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Pharmaceutical Substances Syntheses, Patents, Applications - Part 88 pptx

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HCL fluorobenzene 3-chloro-4-nitro- 3-chloro-4-nitro- benzoyl chloride 4'-fluorobenrophenone Refererlces: DOS 2 029 637 Janssen; appl.. 100 mg Flubendazole Trade Names: D: Flubenol

Trang 1

Fluazacort F 87 1

1 HBr, AcOH

2 BrZ CHCI,

:: :' Br2, diomne

e NYCHz 3 DMF LiBr Li2c03

b

H

O H

(3~.5a.5'p)-2l-acetoxy-3-

hydroxy-2'-methyl-5H-

pregn-9(11)-eno[l7,16-dl-

oxozol-20-one (N)

(5'8)-21 -ocetoxy-2'-methyl-

S'H-pregna-1.4,9(11)-trieno[l7,16-dl-

oxazole-$20-diane (VI)

1 H3C-CO-NU-Br, HCIO,

2 NoOH

3 H2FZ THF

1 N-bromoacetarnide

Fluazocort

L

1 Ac,O, pyridine I KOH

2 I, N C X C ~ ~ N , ~

H3C N H CN

3 H~C-COOH ! N ( c ~ H ~ ) ~

2 rnesyl chlorrde 2 iodine, ozoisobutyronitrile

3 triethylommon~um acetate

(5a,5'@)-3@,1 Ig-dihydroxy-

2'-methyl-SH-pregnano-

[17,16-d]oxozol-20-one

(cf Deflozacort)

0

1 H3C.!-+Br , HCIO,

1 Cr03 2 NoOH

2 Br2 3 HF

3 LizC03 4 Ac20 pyridine

N - VI -,

1 N-brornoocetamide

Reference(s):

a DOS 1 618 613 (Lepetit; appl 7.1.1967; GB-prior 11.1.1966, 11.7.1966,29.9.1966)

US 3 461 119 (Lepetit; 12.8.1969; appl 1967; GB-prior 1.1 1.1966)

Trang 2

872 F Flubendazole

sytlthesis of starting compound:

DE 1 568 971 (Gruppo Lepetit; appl 23.12.1966; GB-prior 11.1 l966, 11.7.1966,29.9.1966)

US 3 624 077 (Gruppo Lepetit; 30.1 1.1971; GB-prior 11.1.1966)

Nathansohn, G et al.: J Med Chem (JMCMAR) 10,799 (1967)

Nathansohn, G et al.: Gazz Chim Ital (GCITA9) 95, 1338 (1965)

review:

Nathanson, G et al.: Steroids (STEDAM) 13,365 (1969)

alternative synthesis of VI:

DOS 1 568 071 (Lepetit; appl 23.12.1966; GB-prior 11.1.1966, 11.7.1966,29.9.1966) DOS 1 568 972 (Lepetit; appl 23.12.1966; GB-prior 11.1.1966, 1 1.7.1966, 29.9.1966)

b Nathansohn, G et al.: J Med Chem (JMCMAR) 10,799 (1967)

Nathansohn, G et al.: Steroids (STEDAM) 13, 383 (1969)

Formulatior2(s): cream 0.025 %

Trade Name(s):

I : Azacortid crema (Lepetit)

Use: anthelmintic

RN: 31430-15-6 MF: C,,H,,FN,O, MW: 3 13.29 EINECS: 250-624-4

LD,,,: ~ 2 5 6 0 mg/kg (M, p.0.);

2560 mgkg (R, p.0.)

CN: [5-(4-fluorobenzoy1)-IH-benzimidazol-2-yl]cbamic acid methyl ester

1 NH3, CH30H,

sulfolone.125 O C

2 HZ Pd-C HCL

fluorobenzene 3-chloro-4-nitro- 3-chloro-4-nitro-

benzoyl chloride 4'-fluorobenrophenone

Refererlce(s):

DOS 2 029 637 (Janssen; appl 16.6.1970; USA-prior 20.6.1969)

US 3 657 267 (Janssen; 18.4.1972; appl 20.6.1969)

Raymaekers, A.H.M et al.: Arzneim.-Forsch (ARZNAD) 28,586 (1978)

3,4-diomino-4'- S-methyl- methyl

Formulation(s): susp 100 mglml; tabl 100 mg

Flubendazole

Trade Name(s):

D: Flubenol (Janssen); wfm F: Fluvermal (Janssen-Cilag)

lluorobenzophenone (1) isothioureo chloroformate

Trang 3

P"

Fluclorolone acetonide F 873

Fluclorolone acetonide

(Flucloronide)

ATC: H02AB Use: topical glucocorticoid

RN: 3693-39-8 MF: C2,H,yC12FOs MW: 487.40 EINECS: 223-010-9

CN: (6a,l 1 P,16a)-9,l I-dichloro-6-fluoro-2l-hydroxy-16,17-[(I-methylethylidene)bis(oxy)]pregna- 1 ,4-diene- 3,20-dione

d

HJC-SOzCI pyridine DMF

21-0-acetyl-6.-fluoro-

16a-hydmxyhydrocortisone

ocetonide

1 CIZ CHCI3

3 KOH

b

1 chlorine

2, selenium dioxide

3 potassium hydroxide

( Fluclarolone occtonide I

Reference(s):

US 3 201 391 (Syntex; 17.8.1965; MEX-prior 18.2.1959, 20.10.1959)

starting material:

Mills, J.S et al.: J Am Chem Soc (JACSAT) 81, 1264 (1959)

Formulation(s): cream 0.025 %, 0.25 %

Trade Name(s):

F: Topilar (Syntex-Daltan); GB: Topilar (Syntex); wfm

wfm

Flucloxacillin

(J3oxacillin)

ATC: JOlCA 1Jse: antibiotic

RN: 5250-39-5 MF: CIyH,,C1FN3OSS MW: 453.88 EINECS: 226-051-0

CN: [2S-(2a,5a,6~)]-6-[[[3-(2-chloro-6-fluorophenyl)-5-methyl-4-isoxazolyl]carbonyl]amin]-3,3-dimethyl- 7-oxo-4-thia-l-azabicyclo[3.2.0]heptane-2-carboxylic acid

monosodium salt

RN: 1847-24-1 MF: C,,H16ClFN3NaOSS MW: 475.86 EINECS: 217-428-0

LD,,: 1360 mglkg (M, i.v.); 7600 mgkg (M, p.0.);

680 mglkg (R, i.v.); 1 1 glkg (R, p.0.);

670 mg/kg (dog, i.v.); >10 glkg (dog, p.0.)

Trang 4

8 7 4 F Fluconazole

2-chloro-6-fluoro-

benzaldehyde

CH, CH3

methyl

ocetoacetate

GB 987 299 (Beecharn; appl 17.10.1962; addition to GB 905 778 from 14.3.1961)

US 3 239 507 (Beecham: 8.3.1966; GB-prior 17.10.1962)

(11) 6-aminopenicillanic

For~nulation(s): cps 272 mg, 544 mg; vial 272 mg, 544 mg, 1088 mg, 2176 mg (as sodium salt hydrate)

Flucloxacillin

Trade Narne(s):

D: Flanomox (Wolfo-comb GB: Floxapen (SmithKline I: Infectrin (Pierrel)-comb Fluxapril (Leder1e)-comb Beecham) with ampicillin Staphylex (SmithKline Magnapen (SmithKline J: Culpen (Fujisawa) Beecham) Beecham)-comb Floxapen (Beecham)

Stafoxil (Yamanouchi)

acid

Fluconazole

(UK-49858)

ATC: J02ACOI; J02AX Use: antifungal (treatment of vaginal, oropharyngeal and atrophic oral candidiasis)

RN: 86386-73-4 MF: C,,H,,F,N,O MW: 306.28

LD,,,: >200 mg/kg (M, i.v.); 1408 mglkg (M, p.o.1;

>200 mg/kg (R, i.v.); 1271 mg/kg (R, p.0.);

>I00 mglkg (dog, i.v.); >300 mglkg (dog, p.0.)

CN: a-(2,4-difluoropheny l)-a-(IN-1,2,4-triazol-l-ylmethyl)-1H-1,2,4-triazole- 1-ethanol

Trang 5

Fluconazole F 875

butyllithium

C I ~ C I

0

,

1 -3-dichloro- ocetone

1 H-1.2.4-

triozole (111)

F

Fluconazole

1,3-difluoro- 2.4-difluoro- 1 -3-dichloro-2-(2,4-difluoro-

benzene (I) phenyllithium phenyl)-2-proponol (11)

chloroacetyl a-chloro-2.4-difluoro- a-(1 H-l,2.4-triozol-1 -yl)-

chloride acetophenone 2,4-difluc~oacetophenone (N)

trirnethylsulfoxonium 1 -[2-(2.4-difluorophenyl)-

iodide 2,3-epoxypropyll- 1 H-

1.2.4-triozole

Reference(s):

GB 2 099 818 (Pfizer; appl 22.4.1982; prior 6.6.1981,4.3.1982)

EP 96 569 (Pfizer; appl: 6.6.1983; GB-prior 9.6.1982, 30.7.1982)

tablet formulation:

EP 178 682 (Schering Corp.; appl 23.4.1986; USA-prior 19.10.1984)

alternative synthesis:

ES 549 684 (Lazlo Int.; appl 6.12.1985)

ES 5 490 202 (Inke S A.; appl 19.1 1.1985)

US 5 710 280 (Dev Center Biotech Taiwan; 20.1.1998; appl 9.7.1996)

WO 9 703 971 (Apotex; appl 17.7.1996; NZ-prior 17.7.1995)

Formulation(s): cps 50 mg, 100 mg, 150 mg, 200 mg; susp 50 mg/5 ml; syrup 50 mgIl0ml; tabl 50 mg,

100 mg, 150 mg, 200 mg; vial 100 mg, 200 mg, 400 mg

Trade Name(s):

D: Diflucan (Pfizer) I: Biozolene (Bioindustria; Elazor (Sigma-Tau)

F: Triflucan (Pfizer; 1989) 1989) J: Diflucan (Pfizer Taito) GB: Diflucan (Pfizer; 1988) Diflucan (Roerig) USA: Diflucan (Pfizer; 1990)

Trang 6

876 F Flucytosine

Use: fungicide

RN: 2022-85-7 MF: C4H4FN30 MW: 129.09 EINECS: 217-968-7

LD,,: 500 mg/kg (M, i.v.); > I 5 g/kg (M, p.0.);

>600 mgkg (R, i.v.); > I 5 g/kg (R, p.0.)

CN: 4-amino-5-fluoropyrimidin-2(IH)-one

H

POCIJ dimethylaniline

0 CI

2.4-dichloro- 5-fluoro- pyrimidine

5-fluoro-2- 4-chloro-5-fluoro-

methylthiourocii 2-methylthio-

(cf fiuorouracil pyrimidine

synthesis)

4-omino-2- chloro-5-fluoro- pyrimidine

a Duschinsky, R et al.: J Am Chem Soc (JACSAT) 79,4559 (1957)

Undheim, K.; Gacek, M.: Acta Chem Scand (ACHSE7) 23, (I), 294 (1969)

US 3 040 026 (Roche; 19.6.1962; appl 3.6.1959)

US 3 185 690 (Roche; 25.5.1965; prior 3.6.1959, 14.9.1961)

b US 2 945 038 (Roche; 12.7.1960; prior 26.9.1956)

US 2 802 005 (Roche; 6.8.1957; prior 26.9.1956)

medical use:

US 3 368 938 (Roche; 13.2.1968; prior 2.3.1962)

Formulation(s): cps 250 mg, 500 mg; tabl 500 mg; vial 2.5 g1250 rnl

Trade Name(s):

D: Ancotil Roche (ICN) GB: Alcobon (Roche); wfm J: Ancotil (Roche)

F: Ancotil (Roche) I: Ancotil (Roche) USA: Ancobon (Roche)

Fludarabine phosphate

(2-fluoro-ara-AMP)

ATC: LOlBB05 Use: antineoplastic, antimetabolite, treatment of chronic lymphocytic leucemia

RN: 75607-67-9 MF: C,,H,,FN,O,P MW: 365.21

LD,,,: 375 mglkg (M, i.p.); 1236 mgkg (M, i.v.)

CN: 2-fluoro-9-(5-O-phosphono-~-~-arabinofuranosyl)-9H-purin-6-amine

fludarabine

RN: 21679-14-1 MF: C,,H,,FNSO4 MW: 285.24 EINECS: 244-525-5

Trang 7

Fludarabine phosphate F 877

k

H2N N

2,4,5,6-tetroornino- forrnornide 2-omino-

pyrimidine

orobinofuronose

adenine (I)

1 NoOCH,, CH,OH 1 BCI* CH,CI,

If Z

2 tetrofluaroboric acid 1 boron trichloride

sodium nitrite 2 phosphorus oxychloride,

triethyl phosphate

9-(2,3,5-tri-0-benzyl- Fludorobine 8-D-orobinofuronosyl)- phosphate 2-fluoroodenine

Reference(s):

US4 357 324 (Department of Health of USA; 2.1 1.1982; appl 24.2.1981)

synthesis of 9-P-D-arabinofuranosyl-2-fluoroadenine:

US 4 210 745 (Department of Health of USA; 1.7.1980; appl 20.1 1.1978; prior 10.3.1978,4.1 l978)

Montgomery, J.A et al.: J Heterocycl Chem (JHTCAD) 16, 157 (1979)

Montgomery, J.A.; Hewson, K.: J Med Chem (JMCMAR) 12,498 (1961)

synthesis of Zaminoadenine:

Robins, R.K et al.: J Am Chem Soc (JACSAT) 75,263 (1953)

Formulation(s): vial (lyo.) 5 mg, 50 mg

Trade Name(s):

D: Fludara (rneda; Schering) 'GR: Fludara (Schering)

F: Fludara (Schering) USA: Fludara (Berlex; 1991)

Trang 8

878 F Fludrocortisone

S03CA05 Use: glucocorticoid

IRN: 127-31-1 MF: C2,H2,FOs MW: 380.46 EINECS: 204-833-2

LD,,: 170 mglkg (M, i.p.)

CN: (1 1 P)-9-fluoro-ll,l7.21-trihydroxypregn-4-ene-3,20-dione

acetate

RN: 514-36-3 MF: C,,H,,FO, MW: 422.49 EINECS: 208-180-4

LD,,: >I glkg (R, p.0.)

3 s r

' H $ N'

1 N-bromo- ocetamide

/ hydrocortisone 21-ocetote

H2F2

& I C H 3 onhydrous ;130, b or HCIJ/THFc or C H C I ~ / H ~ O / H C I O ~ ~ + I1

me^ H

21-ocetoxy-3.20-dioxo-98.118-

epoxy-17-hydroxy-4-pregnene ( I )

( fludrocortisone ocetote (11) Fludrocortisone

Refennce(s):

a Fried, J.; Sabo, E.F.: J Am Chem Soc (JACSAT) 76, 1455 (1954)

b GB 792 224 ( O h Mathieson; appl 1954; USA-prior 1954)

c DE 1 035 133 (Merck & Co.; appl 1956; USA-prior 1955)

Hirschmann, R.F et al.: J Am Chem Soc (JACSAT) 78,4956 (1956)

d US 2 894 007 (Merck & Co.; 7.7.1959)

e DE 1 028 572 (Schering AG; appl 2 1.1.1 957)

synthesis of hydrocortisone acetate:

Fried, J.; Sabo, E.F.: J Am Chem Soc (JACSAT) 75,2273 (1953)

US 2 771 475 (Upjohn; 1956, appl 1953)

GB 792 224 (Olin Mathieson; appl 1954; USA-prior 1954)

alternative syntheses:

US 2 771 475 (Upjohn; 1956; appl 1953)

US 2 799 688 (Upjohn; 1957; appl 1954)

US 2 852 51 1 (Olin Mathieson; 1958; prior 1953)

US 4 041 055 (Upjohn; 9.8.1977; appl 17.1 1 l975)

Trang 9

Fludroxycortide F 879

Formulation(s): ear drops 8 mgI8 ml in comb with polymyxin B; ointment 0.001 %; tabl 0.1 mg (as acetate)

Trade Name(s):

D: Astonin H (Merck) F: Panotile (Zambon)-comb USA: Florinef (Apothecon) Fludrocortison (Bristol- GB: Florinef (Bristol-Myers

Myers Squibb) Squibb; as acetate)

Panotile (Zambon)-comb J: Florinef (Bristol Squibb)

Fludroxycortide

(Flurandrenolide)

ATC: D07AC07 Use: glucocorticoid, anti-inflammatory

RN: 1524-88-5 MF: C24H33FOh MW: 436.52 EINECS: 216-196-8

CN: (6a,11 ~,16a)-6-fluoro-11,21-dihydroxy-16,17-[(1-methylethylidene)bis(oxy)]pregn-4-ene-3,20-dione

21-acetoxy-16a.17-epoxy-

3P-hydroxy-20-0x0-5-pregnene

(from pregnenolone)

0 , CH2C12, - 80 "C b &FH3

hydrogen N-bromo-

fluoride ocetamide H ti

F

1 Cr03

2 HBr, CH3COOH

1 CH3COOK CH3COOH

2 No2C05 CH30H

I , 11

1 , chromium(VI) oxide

2 acetic anhydride

microbiological hydroxylation

[Arthrobotrys s u p e r b 0 vor oligospora (ATCC 11572)]

or [Cunninghamello blakesleeana (ATCC 8688b)I

0 z

o=tcH3

CH3

ocetone

HCIO,

Trang 10

880 F Flufenamic acid

Reference(s):

a US 3 014 938 (Syntex; 26.12.1961; appl 23.8.1960; MEX-prior 7.9.1959)

US 3 119 749 (Syntex; 28.1.1964; appl 17.1 1.1961; MEX prior 7.6.1961)

US 3 124 571 (Syntex; 10.3.1964; MEX-prior 26.1.3960)

starting material:

Julian, P.L.: J Am Chem Soc (JACSAT) 72,5145 (1950)

US 2 678 932 (Sterling Drug; 1954; prior 1951)

b US 3 126 375 (Syntex; 24.3.1964; appl 11.6.1959; MEX-prior 13.6.1958)

DE 1 131 213 (Syntex; appl 6.6.1959; MEX-prior 13.6.1958)

alternative syntheses:

Mills, J.S et al.: J Am Chem Soc (JACSAT) 82, 3399 (1960); 81, 1264 (1959)

[JS 3 203 869 (Syntex; 31.8.1965; MEX-prior 11.10.1962)

Formulation(s): lotion 0.05 % (15 ml, 60 ml); tape 4pg/cm2

Trade Name(s):

D: Sermaka (Lilly) I: Drenison (Lilly); wfm J: Drenison Q (Lilly-

GB: Drenison (Lilly); wfm Drenison Neomicina Dainippon)

Haclan (Dista); wfm (Li1ly)-comb.; wfm USA: Cordran (Oclassen)

(Acide flufenamique) Use: anti-inflammatory, antirheumatic

RN: 530-78-9 MF: C14HloF1N02 MW: 281.23 EINECS: 208-494-1

LD,,: 158mg/kg(M,i.v.);490mglkg(M,p.o.):

98 m g k g (R, i.v.); 249 mglkg (R, p.0.)

CN: 2-[[3-(trifluoromethyl)phenylJamino]benzoic acid

aluminum salt

RN: 16449-54-0 MF: C4,H,AIF9N306 MW: 867.66 EINECS: 240-498-9

LD,,,: 1460 mglkg (M, p.0.);

550 mglkg (R, p.0.)

2-chloro- 3-trifluoro-

benzoic methylonilhe

ocid

COOH

Flufenornic ocid

I

Reference (s):

FR 1 341 M (Parke Davis; appl 1 1.8.1961)

Moffett, R.B.; Aspergen, B.D.: J Am Chem Soc (JACSAT) 82, 1605 (1960)

salts with amines:

DOS 2 758 787 (T Eckert; appl 29.12.1977)

Formulation(s): ointment 3 g/100 g (3 %); sol 25 mglg

Trade Name(s):

D: Algesalona (Sohay)-comb Rheuma Lindofluid Meralen (Merrell); wfm

Dignodolin (Sankyo) (Lindopharm) I: Mobilisin (Luitpold)-comb Mobilisin (Sankyo)-comb F: Arlef (Parke Davis); wfrn J: Achless (Tatsumi)

GB: Arlef (Parke Davis); wfm Arlef (Parke Davis-Sankyo)

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