CN100999453B - Raw material formule for preparing keto isophorone and its method - Google Patents

Raw material formule for preparing keto isophorone and its method Download PDF

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CN100999453B
CN100999453B CN200710008464A CN200710008464A CN100999453B CN 100999453 B CN100999453 B CN 100999453B CN 200710008464 A CN200710008464 A CN 200710008464A CN 200710008464 A CN200710008464 A CN 200710008464A CN 100999453 B CN100999453 B CN 100999453B
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isophorone
ketone
solvent
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catalyzer
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CN100999453A (en
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董声雄
黄聿魏
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Fuzhou University
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Abstract

The present invention provides a preparation method of keto-isophorone and its formula of raw materials. The formula of raw materials: solvent; Organic base; Catalyst; beta - isophorone; Catalyst is metal-organic ligand combined by copper ions and Schiff base that takes salicylaldehyde or its derivatives as the main structure with 10% of the metal-organic ligand; The Preparation : According to the above formula, first add solvent, organic base and catalyst into reactor, and then add beta - isophorone; put in adequate oxygen, and then pressurized to 0 to 1MPa, control the whole reaction temperature at 20 to 00deg, the reaction time for one to eight hours, at last obtain keto-isophorone. The features are the speed reaction, high-yield, production time and space efficiency is greatly enhanced.

Description

Preparation ketone is for the composition of raw materials and the method for isophorone
Technical field
The present invention relates to organic preparation method, more specifically relate to a kind of composition of raw materials and method for preparing ketone for isophorone.
Background technology
Ketone is a kind of natural product for isophorone (formal name used at school 3,5,5-3-methyl cyclohexanol-2-alkene-1,4-diketone), can be used as food flavouring or spices in food or the cosmetic formulations, and various cigarette are all had significant perfuming effect; Still the important intermediate for preparing multiple carotenoid, VITAMIN, spices, medicine etc.Therefore, since the seventies in 20th century, synthetic ketone has obtained extensive concern at home and abroad for isophorone.Divide main technology of preparing to have following from the kind of reacting the catalyzer that adopts:
With oxygen or oxygen-containing gas is oxygenant, salt with aluminium, vanadium, chromium, manganese, iron or cobalt is catalyzer, in the presence of machine nitrogen base (as pyridine), β-isophorone oxidation is prepared the method for ketone for isophorone, the mol ratio of recommending β-isophorone and pyridine simultaneously is 130: 330, and reaction yield is 68-80%.Though this method has very high transformation efficiency, this reaction makes β-isophorone anteiso-constitute α-isophorone easily, and side reaction is a lot, makes selection rate not high.In addition, this method also will remove a large amount of nitrogenous organic bases and makes this method energy consumption big (as patent: US4046813).
With Mn or Co-Salen derivative is catalyzer, tripropylamine etc. are organic bases, prepare the method for ketone for isophorone with molecular oxygen oxidation β-isophorone oxygen respectively in dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMAC), N-Methyl pyrrolidone organic solvents such as (NMP).Special recommendation as organic bases, serves as preferential combination with dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMA) organic solvent with tripropylamine.But the shortcoming of a maximum of these methods is reaction is easy to generate 3,5,5-3-methyl cyclohexanol-2-alkene-1-ketone, 2,2,6-trimethyl-cyclohexane-1, by products such as 4-diketone because these by product molecular weight and other rerum natura are similar for isophorone to product ketone, make ketone for the purifying of isophorone quite difficult (as patent: US4026947, US6166261 and CN1281844).
Porphyrin or phthalocyanine with Co, Mn are catalyzer, are organic bases with the triethylamine, and in the glycol dinitrate ether solvents, catalyzed oxidation β-isophorone system ketone is for the method for isophorone.Though this method yield height (can reach 95%), its catalyzer is relatively costly, makes technology cost height, and the low industrialization of diglyme flash-point will just can be implemented under the preventive measures of extremely safe (as patent: US4898985).
In sum, be that raw material system ketone all is in the presence of some additives (as solvent, promotor) for isophorone technology with β-isophorone at present, be oxygenant with the molecular oxygen, be catalyzer with the organic coordination compound of transition metal.There is long reaction time (all more than 10 hours) in these technologies; Mainly be to use with Co, heavy metal big for environment pollution such as Mn is that the organic coordination compound of core is a catalyzer; The low shortcomings such as (weight content＜30%) of reacting body β-isophorone content.
Summary of the invention
The present invention seeks at the problems referred to above, a kind of composition of raw materials and method for preparing ketone for isophorone is provided.
The present invention prepares ketone: solvent; Organic bases; Catalyzer; 3,5,5-3-methyl cyclohexanol-3-alkene-1-ketone, i.e. β-isophorone; Described catalyzer is to be the Schiff's base of agent structure and the cvdmetallorganiccvd ligand that cupric ion fits in the salicylic aldehyde or derivatives thereof, and the molecular formula of described cvdmetallorganiccvd ligand is as follows:
Figure G2007100084647D00021
R 11And R 12, R 21And R 22Be identical or separate respectively electrophilic or electron-donating group, described electrophilic or electron-donating group are H, and X is a halogen, OH, NO 2, COR 4, OCOR 4, COOR 4Or SO 3R 4In a kind of, R wherein 4Be H or C 1～C 4Alkyl; R 31, R 32Be identical or independently electrophilic or electron-donating group mutually, described electrophilic or electron-donating group are H, R 6, R 5X, R 5OH, R 5NO 2, R 5COR 6, R 5OCOR 6, R 5COOR 6Or R 5SO 3R 6In a kind of, R wherein 5Be zero alkyl to four carbon, R 6It is the alkyl of H or C1～C4; The title complex central ion is a cupric ion.
The present invention prepares ketone: earlier solvent, organic bases and catalyzer are added in the reaction vessel according to above-mentioned prescription, again β-isophorone is added in the reaction vessel, in reaction vessel, feed enough oxygen, being pressurized to gauge pressure then is 0～1MPa, control entire reaction temperature is at 20～100 ℃, reaction times is 1～8 hour, prepares ketone for isophorone.
The inventive method has been compared following advantage with above-mentioned patent:
1. use the little cvdmetallorganiccvd ligand of forming as the Schiff's base and the cupric ion of agent structure with the salicylic aldehyde or derivatives thereof of environmental pollution to be catalyzer.
2. speed of reaction is fast, primitive reaction fully (transformation efficiency＞96%) in 6 hours, and yield is higher can reach 90%.
3. β in the reacting body-isophorone content height (weight content＞50% can reach 85%), this makes that producing spatiotemporal efficiency improves greatly.
Embodiment
Solvent, organic bases and catalyzer are added in the reaction vessel, again β-isophorone is added in the reaction vessel, in reaction vessel, feed enough oxygen, be pressurized to 0～1MPa then, control entire reaction temperature is at 20～100 ℃, and the reaction times is 1～8 hour, prepares ketone for isophorone.
Wherein, each composition weight umber of composition of raw materials is: solvent: 0～2 part; Organic bases: 2～0.002 parts; Catalyzer: 0.0001～0.05 part; β-isophorone: 1 part.
Solvent is inert solvent or the solvent with metal registration property, and wherein inert solvent is one or more mixtures in methyl alcohol, acetone, ethanol, ethyl acetate and the toluene; The solvent of metal registration property is one or more mixtures in dimethyl formamide, N,N-DIMETHYLACETAMIDE and the dimethyl sulfoxide (DMSO).
Organic bases is one or more mixtures in quadrol, triethylamine, tripropyl amine, pyridine and the pyrimidine.
β in the preparation process-isophorone adding mode is disposable feeding intake or fed batch, and be 0.5～2 hour the pitch time of fed batch.
The present invention is specifically as follows for embodiment:
Be prepared as follows catalyzer:
Figure G2007100084647D00031
1# R 11＝H R 12＝H R 21＝H R 22＝H R 31＝CH 2C 6H 5 R 32＝CH 2C 6H 5
2# R 11＝H R 12＝H R 21＝CH 3 R 22＝CH 3 R 31＝CH 2CH 2SO 3H R 32＝CH 2CH 2SO 3H
3# R 11＝H R 12＝H R 21＝SO 3H R 22＝SO 3H R 31＝CH 2CH 2SO 3H R 32＝CH 2CH 2SO 3H
4# R 11＝CH 3 R 12＝CH 3 R 21＝H R 22＝H R 31＝CH 3CH 2CH 3 R 32＝CH 3CH 2CH 3
5# R 11＝CH 3 R 12＝CH 3 R 21＝CH 3 R 22＝CH 3 R 3＝CH 2CH 2SO 3H R 32＝CH 2CH 2SO 3H
6# R 11＝CH 3 R 12＝CH 3 R 21＝SO 3H R 22＝SO 3H R 31＝CH 2C 6H 5 R 32＝CH 2C 6H 5
7# R 11＝Cl R 12＝Cl R 21＝H R 22＝H R 31＝CH 2CH 2SO 3H R 32＝CH 2CH 2SO 3H
8# R 11＝Cl R 12＝Cl R 21＝CH 3 R 22＝CH 3 R 31＝CH 2C 6H 5 R 32＝CH 2C 6H 5
9# R 11＝Cl R 12＝Cl R 21＝SO 3H R 22＝SO 3H R 31＝CH 3CH 2CH 3 R 32＝CH 3CH 2CH 3
Embodiment 1
8ml acetone, 2g triethylamine and 0.02mmol catalyzer 1# are added band magnetic agitation pressure reaction still, and in the reactor that 2.5g β-isophorone is added, the air in the logical replacement of oxygen reactor is pressurized to 0.16MPa for several times then again.Control reaction temperature begins reaction at 30 ℃.And every interval throws 2.5g β-isophorone half an hour again, throws 10g β-isophorone altogether.Continue reaction 2.5 hours after adding whole β-isophorones, total coreaction 4 hours.Using gas Chromatographic Determination ketone after reaction finishes is 84.6% for the yield of isophorone.
Embodiment 2
8ml DMF, 2g tripropyl amine and 0.02mmol catalyzer 2# are added band magnetic agitation pressure reaction still, and in the reactor that 2.5g β-isophorone is added, the air in the logical replacement of oxygen reactor is pressurized to 0.16MPa for several times then again.Control reaction temperature begins reaction at 80 ℃.And every interval throws 2.5g β-isophorone half an hour again, throws 10g β-isophorone altogether.Continue reaction 2.5 hours after adding whole β-isophorones, total coreaction 4 hours.Using gas Chromatographic Determination ketone after reaction finishes is 91.0% for the yield of isophorone.
Embodiment 3
8ml toluene, 2g tripropyl amine and 0.02mmol catalyzer 3# are added band magnetic agitation pressure reaction still, and in the reactor that 10g β-isophorone is added, the air in the logical replacement of oxygen reactor is pressurized to 0.16MPa for several times then again.Control reaction temperature begins reaction at 60 ℃.Reacted 4 hours, using gas Chromatographic Determination ketone after reaction finishes is 84.2% for the yield of isophorone.
Embodiment 4
2g triethylamine and 0.02mmol catalyzer 4# are added band magnetic agitation pressure reaction still, and in the reactor that 2.5g β-isophorone is added, the air in the logical replacement of oxygen reactor is pressurized to 0.16MPa for several times then again.Control reaction temperature begins reaction at 50 ℃.And every interval throws 2.5g β-isophorone half an hour again, throws 10g β-isophorone altogether.Continue reaction 2.5 hours after adding whole β-isophorones, total coreaction 4 hours.Using gas Chromatographic Determination ketone after reaction finishes is 83.0% for the yield of isophorone.
Embodiment 5
2g tripropyl amine and 0.02mmol catalyzer 5# are added band magnetic agitation pressure reaction still, and in the reactor that 10g β-isophorone is added, the air in the logical replacement of oxygen reactor is pressurized to 0.16MPa for several times then again.Control reaction temperature begins reaction at 75 ℃.Reacted 4 hours, using gas Chromatographic Determination ketone after reaction finishes is 84.4% for the yield of isophorone.
Embodiment 6
8ml acetone, 2g pyridine and 0.02mmol catalyzer 6# are added band magnetic agitation pressure reaction still, and in the reactor that 2.5g β-isophorone is added, the air in the logical replacement of oxygen reactor is pressurized to 0.16MPa for several times then again.Control reaction temperature begins reaction at 30 ℃.And every interval throws 2.5g β-isophorone half an hour again, throws 10g β-isophorone altogether.Continue reaction 2.5 hours after adding whole β-isophorones, total coreaction 4 hours.Using gas Chromatographic Determination ketone after reaction finishes is 88.7% for the yield of isophorone.
Embodiment 7
8ml toluene, 2g triethylamine and 0.02mmol catalyzer 7# are added band magnetic agitation pressure reaction still, and in the reactor that 2.5g β-isophorone is added, the air in the logical replacement of oxygen reactor is pressurized to 0.16MPa for several times then again.Control reaction temperature begins reaction at 80 ℃.And every interval throws 2.5g β-isophorone half an hour again, throws 10g β-isophorone altogether.Continue reaction 2.5 hours after adding whole β-isophorones, total coreaction 4 hours.It is 89.9% for the yield of isophorone that reaction has finished to use gas Chromatographic Determination ketone.
Embodiment 8
8ml acetone, 2g tripropyl amine and 0.02mmol catalyzer 8# are added band magnetic agitation pressure reaction still, and in the reactor that 2.5g β-isophorone is added, the air in the logical replacement of oxygen reactor is pressurized to 0.16MPa for several times then again.Control reaction temperature begins reaction at 60 ℃.And every interval throws 2.5g β-isophorone half an hour again, throws 10g β-isophorone altogether.Continue reaction 2.5 hours after adding whole β-isophorones, total coreaction 4 hours.It is 91.3% for the yield of isophorone that reaction has finished to use gas Chromatographic Determination ketone.
Embodiment 9
2g pyridine and 0.02mmol catalyzer 9# are added band magnetic agitation pressure reaction still, and in the reactor that 2.5g β-isophorone is added, the air in the logical replacement of oxygen reactor is pressurized to 0.16MPa for several times then again.Control reaction temperature begins reaction at 50 ℃.Reacted 4 hours, using gas Chromatographic Determination ketone after reaction finishes is 87.3% for the yield of isophorone.Each embodiment reaction result is listed in table one
Table one
Embodiment β-isophorone/g Catalyzer/mmol Solvent Organic bases Temperature of reaction/℃ Reaction times/hr Yield/%
1 10 1#0.02 Acetone Triethylamine 30 4 84.6
2 10 2#0.02 DMF Tripropyl amine 80 4 91.0
3 10 3#0.02 Toluene Pyridine 60 4 84.2
4 10 4#0.02 —— Triethylamine 50 4 83.0
Embodiment β-isophorone/g Catalyzer/mmol Solvent Organic bases Temperature of reaction/℃ Reaction times/hr Yield/%
5 10 5#0.02 —— Tripropyl amine 75 4 84.4
6 10 6#0.02 Acetone Pyridine 30 4 88.7
7 10 7#0.02 Toluene Triethylamine 80 4 89.9
8 10 8#0.02 Acetone Tripropyl amine 60 4 91.3
9 10 9#0.02 —— Pyridine 50 4 87.3

Claims (6)

1. method for preparing ketone for isophorone, it is characterized in that: described ketone for each component of composition of raw materials of isophorone is: solvent; Organic bases; Catalyzer; 3,5,5-3-methyl cyclohexanol-3-alkene-1-ketone, i.e. β-isophorone; Described catalyzer is a cvdmetallorganiccvd ligand, and structural formula is as follows:
Figure F2007100084647C00011
R 11＝H R 12＝H R 21＝H R 22＝H R 31＝CH 2C 6H 5 R 32＝CH 2C 6H 5；
R 11＝H R 12＝H R 21＝CH 3 R 22＝CH 3 R 31＝CH 2CH 2SO 3H R 32＝CH 2CH 2SO 3H；
R 11＝H R 12＝H R 21＝SO 3H R 22＝SO 3H R 31＝CH 2CH 2SO 3H R 32＝CH 2CH 2SO 3H；
R 11＝CH 3 R 12＝CH 3 R 21＝CH 3 R 22＝CH 3 R 3＝CH 2CH 2SO 3H R 32＝CH 2CH 2SO 3H；
R 11＝CH 3 R 12＝CH 3 R 21＝SO 3H R 22＝SO 3H R 31＝CH 2C 6H 5 R 32＝CH 2C 6H 5；
R 11＝Cl R 12＝Cl R 21＝H R 22＝H R 31＝CH 2CH 2SO 3H R 32＝CH 2CH 2SO 3H；
R 11＝Cl R 12＝Cl R 21＝CH 3 R 22＝CH 3 R 31＝CH 2C 6H 5 R 32＝CH 2C 6H 5；
The title complex central ion is a cupric ion;
The parts by weight of described each component of composition of raw materials are: solvent: 0～2 part; Organic bases: 2～0.002 parts; Catalyzer: 0.0001～0.05 part; β-isophorone: 1 part;
Earlier solvent, organic bases and catalyzer are added in the reaction vessel according to described proportioning, again β-isophorone is added in the reaction vessel, in reaction vessel, feed enough oxygen, being pressurized to gauge pressure then is 0～1MPa, control entire reaction temperature is at 20～100 ℃, reaction times is 1～8 hour, prepares ketone for isophorone.
2. the method for preparing ketone for isophorone according to claim 1 is characterized in that: described solvent is inert solvent or the solvent with metal registration property.
3. the method for preparing ketone for isophorone according to claim 2 is characterized in that: described inert solvent is one or more mixtures in methyl alcohol, acetone, ethanol, ethyl acetate and the toluene.
4. the method for preparing ketone for isophorone according to claim 2 is characterized in that: described solvent with metal registration property is one or more mixtures in dimethyl formamide, N,N-DIMETHYLACETAMIDE and the dimethyl sulfoxide (DMSO).
5. the method for preparing ketone for isophorone according to claim 1 is characterized in that: described organic bases is one or more mixtures in quadrol, triethylamine, tripropyl amine, pyridine and the pyrimidine.
6. the method for preparing ketone for isophorone according to claim 1 is characterized in that: described β-isophorone adding mode is disposable feeding intake or fed batch, and be 0.5～2 hour the pitch time of fed batch.
CN200710008464A 2007-01-19 2007-01-19 Raw material formule for preparing keto isophorone and its method Expired - Fee Related CN100999453B (en)

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CN103962182A (en) * 2014-05-20 2014-08-06 武汉工程大学 Heteropoly acid doped Schiff base mononuclear manganese complex catalyst as well as synthesis method and application thereof
CN105541588B (en) * 2016-02-25 2017-12-01 济南悟通生物科技有限公司 A kind of synthetic method of diacetyl
CN115703702A (en) * 2021-08-16 2023-02-17 安徽圣诺贝化学科技有限公司 Method for preparing tea scented ketone by oxidizing alpha-isophorone

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1281844A (en) * 1999-06-25 2001-01-31 Basf公司 Preparation method of oxoisophorone
CN1287110A (en) * 1999-06-25 2001-03-14 Basf公司 Process for producing ketoisophorone with additives
CN1865210A (en) * 2006-01-25 2006-11-22 浙江大学 Process for preparing ketoisophorone

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1281844A (en) * 1999-06-25 2001-01-31 Basf公司 Preparation method of oxoisophorone
CN1287110A (en) * 1999-06-25 2001-03-14 Basf公司 Process for producing ketoisophorone with additives
CN1865210A (en) * 2006-01-25 2006-11-22 浙江大学 Process for preparing ketoisophorone

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