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Pharmaceutical Substances Syntheses, Patents, Applications - Part 113 potx

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20 mg, 40 mg Trade Natnes: I : Perketan Inverni della Serepress Formenti... iodide 100 mg; vial 100 mg Trade Names: D: Alrheumun Bayer Vital; 1975 Orudis RhGne-Poulenc Rorer F: Bi-Pr

Trang 1

Ketamine K 1121

starting material:

Kiihn, M.: J Prakt Chem (JPCPAO) 156 (11), 103 (1940)

b AT 198 263 (Synfarma; appl 1955)

Formulation(s): amp 1 gl5 ml; cps 250 mg

Trade Name(s):

Use: analgesic, anesthetic

LD,,: 77 mgkg (M, i.v.)

CN: (f)-2-(2-~hlorophenyI)-2-(methylamino)cyclohexanone

monohydrochloride

RN: 1867-66-9 MF: C,3H,,CIN0 HCI MW: 274.19 EINECS: 217-484-6

2-chloro- cyclopentyl-

benzonitrilc magnesium

bromide

(2-chloro- benzoyl)- cyclopentone

methylamine

Reference(s):

US 3 254 124 (Parke Davis; 31.5.1966; prior 31.7.1961,29.6.1962)

BE 634 208 (Parke Davis; appl 27.6.1963; USA-prior 29.6.1962)

Formulation(s): amp 50 mg/5 ml, 100 mg/2 ml, 500 mg/lO ml; inj 5 mg/ml, 10 mglml, 25 mglml, 50 mglml

(as hydrochloride)

Trade Name(s):

USA: Ketaject (Bristol); wfm

Trang 2

1122 K Ketanserin

Use: antihypertensive

CN: 3-[2-[4-(4-fluorobenzoy1)- 1-piperidinyllethyll-2,4(1 H,3H)-quinazolinedione

1 -benzyl-4-cyano- 4-fluorophenyl-

piperidine magnesium

bromide

ethyl chloro-

formate (11)

0

ethyl

anthranilate

1 S0Cl2

2 I11

chlaride

0

4-(4-fluarabenzoyl)- piperidine (111)

3-(2-hydraxyethy1)- 2,4(1 H.3H)-quinozo- linedione (N)

EP 13 612 (Janssen; appl 7.1.1980; USA-prior 8.1.1979, 12.10.1979)

US 4 335 127 (Janssen; 15.6.1982; prior 8.1.1979, 12.10.1979)

alternative synthesis:

EP-appl 98 499 (Ravizza; appl 27.6.1983; I-prior 6.7.1982)

Formulation(s): amp 10 mg/2 ml, 50 mgllO ml; tabl 20 mg, 40 mg

Trade Natne(s):

I : Perketan (Inverni della Serepress (Formenti)

Trang 3

Ketazolam K 1123

Use: tranquilizer

LD,,: 2 gikg (M, p.0.);

5 gtkg (R, p.0.)

CN: 1I-chloro-8,12b-dihydro-2,8-dimethyl-12b-phenyl-4H-[l,3]oxazino~3,2-d][l,4]benzodiazepine-4,7(6H)-

dione

2 NHJ

-+ CI

bromide

2-amino-5- dimethyl 5-chloro-2-

chlarobenzo- sulfate rnethylomino-

diketene (11)

L-2Ez-J

Ketozolam

H3C

Referenceis):

a US 3 575 965 (Upjohn; 20.4.1971; prior 20.10.1969)

b S~muskovicz, J et al.: Tetrahedron Lett (TELEAY) 1971,3665

DOS 1 947 226 (Upjohn; appl 18.9.1969; USA-prior 19.9.1968, 27.3.1969)

Formulariort(s): cps 15 mg, 30 mg, 45 mg

Trade Name(s):

Trang 4

1124 K Ketobemidone

Ketobemidone

(Cetobemidone)

Use: analgesic

LD,,,: 14 mglkg (M, i.v.);

10 m g k g (R, i.v.)

CN: 1-14-(3-hydroxy phenyl)-1-methyl-4-piperidiny1]-l-propanone

hydrochloride

RN: 5965-49- 1 MF: C,,H2,N02 HCl MW: 283.80

0rMgACH3

-+ 1

4-(3-methoxypheny1)- Ketobemidone

1 -methyl-4-propionyl-

piperidine (I)

Reference(s):

DRP 752 755 (1 G Farben; appl 1942)

alternative synthesis:

Kiigi, H.; ~ i e s c h e r , K.: Helv Chim Acta (HCACAV) 32,2489 (1949)

Formulation(s): amp 2 mg12 ml, 10 mg/lO ml, 5 0 mg150 ml; tabl 5 mg (as hydrochloride)

Trade Name(s):

Ketoconazole ATC: DO 1AC08; GOlAF11; J02AB02

Use: antimycotic RN: 65277-42- 1 M E C2,H2,C12N404 MW: 53 1.44 EINECS: 265-667-4

LD,,: 32 mglkg (M, i.v.); 618 m g k g (M, p.0.);

86 m g k g (R, i.v.); 166 mglkg (R, p.0.);

23.3 mglkg (dog, i.v.); 178 m g k g (dog, p.0.)

CN: cis- 1 -acetyl-4-[4-[[2-(2,4-dichloropheny1)-2-1 H-imidazol-1 -ylmethyl)- l,3-dioxolan-4-

yl]methoxy]phenyl]piperazine

Trang 5

Ketoprofen K 1125

-

2.4-dichloro- glycerol cis-2-(2,4-dichloro- *' imidozole

methyl-1.3-dioxolane

1 NaOH

0

NaH

sodium hydride

OH

1 -ocetyl-4-(4-

hydroxypheny1)-

piperazine

Ketoconazole I

Reference (s):

DOS 2 804 096 (Janssen; appl 3 1.1.1978; USA-prior 3 1.1.1977,21.11.1977)

US 4 335 125 (Janssen; 15.6.1982; prior 31.1.1977)

Formulaiion(s): cream 20 mg/g (2 %); shampoo 2 %; sol 20 mgiml; susp 100mg; tabl 200 mg

Trade Name(s):

Use: analgesic, anti-inflammatory RN: 2207 1-1 5-4 MF: C,,H,,O, MW: 254.29 EINECS: 244-759-8

LD,,: 500 mgkg (M, i.v.); 360 mgkg (M, p.0.);

350 mglkg (R, i.v.); 62.4 mglkg (R, p.0.)

CN: 3-benzoyl-a-methylbenzeneacetic acid

lysine saIt

RN: 57469-78-0 MF: Cz2Hz8NzOs MW 4 0 4 8

Trang 6

1126 K Ketorolac

3-methylbenzo-

phenone

3-bromomethyl- benzophenone

(3-benzoylphenyl)- diethyl carbonate

acetonitrile (I)

Reference(s):

US 3 641 127 (Rh8ne-Poulenc; 8.2.1972; F-prior 27.1.1967)

DE 1 668 648 (Rhhe-Poulenc; appl 26.1.1968; F-prior 27.l.l967),

methyl

alternative syntheses:

Ketoprofen

DOS 2 646 792 (Mitsubishi Petrochemical; appl 16.10.1976; J-prior 23.lO.l975,31.7.1976)

US 4 097 522 (Aziende Chim Riun Angelini Francesco; 27.6.1978; I-prior 5.6.1975) '

DOS 2 744 832 (LEK; appl 5.10.1977; YU-prior 18.10.1976)

DOS 2 744 833 (LEK; appl 5.10.1977; YU-prior 18.10.1976)

DOS 2 744 834 (LEK; appl 5.10.1977; YU-prior 18.10.1976)

iodide

100 mg; vial 100 mg

Trade Name(s):

D: Alrheumun (Bayer Vital;

1975)

Orudis (RhGne-Poulenc

Rorer)

F: Bi-Proftnid (Specia)

KCtum (MCnarini)

Profhid (Specia)

Toprec (ThCraplix)

GB: Ketocid (Trinity)

Orudis (Rhhe-Poulenc

Rorer)

Oruvail (Rh8ne-Poulenc

Rorer)

Powergel (Searle) I: Artrosilene (Dompt; as lysine salt)

Fastum (Menarini) Flexen (Lifepharma) Isok (San Carlo) Ketartrium (Esseti) Ketodol (Drug Research) Ketofen (Delsaz &

Filippini; as lysine salt) Meprofen (AGIPS) Orudis (Rh8ne-Poulenc Rorer)

Profend (Drug Research) Reuprofen (Terapeutico M.R.)

Salient (Biomedica Foscama) Sinketol (Locatelli) J: Capisten (Kissei) Orudis (Hokuriku) USA: Orudis (Wyeth-Ayerst; 1977)

Oruvail (Wyeth-Ayerst)

Use: non-steroidal anti-inflammatory, analgesic

LD,,,: 200 mglkg (M, p.0.)

CN: (+)-5-benzoyl-2,3-dihydro-1H-pyrrolizine-l-carboxylic acid

Trang 7

Ketorolac K 1127

tromethamine salt

RN: 74103-07-4 MF: C,,H,,NO, C4H,,N03 MW: 376.41

monosodium salt

succinimide benzamide chloride

pyrrole (I) dimethyl

sulfide

2-(methylthio)- pyrrole

5-benzoyl-2-(methyl- 6.6-dimethyl-5.7-dioxo- 1 -[2-(4.6-dioxo-2.2-dimethyl-

thio)pyrrole (11) spiro[2.5]octone- 1,3-dioxon-5-yl)ethyl]-2-

4.8-dione (111) (rnethy1thio)-5-benzoylpyrrole (N)

2 HCI , CH OH

J

1 3-chloroperbenzoic

acid

2 rnethonol

1 Ketoroloc I

1 KOH CH30H

2 HCI

'

f

dimethyl 5-benzoyl-1,2- dihydro-3H-pyrrolo[l,2-a]- pyrrole-l , l -dicarboxylate (V)

"W""?rCOOH

1 I11 , NOH

2 HCI

4 KOH CH30H

5 HCI

- ,

0 H o

ocid

Trang 8

1128 K Ketotifen

2-chloro- pyrrole

2-chloro-5- benzoylpyrrole (VI)

I NOH, DMF

CH3

Reference(s):

a,b US 4 347 186 (Syntex; 31.8.1982; appl 20.10.1980)

US 4 458 081 (Syntex; 3.7.1984; appl 11.6.1982; prior 20.10.1980)

c US 4 873 340 (Syntex; 10.10.1989; appl 29.5.1986)

alternarive synthesis:

DE 2 760 330 (Syntex; appl 13.7.1977; USA-prior 14.7.1976, 23.2.1977)

DE 2 731 678 (Syntex; appl 13.7.1977; USA-prior 14.7.1976,23.2.1977)

US 4 087 539 (Syntex; 5.2.1978; appl 23.2.1977; prior 14.7.1976)

US 4 089 969 (Syntex; 16.5.1978; appl 23.2.1977; prior 14.7.1976; 23.2.1977)

US 4 097 579 (Syntex; 27.6.1978; appl 31.3.1977)

Muchowski, J.M et al.: J Med Chem (JMCMAR) 28,1037 (1985)

synthesis of enantiomers:

EP 264 429 (Wisconsin Ala Res Found.; appl 2.4.1987; USA-prior 6.11.1986, 16.4.1986)

Gazman, A et al.: J Med Chem (JMCMAR) 29,589 (1986)

Formularion(s): amp 10 mg, 15 mg, 30 mg; eye drops 0.5 %; suppos 30 mg; tabl 10 mg (as tromethamine

salt)

Trade Name(s):

Use: antiasthmatic, antihistaminic

LDso: 179 mglkg (M, p.0.)

CN: 4,9-dihydro-4-(l-methyl-4-piperidinylidene)-1OH-henzo[4,5]cyclohepta[1,2-b]thiophen-l0-onc

fumarate

Trang 9

Ketotifen K 1129

benzoyl peroxide KOH CH30H

- 1

0 ti-bromosuccinimide 0

4-0x0-9.10-dihydro-

4H-benzo[4.5]cyclo-

hepto[l.2-blthiophene

(cf pizotifen

synthesis)

, THF

1 -methylpiperidin-

chloride

9- ond 10-bromo-4-0x0-4H-

benzo[4.5]cyclohepta[1.2-blthiophene (I)

seporotion over silica gel

2N HCI

_,

I Ketotifen 1

Trang 10

1130 K Khellin

Reference(s):

DAS 2 11 1 071 (Sandoz; appl 9.3.1971; CH-prior 11.3.1970, 31.7.1970)

US 3 682 930 (Sandoz; 8.8.1972; CH-prior I 1.3.1970,3 1.7.1970)

DOS 2 144 490 (Sandoz; appl 6.9.197 1; CH-prior 24.9.1970,4.2.1971)

US 3 749 786 (Sandoz; 8.8.1972; CW-prior 11.3.1970)

alternative syntheses:

DOS 2 302 970 (Sandoz; appl 22.1.1973; CH-prior 24.1.1972)

US 3 960 894 (Sandoz; 1.6.1976; CH-prior 21.1.1972)

US 4 128 549 (Sandoz; 5.12.1978; prior 19.1.1973, 26.7.1974, 27.2.1976,3.2.1977)

medical use as antiasthmatic:

US 4 073 915 (Sandoz; 14.2.1978; CH-prior 20.5.1975)

Formulation(s): cps 1 mg; syrup 0.02 %; tabl 1 mg, 2 mg (as fumarate)

Trade Name(s):

Use: vasodilator

LDs,,: 30.6 mglkg (M, i.v.); 50.8 mglkg (M, p.0.);

34.4 mglkg (R, i.v.); 68.8 mglkg (R, p.0.)

CN: 4,9-dimethoxy-7-methyl-5H-furo[3,2-g][1]benzopyran-5-one

I Khellin

Isolation from ethanolic extracts of fruits of Umbellifera Ammi visnaga

Reference(s):

Spath, E ; Gruber, W.: Ber Dtsch Chem Ges (BDCGAS) 71, 106 (1938)

Abu-Shady, H.; Soine, T.O.: J Am Pharm Assoc (JPHAA3) 41,481 (1952)

total syntheses:

Baxter, R.H et al.: J Chem Soc (JCSOA9) 1949,30

Clarke, J.R.; Robertson, A.: J Am Chem Soc (JACSAT) 71, 362 (1949)

Clarke, J.R.; Robertson, A,: J Chem Soc (JCSOA9) 1949,302

Geissman, T.A.; Halsall, T.G.: J Am Chem Soc (JACSAT) 73, 1280 (1951)

Formulation(s): cps 10 mg, 12 mg; drg 1.25 mg, 10 mg; drops 50 mgl100 ml; ointment 0.1 g1100 g,

0.01 g1100 g; sol 0.025 gll00 ml; suppos 2.5 mg, 5 mg; tabl 25 mg

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