CS219190B1 - Method of making the 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane with contents of 1,4-dinitrotetrahydroimidazo/4,5-d/-iimidazole-2,5 lh,3h/-dione - Google Patents
Method of making the 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane with contents of 1,4-dinitrotetrahydroimidazo/4,5-d/-iimidazole-2,5 lh,3h/-dione Download PDFInfo
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- CS219190B1 CS219190B1 CS584781A CS584781A CS219190B1 CS 219190 B1 CS219190 B1 CS 219190B1 CS 584781 A CS584781 A CS 584781A CS 584781 A CS584781 A CS 584781A CS 219190 B1 CS219190 B1 CS 219190B1
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- Prior art keywords
- tetraazacyclooctane
- dione
- dinitro
- endomethylene
- dinitrotetrahydroimidazo
- Prior art date
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- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 11
- 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 abstract description 8
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 claims abstract description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000003776 cleavage reaction Methods 0.000 abstract description 3
- 230000007017 scission Effects 0.000 abstract description 3
- 238000006396 nitration reaction Methods 0.000 abstract description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 8
- 239000000028 HMX Substances 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 4
- 239000004312 hexamethylene tetramine Substances 0.000 description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ZNXALBRTUNJVIH-UHFFFAOYSA-N 1,3,5,7-tetrazocane Chemical compound C1NCNCNCN1 ZNXALBRTUNJVIH-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical compound C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 1
- 241001279686 Allium moly Species 0.000 description 1
- 241000566515 Nedra Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000004941 influx Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
Vynález sa týká výroby 1,3,5,7-tetranitro1.3.5.7-tetraazacyklooktánu s obsahom 1,4-dinitro-tetrahydroimidazo[4,5-d]-imidazol-2,5 (lH,3H)-diónu nitračným štiepeňím, 1,5-endometylén-3,7-dinitro-l,3,5,7-tetraazacyklooktánu. Podstatou vynálezu je priaznivé ovplyvnenie výťaznosti a kvality produktu, čoho sa dosahuje aplikáciou v procese nitrolýzy tetrahydroimidazo[4,5-d]-imidazol-2,5(lH,3H)-diónu v množstve 0,001 až 0,100 molu na 1 mól 1,5-endometylén3.7- dinitro-l,3,5,7-tetraazacyklooktánuThe invention relates to the preparation of 1,3,5,7-tetranitrole 1,3,5,7-tetraazacycloctane containing 1,4-dinitro-tetrahydroimidazo [4,5-d] imidazole-2.5 (1 H, 3 H) -dione by nitration cleavage, 1,5-endomethylene-3,7-dinitro-1,3,5,7-tetraazacycloctane. The object of the invention is to favorably influence product quality, what is achieved by application in the process of nitrolysis of tetrahydroimidazo [4,5-d] imidazole-2,5 (1H, 3H) -dione in quantity From 0.001 to 0.100 mol per 1 mole of 1,5-endomethylene. dinitro-l, 3,5,7-tetraazacyklooktánu
Description
Vynález sa týká výroby 1,3,5^7-tetranitrO“BACKGROUND OF THE INVENTION 1. Field of the Invention
1.3.5.7- tetraazacyklooktánu s obsahom 1,4-dinitrotetrahydroimidazo[4,5-d]-imidazol2,5(lH,3H)-diónu nitračným štiepením 1,5-endometylén-3,7-dinitro-1,3,5,7-tetraazacyklooktánu v prostředí vytvorenom acetanhydridom, pričom podmienky reakcie sú modifikované tak, že priaznivo ovplyvňujú ekonomiku procesu.1,3.5.7-tetraazacyclooctane containing 1,4-dinitrotetrahydroimidazo [4,5-d] imidazole-2,5 (1H, 3H) -dione by nitration cleavage of 1,5-endomethylene-3,7-dinitro-1,3,5, 7-tetraazacyclooctane in an acetic anhydride formed medium, the reaction conditions being modified so as to favorably influence the economics of the process.
1,3,5,7-tetranitro-l,3,5,7-tetraazacykIooktán, nazývaný tiež oktogén a označovaný kódom HMX, sa bežne vyrába nitrolýzou hexametyléntetramínu (HMT) alebo štruktúrnych analógov ako sú 1,5endometyIén-3,7-dinitro-l,3,5,7-tetraazacyklo- oktan (DPT), l,5-diacetyl-3,7-dipitro-l,3,5,7-tetraazacyklooktán (DADN) a l,5-dialkanoyl-3,7endometylén-1,3,5,7-tetraazacykloóktány.1,3,5,7-tetranitro-1,3,5,7-tetraazacycloctane, also called octogen and designated HMX, is commonly produced by nitrolysis of hexamethylenetetramine (HMT) or structural analogues such as 1,5endomethylene-3,7-dinitro -1,3,5,7-tetraazacyclococtane (DPT), 1,5-diacetyl-3,7-dipitro-1,3,5,7-tetraazacyclooctane (DADN) and 1,5-dialkanoyl-3,7endomethylene- 1,3,5,7-tetraazacycllooctans.
Ako je známe (viď napr. bibliografiu E. Ju. Orlova a kok: Oktogen — termostojkoe vzryvčatoe veščestvo, Izdat. Nedra, 1975), syntéza 1,3,5,7tetranitro-l,3,5,7-tetraazacyklooktánu z hexametyléntetramínu prebieha cez l,5-endometylén43,7dinitro-l,3,5,7-tetraazacyklooktán ako medziprodukt. Z hradiska zabezpečenia maximálneho výťažku oktogénu je vhodné nitrolýzu hexametyléntetramínu realizo^vaú tak, že najprv sa syntetizujeAs is known (see, for example, the bibliography of E. Ju. Orlov and coke: Oktogen - thermostojkoe vzryvčatoe veščestvo, Izdat. Nedra, 1975), synthesis of 1,3,5,7tetranitro-1,3,5,7-tetraazacycloctane from hexamethylenetetramine takes place via 1,5-endomethylene43,7-dinitro-1,3,5,7-tetraazacyclooctane as an intermediate. In order to ensure the maximum yield of octogen, nitrolysis of hexamethylenetetramine is suitable by first synthesizing
1,5-endometylén-3,7-dinitro-l,3,5,7-tetraazacyklooktán a ten sa v ďalšom stupni nitrolyzuje na HMX. Všeobecne nitrolýzu l,5-endometylén-3,7dinitro-l,3,5,7-tetraazacyklooktánu je možné realizovat’ 99%-nou kyselinou dusičnou, roztokom dusičnanu amónneho v dýmavej kyselině dusičnej a naopak roztokom dusičnanu amónneho v dýmavej kyselině dusičnej v prostředí acetanhydridu.1,5-endomethylene-3,7-dinitro-1,3,5,7-tetraazacyclooctane and this is nitrolyzed to HMX in the next step. Generally, nitrolysis of 1,5-endomethylene-3,7-dinitro-1,3,5,7-tetraazacyclooctane can be accomplished with 99% nitric acid, a solution of ammonium nitrate in fuming nitric acid and, conversely, a solution of ammonium nitrate in fuming nitric acid in the environment acetic anhydride.
Podía najnovších póznatkov na vznik oktogénu pri nitrolýze l,5-endometylén-3,7-dinitro-l,3,5,7tetraazacyklooktánu priaznivo vplýva přítomnost’ močovinoformaldehydového kondenzátu (čs. autorské osvedčenie č, 2 2 7 9 0 7 .Vplyv močovinoformaldehydového kondenzátu spočívá pravděpodobně v tom, že vzhíadom na přítomnost’ elektronegatívnych karbonylových skupin v molekule týchto kondenzátov sú v danom reakčnom pros’tredí generované karbamóniové ióny. Karbamóniové ióny sa potom móžu zúčastňovat' v nitrolyzačnej zmesi a predchádzať tak nežiadúcim štiepeniam 1,3,5,7-tetraazacyklooktanového skeletu.According to the latest positives for the formation of octogen in the nitrolysis of 1,5-endomethylene-3,7-dinitro-1,3,5,7-tetraazacyclooctane, the presence of urea-formaldehyde condensate positively influences the effect of urea-formaldehyde condensate. it is believed that due to the presence of electronegative carbonyl groups in the condensate molecule, carbamonium ions are generated in the reaction environment, and the carbammonium ions can then participate in the nitrolysis mixture to prevent undesirable cleavages 1,3,5,7 -tetraazacyclooctane skeleton.
Podobného priaznivého účinku sa dosahuje týmto vynálezom, podía ktorého spósob výrobyA similar beneficial effect is achieved by the present invention according to which method of manufacture
1.3.5.7- tetranitro- 1,3,5,7-tetraazacyklooktánu s obsahom 1,4-dinitrotetrahydroimidazo[4,5-dJimidazol-2,5(lH,3H)-diónu nitrolýzou, 1,5-endometyIén-3,7-dinitro- 1,3,5,7-tetraazacyklooktánu v prostředí acetanhydridu uskutočňuje sa tak, že proces nitrolýzy sa robí v přítomnosti tetrahydroimidazo[4,5-d]-imidazol-2,5-(lH,3H)-diónu do reakčného systému přidávaného v množstve 0,001 až 0,100 molu na 1 mol do procesu braného1,3.5.7-Tetranitro-1,3,5,7-tetraazacycloctane containing 1,4-dinitrotetrahydroimidazo [4,5-d] imidazole-2,5 (1H, 3H) -dione by nitrolysis, 1,5-endomethylene-3,7 -dinitro-1,3,5,7-tetraazacyclooctane in acetic anhydride is carried out by carrying out the nitrolysis process in the presence of tetrahydroimidazo [4,5-d] -imidazole-2,5- (1H, 3H) -dione into the reaction of the system added in an amount of 0.001 to 0.100 moles per mole to the process taken
1.5- endometylén-3,7-dinitro-l,3ř5,7-tetraazacyklooktánu.-1,5-endomethylene-3,7-dinitro-l, 3 of 5,7-tetraazacyklooktánu.
Výhodou postupu podía vynálezu je zvýšenie výťažnosti procesu, teda zvýšenie využitia metylénovej bázy východiskového l,5-endometylén-3,7dinitro-1,3,5,7-tetraazacyklooktánu.An advantage of the process according to the invention is to increase the process yield, i.e. to increase the utilization of the methylene base of the starting 1,5-endomethylene-3,7-dinitro-1,3,5,7-tetraazacyclooctane.
Z reakcie v zmysle vynálezu rezultuje zmes ‘ l,3,5,7-tetranitro-l,3,5,7-tetraazacyklooktánu s 1,4-dinitrotetrahydroimidazo[4,5-d]-imidazoI2.5- (lH,3H)-dionom (DINGU). Prítomnosť DINGU v okťogéne je vítané, čoho dokladom je Belgický patentový spis č. 863 738, v ktorom sa popisuje jeho záměrné pridávanie k cyklickým nitramínom za účelom výroby cyklotolov respektive oktolov.The reaction according to the invention results in a mixture of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane with 1,4-dinitrotetrahydroimidazo [4,5-d] imidazol-2,5- (1H, 3H) -dione (DINGU). The presence of DING in the octogen is welcome, as evidenced by Belgian Patent Specification 863 738, which describes its deliberate addition to cyclic nitramines to produce cyclotols and octols, respectively.
Ako vyplývá z príkladovej časti tohto vynálezu je výhodné použiť minimálně 0,0078 mólu tetrahydroimidazo[4,5-d]-imidazol-2,5-(lH,3H)-diónu na 1 mol do reakcie braného DPT. Horná hranica sa pohybuje okolo 0,1 molu a len výnimočne je i potřebné aplikovat’ váčšie množstvo.As is apparent from the example section of the present invention, it is preferred to use at least 0.0078 moles of tetrahydroimidazo [4,5-d] -imidazole-2,5- (1H, 3H) -dione per mole for the reaction taken by DPT. The upper limit is around 0.1 mole, and rarely you need to apply a larger amount.
Účinok, dosahovaný v zmysle tohto vynálezu nebol v literatúre doposiaí popísaný a dokumentuje ho nasledujúci příklad. vThe effect achieved according to the invention has not been described in the literature so far and is illustrated by the following example. in
Příklad 1Example 1
9,8 g (0,045 mol) l,5-endometylén-3,7-dinitro1,3,5,7-tetraazacyklooktánu sa suspenduje v 46 ml 96,8%-ného acetanhydridu (0,472 mol). Krezultujúcej suspenzii sa v priebehu 5 až 6 minút za ; miešania dávkuje roztok 11,3 g dusičnanu amónneho, obsahujúceho 0,67 % vlhkosti (0,140 mol dusičnanu .amónneho) v 13,4 m!98,l%-nej kyseliny dusičnej (0,313 mol mol kyseliny dusičnej). Pri nátoku kyseliny dusičnej sa teplota reakčnej zmesi chladením udržuje v rozmedzí 60 až 64 °C. Po skončení nátoku kyseliny sa realizuje 10-minútové doreagovanie pri teplote 58 až 62 °C. Potom sa přidá do reakčnej zmesi 200 g 75 až 85 °C teplej vody. Vzniklá suspenzia sa 30 minút refluxuje a po přidaní cca 0,1 g tenzidů — Slovaponu N (vodný roztok pěnivého neiónového biologicky odbúrateíného tenzidů na báze zmesi oxyetylovaných mastných alkoholov s 15 % hmot. vody) sa za horúca filtruje. Po premytí produktu do vymiznutia kyslej reakcie filtrátu sa realizuje jeho sušenie pri teplote 80 až 85 °C.9.8 g (0.045 mol) of 1,5-endomethylene-3,7-dinitro-1,3,5,7-tetraazacyclooctane are suspended in 46 ml of 96.8% acetic anhydride (0.472 mol). The resulting suspension is stirred for 5 to 6 minutes ; with stirring, a solution of 11.3 g of ammonium nitrate containing 0.67% moisture (0.140 moles of ammonium nitrate) in 13.4 ml of 98.1% nitric acid (0.313 moles of nitric acid) was added. When the nitric acid is introduced, the temperature of the reaction mixture is kept at 60-64 ° C by cooling. After the acid influx is complete, the reaction is carried out for 10 minutes at 58-62 ° C. 200 g of 75-85 ° C warm water are then added to the reaction mixture. The resulting suspension is refluxed for 30 minutes and after adding about 0.1 g of Slovapone N surfactants (an aqueous solution of foaming nonionic biodegradable surfactant based on a mixture of oxyethylated fatty alcohols with 15% by weight of water) is filtered hot. After washing the product until the acidic reaction of the filtrate disappears, it is dried at 80-85 ° C.
Postup je 7-krát opakovaný vždy s obsahom určitého množstva tetrahydroimidazo[4,5-d]-imidazol-2,5(lH,3H)-diónu v reakčnom systéme. Výsledky prezentuje nasledujúca tabulka číslo 1:The procedure was repeated 7 times with a certain amount of tetrahydroimidazo [4,5-d] imidazole-2,5 (1H, 3H) -dione in the reaction system. The results are presented in Table 1 below:
Tabulka 1Table 1
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS584781A CS219190B1 (en) | 1981-07-31 | 1981-07-31 | Method of making the 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane with contents of 1,4-dinitrotetrahydroimidazo/4,5-d/-iimidazole-2,5 lh,3h/-dione |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS584781A CS219190B1 (en) | 1981-07-31 | 1981-07-31 | Method of making the 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane with contents of 1,4-dinitrotetrahydroimidazo/4,5-d/-iimidazole-2,5 lh,3h/-dione |
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| Publication Number | Publication Date |
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| CS219190B1 true CS219190B1 (en) | 1983-03-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS584781A CS219190B1 (en) | 1981-07-31 | 1981-07-31 | Method of making the 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane with contents of 1,4-dinitrotetrahydroimidazo/4,5-d/-iimidazole-2,5 lh,3h/-dione |
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| Country | Link |
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| CS (1) | CS219190B1 (en) |
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1981
- 1981-07-31 CS CS584781A patent/CS219190B1/en unknown
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