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Pharmaceutical Substances Syntheses, Patents, Applications - Part 134 pps

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Midodrine M 1331 Reference(s): DE 2 004 686 (Meiji; prior. 3.2.1970). US 3 761 588 (Meiji; 25.9.1973; J-prior. 25.9.1969). DOS 2 835 547 (Meiji; appl. 14.8.1978; J-prior. 15.8.1977). DOS 2 537 375 (Meiji; appl. 22.8.1975; J-prior. 27.8.1974). US 4 017 607 (Meiji; 12.4.1977; J-prior. 27.8.1974). US 4 188 480 (Meiji; 12.2.1980; J-prior. 15.8.1977). Omoto, S. et al.: J. Antibiot. (JANTAJ) 24, 536 (1976). Nakamura, K. et al.: Chem. Lett. (CMLTAG) 1978, 1293. Formulation(s): tabl. 400 mg Trade Name(s): F: Mosil (Menarini) Miocamen (Menarini; J: Miocamycin (Meiji Seika; I: Macroral (Malesci; 1985) 1985) 1985) Miokacin (Firma; 1986) Midodrine ATC: ~01~~17 Use: antihypotensive, a-adrenergic, vasoconstrictor RN: 97476-58-9 MF: CI2Hl8N2O4 MW: 254.29 CN: (+)-2-amino-N-[2-(2,5-dimethoxyphenyl)-2-hydroxyethyl]acetamide monohydrochloride RN: 3092-17-9 MF: C,2Hl,N,04. HCl MW: 290.75 LD,,: 56.2 mglkg (M, i.v.); 246 mgkg (M, p.0.); 18.2 mglkg (R, i.v.); 68.8 mglkg (R, p.0.); 150 mglkg (dog, p.0.) 2-omino-2',5'-di- chloroacetyl methoxyacetophenone chloride FH3 NaBH,, Pd-C b sodium borohydride Reference (s): DAS 2 523 735 (Lentia; appl. 28.5.1975; A-prior. 24.7.1974). 7% t- OH (1) alternative syntheses: Midodrine AT 241 435 i~sterr. Stickstoffwerke Linz; appl. 11.6.1963; valid from 15.12.1964). DOS 2 506 110 (Lentia; appl. 13.2.1975). BE 838 512 (Chemie Linz AG; appl. 12.8.1976; D-prior. 13.2.1975). 1332 M Midoriamin Formulation(s): amp. 5 mg; drops 10 mgtml; tabl. 2.5 mg, 5 mg (as hydrochloride) Trade Nume(s): D: Gutron (Nycomed) I: Gutron (Guidotti) USA: ProAmatine (Roberts) F: Gutron (Nycomed SA) J: Metligine (Taisho) Midoriamin (Thiamine cobaltichlorophylline complex) ATC: A02B Use: ulcer therapeutic RN: 8721 1-44-7 MF: C4,HS3CoN,O,S MW, 952.98 LD,,: 209 mglkg (M, i.p.); 3066 mg/kg (M, p.0.); 406 rnglkg (M, s.c.); 82 mgkg (R, i.p.); 3590 mglkg (R, p.0.); 201 mglkg (R, s.c.) CN: [OC-6-24-(2S-tra1~s)]-[N-[(4-amino-2-methyl-5-pynmidinyl)methyl]-N-(4-hydroxy-2-mercapto-l- methyl-l-butenyl)formamide]aqua[18-carboxy-20-(carboxymethyl)-8-ethenyl-l3-ethyl-2,3-dihydro- 3,7,1 2,17-tetramethyl-21H,23H-porphine-2-propan0at0(5-)-fl',fl2,~3,~]dihy&0genc0ba1tate(2-) @% H3C H2N 3. silica gel or gel permeation chrornatogrophy -N_ ''I / CH~ 7. Co(11) acetate ~3~'"' COOH 2. thiamine COOH COOH chlorine eg I Midoriamin Mifevristone M 1333 Reference(s): JP 1 052 779 (Green Cross; appl. 15.7.1988). JP 63 264 483 (Green Cross; appl. 11.3.1988). JP 63 264 420 (Green Cross; appl. 11.3.1988). JP 57 062 281 (Green Cross; Nisshin Flour Mill; appl. 1.10.1980). JP 58 041 885 (Green Cross, Nisshin Flour Mill; appl. 1.4.1982). medical use for treatment of gastritis: JP 2 149 522 (Green Cross; appl. 30.1 1.1988). Fonizulation(s): tabl. 5 mg Trade Name(s): J: Midoriamin (Green Cross; Nisshin Flour; 1988) Mifepristone ATC: G03A; G03D; GO~XBO~ (RU-486) Use: abortifacient, orally active progesterone and glucocorticoid receptor antagonist, contraceptive RN: 84371-65-3 MF: C,,H35N0, MW: 429.60 CN: (1 1 P, 17P)- 11-[4-(dimethylamino)phenyl]-l7-hydroxy-17-(l-propynyl)estra-4,9-dien-3-one estro-4.9-diene- ethylene I -propynylmognesium bromide FH3 I1 + N H3c' OLMqBr 4-dimethylaminophenyl- magnesium bromide dien-17-one (I) 7'43 1 Mifepristane 1334 M Miglitol Referencefs): EP 57 1 15 (Roussel-Uclaf; appl. 8.1.1982; F-prior. 9.1.1981). US 4 386 085 (Roussel-Uclaf; 3 1.5.1983; appl. 10.6.1982; F-prior. 9.1.1981). US 4 447 424 (Roussel-Uclaf; 8.5.1984; appl. 10.6.1982; F-prior. 9.1.1981). US 4 5 19 946 (Roussel-Uclaf; 28.5.1985; appl. 25.5.1984; prior. 9.1.1982, 10.6.1982,30.3.1984; F-prior. 9.1.1981). US 4 634 695 (Roussel-Uclaf; 6.1.1987; appl. 22.1.1985; prior. 9.1.1982, 25.5.1984, 10.6.1982, 30.3.1984; F-prior. 9.1.1981). synthesis of 3,3-(ethy1enedioxy)estra-5(10),9(11)-dien- 17-one: BE 651 813 (Merck & Co.; appl. 1964). alternative synthesis: FR 1 336 083 (Roussel-Uclaf; appl. 1962). NL 6 406 712 (Roussel-Uclaf; appl. 1964; F-prior. 1963). BE 651 812 (Merck & Co.; appl. 1964). Trade Namefs): F: Mifkgyne (Exelgyn) GB: Mifegyne (Exelgyn) Miglitol (Bay-m- 1099) ATC: AlOBF02 Use: antidiabetic, a-glucosidase inhibitor RN: 72432-03-2 MF: C,HI,NOs MW: 207.23 EINECS: 276-661-6 CN: [2R-(2a,3P,4a,5P)]-1-(2-Hydroxyethyl)-2-(hydroxymethyl)-3,4,5-piperidinetriol NH,, 2. enzymatic oxidation 3. deprotection with H+ CHO H2. Raney-Ni I * ethylene 0 H oxide (11) 0 H 6-deoxy-6- amino-L-sorbose (I) pi Miglitol Milnacipran hydrochloride M 1335 1. Gluconobocter oxydons. MgSO,, H,O -1 2. HZ, cat. Miglitol preparution of moranoline via N-formyl-6-amino-6-deoxy-L-sorbose: DE 3 61 1 841 (Bayer; appl. 9.4.1986; D-prior. 9.4.1986). a DE 2 758 025 (Bayer AG; 12.7.1979; appl. 24.12.1977; D-prior. 27.8.1977). EP49 858 (Bayer AG; appl. 7.10.1981; D-prior. 15.10.1981). JP 54 106 477 (Nippon Shinyaku; appl. 3.2.1978). b DE 3 024 901 (Bayer AG; appl. 1.7.1980). c EP 477 160 (Monsanto Co.; 25.3.1992; appl. 19.9.1991; USA-prior. 20.9.1990). Formulution(s): tabl. 25 mg, 50 mg, 100 mg Trude Numtfs): D: Diastabol (Sanofi- USA: Glyset (Pharmacia & Synthelabo; 1998) Upjohn; 1999) Milnacipran hydrochloride (Midalcipran hydrochloride) ATC: N06AX17 Use: antidepressant, 5-HT and norepinephrine reuptake-inhibitor RN: 101 152-94-7 MF: C,sH22N20 . HC1 MW: 282.82 CN: (+)-cis-2-(Aminomethyl)-N,N-diethyl- 1-phenylcyclopropanecarboxamide monohydrochloride (+)-cis-base RN: 92623-85-3 MF: C,,H2,N2O MW: 246.35 1336 M Milnacipran hydrochloride synthesis of intermediate I: 2-0x0-1 -phenyl-3- oxabicyclo[3.1 .O]hexone 1. 1 50°C, 45 min 1. NoNH2, benzene 2. distillotion 2. 0 or %cl 1. KOH 3. H+ LCN - 1. sodium omide OH 2. (?)-epichlorohydrin benzyl 2-(hydroxymethy1)- cyanide 2-phenylcyclo- propanecorboxylic acid ((f)-cis-trons- mixture) finalisation of Milnocipron hydrochloride 1. SOBr2. C2H50H 2. rCH3 tN 2. NH3 Et2O L~~3 3. NoOH, H20 %ooh 3. HC C2H50H . - 1. thionyl bromide 2. diethylamine (Il) h (+)-2-0x0- 1 - phenyl-3-0x0- bicyclo[3.1.0]- hexane (I) Milnocipran hydrochloride 1. SOCI,. CH2C12 AIC13, CH2C12 0 ~+n -, HO 1. thionyl chloride 2. phthalimide (+)-cis-2-hydraxy- potassium (111) methyl-N.N-diethyl 1 -phenylcyclopropone- corboxomide 1. N2H,, C2HSOH 2. HCI, C2HSOH A Milnocipron hydrochloride (N) 1. N2H4, C2H50H DMF 2. HCI. CPHSOH r +ru do Y Y - Milnacipran hydrochloride M 1337 (*)-cis- 1 -phenyl- 2-(brornornethy1)- cyclopropane- carboxylic acid hexa- rnethylene- tetrarnine 1. N2H,, C2H50H DMF 2. HCI, C2H50H Milnacipran V + IU + N - hydrochloride hydrochlaride synthesis of intertnediate I: Mouzi, G.; Cousse, H.; Bonnaud, B: Synthesis (SYNTBF) 1978 (4), 304. a EP 068 999 (Pierre Fabre S. A.; appl. 21.6.1982; F-prior. 23.6.1981). b EP 377 381 (Pierre Fabre S. A,; appl. 27.12.1987; F-prior. 28.12.1988). c EP 200 638 (Pierre Fabre S. A.; appl. 22.4.1986; F-prior. 25.4.1985). d FR 2 58 1 060 (Pierre Fabre Medicament; appl. 3 1.10.1986; F-prior. 25.4.1985). synthesis of I -aryl-2-(aminomethyl)cyclopropanecarboxylic acid derivatives: Bonnaud, B. et a].: J. Med. Chem. (JMCMAR) 30,318 (1987) alternative syntheses: Shuto, S. eta].: J. Org. Chem. (JOCEAH) 61,915 (1996) Shuto, S. et a].: J. Med. Chem. (JMCMAR) 38, 2964 (1995) prolonged-release pharmaceuticals containing milnacipran: WO 9 808 495 (Pierre Fabre S. A,; appl. 26.8.1997; F-prior. 28.8.1996) cotnpositions containing milnacipran and idazoxan: WO 9 735 574 (Pierre Fabre S. A.; appl. 25.3.1997; F-prior. 25.3.1996) Formulation(s): cps. 50 mg (as hydrochloride) Trade Name(s): F: Ixel (Pierre Fabre; 1997) 1338 M Milrinone Milrinone ATC: COlCE02 Use: cardiotonic, phosphodiesterase 111- inhibitor RN: 7841 5-72-2 MF: C,,HYN3O MW: 21 1.22 EINECS: 278-903-6 LDS,,: 79mgkg(M,i.v.); 137mgkg(M,p.o.); 73 mgkg (R, i.v.); 91 mgkg (R, p.0.) CN: 1,6-dihydro-2-methyl-6-oxo[3,4'-bipyridine]-5-carbonitrile lactate RN: 100286-97-3 MF: C1,HYN3O. xC3H,03 MW: unspecified 4-picoline ethyl ocetote 1 -(4-pyridyl)-2- proponone 4-dimethylomino-3-(4- 2-cyanoacetarnide pyridy1)-3-buten-Zone (I) dirnethylforrnarnide dimethyl acetal Milrinone DOS 3 044 568 (Sterling Drug; appl. 26.1 1.1980; USA-prior. 26.1 1.1979, 20.10.1980, 28.3.1980, 6.1 1.1980). US 4 312 875 (Sterling Drug; 26.1.1982; prior. 26.1 1.1979, 20.10.1980, 28.3.1980,6.11.1980). US 4 313 95 1 (Sterling Drug; 2.2.1982; prior. 26.1 1.1979, 20.10.1980,28.3.1980, 6.1 1.1980). Singh, B.: Heterocycles (HTCYAM) 23, 1479 '(1985). alternative synthesis: ES 544 504 (Inke; appl. 25.6.1985). DD 274 620 (Arzneimittelwerk Dresden; appl. 2.8.1988). DD 256 13 1 (Akademie der Wissenschaften; appl. 4.7.1986). sustained release pharmaceutical composition: EP 164 959 (Sterling Drug; appl. 30.5.1985; GB-prior. 4.6.1984, 30.5.1985). Formulation(s): amp. 10 mg1lO ml (as free base); USA: bag 100 ml, 200 ml (200 pglml); vial 10 ml, 20 ml (1 mglml) (as lactate) Trade Name(s): D: Corotrop (Sanofi Winthrop) F: Corotrope (Sanofi J: Milrila (Yamanouchi) Winthrop; as lactate) USA: Primcor (Sanofi) Miltefosine M 1339 Miltefosine (D 18506; Hexadecylphosphocholine) ATC: LOlXXO9 Use: antitumor (topical treatment) RN: LD,,: CN: (3 58066-85-6 MF: C,,H4,N04P MW: 407.58 246 mglkg (R, p.0); 680 mglkg (Mm, p.0); 603 mgkg (Mf, p.0). 2-[[(Hexadecyloxy)hydroxyphosphinyl]oxy]-N,N,N-trimethylethanaminium inner salt 1. POC13. THF, NEt3 2. 3. H20, HCOOH H3C-(CH2),5-0\ 9 H3C (CHz)15-OH P P 1. phosphoric trichloride HO/ \O-NH2 hexadeconol (1) 2. ethonolamine (11) 2-chloro- 1,3,2-dioxo- phospholone 2-oxide dimethyl sulfote 3. HpO H3C-(CH2)15-0\ /P I P Miltefosine 2. 2-bromoethonol HO/ \O/\/Br Miltetosine 1. POCI3. CHCI3, pyridine 3. H20 I Miltefosine 2. choline tosylate 1340 M Minaprine Reference (s): a Kaatze, U. et al.: Chem. Phys. Lipids (CPLIA4) 27 (3), 263-280 (1980). EP 225 608 (Max-Planck-Ges.; appl. 4.1 2.1986; D-prior. 4.12.1985). preparation of quuternized ethunamine phosphate estersfor oral or topical treulment of leishmaniasis: EP 534 445 (Max-Planck-Ges.; appl. 24.9.1992; D-prior. 27.9.1991). b Eibl, H.; Engel, J.: Prog. Exp. Tumor Res. (EXPTAR) 34, 1 (1992). Kamctani, F. et al.: Nippon Kagaku Kaishi (NKAKB8) 9, 1452-1458 (1984). c Nuhn, P. et al.: Pharmazie (PHARAT) 37 (lo), 706-708 (1982). d EP 521 297 (ASTA Medica; appl. 26.6.1992; D-prior. 4.7.1991). synergistic antitumor pharmuceuticals containing them and allylglycerins: AT 393 505 (Max-Planck-Gesellschaft; appl. 27.4.1987). Formulation(s): sol. 60 mg/ml(lO ml bottles) Trade Name(s): D: Miltex (ASTA Mcdica AWD) Minaprine ATC: N06AX07 Use: antidepressant RN: 25905-77-5 MF: Cl,H,2N40 MW: 298.39 EINECS: 247-329-8 CN: N-(4-methyl-6-phenyl-3-pyridazinyl)-4-morpholineethanamine dihydrochloride RN: 25953-17-7 MF: Cl,H22N,0 .2HCI MW: 37 1.3 1 LD,,,: 63 mgkg (M, i.p.) Cu, butanol,A + Reference (s): DOS 2 229 215 (CEPBEPE; appl. 15.6.1972; GB-prior. 18.6.1971). GB 1 345 880 (CEPBEPE; valid from 16.6.1972; prior. 18.6.1971). ZA 730 671 (CEPBEPE; appl. 3.1.1 973). medical use: US 4 169 158 (Laborit Henri; 25.9.1979, GB-prior. 18.6.1971). Formulation(s): drops 5 %; tabl. 50 mg, 100 mg (as dihydrochloride) Trade Name(s): F: Cantor (Clin-Comar-Byla; Cantor (Clin-Midy); wfm J: 1980); wfm I: Cantor (Midy; 1984) Alcas (Taisho) . [OC- 6-2 4-( 2S-tra1~s) ]-[ N-[(4-amino-2-methyl-5-pynmidinyl)methyl]-N-(4-hydroxy-2-mercapto-l- methyl-l-butenyl)formamide]aqua[18-carboxy-2 0-( carboxymethyl )-8 -ethenyl-l3-ethyl-2,3-dihydro- 3,7,1. 1 1-[ 4-( dimethylamino)phenyl]-l7-hydroxy-1 7-( l-propynyl)estra-4,9-dien-3-one estro-4.9-diene- ethylene I -propynylmognesium bromide FH3 I1 + N H3c' OLMqBr 4-dimethylaminophenyl- magnesium bromide dien-17-one. 1,6-dihydro-2-methyl-6-oxo[3,4'-bipyridine ]-5 -carbonitrile lactate RN: 10028 6-9 7-3 MF: C1,HYN3O. xC3H,03 MW: unspecified 4-picoline ethyl ocetote 1 -( 4-pyridyl )-2 - proponone 4-dimethylomino- 3-( 4- 2-cyanoacetarnide

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