* 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.
With diphenylsilane; caesium carbonate In acetonitrile at 80℃; for 72 h; Schlenk technique; Inert atmosphere
1) In a glove box, 0.25 mmol of amantadine,6 equiv (1.5 mmol) of diphenylsilane,10 molpercent (based on amantadine) Cesium carbonate,1.6 ml of acetonitrile solvent was added to 50 ml of a Schlenk tube protected with N2. 2) The N2 in the Schlenk tube was replaced by CO2 in the double-row tube under refrigeration vacuum operation,The pressure of CO2 is 1 bar. 3) using said cesium carbonate as a catalyst,Said carbon dioxide being a C1 source,The diphenylsilane is used as a reducing agent,The amantadine was reacted in an acetonitrile solvent at 80 ° C for 72 hours. 4) After completion of the reaction,To the Schlenk tube was added 0.2 mmol of ferrocene as the internal magnetic standard. 5) By Bruker NMR analysis,The NMR spectra of the resulting product are consistent with the literature (P. Besenius, P. A. G. Cormack, R. F. Ludlow, S. Otto, D. C. Sherrington, Chem. Commun. 2008,In the report of the corresponding pure substance spectrum consistent,In this embodimentN-methylamantanamineYield> 95percent.
Reference：
[1] Patent: CN105753715, 2016, A, . Location in patent: Paragraph 0029; 0030; 0031; 0032; 0033; 0034; 0035
[2] ACS Catalysis, 2016, vol. 6, # 11, p. 7876 - 7881
2
[ 124-38-9 ]
[ 768-94-5 ]
[ 3717-40-6 ]
[ 3717-38-2 ]
Yield
Reaction Conditions
Operation in experiment
55%
With hydrogen In hexane at 140℃; for 7 h; Autoclave; Inert atmosphere
To a volume of 50 mL of Hastelloy autoclave was placed 10 mL of solvent n-hexane,1 mmol of amantadine,A certain amount of Au / Al2O3 catalyst (containing 5μmol)The autoclave was sealed and the inside of the autoclave was replaced with nitrogen three times,And then into the 1MPa of CO2 gas and 3MPa of H2,Keep the kettle gas pressure at 4MPa,Placed on the chassis with aluminum block on the magnetic stirrer,So that the temperature quickly rose to 140 ,Open the magnetic stirring,Stirring at 1000 rpm for 7 hours,After cooling, add a certain amount of n-octane as the internal standard,Using gas chromatography (FID detector),N-methylamine adamantine yield was 55percentThe yield of N, N-dimethyl-amantadine was 45percentNo other byproducts are generated.
Reference：
[1] Patent: CN106316866, 2017, A, . Location in patent: Paragraph 0143; 0144
3
[ 768-94-5 ]
[ 74-88-4 ]
[ 3717-38-2 ]
Reference：
[1] Chemical Communications, 2008, # 24, p. 2809 - 2811
4
[ 67-56-1 ]
[ 768-94-5 ]
[ 3717-40-6 ]
[ 3717-38-2 ]
Yield
Reaction Conditions
Operation in experiment
37 %Chromat.
at 150℃; for 5 h; Autoclave
6.0 mg (0.01 mmol) of complex 1 produced in Reference Example 1 and 303 mg (2 mmol) of 1-adamantylamine were added to a 100 ml stainless autoclave, nitrogen substitution was conducted, and 2 ml of methanol was then added thereto. Next, 1.1 ml (1.2 mmol) of 1.13 M methanol solution of NaOMe was added, and the mixture was then stirred at 150° C. for 5 hours. After cooling, the reactant was analyzed by GC, and N-methyladamantylamine was obtained at a GC yield of 19percent and N,N-dimethyladamantylamine was obtained at a GC yield of 37percent.
Reference：
[1] Angewandte Chemie - International Edition, 2018, vol. 57, # 21, p. 6166 - 6170[2] Angew. Chem., 2018, vol. 130, p. 6274 - 6278,5
[3] Patent: US2016/9632, 2016, A1, . Location in patent: Paragraph 0186; 0187
Illustrative salts coming within the scope of this invention include salts of 6,7-dibromo-3,4-dihydro-3-oxo-2-quinoxaline carboxylic acid and the following hindered amines. 1-adamantylamine 2-adamantylamine 3,5-dimethyl-1-adamantylamine 1-methylaminoadamantane 3-dimethylaminotricyclo[4.3.3.1.3,8 ] undecane dl-cyclo-octane 1amino-1-(1-adamantyl)ethane, 1-N-methylaminoadamantane 1-N-ethylaminoadamantane ...
Illustrative salts coming within the scope of this invention include salts of 6,7-dibromo-3,4-dihydro-3-oxo-2-quinoxaline carboxylic acid and the following hindered amines. ... 1-methylaminoadamantane 3-dimethylaminotricyclo[4.3.3.1.3,8 ] undecane dl-cyclo-octane 1amino-1-(1-adamantyl)ethane, 1-N-methylaminoadamantane 1-N-ethylaminoadamantane 1-N-benzylaminoadamantane
28
[ 286-20-4 ]
[ 3717-38-2 ]
2-(adamantan-1-yl-methyl-amino)-cyclohexanol[ No CAS ]
EXAMPLE 113 Preparation of (2S)-(-)-1-(4-indolyloxy)-3-(1-methyl-1-adamantylamino)-2-propanol hydrochloride A mixture of (S)-(+)-4-(oxiranylmethoxy)-1H-indole (0.511 g, 2.7 mmol) and 1-methyl-1-adamantylamine (see Org. Syn., Coll. Vol. 7, 433) (0.486 g, 2.9 mmol) in methanol (15 mL) was heated to reflux for 18 h. The methanol was evaporated and flash chromatography [silica gel, methylene chloride/methanol/ammonium hydroxide (100/3/0.5)] yielded 0.787 g oil. Crystallization as the hydrochloride salt from acetonitrile provided 0.623 g of colorless crystals. Mp 241 C. Mass spectrum, m+ =355. [alpha]23589 =-16.6 (C=0.0073 g/mL, MeOH). Anal (C22 H31 ClN2 O2) theory C, 67.58; H, 7.99; N, 7.17; found C, 67.35; H, 8.18; N, 7.15.
In methanol; acetonitrile;
EXAMPLE 113 Preparation of (2S)-(-)-1-(4-indolyloxy)-3-(1-methyl-1-adamantylamino)-2-propanol hydrochloride A mixture of (S)-(+)-4-(oxiranylmethoxy)-1H-indole (0.511 g, 2.7 mmol) and 1-methyl-1-adamantylamine (see Org. Syn., Coll. Vol. 7, 433) (0.486 g, 2.9 mmol) in methanol (15 mL) was heated to reflux for 18 h. The methanol was evaporated and flash chromatography [silica gel, methylene chloride/methanol/ammonium hydroxide (100/3/0.5)] yielded 0.787 g oil. Crystallization as the hydrochloride salt from acetonitrile provided 0.623 g of colorless crystals. Mp 241 C. Mass spectrum m+ =355. [alpha]23589 =-16.6 (C=0.0073 g/mL, MeOH). Anal (C22 H31 ClN2 O2) theory C, 67.58; H, 7.99; N, 7.17; found C, 67.35; H, 8.18; N, 7.15.
In methanol; acetonitrile;
EXAMPLE 113 Preparation of (2S)-(-)-1-(4-indolyloxy)-3-(1-methyl-1-adamantylamino)-2-propanol hydrochloride A mixture of (S)-(+)-4-(oxiranylmethoxy)-1H-indole (0.511 g, 2.7 mmol) and 1-methyl-1-adamantylamine (see Org. Syn., Coll. Vol. 7, 433) (0.486 g, 2.9 mmol) in methanol (15 mL) was heated to reflux for 18 h. The methanol was evaporated and flash chromatography ?silica gel, methylene chloride/methanol/ammonium hydroxide[(100/3/0.5)] yielded 0.787 g oil. Crystallization as the hydrochloride salt from acetonitrile provided 0.623 g of colorless crystals. Mp 241 C. Mass spectrum, m+ =355. [alpha]23589 =-16.6 (C=0.0073 g/mL, MeOH). Anal (C22 H31 ClN2 O2) theory C, 67.58; H, 7.99; N, 7.17; found C, 67.35; H, 8.18; N, 7.15.
In methanol; acetonitrile;
Example 113 Preparation of (2S)-(-)-1-(4-indolyloxy)-3-(1-methyl-1-adamantylamino)-2-propanol hydrochloride A mixture of (S)-(+)-4-(oxiranylmethoxy)-1H-indole (0.511 g, 2.7 mmol) and 1-methyl-1-adamantylamine (see Org. Syn., Coll. Vol. 7, 433) (0.486 g, 2.9 mmol) in methanol (15 mL) was heated to reflux for 18 h. The methanol was evaporated and flash chromatography ?silica gel, methylene chloride/methanol/ammonium hydroxide[(100/3/0.5)] yielded 0.787 g oil. Crystallization as the hydrochloride salt from acetonitrile provided 0.623 g of colorless crystals. Mp 241 C. Mass spectrum, m+ =355. [alpha] 23589 =-16.6 (C=0.0073 g/mL, MeOH). Anal (C22 H31 ClN2 O2) theory C, 67.58; H, 7.99; N, 7.17; found C, 67.35; H, 8.18; N, 7.15.
1-methyl-3-[6-(N-adamantyl-N-methylamino)hexanoyl]indole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
EXAMPLE 74 1-Methyl-3-[6-(N-adamantyl-N-methylamino)hexanoyl]indole (Compound No. 1-289) A procedure similar to that described in Example 53 was repeated, but using 1-methyl-3-(6-bromohexanoyl)indole and N -adamantyl- N -methylamine as starting materials, in relative proportions similar to those used in that Example, to obtain the title compound as an oil, with an Rf value of 0.24, using ethyl acetate as developing solvent.
bis(1-methylammoniumadamantane) tetrathiomolybdate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
97%
In water; isopropyl alcohol; at 20 - 25℃; for 0.5h;
1-Methylaminoadamantane (0.99 g, 5.98 mmol, Aldrich) was dissolved in 2- propanol (75 mL) and added to 6w(ammonium) tetrathiomolybdate (780 mg, 2.99 mmol) in water (ASTMl, 100 mL) at RT. After mixing for 30 mins, the 2-propanol was removed on a rotary evaporator at RT. The remaining aqueous mixture was stored for 2 h in a refrigerator. The dark orange solid was filtered and washed with cold water (15 mL) and diethyl ether (15 mL). The solid was dried to a constant weight at RT. The product was <n="29"/>iw(l-methylammoniumadamantane) tetrathiomolybdate (1.60 g, 97% yield) as an orange solid (melting point; 168C dec). Its spectra are as follows:1H NMR (300 MHz, DMSOd6): delta 7.49 (br s, 6H), 2.52 (s, 4H), 1.94 (s, 6H), 1.60 (m, 12H), 1.50 (s, 12H); 13C NMR (75 MHz, DMSOd6): delta 50.42, 8.75, 36.08, 31.60, 27.37;UV-Vis (ethanol): 318, 243, 193; andCHN analysis: Calculated for: C22H40MoN2S4.Calculated: C: 47.46; H: 7.24; N: 5.03; S: 23.04;Found: C: 47.41; H: 7.47; N: 5.05; S: 23.05.
General procedure: A solution of phosphorusoxychloride (0.047 mL, 5.18 mmol) in benzene (2.5 mL) was added dropwise to a solution of Nmethyl-N-(1-adamantyl)formamide (1 g, 5.18 mmol) in benzene (2.5 mL) over a period of 10min and allowed to stir for a further 40 min at room temperature. A solution of N-methyl-N-(1-adamantyl)amine (0.85 g, 5.18 mmol) in benzene (3 mL) was added and the reaction mixturewas left at room temperature for 16 h followed by refluxing for 4 h. The benzene wasevaporated, and the resulting residue was dried in vacuum at 90 C for 1 h, then washed withsmall volumes of hexanes. The product was dissolved in boiling water (50 mL), to which a smallamount of charcoal was added. Following filtration of the hot solution, perchlorate 3 wasprecipitated with an excess of sodium perchlorate, filtered off and dried. Yield: 1.37 g, 60%, mp229 - 231 C (from 2-ethoxyethanol). Found: C, 62.4; H, 8.6; Cl, 8.1; N, 6.4. Calc. forC23H37CIN2O4: C, 62.6; H, 8.5; Cl, 8.0; N, 6.4%. dH (400 MHz, DMSO-d6, Me4Si): 1.66 (12H,m), 1.96 (12H, m), 2.16 (6H, m) (Ad), 3.19 (6H, s, CH3), 7.80 (1H, s, CHN); dC (100 MHz,DMSO-d6, Me4Si): 32.7 (CH3), 28.7, 34.5, 39.1, 61.6 (Ad), 153.7 (CHN).
With C29H29ClNOP2Ru; sodium methylate; at 150℃; for 5h;Autoclave;
6.0 mg (0.01 mmol) of complex 1 produced in Reference Example 1 and 303 mg (2 mmol) of 1-adamantylamine were added to a 100 ml stainless autoclave, nitrogen substitution was conducted, and 2 ml of methanol was then added thereto. Next, 1.1 ml (1.2 mmol) of 1.13 M methanol solution of NaOMe was added, and the mixture was then stirred at 150 C. for 5 hours. After cooling, the reactant was analyzed by GC, and N-methyladamantylamine was obtained at a GC yield of 19% and N,N-dimethyladamantylamine was obtained at a GC yield of 37%.
2-chloro-N-[2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)phenyl]acetamide[ No CAS ]
2-[adamantan-1-yl(methyl)amino]-N-[2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)phenyl]acetamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
56%
With potassium carbonate; In acetonitrile; at 80℃; for 28h;
General procedure: Compound 1 (1.27 g, 4.78 mmol) was added to a stirred solution of K2CO3 (1.32 g, 9.55 mmol) and Et2NH (1.00 mL, 9.55 mmol) in MeCN(30.0 mL) in a round-bottomed flask. The orange-coloured solutio nwas then heated to reflux temperature (~80 C). The reaction progress was monitored by TLC, and the reflux was stopped after 24 h. The mixture appeared dark brown with light brown precipitate. The mixture was allowed to cool to r.t., and then it was gravity filtered and the solution was left to evaporate to give a compound that appeared brown in colour and waxy in composition. The compound was purified by DCFC and the product was collected as a yellow-coloured oil from fractions 8 to 18 (1.1 g, 69% yield)
With diphenylsilane; caesium carbonate; In acetonitrile; at 80℃; under 750.075 Torr; for 72h;Schlenk technique; Inert atmosphere;
1) In a glove box, 0.25 mmol of amantadine,6 equiv (1.5 mmol) of diphenylsilane,10 mol% (based on amantadine) Cesium carbonate,1.6 ml of acetonitrile solvent was added to 50 ml of a Schlenk tube protected with N2. 2) The N2 in the Schlenk tube was replaced by CO2 in the double-row tube under refrigeration vacuum operation,The pressure of CO2 is 1 bar. 3) using said cesium carbonate as a catalyst,Said carbon dioxide being a C1 source,The diphenylsilane is used as a reducing agent,The amantadine was reacted in an acetonitrile solvent at 80 C for 72 hours. 4) After completion of the reaction,To the Schlenk tube was added 0.2 mmol of ferrocene as the internal magnetic standard. 5) By Bruker NMR analysis,The NMR spectra of the resulting product are consistent with the literature (P. Besenius, P. A. G. Cormack, R. F. Ludlow, S. Otto, D. C. Sherrington, Chem. Commun. 2008,In the report of the corresponding pure substance spectrum consistent,In this embodimentN-methylamantanamineYield> 95%.
With hydrogen; In hexane; at 140℃; under 7500.75 - 30003 Torr; for 7h;Autoclave; Inert atmosphere;
To a volume of 50 mL of Hastelloy autoclave was placed 10 mL of solvent n-hexane,1 mmol of amantadine,A certain amount of Au / Al2O3 catalyst (containing 5mumol)The autoclave was sealed and the inside of the autoclave was replaced with nitrogen three times,And then into the 1MPa of CO2 gas and 3MPa of H2,Keep the kettle gas pressure at 4MPa,Placed on the chassis with aluminum block on the magnetic stirrer,So that the temperature quickly rose to 140 ,Open the magnetic stirring,Stirring at 1000 rpm for 7 hours,After cooling, add a certain amount of n-octane as the internal standard,Using gas chromatography (FID detector),N-methylamine adamantine yield was 55%The yield of N, N-dimethyl-amantadine was 45%No other byproducts are generated.
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