CN109627184A - A kind of preparation method of 2,6- diethyl -4- aminomethyl phenyl malononitrile - Google Patents
A kind of preparation method of 2,6- diethyl -4- aminomethyl phenyl malononitrile Download PDFInfo
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- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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Abstract
The present invention relates to the preparation method of one kind 2,6- diethyl -4- aminomethyl phenyl malononitrile, 2,6- diethyl -4- methyl bromobenzenes in the presence of a catalyst, react to obtain 2,6- diethyl -4- aminomethyl phenyl malononitrile in atent solvent with malononitrile and alkali；Catalyst is palladium (II) complex；Palladium (II) complex is to be prepared by palladium chloride, acid chloride or palladium sulfate with the ligand being suitble to；2,6- diethyl -4- aminomethyl phenyl the malononitrile is as the application for preparing herbicide pinoxaden intermediate.In present invention process, complex-catalyzed 2 formed using biphosphine ligand and palladium chloride, the acid chloride or palladium sulfate to air-stable, 6- diethyl -4- methyl bromobenzene, malononitrile and alkali reaction preparation 2,6- diethyl -4- aminomethyl phenyl malononitrile, not only reaction yield is high, stability is good, and palladium catalyst catalytic activity is high, and dosage is few, can be substantially reduced production cost, so that technique is more environmentally friendly, the high yield that reaches and it is highly selective be unexpected.
Description
Technical field
The present invention relates to a kind of preparation method of 2,6- diethyl -4- aminomethyl phenyl malononitrile and its as preparing herbicide
The application of pinoxaden intermediate.
Background technique
2,6- diethyl -4- aminomethyl phenyl malononitrile is the key that in synthesis neophyl pyrazolines herbicide pinoxaden
Mesosome.Palladium complex catalyst 2,6- diethyl -4- methyl bromide is reported in patent WO0078712 and patent WO2004050607
The method of benzene, malononitrile and highly basic reaction preparation 2,6- diethyl -4- aminomethyl phenyl malononitrile, reaction conversion ratio can reach 97%
More than, but the preparation method, due to using monophosphorus ligand, the palladium complex formed in reaction compares air-sensitive, reaction condition
Harshness, the cost of raw material are higher.
Patent CN106928253 describes another preparation method, and 2,6- diethyl -4- methylanilines pass through
Sandmeyer reacts to obtain 2,6- diethyl -4- methyl bromobenzene, then with malononitrile in cuprous iodide, cuprous bromide or double three
Phenylphosphine nickel chloride is that coupling obtains 2,6- diethyl -4- aminomethyl phenyl malononitrile under catalyst.In this method, valence is used
Cuprous iodide, cuprous bromide or the bi triphenyl phosphine nickel chloride of lattice relative moderate make catalyst, although catalyst cost obviously drops
It is low, but this method reaction time is long, conversion ratio is obviously relatively low, and reaction yield only has 60-78%.
Summary of the invention
In view of this, the purpose of the present invention, is to provide a kind of system for preparing 2,6- diethyl -4- aminomethyl phenyl malononitrile
Preparation Method, the preparation method use biphosphine ligand and palladium chloride to air-stable, acid chloride or palladium sulfate to form complex and make
For catalyst, it is catalyzed 2,6- diethyl -4- methyl bromobenzene, malononitrile and alkali reaction preparation 2,6- diethyl -4- aminomethyl phenyl third
Dintrile, not only reaction yield is high, and stability is good, and catalyst activity is high, and dosage is few, can be substantially reduced and be produced into
This.
Present invention provide the technical scheme that
The preparation method of one kind 2,6- diethyl -4- aminomethyl phenyl malononitrile, 2,6- diethyl -4- methyl bromobenzenes are being catalyzed
In the presence of agent, react to obtain 2,6- diethyl -4- aminomethyl phenyl malononitrile in atent solvent with malononitrile and alkali.
[chemical formula 1]
Further, the preparation method of 2, the 6- diethyl -4- aminomethyl phenyl malononitrile, palladium (II) complex to 2,
The catalysis of the C-C coupling reaction of 6- diethyl -4- methyl bromobenzene, malononitrile and alkali, palladium (II) complex is by palladium chloride, acetic acid
What palladium or palladium sulfate and required ligand prepared.Palladium (II) complex is either respectively by palladium chloride, acid chloride or sulphur
Sour palladium and required ligand are directly added into reaction system and carry out catalysis reaction, are also possible to palladium chloride, acid chloride or sulphur respectively
Sour palladium and required ligand, which are first worked good, to be added reaction system and carries out catalysis reaction, it is advantageous to which palladium chloride can be with dense salt
Acid forms 20% palladium chloride concentrated hydrochloric acid solution form as cosolvent N, uses in the presence of N- dimethyl amine, acid chloride
It is substantially dissolved in tetrahydrofuran.
Further, the catalyst is palladium (II) complex；The alkali is selected from sodium hydroxide, potassium hydroxide, the tert-butyl alcohol
Sodium, potassium tert-butoxide, any one in sodium hydride；It is sub- that the atent solvent is selected from dimethylbenzene, N-Methyl pyrrolidone, dimethyl
Any one in sulfone.
Further, palladium (II) complex is with palladium chloride, acid chloride or palladium sulfate and the ligand being suitble to
Preparation.
Further, it is suitble to the ligand of palladium (II) cooperation be biphosphine ligand, suitable biphosphine ligand ligand is selected from (R)-
1- [(S) -2- (diphenylphosphine) ferrocenyl] ethyl double -3,5- xylyl phosphines (Xyliphos), 1- [bis- (1,1- dimethyl
Ethyl) phosphine] -2- [1- [bis- (2- aminomethyl phenyl) phosphines] ethyl] ferrocene (JOSIPHOS), the bis- diphenylphosphine -9,9- diformazans of 4,5-
Bis- [(2- methoxyphenyl) phenyl phosphorus] ethane (DIPAMP) of base xanthene (XantPhos), 1,2- or (6,6'- dimethoxy connection
Benzene -2,2'- base) any one in bis- (diphenylphosphines) (MeO-BIPHEP).
Further, the molar ratio of palladium chloride, acid chloride or palladium sulfate and ligand is 1:1.0-3.0.
Further, the molar ratio of 2, the 6- diethyl -4- methyl bromobenzene and catalyst, malononitrile, alkali are as follows: 1:
0.0001-0.01:1.0-2.0:2.0-5.0。
Preferably, the molar ratio of 2, the 6- diethyl -4- methyl bromobenzene and catalyst, malononitrile, alkali are as follows: 1:
0.0005-0.005:1.0-1.2:2.5-3.5。
Further, the reaction temperature is 25-140 DEG C.
Preferably, the reaction temperature is 100-130 DEG C.
Further, 2,6- diethyl -4- aminomethyl phenyl malononitrile is as preparing answering for herbicide pinoxaden intermediate
With.
Advantageous effects:
In present invention process, matched using the biphosphine ligand to air-stable with what palladium chloride, acid chloride or palladium sulfate were formed
Object catalysis 2,6- diethyl -4- methyl bromobenzene, malononitrile and alkali reaction preparation 2,6- diethyl -4- aminomethyl phenyl malononitrile are closed,
Not only reaction yield is high, and stability is good, and palladium catalyst catalytic activity is high, and dosage is few, can be substantially reduced production cost, make
Technique is more environmentally friendly, the high yield that reaches and it is highly selective be unexpected.
Specific embodiment
The present invention is described in further detail combined with specific embodiments below, and the present invention is not limited to these implementations
Example, the example all and of the present invention for solving the problems, such as that thinking is adaptable, is within the scope of the invention.
Embodiment 1
Under nitrogen protection, at room temperature, 11.0g potassium tert-butoxide, 60mL 1- methyl -2- pyrrole are added into 100mL four-hole boiling flask
Pyrrolidone and 8.0g 2,6- diethyl -4- methyl bromobenzene add 2.8g malononitrile, stir and are warming up to reaction mixture
102 DEG C, the solution that the palladium chloride concentrated hydrochloric acid solution and 5mL n,N-dimethylacetamide that 0.3g 20% is added are prepared, and
Double -3,5- xylyl the phosphines of 0.47g (R) -1- [(S) -2- (diphenylphosphine) ferrocenyl] ethyl and 10mL 1- methyl -2- pyrrole
The solution of pyrrolidone is warming up to 130 DEG C and reacts 3 hours, while collecting the low-boiling-point substance about 12mL steamed, reaction by distilling apparatus
Terminate, be cooled to 40 DEG C, 40g mixture of ice and water stirring and dissolving solid is added into reaction solution, stratification separates lower water
Solid, filtering is precipitated with hydrochloric acid tune pH to 4-5 in phase, and solid is washed with water to neutrality, dries, obtains faint yellow 2,6- diethyl -4-
Aminomethyl phenyl malononitrile 7.3g, yield 97.3%.
Embodiment 2
At room temperature, 1.0g malononitrile, 30mL dimethyl sulfoxide, stirring and dissolving, to this solution are added into 100mL three-necked flask
In be slowly added to 0.81g sodium hydride (60%), the yellow suspension to be formed is stirred at room temperature 1 hour, be added 2.3g 2,6- diethyl
Base -4- methyl bromobenzene, 0.01g palladium sulfate, 0.07g 4, bis- diphenylphosphine -9, the 9- xanthphos of 5- are stirred and will be reacted
Mixture is warming up to 130 DEG C and reacts 12 hours, and reaction terminates, and is cooled to 40 DEG C, and 30g mixture of ice and water is added into reaction solution and stirs
It mixes dissolved solid, and with 1N hydrochloric acid tune pH to 3-4, and is extracted with ether, with the dry combined ether extraction liquid of anhydrous sodium sulfate,
Concentration, crude product obtain white 2,6- diethyl -4- first by silica gel chromatography (eluant, eluent: ethyl acetate/hexamethylene=1/10)
Base phenyl malononitrile 1.8g, yield 84.0%.
Embodiment 3
Under nitrogen protection, at room temperature, to 1000mL with distilling apparatus four-hole boiling flask in be added 105.0g sodium tert-butoxide,
500mL dimethylbenzene and 79.5g 2,6- diethyl -4- methyl bromobenzene add 24.3g malononitrile, stir and by reaction mixture
102 DEG C are warming up to, 0.08g acid chloride, 0.45g (R) -1- [(S) -2- (diphenylphosphine) ferrocenyl] ethyl double -3,5- is added
The solution of xylyl phosphine and 15mL tetrahydrofuran is warming up to 125-130 DEG C and reacts 2 hours, while being collected by distilling apparatus
The low-boiling-point substance steamed about 100mL, reaction terminate, and are cooled to 45 DEG C, and 300g mixture of ice and water stirring and dissolving is added into reaction solution
Solid, stratification separate lower layer's water phase, and solid, filtering is precipitated with hydrochloric acid tune pH to 4-5, and solid is washed with water to neutrality, dries
It is dry, obtain faint yellow 2,6- diethyl -4- aminomethyl phenyl malononitrile 73.6g, yield 99.1%.
Embodiment 4
At room temperature, 12.0g sodium hydroxide and 200mL 1-Methyl-2-Pyrrolidone are added into 500mL four-hole boiling flask, then
8.8g malononitrile, 27.3g 2 is added, 6- diethyl -4- methyl bromobenzene leads to nitrogen protection, stirs and reaction mixture heats up
To 100 DEG C, 0.02g palladium chloride, 0.12g 1- [bis- (1,1- dimethyl ethyl) phosphines] -2- [1- [bis- (2- aminomethyl phenyls) is added
Phosphine] ethyl] ferrocene, it keeps the temperature 140 DEG C and reacts 4 hours, cooling, decompression steams solvent, and 200g water is added into residue, uses salt
Acid adjusts pH to 3-4 that solid, filtering is precipitated, and solid is washed with water to neutrality, dries, obtains yellow 2,6- diethyl -4- aminomethyl phenyl
Malononitrile 23.9g, yield 93.7%.
Embodiment 5
Under nitrogen protection, at room temperature, 11.0g potassium tert-butoxide, 60mL 1- methyl -2- pyrrole are added into 100mL four-hole boiling flask
Pyrrolidone and 8.0g 2,6- diethyl -4- methyl bromobenzene add 2.3g malononitrile, stir and are warming up to reaction mixture
102 DEG C, the solution that the palladium chloride concentrated hydrochloric acid solution and 5mL n,N-dimethylacetamide that 0.3g 20% is added are prepared, and
The solution of 0.59g (6,6'- dimethoxy-biphenyl -2,2'- yl) bis- (diphenylphosphines) and 20mL 1-Methyl-2-Pyrrolidone rises
The low-boiling-point substance about 12mL that temperature is reacted 3 hours to 130 DEG C, while being steamed by distilling apparatus collection, reaction terminate, and are cooled to 40
DEG C, 40g mixture of ice and water stirring and dissolving solid is added into reaction solution, stratification separates lower layer's water phase, extremely with hydrochloric acid tune pH
Solid, filtering is precipitated in 4-5, and solid is washed with water to neutrality, dries, obtains faint yellow 2,6- diethyl -4- aminomethyl phenyl malononitrile
7.3g, yield 97.6%.
Embodiment 6
Under nitrogen protection, at room temperature, 8.5g potassium hydroxide and 120mL 1- methyl -2- are added into 250mL four-hole boiling flask
Pyrrolidones, adds 5.4g malononitrile, and negative pressure is warming up to 80-100 DEG C and steams 10mL solution, is added in the case where determining normal pressure
12.4g2,6- diethyl -4- methyl bromobenzene stir and reaction mixture are simultaneously warming up to 125 DEG C, be added 1.23mg acid chloride,
The solution of 7.51mg1,2- bis- [(2- methoxyphenyl) phenyl phosphorus] ethane and 2mL tetrahydrofuran keeps the temperature 130 DEG C and reacts 3 hours,
Cooling, decompression steam solvent, and 80g water is added into residue, and solid, filtering, solid water is precipitated with 1N hydrochloric acid tune pH to 3-4
Washing to neutrality, drying obtains yellow 2,6- diethyl -4- aminomethyl phenyl malononitrile 10.6g, yield 91.6%.
Embodiment 7
Under nitrogen protection, at room temperature, 11.0g potassium tert-butoxide, 60mL 1- methyl -2- pyrrole are added into 100mL four-hole boiling flask
Pyrrolidone and 8.0g 2,6- diethyl -4- methyl bromobenzene add 2.8g malononitrile, stir and are warming up to reaction mixture
102 DEG C, addition 0.06g palladium chloride, 0.22g (R) -1- [(S) -2- (diphenylphosphine) ferrocenyl] ethyl pair -3,5- dimethylbenzene
Base phosphine is warming up to 130 DEG C and reacts 3 hours, while collecting the low-boiling-point substance about 12mL steamed by distilling apparatus, and reaction terminates, and drops
40g mixture of ice and water stirring and dissolving solid is added into reaction solution to 40 DEG C for temperature, and stratification separates lower layer's water phase, uses hydrochloric acid
Adjust pH to 4-5 that solid, filtering is precipitated, solid is washed with water to neutrality, dries, obtains faint yellow 2,6- diethyl -4- aminomethyl phenyl
Malononitrile 6.9g, yield 92.7%.
Embodiment 8
Under nitrogen protection, at room temperature, to 2000mL with distilling apparatus four-hole boiling flask in be added 168.0g sodium tert-butoxide,
800mL dimethylbenzene, then the malononitrile of 46.2g fusing is instilled, it drips and finishes addition 79.5g 2,6- diethyl -4- methyl bromobenzene, stirring
And reaction mixture is warming up to 105 DEG C, 0.08g acid chloride, 0.40g (R) -1- [(S) -2- (diphenylphosphine) ferrocene is added
Base] ethyl pair -3,5- xylyl phosphine and 10mL tetrahydrofuran solution, it is warming up to 125 DEG C and reacts 2 hours, while passing through steaming
Distillation unit collects the low-boiling-point substance about 120mL steamed, and reaction terminates, and is cooled to 45 DEG C, and the mixing of 400g ice water is added into reaction solution
Object stirring and dissolving solid, stratification separate lower layer's water phase, solid, filtering are precipitated with hydrochloric acid tune pH to 4-5, solid is washed with water
It washs to neutrality, drying obtains faint yellow 2,6- diethyl -4- aminomethyl phenyl malononitrile 70.2g, yield 94.5%.
Embodiment 9
Under nitrogen protection, at room temperature, 138.3g potassium tert-butoxide, 600mL 1- methyl-are added into 1000mL four-hole boiling flask
2-Pyrrolidone and 80.0g 2,6- diethyl -4- methyl bromobenzene add 27.9g malononitrile, stir and by reaction mixture
101 DEG C are warming up to, palladium chloride concentrated hydrochloric acid solution, the 3.6g (6,6'- dimethoxy-biphenyl -2,2'- yl) that 1.6g 20% is added are double
The solution of (diphenylphosphine) and 60mL 1-Methyl-2-Pyrrolidone is warming up to 125 DEG C and reacts 4 hours, while passing through distillation dress
The low-boiling-point substance about 125mL for collecting and steaming is set, reaction terminates, and is cooled to 40 DEG C, and 400g mixture of ice and water is added into reaction solution and stirs
Dissolved solid is mixed, stratification separates lower layer's water phase, solid, filtering is precipitated with hydrochloric acid tune pH to 4-5, solid is washed with water to
Neutrality, drying, obtains faint yellow 2,6- diethyl -4- aminomethyl phenyl malononitrile 73.4g, yield 98.2%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent substitution, improvement and etc. done be should be included within the scope of the present invention.
Claims (10)
1. one kind 2, the preparation method of 6- diethyl -4- aminomethyl phenyl malononitrile, which is characterized in that 2,6- diethyl -4- methyl
Bromobenzene reacts to obtain in atent solvent 2,6- diethyl -4- aminomethyl phenyl the third two in the presence of a catalyst, with malononitrile and alkali
Nitrile.
2. the preparation method of 2,6- diethyl -4- aminomethyl phenyl malononitrile according to claim 1, which is characterized in that institute
Stating catalyst is palladium (II) complex；Palladium (II) complex is matched by palladium chloride, acid chloride or palladium sulfate and be suitble to ligand
Close preparation.
3. the preparation method of 2,6- diethyl -4- aminomethyl phenyl malononitrile according to claim 1, which is characterized in that alkali
Any one in sodium hydroxide, potassium hydroxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydride；Atent solvent is selected from diformazan
Benzene, N-Methyl pyrrolidone, any one in dimethyl sulfoxide.
4. the preparation method of 2,6- diethyl -4- aminomethyl phenyl malononitrile according to claim 2, which is characterized in that suitable
The ligand of conjunction is biphosphine ligand；Selected from the double -3,5- xylyl phosphine of (R) -1- [(S) -2- (diphenylphosphine) ferrocenyl] ethyl,
1- [bis- (1,1- dimethyl ethyl) phosphines] -2- [1- [bis- (2- aminomethyl phenyl) phosphines] ethyl] ferrocene, the bis- diphenylphosphines -9 of 4,5-,
Bis- [(2- methoxyphenyl) phenyl phosphorus] ethane of 9- xanthphos, 1,2- or (6,6'- dimethoxy-biphenyl -2,2'- base)
Any one in bis- (diphenylphosphines).
5. preparation method according to claim 2, which is characterized in that palladium chloride, acid chloride or palladium sulfate and ligand rub
You are than being 1:1.0-3.0.
6. the preparation method of 2,6- diethyl -4- aminomethyl phenyl malononitrile according to claim 1, which is characterized in that institute
The molar ratio of the 2,6- diethyl -4- methyl bromobenzene and catalyst, malononitrile, alkali stated are as follows: 1:0.0001-0.01:1.0-2.0:
2.0-5.0。
7. the preparation method of 2,6- diethyl -4- aminomethyl phenyl malononitrile according to claim 1, which is characterized in that institute
2,6- diethyl -4- methyl the bromobenzene and the molar ratio of catalyst, malononitrile, alkali stated are preferred are as follows: 1:0.0005-0.005:1.0-
1.2:2.5-3.5。
8. the preparation method of 2,6- diethyl -4- aminomethyl phenyl malononitrile according to claim 1, which is characterized in that institute
The reaction temperature stated is 25-140 DEG C.
9. preparation method according to claim 1, which is characterized in that the reaction temperature are as follows: 100-130 DEG C.
10. a kind of any 2, the 6- diethyl -4- aminomethyl phenyl malononitrile of claim 1-9, which is characterized in that as system
The application of standby herbicide pinoxaden intermediate.
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Cited By (1)
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| CN109912457A (en) * | 2019-05-06 | 2019-06-21 | 浙江中山化工集团股份有限公司 | A kind of preparation method of 2,6- diethyl -4- aminomethyl phenyl malononitrile |
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| CN109320435A (en) * | 2018-11-30 | 2019-02-12 | 江苏富鼎化学有限公司 | The synthetic method of 2- (2,6- diethyl -4- methylbenzene) malononitrile |
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