TW204351B - 2,3,4,5,-substituted furo [2,3-c] pyrazole - Google Patents

Abstract

Compounds of the formula (B) and their drug-making tolerable salts (see claim 1) in which R2=C1-11alkyl; hydroxy C1-4alkyl; X=halogen; R=H or C1-6 alkyl, n=1 or 2; R3=C1-9 alkyl; R4=C1-9 alkyl; R5=H;-COR; -CH2OH; -CH2OCOR1; -COX, X=halogen;

Description

204351 V. Description of the invention () Background of the invention Jian Yufur. South 丨 2,3, c】 In the study of azole compounds, only Guo of the present inventors, L. J. Haung, S. C. Kuo and Η. Τ. L. J. Taiwan Pharm. Assoc. 30 (1), 47-55 (1979), etc. using 5_ gas_ 3-methyl-1-benzyl p-bite-4-carboxylic acid (5-.111〇1: 〇-3-1116 seven 1171-1 · 1 ^ 1 ^ 1 ?; ^ 320: 1 ^ -4-0 31 " 13 0 伂 31 (^ 1 ^ < ^) (1) Boxed with ethylglycolate (2) Cheng Jia-1-Benji * fu " South 胼 [2,3-c] 〇bibit-5-Yuanqi Cg purpose (ethyl 3-methyl-l-phenylfuro [2,3-.]? 3 ^ 32〇16-5-〇31 " 15〇 乂 71316) (3) or using 5-methyl-3-methyl-1-benzylpyrazole-4 · formaldehyde C (5-hydroxy-3-methyl-l -phenylpyrazole-4-carboxaldehyde acetate) (4) combined with Chinese C * L * ethylbromoacetate (5) (process 1), due to the products obtained by these two methods, the yield is extremely low, and The product is very unstable, so only one compound, compound 3, has been synthesized without further discussion. (Please w please back to the precautions # 蜞 妙 此 页) installation. Order · Line-Central Standard of Ministry of Economic Affairs ! 5 Printed copies of industrial and consumer cooperatives "Scale side" + a «home Mei Bi (CNS) τ 4 size (210x297 well; it) 3 V. invention is described in () h3cv cho

NaH

N + HOCH2COOCH2CH3 Λ 6 Π 6 ό

DMF (2) ⑴

h3cv __ ^ cho Ji

NaH

H3C ^ / CHO N SN 0H + BrCH: COOCH2CH3 OCH2COOCH2CH3 (please read the notes to the back #Item to write this page) ό

DMF (5) ό ⑷ ⑹ • Compound 1 in Scheme 1 is a N1-substituted furo [2,3-c] pyraZ〇le derivative (A) As for the N2-substituted derivative B, there has been no report of Wenyue so far. Ministry of Economic Affairs + Central Development Bureau EJ: Gongxiao # Cooperative Printed

'R5 R1 ㈧

• Rs Summary of the invention The present invention provides the above-mentioned derivative b and has one of the following formula series-4-This Kft scale uses the National Standards (CNS) T4 regulation (2 丨 0x297 male dragon) 204351 Λ 6η 6 5. Description of the invention () The novel 2,3,4,5-substituted furanopyridine [2,3 <] pyrazole derivatives, whose synthesis method is simple and high in yield, are suitable for industrial production. In the middle, some compounds have obvious platelet aggregation inhibitory effect, and some compounds have the anti-allergic effect of Mingying

(B) Read the notes first and back. Note the matter and then fill% in this page where R2 »'-ηalkyl; alkyl;

-CH CH ‘

-CH? -〇-) — ’Xs * halogen; (OR) n;

Rn -CH2-0-

CH

-CH COR;) COOR 5 CONHR; or

-cvr, where Ar «VH Ministry of Economy Central Standards Bureau A Industrial Consumers ¢ :: printed by cooperatives R = H or C16 alkyl, η c19 alkyl ;. Alkyl; 1 or 2 Η; -COR; -CH2〇H; -CH2〇COR1; -COX, x = halogen-COOR; -CONHR; a The size of this paper uses the Chinese National Standard (CNS) T4 specification (210x297 Public; Jt) 204351 Λ 6 Π 6 V. Description of the invention (-CONR1R1; -CO —N: " " " ^ -COHNAr ,; t-CO —fsj 0

-CO-N

-CONH (CH2) mN

-CONH (CH2> nN, Ar. -CO—N ^ o; Γ ~ \ -CO—N ^ NR; -CO — ^ / N— Ar -CONH (CH2) nAr3n -CH-CHCONHR; -CH = CH- COOR; -CH-C (COOR) 2; -CONHNHCOOR; or 3 readings in the contrary • > main matters%

Or N-N-C (ΛΛ N-COCH, printed by the Beigong Consumer Cooperatives of the Central Bureau of Economics of the Ministry of Economic Affairs, where Ari, 10 ~ c〇〇R or 1

Ar,: or ~ Ό 1-3, R and n are as defined above, \-C16 embankment, R,, Ar, the standard of the paper is used in the national standard (CNS) Ή regulation (210X297 male dragon) 204351 Λ β li 6 5. Description of the invention R or C3 cycloalkyl, Rb-Η, halogen or -〇CH. Description of the invention 1) Bi7 / solvent

2) NaHS〇3 (1) 2,3,4 -Triple substitutions "Manufacture of Fu Wei Piao [2,3_clv than bite_5-shuoqi (hi) (2,3,4-Trisbubstituted furo [2,3- c】 pyrazole-5-carboxylic acid (III)) R2

-················ (Please read the notes beforehand and write this page) The Central Ministry of Economic Affairs prints R2, R3, R4, the same formula (B) Process 2 The starting material used in the present invention is 2,3,4-trisubstituted thione [2,3-c] 0rt; ^ -6-63 (I> （（2,3, 4-trisubstitutedpyrano [2,3-c] pyrazol-6-ones (I)> refers to the inventor of the present invention Guo et al. Sc Kuo, LJ, Huang, H. Nakamura, J. Med. Chem ,, 27-539-44 ( 1984) and the literature method reported by LJ Haung, SC Kuo, Chem. Pharm. Bull, in press ·, that is, the reaction of hydrazine with the responsible C & Ucyl acetate) to form 3,4 -Secondary replacement. Nangeng [2,3-c] ton bite -6-vehicle (3,4-disubstituted pyrano [2,3-c] pyrazol-6-ones) and then can be obtained with various base Corresponding to 2,3,4. Tri-substituted pyridoxine [2,3-c] pyridin-6-one. Installation · Line-1 paper scale side use a B home standard (CNS) T4 specification (210x297 Λ) 204351 Repair jT.

AC Λ 6 U6 5. Description of the invention Further as shown in Scheme 2, compound I is dissolved in a suitable organic solvent (such as CHC13), first streamed with Mohr Br · 2 and then treated with NaHS〇3 for removal One molecule of HBr can get the corresponding 2,3,4 · three substitution _5_ 涣 -〇Bikou Legeng [2,3, 〇] ordered -6-copper (II) (2,3, 4-trisubstituted-5. Br〇m〇-Pyran〇 [2,3-c] pyrazol-6_one) 〇 煗 and dissolve compound II in a solvent (such as n-BuOH) heated to the point of Futeng deposit Add a strong base (such as n-BuONa) and wait for the reaction to be completed (confirmed by thin-layer chromatography> 'After purification and purification by column chromatography and recrystallization, the corresponding 2, 3 can be obtained , 4-trisubstituted furazoline [2,3-c] azole-S-carboxy (III, R_H) 〇 (please nil first please note the matter before writing the letter ΪΓ} Ministry of Economic Affairs ^ quasi Bureau employee consumption ^ Cooperative seal 51 Example 1-1 (1). 5 · Bromo · 2,3,4 · Trimethyl hydrazine i〇 南 胼 [2, 3-c] Gu-6 (1Η>-嗣 (H -1) g '〇28mol) dissolved in 75ml of gaseous imitation, under the chamber culvert so that dropwise added 奂-gas imitation solution [Australia (4.5g, 0.028mol) dissolved in 5〇 Nothing ] After the reaction is completed, add sub-warm argon until the color turns pale yellow, and the filtrate is washed with water. After dehydration with anhydrous sulfur, the solvent is distilled off. The resulting residue is white crystalline powder. Recrystallization of the mixed solution of gaseous alcohol (I: 3) can obtain compound II-1. White needle crystals' yield 6.5 g (90%). Mp: 203-206 C; IR (KBr) i /: 1720 ( C-〇) cm.1. -7 The Central Ministry of Economic Affairs, Ministry of Economy, Industry and Consumer Goods Cooperative Printing 51 51. Description of Invention () 4-CH3), 2.36 (s, 3H.C-3-CH), 3.83 (s, 3H, N-CH); MS, —om / z: 257 (H +), elemental analysis: calculated values c: 42 〇5, H: 3.53, N: 10.09, experimental values c: 42.11, H: 3.50, N: 10.95. ( 2) · 2'3,4-Trimethyl * family " Nanpin [2,3-c] commanded gu-5-shuo defeat (iil-l> Method 1: Put the metal on the ground (0.2g, 0 .〇〇87 Mojie> dissolved in 200 ml of C yeast, to obtain G sodium oxide solution. The compound II-1 (〇_5 g, 〇〇〇〇2mol) was suspended in 25 ml of G drunk , Make it drop by heating under reflux L sodium oxide solution, continue to stir 'When the reaction is completed, add 100 milliliters of water, heat to reflux for 10 minutes, and evaporate the solvent' residue. Wash the spines with water, the water layer is then treated with the wind solution, and the precipitate is In case of Yun, recrystallized with drunk, you can get compound III-1 0 yellow brown crystals, yield 0.06 g (15〇. mp: 206-208〇C; IR (KBr) v: 3050 < COOH) cm'1, 1670 -1 I (CO) cm; UV (CHC13) A ^^ father: 280nm; H-NMR (DMSO-dg) §: 2.43 (s, 6H'C-3-C denier & C-4-C denier), 3.76 (s, 3H, N_CH). MS m / z: 194 (M +), elemental analysis: C9Hi〇N2〇 3. Calculated values c: 55 67, Η: 5.19, Ν: 14.43, experimental values C: 55.70, H: 5.22, N: 14.50. Method II: Dissolve sodium metal (0.2 g, 0.087 mol) in 100 ml of the converted solution, evaporate the solvent, add 50 mmol and 7 drops of crown ether, and mix well. Then dissolve compound II-1 (1.0g, 0.0〇4mol) in 300ml, and use it at 70-9-the size of this paper. A B Home Shubi (CNS) T4 regulation (210x297 Male Dragon) (Please Ittl first, please take note of this-jn- 蜞 write this page) Pack. Order · Thread-81.12.-7

t: make the above mixed solution dropwise, heat and reflux for 1 hour, add 100 ml of water, heat and reflux for 10 cents pounds, the reaction solution is taken with water pomelo, the water is drawn out and then the solution is precipitated with 10 * Zhangqi solution, precipitate After encountering, recrystallizing with a ball, that is compound III-1. Printed by the Central Bureau of Economic Affairs of the Ministry of Economic Affairs, A Gongxiaot Cooperative Society 3i V. Description of the invention () Yellow-brown needle-like crystals, yield 0.42 g (550.P: 206-208 ° C; this product and the compound III obtained by Method I -1 After comparing its 1R and doing a blending test, the results are exactly the same, confirming that it is the same compound. Method III: Dissolving sodium metal (2 g, 0.087 mole) in 200 ml of n-butyl alcohol To obtain sodium butyrate solution. Then dissolve compound 11-1 (5 g, 0.02 mole) in 25 mL of n-butanol, and raise the temperature to l20t: to make sodium butoxide solution dropwise, Continue stirring. After the reaction is completed, add 100 ml of water and heat to reflux for 10 minutes. The reaction mixture is washed with water. The water layer is then treated with 10% solution (pH-ι). The precipitate is filtered. ， Recrystallized with G 崞, you can get compound H1. 1. Yellow-brown needle crystals, yield 2.32 g (65〇. Mp: 2〇6-2〇8C; this product and method 1, 11 The compound m-1 was compared with its 1R, and the blending test was performed, and the results were completely the same. It was confirmed that the compound was the same compound. Example 1-2 (1). 5-July 2 has 3,4-monomethyl ton. 2,3 ·. 丨 Tong bite copper (II-2) -10-(please read the back and the precautions # Crucible to write this page) 装-线-204351 Λ 6 li 6 Description of the invention () will 2- -3,4-Dimethylpyridine [2.3-c] pyrazole-6 (2H> -Tuna (I-2) (5g, 0.026mol) was dissolved in 75ml of gaseous At room temperature, make a drop of E-chloroform solution [Australian 5g, 0.028mol) dissolved in 50ml of gaseous form], when the reaction is completed, add sulfoxirane until the color becomes pale yellow, after Then, the filtrate was washed with water several times, and the gas-like layer was dehydrated with anhydrous thiomagnesium, and the solvent was distilled off, and the resulting residue was recrystallized with a gas-like scorpion mixed solvent, that is, compound II-2. White needle crystal, produced Rate 6.5 grams (85〇〇mp: 135-137〇C; IR (KBr) v: 1720 (CO) cm 'max

UV (CHC1.) Λ: 315.5nm; H-NMR (CDC10) δ: 1.37 (t 3H λ in S X 4 \ w, ^,

-CH2CH3), 2.23 (s, 3H, C-4-CHq), 2.43 (s, 3H, C-3-CH 4.07 (q, 2H, -C); [2CH3); MS, m / z: 271 ( M), elemental analysis: C1〇HnBrN2〇2, calculated values C: 44.30, H: 4.09, N: 10.33, experimental values C: 44.20, H: 4.00, N: 10.31〇 (please read the notes on the contrary Write this page) Installed-Line · Printed by the Ministry of Economy +. 極 楳 扃 剃 Employee Consumer Cooperatives -11-Λ 6 η 6 204351 5. Description of the invention () mp: 203-20510; IR (KBr) y: 2500- 3300 < -OH) cm " 1, 1 max 1690 (C-0) cm; UV (C h 〇H) person: 285nm; 1H-NMR (DMS0- ^ D max dg) S: 1.33 (t, 3H,- CH2CH3) (2.47 (s> 6H, C-3-CH3 & C-4-C10H12N2〇3, calculated value C: 57.69, H: 5.81, N: 13_45, experimental value C: 57.72, H: 5.63, N: 13.39 〇Example 1-3 (1) 5-bromo-2 · isopropyl-3,4-dimethylpyridine [2,3-Cjpyrazol-6 (2H> -one (II-3) to 2 _Isopropyl_3,4 · dimethyl dimethylamine [23_c Bubixia_6 (2Η) · ketone (ι · 3) (5 g, 0.024 mole) as raw material, refer to compound II; L The synthesis and purification method, that is T to obtain compound H-3. White needle crystals 'yield 6.5 g (85%). Mp: 164-166〇C; IR (KBr) max: 1720 (C-0) cm' 1; UV (CHC13) λ max: 316 nm (ε ~ 3.7 × 1〇4); 1H-NMR (CDC13) 5: 1.33 (d, 6H, -CH (CH3) 2,2.43 (s, 3H, C-4-CH) , 2.50 (s, 3H, C-3-CH), ° a 3 5 * 43 (s'lH'-CH ·); MS, m / z: 284 (M +), elemental analysis.

CllH13BrN2〇2, calculated value C: 46.34, H: 4.60, N: 9_82, experimental value C: 46.30, H: 4.66, N: 9.73 〇 (2). 2-isopropyl-3,4-dimethyl fur [He] Pyrazole 5 is based on compound H · 3 (5 g, 0. (US mole)> as the raw material, referring to the synthesis and purification methods of compound ιιι-ι, that is, compound ιιΐ 3. -12-Original paper ? Good standard side use Chinese a home sample (CNS) Yuan 4 specifications (2 丨 0X297 public goods> '" ~~ ----- (please read the back to the precautions # fill this page) Apparel · Ministry of Economic Affairs, Central Standards, Employee Price Reduction, Du Yin 51 Λ 6 η 6 204351 V. Description of invention () White crystal, yield 2.2 g (56%). Mp: 185-187¾; IR (KBr) v: 2250-3300 (-〇H) cm'1, 1 max 1720 (C-0) cm; UV (CH OH) Λ: 286.5nm (ε -4.2xl〇4); 1 z 0 max H-NMR < DMS0- d) 5: 1.33 (d, 6H, -CH (CH)), 2.48 < s, 6H,

—3 Z C-3-CH3 & C-4-CH3 >, 4.52 (mi1H (.Ch_). MS, m / z: 222 (M +), elemental analysis: CllH14N2〇3, calculated value C: 59.45, H : 6.35, N: 12.60, experimental value C: 59.40, H: 6.38, N: 12.73. Example 1-4 (1) 5-Han-2-propane, 々-dimethylpyridine ^^ 咣"Don't-" (please read the precautions first and then write this page) The Ministry of Economic Affairs standard and the β Gongxiaoji Cooperative Printed Xiaoxiao ruled paper (ΙΙ-4) with 2C-3,4 -Dimethyl Nanpin [2,3_c] ^ bite (5 g, 0.024 mole) as raw material, refer to compound ii; l synthesis and purification method, that is T to obtain compound n_4. White crystals, yield 5.5 Gram (8U). Mp: 108-110 »C; IR (KBr), max: 172〇 (c" 〇) cm-l; uv (CHCl3) λ max, 3〇2nm (£ -8.4xl〇4); 1H-NMR (CDC1; 3) δ: 1.33 (t, 3H, -CH2CH2CH3) 12.41 (s13HiC-4-CH3), 2.36 (s> 3H, C-3-CH3), 4.52 (m, 4H, _CVv); MSm / z: 284 (M +), elemental analysis of a CllH13BrN2〇2's ten values C: 46.34, H: 4.60, N: 9.82, experimental value C: 46.39, H: 4.67, N: 9.70 〇 (2). 2_propane_3,4-dimethylfuran [2,3-c] oxazolidine-carboxyl (III-4) as compound II-4 (5 g, 0.015 "Mohr" is the raw material, referring to compound binding 13-204351 Λ 6 Η 6 Central Ministry of Economic Affairs β 工 消 " Cooperative Print 54 54. Description of the invention () The synthesis and purification method of the compound III-1, that is, the compound 5H is obtained Ο White crystals, yielding I · 7 g (30%> 〇mp: 180-182〇C; IR (KBr) v: 2500-3000 (-OH) 010-1,1720 ID d X (CO) cm 1; UV (C2H5〇H) Λmax: 280nm (ε-2.8xl〇4); 1H-NMR (DMS0-d6) 3: 1.33 (t, 3H, -CH2CH2C_ ^ 3), 2.47 (s, 6H, C-3- CH3 & C-4-CH3), 4.52 (m, 4H, -CH2CH2-), 5.72 (s, 1H, C-5-H); MS, m / z: 222 (M +), elemental analysis: calculated value C : 59.45, H: 6.35, N: 12.60, experimental value c: 59.39, H: 6.31, N: 12.68ο Example 1.5 (1> · 5-bromo-2-methane CJ-3,4-dimethylpyridine Di [2,3_cj pyrazole-6 (1H> -vehicle (II-5) was blown with 2- | SC * -3,4-dimethyl. Nanshao [23_c Bubibit_6 (1Η) _one (1-5) (5 g, 0.024 mol) as raw material, refer to compound];];-] _ Synthesis and synthesis and purification methods, This gives compound Η-5. ♦ White crystals, yield 4.8 g (700. mp: 152-153〇C; IR ^ KBr ^ vmax: 3500-2 500 (-OH) cm'1, 1720 (C-0) cm 1; UV ( CH 〇H) Λ: 301nm (ε-4.4xl〇4); ^ D max H-NMR (DMSO-d6) 3: 2.36 (s, 6H, C-3-C ^ 3 & C-4-C ^ 3 〉, 3.72 (t, 2H, -NCH-), 3.98 (t, 2H, -CH „OH), 4.70 < br, lH, OH), —2 — 5.72 (m, lH, C-5-dan) ; MS, m / z: 287 (M +>, elemental analysis: C10HllBrN2〇3 'Calculated value C: 41.83, H: 3.86, N: 9.76, experimental value C: 41.70, H: 3.82, N: 9.86 〇-14- (Please read the notes on the back of this page first.) This paper is based on the Chinese standard Hsuanbi (CNS) Τ4 regulation (210X297; ":) 204351 d λ 6 5. Description of invention () (2>. 2-Rent G-3, Dimethylfuran [2,3-c] pyrazole-5-carbopyridine (III-5> Compound II-5 (5 g, 0.015 mole) as raw material According to the synthesis and purification methods of compound III-1, compound III · 5 can be obtained. White crystals, yield 1.7 g (35 *). Mp: 203-2061C; IR (KBr) 1 /: 2500-3000 ¢- 〇H) cm'1, max 168〇 (C-.〇) cm'1; UV (CH OH) λ: 283nm < ε -3.2xl〇4); 2 5 max H-NMR (DMSO-d) ： 2.45 (s (6H, C-3-CH0 & C-4-CH ^) (3.71 (t, 2H, -NCH2-), 4.08 (t, 2H, -CH2〇H), 4.83 (t, 1H, OH), 5.72 (m, lH, C-5-denier); MS, m / z: 224 (M +), elemental analysis: C10H12N204, calculated value C: 53.57, H: 5.39, N: 12.49, experimental value C: 53.60, H: 5.41, N: 12.53 〇Example 1-6 (1>. 5-bromo-2-benzyl-3,4-dimethyl hydrazine [2,3- £:] ton Jun-6 (1 } 〇-ketone (ΙΙ · 6) with 2.benzyl, 4-dimethyl hydrazine [2,3-c] azole-6 (1Η) -one (I-6) (5 g, 〇.〇 2〇mol) is the raw material, and the compound Ι · 6 can be obtained by referring to the synthesis and purification methods of the compound. The yield of white crystals was 5.4 g (81 *). Yin Hong, Ministry of Economic Affairs, Ministry of Economic Affairs, Bureau of Industry and Commerce, Yinhong (please read the precautions before writing this page) n »P: 176-177〇C; IR (KBr), ax: l72〇 ( c_〇> cm-l; uv (CHC1)

Amax: 317,5nm (ε &quot; 1.6x10 &gt;; 1h-NMR (CDC13> δ: 2.43 (si3H, C-4-CH3) i2.50 (s &gt; 3H1C-3-CH3) i 5.43 (s, 2H, -CH2-W), 7.25 (m, 5H, -CH2-C6 ^ 5); MS, m / z: 332 (M +); elemental analysis: C15H13BrN2〇2, calculated value C: 54.〇7, h: 3.93 , N: 8.41, -15-This paper scale is used in the edge of a sleepy family tree iMCNS) A 4 specifications (210x297 g; 40 -------- 204351 81.12.-7 Λ 6 Π6 V. Description of invention () Experimental value c: 54.15, H: 3.81, N: 8.40 (2) · 2-benzyl-3,4-dimethyl》 Fu Wei Pin [2,3- (:] Instructed Gu-5-Banqi (111 -6) Using compound II-6 (5 g, 0.015 mol) as the raw material, referring to the synthesis and purification method of compound III-1, compound 111_6 can be obtained. Yellow-brown crystal, 32 g (product Mou 81 *). mp: 196-198〇C; IR (KBr) 1 /: 2250-3300 &lt; 0-H): 1720 max (CO) cm'1; UV (〇2H5〇H) Λ max: 28A.5nm (e: 2.2 xl〇4); ^ Ή-ΝΜΚζΟΜεΟ-ά) δ: 2.47 (s, 6H, C-3-CH, C-4-CH), 〇—3 —3 5.37 (s, 2H, -CW5), 7.25 ( m, 5H, -CH2-C6 ^ 5); MS, m / z: 270 (M +>; elemental analysis: C15H14N2〇3, calculated value C: 66.66, Η: 5.22, Ν: 10.36, experimental value C: 66.73, H: 5.29, N: 10.47. Example 1-7 (1). 5-Huan-2- (2-Cetylmethyl) -3,4-Dimethyl pinnate [2,3-c] Bite-6 (2H> -ketone (II- 7) Combine 2_ (2 · Gabenbenmethyl) _3,4-dimethylpyrrolidine [2,3-c] pyrazole-6 (2H) -dionysine (1-7) (5.00 g, Ο.ου Molar) was dissolved in 100 ml of gaseous chloroform, and the dropwise addition of bromine-gasoline solution [bromine (5.00 g, 0.0 mol) in 50 ml of chloroform], when the reaction was completed ， Add sodium disulfite (sodiuin bisulfite) until the reaction solution fades to colorless. In case of solution, the solution is washed with water until it has no property; after the gas-like layer is dehydrated by anhydrous sulfur solution, the solution will pass The solvent was distilled off under reduced pressure, and the resulting residue was recrystallized with a mixed solution of chloroform to obtain compound II-7. -16-The ft scale of this paper is installed in the middle of the beta B home sample (CNS) 4 specifications (210X297 male dragon). Line-r Printed by the Ministry of Economic Affairs, the Central Bureau of Economics and Trade and Industry Co., Ltd. Du Printing ^ 04351 Μ Ministry of Economic Affairs Printed by Beigong Consumer Cooperative of Central Bureau of Standards 5. Description of invention () White needle crystal, yield 5.95 g (95.10. Ιηρ: 206-2〇8αΊ〇; IR (KBr) ^ m & x: 1712 (0-0) ^,-1; uv (CHC13) λmax: 3l8nm (ε -2.47x10); 1H-NMR (CDC13) g: 2.482 (s, 3H, C-4-CH3), 2.55 (s, 3H, C-3- CH3), 5.4〇 &lt; S) 2H, -CH2-), 6.82 (t, lH, 5, -H), 7.12-7.46 (m, 3H, 3 ,, 4, & δ *-!!); MS, m / z: 368 (M +); elemental analysis: Ci5H12BrClN2〇2, calculated value C: 49.〇l. H: 3.29, N: 7.62, experimental value: c: 49.20, H: 3.35 N: 7.69 o &lt; 2). 2- (2-Gabenben) -3.4-dimethyl "^ 夫 &lt; &gt; Nanpin [2,3-c] Bing-5 (2H) -carboxyl (III -7) Dissolve sodium metal (1.0 g, 〇43 mole) in 400 ml of n-butyl alcohol to obtain a solution of sodium butoxide; another compound II-7 (5.00 g , 0.014 mol) dissolved in n-butyl alcohol, wait for the temperature to rise to l20 ° C, then slowly add Ding Radon After the completion of the reaction, the reaction solution was distilled off to remove the solvent. After the residue was dissolved in water, it was then reconstituted with a 1N solution, and a precipitate precipitated out. The precipitate was taken and recrystallized from methanol. That is ▼ to obtain compound III-7. Light yellow crystals, yield 1.66 g (39.0%). mp: 218〇C &lt;dec.); IR (KBr) v: 2300-3100 (0-H), 1663 1 H0X (CO) cm '; UV (CH OH) Λ: 280nm (e-1.82xl〇4) ; ΧΗ- ^ 3 max *, NMR (DMS0-d6> Q: 2.48 (s, 3H, C-4-CH3), 2.50 (s, 3H, C-3-CH3>, 5.44 (s, 2H, -CH2 -), 6.79 &lt; t, lH, 5, -H), 7.25-7.55 (m'3H, 3, 'V & 6 * -denier); MS, m / z: 304 (M +); Elemental analysis: -17-(Please read the precautions before writing this page) The standard size of this paper is in the middle Η Η 家 t ^ MCNS) T4 specification (210x297 g; ϋ;) 5. Description of the invention () C15H13C1N2〇3, calculation Values C: 59.12, Η: 4.30, N: 9.19, experimental values: C: 59.25, H: 4.34, N: 9.20o Examples 1-8 (1>. 5 · Ao · 2 · (3. Qibenjia Base> _3 4 dimethyl hydrazine [23 c] to be azole-6 (2H> -one (II-8) to 2 · (3-gas pen methyl). 3,4 • dimethyl ^ flavor ㈣ 6 ^ > -Vehicle (1-8> (5.00g '0.017mol)> as raw material, referring to the synthesis and treatment purification method of compound II-1, that is, compound 118. Pale yellow crystals' yield 5.78g (92.4 %). Mp: 148-149 ° C; IR &lt; ^ r), max: l712 (c_〇) cm-1; ^ (CHC13) λ max. 318nm (ε-1.66xl〇4); 1H-NMR ( DMSO-d6) δ 2.53 (ά, 3Η, α-1.2Ηζ, α-4-αΗ3), 2.56 (Si3H, C-3-CH3), 5.41 (s, 2H, .C) i2-), 7.16.7.42 (111, paper and pen Ring proton <^ 2 ring prQt〇nS)); MS, m / z: 368 (M +); elemental analysis: ch * I m t. 15 12 n2〇2, calculated value C: 01, Η: 3 · 29, N: 7 62, experimental value: c: 49.18, H: 3.20, N: 7.54 〇Ministry of Economics, Central Bureau of Industry and Commerce β 工 消 &quot; Cooperative Du Yinlinong (2). 2- (3-chloro Stupid methyl) _3,4 · dimethylfuranhydrazine [23 &lt;] pyrazole-5 (2H) -carboxylic acid (III-8) with compound Ι · 8 (5.0 g, 14 moles) as For the raw materials, refer to the synthesis, treatment and purification methods of compound III-1, that is, the compound III-8-8 was yellow crystals. The yield was 2.42 g (56.9%). -18-This paper is used in the middle of a Η home standard (CNS) Τ4 specification (210x297 mm) -------- 204351 &lt; r Λ 6 Π6 Printed by the ex-consumer cooperative of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs 5i 5. Description of the invention () mp: 2041C (dec.); IR (KBr) u max: 2000-3200 (〇-H>, 1665 &lt; C-0) cm 1; UV (C2H5〇H) Amax: 28 〇nm &lt;e-1.98xl〇4); ^ -NHRCDMSO-d ^ δ: 2.48 (S, 6H.C-3 &amp; 0-4-0 ^), 5. Al (s, 2H, -0 Dan 2 -), 7.12-7.41 (m, 4H, stupid ring proton (benzene is called protons>; MS, m / z: 304 &lt;: M +); elemental analysis: Ci5h13C1N2〇3, calculated value C: 59 ,: L2, Η : 4.3〇, Ν: 9.19, experimental values: c: 59 36, H: 4.28, N: 9.11〇 Example 1-9 (1>. S-bromo-2- (4-chlorobenzylmethyl) _34_ Dimethyl hydrazide [23 c] · pyrazole-6 (2H) -bromide (11-9> 2- (4 · chlorobenzylmethyl) · 3,4_dimethyl dimethylpyrazine Ο.】 Zidazole_6 (2H) -one (1-9) (5_00 g, 0.017 mole) is used as the raw material, referring to the synthesis and treatment purification method of compound Ι-1 (Vinegar G 醏 for recrystallization solvent>, The compound H-9 was obtained as light yellow crystals, yielding 5.60 g (89.5%). Mp: 149-152 * t :; IR (KBr) i / max: l 715 (c_〇> cni-l; uv (CHC13) λ max: 316nm (^ = 1.58X104); lH._ (CDCl3) δ: 2.46 (d) 3H, J-1.2Hz, G-4-CH3) l2.51 (s, 3H, C-3-CH3), 5.26 (s, 2H, -CH2-), ^ .Οδζά ^ Η ^ -β.ΑΗζ ^^ ό ^ Η), 7.30 (d, 2H, J -8.4Hz, 3 '&amp;5'-blue); MS | m / z: 368 (M +); Elemental analysis: C15H12BrC1N2〇2, calculated value C: 49.〇l, H: 3.29, N: 7.62, Experimental values: (3: 49.21, H: 3.18, N: 7.71. -19-This paper uses the National Standard (CNS) TM specification (210x297 g *) (Please read the note of Jingbei 1 (0 Matter #Crucible to write this page) Installation &Line; Μ 204.351 5. Description of the invention () (2). 2- (4-chlorobenzylmethyl) _3,4-dimethylfurfural [2,3-c ] Ebit. 5 (2H) · Carboxylic acid (Ili-g) Using compound II · 9 (5.00g '〇.〇1414 mole) as a raw material, the synthesis and treatment of ginseng compound 111-1 purification method can be Compound III-9 was obtained as white crystals with a yield of 1.51 g (35.5 *>). mp: 218Q (dec.); IR (KBr) i / ^^^: 2400-360〇 (〇.fj ^ 1685 (C-Ocm'SuV &lt; C2H5〇H) λ ffiax: 282nm (ε-2.83x1ο4) ; NMR (DMSO-dg) δ: 2.47 (s, 3H, C_4-C ^ 3>, 2.48 (s, 3H, C-3_CH3), 5.38 (s, 2H, -CH2-), 7. ^ (Ά , ΣΗ, α ^ δ.δΗζ, 2 ^ 6 ^ H), 7.41 (d, 2H, J «8.6Hz, 3 '&amp; 5, -denier); MS, m / z: 3〇4 (M + ); Elemental analysis: C15H13C1N2〇3, calculated values C: 59 · 12, H: 4.30, N: 9.19, experimental values: C: 59.24, H26, N: 9.10. Example 1-1 0 5-Dec-2 · (2. Methyl> · 3,4 • Dimethyl compound [23c] · Pyrazole-6 (2H) -one (Ii-10) 2- (2-Methoxybenzyl >> 3,4 . Dimethyl instructed Wei Pin [23c instructed that the seven knees are hungry.... G, .. phase mole) as the raw material, referring to the compound method of compound compound ιι · ι, g. White crystals, yielding 6.05g (92 6%) 〇mp: 212-214〇C; IR (KBr) v. 179Wr, -1

max · 1721 (C ·.> cm; UV: 320nm (£ «-i 8Svin ^ \ 1 -o ^ xlO); H-NMR (CDC1) Q: 2.49 (s, 3H, C-4-CH) 2 3 -3; -2-52 &lt; s, 3H, C-3-CH3), 3.87 (s, 3H, (please pay attention to wlf first, Sun Guo writes this page), install. Order, line. ⑴ Ministry of Economic Affairs Standard (CHCVAnax Worker-20.

5. Description of the invention () -OCH3), 5.29 (s (2H (.CH2-), 6.83-6.91 &lt; m, 3H, 3 ^, 5 ^ 6 ^ H) 16, 7.18-7.37 (111,; ^, 4'-denier); ^ 111/2: 3630+>; elemental analysis: (3 Η15ΒΓΝ203, calculated value C: 52.91, H: 4.16, N: 7.71, experimental value: C: 52.95, Η: 4.20, N : 7.68 ο (2〉. 2- (2 -Methoxymethyl) · 3,4-dimethyl * fu "Nan Pin [2,3-c] Bing-5 (2H> -Carbohydrate (lιυο ) Using compound 11-10 (5.00 g, 0.01 mol) as the raw material, referring to the synthesis and treatment purification method of compound ΙΗ-1, compound III-10 can be obtained as pale yellow crystals with a yield of 3.01 g ( 71.7%). Mp: 170 ° C (dec.); IR (KBr) v max: 2050-3600 (〇.H), 1685 (C-Ocm ^ V (C2H5〇H) Amax: 280nm &lt; el.53xl 〇4); NMR (DMS0-d6) S: 2.37 (S, 3H, C-4-CJ ^ 3), 2.43 (s, 3H, C.3_CH3), 3.84 (s (3H, -OCH3) (5.22 (s, 2H, -CH2-) i6.6〇 (; dilHi 3, -H), 6.88 (t, lH> 5, -H), 7.0i (d, lH16, -H) i7.27 ( t) lH4, -H) ,; MS, m / z: 300 (M +); elemental analysis: c16h16n2〇4, calculated value C: 63.99, H: 5.37, N: 9.93, experimental value: C: 63.8. , H: 5 31, N: 9.83 o Example 1-1 1 d> · 5-bromo-2- (3-methoxybenzylmethyl) -3,4- Methyl sulfonate [23_cI 呲 嗤 -6 (2H) -one (Il-ii) with 2_ (3_ methyl gas stupid methyl) _3,4- dimethyl sulfonate [He] oxazole 21 204351 Λ 6 It 6 Printed 5i printed by the Zhenggong Anti-crime Cooperative of the Ministry of Economic Affairs. 5. Description of the invention () -6 (2H) -vehicle (Ι-11> (5.00 g, 0.018 moong>) as raw material, Referring to the synthesis and treatment method of compound Ι-1, the residue obtained at the end is first separated by column lamination method (silicon transfer ·· gas imitation), and then recrystallized with a gas imitation-ditol mixture solvent to obtain Compounds 11-11. White crystals, yield 6.12 g (93.70.mp: 148-151 ° C; IR (KBr) 1 /: 1712 &lt; C-0) cm'1; UV (chci3 &gt; λ max: 318nm (£ -2.07X104); 1h-nmr (cdci3) δ: 2,46 (d, 3Η, C-4-Cdan 3), 2.51 (s, 3H, C-3-CM3), 3.76 (s, 3Η , -OC Dan 3), 5.26 (s, 2Η, -C Dan 2-), 6.66-6.87 (m,-Η), 7_25 ", 111, 5,-mutual> Chuan 3, 111/2: 363 ^ + > Elemental analysis: (: Η Br 16 15 ν2〇3, calculated value C: 52.91, Η: 4.16, Ν: 7.71, experimental value: c: 52.80, H: A.ll, N: 7.80〇 (2 ). 2 · (3 · Methoxybenzylmethyl) -3,4 · Dimethylfuranhydrazine [2,3_c] pyrazole_5 (2H)- (III-11) Using compound 11-11 (5.00 g, 0_014 mole) as the raw material, referring to the synthesis and treatment purification method of compound III-1, compound III-11 can be obtained as yellow crystals, yielding 1.26 Gram (30.0 *) 〇mp: 214〇C (dec.); IR (KBr) v max: 2000-3200 (〇.H), ι7〇7 (C-Ocm ^ iUV &lt; CHC13) Λ max: 292nm &lt;ε-1.68xl〇4); 1H-NMR (MeOH-d4> 3: 2.44 (s, 3H, C-4-C ^ 3), 2.52 (s, 3H, c-3-CH3), 3.69 (s, 3H, -0CH3), 5.34 (s, 2H, -CH2-), 6.19.6.85 (mI3H, 2 &gt; & 4 &lt; &amp; 6 &gt; -H) &gt; 7.13-7.53 (m, lH, 5 &gt; -H ); MS, m / z: 300 -22-(please read the back-to-back precautions # 蜞 write this page) This paper uses the standard BB home sample standard (CNS) T4 regulation (210X297 public; Jt) 204351 Λ6 Printed by the Ministry of Economic Affairs + Central Government Bureau of Industry and Commerce β · Cooperative V. Description of the invention () (M +); elemental analysis: C16H16N2〇4, calculated value C: 63.99, H: 5.37, N: 9.93, Experimental values: C: 63_91, Η: 5.32, N: 10.〇3. Example 1-1 2 (1> _ 5-Huan-2- (4-Methoxybenzylmethyl> -3,4-dimethylpyridine [2,3-c] pyrazole · 6 (2Η)- Ketone (11-12) with 2- (4-methoxybenzylmethyl) -3,4-dimethylpyran [2,3_c] _pyrazin-6 (2! H) -one (1-12 ) (5.00g, O.OU mole) as the raw material, the compound can be obtained by referring to the synthesis and processing and purification methods of compound II-1. White crystals, yield 6.18g (94.6 *>. Mp: 169-172〇C ; IR (KBr) ν: 1712 (C-0) cm -1; UV (CHC1,) Amax: 32〇nm (ε &quot; 2.83χ1〇4): 1h-NHR (CDC13) §: 2.47 (d, 3H , C-4-CH3), 2.50 (8,3H, C-3-CH), 3.77 (s, 3H, -〇CH), J —3y * 5.22 &lt; s, 2HI-CH2-), 6.83 (dI2H1J -8.8Hz, 3, &amp; 5f-H), 7.12 (d, 2H, J-8.8Hz, 2 '&amp;6'-denier); MS, m / z: 363 (M +); Elemental analysis: C16H15BrN2. 3. Calculated value C: 52.91, Η: 4.16, Ν: 7.71, experimental value: C: 52.79, Η: 4, 01, Ν: 7.63〇 (2). 2- (4-甲 气 笨 甲(2H) -Carboxylic acid (III-12) Using compound 11-12 (5.0 g, 0.0014 mole) as raw material, refer to the synthesis, treatment and purification methods of compound ΙΙ1-1 (recrystallization solvent is vinegar)睃 G vinegar-a drunk mixed solvent), that is to call the compound .Pale yellow needle crystal, yield 3.37 g (80,2%). -23-(please read the notes on the back of the first page # 蜞 妙 此 页} 装 · 定 _ 线 &lt; This paper is used in ft scale side a National Tsinghua University (CNS) T4 regulation (210x297 ^ 〇435 &gt;-V. Description of the invention) mp: 210C (dec.); IR (KBr) ^ 〇 &amp; χ: 2050-3300 (〇.H), X667 (please read the precautions before writing this page) &lt; 〇-0) 〇.-; UV &lt; 〇2Η5〇Η) λω3χ: 282ηΒ (ε.2.8〇χ1〇4); 1h_ orbit ( M_-V δ: 2.36 (S, 3H, C-4_CV, 2 5〇 (s 3h c 3. CH3) (3.71 &lt; sI3H, -0CH3) 15.21 (s, 2H, .cH2-), 6.80 (d &gt; 2H, elemental analysis: C16H16N2〇4 'Calculated value C: 63.99, H: 5.37, N: 9 93, experimental value: C: 63_89, H: 5.42, N: 9.90ο Example 1-1 3 ⑴.5-Bromo- 2-0,4-Dimethoxybenzylmethyl> _3.4 · Dimethyl 23c pyrazole (2H) -one (11-13) with 2- (3,4-dimethoxybenzyl ) _3,4-Dimethyl 11 pyran [2,3_. 】 Tonazol-6 (2 ^ 〇_one (1-13) (5.00 g, 0.016 mol) as a raw material, referring to the compound II-1 synthesis and treatment purification method, you can get compound 11-13 〇

White crystals, yield 6.17 g (98.10. Mp: 177-18 ° C; IR (KBr) V: 1712 (C-0) cm'1; UV

ID £ 1X 4 1 (CHC13) Amax: 318nm &lt; e-2-28Xl °): H-NMR (CDC13 ^: 2.48 (s, 3H, C-4-CH3) i2.50 (si3H, C-3-CH3 ), 3.83 &amp; 3.85 (s, the Ministry of Economic Affairs # 揮 央 # quasi-bureau A industrial consumer cooperation cooperative seal 51 6H, 2x-0C) i3), 5.22 (s, 2H, -C) i2-). 6.73-6.87 (m , 3H, benzene ring protons); MS, m / z: 393 (M +); elemental analysis: C17H17BrN2〇4, calculated value: C: 51, 92 ′ H: 4.36, Ν: 7.12 , Experimental value: C: 51.85, H: 4.31, Ν: 7 · 〇8〇-24-National paper size (CNS) T4 regulation tM2] OX2iU public it) 204351 Jingyaobiyang The quasi-bureau A industrial price cooperative cooperative printed 5i. V. Description of the invention () (2). 2- (3,4-Dimethoxybenzyl) · 3 t dimethylfuridine hydrazine 丨 2,3. 】 Pyrazole-5 (2H> -Carboxylic acid (mu>) Using compound 11-13 (5.0 g, 0.013 mol) as raw material, referring to the synthesis, treatment and purification methods of compound ΙΙΙ-1 Compound ΙΙΙ-13 〇 white crystals, yield 1.20 g (28.〇〇. Mp: 182〇C (dec.); IR (KBr) i /: 2200-3600 (〇.H), 1682 -1 * (CO ) cm; UV &lt; CHC13) Λmax: 290nm (ε-2.21x1ο4). 1H. NMR (DMS0-d6) δ: 2.47 (s, 6H, 2x-CH3), 3.72 (s, 6H12x-) &gt; 5. 28 (s, 2H,), 6.67 (m, 1H, 6 *-il) t 6.86-6.95 (m, 2H, 2 '&amp; 5'-] i); MS, m / Z: 330 (M +); Elemental analysis. C η M 17 18 2〇5, calculated values: C: 61.18, H: 5.49, N: 8.48, experimental values: 0.600, H: 5.40, N: 8.56 〇Example 1-1 4 (1) . 5-Bromo-2- (2-phenanthrenyl) -3,4-dimethyl sessine 42,34] Tonazol-6 (2H) -one (11-14) (5-bromo-2 -(2-thienylmethyl) -3,4-dimethylpy-rano [2,3-c] pyrazol-6 (2H) -〇ne (11-14)) with 2- (2- phenphenmethyl) -3, 4-Dimethylpyridine [He] 咣 嗤 _6 (2H) -one (1-14) (5.0 〇g 〇.〇19 Mole) as a raw material, refer to the synthesis of compound II-1 Treatment purification method, namely T Compound HM. White crystals, yield 6.25 g (97.〇 *) 〇mp: 164-167, IR (KBr) v: 1713 (C-0> cm 1; UV -25-(please read the back first Matters Sun Yaoqiao this page) Binding · Binding-Line. This paper is used in the standard side a Η 家 橒 准 (CNS) f 4 specifications (210X297 male dragon) Λ 6 116 204351 V. Description of invention ()

&lt; CHC13) Λ max: 318 nm (ε-2.24xl〇4); 1H-NMR &lt; DMSO-d6) Q: 2.51 (s, 3H.C-4-C Dan 3), 2.60 (s, 3Η, C-3-C Dan 3), 5.55 (s, 2Η, -CH2-), 6.95-7.16 &lt; m, 2H, 3 &lt; &amp; 4i-H), 7.47 (dd, 1Η, J1.2 Hz, J -4.7Hz, 5'-denier); MS, m / z: 339 (M +); elemental analysis: Ci3Hii BrN2〇2S, calculated value: C: 46.〇3, H: 3_27, N: 8.26, Ben test Values: C: 46.15, H: 3.36, N: 8.40 〇 (2). 2- (2 · phenanthrenyl) _3,4 · dimethylfurfurone [2,3_c] pyrazole_5 (2H> · Carboxylic acid (111-14> Using compound II-14 (5.00 g, 0.015 mol) as raw material, referring to the synthesis and treatment purification method of compound III-1, compound III-14 can be obtained as pale yellow crystals, yield 2.33g (56.3〇.mp: 189 ° C (dec.); IR (KBr) v: 2200-3500 &lt; 0-H) 1707 max (CO) cm-1; UV (HOH) A: 280nm (ε-1.66 xl〇4) ^ Ή-2 5 max 'NMR (DMSO-d.) δ: 2.46 (s, 3H, C-4-CH〇), 2.52 (s, 3H, C-3-C ^ 3>, 5.55 (s, 2H, -C ^ 2-), 6.93-7.13 (m, 2H, 3 '&amp; 4' · Dan),

7.46 (dd, lH, 5 '-] i); MS, ni / Z: 276 (M +); elemental analysis: C H19N 13 12 ^ 〇3S, calculated values: C: 56.51, H: 4.38, N: 10.14, Experimental value: c: 56.62, H: 4.42, N: 10.19 〇Example 1- 1 5 (1). 5-bromo-2- (2-phenylmethyl) -3,4-dimethylpyridine 【 2,3-c】 Pyridin-6 (2H) -one (11-15) -26-This paper is not used in China National Standards (CNS) A 4 specifications (210x297 g; ":" (please read诮 背 而 之 注 问题 # 塡 ¾This page) -Installation · Line-Ministry of Economic Affairs

V. Description of the invention () The Ministry of Economic Affairs + Central Bureau of Standards s: Industrial and Consumer Cooperatives printed 5i. 2- (2-Pyridinylmethyl) -3,4-Dimethylpyridine [23c] Boom · 6 ( 2h>-Turtle (1-15) (5.00 g, 0.02 mol) was dissolved in 100 ml of gaseous solution, and a bromine-gaseous solution was slowly added dropwise at room temperature [Bromo (5.00 g, 0 mol) Ear> Dissolve in 50 ml of gaseous imitation] 'When the reaction is completed, add sulfinic argon potential until the reaction solution is almost colorless.' In case, collect the quick liquid. For the sink, add water for about 400. Milliliters to dissolve excess sulfite argonine, insolubles are washed with 10% broken thorium solution, and then dissolved with gas imitation, combined with the previous gas imitation solution, washed with water several times, the gas imitation layer is dried over anhydrous sulfur After dehydration, the solvent is again encountered, and the filtrate is evaporated under reduced pressure to remove the solvent. The resulting residue is recrystallized with a mixed solvent of gaseous drunk, that is, T to obtain compound II-15. Light yellow diamond crystal, yield 6.52 g (97 · 3%). Mp: 179-182 ...; IR (KBr) 1 /: 1715 (C_0) cm_1; UV max (CHCl) Ama: 3118nm (ε-1.34xl〇4); 1H-NMR (CDC1) δ: • 3 Π1 α X j 2.52 &lt; s, 3H, C-4-CH), 2.56 &lt; s, 3H, C-3-CHo ), 5.40 (s, 2H &gt; one j -3-CH2-), 7.07-7.33 (m, 2H, 3, & 4, H), 7.67 (dt, 1H, Jl.9Hz, J-7 · 6Ηζ , ν-dan> -and); MS, m / z: 335 (M +); elemental analysis: C14H12BrN3〇2, calculated position: C: 50.32, Η: 3.62, N: 12.57, experimental value: C: 50.39 ， Η: 3.49, Ν: 12 · 62〇 (2> · 2- (2 · pyridylmethyl) _3,4_dimethyl, Fudi 胼 [2,3-c] pyridine-5 (2Η>- Carboxylic acid (111-15> Using compound 11-15 (5.00 g, 0.015 mol) as the raw material, referring to the synthesis, treatment and purification methods of compound ΙΙΙ-1, you can obtain compound ΙΙΙ-15 〇-27-(please read first Please keep in mind #Items to write this page} Binding &lt; Order · Line · This paper is used in ft scale side "S Family Sample (CNS) T4 Specification (2 丨 0x297g; ¢) 5 3 420 66 ΛΒ Ministry of Economic Affairs Printed by the Employee Consumer Cooperative of the Central Bureau of Labor and Development Fifth, the description of the invention () The yellow product's yield is 3.55 first (87 30. mp: 192 ^ (dec.); IR (KBr), max: 21〇.355 〇 (〇.H) 1682 (C-〇) Cm'1: UV (C2H5〇H> Amax: 282nm (e.2.2〇xl〇4): lH. NMR &lt; Me0H-d4) S: 2.51 (s, 3H , C-4-CH3) (2.54 &lt; s (3H, C.3-CH3), 5.46Cs, 2H, -CH2-), 7.05 (d, lHI3 ^ H), 7.31 (t &gt; lH, 5 i -H>, 7.78 (dt, lH, 4D, 8.5 () (d, lH, 6, denier); (M +); elemental analysis: C14H13N3〇3, calculated value: 0: 61.99, H-.4.83, N : 15.49, experimental values: C: 61.85, η: 4.89, N: 15.54. Example 1-1 6 (1>. 5 · Bromo-2- (3-pyridinylmethyl> _3,4_dimethylpyridine [23c] pyridine_6 (2H> -Illustration (11-16) Using 2- (3-pyridylmethyl) _3,4 · dimethylpyridazine [Hu pyrazole 6 UH) -one (1-16) (5.00 g, 0.02 mole) as reference Compound II-1 synthesis and treatment purification method, you can get compound 1116. White crystals, yield 6.40 grams (95. 5 *). Mp: 191-193〇C; IR &lt; KBr) y max: 1715 ( C »〇) cm'1; UV (CHC13> Λ max: 316nm (ε-2.18x10); 1H-NMR (CDC13) δ: 2.51 (s, 3H, C-4-CH3) 12.52 (s, 3H, C -3-CH3) .S.aaCs ^ H, -CH2 Ο, / ^ Βζί, ΙΗ, δ1-]!), 7.54 (ά, ΙΗ, 4 ».Η) 855ζπ12Η) 2 '&amp; 6, -dan) "3 ^ / 2: 335" +); elemental analysis: (: 144231_1 ^ 〇2, calculated value: C: 50.32, Η: 3 · 62, Ν: 12.57, experimental value: c: 50〇44, H: 3.49 , N: 12.63 ο -28-(please read the back-end precautions # fill in this page) the size of this paper is t «B Jia Shu Bi (CHS) &lt; P4 specification (210x297 g *) A 6 B 6 2043¾12 ^ V. Description of invention () (please read the precautions and fill in this page first) (2). 2- (3-pyridylmethyl) · 3,4-dimethyl, husband骈 [2,3-c] pyridine-5 (2H> -carboxylic acid (111-16> Using compound 11-16 (5.00 g, 0.015 mol) as raw material, refer to the synthesis and treatment purification method of compound III-1 , You can get compound III-16 〇 yellow crystals, yielding 3.00 g (73.8 *) 〇mp: 214〇C (dec.); IR (KBr) i /: 2100-3600 (0-H), 1687 max ' (CO) cm 1; UV (CH OH) Λ: 280nm (e -2.62xl〇4); 1H-z-> max NMR (DMS0-d) §: 2.48 (s> 3H, C-4-CH " ), 2.51 (sI3H, C-3- ° —3 CH3), 5.44 (s, 2H, -CH2-), 7.36 (t, lH, 5, -H), 7.58 &lt; d, lH, V-dan) , 8.47-8.49 (m, 2H, 2 '&amp; 6' _ mutual); MS, m / z: 271 (M +); elemental analysis: C14H13N3〇3, calculated value: c: 61.99, H: 4.83, N: 15.49, experimental values: C: 62_03, H: 4.92, N: 15.54. Example 1-1 7 (1). 5-Bromo-2- (4-vft bite methyl dimethyl ton 0 South scorpion [23_cjt bite _6 (2H) -Illustration (11-17) Central Bureau of Standards, Ministry of Economic Affairs Printed by the β-consumer cooperatives with 2- (4-pyridinyl dimethyl siphon [2,3_c] pyrazol-6 (2H) -one (1-17) (5.0 g, 〇. .〇2〇mol) as a raw material, referring to the compound II-1 synthesis and processing purification method, you can get compound n_l7 〇 light yellow crystals, a yield of 6.45 g (963%>. MP: 177-18〇t : IR (KBr) i; max: 1712 (c_〇) cm-l; uv (CHClg) λ max: 316ηιηζ ε-^ 7χ1〇4); 1H-NMR (CDC13) q: 2.47 (s13H, C- 4-CH3), 2.53 (s13H, C-3-CH3) i 5.33 (s, 2H, -29-This paper is used for a standard 8 a standard iMCNS) Τ4 regulation (210x297 g *)% 04351 A 6 H 6 V. Description of the invention () -CH2-), 7.02 &lt; d, 2H, J_6.1Hz, 3, &amp; 57-H), 8.57 (dd, 2H, J-1 · 5Hz'J-6 · 1Hz ' -Dan>; MS, m / z: 33 5 (M +); elemental analysis: C14H12BrN3〇2, calculated value: C: 50.32, H: 3_62, N: 12.57, inspection value: C: 50.28, Η: 3 · 51, Ν: 12 · 39〇 (2). 2- (4-pyridylmethyl) _3,4 · dimethylfuranhydrazine [He] 咣 嗤 · 5 (2Η> carboxy 睃 （ΙΙΙ-17) to compound 11-17 (5.0 g, 0.01 Smol) as the raw material, referring to the synthesis and treatment purification method of compound ΙΙ1-1, compound III-17-17 can be obtained as yellow crystals with a yield of 2.20 g (54.1.mp : 228 (dec.); IR (KBr) y nax: 2100-3600 (〇.η), 1685 (C = 0) cm; UV (CH OH) Δ: 28〇nm (ε -1.65xl〇4v 1H- 2 5 max υ} n NMR (Me0H-d4) S: 2.51 (s, 3H, C-4-C ^ 3), 2.59 (s, 3H, C-3-CH3), 5.50 (s, 2H, -CH2 -), 7.07 (d, 2H, 3-H) &gt; 8.52 (dj2H, 2, &amp; 6, once); MS, m / z: 271 (M +); elemental analysis: C14Hi3N3〇3, calculated value: C: 61.99, H: 4.83, N: 15.49, experimental values: C: 61.85, Η: 4.68, N: 15.30 〇 (please read the back to the notes first # fill in this page)

Printed 3i -30 by the Central Bureau of Economic Affairs of the Ministry of Economic Affairs κχ 工 氣 price Cooperation Co., Ltd.-This paper is used in the middle of the HB home sample (CNS) TM regulation (210X297) ¢ 351, the invention description () (2). 2- , 3-, 4_ tri-substituted furosemide [2 3 cj pyrazole _5 · formaldehyde (V) manufacturing

POC13 DMF R2〆,

CHO Yaji Ministry of Fire and Industry Engineering Cooperation Du Yin 5i R2, R3,%, the same formula (B) Scheme 3 As shown in Scheme 3, compound III is dissolved in an appropriate solvent (such as sulfoline) in a metal catalyst ( Such as activated copper) heating to carry out decarburization reaction, after the reaction is complete, after purification by column layer analysis and recrystallization method, you can get the corresponding 2,3,4-tri-substituted "Fransuan [2, 3- £ ^ pyrazole (^) (2,3,4-trisubstituted furo [2,3-c] pyrazole (IV), dissolve compound IV in an appropriate solvent (such as DMF) to perform vielsmieir formation ( f ormylation) to obtain the corresponding 2,3,4_tri-substituted cough β Nanpin [2,3-c] product of valer-5-carbaldehyde (V>. Example 2-1 (1). 2, 3,4-Trimethylfuran [2,3-c] pyrazole (IV-1) Preparation of active copper: dissolve copper thiosulfate (10g) in water and add in portions; ^ 語 粉 （3_ 〇g), there will be Shen Che, in case of Yun, then wash the strip with 10 »application solution, then wash with water, dry * dry, it is available active copper. -31-Regulation (2 丨 0X297 male; ^ (Please read the back and the precautions ## to write this page) installed · Λ 6 Η 6 Ministry of Economic Affairs, Central Bureau of CXC Printed by Xiaozuo Cooperative V. Description of the invention () Dissolve compound III-1 (5 g, 0.026 mol) in anhydrous quinces (60 mL), and add active copper (1 g, 0.016 mol) ), Sample the sample at 20〇t for 30 minutes, after the reaction is completed, cool to room temperature, trick with 10% Rifido solution, Yu Yun, "Liquid is extracted again with gas imitating, water washing gas imitating layer several times After dehydration with anhydrous magnesium sulfate, the solvent was evaporated to remove the solvent, and the residue was purified by column laminar folding method (silicon-gas imitation) to obtain compound IV-1. Light brown crystals with a yield of 0.25 g (6.5. Mp: 68-7l10; UV (CHCl3) Anax: 249nm; iH-NMIUCDCiyg: 2.06 (s, 3H, C-4-C Dan 3), 2.33 (s, 3H, C-3-C Dan 3 >, 3.37 (s, 3H, [^ • (: mutual 3), 6.86 (3, 111, .-5-dan); 1 «13, 111/2: 15〇0 +); elemental analysis:% Η1〇Ν2〇, calculated value: C: 63.98, H: 6.71, Ν: 18 · 65, inspection value: 0: 63.79, H: 6.75, N: 18.504 (2). 5 · 甲 醢 -2 , 3,4 · Trimethylfurfuran "Nansang [2,3-c] pyrazole (νο at 5-10 ° C, press N, N-bismethylmethylamine amine (DMF) (30g, 〇.41 mol) was added dropwise to vaporized phosphate (10 g, 〇.〇65 Mo ), Below 10 〇c: After stirring for 20 minutes, the compound IV-1 (1 g, 〇〇〇〇67 mole) dissolved in bismethylmethanamine (20 ml) was allowed to drop After entering, remove 30 cents pounds at 0-5 ° C, stir at room temperature for 30 minutes, then pour the reaction solution into ice water, add sodium sulphate to neutralize, and let stand for 8 hours. Extracted with gas imitation, dehydrated with anhydrous sulfur, dehydrated the solvent, the residue was purified by column laminar folding method (silicone knee_air imitation>) to obtain compound V-1 〇 pale yellow crystals, yield 〇. 95g (80 *) ° mp: 122-124 ° Q; IR (KBr) ^: 1645 (C-0) cm 1; UV IQ £ 1X -32-(please read the precautions before writing the book Page) Binding · Binding _ Line-This paper is used in the national standard of a standard size (CNS &gt; T4 specification (210x297cm ;! t) Λ 6 Π 6 204351 V. Description of the invention () (° Η013) λ max: 320nm; 1H-NMR (CDC13) δ: 2 · 5〇 (s, 3h,-3. CH3), 2.53 (s, 3H , C-4-CH3), 3.86 &lt; s, 3HiN-CH3), 9.69 (Si 1 ^ 1,-(: den 0); {&gt; 13,111 / 2: 178 (1 &gt;1+); element Analysis: ./1〇1^2〇2, calculated values: C: 60.70, H: 5.66, Ν: 15.72, experimental values: C: 60.74, h: 5.53, N: 15.62 〇 Example 2-2 (1 ) · 2-G-3.4-Dimethylfuranhydrazine [2,3-cl oxazole (iv_2> active copper preparation: dissolve copper thiosulfate (10 g) in water, add fenfan powder in portions. G), there will be precipitation, if it is filtered, it is washed with 10 * 氲 睃 solution, then washed with water, and dried, which is available active copper. Compound III-2 (5 g, 0.024 mol) Dissolve in anhydrous sodium chloride (60 ml), add active copper (1 g, 0.016 mol), and remove it under 200 ° C. After the reaction is completed, cool to room temperature and treat with 10% acid solution In case of runoff, the runoff liquid is then extracted with gaseous imitation, washed with chloroform layer several times, dehydrated with anhydrous sulfur, the filtrate is evaporated to remove the solvent, and the residue is purified by column chromatography (miao shift 1_air imitation). Compound I V-2. Light yellow crystals, yield 3_2 g (80 *). Mp: 32-34 ° C; UV (CHC13> Λ: 259nm; 1H-NMR (CDC13) §: 1.4 (t, 3H, -CW, 2. l (s, 3H.C-4-C_ ^ 3), 2.4 (s, 3H, C-3-CH3), 4,03 (q, 2H, -CH2CH3), 6.9 (s, 1H, C- 5 -H); MS.m / z: 164 (M +); elemental analysis: C9H12N2〇, calculated value: C: 65.83, η: 7.37, N: 17.06, experimental value: C: 65.80, H: 7.34, N: 17.l7〇-33-The BB standard of this paper is used in the BB home «quasi (CNS) Ή regulation 怙 (210x297 male dragon) (please first ffl-ift the back« (ό Cautions of Sunguo writing book If) installed线 经济 部 屮 央 #Public Bureau KX 工 消 諀 貀 社 訊 社 印 Μ Λ 6 Π 6 V. Description of the invention () (2). 2-dagger-3, dimethyl * furan [2,3-c] pyridine嗤 -5-Formaldehyde (V-2) Under 5-1010, hit N, N_bismethylmethylamine <DMF> (30g, 0.41 Mojie) to make dropwise to the gasification dish male (Phosphoryl chloride) (l〇g '0 065 mole), after stirring for 20 minutes at less than 10Ό, the compound IV-2 (1g, 0.0061) dissolved in bismethylmethylamine (20ml) Mohr) After dropping, stir at 0-5 ° C for 30 minutes, and then stir at room temperature for 30 minutes. Into ice-water was added and the breaking rates Suo, allowed to stand, the crystals deposited there, too suddenly, the crystals were collected, drained, to obtain compound V · 2. Light yellow needle crystal, yield 0.8 g (68. mp: 93-94 ° 〇; IR (KBr) u: 2720 (-CH0), 1680 (C-0) cm * 1 max; UV (CHCl〇) Λ: 320nm; 1H-NMR (CDC1) 8: 1.43 &lt; t, 3H, 3 max ^ -CH2CH3 &gt;, 2.53 (s, 3H, C-4-CH3), 2.57 (s, 3H, C-3-CH3 &gt;;, 4.13 (q, 2H, -0HoCHo), 9.65 (s, 1H, -CHO); MS, m / z: 192 (M +) ~ 2 3: Elemental analysis: C1 () H12N2〇2, calculated value: C : 62.49, H: 6.29, N: 14.57, experimental values: C: 62.35, H: 6.40, N: 15.63. (Please read the notes before M and then write this page) Ministry of Economic Affairs Central Bureau κχ Printed by the Gongxiaozuo Cooperative Society, 31 papers are printed on China's S Jiayubi (CNS) Ή specifications (210x297 gong) ^ 04¾¾1 Λ 6 Η 6 V. Description of invention () (3) · 2,3,4-Triple substitution -5-weight base * Fu Yan Piao [2,3-cl pyrazole (VI) manufacturing (2-, 3-, 4-trisubstituted-5-acylfuro [2,3-cI pyrazoles (VI))

RCOX (RCO) 2 O Lewis acid

R

COR (VI) R2, R3. R4, the same formula (B) Scheme 4 The compound IV is dissolved in an appropriate solvent (such as Shuobeng) in the presence of Lewis acid (such as 98% of ^ 卩 〇4) for ballasting 'After the reaction, after purification by column chromatography and recrystallization, the corresponding target VI is obtained. (Please take note of Iwlft ’s consideration first.) The real bureau of the Ministry of Economic Affairs is the CX Gongye *: printed by the cooperative. Example 3-1 5-Dagger Weight-2,3,4-Sanpingji, Furan胼 [2,3-. ] Pyrrh (71-1) First, prepare a mixture of 9 ^ phosphorus and vinegar (10 g). After mixing compound IV-1 (1 g, 0.0067 moles) and vinegar (I8.8 g 0.2 moles), heat to 35 ° C, and make the mixture dropwise (the temperature should not be exceeded) After 40 ° C>, after stirring for 90 minutes at 55-6 ° C, the temperature was lowered to below 2.0%, and 80 ml of water was added. After a minute, the reaction solution was extracted with chloroform, 100 ml of water and 10% potassium solution Washing, washing again with water, dehydrating with anhydrous thiomagnesium, the solvent is distilled off, and the retentate is subjected to column chromatography -35-

The size of the paper is used in the BB family sample (CHS) 4 specifications (210X297 public: 4) Λ 6 Η 6 204 sister five, invention description () tituted furo [2,3-c] pyrazole-5-carboxylic acid chl 〇, ride (VII)) 'It is possible to dissolve compound VII in a common solvent (such as stupid). Please read the back first and pay attention to the matter # 淒 苒 木 页) react with various amines by column chromatography After purification by recrystallization, the corresponding target VIII 0 can be obtained. Example 4-1 (1) .2,3,4-Trimethyl * Fu Pinpin [2,3- £:] Bite-5- Male chloride (711-1) The compound III-1 (1 g, 0.0052 mol) was suspended in 100 ml of benzine, and two gasification sulfite ^ (thionyl chl〇ride) (5 g, 0. 〇42Moong> After heating and refluxing until the reaction is completed, the solvent is distilled off, the residue is washed with n-hexane, the petroleum bond and vinegar C_ »S | i (petroleum ether. Ethyl acetate) are recrystallized to obtain compound VII -; L 〇 white crystals, yield 0.93 g (85 *). Line IR (KBr) ν max: 1720 (0-0) 0111-1; 1Η-NMR (CDC13) §: 2.5〇 (s, 6H, C-3-CH3 & C-4-CH3), 3.83 (s, 3H, NC ^); MS, m / z: 212 (M +); elemental analysis: C9H19 ClN2〇2, calculated values: c: 50.84, Η: 4.27, N: 13.17, experimental values: C: 50.65, H: 4.42, N: 13.40 (2). 2, 3, 4-three Methyl Fusarone [2,3-c] pyrazole-5-carboxamide was tested by the β part of the center ^ β Gong Xiao &quot; Cooperative Society κ compound compound VII-1 (1 g, 〇.〇〇 47 moles) dissolved in 40 ml of stupid gas, mixed with gas and gas. After the reaction is completed, the solid part is washed with water, the solid part is washed with water, and the dry part of the filtrate is washed with water, dehydrated with anhydrous sulfuric acid, and steamed. After removing the solvent, the residue is combined with the solid, and separated by the column-folding method (silicone, gas imitation) to obtain the compound VIII-1. -37-Λ 6 116 Ministry of Economic Affairs, Central Bureau of Economic Development cx 工 消費 $ :: Cooperative printing 3i V. Description of the invention () White crystal, yielding 0.55 g (6U). Mp: 148-15〇Ί〇; IR (KBr) v: 3300, 3120 &lt; NHo), 1670 max 2 (CO) cm ' 1; UV (CHC1 „) Λ: 288nm; 1H-NMR &lt; CF3COOD) §: 3 max 2.66 (s (3H, C-3-CH0 or C-4-CH0) (2.73 (s, 3H (C-3- CH0 or —3 — 3 — 3 C-4-C (3), 4.17 (s, 3H, N-CM3); MS, m / z: 193 (M +); elemental analysis: C9HnN3〇2, calculated value: C : 55.95, H: 5.74, N: 21.75, experimental value: C: 55.83, Η: 5 · 70, N: 21.71o Example 4-2 N-A · 2,3,4-trimethylfurfurine [2,3-c] benzo-5-carboxamide (VIII-2) Compound VII-1 (1g, 0.0〇47mol) was dissolved in 40mL of benzine and stirred with methylamine. After the reaction was completed, it was washed with water and dehydrated with anhydrous thiomagnesium. The material was purified by column chromatography (silica methane · gasoline>, that is, T gave compound VIII-2 0 as yellow crystals, with a yield of 0.8 g (82 *>). .1 mp: 186-188 T1: IR (KBr) y: 3340 (NH), 16 30 (C-0) cm ^ max; UV (CHCl ^) Λ: 279nm; 1H-NMR &lt; CDC10) δ: 2.40 ( s, 3H, 3 max j C-3-C ^ 3 or C-4-C ^ 3), 2.50 (s, 3H, C-3-C ^ 3 or C-4-C ^ 3), 2.93 (d , 3H, -C0NH-CHo), 3.79 (s) 3H, N-CH "), 6.50 (s, lHI -3-j N denier); MS, m / Z: 207 (M +); elemental analysis: C1QH13N3 〇2, calculated value: C: 57.96, Η: 6.32, N: 20.28, experimental value: C: 57.79, Η: 6.30, N: 20.28 ο -38-(please read the precautions first Item write this page) Threading · The size of this paper is used in the aa family ttiMCNS) T4 specifications (2 丨 0x297 male dragon) Λ 6 116 2,04351 V. Description of invention () Example 4-3 N · C · -2, 3,4-Trimethylfurfural [2,3_c] 咣 · 5 · Carboxy weight amine (VIII-3) Compound VII-1 (1 g, 〇〇〇〇47 Modou) dissolved in Ben 4 Milliliters, add daggeramine (2g, 0_〇44mol) and stir. After the reaction is completed, wash with water, dehydrated with anhydrous thiomagnesium, the filtrate is evaporated to remove the solvent, and the residue is subjected to column delamination method (broken knee-gas Imitation) purification to obtain compound VIII-3. Yellow crystals, yield 0.98 g (94 *). Mp: 172-174〇C; IR ( KBr) v: 3360 (NH), 1630 (0-0) 0111-1

IQ α X; UV &lt; CHC13) Λmax: 285nm; 1H-NMR (CDC1) §: 1.40 (t, 3H, (please read back to the precautions # fill in this page) f -CH2 &lt; ^ 3), 2.43 ( s, 3H, C-3-C blue 3 or C-4-C Dan 3), 2.53 (s, 3H, C-3-C Dan 3 or C-4-C Dan 3), 3.43 (m, 2H, NHC (2CH3), 3.8 (s, 3H, NC 3), 6.57 (s, 1H, N); MS, m / z: 221 (M +>, 177 (M + -44>; elemental analysis: (31 : ΙΗ15Ν3〇2, calculated value: c: 59.71, h: 6.83. N: 18.99, experimental value: C: 59.79, H: 6.69, N: 18.87 Xiao 1Y-Cooperative Society ¾. Example 4 · 4 N-isopropyl_2,3,4 · trimethylfuranhydrazine [2,3_c] pyrazole_5 · carboxamide (VIII-4) Compound VH-iL (: L grams, 0.047 moles) dissolved in 40 ml of stupid, add isopropylamine (2 grams, 0.033 moles) and stir, referring to the compound synthesis method, using the same reaction conditions and treatment methods , You can get compound VIII-4 〇 yellow crystals, a yield of 1.0 g (98%>. 鈑 度 尺 张纸 本 -39-% Λ 6 II 6 V. Description of the invention () mp: 168-1701C; IR ( KBr) v max: 3400 (NH), 1630 (CO) cm K5 Gongxiao of Shiyangbei Bureau of Economic Development &lt; v Zuoshe 5i; UV (CHC13) Λ max: 280nm; H-NMR (CDC31) δ: 1.27 (d, 6Ht-CH (CH3> 2), 2.47 &lt; s, 3H, C-3-CH3 〇r C -4-CH3), 2.50 (s, 3H, C-3-C Dan 3 or C-4-Cji3), 3.83 (s, 3H, NC Dan 3), 4.17 (m, 1H, -CH (CH3) 2 ), 6.20 (s.IH.NH); MS, m / z: 235 (M +), 177 (M + 58); elemental analysis: C12H17N3〇2, calculated value: c: 61.26, H: 7.28, N: 17.86, Experimental value: C: 61_30, H: 7.35, Ν: 17 · 69〇Example 4-5 N-isopentane-2,3,4 · trimethylfurfural [He] pyridine · 5 · carboxamide ( VIII-5) Referring to the synthesis method of compound VIII-1, under the same reaction conditions and treatment methods, isoamylamine (3 g, 0.034 mole) was reacted with compound VII-1 (1 g, 0.0047 mole). To obtain compound VIII-5. Yellow crystals, yield 1.2 g (97 *). mp: 146-148〇C; IR (KBr) u: 3330 (NH), 1630 (C-0) cm'1 max; UV (CHC10) Λ: 285nm; 1H-NMR (CDC10) Q: 0.93 (d, 6H, 3 max J -CH (CH3) 2>, 1.33-2.00 (m, 3H, -CH2-CH (CH3) 2>, 2.43 (5, 3H, C-3-CH „or C-4-CH0) , 2.53 (s, 3H, C-3-CH0 or C-4- _3 —J —3 CH0), 3.37 (m, 2H, -NHCH.CH .-), 3.77 (s, 2H, N-CH-) , 6.40 —3 L mono / mono / (s, lH, NH); MS, πl / z: 263 (M +), 177 (M + -86); elemental analysis: C 丄 Η Η21Ν3〇2, calculated value: c: 63.85, Η ·· 8.04, Ν: 15 · 96, experimental value 0: 63.77, Η: 8.14, Ν: 15.87 〇40-(please read back on W1 first ((0 的 許 訊 資 記 #Fill in this page) Order · This paper is used in the B national standard (CNS) Ή specification (2) 0X297 Gonglong &gt; printed by the GX Industrial and Consumer Cooperative of the Central Bureau of the Ministry of Economic Affairs 2,0 V. Description of invention () Example 4- 6 N-cyclohexyl 2,3,4-trimethylfuranhydrazine [2,3_c] pyridine · 5 · pyramide (VIII-6) Refer to the synthesis method of compound VIII-1 with the same reaction conditions and treatment Method, by reacting cyclohexylamine (3 g, 0.0047 mole) with compound VII-1 (1 g, 0_0047 mole), compound νιιι · 6 can be obtained. Black red crystal Yield 0.15 g (6M). Mp: 138-140 °; IR &lt; KBr) y: 3350 &lt; NH), 1630 (0-0) 0111-1; UV (CHC1) λ: 280nm; 1H-NMR ( CDC10) §: 0.73-2.10 «3 Melon α X j (m, 11H, cyclohexyl protons), 2.30 (s, 3H, C-3-GH0 or C- 1 3 4-CH), 2.40 (s, 3H, C -3-CH orC-4-CH0), 3.70 (s, 3H, N- ° one o one 3 C) ^ 3), 6.17 (s, lH, N) p; MS, m / z: 275 (M +) , 177 (M + -98); S elemental analysis: C15H21N3〇2, calculated value: c: 65.43, H: 7.69, N: 15.26, experimental value: C: 65.49, H: 7.61, N: 15.320 Example 4-7 N -(N *, N '-&gt; monomethylaminopropylamino) -2,3,4-trimethyl * buminan [2,3-c] pyrazole_5 · carboxamide (VIII-7 ) Referring to the synthesis method of compound VIII-1, using the same reaction conditions and treatment methods, make N, N-dimethyltrimethyldiamine (N, N_dimsthyltriine-thylenediamine) (4 g, 〇.〇4 Moong;) and Compound vHa (1 g, 0.047 mole) is reacted to obtain compound vιΙ · 7. Yellow crystal, yield 0.6g (50 *) 〇mp: 235-238〇C; IR (KBr) υ: 3410 (NH), 1630 (C-0) max -41-Λ 6 Η 6 (please read the back first And pay attention to this item # Crucible to write this page) Install-Bookmark _ Line. This paper is used in the standard 曒 家 曒 Bi (CNS) regulations IM210X297 male dragon) Employee consumption cooperation of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs Duin 3i __Π6__ 5 , Description of the invention () cm &quot;1; UV (CHC10) Λ: 286nm; -NMR (CDC1 ^): 1.67 3 max J (m, 2H, NH-CH2C ^ 2CH2-), 2.20 (s, 6H, N (C Once 3) 2), 2.33 (s, 3Η · C-3-CH „or C-4-CH.), 2.50 &lt; s, 3H, C-3-CH or C-4-CH), 3.30 (t , 2H, -CH2CH2N &lt;), 3.43 &lt; m, 2H, NHCH2), 3.8〇 &lt; s, 3H, N-CH.), 7.67 (s, lH, NH); MS, m / z: 278 (M + ), 177 (M + -101); Yuan-3 elemental analysis: C14H22N4〇2, calculated value: c: 60.41, H: 7.97, N: 20.13, experimental value: C: 60.40, H: 7.89, N: 20.23 Example 4-8 N- (p-Coxycarbonylmethylenebenzyl) _2,3,4 · trimethylfuranhydrazine [2.3-c] pyrazole-5-carboxamide (VIII-8) Reference compound VIII- The synthesis method of 1, using the same reaction conditions and processing methods, make 1- (4-amine stupid) L 爃 CSg (2.83 g, 0.016 mol) and compound VII-1 (1.7 g, 0.08 mol) ) Reaction, compound VIII-8 〇 yellow crystals, yield 1.1 g (66%). Mp: 213-215〇C; IR (KBr) v: 3300 (NH), 1730 (0-0), max 1660 (C-0) cm '; UV (CHC10) λ: 305nm; 1H-NMR (CDC1 ") 3 max 3 §: 1.23 (t, 3H, -CHC0H3), 2.43 (s, 3H, C-3-CH0 or C-4- 2 —3 C ^ 3), 2.60 (s, 3H, C-3-C ^ 3 or C-4-C ^ 3>, 3.57 (s, 2H, C6H5-C) ^ 2-C0 -), 3.80 (s, 3H, N-CM3), 4.13 (q, 2H, OC ^ 2CH3), 7.23 (d, 2H, J-8Hz, 3, &amp; 5, denier), 7.60 (d, 2H , J_8Hz, 2, & 6, and-, 8.13 (3, 11 calls); "3 ,! 11/2: 3550+); Elemental analysis: (: 19th 2 / 3〇4, calculated value: C : 64.21, Η: 5.96, Ν: 11 · 82, experimental value: C: 64.30, -42-(please read the notes before Ml and fill in the wooden page) a Η Family Sample Standard (CNS) T4 regulation (210x297 g; it) Printed by the Ministry of Economic Affairs, Central Bureau of Labor and Social Security, β Industrial Consumer Cooperatives V. Description of the invention () H: 5.84, N: 11.70 〇Example 4-9 1 ^, Heart dimethyl-2,3,4-trimethylfuranhydrazine [2,3-(: 1pyrazole-5-carboxyl chain amine (VIII-9) Refer to the synthesis method of compound VIII-1, the same The reaction conditions and treatment methods make Methylamine (2 g, 0 · 044 mole) is reacted with compound VII-1 (1 g, 0.0〇47 Mo circles), to give compound VIII-9 billion yellow crystals, yield 0.94 g (89%). mp: 116-118〇C; IR (KBr) v: 1610 (C-0) cm-1; UV max 1 (CHCl) Λ: 285nm; 1H-NMR (CDC1) Q: 2.43 (s, 3H, C- 3 -ό max 〇CH. Or CA-CH.), 2.46 (s, 3H, C-3-CH0 or C-4-CH „), 3.17 —j 一 j —3 —3 (s, 6H, N ( CH3) 2), 3.80 (s, 3H, N-CH3); MS, m / z: 221 (M +), 177 (M + -44); elemental analysis :, calculated value: C: 59.71, H: 6.83, Ν : 18 · 99, experimental value: C: 59.60, H: 6.71, N: 18.75. Example 4-1 0 1 heart dihex-2,3,4-trimethylfuranhydrazine [2,3 &lt;] Azole-5-carboxyl chain amine (VIII-10) Referring to the synthesis method of compound VIII-1, using the same reaction conditions and processing methods, di-G-based amine (2 g, 0.027 mole) and compound VII-1 (1g, 0.0047mol) reaction to obtain compound VIII-10. Yellow crystals, yield 0.19g (81%). Mp: 152-154〇C; IR (KBr) i ^: 1605 (C-0 ) cm_1; UV max * -43-(Please read IK1 first and read the notes #fill this page) This paper is used in the national standard (CNS) T4 regulation ΙΜ2Κ1Χ297 g; it) Bi Yangmu, Ministry of Economic Affairs Printed by the quasi-bureau β industry consumer cooperative 5i V. Description of the invention () (CHt313) λ max: 285nm: 1H-NMR (CDC13) δ: 1.16 (m, 6H, N (CH2CH3) 2), 2.33 (Si6H, C-3-CH3 & C-4-GH3), 3.37 &lt; m, 4H, N (CH2CH3) 2), 3.70 (s, 3H, N-CH3); MS, m / z: 249 (M +), 177 (»+ -72>; elemental analysis: 〇1; ^ 1 / 3〇2, calculated value: (;: 62.63,11: 7 68, N: 16.85, experimental value: C: 62.71, Η: 7 · 60, N: 16.81. Example 4-1 1 5- (N-hexakistriphenyl carbonyl> · 2,3,4 · trimethylfurfurone [2,3 _c] ^ Bite ( VIII-11) With reference to the synthesis method of compound VIII-1, with the same reaction conditions and treatment methods, make six gas tons (piperidine) (3 g, 0.034 mole) and compound VII-1 (1 g, 0 .〇〇47 mole> reaction, that is, the compound VIII-11〇 white crystals, yield 1.05 g (8M> 〇mp: 156-158〇C; IR (KBr) u: 1610 &lt; C-0 ) cm'1; UV max (CHCl〇) Λ: 280nm; 1H-NMR (CDCl0) §: 1.67 (m, 6H, i max J CHftCHrt 2-2 -N &lt; &gt; CH) CH0CH0 '-2'2_37 ( s, 6H, C-3-CH. &amp; C-4-CH〇), 3.57 2 -2 -3 -i ch2ch2 (m, 4H, 'N &lt; CH2CH2 & CH2), 3.80 (s, 3H, N-CH3); MS, m / z: 261 (M +), 177 (M + -84), 150 (M + -111); elemental analysis: C14H19N3 〇2, calculated values: C: 64.35, H: 7.33, N: 16.08, experimental values: C: 64.22, H: 7.30 , N: 16.12〇-44-(please first-ift 背 而 之 之 見見 資 #Fill in this page) Binding-Order _ Line. The size of this paper is "Chinese a B home standard pregnancy (CNS) T4 specification (210X297 male dragon ) Fifth, the description of the invention () Example 4-1 2 5- (N-morphofungon carbonyl> _2,3,4-trimethylfuranhydrazine 2 3 cl (VIII-12) Refer to compound VIII-1 Synthetic method, with the same reaction conditions and processing methods, make xifu ton; (mQrpholine) (3 g, 0.03 mole) and compound VII-1 (1 g, 0.0047 mole), ie Available compound VIII -12 〇

White crystals, yielding 1.1 grams (89%). mp: 183-18510; IR (KBr) v: 1610 (0-0) 00 ^ -UV max 1 (CHC13) λ max: 280nm; 1h-NMR (CDC1) δ: 2.37 (S, 3H, C-3- CH3 or C-4-CH), 2.39 (s, 3H, C-3-CH or C-4-CH), 3.67 —j —3 CH0CH0 —2—2 -N &lt; 〇 \ (s, 8H, CH2CH2 ;, 3.76 (s, 3H, N-CH3); MS, m / 2: 263 〇4 +), 177 (1 &lt; 1 + -86>; elemental analysis: (; 13111: ^ 3〇3, calculated value: (;: 59.30, Η: 6.51, Ν: 15 · 96, experimental values: C: 59_20, H: 6.39, N: 15.81 〇 Example 4 · 1 3 Ministry of Economic Affairs + Central # quasi bureau Beigong Xiaobi cooperative print 3i (please read the back-end precautions # item to write this page) N- (NT-Hexaargonium) -2,3,4 · Trimethylfurazane [2,3-.] Pyrazole -5-Carboxamide (VIII-13) Referring to the synthesis method of compound VIII-1, using the same reaction conditions and processing methods, make methyl hexa-I-tonzaki (N-methylpiperazine) (3 g, 0.03 mol) > Reaction with compound VII-1 (1 g, 0.0047 mol), that is, T gives compound VIII-13. -45-This paper is used in the standard a B home standard (CNS) T4 specification (210x297 *) A 6 116 E3, Central Bureau of Standards, Ministry of Economic Affairs: 5i printed by the industrial and consumer cooperative. V. Description of invention () Yellow knot , Production Mu 1.2 first (92〇〇mp: 145-147〇C; ir (KBr) ^: 1615 (0-0) 001-1; UV Ql & X (CHCl) Λ: 288nm. H-NMlUCDCl.> δ: 2.33 (s, 3H, -N- • j ID 3 X * 3 N-CH), 2.40 (s, 6H, C-3-CH. & C-4-CH0), 2.43 (m, 4H, j —j 3 ch2cM2 ch2ch2 -N &lt; CH2CH2 &gt; N-CH3 \ 3.67 (m, 4H1-N &lt; CH2CH2 &gt; N-CH3 &gt;, 3.83 (s, 3H, N-CH3); MS, m / z: 276 ( M +), 177 &lt; M + -99), 99 (M + -177); elemental analysis: C14H2〇N4〇2, calculated values: C: 60_85, H: 7.29, N: 20.27, experimental values: c: 60.74, H: 7.32, N: 20.35 〇Example 4-1 4 N-propane-2,3,4-trimethylfurfurazide [2,3_c] pyridinecarboxamide (VIII-14) Reference compound VIII-1 synthesis method Under the same reaction conditions and treatment methods, propylamine (0.61 g, 0.011 mole) and compound VII-1 (1 g, 0.0047 mole) were reacted to obtain compound νιΙΙ_14. Yellow crystals, yield 0.7g (63%). mp: 113-115〇C; IR (KBr) v: 3270 (NH), 1630 (C-0) cm_1 max; UV (CHC13) λ max: 275 nm; 1H-NMR &lt; CDCl3) g: 0.94 (t, 3H, NH (CH2) 2C ^ 3), 1.53 (m, 2H,-NHCH2C] ^ 2CH3>, 2.37 (s, 3H, C-4 -C Dan 3), 2.49 (s, 3H, C-3-C Dan 3 ), 3.33 (^, 2H, -NHC ^ 2CH2CH3), 3.76 (s, 3H, N-CH3), 6.23-6.63 (br, 1H, -NH-); MS.m / z: 235 (M +); element Analysis: C12Hl7N3〇2, calculated value: c: 61.26. H: 7.28, N: 17.86, experimental value: C: 61.35, h: 7.31, N: 17.69〇-46-(please read the notes on »lq first #Fill in this page) This paper uses 8 Chinese samples of Zhongqu (CNS) &lt; P4 regulations (2 丨 0 &gt; &lt; 297 male dragons) 2 Λ 6 Η 6 β 工 消 讀 of the Central Standards Bureau of the Ministry of Economic Affairs Cooperative Society Printing Κ 5. Description of the invention () Example 4-1 5N-butane-2,3,4-trimethylfurfural [2,3-c] pyrazole-5-carboxamide (VIII-15) For the synthesis method of compound VIII-1, butylamine (0.75 g, 0.011 mol) and compound VII-1 (1 g, 0.0047 mol) can be reacted with the same reaction conditions and processing methods. Compound VIII_15 was obtained. Yellow-white complex, yield 1 g &lt;; 8 5 *>. Mp: 109-110 ° C; IR (KBr) v: 3 300 (NH), 1630 (0-0) 010-1 max; UV (CHC13) Λmax: 284nm; 1H-NMR (CDC13) §: 0.93 (t, 3H, -NH (CH) CH), 1.20-1.71 (m, 4H, -NHCH0CH0CH0CH0), 2.40 Z j 2-2 —2 3 (s, 3H, C-4-CH „), 2.53 (s, 3H, G-3-CHo), 3.20-3.60Cni, 2HI-J —3- -NHCH2CH2CH2CH3), 3.78 (s, 3H, N -CH3), 6.20-6.57 (br, 1H, -N denier-); MS, m / z: 249 (M +); elemental analysis: Ci3H19N3〇2, calculated value: C: 62.63, Η: 7.68, N : 16.85, experimental value: C: 62.60, H: 7.64, N: 16.83 〇Example 4-1 6N-penta-2,3,4 · trimethylfurfurazide [2,3-c] 咣 嗤 -5 · Carboxamide (VIII-16) refers to the synthesis method of compound νιιι-1, using the same reaction conditions and processing methods, to make pentylamine (0.96 g, 0.011 Moong) and compound VII-1 (1 g, 0.047) Mohr) reaction to obtain compound VIII-16. Light yellow crystals, yield 0.9g (73%). mp: 106-107t:; IR (KBr) v max: 3360 (NH), 1630 (C-0) cm '-47-(please read the precautions before Sun fills this page) This paper is used for ft scale China a S Home Bibi (CNS) Τ4 specification (210x297 g; a :) Ministry of Economic Affairs, Central Standards Bureau 13: printed by the industrial and commercial cooperatives Λ 6 Π6 V. Description of invention (); UV (CHC1) Λ: 285nm ; 1H-NMR (CDC10) δ: 0.65-1.05 (m, 3H, -NH (CH2) 4-CJ ^ 3), 1.08-1.72 (m, 6H, -NHCH2C]; [2Cji2 CH2CH3> , 2.37 (s, 3H, C-4-CH3), 2.49 (s, 3H (C-3-CH3>, 3.30-3.52 (ni, 2H, -NHCli2- (CH2> 3CH3), 3.74 (S, 3H, NC ^ 3>, 6.15 · 6.52 (br, lH, -N and-); MS, m / z: 263 (M +); elemental analysis: C14H21N3 〇2, calculated value: C: 63.85, H: 8.04, N : 15.96, experimental values: C: 63.91, H: 8.12, N: 15.84. Example 4-1 7 (1). 2-dagger-3, 4-dimethyl, furan pin [2, 3 _ c Bubi Azole-5 -carboxychloride (v 11-2) compound III · 2 (1 g, 0.048 mole) was suspended in 100 ml of anhydrous stupid and added with digaseous sulfite (4.6 G, 〇39.39Moong>, heated to reflux until the reaction is completed 'evaporate the solvent, the residue was washed with petroleum ether, dried, you can get Compound VII-2. Yellow-colored crude product, yield 1 g (92 *> 〇 (2). 2-Cj-3,4-dimethyl * fu * nanpin [2,3-c] Bite- 5-Sutramine (〃111-17) Dissolve compound VII-2 (1 g, 0.0044 mole) in 100 ml of agar, ventilate with gas, and heat to reflux. After the reaction is completed, filter all over , The solid part was washed with water and dried. The filtrate part was washed with water, dehydrated with anhydrous thiomagnesium, the solvent was distilled off, the residue was combined with the solid, and separated by column chromatography (miao shift gas imitation), that is Available compound VIII_17. Pale yellow crystals' yield 0.65 g (71 *). Mp: 265-267〇C; IR (KBr), ax: 3300, 3150 (NH2), 1680-4 8-(please first (Please read the back and forth precautions #items to write this page) Pack. Line-Λ Λ A 5t paper (CN home I side I *) 204351 Μ Economic Ministry 屮 央 # quasi-bureau β 工 消 你 Cooperation Du Yin ¾. V. Description of the invention () -1 I (CO) cm; UV (C Η OH) λ: 283nm; H-NMR &lt; DMSO-d) § λ. D IQ 3 X ^: 1.14 (t, 3H, N-CH CH), 2.37 (s, 6H, C-4-CH &amp; C-3-CH), zj one 3 one 3 3.98 &lt; q, 2H, -CH2CH3), 6.97-7.42 (br, 2H, -NH2) ; MS.m / z: 207 (M +); elemental analysis: C1 () H13N3〇2 , Calculated value: C: 57.96, H: 6.32, N: 20.28, Experimental value: C: 57.79, H: 6.38, N: 20.34. Example 4-1 8 N-A-2- Cj-3, 4-Di A基》 夫 b 南 拼 [2,3-c] Instructed Jun-5-Brozoamine (VIII-18) to treat compound VII-2 (1 g, 〇〇〇44 Molar> dissolved in 100 ml of stupid, pass The solution was heated to reflux with methylamine until the reaction was completed and washed with water. After the dehydration layer was dehydrated with anhydrous sulfur dissolve, the filtrate was evaporated to remove the solvent. The residue was purified by column chromatography (silica gel-gasoline) to obtain compound VIII 18 〇 light yellow crystals, yield 0.85 g (87%). mp: 171-172〇C; IR (KBr) 1 /: 3340 (NH), 1640 (0-0) 010-1; UV (CHC1.) Λ: 277nm; 1H-NMR (GDC10) §: 1.41 (t , 3H, 3 max 3 -CH.CH.), 2.43 (s, 3H, C-4-CH) f2.55 (s, βΗ, Ο-3-CH0), 2.94 (d, 3H, -NHG ^ 3 >, 4.09 (q, 2H, -C ^ 2CH3), 6.16-6.57 (br, lH, -N) iCH3>; MS, m / Z: 221 (M +); elemental analysis: CnH15N3〇2, calculated value: C : 59.71, H: 6.83, N: 18.99, experimental values: C: 59.65, H: 6.80, N: 18.95 〇Example 4-1 9 heart has-2-hexane-3,4-dimethylfurananhydrazine [ 2,3-(:) pyrazole-5-iron weight amine-49-(please read the notes before filling #filling this page). Binding. Thread-This paper scale is used in "Η 家 楳Standard (CNS) T &lt; 1 specification (210X297 male dragon) 2 * 0 Μ Central Ministry of Economic Affairs β Bureau of Industry and Commerce *: printed by the cooperative 5i V. Description of the invention () (VIII-19) Compound VII-2 (1 g , O.OO44 mole), dissolved in 100 ml of Ben, heated with Cj amine to avoid the flow until the reaction is complete, washed with water, after the Ben layer was dehydrated by anhydrous sulfur, the solvent was distilled off, and the residue was passed through the column Chromatography (silica methane-gas imitation> purification, you can get the chemical compound VIII-19. Light yellow crystals, yield 0.6g S8%). Mp: 129-131〇C; IR (KBr) ^ max: 3360 (NH), 1640 (C-0) cm'1; UV (CHC13) λmax: 281nm; 1H-NMR (CDC13) §: 1.〇3.1.53 (m, 6H, N-N_CH2-C) i3 &amp; -CONHCW, 2.43 (s, 3H, C-4. ^ I2.55 (s, 3H, C-3-CH ^), 3.13-3.70 (m, 2Ht-CONHGH ^ CH3), 4.07 (q, 2H, NN-CH2CH3) (5.97-6.53 (br, lHf-NH); MS, m / z: 235 (M +); elemental analysis: C12Hl7N3 〇2, calculated values: C: 61.26, H: 7.28, N: 17.86, experimental values: C: 61_32, H: 7.32, N: 17.750 Example 4-2 0 N-propan-2-C * -3, 4. Dimethyl "• Fenan Pin [2,3-c] ^ Bite · 5_ fusarium (VIII-20) Compound VII-2 (1 g, 0.044 mole) was dissolved in Ben 100 Ml, add propylamine (0.6g, 0.0097mol) and heat to reflux until the reaction is complete. Wash with water. After dehydrating the anhydrous layer with anhydrous magnesium sulfate, the solvent is distilled off, and the residue is passed through the column layer. Purification method (silica gel-aeroform) to obtain compound VIII-20 〇 pale yellow crystals, yield 0.65 g (S9 *) 〇mp: 113-115〇C; IR (KBr) »/: 3360 ( NH), 1640 (C-0) cm * 1 -50-The paper is used in the standard side a B Jiayubi (CN5) f 4 gauge (210X297 male dragon) (jingxian nil reading back The Notes # Xiaoshan awakened this ΪΙ) i installed. _ Set line. Coffee Μ Λβ ____________ Η 6

The Ministry of Economic Affairs + Central Government and the β Gongxiao IV Cooperative Society printed 5i V. Description of the invention (); UV (CHC13) Λffiax: 275nm; 1H-NMR (CDC13) δ: Ο · 96 (t, 3H, -N (CH2) 2C denier 3), 1.42 (t, 3H,-NCH2C_ ^ 3), 1.55 (m, 2H, N-CH2 C ^ 2CH3), 2.43 (s, 3H, C-4-C Dan 3), 2.55 ( s, 3H, C-3-Cdan 3), 3.13 -3.61 (m, 2H, NC_ ^ 2CH2CH3), 3.85-4.37 (m, 2H, N -CM2CH3), 6.31-6.57 (br, lH, -N and ); MS, m / z: 249 (M +); elemental analysis: c ′ 13 H19N3〇2, calculated value: C: 62.63, Η: 7.68, N: 16.85, experimental value: C.-62.70, H : 7.72, N: 16.85 〇Example 4-2 1 N -butan-2-L »· 3,4-dimethyl efu" Nanpin 【2,3-c】 Gou_5 · Jun chain amine (VIII -21) Compound VII-2 (1 g, 0.044 mole) was dissolved in 100 ml of benzene, butylamine (0.8 g, 0.097 mole) was added and heated to reflux until The reaction is completed, washed with water, after the dehydration layer is dehydrated with anhydrous sulfur, the solvent is distilled off, and the residue is purified by column chromatography (silica gel-aeroform) to obtain compound VIII-21 0 as pale yellow crystals. Rate 〇.64 g (560. mp: 79-801C; IR (KBr) v: 3370 (NH), 1640 (C-0) cm'1 * max * UV (CHC1) λ: 286nm; ^ -NMIUCDCl.) δ: 0.93 (m, 3H, -N ^ ni dx 3 (CH2) 3CH3), 1.17-1.60 (m, 7H, N-CH2CH2CH2CH3 &amp; N-CH2 CH) &gt; 2.45 (s, 3H, C-4-CH0), 2.53 (s &gt; 3H, C-3-CH „), 3.17- A J — &lt; 3 — 3 3.52 &lt; m, 2H, NCH2CH2CH2CH3), 4.10 (q, 2H, N-CH2CH3), 6.13-6.60 (br, lH,-knock-); &quot; 3, 1] 1/2: 263 (11+); elemental analysis: 〇14 \ 11 ^ 3 〇2, calculated value ： C: 63.85, H: 8.〇4, Ινίδιό, experimental value: c: -51-This "Standard iAW SB Family Sample Standard (CNS) T * I specification (210x297 male dragon) in Zhang scale (210x297 male dragon) And pay attention to if #item page j install. Order · line. Ministry of Economic Affairs Bureau of Central Standards cx industry consumer 1V cooperation Du Yin 5i 5. Description of invention () 63.80, H: 8.16, N: 15.92〇 Example 4- 2 2 N-isopropyl_2 · C · 3,4-Dimethyl * Fu 胀 胼 【He】 嘥 嗤 _5 · Carboxylamine (VIII-22) Refer to the synthesis method of compound VIII-1, the same reaction Conditions and treatment methods, isopropyl ketone (0.6g, 0.0〇97mol) was reacted with compound νιι2 (1g, 0.0044mol), namely compound VIII-22. Light yellow crystals, yield 0.75 g (68 *) 〇mp: 110-113eC; IR (KBr) v: 3400 (NH), 1630 (C-0) cm_1 mx; UV (CHC13> λmax: 286nm; 1H -NMR (CDC13) δ: 0.58-1.72 (m, 10H, -N-CH- (CH3> 2 & N-CH2CH3), 2.44 &lt; s, 3H, C-4-CH3), 2.57 (s, 3H, C-3-C Dan 3), 4. ll (q, 2H, N-Cj ^ 2CH3); MS, m / z: 249 (M +); elemental analysis: C13H19N3〇2, calculated value: c: 62.63, H: 7.68, N: 16.85, experimental values: C: 62.59, H: 7.60, N: 16.74. Example 4-2 3 1 ^, 1 ^ -dihex-2-hex-3,4-di Methylfurfural [2,3- £:] pyrazole-5-carboxamide (VIII-23> Referring to the synthesis method of compound VIII-1, using the same reaction conditions and treatment method, di-Gamine (0.7 g , 〇.〇〇97mol> reaction with compound VII-2 (1g, 0_0〇44mol), you can get compound VIII-23 〇 light star crystals, yield 0.55g (47 *) 〇mp: 63-65〇C; IR &lt; KBr) v: ΙόΙΟζΟ-Οοιη * 1; UV (CHC1 „) max 3 -52-(please read the back and forth precautions # 蜞 写 此 页) outfit-line · book In the paper scale, 8 B standards (CNS) &gt; P4 specifications (210x297 male dragon) 204351 Λ 6 116 V. Description of invention ( Max: 275nm; H-NMR (CDC13> Q: 0.91 -1.72 &lt; m, 9H, N &lt; CH2C »3 CH2CH3 & N-CH2CH3), 2.43 (S) 6H, C-4-CH &amp; C- 3-CH, C «2CH3 3.44 (q, 4H, &lt;. once., ', 4 · 06 (q · 2H, N-. Denier /%); M3, m / z: 263 (M); element Analysis: C14H21N3〇2, calculated values: c: 63 85, H: 8.04, N: 15.96, experimental values: C: 63.88, H: 8.15, N: 15.92 ^ Example 4-2 4 Synthesis of N-benzyl-2-C · -3,4-dimethyl "• Fr. Nanshao [23_c] tonbite · 5 streakamine (VIII-24) with reference to compound VIII-1 Method, using the same reaction conditions and treatment methods, react stupid methylamine (1.03 g, 0.0097 Molong) with compound VII_2 (1 g, 0.0004 Mohr) to obtain the compound νιιι · 24. Light star crystals, yield 0.6 g (46 *). mp: 133-135〇C; IR (KBr) 1 /: 3480 (NH), 1640 (0-0) 00 ^; UV (CHC13> λmax: 280nm; 1H-NMR (CDC13) §: 1.40 (t, 3H , N-CH2CH3), 2.43 (s, 3H, C-4-CH), 2.57 (s, 3H, C-3-CH), 3.90-4.23 (m, 2H, -N-CH2-C6H5) I4.57 (q, 2H, N-CH2CH3), 7.30 (m'5H, -CH2-C6H5); MS, m / z: 297 (M +); elemental analysis: C17 H19N3〇2, calculated value: C: 68 · 67 , Η: 6.44, N: 14.13, experimental values: 0: 68.74, H: 6.49, N: 14.00〇53-(please read the precautions before writing this page) Install ·-line-this paper Standard side use of China a coal (iMCNS) 1 Μ specification (210x297 male tf) ta., Λ c 6U ΛΙΙ

Printed by the EX Industrial and Consumer Cooperatives, Bureau of Standards, Ministry of Economic Affairs, M. V. Description of Invention () Example 4-2 5 ν · [2- (ν ', N, dimethylamino group> l group] -2_ 已 _3 4_ Dimethyl, fendi [2,3- (:] oxazole-5-carboxamide) (^ 111_25) Referring to the synthesis method of compound VIII-1, using the same reaction conditions and treatment methods, make Ν, Ν- 双Methyl hexamethylenediamine (0.85 g, 0.0097 mole) reacted with compound VII · 2 (1 g, 0.044 mole) to obtain compound VIII-25. Light yellow product, yield 0.95 G (77%). Mp: 55-5610; IR (KBr) 1 /: 3340 (NH), 1635 (0-0) 010 ^; m & x UV (CHC13> λ max: 276nm; 1H-NMR ( CDC13) §: 1.42 (t, 3H, N- CH CH), 2.20-2.73 (m, 14H, C-4-CH0 &amp; C-3-CH & -CH ° —3—32 Cji2N (CM3) 2 ), 3.47 (m, 2H, -NC ^ 2-CH2N &lt;), 4.07 (q, 2H, NC) i2CH3>; MS, m / Z: 278 (M +); elemental analysis: ci4H22N4〇2, calculated value: C: 60_41, H: 7_97, N: 20 · 13, experimental values: c: 60.43, H: 7.97, N: 20.20. Example 4-2 6 N- (3,3-dibenzyl)- 2-G-3,4-dimethyl, fumarozide [2,3-c] oxazole-5-carboxamide (VIII-26) Refer to the synthesis method of compound VIII-1 With the same reaction conditions and treatment methods, 3 · diphenylpropanamine (2.1 g, 0.0097 moles) was reacted with compound VH · 2 (1 g, 0.0004 moles) to obtain compound νιΙΙ · 26 Ο Light yellow crystal, 1.4 g of soap (76 *) 〇-54-(please read the notes first and then write this page) Packed. Ordered · The paper size is the same as that of country B ( CNS) Ή Regulation «5 (210X297 public; η A 6 H 6 2〇435i V. Description of the invention) mp: 134-135 * 0; IR (KBr) v: 3395 (NH), 1630 (0-0) 001-1 max 1 (please read the precautions written by Er Qiao first); UV (CHCl〇) Λ: 286nm; H-NMR (CDC1.) Δ: 1.37 (t, 3H, 3 max 3 N- CH2CH3), 2.25 (m, lH, -CH (C6H5) 2), 2.38 (s, 3H, C-4-CH3), 2.51 (s, 3H, C-3-Cji3), 3_32 (m, 2H,- NCH2C ^ 2CH〇, 3.81-4 · 23 (m, 4H, -N-CM2-CH2-CH &lt;, N-C_ ^ 2CH3>, 6.17-6.53 (br, 11-ton-), 7.23 (1! 1, 1 (^, 2 public 1: and) Chuan 3, 111/2: 401 ^ +); Elemental analysis: C25H27N3〇2, calculated values: C: 74.79, H: 6.78, N: 10.47, experimental value: C: 74.84 ,. H: 6.69, N: 10.52〇Example 4-2 7 5- (4-benzylhexakrypton carbonyl) -2 · hex-3,4-dimethyl · fu [2,3-c] pyrrolidine (VIII-27) Referring to the synthesis method of compound VIII-1, using the same reaction conditions and processing methods, N-penyl six-tonne (N-phenylpiperazine &gt; (l 6 grams, 0.097 moles> react with compound VII-2 (1 grams, 0.040 moles) to obtain compound VIII-27.

Light yellow crystal, soap production 0.85 g (55. mp: 128-130 ° C; IR (KBr) u: 1625 (0-0) 001 ^-, UV max (CHCl〇) Λ: 277nm; 1H- NMR (CDC10) δ: 1 · 43 (t, 3H, N- ό 0161X 3 Printed by the Ministry of Economic Affairs, Bureau of Industry and Commerce, Co., Ltd. $ i CH CH0), 2.43 &lt; s, 6H, C-4-CH0 &amp; C-3-CH0), 3.06-3.30 (m, i —3 —3 —3 ch2ch2 ch2ch2 4H,-N &lt; CH CH &gt; N_), 3.76-3.9 6 (m, 4H,-N &lt; CH, 4.06 (q, 2H, N-CHoCHo), 6.73-7.10 (m, 5H, ArH); MS, m / z: 352 3-(M +); elemental analysis: C2QH24N4〇2, calculated value: C: 68_16, Η : 6 · 86, -55-The Chinese standard (CNS) IM regulations (210X29 / Gonglong) are used for this paper scale. 2 i5 0Λ Λ 1> Ό V. Description of invention () Ν: 15 · 90, experimental value ： C: 68 2〇, H: 6 9i, n 15 86 〇Example 4-2 8 5- [4- (2-Pyridinyl> Hexaargonium carbonyl] _2-〇_3,4-dimethylfuran Spell [2,3-c] ton bite (VIII_28> Refer to the synthesis method of compound VIII-1, and use the same reaction conditions and processing methods to make 1_ (2 'order bite base) six gas tons (l- (pyridyl) piperazine > (I. 6 g '0_〇〇97 Molar;) reacted with compound VII_2 (1 g, 〇_〇〇44 Molar), ie Available compound VIII-28. Light yellow crystals, yield 0.95 g (61 *). -1; UV 280nm; 1H-NMR (CDC1) §: 1.43 (t, 3HfN-mp: 129-13110; ir (KBr) u: 16l8 (C-0) cm max (CHC1.) Λ ^ 3 max (please read the precautions before filling in this page) _ Pack. Order-Ministry of Economic Affairs + Central Bureau of Quarantine ΚΧ 工 消 作 合作 DU India ¾. CH tons), 2.45 (s, 6H, C-4-CH. &Amp; C-3-CD, 3.60-4.01 (m, ^ 〇— 3 — 3CV Lan 2 8H, 'N &lt; CH2CH2 &gt; N' 5,4.10 &lt; q, 2H, -N-CH2CH3), 6.60-6.73 (m, 2H, 3,, 5, -H), 7.27-7.60 (m, lH &gt; 4, -H); 8.01-8.20 ( m, lH, 6'-mutual); &gt; 13,111 / 2: 3530+); elemental analysis: 〇19112 / 5〇2, calculated value: C: 64.57, H: 6.56, N: l9.82, Experimental values: C: 64.49, Η: 6.46, N: 19.75. Example 4-2 9 N- (C · Gascarbonyl) -2-C-3,4-. Carboxamide (VIII-29) -56 Methyl * Fu Wei Pin [2,3-c Bubiya 5-line-SB Home Standard Pregnancy (CNS) «r 4 Regulations (210X297 public goods) 2〇435i Ciyang Consumers' Bureau of Standards & Technology, Co., Ltd. 51 51. Description of the invention () With reference to the synthesis method of compound VIII-1, using the same reaction conditions and treatment methods, the (Ethyl carbazate) (l g, 0.0097 mol) reacted with compound VII-2 (1 g, 0.0〇44 mol) to obtain compound VIII-29 〇 pale yellow crystals, yield 0.65 g (5〇 »). mp: 225-226〇C; IR (KBr) v: 3290, 3230 (NH). 1740 (-COOC2H5), 1660 (-CONHNH-) cm-1; UV (CHC13) Λmax: 280 nm; 1H-NMR ( CDC13) §: 1.36 (t, 3H, N-CH2CH3>, 1.52 (t, 3H, -C00CHoCHo), 2.46 (s, 3H, C-4 -CH0), 2.55 (s, 3H, C-3- CH0), 2—3 — 3 —3 4.19 (q, 2H, N-CW, 4.23 (q, 2H, -COOC) i2CH3); MS, m / z: 294 (M +); elemental analysis: C13H18N4〇4 , Calculated value: C: 53.05, H: 6.16, N: 19.〇4, Experimental value: C: 53.11, Η: 6 · 10, N: 9.12. Example 4-3 0 (1). 2-isopropyl- 3,4-Dimethylfuranhydrazine [2,3-c] pyridin-5-carboxylic acid gas (VII-3> Take compound III · 3 (1 g, 0.045 mole) suspended in 100 ml After adding sulphur dichloride dichloride (4.6 g, 0.039 mol), heat to reflux until the reaction is complete, evaporate the solvent, wash the residue with petroleum squint, dry it, and use column chromatography Method (silica gel · gas imitate) purification, you can get compound VII-3. White product, yield 0.93 g (8M). Mp: 162-164lC; IR 〇CBr) Vmax: i680 (C-0> cm_1; LJV <C2H5 4 1 〇Η> λmax: 313ηΠ (ε-1.2x10); H-NMR (CDC1) ^: 1.33 -57-(Please read the notes beforehand Note this matter and write this page again) Binding · Binding-Line. The standard of this paper is to use the standard Β Η home standard pregnancy (CNS) A 4 regulations (2 丨 0> &lt; 297 gonglong) A 6 Η 6 Central Ministry of Economic Affairs揣 准 扃 β 工時 訂 訂 Cooperative printed 3i V. Description of the invention () (d, 6H, -CH (GH3 &gt; 2), 2.48 (3,6H, C-4-CH3 & C-3-CH3), 4.52 (m, 1H, -C denier); MS, m / z: 240 (M +); elemental analysis: JIN ..., calculated as 13 2 2 Calculated: C: 54.89, H: 5.44, N: 11.64, experiment Values: C: 54.75, H: 5.40, N: 11.58 〇 (2). Isopropyl-3,4 · Dimethylfurfural [2,3-c] Bite-5. Shuttleamine (VIII-30 ) Dissolve compound VII · 3 (1 g, 0.042 mole) in 100 ml of benzene, pass in methylene fluoride, and boil it under reflux. After the reaction is completed, filter, and wash the solid part with water. The liquid portion was washed with water, the anhydrous sulfur medium was dehydrated, the filtrate was evaporated to remove the solvent, the residue was combined with the solid, and separated by column chromatography (silicone shift_gas imitation), that is, compound VIII-30. White crystals, yield 0.7g (76 »). mp: 176-177lC; HO ^ Br) v max: 3370 (NH), 1680 (CO) cm-1; UV (CHC13) Λ max: 302nm (e-9.4xl〇4) nm; 1H-NMR (CDC13) δ: 1.52 (d, 6H, -NCH (CH3) 2), 2.47 (s, 3H, C-3-CH3), 2.54 (s, 3H, C-4-CHg), 4.48 (m, 1H, -CH ), 6.20-6.50 (br, lH, -NH); MS, m / Z: 221 (M +); elemental analysis: CnH ^ w, calculated value: C: 59.71, H: 6.83, N: 18.99, experimental value: C: 59.68, h: 6.91, N: 8.90 〇Example 4-3 1 N -methyl-2-isopropyl-3,4-dimethylfuranhydrazine [2,3-c] 吭 嗤 · 5_Carboxylamine (VIII-31) -58-This paper uses the Zhongming S home standard (CNS) f 4 regulations «5 (210x297 g; ft) (please read the precautions before filling in this page) · Order-Ministry of Economic Affairs, Ministry of Economic Affairs, Central Bureau of Industry and Commerce β Industrial Consumption Cooperation Duin 5i V. Description of the invention () With reference to the synthesis method of compound viii-i, using the same reaction conditions and processing methods, make methylamine and compound VII-3 (1 Gram, 〇〇〇〇42mol> reaction, you can get the compound νιιι · 3l 0 light yellow crystals, yielding 0.8 grams (85 *>. Mp: 148-150 ° 〇; IR &lt; KBr) v: 3370 ( NH), ΙβδΟζΟ-Οοιη'1 max; UV (CHCl〇) λ: 286nm (ε -3.3xl〇4); 1H-NMR (CDC10) `` 3 m & x 3 5: 1.52 (d , 6H, -NCH (CW>, 2.47 (s, 3H, C-3-C ^ 3), 2.54 (s, 3H, C-4-CH3), 2.92 (d, 3H, NHCH3), 4.48 (m, 1H, -CH), 6.17 -6.52 (br, lH, -ton); MS, m / z: 235 (M +); elemental analysis: C12H17N3〇2, calculated value: C: 61.26, H: 7.28, N: 17.86 , Experimental value: C: 61.31, H: 7.32, N: 17.65 〇Example 4 · 3 2 heart dagger-2-isopropyl-3,4-dimethylfuranhydrazine [2,3 &lt;] pyrazin-5-carboxy Acetamide (VIII-32) Referring to the synthesis method of compound VIII-1, under the same reaction conditions and treatment methods, Gamine was reacted with compound VII-3C1 g (0.0〇42 mole) to obtain compound VIII-32. White crystals, yield 0.6 g (600. mp: 128-130〇C; IR (KBr) u: 3370 (NH), 1650 (0-0 max; UV (CHC1) Λ: 287nm (ε -5.3xl〇4); 1H-NMR (CDC10) j in α X 3 δ: 1.25 (t, 3H, CH2CM3), 1.52 (d. 6H, -NCH (C Dan 3) 2), 2.47 (s, 3H.C-3-CH), 2.54 (s, 3H , C-4-CH0), 3.47 (q, 2H, CH0CH0), 〇-3 a 2 3 4.48 (m, lH, -CH), 6.20-6.52 (br, 1H, -NH); MS, m / z : 249 (M +) -59-(please read the back-to-back attention item Λ-fill this page first). Binding-Thread &lt; This paper uses the Chinese Η 家 烊 毕 (CNS) TM regulation (210X297 Public: Jfc) Λ 6 Π 6 Printed by the Labor and Social Security Cooperative Society of the Ministry of Economic Affairs, Pyongyang Bi 51, 51. Description of the invention (); elemental analysis: C13H19N3〇2, calculated value: c: 62.63, H: 7.68, N: work 6.85 , Experimental value: C: 62.70, Η: 7.72, N: 16.74. Example 4-3 3 N-Prop-2-isopropyl-3,4-Dimethylfuranhydrazine [2,3_c] carbozole Amine (VIII-33) Referring to the synthesis method of compound VIII-1, using the same reaction conditions and treatment methods, propylamine (0.6 g, 0.097 mole) and compound VII-3 (1 g, 0.0〇 42 mol) reaction, that is, the compound VIII-33. Light yellow crystals, yield 0.54 g (5〇 *) 〇mp: 96-98〇C; IR (KBr ) y: 3360 &lt; NH), 1650 (0-0) 010-1; UV (CHC13) Λ max: 288nm (e-1.9xl〇4>; H-NMR (CDC13) δ: 〇.98 (t, 3H , CH2CH2C ^ 3), 1.52 (d, 6H, -NCH (C Dan 3) 2), 1.55 (m, 2H, N-CH2CH2CH3), 2.47 &lt; S &gt; 3H, C-3-CH3) , 2.54 (3,3H.C-4-CH3), 3.45 (m, 2H, N-CH2CH2-CH3), 4.48 (m, 1H, -CH), 6.33-6.54 (1 ^, 111, -call) ' , 111/2: 263 ^ +); elemental analysis: (; 141121% 〇2, calculated value: C: 63.85, H: 8.04, Ν: 15 · 96, experimental value: C: 63.81, Η: 8.10, N: 15.90 〇Example 4-3 4 Ν- 丁 _2_isopropyl_3,4-dimethyl, furan [2 3_cj oxazole · 5 carboxamide (VIII-34) Reference compound VIII-1 synthesis method , Using the same reaction conditions and processing methods, make butylamine (0.8 g, 0.0097 mole) and compound VII-3 -60-(please read the notes before the ## write this page) Order-Line · This paper scale is used in the middle 8 national sample (CNS) T4 regulation (2 丨 0 father 297 disciples) Central Ministry of Economic Affairs β Bureau of Industry and Consumer Goods Cooperative printing level 9,0 _____nj_Five Description () g, 0.02 〇42 Modou) reaction, that is, compound VIII-34 〇 pale yellow crystals, yield 0.72 g (62〇. mp: 1〇4-106〇C; IR (KBr) v: 3 37〇 (NH), 1640 (0-0) 001-1 max; UV (〇2H5〇H) λ max: 285nm (e-1.9xl 〇4); 1H-NMR (CDC13) δ: 0.93 (m, 3H, N-(CH2) 3C Dan 3>, 1.22-1.67 (m, 4H, -NCH2C_ ^ 2 CH2CH3), 2.47 (s, 3H, C -3-CH3), 2.54 (s, 3H, C-4-CH3), 3.22-3.52 (q, 2H, N-CH2CH2CH2-CH3), 4.42 (m, 1H, -CH), 6.17-1.52 (br, lH, -N] p; MS, m / z: 277 (M +); elemental analysis: C15H23N3〇2, calculated value: C: 64.96, H: 8.36, N: 15.15, experimental value: C: 64.85, H: 8.30, N: 15.20. Example 4-3 5N-isopropyl-2-isopropyl-3,4-dimethylfuridine [2,3-c] pyridinecarboxamide (VIII-35) Reference compound VIII -1 synthesis method, using the same reaction conditions and processing methods, make isopropylamine (0.6g, 〇_0〇97mol) react with compound VII-3 (1g, 0.0042mol), that is to call the compound νιΙΙ · 35. Light yellow crystals, yield 0.65 g (59%> 〇mp: 120-122〇C; IR (KBr) v: 3 370 (NH), 1640 (0-0) 010-1 01 X ; UV (CHC13) Λmax: 286nm (ε-1.9xl〇4); 1H-NMR (CDC13) δ: l-20-1.33 (m, 6H, CONHCH (CH3) 2) I1.40-1.52 (d, 6H , .NCH (C ^ 3) 2), 2.47 (S, 3H, C-3-C ^ 3), 2.54 (s, 3H, C-4-C] i3), 3.98-4.67 (m, 2H, CONHCH (CH3) 2> -NCH (CHg) 2), 6.00-6.33 〇> 1 :, 11 ^ .- ton) ^ 3 , 111 / ^: 263 (1'1 +); Elemental analysis: (:% 1 ^ 0, total 1 ^ 21 3 2. -61-(please read the notes on the contrary to write this page by Sun Yao) Order _ This paper uses the Chinese National Standard (CNS) IF4 specification (210x297 male dragon) Λ 6 Η6 2043 ^-V. Description of invention () Calculated value: C: 63.85, H: 8_04, N: 15.96, experiment Value: C: 63.94, Η: 8.15, Ν: 15.86 〇Example 4-3 6 Ν, Ν- 二 G-2-isopropyl-3, -dimethylfuran [2,3-c] 咣 嗤- 5-Carboxyacetamide (VIII-36> Referring to the synthesis method of compound VIII-1, using the same reaction conditions and treatment methods, diethylamine (0.7 g, 0.097 mole) and compound VII-3 (1g, 0.042mol) reaction, compound VIII_36 can be obtained. White crystals, yield 0.65 g (56%). mp: 80-82〇C; IR &lt; KBr) v: 1620 (C-0) cm'1; UV (CHCl) λ max: 293rm (ε duty 3 · lxl〇4); 1h, nmr (cdc13) 5 : 1.15-1.45 (t, 6H, N (CH2CH3) 2), 1 · 52 (d, 6H, NCH (CH3> 2), 2.47 (s, 3H, —2 (please read the precautions before proceeding Write this page}

C-3-cH3), 2.54 (s, 3H, C-4-C denier), 3.33-3.70 (q, 4H, N (CH CH3) 2), 4 '33-4_ 67 (m, 1H'-qp ; MS, m / z: 277 (M +); elemental analysis: C15H23N3〇2, calculated values: C: 64 · 96, H: 8.36, N: 15.15, experimental values · C: 64.87, H: 8.32, N. .15.21. Example 4-3 7 The Ministry of Economic Affairs, U.S. Bureau of Industry and Commerce, Duin 3i N- (Thamboxybenzyl) · 2-isopropyl_3,4_dimethyl, furanhydrazine [23_c] pyridine Carboxamide (VIII-37) Referring to the synthesis method of compound VIII-1, using G guess as the solvent under the same reaction conditions and processing methods, make 2_helyl benzylamine (1 * g, 0.000097 different) and Compound VII-3 (1 g, 0.042 mole) reacted, -62-^ 04351

V. Description of the invention () Compound VIII-37 can be obtained. Yellow crystals, yielding 0.4 g (24.mp: 265-267〇C; IR (KBr> i / nax: 3300 (NH), 1670 (C-0> Cm_1; UV &lt; C2H5〇H) Λmax : 319nm (g-4.lxl〇4); ^ Ή-ΝΜΠίΟΜβΟ-dg) §: 1.33-1.50 (d, 6H, CH (CH3) 2), 2.48 (m, 6H, C-3-CH3l C_4-CJ13 ) '4-33-4-67 (m, lH, -Cjp, 7.00-7.33 (m, 2H, stupid ring proton), 8.00-8.16 (&lt; 1,111, pen ring proton), 8.52-8.70 (&lt; 1,1 ^ 1, stupid ring proton> ,; MS, m / Z: 341 (M +>; elemental analysis: calculated value: C: 63.33, Η: 5.61, N: 12_31, experimental value ： C: 63.31, H: 5.65, N: 12.39 〇 (Please read the precautions first and write this page) Jingxu Bureau of the Ministry of Economic Affairs CX Gongxiao Λ · Cooperative cooperative seal 51 Examples 4-3 8 N-(鈇 L * oxycarbonylbenzyl) -2 -isopropyl-3,4 · dimethylfurfural [2,3-c] tonazole-5_carboxamide (VIII-38> compound VIII-37 (1g, 〇〇〇33mol) dissolved in 100ml of absolute alcohol, add thiosulfone as catalytic catalyst] heated to reflux, until the reaction is completed, then the solvent is distilled off, after 10% After the neutralization of the solution and the extraction of the gas imitation, the gas imitation layer is washed with water and dried After the dehydration of the "re-evaporated solvent" is separated and purified by column chromatography (crushed_gas), compound VIII-38 can be obtained. Table color crystals, yield 1.0g (9Μ) .mp: 155 -158eC; IR (KBr) ι /: 3250 (NH), leyOCC-Ocm'1 max; υν (° 2Η50Η) λmax: 331nm (ε = 2.4xl〇H); H.NMR (DMS〇.d ^ 6 δ ： 1.33-1.54 (m, 9H, CH & CH3) 2, -CH2CH3), 2.480η, 6H.C-3- -63-Binding · Binding · Line · This paper standard is used in a Η home standard (CNS ) τ4 specification (210 father, 297 male dragon) 2〇Λ 6 Η 6 Printed by the Beigong Anti-Crafty Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (). Dan 3. C-4-C Dan 3), 4.33 -4.67 (m, 3H, -C denier (CH3) 2, -CM2CH3), 7.00-7.33 (m, 2H 'stupid ring proton), 8 〇〇816 (d lH, stupid ring proton>, 8.72-8.95 (d , LH, stupid ring proton> ,; MS m / z: 369 (M +>; elemental analysis: C2〇H23N3〇4, calculated value: C: 65.〇3, Η: 6.28, Ν: 11.37.Experimental value: C: 65.15, Η ·· 6.32, N: ll.43〇 Example 4-3 9 (1>. 2_benzyl_3,4 · dimethylfuran hydrazide [2,3-c] pyrronine-carboxyl sugar Gas ... work!:-々) Using compound III-6 (1 g, 0.015 mol) as raw material, According to the synthesis method of compound III-1, compound VII_4 can be obtained. Yellow brown liquid. (2). 2 · Wu · 3,4-Erhuji "Fu B Nanpin [2,3-C] ton bite_5_ shuttlebanamine (VIII-39) The compound VII-4 (1 g, 〇 .〇〇35Mo Lane> Dissolve in 100 ml of stupid, pass helium gas and heat to reflux. After the reaction is complete, the solid part is washed with water and dried. The liquid part is washed with water and dried over anhydrous sulfur. After dehydration, the solvent was distilled off from the filtrate, the residue was combined with the solid, and separated by column chromatography (silica gel-aeroform) to obtain compound VIII-39. White crystals with a yield of 0.81 g (8> 0.8mp: 228 -230〇C; IR (KBr) v: 3300 &lt; NH), 16 27 (0-0) 0111 ^ III &amp; X 4 1; UV (CHC10 &gt; λ: 287nm (ε-8.3x10); H-NMR ( CDC1) 3 max 3 / δ: 2.37 (s, 3H, C-4-CH3), 2.54 (s, 3H, C-3-CH3), 5.25 (s, 2H, -C] i2-C6H5), 6.90- 7_33 (br, 2H, -N Dan 2>, 7.25 (s, 5H,-CH2 -64-(please read the backing notes first # 蜞 write this page) install &lt; order_ line China a 8 standard (CNS) A4 specifications (210x297 male dragon) 204351 Λ 6 Η 6 Ministry of Economic Affairs, Central Bureau of Industry and Commerce β labor consumption tv cooperation Duin 5i V. Description of invention ()-(36 廷 5) # 3,111 / 2: 269 (&gt;1+); elemental analysis: ( : 15111 / 3〇2. Calculated value · c: 66.90, Η: 5.61, Ν: 15.60, experimental value: C: 66.96, Η: 5.67, N: 15.71 ο Example 4-4 0 Ν- 甲-2-fluorene-3,4-dimethylfuran. South hydrazine [2,3-c] pyrazole-5-carboxylamine (VIII-40) Refer to the synthesis method of compound VIII-1, using the same reaction conditions and Treatment method, reacting methylamine with compound (1 g, 0.0035 mol), that is, compound VIII-40. Light yellow crystal, yield 0.75 g (76 *). -1 rnp: 142-144 ° c ; IR (KBr) v: 3450 (NH), 1650 (C-0) cm max 4 1; UV (CHC1) Λ: 286nm (e &quot;1.1xl〇); H-NMR (CDC1) 3 max 3 0 : 2.37 (s, 3H, C-4-CH3), 2.54 (s, 3H, C-3-CH3), 2.90-2.98 (d. 3H, -NHCH.), 5.25 (s, 2H, -CH0-C /:H_),6.33-6.55(br, Yi 3 — L 6 D 1H, -N denier-), 7.25 (s, 5H,-CH2-C6 ^ 5); MS, m / z: 283 (M +); Elemental analysis: C16H17N3〇2, calculated values: C: 67.83, H: 6.05, N: 14.83, experimental values: C: 67_88. H: 6_14, N: 14.93. Example 4-4 1 ^ Has-2-year-3 , 4-Dimethylfuranhydrazine [2,3-〇] pyridine-5-carboxamide (VIII-41) Referring to the synthesis method of compound VIII-i, using the same reaction conditions and treatment methods, the dagger amine and the compound VII-4 ( 1 gram, 〇.〇〇35 Modou) Reaction-65-(please read the precautions before filling in this page) Binding-Order-Line &lt; This paper size is used in the aa home sample (CNS) T4 specifications (2 丨 〇 297 male dragon) Ministry of Economic Affairs, Bureau of Economics, Central Bureau of Industry and Commerce β Industrial and Financial Cooperation Cooperative printed 5i V. Description of the invention (), you can obtain compound VIII-41 〇 pale yellow crystals, yield 〇.65 g (63〇〇mp: 110-11210; IR (KBr) υ: 3400 (ΝΗ), 1640 (0-0) 001 ^ max; UV (CHC1 ") Λ: 286nm (ε-6 · 7xl〇4); 1H -NMR (CD01o) 3 max 3 8: 1.30-1.58 (t, 3Η, -NHCH0CH0), 2.37 (s, 3Η, C-4-CH „), 2-3 3-4 2.54 (s, 3H, C-3 -C] i3), 4.34-4.55 (q, 2H, -NHC] i2CH3), 5.25 (s, 2Η, -CH2-C6H5>, 6.90-7.33 (br, lH, -NH-), 7.25 (s, 5H ,-. 112-0: 6 denier 5> # 3,01 / 2: 297 (&gt;1+); elemental analysis: 〇17111 / 3〇2, calculated value: 0: 68.67, Η: 6.44, Ν: 14.13, experimental value : 0: 68.74, Η: 6.54, Ν: 14.30 ο Example 4 · 4 2 Ν-propan-2-fluorene-3,4-dimethylfuranhydrazine [2,3-c] pyridin-5-carboxylic acid Amine (VIII-42> Referring to the synthesis method of compound VIII-1, using the same reaction conditions and treatment methods, propylamine was reacted with compound VII · 4 (1 g, 0.0〇35 mole) to obtain compound VIII-42. Light yellow crystals, yield 0.65g (63〇.mp: 148-150〇C; IR (KBr) V: 3350 (NH), 1640 (0-0) 00 ^ max 4 1; UV (CHCU) Λ : 285nm (e-2.6x10); H-NMR (CDCl ^) 3 max 3 δ: 0.66-1.25 (t (3H, -NHCH0CH0CH0), 1.33-1.70 (m, 2H, zz ~ 3-NHCHnCH "CH.) , 2.37 (s, 3H, C-4-CH.), 2.54 (s, 3H. C-3-CH. 2-2 3-3-3), 3.17-3.54 (q, 2H, -NHCM2CH2- CH3), 5.25 (s, 2H, -C Dan 2-W, 6.17 · 6 · 66 (br, 1H, · Ν Dan ·), 7.25 (s, 5H, · ΟΗ2- (36Μ5); -66- Λ 6 II 6 (please read the notes on the back of this page first to write this page). Packing, ordering, and threading. This paper standard is used in the HS family standard 1MCNS) T4 regulation tM2Klx297 public: ¾) Λ 6 It 6 2〇435l V. Description of invention () (please read the precautions before writing this page) MS, m / Z: 311 (M +); elemental analysis: C18H21N3〇2, calculated value · C: 69.43, H: 6.80, N: 13.49, experimental value: C: 69.40, Η: 6.71 · Ν: 13.35 〇 'Example 4-4 3 Ν- 丁 -2 · 爷 -3,4-dimethylfuran 2,3-c] pyrazole-5. Carboxamide (VIII-43) Referring to the synthesis method of compound VIII-1, using the same reaction conditions and treatment methods, make butylamine (0.8 g, 0.0097 Molong) and Compound VII-4 (1 g, 0.0〇35Moong> reaction, you can get compound VIII-43. Light yellow crystals, yield 0.85 g (74 *>. Mp: 128-130〇C; IR (KBr) »/: 3370 (NH), 1640 (C-0) cm_ 1 max; UV (CHC13> Λmax: 285nm (ε -2.0xl04); 1H-NMR (CDC13) 8: 〇.95 -1.10 (t, 3H, -NH (CH2) 3CH3), 1.33-1.66 (br, 4H, -NHCH2 (CH2) 2CH3), 2.37 (s) 3HiC-4-CH3) i2.54 (s) 3H, C-3-CH3), 3.17 -3.54 &lt; q &gt; 2H, -NHCH2- (CH2) 2CH3), 5.25 (s, 2H, -CH2-〇6H5), 6.17-6.66 (br, lH, -NH-), 7.25 (s, 5H,- CH2-C6H5); MS, m / z: 325 (M +); elemental analysis: Ci9H23N3〇2, calculated values: C: 70.13, H: 7.12, N: 12.91. Experimental values: C: 70.30, H: 7.23 , The Ministry of Economic Affairs is accurate and the CX industry and consumer cooperation Du Yin 51 N: 12.80 〇 Example 4-4 4 N-isopropyl-2-benzyl_3,4-dimethyl * husband "Nanpin [2,3 -c] Bite · 5_ Carboxamide (VIII-44) -67-

This paper is used in the ft scale. A 9 揳 Bi (CNS) «r 4 specifications (210x297 g; SO 204351 Λ 6 H6 Central Bureau of Economic Affairs, Ministry of Economic Affairs £ 3: Industrial Consumers & Co., Ltd. ^ V. Description of invention ( ) Referring to the synthesis method of compound VIII-1, using the same reaction conditions and treatment methods, isopropylamine (0.6 g, 0.097 mole) and compound VII-4 (1 g, 0_0〇35 mole) After reaction, compound νllIII_44 is obtained. Light yellow crystals, yield 0.74 g (69%>. Mp: 148-150 ° C; IR &lt; KBr) y: 3360 &lt; NH), 1640 (C-0) cm * 1; UV (CHC13> λmax: 285nm (ε-2.0xl〇4); 1H-NMR (CDC1) 8: ll〇-1.33 (d, 6H, -NHCH (CH)), 2.37 (s, 3HIC-4 -CH), ^ / 3 2.5A (s, 3H, C-3-CH3), 4.00-4.45 (m, 1H, -NHCH), 5.25 (s, 2H --CH2-C6H5), 6.00-6.33 ( br) lH, -NH-), 7.25 &lt; m (5H, -CH2-C6M5 &gt;; MS, m / z: 311 (M +); elemental analysis: Cl8H21N3〇2, calculated value: C: 69.43, H: 6.8 〇, N: 13.49, experimental values: C: 69.38, H: 6.62, N: 13.35 〇Example 4-4 5 〃, heart dihex-2-benzyl-3,4-dimethylfurananhydrazide [2, 3-〇] oxazole-5-carboxamide (VIII-45> Refer to the synthesis method of compound VIII-1, the same reaction Conditions and treatment methods, diethylamine (0.7 g, 0.0097 mole) and compound VII-4 (1 g, 0.0〇35 mole) are reacted to obtain compound VIII-45. Light yellow crystals, Yield 0.73 g (65 *). Mp: 132-134 °; IR (KBr) v: 1690 (C = O> cm_1; UV max (CHCl)) λ: 299nm &lt;e-9.8xl〇4); 1H- NMR &lt; CDC1n) Q: • 3 oi 3 x 3 ll〇-1.38 (tI6H, -N &lt; CH2CH3) 2)) 2.42 &lt; s, 6H) C-4-CH3, C-3-CH3), 3.33-3.68 (q, 4H, -N (CH2CH3) 2), 5.25 (s, 2H, -C ^--68-(please read the back and notes beforehand #items to write this page) This paper size is used a B Homestead Biography (CNS) T4 Specification (210X297 Public) 204351

5. Description of the invention () C6H5>, 7.25 (m '5Η' · σΗ2-〇6] ^ 5); MS, m / z: 325 (M +); elemental calculated value: c: 70 · 13, H : 7.12, N: 12.91, experimental values: C: 70.31, h: 7.22, N: 12.72. (五> 2,3,4-Trisubstituted_5-hydroxymethylfuranhydrazine [23c] Manufacture of pyrazole (IX> (2,3,4-Trisubstituted-5-hydroxyinethylfur〇 [2,3-c 】 Pyraz〇les (IX))

^ 丨 N &lt; 、 L; UOR '' Z ^ (VII) (III) (IX) (please pay attention to the matter beforehand # 项 窎 this page) Install · R2, R3, R4, the same type ( B) Scheme 6 Heat the compound VII with various intoxicants to carry out the acetylation reaction, and the corresponding 2,3,4 · trisubstituted _ 5 _hydroxymethylfurfural [2,3 _c] 咄 嚷 · 5 -Carboxylic acid (III) and dissolve this vinegar compound in a solvent (such as THF), and carry out the original reaction (such as LiAlH4) to carry out the original reaction reticle column folding method and recrystallization method After purification, the corresponding 5 · methyl group IX can be obtained. Example 5-1 (1>. Butan-2-G-3,4-Dimethyl hydrazide [2,3_cl pizi · 5. Carboxytetrazine-69 * Λ1 in «Β 家 样 毕 (CNS) &lt; P4 Regulations (2 丨 〇 &gt; &297; Gonglong) Line · Ministry of Economic Affairs 屮 央 擂 准 and 13: Gongxiao fr cooperative cooperative printed 5i original paper 2〇435i Ministry of Economic Affairs 揮 楛 斛 局 A Gong **: Cooperation Du Yinsi V. Description of invention () S purpose (111 -18) Compound VII-2 (1 g, 0.0047 mole) was dissolved in 100 ml of n-butanol, heated to reflux for 4 hours After that, the solvent was evaporated to dryness, and the residue was purified by column chromatography (silicone-chloroform> to obtain compound 11]; _18. Light yellow liquid, yield 1.0 g (79%). IR (KBr) v: 1700 (C-0) cm'1; UV (CHC1) A: 276nm; 1 max H-NMR (CDC13) δ: 0.93 (t, 3H,-(ewe Dan 3), 1.27-1.80 (m, 7H , -OCH2CH2CH2CH3, N-CH2CH3), 2.47 (s, 3H, C-4-CH3>, 2.50 (s, 3H, C-3-CH), 3,87-4.43 &lt; m, 4H, -OCH CH CH CH, J — 2 2 2 3 'NC] i2CH3); MS, m / Z: 264 (M +); elemental analysis: Ci4H2〇N2〇3, calculated value: C: 63.62, H: 7.63, N: 10.60, experiment Value: c: 62_55, H: 7.70, N: 10.72〇 (2). 5-Meth-2--2--3,4-dimethyl * Fudi, 2,3-c] 咣(IX) Lithium aluminum hydride (0.5g, 0.013mol) was added to 30ml of anhydrous G ether, and the compound (〇5g, 〇〇〇19mol) dissolved in anhydrous ethyl bond was slowly dropped Add to the reaction mixture and stir at room temperature. After the reaction is completed, add 1 ml of water and continue to stir. When filtered, the filtrate is dehydrated with anhydrous magnesium sulfite, and the solvent is evaporated to remove the solvent. After separation and purification by column chromatography (silica gel_chloroform), compound Ιχ can be obtained. White crystals, yield 0.3g (81%). Mp: 124-126¾; IR (KBr) ι /: 3250 (OH) cm '1; UVmax (CHC13) λ max: 252nm; 1H-NMR (CDC13> δ: 1.38 (t, 3H, N-CH2 CH3), 2.15 (s, 3H.C-4-CH), 2.38 (s, 3H , C-3-CH0), 4.07 (q, j —3 -70-(Please read the precautions first and then write this page) Binding · Ordering-Line. This paper is printed with the Chinese B house. Quasi (CNS) T4 gauge (210x2 ^ 7 ^ 7 Μ V. Description of the invention) Example 6-1 (1). N- (ethyl radon carbonylamino) _2,3,4 · trimethyl • furan [2,3 c] Benzazole% iron acetamide U-1) Referring to the synthesis method of compound VIII-1, using G dragon as the solvent under the same reaction conditions and treatment methods, make hydrazine Suo G pickled compound VII-1 (1 g, 〇.〇〇47 mole) were reacted to give compound X1. Yellow crystals, yield 0.75 g (55 *). mp: 218-219〇C; IR (KBr) ι /: 3360 &lt; NH), 1730 &lt; CO〇CH) IQ 3 XO c ^, 1660 (CONHNH) cm_1; uv (CHCl) λ: 287nm (e-2.2 x ^ 3 max 10); 1H-NMR (CDC1) g: 1.05-1.33 (t) 3Hi.CHCH) (247 ° 2-3 (s, 6H, C-4-CH3, C-3-CH3), 3.83 ( s, 3H, -NCH3), 3.90-4.25 &lt; q, 2H, -CH2CH3), 8.85-9.00 (br, lH, -NHNH), 9.90-10.0 (br, lH, -NHN denier); MS, m / z: 280 (M +); elemental analysis: C12H16N4O4, calculated value: C: 51.42, H: 5.75, N: 19.99, experimental value: C: 51.49, H: 5.68, N: 19.85 〇 (please read it first. (Notes and fill in this page again) Install & Thread · The Ministry of Economic Affairs Shiyang Prefectural Bureau β Engineering Consumer Cooperatives Cooperative 3i (2). 5- (2,3-Diargon-2-gas-1,3,4- Adenin-5-yl> -2,3,4-trimethylfurazide [2,3-c] pyrazole UI-1) Heat 100 ml of dibenzyl ether to 240 ° C and add compound X -1 (1 g, 0.0〇36 different) heated to reflux, after the reaction is completed, after cooling and extinction, the sink is washed with n-hexane and dried, then recrystallized with L drunk to obtain compound XI- 1 〇 light yellow crystals, yield 〇 85 grams (98 *) 〇mp: 236-239 * 0; IR (KBr) v: 3050 (NH), 178〇 (C-0) cm 1 max -72-This paper is used in the margin of a 8 (CNS) &lt; F4 specifications (210x297 male dragon) Ministry of Economic Affairs + Central Bureau of Industry and Commerce &quot; Cooperative cooperative printing 54 Λ 6 Η 6 V. Description of invention (): (C2H5〇H) Λmax: 287nm (e-3.0x104); 1H-NMR (DMSO-d6> δ: 2.45 (s, 6H, C-4-CH3, C-3-CH3), 3.83 (s , 3H, -NCH3); of, 11/2: 2340+); elemental analysis: (: 1 (^ 1 (^ 4〇3, calculated value: C: 51.28, H: 4.30, N: 23.92, experimental value ： C: 51.34, Η: 4 · 39. N: 23.90 〇Example 6-2 (1) · N- (oxocarbonylamino) -2-hex-3,4-dimethylfuridine [2, 3-c] oxazole_5 • Carboxamide (X-2) Referring to the method of synthesizing compound X-1, using the same reaction conditions and treatment methods, make hydrazine methylpyridine S compound and compound VII-2 (1 g, 〇.〇〇44 Mohr) reaction, you can get compound X-2 〇 浃 yellow crystals, yield 0.65 g (500. mp: 225-226 * 0; IR (KBr) v: 3290-3230 (NH), 1740 max (cooc H ^) (166〇CCONHNH) cm'1; UV (CHC10) Λ: 280nm I 5 3 max &lt; ε »1.4xl〇4); 1H-NMR (CDC13) δ: 1.36 (t, 3H, N-CH2CH3), 1-52 (t, 3H, C00CH〇CH"), 2.46 (3, 3H, C-4 -CH0), 2.55 (s, 3H, c * 3-CH3), 4.19 (q, 2H, N-CH2CH3), 4.23 (q, 2H, COOCH2CH3); MS, m / z: 294 (M +); elemental analysis : C13H18N4〇4, calculated values: C: 53.〇5, H: 6 · 16, N: 19.04, experimental values: C: 53.16, H: 6.20, N: 19.24 o (2). 5- (2,3 -Dihydro-2-oxo-1,3,4-purindioxan-5-yl) -2-hex-3,4-dimethylfuridine [2,3-c] pyrazole (XI-2 ) -73-This paper is used in the ft scale side a 揳 家 楳 准 (CNS> Ή specification (210x297 g *) (please read the precautions before writing this page) Install-Line · Ministry of Economic Affairs Bureau of Standards Ex 5x5. V. Description of the invention () ΙοΙτ Solvent 2 Strategy Mystery 100ml is heated to 24 ° C. Compound X · 2 (3 • g, 0.0〇34mol) is added> Heat to reflux and wait for reaction After completion, after cooling and filtering, the spatter is washed with n-hexane and dried, and then separated and purified by column laminar folding method (silicone «Zhejiang ester) To obtain the compound χι2 〇 light yellow crystals, yield 0.80 g (95 *) 〇mp: 243-2451; (dec.); IR (KBr) v: 3100 (NH), 1760 (0-1 max 〇) cm; UV &lt; 〇2Η5〇Η) Λmax: 296nm (e-5.2xl〇4); 1H-NMR (DMSO-d6) §: 1.33 (t &gt; 3H, N-CH2CH3), 2.46 (s, 6H , C-4-CH3, C-3_Cii3>, 4.17 (q, 2H, NC) i2CH3>; MS.m / z: 248 (M +); elemental analysis: C1; LH12N4〇3, calculated value: C: 53.22, H: 4.87, N: 22.57, experimental values: C: 53.41, H: 4.90, N: 22.60 o Example 6-3 (1). N- (Goxycarbonylamino) -2 · isopropyl-3,4- Dimethylfurfural [2,3-c] oxan-5-carboxamide (X-3> refers to the synthesis method of compound X-1, using the same reaction conditions and treatment methods, the Compound VII-3 (1g, 0.0〇42mol) reaction, compound X-3 can be obtained. Light yellow crystals, yield 0.65 g (500.mp: 160-163〇C; IR (KBr) v: 3320-3200 (NH), 1730 max &lt; C00CoHc), 1640 &lt; CONHNH) cm'1; UV (CHC1.) Λ: 287nm 2 o 3 max (ε-4.5xl〇3); 1H-NMR (CDC13) δ: 1.17-1.42 (t, 3H, C00CHoCHo), 1.47-1.54 &lt; d, 6H, -CH (CH0) 0), 2.46 (s, 3H, 2-3 -J Z-74-This paper is used in the edge of the asa family standard (CHS) &lt; T4 specifications (210X297 male tf) (please read W1 first and back (Notes on this page will be re-written on this page.) F Binding · Order-Line. The Ministry of Economic Affairs is accurate and printed by β Gongxiao tv- cooperatives A 6 η 6 V. Description of invention () ¢ 3-4-(^), 2.55 (8,31 (:-3-0: 1), 4.00-4.67 (111,311 ^-(^ ° —3 — (CH3) 2, COOC mutual 2CH3>; MS, rn / z: 308 (M +); element Analysis: C14H20N4〇4, calculated values: C: 54.54, H: 6 · 54, N: 18 · 1 ?, experimental values: C: 54.60, Η: 6.60, ν: 18 · 23〇 (2). 5- (2,3-Di-Krypton-2-oxo-1,3,4_purindiazole_5_yl> _2 · isopropyl-3,4-dimethyl ^ l ^ fu &lt; «南 拼 [2, 3-c] Sound bite (XI-3) Referring to the synthesis method of compound ΧΙ-1, using the same reaction conditions and treatment methods, adding compound X-3 (1 g, 0.000032 Molong) to react, you can get Chemical compound ΧΙ-3. Light yellow crystals, producing 0.77 g of soap (93. mp: 195-198 ° C; IR (KBr) v: 3100 (NH), 1780 (C-0) cm * 1 max; UV (CHC13) λ max: 300nm (ε-9 · 2xl〇3); 1H-NMR (DMS0-d6) δ: 1-33-1.50 (d, 6H, CH (CH)), 2.43 (s, 3H, C-4- CH.), One j Z — 3. 2.33 (s, 3H, C-3-CH3>, 4.52 (m, lH, -CH-); MS, m / z: 262 (M +): elemental analysis: C12H14N4〇3 , Calculated value: C: 54.96, Η: 6.38, N: 21.36, experimental value: 0: 54.99, H: 6.30, N: 21.47. Example 6-4 (1>. N- (Goxycarbonylamino) -2-benzyl-3,4-dimethylfuran [2,3-c] oxazole-5-carboxamide (X-4> Referring to the synthesis method of compound xl, using the same reaction conditions and processing methods, make N-Aminomethyl methyl group is reacted with compound VII-4 (1 g, 0.0〇38 mole) to obtain compound X-4. -75-The size of this paper is based on the Chinese B Family Standard (CNS) T4 specification (210X297 male dragon) (please read the precautions before filling out this page) Binding · Order-Λ 6 It 6 V. Description of invention ( ) Light yellow crystals, yield 0.90 g (67〇〇mp: 220-222〇C; IR (KBr) 1 / max: 3200 (NH), 1740 (000〇2Η5>. 1640 (CONHNH) cm'1; UV (CHC13) A_one: 288 nm (ε -4.2 χ max 10); H-NMR (CDC13) δ: 0.95-1.25 (t, 3H, COOCH2CH3), 2.46 (s, 6H, C-4-CHn, C- 3-CHo) I3.90-4.33 (q, 2H, -COOCH Λ — X — * -3 _ CH3), 5.25 (s, 2H, -CH2-C6H5), 7.25 (.11,5H, -CH2- C6H5); MS, m / Z: 356 (M +); elemental analysis: Cl8H2 () N4〇4, calculated values: C: 60.66, H: 5.66, N: 15.72, experimental values: C: 60.71, H: 5.62, N: 15.73 〇 (please read the precautions of ΙΓΠ first, and then fill out this page) 5i (2>. 5- (2,3-diazo-2_oxygen _1,3,4-indadiazol-5-yl) -2-benzyl-3,4-dimethylfuridine [2,3 -c 1 (XI -4) refers to compound XI-1 Synthetic method, using the same reaction conditions and processing methods, adding compound X-4 (1 g, 〇〇〇2828ear> reaction, Compound XI-4 can be obtained. Pale yellow crystals, yield 0.80 g (92 *) 〇mp: 240-243〇C; IR (KBr) v: 3000 &lt; NH), 1710 (0 = 0) 0111-1 ^ max 4 1; UV (CftHr0H) Λ: 302nm (e * »1.2x10); H-NMR (DMS0-2 5 max d £) §: 2.47 (s, 6H, C-4-CH0, C-3- CH.>, 5.37 (s, 2H, -CH -o — J-J-z C6H5), 7.25 (m, 5H, -CH2-C6 ^ 5); MS, m / z: 310 (M +); Elemental analysis: Calculated values: C: 61.93, H: 4.55, N: 18.06, real 16 14 4 3 Check values: C: 61.96, Η: 4.62, Ν: 18 · 17. -76 装 · 线 · 本 纸Aa family «Ping (CHS) T4 regulations (210x297 g)) A 6 H6 Central Ministry of Economic Affairs Ministry of Economic Affairs ία: Gongxiao 1V> Cooperative Society printed 3i V. Description of invention () (VII). 5- (2,3-Di-Krypton-2-oxo-3-acetyl-l, 3,4-pf diazol-5-yl> -2,3,4-trisubstituted, fuhydrazine [2,3_c] 咣Production of azole (XII> (5- (2,3-Dihydro-2-ox〇-3-acyl-l, 3, A-oxadiazol-5-yl)-2,3,4-trisubstituted-furo [2, 3-c] pyra- zoles (XII)) j4 RCOXj ™ 2 N 0 solvent (XI) 0 0 R2. R3, R4, the same formula (B> Scheme 8) Dissolve compound xi in an appropriate solvent (such as G) In the use of chained engraving of Daodang (such as G酑) 醢 化 'can get the corresponding compound XII 〇 Example 7-1 5-(2' 3-. One gas-2-gas-3 Jj chain-1, 3, 4-today two bite -5 -Yl) -2 · A-3,4-dimethyl cough 0 Nansuan [2,3- £: 1 参 11 (> 11-1> Compound XI-1 (1 g, 0.0〇43mol) Dissolve in 10 milliliter of vinegar and 1 milliliter of vinegar, after heating to 100¾ and reacting for 1 hour, pour into cold water. After encountering it, wash with water and dry to obtain compound XII -1. -77-

(Please read the notes for the back page # 导 写 this page) Binding, binding, thread. This paper is used in the standard side a Η 家 标 iMCNS) T4 specification (210X297 male dragon)

—J Λ6 __ n 6 Employee consumption of the Central Bureau of Standards of the Ministry of Economic Affairs ·· Cooperatives printed 5i V. Description of invention () Light yellow crystal, 1.0 g of soap production (85 *) 〇mp: 236-239¾; IR (KBr) 1 / : 30 50 (NH), 1720 (0-0) 001-1 max; uv (〇2Η5〇Η) λ max: 314nm (ε-3.5x1〇3); 1Η-NMR (DMSO-dg) δ: 2.45 ( mp9H, C-4-CH C-3-CH0> -C0CHo), 3.83 (s, 3H, N-3-3-3 C Dan 3>; MS, m / z: 276 (M +); elemental analysis: Ci2H12N4〇4, calculated values: C: 52.17, H: 4.38, Ν: 20 · 28, experimental values: C: 52.20, Η: 4.43, N: 20.32 ο Example 7-2 5- (2,3-two Argon-2-oxo-3-acetin-1,3,4-purindiazol-5-yl> -2-G-3,4 · dioxylfur》 Nanso [2,3-c] 咁 嗤(XI1-2) With reference to the synthesis method of compound XI-1, under the same reaction conditions and treatment methods, compound XI · 2 (1 g, 0.0040 Modou) was added to react to obtain compound XII · 2. Pale yellow crystal, produced Rate 1.0 g (81〇. Mp: 208-2101C; IR (KBr) 1 /: 3300 (NH), 1740 (C-0), max 1640 (C-0) cm '; UV &lt; CH OH) λ: 311nm (ε-5.5xl〇3); I 5 max H-NMR (DMS0-d) δ: 1.33 (t, 3H, N-CH0CH0), 2.46 (m, 9H, CD 2-3 4-CH3, C-3-CH3, -C0 CH3), 4.17 (q, 2H.N-CH2CH3); MS, m / z: 290 (M +); elemental analysis: C13H14N4〇4, calculated value: C: 53.79, H: 4.86, N: 19.30, experimental value: C: 53.82, H: 4.74, N: 19.26 〇Example 7 · 3 5- (2,3-dihydro-2-oxo-3-hexyl-1,3,4-dioxin-5-yl)- 2- -78-(please read the precautions of 110 before wl # fill in this page) 装 · 线-This paper is used in the standard a B home standard (CNS) T4 specification (210X297 male dragon) A 6 H6 Ministry of Economic Affairs Printed by the Central Bureau of Labor and Economics of the Central Bureau of Industry and Commerce. 5. Description of the invention () Isopropyl-3,4-dimethylfuranhydrazine [2,3-c] pyridine (XI1-3) Reference compound synthesis method, With the same reaction conditions and treatment methods, compound XI-3 (1 g, 0.0038 moong) was added to react to obtain compound XII · 3. Yellow crystals, yield 0.9g (77〇.mp: 208-2101C; IR (KBr) U: 3000 (NH), 1730 (0-0), max -1 4 1640 (C-0) cm; UV (CHCl〇) A: 314nm (e -3.5x10); j max 1 H-NMR (DMS0-d6) δ: 1.33-1.50 (d, 6H (t, 3H, CH (CM3) 2), 2.48 (01 , 9H, C-4-CH., C-3-CH. (-COCH ^), 4.33-4.67 (m, 1H, JJ-3 -qi); MS, m / Z: 304 (M +); elemental analysis : Ci4Hi6N4〇4, calculated value: C: 55.26, H: 5.30, Ν: 18 · 41, experimental value: c: 55.40, H: 5.51, N: 18.46 〇Example 7-4 5- (2,3-diazo -2-oxo-3 -L »醢 -i, 3,4_ humeran-5-yl>-2- + -3,4-dimethyl * funanase [2,3-c] (XII-4) Referring to the synthesis method of compound XIII-1, under the same reaction conditions and treatment methods, compound XI-4 (1 g, 0.0032 mole) was added to react, that is, compound XII-4 was obtained as pale yellow crystals. Rate 1.0 g (88 *) 〇mp: 168-17〇1〇; IR (KBr) 1 /: 3200 (NH), 1740 (0-0), 1640 &lt; C-0) cm 1; UV (〇2Η5〇 Η) Λmax: 297nm (ε-2.Oxl〇4); H-NMR (DMS0-d) §: 2.47 (m, 9H, C-4-CH. C-3-CH, -COCH ° -3 -3 —3), 5.37 (s, 2H, -C Dan 2-C6H5), 7.25 (πι, 5H, -CH2_C6 Dan 5> MS, -79-(please read the precautions first and then write this page) This paper is used in the country B (CNS &gt; A4 regulations) (210x297 public address) V. Description of invention () m / Z: 352 (M +); elemental analysis: C18H16N4〇4, calculated value: C: 61.36, Η: 4.58, Ν: 15.90, experimental value: C: 61.40, H: 4.63, N: 15.96〇 ( VIII) · Manufacturing of 2,3,4-trisubstituted "Furano [2,3-c] pyrazole-5-propene (XIII) and its self-determined derivatives (Q11) (2,3 , 4-1 ^ 311151: let 1 ^ 6 £ 1 furo [2,3-c] pyrazole-5-acrylic acid (XIII) and its esters (XVI1))

,

CH * CHCOOH

CH «C (COOH) 2 (XVI) t HCI (please read the notes before you # fill in this page) r / CO〇H CH2, COOH pyridine piperidine R2〆

Outfit · order ·

CHO piperidine CH2 (COOEt) 2

10% Na OH

COOEt COOEt line. Central Bureau of Standards of the Ministry of Economic Affairs κχ Industrial and Consumer Cooperative Printed 31

CH = C-COOE t R2, R3, the same type (B) Process 9 -80-This paper uses the Chinese Standard (CNS) T4 specification (210x297 male dragon), the central standard of the Ministry of Economics, and the β labor consumption &quot; Cooperation Duyin 31 Μ Λ β ^ _Π6 ___ V. Description of the invention () As shown in the process 9, there are three different ways to manufacture the target compound: Method 1 Dissolve the recovery (V> in a solvent (such as stupid) , Heating in the presence of alkali (such as pyridine) to carry out the condensation reaction 'After purification by column layer folding method or recrystallization method, you can get the corresponding 2,3, three substitution' &quot; Fu ° Nanpin [2,3 &lt;; 1 Ego-5 · ylmethylene bis-dipyridyl ester (3 [") (2,3,4-1: 1 &quot; ^ 11133 |:; 11 ^ seven" "1′〇l2,3-〇] pyrazol-5-yl methylidene malonate (XlV)), and then the compound XIV is hydrolyzed with a strong base (such as NaOH) and then mineralized (such as HC1). After the conversion, it is crystallized with an appropriate solvent compound to obtain the corresponding acrylic acid ( XIII) 0 Method 2 Dissolve malondipine in a common solvent (such as pyrazine), heat it with compound V in the presence of a base (such as pyridine) to carry out a condensation reaction, and after undergoing condensate, pass column chromatography Method or recrystallization After purification, the corresponding target substance (XIII> 0) Method 3 The Wittig test rule (PhJ-CHCOOR :) is dissolved in a common solvent (such as MeOH), and the Wittig reaction is performed with the compound V under weak test conditions You can get the corresponding 2,3,4-trisubstituted "furan pin [2,3-c] pyridine_5 · acrylic acid (2,3,4-trisubstituted furo [2,3-c] pyrazol -5-acrylate) (XVII) and a part of it is hydrolyzed (χιιι). * 81-This paper recognizes / tiAW + a S-#: «^ (CNS) T ^ 210X297 ^ '^) ....... ....... n ........ Smoke :: · Ό (Please read the notes on the back of this page first) Λ 6 Π 6 5. Description of the invention () Example 8 -1, 2,3,4-trimethyl * fuweili [2,3-c] Blow Jun-5 -Propane (X111 -1) Method 2: Bring anhydrous propane (1 g, 0.0.0) 〇97 mol) dissolved in pyridine (20 ml, 0.25 mol), add compound vl (0.623 g, 0.0035 mol), then add "nong bite (1 ml, o.oii mol)) to settle, under muse After heating and avoiding the flow for 2 hours, add stupid to evaporate the solvent, add ice water, after the crystal is precipitated, filter the precipitate in case of filtration, wash the strip with water, add 10 * broken argon The dilute solution dissolves the Shen Ji, imitates washing with gas, and the water layer is degraded by the] _〇 * Liba solution. Stirring and cooling are required during the acidification process, and then stand in an ice bath for 1 hour to take the precipitate, After washing with water and drying, the residue was separated and purified by column chromatography (crushed gas-amplitude &amp; C * drunk) to obtain compound XIII-1 Ο yellow crystals, yield 0.6 g (78 *) . mp: 254-256 t:; IR (KBr) v: 2700-3000 (COOH), 1685 max

(CH-CH-COOH) cm'1; UV (CHClo) A: 350nm; 1H-NMR 3 max (DMSO-d) 8: 2.28 (s, 3H, C-4-CH), 2.43 (s, 3H, C-3-CH), 3.70 (s, 3H, N-CH3), 5.97 (d, 1H, J-16Hz, -CH = CHC00H), the Ministry of Economic Affairs, Bureau of Standards, Beta Workers, Cooperative Society, Inno (please first Read the notes to the contrary Sun fills this page) 7.37 (d, lH, J-16Hz, -CH-CH-C00H); MS, m / z: 220 (M +); elemental analysis: C1; LH12N2〇3, calculation Values: c: 59.99, H: 5.49, N: 12.72, experimental values: C: 60.08, H: 5.54, N: 12.62. Method 1: (1). 2,3,4-Trimethylfuranhydrazine [2,3_c] vftazole · 5 · yl-methylenepropanediamine-82 Standard (CHS) Τ4 regulation (210x297 g *)

Μ 5. Description of the invention ()

Sl (xiv-i) The compound ν-ι (0.623 g, 0.0035 moles) was dissolved in 80 ml of benzine, and propane diazepam (15 g, 0.009 moles) was added After mixing with dipyridin (ml, 0.011 mol), heat to reflux for 2 hours. The reaction period is called to remove the water formed by the reaction. After the reaction is completed, wash the strip with water, dehydrate it with anhydrous thief, and remove the liquid. The solvent and the residue were separated and purified by column chromatography (silica gel. Gaseous imitation), that is, T obtained compound XIV-1 〇 yellow crystals, yield 1.1 g (61%>. ®P: 76-78〇C; IR ( KBr) y max: 1730 (C-〇), i7〇〇 (c-〇) c〇-1; H-NMR (CDC13) g: 1.07-1.73 (m, 6HIC (CO〇CH2CH3) 2) &gt; 2 3〇 (S, 3H, C'4'C-3) i2-40 &lt; s-3H &gt; C-3-CH3), 3.77 (s, 3H, N-ch) 3.90-4.60 (m, 4H &gt; C (COOCH2CH3) 2), 7.37 (s, lH1-CH-C &lt;^; MS, m / z: 320 (M +) 〇 (2) _ 2, 3, private trimethyl furfural [2, 3_c] Oxazolam · propylene disulfide (χlι ^) compound xiv-i (ι · ι g, 0.03 mol) was suspended in i〇 * sodium oxyoxide solution, and stirred at 70t for 8 hours! Afterwards, the filtrate was washed with Bayu, and then treated with 10% solution ， In the process of stagnation, it must be mixed and purinated, then let stand for 1 hour in ice cream, take the gargle, then wash with water, dry it, the precipitate is recrystallized with G drunk, you can get the compound χιηι The color crystal's yield was 0.42 g (63%). The name was: 254-25610; this product was compared with the compound uhq obtained by method j for IR and TLC, and the blending test was performed. The results were completely the same. The same compound. The standard of this paper meets ^ &quot; ^ 8 samples ([Ν5) Ή regulations 《5 (210X297 公; if)-83-

5. Description of the invention () Method 3: The compound (XIII-1) can also be obtained by the following Wittig method: (1). 2.3.4-Trimethylfurfural [2,3-c] zole_5_ Propylenedimethicone (XVII.U first prepare Wittig test stab: dissolve chlorhexidine (0.4g, 0.0028 mol) in 1.5ml of stupid, add tribenin (0.75g, 0_0 〇28 mol), heated to stay for 2 hours, the resulting precipitate is the ylide (ylide), Ph3P-CH-COOEt, this precipitate was dissolved in 20 mL of methyl alcohol, compound Vl (〇.5 G, 〇〇〇28mol), add 1 of the broken platinum solution under the chamber, after the reaction is completed, the nails are distilled off, and then extracted with a gas-like extract, and the gas-like extract is dehydrated by anhydrous sulfur. , The solvent was distilled off, the residue was separated by column lamina fold method (silicone · gas imitation), and then recrystallized with G, to obtain compound XVII-1 〇 yellow needle crystals, yield 0.29 g ( 45%). Mp: 146-148〇C; IR (KBr) v: 1710 (-CH-CH-COcm'1; max UV (CHC1) λ: 344nm; 1H-NMR (CDC10) §: 2.13 (s, 3H, J 01 α X 3 C-4-CH), 2.30 (s, 3H, C-3-CH), 3.70 (s, 6H, N-CHo &amp; 0- 〇 一 ό -3 C Dan 3), 6.10 (d, lH, J-16Hz, -CH-CH-CO>, 7.33 (d, lH, J-16Hz, -CH-CH-C00CH3); MS, m / z: 234 (M +), 203 (M + -31) 〇 (2>. 2,3,4-top three) Fusaki hydrazide [2,3-.] Instruct the gu_5_propene to separate the water layer to 10 * Lijun solution Junhua, that is, a yellow sink is produced. In case of filtration, the precipitate is collected by filtration, washed with water, dissolved with 10% kryptonite solution, and then washed with chloroform. The aqueous layer is then treated with 10% argon solution , It must be agitated and cooled during the process, then let stand for 1 hour in an ice bath, filter the precipitate, wash it with water, and dry it. The precipitate is subjected to column chromatography (Silicon 84-this paper is for standard use China Β B 楳 戳 Bi (CNS) Ή regulations t »(210x297 public« :) (please read the precautions before filling in this 5 pack-line. Employee of the Ministry of Economic Affairs Bureau of the Ministry of Economic Affairs and Cooperation Du Yin 5i

Fifth, the description of the invention () shift · -qifanpan) was separated and purified to obtain the compound (XIII D 〇 yellow crystals, yield 0.31 g (39%). Mp: 254-2561〇; this product and the method obtained After comparing the IR and TLC of the compound ΧΙΙΙ-1, and doing a blending test, the results are exactly the same, and it is indeed the same compound. The Ministry of Economic Affairs, Central Bureau of Industry and Engineering, β Gongxiao Cooperative Printed 5i Example 8-2 (1>. 2-C ·· 3,4-Dimethyl, Fu 0 Nan Pin [He] Deng Gu 5 propylene dicarbamide (XIII-2) Dissolve anhydrous propargyl (1.0 g, 〇.〇〇97 mole)> To the bite (20 mL, 0.25 mol), add compound ν · 2 (〇67 g, 〇〇〇35 mol> mixed with saki bite (1 mL, 0.011 mol>), under 11〇_115l> c After refluxing for 2 hours, add stupid to evaporate the solvent and add ice water. After the crystals are precipitated, wash them with water and add 10% broken argon thymium solution to dissolve the precipitate and move to the point. The liquid funnel was washed several times with chloroform. The water layer was then warmed with a 10% solution. The process of stirring must be stirred and cooled, and then allowed to stand for 1 hour in an ice bath. After washing and drying, the residue was separated and purified by column chromatography (miaojiao-qi imitation drunk) to obtain compound XIII-2. Yellow crystal, 0.67g (82%) of soap production. Mp: 215-217lC; IR (KBr) v: 3100-2500 (OH), 1690 (0 = max 0), 1600 (-CH-CH-C00H) cm * 1; UV (CH OH) Λ: 355nm; 1 25 max H-NMR ( DMS0-de) Q: 1.3〇 (t, 3H, N-CH2CH3)) 2.25 (s13HlC-4-CH3), 2.42 &lt; s, 3H.C-3-CH), Α.Οβζς, ζΗ, Ν-ΟΗ ,, ΟΗ ^), 5.97 —3 —2 3 * 8 5-This paper is used in the standard aa home standard (cns) A 4 rules (the precautions between Jing Xian and back to back ¾ wood page) Order_ Line ·

V. Description of the invention () Printed by the Ministry of Economic Affairs Standards Bureau s Gongxiao 1'i * Cooperative Society ¾

Cd, lH, J-16Hz1-CH-CH-COOH), 7.37 (d, lH, J-16HZ, -CH-CH-C〇〇H>; MS, elemental analysis: Ci2Hij2〇3, calculated value: C : 61.53, Η: 6.02, Ν: 11 · 96, experimental value: c: 616〇, H: 6 15 .N: 11.99 ο (2). 2-C »-3,4-dimethyl ketananhydrazide [2,3-c] Tongu · 5. Prosthetic acid (XVII-2) Compound XIII-2 (1 g, 0.043 mole) was dissolved in 100 ml of absolute alcohol and added Sulfur is a catalytic thorn, heated to reflux until the reaction is completed, the solvent is distilled off, neutralized with 10% cracked surface solution, taken with the bonded leather, the G ether layer is washed several times with water, and dehydrated by anhydrous sulfuric acid. The solvent was distilled off, and the residue was separated and purified by column chromatography (silica gel-aeroform) to obtain compound XVII-2. Pale yellow crystal, 0.76 g (68 *) of soap produced. Mp: 109-112〇C ; IR (KBr) v: 1700 (C-0), 1600 (CC) max • 1 1 cm; UV (CHC1) Λ: 348nm; H-NMR (CDC10) §: 1.32 j max 3 (t, 3H, N -CW, l_42 (t, 3H,-COOCW, 2.27 (s, 3H, C-4-C ^), 2.43 (s, 3H, C-3-CD, 4.10 (q, 2H, N-CHoCHo), 4.79 j a 3 -2 3 &lt; q, 2H, -C00CH2CH3), 6.28 (d, 1H, J-16Hz, -CH-CH-COOH), 7.48 (d, lH, J-16Hz, -C HC mutual-C00H); MS, m / z: 262 (M +); elemental analysis: C14H18N203, calculated value: c: 64.11, Η: 6.92, N: 10.68, experimental value: c: 64.11, H: 6.98, N: 10.75〇-86-The size of this paper is BB home brown half (CNS) T4 regulation (2 丨 0 father 297 public goods) (please read the back-end notes #item writing wooden page) f Binding · Binding-Line-A 6 Η 6 V. Description of the invention () (9). 2,3,4-Trisubstituted furosemidine [2,3-c] pyrazole-5-propenylamine to) ( 2,3,4-Trisubstituted furo [2,3-c] pyrazole-5 · acrylamides (XIX))

CH = CHCOOH (XIII)

CH = CHCOCI

(XIX) (Please M first, please memorize 1 (Notes on 6 Er Λ 5 to write this page). Pack. Order 5i R2, R3, R4, same type (B), as printed by the Ministry of Economic Affairs, Bureau of Standards, Bureau of Labor Standards, B1. Process 1 0 Dissolve compound XIII in a solvent (such as stupid) and treat it with sulfurous dichloride (soci2) to recrystallize it with a solvent (such as petroleum ether + C ether) after the gasification reaction. Obtain the corresponding chlorinated XVIII, and finally dissolve this intermediate XVIII in a common solvent (such as stupid), and react with various amines to obtain the corresponding target XIX. Example 9-1 (1). 2- G-3,4-Dimethylfurazide [2,3-c] pyrazole-5-acryloyl chloride-87-5 good-quality side papers in the paper S8 home 楳 rule IM210X29Y public) line · test department屮 央 斀 擀 而 β 工 消 &quot; Cooperative Du Yin 51 φ died _ V. Description of invention () (XVIII-2) Dissolve compound XIII-2 (1 g, 〇_〇〇43 Molong) dissolved in 100 ml of anhydrous In Benzhong, add thionyl chloride (4.1 g, 0.035 mol) and stir with heating. After the reaction is completed, the solvent is distilled off, and the solid residue is washed with petroleum ether and dried to obtain compound XVIII- 2. Crude brown product with a yield of 1.1 g (920. (2). 2-Hexan-3,4-dimethylfuran [2,3-C] pyrazole-5-propenamide (XIX-2) Compound XVIII-2 (1 g, 0.04 mol) was dissolved in 100 ml of anhydrous benzene, stirred, and bubbled with hydrogen. After the reaction was completed, the solid part was washed with water and dried. Partially washed with water several times, dehydrated with anhydrous thiomagnesium, passed through, the filtrate was evaporated to remove the solvent, the residue was combined with the solid part, and recrystallized with G drunk-gas mixed solvent to obtain compound XIX-2. Yellow Crystallization, yield 0.54g (5M). Mp: 258-260〇C; IR (KBr) u: 3190, 3380 (NH), 1660 max (C-0), ΙόΟΟζΟ-Οοπι'1; UV (C „Hr0H ) λ: 333nm; 1H-NMR 2 5 max (DMS0-O δ: l-30 (t, 3H, N-CHoCH.), 2.27 (s, 3H, C-4-CH.), 6 Z ~ d 2 43 (s, 3H, C-3-C Dan 3), 4.07 (q, 2H, NC) ^ 2CH3), 6.27 (d, 1H, J-16Hz, -CH * CH-C0NHrt), 7.23 (d, 1H, J-16Hz, -CH-CH-C0NHo — 2 _ 2); MS, m / Z: 233 (M +>; elemental analysis: C12H15N3〇2, calculated value: C: 61.79, H: 6_48, Ν: 18 · 01, experimental value: C: 61.82, H: 6.53, N: 18.17 〇-88- Λ 6η 6 (please note back to the first page # 蜞 乔 this page) The standard of this paper is easy to use a Η home standard pregnancy (CNS) Τ4 regulations (2 丨 0X297 Gong; «:) Jing Jiang Bei Central 51艃 贝 工 工 諀 軀 社 社 Innu Λ 6 Π 6 V. Description of the invention () X. Cai Li experimental method (1) Anti-allergic activity test (Rat PCA Test) This experiment uses 15 to 22 grams of Wistar male male White mice were injected subcutaneously with 0.1 ml of diluted mouse antiserum egg protein in two places on their abdomen. After 48 hours, 1 ml of 0.5 * Evans blue solution containing 2 mg of egg protein antigen was injected from the tail vein for about 30 minutes After that, the rats were killed, and the area and depth of the blue area were measured from the abdomen skin, and the average value of the measured value of the pigment spots was the response value of each mouse. 〇. 5% xanthan gum (gum tragacanth> aqueous solution is dissolved, or made into a suspension, 5 minutes before the injection of Evans blue solution, intravenous injection or 1 hour before oral administration. (2) Anti-platelet concentration test (A) Preparation of small plate trigger (1) Dissolve the original (bovine skin) in a 15 mM gambling water solution and grind it into a homogenous suspension under ye, Dispense into 1mg / ml solubility, store under 70 ℃, thaw and grind evenly before use. (2) PAF is dissolved in four-gasification cracking (CC14), stored under · 20 ρ, and diluted with deionized water before use. <3) ADP ball adenosine hphosphaty and peanut arachidonate (Sodium arachidonate (A'A)) are dissolved in deionized water for use. -89 ............... C ........ ^ · ·· * ^ · ···% ···. F Please read the back-to-back precautions #Code Tips This page} Jiayou standard (CNS) T4 specifications (210x297 (Public goods) Printed by the Central Standards Bureau, Ministry of Economic Affairs, A Industrial and Consumer Cooperatives Co., Ltd. 51 V. Description of the invention () (B) Preparation of platelet suspension Preparation of platelet suspension According to Wen Xu ’s method, EDTA and rabbit ear veins were used in 100% Bleeding blood was mixed in the ratio of 1 :; u, centrifuged immediately at room temperature for 12 minutes at 120g, and the upper layer of platelet-rich blood was taken out and centrifuged at 500g for 10 minutes. After removing the plasma, the lower jfe plate was Tyrode solution containing EDTA (2ιηΜ) and bovine serum egg stage (3.5 mg / ml) was suspended, and centrifuged at the same speed for 10 minutes. The resulting plate was suspended without EDTA &lt; Tyrode solution. Adjust the platelet count to about 4 Sx 10 / m2 'and add ImM ion consuming (Ca2 +) for 30 minutes, then carry out the experiment. Tyrode composition: bovine serum protein, NaCl (136 .9), KC1 (2.7), Na2P〇4 (〇.4), NaHC〇3 (ll.9), glucose (11 .; 〇. (C) Platelet aggregation and ATP release reaction test Root Ken Wen and Cross (I963) 's method for measuring the mixture' was measured with a Lumi agglutination meter (Model 1020, Payton, Canada). Buckle the small plate suspension 0.4 ml into a silicone-coated small slope glass tube, and Use a small magnetic rod to mix at 900 ° per minute. If not stated otherwise, the first 1 pound is added before the trigger is added. Antagonism is applied. All reaction processes are expressed at 37 °. As follows: Absorbance before addition of agglutination-Absorbance after addition of agglutination (%)------------- x100% Absorbance before addition of agglutination-Absorbance of Tyrode solution -90 -(Please read the precautions and fill in this page first) The size of this paper is used + H National Standard (CNS) T4 specifications (2) 0x297 public A 6 η 6 V. Description of invention () In some experiments, luciferase-luciferin mixture 25 / ^ 1 was added, and the fluorescence produced by the reaction with ATP was used to determine the size and extent of the platelet release reaction. The value represents the results of pharmacological tests: TABLE 1 N- corpus alkoxy _2,3,4- trimethylfuro [2,3-c] pyrazol-2carboxamide _5 of Rat-PCA Test Method Results

ch3 ch3 CHo— N 7—COB (please note back first # 蜞 写 木 页). Installed. Ministry of Economic Affairs 屮 央 # quasi-only labor elimination cooperative cooperative printed rainbow compound R thorn amount (mg / kg) oral Number of mice No. inhibition rate <%) Scoring control 80 3 0 0 nhch2ch3 80 3 49.0 5 NHCH2CH2CH (CH,) 80 r 2 3 29.6 3 n (ch3) 2 80 3 20.2 3 nh (Ch2) 2ch3 80 4 31.0 4 n_2) 3ch3 80 4 31.3 4 Theophyllin 80 4 67.8 6 -91-Order-Line-This paper is used in the edge of the paper (CNS) &lt; f 4 specifications (210X297; it) c \ bS &gt; ^ a 6_l] _6_ V. Description of the invention () Table 2N- 垸 -2-G-3,4-Dimethylfuran [2,3-c] Pyrazole-5-carboxamide -PCA method test results

CH3CH2 — 'N CH3 PH3

COR, Ministry of Economic Affairs, Yang Yongjun, Cooperating with Employees to Eliminate Duin) 11 '| 4 Compound R (mg / kg) No. of Oral Rats Inhibition Rate (%) Scoring Control 80 4 0 0 nhch3 80 4 51.6 6 nhgh2ch3 80 3 19.9 2 nh (ch2) 2ch3 80 3 23.1 3 _2) 3ch3 80 4 32.4 4 nhch (ch3) 2 80 3 26.2 3 n (c2V2 80 4 30.1 4 nh (ch2) 2ch (c6 V2 80 4 21.2 3 CH -CHOOH 80 4 31.6 4 -92-(please read the back-end precautions # items to write this page) Binding · Binding-Line · This paper is used in the standard 8 Η 家 楳 准 (€ Ν5) Ή regulations «5 (210X297mm) Λ 6 Η 6 V. Description of the invention () Table 3 Rat-PCA method test of 2- 垸 -3,4-dimethylfuridine, U, 3-cl oxazol-5-pyridamine result

-COR 'Compound R then amount R' (mg / kg) Oral number of rats No. Inhibition rate (%) Scoring control 80 4 0 0 -ch (ch3) 2 -NH2 80 3 36.5 4 -CH (CH3) 2- NHCH3 80 4 53.5 6 -ch (ch3) 2 -ΝΗ〇2Η5 80 4 30.5 4 (please read the precautions first and write this page) install and order the Ministry of Economic Affairs, Bureau of Standards, Beigong Consumer «Cooperative Print 5i The paper is used in the middle of the paper. B Η 楳 楳 准 (CNS) Ή regulations (210x297 g; tt) -93 Λ 6 Η 6 _ 5. Description of the invention () Table 4 5- (2,3-Diargon-2-oxygen -1,3,4-Pyridinediazol-5-yl) -2-alkan-3,4-dimethylcranone [2,3-c] pyridine Rat-PCA method test results ch3 CH3 R ' R -N, N ^ cV o ^ o compound scored rat number inhibition rate score R R '(mg / kg) No. (%) oral control 80 4 0 0 -CH3 -H 80 3 53.0 6 -CH2CH3 -H 80 4 14.1 2 -ch (ch3) 2 -H 80 4 46.1 5 -CH2-C6H5 -H 80 4 -27.3 1 Pack- (please read the precautions before writing this page)

The Ministry of Economy ’s Central Standards Bureau κχ 工 Consumer Cooperatives Cooperative Printing M-94-This paper size is used in China National Standard B (CNS) T4 specifications (210 father 297 male dragons) Λ 6 Η 6 V. Invention description () Table 5 : Platelet aggregation inhibitory activity of furan [2,3-c] pyridine

r2-n, volume

R5 R2 “g / ml ADP Luji AA Collagen PAF (20yM) (100” M) (10wg / ml) 2ng / ml (please read the notes before you write this page) Control 83.0 + 2.5 88.6+ 1.1 87.6 + 3.0 90.0 + 2.0 -COOH -CH2- / 100 67.2 + 2.7 0.0 + 0.0 63.8 + 1.1 84.1 + 2.4 • COOH -CH 100 66.6 + 2.7 6.4 + 3.8 46.7 + 8.8 80.4 + 1. -C00H 100 51.1 + 4.5 21.4 + 1.5 2.0 + 1.4 75.7 + 4.7 The Ministry of Economic Affairs' Central Bureau of Biology CI: Industrial Consumers Cooperatives Innu NN O, 〇NN Suo-CL2 -CH2CH3 100 40.2 + 11.9 8.9 + 7.3 80.9 + 5.6 87.3 + 2.6 -CH (CH3) 2 100 27.0 + 11.0 1.3 + 1.0 63.3 + 10.5 90.0 + 1.3 -CH „-C6H5 100 64.2 + 3.1 0.0 + 0.0 77.0 + 6.9 86.6 + 3.6 This paper scale uses the Chinese S family sample (COS) A 4 Regulation tM210x297 male dragon) 95

Claims (1)

Six, the application for the patent range of amendments to the heart supplement this month-. A __A7 aV C7 Ά Df (Amended in December 1981). A compound of the following formula (B) and its pharmaceutical R-2 (B) -CH, Rn; -CH2 《~ yf— Xn 'X »* Dental CH, (OR) n; or (please listen to the notes on the back before filling this page) • CH 2Ar, where Ar R . RH or 6 pit base, n-1 or 2; ci _ 9 burned base; H; -COR; -CH2〇H; -CH2〇COR1; -COX, x-ii element; y) -COOR; -CONHR; a Printed CONR1R1 by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs; CO —N:) ϊ-CO — N y -CO * -N -COHNAr ,; 96 paper ft scales, the Chinese National Standard Rate (CNS) T4 Specification (210X297mm)% A7B7C7D7 VI. Patent application range -CONH (CH2) mN • Ar · -CONH (CH2) nN Αν · CO —Ν, / CO 一 Ν. Ο NR -CO —N N- Ar -CONH (CH2) nAr3n -CH-CHCONHR; -CH = CH-COOR; -CH «C (COOR) 2; -CONHNHCOOR; or 3 (please read the precautions on the back before filling this page), nn: h or Printed by Beigong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs m = 1-3, R and η are as defined above, \ alkyl, R-R or C cycloalkyl, R-H 'halogen or -OCH. a 3 · ο ο 〇97 The standard of this paper is in the B country »quasi (CNS) T4 specification (210X297 g *) 6. Application for patent patent®2. — A composition of medical Cai used to inhibit platelet aggregation and resist anti-min It contains the compound B as described in item 1 of the patent application or its pericarp as an effective ingredient. (Please flash the precautions on the back before writing this page). Installed. Printed by the Central Bureau of the Ministry of Marriage, Beigong Xiaozhi Cooperative 'line · -98-This paper size is applicable to the BS standard (CNS) ) A 4 specifications (210x297 mm) 丨 ΓΠΙ 丨 丨 -----