CS237742B1 - Production method of 4-4-bis-(4,6-diphenyl-5-cyanogen-2-pyridyl)biphenyles - Google Patents
Production method of 4-4-bis-(4,6-diphenyl-5-cyanogen-2-pyridyl)biphenyles Download PDFInfo
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- CS237742B1 CS237742B1 CS84572A CS57284A CS237742B1 CS 237742 B1 CS237742 B1 CS 237742B1 CS 84572 A CS84572 A CS 84572A CS 57284 A CS57284 A CS 57284A CS 237742 B1 CS237742 B1 CS 237742B1
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- Prior art keywords
- pyridyl
- diphenyl
- formula
- bis
- carbon atoms
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- 235000010290 biphenyl Nutrition 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 10
- -1 4,6-diphenyl- -p-cyan-2-pyridyl Chemical group 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 150000004074 biphenyls Chemical class 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000005695 Ammonium acetate Substances 0.000 claims description 5
- 235000019257 ammonium acetate Nutrition 0.000 claims description 5
- 229940043376 ammonium acetate Drugs 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 150000002828 nitro derivatives Chemical class 0.000 claims 1
- QCZZSANNLWPGEA-UHFFFAOYSA-N 1-(4-phenylphenyl)ethanone Chemical group C1=CC(C(=O)C)=CC=C1C1=CC=CC=C1 QCZZSANNLWPGEA-UHFFFAOYSA-N 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- YBYASPTYTBIGLE-UHFFFAOYSA-N 1-(1-acetyl-4-phenylcyclohexa-2,4-dien-1-yl)ethanone Chemical group C1=CC(C(=O)C)(C(C)=O)CC=C1C1=CC=CC=C1 YBYASPTYTBIGLE-UHFFFAOYSA-N 0.000 description 1
- UMSGIWAAMHRVQI-UHFFFAOYSA-N 1-ethyl-4-(4-ethylphenyl)benzene Chemical group C1=CC(CC)=CC=C1C1=CC=C(CC)C=C1 UMSGIWAAMHRVQI-UHFFFAOYSA-N 0.000 description 1
- ICMQOAIMMZNGIQ-UHFFFAOYSA-N 6-[4-[4-(5-cyano-4,6-diphenylpyridin-2-yl)phenyl]phenyl]-2,4-diphenylpyridine-3-carbonitrile Chemical group N#CC1=C(C=2C=CC=CC=2)C=C(C=2C=CC(=CC=2)C=2C=CC(=CC=2)C=2N=C(C(C#N)=C(C=3C=CC=CC=3)C=2)C=2C=CC=CC=2)N=C1C1=CC=CC=C1 ICMQOAIMMZNGIQ-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
Abstract
Způsob výroby 4,4 -bis-(4,6-difenyl- -p-kyan-2-pyridyl)bifenylů vzorce I podle vynálezu spočívá v tom, že se nechej! reagovat sloučeniny vzorce II xc6h4coc(cn) = chc6h4i (II), kd« X a X značí vodík nebo alkyl s 1 až 4 atomy uhlíku v alkylovám řatšzci nebo feoyl, a 4,4 -dlacetylbifenyltm v přítomnosti kondenzačních činidel a vhodného oxidovadle, ze zvýšené teploty v organickém rospouštčdle. Výhodou tohoto způsobu je snadná dostupnost výchozích komponent, získaná látky jsou potenciálními acintilAtory a fotostabilizatory.Production Method 4,4-bis (4,6-diphenyl- -p-cyan-2-pyridyl) biphenyls of formula I according to the invention, it is that you leave! reacting compounds of formula II xc6h4coc (cn) = chc6h4i (II) X 1 and X 2 are hydrogen or alkyl of 1 to 1; 4 carbon atoms in the alkyl chain or phenoyl, and 4,4-acetylbiphenyl in the presence condensing agents and suitable oxidant, from an elevated temperature in the organic rospouštčdle. The advantage of this method is Easy availability of default components the substances obtained are potential acintilizers and photostabilizatory.
Description
(54) Způsob výroby 4,4'-bis-(4,6-difenyl-5-kyan-2-pyridyl)bifenyiů(54) A method for producing 4,4'-bis- (4,6-diphenyl-5-cyano-2-pyridyl) biphenyls
Způsob výroby 4,4 -bis-(4,6-difenyl-p-kyan-2-pyridyl)bifenylů vzorce I podle vynálezu spočívá v tom, že se nechej! reagovat sloučeniny vzorce II xc6h4coc(cn) = chc6h4i (II), kd« X a X značí vodík nebo alkyl s 1 až 4 atomy uhlíku v alkylovám řatšzci nebo feoyl, a 4,4 -dlacetylbifenyltm v přítomnosti kondenzačních činidel a vhodného oxidovadle, ze zvýšené teploty v organickém rospouštčdle. Výhodou tohoto způsobu je snadná dostupnost výchozích komponent, získaná látky jsou potenciálními acintilAtory a fotostabilizatory.The process for the preparation of the 4,4-bis- (4,6-diphenyl-p-cyano-2-pyridyl) biphenyls of the formula I according to the invention is characterized in that reacting compounds of formula II xc 6 h 4 coc (cn) = chc 6 h 4 i (II), when X and X are hydrogen or alkyl of 1 to 4 carbon atoms in the alkyl chain or feoyl, and 4,4-acetylbiphenyl the presence of condensing agents and a suitable oxidizing agent, from an elevated temperature in the organic solvent. The advantage of this method is the easy availability of the starting components, the obtained substances being potential acintillators and photostabilizers.
Vynález a· týká způsobu výroby 4,4 '-bi*-(4,6-difenyl-5-kyan-2-pyridyl)bifenylů obecného vzorce 1The invention relates to a process for the preparation of 4,4'-b '- (4,6-diphenyl-5-cyan-2-pyridyl) biphenyls of the general formula 1
4-XCeH4~ NC—<4-XC e H 4 - NC - <
-YC6H4 (I) kde X a Ϊ značí vodík nebo alkyl s 1 až 4 atomy áhlíku v alkylovém řetězci nebo fenyl.-YC 6 H 4 (I) wherein X and Ϊ denote hydrogen or alkyl of 1 to 4 carbon atoms in the alkyl chain or phenyl.
Látka vzorce I nebyly dosud v literatuře popsány. Vynález ee týká způsobu výroby těchto látek. Podstatou vynálezu je, že se nechají reagovat sloučeniny vzorce IIThe compound of formula I has not been described in the literature. The invention relates to a process for the preparation of these substances. It is an object of the invention to react the compounds of formula II
X06H4C0C(CN) CHC6H4Y (II) s 4,4'-diecetylbifenylem v přítomnosti kondenzačních činidel, jako jsou amonná soli karboxylových a minerálních kyselin a vhodného oxidovadla, jako ja vzdušný kyslík, nltrolátky nebo ferrikyanidy alkalicltfch kovů za teploty 50 až 200 °C v organlekéa rozpouštědle, jako je etanol nebo dimetylformamid.X0 6 H 4 COC (CN) CHC 6 H 4 Y (II) with 4,4'-diecetylbiphenyl in the presence of condensation agents such as ammonium salts of carboxylic and mineral acids and a suitable oxidant such as air oxygen, alkali metal or ferricyanides of alkali metal at 50 to 200 ° C in an organic solvent such as ethanol or dimethylformamide.
Výhodou způsobu výroby 4,4'-ble-(4,6-difenyl-5-kyan-2-pyrldyl)bifenylů podle vynálezu je snadná dostupnost výchozích komponent vzorca II, to je nenasycených kyanketonů.An advantage of the process according to the invention for the preparation of the 4,4'-ble- (4,6-diphenyl-5-cyano-2-pyridyl) biphenyls is the easy availability of the starting components of formula II, i.e. unsaturated cyanketones.
K dosažení uspokojivé konverze rsakčníeh komponent na požadované produkty podle vzorca I je nezbytná zvýšená teplota 50 až 200 °C a přiměřená reakčnl doba β až 20 hodin a vhodné dávkování komponent. Za uvedených podmínek látky I krystalují obvykle z reakční směsi a lze je snadno isolovat a rafinovat.In order to achieve a satisfactory conversion of the reaction components to the desired products of the formula I, an elevated temperature of 50 to 200 ° C and an adequate reaction time of β to 20 hours and an appropriate dosage of the components are necessary. Under these conditions, the compounds I usually crystallize from the reaction mixture and can be easily isolated and refined.
Způeob výroby 4,4‘-bie-(4,6-diýenyl-5-kyan-2-pyrldyl)bifenylů podle vynálezu je blíže objasněn na několika příkladech provedení.The preparation of 4,4‘-bie- (4,6-dienyl-5-cyano-2-pyrldyl) biphenyls according to the invention is illustrated in more detail by way of several examples.
PřikladlHe did
Způsob výroby 4,4'-bie/6-(4-blfenyl)-4-fenyl-5-kyan-2-pyridyl/bifenyluProcess for preparing 4,4'-bie / 6- (4-biphenyl) -4-phenyl-5-cyano-2-pyridyl / biphenyl
Směs 0,62 g benzyliden-4-fenylbenzoylacetonltrilu, 0,24 g 4,4'-diaeetylbifenylu,A mixture of 0.62 g of benzylidene-4-phenylbenzoylacetoniltril, 0.24 g of 4,4 ' -diethylbiphenyl,
0,15 g octanu amonného, 5 ml athanolu a 5 ml diaetylformamidu byla zahřívána za přítomnosti vzdušného kyslíku 8 hodin na 150 °C. V průběhu táto doby se z reakční směsi sačala vylučovat sraženina, která byla po ochlazení na laboratorní teplotu odsáta, promyta vodou a etanolem. Překrystalizováním z dimetylforaaaidu bylo získáno 0,20 g prvého podílu požadovaného produktu teploty tání 335 až 337 °C. Zředěním matečných louhů po kryatalizaei přídavkem 100 ml se vyloučila sraženina nesiproduktu, která byla odsáta, promyta vodou, vysušena na vzduchu a smíchána a 0,18 g bensyliden-4-fenylbenzoylacetonitrilu, 0,04 g octanu amonného, 5 ml etanolu a 5 ml diaetylformamidu. Vzniklá směs byla zahřívána k varu za přístupu vzdušného kyslíku po dobu 16 hodin. Po ochlazení byla vyloučená sraženina v množství 20 g odsáta, promyta vodou, etanolem a překryatalována z dimethelforaaaidu. Byl tak získán druhý podíl produktu teploty tání 335 až 337 °C.0.15 g of ammonium acetate, 5 ml of ethanol and 5 ml of diaethylformamide was heated to 150 ° C in the presence of atmospheric oxygen for 8 hours. During this time, a precipitate precipitated from the reaction mixture, which, after cooling to room temperature, was filtered off with suction, washed with water and ethanol. Recrystallization from dimethylformaaid gave 0.20 g of the first crop of the desired product, mp 335-337 ° C. Dilution of the mother liquors after crystallization by addition of 100 ml resulted in the precipitation of the non-product, which was aspirated, washed with water, air-dried and mixed with 0.18 g of bensylidene-4-phenylbenzoylacetonitrile, 0.04 g of ammonium acetate, 5 ml of ethanol and 5 ml of diaethylformamide. . The resulting mixture was heated to boiling under atmospheric oxygen for 16 hours. After cooling, the precipitate (20 g) was filtered off with suction, washed with water, ethanol and recrystallized from dimethelforaaid. A second crop of melting point 335-337 ° C was obtained.
P ř í k 1 a d 2Example 1 a d 2
Způsob výroby 4,4'-ble/6-fenyl-5-kyan-4-tolyl-2-pyridyl/bifenyluProcess for preparing 4,4'-ble (6-phenyl-5-cyano-4-tolyl-2-pyridyl) biphenyl
Směs 0,62 g 4-metylbenzýlidenbenzoylacetonltrilu, 0,2 g 4,4‘-dlacetylbifenylu, 0,1 0,19 g octanu amonného, 2 al dimetylformamidu a 5 ml etanolu byla zahřívána za přístupu vzdušného kyslíku na teplotu 130 °C po dobu 16 hodin. Po ochlazení na laboratorní teplotu byla vyloučená sraženina odsáta, promyta vodou a etanolem a přakrystalisována z toluenu. Bylo získáno 0,30 g požadovaného produktu, který byl přečištěn chromatografli na sloupci 60 g silikagelu vymýváním chloroformem, teplota tání 345 až 346 °C.A mixture of 0.62 g of 4-methylbenzylidene-benzoylacetoniltrile, 0.2 g of 4,4'-acetylbiphenyl, 0.1 0.19 g of ammonium acetate, 2 [mu] l of dimethylformamide and 5 ml of ethanol was heated to 130 [deg.] C. under atmospheric oxygen. 16 hours. After cooling to room temperature, the precipitate formed was filtered off with suction, washed with water and ethanol and recrystallized from toluene. 0.30 g of the desired product was obtained, which was purified by chromatography on a 60 g silica gel column eluting with chloroform, m.p. 345-346 ° C.
Příklad 3Example 3
Způsob výroby 4,4*-bie(4,6-difenyl-5-kyan-2-pyridyl)bifenyluA process for the preparation of 4,4'-bis (4,6-diphenyl-5-cyano-2-pyridyl) biphenyl
Směs 1 g benzylidenbenxoylacetonitrilu, 0,51 g 4,4 -diacetylbifenylu, 0,32 g octanu amonného, 5 ml dimetylformamidu a 5 ml atanolu byla zahřívána za přístupu vzdušného kyslíku na teplotu 160 °C po dobu 12 hodin. Po ochlazení na laboratorní teplotu byla vyloučená sraženina odaáta, pronyta vodou a etanolem a překrystalovánm z dimetylformamidu.A mixture of 1 g of benzylidene-xenoxyacetonitrile, 0.51 g of 4,4-diacetylbiphenyl, 0.32 g of ammonium acetate, 5 ml of dimethylformamide and 5 ml of atanol was heated at 160 ° C for 12 hours under atmospheric oxygen. After cooling to room temperature, the precipitate formed was filtered off with suction, washed with water and ethanol and recrystallized from dimethylformamide.
Bylo získáno 0,19 g požadovaného produktu o teplotě tání 342 až 344 ?C.0.19 g of the expected product is obtained, m.p. 342-344 ° C.
Uvedené 4,4*-bie-(4,6-di£enyl-5-kyan-2-pyridyl)blfenyly jsou potenciálními scintilátory a fotoatabilizátory plastů.Said 4,4 ' -bis- (4,6-diphenyl-5-cyano-2-pyridyl) -phenyls are potential plastic scintillators and photoatabilizers.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS84572A CS237742B1 (en) | 1984-01-25 | 1984-01-25 | Production method of 4-4-bis-(4,6-diphenyl-5-cyanogen-2-pyridyl)biphenyles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS84572A CS237742B1 (en) | 1984-01-25 | 1984-01-25 | Production method of 4-4-bis-(4,6-diphenyl-5-cyanogen-2-pyridyl)biphenyles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS57284A1 CS57284A1 (en) | 1984-10-15 |
| CS237742B1 true CS237742B1 (en) | 1985-10-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS84572A CS237742B1 (en) | 1984-01-25 | 1984-01-25 | Production method of 4-4-bis-(4,6-diphenyl-5-cyanogen-2-pyridyl)biphenyles |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS237742B1 (en) |
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1984
- 1984-01-25 CS CS84572A patent/CS237742B1/en unknown
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| Publication number | Publication date |
|---|---|
| CS57284A1 (en) | 1984-10-15 |
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