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Pharmaceutical Substances Syntheses, Patents, Applications - Part 41 ppt

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anhydrous crystal modification: DOS 3 313 818 Hoechst; appl.. COOH O tetrozole-1- sparonic acid cf... cefotoxime synthesis ethyl 2-2-chloroocet- omido-4-thiozolyl-2- methoxyiminoocet

Trang 1

Ceftazidime C 401

0 0 NoN02, CH3COOH 0 0 S02C12, CH2CI2 0 0

H3C I V 1 0 ^ C H 3 H 3 c V O ^ C H 3 - c'+O^CH,

ethyl acetoocetote ethyl 2-hydroxy- ethyl 4-chloro-2-

irninoocetoocetote hydroxyirnino-

ocetoacetote (I)

thioureo

H2NL -N 0 '+0^CH3

N ' ~ H

ethyl (Z)-2-(2-amino- thiazol-4-yl)-2-hydroxy- irninoacetote

11 trityl chloride

ethyl (2)-2-hydroxyimino- tert-butyl

2-(2-tritylorninothiozol-4- 2-bromo-2-

y1)acetate (II) methyl-

propionate

1 CH,OH NoOH

2 HCI

ethyl (2)-2-(1 -tert-butoxy- corbonyl- 1 -methylethoxyimino)- 2-(2-tritylominothiozol-4- yl)ocetote (111)

(Z)-2-(1 -tert-butaxycarbanyl-

1 -rnethylethoxyimino)-2-

(2-tritylaminothiozol-4-yl)-

Trang 2

402 C Ceftazidime

cefoloridine

(4 v.)

7(R)-ornino-3-(1- pyridiniomethy1)-3- cephem-4-carboxylic acid chloride monohydrochloride (V)

Reference (s):

DOS 2 921 3 16 (Glaxo; appl 25.5.1979; GB-prior 26.5.1978)

US 4 258 041 (Glaxo; 24.3.1981; GB-prior 26.5.1978)

GB 2 025 398 (Glaxo; appl 25.5.1979; GB-prior 26.5.1978)

US 4 525 587 (Eli Lilly; 25.6.1985; prior 27.12.1982, 3.2.1984)

intertnediate IV:

US 4 497 956 (Glaxo; 5.2.1985; GB-prior 13.11.1981)

acid chloride of IV:

EP 101 148 (Glaxo; appl 28.4.1983; GB-prior 29.4.1982)

intermediate V:

EP 135 258 (Eli Lilly; appl 18.6.1984; USA-prior 20.6.1983)

EP 70 706 (Glaxo; appl 16.7.1982; GB-prior 17.7.1981)

salts and crystal modiJications:

crystalline dihydrochloride:

US 4 467 086 (Glaxo; 21.8.1984; GB-prior 2.10.1979)

Trang 3

Ceftezole C 403

pentahydrate:

DOS 3 037 102 (Glaxo; appl 1.10.1980; GB-prior 2.10.1979)

GB 2 063 871 (Glaxo; appl 1.10.1980; GB-prior 2.10.1979)

US 4 329 453 (Glaxo; 1 1.5.1982; appl 9.9.1980; GB-prior 2.10.1979)

sesquihydrate:

DOS 3 313 816 (Hoechst; appl 16.4.1983)

EP 122 584 (Hoechst; appl 10.4.1984; D-prior 16.4.1983)

anhydrous crystal modification:

DOS 3 313 818 (Hoechst; appl 16.4.1983)

EP 122 585 (Hoechst; appl 10.4.1984; D-prior 16.4.1983)

pharmaceutical formulations:

DOS 3 332 616 (Glaxo; appl 9.9.1983; GB-prior 10.9.1982)

Formulation(s): vial 250 mg, 500 mg, 1 g, 2 g, 3 g

Trade Name(s):

F: Fortum (Glaxo Wellcome) Glazidim (Glaxo) USA: Ceptaz (Glaxo)

Use: antibiotic RN: 26973-24-0 MF: C,,H,,N,O,S, MW: 440.49

CN: (6R-trans)-8-0x0-7-[(I H-tetrazol- 1 -ylacetyl)amino]-3-[(1,3,4-thiadiazol-2-ylthio)methyl]-5-thia- 1

azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid

3

COOH O

tetrozole-1- sparonic acid (cf cefazolin) (I)

acetic acid

1 -3.4-thiodiazole

Reference(s):

DE 1 770 168 (Fujisawa; appl 10.4.1968; J-prior 15.4.1967, 23.10.1967, 28.10.1967)

US 3 516 997 (Fujisawa; 23.6.1970; J-prior 15.4.1967, 24.10.1967, 28.10.1967)

GB 1 206 305 (Fujisawa; appl 11.4.1968; J-prior 15.4.1967, 24.10.1967, 28.10.1967)

combination with penicillins:

DOS 2 508 443 (~ujisawa; appl 27.2.1975; J-prior 28.2.1974, 27.3.1974)

Trang 4

404 C Ceftizoxime

Trade Name(s):

Use: p-lactam antibiotic (cefalosporin derivative)

RN: 68401-81-0 MF: C13H13N,0,S2 MW: 383.41

CN: [6R-[6a,7~(Z)]]-7-[[(2-amino-4-thiazolyl)(methoxyimino)acetyl]a~in]-8-o~~-5-thia-l- azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid

monohydrochloride

RN: 68401-80-9 MF: C13H13NS05S2 HC1 MW: 419.87

monosodium salt

RN: 68401-82-1 MF: Cl,HI,N,NaO,S, MW: 405.39

LD,,,: 5150 m g k g (M, i.v.); > I 0 g/kg (M, p.0.);

5570 mglkg (R, i.v.); >lO glkg (R, p.0.)

4-nitrobenzyl 3-hydroxy-7(R)-

phenylocetomido-3-cephem-4-

corboxylate

(cf cefoclor synthesis)

4-nitrobenzyl 3-h~droxy-7(R)- phenylocetornidocephom-4- corboxylote (1)

4-nitrobenzyl 7 ( ~ ) - ~ h e n ~ l

ocetornido-3-cephem-4-

corboxylate (11)

Trang 5

Ceftriaxone C 405

?

1 N-(trimethylsilyl)ocetomide

2 2-(2-formamido-4-thiozolyl)-2-

methoxyiminoacetic acid

Reference(s):

US 4 427 674 (Fujisawa; 24.1.1984; GB-prior 14.3.1977, 12.7.1977, 11.10.1977, 3.1.1978)

US 4 463 002 (Fujisawa; 3 1.7.1984; J-prior 21.5.198 I)

Formula~ion(s): vial 0.25 g, 0.5 g, 1 g, 2 g (as sodium salt)

Trade Name(s):

D: Ceftix (Roche; 1983) GB: Cefizox (Wellcome); wfm J: Epocelin (Fujisawa)

F: Cefizox (Bellon) I: Eposerin (Farmitalia) USA: Cefizox (Fujisawa; 1983)

Use: P-lactam antibiotic (cefalosporin derivative)

RN: 73384-59-5 MF: CI8HI8N8O7S3 MW: 554.59 EINECS: 277-405-6

CN: [6R-[6a,7~(Z)J]-7-[[(2-amino-4-thiazolyl)(methoxyimino)acetyl]amino]-X-oxo-3-[[(1,2,5,6-tetrahydro-2- methyl-5,6-dioxo-1,2,4-triazin-3-yl)thio]methyl]-5-thia-l-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid

disodium salt

RN: 74578-69-1 MF: C18H,6N,Na,07S3 MW: 598.55 EINECS: 277-930-0

LD,: 2200 mgkg (M, i.v.); >10 glkg (M, p.0.);

1900 m g k g (R, i.v.); > I 0 g k g (R, p.0.)

d' "' N.N-dimethyl- '-y"O"CH3

ocetomide

ethyl 2-(2-omino- chloro-

4-thiozalyl)-2-(meth- ocetyl

oxyimino)ocetate chloride

(cf cefotoxime

synthesis)

ethyl 2-(2-chloroocet- omido-4-thiozolyl)-2- methoxyiminoocetote (I)

Trang 6

406 C Ceftriaxone

KOH, H20 ''>NH CH2CIp N(C&,)3,

I -+ s+coo~

s+cl

N \ O / C H 3

2-(2-chloroocetomido- 4-thiozoly1)-2-methoxy- iminoocetyl chloride (11)

H3C\N/NH2 NoOCH,, CH,OH H3C\N/NH2 H + K S C N + s A N H ~ - dimethyl oxolate

methyl- potassium N-omino-

hydrozine rhodanide N-melhyl-

thiourea

7-orninocephalo-

sporonic ocid

7(R)-omino-3-[[(2,5-dihydro- 6-hydroxy-2-methyl-50x0-

1,2,4-triazin-3-yl)thio]methyl]-

3-cephem-4-corboxylic acid (N)

I , NoHC03

HZN NH,

2 HCOOH

Ceftrioxone

Reference(s):

DOS 2 922 036 (Roche; appl 30.5.1979; CH-prior 30.5.1978, 8.3.1979)

US 4 327 210 (Roche; 27.4.1 982; appl 24.1 1 l978; CH-prior 30.5.1978)

alternative synthesis,from cefotaxime and 2,5-dihydro-6-hydroxy-2-methyl-3-mercapto-5-oxo-l,2,4-triazine:

US 4 431 804 (Roche; 14.2.1984; CH-prior 17.2.1981)

Formulation(s): inj powder 250 m g , 1 g, 2 g

Trade Name(s):

D: Rocephin (Roche; 1983) F: RocCphine (Roche) GB: Rocephin (Roche)

Trang 7

Cefuroxime C 407

[ I: Rocefin (Roche) USA: Rocefin (Roche Labs.;

Use: antibiotic

RN: 55268-75-2 MF: C,6H16N408S M W : 424.39 EINECS: 259-560-1

LD,,: 10.4 g k g (M, i.v.); >10 g k g (M, p.0.);

>8 g/kg (R, i.v.); 10 glkg (R, p.0.)

CN: [6R-[6a,7~(Z)]]-3-[[(aminocarbonyl)oxy]methyl]-7-[[2-furanyl(methoxyimino)acetyl]amino]-8-oxo-5- thia-l-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid

sodium salt

RN: 56238-63-2 MF: C,,H15N4Na0,S M W : 446.37

q C H 3

NaNOZ, conc HCI

0-methylhyd;oxyl- , q c o o H

r\

2 diphenylmethyl 7-amino-

cephalosporanate

1 HZO, OH- or esterases

2 CIS0,-NCO, acetonitrile

3 H,O

4 F3CCOOH, anisole

n

2 chlorosulfonyl isocyanate

V

omine hydrochloride 2-fury-

glyoxylic ocid

I Cefuroxime

syn-2-methoxy- imino-2-(2-furyl)- acetic ocid (I)

1 PCI5 CH2C12 N,N-dimethyiacetamide

2

3 HCI

2 7-amino-3-aminocarbonyloxymethyl-

Trang 8

408 C Cefuroxime

Reference(s):

GB 1 453 049 (Glaxo; appl 21.8.1973; valid from 13.8.1974)

DAS 2 439 880 (Glaxo; appl 20.8.1974; GB-prior 21.8.1973)

DOS 2 462 376 (Glaxo; appl 20.8.1974; GB-prior 21.8.1973)

DOS 2 204 060 (Glaxo; appl 28.1.1972; GB-prior 29.1.1971, 1.10.1971 and 14.1.1972)

DOS 2 223 375 (Glaxo; appl 12.5.1972; GB-prior 14.5.1971 and 1 lO.l97 1)

DOS 2 265 234 (Glaxo; appl 12.5.1972; GB-prior 14.5.1971 and 1.10.1971)

US 3 966 717 (Glaxo; 29.6.1976; GB-prior 14.5.1971, 1.10.1971, 21.8.1973)

DOS 2 439 880 (Glaxo; appl 20.8.1974; GB-prior 21.8.1973)

US 3 971 778 (Glaxo; 27.7.1976; GB-prior 25.10.1972)

US 3 974 153 (Glaxo; 10.8.1976; GB-prior 14.5.1971, 1 lO.l97l, 21.8.1973)

cryslalline sodium salt:

DOS 2 901 730 (Glaxo; appl 17.1 l979; GB-prior 17.1 l978)

syn-2-methoxyimino-2-(2-fury1)acetic acid, resp -acetyl chloride:

US 4 017 515 (Glaxo; 12.4.1977; GB-prior 14.5.1971, 1.10.1971, 12.5.1972 and 25.10.1972)

2-furylglyoxylic acid:

GB I 503 649 (Glaxo; appl 28.6.1974; valid from 27.6.1975)

US 4 013 680 (Glaxo; 22.3.1977; prior 18.6.1975)

L-lysine salt of cefuroxime:

US 4 128 715 (Glaxo; 5.12.1978; GB-prior 28.4.1976)

DOS 2 718 730 (Glaxo; appl 27.4.1977; GB-prior 28.4.1976)

DE 1 545 915 (Glaxo; appl 29.10.1965; GB-prior 30.10.1964,27.1.1965, 19.10.1965)

DOS 2 745 219 (Glaxo; appl 7.10.1977; GB-prior 8.10.1976)

DAS 1 795 777 (Glaxo; appl 29.10.1965; GB-prior 30.10.1964, 27.1.1965, 19.10.1965)

GB 1 474 519 (Glaxo; appl 14.5.1973; valid from 6.5.1974)

hydroxyntethyl-derivatives (enzymatic with 0-transcarbantoylase):

US 4 075 061 (Glaxo; 21.2.1978; GB-prior 19.2.1976)

US 4 164 447 (Glaxo; 14.8.1979; GB-prior 19.2.1976)

US 4 164 447 (Glaxo; 14.8.1979; GB-prior 19.2.1976)

(also reaction of the hydroxymethyl-compd with chlorosulfonyl isocyanate corresponding at the cefoxitin- synthesis, q v.)

tabl 125 mg, 250 mg, 500 mg

Trade Nante(s):

D: Elobact (Glaxo Wellcome1

Cascan)

Zinacef (Glaxo Wellcome;

Hoechst; 1977)

Zinnat (Glaxo Wellcome)

F: Cepazine (Sanofi

Winthrop)

Zinnat (Glaxo Wellcome)

GB: Zinacef (Glaxo Wellcome)

I: Biociclin (Delsaz &

Filippini)

Biofurex (KBR)

Bioxima (Kemyos)

Cefamar (Firma) Cefoprim (Esseti) Cefumax (Locatelli) Cefur (Eurofarmaco) Cefurex (Salus Research) Cefurin (Magis)

Coliofossim (Coli) Curoxim (Glaxo) Deltacef (Pulitzer) Duxima (Ecobi) Gibicef (Metapharma) Ipacef (IPA)

Itorex (Biotekfarma)

Kefox (CT) Kesint (Mendelejeff) Lafurex (Lafare) Lamposporin (Leben's) Medoxim (Medici) Polixima (Sifarma) Supero (Francia Farm.) J: Oracef (Shin Nihon-Glaxo) USA: Kefurox (Glaxo Wellcome; 1986)

Zinacef (Glaxo Wellcome; 1983)

Trang 9

Celecoxib C 409

Celecoxib

(SC-58635; YM- 177)

ATC: MOl AH01 Use: anti-inflammatory, cyclooxygenase-2 inhibitor

RN: 169590-42-5 MF: C,,H,,F,N,O,S MW: 381.38

CN: 4-[5-(4-Methylpheny1)-3-(trifluoromethy1)-1 H-pyrazol-1-y l]benzenesulfonamide

I

CH3 ethyl trifluoroocetate

4'-methylaceto-

phenone

4,4,4-trifluoro- 1 -

(4-rnethylpheny1)- butane-1,s-diane (I)

Celecoxib

I

WO 9 515 316 (Searle & Co.; appl 14.11.1994; USA-prior 30.1 1.1993,6.4.1994)

WO 9 637 476 (Searle & Co.; appl 23.5.1996; USA-prior 25.5.1995)

US 5 892 053 (Searle & Co.; 6.4.1999; USA-prior 25.5.1995)

Penning, T.D eta].: J Med Chem (JMCMAR) 40 (9), 1347 (1997)

De Vleeschauwer, M.; Gauthier, J.Y.: Synlett (SYNLES) 1997 (4), 375

Formulation(s): cps 100 mg, 200 mg

Trade Name(s):

USA: Celebrex (Pfizer; Searle;

1999)

Celiprolol

(ST- 1396)

ATC: C07AB08 Use: cardioselective 0-receptor antagonist *

RN: 56980-93-9 MF: C2,H3,N,O4 MW: 379.50 EINECS: 260-497-7

CN: h~-[3-acetyl-4-[3-[(1,1-dimethylethyl)amino]-2-hydroxypropoxy]phenyl]-N,N-diethylurea

monohydrochloride

RN: 57470-78-7 MF: C2,H,,N3O4 HC1 MW: 415.96 EINECS: 260-752-2

LD,,: 42.3 mglkg (M, i.v.); 1362 mg/kg (M, p.0.);

68.3 mglkg (R, i.v.); 2157 m g k g (R, p.0.)

Trang 10

4 1 0 C Cerivastatin sodium

0

H 3 C H D N H , 0 +

hydroxyoniline chloride 4-hydroxypheny1)ureo (I)

0

l 4 ~ NoOH 1

2 (H,C),C-NH,

1 epichlorohydrin

2 tert-butylamine

Celiprolol

DOS 2 458 624 (Lentia; appl 11.12.1974; A-prior 20.12.1973, 19.1 1.1974, 20.1 l.l974,25.ll.l974)

US 4 034 009 (Chemie Linz 5.7.1977; appl 17.12.1974; A-prior 20.12.1973)

purification:

EP 229 947 (Lentia; appl 2.12.1986; D-prior 13.12.1985)

synthesis of enantiomers:

EP 135 162 (Chemie Linz; appl 17.8.1984; D-prior 19.8.1983)

EP 155 518 (ChemieLinz; appl 20.2.1985; D-prior 21.3.1984)

ophthalmic formulation:

EP 366 765 (Alcon; appl 26.4.1989; USA-prior 26.4.1988)

EP 109 561 (Rorer; appl 20.10.1983; USA-prior 27.10.1982)

sustained release formulation:

EP 285 871 (Lentia; appl 16.3.1988; D-prior 10.4.1987)

EP 268 8 13 (Lentia; appl 16.10.1987; D-prior 24.10.1986)

Formulation(s): f c tabl 100 mg, 200 mg (as hydrochloride)

Trade Namefs):

D: Celipro Lich (Lichtenstein) F: CClectol (Bellon)

Select01 (Pharmacia & GB: Celectol (Rh6ne-Poulenc

Cerivastatin sodium

(Avastatin; Bay-W-6228; Rivastatin)

Use: hyperlipidemic, HMG-CoA- reductase inhibitor, antihypercholesterolemic agent RN: 143201 -1 1-0 MF: C,,H,,FNNaO, MW: 481.54

CN: [S-[R*,S*-(E)J]-7-[4-(4-fluorophenyl)-5-(methoxymethyl)-2,6-bis(l-methylethyl)-3-pyridinyl]-3,5-

dihydroxy-6-heptenoic acid monosodium salt

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