CN103965100A - Method for preparing imidazolinone weed killer intermediate - Google Patents
Method for preparing imidazolinone weed killer intermediate Download PDFInfo
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- CN103965100A CN103965100A CN201310030106.1A CN201310030106A CN103965100A CN 103965100 A CN103965100 A CN 103965100A CN 201310030106 A CN201310030106 A CN 201310030106A CN 103965100 A CN103965100 A CN 103965100A
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- 0 *c1cc(*)c(C(CC2)/C=C(\*)/C/C(/*)=C2/C2=C*2)cc1 Chemical compound *c1cc(*)c(C(CC2)/C=C(\*)/C/C(/*)=C2/C2=C*2)cc1 0.000 description 1
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- 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
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Abstract
The present invention belongs to the field of organic synthesis, and particularly relates to a method for preparing an imidazolinone weed killer intermediate. According to the present invention, the imidazolinone weed killer intermediate preparation reaction formula is as the follow, and a compound 1 is adopted as a raw material and reacts in a polar solvent through ceric ammonium nitrate to obtain an intermediate, ie., 5-methylpyridine-2,3-dicarboxylic acid diester or 5-methoxymethylpyridine-2,3-dicarboxylic acid diester, wherein R1 is methyl or methoxymethyl, and R2 is methyl or ethyl; and the method has characteristics of simple reparation process, simple operation and easily available raw materials, and is the method for easily preparing a large amount of the imidazolinone weed killer intermediate 5-methyl or 5-methoxymethyl pyridine-2,3-dicarboxylic acid diester.
Description
Technical field
The invention belongs to organic synthesis field, specifically a kind of method of preparing imidazolinone herbicide intermediate.
Background technology
5-methyl or 5-methoxyl methyl pyridine-2, 3-dicarboxylic diester is the key intermediate of imidazolinone herbicide, synthetic upper adopt quinoline or quinoline oxidation to carry out again esterification to obtain (US5281713 for example, 1994), or adopt two enamine succinates and the condensation of propylene aldehydes to synthesize (JP for example, 1-143857, 1989), or adopt butene dioic acid halo derivatives and the condensation under ammonia or the existence of ammonia salt of propylene aldehydes (EP0461401A1 for example, 1991) etc., these methods or by-product are unfavorable for the purifying of intermediate more, or transformation efficiency is lower, or intermediate is stable and not easy to operate not.
Summary of the invention
The object of the present invention is to provide a kind of method of preparing imidazolinone herbicide intermediate.
The technical solution used in the present invention is for achieving the above object:
A kind of method of preparing imidazolinone herbicide intermediate, prepare imidazolinone herbicide intermediate reaction formula as follows, the compound (1) of take reacts to obtain intermediate as raw material in polar solvent through ceric ammonium nitrate, be 5-picoline-2,3-dicarboxylic diester or 5-methoxyl methyl pyridine-2,3-dicarboxylic acid diester; Reaction formula is as follows:
In formula: R
1for methyl or methoxyl methyl; R
2for methyl or ethyl; R
3, R
4difference, is selected from respectively hydrogen or methoxyl group, i.e. R
3with R
4when different, be hydrogen or methoxyl group.
Compound (1) and ceric ammonium nitrate, in polar solvent, stir lower reaction and within 0.5-12.0 hour, make 5-picoline-2,3-dicarboxylic diester or 5-methoxyl methyl pyridine-2,3-dicarboxylic acid diester in-20-80 ° C; Wherein ceric ammonium nitrate consumption with the 2.0-10.0 that mole counts compound (1) doubly.
Further preferably, compound (1), stirs lower reaction and within 0.5-6.0 hour, makes 5-picoline-2,3-dicarboxylic diester or 5-methoxyl methyl pyridine-2,3-dicarboxylic acid diester in-10-50 ° C with ceric ammonium nitrate in polar solvent; Wherein ceric ammonium nitrate consumption with the 2.5-7.0 that mole counts compound (1) doubly; Polar solvent is acetonitrile, acetone, acetonitrile/water or acetone/water.
Further preferred, compound (1) and ceric ammonium nitrate, in polar solvent, stir lower reaction and within 0.5-3.0 hour, make 5-picoline-2,3-dicarboxylic diester or 5-methoxyl methyl pyridine-2,3-dicarboxylic acid diester in-5-30 ° C; Wherein ceric ammonium nitrate consumption with the 3.0-6.0 that mole counts compound (1) doubly; Polar solvent is acetonitrile/water or acetone/water, and the volume ratio of acetonitrile or acetone and water is 1/1-5/1.
Described compound (1) can be according to reference Organic & Biomolecular Chemistry, 2009,7 (23), instruction in 4943-4953 is carried out, and adopts olefine aldehydr to react and within 8-12 hour, obtain compound (1) at 140-200 ° of C with acetylenedicarboxylic acid ester with the alkene imine intermediate original position that p-anisidine produces with o-methoxyaniline or olefine aldehydr.
The present invention has advantages of:
Preparation process of the present invention is easy and simple to handle, and raw material is easy to get, and reaction conditions is gentle, and aftertreatment is easy, is a kind of method that is easy to prepare in a large number imidazolinone herbicide intermediate 5-methyl or 5-methoxyl methyl pyridine-2,3-dicarboxylic acid diester.
Embodiment
Unless the present embodiment Special Statement, palladium salt, formic acid are with gram (g) metering, and acetic acid is in milliliter (mL), and raw material is with gram (g) metering.
Reaction formula is as follows, and the compound (1) of take reacts to obtain intermediate as raw material in polar solvent through ceric ammonium nitrate, i.e. 5-picoline-2,3-dicarboxylic diester or 5-methoxyl methyl pyridine-2,3-dicarboxylic acid diester;
Compound (1) under ceric ammonium nitrate exists in acetonitrile/water or ketone/water stirred for several within ten minutes, to a few hours, obtain 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, under stirring, add solid nitric acid cerium ammonium to complete reaction; Or adopt and first compound (1) to be dissolved in acetonitrile or acetone, stir the lower ceric ammonium nitrate aqueous solution that drips and complete reaction.When preparing in a small amount, react very easy to control; During a large amount of preparation, because the reaction heat producing is difficult for getting rid of in time, cause reaction too violent, therefore ceric ammonium nitrate reagent should not once add, to add safer in batches, and for offsetting the reaction heat producing and controlling reaction starting velocity, reaction is carried out at low temperatures.Typical experimental implementation is as follows: compound (1) is dissolved in to acetonitrile or acetone/water or is dissolved in respectively in acetonitrile or acetone, under stirring, add molar weight 2.0-10.0 times of solid nitric acid cerium ammonium of compound (1) or the ceric ammonium nitrate aqueous solution under in-5 ° of C to room temperature, material room temperature stirred for several ten minutes is after a few hours, reactant is evaporated to 1/4, by in suitable quantity of water impouring concentrated solution, with ethyl acetate, extract, extraction liquid is dry, reclaim under reduced pressure ethyl acetate obtains product, and in water, ceric ammonium 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 solution (3/1, v/v), room temperature, under stirring, add 17.9g ceric ammonium nitrate, mixture stirs after 2 hours at this temperature, be evaporated to approximately 1/4 volume, 50ml water will be added in concentrated solution, by ethyl acetate, extract 4 times again, each with the extraction of 50ml ethyl acetate, merge each extraction liquid, with dried over sodium sulfate extraction liquid, reclaim under reduced pressure ethyl acetate, obtain 5-methoxyl methyl pyridine-2, 3-diethyl dicarboxylate product 1.83g, yield 76.57%.
1H-NMR（300MHz，CDCl3）：δ8.60（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 solution (3/1, v/v), under room temperature, stirring, add 17.9g ceric ammonium nitrate, mixture stirs after 3 hours at this temperature, be evaporated to approximately 1/4 volume, add 50ml water, with each 50ml ethyl acetate extraction 4 times, combining extraction liquid, dried over sodium sulfate, reclaim under reduced pressure ethyl acetate, obtains 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) and, 4.60(s, 2H), 4.46(q, 2H) and, 4.42(q, 2H), 3.42(s, 3H) and, 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 solution (3/1, v/v), under room temperature, stirring, add 17.9g ceric ammonium nitrate, mixture stirs after 2 hours at this temperature, be evaporated to approximately 1/4 volume, add 50ml water, with each 50ml ethyl acetate extraction 4 times, combining extraction liquid, dried over sodium sulfate, reclaim under reduced pressure ethyl acetate, obtains 5-picoline-2,3-diethyl dicarboxylate product 1.74g, yield 72.80%.
1H-NMR（300MHz，CDCl3）：δ8.60（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 solution (3/1, v/v), under room temperature, stirring, add 17.9g ceric ammonium nitrate, mixture stirs after 3 hours at this temperature, be evaporated to approximately 1/4 volume, add 50ml water, with each 50ml ethyl acetate extraction 4 times, combining extraction liquid, dried over sodium sulfate, reclaim under reduced pressure ethyl acetate, obtains 5-methoxyl methyl pyridine-2,3-diethyl dicarboxylate product 2.44g, yield 90.71%.
1H-NMR（300MHz，CDCl3）：δ8.66（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 solution (3/1, v/v), under room temperature, stirring, add 17.9g ceric ammonium nitrate, mixture stirs after 2 hours at this temperature, be evaporated to approximately 1/4 volume, add 50ml water, with each 50ml ethyl acetate extraction 4 times, combining extraction liquid, dried over sodium sulfate, reclaim under reduced pressure ethyl acetate, obtains 5-picoline-2,3-diethyl dicarboxylate product 1.93g, yield 80.75%.
1H-NMR（300MHz，CDCl3）：δ8.60（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 solution (3/1, v/v), under room temperature, stirring, add 17.9g ceric ammonium nitrate, mixture stirs after 3 hours at this temperature, be evaporated to approximately 1/4 volume, add 50ml water, with each 50ml ethyl acetate extraction 4 times, combining extraction liquid, dried over sodium sulfate, reclaim under reduced pressure ethyl acetate, obtains 5-methoxyl methyl pyridine-2,3-diethyl dicarboxylate product 2.19g, yield 81.41%.
1H-NMR（300MHz，CDCl3）：δ8.66（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 solution (3/1, v/v), room temperature, the lower 26.7g of stirring add ceric ammonium nitrate, mixture stirs after 2 hours at this temperature, be evaporated to approximately 1/4 volume, add 50ml water, with each 50ml ethyl acetate extraction 4 times, combining extraction liquid, dried over sodium sulfate, reclaim under reduced pressure ethyl acetate, obtains 5-picoline-2,3-diethyl dicarboxylate product 2.18g, yield 91.21%.
1H-NMR（300MHz，CDCl3）：δ8.60（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, under stirring at room, drip 17.9g ceric ammonium nitrate and be dissolved in the 5ml aqueous solution, within 20 minutes, add, mixture stirs after 2 hours at this temperature, be evaporated to approximately 1/4 volume, add 50ml water, with each 50ml ethyl acetate extraction 4 times, combining extraction liquid, dried over sodium sulfate, reclaim under reduced pressure ethyl acetate, obtains 5-picoline-2,3-diethyl dicarboxylate product 1.92g, yield 80.33%.
1H-NMR（300MHz，CDCl3）：δ8.60（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. a method of preparing imidazolinone herbicide intermediate, it is characterized in that: prepare imidazolinone herbicide intermediate reaction formula as follows, the compound (1) of take reacts to obtain intermediate as raw material in polar solvent through ceric ammonium nitrate, be 5-picoline-2,3-dicarboxylic diester or 5-methoxyl methyl pyridine-2,3-dicarboxylic acid diester; Reaction formula is as follows:
In formula: R1 is methyl or methoxyl methyl; R2 is methyl or ethyl; R3, R4 are different, are selected from respectively hydrogen or methoxyl group.
2. by the method for preparing imidazolinone herbicide intermediate described in claim 1, it is characterized in that: compound (1) and ceric ammonium nitrate are in polar solvent, in-20-80 ° of C, stir lower reaction and within 0.5-12.0 hour, make 5-picoline-2,3-dicarboxylic diester or 5-methoxyl methyl pyridine-2,3-dicarboxylic acid diester; Wherein ceric ammonium nitrate consumption with the 2.0-10.0 that mole counts compound (1) doubly.
3. by the method for preparing imidazolinone herbicide intermediate described in claim 2, it is characterized in that: compound (1) and ceric ammonium nitrate are in polar solvent, in-10-50 ° of C, stir lower reaction and within 0.5-6.0 hour, make 5-picoline-2,3-dicarboxylic diester or 5-methoxyl methyl pyridine-2,3-dicarboxylic acid diester; Wherein ceric ammonium nitrate consumption with the 2.5-7.0 that mole counts compound (1) doubly; Polar solvent is acetonitrile, acetone, acetonitrile/water or acetone/water.
4. by the method for preparing imidazolinone herbicide intermediate described in claim 3, it is characterized in that: compound (1) and ceric ammonium nitrate are in polar solvent, in-5-30 ° of C, stir lower reaction and within 0.5-3.0 hour, make 5-picoline-2,3-dicarboxylic diester or 5-methoxyl methyl pyridine-2,3-dicarboxylic acid diester; Wherein ceric ammonium nitrate consumption with the 3.0-6.0 that mole counts compound (1) doubly; Polar solvent is acetonitrile/water or acetone/water, and the volume ratio of acetonitrile or acetone and water is 1/1-5/1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114644565A (en) * | 2020-12-17 | 2022-06-21 | 江苏中旗科技股份有限公司 | Synthesis method of key intermediate of imidazolone compound |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114644565A (en) * | 2020-12-17 | 2022-06-21 | 江苏中旗科技股份有限公司 | Synthesis method of key intermediate of imidazolone compound |
| 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 |
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