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1

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With tetra-alkylammonium iodide Heating;

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Linstad, Ethan J.; Vāvere, Amy L.; Hu, Bao; Kempinger, Jayson J.; Snyder, Scott E.; DiMagno, Stephen G.

Organic and Biomolecular Chemistry, 2017 , vol. 15, # 10 p. 2246 - 2252 Title/Abstract Full Text View citing articles Show Details

2

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85%

With potassium carbonate in neat (no solvent) T=20°C; 2 h; Hide Experimental Procedure

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Massah, Ahmad R.; Gharaghani, Sajjad; Lordejani, Hamid Ardeshiri; Asakere, Nahad

Medicinal Chemistry Research, 2016 , vol. 25, # 8 p. 1538 - 1550 Title/Abstract Full Text View citing articles Show Details

Synthesis of 7-chloro-1-methyl-5-phenyl-1H-benzo[e][1,4]diazepin-2(3H)-one (diazepam) (4)

To a vigorously stirredmixture of nordiazepam (1) (0.27 g, 1 mmol) andpowder of K2CO3 (0.42 g, 3 mmol), dimethyl sulfate(0.37 mL, 4 mmol) was added. The progress of the reactionwas monitored by TLC. After completion of thereaction (2 h), water (3 9 10 mL) was added and the7-chloro-1-methyl-5-phenyl-1H-benzo[e][1,4]diazepin-2(3H)-one (diazepam) was easily isolated by a simple filtration in85 percent yield and high purity. m.p = 130–132° C [129–132° C (Grant et al., 2010)]; IR (KBr, cm-1): 701, 1653,1675, 2939, 2978; 1H NMR(CDCl3, 400 MHz):δ 4.34 (s,2H), 5.22 (s, 3H), 7.43 (d, 4H, J = 11.4 Hz), 7.56 (d, 1H,J = 6.9 Hz), 7.77 (d, 2H, J = 6.7 Hz), 8.52 (d, 1H,J = 8.2). With sodium methylate in methanol

T=5°C; Methylation;

Markovic, Dean; Hamersak, Zdenko; Visnjevac, Aleksandar; Kojic-Prodic, Biserka; Sunjic, Vitomir

Helvetica Chimica Acta, 2000 , vol. 83, # 3 p. 603 - 615 Title/Abstract Full Text View citing articles Show Details

3

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Rx-ID: 41975305 Find similar reactions

67%

Stage #1: N-(2-benzoyl-4-chlorophenyl)-Nmethylnitrous amide With iron; ammonium chloride in ethanol

T=80°C; 6 h; Stage #2: glycine ethyl ester hydrochloride With acetic acid in ethanol

3 h; Reflux;

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Wu, Yinuo; Sun, Lei; Chen, Yunyun; Zhou, Qian; Huang, Jia-Wu; Miao, Hui; Luo, Hai-Bin

Journal of Organic Chemistry, 2016 , vol. 81, # 3 p. 1244 - 1250 Title/Abstract Full Text View citing articles Show Details

4

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Rx-ID: 41975307 Find similar reactions

Wu, Yinuo; Sun, Lei; Chen, Yunyun; Zhou, Qian; Huang, Jia-Wu; Miao, Hui; Luo, Hai-Bin

Journal of Organic Chemistry, 2016 , vol. 81, # 3 p. 1244 - 1250 Title/Abstract Full Text View citing articles Show Details


5

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Rx-ID: 41975365 Find similar reactions

Wu, Yinuo; Sun, Lei; Chen, Yunyun; Zhou, Qian; Huang, Jia-Wu; Miao, Hui; Luo, Hai-Bin

Journal of Organic Chemistry, 2016 , vol. 81, # 3 p. 1244 - 1250 Title/Abstract Full Text View citing articles Show Details

6

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Rx-ID: 42274263 Find similar reactions

Stage #1: in 1-methyl-pyrrolidin-2-one

T=90°C; 0.155 h; Flow reactor; Stage #2: With ammonia in 1-methylpyrrolidin-2-one; methanol; water

T=130°C; P=12751.3 Torr; 0.065 h; Flow reactor;

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Adamo, Andrea; Beingessner, Rachel L.; Behnam, Mohsen; Chen, Jie; Jamison, Timothy F.; Jensen, Klavs F.; Monbaliu, Jean-Christophe M.; Myerson, Allan S.; Revalor, Eve M.; Snead, David R.; Stelzer, Torsten; Weeranoppanant, Nopphon; Wong, Shin Yee; Zhang, Ping

Science, 2016 , vol. 352, # 6281 p. 61 - 67 Title/Abstract Full Text View citing articles Show Details

A

B

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7

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A: 55% B: 39%

With N-ethylmorpholine; in N,N-dimethylformamide

T=-20 - 20°C; 19 h; Inert atmosphere; Hide Experimental Procedure

REGENTS OF THE UNIVERSITY OF MINNESOTA; SIEGEL, Ronald, A.; KAPOOR, Mamta; CHERYALA, Narsihmulu; GEORG, Gunda, I.; CLOYD, James, C.

Patent: WO2016/149540 A1, 2016 ; Location in patent: Page/Page column 30-31 ; Title/Abstract Full Text Show Details

1:Di-ferf-butyl (6-((2-((2-Benzoyl-4-chlorophenyl)(methyl)amino)-2-oxoethyl)amino)-6-oxohexane- -diyl)(S dicarbamate (7)

Di-ferf-butyl (6-((2-((2-Benzoyl-4-chlorophenyl)(methyl)amino)-2-oxoethyl)amino)-6-oxohexane- -diyl)(S dicarbamate (7): 5 7 8 To aminoketone 5 (2.50 g, 6.52 mmol) and Boc-Z-Lys(Boc)-OSu (6, 2.90 g, 6.52 mmol) in dry DMF (60 mL) was added N-ethylmorpholine (0.825 mL, 6.52 mmol) at -20 °C under nitrogen. The reaction mixture was stirred for 1 h at the same temperature and 2 h at 0 °C, then stirring was continued for 16 h at room temperature. The reaction was diluted with ethyl acetate (150 mL), washed with water (2 x 100 mL), brine (100 mL), dried over Na2S04, filtered and then the volatiles were evaporated in vacuo. The crude residue was purified by flash column chromatography (silica gel, 0-75percent ethyl acetate in hexanes) to furnish 7 (2.26 g, 55percent) as a colorless powder and diazepam (8, 722 mg, 39percent) as a colorless powder. Compound 7: The presence of rotamers precluded a comprehensive assignment of all proton and carbon resonances. R/ 0.53 (hexanes/ethyl acetate, 1:1); 'H NMR (400 MHz, CDC13) δ 7.79- 7.71 (m, 2H), 7.66-7.41 (m, 5H), 7.32 (dd, J= 8.4, 4.2 Hz, 0.79H), 7.21 (d, J= 8.5 Hz, 0.21H), 6.81 (dt, J= 9.7, 4.6 Hz, 0.76H), 6.69 (d, J= 4.3 Hz, 0.19H), 5.11 (s, 1H), 4.81 - 4.54 (m, 1H), 4.09 (dt, J = 7.1, 3.7 Hz, 1H), 3.89 (dd, J= 17.4, 5.2 Hz, 1H), 3.68 (dd, J= 17.4, 3.7 Hz, lH), 3.24 (s, 0.63H), 3.04 (s, 4.34H), 1.86-1.71 (m, 1H), 1.66-1.53 (m, 1H), 1.52-1.24 (m, 22H); 13C NMR (100 MHz, CDC13) 5 194.54, 193.47, 172.00, 168.67, 156.26, 155.72, 140.24, 139.02,

138.68, 138.20, 136.57, 135.97, 134.84, 134.46, 133.65, 133.16, 132.63, 132.17, 131.25, 130.25, 129.11, 128.63, 80.11, 79.18, 54.48, 42.24, 41.68, 40.24, 38.17, 37.73, 32.70, 29.81, 28.59, 22.73; HRMS (ESI+) calculated for C32H43CIN4O7 [M + Na+] 653.2712, found 653.2710; [a]D22 -10.6 (c = 0.5, CH3OH). Compound 8: R 0.24 (hexanes/ethyl acetate, 1:1); mp 126-130 °C (lit 129-131.5 °C) (Gates, M., New synthesis of diazepam. Journal of Organic Chemistry 1980, 45, 1675-81); FontWeight="Bold" FontSize="10" H NMR (400 MHz, CDCI3) δ 7.62-7.58 (m, 2H), 7.53-7.45 (m, 2H), 7.41 (dd, J= 8.2, 6.6 Hz, 2H), 7.31-7.27 (m, 2H), 4.83 (d, J= 10.8 Hz, 1H), 3.77 (d, J= 10.8 Hz, 1H), 3.39 (s, 3H); 13C NMR (101 MHz, CDC13) 5 170.13, 169.11, 142.80, 138.37, 131.65, 130.89, 130.27, 130.09, 129.66, 129.46, 128.60, 122.71, 57.18, 35.07; HRMS (ESI+) calculated for C16H13C1N20 [M + H*] 285.0789, found 285.0788.

8

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Rx-ID: 43901298 Find similar reactions

REGENTS OF THE UNIVERSITY OF MINNESOTA; SIEGEL, Ronald, A.; KAPOOR, Mamta; CHERYALA, Narsihmulu; GEORG, Gunda, I.; CLOYD, James, C.

Patent: WO2016/149540 A1, 2016 ; Title/Abstract Full Text Show Details

9

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Massah, Ahmad R.; Gharaghani, Sajjad; Lordejani, Hamid Ardeshiri; Asakere, Nahad

Medicinal Chemistry Research, 2016 , vol. 25, # 8 p. 1538 - 1550 Title/Abstract Full Text View citing articles Show Details


10

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Rx-ID: 5288415 Find similar reactions

76%

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With P-tris(dimethylamino)-Cdimethylphosphonium ylide in tetrahydrofuran

T=-78 - 20°C; Methylation; 3 h;

Goumri-Magnet; Guerret; Gornitzka; Cazaux; Bigg; Palacios; Bertrand

Journal of Organic Chemistry, 1999 , vol. 64, # 10 p. 3741 - 3744 Title/Abstract Full Text View citing articles Show Details

With NaOD in water-d2; acetone

Methylation; Heating;

Sassaman, Mark B.; Panico, Mariarosaria; Schmall, Bernard; Eckelman, William C.

Journal of Labelled Compounds and Radiopharmaceuticals, 1999 , vol. 42, # 13 p. 1229 - 1233 Title/Abstract Full Text View citing articles Show Details

11

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T=20°C; var. pH, var. temp., E(a), ΔH(excit.), ΔS(excit.), ΔG(excit.); Thermodynamic dataMechanismKinetics;

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Rx-ID: 5114681 Find similar reactions

Yang, Shen K.

Journal of the Chinese Chemical Society, 1998 , vol. 45, # 5 p. 635 - 642 Title/Abstract Full Text View citing articles Show Details

12

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Rx-ID: 6057831 Find similar reactions

Aki,O. et al.

Chemical and Pharmaceutical Bulletin, 1972 , vol. 20, p. 2372 - 2376


Full Text View citing articles Show Details

Yamamoto et al.

Chemische Berichte, 1968 , vol. 101, # 12 p. 4245 Full Text View citing articles Show Details

Sumitomo Chem. Co.

Patent: ZA6803041 , 1967 ; Chem.Abstr., 1969 , vol. 71, # 124519m Full Text Show Details

Hoffmann-LaRoche

Patent: US3996209 , 1976 ; Chem.Abstr., vol. 86, # 140097 Full Text Show Details

Natsugari et al.

Chemical and Pharmaceutical Bulletin, 1979 , vol. 27, p. 2084,2090 Full Text Show Details

Vane; Benz

Organic Mass Spectrometry, 1979 , vol. 14, p. 233,234 Full Text Show Details

Bell et al.

Journal of Organic Chemistry, 1962 , vol. 27, p. 562,563 Full Text Show Details

Sternbach; Reeder

Journal of Organic Chemistry, 1961 , vol. 26, p. 4936,4939 Full Text Show Details

Meguro; Kuwada

Yakugaku Zasshi, 1973 , vol. 93, p. 1263,1266 Chem.Abstr., 1974 , vol. 80, # 27224 Full Text Show Details

Takeda Chem. Ind., Ltd.

Patent: DE1944404 , 1968 ; Chem.Abstr., 1970 , vol. 72, # 100775m Full Text Show Details

Hoffmann-La Roche

Patent: BE620773 , 1962 ; Chem.Abstr., 1963 , vol. 59, # 10094e Full Text Show Details

Delmar Chem. Ltd.

Patent: NL6500446 , 1964 ; Chem.Abstr., 1966 , vol. 64, # 5120 Full Text Show Details

Hoffmann-La Roche

Patent: DE1145626 , 1963 ; Chem.Abstr., 1964 , vol. 60, # 12033h Full Text Show Details

Hoffmann-La Roche

Patent: DE1136709 , 1962 ; Chem.Abstr., 1963 , vol. 59, # 12827 Full Text Show Details

Reeder; Sternbach

Patent: US3136815 , 1960 ; Chem.Abstr., 1964 , vol. 61, # 9515f Full Text Show Details

Hoffmann-La Roche

Patent: CH414652 , 1959 ; Chem.Abstr., 1968 , vol. 68, # 69054s Full Text Show Details

Hoffmann-La Roche Inc.

Patent: US3131178 , 1964 ; Chem.Abstr., 1964 , vol. 61, # 4383c Full Text Show Details

Hoffmann-La Roche

Patent: US3402171 , 1960 ; Chem.Abstr., 1969 , vol. 70, # 37850y Full Text Show Details

Ishuzimi et al.

Chemical and Pharmaceutical Bulletin, 1975 , vol. 23, p. 2169,2171 Full Text Show Details

Hsi

Journal of Labelled Compounds, 1974 , vol. 10, p. 389,394 Full Text Show Details

Bahr et al.

Patent: DD61268 , 1968 ; Chem.Abstr., 1969 , vol. 70, # 68444y Full Text Show Details

Bogatskii et al.

Pharmaceutical Chemistry Journal, 1970 , # 1 p. 3 Khimiko-Farmatsevticheskii Zhurnal, 1970 , # 1 p. 5 Full Text View citing articles Show Details

Andronati et al.

J. Gen. Chem. USSR (Engl. Transl.), 1970 , vol. 40, p. 1881,1862,1863,1868 Full Text Show Details Ellaithy et al. Collection of Czechoslovak Chemical Communications, 1976 , vol. 41, p. 3014,3016,3017,3019 Full Text View citing articles Show Details Oelschlaeger et al. Collection of Czechoslovak Chemical Communications, 1966 , vol. 31, p. 1264,1270


Full Text Show Details

Hoffmann-La Roche

Patent: ZA6800796 , 1967 ; Chem.Abstr., 1969 , vol. 70, # 78029f Full Text Show Details

Lab. Pharmedical

Patent: DE2159920 , 1972 ; Chem.Abstr., vol. 77, # 114440 Full Text Show Details

Schering

Patent: US4155904 , 1979 ; Chem.Abstr., vol. 91, # 108016 Full Text Show Details

Sumitomo Ltd.

Patent: DE2151540 , 1972 ; Chem.Abstr., vol. 77, # 126709 Full Text Show Details

Scherico Ltd.

Patent: DE2640599 , 1978 ; Chem.Abstr., vol. 88, # 190921 Full Text Show Details

Schmitt et al.

Industrie Chimique Belge, 1967 , vol. 32, p. 184,185-187 Chem.Abstr., 1969 , vol. 70, # 96776b Full Text Show Details

Schmitt et al.

Chimica Therapeutica, 1969 , vol. 4, p. 239,244 Full Text Show Details

Etabl.Clin-Byla

Patent: NL6507637 , 1964 ; Chem.Abstr., 1966 , vol. 64, # 15902g Full Text Show Details

Nedenskov; Mandrup

Acta Chemica Scandinavica, Series B: Organic Chemistry and Biochemistry, 1977 , vol. 31, p. 701,704 Full Text Show Details

Sugasawa et al.

Journal of Heterocyclic Chemistry, 1979 , vol. 16, p. 445,448 Full Text Show Details

Hoffmann-La Roche

Patent: CH599176US3873525 , 1978 ; Chem.Abstr., vol. 83, # 58894 Full Text Show Details

Sumitomo

Patent: DE2017060 , 1970 ; Chem.Abstr., 1971 , vol. 74, # 22904 Full Text Show Details

Sumitomo Chemical Co., Ltd.

Patent: JP6917138 , 1966 ; Chem.Abstr., 1970 , vol. 72, # 12779k Full Text Show Details

CRC

Patent: DE2016084 , 1971 ; Chem.Abstr., 1971 , vol. 75, # 36155 Full Text Show Details

Specta Intern.

Patent: FR2260580DE2504937 , 19751975 ; Chem.Abstr., vol. 84, # 44186 Full Text Show Details

Hoffmann-LaRoche

Patent: US3322753 , 1965 ; Chem.Abstr., vol. 68, # 39663x Full Text Show Details

Hoffmann-LaRoche

Patent: AT334376DE2233482 , 1977 ; Chem.Abstr., vol. 78, # 111385 Full Text Show Details

Shenoy et al.

Indian Journal of Pharmacy, 1972 , vol. 3, # 2 p. 48 Full Text Show Details

Hoffmann-LaRoche

Patent: US3376290 , 1965 ; Chem.Abstr., 1968 , vol. 69, # 59299g Full Text Show Details

Reeder; Sternbach

Patent: US3141890US3136815 , 19621960 ; Chem.Abstr., 1964 , vol. 61, # 9514e Full Text Show Details

Polfa

Patent: PL60627 , 1970 ; Chem.Abstr., 1971 , vol. 74, # 88082q Full Text Show Details

Blazevic; Kajfez

Journal of Heterocyclic Chemistry, 1970 , vol. 7, p. 1173 Full Text Show Details

Chugai Seiyakn Kabushiki Kaisha; Japan

Patent: DE1957420 , 1970 ;


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Takeda yakukhin Kogyo

Patent: JP26302 , 1969 ; Ref. Zh., Khim., 1970 , vol. 13, # N455P Full Text Show Details

Hoffmann-La Roche F. und Co. AG

Patent: FR1503346 , 1967 ; Chem.Abstr., 1969 , vol. 70, # 35610t Full Text Show Details

F. Hoffmann-La Roche and Co. AG Patent: CH567006 , 1975 ; Chem.Abstr., vol. 79, # 42575 Full Text Show Details Sumitomo Patent: DE2113122 , 1971 ; Chem.Abstr., 1972 , vol. 76, # 3914f Full Text Show Details Sumitomo Chemical Company Patent: CH599175DE2508332 , 1978 ; Chem.Abstr., vol. 83, # 206341 Full Text Show Details Japan Synthetic. Chem. Ind. Co. Ltd. Patent: JP7031303 , 1970 ; Chem.Abstr., vol. 74, # 53864 Full Text Show Details Kali-Chemie AG Patent: DE2221536 , 1972 ; Chem.Abstr., vol. 80, # 37190 Full Text Show Details Aktieselskabet Dumex Patent: ZA6705130 , 1966 ; Chem.Abstr., 1969 , vol. 70, # 28964m Full Text Show Details Inaba et al. Chemical and Pharmaceutical Bulletin, 1975 , vol. 23, p. 2421,2422, 2423, 2424 Full Text View citing articles Show Details Camps et al. Anales de Quimica (1968-1979), 1974 , vol. 70, p. 848 Full Text Show Details Dumex Ltd. Patent: ZA6707791 , 1968 ; Chem.Abstr., 1969 , vol. 70, # 57916c Full Text Show Details Sumitomo Chemical Co. Ltd. Patent: FR2002315 , 1969 ; Chem.Abstr., 1970 , vol. 72, # 67002g Full Text Show Details Hoffmann-La Roche Patent: CH414652US3427304 , 1966 ; Full Text Show Details

Hoffmann-La Roche

Patent: NL6407739 , 1965 ; Chem.Abstr., 1965 , vol. 62, # 16281b Full Text Show Details

Hoffmann-La Roche and Co.

Patent: AT341527DE2340159 , 1973 ; Chem.Abstr., 1974 , vol. 80, # 133491 Full Text Show Details

Cassella

Patent: DE1942743 , 1971 ; Chem.Abstr., 1971 , vol. 74, # 100116 Full Text Show Details

Sumitomo Chemical Co., Ltd.,

Patent: DE1920207 , 1970 ; Chem.Abstr., 1970 , vol. 72, # 90540q Full Text Show Details

Hoffmann-LaRoche Inc.

Patent: US3681341 , 1970 ; Chem.Abstr., vol. 77, # 126706 Full Text Show Details

Hoffmann-LaRoche

Patent: NL6407796 , 1963 ; Chem.Abstr., 1965 , vol. 63, # 1808g Full Text Show Details

Rexolin Chem. Akt.

Patent: NL6613087 , 1967 ; Chem.Abstr., vol. 67, # 82225 Full Text Show Details

Sankyo Co. Ltd.

Patent: DE2164154 , 1971 ; Chem.Abstr., vol. 77, # 126704 Full Text Show Details

Gedeon Richter Veg. Gyar R:T.

Patent: HU155373 , 1966 ; Chem.Abstr., 1969 , vol. 70, # 87865c


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Hoffmann-LaRoche

Patent: US3546212 , 1970 ; Chem.Abstr., vol. 74, # 112062 Full Text Show Details

Hoffmann-La Roche Inc.

Patent: US3534021 , 1970 ; Chem.Abstr., 1971 , vol. 74, # 53870 Full Text Show Details

Sumitomo Chemical

Patent: JP7006029 , 1966 ; Chem.Abstr., 1970 , vol. 72, # 121597v Full Text Show Details

HeimittelW. Wien GmbH

Patent: AT339319DE2333382 , 1977 ; Chem.Abstr., vol. 82, # 171106 Full Text Show Details

Krka tovarna zdravil

Patent: CH567487DE2211647 , 1972 ; Chem.Abstr., 1973 , vol. 79, # 115647 Full Text Show Details

Petersen; Lakowitz

Acta chemica Scandinavica, 1969 , vol. 23, # 3 p. 971 - 974 Title/Abstract Full Text View citing articles Show Details

Felix et al.

Journal of Heterocyclic Chemistry, 1968 , vol. 5, p. 731 Full Text Show Details

Sternbach et al.

Journal of Organic Chemistry, 1962 , vol. 27, p. 3781,3782, 3786 Full Text View citing articles Show Details

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Research Development Corp. of Japan; Stanley Electric Co., Ltd.

Patent: US5354563 A1, 1994 ; Title/Abstract Full Text Show Details

3:EXAMPLE 3

Diazepam: m.p. 130°-134° C. (psychotropic agent; crystalline powder)

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Conrex Pharmaceutical Corporation

Patent: US5731303 A1, 1998 ; Title/Abstract Full Text Show Details

17:Percutaneous Absorption Diazepam

EXAMPLE 17 Percutaneous Absorption Diazepam The procedure of example 15 was repeated except that 14 C diazepam, diluted 1,000 fold with cold diazepam, was used. The propylene glycol solution contained 18.9 mg/ml of diazepam and 2percent (w/v) of cyclopentadecanone.

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Lipotec S.A.

Patent: US5736161 A1, 1998 ; Title/Abstract Full Text Show Details

non-steroidal anti-inflammatory agents selected from the group consisting of indomethacin, ibuprofen, sulindac, diclofenac, ketorolac and naproxen; dexametasone; anti-glaucoma agents selected from pilocarpine or thymolol; lidocaine; codeine; alpha-tocopherol; thymine; diazepam;

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Hoffmann-La Roche Inc.

Patent: US4898861 A1, 1990 ; Title/Abstract Full Text Show Details


The compounds and symbols utilized in the figures were: ... 2. 7-chloro-5-(4-methoxyphenyl)-1-methyl-3H-1,4-benzodiazepin-2(1H)-one (°); 3. 5-(4-chlorophenyl)-7-fluoro-1-methyl-3H-1,4-benzodiazepin-2(1H)-one (); 4. diazepam () and 5. 1-methyl-5-(4-fluorophenyl)-3H-1,4-benzodiazepin-2(1H)-one ().

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Hoffmann-La Roche Inc.

Patent: US4898861 A1, 1990 ; Title/Abstract Full Text Show Details

Values for the compounds are plotted in FIG. 4, each value being the mean of at least four experiments. ... 1. Diazepam (12) 2. 7-chloro-5-(2-chlorophenyl)-1,3-dihydro-1-methyl-2H-1,4-benzodiazepin-2-one(5) 3. 1,3-dihydro-1-methyl-5-phenyl-2H-1,4-benzodiazepin-2-one(8) ...

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Clin Midy

Patent: US3966793 A1, 1976 ; Title/Abstract Full Text Show Details

16:7-Chloro-1-methyl-5-phenyl-2-oxo-2,3-dihydro-1H-benzo[f]-1,4-diazepine (B)

EXAMPLE 16 7-Chloro-1-methyl-5-phenyl-2-oxo-2,3-dihydro-1H-benzo[f]-1,4-diazepine (B) 6 g. of compound 4361 CB are heated under reflux for 15 minutes in 25 ml. of acetic acid. The acetic acid is removed in vacuo and the residue is taken up in water and a little ether. A yellowish solid separates; m.p. 130°C.; the yield is substantially quantitative. It is recrystallized from diisopropyl ether. Yellowish crystals are obtained (4.4 g.); m.p. 132°C.: yield 85percent in the first batch. The product is identical with the known product (see reference above in Example 14).

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Sumitomo Chemical Company, Limited

Patent: US3991048 A1, 1976 ; Title/Abstract Full Text Show Details

2:EXAMPLE 2

EXAMPLE 2 Example 1-(2) was repeated, except that the solvent pyridine was replaced by toluene and the reflux was conducted for 4.5 hours, to obtain 1-methyl-5-phenyl- 7-chloro-1,3-dihydro-2H-1,4-benzodiazepin-2-one having a melting point of 127° to 130° C.

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The Regents of the University of Michigan

Patent: US4034087 A1, 1977 ; Title/Abstract Full Text Show Details

14. and at least one number selected from the group consisting of ... Phenacemide Dipyridamol Indomethacin Nicotinamide Diazepam Disodium chromoglycate Levamisole Aldosterone ...

13


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Rx-ID: 2889657 Find similar reactions

T=130°C; 0.5 h; Mechanism;

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Pinto; Fryer

Journal of Heterocyclic Chemistry, 1993 , vol. 30, # 4 p. 939 - 943 Title/Abstract Full Text View citing articles Show Details

A

B

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14

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Rx-ID: 2889658 Find similar reactions

A: 39% B: 38%

T=130°C; 0.5 h;

Pinto; Fryer

Journal of Heterocyclic Chemistry, 1993 , vol. 30, # 4 p. 939 - 943 Title/Abstract Full Text View citing articles Show Details

15

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With sodium hydrogensulfite in ethanol; water

12 h; Heating;

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Rx-ID: 2097663 Find similar reactions

Gates, Marshall

Journal of Organic Chemistry, 1980 , vol. 45, # 9 p. 1675 - 1681 Title/Abstract Full Text View citing articles Show Details

A

B

C


16

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A

B

C

D

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B

C

D

A: 5% C: 21%

With sulfuric acid in methanol

3.25 h; Heating; Yield given;

Gates, Marshall

Journal of Organic Chemistry, 1980 , vol. 45, # 9 p. 1675 - 1681 Title/Abstract Full Text View citing articles Show Details

A: 5%

With sulfuric acid in methanol

3.25 h; Heating; Yields of byproduct given;

Gates, Marshall

Journal of Organic Chemistry, 1980 , vol. 45, # 9 p. 1675 - 1681 Title/Abstract Full Text View citing articles Show Details

17

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A: 5.1% B: 0.5% C: 41.7% D: 0.6%

With potassium permanganate in water

T=15°C; 1.16667 h;

Milkowski; Hueschens; Kuchenbecker

Journal of Heterocyclic Chemistry, 1980 , vol. 17, # 2 p. 373 - 376 Title/Abstract Full Text View citing articles Show Details

A: 5.1% B: 0.5% C: 41.7% D: 0.6%

With potassium permanganate in water

T=15°C; 1.16667 h;

Milkowski; Hueschens; Kuchenbecker

Journal of Heterocyclic Chemistry, 1980 , vol. 17, # 2 p. 373 - 376 Title/Abstract Full Text View citing articles Show Details

A

18


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A

B

C

D

E

F

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C

D

A: 13.1% B: 2.7% C: 1.3% D: 21.8%

With chromium(VI) oxide in pyridine

93 h;

Milkowski; Hueschens; Kuchenbecker

Journal of Heterocyclic Chemistry, 1980 , vol. 17, # 2 p. 373 - 376 Title/Abstract Full Text View citing articles Show Details

A: 13.1% B: 2.7% C: 1.3% D: 21.8%

With chromium(VI) oxide in pyridine

93 h;

Milkowski; Hueschens; Kuchenbecker

Journal of Heterocyclic Chemistry, 1980 , vol. 17, # 2 p. 373 - 376 Title/Abstract Full Text View citing articles Show Details

A: 13.1% B: 2.7% C: 1.3% D: 21.8%

With chromium(VI) oxide in pyridine

93 h;

Milkowski; Hueschens; Kuchenbecker

Journal of Heterocyclic Chemistry, 1980 , vol. 17, # 2 p. 373 - 376 Title/Abstract Full Text View citing articles Show Details

19

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F: 65%

With ammonia in ethanol

T=80°C; 2 h; further reagent; Mechanism;

Clarke, George M.; Lee, J. Barry; Swinbourne, Frederick J.; Williamson, Basil

Journal of Chemical Research, Miniprint, 1980 , # 12 p. 4745 - 4761 Title/Abstract Full Text Show Details

A

20

B


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D: 65%

With ammonia in ethanol

T=80°C; 2 h; Further byproducts given;

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Clarke, George M.; Lee, J. Barry; Swinbourne, Frederick J.; Williamson, Basil

Journal of Chemical Research, Miniprint, 1980 , # 12 p. 4745 - 4761 Title/Abstract Full Text Show Details

21

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With 1,3,5,7-tetraazatricyclo[5.1.1.13,5]decane; ammonia; nitric acid in methanol; water; toluene

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Hoffmann-La Roche Inc.

Patent: US3996209 A1, 1976 ; Title/Abstract Full Text Show Details

9:EXAMPLE 9

EXAMPLE 9 A mixture of hexamethylenetetramine (17.5 g., 0.125 mol), methanol (135.5 ml) and 2(2-chloro-N-methylacetamido)-5-chlorobenzophenone (80.5 g., 0.25 mol) was saturated with ammonia. Heat the stirred mixture slowly to reflux with a steady stream of ammonia flowing through the mixture. During the course of the reaction STR5 was prepared. The product was not isolated. Hold at reflux for 6 hours. Stop the flow of ammonia and remove the solvent under vacuum. Take up the residue in a mixture of toluene (500 ml.) and hot water (500 ml). Separate the toluene phase and add to it, with stirring, 3N nitric acid (169 ml). The crystals which separate are filtered, wash with toluene (50 mls) and resuspended in a mixture of toluene (250 ml) and water (250 ml). Concentrated ammonia (30 ml) is added to pH 8. The toluene phase is separated, washed with water (250 ml) and then distilled to dryness in vacuo yielding 96.09percent of 7-chloro-1-methyl-1,3-dihydro-5-phenyl-2H-1,4-benzodiazepin-2-one, melting point 125° to 127° C. 90%

With 1,3,5,7-tetraazatricyclo[5.1.1.13,5]decane; [HHMTA]Cl in ethanol

Heating;

Clarke, George M.; Lee, J. Barry; Swinbourne, Frederick J.; Williamson, Basil

Journal of Chemical Research, Miniprint, 1980 , # 12 p. 4777 - 4793 Title/Abstract Full Text Show Details

With 1,3,5,7-tetraazatricyclo[5.1.1.13,5]decane in ethanol; toluene

Hoffmann-La Roche Inc.

Patent: US3996209 A1, 1976 ;

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Title/Abstract Full Text Show Details

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10:EXAMPLE 10

EXAMPLE 10 A mixture of ethanol (600 ml) and hexamethylenetetramine (39.1 g., 0.279 mol) was stirred and saturated with ammonia. With ammonia bubbling into the mixture it was slowly heated to reflux. Over a period of 41/2 hours, 2-(2-chloro-N-methylacetamido)-5-chlorobenzophenone (40 g., 0.124 mol) was added in increments yielding STR6 which was not isolated. Refluxing was continued for 2 hours longer. The reaction mixture was then distilled to dryness in vacuo at 50° C. The residue was stirred with toluene (250 ml), heated to reflux and heated with two increments of para-toluene sulfonic acid. Reflux was continued for one hour. After cooling to 70° C., the toluene was washed with hot water to remove soluble salts and distilled to dryness in vacuo. The residue was dissolved in hot ethanol (111 mol) and the solution cooled at -10° C. for one hour. The crystalline 7-chloro-1,3-dihydro-1-methyl-5-phenyl-2H-1,4-benzodiazepin-2-one obtained was isolated and weighed 29 g., melting point 129° to 131° C. Concentration of the mother liquor by ca. 50percent gave a second crop weighing 2.0 g. melting at 127° C.

22

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Rx-ID: 18048009 Find similar reactions

Multi-step reaction with 2 steps 1: 92 percent / aq.NaHCO3 / toluene / 2 h / 40 °C 2: 65 percent / NH3 / ethanol / 2 h / 80 °C View Scheme

Clarke, George M.; Lee, J. Barry; Swinbourne, Frederick J.; Williamson, Basil

Journal of Chemical Research, Miniprint, 1980 , # 12 p. 4745 - 4761 Title/Abstract Full Text Show Details

Multi-step reaction with 3 steps 1: 1.45 g / CH2Cl2 / Ambient temperature 2: 82.2 percent / NH2OH*HCl / pyridine / 45 h / 70 °C 3: 89.3 percent / NaHSO3 / ethanol; H2O / 12 h / Heating View Scheme

Gates, Marshall

Journal of Organic Chemistry, 1980 , vol. 45, # 9 p. 1675 - 1681 Title/Abstract Full Text View citing articles Show Details

23

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Multi-step reaction with 2 steps 1: 82.2 percent / NH2OH*HCl / pyridine / 45 h / 70 °C 2: 89.3 percent / NaHSO3 / ethanol; H2O / 12 h / Heating View Scheme

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Rx-ID: 21245679 Find similar reactions

Gates, Marshall

Journal of Organic Chemistry, 1980 , vol. 45, # 9 p. 1675 - 1681 Title/Abstract Full Text View citing articles Show Details


24

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With sodium hydroxide; dimethyl sulfate in dichloromethane; water

Schering Corporation

Patent: US4155904 A1, 1979 ;

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4:7-Chloro-1,3-dihydro-1-methyl-5-phenyl-2H-1,4-benzodiazepin-2-one

EXAMPLE 4 7-Chloro-1,3-dihydro-1-methyl-5-phenyl-2H-1,4-benzodiazepin-2-one Dissolve 5.4 g. (0.02 moles) of 7-chloro-1,3-dihydro-5-phenyl-2H-1,4-benzodiazepin-2-one (e.g. product of Example 3) in 35 ml. of dichloromethane and add to this solution 1.2 g. of NaOH (1.5 moles) dissolved in 17 ml. of water. Cool the mixture with good agitation to 0° C. and add slowly 3.8 g. (0.03 moles) of dimethyl sulfate with good cooling and stirring. After all the dimethyl sulfate is added remove the cooling bath and continue stirring for an additional 2 hours. Add water and methylene chloride to the reaction mixture. Separate the layers and wash the methylene chloride layers with water. Dry the organic solution over anhydrous sodium sulfate and evaporate. After recrystallization, 7-chloro-1,3-dihydro-1-methyl-5-phenyl-2H-1,4-benzodiazepin-2-one is obtained which after drying under vacuum at 110° C. shows a melting point of 129.5°-130.5° (corr.) and no depression on mixed melt with an authentic sample.

25

Synthesize Find similar With tetrabutylammonium fluoride; 1,3,5,7tetra-azatricyclo[5.1.1.13,5]decane in aqueous isopropyl alcohol

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Schering Corporation

Patent: US4155904 A1, 1979 ; Title/Abstract Full Text Show Details

2:7-Chloro-1,3-dihydro-1-methyl-5-phenyl-2H-1,4-benzodiazepin-2-one

EXAMPLE 2 7-Chloro-1,3-dihydro-1-methyl-5-phenyl-2H-1,4-benzodiazepin-2-one Reflux 1.8 g. (0.005 moles) of 2-(2-bromo-N-methylacetamido)-5-chlorobenzophenone, 2.8 g. (0.020 moles) of hexamethylenetetramine and 1.96 g. (0.020 moles) of ammonium bromide together for 2 hours in 14 ml. of 85percent (v/v) aqueous isopropyl alcohol. Pour the reaction mixture into water and extract the product with benzene. Wash the benzene solution with water, dry over anhydrous sodium sulfate, filter and evaporate to dryness. After recrystallization, 7-chloro-1,3-dihydro-1-methyl-5-phenyl-2H-1,4-benzodiazepin-2-one is obtained. The material gives a single spot by thin layer chromatography, and after drying under vacuum at 110° C., shows no depression on mixed melting point with an authentic sample (M.P. 129.5°-130.5° C.).


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