CN103570583A - Method for preparing 2-(3,4-dimethoxymethyl)-3-methylbutylnitrile - Google Patents
Method for preparing 2-(3,4-dimethoxymethyl)-3-methylbutylnitrile Download PDFInfo
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Abstract
The invention discloses a method for preparing 2-(3,4-dimethoxymethyl)-3-methylbutylnitrile from a benzofuranol byproduct 4-(2-methallyl)-1,2-benzenediol serving as a raw material. A chemical reaction equation is shown in the specification. According to the method, the 2-(3,4-dimethoxymethyl)-3-methylbutylnitrile content is high, and the mass content is 98.5 to 99.5 percent; the product 2-(3,4-dimethoxymethyl)-3-methylbutylnitrile is high in yield, and the overall yield is 65.6 to 79.7 percent; the byproduct 4-(2-methallyl)-1,2-benzenediol produced in a benzofuranol production process is used as a starting raw material, so that the raw material is readily available, the method is low in cost and favorable for industrial production, and has environment-friendly benefits, and a process is simple.
Description
Technical field
The present invention relates to 2-(3, the preparation method of 4-Dimethoxyphenyl)-3-methylbutyronitrile, especially a kind of with benzofuranol by product 4-(2-methacrylic)-1,2-dihydroxy-benzene is the method that raw material is prepared 2-(3,4-Dimethoxyphenyl)-3-methylbutyronitrile.
Background technology
2-(3,4-Dimethoxyphenyl)-3-methylbutyronitrile is the key intermediate of synthetic verapamil (verapamil).Verapamil is selectivity calcium ion channel blocker, applicating history is clinically long, there is multiple pharmacotoxicological effect, as slow down heart rate, increase coronary flow and renal blood flow, diastole peripheral blood vessel, reduces myocardial consumption of oxygen, increases antitumor drug and kills and wounds the tumour cell of several drug resistance, the effect of reversing drug resistance etc.2-(3,4-Dimethoxyphenyl)-3-methylbutyronitrile structural formula:
There is at present synthetic 2-(3,4-the Dimethoxyphenyl)-3-methylbutyronitrile of report to be mainly guaiacol method: methyl catechol is refluxed and obtains methylate with methyl-sulfate under NaOH alkaline condition; With HCl and paraformaldehyde, on phenyl ring, generate and replace chloroethyl again, obtain 3,4-dimethoxy Benzyl Chloride; With excessive sodium cyanide, carry out cyanogenation again, obtain 3,4-dimethoxybenzeneacetonitrile; And then under highly basic catalysis, react and obtain 2-(3,4-Dimethoxyphenyl)-3-methylbutyronitrile with bromine isopropyl alkane, synthetic total recovery is lower.
Both at home and abroad the study on the synthesis of 2-(3,4-Dimethoxyphenyl)-3-methylbutyronitrile is mainly concentrated on optimum conditions.
Tian Shu (prints 2001,15 (7): 31-34) verapamil production technique is improved during chemical industry.Work out synthetic 2-(3,4-Dimethoxyphenyl)-cyanation preferred process in the 3-methylbutyronitrile stage, make in nitrilation step veratrole acetonitrile yield bring up to 68% from 45%, verapamil finished product total recovery reaches 11.3%.
Huang Wei (contemporary Chinese medicinal application, 2008,2 (23): 18-19) adopt the synthetic 2-(3 of microwave method, 4-Dimethoxyphenyl)-3-methylbutyronitrile: with 3,4-dimethoxy benzene second eyeball and 2-N-PROPYLE BROMIDE are raw material, add phase-transfer catalyst benzyltriethylammoinium chloride, utilize microwave reactor to carry out alkylation reaction and obtain target compound.When result shows under electric current 30mA radiation 6min, reaction yield is the highest, can reach 64.5%.
Current domestic employing pyrocatechol is raw material production benzofuranol, annual output is about 6000 tons, its Main By product 4-(2-methacrylic)-1, approximately 700 tons of 2-dihydroxy-benzenes, owing to not developing suitable derived product, manufacturer is not separated from rectifying still raffinate by it, only it is processed as astatki, and added value is low.
Summary of the invention
The object of this invention is to provide a kind ofly with benzofuranol by product 4-(2-methacrylic)-1,2-dihydroxy-benzene is the method that raw material is prepared 2-(3,4-Dimethoxyphenyl)-3-methylbutyronitrile, and chemical equation is:
Concrete technology step of the present invention is as follows:
1. prepare 1,2-dimethoxy-4 '-(2-methacrylic) benzene
With benzofuranol by product 4-(2-methacrylic)-1,2-dihydroxy-benzene is raw material, carries out methoxylation obtain 1,2-dimethoxy-4 '-(2-methacrylic) benzene with methyl-sulfate, sodium hydroxide.4-(2-methacrylic)-1, the mol ratio of 2-Ben bis-Fen ︰ Liu acid two Jia Zhi ︰ sodium hydroxide is 1 ︰ 1.1～3.3 ︰ 2.4～6.8,50～90 ℃ of methoxylation temperature, reaction times 3～6h.Reaction finishes rear rectification under vacuum and obtains 1,2-dimethoxy-4 '-(2-methacrylic) benzene.
2. prepare 1,2-dimethoxy-4 '-(2-methylpropenyl) benzene
In solvent, n-butanol, under alkali and phase-transfer catalyst effect, there is isomerization reaction and obtain 1,2-dimethoxy-4 '-(2-methylpropenyl) benzene in 1,2-dimethoxy-4 '-(2-methacrylic) benzene.Alkali is KOH, PEG-400 is phase-transfer catalyst, the consumption of solvent, n-butanol is 1,0.5～5 times of 2-dimethoxy-4 '-(2-methacrylic) benzene quality, 1, the mass ratio of 2-dimethoxy-4 '-(2-methacrylic) benzene and KOH, PEG-400 is 100 ︰ 10～30 ︰ 1～10,60～110 ℃ of isomerization reaction temperature, reaction times 3～8h.Reaction finishes rear underpressure distillation and obtains 1,2-dimethoxy-4 '-(2-methylpropenyl) benzene.
3. prepare 4-(the bromo-2-methyl-propyl of 1-)-1,2-dimethoxy benzene
1,2-dimethoxy-4 '-(2-methylpropenyl) benzene issues raw Radical Addition and obtains 4-(the bromo-2-methyl-propyl of 1-)-1,2-dimethoxy benzene in free radical HBr, solvent existence.Described 1, the mol ratio of 2-dimethoxy-4 '-(2-methylpropenyl) benzene and HBr is 1 ︰ 1～3, solvent is any one in normal hexane, hexanaphthene, normal heptane, octane, solvent load is 1,3～8 times of 2-dimethoxy-4 '-(2-methylpropenyl) benzene volume, 60～100 ℃ of Radical Addition temperature, reaction times 0.5～2h.Reaction finishes rear underpressure distillation and obtains 4-(the bromo-2-methyl-propyl of 1-)-1,2-dimethoxy benzene.
4. prepare 2-(3,4-Dimethoxyphenyl)-3-methylbutyronitrile
4-(the bromo-2-methyl-propyl of 1-)-1 there is cyanation and obtains 2-(3,4-Dimethoxyphenyl)-3-methylbutyronitrile in 2-dimethoxy benzene and cyanating reagent NaCN under catalyst of triethylamine effect.Described 4-(the bromo-2-methyl-propyl of 1-)-1,2-dimethoxy benzene and NaCN mol ratio are 1:1～1.5, and the amount of catalyst of triethylamine is 4-(the bromo-2-methyl-propyl of 1-)-1,5% of 2-dimethoxy benzene molar weight, 60～100 ℃ of cyanogenation temperature, cyanogenation time 1～8h.After desolvation, recrystallization obtains 2-(3,4-Dimethoxyphenyl)-3-methylbutyronitrile.
Benzofuranol by product 4-of the present invention (2-methacrylic)-1,2-dihydroxy-benzene, is to obtain by high vacuum rectification with benzofuranol distillation residual liquid, gained 4-(2-methacrylic)-1, the quality percentage composition of 2-dihydroxy-benzene is greater than 90%.
Compare with the preparation method of other 2-(3,4-Dimethoxyphenyl)-3-methylbutyronitrile, the present invention has the following advantages:
1) product 2-(3,4-Dimethoxyphenyl)-3-methylbutyronitrile content is high, and mass content is 98.5%～99.5%(liquid chromatography, external standard);
2) product 2-(3,4-Dimethoxyphenyl)-3-methylbutyronitrile yield is high, and total recovery is 65.6%～79.7% (with 4-(2-methacrylic)-1,2-dihydroxy-benzene meter);
3) starting raw material is the by product 4-(2-methacrylic)-1 in benzofuranol generative process, 2-dihydroxy-benzene, and raw material is easy to get, with low cost, and has environmental benefit;
4) other raw materials and the solvent that use are all cheaply easy to get, and technique is simple, is conducive to suitability for industrialized production.
Embodiment
First carry out 4-(2-methacrylic)-1, the extraction of 2-dihydroxy-benzene, prepares the raw material of 2-(3,4-Dimethoxyphenyl)-3-methylbutyronitrile as following examples
Containing 230.8g(1.4mol) 4-(2-methacrylic)-1, the 820.0g benzofuranol distillation residual liquid rectifying of 2-dihydroxy-benzene, get the cut that boiling range is 126-129 ℃/5mmHg, obtain 159.0g colourless viscous liquid crude product 4-(2-methacrylic)-1,2-dihydroxy-benzene, content 91.7%, yield 63.2%.4-(2-methacrylic)-1,2-dihydroxy-benzene is white solid; LC-MS (m/z): 163.0(M-H
+);
1h NMR (CDCl
3, 400MHz) δ: 1.66 (s, 3H, CH
3), 3.20 (s, 2H, ArCH
2), 4.72 (s, 1H, OH), 4.78 (s, 1H, OH), 5.29 (s, 2H, C=CH
2), 6.57 (dd, J=8.0Hz, J=2.0Hz, 1H, phenyl ring 5-H), 6.72 (d, J=2.0Hz, 1H, phenyl ring 3-H), 6.78～6.80 (d, J=8.0Hz, 1H, phenyl ring 6-H).
Embodiment 1
Synthesizing of 1,2-dimethoxy-4 '-(2-methacrylic) benzene
Dropping 240.0g15%(0.9mol) aqueous sodium hydroxide solution is to containing 63.0g(91.7%, 0.35mol) crude product 4-(2-methacrylic)-1, in 2-dihydroxy-benzene, after stirring, splash into 75.7g(0.6mo1) methyl-sulfate, finish 60 ℃ of reaction 2h, add 53.3g15%(0.2mol) aqueous sodium hydroxide solution and 12.6g(0.10mol) methyl-sulfate, continues reaction 2h.Cooling, add 200mL toluene, branch vibration layer, add 2.5g4-TBC, adopt ceramic random packing tower rectifying (reflux ratio is 8: 1), get the cut that boiling range is 110-112 ℃/5mmHg, obtain 64.9g colourless liquid 1,2-dimethoxy-4 '-(2-methacrylic) benzene, content 97.1%, yield 96.4%.
1H?NMR(CDCl
3，400MHz)δ:1.67(s，3H，CH
3)，3.26(s，2H，ArCH
2)，3.85(s，6H，2×OCH
3)，4.73(s，1H，C=CH)，4.80(s，1H，C=CH)，6.71(s，1H，C
6H
33-H)，6.72(d，J=8.0Hz，1H，C
6H
35-H)，6.79(d，J=8.0Hz，1H，C
6H
36-H)。
Synthesizing of 1,2-dimethoxy-4 '-(2-methylpropenyl) benzene
23.8g (content 97.1%, 0.12mol) 1,2-dimethoxy-4 '-(2-methacrylic) benzene, 4.2g (0.075mol) KOH, 0.5g PEG-400 and 25mL propyl carbinol, be heated to 90 ℃ of reaction 4h, after reaction finishes, reaction solution is carried out to underpressure distillation and obtain 22.4g light yellow liquid 1,2-dimethoxy-4 '-(2-methylpropenyl) benzene, content 97.8%, yield 94.8%.
1H?NMR(CDCl
3，300MHz)δ:1.75(d，J=1.2Hz，3H，CH
3)，1.83(d，J=1.2Hz，3H，CH
3)，3.86(s，6H，2×OCH
3)，6.17(s，1H，ArCH)，6.97-7.21(m，3H，C
6H
3)。
4-(the bromo-2-methyl-propyl of 1-)-1,2-dimethoxy benzene synthetic
In four-hole bottle, add 57.7g (0.30mol) 1,2-dimethoxy-4 '-(2-methylpropenyl) benzene, 250mL normal heptane and 2.5g Diisopropyl azodicarboxylate (AIBN), stirring is warming up to 80 ℃, passes into 29.2g (0.36mol) HBr gas and react in 1h.After reaction finishes, reaction solution is carried out to underpressure distillation and obtain 77.8g light yellow liquid 4-(the bromo-2-methyl-propyl of 1-)-1,2-dimethoxy benzene, content 98.0%, yield 93.0%.
1H?NMR(CDCl
3，300MHz)δ:0.88(d，J=6.3Hz，3H，CH
3)，0.93(d，J=6.3Hz，3H，CH
3)，2.71(m，1H，CH)，3.85(s，6H，2×OCH
3)，4.79(d，J=6.9Hz，1H，ArCH)，6.72-6.96(m，3H，C
6H
3)。
Synthesizing of 2-(3,4-Dimethoxyphenyl)-3-methylbutyronitrile
5.9g (0.12mol) NaCN is dissolved in 5mL water, add people 0.5g triethylamine, be heated to 80 ℃, slowly drip 100mL containing 27.9g (content 98%, 0.10mol) 4-(the bromo-2-methyl-propyl of 1-)-1, the toluene solution of 2-dimethoxy benzene, stirring reaction 2.5h, then adds 50mL water. stir again 5min, standing branch vibration layer, organic layer Distillation recovery toluene, resistates joins stirred crystallization in 100mL water, leaches rear with ethyl alcohol recrystallization, obtain 20.1g2-(3,4-Dimethoxyphenyl)-3-methylbutyronitrile, content 99.5%, yield 91.5%.Fusing point 48.7-49.3 ℃,
1h NMR (CDCl
3, 300MHz) δ: 0.98 (d, J=6.3Hz, 6H, 2 * CH
3), 2.66 (m, 1H, CH), 3.78 (s, 6H, 2 * OCH
3), 4.74 (d, J=6.9Hz, 1H, ArCH), 6.84-6.81 (m, 3H, C
6h
3).
Embodiment 2
Synthesizing of 1,2-dimethoxy-4 '-(2-methacrylic) benzene
Dropping 186.7g15%(0.7mol) aqueous sodium hydroxide solution is to containing 63.0g(91.7%, 0.35mol) crude product 4-(2-methacrylic)-1, in 2-dihydroxy-benzene, after stirring, splash into 44.2g(0.35mo1) methyl-sulfate, finish, 90 ℃ of reaction 2h, add 37.3g15%(0.14mol) aqueous sodium hydroxide solution and (4.4g, 0.035mol) methyl-sulfate, continue reaction 1h.Cooling, add 200mL toluene, branch vibration layer, add 2.5g4-TBC, adopt ceramic random packing tower rectifying (reflux ratio is 8: 1), get the cut that boiling range is 110-112 ℃/5mmHg, obtain 62.6g colourless liquid 1,2-dimethoxy-4 '-(2-methacrylic) benzene, content 96.0%, yield 92.0%.
Synthesizing of 1,2-dimethoxy-4 '-(2-methylpropenyl) benzene
23.8g (content 97.1%, 0.12mol) 1,2-dimethoxy-4 '-(2-methacrylic) benzene, 7.1g (0.13mol) KOH, 0.24g PEG-400 and 15mL propyl carbinol, be heated to 110 ℃ of reaction 3h, after reaction finishes, reaction solution is carried out to underpressure distillation and obtain 21.6g light yellow liquid 1,2-dimethoxy-4 '-(2-methylpropenyl) benzene, content 96.2%, yield 90.0%.
4-(the bromo-2-methyl-propyl of 1-)-1,2-dimethoxy benzene synthetic
In four-hole bottle, add 57.7g (0.30mol) 1,2-dimethoxy-4 '-(2-methylpropenyl) benzene, 150mL octane and 2.5g Diisopropyl azodicarboxylate (AIBN), stirring is warming up to 100 ℃, passes into 24.3g (0.3mol) HBr gas and react in 0.5h.After reaction finishes, reaction solution is carried out to underpressure distillation and obtain 75.9g light yellow liquid 4-(the bromo-2-methyl-propyl of 1-)-1,2-dimethoxy benzene, content 95.0%, yield 88.0%.
Synthesizing of 2-(3,4-Dimethoxyphenyl)-3-methylbutyronitrile
4.9g (0.10mol) NaCN is dissolved in 5mL water, add people 0.5g triethylamine, be heated to 60 ℃, slowly drip 100mL containing 27.9g (content 98%, 0.10mol) 4-(the bromo-2-methyl-propyl of 1-)-1, the toluene solution of 2-dimethoxy benzene, stirring reaction 8h, then adds 50mL water.Stir again 5min, standing branch vibration layer, organic layer Distillation recovery toluene, resistates joins stirred crystallization in 100mL water, leaches the rear ethyl alcohol recrystallization of using, and obtains 20.0g2-(3,4-Dimethoxyphenyl)-3-methylbutyronitrile, content 98.5%, yield 90%.
Embodiment 3
Synthesizing of 1,2-dimethoxy-4 '-(2-methacrylic) benzene
Dropping 560.0g15%(2.1mol) aqueous sodium hydroxide solution is to containing 63.0g(91.7%, 0.35mol) crude product 4-(2-methacrylic)-1, in 2-dihydroxy-benzene, after stirring, splash into 132.5g(1.05mo1) methyl-sulfate, finish, 50 ℃ of reaction 4h, add 74.6g15%(0.28mol) aqueous sodium hydroxide solution and (13.3g, 0.105mol) methyl-sulfate, continue reaction 2h.Cooling, add 200mL toluene, branch vibration layer, add 2.5g4-TBC, adopt ceramic random packing tower rectifying (reflux ratio is 8: 1), get the cut that boiling range is 110-112 ℃/5mmHg, obtain 62.6g colourless liquid 1,2-dimethoxy-4 '-(2-methacrylic) benzene, content 98.2%, yield 94.0%.
Synthesizing of 1,2-dimethoxy-4 '-(2-methylpropenyl) benzene
23.8g (content 97.1%, 0.12mol) 1,2-dimethoxy-4 '-(2-methacrylic) benzene, 2.4g (0.043mol) KOH, 2.4g PEG-400 and 125mL propyl carbinol, be heated to 60 ℃ of reaction 8h, after reaction finishes, reaction solution is carried out to underpressure distillation and obtain 21.5g light yellow liquid 1,2-dimethoxy-4 '-(2-methylpropenyl) benzene, content 98.3%, yield 91.5%.
4-(the bromo-2-methyl-propyl of 1-)-1,2-dimethoxy benzene synthetic
In four-hole bottle, add 57.7g (0.30mol) 1,2-dimethoxy-4 '-(2-methylpropenyl) benzene, 400mL hexanaphthene and 2.5g Diisopropyl azodicarboxylate (AIBN), stirring is warming up to 60 ℃, passes into 73.0g (0.9mol) HBr gas and react in 2h.After reaction finishes, reaction solution is carried out to underpressure distillation and obtain 75.7g light yellow liquid 4-(the bromo-2-methyl-propyl of 1-)-1,2-dimethoxy benzene, content 97.8%, yield 90.3%.
Synthesizing of 2-(3,4-Dimethoxyphenyl)-3-methylbutyronitrile
7.4g (0.15mol) NaCN is dissolved in 5mL water, add people 0.5g triethylamine, be heated to 100 ℃, slowly drip 100mL containing 27.9g (content 98%, 0.10mol) 4-(the bromo-2-methyl-propyl of 1-)-1, the toluene solution of 2-dimethoxy benzene, stirring reaction 1h, then adds 50mL water. stir again 5min, standing branch vibration layer, organic layer Distillation recovery toluene, resistates joins stirred crystallization in 100mL water, leaches rear with ethyl alcohol recrystallization, obtain 20.1g2-(3,4-Dimethoxyphenyl)-3-methylbutyronitrile, content 99.1%, yield 91.3%.
Claims (3)
1.2-(3, the preparation method of 4-Dimethoxyphenyl)-3-methylbutyronitrile, it is characterized in that with benzofuranol by product 4-(2-methacrylic)-1, 2-dihydroxy-benzene is raw material, with methyl-sulfate, sodium hydroxide carries out methoxylation and obtains 1, 2-dimethoxy-4 '-(2-methacrylic) benzene, then in propyl carbinol solvent, under alkali and phase-transfer catalyst effect, there is isomerization reaction and obtain 1, 2-dimethoxy-4 '-(2-methylpropenyl) benzene, again at free radical HBr, solvent existence issues raw Radical Addition and obtains 4-(the bromo-2-methyl-propyl of 1-)-1, 2-dimethoxy benzene, under catalyst of triethylamine effect, there is cyanation and obtain 2-(3 in last and cyanating reagent NaCN, 4-Dimethoxyphenyl)-3-methylbutyronitrile, chemical equation is:
In described isomerization reaction, alkali used is KOH, and phase-transfer catalyst used is PEG-400, and in Radical Addition, solvent for use is any one in normal hexane, hexanaphthene, normal heptane, octane.
2. the preparation method of 2-according to claim 1 (3,4-Dimethoxyphenyl)-3-methylbutyronitrile, is characterized in that:
In methoxylation, 4-(2-methacrylic)-1, mole proportioning of 2-Ben bis-Fen ︰ Liu acid two Jia Zhi ︰ sodium hydroxide is 1 ︰ 1.1～3.3 ︰ 2.4～6.8,50～90 ℃ of methoxylation temperature, reaction times 3～6h;
In isomerization reaction, the consumption of solvent, n-butanol is 1,0.5～5 times of 2-dimethoxy-4 '-(2-methacrylic) benzene quality, 1, the mass ratio of 2-dimethoxy-4 '-(2-methacrylic) benzene and KOH, PEG-400 is 100 ︰ 10～30 ︰ 1～10,60～110 ℃ of isomerization reaction temperature, reaction times 3～8h;
In Radical Addition, the consumption of solvent normal hexane or hexanaphthene, normal heptane, octane is 1,3～8 times of 2-dimethoxy-4 '-(2-methylpropenyl) benzene volume, 1, mole proportioning of 2-dimethoxy-4 '-(2-methylpropenyl) benzene and HBr is 1 ︰ 1～3,60～100 ℃ of Radical Addition temperature, reaction times 0.5～2h;
In cyanation, 4-(the bromo-2-methyl-propyl of 1-)-1,2-dimethoxy benzene and NaCN mol ratio are 1:1～1.5, the amount of catalyst of triethylamine is 4-(the bromo-2-methyl-propyl of 1-)-1,5% of 2-dimethoxy benzene molar weight, 60～100 ℃ of cyanogenation temperature, cyanogenation time 1～8h.
3. 2-(3 according to claim 1, the preparation method of 4-Dimethoxyphenyl)-3-methylbutyronitrile, it is characterized in that raw material 4-(2-methacrylic)-1,2-dihydroxy-benzene, to obtain by high vacuum rectification with benzofuranol distillation residual liquid, gained 4-(2-methacrylic)-1, the quality percentage composition of 2-dihydroxy-benzene is greater than 90%.
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| CN112574065A (en) * | 2020-12-30 | 2021-03-30 | 宁波职业技术学院 | Preparation method of (benzene-1, 3, 5-triacyl) acetonitrile |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102503788A (en) * | 2011-11-21 | 2012-06-20 | 湖南大学 | Application of 4-(2-methylallyl)-1,2-dihydroxybenzene in preparation of perfume |
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Cited By (1)
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| CN112574065A (en) * | 2020-12-30 | 2021-03-30 | 宁波职业技术学院 | Preparation method of (benzene-1, 3, 5-triacyl) acetonitrile |
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Application publication date: 20140212 |