Synthesis method of ethyoxyl cyclododecyloxymethane

Abstract

The invention relates to the technical field of organic synthesis, in particular to a synthesis method of ethyoxyl cyclododecyloxymethane, which comprises the following steps: S1, heating and mixing diethoxymethane and cyclododecanol, adding an acid catalyst, and stirring to react; and S2, after the reaction is finished, introducing into a reactor containing a potassium carbonate aqueous solution, taking an upper-layer solution, and carrying out rectification separation, thereby obtaining the product. According to the synthesis method of ethyoxyl cyclododecyloxymethane, provided by the invention, the raw materials can be fully utilized, the single-time yield reaches 80% or above, the yield after recycling reaches 95% or above, meanwhile, continuous reaction can be realized, the production efficiency is high, and the method has relatively high economic value.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a method for synthesizing ethoxycyclododecyloxymethane. Background Art

[0002] Ethoxycyclododecyloxymethane, also known as ambergris, ethoxymethoxycyclododecane or succinic ether, is a novel woody fragrance with a light and long-lasting scent that is neither too strong nor easy to dissipate quickly. Therefore, it is regarded as a representative of elegance and freshness.

[0003] At present, except for the Japanese Kao Spanish factory, there are basically no domestic companies producing ethoxycyclododecyloxymethane. For example, Chinese patent CN102558134A discloses an ambergris fragrance, which has an ambergris smell and a particularly strong internal adhesion, and is particularly suitable for use in spice mixtures. By using specific compounds and mixtures, the fragrance retention and retention of spice mixtures can be improved. However, the ambergris fragrance prepared by this technology is not ambergris, and the domestic market needs to rely on imports to meet the demand for ethoxycyclododecyloxymethane. And as its demand in the high-end flavor market at home and abroad gradually increases, inventing a method for synthesizing ethoxycyclododecyloxymethane may have higher economic value. Summary of the invention

[0004] In order to solve the problems in the prior art, the present invention provides a method for synthesizing ethoxycyclododecyloxymethane, comprising the following steps:

[0005] S1, heating and mixing diethoxymethane and cyclododecanol, adding an acidic catalyst and stirring to react;

[0006] S2. After the reaction is completed, the solution is passed into a reactor containing an aqueous solution of potassium carbonate, and the upper layer is separated by distillation to obtain the product.

[0007] In one embodiment, the molar ratio of cyclododecanol to diethoxymethane is 1:(5-10).

[0008] In a preferred embodiment, the molar ratio of cyclododecanol to diethoxymethane is any one of 1:5, 1:6, 1:7, 1:8, 1:9, and 1:10.

[0009] In a more preferred embodiment, the molar ratio of cyclododecanol to diethoxymethane is 1:6.

[0010] In one embodiment, the mass of the acidic catalyst accounts for 0.2%-0.5% of the mass of cyclododecyl alcohol.

[0011] In a preferred embodiment, the mass of the acidic catalyst accounts for any one of 0.2%, 0.3%, 0.4% and 0.5% of the mass of cyclododecyl alcohol.

[0012] In a preferred embodiment, the mass of the acidic catalyst accounts for 0.2% of the mass of cyclododecyl alcohol.

[0013] In one embodiment, the acidic catalyst is selected from at least one of toluenesulfonic acid, concentrated sulfuric acid, 36wet acidic resin, HND-8 solid acid, and HND-53 solid acid.

[0014] In a preferred embodiment, the acidic catalyst is concentrated sulfuric acid.

[0015] In one embodiment, the temperature of the heating and mixing in step S1 is 88°C-93°C.

[0016] In a preferred embodiment, the temperature of the heating and mixing in step S1 is selected from any one of 88°C, 89°C, 90°C, 91°C, 92°C, and 93°C.

[0017] In a more preferred embodiment, the temperature of the heating and mixing in step S1 is 88°C.

[0018] In one embodiment, during the stirring reaction in step S1, the azeotrope distilled out during the reaction process is recovered, and the azeotrope is an azeotrope of ethanol and diethoxymethane.

[0019] In one embodiment, the recycling process includes: mixing the azeotrope distilled from the reaction process with water in a mass ratio of 1:0.5, washing 2-3 times, and collecting the upper oil phase. The mass proportion of diethoxymethane in the upper oil phase is 97%. The upper oil phase can be recycled as a reaction raw material.

[0020] In the system of the present invention, the byproduct of the reaction of cyclododecanol and diethoxymethane is ethanol, which reacts with sulfuric acid or cyclododecanol to generate a small amount of water, thereby hydrolyzing ethoxycyclododecyloxymethane. In the present invention, cyclododecanol and diethoxymethane, raw materials for preparing ethoxycyclododecyloxymethane, are reacted with an acidic catalyst under normal pressure conditions of 88° C.-93° C. in a slightly boiling state. During the reaction, the byproduct ethanol and diethoxymethane azeotrope to form an azeotrope. By recycling the azeotrope, the influence of the byproduct ethanol on the preparation of subsequent products can be avoided, and the utilization rate of diethoxymethane can also be improved.

[0021] In one embodiment, the stirring reaction time in step S1 is 3-5 hours.

[0022] In a preferred embodiment, the stirring reaction time in step S1 is selected from any one of 1 h, 2 h, 3 h, 4 h, and 5 h.

[0023] In a more preferred embodiment, the stirring reaction time in step S1 is 3 hours.

[0024] In one embodiment, the molar ratio of potassium carbonate to the acidic catalyst in the potassium carbonate aqueous solution in step S2 is 1.5:1.

[0025] In one embodiment, the mass percentage of potassium carbonate in the potassium carbonate aqueous solution is 5 wt %.

[0026] In one embodiment, the distillation specifically comprises: heating the upper solution from 30°C to 90°C and distilling under reduced pressure until no more fraction is produced, then decompressing the solution for a second time and heating the solution to 170°C, and collecting ethoxycyclododecyloxymethane through a condenser.

[0027] In one embodiment, the time for heating from 30°C to 90°C is 2-3 hours, which may be 2 hours, 2.5 hours, or 3 hours.

[0028] In a preferred embodiment, the time for heating from 30°C to 90°C is 2.5h.

[0029] In one embodiment, the pressure of the reduced pressure distillation is 9000-10000 Pa.

[0030] In a preferred embodiment, the pressure of the reduced pressure distillation is any one of 9000Pa, 9500Pa, and 10000Pa.

[0031] In a more preferred embodiment, the pressure of the reduced pressure distillation is 10000 Pa.

[0032] In one embodiment, the pressure of the secondary decompression is 1000Pa.

[0033] In a preferred embodiment, the distillation specifically includes: heating the upper solution from 30°C to 90°C for 2.5h and distilling at 10000Pa until no more fraction is produced, then reducing the pressure to 1000Pa for a second time and heating to 170°C, and collecting ethoxycyclododecyloxymethane through a condenser.

[0034] In the system of the present invention, diethoxymethane and cyclododecanol are not completely consumed after the reaction is completed, and continued reaction will produce impurities that affect the purity of ethoxycyclododecyloxymethane. The rectification process of the present invention adopts four-stage collection. During the temperature rise process from 30°C to 90°C, diethoxymethane with a relatively low boiling point is distilled and collected at this stage and then used as a raw material for the reaction; during the secondary decompression and temperature rise to 170°C, since the relative boiling points of cyclododecanol and ethoxycyclododecyloxymethane are close, cyclododecanol will be distilled out first, followed by a blend of cyclododecanol and ethoxycyclododecyloxymethane, and finally ethoxycyclododecyloxymethane. The collected diethoxymethane and cyclododecanol can be directly reused as raw materials for the reaction, and the collected blend of cyclododecanol and ethoxycyclododecyloxymethane can repeat the rectification process to improve the yield of ethoxycyclododecyloxymethane.

[0035] Beneficial Effects

[0036] 1. The synthesis method of ethoxycyclododecyloxymethane provided by the present invention has a single yield of more than 80% and a yield of more than 95% after recycling.

[0037] 2. The method for synthesizing ethoxycyclododecyloxymethane provided by the present invention can completely recycle the raw materials cyclododecanol and diethoxymethane for preparation, thereby improving the utilization rate of raw materials.

[0038] 3. In the present invention, the raw materials and the acidic catalyst are reacted at 88°C-93°C for 3 hours, the reaction temperature is low, the reaction time is short, the reaction energy consumption is low, and the influence of the reaction by-product ethanol on the subsequent preparation is avoided.

[0039] 4. The distillation process of the present invention adopts four-stage collection, and the yield of ethoxycyclododecyloxymethane is improved by respectively collecting the distilled diethoxymethane, cyclododecyl alcohol, a blend of cyclododecyl alcohol and ethoxycyclododecyloxymethane and the final product ethoxycyclododecyloxymethane.

[0040] 5. The synthesis method of ethoxycyclododecyloxymethane provided by the present invention can react continuously, has high production efficiency and high economic value. DETAILED DESCRIPTION

[0041] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with the examples. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. The experimental methods in the examples without specifying specific conditions are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used without specifying the manufacturer are all conventional products that can be purchased commercially.

[0042] Example 1

[0043] This embodiment provides a method for synthesizing ethoxycyclododecyloxymethane, comprising the following steps:

[0044] S1, heating and mixing diethoxymethane and cyclododecanol, adding an acidic catalyst and stirring to react;

[0045] S2. After the reaction is completed, the solution is passed into a reactor containing an aqueous solution of potassium carbonate, and the upper layer is separated by distillation to obtain the product.

[0046] The molar ratio of the cyclododecanol to diethoxymethane is 1:6.

[0047] The acid catalyst is concentrated sulfuric acid, and the mass of the acid catalyst accounts for 0.2% of the mass of cyclododecyl alcohol.

[0048] The temperature of heating and mixing in the step S1 is 88°C.

[0049] In the step S1, the azeotrope distilled out during the stirring reaction is recovered, and the azeotrope is the azeotrope of ethanol and diethoxymethane.

[0050] The recycling process includes: mixing the azeotrope distilled from the reaction process with water in a mass ratio of 1:0.5, washing 2-3 times, and collecting the upper oil phase. The mass proportion of diethoxymethane in the upper oil phase is 97%.

[0051] The stirring reaction time in step S1 is 3 hours.

[0052] The molar ratio of potassium carbonate to the acidic catalyst in the potassium carbonate aqueous solution in step S2 is 1.5: 1. The mass proportion of potassium carbonate in the potassium carbonate aqueous solution is 5 wt%.

[0053] The distillation specifically includes: heating the upper solution from 30° C. to 90° C. for 2.5 hours and distilling at 10000 Pa until no more fraction is produced, then reducing the pressure to 1000 Pa for a second time and heating to 170° C., and collecting ethoxycyclododecyloxymethane through a condenser.

[0054] Example 2

[0055] This embodiment provides a method for synthesizing ethoxycyclododecyloxymethane, comprising the following steps:

[0056] S1, heating and mixing diethoxymethane and cyclododecanol, adding an acidic catalyst and stirring to react;

[0057] S2. After the reaction is completed, the solution is passed into a reactor containing an aqueous solution of potassium carbonate, and the upper layer is separated by distillation to obtain the product.

[0058] The molar ratio of the cyclododecanol to diethoxymethane is 1:6.

[0059] The acid catalyst is concentrated sulfuric acid, and the mass of the acid catalyst accounts for 0.3% of the mass of cyclododecyl alcohol.

[0060] The temperature of heating and mixing in the step S1 is 88°C.

[0061] In the step S1, the azeotrope distilled out during the stirring reaction is recovered, and the azeotrope is the azeotrope of ethanol and diethoxymethane.

[0062] The recycling process includes: mixing the azeotrope distilled from the reaction process with water in a mass ratio of 1:0.5, washing 2-3 times, and collecting the upper oil phase. The mass proportion of diethoxymethane in the upper oil phase is 97%.

[0063] The stirring reaction time in step S1 is 3 hours.

[0064] The molar ratio of potassium carbonate to the acidic catalyst in the potassium carbonate aqueous solution in step S2 is 1.5: 1. The mass proportion of potassium carbonate in the potassium carbonate aqueous solution is 5 wt%.

[0065] The distillation specifically includes: heating the upper solution from 30° C. to 90° C. for 2.5 hours and distilling at 10000 Pa until no more fraction is produced, then reducing the pressure to 1000 Pa for a second time and heating to 170° C., and collecting ethoxycyclododecyloxymethane through a condenser.

[0066] Example 3

[0067] This embodiment provides a method for synthesizing ethoxycyclododecyloxymethane, comprising the following steps:

[0068] S1, heating and mixing diethoxymethane and cyclododecanol, adding an acidic catalyst and stirring to react;

[0069] S2. After the reaction is completed, the solution is passed into a reactor containing an aqueous solution of potassium carbonate, and the upper layer is separated by distillation to obtain the product.

[0070] The molar ratio of the cyclododecanol to diethoxymethane is 1:6.

[0071] The acid catalyst is concentrated sulfuric acid, and the mass of the acid catalyst accounts for 0.4% of the mass of cyclododecyl alcohol.

[0072] The temperature of heating and mixing in the step S1 is 88°C.

[0073] In the step S1, the azeotrope distilled out during the stirring reaction is recovered, and the azeotrope is the azeotrope of ethanol and diethoxymethane.

[0074] The recycling process includes: mixing the azeotrope distilled from the reaction process with water in a mass ratio of 1:0.5, washing 2-3 times, and collecting the upper oil phase. The mass proportion of diethoxymethane in the upper oil phase is 97%.

[0075] The stirring reaction time in step S1 is 3 hours.

[0076] The molar ratio of potassium carbonate to the acidic catalyst in the potassium carbonate aqueous solution in step S2 is 1.5: 1. The mass proportion of potassium carbonate in the potassium carbonate aqueous solution is 5 wt%.

[0077] The distillation specifically includes: heating the upper solution from 30° C. to 90° C. for 2.5 hours and distilling at 10000 Pa until no more fraction is produced, then reducing the pressure to 1000 Pa for a second time and heating to 170° C., and collecting ethoxycyclododecyloxymethane through a condenser.

[0078] Example 4

[0079] This embodiment provides a method for synthesizing ethoxycyclododecyloxymethane, comprising the following steps:

[0080] S1, heating and mixing diethoxymethane and cyclododecanol, adding an acidic catalyst and stirring to react;

[0081] S2. After the reaction is completed, the solution is passed into a reactor containing an aqueous solution of potassium carbonate, and the upper layer is separated by distillation to obtain the product.

[0082] The molar ratio of the cyclododecanol to diethoxymethane is 1:6.

[0083] The acid catalyst is concentrated sulfuric acid, and the mass of the acid catalyst accounts for 0.5% of the mass of cyclododecyl alcohol.

[0084] The temperature of heating and mixing in the step S1 is 88°C.

[0085] In the step S1, the azeotrope distilled out during the stirring reaction is recovered, and the azeotrope is the azeotrope of ethanol and diethoxymethane.

[0086] The recycling process includes: mixing the azeotrope distilled from the reaction process with water in a mass ratio of 1:0.5, washing 2-3 times, and collecting the upper oil phase. The mass proportion of diethoxymethane in the upper oil phase is 97%.

[0087] The stirring reaction time in step S1 is 3 hours.

[0088] The molar ratio of potassium carbonate to the acidic catalyst in the potassium carbonate aqueous solution in step S2 is 1.5: 1. The mass proportion of potassium carbonate in the potassium carbonate aqueous solution is 5 wt%.

[0089] The distillation specifically includes: heating the upper solution from 30° C. to 90° C. for 2.5 hours and distilling at 10000 Pa until no more fraction is produced, then reducing the pressure to 1000 Pa for a second time and heating to 170° C., and collecting ethoxycyclododecyloxymethane through a condenser.

[0090] Example 5

[0091] The specific implementation of this embodiment is the same as that of Example 1, except that the molar ratio of cyclododecanol to diethoxymethane in this embodiment is 1:5.

[0092] Example 6

[0093] The specific implementation of this embodiment is the same as that of Example 1, except that the molar ratio of cyclododecanol to diethoxymethane in this embodiment is 1:7.

[0094] Example 7

[0095] The specific implementation of this embodiment is the same as that of Example 1, except that the molar ratio of cyclododecanol to diethoxymethane in this embodiment is 1:8.

[0096] Example 8

[0097] The specific implementation of this embodiment is the same as that of Example 1, except that the molar ratio of cyclododecanol to diethoxymethane in this embodiment is 1:9.

[0098] Example 9

[0099] The specific implementation of this embodiment is the same as that of Example 1, except that the molar ratio of cyclododecanol to diethoxymethane in this embodiment is 1:10.

[0100] Example 10

[0101] The specific implementation of this embodiment is the same as that of Example 1, except that the stirring reaction time in step S1 of this embodiment is 4 hours.

[0102] Embodiment 11

[0103] The specific implementation of this embodiment is the same as that of Example 1, except that the stirring reaction time in step S1 of this embodiment is 5 hours.

[0104] Comparative Example 1

[0105] The specific implementation of this comparative example is the same as that of Example 1, except that the recovery treatment in this comparative example includes: directly refluxing the azeotrope distilled out during the reaction process to the reactor for reaction.

[0106] Comparative Example 2

[0107] The specific implementation of this comparative example is the same as that of Example 1, except that the acid catalyst in this comparative example is p-toluenesulfonic acid, and the mass of the acid catalyst accounts for 1% of the mass of cyclododecyl alcohol.

[0108] Comparative Example 3

[0109] The specific implementation of this comparative example is the same as that of Example 1, except that the acid catalyst in this comparative example is 36wet acid resin, and the mass of the acid catalyst accounts for 5% of the mass of cyclododecyl alcohol.

[0110] Comparative Example 4

[0111] The specific implementation of this comparative example is the same as that of Example 1, except that the mass of the acidic catalyst in this comparative example accounts for 0.1% of the mass of cyclododecyl alcohol.

[0112] Comparative Example 5

[0113] The specific implementation of this comparative example is the same as that of Example 1, except that the molar ratio of cyclododecanol to diethoxymethane in this comparative example is 1:2.

[0114] Comparative Example 6

[0115] The specific implementation of this comparative example is the same as that of Example 1, except that the molar ratio of cyclododecanol to diethoxymethane in this comparative example is 1:3.

[0116] Comparative Example 7

[0117] The specific implementation of this comparative example is the same as that of Example 1, except that the molar ratio of cyclododecanol to diethoxymethane in this comparative example is 1:4.

[0118] Comparative Example 8

[0119] The specific implementation of this comparative example is the same as that of Example 1, except that the stirring reaction time in step S1 in this comparative example is 1 hour.

[0120] Comparative Example 9

[0121] The specific implementation of this comparative example is the same as that of Example 1, except that the stirring reaction time in step S1 in this comparative example is 2 hours.

[0122] Comparative Example 10

[0123] The specific implementation of this comparative example is the same as that of Example 1, except that the temperature of heating and mixing in step S1 of this comparative example is 65°C.

[0124] Comparative Example 11

[0125] The specific implementation of this comparative example is the same as that of Example 1, except that the temperature of heating and mixing in step S1 of this comparative example is 70°C.

[0126] Comparative Example 12

[0127] The specific implementation of this comparative example is the same as that of Example 1, except that the temperature of heating and mixing in step S1 of this comparative example is 75°C.

[0128] Performance Testing

[0129] The ethoxycyclododecyloxymethane content (product content), the residual amount of cyclododecanol and the impurity content were tested for the examples and comparative examples, and the test data are listed in Table 1.

[0130] Table 1

[0131]

[0132]

Claims

1. A method for synthesizing ethoxycyclododecyloxymethane, characterized in that: The following steps are involved: S1, heating and mixing diethoxymethane and cyclododecanol, adding an acidic catalyst and stirring to react; S2. After the reaction is completed, the solution is passed into a reactor containing an aqueous solution of potassium carbonate, and the upper layer is separated by distillation to obtain the product.

2. The method for synthesizing ethoxycyclododecyloxymethane according to claim 1, characterized in that: The molar ratio of the cyclododecanol to diethoxymethane is 1:(5-10).

3. The method for synthesizing ethoxycyclododecyloxymethane according to claim 1, characterized in that: The mass of the acidic catalyst accounts for 0.1%-0.5% of the mass of cyclododecyl alcohol.

4. The method for synthesizing ethoxycyclododecyloxymethane according to claim 3, characterized in that: The acid catalyst is selected from at least one of toluenesulfonic acid, concentrated sulfuric acid, 36wet acidic resin, HND-8 solid acid, and HND-53 solid acid.

5. The method for synthesizing ethoxycyclododecyloxymethane according to claim 1, characterized in that: The temperature of the heating and mixing in the step S1 is 80°C-93°C.

6. The method for synthesizing ethoxycyclododecyloxymethane according to claim 5, characterized in that: The stirring reaction time in step S1 is 3-5 hours.

7. The method for synthesizing ethoxycyclododecyloxymethane according to claim 1, characterized in that: In the step S2, the molar ratio of potassium carbonate to the acidic catalyst in the potassium carbonate aqueous solution is 1.5:

1.

8. The method for synthesizing ethoxycyclododecyloxymethane according to claim 7, characterized in that: The mass percentage of potassium carbonate in the potassium carbonate aqueous solution is 5 wt %.

9. The method for synthesizing ethoxycyclododecyloxymethane according to any one of claims 1 to 8, characterized in that: The distillation specifically includes: heating the upper solution from 30° C. to 90° C. and distilling under reduced pressure until no more fraction is produced, then reducing the pressure for a second time and heating to 170° C., and collecting ethoxycyclododecyloxymethane through a condenser.

10. The method for synthesizing ethoxycyclododecyloxymethane according to claim 9, characterized in that: The pressure of the reduced pressure distillation is 9000-10000Pa.

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