CN1775358A - Zinc cyclohexanebutyrate is used for the preparation of N-substituted carbamate - Google Patents
Zinc cyclohexanebutyrate is used for the preparation of N-substituted carbamate Download PDFInfo
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- CN1775358A CN1775358A CN 200510048150 CN200510048150A CN1775358A CN 1775358 A CN1775358 A CN 1775358A CN 200510048150 CN200510048150 CN 200510048150 CN 200510048150 A CN200510048150 A CN 200510048150A CN 1775358 A CN1775358 A CN 1775358A
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- carbonate
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- cyclohexanebutyrate
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- 150000004657 carbamic acid derivatives Chemical class 0.000 title claims abstract description 16
- KVSXXOUZYJZCPY-UHFFFAOYSA-L zinc;4-cyclohexylbutanoate Chemical compound [Zn+2].[O-]C(=O)CCCC1CCCCC1.[O-]C(=O)CCCC1CCCCC1 KVSXXOUZYJZCPY-UHFFFAOYSA-L 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- -1 amino compound Chemical class 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- 150000005677 organic carbonates Chemical class 0.000 claims abstract description 11
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- GJGOEGDBGIUFRH-UHFFFAOYSA-L zinc;4-cyclohexylbutanoate;dihydrate Chemical group O.O.[Zn+2].[O-]C(=O)CCCC1CCCCC1.[O-]C(=O)CCCC1CCCCC1 GJGOEGDBGIUFRH-UHFFFAOYSA-L 0.000 claims description 3
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical compound C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 claims description 2
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 claims description 2
- OHKOAJUTRVTYSW-UHFFFAOYSA-N 2-[(2-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC=C1CC1=CC=CC=C1N OHKOAJUTRVTYSW-UHFFFAOYSA-N 0.000 claims description 2
- UTNMPUFESIRPQP-UHFFFAOYSA-N 2-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC=C1N UTNMPUFESIRPQP-UHFFFAOYSA-N 0.000 claims description 2
- SDYWXFYBZPNOFX-UHFFFAOYSA-N 3,4-dichloroaniline Chemical compound NC1=CC=C(Cl)C(Cl)=C1 SDYWXFYBZPNOFX-UHFFFAOYSA-N 0.000 claims description 2
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 claims description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- XTBFPVLHGVYOQH-UHFFFAOYSA-N methyl phenyl carbonate Chemical compound COC(=O)OC1=CC=CC=C1 XTBFPVLHGVYOQH-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- OARQUKGJHSXVJI-UHFFFAOYSA-L zinc;butanoate;cyclohexane Chemical compound [Zn+2].CCCC([O-])=O.CCCC([O-])=O.C1CCCCC1 OARQUKGJHSXVJI-UHFFFAOYSA-L 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 6
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 5
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- HJOVHMDZYOCNQW-UHFFFAOYSA-N Isophorone Natural products CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000007083 alkoxycarbonylation reaction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- TZIHFWKZFHZASV-UHFFFAOYSA-N anhydrous methyl formate Natural products COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical class OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- IFNXAMCERSVZCV-UHFFFAOYSA-L zinc;2-ethylhexanoate Chemical compound [Zn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O IFNXAMCERSVZCV-UHFFFAOYSA-L 0.000 description 1
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 description 1
- XDWXRAYGALQIFG-UHFFFAOYSA-L zinc;propanoate Chemical compound [Zn+2].CCC([O-])=O.CCC([O-])=O XDWXRAYGALQIFG-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种环己烷丁酸锌用于制备N－取代氨基甲酸酯的方法是将环己烷丁酸锌催化剂、氨基化合物与有机碳酸酯混合，其加入量为按氨基化合物∶有机碳酸酯摩尔比为10～40∶1，环己烷丁酸锌催化剂∶氨基化合物的质量比为0.05～0.5∶1，在反应温度为90～200℃；反应压力为0.2～1.0MPa条件下反应2～12小时。本发明具有该催化剂为化工产品，易于购得，催化剂活性高，用量少，目的产物选择性好的优点。A kind of method that zinc cyclohexanebutyrate is used for preparing N-substituted carbamate is that zinc cyclohexanebutyrate catalyst, amino compound and organic carbonate are mixed, and its addition is amino compound: organic carbonate mole The ratio is 10-40:1, the mass ratio of zinc cyclohexanebutyrate catalyst: amino compound is 0.05-0.5:1, and the reaction temperature is 90-200°C; the reaction pressure is 0.2-1.0MPa and the reaction is 2-12 Hour. The invention has the advantages that the catalyst is a chemical product, is easy to purchase, has high catalyst activity, less consumption and good selectivity of the target product.
Description
Technical Field
The invention belongs to a method for preparing N-substituted carbamate, and particularly relates to a method for preparing N-substituted carbamate by using zinc cyclohexanebutyrate.
Background
The N-substituted carbamate is a very important organic intermediate, can be widely used for synthesizing agricultural chemicals, dyes, medicines, urea compounds and corresponding various isocyanate products, and can also be used as a protecting group of amino in various organic synthesis processes. Industrially, N-substituted carbamates are usually prepared by reacting alcohols with isocyanates or amines with chloroformates, which are obtained by reacting highly toxic phosgene with the corresponding amines or the corresponding hydroxyl compounds. It can be said that the current industrial process for preparing N-substituted carbamates is actually an indirect phosgene process. With the knowledge of the relationship between resources, environment and sustainable development in all world, people are strongly demanding to establish a clean production-ecological economy new process which is friendly to the environment so that the human society can develop healthily and continuously. The use of highly toxic phosgene clearly contradicts this theme. The method for preparing the N-substituted carbamate by using the green nontoxic or low toxic organic carbonate as the alkoxy carbonylation reagent to react with the amino compound is a feasible process route for preparing the N-substituted carbamate without phosgene.
In the preparation of N-substituted carbamates by reacting aromatic amines with organic carbonates, U.S. Pat. No. 3,763,217 proposes the use of AlCl3、FeCl3、UO2(NO)2When Lewis acid is used as a catalyst for the reaction, the yield of the corresponding N-substituted carbamate is about 20 percent under the reflux condition. U.S. Pat. No. 4,268,683 proposes the use of zinc salts of organic acids having pKa values greater than 2.8, such as zinc acetate, zinc propionate, and naphthaleneThe zinc salt is used as the catalyst of the reaction, so that the yield of the mono-N-substituted carbamate can reach about 70 percent, but the catalytic effect on diamino derivatives of aromatic hydrocarbon is poor, and the yield of the di-N-substituted carbamate is about 18 to 36 percent. U.S. Pat. No. 4,268,684 proposes the use of anhydrous or dihydrate zinc acetate in the preparation of 4, 4 '-methylenediphenyl di-N-substituted carbamate (MDC) by reaction of 4, 4' -Methylenedianiline (MDA) with dimethyl carbonate, with a conversion of MDA of more than 99% and a selectivity of MDC of more than 97% after 1.5 hours at 140 ℃, and U.S. Pat. No. 5,688,988 proposes the use of basic carbonates of Zn or Cu as catalyst, with a selectivity of MDC of 98% and a yield of MDC of 97.5% by reacting MDA with DMC for 6 hours at 180 ℃ under 4.5 atm. In the process of preparing isophorone diisocyanate (IPDI), U.S. Pat. No. 5,789,614 use sodium methoxide as a catalyst, isophorone diamine (IPDA) and dimethyl carbonate react at 70 ℃ for 3 hours, and the yield of isophorone diamino methyl formate (IPDC) is 99.5%. However, the reaction is carried out under anhydrous conditions, since water deactivates the catalyst. Pat.5,698,731 uses NxOy(OCONR’)zThe catalyst of the form wherein x 1-4 is an integer, y is an integer of 0-1, z is an integer of 1-6, R' represents C1～C12Straight or branched alkyl or C5～C7Cycloalkyl or aralkyl radicals for catalysing the reaction of TDA with MDA and conversion of the corresponding 2, 4-diaminotolueneThe ratio is 79-99%, and the selectivity of 2, 4-toluene dicarbamate is 63-99%. WO98/55450 supports zinc organic acid such as zinc acetate and zinc 2-ethylhexanoate on TiO2，Al2O3Or SiO2And (3) catalyzing MDA and DMC to react at 180 ℃ on an inert carrier (the weight percentage of zinc is 6 wt%), converting MDA 100% after 2 hours, and enabling the selectivity of MDC to reach 96.3%.
One disadvantage of the above catalysts is that the selectivity of the desired product during the reaction is not very good and that the catalytic activity of some catalysts is limited by the type of amino compound.
Disclosure of Invention
The invention aims to provide a method for preparing aryl carbamate by using zinc cyclohexanebutyrate with wide application range and good catalytic activity in the reaction of amino compounds and organic carbonates.
The zinc cyclohexanebutyrate catalyst used in the present invention comprises zinc cyclohexanebutyrate dihydrate or anhydrous zinc cyclohexanebutyrate
The catalyst of the present invention is suitable for the following reactions:
mixing the catalyst, the amino compound and the organic carbonate, wherein the adding amount is as follows: the mol ratio of the organic carbonate is 10-40: 1, the mass ratio of the catalyst to the amino compound is 0.05-0.5: 1, and the reaction temperature is 90-200 ℃; the reaction is carried out under the condition that the reaction pressure is 0.2-1.0 Mpa for 2-12 hours.
The amino compounds mentioned above are: and amino compounds such as hexamethylenediamine, octylamine, aniline, 4-chloroaniline, p-toluidine, 2, 4 ' -diamino-diphenylmethane, 3, 4-dichloroaniline, 2, 2 ' -diamino-diphenylmethane, 4 ' -diamino-diphenylmethane, 1, 5-naphthalene-diamine, 1, 8-naphthalene-diamine, 2, 6-dinaphthylamine, 2, 4-toluenediamine, 2, 6-toluenediamine, and polyaminopolyphenyl methane.
The organic carbonates as mentioned above are: carbonate compounds such as ethylene carbonate, dimethyl carbonate, propylene carbonate, diethyl carbonate, diphenyl carbonate, methylphenyl carbonate, dipropyl carbonate, and dibutyl carbonate.
The invention has the following advantages:
1) the catalyst is a chemical product and is easy to purchase.
2) The catalyst has high activity, less consumption and good selectivity of target products.
Detailed Description
Example 1:
in an 80ml autoclave, 10g of 4, 4' -diamino-diphenylmethane (50.5mmol), 45.5g (505mmol) of dimethyl carbonate and 0.1g of anhydrous zinc cyclohexanebutyrate catalyst were charged, the atmosphere in the autoclave was replaced with high-purity nitrogen gas for 5 minutes, and then the temperature was raised to 90 ℃ with stirring, the pressure in the autoclave was adjusted to 0.2MPa with nitrogen gas, and the reaction was carried out for 12 hours. After the reaction, the excess dimethyl carbonate was distilled off, then N, N-Dimethylformamide (DMF) was added to the residue to dissolve the reaction product, the catalyst was removed by filtration, and analysis was performed by high performance liquid chromatography, and the conversion of 4, 4' -diamino-diphenylmethane was 100%, and the selectivity of the corresponding aryl carbamate was 99.75%.
Example 2
The amounts of the starting materials and the catalyst charged were the same as in example 1, and the conversion of 4, 4' -diamino-diphenylmethane was 100% and the selectivity for the corresponding aryl carbamate was 99.31% at 145 ℃ and 0.5MPa for 6 hours of the reaction.
Example 3
The amounts of the starting materials and the catalyst charged were the same as in example 1, and the conversion of 4, 4' -diamino-diphenylmethane was 100% and the selectivity for the corresponding aryl carbamate was 95.82% at 200 ℃ and 1MPa for 2 hours.
Example 4
5g of 1, 5-naphthalenediamine (31.6mmol), 56.88g (632mmol) of dimethyl carbonate and 1.27g of zinc cyclohexanebutyrate dihydrate catalyst were charged into an 80-ml autoclave, the temperature was raised to 160 ℃ and the pressure in the autoclave was adjusted to 0.8MPa with nitrogen gas, and the reaction was carried out for 5 hours with a conversion of 1, 5-naphthalenediamine of 100% and a selectivity of the corresponding arylcarbamate of 99.03%.
Example 5
2.5g of 1, 5-naphthalenediamine (15.8mmol), 56.88g (632mol) of dimethyl carbonate and 1.27g of a catalyst were charged into an 80ml autoclave, the temperature was raised to 160 ℃ and the pressure in the autoclave was adjusted to 1MPa with nitrogen gas, and the reaction was carried out for 2 hours with a conversion of 1, 5-naphthalenediamine of 100% and a selectivity of the corresponding aryl carbamate of 99.01%.
Example 6
10g of aniline (107.5mmol), 19.35g (215mol) of dimethyl carbonate and 5g of anhydrous zinc cyclohexanebutyrate catalyst are added into an 80ml autoclave, the temperature is raised to 120 ℃, the pressure in the autoclave is adjusted to 0.4MPa by nitrogen, the reaction is carried out for 8 hours, the conversion rate of the aniline is 100 percent, and the selectivity of the corresponding aryl carbamate is 99.68 percent.
Example 7
2.5g of 2, 4-toluenediamine (20.49mmol), 55.32g (614.67mmol) of dimethyl carbonate and 0.5g of a catalyst were charged into an 80ml autoclave, the atmosphere in the autoclave was replaced with high-purity nitrogen for 5 minutes, and then the temperature was raised to 170 ℃ with stirring, and the pressure in the autoclave was adjusted to 0.9MPa with nitrogen, and the reaction was carried out for 4 hours. After the reaction, the excess dimethyl carbonate was distilled off, then N, N-Dimethylformamide (DMF) was added to the residue to dissolve the reaction product, the catalyst was removed by filtration, and the conversion of 2, 4-toluenediamine was 100% and the selectivity of the corresponding aryl carbamate was 98.49% by high performance liquid chromatography.
Claims (3)
1. A method for preparing N-substituted carbamate by using zinc cyclohexanebutyrate, which is characterized by comprising the following steps:
mixing zinc cyclohexanebutyrate catalyst, an amino compound and an organic carbonate in the following amounts: the organic carbonate molar ratio is 10-40: 1, and the cyclohexane zinc butyrate catalyst is: the mass ratio of the amino compound is 0.05-0.5: 1, and the reaction temperature is 90-200 ℃; the reaction is carried out under the condition that the reaction pressure is 0.2-1.0 Mpa for 2-12 hours.
2. The method of claim 1, wherein the zinc cyclohexanebutyrate is zinc cyclohexanebutyrate dihydrate or anhydrous.
3. The method for producing N-substituted carbamic acid ester using zinc cyclohexanobutyrate according to claim 1, wherein the amino compound is hexamethylenediamine, octylamine, aniline, 4-chloroaniline, p-toluidine, 2, 4 ' -diamino-diphenylmethane, 3, 4-dichloroaniline, 2, 2 ' -diamino-diphenylmethane, 4 ' -diamino-diphenylmethane-1, 5-naphthalene-diamine, 1, 8-naphthalene diamine, 2, 6-dinaphthylamine, 2, 4-toluene diamine, 2, 6-toluene diamine or polyaminopolyphenyl methane. 4. The method according to claim 1, wherein the organic carbonate is ethylene carbonate, dimethyl carbonate, propylene carbonate, diethyl carbonate, diphenyl carbonate, methylphenyl carbonate, dipropyl carbonate or dibutyl carbonate.
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| CNB2005100481500A CN100369671C (en) | 2005-12-01 | 2005-12-01 | Zinc cyclohexanebutyrate is used for the preparation of N-substituted carbamate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786967A (en) * | 2010-03-22 | 2010-07-28 | 哈尔滨理工大学 | Method for auxiliary synthesis of 4,4'-diphenyl methane diamino acid methyl ester by microwave |
| CN102131770B (en) * | 2008-08-22 | 2014-08-06 | 巴斯夫欧洲公司 | Method for producing urethanes composed of di-functional aromatic amines and dialkyl carbonates |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU8211798A (en) * | 1997-06-09 | 1998-12-30 | Huntsman Ici Chemicals Llc | Process for the production of organic isocyanates |
| US6133473A (en) * | 1998-06-25 | 2000-10-17 | Rohm And Haas Company | Synthesis of carbamate compounds |
| US7232924B2 (en) * | 2001-06-11 | 2007-06-19 | Xenoport, Inc. | Methods for synthesis of acyloxyalkyl derivatives of GABA analogs |
| JP4107845B2 (en) * | 2002-01-24 | 2008-06-25 | 三井化学ポリウレタン株式会社 | Method for producing alkyl carbamate |
| CN1176065C (en) * | 2003-01-26 | 2004-11-17 | 河北工业大学 | The synthetic method of methyl 1,5-naphthalene dicarbamate |
| CN100408557C (en) * | 2003-08-26 | 2008-08-06 | 河北工业大学 | A kind of method for preparing 2,4-toluene dicarbamate methyl ester |
-
2005
- 2005-12-01 CN CNB2005100481500A patent/CN100369671C/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102131770B (en) * | 2008-08-22 | 2014-08-06 | 巴斯夫欧洲公司 | Method for producing urethanes composed of di-functional aromatic amines and dialkyl carbonates |
| CN101786967A (en) * | 2010-03-22 | 2010-07-28 | 哈尔滨理工大学 | Method for auxiliary synthesis of 4,4'-diphenyl methane diamino acid methyl ester by microwave |
| CN101786967B (en) * | 2010-03-22 | 2013-02-13 | 哈尔滨理工大学 | Microwave-assisted synthesis of methyl 4,4'-diphenylmethanedicarbamate |
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