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Structure of 13352-75-5
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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.
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CAS No. : | 13352-75-5 |
Formula : | C6H14O5 |
M.W : | 166.17 |
SMILES Code : | COCOCOCOCOC |
MDL No. : | MFCD26792350 |
GHS Pictogram: |
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Signal Word: | Danger |
Hazard Statements: | H226-H315-H318-H335 |
Precautionary Statements: | P210-P233-P240-P241-P242-P243-P261-P264-P271-P280-P303+P361+P353-P304+P340+P312-P305+P351+P338+P310-P332+P313-P370+P378-P403+P233-P403+P235-P405-P501 |
Class: | 3 |
UN#: | 1993 |
Packing Group: | Ⅲ |
* 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 |
---|---|---|
With sulfuric acid; at 55 - 115℃;Inert atmosphere; | Paraformaldehyde (45 g 1.5 mol, 30 g/mol CH2O eq.) was weighed into a 500 ml. heavy walled glass reactor fitted with an O-ring joint with a polytetrafluoroethylene (PTFE) seal and KONTES 0-4 mm Hivac Stopcock (Kontes Glass Company, Vineland, New Jersey, United States of America). A magnetic stirrer bar was introduced and the joint sealed. The reactor was flushed with dry nitrogen. Methylal (48 mL, 41.3 g, 0.54 mol) was added and stirring at 100 rpm was initiated. After thorough mixing, 1.0 mL (2 g) reagent grade sulfuric acid was added. The hotplate-stirrer was set to 55 0C and after a minute or so of boiling when methylal vapor reached the stopcock base, the stopcock was closed. At 30 minute intervals the temperature was raised to 65 0C, 75 0C, then to 85 0C where it remained overnight. The next day the temperature was increased at 2 hour (hr) intervals to 95 0C, 105 0C and to 1 15 0C overnight. The next day the reactor was cooled while stirring, opened and the contents were neutralized and made basic by careful addition of 100 ml. of sodium methoxide/methanol solution made by reacting/dissolving 1.6 g freshly cut sodium metal in 100 mL of dry methanol.The mixture of solid and liquid was filtered using a Buchner funnel and cellulose filter paper. The solid was washed several times with dry methanol. The washings were added to the filtrate. The combined filtrate washings were transferred to a 250 mL 14/20 flask with stir-bar and rigged for fractional distillation through a 12 cm Vigreaux column. Methanol/methylal was distilled off until the head reached 70 0C. The pot material, a mixture of liquid and solid, was transferred to a 100 mL 14/20 flask and rigged for high vacuum distillation in a special still designed to strip volatiles from lower volatility oil under dynamic vacuum. Thus residual methanol, methylal, trioxane and CH3O(CH2O)nCH3 (n = 2 and 3) were removed while the distilling oil (5-10 mL) was identified by 1H NMR as almost pure CH3O(CH2O)4CH3, a free-flowing colorless oil. The approximately 20 mL of pot residue semi-solidified on cooling and was extracted with chloroform to yield about 10 mL Of CH3O(CH2O)nCH3 (n = 6 and 7), an oily colorless liquid, confirmed by 1H NMR after removal of the chloroform.The filter cake from the Buchner filtration was placed in a cellulose extraction thimble and extracted with chloroform in a Soxhlet extractor for two days. On removal of the chloroform the extract yielded about 15 grams of CH3O(CH2O)nCH3 (n = 8-13) which yielded about 5 grams of the oligomer where n= 8 and 9, a waxy semisolid, which was petroleum ether soluble, and about 5 g of n = 1 1-13, a white friable solid, which was insoluble in petroleum ether. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
22.4%; 17.5%; 8.4% | With La2O3 doped titania; at 130℃; under 4500.45 Torr; for 4.0h;Autoclave; | catalyst was added in the 300 ml autoclave reactorCl-/ of TiO2-La2O3Wherein the Cl-content of TiO2-La2O35% by weight, TiO2And La2O3Were reacted with 20, 100 g of methylal and 100 g of paraformaldehyde at 130 C and 0.6 MPa autogenous pressure for 4 h. The samples were centrifuged and analyzed by gas chromatography.The product contains polyoxymethylene ether as well as unreacted raw materials methylal and paraformaldehyde, the composition of which is shown in Table 1 |
With macroporous strong acidic styrene type cation exchange resin catalyst; at 100℃; under 15001.5 Torr; for 10.0h; | Embodiment 2 The process flow of this embodiment is the same as Embodiment 1. The reaction feedstock and conditions of this embodiment are similar to Embodiment 1, and the difference is that the reaction temperature is controlled at 100C all the time, after 10 hours the reaction is completed. The final overall yield of the target product is 51.66wt.%, DMM8 is not detected throughout the reaction. [0037] The concentration distribution of final products in Embodiment 1 and Embodiment 2 is shown in the following table. Serial number DMM2 DMM3 DMM4 DMM5-8 DMMn>8 Embodiment 1 25.45wt.% 15.12wt.% 8.73wt.% 9.44wt.% ?0 Embodiment 2 22.98wt.% 13.72wt.% 7.33wt.% 7.63wt.% ?0 [0038] As can be seen by analyzing the table, after the same reaction time of 10 hours, the operation scheme of successive stepwise cooling is compared with the isothermal reaction in which the temperature is kept at the initial temperature of the aforementioned successive cooling, and it is found that the concentration of each kind of the target product of the former is higher than the latter, the overall yield of SigmaDMM2-8 is increased by about 7 percentage points, the proportion of DMM5-8 in the target product is also higher. It is clearly indicated that successive cooling indeed promote the equilibrium of the reaction system to shift in the direction of producing the target product, and it can not only increase the one-way overall yield of the target product, but also improve the selectivity of target products with higher degree of polymerization of methoxy groups, thus strengthen the synthesis reaction. | |
With Cl -/TiO2-La2O3/SBA-15 (Si/Al=38); at 130℃; under 4500.45 Torr; for 4.0h; | In 300 ml of reactor by adding 2 g catalyst Cl -/TiO2-La2O3/SBA-15 (Si/Al=38), wherein the modified solid super strong acid with molecular sieve carrier SBA-15 than is the mass fraction of 70:30, Cl- content is TiO2-La2O3 weight 5%, TiO2 and La2O3 molar ratio of 20,100 g methylal and 100 g paraformaldehyde, reaction under 130 C and 0.6 MPa autogenous pressure for 4h, the sample extracted by the gas chromatographic analysis. Comprising polyoxymethylene dimethyl ether in the product not of the raw material and methylal and paraformaldehyde, its composition distribution as shown in table 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With strong acidic styrene type cation exchange resin catalyst; at 80 - 100℃; under 15001.5 Torr; for 3.0h; | Embodiment 5 [0043] Experimental device of the process flow of this embodiment is shown in Figure 1. The feedstock solution is prepared according to a 1.5:1 molar ratio of trioxane metered in formaldehyde units to methylal, the solution is added into a 0.3L single-stage stirred tank reactor, and then 001x7 strong acidic styrene type cation exchange resin catalyst at the amount of 3wt% of the overall feedstock is added. The initial pressure of the reaction is controlled at about 2.0MPa, and stirring speed is 250r/min. And the isothermal reaction experiment using stepwise cooling is carried out in accordance with the following procedures: the reaction mixture is rapidly heated to 100C, after that the isothermal reaction is carried out for 1 hour; the reaction temperature is rapidly cooled to 90C, then the isothermal reaction is carried out for 1 hour again; the reaction temperature is rapidly cooled to 80C in a few minutes, then the isothermal reaction is carried out for 1 hour, and the reaction is completed after 3 hours in total of reaction. The sampling is started from when the reaction temperature reaches 100C and the timing is started, thereafter samples are taken once per hour for analysis of product composition. [0044] The final overall yield of the target product is 47.55wt.% after 3 hours. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With C16H36NO3S(1+)*CH3O4S(1-); at 125 - 130℃; under 26252.6 - 30003 Torr;Inert atmosphere; | To the reactor R1, the ionic liquid catalyst IL1 was added at a feeding speed of 9.8 g/h. When the catalystsolution began to circulate, the feeding was stopped, and the concentration of the catalyst was kept to be not less than4 wt.%. The initial feeding speeds of paraformaldehyde and methanol were 72 g/h and 47.5 mL/h, respectively. Whenthe reaction materials began to circulate, the feeding speeds of the formaldehyde and methanol were 34 g/h and 36mL/h, respectively. The operation conditions of the reactor R1 were controlled as 125?130C and 3.5?4.0 MPa. Thereactor effluent liquid was fed into the extraction tower C2. The feeding speed of the extraction agent, benzene, was245 mL/h (being 1 fold more than the volume of the reaction liquid). The heavy phase (the catalyst, aqueous formaldehydesolution) was continuously fed into the film evaporator S2 from the tower bottom, where most of water was removed at65C/-0.085 MPa, was after that the heavy phase was fed into the reactor for reuse. The light phase (the product phase)was continuously fed into the rectification tower C3 from the tower top. The light components, DMM1, formaldehyde andmethanol were continuously distilled from the tower top at 40?65C, and fed back into the reaction unit for reuse, whilethe tower bottom liquid was fed into the rectification tower C4. The extraction agent, benzene, distilled from the towertop at 78?80C was fed back into the storage tank V1 for reuse, while the tower bottom liquid was fed into the rectificationtower C5. DMM2 and trioxymethylene (the by-product) distilled from the tower top at 98?110C were fed back to thereaction unit for reuse, while the product DMM3-8 flowing out from the tower bottom was fed into the product storage tank. Quantitative analysis of the samples taken from the reaction liquid, the extract, the aqueous catalyst solution,the recycled material and the product at certain interval was carried out by using the gas chromatograph. The test wasrun for 100 h totally. The average values of the test result were listed in Table 2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With C16H36NO3S(1+)*CH3O4S(1-); at 125 - 130℃; under 26252.6 - 30003 Torr;Inert atmosphere; | To the reactor R1, the ionic liquid catalyst IL1 was added at a feeding speed of 9.8 g/h. When the catalystsolution began to circulate, the feeding was stopped, and the concentration of the catalyst was kept to be not less than4 wt.%. The initial feeding speeds of the concentrated formaldehyde and methanol were 170 mL/h and 68 mL/h, respectively.When the reaction materials began to circulate, the feeding speed of the formaldehyde was 70 mL/h. The operationconditions of the reactor R1 were controlled as 125?130C and 3.5?4.0 MPa. The reactor effluent liquid was fed intothe extraction tower C2. The feeding speed of the extraction agent, benzene, was 250 mL/h (being 1 fold more than thevolume of the reaction liquid). The heavy phase (the catalyst and aqueous formaldehyde solution) was continuously fedinto the film evaporator S2 from the tower bottom, where most of water was removed at 65C/-0.085 MPa, after that theheavy phase was fed into the reactor for reuse. The light phase (the product phase) was continuously fed into therectification tower C3 from the tower top. The light component, DMM1, methanol and formaldehyde, was continuously distilled from the tower top at 40?65C, and was fed back into the reaction unit for reuse, while the tower bottom liquidwas fed into the rectification tower C4. The extraction agent, benzene, distilled from the tower top at 78?80C was fedback into the storage tank V1 for reuse, while the tower bottom liquid was fed into the rectification tower C5. DMM2 andtrioxymethylene (the by-product) distilled from the tower top at 98?110C were fed back to the reaction unit for reuse,while the product, DMM3-8, flowing out from the tower bottom was fed into the product storage tank. Quantitative analysis of the samples taken from the reaction liquid, the extract, the aqueous catalyst solution,the recycled material and the product at certain interval was carried out by using the gas chromatograph. The test wasrun for 100 h totally. The average values of the test result were listed in Table 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With C16H36NO3S(1+)*CH3O4S(1-); In water; at 125 - 130℃; under 26252.6 - 30003 Torr; | [0105] In the process shown in FIG. 1, the reactor R1 was a shell and tube reactor. The reactor R1 and the reactor heat exchanger were communicated with each other circularly, the reaction liquid was circulated in the reactor and the heat exchanger, and the volume was 500 mL. [0106] The air in the system was replaced by purging with high-purity nitrogen. To the formaldehyde concentrator S1, an aqueous formaldehyde solution having a concentration of 37 wt. % was continuously added at a feeding speed of 135 mL/h. The temperature of the concentrator S1 was controlled at 8090 C., and the vacuum degree thereof was controlled at -0.05-0.06 MPa. The vapor phase was fed into the dilute-aldehyde condenser E2 through the pipeline 3, and condensed to form liquid dilute formaldehyde, which was fed into the dilute-aldehyde receiving tank V3 through the pipeline 7 at a flow rate of 65 mL/h. The liquid phase was a formaldehyde solution of 60 wt. %, and delivered into the acetalization reactor R1 in C zone through the pipeline 5 at a flow rate of 70 mL/h. [0107] To the reactor R1, the ionic liquid catalyst IL1 was added at a feeding speed of 9.8 g/h. When the catalyst solution began to circulate, the feeding was stopped, and the concentration of the catalyst was kept to be not less than 4 wt. %. The initial feeding speeds of the concentrated formaldehyde and methanol were 170 mL/h and 68 mL/h, respectively. When the reaction materials began to circulate, the feeding speed of the formaldehyde was 70 mL/h. The operation conditions of the reactor R1 were controlled as 125130 C. and 3.54.0 MPa. The reactor effluent liquid was fed into the extraction tower C2. The feeding speed of the extraction agent, benzene, was 250 mL/h (being 1 fold more than the volume of the reaction liquid). The heavy phase (the catalyst and aqueous formaldehyde solution) was continuously fed into the film evaporator S2 from the tower bottom, where most of water was removed at 65 C./-0.085 MPa, after that the heavy phase was fed into the reactor for reuse. The light phase (the product phase) was continuously fed into the rectification tower C3 from the tower top. The light component, DMM1, methanol and formaldehyde, was continuously distilled from the tower top at 4065 C., and was fed back into the reaction unit for reuse, while the tower bottom liquid was fed into the rectification tower C4. The extraction agent, benzene, distilled from the tower top at 7880 C. was fed back into the storage tank V1 for reuse, while the tower bottom liquid was fed into the rectification tower C5. DMM2 and trioxymethylene (the by-product) distilled from the tower top at 98110 C. were fed back to the reaction unit for reuse, while the product, DMM3-8, flowing out from the tower bottom was fed into the product storage tank. [0108] Quantitative analysis of the samples taken from the reaction liquid, the extract, the aqueous catalyst solution, the recycled material and the product at certain interval was carried out by using the gas chromatograph. The test was run for 100 h totally. The average values of the test result were listed in Table 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
23%; 23.3%; 14.9% | With ZrO2#dotLa2O3; at 130℃; under 6000.6 Torr; for 4.0h; | In a 300 ml reactor, 2 g of catalyst was added SO42-/ of ZrO2-La2O3, Where SO42-content of ZrO2-La2O35% by weight, ZrO2And La2O3Was reacted with 1,100 g of methanol and 100 g of paraformaldehyde at 130 C and 0.8 MPa autogenous pressure for 4 h. The sample was centrifuged and analyzed by gas chromatography.The product contains polyoxymethylene ether as well as unreacted starting materials methanol and paraformaldehyde, the composition of which is shown in Table 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With SO42-/ZrO2-La2O3/SBA-15 (Si/Al=25); at 130℃; under 6000.6 Torr; for 4.0h; | In 300 ml of reactor by adding 2 g catalyst SO42-/ZrO2-La2O3/SBA-15 (Si/Al=25), wherein the modified solid super strong acid with molecular sieve carrier SBA-15 than is the mass fraction of 20:80, SO42- content is ZrO2-La2O3 weight 5%, ZrO2 and La2O3 molar ratio of 1,100 g methanol, and 100 g paraformaldehyde, reaction under 130 C and 0.8 MPa autogenous pressure for 4h, the sample extracted by the gas chromatographic analysis. polyoxymethylene dimethyl ether in the product and comprising unreacted raw material methanol and paraformaldehyde, its composition distribution as shown in table 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42%Chromat.; 29%Chromat.; 14%Chromat. | With Amberlyst A15 resin; at 50℃; for 1.0h; | 100 g of methylal (also called dimethoxymethane CH3-OCH2-OCH3) (1.32 mol) and 30 g of trioxane (1 mol) were loaded into a 500 ml jacketed Schott reactor equipped with mechanical stirring, a condenser, and a temperature probe). 5 g of AmberlystR A15 resin, previously washed with methanol and dried under vacuum, are added. The mixture is heated to 50 C. and allowed to react for 1 hour. The reaction mixture is filtered and then washed with 10 g of 15% aqueous sodium hydroxide solution. The methylal is removed by evaporation under reduced pressure (90 C., 600 mBar (60,000 Pa) measured at the evaporator) on a rotary evaporator, then the POMM2 and the residual water are then removed by vacuum distillation. (Oldershaw type column with 10 trays) operating at a pressure of 200 mBar (20,000 Pa) at 90 C. 32 g of a cut POMM3-8 (CH3-(CH2O)n-OCH3 where n is 3 to 8) are obtained. (0061) The mass distribution of the product obtained is determined by GPC analysis as shown in Table 2. |