PL433281A1 - 1,2-di(methoxycarbonyl)benzo[1,2-j]coronene and the method of its preparation - Google Patents
1,2-di(methoxycarbonyl)benzo[1,2-j]coronene and the method of its preparationInfo
- Publication number
- PL433281A1 PL433281A1 PL433281A PL43328120A PL433281A1 PL 433281 A1 PL433281 A1 PL 433281A1 PL 433281 A PL433281 A PL 433281A PL 43328120 A PL43328120 A PL 43328120A PL 433281 A1 PL433281 A1 PL 433281A1
- Authority
- PL
- Poland
- Prior art keywords
- methoxycarbonyl
- benzo
- perylene
- mmol
- reactor
- Prior art date
Links
- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 title abstract 8
- 125000005605 benzo group Chemical group 0.000 title abstract 6
- 238000000034 method Methods 0.000 title abstract 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 abstract 5
- 239000000203 mixture Substances 0.000 abstract 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract 3
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 abstract 3
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 abstract 3
- 239000011541 reaction mixture Substances 0.000 abstract 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 abstract 2
- 238000004440 column chromatography Methods 0.000 abstract 2
- GZDAIUJPGGAHFR-UHFFFAOYSA-N dimethyl hexacyclo[12.8.0.02,11.03,8.04,21.017,22]docosa-1(14),2(11),3(8),4,6,9,12,15,17(22),18,20-undecaene-7,8-dicarboxylate Chemical group COC(=O)c1c(C(=O)OC)c2ccc3cccc4c5cccc6ccc1c(c56)c2c34 GZDAIUJPGGAHFR-UHFFFAOYSA-N 0.000 abstract 2
- 239000011261 inert gas Substances 0.000 abstract 2
- 239000007788 liquid Substances 0.000 abstract 2
- 229930195734 saturated hydrocarbon Natural products 0.000 abstract 2
- 239000000741 silica gel Substances 0.000 abstract 2
- 229910002027 silica gel Inorganic materials 0.000 abstract 2
- XBHPFCIWRHJDCP-UHFFFAOYSA-N (2-trimethylsilylphenyl) trifluoromethanesulfonate Chemical compound C[Si](C)(C)C1=CC=CC=C1OS(=O)(=O)C(F)(F)F XBHPFCIWRHJDCP-UHFFFAOYSA-N 0.000 abstract 1
- 230000005526 G1 to G0 transition Effects 0.000 abstract 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 abstract 1
- 238000009835 boiling Methods 0.000 abstract 1
- YTIVTFGABIZHHX-UHFFFAOYSA-N butynedioic acid Chemical compound OC(=O)C#CC(O)=O YTIVTFGABIZHHX-UHFFFAOYSA-N 0.000 abstract 1
- 238000006352 cycloaddition reaction Methods 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- VHILMKFSCRWWIJ-UHFFFAOYSA-N dimethyl acetylenedicarboxylate Chemical compound COC(=O)C#CC(=O)OC VHILMKFSCRWWIJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000003480 eluent Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002430 hydrocarbons Chemical class 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Przedmiotem wynalazku jest 1,2-di(metoksykarbonylo)benzo[1,2-j]koronen przedstawiony wzorem 1. Istotę wynalazku stanowi również sposób otrzymywania 1,2-di(metoksykarbonylo)benzo[1,2-j]koronenu przedstawionego wzorem 1, polegający na tym, że w pierwszym etapie do reaktora wprowadza się, w atmosferze gazu obojętnego, perylen i dienofil w postaci acetylenodikarboksylanu dimetylowego, przy czym nadmiar dienofila jest co najmniej trzykrotny, a następnie zamyka się reaktor i zawartą w nim mieszaninę reakcyjną ogrzewa się przez co najmniej 6 godzin, w temperaturze nie niższej niż 160°C, ale nie wyższej od temperatury rozkładu mieszaniny reakcyjnej, po czym oddestylowuje się nadmiarowy acetylenodikarboksylan, a pozostałość poddaje się oczyszczaniu za pomocą chromatografii kolumnowej na żelu krzemionkowym, stosując jako eluent niskowrzący nasycony węglowodór lub mieszaninę takich węglowodorów, co pozwala otrzymać produkt o czystości >98% z wydajnością do 95%. W etapie drugim, do reaktora odizolowanego od dostępu światła wprowadza się 1,2-di(metoksykarbonylo)benzo[ghi]perylen otrzymany w etapie pierwszym, mieszaninę stopionego sukcynonitrylu z 1,2-dimetoksyetanem w stosunku objętościowym mieszaniny od 3:1 do 1:3, w ilości od 5 do 20 ml tej mieszaniny na 1 mmol 1,2-di(metoksykarbonylo)benzo[ghi]perylenu, oraz fluorek cezu w ilości od 2 do 8 mmoli na 1 mmol 1,2-di(metoksykarbonylo)benzo[ghi]perylenu, następnie do mieszaniny reakcyjnej wprowadza się triflat 2-trimetylosililofenylu w ilości od 2 do 8 mmoli, na 1 mmol 1,2-di(metoksykarbonylo)benzo[ghi]perylenu, po czym zawartość reaktora miesza się w temperaturze od 40 do 100°C, w atmosferze gazu obojętnego, przez co najmniej 12 godzin, po czym, po zakończeniu reakcji cykloaddycji benzynu, chłodzi się zawartość reaktora do temperatury nie wyższej niż 50°C, i odparowuje lotne frakcje, zaś pozostałość przemywa się kilka razy ciekłym nasyconym węglowodorem alifatycznym, następnie kilka razy wodą, po czym przeprowadza się dalsze oczyszczanie metodą chromatografii kolumnowej w układzie faz normalnych, gdzie faza stacjonarna to żel krzemionkowy, faza ruchoma to mieszanina nasyconego ciekłego węglowodoru z chlorkiem metylenu w stosunku objętościowym od 10:1 do 1:1, otrzymując w efekcie produkt w postaci 1,2-di(metoksykarbonylo)benzo[1,2-j]koronenu o czystości >98% z wydajnością do 65%.The subject of the invention is 1,2-di (methoxycarbonyl) benzo [1,2-j] coronene represented by the formula 1. The invention also relates to the method of obtaining 1,2-di (methoxycarbonyl) benzo [1,2-j] coronene represented by the formula 1 , consisting in the fact that in the first stage, perylene and dienophile in the form of dimethyl acetylenedicarboxylate are introduced into the reactor under an inert gas atmosphere, the excess of dienophile being at least three times, and then the reactor is closed and the reaction mixture contained therein is heated by at least 6 hours at a temperature not lower than 160 ° C but not higher than the decomposition temperature of the reaction mixture, then excess acetylenedicarboxylate is distilled off, and the residue is purified by column chromatography on silica gel using a low-boiling saturated hydrocarbon as eluent, or a mixture of such hydrocarbons, which allows a product of> 98% purity to be obtained with a yield of up to 95%. In the second stage, 1,2-di (methoxycarbonyl) benzo [gh] perylene obtained in the first stage, a mixture of molten succinonitrile with 1,2-dimethoxyethane in a volume ratio of 3: 1 to 1, is introduced into the reactor isolated from the access of light: 3, in an amount of 5 to 20 ml of this mixture per 1 mmol of 1,2-di (methoxycarbonyl) benzo [gh] perylene, and cesium fluoride in an amount of 2 to 8 mmol per 1 mmol of 1,2-di (methoxycarbonyl) benzo [ghi] perylene, then 2-trimethylsilylphenyl triflate is introduced into the reaction mixture in an amount of 2 to 8 mmol, per 1 mmol of 1,2-di (methoxycarbonyl) benzo [ghi] perylene, and then the contents of the reactor are stirred at a temperature of 40 to 100 ° C, in an inert gas atmosphere, for at least 12 hours, then, after completion of the gasoline cycloaddition reaction, the contents of the reactor are cooled to a temperature of not more than 50 ° C, and volatile fractions are evaporated, and the residue is washed several times with liquid saturated aliphatic hydrocarbon, then several times with water, after further purification by normal phase column chromatography is carried out, where the stationary phase is silica gel, the mobile phase is a mixture of saturated hydrocarbon liquid with methylene chloride in a volume ratio of 10: 1 to 1: 1, resulting in a product in the form of 1, 2-di (methoxycarbonyl) benzo [1,2-j] coronene with purity> 98% in yield up to 65%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL433281A PL240179B1 (en) | 2020-03-18 | 2020-03-18 | 1,2-di(methoxycarbonyl)benzo[1,2-j]coronene and the method of its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL433281A PL240179B1 (en) | 2020-03-18 | 2020-03-18 | 1,2-di(methoxycarbonyl)benzo[1,2-j]coronene and the method of its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| PL433281A1 true PL433281A1 (en) | 2021-09-20 |
| PL240179B1 PL240179B1 (en) | 2022-02-28 |
Family
ID=77746071
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PL433281A PL240179B1 (en) | 2020-03-18 | 2020-03-18 | 1,2-di(methoxycarbonyl)benzo[1,2-j]coronene and the method of its preparation |
Country Status (1)
| Country | Link |
|---|---|
| PL (1) | PL240179B1 (en) |
-
2020
- 2020-03-18 PL PL433281A patent/PL240179B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| PL240179B1 (en) | 2022-02-28 |
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