SE9302299A1 - New polycyclic polyamides as precursor compounds for energy-rich polycyclic polynitramine oxidizers - Google Patents

Abstract

P.ans. No. 9302299-4 26864 / HP / UH SUMMARY Hexabenzylhexaazaisowurtzitan is converted to tetraacetyl, dibenzyl-azaisowurtzitan. The benzyl groups are removed by catalytic transfer hydrogenolysis, leaving a pair of available nitrogen. The available nitrogen is acetylated and the resulting intermediate is converted to CL-20 with a strong nitrating agent.

Description

P.ans. No. 9302299-4 26864 / HP / UH NEW POLYCYCLIC POLYAMIDES AS PRE-STAGE ASSOCIATIONS FOR ENERGY-RICH POLYCYCLIC POLYNITRAMINE OXIDIZERS The present invention of nitrogen compounds with cage structure, in particular derivatives of hexaazaisowurtzitan, and procedures for the synthesis of these compounds.

Background of the invention Arnold T. Nielsen describes in an essay entitled "Synthesis of 2,4,6,8,10,12-Hexabenzy1-2,4,6,8,10,12-hexaazaisowurtzitane" the synthesis of the compound mentioned in the heading. This association is referred to in the following HBIW. The more formal chemical name of this compound is 2,4,6,8,10,12-hexabenzyl-2,4,6,8,10,12-hexaazatetracyclo [5.5.0.03'110.'9] dodecane. Nielsen et al describe in essays entitled "Polynitroplyaza Caged Explosives Parts 5 & 6" (Part 6 Ar classified) and "Synthesis of a Caged Nitramine" (classified), prepared for the Naval Weapons Center, China Lake, CA, the synthesis of 2, 4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaaya-tetracyclo [5.5.0.0.3.110. ") Dodecane, which is a candidate for the field of fuel / explosives as CL-20 (this association is hereinafter referred to as CL-20.) The above-mentioned works by Nielsen and Nielsen et al are incorporated herein by reference.

CL-20 8r is an oxidizing agent with great potential for use in high energy compositions, such as propellants, gasifiers, explosives or the like. CL-20 has a high detonation rate, which is manageable to its high heat of formation. It is also advantageous because of its high density, which is a result of the cage structure. It has 2 special applicability for preparations with minimal smoke formation (generally non-aluminized preparations). It also has special applicability in explosive compositions.

HBIW has the following chemical structure; the stated numbering of the carbon and nitrogen atoms contained in the ring is meant to be bile throughout this description: 202 (142.e Bob._C H18 Na SCH2N CH2.0 It should be noted that in the formula above, the identical 2-, 6-, 8- and 12-can veins are in 5- and 6-membered rings, while the 4- and 10-can bes are in 6- and 7-membered rings. It has been found that in many chemical reactions the four identical nitrogen reacts differently from the two identical nitrogen. These different nitrogen are hereinafter referred to as the 2-6-8-12 nitrogen and the 4-10 nitrogen, respectively.

CL-20 has the following chemical structure: NO2 02t * LN / NO2 02NN.H 02NN NO2 (1) C L- 3 In the first step of the process for the conversion of HBIW (I) to CL-20 (II), HBIW is converted to 2,6,8,12-tetraacetyl-4,10, dibenzyl-hexaazaisowurtzitan, hereinafter referred to as compound IIIA ( 8ven in the present context is referred to as TADB), with the formula shown below: CH3 OC 0130C COCH3 COCH3 N.C11 SCH2-N The conversion from HBIW (I) to compound IIIA is accomplished, for example, with hydrogen in the presence of a palladium hydroxide-Okol catalyst and acetic anhydride using a bromobenzene catalyst. Subsequent conversion of compound IIIA to CL-20 is accomplished using the nitrating agents NOBF4 and NO2BF4, respectively. These nitrates are very expensive. Due to the presence of fluoride, waste products also cause significant environmental problems. The cost of producing CL-20 by this synthesis constitutes a significant limitation on its general applicability in the fuel and explosives industries.

Accordingly, it is a general object of the invention to provide all processes for the synthesis of CL-20 and related energy-rich compounds, which processes involved an improvement in terms of cost and environment. A further object of the invention is to provide all new chemical intermediates which can be converted to CL-20 and related high energy caged nitrogen compounds. 4 Summary of the Invention In accordance with the invention, HBIW (Compound I) is chemically converted to an intermediate of the general formula: The substituents in the R substituents are the same or different and are selected from the group consisting of alkyl, cycloalkyl, aryl, arylalkyl, alkene, alkyne, substituted forms of any of these groups, for example with halogens or nitro groups and H; a group consisting of (HK) (a water ion and a complementary anion) is present on either, one or both of the 4- and 10-nuclei. Equivalent divalent anions can complement the H4 ions on the two 4- and 10-nuclei. Compounds of general formula (IV) can be prepared, for example, by first converting HBIW to compound IIIA by the above method of A.T. Nielsen (see above) and then converts compound IIIA to a compound of formula (IV) by catalytic transfer hydrogenolysis.

Compounds of formula (IV) may be nitrated to give a compound of formula 02N VN ... NO2 NN 02NN YNN / NO2 ON / " le Kto ik " habit in a group (WA-) is present on either of, one of or both 4- and 10-kvdvena. Compounds of formula (V) having two (HK) groups (bis-salt) and van in A- are an energy-rich anion, such as NO3- or C4-, are useful high energy compounds.

Compounds of formula (IV) may also be reacted with an acylating agent, such as an acid anhydride or an acid chloride, to produce a hexamide of the following formula: The substituents in the R substituents are the same or different and are selected from the group consisting of alkyl, cycloalkyl, aryl, arylalkyl, alkene, alkyne, substituted forms of any of these groups, for example with halogens or nitro groups, or H.

Compounds of formula (VI) can be converted by nitrolysis nitration to CL-20 using a strong nitrating agent.

COR COR NN COR ROC Detailed description of certain preferred embodiments .

In accordance with the improved synthesis of CL-20, HBIW of formula (I) is generally chemically converted to a hexamide of formula (VI). A hexamide of formula (VI) can be reacted with a strong nitrating agent, such as N 2 O in nitric acid or a nitric acid / sulfuric acid mixture, to form CL-20. These nitrating agents are much cheaper than NOBF4 and NO2BF4, which have hitherto been required by the above method by A.T. Nielsen et al for the production of CL-20. HBIW dr and kdnd 6 association and its synthesis will not be further described in the present context. It is understood that equivalents of HBIW (I) could also be used, for example HBIW (I) with substitutions on one or more of the aromatic rings.

The presently preferred method of converting HBIW to a compound of formula (VI) is to first convert HBIW to a compound of formula (III) by the above method of A.T. Nielsen et al; the formula (III) is as follows: oc Z.N, coR 9oc VX /, c0.R NN NrICH2 N CH20 I "" The substituents in the R substituents are the same or different and are selected from the group consisting of alkyl, cycloalkyl, aryl, arylalkyl, alkene, alkyne, substituted forms of any of these groups or H. (FoRening (IIIA) is the compound of the formula (III) van in all four R substituents are CH 3 and Ar 8r phenyl). Ar is generally a phenyl group, although another aromatic group, substituted or unsubstituted, is considered equivalent.

Compounds of formula (III) are converted to compounds of general formula (IV) by hydrogenolysis. At present, catalytic transfer hydrogenolysis is used. Catalytic transfer hydrogenolysis and reagents and catalysts have been described, for example, in R.A.W. Johnstone et al Chem Rev., 85, 129-170 (1985), the contents of which are incorporated herein by reference. A useful method of achieving catalytic transfer 7 Hydrogenolysis is the use of formic acid as a water donor in the presence of a palladium-O-carbon catalyst. The formic acid is generally used in large molar excess, for example as a solvent for the reaction. Depending on the reaction conditions used, a compound of formula (IV) is prepared which is the bis-salt ((two HK) groups (A: is having the formate anion)), the monoformate salt or the free base. It has been found that, when formic acid is used pure with the Pd / C catalyst, the bis-salt has a tendency to form, a mixed water / formic acid solvent system has a tendency to give the monosalt; and a formic acid / methanol solvent system tends to provide the free base. Synthesis of the free base is often preferred over synthesis of either the bis or monosalt; however, the synthesis of the free base is less reproducible than the synthesis of the bis- or mono-salt.

These reactions are exemplified as follows: CHOCCOCH3 CH3 OC 2iiiiH ‘ 11 "1 * D / It b1'44ZH Hox13 bis-salt COCH3 C1130CCOCH3 CH 3 OC, COCH 3 NN AATAD6 At gc.H2 — N • -dm A- CH2X 8 NA. tic001 / 11z0 H N EA, 4. „. 16Nii H cap CH3 OC CH3 OC / COCH3 COCH3 CH3 OC NCOCH3up 6 r 1! -: \ ) ( 14CH2 —N m AN - CH 2 CH3 OCCOCH3 mono-salt CI130CCOCH3 CH3OCN NN CHOC N CH30C N \ __ 4 N IV A-free FgA Hcoon / Me OH 7 DIA N CH24, The novel compounds of formula (IV) are important intermediates for the preparation of CL-20 or for the compounds of formula (V).

The bis or mono-salts of formula (IV) can be converted to the free base by reaction with a strong base, such as an aqueous solution of sodium hydroxide or a strongly basic anion exchange resin, for example Dowex-R in the OH form. The 4- and 10-nitrogen atoms of the compounds of formula (IV) may be converted into hexamide compounds of formula (VI) by reaction with an acylating agent such as an acid anhydride in the presence of a basic catalyst such as pyridine. An acyl halide may alternatively be used as an acylating agent. If the free base is used, the reaction of the 4-10 nitrogen is a simple acylation. If the bis- or mono-salt formate is acylated 9 with acetic anhydride, the corresponding bis- or monoN-formyl compound is obtained. Thus, in the following reactions, acylation using attic acid anhydride of the bisformate salt, the monoformate salt and the free base of compounds of formula (IV) is compared: CH 3 OC, CH 3 OC N / COCH 3 COCH3 acetic acid NN anhydride pyridine HRS, TSCA -free CH 3 OC, COCH3 N, CH 3 OC UN // COCH 3 NN CH 3 OC, A COCH3 CH 3 OC, N CO pyridine hrs Nc lviA nem) et4 4eN tic ° COCH3 \ ZN / d „COCH3 NN 2 CH 3 OC, CH 2 O 3 acetic anhydride pyridine CH 3 OC, C, H 3 OC ,, COCH3 COCH3 NN, hrs -i4 / 163 b., h 14 4 \ e tio0 HCOtP COCH3 COCH3 NN „CHO CHO, (- 3 10 Although the products of each reaction differ slightly from At, each of the products has the general formula (VI). Compounds of formula (VI) are also important intermediates in the synthesis of CL-20.

Compounds of formula (VI) are converted to CL-20 by strong nitrating agents which give nitramine groups in the 2-, 4-, 6-, 8-, 10- and 12-positions of the cage structure. Lamping agents include, but are not limited to, N 2 O in nitric acid or a nitric acid / sulfuric acid mixture. This reaction is as follows: ROC „ N COR ROC \ COR NN ROC „CDR nitrolysis nitration 02 N NN NO2 02N „, NO2 NN N NO2 As mentioned above, compounds of formula (IV) may also be converted to compounds of formula (V) by nitrolysis nitration by reaction with a strong nitrating agent, such as N 2 O / nitric acid or nitric acid / sulfuric acid, to form a compound of formula (V). Subsequent reaction with an acid with an energy-rich anion, such as NO 1 or C4, gives an extremely energy-rich compound of formula (V). These reactions are like 11 Roc, 'INN ■ CO R (0 nitrolysis Roc \ / 'N / Co " / 02NN \ ZN /, NO2 \ t4 NO H2N ®eNH2 1403- nitration Tr Nitrolysis nitration of a compound of formula IV may also give a certain amount of CL-20.

Compounds of formula V are most energy-rich in the form of the side salts of energy-rich anions, such as NO3- or C4-. The nitration reaction gives the bis-nitrate salt. To a more energy-rich salt, the nitrate salt can be converted to a free base, for example by reaction with a base such as NaOH, and then reacted with an acid having the energy-rich anion. Alternatively, the nitrate salt can be converted to a more energy rich salt directly with a suitable anion exchange resin.

As an alternative method of converting a compound of formula (IV) to CL-20, the compound is reacted with a nitrite, for example sodium nitrite in an aqueous acid, to give a compound of formula (VII) as shown in the following reaction.

TV Roc, Roc co R /, COR NN -N ROC% VNN CO IX Roc ,. \ VN./coR N 11%.? „. \ to A- NN "; 1. A- 12 This compound VII, upon nitration with strong nitrating agent, such as N 2 O in nitric acid or a nitric acid / sulfuric acid mixture, undergoes a nitrolysis nitration reaction to form CL-20 as follows: oc,, / '/ N, co it nitrolysis RVN /, COP nitriding N Ntp0 02.N / N ° 2 * 4% N 02N. \ //, NO2 CLO NN No The invention is described in more detail below by means of exemplary embodiments.

Example 1 III A (TADB) Me OH, formic acidIV A free 5% Pd / C To a stirred slurry of 48.0 mg (0.093 mmol) of TADB in 4 ml of methanol and 0.2 ml of formic acid was added 51 mg of 5% Pd / C. The reaction mixture was heated to -60 ° C for 18 hours. Pd / C and the product was removed by filtration. Extraction of Pd / C with DMSO gay the desired product.

1 H NMR (DMSO): δ 1.8-2.1 (multiplet, 12H, CH 3 CO), 4.02-4.25 (multiplet, 2H, NH), 5.2-5.3 (multiplet, 4H, CH), 6.0-6.5 (multiplet, 2H, CH) .

When heated to 1 ° C, the multiple at 1.82.1 collapses into a singlet at 2.0, the multiple at 4.02-4.25 collapses into a singlet at 3.7, the multiple at 5.2-5.3 collapses into a singlet at 5.3 and the multiple at 6.0-6.5 collapses into a singlet at 6.3. 13 Example 2 III A (TADB) formic acid / waterIV A mono Pd / C 60 ° C To a vigorously stirred solution of 10.0 g (19.36 mmol) of TDAB in 200 ml of water was added 40 ml of formic acid; then 10.0 g of 5% Pd / C was added. The reaction mixture was heated to 60 ° C. After 18.5 hours, the solid was filtered off from the solution and the volatile material was removed under reduced pressure to give 7.9 g (106.7%) of the monoformate salt.

NMR (DMSO): δ 1.7-2.3 (multiplet, 1211, CH 3 CO), 4.7-4.9 (broad doublet, 1H, NH, J = 9.0112) 5.5-5.7 (multiplet, 211, CH), 6.0-6.8 (multiplet 411, CH), 8.3 (broad singlet, 411, NH, HCO 2 H).

When heated to 1 ° C, the multiplet collapses at 172.3 to 2s, the broad doublet at 4.7-4.9 moves to 4.3 and widens, the multiplet at 5.5-5.7 collapses into a doublet at 5.6 (J = 6 Hz), and the broad singlet at 8.3 split into two singlets at 8.32 and 8.39.

Example 3 III A (TADB) formic acid IV A bis Pd / C To a stirred slurry of 10.0 g (19.36 mmol) of TADB in 200 ml of formic acid was added 10.0 g of 5% Pd / C. After 18 hours, Pd / C was removed by filtration and the formic acid was removed under reduced pressure to give 8.78 g (104%) of the desired bis-salt. 11-1 NMR (DMSO): δ 1.9-2.2 (multiplet, 1211, CH 3 CO), 6.1-6.8 (multiplet, 611, CH), 8.1-8.4 (multiplet, CH, NH, HCO 2 H). 14 When heated to 1 ° C, the multiplet at 1.92.2 collapses into a singlet and the Other TWA multiplets begin to collapse.

Example 4 IV A_1) 2) NaOH, H 2 O. i> VI A Attic acid, pyridine To 500 mg (1.17 mmol) of the bis-formate salt was added 2.4 mL of 1M NaOH. Alit volatile material was deposited under reduced pressure. The residue was dissolved in 20 ml of acetic anhydride and 5 ml of pyridine and heated at 60 ° C overnight. After 18 hours, the volatiles were removed and the residue was treated with 10 mL of EtOAc. The solution was filtered and concentrated. The residue was passed through a plug of silica gel using acetone as eluent, leaving gay IVA as an impure solid. 1 H NMR (CHCl 3): δ 2.05-2.2 (multiplet, 12H CH 3 CO), 2.45 (singlet, 6H, CH 3 CO), 6.3-6.5 (multiplet, 4H, CH), 6.8-7.0 (multiplet, 2H, CH).

When heated to 1 ° C (DMS0 solvent), the multiplet collapses at 2.05-2.2 into a singlet. The multiplets at 6.3-6.5 and 6.8-7.0 are starting to collapse.

Example IV A monoPyridine, attic anhydride, VI B To a stirred slurry of 5.0 g (13.1 mmol) of the monoformate salt in 200 ml of attic anhydride was added 50 ml of pyridine. After 20 hours, all volatile material was removed under reduced pressure. The residue was then treated with 100 ml of EtOAc. A formation was formed which was removed by filtration. The solvent was removed and Aterstoden was allowed to pass a plug of silica gel using acetone as eluent.

1 H NMR (CHCl 3): δ 2.06, 2.09, 2.12, 2.14 (4 singlet, 12H, CH 3 CO), 2.42 (singlet, 3H, CH 3 CO), 6.0-7.0 (multiplet, 6H, CH), 8.3 (singlet, 1H, CHO ).

Example 6 IV A bisPyridine, acetic anhydride VI C To a stirred slurry of 5.0 g (11.67 mmol) of the bisformate salt (IV A bis) in 200 ml of attic anhydride was added 50 ml of pyridine. After hours, all volatile material was removed under reduced pressure. The residue was then treated with 100 ml of EtOAc. A precipitate formed which was removed by filtration. The solvent was removed and the residue was allowed to pass through a plug of silica gel using acetone as eluent. 4.5 g (98.3%) of yield of bis-formylphthyrene were obtained. Rf = 0.35 (acetone).

1 H NMR (CHCl 3): δ 2.0-2.3 (multiplet, 12H, CH 3 CO), 6.06 (doublet, 0.2H, CH, J = 4.8 Hz), 6. (broad singlet, 0.45H, CH), 6.26 (doublet, 1.5 H, CH, J = 7.8, 1.8 Hz), 6.46 (singlet, 1.7H, CH), 6.67 (doublet, 1.5H, CH, J = 7.8, 1.81 Hz), 6.75-6. 81 (multiplet, 0.65H, CH).

Example 7 VI CN2051 HNO3CL - To 10 mg (0.026 mmol) of the diformyltetraacetyl compound VI C was added 2 ml of 5% N 2 O in nitric acid at 0 ° C for 4.5 hours; the mixture was then sprinkled with water. The aqueous solution was extracted 4X with ethyl acetate. The organic material was dried (MgSO 4) and concentrated to dryness. By thin layer chromatography (silica gel, multiple solvent systems). The product showed an Rf identical to the value of CL-20 and a superimposable 1 H NMR spectrum. 16 Example 8 IV A freeNaNO2, attic acid waterVII A To 1.0 g of tetraacetyl (IV A free) in 2 ml of water and 2 ml of acetic acid was added 0.70 g of NaNO 2 in 2 ml of water at 0 ° C. The reaction mixture was stirred for 18 hours at room temperature. The desired product precipitated from the reaction mixture and was collected by filtration in quantitative yield.

Although the invention has been described in the form of certain preferred embodiments, modifications may be made as will be apparent to those skilled in the art without departing from the scope of the present invention.

Various features of the invention are set forth in the following claims.

Claims (14)

Pane. No. 9302299-4 26864 / HP / UH EATENTKRAV 1. Association selected from the group consisting of R at, R CC.% \ / \\, / "CO R NN tor) (Or and ROC., 4N ROC„% / COR ROCs.4,, COR k N 2 the R substituents are the same or different and selected from the group consisting of alkyl, cycloalkyl, aryl, arylalkyl, alkene, alkyne or substituted forms of flakes of these groups and H and wherein a group consisting of a hydrogen ion (Hi) and a complementary anion to the present on either of, one of or both the nuclei in the 4- and 10-positions. A compound according to claim 1 of formula (IV). A compound according to claim 2, used in all R substituents on CH 3. A compound according to claim 1 of formula (V). A compound according to claim 4 having a hydrogen ion and an anion associated with the nitrogen in each of the 4- and 10-positions, said anion being an energy-rich anion. A compound according to claim 5, which is in the anion of NO: or C4-. A compound according to claim 1 of formula (VI), used in all R substituents on CH 3 or H. Process for the preparation of the energy-rich compound of the formula II: 3 C, L-. k annetecknatdirav, that one nitrates a compound of formula VI Roc. ,, COR. N Roc: IVN / con. ROC., COR van in R is selected from the group consisting of alkyl, cycloalkyl, aryl, arylalkyl, alkene, alkyne, substituted forms of any of these groups and H, with a strong nitrating agent. The method of claim 8, wherein the strong nitrating agent is HNO 3 or a 1NO 3/112504 mixture. 4 A process according to claim 8, wherein the compound of formula VI is obtained by acylating a compound of formula IV: wherein in said formula IV a member of the group consisting of water ion and a complementary anion is present on either of, one of or both the nitrogen in the 4- and 10-positions, in the presence of at least one acylating agent. The method of claim 10, wherein the acylating agent is an acid chloride or carboxylic acid hydride. A process according to claim 10, wherein the compound of formula IV is obtained by catalytic Transfer Hydrogenolysis of a compound of formula (III): icH 2 - - CH 21, PA. "R OC ROC \ N cO R COA A process according to claim 12, wherein the hydrogenolysis is carried out in the presence of a palladium-pd-carbon catalyst. A process for the preparation of a compound of formula IV: wherein in said formula IV each R is independently selected from the group consisting of alkyl, cycloalkyl, aryl, arylalkyl, alkene, alkyne, a substituted form of any of these groups and H, and wherein a member of the group consisting of a water anion and a complementary anion is present in either, one or both of the quadratic 4- and 10-positions of said formula IV, characterized in that hydrogenolysing a compound of formula III C1130C, COCH3 CH3OC. VN / CO% N scH2— N CH211 P.ans. No. 9302299-4 26864 / HP / UH SUMMARY Hexabenzylhexaazaisowurtzitan is converted to tetraacetyl, dibenzyl azaisowurtzitan. The benzyl groups are removed by catalytic transfer hydrogenolysis, leaving a pair of available nitrogen. The available nitrogen is acetylated and the resulting intermediate is converted to CL-20 with a strong nitrating agent.