CN103304387A - Preparation method of hydratropic aldehyde - Google Patents
Preparation method of hydratropic aldehyde Download PDFInfo
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- CN103304387A CN103304387A CN2013102191475A CN201310219147A CN103304387A CN 103304387 A CN103304387 A CN 103304387A CN 2013102191475 A CN2013102191475 A CN 2013102191475A CN 201310219147 A CN201310219147 A CN 201310219147A CN 103304387 A CN103304387 A CN 103304387A
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- black nightshade
- nightshade aldehyde
- alkali
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- IQVAERDLDAZARL-UHFFFAOYSA-N 2-phenylpropanal Chemical compound O=CC(C)C1=CC=CC=C1 IQVAERDLDAZARL-UHFFFAOYSA-N 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 33
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003513 alkali Substances 0.000 claims abstract description 18
- 239000012044 organic layer Substances 0.000 claims abstract description 15
- 150000002148 esters Chemical class 0.000 claims abstract description 12
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000006482 condensation reaction Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 235000002594 Solanum nigrum Nutrition 0.000 claims description 53
- 240000002307 Solanum ptychanthum Species 0.000 claims description 53
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 21
- -1 halogenated acetic acids ester Chemical class 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 7
- 238000006317 isomerization reaction Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 claims description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 4
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- LMHHRCOWPQNFTF-UHFFFAOYSA-N s-propan-2-yl azepane-1-carbothioate Chemical compound CC(C)SC(=O)N1CCCCCC1 LMHHRCOWPQNFTF-UHFFFAOYSA-N 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000011449 brick Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000005194 fractionation Methods 0.000 claims description 2
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical compound COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 12
- 229910052736 halogen Inorganic materials 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract description 7
- 150000001242 acetic acid derivatives Chemical class 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- 230000029219 regulation of pH Effects 0.000 abstract 1
- 150000001299 aldehydes Chemical class 0.000 description 43
- 238000003756 stirring Methods 0.000 description 32
- 239000000047 product Substances 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000000746 purification Methods 0.000 description 5
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000006114 decarboxylation reaction Methods 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 230000005311 nuclear magnetism Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- FTOZMXOHOKRHNL-UHFFFAOYSA-N ethyl 2,3-dihydroxypropanoate Chemical compound CCOC(=O)C(O)CO FTOZMXOHOKRHNL-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000013599 spices Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical class [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- 238000003476 Darzens condensation reaction Methods 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- ZVFCNYSWQVMDQJ-UHFFFAOYSA-M [Br-].CC([Mg+])C1=CC=CC=C1 Chemical compound [Br-].CC([Mg+])C1=CC=CC=C1 ZVFCNYSWQVMDQJ-UHFFFAOYSA-M 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- LPHFLPKXBKBHRW-UHFFFAOYSA-L magnesium;hydrogen sulfite Chemical compound [Mg+2].OS([O-])=O.OS([O-])=O LPHFLPKXBKBHRW-UHFFFAOYSA-L 0.000 description 1
- YDCHPLOFQATIDS-UHFFFAOYSA-N methyl 2-bromoacetate Chemical class COC(=O)CBr YDCHPLOFQATIDS-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of hydratropic aldehyde. The method comprises the following steps: performing condensation reaction on acetophenone and halogenated acetate used as raw materials to obtain 3-methyl-3-phenyl glycidic ester, hydrolyzing in an alkali water solution to obtain 3-methyl-3-phenyl glycerate, performing pH regulation and acidification, performing isomerism reaction to obtain a hydratropic aldehyde rough product, reacting with hydrosulphite to obtain hydratropic aldehyde sulfonate, adding alkali to neutralize to obtain an organic layer, separating, washing and drying to obtain the target product hydratropic aldehyde.
Description
Technical field
The technology of the present invention relates to chemical technology field, particularly the synthetic field of spices.
Background technology
The chemical name of black nightshade aldehyde is the 2-phenylpropionaldehyde, and is English by name: Hydratropic aldehyde or 2-Phenyl propional dehyde, and the CAS registration number is [93-53-8], chemical structural formula is:
Black nightshade aldehyde is a kind of spices of preciousness, also is important industrial chemicals, is widely used in the industries such as spices, medicine, fuel and agricultural chemicals.During the industrial process of black nightshade aldehyde take methyl phenyl ketone and ethyl chloroacetate as raw material, by the Darzens method (refer to that aldehydes or ketones is at highly basic＜such as sodium amide, sodium alkoxide〉effect lower with the reaction of alpha-halogenated carboxylic acids ester, generation α, the reaction of beta epoxide acid esters.With discoverer's Bille August George Da Jin＜1867-1954〉name.Product α, the beta epoxide carboxylicesters is also referred to as " glycidic ester ", can obtain aldehyde and ketone through hydrolysis).Condensation is synthetic.Concrete synthetic method is that methyl phenyl ketone and ethyl chloroacetate make aminomethyl phenyl epoxy acrylate (methyl phenyl ethylglycidate) under the effect of highly basic, this ester through saponification, neutralize, be hydrolyzed into acid, should the acid thermal degradation obtain black nightshade aldehyde again.The method complicated operation, the finished product obtain by rectifying, and productive rate and product purity are not high.In order to seek more suitable synthetic route, many people are being engaged in the research of this respect.
The people such as Rivero (Rivero1.A.Org.Prep.Proced.Int., 1993,24,363) propose with the standby black nightshade aldehyde of 2-aminomethyl phenyl oxidation of ethanol legal system, although productive rate is higher, and severe reaction conditions, and also raw material is special, is unfavorable for suitability for industrialized production.Old Wan Zhi etc. (old ten thousand it, SCI, 1993,14,1265) utilize various Chelate rhodium complexes as catalyzer the vinylbenzene hydroformylation to be prepared black nightshade aldehyde, be a kind of new synthetic method, but cost are higher.(Guo Tingqiao, fine chemistry industry, 2001 such as Guo Tingqiao, 18,34) etc. take alpha-methyl styrene as raw material, Peracetic Acid is epoxidation reagent, prepare 2-benzyl ring Ethylene Oxide, re-isomerization makes black nightshade aldehyde, and it is few that this method has step, raw material is cheap to be easy to get, and cost is low, the productive rate advantages of higher, but Peracetic Acid has unstable, easily decomposing, be difficult for storing, is not a kind of desirable oxygenant.(the Liu Chengwei etc. such as Liu Chengwei, CN101134718A) this method is improved, take superoxide such as SPC-D as epoxidation reagent, in the presence of diacetyl oxide, solvent and phase-transfer catalyst, make 2-benzyl ring Ethylene Oxide through epoxidation reaction, then with the preparation 2-benzyl ring Ethylene Oxide in the presence of catalysts and solvents, obtain black nightshade aldehyde through isomerization reaction.Cost is low although the method has, reaction temperature and, the advantage such as reactions steps is few, used catalyzer in the technique, the reagent such as diacetyl oxide and oxygenant, the security of technique, to the friendly of environment, and process costs has restricted the industrialization use.(history is true, SCI, 2001,22,1352 for Shi Zhen etc.; CN101134718A) generate benzoglyoxaline alkane intermediate with benzoglioxaline salt and α-phenylethyl magnesium bromide addition, hydrolysis just can obtain black nightshade aldehyde under acidic conditions again, it is higher that this method has a productive rate, good product purity, the advantage such as easy and simple to handle, but this method raw material is difficult to obtain, and wants really to be applied to actual production, also needs to carry out a large amount of research work.
Summary of the invention
Goal of the invention: for overcoming defects, the invention provides that a kind of technological operation is simple, cost is low, improve product yield and purity processing method.
Technical scheme: a kind of preparation method of black nightshade aldehyde, adopt fractionation, the method comprises the steps:
1) preparation of 3-methyl-3-phenyl glycidyl acid esters:
Take methyl phenyl ketone and halogenated acetic acids ester as raw material, in the presence of alkali, through the Darzens reaction (refer to aldehydes or ketones highly basic (such as sodium amide, sodium alkoxide) effect lower with the reaction of alpha-halogenated carboxylic acids ester, generation α, the reaction of beta epoxide acid esters.With discoverer's Bille August George Da Jin (1867-1954) name).Condensation reaction makes 3-methyl-3-ethyl phenylglycidate, and wherein the halogenated acetic acids ester comprises chloro, the monobromo-acetic acid methyl esters, and ethyl ester, and the ester of other C1-C5 are wherein especially with the ethyl acetate best results of chloro; Described alkali includes but not limited to following alkali: sodium methylate, sodium ethylate, sodium isopropylate, sodium tert-butoxide, sodium amide; Described solvent is a kind of among dichloromethane a heatable brick bed, chloroform, toluene, the R1-ONa, and R1 is the normal chain alkyl that contains 2～5 carbon atoms in the formula, and reaction equation is:
2) preparation of 3-methyl-3-phenyl glycidyl hydrochlorate:
The 3-methyl of above-mentioned steps preparation-3-phenyl glycidyl acid esters is hydrolyzed in the aqueous solution of alkali and obtains 3-methyl-3-phenyl glycidyl hydrochlorate; Described alkali includes but not limited to sodium hydroxide, potassium hydroxide, lithium hydroxide; Reaction equation is:
3) preparation of black nightshade aldehyde crude product:
The 3-methyl of above-mentioned steps preparation-3-phenyl glycidyl hydrochlorate is acidified to pH=1-4, obtains black nightshade aldehyde through isomerization reaction in the presence of acid and solvent.Mineral acid or the organic acid of described acid for often having, as: hydrochloric acid, sulfuric acid, phosphoric acid, Glacial acetic acid, methylsulfonic acid etc.; Described solvent is water, ethyl acetate, a kind of in methylene dichloride, the toluene.Reaction equation is:
4) black nightshade aldehyde crude product refining:
Traditional method of refining black nightshade aldehyde is to utilize rectificating method, and this method power consumption is large, and the yield of the product that obtains is low, and the purity difference of product, what the present invention innovated utilizes chemically separated method at normal temperatures and pressures, by simple operation, high yield, high-quality acquisition black nightshade aldehyde.
Concrete method:
A) sulfonate of black nightshade aldehyde preparation
Black nightshade aldehyde crude product and the hydrosulphite of above-mentioned steps preparation are reacted in solvent, obtained solid sulfoacid salt through filtering, wash, the dry routine operation that waits has obtained sulfonate.Described hydrosulphite includes but not limited to sodium bisulfite, Potassium hydrogen sulfite, magnesium bisulfite. reaction equation is:
B) sulfonate of black nightshade aldehyde is free
React in the sulfonate of the black nightshade aldehyde of above-mentioned steps preparation and the buck, obtained organic layer through separating, washing, the routine operation such as dry has obtained high-quality black nightshade aldehyde.Described alkali includes but not limited to sodium hydroxide, potassium hydroxide, lithium hydroxide.Reaction equation is:
Useful effect: of the present invention in the process of preparation black nightshade aldehyde, utilization is to the control of acidulated condition, make the normal temperature and pressure decarboxylation in acidization of 3-methyl-3-phenyl glycidyl hydrochlorate replace high temperature decarboxylation in the traditional technology, isomerization obtains black nightshade aldehyde, and this method has no report at the document of preparation black nightshade aldehyde; The acid of adopting can make mineral acid or organic acid, certainly the factor of considering cost and effect, preferably hydrochloric acid and sulfuric acid.PH is controlled at 1-4, preferred pH=1.
Compare present traditional method, the present invention utilizes the control to acidulated condition in isomerization (step 3), make the normal temperature and pressure decarboxylation in acidization of 3-methyl-3-phenyl glycidyl hydrochlorate replace high temperature decarboxylation in the traditional technology, isomerization obtains black nightshade aldehyde.In the refined product process, the Methods For Purification product that utilizes black nightshade aldehyde and hydrosulphite to generate solid sulfoacid salt replaces traditional purifying with rectificating method, processing method raw material of the present invention obtains simple, reactions steps is easy, the technique environmental protection, product purity and productive rate are higher, and cost is lower, be easy to realize industry.
Secondly utilize black nightshade aldehyde and the hydrosulphite of innovation generate the Methods For Purification product of solid sulfoacid salt, and this is that present document prepares the novel method that the purification black nightshade aldehyde has no report.And traditional method of purification is to purify with rectificating method, because the raw material of black nightshade aldehyde and reaction, and the byproduct similar that produces in the reaction, boiling point is very approaching, so the purity difference of rectification method refined product, yield is low, and power consumption is large.The hydrosulphite that novel method adopts can be the metallic salts such as sodium salt, sylvite, lithium salts, magnesium salts, the factor of certain considering cost and effect, particular certain cancers and sylvite; In salification process, it is abundant that excessive hydrosulphite is conducive to salify, the factor of certain considering cost and effect, and preferred crude product aldehyde and hydrosulphite mol ratio are 1: 1-1: 3.The present invention becomes the method for solid sulfoacid salt refined product to put forward new approach for the purification of other similar aldehyde with black nightshade aldehyde with hydrosulphite.
Embodiment
Below in conjunction with specific examples the technology of the present invention is described further, but protection scope of the present invention is not limited to following example.
Embodiment 1:
Take by weighing the 5000g20% sodium methylate and join in the 10L reaction flask, the control temperature is down to 20 ℃ with in the 1200g methyl phenyl ketone adding 10L reaction flask, and the 1.5Kg methyl chloroacetate is slowly dripped, and after 1h dropwises, stirs 2h, and censorship is surveyed, and the result shows that reaction is substantially complete.Remove ethanol, rectification under vacuum obtains the 3-methyl of content 〉=98%-3-phenyl glycidyl acid methyl esters, and productive rate is 70-80%.
In the there-necked flask that thermometer, stirring, 10L are housed, the above-mentioned 3-methyl that makes of adding 1kg-3-phenyl glycidyl acid methyl esters, 20% aqueous sodium hydroxide solution 1L, stirring reaction, the chromatogram tracking reaction, until glycerate transforms fully, the reaction times approximately filtered and obtains 3-methyl-3-phenyl glycidyl sodium salt in 4 hours, and productive rate is 90-100%.
The above-mentioned 3-methyl that makes of adding 1000g-3-phenyl glycidyl sodium salt in the there-necked flask that thermometer, stirring, 10L are housed, the 1L pure water under agitation drips concentrated hydrochloric acid, control pH=1, dropwise rear stirring 1 hour, standing demix is collected the organic layer on upper strata.
Stir in the lower saturated sodium sulfite solution with above-mentioned organic layer adding equimolar amount, a large amount of solids are separated out, and filter, and filter cake washes with water, drying, and oven dry obtains white solid, and productive rate is 90-95%.
The above-mentioned black nightshade aldehyde sulfonate sodium that makes that in the there-necked flask that thermometer, stirring, 10L are housed, adds 1kg, stir in the buck of the equimolar amount that joins down 1L, stirred 1 hour, standing demix is collected the organic layer on upper strata, drying, obtain the product black nightshade aldehyde, product is colourless liquid, productive rate 90-95%, and nuclear-magnetism, mass spectrum, infrared and the ultimate analysis data are consistent with bibliographical information.
Embodiment 2:
Take by weighing the 3000g20% sodium ethylate and join in the 10L reaction flask, the control temperature is down to 10 ℃ with in the 1500g methyl phenyl ketone adding 10L reaction flask, and the 1.5Kg ethyl chloroacetate is slowly dripped, and after 1h dropwises, stirs 2h, send GC to detect, and the result shows that reaction is substantially complete.Remove ethanol, rectification under vacuum obtains the 3-methyl of content 〉=98%-3-ethyl phenylglycidate, and productive rate is 70-80%.
In the there-necked flask that thermometer, stirring, 10L are housed, the above-mentioned 3-methyl that makes of adding 1kg-3-ethyl phenylglycidate, 20% aqueous sodium hydroxide solution 1L, stirring reaction, the chromatogram tracking reaction, until ethyl glycerate transforms fully, the reaction times approximately filtered and obtains 3-methyl-3-phenyl glycidyl sodium salt in 10 hours, and productive rate is 90-100%.
The above-mentioned 3-methyl that makes of adding 1kg-3-phenyl glycidyl sodium salt in the there-necked flask that thermometer, stirring, 10L are housed, the 1L pure water under agitation drips concentrated hydrochloric acid, control pH=1, dropwise rear stirring 1 lab scale, standing demix is collected the organic layer on upper strata.
Stir in the lower saturated sodium sulfite solution with above-mentioned organic layer adding equimolar amount, a large amount of solids are separated out, and filter, and filter cake washes with water, drying, and oven dry obtains white solid, and productive rate is 90-95%.
The above-mentioned black nightshade aldehyde sulfonate sodium that makes that in the there-necked flask that thermometer, stirring, 10L are housed, adds 1kg, stir in the buck of the equimolar amount that joins down 1L, stirred 1 hour, standing demix is collected the organic layer on upper strata, drying, obtain the product black nightshade aldehyde, product is colourless liquid, productive rate 90-95%, and nuclear-magnetism, mass spectrum, infrared and the ultimate analysis data are consistent with bibliographical information.
Embodiment 3:
Take by weighing the 3600g20% sodium isopropylate and join in the 10L reaction flask, the control temperature is down to 40 ℃ with in the 1200g methyl phenyl ketone adding 10L reaction flask, and the 2.4Kg ethyl chloroacetate is slowly dripped, and after 1h dropwises, stirs 5h, and censorship is surveyed, and the result shows that reaction is substantially complete.Remove ethanol, decompression (1mmHg) rectifying obtains the 3-methyl of content 〉=98%-3-ethyl phenylglycidate, and productive rate is 70-80%.
In the there-necked flask that thermometer, stirring, 10L are housed, the above-mentioned 3-methyl that makes of adding 1kg-3-ethyl phenylglycidate, 20% aqueous sodium hydroxide solution 1L, stirring reaction, the chromatogram tracking reaction, until ethyl glycerate transforms fully, the reaction times approximately filtered and obtains 3-methyl-3-phenyl glycidyl sodium salt in 24 hours, and productive rate is 90-100%.
The above-mentioned 3-methyl that makes of adding 1kg-3-phenyl glycidyl sodium salt in the there-necked flask that thermometer, stirring, 10L are housed, the 1L pure water under agitation drips concentrated hydrochloric acid, control pH=2, dropwise rear stirring 1 lab scale, standing demix is collected the organic layer on upper strata.
Stir in the lower saturated bisulfite potassium solution with above-mentioned organic layer adding equimolar amount, a large amount of solids are separated out, and filter, and filter cake washes with water, drying, and oven dry obtains white solid, and productive rate is 90-95%.
The above-mentioned black nightshade aldehyde sulfonic acid potassium salt that makes that in the there-necked flask that thermometer, stirring, 10L are housed, adds 1kg, stir in the buck of the equimolar amount that joins down 1L, stirred 1 hour, standing demix is collected the organic layer on upper strata, drying, obtain the product black nightshade aldehyde, product is colourless liquid, productive rate 90-95%, and nuclear-magnetism, mass spectrum, infrared and the ultimate analysis data are consistent with bibliographical information.
Embodiment 4:
Take by weighing the 4000g20% sodium tert-butoxide and join in the 10L reaction flask, the control temperature is down to 50 ℃ with in the 1500g methyl phenyl ketone adding 10L reaction flask, and the 2Kg ethyl chloroacetate is slowly dripped, and after 1h dropwises, stirs 5h, and censorship is surveyed, and the result shows that reaction is substantially complete.Remove ethanol, decompression (1mmHg) rectifying obtains the 3-methyl of content 〉=98%-3-ethyl phenylglycidate, and productive rate is 72-82%.
In the there-necked flask that thermometer, stirring, 10L are housed, the above-mentioned 3-methyl that makes of adding 1kg-3-ethyl phenylglycidate, 20% potassium hydroxide aqueous solution 1L, stirring reaction, the chromatogram tracking reaction, until ethyl glycerate transforms fully, the reaction times approximately filtered and obtains 3-methyl-3-phenyl glycidyl sodium salt in 24 hours, and productive rate is 87-95%.
The above-mentioned 3-methyl that makes of adding 1kg-3-phenyl glycidyl sodium salt in the there-necked flask that thermometer, stirring, 10L are housed, the 1L pure water under agitation drips concentrated hydrochloric acid, control pH=4, dropwise rear stirring 1 lab scale, standing demix is collected the organic layer on upper strata.
Stir in the lower saturated bisulfite potassium solution with above-mentioned organic layer adding equimolar amount, a large amount of solids are separated out, and filter, and filter cake washes with water, drying, and oven dry obtains white solid, and productive rate is 88-92%.
The above-mentioned black nightshade aldehyde sulfonic acid potassium salt that makes that in the there-necked flask that thermometer, stirring, 10L are housed, adds 1kg, stir in the buck of the equimolar amount that joins down 1L, stirred 1 hour, standing demix is collected the organic layer on upper strata, drying, obtain the product black nightshade aldehyde, product is colourless liquid, productive rate 82.5-88%, and nuclear-magnetism, mass spectrum, infrared and the ultimate analysis data are consistent with bibliographical information.
Claims (6)
1. the preparation method of a black nightshade aldehyde adopts fractionation, and the method comprises the steps:
(1), the preparation of 3-methyl-3-phenyl glycidyl acid esters:
Take methyl phenyl ketone and halogenated acetic acids ester as raw material, in the presence of alkali, under 10-50 ℃, make 3-methyl-3-ethyl phenylglycidate through 1-24 hour condensation reaction, the mol ratio of described alkali and methyl phenyl ketone is 1.0-3.0: 1; The mol ratio of described halogen ester and methyl phenyl ketone is 1.0-2.0: 1;
(2), the preparation of 3-methyl-3-phenyl glycidyl hydrochlorate:
The 3-methyl of above-mentioned steps preparation-3-phenyl glycidyl acid esters is hydrolyzed in the aqueous solution of alkali, under 0-50 ℃ of temperature, pH is between 1-4, through reaction in 1-24 hour, obtain 3-methyl-3-phenyl glycidyl hydrochlorate, described alkali and 3-methyl-3-phenyl glycidyl acid esters mol ratio is 1.0-3.0: 1;
(3), the preparation of black nightshade aldehyde crude product:
The 3-methyl of above-mentioned steps preparation-3-phenyl glycidyl hydrochlorate is acidified to pH=1-4, obtains the black nightshade aldehyde crude product through isomerization reaction in the presence of acid and solvent; Mineral acid or the organic acid of described acid for often having; Described solvent is water, ethyl acetate, a kind of in methylene dichloride, the toluene; Stating the 3-methyl of preparation-3-phenyl glycidyl acid esters is hydrolyzed in the aqueous solution of alkali and obtains 3-methyl-3-phenyl glycidyl hydrochlorate; Described alkali is sodium hydroxide, hydroxide clock, a kind of in the lithium hydroxide;
(4), the preparation of black nightshade aldehyde sulfonate:
In solvent, under 0-50 ℃ of temperature, the reaction through 1-24 hour has obtained solid sulfoacid salt, through filtering, washs with the black nightshade aldehyde crude product of above-mentioned steps preparation and hydrosulphite, and drying has obtained black nightshade aldehyde sulfonate;
(5), the preparation of black nightshade aldehyde sterling:
In the black nightshade aldehyde sulfonate and alkali with the above-mentioned steps preparation, under 0-50 ℃ of temperature, the reaction through 1-24 hour obtains organic layer, and is dry through separating, washing, and obtained the target compound black nightshade aldehyde.
2. the preparation method of black nightshade aldehyde according to claim 1, it is characterized in that: the alkali in the described step (1) is sodium methylate, sodium ethylate, sodium isopropylate, sodium tert-butoxide, a kind of in the sodium amide; Halogen ester described in the step (1) is ethyl chloroacetate, a kind of in the methyl chloroacetate; Described solvent is a kind of in dichloromethane a heatable brick bed, chloroform, the toluene organic solvent.
3. the preparation method of black nightshade aldehyde according to claim 1, it is characterized in that: the alkali in the described step (2) is sodium hydroxide, a kind of in the potassium hydroxide.
4. the preparation method of black nightshade aldehyde according to claim 1, it is characterized in that: the acid in the described step (2) is hydrochloric acid, a kind of in the sulfuric acid.
5. the preparation method of black nightshade aldehyde according to claim 1 is characterized in that: the hydrosulphite in the described step (4) is a kind of in sodium bisulfite, the Potassium hydrogen sulfite.
6. the preparation method of black nightshade aldehyde according to claim 1, it is characterized in that: 9, the preparation method of black nightshade aldehyde according to claim 1 is characterized in that: the alkali in the described step (5) is a kind of in sodium hydroxide, the potassium hydroxide.
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| CN106831408A (en) * | 2015-12-03 | 2017-06-13 | 江苏国泰超威新材料有限公司 | A kind of 2,8- dimethyl azelaic acid, its synthetic method and application |
| CN111320540A (en) * | 2020-02-20 | 2020-06-23 | 东莞波顿香料有限公司 | Preparation method of cucumis melo aldehyde, cucumis melo aldehyde and application |
| CN114315927A (en) * | 2022-01-20 | 2022-04-12 | 东莞波顿香料有限公司 | Berry aroma compound, preparation method thereof and strawberry aroma type essence |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106831408A (en) * | 2015-12-03 | 2017-06-13 | 江苏国泰超威新材料有限公司 | A kind of 2,8- dimethyl azelaic acid, its synthetic method and application |
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| CN111320540A (en) * | 2020-02-20 | 2020-06-23 | 东莞波顿香料有限公司 | Preparation method of cucumis melo aldehyde, cucumis melo aldehyde and application |
| CN114315927A (en) * | 2022-01-20 | 2022-04-12 | 东莞波顿香料有限公司 | Berry aroma compound, preparation method thereof and strawberry aroma type essence |
| CN114315927B (en) * | 2022-01-20 | 2023-11-17 | 东莞波顿香料有限公司 | Berry aroma compound, preparation method thereof and strawberry aroma essence |
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