PL210184B1 - New dicyanostyril compounds and method for their manufacture - Google Patents
New dicyanostyril compounds and method for their manufactureInfo
- Publication number
- PL210184B1 PL210184B1 PL379139A PL37913906A PL210184B1 PL 210184 B1 PL210184 B1 PL 210184B1 PL 379139 A PL379139 A PL 379139A PL 37913906 A PL37913906 A PL 37913906A PL 210184 B1 PL210184 B1 PL 210184B1
- Authority
- PL
- Poland
- Prior art keywords
- formula
- butyl
- compound
- compounds
- new
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 title claims description 15
- 238000000034 method Methods 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- -1 dicyanostyryl compounds Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003211 polymerization photoinitiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Przedmiotem wynalazku są nowe związki dicyjanostyrylowe oraz sposób ich wytwarzania. Związki te działają, jako fotoinicjatory polimeryzacji.The present invention relates to novel dicyanostyril compounds and a process for their preparation. These compounds act as polymerization photoinitiators.
Znane są związki dicyjanostyrylowe o wzorze 4, w którym R1 i R2 oznaczają razem lub niezależnie od siebie grupę metylową, etylową, etanolową, cyjanoetylową. Związki te otrzymuje się w reakcji pochodnych aldehydu benzoesowego zawierających w pozycji para grupę NR1R2, w której R1 i R2 oznaczają razem lub niezależnie od siebie grupę metylową, etylową, etanolową, cyjanoetylową, z dinitrylem malonowym w obecnoś ci 99%-owego kwasu octowego i octanu amonowego, w ś rodowisku toluenu.Dicyanostyryl compounds of formula IV are known in which R1 and R2 represent together or independently of each other a methyl, ethyl, ethanol, cyanoethyl group. These compounds are obtained by reacting benzaldehyde derivatives containing the NR1R2 group in the para position, in which R1 and R2 are together or independently of each other a methyl, ethyl, ethanol, cyanoethyl group, with malonic dinitrile in the presence of 99% acetic acid and acetate ammonia, in the toluene environment.
Wynalazek dotyczy nowych związków dicyjanostyrylowych o wzorze 1, w którym R1 i R2 oznaczają razem lub niezależnie od siebie grupę metylową, etylową, etanolową, cyjanoetylową, R3 oznacza grupę alkilową, zaś Y oznacza anion związku o wzorze 2, w którym R4 oznacza grupę fenylową, n-butylową, sec-butylową lub tert-butylową.The invention relates to novel dicyanostyryl compounds of formula I, in which R1 and R2 are together or independently of each other a methyl, ethyl, ethanol, cyanoethyl group, R3 is an alkyl group and Y is an anion of a compound of formula II in which R4 is a phenyl group, n-butyl, sec-butyl or tert-butyl.
Nowe związki wykazują działanie fotopolimeryzujące.The new compounds show photopolymerizing activity.
Sposób wytwarzania nowych związków polega na tym, że związek o wzorze 4, w którym R1 i R2 mają wyżej podane znaczenie, poddaje się reakcji z siarczanem dimetylowym przy stosunku molowym substratów 1:60 w temperaturze 110-115°C w czasie 15-20 godzin, po czym całość wylewa się do wody, ogrzewa w temperaturze 50-55°C w czasie 5-15 godzin i zobojętnia ługiem sodowym do odczynu obojętnego. Otrzymany w wyniku tego związek, po odfiltrowaniu i przemyciu acetonem, poddaje się reakcji z boranem o wzorze 2, w którym R4 ma wyżej podane znaczenie, zaś T oznacza Na lub kation tetrametyloamoniowy, w acetonitrylu przy stosunku molowym substratów 1:1 w temperaturze 69-70°C w czasie 0,3-1 godzina, po czym roztwór odizolowuje się od światła, dodaje wodę i wolno schładza.The method of producing the new compounds consists in reacting the compound of formula 4, in which R1 and R2 are as defined above, with dimethyl sulphate with a molar ratio of reactants 1:60 at a temperature of 110-115 ° C for 15-20 hours. and then poured into water, heated at 50-55 ° C for 5-15 hours and neutralized with sodium hydroxide solution until neutral. The resulting compound, after filtration and washing with acetone, is reacted with a borane of formula 2, in which R4 is as defined above, and T is Na or a tetramethylammonium cation, in acetonitrile at a molar ratio of substrates of 1: 1 at a temperature of 69- 70 ° C for 0.3-1 hour, after which the solution is isolated from light, added water and slowly cooled.
Przedmiot wynalazku ilustruje poniższy przykład. Części podane w przykładzie oznaczają części wagowe.The following example illustrates the subject of the invention. The parts in the example are parts by weight.
P r z y k ł a d.P r z k ł a d.
2,1 części związku o wzorze 4, w którym R1 i R2 oznaczają grupy etanolowe, rozpuszczono w 80 częściach siarczanu dimetylu i nastę pnie ogrzewano w zakresie temperatur 110-115°C w czasie około 18 godzin. Po zakończeniu procesu metylowania (kontrola chromatograficzna) całość wylano do 80 części wody i ogrzewano w czasie 10 godzin w zakresie temperatur 50-55°C. Po tym czasie mieszaninę reakcyjną zobojętniono ługiem sodowym do odczynu obojętnego. Uzyskany produkt odfiltrowano i przemyto acetonem.2.1 parts of the compound of Formula 4, where R1 and R2 are ethanol, were dissolved in 80 parts of dimethyl sulfate and then heated to 110-115 ° C for about 18 hours. After the end of the methylation process (chromatographic control), the mixture was poured into 80 parts of water and heated for 10 hours in the temperature range 50-55 ° C. After this time, the reaction mixture was neutralized to neutral with sodium hydroxide solution. The resulting product was filtered off and washed with acetone.
1,85 części otrzymanego produktu i 1,71 części tetrafenyloboranu sodu rozpuszczono w 100 częściach acetonitrylu. Całość ogrzewano w czasie 30 minut w zakresie temperatur 60-70°C, po czym roztwór odizolowano od dostępu światła, dodano 50 części wody i powoli ochłodzono.1.85 parts of the obtained product and 1.71 parts of sodium tetraphenylborate were dissolved in 100 parts of acetonitrile. It was heated for 30 minutes in the temperature range of 60-70 ° C, then the solution was isolated from light, 50 parts of water were added and it was slowly cooled.
Otrzymano 0,95 części związku o wzorze 3 w postaci jasnożółtego proszku.0.95 parts of the compound of formula 3 are obtained in the form of a light yellow powder.
Widmo 1H NMR związku: 3,29 (8H, s); 3,37 (5H, s); 6,80 (4H, t, J 7); 6,91 (8H, t, J 7,3); 7,14 - 7,19 (9H, m); 7,25 - 7,50 (2H, m) 7,70-785 (1H, m); 7,98 (1H, s) potwierdziło jego budowę. Compound 1 H NMR spectrum: 3.29 (8H, s); 3.37 (5H, s); 6.80 (4H, t, J 7); 6.91 (8H, t, J 7.3); 7.14 - 7.19 (9H, m); 7.25-7.50 (2H, m) 7.70-785 (1H, m); 7.98 (1H, s) confirmed its structure.
Otrzymany związek zastosowano do polimeryzacji akrylanu etylu światłem o długości fali 350 nm.The obtained compound was used to polymerize ethyl acrylate with light having a wavelength of 350 nm.
Wyznaczona szybkość polimeryzacji była równa 1,72 μmol s-1.The determined polymerization rate was 1.72 μmol s -1 .
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL379139A PL210184B1 (en) | 2006-03-07 | 2006-03-07 | New dicyanostyril compounds and method for their manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL379139A PL210184B1 (en) | 2006-03-07 | 2006-03-07 | New dicyanostyril compounds and method for their manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| PL379139A1 PL379139A1 (en) | 2007-09-17 |
| PL210184B1 true PL210184B1 (en) | 2011-12-30 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PL379139A PL210184B1 (en) | 2006-03-07 | 2006-03-07 | New dicyanostyril compounds and method for their manufacture |
Country Status (1)
| Country | Link |
|---|---|
| PL (1) | PL210184B1 (en) |
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2006
- 2006-03-07 PL PL379139A patent/PL210184B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| PL379139A1 (en) | 2007-09-17 |
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Legal Events
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| LAPS | Decisions on the lapse of the protection rights |
Effective date: 20120307 |