CN103755551A - 5-oxo-octadecanoic acid synthesis method - Google Patents
5-oxo-octadecanoic acid synthesis method Download PDFInfo
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- CN103755551A CN103755551A CN201410024326.8A CN201410024326A CN103755551A CN 103755551 A CN103755551 A CN 103755551A CN 201410024326 A CN201410024326 A CN 201410024326A CN 103755551 A CN103755551 A CN 103755551A
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- acrylate
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- UIROXHXJKJUFSV-UHFFFAOYSA-N 5-Oxooctadecanoic acid Chemical compound CCCCCCCCCCCCCC(=O)CCCC(O)=O UIROXHXJKJUFSV-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 238000001308 synthesis method Methods 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- -1 3-oxo-hexadecanoic acid carboxylate Chemical class 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- 238000007127 saponification reaction Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000006957 Michael reaction Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
- MNWFXJYAOYHMED-UHFFFAOYSA-N hexane carboxylic acid Natural products CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000010189 synthetic method Methods 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001348 alkyl chlorides Chemical class 0.000 claims description 2
- 150000001350 alkyl halides Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000006166 lysate Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000006845 Michael addition reaction Methods 0.000 abstract description 5
- 238000006114 decarboxylation reaction Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl hexadecanoate Natural products CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- ALPLXHWAHWCMFP-UHFFFAOYSA-N 2-tridecylcyclopentan-1-one Chemical compound C(CCCCCCCCCCCC)C1C(CCC1)=O ALPLXHWAHWCMFP-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclo-pentanone Natural products O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940067592 ethyl palmitate Drugs 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- XIRNKXNNONJFQO-UHFFFAOYSA-N hexadecanoic acid ethyl ester Natural products CCCCCCCCCCCCCCCC(=O)OCC XIRNKXNNONJFQO-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
- C07C51/38—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups by decarboxylation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a 5-oxo-octadecanoic acid synthesis method which comprises the following steps of Michael reaction, saponification reaction, acidification and decarboxylation reaction, and crystallization purification. The synthesis method has the following beneficial effects: raw materials 3-oxo-hexadecanoic acid carboxylate and acrylate are accessible; a catalyst FeCl3.6H2O is cheap and accessible; the yield is high through Michael addition; the reaction conditions are mild; and the equipment is low in requirement and simple to operate.
Description
Technical field
The present invention relates generally to synthetic field, relates in particular to the stearic synthetic method of a kind of 5-oxo.
Background technology
5-oxo stearic acid is a kind of important organic synthesis intermediate, is the important source material of preparation fourth position stearolactone.
About the stearic synthetic document of 5-oxo seldom, but have many documents for 5-oxoalkyl group acid compounds.Be summed up and can be divided three classes: 1. alkyl cyclopentanone oxidation style; 2. 3-oxoalkyl group acid esters and acrylate Michael addition, hydrolysis decarboxylation method; 3. Pyroglutaric acid, haloalkane Grignard reagent additive process.For method 1, be mainly used in low-carbon (LC) 5-oxoalkyl group acid preparation, and for preparation 5-oxo stearic acid, become very difficult, intermediate tridecyl cyclopentanone is difficult for preparation, and conversion rate of oxidation is low, and product purity is low; Method 2, document generally adopts base catalysis Michael addition at present, often occurs the by products such as secondary addition, cyclization, and poor selectivity, separation difficulty need further to be studied; Method 3, it is low that this technique is prepared yield, and halo tridecane is difficult to obtain, and the shortcomings such as production cost height are unsuitable for amplifying and generate.
Summary of the invention
The object of the invention is the problem for above-mentioned existence, proposed to prepare the stearic method of 5-oxo with FeCl36H2O catalysis 3-oxo ten hexacarboxylic acid esters and acrylate Michael addition, saponification, acidifying decarboxylation, recrystallization.
The present invention is achieved by the following technical solutions:
The stearic synthetic method of 5-oxo, comprises the following steps:
(1) Michael reaction
3-oxo ten hexacarboxylic acid esters and acrylate are put in the reactor of organic solvent haloalkane, with FeCl
36H
2o is catalyzer, controls temperature of reaction 30-90 ℃, and reaction times 3-10h, after reaction finishes, reclaims solvent, water pump concentrating under reduced pressure through washing, air distillation;
Wherein said raw material 3-oxo ten hexacarboxylic acid esters (mol): acrylate (mol): FeCl
36H
2o(mol): alkyl chloride (mL)=1:(1-1.1): (0.01-0.05): 500;
(2) saponification reaction
In step (1) products therefrom, add the aqueous sodium hydroxide solution of 5-6%, stirring reaction 4-6h at 35-45 ℃;
Wherein said sodium hydroxide mole dosage be 3-oxo ten hexacarboxylic acid esters and acrylate molar weight sum 1-1.2 doubly;
(3) acidifying decarboxylic reaction
After the saponification reaction of step (2) finishes, with 30-35% concentrated hydrochloric acid or 20-35% sulfuric acid, regulate PH=3-4, with methylene dichloride lysate crude product, through washing, sodium bicarbonate aqueous solution, wash to PH=5-6, normal pressure reclaims solvent, water pump concentrating under reduced pressure obtains crude product;
(4) crystallization purifying
In step (3) gained crude product, add crude product weight 3-5 solvent doubly, heating for dissolving, crystallisation by cooling at 0 ℃, suction filtration, dries to obtain 5-oxo stearic acid of the present invention;
Described solvent is one or more in normal hexane, hexanaphthene, 60-90 ℃ sherwood oil
Advantage of the present invention is:
(1) 3-oxo ten hexacarboxylic acid esters, acrylate raw material are easy to get;
(2) catalyst Fe Cl36H2O inexpensive, be easy to get, Michael addition yield is high;
(3) reaction conditions is gentle, equipment requirements is low, simple to operate.
Embodiment
Embodiment 1:
In 500 ml flasks of magnetic agitation, temperature, reflux condensate device are housed, add respectively 3-oxo methyl palmitate 56.8g(0.2mol), methyl acrylate 17.2g (0.2mol), trichloromethane 100mL and FeCl36H2O 1.1g(0.004mol), heat up 60 ℃, insulated and stirred reaction 6h.Cooling room temperature, 100mL 2% hydrochloric acid washs at twice, and rear 5% sodium bicarbonate washing is to neutral, and air distillation is reclaimed and is dissolved, water pump concentrating under reduced pressure.
In above-mentioned reaction solution, add sodium hydroxide 17.6g(0.44mol) and water 334.4g, 40 ℃ of left and right stirring reaction 5h.With 33% hcl acidifying PH=3-4, the 100mL that adds methylene chloride, stir solids is dissolved, and separates organic layer, and 5% sodium bicarbonate aqueous solution washing, regulates PH=5-6, reclaims solvent, and rear concentrating under reduced pressure, obtains 59 grams of still liquid.
Add 200 grams of normal hexanes, reflux, dissolving, 0 ℃ of cooling, crystallization.Suction filtration, dry, obtains 50 grams of products, fusing point 87.7-88.9 ℃.
Embodiment 2:
In 500 ml flasks of magnetic agitation, temperature, reflux condensate device are housed, add respectively 3-oxo methyl palmitate 56.8g(0.2mol), methyl acrylate 18.9g (0.22mol), methylene dichloride 100mL and FeCl36H2O 2.2g(0.008mol), temperature rising reflux reaction 10h.Cooling room temperature, 100mL 2% hydrochloric acid washs at twice, and rear 5% sodium bicarbonate washing is to neutral, and air distillation is reclaimed and is dissolved, water pump concentrating under reduced pressure.
In above-mentioned reaction solution, add sodium hydroxide 18.4g(0.46mol) and water 350g, 40 ℃ of left and right stirring reaction 5h.With 33% hcl acidifying PH=3-4, the 100mL that adds methylene chloride, stir solids is dissolved, and separates organic layer, and 5% sodium bicarbonate aqueous solution washing, regulates PH=5-6, reclaims solvent, and rear concentrating under reduced pressure, obtains 60 grams of still liquid.
Add 200 grams of 60-90 ℃ of sherwood oils, reflux, dissolving, 0 ℃ of cooling, crystallization.Suction filtration, dry, obtains 46 grams of products, fusing point 86.3-88.2 ℃.
Embodiment 3:
In 500 ml flasks of magnetic agitation, temperature, reflux condensate device are housed, add respectively 3-oxo ethyl palmitate 59.6g(0.2mol), methyl acrylate 17.2g (0.2mol), 1,2-ethylene dichloride 100mL and FeCl36H2O 1.1g(0.004mol), heat up 90 ℃, stirring reaction 3h.Cooling room temperature, 100mL 2% hydrochloric acid washs at twice, and rear 5% sodium bicarbonate washing is to neutral, and air distillation is reclaimed and is dissolved, water pump concentrating under reduced pressure.
In above-mentioned reaction solution, add sodium hydroxide 17.6g(0.44mol) and water 334.4g, 40 ℃ of left and right stirring reaction 6h.With 33% hcl acidifying PH=3-4, the 100mL that adds methylene chloride, stir solids is dissolved, and separates organic layer, and 5% sodium bicarbonate aqueous solution washing, regulates PH=5-6, reclaims solvent, and rear concentrating under reduced pressure, obtains 60 grams of still liquid.
Add 200 grams of normal hexanes, reflux, dissolving, 0 ℃ of cooling, crystallization.Suction filtration, dry, obtains 48 grams of products, fusing point 86.1-88.2 ℃.
Claims (1)
1. the stearic synthetic method of 5-oxo, is characterized in that comprising the following steps:
(1) Michael reaction
3-oxo ten hexacarboxylic acid esters and acrylate are put in the reactor of organic solvent haloalkane, with FeCl
36H
2o is catalyzer, controls temperature of reaction 30-90 ℃, and reaction times 3-10h, after reaction finishes, reclaims solvent, water pump concentrating under reduced pressure through washing, air distillation;
Wherein said raw material 3-oxo ten hexacarboxylic acid esters (mol): acrylate (mol): FeCl
36H
2o(mol): alkyl chloride (mL)=1:(1-1.1): (0.01-0.05): 500;
(2) saponification reaction
In step (1) products therefrom, add the aqueous sodium hydroxide solution of 5-6%, stirring reaction 4-6h at 35-45 ℃;
Wherein said sodium hydroxide mole dosage be 3-oxo ten hexacarboxylic acid esters and acrylate molar weight sum 1-1.2 doubly;
(3) acidifying decarboxylic reaction
After the saponification reaction of step (2) finishes, with 30-35% concentrated hydrochloric acid or 20-35% sulfuric acid, regulate PH=3-4, with methylene dichloride lysate crude product, through washing, sodium bicarbonate aqueous solution, wash to PH=5-6, normal pressure reclaims solvent, water pump concentrating under reduced pressure obtains crude product;
(4) crystallization purifying
In step (3) gained crude product, add crude product weight 3-5 solvent doubly, heating for dissolving, crystallisation by cooling at 0 ℃, suction filtration, dries to obtain 5-oxo stearic acid of the present invention;
Described solvent is one or more in normal hexane, hexanaphthene, 60-90 ℃ sherwood oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410024326.8A CN103755551A (en) | 2014-01-20 | 2014-01-20 | 5-oxo-octadecanoic acid synthesis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410024326.8A CN103755551A (en) | 2014-01-20 | 2014-01-20 | 5-oxo-octadecanoic acid synthesis method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103755551A true CN103755551A (en) | 2014-04-30 |
Family
ID=50522915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410024326.8A Pending CN103755551A (en) | 2014-01-20 | 2014-01-20 | 5-oxo-octadecanoic acid synthesis method |
Country Status (1)
| Country | Link |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3592948A (en) * | 1968-03-08 | 1971-07-13 | Pennwalt Corp | Addition reaction involving diperoxyfumarate to form compounds having diperoxysuccinyl groups |
| JP2006281203A (en) * | 2005-03-10 | 2006-10-19 | Osaka Univ | Catalyst composition containing metal vanadate apatite, and carbon-carbon bond forming method using the catalyst composition |
-
2014
- 2014-01-20 CN CN201410024326.8A patent/CN103755551A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3592948A (en) * | 1968-03-08 | 1971-07-13 | Pennwalt Corp | Addition reaction involving diperoxyfumarate to form compounds having diperoxysuccinyl groups |
| JP2006281203A (en) * | 2005-03-10 | 2006-10-19 | Osaka Univ | Catalyst composition containing metal vanadate apatite, and carbon-carbon bond forming method using the catalyst composition |
Non-Patent Citations (2)
| Title |
|---|
| ALFRED CAMPBELL: "A new synthesis of (±)-5 : 8-thioctic acid", 《J. CHEM. SOC.》, 31 December 1955 (1955-12-31), pages 4218 - 4220 * |
| JENS CHRISTOFFERS: "Iron(Ⅲ) catalysis of the Michael reaction of 1,3-dicarbonyl compounds and enones", 《CHEM. COMMUN.》, 31 December 1997 (1997-12-31), pages 943 - 944 * |
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