CS223661B1 - Method of making the 1,4-dinitro-tetrahydroimidazo/4,5-d/-imidazol-2,5/1h,3h/-dion - Google Patents
Method of making the 1,4-dinitro-tetrahydroimidazo/4,5-d/-imidazol-2,5/1h,3h/-dion Download PDFInfo
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- CS223661B1 CS223661B1 CS791380A CS791380A CS223661B1 CS 223661 B1 CS223661 B1 CS 223661B1 CS 791380 A CS791380 A CS 791380A CS 791380 A CS791380 A CS 791380A CS 223661 B1 CS223661 B1 CS 223661B1
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- Prior art keywords
- tetrahydroimidazo
- nitration
- dione
- imidazole
- dinitro
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- 238000004519 manufacturing process Methods 0.000 title abstract 3
- 238000006396 nitration reaction Methods 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 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 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 2
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 abstract 1
- 235000019271 petrolatum Nutrition 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- -1 aliphatic alcohols Chemical class 0.000 description 1
- 238000007630 basic procedure Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical group CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Vynález sa týká výroby l,4-dinitro-retra- hydroimidazo [ 4,5-d ] -imidazol-2,5 ( 1H, 3H J - -diónu nitráciou tetrahydroimidazo [ 4,5-d j- -imidazol-2,5 (1H, 3H)-diónu v prostředí ky seliny dusičnej, pričom podmienky nitrácie sú volené v přítomnosti močoviny, čo má za následok zvýšenie výťažnosti a bezpeč nosti procesu. Vynález je možné bez problé- mov využívat pri výrobě titulnej substancie.invention the relates to manufacturing l, 4-dinitro-retra- dihydroimidazo [ 4,5-a ] imidazole-2,5 ( 1H, 3H J - -dione nitration imidazo [ 4,5-a j imidazole-2,5 (1 H, 3H) -dione in environment ky petroleum jelly nitric while conditions nitration They are elected in presence urea what my for result increase recovery and safety the company process. invention is a possible without prob- mov exploit at production the title substances.
Description
Vynález sa týká výroby 1,4-dinitroderivátu tetrahydroimidazo [ 4,5-d] -imidazol-2,5(1H, 3H)-diónu nitráciou tetrahydroimidazo [4,5-d]-imidazol-2,5(1H, 3Hj-diónu v prostředí kyseliny dusičnej, pričom podmlenky sú volené tak, že priaznivo ovplyvňujú výťažok a bezpečnost procesu.The present invention relates to the preparation of the 1,4-dinitro derivative of tetrahydroimidazo [4,5-d] -imidazole-2,5 (1H, 3H) -dione by nitration of tetrahydroimidazo [4,5-d] -imidazole-2,5 (1H, 3H) - % of dione in nitric acid medium, the conditions being selected such that they favorably affect the yield and process safety.
Dinitroderiváty tetrahydroimidazo [4,5-d ] -imidazol-2,5(lH, 3H]-diónu známe tiež pod názvom dinitroglykolurily označované kódom DINGU, je možné získat nitráciou v prostředí kyseliny dusičnej a/alebo kyselinou dusičnou v prostředí acetanhydridu. Z prvého uvedeného variantu sa uvádza vznik zmesi 1,4-; 1,6-; a 1,3-dinitroderivátov (Encyclopedia of Explosives and Related Items. Vol. 6, PATR 2700, Picatinny Arsenal, Dover, 1974, str. G 117 až 118). 1,3-dinitroglykoluril je nestabilný a 1'ahko sa rozkládá vo vriacej vodě, čo umožňuje vhodnú volbu spůsobu izolácie produktu z nitrácie glykolurilu v prostředí kyseliny dusičnej s možnosťou získania zmesi izomérov s vysoko prevládajúcim obsahom 1,4-dinitroglykolurilu a prakktltíky neobsahujúcu 1,3-dinitroglykoluril.Tetrahydroimidazo [4,5-d] -imidazole-2,5 (1H, 3H) -dione dinitroderivatives, also known as dinitroglycolurils, designated DINGU, can be obtained by nitration in nitric acid and / or nitric acid in acetic anhydride. said variant discloses the formation of a mixture of 1,4-, 1,6- and 1,3-dinitroderivatives (Encyclopedia of Explosives and Related Items. Vol. 6, PATR 2700, Picatinny Arsenal, Dover, 1974, pp. 117-118) The 1,3-dinitroglycoluril is unstable and readily decomposes in boiling water, allowing a suitable choice of the method of isolation of the product from nitration of glycoluril in nitric acid, with the possibility of obtaining a mixture of isomers with a predominant 1,4-dinitroglycoluril content and 1,3-dinitroglycoluril.
Výťažok dinitroglykolurilov je vedla všeobecnej závislosti na reakčných podmienkach daný stabilitou glykolurilu, teda 2,4,6,8-tetraazalbicyklo-[ 3.3.0] oktánového skeletu v reakčnom prostředí. V prostředí dymivej kyseliny dusičnej je dominujúcou ved1'ajšou reakciou acldolýza glykolurilu, ktorú je možné do určitej mlery potlačit prídavkom substancie schopnej v acidolytických rovnovážných reakciách vystupovat na straně produktov reakcie.The yield of dinitroglycolurils is in addition to the general dependence on reaction conditions given by the stability of glycoluril, i.e., 2,4,6,8-tetraazalbicyclo [3.3.0] octane skeleton in the reaction medium. In the environment of fuming nitric acid, the dominant side reaction is the acldolysis of glycoluril, which can be suppressed to a certain extent by the addition of a substance capable of acting on the reaction products side in acidolytic equilibrium reactions.
Podl'a tohto vynálezu sposob výroby 1,4-dinitro-tetrahydroimidazo [ 4,5-d ] -imidazol-2,5 (1H, 3H)-diónu nitráciou tetrahydroimidazo [4,5-d]-imidazol-2,5(lH, 3H)-diónu v prostředí kyseliny dusičnej sa uskutočňuje tak, že proces nitrácie prebieha v přítomnosti močoviny pridávanej do nltračného systému naraz alebo postupné v množstve 0,05 až 15 % hmot., s výhodou v množstve 0,4 až 11,0 % hmot. vztiahnuté na hmotnost do reakcie braného tetrahydroimidazo [4,5-d ] -imidazol-2,5- (1H, 3H j -diónu.According to the present invention, a process for the preparation of 1,4-dinitro-tetrahydroimidazo [4,5-d] -imidazole-2,5 (1H, 3H) -dione by nitration of tetrahydroimidazo [4,5-d] -imidazole-2,5 ( The 1 H, 3 H) -dione in the nitric acid medium is carried out in such a way that the nitration process takes place in the presence of urea added to the filtration system simultaneously or sequentially in an amount of 0.05 to 15% by weight, preferably in an amount of 0.4 to 11.0 % wt. based on the weight of the reaction taken tetrahydroimidazo [4,5-d] -imidazole-2,5- (1H, 3H) -dione.
Výhodou spůsobu podl’a vynálezu je tá skutočnost, že přítomnost močoviny v reakčnej zmesi priaznivo ovplyvňuje selektivitu a výťažnosť procesu v celom výhodnom rozsahu. Optimálny obsah močoviny prida61 ný ku kyselině dusičnej před nitráciou jeAn advantage of the process according to the invention is that the presence of urea in the reaction mixture favorably affects the selectivity and yield of the process to the full advantageous extent. The optimum urea content added to nitric acid prior to nitration is
1,1 až 1,7 °/o hmot. na navážku glykolurilu. Pozitivny, avšak menej výrazný vplyv na výtažky dinitroglykolurilu má aj močovina vnášaná do reakčného systému ako aditívum aplikovaného glykolurilu.1.1 to 1.7% w / w; for glycoluril loading. Urea introduced into the reaction system as an additive of applied glycoluril also has a positive but less pronounced effect on dinitroglycoluril extracts.
Vedla uvedeného ekonomického efektu je výhodou tohto vynálezu aj zvýšenie stability reakčnej zmesi a teda bezpečnosti procesu v důsledku přítomnosti močoviny. Stabilizujúci vplyv močoviny pri nitrolýzach v prostředí kyseliny dusičnej (čs. pat. číslo 97100, čs. autorské osvedčenie č. 227 903). alebo esterifikáciách alifatických alkoholov kyselinou dusičnou alebo zmesou kyseliny dusičnej s kyselinou sírovou (čs. autorské osvedčenie č. 168 189) je dobré známy, a tak isto dobře interpretovaný v prácach V. Kadeřábek a J. Denkstein: Coll. Czech. Chem. Comun. 1960, 25, 1070; alebo tiež čs. autorské osvedčenie č. 227 903.In addition to said economic effect, the advantage of the present invention is also an increase in the stability of the reaction mixture and hence process safety due to the presence of urea. Stabilizing effect of urea in nitrolysis in nitric acid environment (US Pat. No. 97100, US Pat. No. 227 903). or esterification of aliphatic alcohols with nitric acid or a mixture of nitric acid with sulfuric acid (cf. No. 168,189) is well known and also well interpreted in V. Kadeřábek and J. Denkstein: Coll. Czech. Chem. Comun. 1960, 25, 1070; or also MS. author's certificate no. 227 903.
Nový a vyšší účinok dosahovaný v zmysle tohto vynálezu nebol v literatúre doposial' popísaný a je dokumentovaný nasledujňcimi príkladmi.The novel and higher effect achieved for the purposes of the present invention has not been described in the literature so far and is illustrated by the following examples.
Příklad 1 hmot. dielov glykolurilu (90 min sušeného pri teplote 80 až 85 °C) sa za stálého miešania po dobu 4 až 5 minút vnáša do 500 obj. dielov kyseliny dusičnej 99,15%-nej. Pri vnášení glykolurilu je teplota reakčnej zmesi vonkajším chladením udržovaná ná 24 až 27 °C. Potom následuje zvýšenie teploty reakčnej zmesi vonkajším ohrevom v priebehu 6 až 7 minút na 50 až 53 °C a v tomto teplotnom rozmedzí sa udržuje po dobu 45 minút. Po tejto době je nitračná zmes tenkým prúdom opatrné vedená do 1000 obj. dielov variacej vody. Vzniknutá suspemzia je 10 minút refluxovaná a po vychladnutí na 15 až 20 °C je produkt izolovaný filtráciou, na filtri premytý vodou do neutoálaaej reakcie odchádzajúceho filtrátu, a potom sušený v tenkej vrstvě 4 hodiny pri teplote 80 až 85 °C.Example 1 wt. parts of glycoluril (90 min dried at 80-85 ° C) are added to 500 vol. parts of nitric acid 99.15%. When the glycoluril is introduced, the temperature of the reaction mixture by external cooling is maintained at 24 to 27 ° C. This is followed by an increase in the temperature of the reaction mixture by external heating over a period of 6 to 7 minutes to 50 to 53 ° C, and is maintained in this temperature range for 45 minutes. After this time, the nitration mixture is carefully fed to 1000 vol. parts of variation water. The resulting suspension is refluxed for 10 minutes, and after cooling to 15-20 ° C, the product is isolated by filtration, washed on the filter with water until the reaction of the effluent is discontinuous, and then dried in a thin layer at 80-85 ° C for 4 hours.
Tento základný postup bol ešte páťkrát reprodukovaný s tým, že před vlastným vnášaním glykolurilu je v predloženej kyselině dusičnej rozpuštěné vždy určité množstvo močoviny. Výsledky prezentuje nasledujúca tabulka:This basic procedure has been reproduced five more times, with a certain amount of urea being dissolved in the present nitric acid before the glycoluril is introduced. The results are presented in the following table:
Množstvo močoviny v predlože- Výtažky 1,4-dinitro-glykolurilu nej kyselině dusičnej hmot. diely hmot. % na návažok hmot. diely % oproti teórii glykoluriluThe amount of urea in the feedstock - 1,4-Dinitro-glycoluril extracts to nitric acid. parts by mass % by weight parts% versus glycoluril theory
222661222661
Příklad 2Example 2
Nitrácia glykolurilu sa robí ako v příklade 1, len s tým rozdielom, že použitý glykoluril v množstve 50 hmot. dielov je před vnášaním do kyseliny dusičnej zmiešaný s 1 hmot. dielom močoviny rovnakej kvality ako v příklade 1. Vzniká 67,9 hmot. dielov dinitroglykolurilu, čo představuje 83,14 % oproti teorii.Glycoluril nitration is performed as in Example 1, except that the glycoluril used is 50 wt. parts are mixed with 1 wt. of urea of the same quality as in Example 1. 67.9 wt. parts of dinitroglycoluril, which represents 83.14% of theory.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS791380A CS223661B1 (en) | 1980-11-20 | 1980-11-20 | Method of making the 1,4-dinitro-tetrahydroimidazo/4,5-d/-imidazol-2,5/1h,3h/-dion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS791380A CS223661B1 (en) | 1980-11-20 | 1980-11-20 | Method of making the 1,4-dinitro-tetrahydroimidazo/4,5-d/-imidazol-2,5/1h,3h/-dion |
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| Publication Number | Publication Date |
|---|---|
| CS223661B1 true CS223661B1 (en) | 1983-11-25 |
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| CS791380A CS223661B1 (en) | 1980-11-20 | 1980-11-20 | Method of making the 1,4-dinitro-tetrahydroimidazo/4,5-d/-imidazol-2,5/1h,3h/-dion |
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1980
- 1980-11-20 CS CS791380A patent/CS223661B1/en unknown
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