合成路线1
该中间体在本合成路线中的序号:
(I) Treatment of cyclopentylamine (I) with potassium trichloroaminoplatinate and potassium iodide in H2O provides a mixture of platinum complexes (II) and (III), which is then subjected to reaction with silver (S)-(-)-malate (IV) in H2O to furnish the desired platinum complex.
【1】
Cheltsov-Bebutov, P.A.; Kravchenko, A.N.; Schelokov, R.N.; Konovalova, A.L.; Presnov, M.A.; Ivanov, V.B. (Inst. Obs. Neorg. Khim. Imeni; Vse. Onkol. Nauch. Tsentr Ak.); Carboxylatoplatinum(II) complexes and process for their preparation. FR 2563524 . |
中间体序号 |
中间体编号 |
品名 |
CAS号 |
分子式 |
供应商 |
用于合成 |
(I) |
28850 |
cyclopentanamine
|
1003-03-8 |
C5H11N |
详情 | 详情
|
(II) |
50818 |
platinum(2+) chloride iodide cyclopentanamine ammoniate
|
|
C5H14ClIN2Pt |
详情 |
详情
|
(III) |
50820 |
|
|
C5H14I2N2Pt |
详情 |
详情
|
(IV) |
50819 |
|
|
C4H4AgO5 |
详情 |
详情
|
合成路线2
该中间体在本合成路线中的序号:
(I) The reaction of cyclopentylamine (I) with tertbutyl bromoacetate (II) by means of NH3 in acetonitrile gives N-cyclopentylglycine tert-butyl ester (III), which is condensed with 3-(acetylthio)-2-methylpropionyl chloride (IV) [prepared from the corresponding acid (V) with SOCl2] by means of triethylamine in dioxane to yield the acylated glycine (VI). Deacetylation of (VI) with dry ammonia in methanol affords the mercapto derivative (VII), which is acylated with pivaloyl chloride (VIII) in the usual way giving the corresponding thio ester (IX). Finally, this compound is hydrolyzed partially with trimethylsilyl iodide in methylene chloride.
【1】
Suh, J.T.; et al.; Angiotensin-converting enzyme inhibitors. New orraly active antihypertensive (mercaptoalkanoyl)- and [(acylthio)alkanoyl]glycine derivatives. J Med Chem 1985, 28, 1, 57-66.
|
【2】
Castaner, J.; Serradell, M.N.; Pivopril. Drugs Fut 1986, 11, 2, 116.
|
中间体序号 |
中间体编号 |
品名 |
CAS号 |
分子式 |
供应商 |
用于合成 |
(I) |
28850 |
cyclopentanamine
|
1003-03-8 |
C5H11N |
详情 | 详情
|
(II) |
17430 |
2-Bromoacetic acid tert-butyl ester; tert-butyl 2-bromoacetate; tert-Butyl bromoacetate
|
5292-43-3 |
C6H11BrO2 |
详情 | 详情
|
(III) |
28851 |
tert-butyl 2-(cyclopentylamino)acetate
|
|
C11H21NO2 |
详情 |
详情
|
(IV) |
28852 |
(2R)-3-Acetylthio-2-methylpropionyl chloride;L-3-(Acetylthio)-2-methylpropanoyl chloride ;S-[(2R)-3-chloro-2-methyl-3-oxopropyl] ethanethioate |
74345-73-6 |
C6H9ClO2S |
详情 | 详情
|
(V) |
28853 |
(2R)-3-(acetylsulfanyl)-2-methylpropionic acid;(R)-3-(acetylthio)-2-methylpropanoic acid |
74431-52-0 |
C6H10O3S |
详情 | 详情
|
(VI) |
28854 |
tert-butyl 2-[[(2S)-3-(acetylsulfanyl)-2-methylpropanoyl](cyclopentyl)amino]acetate
|
|
C17H29NO4S |
详情 |
详情
|
(VII) |
28855 |
tert-butyl 2-[cyclopentyl[(2S)-2-methyl-3-sulfanylpropanoyl]amino]acetate
|
|
C15H27NO3S |
详情 |
详情
|
(VIII) |
13597 |
2,2-Dimethylpropanoyl chloride; Pivaloyl chloride
|
3282-30-2 |
C5H9ClO |
详情 | 详情
|
(IX) |
28856 |
tert-butyl 2-(cyclopentyl[(2S)-3-[(2,2-dimethylpropanoyl)sulfanyl]-2-methylpropanoyl]amino)acetate
|
|
C20H35NO4S |
详情 |
详情
|
合成路线3
该中间体在本合成路线中的序号:
(II) Treatment of 2,4-difluoronitrobenzene (I) with cyclopentylamine (II) in the presence of K2CO3 in THF afforded 2-cyclopentylamino-4-fluoronitrobenzene (III). Subsequent condensation of (III) with 2-fluorophenylacetonitrile (IV) by means of potassium tert-butoxide, followed by oxidative treatment of the intermediate nitrile (V) with H2O2 generated benzophenone (VI). The nitro group of (VI) was then reduced by hydrogenation over Raney Nickel yielding diamine (VII), which was cyclized to benzimidazole (VIII) upon treatment with cyanogen bromide. Addition of the lithium anion of N-methyl-N-(trimethylsilyl)acetamide to (VIII) gave beta-hydroxyamide (IX). Finally, acid promoted dehydration of (IX) furnished the corresponding alpha,beta-unsaturated amide, whic was isolated as the hydrochloride salt.
【1】
Jungheim, L.N.; Shepherd, T.A.; Spitzer, W.A.; Tebbe, M.J. (Eli Lilly and Company); Anti-viral cpds.. EP 0906097; WO 9746237 .
|
中间体序号 |
中间体编号 |
品名 |
CAS号 |
分子式 |
供应商 |
用于合成 |
(I) |
32036 |
2,4-difluoro-1-nitrobenzene
|
446-35-5 |
C6H3F2NO2 |
详情 | 详情
|
(II) |
28850 |
cyclopentanamine
|
1003-03-8 |
C5H11N |
详情 | 详情
|
(III) |
37895 |
N-cyclopentyl-N-(5-fluoro-2-nitrophenyl)amine; N-cyclopentyl-5-fluoro-2-nitroaniline
|
|
C11H13FN2O2 |
详情 |
详情
|
(IV) |
37888 |
2-(2,3-difluorophenyl)acetonitrile
|
145689-34-5 |
C8H5F2N |
详情 | 详情
|
(V) |
37896 |
2-[3-(cyclopentylamino)-4-nitrophenyl]-2-(2-fluorophenyl)acetonitrile
|
|
C19H18FN3O2 |
详情 |
详情
|
(VI) |
37897 |
[3-(cyclopentylamino)-4-nitrophenyl](2-fluorophenyl)methanone
|
|
C18H17FN2O3 |
详情 |
详情
|
(VII) |
37898 |
[4-amino-3-(cyclopentylamino)phenyl](2-fluorophenyl)methanone
|
|
C18H19FN2O |
详情 |
详情
|
(VIII) |
37899 |
(2-amino-1-cyclopentyl-1H-benzimidazol-6-yl)(2-fluorophenyl)methanone
|
|
C19H18FN3O |
详情 |
详情
|
(IX) |
37900 |
3-(2-amino-1-cyclopentyl-1H-benzimidazol-6-yl)-3-(2-fluorophenyl)-3-hydroxy-N-methylpropanamide
|
|
C22H25FN4O2 |
详情 |
详情
|
合成路线4
该中间体在本合成路线中的序号:
(IV) The title compound is prepared by two methods. Chlorination of 2',3'-O-isopropylideneinosine-5'-uronic acid (I) with SOCl2 in the presence of DMF produces the chloropurine acid chloride (II), which is further converted into the amide (III) upon treatment with ethylamine. Subsequent displacement of the purine 6-chloro group of (III) with cyclopentylamine (IV) furnishes the cyclopentylamino purine (V). Finally, acidic ketal hydrolysis in (IV) gives rise to the target compound.
中间体序号 |
中间体编号 |
品名 |
CAS号 |
分子式 |
供应商 |
用于合成 |
(I) |
61423 |
(3aR,4S,6R,6aR)-2,2-dimethyl-6-(6-oxo-1,6-dihydro-9H-purin-9-yl)tetrahydrofuro[3,4-d][1,3]dioxole-4-carboxylic acid
|
|
C13H14N4O6 |
详情 |
详情
|
(II) |
61424 |
(3aR,4S,6R,6aR)-6-(6-chloro-9H-purin-9-yl)-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxole-4-carbonyl chloride
|
|
C13H12Cl2N4O4 |
详情 |
详情
|
(III) |
61425 |
(3aR,4S,6R,6aR)-6-(6-chloro-9H-purin-9-yl)-N-ethyl-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxole-4-carboxamide
|
|
C15H18ClN5O4 |
详情 |
详情
|
(IV) |
28850 |
cyclopentanamine
|
1003-03-8 |
C5H11N |
详情 | 详情
|
(V) |
61426 |
(3aR,4S,6R,6aR)-6-[6-(cyclopentylamino)-9H-purin-9-yl]-N-ethyl-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxole-4-carboxamide
|
|
C20H28N6O4 |
详情 |
详情
|
合成路线5
该中间体在本合成路线中的序号:
(V) Alternatively, the inosine uronic acid (I) is converted to ethyl ester (II) by sequential treatment with thionyl chloride and then ethanol. Subsequent reaction with acetic anhydride in pyridine gives rise to diacetate (III). Chlorination of the inosine ring of (III) to produce (IV) is accomplished by treatment with phosphoryl chloride in the presence of tetraethylammonium chloride. Displacement of the 6-chloro group of (IV) with cyclopentylamine (V) yields amino purine (VI). Finally, aminolysis of the ester groups of (VI) with ethanolic ethylamine leads to the title compound.
中间体序号 |
中间体编号 |
品名 |
CAS号 |
分子式 |
供应商 |
用于合成 |
(I) |
61423 |
(3aR,4S,6R,6aR)-2,2-dimethyl-6-(6-oxo-1,6-dihydro-9H-purin-9-yl)tetrahydrofuro[3,4-d][1,3]dioxole-4-carboxylic acid
|
|
C13H14N4O6 |
详情 |
详情
|
(II) |
61427 |
ethyl (3aR,4S,6R,6aR)-2,2-dimethyl-6-(6-oxo-1,6-dihydro-9H-purin-9-yl)tetrahydrofuro[3,4-d][1,3]dioxole-4-carboxylate
|
|
C15H18N4O6 |
详情 |
详情
|
(III) |
61428 |
ethyl (2S,3R,4R,5R)-3,4-bis(acetyloxy)-5-(6-oxo-1,6-dihydro-9H-purin-9-yl)tetrahydro-2-furancarboxylate
|
|
C16H18N4O8 |
详情 |
详情
|
(IV) |
61429 |
ethyl (2S,3R,4R,5R)-3,4-bis(acetyloxy)-5-(6-chloro-9H-purin-9-yl)tetrahydro-2-furancarboxylate
|
|
C16H17ClN4O7 |
详情 |
详情
|
(V) |
28850 |
cyclopentanamine
|
1003-03-8 |
C5H11N |
详情 | 详情
|
(VI) |
61430 |
ethyl (2S,3R,4R,5R)-3,4-bis(acetyloxy)-5-[6-(cyclopentylamino)-9H-purin-9-yl]tetrahydro-2-furancarboxylate
|
|
C21H27N5O7 |
详情 |
详情
|
合成路线6
该中间体在本合成路线中的序号:
(V) Condensation of S-methylisothiourea (I) and cyano acetate derivative (II) by means of NaOMe in MeOH affords pyrimidine derivative (III), whose hydroxy group is converted into chloro by means of refluxing POCl3, yielding derivative (IV). Alkylation of (IV) with cyclopentylamine (V) and Et3N in CH2Cl2 provides derivative (VI), whose nitrile group is then reduced by means of LiAlH4 in THF to afford aminomethyl compound (VII). Treatment of (VII) with 1,1-carbonyldiimidazole (CDI) in refluxing THF gives pyrimidopyrimidinone (VIII), whose methylsulfanyl group is oxidized with 3-phenyl-2-(phenylsulfonyl)oxaziridine (IX) in CHCl3 to afford methyl sulfoxide derivative (X). Displacement of the methyl sulfoxide group of (X) with substituted aniline (XI) in TFA/acetonitrile yields 3,4-dihydropyrimidopyrimidinone (XII), which is finally oxidized by means of KOtBu in THF or DMSO.
【1】
Kramer, J.B.; et al.; Synthesis and biological activity of a novel series of pyrimidopyrimidinones as inhibitors of cyclin-dependent kinases. 219th ACS Natl Meet (March 26 2000, San Francisco) 2000, Abst MEDI 40.
|
【2】
Dobrusin, E.M.; Showalter, H.D.H.; Schroeder, M.C.; Toogood, P.; Kramer, J.B.; Trumpp-Kallmeyer, S.A.; Hamby, J.M. (Pfizer Inc.); Bicyclic pyrimidines and bicyclic 3,4-dihydropyrimidines as inhibitors of cellular proliferation. WO 9961444 .
|
中间体序号 |
中间体编号 |
品名 |
CAS号 |
分子式 |
供应商 |
用于合成 |
(IIa) |
43041 |
ethyl (Z)-2-cyano-3-ethoxy-2-propenoate
|
94-05-3 |
C8H11NO3 |
详情 | 详情
|
(IIb) |
43563 |
ethyl (E)-2-cyano-3-ethoxy-2-propenoate;(E)-ethyl 2-cyano-3-ethoxyacrylate |
94-05-3 |
C8H11NO3 |
详情 | 详情
|
(I) |
10272 |
[[Amino(imino)methyl]sulfanyl]methane
|
2986-19-8 |
C2H6N2S |
详情 | 详情
|
(III) |
43555 |
4-hydroxy-2-(methylsulfanyl)-5-pyrimidinecarbonitrile
|
|
C6H5N3OS |
详情 |
详情
|
(IV) |
43556 |
4-chloro-2-(methylsulfanyl)-5-pyrimidinecarbonitrile
|
|
C6H4ClN3S |
详情 |
详情
|
(V) |
28850 |
cyclopentanamine
|
1003-03-8 |
C5H11N |
详情 | 详情
|
(VI) |
43557 |
4-(cyclopentylamino)-2-(methylsulfanyl)-5-pyrimidinecarbonitrile
|
|
C11H14N4S |
详情 |
详情
|
(VII) |
43558 |
N-[5-(aminomethyl)-2-(methylsulfanyl)-4-pyrimidinyl]-N-cyclopentylamine; 5-(aminomethyl)-N-cyclopentyl-2-(methylsulfanyl)-4-pyrimidinamine
|
|
C11H18N4S |
详情 |
详情
|
(VIII) |
43559 |
1-cyclopentyl-7-(methylsulfanyl)-3,4-dihydropyrimido[4,5-d]pyrimidin-2(1H)-one
|
|
C12H16N4OS |
详情 |
详情
|
(IX) |
31834 |
3-phenyl-2-(phenylsulfonyl)-1,2-oxaziridine;2-(Phenylsulfonyl)-3-phenyloxaziridine;2-Benzenesulfonyl-3-phenyloxaziridine;3-Phenyl-2-phenylsulfonyloxaziridine;3-Phenyl-N-phenylsulfonyloxaziridine;N-(Phenylsulfonyl)phenyloxaziridine;N-Benzenesulfonyl-3-phenyloxaziridine |
63160-13-4 |
C13H11NO3S |
详情 | 详情
|
(X) |
43560 |
1-cyclopentyl-7-(methylsulfinyl)-3,4-dihydropyrimido[4,5-d]pyrimidin-2(1H)-one
|
|
C12H16N4O2S |
详情 |
详情
|
(XI) |
43561 |
1-(4-aminophenyl)-4-piperidinol
|
|
C11H16N2O |
详情 |
详情
|
(XII) |
43562 |
1-cyclopentyl-7-[4-(4-hydroxy-1-piperidinyl)anilino]-3,4-dihydropyrimido[4,5-d]pyrimidin-2(1H)-one
|
|
C22H28N6O2 |
详情 |
详情
|
合成路线7
该中间体在本合成路线中的序号:
(XVI) Carboxylic acid (XV) was coupled with cyclopentylamine (XVI) using EDC and HOBt to produce amide (XVII), which was cyclized to the fused pyrazinone derivative (XVIII) by treatment with pyridinium p-toluenesulfonate in toluene. The benzyloxycarbonyl group of (XVIII) was then removed by catalytic hydrogenation to give amine (XIX). This was finally coupled with (3,4,5-trimethoxyphenyl)glyoxylic acid (XX) to yield the title amide.
【1】
Reich, S.; Guo, C.X.; Villafranca, E.; Showalter, R.; Dong, L.; A concise synthesis of AG5473/5507 utilizing N-acyliminium ion chemistry. Tetrahedron Lett 2000, 41, 28, 5307.
|
【2】
Tada, H.; Kalish, V.; Kato, S.; Villafranca, J.E.; Tatlock, J.H.; Linton, M.A.; Kawakami, H. (Agouron Pharmaceuticals, Inc.); Cpds., compsns., and methods for stimulating neuronal growth and elongation. WO 0004020 .
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中间体序号 |
中间体编号 |
品名 |
CAS号 |
分子式 |
供应商 |
用于合成 |
(XV) |
43303 |
2-[9-[(benzyloxy)carbonyl]-2-(dimethoxymethyl)-4-oxo-3,9-diazabicyclo[3.3.1]non-3-yl]acetic acid
|
|
C20H26N2O7 |
详情 |
详情
|
(XVI) |
28850 |
cyclopentanamine
|
1003-03-8 |
C5H11N |
详情 | 详情
|
(XVII) |
43313 |
benzyl 3-[2-(cyclopentylamino)-2-oxoethyl]-2-(dimethoxymethyl)-4-oxo-3,9-diazabicyclo[3.3.1]nonane-9-carboxylate
|
|
C25H35N3O6 |
详情 |
详情
|
(XVIII) |
43314 |
benzyl 4-cyclopentyl-5,8-dioxo-4,7,13-triazatricyclo[7.3.1.0(2,7)]tridec-2-ene-13-carboxylate
|
|
C23H27N3O4 |
详情 |
详情
|
(XIX) |
43315 |
4-cyclopentyl-4,7,13-triazatricyclo[7.3.1.0(2,7)]tridec-2-ene-5,8-dione
|
|
C15H21N3O2 |
详情 |
详情
|
(XX) |
30046 |
2-oxo-2-(3,4,5-trimethoxyphenyl)acetic acid
|
|
C11H12O6 |
详情 |
详情
|
合成路线8
该中间体在本合成路线中的序号:
(IX) Amination of 5-bromo-2,4-dichloropyrimidine (VIII) with cyclopentylamine (IX) in EtOH gives 5-bromo-2-chloro-4-(cyclopentylamino)pyrimidine (X), which is then cyclized with crotonic acid (XI) by means of DIEA, TOTP, PdCl2(PhCN)2 in THF at 70 °C followed by treatment with Ac2O to yield the 8H-pyrido[2,3-d]pyrimidinone derivative (XII). Bromination of compound (XII) with Br2 in the presence of NaOAc in AcOH provides the 6-bromopyrido[2,3-d]pyrimidinone derivative (XIII), which is then coupled with the aminopyridine derivative (IV) in the presence of LiHMDS in toluene to afford intermediate (V). Condensation of the bromo derivative (V) with butylvinylether (XIV) in the presence of DIEA, PdCl2(dppf)2.CH2Cl2 complex in n-BuOH at 95 °C affords the 6-(1-butoxyvinyl)dihydropyrido[2,3-d]pyrimidine derivative (XV) . Finally, intermediate (XV) is treated with isethionic acid (XVI) —previously prepared by acidification of sodium isethionate (XVII) with HCl in i-PrOH in MeOH/H2O at 55 °C followed by TEA in MeOH .
The aminopyridine intermediate (IV) can be prepared by condensation of Boc-piperazine (XVIII) with 5-bromo-2-nitropyridine (XIX) in the presence of TEA in DMSO at 65-70 °C to give the nitropyridine derivative (XX), which is then reduced in the presence of H2 over Pd(OH)2/C in i-PrOH .
The key intermediate diarylamine adduct (V) can also be obtained directly by coupling aminopyridine derivative (IV) with the 2-methanesulfonylpyrido[2,3-d]pyrimidinone derivative (XXI) .
【1】
Toogood, P.L., Harvey, P.J., Repine, J.T. et al. Discovery of a potent and selective inhibitor of cyclin-dependent kinase 4/6. J Med Chem 2005, 48(7): 2388-406. |
【2】
Barvian, M.R., Quin, J. III, Sheehan, D.J. et al. (Pfizer Inc.). 2-(Pyridin-2-ylamino)-pyrido[2,3-d]pyrimidin-7-ones. EP 1470124, JP 2005519909, US 2003149001, US 6936612, WO 2003062236. |
【4】
Beylin, V.G., Blackburn, A.C., Erdman, D.T., Toogood, P.L. (Pfizer, Inc.).Isethionate salt of a selective CDK4 inhibitor. EP 1648889, JP 2007530425, US 2005059670, WO 2005005426. |
【3】
Erdman, D.T., Flamme, C.M., Nelson, J.D. (Pfizer Products, Inc.). Synthesis of 2-(pyridine-2-ylamino)-pyrido[2,3-d]pyrimidin-7-ones. EP 2069344, JP 2008094834, US 2008125588, US 7781583, WO 2008032157. |
中间体序号 |
中间体编号 |
品名 |
CAS号 |
分子式 |
供应商 |
用于合成 |
(IV) |
68144 |
tert-butyl 4-(6-aminopyridin-3-yl)piperazine-1-carboxylate |
|
C14H22N4O2 |
详情 | 详情
|
(V) |
68145 |
tert-butyl 4-(6-((6-bromo-8-cyclopentyl-5-methyl-7-oxo-7,8-dihydropyrido[2,3-d]pyrimidin-2-yl)amino)pyridin-3-yl)piperazine-1-carboxylate |
|
C27H34BrN7O3 |
详情 |
详情
|
(VIII) |
68146 |
5-bromo-2,4-dichloropyrimidine |
36082-50-5 |
C4HBrCl2N2 |
详情 | 详情
|
(IX) |
28850 |
cyclopentanamine
|
1003-03-8 |
C5H11N |
详情 | 详情
|
(X) |
68147 |
5-bromo-2-chloro-N-cyclopentylpyrimidin-4-amine;5-bromo-2-chloro-4-(cyclopentylamino)pyrimidine |
|
C9H11BrClN3 |
详情 | 详情
|
(XI) |
20599 |
(E)-2-butenoic acid; crotonic acid |
3724-65-0 |
C4H6O2 |
详情 | 详情
|
(XII) |
68148 |
2-chloro-8-cyclopentyl-5-methylpyrido[2,3-d]pyrimidin-7(8H)-one |
|
C13H14ClN3O |
详情 | 详情
|
(XIII) |
68149 |
6-bromo-2-chloro-8-cyclopentyl-5-methylpyrido[2,3-d]pyrimidin-7(8H)-one |
|
C13H13BrClN3O |
详情 | 详情
|
(XIV) |
59983 |
1-butoxyethylene; butyl vinyl ether
|
111-34-2 |
C6H12O |
详情 | 详情
|
(XV) |
68150 |
tert-butyl 4-(6-((6-(1-butoxyvinyl)-8-cyclopentyl-5-methyl-7-oxo-7,8-dihydropyrido[2,3-d]pyrimidin-2-yl)amino)pyridin-3-yl)piperazine-1-carboxylate |
|
C33H45N7O4 |
详情 | 详情
|
(XVI) |
13359 |
2-Hydroxy-1-ethanesulfonic acid
|
107-36-8 |
C2H6O4S |
详情 | 详情
|
(XVII) |
68151 |
sodium isethionate;sodium 2-sulfoethanolate |
|
C2H5NaO4S |
详情 | 详情
|
(XVIII) |
13225 |
N-tert-Butoxycarbonyl piperazine; tert-butyl 1-piperazinecarboxylate;tert-butyl piperazine-1-carboxylate |
143238-38-4 |
C9H18N2O2 |
详情 | 详情
|
(XIX) |
68152 |
5-bromo-2-nitropyridine;2-Nitro-5-bromopyridine;3-Bromo-6-nitropyridine |
39856-50-3 |
C5H3BrN2O2 |
详情 | 详情
|
(XX) |
68153 |
tert-butyl 4-(6-nitropyridin-3-yl)piperazine-1-carboxylate |
|
C14H20N4O4 |
详情 | 详情
|
(XXI) |
68154 |
6-bromo-8-cyclopentyl-5-methyl-2-(methylsulfonyl)pyrido[2,3-d]pyrimidin-7(8H)-one |
|
C14H16BrN3O3S |
详情 | 详情
|