CN1098852C - Process for preparing 1,8-diazadicyclo [5,4,0] undecene - Google Patents
Process for preparing 1,8-diazadicyclo [5,4,0] undecene Download PDFInfo
- Publication number
- CN1098852C CN1098852C CN99112071A CN99112071A CN1098852C CN 1098852 C CN1098852 C CN 1098852C CN 99112071 A CN99112071 A CN 99112071A CN 99112071 A CN99112071 A CN 99112071A CN 1098852 C CN1098852 C CN 1098852C
- Authority
- CN
- China
- Prior art keywords
- hexanolactam
- dbu
- catalyzer
- improved
- catalyst
- 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.)
- Expired - Fee Related
Links
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 5
- -1 cyanoethyl caprolactam Chemical compound 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims abstract 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- 238000007259 addition reaction Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- SSUJUUNLZQVZMO-UHFFFAOYSA-N 1,2,3,4,8,9,10,10a-octahydropyrimido[1,2-a]azepine Chemical compound C1CCC=CN2CCCNC21 SSUJUUNLZQVZMO-UHFFFAOYSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- VJHVMUKJJQILHO-UHFFFAOYSA-N 3-(2-oxoazepan-3-yl)propanenitrile Chemical compound O=C1NCCCCC1CCC#N VJHVMUKJJQILHO-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- RKDATCAHDAFNEL-UHFFFAOYSA-N 3-(3-aminopropyl)azepan-2-one Chemical compound NCCCC1CCCCNC1=O RKDATCAHDAFNEL-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000000911 decarboxylating effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002081 enamines Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000003351 stiffener Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a method using caprolactam and acrylonitrile as raw materials to prepare 1, 8-diazabicyclo [5, 4, 0] undecene by reactions of addition, hydrogenization and cyclization. The present invention is characterized in that the mixture of organic alkali (DBU) and inorganic alkali (KOH) is used as a catalyst, and the catalyst is added in the reaction for several times. The present invention has the advantages that the conversion rate of the raw materials is improved to 96% from 90%, the yield of an intermediate (cyanoethyl caprolactam) is improved to 90% from 81%, and the total yield of DBU is improved to 74% from 56%. The catalytic capability of the catalyst is improved, the quality of products is improved, the difficulty of subsequent treating work is lowered, production period is shortened, and three wastes are reduced.
Description
The present invention relates to the chemical synthesis process of medicine intermediate, particularly prepare a kind of catalyzer 1, the method for 8-diaza-bicyclo [5,4,0] hendecene (hereinafter to be referred as DBU), that is:
With enamine, vinyl cyanide in oneself is raw material, makes through addition reaction, hydrogenation reaction, ring-closure reaction.
DBU is used for the catalyzer of polyurethane and the production of other chemical preparationss, reacts the generation piperazine as ammonia and ethylene dichloride in the presence of it; It still is a kind of good decarboxylating agent, the stiffening agent of Resins, epoxy, rust-preventive agent, also can prepare senior inhibiter, be widely used in the semisynthetic antibiotics medicine production.
The existing synthesis technique of DBU divided for three steps:
The first step: hexanolactam adds an amount of solvent, is catalyzer with KOH, under 70～90 ℃ of temperature, drips vinyl cyanide, after the addition reaction, through distillation, purification, gets the cyanoethyl hexanolactam.The transformation efficiency of hexanolactam is 90%, and this step yield is 81%.
Second step: the cyanoethyl hexanolactam is solvent with ethanol, and hydrogenation reaction gets the aminopropyl hexanolactam.
The 3rd step: the aminopropyl hexanolactam is refining DBU after cyclization, total recovery 56%.
Existing technology has the following disadvantages:
(1) yield of addition reaction is low, has only 81%, and the hexanolactam that accounts for the raw materials cost maximum fails to make full use of, and transformation efficiency has only 90%, thereby causes raw materials cost higher; (2) it is more respectively to go on foot the impurity of reaction product, and the purification operations difficulty is big, influences quality product; (3) amount of alcohol is big in the hydrogenation reaction, and it is big to recycle difficulty.
The objective of the invention is to overcome above-mentioned defective, provide a kind of and can reduce raw materials cost, improve the quality, simplify the operation, reduce the method for polluting for preparing DBU.
The present invention is achieved through the following technical solutions:
A kind of is raw material with the hexanolactam vinyl cyanide, through addition reaction, hydrogenation reaction, ring-closure reaction, prepares the method for DBU, it is characterized in that:
The mixture that adopts organic bases and mineral alkali is as catalyzer.
The present invention is with the mixture of organic bases and mineral alkali, as the catalyzer of addition reaction, preferably KOH
Mixture with DBU.In use, preferably add catalyzer at twice, the catalyzer add 70% amount for the first time when hexanolactam begins to add vinyl cyanide was added to 80% o'clock at vinyl cyanide, with the catalyzer adding of remainder.
The weight proportion of KOH and DBU is 1: 2.The parts by weight of hexanolactam and catalyzer are: 200 parts of hexanolactams, 0.3 part of KOH, 0.6 part of DBU.
Present method is made solvent with methyl alcohol in the hydrogenation reaction.
Preparation method provided by the invention has following advantage:
(1) feed stock conversion improves, and brings up to 96% by former 90%, and the yield of intermediate cyanoethyl hexanolactam brings up to 90% by 81%, and the total recovery of DBU is brought up to more than 74% by 56%, has reduced raw materials cost widely; (2) improve the catalytic capability of catalyzer, improved the quality of product, reduced the difficulty of subsequent disposal work; (3) shortened the production cycle,, reduced to about 130 hours by 155～160 hours of former technology; (4) reduced " three wastes ", be suitable for suitability for industrialized production more.
The invention will be further described below in conjunction with the comparative example:
Embodiment 1:
Existing technology:
In the four-hole bottle of 500ml, add the 200g hexanolactam, 75g toluene, when being warming up to 55～60 ℃, under agitation condition, make catalyzer with 0.3gKOH and 0.6gDBU mixed solution, earlier 70% of catalyzer is added in the four-hole bottle, begin to drip the 96kg vinyl cyanide simultaneously, be added drop-wise at 80% o'clock at vinyl cyanide, again 30% of the catalyzer of remainder be added in the four-hole bottle, after reaction finishes, through steaming toluene, lower the temperature the crude product of intermediate, the transformation efficiency of hexanolactam is 96%, again through purify high-quality cyanoethyl hexanolactam, its yield is 91.5% (is benchmark with the hexanolactam); With intermediate cyanoethyl hexanolactam is being solvent with methyl alcohol, and active nickel is under the condition of catalyzer, logical hydrogen, and temperature of reaction is controlled at 93～118 ℃, gets another step intermediate aminopropyl hexanolactam after removing methyl alcohol, and yield is 90.5%; With this aminopropyl hexanolactam 360g, be catalyzer again, under 150～160 ℃ of temperature, reacted 35～40 hours that through refining finished product DBU, total recovery is 74.61% with tosic acid 3.4g.
Former technology:
Once add in four-hole bottle with 0.8gKOH, catalysis 200g hexanolactam drips vinyl cyanide; Hydrogenation reaction is made solvent with ethanol, and other condition is constant, with above-mentioned technology, makes finished product DBU, and the hexanolactam transformation efficiency is 90%; The DBU total recovery is 55.97%.
Claims (2)
1, a kind of is raw material with hexanolactam, vinyl cyanide, through addition reaction, hydrogenation reaction, ring-closure reaction preparation 1, the method of 8-diaza-bicyclo [5,4,0] hendecene, it is characterized in that using in the addition reaction mixture as catalyst of KOH and DBU, the weight proportion of KOH and DBU is 1: 2, and the catalyzer add 70% amount for the first time when hexanolactam begins to add vinyl cyanide was added to 80% o'clock at vinyl cyanide, the catalyzer of remainder is added, make solvent with methyl alcohol in the hydrogenation reaction.
2, method according to claim 1 is characterized in that the parts by weight of hexanolactam and catalyzer are: 0.6 part of 200 parts of hexanolactam, KOH0.3 part, DBU.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99112071A CN1098852C (en) | 1999-02-03 | 1999-02-03 | Process for preparing 1,8-diazadicyclo [5,4,0] undecene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99112071A CN1098852C (en) | 1999-02-03 | 1999-02-03 | Process for preparing 1,8-diazadicyclo [5,4,0] undecene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1262274A CN1262274A (en) | 2000-08-09 |
| CN1098852C true CN1098852C (en) | 2003-01-15 |
Family
ID=5275412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99112071A Expired - Fee Related CN1098852C (en) | 1999-02-03 | 1999-02-03 | Process for preparing 1,8-diazadicyclo [5,4,0] undecene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1098852C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279973B (en) * | 2008-05-22 | 2010-06-02 | 山东新华万博化工有限公司 | Preparation of 1,8-diazabicyclo[5.4.0] hendecene |
| CN112316949A (en) * | 2020-11-05 | 2021-02-05 | 山东中科新材料研究院有限公司 | Preparation method and use method of carbon-containing supported nickel alloy catalyst |
| CN112500418A (en) * | 2020-12-31 | 2021-03-16 | 山东中科新材料研究院有限公司 | Method for synthesizing 1, 8-diazabicycloundecen-7-ene by adopting loop reactor |
| IT202100005336A1 (en) | 2021-03-08 | 2022-09-08 | Versalis Spa | METHOD FOR THE PREPARATION OF AMIDINE. |
| CN116940556A (en) * | 2021-03-08 | 2023-10-24 | 维尔萨利斯股份公司 | Process for preparing amidines |
| CN114478540B (en) * | 2022-02-16 | 2024-08-30 | 玉门千华制药有限公司 | DBU synthesis method |
| IT202200018231A1 (en) | 2022-09-07 | 2024-03-07 | Versalis Spa | METHOD FOR PREPARATION OF AMIDINES FROM N-(ALKYL LACTAMS) |
| CN119661435A (en) * | 2023-09-19 | 2025-03-21 | 中国科学院大连化学物理研究所 | A method for synthesizing N-(2-cyanoethyl)-caprolactam |
| CN120025273B (en) * | 2025-04-17 | 2025-08-29 | 中国天辰工程有限公司 | Preparation method of N-cyanoalkyl substituted lactam |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4943633A (en) * | 1988-06-22 | 1990-07-24 | Air Products And Chemicals, Inc. | Catalytic preparation of cyanoalkyl lactams |
-
1999
- 1999-02-03 CN CN99112071A patent/CN1098852C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4943633A (en) * | 1988-06-22 | 1990-07-24 | Air Products And Chemicals, Inc. | Catalytic preparation of cyanoalkyl lactams |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1262274A (en) | 2000-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111574400B (en) | Separation method of ammoniated and dehydrated product of caprolactam and synthesis method of hexamethylene diamine | |
| CN1098852C (en) | Process for preparing 1,8-diazadicyclo [5,4,0] undecene | |
| CN102311332B (en) | Method for producing succinic acid | |
| CN113480421B (en) | System and method for preparing succinic acid by maleic anhydride hydrogenation | |
| CN114436741B (en) | Preparation method of cyclopentene | |
| CN114014768A (en) | Tranexamic acid without barium salt impurity and preparation method and preparation composition thereof | |
| CN101279973B (en) | Preparation of 1,8-diazabicyclo[5.4.0] hendecene | |
| CN111217684A (en) | Production method for improving yield of cyclohexanone | |
| CN102372666A (en) | Method for synthesizing alfa-methylpyridine through continuous catalytic distillation | |
| CN101580486A (en) | Method for synthesizing N-methylpyrrolidone catalyzed by particle type solid superacid | |
| CN102020543B (en) | Method for producing 9-fluorenone | |
| CN112279781B (en) | Synthetic method of p-hydroxybenzonitrile | |
| CN117209361B (en) | Bisphenol F preparation method | |
| CN1022483C (en) | Process for preparing 2, 4-dimethylaniline and 2, 6-dimethylaniline | |
| CN113563225B (en) | Method for synthesizing benzonitrile by recycling benzomelamine byproduct | |
| CN101108366B (en) | Method for manufacturing catalyst used for synthesizing 2-picoline | |
| CN1268627C (en) | Process for preparing 1.8-diazadicyclo [5,4,0] -7 undecene | |
| CN118290426A (en) | Synthesis method of 1, 8-diazabicyclo-bicyclo (5, 4, 0) -7-undecene | |
| CN117924095A (en) | Process for producing dibenzylamine | |
| CN118184479A (en) | Preparation method of norbornene | |
| CN111205155B (en) | Method for synthesizing adamantane from tetrahydrodicyclopentadiene | |
| CN114907263A (en) | Refining method of caprolactam | |
| CN112279783B (en) | Method for preparing 3-hydroxypropionitrile under supercritical condition | |
| CN114685271B (en) | Method for preparing compound using isobutyric acid and acetic anhydride and device for preparing compound using isobutyric acid and acetic anhydride | |
| CN116041279B (en) | A method for preparing piperidine using an autoclave device and a ruthenium-containing catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |