CN111732526A - A diphenyl sulfone derivative composition and its preparation method - Google Patents
A diphenyl sulfone derivative composition and its preparation method Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 70
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical class C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000002904 solvent Substances 0.000 claims abstract description 34
- -1 haloethyl ether Chemical compound 0.000 claims abstract description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006467 substitution reaction Methods 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 23
- 238000002844 melting Methods 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- ZNSMNVMLTJELDZ-UHFFFAOYSA-N Bis(2-chloroethyl)ether Chemical group ClCCOCCCl ZNSMNVMLTJELDZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 8
- 239000003880 polar aprotic solvent Substances 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 239000003586 protic polar solvent Substances 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 3
- 150000007530 organic bases Chemical class 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 5
- 238000006386 neutralization reaction Methods 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007806 chemical reaction intermediate Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000007039 two-step reaction Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- SCZNXLWKYFICFV-UHFFFAOYSA-N 1,2,3,4,5,7,8,9-octahydropyrido[1,2-b]diazepine Chemical compound C1CCCNN2CCCC=C21 SCZNXLWKYFICFV-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A diphenyl sulfone derivative composition and its preparation method are provided. The composition of the diphenyl sulfone derivative comprises a compound with n being 1 and a compound with n being 2, wherein the weight ratio of the compound with n being 1 to the compound with n being 2 is 2.16:1 to 2.41: 1. The preparation method of the diphenyl sulfone derivative composition comprises the following steps: pre-reacting 4,4 '-dihydroxydiphenyl sulfone, a first solvent and an alkaline aqueous solution to obtain 4,4' -dihydroxydiphenyl sulfone salt; isolating the 4,4' -dihydroxydiphenyl sulfone salt; subjecting the separated 4,4' -dihydroxydiphenyl sulfone salt, a second solvent and a haloethyl ether to a substitution reaction; and adding an acid solution for neutralization to obtain the diphenyl sulfone derivative composition.
Description
Technical Field
The invention relates to a diphenyl sulfone derivative composition and a preparation method thereof, in particular to a method for preparing a diphenyl sulfone derivative composition by a two-step reaction taking 4,4' -dihydroxy diphenyl sulfone salt as an intermediate.
Background
As a color developer for thermal paper, diphenyl sulfone derivatives have excellent coloring sensitivity, storage stability and heat resistance, and are mainly used in facsimile machines, receipts, electronic invoices, cash registers and the like.
The traditional preparation method of the diphenyl sulfone derivative is to dissolve Bisphenol S (BPS) in a two-phase reaction system consisting of an alkaline aqueous solution and a water-immiscible organic solvent, and add alkyl halide for reaction. However, the diphenyl sulfone derivatives obtained by this method have a low purity and a wide range of melting point differences, so that the performance in color development applications is affected.
In addition, in the purification stage, the traditional preparation method uses hydrochloric acid for neutralization, and then uses methanol for washing and filtration, so that the situation of caking is caused, the industrial production is not facilitated, and the use of a large amount of volatile organic solvents is also easy to cause harm to human bodies.
In view of the above, it is necessary to provide a composition of diphenyl sulfone derivatives with a small range of melting point difference and high purity, and a preparation method for effectively improving the purity of the product, so as to solve the problems in the prior art.
Disclosure of Invention
In order to solve the above problems, the present invention provides a diphenyl sulfone derivative composition comprising a compound having n as 1 and a compound having n as 2, which have the following formula (I),
and the weight ratio of the compound with n being 1 to the compound with n being 2 is 2.16:1 to 2.41: 1.
In one embodiment of the diphenyl sulfone derivative composition of the present invention, the difference between the melting points of the composition ranges from 12 ℃ to 14 ℃.
The invention also provides a preparation method of the diphenyl sulfone derivative composition, which comprises the following steps: dissolving 4,4 '-dihydroxydiphenyl sulfone in a first solvent, and adding an aqueous alkaline solution for pre-reaction to form a 4,4' -dihydroxydiphenyl sulfone salt, wherein the weight ratio of the reaction alkali to water of the aqueous alkaline solution is 35:65 to 50: 50; isolating the 4,4' -dihydroxydiphenyl sulfone salt; and mixing the separated 4,4' -dihydroxydiphenyl sulfone salt with a second solvent and haloethyl ether to form a reaction system for substitution reaction; and adding an acid solution after the substitution reaction is completed to obtain the composition of the diphenyl sulfone derivative.
In one embodiment of the preparation method of the present invention, the first solvent is selected from a polar protic solvent or a polar aprotic solvent, for example, the polar protic solvent is at least one selected from the group consisting of water, methanol, ethanol, propanol, butanol and isopropanol; the polar aprotic solvent is at least one selected from the group consisting of acetone, dimethyl sulfoxide, dimethylformamide and tetrahydrofuran. In a preferred embodiment, the first solvent is tetrahydrofuran.
In one embodiment of the preparation method of the present invention, the pre-reaction is performed at 15 ℃ to 40 ℃ for 0.5 to 2 hours.
In one embodiment of the preparation method of the present invention, the reaction base is one selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates and organic bases. In a preferred embodiment, the reaction base is sodium hydroxide.
In one embodiment of the preparation method of the present invention, the second solvent is water or an aqueous ethanol solution. In another embodiment, the water is present in an amount of 25 wt% to 60 wt% based on the weight of the reaction system.
In a preferred embodiment of the preparation process of the present invention, the haloethyl ether is bis (2-chloroethyl) ether.
In an embodiment of the preparation method of the present invention, the method further comprises dissolving the separated 4,4' -dihydroxydiphenyl sulfone salt in a second solvent before the substitution reaction, and then adding the haloethyl ether to the second solvent in which the 4,4' -dihydroxydiphenyl sulfone salt is dissolved, wherein the addition flow rate of the haloethyl ether to the 4,4' -dihydroxydiphenyl sulfone is 0.15 wt% to 0.25 wt% per minute. Further, according to an embodiment of the present invention, the haloethyl ether is added dropwise to the second solvent in which the 4,4' -dihydroxydiphenylsulfone salt is dissolved. In another embodiment, the haloethyl ether is added for a time of 1 to 3 hours.
In one embodiment of the preparation method of the present invention, the temperature of the substitution reaction is 80 ℃ to 110 ℃.
In one embodiment of the preparation process of the present invention, the substitution is carried out at a temperature ranging from 80 ℃ to 110 ℃ for 8 to 16 hours after the addition of the haloethyl ether is completed.
In an embodiment of the preparation method of the present invention, the acid solution is sulfuric acid.
In an embodiment of the preparation method of the present invention, the method further comprises washing and filtering the crystals using a liquid in which the diphenyl sulfone derivative composition is not soluble after adding the acid solution to obtain the crystals of the diphenyl sulfone derivative composition, wherein the liquid contains water. In one embodiment, the liquid of the composition of insoluble diphenyl sulfone derivatives is at least one selected from the group consisting of ethanol, isopropanol and acetone. Preferably the liquid of the composition of insoluble diphenyl sulfone derivatives is ethanol.
In the preparation method of the diphenyl sulfone derivative composition, the 4,4' -dihydroxy diphenyl sulfone salt is firstly formed as a reaction intermediate through two-step reaction, and then substitution reaction is carried out, so that the synthesis reaction path is effectively controlled, the reaction achieves the effect of high selectivity, and the high-purity diphenyl sulfone derivative is prepared.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and those skilled in the art can easily understand the advantages and effects of the present invention from the disclosure of the present specification. The invention is capable of other and different embodiments and its several details are capable of modification in various other respects, all without departing from the spirit and scope of the present disclosure. Moreover, all ranges and values herein are inclusive and combinable. Any number or point within the ranges set forth herein, e.g., any integer, may be treated as the minimum or maximum value to derive a lower range, etc.
According to the present invention, a composition of diphenyl sulfone derivatives comprises: a compound having n of 1 and a compound having n of 2 of the following formula (I), wherein the weight ratio of the compound having n of 1 to the compound having n of 2 is 2.16:1 to 2.41: 1. Other ratios that may be considered minimum or maximum values are 2.32:1 and 2.37: 1.
Compared with the existing diphenyl sulfone derivative, the composition of the diphenyl sulfone derivative disclosed by the invention mainly comprises the compound with n being 1 and the compound with n being 2 in the structures shown in the formula (I), and the weight ratio of the compound with n being 1 is higher than that of the compound with n being 2, so that the composition disclosed by the invention has stable color development performance.
In one embodiment, the difference in melting points of the composition of diphenyl sulfone derivatives ranges from 12 ℃ to 14 ℃. The melting point range is related to the purity of the compound, with higher purity compounds having a narrower melting point range. Therefore, when the weight ratio of the compound with n being 1 is higher, the purity of the composition representing the diphenyl sulfone derivative is higher, and the melting point range is smaller.
The invention also provides a preparation method of the diphenyl sulfone derivative composition, which comprises the following steps: dissolving 4,4 '-dihydroxydiphenyl sulfone in a first solvent, and adding an aqueous alkaline solution for pre-reaction to form a 4,4' -dihydroxydiphenyl sulfone salt, wherein the weight ratio of the reaction alkali to water of the aqueous alkaline solution is 35:65 to 50: 50; isolating the 4,4' -dihydroxydiphenyl sulfone salt; mixing the separated 4,4' -dihydroxydiphenyl sulfone salt with a second solvent and haloethyl ether to form a reaction system for substitution reaction; and adding an acid solution after the substitution reaction is completed to obtain the composition of the diphenyl sulfone derivative.
First, in the preparation method of the present invention, the first solvent may be a polar protic solvent or a polar aprotic solvent, and particularly, a polar aprotic solvent is preferable. In one embodiment, the first solvent is a polar protic solvent and is at least one selected from the group consisting of water, methanol, ethanol, propanol, butanol and isopropanol. In another embodiment, the first solvent is a polar aprotic solvent and is at least one selected from the group consisting of acetone, dimethyl sulfoxide, dimethylformamide, and tetrahydrofuran, preferably the polar aprotic solvent is tetrahydrofuran.
In one embodiment, the reaction base comprises an alkali metal hydroxide, such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; alkali metal carbonates such as calcium carbonate; and organic bases such as triethylamine, pyridine and diazabicyclo [5.4.0] undec-7-ene. In one embodiment, the weight ratio of the reaction base to the 4,4' -dihydroxydiphenyl sulfone is 1: 3.125.
Preferably, the reaction base is an alkali metal hydroxide, wherein the alkali metal hydroxide is sodium hydroxide. In one embodiment, the purity of the sodium hydroxide is preferably 98% or more. The purity of the 4,4' -dihydroxydiphenyl sulfone is preferably 99% or more.
In the preparation method of the present invention, the pre-reaction is usually carried out at room temperature, at a temperature ranging from 15 to 40 ℃, for example, 15 ℃, 16 ℃, 17 ℃, 18 ℃, 19 ℃, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃, 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 or 40 ℃, and the pre-reaction is allowed to proceed for 0.5 to 2 hours, for example, 0.5 hour, 1 hour, 1.5 hours or 2 hours. In one embodiment, the pre-reaction temperature may be 25 ℃. In another embodiment, the pre-reaction time may be 0.5 to 1 hour.
To avoid affecting the degree of salting of 4,4' -dihydroxydiphenyl sulfone, the amount of water used in the pre-reaction process must be controlled. If the degree of salinization is not complete, the solubility of the 4,4' -dihydroxydiphenyl sulfone salt in water will be affected, and the subsequent substitution reaction will be affected. For example, when the preliminary reaction is carried out by adding an aqueous alkaline solution, the weight ratio of the reaction alkali to water of the aqueous alkaline solution is 35:65 to 50: 50. E.g., 35:65, 36:64, 37:63, 38:62, 39:61, 40:60, 41:59, 42:58, 43:57, 44:56, 45:55, 46:54, 47:53, 48:52, 49:50, or 50: 50. In one embodiment, the weight ratio of sodium hydroxide to water may be 50: 50.
According to the invention, the 4,4' -dihydroxydiphenyl sulfone salt is firstly formed to be used as a reaction intermediate, so that the synthetic route of the diphenyl sulfone derivative can be effectively controlled, and the aim of improving the selectivity of the composition of the diphenyl sulfone derivative is fulfilled.
The isolation procedure after the pre-reaction is to separate the 4,4' -dihydroxydiphenyl sulfone salt from the first solvent to avoid excessive solvent affecting the yield.
The substitution reaction is carried out at a temperature ranging from room temperature to the boiling point of the second solvent, so that the halogen atom is removed from the haloethyl ether and the haloethyl ether is combined with the 4,4' -dihydroxydiphenyl sulfone ion in the solution.
In one embodiment, the second solvent is selected from the group consisting of water and an aqueous ethanol solution. The second solvent may not account for too high a weight of the reaction system to avoid affecting the progress of the substitution reaction. Wherein the second solvent is preferably water, and the proportion of water by weight of the reaction system is 25 wt% to 60 wt%, for example, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt% or 60 wt%. Preferably, the proportion of water is 25 to 27% by weight of the reaction system.
In one embodiment, the haloethyl ether is bis (2-chloroethyl) ether. In one embodiment, the bis (2-chloroethyl) ether is preferably more than 99% pure.
The method for preparing the diphenyl sulfone derivative composition of the present invention may further comprise dissolving the separated 4,4' -dihydroxydiphenyl sulfone salt in a second solvent before the substitution reaction, and then adding the haloethyl ether to the second solvent in which the 4,4' -dihydroxydiphenyl sulfone salt is dissolved, wherein the addition rate of the haloethyl ether to the 4,4' -dihydroxydiphenyl sulfone is 0.15 wt% to 0.25 wt% per minute, for example, 0.15 wt%, 0.16 wt%, 0.17 wt%, 0.18 wt%, 0.19 wt%, 0.20 wt%, 0.21 wt%, 0.22 wt%, 0.23 wt%, 0.24 wt%, or 0.25 wt%. In another embodiment, the haloethyl ether is added in portions or intervals, for example, the haloethyl ether is added dropwise to the second solvent in which the 4,4' -dihydroxydiphenylsulfone salt is dissolved. In another embodiment, the haloethyl ether is added for a period of time ranging from 1 to 3 hours, for example, 1 hour, 2 hours, or 3 hours.
In one embodiment, the substitution reaction temperature is from 80 ℃ to 110 ℃, e.g., 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 100 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 105 ℃, 106 ℃ or 107 ℃, 108 ℃, 109 ℃, 110 ℃. In another embodiment, the substitution reaction is carried out at a temperature in the range of 80 ℃ to 110 ℃ for 8 to 16 hours, e.g., 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, or 16 hours, after the addition of the haloethyl ether is complete. In another embodiment, the substitution reaction is carried out at 100 ℃ to 110 ℃ for 8 to 9 hours.
In still another embodiment, the diphenyl sulfone derivative composition of the present invention is prepared by dissolving the separated 4,4' -dihydroxydiphenyl sulfone salt in a second solvent before the substitution reaction, then dropwise adding the haloethyl ether to the second solvent in which the 4,4' -dihydroxydiphenyl sulfone salt is dissolved within 1 to 3 hours at a dropwise addition rate of 0.15 to 0.25 wt% per minute relative to the 4,4' -dihydroxydiphenyl sulfone, and after completion of the dropwise addition of the haloethyl ether, performing the substitution reaction at a temperature ranging from 80 to 110 ℃ for 8 to 16 hours.
In one embodiment, the acid solution is sulfuric acid. The sulfuric acid is used for neutralization, and the method is characterized in that no lump aggregation is formed at the end point of dripping, the condition that a byproduct is coated in a lump is improved, and the purification process can be simplified; the use of hydrochloric acid has a problem that the subsequent treatment step is complicated.
Further, the method for producing the diphenyl sulfone derivative composition of the present invention further comprises washing and filtering the crystals using a liquid in which the diphenyl sulfone derivative composition is not soluble after the crystals of the diphenyl sulfone derivative composition are obtained by adding the acid solution, wherein the liquid contains water. In one embodiment, the filtration temperature may be from 25 ℃ to 60 ℃.
By this method, unreacted bisphenol S, by-products and other impurities can be removed, which can degrade the performance of the composition of the diphenyl sulfone derivative as a developer, and there is no need to wait for the solution to be cooled to a low temperature, and there is no need to use a highly volatile organic solvent, which contributes to the improvement of the purity of the composition of the diphenyl sulfone derivative, and further yields a composition of the diphenyl sulfone derivative having excellent performance as a developer.
In one embodiment, the liquid in which the diphenyl sulfone derivative composition is insoluble is at least one selected from the group consisting of ethanol, isopropanol, and acetone. Preferably, the liquid in which the composition of diphenyl sulfone derivatives is insoluble is ethanol and is dissolved in water to form an aqueous ethanol solution.
The ethanol concentration of the ethanol aqueous solution is preferably 50 vol%, and the number of washing can be reduced.
The preparation method comprises two reaction steps and purification steps, such as washing and filtering, so that the product is separated from impurities; after the purification step is completed, process steps for isolating the composition of the diphenyl sulfone derivative, such as crystallization, distillation, filtration and recrystallization, may also be included; and process steps particularly required for industrial production, such as drying and solvent recovery, and each process step may be a combination of two or more times.
The diphenyl sulfone derivative composition obtained by the above-mentioned preparation method of the present invention has good coloring sensitivity and preservability, and is useful for products such as color-developing agents for thermal paper.
The present invention is further illustrated in detail by examples.
Comparative example 1:
47.5mL of distilled water, 25.6g of sodium hydroxide and 80g of 4,4' -dihydroxydiphenyl sulfone were placed in a vessel (GL vessel) whose inner wall was lined with glass, heated to 110 ℃ and stirred for 4 hours to dissolve the above substances.
To the resulting solution was added 20.34g of bis (2-chloroethyl) ether at 110 ℃ and stirring was continued at the same temperature for 8 hours. 108.1mL of hot water was added to the solution, it was allowed to cool to 70 ℃, 167.4mL of 90% strength by volume aqueous methanol was added and stirred for 30 minutes to homogenize. Thereafter, 116.4g of 10 wt% hydrochloric acid was slowly added dropwise at 71 ℃ to bring the pH to 4 to 5, and the temperature was maintained for 1 hour. After cooling to 25 to 30 ℃, the temperature was maintained for 8 hours. Washing and drying at 30 deg.C with 50% volume methanol aqueous solution to obtain 56.95g of diphenyl sulfone derivative composition in powder form, and mixing the yield and the weight ratio (n) of the diphenyl sulfone derivative composition1Is a compound of formula (I) where n is 1, n2Compound n ═ 2 for formula (I), melting point values and ranges of melting point spread are reported in table 1.
The composition of diphenyl sulfone derivative is obtained by High Performance Liquid Chromatography (HPLC) analysis using Polaris 5C-18(25cm × 6mm) column and ACN: H2O60: 40 as mobile phase, and ultraviolet wavelength is 280 nm.
Comparative example 2:
40mL of distilled water, 25.6g of sodium hydroxide, 80g of 4,4' -dihydroxydiphenyl sulfone and 40g of ethanol were placed in a GL vessel, and the mixture was stirred at 85 ℃ for 4 hours to dissolve the above substances.
To the resulting solution was added 20.34g of bis (2-chloroethyl) ether at 85 ℃ and stirred at the same temperature for 8 hours. 108mL of hot water was added to the solution and cooled to 70 ℃, 167mL of an aqueous 95% strength by volume ethanol solution was added and stirred for 30 minutes to homogenize. Thereafter, 78.48g of 20 wt% sulfuric acid was slowly added dropwise to bring the pH to 4 to 5, and stirring was continued for 1 hour, and cooling to room temperature and holding for 8 hours. Washing and drying at 55 ℃ with 50% by volume aqueous ethanol solution gave 41.7g of the diphenyl sulfone derivative composition in powder form, and the yield, the composition in weight ratio of the diphenyl sulfone derivative composition, the melting point value and the range of the melting point difference were recorded in Table 1.
Example 1:
80g of 4,4 '-dihydroxydiphenyl sulfone was dissolved in 170mL of ethanol, and 51.2g of 50 wt% aqueous sodium hydroxide solution was added, and the mixture was placed in a GL container and reacted at 25 ℃ for 1 hour to obtain 4,4' -dihydroxydiphenyl sulfone sodium salt.
The 4,4 '-dihydroxydiphenyl sulfone sodium salt was filtered, dried, mixed with 48g of distilled water, and 20.34g of bis (2-chloroethyl) ether was added dropwise at an addition rate of 0.21 wt% per minute for two hours (the addition rate was the amount of the bis (2-chloroethyl) ether to the 4,4' -dihydroxydiphenyl sulfone), and the mixture was stirred at 110 ℃ for 8 hours to carry out substitution reaction. After the reaction was completed, 108mL of hot water was added and cooled to 80 ℃, and then 167mL of 95% ethanol aqueous solution by volume was added at 70 ℃ and stirred for 30 minutes to homogenize. Thereafter, 78.48g of 20 wt% sulfuric acid was added dropwise to bring the pH to 4 to 5, and after stirring was continued for one hour, the mixture was cooled to room temperature and held for 8 hours. The washing and drying at 55 ℃ with 50% by volume aqueous ethanol solution gave 62.3g of a composition of diphenyl sulfone derivative in powder form, the yield of which, the composition of the composition in weight proportions of the diphenyl sulfone derivative, the melting point values and the ranges of the melting point spread are reported in table 1.
Example 2:
the same procedure as in example 1, but replacing the ethanol in which the 4,4' -dihydroxydiphenyl sulfone was dissolved with Tetrahydrofuran (THF), gave 62.8g of a composition of diphenyl sulfone derivatives in powder form, and the yield, the composition of the composition in weight proportions of the diphenyl sulfone derivatives, the melting point values and the ranges of the melting point differences are reported in table 1.
Example 3:
the same procedure as in example 1, but with a substitution reaction temperature of 105 ℃ was followed, 51.6g of the diphenyl sulfone derivative composition in powder form was obtained, and the yield, the composition of the composition in weight ratio of the diphenyl sulfone derivative, the melting point values and the ranges of the melting point differences were recorded in Table 1.
Example 4:
the same procedure as in example 1 was followed, except that acetone was used instead of ethanol in which 4,4' -dihydroxydiphenyl sulfone was dissolved, and 50% by volume aqueous acetone was used instead of 50% by volume aqueous ethanol, followed by washing and drying, 58.4g of a diphenyl sulfone derivative composition in the form of powder was obtained, and the yield thereof, the composition of the diphenyl sulfone derivative composition in terms of weight ratio, the melting point value and the range of the difference in melting point were recorded in Table 1.
TABLE 1
In summary, the preparation method of the diphenyl sulfone derivative composition of the present invention comprises the steps of carrying out a two-step reaction, firstly forming the 4,4' -dihydroxy diphenyl sulfone salt as a reaction intermediate, and then carrying out a substitution reaction to effectively control the synthesis reaction path, so that the reaction achieves the effect of high selectivity, thereby obtaining the high purity diphenyl sulfone derivative.
The above embodiments are merely illustrative, and not restrictive, of the invention. Modifications and variations can be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the present invention. Therefore, the scope of the invention is defined by the appended claims, and is covered by the disclosure unless it does not affect the effect and the implementation of the invention.
Claims (21)
1. A diphenyl sulfone derivative composition comprising a compound of the following formula (I) wherein n is 1 and a compound of the following formula (I) wherein n is 2,
and the weight ratio of the compound with n being 1 to the compound with n being 2 is 2.16:1 to 2.41: 1.
2. The diphenyl sulfone derivative composition as set forth in claim 1, which has a difference in melting points ranging from 12 ℃ to 14 ℃.
3. A process for the preparation of a composition of diphenyl sulfone derivatives as set forth in claim 1, comprising:
dissolving 4,4 '-dihydroxydiphenyl sulfone in a first solvent, and adding an aqueous alkaline solution for pre-reaction to form a 4,4' -dihydroxydiphenyl sulfone salt, wherein the weight ratio of the reaction alkali to water of the aqueous alkaline solution is 35:65 to 50: 50;
isolating the 4,4' -dihydroxydiphenyl sulfone salt;
mixing the separated 4,4' -dihydroxydiphenyl sulfone salt with a second solvent and haloethyl ether to form a reaction system for substitution reaction; and
adding an acid solution after the substitution reaction is completed to obtain the composition of the diphenyl sulfone derivative.
4. The method of claim 3, wherein the first solvent is selected from a polar protic solvent or a polar aprotic solvent.
5. The method according to claim 4, wherein the polar protic solvent is at least one selected from the group consisting of water, methanol, ethanol, propanol, butanol and isopropanol.
6. The method according to claim 4, wherein the polar aprotic solvent is at least one selected from the group consisting of acetone, dimethyl sulfoxide, dimethylformamide and tetrahydrofuran.
7. The method of claim 3, wherein the pre-reaction is carried out at 15 to 40 ℃ for 0.5 to 2 hours.
8. The method of claim 3, wherein the reaction base is one selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, and organic bases.
9. The method of claim 8, wherein the reaction base is sodium hydroxide.
10. The method of claim 3, wherein the second solvent is water or an aqueous ethanol solution.
11. The method according to claim 10, wherein the second solvent comprises water in a proportion of 25 to 60 wt% based on the weight of the reaction system.
12. The method of claim 3, wherein the haloethyl ether is bis (2-chloroethyl) ether.
13. The method of claim 3, further comprising adding the haloethyl ether to the second solvent in which the 4,4' -dihydroxydiphenyl sulfone salt is dissolved after the separated 4,4' -dihydroxydiphenyl sulfone salt is dissolved before the substitution reaction, wherein the addition rate of the haloethyl ether to the 4,4' -dihydroxydiphenyl sulfone is 0.15 wt% to 0.25 wt% per minute.
14. The method of claim 13, wherein the haloethyl ether is added dropwise to the second solvent in which the 4,4' -dihydroxydiphenylsulfone salt is dissolved.
15. The process of claim 13, wherein the haloethyl ether is added for a period of time of 1 to 3 hours.
16. The method of claim 3, wherein the substitution reaction temperature is 80 ℃ to 110 ℃.
17. The method of claim 3, wherein the substitution reaction is carried out at a temperature ranging from 80 ℃ to 110 ℃ for 8 to 16 hours after the addition of the haloethyl ether is completed.
18. The method of claim 3, wherein the acid solution is sulfuric acid.
19. The production method according to claim 3, further comprising washing and filtering the crystals using a liquid in which the diphenyl sulfone derivative composition is insoluble after the crystals of the diphenyl sulfone derivative composition are obtained by adding the acid liquid, wherein the liquid contains water.
20. The method of claim 19, wherein the liquid in which the diphenyl sulfone derivative composition is insoluble is at least one selected from the group consisting of ethanol, isopropanol and acetone.
21. The method of claim 20, wherein the liquid in which the diphenyl sulfone derivative composition is insoluble is ethanol.
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| WO2004089883A1 (en) * | 2003-04-03 | 2004-10-21 | Sanko Chemical Industry Co., Ltd. | Method for producing 3,3’-diallyl-4,4’-dihydroxydiphenylsulfone |
| JP5090529B2 (en) * | 2008-06-18 | 2012-12-05 | 日本曹達株式会社 | Developable composition and recording material containing the same |
| CN102112321B (en) * | 2008-08-04 | 2014-03-12 | 日本曹达株式会社 | Color developing composition containing molecular compound, and recording material |
| CN107793567B (en) * | 2016-12-20 | 2020-04-14 | 金发科技股份有限公司 | Polyether sulfone resin containing methoxyl diphenyl sulfone ether group and synthetic method and application thereof |
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| JP2000255168A (en) * | 1999-03-08 | 2000-09-19 | Oji Paper Co Ltd | Adhesive sheet for heat sensitive recording and method for using the sheet |
| JP2001030635A (en) * | 1999-07-26 | 2001-02-06 | Nippon Steel Chem Co Ltd | Heat-sensitive recording material |
| JP2001138638A (en) * | 1999-11-10 | 2001-05-22 | Mitsubishi Paper Mills Ltd | Multi-color heat sensitive recording material |
| CN102015320A (en) * | 2008-05-07 | 2011-04-13 | 日本曹达株式会社 | Color-developing composition and recording material containing same |
| JP2010149453A (en) * | 2008-12-26 | 2010-07-08 | Hokuetsu Kishu Paper Co Ltd | Thermal recording paper |
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