CN101289375A - Process for preparing alpha-methyl p-tert-butylbenylpropyl aldehyde - Google Patents
Process for preparing alpha-methyl p-tert-butylbenylpropyl aldehyde Download PDFInfo
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- CN101289375A CN101289375A CNA200810038650XA CN200810038650A CN101289375A CN 101289375 A CN101289375 A CN 101289375A CN A200810038650X A CNA200810038650X A CN A200810038650XA CN 200810038650 A CN200810038650 A CN 200810038650A CN 101289375 A CN101289375 A CN 101289375A
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- tert
- jiduishudingjibenbingquan
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- butyl
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- 238000004519 manufacturing process Methods 0.000 title description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 24
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 claims abstract description 21
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 230000035484 reaction time Effects 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 35
- 239000012074 organic phase Substances 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 229960003328 benzoyl peroxide Drugs 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 8
- 230000006837 decompression Effects 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 6
- 238000003810 ethyl acetate extraction Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000009833 condensation Methods 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 abstract description 2
- 238000006136 alcoholysis reaction Methods 0.000 abstract description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 5
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- OTXINXDGSUFPNU-UHFFFAOYSA-N 4-tert-butylbenzaldehyde Chemical compound CC(C)(C)C1=CC=C(C=O)C=C1 OTXINXDGSUFPNU-UHFFFAOYSA-N 0.000 description 2
- 101100007699 Emericella nidulans (strain FGSC A4 / ATCC 38163 / CBS 112.46 / NRRL 194 / M139) creB gene Proteins 0.000 description 2
- 101100402271 Haemophilus influenzae (strain ATCC 51907 / DSM 11121 / KW20 / Rd) molB gene Proteins 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000007265 chloromethylation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- OSOLHARQJQEMBZ-UHFFFAOYSA-N 1-chloropentylbenzene Chemical group CCCCC(Cl)C1=CC=CC=C1 OSOLHARQJQEMBZ-UHFFFAOYSA-N 0.000 description 1
- WAXIFMGAKWIFDQ-UHFFFAOYSA-N 1-tert-butyl-4-(chloromethyl)benzene Chemical compound CC(C)(C)C1=CC=C(CCl)C=C1 WAXIFMGAKWIFDQ-UHFFFAOYSA-N 0.000 description 1
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000755716 Convallaria Species 0.000 description 1
- 235000009046 Convallaria majalis Nutrition 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 238000006007 Sommelet synthesis reaction Methods 0.000 description 1
- 238000005874 Vilsmeier-Haack formylation reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- QQVDYSUDFZZPSU-UHFFFAOYSA-M chloromethylidene(dimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)=CCl QQVDYSUDFZZPSU-UHFFFAOYSA-M 0.000 description 1
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical group C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229940031815 mycocide Drugs 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a novel preparation method of alpha-methyl p-tert-butyl benzene propionaldehyde. The p-tert-butyl benzene is used as the raw material to react with acetic anhydride condensation compound of methacrolein under the existence of the catalyst of SnCl4 and then 3-(p-tert-butyl phenyl)-2-methyl-1- acetoxy-2- propylene is produced. The compound does not need to be separated and the product of the alpha-methyl p-tert-butyl benzene propionaldehyde is produced by alkaline alcoholysis at indoor temperature directly. The reaction conditions are tender; the reaction time is short and the product yield reaches above 56 percent. The preparation method has the advantages of having low cost and high yield and greatly reducing the quantities of three wastes.
Description
Technical field:
The present invention relates to the synthetic perfume field, relate in particular to a kind of new method for preparing α-Jia Jiduishudingjibenbingquan.
Background technology:
α-Jia Jiduishudingjibenbingquan has another name called Ling Lanquan, is a kind of spices of synthetic.Has the lily of the valley, flower of Greenish Lily fragrance.Be characterized in that fragrance is soft pure and fresh, lasting is lasting.α-Jia Jiduishudingjibenbingquan is stable to alkali, and is little to skin irritation, be widely used in the production of perfumed soap and bouquet type composition, and be a kind of large-tonnage perfume material kind.Simultaneously, Ling Lanquan also is widely used and does mycocide.
The classical synthetic method of α-Jia Jiduishudingjibenbingquan (N.H. Bo Latusi, " flavor chemistry ", light industry press, P222,1984) be to be raw material, by tert.-butylbenzene, in the presence of hydrogen chloride gas, carry out chloromethylation with formaldehyde, concentrated hydrochloric acid, make 4 tert butylbenzyl chloride.Carry out Sommelet prepared in reaction p-t-Butylbenzaldehyde by tertiary butyl benzyl chloride and urotropine then.After p-t-Butylbenzaldehyde and the condensation of propionic aldehyde alkalescence, make 3-(to tert-butyl-phenyl)-2-methyl isophthalic acid-propenal, carry out selective hydration again, make α-Jia Jiduishudingjibenbingquan.The synthetic need through four-step reaction, total recovery is lower than 27%.In addition, this technology chloromethylation, Sommelet reaction and propionic aldehyde alkalescence condensation three-step reaction all have the more three wastes to produce.
Reaction formula:
Since the classical synthetic method of α-Jia Jiduishudingjibenbingquan on the yield, the three wastes are not fully up to expectations on producing.For many years, be that the essence and flavoring agent company of representative has researched and developed some new synthetic methods with Switzerland Qi Huadun company.1961, Scriabine etc. were at Bull.Soc.Chim.Fr, and 1194 (1961) have delivered employing at a large amount of TiCl
4And BF
3-Et
2The O catalyzer makes the direct and methacrylic aldehyde reaction of tert.-butylbenzene, generates the method that yield is lower than 10% α-Jia Jiduishudingjibenbingquan.Because yield is low excessively, hydrolysis TiCl
4The generation quantity of three wastes is big, and this method is industrial nonsensical.
Nineteen eighty-two, Switzerland Qi Huadun company has delivered DE 2,851, and 024 patent is by p-tert.-butyl acetophenone and DMF, POCl
3The Vilsmeier reagent react that forms, make 3-(to tert-butyl-phenyl)-3-chloro-methacrolein with 46% yield, hydrogenation is sloughed chlorine under Pd/C catalysis again, and double-bond hydrogenation becomes α-Jia Jiduishudingjibenbingquan simultaneously, hydrogenation yield 76%, total recovery 35%.This method yield is still low, and the Vilsmeier reaction has the more three wastes to produce.
Summary of the invention:
The technical problem to be solved in the present invention is to provide a kind of new method for preparing α-Jia Jiduishudingjibenbingquan.The employing tert.-butylbenzene is a raw material, directly and the acid anhydrides condenses (B) of Methylacrylaldehyde at catalyzer tin tetrachloride (SnCl
4) there is reaction down, generate 3-(to tert-butyl-phenyl)-2-methyl isophthalic acid-acetoxyl group-2-propylene intermediate (A).This intermediate need not separate, and directly in the alcoholysis of methyl alcohol neutral and alkali, high yield is made the α-Jia Jiduishudingjibenbingquan product after sloughing excessive tert.-butylbenzene.This method has solved the shortcoming that reactions steps is long in the classical way, yield is low, has also reduced the generation of the three wastes significantly.
A kind of new method for preparing α-Jia Jiduishudingjibenbingquan provided by the invention comprises the steps:
Reaction formula:
(i)
(ii)
The condenses (B) of Methylacrylaldehyde in the reaction formula (i) and acetic anhydride is dissolved in the tert.-butylbenzene; At SnCl
4Under catalyzer exists, be solvent with the tert.-butylbenzene, the condenses of tert.-butylbenzene, Methylacrylaldehyde and acetic anhydride and catalyst reaction 1.5-4 hour generation 3-(to tert-butyl-phenyl)-2-methyl isophthalic acid-acetoxyl group-2-propylene intermediate (A); Recommend every mole of B to dissolve with tert.-butylbenzene 120-240g.
After reaction is finished, will react the feed liquid hydrochloric acid hydrolysis, and wash then, water is incorporated organic phase into after with ethyl acetate extraction.Ethyl acetate and excessive tert.-butylbenzene are sloughed in organic phase drying, decompression, and residue (A) is directly used in next step reaction.
(A) is dissolved in the methyl alcohol with residue, stirs to add anhydrous Na down
2CO
3Under room temperature, react.
Splash into acetic acid after the reaction and be neutralized to neutrality (pH=7), methyl alcohol is sloughed in decompression, adds acetic acid ethyl dissolution, washing.After the drying, ethyl acetate is sloughed in decompression, gets the α-Jia Jiduishudingjibenbingquan crude product, content 78-86% (GC).Obtain α-Jia Jiduishudingjibenbingquan content＞90% highly finished product after the crude product rectifying.
Tert.-butylbenzene in the step (1) uses as reaction solvent again both as reaction mass.
Catalyst S nCl
4Consumption be 0.1-0.8mol/molB, preferred consumption is 0.4-0.6mol/molB.Work as SnCl
4Reaction not exclusively caused cost to rise when consumption was very few when consumption is too much.
Every 0.4-0.6mol SnCl
4Catalyzer need dissolve with the 650-770g tert.-butylbenzene, and heat release in the time of making dropwise reaction like this, reacting balance carry out, and are easy to control reaction temperature.
The dropping time is generally 0.5-5.0hr.The preferred dropping time is 1.5-2.5hr.
Temperature of reaction can be carried out in-50～50 ℃, and preferable reaction temperature is-30～-10 ℃.
After being added dropwise to complete, can under-10～0 ℃ of temperature, continue reaction 1-1.5hr, make to react completely.
After reaction is finished, the reaction solution of every mole of B with 60-90ml 6N equivalent hydrochloric acid 0 ℃ of left and right sides hydrolysis, tell organic phase after, use 200ml * 2 washings again.Water is incorporated organic phase into after with 100ml * 2 ethyl acetate extractions.The anhydrous MgSO of organic phase
4Drying carefully with the solid filter to the greatest extent, obtains clarifying organic phase.
When ethyl acetate and excessive tert.-butylbenzene, should adopt the method for underpressure distillation in steam removing organic phase, temperature is lower than 50 ℃ and carries out in making.Too high distillation temperature can cause the feed liquid decomposition, produces by product.When distillation, also can add the stopper about 0.1-0.2% slightly, as Resorcinol.
Residual material (A) is used dissolve with methanol.Every 100g material (A) is used 50-500g methyl alcohol, and preferable amount is a 100-200g methyl alcohol.
The anhydrous Na that adds in the methyl alcohol A solution after the dissolving
2CO
3Solid, every 100g material A Na
2CO
312-16g.Very few Na
2CO
3Reaction not exclusively can not make reaction faster in the time of too much, and yield is improved, and has also strengthened the acetic acid amount of neutralization usefulness.
(22-25 ℃), reaction times 20-30hr are at room temperature carried out in reaction.
Splash into the acetic acid neutralization after reaction is finished, the acetic acid amount of splashing into is as the criterion to reach material liquid pH=7.
Answer decompression operation during the distillation separating methanol, temperature is no more than 40 ℃ in making.The too high meeting of temperature causes side reaction.
Methyl alcohol steams to the greatest extent, and the back adds ethyl acetate.The every 100g A of add-on adds the 80-120ml ethyl acetate and gets final product.After using 60ml * 3 washings then, tell organic phase, the anhydrous MgSO of organic phase
4Drying carefully leaches clear liquid.
Organic phase leaches clear liquid under reduced pressure, and interior temperature is no more than 45 ℃ and boils off ethyl acetate, promptly obtains the α-Jia Jiduishudingjibenbingquan crude product, GC content 78-85%.Crude product steams 126-127 ℃ of fraction, the highly finished product of content＞90.0% under 6mmHg.
Embodiment
Following examples help to understand the present invention, but are not limited to content of the present invention.
Embodiment 1: the preparation of compd A
In the 250ml reaction flask, add compd B 25g (0.145mol), tert.-butylbenzene 25g stirs down, is cooled to below-15 ℃ with ice/methanol bath.
SnCl
4(17.8g 0.068mol) is dissolved in the 100g tert.-butylbenzene 8ml, under the vigorous stirring, splashes into a bottle internal reaction in-15～-10 ℃.1.5hr add, again in-5～0 ℃ of reaction 1hr.
Add the normal hydrochloric acid hydrolysis of 12ml 6N, tell organic phase.After 60ml * 2 washings.Water is integrated with organic phase, anhydrous MgSO with 15ml * 2 ethyl acetate extractions
4After the drying, leach clear liquid with three metafiltration paper.
The organic phase clear liquid is at pump vacuum, under 45 ℃ of the interior temperature, boils off ethyl acetate, boils off tert.-butylbenzene again under 5mmHg.Residue (A) nearly weighs 35-37g, can be directly used in next step reaction.
Embodiment 2: the preparation of α-Jia Jiduishudingjibenbingquan
Above-mentioned residue (A) is complete with the 50ml dissolve with methanol, add the 5g anhydrous Na
2CO
3, stir room temperature reaction 26hr down.Drip acetic acid and make pH=7.Pressure reducing and steaming methyl alcohol adds ethyl acetate 50ml, after 30ml * 2 washings, tells organic phase.
The anhydrous MgSO of organic phase
4After the drying, carefully leach clear liquid.The pressure reducing and steaming ethyl acetate gets 20-21g crude product α-Jia Jiduishudingjibenbingquan.GC content 78-82%, yield 56% (in B).
126-128 ℃/6mmHg fraction is collected in crude product decompression rectifying down, for content greater than 90.0% refining α-Jia Jiduishudingjibenbingquan.
GC-MS analyzes: m/z 204 (M
+22) 189 (100) 147 (33.6) 131 (24.3) 117 (16.2) 91 (13.9)
1H?NMR(CDCl
3，500MHz)δ/ppm：1.12(d，3H，CH
2CHCH
3CHO)1.33(s，9H，C(CH
3)
3)2.58-3.09(m，2H，CH
2CHCH
3CHO)2.69(dd，1H，CH
2CHCH
3CHO)7.13-7.34(m，4H，C
6H
4)9.74(s，1H，CHO)
Claims (8)
1, a kind of method for preparing α-Jia Jiduishudingjibenbingquan is characterized in that obtaining by following (1)～(3) step:
(1) at SnCl
4The existence of catalyzer is a solvent with the tert.-butylbenzene down and under-50～50 ℃ of temperature, the condenses B of tert.-butylbenzene, Methylacrylaldehyde and acetic anhydride and catalyst reaction 1.5-4 hour generation 3-(to tert-butyl-phenyl)-2-methyl isophthalic acid-acetoxyl group-2-propylene A; The condenses of described Methylacrylaldehyde and acetic anhydride and the mol ratio of catalyzer are 1: 0.1-0.8;
(2) with the product reaction solution hydrochloric acid hydrolysis of above-mentioned (1), washing then, water is incorporated organic phase into after with ethyl acetate extraction; Ethyl acetate is sloughed in organic phase drying, decompression and excessive tert.-butylbenzene obtains 3-(to tert-butyl-phenyl)-2-methyl isophthalic acid-acetoxyl group-2-propylene;
(3), 3-(to the tert-butyl-phenyl)-2-methyl isophthalic acid-acetoxyl group-2-propylene in (2) is dissolved in the methyl alcohol, stirs adding anhydrous Na down
2CO
3Under room temperature, react reaction times 20-30 hour; Splash into acetic acid after the reaction and be neutralized to neutrality, methyl alcohol is sloughed in decompression, adds acetic acid ethyl dissolution, washing; After the drying, ethyl acetate is sloughed in decompression, gets the α-Jia Jiduishudingjibenbingquan crude product; Or obtain the α-Jia Jiduishudingjibenbingquan highly finished product after the crude product rectifying;
The structural formula of the condenses B of described 3-(to tert-butyl-phenyl)-2-methyl isophthalic acid-acetoxyl group-2-propylene A and Methylacrylaldehyde and acetic anhydride is as follows:
2, a kind of method for preparing α-Jia Jiduishudingjibenbingquan as claimed in claim 1 is characterized in that preferred Methylacrylaldehyde described in the step (1) and acetic anhydride condenses are 1 to the mol ratio of catalyzer: 0.4-0.6.
3, a kind of method for preparing α-Jia Jiduishudingjibenbingquan as claimed in claim 1, the condenses B that it is characterized in that every mole of Methylacrylaldehyde described in the step (1) and acetic anhydride is with tert.-butylbenzene 120-240g dissolving.
4, a kind of method for preparing α-Jia Jiduishudingjibenbingquan as claimed in claim 1 is characterized in that the SnCl of the every 0.4-0.6 mole of catalyzer described in the step (1)
4Catalyzer need dissolve with the 650-770g tert.-butylbenzene.
5, a kind of method for preparing α-Jia Jiduishudingjibenbingquan as claimed in claim 1 is characterized in that the reaction described in the step (1) ,-30～-10 ℃ of reactions 1.5-2.5 hour, and then continues reaction 1-1.5 hour under-10～0 ℃ of temperature.
6, a kind of method for preparing α-Jia Jiduishudingjibenbingquan as claimed in claim 1 is characterized in that the hydrochloric acid hydrolysis described in the step (2), and the reaction solution of the product of every mole (1) uses 60-90ml 6N equivalent hydrochloric acid 0 ℃ of left and right sides hydrolysis, after telling organic phase, use 200ml * 2 washings again; Water is incorporated organic phase into after with 100ml * 2 ethyl acetate extractions; The anhydrous MgSO of organic phase
4Drying with the solid filter to the greatest extent, obtains clarifying organic phase.
7, a kind of method for preparing α-Jia Jiduishudingjibenbingquan as claimed in claim, 3-(to the tert-butyl-phenyl)-2-methyl isophthalic acid-acetoxyl group-2-propylene that it is characterized in that (2) described in the step (3) is dissolved in methyl alcohol, use dissolve with methanol, every 100g 3-(to tert-butyl-phenyl)-2-methyl isophthalic acid-acetoxyl group-2-propylene 50-500g dissolve with methanol.
8, a kind of method for preparing α-Jia Jiduishudingjibenbingquan as claimed in claim as claimed in claim 1, it is characterized in that after 3-(to tert-butyl-phenyl)-2-methyl isophthalic acid-acetoxyl group-the 2-propylene is dissolved in methyl alcohol of (2) described in the step (3), every 100g 3-(to tert-butyl-phenyl)-2-methyl isophthalic acid-acetoxyl group-2-propylene adds Na
2CO
3The 12-16g reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200810038650XA CN101289375A (en) | 2008-06-06 | 2008-06-06 | Process for preparing alpha-methyl p-tert-butylbenylpropyl aldehyde |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200810038650XA CN101289375A (en) | 2008-06-06 | 2008-06-06 | Process for preparing alpha-methyl p-tert-butylbenylpropyl aldehyde |
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| Publication Number | Publication Date |
|---|---|
| CN101289375A true CN101289375A (en) | 2008-10-22 |
Family
ID=40033852
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| Application Number | Title | Priority Date | Filing Date |
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| CNA200810038650XA Pending CN101289375A (en) | 2008-06-06 | 2008-06-06 | Process for preparing alpha-methyl p-tert-butylbenylpropyl aldehyde |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106699534A (en) * | 2016-11-15 | 2017-05-24 | 山东新和成药业有限公司 | Preparation method of lily aldehyde |
| CN112552153A (en) * | 2020-12-25 | 2021-03-26 | 厦门中坤化学有限公司 | Synthesis method of tert-butyl phenylpropyl aldehyde |
-
2008
- 2008-06-06 CN CNA200810038650XA patent/CN101289375A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106699534A (en) * | 2016-11-15 | 2017-05-24 | 山东新和成药业有限公司 | Preparation method of lily aldehyde |
| CN106699534B (en) * | 2016-11-15 | 2019-07-23 | 山东新和成药业有限公司 | A kind of preparation method of lilial |
| CN112552153A (en) * | 2020-12-25 | 2021-03-26 | 厦门中坤化学有限公司 | Synthesis method of tert-butyl phenylpropyl aldehyde |
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