CN107892660A - 1 nitrine acetoxyl group, the 2,2 two-fold azido propane compounds of N-methyl 3 - Google Patents

1 nitrine acetoxyl group, the 2,2 two-fold azido propane compounds of N-methyl 3 Download PDF

Info

Publication number
CN107892660A
CN107892660A CN201711294827.8A CN201711294827A CN107892660A CN 107892660 A CN107892660 A CN 107892660A CN 201711294827 A CN201711294827 A CN 201711294827A CN 107892660 A CN107892660 A CN 107892660A
Authority
CN
China
Prior art keywords
nitrine
fold
methyl
acetoxyl group
azidos
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201711294827.8A
Other languages
Chinese (zh)
Inventor
刘亚静
姜菡雨
汪营磊
姬月萍
莫洪昌
闫峥峰
陈斌
卢先明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian Modern Chemistry Research Institute
Original Assignee
Xian Modern Chemistry Research Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xian Modern Chemistry Research Institute filed Critical Xian Modern Chemistry Research Institute
Priority to CN201711294827.8A priority Critical patent/CN107892660A/en
Publication of CN107892660A publication Critical patent/CN107892660A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C247/00—Compounds containing azido groups
    • C07C247/02—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton
    • C07C247/12—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton being further substituted by carboxyl groups

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of 1 nitrine acetoxyl group 2, the 2 two-fold azido propane compounds of N-methyl 3, its structural formula is such as shown in (I)：

Description

Two-fold N-methyl -3- azidos the propane compounds of 1- nitrine acetoxyl groups -2,2-
Technical field
The present invention relates to a kind of two-fold N-methyl -3- azidos propane compounds of 1- nitrine acetoxyl group -2,2-, belong to and contain Can Material Field.
Background technology
Energetic plasticiser is one of indispensable major function auxiliary agent in explosive wastewater product, and it is fried that its application can expand fire The use temperature range of medicine product, horizontal integral energy, improvement processing technology are improved, improves cryogenic mechanics performance, substantially reduce Its vulnerability.Organic azide is a kind of excellent energetic material, be widely used in energetic binder, energetic plasticiser, All many-sides such as oxidant, it is the important channel for the energy level and technical performance for improving energetic material.Such as 2005, Unkelbach, G. etc. are in article《Synthesis and Characterization of new triazido- plasticizers》Disclosed in two-fold N-methyl -3- azidos propane (TAP-Ac) compounds of 1- acetoxyl groups -2,2- knot The performance of structure and the compound, its structure is such as shown in (I)：
The compound density is 1.244g/cm3, nitrogen content 49.80%, enthalpy of formation 595.36KJ/mol.The compound Nitrogen content is not up to 50%, and nitrogen content is not high, and the enthalpy of formation is not high.
The content of the invention
The technical problems to be solved by the invention are in view of the shortcomings of the prior art, there is provided a kind of nitrogen content and the enthalpy of formation compared with The high two-fold N-methyl -3- azidos propane compounds of 1- nitrine acetoxyl groups -2,2-.
The synthetic route of the two-fold N-methyl -3- azidos propane compounds of 1- nitrine acetoxyl groups -2,2- of the present invention：
Using dimethyl sulfoxide (DMSO) as solvent, tribromoneoamyl alcohol and reaction of sodium azide generate three nitrine neopentyl alcohols, then, first For benzene as solvent, p-methyl benzenesulfonic acid is catalyst, and esterification generation 1- nitrine second occurs for three nitrine neopentyl alcohols and nitrine acetic acid Two-fold N-methyl -3- azidos the propane of acyloxy -2,2-.
Two-fold N-methyl -3- azidos the propane compounds of 1- nitrine acetoxyl groups -2,2- of the present invention, its structural formula is such as (II) shown in：
The synthetic method of the two-fold N-methyl -3- azidos propane of 1- nitrine acetoxyl groups -2,2- of the present invention, including it is following Step：
The synthesis of (1) three nitrine neopentyl alcohol
Under stirring, in 20 DEG C~25 DEG C of temperature, tribromoneoamyl alcohol is added in dimethyl sulfoxide (DMSO), then portioning adds NaN3, after reacting 10h~15h, react and extracted through dichloromethane, repeatedly obtain three nitrine neopentyl alcohols after washing, reclaim reagent.Tribromo Neopentyl alcohol and NaN3Mol ratio is 1:3~3.9.
(2) synthesis of the two-fold N-methyl -3- azidos propane of 1- nitrine acetoxyl group -2,2-
Under stirring, in 25 DEG C~30 DEG C of temperature, three nitrine neopentyl alcohols are added in toluene, stir lower addition nitrine second Acid, p-methyl benzenesulfonic acid, back flow reaction 12h~15h, room temperature is naturally cooled to, be repeatedly washed to neutrality, be evaporated under reduced pressure and remove first Benzene, obtain the two-fold N-methyl -3- azidos propane of 1- nitrine acetoxyl groups -2,2-.Three nitrine neopentyl alcohols and nitrine acetic acid mol ratio For 1:1~1.4.
Advantages of the present invention：Two-fold N-methyl -3- azidos the propane compounds of 1- nitrine acetoxyl groups -2,2- of the present invention Nitrogen content it is higher, be 57.14%, and the nitrogen content of the TAP-Ac compounds of documents be 49.80%；1- nitrine acetyl oxygen The carbon content of the two-fold N-methyl -3- azidos propane compounds of base -2,2- is relatively low, is 28.57%, and the TAP-Ac of documents The carbon content of compound is 33.20%；The life of the two-fold N-methyl -3- azidos propane compounds of 1- nitrine acetoxyl groups -2,2- Cheng Han is higher, is 984.9KJ/mol, and the enthalpy of formation of the TAP-Ac compounds of documents is 595.36KJ/mol；The present invention It is esterified after synthetic method elder generation Azide, avoids steric effect caused by Azide after first esterification, reaction condition is gentle, and reaction is received Rate is higher.
Embodiment
The present invention is described in further detail with reference to embodiments.It should be noted that these embodiments are more excellent Example, be mainly used in understanding the present invention, but the invention is not restricted to these embodiments.
Embodiment 1：
The synthesis of (1) three nitrine neopentyl alcohol
Under stirring, in 20 DEG C~25 DEG C of temperature, 9.75g (0.03mol) tribromoneoamyl alcohol is added to 50mL dimethyl Asia In sulfone, then portioning adds 6.4g (0.1mol) NaN3, after 85 DEG C~90 DEG C are reacted 15h, react and extracted through dichloromethane, repeatedly Three nitrine neopentyl alcohol 5.8g, yield 91.6% are obtained after washing, reclaim reagent.
Structural Identification：
Infrared spectrum：IR(KBr,cm-1),υ:3466,1046(-OH),2937,2873(-CH2),2103(-N3)。
Nuclear magnetic spectrum：1HNMR(CDCl3,500Hz)δ:3.55(2H,s,CH2),3.38(6H,s,3CH2), 1.60 (1H, s, OH)。
13C NMR(CDCl3,125Hz)δ:62.2(C),51.6(CH2N3),44.7(CH2O)。
It is strictly three nitrine neopentyl alcohols that said structure appraising datum, which confirms to obtain material,.
(2) synthesis of the two-fold N-methyl -3- azidos propane of 1- nitrine acetoxyl group -2,2-
Under stirring, in 25 DEG C~30 DEG C of temperature, the nitrine neopentyl alcohols of 1g (4.7mmol) three are added in 20mL toluene, stirred Mix lower addition 0.51g (5.2mmol) nitrine acetic acid, 0.05g p-methyl benzenesulfonic acid, 105 DEG C~110 DEG C back flow reaction 10h are naturally cold But to room temperature, neutrality is repeatedly washed to, is evaporated under reduced pressure and removes toluene, obtain the two-fold N-methyl -3- of 1- nitrine acetoxyl groups -2,2- and fold Nitrogen base propane 1.2g, yield 86%.
Structural Identification：
Infrared spectrum：IR(KBr,cm-1),υ:2935,2873(-CH2),2103,(-N3), 1752 (C=O), 1189, 1017(COC),554(C-N)。
Nuclear magnetic spectrum：1H NMR(CDCl3,500Hz)δ:4.12(2H,s,CH2),3.93(2H,s,CH2N3),3.40(6H, s,3CH2)。13C NMR(CDCl3,125Hz)δ:167.6 (C=O), 64.3 (C), 51.6 (3CH2N3),50.41(CH2N3),43.4 (CH2O)。
Elementary analysis：Molecular formula C7H10O2N12
Theoretical value (%)：C 28.57,H 3.401,N 57.14
Measured value (%)：C 28.08,H 3.344,N 57.02；
It is strictly that the two-fold N-methyl -3- of 1- nitrine acetoxyl group -2,2- are folded that said structure appraising datum, which confirms to obtain material, Nitrogen base propane.
Embodiment 2：
The synthesis of (1) three nitrine neopentyl alcohol
Under stirring, in 20 DEG C~25 DEG C of temperature, 10.0g (0.031mol) tribromoneoamyl alcohol is added to 60mL dimethyl Asia In sulfone, then portioning adds 7.88g (0.12mol) NaN3, after 85 DEG C~90 DEG C are reacted 12h, react and extracted through dichloromethane, it is more Three nitrine neopentyl alcohol 5.75g, yield 90.8% are obtained after secondary washing, reclaim reagent.
(2) synthesis of the two-fold N-methyl -3- azidos propane of 1- nitrine acetoxyl group -2,2-
Under stirring, in 25 DEG C~30 DEG C of temperature, the nitrine neopentyl alcohols of 1g (4.7mmol) three are added in 20mL toluene, stirred Mix lower addition 0.56g (5.7mmol) nitrine acetic acid, 0.05g p-methyl benzenesulfonic acid, 105 DEG C~110 DEG C back flow reaction 15h are naturally cold But to room temperature, neutrality is repeatedly washed to, is evaporated under reduced pressure and removes toluene, obtain the two-fold N-methyl -3- of 1- nitrine acetoxyl groups -2,2- and fold Nitrogen base propane 1.12g, yield 80.3%.
The nitrogen content of the two-fold N-methyl -3- azidos propane compounds of 1- nitrine acetoxyl groups -2,2- of the present invention and life Calculated into enthalpy：
(1) nitrogen content
Two-fold N-methyl -3- azidos propane compounds molecular formula the C of 1- nitrine acetoxyl groups -2,2-7H10O2N12, according to member It is 57.02% that element analysis, which measures its nitrogen content, theoretical value 57.14%.
(2) enthalpy of formation
The two-fold n-formyl sarcolysine of 1- nitrine acetoxyl group -2,2- is calculated using DFT method B3LYP/6-311++G (d, p) The enthalpy of formation of base -3- azido propane compounds is 984.9KJ/mol.

Claims (1)

1. a kind of two-fold N-methyl -3- azidos propane compounds of 1- nitrine acetoxyl group -2,2-, its structural formula is such as shown in (I)：
CN201711294827.8A 2017-12-08 2017-12-08 1 nitrine acetoxyl group, the 2,2 two-fold azido propane compounds of N-methyl 3 Pending CN107892660A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711294827.8A CN107892660A (en) 2017-12-08 2017-12-08 1 nitrine acetoxyl group, the 2,2 two-fold azido propane compounds of N-methyl 3

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711294827.8A CN107892660A (en) 2017-12-08 2017-12-08 1 nitrine acetoxyl group, the 2,2 two-fold azido propane compounds of N-methyl 3

Publications (1)

Publication Number Publication Date
CN107892660A true CN107892660A (en) 2018-04-10

Family

ID=61807723

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711294827.8A Pending CN107892660A (en) 2017-12-08 2017-12-08 1 nitrine acetoxyl group, the 2,2 two-fold azido propane compounds of N-methyl 3

Country Status (1)

Country Link
CN (1) CN107892660A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109293527A (en) * 2018-09-19 2019-02-01 湖州练市飞迪电器塑料有限公司 A kind of synthetic method of plasticizer DAMNP

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105358146A (en) * 2013-03-08 2016-02-24 波利艾克蒂瓦有限公司 Polymer conjugate for delivery of a bioactive agent

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105358146A (en) * 2013-03-08 2016-02-24 波利艾克蒂瓦有限公司 Polymer conjugate for delivery of a bioactive agent

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
CHANDRA SHEKHAR PANT: "Synthesis and Characterization of Two Potential Energetic Azido Esters", 《PROPELLANTS, EXPLOSIVES, PYROTECHNICS》 *
KAVITA GHOSH: "Studies on Triple Base Gun Propellant Based on Two Energetic Azido Esters", 《JOURNAL OF ENERGETIC MATERIALS》 *
NARGES ZOHARI ETAL: "A novel simple correlation for predicting glass transition temperature of energetic azido-ester plasticizers through molecular structures", 《J THERM ANAL CALORIM》 *
UNKELBACH G ETAL: "Synthesis and characterization of new triazido-plasticizers", 《 IN 36TH INTERNATIONAL ANNUAL CONFERENCE ICT》 *
姬月萍等: "1, 1 , 1-三叠氮甲基乙烷合成与性能研究", 《含能材料》 *
杨俊清等: "1，3-二叠氮乙酰氧基-2，2-二叠氮甲基丙烷( PEAA)的结构、性能与热分解机理的理论研究", 《爆破器材》 *
欧育湘: "《化学工程与技术 炸药学》", 31 December 2006 *
田德余: "《固体推进剂配方优化设计》", 31 December 2013 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109293527A (en) * 2018-09-19 2019-02-01 湖州练市飞迪电器塑料有限公司 A kind of synthetic method of plasticizer DAMNP

Similar Documents

Publication Publication Date Title
CN108002988B (en) Preparation method of 1, 2-di (2- (2, 6-dimethoxyphenoxy) ethoxy) ethane
CN110240568A (en) Three replace pyridazine analog derivative and preparation method thereof
CN113072436A (en) Preparation method of benzyl aryl ether
CN105130885B (en) A kind of aromatic diamines and its synthetic method containing bipyridyl structure
CN107892660A (en) 1 nitrine acetoxyl group, the 2,2 two-fold azido propane compounds of N-methyl 3
CN113024358A (en) Method for catalytically synthesizing phenyl diether fluorene by ethylene oxide
CN112358454A (en) Preparation method of 4, 5-dihydroisoxazole derivative
CN111995520A (en) Synthetic method of 4-formyl-2- (trifluoromethyl) benzoic acid
CN111138285A (en) Method for synthesizing organic carbonate from carbon dioxide, alcohol and brominated alkanes under mild condition
CN102531970B (en) Carbohydrazide and fast synthesis method thereof
CN113620968A (en) Rigid bio-based diol monomer with cyclic acetal structure, and preparation method and application thereof
BR102018002942B1 (en) method for preparing azoxystrobin
CN109824501B (en) Aryl iodine compound containing carboxydifluoro methylene at ortho position and preparation method thereof
Liu et al. A general and efficient method for synthesis of enaminones and enamino esters catalyzed by NbCl 5 under solvent-free conditions
CN108727179B (en) Synthetic method of alpha-allyl substituted alpha, beta-unsaturated ketone, ester or nitrile compound
CN108117668B (en) Flame retardant containing melamine structure, preparation method and application thereof
Jin et al. A contribution to the study of the modified Marschalk reaction: Hydroxymethylation of 6, 8-O-dimethyl emodin
CN105085263B (en) Preparation method and intermediate of 2-alkylacylmethyl-1,4-succinic acid derivative
CN110938015B (en) Preparation method of azido-substituted salicylic acid derivative
CN106631842A (en) Synthetic method for N-substituent-3-aminoacrolein
CN113372200B (en) Preparation method of 2-bromo-6-fluoroanisole
CN113548948B (en) Preparation method of methyl octabromoether
CN114195832B (en) Fluorinating agent for dichloro sulfonyl imine fluorination reaction, preparation method and application thereof
JP5178098B2 (en) Alicyclic vinyl ether compounds
CN115947705B (en) Method for preparing 1-nitrodibenzofuran by using ligand and o-bromophenol as raw materials

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20180410

RJ01 Rejection of invention patent application after publication