CN101302154B - Acrylic ester type benzocyclobutene monomer and preparation thereof - Google Patents
Acrylic ester type benzocyclobutene monomer and preparation thereof Download PDFInfo
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- CN101302154B CN101302154B CN 200810044758 CN200810044758A CN101302154B CN 101302154 B CN101302154 B CN 101302154B CN 200810044758 CN200810044758 CN 200810044758 CN 200810044758 A CN200810044758 A CN 200810044758A CN 101302154 B CN101302154 B CN 101302154B
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Abstract
The invention discloses acrylic ester benzocyclobutene monomers such as acrylic acid-4-benzocyclobutenyl ester shown in a chemical structural formula (IV) and so on, and a preparation method thereof. The preparation method of the compound is as follows: 4-hydroxy-benzocyclobutene and acryloyl chloride are taken according to the mol ratio of between 1 to 1.0 and 2.0, and are respectively dissolvedin diluting solvent methylene dichloride; in a water-free and oxygen-free reaction system, a methylene dichloride solution of the 4-hydroxy-benzocyclobutene and organic base are mixed and dripped into a methylene dichloride solution of the acryloyl chloride, the dripping is performed under ice bath when the stirring is carried out, the mixture is stirred to react for 7 to 8h at room temperature after the dripping is finished; then reaction liquid is extracted by organic solvent, an organic phase is washed to the neutrality and is dried and condensed, column chromatography is used to perform the separation and purification, organic solvent petroleum ether or/and methylene dichloride are used to leach, and leacheate is condensed to a dry state to produce a product. The compound can produce good thermosetting polymer materials through polymerization, which are used for high-performance dielectric film materials in the microelectronic industry.
Description
Technical field
The invention belongs to a kind of isocyclic compound and preparation method thereof, relate to acrylic ester type benzocyclobutene monomer and preparation method thereof.The acrylic ester type benzocyclobutene monomer of preparation is suitable for use as the monomer of preparation benzocyclobutane alkene polymer or prepares the raw material of other benzocyclobutene monomer.
Background technology
Benzocyclobutene (BCB) family macromolecule material is the novel high polymer material with excellent high temperature resistance performance, dielectric properties and hydrophobicity performance.On material and structure, materials such as high-performance dielectric film material based on benzocyclobutene, high temperature material, nonlinear optical material, matrix material have been developed.From Application Areas, the BCB base polymer is in microelectronics industry field extensive application, mcm (MCM), microelectromechanical-systems (MEMS) have been used for abroad, fields such as liquid-crystal display encapsulation, macromolecule membrane waveguide, biocompatibility micro element, minority developed country has been used for this technology fields such as space flight, military affairs.Benzocyclobutene (BCB) family macromolecule material can be by the derivative preparation of benzocyclobutene, and the kind of benzocyclobutane ene derivative is more, and report is all arranged in following document: Cyclobutarenes and RelatedCompounds, Chemical Reviews, 2003,103,1539-1602; Recent Chemistry ofBenzocyclobutenes, Tetrahedron, 2001,57,625-659; Benzocyclobutenes inPolymer Chemistry, Progress in Polymer Science, 1996,21,505-555; Benzo-cyclobutenes in Polymer Synthesis, 1993,18,85-185; Benzocyclobutene andRelated Compounds, Account Chemical Research, 1980,13,70-76.Can prepare multiple benzocyclobutene monomer and benzocyclobutene family macromolecule material by these derivatives.
Benzocyclobutene can form 4-bromobenzene and cyclobutene or 1-bromobenzene and cyclobutene under the effect of bromine or bromo-succinimide, substitution reaction can take place under certain condition in 4-bromobenzene and cyclobutene or 1-bromobenzene and cyclobutene, generate 1-hydroxy benzo cyclobutene, 4-hydroxy benzo cyclobutene, 1-(1-hydroxyethyl) benzocyclobutene.For example: 4-bromobenzene and cyclobutene are at TiCl
4, Cl
2CHCOCH
3Effect generate down 4-carboxaldehyde radicals benzocyclobutene, 4-carboxaldehyde radicals benzocyclobutene generates 4-hydroxy benzo cyclobutene under the effect of permonophosphoric acid.Benzocyclobutane ene derivative shown in chemical structural formula (I), (II), (III) is all existing report in above and other document.
Summary of the invention
Purpose of the present invention aims to provide a kind of new acrylic ester type benzocyclobutene monomer and preparation method thereof; Novel monomeric provided by the present invention (IV), (V) and (VI) be the new compound of not seeing bibliographical information, they can obtain linear polymer by light-initiated or radically homo or with other monomer copolymerization, further carry out ring-opening polymerization again and obtain novel cross-linking type polyester, have a extensive future.
Content of the present invention is: vinylformic acid-4-benzocyclobutene ester is characterized in that this compound has the chemical structural formula of (IV):
This compound acrylic acid-4-benzocyclobutene ester (IV) is a colourless liquid, and structural characterization is as follows: nucleus magnetic resonance
1H NMR (600MHz, CDCl
3), δ: 3.15 (d, 4H, J=3.1, CH
2CH
2), 5.98 (dd, 1H, J=1.2,10.4 ,-CH=CH
2), 6.31 (dd, 1H, J=10.6,17.4 ,-CH=CH
2), 6.58 (dd, 1H, J=1.2,10.4 ,-CH=CH
2), 6.83 (s, 1H ,-ArH), 6.89 (dd, 1H, J=1.8,7.9 ,-ArH), 7.04 (s, 1H ,-ArH).Nucleus magnetic resonance
13C NMR (100MHz, CDCl
3) δ: 29.03 (CH
2CH
2), 29.07 (CH
2CH
2), 116.51 (CH=CH
2), 120.20 (Ar-C), 123.61 (Ar-C), 128.11 (Ar-C), 132.28 (CH=CH
2), 143.11 (Ar-C), 146.42 (Ar-C), 149.78 (Ar-C), 165.04 (C=O).(KBr's infrared spectra IR films, cm
-1): 3035.9 (w), 2933.1 (s), 1742.7 (vs), 1634.5 (s), 1592.6 (w), 1606.0 (w), 1467. (s), 1402.9 (s), 1244.9 (s), 1158.9 (vs), 1117.6 (w), 983.8 (s), 902.3 (s), 822.3 (w), 777.3 (w).Mass spectrum EI-MS (m/z, %): 174.0 (M
+, 100), 120.0 (M
+-54,80).
Content of the present invention also comprises: the preparation method of vinylformic acid-4-benzocyclobutene ester is characterized in that comprising the following steps:
A, batching: by 4-hydroxy benzo cyclobutene: acrylate chloride is 1: the molar ratio of 1.0-2.0 is got each component, and be dissolved in respectively in the diluting solvent methylene dichloride (solvent load can for the 1-20 of 4-hydroxy benzo cyclobutene molar weight doubly, also can adopt other organic solvent); By 4-hydroxy benzo cyclobutene: organic bases is 1: the molar ratio of 1.0-3.0 is got organic bases (organic bases is used for the hydrogenchloride that neutralization reaction generates);
B, ready reaction system: the reaction system that at room temperature will comprise reactor vacuumizes, logical nitrogen (repeatedly three times or more times), anhydrous and oxygen-free to the reaction system;
C, dropwise reaction: in reaction system, mix, be added drop-wise to again the dichloromethane solution of 4-hydroxy benzo cyclobutene in the dichloromethane solution of acrylate chloride with organic bases, or the dichloromethane solution of acrylate chloride is added drop-wise in the dichloromethane solution and organic bases mixed solution of 4-hydroxy benzo cyclobutene, under ice bath, drip and stir, the dropping time is 30-90min, stirring reaction 7-8h at room temperature after dripping;
D, separation are purified: with in the reaction solution impouring distilled water, standing demix divided three extractions with methylene chloride after reaction stopped, and collected to merge organic phase; Extremely neutral with 5% aqueous sodium carbonate washing organic phase, usefulness distilled water wash organic phase again, use the inorganic salt siccative with the organic phase dried overnight again; Isolate siccative again, concentrate organic phase, use column chromatography purification, or/and eluent methylene chloride, leacheate is concentrated into dried, make colourless liquid product vinylformic acid-4-benzocyclobutene ester (IV) with the solvent sherwood oil.
The vinylformic acid that makes-4-benzocyclobutene ester (IV) is a colourless liquid, and structural characterization is as follows: nucleus magnetic resonance
1H NMR (600MHz, CDCl
3), δ: 3.15 (d, 4H, J=3.1, CH
2CH
2), 5.98 (dd, 1H, J=1.2,10.4 ,-CH=CH
2), 6.31 (dd, 1H, J=10.6,17.4 ,-CH=CH
2), 6.58 (dd, 1H, J=1.2,10.4 ,-CH=CH
2), 6.83 (s, 1H ,-ArH), 6.89 (dd, 1H, J=1.8,7.9 ,-ArH), 7.04 (s, 1H ,-ArH).Nucleus magnetic resonance
13C NMR (100MHz, CDCl
3) δ: 29.03 (CH
2CH
2), 29.07 (CH
2CH
2), 116.51 (CH=CH
2), 120.20 (Ar-C), 123.61 (Ar-C), 128.11 (Ar-C), 132.28 (CH=CH
2), 143.11 (Ar-C), 146.42 (Ar-C), 149.78 (Ar-C), 165.04 (C=O).(KBr's infrared spectra IR films, cm
-1): 3035.9 (w), 2933.1 (s), 1742.7 (vs), 1634.5 (s), 1592.6 (w), 1606.0 (w), 1467. (s), 1402.9 (s), 1244.9 (s), 1158.9 (vs), 1117.6 (w), 983.8 (s), 902.3 (s), 822.3 (w), 777.3 (w).Mass spectrum EI-MS (m/z, %): 174.0 (M
+, 100), 120.0 (M
+-54,80).
Among the preparation method of described vinylformic acid-4-benzocyclobutene ester, organic bases is triethylamine, pyridine or Tributylamine described in the step (a), and inorganic salt siccative described in the step (d) is that anhydrous sodium sulphate or anhydrous magnesium sulfate, described column chromatography are silica gel column chromatographies.
Another content of the present invention is: vinylformic acid-1-benzocyclobutene ester is characterized in that this compound has the chemical structural formula of (V):
This compound acrylic acid-1-benzocyclobutene ester is (V) colourless liquid, and structural characterization is as follows:
1H NMR (600MHz, CDCl
3) δ: 3.27 (d, 1H, J=14.3 ,-CHCH
2), 3.70 (dd, 1H, J=4.5,14.3 ,-CHCH
2), 5.86 (dd, 1H, J=1.5,10.6 ,-CH=CH
2), 6.01 (dd, 1H, J=1.7,4.5 ,-CHCH
2), 6.17 (dd, 1H, J=10.4,17.3 ,-CH=CH
2), 6.47 (dd, 1H, J=1.3,17.4 ,-CH=CH
2) .7.16 (d, 1H, J=7.4 ,-ArH), 7.25-7.28 (m, 2H ,-ArH), 7.30-7.35 (m, 1H ,-ArH).Nucleus magnetic resonance
13C NMR (150MHz, CDCl
3) δ: 38.98 (CH
2CH-), 71.66 (CH
2CH-), 123.22 (CH=CH
2), 123.64 (Ar-C), 127.56 (Ar-C), 128.30 (Ar-C), 130.04 (Ar-C), 131.07 (Ar-C), 142.74 (Ar-C), 144.15 (CH=CH
2), 166.14 (C=O).(KBr's infrared spectra IR films, cm
-1): 3067.2 (w), 2925.4 (w), 1742.7 (vs), 1634.7 (w), 1458.4 (w), 1406.7 (s), 1294.4 (w), 1271.4 (s), 1186.9 (s), 1053.4 (w), 985.8 (w), 809.8 (w), 744.6 (s), 708.8 (w).Mass spectrum EI-MS (m/z, %): 174.0 (M
+, 30), 103.0 (M
+-71,100).
The preparation method of vinylformic acid-1-benzocyclobutene ester is characterized in that comprising the following steps:
A, batching: by 1-hydroxy benzo cyclobutene: acrylate chloride is 1: the molar ratio of 1.0-2.0 is got each component, and be dissolved in respectively in the diluting solvent methylene dichloride (solvent load can for the 1-20 of 1-hydroxy benzo cyclobutene molar weight doubly, also can adopt other organic solvent); By 1-hydroxy benzo cyclobutene: organic bases is 1: the molar ratio of 1.0-3.0 is got organic bases (organic bases is used for the hydrogenchloride that neutralization reaction generates);
B, ready reaction system: the reaction system that at room temperature will comprise reactor vacuumizes, logical nitrogen (repeatedly three times or more times), anhydrous and oxygen-free to the reaction system;
C, dropwise reaction: in reaction system, mix, be added drop-wise to again the dichloromethane solution of 1-hydroxy benzo cyclobutene in the dichloromethane solution of acrylate chloride with organic bases, or the dichloromethane solution of acrylate chloride is added drop-wise in the dichloromethane solution and organic bases mixed solution of 1-hydroxy benzo cyclobutene, under ice bath, drip and stir, the dropping time is 30-90min, stirring reaction 9-10h at room temperature after dripping;
D, separation are purified: with in the reaction solution impouring distilled water, standing demix divided three extractions with methylene chloride after reaction stopped, and collected to merge organic phase; Extremely neutral with 5% aqueous sodium carbonate washing organic phase, usefulness distilled water wash organic phase again, use the inorganic salt siccative with the organic phase dried overnight again; Isolate siccative again, concentrate organic phase, use column chromatography purification, or/and eluent methylene chloride, leacheate is concentrated into dried, make colourless liquid product vinylformic acid-1-benzocyclobutene ester (V) with the solvent sherwood oil.
Vinylformic acid-1-benzocyclobutene the ester (V) of preparation is a colourless liquid, and structural characterization is as follows:
1H NMR (600MHz, CDCl
3) δ: 3.27 (d, 1H, J=14.3 ,-CHCH
2), 3.70 (dd, 1H, J=4.5,14.3 ,-CHCH
2), 5.86 (dd, 1H, J=1.5,10.6 ,-CH=CH
2), 6.01 (dd, 1H, J=1.7,4.5 ,-CHCH
2), 6.17 (dd, 1H, J=10.4,17.3 ,-CH=CH
2), 6.47 (dd, 1H, J=1.3,17.4 ,-CH=CH
2) .7.16 (d, 1H, J=7.4 ,-ArH), 7.25-7.28 (m, 2H ,-ArH), 7.30-7.35 (m, 1H ,-ArH).Nucleus magnetic resonance
13C NMR (150MHz, CDCl
3) δ: 38.98 (CH
2CH-), 71.66 (CH
2CH-), 123.22 (CH=CH
2), 123.64 (Ar-C), 127.56 (Ar-C), 128.30 (Ar-C), 130.04 (Ar-C), 131.07 (Ar-C), 142.74 (Ar-C), 144.15 (CH=CH
2), 166.14 (C=O).(KBr's infrared spectra IR films, cm
-1): 3067.2 (w), 2925.4 (w), 1742.7 (vs), 1634.7 (w), 1458.4 (w), 1406.7 (s), 1294.4 (w), 1271.4 (s), 1186.9 (s), 1053.4 (w), 985.8 (w), 809.8 (w), 744.6 (s), 708.8 (w).Mass spectrum EI-MS (m/z, %): 174.0 (M
+, 30), 103.0 (M
+-71,100).
Among the preparation method of described vinylformic acid-1-benzocyclobutene ester, organic bases is triethylamine, pyridine or Tributylamine described in the step (a), and the inorganic salt siccative is anhydrous sodium sulphate or anhydrous magnesium sulfate described in the step (d), and described column chromatography is a silica gel column chromatography.
Another content of the present invention is: vinylformic acid-1-benzocyclobutane thiazolinyl methyl esters is characterized in that this compound has the chemical structural formula of (VI):
This compound acrylic acid-1-benzocyclobutane thiazolinyl methyl esters (VI) is a colourless liquid, and structural characterization is as follows: this product
1H NMR (600MHz, CDCl
3) δ: 2.94 (dd, 1H, J=2.2,14.2, CHCH
2), 3.36 (dd, 1H, J=5.2,14.2, CHCH
2), 3.72 (dd, 1H, J=5.2,14.2, CHCH
2), 3.80-3.90 (m, 1H, CHCH
2), 4.30-4.50 (m, 2H, CH
2), 5.84 (dd, 1H, J=1.1,10.5 ,-CH=CH
2), 6.15 (dd, 1H, J=10.5,17.3 ,-CH=CH
2), 6.42 (dd, 1H, J=1.3,17.5 ,-CH=CH
2), 7.09 (d, 2H, J=7.7 ,-ArH), 7.18-7.27 (m, 2H ,-ArH).Nucleus magnetic resonance
13CNMR (100MHz, CDCl
3) δ: 33.59 (CH
2CH-), 41.79 (CH
2CH-), 66.79 (O-CH
2-), 122.43 (Ar-C), 123.10 (Ar-C), 126.98 (Ar-C), 127.90 (Ar-C), 128.49 (Ar-C), 130.81 (CH=CH
2), 143.77 (Ar-C), 145.64 (CH=CH
2), 166.14 (C=O).(KBr's infrared spectra IR films, cm
-1): 3069.5 (vs), 2933.0 (vs), 1724.4 (s), 1634.7 (vs), 1618.9 (w), 1456.7 (vs), 1405.3 (s), 1294.4 (w), 1264.2 (s), 1190.0 (s), 1110.0 (vs), 1052.4 (w), 983.3 (vs), 908.0 (w), 809.7 (s), 745.9 (w).Mass spectrum EI-MS (m/z, %): 174.0 (M
+, 10), 103.0 (M
+-58,100).
The preparation method of vinylformic acid-1-benzocyclobutane thiazolinyl methyl esters is characterized in that comprising the following steps:
A, batching: by 1-methylol benzocyclobutene: acrylate chloride is 1: the molar ratio of 1.0-2.0 is got each component, and be dissolved in respectively in the diluting solvent methylene dichloride (solvent load can for the 1-20 of 1-methylol benzocyclobutene molar weight doubly, also can adopt other organic solvent); By 1-methylol benzocyclobutene: organic bases is 1: the molar ratio of 1.0-3.0 is got organic bases (organic bases is used for the hydrogenchloride that neutralization reaction generates);
B, ready reaction system: the reaction system that at room temperature will comprise reactor vacuumizes, logical nitrogen (repeatedly three times or more times), anhydrous and oxygen-free to the reaction system;
C, dropwise reaction: in reaction system, mix, be added drop-wise to again the dichloromethane solution of 1-methylol benzocyclobutene in the dichloromethane solution of acrylate chloride with organic bases, or the dichloromethane solution of acrylate chloride is added drop-wise in the dichloromethane solution and organic bases mixed solution of 1-methylol benzocyclobutene, under ice bath, drip and stir, the dropping time is 30-90min, stirring reaction 11-12h at room temperature after dripping;
D, separation are purified: with in the reaction solution impouring distilled water, standing demix divided three extractions with methylene chloride after reaction stopped, and collected to merge organic phase; Extremely neutral with 5% aqueous sodium carbonate washing organic phase, usefulness distilled water wash organic phase again, use the inorganic salt siccative with the organic phase dried overnight again; Isolate siccative again, concentrate organic phase, use column chromatography purification, with the solvent sherwood oil or/and eluent methylene chloride, leacheate is concentrated into dried, colourless liquid product vinylformic acid-1-benzocyclobutane thiazolinyl methyl esters (VI).
Vinylformic acid-1-benzocyclobutane thiazolinyl the methyl esters (VI) of preparation is a colourless liquid, and structural characterization is as follows: this product
1H NMR (600MHz, CDCl
3) δ: 2.94 (dd, 1H, J=2.2,14.2, CHCH
2), 3.36 (dd, 1H, J=5.2,14.2, CHCH
2), 3.72 (dd, 1H, J=5.2,14.2, CHCH
2), 3.80-3.90 (m, 1H, CHCH
2), 4.30-4.50 (m, 2H, CH
2), 5.84 (dd, 1H, J=1.1,10.5 ,-CH=CH
2), 6.15 (dd, 1H, J=10.5,17.3 ,-CH=CH
2), 6.42 (dd, 1H, J=1.3,17.5 ,-CH=CH
2), 7.09 (d, 2H, J=7.7 ,-ArH), 7.18-7.27 (m, 2H ,-ArH).Nucleus magnetic resonance
13C NMR (100MHz, CDCl
3) δ: 33.59 (CH
2CH-), 41.79 (CH
2CH-), 66.79 (O-CH
2-), 122.43 (Ar-C), 123.10 (Ar-C), 126.98 (Ar-C), 127.90 (Ar-C), 128.49 (Ar-C), 130.81 (CH=CH
2), 143.77 (Ar-C), 145.64 (CH=CH
2), 166.14 (C=O).(KBr's infrared spectra IR films, cm
-1): 3069.5 (vs), 2933.0 (vs), 1724.4 (s), 1634.7 (vs), 1618.9 (w), 1456.7 (vs), 1405.3 (s), 1294.4 (w), 1264.2 (s), 1190.0 (s), 1110.0 (vs), 1052.4 (w), 983.3 (vs), 908.0 (w), 809.7 (s), 745.9 (w).Mass spectrum EI-MS (m/z, %): 174.0 (M
+, 10), 103.0 (M
+-58,100).
Among described vinylformic acid-1-benzocyclobutane thiazolinyl methyl esters preparation method, organic bases is triethylamine, pyridine or Tributylamine described in the step (a), and the inorganic salt siccative is anhydrous sodium sulphate or anhydrous magnesium sulfate described in the step (d), and described column chromatography is a silica gel column chromatography.
Compared with prior art, the present invention has following characteristics and beneficial effect:
(1) compare with benzocyclobutene, monomer whose has relatively low open loop temperature, and performance etc. are further enhanced;
(2) acrylic ester type benzocyclobutene provided by the invention, after benzocyclobutene has been introduced acrylic, can take place homopolymerization or with other alkene (as vinylbenzene, 4-vinyl benzo cyclobutene etc.) copolymerization, the further polymerization of linear polymer after the polymerization, carry out crosslinking reaction, obtain the novel excellent performance of a class (high thermotolerance, low specific inductivity, good moisture resistivity, good film forming properties,) the thermosetting macromolecule material, the i.e. thin-film material of a class excellent performance, can be used as the high-performance dielectric film material in the microelectronics industry, use very extensive.
(3) product preparation of the present invention is simple and convenient, separates and purifies easily, the productive rate height;
Embodiment
Embodiment given below intends so that the invention will be further described; but can not be interpreted as it is limiting the scope of the invention; the person skilled in art to some nonessential improvement and adjustment that the present invention makes, still belongs to protection scope of the present invention according to the content of the invention described above.
Embodiment 1:
The preparation method of vinylformic acid-4-benzocyclobutene ester (IV) may further comprise the steps:
A, batching: by 4-hydroxy benzo cyclobutene: acrylate chloride is that 1: 2.01 molar ratio is got each component, and is dissolved in respectively in the diluting solvent methylene dichloride; By 4-hydroxy benzo cyclobutene: organic bases is that 1: 2.0 molar ratio is got organic bases;
B, ready reaction system: the reaction system that at room temperature will comprise reactor vacuumizes, logical nitrogen, anhydrous and oxygen-free to the reaction system;
C, dropwise reaction: in reaction system, mix, be added drop-wise to again the dichloromethane solution of 4-hydroxy benzo cyclobutene in the dichloromethane solution of acrylate chloride with organic bases, or the dichloromethane solution of acrylate chloride is added drop-wise in the dichloromethane solution and organic bases mixed solution of 4-hydroxy benzo cyclobutene, under ice bath, drip and stir, the dropping time is 30-90min, stirring reaction 8h at room temperature after dripping;
D, separation are purified: with in the reaction solution impouring distilled water, standing demix divided three extractions with methylene chloride after reaction stopped, and collected to merge organic phase; Extremely neutral with 5% aqueous sodium carbonate washing organic phase, usefulness distilled water wash organic phase again, use the inorganic salt siccative with the organic phase dried overnight again; Isolate siccative again, concentrate organic phase, use column chromatography purification, or/and eluent methylene chloride, leacheate is concentrated into dried, make colourless liquid product vinylformic acid-4-benzocyclobutene ester (IV) with the solvent sherwood oil;
Organic bases described in the step (a) can be triethylamine, pyridine or Tributylamine, and inorganic salt siccative described in the step (d) can be a silica gel column chromatography for anhydrous sodium sulphate or anhydrous magnesium sulfate, described column chromatography.
The vinylformic acid that makes-4-benzocyclobutene ester (IV) is a colourless liquid, and structural characterization is as follows: nucleus magnetic resonance
1H NMR (600MHz, CDCl
3), δ: 3.15 (d, 4H, J=3.1, CH
2CH
2), 5.98 (dd, 1H, J=1.2,10.4 ,-CH=CH
2), 6.31 (dd, 1H, J=10.6,17.4 ,-CH=CH
2), 6.58 (dd, 1H, J=1.2,10.4 ,-CH=CH
2), 6.83 (s, 1H ,-ArH), 6.89 (dd, 1H, J=1.8,7.9 ,-ArH), 7.04 (s, 1H ,-ArH).Nucleus magnetic resonance
13C NMR (100MHz, CDCl
3) δ: 29.03 (CH
2CH
2), 29.07 (CH
2CH
2), 116.51 (CH=CH
2), 120.20 (Ar-C), 123.61 (Ar-C), 128.11 (Ar-C), 132.28 (CH=CH
2), 143.11 (Ar-C), 146.42 (Ar-C), 149.78 (Ar-C), 165.04 (C=O).(KBr's infrared spectra IR films, cm
-1): 3035.9 (w), 2933.1 (s), 1742.7 (vs), 1634.5 (s), 1592.6 (w), 1606.0 (w), 1467. (s), 1402.9 (s), 1244.9 (s), 1158.9 (vs), 1117.6 (w), 983.8 (s), 902.3 (s), 822.3 (w), 777.3 (w).Mass spectrum EI-MS (m/z, %): 174.0 (M
+, 100), 120.0 (M
+-54,80).
Embodiment 2:
Prepare the method for vinylformic acid-4-benzocyclobutene ester (IV), may further comprise the steps:
The 100mL two neck round-bottomed flasks that magnetic stir bar, constant pressure funnel and reflux condensing tube are housed are vacuumized (available heating gun is with its system heating, so that nitrogen is taken away water and oxygen in the system), logical nitrogen, repeatable operation three times is guaranteed the system anhydrous and oxygen-free.
With 4-hydroxy benzo cyclobutene (2.0g, 0.017mol) under ice bath, be dissolved in methylene dichloride (5.3mL) solvent, with its injection of solution in the reaction system of anhydrous and oxygen-free, (4.8mL) also is expelled in the reaction system with triethylamine, ice bath stirs 30min down, with the dichloromethane solution dilution of 4-hydroxy benzo cyclobutene; With acrylate chloride (2.7mL 0.033mol) is dissolved under the ice bath in methylene dichloride (10mL) solvent, with its injection of solution in constant pressure funnel.Under ice bath, the dichloromethane solution of acrylate chloride slowly is added drop-wise in the mixed solution of the dichloromethane solution of 4-hydroxy benzo cyclobutene and triethylamine, the dropping time is 30-90min, dropwises the back room temperature reaction 7-8 hour.With in the reaction solution impouring distilled water, (3 * 30mL) collect the merging organic phase to dichloromethane extraction, and the sodium carbonate solution washing organic phase with 5% uses the distilled water wash organic phase to neutral again, spends the night with anhydrous sodium sulphate or anhydrous magnesium sulfate drying behind the reaction terminating.Isolate siccative, concentrate organic phase, use column chromatography purification, the mixing solutions of sherwood oil and methylene dichloride (volume ratio is 1: 1) is an eluent, the elutriant rotary evaporation that product will be arranged makes vinylformic acid-4-benzocyclobutene ester (IV) the product 2.36g of colourless liquid except that desolvating.
Gas-matter coupling detected result gets purity: 96.3%, and productive rate: 78.4%, structural characterization is as follows: nucleus magnetic resonance
1H NMR (600MHz, CDCl
3), δ: 3.15 (d, 4H, J=3.1, CH
2CH
2), 5.98 (dd, 1H, J=1.2,10.4 ,-CH=CH
2), 6.31 (dd, 1H, J=10.6,17.4 ,-CH=CH
2), 6.58 (dd, 1H, J=1.2,10.4 ,-CH=CH
2), 6.83 (s, 1H ,-ArH), 6.89 (dd, 1H, J=1.8,7.9 ,-ArH), 7.04 (s, 1H ,-ArH).Nucleus magnetic resonance
13C NMR (100MHz, CDCl
3) δ: 29.03 (CH
2CH
2), 29.07 (CH
2CH
2), 116.51 (CH=CH
2), 120.20 (Ar-C), 123.61 (Ar-C), 128.11 (Ar-C), 132.28 (CH=CH
2), 143.11 (Ar-C), 46.42 (Ar-C), 149.78 (Ar-C), 165.04 (C=O).(KBr's infrared spectra IR films, cm
-1): 3035.9 (w), 2933.1 (s), 1742.7 (vs), 1634.5 (s), 1592.6 (w), 1606.0 (w), 1467. (s), 1402.9 (s), 1244.9 (s), 1158.9 (vs), 1117.6 (w), 983.8 (s), 902.3 (s), 822.3 (w), 777.3 (w).Mass spectrum EI-MS (m/z, %): 174.0 (M
+, 100), 120.0 (M
+-54,80).
Embodiment 3:
Prepare the method for vinylformic acid 4-benzocyclobutene ester (IV), may further comprise the steps:
The 100mL two neck round-bottomed flasks that magnetic stir bar, constant pressure funnel and reflux condensing tube are housed are vacuumized (available heating gun is with its system heating, so that nitrogen is taken away water and oxygen in the system), logical nitrogen, repeatable operation three times is guaranteed the system anhydrous and oxygen-free.
With 4-hydroxy benzo cyclobutene (2.00g, 0.017mol) under ice bath, be dissolved in methylene dichloride (5.3mL) solvent, with its injection of solution in the reaction system of anhydrous and oxygen-free, (4.82mL) also is expelled in the reaction system with triethylamine, ice bath stirs 30min down, with the dichloromethane solution dilution of 4-hydroxy benzo cyclobutene; With acrylate chloride (2.03mL 0.025mol) is dissolved under the ice bath in methylene dichloride (7.5mL) solvent, with its injection of solution in constant pressure funnel.Under ice bath, the dichloromethane solution of acrylate chloride slowly is added drop-wise in the mixed solution of the dichloromethane solution of 4-hydroxy benzo cyclobutene and triethylamine, the dropping time is 30-90min, dropwises the back room temperature reaction 7-8 hour.With in the reaction solution impouring distilled water, (3 * 30mL) collect the merging organic phase to dichloromethane extraction, and the sodium carbonate solution washing organic phase with 5% uses the distilled water wash organic phase to neutral again, and anhydrous sodium sulphate or anhydrous magnesium sulfate drying spend the night behind the reaction terminating.Isolate siccative, concentrate organic phase, use column chromatography purification, the mixing solutions of sherwood oil and methylene dichloride (volume ratio is 1: 1) is an eluent, the elutriant rotary evaporation that product will be arranged makes vinylformic acid-4-benzocyclobutene ester (IV) product 2.339 of colourless liquid except that desolvating.
Gas-matter coupling detected result gets purity: 97.1%, and productive rate: 78.0%, structural characterization is as follows: nucleus magnetic resonance
1H NMR (600MHz, CDCl
3), δ: 3.15 (d, 4H, J=3.1, CH
2CH
2), 5.98 (dd, 1H, J=1.2,10.4 ,-CH=CH
2), 6.31 (dd, 1H, J=10.6,17.4 ,-CH=CH
2), 6.58 (dd, 1H, J=1.2,10.4 ,-CH=CH
2), 6.83 (s, 1H ,-ArH), 6.89 (dd, 1H, J=1.8,7.9 ,-ArH), 7.04 (s, 1H ,-ArH).Nucleus magnetic resonance
13C NMR (100MHz, CDCl
3) δ: 29.03 (CH
2CH
2), 29.07 (CH
2CH
2), 116.51 (CH=CH
2), 120.20 (Ar-C), 123.61 (Ar-C), 128.11 (Ar-C), 132.28 (CH=CH
2), 143.11 (Ar-C), 146.42 (Ar-C), 149.78 (Ar-C), 165.04 (C=O).(KBr's infrared spectra IR films, cm
-1): 3035.9 (w), 2933.1 (s), 1742.7 (vs), 1634.5 (s), 1592.6 (w), 1606.0 (w), 1467. (s), 1402.9 (s), 1244.9 (s), 1158.9 (vs), 1117.6 (w), 983.8 (s), 902.3 (s), 822.3 (w), 777.3 (w).Mass spectrum EI-MS (m/z, %): 174.0 (M
+, 100), 120.0 (M
+-54,80).
Embodiment 4-8:
Among the preparation method of vinylformic acid-4-benzocyclobutene ester, the molar ratio of 4-hydroxy benzo cyclobutene and acrylate chloride, triethylamine sees the following form in step (a) batching:
The chemistry of the vinylformic acid that makes-4-benzocyclobutene ester, physical function parameter are with embodiment 1, and other is with embodiment 1,2 or 3, slightly.
Embodiment 9-14:
Among the preparation method of vinylformic acid-4-benzocyclobutene ester, raw material ratio: 4-hydroxy benzo cyclobutene/acrylate chloride=1/2, the dichloromethane solvent consumption sees the following form in step (c) batching:
| The embodiment numbering | 9 | 10 | 11 |
| Material concentration | 1.0mol/L | 2.0mol/L | 3.0mol/L |
| Yield | 75.2 | 78.9 | 82.1 |
The chemistry of the vinylformic acid that makes-4-benzocyclobutene ester, physical function parameter are with embodiment 1, and other is with embodiment 1,2 or 3, slightly.
Embodiment 12:
Prepare the method for vinylformic acid-1-benzocyclobutene ester (V), may further comprise the steps:
A, batching: by 1-hydroxy benzo cyclobutene: acrylate chloride is that 1: 2.0 molar ratio is got each component, and is dissolved in respectively in the diluting solvent methylene dichloride; By 1-hydroxy benzo cyclobutene: organic bases is that 1: 3.0 molar ratio is got organic bases;
B, ready reaction system: the reaction system that at room temperature will comprise reactor vacuumizes, logical nitrogen, anhydrous and oxygen-free to the reaction system;
C, dropwise reaction: in reaction system, mix, be added drop-wise to again the dichloromethane solution of 1-hydroxy benzo cyclobutene in the dichloromethane solution of acrylate chloride with organic bases, or the dichloromethane solution of acrylate chloride is added drop-wise in the dichloromethane solution and organic bases mixed solution of 1-hydroxy benzo cyclobutene, under ice bath, drip and stir, the dropping time is 30-90min, stirring reaction 10h at room temperature after dripping;
D, separation are purified: with in the reaction solution impouring distilled water, standing demix divided three extractions with methylene chloride after reaction stopped, and collected to merge organic phase; Extremely neutral with 5% aqueous sodium carbonate washing organic phase, usefulness distilled water wash organic phase again, use the inorganic salt siccative with the organic phase dried overnight again; Isolate siccative again, concentrate organic phase, use column chromatography purification, or/and eluent methylene chloride, leacheate is concentrated into dried, make colourless liquid product vinylformic acid-1-benzocyclobutene ester (V) with the solvent sherwood oil;
Organic bases is triethylamine, pyridine or Tributylamine described in the step (a), and inorganic salt siccative described in the step (d) can be a silica gel column chromatography for anhydrous sodium sulphate or anhydrous magnesium sulfate, described column chromatography.Vinylformic acid-1-benzocyclobutene the ester (V) of preparation is a colourless liquid, and structural characterization is as follows:
1H NMR (600MHz, CDCl
3) δ: 3.27 (d, 1H, J=14.3 ,-CHCH
2), 3.70 (dd, 1H, J=4.5,14.3 ,-CHCH
2), 5.86 (dd, 1H, J=1.5,10.6 ,-CH=CH
2), 6.01 (dd, 1H, J=1.7,4.5 ,-CHCH
2), 6.17 (dd, 1H, J=10.4,17.3 ,-CH=CH
2), 6.47 (dd, 1H, J=1.3,17.4 ,-CH=CH
2) .7.16 (d, 1H, J=7.4 ,-ArH), 7.25-7.28 (m, 2H ,-ArH), 7.30-7.35 (m, 1H ,-ArH).Nucleus magnetic resonance
13C NMR (150MHz, CDCl
3) δ: 38.98 (CH
2CH-), 71.66 (CH
2CH-), 123.22 (CH=CH
2), 123.64 (Ar-C), 127.56 (Ar-C), 128.30 (Ar-C), 130.04 (Ar-C), 131.07 (Ar-C), 142.74 (Ar-C), 144.15 (CH=CH
2), 166.14 (C=O).(KBr's infrared spectra IR films, cm
-1): 3067.2 (w), 2925.4 (w), 1742.7 (vs), 1634.7 (w), 1458.4 (w), 1406.7 (s), 1294.4 (w), 1271.4 (s), 1186.9 (s), 1053.4 (w), 985.8 (w), 809.8 (w), 744.6 (s), 708.8 (w).Mass spectrum EI-MS (m/z, %): 174.0 (M
+, 30), 103.0 (M
+-71,100).
Embodiment 13:
Prepare the method for vinylformic acid-1-benzocyclobutene ester (V), may further comprise the steps:
The 100mL two neck round-bottomed flasks that magnetic stir bar, constant pressure funnel and reflux condensing tube are housed are vacuumized (available heating gun is with its system heating, so that nitrogen is taken away water and oxygen in the system), logical nitrogen, repeatable operation three times is guaranteed the system anhydrous and oxygen-free.
With 1-hydroxy benzo cyclobutene (2.0g, 0.0167mol) under ice bath, be dissolved in methylene dichloride (5.3mL) solvent, with its injection of solution in the reaction system of anhydrous and oxygen-free, (4.82mL) also is expelled in the reaction system with triethylamine, ice bath stirs 30min down, with the dichloromethane solution dilution of 4-hydroxy benzo cyclobutene; With acrylate chloride (2.71mL 0.0333mol) is dissolved under the ice bath in methylene dichloride (10mL) solvent, with its injection of solution in constant pressure funnel.Under ice bath, the dichloromethane solution of acrylate chloride slowly is added drop-wise in the mixed solution of the dichloromethane solution of 4-hydroxy benzo cyclobutene and triethylamine, the dropping time is 30-90min, dropwises the back room temperature reaction 9-10 hour.With in the reaction solution impouring distilled water, (3 * 30mL) collect the merging organic phase to dichloromethane extraction, and the sodium carbonate solution washing organic phase with 5% uses the distilled water wash organic phase to neutral again, and anhydrous sodium sulphate or anhydrous magnesium sulfate drying spend the night behind the reaction terminating.Isolate siccative, concentrate organic phase, use column chromatography purification, the mixing solutions of sherwood oil and methylene dichloride (volume ratio is 1: 1) is an eluent, the elutriant rotary evaporation that product will be arranged makes colourless liquid vinylformic acid-1-benzocyclobutene ester (V) product 2.4122g except that desolvating.
Gas-matter coupling detected result gets purity: 99.2%, and productive rate: 82.5%, structural characterization is as follows:
1H NMR (600MHz, CDCl
3) δ: 3.27 (d, 1H, J=14.3 ,-CHCH
2), 3.70 (dd, 1H, J=4.5,14.3 ,-CHCH
2), 5.86 (dd, 1H, J=1.5,10.6 ,-CH=CH
2), 6.01 (dd, 1H, J=1.7,4.5 ,-CHCH
2), 6.17 (dd, 1H, J=10.4,17.3 ,-CH=CH
2), 6.47 (dd, 1H, J=1.3,17.4 ,-CH=CH
2) .7.16 (d, 1H, J=7.4 ,-ArH), 7.25-7.28 (m, 2H ,-ArH), 7.30-7.35 (m, 1H ,-ArH).Nucleus magnetic resonance
13C NMR (150MHz, CDCl
3) δ: 38.98 (CH
2CH-), 71.66 (CH
2CH-), 123.22 (CH=CH
2), 123.64 (Ar-C), 127.56 (Ar-C), 128.30 (Ar-C), 130.04 (Ar-C), 131.07 (Ar-C), 142.74 (Ar-C), 144.15 (CH=CH
2), 166.14 (C=O).(KBr's infrared spectra IR films, cm
-1): 3067.2 (w), 2925.4 (w), 1742.7 (vs), 1634.7 (w), 1458.4 (w), 1406.7 (s), 1294.4 (w), 1271.4 (s), 1186.9 (s), 1053.4 (w), 985.8 (w), 809.8 (w), 744.6 (s), 708.8 (w).Mass spectrum EI-MS (m/z, %): 174.0 (M
+, 30), 103.0 (M
+-71,100).
Embodiment 14:
Prepare the method for vinylformic acid-1-benzocyclobutene ester (V), may further comprise the steps:
The 100mL two neck round-bottomed flasks that magnetic stir bar, constant pressure funnel and reflux condensing tube are housed are vacuumized (available heating gun is with its system heating, so that nitrogen is taken away water and oxygen in the system), logical nitrogen, repeatable operation three times is guaranteed the system anhydrous and oxygen-free.
With 1-hydroxy benzo cyclobutene (2.0g, 0.0167mol) under ice bath, be dissolved in methylene dichloride (5.3mL) solvent, with its injection of solution in the reaction system of anhydrous and oxygen-free, triethylamine (4.8mL) also is expelled in the reaction system, and ice bath stirs the dichloromethane solution dilution of 30min with 4-hydroxy benzo cyclobutene down; With acrylate chloride (2.03mL 0.025mol) is dissolved under the ice bath in methylene dichloride (7.5mL) solvent, with its injection of solution in constant pressure funnel.Under ice bath, the dichloromethane solution of acrylate chloride slowly is added drop-wise in the mixed solution of the dichloromethane solution of 4-hydroxy benzo cyclobutene and triethylamine, the dropping time is 30-90min, dropwises the back room temperature reaction 9-10 hour.With in the reaction solution impouring distilled water, (3 * 30mL) collect the merging organic phase to dichloromethane extraction, and the sodium carbonate solution washing organic phase with 5% uses the distilled water wash organic phase to neutral again, and anhydrous sodium sulphate or anhydrous magnesium sulfate drying spend the night behind the reaction terminating.Isolate siccative, concentrate organic phase, use column chromatography purification, the mixing solutions of sherwood oil and methylene dichloride (volume ratio is 1: 1) is an eluent, the elutriant rotary evaporation that product will be arranged makes colourless liquid vinylformic acid-1-benzocyclobutene ester (V) product 2.4122g except that desolvating.Gas-matter coupling detected result gets purity: 99.2%, and productive rate: 82.5%, structural characterization is as follows:
1H NMR (600MHz, CDCl
3) δ: 3.27 (d, 1H, J=14.3 ,-CHCH
2), 3.70 (dd, 1H, J=4.5,14.3 ,-CHCH
2), 5.86 (dd, 1H, J=1.5,10.6 ,-CH=CH
2), 6.01 (dd, 1H, J=1.7,4.5 ,-CHCH
2), 6.17 (dd, 1H, J=10.4,17.3 ,-CH=CH
2), 6.47 (dd, 1H, J=1.3,17.4 ,-CH=CH
2) .7.16 (d, 1H, J=7.4 ,-ArH), 7.25-7.28 (m, 2H ,-ArH), 7.30-7.35 (m, 1H ,-ArH).Nucleus magnetic resonance
13C NMR (150MHz, CDCl
3) δ: 38.98 (CH
2CH-), 71.66 (CH
2CH-), 123.22 (CH=CH
2), 123.64 (Ar-C), 127.56 (Ar-C), 128.30 (Ar-C), 130.04 (Ar-C), 131.07 (Ar-C), 142.74 (Ar-C), 144.15 (CH=CH
2), 166.14 (C=O).(KBr's infrared spectra IR films, cm
-1): 3067.2 (w), 2925.4 (w), 1742.7 (vs), 1634.7 (w), 1458.4 (w), 1406.7 (s), 1294.4 (w), 1271.4 (s), 1186.9 (s), 1053.4 (w), 985.8 (w), 809.8 (w), 744.6 (s), 708.8 (w).Mass spectrum EI-MS (m/z, %): 174.0 (M
+, 30), 103.0 (M
+-71,100).
Embodiment 15-19:
Among the preparation method of vinylformic acid-1-benzocyclobutene ester (V), the molar ratio of 1-hydroxy benzo cyclobutene and acrylate chloride sees the following form in step (a) batching:
The chemistry of the vinylformic acid that makes-1-benzocyclobutene ester, physical function parameter are with embodiment 12, and other is with embodiment 12,13 or 14, slightly.
Embodiment 20-22:
Among the preparation method of vinylformic acid-4-benzocyclobutene ester, raw material ratio: 1-hydroxy benzo cyclobutene/acrylate chloride=1/1.5, the dichloromethane solvent consumption sees the following form in step (c) batching:
| The embodiment numbering | 20 | 21 | 22 |
| Material concentration | 1.0mol/L | 2.0mol/L | 3.0mol/L |
| Yield | 80.3 | 81.7 | 85.8 |
The chemistry of the vinylformic acid that makes-1-benzocyclobutene ester, physical function parameter are with embodiment 12, and other is with embodiment 12,13 or 14, slightly.
Embodiment 23:
The preparation method of vinylformic acid-1-benzocyclobutane thiazolinyl methyl esters (VI), concrete steps are as follows:
A, batching: by 1-methylol benzocyclobutene: acrylate chloride is that 1: 2.0 molar ratio is got each component, and be dissolved in respectively in the diluting solvent methylene dichloride (solvent load be 4-hydroxy benzo cyclobutene 1-20 doubly); By 1-methylol benzocyclobutene: organic bases is that 1: 2.3 molar ratio is got organic bases;
B, ready reaction system: the reaction system that at room temperature will comprise reactor vacuumizes, logical nitrogen, anhydrous and oxygen-free to the reaction system;
C, dropwise reaction: in reaction system, mix, be added drop-wise to again the dichloromethane solution of 1-methylol benzocyclobutene in the dichloromethane solution of acrylate chloride with organic bases, or the dichloromethane solution of acrylate chloride is added drop-wise in the dichloromethane solution and organic bases mixed solution of 1-methylol benzocyclobutene, under ice bath, drip and stir, the dropping time is 30-90min, stirring reaction 11h at room temperature after dripping;
D, separation are purified: with in the reaction solution impouring distilled water, standing demix divided three extractions with methylene chloride after reaction stopped, and collected to merge organic phase; Extremely neutral with 5% aqueous sodium carbonate washing organic phase, usefulness distilled water wash organic phase again, use the inorganic salt siccative with the organic phase dried overnight again; Isolate siccative again, concentrate organic phase, use column chromatography purification, with the solvent sherwood oil or/and eluent methylene chloride, leacheate is concentrated into dried, colourless liquid product vinylformic acid-1-benzocyclobutane thiazolinyl methyl esters (VI);
Organic bases is triethylamine, pyridine or Tributylamine described in the step (a), and inorganic salt siccative described in the step (d) can be a silica gel column chromatography for anhydrous sodium sulphate or anhydrous magnesium sulfate, described column chromatography.
Vinylformic acid-1-benzocyclobutane thiazolinyl the methyl esters (VI) of preparation is a colourless liquid, and structural characterization is as follows: this product
1H NMR (600MHz, CDCl
3) δ: 2.94 (dd, 1H, J=2.2,14.2, CHCH
2), 3.36 (dd, 1H, J=5.2,14.2, CHCH
2), 3.72 (dd, 1H, J=5.2,14.2, CHCH
2), 3.80-3.90 (m, 1H, CHCH
2), 4.30-4.50 (m, 2H, CH
2), 5.84 (dd, 1H, J=1.1,10.5 ,-CH=CH
2), 6.15 (dd, 1H, J=10.5,17.3 ,-CH=CH
2), 6.42 (dd, 1H, J=1.3,17.5 ,-CH=CH
2), 7.09 (d, 2H, J=7.7 ,-ArH), 7.18-7.27 (m, 2H ,-ArH).Nucleus magnetic resonance
13C NMR (100MHz, CDCl
3) δ: 33.59 (CH
2CH-), 41.79 (CH
2CH-), 66.79 (O-CH
2-), 122.43 (Ar-C), 123.10 (Ar-C), 126.98 (Ar-C), 127.90 (Ar-C), 128.49 (Ar-C), 130.81 (CH=CH
2), 143.77 (Ar-C), 145.64 (CH=CH
2), 166.14 (C=O).(KBr's infrared spectra IR films, cm
-1): 3069.5 (w), 2933.0 (w), 1724.4 (vs), 1634.7 (w), 1618.9 (w), 1456.7 (w), 1405.3 (s), 1294.4 (w), 1264.2 (s), 1190.0 (vs), 1110.0 (w), 1052.4 (w), 983.3 (w), 908.0 (w), 809.7 (w), 745.9 (s).Mass spectrum EI-MS (m/z, %): 174.0 (M
+, 10), 103.0 (M
+-58,100).
Embodiment 24:
Prepare the method for vinylformic acid-1-benzocyclobutane thiazolinyl methyl esters (VI), may further comprise the steps:
The 100mL two neck round-bottomed flasks that magnetic stir bar, constant pressure funnel and reflux condensing tube are housed are vacuumized (available heating gun is with its system heating, so that nitrogen is taken away water and oxygen in the system), logical nitrogen, repeatable operation three times is guaranteed the system anhydrous and oxygen-free.
With 1-methylol benzocyclobutene (2.5g, 0.0186mol) under ice bath, be dissolved in methylene dichloride (6.0mL) solvent, with its injection of solution in the reaction system of anhydrous and oxygen-free, (5.37mL) also is expelled in the reaction system with triethylamine, ice bath stirs 30min down, with the dichloromethane solution dilution of 1-methylol benzocyclobutene; With acrylate chloride (3.04mL 0.0373mol) is dissolved under the ice bath in methylene dichloride (12mL) solvent, with its injection of solution in constant pressure funnel.Under ice bath, the dichloromethane solution of acrylate chloride slowly is added drop-wise in the mixed solution of the dichloromethane solution of 4-hydroxy benzo cyclobutene and triethylamine, the dropping time is 30-90min, dropwises the back room temperature reaction 11-12 hour.With in the reaction solution impouring distilled water, (3 * 30mL) collect the merging organic phase to dichloromethane extraction, and the sodium carbonate solution washing organic phase with 5% uses the distilled water wash organic phase to neutral again, and anhydrous sodium sulphate or anhydrous magnesium sulfate drying spend the night behind the reaction terminating.Separation is for drying prescription, concentrate organic phase, use column chromatography purification, the mixing solutions of sherwood oil and methylene dichloride (volume ratio is 1: 1) is an eluent, the elutriant rotary evaporation that product will be arranged gets colourless liquid product vinylformic acid-1-benzocyclobutane thiazolinyl methyl esters (VI) 3.0287g except that desolvating.
Gas-matter coupling detected result gets purity: 94.9%, and productive rate: 81.9%, structural characterization is as follows: this product
1H NMR (600MHz, CDCl
3) δ: 2.94 (dd, 1H, J=2.2,14.2, CHCH
2), 3.36 (dd, 1H, J=5.2,14.2, CHCH
2), 3.72 (dd, 1H, J=5.2,14.2, CHCH
2), 3.80-3.90 (m, 1H, CHCH
2), 4.30-4.50 (m, 2H, CH
2), 5.84 (dd, 1H, J=1.1,10.5 ,-CH=CH
2), 6.15 (dd, 1H, J=10.5,17.3 ,-CH=CH
2), 6.42 (dd, 1H, J=1.3,17.5 ,-CH=CH
2), 7.09 (d, 2H, J=7.7 ,-ArH), 7.18-7.27 (m, 2H ,-ArH).Nucleus magnetic resonance
13CNMR (100MHz, CDCl
3) δ: 33.59 (CH
2CH-), 41.79 (CH
2CH-), 66.79 (O-CH
2-), 122.43 (Ar-C), 123.10 (Ar-C), 126.98 (Ar-C), 127.90 (Ar-C), 128.49 (Ar-C), 130.81 (CH=CH
2), 143.77 (Ar-C), 145.64 (CH=CH
2), 166.14 (C=O).(KBr's infrared spectra IR films, cm
-1): 3069.5 (w), 2933.0 (w), 1724.4 (vs), 1634.7 (w), 1618.9 (w), 1456.7 (w), 1405.3 (s), 1294.4 (w), 1264.2 (s), 1190.0 (vs), 1110.0 (w), 1052.4 (w), 983.3 (w), 908.0 (w), 809.7 (w), 745.9 (s).Mass spectrum EI-MS (m/z, %): 174.0 (M
+, 10), 103.0 (M
+-58,100).
Embodiment 25:
Prepare the method for vinylformic acid-1-benzocyclobutane thiazolinyl methyl esters (VI), may further comprise the steps:
The 100mL two neck round-bottomed flasks that magnetic stir bar, constant pressure funnel and reflux condensing tube are housed are vacuumized (available heating gun is with its system heating, so that nitrogen is taken away water and oxygen in the system), logical nitrogen, repeatable operation three times is guaranteed the system anhydrous and oxygen-free.
With 1-methylol benzocyclobutene (2.5g, 0.0186mol) under ice bath, be dissolved in methylene dichloride (6.0mL) solvent, with its injection of solution in the reaction system of anhydrous and oxygen-free, (5.4mL) also is expelled in the reaction system with triethylamine, with the dichloromethane solution dilution of 1-methylol benzocyclobutene, ice bath stirs 30min down; With acrylate chloride (2.28mL 0.028mol) is dissolved under the ice bath in methylene dichloride (9.0mL) solvent, with its injection of solution in constant pressure funnel.Under ice bath, the dichloromethane solution of acrylate chloride slowly is added drop-wise in the mixed solution of the dichloromethane solution of 4-hydroxy benzo cyclobutene and triethylamine, the dropping time is 30-90min, dropwises the back room temperature reaction 11-12 hour.With in the reaction solution impouring distilled water, (3 * 30mL) collect the merging organic phase to dichloromethane extraction, and the sodium carbonate solution washing organic phase with 5% uses the distilled water wash organic phase to neutral again, and anhydrous sodium sulphate or anhydrous magnesium sulfate drying spend the night behind the reaction terminating.Isolate siccative, concentrate organic phase, use column chromatography purification, the mixing solutions of sherwood oil and methylene dichloride (volume ratio is 1: 1) is an eluent, the elutriant rotary evaporation that product will be arranged gets colourless liquid product vinylformic acid-1-benzocyclobutane thiazolinyl methyl esters (VI) 3.26g except that desolvating.Gas-matter coupling detected result gets purity: 96.2%, and productive rate: 89.3%, structural characterization is as follows: this product
1H NMR (600MHz, CDCl
3) δ: 2.94 (dd, 1H, J=2.2,14.2, CHCH
2), 3.36 (dd, 1H, J=5.2,14.2, CHCH
2), 3.72 (dd, 1H, J=5.2,14.2, CHCH
2), 3.80-3.90 (m, 1H, CHCH
2), 4.30-4.50 (m, 2H, CH
2), 5.84 (dd, 1H, J=1.1,10.5 ,-CH=CH
2), 6.15 (dd, 1H, J=10.5,17.3 ,-CH=CH
2), 6.42 (dd, 1H, J=1.3,17.5 ,-CH=CH
2), 7.09 (d, 2H, J=7.7 ,-ArH), 7.18-7.27 (m, 2H ,-ArH).Nucleus magnetic resonance
13CNMR (100MHz, CDCl
3) δ: 33.59 (CH
2CH-), 41.79 (CH
2CH-), 66.79 (O-CH
2-), 122.43 (Ar-C), 123.10 (Ar-C), 126.98 (Ar-C), 127.90 (Ar-C), 128.49 (Ar-C), 130.81 (CH=CH
2), 143.77 (Ar-C), 145.64 (CH=CH
2), 166.14 (C=O).(KBr's infrared spectra IR films, cm
-1): 3069.5 (w), 2933.0 (w), 1724.4 (vs), 1634.7 (w), 1618.9 (w), 1456.7 (w), 1405.3 (s), 1294.4 (w), 1264.2 (s), 1190.0 (vs), 1110.0 (w), 1052.4 (w), 983.3 (w), 908.0 (w), 809.7 (w), 745.9 (s).Mass spectrum EI-MS (m/z, %): 174.0 (M
+, 10), 103.0 (M
+-58,100).
Embodiment 26-30:
Among the preparation method of vinylformic acid-1-benzocyclobutane thiazolinyl methyl esters, the molar ratio of 1-methylol benzocyclobutene and acrylate chloride sees the following form in step (a) batching:
The chemistry of the vinylformic acid that makes-1-benzocyclobutane thiazolinyl methyl esters, physical function parameter are with embodiment 23, and other is with embodiment 23,24 or 25, slightly.
Embodiment 31-33:
Among the preparation method of vinylformic acid-1-benzocyclobutane thiazolinyl methyl esters, raw material ratio: 1-methylol benzocyclobutene/acrylate chloride=1/1.5, the dichloromethane solvent consumption sees the following form in step (c) batching:
| The embodiment numbering | 31 | 32 | 33 |
| Material concentration | 1.0mol/L | 2.0mol/L | 3.0mol/L |
| Yield | 79.4 | 80.1 | 82.0 |
The chemistry of the vinylformic acid that makes-1-benzocyclobutene ester, physical function parameter are with embodiment 23, and other is with embodiment 23,24 or 25, slightly.
The invention is not restricted to the foregoing description, content of the present invention is described all can implement and have described good result.
Claims (9)
1. vinylformic acid-4-benzocyclobutene ester is characterized in that this compound has the chemical structural formula of (IV):
This compound acrylic acid-4-benzocyclobutene ester (IV) is a colourless liquid, and structural characterization is as follows: nucleus magnetic resonance
1HNMR, 600MHz, CDCl
3: δ: 3.15 (d, 4H, J=3.1, CH
2CH
2), 5.98 (dd, 1H, J=1.2,10.4 ,-CH=CH
2), 6.31 (dd, 1H, J=10.6,17.4 ,-CH=CH
2), 6.58 (dd, 1H, J=1.2,10.4 ,-CH=CH
2), 6.83 (s, 1H ,-ArH), 6.89 (dd, 1H, J=1.8,7.9 ,-ArH), 7.04 (s, 1H ,-ArH); Nucleus magnetic resonance
13C NMR, 100MHz, CDCl
3: δ: 29.03 (CH
2CH
2), 29.07 (CH
2CH
2), 116.51 (CH=CH
2), 120.20 (Ar-C), 123.61 (Ar-C), 128.11 (Ar-C), 132.28 (CH=CH
2), 143.11 (Ar-C), 146.42 (Ar-C), 149.78 (Ar-C), 165.04 (C=O); Infrared spectra IR, KBr films, cm
-1: 3035.9 (w), 2933.1 (s), 1742.7 (vs), 1634.5 (s), 1592.6 (w), 1606.0 (w), 1467. (s), 1402.9 (s), 1244.9 (s), 1158.9 (vs), 1117.6 (w), 983.8 (s), 902.3 (s), 822.3 (w), 777.3 (w); Mass spectrum EI-MS (m/z, %): 174.0 (M
+, 100), 120.0 (M
+-54,80).
2. the preparation method of vinylformic acid-4-benzocyclobutene ester is characterized in that comprising the following steps:
A, batching: by 4-hydroxy benzo cyclobutene: acrylate chloride is 1: the molar ratio of 1.0-2.0 is got each component, and is dissolved in respectively in the diluting solvent methylene dichloride; By 4-hydroxy benzo cyclobutene: organic bases is 1: the molar ratio of 1.0-3.0 is got organic bases;
B, ready reaction system: the reaction system that at room temperature will comprise reactor vacuumizes, logical nitrogen, anhydrous and oxygen-free to the reaction system;
C, dropwise reaction: in reaction system, mix, be added drop-wise to again the dichloromethane solution of 4-hydroxy benzo cyclobutene in the dichloromethane solution of acrylate chloride with organic bases, or the dichloromethane solution of acrylate chloride is added drop-wise in the dichloromethane solution and organic bases mixed solution of 4-hydroxy benzo cyclobutene, under ice bath, drip and stir, the dropping time is 30-90min, stirring reaction 7-8h at room temperature after dripping;
D, separation are purified: with in the reaction solution impouring distilled water, standing demix divided three extractions with methylene chloride after reaction stopped, and collected to merge organic phase; Extremely neutral with 5% aqueous sodium carbonate washing organic phase, usefulness distilled water wash organic phase again, use the inorganic salt siccative with the organic phase dried overnight again; Isolate siccative again, concentrate organic phase, use column chromatography purification, or/and eluent methylene chloride, leacheate is concentrated into dried, make colourless liquid product vinylformic acid-4-benzocyclobutene ester (IV) with the solvent sherwood oil;
The vinylformic acid that makes-4-benzocyclobutene ester (IV) is a colourless liquid, and structural characterization is as follows: nucleus magnetic resonance
1H NMR, 600MHz, CDCl
3: δ: 3.15 (d, 4H, J=3.1, CH
2CH
2), 5.98 (dd, 1H, J=1.2,10.4 ,-CH=CH
2), 6.31 (dd, 1H, J=10.6,17.4 ,-CH=CH
2), 6.58 (dd, 1H, J=1.2,10.4 ,-CH=CH
2), 6.83 (s, 1H ,-ArH), 6.89 (dd, 1H, J=1.8,7.9 ,-ArH), 7.04 (s, 1H ,-ArH); Nucleus magnetic resonance
13C NMR, 100MHz, CDCl
3: δ: 29.03 (CH
2CH
2), 29.07 (CH
2CH
2), 116.51 (CH=CH
2), 120.20 (Ar-C), 123.61 (Ar-C), 128.11 (Ar-C), 132.28 (CH=CH
2), 143.11 (Ar-C), 146.42 (Ar-C), 149.78 (Ar-C), 165.04 (C=O); Infrared spectra IR, KBr films, cm
-1: 3035.9 (w), 2933.1 (s), 1742.7 (vs), 1634.5 (s), 1592.6 (w), 1606.0 (w), 1467. (s), 1402.9 (s), 1244.9 (s), 1158.9 (vs), 1117.6 (w), 983.8 (s), 902.3 (s), 822.3 (w), 777.3 (w); Mass spectrum EI-MS (m/z, %): 174.0 (M
+, 100), 120.0 (M
+-54,80).
3. press the preparation method of the described vinylformic acid of claim 2-4-benzocyclobutene ester, it is characterized in that: organic bases described in the step a is triethylamine, pyridine or Tributylamine, and the siccative of inorganic salt described in the steps d is that anhydrous sodium sulphate or anhydrous magnesium sulfate, described column chromatography are silica gel column chromatographies.
4. vinylformic acid-1-benzocyclobutene ester is characterized in that this compound has the chemical structural formula of (V):
This compound acrylic acid-1-benzocyclobutene ester is (V) colourless liquid, and structural characterization is as follows:
1H NMR, 600MHz, CDCl
3: δ: 3.27 (d, 1H, J=14.3 ,-CHCH
2), 3.70 (dd, 1H, J=4.5,14.3 ,-CHCH
2), 5.86 (dd, 1H, J=1.5,10.6 ,-CH=CH
2), 6.01 (dd, 1H, J=1.7,4.5 ,-CHCH
2), 6.17 (dd, 1H, J=10.4,17.3 ,-CH=CH
2), 6.47 (dd, 1H, J=1.3,17.4 ,-CH=CH
2) .7.16 (d, 1H, J=7.4 ,-ArH), 7.25-7.28 (m, 2H ,-ArH), 7.30-7.35 (m, 1H ,-ArH); Nucleus magnetic resonance
13C NMR, 150MHz, CDCl
3: δ: 38.98 (CH
2CH-), 71.66 (CH
2CH-), 123.22 (CH=CH
2), 123.64 (Ar-C), 127.56 (Ar-C), 128.30 (Ar-C), 130.04 (Ar-C), 131.07 (Ar-C), 142.74 (Ar-C), 144.15 (CH=CH
2), 166.14 (C=O); Infrared spectra IR, KBr films, cm
-1: 3067.2 (w), 2925.4 (w), 1742.7 (vs), 1634.7 (w), 1458.4 (w), 1406.7 (s), 1294.4 (w), 1271.4 (s), 1186.9 (s), 1053.4 (w), 985.8 (w), 809.8 (w), 744.6 (s), 708.8 (w); Mass spectrum EI-MS (m/z, %): 174.0 (M
+, 30), 103.0 (M
+-71,100).
5. the preparation method of vinylformic acid-1-benzocyclobutene ester is characterized in that comprising the following steps:
A, batching: by 1-hydroxy benzo cyclobutene: acrylate chloride is 1: the molar ratio of 1.0-2.0 is got each component, and is dissolved in respectively in the diluting solvent methylene dichloride; By 1-hydroxy benzo cyclobutene: organic bases is 1: the molar ratio of 1.0-3.0 is got organic bases;
B, ready reaction system: the reaction system that at room temperature will comprise reactor vacuumizes, logical nitrogen, anhydrous and oxygen-free to the reaction system;
C, dropwise reaction: in reaction system, mix, be added drop-wise to again the dichloromethane solution of 1-hydroxy benzo cyclobutene in the dichloromethane solution of acrylate chloride with organic bases, or the dichloromethane solution of acrylate chloride is added drop-wise in the dichloromethane solution and organic bases mixed solution of 1-hydroxy benzo cyclobutene, under ice bath, drip and stir, the dropping time is 30-90min, stirring reaction 9-10h at room temperature after dripping;
D, separation are purified: with in the reaction solution impouring distilled water, standing demix divided three extractions with methylene chloride after reaction stopped, and collected to merge organic phase; Extremely neutral with 5% aqueous sodium carbonate washing organic phase, usefulness distilled water wash organic phase again, use the inorganic salt siccative with the organic phase dried overnight again; Isolate siccative again, concentrate organic phase, use column chromatography purification, or/and eluent methylene chloride, leacheate is concentrated into dried, make colourless liquid product vinylformic acid-1-benzocyclobutene ester (V) with the solvent sherwood oil;
Vinylformic acid-1-benzocyclobutene the ester (V) of preparation is a colourless liquid, and structural characterization is as follows:
1H NMR, 600MHz, CDCl
3: δ: 3.27 (d, 1H, J=14.3 ,-CHCH
2), 3.70 (dd, 1H, J=4.5,14.3 ,-CHCH
2), 5.86 (dd, 1H, J=1.5,10.6 ,-CH=CH
2), 6.01 (dd, 1H, J=1.7,4.5 ,-CHCH
2), 6.17 (dd, 1H, J=10.4,17.3 ,-CH=CH
2), 6.47 (dd, 1H, J=1.3,17.4 ,-CH=CH
2) .7.16 (d, 1H, J=7.4 ,-ArH), 7.25-7.28 (m, 2H ,-ArH), 7.30-7.35 (m, 1H ,-ArH); Nucleus magnetic resonance
13C NMR, 150MHz, CDCl
3: δ: 38.98 (CH
2CH-), 71.66 (CH
2CH-), 123.22 (CH=CH
2), 123.64 (Ar-C), 127.56 (Ar-C), 128.30 (Ar-C), 130.04 (Ar-C), 131.07 (Ar-C), 142.74 (Ar-C), 144.15 (CH=CH
2), 166.14 (C=O); Infrared spectra IR, KBr films, cm
-1: 3067.2 (w), 2925.4 (w), 1742.7 (vs), 1634.7 (w), 1458.4 (w), 1406.7 (s), 1294.4 (w), 1271.4 (s), 1186.9 (s), 1053.4 (w), 985.8 (w), 809.8 (w), 744.6 (s), 708.8 (w); Mass spectrum EI-MS (m/z, %): 174.0 (M
+, 30), 103.0 (M
+-71,100).
6. press the preparation method of the described vinylformic acid of claim 5-1-benzocyclobutene ester, it is characterized in that: organic bases described in the step a is triethylamine, pyridine or Tributylamine, the siccative of inorganic salt described in the steps d is anhydrous sodium sulphate or anhydrous magnesium sulfate, and described column chromatography is a silica gel column chromatography.
7. vinylformic acid-1-benzocyclobutane thiazolinyl methyl esters is characterized in that this compound has the chemical structural formula of (VI):
This compound acrylic acid-1-benzocyclobutane thiazolinyl methyl esters (VI) is a colourless liquid, and structural characterization is as follows: this product
1H NMR, 600MHz, CDCl
3: δ: 2.94 (dd, 1H, J=2.2,14.2, CHCH
2), 3.36 (dd, 1H, J=5.2,14.2, CHCH
2), 3.72 (dd, 1H, J=5.2,14.2, CHCH
2), 3.80-3.90 (m, 1H, CHCH
2), 4.30-4.50 (m, 2H, CH
2), 5.84 (dd, 1H, J=1.1,10.5 ,-CH=CH
2), 6.15 (dd, 1H, J=10.5,17.3 ,-CH=CH
2), 6.42 (dd, 1H, J=1.3,17.5 ,-CH=CH
2), 7.09 (d, 2H, J=7.7 ,-ArH), 7.18-7.27 (m, 2H ,-ArH); Nucleus magnetic resonance
13C NMR, 100MHz, CDCl
3: δ: 33.59 (CH
2CH-), 41.79 (CH
2CH-), 66.79 (O-CH
2-), 122.43 (Ar-C), 123.10 (Ar-C), 126.98 (Ar-C), 127.90 (Ar-C), 128.49 (Ar-C), 130.81 (CH=CH
2), 143.77 (Ar-C), 145.64 (CH=CH
2), 166.14 (C=O); Infrared spectra IR, KBr films, cm
-1: 3069.5 (vs), 2933.0 (vs), 1724.4 (s), 1634.7 (vs), 1618.9 (w), 1456.7 (vs), 1405.3 (s), 1294.4 (w), 1264.2 (s), 1190.0 (s), 1110.0 (vs), 1052.4 (w), 983.3 (vs), 908.0 (w), 809.7 (s), 745.9 (w); Mass spectrum EI-MS (m/z, %): 174.0 (M
+, 10), 103.0 (M
+-58,100).
8. the preparation method of vinylformic acid-1-benzocyclobutane thiazolinyl methyl esters is characterized in that comprising the following steps:
A, batching: by 1-methylol benzocyclobutene: acrylate chloride is 1: the molar ratio of 1.0-2.0 is got each component, and is dissolved in respectively in the diluting solvent methylene dichloride; By 1-methylol benzocyclobutene: organic bases is 1: the molar ratio of 1.0-3.0 is got organic bases;
B, ready reaction system: the reaction system that at room temperature will comprise reactor vacuumizes, logical nitrogen, anhydrous and oxygen-free to the reaction system;
C, dropwise reaction: in reaction system, mix, be added drop-wise to again the dichloromethane solution of 1-methylol benzocyclobutene in the dichloromethane solution of acrylate chloride with organic bases, or the dichloromethane solution of acrylate chloride is added drop-wise in the dichloromethane solution and organic bases mixed solution of 1-methylol benzocyclobutene, under ice bath, drip and stir, the dropping time is 30-90min, stirring reaction 11-12h at room temperature after dripping;
D, separation are purified: with in the reaction solution impouring distilled water, standing demix divided three extractions with methylene chloride after reaction stopped, and collected to merge organic phase; Extremely neutral with 5% aqueous sodium carbonate washing organic phase, usefulness distilled water wash organic phase again, use the inorganic salt siccative with the organic phase dried overnight again; Isolate siccative again, concentrate organic phase, use column chromatography purification, with the solvent sherwood oil or/and eluent methylene chloride, leacheate is concentrated into dried, colourless liquid product vinylformic acid-1-benzocyclobutane thiazolinyl methyl esters (VI);
Vinylformic acid-1-benzocyclobutane thiazolinyl the methyl esters (VI) of preparation is a colourless liquid, and structural characterization is as follows: this product
1H NMR, 600MHz, CDCl
3: δ: 2.94 (dd, 1H, J=2.2,14.2, CHCH
2), 3.36 (dd, 1H, J=5.2,14.2, CHCH
2), 3.72 (dd, 1H, J=5.2,14.2, CHCH
2), 3.80-3.90 (m, 1H, CHCH
2), 4.30-4.50 (m, 2H, CH
2), 5.84 (dd, 1H, J=1.1,10.5 ,-CH=CH
2), 6.15 (dd, 1H, J=10.5,17.3 ,-CH=CH
2), 6.42 (dd, 1H, J=1.3,17.5 ,-CH=CH
2), 7.09 (d, 2H, J=7.7 ,-ArH), 7.18-7.27 (m, 2H ,-ArH); Nucleus magnetic resonance
13C NMR, 100MHz, CDCl
3: δ: 33.59 (CH
2CH-), 41.79 (CH
2CH-), 66.79 (O-CH
2-), 122.43 (Ar-C), 123.10 (Ar-C), 126.98 (Ar-C), 127.90 (Ar-C), 128.49 (Ar-C), 130.81 (CH=CH
2), 143.77 (Ar-C), 145.64 (CH=CH
2), 166.14 (C=O); Infrared spectra IR, KBr films, cm
-1: 3069.5 (vs), 2933.0 (vs), 1724.4 (s), 1634.7 (vs), 1618.9 (w), 1456.7 (vs), 1405.3 (s), 1294.4 (w), 1264.2 (s), 1190.0 (s), 1110.0 (vs), 1052.4 (w), 983.3 (vs), 908.0 (w), 809.7 (s), 745.9 (w); Mass spectrum EI-MS (m/z, %): 174.0 (M
+, 10), 103.0 (M
+-58,100).
9. by the described vinylformic acid of claim 8-1-benzocyclobutane thiazolinyl methyl esters preparation method, it is characterized in that: organic bases described in the step a is triethylamine, pyridine or Tributylamine, the siccative of inorganic salt described in the steps d is anhydrous sodium sulphate or anhydrous magnesium sulfate, and described column chromatography is a silica gel column chromatography.
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| KR102308361B1 (en) * | 2013-12-31 | 2021-10-01 | 다우 글로벌 테크놀로지스 엘엘씨 | Crosslinkable polymers and underlayer compositions |
| US10513568B2 (en) * | 2017-12-01 | 2019-12-24 | Rohm and Haas Electronic Materials | Methods of making stable and thermally polymerizable vinyl, amino or oligomeric phenoxy benzocyclobutene monomers with improved curing kinetics |
| CN113773432B (en) * | 2021-09-27 | 2022-07-12 | 中国科学院兰州化学物理研究所 | Low-dielectric-constant shape memory polystyrene and preparation method and application thereof |
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| CN101134706A (en) * | 2007-10-17 | 2008-03-05 | 南京工业大学 | Method for preparing symmetrical benzocyclobutene compound |
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| US5032451A (en) * | 1989-05-30 | 1991-07-16 | Shell Oil Company | Bisbenzocyclobutene/bisimide compositions |
| CN101134706A (en) * | 2007-10-17 | 2008-03-05 | 南京工业大学 | Method for preparing symmetrical benzocyclobutene compound |
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| CN102875373B (en) * | 2012-10-19 | 2014-12-17 | 义乌市中力工贸有限公司 | Different-activity divinyl compound and preparation method thereof |
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