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Pharmaceutical Substances Syntheses, Patents, Applications - Part 176 ppt

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3-2-thieny1- ocrylonitrile acrylamide I N-methvltri- methylenediomine propane sultone References: BE 658 987 Pfizer; appl.. 125 mg, 250 mg as pamoate Trade Names: D: Helmex Pfizer H

Trang 1

Pvrantel P 1751

Tmde Name(s):

F: Norbiline (Bellon)-comb I: Norbiline (RhSne-Poulenc

Rorer)

Use: anthelmintic (nematodes) RN: 15686-83-6 MF: C,,H,,N,S MW: 206.31 EINECS: 239-774-1

LD,,: 175 mg/kg (M, p.0.);

170 mglkg (R, pa.);

2 d k g (dog, p.0.)

CN: (E)-1,4,5,6-tetrahydro-l-methyl-2-[2-(2-thienyl)ethenyI]pyrimidine

tartrate (1:l)

RN: 33401-94-4 MF: ClIHl4N,S C,H,O, MW: 356.40 EINECS: 251-501-8

LD,,: 2220 pg/kg (M, i.v.); 123 mglkg (M, p.0.);

170 mgkg (R, p.0.)

pamoate (1: 1)

RN: 22204-24-6 MF: CIIHl4N,S C,,H,,O, M W 594.69 EINECS: 244-837-1

LD,: 62Q mglkg (M, i.p.1;

535 mglkg (R, i.p.)

+ ,c-coo, CH3COONH,, pyridine

N H 2

thiophene-2- cyanoocetic

carboxaldehyde acid

3-(2-thienyl) 3-(2-thieny1)- ocrylonitrile acrylamide (I)

N-methvltri- methylenediomine propane

sultone

Reference(s):

BE 658 987 (Pfizer; appl 28.1.1965; GB-prior 28.1 l964, 13.8.1964, 26.9.1964)

US 3 502 661 (Pfizer; 24.3.1970; prior 14.2.1967, 5.6.1967, 9.11.1967)

CH 404 677 (Dr A Wander; appl 2.12.1960)

CH 398 620 (Dr A Wander; appl 16.8.1960)

GB 980 853 (Dr A Wander; appl 16.8.1961 ; CH-prior l6.8.l960,2.I2.l960)

NL 147 426 (Dr A Wander; appl 24.5.1963; CH-prior 25.5.1962, 8.6.1962, 5.12.1962, 15.2.1963)

DE 1 280 879 (Wander; appl 7.8.196 1; CII-prior 16.8.1960, 2.12.1960)

US3539573(Wander; 10.11.1970;CH-prior 16.8.1960,2.12.1960,20.7.1961,25.5.1962,5.12.1962,15.2.1963, 22.3.1967, 11.7.1967, 3.11.1967)

Hunziker, F et al.: Helv Chim Acta (HCACAV) 50, 1588 (1967)

Fomulation(s): chewing tabl 250 mg; sol 5 %; susp 250 mg/5 ml, 720 mg; tabl 125 mg, 250 mg (as

pamoate)

Trade Name(s):

D: Helmex (Pfizer) Helmintox (Innotech I: Combantrin (Pfizer)

F: Combantrin (Pfizer) International) J: Combantrin (Pfizer)

GB: Combantrin (Pfizer); wfm

Trang 2

1752 P Pvrazinamide

USA: Antiminth (Pfizer); wfm Antiminth (Roerig); wfm Combantrin (Pfizer); wlm

Use: tuberculostatic, antibacterial RN: 98-96-4 MF: C,H,N,O MW: 123.12 EINECS: 202-717-6

LD,,: 1680 m g k g (M, i.p.); 2793 mglkg (M, s.c.)

CN: pyrazinecarboxamide

CHO

I

CHO

glyoxol o-phenylene- quinoxoline pyrorine-2.3- pyrozine-2-

corboxylic

methyl pyrazine- Pyrozinomide 2-corboxylote

Reference(s):

DRP 632 257 (Merck; 1934)

Hall, S.A et al.: J Am Chem Soc (JACSAT) 62, 664 (1940)

alternative synthesis via 2-cyanopyrazine (from 2-chloropyrazine):

EP 122 355 (Servipharm; appl 25.7.1983; CH-prior 21.3.1983)

Formulation(s): cps 500 mg; drg 300 mg in comb with rifapiam, isoniazide; f c tabl 500 mg; tabl 100 mg,

500 mg

Trade Name(s):

D: Pyrafat (Fatol) F: ' Pirilbne (Marion Merrell) I: Piraldma (Bracco) Pyrazinamid (Hefa Rifater (Marion Merrel1)- J: Pyramide (Sankyo)

Pyrazinamid "Lederle" GB: Rifater (Hoechst)-comb Merrel1)-comb

Rifater (Griinentha1)-comb Dohme)

Pyridinol carbarnate

(Pyricarbate)

ATC: C04AX49 Use: antiarteriosclerotic RN: 1882-26-4 MF: C,,HISN30, MW: 253.26 EINECS: 217-538-9

LD,,,: 3100 m g k g (M, p.0.);

1230 m g k g (R, p.0.);

1 gfkg (dog, p.o.1

CN: 2,6-pyridinedimethanol bis(methy1carbamate)

Trang 3

- Pyridinol carbarnate P 1753

starting product:

dioicolinic acid 2.6-bis(hydroxymethyI)-

pyridine (I)

2.6-bis(acetoxyrnethyI)- pyridine

C12, H2S0,

azobisisobutyronitrile H ~ O / H +

2.6-bis(chloromethyl)- pyridine

final product:

Reference(s):

FR 1 396 624 (M Inoue; appl 13.4.1964; J-prior 13.4.1963)

AT 258 953 (M Inoue; appl 13.4.1964; J-prior 13.4.1963)

AT 258 954 (M Inoue; appl 13.4.1964; J-prior 13.4.1963)

AT 258 955 (M Inoue; appl 8.1 1.1965)

methyl

isocyanate

alternative syntheses Lfrom 2,6-bis(hydroxymethy1)pyridine and N,W-dimethylurea]:

DOS 2 263 812 (Rocador S A.; appl 28.12.1972; E-prior 28.12.1971)

Pyridinol carbamale

yl- and y,-modifications:

DOS 2 702 772 (Richter Gedeon; appl 24.1.1977; H-prior 24.1.1976)

GB 1 548 334 (Richter Gedeon; appl 2 1.1.1977; H-prior 24.1.1976)

2.6-bis(hydroxymethy1)pyridine:

a FR 1 396 624 (M Inoue; appl 13.4.1964; J-prior 13.4.1963)

b Bockelheide, V.; Linn, W.J.: J Am Chem Soc (JACSAT) 76, 1286 (1954)

c FR 1 394 362 (Merck & Co.; appl 3 I 3.1964; USA-prior 2.4.1963)

Trang 4

1754 P Pyridofylline

alternative syntheses:

DAS 2 460 039 (Richter Gedeon; appl 19.12.1974; H-prior 29.12.1973)

DAS 2 614 400 (Richter Gedeon; appl 2.4.1976; H-prior 2.4.1975)

Fortnulation(s): tabl 250 mg

Trade Name(s):

F: Angioxine (Roussel); wfm I: Cicloven (AGIPS) J: Anginin (Banyu)

Use: coronary vasodilator RN: 53403-97-7 MF: C9H,2N406S C8HIIN03 MW: 473.46 EINECS: 258-521 -6

LD,,: 1 glkg(M,i.v.); 1600mg/kg(M,p.o.)

CN: 3,7-dihydro- l,3-dimethyl-7-[2-(sulfooxy)ethyl]-1H-purine-2,6-dione compd with 5-hydroxy-6-methyl-

3,4-pyridinedimcthanol (1 : 1)

pyridoxine

CHC13 CIS03H

chlorosulfonic acid

CZHJOH

Reference(s):

FR-M 828 ( J Debarge; appl 23.12.1960)

Trade Name(s):

F: Atherophyllinc (Merrell);

wfm

0-[2-(7-theophyllinyl)ethyl]

hydrogen sulfote (I)

Pyridofyllinc

Use: parasympathomimctic (cholinesterase blocker), antiniyasthenic, vagotonic RN: 101-26-8 MF: CYH11BrN20Z MW: 261.12 EINECS: 202-929-9

LDs,,: 1500 pglkg (M, i.v.); 16 mglkg (M, p.0.)

CN: 3-[[(dimethylamino)carbonyl]oxy]-I-methylpyridinium bromide

Trang 5

Pyridoxine P 1755

3-hydroxy- dimethyl- 3-(dimethylamino-

pyridine carbomoyl corbony1oxy)-

chloride pyridine

Reference(s1:

CH 246 834 (Roche; appl 1945)

US 2 572 579 (Roche; 1951; CH-prior 1945)

' 3 4 3 Pyridostigmine bromide

Fomulation(s): amp 1 mglml, 5 mglml; drg 60 mg; s r tabl 180 mg; syrup 6 0 mg15 ml; tabl 60 mg

Trade Name(s):

D: Kalymin (ASTA Medica F: Mestinon (Roche) J: Mestinon (Nippon Roche)

Pyridoxine

(Vitamin B,)

ATC:' A I I HA02 Use: vitamin (enzym co-factor)

RN: 65-23-6 MF: CsH,lN03 MW: 169.18 EINECS: 200-603-0

LD,: 545 mglkg (M, i.v.);

657 mglkg (R, i.v.); 4 glkg (R, p.0.)

CN: 5-hydroxy-6-methyl-3,4-pyridinedimcthanol

hydrochloride

RN: 58-56-0 MF: CsH1,NO, HCI MW: 205.64 EINECS: 200-386-2

LD,,: 660 mglkg (M, i.v.); 5500 mglkg (M, p.0.);

530 mglkg (R, i.v.); 4 glkg (R, p.0.);

>SO0 mgkg (dog, p.0.)

@ Marck + Co.:

u

H N 'f C H ~ + H O ~ C H ~ % H 2 ~ x ~ ~ c i 3 ~ c ~ oHc-NH2

DL-olanine (1) (11) DL-olonine ethyl

esler hydrochloride

N-formyl-DL-olanine ethyl ester (N)

5-ethoxy-4- (ocetol f r o m isobutyroldehyde Pyridoxine

+ 2-butene-1.4-diol) rnethyloxozole

Trang 6

1756 P Pyridoxine

cthyl 2-chloro-

acetoacetote

ethyl 4-methyl- 4-methyloxozole- 5-cyono-4- oxozole-5- 5-corboxomide methyloxozole (VII) corboxylote (VI)

dihydro- 1 -3-dioxepin

(ketol from ocetone +

2-butene-l,4-diol)

@ BASF:

0

1 NoOH

2 A @:S"'

3-methylsulfonyl-2,s-dihydro-

4-methyl-

oxoZolc (by addition of methonesulfonyl

bromide to 2,s-dihydrofuron and subsequent HBr elimination with NoOH)

0 COOH

COC12 (C&).+

I + 1 1 + I

'0 O ~ C H ~ omine

I NoOH

0 2 3.v HCI

ethyl 5-ethoxy-4-methyl-

oxozole-2-corboxylote (VIE)

Trang 7

Pyridoxine P 1757

Reference(s):

review of pyridoxine syntheses:

Konig, H.; Boll, W.: Chem.-Ztg (CMKZAT) 100, 105 (1976)

a Harris, E.E et al.: J Org Chem (JOCEAH) 27, 2705 (1962)

DAS 1 470 022 (Merck & Co.; appl 10.5.1962; USA-prior 15.5.1961, 16.1.1962)

US 3 227 721 (Merck & Co.; 4.1.1966; prior 15.5.1961, 16.1.1962, 24.5.1965)

US 3 227 724 (Merck & Co.; 4.1.1966; prior 15.5.1961, 16.1.1962, 16.6.1964)

b US 3 222 374 (Roche; 7.12.1965; prior 22.5.1963, 20.1 1.1964)

US 3 250 778 (Roche; 10.5.1966; appl 29.11.1962)

US 4 026 901 (Roche; 31.5.1977; appl 30.4.1975)

DOS 2 616 349 (Roche; appl 14.4.1976; USA-prior 30.4.1975)

5-cyano-4-methyloxazole:

US 4 093 654 (Roche; 6.6.1978; appl 31.3.1977)

c DAS 2 143 989 (BASF; appl 2.9.197 1)

3-methylsulfonyl-2,5-dihydrofuran:

DOS 2 435 098 (BASF; 22.7.1974)

d Maeda, J et al.: Bull Chem Soc Jpn (BCSJA8) 42, 1435 (1969)

alternative syntheses:

from 5-ethoxy-4-oxazolylacetic acid:

DAS 2 008 854 (Roche; appl 25.2.1970; CH-prior 25.3.1969)

4-methyloxazol from formimino ester hydrochloride and hydroxyacetone:

GB 1 515 737 (BASF; appl 22.1 0.1975; D-prior 31.10.1974)

Formulation(s): amp 25 mg/2 ml, 50 mgl2 ml, 100 mgl2 ml, 300 mg; drg 100 mg, 300 mg; f c tabl 40 mg;

tabl 1 mg, 25 mg, 40 mg, 50 mg, 100 mg, 300 mg (as hydrochloride)

Trade Name(s):

D:

F:

GB:

I:

B,-ASmedic (Dyckerhofo

B,-Vicotrat (Heyl)

BYK (Roche Nicholas)-

comb

Bonasanit (Weimer]

Hexobion (Merck)

Vitamin B, ratiopharm

(ratiopharm)

generics and circa 500

combination preparations

Becilan (Specia)

Dermo-6

(PharmadCveloppement)

Pyridoxine Aguettant

(Aguettant)

Vitamine B, Richard

(Richard)

numerous combination

preparations

Complement Continus

(Napp); wfm

numerous combination

preparations

Acutil Fosforo (SmithKline

Beecham)

Adenoplex (Lepetit)-comb

Alcalosio (SIT)-comb

Antemesyl (Mo1teni)- comb

Antimicotico pom derm

(IF1)-comb

Benadon (Roche) Benexol (Roche)-comb

Coxanturenasi (Teofarma)- comb

Detoxergon (Ba1dacci)- comb

Dobetin (Ange1ini)-comb

Emoferrina B,, os (Piam)- comb

Etanicozid (Piam)-comb

Furanvit (SIF1)-comb

Memosprint (Po1i)-comb

Menalgon (Menarini)- comb

Miazide B, (Wyeth- Leder1e)-comb

Midium (Glaxo)-comb

Mionevrasi forte (Boehringer Mannh.)- comb

Neogeynevral (Geymonat)- comb

Neuraben (Bioindustria)- comb

Neurobionta (Bracco)- comb

Sustenium (Menarini)- comb

Triferon (Sa1us)-comb Trinevrina B, (Chidotti)- comb

Xanturenasi (Teofarma) J: Aderoxin (Sonybod-Torii) Pyridomin (Showa) Sandoxin (Sanko) numerous combination preparations

USA: Aminoxin (Tyson) Beelith (Beach)-comb Lurline (Fielding)-comb Marlyn Formula 50 (Marl yn)-comb

Mega-B (Arco)-comb

Trang 8

1758 P Pyrimethamine

Use: chemotherapeutic (toxoplasmosis and malaria), antimalarial

RN: 58-14-0 MF: CL2HI3C1N4 MW: 248.72 EINECS: 200-364-2

LDs,,: 92 mglkg (M, p.0.);

440 mglkg (R, p.0.)

CN: 5-(4-chloropheny1)-6-ethyl-2,4-pyrimidinediamine

orthoformote 4-chlorobenzyl

cyonide

methyl propionote

US 2 576 939 (Burroughs Wellcome; 1951; prior 1950)

US 2 602 794 (Burroughs Wcllcome; 1952; appl 1950)

US 2 680 740 (Rldne-Poulenc; 1954; F-prior 1951)

Formulation(s): tabl 25 mg

Trade Name(s):

D: Daraprim (Glaxo Fansidar (Roche)-comb USA: Daraprim (Glaxo

F: Fansidar (Roche)-comb I: - Metakelfin (Pharmacia & with sulfadioxine

GB: Daraprim (Burroughs J: Fansidar (Roche)-comb

Wellcomc)

Pyrithione zinc

(Zinc pyrithione)

ATC: D l l A X Use: antiseborrhoic, fungicide, bactericide RN: 13463-41-7 MF: C,,H,N,O,S,Zn MW: 317.71 EINECS: 236-671-3

LD,,,: 160 mg/kg (M, p.0.);

177 mglkg (R, p.0.);

600 mglkg (dog, p.0.)

CN: (T-4)-bis(l-hydroxy-2(1H)-pyridinethionato-O,S)zinc I

Trang 9

Pyrithyldionc P 1759

2-chloro- ocetic acid

2-chloro- 2-mercopto- 1 -hydroxy-2- pyridine pyridine pyridine pyridinethione (I)

/ Pyrithione zinc 1

Reference(s):

GB 761 171 (Olin Mathieson; appl 19.5.1954; USA-prior 29.5.1953)

pyrithione:

US 2 745 826 ( O h Mathieson; 15.5.1956; appl 16.12.1953)

Shaw, E et al.: J Am Chem Soc (JACSAT) 72,4362 (1950)

use:

US 3 236 733 (Procter & Gamble; 22.2.1966; prior 5.9.1963, 1.4.1965)

US 3 281 366 (Procter & Gamble; 25.10.1966; prior 25.8.1964.4.1 1.1965)

Formulation(s): cream 1 gI100 g; shampoo 1 %, 2 %

Trade Name(s):

D: de-squaman hermal Ultrex antipelliculaire (Lab USA: DHS Zinc (Person RL

F: Fonderma (Doms); wfm GB: Polystar AF (Stiefe1)-comb Head & Shoulders (Procter

Use: hypnotic, sedative

RN: 77-04-3 MF: C,H,,NO, MW: 167.21 EINECS: 201-000-5

LD,,: 780 mgkg (R, p.0.)

CN: 3,3-diethyl-2,4(1 H,3H)-pyridinedione

methyl ethyl 2.2-diethyl- ethyl 2.2-diethyl-

formote ocetoocetate y-(hydroxymethy1ene)-

ocetoacetote

Trang 10

1

1760 P Pyritinol

Keference(s):

US 2 090 068 (Hoffmann-La Roche; 1937; D-prior 1935)

Trade Name(s):

D: Perscdon Roche (Roche): I: Hibersulfan (Ecobi)-comb.;

Pyritinol

(Pyrithioxine)

ATC: N06BX02 Use: neurotropic, nootropic RN: 1098-97-1 MF: C,,H20N20,S, MW: 368.48 EINECS: 214- 150- 1

CN: 3,3'-[dithiobis(methylene)]bis[5-hydroxy-6-methyl-4-pyridinemethanol]

dihydrochloride monohydrate

RN: 10049-83-9 MF: Cl6HmN2O4S2 2HCl H20 MW 459.42 EINECS: 233-178-5

LD,,,: 221 mg/kg (M, i.v.); 5786 mglkg (M, p.0.);

300 mglkg (R, i.v.); 6 g/kg (R, pa.)

3.4- bis(bromomethy1)-

5-hydroxy-6-methyl-

pyridine hydrobromide

(from pyridoxine)

potassium ethyl- xonthogenote

HO

Pyritinol

US 3 010 966 (E Merck AG; 28.1 1.1961; D-prior 21.3.1958)

DE 1 135 460 (E Merck AG; appl 21.3.1958)

DE 1 197 455 (E Merck AG; appl 27.8.1960)

alternative syntheses:

DAS 1 210 429 (E Merck AG; appl 3.8.1963)

DE 1 222 062 (E Merck AG; appl 8.2.1964)

DE 1 227 908 (E Merck AG; appl 8.2.1964)

DOS 1 695 402 (E Merck AG; appl 25.3.1967)

Fomulation(s): amp 200 mg; drg 100 mg, 200 mg; susp 80.5 mgf5 ml, 100 mg; syrup 100 mg (as

hydrochloride)

Trade Name(s):

D: Ardeyceryl P F: Biontabol (Merck- I: Encefabol (Bracco)

ClCvcnot); wfm Divalvdn (Nippon Kayaku)

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