TW201125850A - Azetidine-2,4-diketone based compound prepared by using the same, and poly (amide-amine ester) - Google Patents

Abstract

An azetidine-2,4-diketone based compound has the chemical formula represented as the following formula (I), wherein R.sub.1 and R.sub.2 are respectively alkyl groups of C.sub.1-C.sub.6; R.sub.3 is –CH.sub.3, -COOH, or -COCl. Additionally, by taking the azetidine-2,4-diketone based compound of this invention as the initial article, a compound having a specific weight average molecular weight can be precisely prepared by simple alternative synthesis, and the poly(amide-amine ester) prepared by the compound has good mechanical strength.

Description

201125850 VI. Description of the Invention: [Technical Field] The present invention relates to azetidine-2,4-dione-based compound, in particular to a compound having a specific structure synthesized by a nitrogen heterocyclic-2,4-diketone compound, and a poly(p-lysyl urethane) having a hard chain segment of an equal chain length. In recent years, polyurethane materials have been widely used in various fields. Most of the prior art uses a one-pot method or a prepolymer method to produce polyurethane materials. The hard segments in the polyurethanes produced by these methods usually do not appear. The molecular length of the homo-, that is, the molecular weight distribution of the hard segment portion is broad, because the chemical technique of the conventional preparation of the amine ester material cannot effectively and precisely regulate the molecular length of the hard segment therein. However, the existing research indicates that the use of polymers with narrow molecular weight distribution can improve various physical properties of their materials, such as mechanical properties and degree of phase separation. Therefore, in order to improve the mechanical properties of these materials, how to effectively prepare a hardness with equal molecular length The segment is currently a hot research topic. So far, the research reports that have been published to try to prepare hard segments of uniform length are mainly divided into two categories: the first type of method uses the protection and deprotection of chemical reactions with high preparation and complicated procedures, but such methods usually yield. Quite low; the second type is the use of 2,4-toluene diisocyanate (2,4_t〇luene; 2,4_DI) or isophora I-isocyanate (is〇ph〇r〇ne diiS0Cyanate ·. ipdi) isocyanate with two different reactive isocyanate functional groups starting from 201125850, but such methods are limited by the reaction selectivity of isocyanate functional groups, mainly hard The bond segment product is usually accompanied by a by-product of chain extension. US 6,784,273 discloses a biocompatible polyurethane, and in the polyurethane, more than 90% of the diol chain extenders have the same bond length. However, as shown in the examples of this example, the diol bond extender must be reacted with a 6-fold excess of 1,4-butanediol (BDO) in a ratio of diisocyanate (DI) to the molar ratio, and then remaining Io, 4-butanediol removal. This production process must not only waste a lot of raw materials, but also the diol chain extender is limited to one molecular length, namely BDO-DI-BDO, and cannot extend the molecular length of the isomerized diol to more than twice as much as possible. BD0-(DI-BD0)n-DI-(BDO-DI)n-BDO, where η is an integer of 1 or more. In addition, Ming-Chieh Kuo and Shenghong A. Dai et al. used a monoisocyanato-2,4-dione (mono-isocyanato-azetidine-2) with two different reactive functional groups in 2008. , 4-dione; MIA) as a starting material, a compound having a specific molecular weight (length) for use as a hard segment in an alternate synthesis strategy, and these compounds and polyether polyols and diphenyl fluorenyl groups The prepolymer obtained by the reaction of 4,4'-methylene-bis(phenyl isocyanate; 4,4'-MDI) is reacted to form a linear imitation triblock poly(amine ester-urea) copolymer. Linearly pseudo-triblock poly (urethane-urea:). From the data in this document, it was found that the higher the generation of the synthesized compound, the higher the molecular weight distribution index (P〇lydispersity index), and the narrow molecular weight distribution could not be obtained. Based on the existing manufacturing costs of polyurethane materials and the poor mechanical strength due to the different lengths of hard segments, there is still a need to develop a 201125850 polyurethane material with low cost and good mechanical strength. SUMMARY OF THE INVENTION A first object of the present invention is to provide a nitrogen heterocycle, a compound, a compound. Chemical formula: The nitrogen heterocyclic-2,4-birth I compound of the present invention has the following formula (I),

(I) -CH3, -COOH or -COC The second object of the present invention is to provide a poly(amide-urethane) for use in the synthesis of poly(amide-urethane) and has a low process cost. The compound 'is having the following formula (II): Αι-Β (II) wherein 'A! is a monovalent group having the following chemical formula (ΠΙ):

Η (III) In the formula (ΠΙ), R4 and R5 are each a Ci to C6 alkyl group; / \ w2 • W4 — 0 —, and —W] — NN — | Z is \_/ —— W3 — N - or Z and Y are connected to an atom of N or 0, 5 201125850 where, when burning, it is a Cl to Ci2; 垸: W2#:: two c:

W3 is a C2 alkyl to c12 alkyl group; C4 alkyl;

And R6 and R_7 are each B is χ_Α2 or X', wherein X is a divalent group obtained by removing each active hydrogen in two hydroxyl groups on the diol, or a borrowing a divalent: group obtained by removing each of the two amine groups on a diamine, but condition (10), when the amine is an amine, the N is not First order carbon phase; & X is a - valency group obtained by removing an active alcohol on a unit or a unit amine, but conditionally, when the unit amine is a tertiary amine N in the unit amine is not in contact with the primary carbon; the definition of VIII is the same as A 式 in the formula (II); and 201125850

When B is -X-A2, if Υ, η in the formula (III) is an integer of 0 to 4; if γ is Η, η in the formula (III) is an integer of 1 to 4;

Then, η in the formula (III) is an integer from 〇 to 8; if ¥ is Η, η in the formula is an integer from 1 to 8. A third object of the present invention is to provide a poly(amine-amine ester) which has the advantages of low cost and good mechanical strength. The poly(amine-amine ester) of the present invention has a weight average molecular weight of from 25, 〇〇〇 to 300,000 and is a reaction product comprising a mixture of the following components.

a diisocyanate component, a polyol component and a chain extender component, the diisocyanate component comprising at least one diisocyanate; the polyol component comprising at least one species a polyol having a weight average molecular weight of from 8 Å to a side t; and the chain extender component comprises a compound of the formula (II) as described above. 'The two compounds of the high-named heterofunctional functional group of the Indo-Indone, the starting compound', the aza-diketone compound with a brewing gas base, and the synthesis of the four ("four") The different chain elongation agents of different generations can be clothed in the knife of the specific chain long heart 201125850. In addition, the poly (bristamine-amine vinegar) f made with the chain extender is hard because of the uniform chain length. The segment has good mechanical strength, so it can achieve the object of the present invention. [Embodiment] The inventors of the present invention have found that two kinds of bases having high selectivity at room temperature and without catalyst can be obtained through various studies. The group 'is the nitrogen heterocyclic 2,4 bis fluorenyl group and the hydrazine group. Therefore, in the case of borrowing Taian, it is necessary to prepare a compound having a chemical formula (Π). The nitrogen heterocycle ~· biguanide compound, and the nitrogen heterocycle of the present invention covers the nitrogen heterocyclic 2,4-diketone compound having an I chlorine group from the diketone compound and the miscellaneous compound (4) A precursor of a cyclic-2,4-diketone compound. A nitrogen-based nitrogen atom of the present invention has a nitrogen heterocyclic 2,4·diketone compound. The dry formula ⑴ formula: qe are not ⑴ Ο

Ri R2 R2 each (I) is a C to C6 alkyl group; wherein R! and -CH3, -COOH or -COC1 in formula (1), when r3 is a _C0C1 time base nitrogen heterocycle-2,4 - Diketone quaternized character formula (1) is the _-combination of the brewing:: square:: case: preparation = yes (10) is prepared first - the above formula (1) and HCH ^ square > ketone The compound 'is further oxidized to 2, C 〇〇 H, and then the _c 〇〇 H, 3 is oxidized to % 2, 4 · bis 3 + 201125850 -OH is replaced by Cl' to obtain the nitrogen heterocyclic 2,4_biguanide compound having a fluorenyl chloride group; (2) The second method is to directly 4-isocyanate benzoquinone chloride (4-isocyanatobenzoyl chloride), 2-ethylbutyryl chloride and triethylamine are mixed and reacted. Incidentally, in the embodiment of the present invention, the present invention is obtained by mixing p-tolyl isocyanate, 2-ethylbutylphosphonium chloride and triethylamine to obtain the first type. The nitrogen heterocyclic 2,4·diketone compound represented by the above formula (1) and R3 is -CH3 which is required in the method. The present invention has a compound represented by the following formula (A): A!-B (II) wherein 'A! is a monovalent group having the following formula (III):

In formula (III), ® R4 and r5 are each a C1 to C6 alkyl group; —W 广\^—Y2 Z is \ / , —W3—N—or —W4—0—, and Z and The Y-bonded atom is N or 0, wherein is an alkyl group of C] to c6; when w2 is an alkyl group of one to c6, W3 is an alkyl group of C1 to C12, and when W2 is Η, 201125850

W3 is a CH2-C to C12 stretching base; C4 burning base;

W4 is 0

R6 r7 or Η, and each of 尺6 and r7 is B is X_a2 or X', wherein x is a two-base group on the divalent group obtained by removing the _ active gas Each of the two amine groups on the respective amines, or a divalent group obtained by removing one of the two groups, but conditionally, the heterogeneous gas is removed.

N is not,, " monoamine is a -amine, the diamine does not bind to the -carbon; slap T X' is a by removing a unit - hydrogen iTFi il · Or a monovalent group on a monoamine that is removed by the addition of a monovalent amine, but in the case of a primary amine, 兮/condition of 疋, the unit amine Δamine ♦ the N in the early decylamine is not a grade-carbon phase The definition of , is the same as the gossip of the formula (11); and 10 201125850 When B is X-A2, if Y is, then η in the formula (III) is an integer from 0 to 4; , η in the formula (III) is an integer from 1 to 4;

Ο 〇

R7 When B is X', if Y is 〇, η in the formula (III) is an integer from 0 to 8; if Y is H, η in the formula (III) is an integer from 1 to 8. /~\ ——Ν Ν - Preferably, the X is \~/, one 〇-Q-〇一 or -nh-q2-nh- 0 The above Qi is a C! to C12 alkylene group, a C4 to C8 extension ring

Burning base,

or

Or Q4 丫 K, and Q3 is an alkyl or hydrazine of Cl to c4, and Q4 is an alkyl, hydrazine, so2 or c=o of C! to c4. The above Q2 is a c4 to c8 cycloalkyl group, a phenyl group, 11 201125850

Or , and q5 is a Ci to c4 alkyl or o, q6 is a c! to c4 alkyl, o, S〇2 or C = 0 0

/~\ - N N - More preferably, X is \_/ or -NH-Q2-NH-, and q6 is a q to C4 alkylene group. Optionally, X is -, where q2 is

N-D9- and Q6 is a C to alkyl group of c4. Preferably

Ch3 -NH-CH3 In the above X', 0! and 02 are each H or a (^ to C4 alkyl group; D3, D4 and D5 are each an anthracene, a halogen, a phenyl group, a C! to C4 alkane a base, a C! to C4 alkenyl group, a C! to C4 alkynyl group or -O-Mi, and M! is 12 201125850 a C] to c12 alkyl or alkenyl group; D6 is hydrazine or NH. In the above X', 〇7 is an alkyl group CH of <r^^α-Cl to c25 "<V-m2- or M2 is a single bond or a methyl group. In the above X, d8 is -Cdc4 a stretching group or a hydrazine; and hydrazine 9 is a single bond or _吣-〇-, and /^ is a CiiC4 alkylene group. More preferably, X' is preferably, the z in the formula (III) is —W"N'w2 N or W2

W2 is Η, w3 is the inventor of the present invention, which sequentially prepares the compound of formula (II) by an alternate synthesis method, and the starting material used is an at least two active hydrogens having the following chemical formula (IV). a diol or a diamine, or a unit or a unit amine having at least one active hydrogen having the following chemical formula (V), and using a unit amine or diamine having at least two active hydrogens having the following chemical formula (VI) A linking group is provided, and the preparation method of the compound of the formula (II) in the present invention will be further described below. H-X-H (IV) 13 201125850 (V)

X, -H hz-nh2 (1) When B is Χ·α2, the compound of the formula (II) which can be represented by the formula (II) is abbreviated as the compound (111): ^The preparation method of the compound (11-丨) Can be divided into half-generation and full-generation compounds

'The compound (IM) represents the half-generation compound (Π-i) paid for the alternate synthesis reaction. More specifically, when η is 〇, the compound (Π-1) is designated as the 〇.5 generation half-generation compound. Example 5 as described below. 'When η is i, the compound (ΙΜ) is designated as the 15th generation half-generation compound (ΙΙ-1)' as in Example 7 below, and the like, and so on; Y is H, and the compound (π-〗) represents the whole-generation compound (II-1) obtained by the alternate synthesis reaction. More specifically, when n is i, the compound (IM) is designated as the first-generation full-generation compound. (π-ι), as in Example 6 below, when n is 2, the compound (the first generation of the compound is the second generation), as in the following Example 8, and so on: (a) The preparation method of the semi-generation compound (11_1}: the fifth-generation half-generation compound (π-1) is obtained by using a diol or a diamine represented by the above formula (IV) and two of the aforementioned nitrogen having a fluorenyl group. The reaction of the heterocyclic 2,4-dione compound is shown in the reaction formula (ml) in Figure i; and the 15th to 45th generation half-generation compound (打-" is based on the 201125850 sequence. The first to fourth generations of the compound (IM) are reacted with two of the aforementioned nitrogen-containing heterocyclic-2,4-diketone compounds having a chlorinated group, as shown by the reaction formula (m2) in Fig. 2 . Preferably, the reaction represented by the reaction formula (ml) is between one and % ° C. Preferably, the reaction represented by the reaction formula (m2) is between 〇 and 5 ° C. between.

(b) Preparation of a full-generation compound (IM): the second to fourth generation of the full-generation compound (Π-1) is sequentially followed by a 〇·5 to 3,5 generation half-generation compound ^^" The reaction of the unit amine or the diamine represented by the above formula (vi) is as shown in the reaction formula (m3) in Fig. 3. Preferably, the reaction represented by the reaction formula (m3) is in the presence of (7) When B is X', 'Formula (11) can be expressed as the following formula (4)), and the compound of the formula (II) of the above (4) is simply referred to as the compound (11_2) Αι-Χ, (II-2) Similarly, the preparation method of the compound (II_2) can be divided into half generation and full generation ^

R6 Ry , the compound (II_2) represents a semi-generation compound rod_2) obtained by alternately synthesizing the reverse shoulder. More specifically, when #η is g, the compound (4) is designated as the 0.5th generation compound (4), as follows The implementation of the description you 15 201125850 U 'When η is 1, the compound (II-2) is designated as the 1.5th generation of the semi-generation compound (Π-2) 'as in the following Example 13, the rest and so on; The γ is H'. The compound (π_2) represents the whole-generation compound (II-2) obtained by the alternate synthesis reaction. More specifically, when n is i, the compound (ιι_2) is designated as the first! Substituted Compound (II_2) ' As in Example 12 below, when η is 2, the compound (11-21) is designated as the 2nd generation full-generation compound (π_2), as in Example 14 below, and so on. : (a) Method of preparation of semi-generational compound (11_2): the first! The half-generation compound is obtained by reacting a diol or a diamine represented by the above formula (V) with two of the aforementioned nitrogen heterocyclic 2,4-diketone compounds having a fluorenyl chloride group, such as The reaction formula (m4) in Fig. 4; and the first &gt; 5 to 8.5 generations of the compound (1] [_2) are sequentially carried out by a first to eighth generation of a full-generation compound (Π-2) with - The above-mentioned nitrogen heterocyclic-2,4-diketone compound having a fluorenyl group is reacted as shown in the reaction formula (m5) in Fig. 5 . Preferably, the reaction represented by the reaction formula (m4) is between 〇1 &gt; (:: to 5 ° C. Preferably, the reaction represented by the reaction formula (m5) is - Between 〇 &lt; 5 (: to 5 ° ° C. (b) Preparation of the whole-generation compound (Π-2): The first to eighth generation of the full-generation compound (II-2) is sequentially A compound of the fifth to 7.5th generation (11-2) is reacted with a unit amine or a diamine represented by the above formula (VI), as shown in the reaction formula (m6) of Fig. 6. Preferably, The reaction represented by the reaction formula (m6) is between 〇°c and 5 〇 ° C. 16 201125850 The weight average molecular weight of the poly(amine-amine ester) of the present invention is between 25 and 〇〇〇 to 30 Ό, between 〇〇〇, and is a reaction product comprising a mixture of the following components: a diisocyanate component, a polyol component and a chain extender component 'the diisocyanate The component comprises at least one diisocyanate; the polyol component comprises at least one polyol having a weight average molecular weight of between 8 and 4500, and the seam extender component comprises a The compound of the formula (II). Preferably, the content of the diisocyanate component is between 5 wt% and 25 wt%, based on the total weight of the mixture. Preferably, the total weight of the mixture The content of the polyol component is between 25 wt% and 85 wt%. Preferably, the content of the chain extender component is between 10 wt% and 60 wt% based on the total weight of the mixture. Preferably, the content of the compound of formula (II) as described above is between 75 wt% and 1 wt%, based on the chain extender component. The amidoxime-amine ester is produced in the same manner as in the prior art, that is, by mixing and polymerizing the aforementioned diisocyanate component, polyol component and chain extender component. [Examples] The present invention is to be construed as being limited to the following description. &lt;Instrument Equipment&gt; 1. (Fourier Transform Infeared Spectrum 17 201125850, referred to as FT-IR): The model number is Perkin El Mer Spectrum One FTIR Spectrometer. The analysis method used in this case is the smear method, which dissolves the sample to be tested in a solvent, and evenly spreads it on the KBr salt sheet and analyzes it after drying. 2. Nuclear magnetic resonance spectrometer (Nuclear Magnetic Resonance Spectrometer, 1H-NMR for short): The model number is Varian Unity Inova FT-NMR (200, 300 MHz) Spectrometer M3·Mass Spectrometry: The model of the instrument used in this case is Finnigan. /Thermo Quest MAT 95XL apparatus for Fast Atom Bombardment Mass Analysis (FAB-MS) and Electron Ionization Mass Analysis (EI-MS) 〇 4. Refining point meter (Melting) Point Apparatus): The model number is Fargo Melting Point Apparatus MP-2D. 5. Gel Permeation Chromatography (GPC): This is a sample filter using the N-methyl-2-pyrrolidinine (NMP) system and the sample filter used therein. It is MILLIPORE MILLEX® FG 13mm Syringe Filter (CAT No. SLFGO13NK; specification is 0.2 micron); LC pump is Postnova PN1130 Isocratic Pump S/N 0110608; pre-glass glass is [Solation Technologies 7001-05-10 ( The specification is -0.25 micron χ2·1 mm); the column is I-MBLMW-3078 (S/N HI 10211) &amp; I-MBHMW-3078 (S/N H122908) of ViscotekTM ViscoGELTM Column; the RI detector is Shodex® RI-101 ; 18 201125850 (S/Ν) device / PC interface is U-PAD portable acquisition device (SN 3 86); software is DataApex ClarityTM Chromatograph Station; PS standard is in accordance with PPS (Polymer Standard Service). 6. Universal Testing machines ·· The label is Hung Ta Instrument Co.; the model is LTD HT-8504. In this case, the test piece is cut into dumbbell type, and the intermediate test range is 2.0 cmx 0.5 cm. Tested at room temperature for 50 mm/min. 7. Elemental Analyzer (EA): The model number is Luereus CH-N-O-S Rapid Analyzer. The data of the example in this case was obtained by the Zhongxing University Guiyi Center. 8. Matrix assisted laser desorption/ionization time-of-flight Mass spectrometry (VIALDI-TOF MS): Wei brand and model German Bruker Daltonics Apex II 30e, this case The data of the examples were obtained by the Zhongshan University Guiyi Center. Preparation of a nitrogen heterocyclic-2,4-diketone compound _ <Example 1 &gt; This example is to prepare a nitrogen heterocyclic-2,4-dione compound having the following formula (el):

丨Preparation step I (1) Take p-nonylbenzene hydroperoxide (purchased from Alfa; CAS number 622-58- 19 201125850 2) 2 〇. 〇〇克 (15 〇 millimoles) and 2_B Chitin chloroform (purchased from Acr〇s 'CAS No. 2736-40-5) 4 〇 · 44 g (3 〇〇 millimolar) mixed and dissolved in 170 ml of dry xylene, and placed in a 5 〇〇ml three-neck glass in a reaction vessel. (2) Diethylamine (purchased from Tedia; cas number 121-44-8) 60.80 g (600 mmol) and 15 ml dry xylenes (purchased from Tedia; CAS number is 1330-20-7) was mixed and placed in an equal pressure separatory funnel, and dry nitrogen gas was passed over the pressure equalization funnel to obtain a xylene solution containing triethylamine. (3) The temperature in the three-necked glass reactor of the step (1) was raised to 115 by heating in an oil bath. After the hydrazine, the trimethylamine-containing xylene solution of the step (2) is slowly dropped into the reaction vessel, and the reaction temperature is controlled to be between U5t and 12〇t: by refluxing with a serpentine condenser. The reaction was monitored by FT-IR for about 4 hours, and the change of the absorption peak of the NCO functional group (2270 cm·1) of the toluene isocyanate was monitored every hour. After 49 hours, 2270 cm·〗 disappeared completely. , judged as the end of the reaction. (4) After the reaction is completed, the temperature is first lowered to room temperature. Then, the white solid formed by the reaction, ie, the triethylamine hydrochloride, is removed by suction, and the filter cake is washed with dry diphenylbenzene to leave a residue. The product on the cake is rinsed off to obtain a clear, clear yellow, wide liquid. &quot; (5) The yellow filtrate of the step (4) is concentrated under reduced pressure to remove the dioxane, which is decompressed with a water-flow pump (pressure about 15 mm Hg), and the temperature of the 20 201125850 water bath is 30 °C slowly increased to 7 (TC, avoiding the boiling of xylene, thereby obtaining a dark yellow liquid. (6) After adding 60 ml of cyclohexane to the dark yellow liquid of the step (5) and continuing to stir for several hours, Place it in the freezer layer of the refrigerator (OlOt) for 2 hours 'to completely precipitate the salt' and then remove the solid by suction filtration. Take the clear filtrate and concentrate under reduced pressure to remove cyclohexane to obtain a dark yellow. liquid.

(7) Using a micro distiller equipped with four 1 〇〇 ml round bottom bottle rotary receiving device 'A vacuum pump (about 0.3 mm Hg) was applied to the dark yellow liquid of the step (6). . Wherein, the first stage of the distillate is an incompletely reacted 2-ethyl butyl hydrazine gas (boiling point 137 ec to 139 〇 c [K 760 mm Hg]; vapor temperature 54 eC ～ 74 ° C [0.3 mm Hg]); The distillate was the target product of this example (vapor temperature 78 &lt; 5 (: ~ 80 C [0_3 mm Hg]), and the yield of the target product was calculated to be 81%.

The results of FT-IR (cm·1) were as follows: 1851 (C = 0 for gas heterocyclic 2, 4 - diketone), 1742 (c = 0 for nitrogen heterocycle 2, 4 - diketone) &lt;&gt ; NMR was identified as !H NMR (200 MHz, DMSO-rf6), 5 (ppm): 0.915 (t, 6H, H-2, -CH3), 1.787 (q, 4H, Hl, -CH2), 2.305 (s, 3H, H-5, Ar-CH3), 7.274 (d, 2H, H-4, Ar-H), 7.557 (d, 2H, H-3, Ar-H) Identification of 〇EA (%) Results: The theoretical values are c: 72 7〇, H: 7.41, N: 6 〇6; the straightness values are C: 72.19, H, 7.31, N, 5.61. Identification of EI-MS (Da): The theoretical value is 231.13; the measured value is 23^. 21 201125850 The standard product is a nitrogen heterocyclic-2,4-diketone compound having the objective (el) of Example 1 as described above. &lt;Example 2 &gt; Azacyclobutene-2,4-diketone having the following formula (e2) This example is to prepare a compound:

(e2) (1) Take the target product of Example i at 10·00 g (43 mmol), evolved (from Aldrich) 200 mg (1.9 mmol), and acetic acid (expressed from (8) 200 mg ( 1.1 millimoles), manganese acetate (purchased from Akidch) measured in milligrams (1.6 millimoles) and over double oxidized isopropyl stupid (from Aldrich) 400 mg (1.48 millimoles) in 125 ml three In the flask, mix well with 110 ml of acetic acid to obtain a first solution. (2) Inject pure oxygen (〇2(g)) into the gas using a gas dispersi〇n friUed disc. In the first solution, the temperature was controlled at 115. The reaction was carried out under the conditions of 'using a thin layer chromatography (TLC) to monitor the reaction (the volume ratio of ethyl acetate to n-hexane was 1:4) until Example j The target product disappeared (determined as the end point of the reaction), and the reaction lasted for 8 hours. (3) After the completion of the reaction, '800 ml of pure water was added to obtain 2.94 g of a pure white solid product, which was found to have a melting point of 143.5. (: ~144.5 °C, yield 88%. 22 201125850

Identification of 丨 structure identification I FT-IR (cm·1): 2700~3700 (OH of -COOH), 1872 and 1748 (C=0 of nitrogen heterocyclic-2,4-dione), 1731 (-COOH) 00). The NMR results were NMR (200 MHz, DMSO-i/6), 5 (ppm): 0.924 (t, 6H, H-2, -CH3), 1.788 (q, 4H, Hl, -CH2), 7.823 ( Ds 2H, H-4, Ar-H), 8.043 (d, 2H, H-3, Ar-H), 13.184 (broad s, 1H, H-5, -COOH). The results of EA (%) were: C: 64.36, Η: 5.79, N: 5.36; measured values were C: 64.00, Η: 5.28, N: 5.05. Identification of EI-MS (Da): theoretical value is 261.1; measured value is 261.1. From the above test, the product of Example 2 was a nitrogen heterocyclic-2,4-bis-line compound having the above formula (e2). &lt;Example 3 &gt; This example is to prepare a nitrogen heterocyclic-2,4-diketone compound having the following formula (e3):

Preparation Procedure | (1) 5.00 g (19.1 mmol) of the product of Example 2 and 40 ml of the dried cyclohexane were placed in a 125 ml three-neck glass reaction vessel, and the two were mixed for two phases. In a mutually soluble state, a gasified thionyl chloride (available from 'Seedchem; CAS No. 7719-23 201125850 09-2) 22.7 g (190.9 mmol) was added to obtain a reaction solution. (2) The reaction solution was vigorously stirred with a magnet, and the reaction temperature was controlled at 60 ° C by refluxing with a serpentine condenser while monitoring the reaction by TLC (the ratio of ethyl acetate to n-hexane was 丨: 4) After the product of Example 2 disappeared, the reaction was continued for 2 hours and an orange-yellow homogeneous liquid was obtained. (3) Excess sulfinium chloride and cyclohexane in the orange clear liquid of the step (2) were removed by a reduced pressure concentrator to obtain 5.36 g of a solid product. &lt;Example 4 &gt; The nitrogen heterocyclic 2,4·diketone-based compound to be prepared in this example is the same as that of Example 3 except that this example is a 4-isohydroxybenzophenone gas (purchased) From Acros) to do the reactants. i Preparation step (1) Under the condition of 1KTC and under nitrogen atmosphere, 4 ml of dried xylene containing 1 〇1 g of triethylamine (100 mmol) is slowly dropped into the mixture, 4-iso 5 00 g of hydroxybenzhydryl chloride (27 5 mmol) and 7.5 g of 2 -ethyl butyl chloride (55.7 mmol) of diphenylbenzene after drying for about 1 hour to obtain a reaction Solution. (7) The reaction solution of the step (1) was vigorously (4) with a magnet, and the reaction temperature was controlled to liot: by refluxing with a serpentine type condenser for 2 hours. Then, the reaction solution was cooled to room temperature, and filtered to remove the sink to obtain a clear liquid. (3) Excess dimethyl 24 201125850 benzene in the clarified liquid of the step (7) is removed by a vacuum concentrator and recrystallized by using 50 ml of cyclohexane to obtain 3.5 gram of a solid product, which is measured. The results of the identification of the melting point of 1〇7〇c~1〇8〇c 〇FT~IR (cm·1): 1769 (_c醯〇), 1748 and 187〇 (nitrogen heterocycle·2, _c=〇pNMR of 4_dione was identified as ιΗ NMR (20〇MHz, DUSO-d6), δ(ρριη) : 1.04 (t, 6H, -CH3), 1.84 (q, 4H, -CH2- ), 8.02 (d, 2H, ArH), 8.17 (d, 4H, ArH). Identification of EI-MS (Da): theoretical value: 279.07; measured value: 279.2.

Preparation of a compound of formula (II): Ai-B The structural formula of the compound of formula (II) synthesized in all of the following examples is shown in Table 1 below. Further, the compounds prepared in Examples 5 to 10 are Is a compound (II-1) as defined above, that is, a compound represented by when B in the formula (11) is _X-Al; and the compound prepared in Examples 11 to 16 is a compound as defined above (Π) -2), that is, a compound represented by when b in the formula (Π) is -X. 25 201125850 Κ·6,Κ·7 c2h5 1 c2H5 c2h5 c2h5 c2h5 c2h5 c2h5 c2H5 c2h5 c2h5 c2h5 c2h5 y〇 p- Ρί Pi . each. a is the same as the embodiment 5, the same as the embodiment 5, the same as the embodiment 5, the same as the embodiment 5, and the same as the embodiment 5, X Αι and A 〗 R4, R5 1 c2H5 c2h5 c2H5 c2h5 c2h5 1 c2h5 c2h5 C2H5 c2h5 1 _1 C2H5 1 N 1 1 id_2 Φ (N s 1 is the same as Embodiment 6 and Embodiment 6 is the same as Embodiment 6 and Embodiment 6 is the same as Embodiment 6 is the same as Embodiment 6 _i is the same as Embodiment 6 and Embodiment 6 The same as in the sixth embodiment - H rH &lt; N (N m 〇 (N (N m &gt;&lt; X ό X - X 〇 V VIII is the same as in the embodiment 5 and the same as the embodiment 5 is the same as the embodiment 5 The same as Embodiment 5 is the same as Embodiment 5, and Embodiment 11 is the same as Embodiment 11 and Embodiment 11 is the same as Embodiment 11 and is the same as Embodiment 11 PQ ! -x-a2 -x-a2 -x-a2 - X - a2 - x - a2 - x - a2 &gt;&lt; k &gt;&lt;&gt;&lt;&gt;&lt; 1 x Embodiments Example 5 - Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 201125850 Preparation of compound (II-1): Arx-A2 [Examples 5 to 10]

Examples 5 to 1 are to prepare a compound of the formula (e4): bl Λ-\ Η

(e4) This example is to prepare a compound of the above formula (4), and wherein the private is _ Ο

丨Preparation step

(1) In the reaction vessel, the solid product of Example 3, 5% g (yangmole) was dissolved in 5 ml of dry ethyl ethane - _ _ 1 kiss as a coffee; ()) (purchased from JTBaker; CAS number 78_93-3 ), and pass dry nitrogen, 4,4. diaminobenzophenone (4,4, thy thy; 4,4' complement ^) (purchased from A · ; CAS number ιοί- 77-9) I.94 g (9.8 mmol) and triethylamine 3 Buick (π 3 mmol) placed in an isobaric liquid separation wiper and transferred to W ml Qianna K to obtain - the first solution, _ a dry gas gas was passed over the equal pressure separator funnel, and 4,4'-MDA was slowly dropped into the reaction vessel' and the reaction process was removed using an ice bath to generate a large amount of heat. (2) After the end of the reaction (about 10 minutes), the solution and the precipitate (ie, by-product quaternary ammonium salt) were separated by suction filtration, and the filter cake was rinsed with freshly dried MEK to obtain a transparent clear yellow filtrate. . 27 201125850 (3) Drop the clear and clear yellow filter of step (7) into a beaker containing _ml of cyclohexane. At this time, the yellowish color will be precipitated, and the paste will be separated to obtain the pale yellow solid. The pale yellow solid was dried in a vacuum oven at a temperature of 6 (rc and pressure 〇丨_Hg for 1 hour to remove MEK and cyclohexyl. (4) After drying 80 ml of ethanol and the step (3) 5 73 g of light yellow solid was mixed for 2 hours, and filtered by suction to obtain a color solid (the impurity was dissolved in ethanol). (5) The white solid of the step (4) was placed at a temperature of 6 The vacuum oven of 〇ta pressure was 〇imm and dried for 3 hours to completely remove the ethanol, thereby obtaining 5 5 g of a white solid product, which was measured to have a melting point of 162.5. (: ~163.0 ° C, yield was 83%.

Identification of 丨 structure identification I FT-IR (cm·1): 3310 (nh of amine), 1869 and hydrazine (C=〇 of nitrogen heterocycle _ 2,4-dione), 165 〇 (00 of amine) ). The NMR results were 〖H earn (2 〇〇 MHz, DMSO-^6), 5 (ppm): 0.946 (t, 12H, Hl, -CH3), 1.824 (qs 8H H-2 -CH2), 3.894 ( s, 2H, H-8, Ar-CH2-Ar), 7.193(d, 4H, H-7, Ar-H), 7.674(d, 4H, H-3, Ar-H), 7.836(d, 4H , H-6, Ar-H), 8.073 (d, 4H, H-4, Ar-H), i 263 (s 2H H-5, -NH). EA (%): Theoretical value C: 71.9 Bu H: 5.8, N: 8,18; measured values C: 71.77, Η: 5·83, N: 7.92. The result of EI-MS (Da) identification: theoretical value is 684.29; the value of the adjustment is 684.5. The molecular weight distribution index (PDI) = 1.06 was measured by GPC (NMP); the number average molecular weight was 922 g/mol; and the weight average molecular weight (Mw) was 977 g/mol. It can be seen from the above test that the product of Example 5 is a compound represented by the above formula (e4). 201125850 &lt;Example 6&gt; The present example is to prepare a compound represented by the above formula (e4), and wherein &amp; For Q,

I Preparation Steps Each (1) was dissolved in dry dimercaptocaramine (DMF) (purchased from Tedia) at room temperature (20. 〇25. 〇, taking the product of Example 5, 5.5 g (8.0 mmol). CAS number 68-12-2) After 40 liters, add 4-aminobenzyl amine (purchased from Aldrich; CAS number 4403-71-8) 2.16 g (17.7 mmol) The reaction was monitored by TLC (the volume ratio of ethyl acetate to n-hexane was 2··3) until the point representing the product of Example 5 gradually disappeared, and the reaction was continued for 5 minutes to obtain a reaction solution. The reaction solution of the step (1) is dropped into a beaker containing about 9 ml of ultrapure water, at which time a white solid precipitates. A white solid is separated by suction filtration, and the solid product is placed at a temperature. Drying in a vacuum oven at 80 ° C and a pressure of 0.1 mm Hg for 72 hours 'to remove DMF and water' to obtain a pale yellow solid of 6.87 g, which was measured to have a melting point of 203.3 ° C to 204.2 ° C. The rate is 92%.

Identification of 丨 structure identification I FT-IR (cm·1): 3330 (N-H of amine), 1652 (C=0 of amine). The results of Nmr were: iHNMRpOO MHz, DMSO-form), δ(ρρπι): 0.674(t,12H, -CH3), 1.931(q, 8H, H-8, -CH2), 3.884(s, 2H, Hl , Ar-CH2-Ar), 4.171(d, 4H H-ll, -CH2), 4.924(s, 4H, H-14, -NH2), 6.451(d, 4 Η, H-13, Ar-H) , 6.919(d5 29 201125850 4H, H-12, Ar-H), 7.174(d, 4H, H-2, Ar-H), 7.671(d, 4H, H-3, Ar-H), 7.738(d , 4H, H-5, Ar-H), 7.919(d, 4H, H-6, Ar-H), 8.448(t, 2H, H-10, -NH-), l〇.〇87(s, 2H, H_7, Ar-NH-), 10.765 (s, 2H, H-4, -NH-CO). EA (%): theoretical value c ·· 71.10, H: 6.5 卜 N: 12.06; measured value C: 71.06, H: 5.96, n: 11 93 〇EI-MS (Da) identification result. Theoretical value 928.46; measured value 929 ^ measured by GPC (NMP) PDI = 1.10; Mn = 2078 g / mo; Mw = 2286 g / zip code maldl TOFMS (Da) identification results: [M + Na] + = 951.6; [M+K]+=967.6. From the above test, it is understood that the product of Example 6 is a compound represented by the above formula (e4) 实施 &lt;Example 7&gt; This example is to prepare a compound represented by the above formula (e4), and wherein e is Q. C,H&lt; ', 1 fishing

, C2H5 • c2h5 (

I Preparation Step I (1) The same procedure as in Example 3 (but different amounts of reactants) was carried out to prepare the heterocyclic-2,4-diketone compound of the formula (9), and then dissolved. It was placed in a 35 ml dry well and placed in an isocratic separatory funnel to obtain a first solution. (2) The product of Example 6 was taken as 2.77 g (3 〇 mmol) and triethylamine} &amp; gram (1) 3 mmol

In JD1, it is connected to nitrogen. (3) Passing dry nitrogen gas above the isobaric separatory funnel of the step (1), and slowly dripping the person (3) containing the product of the paid 6 product, and the first solution 4 of the three necks In the glass reactor alone 30 201125850, a large amount of heat is generated at this time, so the heat needs to be removed by an ice bath, and in order to make the reaction uniform, stir until overnight. (4) After the reaction is completed, the solution and the precipitate (i.e., by-product quaternary ammonium salt) are separated by suction filtration, and the filter cake is washed with freshly dried MEK to obtain a pale yellow filtered solid. (5) The tilting (4) The light yellow (10) is placed in a beaker of 2 (8) ml of ultrapure water to dissolve the by-products of the fourth-order salt. The solvent is then separated and the sediment is separated, and the filtered solid is placed at -80. Drying in a vacuum chamber at a pressure of 0.1 mm Hg for 1 hour 〇 (6) Mix 200 ml of ethanol with 431 g of the dried pale yellow solid. After 2 hours, filter off by suction to obtain a white solid product (impurity) Dissolved in ethanol), and placed shai white solid product at a temperature of 6 〇 (: and dried in a vacuum oven at a pressure of 0.1 mm Hg for 6 hours to remove ethanol, thereby obtaining a white solid of 3 83 g, measured It is known that the melting point is 183.5 ° C ~ 184.7 ° C, the yield is 91%. 丨 structure is the identification of FT-IR (cm · 1): 3315 (amine group printing, 1869 and mouth similar (nitrogen heterocycle) _ 2,4-dione C = 0) ' 1652 (amine C = 0). NMR was identified as: iH NMR (2 〇〇 MHz, DMSO-J6) ), 6 (ppm): 0.733 (t, 12H, H-9, -CH3), 0.977 (t, 12H, H-18, -CH3), 1.839 (q, 8H, H-8, -CH2), 1.991 (q, 8H, H-17, -CH2), 3.878(s, 2H, Hl, Ar-CH2-Ar), 4.343(d, 4H, H-ll, -CH2), 7.203(d, 4H, H- 12, Ar-H), 7.281(d, 4H, H-2, Ar-H), 7.672(d, 4H, H-15, Ar-H), 7.698(d, 4H, H-4, Ar-H ), 7.790(^ 4H, H-4, Ar-H), 7.861(d, 4H, H-4, Ar-H), 7.956(d, 4H, H-4, Ar-H), 8.096(d, 4H, H-4, Ar-H), 8.596(t, 2H, H-10, -NH-), 10.075(s, 2H, H-14, -NH-CO), 10.267(s,2H,H- 7, Ar-NH-), 10.577 (s, 2H, H-4, -NH-CO). EA (%): theoretical value C: 70.42, H: 6·12, N: 9.8; measured value c : 70.05, H : 5.63, N : 31 201125850 9.98. FAB-MS (Da) identification result: The theoretical value is the material skipping; the measured value is (4) $. Using PPC = P), PDI = U1; Mn = 2496g / m 〇 1; (d). It can be seen from the above test that the product of Example 7 is a compound represented by the above formula (IV) &lt;Example 8&gt;

I Preparation Step I. In this example, a compound was prepared in the same manner as in Example 6, except that the step (1) was to dissolve 1.0 g (0.77 mmol) of the product of Example 7 in a dry state. In 6 ml of DMF, further reacted with 190 mg (1.6 mmol) of 4-aminomoutamine, and the volume ratio of ethyl acetate to n-hexane used in the TLC test was 7:3; in step (2) The ultrapure water was used in an amount of 150 ml, and the obtained product had a melting point of 168.8. 〇173.5. (:; Yield: 90%. 丨 鉴 鉴 · FT-IR (cm·1) Identification results: 3332 (NH of amine), 1651 (amine 〇 0). NMR (300 MHz, DMSO-^6) ), δ(ρριη) : 〇.727(t} 24H, H-9, -CH3), 1.959(q, 16H, H-8, -CH2), 3.879(s, 2H, Hl, Ar-CH2-Ar ), 4.183(d, 4H, H-ll, -CH2), 4.336(d, 4H, H-19, -CH2), 4.923(s, 4H, H-22, -NH2), 6.475(d, 4H, H-21, Ar-H), 6.944 (d, 4H, H-20, Ar-H), 7.201 (d, 4H, H-12, Ar-H), 7.262 (d, 4H, H-2,

Ar-H), 7.693(d, 8H, H-13, H-3, Ar-H), 7.786(d, 8H, H-15, H-5, Ar-H), 7.950(d, 8H, H -6, H-16, Ar-H), 8.443(t, 2H, H-10, -NH-), 8.593(t, 2H, H-26,- 32 201125850 NH-), 10.096(s, 4H, Η-14, Η-17, -NH-CO, Ar-NH-), 10.602(s, 2H, H-7, Ar-NH-), 10.764(s, 2H, H-4, -NH-CO) . EA (%): The theoretical value is c: 7〇 18, H: 6.44, N: 11.81; the measured value is C: 69·72, h: 6_22, N: u 71. FAfi description (Da): The theoretical value is 1658.81; the measured value is 1659. Using GPC(NMP) '• measured PDI=1.12; Λ/η=3834 g/m〇l; Mw = 4294 g/md. The result of identification with y / (Da): [M+Na]+=1682.6; [M+K]+=1698.6. It can be seen from the above test that the product of Example 8 is a compound represented by the above formula (IV) &lt;Example 9&gt;

In this example, a compound was prepared in the same manner as in Example 7, except that the nitrogen heterocyclic diketone compound having the formula (IV) obtained in the step (1) was 〇54 g, and its lyophilized 3G was used.奸魏 meK; the product of the stalk (2) green lion case 8 is still mixed (〇·4 moles) and diethylamine fluorite (5 9 moles) mixed and partially dissolved in milliliters of dryness The dry yellow solid after the drying of the step (6) is 56 g, and the obtained white solid is 0.717 g, and the melting point is 2 〇 7 n &gt; 2 〇 9 rc, and the yield is 8 峨 FT- Identification of IR (cm): 3315 (N_H of amine), 1869 and 1741 (nitrogen heterocycle c-Ο) &gt; 1654 (5$^ c=〇) 〇&gt;H NMR (300 MHz, DMSO-^ 33 201125850 5(ppm) : 0.643(t, 24H, H-9, -CH3), 0.888(t, 12H, H-26, -CH3), 1.752(q, 8H, H-25, -CH2), 1.905( q, 16H, H-8, -CH2), 3.795(s, 2H, Hl, Ar-CH2-Ar), 4.251(ds 8H, H-ll, H-19, -CH2), 7.114(d, 4H, H-2, Ar-H), 7.190 (d, 8H, H-12, H-22, Ar-H), 7.609(d} 12H, H-5, H-15, H-23, Ar-H) , 7.7〇3 (d5 8H, H-6, H-24,

Ar-H), 7.770 (d, 4H, H-16, Ar-H), 7.866 (d, 8H, H-13, H-21, Ar-H), 8.009 (d, 4H, H-3, Ar -H), 8.516(t, 4H, H-10, H-18, -NH) &gt; 9.999(s, 2H, H-17 -NH-CO) &gt; 10.024(s, 2H, H-14, Ar -NH-), 10.197(s, 2H, H-7, Ar-NH-), l〇.5〇3(s, 2H, H-22, -NH-CO), 10.528(s, 2H, H- 4, -NH-CO). The result of EA (%) is: C. 69.94, Η 6.20, N. 10.44; measured value C: 68.93, Η: 6 08, N: 10.46. FAB-MS (Da) identification: theoretical value 2144.99; measured value 2146. PDI = 1.12; Mn = 4251 g/mol; Mw = 4761 g/mol as measured by GPC (NMP). It can be seen from the above test that the product of Example 9 is a compound represented by the above formula (e4). [Example 1〇&gt; This example is to prepare a compound represented by the above formula (e4), and

The preparation procedure was carried out in the same manner as in Example 6 except that the step (1) was that the product of Example 9 was dissolved in 440 mg (0.2 mmol) in dry DMF. In 4 ml, the reaction was carried out by adding 4% basic amine 90 gram (0.7 mmol), and the extract used in the TLc test was ethyl acetate; the amount of ultrapure water in the step (2) was 1 〇〇 ml, 34 201125850 The product obtained had a melting point of 180.8 ° C to 182.3 ° C; the yield was 91%. Structure Identification

The result of FT-IR (cm·1) identification: 3306 (N-H of amine), 1654 (C=0 of amine). 4 NMR (300 MHz, DMSO-i/6) 5 5 (ppm): 0.694 (t, 36H, H-9, -CH3), 1.952 (q, 24H, H-8, -CH2), 3.873 (s, 2H, Hl, Ar-CH2-Ar), 4.175(d, 4H, H-19, -CH2), 4.326(d, 8H, H-27, H-ll, -CH2), 4.921(s, 4H, H -30, -NH2), 6.466(d, 4 Η, H-29, Ar-H), 6.935(d, 4H, H-12, Ar-H), 7.227(d, 12H, H-28, H- 2, H-20, Ar-H), 7.686 (d, 12H, H-3, H-13, H-23, Ar-H), 7.756 (d, 12H, H-24, H-21, H- 15, Ar-H), 7.913 (d, 12H, H-6, H-16, H-5, Ar-H), 8.438(t, 2H, H-10, -NH-), 8.590(t, 4H , H-26, H-18, -NH-), 10.094 (s, 6H, H-25, H-17, H-14, -NH-CO, -NH-CO, Ar-NH-), 10.607 ( s, 4H, H-22, H-7, -NH-CO, Ar-NH-), 10.764 (s, 2H, H-4, -NH-CO). The theoretical value of EA (% ” is C: 69.83, H: 6 4b N: 1172; the measured value is C: 69.08, Η: 6.89, N: 11.25. PDI=U2 is measured by GPC (NMP); Mn= 5476g/ Mol '' Mw = 6133 g/mol. MALDI-TOF MS (Da) was determined as follows: [M+Na]+=2412.2. From the above test, the product of Example l is as above (e4) The compound shown is a compound (II-2): Α^Χ, [Examples 11 to 16] Examples 11 to 16 are to prepare a compound represented by the following formula (e5):

(e5) &lt;Example 11&gt; This example is to prepare a compound represented by the above formula (e5), wherein 仏 is 35 201125850

I Preparation Step I (1) The same procedure as in Example 3 (but different amounts of reactants) was carried out to obtain 3.5 g (12 mmol) of the nitrogen heterocyclic-2,4-dione compound of the formula (e3). After that, in hexane (concentration 2.48 X 10_4 mM), and placed in the first room a first solution. It was dissolved in a dry loop separatory funnel to obtain (2) aniline 1, 2 g (13 mmol), and ethyl fine 1_3 g (13 mmol) in a three-neck glass reaction vessel. Ears, and 50 ml of cyclohexane, and passed through nitrogen. (3) Passing dry nitrogen gas above the isobaric separatory funnel of the step (1), and slowly dropping the first liquid solution into the three-neck glass reaction vessel of the step (2), at this time, a large amount Heat is generated, so it is necessary to remove the heat in an ice bath. After the first solution is dripped, it is continuously stirred for % = clock. (4) After the reaction is completed, the solution and the precipitate are separated by suction filtration. After the solid filter cake was dried, it was extracted with a 1:1 ratio of ethyl acetate/water in a volume ratio, and the organic phase of the towel was concentrated to give a pale yellow solid powder. (5) The pale yellow solid powder of the step (4) is dissolved in 4 G of tetrahydrocyanate (purchased from CAS No. 1G9_99_9), and is precipitated in _ml of cyclohexane. Lin to white m booty. This washing step 3: owing was repeated, and the white solid product was placed at -temperature 6 (TC and pressure (drying in a vacuum supply chamber of π mm Hg for 6 hours) to obtain a white powder product of 41 g, which was measured. Known as i63t~16rc, the yield is 9δ%. — Structure identification _ 36 201125850 NMR identification results are: ^ NMRpOOMHz, acetate-c/6), δ(ρρπι) : 1.03 (t, 6H, -CH3), 1.87 (q, 4H, -CH2-)5 7.09 (t, 1H, ArH), 7.33 (t, 2H, ArH), 7.82 (d, 2H, ArH), 7.92 (d, 2H, ArH), 8.12 (d, 2H, ArH), 9.61 (s, 1H, -NH-) 〇EA (°/〇): theoretical value C: 71.4 b H: 5.99, N: 8.33; measured value c: 70.73, H: 5.90, N : 8.95 ; The molecular formula is C2〇H2〇N2〇3. The structure I of EI-MS (Da) is monitored: theoretical value is 336.15; measured value is 336.4. PDI=i.〇i; Mn measured by GPC (DMF) = 1,687 g/mol 0 According to the above test, the product of Example 11 is a compound represented by the above formula (e5) &lt;Example 12&gt; The present example is to prepare a compound represented by the above formula (e5). Chinese

I Preparation Step (1) 1.0 g (2.9 mmol) of the product of Example 11 and 6 ml of dried DMp were added to a glass reaction vessel at room temperature (2 ° C to 25 ° C) under a gas atmosphere, and the former was dissolved. After the -first solution is obtained. Further, 4-aminoaniline 38 mg (3 μmmol) was dissolved in dry DMF i ml, and the solution was slowly dropped into the first solution to carry out the reaction: the reaction was monitored by TLC (acetic acid ethyl acetate) The volume ratio to the calcined product was 3 ·· 2) until the point representing the product of Example 11 disappeared, and the reaction was continued for 1 hour to obtain a reaction solution. ‘ (2) This step (1) Kirin liquid is about 9 (mL) in the ultra-pure water cup, and 37 201125850 is mixed for a few minutes' at this time there will be a white white solid powder. Sakisaki / the end material, the age is reduced by the age of one. The final prosthesis was placed at a dish size of 60 C and the house power was αι _ % to remove DMF and water, and (10) 5 was dried in the X' phase & 72 hours, #κ&gt; Ψ color solid powder product 1.2 g, It was found to have a melting point of 212 ° C to 2 Torr and a yield of 91%.丨Structure identification 1 Ugly mosquito knot called dereliction of duty (10) Called coffee (4) (4) (d, 2H, ArH), 6, 2 (d, 2H, ΛτΗ), , 05 (t, 1Η, ΛτΗ), 7.31 (t, 2Η, λ, η), , 76 (d, 4Η, ΑΓΗ), , 93 (d, 2Η, ArH), 8.44 (t, 1Η, -ΝΗ-), 10,3(s, 1Η, -ΝΗ,,, 10.78 (s, 1Η, -ΝΗ-). ΕΑ (6): The theoretical value is c: m72, Η: 6 59, ν: ΐ 2 22 ; the measured value is C 70.81 Η . 6.57, Ν . 12·58 ' The formula is c27h30N4O3. The result of EI-MS (Da) was found to be 458.23; the measured value was 458·6. PDI = 1.01 was measured by GPC (DMF); Mn = 4,028 g/mol ° The product of Example 12 was confirmed by the above test. It is a compound represented by the above formula (e5). &lt;Example 13&gt; This example is to prepare a compound represented by the above formula (e5), wherein E2 is

(3) Preparation step 丨 (1) The same procedure as in Example 3 (but different amounts of reactants) was used to prepare the nitrogen of the formula (e3) 38 201125850 Heterocyclic-2,4-dione compound 3.5 g (12 mmol) After the ear, it was dissolved in dry cyclohexane (excitation 2.48 X ΙΟ·4 mM) and placed in an isocratic separatory funnel to obtain a first solution. (2) Reaction in a three-neck glass The product of Example 12 was added to the vessel. 5. gram (u millimolar), = 1.2 g of ethylamine (12 mmol), and 90 ml of dry THF, and passed through a gas atmosphere. - (3) Step (1) is placed above the isostatic separatory funnel with dry nitrogen gas, and the first solution is slowly dropped into the three-neck glass reaction vessel of the step (2), at which time a large amount of heat is generated, so The ice bath removes heat, and after the first solution is dropped, it continues to disturb 3 φ minutes. (4) After the reaction is finished, the solution and the precipitate are separated by suction filtration. / brine extraction, the organic phase is concentrated to give a pale yellow solid powder. (5) The pale yellow solid powder of the step (4) is dissolved in 30 ml of DMF, and at 12 〇 The precipitate was precipitated in ML ultrapure water, and filtered by suction to obtain a white solid product. The white solid product was dried in a vacuum oven at a temperature of 60 ° C and a pressure of 0.1 mm Hg for 72 hours to obtain a white solid powder of 7.3 g. It has been measured that its melting point is 258 ° C ~ 263 ° C, the yield is 96%. | Structural NMR identification results: W NMR (300 MHz, DMSO-怂), δ (ρριη): 〇. 7〇(t, - 6H, -CH3), 0.95 (t, 6H, -CH3), 1.82 (q, 4H, -CH2-), 1.94 (q, 4H, -CHr), 4.32 V (d, -CH2) -), 7.05 (t, 1H, ArH), 7.25-7.36 (m, 4H, ArH), 7.66-7.86 (m, 8H,

ArH), 7.94 (d, 2H, ArH), 8.07 (d, 2H, ArH), 8.60 (t, 1H, -NH-), 1014 (s, 1H, _ NH-), 10.29 (s, 1H) , -NH-), 10.60 (s, 1H, -NH-). EA (%) identification results: theoretical values C: 70.17, Η: 6.18, N: 9.98; measured values C: 69.57, Η: 6.29, N: 9.98. The result of FAB-MS (Da) identification: the theoretical value is 701.32; the measured value is 7〇24.利 39 201125850 measured by GPC (DMF) pdi = i.oi ; 1^=4,149^11101. It can be seen from the above test that the product of Example 13 is a character of the above formula (Embodiment 14) &lt;Example 14&gt;

(1) Add 2.0 g (2·8 mmol) of the product of Example I3 and dry DMF ml in a glass reaction vessel at room temperature (2 (TC~25.) under a nitrogen atmosphere, after dissolving the former. The -first solution was obtained. Further, 4-aminoaniline 38 mg (3 mmol) was dissolved in 1 ml of dry DMF, and the solution was slowly dropped into the first solution to carry out a reaction, and the reaction was monitored by TLC. The volume ratio of acetic acid to Zhengxie was 3: ^ until the point representing the product of Example B disappeared, and the reaction was carried out for 5 hours to obtain a reaction solution. (2) The reaction solution of the step (1) was dropped. Into a beaker containing about 3 ml of ultrapure water, and mix for a few minutes 'At this time, a solid solid powder will be precipitated, and the white solid will be separated by side extraction_filter. This washing step is repeated at least twice. The final fines were placed in a vacuum chamber with a temperature of 6 ° C and a pressure of 〇 _i _ Hg for 72 hours, U removed DMF and water' to obtain 2 2 g of _ white solid powder, which was measured. Its melting point is 100 ° C ~ 1 HTC, the yield is 94%. | Structural identification is 40 201125850 NMR identification results: iH NMR (400 MHz DMSO-horse), δ(ρριη) : 0.67 (m, 12H, -CH3), 1.91 (m, -8H, -CHr), 4.16 (d, 2H, -CH2-), 4.31 (d, 2H, -CHr) ), 4.92 (s, 2H, -NH2), 6.44 (d, 2H, ArH), 6.93 (d, 2H, ArH), 7.04 (t, 1H, ArH), 7.23-7.34 (m, 4H, ArH), 7.66-7.86 (m, 8H, ArH), 7.91 (t5 4H, ArH), 8.44 (t, 1H, -NH-), 8.58 (t, 1H, -NH-), 10.09 (s, 1H, -NH- ), 10.12 (s, 1H, -ΝΉ-), 10.59 (s, 1H, -NH_), 10.76 (s, 1H, -NH-). EA (%) identification result: theoretical value C: 69.97, Η : 6·48, N: 11.90 ; measured value: C: 68.75, Η: 6.78, N: 11.65; molecular formula is C48H53N7〇6. Structure identification of FAB-MS (Da): theoretical value is 823.41; measured value is 825. Structure identification of MALDI-TOF MS (Da): [M+Na]+= 846.5. PDI=l.〇2; Mn=6,486 g/mo as measured by GPC (DMF) The product of Example 14 was confirmed by the above test. That is, the compound 0 represented by the above formula (e5) &lt;Example 15&gt; The present example is to prepare a compound represented by the above formula (e5), wherein e2 is

|Preparation Procedure| This example was prepared in the same manner as in Example 13 except that the step (2) was obtained by mixing the product of Example 14 with 9.06 g (11 mmol) and triethylamine 12克(12 mmol) and dry DMF 90 ml; and the product obtained in the step (5) has a melting point of 273 ° C to 277 ° C and a yield of 77%. |Structural identification | 41 201125850 NMR identification results:]H NMR (300 MHz, DMSO-for), s as ruthenium (Pillow 'CHr), 4.34 12H, -CH3), 0.97 (t, 6H, -CH3) ), 1.84 (q, 4H, -CHr), 1.96 (qq, 8Ji (d, 4H, -CH2-), 7.07 (t, 1H, ArH), 7.26 (t, 4H, ArH), 7.33 (tj 3 ,ArH),7_68- 8.10 (m,20H,ArH),8.59 (q,2H,-NH-),10.10 (s,1H,-NH,,1Λ Λ !〇.12 (s, 1H,- NH- ), 10.27 (s, 1H, -NH-), 10.61 (s, 1H, -ΝΉ-), 10.62 (s&gt; lu n

C, NMR (150 MHz, DMSCM), 3 (ppm): 8.87, 8.92, 22.74, 27.26, 42.17, 58.62, 71.35, 118.72, 119.40, 120.20, 120.33, 123.47, 127.50 ' Q7.56 , 128.40, 128.43, 128.54, 129.14, 129.43, 129.47, 132.92, 134.66 i. 5 u5.〇3, 135.33, 137.61, 137.91, 139.25, 141.59, 164.29, 164.69, 164.79 5 171.26, 171.61, 172.56. EA (%) identification results: theoretical value C: 69.77, H: 6 is J 'N: 10.50; measured value C: 69.34, H: 6.24, N: 10.37; molecular formula is 52il66N8〇9 = FAB- using MS (Da) identification result: theoretical value 1066.50; measured value Sen, ^ 1〇67.0 GPC (DMF) measured PDI=1.02; Mn=6,563 g/mo of the compound indicated by the above test, the product of Example 15 &lt;Example 16&gt;

I Preparation of the Step I This example was prepared in the same manner as in Example 14 except that the step (2) was replaced by the product of Example 15, 3.0 g (2.8 mmol). Production 42 201125850 substance 2.0 g (2.8 millimoles).丨Structural identification 丨 NMR identification results: NMR (600 ΜΗζ, DMSO-禹), δ (ρρηι): 0.71 (m, 18H, -CH3), 1.92 (m, -12H, -CHr), 4.19 (d, 2H ,-CH2-),4_34 (d,4H,-CHr), 4.92 (s, 2H, -NH2), 6.47 (dd, 2H, ArH), 6.94 (d5 2H, ArH), 7.07 (t, 1H, ArH ), 7.26 (d, 4H, ArH), 7.33 (t, 2H, ArH), 7.69 (dd, 4H, ArH), 7.76-7.97 (m, 14H, ArH), 8.44 (t, 1H, -NH-) , 8.59 (m, 1H, -NH-), 10.10 (s, 1H, -NH-), 10.12 (s, 1H, -NH-), 10.62 (s, 1H, -NH-), 10.64 (s, 1H , -NH-), 10.79 (s, 1H, -NH-); ,3C NMR (150 MHz, DMSO-i/6), 6 (ppm): 8.93, 8.99, 27.25, 27.33, 27.71, 42.19, 42.23, 58.48, 58.62, 113.64, 119.34, 119.41, 120.21, 120.34, 123.47, 126.38, 127.50, 128.21, 128.42, 128.54, 129.43, 129.47, 134.66, 137.91, 139.25, 141.52, 141.57, 141.59, 147.43, 164.69, 164.80, 171.27, 171.36, 172.45, 172_56, 172_58. EA (%) identification results: theoretical values c: 69.68, H: 6.44, N: 11.78; measured values C: 68.11, Η: 7.44, N: 11.49; molecular formula C69H76N1G〇9. FAB-MS (Da) identification: theoretical value 1188 58; measured value 1189. Identification of MALDI-TOF MS (Da): [M+Na]+= 12116. PDI = 1.02 was measured by GPC (DMF); Mn = 8,586 g/mol. It can be seen from the above test that the product of Example 16 is a compound represented by the above formula (e5) to prepare poly(amine-amine ester) &lt;Application Example 1&gt; I Preparation Step 丨(1) This application example is to first Water-dried PTMEG (between Du p〇nt; Type 43 201125850 for Terathane® 2000) 2.06 g, distilled purified diphenylmethyl diisocyanate (4,4'-MDI) (purchased from Dadong resin; CAS No. 101-68-8) 0.45 g and 1.10 g of water-removed toluene, placed in a 250 ml three-neck glass reactor, and then added 20 wt % of dilauric acid Dibutyltin dilaurate (DBTDL; t_12) / toluene solution 10 mg' and stirred with a mechanical stirrer, and a dry nitrogen gas was introduced through a connector inserted into the thermometer, and a serpentine condenser was attached to the other neck. The mixture was refluxed, the reaction temperature was controlled at 80 ° C, and the reaction was continued for 2.5 hours to obtain a prepolymer. (2) 0.66 g of the product of Example 6 and 2.42 g of dehydrated dimethylacetamide (DMAc) were added to the prepolymer obtained in the step (1), and a chain extension reaction was carried out at 80 ° C. When the viscosity is obviously increased and the product is crawling, the stirring is stopped, and the temperature is raised to 1 Torr (rc for ripening for 3 hours to obtain a poly(amine amine), and then about 15 ml of NMP will be used. The poly(stearamine-amine ester) was dissolved and allowed to stand for 1 hour. After the bubbles disappeared, the film was formed at 60 ° C for two days, and then dried in an oven to obtain a dried poly(amidamide-amine ester). Wherein, the molar ratio of the PTMEG/4,4'-MDI/chain extender is 1/1.81/0.72, and the hard segment content of the poly(hamamine) is 35 speaks 0/〇. 2&gt; Application Example 2 The poly(amine-amine ester) of the present invention was prepared in the same manner as in Application Example 1, except that the amounts of the raw materials were different as follows: PTMEG 2·00 g, 4,4·-ΜΟΙ 0.37 g, the product of Example 6 is 0.43 g, wherein the molar ratio of 'PTMEG/M-MDI/bond extender to Mohr ratio=1/152/〇.44, poly(bristamine-amine vinegar) is 35 wt %. &lt;Application Example 3&gt; Application Example 3 S The poly(amine-amine vinegar) of the present invention was prepared in the same manner as in the application example except that the amount of the raw materials was different as follows: 44 201125850 PTMEG 2.01 g, 4,4'-MDI 〇·35 g The product of Example 8 is 0.55 g, wherein the molar ratio of the PTMEG/4,4'-MDI/chain extender is 1/1.40/0.33, and the hard segment content of the poly(amine-amine ester) is 35 wt%. &lt;Comparative Example 1> Comparative Example 1 was prepared by the same procedure as in Application Example 1, except that the amounts of the raw materials were different as follows:

PTMEG 20.03 g, 4,4'-MDI 8.42 g, chain extender 1,4-butanediol 0.2.47 g, DMAc 25.0 g, NMP 150 ml 'of which, PTMEG/4,4'-MDI/chain extender The molar ratio = 1/3.45/2.29, the hard segment content of the polyurethane is 34 wt0 / 〇. Test item j

The inventors of the present invention measured the Mw and PDI of the polyurethanes of the comparative example to the trimeric (melamine-amine ester) and the comparative example i by GPC, and measured the elongation of the application examples 丨 to 3 and the comparative example J by the universal material testing machine. The amount, tension and modulus of extension are shown in Table 3 below. Table 3 I. Mw (g/mol) PDI Elongation (%) Tension (MPa) 100% Extensible Modulus (MPa) Example 1 61533 1.95 411.1 58.9 5 1 Application Example 2 -------- Weighing » Is 62538 2.86 j 733.9 29.1 3.8 Column 3 59151 2.50 577.8 52.8 5.7 38599 2.43 [~35α2 "5.9 3.1 ~~-'---~3.1 As can be seen from Table 3, in terms of mechanical properties, the application of the work to 3 The mechanical strength of the amine amines is better than that of the use of 1,4-butanediol as a chain extender. In summary, the present case has two highly selective iso-f-functional groups. The starting material 'and the (4) single (4) combined age, can be accurately synthesized (four) fixed length rib mouth fixed weight average molecular weight) _ extension _. due to nitrogen conversion # 伽基 and brewing chlorine to mild and no lining conditions, The rapid reaction between the sub-ship and the Weiji does not make the chain extension of the different generations of Heli 45 201125850 have the advantages of precise synthesis, high yield, narrow molecular weight distribution and simple purification. In addition, the polyether produced by the chain extender The indoleamine-amine vinegar also has a good strength due to a hard bond segment having an equal bond length, so that the object of the present invention can be achieved. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the implementation of the present invention by simply limiting the equivalent variation and modification of the invention. , are still within the scope of the patent of the present invention. 乍 [ [Simple description of the schema] fe 〇 [main symbol description] None. 46

Claims (1)

201125850 VII. Patent Application Range: 1. A nitrogen heterocyclic-2,4-diketone compound having the chemical formula shown by the following formula (I): Ο Wherein &amp; and R2 are each a Q to C6 alkyl group; and R3 is -CH3, -COOH or -coa. 2. A compound having the following chemical formula (II): ArB wherein A] is a monovalent group having the formula (III) below: (II) (III) In the formula (ΠΙ), R4 and R5 are each a (^ to (: 6 alkyl group; —Wj—NN—z is \_/ , —w3 w2 I N— or a w4-o , and the atom to which Y is bonded to Y is N or Ο, wherein W! is a Q to C6 alkylene group; When W2 is a Q to C6 alkyl group, W3 is a (^ to (: 12 alkyl group, when \¥2 is 11, W3 is 47 201125850) ; w4 is a C, to C12 alkylene; w5 and W6 are each H or a (^ to (: 4 alkyl; and H, and 1 and 117 are each a Ci to C6 alkyl; and B is -X-A2 or -X', wherein X is a by one of two hydroxyl groups on a diol a monovalent group obtained by removing active hydrogen, or a divalent group obtained by removing one hydrogen from each of two amine groups on a diamine, but conditionally, t When the diterpene-grade amine is in the amine, the N in the amine is not in contact with the first-order carbon; in the case of X'--amine, the ^^-valence in the unit amine will be the shift of the elemental alcohol or the unit shame-neo hydrogen The obtained ^ bei group 'but conditional 暇, when the elemental amine is 1 is not in contact with the primary carbon; and the definition of 八 2 is the same as Al in the formula (Π) η in the formula (111) is an integer from 0 to 4 48 201125850; if Y is Η, η in the formula (III) is an integer from 1 to 4; and Ο 0 Re Ry When B is X', if Y is -, η in the formula (III) is an integer of 0 to 8; if Υ is Η, η in the formula (III) is an integer of 1 to 8. 3. The compound according to claim 2, wherein the X is -Ν Ν - \_/ 一〇 - Q factory 〇 one or one NH-Q2 - ΝΗ -, wherein Qi is Q to C12 An alkyl group, a C4 to C8 cycloalkyl group, Γ~\ •Ν Ν- a C! to C4 alkyl or hydrazine, and Q4 is a C! to C4 alkyl, 0, so2 or C = 0; Q2 is a c4 to c8 cycloalkyl, a phenyl, Or, and Q5 is 49 201125850 a Q to C4 alkyl or hydrazine, Q6 is a C! to c4 alkyl, ο, so2 or c = o. Γ~\ Ν Ν —— 4. The compound according to claim 3, wherein X is \_/ or -ΝΉ-Q2-NH_, and q6 is a Ci to Q alkylene group. 5. The compound according to claim 4, wherein X is _NH_Q2__NH-, wherein q2 is ^^^\ and Q6 is an alkyl group of (^ to c4. 6. According to the scope of claim 2 The compound according to the item, wherein the X' is CH, NH- or NH-CH, wherein 0: and 02 are each an anthracene or a C! to C4 alkyl group; D3, D4 and D5 are each an anthracene, a halogen, a phenyl group, a Q to C4 alkyl group, a Q An alkenyl group to C4, a C; an alkynyl group to C4 or -O-IV^, and a Q or C12 alkyl or alkenyl group; D6 is hydrazine or NH; D7 is a Q to C25 alkyl group, • ch2- or M2 is a single bond or methyl group; D8 is a (^ to C4 alkyl or hydrazine; and D9 is a single bond or -MrO-, and M3 is a Q to C4 alkylene Base. 50 201125850 7. A compound according to claim 6 wherein 乂' is. 8. The compound according to claim 2, wherein Z in the formula (III) is 9. The compound according to item 8 of the patent application, wherein Z in the formula (III) is 'And W2 is Η, W3 is W6 0 10·—Polymer (Siamine-Amine) having a weight average molecular weight of between 25, 〇(8) to 3〇〇, (8) 〇, and a reaction product comprising a mixture of the following components: a diisocyanate component comprising at least one diisocyanate; a polyol component comprising at least one polyol having a weight average molecular weight of between 800 and 4500; and a bond extender group And a compound according to claim 2, wherein the poly(amine-amine vinegar) according to the scope of the patent application ,1〇, the total weight of the mixture is 'S, The content of the diisocyanate component is between 5 wt% and 25 wt%. 12. The poly(indoleamine) according to the scope of claim 1 of the patent application, wherein the content of the polyol component is between 25 wt% and 85 based on the total weight of the mixture. The poly(amine-amine ester) according to claim 10, wherein the chain extender component is present in an amount of from 10 wt% to 60 wt%, based on the total weight of the mixture. 14. The polyamine (amine-amine) according to claim 13 of the scope of the patent application, wherein the content of the compound as described in claim 2 is based on the bond extender group 51 201125850 parts. Between 75 wt% and 100 wt%. 52