs Bureau employee consumer cooperative printed MASS: 430 (M +), 386, 270 (base) Example 49 The following compound was obtained as in Example 19. —139— The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 474811 5. Description of the invention (Saki) tBu A7 B7

-N 乂 S

CONH 2 Printed case R10 of Central China Bureau of Standards, Ministry of Economic Affairs, R10 Physical data 49-1 Me mp: 251-253 ° C (dec.) IR (Nujol): 3400, 3180, 1630, 1605, 1550, 1500 -1 cm x NHR (DMS0-d6, δ): 1.34 (9H, s), 2.64 (3H,-s), 5.59 (2H, s), 7.0-7.15 (4H, m), 7.36 (1H, br s ), 7.45-7.62 (4H, m), 7.64 (1H, d, J = 8.6Hz), 7.82-7.87 (1H, m) MASS: 443 (M +), 425, 270 (base) 49-2 Η mp: 144-145 ° C IR (Nujol): 3400, 3200, 1640, 1610, 1530 cnT1 NMR (DMS0-d6, δ): 1.34 (9H, s), 5.56 (2H, s), 7.08-7.21 (2H, m ), 7.32 (1H, dd, J = 1.8, 8.5Hz), 7.47 (1H, s), 7.50 (1H, d, J = 0.7H2) t 7.56-7.66 (2H, m), 7.67 (1H, d, J = 8.5Hz), 8.14-8.19 (1H, m), 8.17 (1H, s) MASS: 429 (M +), 411, 270 (base) @ L.5iL Example 2 D gives the following compound • 140 · (Please Please read the notes on the back before filling in this page) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) 474811 A7 B7 V. Description of the invention (I)

Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs R12 物理 Physical data 50-1 Η OMe mp: 214-215eC IR (Nujol): 3110, 2230, 1590, 1520 cm-1 NMR. (CDC13, δ): 1.39 ( 9H, s), 2.57 (3H, s), 5.42 (2H, s), 6.98 (1H, s), 7.00 (1H, dd, J = 2.0, 8.5Hz), 7.18-7.34 (5H, in), 7.47 (1H, d, J = 8.5Hz) 7.7-7.74 (1H, m) MASS: 425 (M +), 270 50-2 Η CH mp: 166-167 ° C IR (Nujol): 3130, 2230, 1535, 1500 cm'1 NMR (CDC13, δ): 1.40 (9H, s), 5.43 (2H, s), 6.99 (1H, S), 7.13 (1H, dd, J = 1.8, 8.5Hz) 7.27 (1H, s) r 7.25-7.42 (4H, ra), 7.51 (1H, d, J = 8.5Hz), 7.64 (1H, s), 7.75-7.81 (1H, m) MASS: 411 (M +), 367, 327, 312, 270 50-3 Η N IR (Nujol): 2230, 1500 cm " '' NMR (CDCI3, δ): 1.40 (9H, s) f 5.74 (2H, s), 6.98 (1H, s), 7.20 -7.51 (7H, m), 7.85 (1H, df J = 8.0Hz) MASS: 413 (M + H) + -141- (Please read the precautions on the back before filling this page) This paper size applies to Chinese national standards (CNS) A4 specifications (2 丨 0X297 PCT) 474811 A7 B7 V. invention is described in (...) _ Physical Data Example R12 γ_

50-4 OH N mp: 249-250 " C (Please read the notes on the back before filling this page) IR (Nujol): 3100 (br), 2210, 1570, 1480 cm_l NMR (DMSO-dg, δ): 1.35 (9H, s), 5.85 (2H, s), 7.01 (1H, d, J = 1.9Hz), 7.12 (1H, dd, J = 2.2, 9.1Hz), 7.38 (1H, dd, J = l. 9, 8.5Hz), 7.47 (1H, s), 7.51 (1H, s), 7.68 (1H, d, J = 8.5Hz), 7.70 (1H, d, J = 2.2Hz), 7.86 (1H, d, J = 9.1Hz), 9.90 (1H, S) HASS: 429 (M + H) +

50-5 iPr N mp: 164.5-165.5 ° C IR (Nujol): 2225 cm-1 NMR (DMS0-d6, δ): 1.26 (6H, d, J = 6.9Hz), 1.34 (9H, s), 3.08 (1H, hept, J = 6.9Hz), 5.91 (2H, s), 7.39 (1H, dd, J = 1.7, 8.6Hz), 7.48 (1H, s), 7.51-7.55 (2H, m), 7.65- 7.71 (3H, m), 7.97 (1H, d, J = 8.8Hz) MASS: 455 (M + H) + Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs -142- This paper size applies to Chinese National Standards (CNS) A4 specifications (21 OX 297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 474811 A7 _B7__ V. Description of the invention (⑷) Example 51 Mixed 4 -Third-butyl-2- {5-[(3-Cyano -5-hydroxyindolin-1-yl) methyl] benzofuran-2-yl] pyrazole (250 mg), 2 N-N a N Ο (0.67 7 m 1) and isopropyl Bromide (0.226ml) in isopropanol (5ml) was stirred at 70-8 (TC for 1 day. Cooled to room temperature, poured into dilute hydrochloric acid (1Dml), filtered and precipitated, and subjected to silica gel column chromatography, toluene and ethyl acetate The ester mixed solution was separated. The target substance was collected and concentrated under reduced pressure to give 4-tert-butyl-2-{5-[(3- 3-methyl-5 -isopropoxyindiodo-1 -yl) methyl] benzene. Furan-2-yl] B harmazole (18 0mg). UNujol): 2200, 1220 cm-1 NMR (CDC13, δ): 1.36 (6Η, d, J-β.ΟΗζ), 1.40 (9Η, s), 4.59 (1H, hept, J = 6.0Hz) , 5.38 (2H, s >, 6.90 (1H, dd, J = 2.4, 8.9Hz), 6.99 (1H, s), 7.12 (1H, dd, J = 1.8, 8.5Hz), 7.20 (1H, d, J = 2.4Hz), 7.24 (1H, d, J = 8.9Hz) 7.39 (1H, s), 7.51 (1H, d, J = 8.5Hz), 7.58 (1H, s) MASS: 470 (M + H) + Μ B2 The compound of the following formula 51 was obtained. 4 -Third-butyl-2-{5-[(3 -Cyano-5 -cyclopentyloxyindine-1 -yl) methyl] benzofuran- 2-yl] fftazole IR (Nujol): 2200, 1210 cm-1 NMR (CDCI3, δ): 1.42 (9Η, s), 1.52-1.89 (8H, m), 4.81 (1H, m), 5.38 (2H , s), 6.88 (1H, dd, J = 2.4, 8.9Ηζ), 6.90 (1H, s), 7.09-7.17 (2H, m), 7.23 (1H, d, J = 8.9Hz), 7.42 (2H, br s), 7.51 (1H, d, J = 8.5Hz), 7.57 (1H, s) MASS: 496 (M + H) + -1 4 3- This paper standard is applicable to China National Standard (CNS) A4 specification (210X297mm) ---------- Φ ------ IT ------ 0— (Please read the precautions on the back before filling this page) 474811 A7 _B7___ Five Explanation of the invention (♦) The following compound was obtained as in Example 18. 2- {1- {[2- (4 -Third-butyl azolidin-2-yl) phenylarfuran-5-yl] methyl) indodo-3 -yl}-2 -methylpropionic acid mp: 176-183 ° C (dec.) IR (Nujol): 3700, 1710, 1610, 1580, 1540 cm " 1 NMR (CDC13, δ): 1.39 (9H, s), 1.64 (6H, s), 5.26 (7H , s), 6.95 (1H, s), 6.98 (1H, s), 7.0-7.2 (3H, m), 7.21 (1H, s), 7.25-7.29 (2H, m), 7.42 (1H, d, J = 8.4Hz), 7.72 (1H, d, J = 7.6Hz) MASS: 473 (M + H) +, 427, 270 Example 54 mixed 4-third butyl-2- [5- (3-chloropropyl ) Phenylfuran-2-yl] doze (0.19g), 3-cyano-6-methyl D, B (73mg), Na0H (90mg) and a small amount of hexadecyltrimethyl ammonium vaporized in 1 ml of tetrahydrofuran was stirred at 60 ° C for 1 day. After cooling to room temperature, the insoluble matter was filtered off, and concentrated under reduced pressure to a syrup, and subjected to silica gel column chromatography (n-hexane-ethyl acetate). The fractions containing the target substance were combined and concentrated under reduced pressure to give 4-tert-butyl-2- (5- [3- (3- (3-cyano-6-methylindh-1-yl) propyl] phenylfluorene) -2-yl] ifazole 90mg. IR (Neat): 3100, 3000, 2200, 1585, 1530, 1450 cm—1 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) ) NMR (CDC13, δ): 1.41 (9Η, s), 2.18-2.35 (2Η, πι), 2.48 (3Η, s), 2.73 (2Η, t, J = 7.7Hz), 4.15 (2H, t, J = 7.1Hz), 6.95 (1H, s), 7.11 (1H, dd, J = 1.8, 8.6Hz), 7.13-7.27 (3H, m), 7.37 (1H, s), 7.48 (1H, d, J = 8.6Hz), 7.53 (1H, s), 7.56 (1H, s) HASS: 454 (M + H) + -1 4 4-This paper size applies to China National Standard (CNS) A4 (210X297 mm) 474811 A7 B7 V. Description of the invention (called) Mixed 2- (4-tert-butylcarbazol-2-yl) benzofuran-5-carbonyl gas hydrochloride (140mg), benzyl-3-carboxylic acid benzyl ester (73.3mg), triethylamine (0.089 ral) and H, N-dimethylaminopyridine (4mg) in dichloromethane (4ml). Stir at reflux for 7 hours, cool to room temperature, and use N, N-di Methylene propylene diamine (0.018ml) Diluted with methane, washed with dichloromethane solution in brine, dried over magnesium sulfate, and concentrated under reduced pressure. After silica gel column chromatography, the n-hexane and ethyl acetate mixed solution was used to dissolve the target substance, and concentrated under reduced pressure to give 1- {[2- ( 4-tert-butyltriazol-2-yl) phenylbenzofuran-5-yl] carbonyl} »§ 丨 _-3-carboxylic acid benzyl ester (121 mg) 〇IR (Nujol): 1700, 1580, 1550 cm-1 NMR (CDC13, δ): 1.43 (9H, s), 5.39 (2H, s), 7.06 (1H, s) r 7.30-7.50 (8H, m), 7.60-7.80 (2H, m), 8.05 (1H, s), 8.09 (1H, s), 8.20-8.25 (1H, m), 8.29-8.34 (1H, m) —MASS: 535 (M + H) + Example 5ft Example 55 gives the following compound e t-Bu (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs

R- -14 5 This paper size is applicable to China National Standard (CNS) A4 (210X297 mm)

R 12 474811 A7 B7 V. Description of the invention (< _) Example_R9 R12_Physical data_ 56-1 -CH2COOBzl H IR (Neat): 1730, 1680 cm-1 NMR (CDC13, δ): 1.43 (9H, s), 3.77 (2H, s), 5.15 (2H, s), 7.05 < 1H, s), 7.30-7.42 (9H, m), 7.55 7.76 (3H, m), 8.02 (1H, d, J = l.lHz), 8.38 (1H, d, J = 7.4Hz) MASS: 549 (M + H) + 56-2 -CH2COOBzl No. 2 IR (Nujol): 1725, 1678, 1515, 1335 cm_l NMR (CDCI3, δ): 1.44 (9H, s), 3.82 (2H, s), 5.17 (2H, s), 7.07 (1H, s), 7.33 (5H, s), 7.45 (1H, s), 7.56 (1H, s ), 7.69 (1H, d, " J = 9.0Hz), 7.74 (1H, dd, J = 9.0, 1.5Hz), 8.05 (1H, s), 8.29 (1H, dd, J = 9.1, 2.1Hz) , 8.48 (1H, d, J = 9.1Hz), 8.50 (1H, d, J = 2.1Hz) 1 MASS: 594 (M + H) + m · nn mx mu ml ^^^ 1 (m I-· * (Please read the notes on the back before filling out this page) 56-3 -CH2COOBzl OMe Consumer Cooperation with China Standards Bureau, Ministry of Economic Affairs Du printed IR (Neat): 1730, 1670, 1260 cm-1 NMR (CDC13, δ) : 1.43 (9H, s), 3.73 (2H, s), 3.81 < 3H, s), 5.14 (2H, S), 6.98-7.05 (3H, m), 7.25-7.43 (7H, m), 7.64 ( 1H, d, J = 8.6Hz), 7.72 (1H, dd, J = 8.6, 1.6Hz ), 8.00 (1H, d, J = 1.3Hz), 8.29 (1H, d, J = 9.8Hz) MASS: 579 (M + H) + ·

I • 146 · This paper size applies to China National Standard (CNS) A4 (210X 297mm) 474811

7 B V. Explanation of the invention (· β) Example R9 R12 Physical data 56-4 fCH2f2C00Bzl Η IR (Nujol): 1730, 1675 cm-1 NMR (CDC13, δ): 1.43 (9H, s), 2.75 ( 2H, t, J = 7.5Hz), 3.07 (2H, t, J- = 7.5Hz), 5.10 (211,; 〇, Ί. 0 5 (111, S), 7.14 (1H, s), 7.22- 7.72 (11H, m), 7.95 (1H, s), 8.36 (1H, mountain J = 7.2Hz) MASS: 563 (M + H) + 56-5 -CO-COOBzl Η IR (Nujol): 1725, 1658 cm- ** NMR (DMS0-d6, δ): 1.39 (9H, S) / 5.29 (2H, s), 7.25-7.30 (5H, m), 7.52 (2H, m), 7.58 (1H, s) , 7.65 (1H, s), 7.89 (1H, d), 7.96 (1H, d), 8.25-8.32 (3H, m), 8.57 (1H, sj MASS: 563 (M + H) + (Please read the back first Note for refilling this page) Example S7 Mixed 1- {[2- (4-Third-Butyl Blazol-2-yl) Benzenefuran-5-yl] Carboxyl} -5 -Nitroindole Beta- 3-Benzyl acetate (450mg), iron powder (450mg) A mixed solution of ethanol (7 ffi 1) and water (3 in 1) printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs, stirred and refluxed for 1 hour. Cool to room temperature , The mixture was filtered, the filtrate was concentrated under reduced pressure, and subjected to silica gel column chromatography, Benzene and ethyl acetate were mixed and separated, and the target substance was collected and decompressed to obtain 5-amino-1-{[2- (4-tert-butylcarbazol-2-yl) phenylsulfan-5-yl] carbonyl) Indolin-3-benzyl acetate (2 5 911 ^). -1 4 7-This paper size applies Chinese National Standard (CNS) A · 4 size (210X297 mm) 474811 A7 B7 V. Description of the invention (IR (Neat ): 3500-2800, 1725, 1665, 1615, 1550 cm " (Please read the notes on the back before filling this page) NMR (CDC13, δ): 1.43 (9Η, s), 3.67 (4H, s), 5.14 (2H, s), 6.76 (2H, m), 7.04 (1H, s), 7.24 (1H, s), 7.31 (5H, s), 7.39 (1H, s), 7.63 (1H, d, J = 8.6 Hz), 7.69 (1H, dd, J = 1.5, 8.6Hz), 7.98 (1H, d, J = 1.5Hz), 8.19 (1H, d, J = 9.3HZ) MASS: 564 (M + H) + Example 58 l- {[2- (4-Third-butylifazol-2-yl) benzofuran-5-yl] carboxy} indin-3-carboxylic acid benzyl ester (107 mg) in tetrahydrofuran Under reduced pressure at room temperature, 10% Pd-C (22 mg) was hydrogenated. The catalyst was filtered off, and the filtrate was concentrated under reduced pressure to obtain 1- {[2- (4- third-butyl Ufazol-2-yl) phenylarfuran-5-yl] carboxy} indin-3-carboxylate (7 4 5 mg). IR (Nujol): 1680, 1675, 1550 cm-1 NMR (DMS0-d6 / δ): 1.38 (9H, s), 5.39 (2H, s), 7.46 (2H, s), 7.56 (1H, s), 7.70 (1H, s), 7.80-8.00 (3H, m), 8.13-8.31 (3H, m) MASS: 445 (M + H) + Printed by a Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

2 This paper size is applicable to China National Standard (CNS) A4 (mm) 474811 A7

V. Description of the invention (...) R12 physical data H IR (Nujol): 1700, 1680 cm'1 NMR (CDC13, δ): 1.42 (9H, s), 3.20 (1H, br s), 3.75 (2H, s), 7.04 (1H, s), 7.26-7.80 (7H, ra), 8_02 (1H, d, J = 1.4Hz), 8.35 (1H, dd, J = 7.0, 1.4 Hz) MASS: 459 (M + H) + N02 IR (Nujol): 1670, 1590, 1470 cm-1 NMR (DMSOg, δ): 1.37 (9H, s), 3.53 (2H, S), 6.67 (1H, d), 6.69 (1H, s), 7.23 (1H, s), 7.54 (1H, s), 7.67 (1H, s), 7.73 (1H, d), 7.91 (1H, d), 7.99 (1H, d ), 8.09 (1H, s) 59-3 -CH2C00H NH2 IR (Nujol): 2800-3500, 1670 cm_i NMR (CDCI3, δ): 1.41 (9H, s), 3.58 (2H, s) / 4.78 (2H, br s), 6.74 (1H, d, J = 8.7Hz), 6.87 (1H, s), 7.02 (1H, s), 7.21 (1H, s), 7.37 (1H, s >, 7.59 (1H, d, J = 8.6Hz), 7.67 (1H, d, J = 8.6Hz), 7.93 (1H, s), 8.12 (1H, d, J = 8.7Hz MASS: 474 (M + H) + IR (Nujol) : 1690, 1670, 1265 cm-1 NMR (CDCI3, δ): 1.42 (9H, s), 3.72 (2H, S), 3.88 (3H, s), 6.98-7.04 (3H, m), 7.34 (1H, s), 7.45 (1-H, s), 7.65 (1H, d), 7.73 (1H, dd), 8.01 (1H, s), 8.38 (1H, d ) MASS: 489 (M + H) + see 59-1 R- -ch2cooh

59-2 -CH2COOH 59-4 -CH2C00H 〇Me -149- This paper size applies to China National Standard (CNS) Α · 4 size (210X 297 mm) (Please read the precautions on the back before filling this page)

, 1T 474811

A

7 B V. Description of the invention (< 4) Example R9 R12 Physical data 59-5 fCH2f2C〇〇H Η IR (Nujol): 1700, 1680 cm " 1 NMR (CDC13, δ): 1.41 (9H, s), 2.78 (2H, t, J = = 7.3Hz), 3.06 (2H, t, J = 7.3Hz), 7 .03 (HI, s) f 7.21 (1H, S), 7.35 (2H, m), 7.42 (1H , s), 7.58 (1H, dd, J = 8.4, 1.7Hz), Ί .65 (1H, s), 7.71 (1H, dd, J = 8.6, 1.5Hz), 8 • 34 (1H, d, J = 6.9Hz) MASS: 473 (M + H) + 59-6 COCOOH Η IR (Nujol): 3300, 1755, 1690 cm-1 NMR (DMSO-dg, δ): 1.38 (9H, s), 7.49- 7.53 (2H, m), 7.56 (1H, s), 7.70 (1H, s), " l, .91 (1H, mountain J = 8.6Hz), 7.99 (1H, d, J = 8.6Hz), 8.23 -8.33 (3H, m) 8.55 (1H, s) MASS: 473 (M + H) + Example 60 The following compound was obtained as in Example 17. (Please read the precautions on the back before filling out this page)

-150 This paper size applies to China National Standard (CNS) A4 specification (2 丨 0 '乂 297 mm) 474811 A7 __: _B7 V. Description of the invention (w) Printing example R2 of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economics Physics Data 60-1 Me IR (Neat): NMR (CDC13, J = 7.0Hz), J = 7.0H2 :), 8.09 (1H, MASS 535 1695 cm-1 δ): 1.39 (9H, s), 1.99 (3H , d, 5.41 (2H, s), 5.76 (1H, q, 6.96 (1H, s), 7.08-7.52 (7H, m), s), 8.19 (1H, d, J = 7.9Hz) (M + H ) + 60-2 Et IR (Nujol) NMR (CDC13, (9H, s),: 1700 cm-1 δ): 1.01 (3H, t, J = 7.2Hz), 1.42 2.39 (2H, m), 5.41 ( 2H, s), 5.45 (1H, t, J = 7.2Hz), 6.98 (1H, s), 7.14-7.53 (12H, m), 8.11 (1H, s), 8-17 (1H, dd) MASS: 549 (M + H) + 60-3 Ph IR (Neat): NMR (CDC13, 6.94 (1H, m), 7.60 1.4Hz) 17 0 0 crtT 1 δ): 1.40 (9H, s), 5.36 (2H, s), s), 6.98 (1H, s), 7.09-7.49 (17H, (1H, s), 8.20 (1H, dd, J = 8.3, MASS: 597 (M + H) +

Example 1 follows Example 58 to give the following compound. t-Bu \ -N

-151- (Please read the precautions on the back before filling out this page) This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 474811 A7 B7 V. Description of the invention ((ire? R26_physical data_ 61 ~ 1 Me IR (Nujol): 3500-2500, 1655 cm-1 NHR (DMSO-dg, δ): 1.34 (9H, s), 1.98 (3H, d, J = 6.9Hz), 6.05 (1H, q, J = 6.9Hz), 7.14-7.19 (2H, m), 7.38-7.68 (6H, m), 0.03 (1H, dd, J = 6.1, 3.0Hz), 8.34 (1H, s), 12.08 (1H, br s) MASS: 445 (M + H) + 61-2 Et IR (Nujol): 3500-2400, 1650 cm_1 NHR (DMSO-dg, δ): 0.90 (3H, t, J = 7.5Hz), 1.34 (9H , s), 2.40 (2H, quint), 5.77 (1H, t, J = 7.5Hz), 7.15-7.19 (2H, m), 7.46-7.51 (3H, m), 7.63-7.70 (2H, m), 7.79 (1H, s), 8.01 (1H, br m), 8.39 (1H, s >, 12.08 (1H, s) MASS: 459 (M + H) + 61-3 Ph IR (Nujol ): 3300-2500, 1660 cm-1 NMR (CDC13, δ): 1.40 (9H, s), 6.95 (1H, s), 6.99 (1H, s), 7.11-7.39 (11H, m), 7.53 (1H , d, J = 8.5Hz >, 7.63 (1H, s), 8.23 (1H, d, J = 8.0Hz) MASS: 507 (M + H) Example fi? Printed by the Shellfish Consumer Cooperative of the Central Sample Bureau of the Ministry of Economic Affairs (Please read the note on the back first Please fill in this page again for the matter) The following compound was obtained as in Example 15. 1) 1- {1- [2- (4-Third-Butylbrazol-2-yl) phenylarfuran-5-yl] ethyl) indrine -3 -Carbonitrile-152 This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 474811 A7 B7 V. Description of the invention (…) IR (Nujol): 2200 cm-l NMR (CDC13, δ ): 1.40 (9Η, s), 2.00 (3H, d, J = 7.0Hz), 5.80 (1H, q, J = 7.〇Hz), 6.99 (1H, s), 7.12 (1H, dd, J = 8.6, 1.9Hz), 7.19-7.34 (3H, m), 7.40 (1H, d, J = 1.6Hz), 7.50 (1H, d, J = 8.6Hz), 7.75-7.79 (2H, m) MASS: 426 (M + H) + 2) 1- {1- [2- (4-Third-butyltriazol-2-yl) phenylarfuran-5-yl] propyl} indin-3 -carbonitrile IR ( Neat): 2200 cm-1 NMR (CDC13, δ): 0.96 (3Η, t, J = 7.3Hz), 1.40 (9H, s), 2.39 (2H, quint, J = 7.3Hz), 5.46 (1H, t , J = 7.3Hz), 6.98 (1H, s), 7.14 (1H, dd, J = 8.5, 1.9Hz), 7.2 and 7.40 (4H, m), 7.45 (1H, s), 7.47 (1H, d, J = 8.5Hz), 7.76 (1H, m), 7.83 (1H, s) MASS: 440 (M + H) + 3) 7 -benzyloxy- l- {〔2- (4 -third butyl Azol-2-yl) benzylfuran-5 -yl] methyl) indodol-3 -formaldehyde IR (Nujol ): 1665, 1265 cm " 1 NMR (CDCI3, δ): 1.40 (9Η, s), 5.07 (2Η, s), 5.70 (2H, s), 6.81 (1H, d, J = 7.4Hz), 6.94 ( 1H, dd, J = 8.5, 1.8Hz), 6.97 (1H, s), 7.12-7.36 (8H, m), printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) ) 7.41 (1H, d, J = 8.5Hz), 7.66 (1H, s), 7.95 (1H, dd, J = 8.0, 0.7Hz), 10.0 (1H, s) MASS: 520 (M +), 377 , 271, 256

Example M Analogy Example 2 4 Hydrogenation method to obtain 1-{[2-(4 -Third-butyl ifazole-2 -yl) phenyl sulfan-5-yl] methyl} -5 -hydroxyindBS-3 -acetic acid (O.lg), -1 5 3-This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 474811 A7 B7 V. Description of the invention (α >) Dissolved in ethyl acetate, acetic acid with 4N hydrochloric acid Ethyl acetate treatment, filtration to collect the precipitate, washing with isopropyl ether to obtain 1- {[2- (4- tert-butylcarbazol-2-yl) phenylarfuran-5-yl] methyl) -5 -hydroxyindole Pandol-3-acetic acid hydrochloride (90 mg). mp: 145-150 ° C (dec.) IR (Nujol): 3300, 2500-2700, 1700, 1585, 1460 cm-1 NMR (DMSO-dg, δ): 1.35 (9H, s), 3.56 (2H, s), 5.39 (2H, s), 6.62 (1H, dd, J = 1.6, 8.7Hz), 6.83 (1H, d, J = 1.6Hz), 7.23-7.30 (2H, m), 7.32 (1H, s ), 7.46 (1H, s), 7.49 (1H, s >, 7.57 (1H, br 3), 7.63 (1H, d, J = 8.6Hz), β.0-7.0 (1H, br s) MASS: 461 (H + H) + Example 64 Following Example 25 gives the following compound e 1- {[2- (4-Third-Butyl Blazol-2-yl) phenylarfuran-5-yl] methyl} -5- ( 3 ·, 5 · -bis (trifluoromethyl) benzyloxy) indin-3-acetic acid methyl ester IR (Neat): 1720, 1615, 1485, 1450 cm-1 NMR (CDC13, δ): 1.40 (9Η, s), 3.70 (3Η, s), 3.75 (2Η, s), 5.20 (2H, s), 5.34 (2H, s), 6.93 (1H, dd, J = 2.4, 8.4Hz), 6.97 (1H, s ), 7.10-7.24 (4H, m), 7.36 (1H, s), 7.47 (ΙΗ / d, J = 8.4Hz), 7.84 (2H, m), 7.95 (2H, s) Central Bureau of Standards, Ministry of Economic Affairs Printed by the employee consumer cooperative (please read the precautions on the back before filling out this page) m 6 5 Add diethyl azodicarboxylate (0.095 5 m 1) to 1-{[2-(4- Tertiary butyl conazole-2 -yl) benzofuran-5 -yl] methyl -5 -Hydroxyindole-3 -acetic acid Shinko (0.114g), [1- (hydroxymethyl) cyclopropane] methyl acetate (0 · 1 0 4 g) and triphenyl o- (0 · 1 6 g ) Tetrahydrofuran (5 m 1) solution, room temperature-1 5 4-This paper size is applicable to National Standards (CNS) A · 4 specifications (210X297 mm) 474811 A7 B7 5. Description of the invention () Stir for 3 days, The solvent was removed, and silica gel column chromatography was performed, and the mixed solution of n-hexane and ethyl acetate was separated. The target substance was collected and concentrated under reduced pressure to obtain 1-[{{1-[[2-(4-tert-butyltriazol-2-yl) Phenylfuran-5-yl] methyl) -3- (methoxycarbonylmethyl) B--5-yl} oxy} methyl} cyclopropane} methyl acetate (0.07 g) 〇IR ( Neat): 1730, 1615, 1580, 1480 cm_1 MASS: 601 (M + H) + Example 66 Mix 1- {[2- (4- -Third-butylcarbazol-2-yl) benzofuran-5-yl ] Methyl) -5-(Ν 'Ν'-dimethylamine formamidinemethoxy) indodo-3-methyl acetate (0.15g) and 1N lithium hydroxide (0.52ml) in methanol (2ml) And stirred at room temperature for 8 hours. Remove the solvent, dissolve in water, acidify with dilute hydrochloric acid, collect the precipitate by filtration, and wash with water to obtain 1- {[2- (4-tert-butyltriazol-2-yl) phenylarfuran-5-yl] methyl)- 5- (Ν1, Ν′-dimethylamine formamidinemethyl) indodol-3-acetic acid (80 mg) 〇IR (Nujol): 2500-2700, 1715, 1620, 1570, 1480 cm-1 Economy Printed by the Consumer Standards Cooperative of the Ministry of Standards of the People's Republic of China (Please read the notes on the back before filling this page) NMR (CDC13, δ): 1.40 (9Η, s), 2.94 (3Η, s), 3.06 (3Η, s ), 3.76 (2Η, s), 4.69 (2Η, s), 5.28 (2Η, s), 6.86 (1H, dd, J = 2.3, 8.8Hz), 6.96 (1H, s), 7.05-7.14 (4H, m), 7.20 (1H, s), 7.30 (1H, s), 7.42 (1H, s, J = 8.5Hz) MASS: 546 (M + H) +

gL..6, L At room temperature, NaH (60% oil, 78 mg) was added with 4-(5-H-H-dooxy) ethyl butyrate (0.40g) N, N-di Methylformamide (2ral) solution, room temperature-1 5 5-This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) 474811 A7 B7__ 5. Description of the invention (, M) Stir for 30 minutes, add 4-Third-butyl-2- [5- (nitromethyl) benzofuran-2-yl] pyrazole (0.59 g), stirring continuously for 5 hours, adding ice water, acidifying with dilute hydrochloric acid, acetic acid Extracted with ethyl acetate, washed the organic layer with brine, dried over magnesium sulfate, and decompressed to obtain a slurry. After silica gel column chromatography, the n-hexane and ethyl acetate were warm-liquidly separated. The target substance was collected and decompressed to give 4-{1-{[2- Ethyl (4-tert-butyltriazol-2-yl) benzofuran-5-'yl] methyl) indin-5-yloxy) butanoate (0.2 g). IR (Neat): 3100, 1725, 1615, 1570, 1485, 1440, 1360 cm-1 NMR (CDCI3 / δ): 1.25 (3Η, t, J = 7.1 Hz), 2.12 (2Η, sext, J = 7.4 Hz), 2.53 (2H, t, J = 7.4Hz), 4.04 (2H, t, J = 7.4Hz), 4.13 (2H, q, J = 7.1Hz), 5.37 (2H, s), 6.46 (1H, s), 6.82 (1H, dd, J = 2.4, 8.9Hz), 6.96 (1H, s), 7.06-7.13 (4H, m), 7.17 (1H, d, J = 8.9Hz), 7.32 (1H, s ), 7.43 (1H, s), 7.45 (1H, d, J = 8.5Hz) MASS: 517 (M + H) + Example: Under ice cooling, add phosphorus oxyoxide (0.39g) to N, N -dimethyl Formamidine (2ml), 30 minutes later, human 4- {1- {[2- (4-tert-butyltriazol-2-yl) phenylsulfan-5-yl] methyl) indine was added dropwise 5--5-ylamino} N, N-dimethylformamide solution of ethyl butyrate (2 m 1). Stir at room temperature for 1 hour, printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Pour in sodium bisulfate water, filter the precipitate, wash, and mix with n-hexane and ethyl acetate. Dissolve, collect the target, and decompress to obtain 1-{[2- (4-Third-butylcarazol-2-yl) phenylarfuran-5-yl] methyl) -5- (ethane carbonyl) propane Group] indole-3-formaldehyde (03 2 g). -1 56- The size of this paper applies to Chinese National Standard (CNS) A4 (210X 297 mm) 474811 A7 B7 _ V. Description of the invention (cho) IR (Neat): 3100, 2950, 1720, 1650, 1615, 1575, 1525, 1500 cm_l NMR (CDC13, δ): 1.26 (3Η, t, J = 7.3Hz), 2.07-2.20 (2H, m), 2.53 (2H, t, J = 7.4Hz), 4.09 (2H, t, J = 6.3Hz), 4.17 (2H, q, J = 7.3Hz), 5.41 (2H, s), 6.91 (1H, dd, J = 2.5, 8.9Hz), 6.99 (1H, s), 7.13-7.29 ( 3H, m), 7.41 (1H, s), 7.52 (1H, d, J = 8.7Hz), 7.68 (1H, s), 7.80 (1H, d, J = 2.5Hz), 9.95 (1H, s) MASS : 545 (M + H) + Example R9 Add NaCl (19mg) to 1- {[2- (4-tert-butyltriazol-2-yl) benzylfuran-5-yl] methyl} -5 -[3- (Ethoxycarbonyl) propoxy) indohdo-3-carboxaldehyde (0.31g), water of sodium phosphate 12-hydrate (90mg) and 2-methyl-2-butane (0.27ral) in water (1.5 ml), tetrahydrofuran (2.2 ml) and a third butanol (6.5 ml) were mixed. After 2 days, sodium hydrogen sulfide water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with brine, dried over magnesium sulfate, and concentrated under reduced pressure. After silica gel column chromatography, the mixed solution of toluene and ethyl acetate was dissolved. The target was collected and decompressed to give 1- {[2- (4-tert-butylcarbazol-2-yl) phenylarfuran-5-yl] methyl) -5- [3- (ethoxycarbonyl) propane Oxy] indH-3-carboxylic acid (101 g). IR (Nujol): 2500-2700, 1735, 1655, 1610, 1575, 1525, printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) 1440 cm_l NMR (DMSO-d6, δ): 1.17 (3Η, t, J = 7Hz), 1.34 (9H, s), 1.90-2.05 (2H, m), 2.47 (2H, t, J = 7.1Hz), 3.98 (2H, t, J = 6.2Hz), 4.06 (2H, q, J = 7.1Hz), 5.56 (2H, s), 6.82 (1H, dd, J = 2.2, 9.0Hz), 7.36 (1H, d, J = 8.5Hz), 7.40 -7.50 (4H, m), 7.62 (1H, s), 7.67 (1H, d, J = 8.5Hz), 8.21 (1H, s), 12.01 (1H, s) MASS: 561 (M + H) + * 157— This paper size applies Chinese National Standard (CNS) A4 specification (210 '/; 297 mm) 474811 A7 B7 V. Description of the invention ("Mu" Example 70 Mix 1- {[2- (4 -Third butyl Blazol-2-yl) phenylbenzofuran-5-yl] methyl} -5- [3- (ethanecarbonyl) propoxy) indodol-3-carboxaldehyde (0.19g), malonic acid (73mg ), Pyridine (0.5ml) and pipe trap (0.04ml), stirred at 80 ° C for 3 hours, cooled to room temperature, poured into ice water to acidify with dilute hydrochloric acid, extracted with ethyl acetate, washed the organic layer with brine, and dried over magnesium sulfate , Concentrated under reduced pressure to obtain a slurry, and subjected to silica gel column chromatography, The mixed solution of benzene and ethyl acetate was dissolved, and the target substance was collected and decompressed to obtain (E) -3- {1- {[2- (4-tert-butyltriazol-2-yl) phenylsulfan-5-yl] Methyl} -5- [3- (ethoxycarbonyl) propoxy) indio-3-yl} acrylic acid (2 5 m 1). IR (Nujol): 3300, 2500-2500, 1720, 1670, 1600, 1520 cm-** NMR (CDC13, δ): 1.26 (3Η, t, J = 7.1Hz), 2.12-2.21 (2Η, m) , 2.55 (2H, t, J = 7.2Hz), 4.05-4.21 (4H, m), 5.38 (2H, s), 6.35 (1H, d, J = 15.9Hz), 6.89 (1H, dd, J = 2.28 , 8.9Hz), 6.98 (1H, s), 7.12 (1H, dd, J = 1.8, 8.6Hz), 7.20 (1H, d, J = 8.9Hz), 7.36-7.38 (3H, m), 7.44 (1H , s), 7.48 (1H, d, J = 8.6Hz), 7.98 (1H, d, J = 15.9Hz) MASS: 587 (M + H) + m 7 1 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (Please read the precautions on the back before filling this page) Add NaH (84mg, 60% oil) to 4-tert-butyl-2- [5- (gas methyl) phenylfuran-2-yl] Blazole (0.40 g), indole-6-carboxylic acid methyl ester (0.28 g), potassium iodide (0.22 g) in N, N-dimethylformamide (3 ml), Stir for 5 hours at room temperature, pour into ice water, extract with ethyl acetate, wash with water and brine, dry with magnesium sulfate, concentrate under reduced pressure, and use silica gel column chromatography. Toluene and ethyl-1 58- This paper applies Chinese national standards (CNS) A4 specifications (210X297 mm) 474811 A7 B7_ V. Description of the invention (< ) Ethyl acetate mixed solution dissolves, collect the target, and decompress it to give 1- [[2- (4- tertiary butyl carbazol-2-yl) phenylarfuran-5-yl] methyl) indine-6- Methyl carboxylate (0.40 g). IR (Neat): 1720, 1705, 1605, 1500 cm-1 NMR (CDC13 / δ): 1.40 (9Η, S), 3.91 (3Η, s), 5.48 (2Η, s), 6.61 (1Η, dd, J = 3.1, 0.8Hz), 6.97 (1Η, s), 7.12 (1H, dd, J = 1.8, 8.5Hz), 7.24 (1H, d, J = 0.8Hz), 7.30 (1H, d, J = 3.1Hz ), 7.35 (1H, s), 7.48 (1H, d, J = 8.5Hz), 7.67 (1H, d, J = 8.4Hz), 7.82 (1H, dd, J = 1.3, 8.4Hz), 8.13 (1H , br s) MASS: 445 (M + H) + Example 72 Example 7 1 The following compound was obtained. 5- {1- {[2- (4 -Third-butyl_azol-2-yl) phenylarfuran-5-yl] methyl) indio-6-yl) valerate ethyl IR (Neat): 3100, 1730, 1680, 1630, 1600, 1500, 1350 cm-1 NMR (CDCI3 'δ): 1.22 (3Η, t, J = 7.1Hz), 1.40 (9H, s), staff consumption of the Central Bureau of Standards, Ministry of Economic Affairs Cooperative cooperative policy (please read the precautions on the back before filling this page) 1.60-1.80 (4H, m), 2.30-2.40 (2H, m), 2.70-2.80 (2H, m), 4.09 (2H, q, J = 7.1Hz), 5.39 (2H, s), 6.52 (1H, d, J = 3.1Hz), 6.97 (1H, s), 6.95-7.00 (1H, m), 7.07-7.14 (3H, m), 7.24 (1H, d, J = 0.8Hz), 7.35 (1H, br s), 7.46 (1H, d, J = 8.5Hz), 7.56 (1H, d, J = 8.1Hz) MASS: 515 (M + H) + Example 73 The following compound was obtained by simulating Example 6δ. 1 1 5 9-This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 474811 A7 B7 V. Description of invention (4)

Printed example of employee consumer cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs__Physical Data_ 73-1 -COOMe NMR (DMS〇-dg, δ): 1.45 (9Η, s), 3.86 (3Η, s), 5.78 (2Η, s ), 7.38 (1Η, dd, J = 1.8, 8.5Hz), 7.48 (1H, s), 7.52 (1H, d, J = 0.7Hz), 7.66 (1H, s), 7.71 (1H, d, J = 8.5Hz), 7.88 (1H, dd, J = 1.4, 8.3Hz), 8.24 (1H, d, J = 8.3Hz), 8.26 (1H, br s), 8.70 (1H, s), 10.01 (1H, s ) MASS: 473 (H + H) + 73-2 -fCH2f4COOEt IR (Neat): 3100, 1725, 1655, 1530, 15 0 0 cm-1 NMR (CDC13, δ): 1.22 (3H, t, J = 7.1 Hz), 1.40 (9H, s), 1.60-1.80 (4H, m), 2.30-2.40 (2H, m), 2.70-2.80 (2H, m), 4.10 (2H, q, J = 7.1Hz), 5.34 (2H, s), 6.99 (1H, s), 7.16-7.29 (4H, m), 7.44 (1H, br s), 7.53 (1H, d, J = 8.5Hz), 7.67 (1H, s), 8.23 (1H, d, J = 8.4Hz), 9.97 (1H, s) MASS: 543 (M + H) + (Please read the precautions on the back before filling out this page), va This paper size applies Chinese national standards (CNS ) A4 specification (2 丨 0X 297 mm) —160 474811 A7 B7 V. Description of the invention (IΘ) Example 74 The following compound was obtained by following the preparation example 1.

(Please read the notes on the back before filling out this page) 74-1 -COOMe IR (Nujol) printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs: 3100, 2320, 1710, 1620, 1530, 1500, 1240 cm-1 NMR (CDC13, δ): 1.40] 9Η, s), 3.94 (3Η, s), 5.50 (2Η, s), 7.00 (1Η, s), 7.16 (1Η, dd, J = 1.7, 8.5Hz), 7.25 ( 1H, br s), 7.42 (1H, br s), 7.54 (1H, d, J = 8.5Hz), 7.74 (1H, s), 7.82 (1H, d, J = 8.4Hz), 8.00 (1H, dd , J = l.3, 8.4Hz), 8.20 (1H, s) MASS: 470 (M + H) + 74-2 -fCH2i-4COOEt IR (Neat): 3150, 2230, 1730, 1630, 1600, 1530, 1500 cm-1 NMR (CDCI3, δ): 1.22 (3H, t, J = 7.1Hz), 1.40 (9H, s), 1.60-1.80 (4H, m), 2.30- 2.40 (2H, m), 2.70- 2.80 (2H, m), 4.10 (2H, q, J = 7.1Hz), 5.41 (2H, s), 6.99 (1H, s), 7.16-7.29 (2H, m), 7.28 (1H, s), 7.40 (1H, d, J = 1.3Hz), 7.52 (1H, d, J = 8.5Hz), 7.57 (1H, s), 7.69 (1H, d, J = 8.2Hz) _MASS: 555 (M + H) + , 270__ -161- This paper size applies Chinese National Standard (CNS) A4 specification (210X'297 mm) 474811 A7 B7 V. Description of the invention () Example 75 The following compound was obtained by imitating Preparation Example 2 7. t-Bu

example

R 9 Please read the physical data first and then fill out this page. Printed on 75-1 -CH2COOH IR (Nujol) by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs.: 2700-2500, 1708, 1610, 1575 cm-1 NMR ( DMSO-dg, δ): 1.34 (9H, s), 1.94 (2H, quint ,. J = 7.0Hz), 2.39 (2H, t, J = 7.0Hz), 3.36 (2H, s), 3.94 (2H, t, J = 7.0Hz), 5.44 (2H, s), 6.75 (1H, dd, J = 2.2, 9.0Hz), 7.01 (1H, d, J = 2.2Hz), 7.26 (1H, d, J = 8.6 Hz), 7.36 (1H, d, J = 9.0Hz), 7.38 (1H, s), 7.46 (1H, s), 7.48 (1H, s), 7.56 (1H, s), 7.63 (1H, d, J = 8.6Hz), 12.16 (2H, s) MASS: 547 (M + H) + 75-2 -H IR (Nujol): 2700-2500, 1710, 1610, 1570, 1500, 1485 cm-1 NMR (DMSO- d6, δ): 1.34 (9H, s), 1.89-2.00 (2H, m), 2.38 (2H, t, J = 7.2Hz), 3.94 (2H, t, J = 6.3Hz), 5.48 (2H, s ), 6.39 (1H, d, J = 3.0Hz), 6.73 (1H, dd, J = 2.4, 8.9Hz), 7.05 (1H, d, J = 2.4Hz), 7.26 (1H, d, J = 1.6, 8.6Hz), 7.36 (1H, d, J = 8.9Hz >, 7.46-7.50 (3H, m), 7.53 (1H, s), 7.63 (1H, d, J = 8.6Hz), 12.0-12.5 (1H, br s) MASS ': 489 (M + H) + This paper size applies to China National Standard (CNS) A4 specification (210X 2 97 mm) -162- 474811 A7 B7 V. Description of the invention (~) Example _ ^ _ Physical data_ 75-3 -COOH IR (Nujol): 2500-2700, 1680, 1650, 1610, 1575, 1525 cm-1 NHR (DMSO-dg, δ): 1.3 4 (9FI, s), 1.9-2.0 (2H, m >, 2.40 (2H, t, J-7.2HZ), 3.98 (2H, t, J = 6.5Hz), 5.56 (2H, s), 6.83 (1H, dd, J = 2.4, 9.0Hz), 7.35 (1H, dd, J = l.8, 8.6Hz), 7.45-7.50 (4H, m), 7.62 (1H, s), 7.66 (1H, d, J = 8.6Hz), 8.21 (1H, s) MASS: 533 (M + H) +, 476 75-4 -CH = CH-COOH NMR (DMSO-d6, δ): 1.34 (9H, s), 1.95- (E) 1.99 (2H, m), 2.10 (2H, t, J = 7.2Hz), 4.04 (2H, t, J = 7.2Hz), 5.53 (2H, br s), 6.27 (1H, d, J = 15.8Hz), 6.86 (1H, d, J = 9.0Hz), 7.30-7.35 (2H, m), 7.45-7.50 (3H, m), 7.60-7.70 (2H , m), 7.79 (1H, d, J = 15.8Hz), 8.10 (1H, s) MASS: 559 (M + H) + Example 7fi Example 2 7 The following compounds are obtained. (Please read the precautions on the back before filling this page) 1) l- {[2- (4 -Third-Butyloxazol-2-yl) phenylarfuran-5-yl] methyl} -5- (3 ', ^ -bis (trifluoromethyl) benzyloxy] indodol-3 -acetic acid IR (Nujol): 2 700, 1690, 1615, 1490 cm-1 NMR (CDC13, δ): 1.39 (9Η, s >, 3.78 (2Η, s), 5.18 (2Η, -1 6 3-This paper size applies to Chinese National Standard (CNS)) A4 specifications (210X297 mm) 474811 A7 B7 _ V. Description of the invention (.) S), 5.34 (2H, s), 6.92 (1H, dd, J = 2.4, 8.8Hz), 7.10 (1H, dd, J = 1.8, 8.5Hz), 7.11-7.24 (5H, m), 7.34 (1H, s), 7.45 (1H, d, J = 8.5Hz), 7.82 (1H, s), 7.94 (2H, s) MASS : 687 (M + H) + 2) l- {[2- (4-Third-butyltriazol-2-yl) phenylarfuran-5-yl] methyl) -5- (3 '-(carboxyl ) Benzyloxy] indohido-3-acetic acid TR (Nujol): 3300 (br), 2700-2500, 1690, 1610, 1580, 1480 cia_l NMR (DMSO-dg, δ): 1.35 (9H, s), 3.63 (2H, s), 5.15 (2H, s), 5.45 (2H, s), 6.86 (1H, dd, J = 2.4, 8.9Hz), 7.16 (1H, d, J = 2.4Hz), 7.27 (1H , d, J = 8.5Hz), 7.38-7.73 (8H, m), 7.89 (1H, d, J = 7.7Hz), 8.04 (1H, s), 12.63 (2H, br s) 3) {1- { {{1- {[2- (4-Third-butylthazol-2-yl) phenylarfuran-5-yl] methyl) -3- (carboxymethyl) B Oxy} methyl) cyclopropane) acetic acid IR (Nujol): 3500-2500, 1700 cm-1 NMR (CDC13 / δ): 0.66 (4Η, m), 1.40 (9Η, s), 2.57 (2Η, s), 3.73 (2Η, s), 3.90 (2H, s), 5.30 (2H, s), 6.85 ( 1H, dd), 6.97 (1H, s), 6.99-7.18 (6H, in), 7.44 (1H, d) MASS: 573 (M + H) + Example 77 (Read the precautions on the back before filling this page.) Example 2 7 gives the following compound.

-164- This paper size applies to China National Standard (CNS) A4 (210X 297mm)

A7 B7 、 Explanation ()

Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economy r13 r14 COOH H IR (Nujol): 2500-2700, 1685, 1500, 1300 cm ~: NMR (DHSO-dg, δ): 1.34 (9H, s), 5.64 (2H , s), 6.61 (1H, d, J-3.0HZ), 7.26 (1H, dd, J = 1.8, 8.5Hz), 7.46 (1H, s), 7.50 (1H, d, J = 0.7Hz), 7.52 (1H, br s), 7.64 (2H, s), 7.66 (1H, d, J = 8.5Hz), 7.88 (1H, dd, J = 3.1Hz), 8.10 (1H, s), 12.55 (1H, br s) MASS: 431 (M + H) COOH H mp: 242eC (dec.) IR (Nujol): 2500-2700, 1690, 1630, 1500 cm-1 NMR (DMSO-dg, δ): 1.34 (9H, s ), 5.80 (2H, s), 7.37 (1H, dd, J = 1.9, 8.5Hz), 7.48 (1H, s), 7.52 (1H, s), 7.64 (1H, s >, 7.71 (1H, d, J = 8.4Hz >, 7.86 (1H, dd, 8.5Hz), 8.28 (1H, br s), 8.32 (1H, d, J = 8.5Hz), 8.41 (1H, s) JUT7 \ C? C · * A QQ / HjT 丄 tl \ '-fCH2) " 4COOH H IR (Nujol): 2500-2700, 1710, 1500 cnT1 NMR (CDC13 / δ): 1.40 (9H, s), 1.60-1.80 (4H, rti), 2.30-2.40 (2H, n〇, 2.70-2.80 (2H, m), 5.39 (2H, s), 6.52 (1H, d, J = 3.2Hz), 6.94 (1H, d, J = 8.5Hz >, 6.99 (1H, s), 7.06 (1H, s), 7.12 (1H, d, J = 3.2Hz), 7.15 (1H, d, J = 8.5Hz), 7.25- 7.30 (3H, n〇, 7.46 (1H, d, J = 8.5Hz), 7.55 (1H, d, J = 8.2Hz) MASS: 487 (M + H) +, 288

Tet

lb5. This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) (Please read the notes on the back before filling this page) 474811 A7 B7 V. Description of the invention (from) Example R9 R13 R14

77-4 Tet -fCH2 > 4COOH Η mp: 196-197eC IR (Nujol): 3200-3000, 2500-2700, 1700, 1630, 1610, 1500, 1400, 1260 cm-1 NMR (DMS0-d6, δ): 1.34 (9H, s), 1.44-1.70 (4H, rt〇, 2.24 (2H, t, J = 7.1Hz >), 2.65-2.75 (2H, m), 5.65 (2H, s), 7.12 (1H, d, J = 8.3Hz), 7.37 (1H, d, J = 8.5Hz), 7.47 (1H, s), 7.51 (2H, s), 7.54 (1H, s), 7.66 (1H, br s), 7.69 (1H , d, J = 8.5Hz), 8.13 (1H, d, J = 8.3Hz), 8.14 (1H, s) MASS: 555 (M + H) +

77-5 Tet H -OCH2COOH

mp: 165-168eC IR (Nujol): 3300, 2500-2700, 1720, 1620, 1580, 1500, 1460, 1380, 1200 cm-1 NMR (DMS0-d6, δ): 1.34 (9H, s), 4.87 ( 2H, s), 5.95 (2H, s), 6.82 (1H, d, J = 7.8Hz), 7.14 (1H, t, J = 7.8Hz >, 7.43 (1H, dd, J = 1.7, 8.5Hz), 7.46 (1H, s), 7.47 (1H, s), 7.64 (1H, d, J = 8.5Hz), 7.71 (1H, br s), 7.85 (1H, d, J = 7.8Hz), 8.14 (1H, s} Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) MASS: 529 (M + H) +, 309, 270 Example 7 8 The following compounds were obtained in Example 3 6. -(〔2- (4-Third-butyl-blazol-2-yl) phenylarfuran-5-yl] methyl} -7 -Hydroxyindole B-3-aldehyde-1 6 6-Applicable to this paper size China National Standard (CNS) A4 specification (210X297 mm) 474811 A7 B7 V. Description of the invention (々r) NMR (CDC13, δ): 1.41 (9Η, s), 5.75 (2H, s), 6.68 (1H, d , J = 7.6Hz), 6.99 (1H, s), 7.02-7.43 (5H, m), 7.65 (1H, s), 7.86 (1H, d, J = 7.9Hz), 9.93 (1H, s) 174 MASS : 430 (M +), 287, 272 Example 79 The following compounds were obtained by imitating Preparation Example 1 and Example 25. 1- {[2- (4 -Third-butylcarbazol-2-yl Phenylfuran-5-yl] methyl}-7-(methoxycarbonylmethoxy) indodol-3 -carbonitrile IR (Nujol): 2230, 1750, 1580, 1500, 1460, 1380, 1350 cm- ** NMR (CDC13 / δ): 1.40 (9Η, s), 3.79 (3Η, s), 4.68 (2H, s), 5.85 (2H, s), 6.64 (1H, d, J = 7.4Hz), 6.98 (1H, s), 7.12-7.20 (3H, m), 7.39-7.51 (3H, m), 7.57 (1H, s) MASS: 499 (M +), 270 cases 80 mixed 1- {(2- (4 -Third butyl benzozol-2-yl) benzofuran-5-yl] methyl} -3 -Cyanoindox-5-carboxylic acid methyl ester (1.09g), NaOH (1.5g) in water ( 15 m 1) mixed with methanol (30 m 1), stirred at reflux for 2 hours, cooled, acidified with dilute hydrochloric acid, collected by filtration, and washed with water to obtain 1-{[2-(4 -third butyl Pfazole- 2-yl) phenylbenzofuran-5-yl] methyl} -3 -Cyanoindole, printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) -5-Carboxyl acid. Tetrahydrofuran (1.4 «1) of borane-methylsulfide complex (2.0M) was added to the tetrahydrofuran (25ml) solution of the acid obtained, and the mixture was stirred at room temperature for 1 day. The organic layer was washed with water and brine, dried over barium sulfate, and subjected to silica gel column chromatography. The toluene and ethyl acetate mixed solution was separated, and the target substance was collected and decompressed to obtain 1- {[2- (4 -third butyl_ -1 6 7 -This paper size is in accordance with Chinese National Standard (CNS) A4 (210X 297 mm) 474811 A7 B7 V. Description of the invention (like) azole-2-yl) benzopyran-5-yl] methyl} -5- ( Hydroxymethyl) ind "#-3-carbonitrile (0.87 g). IR (Nujol): 3300, 2230, 1700, 1630, 1530, 1500 cm-1 NMR (CDC13, δ): 1.40 (9Η, s), 2.01 (1H, s), 4.81 (2H, s), 5.43 (2H , s), 6.99 (1H, s), 7.12 (1H, dd, J = 1.9, 8.5Hz), 7.27 (1H, s), 7.34-7.41 (3H, m), 7.51 (1H, d, J = 8.5Hz), 7.65 (1H, s), 7.78 (1H, s) HASS: 442 (M + H) + mixed 1- {[2- (4-tert-butyl azolidin-2-yl) benzofuran -5-yl] methyl) -5- (hydroxymethyl) indodol-3-triazine (0.66g) and sulfenylpyridine (0.5 18 1) in chloroform (2 Q in 1), and in the chamber Stir for 3 hours. The organic layer was washed with brine, neutralized with sodium hydrogensulfonate and extracted with chloroform. The organic layer was dried over magnesium sulfate and evaporated under reduced pressure to give 1-{[2- (4-tert-butyltriazol-2-yl) benzene. Fluorofuran-5 -yl] methyl} -5-(n-methyl) B3I Bdor-3 -carbonitrile (0.67 g). IR (Neat): 3120, 2230, 1700, 1630, 1600 cm-1 NMR (CDC13 / δ): 1.41 (9Η, s), 4.74 (2H, s), 5.43 (2H, s), 7.00 (1H, s ), 7.13 (1H, dd, J = 1.8, 8.5Hz), 7.30 (1H, d, J = 0.8Hz), 7.34-7.40 (3H, m), 7.52 (1H, d, J = 8.5Hz), 7.65 (1H, s >, 7.81 (1H, s) MASS: 460 (M + H) + Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (Please read the precautions on the back before filling out this page) # 11 8 2 Mixed 1 -([2- (4-Tertiarybutylcarbazol-2-yl) phenylarfuran-5-yl] methyl)-5-(chloromethyl > indole-3 -carbonitrile (0. 65 g) and potassium iodide (0.91 g) in acetone (5 Bi Γ) and stirred at room temperature for 1 hour. Evaporate under reduced pressure and dissolve in dichloromethane. Filter off insolubles and evaporate under reduced pressure to obtain 1- {〔2-(4-三 丁丁 -1 6 8-This paper size applies to China's National Standards (CNS) A4 specifications (210X297 mm) 474811 A7 B7 V. Description of the invention (β) Benzazol-2-yl ) Phenylfuran-5-yl] methyl) -5- (iodomethyl) indodol-3 -triazine (0.88 g). Under ice-cooling, it will be added to tetrahydrofuran (15 m 1). Methyl bromide (1M) added dropwise to diethyl malonate (5.4 1 g). Stir at room temperature for 1.5 hours and add 1-{[2-(4-tert-butyltriazole-2 -yl) benzopyranfuran-5 -yl) methyl)- 5- (iodomethyl) ind-3-carbonitrile (0.88 g). After several hours, the layers were separated in dilute hydrochloric acid and ethyl acetate. The ethyl acetate layer was washed with water and brine, and dried over magnesium sulfate. Dry and evaporate under reduced pressure. Chromatograph on a silica gel column and dissolve with toluene and ethyl acetate. Combine the fractions containing the target substance and concentrate under reduced pressure to obtain 3-{1-{[2-(4 -Third-butyl hydrazone stopper Ethazol-2-yl) phenylbenzofuran-5 -yl] methyl) -3-cyanoindole-5 -yl) -2- (ethoxycarbonyl) propanoic acid ethyl ester (0.78 g). IR (Neat): 2200, 1730, 1530, 1500, 1360 cm-1 NMR (CDC13, δ): 1.21 (6Η, t, J = 7.1Hz), 1.40 (9H, s), 3.34 (2H, d, J = 7.8Hz),. 3.69 (1H, t, J = 7.8Hz), 4.17 (1H, q, J = 7.1Hz), 5.40 (2H, s), 6.99 (1H, s), 7.12 (1H, dd, J = 1.8, 8.6Hz), 7.18-7.32 (3H, m), 7.39 (1H, d, J = 1.3Hz), 7.51 (1H, d, J = 8.5Hz), 7.61 (2H, s) MASS: 584 (M + H) +, 286 Example 83 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) Mixed 3- {1- i 〔2- (4 -Third butyl Blazol-2-yl) benzofuran-5 -yl] methyl} -3 -fluoroindolin-5-yl} -2-ethoxycarbonylpropionate ethyl ester (0.72g) and IN NaOH-containing water (5 ml) of methanol (10 ΙΒΙ) and stirred at reflux for 3 hours. After cooling, it was acidified with dilute hydrochloric acid and extracted with ethyl acetate. The ethyl acetate layer was washed with water and brine, dried under magnesium sulfate and decompressed-1 6 9-This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 474811 A7 B7 V. Description of the invention ( ) Evaporate. The residue was dissolved in xylene (1 G m 1) containing acetic acid (7.5 in 1) and stirred at reflux for 7 hours. The solvent was evaporated and the layers were separated in dilute hydrochloric acid and ethyl acetate. The ethyl acetate layer was washed with water and brine, dried over magnesium sulfate and evaporated under reduced pressure. Chromatography on a silica gel column and dissolution using a mixture of aerosol and methanol. Combining the target-containing fraction and concentrating under reduced pressure to obtain 3-[1-{[2-(4 -Third-butylthiazole-2 -yl) benzofuran-5 -yl] methyl}-3 -cyano Indine-5 -yl) propionic acid (0.78 g). IR (Nujol): 3300-3100, 2500-2700, 1630, 1605, 1500, 1250 cm-1 NMR (CDC13, δ): 1.40 (9Η, s), 2.73 (2Η, t, J = 7.6Hz), 3.08 (2H, t, J = 7.6Hz), 5.40 (2H, s), 6.99 (1H, s), 7.12 (1H, dd, J = 1.7, 8.5Hz), 7.16 (1H, dd, J = 1.5, 8.5 Hz), 7.27 (1H, s), 7.31 (1H, d, J = 8.5Hz), 7.38 (1H, d, J = 1.3Hz), 7.51 (1H, d, J = 8.5Hz), 7.61 (2H, s) MASS: 484 (M + H) + M 84 The following compound can be prepared by the method of Example 23. 1-([2-(4 -Third-butylthiazole-2 -yl) benzofuran-5 -yl] methyl)-5 -methylaminoindole II -3 -acetate consumption by employees of the Central Standards Bureau of the Ministry of Economic Affairs Cooperative printed (please read the notes on the back before filling this page) IR (Nujol): 3200-2500, 1700, 1225 cm-1 NMR (CDCI3, δ): 1.40 (9Η, s), 3.78 (2Η, s ), 3.84 (3Η, s >, 5.32 (2Η, s), 6.83 (1Η, dd, J = 8.9, 2.4Hz), 6.96 (1H, s), 7.05-7.26 (5H, m), 7.33 ( 1H, s), 7.44 (1H, d, J = 8.5Hz) MASS: 475 (M + H) + -1 7 0-This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 474811 Economy Printed by A7 B7, Consumer Cooperatives of the Ministry of Standards and Standards of the People's Republic of China 5. Description of the Invention (Cut) Example 85 Add Na Η (60% oil, 5 mg) to ice containing indolin-3 -carboxylic acid under ice cooling N, N-dimethylformamide (2 ml) of benzyl ester (0.311 g). After stirring at the same temperature for 30 minutes, 4 -third butyl-2-[5-(bromoacetamidine) was added. Phenyl) benzofuran-2-yl] Pfazole (0.47 g). After stirring the ore for 3 hours, it was poured into ice water, acidified with dilute hydrochloric acid, and extracted with ethyl acetate. The organic layer was dried with ethyl acetate. Wash with brine, dry under sulphuric acid, and concentrate under reduced pressure to obtain a slurry. Silica-column chromatography and dissociation with a mixture of toluene and ethyl acetate. Combine the part containing the target and concentrate under reduced pressure. Treat to 4 N Ethyl acetate of hydrogenated gas. The precipitate was collected by filtration and washed with diisopropyl ether to obtain the hydrochloride salt of the target substance. This hydrochloride was layered under ethyl acetate and sodium hydrogen sulfonate. The organic layer was separated by It was washed with brine, dried under magnesium sulfate, and concentrated under reduced pressure to obtain 1-{[2-(2-tert-butylPIazole-2-yl) phenylarfuran-5-yl] -2-oxoethyl} ind. Phenyl-3-benzyl 3-carboxylate (0.14 g). IR (Nujol): 1675, 1580, 1530, 1500, 1360 cm-1 Na (CDC13, δ >: 1.42 (9Η, s), 5.39 (2Η, s ), 5.60 (2Η, s), 7.05 (1Η, s), 7.20-7.50 (8H, m), 7.65 (1H, d, J = 8.7Hz), 7.87 (1H, s), 8.02 (1H, dd, J = 1.7, 8.7Hz), 8.20-8.25 (1H, m), 8.31 (1H, d, J = 1.7Hz) MASS: 549 (M + H) +, 505 cases at room temperature and atmospheric pressure will contain 1-{2-[2-(4 -Third-butylbutrazol-2 -yl) benzene cake furan-5 -yl] -2 -ethylethyl} tetrahydrofuran benzyl-3 -carboxylic acid benzyl ester (140mg) (4ml) at 10% Pd- (OH) 2 (22mg) under hydrogen-1 7 1-(Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 474811 A7 _B7___ V. Description of the invention (t7 〇 化。 0. The catalyst was filtered off and the filtrate was concentrated under reduced pressure. Silica gel column chromatography was used to dissolve the β-binding target-containing portion with a mixture of dichloromethane and methanol and concentrated under reduced pressure to obtain 1- {2- [2- (4-tert-butylthizol-2-yl ) Phenylfuran-5 -yl] -2-aminoethyl} indohdo-3 -carboxylic acid (90 mg). IR (Nujol): 2500-2700, 1700, 1650, 1530, 1360 cm-1 NMR (CDC13, δ): 1.43 (9H, s), 5.63 (2H, s), 7.05 (1H, s), 7.20-7.35 (3H, m), 7.43 (1H, s), 7.66 (1H, d, J = 8.7Hz), 7.95 (1H, s), 8.04 (1H, dd, J = 1.7, 8.7Hz), 8.26-8.30 ( 1H, m), 8.33 (1H, d, J = 1.7Hz) MASS: 459 (M + H) + Example 87 Add sodium borohydride (4mg) to the solution containing 1- {2- [2- (4-third Butyl itazole-2 -yl) benzofuran-5 -yl]-2-ethylethyl) indole-3 -carboxylic acid benzyl ester in methanol (1 ml) and tetrahydrofuran (5 ml). After stirring for several hours, it was diluted with g of acetic acid solution and extracted with ethyl acetate. The extract was washed with brine, dried over magnesium sulfate, and concentrated under reduced pressure. Chromatography on a silica gel column and dissolution with a mixture of toluene and ethyl acetate. Combining the part containing the target substance and concentrating under reduced pressure can give 1- {2- [2- (4- (Third-Butyl-2--2-yl) phenylsulfan-5-yl] -2-hydroxyethyl) Indole-3-carboxylic acid benzyl ester (70 mg). IR (Neat): 3400, 1680, 1530, 1360 cm-1 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) NMR (CDCI3, δ): 1.40 (9Η, s ), 2.51 (1Η, d, J = 2.8Hz), 4.34 (1H, d, J = 2.8Hz), 4.37 (1H, s), 5.15 (1H, br s), 5.33 (2H, s), 6.99 ( 1H, s), 7.23-7.55 (11H, m), 7.57 (1H, d, J = 1.5Hz), 8.15 (1H, s), 8.16-8.21 (1H, m) MASS: 551 (M + H) + -1 7 2-This paper size applies Chinese National Standard (CNS) A4 (210X 297 mm) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 474811 A7 B7___ V. Description of the Invention (~ ') Example 88 will contain 1- (2- [2- (4- (Third-butyltriazol-2-yl) benzofuran-5-yl] -2-hydroxyethyl) B-benzyl-3-carboxylic acid benzyl ester (70mg) and Tetrahydrofuran (7 m 1) in IN NaOH (0.13 m 1) was stirred at 50 ° C for 1 day. The solvent was removed, dissolved in water and acidified with dilute hydrochloric acid. The precipitate was collected by filtration and washed with water to obtain 1- {2- [2- (4- (3rd-butyltriazole-2-yl) phenylsulfan-5-yl] -2-hydroxyethyl} indine (50) mg). IR (Nujol): 3350, 1660, 1530, 1360, 1230 cm-1 NMR (DMS0-d6, δ): 1.37 (9H, s), 4.30-4.50 (2H, m), 5.08 (1H, br s), 5.80 (1H, br s), 7.15-7.20 (3H, m), 7.47 (1H, s), 7.49 (1H, d, J = 8.6Hz), 7.52 (1H, s), 7.58-7.70 (3H, m ), 7.78 (1H, s) MASS: 575, 461 (M + H) + Example 89 4-Third-butyl-2- [5- (bromoethylfluorenyl) phenylarfuran-2-yl] Ptazole (0 · 20 g), 3-cyanoindole (75 g) and potassium arsenate (146 mg) were dissolved in methyl ethyl ketone (3 ® 1) and stirred at 4 (TC for 2 hours. Cooling At room temperature, poured into ice water, diluted with dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with brine, dried over magnesium sulfate and concentrated under reduced pressure. Milled with diisopropyl ether to obtain 1- {2 -[2- (4-Third-butylcarbazol-2-yl) phenylarfuran-5-yl] -2-Gasethyl) indole-3 -carbonitrile (0.20 g). IR ( Nujol): 2200, 1690, 1530 cm-1 NMR (CDC13 / δ): 1.43 (9Η, s), 5.67 (2H, s), 7.06 (1H, s), 7.25-7.35 (3H, m), 7.44 ( 1H, s), 7.65 (1H, s), 7.69 (1H, d, J = 8.7Hz), 7.81 (1H, m), 8.04 (1H, dd, J = 8.7, 1.8Hz), 8.34 (1H, d , J = 1.8Hz) MASS: 440 (M + H) + -173- This paper size is applicable to China National Standard (CNS) A4 specification (21 OX 297 mm) ------------ ^^ 衣 1T (Please read the precautions on the back before (Fill in this page) 474811 Μ B7 V. Description of the invention (〇) Example 90 The method of Example 8 7 can be used to prepare the following compounds. 1- {2- [2- (4 -Third-butyltriazol-2-yl) Phenylfuran-5-yl] -2 -hydroxyethyl} indin-3 -carbonitrile IR (Nujol): 3600-3000, 2200 cm ^ NMR (CDC13, δ): 1.39 (9Η, S), 4.39 ( 2Η, mountain J = 5.8Hz), 5.14 (1H, br s), 7.00 (1H, s), 7.23-7.78 (9H, m) MASS: 442 (H + H) + Example Q1 The following compounds were prepared. 4-tertiary butyl-2- {5-[((3 -fluorenyl-2 fluorenyl-Boxazol-2-yl) methyl]

Phenylfuran-2-yl] oxazole mp: 143-144 ° C IR (Nujol): 2200, 1500, 1460, 1380, 1260 cm-1 NMR (CDC13, δ): 1.40 (9H, s), 5.84 ( 2H, s), 6.98 (1H, s), 7.30-7.46 (4H, m), 7.53 (1H, d, J = 8.5Hz), 7.70-7.80 (2H, m), 7.86 (1H, d, J = 8.0Hz) MASS: 413 (M + H) + Example 92 The method shown in Example 3 3 can be used to prepare the following compounds. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) 1) 5- {1- {[2- (4-Third-Butyl Blazol-2-yl) benzene Furan-5-yl] methyl} -5- (1-piperidinecarbonyl-1-methylethoxy) indiodol-3-yl} -1 H-tetrazole-1 7 4-Applicable on this paper China National Standard (CNS) A4 specification (210X 297 mm) 474811 A7 B7 V. Description of invention mp: 137.8 ° C (dec.) IR (Nujol): 3500-2300, 1620, 1250 cm-1 NMR (DMSO-dg , δ): 1.34 (9H, s), 1.50 (6H, br s), 1.51 (6H, s), 3.34 (2H, br s), 3.53 (2H, br s), 5.62 (2H, s), 6.83 (1H, dd, J = 2.4, 8.9Hz), 7.38 (1H, dd, J = 1.7, 8.5Hz), 7.47 (1H, s), 7.51 (1H, s), 7.59 (1H, d, J = 8.9 Hz >, 7.67 (1H, s), 7.69 (1H, d, J = 8.5Hz), 7.78 (1H, d, J = 2.3Hz), 8.16 (1H, s) MASS: 624 (M + H) + 2 ) 5- {l- {[2- (4-tert-butylcarbazol-2-yl) benzofuran-5 -yl] methyl}-5-(2-aminocarbamoyl-2-methyl Propoxy) indole-3-

) -1H-tetrazole mp: > 230 ° C IR (Nujol): 3600-2300, 1650, 1190 cm-1 NMR (DMS〇-d6, δ): 1.22 (6H, s), 1.34 (9H, s), 4.00 (2H, s), 5.64 (2H, s), 6.85-6.95 (2H, m), 7.17 (1H, br s), 7.34 (1H, d, J = 8.5Hz), 7.47 (1H, s), 7.50 (1H, s), 7.56 (1H, d, J = 8.9Hz), 7.62 (1H, s), 7.68 (1H, d, J = 8.5Hz >, 7.72 (1H, s), 8.18 (1H, s) MASS: 570 (M + H) + Example 93 The following compound can be prepared by the method of Example 21 1. 1) 5-{1-{[2-(4 -Third-butyloxazole- 2 -Base) Benzofuran-5-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (Please read the notes on the back before filling out this page) Base] Methyl) Indado-2 -Base}-1 Tetrazole IR (Nujol): 2700-2500, 1590 cm-1 NMR (CDC13, δ): 1.40 (9Η, s), 6.04 (2Η, s >, 6.86 (1Η, dd, 3 = 1.1, 8.3Hz), 6.88 (1H, s), 7.00 (1H, s), 7.07-7.27 (5H, m), 7.34 (1H, d, J = 8.3Hz), 7.58 (1H, d, J = 7.8Hz) MASS: 455 ( M + H) +, 270-1-7 5-This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 474811 A7 B7_ V. Description of the invention (~ 4) 2) 5- {1- { 3 -[2- (4 -Third-butyltriazol-2-yl) phenylarfuran-5-yl] propyl}-5 -methylindolebdo-3 -yl) -1 fluorene -tetrazole IR ( Nujol): 2700-2500, 1620, 1590, 1500, 1460 cm-1 NMR (CDC13, δ): 1.40 (9Η, s), 2.08-2.15 (2Η, m), 2.40 (3Η, s), 2.52-2.60 (2Η, m), 4.04 (2Η, t, J = 6.9Hz), 6.94 (1H, dd, 3 = 1.1, 8.6Hz), 6.96 (1H, s), 7.07 (1H, d, J = 8.6 Hz}, 7.09-7.23 (4H, m), 8.03 (1H, s), 8.09 (1H, s) MASS: 515, 498, 497 (M + H) +, 472 3) 5- {1- {1- [2- (4-Third-butylifazol-2-yl) benzofuran-5 -yl] ethyl) indionium-3 -yl}-1 fluorene -tetrazole IR (Nujol): 3100, 1620 cm -^ NMR (DMSO-dg, δ): 1.34 (9H, s), 2.00 (3H, d, J = 6.7Hz), 6.12 (1H, q), 7.22-7.69 (8H, m), 8.24 (1H , br s), 8.40 (1H, s) MASS: 469 (M + H) + 4) 5- [l- {l- [2- (4-tert-butyllItazol-2-yl) benzofuran -5-yl] propyl) indin-3-yl} -1H-tetrazole IR (Nujol): 3300, 1650 cm-1 NMR (DMS0-d6, δ): 0.96 (3H, t, J = 7.1Hz ), 2.42 (2H, quint, J = 7.1Hz), 5.87 (1H, t, J = 7.1Hz), 7.19-7.30 (2H, m), 7.43-7.50 (3H, m), 7.65-7.77 ( 3H, m), 8.21 Ministry of Economic Affairs Printed by the Consumer Standards Cooperative of the Central Bureau of Standards (please read the notes on the back before filling this page) (1H, m), 8.47 (1H, s) MASS: 483 (M + H) + 5) 5- (1- { 2- [2- (4-Third-butyltriazol-2-yl) benzofuran-5-yl] -2 -hydroxyethyl} indiodol-3 -yl) -1 hydrazone-tetrazole-1 7 6-The size of this paper applies the national standard (CNS) A4 (210 × 297 mm) 474811 A7 B7 V. Description of the invention ('%) IR (Nujol): 3600-3000 cm-1 NMR (DHSO-dg, δ ): 1.37 (9H, s), 4.47 (2H, m), 5.10 (1H, br s), 5.88 (1H, d, J = 4.3Hz), 7.25 (2H, m), 7.48 (1H, s ), 7.52 (2H, s), 7.67 (2H, m), 7.80 (1H, s), 8.12 (1H, s), 8.23 (1H, m) MASS: 485 (M + H) + 6 ) 5-{2-{[2-(4 -Third-butyl Ufazole-2 -yl) phenylsulfanylfuran-5 -yl] methyl) -2H -P 1-11 d-3-yl} -1H -Four sleep

mp: 180-190 ° C IR (Nujol): 3300, 2500-2700, 1500, 1370 cm-1 NMR (DMS〇-d6, δ): 1.34 (9H, s), 6.29 (2H, s), Ί. 25-7.48 (6H, m), 7.6-7.65 (2H, m), 7.75 (1H, d, J = 8.4Hz), 8.15 (1H, br s) MASS: 456 (M + H) +, 431, 413 Example 94 1.97 g of ethyl 2- (2-hydroxymethyl-6-methoxyphenoxy) propionate, 2- (4-tert-butylcarbazol-2-yl) -5-hydroxyphenylhydrazone 1.83 g and 2.83 g of triphenylhydrazone were dissolved in 20 ml of tetrahydrofuran, and a solution of 1.67 g of diethyl azodicarboxylate and 2 ml of tetrahydrofuran was added under ice-cooling. After stirring at the same temperature for 1 hour and room temperature for 1 hour, it was concentrated under reduced pressure and subjected to 25Gbi1 silica gel column chromatography (n-hexane: ethyl acetate = 7: 1) to obtain 2- {2- {[2- (4- Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Third Ministry of Economic Affairs (please read the precautions on the back before filling this page) Butyl B thiazol-2-yl) phenylarfuran-5-yl] oxy] methyl} 31-。 6-methylphenoxy} ethyl propionate 2. 31 g. -17 7- The size of this paper applies Chinese National Standard (CNS) A4 (210X 297 mm) 474811 A7 B7 V. Description of Invention (f%) 185 IR (Film): 1740, 1605 (sh), 1585 cm-1 NMR (CDC13, δ): 1.24 (3H, t, J = 7Hz), 1.40 (9H, s), 3.83 (3H, s), 4.16 (2H, q, J = 7Hz), 4.92 (1H, q, J = 7Hz), 5.23 (1H, d, J = 12.2Hz), 5.33 (1H, d, J = 12.2Hz), 6.84-7.45 (8H, m) Example 95 The following compound was obtained in Example 9 4. t-Bu

(Please read the notes on the back before filling this page) Example r20r21r22r23r24 Physical data 95-1 Me He H OMe Η [α] §7 = 11.85 ° (c = 0.98, CHCI3) ((S) -isomer; IR (Film): 1745, 1260 cm'1 NMR (CDCI3, δ): 1.41 (9H, s), 1.58 Printed bags (3H, s), 3.71 (3H, s), 3.84 ( 3H, s >, 4.91 (1H, q, J = 6.9Hz), 5.22 (1H, d, J = 12.2Hz), 5.32 (1H, d, J = 12.2Hz), 6.88 (1H, dd, J = 2.3 , 7.4Hz), 6.96 (1H, s), 6.97-7.27 (5H, m), 7.43 (1H, d, J = 8.9Hz) MASS: 496 (M + H) + This paper standard is applicable to Chinese National Standard (CNS ) A4 specification (210X 297 mm) -178- 474811 A7 B7 V. Description of the invention (eg r2 〇r2 lp_22j ^ 2 3j ^ 2 4 Physical data 95-2 Bzh nPr H OMe H IR (Film): 1745, 1585 cm -1 NMR (CDC13, δ): 0.85 (3H, t, J = 7Hz), 1.41 (9H, s), 1.40-1.60 (2H, m), 1.93 (2H, m), 3.60 (3H, s), 5.10 (1H, m), 5.10 (1H, d, J = 12Hz), 5.30 (1H, d, J = 12Hz), 6.80- 7.40 (18H, m)

95-3 Me Et H OMe H mp: 80-81 ° C IR (film): 1762, 1580 cm-1 NMR (CDC13, δ): 1.04 (3H, t, J = 7.2Hz), 1.41 (9H, s ), 2.0 (2H, zn >, 3.70 (3H, s), 3.82 (3H, s), 4.87 (1H, q, J = 6Hz), 5.25 (1H, d, J = 12.4Hz), 5.35 (1H, d, J = 12.4Hz)-, 6.80- 7.45 (9H, m) MASS: 510 (M + H) +

95-4 Et Me Me OMe H mp: 123eC 1 IR (film): 1732, 1585 cm 'NMR (CDC13, δ): 1.32 (3H, t, J = 7Hz), 1.41 (9H, s), 1.47 (6H , S), 3.75 (3H, s), 4.24 (2H, q, J = 7Hz), 5.13 (2H, s), 6.8-7.2 (8H, m), 7.28 (1H, s), 7.43 (1H, d Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back before filling this page) J = 9Hz) 95-5 tBu Η H OMe H IR (Film): 1750, 1240 cm-1 NMR (CDCI3 , δ): 1.41 (9H, s), 1.44 (9H, s), 3.86 (3H, s), 4.61 (2H, s), 5.30 (2H, s), 6.89 (1H, dd, J = 2.7, 7.1 Hz), 6.96 (1H, s), 6.99-7.14 (4H, m), 7.15 (1H, d, J = 2.5Hz), 7.42 (1H, d, J = 8.9Hz) MASS: 524 (M + H) + -179- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 474811 A7 B7 V. Example of invention r20r21r22r23r24_Physical data_ 95-6 Me H Me OMe Η [α] §7 = +14.06 ° (c = 0.8, CHC13) ((R) -isomer) IR (Film): 1720, 丄 32ϋ cm 1 NMR (CDCI3, δ): 1.41 (9H, s), 1.57 (3H, d, J = 7Hz) , 3.70 (3H, s), 3.84 (3H, s), 4.91 (1H, dd, J = 12.2Hz), 5.27 (2H, center of a pair of dd, J = 12.2Hz) , 6.87 (1H, dd, J = 2.2, 7 · 5Ηζ), 6.95 (1H, s), 6.99-7.25 (5H, m), 7.25 (1H, s), 7.42 (1H, d, J = 9Hz) MASS: 496 (M + H) + 95-7 Bzh nPr Η H OMe IR (CH2C12): 1750, 1730, 1610, 1585 cm_l NMR (CDCI3, δ): 0.88 (3H, t, J = 7Hz) , 1.41 (9H, s), 1.47 (2H, m), 1.96 (2H, m), 3.58 (3H, s), 4.80 (1H, t, J = 5.6Hz), 5.07 (1H, d, J = ll .7Hz), 5.20 (1H, d, J = 11.7Hz), 6.25 (1H, d, J = 2.2Hz), 6.50 (1H, dd, J = 2.2, 8.4Hz), 6.91 (1H, s), 6.95 (1H, s), 6.99 (1H, dd, J = 2.5, 9.0Hz), 7.1-7.4 (8H, m) (Please read the notes on the back before filling this page) Central Standards Bureau of the Ministry of Economic Affairs-Industrial and Consumer Cooperatives Printed under ice-cold, at 2- [2- (hydroxymethyl) benzene carbamoyl] valeric acid diphenyl methyl ester (1.70 g), 2- (4-tert-butyl Pfazole-2-yl) -5 -Hydroxybenzofuran (2.43g), and triphenylfuran (2.44g) in tetrahydrofuran (40ml) solution is added to -1-8 0-This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 474811 A7 B7 V. Description of the invention (< β) (Please read the notes on the back before filling this page) Tetrahydrogen diethyl dicarboxylate (1.44g) The furan solution (2ffll) was stirred at the same temperature and room temperature for 1 hour, and concentrated under reduced pressure for 1 hour. After silica gel column chromatography (100g), the toluene and n-hexane mixed solution was dissolved (7: 3) to obtain 2- {2- {[2- (4-Third-butylazolizol-2-yl) benzylfuran-5-ylamino] methyl} benzyl) diphenylvalerate (2.16g). IR (Film): 1750 cm-1 NMR (CDC13, δ): 0.91 (3Η, t, J = 7Hz), 1.41 (9H, s), 1.4-1.7 (4H, m), 2.0 (2H, m), 4.84 (1H, t, J = 6Hz), 5.18 (1H, d, J = 12Hz), 5.27 (1H, d, J = 12Hz), 6.65 (1H, d, J = 8Hz), 6.9-7.5 (18H, m) MASS: 646 (M + H) + Example 97 The following compound was obtained as in Example 96. t — Bu Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs -181-

This paper size applies to China National Standard (CNS) A4 (210X297 mm) 474811 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description ('Take') Example R20 R21 R22 R24 R25 97-1 Bzh nPr H -CKCH2) " 3COOEt Η IR (Nujol): 1750, 1730, 1610, 1580, 1500 cm-1 NMR (CDC13, δ): 0.89 (3H, t, J = 7.4Hz), 1.26 (3H, t, J = 7.2Hz), 1.41 (9H, s), 1.4-1.5 (2H, m), 1.90-2.05 (4H, m), 2.42 (2H, q, J = 7.4Hz), 3.65-3.85 (2H, m) , 4.11 (2H, q, J = 7.2Hz), 4.75-4.88 (1H, m), 5.14 (2H, ABq, J = 11.7Hz), 6.23 (1H, d, J = 2.2Hz) 6.48 (1H, dd , J = 2.2, 8.4Hz), 6.91 (1H, s), 6.95 (1H, s), 6.99 (1H, dd, J = 2.6, 8.9Hz), 7.13-7.41 (13H, m) MASS: 776 (M + ), 777.4 (M + H) + 97-2 Bzh nPr H -O ^ CH2 ^ 4COOEt H IR (Nujol): 1740, 1730, 1610, 1590, 1500 cm-1 NMR (CDC13, δ): 0.88 (3H, t, J = 7.4Hz), 1.26 (3H, t, J = 7.1Hz), 1.40 (9H, s), 1.40-1.50 (2H, m), 1.60-1.72 (4H, m), 1.95-2.00 (2H , m), 2.30-2.40 (2H, m), 3.60-3.85 (2H, m), 4.08-4.19 (2H, m), 4.79 (1H, t, J = 7.4Hz), 5.17 (2H, ABq, J = 11.8Hz), 6.23 (1H, d, J = 2.2H z), δ.49 (1H, dd, J = 2.2, 8.6Hz), 6.90 (1H, s), 6.95 (1H, s), 6.99 (1H, dd, J = 2.5, 8.9Hz), 7.13-7.32 (12H, m), 7.39 (IE, d, J = 8.9Hz) MASS: 790 (M + H) + (Please read the precautions on the back before filling out this page) The paper size applies to the Chinese National Standard (CNS) A4 Specifications (210X 297 mm) 182- 474811 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 __'_ B7 V. Description of the invention (β /) Example R20 R21 R22 R24 R25 97_3 Bzh nPr H -0-fCH2) -5COOEt H IR (Nujol): 1750, 1730, 1610, 1585, 1500, 1460, 1380 cm-1 NMR (CDC13, δ): 0.88 (3H, t, J = 7.4Hz), 1.26 (3H, t, J = 7.1Hz ), 1.40 (9H, s), 1.40-1.52 (2H, m), 1.58-1.68 (4H, m), 1.94-2.05 (2H, m), 2.32 (2H, t, J = 7.1Hz), 3.60- 3.80 (2H, m), 4.13 (2H, q, J = 7.1Hz), 4.80 (1H, t, J = 7.0Hz), 5.14 (2H, ABq, J = 11.7Hz), 6.25 (1H, d, J = 2.2Hz), 6.48 (1H, dd, J = 2.2, 8.5Hz), 6.90 (1H, s), 6.95 (1H, s), 6.98 (1H, dd, J = 2.6, 9.0Hz), 7.11-7.32 (13H, m), 7.38 (1H, d, J = 9.8Hz) MASS: 804 (M +) 97-4 Bzl Η H -0-fCH23-3C00Et H IR (Nujol): 1750, 1730, 1610, 1580, 1500 cm-1 NMR (C DCI3, δ): 1.26 (3H, t, J = 7.2Hz), 1.41 (9H, s), 2.08 (2H, quint, J = 6.8Hz), 3.94 (2H, t, J = 6.8Hz), 4.11 ( 2H, q, J = 7.2Hz), 4.72 (2H, s), 5.13 (2H, s), 5.23 (2H, s), 6.36 (1H, d, J = 2.2Hz), 6.53 (1H, dd, J = 2.2, 8.4Hz), 6.96 (1H, s), 7.33 (5H, s), 7.30-7.42 (2H, m) MASS: 658 (M + H) +. (Please read the precautions on the back before filling in this Page) -183- This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) 474811 A7 _: _ B7___ V. Description of the invention (· 〇) Example R20 R21 R22 R24 r25 — 97-5 Me Et H CHCH2 3CO〇Et Η IR (Nujol): 1750, 1730, 1610, 1585, 1500, 1450 cm · 1 NMR (CDC13, δ): 1.05 (3H, L, J- 7., 1.26 (3H, t, J = 7.5Hz), 1.41 (9H, s), 1.93-2.15 (4H, m), 2.50 (2H, t, J = 7.5Hz), 3.76 (3H, s), 3.97 (2H, t, J = 6.1Hz) , 4.14 (2H, q, J = 7.2Hz), 4.64 (1H, t, J = 6.0Hz), 5.13 (1H, d, J = ll.7Hz), 5.28 (1H, d, J = ll.7Hz) , 6.32 (1H, d, J = 2.2Hz), 6.50 (1H, dd, J-2.2, 8.4Hz), 6.95 (1H, s), 7.02 (1H, dd, J = 2.6, 9.0Hz), 7.18 ( 1H, d, J = 2.6Hz), 7.26 (1H, s), 7.36 (1H, d, J = 8.4Hz), 7.42 (1H, d, J = 8.4 Hz) MASS: 610 (M + H) +

97-6 Et Me Me Η H IR (Nujol): 1730, 1585 cm-1 NMR (CDCI3, δ): 1.24 (3H, t, J = 7Hz), 1.41 (9H, s), 1.62 (6H, s) , 4.24 (2H, q, J = 7Hz), 5.17 (2H, s), 6.74 (1H, d, J = 8Hz), 6.96 (1H, s), 7.0-7.5 (7H, m) MASS: 466 (M + H) +

97-7 Bzh nBu Η Η H Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) IR (Film): 1750 cm-1 NMR (CDCI3, δ): 0.82 (3H , t, J = 7Hz), 1.41 (9H, s), 1.2-1.5 (4H, m), 2.0-(2H, m), 4.84 (1H, t, J = 7Hz), 5.18 (1H, d, J = 12.6Hz), 5.28 (1H, d, J = 12.6Hz), 6.66 (1H, d, J = 8Hz), 6.9-7.6 (19H, m) MASS: 660 (M + H) + -184- this paper The scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 474811 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 ______B7 V. Description of the invention) Example R20 R21 R22 R24 R25 97-8 Et Yang 2 Thirty-three Η Η IR (Film): 1725, 1585, 1190 cm-1 NMR (CDC13, δ): 1.16 (3H, t, J = 7Hz), 1.41 (9H, s), 2.0 (2H, m), 2.35-2.55 (2H, m), 2.8 (2H, m), 4.20 (2H, q, J = 7Hz), 5.23 (2H, s), 6.41 (1H, d, J = 8Hz), 6.9-7.5 (8H, m) MASS: 506 (M + H) + 97-9 Me Et Η IR H IR (Nujol): 1750, 1600, 1584 cm-1 NMR (CDCI3, δ): 1.08 (3H, t, J = 7Hz), 1.41 (9H, s ), 2.03 (2H, dt, J = 6, 7Hz), 3.75 (3H, s), 4.69 (1H, t, J = 6Hz), 5.21 (1H, d, J = 13Hz), 5.30 (1H, d, J = 13Hz), 6.75 (1H, d, J = 8Hz), 6.96-7.8 (8H, m) MASS: 480 (M + H) + 97-10 tBu Η Η H -0 * (CH2) " 3C〇0Et mp: 82-82.5 ° C IR (Nujol): 3100, 1760, 1732 cm-1 NMR (CDCI3, δ): 1.24 (3H, d, J = 7Hz), 1.41 (9H, s), 1.48 ( 9H, s), 2.07 (2H, m), 2.49 (2H, t, J = 7Hz), 3.95 (2H, t, J = 6Hz), 4.12 (2H, q, J = 7Hz), 4.54 (2H, s ), 5.22 (2H, s), 6.7 (2H, m), 6. «(1H, s), 7.0-7.3 (4H, m), 7.42 (1H, d, J = 8Hz) 97-11 tBu Η Η H -O-CHj-COOtBu mp: 66-67 ° C IR (Nujol): 1750 cm-1 NMR (CDCI3, δ): 1.42 (9H, s), 1.46 (9H, s), 1.48 (9H, s) , 4.46 (2H, s), 4.'54 (2H, s), 5.21 (2H, s), 6.7-6.8 (2H, m), _6.83 (1H, s), 7.0-7.4 (5H, m ) _ -185- This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling out this page) 474811 A7 _B7__ 5. Description of the Invention (< Section) Example Example 96 gave the following compound. 4- {4- {[2- (4-Third-butyl-pyrazol-2-yl) benzofuran-5-ylamino] methyl} -3 -methylphenoxy} ethyl butyrate (Nujol): 1725, 1610, 1585, 1500, 1450, 1420 cm-1 NMR (CDC13, δ): 1.26 (3Η, t, J = 7.4Hz), 1.41 (9H, s), 2.07-2.18 (2H, m), 2.52 (2H, t, J = 7.4Hz), 3.84 (3H, s), 4.02 (2H, t, J = 7.2Hz), 4.15 (2H, q, J = 7.4Hz), 5.06 ( 2H, s), 6.46 (1H, dd, δ = 2 Λ, 8.0Hz), 6.50 (1H, d, J = 2.2Hz), 6.95 (1H, s), 7.02 (1H, dd, J = 2.7, 8.9 Hz), 7.14 (1H, d, J = 2.7Hz), 7.26 (1H, s), 7.33 (1H, d, J = 8.0Hz), 8.46 (1H, d, J = 8.9Hz) MASS: 524 (M + H) +

# 11 9 Q 2- {2- {[2- (4- (Third-butyltriazol-2-yl) phenylarfuran-5-yloxy] methyl} -6-methoxybenzene at room temperature Gas-based} ethyl propionate (2.30 g) in tetrahydrofuran (30 ml) and methanol (15®1), added with IN NaOH (6.8 m 1), stirred for 2 hours, concentrated under reduced pressure, diluted with water, 1 NHC 1 Acidified, extracted with ethyl acetate, washed the organic layer with brine, and dried over magnesium sulfate to give 2- {2- {[2- (4-tert-butyl Bfazol-2-yl) phenylsulfan-5-yloxy] methyl Group} -6-methoxyphenoxy} propionic acid (2.17 g) amorphous solid. Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back before filling this page) NMR TCDC13, δ): 1.40 (9Η, s), 1.59 (3H, d, J = 7Hz), 3.86 ( 3H, s), 4.88 (1H, q, J = 7Hz), 5.19 (2H, center of a pair of d, J = 12.2Hz), 6.9-7.4 (8H, m) MASS: 482 (M + H) + -186- This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 474811

A B V. Explanation of the invention (•) Example 1 00 Example 9 9 The following compounds are obtained t-Bu

? 〇 V ‘COOH R23 24

R Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Employee Consumer Cooperatives R21 R 22 r23 R 24 Physical data 100-1 Me Η 〇Me Η IR (Nujol): 3500-2500, 1720, ((S)-Lero) 12 60 cru-l NMR (CDC13, δ): 1.40 (9H, s), 1.59 (3H, d, J = 7.0Hz), 3.88 (3H, S) / 4.87 (1H, q, J = 7.0Hz), 5.17 (2H, s), 6.91-7.27 (7H, m), 7.43 (1H, d, J = 8.9Hz) MASS: 482 (M + H) + 100-2 nPr Η OMe Η mp: 111-112.5 ° C IR (Nujol): 1 * 72 8 cm-1 NMR (CDC13, δ): 0.86 (3H, t, J = 7Hz), 1 • 40 (9H, s), 1.58 (2H, m), 1.93 (2H , m), 3.84 (3H, s), 4.90 (1H, t, J = 6Hz), 5 • 20 (2H, a center of a pair of d, J = 12Hz), 6.9-7.28 (7H, m), 7.42 (1H, d, J = 9Hz) MASS: 510 (M + H) + -187. (Please read the precautions on the back before filling out this page) This paper size applies Chinese National Standard (CNS) A4 specification (210X297) (%) 474811 A7 B7 V. Description of the invention (also) Example R21 R22 R23 R24_Physical data_ 100-3 Et H OMe H mp: 117-118 ° C IR (Nujol): 171 0, 1580 cm-** NMR (CDCI3, δ): 1.04 (3H, t, J = 7.5HZ), 1.40 (9H, s), 2.00 (2H, dq, J = 5.4, 7.5Hz), 3.84 ( 3H, s), '4.87 (1H, t, J = 5.4Hz), 5.21 (2H, s), 6.90-7.03 (2H, m), 6.99 (1H, s), 7.08 (7.14 (3H, m), 7.28 (1H, s), 7.42 (1H, d, J = 9Hz) Elemental analysis: lysis Calcd. For C27H29N1〇6S: Calculation: C 64.04, H 6.01, N 2.77 Found: C 64.04, H 6.10, N 2.72 (Please read the precautions on the back before filling this page) 100-4 Me Me OMe H mp: 120-120.8 ° C NMR (CDC13, δ): 1.41 (9H, s ), 1.51 (6H, s), 3.86 (3H, s), 5.09 (2H, s), 6.9-7.0 (3H, m), 7.1-7.2 (1H, m), 7.29 (1H, d, J = lHz ), 7.45 (1H, d, J = 9Hz) MASS: 496.1 (M + H) + 100-5 Η H OMe H mp: 147.5-148 ° C IR (Film): 3200-2600, 1720, 1245 cm- · * · NMR (CDCI3, δ): 1.40 (9H, s) ", 3.90 (3H, s), 4.71 (2H, s), 5.17 (2H, S), 6.93-7.19 (18H, m), 7.27 ( 1H, s), 7.43 (1H, d, J = 9Hz) · MASS: 468 (M + H) + -188- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 474811 A7 B7 Explanation of the invention (,) Example r21 r22 r23 r 24 Physical data 100-6 H Me OMe H IR (Nujol): 3300-3000, 1720, ((R) -isomer) 1580 cm-1 NMR (CDC13, δ): 1.40 (9H, s), 1.55 (3H, d, J = 8.9Hz), 3.85 (3H, s), 4.84 (1H, q, J = 8.9Hz), 5.15 (2H, s), 6.95 (1H , s), 6.91-7.43 (6H, m), 7.42 (1H, d, J = 9Hz) MASS: 482 (M + H) + 100-7 nPr Η H OMe mp: 137.5-137.9 ° C IR (Nujol) : 1740, 1610, 1585 cm_l NMR (CDC13, δ): 0.93 (3H, t, (Please read the precautions on the back before filling out this page) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs will print: 7 Furn -5 hydrogen oxygen of tetrahydrofuran (J = 7Hz), 1.40 (9H, s), 1.54 (2H, m), 2.0 (2H, m), 3.78 (3H, s), 4.84 (1H, t, J = 6Hz), 5.03 (1H, d, J = ll.2Hz), 5.20 (1H, d, J = 11.2Hz), 5.83 (1H, br s), 6.45 (1H, d, J = 2.2Hz), 6.54 (1H, dd, J = 2.2, 8.4Hz), 6.96 (1H, s), 7.01 (1H, dd, J = 2.6, 8.9Hz), 7.18 (1H, d, J = 2.5Hz), 7.26 (1H , s), 7.34 (1H, d, J = 8.3Hz), 7.42 (1H, d, J = 8.9Hz) 骈 ο 3 Benzene · XI / 2 * | 6 (I Ding Pentamyl} 4th group 4 Γν 1 Benzene 2 C} {Methyl-methanol and mixed liquid solution paper size Applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) 474811 A7 _B7_ V. Description of the invention (, Beat) m 1), stirred for 2 hours, concentrated under reduced pressure, diluted with water, 1 NHC 1 acidified, extracted with ethyl acetate, washed the organic layer with brine, and dried with magnesium sulfate to obtain 2- {2-([2- (4- Tributyltriazol-2-yl) phenylbenzofuran-5-ylamino] methyl) phenylamino} valeric acid (901 nig).

mp: 135-136 ° C IR (Nujol): 1720 cm-1 NHR (CDC13, δ): 0.95 (3H, t, J = 7Hz), 1.40 (9H, s), 1.58 (2H, m), 2.0 ( 2H, m), 4.86 (1H, t, J = 6Hz), 5.13 (1H, d, J = 12Hz >, 5.33 (1H, d, J = 12Hz), 6.8-7.5 (9H, m) MASS: 480 ( M + H) + Example 1 02 (Please read the notes on the back before filling this page) Example 1 Q 1 The following compounds are obtained. T-Bu

Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs -19 0- This paper size applies to China National Standard (CNS) A4 (210XW7 mm) 474811

A7 B7 、 Explanation of invention (W) Example R21 R22 R24 R25 102-1 nPr H -CHCH2f3COOH H IR (Nujol): 2700, 1715, 1610, 1585, 1505, 1450 cm-1 NMR (DMSO-dg, δ): 0.86 (3H, t, J = 7.2Hz), 1.36 (9H, s), 1.4-1.5 (2H, m), 1.70-1.95 (4H, m), 2.37 (2H, t, J = 7.3Hz), 3.90-3.95 (2H, in), 4.82 (1H, d, J = 5.8Hz), 5.04 (1H, d, J = 11.7Hz), 5.13 < 1H, d, J = 11.7Hz), 6.44 (1H, d, J = 2.2Hz), 6.53 (1H, dd, J = 2.2, 8.3Hz), 7.03 (1H, dd, J = 2.2, 8.9Hz), 7.15-7.36 (3H, 7.42 (1H, s) , 7.45 (1H, s), 7.58 (1H, d, J = 8.9Hz) MASS: 582 (M + H) + (Please read the precautions on the back before filling out this page) 102-2 nPr H -0-tCH2t4C00H Η mp: 155-155.5eC IR (Nujol): 2700-2500, 1730, 1710, 1610, 1580, 1460, 1380, 1280 cm-1 NMR (DMS〇-d6, δ ): 0.86 (3H, t, J = 7.2Hz), 1.36 (9H, s), 1.35-1.5 (2H, m), 1.6-1.99 (6H, m), 2.25-2.31 (2H, m), 3.90- 4.00 (2H, m), 4.83 (1H, t, J = 6.1Hz), 5.04 UH, d, J = 11.6Hz), 5.12 (1H, d, J = 11.6Hz), 6.43 (1H, d, J = 2.2Hz), 6.53 (1H, dd, J = 2.2, 8.6Hz), 7..03 (1H, dd, J = 2 .5, 9.0Hz), 7.30-7.35 (2H, m), 7.42 (1H, s), 7.46 (1H, s), 7.58 (1H, d, J = 9.0Hz), 12.6-12.8 (2H, br s ) This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm.)

R 24 nPr η A7 B7 R25 -CKCH2f5COOH Η mp: 147-147.5eC IR (Nujol): 2700-2500, 1725, 1705, 1610, 1580, 1500, 1460, 1380 cm " 1 NMR (DMS〇-d6, δ) : 0.86 (3H, t, J = 7.4Hz), 1.36 (9H, s), 1.35-1.85 (11H, m), 2.33 (2H, d, J = 7.0Hz), 3.96 (2H, br s), 4.82 (1H, d, J = 6.lHz), 5.03 (1H, d, J = 11.8Hz), 5.13 (1H, d, J = 11.8Hz>, 6.42 (1H, s), 6.53 (1H, d, J = 8.5Hz), 7.02 (1H, dd, J = 2.4, 9.0Hz), 7.29-7.33 (2H, m), 7.42 (1H, s), 7.46 (1H, -s), 7.58 (1H, d, J = 9.0Hz) MASS: 610 (M + H) + Elemental analysis: lysis Calcd. For Calculated values: C 65.00, H 6.45, N 2.30 Measured values: C 65.43, H 6.55, N 2.26 102-4 Η H -CKCH2, 3COOH H IR (Nujol): 3500-3000, 2700-2500, 1700, 1610, 1580, 1500, 1460, 1380 cm-1 NMR (CDC13, δ): 1.36 (3Η, s), 1.93 (2H, quint, J = 6.9Hz), 2.38 (2H, t, J = 7.2Hz), 3.98 (2H, t, J = 6.9Hz), 4.79 (2H, s), 5.08 (2H, s), 6.54 (1H, s) , 6.58 (1H, d, J = 2.6Hz), 7.04 (1H, dd, J = 2.6, 9.0Hz), 7.30-7.35 (2H, m), 7.44 (1H, d, J = 6.5Hz), 7.45 ( 1H, s), 7.-58 (1H, d, J = 9.0Hz) MASS ： 540 (M + H) + this paper Degree applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling out this page) _ -192- 474811 A7 B7 、 Instructions (丨) 200 cases R21 R22 R24 r25 102- 5 Et H -CHCH2 ^ 3COOH Η IR (Nujol): 3300, 2500, 1700, 1610, 1585, 1500 cm-1 NMR (CDC13, δ): 0.98 (3H, t, J = 7.4Hz), 1.36 (9H, s), 1.80-2.00 (4H, m), 2.37 (2H, d, J = 7.4Hz), 3.95 (2H, t, J = 6.2Hz), 4.80 (1H, t, J = 6.2Hz), 5.05 ( 1H, d, J = 11.8Hz), 5.13 (1H, d, J = 11.8Hz), 6.45 (1H, d, J = 2.0Hz), 6.53 (1H, dd, J = 2.0, 7.8Hz), 7.03 ( 1H, dd, J = 2.6, 9.0Hz), 7.30-7.37 (2H, m), 7.42 (1H, s), 7.45 (1H, s), 7.58 (1H, d, J = 9.0Hz)

102-6 Me Me Η H

mp: 175-176 ° C IR (Nujol): 1710 cm_l NMR (DMSO-dg, δ): 1.36 (9H, s), 1.54 (6H, s), 5.14 (2H, s), 6.82 (1H, d, J = 8Hz), 7.00 (1H, t, J = 8Hz), 7.07 (1H, dd, J = 2, 9Hz), 7.27 (1H, s), 7.30 (1H, d, J = 2Hz), 7.44 (1H , s), 7.46 (1H, s), 7.50 (1H, m), 7.60 (1H, d, J = 9Hz) / Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (Page 13) 13.13 (1H, br s) MASS: 466 (M + H) + -193- This paper size is applicable to Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) 474811 A7 B7, invention description) 201 Example 1 R21 R22 R24 R25 102-7 nBu Η Η Η

mp: 84-86 ° C IR (Nujol): 1720 cm-1 NHR (CDC13, δ): 0.86 (3H, t, J = 7Hz), 1.2-1.6 (4H, m), 1.40 (9H, s), 2.02 (2H, m), 4.85 (1H, t, J = 6Hz), 5.12 (1H, d, J = 12Hz), 5.23 (1H, d, J = 12Hz), 6.9-7.5 (9H, m) MASS: 494 (M + H) +

102-8 Yang 2 ten 3 Η H

mp: 179-180 ° C IR (Nujol): 1720, 1580 cm-1 NMR (CDC13, δ): 1.4 0 (9H, s), 1.96-2.2 (2H, i), 2.44-2.6 (2H, m) , 2.75-2.86 (2H, m), 5.12 (2H, s), 5.96 (1H, m), 6.52 (1H, d, J = 8Hz), 6.96 (1H, s), 7.0-7.06 (2H, m) , 7.1-7.2 (2H, m), 7.26 (1H, s), 7.4-7.5 (2H, m) MASS: 478 (M + H) +

102-9 Et Η Η H mp: 161-162. . IR (Nujol): 1720 cm'1 NMR (CDCI3, δ): 1.01 (3H, t, printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) J = 7Hz), 1.35 (9H, s), 1.92 (2H, m), 4.80 (1H, t, J = 6Hz), 5.20 (2H, s), 6.9-7.1 (3H, m), 7.2-7.3 (2H, m), 7.43 (1H, s), 7.45 (1H, s), 7.4 (1H, m), 7.60 (1H, d, J = 9Hz) —194— This paper size applies to China National Standard (CNS) A4 (210X297 mm) ) 474811 Printed by Shellfish Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs A7 ____B7 V. Examples of Invention R21 R22 R24 R25

102-10 Η Η H -CKCH2f3COOH

mp: 147-148 ° C ir >, (mi) oi): rnr ', ir,'-,. , 1576 cm-1 NMR (CDCI3, δ): 1.38 (9H, s), 1.90 (2H, m), 2.36 (2H, t, J = 7Hz), 3.92 (2H, t, J = 6Hz), 5.16 ( 2H, s), 6.82-7.10 (4H, m), 7.33 (1H, d, J-2.5Hz), 7.44 (1H, d, J ~ 3.4Hz), 7.46 (1H, s), 7.60 (1H , d, J = 9Hz) MASS: 540 (M + H) +

102-11 Η Η H -0CH2C00H

mp: 157-158 ° C IR (Nujol): 1710, 1582 cm_l NMR (CDC13, δ): 1.35 (9H, s), 4.61 (2H, s), 4.74 (2H, s), 5.16 (2H, s) , 6.8-7.1 (4H, m), 7.33 (1H, m), 7.43 (1H, 5), 7.46 (1H, s), 7.60 (1H, d, J = 9Hz), 12.97 (2H, s) MASS: 512.1 (MfH) + m 103 Example 101 gives compound of the formula "4- {4- {[2- (4 -Third-butyl beerazole-2-yl) phenylfluorene-5-furan-5-ylamino] Methyl) -3-methoxyphenoxy} Butyric acid IR (Nujol): 2700, 1705, 1610, 1585, 1500 cm-1 NMR (CDC13, δ): 1.40 (9Η, s), 2.05-2.15 (2H , m), 2.60 (2H, t, J = 7.0Hz), 3.84 (3H, s), 4.03 (2H, t, J = 6.0%), 5.05 (2H, s), 6.45-6.50 (2H, m >, 6.95 (1H, s >, 7.01 (1H, dd, J = 2.7, 8.9Hz), 7.13 (1H, d, this paper size applies the Chinese National Standard (CNS) A4 specification (21OX297 mm) -195 · -(Please read the notes on the back before filling this page) Order 474811 A7 B7 V. Description of the invention (``%) J = 2.7Hz), 7.26 (1H, s), 7.33 (1H, d, J = 8.6Hz ), 7.42 (1H, d, J = 8.9Hz) MASS: 524 (M + H) + Example 104 in 2- {2- {[2- (4- Third butylcarbazol-2-yl) phenylhydrazone Furan 5-yloxy] methyl) -6- Methoxyphenyl} propionic acid (5 8 3 in g) in methanol (5ml), added IN Na0H (1.21ml), concentrated under reduced pressure, dissolved in water (5ml), and lyophilized to give 2- {2- { [2- (4 -Third-butyltriazol-2-yl) phenylarfuran-5-yloxy] methyl} -6-methoxyphenoxy} Sodium propionate (580 mg) Amorphous NMR (DMSO-dg, δ): 1.35 (9Η, s), 1.37 (3Η, d, J = 7Hz), 3.78 (3H, s), 4.62 (1H, q, J = 7Hz), 5.44 ( 1H, d, J = 13Hz), 5.64 (1H, d, J = 13Hz), 6.92 (3H, s), 7.09 (1H, dd, J = 2.5, 9Hz), 7.37 (1H, d, J = 2.5Hz), 7.45 (2H, s), 7.57 (1H, d, J = 9Hz) MASS: 504.0 (M + H) +, 526.0 (M + Na) + Example 105 The following compound was obtained as in Example 104. 1) (S) -2- {2- {[2- (4 -Third-butyl Pfazol-2-yl) phenylarfuran-5-yloxy] methyl} -6-methylaminobenzene } Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economics of Sodium Propionate (please read the notes on the back before filling this page) [α] §7 = -5.44. (C = 0.91, MeOH) IR (Nujol): 1580, 1450, 1260 cm-1 NMR (CDC13, δ): 1.19 (3H, d, J = 6.9Hz), 1.40 (9H, s), 3.39 (3H, s), 4.40 (1H, q, J = 6.9Hz), 4.73 (2H, dd, J = 12.2Hz), 6.39 (1H, br d), 6.78-7.00 (5H, m), 7.03 (1H, s) , 7.24 (1H, d, J = 8.9Hz) MASS: 504 (M + H) +, 526 (M + Na) + -1 9 6- The national standard (CNS) A4 size of this paper is applicable (210X297) (Centi) 474811 A7 B7 _ V. Description of the invention (叩-) 2) (R) -2- {2- {[2- (4-Third-butyltriazol-2-yl) benzofuran-5-yl Oxy] methyl} -6-methylphenoxy} sodium propionate [α] ξ7 = +8.920 (c = 1.11, MeOH) IR (Nujol): 3300-3000, 1580, 1450 cm-1 NMR (DMS〇-d6, δ): 1.35 (9H, s), 1.37 (3H, d, J = 6.8Hz), 3.78 (3H, s >, 4_60 (1H, q, J = 6.8Hz), 5.43 (1H , d, J = 13.4Hz), 5.65 (1H, d, J = 13.4Hz), 6.92 (3H, s), 7.10 (1H, dd, J = 2.5, 9.0Hz), 7.37 (1H, d, J = 2.5Hz), 7.43 (1H, s), 7.45 (1H, s), 7.57 (1H, d, J = 9.0Hz) MASS: 482 (M + H) +

Example 1 OR At room temperature, 2- {2- {[2- (4 -Third-butylxanthazol-2-yl) phenylsulfan-5-yloxy] methyl} -4-methylbenzene Oxy} propionic acid (1.57g) and 1-hydroxybenzitriazole (0.439g) in dimethylformamide (20ml) with 1-ethyl-3- (3'-dimethylaminepropyl) sulfonate Diimine hydrochloride (0.63 g), stirred at room temperature for 1 hour, then cooled with ice, added ammonia (1.1 m 1), stirred for another 1 hour, diluted with water, extracted with ethyl acetate, and separated the organic layer. Wash with sodium bisulfate and brine, and dry with magnesium sulfate. After concentration, the residue (1.50 g) was recrystallized from isopropyl ether, filtered, and dried under reduced pressure to give 2- {2- {[2- (4-tert-butyltriazol-2-yl) benzofuran-5 -Base gas base] methyl} Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page)

-6-methoxyphenoxy} propanamide (1.37 g). mp: 155-156eC IR (Nujol): 3450, 3100, 1682, 1580 cm-1 NMR (CDC13, δ): 1.41 (9H, s), 1.49 (3H, d, J = 7Hz), 1.8 (1H, br s), 3.85 (3H, s), 4.83 (1H, q, J = 7Hz), 5.13 (2H, center of a pair of d, J = 11.5Hz), 5.62 (1H, br s), 6.9-7.16 (6H, m), 7.27 (1H, d, J = 0.8Hz) / 7.44 (1H, d, J = 9Hz) MASS: 481 (M + H) + -1 9 7-This paper size applies to Chinese national standards ( CNS) A4 specification (210X297 mm) 474811 A7 B7__ V. Description of the invention (• Extra) Example 1 07 Example 1 Q 6 The following compounds were obtained. 2-{[2- (4- (Third-butyltriazol-2-yl) benzylfuran-5-ylamino] methyl) -6-methylaminobenzylamine

mp: 119.5-121.5 ° C IR (Nujol): 3500-3000, 1680 cm-1 NMR (CDC13, δ): 1.41 (9Η, s), 3.88 (3Η, s), 4.56 (2Η, s), 5.12 ( 2Η, s), 5.64 (1H, br s), 6.93-7.17 (6H, m), 7.28 (1H, s), 7.44 (lH, d, J = 9.0Hz) MASS: 467 (M + H) + Example 1 08 At room temperature, 2-[2-{[2-(4 -Third-butylifazol-2 -yl) phenylsulfanylfuran-5-yloxy] methyl} phenylamino) valeric acid (5 0 0 mg), and a solution of 1-hydroxybenzitriazole (141 mg) in dimethylformamide (5ιη1) was added with N-ethyl-N '-(3-dimethylaminepropyl) 5diamine. Amine hydrochloride (200mg), stirred at the same temperature for 1 hour and then ice-cold. Add concentrated ammonia (0.3 m 1), stir for 1 hour, dilute with water, extract with ethyl acetate, separate the organic layer, wash with sodium hydrogen sulfonate water and brine, dry with magnesium sulfate, and concentrate to give 2- {2 -[〔2- Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) (4 -Third-butyltriazol-2-yl) benzofuran-5-yloxy Group] methyl} phenoxy} pentamidine (51 Dmg). IR (Nujol): 3300-3150, 1685, 1580 cm-1 NMR (CDC13, δ): 0.92 (3Η, d, J = 7Hz >, 1.41 (9Η, s), 1.54 (2H, m), 1.97 (1H, m), 4.75 (1H, t, J = 5.8Hz), 4.96 (1H, d, J = 10.8Hz), 5.35 (1H, d, J = 10.8Hz), 5.45 (1H, br s), 6.77 (1H, br s), 6.9-7.5 (9H, m) MASS: 479 (M + H) + -1 98- This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 474811 A7 B7 5 2. Description of the invention (i) Example 1 09 The following compound was obtained in the same manner as in Example 1Q8. 2- {2- {[2- (4-Third-butylbrazol-2-yl) phenylsulfan-5-yloxy] methyl } Phenylphenyl} -2-methylpropanamide

mp: 148-149 ° C IR (Nujol): 3450, 3150, 1685, 1610, 1585 cm NMR (DMS〇-d6, δ): 1.36 (9H, s), 1.46 (6H, s), 5.17 (2H, s >, 6.88 (1H, d, J = 8.2Hz >, 7.0-7.5 (9H, m), 7.62 (1H, d, J = 9Hz) MASS: 465 (M + H) + M 110 Example 2 obtained The following compounds: 1) 2- {2- {[2- (4- (Third-butyltriazol-2-yl) phenylarfuran-5-yloxy] methyl} -6-methoxyphenoxy) Propionitrile IR (CH2C12): 1674, 1585, 1480, 1270, 1190 cm-1 NMR (CDC13, δ): 1.41 (9Η, s), 1.76 (3H, d, J = 6.8Hz), 3.90 (3H, s ), 5.16 (1H, q, J = 6.8Hz), 5.17 (1H, d, J = 12Hz), 5.30 (1H, d, J = 12Hz), 6.9-7.2 (6H, m), 7.30 (1H, d , J = 〇.7Hz), 7.43 (1H, d, J = 9Hz) MASS: 463 (M + H) + 2) {2- {[2- (2 -Third-butyltriazol-2-yl) Phenylfuran-5-yloxy Printed by the Consumers' Cooperative of the China Standards Bureau of the Ministry of Economic Affairs (Please read the precautions on the back before filling out this page) Base] Methyl} -6-methoxybenzoyl} Acetonitrile

mp: 80.8-83.4eC IR (Nujol): 1585, 1250 cm ~ ^ NMR (CDC13, δ): 1.41 (9H, s), 3.91 (3H, s >, 4.89 (2H, s), 5.20 (2H, s ), 6.95 (1H, dd, J = 2.7, 7.1Hz), 6.96 (1H, s), 7.02 (1H, dd, J = 2.6, 9.0Hz), 7.1-7.21 (3H, m), 7.28 (1H, s), 7.44 (1H, d, J = 9.0Hz) MASS: 449 (M + H) + -1 9 9- This paper size applies to China National Standard (CNS) 8 4 specifications (210X297 mm) 474811 A7 B7 5 2. Description of the invention (I pair) #ii 111 Under ice-cooling, dissolve phosphorus oxychloride (2 4 5 IB g), dissolve in dimethylformamide (2 ml), and add 2- {2- {[2- (4 -Third butyl carbazol-2-yl) benzofuran-5-ylamino] methyl} phenoxy} pentylamine (51Qnig) e Stir at room temperature for 2 hours, concentrate, dilute with water, and diethyl acetate Ester extraction, washing the organic layer with brine, drying over magnesium sulfate, and concentrating to give 2- {2- {[2- (4-tert-butylcarbazol-2-yl) phenylsulfan-5-ylamino] methyl} Benzyl} valeronitrile (453 mg) 〇IR (Nujol): 1604, 1584 cm-1 NMR (CDCI3 / δ): 0.98 (3Η, d, J = 7.4Hz), 1.50 (9H, s), 1.67 (2H, m), 2.06 (2H, m), 4.87 (1H, d, J = 6.5Hz), 5.08 (1H, d, J = 12Hz), 5.19 (1H, d, J = 12Hz), 6.9-8.0 (9H, m) HASS: 461 (M + H) + Example 1 1 2 Example 1 1 1 gives the following compound. 2- {2- {[2- (4-三 丁丁Benzoxazol-2-yl) phenylbenzofuran-5-ylamino] methyl} phenoxy} -2 -methylpropionitrile

mp: 80-81 ° C IR (Nujol): 1600, 1585 cm-1 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) NMR (DMS0-d6, δ): 1.42 (9H, s), 1.75 (6H, s), 5.09 (2H, s), 6.9-7.5 (9H, m) MASS: 447 (M + H) + Example 1 ”Example 2 1 gives the following compound .

1) 2- (4 -Third-butyl Iphizol-2-yl) -5- {3 -Methoxy-2- [1- (1H -2 0 0-This paper size applies to Chinese National Standard (CNS) A4 specification (2IOX297 mm) 474811 A7 B7 V. Description of the invention (⑼) -tetrazol-5-yl) ethoxy] benzyloxy} phenylbenzofuran mp: 103-104. . IR (Nujol): 2300-2650, 1585 cm-1 NMR (CDC13, δ): 1.42 (9Η, s), 1.78 (3Η, d, J = 6.7Hz), 3.84 (3H, s), 5.01 (1H, d, J = 10.7Hz), 5.30 (1H, d, J = 10.7Hz), 6.13 (1H, q, J = 6.7Hz), 6.9-7.08 (5H, ra), 7.19 (1H, d, J = 2.5 Hz), 7.34 (1H, s), 7.45 (1H, d, J = 9Hz) MASS: 506 (M + H) +

Elemental analysis: C26H27NS 〇4 S Calculated value: c 6 2 · 4 2, H 6. 0 1, N 1 2 · 8 2 Measured value: C 6 3 4 8, H 6. 1 7, N 1 2 7 5 2 ) 2-(4-tertiary butyl Jfazole-2 -yl) -5-{[2-(1 H -tetrazol-5 -yl) methylamino-3-methoxyphenyl] methylamino} Phenylfuran

mp: 154.4-158.4 ° C IR (Nujol): 3200-2100, 1200 cm-1 NMR (CDCI3, δ): 1.41 (9Η, s), 3.89 (3Η, s), 5.18 (2Η, s), 5.64 ( 2H, s), 6.96-7.04 (5H, m), 7.10 (1H, d, J = 7.7Hz), 7.17 (1H, s), 7.43 (1H, d, J = 8.9Hz) MASS: 492 (M + H) + Example 1 1 4 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) will be 2- (2- {[2- (4- 2-yl) benzylfuran- 5-ylamino] methyl) benzyl) valeronitrile (430mg) was dissolved in dimethylformamide (5 m 1), and sodium nitrite (3 6 4 g) was added And gasified ammonium (Q. 3 g), stirred at 120 ° C for 3 hours, cooled, poured into water, extracted with ethyl acetate, and the aqueous layer was then extracted with ethyl acetate. The organic layers were combined and washed with brine. The magnesium sulfate was dried and concentrated. The crude product was chromatographed on a silica gel column (15g), dichloromethane and methanol-2 0 1-this paper is in accordance with the Chinese National Standard (CNS) A4 specification (210X 297 mm) 474811 economic. Printed by the Consumer Bureau of Standards Bureau A7 B7 V. Description of the invention (w) (2% volume ratio) Group) -5- (2- [1- (111-tetrazol-5-yl) butoxy] benzyloxy} benzopyranofuran (400 mg) NMR (CDC13, δ): 0.96 (3Η , d, J = 7Hz), 1.41 (9H, s), 1.55 (2H, m), 2.10 (2H, m), 4.90 (1H, d, J = 10Hz), 5.60 (1H, d, J = 10Hz) , 5.98 (1H, t, J = 6Hz), 6.97-7.5 (9H, m) MASS: 504 (M + H) + Example 1 1 5 Example 1 1 4 gives the following compound. 2- (4-Third-butyl Carbazol-2-yl) -5- {{2- [1- (1H-tetrazol-5-yl) -1-methylethoxy] methoxy} phenylhydrazine NMR (CDC13, δ) : 1.41 (9Η, s), 1.92 (6H, s), 5.17 (2H, s), 6.62 (1H, d, J = 8Hz), 7.0-7.3 (6H, m), 7.45 (2H, m) MASS: 490 (M + H) + Example 1 1 6 Hydroxylamine hydrochloride (174mg) was dissolved in dimethylarylene W (2ml), 28% sodium methoxide in methanol (0.125g) was added, and the mixture was stirred at room temperature for 10 minutes. 2 -{2-{[2- (4- (Third-butyltriazol-2-yl) phenylbenzofuran-5-ylamino] methyl} phenoxy) valeronitrile (224mg), then at 80 ° C Stir for 1 hour. The reaction solution was collected, diluted with water, extracted with ethyl acetate, and the organic layer was washed with brine, dried over magnesium sulfate, and concentrated to give 2- {2-{[2- (4-tert-butylblazol-2-yl) benzofuran. -5-yloxy] methyl} benzyl) pentanamidooxime, an amorphous solid (266fflg). -2 0 2-(Please read the precautions on the back before filling in this page) This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 474811 A7 B7 V. Description of Invention () IR (Nujol): 3250 , 1660, 1585 cm-1 NMR (CDC13, δ): 0.93 (3Η, t, J = 7Hz), 1.41 (9Η, s), 1.50 (2H, m), 1.75-2.0 (2H, m), 4.73 ( 1H, m), 4.81 (2H, br s), 5.03 (1H, d, J = 11.3Hz), 5.27 (1H, d, J = 11.3Hz), 6.96-7.1 (4H, m), 7.16 (1H, d, J = 2Hz), 7.2-7.3 (3H, m), 7.4-7.5 (2H, m) MASS: 494 (M + H) +

M.JLLX Example 1 16 gave the compound of the formula. 2- {2-{[2- (4- (Third-butylazolidin-2-yl) benzylfuran-5-ylamino] methyl} benzyl) -2-methylpropanimoxime. NMR (CDC13, δ): 0.93 (3Η, t, J = 7Hz), 1.41 (9H, s), 1.58 (6H, m), 4.96 (2H, br s), 5.12 (2H, s), 6.96-7.1 (4H, m), 7.0-7.5 (9H, m) MASS: 480 (M + H) + Example 1 1 8 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page)

Add 2- {2-{[2- (4-Third-butyltriazol-2-yl) benzylfuran-5-yloxy] methyl} benzylamine oxime (240mg) and three Ethylamine (61aig) was dissolved in tetrahydrofuran (3ml), and a solution of ethyl fumarate (65mg) in tetrahydrofuran (1 ffl 1) was added under ice-cooling. Stir for 15 minutes, filter, concentrate, dissolve in xylene (4ml), add 1,8-diazepinebicyclo [5.4.0] undec-7-ene (1 5 2 in g), stir at 50 ° C 3 hours, cooled, diluted with toluene, washed sequentially with 0.5 N hydrochloric acid and brine, dried over magnesium sulfate, chromatographed on a silica gel column, dissolved in a mixed solution of methane and methanol (1% by volume), and passed through a silica gel column Analysis, and dissolved with toluene toluate in ethyl acetate (6: 1) to obtain 3-{1-{2-{[2-(4-tert-butylbutrazol-2-yl) benzofuran-5-yloxy Base] methyl) benzene-2 0 3-This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 474811 A7 B7 V. Description of the invention (oxy) butyl} -1,2,4-ming Diazoline-5 -_ (1201 ^). IR (Nujol): 1770, 1585 cm-1 NMR (CDCI3, δ): 0.96 (3Η, t, J = 7Hz), 1.41 (9H, s), 1.53 (2H, m), 1.7-2.1 (2H, m ), 4.85 (1H, d, J = 10.2Hz), 5.93 (1H, t, J = 7Hz), 5.46 (1H, d, J = 10.2Hz), 7.0-7.5 (9H, m), 10.1 (1H, br s) MASS: 520 (M + H) + Example 1 1 9 The following compound was obtained from Example 118. 3-{1-(2-{[2-(4-tert-butyltriazol-2-yl) phenylbenzofuran-5 -ylamino] methyl) benzyloxy) -1-methylethyl } -1,2,4 -B oxadiazolin-5-one

mp: 120-122 ° C IR (Nujol): 1772, 1585 cm-*-NMR (CDCI3, δ): 1.40 (9Η, s), 1.76 (6Η, s), 5.12 (2H, s), 6.9- 7.5 (9H, m), 10.2 (1H, br s) MASS: 506 (M + H) +

H will be 2-{[2- (4 -Third-butyl P thiazolyl-2-yl) phenylsulfan-5-ylamino] methyl} -4- [3- (ethoxycarbonyl) propanyl ] Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs of Phenoxyacetic Acid (Please read the precautions on the back before filling this page) The ester (200fflg) is dissolved in acetonitrile (ΙΟικΙ) and acetone (lull) and added with methanesulfonic Acid (62 mg). Stir at 8 ° C for 2 hours. The reaction was concentrated and diluted with water and neutralized with sodium hydrogen sulfonate. Acidified with 1 N hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with brine and dried under sulfuric acid SM After concentration, it is crystallized from diisopropyl ether and n-hexane (1: 2), filtered and dried to obtain 2-{[2- (4-tert-butylcarbazol-2-yl) benzofuran-5- (Alkoxy) methyl) -2 0 4-This paper size applies to Chinese National Standard (CNS) A4 (2 丨 0'〆297 mm) 474811 A7 B7 _ V. Description of the invention (

-4- [3- (ethoxycarbonyl) propanyl] benzene acetic acid (117 mg). mp: 102-103eC IR (Nujol): 1750 (sh), 1730 cm-1 NMR (CDC13, δ): 1.24 (3H, t, J = 7Hz), 1.48 (9H, s), 2.07 (2H, m) , 2.49 (2H, t, J = 7Hz), 3.95 (2H, t, J = 7Hz), 4.13 (2H, q, J = 7Hz), 4.71 (2H, s), 5.18 (2H, s), 6.79 ( 2H, d, J = 2Hz), 6.96 (1H, s), 7.03 (1H, dd, J = 2.4, 9Hz), 7.19 (1H, d, J = 2.4Hz), 7.26 (1H, d, J = 2.4 Hz), 7.41 (1H, d, J = 9Hz) MASS: 568 (M + H) + 112 丄. At room temperature and under nitrogen, NaH (60 oil, 7.79%) will be reduced to 5 -methyl group- 1H-B Indazole-3-carboxylic acid (17.0 g) of N, N-dimethylformamide (400 ml). After 30 minutes, 4-tert-butyl-2- [5- (3-chloromethyl) benzopyranfuran-2-yl] H azole (29.76 g) was added over 5 minutes. Stir at 45 ° C for 3 hours, pour into ice water (2 1) and wash the reaction tube with water (200 m 1). The combined washings were acidified with 10% hydrochloric acid (5 (] G in 1) and vigorously stirred for 1 hour. The precipitate was collected by filtration, washed with water and air-dried for 1 day. The crude product was treated with isopropanol and isopropyl ether (7: 3 ) Washed and dried under vacuum to give 5-methoxy-1- {[2- (4- tert-butylcarbazol-2-yl) phenylsulfan-5-yl] methyl} azole-3-carboxyl Acid (36 · 5 g) 〇 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) IR (Nujol): 2900-2300, 1685, 1660, 1480, 1460, 1380 cm -1 NMR (DMSO-dg, δ): 1.35 (9H, s), 3.82 (3H, s), 5.84 (2H, s), 7.12 (1H, dd, J = 2.4 and 9.0Hz), 7.35 (1H, dd, J = 1.8 and 8.6Hz), 7.44 (1H, s), 7.45 (1H, d, J = 2.4Hz), 7.48 (1H, d, J = 8.5Hz), 7.64 (1H, s), 7.67 (1H, d, J = 8.6Hz), 7.79 (1H, d, J = 9.0Hz), 12.80-13.20 (1H, br s) -2 0 5-This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) 474811 A7 B7 _ V. Description of the invention *) # 111 2 2 5 -methoxy-l- {[2- (4-tert-butyloxazol-2-yl) benzofuran -5-yl] methyl} »§ 丨 azole-3-carboxylic acid (3.0 g) and concentrated sulfur (0.3 ml of) was dissolved in methanol (3 0 m 1) and refluxed for 6 hours. Cool to room temperature and let stand overnight. The precipitate was collected by filtration and washed with isopropyl ether to give 5-methylamino-1-{[2- (4-tert-butyltriazol-2-yl) benzene. Furan-5-yl] methyl) indazole-3 -carboxylic acid methyl ester IR (Nujol): 1700, 1495, 1480, 1460 cm-1 NMR (CDC13, δ): 1.41 (9Η, s), 3.89 (3Η , s), 4.06 (3Η, s), 5.76 (2H, s), 6.98 (1H, s), 7.20 (1H, dd, J = 2.4 and 8.7Hz), 7.19-7.28 (2H, m), 7.35 ( 1H, s), 7.46 (1H, d, J = 8.7Hz), 7.49 (1H, s), 7.59 (1H, d, J = 2.1Hz) Example 1 2 3 The following compound can be obtained by the method of Example 19. 5-methylamino-1-{[[(2- (4-tert-butylxanthazol-2-yl) phenylbenzofuran-5-yl] methyl) indazole-3 -carboxamidine IR (Nujol) : 3500-3000, 1675 cm-1 NMR (DMSO-dg, δ): 1.34 (9Η, s), 3.80 (3Η, s), 5.81 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the note on the back first) Please fill in this page again) (2Η, s), 7.09 (1Η, dd, J = 2.3 and 9.2Hz), 7.34 (1H, dd, J = 1.8 and 8.6Hz), 7.41 (lH, s), 7.49 (1H , s), 7.51 (1H, s), 7.56 (1H, d, J = 2.3Hz), 7.61 (1H, d, J = 1.8Hz), 7.66 (1H, br s), 7.66 (1H, d, J = 8.6HZ), 7.74 (1H, d, J = 9.2Hz) MASS: 461 (M + H) +-2 0 6-This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 474811 A7 B7 V. Description of the invention (〆) #ll 1 24 The method of Example 44 can obtain the following compound 0 5 -methoxy-1-{C 2-(4 ~ third butyl Ptazole-2-yl) benzene Furan-5 -yl] methyl) Indazole-3 Carboxylamide Example 1 2 5 The method of Example 2 0 can be obtained as the following compound 0 1- {[2-(4 -Third butyl_azole-2- Phenyl) benzofuran-5- Group] methyl} -5 -methoxyindazole-3 -carbonitrile Example 126 A 1N N a 0 Η solution (2 7, 8 ml) was added dropwise to a solution containing 5-{1-{[2-(4- —Butylcarbazole-2 -yl) benzopyranfuran-5 -yl] methyl} -5 -methoxy-1 Η -Pyrazol -3 -yl}-1 Η-tetrafluorene (13.5 g) Acetonitrile (150 ml). Warm to 45 ° C and stir until completely dissolved. Collect the solution at room temperature and wash it with acetonitrile and isopropyl ether (1: 1) to obtain 5- {1-{C 2- (4-tert-butyltriazole. (Please read the precautions on the back before filling in this Page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs -2 -yl) Phenylfuran-5-yl] methyl) -5 -methylamino-1H-B5 丨 azole-3-yl}

-1H-tetrazole sodium salt, colorless powder. mp: > 250 ° C IR (Nujol): 3600-3300, 1640, 1630, 1540, 1510, 1380 cm -1 NMR (DMSO-dg, δ): 1.34 (9H, S), 3.84 (3H, S) , 5.77 (2H, s), 7.04 (1H, dd, J = 2.5 and 9.1Hz), 7.36 (1H, dd, J = 1.6 and 8.8Hz), 7.46 (1H, s), 7.49 (1H, s ), 7.61 (1H, s), 7.61 (1H, d, J = 1.6Hz), 7.63 (1H, d, J = 9.1Hz), 7.83 (1H, d, J = 2.5Hz) '-2 0 7- This paper size applies to China National Standard (CNS) A4 (210X297 mm)

Claims (1)

474811 Patent application No. 86100473 "New thiazolyl benzofuran derivative and its pharmaceutical composition with leukotrisin and allergic slow reactant antagonist or inhibitor activity" (Amended on July 26, 1990 ) A Scope of patent application: 1. A compound of the following formula (I) and its salt 'N R- (I) where R1 is Ci.6 alkyl, butane_L is a single bond or a C: group which can be substituted with phenyl, oxygen or hydroxyl, and is A1 / + 1 L or -1 / 1 / -R8, Or A2 or (^ _6 alkoxy substituted with phenyl, where phenyl is substituted with more than one same or different alkoxy, which can be substituted with cyano, 1_6 alkoxycarbonyl, benzyloxycarbonyl, dibenzyloxycarbonyl , Carboxy'fluorenyl, alkylene, can be substituted with tetrazolyl and oxadiazolinyl heterocyclyl with oxygen, or can be substituted with methyl or hydroxy with (^ .6 alkoxymethyl); where -A ^ Α2-/ ^-is (a) -CR2 = CR3-X-, (b) -N = N-NR4- or (c) -NR5-N = N-, X is S, 474811 6. Scope of patent application R2 and R3 are each hydrogen or a substituent selected from the group consisting of fluorenyl; carboxyl; C] · 6 alkoxycarbonyl; phenyl; and can be substituted with carboxyl, Ci6 oxoyl, halogen, tetrazolyl or cyano Ch6 alkyl group, R4 is hydrogen or an alkyl group which may be substituted with phenyl group, this phenyl group may be substituted with carboxyl group or 6 alkyloxycarbonyl group, and R5 and R6 are the same as R4, and Y is CR1G or N, R7 and R8 Forms a ring with the connected carbon atom, and R7 and R8 have the following structure: -CRn = CR12 -CRI3 = CR14-, R9 is hydrogen, cyano; fluorenyl, carboxyl; benzyloxycarbonyl; C, -6 alkoxycarbonyl; tetrazolyl; can be substituted with benzyloxycarbonyl or alkoxycarbonyl alkyl; or can be substituted With carboxyl or C2.6 alkoxycarbonyl alkenyl, R1D is the same as R9, and only 11,! ^ 2,! ^ 3 and R14 are each hydrogen or the substituent is selected from carboxyl: (V6 alkoxycarbonyl; halogen; nitrate Amino; hydroxy; C3.6 cycloalkoxy; h ^ alkyl may be substituted with halogen, hydroxyl, carboxyl or (3 ^ 6alkoxycarbonyl); and Ci6 alkoxy may be substituted with cyano, tetra Oxazolyl, fluorenyl 'carboxyl, C, .6 alkoxycarbonyl, (^ -6 alkylene, or phenyl which can be substituted with halogen, carboxyl, or protected carboxyl. 2. For the compound in the first scope of the patent application, It has the following formula: 474811 6. Scope of patent application Where R], L and -A ^ A'A3- are as defined in item 1 of the scope of patent application. 3. If the compound in the scope of application for item 1 has the following formula: R7 Υ is CR1 () or NR, R7, RS, R9 and R1Q are each as defined in item 丨 of the scope of patent application. 4. For the compound in the third item of the patent application, wherein Y is N, R9 is tetrazolyl, and R7 and R8 form a ring with the connected carbon atom, and R7 and R8 have the following structure: -CRn = CR12-CR13 = CR14 _, where one of Rn, R12, R13 and R14 is C " hydroalkoxy and the others are hydrogen. 5. For the compound in the scope of application for patent No. 1 in which L is a single bond and Q is (^ .6 alkoxy substituted with phenyl, where phenyl is substituted with more than one same or different alkoxy, it may be Substituted by cyano, c, -6 alkoxyl'oxycarbonyl, dibenzomethoxycarbonyl 'carboxyl, fluorenyl'c, and alkylene, can be substituted by oxygen tetrazolyl and oxadiazolinyl heterocycles Base 'or substitutable 474811. The scope of the application for a patent is a methyl group of hydroxy or (^ _6 alkoxy. 6. For the compound of the scope of application for item 5, wherein Q is a Ch6 alkoxy group substituted with a phenyl group, wherein the phenyl group is substituted with (^ _6 alkoxy group, and (^ _6 alkoxy group is substituted with carboxyl group. 7. —A pharmaceutical composition for preventing and treating allergy or inflammation of humans or animals, containing the first compound as the active ingredient in the scope of patent application, mixed pharmaceutical Non-toxic carriers or excipients are allowed.