CS235585B1 - Method of dinitrotetrahydroimidazo(4,5-d) imidazol-2,5 (1h,3h) dione production - Google Patents
Method of dinitrotetrahydroimidazo(4,5-d) imidazol-2,5 (1h,3h) dione production Download PDFInfo
- Publication number
- CS235585B1 CS235585B1 CS720683A CS720683A CS235585B1 CS 235585 B1 CS235585 B1 CS 235585B1 CS 720683 A CS720683 A CS 720683A CS 720683 A CS720683 A CS 720683A CS 235585 B1 CS235585 B1 CS 235585B1
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- CS
- Czechoslovakia
- Prior art keywords
- dione
- imidazol
- production
- dinitrotetrahydroimidazo
- nitration
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims abstract 5
- CDWCUONHXXVAHD-UHFFFAOYSA-N 3a,6a-dinitro-1,3,4,6-tetrahydroimidazo[4,5-d]imidazole-2,5-dione Chemical compound [N+](=O)([O-])C12NC(NC1(NC(N2)=O)[N+](=O)[O-])=O CDWCUONHXXVAHD-UHFFFAOYSA-N 0.000 title description 2
- 238000006396 nitration reaction Methods 0.000 claims abstract description 10
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 7
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims description 3
- YZTLXSKKFIMAKY-UHFFFAOYSA-N 3,6-dinitro-1,3a,4,6a-tetrahydroimidazo[4,5-d]imidazole-2,5-dione Chemical compound N1C(=O)N([N+]([O-])=O)C2NC(=O)N([N+](=O)[O-])C21 YZTLXSKKFIMAKY-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 3
- 238000007630 basic procedure Methods 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VKGQPUZNCZPZKI-UHFFFAOYSA-N (diaminomethylideneamino)azanium;sulfate Chemical compound NN=C(N)N.NN=C(N)N.OS(O)(=O)=O VKGQPUZNCZPZKI-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 230000009291 secondary effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000011988 third-generation catalyst Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Vynález pojednává o výrobě dinitrotetrahydroimidazo [ 4,5-d ] imidazól-2,5 (1H,3H) - diónu, známého pod kódovým označením DINGU, nitráciou tetrahydroimidazo[4,5-d]- lmidazól-2,5-(lH,3H) diónu kyselinou dusičnou, pri čom je do reakčného systému v procese výroby přidaný postupné, alebo naraz dikyandiamid v množstve 0,01 až 15 % hmot. na hmotnost navážku nitrovanej substancie. Postup podía vynálezu zvyšuje ekonomiku a bezpečnost výroby DINGU.The invention relates to the production of dinitrotetrahydroimidazo [4,5-d] imidazole-2.5 (1H, 3H) - a dione known under the code name DINGU, nitration tetrahydroimidazo [4,5-d] - Imidazole-2,5- (1H, 3H) -dione with nitric acid, wherein the reaction system is in production process added incrementally or at once Dicyandiamide 0.01 to 15% wt. the weight of the nitrated substance. The process of the invention increases the economy and safety of DING production.
Description
Vynález sa týká sposobu výroby dinitrotetrahydroimidazo [ 4,5-d ] imidazól-2,5 (1H,3H) diónu nitráciou tetrahydroimidazo [4,5-d]imidazól-2,5(lH,3H)diónu kyselinou dusičnou za přítomnosti dikyandiamidu v reakčnom systéme.The present invention relates to a process for the preparation of dinitrotetrahydroimidazo [4,5-d] imidazol-2,5 (1H, 3H) dione by nitration of tetrahydroimidazo [4,5-d] imidazol-2,5 (1H, 3H) dione with nitric acid in the presence of dicyandiamide in reaction system.
Pódia najnovších poznatkov je výťažnosť a bezpečnost procesu nitrolýzy a/alebo nitrácie amínov, resp. amidov, na cyklické nitramíny priaznivo ovplyvnená prítomnosťou močoviny, močovinoformaldehydových kondenzátov, amínoguanidínsulfátu a pod. v příslušnéj reakčnej zmesi (viď na pr. čs. autorské osvedčenie č. 206 382, 213 509,The state of the art is the yield and safety of the nitrolysis and / or nitration process, respectively. amides, to cyclic nitramines favorably affected by the presence of urea, urea-formaldehyde condensates, aminoguanidine sulfate and the like. in the respective reaction mixture (see for example the author's certificate No. 206 382, 213 509,
214 311 a ďalšie). Pravděpodobný mechanizmus pósóbenia niektorých z uvedených aditív bol diskutovaný v niektorých prácach, na pr. v čs. autorskom osvědčení č. 206 382; jedná sa v podstate o katalyzátory tretej generácie.214,311 and others). The probable mechanism of affecting some of the above-mentioned additives has been discussed in some papers, e.g. in MS. author certificate no. 206 382; they are basically third generation catalysts.
Podlá tohto vynálezu spočívá spósob výroby dinitrotetrahydr oimidazo [ 4,5-d ] imidazól-2,5 (lH,3H)diónu v nitrácii tetrahydroimidazo [ 4,5-d ] imidazól-2,5 (1H,3H) diónu dýmavou kyselinou dusičnou za přítomnosti 0,01 až 15 % hmot. dikyandiamidu, s výhodou za přítomnosti 0,3 až 11% hmot. dikyandiamidu v reakčnej zmesi, pri čom dikyandiamid je do reakčného systému přidávaný postupné, alebo naraz.According to the present invention, a process for the preparation of dinitrotetrahydr oimidazo [4,5-d] imidazol-2,5 (1H, 3H) dione is nitrated by tetrahydroimidazo [4,5-d] imidazol-2,5 (1H, 3H) dione by fuming nitric acid in the presence of 0.01 to 15 wt. % dicyandiamide, preferably in the presence of 0.3 to 11 wt. dicyandiamide in the reaction mixture, wherein the dicyandiamide is added sequentially or simultaneously to the reaction system.
Výhodou tohto vynálezu je zvýšenie výťažnosti procesu nitrácie technicky dostupným aditívom so sekundárným účinkom v oblasti zvýšenia stability reakčnej zmesi.An advantage of the present invention is to increase the yield of the nitration process by a technically available additive with secondary effect in the field of increasing the stability of the reaction mixture.
Postup podlá tohto vynálezu je dokumentovaný .nasledujúcim príkladom, ktorý však v žiadnom případe nevylučuje možnú variabilitu postupu.The process according to the invention is illustrated by the following example, which in no way excludes the possible variability of the process.
Příklad 1Example 1
Do předložených 200 objm. dielov kyseliny dusičnej 96,1 %-nej o obsahu 0,3 % hmot. analytickej kyseliny dusitej, ochladenej naUp to 200 vol. % by weight of nitric acid 96.1% by weight and 0.3% by weight. Analytical nitric acid, cooled to
5 až 20 °C, je za miešania a chladenia vnášaných 20 hmot. dielov tetrahydroimidazo[4,5-d]imidazól-2,5-(lH,3H)diónu tak, aby teplota reakčnej zmesi bola v rozsahu hodnot 23 až 25 °C. Potom je reakčná zmes vyhriatá na teplotu 62 až 65 °C a na nej za miešania udržiavaná po dobu 35 minút. Nitrácia je ukončená nalitím reakčnej zmesi do 1000 objem, dielov 65 až 70 °C teplej vody; rezultujúca suspenzia je 20 minút miešaná, potom ochladená na teplotu 20 až 24 °C a filtrovaná. Filtračný koláč je 5X ipremytý á 20 objm. dielami vody a sušený 2 hod. pri teplote 90 °C. Z tohto základného postupu rezultuje 24,5 hmot. dielov surového 1,4-dinitr otetrahydr oimidazo [ 4,5-d ] imidazól-2,5 (lH,3H)diónu, kódovo označovaného DINGU, čo je 75 °/o-ný výťažok oproti teórii.5 to 20 ° C, 20 wt. parts of tetrahydroimidazo [4,5-d] imidazol-2,5- (1H, 3H) dione such that the temperature of the reaction mixture was in the range of 23-25 ° C. The reaction mixture is then heated to 62-65 ° C and held there for 35 minutes with stirring. The nitration is terminated by pouring the reaction mixture into 1000 volumes, 65-70 ° C warm water; the resulting suspension is stirred for 20 minutes, then cooled to 20-24 ° C and filtered. The filter cake is washed 5X and washed 20 volumes. with water and dried for 2 hours. at 90 ° C. This basic procedure results in 24.5 wt. parts of crude 1,4-dinitrole tetrahydrofuranimidazo [4,5-d] imidazol-2,5 (1H, 3H) -dione, code-named DINGU, which is 75% yield from theory.
Uvedený základný postup je opakovaný raz s aplikáciou tetrahydroimidazo[4,5-d)imidazól-2,5(lH,3H) diónu s obsahom dikyandiamidu (0,299 % hmot. dikyandiamidu, to je 0,3 % hmot. na návažok substancie) a potom raz s tým, že před započatím nitrácie je vo východiskovej kyselině dusičnej při teplote 10 až 11 °C za dobrého miešania a chladenia rozpuštěných 2,2 hmot. dielov dikyandiamidu (to je 11·% hmot. na návažok nitrovanej substancie). V prvom případe rezultuje 25,1 hmot. dielov DINGU (t. j. 76,8 % oproti teórii), v druhom 26,5 hmot. dielov DINGU (t. j. 81,1 % oproti teorii).Said basic procedure is repeated once with the application of tetrahydroimidazo [4,5-d] imidazol-2,5 (1H, 3H) dione containing dicyandiamide (0.299% by weight of dicyandiamide, i.e. 0.3% by weight of the substance) and then once, before starting the nitration, 2.2 wt.% dissolved in the starting nitric acid at 10 to 11 ° C with good stirring and cooling. parts of dicyandiamide (i.e., 11 · wt.% per weight of nitrated substance). In the first case, 25.1 wt. parts of DING (i.e. 76.8% against theory), in the second 26.5 wt. parts of DING (i.e. 81.1% vs. theory).
Pomocou neizotermickej diferenčnej termické j analýzy (DTA) pracujúcej s rýchlosťou lineárneho vzostupu teploty 5 K . min-1, meriacím rozsahom lmV na škálu stupnice a navážkami 80 až 90 mg vzorky boly nájdené počiatky exotermického rozkladu u DINGU z nitrácie bez aditíva pri 149,9 °C, DINGU z nitrácie s 0,3 % hmot. aditíva pri 151,8 QC a DINGU z nitrácie s 11 % hmot. aditíva pri 152,0 °C.Using a non-isothermal differential thermal analysis (DTA) operating at a linear temperature rise rate of 5 K. min -1 , measuring range 1mV per scale scale and weighing 80-90 mg of sample, found the onset of exothermic decomposition in DING from nitration without additive at 149.9 ° C, DING from nitration with 0.3 wt. additive at 151.8 C and Q DINGU nitration of a 11% by weight. additives at 152.0 ° C.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS720683A CS235585B1 (en) | 1983-06-09 | 1983-06-09 | Method of dinitrotetrahydroimidazo(4,5-d) imidazol-2,5 (1h,3h) dione production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS720683A CS235585B1 (en) | 1983-06-09 | 1983-06-09 | Method of dinitrotetrahydroimidazo(4,5-d) imidazol-2,5 (1h,3h) dione production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS235585B1 true CS235585B1 (en) | 1985-05-15 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS720683A CS235585B1 (en) | 1983-06-09 | 1983-06-09 | Method of dinitrotetrahydroimidazo(4,5-d) imidazol-2,5 (1h,3h) dione production |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS235585B1 (en) |
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1983
- 1983-06-09 CS CS720683A patent/CS235585B1/en unknown
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