CN101928193A - Method for preparing symmetrical disulfide compound - Google Patents
Method for preparing symmetrical disulfide compound Download PDFInfo
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- CN101928193A CN101928193A CN2010102524056A CN201010252405A CN101928193A CN 101928193 A CN101928193 A CN 101928193A CN 2010102524056 A CN2010102524056 A CN 2010102524056A CN 201010252405 A CN201010252405 A CN 201010252405A CN 101928193 A CN101928193 A CN 101928193A
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Abstract
The invention discloses a method for preparing a symmetrical disulfide compound. In the method, a compound shown as a formula (III) is taken as a raw material, and a CoSalen complex shown as a formula (I) or (II) is taken as a catalyst; and the method comprises the following steps of: in an organic solvent, introducing air or oxygen serving as an oxidant, reacting at the temperature of between 20 and 100 DEG C, tracking and monitoring until the reaction is completed, and after the reaction is finished, performing after treatment on reacting fluid to prepare the symmetrical disulfide compound shown as a formula (IV). Compared with the prior art, the method for preparing the symmetrical disulfide compound has the advantages of simple and convenient operation, mild reaction condition, low cost, easy preparation and small dosage of the adopted catalyst, low cost, easy acquirement and cleanness of the adopted oxidant gas, low content of the impurity of disulfide as the finished product, higher yield, commercial prospect and remarkable application value and social and economic benefits.
Description
Technical field
The present invention relates to the novel method that a kind of new catalyzed oxidation thio-alcohol or phenyl-sulfhydrate compounds prepare corresponding symmetrical disulfide compound.The symmetry disulfide compound is the intermediate of the important medicine of a class, agricultural chemicals, dyestuff and macromolecular material.
Background technology
Disulfide claims disulfide again, is mainly made by corresponding sulfhydryl compound oxidation.Before the present invention, symmetrical disulfide mainly contains following bibliographical information its preparation method.(1) people such as Hamid Golchoubian has reported with Mn (III) schiff bases complex as catalyzer, air is as oxygenant, and catalyzed oxidation mercaptan or thiophenol prepare symmetrical disulfide, and yield is at 86-98%(Catalysis Communications. 2007,8,697-700); (2) people such as Wang Hua has described with metal alkyl compound and cupric chloride system catalyzed oxidation mercaptan and has prepared disulfide, and yield is at 85%-95%(CN 101475517).The difficult preparation of the catalyzer of document 1 reported method key; Document 2 reported method relate to the reagent to the water and air sensitivity, must carry out in special container.This makes these methods be subject to many limitations in actual applications.
Summary of the invention
The purpose of this invention is to provide a kind of cleaning, easy, low cost, the catalyzed oxidation of less energy-consumption contains the compound of sulfydryl, thereby prepares the method for corresponding symmetrical disulfide.
For this reason, the technical solution used in the present invention is:
A kind of method for preparing symmetrical disulfide compound, described method is: being raw material suc as formula the compound shown in (III), with the CoSalen title complex shown in formula I or (II) is catalyzer, in organic solvent, bubbling air or oxygen are as oxygenant, and 20 ~ 100 ℃ of temperature condition react down, and tracking monitor is to reacting completely, usually follow the tracks of with TLC and detect, reaction finishes the aftertreatment of afterreaction liquid and makes suc as formula the symmetrical disulfide compound shown in (IV); Described organic solvent is the alcohol of C1 ~ C4, the ester compound of C2 ~ C6, the halogenated hydrocarbon compound of C1 ~ C2, acetonitrile, benzene or alkyl substituted benzene;
R
3SH R
3SS?R
3
（III） （IV）
In described formula (I) or the formula (II), R
1Or R
2Independent separately is H or OCH
3
In described formula (III) or the formula (IV), R
3Be C
6H
5-, p-H
3CC
6H
4-, p-ClC
6H
4-, p-BrC
6H
4-, p-FC
6H
4-, p-(H
3CS) C
6H
4-, p-H
2NC
6H
4-, p-HOC
6H
4-, p-H
3COC
6H
4-, p-O
2NC
6H
4-, o-HOOCC
6H
4-, o-H
2NC
6H
4-, m-ClC
6H
4-, o-ClC
6H
4-, o-O
2NC
6H
4-, o-(C
6H
5NHCO) C
6H
4-, m-H
3COC
6H
4-, m-O
2NC
6H
4-, 3,5-(F
3C)
2C
6H
3-, C
6H
5CH
2-, 2-[4-morpholinodithio base, furfuryl, 2-naphthyl, (H
3C)
2CH-or H
3C (CH
2)
2CH
2-.
Concrete reaction equation is as follows:
Comparatively concrete, described CATALYST Co Salen title complex is N, N '-two salicylidene triethylenediamine cobalts, N, N '-two (4-methoxyl group salicylidene) triethylenediamine cobalt, N, N '-two salicylidenes-1, the 2-propylene diamine closes cobalt or N, N '-two (4-methoxyl group salicylidene)-1, the 2-propylene diamine closes cobalt.
Described organic solvent is preferably methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, methyl acetate, ethyl acetate, propyl acetate, butylacetate, butyl formate, ethyl formate, methylene dichloride, trichloromethane, tetracol phenixin, 1,2-ethylene dichloride, acetonitrile, benzene, toluene, ethylbenzene or dimethylbenzene most preferably are methyl alcohol, ethanol, ethyl acetate, tetracol phenixin or toluene.
Described volume of organic solvent consumption is preferably 10 ~ 30 mL/g to count 5 ~ 100mL/g suc as formula the quality of the compound shown in (III).
Described suc as formula the compound shown in (III) and catalyzer the ratio of amount of substance be 1:0.01 ~ 0.1, preferred 1:0.025 ~ 0.05.
Described temperature is 20 ~ 100 ℃, preferred room temperature or solvent refluxing temperature, and described solvent refluxing temperature is meant that solvent boiling point is lower than 100 ℃ solvent refluxing temperature.
The described reaction times is generally 0.1 ~ 10 hour, preferred 0.3 ~ 1 hour.
Described reaction solution post-treating method is: after reaction finished, reaction solution was cooled to room temperature, and steaming desolventizes, and obtains the symmetrical disulfide compound crude product, and described symmetrical disulfide compound crude product purification processes obtains the pure product of symmetrical disulfide compound.
Comparatively concrete, described purification processing method is one of following:
(A) with symmetrical disulfide compound crude product recrystallization solvent recrystallization, obtain the pure product of symmetrical disulfide compound, described recrystallization solvent is C
5~ C
12Alkane, toluene or C
1~ C
4Alcohol, preferred sherwood oil, toluene or ethanol.
(B) the symmetrical disulfide compound crude product is carried out column chromatography for separation, with C
5~ C
12Alkane, C
2~ C
6Ester, C
1~ C
4Alcohol or C
1~ C
2Halohydrocarbon make eluent, TLC detects, and collects the elutriant that contains symmetrical disulfide compound, eluent is removed in the elutriant distillation, obtains the pure product of symmetrical disulfide compound, described eluent is preferably sherwood oil, ethyl acetate, ethanol or methylene dichloride.
Catalyzer of the present invention can prepare in accordance with the following methods, and described preparation method well known to a person skilled in the art method:
A, N, the preparation of N '-two salicylidene triethylenediamine cobalts:
Salicylic aldehyde and quadrol are in alcohol solvent, and stirring reaction is 1 ~ 2 hour under the room temperature, and suction filtration is dried after the filter cake washing, get schiff bases I, and the ratio of the amount of substance of described salicylic aldehyde and quadrol is 2:1; Schiff bases I and Cobalt diacetate tetrahydrate are in alcohol solvent, stirring reaction is 2 ~ 3 hours under the room temperature, heating reflux reaction is 1 ~ 2 hour then, be cooled to suction filtration after the room temperature, filter cake washing obtains N, N '-two salicylidene triethylenediamine cobalts, described schiff bases I is 1 ~ 1.5:1 with the ratio of the amount of substance of Cobalt diacetate tetrahydrate.
B, N, the preparation of N '-two (4-methoxyl group salicylidene) triethylenediamine cobalt:
4-methoxysalicylaldehyde and quadrol are in alcohol solvent, and stirring reaction is 1 ~ 2 hour under the room temperature, and suction filtration is dried after the filter cake washing, get schiff bases II, and the ratio of the amount of substance of described 4-methoxysalicylaldehyde and quadrol is 2:1; Schiff bases II and Cobalt diacetate tetrahydrate are in alcohol solvent, stirring reaction is 2 ~ 3 hours under the room temperature, heating reflux reaction is 1 ~ 2 hour then, be cooled to suction filtration after the room temperature, filter cake washing obtains N, N '-two (4-methoxyl group salicylidene) triethylenediamine cobalt, described schiff bases II is 1 ~ 1.5:1 with the ratio of the amount of substance of Cobalt diacetate tetrahydrate.
C, N, N '-two salicylidenes-1, the 2-propylene diamine closes the preparation of cobalt:
Salicylic aldehyde and 1,2-propylene diamine are in alcohol solvent, and stirring reaction is 1 ~ 2 hour under the room temperature, and suction filtration is dried after the filter cake washing, get schiff bases III, described salicylic aldehyde and 1, and the ratio of the amount of substance of 2-propylene diamine is 2:1; Schiff bases III and Cobalt diacetate tetrahydrate are in alcohol solvent, stirring reaction is 2 ~ 3 hours under the room temperature, heating reflux reaction is 1 ~ 2 hour then, be cooled to suction filtration after the room temperature, filter cake washing obtains N, N '-two salicylidenes-1, the 2-propylene diamine closes cobalt, and described schiff bases III is 1 ~ 1.5:1 with the ratio of the amount of substance of Cobalt diacetate tetrahydrate.
D, N, N '-two (4-methoxyl group salicylidene)-1, the 2-propylene diamine closes the preparation of cobalt
4-methoxysalicylaldehyde and 1,2-propylene diamine are in alcohol solvent, and stirring reaction is 1 ~ 2 hour under the room temperature, and suction filtration is dried after the filter cake washing, get schiff bases IV, described salicylic aldehyde and 1, and the ratio of the amount of substance of 2-propylene diamine is 2:1; Schiff bases IV and Cobalt diacetate tetrahydrate are in alcohol solvent, stirring reaction is 2 ~ 3 hours under the room temperature, heating reflux reaction is 1 ~ 2 hour then, be cooled to suction filtration after the room temperature, filter cake washing obtains N, N '-two (4-methoxyl group salicylidene)-1, the 2-propylene diamine closes cobalt, and described schiff bases IV is 1 ~ 1.5:1 with the ratio of the amount of substance of Cobalt diacetate tetrahydrate.
The present invention is a raw material with mercaptan or thiophenol, and as oxygenant, metal complexes CoSalen prepares symmetrical disulfide as catalyzer with the cleaning oxidizer air or oxygen.The present invention compared with prior art, easy and simple to handle, reaction conditions is gentle, easy preparation of inexpensive catalyst and consumption are few, cheap and easy to get and the cleaning of used oxygenant air, product disulfide foreign matter content is few, yield is higher, has Commercial Prospect, has tangible implementary value and society, economic benefit.
Embodiment
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited to this.
Preparation of catalysts:
A, N, the preparation of N '-two salicylidene triethylenediamine cobalts:
The preparation of schiff bases I:
Take by weighing salicylic aldehyde 48.8 g(0.4 mol), be dissolved in 240 ml industrial spirit and join in the four-hole boiling flask; Take by weighing quadrol 12.0 g(0.2 mol), be added drop-wise in the reaction flask, open simultaneously and stir, reaction 1 h under the room temperature, suction filtration, and with 200 ml industrial spirit washing leaching cakes, dry, getting light yellow solid (52.0 g), yield is 96%.
CATALYST Co Salon (I, R
1=H) preparation:
Get the above-mentioned schiff bases I that makes 30.0 g(0.112 mol) with 26.7 g(0.107 mol) Cobalt diacetate tetrahydrate is mixed to join in the four-hole boiling flask, adds industrial spirit 225 ml in reaction flask, open and stir, room temperature reaction 2 h; Be heated to 60 ~ 70 ℃ of temperature then, back flow reaction 1 h; Be cooled to 20 ℃, suction filtration, and with 100 ml industrial spirit wash sorrel solid N, N '-two salicylidene triethylenediamine cobalts is CATALYST Co Salon (I, R
1=H) (34.5 g), yield is 95%.
B, N, the preparation of N '-two (4-methoxyl group salicylidene) triethylenediamine cobalt:
The preparation of schiff bases II:
Take by weighing 4-methoxysalicylaldehyde 60.8 g(0.4 mol), be dissolved in 240 ml industrial spirit and join in the four-hole boiling flask; Take by weighing quadrol 12.0 g(0.2 mol), be added drop-wise in the reaction flask, open simultaneously and stir, reaction 1 h under the room temperature, suction filtration, and with 200 ml industrial spirit washing leaching cakes, dry, getting light yellow solid (63.6 g), yield is 96%.
CATALYST Co Salon (I, R
1=OCH
3) preparation
Get the above-mentioned schiff bases II that makes 36.7 g(0.112 mol) with 26.7 g(0.107 mol) Cobalt diacetate tetrahydrate is mixed to join in the four-hole boiling flask, adds industrial spirit 225 ml in reaction flask, open and stir, room temperature reaction 2 h; Be heated to temperature at 60 ~ 70 ℃, back flow reaction 1 h; Be cooled to temperature at 20 ℃, suction filtration, and with 100 ml industrial spirit wash sorrel solid N, N '-two (4-methoxyl group salicylidene) triethylenediamine cobalt is CATALYST Co Salon (I, R
1=OCH
3) (40.2 g), yield is 95%.
C, N, N '-two salicylidenes-1, the 2-propylene diamine closes the preparation of cobalt:
The preparation of schiff bases III:
Take by weighing salicylic aldehyde 48.8 g(0.4 mol), be dissolved in 240 ml industrial spirit and join in the four-hole boiling flask; Take by weighing 1,2-propylene diamine 14.8 g(0.2 mol), be added drop-wise in the reaction flask, open simultaneously and stir, reaction 1 h under the room temperature, suction filtration, and with 200 ml industrial spirit washing leaching cakes, dry, getting light yellow solid (53.0 g), yield is 94%.
CATALYST Co Salon (II, R
2=H) preparation
Get the above-mentioned schiff bases III that makes 31.6 g(0.112 mol) with 26.7 g(0.107 mol) Cobalt diacetate tetrahydrate is mixed to join in the four-hole boiling flask, adds industrial spirit 225 ml in reaction flask, open and stir, room temperature reaction 2 h; Be heated to temperature at 60 ~ 70 ℃, back flow reaction 1 h; Be cooled to 20 ℃, suction filtration, and with 100 ml industrial spirit wash sorrel solid N, N '-two salicylidenes-1, the 2-propylene diamine closes cobalt, is CATALYST Co Salon (II, R
2=H) (35.8 g), yield is 95%.
D, N, N '-two (4-methoxyl group salicylidene)-1, the 2-propylene diamine closes the preparation of cobalt
The preparation of schiff bases IV:
Take by weighing 4-methoxysalicylaldehyde 60.8 g(0.4 mol), be dissolved in 240 ml industrial spirit and join in the four-hole boiling flask; Take by weighing 1,2-propylene diamine 14.8 g(0.2 mol), be added drop-wise in the reaction flask, open simultaneously and stir, reaction 1 h under the room temperature, suction filtration, and with 200 ml industrial spirit washing leaching cakes, dry, getting light yellow solid (62.9 g), yield is 92%.
CATALYST Co Salon (II, R
2=OCH
3) preparation
Get the above-mentioned schiff bases IV that makes 38.3 g(0.112 mol) with 26.7 g(0.107 mol) Cobalt diacetate tetrahydrate is mixed to join in the four-hole boiling flask, adds industrial spirit 225 ml in reaction flask, open and stir, room temperature reaction 2 h; Be heated to temperature at 60 ~ 70 ℃, back flow reaction 1 h; Be cooled to 20 ℃, suction filtration, and with 100 ml industrial spirit wash sorrel solid N, N '-two (4-methoxyl group salicylidene)-1, the 2-propylene diamine closes cobalt, is CATALYST Co Salon (II, R
2=OCH
3) (41.5 g), yield is 95%.
Embodiment 1 substrate is a 2-mercaptobenzothiazole, and catalyzer is N, N '-two salicylidene triethylenediamine cobalts, and organic solvent is a dehydrated alcohol.The amount of substance that feeds intake ratio is substrate: catalyzer 1:0.025, mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10.
With 50.1 g(0.3 mol) 2-mercaptobenzothiazole and 2.44 g(0.0075 mol) catalyzer (I) mixing, join and be equipped with in thermometer and the churned mechanically 1000 ml there-necked flasks, add 500 ml dehydrated alcohols again, open and stir, blowing air is heated to 60 ℃, insulation reaction, TLC follows the tracks of detection, and reaction in 1 hour finishes.Naturally cool to 20 ℃, steaming desolventizes, with obtaining light yellow solid 45.7 g behind the 50 ml toluene recrystallizations, and yield 91.8%, purity 99.1%, m.p.178 ~ 179 ℃;
1H NMR (500 MHz, CDCl
3): δ 8.01 (d,
J=8.0 Hz, 2H), 7.85 (d,
J=8.0 Hz, 2H), 7.54 (d,
J=7.5 Hz, 2H), 7.43 (d,
J=7.0 Hz, 2H).IR?(?KBr?)：2922，,669，443?cm
-1。MS?(?EI,?70?eV?):?m/z=332（100，M
+）。
Embodiment 2
Substrate changes thiophenol 33.0 g(0.3 mol into), catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition and preparation process are all with embodiment 1.Obtain Off-white solid 29.5 g, yield 90%, purity 99.2%, 60 ~ 61 ℃ of m.p.
1H?NMR(500?MHz，CDCl
3)：δ7.50?(d,?
J=8.5?Hz,?4H),?7.31?(t,?
J=7.5?Hz,?4H),?7.25?(t,?
J=7.0?Hz,?2H)。IR?(?KBr?)：3070，,685，461?cm
-1。MS?(?EI,?70?eV?):?m/z=218（100，M
+）。
Embodiment 3
Substrate changes 4-methylbenzene thiophenol 37.2 g(0.3 mol into), catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition and preparation process are all with embodiment 1.Obtain oyster white crystal 3 4.3 g, yield 92.8%, purity 99.3%, m.p.44 ~ 45 ℃.
1H?NMR(500?MHz,CDCl
3)：δ7.35?(d,?
J=8.0?Hz,?4H),?7.10?(d,?
J=8.0?Hz,?4H),?2.31?(s,?6H)。IR?(?KBr?)：3019，1488，,801，479?cm
-1。MS?(?EI,?70?eV?):?m/z=278（100，M
+）。
Embodiment 4
Substrate changes 4-chlorothio-phenol 43.4 g (0.3 mol) into, catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition and preparation process are all with embodiment 1.Obtain pale yellow crystals 40.8 g, yield 94.7%, purity 99.0%; M.p.72 ~ 73 ℃.
1H?NMR(500?MHz,CDCl
3)：δ7.41?(d,?
J=9.0?Hz,?4H),?7.26?(d,?
J=8.5?Hz,?4H)。IR?(?KBr?)：3077，516?cm
-1。MS?(?EI,?70?eV?):?m/z=286（100，M
+），288（74，M
++2）,?290（74，M
++4）。
Embodiment 5
Substrate changes 4-bromo thiophenol 56.7 g (0.3 mol) into, catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition and preparation process are all with embodiment 1.Obtain product 53.4 g, yield 89.9%, purity 99.1%; M.p.91 ~ 93 ℃.
1H?NMR(500?MHz,CDCl
3)：δ7.93?(d,?
J=8.5?Hz,?4H),?7.60?(d,?
J=8.5?Hz,?4H)。MS?(?EI,?70?eV?):?m/z=374（50，M
+-2）376（100，M
+）,?378（55，M
++2）。
Embodiment 6
Substrate changes 4-fluoro thiophenol 3.84 g into, and (30 mmol), catalyst levels change 244 mg (0.75 mmol) into, and method of purification changes column chromatography into, and other condition and preparation process are all with embodiment 1.Crude product is made eluent through column chromatography for separation with sherwood oil, and TLC detects, and collects the elutriant that contains product, and eluent is removed in the elutriant distillation, obtains oily liquids 3.3 g, yield 86.5%, purity 99.0%;
1H NMR (500 MHz, CDCl
3): δ 7.69 (d,
J=8.0 Hz, 4H), 7.38 (d,
J=7.5 Hz, 4H).MS?(?EI,?70?eV?):?m/z=254（100，M
+）。
Embodiment 7
Substrate changes 4-methyl mercapto thiophenol 46.8 g (0.3 mol) into, catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition and preparation process are all with embodiment 1.Obtain product 42.3 g, yield 91%, purity 99.1%; M.p.41 ~ 42 ℃.
1H?NMR(500?MHz，CDCl
3)：δ7.6?(d,?4H),?7.39?(d,?4H)，2.53(s,?6H)。MS?(?EI,?70?eV?):?m/z=246（100，M
+）。
Embodiment 8
Substrate changes 4-aminothiophenol 37.5 g (0.3 mol) into, catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition and preparation process are all with embodiment 1.Obtain pale yellow crystals 34.4 g, yield 92.4%, purity 99.1%; M.p.72 ~ 73 ℃.
1H?NMR(500?MHz,CDCl
3)：δ7.46?(d,?4H),?6.82(d,?4H)，6.27(s,?4H)。MS?(?EI,?70?eV?):?m/z=248（100，M
+）。
Embodiment 9
Substrate changes 4-hydroxythiophenol 37.8 g (0.3 mol) into, catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition and preparation process are all with embodiment 1.Obtain canescence crystal 3 2.7 g, yield 87.0%, purity 98.8%; M.p.150 ~ 151 ℃.
1H?NMR(500?MHz,CDCl
3)：δ7.61?(d,?4H),?7.00?(d,?4H)，5.35(s,?2H)；MS?(?EI,?70?eV?):?m/z=250（100，M
+）。
Embodiment 10
Substrate changes 4-methoxybenzenethiol 42.0 g (0.3 mol) into, catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition and preparation process are all with embodiment 1.Obtain pale yellow powder 38.1 g, yield 91.0%, purity 99.3%; M.p.43 ℃;
1H NMR (500 MHz, CDCl
3): δ 7.71 (d, 4H), 7.64 (d, 4H), 3.83 (s, 2H); MS (EI, 70 eV): m/z=278(100, M
+).
Embodiment 11
Substrate changes 4-nitro thiophenol 46.5 g (0.3 mol) into, catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition and preparation process are all with embodiment 1.Obtain pale yellow crystals 42.3 g, yield 91.5%, purity 99.2%; M.p.180 ~ 181 ℃.
1H?NMR(500?MHz,CDCl
3)：δ8.28?(d,?4H),?7.90(d,?4H)。MS?(?EI,?70?eV?):?m/z=308（100，M
+）。
Embodiment 12
Substrate changes thiosalicylic acid 46.2 g (0.3 mol) into, catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition and preparation process are all with embodiment 1.Obtain off-white color solid 41.4 g, yield 90%, purity 97.8%; M.p.288 ~ 290 ℃.
1H?NMR(500?MHz,DMSO)：δ13.40?(s,?2H),?8.04?(d,?
J=8.0?Hz,?2H),?7.61?(d,?
J=7.5?Hz,?2H),?7.57?(d,?
J=7.5?Hz,?2H)，7.34?(d,?
J=8.0?Hz,?2H)。IR?(?KBr?)：3000，1680?，551?cm
-1。MS?(?EI,?70?eV?):?m/z=306（9.9，M
+）。
Embodiment 13
Substrate changes 2-aminothiophenol 37.5 g (0.3 mol) into, catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition and preparation process are all with embodiment 1.Obtain white crystal 32.3 g, yield 86.7%, purity 98.6%; M.p.89 ~ 92 ℃.
1H?NMR(500?MHz，CDCl
3)：δ7.52?(d,?2H),?7.20(d,?2H),?6.91?(d,?2H),?6.65(d,?2H),?6.27(s,?4H)。MS?(?EI,?70?eV?):?m/z=248（100，M
+）。
Embodiment 14
Substrate changes 2-chlorothio-phenol 43.4 g (0.3 mol) into, catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition and preparation process are all with embodiment 1.Obtain pale yellow crystals 40.1 g, yield 93%, purity 99.0%; M.p.77 ~ 78 ℃.
1H?NMR(500?MHz，CDCl
3)：δ7.88?(d,?2H),?7.57(d,?2H),?7.34?(d,?4H)。MS?(?EI,?70?eV?):?m/z=286（100，M
+），288（72，M
++2），290（12，M
++4）。
Embodiment 15
Substrate changes 2-nitro thiophenol 46.5 g (0.3 mol) into, catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition and preparation process are all with embodiment 1.Obtain yellow solid 42.2 g, yield 91.3%, purity 98.5%; M.p.194 ~ 196 ℃.
1H?NMR(500?MHz，CDCl
3)：δ8.3?(d,?2H),?7.97(d,?2H),?7.78?(d,?2H)?,?7.65?(d,?2H)。MS?(?EI,?70?eV?):?m/z=308（100,?M
+）。
Embodiment 16
Substrate changes 2-benzamide base thiophenol 68.7 g (0.3 mol) into, catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition and preparation process are all with embodiment 1.Obtain off-white color solid 56.8 g, yield 83.0%, purity 97.8%; M.p.145 ~ 146 ℃.
Embodiment 17
Substrate changes 3-chlorothio-phenol 4.32 g into, and (30 mmol), catalyst levels change 244mg (0.75 mmol) into, and method of purification changes column chromatography into, and other condition and preparation process are all with embodiment 1.Crude product is made eluent through column chromatography for separation with sherwood oil, and TLC detects, and collects the elutriant that contains product, and eluent is removed in the elutriant distillation, obtains light yellow liquid 3.8 g, yield 88.2%, purity 98.7%;
1H NMR (500 MHz, CDCl
3): δ 7.89 (m, 2H), 7.59 (m, 2H), 7.43 (m, 2H), 7.34 (m, 2H).MS?(?EI,?70?eV?):?m/z=286（100，M
+），288（73，M
++2），290（14，M
++4）。
Embodiment 18
Substrate changes 3-nitro thiophenol 46.5 g (0.3 mol) into, catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition and preparation process are all with embodiment 1.Obtain yellow crystals 42.6 g, yield 92.1%, purity 98.7%; M.p.82 ~ 83 ℃.
1H?NMR(500?MHz，CDCl
3)：δ8.5?(s,?2H),?8.21(m,?2H),?8.12?(m,?2H)?,?7.76(m,?2H)。MS?(?EI,?70?eV?):?m/z=308（100,?M
+）。
Embodiment 19
Substrate changes 3 into, 5-two (trifluoromethyl) thiophenol 73.8 g (0.3 mol), catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition and preparation process are all with embodiment 1.Obtain oyster white crystal 70.1 g, yield 95.3%, purity 98.3%; Purity 98.5%; M.p.71 ~ 72 ℃.
1H?NMR(500?MHz，CDCl
3)：δ7.77?(s,?2H),?7.92?(s,?4H)。IR?(?KBr?)：1384?，682?cm
-1。MS?(?EI,?70?eV?):?m/z=490?(100，M
+)。
Embodiment 20
Substrate is 3, two (trifluoromethyl) thiophenol 73.8 g (0.3 mol) of 5-, catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, temperature of reaction changes room temperature into, and other condition preparation process is all with embodiment 19.Obtain oyster white crystal 6 9.8 g, yield 95.0%., purity 98.3%; M.p.71 ~ 72 ℃.
Embodiment 21
Substrate is 3, two (trifluoromethyl) thiophenol 73.8 g (0.3 mol) of 5-, catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, reaction times changes 0.3 hour into, and other condition preparation process is all with embodiment 20.Obtain oyster white crystal 6 9.9 g, yield 95.0%, purity 98.2%; M.p.71 ~ 72 ℃.
Embodiment 22
Substrate changes benzyl mercaptan 60.0 g (0.3 mol) into, catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition preparation process is all with embodiment 1.Obtain white crystal 16.6 g, yield 45.0%, purity 98.6%; M.p.72 ~ 73 ℃.
Embodiment 23
Substrate is benzyl mercaptan 60.0 g (0.3 mol), catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and temperature of reaction changes reflux temperature into, and other condition preparation process is all with embodiment 22.Obtain white crystal 19.0 g, yield 51.4%, purity 98.1%; M.p.71 ~ 73 ℃.
Embodiment 24
Substrate is benzyl mercaptan 60.0 g (0.3 mol), catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and the reaction times changes 10 hours into, and other condition preparation process is all with embodiment 23.Obtain white crystal 29.7 g, yield 80.3%, purity 98.3%; M.p.70 ~ 72 ℃.
Embodiment 25
Substrate changes furfuryl mercaptan 34.2 g (0.3 mol) into, and the amount of substance that feeds intake is than substrate: catalyzer is 1:0.025, and mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition preparation process is all with embodiment 24.Obtain product 27.2 g, yield 80.0%, purity 98.1%; M.p.109 ~ 112 ℃.
1H?NMR(500?MHz,CDCl
3)：δ7.57?(m,?2H),?6.40?(m，2H),?6.08?(m,?2H),?3.67(s,?4H)。MS?(?EI,?70?eV?):?m/z=258?(100，M
+)。
Embodiment 26
Substrate changes 2-mercaptonaphthalene 48.0 g (0.3 mol) into, and the amount of substance that feeds intake is than substrate: catalyzer is 1:0.025, and mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition preparation process is all with embodiment 24.Obtain pale yellow crystals 39.6 g, yield 83.0%, purity 98.8%; M.p.136 ℃.
1H?NMR(500?MHz,CDCl
3)：δ8.08?(m,?6H),?7.54?(m,?8H)。MS?(?EI,?70?eV?):?m/z=318?(100，M
+)。
Embodiment 27
Substrate changes isopropyl mercaptan 2.28 g into, (30 mmol), catalyst levels changes 244mg (0.75 mmol) into, method of purification changes column chromatography into, feed intake amount of substance than substrate: catalyzer is 1:0.025, mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition preparation process is all with embodiment 24.Crude product is made eluent through column chromatography for separation with methylene dichloride, and TLC detects, and collects the elutriant that contains product, and eluent is removed in the elutriant distillation, obtains reddish-brown liquid 1.8 g, yield 80.0%.
1H?NMR(500?MHz，CDCl
3)：δ2.88?(m,?2H),?1.34?(m,?12H)。MS?(?EI,?70?eV?):?m/z=150?(11，M
+)。
Embodiment 28
Substrate changes n-butyl mercaptan 2.7 g into, (30 mmol), catalyst levels change 244 mg (0.75 mmol) into, and the amount of substance that feeds intake is than substrate: catalyzer is 1:0.025, mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition preparation process is all with embodiment 27.Obtain colourless oil liquid 1.9 g, yield 71.0%.
1H?NMR(500?MHz,CDCl
3)：δ2.56?(m,?4H),?1.56?(m,?4H),?1.44?(m,?4H),?0.98(t,?6H)。MS?(?EI,?70?eV?):?m/z=178?(9，M
+)。
Embodiment 29
Substrate is 2-mercaptobenzothiazole 50.1 g (0.3 mol), catalyzer changes N into, N '-two (4-methoxyl group salicylidene) triethylenediamine cobalt, its consumption 2.66 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition preparation process is all with embodiment 1.Obtain light yellow solid 46.7 g, yield 93.7%, purity 99.5%; M.p.178 ~ 179 ℃.
Embodiment 30
Substrate is 2-mercaptobenzothiazole 50.1 g(0.3 mol), catalyzer changes N into, N '-two salicylidenes-1, the 2-propylene diamine closes cobalt, its consumption 2.54 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition preparation process is all with embodiment 1.Obtain light yellow solid 40.5 g, yield 81.3%, purity 98.9%; M.p.177 ~ 179 ℃.
Embodiment 31
Substrate is 2-mercaptobenzothiazole 50.1 g(0.3 mol), catalyzer changes N into, N '-two (4-methoxyl group salicylidene)-1, the 2-propylene diamine closes cobalt, its consumption 2.77 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition preparation process is all with embodiment 1.Obtain yellow solid 38.5 g, yield 77.3%, purity 98.8%; M.p.177 ~ 179 ℃.
Embodiment 32
Substrate is 2-mercaptobenzothiazole 50.1 g(0.3 mol), catalyzer is N, N '-two salicylidene triethylenediamine cobalts, its consumption are 1.0 g(0.003 mol), the reaction times is 2 hours, other condition preparation process is all with embodiment 1.Obtain light yellow solid 25.1 g, yield 50.5%, m.p.178 ~ 180 ℃.
Embodiment 33
Substrate is 2-mercaptobenzothiazole 50.1 g(0.3 mol), catalyzer is N, N '-two salicylidene triethylenediamine cobalts, its consumption 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, reaction times changes 5 hours into, and other condition preparation process is all with embodiment 32.Obtain light yellow solid 42.9 g, yield 86.1%, m.p.178 ~ 180 ℃.
Embodiment 34
Substrate is 2-mercaptobenzothiazole 50.1 g(0.3 mol), catalyzer is N, N '-two salicylidene triethylenediamine cobalts, its consumption are 9.8 g(0.03 mol), the reaction times is 0.3 hour, other condition preparation process is all with embodiment 1.Obtain light yellow solid 47.1 g, yield 94.6%, purity 98.9%; M.p.178 ~ 180 ℃.
Embodiment 35
Substrate is 2-mercaptobenzothiazole 50.1 g(0.3 mol), reaction solvent changes methyl alcohol into, catalyzer is N, N '-two salicylidene triethylenediamine cobalts, its consumption 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition preparation process is all with embodiment 1.Obtain light yellow solid 44.2 g, yield 88.8%, purity 97.9%; M.p.177 ~ 179 ℃.
Embodiment 36
Substrate is 2-mercaptobenzothiazole 50.1 g(0.3 mol), solvent changes ethyl acetate into, catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition preparation process is all with embodiment 1.Obtain light yellow solid 37.4 g, yield 75.1%, purity 98.9%; M.p.178 ~ 179 ℃.
Embodiment 37
Substrate is 2-mercaptobenzothiazole 50.1 g(0.3 mol), solvent changes tetracol phenixin into, catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition preparation process is all with embodiment 1.Obtain light yellow solid 41.9 g, yield 84.1%, purity 98.3%; M.p.177 ~ 179 ℃.
Embodiment 38
Substrate is 2-mercaptobenzothiazole 50.1 g(0.3 mol), solvent changes toluene into, catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition preparation process is all with embodiment 1.Obtain light yellow solid 42.9 g, yield 86.1%, purity 98.2%; M.p.177 ~ 179 ℃.
Embodiment 39
Substrate is 2-mercaptobenzothiazole 50.1 g(0.3 mol), the consumption of etoh solvent is 250 ml, other condition preparation process is all with embodiment 1.Obtain light yellow solid 45.2 g, yield 90.7%, purity 98.6%; M.p.178 ~ 180 ℃.
Embodiment 40
Substrate is 2-mercaptobenzothiazole 50.1 g(0.3 mol), the consumption of etoh solvent is 1000 ml, other condition preparation process is all with embodiment 1.Obtain light yellow solid 44.4 g, yield 89.1%, purity 98.7%; M.p.178 ~ 180 ℃.
Embodiment 41
Substrate is 2-mercaptobenzothiazole 50.1 g(0.3 mol), temperature of reaction changes 40 ℃ into, catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition preparation process is all with embodiment 1.Obtain light yellow solid 40.7 g, yield 81.7%, purity 98.6%; M.p.178 ~ 180 ℃.
Embodiment 42
Substrate is 2-mercaptobenzothiazole 50.1 g(0.3 mol), temperature of reaction changes reflux temperature into, catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition preparation process is all with embodiment 1.Obtain light yellow solid 46 g, yield 92.4%, purity 98.2%; M.p.178 ~ 180 ℃.
Embodiment 43
Substrate is 2-mercaptobenzothiazole 50.1 g(0.3 mol), reaction times changes 0.5 hour into, catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition preparation process is all with embodiment 1.Obtain light yellow solid 39.8 g, yield 80.0%, purity 98.7%; M.p.178 ~ 180 ℃.
Embodiment 44
Substrate is 2-mercaptobenzothiazole 50.1 g(0.3 mol), reaction times changes 10 hours into, catalyst levels 2.44 g(0.0075 mol), mass volume ratio substrate (g) feeds intake: solvent volume (ml) is 1:10, and other condition preparation process is all with embodiment 1.Obtain light yellow solid 46.6 g, yield 93.6%, m.p.178 ~ 180 ℃.
Embodiment 45
Substrate is 2-mercaptobenzothiazole 50.1 g(0.3 mol), catalyst levels is 2.44 g(0.0075 mol), reaction solvent is a toluene, and temperature of reaction is 100 ℃, and the reaction times is 0.1 hour, and other condition preparation process is all with embodiment 1.Obtain light yellow solid 45.1 g, yield 90.6%, purity 97.9%; M.p.176 ~ 179 ℃.
Embodiment 46
Substrate is 2-mercaptobenzothiazole 50.1 g(0.3 mol), catalyst levels is 2.44 g(0.0075 mol), aerating oxygen, the reaction times is 0.2 hour, other condition preparation process is all with embodiment 1.Obtain light yellow solid 46.1 g, yield 92.4%, purity 98.7%; M.p.176 ~ 179 ℃.
Embodiments of the invention only are used for explanation and non-limiting technical scheme of the present invention; the described catalyzer of technical solution of the present invention, substrate structure are not limited to above-mentioned several, and the catalyzer of the basic structure that similar the present invention is cited and substrate all belong to protection scope of the present invention.Temperature of reaction in addition, the reaction times can be adjusted accordingly according to the difference of the physico-chemical property of raw material and product, and this is conspicuous for those skilled in the art.
Claims (10)
1. method for preparing suc as formula the symmetrical disulfide compound shown in (IV) is characterized in that described method is:
Being raw material suc as formula the compound shown in (III), with the CoSalen title complex shown in formula I or (II) is catalyzer, in organic solvent, bubbling air or oxygen are as oxygenant, 20 ~ 100 ℃ of temperature condition reactions down, tracking monitor is to reacting completely, and reaction finishes the aftertreatment of afterreaction liquid and makes suc as formula the symmetrical disulfide compound shown in (IV); Described organic solvent is the alcohol of C1 ~ C4, the ester compound of C2 ~ C6, the halogenated hydrocarbon compound of C1 ~ C2, acetonitrile, benzene or alkyl substituted benzene;
R
3SH R
3SS?R
3
（III） （IV）
In described formula (I) or the formula (II), R
1Or R
2Independent separately is H or OCH
3
In described formula (III) or the formula (IV), R
3Be C
6H
5-, p-H
3CC
6H
4-, p-ClC
6H
4-, p-BrC
6H
4-, p-FC
6H
4-, p-(H
3CS) C
6H
4-, p-H
2NC
6H
4-, p-HOC
6H
4-, p-H
3COC
6H
4-, p-O
2NC
6H
4-, o-HOOCC
6H
4-, o-H
2NC
6H
4-, m-ClC
6H
4-, o-ClC
6H
4-, o-O
2NC
6H
4-, o-(C
6H
5NHCO) C
6H
4-, m-H
3COC
6H
4-, m-O
2NC
6H
4-, 3,5-(F
3C)
2C
6H
3-, C
6H
5CH
2-, 2-[4-morpholinodithio base, furfuryl, 2-naphthyl, (H
3C)
2CH-or H
3C (CH
2)
2CH
2-.
2. the method for claim 1, it is characterized in that described organic solvent is methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, methyl acetate, ethyl acetate, propyl acetate, butylacetate, butyl formate, ethyl formate, methylene dichloride, trichloromethane, tetracol phenixin, 1,2-ethylene dichloride, acetonitrile, benzene, toluene, ethylbenzene or dimethylbenzene.
3. the method for claim 1, what it is characterized in that described amount of substance suc as formula the compound shown in (III) and catalyzer compares is 1:0.01 ~ 0.1.
4. the method for claim 1 is characterized in that described volume of organic solvent consumption is to count 5 ~ 100mL/g suc as formula the quality of the compound shown in (III).
5. the method for claim 1, it is characterized in that described reaction solution post-treating method is: after reaction finishes, reaction solution is cooled to room temperature, steaming desolventizes, obtain the symmetrical disulfide compound crude product, described symmetrical disulfide compound crude product purification processes obtains the pure product of symmetrical disulfide compound.
6. method as claimed in claim 5 is characterized in that described purification processing method is: with symmetrical disulfide compound crude product recrystallization solvent recrystallization, obtain the pure product of symmetrical disulfide compound, described recrystallization solvent is C
5~ C
12Alkane, toluene or C
1~ C
4Alcohol.
7. the method for claim 1 is characterized in that described purification processing method is: the symmetrical disulfide compound crude product is carried out column chromatography for separation, with C
5~ C
12Alkane, C
2~ C
6Ester, C
1~ C
4Alcohol or C
1~ C
2Halohydrocarbon make eluent, TLC detects, and collects the elutriant that contains symmetrical disulfide compound, eluent is removed in the elutriant distillation, obtains the pure product of symmetrical disulfide compound.
8. the method for claim 1 is characterized in that described temperature of reaction is room temperature or solvent refluxing temperature.
9. the method for claim 1 is characterized in that described ratio suc as formula the compound shown in (III) and the amount of substance of catalyzer is 1:0.025 ~ 0.05.
10. the method for claim 1 is characterized in that described organic solvent is methyl alcohol, ethanol, ethyl acetate, tetracol phenixin or toluene.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167686A (en) * | 2011-03-17 | 2011-08-31 | 郑州大学 | Method for preparing 2,2'-dibenzothiazyl disulfide by catalyzing oxidation through molecular oxygen |
| CN102304074A (en) * | 2011-06-21 | 2012-01-04 | 聊城大学 | Method for preparing rubber peptizing agent, namely 2,2'-dibenzamido diphenyl disulfide compound |
| CN102351622A (en) * | 2011-08-19 | 2012-02-15 | 浙江大学 | Method for preparing (Z)-1,2-disulfide-1-olefin by catalysis of metal copper salt |
| CN105294371A (en) * | 2015-10-30 | 2016-02-03 | 镇江伟泽生物医学科技有限公司 | Method for preparing disulfide bond containing compound by using TEMPO catalyst through aerobic oxidation |
| CN109134299A (en) * | 2018-09-06 | 2019-01-04 | 桂林理工大学 | A kind of preparation method of 1,2- Propane Diamine 5- fluorine salicylide Bis-Schiff Bases corrosion inhibiter |
| CN113603656A (en) * | 2021-10-08 | 2021-11-05 | 科迈化工股份有限公司 | Production process of rubber vulcanization accelerator MBTS |
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2010
- 2010-08-13 CN CN2010102524056A patent/CN101928193A/en active Pending
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| Title |
|---|
| 《应用化学》 20010425 马会宣等 "负载型壳聚糖双水杨叉乙二胺合钴配合物的制备及其对乙硫醇的催化氧化" 290-294 1-10 第18卷, 第4期 * |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167686A (en) * | 2011-03-17 | 2011-08-31 | 郑州大学 | Method for preparing 2,2'-dibenzothiazyl disulfide by catalyzing oxidation through molecular oxygen |
| CN102167686B (en) * | 2011-03-17 | 2013-08-07 | 郑州大学 | Method for preparing 2,2'-dibenzothiazyl disulfide by catalyzing oxidation through molecular oxygen |
| CN102304074A (en) * | 2011-06-21 | 2012-01-04 | 聊城大学 | Method for preparing rubber peptizing agent, namely 2,2'-dibenzamido diphenyl disulfide compound |
| CN102304074B (en) * | 2011-06-21 | 2013-07-17 | 聊城大学 | Method for preparing rubber peptizing agent, namely 2,2'-dibenzamido diphenyl disulfide compound |
| CN102351622A (en) * | 2011-08-19 | 2012-02-15 | 浙江大学 | Method for preparing (Z)-1,2-disulfide-1-olefin by catalysis of metal copper salt |
| CN102351622B (en) * | 2011-08-19 | 2013-12-25 | 浙江大学 | Method for preparing (Z)-1,2-disulfide-1-olefin by catalysis of metal copper salt |
| CN105294371A (en) * | 2015-10-30 | 2016-02-03 | 镇江伟泽生物医学科技有限公司 | Method for preparing disulfide bond containing compound by using TEMPO catalyst through aerobic oxidation |
| CN109134299A (en) * | 2018-09-06 | 2019-01-04 | 桂林理工大学 | A kind of preparation method of 1,2- Propane Diamine 5- fluorine salicylide Bis-Schiff Bases corrosion inhibiter |
| CN113603656A (en) * | 2021-10-08 | 2021-11-05 | 科迈化工股份有限公司 | Production process of rubber vulcanization accelerator MBTS |
| CN113603656B (en) * | 2021-10-08 | 2022-03-15 | 科迈化工股份有限公司 | Production process of rubber vulcanization accelerator MBTS |
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