CS219191B1 - Method of making the mixture of cyclic nitramines - Google Patents
Method of making the mixture of cyclic nitramines Download PDFInfo
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- CS219191B1 CS219191B1 CS634981A CS634981A CS219191B1 CS 219191 B1 CS219191 B1 CS 219191B1 CS 634981 A CS634981 A CS 634981A CS 634981 A CS634981 A CS 634981A CS 219191 B1 CS219191 B1 CS 219191B1
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- Czechoslovakia
- Prior art keywords
- mixture
- hexamethylenetetramine
- weight
- imidazole
- dione
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 11
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000006396 nitration reaction Methods 0.000 claims abstract description 6
- 238000003776 cleavage reaction Methods 0.000 claims abstract description 5
- 230000007017 scission Effects 0.000 claims abstract description 5
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 34
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 17
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000000802 nitrating effect Effects 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 abstract 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 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 description 7
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 description 6
- 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 description 5
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 235000011054 acetic acid Nutrition 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 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 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- POCJOGNVFHPZNS-ZJUUUORDSA-N (6S,7R)-2-azaspiro[5.5]undecan-7-ol Chemical compound O[C@@H]1CCCC[C@]11CNCCC1 POCJOGNVFHPZNS-ZJUUUORDSA-N 0.000 description 1
- BSPUVYFGURDFHE-UHFFFAOYSA-N Nitramine Natural products CC1C(O)CCC2CCCNC12 BSPUVYFGURDFHE-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
- 150000001243 acetic acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- POCJOGNVFHPZNS-UHFFFAOYSA-N isonitramine Natural products OC1CCCCC11CNCCC1 POCJOGNVFHPZNS-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
Vynález sa týká spósobu výroby zmesi cyklických nitramínov nitračným štiepením hexamety- .léntetramínu v prostředí vytvorenom kyselinou octovou a acetanhydridom. Podstatou vynálezu je zvýšenie výťaznosti nitračného štiepenia čoho sa dosahuje prítomnosťou tetrahydroimidazo[4,5-d]-imidazol-2,5(lHs3H) diónu.The invention relates to a process for the production of a cyclic mixture nitramines by nitration cleavage with hexamethy- nentetramine in an acidic medium acetic acid and acetic anhydride. The object of the invention is to increase the nitrate yield cleavage of what is achieved by the presence tetrahydroimidazo [4,5-d] imidazole-2,5 (1Hs3H) dione.
Description
Vynález sa týká spósobu výroby zmesi cyklicr kých nitramínov nitračným štiepením hexametyjr léntetramínu v prostředí vytvorenom kyselinoů octovou a acetanhydridom, pričom podmienky sú modifikované tak, že pozitivně ovplyvňujú výťažok reakcie.The present invention relates to a process for the preparation of a mixture of cyclic nitramines by nitration of hexamethylenetetramine in an environment formed with acetic acids and acetic anhydride, the conditions being modified to positively affect the yield of the reaction.
Podfa najnovších poznatkov je pri nitračnom štiepení hexametyléntetramínu tvorba cyklických nitramínov priaznivo ovplyvnená, v reakčnej zmesi, prítomnosťou močoviny, močovinoformaldehydových kondenzátov, resp. aj iných amidov kyselin a ich derivátov aplikovaných individuálně, alebo v zmesiach viacerých látok. [čs. autorské osvedčenieč. 227 903, č. 206 382According to the state of the art, the formation of cyclic nitramines in the reaction mixture, in the reaction mixture, in the reaction mixture, by the presence of urea, urea-formaldehyde condensates, resp. and other acid amides and their derivatives applied individually or in mixtures of several substances. [MS. author certificate. 227 903, no. 206 382
č. 2 2 7 9 0 5 ;č> 2 2 7 9 0 6 , č.no. 2 2 7 9 0 5; n> 2 2 7 9 0 6, n.
2 7 9 I 1 , č. 2 1 3 5 0 9 , Č.2 7 9 I 1, no. 2 1 3 5 0 9, Art.
14 3 1 ťj. Mechanizmus pósobenia aditiv v procese nitračného štiepenia hexametyléntetramínu bol formou hypotézy naznačený v dvoch prácach [čs. autorské osvedčenie č. 2 2 7 903 'ač. 227 905 J.14 3 1 The mechanism of additive multiplication in the process of nitrous cleavage of hexamethylenetetramine has been suggested by hypothesis in two papers [cf. author's certificate no. 2 2 7 903 ' 227 905 J.
Podfa tohto vynálezu spósob výroby zmesi cyklických nitramínov nitračným štiepením hexametyléntetramínu v prostředí vytvorenom kyselinou octovou a acetanhydridom sa uskutočňuje tak, že proces nitračného štiepenia prebieha v přítomnosti tetrahydroimidazo[4,5-dj-imidazol-2,5(lH,3H)diónu, přidávaného do reakčného systému naraz, alebo postupné v množstve 0,01 až 50,00 % hmot., s výhodou v množstve 0,47 až 30,00 % hmot. vztiahnuté na hmotnost’ do reakcie braného hexametyléntetramínu.According to the present invention, a process for producing a mixture of cyclic nitramines by nitration of hexamethylenetetramine in acetic acid and acetic anhydride is carried out by carrying out the nitration process in the presence of tetrahydroimidazo [4,5-d] imidazole-2,5 (1H, 3H) dione added. to the reaction system at once or sequentially in an amount of 0.01 to 50.00% by weight, preferably in an amount of 0.47 to 30.00% by weight. % by weight ’reaction of the taken hexamethylenetetramine.
Výhodou postupu za tzv; Bachmannových podmienok, podfa vynálezu, je zvýšenie výťažnosti procesu, teda zvýšenie využitia metylénovej bázy východiskového hexametyléntetramínu.The advantage of the procedure for so-called; The Bachmann conditions according to the invention are to increase the process yield, thus increasing the utilization of the methylene base of the starting hexamethylenetetramine.
Z reakcie, v zmysle vynálezu, rezultuje zmes l,3,5-trinitro-l,3,5-triazacyklohexánu (RDX), l,3,5,7-tetranitro-l,3,5,7-tetraazacyklooktánu (HMX) a 1,4-dinitro-tetrahydroimidazo[4,5-dJimidazol-2,5(lH,3H)-diónu (DINGU), ktorá je vhodná pre výrobu zmesi hexotolov, resp. oktolov (Belgický patentový spis č. 863 738).The reaction according to the invention results in a mixture of 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) and 1,4-dinitro-tetrahydroimidazo [4,5-d] imidazole-2,5 (1H, 3H) -dione (DINGU), which is suitable for the preparation of a mixture of hexotols, respectively. octols (Belgian Patent Specification 863 738).
Ako vyplývá z príkladovej časti tohto vynálezu najvyššieho využitia metylénovej bázy pre tvorbu cyklických nitramínov je dosiahnuté v nitrolýze zmesi hexametyléntetramínu (HMT) s tetrahydroimidazo[4,5-d]-imidazol-2,5(lH,3H)diónu (GU) s obsahom posledně menovaného zhruba 0,5 až 5,0 % hmot. Ako vyplývá z práce čs. autorské osvedčenie č. . 2 2 9 9 6 1 vyznačujú ša zmesi uvedeného typu i stálosťou yoči aglomerácii.As is apparent from the example section of this invention, the highest utilization of methylene base for cyclic nitramine formation is achieved by nitrolysis of a mixture of hexamethylenetetramine (HMT) with tetrahydroimidazo [4,5-d] -imidazole-2,5 (1H, 3H) dione (GU) containing 0.5 to 5.0 wt. As follows from the work of MS. author's certificate no. . 2 2 9 9 6 1 are characterized by their mixtures and their agglomeration stability.
Vyšší účinok, dosahovaný v zmysle tohto vynálezu, nebol v literatúre doposiaT popísaný a dokumentujú ho nasledujúce příklady.The higher effect achieved in the sense of the present invention has not been described in the literature so far and is illustrated by the following examples.
Příklad 1 g hexametyléntetramínu s obsahom 0,32 % hmot. vlhkosti (0,071 mol hexametyléntetramínu) je rozpuštěných v 17 ml 97,2%-nej kyseliny octovej* (0,288 mol kyseliny octovej); tento roztok je v ďalšom označený ako „roztok A“. Roztok B je připravený rozpuštěním 18 g dusičnanu amónnehp s obsahom 0,8 % hmot. vlhkosti (0,221 mol dusičnanu amónneho) v 13 ml 98,3%-nej kyselině dusičnej (0,306 mol kyseliny dusičnej) s obsahom pod 0,1 % hmot. analytickej kyseliny dusitej.Example 1 g of hexamethylenetetramine with 0.32 wt. moisture (0.071 mol hexamethylenetetramine) is dissolved in 17 ml 97.2% acetic acid * (0.288 mol acetic acid); this solution is hereinafter referred to as "solution A". Solution B is prepared by dissolving 18 g of ammonium nitrate containing 0.8 wt. moisture (0.221 mol of ammonium nitrate) in 13 ml of 98.3% nitric acid (0.306 mol of nitric acid) with a content below 0.1% by weight. analytical nitric acid.
Do nitračného aparátu s vrtulovým miešadlom a plášťovým chladením, resp. ohrevom, je předložených 42 ml 99,8%-ného acetanhydridu (0,444 mol acetanhydridu). Za stálého miešania a teploty v rozmedzí 50 až 55 °C sa po dobu 10 až 12 minút do předloženého acetanhydridu súprudne dávkujú roztoky A a B. Po ich nadávkovaní sa teplota zmesi zvýši na 70 až 72 °C a po dobu 30 minút udržuje v teplotnom rozmedzí do 76 °C. Potom je reakčná zmes naliata do 180 ml vody 65 až 70 °C teplej a rezultujúca suspenzia je 30 minút refluxovaná. Po ochladení na 20 až 25 °C je potom suspenzia! filtrovaná, produkt na filtri je premytý vodou do neutrálnej reakcie filtrátu a sušený pri 90 až 100 °C. Uvedený postup je 4 krát opakovaný s 10 g zmesi hexametyléntetramínu s určitým množstvom tetrahydroimidazo[4,5-d]-imidazol-2,5(lH,3H)diónu. Výsledky jednotlivých nitrolýz prezentuje tabulka číslo 1.For nitration apparatus with propeller stirrer and jacket cooling, resp. by heating, 42 ml of 99.8% acetic anhydride (0.444 mol of acetic anhydride) are introduced. While stirring at a temperature in the range of 50 to 55 ° C, solutions A and B are co-metered into the present acetic anhydride for 10 to 12 minutes. up to 76 ° C. The reaction mixture is then poured into 180 ml of water at 65 to 70 ° C warm and the resulting suspension is refluxed for 30 minutes. After cooling to 20 to 25 ° C, the suspension is then formed. filtered, the product on the filter is washed with water to neutralize the filtrate and dried at 90-100 ° C. This procedure is repeated 4 times with 10 g of a mixture of hexamethylenetetramine with some tetrahydroimidazo [4,5-d] imidazole-2,5 (1H, 3H) dione. The results of individual nitrolysis are presented in Table 1.
Příklad 2Example 2
Postupuje sa ako v příklade 1, ale s tým rozdielom, že sa použije navážka 9,5 g hexametyléntetramínu (0,067 mol HMT). Další postup je taký, že k předloženému acetanhydridu je přidaných 0,5 g tetrahydroimidazo[4,5-d]-imidazol2,5(lH,3H)-diónu, a až potom je začaté s dávkováním roztokov A a B. Vzniká ll,9g produktu s obsahom 12,4 % hmot. 1,3,5,7-tetranitro1,3,5,7-tetraazacyklooktánu (HMX) a 0,84% hmot. 1,4-dinitro-tetrahydroimidazo[4,5-d]-imidazol-2,5(lH,3H)-diónu (DINGU). Výťažok DINGU robí 12,25 % oproti teorii, výťažok HMX 7,31 % a RDX 68,90% oproti teorii. Využitie metylénovej bázy HMT je 39,3 % oproti teorii.The procedure was as in Example 1, except that a portion of 9.5 g of hexamethylenetetramine (0.067 mol HMT) was used. A further procedure is that 0.5 g of tetrahydroimidazo [4,5-d] -imidazole-2,5 (1H, 3H) -dione is added to the present acetic anhydride before dosing of solutions A and B is started. 9g of a product containing 12.4 wt. % Of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) and 0.84 wt. 1,4-dinitro-tetrahydroimidazo [4,5-d] -imidazole-2,5 (1H, 3H) -dione (DINGU). The DING yield is 12.25% compared to the theory, the HMX yield is 7.31% and the RDX is 68.90% compared to the theory. The utilization of the methylene base of HMT is 39.3% compared to the theory.
Tabufka 1Table 1
Obsah glykolurilu v HMT (% hmot.)Glycoluril content in HMT (% by weight)
Množstvo produktu (g)Product Quantity (g)
Počiatky teploty topeniaMelting point origins
COWHAT
Obsah zložiek v produkte (% hmot.)Content of ingredients in product (% by weight)
HMX DINGUHMX DINGU
Výťažok DINGU oproti teorii (% hmot.)DING yield vs. theory (% w / w)
Výťažky zložiek oproti teorii (% hmot.)Component yields vs. theory (% w / w)
HMX RDXHMX RDX
Využitie metylénovej bázy v HMT oproti teorii (% hmot.)Utilization of methylene base in HMT vs. theory (% by weight)
PREDMETSUBJECT
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS634981A CS219191B1 (en) | 1981-08-26 | 1981-08-26 | Method of making the mixture of cyclic nitramines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS634981A CS219191B1 (en) | 1981-08-26 | 1981-08-26 | Method of making the mixture of cyclic nitramines |
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| Publication Number | Publication Date |
|---|---|
| CS219191B1 true CS219191B1 (en) | 1983-03-25 |
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| Application Number | Title | Priority Date | Filing Date |
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| CS634981A CS219191B1 (en) | 1981-08-26 | 1981-08-26 | Method of making the mixture of cyclic nitramines |
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| CS (1) | CS219191B1 (en) |
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1981
- 1981-08-26 CS CS634981A patent/CS219191B1/en unknown
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