CS202272B1 - Dinitriderivates of 9,10-dihydro-9,10-ethanoanthracene and process for preparing thereof - Google Patents
Dinitriderivates of 9,10-dihydro-9,10-ethanoanthracene and process for preparing thereof Download PDFInfo
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- CS202272B1 CS202272B1 CS439778A CS439778A CS202272B1 CS 202272 B1 CS202272 B1 CS 202272B1 CS 439778 A CS439778 A CS 439778A CS 439778 A CS439778 A CS 439778A CS 202272 B1 CS202272 B1 CS 202272B1
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- anhydride
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- VPPCQVCZKDIGGG-UHFFFAOYSA-N dibenzobicyclo[2.2.2]octadiene Chemical compound C12=CC=CC=C2C2CCC1C1=CC=CC=C12 VPPCQVCZKDIGGG-UHFFFAOYSA-N 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 11
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 10
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 230000000802 nitrating effect Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 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 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 3
- 239000000047 product Substances 0.000 claims 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- -1 NH 4 Chemical compound 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000000706 filtrate Substances 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 150000002828 nitro derivatives Chemical class 0.000 claims 1
- 239000012265 solid product Substances 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims 1
- 238000006396 nitration reaction Methods 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Vynález se týká dinitroderivátů 9,10-dihydro-9,10-ethanoanthracenů a způsobu jejich přípravy, spočívající v nitraci 9,10-dihydro-9,10-ethanoanthracenů, případně v přítomnosti kyseliny octové, kyseliny síťové, ecetanhydridu či jejich směsí.The invention relates to dinitroderivatives of 9,10-dihydro-9,10-ethanoanthracenes and a process for their preparation by nitration of 9,10-dihydro-9,10-ethanoanthracenes, optionally in the presence of acetic acid, lactic acid, ecetanhydride or mixtures thereof.
Dinitroderiváty 9,10-dihydro-9,10-ethanoanthracénů nebyly dosud v dostupné literatuře popsány.Dinitroderivatives of 9,10-dihydro-9,10-ethanoanthracenes have not been previously described in the available literature.
Předmětem tohoto vynálezu jsou dinitroderiváty 9,10-dihydro-9,10-ethanoanthracenů obecného vzorce I,The present invention provides dinitroderivatives of 9,10-dihydro-9,10-ethanoanthracenes of the general formula I,
kde R| a R2 značí -COOR3, přičemž R3 je vodík, alkyl s počtem uhlíků 1 až 4 nebo sodík, draslík, skupina NH,, vápník, baryum, hořčík anebo R| a R2 spolu tvoří anhydridické seskupení a připravují se tak, že se působí na sloučeniny obecného vzorce II,where R | and R 2 is -COOR 3 , wherein R 3 is hydrogen, alkyl having 1 to 4 carbons or sodium, potassium, NH, calcium, barium, magnesium or R 1; and R 2 together form an anhydride group and are prepared so that they act on the compound of formula II,
kde R) a R2 má výše uvedený význam, nitračními činidly.wherein R 1 and R 2 are as defined above, with nitrating agents.
Sloučeniny obecného vzorce II se získají známým způsobem z anthracenů reakcí s kyselinou maleinovou, fumarovou, maleinanhydridem anebo estery či solemi uvedených kyselin. ,The compounds of the formula II are obtained in known manner from anthracenes by reaction with maleic acid, fumaric acid, maleic anhydride and / or esters or salts of said acids. ,
Vlastní nitrace sloučenin vzorce II lze provádět např. tak, že se zvolený anthracenový adukt smísí s kyselinou sírovou případně oleem a do směsi se přidá nitrační činidlo. Volba poměru mezi použitou kyselinou sírovou či oleem a zvolenou sloučeninou vzorce II je do značné míry ovlivněna její rozpustností. Zpravidla je výhodné volit technicky únosný nadbytek kyseliny sírové či olea, v nichž se adukt II rozpustí. Při nitraci není rozhodující, zdali se přidává organická látka do nitračního činidla či obráceně. Lze postupovat i tak, že se připraví suspenze aduktu vzorce II v kyselině sírové a ta se podrobí nitraci.The actual nitration of the compounds of the formula II can be carried out, for example, by mixing the selected anthracene adduct with sulfuric acid or oleum and adding a nitrating agent to the mixture. The choice of the ratio between the sulfuric acid or oleic acid used and the selected compound of formula II is largely influenced by its solubility. As a rule, it is preferable to select a technically acceptable excess of sulfuric acid or oleate in which the adduct II is dissolved. In nitration, it is not critical whether the organic substance is added to the nitrating agent or vice versa. Alternatively, a suspension of the adduct of formula II in sulfuric acid can be prepared and nitrated.
Jiná varianta nitrace spočívá v tom, že se sloučeniny obecného vzorce II smísí s kyselinou octo202272 vou, acetanhydridem anebo směsí kyseliny octové a acetanhydridem a do tohoto systému se přidá zvolené nitrační činidlo. 1 v tomto uspořádání je možný obrácený postup, kdy se směs látek vzorce II s rozpouštědly přivádí do nitračního činidla.Another variant of nitration is that the compounds of formula II are mixed with acetic acid, acetic anhydride or a mixture of acetic acid and acetic anhydride and the selected nitrating agent is added to the system. In this arrangement, a reverse process is possible in which a mixture of the compounds of formula II with solvents is fed to the nitrating agent.
S výhodou lze nové dinitrosloučeniny vzorce I připravovat tak, že se na adukty obecného vzorce II působí nadbytkem kyseliny dusičné, která v tomto uspořádání přejímá funkci rozpouštědla. Tak lze např. do nadbytku kyseliny dusičné, koncentrace kolem 67 % hm., zahřáté na 60 až 70 °C přidávat adukt připravený z anthracenu a maleinanhydridu; po přidání dochází k rozpouštění a nitraci. Analogicky lze použít kyseliny dušičné jiných koncentrací. Výhodou tohoto postupu je vyloučení vzniku sulfoderivátů, které jako vedlejší produkty provázejí nitrace v prostředí kyseliny sírové.Advantageously, the novel dinitro compounds of formula I may be prepared by treating the adducts of formula II with an excess of nitric acid, which in this arrangement assumes the function of a solvent. Thus, for example, an adduct prepared from anthracene and maleic anhydride may be added to an excess of nitric acid at a concentration of about 67% by weight heated to 60-70 ° C; upon addition, dissolution and nitration occur. Analogously, nitric acids of other concentrations can be used. The advantage of this process is the elimination of the formation of sulfoderivatives, which by-products accompany nitrations in sulfuric acid.
Vznikající dinitroderiváty 9,10-dihydro-9,10-ethanoanthracenů obecného vzorce I jsou téměř nerozpustné ve zředěných kyselinách a lze je snadno získat v pevné formě zředěním reakčních směsí vodou či ledem a následující chemickou separací.The resulting dinitroderivatives of 9,10-dihydro-9,10-ethanoanthracenes of the formula I are almost insoluble in dilute acids and can be readily obtained in solid form by diluting the reaction mixtures with water or ice followed by chemical separation.
Příklad 1Example 1
27,6 g aduktu připraveného z anthracenu a maleinanhydridu se po částech přidá do 100 ml 100% kyseliny sírové (monohydrátu) při 25 °C a míchá se 1/2 hodiny. Do vzniklé suspense se během 20 minut přikape 14,8 ml kyseliny dusičné 67%, přičemž se zevní chladicí lázní udržuje teplota na 30 až 35 °C. Potom se reakční směs zahřeje — prostřednictvím vodní lázně — na 65 °C a na této teplotě se udržuje po dobu27.6 g of an adduct prepared from anthracene and maleic anhydride are added portionwise to 100 ml of 100% sulfuric acid (monohydrate) at 25 ° C and stirred for 1/2 hour. 14.8 ml of 67% nitric acid is added dropwise to the suspension over 20 minutes while maintaining the temperature at 30-35 ° C from the external cooling bath. Thereafter, the reaction mixture is heated - via a water bath - to 65 ° C and maintained at this temperature for a period of time
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS439778A CS202272B1 (en) | 1978-07-03 | 1978-07-03 | Dinitriderivates of 9,10-dihydro-9,10-ethanoanthracene and process for preparing thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS439778A CS202272B1 (en) | 1978-07-03 | 1978-07-03 | Dinitriderivates of 9,10-dihydro-9,10-ethanoanthracene and process for preparing thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS202272B1 true CS202272B1 (en) | 1980-12-31 |
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ID=5386617
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS439778A CS202272B1 (en) | 1978-07-03 | 1978-07-03 | Dinitriderivates of 9,10-dihydro-9,10-ethanoanthracene and process for preparing thereof |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS202272B1 (en) |
-
1978
- 1978-07-03 CS CS439778A patent/CS202272B1/en unknown
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