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The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
Thiohexam is a rubber cure accelerator. Thiohexam is also a known allergen and dermatological sensitizer
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Tire Wear Emissions by Highways: Impact of Season and Surface Type
Miech, Jason A ; Aker, Saed ; Zhang, Zhaobo ; Ozer, Hasan ; Fraser, Matthew P ; Herckes, Pierre
Abstract: With the increasing number of electric vehicles taking to the roads, the impact of tailpipe emissions on air quality will decrease, while resuspended road dust and brake/tire wear will become more significant. This study quantified PM10 emissions from tire wear under a range of real highway conditions with measurements across different seasons and roadway surface types in Phoenix, Arizona. Tire wear was quantified in the sampled PM10 using benzothiazoles (vulcanization accelerators) as tire markers. The measured emission factors had a range of 0.005-0.22 mg km−1 veh−1 and are consistent with an earlier experimental study conducted in Phoenix. However, these results are lower than values typically found in the literature and values calculated from emissions models, such as MOVES (MOtor Vehicle Emission Simulator). We found no significant difference in tire wear PM10 emission factors for different surface types (asphalt vs. diamond grind concrete) but saw a significant decrease in the winter compared to the summer.
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Keywords: tire wear ; PM10 ; highway emissions ; pavement surface type ; MOVES model
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| CAS No. : | 95-33-0 |
| Formula : | C13H16N2S2 |
| M.W : | 264.41 |
| SMILES Code : | C1(SNC2CCCCC2)=NC3=CC=CC=C3S1 |
| English Name : | N-Cyclohexyl-2-benzothiazolesulfenamide |
| MDL No. : | MFCD00022872 |
| InChI Key : | DEQZTKGFXNUBJL-UHFFFAOYSA-N |
| Pubchem ID : | 7232 |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 99.5% | Stage #1: benzothiazole sulfenamide; cyclohexylamine In water at 30 - 40℃; for 3h; Stage #2: With sodium hydroxide In water at 35 - 85℃; for 1.5h; | 1 Example 1 In the with a stirrer, a thermometer, a reflux condenser of the 500 ml four flasks adding water in 160 ml, with stirring, at room temperature is added in batches under 68g (0.2 µM) disulphide benzothiazole, after adding stirring for half an hour, then add 30g (0.3 µM) cyclohexylamine, adding temperature control in the 30 - 35 °C, adding time 30 minutes, after adds the link cyclohexylamine in the 30 - 35 °C maintain 2 hours, the maintenance is finished, in the 35 - 40 °C, for 30 minutes add 30% sodium hydroxide 20 ml, added after the end of the raising the temperature to 80 - 85 °C to continue to maintain the 1 hour, stirring under cooling to 15 - 20 °C, filtering, for 40 ml of water washing four times, the washing water with a mother liquor combined distillation recovery cyclohexylamine, residual liquid concentrated mechanically as a next batch of catalyst and reaction water, solid product in 50 °C drying, sampling analysis, weighing, shall 52.8g finished product, melting point 103 °C, CBS yield 99.5%, methanol insoluble 0.1%. |
| at 50℃; for 2h; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With water |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 95.2% | Stage #1: cyclohexylamine; sodium 2-mercaptobenzothiazole With sulfuric acid; dihydrogen peroxide In water at 40 - 45℃; for 3 - 5h; Alkaline conditions; Stage #2: With sodium hypochlorite In water for 0.166667 - 0.633333h; | 1 Beispiel 1 In einen Reaktor wurden 995,94 g einer wssrigen, 20 %igen Lsung von Natrium-2-Mercaptobenzthiazol gegeben und zu dieser wssrigen Lsung 139,35 g Cyclohexylamin (100 %ig) unter intensivem Mischen (Mischleistung 0,4 Watt/l) hinzugefgt. Die Reinheit des eingesetzten Natrium-Mercaptobenzthiazols betrug 95 %. Das Molverhltnis von reinem Ntrium-Mercaptobenzthiazol zu Cyclohexylamin betrug 1 : 1,4 mol; d.h. auf 100 mol-% Natrium-Mercaptobenzthiazol mit einer Reinheit von 95 % wurden 133 mol-% an Cyclohexylamin eingesetzt. Der Reaktor war mit einem Rckflusskhler, einem Thermometer und einer pH-Messelektrode ausgestattet. Mit Hilfe einer 20 %igen Schwefelsure wurde der pH-Wert des Reaktionsgemisches bei 40C auf 10,6 eingestellt und die Temperatur whrend der gesamten Reaktion auf 40C belassen. Innerhalb eines Zeitraums von 5 Stunden wurde gleichmig 0,821 mol Wasserstoffperoxid (10 %ig) dem Reaktionsgemisch hinzugefgt. Dies bedeutet, dass 78 mol-% an Wasserstoffperoxid auf 100 mol-% an 95 %igem Natrium-Mercaptobenzthiazol eingesetzt wurden. Nach der Zugabe des Wasserstoffperoxids wurde innerhalb von 38 Minuten 13 %iges Natriumhypochlorit in einer Menge von 202 g dem Reaktionsgemisch hinzugegeben und nach dem Ende der Reaktion durch Zugabe von 50 %igem wssrigen Natriumhydroxid der pH-Wert auf 11,8 erhht. Die Reaktionsmischung wurde anschlieend auf 30C abgekhlt, filtriert, mit 10 %igem Cyclohexylamin gewaschen, danach nochmals mit Wasser nachgewaschen und das ausgefallene Produkt getrocknet. Erhalten wurden 245,56 g an Benzthiazolylsulfenamid, was eine Ausbeute von 97,76 %, bezogen auf reines Natrium-Mercaptobenzthiazol, bedeutet. Die Umsatzrate betrug 99,4 %, bezogen auf reines NaMBT. Das erhaltene Produkt besa eine Reinheit von 99,2 %, bestimmt durch Titration nach ASTM D 4936 (MBT). Bei der Umsetzung betrugt die Summe an eingesetztem Wasserstoffperoxid und eingesetzem Alkalimetallhypochlorit insgesamt 112 mol-%, bezogen auf die eingesetzte Menge an 95 %igem Natrium-Mercaptobenzthiazol.Beispiel 2 Es wurde wie unter Beispiel 1 gearbeitet, jedoch mit dem Unterschied, dass 1,06 mol 10 %iges Wasserstoffperoxid (101 mol-%, bezogen auf 100 mol-%iges Natrium-Mercaptobenzthiazol) eingesetzt wurden. Wasserstoffperoxid wurde innerhalb von 4 Stunden bei 40C Reaktionstemperatur zudosiert. Innerhalb von 10 Minuten wird weiter oxidiert mit 57,8 g einer 13 %igen NaOCl-Lsung. Die Ausbeute betrug 96,8 %, die Reinheit 99,2 % und die Umsatzrate 99,4 %. Beispiel 3 Es wurde wie unter Beispiel 2 gearbeitet, jedoch wurde das Wasserstoffperoxid innerhalb von 3 Stunden bei 40C Reaktionstemperatur zudosiert. Innerhalb von 12 Minuten wird weiter oxidiert mit 61,6 g einer 13 %igen NaOCl-Lsung. Die Ausbeute betrug 96,6 %, die Reinheit 98,1.% und die Umsatzrate 99,4 %. Beispiel 4 Dieses Beispiel wurde analog Beispiel 1 durchgefhrt, jedoch mit 1,10 ml Cyclohexylamin und mit 90 mol-% Wasserstoffperoxid (10 %ig). Das Wasserstoffperoxid wurde innerhalb von 4 Stunden bei 45C Reaktionstemperatur dem Reaktionsgemisch zugegeben. Innerhalb von 35 Minuten wird weiter oxidiert mit 182 g einer 13 %igen NaOCl-Lsung. Die Ausbeute betrug 95,2 %, die Reinheit 97,5 % und die Umsatzrate 99,4 %. Beispiel 5 Entsprechend dem Beispiel 1 wurde die Reaktion durchgefhrt. Eingesetzt wurde Natrium-Mercaptobenzthiazol mit einer Reinheit von 93 %. Die Menge an Cyclohexylamin betrug 1,43 mol, bezogen auf das eingesetzte 100 % reine Natrium-Mercaptobenzthiazol. Es wurden 90 mol-% 10 %iges Wasserstoffperoxid innerhalb von 4 Stunden bei einer Reaktionstemperatur von 40C dem Reaktionsgemisch zugegeben. Innerhalb von 24 Minuten wird weiter oxidiert mit 12 g einer 13 %igen NaOCl-Lsung. Die Ausbeute betrug 97,8 %, die Reinheit 98,9 % und die Umsatzrate 99,4 %. |
| 84% | With sulfuric acid; dihydrogen peroxide In water at 50℃; for 2h; | 6 Vergleichsbeispiel 6 In einen Reaktor wurden 397,89 g einer wssrigen 50 %ige Lsung von Natrium 2-Mercaptobenzothiazol gegeben und zu dieser wssrigen Lsung 187,57 g Cyclohexylamin 100 %ig und 1684 g Wasser unter Mischen hinzugefgt. Die Reinheit des eingesetzte Natrium-Mercaptobenzothiazols betrug 95 %. Anschlieend wurden 368,4 g einer 20 %igen Schwefelsure bei 50C zum Reaktionsgemisch gegeben. Innerhalb eines Zeitraums von 2 Stunden wurde gleichmig 1 mol Wasserstoffperoxid (30%ig) dem Reaktionsgemisch bei 50C hinzugefgt. Nach dem Ende der Reaktion wurde 73,68 g einer wssrigen 50 %igen Lsung von Natriumhydoxid zum Reaktionsgemisch gegeben. Die Reaktionsmischung wurde anschlieend 30 Minuten nachgerhrt, auf 30C abgekhlt, filtriert, mit Wasser gewaschen und das ausgefallene Produkt getrocknet. Erhalten wurde 222,1 g an Benzthiazolsulfenamid was eine Ausbeute von 84 %, bezogen auf reines Natrium-Mercaptobenzothiazol bedeutet. Das erhaltene Produkt besa eine Reinheit von 99%, bestimmt durch Titration nach ASTM D 4936. Die Mutterlauge enthlt noch 34,29 g Natrium-mercaptobenzothiazol wodurch die Umsatzrate 81,87 % betrug. |
| With alkaline aqueous solution; chloro-air mixture |
| With sulfuric acid; dihydrogen peroxide | ||
| With sodium hypochlorite; water; sodium sulfate | ||
| With alkaline aqueous solution; bromine | ||
| With alkaline aqueous solution; iodine; potassium iodide |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With diethyl ether |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| In diethyl ether |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| In benzene |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With hydrogen sulfide | ||
| With tiolacetic acid |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With hydrogenchloride |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With acetic anhydride |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 94.3% | With acetic anhydride In n-heptane at 68 - 70℃; for 1.41667h; Inert atmosphere; Autoclave; Large scale; | 1 A method for the synthesis of N-cyclohexyl-bis (benzothiazolyl) sulfenamide (CBBS) as a vulcanization accelerator is as follows: (1) After the nitrogen was replaced in the autoclave,Put 600kg n-heptane,600 kg 120 solvent oil and 390 kg acetic anhydride,well mixed,After warming to 68-70 ° C,Stir to join 500kgCBS,CBS 4 times to join,Each 125kg,Each time interval 15min,CBS all finished,Continue stirring at this temperature for 70 min to give a mixture;(2) to the reactor by adding the concentration of 5-10% sodium hydroxide solution,Adjust the PH value of 7,Stirring up to 85-95 ° C,Distillation recovery solvent,After the solvent is distilled, it is collected into the tank,As an organic solvent cycle.Reactor material filtration,The resulting cake is wet CBBS,The wet product is dried,A gray solid CBBS 383 kg was obtained,The purity was 96% by HPLC,The CBS yield was 94.3%.Filtered mother liquor sodium hydroxide solution, cyclohexane amide into cyclohexylamine, and then the mother liquor evaporated,Recycle of cyclohexylamine and sodium acetate. |
| With maleic anhydride | ||
| With phthalic anhydride |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With sodium tetrahydroborate In ethanol |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 97.2% | With (tetraphenylporphyrin)copper(II); oxygen In tetrachloromethane at 35℃; for 0.5h; Molecular sieve; Autoclave; | 1-6 (a) First, disperse 50g of 2-mercaptobenzothiazole in 500ml of carbon tetrachloride to obtain a solution of 2-mercaptobenzothiazole, and then add 2g of copper tetraphenylporphyrin immobilized on a molecular sieve to obtain Add the reaction solution into a 1L autoclave;(b) Turn on stirring and heating in the autoclave. When the temperature rises to 35°C, pass oxygen to make the pressure in the autoclave reach 0.35MPa, and then add 53..4g cyclohexylamine at a certain rate to react.As the reaction progresses, the pressure drops, and oxygen is added to 0.35 MPa at any time. After the addition of cyclohexylamine is completed and the reaction pressure no longer changes for 30 minutes, the reaction ends, and a post-reaction solution is obtained;(c). After the reaction solution obtained in step (b) is lowered to room temperature, the copper tetraphenylporphyrin immobilized on the molecular sieve is filtered and recovered, and then the carbon tetrachloride and the carbon tetrachloride in step (a) are recovered by distillation under reduced pressure. The reacted cyclohexylamine is then dried at 80°C and pulverized to obtain a rubber vulcanization accelerator CBS. |
| 96% | With oxygen In water at 60℃; for 4h; Autoclave; | 1-8 Specific example 8: 2 mmol of 2-mercaptobenzothiazole, 8 mmol of cyclohexylamine, 1 wt% of cobalt catalyst, 8 mL of water were added to a high-pressure reaction kettle, and oxygen was passed in until the pressure stabilized at 0.4 MPa and heated in an oil bath At 60 ° C. for 4 h, a white solid was formed, filtered, washed, and dried, and the yield was 96%. |
| 90% | With oxygen In water at 60℃; for 4h; |
| 88% | In ethanol at 20℃; Electrochemical reaction; Green chemistry; | 3.4. Electrochemical synthesis of sulfonamides (SO1eSO3) andsulfenamides (SE4-SE6) General procedure: For the synthesis of sulfonamides SO1eSO3, an 80 ml solutioncontaining phosphate buffer (pH 8.0, c 0.2 M)/ethanol (20/80 v/v) was pre-electrolyzed in an undivided cell. Then 0.5 mmol ofMBO, 1.5 mmol of amine (AM1, AM2 or AM3) was subjected toelectrolysis at constant current of 10 mA (0.26 mA cm2), in an undivided cell. The progress of the electrolysis was followed by TLCusing n-hexane/ethyl acetate (2:1) and also cyclic voltammetry. Atthe end of electrolysis, the reaction mixture was filtered and thenthe ethanol was removed under vacuum. The residual was extractedwith 3 10 ml of ethyl acetate. The extracted organic phasewasdried over anhydrous sodium sulphate, filtered and evaporatedunder reduced pressure. The resulting residuewas purified by flashchromatography on silica gel (eluent 2:1 n-hexaneeethyl acetate)to afford the corresponding sulfonamide (Table 1). |
| 83% | In dimethyl sulfoxide at 80℃; for 16h; | 4 Example 4: Add 1 mmol of 2-mercaptobenzothiazole and 4 mmol of cyclohexylamine to the reaction tube,0.05 g of metallic Co-Zn nano catalyst,And 10 ml of dimethyl sulfoxide solvent,At the same time, it was filled with air and magnetically stirred at 80°C for 16 hours.After the reaction stopped,Remove the solid catalyst by filtration, extract, dry, pass through a silica gel column,The product is obtained by drying, and the yield is 90% as determined by gas chromatography.The isolated yield was 83%.The catalyst obtained after filtration can be reused many times after being washed and dried. |
| 73% | With tetrabutylammonium tetrafluoroborate In acetonitrile at 20℃; for 10h; Sealed tube; Electrochemical reaction; | |
| 70% | With oxygen In N,N-dimethyl-formamide at 20℃; for 6h; Irradiation; | |
| 65.7% | With sodium hypochlorite at 45℃; | 4.2.10 General procedure for the synthesis of compounds 18,19 General procedure: To a stirred solution of benzothiazole-2-thiol (1equiv) and cyclohexylamine (2.5equiv), the sodium hypochlorite solution was added slowly at 45°C. The completion of oxidation was confirmed by bluestone solution and KI starch solution. The reaction solution was cooled to room temperature and the precipitate was separated out. Then precipitate was washed by 9% cyclohexylamine aqueous solution. Without further purification, the precipitate was filtered off to give the products. |
| With tetraethylammonium perchlorate In N,N-dimethyl-formamide for 24h; (electrolysis); | ||
| With sodium hypochlorite | ||
| 263.3 g | Stage #1: cyclohexylamine; 2-Mercaptobenzothiazole In water at 20℃; for 1h; Stage #2: With oxygen In water at 35 - 45℃; for 1h; | 3 186 g of crude 2-mercaptobenzothiazole (about 90% pure) was combined with 140 g of deionized water and 0. 2 g of non-aqueous Mixing 198 g of cyclohexylamine with 350 g of aqueous solution, and then adding the mixture into the reaction kettle at room temperature for 1 hour. The temperature is raised to 35 ° C to 45 ° C, and the temperature of the reaction mixture is increased to 35 ° C to 45 ° C. C after 0.21L / min into the oxygen (17. 6 grams) by the ozone plasma generator of activated oxygen, the oxidation reaction, the reaction 1 hour sample observation of white materials, to stop the reaction; Cooled to room temperature, filter the mother liquor to be recycled after recycling, washing to neutral, After drying was 261. 6 G of rubber accelerator CBS, the yield was 98.9%. The reaction process was carried out in the same manner as in Example 1 except that the rate of oxygen was changed to 0.28 L / min. Oxygen gas (24 g) was activated by the ozone plasma generator, and the oxidation reaction was carried out , The material was filtered and washed to neutral. After drying, 263. 3 g of rubber accelerator CBS was obtained, and the yield was 99.6%. |
| With sodium hypochlorite at 35℃; | 1 Example 1: As shown in Figure 1N-cyclohexyl-2-benzothiazole sulfenamide,Including the following steps:step one:Feeding:A concentration of 16% cyclohexylamine was added to the oxidation tank,The cyclohexylamine solution was stirred and 2-mercaptobenzothiazole was addedForming a mixed solution,The amine ratio of cyclohexylamine to 2-mercaptobenzothiazole is 2.3;Step two:Oxidation:Stir the mixture thoroughly,Then cooled to 35 ° C,And then slowly adding a solution of 5% sodium hypochlorite solution to the mixed solution to form a reaction solution,Until there isN-cyclohexyl-2-benzothiazole sulfenamidegenerate,The reaction solution of 2-mercaptobenzothiazole thiazole yellow granules disappears;Step three:Stirring the oxidized reaction solution and pouring it into a suction tank for filtration,The filtered N-cyclohexyl-2-benzothiazole sulfonamide was washed with hot water to neutral,And then centrifuged and dried and dried at 60 ° CN-cyclohexyl-2-benzothiazole sulfenamide finished product;The filtrate was evaporated to the distillation vessel and the cyclohexylamine was distilled off in vacuo.Until the amount of amine in the filtrate is below 1%. | |
| 92 % | With oxygen; potassium carbonate In dimethyl sulfoxide at 60℃; | |
| 96 % | With oxygen In acetonitrile at 60℃; Autoclave; | |
| 80 % | Stage #1: 2-Mercaptobenzothiazole With dimethylbromosulphonium bromide In dichloromethane at 0℃; Inert atmosphere; Schlenk technique; Stage #2: cyclohexylamine With caesium carbonate In dichloromethane at 20℃; Inert atmosphere; Schlenk technique; | 4 Example 4: Synthesis of S-(benzo[d]thiazol-2-yl)-N-cyclohexylthiolamine under nitrogen protection,Into a Schlenk reaction tube equipped with a magnetic stir bar2-Mercaptobenzothiazole (83.6mg, 1equiv),Dimethylsulfur bromide (110.9mg, 1equiv),DCM (5 mL) was added to dissolve at 0°C to form a mixed solution,Stir for 5min,After adding cesium carbonate (244.4mg, 1.5equiv) to react for a period of time,Cyclohexylamine (148.75 mg, 171.6 μL) was slowly added dropwise,The dropping time was controlled at 30min.After the addition is complete,naturally warmed to room temperature,Continue to react for 14h,After the reaction is complete,Extraction was carried out 3 times with dichloromethane,Each time 10mL, combine the organic phase,S-(benzo[d]thiazol-2-yl)-N-cyclohexylthiolamine 106 mg was obtained by rotary evaporation and column chromatography, with a yield of 80%. |
| 88 % | With oxygen In acetonitrile at 20℃; Irradiation; |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 1: 63% 2: 21.4% | at 130℃; for 3h; | |
| 1: 21.4% 2: 63% | at 130℃; for 3h; |