CN102167686B - Method for preparing 2,2'-dibenzothiazyl disulfide by catalyzing oxidation through molecular oxygen - Google Patents
Method for preparing 2,2'-dibenzothiazyl disulfide by catalyzing oxidation through molecular oxygen Download PDFInfo
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000003647 oxidation Effects 0.000 title claims abstract description 30
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910001882 dioxygen Inorganic materials 0.000 title claims abstract description 17
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 22
- -1 transition metal salt Chemical class 0.000 claims abstract description 21
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- 239000005864 Sulphur Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 claims description 3
- FSEUPUDHEBLWJY-HWKANZROSA-N diacetylmonoxime Chemical compound CC(=O)C(\C)=N\O FSEUPUDHEBLWJY-HWKANZROSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 239000010970 precious metal Substances 0.000 abstract description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 abstract 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000003446 ligand Substances 0.000 abstract 1
- 239000012452 mother liquor Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 14
- 238000005406 washing Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 4
- 230000001143 conditioned effect Effects 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
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- 230000008901 benefit Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- OVBJJZOQPCKUOR-UHFFFAOYSA-L EDTA disodium salt dihydrate Chemical compound O.O.[Na+].[Na+].[O-]C(=O)C[NH+](CC([O-])=O)CC[NH+](CC([O-])=O)CC([O-])=O OVBJJZOQPCKUOR-UHFFFAOYSA-L 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- JGUQDUKBUKFFRO-UHFFFAOYSA-N chembl3184098 Chemical class ON=C(C)C(C)=NO JGUQDUKBUKFFRO-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 150000003952 β-lactams Chemical class 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for preparing 2,2'-dibenzothiazyl disulfide by catalyzing oxidation through molecular oxygen. In the method, a composition consisting of transition metal salt and an organic compound containing N or/and O and used as a ligand is taken as a catalyst, 2-mercaptobenzothiazole is reacted at the temperature of between 20 and 120DEG C under the pressure of between 0.01 and 2.00MPa for 1 to 30 hours in the presence of a solvent in the atmosphere of oxygen or air to be synthesized into the 2,2'-dibenzothiazyl disulfide. The catalyst does not contain precious metals, can be recycled, ensures a few wastes, is environment-friendly and has better industrial application prospect; the synthesis process is simple, the catalytic activity is high, and the reaction efficiency is high; the synthesized reaction product has high selectivity and byproducts are a few; and in the synthesis reaction, alkali, acid or other additives are not needed.
Description
Technical field
The invention belongs to 2,2 '-two sulphur di-benzothiazole synthesis technical field, be specifically related to the oxidation of a kind of catalytic molecular oxygen and prepare 2, the method for 2 '-two sulphur di-benzothiazoles.
Background technology
2,2 '-two sulphur di-benzothiazoles (DM) are domestic and international application one of vulcanization accelerators the most widely as the universal promotor of a kind of natural gum, synthetical glue and reclaimed rubber.In addition, DM can also be as medicine intermediate, medicines such as synthetic beta-lactam and the plain class of cephalo.
At present, the industrial production of DM mainly is to prepare by oxidation 2-mercaptan benzothiazole (M), more generally the oxygenant of Shi Yonging is Sodium Nitrite and chlorine, can produce obnoxious flavoures such as oxynitride and hydrogenchloride in process of production, the more seriously a large amount of brine waste of association, the aftertreatment difficulty is difficult to realize cleaner production, does not meet the production requirement of national environmental protection policy and energy-saving and emission-reduction.And, products obtained therefrom second-rate, fusing point is lower, is difficult to reach the index of top grade product, can't be used for the production of pharmaceutical prod as raw material.
Prepare the method (seeing reaction formula 1) of DM with molecular oxygen (oxygen or air) oxidation M because have that cost is low, oxygenant is easy to separation from system, green non-pollution, product purity advantages of higher, more and more come into one's own.Its key is the simple cheap highly active catalyzer of exploitation, and relevant Technology easy and simple to handle.
Chinese patent CN 101215272 A have reported and have a kind ofly prepared the method for DM with molecular oxygen (oxygen or air) oxidation M, and this method is made solvent with ammoniacal liquor, carry out oxidation again after the M dissolving is converted into the M ammonium salt, and the catalyzer code name that uses is KM-014.Adopt Chinese patent CN 101139338 A and Chinese patent CN101717378 A in addition by M ammonium salt method for oxidation, its catalyzer is mantoquita.Similarly, Chinese patent CN101134748A has reported that a kind of elder generation is converted into the method that the M sodium salt reoxidizes with M, and the catalyzer code name that uses is KM-01.These methods all are to react in alkaline aqueous solution, are difficult to avoid the generation of brine waste.
United States Patent (USP) (US006124467A) has reported and has a kind ofly prepared the method for DM with molecular oxygen (oxygen or air) oxidation M in organic solvent or water that the catalyzer that uses is ferrous porphyrin and phthalocyanine iron compounds.Still need to add organic bases or mineral alkali in the reaction process.
Above-mentioned relatively first kind chemical oxidization method, the second class catalytic oxidation has the advantages that oxygenant is easy to separate from system, but all need add organic bases or mineral alkali in reaction process, thereby has limited the use of these methods.
Summary of the invention
The object of the present invention is to provide a kind of environmentally friendly catalytic molecular oxygen oxidation to prepare 2, the method for 2 '-two sulphur di-benzothiazoles.
The present invention is by the following technical solutions:
The oxidation of a kind of catalytic molecular oxygen prepares 2, the method of 2 '-two sulphur di-benzothiazoles, with transition metal salt with a kind ofly contain N or/and the mixture that the organic compound of O is formed is catalyzer as what part used, make the 2-mercaptan benzothiazole in oxygen or air ambient, in pressure 0.01-2.00MPa, temperature 20-120 ℃ 1-30 hour synthetic 2,2 '-two sulphur di-benzothiazoles of reaction under the solvent condition be arranged.
Described transition metal salt is one of hydrochloride, vitriol, nitrate, acetate and hydrate thereof of Co, Ce, Cu, Fe, Mn, Ni or two or more combinations, the described organic compound that uses as part is 2,2, one of 6,6-tetramethyl piperidine-N-oxyradical, dimethylglyoxime, biacetyl monoxime, ethylenediamine tetraacetic acid (EDTA), disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, diethylene triamine pentacetic acid (DTPA), methyl ethyl diketone and oxalic acid or two or more combination.
The mass ratio of described transition metal salt and part is 0.2-8:1.
The mass ratio of described transition metal salt and part is 0.5-2:1.
Described catalyst consumption is the 0.5-30% of 2-mercaptan benzothiazole quality.
Described solvent is methyl alcohol, ethanol or acetonitrile, and solvent load is 1-20 times of 2-mercaptan benzothiazole quality.
Described reaction pressure is that 0.15-0.6Mpa, temperature are that 60-80oC, reaction times are 4-12 hour, and catalyst consumption is the 3-15% of 2-mercaptan benzothiazole quality, and solvent load is 5-10 times of 2-mercaptan benzothiazole quality.
Metal in the transition metal salt among the present invention in the catalyst system therefor comprises Co, Ce, Cu, Fe, Mn, Ni etc., transition metal salt can exist with the form of hydrochloride, vitriol, nitrate or acetate, and transition metal wherein can be any valence state or mixed valence that can stable existence.The single component transition metal-salt that is used for catalyzer is the Chemicals of directly buying; The transition metal salt that is used for catalyzer can be formed by directly mixing by two or more transition metal salts, and there is no particular limitation for the mass ratio between the transition metal salt component, can be arbitrary proportion.
Among the present invention, contain N or/and the mixture that the organic compound of O is formed is catalyzer with transition metal salt with as what part used, directly come into operation, two kinds of components first original position in reaction process generates title complex and then brings into play katalysis.The transition metal salt and the part that are used for catalyzer can be made corresponding title complex earlier, re-use, and also can directly buy corresponding Chemicals title complex.
The present invention is by in the synthetic DM process of M oxidation, and oxidation effectiveness increases with catalyst levels and improves, and also increases but catalyst levels increases production cost thereupon; Carried out in solvent by the synthetic DM process of M oxidation, solvent for use has the ability of dissolving M and catalyzer, and solvent is methyl alcohol, ethanol or acetonitrile, and solvent load is 1-20 times of M quality, and preferred 5-10 doubly.
After building-up reactions finishes among the present invention, the aftertreatment technology process is not particularly limited, product D M separates purification can carry out by the following method: after oxidizing reaction finishes, place cooling, by filter with DM with contain the mother liquor of catalyzer with unreacted M and separate, through recrystallization and oven dry, obtain product D M again.
Oxidizing reaction of the present invention finishes to isolate the later mother liquor of DM can reuse the effect that continues the performance catalyzer, utilize that number of times is more many more saves production cost, but after repeatedly utilizing, because water content increases in the mother liquor, can influence the carrying out of oxidizing reaction, the speed of reaction of M and transformation efficiency descend.Suitable mother liquor utilizes number of times to be 2-10 time, and the mother liquor after the utilization can pass through distillating recovering solvent, and recovered solvent can be used as novel solvent and uses.
Preparation method of the present invention compared with prior art has following advantage: used catalyzer does not contain precious metal, can repeatedly utilize, and refuse is few, and environmental friendliness has stronger prospects for commercial application; Synthesis technique is simple and direct, catalytic activity height, reaction efficiency height; Building-up reactions selectivity of product height, by product is few; Need not to use any alkali, acid or other additive in the building-up reactions.
Description of drawings
Fig. 1 is the infared spectrum of embodiment 1 product DM.
Embodiment
Embodiment 1: synthetic 2,2 '-two sulphur di-benzothiazoles (DM) of 2-mercaptan benzothiazole (M) catalyzed oxidation in oxygen atmosphere
In the reactor of 500 L, drop into 30 kg M, 2.1 kg Co (NO
3)
26H
2O, 2.5 kg methyl ethyl diketones and 300 L methyl alcohol; Stir down heat temperature raising to 100 ℃, aerating oxygen keeps that pressure is 0.15 MPa in the reactor, react stopped reaction after 15 hours, cooling is filtered, 30 L methanol wash, the washing, dry product DM28.6 kg, the infared spectrum of product as shown in Figure 1, its infared spectrum and DM standard infared spectrum are in full accord, yield is 96%, fusing point is 180-181 ℃, liquid chromatograph is analyzed, and products obtained therefrom has identical retention time with the DM standard specimen, and content is 99.5%.
The mother liquor and the washing and recycling methyl alcohol that filter to isolate DM merge, and return reactor, drop into 30 kg M again, need not to drop into again catalyzer, continue to press original conditioned response 15 hours, the final 27.4 kg DM that get, yield is 92%, and fusing point is 178-180 ℃, and it is 99% that liquid chromatograph is analyzed DM content.So recycle mother liquor under the same terms 10 times, each time yield is all more than 95%.Utilize for the 10th time, the final 28.3 kg DM that get, yield is 95%, fusing point is 172-176 ℃.
Distillation utilizes the mother liquor after 10 times, reclaims solvent methanol 310 L, and the Methanol Recovery rate is 54%, and the methyl alcohol that the Methanol Recovery rate reclaims for distillation accounts for the ratio of the total consumption of reaction process methyl alcohol.
Embodiment 2: the synthetic DM of M catalyzed oxidation in air atmosphere
In the reactor of 500 L, drop into 60 kg M, 0.1 kg Ce (NO
3)
36H
2O, 0.1 kg Mn (OAc)
24H
2O and 0.1 kg 2,2,6,6-tetramethyl piperidine-N-oxyradical and 300 L ethanol; Stir down heat temperature raising to 120 ℃, be pressed into air, keep that pressure is 2.0 MPa in the reactor, react stopped reaction after 20 hours, cooling is filtered, 30L washing with alcohol, washing, dry product 57.2 kg DM, yield is 96%, fusing point is 180-182 ℃, it is 99% that liquid chromatograph is analyzed DM content.
The mother liquor and the washing and recycling ethanol that filter to isolate DM merge, and return reactor, drop into 60 kg M again, need not to drop into again catalyzer, continue to press original conditioned response 20 hours, the final 54.9 kg DM that get, yield is 92%, and fusing point is 180-181 ℃, and it is 99% that liquid chromatograph is analyzed DM content.So recycle mother liquor under the same terms 5 times, each time yield is all more than 94%.The 5th is utilized, the final 28.3 kg DM that get, and yield is 95%, fusing point is 172-176 ℃.
Distillation utilizes the mother liquor after 5 times, reclaims etoh solvent 400 L, and the ethanol rate of recovery is 90%.
Embodiment 3: the synthetic DM of dioxygen oxidation under the normal pressure
In the 500 L reactors of the ventpipe bottom condenser being housed and inserting, drop into 90 kg M, 4.0 kg CuSO
45H
2O, 0.5 kg oxalic acid and 200 L acetonitriles; Stir down heat temperature raising to 80 ℃, aerating oxygen begins reaction continuously; React stopped reaction after 25 hours, cooling is filtered, the washing of 90 L acetonitriles, washing, dry product 84.1 kg DM, yield is 94%, fusing point is 179-181 ℃, it is 99.4% that liquid chromatograph is analyzed DM content.
The mother liquor and the washing and recycling acetonitrile that filter to isolate DM merge, and return reactor, drop into 90 kg M again, need not to drop into again catalyzer, continue to press original conditioned response 25 hours, the final 81.4 kg DM that get, yield is 91%, and fusing point is 178-180 ℃, and it is 99% that liquid chromatograph is analyzed DM content.So recycle mother liquor under the same terms 3 times, each time yield is all more than 95%.Utilize for the 3rd time, the final 84.9 kg DM that get, yield is 95%, fusing point is 172-176 ℃.
Distillation utilizes the mother liquor after 3 times, reclaims solvent acetonitrile 140 L, and the acetonitrile rate of recovery is 30%.
Embodiment 4: the synthetic DM of atmospheric oxidation under the normal pressure
In the 500 L reactors of the ventpipe bottom condenser being housed and inserting, drop into 20 kg M, 0.5 kg Fe (NO
3)
39H
2O, 2.5 kg dimethylglyoximes and 400 L methyl alcohol; Stir down heat temperature raising to 20 ℃, bubbling air begins reaction continuously; React stopped reaction after 30 hours, cooling is filtered, 30 L methanol wash, washing, dry product 18.5 kg DM, yield is 93%, fusing point is 181-182 ℃, it is 99.6% that liquid chromatograph is analyzed DM content.
The mother liquor and the washing and recycling methyl alcohol that filter to isolate DM merge, and return reactor, drop into 20 kg M again, need not to drop into again catalyzer, continue to press original conditioned response 30 hours, the final 18.7 kg DM that get, yield is 93%, and fusing point is 181-182 ℃, and it is 99.5% that liquid chromatograph is analyzed DM content.
Distillation utilizes the mother liquor after 2 times, reclaims solvent methanol 410 L, and the Methanol Recovery rate is 90%.
Embodiment 5: the synthetic DM of M catalyzed oxidation in oxygen atmosphere
In the reactor of 500 L, drop into 100 kg M, 0.2 kg Ni (OAc)
24H
2O, 0.2 kg diethylene triamine pentacetic acid (DTPA), 0.2 kg dimethylglyoxime and 120 L methyl alcohol; Stir down heat temperature raising to 60 ℃, aerating oxygen, keeping the interior pressure of reactor is 0.3 MPa, reacts stopped reaction after 8 hours, cooling, filter 50 L methanol wash, washing, dry product 93.4 kg DM, yield is 94%, and fusing point is 180-182 ℃, and it is 99.5% that liquid chromatograph is analyzed DM content.The distillation mother liquor reclaims solvent methanol 145 L, and the Methanol Recovery rate is 85%.
Embodiment 6: DM is synthesized in the M oxidation under the different condition
Carry out oxidizing reaction by embodiment 1 identical method with identical M charging capacity, different is that catalyzer is formed and various reaction conditions, and reaction result sees Table 1.
DM is synthesized in M oxidation under table 1 different condition
As seen from the above embodiment, adopt preparation method of the present invention, yield has all reached 90%, and the catalyzer that this preparation method adopts can not pollute environment, catalytic activity height, reaction efficiency height.
Claims (6)
1. catalytic molecular oxygen oxidation prepares 2, the method of 2 '-two sulphur di-benzothiazoles, it is characterized in that: with transition metal salt with a kind ofly contain N or/and the mixture that the organic compound of O is formed is catalyzer as what part used, make the 2-mercaptan benzothiazole in oxygen or air ambient, in pressure 0.01-2.00MPa, temperature 20-120 ℃ 1-30 hour synthetic 2,2 '-two sulphur di-benzothiazoles of reaction under the solvent condition be arranged; Described transition metal salt is one of hydrochloride, vitriol, nitrate, acetate and hydrate thereof of Fe or two or more combinations, the described organic compound that uses as part is 2,2,6,6-tetramethyl piperidine-N-oxyradical, dimethylglyoxime or biacetyl monoxime.
2. catalytic molecular oxygen as claimed in claim 1 oxidation prepares 2, and the method for 2 '-two sulphur di-benzothiazoles is characterized in that: the mass ratio of described transition metal salt and part is 0.2-8:1.
3. catalytic molecular oxygen as claimed in claim 2 oxidation prepares 2, and the method for 2 '-two sulphur di-benzothiazoles is characterized in that: the mass ratio of described transition metal salt and part is 0.5-2:1.
4. oxidation prepares 2 as the arbitrary described catalytic molecular oxygen of claim 1-3, and the method for 2 '-two sulphur di-benzothiazoles is characterized in that: described catalyst consumption is the 0.5-30% of 2-mercaptan benzothiazole quality.
5. catalytic molecular oxygen as claimed in claim 4 oxidation prepares 2, and the method for 2 '-two sulphur di-benzothiazoles is characterized in that: described solvent is methyl alcohol, ethanol or acetonitrile, and solvent load is 1-20 times of 2-mercaptan benzothiazole quality.
6. catalytic molecular oxygen as claimed in claim 5 oxidation prepares 2, the method of 2 '-two sulphur di-benzothiazoles, it is characterized in that: described reaction pressure is that 0.15-0.6Mpa, temperature are that 60-80oC, reaction times are 4-12 hour, catalyst consumption is the 3-15% of 2-mercaptan benzothiazole quality, and solvent load is 5-10 times of 2-mercaptan benzothiazole quality.
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|---|---|---|---|---|
| CN102367237A (en) * | 2011-09-20 | 2012-03-07 | 科迈化工股份有限公司 | Method for producing medical DM by taking oxygen as oxidizing agent |
| CN103145642A (en) * | 2013-03-29 | 2013-06-12 | 贾占军 | Refining method of mercaptobenzothiazole disulfide |
| 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 |
| CN106831644B (en) * | 2017-01-24 | 2019-07-12 | 郑州大学 | The method of catalytic molecular oxygen oxidation 2,2 '-two sulphur union II benzothiazoles of preparation in water phase |
| CN108727296A (en) * | 2017-10-23 | 2018-11-02 | 内蒙古科迈化工有限公司 | A kind of dioxygen oxidation one-step synthesis technique of rubber accelerator dibenzothiazyl disulfide |
| CN117720480B (en) * | 2023-12-20 | 2024-06-18 | 平乡县丰业橡胶助剂有限公司 | High-purity rubber vulcanization accelerator DM and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928193A (en) * | 2010-08-13 | 2010-12-29 | 浙江工业大学 | Method for preparing symmetrical disulfide compound |
Family Cites Families (1)
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| JP2002088056A (en) * | 2000-09-13 | 2002-03-27 | Sanshin Chem Ind Co Ltd | Oxidation method |
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Non-Patent Citations (3)
| Title |
|---|
| erobic oxidation of thiols to disulfides catalyzed by a manganese(III)Schiff-base complex;Hamid Golchoubian, Farideh Hosseinpoor,;《Catalysis Commmunications》;20061231;第8卷;第697-700页 * |
| Hamid Golchoubian, Farideh Hosseinpoor,.erobic oxidation of thiols to disulfides catalyzed by a manganese(III)Schiff-base complex.《Catalysis Commmunications》.2006,第8卷第697-700页. |
| JP特开2002-88056A 2002.03.27 |
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