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AU611566B2 - New process for the preparation of n-(23-vinblastinoyl) derivatives of 1-amino-methyl-phosphonic acid - Google Patents
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AU611566B2 - New process for the preparation of n-(23-vinblastinoyl) derivatives of 1-amino-methyl-phosphonic acid - Google Patents

New process for the preparation of n-(23-vinblastinoyl) derivatives of 1-amino-methyl-phosphonic acid Download PDF

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Publication number
AU611566B2
AU611566B2 AU36200/89A AU3620089A AU611566B2 AU 611566 B2 AU611566 B2 AU 611566B2 AU 36200/89 A AU36200/89 A AU 36200/89A AU 3620089 A AU3620089 A AU 3620089A AU 611566 B2 AU611566 B2 AU 611566B2
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Australia
Prior art keywords
radical
general formula
carbon atoms
formula
derivatives
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AU36200/89A
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AU3620089A (en
Inventor
Patrick Hautefaye
Gilbert Lavielle
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ADIR SARL
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ADIR SARL
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/547Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6561Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)

Description

COMMONWEALTH OF AUSTRALIA An~ Fr PATENTS ACT 1952-69 COMPLETE SPECIFICATION
(ORIGINAL)
Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Int. Class IVr~rity: *Relted Art: *0 0 0 fanje of Applicant: Address of Applicant: ADIR ET COMPAGNIE 22 Rue Garmier, F-92201 Neuilly Sur Seine, France Actual Inventor: GILBERT LAVIELLE and PATRICK HAUTEFAYE 5.
S
Address for Service =WWW~iX VWatermark Patent Trademark Attorneys 50 QUEEN STREET, MELBOURNE, AUSTRALIA, 3000.
Complete Specification for the invention entitled: NEW PROCESS FOR THE PREPARATION OF N-(23-VINBLASTINOYL) DERIVATIVES OF 1-AMINO-METHYL-PHOSPHONIC ACID The following statement is a full description of this invention, including the best method of performing it known to us 1 00 a 4 00 0 0
*.S
S.
S
'4 SO0 -4 5 744 The present invention relates to a new process for preparing N-(23-vinblastinoyl) derivatives of 1aminomethylphosphonic acid.
Some N-(23-vinblastinoyl) derivatives of 1aminomethylphosphonic acid are described in French Patent Application No. 87/16,327. The compounds claimed possess much greater antitumor activity than all known vinblastine derivatives. According to the preparation process described in the application referred to above, the bisindole derivatives are obtained by condensation of the appropriate aminophosphonates with 3-decarbomethoxy-4-0deacetylvinblastine-3-carboxazide. This azide is prepared from vinblastine by hydrazinolysis followed by nitrosation, which necessitates the use of anhydrous hydrazine, 15 a very dangerous and toxic reagent.
Belgian Patent No. 904,064 describes a process for preparing some N-(23-vinblastinoyl) derivatives of aminoacids and peptides by the mixed anhydride method.
However, this process is of little industrial importance, 20 since it necessitates at least two separate preparation stages.
The Applicant has now discovered a new process for preparing N-(23-vinblastinoyl) derivatives of 1aminomethylphosphonic acid which is very advantageous 25 compared with the already known processes.
In effect, this process enables the derivatives of general formula I to be obtained from vinblastinoic acid in a single stage and in good yield, and the reagents used are commercially available, inexpensive and easy to handle.
The subject of the invention is, more precisely, a process for preparing the derivatives of general formula I, 2 8' 7' a S. S .a a S a
S~
CO NH -CH 23 /ORi
P
l\O 0 in which: RI denotes a hydrogen atom, a linear or branched alkyl radical containing from 1 to 6 carbon atoms, a linear or branched alkylene radical containing from 1 to 6 carbon atoms, an arylalkyl radical having 7 to carbon atoms which can bear as a substituent on the aromatic ring a halogen atom, a hydroxyl radical or an alkyl or alkoxy radical each containing from 1 to carbon atoms, a 2-indolylmethyl radical, a 4-imidazolylmethyl radical or an alkoxycarbonylmethyl radical containing from 3 to 11 carbon atoms, and
R
2 and R 3 which may be identical or different, each denote a linear or branched alkyl radical containing from 1 to 6 carbon atoms, wherein vinblastinoic acid, the compound of formula II
U
-3 71 OH 12' 6 Y io I 0' 10
(II)
CO OH 23 a. a a a.
a a a. a.
a a a a a a a.
a a a.
a a a. a is condensed with N,N'-carbonyldiimidazole, the compound of formula III: N N -N
(III)
at room temperature, in an anhydrous polar solvent such as dimethylformamide and under an inert atmosphere, then wherein an aminopho sphonate of general formula
IV:
SOR 2 R-CH P 1 11-OR 3 NH, 0
(IV)
in which R 1
R
2 and R, have the same meaning as that stated in the formula I, is introduced to react in the reaction medium, and thereafter, wherein the medium is hydrolyzed with distilled 4 water and wherein the expected compouunds of general formula I are extracted by means of a chlorinated hydrocarbon such as dichloromethane.
Vinblastinoic acid, the compound of formula II may be prepared according to the method described in French Patent Application No. 75/31,159.
N,N'-Carbonyldiimidazole is a commercially available product (Aldrich®).
The compounds of general formula IV are prepared according to the methods described in French Patent Application No. 87/16,327.
According to the process of the invention, the 15 compounds of formula I are obtained in the form of free bases.
bTo form addition salts of the compounds of general formula I, pharmaceutical acceptable organic or inorganic acids may be used. Among these acids, hydro- 99 chloric, phosphoric, fumaric, citric, oxalic, sulfuric, tartaric, maleic and methanesulfonic acids, and the like, may be mentioned.
The examples which follow, given without implied limitation, illustrate the invention.
The melting points stated are measured according to the micro-Kofler technique.
The mass spectra (F A B+ and F A are obtained with a NERMAG® 10-10C mass spectrometer with a quadripole filter.
Matrix: mixture of glycerol and thioglycerol (50:50 v/v).
Incident gas: krypton Energy: 6 to 8 keV.
EXAMPLE 1 Diethyl 4-O-deacet'.-23-vinblastinoyl) aminomethylphosphonate mg of N,N'-carbonyldiimidazole are added under argon to a solution of 100 mg of vinblastinoic acid in I_ 5 ml of anhydrous dimethylformamide. The mixture is stirred for one hour at room temperature before a solution of 100 mg of diethyl aminomethylphosphonate in 1 ml of anhydrous dimethylformamide is added. The mixture is kept stirred at room temperature and under argon for 24 hours. The medium is hydrolyzed by means of 25 ml of distilled water and the product extracted by means of 3 times 25 ml of dichloromethane. The organic phases are combined, washed once with saline solution and once with water and dried over anhydrous magnesium sulfate.
After evaporation of the solvent, the residue is purified by colimn chromatography, using 170 g of Lichrosorb RP 18 (Merck®) as the stationary phase and a mixture of methanol and 0.01 M disodium phosphate (70:30 15 v/v) as the elution solvent.
~Yield: 50 Diethyl N-(4-O-deacetyl-23-vinblastinoyl)aminomethylphosphonate sulfate was obtained after adding 2 ~strength ethanolic sulfuric acid.
Melting point: 194-204 0 C (decomposition).
Mass spectrum, FAB+ 904 651, 562, 550, 355.
EXAMPLE 2 Diethyl N-(4-O-deacetyl-23-vinblastinoyl)-1- 25 amino-2-methylpropylphosphonate This compound was prepared according to the process described in Example 1, but using diethyl 1amino-2-methylpropylphosphonate instead of diethyl aminomethyl phosphonate.
The product derived from the reaction was purified, after evaporation of the solvent, on a chromatographic column, using silica (230-400 mesh) as the stationary phase and a mixture of toluene and ethanol as the elution solvent.
Yield: 35 Mass spectrum, FAB 946 709, 651.
Mass spectrum, FAB- 944 926, 916, 806, 180, 152, 137, 108.

Claims (2)

1. A process for preparing the derivatives of general formula I OH 11 8 7 12 6' N 21 13 18' CH30 8 7 14* 6 IH 5 12 5 2j 0HH CH3 R I CO NH CH S* in which: 6 carbon atoms, an arylalkyl radical having 7 to Scarbon atoms which can bear as a substituent on the aromatic ring a halogen atom, a hydroxyl radical or an alkyl or alkoxy radical each containing from 1 to carbon atoms, a 2-indolylmethyl radical, a 4-imidazolyl- methyl radical or an alkoxycarbonylmethyl radical con- taining from 3 to 11 carbon atoms, and R2 and Ratoms which may be identical or diffsubstitu erent, I- i Iriilllili "i ~r i;~iii i i 7 each denote a linear or branched alkyl radical containing from 1 to 6 carbon atoms, wherein vinblastinoic acid, the compound of formula II 8' 7' (II) 4* a a a 4 4 a 4 4 4 4 S. 4 4«
4. 44 9D 0 CO OH 23 is condensed with N,N'-carbonyldiimidazole, the compound of formula III: N N-C -N 0 (III) at room temperature, in an anhydrous polar solvent and under an inert atmosphere, then wherein an aminophosponate of general formula IV: 8 OR 2 RI-CH- P (IV) I 11'"OR3 NH 2 0 in which R 1 R 2 and R, have the same meaning as that stated in the formula I, is introduced to react in the reaction medium, and thereafter, wherein the medium is hydrolyzed with distilled water and wherein the expected compounds of general formula 10 I are extracted by means of a chlorinated hydrocarbon. 2. The process as claimed in claim 1, wherein the condensation of vinblastinoic acid with N,N'-carbonyl- *C diimidazole and an aminophosphonate of general formula IV, as claimed in claim 1, is carried out under an inert atmosphere in the presence of argon. 3. The process as claimed in claim 1, wherein the condensation of vinblastinoic acid with N,N'-carbonyl- diimidazole and an aminophosphonate of general formula IV, as claimnjd in claim 1, is carried out in a single stage. 4. The process as claimed in claim 1, wherein the condensation of vinblastinoic acid with N,N'-carbonyl- diimidazole and an aminophosphonate of general formula IV, as claimed in claim 1, is carried out in dimethyl- formamide. DATED this 8th day of June 1988 ADIR ET COMPAGNIE WATERMARK PATENT TRADEMARK ATTORNEYS QUEEN STREET MELBOURNE. VIC. 3000.
AU36200/89A 1988-06-10 1989-06-09 New process for the preparation of n-(23-vinblastinoyl) derivatives of 1-amino-methyl-phosphonic acid Ceased AU611566B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8807742 1988-06-10
FR8807742A FR2632643B1 (en) 1988-06-10 1988-06-10 NOVEL PROCESS FOR THE PREPARATION OF N- (VINBLASTINOYL-23) DERIVATIVES OF 1-AMINO METHYLPHOSPHONIC ACID

Publications (2)

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AU3620089A AU3620089A (en) 1989-12-14
AU611566B2 true AU611566B2 (en) 1991-06-13

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AU36200/89A Ceased AU611566B2 (en) 1988-06-10 1989-06-09 New process for the preparation of n-(23-vinblastinoyl) derivatives of 1-amino-methyl-phosphonic acid

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EP (1) EP0346235A1 (en)
JP (1) JPH0236187A (en)
AU (1) AU611566B2 (en)
DK (1) DK284789A (en)
FR (1) FR2632643B1 (en)
NZ (1) NZ229479A (en)
OA (1) OA09421A (en)
PT (1) PT90807A (en)
ZA (1) ZA894386B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2672287B1 (en) * 1991-01-31 1994-07-22 Adir NEW INDUSTRIAL PROCESS FOR THE PREPARATION OF N- (DESACETYL-O-4 VINBLASTINOYL-23) AMINO-1 METHYL-2 PROETYLPHOSPHONATE (1S) AND ITS SALTS.
US5473092A (en) * 1992-11-20 1995-12-05 Monsanto Company Synthesis of optically-active phosphono analogs of succinates
FR2905949B1 (en) * 2006-09-20 2008-11-21 Pierre Fabre Medicament Sa FLUORINE DERIVATIVES OF CATHARANTHIN, PREPARATION THEREOF AND THEIR USE AS PRECURSORS OF ALKALOIDS DIMERES DE VINCA

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU607554B2 (en) * 1987-11-25 1991-03-07 Les Laboratoires Servier New n-(23-vinblastinoyl) derivatives of 1-aminomethyl- phosphonic acid, processes for preparing them and pharmaceutical compositions containing them

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JPS56125335A (en) * 1980-03-06 1981-10-01 Fujisawa Pharmaceut Co Ltd 1,4-naphthoquinone derivative, its preparation, and its use

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU607554B2 (en) * 1987-11-25 1991-03-07 Les Laboratoires Servier New n-(23-vinblastinoyl) derivatives of 1-aminomethyl- phosphonic acid, processes for preparing them and pharmaceutical compositions containing them

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PT90807A (en) 1989-12-29
ZA894386B (en) 1990-02-28
NZ229479A (en) 1990-12-21
JPH0236187A (en) 1990-02-06
DK284789D0 (en) 1989-06-09
EP0346235A1 (en) 1989-12-13
OA09421A (en) 1992-10-15
AU3620089A (en) 1989-12-14
FR2632643B1 (en) 1990-09-07
FR2632643A1 (en) 1989-12-15
DK284789A (en) 1989-12-11

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