CN105016979B - A kind of method for synthesizing 4 alkyl fortified phenols - Google Patents
A kind of method for synthesizing 4 alkyl fortified phenols Download PDFInfo
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- CN105016979B CN105016979B CN201510477759.3A CN201510477759A CN105016979B CN 105016979 B CN105016979 B CN 105016979B CN 201510477759 A CN201510477759 A CN 201510477759A CN 105016979 B CN105016979 B CN 105016979B
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- Prior art keywords
- alkyl
- aniline
- acid
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- synthesis
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- 238000000034 method Methods 0.000 title claims abstract description 21
- 150000002989 phenols Chemical class 0.000 title claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 title abstract 4
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011592 zinc chloride Substances 0.000 claims abstract description 9
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- 125000005233 alkylalcohol group Chemical group 0.000 claims abstract description 5
- 150000001448 anilines Chemical class 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Substances [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 2
- 235000010288 sodium nitrite Nutrition 0.000 claims description 2
- 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
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229920002472 Starch Polymers 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 6
- 235000019698 starch Nutrition 0.000 description 6
- 239000008107 starch Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000029936 alkylation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- RZJRJXONCZWCBN-UHFFFAOYSA-N alpha-octadecene Natural products CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KJWMCPYEODZESQ-UHFFFAOYSA-N 4-Dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=C(O)C=C1 KJWMCPYEODZESQ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000017858 demethylation Effects 0.000 description 2
- 238000010520 demethylation reaction Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- SOANRMMGFPUDDF-UHFFFAOYSA-N 2-dodecylaniline Chemical compound CCCCCCCCCCCCC1=CC=CC=C1N SOANRMMGFPUDDF-UHFFFAOYSA-N 0.000 description 1
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 1
- OGIQUQKNJJTLSZ-UHFFFAOYSA-N 4-butylaniline Chemical class CCCCC1=CC=C(N)C=C1 OGIQUQKNJJTLSZ-UHFFFAOYSA-N 0.000 description 1
- CYYZDBDROVLTJU-UHFFFAOYSA-N 4-n-Butylphenol Chemical compound CCCCC1=CC=C(O)C=C1 CYYZDBDROVLTJU-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- SZYWUQQAVKOBQA-UHFFFAOYSA-N [Si].CI(C)C Chemical compound [Si].CI(C)C SZYWUQQAVKOBQA-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- -1 alkyl bromo-derivative Chemical compound 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/045—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of a group bound to the ring by nitrogen
- C07C37/05—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of a group bound to the ring by nitrogen by substitution of a NH2 group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method for synthesizing 4 alkyl fortified phenols, under zinc chloride catalysis, the alkyl alcohol that aniline and carbon number are 4 30 is reacted in toluene or dimethylbenzene and obtains 4 alkyl substituted anilines, 4 alkyl fortified phenols are then obtained with natrium nitrosum and acid reaction；The present invention is simple to operate, and intermediate need not isolate and purify, you can enters and reacts in next step, improves reaction yield.Finished product purity is high, and the depth of parallelism is good during reproduction, and process conditions are adapted to amplification quantity production.
Description
Technical field
The present invention relates to a kind of method of synthesis 4- alkyl fortified phenols, belong to organic synthesis field.
Background technology
It is mainly used in the weight of the preparation of advanced liquid crystal material, lube oil additive and industrial surface activity agent to alkylphenol
Want one of raw material.Though having manufacturer production at present, yield is small, technology is complicated, cost is high, environmental pollution can not meet greatly city
The needs of field；And it is of poor quality, liquid crystal material can not be met, prepare the quality of raw material needed for senior lubricant and surfactant
It is required that.
Prior art mainly includes two methods：
Method one, set out using methyl phenyl ethers anisole, occur to pay a gram alkylation first in the presence of alchlor, then restore carbonyl
Base finally obtains target product into alkyl substituents using demethylation.The method step is more, it is necessary to equivalent above catalyst, ring
Border pollution is larger.
Method two, set out using para-bromoanisole, be first prepared into after grignard reagent reacts with corresponding alkyl bromo-derivative
To alkyl-substituted methyl phenyl ethers anisole, target product is finally obtained using demethylation.The method step is more, it is necessary to more than equivalent be catalyzed
Agent, environmental pollution is larger, to equipment requirement height.
The content of the invention
For overcome the deficiencies in the prior art, the present invention provides a kind of two step synthesis sides that easily can industrially produce
Case, it is readily available in raw materials market, and it is cheap.
To achieve these goals, the present invention adopts the following technical scheme that：A kind of side of synthesis 4- alkyl fortified phenols
Method, comprise the following steps：
1., the alkyl alcohol that aniline and carbon number are 4-30 add toluene or dimethylbenzene 110-140 DEG C under zinc chloride catalysis
Back flow reaction, when reaction solution goes out there is no moisture, 4- alkyl substituted benzene amine aqueous solutions are obtained after cooling.
2., by step 1. in obtained 4- alkyl substituted benzenes amine and acid be sufficiently mixed, discard organic layer, waterlayer control temperature
Sodium nitrite in aqueous solution is added dropwise under the conditions of 0-60 DEG C of degree.After reaction terminates, it is layered while hot, the substitution of 4- alkyl is obtained after rectification under vacuum
Phenol.
Further, in the above-mentioned technical solutions, the mol ratio of the step 1. middle aniline and alkyl alcohol, zinc chloride is
1:1-1.2:0.02-0.05。
Further, in the above-mentioned technical solutions, 2. middle acid is selected from watery hydrochloric acid or dilute sulfuric acid to the step.
Further, in the above-mentioned technical solutions, the step 2. middle 4- alkyls substituted aniline and natrium nitrosum, acid
Mol ratio is 1:1-2:1-2.
Invention beneficial effect
The inventive method make use of the high activity of aniline, and amino is without protection, using catalytic amount anhydrous zinc chloride catalyst
The high selectivity alkylation based on the 4- positions of aniline can be achieved.Then using conventional diazotising, amino is transformed into hydroxyl,
So as to avoid in conventional process conditions under condition of ultralow temperature, deprotected using Boron tribromide or trimethyl iodine silicon.
The invented technology operating procedure is short, and we are common a large amount of existing aniline and alkanol through alkylation using raw material
Two-step reaction is hydrolyzed with diazonium and obtains low cost, high income, pollution subenvironment close friend.Synthesize in practice it is superior into
Product.
Intermediate need not isolate and purify, you can enter and react in next step, improve reaction yield.Finished product purity is high,
The depth of parallelism is good during reproduction, and process conditions are adapted to amplification quantity production.
Embodiment
Embodiment 1
The synthesis of 4- normal butane base phenol
In the reaction bulb equipped with mechanical agitation and reflux water-dividing device, aniline (0.1 mole), n-butanol (0.11 are added
Mole) and 120 milliliters of toluene, anhydrous zinc chloride (2 mmoles) is then added, 110 DEG C of reactions is heated to and is stirred overnight.Detection reaction
Completely, it is directly used in after cooling in reacting in next step.
0 DEG C is cooled to, upper step solution is added into 0.15 mole of 20% dilute sulfuric acid aqueous solution, control exothermic heat of reaction temperature does not surpass
20 DEG C are crossed, toluene layer discards.Natrium nitrosum (0.15 mole) is dissolved in 300 milliliters of water, is slowly added dropwise under agitation above-mentioned
4- n-butyl anilines dilution heat of sulfuric acid in, controlling reaction temperature be 20-40 DEG C, reaction end uses starch potassium iodide paper
Examine, when reaction solution makes starch potassium iodide become blue and color is no longer taken off, stop being added dropwise.If natrium nitrosum amount deficiency
Continue to be added dropwise, until reaction is reached home.Then reaction solution is kept to continue to stir at 40 DEG C, there is no bubble until reaction solution
Generation, shows that hydrolytic process terminates.After being layered while hot, upper strata crude product rectifying obtains 4- normal-butyl phenol, HPLC purity
99.1%, two step yields 52%.
Embodiment 2
The synthesis of 4- dodecyl phenol
In the reaction bulb equipped with mechanical agitation and reflux water-dividing device, aniline (0.1 mole), n-dodecanol are added
(0.12 mole) and 170 milliliters of dimethylbenzene, anhydrous zinc chloride (5 mmoles) is then added, 140 DEG C of reactions is heated to and is stirred overnight.
Detection reaction is complete, is directly used in after cooling in reacting in next step.
0 DEG C is cooled to, upper step solution is added in 0.20 mole of 15% watery hydrochloric acid, control exothermic heat of reaction temperature is no more than 20
DEG C, diformazan benzene layer discards.Natrium nitrosum (0.20 mole) is dissolved in 260 milliliters of water, is slowly added dropwise under agitation above-mentioned
In the dilute hydrochloric acid solution of the positive dodecyl aniline of 4-, controlling reaction temperature is 30-50 DEG C, and reaction end uses starch potassium iodide paper
Examine, when reaction solution makes starch potassium iodide become blue and color is no longer taken off, stop being added dropwise.If natrium nitrosum amount deficiency
Continue to be added dropwise, until reaction is reached home.Then reaction solution is kept to continue to stir at 40 DEG C, there is no bubble until reaction solution
Generation, shows that hydrolytic process terminates.It is layered while hot, 4- dodecyl phenol sterlings, HPLC is obtained after the crude product rectification under vacuum of upper strata：
98.2%, two step yields 57%.
Embodiment 3
The synthesis of 4- n-octadecane base phenol：
In the reaction bulb equipped with mechanical agitation and reflux water-dividing device, aniline (0.1 mole), positive octadecyl alcolol are added
(0.12 mole) and 180 milliliters of dimethylbenzene, anhydrous zinc chloride (5 mmoles) is then added, 140 DEG C of reactions is heated to and is stirred overnight.
Detection reaction is complete, is directly used in after cooling in reacting in next step.
0 DEG C is cooled to, upper step solution is added into 0.14 mole of 20% dilute sulfuric acid aqueous solution, control exothermic heat of reaction temperature does not surpass
20 DEG C are crossed, diformazan benzene layer discards.Natrium nitrosum (0.14 mole) is dissolved in 250 milliliters of water, is slowly added dropwise under agitation
In the dilution heat of sulfuric acid for the 4- n-octadecane base aniline stated, controlling reaction temperature is 30-50 DEG C, and reaction end uses starch iodate
Potassium test paper is examined, and when reaction solution makes starch potassium iodide become blue and color is no longer taken off, stops being added dropwise.If natrium nitrosum amount
It is insufficient then continue to be added dropwise, until reaction is reached home.Then keep reaction solution continue to stir at 50 DEG C, until reaction solution no longer
There is bubble formation, show that hydrolytic process terminates.It is layered while hot, 4- n-octadecane base phenol is obtained after the crude product rectification under vacuum of upper strata,
HPLC:98.4%, two-step reaction yield 48%.
The preferable embodiment of the present invention is these are only, but protection scope of the present invention is not limited thereto, it is any
Those familiar with the art is in the technical scope of present disclosure, technique according to the invention scheme and its invention
Design is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (3)
- A kind of 1. method of synthesis 4- alkyl fortified phenols, it is characterised in that comprise the following steps：1., the alkyl alcohol that aniline and carbon number are 4-30 add toluene or dimethylbenzene 110-140 DEG C under anhydrous zinc chloride catalysis Back flow reaction, when reaction solution goes out there is no moisture, 4- alkyl substituted aniline solution is obtained after cooling；2., by step 1. in obtained 4- alkyls substituted aniline and acid be sufficiently mixed, discard organic layer, waterlayer control temperature 0- Sodium nitrite in aqueous solution is added dropwise under the conditions of 60 DEG C；After reaction terminates, it is layered while hot, 4- nalkas is obtained after the crude product rectification under vacuum of upper strata Base fortified phenol；1. the mol ratio of middle aniline and alkyl alcohol, anhydrous zinc chloride is 1 to the step:1-1.2:0.02-0.05.
- A kind of 2. method of synthesis 4- alkyl fortified phenols according to claim 1, it is characterised in that：The step is 2. Middle acid is selected from watery hydrochloric acid or dilute sulfuric acid.
- A kind of 3. method of synthesis 4- alkyl fortified phenols according to claim 1, it is characterised in that：The step is 2. The mol ratio of middle 4- alkyls substituted aniline and natrium nitrosum, acid is 1:1-2:1-2.
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| CN201510477759.3A CN105016979B (en) | 2015-08-07 | 2015-08-07 | A kind of method for synthesizing 4 alkyl fortified phenols |
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| CN201510477759.3A CN105016979B (en) | 2015-08-07 | 2015-08-07 | A kind of method for synthesizing 4 alkyl fortified phenols |
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Inventor after: Li Yuxia Inventor after: Li Yingju Inventor after: Loyalty Hall Inventor after: Zhu Jianjun Inventor before: Yang Hui Inventor before: Zhang Chuanjun |
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Effective date of registration: 20171025 Address after: 030000 No. 6, building 75, 12 Park Road, Wan Berlin District, Shanxi, Taiyuan Applicant after: Li Yuxia Address before: 441021, Xiangcheng province Xiangfan District, Hubei Province Lake Industrial Park Applicant before: HUBEI JINGHONG CHEMICAL Co.,Ltd. |
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