CN114276380A - Polyalkynylbenzene conjugated compound and synthetic method thereof - Google Patents
Polyalkynylbenzene conjugated compound and synthetic method thereof Download PDFInfo
- Publication number
- CN114276380A CN114276380A CN202111624909.0A CN202111624909A CN114276380A CN 114276380 A CN114276380 A CN 114276380A CN 202111624909 A CN202111624909 A CN 202111624909A CN 114276380 A CN114276380 A CN 114276380A
- Authority
- CN
- China
- Prior art keywords
- compound
- poly
- reaction
- alkynylbenzene
- conjugated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 63
- 238000010189 synthetic method Methods 0.000 title claims description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 12
- 229940125904 compound 1 Drugs 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000001308 synthesis method Methods 0.000 claims description 8
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 7
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 6
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 6
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 claims description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 5
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 5
- 239000012312 sodium hydride Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- BPVHWNVBBDHIQU-UHFFFAOYSA-N 2-bromoethynylbenzene Chemical compound BrC#CC1=CC=CC=C1 BPVHWNVBBDHIQU-UHFFFAOYSA-N 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005698 Diels-Alder reaction Methods 0.000 abstract description 3
- -1 aromatic alkyne Chemical class 0.000 abstract description 3
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007142 ring opening reaction Methods 0.000 abstract description 3
- 150000001345 alkine derivatives Chemical class 0.000 abstract description 2
- 150000001491 aromatic compounds Chemical class 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 230000006698 induction Effects 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 230000003335 steric effect Effects 0.000 abstract description 2
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 33
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 8
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 7
- 238000004440 column chromatography Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 6
- 150000002678 macrocyclic compounds Chemical class 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- AZQCFLDDJHERFZ-UHFFFAOYSA-N Br.C#Cc1ccccc1 Chemical compound Br.C#Cc1ccccc1 AZQCFLDDJHERFZ-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229920001197 polyacetylene Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- QRVSDVDFJFKYKA-UHFFFAOYSA-N dipropan-2-yl propanedioate Chemical compound CC(C)OC(=O)CC(=O)OC(C)C QRVSDVDFJFKYKA-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- KLYCPFXDDDMZNQ-UHFFFAOYSA-N Benzyne Chemical compound C1=CC#CC=C1 KLYCPFXDDDMZNQ-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- NGKSKVYWPINGLI-UHFFFAOYSA-N prop-2-ynylbenzene Chemical compound C#CCC1=CC=CC=C1 NGKSKVYWPINGLI-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- LBNVCJHJRYJVPK-UHFFFAOYSA-N trimethyl(4-trimethylsilylbuta-1,3-diynyl)silane Chemical compound C[Si](C)(C)C#CC#C[Si](C)(C)C LBNVCJHJRYJVPK-UHFFFAOYSA-N 0.000 description 1
- VOYMPSZBODLRKS-UHFFFAOYSA-N trimethylsilanylium Chemical compound C[Si+](C)C VOYMPSZBODLRKS-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Compared with the prior art, the invention provides a method for synthesizing a poly (alkynylbenzene) conjugated compound, which comprises the step of heating 1,4, bis (trimethylsilyl) -1, 3-diacetylene and a tetraalkyne compound in an organic solvent for reaction. The reaction takes a phenylalkyne intermediate with extremely high activity as an induction reaction, realizes the reaction of a diyne derivative and alkyne without an additional metal catalyst, also overcomes the consistent tendency that phenylalkyne and a diyne compound are easy to form rings, overcomes the steric effect of trimethylsilane, overcomes the defect of synthesizing a six-membered stable ring structure, finally forms a stable chain-like poly-alkynylbenzene conjugated compound through ring opening by HDDA and Diels-Alder reaction and unstable four rings, brings great breakthrough to the synthesis of an aromatic alkyne poly-conjugated chain compound, has important significance to the synthesis of an aromatic compound containing Si, and provides a brand new way for developing the poly-alkynylbenzene conjugated compound.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a poly-alkynylbenzene conjugated compound and a synthesis method thereof.
Background
The aryne macrocyclic compound is a new carbon-rich conjugated macrocyclic molecule in the last 10 years, rapidly develops to nearly 100, can be widely applied to optical, electric, magnetic, nano and other functional materials, and arouses great interest of people.
The study on the aryne macrocyclic compounds shows that the annular aryne macrocyclic compounds mainly comprise phenylacetylene macrocyclic PAMs, diacetylene benzene macrocyclic PDMs, aryne three-dimensional polycyclic compounds, substituted derivatives thereof and the like, and are novel polygonal macrocyclic hydrocarbons formed by aromatic rings and alkyne bonds with fixed structures and regular shapes in recent years. Since the 90 s of the 20 th century, the development of aryne macrocyclic compounds is very rapid, several species are developed to nearly one hundred species at present, and the great potential of the aryne macrocyclic compounds as functional molecules causes great attention and attention of supramolecular chemists and material scientists.
However, the synthesis of the benzyne conjugated chain compound is not satisfactory, and the aryne chain conjugated compound has smaller steric hindrance due to the fact that the molecular skeleton is different from that of the cyclic conjugated compound, so that the aryne chain conjugated compound also has important research significance for developing novel optical, electric, magnetic and nano materials, and also has important scientific research significance for researching domino reaction and aromatic conjugated compounds containing hetero elements.
Disclosure of Invention
The invention aims to provide a poly-alkynylbenzene conjugated compound and a synthetic method thereof, which have simple reaction and provide a brand new approach for developing aromatic poly-alkynylbenzene conjugated single-chain macromolecular organic materials.
The specific technical scheme of the invention is as follows:
a synthetic method of a poly-alkynylbenzene conjugated compound comprises the following steps:
reacting 1,4, bis (trimethylsilyl) -1, 3-diacetylene with a tetraalkyne compound in an organic solvent, and separating and purifying after the reaction is finished to obtain the poly-alkynylbenzene conjugated compound.
The structural formula of the 1,4, bis (trimethylsilyl) -1, 3-diacetylene is as follows:
the reaction is specifically as follows: reacting at 100-105 ℃ for 12-15 hours;
the organic solvent is anhydrous toluene or acetonitrile;
the mass ratio of the tetraalkyne compound to the 1,4, bis (trimethylsilyl) -1, 3-diacetylene is 1-1.2: 1.
the concentration of the 1,4, bis (trimethylsilyl) -1, 3-diacetylene in the organic solvent is 0.33-0.35 mol/L;
the separation and purification method comprises the following steps: washing the crude product with saturated aqueous sodium chloride solution, extracting with ethyl acetate, performing reduced pressure spin drying, performing wet column packing, and performing column packing by using a volume ratio of 1: 80-140 ethyl acetate: performing column chromatography separation and purification on the petroleum ether serving as an eluent to obtain a light yellow oily substance, and recrystallizing to obtain a light yellow crystalline solid product, namely the poly-alkynylbenzene conjugated compound;
the eluent is preferably a mixture of 1: ethyl acetate of 120: petroleum ether.
The structural formula of the tetrayne compound is as follows:
wherein E1And E2Same as CO2R and R are linear alkyl, branched alkyl, saturated hydrocarbon, unsaturated hydrocarbon or aromatic hydrocarbon groups; preferably, R is a straight or branched alkyl group; more preferably, R is a straight chain alkyl group of four carbons or less or a branched alkyl group of four carbons or less;
the preparation method of the tetraalkyne compound comprises the following steps:
1) adding malonate and propargyl bromide into anhydrous acetonitrile, performing ice-water bath, reacting by using sodium hydride as an alkali, and then purifying and separating to obtain a compound 1;
2) mixing the compound 1 prepared in the step 1) with phenylethynyl bromide in an anhydrous oxygen-free catalytic system of CuCl, adding n-butylamine aqueous solution and hydroxylamine hydrochloride, stirring for reaction under ice bath, and separating and purifying a product to obtain the tetraalkyne compound.
Further, the molar ratio of the sodium hydride, the malonate, the propargyl bromide and the anhydrous acetonitrile in the step 1) is 4-5: 1: 2.1-2.4: 20-23.
Preferably, the malonate in step 1) is selected from diisopropyl malonate.
In the step 1), the reaction temperature is 0-5 ℃ under the condition of ice-water bath; the reaction time is more than 8 hours; the preferable reaction time is 8.5 h;
the purification and separation in the step 1) are specifically as follows: the product was washed with saturated aqueous sodium chloride solution, extracted with ethyl acetate, dried under reduced pressure using ethyl acetate: and (3) performing column chromatography on the mixed solvent of petroleum ether and 1:80 to obtain the product, namely the compound 1.
The structural formula of the compound 1 in the step 1) is as follows:
wherein E1And E2Same as CO2R is CO2R and R are linear alkyl, branched alkyl, saturated hydrocarbon, unsaturated hydrocarbon or aromatic hydrocarbon groups; preferably, R is a straight or branched alkyl group; more preferably, R is a straight chain alkyl group of four carbons or less or a branched alkyl group of four carbons or less; more preferably, R is a straight chain alkyl group of four carbons or less or a branched chain alkyl group of four carbons or less.
More preferably, the compound 1 has the structural formula:
in step 2), the compound 1, phenylethynyl bromide: CuCl: the molar ratio of hydroxylamine hydrochloride is 1: 2-2.5: 0.15-0.16: 0.07-0.08.
The n-butylamine aqueous solution is used as a solvent in the step 2), and the mass concentration of the n-butylamine aqueous solution is 30%; the hydroxylamine hydrochloride is alkali, and hydrogen on the diyne is extracted.
In the step 2), the dosage ratio of the compound 1 to the n-butylamine aqueous solution is 0.4-0.5 mol/L;
in the step 2), the stirring reaction time is at least 12 hours;
in the step 2), the preparation method of phenylacetylene bromide comprises the following steps: taking phenylacetylene and N-bromosuccinimide in acetone solvent, AgNO3Reacting for 3 hours at room temperature under the catalysis of a catalyst, washing a crude product by using a saturated sodium chloride aqueous solution, and extracting by using normal hexane to obtain phenylacetylene bromide;
wherein the ratio of phenylacetylene: n-bromosuccinimide and AgNO3The molar ratio is 1: 1-1.2: 0.05.
in step 2), the separation and purification means: the product was washed with saturated sodium chloride solution, extracted with dichloromethane, spin-dried under reduced pressure and concentrated under reduced pressure using ethyl acetate: separating by column chromatography with petroleum ether at a ratio of 1:60-80 to obtain a light yellow solid product, namely a tetraalkyne compound;
the invention provides a poly-alkynylbenzene conjugated compound, which is synthesized by the method, and the structural formula of the poly-alkynylbenzene conjugated compound is as follows:
wherein E1And E2Same as CO2R and R are linear alkyl, branched alkyl, saturated hydrocarbon, unsaturated hydrocarbon or aromatic hydrocarbon groups;
preferably, the structural formula of the poly-alkynylbenzene conjugated compound is as follows:
compared with the prior art, the invention provides a method for synthesizing a poly-alkynylbenzene conjugated compound, which comprises the step of heating 1,4, bis (trimethylsilyl) -1, 3-diacetylene and a tetraalkyne compound in an organic solvent for reaction. The reaction takes a phenylalkyne intermediate with extremely high activity as an induction reaction, realizes the reaction of a diyne derivative and alkyne without an additional metal catalyst, also overcomes the consistent tendency that phenylalkyne and a diyne compound are easy to form rings, overcomes the steric effect of trimethylsilane, overcomes the defect of synthesizing a six-membered stable ring structure, finally forms a stable chain-like poly-alkynylbenzene conjugated compound through ring opening by HDDA and Diels-Alder reaction and unstable four rings, brings great breakthrough to the synthesis of an aromatic alkyne poly-conjugated chain compound, has important significance to the synthesis of an aromatic compound containing Si, and provides a brand new way for developing the poly-alkynylbenzene conjugated compound.
Drawings
FIG. 1 is a structural formula of a poly-alkynylbenzene conjugated compound of the present invention; wherein E1And E2Same as CO2R and R are linear alkyl, branched alkyl, saturated hydrocarbon, unsaturated hydrocarbon or aromatic hydrocarbon groups;
FIG. 2 is a scheme showing the synthesis of a poly-alkynylbenzene conjugated compound according to the present invention;
FIG. 3 is a scheme for the synthesis of a poly-alkynylbenzene conjugate compound prepared in example 1;
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of a polyacetylene benzene conjugated compound prepared in example 1;
FIG. 5 is a nuclear magnetic resonance carbon spectrum of a polyacetylene benzene conjugated compound prepared in example 1;
FIG. 6A shows the mechanism of synthesis of the tetraalkynes of example 1;
FIG. 6B shows the reaction mechanism of the tetraalkynes of example 1 with 1,4, bis (trimethylsilyl) -1, 3-diacetylene;
fig. 7 is a single crystal diagram of a polyacetylene benzene conjugated compound prepared in example 1.
Detailed Description
Example 1
A synthetic method of a poly-alkynylbenzene conjugated compound comprises the following steps:
1)1,4, bis (trimethylsilyl) -1, 3-diacetylene with a purity of > 99.97%, TCL company;
2) adding 200mmol of diisopropyl malonate and 440mmol of propargyl bromide into 210mL of anhydrous acetonitrile by using 830mmol of sodium hydride as a catalyst, stirring and reacting for 8 hours in an ice-water bath at the temperature of 0-5 ℃, adding a saturated sodium chloride aqueous solution to wash a product, extracting with ethyl acetate, performing reduced pressure spin drying, and performing reaction on the product by adopting a volume ratio of ethyl acetate: performing column chromatography with mixed solvent of petroleum ether 1:80 to obtain product, i.e. compound 1 with structural formula
3) 100mmol phenylacetylene (10.2g) and 120mmol N-bromosuccinimide (21.36g) are put into a two-neck flask, an appropriate amount of acetone solvent is added (the solvent is used for submerging the solid reactant by 0.5 cm), and 5mmol (0.85g) AgNO is added3Catalyzing with catalyst, magnetically stirring, reacting at room temperature for 3 hours to obtain phenylacetylene bromide.
4) In a 500ml three-necked flask, 40mmol of Compound 1, 0.2g of hydroxylamine hydrochloride as a base, were mixed with 0.6g of CuClIn an anhydrous anaerobic catalytic system (a vacuum device for vacuumizing and releasing argon is adopted, vacuumizing and releasing is firstly carried out, and the vacuumizing and releasing is repeated for 3 times), then 100ml of an n-butylamine aqueous solution with the mass fraction of 30% (63g of water +27g of n-butylamine) is used as a solvent, a half of the solvent is firstly poured, 90mmol of phenylacetylene bromide prepared in the step 3) is poured, finally the rest solvent is poured, magnetic stirring reaction is carried out for 12 hours under ice bath, a product is washed by a saturated sodium chloride solution, dichloromethane is used for extraction, decompression and spin drying is carried out, and column chromatography (volume ratio of ethyl acetate: petroleum ether 1:80) to give a pale yellow solid product, i.e. a tetraalkynes compound of formula
4) Reacting 1.0mmol of 1,4, bis (trimethylsilyl) -1, 3-diacetylene prepared in the step 1) and 1.0mmol of tetraalkyne compound prepared in the step 3) in 3mL of anhydrous toluene solvent for 15 hours at 105 ℃ to obtain a crude product of the propargylbenzene conjugated compound; washing the crude product with saturated aqueous sodium chloride solution, extracting with ethyl acetate, performing reduced pressure spin drying, performing wet column packing, and performing column packing by using a solvent prepared from ethyl acetate: petroleum ether is 1: and (3) performing 120 column chromatography separation to obtain a light yellow oily product, namely the poly (alkynylbenzene) conjugated compound, wherein the column chromatography yield is about 60%, and the synthesized poly (alkynylbenzene) conjugated compound has a structural formula:
the product structure is passed through1H NMR、13C NMR, as follows:
1HNMR(400MHz,CDCl3)δ7.63-7.62(d,2H),7.48-7.29(m,9H),5.15-5.09(m,2H),3.82-3.76(d,4H),1.33-1.30(s,12H),0.28(s,9H)；
13C NMR(125MHz,CDCl3)δ170.95，143.75,142.86,142.74，139.47，129.28,128.33,127.72,123.11,119.18,117.16,98.18,92.40,87.80,86.95,77.06,76.74,74.59,69.53,59.13,41.13,40.55,21.61,21.59。
the reaction mechanism of embodiment 1 of the present invention is shown in fig. 6A and 6B, in fig. 6B, a tetraalkyne compound a undergoes a [3+2] HDDA reaction at a high temperature to generate a phenylalkyne compound B, the phenylalkyne compound B reacts with 1,4, bis (trimethylsilyl) -1, 3-butadiyne c in a toluene solvent at 105 ℃ for 15 hours, and then undergoes a [2+2] Diels-Alder reaction to form an intermediate compound d, a tetracycle in the intermediate compound d is unstable, a trimethylsilyl cation is removed by a ring-opening reaction, a compound f is formed via the intermediate compound e, and the compound f carries a negative ion, and abstracts H in water in the solvent to finally form a compound g.
The synthesis method is simple, convenient and efficient, and has short reaction time and high efficiency. The method breaks through the limitation that the prior ferrocene can not generate cycloaddition reaction, and has wider application and scientific research prospect in chemical production and clinical medicine.
The above detailed description of the synthesis of the poly-alkynylbenzene conjugated compounds with reference to the examples is illustrative and not restrictive, and several examples can be cited within the limits of the present invention, and thus variations and modifications thereof without departing from the general concept of the present invention shall fall within the scope of the present invention.
Claims (10)
1. A synthetic method of a poly-alkynylbenzene conjugated compound is characterized by comprising the following steps:
reacting 1,4, bis (trimethylsilyl) -1, 3-diacetylene with a tetraalkyne compound in an organic solvent, and separating and purifying after the reaction is finished to obtain the poly-alkynylbenzene conjugated compound.
2. The synthesis method according to claim 1, characterized in that the reaction is in particular: reaction at 100-105 deg.c for 12-15 hr.
3. The synthetic method of claim 1 wherein the organic solvent is anhydrous toluene or acetonitrile.
4. The method of synthesis according to claim 1, wherein the ratio of the amount of substance between the tetraalkynes and 1,4, bis (trimethylsilyl) -1, 3-diacetylene is 1-1.2: 1.
5. the synthesis method according to claim 1, wherein the concentration of 1,4, bis (trimethylsilyl) -1, 3-diacetylene in the organic solvent is 0.33-0.35 mol/L.
6. The method of claim 1, wherein the tetrayne compound has the formula:
wherein E1And E2Same as CO2R and R are linear alkyl, branched alkyl, saturated hydrocarbon, unsaturated hydrocarbon or aromatic hydrocarbon groups.
7. The synthesis method according to claim 1 or 6, wherein the preparation method of the tetraalkynes compound is as follows:
1) adding malonate and propargyl bromide into anhydrous acetonitrile, performing ice-water bath, reacting by using sodium hydride as an alkali, and then purifying and separating to obtain a compound 1;
2) mixing the compound 1 prepared in the step 1) with phenylethynyl bromide in an anhydrous oxygen-free catalytic system of CuCl, adding n-butylamine aqueous solution and hydroxylamine hydrochloride, stirring for reaction under ice bath, and separating and purifying a product to obtain the tetraalkyne compound.
8. The synthesis method according to claim 7, wherein the molar ratio of the sodium hydride, the malonate, the propargyl bromide and the anhydrous acetonitrile in the step 1) is 4-5: 1: 2.1-2.4: 20-23.
9. The synthesis method according to claim 7, wherein in step 2), the compound 1, phenylethynyl bromide: CuCl: the molar ratio of hydroxylamine hydrochloride is 1: 2-2.5: 0.15-0.16: 0.07-0.08.
10. The synthesis method of any one of claims 1 to 9The poly (alkynylbenzene) conjugate compound is characterized in that the structural formula of the poly (alkynylbenzene) conjugate compound is as follows:
wherein E1And E2Same as CO2R and R are linear alkyl, branched alkyl, saturated hydrocarbon, unsaturated hydrocarbon or aromatic hydrocarbon groups.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111624909.0A CN114276380A (en) | 2021-12-28 | 2021-12-28 | Polyalkynylbenzene conjugated compound and synthetic method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111624909.0A CN114276380A (en) | 2021-12-28 | 2021-12-28 | Polyalkynylbenzene conjugated compound and synthetic method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114276380A true CN114276380A (en) | 2022-04-05 |
Family
ID=80877577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111624909.0A Pending CN114276380A (en) | 2021-12-28 | 2021-12-28 | Polyalkynylbenzene conjugated compound and synthetic method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114276380A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108774272A (en) * | 2018-05-29 | 2018-11-09 | 安徽师范大学 | A kind of ferrocene derivatives and preparation method thereof |
| CN108774189A (en) * | 2018-06-08 | 2018-11-09 | 安徽师范大学 | Yi Zhong oxazine phenylate derivatives and preparation method thereof |
| CN108821975A (en) * | 2018-06-08 | 2018-11-16 | 安徽师范大学 | A kind of hydrogenation phenanthrene derivatives and preparation method thereof containing exocyclic double bond |
| CN110746305A (en) * | 2019-11-19 | 2020-02-04 | 安徽师范大学 | Polysubstituted dibenzoylbenzene derivative and synthetic method thereof |
| CN113045586A (en) * | 2021-03-26 | 2021-06-29 | 安徽师范大学 | Synthetic method of benzoxazole alkane derivative |
| CN113354691A (en) * | 2021-06-04 | 2021-09-07 | 安徽师范大学 | Synthetic method of ferrocene derivative luminescent material |
-
2021
- 2021-12-28 CN CN202111624909.0A patent/CN114276380A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108774272A (en) * | 2018-05-29 | 2018-11-09 | 安徽师范大学 | A kind of ferrocene derivatives and preparation method thereof |
| CN108774189A (en) * | 2018-06-08 | 2018-11-09 | 安徽师范大学 | Yi Zhong oxazine phenylate derivatives and preparation method thereof |
| CN108821975A (en) * | 2018-06-08 | 2018-11-16 | 安徽师范大学 | A kind of hydrogenation phenanthrene derivatives and preparation method thereof containing exocyclic double bond |
| CN110746305A (en) * | 2019-11-19 | 2020-02-04 | 安徽师范大学 | Polysubstituted dibenzoylbenzene derivative and synthetic method thereof |
| CN113045586A (en) * | 2021-03-26 | 2021-06-29 | 安徽师范大学 | Synthetic method of benzoxazole alkane derivative |
| CN113354691A (en) * | 2021-06-04 | 2021-09-07 | 安徽师范大学 | Synthetic method of ferrocene derivative luminescent material |
Non-Patent Citations (2)
| Title |
|---|
| JAN MAIER ET AL.: "Highly Conjugated π-Systems Arising from Cannibalistic Hexadehydro-Diels-Alder Couplings: Cleavage of C-C Single and Triple Bonds", 《CHEMISTRY - A EUROPEAN JOURNAL》, vol. 26, no. 68, pages 15989 - 16000 * |
| X. XIAO ET AL.: "Cu(I)-Mediated Bromoalkynylation and Hydroalkynylation Reactions of Unsymmetrical Benzynes: Complementary Modes of Addition", 《ANGEWANDTE CHEMIE INTERNATIONAL EDITION》, vol. 57, no. 50, pages 16564 - 16568 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Eliseeva et al. | Pushing the Ir-catalyzed C–H polyborylation of aromatic compounds to maximum capacity by exploiting reversibility | |
| Azizi et al. | Green procedure for the synthesis of bis (indolyl) methanes in water | |
| Suzuki et al. | Straightforward synthesis of five-membered metallacycloallenes: 1-Zirconacyclopenta-2, 3-diene compounds derived from 1, 3-enynes | |
| CN106749139B (en) | Polysubstituted condensed benzofuran derivative of one kind and preparation method thereof | |
| Guha et al. | TMS· OTf-Catalyzed α-bromination of carbonyl compounds by N-bromosuccinimide | |
| Yadav et al. | The reductive etherification of carbonyl compounds using polymethylhydrosiloxane activated by molecular iodine | |
| Manick et al. | Access to Fluorenones Using Benzocyclopentynone Surrogate as Partner for the [2+ 2+ 2] Cycloaddition Reaction | |
| CN106946704B (en) | A kind of polysubstituted condensed aromatics analog derivative and preparation method thereof | |
| Morita et al. | Synthesis of multisubstituted 1, 3-butadienes using the ruthenium-catalysed double addition of trimethylsilyldiazomethane to alkynylboronates | |
| CN109776562A (en) | A kind of epoxy bridging anthracene derivant and preparation method thereof | |
| CN114276380A (en) | Polyalkynylbenzene conjugated compound and synthetic method thereof | |
| Schneider et al. | Synthesis of enantiopure planar-chiral thiourea derivatives | |
| Veguillas et al. | Synthesis of Benzo‐and Naphthoquinonyl Boronic Acids: Exploring the Diels–Alder Reactivity | |
| CN110746305A (en) | Polysubstituted dibenzoylbenzene derivative and synthetic method thereof | |
| Kumaraswamy et al. | An organocatalytic enantioselective synthesis of (+)-duryne | |
| CN113354691A (en) | Synthetic method of ferrocene derivative luminescent material | |
| Cheng et al. | Intramolecular Cyclization of Ruthenium Vinylidene Complexes with a Tethering Vinyl Group: Facile Cleavage and Reconstruction of the C− C Double Bond | |
| CN113387886A (en) | 2-aminodibenzo [ c, e ] azepine compound and synthetic method thereof | |
| CN107641080A (en) | A kind of dihydronaphthalene ketones derivant containing spirane structure and preparation method thereof | |
| Lasri et al. | Solvent-dependent reactivities of acyclic nitrones with β-diketones: Catalyst-free syntheses of endiones and enones | |
| CN108383754B (en) | Preparation method and application of aryl oxime ester compound | |
| CN107954873B (en) | Polysubstituted olefine acid ester derivative and preparation method thereof | |
| Tapuhi et al. | The stereochemistry of overcrowded homomerous bistricyclic aromatic enes with alkylidene bridges | |
| CN109879830A (en) | A kind of oxaza heptane derivative and preparation method thereof containing exocyclic double bond | |
| Wu et al. | TfOH-catalyzed allylation of alkynes with cyclic Baylis–Hillman alcohols |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |