CN117550953A - Method for preparing benzene diphenol key intermediate di- (2-hydroxyisopropyl) benzene - Google Patents
Method for preparing benzene diphenol key intermediate di- (2-hydroxyisopropyl) benzene Download PDFInfo
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- CN117550953A CN117550953A CN202311631777.3A CN202311631777A CN117550953A CN 117550953 A CN117550953 A CN 117550953A CN 202311631777 A CN202311631777 A CN 202311631777A CN 117550953 A CN117550953 A CN 117550953A
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- benzene
- oxygen
- hydroxyisopropyl
- diisopropylbenzene
- base
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- 238000000034 method Methods 0.000 title claims abstract description 34
- RFXSFVVPCLGHAU-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1 RFXSFVVPCLGHAU-UHFFFAOYSA-N 0.000 title description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 claims abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001301 oxygen Substances 0.000 claims abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000002585 base Substances 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 17
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 16
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims abstract description 12
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- -1 dicumyl hydroperoxide Chemical compound 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- SPPWGCYEYAMHDT-UHFFFAOYSA-N 1,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C(C)C)C=C1 SPPWGCYEYAMHDT-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 description 5
- LEARFTRDZQQTDN-UHFFFAOYSA-N 2-[4-(2-hydroxypropan-2-yl)phenyl]propan-2-ol Chemical compound CC(C)(O)C1=CC=C(C(C)(C)O)C=C1 LEARFTRDZQQTDN-UHFFFAOYSA-N 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 241001521402 Maackia <angiosperm> Species 0.000 description 4
- 238000004811 liquid chromatography Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- UGPWRRVOLLMHSC-UHFFFAOYSA-N 2-[3-(2-hydroxypropan-2-yl)phenyl]propan-2-ol Chemical compound CC(C)(O)C1=CC=CC(C(C)(C)O)=C1 UGPWRRVOLLMHSC-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- LECYCYNAEJDSIL-UHFFFAOYSA-N 1-bromo-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1Br LECYCYNAEJDSIL-UHFFFAOYSA-N 0.000 description 1
- 206010017533 Fungal infection Diseases 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 208000031888 Mycoses Diseases 0.000 description 1
- 239000005590 Oxyfluorfen Substances 0.000 description 1
- OQMBBFQZGJFLBU-UHFFFAOYSA-N Oxyfluorfen Chemical compound C1=C([N+]([O-])=O)C(OCC)=CC(OC=2C(=CC(=CC=2)C(F)(F)F)Cl)=C1 OQMBBFQZGJFLBU-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- BXNANOICGRISHX-UHFFFAOYSA-N coumaphos Chemical compound CC1=C(Cl)C(=O)OC2=CC(OP(=S)(OCC)OCC)=CC=C21 BXNANOICGRISHX-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 231100001081 no carcinogenicity Toxicity 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- YGSFNCRAZOCNDJ-UHFFFAOYSA-N propan-2-one Chemical compound CC(C)=O.CC(C)=O YGSFNCRAZOCNDJ-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/78—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by condensation or crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/26—Polyhydroxylic alcohols containing only six-membered aromatic rings as cyclic part
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for preparing a key intermediate of benzenediol, namely di- (2-hydroxyisopropyl) benzene. There is provided a process for preparing di- (2-hydroxyisopropyl) benzene comprising the steps of: (1) Reacting diisopropylbenzene with an oxygen-containing gas in the presence of a base and an initiator to obtain a liquid comprising di- (2-hydroxyisopropyl) benzene solids; (2) Separating di- (2-hydroxyisopropyl) benzene solid and purifying to obtain di- (2-hydroxyisopropyl) benzene product with content more than 99.95%, wherein the initiator comprises one or more of azodiisobutyronitrile, dicumyl peroxide and dicumyl peroxide, the alkali comprises sodium hydroxide, potassium hydroxide or a combination thereof, and the oxidation reaction in the step (1) has a temperature of 80-150 ℃ and a pressure of 0.3-1.8MPa.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a novel method for preparing a key intermediate di- (2-hydroxyisopropyl) benzene of benzenediol.
Background
Bis- (2-hydroxyisopropyl) benzene (also known as α, α' -dihydroxy-diisopropylbenzene) is a key feedstock for the preparation of benzenediol. The benzenediol can be synthesized into pesticides (coumaphos, etc.), herbicides (oxyfluorfen, etc.), etc., or can be prepared into ointment medicine for external application to treat dermatologic diseases of fungal infection. The benzenediol has the advantages of biological safety because of no carcinogenicity, no teratogenesis and no bioaccumulation.
Synthetic studies and production are reported by Hercules, germany Bayer, japan Mitsui petrochemical company, etc., but there is no report in this regard. Therefore, it is necessary to examine the synthesis of di- (2-hydroxyisopropyl) benzene.
There are basically two routes for preparing DC, namely, diisopropylbenzene (DIPB) is taken as a starting material, and p-diisopropylbenzene is taken as an example in the following reaction formula.
Route 1: diisopropylbenzene is halogenated (e.g., brominated) to produce di (2-bromoisopropyl) benzene, which is then hydrolyzed to di- (2-hydroxyisopropyl) benzene.
Route 2: in a special reactor, diisopropylbenzene is oxidized by oxygen under the action of cobalt salt to obtain di- (2-hydroxyisopropyl) benzene.
CN103396292a discloses a new method for preparing di- (2-hydroxyisopropyl) benzene, which is specifically as follows:
CN115403446a discloses that under the action of an active agent, 1, 3-diisopropylbenzene reacts with oxygen in the air to generate di- (2-hydroxyisopropyl) benzene, etc., wherein under the catalytic action of cobalt ions, hydroperoxide is decomposed into alcohol, free radicals are released, and other raw materials are oxidized, so that di- (2-hydroxyisopropyl) benzene is obtained by a one-step method.
Therefore, there is an urgent need in the art for a new method for synthesizing di- (2-hydroxyisopropyl) benzene, which has a simple operation procedure, can obtain di- (2-hydroxyisopropyl) benzene with high yield and high selectivity, has mild reaction conditions, is easy to control, and is suitable for industrialization.
Disclosure of Invention
The purpose of the application is to provide a novel method for synthesizing the key intermediate di- (2-hydroxyisopropyl) benzene of the benzenediol, which has simple operation flow, can obtain the di- (2-hydroxyisopropyl) benzene with high yield and high selectivity, has mild reaction conditions, is easy to control, and is suitable for industrialization.
The inventor of the application finds that the di- (2-hydroxy isopropyl) benzene can be directly obtained by oxidizing the diisopropylbenzene under a sufficient alkali atmosphere, a cobalt catalyst is not needed to be added, and the conversion rate and the selectivity of the diisopropylbenzene are greatly improved, so that the process is simplified and the cost is reduced.
In one aspect, the present application provides a process for preparing a key intermediate of benzenediol, di- (2-hydroxyisopropyl) benzene, comprising the steps of:
(1) Reacting diisopropylbenzene with an oxygen-containing gas in the presence of a base and an initiator to obtain a liquid comprising di- (2-hydroxyisopropyl) benzene solids;
(2) Separating and purifying the di- (2-hydroxy isopropyl) benzene solid to obtain a di- (2-hydroxy isopropyl) benzene product with the content of more than 99.95 percent,
wherein the initiator comprises one or more of azodiisobutyronitrile, dicumyl peroxide and dicumyl peroxide,
the base comprises sodium hydroxide, potassium hydroxide or a combination thereof,
the temperature of the oxidation reaction in the step (1) is 80-150 ℃ and the pressure is 0.3-1.8MPa.
In another aspect, the present application provides a key intermediate of benzenediol, di- (2-hydroxyisopropyl) benzene, prepared by the process of the present application.
Detailed Description
The "ranges" disclosed herein are defined as lower and upper limits, with the given ranges being defined by selecting a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular ranges. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4 and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values. When a certain parameter is expressed as an integer of 2 or more, it is disclosed that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12 or the like.
In this application, all embodiments and preferred embodiments mentioned herein can be combined with each other to form new solutions, unless specifically stated otherwise.
In the present application, all technical features mentioned herein as well as preferred features may be combined with each other to form new solutions, if not specifically stated.
In the present application, all steps mentioned herein may be performed sequentially or randomly, but are preferably performed sequentially, unless otherwise specified. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), may include steps (a), (c) and (b), may include steps (c), (a) and (b), and the like.
In the present application, references herein to "comprising" and "including" mean open, and may be closed, unless otherwise specified. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
In the description herein, unless otherwise indicated, "above" and "below" are intended to include the present number, and "one or more" means two or more.
In the description herein, unless otherwise indicated, the term "or" is inclusive. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or absent); a is false (or absent) and B is true (or present); or both A and B are true (or present).
In this context, unless otherwise specified, the percentages (%) or parts refer to weight percentages or parts by weight relative to the composition.
In this context, the sum of the contents of the individual components in the composition is 100%, if not stated to the contrary.
In this context, the sum of the parts of the components in the composition may be 100 parts by weight, if not stated to the contrary.
In this context, unless otherwise indicated, "a combination thereof" means a multicomponent mixture of the elements, e.g., two, three, four, and up to the maximum possible multicomponent mixture.
The term "a" as used in this specification means "at least one" unless specifically indicated.
In this context, unless otherwise indicated, each reaction is carried out at ambient temperature and pressure.
In one aspect, the present application provides a process for preparing a key intermediate of benzenediol, di- (2-hydroxyisopropyl) benzene, comprising the steps of:
(1) Reacting diisopropylbenzene with an oxygen-containing gas in the presence of a base and an initiator to obtain a liquid comprising di- (2-hydroxyisopropyl) benzene solids;
(2) Separating and purifying the di- (2-hydroxy isopropyl) benzene solid to obtain a di- (2-hydroxy isopropyl) benzene product with the content of more than 99.95 percent,
wherein the initiator comprises one or more of azodiisobutyronitrile, dicumyl peroxide and dicumyl peroxide,
the base comprises sodium hydroxide, potassium hydroxide or a combination thereof,
the temperature of the oxidation reaction in the step (1) is 80-150 ℃ and the pressure is 0.3-1.8MPa.
In this application, the diisopropylbenzene may be a diisopropylbenzene product commonly used in the art, which may be prepared according to a method commonly used in the art, or may be a commercially available product. Typically, diisopropylbenzene is in liquid form, but also in solution form.
In the present application, the initiator includes one or more of azobisisobutyronitrile, dicumyl hydroperoxide and dicumyl peroxide. The initiator with a similar structure to the raw material diisopropylbenzene is selected, and the oxidation activity is higher in the reaction process, so that the selectivity and the yield of the di- (2-hydroxyisopropyl) benzene are improved.
In one example of the present application, the initiator may be used in an amount of 0.01% to 20%, preferably 0.05% to 15%, more preferably 0.1% to 10% by weight of the diisopropylbenzene.
In this application, the oxygen-containing gas represents any gas containing oxygen, for example a gas containing 1 to 100% by volume of oxygen, and also includes a gas capable of generating oxygen during the reaction. In one example of the present application, the oxygen-containing gas represents a gas comprising 10-100% by volume oxygen. In another example of the present application, the oxygen-containing gas represents air.
In the present application, the oxygen is used in an amount of 0.2 to 6 times, for example 0.5 to 5 times or 1 to 4 times the weight of the diisopropylbenzene, based on the weight of oxygen in the oxygen-containing gas.
In this application, the base is a strong base to increase the reactivity, e.g., to increase the selectivity, yield, and conversion of the reaction. In one example of the present application, the base includes sodium hydroxide, potassium hydroxide, or a combination thereof. The base may be in the form of a solution of the base or may be a solid. In the case of an alkaline solution, the solvent may be a solvent commonly used in the art, including but not limited to water. In a preferred example of the present application, the alkali is an aqueous solution of sodium hydroxide or potassium hydroxide, and the mass content is 1 to 20%. The base (in the case of an alkaline solution, based on the weight of the base in solution) is used in an amount of 10% to 100%, preferably 20% to 90%, more preferably 30% to 70% by weight of the diisopropylbenzene.
In the method of the present application, the temperature of the oxidation reaction in the step (1) is 80 to 150 ℃ (preferably 80 to 120 ℃) and the pressure is 0.3 to 1.8MPa (preferably 0.5 to 1.5 MPa) for obtaining a good effect.
In the process of the present application, the step (1) preferably does not use a cobalt-containing catalyst. The applicant has found that, unlike the prior art disclosures, better technical results, such as higher conversions, selectivities and yields (yields), can be obtained without the use of cobalt-containing catalysts under the specific starting materials and reaction conditions of the present application.
In the method of the present application, the separation step in the step (2) may be performed by a method commonly used in the art, including, but not limited to, filtration, centrifugation, and the like. The separation step may be performed at normal temperature or under heating. In one example of the present application, the temperature of the separation step is 10-100 ℃, preferably 20-70 ℃.
In the method of the present application, the purification step in the step (2) may be a purification method commonly used in the art, including, but not limited to, recrystallization, and the like. The recrystallization method can be carried out by using solvents commonly used in the art, including but not limited to one or more of methanol, ethanol, acetone, methyl isobutyl ketone, methyl acetate, ethyl acetate and butyl acetate, and the dosage is 1-10 times of the weight of the product, and the crystallization temperature is 30-80 ℃.
In another aspect, the present application provides a key intermediate of benzenediol, di- (2-hydroxyisopropyl) benzene, prepared by the process of the present application.
In one example of the present application, the di- (2-hydroxyisopropyl) benzene has a purity of greater than 99.5%.
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
Experimental main reagent
| Reagent(s) | Type(s) | Manufacturing factories |
| Para-diisopropylbenzene | Analytical grade | Chengdu Maackia chemical Co., ltd |
| M-diisopropylbenzene | Analytical grade | Chengdu Maackia chemical Co., ltd |
| Azobisisobutyronitrile | Analytical grade | Chengdu Maackia chemical Co., ltd |
| Sodium hydroxide | Analytical grade | Jiangsu Yangnong chemical group Co., ltd |
| Ethanol | Analytical grade | Chengdu Maackia chemical Co., ltd |
Main experimental instrument
| Instrument name | Model number | Manufacturing factories |
| Electronic balance | JA31002 | Shanghai Instrument and science instruments Co., ltd |
| 1L reaction kettle | J2-04 | Kadsura Co., ltd |
| Liquid chromatograph | LC | Agilent technologies Co Ltd |
The experimental method comprises the following steps:
diisopropylbenzene conversion: (amount of converted diisopropylbenzene substance/amount of diisopropylbenzene substance charged to the total reaction) ×100%
Di- (2-hydroxyisopropyl) benzene selectivity: (amount of actually formed di- (2-hydroxyisopropyl) species/amount of converted diisopropylbenzene species) ×100% of
Yield of di- (2-hydroxyisopropyl) benzene: p-diisopropylbenzene conversion Di- (2-hydroxyisopropyl) benzene selectivity
Yield of di- (2-hydroxyisopropyl) benzene crystallization: (mass after recrystallization)/(mass before recrystallization) ×100%
Liquid phase test conditions
Example 1
162.2g of p-diisopropylbenzene, 0.2g of azobisisobutyronitrile and 405.5g of 20% sodium hydroxide aqueous solution were charged into a 1L reaction vessel, and the temperature was raised to 80 ℃. 3244.0g of air was introduced under 0.5MPa, and the reaction was stopped by co-aeration for 12 hours to obtain a reaction solution containing α, α' -dihydroxy-1, 4-diisopropylbenzene (the peak time of the liquid chromatography is shown in Table 4). The conversion rate of the p-diisopropylbenzene is 97.0%, the selectivity of the alpha, alpha' -dihydroxyl-1, 4-diisopropylbenzene is 99.0%, and the yield is 96.0%.
And (3) carrying out solid-liquid separation on the reaction liquid. And then, continuously applying the p-diisopropylbenzene which is not completely converted in the upper layer oil layer and the lower layer liquid alkali into the reaction kettle. The crude α, α '-dihydroxy-1, 4-diisopropylbenzene obtained by filtration was recrystallized from ethanol at 50℃to obtain 178.8g of α, α' -dihydroxy-1, 4-diisopropylbenzene (peak time of liquid chromatography is shown in Table 4). The crystallization yield is 96.0%, the total yield is 92.2%, and the product purity is 99.98%.
Example 2
162.2g of m-diisopropylbenzene, 0.2g of azobisisobutyronitrile and 405.5g of 20% sodium hydroxide aqueous solution were charged into a 1L reaction vessel, and the temperature was raised to 80 ℃. 3244.0g of air was introduced under 0.5MPa, and the reaction was stopped by co-aeration for 12 hours to obtain a reaction solution containing α, α' -dihydroxy-1, 3-diisopropylbenzene (the peak time of the liquid chromatography is shown in Table 5). The conversion rate of the m-diisopropylbenzene is 95.0%, the selectivity of the alpha, alpha' -dihydroxyl-1, 3-diisopropylbenzene is 97.0%, and the yield is 92.2%.
And (3) carrying out solid-liquid separation on the reaction liquid. And then, continuously applying the m-diisopropylbenzene which is not completely converted in the upper oil layer and the lower liquid alkali into the reaction kettle. The crude α, α '-dihydroxy-1, 3-diisopropylbenzene obtained by filtration was recrystallized from methanol at 50℃to obtain 169.8g of α, α' -dihydroxy-1, 3-diisopropylbenzene (peak time of liquid chromatography is shown in Table 5), crystallization yield 95.0%, total yield 87.5% and product purity 99.96%.
Examples 3 to 12
The different initiators were replaced on the basis of example 1:
TABLE 1 evaluation results of initiator
From the data in table 1, it can be seen that: azobisisobutyronitrile, 1, 4-dihydroperoxide diisopropylbenzene and 1, 4-monoperoxydiisopropylbenzene have higher oxidation activity and alpha, alpha' -dihydroxy-1, 4-diisopropylbenzene selectivity. The free radical initiator can promote oxidation reaction, and the initiator with similar structure to the raw material can improve the reactivity.
Examples 13 to 19
The different reaction temperatures and pressures were changed on the basis of example 1:
table 2 evaluation results of temperature and pressure
From the data in table 2, it can be seen that: the reaction temperature is 80-100 ℃ and the pressure is 0.1-1.5 MPa, and the raw material diisopropylbenzene has higher conversion rate and the selectivity of the product alpha, alpha' -dihydroxy-1, 4-diisopropylbenzene.
Examples 20 to 27
The crystallization temperature and the solvent were changed on the basis of example 1:
TABLE 3 evaluation results of the influence of temperature and solvent on crystallization
| Examples | Temperature/. Degree.C | Solvent(s) | Yield/%of alpha, alpha' -dihydroxy-1, 4-diisopropyl crystals |
| 20 | 50 | Methanol | 95.3 |
| 21 | 50 | Acetone (acetone) | 94.7 |
| 22 | 50 | Methyl isobutyl ketone | 96.0 |
| 23 | 50 | Acetic acid methyl ester | 93.2 |
| 24 | 50 | Acetic acid ethyl ester | 96.0 |
| 25 | 50 | Butyl acetate | 95.1 |
| 26 | 30 | Ethanol | 76.8 |
| 27 | 70 | Ethanol | 98.5 |
Table 4 Components and Peak time
Table 5 Components and Peak time
The content is not limited to the embodiments of the present invention.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that the above-mentioned preferred embodiment should not be construed as limiting the invention, and the scope of the invention should be defined by the appended claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (10)
1. A process for preparing a key intermediate of benzenediol, di- (2-hydroxyisopropyl) benzene, comprising the steps of:
(1) Reacting diisopropylbenzene with an oxygen-containing gas in the presence of a base and an initiator to obtain a liquid comprising di- (2-hydroxyisopropyl) benzene solids;
(2) Separating and purifying the di- (2-hydroxy isopropyl) benzene solid to obtain a di- (2-hydroxy isopropyl) benzene product with the content of more than 99.95 percent,
wherein the initiator comprises one or more of azodiisobutyronitrile, dicumyl peroxide and dicumyl peroxide,
the base comprises sodium hydroxide, potassium hydroxide or a combination thereof,
the temperature of the oxidation reaction in the step (1) is 80-150 ℃ and the pressure is 0.3-1.8MPa.
2. The method of claim 1, wherein the initiator comprises one or more of azobisisobutyronitrile, dicumyl hydroperoxide, and dicumyl peroxide.
3. The process according to claim 1, wherein the initiator is used in an amount of 0.01% to 20%, preferably 0.05% to 15%, more preferably 0.1% to 10% by weight of the diisopropylbenzene.
4. The method according to claim 1, wherein the oxygen containing gas is an oxygen containing gas or a gas capable of generating oxygen during the reaction, such as a gas comprising 1-100 vol.% oxygen; preferably, the oxygen-containing gas represents a gas comprising 10-100% by volume of oxygen; preferably, the oxygen-containing gas represents air.
5. The method of claim 1, wherein the amount of oxygen is 0.2-6 times, such as 0.5-5 times or 1-4 times the weight of diisopropylbenzene based on the weight of oxygen in the oxygen-containing gas.
6. The method of claim 1, wherein the base is a strong base; preferably, the base comprises sodium hydroxide, potassium hydroxide, or a combination thereof; preferably, the base is in the form of a solution of base; preferably, the alkali is aqueous solution of sodium hydroxide and potassium hydroxide; preferably, the base is used in an amount of 10% to 100%, preferably 20% to 90%, more preferably 30% to 70% by weight of diisopropylbenzene based on the weight of diisopropylbenzene.
7. The process according to claim 1, wherein the oxidation reaction in step (1) is carried out at a temperature of 80-150 ℃ (preferably 80-120 ℃) and a pressure of 0.3-1.8MPa (preferably 0.5-1.5 MPa).
8. The process of claim 1, wherein step (1) does not use a cobalt-containing catalyst.
9. The method of claim 1, wherein the purifying step in step (2) comprises recrystallization.
10. A key intermediate of benzenediol, di- (2-hydroxyisopropyl) benzene, prepared by the process of the present application; preferably, the purity of the di- (2-hydroxyisopropyl) benzene is greater than 99.5%.
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