DE1670727A1 - Process for the preparation of derivatives of naphthalene-1,4,5,8-tetracarboxylic diimide - Google Patents
Process for the preparation of derivatives of naphthalene-1,4,5,8-tetracarboxylic diimideInfo
- Publication number
- DE1670727A1 DE1670727A1 DE19641670727 DE1670727A DE1670727A1 DE 1670727 A1 DE1670727 A1 DE 1670727A1 DE 19641670727 DE19641670727 DE 19641670727 DE 1670727 A DE1670727 A DE 1670727A DE 1670727 A1 DE1670727 A1 DE 1670727A1
- Authority
- DE
- Germany
- Prior art keywords
- naphthalene
- bis
- tetracarboxylic acid
- derivatives
- carbon atoms
- 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.)
- Pending
Links
- RJCHVBHJXJDUNL-UHFFFAOYSA-N 5,8-dicarbamoylnaphthalene-1,4-dicarboxylic acid Chemical class C1=CC(C(O)=O)=C2C(C(=N)O)=CC=C(C(O)=N)C2=C1C(O)=O RJCHVBHJXJDUNL-UHFFFAOYSA-N 0.000 title claims description 6
- 238000000034 method Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 2
- 208000015181 infectious disease Diseases 0.000 description 10
- -1 alkyl radicals Chemical class 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- UCSJYZPVAKXKNQ-HZYVHMACSA-N streptomycin Chemical compound CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](NC(N)=N)[C@H](O)[C@@H](NC(N)=N)[C@H](O)[C@H]1O UCSJYZPVAKXKNQ-HZYVHMACSA-N 0.000 description 6
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 5
- 229910000071 diazene Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 241000699670 Mus sp. Species 0.000 description 4
- 230000004083 survival effect Effects 0.000 description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229960005322 streptomycin Drugs 0.000 description 3
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 3
- 230000001225 therapeutic effect Effects 0.000 description 3
- 201000008827 tuberculosis Diseases 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CEVSKNXUESNSEC-UHFFFAOYSA-N N',N'-diethyl-N-propylmethanediamine Chemical compound CCCNCN(CC)CC CEVSKNXUESNSEC-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 244000052616 bacterial pathogen Species 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- PNAHSQGXRFYWTL-UHFFFAOYSA-N n-(piperidin-1-ylmethyl)ethanamine Chemical compound CCNCN1CCCCC1 PNAHSQGXRFYWTL-UHFFFAOYSA-N 0.000 description 2
- AKGUAJOELFXZRU-UHFFFAOYSA-N n-(pyrrolidin-1-ylmethyl)propan-1-amine Chemical compound CCCNCN1CCCC1 AKGUAJOELFXZRU-UHFFFAOYSA-N 0.000 description 2
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- JSZOAYXJRCEYSX-UHFFFAOYSA-N 1-nitropropane Chemical compound CCC[N+]([O-])=O JSZOAYXJRCEYSX-UHFFFAOYSA-N 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000037396 body weight Effects 0.000 description 1
- 125000006264 diethylaminomethyl group Chemical group [H]C([H])([H])C([H])([H])N(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ACGUYXCXAPNIKK-UHFFFAOYSA-N hexachlorophene Chemical compound OC1=C(Cl)C=C(Cl)C(Cl)=C1CC1=C(O)C(Cl)=CC(Cl)=C1Cl ACGUYXCXAPNIKK-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000002475 laxative effect Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SBLHFLBMDYPOJU-UHFFFAOYSA-N n-(pyrrolidin-1-ylmethyl)ethanamine Chemical compound CCNCN1CCCC1 SBLHFLBMDYPOJU-UHFFFAOYSA-N 0.000 description 1
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/06—Peri-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Verfahren zur Herstellung-von Derivaten des Naphthalin-1,4,5,8-tetracarbonsäurediimids Es wurde gefunden, daß Derivate des Naphthalin-1, 4,5,8-gtetracarbonsäurediimids der allgemeinen Formel in der R eine verzweigte oder unverzweigte Alkylgxuppe mit 1 bis 6 Kohlenstoffatomen, Ri und R, Alkylreste mit l bis 6 Kohlenstoffatomen, die gegebenenfalle auch über ein Heteroatom wie ein Stickstoff-, Sauerstoff- oder Schwefelatom mitelinander verbunden sein können bedeutet, ale souche oder in For ihrer Salze mit nichttoxischen anorganischen Säuren wertvolle biologische Eigenschaften besitzen. Sie wirken gegen Tuberkuloseinfektionen und gegen Krankheiten, die durch Ambben, Lamblien und Oxyuren verursacht werden. Außerdem haben aie laxierende Wirkung. Dagegen sind die bekannten nichtbasischen Imide der Naphthalin-1, 4, 5,8-tetracarbonsäure [deutsche Patentschrift 552 760, liebig's Zanni d. Chemie 531 (1937), S. 1; Helv. Chim. Acta 21 (1938). S. 1466 ; US.-Patentschrift 2. 914.531] unwirksam.Process for the preparation of derivatives of naphthalene-1,4,5,8-tetracarboxylic acid diimide It has been found that derivatives of naphthalene-1,4,5,8-tetracarboxylic acid diimide of the general formula in which R is a branched or unbranched alkyl group with 1 to 6 carbon atoms, Ri and R, alkyl radicals with 1 to 6 carbon atoms, which can optionally also be linked together via a heteroatom such as a nitrogen, oxygen or sulfur atom, ale souche or in For their salts with non-toxic inorganic acids possess valuable biological properties. They work against tuberculosis infections and against diseases caused by ambergris, lamblia and oxyurs. They also have a laxative effect. In contrast, the known non-basic imides of naphthalene-1, 4, 5,8-tetracarboxylic acid [German patent 552 760, liebig's Zanni d. Chemie 531 (1937), p. 1; Helv. Chim. Acta 21 (1938). P. 1466; U.S. Patent 2,914,531] is ineffective.
Die Herstellung der Verbindungen der oben angegebenen allgemeinen Formel erfolgt, indem man Naphthalin-1, 4,5,8-tetracarbonsäuredianhydrid mit Amineri der allgemeinen Formel worin R, R, und Ri die oben angegebene Bedeutung besitzen, in Abwesenheit oder in einem geeigneten Lösungs- oder Verdünnungsmittel miteinander umsetzt, wobei die Reaktion bei erhdhter Temperatur besonders rasch verläuft.The compounds of the general formula given above are prepared by converting naphthalene-1,4,5,8-tetracarboxylic dianhydride with amines of the general formula in which R, R and Ri have the meaning given above, are reacted with one another in the absence or in a suitable solvent or diluent, the reaction proceeding particularly rapidly at elevated temperature.
Die neuen Verbindungen zeichnen sich durch eine gute Wirkung gegenüber solchen Tuberkelbazillen aus, die gegen eine Behandlung durch'Isonicotinsaurehydrazid (INH) und Streptomycin resistent gewoiden sind. Infiziert man Mäuee intravenös mit etwa 107 derartiger Keime, so gehen die nicht behandelten Tiere etwa um den 20. Tag nach der Infektion zu 100 % an einer Tuberkulose ein.The new compounds are characterized by a good effect against those tubercle bacilli that are against a treatment by'Isonicotinsaurehydrazid (INH) and streptomycin are resistant. One infects Mäuee intravenously with about 107 such germs, the untreated animals go around the 20th 100% tuberculosis one day after infection.
Jeweils 10 auf diese Weise infizierte Mäuse wurden zu einer Behandlungsgruppe zusammengefaßt und mit einer Standarddoeierung von 30 mg/kg Kdrpergewicht einmal täglich über einen Zeitraum von 4 Wochen bei 5 Applikationen pro Woche mittele Schlundsonde behandelt. An den Stichtagen 15., 20., 25., 30., 35., 40. und 50.Each 10 mice infected in this way became a treatment group summarized and with a standard dose of 30 mg / kg body weight once daily over a period of 4 weeks with 5 applications per week by means of a pharyngeal tube treated. On the reference dates 15th, 20th, 25th, 30th, 35th, 40th and 50th
Tag nach der Infektion wurde die Ueberlebenszahl jeder Mäusegruppe bestimmt. Bei verwertbarem Infektionsablauf lebten am 15. Tag. alle Moues ; am 25. Tag waren unbehandelte bzw. ohne Therapieeffekt behandelte M§uee an einer Tuberkulose eingegangen.The day after the infection, the survival number of each group of mice was determined certainly. If the course of the infection was usable, they lived on the 15th day. all moues; on the 25th. Day were untreated or treated with no therapeutic effect muee from tuberculosis received.
Aus diesem Infektionsablauf resultiert die Berechnung des"Ueberlebens-Index".The calculation of the "survival index" results from this infection process.
Die Summe der überlebenden Mäuse einer Behandlungsgruppe an den genannten Stichtagen wurde durch die Summe der überlebenden Mäuse der Infektionskontrolle dividiert. Bei sieben Werterhebungen ist 70 der gröte erreichbare Summenwert und 10 der niedrigste Summenwert für die Infektionskontrolle. Somit besteht 7 als Höchstwert für den Ueberlebens-Index und 1 bedeutet keine therapeutische Wirksamkeit; d. h. die Ueberlebenswerte der Behandlungsgruppe entsprechen. im letzteren Falle denen der Infektionskontrolle. Bei, normalem Infektionsablauf mit einem Summenwert um 20 für die Infektionskontrolle ergeben sich bei einem deutlichen Therapieeffekt Index-Werte-ab 2. Die erfindungsgemap hergestellten im Vergleich zu INH und Streptomycin Substanzen erreichen in diesem Versuchzdie folgenden werte : ~ Verbindung Index INH 1, 2 Streptomycin 0, 9 Beispiel 1 2, 1 Beispiel 4 2, 7 Beispiel 5 3,1 Beispiel 6 2, 8 Beispiel 1 Zu einer Suspension von 15 g Naphthalin-1,4,5,8-tetracarbonsäuredianhydrid in 150 ml wasserfreiem Toluol tropft man bei 100° C unter Rühren eine Lösung von 25, 7 g a, a-Bis- (dibutylaminomethyl)-äthylamin in 50 ml wasserfreiem Toluol. Dann wird das Gemisch so lange unter Rückfluß gekocht, bis sich in einem Wasserabscheider kein Reaktionswasser mehr abscheidet (ca. 5-6 Stdn.).The sum of the surviving mice of a treatment group on the named Cutoff dates were determined by the sum of the surviving mice of the infection control divided. With seven value surveys, 70 is the highest achievable total value and 10 the lowest total value for infection control. So there is a maximum of 7 for the survival index and 1 means no therapeutic effectiveness; d. H. the survival values correspond to the treatment group. in the latter case, those infection control. In the case of a normal course of infection with a sum value around 20 for infection control result in a clear therapeutic effect Index values-from 2. The inventions produced in comparison to INH and streptomycin Substances achieve the following values in this experiment: Compound index INH 1, 2 Streptomycin 0, 9 Example 1 2, 1 Example 4 2, 7 Example 5 3.1 Example 6 2, 8 Example 1 To a suspension of 15 g of naphthalene-1,4,5,8-tetracarboxylic acid dianhydride a solution of is added dropwise to 150 ml of anhydrous toluene at 100 ° C. while stirring 25.7 g of a, a-bis (dibutylaminomethyl) ethylamine in 50 ml of anhydrous toluene. then the mixture is refluxed until it is in a water separator no more water of reaction separates (approx. 5-6 hours).
Danach wird das Lösungsmittel abdestilliert und der Rückstand in 10 proz. Salzsäure aufgenommen. Die salzsaure Lösung wird mit verd. Natronlauge alkalisch gestellt. Der Niederschlag wird abfiltriert, mit Wasser gewaschen, getrocknet und aus Ligroin umkristallisiert. lagan erhält so 20 g N, N'-Bis-a, a-bis- (dibutylaminomethyl)-äthyl/-naphthalin- (l, 4, 5, 8)-tetracarbonsäurediimid.The solvent is then distilled off and the residue in 10 percent Hydrochloric acid added. The hydrochloric acid solution becomes alkaline with dilute sodium hydroxide solution posed. The precipitate is filtered off, washed with water, dried and recrystallized from ligroin. lagan thus receives 20 g of N, N'-bis-a, a-bis- (dibutylaminomethyl) -ethyl / -naphthalene- (1,4,5,8) -tetracarboxylic acid diimide.
F. 108-110° C.108-110 ° C.
Beispiel 2 Aus Naphtalin-1,4,5,8-tetracarbonsäure-dianhydrid und α, a-Bis-(pyrrolidinomethyl)-äthylamin erhält man analog Beispiel 1: N, N'-Bis-[α,α-bis-(pyrrolidinomethyl)-äthyl]-naphthalin-(1,4,5,8)-tetracarbonsäurediimid. F. 137-139° C.Example 2 From naphthalene-1,4,5,8-tetracarboxylic acid dianhydride and α, α-Bis (pyrrolidinomethyl) ethylamine is obtained analogously to Example 1: N, N'-bis [α, α-bis (pyrrolidinomethyl) ethyl] naphthalene (1,4,5,8) tetracarboxylic acid diimide. 137-139 ° C.
Beispiel 3 Aus Naphthalin-1,4,5,8-tetracarbonsäure-dianhydrid und a, a-Bis-(piperidinomet-hyl)-äthylamin erhält man analog Beispiel 1: N, N'-Bis-[α,α-bis-(piperidinomethyl)-äthyl]-naphthalin-1,4,5,8-tetracarbonsäurediimid. F. 146-148° C.Example 3 From naphthalene-1,4,5,8-tetracarboxylic acid dianhydride and a, a-Bis (piperidinomethyl) ethylamine is obtained analogously to Example 1: N, N'-bis [α, α-bis (piperidinomethyl) ethyl] naphthalene-1,4,5,8- tetracarboxylic acid diimide. 146-148 ° C.
Beispiel 4 Aus Naphthalin-1,4,5,8-tetracarbonsäure-dianhydrid und aga-Bis-(diähylaminomethyl)-propylamin erhält man analog Beispiel li N, N'Bis-[α,α-bis-(diäthylaminomethyl)-propyl]-naphthalin-(1, 4, 5, 8)-tetracarbonsäurediimid. F. 108-110° C.Example 4 From naphthalene-1,4,5,8-tetracarboxylic acid dianhydride and aga-bis (diethylaminomethyl) propylamine is obtained analogously to Example li N, N'Bis- [α, α-bis- (diethylaminomethyl) propyl] -naphthalene- (1, 4, 5, 8) tetracarboxylic acid diimide. 108-110 ° C.
Beispiel 5 Aus Naphthalin-1, 4,5,8-tetracaronsäure-dianhydrid und a, a-Bis-(pyrrolidinomethyl)-propylamin erhält man analog Beispiel 1: N,N'-Bis-[α,α-bis(pyrrolidinomethyl)-propyl]-naphthalin-(1, 4, 5, 8)-tetracarbonsäurediimid. F. 104-106° C.Example 5 From naphthalene-1, 4,5,8-tetracaronic acid dianhydride and a, a-Bis (pyrrolidinomethyl) propylamine is obtained analogously to Example 1: N, N'-bis [α, α-bis (pyrrolidinomethyl) propyl] naphthalene- (1, 4, 5, 8) tetracarboxylic acid diimide. 104-106 ° C.
Beispiel 6 Aus Naphthalin-1,4,5,8-tetracarbonsäure-dianhydrid und α,α-Bis-(piperidinomethyl)-propylamin erhält man analog Beispiel li N, N'-:, a-bis-(piperidinomethyl)-propyl~7-naphthalin-(1, 4, 5, 8)-tetracarbonsäurediimid. F. 112-114° C.Example 6 From naphthalene-1,4,5,8-tetracarboxylic acid dianhydride and α, α-Bis (piperidinomethyl) propylamine is obtained analogously to Example left N, N'- :, a-bis- (piperidinomethyl) -propyl-7-naphthalene- (1, 4, 5, 8) -tetracarboxylic acid diimide. 112-114 ° C.
Die in den vorstehenden Beispielen benotigten mehrwertigen Amine erhält man wie folgt : Setzt man 1 Mol Nitroäthan mit 2 Mol Formaldehyd und 2 Mol Pyrrolidin oder 2 Mol Piperidin oder 2 Mol Dibutylamin nach Art einer Mannich-Reaktion um und reduziert katalytisch mit Raney-Nickel die dabei entstehenden Nitroverbindungen, so erhält man folgende Amines α,α-Bis-(dibutylaminomethyl)-äthylamin, Kp0,3 132-136°C.The polyvalent amines required in the preceding examples are obtained is as follows: 1 mole of nitroethane is added to 2 moles of formaldehyde and 2 moles of pyrrolidine or 2 moles of piperidine or 2 moles of dibutylamine in the manner of a Mannich reaction around and catalytically reduces the resulting nitro compounds with Raney nickel, the following amines are obtained α, α-bis (dibutylaminomethyl) ethylamine, Bp 0.3 132-136 ° C.
C<,C<-Bis-(pyrrolidinomethyl)-äthylamin,Kp,148-152°C.C <, C <-Bis- (pyrrolidinomethyl) -ethylamine, b.p. 148-152 ° C.
α,α-Bis-(piperidinomethyl)-äthylamin, Kp0,3 156-158°C.α, α-Bis (piperidinomethyl) ethylamine, bp 0.3 156-158 ° C.
Analog erhält man, wenn man statt Nitroäthan 1-Nitropropan mit Formaldehyd und sek. Aminen umsetzt und anschließend reduziert : α,α-Bis-(diäthylaminomethyl)-propylamin, Kp0,3 150-152°C. o α-Bis-(pyrrolidinomethyl)-propylamin, Kp0,3 153-155°C.Analogously, if 1-nitropropane is used with formaldehyde instead of nitroethane and sec. Converts amines and then reduces: α, α-bis (diethylaminomethyl) propylamine, Bp 0.3 150-152 ° C. o α-bis (pyrrolidinomethyl) propylamine, b.p. 0.3 153-155 ° C.
, OL-Bls-(piperidinomethyl)-propylamin, Kp0,3 160-163°C., OL-Bls- (piperidinomethyl) propylamine, b.p. 0.3 160-163 ° C.
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF0049897 | 1964-06-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1670727A1 true DE1670727A1 (en) | 1971-01-21 |
Family
ID=7103360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19641670727 Pending DE1670727A1 (en) | 1964-06-05 | 1964-06-05 | Process for the preparation of derivatives of naphthalene-1,4,5,8-tetracarboxylic diimide |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1670727A1 (en) |
-
1964
- 1964-06-05 DE DE19641670727 patent/DE1670727A1/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE2402398C3 (en) | Aromatic carboxamide derivatives, processes for their preparation and pharmaceutical compositions | |
| DE1470439B1 (en) | Quinoline derivatives and processes for their preparation | |
| DE2047658B2 (en) | 2-Styryl- and 2-Phenyläthinylbenzylamine derivatives, processes for their preparation and medicaments containing them | |
| DE2166381A1 (en) | GAMMA PIPERIDINOBUTYROPHENONE DERIVATIVES, METHOD FOR THEIR MANUFACTURING AND MEDICINAL PREPARATIONS | |
| DE1670935B2 (en) | 2-methyl-3-carboxamidoquinoxaline-1,4-di-N-oxides, a process for their preparation and antibacterial agents containing these compounds | |
| DE2745598A1 (en) | ARYL SULFUR COMPOUNDS, THE PROCESS FOR THEIR MANUFACTURING AND THE PHARMACEUTICAL AGENT CONTAINING THEM | |
| DE1230031B (en) | Process for the preparation of derivatives of naphthalene-1, 4, 5, 8-tetracarboxylic acid diimide | |
| CH623336A5 (en) | ||
| DE1670727A1 (en) | Process for the preparation of derivatives of naphthalene-1,4,5,8-tetracarboxylic diimide | |
| CH624104A5 (en) | ||
| DE2003144A1 (en) | Process for the preparation of 5-imino-1,2,4-triazine derivatives | |
| DE1195762B (en) | Process for the preparation of new naphthalene-1, 4, 5, 8-tetracarboxylic acid diimides | |
| CH520117A (en) | 5h-dibenzo-a d-10 11-dihydro-cyclohepten-5-one oximes | |
| DE1670143C3 (en) | ||
| DE1258412B (en) | Process for the preparation of 5,5-bis- (p-hydroxyphenyl) -imidazolinonen- (4) and their salts | |
| DE1035150B (en) | Process for the preparation of N-monosubstituted ª ‡ - (tert-aminoalkyl) -ª ‡ -phenyl acetamides | |
| DE2350395C3 (en) | N- (m-Trifluoromethylthiophenyl) piperazine, its salts, process for their preparation and their use as an intermediate compound for the preparation of piperazine derivatives | |
| DE1543536C3 (en) | S-Nitro ^ -furyl-nitronic acid derivatives and process for their preparation | |
| DE2147852A1 (en) | New penicillins and processes for their production | |
| DE1225190B (en) | Process for the preparation of naphthalene-1, 4, 5, 8-tetracarboxylic acid diimide derivatives | |
| DE1443403C (en) | N Cyclopropyl 1 aminoindan derivatives and process for their preparation | |
| DE1443376C3 (en) | Process for the preparation of 2-amino-alpha-substituted benzylideneamines, as well as new 2-amino-alpha-substituted benzylideneamines as such | |
| CH398613A (en) | Process for the production of new piperazines | |
| AT277249B (en) | Process for the preparation of new quinoline derivatives | |
| AT234707B (en) | Process for the preparation of new 2-sulfa-4, 6-dialkyl-s-triazines |