Progress in the Synthesis of Energetic Salts Based on Pyrazole

doi:10.6023/cjoc202009019

Abstract

The pyrazole ring has three modifiable carbon sites and one modifiable NH site. Based on the pyrazole ring, a variety of pyrazole energetic compounds can be designed by the introduction of nitro, nitramino, amino and hydroxyl group and the formation of fused rings. At the same time, compared with conventional energetic compounds such as 2,4,6-trinitro- benzene (TNT), hexahydro-1,3,5-trinitro-triazine (RDX) and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX), energetic pyrazoles have the advantages of high nitrogen content, high enthalpy of formation and low sensitivities. In recent years, a large number of energetic salts based on pyrazole have been designed and synthesized around the world, including monocyclic energetic salts, bicyclic energetic salts and fused energetic salts based on pyrazole. Many of them exhibit the characteristics of high energy and low sensitivity. The synthesis and properties of recently reported energetic salts based on pyrazole are reviewed, and their applications in the field of energetic materials are prospected.

Key words: energetic material, energetic salt, pyrazole, nitramino

Cite this article

Guanglei Li, Haifeng Huang, Jun Yang, Hongzhen Duan. Progress in the Synthesis of Energetic Salts Based on Pyrazole[J]. Chinese Journal of Organic Chemistry, 2021, 41(4): 1466-1488.

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Compd.		T_m^a/℃	T_d^b/℃	d^c/(g?cm^–3)	Δ_fH^d/(kJ?mol^–1)/(kJ?g^–1)	P^e/GPa	D^f/(m?s^–1)	IS^g/J	FS^h/N
2a		—	224	1.73	60.5/0.28	29.9	8461	40	—
2b		158	167	1.69	299.0/1.10	25.6	7871	>40	—
2c		171	171	1.71	273.5/0.95	26.0	7972	>40	—
2d		168	168	1.77	401.2/1.40	31.9	8543	>40	—
2e		188	196	1.76	235.6/0.78	27.7	8216	>40	—
2f		—	243	1.68	452.3/0.75	24.3	7817	>40	—
2g		163	235	1.66	28.3/0.11	24.7	7865	>40	—
2h		136	222	1.69	133.6/0.48	26.9	8134	>40	—
2i		206	206	1.76	355.0/1.12	28.8	8359	>40	—
2j		166	219	1.61	375.0/1.19	23.7	7586	>40	—
2k		120	167	1.64	459.8/1.45	25.2	7922	35	—
2l		122	197	1.62	246.5/0.84	25.3	7983	>40	—
2m		125	184	1.65	352.7/1.15	27.2	8236	>40	—
4		—	176	1.82	35.1/0.15	35.1	8676	6	—
6a		—	171	1.72	3.1/0.01	28.8	8176	>40	—
6b		—	140	1.73	274.9/0.95	29.5	8175	>40	—
6c		—	132	1.73	250.5/0.83	29.2	8177	>40	—
6d		—	118	1.74	381.6/1.26	30.8	8345	>40	—
6e		—	186	1.76	213.7/0.67	29.7	8261	>40	—
6f		—	185	1.77	331.9/1.00	31.1	8442	>40	—
11a		—	147	1.80	54.2/0.19	37.4	9013	30	—
11b		—	171	1.75	274.7/0.97	33.8	8917	5	—
11c		—	115	1.64	544.6/1.53	25.3	7921	>40	—
11d		—	167	1.75	496.6/1.29	27.9	8244	>40	—
11e		103	118	1.74	762.9/1.98	29.7	8452	>40	—
11f		—	170	1.71	452.4/1.09	27.1	8196	>40	—
11g		—	194	1.71	718.2/1.61	27.9	8342	>40	—
11h		—	229	1.66	–0.8/–0.01	24.3	7920	>40	—
11i		—	180	1.64	227.9/0.62	25.5	8117	>40	—
11j		—	178	1.65	464.1/1.17	27.5	8385	>40	—
11k		—	172	1.65	701.5/1.65	28.9	8581	23	—
11l		132	189	1.69	–362.8/–0.86	23.3	7713	>40	—
11m		—	144	1.81	–108.6/–0.35	30.4	8378	5	—
11n		—	166	1.72	–229.4/–0.72	24.4	7799	>40	—
15a		—	141	1.85	264.2/0.77	40.2	9410	8	80
15b		—	152	1.75	489.3/1.42	35.7	9066	5	60
18a		—	166	1.86	193.7/0.77	38.5	9195	10	80
18b		—	180	1.86	293.7/1.17	38.7	9176	10	120
18c		—	171	1.72	122.3/0.44	28.3	8319	40	360
Compd.	T_m^a/℃		T_d^b/℃	d^c/(g?cm^–3)	Δ_fH^d/(kJ?mol^–1)/(kJ?g^–1)	P^e/GPa	D^f/(m?s^–1)	IS^g/J	FS^h/N
18d	—		200	1.79	232.3/0.80	32.2	8745	24	160
18e	—		177	1.78	488.9/1.62	31.9	8645	20	160
18f	—		183	1.81	320.4/1.01	31.5	8629	30	240
18g	—		153	1.84	720.5/2.27	37.4	9170	6	60
18h	—		142	1.77	416.7/0.79	32.8	8652	20	120
18i	—		130	1.88	450.0/1.34	39.5	9237	8	80
22a	—		244	1.62	–147.3/–0.92	20.3	7776	28	240
22b	—		181	1.64	–93.3/–0.53	22.8	7929	26	240
22c	—		223	1.63	8.8/0.05	23.8	8339	23	240
23b	—		204	1.71	12.4/0.05	26.4	8200	40	360
23c	—		169	1.71	219.8/0.79	28.0	8540	40	360
23d	—		214	1.75	337.2/1.15	30.7	8877	40	360
26a	—		167	1.68	68.7/0.36	28.2	8279	10	360
26b	—		180	1.70	27.0/0.12	25.1	8063	30	360
26c	132		169	1.64	144.9/0.58	24.7	8021	10	360
27a	—		224	1.62	–253.4/–1.21	24.4	7909	30	288
27b	—		266	1.68	7.8/0.03	24.2	7935	40	360
27c	—		131	1.68	115.2/0.46	25.7	8159	10	360
31	—		129	1.80	194.8/0.78	33.8	8790	7	192
36a	—		141	1.78	85.4/0.36	33.0	8601	>20	192
36b	—		166	1.80	135.5/0.54	34.1	8700	>20	162
36c	—		161	1.72	43.8/0.16	28.7	8256	>20	240
36d	—		140	1.71	231.4/0.78	30.1	8480	>20	252
TNTⁱ	81		290	1.65	–55.5/–0.24	23.5	7459	15	353
RDXⁱ	205		210	1.81	86.3/0.39	38.0	8983	7.5	120
HMXⁱ	275		279	1.90	116.1/0.39	41.5	9221	7	112
CL-20ⁱ	—		215	2.03	365.4/0.83	46.7	9455	4	48

Compd.		T_m^a/℃	T_d^b/℃	d^c/(g?cm^–3)	Δ_fH^d/(kJ?mol^–1)/(kJ?g^–1)	P^e/GPa	D^f/(m?s^–1)	IS^g/J	FS^h/N
2a		—	224	1.73	60.5/0.28	29.9	8461	40	—
2b		158	167	1.69	299.0/1.10	25.6	7871	>40	—
2c		171	171	1.71	273.5/0.95	26.0	7972	>40	—
2d		168	168	1.77	401.2/1.40	31.9	8543	>40	—
2e		188	196	1.76	235.6/0.78	27.7	8216	>40	—
2f		—	243	1.68	452.3/0.75	24.3	7817	>40	—
2g		163	235	1.66	28.3/0.11	24.7	7865	>40	—
2h		136	222	1.69	133.6/0.48	26.9	8134	>40	—
2i		206	206	1.76	355.0/1.12	28.8	8359	>40	—
2j		166	219	1.61	375.0/1.19	23.7	7586	>40	—
2k		120	167	1.64	459.8/1.45	25.2	7922	35	—
2l		122	197	1.62	246.5/0.84	25.3	7983	>40	—
2m		125	184	1.65	352.7/1.15	27.2	8236	>40	—
4		—	176	1.82	35.1/0.15	35.1	8676	6	—
6a		—	171	1.72	3.1/0.01	28.8	8176	>40	—
6b		—	140	1.73	274.9/0.95	29.5	8175	>40	—
6c		—	132	1.73	250.5/0.83	29.2	8177	>40	—
6d		—	118	1.74	381.6/1.26	30.8	8345	>40	—
6e		—	186	1.76	213.7/0.67	29.7	8261	>40	—
6f		—	185	1.77	331.9/1.00	31.1	8442	>40	—
11a		—	147	1.80	54.2/0.19	37.4	9013	30	—
11b		—	171	1.75	274.7/0.97	33.8	8917	5	—
11c		—	115	1.64	544.6/1.53	25.3	7921	>40	—
11d		—	167	1.75	496.6/1.29	27.9	8244	>40	—
11e		103	118	1.74	762.9/1.98	29.7	8452	>40	—
11f		—	170	1.71	452.4/1.09	27.1	8196	>40	—
11g		—	194	1.71	718.2/1.61	27.9	8342	>40	—
11h		—	229	1.66	–0.8/–0.01	24.3	7920	>40	—
11i		—	180	1.64	227.9/0.62	25.5	8117	>40	—
11j		—	178	1.65	464.1/1.17	27.5	8385	>40	—
11k		—	172	1.65	701.5/1.65	28.9	8581	23	—
11l		132	189	1.69	–362.8/–0.86	23.3	7713	>40	—
11m		—	144	1.81	–108.6/–0.35	30.4	8378	5	—
11n		—	166	1.72	–229.4/–0.72	24.4	7799	>40	—
15a		—	141	1.85	264.2/0.77	40.2	9410	8	80
15b		—	152	1.75	489.3/1.42	35.7	9066	5	60
18a		—	166	1.86	193.7/0.77	38.5	9195	10	80
18b		—	180	1.86	293.7/1.17	38.7	9176	10	120
18c		—	171	1.72	122.3/0.44	28.3	8319	40	360
Compd.	T_m^a/℃		T_d^b/℃	d^c/(g?cm^–3)	Δ_fH^d/(kJ?mol^–1)/(kJ?g^–1)	P^e/GPa	D^f/(m?s^–1)	IS^g/J	FS^h/N
18d	—		200	1.79	232.3/0.80	32.2	8745	24	160
18e	—		177	1.78	488.9/1.62	31.9	8645	20	160
18f	—		183	1.81	320.4/1.01	31.5	8629	30	240
18g	—		153	1.84	720.5/2.27	37.4	9170	6	60
18h	—		142	1.77	416.7/0.79	32.8	8652	20	120
18i	—		130	1.88	450.0/1.34	39.5	9237	8	80
22a	—		244	1.62	–147.3/–0.92	20.3	7776	28	240
22b	—		181	1.64	–93.3/–0.53	22.8	7929	26	240
22c	—		223	1.63	8.8/0.05	23.8	8339	23	240
23b	—		204	1.71	12.4/0.05	26.4	8200	40	360
23c	—		169	1.71	219.8/0.79	28.0	8540	40	360
23d	—		214	1.75	337.2/1.15	30.7	8877	40	360
26a	—		167	1.68	68.7/0.36	28.2	8279	10	360
26b	—		180	1.70	27.0/0.12	25.1	8063	30	360
26c	132		169	1.64	144.9/0.58	24.7	8021	10	360
27a	—		224	1.62	–253.4/–1.21	24.4	7909	30	288
27b	—		266	1.68	7.8/0.03	24.2	7935	40	360
27c	—		131	1.68	115.2/0.46	25.7	8159	10	360
31	—		129	1.80	194.8/0.78	33.8	8790	7	192
36a	—		141	1.78	85.4/0.36	33.0	8601	>20	192
36b	—		166	1.80	135.5/0.54	34.1	8700	>20	162
36c	—		161	1.72	43.8/0.16	28.7	8256	>20	240
36d	—		140	1.71	231.4/0.78	30.1	8480	>20	252
TNTⁱ	81		290	1.65	–55.5/–0.24	23.5	7459	15	353
RDXⁱ	205		210	1.81	86.3/0.39	38.0	8983	7.5	120
HMXⁱ	275		279	1.90	116.1/0.39	41.5	9221	7	112
CL-20ⁱ	—		215	2.03	365.4/0.83	46.7	9455	4	48

Entry	Starting material	Reagent	Yield/%
1	LLM-116	H₂O₂/H₂SO₄	93
2	LLM-116	H₂S₂O₈	93
3	LLM-116	Oxone	85
4	ADNP	NaNO₂/H₂SO₄	80
5	ADNP	H₂S₂O₈	37
6	TIP	HNO₃/SiO₂/H₂SO₄	92

Entry	Starting material	Reagent	Yield/%
1	LLM-116	H₂O₂/H₂SO₄	93
2	LLM-116	H₂S₂O₈	93
3	LLM-116	Oxone	85
4	ADNP	NaNO₂/H₂SO₄	80
5	ADNP	H₂S₂O₈	37
6	TIP	HNO₃/SiO₂/H₂SO₄	92

Compd.	T_m^a/℃	T_d^b/℃	d^c/(g?cm^–3)	Δ_fH^d/(kJ?mol^–1)/(kJ?g^–1)	P^e/GPa	D^f/(m?s^–1)	IS^g/J	FS^h/N
39	—	262	1.88	274.7/0.79	34.6	8615	>40	—
41a	—	228	1.73	246.5/0.63	27.3	8041	>40	—
41b	249	272	1.67	506.4/1.26	27.1	8088	>40	—
41c	210	272	1.71	448.8/1.07	27.9	8201	>40	—
41d	212	266	1.72	558.0/1.29	29.0	8339	>40	—
41e	—	259	1.75	331.2/0.91	31.1	8330	>40	—
41f	247	297	1.82	557.0/1.26	31.0	8449	>40	—
41g	166	261	1.72	700.4/1.63	28.9	8231	>40	—
41h	—	260	1.80	428.1/1.19	32.8	8536	>40	—
44a	132	285	1.73	622.8/2.06	31.6	8621	>40	>360
44b	—	215	1.76	709.9/2.23	34.4	8832	33	252
44c	—	241	1.74	811.4/2.56	32.9	8798	>40	>360
44d	—	340	1.78	624.1/1.81	31.1	8660	>40	>360
44e	—	281	1.65	728.9/2.03	26.5	8236	>40	>360
44f	233	262	1.70	831.7/2.22	28.9	8541	27	240
44g	—	242	1.71	941.4/2.42	30.0	8685	20	216
44h	—	279	1.72	828.3/2.16	28.0	8363	>40	252
44i	—	222	1.80	1211.7/3.15	35.2	9031	12	252
44j	—	292	1.74	944.8/2.37	29.5	8555	>40	>360
44k	—	303	1.77	1166.1/2.65	30.5	8647	20	>360
49a	186	260	1.68	422.3/1.55	25.1	8153	>40	>360
49b	192	200	1.65	573.8/2.00	25.6	8264	>40	>360
49c	224	260	1.75	470.2/1.62	29.8	8592	>40	>360
52a	—	156	1.64	793.0/2.66	25.8	8167	>40	>360
52b	—	137	1.72	937.1/2.99	29.7	8640	28	240
52c	—	151	1.76	834.3/2.66	32.2	8747	32	>360
55a	—	216	1.72	763.6/2.96	31.3	8745	40	360
55b	—	171	1.84	805.8/2.94	38.3	9295	35	216
55c	—	196	1.77	910.0/3.15	35.0	9162	10	160
55d	—	257	1.74	729.1/2.43	29.6	8668	40	360
55e	195	221	1.61	834.7/2.65	25.4	8229	37.5	252
55f	178	216	1.70	935.9/2.83	29.3	8712	30	240
55g	188	208	1.66	1049.2/3.04	28.6	8657	12.5	216
55h	—	216	1.76	930.3/2.73	29.5	8649	40	324
55i	—	239	1.74	1049.8/2.96	29.6	8701	35	360
55j	—	270	1.72	1275.2/3.23	28.6	8562	40	360
Compd.	T_m^a/℃	T_d^b/℃	d^c/(g?cm^–3)	Δ_fH^d/(kJ?mol^–1)/(kJ?g^–1)	P^e/GPa	D^f/(m?s^–1)	IS^g/J	FS^h/N
56a	—	229	1.75	547.1/2.25	28.9	8801	35	360
56b	—	187	1.78	445.0/1.82	29.9	8818	32	360
56c	—	251	1.70	399.1/1.75	24.9	8286	40	>360
56d	—	224	1.69	485.5/1.70	23.9	8244	40	>360
56e	—	287	1.72	337.7/1.03	23.6	8138	40	>360
63a	—	137	1.85	220.6/0.58	35.8	8851	8	240
63b	94	155	1.77	220.9/0.56	31.5	8670	10	240
63c	—	193	1.76	116.2/0.33	29.4	8343	10	240
63d	—	196	1.70	353.3/0.76	25.2	8136	15	360
63e	185	186	1.75	791.9/1.55	27.3	8306	16	360
63f	—	206	1.76	565.4/1.10	26.5	8219	12	360
63g	187	193	1.81	1359.4/2.64	34.2	8952	10	360
63h	—	250	1.80	1269.7/2.04	28.9	8542	18	360
67a	—	187	1.76	711.4/1.77	30.0	8680	>40	>360
67b	—	171	1.79	842.0/1.92	33.6	9077	>40	>360
67c	—	187	1.73	1062.4/2.46	30.2	8759	>40	>360
67d	—	195	1.71	677.9/1.40	25.1	8193	>40	>360
67e	—	191	1.71	1068.7/2.07	27.3	8502	>40	>360
67f	—	208	1.75	1014.6/1.85	29.7	8705	22.4	>360
67g	—	169	1.72	1300.5/2.58	25.7	8117	>40	>360
67h	—	176	1.72	1511.2/2.39	25.9	8143	>40	>360
67i	—	190	1.74	1270.5/2.84	26.0	8159	>40	>360
70b	—	209	1.71	432.7/1.44	24.3	8062	20	360
70c	—	254	1.67	348.4/1.25	28.3	8431	5	360
70d	—	197	1.69	425.1/1.44	31.0	8648	10	360
70f	—	168	1.76	820.6/2.52	27.9	8441	2	192
70h	—	240	1.73	298.0/0.71	18.8	7364	40	>360
72a	—	250	1.68	405.1/1.58	22.4	7714	8	>360
74a	—	218	1.75	390.9/1.30	27.2	8223	15	>360
74b	251	286	1.68	–50.4/–0.17	23.0	7689	40	>360
74c	—	230	1.76	303.7/1.00	28.6	8271	10	>360
74e	—	240	1.66	740.7/1.75	21.6	7563	10	>360
76a	—	201	1.81	295.7/0.85	32.8	8673	2	216
79a	—	225	1.77	291.0/1.07	28.6	8516	25	168
79b	220	289	1.81	287.3/0.92	29.0	8257	18	160
79c	—	174	1.82	1404.5/2.68	30.4	8641	25	240
79d	240	254	1.81	153.0/0.35	26.4	8109	20	240
79e	—	202	1.75	–196.3/–0.42	23.8	7745	25	288
79f	—	213	1.76	346.3/1.02	25.7	8228	50	>360
79g	—	261	1.81	1566.2/2.65	30.6	8952	50	360
80	—	315	2.15	45.7/0.11	31.1	8275	1.5	60
82a	—	304	1.78	327.4/0.71	28.0	8391	>40	>360
82b	—	195	1.79	535.4/1.09	29.5	8632	>40	216
82c	—	183	1.73	1013.5/1.84	29.6	8731	2	54
82d	—	206	1.80	767.4/1.42	28.6	8461	>40	>360
82e	—	257	1.81	329.1/0.87	32.2	8638	7.5	>360
82f	—	156	1.84	634.5/1.56	35.5	9038	4	192
82g	—	244	1.70	1040.1/1.82	26.0	8224	37.5	>360
TNTⁱ	81	290	1.65	–55.5/–0.24	23.5	7459	15	353
RDXⁱ	205	210	1.81	86.3/0.39	38.0	8983	7.5	120
HMXⁱ	275	279	1.90	116.1/0.39	41.5	9221	7	112
CL-20ⁱ	—	215	2.04	365.4/0.83	46.7	9455	4	48

吡唑含能离子盐的合成研究进展