CN103965100B - A kind of method preparing imidazolinone herbicide intermediate - Google Patents
A kind of method preparing imidazolinone herbicide intermediate Download PDFInfo
- Publication number
- CN103965100B CN103965100B CN201310030106.1A CN201310030106A CN103965100B CN 103965100 B CN103965100 B CN 103965100B CN 201310030106 A CN201310030106 A CN 201310030106A CN 103965100 B CN103965100 B CN 103965100B
- Authority
- CN
- China
- Prior art keywords
- compound
- ceric nitrate
- ammonium ceric
- imidazolinone herbicide
- methyl
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention belongs to organic synthesis field, specifically a kind of method preparing imidazolinone herbicide intermediate.Prepare imidazolinone herbicide intermediate reaction formula as follows, in polar solvent, react to obtain intermediate, i.e. 5-picoline-2,3-dicarboxylic diester or 5-methoxyl methyl pyridine-2,3-dicarboxylic acid diester with compound 1 through ammonium ceric nitrate for raw material；Wherein R1For methyl or methoxyl methyl, R2For methyl or ethyl.Preparation process of the present invention is easy and simple to handle, and raw material is easy to get, and is a kind of method being prone to prepare imidazolinone herbicide intermediate 5-methyl or 5-methoxyl methyl pyridine-2,3-dicarboxylic acid diester in a large number.
Description
Technical field
The invention belongs to organic synthesis field, specifically a kind of method preparing imidazolinone herbicide intermediate.
Background technology
5-methyl or 5-methoxyl methyl pyridine-2, 3-dicarboxylic diester is the key intermediate of imidazolinone herbicide, synthesis adopt quinoline or quinoline oxidation carry out esterification again and obtain (such as US5281713, 1994), or adopt two enamine succinates and propylene aldehydes condensation synthesis (such as JP, 1-143857, 1989), or adopt butene dioic acid halo derivatives and propylene aldehydes condensation (such as EP0461401A1 under ammonia or ammonia salt exist, 1991) etc., these methods or by-product are unfavorable for the purification of intermediate more, or conversion ratio is relatively low, or intermediate is not sufficiently stable and not easily operates.
Summary of the invention
It is an object of the invention to provide a kind of method preparing imidazolinone herbicide intermediate.
The technical solution used in the present invention is for achieving the above object:
A kind of method preparing imidazolinone herbicide intermediate, prepare imidazolinone herbicide intermediate reaction formula as follows, in polar solvent, intermediate is reacted to obtain through ammonium ceric nitrate for raw material with compound (1), i.e. 5-picoline-2,3-dicarboxylic diester or 5-methoxyl methyl pyridine-2,3-dicarboxylic acid diester；Reaction equation is as follows:
In formula: R1For methyl or methoxyl methyl；R2For methyl or ethyl；R3、R4Difference, is respectively selected from hydrogen or methoxyl group, i.e. R3With R4It is asynchronously hydrogen or methoxyl group.
Compound (1) and ammonium ceric nitrate are in polar solvent, in-20-80 ° of lower 0.5-12.0 hour prepared 5-picoline-2 of reaction of C stirring, 3-dicarboxylic diester or 5-methoxyl methyl pyridine-2,3-dicarboxylic acid diester；Wherein ammonium ceric nitrate consumption is 2.0-10.0 times of compound (1) in mol.
Further preferably, compound (1) and ammonium ceric nitrate are in polar solvent, in-10-50 ° of lower 0.5-6.0 hour prepared 5-picoline-2 of reaction of C stirring, 3-dicarboxylic diester or 5-methoxyl methyl pyridine-2,3-dicarboxylic acid diester；Wherein ammonium ceric nitrate consumption is 2.5-7.0 times of compound (1) in mol；Polar solvent is acetonitrile, acetone, acetonitrile/water or acetone/water.
Further preferred, compound (1) and ammonium ceric nitrate are in polar solvent, in-5-30 ° of lower 0.5-3.0 hour prepared 5-picoline-2 of reaction of C stirring, 3-dicarboxylic diester or 5-methoxyl methyl pyridine-2,3-dicarboxylic acid diester；Wherein ammonium ceric nitrate consumption is 3.0-6.0 times of compound (1) in mol；Polar solvent is the volume ratio of acetonitrile/water or acetone/water, acetonitrile or acetone and water is 1/1-5/1.
Described compound (1) can according to list of references Organic&BiomolecularChemistry, 2009,7 (23), instruction in 4943-4953 carries out, and namely the alkene imine intermediate original position of employing olefine aldehydr and o-methoxyaniline or olefine aldehydr and the generation of p-aminoanisole and acetylenedicarboxylic acid ester react 8-12 hour at 140-200 ° of C and obtain compound (1).
Advantage for present invention:
Preparation process of the present invention is easy and simple to handle, and raw material is easy to get, and reaction condition is gentle, and post processing is easy, is a kind of method being prone to prepare imidazolinone herbicide intermediate 5-methyl or 5-methoxyl methyl pyridine-2,3-dicarboxylic acid diester in a large number.
Detailed description of the invention
Unless otherwise specified, palladium salt, formic acid are with gram (g) metering, and acetic acid is in milliliter (mL), and raw material is with gram (g) metering for the present embodiment.
Reaction equation is as follows, reacts to obtain intermediate, i.e. 5-picoline-2,3-dicarboxylic diester or 5-methoxyl methyl pyridine-2,3-dicarboxylic acid diester with compound (1) through ammonium ceric nitrate for raw material in polar solvent；
Compound (1) stirs several tens minutes to a few hours under ammonium ceric nitrate exists in acetonitrile/water or ketone/water, obtains 5-methyl-2,3-dicarboxylic ester pyridine or 5-methoxyl methyl-2,3-dicarboxylic ester pyridine.Or reactant compound (1) can adopt and be dissolved in acetonitrile/water or acetone/water, the lower solid nitric acid cerium ammonium that adds of stirring completes to react；Or compound (1) is first dissolved in acetonitrile or acetone by employing, stirring lower dropping ammonium ceric nitrate aqueous solution completes reaction.When preparing in a small amount, react very easy to control；During a large amount of preparation, the reaction heat owing to producing not easily is got rid of in time and is caused reaction excessively violent, therefore ammonium ceric nitrate reagent should not once add, and is dividedly in some parts comparison safe, and for offsetting the reaction heat produced and controlling reaction starting velocity, reaction carries out at low temperatures.Typical experimental implementation is as follows: compound (1) is dissolved in acetonitrile or acetone/water or is dissolved separately in acetonitrile or acetone, under-5 ° of C to room temperature, compound (1) mole 2.0-10.0 times of solid nitric acid cerium ammonium or ammonium ceric nitrate aqueous solution is added under stirring, material room temperature stirred for several ten minutes is after a few hours, reactant is evaporated to 1/4, suitable quantity of water is poured in concentrated solution, with extraction into ethyl acetate, extract dries, recovered under reduced pressure ethyl acetate obtains product, and in aqueous phase, ammonium ceric nitrate is recycling after treatment.
Embodiment 1
By 3.75g4-hydrogen-5-methoxyl methyl-1-(p-methoxyphenyl) pyridine-2, 3-diethyl dicarboxylate (compound (1)) adds in 250mL there-necked flask, add 20ml acetonitrile/water mixed liquor (3/1, v/v), room temperature, stirring is lower adds 17.9g ammonium ceric nitrate, after mixture stirs 2 hours at this temperature, it is evaporated to about 1/4 volume, concentrated solution will add 50ml water, undertaken extracting 4 times by ethyl acetate extraction again, use 50ml extraction into ethyl acetate every time, merge each extract, with dried over sodium sulfate extract, recovered under reduced pressure ethyl acetate, obtain 5-methoxyl methyl pyridine-2, 3-diethyl dicarboxylate product 1.83g, yield 76.57%.
1H-NMR(300MHz, CDCl3): δ 8.60(s, 1H), 8.08(s, 1H), 4.44(q, 2H), 4.40(q, 2H), 2.41(s, 3H), 1.42(t, 3H), 1.38 (t, 3H)
Embodiment 2
By 3.75g4-hydrogen-5-methoxyl methyl-1-(p-methoxyphenyl) pyridine-2,3-diethyl dicarboxylate adds in 250mL there-necked flask, add 25ml acetonitrile/water mixed liquor (3/1, v/v), room temperature, stirring lower addition 17.9g ammonium ceric nitrate, after mixture stirs 3 hours at this temperature, it is evaporated to about 1/4 volume, adds 50ml water, with each 50ml extraction into ethyl acetate 4 times, combining extraction liquid, dried over sodium sulfate, recovered under reduced pressure ethyl acetate, obtain 5-methoxyl methyl pyridine-2,3-diethyl dicarboxylate product 2.34g, yield 86.99%.
1H-NMR(300MHz, CDCl3): δ 8.66(s, 1H), 8.12(s, 1H), 4.60(s, 2H), 4.46(q, 2H), 4.42(q, 2H), 3.42(s, 3H), 1.42(t, 3H), 1.38 (t, 3H) embodiment 3
By 3.45g4-hydrogen-5-methyl isophthalic acid-(o-methoxyphenyl) pyridine-2,3-diethyl dicarboxylate adds in 250mL there-necked flask, add 25ml acetonitrile/water mixed liquor (3/1, v/v), room temperature, stirring lower addition 17.9g ammonium ceric nitrate, after mixture stirs 2 hours at this temperature, it is evaporated to about 1/4 volume, adds 50ml water, with each 50ml extraction into ethyl acetate 4 times, combining extraction liquid, dried over sodium sulfate, recovered under reduced pressure ethyl acetate, obtain 5-picoline-2,3-diethyl dicarboxylate product 1.74g, yield 72.80%.
1H-NMR(300MHz, CDCl3): δ 8.60(s, 1H), 8.08(s, 1H), 4.44(q, 2H), 4.40(q, 2H), 2.41(s, 3H), 1.42(t, 3H), 1.38 (t, 3H)
Embodiment 4
By 3.75g4-hydrogen-5-methoxyl methyl-1-(o-methoxyphenyl) pyridine-2,3-diethyl dicarboxylate adds in 250mL there-necked flask, add 25ml acetonitrile/water mixed liquor (3/1, v/v), room temperature, stirring lower addition 17.9g ammonium ceric nitrate, after mixture stirs 3 hours at this temperature, it is evaporated to about 1/4 volume, adds 50ml water, with each 50ml extraction into ethyl acetate 4 times, combining extraction liquid, dried over sodium sulfate, recovered under reduced pressure ethyl acetate, obtain 5-methoxyl methyl pyridine-2,3-diethyl dicarboxylate product 2.44g, yield 90.71%.
1H-NMR(300MHz, CDCl3): δ 8.66(s, 1H), 8.12(s, 1H), 4.60 (s, 2H), 4.46(q, 2H), 4.42(q, 2H), 3.42(s, 3H), 1.42(t, 3H), 1.38 (t, 3H)
Embodiment 5
By 3.45g4-hydrogen-5-methyl isophthalic acid-(p-methoxyphenyl) pyridine-2,3-diethyl dicarboxylate adds in 250mL there-necked flask, add 20ml acetone/water mixed liquor (3/1, v/v), room temperature, stirring lower addition 17.9g ammonium ceric nitrate, after mixture stirs 2 hours at this temperature, it is evaporated to about 1/4 volume, adds 50ml water, with each 50ml extraction into ethyl acetate 4 times, combining extraction liquid, dried over sodium sulfate, recovered under reduced pressure ethyl acetate, obtain 5-picoline-2,3-diethyl dicarboxylate product 1.93g, yield 80.75%.
1H-NMR(300MHz, CDCl3): δ 8.60(s, 1H), 8.08(s, 1H), 4.44(q, 2H), 4.40(q, 2H), 2.41(s, 3H), 1.42(t, 3H), 1.38 (t, 3H)
Embodiment 6
By 3.75g4-hydrogen-5-methoxyl methyl-1-(p-methoxyphenyl) pyridine-2,3-diethyl dicarboxylate adds in 250mL there-necked flask, add 25ml acetone/water mixed liquor (3/1, v/v), room temperature, stirring lower addition 17.9g ammonium ceric nitrate, after mixture stirs 3 hours at this temperature, it is evaporated to about 1/4 volume, adds 50ml water, with each 50ml extraction into ethyl acetate 4 times, combining extraction liquid, dried over sodium sulfate, recovered under reduced pressure ethyl acetate, obtain 5-methoxyl methyl pyridine-2,3-diethyl dicarboxylate product 2.19g, yield 81.41%.
1H-NMR(300MHz, CDCl3): δ 8.66(s, 1H), 8.12(s, 1H), 4.60(s, 2H), 4.46(q, 2H), 4.42(q, 2H), 3.42(s, 3H), 1.42(t, 3H), 1.38 (t, 3H)
Embodiment 7
By 3.45g4-hydrogen-5-methyl isophthalic acid-(p-methoxyphenyl) pyridine-2,3-diethyl dicarboxylate adds in 250mL there-necked flask, add 25ml acetonitrile/water mixed liquor (3/1, v/v), room temperature, the lower 26.7g of stirring add ammonium ceric nitrate, after mixture stirs 2 hours at this temperature, it is evaporated to about 1/4 volume, adds 50ml water, with each 50ml extraction into ethyl acetate 4 times, combining extraction liquid, dried over sodium sulfate, recovered under reduced pressure ethyl acetate, obtain 5-picoline-2,3-diethyl dicarboxylate product 2.18g, yield 91.21%.
1H-NMR(300MHz, CDCl3): δ 8.60(s, 1H), 8.08(s, 1H), 4.44(q, 2H), 4.40(q, 2H), 2.41(s, 3H), 1.42(t, 3H), 1.38 (t, 3H)
Embodiment 8
By 3.45g4-hydrogen-5-methyl isophthalic acid-(p-methoxyphenyl) pyridine-2,3-diethyl dicarboxylate adds in 250mL there-necked flask, add 20ml acetonitrile, lower dropping 17.9g ammonium ceric nitrate is stirred at room temperature and is dissolved in 5ml aqueous solution, within 20 minutes, add, after mixture stirs 2 hours at this temperature, it is evaporated to about 1/4 volume, adds 50ml water, with each 50ml extraction into ethyl acetate 4 times, combining extraction liquid, dried over sodium sulfate, recovered under reduced pressure ethyl acetate, obtain 5-picoline-2,3-diethyl dicarboxylate product 1.92g, yield 80.33%.
1H-NMR(300MHz, CDCl3): δ 8.60(s, 1H), 8.08(s, 1H), 4.44(q, 2H), 4.40(q, 2H), 2.41(s, 3H), 1.42(t, 3H), 1.38 (t, 3H).
Claims (4)
1. the method preparing imidazolinone herbicide intermediate, it is characterized in that: prepare imidazolinone herbicide intermediate reaction formula as follows, in polar solvent, intermediate is reacted to obtain through ammonium ceric nitrate for raw material with compound (1), i.e. 5-picoline-2,3-dicarboxylic diester or 5-methoxyl methyl pyridine-2,3-dicarboxylic acid diester；Reaction equation is as follows:
In formula: R1For methyl or methoxyl methyl；R2For methyl or ethyl；R3、R4Difference, is respectively selected from hydrogen or methoxyl group；Polar solvent is acetonitrile/water or acetone/water.
2. by the method preparing imidazolinone herbicide intermediate described in claim 1, it is characterized in that: compound (1) and ammonium ceric nitrate are in polar solvent, in the lower 0.5-12.0 hour prepared 5-picoline-2 of reaction of-20-80 DEG C of stirring, 3-dicarboxylic diester or 5-methoxyl methyl pyridine-2,3-dicarboxylic acid diester；Wherein ammonium ceric nitrate consumption is 2.0-10.0 times of compound (1) in mol.
3. by the method preparing imidazolinone herbicide intermediate described in claim 2, it is characterized in that: compound (1) and ammonium ceric nitrate are in polar solvent, in the lower 0.5-6.0 hour prepared 5-picoline-2 of reaction of-10-50 DEG C of stirring, 3-dicarboxylic diester or 5-methoxyl methyl pyridine-2,3-dicarboxylic acid diester；Wherein ammonium ceric nitrate consumption is 2.5-7.0 times of compound (1) in mol.
4. by the method preparing imidazolinone herbicide intermediate described in claim 3, it is characterized in that: compound (1) and ammonium ceric nitrate are in polar solvent, in the lower 0.5-3.0 hour prepared 5-picoline-2 of reaction of-5-30 DEG C of stirring, 3-dicarboxylic diester or 5-methoxyl methyl pyridine-2,3-dicarboxylic acid diester；Wherein ammonium ceric nitrate consumption is 3.0-6.0 times of compound (1) in mol；The volume ratio of acetonitrile or acetone and water is 1/1-5/1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310030106.1A CN103965100B (en) | 2013-01-25 | 2013-01-25 | A kind of method preparing imidazolinone herbicide intermediate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310030106.1A CN103965100B (en) | 2013-01-25 | 2013-01-25 | A kind of method preparing imidazolinone herbicide intermediate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103965100A CN103965100A (en) | 2014-08-06 |
| CN103965100B true CN103965100B (en) | 2016-06-29 |
Family
ID=51235159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310030106.1A Active CN103965100B (en) | 2013-01-25 | 2013-01-25 | A kind of method preparing imidazolinone herbicide intermediate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103965100B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114644565B (en) * | 2020-12-17 | 2024-05-03 | 江苏中旗科技股份有限公司 | Synthesis method of key intermediate of imidazolinone compound |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0461401A1 (en) * | 1990-06-15 | 1991-12-18 | American Cyanamid Company | Process for the preparation of dialkyl, pyridine-2,3-dicarboxylates and derivatives thereof from dialkyl dichloromaleate |
| US5281713A (en) * | 1991-12-20 | 1994-01-25 | American Cyanamid Company | Process for the manufacture of 2-alkoxymethylacrolein |
| US5925764A (en) * | 1998-06-15 | 1999-07-20 | Wu; Wen-Xue | Process and intermediated for the manufacture of pyridine-2, 3-dicarboxylate compounds |
| CN101875630A (en) * | 2009-04-29 | 2010-11-03 | 中国中化股份有限公司 | Preparation method of pyridine-2,3-dicarboxylic ester |
| CN101648902B (en) * | 2009-09-15 | 2012-11-21 | 中国药科大学 | Dihydropyridine type tumor chemotherapeutic sensitizer and application thereof |
-
2013
- 2013-01-25 CN CN201310030106.1A patent/CN103965100B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103965100A (en) | 2014-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104447396B (en) | Benzoin oxime derivative and preparation method thereof | |
| CN104876995A (en) | A preparing method of a chenodeoxycholic acid derivative | |
| CN106365986B (en) | Compound and preparation method thereof and the purposes in synthesis Bu Waxitan | |
| CN104045602A (en) | Improved method for preparing tetrazole for valsartan | |
| CN106397519A (en) | Preparation method of altrenogest | |
| CN101985424B (en) | Method for synthesizing o-nitroacetophenone compound | |
| CN103965100B (en) | A kind of method preparing imidazolinone herbicide intermediate | |
| CN105693737B (en) | Bipyridine ligand with axial chirality and synthetic method thereof | |
| CN103880756B (en) | The preparation method of a kind of Azilsartan intermediate | |
| CN104086456B (en) | A kind of synthetic method of sartanbiphenyl | |
| CN107417606B (en) | Method for converting N-cyanomethyl bis (trifluoromethyl) nicotinamide into flonicamid and application | |
| CN103922934B (en) | The alkylation of active methylene compound | |
| CN103664766B (en) | Preparation method of 2-aminopyridine-4-methyl alcohol | |
| CN103232344B (en) | A kind of method of synthesizing S-2-methyl chloropropionate | |
| CN104370961B (en) | The method of iso-octyl phosphine monooctyl acid monooctyl ester is prepared in a kind of phase transfer catalysis (PTC) hydrolysis | |
| CN102942553B (en) | Preparation method for 6-carboxylfluorescein | |
| CN103601671A (en) | Preparation method of iodo trifluoro methyl pyridine | |
| CN113329994A (en) | Method for continuously preparing 5-cyanodiol | |
| CN105061375A (en) | Method for preparing 3-isochromanone | |
| CN104496845B (en) | Synthesis method of tri(azidoacetyloxymethyl)nitromethane | |
| CN111138269A (en) | Process method for preparing 2-butanone acid sodium salt | |
| CN104030906A (en) | Method for preparing 9-fluorenone by liquid-phase oxidation | |
| CN115215767B (en) | Process for preparing 2-cyano-3-ethoxyacrylic acid ethyl ester derivative | |
| CN103601640A (en) | Preparation method of cyclohexane trione compounds | |
| CN104370807B (en) | The synthetic method of a kind of 6-hydroxyl-5-nitronicotinic acid and process for separation and purification thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20160113 Address after: 110021 Liaodong Road, Tiexi District, Liaoning, No. 8-1, No. Applicant after: SHENYANG SINOCHEM PESTICIDE CHEMICAL RESEARCH AND DEVELOPMENT CO., LTD. Address before: 100031 Beijing, Xicheng District, the door of the revitalization of the main street, No. 28 Applicant before: Sinochem Corporation Applicant before: Shenyang Research Institute of Chemical Industry |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |