CN107879952A - 一种丙基硝基胍的制备方法 - Google Patents
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- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012153 distilled water Substances 0.000 claims abstract description 12
- 230000035484 reaction time Effects 0.000 claims abstract description 12
- 238000001953 recrystallisation Methods 0.000 claims abstract description 11
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 235000019441 ethanol Nutrition 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 7
- 125000004888 n-propyl amino group Chemical class [H]N(*)C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- LWPLPMSGDZDOLW-UHFFFAOYSA-N 2-amino-1-nitroguanidine Chemical compound NNC(=N)N[N+]([O-])=O LWPLPMSGDZDOLW-UHFFFAOYSA-N 0.000 description 2
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 150000001409 amidines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 description 1
- 238000006698 hydrazinolysis reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C277/08—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups of substituted guanidines
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开一种丙基硝基胍的制备方法，该法以硝基胍和正丙胺为原料，包括如下步骤：将蒸馏水加入反应瓶中，再依次加入硝基胍和正丙胺进行反应，反应温度30℃～60℃，反应时间1h～4h，用无机酸调节反应体系pH值1～6，过滤、重结晶得丙基硝基胍。其中硝基胍、正丙胺、水的质量比为1：0.3～0.6：5～20，重结晶溶剂为有机溶剂。本发明是为了解决丙基硝基胍制备过程反应步骤多、原材料种类多、成本高、收率低等问题。主要用于丙基硝基胍的制备。
Description
技术领域
本发明涉及硝基胍烷基化，具体地说是一种丙基硝基胍的制备方法，属有机合成。
背景技术
丙基硝基胍是一种重要的有机化合物，不仅可作为单质炸药用于不敏感混合炸药和低易损发射药等武器装备，还可以作为药物中间体用于抗菌、抗病毒等医药的合成。
丙基硝基胍的合成方法主要是以硝酸胍或硝基胍为原料，先合成出胍基化试剂，再与胺类进行反应制得目标物。新疆大学郭瑾烨等人在新疆大学学报(自然科学版)，2009,26(2):207-211《胍基化试剂的制备及其应用》一文公开了一种丙基硝基胍的合成方法，将硝基胍肼解后得N-氨基-N’-硝基胍，再与2,4-戊二酮反应制得胍基化试剂N-硝基-1-(3,5-二甲基吡唑)脒(DMNPC)，然后将正丙胺溶于乙醇与胍基化试剂反应制备出丙基硝基胍，N-氨基-N’-硝基胍收率为32％，N-硝基-1-(3,5-二甲基吡唑)脒收率为70％，丙基硝基胍收率83％，总收率为18.6％。该方法存在反应步骤多、原材料种类多、成本高、收率低等问题，难以实现规模化制备。
发明内容
本发明要解决的技术问题是克服背景技术中的反应步骤多、原材料种类多、成本高、收率低等不足和缺陷，提供一种单步反应、原材料种类少、成本低、收率高的丙基硝基胍合成方法。
本发明构思：针对丙基硝基胍制备方法中，反应步骤过多、使用肼、2,4-戊二酮、乙酸等原料成本较高、反应收率较低的现状，拟寻找一种反应步骤较少、原材料便宜、收率较高的制备方法。通过设计新的反应体系、控制反应温度和时间、调节体系pH值等，能够提高收率、降低成本。发明人研究发现，利用水作为反应媒介，硝基胍和正丙胺可直接反应制备丙基硝基胍，反应可一步完成且收率较高，降低了制备成本。
本发明提供一种丙基硝基胍的制备方法，包括如下步骤：
将蒸馏水加入反应瓶中，再依次加入硝基胍和正丙胺进行反应，反应温度30℃～60℃，反应时间1h～4h，用无机酸调节反应体系pH值1～6，过滤、重结晶得丙基硝基胍。其中硝基胍、正丙胺、水的质量比为1：0.3～0.6：5～20，无机酸为盐酸、硫酸、硝酸、磷酸等，重结晶溶剂为乙醇、丙酮、甲苯、苯、乙腈、石油醚等有机溶剂。
本发明优选的丙基硝基胍的制备方法，将蒸馏水加入反应瓶中，再依次加入硝基胍和正丙胺进行反应，反应温度50℃，反应时间2h，用盐酸调节反应体系pH＝3，过滤、乙醇重结晶得丙基硝基胍；硝基胍、正丙胺、水的质量比为1：0.4：10。
本发明有益效果：
⑴本发明采用水作为反应媒介，硝基胍和正丙胺可直接反应制备丙基硝基胍，反应步骤由三步缩减至一步，收率由18.6％提高到68％。
⑵本发明采用水、乙醇、盐酸作为原料，避免使用肼、2,4-戊二酮、乙酸等成本较高的原料，解决了丙基硝基胍成本较高的问题。
具体实施方式
实施例1
丙基硝基胍的制备
将104g蒸馏水加入到装磁力搅拌器、温度计和尾气接收瓶的玻璃反应瓶中，开启搅拌，再依次加入10.4g硝基胍和4.2g正丙胺，反应温度50℃时，反应时间2h，用滴管滴加盐酸调节反应体系pH＝3，过滤得固体，然后用乙醇重结晶，得到产品丙基硝基胍9.9g，收率68.5％，纯度≥99.3％。
丙基硝基胍的结构鉴定：
元素分析:146C4H10N4O2，计算值C32.88,H 6.85,N 38.36，
实测值C 32.93,H 6.87,N 38.41。
IR(KBr),υ/cm-1:3308，3296，1620，1576，909。
1H NMR(DMSO-d6,δ,ppm):8.25(s,2H,NH2),7.70(s,1H,NH),2.65(m,2H,-CH2-N)，1.58(m,2H,CH2)，0.96(m,3H,CH3)。
经分析检测证实本发明所得的产物为丙基硝基胍。
实施例2
丙基硝基胍的制备
将104g蒸馏水加入到装磁力搅拌器、温度计和尾气接收瓶的玻璃反应瓶中，开启搅拌，再依次加入10.4g硝基胍和4.2g正丙胺，反应温度40℃时，反应时间2h，用滴管滴加盐酸调节反应体系pH＝4，过滤得固体，然后用乙醇重结晶，得到产品丙基硝基胍9.1g，收率62.3％，纯度≥98.9％。
实施例3
丙基硝基胍的制备
将156g蒸馏水加入到装磁力搅拌器、温度计和尾气接收瓶的玻璃反应瓶中，开启搅拌，再依次加入10.4g硝基胍和3.2g正丙胺，反应温度60℃时，反应时间1h，用滴管滴加盐酸调节反应体系pH＝3，过滤得固体，然后用乙醇重结晶，得到产品丙基硝基胍7.6g，收率52.1％，纯度≥99.1％。
实施例4
丙基硝基胍的制备
将156g蒸馏水加入到装磁力搅拌器、温度计和尾气接收瓶的玻璃反应瓶中，开启搅拌，再依次加入10.4g硝基胍和4.2g正丙胺，反应温度40℃时，反应时间3h，用滴管滴加盐酸调节反应体系pH＝1，过滤得固体，然后用乙醇重结晶，得到产品丙基硝基胍8.2g，收率56.2％，纯度≥98.5％。
实施例5
丙基硝基胍的制备
将104g蒸馏水加入到装磁力搅拌器、温度计和尾气接收瓶的玻璃反应瓶中，开启搅拌，再依次加入10.4g硝基胍和5.2g正丙胺，反应温度30℃时，反应时间4h，用滴管滴加盐酸调节反应体系pH＝6，过滤得固体，然后用乙醇重结晶，得到产品丙基硝基胍8.6g，收率58.9％，纯度≥99.0％。
实施例6
丙基硝基胍的制备
将104g蒸馏水加入到装磁力搅拌器、温度计和尾气接收瓶的玻璃反应瓶中，开启搅拌，再依次加入10.4g硝基胍和5.2g正丙胺，反应温度40℃时，反应时间2h，用滴管滴加盐酸调节反应体系pH＝3，过滤得固体，然后用乙醇重结晶，得到产品丙基硝基胍9.4g，收率64.4％，纯度≥98.8％。
实施例7
丙基硝基胍的制备
将208g蒸馏水加入到装磁力搅拌器、温度计和尾气接收瓶的玻璃反应瓶中，开启搅拌，再依次加入10.4g硝基胍和6.2g正丙胺，反应温度50℃时，反应时间3h，用滴管滴加盐酸调节反应体系pH＝1，过滤得固体，然后用乙醇重结晶，得到产品丙基硝基胍8.8g，收率60.3％，纯度≥98.1％。
Claims (2)
1.一种丙基硝基胍的制备方法，包括以下步骤：将蒸馏水加入反应瓶中，再依次加入硝基胍和正丙胺进行反应，反应温度30℃～60℃，反应时间1h～4h，用无机酸调节反应体系pH值1～6，过滤、重结晶得丙基硝基胍；硝基胍、正丙胺、水的质量比为1：0.3～0.6：5～20；所述无机酸为盐酸、硫酸、硝酸或磷酸；所述重结晶是以乙醇、丙酮、甲苯、苯、乙腈或石油醚为重结晶溶剂。
2.根据权利要求1所述的丙基硝基胍的制备方法，包括如下步骤：将蒸馏水加入反应瓶中，再依次加入硝基胍和正丙胺进行反应，反应温度50℃，反应时间2h，用盐酸调节反应体系pH＝3，过滤、乙醇重结晶得丙基硝基胍；硝基胍、正丙胺、水的质量比为1：0.4：10。
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4677226A (en) * | 1985-07-29 | 1987-06-30 | American Cyanamid Company | Alkyl-, alkenyl- and alkynylnitroguanidines as cytokinin plant growth regulants |
| CN1328542A (zh) * | 1998-11-25 | 2001-12-26 | 狄纳米特诺贝尔爆炸材料和系统技术股份有限公司 | 制备n－烷基－n′－硝基胍的方法 |
-
2017
- 2017-12-08 CN CN201711294005.XA patent/CN107879952A/zh active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4677226A (en) * | 1985-07-29 | 1987-06-30 | American Cyanamid Company | Alkyl-, alkenyl- and alkynylnitroguanidines as cytokinin plant growth regulants |
| CN1328542A (zh) * | 1998-11-25 | 2001-12-26 | 狄纳米特诺贝尔爆炸材料和系统技术股份有限公司 | 制备n－烷基－n′－硝基胍的方法 |
Non-Patent Citations (2)
| Title |
|---|
| YANG SHAOXIANG等: "Design, Synthesis, and Insecticidal Activity of 1,5-Diphenyl-1-pentanone Analogues", 《CHIN. J. CHEM.》 * |
| 郭瑾烨等: "胍基化试剂的制备及其应用", 《新疆大学学报(自然科学版)》 * |
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