CN1031131C - Preparation method of 6-methoxy naphthaldehyde - Google Patents
Preparation method of 6-methoxy naphthaldehyde Download PDFInfo
- Publication number
- CN1031131C CN1031131C CN 92108127 CN92108127A CN1031131C CN 1031131 C CN1031131 C CN 1031131C CN 92108127 CN92108127 CN 92108127 CN 92108127 A CN92108127 A CN 92108127A CN 1031131 C CN1031131 C CN 1031131C
- Authority
- CN
- China
- Prior art keywords
- methoxynaphthalene
- reaction
- methyl
- mole ratio
- hydrazine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- RQSRLHYBIGCTIS-UHFFFAOYSA-N 6-methoxynaphthalene-1-carbaldehyde Chemical compound O=CC1=CC=CC2=CC(OC)=CC=C21 RQSRLHYBIGCTIS-UHFFFAOYSA-N 0.000 title abstract 2
- 238000002360 preparation method Methods 0.000 title description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- LUZDYPLAQQGJEA-UHFFFAOYSA-N 2-Methoxynaphthalene Chemical compound C1=CC=CC2=CC(OC)=CC=C21 LUZDYPLAQQGJEA-UHFFFAOYSA-N 0.000 claims description 11
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 230000032050 esterification Effects 0.000 claims description 9
- 238000005886 esterification reaction Methods 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- 229940072033 potash Drugs 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 9
- 235000015320 potassium carbonate Nutrition 0.000 claims description 9
- BYGOPQKDHGXNCD-UHFFFAOYSA-N tripotassium;iron(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] BYGOPQKDHGXNCD-UHFFFAOYSA-N 0.000 claims description 9
- DERLQZITWLHADX-UHFFFAOYSA-N C(=O)NN.COC=1C=C2C=CC=CC2=CC1 Chemical compound C(=O)NN.COC=1C=C2C=CC=CC2=CC1 DERLQZITWLHADX-UHFFFAOYSA-N 0.000 claims description 8
- MZHNJQMTEJGQLR-UHFFFAOYSA-N C=O.COC=1C=C2C=CC=CC2=CC1 Chemical compound C=O.COC=1C=C2C=CC=CC2=CC1 MZHNJQMTEJGQLR-UHFFFAOYSA-N 0.000 claims description 8
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- UXVWRCXRYPZJBN-UHFFFAOYSA-N C(=O)O.COC=1C=C2C=CC=CC2=CC1 Chemical compound C(=O)O.COC=1C=C2C=CC=CC2=CC1 UXVWRCXRYPZJBN-UHFFFAOYSA-N 0.000 claims description 4
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- JCJUKCIXTRWAQY-UHFFFAOYSA-N 6-hydroxynaphthalene-1-carboxylic acid Chemical compound OC1=CC=C2C(C(=O)O)=CC=CC2=C1 JCJUKCIXTRWAQY-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical group CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- XZBIXDPGRMLSTC-UHFFFAOYSA-N formohydrazide Chemical compound NNC=O XZBIXDPGRMLSTC-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 4
- 229910021529 ammonia Inorganic materials 0.000 claims 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 3
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 2
- ACJCVBMVRMXKHJ-UHFFFAOYSA-N 2-hydroxy-6-methoxynaphthalene-1-carboxylic acid Chemical compound OC(=O)C1=C(O)C=CC2=CC(OC)=CC=C21 ACJCVBMVRMXKHJ-UHFFFAOYSA-N 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 abstract 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 150000007970 thio esters Chemical class 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 239000007818 Grignard reagent Substances 0.000 description 6
- 150000004795 grignard reagents Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- DAOUVKSHEHYOEW-UHFFFAOYSA-N C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.S(O)(O)(=O)=O Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.S(O)(O)(=O)=O DAOUVKSHEHYOEW-UHFFFAOYSA-N 0.000 description 3
- 238000003747 Grignard reaction Methods 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- -1 6-methoxy naphthyl Chemical group 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- APSMUYYLXZULMS-UHFFFAOYSA-N 2-bromonaphthalene Chemical compound C1=CC=CC2=CC(Br)=CC=C21 APSMUYYLXZULMS-UHFFFAOYSA-N 0.000 description 1
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 1
- FSUYQOYAPVYVHS-UHFFFAOYSA-N 6-bromonaphthalen-1-ol Chemical compound BrC1=CC=C2C(O)=CC=CC2=C1 FSUYQOYAPVYVHS-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- BLXXJMDCKKHMKV-UHFFFAOYSA-N Nabumetone Chemical compound C1=C(CCC(C)=O)C=CC2=CC(OC)=CC=C21 BLXXJMDCKKHMKV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000036592 analgesia Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229960004270 nabumetone Drugs 0.000 description 1
- 239000002547 new drug Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing 6-methoxy naphthaldehyde by 6-methoxy (hydroxyl) naphthoic acid through ester forming (ether forming), hydrazide reaction and oxidation. The present invention features that ester forming reaction takes thioester dimethyl ester as esterifying (etherifying) agent and methanol as reaction solvent, and the generated sulfuric acid has catalytic action and the reaction is maintained in acid state. Since methanol and dimethyl sulfate have the same-OCH3The groups break the balance of reversible reaction, so that the reaction is carried out towards the direction of ester formation, and reactants are almost converted into products according to the theoretical amount. The reaction conditions of the three steps of ester formation , hydrazide reaction and oxidation are mild, the product quality is good, the post-treatment is convenient and simple, the yield is high, and the total yield of the three steps of reaction is 80-82%.
Description
The invention belongs to organic synthesis and chemical pharmacy field.Relate to a kind of method that makes 6-methoxynaphthalene formaldehyde by 6-methoxyl group (or hydroxyl) naphthoic acid through esterification (etherificate), hydrazidesization, oxidation.The present invention is mainly used in the synthetic preparation of anti inflammation and heat resolution analgesia new drug nabumetone.
All relating to a kind of in the 46th page-51 pages of the 428th page-page 435 pages of " chemical pharmacy circular " the 2nd phases of nineteen eighty-two and " India's chemistry can will " first phases nineteen eighty-two is raw material prepares 6-methoxynaphthalene formaldehyde through grignard reaction method by 6-methoxyl group-2-bromonaphthalene.The weak point of above method is that the Grignard reagent price is expensive, the cost height, and the grignard reaction anhydrous condition requires high, and product separation and purification difficulty is difficult to adapt to suitability for industrialized production.
The vestige water gaging all can influence the preparation of Grignard reagent theoretically.The Grignard reagent activity is extremely strong in addition, very easily produces side reaction in the replacement process.Prepare 6-methoxynaphthalene formaldehyde with Grignard reagent and experienced three processes.Be the Grignard reagent preparation, replace and decompose that these three reactions all easily produce side reaction.The preparation Grignard reagent adopts anhydrous tetrahydro furan, and anhydrous dimethyl formamide is difficult to reach anhydrous fully in actual production process.Grignard reaction is a raw material with 6-bromonaphthalene sweet smell, so at first will prepare the 6-Bromonaphthol, its preparation needs heavy metal tin and deep-etching stimulant bromine, the unit consumption height of bromine, and the cost height, serious to equipment corrosion, three-waste pollution is serious.
The objective of the invention is for the deficiency of avoiding aforesaid method provides a kind of prices of raw and semifnished materials cheap, the reaction conditions gentleness, the product separation and purification is easy, the method for preparing 6-methoxynaphthalene formaldehyde that the good product quality suitability for industrialized is produced.
Purpose of the present invention can realize by following measure.
With 6-methoxyl group (or hydroxyl) naphthoic acid is raw material, makes 6-methoxynaphthalene formaldehyde through esterification (etherificate), hydrazidesization, oxidation.
Esterification (etherificate) reaction is that 6-methoxynaphthalene formic acid reacts with esterification (etherificate) system methyl-sulfate in methyl alcohol, generates 6-methoxynaphthalene methyl-formiate, and reaction formula is:
Esterification is reversible reaction, and conventional esterification all generates water, makes reaction reach balance very soon, so transformation efficiency is low.It is that solvent has increased-OCH that the present invention adopts methyl alcohol
3The concentration of group, the sulfuric acid that reaction generates plays katalysis, and keeps to be reflected under the acidic conditions and carry out, thereby has broken molecular balance.Reaction is carried out to the direction that generates 6-methoxynaphthalene methyl-formiate.Two-the OCH of sulfuric acid dioctyl phthalate under this condition
3Base all can be participated in reaction.Thereby the mole ratio of 6-methoxynaphthalene formic acid and methyl-sulfate is 1: 0.5-1.5, with 1: 0.5-0.7 is the best.The mole ratio of 6-hydroxynaphthoic acid and methyl-sulfate is 1: 1-2, with 1: 1-1.2 is the best.Under the reflux state, react end in 0.5-8 hour.Make reflux into water distilling apparatus, solvent methanol directly from reaction mass the distillation and remove crude product.Collect distilled methyl alcohol, be directly used in next reaction solvent.The washing crude product, dry 6-methoxynaphthalene methyl-formiate, the yield 98-100% of getting.
The hydrazides reaction is that 6-methoxynaphthalene methyl-formiate and hydrazine hydrate react generation 6-methoxynaphthalene formyl hydrazine in pure liquid.Alcohol can adopt ethanol, Virahol, butanols, amylalcohol, is best with ethanol.The mole ratio of 6-methoxynaphthalene methyl-formiate and hydrazine hydrate is 1: 1-1: 5, and be the best with 1: 3.The proportioning of hydrazine hydrate and alcohol is 1: 1-1: 5, and be the best with 1: 3.
Its reaction formula is:
Oxidizing reaction is 6-methoxynaphthalene formyl hydrazine and ammoniacal liquor, and the red prussiate of potash aqueous solution reacts in organic solvent and generates 6-methoxynaphthalene formaldehyde.Red prussiate of potash is that oxygenant, ammoniacal liquor are catalyzer.Ammoniacal liquor, the red prussiate of potash aqueous solution and organic solvent are divided into two-phase, form phase transfer reaction.Reaction on one side, will react the aldehyde solution transfer that generate to organic phase on one side, thereby avoided the aldehyde of generation further to be oxidized to acid, improved the quality and the yield of product.Organic phase can be benzene,toluene,xylene, ethyl acetate, is best with toluene.
Its reaction formula is:
The mole ratio of 6-methoxynaphthalene formyl hydrazine and red prussiate of potash is 1: 2-1: 4, and be the best with 1: 2.2.6-methoxynaphthalene formyl hydrazine and concentration are that the mole ratio of 20% ammoniacal liquor is 1: 4-1: 9, and with 1: 5-1: 6 is the best.
Be described in further detail below in conjunction with embodiment:
Embodiment 1: prepare 6-methoxyl group-2-2-methyl naphthoate by 6-methoxyl group-2-naphthoic acid.
28kg6-methoxyl group-2-naphthoic acid is dropped into adding methyl alcohol 140L in the glass-lined reactor, sulfuric acid dioctyl phthalate 9kg finished, stirs down temperature rising reflux 2 hours, refluxed and finished underpressure distillation methyl alcohol near dried, add ordinary water 140L, after the dispersed with stirring, centrifuging, washing, drying, drying get 6-methoxyl group-2-2-methyl naphthoate, be white or little yellow crystalline powder, fusing point 128-130 ℃, content is greater than 98%, and yield is more than 98%.Steam methyl alcohol and make next reaction solvent.
Embodiment 2: prepare 6-methoxyl group-2-2-methyl naphthoate by 6-hydroxyl-2-naphthoic acid.
37.6kg6-hydroxyl-2-naphthoic acid is dropped in the glass-lined reactor, add methyl alcohol 150L, sulfuric acid dioctyl phthalate 15kg, finish, temperature rising reflux is 6 hours under stirring, and refluxes and finishes, underpressure distillation methyl alcohol is done near, add ordinary water 150L, after the dispersed with stirring, centrifuging, washing, drying, the dry 6-methoxyl group-2-2-methyl naphthoate that gets, be white crystalline powder, fusing point 128-130 ℃, content is greater than 98%, and yield is more than 98%.Steaming methyl alcohol can directly apply mechanically.
Example 3: prepare 6-methoxyl group-2-naphthoyl hydrazine by 6-methoxyl group-2-2-methyl naphthoate.
With 6-methoxyl group-2-2-methyl naphthoate 30kg, drop in the glass-lined reactor, add 80% hydrazine hydrate 30kg, ethanol 80L, the temperature rising reflux reaction is more than 5 hours, reaction is complete to be cooled to below 10 ℃, and centrifuging, washing, drying get 6-methoxyl group-2-naphthoyl hydrazine.This product is white or light grey needle crystal.Fusing point 182-184 ℃, content is greater than 98%.
Embodiment 4: prepare 6-methoxyl group-2-naphthaldehyde by 6-methoxyl group-2-naphthoyl hydrazine.
With 6-methoxyl group-2-naphthoyl hydrazine 28kg, toluene 360L, 20% ammoniacal liquor 60kg, water 160L adds in the retort, stirs down in about 30 ℃, drip red prussiate of potash solution (red prussiate of potash 94kg is dissolved in the 500L water), dripped complete stirring reaction 0.5 hour, standing demix, organic phase is with 5% hydrochloric acid 50L, 5% sodium carbonate solution 50L, water 100L, washing respectively, standing demix gets toluene liquid.Change underpressure distillation in the retort over to.Residue put into dish solidify product, fusing point 78-80 ℃.Content is greater than 96%, yield 85%.
The present invention has following remarkable advantage compared with the prior art:
1. reaction condition gentleness. The reaction bar of each step reaction among the present invention Part is all very gentle, carries out at normal temperatures and pressures, and equipment is not had special wanting Ask, in the glass-lined reactor of routine, just can finish.
2. easy and simple to handle. Each step operation of the present invention is very easy, especially Esterification (etherificate), hydrazides, only just can be complete by normal reflux Become, post processing is very convenient.
3. good product quality, the yield height. Physique in the middle of each step of the present invention Measure. The yield height, esterification is become by reversible reaction can not be converse Should, and do not have the side reaction generation, transform by theoretical amount. By the 6-methoxy Base (or hydroxyl) naphthoic acid prepares the 6-methoxy naphthyl aldehyde, the total receipts Rate is about 82%.
4. raw material of the present invention are easy to get, and low price is suitable for industry Change large-scale production.
Claims (7)
1. one kind prepares the method for 6-methoxynaphthalene formaldehyde by 6-methoxyl group (or hydroxyl) naphthoic acid, comprising:
A, 6-methoxyl group (or hydroxyl) naphthoic acid and methyl-sulfate react in methyl alcohol and generate 6-methoxynaphthalene methyl-formiate, and reaction formula is
Wherein the mole ratio of 6-methoxynaphthalene formic acid and methyl-sulfate is 1: 0.5-1.5, and the mole ratio of 6-hydroxynaphthoic acid and methyl-sulfate is 1: 1-2;
B, 6-methoxynaphthalene methyl-formiate and hydrazine hydrate react in alcoholic solution and generate 6-methoxynaphthalene formyl hydrazine, and reaction formula is:
Wherein the mole ratio of 6-methoxynaphthalene methyl-formiate and hydrazine hydrate is 1: 1-1.5, and hydrazine hydrate is 1 with the proportioning of alcohol: 1-1.5;
C, 6-methoxynaphthalene formyl hydrazine and ammoniacal liquor, the red prussiate of potash aqueous solution react in organic solvent and generate 6-methoxynaphthalene formaldehyde, and reaction formula is:
Wherein the mole ratio of 6-methoxynaphthalene formyl hydrazine and red prussiate of potash is 1: 3-1: 4, and 6-methoxynaphthalene formyl hydrazine and concentration are that 20% ammonia mol ratio is 1: 4-9;
2. according to the process of claim 1 wherein that the mole ratio of 6-methoxynaphthalene formic acid and methyl-sulfate is 1: 0.5-0.7, the mole ratio of 6-hydroxynaphthoic acid and methyl-sulfate is 1: 1-1.2.
3. according to the method for claim 1 or 2, be heated to backflow when wherein the esterification of a (etherificate) is reacted, reacted 0.5-4 hour.
4. the alcohol when the process of claim 1 wherein the hydrazides of b is ethanol, Virahol, butanols, amylalcohol.
5. the mole ratio of 6-methoxynaphthalene methyl-formiate and hydrazine hydrate is 1: 3 when the process of claim 1 wherein the b hydrazides, and hydrazine hydrate is 1: 3 with the proportioning of alcohol.
6. the organic solvent when the process of claim 1 wherein the c oxidation is benzene,toluene,xylene, ethyl acetate.
When the process of claim 1 wherein the c oxidation 6-methoxynaphthalene formyl hydrazine and red prussiate of potash mole ratio be 1: 2,2,6-methoxynaphthalene formyl hydrazine and concentration are that 20% ammonia mol ratio is 1: 5-6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92108127 CN1031131C (en) | 1992-05-08 | 1992-05-08 | Preparation method of 6-methoxy naphthaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92108127 CN1031131C (en) | 1992-05-08 | 1992-05-08 | Preparation method of 6-methoxy naphthaldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1067044A CN1067044A (en) | 1992-12-16 |
| CN1031131C true CN1031131C (en) | 1996-02-28 |
Family
ID=4943250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92108127 Expired - Fee Related CN1031131C (en) | 1992-05-08 | 1992-05-08 | Preparation method of 6-methoxy naphthaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1031131C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2752877B2 (en) * | 1993-03-24 | 1998-05-18 | 株式会社上野製薬応用研究所 | Preparation of ether esters of hydroxynaphthoic acids |
| JP2752878B2 (en) * | 1993-03-24 | 1998-05-18 | 株式会社上野製薬応用研究所 | Preparation of ether esters of hydroxynaphthoic acids |
| JP2006131568A (en) * | 2004-11-08 | 2006-05-25 | Ueno Seiyaku Oyo Kenkyusho:Kk | Hydroxynaphthoic acid hydrazide, derivative thereof and method for producing the same |
| FI120684B (en) * | 2005-10-21 | 2010-01-29 | Valtion Teknillinen | Process for the preparation of oligo- / polyesters from a carboxylic acid mixture of suberin and / or cutin |
| CN104447252A (en) * | 2013-09-18 | 2015-03-25 | 浙江天新药业有限公司 | Method for preparing 6-methoxyl-2-naphthaldehyde |
-
1992
- 1992-05-08 CN CN 92108127 patent/CN1031131C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1067044A (en) | 1992-12-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5998658A (en) | Catalytic processes for the preparation of acetic esters | |
| CN1031131C (en) | Preparation method of 6-methoxy naphthaldehyde | |
| CN1036648C (en) | Method and equipment for continuous catalyzing rectifying production of n-butyester acetate | |
| CN102060767A (en) | Method for producing caprolactam by methylbenzene | |
| CN109956849B (en) | Method for preparing ethylene glycol diacetate and sec-butyl alcohol, catalytic system and device | |
| US5719311A (en) | Catalytic processes for esterification of carboxylic acids | |
| CN1114600C (en) | Process for continuously synthesizing coumarin | |
| CN113666837A (en) | Preparation method of 1, 4-dimethyl pentylamine hydrochloride | |
| CN1332153A (en) | preparation method of tetraacetylethylenediamine | |
| CN1066442A (en) | Novel process with preparing aminic acid by methyl formate hydrolysis | |
| CN113233983A (en) | Method for catalytically synthesizing linalyl acetate by using acidic deep eutectic solvent | |
| CN1915984A (en) | Method for preparing whisky lactone | |
| CN1049885C (en) | Method for preparation of N-methyl formamide | |
| WO2020155145A1 (en) | Method for preparing ketone organics | |
| CN101691325B (en) | Preparation method and device of raw materials needed in preparing acetic anhydride by carbonylation | |
| CN1029478C (en) | Process for preparing aromatic esters or ethers | |
| CN116655566B (en) | Method for synthesizing 2, 5-furandicarboxylic acid by one step through 2, 5-furandicarboxaldehyde without participation of oxygen | |
| CN102260170A (en) | Method for microwave pipeline production of butyl acetate | |
| CN1197790A (en) | Preparation of acetate product | |
| CN117603097B (en) | Method for rapidly preparing 2-bromo-5-nitrobenzenesulfonyl chloride | |
| US3089898A (en) | Preparation of methyl acrylate | |
| CN111517936B (en) | Method for preparing ketone organic matter | |
| CN1944370A (en) | Synthesizing and preparing method for acetylacetone | |
| CN115160122A (en) | Novel process for preparing glycollic acid by hydrolyzing methyl glycolate | |
| CN1127469C (en) | Method for synthesizing pseudoionone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |