CN101844984B - Preparation method of 1,2,3-cyclopropyl tricarboxylate - Google Patents
Preparation method of 1,2,3-cyclopropyl tricarboxylate Download PDFInfo
- Publication number
- CN101844984B CN101844984B CN 201010197340 CN201010197340A CN101844984B CN 101844984 B CN101844984 B CN 101844984B CN 201010197340 CN201010197340 CN 201010197340 CN 201010197340 A CN201010197340 A CN 201010197340A CN 101844984 B CN101844984 B CN 101844984B
- Authority
- CN
- China
- Prior art keywords
- ring
- preparation
- acid triethyl
- tricarballylic acid
- reaction
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- YVPJCJLMRRTDMQ-UHFFFAOYSA-N ethyl diazoacetate Chemical compound CCOC(=O)C=[N+]=[N-] YVPJCJLMRRTDMQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 3
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 claims description 58
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-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
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-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
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical group [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- 229940045803 cuprous chloride Drugs 0.000 claims description 4
- JXSRRBVHLUJJFC-UHFFFAOYSA-N 7-amino-2-methylsulfanyl-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitrile Chemical compound N1=CC(C#N)=C(N)N2N=C(SC)N=C21 JXSRRBVHLUJJFC-UHFFFAOYSA-N 0.000 claims description 3
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 3
- 229960003280 cupric chloride Drugs 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- JNGRYGYMVRKYBE-UHFFFAOYSA-N copper;2,2,2-trifluoroacetic acid Chemical compound [Cu].OC(=O)C(F)(F)F JNGRYGYMVRKYBE-UHFFFAOYSA-N 0.000 claims description 2
- OXADXHFBOONPIC-UHFFFAOYSA-N copper;4-methylbenzenesulfonic acid Chemical compound [Cu].CC1=CC=C(S(O)(=O)=O)C=C1 OXADXHFBOONPIC-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000012847 fine chemical Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- -1 (2 * 10ml) washings Chemical compound 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- TXTWXQXDMWILOF-UHFFFAOYSA-N (2-ethoxy-2-oxoethyl)azanium;chloride Chemical compound [Cl-].CCOC(=O)C[NH3+] TXTWXQXDMWILOF-UHFFFAOYSA-N 0.000 description 1
- UPWZWQGQRNPKTE-UHFFFAOYSA-N 1,2,3-trimethylidenecyclopropane Chemical compound C=C1C(=C)C1=C UPWZWQGQRNPKTE-UHFFFAOYSA-N 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- ZHKFMQNJQCOFOC-UHFFFAOYSA-N acetic acid;ethyl 2-aminoacetate Chemical compound CC(O)=O.CCOC(=O)CN ZHKFMQNJQCOFOC-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- DAUSJTSCCQWWDI-UHFFFAOYSA-N chloroform;1,2-dichloroethane;dichloromethane Chemical compound ClCCl.ClCCCl.ClC(Cl)Cl DAUSJTSCCQWWDI-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- ZWTRZSCYTXXULL-UHFFFAOYSA-N triethyl cyclopropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)C1C(C(=O)OCC)C1C(=O)OCC ZWTRZSCYTXXULL-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N trifluoroacetic acid Substances OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of 1,2,3-cyclopropyl tricarboxylate, comprising the following steps of: heating ethyl diazoacetate as a raw material for carrying out a cyclization reaction in the presence of organic solvents and catalysts at the reaction temperature of 35-110DEG C for 2-6h, wherein the mass ratio of the catalysts to the ethyl diazoacetate is 1:10-50; and rectifying after the reaction is finished to obtain the 1,2,3-cyclopropyl tricarboxylate. The method for preparing the 1,2,3-cyclopropyl tricarboxylate has the characteristics of concise process, high yield, low cost and less discharge of three wastes.
Description
Technical field
The present invention relates to a kind of synthetic method of organic compound, particularly 1,2, the synthetic method of 3-ring tricarballylic acid triethyl (1,2,3-Cyclopropanetricarboxylic acid triethyl ester).
Background technology
1,2,3-ring tricarballylic acid triethyl, its molecular formula is C
12H
18O
6, its structural formula is shown in S-1; Being dissolved in hexanaphthene, methylene dichloride, ethylene dichloride etc., being dissolved in hardly cold water, is a kind of important fine-chemical intermediate, be mainly used in synthetic 1,2,3-trimethylene cyclopropane (CAS:66767-55-3), cyclopropane-1, the products such as 2,3-triamine (CAS:5794-73-0).
The comprehensive literature report, present 1,2, following several method is mainly adopted in the preparation of 3-ring tricarballylic acid triethyl: 1, adopt butenoic acid diethyl ester and ethyl diazoacetate to react under the effect of catalyzer and generate 1,2,3-ring tricarballylic acid triethyl, reaction formula is (U.S.Pat.Appl.Publ. shown in S-2,2010076239,25Mar 2010); 2, adopt butenoic acid diethyl ester and S, S-dimethyl acetic acid ethyl ester reacts under the effect of catalyzer and generates 1,2,3-ring tricarballylic acid triethyl, reaction formula is (e-EROS Encyclopedia of Reagents for Organic Synthesis, No pp.given shown in S-3; 2001); 3, adopt ethyl diazoacetate to react under the effect of catalyzer and generate 1,2,3-ring tricarballylic acid triethyl, reaction formula is (Organometallics, 21 (18), 3823-3826,2002) shown in S-4.For first method, need to adopt 5,15-two [2,6-two [[[((1S)-2,2-dimethyl cyclopropyl) carbonyl] amino] phenyl]-10,20-two (3, the 5-di-tert-butyl-phenyl) porphines acid group] cobalt (CAS:811435-11-7) is as catalyzer, and therefore its preparation difficulty, expensive is not suitable for for industrial production 1,2,3-ring tricarballylic acid triethyl; For second method, raw material S, S-dimethyl acetic acid ethyl ester are difficult to preparation, and reaction can produce dimethyl sulphide, contaminate environment; For the third method, need to adopt that dichloro three-(triphenylphosphine) ruthenium (CAS:15529-49-4) is as catalyzer, it is expensive, and when adopting this technique, the yield of 1,2,3-ring tricarballylic acid triethyl only has 10%.
Summary of the invention
The technical problem to be solved in the present invention provide that a kind of technique is succinct, yield is high, cost is low, three waste discharge is few 1,2, the preparation method of 3-ring tricarballylic acid triethyl.
In order to solve the problems of the technologies described above, the invention provides a kind of 1,2, the preparation method of 3-ring tricarballylic acid triethyl is take ethyl diazoacetate as raw material, under the condition that organic solvent, catalyzer exist, ring-closure reaction is carried out in heating, the mass ratio of catalyzer and ethyl diazoacetate is 1: 10～50, and temperature of reaction is 35～110 ℃, and the reaction times is 2～6 hours; Rectifying after reaction finishes gets 1,2,3-ring tricarballylic acid triethyl.
As of the present invention 1,2, the preparation method's of 3-ring tricarballylic acid triethyl improvement: catalyzer is copper powder, cuprous chloride, cupric chloride, neutralized verdigris, copper stearate, trifluoroacetic acid copper, trichoroacetic acid(TCA) copper or p-methyl benzenesulfonic acid copper.
As of the present invention 1,2, the preparation method's of 3-ring tricarballylic acid triethyl further improvement: organic solvent is aliphatic hydrocarbon, aromatic hydrocarbon or halogenated alkane, and organic solvent and ethyl diazoacetate mass ratio are 2～10: 1.
As of the present invention 1,2, the preparation method's of 3-ring tricarballylic acid triethyl further improvement: aliphatic hydrocarbon is hexanaphthene or normal hexane; Aromatic hydrocarbon is benzene or toluene; Halogenated alkane is methylene dichloride, ethylene dichloride or trichloromethane.
As of the present invention 1,2, the preparation method's of 3-ring tricarballylic acid triethyl further improvement: rectifying carries out under normal pressure, collects tower top temperature and be the cut between 110～113 ℃, gets 1,2,3-ring tricarballylic acid triethyl.
In the present invention, ethyl diazoacetate feeds intake in the mode that drips, the described reaction times for drip ethyl diazoacetate time+time=2 that continuations reacted～6 hours.
In the present invention, select by glycine ethyl ester acetate and Sodium Nitrite reaction and generate ethyl diazoacetate, concrete preparation method is with reference to " fine-chemical intermediate " 2008,38 (1): 40～43.
Preparation 1,2 of the present invention, the reaction equation of 3-ring tricarballylic acid triethyl is as follows:
Catalyzer of the present invention be easy to get and cost low; Therefore adopt method of the present invention to prepare 1,2,3-ring tricarballylic acid triethyl and have advantage with low cost, and yield can be up to 95.1%.
Embodiment
Embodiment 1, a kind of 1,2, the preparation method of 3-ring tricarballylic acid triethyl, carry out following steps successively:
Step 1), preparation ethyl diazoacetate:
14.0g (0.1mol) glycine ethyl ester hydrochloride, 20ml water, 1ml mass concentration 98% vitriol oil, 50ml ethylene dichloride are put in the 250ml flask, be cooled to 10 ℃, under agitation condition, drip 25ml sodium nitrite in aqueous solution (27.5%, 0.11mol), 20min drips off, stopped reaction behind the stirring 30min.Separatory, (2 * 20ml) extract water with ethylene dichloride, (2 * 10ml) washings, anhydrous magnesium sulfate drying are (with reference to " fine-chemical intermediate " 2008 through saturated sodium bicarbonate solution for the organic phase that merges, 38 (1): 40～43), (it is 9.1% that GC analyzes ethyl diazoacetate content to obtain the dichloroethane solution 118.0g of ethyl diazoacetate, amount to pure ethyl diazoacetate 10.7g), the dichloroethane solution of the ethyl diazoacetate of gained carries out following step 2) reaction.
Step 2):
Add 1g cuprous chloride, 50ml ethylene dichloride in the 250ml flask, be warming up to 40 ℃, drip step 1) the 118.0g ethyl diazoacetate solution of gained, 2h drips off (insulation), and insulation continues to react stopped reaction behind the 0.5h.Filter out catalyzer, the product atmospheric distillation, the collection tower top temperature is 110～113 ℃ cut, namely gets product 1,2,3-ring tricarballylic acid triethyl.1,2 of this method production, 3-ring tricarballylic acid triethyl, gas chromatographic analysis content is about 99.5%, and yield reaches 95.1%.
Embodiment 2～8:
Step 1) with embodiment 1.
The step 2 of change embodiment 1) the following reaction conditions in:
Step 2) organic solvent in (being called for short S), the quality of organic solvent and ethyl diazoacetate quality ratio in the step 2 (are called for short R
1), catalyzer in the step 2 (being called for short C), the quality of catalyzer and ethyl diazoacetate quality ratio in the step 2 (are called for short R
2), temperature of reaction in the step 2 (being called for short T) in the reaction times in the step 2 (being called for short t), drips ethyl diazoacetate time (abbreviation t in the step 2
1), continue the reaction times in the step 2 (to be called for short t
2), t=t
1+ t
2, obtain embodiment 2～8, thus obtain corresponding 1,2, the yield (being called for short Y) of 3-ring tricarballylic acid triethyl.Particular content and data results see Table 1.
Table 1
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| S | Ethylene dichloride | Methylene dichloride | Trichloromethane | Hexanaphthene | Ethylene dichloride | Benzene | Toluene | Normal hexane |
| R 1 | 6∶1 | 3∶1 | 10∶1 | 2∶1 | 5∶1 | 5∶1 | 2∶1 | 3∶1 |
| C | Cuprous chloride | Copper powder | Cupric chloride | Neutralized verdigris | Copper stearate | P-methyl benzenesulfonic acid copper | Trifluoroacetic acid copper | Trichoroacetic acid(TCA) copper |
| R 2 | 1∶11 | 1∶20 | 1∶50 | 1∶20 | 1∶35 | 1∶30 | 1∶40 | 1∶10 |
| T(℃) | 40 | 35 | 50 | 60 | 80 | 55 | 110 | 50 |
| t(h) | 2.5 | 4 | 5.5 | 3.5 | 4 | 2 | 6 | 3 |
| t 1(h) | 2 | 3 | 4.5 | 3 | 3.5 | 1.5 | 5 | 2.5 |
| t 2(h) | 0.5 | 1 | 1 | 0.5 | 0.5 | 0.5 | 1 | 0.5 |
| Y(％) | 95.1 | 85.6 | 88.0 | 91.5 | 92.0 | 90.5 | 91.0 | 94.5 |
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (4)
1. one kind 2, the preparation method of 3-ring tricarballylic acid triethyl, it is characterized in that: take ethyl diazoacetate as raw material, under the condition that organic solvent, catalyzer exist, ring-closure reaction is carried out in heating, the mass ratio of catalyzer and ethyl diazoacetate is 1: 10～50, and temperature of reaction is 35～110 ℃, and the reaction times is 2～6 hours; Rectifying after reaction finishes gets 1,2,3-ring tricarballylic acid triethyl;
Described catalyzer is cuprous chloride, cupric chloride, neutralized verdigris, copper stearate, trifluoroacetic acid copper, trichoroacetic acid(TCA) copper or p-methyl benzenesulfonic acid copper.
2. according to claim 11,2, the preparation method of 3-ring tricarballylic acid triethyl, it is characterized in that: described organic solvent is aliphatic hydrocarbon, aromatic hydrocarbon or halogenated alkane, organic solvent and ethyl diazoacetate mass ratio are 2～10: 1.
3. according to claim 21,2, the preparation method of 3-ring tricarballylic acid triethyl, it is characterized in that: described aliphatic hydrocarbon is hexanaphthene or normal hexane; Aromatic hydrocarbon is benzene or toluene; Halogenated alkane is methylene dichloride, ethylene dichloride or trichloromethane.
4. according to claim 1～3 any one 1,2, the preparation method of 3-ring tricarballylic acid triethyl, it is characterized in that: described rectifying carries out under normal pressure, collects tower top temperature and be the cut between 110～113 ℃, gets 1,2,3-ring tricarballylic acid triethyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010197340 CN101844984B (en) | 2010-06-08 | 2010-06-08 | Preparation method of 1,2,3-cyclopropyl tricarboxylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010197340 CN101844984B (en) | 2010-06-08 | 2010-06-08 | Preparation method of 1,2,3-cyclopropyl tricarboxylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101844984A CN101844984A (en) | 2010-09-29 |
| CN101844984B true CN101844984B (en) | 2013-01-02 |
Family
ID=42769821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010197340 Expired - Fee Related CN101844984B (en) | 2010-06-08 | 2010-06-08 | Preparation method of 1,2,3-cyclopropyl tricarboxylate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101844984B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127052B (en) * | 2011-01-25 | 2013-05-01 | 浙江大学 | Method for synthesizing 1,4-benzdioxan-2-carboxylic acid |
| CN102617545B (en) * | 2011-01-27 | 2015-09-09 | 大连大学 | The method of synthesis 2-thia two ring [3.1.0]-3-hexene-6-manthanoate |
| CN106316845A (en) * | 2016-08-24 | 2017-01-11 | 江苏优普生物化学科技股份有限公司 | Preparing method of cis, trans-ethyl 2, 2-dimethyl-3-(1-isobutenyl)cyclopropane-1-carboxylate |
| CN109776351B (en) * | 2017-11-15 | 2021-11-09 | 江苏优士化学有限公司 | Diazoacetic ester continuous synthesis method |
| CN114478387B (en) * | 2020-10-28 | 2023-08-15 | 中国科学院大连化学物理研究所 | Synthesis method of 1,3, 4-trimethyl-1H-pyrazole-5-carboxylic acid ethyl ester compound |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6033100B2 (en) * | 1976-12-14 | 1985-08-01 | 電気化学工業株式会社 | Method for producing cyclopropane tricarboxylic acid ester |
-
2010
- 2010-06-08 CN CN 201010197340 patent/CN101844984B/en not_active Expired - Fee Related
Non-Patent Citations (5)
| Title |
|---|
| Eric Graban,et al..Stereoselective Generation of Cis or Trans Olefins from the RuCl2(PPh3)3-Catalyzed Diazo Coupling of Ethyldiazoacetate.《Organometallics》.2002,第21卷(第18期),3823-3827. |
| ErnestWenkert et al..Reactions of Ethyl Diazoacetate with Thianaphthene |
| JP特开昭53-73542A 1978.06.30 |
| Reactions of Ethyl Diazoacetate with Thianaphthene,Indoles,and Benzofuran;Ernest Wenkert,et al.;《J.Org.Chem.》;19771231;第42卷(第24期);3945-3949 * |
| Stereoselective Generation of Cis or Trans Olefins from the RuCl2(PPh3)3-Catalyzed Diazo Coupling of Ethyldiazoacetate;Eric Graban,et al.;《Organometallics》;20020731;第21卷(第18期);3823-3827 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101844984A (en) | 2010-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101844984B (en) | Preparation method of 1,2,3-cyclopropyl tricarboxylate | |
| Zhou et al. | A Convenient and General Iron‐Catalyzed Reduction of Amides to Amines | |
| Liu et al. | Highly efficient and convenient asymmetric hydrosilylation of ketones catalyzed with zinc Schiff base complexes | |
| EP3233778B1 (en) | Method for producing optically active carbonyl compounds | |
| TW548265B (en) | Process for preparing 1-octene | |
| JP2019501908A (en) | Improved method for enriching alpha-tocotrienol from a mixed tocol composition | |
| CN105339352B (en) | The method that pyrazolecarboxamide is prepared for stereoselectivity | |
| Prakash et al. | New ruthenium (II) carbonyl complexes bearing disulfide Schiff base ligands and their applications as catalyst for some organic transformations | |
| US9187404B2 (en) | Method for producing polyalkylene glycol derivative having amino group at end, with narrow molecular weight distribution | |
| Mitamura et al. | Highly regioselective double hydrothiolation of terminal acetylenes with thiols catalyzed by palladium diacetate | |
| Lalic et al. | Enantioselective rhodium (I)-triethylamine catalyzed addition of potassium isopropenyl trifluoroborate to enones | |
| CN104163775B (en) | A kind of production method of o-methyl-phenyl-azanol | |
| Alonso et al. | Conjugate reduction of α, β-unsaturated carbonyl compounds promoted by nickel nanoparticles | |
| WO2013161594A1 (en) | Method for producing hydroxyphenylcyclohexanol compound | |
| CN102367230A (en) | Method for synthesizing nitrile from aldoxime | |
| EP2891647A1 (en) | Method for producing (r)-1,1,3-trimethyl-4-aminoindane | |
| JP3861570B2 (en) | Method for producing cyclododecene | |
| CN109535120A (en) | The preparation method of 7- substitution -3,4,4,7- tetrahydro cyclobutane and cumarin -5- ketone | |
| CN101337858A (en) | Process and equipment for preparing 1,2-butadiene by continuous method | |
| Ohnemueller et al. | A versatile access to enantiomerically pure 5-substituted 4-hydroxycyclohex-2-enones: an advanced hemisecalonic acid a model | |
| CN115197048A (en) | Preparation method of hydrogenated bisphenol A | |
| CN105348057A (en) | Synthetic method of tebuconazole intermediate | |
| Tong et al. | Synthesis of N, N-dimethyl-2-amino-1, 2-dicyclohexylethanol and its application in the enantioselective conjugate addition of diethylzinc to enones: a convenient upgrade of the chiral ligand via hydrogenation | |
| CN101555205B (en) | Preparing method of 3-oxo-1-cyclobutane-carboxylic acid | |
| JP2022514224A (en) | Recovery method and reuse method of selective uniform hydrogenation 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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130102 Termination date: 20130608 |