Structure of 2,6-Dimethylheptan-4-ol
CAS No.: 108-82-7
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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.
Synonyms: Diisobutyl carbinol
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CAS No. : | 108-82-7 |
Formula : | C9H20O |
M.W : | 144.26 |
SMILES Code : | CC(C)CC(O)CC(C)C |
Synonyms : |
Diisobutyl carbinol
|
MDL No. : | MFCD00008944 |
InChI Key : | HXQPUEQDBSPXTE-UHFFFAOYSA-N |
Pubchem ID : | 7957 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
* 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 |
---|---|---|
95% | With 1?methyl?2?azaadamantane?N?oxyl; sodium hypochlorite pentahydrate; tetra(n-butyl)ammonium hydrogensulfate; In dichloromethane; at 25 - 30℃; for 3.25h; | Instead of TEMPO used in Example 21-methyl-2-azaadamantane-N-oxyl(Commonly known as 1-Me-AZADO) Except that 2.31 g (14.0 mmol) of powdery crystals of sodium hypochlorite pentahydrate was used in place of 0.0162 g (0.10 mmol)Oxidation reaction was carried out in the same manner as in Example 2. 30 minutes after the start of the reaction at the time of the addition of the oxidizing agent, internal standard analysis was carried out by GC in the same manner as in Example 1 to find that 2,6-dimethyl-4-heptanone was produced at a yield of 95%. |
88% | With sodium hypochlorite; tetrabutylammomium bromide; potassium bromide;1-methyl-2-azaadamantane-N-oxyl; In dichloromethane; at 0℃; for 0.333333h;Product distribution / selectivity; | Then, using 1-methyl-AZADO synthesized, the activities thereof as an oxidation catalyst were estimated in the same manner using various secondary alcohols specified in Tables 2 and 3. As for the reaction conditions, the catalyst amount was 0.01 eq. in CH2Cl2, and KBr (0.1 eq.), n-Bu4NBr (0.05 eq.) and NaOCl (1.4 eq.) were further added, and the reaction was carried out under ice cooling. The reaction time was 20 minutes. After completion of the reaction, the percent yield of each product was determined. The percent yield was calculated by the formula: (actual yield, i.e., the amount of product)/(theoretical yield, i.e., calculated from the amount of consumed starting material) x 100 (%). For comparative examples, runs were carried out under the same reaction conditions using TEMPO, and each comparative yield was calculated. The results thus obtained are shown in Tables 2 and 3. Table 2 [Show Image] Test No. Alcohol species Yield (%) Catalyst Me-AZADO (Invention) TEMPO (Compar. Ex.) 2-1[Show Image] 84 83 2-2[Show Image] 91 5 2-3[Show Image] 99 16 2-4[Show Image] 93 15 2-5[Show Image] 100 8 2-6[Show Image] 100 12Table 3 Test No. Alcohol species Yield (%) Catalyst Me-AZADO (Invention) TEMPO (Compar. Ex.) 2-7[Show Image] 99 84 2-8[Show Image] 92 68 2-9[Show Image] 89 0 2-10[Show Image] 88 0 2-11[Show Image] 91 5 In the case of secondary alcohols having a relatively simple steric configuration (e.g. Test No. 2-1 and No. 2-7), the use of 1-methyl-AZADO of the invention as an oxidation catalyst and the use of TEMPO for comparison both gave target products in high yields. On the other hand, in the case of secondary alcohols having a sterically bulky, complicated structure, it was found that the use of 1-methyl-AZADO of the invention resulted in rapid oxidation, giving target products in high yields, whereas the use of TEMPO for comparison gave target products only in low yields. In view of such results, it is evident that 1-methyl-AZADO is a catalyst useful as an oxidation catalyst not only for primary alcohols but also secondary alcohols. |
0% | With sodium hypochlorite; tetrabutylammomium bromide; potassium bromide;2,2,6,6-tetramethyl-piperidine-N-oxyl; In dichloromethane; at 0℃; for 0.333333h;Product distribution / selectivity; | Then, using 1-methyl-AZADO synthesized, the activities thereof as an oxidation catalyst were estimated in the same manner using various secondary alcohols specified in Tables 2 and 3. As for the reaction conditions, the catalyst amount was 0.01 eq. in CH2Cl2, and KBr (0.1 eq.), n-Bu4NBr (0.05 eq.) and NaOCl (1.4 eq.) were further added, and the reaction was carried out under ice cooling. The reaction time was 20 minutes. After completion of the reaction, the percent yield of each product was determined. The percent yield was calculated by the formula: (actual yield, i.e., the amount of product)/(theoretical yield, i.e., calculated from the amount of consumed starting material) x 100 (%). For comparative examples, runs were carried out under the same reaction conditions using TEMPO, and each comparative yield was calculated. The results thus obtained are shown in Tables 2 and 3. Table 2 [Show Image] Test No. Alcohol species Yield (%) Catalyst Me-AZADO (Invention) TEMPO (Compar. Ex.) 2-1[Show Image] 84 83 2-2[Show Image] 91 5 2-3[Show Image] 99 16 2-4[Show Image] 93 15 2-5[Show Image] 100 8 2-6[Show Image] 100 12Table 3 Test No. Alcohol species Yield (%) Catalyst Me-AZADO (Invention) TEMPO (Compar. Ex.) 2-7[Show Image] 99 84 2-8[Show Image] 92 68 2-9[Show Image] 89 0 2-10[Show Image] 88 0 2-11[Show Image] 91 5 In the case of secondary alcohols having a relatively simple steric configuration (e.g. Test No. 2-1 and No. 2-7), the use of 1-methyl-AZADO of the invention as an oxidation catalyst and the use of TEMPO for comparison both gave target products in high yields. On the other hand, in the case of secondary alcohols having a sterically bulky, complicated structure, it was found that the use of 1-methyl-AZADO of the invention resulted in rapid oxidation, giving target products in high yields, whereas the use of TEMPO for comparison gave target products only in low yields. In view of such results, it is evident that 1-methyl-AZADO is a catalyst useful as an oxidation catalyst not only for primary alcohols but also secondary alcohols. |
95%Chromat. | With 1-Me-AZADO+; sodium hypochlorite pentahydrate; tetra(n-butyl)ammonium hydrogensulfate; In dichloromethane; at 20℃; for 0.5h; | General procedure: NaOCl·5H2O crystals (2.0 g, 12.2 mmol) were added in oneportion to a mixture of Bu4NHSO4 (0.17 g, 0.50 mmol),TEMPO (21 mg, 0.13 mmol), and 1 (1.30 g, 10.0 mmol) inCH2Cl2 (10 mL) at 5 C. After 15 min, GC monitoringshowed that 1 had been consumed. The reaction was stoppedafter 0.5 h by quenching with aq sat. Na2SO3 solution (20mL). The organic layer was separated, and the aqueous layerwas extracted with CH2Cl2 (30 mL). The combined organiclayers were washed with H2O (30 mL), dried over Na2SO4,and concentrated to give 2 as colorless oil (1.27 g, crudeyield of 99.2%, GC analysis showed the product to be 96.8%pure). A 0.42 g portion of the crude 2 was purified by bulbto-bulb distillation (6 kPa, 120-130 C) to afford pure 2(0.40 g, 95%). GC-MS analysis gave identical results tothose of an authentic sample. |
95%Chromat. | With 1?methyl?2?azaadamantane?N?oxyl; sodium hypochlorite pentahydrate; tetra(n-butyl)ammonium hydrogensulfate; In dichloromethane; at 20℃; for 0.5h; | General procedure: NaOCl5H2O crystals (12.0e18.0 mmol) wereadded in one portion to a mixture of Bu4NHSO4 (0.170 g,0.50 mmol), TEMPO (15.6 mg, 0.10 mmol), and alcohols (10.0 mmol)in dichloromethane (10 mL or 30 mL) at several temperature. Afterstirring for an appropriate time, 0.5 mL of the organic layer and0.03 g weighed of PCBTF as an internal standard were added to1e2 mL of CH2Cl2 for GC analysis. GCeMS analyses of the productswere identical with authentic samples. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen; at 160℃; under 15751.6 Torr; for 2.8h;Autoclave; | agitator, thermocouple, pressure gauge and heating mantle JGC Catalysts and Chemicals as autoclave Mitsui Chemicals Co., Ltd. DIBK308g a catalyst having an Ltd. N203SD (Cu-Cr-based catalyst) 3.1 g ( was added 1 wt%) with respect to DIBK, it was reacted for 2.8 hours the hydrogenation.The hydrogenation temperature is 160 by using a mantle heater, hydrogenation pressure was controlled to 2.1MPa.Stop the hydrogenation reaction was completed after heating, the temperature was lowered to become 50 C. while maintaining the hydrogenation pressure, filtration with sintered metal filter and the GC analysis of the resulting reaction solution.As a result, DIBK conversion after cooling operation is 97.3%, DIBC selection rate (reacted DIBK basis, hereinafter the same) was 99.9% or more, ketone body residual rate was 2.7%. |