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CAS No. : | 106-23-0 | MDL No. : | MFCD00038090 |
Formula : | C10H18O | Boiling Point : | - |
Linear Structure Formula : | (CH3)2CCHCH2CH2CH(CH3)CH2COH | InChI Key : | NEHNMFOYXAPHSD-UHFFFAOYSA-N |
M.W : | 154.25 | Pubchem ID : | 7794 |
Synonyms : |
|
Chemical Name : | 3,7-Dimethyloct-6-enal |
Signal Word: | Danger | Class: | 9 |
Precautionary Statements: | P501-P273-P260-P270-P264-P280-P391-P314-P337+P313-P305+P351+P338-P301+P312+P330 | UN#: | 3082 |
Hazard Statements: | H302-H319-H372-H410 | Packing Group: | Ⅲ |
GHS Pictogram: |
* 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;cetyltrimethylammonim bromide; In water; at 35℃; for 5.0h; | A method for carrying out this invention is as indicated below. The actual detail of the processing will be known to those skilled in the art:1. A solution of hexadecyltrimethylammonium bromide (0.05%) in 5% sulphuric was charged into a reactor and vigorously stirred. Citronellal in an amount equivalent to 33.32.% of the total charge was fed into the reactor over a five hour period with the temperature being maintained at or below 350C. Stirring was continued for a further three hours.2. The stirring was stopped and the two phases were allowed to separate. The lower aqueous acid solution was run off to be used in further batches. The temperature should be maintained above 30C for ease of separation. <n="15"/>3. The organic layer was washed with a solution of mild alkali such as sodium carbonate or sodium bicarbonate to remove residual acid until an aliquot shaken with water showed a pH of 5.0 - 8.0. The product was filtered through a lOOmuM filter to remove residual water and any suspended solids.4. The resultant product is a clear or slightly opaque almost colourless, moderately viscous liquid with a slight pleasant floral odour quite unlike that of the starting material.Analysis of the product of the above process shows a typical composition: PMD-citronellal acetal 5-12%Isopulegole 7-14%/?alphara-menthane-3,8-diol remainder |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
<= 7%; <= 10%; 90% | sulfuric acid; In water; at 60℃; for 7.0h; | A bench-scale PMD synthesis reaction was carried out using a 500 ml jacketed glass reactor, a heated feed vessel, and an over-head stirrer fitted with a four-blade stainless steel impeller, thermometer and two integral baffles. The reactor temperature was set to a temperature of 60 deg C by circulating heating fluid, kept at the desired constant temperature (+/- 0.5 deg C) in a constant temperature bath. Dilute sulphuric acid (14Og of a 0.53% (m/m) solution 0.00757mol) was added to the reactor and allowed to equilibrate to the desired reaction temperature. Citronellal (30.08g; 0.193mol), pre-heated to the desired reaction temperature, was added to the reactor drop-wise over a period of 60 minutes, while the reactor was agitated at a stirring rate of 2000 rpm. The reaction was allowed to proceed for a further 6 hours following completion of the citronellal addition step.Once the reaction had stopped, the reactor contents were drained into a separating funnel and allowed to settle for 1 minute after which the aqueous phase was drained off. The organic phase was washed with 5Og of a 2.5% (w/v) solution of NaHCO3 to remove any residual sulphuric acid catalyst. The mixture was allowed to settle for approximately 2 minutes after which the bottom aqueous phase was drained off.Residual water was removed from the organic phase on a rotary evaporator. The crude product was then distilled under vacuum (1 15 deg C and 8 mBar) to recover citronellal and pulegol. The desired product PMD was recovered as a thick viscous liquid from the bottom of the still and analyzed by means of gas chromatography. In different embodiments, the yield of PMD varied between 80 - 90 % and typically contained up to about 10 % of pulegol, up to about 7% PMD-acetal and about 2- 5% of un-reacted citronellal. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With sulfuric acid; In water; at 100℃; for 4.0h;Green chemistry; | Citronellal (30.08 g, 0.193 mol) was added into stirred dilutesulphuric acid (140 g, 0.0076 mol of a 0.3% (v/v)) solution at atemperature of 100 C. After 4 hour of stirring the aqueousphase was separated from the organic oil phase. The organicphase was neutralised with 50 mL of 2.5% (v/v) sodium hydrogen carbonate (NaHCO3) solution to remove the remains ofsulphuric acid catalyst and dried (MgSO4). The product was recrystallized from n-hexane at -18 C for 24 hours. p-Menthane-3,8-diol (3) was obtained as white crystals (96%). 1H NMR(400 MHz, CDCl3, ppm) delta0.80-0.96 (m, 3H), 0.89-0.90 (m,1H), 0.99-1.03 (m, 2H), 1.11-1.19 (m, 3H), 1.33 (s, 3H),1.66-1.68 (m, 2H), 1.72-1.82 (m, 3H), 3.40 (s, 2H) and 4.38(br s, 1H); 13C NMR(100 MHz, CDCl3, ppm) delta20.2, 22.1,25.5, 28.6, 29.9, 34.8, 42.4, 49.2, 67.7 and 73.2; FTIR (cm-1):3220, 2941, 2911, 1158 and 931; m/z(CI) 172 (M+, 1), 157 (9),139 (20), 96 (50), 81 (100) and 59 (90); GC tR= 15.0 min. |
sulfuric acid; In water; at 90℃; for 0.5h;Product distribution / selectivity; | The experiment described in Example 1 was repeated several times with slight modifications in the reaction temperature, amount of catalyst used, and the ratio of the aqueous catalyst phase relative to the organic citronellal phase as indicated in Table 1. In all of the examples of Table 1 , the citronellal starting material was added in a single batch to the pre-heated aqueous catalyst mixture, and the reaction was allowed to proceed for only 30 minutes before the reaction was stopped and worked up as described for Example 1. The results obtained for these experiments, namely the amount of citronellal (mmol), amount of PMD (mmol), and amount of PMD-acetal (mmol) are summarised in Table 1. | |
64.2 g | With sulfuric acid; water; In toluene; at 70℃; for 11.0h; | Example 2 Synthesis of (IRS)-p-Menthane-3,8-diol Isomer Mixture By using 77.1 g of dl-citronellal (manufactured by Takasago International Corporation) containing 50% by mass of d-citronellal and 50% by mass of 1-citronellal as a raw material, 64.2 g of a (1RS)-p-menthane-3,8-diol isomer mixture was obtained by the same synthetic method as in [Example 1]. In this isomer mixture, (1R)-isomers accounted for 50% by mass of the entire composition, and (1S)-isomers accounted for 50% by mass of the entire composition (more specifically, the (1S,3R,4S) isomer accounted for 33% by mass of the entire composition, and the (1R,3S,4R) isomer accounted for 33% by mass of the entire composition). |
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