| 86% |
With pyridinium chlorochromate; In dichloromethane; at 20℃; for 1h; |
To a suspension of pyridinium chloro chromate (23.17 g, 107.5 mmol) in DCM(150 mL) was added adamant- 1-ylmethanol (10.5 g, 63.2 mmol) in DCM (100 mL) under stirring. The resulting dark brown coloured reaction mixture was stirred at RT for 1 h. Reaction mixture was diluted with diisopropyl ether (750 mL) and filtered through celite, the filtrate was washed with aqueous IN NaOH (1 x 250 mL ) solution and water (2 x 150 mL). The organic layer was dried over anhydrous sodium sulphate, concentrated to afford the pure title compound (8.94 g, 86% yield). |
| 85% |
With pyridinium chlorochromate; In Dichlorodifluoromethane; at 20℃; for 2h; |
EXAMPLE 31 Preparation of Adamantane-1-carbaldehyde To a suspension of pyridinium chlorochromate (3.88 g, 18 mmol) in methylene chloride (100 ml) is added a solution of <strong>[770-71-8]1-adamantanemethanol</strong> (2.0 g, 12 mmol) in methylene chloride (30 ml) in one portion. After stirring for 2 h at room temperature, the reaction mixture is diluted with ether (50 ml). The mixture is filtered through a funnel packed with silica gel (20 g) and washed with ether. The filtrate is concentrated to afford the title compound 1.7 g (85%) as a white solid. mp: 132-135 C. MS (+) ES: 165 (M+H)+. |
| 83% |
With pyridinium chlorochromate; In dichloromethane; at 0 - 20℃; for 1.66667h; |
1-adamantanecarboaldehyde (49)To a solution of <strong>[770-71-8]1-adamantanemethanol</strong> (1.66g, lOmmol) in CH2Cl2 was added PCC (4.3g, 20mmol) at 00C. The resulting mixture was stirred at the same temperature for lOmins before warming to ambient temperature. Stirring was continued for 1.5hrs until thedisappearance of starting material as checked by TLC. Water was added and extracted with CH2Cl2 for 3 times. The combined organic phase was dried over MgSO4, filtrated and concentrated in vacuo. The crude mixture was separated by flash chromatography (50%- 100% CH2C12/Hexane) to give 49 as white solid (1.36g, Yield: 83%). 1H-NMR (360 MHz, CDCl3) delta 9.32 (s, IH), 2.07 (br s, 3H), 1.77 (br s, 6H), 1.72 (br s, 6H); 13C-NMR (90 MHz, CDCl3) delta 206.07, 45.03, 37.25, 36.10, 27.61; ESI-MS: Calculated for C11H16O (M + H)+ 165.2, Found: 165.5. |
| 76% |
With 2-azatricyclo[3.3.1.13,7]dec-2-yloxidanyl; [bis(acetoxy)iodo]benzene; In N,N-dimethyl-formamide; at 20℃; for 2h;Inert atmosphere; |
General procedure: To a solution of 1-(p-bromophenyl)ethanol I-23 (201 mg, 1.0 mmol) in DMF (2.0 mL) was added HIO3 (194 mg, 1.1 mmol) and TEMPO (7.8 mg, 0.05 mmol). The mixture was stirred for 2 h at room temperature under an Ar atmosphere. After the reaction, the reaction mixture was poured into aq Na2S2O3, and extracted with a mixture of Et2O: hexane=1:1 (3*10 mL). Then, the organic layer was poured into satd NaCl (10 mL) and extracted with Et2O (10 mL). The organic layer was dried over Na2SO4. After being filtration and removal of the solvent under reduced pressure, the residue was purified by flash short column chromatography on silica gel (EtOAc-hexane, 1:4) to give p-bromoacetophenone II-23 in 99% yield. |
| 74% |
With sodium hypochlorite; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; potassium bromide; In dichloromethane; water; for 0.333333h;pH 8.6;Cooling with ice; |
General procedure: (1-Adamantyl)methanol (3.0 g, 18 mmol), KBr (214 mg, 1.8 mmol) and TEMPO (28 mg, 0.18 mmol)2 were dissolved in DCM (50 mL). The solution was cooled in an icebath. A commercial 5 % bleach-solution (30 mL) was buffered to pH 8.6 using solid NaHCO3 and then added to the TEMPOsolution. After 20 min of rapid stirring, the layers were separated. The DCM layer was dried over Na2SO4, filtered and concentrated in vacuo. This affords the product as a white to light-orange solid (2.25 g, 74%) |
| 71.2% |
|
General procedure: A solution of BTC (0.41 g, 1.39 mmol) in dry CH2Cl2 (5 mL) was cooled in an ice-salt bath under an atmosphere of N2. A solution of I (1.24 g, 4.17 mmol) in dry CH2Cl2 (5 mL) was added dropwise for 0.5 h, at -15 C. Stirring was continued for 0.5 h, and a solution of benzyl alcohol (0.3 g, 2.78 mmol) in dry CH2Cl2 (5 mL) was added dropwise for 0.5 h, at-15 C. After stirring for 0.5 h, Et3N (0.84 g, 8.34 mmol) was added slowly while the temperature should be controlled below -15 C. When the reaction was completed, 10% HCl solution in water was added dropwise until the pH of the reaction solution reached 2 under ice bath. The mixture was extracted with n-hexane or petroleum ether (10 mL x 2),decanted. The product was acquired after organic layer was concentrated and purified by flash chromatography (SiO2; n-hexane). (0.27 g, 92%). The water layer was used for the recovery of V and the excess I. |
|
With Dess-Martin periodane; In dichloromethane; at 0 - 20℃; for 1h; |
Synthesis of Compound 704Adamantyl-methanol 701 (5.0 g, 30 mmol) was dissolved in 40 mL of dry dichloromethane and to it was added portion- wise Dess-Martin Periodinate (13 g, 32 mmol) at 00C. The resulting mixture was allowed to stir at room temperature for 1 h. After completion of the reaction, the reaction mixture was poured into water, and the organic layer was separated, washed with sodium bisulfite and brine, and dried over sodium sulfate. Evaporation of the organic layer provided 4.3 g of the corresponding aldehyde 702. |
| 6%Chromat. |
Cu/HT; In toluene; at 110℃; for 24h;Inert atmosphere;Product distribution / selectivity; |
Example 3-15 A mixture of 1 mmol of 1-hydroxymethyladamantane, 5 mL of toluene, and 0.1 g (Cu: 3.0 percent by mole) of the catalyst prepared from Example 3-0 and including Cu particles immobilized on a hydrotalcite surface was stirred at 110 C. in an argon atmosphere for 24 hours and thereby yielded a corresponding carbonyl compound (1-adamantanal) in a yield equivalent to a gas chromatographic (GC) yield of 6%. |
| 0.052 g |
|
General Procedure: To a dry 25 ml 3-neck round bottom flask equipped with magnetic stirring bar, thermometer, Ar inlet, and dropping funnel was added dry dimethyl sulfoxide (4 mmol, 0.32g, 0.29 ml) diluted with dry DCM ((3 ml), and the solution was cooled bellow -60 C in dry ice-acetone bath. Then trifluoroacetic anhydride (3 mmol, 0.63 g, 0.42 ml), in 2 ml of dry DCM was added. After 10 min of efficient stirring 1-adamantane methanol (2 mmol, 0.33 g) in 2 ml of dry DCM was added dropwise. The rate of addition of alcohol was controlled to keep temperature bellow -60 C. Mixture was stirred for 20 min at -65 C, then ice bath was removed and mixture was allowed to warm up to room temperature. Next, triethylamine (0.8 ml) was added in portions during 10 minutes, and mixture was stirred for another 10 minutes. The reaction mixture was poured into separatory funnel and washed with diluted HCl, then with water, and combined aqueous fractions were extracted once with DCM. Organic fractions were combined, dried over sodium sulfate, and solvent was evaporated. Residue was dried in vacuum giving yellow solid (0.052 g). |
|
|
Example- 7; Charge MDC (400 ml) into dry RBF. Cool the reaction mass to 0-5C. Slowly add oxalyl chloride (150 gm) into the reaction mass at 0C-5C under nitrogen atmosphere. Stir the reaction mixture at 0C-5C for 10 minutes. Cool the reaction mass to -60 to -70C. Add DMSO (135 ml) and MDC (100 ml) solution to reaction mass at -60 to-70C. Stir for 10 minutes at -65C. Add compound XIV (100 gm) and MDC (600 ml) solution to reaction mass at -60 to -70C. Maintain the reaction mass for 30 min at -60 to -70C. Add triethylamine (420 ml) slowly to the reaction mass at -60 to-70C. Maintain the reaction mass for 20-30 min at -60 to-70C. Check TLC. Slowly raise the reaction mass temperature to 25 to35C. Quench reaction mass into KH2SO4 solution at 25 to35C. Stir the reaction mass for 10 minutes. Settle the reaction mass and separate the organic layer. Wash the MDC layer with KH2SO4 solution. Dry the MDC layer with sodium sulfate. Distill out the MDC completely under vacuum below 50C. Residue weight: 80 gm. (Compound XV). |
| 41 g |
|
The 50g, (0.3 moles) of compound-II was dissolved in 500mL of MDC and76g (0.9M) of sodium bi carbonate and7.2g (0.06M) of KBr were added at room temperature and reaction mass was cooled to 0-5C and stirred for 15 minutes. O. l g of TEMPO solution was added at 0-5C and then 225mL of sodium hypo chloride (1 1% chlorine content) solution was slowly added for 60-90 minutes at 0-5 C. Reaction mass was stirred for 2-3 hours at 0-5C till reaction was completed. After completion of the reaction, 10% (500 ml) sodium bi sulphate solution was added at 0-5C. Temperature was slowly, raised to room temperature and 350mL of DM water was added and reaction mass was stirred for 30 minutes and both the layers were separated. The aqueous layer was extracted with 300mL of MDC and total organic layer was combined and organic layer was washed with 25mL saturated sodium chloride solution. The organic layer was dried over sodium sulphate and the organic layer was distilled under vacuum at below 35C to obtain 41 gm of semisolid Step-A aldehyde compound having 99 % of purity by GC analysis. |
|
|
To a -60 C cold solution of 0.86 mL of oxalyl chloride (12.99 mmol, 1.2 eq) in 20 mL of abs. dichloromethane were added 2 mL of abs. DMSO dropwise and the solution was diluted with 5 mL of dichloromethane. Afterstirring for 30 min at -60 C a solution of 1.80 g of hydroxymethyladamantane, S14, (10.83 mmol, 1.0 eq) in 20mL of abs. dichloromethane was added and the mixture was stirred for 1 hour at -60 C. The reactions mixturewas brought to room temperature after adding 7.5 mL of triethylamin (54.1 mmol, 5.0 eq). Next 20 mL of water were added and the biphasic mixture was stirred for additional 15 min. The layers were separated and the aqueous phase was extracted twice with dichloromethane (75 mL). The combined organic phases were washedwith water (3 x 150 mL), dried over Na2SO4, filtered and the solvent was removed under reduced pressure to give 1.40 g (79%) white solid. |
| 46%Spectr. |
In ethyl acetate; at 45℃; for 10h;Inert atmosphere; Irradiation; |
General procedure: To a three-necked, cylindrical Pyrex glass reaction vessel equipped with a rubber balloon, rubberseptum, and glass stopper, a N2 atmosphere was introduced by flowing via cannula for 5 min. Au(0.6 wt %)/TiO2 (117.3 mg, 0.17 mol % Au), 1a (271.5 mg, 1.99 mmol), and dehydrated ethylacetate (25 mL) were added successively to the vessel. After N2 gas was reintroduced more than 5min, the rubber balloon was connected to the vessel and the mixture was sonicated. The vessel wasimmersed in a oil bath (kept at 45 oC) and stirred for 10 h under irradiation (lambda = 300-470 nm). 1HNMR analysis of this crude mixture using mesitylene as an internal standard indicated 97%conversion of 1a and the formation of 2a in 86% yield, as determined based on the signals at delta 3.61ppm and 2.94 ppm (shifted from 2.89 ppm due to the presence of ethyl acetate), respectively. Theproduct was purified by silica gel column chromatography (n-hexane/ethyl acetate 3:1) to afford 2a(180 mg, 66% yield, with inclusion of small amounts of unidentified impurities). |
| 135.9 g |
With sodium hypochlorite; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; sodium bromide; In dichloromethane; water; at 5 - 30℃; for 12h; |
To a 2000 ml four-necked reaction flask was added 0.83 mol of adamantane-1-carboxylic acid, followed by the addition of 600 ml of THF to stir. After the basic solid was dissolved, the ice bath was cooled to about 5 C; 0.75 mol (28.3 g) of NaBH4 was added in portions and the temperature was controlled to (about 30min drop finished); retreat ice bath, natural Heat to room temperature (25-30 C) and at room temperature. The reaction was stirred at this temperature for 2 hours. After the disappearance of adamantane-1-carboxylic acid, the reaction system was cooled to ); reaction 12 hours after standing, the water phase with 500mlDCM extraction, combined organic phase. Washed twice with 500 ml of semi-saturated sodium bicarbonate (500 ml * 2), dried over anhydrous sodium sulfate for 15 min and then filtered. The filtrate was concentrated under reduced pressure at 45 C to give a red semi-solid compound adamantane-1-carbaldehyde (Formula II) 135.9g. Yield 99.4%, GC purity 95.5% (containing 4.2% TEMPO by-product). |
| 90%Spectr. |
With Iron(III) nitrate nonahydrate; 9-azabicyclo<3.3.1>nonane-N-oxyl; In acetonitrile; at 20℃; for 6h;Green chemistry; |
Fe (NO3) 3.9H2O (40.4 mg, 10 mol%), ABNO (7 mg, 5 mol%),Adamantane methanol (166 mg, 1 mmol) was added to a 10 ml reaction tube,Then add 2ml of acetonitrile as solvent, open reaction at room temperature,The degree of reaction was then checked by GC-MS. After the reaction, add internal biphenyl,Quantitative analysis of the product adamantane formaldehyde yield with GC. Reaction 6h, adamantane formaldehyde yield was 90%, selectivity greater than 99%. |
|
With pyridinium chlorochromate; In dichloromethane; at 0 - 20℃; for 2h; |
To a stirred solution of compound 10 (1 g, 1 eq) in DCM (10 mL) at 0 00 P00 (1.42 g, 1.1 eq) was added portion wise. The resulting reaction mass was stirred at room temperature for 2 h. The progress of the reaction was monitored by TLC. After completion, the resulting mixture was filtered over a pad of celite. The filtrate was washed with water; the organic layer was separated; dried over anhydrous sodium sulfate and concentrated under reduced pressure to provide the title compound 11. |
|
With pyridinium chlorochroniate; In ethanol; dichloromethane; at 20 - 25℃; for 1.5h; |
To a suspension of 3 g of pyridinium chlorochroniate in 20 mL of anhydrous dichioromethane at 20-2.VC, was added a solution of ig of adamantylmethanol In dry ethanol. The mixture was stirred at room temperature over 90 mm and then wasfiltered under neutral silica. The filtrate was collected and the solvent removed under vacuum. The crude aldehyde was obtained and used at step 2 without further purification |
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