* 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 phosphorus tribromide In dichloromethane at 0℃; for 3 h;
To a solution of (3,4-dimethylphenyl)methanol (1.00 g, 7.34 mmol) in dichloromethane (10 mL) at 0 °C was added tribromophosphine (1.2 g, 4.41 mmol) and the mixture was stirred for 3 hours. The reaction was quenched with water (20 mL) and the organics extracted with dichloromethane (20 mL x 3). The combined organic phase was washed with brine (40 mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure to afford the title compound as an oil (1.2 g, Yield: 82percent). 1H NMR (400 MHz, CDCI3) 6 7.17 (s, 1 H), 7.15-7.09 (m, 2 H), 4.47 (s, 2 H), 2.25 (s, 6 H) ppm.
Reference:
[1] Organic and biomolecular chemistry, 2003, vol. 1, # 17, p. 3033 - 3037
[2] Polish Journal of Chemistry, 2007, vol. 81, # 5-6, p. 947 - 969
[3] Patent: WO2013/81642, 2013, A1, . Location in patent: Page/Page column 94
[4] Chemical & Pharmaceutical Bulletin, 1983, vol. 31, # 11, p. 4189 - 4192
[5] Pest Management Science, 2000, vol. 56, # 10, p. 875 - 881
[6] Synlett, 2005, # 14, p. 2130 - 2134
[7] European Journal of Medicinal Chemistry, 2012, vol. 55, p. 125 - 136
2
[ 6966-10-5 ]
[ 102-46-5 ]
Reference:
[1] Monatshefte fur Chemie, 1996, vol. 127, # 2, p. 185 - 200
[2] Bulletin of the Korean Chemical Society, 2010, vol. 31, # 11, p. 3434 - 3436
[3] Journal of the American Chemical Society, 1957, vol. 79, p. 4229,4230
[4] Journal of the American Chemical Society, 1990, vol. 112, # 21, p. 7537 - 7540
[5] Journal of Medicinal Chemistry, 1989, vol. 32, # 8, p. 1757 - 1763
3
[ 95-63-6 ]
[ 16308-92-2 ]
[ 6966-10-5 ]
[ 496-78-6 ]
[ 2416-94-6 ]
[ 697-82-5 ]
[ 53957-33-8 ]
Reference:
[1] Chemistry - A European Journal, 2017, vol. 23, # 71, p. 17981 - 17991
Reference:
[1] Monatshefte fur Chemie, 1996, vol. 127, # 2, p. 185 - 200
[2] Phytochemistry, 2002, vol. 59, # 1, p. 9 - 21
[3] Chemistry - A European Journal, 2012, vol. 18, # 29, p. 9011 - 9018
[4] Journal of the American Chemical Society, 1990, vol. 112, # 21, p. 7537 - 7540
[5] European Journal of Organic Chemistry, 2013, # 11, p. 2061 - 2065
[6] Angewandte Chemie - International Edition, 2014, vol. 53, # 33, p. 8722 - 8726[7] Angew. Chem., 2014, vol. 126, # 33, p. 8867 - 8871,5
[8] ChemSusChem, 2013, vol. 6, # 6, p. 1001 - 1005
7
[ 5973-71-7 ]
[ 6966-10-5 ]
Reference:
[1] Journal of Organic Chemistry, 2018, vol. 83, # 4, p. 2274 - 2281
[2] European Journal of Medicinal Chemistry, 2012, vol. 55, p. 125 - 136
[3] Journal of Materials Chemistry A, 2018, vol. 6, # 37, p. 18242 - 18251
8
[ 619-04-5 ]
[ 6966-10-5 ]
Reference:
[1] Polish Journal of Chemistry, 2007, vol. 81, # 5-6, p. 947 - 969
[2] Pest Management Science, 2000, vol. 56, # 10, p. 875 - 881
[3] Phytochemistry, 2002, vol. 59, # 1, p. 9 - 21
[4] Monatshefte fur Chemie, 1996, vol. 127, # 2, p. 185 - 200
[5] Journal of the American Chemical Society, 1990, vol. 112, # 21, p. 7537 - 7540
9
[ 33499-44-4 ]
[ 6966-10-5 ]
Reference:
[1] Journal of the American Chemical Society, 1948, vol. 70, p. 229
10
[ 95-47-6 ]
[ 6966-10-5 ]
Reference:
[1] Journal of the American Chemical Society, 1990, vol. 112, # 21, p. 7537 - 7540
[2] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1913, vol. 157, p. 1445
[3] Bulletin de la Societe Chimique de France, 1939, vol. <5> 6, p. 1025,1033
11
[ 693-98-1 ]
[ 6966-10-5 ]
[ 70759-03-4 ]
Reference:
[1] Synthesis, 2004, # 15, p. 2540 - 2544
12
[ 583-71-1 ]
[ 6966-10-5 ]
Reference:
[1] Journal of the American Chemical Society, 1990, vol. 112, # 21, p. 7537 - 7540
13
[ 1309380-74-2 ]
[ 6966-10-5 ]
Reference:
[1] Journal of Organic Chemistry, 2011, vol. 76, # 11, p. 4652 - 4660
14
[ 319914-16-4 ]
[ 6966-10-5 ]
Reference:
[1] Journal of Organic Chemistry, 2011, vol. 76, # 11, p. 4652 - 4660
15
[ 102-46-5 ]
[ 6966-10-5 ]
Reference:
[1] Bulletin de la Societe Chimique de France, 1939, vol. <5> 6, p. 1025,1033
[2] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1913, vol. 157, p. 1445
16
[ 349109-03-1 ]
[ 6966-10-5 ]
Reference:
[1] Chemische Berichte, 1955, vol. 88, p. 301,307
17
[ 1309380-84-4 ]
[ 6966-10-5 ]
[ 65609-15-6 ]
Reference:
[1] Journal of Organic Chemistry, 2011, vol. 76, # 11, p. 4652 - 4660
18
[ 95-63-6 ]
[ 16308-92-2 ]
[ 6966-10-5 ]
[ 496-78-6 ]
[ 2416-94-6 ]
[ 697-82-5 ]
[ 53957-33-8 ]
Reference:
[1] Chemistry - A European Journal, 2017, vol. 23, # 71, p. 17981 - 17991
With phosphorus tribromide; In dichloromethane; at 0℃; for 3h;
To a solution of <strong>[6966-10-5](3,4-dimethylphenyl)methanol</strong> (1.00 g, 7.34 mmol) in dichloromethane (10 mL) at 0 C was added tribromophosphine (1.2 g, 4.41 mmol) and the mixture was stirred for 3 hours. The reaction was quenched with water (20 mL) and the organics extracted with dichloromethane (20 mL x 3). The combined organic phase was washed with brine (40 mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure to afford the title compound as an oil (1.2 g, Yield: 82%). 1H NMR (400 MHz, CDCI3) 6 7.17 (s, 1 H), 7.15-7.09 (m, 2 H), 4.47 (s, 2 H), 2.25 (s, 6 H) ppm.
With phosphorus tribromide; In dichloromethane; at 0℃; for 0.5h;
General procedure: To a solution of phenylmethanols 5a-w (5 mmol) dissolved in methylene chloride (50 mL) in an ice-water bath was added phosphorus tribromide (5.5 mmol), and the mixture was stirred at the same temperature for 30 min. The mixture was washed with cool water, dried over anhydrous Na2SO4 and concentrated under reduced pressure to yield (bromomethyl)benzenes 6aew as offwhite solids or light yellow oils
Example 2:; This example teaches the preparation of [2-(lH-benzoimidazol-2-yl)-ethyl]-carbamic acid 3,4- dimethyl-benzyl ester. To a solution of <strong>[6966-10-5]3,4-dimethylbenzyl alcohol</strong> (1.5 g, 11.0 mmol) in toluene (20 mL) was added phosgene (13 mL, 24.3 mmol, 20% in toluene). After stirring at room temperature overnight, excess phosgene and toluene was removed in vacuo, and dried under high vacuum for 2 h. providing 3, 4-dimethylbenzylchloroformate (1.8 g) as an oil at 80 % yield. (reference: Nagele, E.; Schelhaas, M.; Kuder, N.; Waldmann, H. J. Am. Chem. Soc. 1998, 120, 6889)
With N-ethyl-N,N-diisopropylamine; In dichloromethane; toluene; at 20℃; for 2h;
Example 39; 3',4'-Dimethvlphenylmethyl 2-cvanopvrazolidine-1 -carboxylate (39)3',4'-Dimethylphenylmethyl chloroformate was prepared by dissolving <strong>[6966-10-5]3,4-dimethylbenzyl alcohol</strong> (94.0 mg, 0.69 mmol) was in 3 ml_ dichloromethane followed by diisopropylethylamine (145 uL, 0.83 mmol). 20% Phosgene in toluene (473 uL, 0.83 mmol) was added dropwise and the reaction mixture was allowed to stir at room temperature for 2 hours.4 was prepared according to Example 4. To this was added the 4'-acetylaminophenyl chloroformate in one portion and the reaction mixture was stirred overnight at room temperature. After removal of solvent by rotary evaporation, the title compound was purified by silica gel chromatography (CombiFlash, 20% ethyl acetate in hexanes to 100% ethyl acetate over 10 minutes.) The appropriate fractions were collected, combined and evaporated to dryness to yield 39 (57.0 mg, 31.9%), ESMS 260.4 (M+H+).
With n-butyllithium; sulfuric acid; iodine; In tetrahydrofuran; hexane; pentane;
109.1 A solution, cooled to 0 C., of 6.81 g of <strong>[6966-10-5]3,4-dimethylbenzyl alcohol</strong> and 11.62 ml of N,N,N',N'-tetramethyl-ethylenediamine in 150 ml of pentane was treated with 62.5 ml of n-butyllithium solution (1.6M in hexane). The reaction mixture was boiled at reflux for 11 hrs. Then, 12.69 g of iodine in 50 ml of THF were added dropwise at -30 C. The mixture was stirred for 15 min. at -30 C. and then left to warm to room temperature. The reaction mixture was added to 100 ml of 10% sulphuric acid. The crude product was isolated by extraction and purified by chromatography on silica gel. There were obtained 2.95 g of (2-iodo-4,5-dimethyl-phenyl)-methanol as a light yellow solid.
...ein R6 represents a methyl or ethyl group substituted with at least one member selected from the aryl group which may be substituted as defined above, a cyano group; or the alkynyl group, include, for example, aralkyl alcohols such as: benzyl alcohol, 2-methyl-3-phenylbenzyl alcohol, ... (2,3-dimethylphenyl)methyl alcohol, (2,4-dimethylphenyl)methyl alcohol, (2,5-dimethylphenyl)methyl alcohol, (2,6-dimethylphenyl)methyl alcohol, (3,4-dimethylphenyl)methyl alcohol, (2,3,4-trimethylphenyl)methyl alcohol, (2,3,5-trimethylphenyl)methyl alcohol, (2,3,6-trimethylphenyl)methyl alcohol, ...
71
[ 6966-10-5 ]
[ 1972-28-7 ]
2-[(3,4-Dimethyl-benzyl)-(5-pyridin-2-yl-thiophene-2-sulfonyl)-amino]-N-hydroxy-3-methyl-benzamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With triphenylphosphine; In tetrahydrofuran; dichloromethane; trifluoroacetic acid;
2-[(3,4-Dimethyl-benzyl)-(5-pyridin-2-yl-thiophene-2-sulfonyl)-amino]-N-hydroxy-3-methyl-benzamide To a suspension of[(5-pyridin-2-yl-thiophene-2-sulfonyl)-amino]-N-hydroxy-3-methyl-benzamide on Wang resin, the product of Example 407 (100 mg, 0.84 mmol/g), in a solution of 3,4 dimethylbenzyl alcohol (0.485 mmol) in THF (1 mL) was added a solution of triphenylphosphine (0.485 mmol) and diethyl azodicarboxylate (0.485 mmol) in THF (1.24 mL). The resultant mixture was shaken for 4 h at room temperature. The resin was filtered, washed with THF (4*3 mL) and dichloromethane (4*3 mL), and dried under vacuum. The resin was suspended in trifluoroacetic acid/ dichloromethane (1:1, 2 mL) and allowed to sit for 1 h. The resin was filtered and washed with DCM (2*1.5 mL). The combined filtrates were evaporated to dryness, and the crude product was purified on a solid phase extraction cartridge (reverse phase) to give 18.1 mg of product Mass Spec: expected 507.1286, found 507.9.
With triphenylphosphine; In tetrahydrofuran; dichloromethane; trifluoroacetic acid;
2-[(3,4-Dimethyl-benzyl)-(5-pyridin-2-yl-thiophene-2-sulfonyl)-amino]-N-hydroxy-3-methyl-benzamide To a suspension of (5-pyridin-2-yl-thiophene-2-sulfonyl)-amino]-N-hydroxy-3-methyl-benzamide on Wang resin, the product of Example 407 (100 mg, 0.84 mmol/g), in a solution of <strong>[6966-10-5]3,4-dimethylbenzyl alcohol</strong> (0.485 mmol) in THF (1 mL) was added a solution of triphenylphosphine (0.485 mmol) and diethyl azodicarboxylate (0.485 mmol) in THF (1.24 mL). The resultant mixture was shaken for 4 h at room temperature. The resin was filtered, washed with THF (4 X 3 mL) and dichloromethane (4 X 3 mL), and dried under vacuum. The resin was suspended in trifluoroacetic acid/ dichloromethane (1:1, 2 mL) and allowed to sit for 1 h. The resin was filtered and washed with DCM (2 X 1.5 mL). The combined filtrates were evaporated to dryness, and the crude product was purified on a solid phase extraction cartridge (reverse phase) to give 18.1 mg of product. Mass Spec: expected 507.1286, found 507.9.
1-benzoyl-3-[-(3,4-dimethylbenzyl)piperid-4-yl]urea[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With thionyl chloride; triethylamine; In N-methyl-acetamide; ethanol; chloroform; benzene;
EXAMPLE 6 1-Benzoyl-3-[1-(3,4-dimethylbenzyl)piperid-4-yl]urea 3,4-Dimethylbenzyl alcohol (0.68 g, 0.005 m) in dry benzene (10 cm3) was treated with thionyl chloride (3 cm3) and refluxed for 3 hours. The solvent was evaporated and the residue treated with benzene (3 times) and evaporated. 4-Benzoylureidopiperidine (1.28 g, 0.05 m), triethylamine (1.5 g, 0.015 m) and dimethylformamide (25 cm3) were added to the residue and the reaction mixture stirred at 50 C. for 2 hours. The solution was filtered and the filtrate diluted with water. The precipitated solid was filtered, dissolved in chloroform and washed well with water, dried (MgSO4) and evaporated to give a solid. The solid was suspended in ethanol and acidified with ethanolic HCl to give the title compound, which was recrystallized from ethanol as the hydrochloride, quarterhydrate, m.p. 239-240 C. Analysis: C22 H27 N3 O2.HCl.1/4H2 O requires: C, 65.01; H, 7.07; N, 10.34%. Found: C, 64.62; H, 7.05; N, 10.15%.
7-[3-aminomethyl-4-(3',4'-dimethylbenzyloxyimino)pyrrolidin-1-yl]-1-cyclopropyl-6-fluoro-1,4-dihydro-4-oxo-1,8-naphthyridine-3-carboxylic acid dimesylate[ No CAS ]
With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; ammonium hydroxide; copper(I) bromide; at 80℃; for 20h;
The reactants used were 3,4-dimethylbenzyl alcohol (i.e., R1 in the formula (I) was a para, meta-two CH3)1.0 mmol (136.2 mg), the experimental procedure and procedure were the same as Example 1, aqueous ammonia (1.8 mol / L) 5.0 mL, the catalyst cuprous bromide was used in an amount of 5 mol% (7.2 mg), TEMPO was used in an amount of 5 mol% ), The reaction temperature was 80 , the reaction time was 20 h,The crude product was purified by column chromatography (petroleum ether: ethyl acetate = 10: 1) to give the pure title product in 128.6 mg yield 98%.
87%
With 1,4-diaza-bicyclo[2.2.2]octane; TEMPOL; ammonia; copper(l) chloride; In water; acetonitrile; at 20℃; for 24h;
General procedure: To a 25-mL Schlenk tube equipped with a magnetic stirrer, CuCl (0.05 mol, 5 mol%), DABCO (0.10 mol, 10 mol%), 4-HO-TEMPO (0.05 mmol, 5 mol%) were added. Substrates 1 (1 mmol) and NH3 (aq, 25-28%, 3 mmol, 3.0 equiv) in CH3CN (2 mL) were added subsequently. Then the reaction mixture was stirred at room temperature for 24 h in the presence of an air balloon. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was diluted with water and extracted with ethyl acetate. The organic layer was dried over anhydrous MgSO4. Subsequently, the combined organic layer was concentrated under reduced pressure and the crude product was purified by column chromatography to afford the corresponding products.