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【结 构 式】 
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【分子编号】22416 【品名】3-chloro-3-methyl-1-butyne 【CA登记号】1111-97-3 |
【 分 子 式 】C5H7Cl 【 分 子 量 】102.56328 【元素组成】C 58.55% H 6.88% Cl 34.57% |
合成路线1
该中间体在本合成路线中的序号：(II)1) The cyclization of 4-cyanophenol (I) with 3-chloro-3-methylbutine (II) by means of benzyltrimethylammonium hydroxide in methanol-CH2Cl2 gives 6-cyano-2,2-dimethyl-2H-benzo[b]pyran (III), which is treated with N-bromosuccinimide in DMSO to afford 6-cyano-trans-3-bromo-3,4-dihydro-2,2-dimethyl 2H benzo[b]pyran-4-ol (IV). Epoxidation of (IV) by means of NaOH in dioxane-water yields 6-cyano-3-(4-dihydro-3,4-epoxy-2,2-dimethyl-2H-benzo[b]pyran (V), which is finally treated with 4-aminobutyric acid (VI) and NaHCO3 in refluxing ethanol. 2) By reaction of epoxide (V) with 2-pyrrolidone (X) by means of NaH in DMSO.
| 【1】 Evans, J.M.; Buckingham, R.E.; Willcocks, K. (SmithKline Beecham plc); Benzopyrans. EP 0076075; JP 3014573; JP 5202034; US 4446113 . |
| 【2】 Faruk, E.A. (SmithKline Beecham plc); Antihypertensive chromenes and chromans. EP 0093535; US 4510152 . |
| 【3】 Castaner, J.; Mannhold, R.; BRL-34915. Drugs Fut 1986, 11, 3, 175. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (A) | 27394 | Trimethylbenzylammonium Hydroxide; N,N,N-trimethyl(phenyl)methanaminium hydroxide; Triton B; Benzyltrimethylammonium hydroxide | 100-85-6 | C10H17NO | 详情 | 详情 |
| (I) | 25109 | 4-hydroxybenzonitrile | 767-00-0 | C7H5NO | 详情 | 详情 |
| (II) | 22416 | 3-chloro-3-methyl-1-butyne | 1111-97-3 | C5H7Cl | 详情 | 详情 |
| (III) | 27395 | 2,2-dimethyl-2H-chromene-6-carbonitrile | C12H11NO | 详情 | 详情 | |
| (IV) | 27396 | 3-bromo-4-hydroxy-2,2-dimethyl-6-chromanecarbonitrile | C12H12BrNO2 | 详情 | 详情 | |
| (V) | 12861 | 2,2-Dimethyl-1a,7b-dihydro-2H-oxireno[2,3-c]chromene-6-carbonitrile | C12H11NO2 | 详情 | 详情 | |
| (VI) | 13620 | 4-Amino-n-butyric acid; 4-Aminobutyric acid;Piperidinic acid;Piperidic acid | 56-12-2 | C4H9NO2 | 详情 | 详情 |
| (X) | 27397 | 2-Pyrrolidinone | 616-45-5 | C4H7NO | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(II)The reaction of epoxide (V) with ammonia in ethanol gives 4-amino-6-cyano-3,4-dihydro-2,2-dimethyl-trans-2H-benzo[b]pyran-3-ol (VII), which is condensed with 4-chlorobutyryl chloride (VIII) by means of NaOH in CHCl3 yielding 6-cyano-3,4-dihydro-2,2-dimethyl-trans-4-(4-chlorobutyrylamino)-2H-benzo[blpyran 3-ol (IX). Finally, this compound is cyclized by means of NaH in THF.
| 【1】 Faruk, E.A. (SmithKline Beecham plc); Antihypertensive chromenes and chromans. EP 0093535; US 4510152 . |
| 【2】 Evans, J.M.; Buckingham, R.E.; Willcocks, K. (SmithKline Beecham plc); Benzopyrans. EP 0076075; JP 3014573; JP 5202034; US 4446113 . |
| 【3】 Castaner, J.; Mannhold, R.; BRL-34915. Drugs Fut 1986, 11, 3, 175. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (A) | 27394 | Trimethylbenzylammonium Hydroxide; N,N,N-trimethyl(phenyl)methanaminium hydroxide; Triton B; Benzyltrimethylammonium hydroxide | 100-85-6 | C10H17NO | 详情 | 详情 |
| (I) | 25109 | 4-hydroxybenzonitrile | 767-00-0 | C7H5NO | 详情 | 详情 |
| (II) | 22416 | 3-chloro-3-methyl-1-butyne | 1111-97-3 | C5H7Cl | 详情 | 详情 |
| (III) | 27395 | 2,2-dimethyl-2H-chromene-6-carbonitrile | C12H11NO | 详情 | 详情 | |
| (IV) | 27396 | 3-bromo-4-hydroxy-2,2-dimethyl-6-chromanecarbonitrile | C12H12BrNO2 | 详情 | 详情 | |
| (V) | 12861 | 2,2-Dimethyl-1a,7b-dihydro-2H-oxireno[2,3-c]chromene-6-carbonitrile | C12H11NO2 | 详情 | 详情 | |
| (VII) | 27398 | (3S,4R)-4-amino-3-hydroxy-2,2-dimethyl-3,4-dihydro-2H-chromene-6-carbonitrile | C12H14N2O2 | 详情 | 详情 | |
| (VIII) | 11265 | 4-Chlorobutanoyl chloride; 4-Chlorobutyric acid chloride | 4635-59-0 | C4H6Cl2O | 详情 | 详情 |
| (IX) | 27399 | 4-chloro-N-[(3S,4R)-6-cyano-3-hydroxy-2,2-dimethyl-3,4-dihydro-2H-chromen-4-yl]butanamide | C16H19ClN2O3 | 详情 | 详情 |
合成路线3
该中间体在本合成路线中的序号：(XIV)2) The condensation of 5,7-dihydroxy-4-propyl-2H-1-benzopyran-2-one (III) with N-methylformanilide (XII) by means of POCl3 in hot dichloromethane gives the carbaldehyde (XIII), which is cyclized with 3-chloro-3-methyl-1-butyne (XIV) by means of ZnCl2 /K2CO3 in hot 2-butanone/DMF, yielding the benzodipyran-carbaldehyde (XV). The enantioselective reaction of (XV) with 2(E)-butene and the chiral borane (+)-(E)-crotyldiisopinocamphenylborane (XVI) affords the single (R, R)-enatiomer (XVII). The selective silylation of (XVII) with TBDMS-Cl as usual gives the monosilyl ether (XVIII), which is cyclized by means of mercuric acetate and NaBH4 in THF, yielding the silylated (10R,11R,12R)-benzotripyran (XIX). The desilylation of (XIX) with tetrabutylammonium fluoride in THF gives the (10R,11S,12R)-benzotripyran (XX) (calanolide B), which is converted into calanolide A by inversion of the C-12 OH-group carried out with a modified Mitsunobu reaction with dimethyl azodicarboxylate (DEAD)/trimethylphosphine/chloroacetic acid in toluene/THF, followed by treatment with NH4OH in methanol.
| 【1】 Tagliaferri, F.; Deshpande, P.P.; Yan, S.; Victory, S.F.; Baker, D.C.; Synthesis of optically active calanoides A and B. J Org Chem 1995, 60, 10, 2964. |
| 【2】 Castañer, J.; Leeson, P.; Sorbera, L.A.; Calanolide A. Drugs Fut 1999, 24, 3, 235. |
| 【3】 Tagliaferri, F.; Yan, S.; Deshpande, P.P.; Baker, D.C.; Victory, S.F. (University of Tennessee, Knoxville); Synthesis of optically active calanolides A and B . US 5608085; WO 9626934 . |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| 17343 | 2-Butene-cis; (Z)-2-butene | 590-18-1 | C4H8 | 详情 | 详情 | |
| (III) | 22405 | 5,7-dihydroxy-4-propyl-2H-chromen-2-one | C12H12O4 | 详情 | 详情 | |
| (XII) | 20360 | methyl(phenyl)formamide;N-Methylformanilide;N-Formyl-N-methylaniline;Methylphenylformamide;N-methyl-N-phenylformamide;N-Methyl-N-formylaniline;N-Formyl-N-methylaniline | 93-61-8 | C8H9NO | 详情 | 详情 |
| (XIII) | 22415 | 5,7-dihydroxy-2-oxo-4-propyl-2H-chromene-8-carbaldehyde | C13H12O5 | 详情 | 详情 | |
| (XIV) | 22416 | 3-chloro-3-methyl-1-butyne | 1111-97-3 | C5H7Cl | 详情 | 详情 |
| (XV) | 22417 | 5-hydroxy-2,2-dimethyl-8-oxo-10-propyl-2H,8H-pyrano[2,3-f]chromene-6-carbaldehyde | C18H18O5 | 详情 | 详情 | |
| (XVI) | 22418 | (E)-2-butenyl[bis(2,6,6-trimethylbicyclo[3.1.1]hept-3-yl)]borane | C24H41B | 详情 | 详情 | |
| (XVII) | 22419 | 5-hydroxy-6-[(1R,2R)-1-hydroxy-2-methyl-3-butenyl]-2,2-dimethyl-10-propyl-2H,8H-pyrano[2,3-f]chromen-8-one | C22H26O5 | 详情 | 详情 | |
| (XVIII) | 22420 | 6-((1R,2R)-1-[[tert-butyl(dimethyl)silyl]oxy]-2-methyl-3-butenyl)-5-hydroxy-2,2-dimethyl-10-propyl-2H,8H-pyrano[2,3-f]chromen-8-one | C28H40O5Si | 详情 | 详情 | |
| (XIX) | 22421 | (10R,11R,12R)-12-[[tert-butyl(dimethyl)silyl]oxy]-6,6,10,11-tetramethyl-4-propyl-11,12-dihydro-2H,6H,10H-dipyrano[2,3-f:2,3-h]chromen-2-one | C28H40O5Si | 详情 | 详情 | |
| (XX) | 22413 | (10R,11S,12R)-12-hydroxy-6,6,10,11-tetramethyl-4-propyl-11,12-dihydro-2H,6H,10H-dipyrano[2,3-f:2,3-h]chromen-2-one | C22H26O5 | 详情 | 详情 |
合成路线4
该中间体在本合成路线中的序号：(V)The reaction of 5,7-dihydroxy-4-propyl-2H-1-benzopyran-2-one (I) with TsCl (or MsCl) and pyridine gives the ditosylate (II), which is selectively desulfonated by means of TBAF in THF at 0 C to yield monotosylate (III). The cyclization of (III) with 3-chloro-3-methyl-1-butyne (IV) by means of K2CO3, Bu4N+I- and ZnCl2 in butanone/DMF affords the benzodipyran (V), which is detosylated with TBAF in THF at 20 C to provide the hydroxy derivative (VI). Finally, the OH group of (VI) is enantioselectively alkylated with the mixed carbonate ester (VII) by means of Pd2dba3 ,Cs2CO3 and a (S,S)-chiral ligand in THF to furnish the target chiral intermediate (VIII) (see scheme no. 20433103a, intermediate (XXVII)).
| 【1】 Fox, M.E.; et al.; A novel synthesis of 5-hydroxy-2,2-dimethyl-10-propyl-2H-pyrano[2,3-f]chromen-8-one. Tetrahedron Lett 2002, 43, 16, 2899. |
| 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) | 22405 | 5,7-dihydroxy-4-propyl-2H-chromen-2-one | C12H12O4 | 详情 | 详情 | |
| (II) | 58650 | 5-{[(4-methylphenyl)sulfonyl]oxy}-2-oxo-4-propyl-2H-chromen-7-yl 4-methylbenzenesulfonate | C26H24O8S2 | 详情 | 详情 | |
| (III) | 58651 | 5-hydroxy-2-oxo-4-propyl-2H-chromen-7-yl 4-methylbenzenesulfonate | C19H18O6S | 详情 | 详情 | |
| (IV) | 58652 | 2,2-dimethyl-8-oxo-10-propyl-2H,8H-pyrano[2,3-f]chromen-5-yl 4-methylbenzenesulfonate | C24H24O6S | 详情 | 详情 | |
| (V) | 22416 | 3-chloro-3-methyl-1-butyne | 1111-97-3 | C5H7Cl | 详情 | 详情 |
| (VI) | 58653 | 5-hydroxy-2,2-dimethyl-10-propyl-2H,8H-pyrano[2,3-f]chromen-8-one | C17H18O4 | 详情 | 详情 | |
| (VII) | 22426 | methyl (E)-2-methyl-2-butenyl carbonate | C7H12O3 | 详情 | 详情 | |
| (VIII) | 22428 | 5-[[(1S)-1,2-dimethyl-2-propenyl]oxy]-2,2-dimethyl-10-propyl-2H,8H-pyrano[2,3-f]chromen-8-one | C22H26O4 | 详情 | 详情 |
合成路线5
该中间体在本合成路线中的序号：(IX)An enantioselective total synthesis of (+)-calanolide A has been reported: The silylation of 2'-hydroxy-4',6'-dimethoxybutyrophenone (I) with TIPS-Cl by means of benzylltriethylammonium chloride and NaOH in benzene gives the silyl ether (II), which is demethylated with BCl3 in dichloromethane yielding 2'-hydroxy-4'-methoxy-6'-(triisopropylsilyloxy)butyrophenone (III). The Wittig condensation of (III) with the phosphorane (IV) in N,N-diethylaniline with simultaneous cyclization, affords the benzopyranone (V), which is submitted to a Friedel-Crafts condensation with the acyl chloride (VI) by means of SnCl4 in dichloromethane to provide the 8-acylbenzopyranone (VII). The desilylation of (VII) by means of TBAF in THF/dichloromethane gives the 5-hydroxy compound (VIII) which is submitted to a propargylation with alcohol (IX) and DBU and then to a Claisen rearrangement with N,N-diethylaniline affording the pyrano-benzopyran (X). Demethylation of (X) with MgI2 in refluxing benzene gives the phenol (XI), which is submitted to a (-)-quinine-catalyzed asymmetric intramolecular oxo-Michael addition in chlorobenzene yielding an 80:20 mixture of the chiral cis- and trans-benzotripyrans (XII) (94% ee) and (XIII), respectively. Since the desired compound is the minor component (XIII), the preceding mixture is treated with MgI2 in refluxing benzene to afford an equilibrated 50:50 mixture that is separated by chromatography, and the undesired cis-isomer can be recycled by repeating the MgI2 treatment. The enantiomerically rich trans-isomer (XIII) is finally reduced with LiAlH(Ot-Bu)3 in THF.
| 【1】 Tanaka, T.; et al.; Enantioselective total synthesis of anti HIV-1 active (+)-calanolide A through a quinine-catalyzed asymmetric intramolecular oxo-Michael addition. Tetrahedron Lett 2000, 41, 52, 10229. |
| 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) | 45726 | 1-(2-hydroxy-4,6-dimethoxyphenyl)-1-butanone | C12H16O4 | 详情 | 详情 | |
| (II) | 45727 | 1-[2,4-dimethoxy-6-[(triisopropylsilyl)oxy]phenyl]-1-butanone | C21H36O4Si | 详情 | 详情 | |
| (III) | 45728 | 1-[2-hydroxy-4-methoxy-6-[(triisopropylsilyl)oxy]phenyl]-1-butanone | C20H34O4Si | 详情 | 详情 | |
| (IV) | 14689 | Methyl (triphenylphosphoranylidene)acetate; (methoxycarbonylmethylene)triphenylphosphorane；Methyl 2-(triphenyl-lambda(5)-phosphanylidene)acetate | 2605-67-6 | C21H19O2P | 详情 | 详情 |
| (V) | 45729 | 7-methoxy-4-propyl-5-[(triisopropylsilyl)oxy]-2H-chromen-2-one | C22H34O4Si | 详情 | 详情 | |
| (VI) | 45730 | Tigloyl chloride; (E)-2-methyl-2-butenoyl chloride | 35660-94-7 | C5H7ClO | 详情 | 详情 |
| (VII) | 45731 | 7-methoxy-8-[(E)-2-methyl-2-butenoyl]-4-propyl-5-[(triisopropylsilyl)oxy]-2H-chromen-2-one | C27H40O5Si | 详情 | 详情 | |
| (VIII) | 45732 | 5-hydroxy-7-methoxy-8-[(E)-2-methyl-2-butenoyl]-4-propyl-2H-chromen-2-one | C18H20O5 | 详情 | 详情 | |
| (IX) | 22416 | 3-chloro-3-methyl-1-butyne | 1111-97-3 | C5H7Cl | 详情 | 详情 |
| (X) | 45733 | 5-methoxy-2,2-dimethyl-6-[(E)-2-methyl-2-butenoyl]-10-propyl-2H,8H-pyrano[2,3-f]chromen-8-one | C23H26O5 | 详情 | 详情 | |
| (XI) | 45734 | 5-hydroxy-2,2-dimethyl-6-[(E)-2-methyl-2-butenoyl]-10-propyl-2H,8H-pyrano[2,3-f]chromen-8-one | C22H24O5 | 详情 | 详情 | |
| (XII) | 22411 | (10R,11S)-6,6,10,11-tetramethyl-4-propyl-10,11-dihydro-2H,6H,12H-dipyrano[2,3-f:2,3-h]chromene-2,12-dione | C22H24O5 | 详情 | 详情 | |
| (XIII) | 22410 | (10R,11R)-6,6,10,11-tetramethyl-4-propyl-10,11-dihydro-2H,6H,12H-dipyrano[2,3-f:2,3-h]chromene-2,12-dione | C22H24O5 | 详情 | 详情 |
合成路线6
该中间体在本合成路线中的序号：(II)The cyclization of 4-hydroxyacetophenone (I) with 3-chloro-3-methyl-1-butyne (II) gives 6-acetyl-2,2-dimethyl-2H-1-benzopyran (III), which is enantioselectively epoxidized by means of Mn+3 salen catalysts, yielding the chiral epoxide (IV). The cleavage of the epoxide ring of (IV) with ammonia in ethanol affords the (3R,4S)-trans-aminoalcohol (V). The acylation of (V) with 3-chloro-4-fluorobenzoyl chloride (VI) and triethylamine yields the (3R,4S)-trans-amide (VII). The cyclization of (VII) by means of diethylaminosulfur trifluoride (DAST) in dichloromethane affords the (3aS-cis)-oxazoline (VIII), which is finally treated with 5N H2SO4.
| 【1】 Chan, W.N.; et al.; Synthesis of novel trans-4-(substituted-benzamido)-3, 4-dihydro-2H-benzo[b]-pyran-3-ol derivatives as potential anticonvulsant agents with a distinctive binding profile. J Med Chem 1996, 39, 23, 4537. |
| 【2】 Castañer, J.; Leeson, P.; Rabasseda, X.; Tonabersat. Drugs Fut 1999, 24, 10, 1078. |
| 【3】 Chan, W.N.; Morgan, H.K.A.; Thompson, M.; Evans, J.M. (SmithKline Beecham plc); Benzopyrans and their use as therapeutic agents. EP 0764157; JP 1998501251; US 5760074; WO 9534545 . |
| 【4】 Thompson, M.; Evans, J.M.; Upton, N.; Chan, W.N.; Vong, K.K.; Willette, R.N. (SmithKline Beecham plc); Bicyclic cpds. with pharmaceutical activity. EP 0673373; JP 1996505132; US 5908860; WO 9413656 . |
| 【5】 Attrill, R.P.; Bell, D.; Miller, D. (SmithKline Beecham plc); Chiral catalysts and epoxidation reactions catalyzed thereby. WO 9403271 . |
| 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) | 18123 | 1-(4-hydroxyphenyl)-1-ethanone; 4'-Hydroxyacetophenone | 99-93-4 | C8H8O2 | 详情 | 详情 |
| (II) | 22416 | 3-chloro-3-methyl-1-butyne | 1111-97-3 | C5H7Cl | 详情 | 详情 |
| (III) | 28706 | 1-(2,2-dimethyl-2H-chromen-6-yl)-1-ethanone | C13H14O2 | 详情 | 详情 | |
| (IV) | 28707 | 1-[(1aR,7bR)-2,2-dimethyl-1a,7b-dihydro-2H-oxireno[2,3-c]chromen-6-yl]-1-ethanone | C13H14O3 | 详情 | 详情 | |
| (V) | 28708 | 1-[(3R,4S)-4-amino-3-hydroxy-2,2-dimethyl-3,4-dihydro-2H-chromen-6-yl]-1-ethanone | C13H17NO3 | 详情 | 详情 | |
| (VI) | 24370 | 3-chloro-4-fluorobenzoyl chloride | 65055-17-6 | C7H3Cl2FO | 详情 | 详情 |
| (VII) | 28709 | N-[(3R,4S)-6-acetyl-3-hydroxy-2,2-dimethyl-3,4-dihydro-2H-chromen-4-yl]-3-chloro-4-fluorobenzamide | C20H19ClFNO4 | 详情 | 详情 | |
| (VIII) | 28713 | 1-[(3aS,9bS)-2-(3-chloro-4-fluorophenyl)-4,4-dimethyl-3a,9b-dihydro-4H-chromeno[4,3-d][1,3]oxazol-8-yl]-1-ethanone | C20H17ClFNO3 | 详情 | 详情 |
合成路线7
该中间体在本合成路线中的序号：(II)The cyclization of 4-hydroxyacetophenone (I) with 3-chloro-3-methyl-1-butyne (II) gives 5-acetyl-2,2-dimethyl-2H-1-benzopyran (III), which is enantioselectively epoxidized catalyzed by chiral salen Mn(III) catalysts to yield the (3R,4R)-epoxide (IV). The reaction of (IV) with ammonia in ethanol affords the (3R,4S)-aminoalcohol (V), which is finally acylated with 4-fluorobenzoyl chloride (VI) and TEA in dichloromethane to provide the target amide. Alternatively, the target amide can also be obtained by direct cleavage of the epoxide ring of (IV) with 4-fluorobenzamide (VII) by means of tBu-OK in tert-butanol.
| 【1】 Chan, W.N.; et al.; Synthesis of novel trans-4-(substituted-benzamido)-3, 4-dihydro-2H-benzo[b]-pyran-3-ol derivatives as potential anticonvulsant agents with a distinctive binding profile. J Med Chem 1996, 39, 23, 4537. |
| 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) | 18123 | 1-(4-hydroxyphenyl)-1-ethanone; 4'-Hydroxyacetophenone | 99-93-4 | C8H8O2 | 详情 | 详情 |
| (II) | 22416 | 3-chloro-3-methyl-1-butyne | 1111-97-3 | C5H7Cl | 详情 | 详情 |
| (III) | 28706 | 1-(2,2-dimethyl-2H-chromen-6-yl)-1-ethanone | C13H14O2 | 详情 | 详情 | |
| (IV) | 28707 | 1-[(1aR,7bR)-2,2-dimethyl-1a,7b-dihydro-2H-oxireno[2,3-c]chromen-6-yl]-1-ethanone | C13H14O3 | 详情 | 详情 | |
| (V) | 28708 | 1-[(3R,4S)-4-amino-3-hydroxy-2,2-dimethyl-3,4-dihydro-2H-chromen-6-yl]-1-ethanone | C13H17NO3 | 详情 | 详情 | |
| (VI) | 17263 | 4-fluorobenzoyl chloride | 403-43-0 | C7H4ClFO | 详情 | 详情 |
| (VII) | 37090 | 4-fluorobenzamide | 824-75-9 | C7H6FNO | 详情 | 详情 |
合成路线8
该中间体在本合成路线中的序号：(X)The intermediate 4-(4-methoxyphenyl)-2-methylpyridine (IV) was obtained by two different procedures. Acylation of 2-picoline (I) with ethyl chloroformate, followed by addition of the Grignard reagent (II), prepared from 4-bromoanisole and magnesium, furnished the 4-aryl dihydropyridine (III). Aromatization of (III) by heating at 200 C with sulfur in decahydronaphthalene produced the phenylpyridine (IV). In an alternative method, 2-methylpyridine (I) was converted to the N-aminopyridinium salt (V) by reaction with hydroxylamine-O-sulfonic acid. This was then condensed with dehydroacetic acid (VI) under acidic conditions to produce the bipyridinium derivative (VII), which was isolated as the tetrafluoroborate salt. Alternatively, addition of 4-methoxyphenylmagnesium bromide (II) to (VII) yielded the phenyl bipyridinone (VIII), which upon elimination of the dimethylpyridone moiety in refluxing DMF generated the intermediate phenyl pyridine (IV). Methyl ether cleavage of (IV) in refluxing HBr afforded phenol (IX). This was then alkylated with 3-chloro-3-methylbutyne (X) to yield the aryl propargyl ether (XI) ,which was subjected to a Claisen rearrangement in hot ortho-dichlorobenzene to produce chromene (XII).
| 【1】 Manley, P.W. (Novartis AG; Novartis Deutschland GmbH); 2,2-Dialkyl- and 2,2-dialkyl-3, 4-dihydro-3-hydroxy-2H-1-benzopyrans, their use as pharmaceuticals. EP 0623129; WO 9412493 . |
| 【2】 Manley, P.W. (Novartis AG); 2,2-Dialkyl- and 2,2-dialkyl-3, 4-dihydro-3-hydroxy-2H-1-benzopyrans. US 5574049 . |
| 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) | 17590 | 2-methylpyridine; 2-picoline | 109-06-8 | C6H7N | 详情 | 详情 |
| (II) | 37674 | Bromo(4-methoxyphenyl)magnesium; 4-Methoxyphenylmagnesium bromide | 352-13-6 | C7H7BrMgO | 详情 | 详情 |
| (III) | 50053 | ethyl 4-(4-methoxyphenyl)-2-methyl-1(4H)-pyridinecarboxylate | C16H19NO3 | 详情 | 详情 | |
| (IV) | 50055 | 4-(4-methoxyphenyl)-2-methylpyridine; methyl 4-(2-methyl-4-pyridinyl)phenyl ether | C13H13NO | 详情 | 详情 | |
| (V) | 50051 | 1-amino-2-methylpyridinium hydrogen sulfate | C6H10N2O4S | 详情 | 详情 | |
| (VI) | 43660 | 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione | 520-45-6 | C8H8O4 | 详情 | 详情 |
| (VII) | 50052 | C13H15BF4N2O | 详情 | 详情 | ||
| (VIII) | 50054 | C20H22N2O2 | 详情 | 详情 | ||
| (IX) | 50056 | 4-(2-methyl-4-pyridinyl)phenol | C12H11NO | 详情 | 详情 | |
| (X) | 22416 | 3-chloro-3-methyl-1-butyne | 1111-97-3 | C5H7Cl | 详情 | 详情 |
| (XI) | 50057 | 1,1-dimethyl-2-propynyl 4-(2-methyl-4-pyridinyl)phenyl ether; 4-[4-[(1,1-dimethyl-2-propynyl)oxy]phenyl]-2-methylpyridine | C17H17NO | 详情 | 详情 | |
| (XII) | 50058 | 4-(2,2-dimethyl-2H-chromen-6-yl)-2-methylpyridine | C17H17NO | 详情 | 详情 |
合成路线9
该中间体在本合成路线中的序号：(IV)The benzoacridine system (III) was obtained by condensation 3-amino-2-naphthalenecarboxylic acid (I) with phloroglucinol (III) in the presence of p-toluenesulfonic acid in refluxing 1-heptanol. Regioselective O-alkylation of (III) with 3-chloro-3-methylbut-1-yne (IV) in DMF at 65 C gave the intermediate propargyl ether (V), which upon further heating at 130 C underwent Claisen rearrangement to produce the pentacyclic compound (VI). Methylation of (VI) with an excess of dimethyl sulfate in the presence of NaH yielded the O,N-dimethyl derivative (VII). The racemic cis diol (VIII) was obtained by OsO4-catalyzed oxidation of (VII) using N-methylmorpholine-N-oxide. Finally, diol (VIII) esterification with Ac2O in pyridine afforded the title diacetate ester.
| 【1】 Michel, S.; Costes, N.; Le Deit, H.; et al.; Synthesis and cytotoxic and antitumor activity of benzo[b]pyrano[3,2-h]acridin-7-one analogues of acronycine. J Med Chem 2000, 43, 12, 2395. |
| 【2】 Pfeiffer, B.; Michel, S.; Koch, M.; Pierre, A.; Renard, P.; Tillequin, F.; Atassi, G. (ADIR et Cie.); Novel acronycine derivs., preparation method and pharmaceutical compsns.. EP 1042326; FR 2772765; WO 9932491 . |
| 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) | 47431 | 3-amino-2-naphthoic acid | 5959-52-4 | C11H9NO2 | 详情 | 详情 |
| (II) | 11799 | 1,3,5-Benzenetriol; Fluoroglucinol | 108-73-6 | C6H6O3 | 详情 | 详情 |
| (III) | 47432 | 1,3-dihydroxybenzo[b]acridin-12(5H)-one | C17H11NO3 | 详情 | 详情 | |
| (IV) | 22416 | 3-chloro-3-methyl-1-butyne | 1111-97-3 | C5H7Cl | 详情 | 详情 |
| (V) | 47433 | 3-[(1,1-dimethyl-2-propynyl)oxy]-1-hydroxybenzo[b]acridin-12(5H)-one | C22H17NO3 | 详情 | 详情 | |
| (VI) | 47434 | 6-hydroxy-3,3-dimethyl-3,14-dihydro-7H-benzo[b]pyrano[3,2-h]acridin-7-one | C22H17NO3 | 详情 | 详情 | |
| (VII) | 47435 | 6-methoxy-3,3,14-trimethyl-3,14-dihydro-7H-benzo[b]pyrano[3,2-h]acridin-7-one | C24H21NO3 | 详情 | 详情 | |
| (VIII) | 47436 | (1S,2S)-1,2-dihydroxy-6-methoxy-3,3,14-trimethyl-1,2,3,14-tetrahydro-7H-benzo[b]pyrano[3,2-h]acridin-7-one | C24H23NO5 | 详情 | 详情 |
合成路线10
该中间体在本合成路线中的序号：(II)4-Methyl-7-hydroxycoumarin (I) was alkylated with 3-chloro-3-methyl-1-butyne (II) in the presence of K2CO3 and KI to afford the corresponding aryl propargyl ether (III). Claisen rearrangement of (III) in refluxing diethylaniline furnished the tricyclic system (IV). The target 3'R,4'R-dihydroxylated derivative (V) was obtained by Sharpless asymmetric dihydroxylation of (IV) with hydroquinine 2,5-diphenyl-4,6-pyrimidinediyl diether ((DHQ)2-PYR) as the chiral catalyst. Diol (V) was finally esterified with (-)-S-camphanoyl chloride (VI) to afford the title diester.
| 【1】 Xie, L.; Takeuchi, Y.; Cosentino, L.M.; Lee, K.-H.; Anti-AIDS agent 33. Synthesis and anti-HIV activity of mono-methyl substituted 3',4'-di-O-(-)-camphanoyl-(+)-cis-khellactone (DCK) analogues. Bioorg Med Chem Lett 1998, 8, 16, 2151. |
| 【2】 Takeuchi, Y.; Xie, L.; Lee, K.-H.; Cosentino, L.M.; Anti-AIDS agents. 37.(1) synthesis and structure-activity relationships of (3'R,4'R)-(+)-cis-khellactone derivatives as novel potent anti-HIV agents. J Med Chem 1999, 42, 14, 2662. |
| 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) | 47997 | 7-hydroxy-4-methyl-2H-chromen-2-one | 90-33-5 | C10H8O3 | 详情 | 详情 |
| (II) | 22416 | 3-chloro-3-methyl-1-butyne | 1111-97-3 | C5H7Cl | 详情 | 详情 |
| (III) | 47998 | 7-[(1,1-dimethyl-2-propynyl)oxy]-4-methyl-2H-chromen-2-one | C15H14O3 | 详情 | 详情 | |
| (IV) | 47999 | 4,8,8-trimethyl-2H,8H-pyrano[2,3-f]chromen-2-one | C15H14O3 | 详情 | 详情 | |
| (V) | 48000 | (9R,10R)-9,10-dihydroxy-4,8,8-trimethyl-9,10-dihydro-2H,8H-pyrano[2,3-f]chromen-2-one | C15H16O5 | 详情 | 详情 | |
| (VI) | 41620 | (1R,4S)-4,7,7-trimethyl-3-oxo-2-oxabicyclo[2.2.1]heptane-1-carbonyl chloride | C10H13ClO3 | 详情 | 详情 |
合成路线11
该中间体在本合成路线中的序号：(VI)Vilsmeier formylation of orcinol (I) by means of POCl3 and DMF afforded 2,4-dihydroxy-6-methylbenzaldehyde (II). Coumarin (V) was then prepared by Wittig condensation of (II) with carbethoxymethylene triphenylphosphorane (III) followed by intramolecular cyclization in refluxing xylene. Alkylation of (V) with 3-chloro-3-methyl-1-butyne (VI) in the presence of K2CO3 and KI produced the corresponding alpha,alpha-dimethylpropargyl ether (VII), and subsequent thermal cyclization in refluxing N,N-diethylaniline gave rise to the tricyclic system (VIII). Osmium-catalyzed asymmetric dihydroxylation of (VIII) in the presence of the enantioselective ligand hydroquinone 2,5-diphenyl-4,6-pyrimidinediyl diether [(DHQ)2-PYR] produced the required (R,R)-(+)-cis-diol (IX). This was finally acylated with (S)-(-)-camphanic chloride (X) in the presence of pyridine to produce the target dicamphanoyl ester.
| 【1】 Takeuchi, Y.; Xie, L.; Lee, K.-H.; Cosentino, L.M.; Anti-AIDS agents. 37.(1) synthesis and structure-activity relationships of (3'R,4'R)-(+)-cis-khellactone derivatives as novel potent anti-HIV agents. J Med Chem 1999, 42, 14, 2662. |
| 【2】 Xie, L.; Takeuchi, Y.; Cosentino, L.M.; Lee, K.-H.; Anti-AIDS agent 33. Synthesis and anti-HIV activity of mono-methyl substituted 3',4'-di-O-(-)-camphanoyl-(+)-cis-khellactone (DCK) analogues. Bioorg Med Chem Lett 1998, 8, 16, 2151. |
| 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) | 27257 | 5-Methyl-1,3-benzenediol; Orcinol | 505-15-4 | C7H8O2 | 详情 | 详情 |
| (II) | 34435 | 2,4-dihydroxy-6-methylbenzaldehyde | C8H8O3 | 详情 | 详情 | |
| (III) | 14182 | ethyl 2-(triphenyl-lambda(5)-phosphanylidene)acetate; (Carbethoxymethylene)triphenylphosphorane | 1099-45-2 | C22H21O2P | 详情 | 详情 |
| (IV) | 34436 | ethyl (E)-3-(2,4-dihydroxy-6-methylphenyl)-2-propenoate | C12H14O4 | 详情 | 详情 | |
| (V) | 34437 | 7-hydroxy-5-methyl-2H-chromen-2-one | C10H8O3 | 详情 | 详情 | |
| (VI) | 22416 | 3-chloro-3-methyl-1-butyne | 1111-97-3 | C5H7Cl | 详情 | 详情 |
| (VII) | 34438 | 7-[(1,1-dimethyl-2-propynyl)oxy]-5-methyl-2H-chromen-2-one | C15H14O3 | 详情 | 详情 | |
| (VIII) | 34439 | 5,8,8-trimethyl-2H,8H-pyrano[2,3-f]chromen-2-one | C15H14O3 | 详情 | 详情 | |
| (IX) | 34440 | (9R,10R)-9,10-dihydroxy-5,8,8-trimethyl-9,10-dihydro-2H,8H-pyrano[2,3-f]chromen-2-one | C15H16O5 | 详情 | 详情 | |
| (X) | 16583 | (1S,4R)-4,7,7-trimethyl-3-oxo-2-oxabicyclo[2.2.1]heptane-1-carbonyl chloride; (-)-Camphanic chloride | 39637-74-6 | C10H13ClO3 | 详情 | 详情 |
合成路线12
该中间体在本合成路线中的序号：(VIII)In a different method, sodium 4-hydroxybenzenesulfonate (V) was converted to the sulfonyl chloride (VI) upon treatment with thionyl chloride in hot 1,2-dichloroethane. Reaction of acid chloride (VI) with aniline provided sulfonamide (VII). Alkylation of the phenolic hydroxyl group of (VII) with 3-chloro-3-methyl-1-butyne (VIII) in the presence of DBU and CuCl gave the propargyl ether (IX), which was then cyclized to benzopyran (IV) under Claisen rearrangement conditions.
| 【1】 Manley, P.W. (Novartis AG; Novartis Deutschland GmbH); Benzopyrans and pharmaceutical compsns. containing them. EP 0828733; JP 1999505820; US 5905156; WO 9637490 . |
| 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) | 54658 | 2,2-dimethyl-N-phenyl-2H-chromene-6-sulfonamide | C17H17NO3S | 详情 | 详情 | |
| (V) | 54659 | sodium 4-hydroxybenzenesulfonate | C6H5NaO4S | 详情 | 详情 | |
| (VI) | 54660 | 4-hydroxybenzenesulfonyl chloride | C6H5ClO3S | 详情 | 详情 | |
| (VII) | 54661 | 4-hydroxy-N-phenylbenzenesulfonamide | C12H11NO3S | 详情 | 详情 | |
| (VIII) | 22416 | 3-chloro-3-methyl-1-butyne | 1111-97-3 | C5H7Cl | 详情 | 详情 |
| (IX) | 54662 | 4-[(1,1-dimethyl-2-propynyl)oxy]-N-phenylbenzenesulfonamide | C17H17NO3S | 详情 | 详情 |
合成路线13
该中间体在本合成路线中的序号：(V)7-Aminoquinolin-2-one (III) was prepared by Knorr cyclization of m-phenylenediamine (I) with ethyl acetoacetate (II). Subsequent diazotization of (II), followed by acid hydrolysis gave rise to the 7-hydroxyquinolinone (IV). Alkylation of (IV) with 3-chloro-3-methylbut-1-yne (V), followed by Claisen rearrangement of the resulting propargyl ether (V) afforded the pyranoquinolinone (VII). This was protected as the N-Boc derivative (VIII) by treatment with Boc2O and Et3N. Sharpless asymmetric dihydroxylation of (VIII) using dihydroquinine 2,5-diphenyl-4,6-pyrimidinediyl diether ((DHQ)2-PYR) as the chiral catalyst furnished the (R,R)-diol (IX), which was esterified with (-)-(S)-camphanoyl chloride (X) to produce diester (XI). The Boc protecting group of (XI) was finally removed by treatment with trifluoroacetic acid.
| 【1】 Cosentino, L.M.; Xia, Y.; Yang, Z.-Y.; Brossi, A.; Lee, K.-H.; Anti-AIDS agents Part 41: Synthesis and anti-HIV activity of 3',4'-di-O-(-)-camphanoyl-(+)-cis-khellactone (DCK) lactam analogues. Bioorg Med Chem Lett 2000, 10, 10, 1003. |
| 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) | 41612 | 1,3-benzenediamine; 3-aminophenylamine | 108-45-2 | C6H8N2 | 详情 | 详情 |
| (II) | 11819 | ethyl acetoacetate; ethyl 3-oxobutanoate；Acetoacetic ester;Ethyl beta-ketobutyrate;ethyl 3-oxobutyrate | 141-97-9 | C6H10O3 | 详情 | 详情 |
| (III) | 41613 | 7-amino-4-methyl-2(1H)-quinolinone | 19840-99-4 | C10H10N2O | 详情 | 详情 |
| (IV) | 41614 | 7-hydroxy-4-methyl-2(1H)-quinolinone | C10H9NO2 | 详情 | 详情 | |
| (V) | 22416 | 3-chloro-3-methyl-1-butyne | 1111-97-3 | C5H7Cl | 详情 | 详情 |
| (VI) | 41615 | 7-[(1,1-dimethyl-2-propynyl)oxy]-4-methyl-2(1H)-quinolinone | C15H15NO2 | 详情 | 详情 | |
| (VII) | 41616 | 4,8,8-trimethyl-1,8-dihydro-2H-pyrano[2,3-h]quinolin-2-one | C15H15NO2 | 详情 | 详情 | |
| (VIII) | 41617 | tert-butyl 4,8,8-trimethyl-2-oxo-2H-pyrano[2,3-h]quinoline-1(8H)-carboxylate | C20H23NO4 | 详情 | 详情 | |
| (IX) | 41618 | tert-butyl (9R,10R)-9,10-dihydroxy-4,8,8-trimethyl-2-oxo-9,10-dihydro-2H-pyrano[2,3-h]quinoline-1(8H)-carboxylate | C20H25NO6 | 详情 | 详情 | |
| (X) | 41620 | (1R,4S)-4,7,7-trimethyl-3-oxo-2-oxabicyclo[2.2.1]heptane-1-carbonyl chloride | C10H13ClO3 | 详情 | 详情 | |
| (XI) | 41619 | tert-butyl (9R,10R)-4,8,8-trimethyl-2-oxo-9,10-bis([[(4S)-4,7,7-trimethyl-3-oxo-2-oxabicyclo[2.2.1]hept-1-yl]carbonyl]oxy)-9,10-dihydro-2H-pyrano[2,3-h]quinoline-1(8H)-carboxylate | C40H49NO12 | 详情 | 详情 |
合成路线14
该中间体在本合成路线中的序号：(VI)(S)-Piperazine-2-carboxylic acid (I) was sequentially protected as the 4-Boc derivative (II) and then as the 1-Alloc-4-Boc-piperazine (III). After conversion of (III) to benzyl ester (IV), its N-Boc group was selectively removed by treatment with trifluoroacetic acid. The resultant 4-deprotected piperazine (V) was then alkylated with 3-chloro-3-methyl-1-butyne (VI) yielding (VII). Copper-promoted coupling of 4-hydroxy-3,5-diiodopyridine (IX) prepared by halogenation of 4-hydroxypyridine (VIII) with N-iodosuccinimide with the propargyl piperazine (VII) gave rise to the furo[3,2-c]pyridine derivative (X). The N-Alloc protecting group was then replaced by the N-Boc group to yield (XII) via palladium catalyzed deprotection of (X), followed by treatment of the resultant piperazine (XI) with Boc2O. Simultaneous hydrogenolysis of the benzyl ester and the iodo substituent of (XII) led to acid (XIII). After coupling of (XIII) with 2,2,2-trifluoroethylamine, acidic cleavage of the N-Boc group furnished the piperazine-2-carboxamide (XIV).
| 【1】 gamma-Hydroxy-2-(fluoroalkylaminocarbonyl)-1-piperazinepentanamides as HIV protease inhibitors. EP 1242426; WO 0138332 . |
| 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) | 16266 | (2S)-hexahydro-2-pyrazinecarboxylic acid; (S)-Piperazine-2-carboxylic acid | C5H10N2O2 | 详情 | 详情 | |
| (II) | 51591 | (2R)-4-(tert-butoxycarbonyl)-2-piperazinecarboxylic acid | C10H18N2O4 | 详情 | 详情 | |
| (III) | 56252 | (2S)-1-[(allyloxy)carbonyl]-4-(tert-butoxycarbonyl)-2-piperazinecarboxylic acid | C14H22N2O6 | 详情 | 详情 | |
| (IV) | 56253 | 1-allyl 2-benzyl 4-(tert-butyl) (2S)-1,2,4-piperazinetricarboxylate | C21H28N2O6 | 详情 | 详情 | |
| (V) | 56254 | 1-allyl 2-benzyl (2S)-1,2-piperazinedicarboxylate | C16H20N2O4 | 详情 | 详情 | |
| (VI) | 22416 | 3-chloro-3-methyl-1-butyne | 1111-97-3 | C5H7Cl | 详情 | 详情 |
| (VII) | 56255 | 1-allyl 2-benzyl (2S)-4-(1,1-dimethyl-2-propynyl)-1,2-piperazinedicarboxylate | C21H26N2O4 | 详情 | 详情 | |
| (VIII) | 56256 | 4-Hydroxypyridine; 4-Pyridinol; 4(1H)-Pyridone; 4-Pyridol; 4-Pyridone; gamma-Pyridone | 626-64-2 | C5H5NO | 详情 | 详情 |
| (IX) | 56257 | 3,5-diiodo-4-pyridinol | C5H3I2NO | 详情 | 详情 | |
| (X) | 56258 | 1-allyl 2-benzyl (2S)-4-[1-(7-iodofuro[3,2-c]pyridin-2-yl)-1-methylethyl]-1,2-piperazinedicarboxylate | C26H28IN3O5 | 详情 | 详情 | |
| (XI) | 56259 | benzyl (2S)-4-[1-(7-iodofuro[3,2-c]pyridin-2-yl)-1-methylethyl]-2-piperazinecarboxylate | C22H24IN3O3 | 详情 | 详情 | |
| (XII) | 56260 | 2-benzyl 1-(tert-butyl) (2S)-4-[1-(7-iodofuro[3,2-c]pyridin-2-yl)-1-methylethyl]-1,2-piperazinedicarboxylate | C27H32IN3O5 | 详情 | 详情 | |
| (XIII) | 56261 | (2S)-1-(tert-butoxycarbonyl)-4-(1-furo[3,2-c]pyridin-2-yl-1-methylethyl)-2-piperazinecarboxylic acid | C20H27N3O5 | 详情 | 详情 | |
| (XIV) | 56262 | (2S)-4-(1-furo[3,2-c]pyridin-2-yl-1-methylethyl)-N-(2,2,2-trifluoroethyl)-2-piperazinecarboxamide | C17H21F3N4O2 | 详情 | 详情 |
合成路线15
该中间体在本合成路线中的序号：(II)Condensation of methyl 3,5-dihydroxybenzoate (I) with 3-chloro-3-methyl-1-butyne (II) in the presence of CuI, followed by thermal cyclization at 75 C, gives rise to a mixture of two regioisomeric chromenes (III) and (IV). After chromatographic separation, the desired isomer (III) is reduced with LiAlH4 to provide alcohol (V). Copper-catalyzed coupling of the phenolic chromene (V) with sodium 2-iodobenzoate (VI) leads to the diaryl ether (VII), which is further cyclized to the pyranoxanthenone (VIII) in the presence of trifluoroacetic anhydride. After basic hydrolysis of the trifluoroacetate ester (VIII), the resultant alcohol (IX) is converted to mesylate (X) by treatment with methanesulfonyl chloride and triethylamine. Finally, displacement of the mesylate group of (X) with N,N-diethyl ethylenediamine (XI) furnishes the title compound.
| 【1】 Kolokythas, G.; et al.; Design and synthesis of some new pyranoxanthenone aminoderivatives with cytotoxic activity. Bioorg Med Chem Lett 2002, 12, 11, 1443. |
| 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) | 25155 | methyl 3,5-dihydroxybenzoate | 2150-44-9 | C8H8O4 | 详情 | 详情 |
| (II) | 22416 | 3-chloro-3-methyl-1-butyne | 1111-97-3 | C5H7Cl | 详情 | 详情 |
| (III) | 57036 | methyl 7-hydroxy-2,2-dimethyl-2H-chromene-5-carboxylate | C13H14O4 | 详情 | 详情 | |
| (IV) | 57037 | methyl 5-hydroxy-2,2-dimethyl-2H-chromene-7-carboxylate | C13H14O4 | 详情 | 详情 | |
| (V) | 57039 | 5-(hydroxymethyl)-2,2-dimethyl-2H-chromen-7-ol | C12H14O3 | 详情 | 详情 | |
| (VI) | 57038 | sodium 2-iodobenzoate | C7H4INaO2 | 详情 | 详情 | |
| (VII) | 57040 | 2-{[5-(hydroxymethyl)-2,2-dimethyl-2H-chromen-7-yl]oxy}benzoic acid | C19H18O5 | 详情 | 详情 | |
| (VIII) | 57041 | (2,2-dimethyl-6-oxo-2H,6H-pyrano[3,2-b]xanthen-5-yl)methyl 2,2,2-trifluoroacetate | C21H15F3O5 | 详情 | 详情 | |
| (IX) | 57042 | 5-(hydroxymethyl)-2,2-dimethyl-2H,6H-pyrano[3,2-b]xanthen-6-one | C19H16O4 | 详情 | 详情 | |
| (X) | 57043 | (2,2-dimethyl-6-oxo-2H,6H-pyrano[3,2-b]xanthen-5-yl)methyl methanesulfonate | C20H18O6S | 详情 | 详情 | |
| (XI) | 12420 | N-(2-Aminoethyl)-N,N-diethylamine; N,N-Diethylethylene-diamine; N(1),N(1)-Diethyl-1,2-ethanediamine | 100-36-7 | C6H16N2 | 详情 | 详情 |