CS261433B1 - Photochrome 1,5-bis/substituted phenyl/-3,3-diphenyl-1,5-pentandiones and method of their production - Google Patents
Photochrome 1,5-bis/substituted phenyl/-3,3-diphenyl-1,5-pentandiones and method of their production Download PDFInfo
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- CS261433B1 CS261433B1 CS874541A CS454187A CS261433B1 CS 261433 B1 CS261433 B1 CS 261433B1 CS 874541 A CS874541 A CS 874541A CS 454187 A CS454187 A CS 454187A CS 261433 B1 CS261433 B1 CS 261433B1
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- diphenyl
- bis
- substituted phenyl
- production
- pentandiones
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title claims abstract description 5
- 238000000034 method Methods 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 6
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012965 benzophenone Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002585 base Substances 0.000 claims description 5
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims description 2
- 150000008046 alkali metal hydrides Chemical class 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 125000005594 diketone group Chemical group 0.000 description 6
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 description 2
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 1
- PMQLXPTVUKLMJN-UHFFFAOYSA-N 3,3-diphenylpentanedial Chemical compound C=1C=CC=CC=1C(CC=O)(CC=O)C1=CC=CC=C1 PMQLXPTVUKLMJN-UHFFFAOYSA-N 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Fotochromné 1,5-bis(subst.fenyl) 3,3-difenyl-l,5-pentadióny obecného vzorca I, kde X je alkyl s počtom uhlíkov 1 až 2, alkoxyl s počtom uhlíkov 1 až 2 alebo halogén, majú fotochromné vlastnosti. Sposob ich výroby spočívá v tom, že sa posobí bázou na zmes zlúčeniny II, kde X má vyššie uvedený vý znam a benzofenónu v bezvodom éteri, tetrahydrofuráne či dioxáne pri teplotách od —30 do +50 °C.Photochromic 1,5-bis (subst. Phenyl) 3,3-diphenyl-1,5-pentadiones of formula (I) wherein X is alkyl of 1 to 2, alkoxy having carbon numbers of 1 or 2, or halogen, have photochromic properties. The way of their production it consists in basing it on the mixture Compound II wherein X is as defined above; benzophenone in anhydrous ether, tetrahydrofuran or dioxane at temperatures from -30 to + 50 ° C.
Description
Vynález sa týká 1,5-bis (subst. ,fenyl}3,3-difenyl-l,5-pentándiónGB(ř (^ecaaplíp «zoreatd, kde X je alkyl s počtom uhlíkov 1 až 2, alkoxyl s počtom uhlíkov 1· až P2 alebQ, halogen.The present invention relates to 1,5-bis (subst., Phenyl) 3,3-diphenyl-1,5-pentanedione GB (η (ε-α-β-piperazine) wherein X is alkyl having a carbon number of 1 to 2, alkoxyl having a carbon number of 1 to 2). to P 2 or Q, halogen.
Doposia! bol připravený len derivát, v ktorom substituenty X sú vodíkové atomy a to z acetofenónu a benzofenónu pósobením bázy.So far the! only a derivative in which the X substituents are hydrogen atoms from acetophenone and benzophenone by base treatment was prepared.
Novo připravené diketóny vykazujú v kryštalickom stave výrazná fotochromiu po ožiarení slnečným svetlom. Uvedené 1,5-diketóny sú potenciálnymi prekurzormi pre syntézu heterocyklickýoh zlúčenín a móžu byť využité ako zložky fotochrómnych zmesi s aplikáciou vo výrobě fotomateriálov alebo materiálov pre mikroelektroniku. Nové diketóny můžu sa popžívat pre syntézu nových heierocyklických zlúčenín s fotochromnými vlastnosťami. Spósob výroby 1,3,3,5-tetrafenyl-l,5-pentándiónov obecného vzorca I, kde X má vyššie uvedený význam podlá vynálezu, spočívá v pósobení bázy na zmes zlúčeniny II, kde X má vyššie uvedený význam a benzofenónu. Ako· bázy sa používajú hydridy, amidy alebo alkoxidy alkalických kovov. Reakcia sa prevádza v bez- vodom éteri, tetrahydrofuráne či dioxáne pri teplotách od —30 do +50 °C.Newly prepared diketones exhibit in the crystalline state significant photochromia after irradiation with sunlight. Said 1,5-diketones are potential precursors for the synthesis of heterocyclic compounds and can be used as components of photochromic compositions for use in the manufacture of photomaterials or materials for microelectronics. The novel diketones can be used to synthesize new heierocyclic compounds with photochromic properties. A process for the preparation of 1,3,3,5-tetrafenyl-1,5-pentanediones of formula I wherein X is as defined hereinabove is to treat the base with a mixture of compound II, wherein X is as defined above and benzophenone. Alkali metal hydrides, amides or alkoxides are used as bases. The reaction is carried out in anhydrous ether, tetrahydrofuran or dioxane at temperatures from -30 to +50 ° C.
Spósob výroby diketónov I a ich fotochrómne vlastnosti sú uvedené v následujúcich príkladoch.The process for producing diketones I and their photochromic properties are shown in the following examples.
Příklad 1Example 1
Spósob výroby diketónu I (X=CH3)Method of production of diketone I (X = CH3)
Do miešanej a chladenej suspenzie 8 g (0,2 mólu) amidu sodného bol prillaty roztok 9,0 g (0,05 mólu) benzonfenónu a 13,4 g (0,1 mólu) p-metylacetofenónu v 25 ml éteru. Zmes bola miešaná 3 hodiny pri 0 °C a potom 2 dni pri laboratórnej teplote. Po rozložení vodou a extrakcii vodné] fázy benzénom boli spojené organické podiely destilované vodnou parou. Destilačný zvyšok bol vytrepaný do benzénu, spojené organické podiely boli sušené síranom sodným. a po vákuovom odpaření rozpúšťadla bol získaný olej převrstvený éterom. Bolo získané 4,5 g 1,5-bis (p-tolyl )-3,3-difenyl-l,5-pentadiónu (21 %-ný výťažok) o teplote topenia 113 až 116 °C.To a stirred and cooled suspension of 8 g (0.2 mol) of sodium amide was added a solution of 9.0 g (0.05 mol) of benzonphenone and 13.4 g (0.1 mol) of p-methylacetophenone in 25 ml of ether. The mixture was stirred at 0 ° C for 3 hours and then at room temperature for 2 days. After decomposition with water and extraction of the aqueous phase with benzene, the combined organic fractions were distilled with steam. The distillation residue was taken up in benzene, the combined organics were dried over sodium sulfate. and after evaporation of the solvent in vacuo, the oil was overlaid with ether. 4.5 g of 1,5-bis (p-tolyl) -3,3-diphenyl-1,5-pentadione (21% yield), m.p. 113-116 ° C, were obtained.
. Příklad 2. Example 2
Spósob výroby diketónu I (X=OCHójMethod for producing diketone I (X = OCH 3)
Do miešanej a chladenej suspenzie 8 g (0,2 molu] amidu sodného bol priliaty roztok 9,0 g (0,05 mólu] benzofenónu a 15,0 g (0,1 mólu) p-metoxyacetofenónu· v 25 ml éteru. Reakčná zmes bola spracovaná obdobným spósobom ako v příklade.. 1,..pričom bolo získané 4,1 g 1,5-bis (p-methoxyf enyl j< -3i3-difenyl-l,5.-pentadiónu (18 %-ný výtažok) o teplote topenia 156 až 157 °C. Příklad 3To a stirred and cooled suspension of 8 g (0.2 mol) of sodium amide was added a solution of 9.0 g (0.05 mol) of benzophenone and 15.0 g (0.1 mol) of p-methoxyacetophenone in 25 ml of ether. The mixture was worked up in a similar manner to Example 1 to give 4.1 g of 1,5-bis (p-methoxyphenyl) -3,3-diphenyl-1,5-pentadione (18% yield). mp 156-157 ° C. Example 3
Spósob výroby diketónu I (X—Br)Method for producing diketone I (X-Br)
Do miešanej a chladenej suspenzie 8 g (0,2 mólu) amidu sodného hol priliaty roztok 9,0 g (0,05 mólu) benzofenónu a 19,9 g (0,1 mólu) p-brómacetofenónu v 25 ml éteru. Reakčná zmes bola spracovaná a produkt bol izolovaný obdobným sposobom aiko v příklade 1. Bolo získané 8,1 g 1,5-bis (p-bromf enyl) 3,3-dif enyl-l,5-pentadiónu (45 %-ný výťažok), ktorý po rekryštalizácii zo zmesi benzén-petroléter mal teplotu topenia 195 až 196 °C. Analogicky bol připravený 1,5-bis (p-f luorf enyl) -3,3-dif enyl-1,5-pentadión (X=F) vo 26 %-nom výtažku s t. t. 174 až 177 °C.To a stirred and cooled suspension of 8 g (0.2 mol) of sodium amide was added a solution of 9.0 g (0.05 mol) of benzophenone and 19.9 g (0.1 mol) of p-bromoacetophenone in 25 ml of ether. The reaction mixture was worked up and the product was isolated in a similar manner to that in Example 1. 8.1 g of 1,5-bis (p-bromophenyl) 3,3-diphenyl-1,5-pentadione (45% yield) were obtained. ), which after recrystallization from benzene-petroleum ether had a melting point of 195-196 ° C. Analogously, 1,5-bis (p-fluorophenyl) -3,3-diphenyl-1,5-pentadione (X = F) was prepared in 26% yield with m.p. t. Mp 174-177 ° C.
Příklad 4Example 4
Fotochrómne vlastnosti látok IPhotochromic properties of substances
Svetlom indukovaná farebná. změna u látok I bola pozorovaná v tuhom stave. Pri ozařovaní krystalických vzoriek látok I působením -slnečného světla sa potřebná doba expozície pohybuje od zlomkov sekund až po nie.kofko minút. Přechováváním, farebných kryštálov v temne dochádza i spatné behom niekolkých hodin k strate farby. Obdobného efektu je možné dosiahnuť i pri rozpuštění látky alebo pri jej zahriatí.Light induced color. change in substances I was observed in the solid state. When irradiating crystalline samples of substances I under the influence of sunlight, the required exposure time varies from fractions of a second to a few minutes. By keeping the colored crystals in the dark, there is a loss of color even within a few hours. A similar effect can also be obtained if the substance is dissolved or heated.
Látka ISubstance I
X=HX = H
X=CH2X = CH 2
Farba látky před ožiarenímColor of the substance before irradiation
Farba látky po ožiarení bezfarebná fialová bezfarebná červenáColor of the substance after irradiation colorless violet colorless red
2B14332B1433
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS874541A CS261433B1 (en) | 1987-06-19 | 1987-06-19 | Photochrome 1,5-bis/substituted phenyl/-3,3-diphenyl-1,5-pentandiones and method of their production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS874541A CS261433B1 (en) | 1987-06-19 | 1987-06-19 | Photochrome 1,5-bis/substituted phenyl/-3,3-diphenyl-1,5-pentandiones and method of their production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS454187A1 CS454187A1 (en) | 1988-06-15 |
| CS261433B1 true CS261433B1 (en) | 1989-02-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS874541A CS261433B1 (en) | 1987-06-19 | 1987-06-19 | Photochrome 1,5-bis/substituted phenyl/-3,3-diphenyl-1,5-pentandiones and method of their production |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS261433B1 (en) |
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1987
- 1987-06-19 CS CS874541A patent/CS261433B1/en unknown
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| Publication number | Publication date |
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| CS454187A1 (en) | 1988-06-15 |
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