CN104292082A - Preparation method for hydroquinone monoether compound - Google Patents
Preparation method for hydroquinone monoether compound Download PDFInfo
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- CN104292082A CN104292082A CN201410449009.0A CN201410449009A CN104292082A CN 104292082 A CN104292082 A CN 104292082A CN 201410449009 A CN201410449009 A CN 201410449009A CN 104292082 A CN104292082 A CN 104292082A
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- preparation
- phenol
- alcohol
- acid
- resorcinol
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 title abstract 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 7
- -1 monoalkyl ether Chemical class 0.000 claims abstract description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 46
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims description 5
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 claims description 3
- COVZYZSDYWQREU-UHFFFAOYSA-N Busulfan Chemical compound CS(=O)(=O)OCCCCOS(C)(=O)=O COVZYZSDYWQREU-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000003321 amplification Effects 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 abstract 1
- 238000006266 etherification reaction Methods 0.000 abstract 1
- 150000002989 phenols Chemical class 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ZSBDGXGICLIJGD-UHFFFAOYSA-N 4-phenoxyphenol Chemical compound C1=CC(O)=CC=C1OC1=CC=CC=C1 ZSBDGXGICLIJGD-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 150000005826 halohydrocarbons Chemical class 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- NIONDZDPPYHYKY-SNAWJCMRSA-N (2E)-hexenoic acid Chemical compound CCC\C=C\C(O)=O NIONDZDPPYHYKY-SNAWJCMRSA-N 0.000 description 1
- WTAUMGJJFXKZLQ-UHFFFAOYSA-N 2-hexoxyphenol Chemical compound CCCCCCOC1=CC=CC=C1O WTAUMGJJFXKZLQ-UHFFFAOYSA-N 0.000 description 1
- ZNCUUYCDKVNVJH-UHFFFAOYSA-N 2-isopropoxyphenol Chemical compound CC(C)OC1=CC=CC=C1O ZNCUUYCDKVNVJH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical compound [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 229940045029 cobaltous nitrate hexahydrate Drugs 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229940001516 sodium nitrate Drugs 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003469 sulfuric acid diesters Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method for a hydroquinone monoether compound. The method is characterized in that: hydroquinone is adopted as the raw material, and an organic alcohol/phenolic compound is adopted as an etherification agent to prepare the hydroquinone monoether compound under the action of a sulfonic acid main catalyst and a nitrated matter cocatalyst. The method provided by the invention has the advantages that: 1) the process is simple, the raw materials are cheap and easily available, amplification of the operation process and industrialized production can be easy to realize; and 2) the preparation method has wide applicability, can synthesize a variety of hydroquinone monoether compounds including monoalkyl ether, mono-aromatic hydrocarbon ether and monoolefine ether of hydroquinone, and is a general preparation technology for hydroquinone monoether compounds.
Description
technical field
The present invention relates to a kind of preparation method of Resorcinol monoether compound, particularly relate to a kind of catalyzer can preparing various Resorcinol monoether compound.
background technology
Resorcinol monoether compound, it is important organic synthesis intermediate, the main stopper being used as the monomers such as vinyl cyanide, vinylformic acid, methacrylic acid, hexenoic acid, the antioxidant of food oils and makeup, the stablizer of photochromics, is also used as the intermediate etc. of anti-aging agent, softening agent and pharmaceutical synthesis.
The preparation method of Resorcinol monoether compound is more, usually using Resorcinol as raw material, according to following three kinds of methods preparation: 1) using sulfuric acid diester species as etherifying reagent, this method advantage is sufficient raw, yield is higher, shortcoming is that sulfuric acid two ester compound is usually hypertoxic, is unfavorable for suitability for industrialized production; 2) using halohydrocarbon as etherifying reagent, this method reactions steps is few, and long carbon bond halogenated alkane also can react, shortcoming be halohydrocarbon cost compared with high, toxicity large, product yield is lower; 3) under para benzoquinone exists, take alcohol as etherifying reagent, this technique easy handling, raw material is easy to get, low price, therefore attracts attention.But most patent reports (CN102775282A, CN201010287410.0) are confined to the preparation of hydroquinone monomethyl ether, lack a kind of preparation method of general Resorcinol monoether compound.
The present invention for starting raw material, under the condition not using para benzoquinone, has invented a kind of preparation method of general Resorcinol monoether compound with Resorcinol and various alcohol compound.
summary of the invention
The object of the present invention is to provide a kind of preparation method of general Resorcinol monoether compound, to realize the easy synthesis of various Resorcinol monoether compound.
Above object is realized by following approach: by a certain percentage Resorcinol, Organic Alcohol/phenol and catalyzer are added reactor mixing, and keep whipped state; After reaction terminates, evaporation removing alcohol, realizes product separation by the Resorcinol monoether compound in mixture after extractive reaction.Reaction formula is as follows:
Wherein, substituent R can be C
1-C
6straight-chain paraffin base, sec.-propyl, propenyl or phenyl.
Primary Catalysts of the present invention is the combination of one or more in sulfuric acid, organic sulfonic acid (part halogenated alkylsulfonic acids, aromatic sulphonic acid, whole haloalkyl sulfonic acid etc.), heteropolyacid, macropore sulfuric acid resin, perfluorinated sulfonic resin.Preferably, Primary Catalysts comprises the combination of one or more in sulfuric acid, methanesulfonic, trifluoromethanesulfonic acid, tosic acid, Amberlyst 15, Nafion-H.
Promotor of the present invention is itrated compound, can be selected from the combination of one or more in (Asia) nitric acid and ammonium salt thereof, metal (Asia) nitrate (metal comprises: Li, Na, K, Mg, Ca, Fe, Cu, Zn, Ni, Al, Ag, Au, Mn, Co).
The proportioning of Resorcinol used in the present invention, Organic Alcohol/phenol, Primary Catalysts and promotor is:
The volumetric molar concentration of Resorcinol in alcohol is 0.01-10 M, preferably 1.6 M.
The volumetric molar concentration of Primary Catalysts in alcohol is 0.1-10 M, preferably 2.0 M.
The volumetric molar concentration of promotor in alcohol is 0.1-10 M, preferably 0.12 M.
Further, temperature of reaction of the present invention is at 10-100
obetween C, and preferably at 20-35
obetween C.
Further, the reaction times of the present invention between 1-48 hour, and preferably between 1-24 hour.
Product of the present invention is after underpressure distillation removes alcohol/phenol, ether, ethyl acetate, methylene dichloride, chloroform or tetracol phenixin etc. can be used to separate from the rear mixture of reaction as extraction agent, thick product can use petrol ether/ethyl acetate to carry out recrystallizing and refining, and solvent for use can recycle.
Compared with prior art, the present invention has the following advantages:
1) the present invention is suitable for preparing various types of Resorcinol monoether compound, has suitability widely;
2) abundant raw material source that the present invention is used, cheap, synthetic method is simply efficient, the amplification of easy handling process and realize suitability for industrialized production;
embodiment
Below in conjunction with embodiment, the specific embodiment of the present invention is described in further detail.To contribute to understanding the present invention by following embodiment, but not limit content of the present invention.
Embodiment 1:
Resorcinol (4.4g, 40mmol), methyl alcohol (20g, 25mL), lithium nitrate (0.21g, 3mmol) and 98% sulfuric acid (2.7mL, 50mmol) is added, in 20 in 100ml reaction flask
oc reacts 24 hours, and underpressure distillation removing methyl alcohol, under agitation adds anhydrous diethyl ether (20mL × 2) and extract, and extraction liquid is merged underpressure distillation removing, obtains p methoxy phenol crude product (4.46g, 36mmol), yield 90%.
Embodiment 2-7:
Experimental procedure is identical with embodiment 1, and only use other sulfonic acid to replace in 98% sulfuric acid, reaction result is as shown in the table:
| Project | Primary Catalysts (g) | Yield (%) |
| 1. | -- | 0 |
| 2. | Methanesulfonic (4.8) | 81 |
| 3. | Trifluoromethanesulfonic acid (7.5) | 89 |
| 4. | Tosic acid (8.6) | 71 |
| 5. | Amberlyst 15（5） | 76 |
| 6. | Nafion-H（5） | 90 |
Embodiment 8-13:
Experimental procedure is identical with embodiment 1, and only replaced by other itrated compound of lithium nitrate, reaction result is as shown in the table:
| Project | Promotor (g, mmol) | Yield (%) |
| 1. | Nitric acid (0.28,3) | 81 |
| 2. | Ammonium nitrite (0.19,3) | 82 |
| 3. | Sodium Nitrite (0.21,3) | 72 |
| 4. | SODIUMNITRATE (0.26,3) | 65 |
| 5. | Gerhardite (0.72,3) | 70 |
| 6. | Cobaltous nitrate hexahydrate (0.87,3) | 68 |
Embodiment 14-18:
Experimental procedure is identical with embodiment 1, and only the volumetric molar concentration of Resorcinol changed, reaction result is as shown in the table:
| Project | Resorcinol (g, mmol, M) | Yield (%) |
| 1. | 0.03，0.28，0.01 | 83 |
| 2. | 0. 30，2.8，0.1 | 85 |
| 3. | 3.04，27.8，1.0 | 89 |
| 4. | 15.2，139，5.0 | 71 |
| 5. | 30.4，278，10 | 57 |
Embodiment 19-22:
Experimental procedure is identical with embodiment 1, and only the volumetric molar concentration of sulfuric acid changed, reaction result is as shown in the table:
| Project | 98% sulfuric acid (mL, mmol, M) | Yield (%) |
| 1. | 0.14，2.5，0.1 | 34 |
| 2. | 1.4，25.0，1.0 | 85 |
| 3. | 6.75，125， 5.0 | 89 |
| 4. | 13.5，250， 10.0 | 76 |
Embodiment 23-25:
Experimental procedure is identical with embodiment 1, and only the volumetric molar concentration of lithium nitrate changed, reaction result is as shown in the table:
| Project | Lithium nitrate (g, mmol, M) | Yield (%) |
| 1. | 0.17，2.5，0.1 | 78 |
| 2. | 1.72，25.0，1.0 | 72 |
| 3. | 17.24，250，10.0 | 20 |
Embodiment 26-29:
Experimental procedure is identical with embodiment 1, only temperature of reaction is changed, and reaction result is as shown in the table:
| Project | Temperature ( oC) | Yield (%) |
| 1. | 10 | 80 |
| 2. | 35 | 87 |
| 3. | 80 | 74 |
| 4. | 100 | 61 |
Embodiment 30-32:
Experimental procedure is identical with embodiment 1, and only will change in the reaction times, reaction result is as shown in the table:
| Project | Time (hour) | Yield (%) |
| 1. | 1 | 52 |
| 2. | 10 | 73 |
| 3. | 48 | 71 |
Embodiment 33-36:
Experimental procedure is identical with embodiment 1, and only replaced by other alcohol/phenol of methyl alcohol, reaction result is as shown in the table:
| Project | Alcohol/phenol (g, mL) | Yield (%) |
| 1. | Hexanol (20.5,25) | 80 |
| 2. | Virahol (19.5,25) | 81 |
| 3. | Vinylcarbinol (21,25) | 75 |
| 4. | Phenol (25,265.6) | 70 |
Because of length restriction, the present invention does not illustrate one by one to all preferred example, but the technical scheme adopting the mode of carrying out equivalent replacement or equivalent transformation to the key element of this technology to obtain all is in protection scope of the present invention.
P methoxy phenol:
1H?NMR?(CDCl
3,?600?MHz)?δ:?3.80?(s,?3H);?5.38?(s,?1H);?6.92?(m,?4H).
13C?NMR?(CDCl
3)?δ:154.0,?149.9,?116.1,?115.0,?56.0.
To hexyloxy-phenol:
1H?NMR?(CDCl
3,?600?MHz)?δ:?0.90?(t,?
J?=?6.8?Hz,?3H),?1.26-1.40?(m,?4H),?1.40-1.52?(m,?2H),?1.70-1.80?(m,?2H),?3.90?(t,?
J?=?6.5?Hz,?2H),?4.74?(s,?1H),?6.73-6.81(m,?4H).?
13C?NMR?δ:?14.2,?22.7,?25.9,?29.5,?31.7,?68.9,115.8,?116.1,?149.5,?153.4;
To isopropoxy phenol:
1H?NMR?(CDCl
3,?600?MHz)?δ:?4.44?(m,?6H);?5.92?(s,?1H);?6.80?(m,?4H).
13C?NMR?(CDCl
3)?δ:151.8,?149.9,?118.1,?116.2,?71.8,?22.2.
To propenyloxy group phenol:
1H?NMR?(CDCl
3,?600?MHz)?δ:?6.84?(d,?
J=9.0?Hz,?2H),?6.79?(d,?
J=9.0?Hz,?2H),?6.07?(m,?1H),?5.42?(dd,?
J=1.8,?16.8?Hz,?1H),?5.27?(dd,?
J=1.8,?10.2?Hz,?1H,),?4.73?(s,?1H),?4.51?(d,?
J=5.4?Hz,?2H).?
13C?NMR?(CDCl
3)?δ:?152.78,?149.62,?113.57,?117.59,?116.03,?115.97,?69.71.
P-phenoxyphenol:
1H?NMR?(DMSO-
d6,?400?MHz)?δ:?6.75–6.78?(m,?2H),?6.85–6.87?(m,?3H),?7.01?(dd,?
J?=?7.6,?7.2?Hz,?1H),?7.30?(dd,?
J?=8.0,?7.6?Hz,?2H),?9.31?(s,?1H).?
13C?NMR?(DMSO-
d6)?δ:?116.2,?116.8,?120.9,?122.1,?129.7,?147.7,?153.8,?158.3.
Claims (9)
1. the present invention discloses a kind of preparation method of Resorcinol monoether compound at this, it is characterized in that: with Resorcinol and various Organic Alcohol/phenol for raw material, under sulphonic acids Primary Catalysts and the effect of itrated compound promotor, prepare various Resorcinol monoether compound, it has following structural formula:
Wherein, substituent R can be C
1-C
6straight-chain paraffin, sec.-propyl, allyl group or phenyl.
2. preparation method according to claim 1, is characterized in that the Organic Alcohol/phenol used comprises C
1-C
6straight chain saturated alcohol, Virahol, vinylcarbinol, phenol.
3. preparation method according to claim 1, described sulphonic acids Primary Catalysts comprises the combination of one or more in sulfuric acid, organic sulfonic acid (part halogenated alkylsulfonic acids, aromatic sulphonic acid, whole haloalkyl sulfonic acid etc.) macropore sulfuric acid resin, perfluorinated sulfonic resin, preferably, Primary Catalysts comprises the combination of one or more in sulfuric acid, methanesulfonic, trifluoromethanesulfonic acid, tosic acid, Amberlyst 15, Nafion-H.
4. preparation method according to claim 1, the itrated compound promotor that it is characterized in that using is (Asia) nitric acid and ammonium salt thereof, one or more in metal (Asia) nitrate (metal comprises: Li, Na, K, Mg, Ca, Fe, Cu, Zn, Ni, Al, Ag, Au, Mn, Co).
5. preparation method according to claim 1, the volumetric molar concentration of described Resorcinol in alcohol/phenol is 0.01-10 M, preferably 1.6 M.
6. preparation method according to claim 1, the volumetric molar concentration of described sulphonic acids Primary Catalysts in alcohol/phenol is 0.1-10 M, preferably 2.0 M.
7. preparation method according to claim 1, the volumetric molar concentration of described promotor in alcohol/phenol is 0.1-10 M, preferably 0.12 M.
8. preparation method according to claim 1, described temperature of reaction is at 10-100
obetween C, and preferably at 20-35
obetween C.
9. preparation method according to claim 1, the described reaction times between 1-48 hour, and preferably between 1-24 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410449009.0A CN104292082A (en) | 2014-09-05 | 2014-09-05 | Preparation method for hydroquinone monoether compound |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410449009.0A CN104292082A (en) | 2014-09-05 | 2014-09-05 | Preparation method for hydroquinone monoether compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104292082A true CN104292082A (en) | 2015-01-21 |
Family
ID=52312076
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| CN106957218A (en) * | 2017-03-21 | 2017-07-18 | 山东省分析测试中心 | A kind of solid phase synthesis process of PBBs ether monomer and application |
| CN117603020A (en) * | 2023-11-22 | 2024-02-27 | 康羽生命科学技术(苏州)有限公司 | Method for synthesizing p-methoxyphenol by catalytic oxidation of phenol |
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