CN115417790A - Novel azo foaming agent and synthesis method thereof - Google Patents
Novel azo foaming agent and synthesis method thereof Download PDFInfo
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- CN115417790A CN115417790A CN202211226153.9A CN202211226153A CN115417790A CN 115417790 A CN115417790 A CN 115417790A CN 202211226153 A CN202211226153 A CN 202211226153A CN 115417790 A CN115417790 A CN 115417790A
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- compound
- aminocyclohexane
- carboxylate
- foaming agent
- chlorine
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- 239000004088 foaming agent Substances 0.000 title claims abstract description 32
- 238000001308 synthesis method Methods 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- KRDTUMQGDPZWMF-UHFFFAOYSA-N methyl 1-aminocyclohexane-1-carboxylate Chemical compound COC(=O)C1(N)CCCCC1 KRDTUMQGDPZWMF-UHFFFAOYSA-N 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- -1 azo compound Chemical class 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- HUMMCZRNZCKXHL-UHFFFAOYSA-N 1-aminocyclohexane-1-carbonitrile Chemical compound N#CC1(N)CCCCC1 HUMMCZRNZCKXHL-UHFFFAOYSA-N 0.000 claims description 3
- KUAFMPWKUNNUEC-UHFFFAOYSA-N ethyl 1-aminocyclohexane-1-carboxylate Chemical compound CCOC(=O)C1(N)CCCCC1 KUAFMPWKUNNUEC-UHFFFAOYSA-N 0.000 claims description 3
- XTFPABXREBHJQI-UHFFFAOYSA-N propan-2-yl 1-aminocyclohexane-1-carboxylate Chemical compound CC(C)OC(=O)C1(N)CCCCC1 XTFPABXREBHJQI-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001263 acyl chlorides Chemical group 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000001041 indolyl group Chemical group 0.000 claims description 2
- VLNNACMZTDZCFH-UHFFFAOYSA-N methyl 1-aminocyclopentane-1-carboxylate Chemical compound COC(=O)C1(N)CCCC1 VLNNACMZTDZCFH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004604 Blowing Agent Substances 0.000 claims 1
- 238000005187 foaming Methods 0.000 abstract description 3
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 23
- 238000001228 spectrum Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 238000009413 insulation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- WOXWUZCRWJWTRT-UHFFFAOYSA-N 1-amino-1-cyclohexanecarboxylic acid Chemical compound OC(=O)C1(N)CCCCC1 WOXWUZCRWJWTRT-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- 102100032373 Coiled-coil domain-containing protein 85B Human genes 0.000 description 1
- 101000868814 Homo sapiens Coiled-coil domain-containing protein 85B Proteins 0.000 description 1
- 101000663001 Mus musculus TNFAIP3-interacting protein 1 Proteins 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- KLHVMALYHBTUGK-UHFFFAOYSA-N cyclohexanamine methyl formate Chemical compound COC=O.NC1CCCCC1 KLHVMALYHBTUGK-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/04—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The invention provides a novel azo foaming agent and a synthesis method thereof, and the novel azo foaming agent has a structural general formula shown in a formula I: the azo foaming agent has good foaming performance and does not generate harmful components, the preparation method adopts a direct azo method to synthesize the novel azo foaming agent, the synthesis method is simple and economic, and the azo foaming agent has extremely high application value.
Description
Technical Field
The invention relates to a novel azo foaming agent and a synthesis method thereof, belonging to the technical field of organic chemical synthesis.
Background
The foaming agent is used as an important chemical product, has wide application in the fields of food additives, household and building heat-insulating materials, cold-chain logistics and the like, and has great market demand, so that the synthesis research of the novel foaming agent has important significance.
The foaming agent can be uniformly dispersed in the resin, can be decomposed by heating, and has various excellent performances of heat preservation, heat insulation, sound insulation, shock resistance, light weight, strong elasticity, electric insulation and the like. There are many kinds of foaming agents, and they are mainly classified into organic foaming agents (azo compounds, sulfonyl hydrazide compounds, nitroso compounds, etc.) and inorganic foaming agents (carbonates, water glass, silicon carbide, carbon black, etc.). Among them, azo compounds are used as a large class of organic foaming agents, and there are many kinds of such organic foaming agents, for example, azodicarbonamide (foaming agent AC for short), diisopropyl azodicarboxylate (foaming agent DIPA for short), azobisisobutyronitrile (ABIN for short), and the like, and are widely used in the material fields of PE, PVC, PS, PP, ABS, and the like. The decomposition product of the azo foaming agent is nontoxic, odorless and pollution-free, and the generated bubbles are uniform and compact and can be added into rubber products. Then, the expansion rate of the rubber can be increased by changing the type and the amount of the foaming agent, and the crosslinking density of the vulcanized rubber can be reduced, so that the mechanical property and the like of the rubber product can be improved.
Currently, azo foaming agents are mainly synthesized by condensation and oxidation, the industrial synthesis mode is single, hydrazine compounds are synthesized primarily in the synthesis process, and further the oxidation strategy is adopted, the reaction conditions are severe, and the azo foaming agents have the defects of strong pollution and danger and the like.
In view of the huge market potential of azo foaming agents, the research and development of a novel azo foaming agent and a synthetic method with low cost and simple synthetic mode are urgently needed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a novel azo foaming agent and a synthetic method thereof.
The azo foaming agent has good foaming performance and does not generate harmful components.
The method adopts a direct azo method to synthesize the novel azo foaming agent, has simple and economic synthesis mode and extremely high application value.
The invention is realized by the following technical scheme:
a novel azo foaming agent has a structural general formula shown in a formula I:
in formula I, n =1-13,
r is one of hydrogen, alkyl, alkenyl, aryl, fluorine, chlorine, bromine, iodine, trifluoromethyl, sulfur trifluoromethyl, oxygen trifluoromethyl, carboxyl, ester group, amido, acyl chloride group, sulfonyl, sulfonate group, indolyl and carbazolyl.
Preferred aryl groups according to the invention are substituted phenyl, substituted naphthyl, substituted heteroaromatic rings.
According to the invention, the synthesis method of the novel azo compound comprises the following steps:
dissolving the compound a and alkali in a solvent A, then introducing chlorine, stirring for reaction, extracting by using dichloromethane and water after the reaction is finished, and removing the solvent by reduced pressure distillation to obtain the target compound.
According to the invention, compound a is preferably 1-aminocyclohexane-1-carboxylic acid methyl ester, 1-aminocyclohexane-1-carboxylic acid ethyl ester, 1-aminocyclohexane-1-carboxylic acid isopropyl ester, 1-aminocyclohexane-1-carbonitrile or 1-aminocyclopentane-1-carboxylic acid methyl ester.
Most preferably, compound a is methyl 1-aminocyclohexane-1-carboxylate.
According to the invention, the solvent A is preferably dichloromethane, toluene, acetonitrile, tetrahydrofuran, 1,2-dichloroethane, ethyl acetate, methanol, ethanol or water.
Most preferably, the solvent A is water.
According to the invention, the molar ratio of compound a to chlorine is preferably 1: (1.0-5.0).
Further preferably, the molar ratio of the compound a to chlorine is 1: (2.0-3.0).
Most preferably, the molar ratio of compound a to chlorine is 1.
According to the present invention, preferably, the base is sodium hydroxide, sodium carbonate, pyridine, sodium bicarbonate or triethylamine.
Most preferably, the base is triethylamine.
According to the invention, the molar ratio of compound a to base is preferably 1 (1-5).
Most preferably, the molar ratio of compound a to base is 1:2.
According to the invention, the reaction temperature is preferably from 0 to 50 ℃.
Further preferably, the reaction temperature is 20 to 40 ℃.
Most preferably, the reaction temperature is 25 ℃.
According to the invention, the reaction time is preferably from 1 to 24 hours.
More preferably, the reaction time is 10 to 15 hours.
Most preferably, the reaction time is 12 hours.
The synthetic route of the invention is shown as the following formula II:
the invention has the technical characteristics and advantages that:
1. the invention successfully synthesizes a novel azo foaming agent by adopting a cheap primary amine compound and a direct azo method, and has higher application value; cheap raw materials, low cost, low energy consumption, low equipment requirement and strong industrial production value, and can be carried out at room temperature.
2. Compared with the method for synthesizing the azo foaming agent by initially synthesizing the hydrazine compound and then oxidizing, the method has the advantages of mild reaction conditions (insensitivity to air and water), simple and convenient manufacturing process, larger production profit margin, better environmental friendliness and the like.
3. The novel azo foaming agent synthesized by the invention has better foaming performance, does not generate harmful components, and has great application prospect in materials such as rubber, plastic and the like.
Drawings
FIG. 1 is a drawing showing methyl 1-aminocyclohexane-1-carboxylate obtained in example 1 1 H-NMR spectrum;
FIG. 2 is a drawing showing methyl 1-aminocyclohexane-1-carboxylate obtained in example 1 13 A C-NMR spectrum;
FIG. 3 shows the dimethyl 1,1' - (diazene-1,2-diyl) (E) -bis (cyclohexane-1-carboxylate) ester prepared in example 2 1 H-NMR spectrum;
FIG. 4 shows the dimethyl 1,1' - (diazene-1,2-diyl) (E) -bis (cyclohexane-1-carboxylate) ester prepared in example 2 13 A C-NMR spectrum;
Detailed Description
The present invention is further illustrated by, but not limited to, the following specific examples.
Example 1
Preparation of 1-aminocyclohexane-1-carboxylic acid methyl ester:
thionyl chloride (40mmol, 2.9mL) was added to a solution of 1-amino-1-cyclohexanecarboxylic acid (20mmol, 2.86g) in methanol (50 mL), the reaction was stirred at 25 ℃ for 12 hours, after completion of the reaction, the solvent and excess thionyl chloride were removed by evaporation concentration, and the organic phase was concentrated by extraction with dichloromethane and saturated sodium bicarbonate solution to give the compound methyl 1-aminocyclohexane-1-carboxylate as a pale yellow oil with a yield of 95%. The synthetic route is shown as the following formula III.
Process for preparing methyl 1-aminocyclohexane-1-carboxylate 1 The H-NMR spectrum is shown in figure 1, 13 the C-NMR spectrum is shown in FIG. 2.
Nuclear magnetic data:
1 H NMR(500MHz,CDCl 3 ):δ3.68(s,3H),1.89(t,J＝9.5Hz,2H),1.66–1.57(m,2H),1.52(s,2H),1.48–1.40(m,5H),1.36(td,J＝10.3,9.0,2.9Hz,1H)；
13 C NMR(126MHz,CDCl 3 ):δ177.9,57.4,52.1,35.5,25.5,22.0。
example 2
Synthesis of 1,1' - (diazene-1,2-diyl) (E) -bis (cyclohexane-1-carboxylate) dimethyl ester
Chlorine (50 mmol) is introduced into 1-aminocyclohexane-1-methyl formate (20mmol, 3.14g) and triethylamine (40mmol, 5.6mL) in water (20 mL), the stirring reaction is carried out for 12 hours at 25 ℃, after the reaction is finished, dichloromethane and water are used for extraction, and an organic phase is concentrated to obtain a compound 1,1' - (diazene-1,2-diyl) (E) -bis (cyclohexane-1-carboxylate) dimethyl ester which is a white solid, wherein the yield is 80%, and the synthetic route is shown in the following formula IV.
Preparation of the compound 1,1' - (diazene-1,2-diyl) (E) -bis (cyclohexane-1-carboxylate) dimethyl ester 1 The H-NMR spectrum is shown in figure 3, 13 the C-NMR spectrum is shown in FIG. 4.
Nuclear magnetic data:
1 H NMR(500MHz,CDCl 3 ):δ3.64(s,6H),2.04–1.92(m,8H),1.67–1.61(m,4H),1.54–1.39(m,8H)；
13 C NMR(126MHz,CDCl 3 ):δ172.6,79.4,51.8,32.0,25.3,22.3。
example 3
The preparation method is the same as that described in example 2, except that:
1-aminocyclohexane-1-carboxylic acid methyl ester was replaced with 1-aminocyclohexane-1-carboxylic acid ethyl ester, and the other parameters and conditions were as in example 2.
Example 4
The preparation method is the same as that described in example 2, except that:
1-aminocyclohexane-1-carboxylic acid methyl ester was replaced with 1-aminocyclohexane-1-carboxylic acid isopropyl ester, the other parameters and conditions were as in example 2.
Example 5
The preparation method is the same as that described in example 2, except that:
1-aminocyclohexane-1-carboxylic acid methyl ester was replaced with 1-aminocyclohexane-1-carbonitrile, and the other parameters and conditions were carried out as in example 2.
Claims (10)
1. A novel azo foaming agent has a structural general formula shown in a formula I:
in formula I, n =1-13,
r is one of hydrogen, alkyl, alkenyl, aryl, fluorine, chlorine, bromine, iodine, trifluoromethyl, sulfur trifluoromethyl, oxygen trifluoromethyl, carboxyl, ester group, amido, acyl chloride group, sulfonyl, sulfonate group, indolyl and carbazolyl.
2. The novel azo blowing agent of claim 1, wherein the aryl group is a substituted phenyl, substituted naphthyl, or substituted aromatic heterocycle.
3. The process for synthesizing the novel azo compound according to claim 1, comprising the steps of:
dissolving the compound a and alkali in a solvent A, then introducing chlorine, stirring for reaction, after the reaction is finished, extracting by adopting dichloromethane and water, and removing the solvent by reduced pressure distillation to obtain the target compound.
4. The process according to claim 3, wherein the compound a is methyl 1-aminocyclohexane-1-carboxylate, ethyl 1-aminocyclohexane-1-carboxylate, isopropyl 1-aminocyclohexane-1-carboxylate, 1-aminocyclohexane-1-carbonitrile or methyl 1-aminocyclopentane-1-carboxylate, preferably the compound a is methyl 1-aminocyclohexane-1-carboxylate.
5. The method according to claim 3, wherein the solvent A is dichloromethane, toluene, acetonitrile, tetrahydrofuran, 1,2-dichloroethane, ethyl acetate, methanol, ethanol or water, preferably, the solvent A is water.
6. The process according to claim 3, wherein the molar ratio of compound a to chlorine is 1: (1.0-5.0).
7. The process according to claim 3, wherein the molar ratio of compound a to chlorine is 1: (2.0-3.0).
8. The process according to claim 3, wherein the molar ratio of compound a to chlorine is 1:2.5.
9. the preparation method according to claim 3, wherein the base is sodium hydroxide, sodium carbonate, pyridine, sodium bicarbonate or triethylamine, the molar ratio of the compound a to the base is 1 (1-5), the reaction temperature is 0-50 ℃, and the reaction time is 1-24 hours.
10. The preparation method of claim 3, wherein the base is triethylamine, the molar ratio of the compound a to the base is 1 (2), the reaction temperature is 20-40 ℃, and the reaction time is 10-15 hours.
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