CN110218153A - A kind of preparation method of midbody compound 2,6- diethyl -4- methylbenzene malonate - Google Patents
A kind of preparation method of midbody compound 2,6- diethyl -4- methylbenzene malonate Download PDFInfo
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Abstract
A kind of midbody compound 2, the preparation method of 6- diethyl -4- methylbenzene malonate, with 2, 6- diethyl -4- methylaniline is raw material, through diazotising, iodate obtains 2, 6- diethyl -4- methyl iodobenzene, then using CuI and L-PROLINE as catalyst system, make 2, coupling reaction occurs for 6- diethyl -4- methyl iodobenzene and diester malonate, 40-60 DEG C of reaction temperature, obtain 2, 6- diethyl -4- methylbenzene malonate, this method reaction condition is mild, raw material sources are extensive, synthetic route is short, catalyst used is cheap, two-step reaction total recovery reaches 70% or more, 98% or more target product purity, preparation method simple process, lower production costs, consersion unit is required low, it can effectively reduce energy consumption, industrialized production with higher Value.
Description
Technical field
The invention belongs to the preparation fields of herbicide raw medicine intermediate, and in particular to a kind of midbody compound 2,6- diethyl
The preparation method of base -4- methylbenzene malonate.
Background technique
The general entitled pinoxaden of pinoxaden English；Chemical name: 8- (2,6- diethyl -4- aminomethyl phenyl) -1,2,
4,5- tetrahydro -7- oxo -7H- pyrazolo [1,2-d] [1,4,5] oxa- diazepine -9- base 2,2- dimethyl propylene acid esters；Molecule
Formula: C23H32N2O4；Relative molecular mass: 400.5；CAS accession number: [243973-20-8]；Trade name: love show, Axial etc.,
Structural formula is as follows:
Pinoxaden is to possess unique chemistry by the phenylpyrrazolin class herbicide of Syngenta discovery, exploitation and production
Structure, it can inhibit the activity of acetyl-CoA carboxylase (ACCase), hinder the biosynthesis of fatty acid, interfere cell membrane shape
At, cause weed growth to stop, it is final dead.
Pinoxaden is selectivity, inner sucting conduction type gramineous weed weedicide, and efficiently, wide spectrum is quickly inhaled by cauline leaf
It receives.1~3 week after medication, there is phytotoxicity symptom, separate living tissue stops growing quickly, and necrosis rapidly.Bud rear defence removes wheat
With barley field annual gramineous weed, as amur foxtail, Alopecurus, wild avena sativa, rye grass, Phalaris grass, herba setariae viridis, hard grass,
Wang grass and caput grass etc..Currently, pinoxaden is mainly used for two big fields: cereal (wheat and barley etc.) and non-crop field
(lawn and gardening etc.).Cereal is the most important application market of pinoxaden, is secondly non-crop, and the market share of the two is distinguished
Account for about 60% and 40%.Pinoxaden is seldom by root absorption, therefore, soil activation very little.
Pinoxaden is there are two key intermediate, first is that [Isosorbide-5-Nitrae, 5] oxygen diaza heptane dihydrobromide, the other is 2,
6- diethyl -4- methylbenzene dimethyl malenate, structural formula difference are as follows:
The preparation route of pinoxaden is unfolded around two key intermediates, and two intermediates are by condensation, so
It reacts to obtain pinoxaden with pivaloyl chloride afterwards, route is as follows:
Currently, key intermediate 2, the synthetic method of 6- diethyl -4- methylbenzene dimethyl malenate mainly have following several
Route:
Synthetic route 1:
Patent document WO0078712 report route with -4 monomethyl aniline (MMA) of 2,6- diethyl be raw material, through diazotising, bromine
Change obtains 2,6- diethyl -4- methyl bromobenzene, intermediate and malononitrile coupling reaction, the phenylpropyl alcohol dintrile replaced, intermediate
Alcoholysis in methyl alcohol again, obtains key intermediate 2,6- diethyl -4- methylbenzene dimethyl malenate, in this route, reaction temperature
Degree is at 140 DEG C or so, the high requirements on the equipment, and coupling reaction needs to use bi triphenyl phosphorus palladium chloride as being catalyzed
Agent, expensive, reaction temperature is higher, and production cost is higher.
Synthetic route 2:
The route of patent document WO0078881 report: starting material 2,6- dibromo open-chain crown ether, 2,6- dibromos are to first
First with vinylidene chloride substitution reaction occurs for base aniline, and the bromo- 4- methyl of 2,6- bis- can be obtained using being esterified after hydrolysis
Ethyl phenylacetate, then the α position hydrogen under basic conditions on substituted carbonyl and reacting with vinyl tributyl stannane obtains this
The precursor of product, final step react to obtain required product by hydrogenation catalyst.
In the route, reactant ethylene base tributyl stannane is more toxic, and price is higher, is easy to produce in use
Raw security risk, and need expensive palladium catalyst；Final step needs to carry out hydrogenation, increases cost, this is initial stage
The route of pinoxaden is synthesized, step is more, is not suitable for industrialization.
Synthetic route 3:
Document The Journal of Organic Chemistry, 2011,76 (19): 8107-8112, the synthesis of report
Route is more similar with synthetic route 1, and grignard reaction first occurs for 2,6- diethyl -4- methyl bromobenzenes, then with trialkyl boric acid
Reaction then occurs substitution reaction with bromoacetate, obtains product precursor, finally the hydrogen under basic conditions on substituted carbonyl
Substitution reaction occurs with bromine Ethyl formate, obtains required product.
Route reaction yield during synthesizing boronic acid intermediate is lower, and is difficult to be promoted, and only about 30%, limit
The feasibility for carrying out industrialized production is made.
Route 4:
The route of patent document WO200078881A2 report uses 3,5- diethyl phenol as starting material, with chloromethane
Acetoacetic ester reaction, protects the hydroxyl of reactant, aligns in acid condition at it carry out chloromethylation later, then cyanogen
Base replaces chlorine, then sloughs hydroxy-protective group, methylates with iodomethane reaction, cyano is hydrolyzed to carboxylic under alkaline condition
Acid, then esterification is carried out with ethyl alcohol, finally the position the α hydrogen of substituted carbonyl reacts to obtain most with ethyl chloroformate under basic conditions
Final product.
The synthetic route synthesis step is excessive, and trivial operations, by multistep reaction, overall yield is relatively low, production cost
Height, and substrate potassium cyanide and iodomethane that two are more toxic have been used, post-processing is complicated, and operation difficulty is larger.
Summary of the invention
The purpose of the present invention is to provide a kind of preparations of midbody compound 2,6- diethyl -4- methylbenzene malonate
Method, preparation process overall yield of reaction reach 70% or more, and 98% or more target product purity, reaction condition is mild, synthesize road
Line is short, and raw material is easy to get, is cheap, and reaction temperature is lower, and energy consumption can be effectively reduced, and requires low, production cost to consersion unit
Lower, Environmental Safety is suitable for industrialized production.
In order to achieve the above object, the invention provides the following technical scheme:
A kind of midbody compound 2, the preparation method of 6- diethyl -4- methylbenzene malonate, comprising the following steps:
1) iodination reaction
2,6- diethyl -4- methylaniline is dissolved in acid, sodium nitrite in aqueous solution is added dropwise into system, carries out diazonium
Change, 0-5 DEG C of reaction temperature, reaction time 0.5-2h；Then addition iodo reagent, progress iodination reaction, reaction time 10-24h,
Extraction reaction solution, drying, precipitation obtain 2,6- diethyl -4- methyl iodobenzene after reaction, are directly used in without purifying next
Step reaction；
Wherein, the molar ratio of each reactant is 2,6- diethyl -4- methylaniline: acid: sodium nitrite: iodo reagent=1:
3-6:1-1.5:1-2；
2) coupling reaction
Under nitrogen protection atmosphere, by 2,6- diethyl -4- methyl iodobenzene, diester malonate, cuprous iodide, L-PROLINE,
Cesium carbonate, DMSO mixing, is heated to 40-60 DEG C, insulated and stirred 10-24h, after reaction, solvent extraction is added, removes solvent
After obtain 2,6- diethyl -4- methylbenzene malonate；
Wherein, the molar ratio of each reactant is 2,6- diethyl -4- methyl iodobenzene: malonate: cuprous iodide: L- dried meat ammonia
Acid: cesium carbonate=1:1-2:0.01-0.2:0.02-0.4:4-5, the dosage of solvent DMSO are 2,6- diethyl -4- methyl iodobenzene
5-20 times of quality；
Reaction equation is as follows:
Preferably, in step 1), the acid is sulfuric acid or hydrochloric acid.
Also, iodo reagent described in step 1) is potassium iodide or sodium iodide.
Preferably, in step 1), in the sodium nitrite in aqueous solution, the mass fraction of sodium nitrite is 30-40%.
Also, the iodo reagent is to be added dropwise to reaction system by aqueous solution form in step 1).
Further, in the aqueous solution of step 2) the iodo reagent, the mass fraction of iodo reagent is 30-40%.Into one
Step, diester malonate described in step 2) are dimethyl malenate or diethyl malonate.
Also, the extractant is selected from ethyl acetate, methylene chloride, dichloroethanes or first in step 1) and/or step 2)
Base tertbutyl ether.
The present invention, for raw material, obtains 2,6- diethyl -4- first through diazotising, iodate with 2,6- diethyl -4- methylaniline
Base iodobenzene, 2,6- diethyl -4- methyl iodobenzenes and diester malonate are catalysis with cuprous iodide and L-PROLINE (L-Proline)
System, using cesium carbonate as alkali, DMSO is solvent, and at 40-60 DEG C through coupling reaction, 2,6- diethyl -4- methylbenzene the third two is made
Acid esters；Under reaction system of the invention, cuprous iodide and L-PROLINE form cuprous salt complex compound, improve cuprous iodide
Dissolubility makes 2,6- diethyl -4- methyl iodobenzene and diester malonate so that in the system, cesium carbonate has good solubility
In 40-60 DEG C of at a temperature of generation C-H activation coupling reaction, reaction condition of the present invention improves catalyst activity, hinders catalysis
The decomposition of agent, mild condition reduce the generation of by-product, and atom utilization is high, improve reaction yield, two-step reaction it is total
Yield can achieve 70% or more.
Compared with prior art, the invention has the following beneficial effects:
The present invention synthesizes 2,6- diethyl -4- methyl iodobenzene through sandmeyer reaction by 2,6- diethyl -4- methylaniline,
Stable reaction, reproducible, simple process, raw material sources are extensive, and price is low.
2, the 6- diethyl -4- methyl iodobenzene that the present invention obtains can be used to coupling reaction without purifying, in coupling reaction
In, it avoids improving atom utilization using cuprous iodide and L-PROLINE as catalyst system using expensive palladium catalyst, and
Coupling reaction yield is good, and raw material is easy to get, and reaction temperature is low, and 40-60 DEG C, with regard to achievable reaction, effectively reduces energy consumption.
Synthetic route of the invention is short, high income, and iodate and the total recovery for being coupled two-step reaction can achieve 70% or more,
Lower production costs, industrial production value with higher.
Specific embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1:
2,6- diethyl -4- methylaniline (60g, 98%, 0.36mol) is added in reaction flask, is added dropwise hydrochloric acid (6M)
240ml, be slowly added dropwise control 10 DEG C of temperature be cooled to 0~5 DEG C hereinafter, dripping off, start be added dropwise plus sodium nitrite (27.6g,
Aqueous solution (wherein water be 56g) 0.4mol), when dropwise addition, are kept for 0~5 DEG C of temperature, drip off insulated and stirred 1h.Then iodate is added dropwise
Water (150ml) solution of potassium (71.7g, 0.43mol) keeps 5 DEG C of temperature hereinafter, dripping off insulated and stirred 1h, slowly restores to room
Temperature is stirred overnight, fully reacting.Post-processing is extracted with ethyl acetate twice, merges organic phase, molten with saturated sodium carbonate acid respectively
Liquid and sodium chloride solution wash once liquid separation, and organic phase anhydrous sodium sulfate is dry, filter and remove desiccant, and revolving removes solvent and obtains
2,6- diethyl -4- methyl iodobenzenes, 83.9g, yield 85% are directly used in next step without purifying.
Upper step product is added in reaction flask, under nitrogen protection, addition dimethyl malenate (49.1g, 0.37mol),
CuI (2.9g, 0.0153mol), L-PROLINE (3.52g, 0.0306mol), cesium carbonate (397.5g, 1.22mol), DMSO
Then 600ml begins heat to 40 DEG C, for 24 hours, fully reacting is added saturated ammonium chloride solution and is quenched, with acetic acid second insulated and stirred
Ester is extracted twice, liquid separation, merges organic phase, and washing organic phase is primary, liquid separation, and anhydrous sodium sulfate is dry, is filtered and is removed desiccant,
It rotates solvent and obtains 2,6- diethyl -4- methyl phenylmalonate carbomethoxyphenyl crude product, purified with recrystallizing methanol, obtain 2,6- diethyl
Base -4- methyl phenylmalonate carbomethoxyphenyl sterling, 70.6g, product purity 99.2%, yield 83%,1H NMR(CDCl3,
300Hz): d 1.18 (t, 6H), 2.30 (s, 3H), 2.64 (q, 4H), 3.73 (s, 6H), 5.06 (s, 1H), 6.93 (s, 2H).
Embodiment 2
2,6- diethyl -4- methylaniline (30g, 98%, 0.18mol) is added in reaction flask, is added dropwise hydrochloric acid (6M)
115ml, be slowly added dropwise control 10 DEG C of temperature be cooled to 0~5 DEG C hereinafter, dripping off, start be added dropwise plus sodium nitrite (27.6g,
0.4mol) aqueous solution (amounting to 83.6g, wherein water is 56g), is slowly added dropwise 0~5 DEG C of temperature of holding, drips off insulated and stirred 2h；So
Water (60ml) solution of sodium iodide (32.2g, 0.215mol) is added dropwise afterwards, keeps 5 DEG C of temperature hereinafter, dripping off insulated and stirred 1h, delays
It is slow to restore to room temperature, it is stirred overnight, fully reacting.
Reaction solution is extracted with ethyl acetate twice, merges organic phase, molten with saturated sodium carbonate acid solution and sodium chloride respectively
Liquid washes once liquid separation, and organic phase anhydrous sodium sulfate is dry, filters and removes desiccant, rotates solvent and obtain 2,6- diethyl -4- first
Base iodobenzene, 42.9g, yield 87% are directly used in next step without purifying.
Upper step product is added in reaction flask, under nitrogen protection, addition diethyl malonate (56.05g, 0.35mol),
CuI (5.96g, 0.0313mol), L-PROLINE (7.2g, 0.0626mol), cesium carbonate (199.4g, 0.612mol), DMSO
429ml, then begins heat to 55 DEG C, insulated and stirred 12h, and fully reacting is added saturated ammonium chloride solution and is quenched, with acetic acid second
Ester is extracted twice, liquid separation, merges organic phase, and washing organic phase is primary, liquid separation, and anhydrous sodium sulfate is dry, is filtered and is removed desiccant,
Revolving removes solvent and obtains 2,6- diethyl -4- methylbenzene diethyl malonate, 39.3g, product purity 98.3%, yield 82%.
Embodiment 3
2,6- diethyl -4- methylaniline (20g, 98%, 0.12mol) is added in reaction flask, is added dropwise hydrochloric acid (6M)
87.0ml, be slowly added dropwise control 10 DEG C of temperature be cooled to 0~5 DEG C hereinafter, dripping off, start be added dropwise plus sodium nitrite (9.2g,
0.13mol) aqueous solution (28.0g) is slowly added dropwise 0~5 DEG C of temperature of holding, drips off insulated and stirred 1h；Then sodium iodide is added dropwise
Water (120ml) solution of (27.0g, 0.18mol) keeps 5 DEG C of temperature hereinafter, dripping off insulated and stirred 1h, slowly restores to room temperature,
It is stirred overnight, fully reacting.
Reaction solution is extracted with ethyl acetate twice, merges organic phase, molten with saturated sodium carbonate acid solution and sodium chloride respectively
Liquid washes once liquid separation, and organic phase anhydrous sodium sulfate is dry, filters and removes desiccant, rotates solvent and obtain 2,6- diethyl -4- first
Base iodobenzene 28.6g, yield 87.0% are directly used in next step without purifying.
Upper step product is added in reaction flask, under nitrogen protection, addition diethyl malonate (35.08g,
0.219mol), CuI (3.11g, 0.01635mol), L-PROLINE (3.76g, 0.0327mol), cesium carbonate (142.7g,
0.438mol), DMSO 240ml, then begins heat to 60 DEG C, insulated and stirred 22h, and it is molten that saturated ammonium chloride is added in fully reacting
Liquid is quenched, and liquid separation twice is extracted with ethyl acetate, and merges organic phase, and washing organic phase is primary, liquid separation, and anhydrous sodium sulfate is dry,
It filters and removes desiccant, revolving removes solvent and obtains 2,6- diethyl -4- methylbenzene diethyl malonate, 26.2g, product purity
98.5%, yield 82%.
Embodiment 4
2,6- diethyl -4- methylaniline (300g, 98%, 1.8mol) is added in reaction flask, is added dropwise hydrochloric acid (6M)
1.2L, be slowly added dropwise control 10 DEG C of temperature be cooled to 0~5 DEG C hereinafter, dripping off, start be added dropwise plus sodium nitrite (138.0g,
2.0mol) aqueous solution (400g) is added dropwise and is kept for 0~5 DEG C of temperature, drip off insulated and stirred 2h；Then be added dropwise sodium iodide (322.5g,
Water (600ml) solution 2.15mol) keeps 5 DEG C of temperature hereinafter, dripping off insulated and stirred 1h, slowly restores to room temperature, stirred
Night, fully reacting.
Reaction solution is extracted with ethyl acetate twice, merges organic phase, molten with saturated sodium carbonate acid solution and sodium chloride respectively
Liquid washes once liquid separation, and organic phase anhydrous sodium sulfate is dry, filters and removes desiccant, and revolving removes solvent and obtains 2,6- diethyl -4-
Methyl iodobenzene 429.3g, yield 87% are directly used in next step without purifying.
Upper step product is added in reaction flask, under nitrogen protection, addition dimethyl malenate (231.1g, 1.75mol),
CuI (59.59g, 0.313mol), L-PROLINE (72g, 0.626mol), cesium carbonate (2.04kg, 6.26mol), DMSO 4.2L,
Then 60 DEG C are begun heat to, for 24 hours, fully reacting is added saturated ammonium chloride solution and is quenched, is extracted with ethyl acetate insulated and stirred
Twice, liquid separation merges organic phase, and washing organic phase is primary, liquid separation, and anhydrous sodium sulfate is dry, filters and removes desiccant, and revolving is removed
Solvent is gone to obtain 2,6- diethyl -4- methylbenzene dimethyl malenate, 361.7g, product purity 98.3%, yield 83.0%.
Comparative example
By diethyl malonate (20.0g, 0.125mol), 2,6- diethyl -4- methyl iodobenzene (17.1g, 0.062mol)
DMSO 100ml is added in CuI (2.38g, 0.0125mol), potassium carbonate (138.2g, 1.0mol), is then heated to 120 DEG C, heat preservation
20h is stirred, monitoring is extracted reaction solution, does not react between substrate.
Claims (8)
1. a kind of midbody compound 2, the preparation method of 6- diethyl -4- methylbenzene malonate, comprising the following steps:
1) iodination reaction
2,6- diethyl -4- methylaniline is dissolved in acid, sodium nitrite in aqueous solution is added dropwise into system, carries out diazotising, instead
0-5 DEG C of temperature is answered, reaction time 0.5-2h；Then iodo reagent is added, carries out iodination reaction, reaction time 10-24h, reaction
After extract reaction solution, drying, precipitation obtain 2,6- diethyl -4- methyl iodobenzene, be directly used in without purifying anti-in next step
It answers；
Wherein, the molar ratio of each reactant is 2,6- diethyl -4- methylaniline: acid: sodium nitrite: iodo reagent=1:3-6:
1-1.5:1-2；
2) coupling reaction
Under nitrogen protection atmosphere, by 2,6- diethyl -4- methyl iodobenzene, diester malonate, cuprous iodide, L-PROLINE, carbonic acid
Caesium mixes in solvent DMSO, is heated to 40-60 DEG C, insulated and stirred 10-24h, after reaction, solvent extraction is added, removes
Solvent obtains 2,6- diethyl -4- methylbenzene malonate；
Wherein, the molar ratio of each reactant is 2,6- diethyl -4- methyl iodobenzene: malonate: cuprous iodide: L-PROLINE:
Cesium carbonate=1:1-2:0.01-0.2:0.02-0.4:4-5；The dosage of solvent DMSO is 2,6- diethyl -4- methyl iodobenzene quality
5-20 times；
Reaction equation is as follows:
2. midbody compound 2 according to claim 1, the preparation method of 6- diethyl -4- methylbenzene malonate is special
Sign is, in step 1), the acid is sulfuric acid or hydrochloric acid.
3. midbody compound 2 according to claim 1, the preparation method of 6- diethyl -4- methylbenzene malonate is special
Sign is that iodo reagent described in step 1) is potassium iodide or sodium iodide.
4. midbody compound 2 according to claim 1, the preparation method of 6- diethyl -4- methylbenzene malonate is special
Sign is, in step 1), in the sodium nitrite in aqueous solution, the mass fraction of sodium nitrite is 30-40%.
5. midbody compound 2 according to claim 1, the preparation method of 6- diethyl -4- methylbenzene malonate is special
Sign is, in step 1), the iodo reagent is to be added dropwise to reaction system by aqueous solution form.
6. midbody compound 2 according to claim 5, the preparation method of 6- diethyl -4- methylbenzene malonate is special
Sign is, in the aqueous solution of step 1) the iodo reagent, the mass fraction of iodo reagent is 30-40%.
7. midbody compound 2 according to claim 1, the preparation method of 6- diethyl -4- methylbenzene malonate is special
Sign is that diester malonate described in step 2) is dimethyl malenate or diethyl malonate.
8. midbody compound 2 according to claim 1, the preparation method of 6- diethyl -4- methylbenzene malonate is special
Sign is, in step 1) and/or step 2), the extractant is selected from ethyl acetate, methylene chloride, dichloroethanes or methyl- tert
Butyl ether.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110950778A (en) * | 2019-12-24 | 2020-04-03 | 安徽省化工研究院 | Process and catalyst system for preparing aromatic malononitrile |
| CN113121341A (en) * | 2019-12-31 | 2021-07-16 | 江苏中旗科技股份有限公司 | Method for synthesizing 2, 6-diethyl-4-methyl phenylacetate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110950778A (en) * | 2019-12-24 | 2020-04-03 | 安徽省化工研究院 | Process and catalyst system for preparing aromatic malononitrile |
| CN113121341A (en) * | 2019-12-31 | 2021-07-16 | 江苏中旗科技股份有限公司 | Method for synthesizing 2, 6-diethyl-4-methyl phenylacetate |
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Application publication date: 20190910 |