CN1067370C - Synthesis of p-benzaldehyde - Google Patents
Synthesis of p-benzaldehyde Download PDFInfo
- Publication number
- CN1067370C CN1067370C CN97106992A CN97106992A CN1067370C CN 1067370 C CN1067370 C CN 1067370C CN 97106992 A CN97106992 A CN 97106992A CN 97106992 A CN97106992 A CN 97106992A CN 1067370 C CN1067370 C CN 1067370C
- Authority
- CN
- China
- Prior art keywords
- aminobenzaldehyde
- reaction
- nitrotoluene
- para
- sodium
- Prior art date
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- 230000015572 biosynthetic process Effects 0.000 title 1
- 238000003786 synthesis reaction Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 16
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims abstract description 8
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000006193 diazotization reaction Methods 0.000 claims abstract description 6
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000007323 disproportionation reaction Methods 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims abstract description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims abstract 2
- VATYWCRQDJIRAI-UHFFFAOYSA-N p-aminobenzaldehyde Chemical compound NC1=CC=C(C=O)C=C1 VATYWCRQDJIRAI-UHFFFAOYSA-N 0.000 claims description 28
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- 239000003444 phase transfer catalyst Substances 0.000 claims description 9
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001256 steam distillation Methods 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 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 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 3
- 229920001021 polysulfide Polymers 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- MQHYHHITRWRJSI-UHFFFAOYSA-N [Cu].Br Chemical compound [Cu].Br MQHYHHITRWRJSI-UHFFFAOYSA-N 0.000 claims description 2
- 230000031709 bromination Effects 0.000 claims description 2
- 238000005893 bromination reaction Methods 0.000 claims description 2
- 229960002798 cetrimide Drugs 0.000 claims description 2
- 239000012954 diazonium Substances 0.000 claims description 2
- 150000001989 diazonium salts Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 235000010288 sodium nitrite Nutrition 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 2
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- -1 trifluoromethyl cerous sulfate Chemical compound 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a process for synthesizing p-bromobenzoformaldehyde by using p-nitrotoluene as a raw material, which comprises such steps as the dismutation reaction of p-nitrotoluene under the action of sodium polysulfide to generate p-aminobenzoform-aldehyde, the diazotization reaction of the p-aminobenzoform-aldehyde, and under the catalysis of cuprous bromide or copper, p-bromobenzoformaldehyde is generated in hydrobromic acid.
Description
The present invention relates to a kind of method of synthetic p-bromobenzaldehyde, p-bromobenzaldehyde is a kind of important medicine and dyestuff intermediate.
The method of existing synthetic p-bromobenzaldehyde mainly is to be raw material with the para-bromo toluene, and a kind of is to generate cyclite through photochemical bromo-reaction, obtains through hydrolysis again, and this method has realized industrialization, and another kind is to be that the oxygenant oxidation gets with the trifluoromethyl cerous sulfate.Their common drawback is the raw materials cost height, and the former liquid bromine of having adopted highly volatile, having had hazardness, and the oxidation style that the latter adopts is industrial wayward.
It is the method for the synthetic p-bromobenzaldehyde of raw material with the para-nitrotoluene that the present invention proposes a kind of.
The present invention is raw material with the para-nitrotoluene, disproportionation reaction is taking place under the catalysis of phase-transfer catalyst with under the sodium polysulfide solution effect, generate p-Aminobenzaldehyde, then by p-Aminobenzaldehyde through under the catalysis of cuprous bromide or copper, generating p-bromobenzaldehyde after the acidifying diazotization.
Sodium polysulfide solution is by sodium sulphite (Na
2S9H
2O) generate with the elemental sulfur effect.The mol ratio of sodium sulphite and sulphur is 1: 2-1: 4.
Sodium polysulphide and para-nitrotoluene generate p-Aminobenzaldehyde under the effect of phase-transfer catalyst in the ethanolic soln of 95%-65%, and have a small amount of para-totuidine to produce.The mol ratio of sodium polysulphide and para-nitrotoluene is 1: 3-1: 5, and the addition of phase-transfer catalyst is for participating in the 1%-5% of the para-nitrotoluene amount of reacting, and the 1mol para-nitrotoluene is participated in reaction and is needed 95% ethanol 400-600ml, and temperature of reaction is 80-90 ℃.Under the above-mentioned condition, the yield of p-Aminobenzaldehyde＞90%.
The phase-transfer catalyst that is adopted is a kind of in bromination tetrabutylammonium, CETRIMIDE POWDER, tetrabutylammonium iodide, dinethylformamide, the tween or two kinds mixture wherein, adopts mixed phase transfer catalyst better effects if.
The p-Aminobenzaldehyde that makes is through steam distillation, the wet product that crystallisation by cooling obtains, and drying is not directly participated in next step reaction.
The acidifying of p-Aminobenzaldehyde is souring agent with sulfuric acid, is diazo reagent with Sodium Nitrite.Diazotization splashes into the cuprous bromide hydrobromic acid solution of new system or going back in the native copper Hydrogen bromide suspension liquid, after dripping off of new system with diazonium salt solution after finishing, allow solution slowly be warming up to 60 ℃, be incubated one hour, carry out steam distillation, distillate filters, washs colourlessly or light yellow p-bromobenzaldehyde.Purity＞98%.
The 1mol p-Aminobenzaldehyde is participated in reaction and is needed also native copper of 0.5-1mol cuprous bromide or 0.05-0.1mol, needs the 2-3mol Hydrogen bromide, and usual method is adopted in the preparation of cuprous bromide.P-bromobenzaldehyde is 55-65% with respect to the yield of para-nitrotoluene.
The invention provides a kind of is the method for the synthetic p-bromobenzaldehyde of raw material with the para-nitrotoluene.Adopt this method to synthesize p-bromobenzaldehyde, raw materials cost is low, easily realize industrialization, and product purity reaches 99%.
Embodiment: in thermometer, agitator, reflux exchanger, dropping funnel, 1000ml four-necked bottle are housed, add the 50g para-nitrotoluene, 250m195% ethanol, 2.5g mixed phase transfer catalyst, be warming up to 80 ℃, in 1 hour, splash into the 0.09mol sodium polysulfide solution, be incubated 2 hours again, steam distillation, crystallisation by cooling get yellow p-Aminobenzaldehyde.Wet product p-Aminobenzaldehyde adds in another 1000ml three-necked bottle, adds 260g40%H
2SO
4, in 80 ℃ the reaction half an hour, be cooled to 0-3 ℃, add 25gNaNO fast
2, keep half an hour then, solution is splashed in half an hour in the 2000ml flask that fills 104m140%HBr and 0.189mol cuprous bromide solution, slowly be warming up to 60 ℃ then, be incubated 1 hour, steam distillation gets the 40.7g p-bromobenzaldehyde, purity 99%.
Claims (6)
1. the method for a synthetic p-bromobenzaldehyde, it is characterized in that with the para-nitrotoluene being raw material, disproportionation reaction is taking place under the catalysis of phase-transfer catalyst and under the sodium polysulfide solution effect, generate p-Aminobenzaldehyde, sodium polysulfide solution is formed by elemental sulfur and sodium sulphite effect, the mol ratio of sodium sulphite and sulphur is 1: 2-1: 4, p-Aminobenzaldehyde is through acidifying, after the diazotization, diazonium salt solution is splashed into the hydrobromic acid solution of cuprous bromide or go back in the native copper Hydrogen bromide suspension liquid, slowly be warming up to 60 ℃, be incubated one hour, carry out steam distillation, distillate filters, obtain p-bromobenzaldehyde after the washing.
2. method according to claim 1 is characterized in that disproportionation reaction is to carry out in the ethanolic soln of 95%-65%, the mol ratio of sodium polysulphide and para-nitrotoluene is 1: 3-1: 5.
3. method according to claim 1, it is characterized in that in the disproportionation reaction process, the addition of phase-transfer catalyst is for participating in the 1%-5% of the para-nitrotoluene amount of reacting, the 1mol para-nitrotoluene is participated in reaction and is needed 95% ethanol 400-600ml, temperature of reaction is 80-90 ℃, the yield of p-Aminobenzaldehyde＞90%.
4. method according to claim 1 is characterized in that the phase-transfer catalyst that is adopted is a kind of in bromination tetrabutylammonium, CETRIMIDE POWDER, tetrabutylammonium iodide, N-diformamide, the tween or two kinds mixture wherein.
5. method according to claim 1, the acidifying that it is characterized in that p-Aminobenzaldehyde is souring agent with sulfuric acid, diazotization reaction is to be diazotization agent with the Sodium Nitrite.
6. method according to claim 1 is characterized in that 1mol p-Aminobenzaldehyde participation reaction needs also native copper of 0.5-1mol cuprous bromide or 0.05-0.1mol, needs the 2-3mol Hydrogen bromide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106992A CN1067370C (en) | 1997-06-06 | 1997-06-06 | Synthesis of p-benzaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106992A CN1067370C (en) | 1997-06-06 | 1997-06-06 | Synthesis of p-benzaldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1201777A CN1201777A (en) | 1998-12-16 |
| CN1067370C true CN1067370C (en) | 2001-06-20 |
Family
ID=5169188
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97106992A Expired - Fee Related CN1067370C (en) | 1997-06-06 | 1997-06-06 | Synthesis of p-benzaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1067370C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113979878B (en) * | 2021-10-29 | 2024-05-03 | 浙江工业大学 | Preparation method of 2-aminobenzaldehyde |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4585898A (en) * | 1984-12-18 | 1986-04-29 | Hardwicke Chemical Company | Preparation of substituted benzaldehydes |
| US4645186A (en) * | 1984-07-18 | 1987-02-24 | Outokumpu Oy | Apparatus for processing sulphide concentrates and sulphide ores into raw material |
-
1997
- 1997-06-06 CN CN97106992A patent/CN1067370C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4645186A (en) * | 1984-07-18 | 1987-02-24 | Outokumpu Oy | Apparatus for processing sulphide concentrates and sulphide ores into raw material |
| US4585898A (en) * | 1984-12-18 | 1986-04-29 | Hardwicke Chemical Company | Preparation of substituted benzaldehydes |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1201777A (en) | 1998-12-16 |
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| 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 |