DE280973C - - Google Patents
Info
- Publication number
- DE280973C DE280973C DENDAT280973D DE280973DA DE280973C DE 280973 C DE280973 C DE 280973C DE NDAT280973 D DENDAT280973 D DE NDAT280973D DE 280973D A DE280973D A DE 280973DA DE 280973 C DE280973 C DE 280973C
- Authority
- DE
- Germany
- Prior art keywords
- benzoyl
- cyano
- cyanquinoline
- dihydroquinoline
- phosphorus pentachloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- UHZYTMXLRWXGPK-UHFFFAOYSA-N Phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 5
- WDXARTMCIRVMAE-UHFFFAOYSA-N quinoline-2-carbonitrile Chemical compound C1=CC=CC2=NC(C#N)=CC=C21 WDXARTMCIRVMAE-UHFFFAOYSA-N 0.000 claims description 5
- FYSNRJHAOHDILO-UHFFFAOYSA-N Thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 4
- YBBRCQOCSYXUOC-UHFFFAOYSA-N Sulfuryl chloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims 1
- 239000003701 inert diluent Substances 0.000 claims 1
- HJHXYSBRTVFEDD-UHFFFAOYSA-N isoquinoline-1-carbonitrile Chemical compound C1=CC=C2C(C#N)=NC=CC2=C1 HJHXYSBRTVFEDD-UHFFFAOYSA-N 0.000 claims 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- PASDCCFISLVPSO-UHFFFAOYSA-N Benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N Phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 3
- HUMNYLRZRPPJDN-UHFFFAOYSA-N Benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- -1 Quinaldinic acid nitrile Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229940095076 benzaldehyde Drugs 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- XAAKCCMYRKZRAK-UHFFFAOYSA-N isoquinoline-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=NC=CC2=C1 XAAKCCMYRKZRAK-UHFFFAOYSA-N 0.000 description 1
- 150000002537 isoquinolines Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 239000001187 sodium carbonate Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
- C07D217/22—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the nitrogen-containing ring
- C07D217/26—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
- J& 280973 KLASSE \2p. GRUPPE- J & 280973 CLASS \ 2p. GROUP
Durch Einwirkung von konzentrierter Salzsäure auf das i-Benzoyl-2-cyan-i · 2-dihydrochinolin bzw. auf das i-Cyan-2-benzoyl-i · 2-dihydroisochinolin erhielt Reißert (vgl. Ber. 38 [1905], S. 1606, 1610 bis 1612 und S. 3427 bis 3429) die Chinolin-2-carbonsäure bzw. die Isochinolin-i-carbonsäure neben den entsprechenden Säureamiden und Benzaldehyd By the action of concentrated hydrochloric acid on the i-benzoyl-2-cyano-i · 2-dihydroquinoline or the i-cyano-2-benzoyl-i · 2-dihydroisoquinoline received Reissert (cf. Ber. 38 [1905], pp. 1606, 1610 to 1612 and pp. 3427 to 3429) the quinoline-2-carboxylic acid or the isoquinoline-i-carboxylic acid in addition to the corresponding acid amides and benzaldehyde
In diesen Veröffentlichungen ist die Vermutung ausgesprochen, daß die Bildung der erwähnten Produkte unter Zwischenbildung der zugehörigen Nitrile verläuft. Die Abscheidung des 2-Cyanchinolins und i-Cyanisochinolins ist Reißert demnach nicht gelungen.In these publications the assumption is made that the formation of the mentioned products proceeds with intermediate formation of the associated nitriles. The deposition des 2-cyanoquinoline and i-cyanoisoquinoline So it didn’t succeed.
Es wurde nun gefunden, daß i-Benzoyl-2-cyan-i · 2-dihydrochinolin bzw. das entsprechende Isochinolinderivat beim Behandeln mit Phosphorpentachlorid in Gegenwart indifferenter, wasserfreier Verdünnungsmittel glatt in Phosphortrichlorid, Benzoylchlorid, Salzsäure und 2-Cyanchinolin bzw. i-Cyanisochinolin zerfallen. It has now been found that i-Benzoyl-2-cyano-i · 2-dihydroquinoline or the corresponding isoquinoline derivative when treating with Phosphorus pentachloride in the presence of inert, anhydrous diluents smoothly in Phosphorus trichloride, benzoyl chloride, hydrochloric acid and 2-cyanquinoline or i-cyanisoquinoline disintegrate.
Die Nitrile sind als Ausgangsstoffe zur Herstellung von Farbstoffen und pharmazeutischen Produkten wertvoll.The nitriles are used as starting materials for the manufacture of dyes and pharmaceuticals Products valuable.
-Beispiel 1.
ι Teil Benzoyl-2-cyan-i · 2-dihydrochinolin:-Example 1.
ι Part benzoyl-2-cyano-i 2-dihydroquinoline:
COC6H5 COC 6 H 5
werden in etwa io Teilen Chloroform gelöst und allmählich ι Teil Phosphorpentachlorid in die Lösung eingetragen. Es entweicht lebhaft Salzsäuregas, während die Flüssigkeit dunkelrot gefärbt wird. Nach beendeter Reaktion wird mit Eis versetzt und dann mit Natriumcarbonatlösung geschüttelt, bis der Benzoylchloridgeruch verschwunden ist. Bei der nachfolgenden Wasserdampfdestillation geht vorerst das Chloroform, dann das 2-Cyanchinolin (Chinaldinsäurenitril) rein in weißen Kristallen ■vom Schmelzpunkt 94° über.are dissolved in about 10 parts of chloroform and gradually ι part of phosphorus pentachloride in entered the solution. Hydrochloric acid gas escapes vigorously while the liquid is colored dark red. After the reaction has ended ice is added and then shaken with sodium carbonate solution until the benzoyl chloride odor disappeared. In the subsequent steam distillation, the chloroform goes first, then the 2-cyanquinoline (Quinaldinic acid nitrile) in pure white crystals ■ with a melting point of 94 ° above.
Statt mit Wasser zu zersetzen, kann die Reaktionsflüssigkeit unmittelbar auch der fraktionierten Destillation unterworfen werden. Nach dem Verdampfen von Chloroform und Phosphortrichlorid destilliert im Vakuum vorerst Benzoylchlorid, dann unter ungefähr 23 mm Druck zwischen 150 bis 160 ° das 2-Cyanchinolin über.Instead of decomposing with water, the reaction liquid can also be fractionated directly Be subjected to distillation. After the evaporation of chloroform and phosphorus trichloride, it is distilled in vacuo for the time being Benzoyl chloride, then under about 23 mm pressure between 150 to 160 ° the 2-cyanquinoline above.
Statt Chloroform kann als Verdünnungsmittel auch Phosphortrichlorid oder Benzol zur Verwendung kommen. Schließlich kann man an Stelle von Phosphorpentachlorid Sulfuryl- oder Thionylchlorid in Anwendung bringen.Instead of chloroform, phosphorus trichloride or benzene can also be used as diluents come to use. Finally, instead of phosphorus pentachloride, sulfuryl or bring thionyl chloride into use.
ι Teil 2-Benzoyl-i-cyan-i · 2- dihydroisochinolin: ι Part 2-Benzoyl-i-cyano-i 2- dihydroisoquinoline:
CH.CH.
N-COC6H6 N-COC 6 H 6
5555
6060
7070
werden mit' ι Teil Phosp'horpentachlorid fein zerrieben und vorsichtig angewärmt. Ist die erste Reaktion vorüber, so wird noch so lange auf etwa ioo° erhitzt, bis keine Salzsäure mehr entweicht.be fine with 'ι part of phosphorus pentachloride grated and carefully warmed. If the first reaction is over, it will take so long heated to about 100 ° until no more hydrochloric acid escapes.
Die Aufarbeitung erfolgt wie bei dem isomeren Chinolinderivat i-Cyanisochinolin (Isochinaldinsäurenitril) kristallisiert aus Ligroin in weichen weißen Nadeln und schmilzt bei 780.The processing takes place as in the isomeric quinoline derivative i-Cyanisochinolin (Isochinaldinsäurenitril) crystallized from ligroin in soft white needles, and melts at 78 0th
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE280973C true DE280973C (en) |
Family
ID=536752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT280973D Active DE280973C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE280973C (en) |
-
0
- DE DENDAT280973D patent/DE280973C/de active Active
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