PL145536B1 - Method of obtaining 2-chloro-1-/2-hydroxy-3-metoxy-propyl/-4-nitroimidazole - Google Patents

Method of obtaining 2-chloro-1-/2-hydroxy-3-metoxy-propyl/-4-nitroimidazole Download PDF

Info

Publication number
PL145536B1
PL145536B1 PL25588385A PL25588385A PL145536B1 PL 145536 B1 PL145536 B1 PL 145536B1 PL 25588385 A PL25588385 A PL 25588385A PL 25588385 A PL25588385 A PL 25588385A PL 145536 B1 PL145536 B1 PL 145536B1
Authority
PL
Poland
Prior art keywords
nitroimidazole
chloro
preparation
hydroxy
chro
Prior art date
Application number
PL25588385A
Other languages
Polish (pl)
Other versions
PL255883A1 (en
Inventor
Jerzy Suwinski
Ewa Salwinska
Krzysztof Walczak
Jan Watras
Maria Widel
Original Assignee
Politechnika Slaska Im Wincent
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Politechnika Slaska Im Wincent filed Critical Politechnika Slaska Im Wincent
Priority to PL25588385A priority Critical patent/PL145536B1/en
Publication of PL255883A1 publication Critical patent/PL255883A1/en
Publication of PL145536B1 publication Critical patent/PL145536B1/en

Links

Landscapes

  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Description

Przedmiotem wynalazku jest sposób otrzymywania 2-chloro-1-/2-hydroksy-3-metoksy- propylo/-*f-nitroimidazolu.Stwierdzono, ze mozna otrzymac nieznana dotad pochodna nitroimidazolu, a mianowi¬ cie 2-chloro-1-/2-hydroksy-3-metoksypropylo/-Jl-nitroimidazol o wzorze 1, nazywany w dal¬ szej tresci opisu preparatem P-40, która w odróznieniu od innych 4-nitroimidazoli charak¬ teryzuje sie wysoka zdolnoscia promieniouczulajaca w stosunku do niedotlenowanych komórek nowotworowych. Nitroimidazole sa jak dotad najefektywniejszymi preparatami promieniouczu- lajacymi# Niektóre 2-nitro i 5-nitroimidazole jak na przyklad misonidazol lub metronidazol sa juz stosowane w klinice promienio terapii nowotworów. Ograniczeniem w Stosowaniu-itroimi- dazoli zawierajacych grupy nitrowe w pozycjach 2 lub 5 jest ich wysoka toksycznosc w sto¬ sunku do komórek dobrze natlenowanych. Preparat P-40 pozbawiony jest tych wad.Sposób otrzymywania 2-chloro-1-/2-hydroksy-3-metoksypropylo/-4-nitroimidazolu o wzorze 19 nazywanego w opisie preparatem P-*lO, wedlug wynalazku polega na tym, ze 2,4/5/-dinitroimidazol poddaje sie reakcji z wrzacym stezonym kwasem solnym stosowanym w nadmiarze, a otrzymany 2-chloro-4/5/-nitroimidazol poddaje sie reakcji z /metoksymety- lo/oksiranem w obecnosci bezwodnego weglanu potasu w podwyzszonej temperaturze otrzymujac zwiazek o wzorze 1f który po oczyszczeniu przez krystalizacje mozna stosowac jako preparat promieniouczulajacy. Powyzsze reakcje przedstawia schemat.Zdolnosc promieniouczulajaca preparatu P-^O jest zblizona do zdolnosci promieni o- uczulajacej 2-nitroimidazoli np, misonidazolu. W stosunku do komórek czy tkanek dobrze natlenowanych preparat P-UO jest mniej toksyczny od misonidazolu czy raetronidazolu i po-2 1^5 536 dobnie jak te preparaty nie podnosi ich promieniowrazliwosci. Tak zwany wspólczynnik terapeutyczny preparatu P-*lO wynosi okolo 10, przewyzszajac znacznie wartosci od 2 do 3 uzyskiwane dla znanych preparatów promieniouczulajacych z grupy nitroimidazoli. Prepa¬ rat jest aktywny tak w warunkach in vitro jak in vivo.Ocena radiobiologiczna preparatu P-40: 1. V warunkach in vitro w stosunku do komórek V79-379A chomika chinskiego maksymalny wspólczynnik wzmozenia ER x =2.5 skutecznosc promieniouczulajaca C , =0.7 nM chroniczna cytotoksycznosc aerobowa C =7.0 mM wspólczynnik terapeutyczny C /O. ^ =10 2. W warunkach in vivo w stosunku do guzów szczurzych Rhabdomyosarcoma R1 /poczatkowa 3 srednia objetosc guzów 0.31 cm , ilosc szczurów w grupie 15-30 sztuky naswietlanie 15 x 370 radów 5 razy w tygodniu/ kontrola /tylko naswietlanie/ 4*l. 156 wyleczen 0.1 mg P-*lO na g wagi ciala 68. 8# wyleczen* 0.15 mg P-40 na g wagi ciala 83.3# wyleczen* * preparat P-*lO podawano dootrzewnowe* przed kazdym naswietlaniem Przyklad. 2,4/5/-Dinitroimidazol /79 gt °*5 mola/ ogrzewa sie do wrzenia przez 6 godzin ze 170 cm kwasu solnego o gestosci 1.16 g/cm . Otrzymana mieszanine chlo¬ dzi sie do temperatury okolo O C, odfiltrowuje wykrystalizowany osad, przemywa go woda i suszy w temperaturze do 100°C do stalej wagi uzyskujac 58-62 g /80-85#/2-chloro-V5/- nitroimidazolu topniejacego w temperaturze 219-220 C. Produkt ten bez dalszego oezysz- czania miesza sie z bezwodnym weglanem potasu /6 g/ i /metoksymetylo/oksiranem /225 cm , ok. 3 moli/. Otrzymana zawiesine ogrzewa sie przy mieszaniu w temperaturze 60 C przez k godziny. Nastepnie dodaje sie do niej 1 dcm wody destylowanej i calosc odparowuje pod cisnieniem zmniejszonym do 60 hPa na lazni wodnej o temperaturze okolo 70°C# Do po- zostalosci dodaje sie dwukrotnie po 0.8 denr wody destylowanej i kazdorazowo ponownie oddestylowuje pod zmniejszonym cisnieniem czesci lotne. Pólstala pozostalosc rozpuszcza sie w mozliwie malej objetosci wody destylowanej o temperaturze 70°Cf dodaje 2-3 g wegla aktywnego, miesza kilka minut i saczy. Przesacz chlodzi sie do temperatury 0°C i po 12 godzinach odsacza 50-60 g /53-62#/ chromatograficznie czystego bialego, krys¬ talicznego 2-chloro-1-/2-hydroksy-3-metoksypropylo/-*f-nitroimidazolu topniejacego w tem¬ peraturze 89-90°C nazywanego w tresci opisu preparatem P-*lO.Potencjal redukcji polarograficznej preparatu P-*fO mierzony w buforze Brittona- Robinsona o pH 7 wynosi -0.48.Y. W roztworze wodnym maksimum absorpcji preparatu w za¬ kresie UV przypada przy 310 nm. Wspólczynnik podzialu pomiedzy n-oktano 1 i wode wynosi 0.91.Zastrzezenie patentowe Sposób otrzymywania 2-chloro-1-/2-hydroksypropylo/-4-nitroimidazolu, znamienny tym, ze 2,4/5/-dinitroimidazol poddaje sie reakcji z wrzacym stezonym kwasem solnym stosowanym w nadmiarze, a otrzymany 2-chloro-**/5/-nitroimidazol poddaje sie reakcji z /metoksymetylo/oksiranem w obecnosci bezwodnego weglanu potasu w podwyzszonej temperaturze.1^5 536 OH CHi-CH-CHrO-CH, Q-a aN P-40.Hzór 1 *nA.|/ H Nv k,« HCl -NO, —-- H i Q,N tr A CH^-CH-CHrO-CH, KtCO, OH CHrCH-CHrO-CH$ Cr O.N schemat 1 PLThe subject of the invention is a method for the preparation of 2-chloro-1- (2-hydroxy-3-methoxy-propyl) - * p-nitroimidazole. It has been found that a so far unknown derivative of nitroimidazole can be obtained, namely 2-chloro-1- / 2 -hydroxy-3-methoxypropyl) -l-nitroimidazole of the formula (I), hereinafter referred to as the P-40 preparation, which, unlike other 4-nitroimidazoles, is characterized by a high radiosensitizing capacity towards hypoxic tumor cells. Nitroimidazoles are so far the most effective radiosensitizing preparations # Some 2-nitro and 5-nitroimidazoles, such as misonidazole or metronidazole, are already used in the clinic for radiotherapy cancer therapy. A limitation in the use of -itroimidazoles containing nitro groups in the 2 or 5 positions is their high toxicity to well-oxygenated cells. The P-40 preparation is devoid of these drawbacks. The method of obtaining 2-chloro-1- (2-hydroxy-3-methoxypropyl) -4-nitroimidazole of the formula 19, referred to in the description as the P- * 10 preparation, according to the invention consists in the fact that 2 , 4/5 / -dinitroimidazole is reacted with excess boiling concentrated hydrochloric acid and the resulting 2-chloro-4/5 / -nitroimidazole is reacted with / methoxymethyl / oxirane in the presence of anhydrous potassium carbonate at elevated temperature to give a compound of formula 1f which, after purification by crystallization, can be used as a radiation sensitizing preparation. The above reactions are presented in the diagram. The radiosensitizing capacity of the P- ^ O preparation is similar to the radiation sensitizing capacity of 2-nitroimidazoles, eg misonidazole. In relation to well-oxygenated cells or tissues, the P-UO preparation is less toxic than misonidazole or raetronidazole and also less toxic than these preparations do not increase their radiosensitivity. The so-called therapeutic factor of the P-* 10 preparation is about 10, significantly exceeding the values from 2 to 3 obtained for known radiosensitizers from the nitroimidazole group. The preparation is active both in vitro and in vivo. Radiobiological evaluation of P-40 preparation: 1. In in vitro conditions against Chinese hamster V79-379A cells, maximum ER enhancement factor x = 2.5 radiosensitizing efficiency C, = 0.7 nM chronic aerobic cytotoxicity C = 7.0 mM therapeutic factor C / O. ^ = 10 2. In vivo in relation to Rhabdomyosarcoma R1 rats tumors / initial 3, mean volume of tumors 0.31 cm, number of rats in the group 15-30 pieces irradiation 15 x 370 rad 5 times a week / control / only irradiation / 4 * l. 156 cures 0.1 mg P- * 10 per g body weight 68. 8 # cures * 0.15 mg P-40 per g body weight 83.3 # cures * * P- * 10 treatment was administered intraperitoneally * before each irradiation Example. 2.4 (5) -Dinitroimidazole (79 gt * 5 moles) is boiled for 6 hours with 170 cm of hydrochloric acid at a density of 1.16 g / cm. The obtained mixture is cooled to about 0 ° C, the crystallized precipitate is filtered off, washed with water and dried at a temperature of up to 100 ° C to a constant weight, yielding 58-62 g (80-85%) of 2-chloro-V5) -nitroimidazole melting in at 219-220 C. The product is mixed without further purification with anhydrous potassium carbonate (6 g) and (methoxymethyl) oxirane (225 cm, ca. 3 moles). The resulting suspension is heated with stirring at 60 ° C for k hours. Then 1 dcm of distilled water is added to it and the whole is evaporated under a pressure reduced to 60 hPa in a water bath at a temperature of about 70 ° C # The residue is added twice with 0.8 denier of distilled water and each time the volatile parts are distilled again under reduced pressure. The semi-solid residue is dissolved in the smallest possible volume of distilled water at the temperature of 70 ° Cf, 2-3 g of activated carbon are added, mixed for a few minutes and sucked. The filtrate is cooled to 0 ° C and, after 12 hours, 50-60 g (53-62%) of chromatographically pure white, crystalline 2-chloro-1- (2-hydroxy-3-methoxypropyl) - .f-nitroimidazole are filtered off. P-* 10 preparation melting at 89-90 ° C. The polarographic reduction potential of P-* fO preparation measured in Britton-Robinson buffer at pH 7 is -0.48.Y. In aqueous solution, the maximum absorption of the formulation in the UV range is at 310 nm. The partition coefficient between n-octane 1 and water is 0.91. Patent claim A method for the preparation of 2-chloro-1- (2-hydroxypropyl) -4-nitroimidazole, characterized in that 2,4 (5) -dinitroimidazole is reacted with boiling and concentrated hydrochloric acid used in excess, and the resulting 2-chloro - ** (5) -nitroimidazole is reacted with (methoxymethyl) oxirane in the presence of anhydrous potassium carbonate at elevated temperature. 1 ^ 5 536 OH CHi-CH-CHrO-CH, Qa aN P-40.Hor 1 * nA. | / H Nv k, «HCl -NO, —-- H i Q, N tr A CH ^ -CH-CHrO-CH, KtCO, OH CHrCH-CHrO-CH $ Cr ON diagram 1 PL

Claims (2)

Zastrzezenie patentowe 1. Sposób otrzymywania 2-chloro-1-/2-hydroksypropylo/-4-nitroimidazolu, znamienny tym, ze 2,4/5/-dinitroimidazol poddaje sie reakcji z wrzacym stezonym kwasem solnym stosowanym w nadmiarze, a otrzymanyClaim 1. A method for the preparation of 2-chloro-1- (2-hydroxypropyl) -4-nitroimidazole, characterized by reacting 2,4 (5) -dinitroimidazole with excess concentrated boiling hydrochloric acid and 2. -chloro-**/5/-nitroimidazol poddaje sie reakcji z /metoksymetylo/oksiranem w obecnosci bezwodnego weglanu potasu w podwyzszonej temperaturze.1^5 536 OH CHi-CH-CHrO-CH, Q-a aN P-40. Hzór 1 *nA.|/ H Nv k,« HCl -NO, —-- H i Q,N tr A CH^-CH-CHrO-CH, KtCO, OH CHrCH-CHrO-CH$ Cr O.N schemat 1 PL2.-Chloro ** (5'-nitroimidazole) is reacted with (methoxymethyl) oxirane in the presence of anhydrous potassium carbonate at elevated temperature. 1 ^ 5 536 OH CHi-CH-CHrO-CH, Q-a aN P-40. Hzor 1 * nA. | / H Nv k, «HCl -NO, —-- H i Q, N tr A CH ^ -CH-CHrO-CH, KtCO, OH CHrCH-CHrO-CH $ Cr O.N scheme 1 PL
PL25588385A 1985-10-21 1985-10-21 Method of obtaining 2-chloro-1-/2-hydroxy-3-metoxy-propyl/-4-nitroimidazole PL145536B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL25588385A PL145536B1 (en) 1985-10-21 1985-10-21 Method of obtaining 2-chloro-1-/2-hydroxy-3-metoxy-propyl/-4-nitroimidazole

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PL25588385A PL145536B1 (en) 1985-10-21 1985-10-21 Method of obtaining 2-chloro-1-/2-hydroxy-3-metoxy-propyl/-4-nitroimidazole

Publications (2)

Publication Number Publication Date
PL255883A1 PL255883A1 (en) 1987-05-04
PL145536B1 true PL145536B1 (en) 1988-09-30

Family

ID=20028707

Family Applications (1)

Application Number Title Priority Date Filing Date
PL25588385A PL145536B1 (en) 1985-10-21 1985-10-21 Method of obtaining 2-chloro-1-/2-hydroxy-3-metoxy-propyl/-4-nitroimidazole

Country Status (1)

Country Link
PL (1) PL145536B1 (en)

Also Published As

Publication number Publication date
PL255883A1 (en) 1987-05-04

Similar Documents

Publication Publication Date Title
US4169204A (en) Psoralens
DE69033414T2 (en) Tricyclic pteridinones and a process for their preparation
US5700825A (en) Radiosensitizing diamines and their pharmaceutical preparations
US4757148A (en) Intermediate 1-(2-nitro-1-imidazolyl)-3-substituted amino-2-propanols and the corresponding 2,3-butanediols
US4066650A (en) Keto-aldehyde-amine addition products and method of making same
DE3854645T2 (en) Nitro substituted aromatic and heteroaromatic compounds for cancer treatments.
PL145536B1 (en) Method of obtaining 2-chloro-1-/2-hydroxy-3-metoxy-propyl/-4-nitroimidazole
FI62089C (en) FREQUENCY REQUIREMENT FOR THE PERFORMANCE OF PERIPHERAL BLODOMLOPPET NETWORK 7- (N- (3-PHENOXY-2-HYDROXIPROPYL) -N-AMINO) -1,3-DIALKYL-XANTINDERIVAT
FI82451B (en) FOERFARANDE FOER FRAMSTAELLNING AV TERAPEUTISKT ANVAENDBARA KINOLINDERIVAT.
JP4598227B2 (en) Compounds that are sensitizers in radiation and chemotherapy and methods for their production and use
US3265574A (en) Method of enhancing the effect of X-ray and radium treatment
US4349546A (en) D-Allose derivative and preparation method therefor
US4314076A (en) Cystamine derivatives suitable for use as medicaments
JP2848602B2 (en) New fluorine-containing 2-nitroimidazole and radiosensitizer containing the same
WO2024108687A1 (en) Mitomycin c prodrug, and preparation method therefor and use thereof
DE4134224C2 (en) New 1-heterocyclylmethyl-3-nitro-1,2,4-triazoles
CN101309976B (en) High-purity texaphyrin metallic complex
Upadhyay et al. Studies on spiroheterocycles: Synthesis of new spiro-4-thiazolidinones as possible biodynamics
JPH0586791B2 (en)
CN113717226A (en) Heptamethine cyanine micromolecule compound containing diphosphonic acid structure, preparation method and application
JPH06298739A (en) Radiosensitizer for hypoxic cell
Fong et al. Synthesis of 1‐(2, 3‐dihydroxypropyl)‐2‐nitro‐1H‐imidazole‐2‐14C and N‐(2‐hydroxyethyl)‐2‐(2‐nitro‐1H‐imidazol‐1‐YL‐2‐14C) acetamide
JPS6212763A (en) Imidazole derivative
Mansfield et al. The search for new hypoxic cell radiosensitizers
JPS63170394A (en) 3-nitro-1,2,4-triazole derivative, preparation thereof and radiation sensitizer containing said derivative as active component