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Pharmaceutical Substances Syntheses, Patents, Applications - Part 213 ppsx

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25 mg, 100 mg as maleate Trade Names: D: Hexphonal ASTA Medica F: Surmontll Specia Surmontil RhBne-Poulcnc Rorer I: Surmontil RhBne-Poulenc USA: Surmont~l Wyeth-Ayerst Trimipramin-neur

Trang 1

Trimipramine T 21 21

Reference(s):

GB 1 345 502 (Parke Davis & Co.; appl 6.7.1972; GB-prior 6.7.1972)

EP 5 145 (Warner-Lambert Co.; appl 26.10.198 1; USA-prior 29.1.1982)

lyophilic formulation:

JP06 172 177 (Dainippon Pharm.; appl 10.12.1992; J-prior 10.12.1992)

Formulation(s): vial 25 mg

Trade Nume(s):

F: Neutrexin (IpsedBiotech) I: Neutrexin (lpsen)

GB: Neutrexin (Speywood) USA: Ncutrexin (US Bioscience)

Use: antidepressant RN: 739-7 1-9 MF: CzoHz6Nz MW: 294.44 EINECS: 212-008-3

LD,,: 42 mglkg (M, i.v.); 250 mgtkg (M, p.0.)

CN: 10.1 1 -dihydr0-N,N,~-trimethyl-5H-dibenz[b,,flaze~inc-5-~ropanamine

maleate (1:l)

RN: 521-78-8 MF: CX,Hz6N2 C4H404 MW: 410.51 EINECS: 208-318-3

LD,: 40 m g k g (M, i.v.); 425 rngtkg (M, p.0.);

38 mglkg (R, i.v.); 800 mglkg (R, p.0.)

monomesylate

RN: 25332-1 3-2 MF: C2,,H2,N2 CH403S MW: 390.55 EINECS: 246-852-9

2-methylpropyl 10,ll-dihydra-SH- chloride Trimipramine

dibenz[b.f]ozepine

Reference(s):

FR 1 172 014 (RhGne-Poulcnc; appl 14.12.l955)

Jacob, R.M.; Messer, M.: C R Hebd Seances Acad Sci (COREAF) 252, 21 17 (1961)

Formulation(s): amp 25 mglml; cps 25 mg, 5 0 mg, 100 mg; drops 5.3 g1100 ml (as monomesylate); f c tab1

25 mg; tabl 25 mg, 100 mg (as maleate)

Trade Name(s):

D: Hexphonal (ASTA Medica F: Surmontll (Specia) Surmontil (RhBne-Poulcnc

Rorer) I: Surmontil (RhBne-Poulenc USA: Surmont~l (Wyeth-Ayerst) Trimipramin-neuraxpharm Rorer)

(neuraxpharm)

Trang 2

2122 T Tripamide

Use: antihypertensive, diuretic RN: 73803-48-2 MF: C,,H20C1N,0,S MW: 369.87

LD,,,: > 5 glkg (M, p.0.);

28 gikg (R, p.0.);

22 gikg (dog, p.o.1

CN: (3aol,4a,7a,7acr)-3-(aminosulfonyl)-4-chloro-N-(octahydro-4,7-methano-2H-isoindol-2-yl)benzamide

1 chlorosul- n thionyl

4-chlorobenzoic

acid

u - '

N H 2 4-chlaro-3-sulf- ornoylbenzoic acid

1 NoN02

2 Zn, CHJCOOH

endo-hexo-

hydro-6,7-

methono-

isoindoline

Reference(s):

2-omino-endo- hexohydro-6.7- rnethonoiso- indoline

4-chloro-3-suli arnoylbenzoyl chloride (I)

oQ%

Tripomide N H 2

US 3 787 440 (Eisai; 22.1.1974; appl 9.1 1.1971; J-prior 9.1 1.1970)

DOS 2 155 660 (Eisai; appl 9.1 1.197 1; J-prior 9.1 1.1970)

Nakamura, T ct al.: J Labelled Compd Radiopharm (JLCRD4) 14, 191 (1978)

JP 7 121 708 (Eisaei; appl 17.8.1967)

Fqrmulation(s); tabl 15 mg

Trade Name(s):

J: Normonal (Eisai; 1982)

Use: antihistaminic RN: 91-81-6 MF: C,,H,,N, MW: 255.37 EINECS: 202-100-1

LD,,,: 23 mglkg (M, i.v.); 152 mglkg (M, p.0.)

CN: N,N-dimethyl-N-(phenylmethy1)-N'-2-pyridiny- 1,2-ethanediamine

monohy drochloride

RN: 154-69-8 MF: CI,H2,N3 HCI MW: 291.83 EINECS: 205-833-5

LD,,,: 9 mglkg (M, i.v.); 97 mglkg (M, p.0.);

12 mglkg (R, i.v.); 469 mglkg (R, p.0.)

Trang 3

Triprolidine T 2123

2-benzylomino- 2-(dimethylamino)- I Tripelennomine I

pyridine ethyl chloride

Reference(s):

US 2 406 594 (Ciba; 1946; prior 1943)

US 2 502 151 (Rhhe-Poulenc; 1950; F-prior 1943)

Formulation(s): stick 115 mg15.75 g (as hydrochloride)

Trade Name(s):

D: Azaron Stift (Chefaro) I: Sedilene (Montefarmaco); USA:

F: Anachoc (Lipha)-comb.; wfm

Takeda)

PBZ-SR (Geigy); wfm Pyribenzamine (Ciba); wfrn Tripelennamine HCI Tablets (Danbury); wfm

Use: antihistaminic RN: 486-12-4 MF: ClYHz2N2 MW 278.40 EINECS: 207-627-0

CN: (E)-2-[1-(4-methylphenyl)-3-(1-pyrrolidinyl)-1-propenyl]pyridine

monohydroshloride

RN: 550-70-9 MF: C, yH22N2 HCI MW: 3 14.86 EINECS: 208-985-0

LDso: 21 mglkg (M, i.v.); 495 mglkg (M, p.0.);

840 mglkg (R, p.0.)

u

UcH, 2 2-"0-0-

ovridine

, ,

4'-methyl- paraform- pyrrolidine 4'-methyl-3-

acetophenone aldehyde pyrrolidino-

propiophenone

Q seporation

by ion exchanger

-

C H 3 C H 3

Triprolidine

u

Reference(s):

US 2 712 020 (Burroughs Wellcome; 1955; GB-prior 1948)

US 2 712 023 (Burroughs Wellcome; 1955; GB-prior 1948)

Formulation(s): syrup 1.25 mg15 ml; tabl 1.25 mg, 2.5 mg (as hydrochloride)

Trang 4

2124 T Tritoaualine

Trade Name(s):

F: Actifed (Warner-Lambert) Pro-Entra (Wellcome-

GB: Sudafed (Warner-Lambert)- Tanabe)

Use: antiallergic RN: 14504-73-5 MF: CxH,,N108 MW: 500.55

LD,,,: > I 5 glkg (M, p.0.);

> I 5 glkg (R p.0.)

CN: 7-amino-4,5,6-triethoxy-3-(5,6,7,8-tetrahydro-4-methoxy-6-methyl-1,3-dioxolo[4,5-g]isoquinolin-5-yl)-

l(3 H)-isobenzofuranone

cotornine 7-nitro-4.5.6-tri-

ethoxyphthalide

Tritoqualine

Reference(s):

DE 1 206 909 (M Jeanson, Paris; appl 14.8.1959)

Formulation(s); drops 180 mg; tabl 100 mg

Trade Narnefs):

D: Inhibostamin (Swiss- Inhibostarnin (Zyma); wtm I: Hypostamin (SIT); wfm

Pharma); wfm F: Hypostamine (Promedica) Hypostarnine (Zyma); wfm

Trofosfamide

(Trophosphamide)

ATC: LOIAA07 Use: antineoplastic RN: 22089-22-1 MF: C,Hr,C13N,0,P MW: 323.59 EINECS: 244-770-8

LD,,,: 157 mglkg (M, i.v.); 464 mg/kg (M, p.0.);

9 0 m g k g (R, i.v.); 202 mglkg (R, p.0.)

CN: N,N,3-tris(2-chloroethyl)tetrahydro-2H-1,3,2-oxazaphosphorin-2-amine 2-oxide

Trang 5

Troglitazone T 2125

OH HCI +

CI, 1

/ $0

C I amine

N-(2-chlor0ethyl)-3- N,N-bis(2-chloro-

hydroxypropylarnine ethyl)phasphorarnidic

hydrochloride dichloride

Reference(s):

DOS 1 645 921 (ASTA-Werke; appl 1 1.7.1966)

GB 1 188 159 (ASTA-Werke; appl 11.7.1967; D-prior 11.7.1966)

US 3 732 340 (ASTA-Werke; 8.5.1973; prior 30.6.1967, 11.9.1970, 14.1.1971)

for mu lab ion(.^): f c tabl 50 mg

Trade Namc(s):

D: Ixoten (ASTA Medica I: Ixoten (Schering); wfm

AW D)

Troglitazone

(CI-991; CS 045; GR-92 132X)

ATC: AlOBGOl Use: antidiabetic, insulin enhancer, antioxidant

RN: 97322-87-7 MF: C,H2,N05S MW: 441.55

LD,: > 5 g k g (R, p.0.)

CN: 5-[[4-(3,4-dihydro-6-hydroxy-2,5,7,8-tetramethyl-2-1-benzopyran-2-yl)methoxy]phenyl]methyl-2,4-

thiazolidinedione

monosodium saIt

RN: 97323-06-3 MF: C,H,NNaO, MW: 431.46

CI.-.o/CH3

H 3 C w O H LiAIH4, H * Z H A NaH, THF III

HO HO rnethoxymethyl

(+)-6-hydroxy-2.5,7.8- (+)-6-h~droxy-2.5.7.8-

letromethylchroman-2- tstrarnethylchrornon-

corboxylic acid (I) 2-ylrnethonol (+)-(I()

CH3 CH3 NOH, DMF

H A0 , 0 CI '

(11') p-chloronitro-

benzene

(+)-6-(rnethoxyrnethoxy)-

2.5.7.8-tetrarnethyl-2-

(4-nitrophenoxyrnethyl)-

chrornon (N)

Trang 6

2126 T Troglitazone

tetromethylchromon (VI)

1 NoN02, H20,

HCI, ocetone

2 HZC'+OvC"3

0

CupO 40 O C

VI _*

2 ethyl acrylote

CH3

NoOH C2H50H THF

2.5.7.8-tetromethylchromon-2-yl)- rnethoxy]phenyl]prapionic acid (vIU)

@ starting material I: I K2C03

2 H3C-Li

1 sulfolane 120 "C

VIII

2,3,5-trimethyl-

hydroquinone (M)

thiourea

5'.4',6' trimethyl- 2'3'-dihydroxy- ocetophenone (X)

CH3

Troglitazone

ethyl 6-hydroxy-5.7.8- trimethyl-4-0x0-4H-

Trang 7

Troglitazone T 2127

1 HZ Pd-C DMF

2 Clr\O/CH3 ,

NOH, THF

3 H~C-L~ ,H3C 1 H 3 c w, 0 n c H 3

'0-0

methyl vinyl

ketane

2 V , pyridine

H3C

6-hydroxy-2-methoxy-

2,5,7,8-tetramethyl-

chromane (XI)

1 OMF

2 HCI 90 O C

4-bromo-3-methyl- 2-butenyl acetote (XN)

XIV

HO H c K ??

0

4-(p-nitrophenoxy)-3- methyl-2-butenyl ocetate (XV)

Trang 8

2128 T Troglitazone

2-i4-(p-nitrophenoxy)-3-

methyl-2-butenyll-3,5.6-

trirnethylhydroquinone (XVI)

+

Q^" CH,

CH3

(unprotected N)

triphenylphosphine

piperidine

2-methoxyethanol

0

phenoxyrnathyl)-2.5.7.8- dinedione

tetrornethylchrornan (XVII)

H, Pd-C

5-[4-(6-benzyloxy-2,5,7,8-tetro-

rnethylchrornon-2-ylrnethoxy)-

benzylideneJ-2.4-thiazolidine-

dione (XVIII)

@ olternative synthesis of VI:

.I

u * A

+ H 3 C r 0 - - 7 + M X pyrrol~dtne

5'-ocetoxy-2'-hydrony-

3.4'6-trimethyi-

ocetophenone

1 NaBH,, C H P H

J N

0 2 Tos-OH, benzene

3 Hz Pd-C CHJOH

CH30

6-acetoxy-2.5.7.8-tetromethyl-

2-(4-nitrophenoxyrnethy1)-

Trang 9

Troglitazone T 2129

@ intermediate 11:

s-collidine, -40°C

CH3S,CH3

1 H, Pd

2 HCI

2-methyl-2- viny loxirane

Trang 10

1

2130 T Trolnitrate

Re-ferencr(sJ:

a Yoshioka, T et a].: J Med Chem (JMCMAR) 32, 421 (1989)

EP 207 581 (Sankyo Co.; appl 26.2.1986; J-prior 26.2.1985)

aa Witiak, D.T et al.: J Med Chem (JMCMAR) 18 (9), 934 (1975)

EP 139 421 (Sankyo Co.; appl 28.8.1984; prior 30.8.1983)

US 4 572 912 (Sankyo; 25.2.1986, J-prior 30.8.1983)

ab Scott, J.W et al.: J Am Chem Soc (JACSAT) 51,200 (1974)

b EP 670 300 (Eisai Chem Co.; appl 1.3.1995; J-prior 2.3.1994)

EP 543 346 (LonzatSankyo; appl 17.1 1.1992; CH-prior 20.1 1.1991)

c EP454 501 (Sankyo Co.; appl 29.4.1991; J-prior 27.4.1990)

ea DE 3 010 504 (BASF AG; appl 19.3.1980)

eb JP 08 1 19 958 (Kwaray Co.; appl 18.10.1994)

JP 08 119 957 (Kwaray Co.; appl 18.10.1994)

ec JP 01 068 366 (Eisai Co.; appl 9.9.1987)

ed Tanabe, K et al.: Chem Lett (CMLTAG) 5,561 (1985)

ef Sakito, Y et al.: Tetrahedron Lett (TELEAY) 23 (47), 4953 (1982)

EP 65 368 (Sumitorno Chem.; appl 28.4.1982; J-prior 30.4.1981)

kinetic resolution of intermediate 11:

Hyatt, J.A.; Skelton, C.: Tetrahedron: Asymmetry (TASYE3) 8 (4), 523 (1997)

preparation of (+)-enantiomer by yeast reductase:

WO 9 310 254 (SmithKline Beecham; appl 19.11.1992; GB-prior 19.11.1991)

Formularion(s): tabl 100 mg, 200 mg, 300 mg, 400 mg

Trade Nume(s):

Warner-Lambert); wfm

1 Jse: coronary vasodilator RN: 7077.34- 1 MF: C,H,,N40, MW: 284.18 EINECS: 230-376-3

CN: 2,2',2"-nitrilotrisethanol trinitrate (ester)

diphosphate

RN: 588-42- 1 MF: C,H,,N@, 2H3P04 MW: 480.17 EINECS; 209-61 7- 1

LD,,,: lOOmg/kg(M,i.v.); 330mg/kg(M,p.o.);

130 mgkg (R, p.0.)

triethanalarnine

Rejerence(s):

FR 984 523 (J Metadier; appl 1949)

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