CN110028392A - A kind of method of methyl butynol iso-synthesis isoamyl olefine aldehydr - Google Patents
A kind of method of methyl butynol iso-synthesis isoamyl olefine aldehydr Download PDFInfo
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
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- C07—ORGANIC CHEMISTRY
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Abstract
The present invention provides a kind of method of methyl butynol iso-synthesis isoamyl olefine aldehydr, the method, the catalyst used is mixed catalyst, it is made of major catalyst, co-catalyst, organic acid, reaction temperature is 70-105 DEG C under normal pressure, isoamyl olefine aldehydr selectively can achieve 95% or more, and methyl butyne alcohol conversion reaches 90% or more, and yield is 85% or more.Present invention generation heel is less, every every batch reaction of 260g raw material, increases heel 4.96-7.2g newly；Raw material methyl butynol of the present invention is low to water content requirement, and water content advantageously reduces cost less than 1%.
Description
Technical field
The present invention relates to a kind of raw catelysts for synthesizing isoamyl olefine aldehydr, belong to technical field of fine.
Background technique
The entitled 3- methyl-2-butene -1- aldehyde of chemistry of isoamyl olefine aldehydr, is the important source material for synthesizing large fragrance citral,
By citral, it is a variety of that basal nutrient product vitamin A and irisone, geraniol, citronellol, menthol etc. can be synthesized
Fragrance, studying it is highly desirable.
Currently, the synthesis of isoamyl olefine aldehydr mainly has with prenol, 3- methyl-3-butene-1-alcohol, 2- methyl -3- butine -
2- alcohol is raw material, resets synthesis isoamyl olefine aldehydr, another kind of such as isopentyl aldehyde dehydrogenation by different oxidations.Existing isoamyl olefine aldehydr production
Technique there are raw material consumptions big, conversion ratio, selectivity is low, and catalyst is costly and difficult to the problems such as applying.
Patent US2524866, is related to gas phase conversion of the 1- alkynol under catalyst, and product can be beta-unsaturated ketone, insatiable hunger
And aldehyde.It include 3- methyl-1-butine-3- alcohol in alkynol, conversion ratio is more than 95%.Using by tin, cadmium, zinc, tungsten, nickel, copper, thorium, magnesium
The phosphate solution of equal metals is immersed in the catalyst prepared on suitable inert carrier, and 150-250 DEG C, carrier uses titanium dioxide
Silicon can also use silica combined aluminum oxide and silica gel.Reaction needs plus water, to guarantee that product turns to unsaturated aldehyde ketone
Becoming, catalyst is supported catalyst, complex manufacturing process and difficulty, it is at high cost, it is not easy preparation of industrialization；
Patent US2005/143597 is using methyl butynol as raw material, and methyl (triphenyl phosphorus) gold is catalyst preparation with sulfuric acid
Isoamyl olefine aldehydr, yield lower only 44%, and catalyst methyl (triphenyl phosphorus) gold needs to dissolve in methyl alcohol, and sulfuric acid uses
Aqueous solution, reaction system is complicated, and solvent is used in reaction process.
It is mentioned in patent CN105503553 using cation-modified montmorillonite as catalyst, substitution propargyl alcohol is raw material, benefit
It is reset with Meyer-Schuster and α, the method for beta-unsaturated carbonyl compound, with metal-modified illiteracy is prepared by substitution propargyl alcohol
De- soil makees catalyst, and the reaction time is up to 36 hours, and uses nitromethane in patent and make solvent, and risk is larger.
Similar reaction is mentioned in patent WO2016059155 (A1), beta-unsaturated ketone processed is reset by substituted propargyl alcohol, with levulinic
Ketone oxygen titanium, stannous chloride make catalyst, carry out reaction as solvent using toluene by reaction in 18 hours and prepare target compound, react
Time is longer.
Patent CN109336750A discloses a kind of synthesis technology of isoamyl olefine aldehydr, using metal oxide as catalyst,
Under the conditions of auxiliary agent is existing, isoamyl olefine aldehydr is prepared using 2- methyl -3- butyne-2-alcohol as catalytic material rearrangement, in synthetic reaction,
The content of raw material 2- methyl -3- butyne-2-alcohol from 99.7% be down to 56% after no longer change, i.e., conversion ratio is constant, reaction balance, reach
To terminal, it is seen then that the conversion per pass of the 2- methyl -3- butyne-2-alcohol of raw material is only 43.8%；The one-way yield of isoamyl olefine aldehydr
It is lower.
CN101381292A discloses a kind of method of continuous production 3- methyl-2-butene aldehyde, using titanium catalyst, copper
The composite catalyst of catalyst and organic acid composition realizes 2- methyl -3- butyne-2-alcohol by reactive distillation coupling technique and arrives
The continuous production of isoamyl olefine aldehydr, comprehensive yield is up to 88-93%, but it uses rectifying column, and energy consumption of reaction is larger, and generates
Heel it is more.
Summary of the invention
In order to overcome the problems of the above-mentioned prior art, the present invention provides a kind of methyl butynol iso-synthesis iso-amylene
The method of aldehyde realizes following goal of the invention:
(1) conversion per pass of raw material is improved；
(2) one-way yield of isoamyl olefine aldehydr product is improved；
(3) yield of heel is reduced；
(4) reaction temperature is reduced.
In order to solve the above technical problems, the present invention takes following technical scheme (1):
In a kettle, raw material 3- methyl-1-butine-3- alcohol (following is methyl butynol) and catalyst are put into, catalyst
Addition sequence is co-catalyst, major catalyst, organic acid catalyst, opens and stir and heat up, and stops adding after reaching reaction temperature
Heat starts to react, and iso-amylene aldehyde reaches 80% or more stopping reaction.Reaction solution after reaction is carried out at de- heavy, rectifying
Reason, obtains product isoamyl olefine aldehydr.
The catalyst is a kind of mixed catalyst, is grouped as by three groups.Major catalyst plays major catalytic,
Promote the formation of connection alkene intermediate during the reaction；Speculate co-catalyst during the reaction with the hydroxy combining of protonation simultaneously
Promote hydroxyl to leave away, forms carbonium ion；Acid catalyst mainly promotes hydroxyl oxygen atom to protonate.
The major catalyst be triphenyl phosphorus palladium, diphenylphosphine palladium, two triphenyl phosphorus palladium of dichloro, methyl triphenyl phosphorus palladium,
(diphenylphosphine) ethyl of 1,2- bis- palladium, triphenyl phosphorus palladium chloride are one such.
The co-catalyst is zinc acetate.
The organic acid is succinic acid, malonic acid, propionic acid, oxalic acid, tartaric acid, glutaric acid, styrene acid, phenylacetic acid, neighbour
One of phthalic acid.
In the composition of the catalyst system, the dosage of palladium catalyst is the 0.01-2wt% of material quality, co-catalyst
Dosage is the 0.1-5wt% of material quality, and organic acid dosage is the 0.1-10wt% of material quality.
The reaction temperature of the reaction system is 70-105 DEG C.
The reaction pressure of the reaction system is normal pressure.
The raw material is 3- methyl-1-butine-3- alcohol, is liquid under room temperature, and content is greater than 99%, and water content is less than 1%.
Major catalyst, co-catalyst, organic acid catalyst in the catalyst system are urged by the way of individually feeding intake
Agent is all dissolved in reaction solution with the raising of reaction temperature.
Sampling GC is detected after reacting one section of 4h, and reaction was completed by content > 80%, and reaction solution is carried out de- weight, rectifying post-processing,
Obtained isoamyl olefine aldehydr finished product, GC detection, content > 96%.
Heel of the reaction solution after de- weight can apply.
Optimal technical scheme (2) are as follows:
The major catalyst is one kind of triphenyl phosphorus palladium, diphenylphosphine palladium, methyl triphenyl phosphorus palladium, triphenyl phosphorus palladium chloride；
The organic acid is one of succinic acid, propionic acid, tartaric acid, styrene acid, phthalic acid；
In the composition of the catalyst system, the dosage of palladium catalyst is the 0.38-2wt% of material quality, the dosage of co-catalyst
For the 0.38-5wt% of material quality, organic acid dosage is the 0.19-10wt% of material quality；Remaining reaction condition is the same as above-mentioned technology
Scheme (1).
Above-mentioned technical proposal, raw material conversion per pass are 91-93.5%, and the one-way yield of isoamyl olefine aldehydr is 86.65-
90.13%, selectivity is 95.05-96.4%；Each reaction increases heel 5-6.7g newly；Reaction time is 6h.
Most preferred technical solution (3) are as follows:
The major catalyst is triphenyl phosphorus palladium；
The organic acid is styrene acid；
In the composition of the catalyst system, the dosage of palladium catalyst is the 1-2wt% of material quality, and the dosage of co-catalyst is
The 2-5wt% of material quality, organic acid dosage are the 3.5-10wt% of material quality；Reaction time is 5.5-6.5h, each reaction
Newly-increased charging is 4.96-6.5g；The one-way yield of isoamyl olefine aldehydr is 88.23-90.13%, and the conversion per pass of raw material is 92.1-
93.5%；Selectivity is 95.2-96.4%；
The same above-mentioned technical proposal of remaining reaction condition (1).
Compared with prior art, the invention has the following advantages:
(1) the method for the invention, Dan journey Zhuanization Shuai≤90% of raw material or more；One-way yield is 85.56-90.13%；Selectivity
≧95%；
(2) reaction temperature of the present invention is lower, at 70-105 DEG C；
(3) present invention generation heel is less, and every every batch reaction of 260g raw material increases heel 4.96-7.2g newly；
(4) raw material methyl butynol of the present invention requires water content low, and water content advantageously reduces cost less than 1%；
(5) after de- weight heel of the present invention applies 20 times, one-way yield only reduces by 1.6%.
Specific embodiment
(in following embodiment the dosage of catalyst be to synthesis iso-amylene aldehyde new catalyst system dosage illustration and
It explains, is not used to limit the dosage of this catalyst system.In addition, catalyst involved in the embodiment of the present invention, raw material
It is commercially available), reaction solution, finished product detection instrument is using Agilent gas chromatograph, and raw material moisture is detected as
Karl Fischer Moisture Meter.
The main content of methyl butynol of the present invention is gas phase content.
Reaction equation of the invention are as follows:
By taking embodiment 1 as an example, illustrate the calculating process of conversion ratio of the invention, selectivity, yield
Conversion ratio=(reaction raw materials gross mass-unreacted recycles quality)/reaction raw materials gross mass * 100%
Conversion ratio=(257.9239-20.84*99%)/257.92*100%=92%
The raw material of selectivity=generation product consumption/(reaction raw materials gross mass-unreacted recycles quality) * 100%
The quality of=target product/(reaction raw materials gross mass-unreacted recycles quality) * 100%
Selectivity=230.41*98.35%/(257.92-20.84*99%) * 100%=95.5%；
Yield=conversion ratio * selectivity
Yield=92%*95.5%=87.86%.
Remarks: because being detected when water content using karl Fischer moisture instrument, moisture in vapor detection do not examine by appearance, gas phase
The content of the methyl butynol measured is the content deducted after moisture, therefore first removes water when calculating methyl butynol quality
Quality.
Embodiment 1
Methyl butynol 260g(water content 0.3%, main content 99.5% are added into 500mL three-necked flask), zinc acetate 13g, two
Phenyl phosphorus palladium 5.2g, succinic acid 26g feed intake complete, open agitating and heating heating, stop heating when temperature reaches 90 DEG C, start anti-
It answers, temperature flows back when reaching 104 DEG C.From timing is begun to warm up, reaction 4h starts sample detection, and iso-amylene aldehyde reaches
80% or more stops reaction.Reaction solution carries out de- weight, rectifying obtains isoamyl olefine aldehydr finished product 230.41g(iso-amylene aldehyde
98.35%)；Recycle methyl butynol 20.84g(methyl butyne alcohol content 99%), it is computed conversion ratio 92.0%, selectivity
95.5%, yield 87.86%.
Embodiment 2
Methyl butynol 260g(water content 0.3%, main content 99.5% are added into 500mL three-necked flask), zinc acetate 6.5g, three
Phenyl phosphorus palladium 4.10g, styrene acid 15g feed intake complete, open agitating and heating heating, stop heating when temperature reaches 90 DEG C, start
Reaction, temperature flow back when reaching 104 DEG C.From timing is begun to warm up, reaction 4h starts sample detection, and iso-amylene aldehyde reaches
Stop reaction to 80% or more.Reaction solution carries out de- weight, rectifying obtains isoamyl olefine aldehydr finished product 234.59g(iso-amylene aldehyde
99.1%)；Recycle methyl butynol 16.95g(methyl butyne alcohol content 98.9%), it is computed conversion ratio 93.5%, selectivity
96.4%, yield 90.13%.
Embodiment 3
Methyl butynol 260g(water content 0.3%, main content 99.5% are added into 500mL three-necked flask), zinc acetate 2.6g, two
Chlorine two triphenyl phosphorus palladium 3.0g, malonic acid 5g feed intake complete, open agitating and heating heating, stop heating when temperature reaches 90 DEG C, open
Begin to react, temperature flows back when reaching 104 DEG C.From timing is begun to warm up, reaction 4h starts sample detection, iso-amylene aldehyde
Reach 80% or more stopping reaction.Reaction solution carries out de- weight, rectifying obtains isoamyl olefine aldehydr finished product 223.97g(iso-amylene aldehyde
98.57%)；Recycle methyl butynol 25.79g(methyl butyne alcohol content 99%), it is computed conversion ratio 90.1%, selectivity
95.0%, yield 85.60%.
Embodiment 4
Methyl butynol 260g(water content 0.3%, main content 99.5% are added into 500mL three-necked flask), zinc acetate 1.0g, first
Base triphenyl phosphorus palladium 1.0g, propionic acid 10.0g feed intake complete, open agitating and heating heating, stop heating when temperature reaches 90 DEG C, open
Begin to react, temperature flows back when reaching 104 DEG C.From timing is begun to warm up, reaction 4h starts sample detection, iso-amylene aldehyde
Reach 80% or more stopping reaction.Reaction solution carries out de- weight, rectifying obtains isoamyl olefine aldehydr finished product 225.84g(iso-amylene aldehyde
99%)；Recycle methyl butynol 22.92g(methyl butyne alcohol content 99.05%), it is computed conversion ratio 91.2%, selectivity
95.01%, yield 86.65%.
Embodiment 5
Methyl butynol 260g(water content 0.3%, main content 99.5% are added into 500mL three-necked flask), zinc acetate 0.26g,
1,2- bis- (diphenylphosphine) ethyl palladium 1.5g, oxalic acid 3.0g feed intake complete, open agitating and heating heating, stop when temperature reaches 90 DEG C
It only heats, starts to react, temperature flows back when reaching 104 DEG C.From timing is begun to warm up, reaction 4h starts sample detection, different
Amylene aldehyde reaches 80% or more stopping reaction.Reaction solution carries out de- weight, rectifying obtains isoamyl olefine aldehydr finished product 224.92g(isoamyl
Olefine aldehydr content 98.6%)；Recycle methyl butynol 24.70g(methyl butyne alcohol content 99.2%), it is computed conversion ratio 90.5%, is selected
Selecting property 95.01%, yield 85.98%.
Embodiment 6
Methyl butynol 260g(water content 0.3%, main content 99.5% are added into 500mL three-necked flask), zinc acetate 10g, three
Phenyl phosphorus palladium chloride 2g, tartaric acid 0.5g feed intake complete, open agitating and heating heating, stop heating when temperature reaches 90 DEG C, start
Reaction, temperature flow back when reaching 104 DEG C.From timing is begun to warm up, reaction 4h starts sample detection, and iso-amylene aldehyde reaches
Stop reaction to 80% or more.Reaction solution carries out de- weight, rectifying obtains isoamyl olefine aldehydr finished product 228.41g(iso-amylene aldehyde
98.69%)；Recycle methyl butynol 21.36g(methyl butyne alcohol content 99.0%), it is computed conversion ratio 91.8%, selectivity
95.2%, yield 87.39%.
Embodiment 7
Methyl butynol 260g(water content 0.3%, main content 99.5% are added into 500mL three-necked flask), zinc acetate 8.0g, three
Phenyl phosphorus palladium 3.0g, glutaric acid 10g feed intake complete, open agitating and heating heating, stop heating when temperature reaches 90 DEG C, start anti-
It answers, temperature flows back when reaching 104 DEG C.From timing is begun to warm up, reaction 4h starts sample detection, and iso-amylene aldehyde reaches
80% or more stops reaction.Reaction solution carries out de- weight, rectifying obtains isoamyl olefine aldehydr finished product 224.06g(iso-amylene aldehyde
98.74%)；Recycle methyl butynol 25.59g(methyl butyne alcohol content 99.3%), it is computed conversion ratio 90.15%, selectivity
95.15%, yield 85.78%.
Embodiment 8
To addition methyl butynol 260g(water content 0.3%, main content 99.5% into 500mL three-necked flask), zinc acetate 10.0,
Methyl triphenyl phosphorus palladium 5.2g, phenylacetic acid 20g feed intake complete, open agitating and heating heating, stop heating when temperature reaches 90 DEG C,
Start to react, temperature flows back when reaching 104 DEG C.From timing is begun to warm up, reaction 4h starts sample detection, and isoamyl olefine aldehydr contains
Amount reaches 80% or more stopping reaction.Reaction solution carries out de- weight, rectifying obtains isoamyl olefine aldehydr finished product 224.05g(iso-amylene aldehyde
98.5%)；Recycle methyl butynol 26.03g(methyl butyne alcohol content 99.06%), it is computed conversion ratio 90.0%, selectivity
95.07%, yield 85.56%.
Embodiment 9
Methyl butynol 260g(water content 0.3%, main content 99.5% are added into 500mL three-necked flask), zinc acetate 5.0g, three
Phenyl phosphorus palladium 3.0g, phthalic acid 10g feed intake complete, open agitating and heating heating, stop heating when temperature reaches 90 DEG C, open
Begin to react, temperature flows back when reaching 104 DEG C.From timing is begun to warm up, reaction 4h starts sample detection, iso-amylene aldehyde
Reach 80% or more stopping reaction.Reaction solution carries out de- weight, rectifying obtains isoamyl olefine aldehydr finished product 228.02g(iso-amylene aldehyde
98.2%)；Recycle methyl butynol 23.44g(methyl butyne alcohol content 99%), it is computed conversion ratio 91.0%, selectively 95.4%,
Yield is 86.81%.
Data summarization in above-described embodiment is as follows:
Embodiment 10
Methyl butynol 260g(water content 0.3%, main content 99.5% are added into 500mL three-necked flask), zinc acetate 0.26g,
Triphenyl phosphorus palladium 0.026g, styrene acid 0.26g, feeds intake complete, opens agitating and heating heating, stops adding when temperature reaches 90 DEG C
Heat starts to react, and temperature flows back when reaching 104 DEG C.From timing is begun to warm up, reaction 4h starts sample detection, iso-amylene
Aldehyde reaches 80% or more stopping reaction.Reaction solution carries out de- weight, rectifying obtains isoamyl olefine aldehydr finished product 223.89g(isoamyl olefine aldehydr
Content 98.95%)；Recycle methyl butynol 24.72g(methyl butyne alcohol content 99.1%), it is computed conversion ratio 90.5%, is selected
Property 95.1%, yield 86.06%.
Embodiment 11
Methyl butynol 260g(water content 0.3%, main content 99.5% are added into 500mL three-necked flask), zinc acetate 13.0g,
Triphenyl phosphorus palladium 5.2g, styrene acid 26.0g, feeds intake complete, opens agitating and heating heating, stops heating when temperature reaches 90 DEG C,
Start to react, temperature flows back when reaching 104 DEG C.From timing is begun to warm up, reaction 4h starts sample detection, and isoamyl olefine aldehydr contains
Amount reaches 80% or more stopping reaction.Reaction solution carries out de- weight, rectifying obtains isoamyl olefine aldehydr finished product 233.14g(iso-amylene aldehyde
98.79%)；Recycle methyl butynol 16.15g(methyl butyne alcohol content 99%), it is computed conversion ratio 93.8%, selectivity
95.2%, yield 89.30%.
Embodiment 12
Methyl butynol 260g(water content 0.3%, main content 99.5% are added into 500mL three-necked flask), zinc acetate 6.5g, three
Phenyl phosphorus palladium 2.6g, styrene acid 13g feed intake complete, open agitating and heating heating, stop heating when temperature reaches 90 DEG C, start
Reaction, temperature flow back when reaching 104 DEG C.From timing is begun to warm up, reaction 4h starts sample detection, and iso-amylene aldehyde reaches
Stop reaction to 80% or more.Reaction solution carries out de- weight, rectifying obtains isoamyl olefine aldehydr finished product 231.64g(iso-amylene aldehyde
98.68%)；Recycle methyl butynol 19.53g(methyl butyne alcohol content 99.05%), it is computed conversion ratio 92.5%, selectivity
95.8%, yield 88.2%.
Data summarization in above-described embodiment is as follows:
Embodiment 13
Methyl butynol 260g(water content 0.3%, main content 99.5% are added into 500mL three-necked flask), zinc acetate 6.0g, three
Phenyl phosphorus palladium 3.0g, styrene acid 10g feed intake complete, open agitating and heating heating, start to react when temperature reaches 85 DEG C, temperature
It flows back when reaching 104 DEG C, continues heating and reacted.From timing is begun to warm up, reaction 4h starts sample detection, iso-amylene
Aldehyde reaches 80% or more stopping reaction.Reaction solution carries out de- weight, rectifying obtains isoamyl olefine aldehydr finished product 230.14g(isoamyl olefine aldehydr
Content 98.88%)；Recycle methyl butynol 20.59g(methyl butyne alcohol content 99.0%), it is computed conversion ratio 92.1%, is selected
Property 95.8%, yield 88.23%.The de- weight total 24g(19g containing catalyst of heel, increases heel 5g newly).
Embodiment 14(heel is applied for the first time)
Methyl butynol is added into 500mL three-necked flask, and (for water content less than 0.5%, main content is greater than 99%) 260g, applies reality
It applies and takes off weight heel 24g in example 13, feed intake complete, open agitating and heating heating, start to react when temperature reaches 85 DEG C, temperature reaches
It flows back at 104 DEG C, continues heating and reacted.From timing is begun to warm up, reaction 4h starts sample detection, and isoamyl olefine aldehydr contains
Amount reaches 80% or more stopping reaction.Reaction solution carries out de- weight, rectifying obtains isoamyl olefine aldehydr finished product 230.15g(iso-amylene aldehyde
98.46%)；Recycle methyl butynol 20.84g(methyl butyne alcohol content 99.0%), it is computed conversion ratio 92.0%, selectivity
95.5%, yield 87.86%；The de- weight total 28g(of heel increases heel 4g newly containing heel 24g is applied).
It applies for embodiment 15(heel the 5th time)
Methyl butynol is added into 500mL three-necked flask, and (water content less than 0.5%, main content is greater than 99%) 260g, applies the
Four secondary response heel 40.6g, feed intake complete, open agitating and heating heating, start to react when temperature reaches 85 DEG C, temperature reaches 104
DEG C when flow back, continue heating reacted.From timing is begun to warm up, reaction 4h starts sample detection, iso-amylene aldehyde
Reach 80% or more stopping reaction.Reaction solution carries out de- weight, rectifying obtains isoamyl olefine aldehydr finished product 228.17g(iso-amylene aldehyde
98.57%)；Recycle methyl butynol 22.14g(methyl butyne alcohol content 99.0%), it is computed conversion ratio 91.5%, selectivity
95.3%, yield 87.20%；The de- weight total 44.7g(of heel increases heel 4.1g newly containing heel 40.6g is applied).
It applies for embodiment 16(heel the 20th time)
Methyl butynol is added into 500mL three-necked flask, and (water content less than 0.5%, main content is greater than 99%) 260g, applies the
19 secondary response heel 100.3g, feed intake complete, open agitating and heating heating, stop heating when temperature reaches 90 DEG C, start to react,
Temperature flows back when reaching 104 DEG C.From timing is begun to warm up, reaction 4h starts sample detection, and iso-amylene aldehyde reaches 80%
It is above to stop reaction.Reaction solution carries out de- weight, rectifying obtains isoamyl olefine aldehydr finished product 227.3g(iso-amylene aldehyde 98.5%)；It returns
Receive methyl butynol 23.97g(methyl butyne alcohol content 99.0%), it is computed conversion ratio 90.8%, selectivity 95.6%, yield is
86.80%；The de- weight total 104.4g(of heel increases heel 4.1g newly containing heel 100.3g is applied).
Each testing result in above-described embodiment is summarized as follows:
Embodiment 17
Methyl butynol 260g(water content 0.1%, main content 99% are added into 500mL three-necked flask), zinc acetate 6.5g, triphen
Base phosphorus palladium 4.10g, styrene acid 15g feed intake complete, open agitating and heating heating, start to react when temperature reaches 70 DEG C, stop plus
Heat, from timing is begun to warm up, reaction 4h starts sample detection, and iso-amylene aldehyde reaches 80% or more stopping reaction.Reaction solution into
The de- weight of row, rectifying obtain isoamyl olefine aldehydr finished product 233.6g(iso-amylene aldehyde 99%)；Recycle methyl butynol 17.23g(methyl
Butine alcohol content 98.5%), it is computed conversion ratio 93.4%, selectivity 96.3%, yield 89.94%；The de- weight total 31g(of heel, which contains, to be urged
Agent 25.6g increases heel 5.4g newly).
Embodiment 18
Methyl butynol 260g(water content 0.5%, main content 99% are added into 500mL three-necked flask), zinc acetate 6.5g, triphen
Base phosphorus palladium 4.10g, styrene acid 15g feed intake complete, open agitating and heating heating, start to react when temperature reaches 70 DEG C, stop plus
Heat, from timing is begun to warm up, reaction 4h starts sample detection, and iso-amylene aldehyde reaches 80% or more stopping reaction.Reaction solution into
The de- weight of row, rectifying obtain isoamyl olefine aldehydr finished product 233.87g(iso-amylene aldehyde 98.5%)；Recycle methyl butynol 16.7g(first
Base butine alcohol content 98.4%), it is computed conversion ratio 93.5%, selectivity 96.2%, yield 89.95%；The de- weight total 31g(of heel contains
Catalyst 25.6g increases heel 5.4g newly).
Embodiment 19
Methyl butynol 260g(water content 1%, main content 99% are added into 500mL three-necked flask), zinc acetate 6.5g, triphenyl
Phosphorus palladium 4.10g, styrene acid 15g, feeds intake complete, opens agitating and heating heating, starts to react when temperature reaches 70 DEG C, stops adding
Heat, from timing is begun to warm up, reaction 4h starts sample detection, and iso-amylene aldehyde reaches 80% or more stopping reaction.Reaction solution into
The de- weight of row, rectifying obtain isoamyl olefine aldehydr finished product 230.28g(iso-amylene aldehyde 98.8%)；Recycle methyl butynol 18.08g(first
Base butine alcohol content 98.6%), it is computed conversion ratio 93%, selectivity 96%, yield 89.28%；The de- weight total 31.3g(of heel, which contains, to be urged
Agent 25.6g increases heel 5.7g newly).
The data summarization of embodiment 17-19 is as follows:
Embodiment 20
Methyl butynol 260g(water content 0.5%, main content 99.5% are added into 500mL three-necked flask), zinc acetate 6.0g, three
Phenyl phosphorus palladium 4.0g, styrene acid 10g feed intake complete, open agitating and heating heating, start to react when temperature reaches 70 DEG C, stop
Heating, temperature flows back when reaching 104 DEG C, from beginning to warm up timing.From timing is begun to warm up, reaction 4h starts sampling inspection
It surveys, iso-amylene aldehyde reaches 80% or more stopping reaction.Reaction solution carries out de- weight, rectifying obtains isoamyl olefine aldehydr finished product 236.92g
(iso-amylene aldehyde 98.6%)；Recycle methyl butynol 16.54g(methyl butyne alcohol content 99.0%), it is computed conversion ratio
93.2%, selectivity 96.4%, yield 89.84%.The de- weight total 24.96g(20g containing catalyst of heel, increases heel 4.96g newly)
Embodiment 21
Methyl butynol 260g(water content 0.5%, main content 99.5% are added into 500mL three-necked flask), zinc acetate 6.0g, three
Phenyl phosphorus palladium 4.0g, styrene acid 10g feed intake complete, open agitating and heating heating, and temperature flows back when reaching 104 DEG C, work as temperature
Stop heating when reaching 105 DEG C.From timing is begun to warm up, reaction 4h starts sample detection, and iso-amylene aldehyde reaches 80% or more
Stop reaction.Reaction solution carries out de- weight, rectifying obtains isoamyl olefine aldehydr finished product 237.18g(iso-amylene aldehyde 98.5%)；Recycle first
Base butynol 15.76g(methyl butyne alcohol content 99.0%), it is computed conversion ratio 93.5%, selectivity 96.1%, yield is
89.85%.The de- weight total 25.06g(20g containing catalyst of heel, increases heel 5.06g newly)
The data summarization of embodiment 20 and 21 is as follows:
Above-mentioned conversion ratio is conversion per pass, and the yield is one-way yield.
Unless specifically indicated, the percentage that the present invention uses is mass percent, and the ratio is mass ratio.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (8)
1. a kind of method of methyl butynol iso-synthesis isoamyl olefine aldehydr, which is characterized in that the method, the catalyst used for
For mixed catalyst, it is made of major catalyst, co-catalyst, organic acid.
2. a kind of method of methyl butynol iso-synthesis isoamyl olefine aldehydr according to claim 1, which is characterized in that described
Major catalyst is triphenyl phosphorus palladium, diphenylphosphine palladium, two triphenyl phosphorus palladium of dichloro, methyl triphenyl phosphorus palladium, bis- (diphenyl of 1,2-
Phosphorus) ethyl palladium, triphenyl phosphorus palladium chloride be one such.
3. a kind of method of methyl butynol iso-synthesis isoamyl olefine aldehydr according to claim 1, which is characterized in that described
Co-catalyst is zinc acetate.
4. a kind of method of methyl butynol iso-synthesis isoamyl olefine aldehydr according to claim 1, which is characterized in that described
Organic acid is succinic acid, malonic acid, propionic acid, oxalic acid, tartaric acid, glutaric acid, styrene acid, phenylacetic acid, phthalic acid, wherein
One kind.
5. a kind of method of methyl butynol iso-synthesis isoamyl olefine aldehydr according to claim 1, which is characterized in that described
The dosage of major catalyst is the 0.01-2wt% of raw material methyl butynol quality, and the dosage of co-catalyst is raw material methyl butynol
The 0.1-5wt% of quality, organic acid dosage are the 0.1-10wt% of raw material methyl butynol quality.
6. a kind of method of methyl butynol iso-synthesis isoamyl olefine aldehydr according to claim 1, which is characterized in that described
Method, reaction temperature are 70-105 DEG C.
7. a kind of method of methyl butynol iso-synthesis isoamyl olefine aldehydr according to claim 1, it is characterised in that: described
Method, reaction pressure are normal pressure.
8. a kind of method of methyl butynol iso-synthesis isoamyl olefine aldehydr according to claim 1, it is characterised in that: described
Methyl butynol, main content are greater than 99 %(GC), water content is less than 1wt%.
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| PCT/CN2020/083522 WO2020220944A1 (en) | 2019-04-29 | 2020-04-07 | Method for synthesizing isopentenol by isomerization of methyl butynol |
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| WO2020220944A1 (en) * | 2019-04-29 | 2020-11-05 | 浙江新和成股份有限公司 | Method for synthesizing isopentenol by isomerization of methyl butynol |
| CN114773168A (en) * | 2022-04-28 | 2022-07-22 | 江苏宏邦化工科技有限公司 | Method for synthesizing cis/trans-prenyl-3-methyl butadiene ether by using methyl butynol and isopentenol |
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| CN110330416A (en) * | 2019-07-05 | 2019-10-15 | 安徽智新生化有限公司 | A kind of preparation method of isoamyl olefine aldehydr |
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| CN114773168B (en) * | 2022-04-28 | 2024-08-13 | 江苏宏邦化工科技有限公司 | Method for synthesizing cis/trans-prenyl-3-methyl butadiene ether by using methyl butynol and isopentenol |
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