* 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.
Reference:
[1] Canadian Journal of Chemistry, 1987, vol. 65, p. 2428 - 2433
6
[ 768-90-1 ]
[ 75-76-3 ]
[ 702-79-4 ]
[ 281-23-2 ]
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Reference:
[1] Journal of Organic Chemistry USSR (English Translation), 1981, vol. 17, # 7, p. 1203 - 1208[2] Zhurnal Organicheskoi Khimii, 1981, vol. 17, # 7, p. 1357 - 1363
[3] Journal of Organic Chemistry USSR (English Translation), 1981, vol. 17, # 7, p. 1203 - 1208[4] Zhurnal Organicheskoi Khimii, 1981, vol. 17, # 7, p. 1357 - 1363
7
[ 75-76-3 ]
[ 935-56-8 ]
[ 702-79-4 ]
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Reference:
[1] Journal of Organic Chemistry USSR (English Translation), 1981, vol. 17, # 7, p. 1203 - 1208[2] Zhurnal Organicheskoi Khimii, 1981, vol. 17, # 7, p. 1357 - 1363
[3] Journal of Organic Chemistry USSR (English Translation), 1981, vol. 17, # 7, p. 1203 - 1208[4] Zhurnal Organicheskoi Khimii, 1981, vol. 17, # 7, p. 1357 - 1363
8
[ 75-76-3 ]
[ 281-23-2 ]
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Reference:
[1] Journal of Organic Chemistry USSR (English Translation), 1983, p. 297 - 300[2] Zhurnal Organicheskoi Khimii, 1983, vol. 19, # 2, p. 339 - 343
9
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Reference:
[1] Canadian Journal of Chemistry, 1987, vol. 65, p. 2428 - 2433
10
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Reference:
[1] Journal of Organic Chemistry USSR (English Translation), 1983, p. 297 - 300[2] Zhurnal Organicheskoi Khimii, 1983, vol. 19, # 2, p. 339 - 343
11
[ 768-90-1 ]
[ 75-76-3 ]
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Reference:
[1] Journal of Organic Chemistry USSR (English Translation), 1983, p. 297 - 300[2] Zhurnal Organicheskoi Khimii, 1983, vol. 19, # 2, p. 339 - 343
12
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[ 75-16-1 ]
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Reference:
[1] Canadian Journal of Chemistry, 1987, vol. 65, p. 2428 - 2433
13
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[ 702-79-4 ]
[ 4045-44-7 ]
[ 281-23-2 ]
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[ 768-91-2 ]
[ 108-88-3 ]
Reference:
[1] Angewandte Chemie - International Edition, 2013, vol. 52, # 44, p. 11564 - 11568[2] Angew. Chem., 2013, vol. 125, # 44, p. 11778 - 11782,5
14
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[ 702-79-4 ]
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Reference:
[1] Journal of Organic Chemistry USSR (English Translation), 1983, p. 297 - 300[2] Zhurnal Organicheskoi Khimii, 1983, vol. 19, # 2, p. 339 - 343
15
[ 768-90-1 ]
[ 75-76-3 ]
[ 702-79-4 ]
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Reference:
[1] Journal of Organic Chemistry USSR (English Translation), 1983, p. 297 - 300[2] Zhurnal Organicheskoi Khimii, 1983, vol. 19, # 2, p. 339 - 343
16
[ 75-76-3 ]
[ 935-56-8 ]
[ 702-79-4 ]
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[ 1687-36-1 ]
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Reference:
[1] Journal of Organic Chemistry USSR (English Translation), 1983, p. 297 - 300[2] Zhurnal Organicheskoi Khimii, 1983, vol. 19, # 2, p. 339 - 343
17
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Reference:
[1] Journal of Organic Chemistry USSR (English Translation), 1983, p. 297 - 300[2] Zhurnal Organicheskoi Khimii, 1983, vol. 19, # 2, p. 339 - 343
18
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Reference:
[1] Journal of Organic Chemistry USSR (English Translation), 1986, vol. 22, p. 481 - 483[2] Zhurnal Organicheskoi Khimii, 1986, vol. 22, # 3, p. 540 - 542
[3] Dalton Transactions, 2014, vol. 43, # 22, p. 8530 - 8542
[4] Canadian Journal of Chemistry, 1987, vol. 65, p. 2428 - 2433
[5] Bulletin of the Chemical Society of Japan, 2001, vol. 74, # 2, p. 339 - 345
[6] Journal of Organic Chemistry, 1998, vol. 63, # 14, p. 4581 - 4586
[7] MedChemComm, 2017, vol. 8, # 1, p. 135 - 147
[8] Journal of the American Chemical Society, 1993, vol. 115, # 16, p. 7293 - 7299
[9] Asian Journal of Chemistry, 2012, vol. 24, # 4, p. 1756 - 1758
[10] Tetrahedron Letters, 2009, vol. 50, # 50, p. 6938 - 6940
[11] Chemische Berichte, 1960, vol. 93, p. 1366 - 1371
[12] Journal of the American Chemical Society, 1991, vol. 113, # 6, p. 2065 - 2071
[13] Synthetic Communications, 2006, vol. 36, # 15, p. 2113 - 2119
[14] Journal of the American Chemical Society, 1991, vol. 113, # 6, p. 2177 - 2194
[15] Patent: US2004/127715, 2004, A1, . Location in patent: Page 11
19
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Yield
Reaction Conditions
Operation in experiment
99%
Sealed tube; Inert atmosphere
General procedure: The reactions were carried out in glass ampoules (20 mL) or in a pressure microreactor of stainless steel (17 mL). The results of parallel experiments were identical. Into the microreactor (ampoule) in an argon atmosphere was charged 0.3 mmol of Fe(acac)3, 10 mmol of initial adamantane, 10 mmol of CBr4, and 150 mmol of CH2Br2. The reactor was hermetically closed (the ampoule was sealed) and heated while stirring. On the completion of the reaction the reactor (ampoule) was cooled to room temperature, opened, the solvent was distilled off, the residue was crystallized from hexane or ethanol. Yields are given in respect to converted adamantane (adamantine derivatives) (GLC procedure, internal reference decene; correction factor for adamantane 1.09, for bromoadamantane 1.53). The structure of compounds obtained was proved by comparison with known samples and published data.
Reference:
[1] Russian Journal of Organic Chemistry, 2015, vol. 51, # 2, p. 184 - 187[2] Zh. Org. Khim., 2015, vol. 51, # 2, p. 196 - 199
[3] Tetrahedron Letters, 1986, vol. 27, # 12, p. 1399 - 1402
[4] Journal of Organic Chemistry USSR (English Translation), 1984, vol. 20, p. 2041[5] Zhurnal Organicheskoi Khimii, 1984, vol. 20, # 10, p. 2239 - 2240
20
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Yield
Reaction Conditions
Operation in experiment
35 %Spectr.
With tert-butyl hypobromite; carbon tetrabromide In dichloromethane at 40℃; for 90 h; Darkness
tert-Butyl hypobromite 50 (0.33 mL, freshly prepared and used immediately, 0.05 mmol, 0.1 eq.), adamantane 18 (68 mg, 0.5 mmol), carbon tetrabromide (166 mg, 0.5 mmol, 1 eq.) and dichloromethane (3.13 mL) were added to an oven-dried pressure tube and the reaction mixture was stirred at 40 °C for 90 h in the dark. The reaction mixture was cooled to RT and quenched with aqueous hydrochloric acid (1 M, 5 mL) and extracted with dichloromethane (4 x 10 mL). The organic phases were combined, dried over Na2SO4, filtered and concentrated in vacuo. The yield of adamantane 18 (29percent), 1-bromoadamantane 31 (35percent), 2-bromoadamantane 51 (14percent) and 1,3-bromoadamantane 52 (11percent) were determined by adding 1,3,5-trimethoxybenzene to the crude mixture as an internal standard for 1H-NMR.
Reference:
[1] Molecules, 2018, vol. 23, # 5,
21
[ 935-56-8 ]
[ 768-90-1 ]
[ 7314-85-4 ]
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Reference:
[1] Journal of the Chemical Society, Chemical Communications, 1987, # 13, p. 1013 - 1014
[2] Journal of the Chemical Society, Chemical Communications, 1987, # 13, p. 1013 - 1014
22
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[ 33803-54-2 ]
Reference:
[1] Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation), 1991, vol. 40, # 12, p. 2528 - 2529[2] Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1991, vol. 40, # 12, p. 2897 - 2898
23
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[ 52804-26-9 ]
Reference:
[1] Journal of Organic Chemistry USSR (English Translation), 1987, vol. 23, # 9, p. 1672 - 1675[2] Zhurnal Organicheskoi Khimii, 1987, vol. 23, # 9, p. 1882 - 1886
24
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[ 5001-18-3 ]
Yield
Reaction Conditions
Operation in experiment
38%
With oxygen In acetic acid tert-butyl ester at 100℃; for 96 h;
The procedure of Example 1 was repeated, except that the catalyst was replaced by a catalyst that vanadium (18 μmol) is supported on montmorillonite (i.e., a V/Mont. catalyst); the amount of adamantane employed was changed to 3 mmol; t-butyl acetate was employed as a solvent; and reaction was performed at 100° C. for 96 hours. The V/Mont. catalyst was formed through the catalyst preparation process described in Japanese Patent Application Laid-Open (kokai) No. 2004-2234. Specifically, the catalyst was obtained by adding an aqueous vanadium(III) chloride solution to montmorillonite (Kunipia F, product of Kunimine Industries Co., Ltd.), followed by ion exchange, filtration, washing with water, drying, and firing in air at 800° C.
Reference:
[1] Journal of the American Chemical Society, 1989, vol. 111, # 17, p. 6749 - 6757
[2] Journal of the American Chemical Society, 2005, vol. 127, # 44, p. 15391 - 15393
[3] Tetrahedron Letters, 1999, vol. 40, # 11, p. 2165 - 2168
[4] Tetrahedron Letters, 1999, vol. 40, # 11, p. 2165 - 2168
[5] Patent: US2006/235245, 2006, A1, . Location in patent: Page/Page column 6-7
[6] Journal of Organic Chemistry, 1996, vol. 61, # 14, p. 4520 - 4526
[7] Tetrahedron Letters, 1996, vol. 37, # 28, p. 4993 - 4996
[8] Journal of the American Chemical Society, 1989, vol. 111, # 17, p. 6749 - 6757
[9] Journal of the American Chemical Society, 1992, vol. 114, # 26, p. 10660 - 10662
[10] Heterocycles, 1995, vol. 40, # 2, p. 867 - 904
[11] Journal of the American Chemical Society, 1989, vol. 111, # 17, p. 6749 - 6757
[12] Tetrahedron Letters, 1996, vol. 37, # 28, p. 4993 - 4996
[13] Journal of Organic Chemistry, 2000, vol. 65, # 26, p. 9186 - 9193
[14] Chemical Communications, 2001, # 2, p. 191 - 192
[15] Chemistry Letters, 2005, vol. 34, # 12, p. 1626 - 1627
[16] Journal of Organic Chemistry, 2000, vol. 65, # 26, p. 9186 - 9193
[17] Chemistry - A European Journal, 2006, vol. 12, # 12, p. 3401 - 3409
[18] Organic and Biomolecular Chemistry, 2011, vol. 9, # 7, p. 2258 - 2265
[19] Journal of the American Chemical Society, 2011, vol. 133, # 21, p. 8074 - 8077
[20] Chemistry - A European Journal, 2013, vol. 19, # 43, p. 14697 - 14701
25
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Yield
Reaction Conditions
Operation in experiment
25%
at 75℃; for 6 h;
The procedure of Example 1 was repeated, except that the catalyst was replaced by NHPI (1 mmol) and VO(acac)2 (50 μmol); the amount of acetic acid serving as a solvent was changed to 25 mL; and the reaction temperature was changed to 75° C.
Reference:
[1] Tetrahedron Letters, 1990, vol. 31, # 21, p. 3067 - 3070
[2] Journal of the American Chemical Society, 2002, vol. 124, # 47, p. 13978 - 13979
[3] Organic Letters, 2014, vol. 16, # 24, p. 6504 - 6507
[4] Tetrahedron Letters, 1999, vol. 40, # 11, p. 2165 - 2168
[5] Synthetic Communications, 1996, vol. 26, # 8, p. 1555 - 1562
[6] Chemical Communications, 2004, # 7, p. 798 - 799
[7] Chemistry - A European Journal, 2015, vol. 21, # 44, p. 15564 - 15569
[8] Patent: US2006/235245, 2006, A1, . Location in patent: Page/Page column 6-7
[9] Tetrahedron Letters, 1990, vol. 31, # 21, p. 3067 - 3070
[10] Journal of the American Chemical Society, 1996, vol. 118, # 37, p. 8961 - 8962
[11] Tetrahedron Letters, 1990, vol. 31, # 21, p. 3067 - 3070
[12] Journal of the American Chemical Society, 1992, vol. 114, # 4, p. 1346 - 1351
[13] Organic Letters, 2005, vol. 7, # 2, p. 263 - 266
[14] Patent: US6403521, 2002, B1,
[15] Organic and Biomolecular Chemistry, 2012, vol. 10, # 15, p. 3122 - 3130
[16] Chemistry - A European Journal, 2013, vol. 19, # 43, p. 14697 - 14701
[17] RSC Advances, 2016, vol. 6, # 96, p. 93756 - 93767
[18] Chemistry - An Asian Journal, 2018, vol. 13, # 17, p. 2458 - 2464
26
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Yield
Reaction Conditions
Operation in experiment
31.6%
at 120℃; for 6 h;
The procedure of Example 1 was repeated, except that the acetic acid serving as a solvent was replaced by propionic acid. Example 7 The procedure of Example 6 was repeated, except that the amount of the catalyst was changed to 10 μmol. Example 8 The procedure of Example 6 was repeated, except that the amount of the catalyst was changed to 1.3 μmol.
25.1%
at 100℃; for 6 h;
The procedure of Example 9 was repeated, except that methanesulfonic acid [CH3SO3H] was added in an amount of 0.004 mL.
23.2%
at 100℃; for 6 h;
The procedure of Example 9 was repeated, except that europium triflate [Eu(OTf)3] was added in an amount of 10 μmol.
21.7%
at 110℃; for 6 h;
The procedure of Example 6 was repeated, except that the amount of adamantane employed was changed to 5 mmol, and the catalyst was replaced by Co(acac)2.2H2O.
15.3%
at 120℃; for 6 h;
The procedure of Example 1 was repeated, except that the catalyst was replaced by a vanadium oxide-TPP complex [VOTPP].
15.5%
at 100℃; for 6 h;
The procedure of Example 6 was repeated, except that the amount of adamantane employed was changed to 5 mmol, and the reaction temperature was changed to 100° C.
Firstly, to a solution of adamantane (2.59g, 19mmol) in a mixture of acetic acid (100mL) and concentrated sulphuric acid (0.52mL 9.5mmol) was slowly added chromium trioxide (7.6g, 76mmol). The resultant reaction system was stirred at 80°C for 2h. Then the mixture was concentrated, washed with 30percent NaOH solution, and extracted with ethyl acetate. The organic extract was cooled down at room temperature overnight to give a white precipitate which was recrystallized from a mixed solvent of ethanol and hexane to afford white solid 1. 1H NMR (300MHz, DMSO-d6): δ 1.360–1.476 (m, 12H), 2.104 (s, 2H), 4.390 (s, 2H).
Reference:
[1] Chinese Chemical Letters, 2014, vol. 25, # 2, p. 367 - 369
[2] Tetrahedron Letters, 1996, vol. 37, # 28, p. 4993 - 4996
[3] Chemische Berichte, 1960, vol. 93, p. 1366 - 1371
[4] Patent: US7078562, 2006, B2, . Location in patent: Page/Page column 16-17; 19-20
[5] Organic and Biomolecular Chemistry, 2011, vol. 9, # 7, p. 2258 - 2265
[6] MedChemComm, 2017, vol. 8, # 1, p. 135 - 147
With hydrogenchloride; sodium hydroxide; sodium hypochlorite In water; ethyl acetate
EXAMPLE 1 Into a 10-L five-necked jacketed flask equipped with a stirring device, a thermometer, a Dimroth condenser and a pH electrode, were charged 408 g (3 mol) of adamantane, 3000 mL of ethyl acetate, 20 g of ruthenium chloride n-hydrate (corresponding to 82 mmol of dihydrate) and 500 g of water. After heating to 46° C, the pH was adjusted to 4. Then, a 12percent aqueous solution of sodium hypochlorite was started to be added dropwise. The dropping speed was regulated so as to add 4120 g (7.5 mol) of the aqueous solution of sodium hypochlorite over 400 min as calculated from the reaction rate previously measured. The content of the free alkali in the aqueous solution of sodium hypochlorite was 0.5percent. The reaction was continued by maintaining the pH of the reaction system at 4.0 to 4.5 by adding a 5percent hydrochloric acid in an amount equivalent to the free alkali in the aqueous solution of sodium hypochlorite. During the reaction, the hypochlorite concentration in the water phase varied between 0.03 and 0.09 mmol/g. After the addition of the sodium hypochlorite was completed, 80 g of a 25 wt percent NaOH aqueous solution and 3000 mL of hexanol were added to separate the reaction mixture into the organic phase and the water phase. The gas chromatographic analysis on each phase showed that the conversion of adamantane was 100percent, the yield of 1-adanantanol was 9percent, the yield of 1,3-adamantanediol was 70percent, and the yield of 1,3,5-adamantanetriol was 14percent. The ruthenium catalyst was recovered as black precipitates by filtering the water phase.
The procedure of Example 1 was repeated, except that the catalyst was replaced by acetylacetonatovanadium [V(acac)3].
18%
at 120℃; for 6 h;
Adamantane (10 mmol, 1.36 g) and acetylacetonatovanadyl [VO(acac)2] (5 μmol, 1.3 mg) serving as a catalyst were dissolved in acetic acid (10 mL) placed in a three-neck flask, and oxygen (1 atm) was continuously blown into the flask at a flow rate of 10 mL/min under stirring with a stirrer, to thereby allow partial oxidation of adamantane (ADM) to proceed for six hours at 120° C. The resultant product was subjected to quantitative analysis by means of a gas chromatograph, and as a result, the product was found to contain 1-adamantanol (1-AdOH), 2-adamantanol (2-AdOH), 1,3-adamantanediol (1,3-(AdOH)2), acetic acid esters of them, and 2-adamantanone (2-Ad=O). In the case of this product, adamantane conversion, total yield, and turnover number (TON) were found to be 37.0percent, 25.8percent, and 517, respectively. The results are shown in Table 1. Table 1 also shows analysis results for the cases of the below-described Examples and Referential Examples. As used herein, the turnover number is obtained by use of the following equation: [amount (mol) of adamantane consumed through reaction/amount (mol) of active metal (e.g., vanadium or cobalt) contained in the employed catalyst]. The greater the turnover number, the higher the reaction rate. Example 2 The procedure of Example 1 was repeated, except that the amount of adamantane employed was changed to 5 mmol.
10.1%
at 120℃; for 6 h;
The procedure of Example 1 was repeated, except that the catalyst was replaced by ammonium metavanadate [NH4VO3].
Step one, equipped with a condenser, a thermometer and a tail gas absorption 5L four reaction flask, 108g of iron powder was added slowly dropwise over anhydrous bromine 400ml, about half an hour dropwise, stirred for 30 minutes after completion; document.write(""); Step two, the remaining bromine was added dropwise to the reaction flask. After completion, was heated to 45-50 deg.] C, 600g adamantane slowly added to the reaction system, the reaction temperature was raised to 62-65 deg.] C to reflux. The reaction to 65 hours have small sample measured GC showed starting material consumed. (In the control 1) document.write(""); Wherein the molar ratio of adamantane, anhydrous bromine, iron powder is 1: 10.6: 0.44.document.write(""); Step III After completion of the reaction, the recovered bromine atmospheric distillation, and the reaction mixture was poured into ice containing 3.5L bucket chloroform, stirred 10min, filtered through celite pad.document.write(""); Step four, the filtrate was washed with a saturated aqueous solution of sodium bisulfite and excess bromine (note cooled) solid sodium bisulfite consumption 5kg. document.write(""); Fifth, the organic layer was washed organic layer with water 3kg * 2 step was concentrated to dryness to give a crude product 1.95kg. document.write(""); Step six, 13L with methanol, heated and melted, add 65g active carbon, filtered hot, the filtrate was stirred for crystallization (cooling with ice). And filtered to give 1.19kg quality, the mother liquor was concentrated to about one-third of the original volume and stirred for crystallization, and filtered to give 250g white fine.
Reference:
[1] Chemische Berichte, 1960, vol. 93, p. 1366 - 1371
[2] Journal of Organic Chemistry, 2004, vol. 69, # 4, p. 1010 - 1019
[3] Chemistry - An Asian Journal, 2011, vol. 6, # 6, p. 1450 - 1455
[4] Journal of Organic Chemistry, 2014, vol. 79, # 14, p. 6738 - 6742
[5] Patent: CN104628526, 2016, B, . Location in patent: Paragraph 0069-0075
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[ 67422-73-5 ]
[ 67396-54-7 ]
[ 34059-96-6 ]
[ 106578-84-1 ]
[ 106578-85-2 ]
Reference:
[1] Journal of Organic Chemistry USSR (English Translation), 1986, vol. 22, p. 481 - 483[2] Zhurnal Organicheskoi Khimii, 1986, vol. 22, # 3, p. 540 - 542
Stage #1: With Al2Br7(1-)*CBr3(1+) In 1,2-dibromomethane at 0℃; for 3 h; Stage #2: With water In 1,2-dibromomethaneCooling
At room temperature, CBr4*2AlBr3 was prepared by stirring CBr4 with AlBr3 in a molar ratio of 1-2 in anhydrous CH2Br2. Next, at 0 °C under atmospheric CO pressure, AdH (1) (1.43 mmol) was added to the freshly prepared CBr4*2AlBr3 (2.87 mmol) in CH2Br2 (3 mL). The mixture was stirred for 3 h. Then at atmospheric CO pressure, H2O (15 mL) was added carefully with cooling. The reaction mixture was kept for 1-2 d until the precipitation of 1,3-Ad(COOH)2 was complete. The Ad(COOH)2 was filtered, washed with H2O, dried, and crystallized from AcOH. The yield of analytically pure compound was 80percent with respect to 1. Mp 285-286 °C. Calcd. for C12H16O4, (percent): C, 64.27; H, 7.19. Found (percent): C, 64.21; H, 7.24.
Reference:
[1] Tetrahedron Letters, 2012, vol. 53, # 27, p. 3493 - 3496
[2] Journal of Organic Chemistry, 1998, vol. 63, # 2, p. 222 - 223
[3] Journal of Organic Chemistry, 1978, vol. 43, p. 4978 - 4980
Preparation 13 200 g of bromine and 0.43 g of electrolytic iron were placed into a 1L four-necked flask, and 34.1 of adamantane was gradually placed therein while ice-cooling.Thereafter, the material was diluted with 400 ML of methylene chloride, a 10% aqueous sodium sulfite solution was added, and the mixture was stirred well.The aqueous layer was removed, and the organic layer was washed with 200 ML of water two times.The organic layer was concentrated, 50 ML of diethyl ether was added to the resulting crude product, 500 ML of methanol was further added, and the mixture was stirred well.The precipitated crystals were filtered, and dried to obtain 46.2 g of 1,3-dibromoadamantane.
Step one, equipped with a condenser, a thermometer and a tail gas absorption 5L four reaction flask, 108g of iron powder was added slowly dropwise over anhydrous bromine 400ml, about half an hour dropwise, stirred for 30 minutes after completion; document.write(""); Step two, the remaining bromine was added dropwise to the reaction flask. After completion, was heated to 45-50 deg.] C, 600g adamantane slowly added to the reaction system, the reaction temperature was raised to 62-65 deg.] C to reflux. The reaction to 65 hours have small sample measured GC showed starting material consumed. (In the control 1) document.write(""); Wherein the molar ratio of adamantane, anhydrous bromine, iron powder is 1: 10.6: 0.44.document.write(""); Step III After completion of the reaction, the recovered bromine atmospheric distillation, and the reaction mixture was poured into ice containing 3.5L bucket chloroform, stirred 10min, filtered through celite pad.document.write(""); Step four, the filtrate was washed with a saturated aqueous solution of sodium bisulfite and excess bromine (note cooled) solid sodium bisulfite consumption 5kg. document.write(""); Fifth, the organic layer was washed organic layer with water 3kg * 2 step was concentrated to dryness to give a crude product 1.95kg. document.write(""); Step six, 13L with methanol, heated and melted, add 65g active carbon, filtered hot, the filtrate was stirred for crystallization (cooling with ice). And filtered to give 1.19kg quality, the mother liquor was concentrated to about one-third of the original volume and stirred for crystallization, and filtered to give 250g white fine.
With iron(III)-acetylacetonate; carbon tetrabromide;Sealed tube; Inert atmosphere;
General procedure: The reactions were carried out in glass ampoules (20 mL) or in a pressure microreactor of stainless steel (17 mL). The results of parallel experiments were identical. Into the microreactor (ampoule) in an argon atmosphere was charged 0.3 mmol of Fe(acac)3, 10 mmol of initial adamantane, 10 mmol of CBr4, and 150 mmol of CH2Br2. The reactor was hermetically closed (the ampoule was sealed) and heated while stirring. On the completion of the reaction the reactor (ampoule) was cooled to room temperature, opened, the solvent was distilled off, the residue was crystallized from hexane or ethanol. Yields are given in respect to converted adamantane (adamantine derivatives) (GLC procedure, internal reference decene; correction factor for adamantane 1.09, for bromoadamantane 1.53). The structure of compounds obtained was proved by comparison with known samples and published data.
With oxygen;vanadium on montmorillonite; In acetic acid tert-butyl ester; at 100℃; under 760.051 Torr; for 96h;Product distribution / selectivity;
The procedure of Example 1 was repeated, except that the catalyst was replaced by a catalyst that vanadium (18 mumol) is supported on montmorillonite (i.e., a V/Mont. catalyst); the amount of adamantane employed was changed to 3 mmol; t-butyl acetate was employed as a solvent; and reaction was performed at 100 C. for 96 hours. The V/Mont. catalyst was formed through the catalyst preparation process described in Japanese Patent Application Laid-Open (kokai) No. 2004-2234. Specifically, the catalyst was obtained by adding an aqueous vanadium(III) chloride solution to montmorillonite (Kunipia F, product of Kunimine Industries Co., Ltd.), followed by ion exchange, filtration, washing with water, drying, and firing in air at 800 C.
With oxygen; acetic acid;N-hydroxyphthalimide; bis(acetylacetonate)oxovanadium; at 75℃; under 760.051 Torr; for 6h;Product distribution / selectivity;
The procedure of Example 1 was repeated, except that the catalyst was replaced by NHPI (1 mmol) and VO(acac)2 (50 mumol); the amount of acetic acid serving as a solvent was changed to 25 mL; and the reaction temperature was changed to 75 C.
A gas chromatographic analysis of products in a reaction mixture found that 1-adamantanol and 1,3-adamantanediol were formed in yields of 38% and 4%, respectively, with a conversion rate from adamantane of 48%.
Adamantane was brominated with bromine/AlBr3 as described in G. S. Lee et al., Org. Lett. Vol. 6, No. 11, 2004, 1705-1707, scheme 2a, (a). The title compound (1) was obtained in 85% yield.
At room temperature, CBr4*2AlBr3 was prepared by stirring CBr4 with AlBr3 in a molar ratio of 1-2 in anhydrous CH2Br2. Next, at 0 °C under atmospheric CO pressure, AdH (1) (1.43 mmol) was added to the freshly prepared CBr4*2AlBr3 (2.87 mmol) in CH2Br2 (3 mL). The mixture was stirred for 3 h. Then at atmospheric CO pressure, H2O (15 mL) was added carefully with cooling. The reaction mixture was kept for 1-2 d until the precipitation of 1,3-Ad(COOH)2 was complete. The Ad(COOH)2 was filtered, washed with H2O, dried, and crystallized from AcOH. The yield of analytically pure compound was 80percent with respect to 1. Mp 285-286 °C. Calcd. for C12H16O4, (percent): C, 64.27; H, 7.19. Found (percent): C, 64.21; H, 7.24.
With oxygen; propionic acid;bis(acetylacetonate)oxovanadium; at 120℃; under 760.051 Torr; for 6h;Product distribution / selectivity;
The procedure of Example 1 was repeated, except that the acetic acid serving as a solvent was replaced by propionic acid. Example 7 The procedure of Example 6 was repeated, except that the amount of the catalyst was changed to 10 mumol. Example 8 The procedure of Example 6 was repeated, except that the amount of the catalyst was changed to 1.3 mumol.
4.2%; 25.1%; 3.9%; 2.4%
With methanesulfonic acid; oxygen; propionic acid;bis(acetylacetonate)oxovanadium; at 100℃; under 760.051 Torr; for 6h;Product distribution / selectivity;
The procedure of Example 9 was repeated, except that methanesulfonic acid [CH3SO3H] was added in an amount of 0.004 mL.
4.1%; 23.2%; 3.3%; 1.4%
With oxygen; propionic acid;bis(acetylacetonate)oxovanadium; at 100℃; under 760.051 Torr; for 6h;Product distribution / selectivity;
The procedure of Example 9 was repeated, except that europium triflate [Eu(OTf)3] was added in an amount of 10 mumol.
2.9%; 21.7%; 2.5%; 1.4%
With oxygen; propionic acid;cobalt acetylacetonate; at 110℃; under 760.051 Torr; for 6h;Product distribution / selectivity;
The procedure of Example 6 was repeated, except that the amount of adamantane employed was changed to 5 mmol, and the catalyst was replaced by Co(acac)2.2H2O.
2.4%; 15.3%; 2.7%; 1.5%
With oxygen; acetic acid;oxovanadium(IV) tetraphenylporphyrin; at 120℃; under 760.051 Torr; for 6h;Product distribution / selectivity;
The procedure of Example 1 was repeated, except that the catalyst was replaced by a vanadium oxide-TPP complex [VOTPP].
2.0%; 15.5%; 2.3%; 0.7%
With oxygen; propionic acid;bis(acetylacetonate)oxovanadium; at 100℃; under 760.051 Torr; for 6h;Product distribution / selectivity;
The procedure of Example 6 was repeated, except that the amount of adamantane employed was changed to 5 mmol, and the reaction temperature was changed to 100 C.
Adamantine (1.01 g, 6.68 mmol, 2.1 equiv) was dissolved in30 mL of dried DMF and 10 mL of Et3N. The mixture wascooled to 273 K under an inert atmosphere and EDTA anhydride(0.82 g, 3.20 mmol, 1 equiv) was added portionwise.After 16 h of stirring under inert atmosphere, the solvent wasremoved under vacuum, and 10 mL of water was added and thesolution was neutralized by HCl. The precipitate was washedwith water, dried under reduced pressure then recrystallized inMeOH to obtain the diacidic compound. The diacid (814 mg,1.46 mmol, 1 equiv) was suspended in water (10 mL) andNaOH (116 mg, 2.90 mmol, 2 equiv) was added. The mixturewas sonicated for 10 min and the product precipitated by additionof 100 mL of acetone. The solid was filtered, washed withacetone and dried under reduced pressure to obtain ADAdim 4as a white powder (m = 420 mg), with a yield of 52% over thetwo steps. The analyses are in full agreement with the literature[36]. Mp 505-506 K; 1H NMR (DMSO-d6, 300.13 MHz) delta 7.47(NH, 2H), 3.37 (Hf, 4H), 3.15 (Hd, 4H), 2.72 (He, 4H), 1.99(Hb, 6H), 1.91 (Ha, 12H), 1.60 (Hc, 12H); 13C NMR (DMSOd6,75.77 MHz) delta 172.5, 169.3, 58.8, 55.9, 52.4, 50.8, 41.1,36.1, 29.0; HRMS-ESI (m/z): [M + Na]+ calcd forC30H46N4O6Na, 581.3315; found, 581.3299.
With tert-butyl hypobromite; carbon tetrabromide; In dichloromethane; at 40℃; for 90h;Darkness;
tert-Butyl hypobromite 50 (0.33 mL, freshly prepared and used immediately, 0.05 mmol, 0.1 eq.), adamantane 18 (68 mg, 0.5 mmol), carbon tetrabromide (166 mg, 0.5 mmol, 1 eq.) and dichloromethane (3.13 mL) were added to an oven-dried pressure tube and the reaction mixture was stirred at 40 C for 90 h in the dark. The reaction mixture was cooled to RT and quenched with aqueous hydrochloric acid (1 M, 5 mL) and extracted with dichloromethane (4 x 10 mL). The organic phases were combined, dried over Na2SO4, filtered and concentrated in vacuo. The yield of adamantane 18 (29%), 1-bromoadamantane 31 (35%), 2-bromoadamantane 51 (14%) and 1,3-bromoadamantane 52 (11%) were determined by adding 1,3,5-trimethoxybenzene to the crude mixture as an internal standard for 1H-NMR.