专利号:US-10556913-B2 优先权日:2015-07-21 标 题:Asymmetric process for the preparation of thieno-indoles derivatives 发明人:BERIA ITALO; CARUSO MICHELE; DONATI DANIELE; ORSINI PAOLO 权利人:NERVIANO MEDICAL SCIENCES SRL 摘要:The present invention relates to a new process for the preparation of thieno-indole derivatives of formula (Ia) or (Ib), exploiting an asymmetric synthesis for the preparation of key (8S) or (8R) 8-(halomethyl)-1-alkyl-7,8-dihydro-6H-thieno[3,2-e]indol-4-ol intermediates, and to useful intermediate compounds of such process. n Thieno-indole derivatives are described and claimed in GB2344818, WO2013/149948 and WO2013/149946, which also disclose processes for their preparation. n Thieno-indole enantiopure derivatives can now be advantageously prepared through a new asymmetric synthesis of the key 8-(halomethyl)-7,8-dihydro-6H-thieno[3,2-e]indol intermediates, which, avoiding the chiral resolution step, provides benefits in terms of reducing time and costs of the whole process for their preparation. The synthesis starts from the N-alkylation of 5-amino-4-halo-3-alkyl-1-benzothiophene-7-ol derivatives with enantiopure glycidyl 3-nosylate, followed by intramolecular 6-endo-tet cyclization using alkyl Grignard reagents; Mitsunobu activation of the secondary alcohol promotes internal spirocyclization, affording the 4,4a,5,6-tetrahydro-8H-cyclopropa[c]thieno[3,2-e]indol-8-one derivatives; finally, stereo-electronically controlled regioselective cyclopropane opening yields the key enantiopure 8-(halomethyl)-1-alkyl-7,8-dihydro-6H-thieno[3,2-e]indol-4-ol intermediates; which can be further derivatized following teachings disclosed in WO2013/149948 or WO2013/149946, to prepare the final thieno-indole derivatives of formula (Ia) or (Ib). n Such compounds are disclosed to be alkylating compounds with cytotoxic activity, therefore useful as such in the treatment of a variety of cancers and in cell proliferative disorders, or, conjugated with different types of nucleophiles, in the preparation of Antibody Drug Conjugated derivatives.
专利号:US-8877977-B2 优先权日:2011-11-25 标题 :Synthesis of polyalkylenepolyamines having a low color index by homogeneously catalyzed alcohol amination in the presence of hydrogen 发明人:STRAUTMANN JULIA; SCHAUB THOMAS; HUEFFER STEPHAN; MAAS STEFFEN; PACIELLO ROCCO 权利人:STRAUTMANN JULIA; SCHAUB THOMAS; HUEFFER STEPHAN; MAAS STEFFEN; PACIELLO ROCCO; BASF SE 摘要:Process for the preparation of polyalkylenepolyamines by homogeneously catalyzed alcohol amination, in which aliphatic amino alcohols are reacted with one another or aliphatic diamines or polyamines are reacted with aliphatic diols or polyols with the elimination of water in the presence of a homogeneous catalyst and in the presence of hydrogen gas. Polyalkylenepolyamines obtainable by such processes and polyalkylenepolyamines comprising hydroxy groups, secondary amines or tertiary amines. Uses of such polyalkylenepolyamines as adhesion promoters for printing inks, adhesion promoters in composite films, cohesion promoters for adhesives, crosslinkers/curing agents for resins, primers for paints, wet-adhesion promoters for emulsion paints, complexing agents and flocculating agents, penetration assistants in wood preservation, corrosion inhibitors, immobilizing agents for proteins and enzymes.
专利号:WO-2013076053-A1 优先权日:2011-11-25 标题:Synthesis of polyalkylene polyamines with low color index by homogeneously catalyzed alcohol amination in the presence of hydrogen 发明人:STRAUTMANN JULIA; SCHAUB THOMAS; HUEFFER STEPHAN; MAAS STEFFEN; PACIELLO ROCCO 权利人:BASF SE; STRAUTMANN JULIA; SCHAUB THOMAS; HUEFFER STEPHAN; MAAS STEFFEN; PACIELLO ROCCO 摘要:The invention relates to a method for the production of polyalkylene polyamines by homogeneously catalyzed alcohol amination, wherein aliphatic alkanolamines are reacted with each other or aliphatic diamines or polyamines are reacted with aliphatic diols or polyols in the presence of a homogeneous catalyst while eliminating water and in the presence of hydrogen gas. The invention further relates to polyalkylene polyamines, which can be obtained by said methods, and to polyalkylene polyamines which contain hydroxyl groups, secondary amines or tertiary amines. The invention finally relates to uses of said polyalkylene polyamines as adhesion promoters in inks, adhesion promoters in composite films, cohesion promoters in adhesives, cross-linkers/hardeners for resins, primers for paints, wet adhesion promoters for dispersion paints, complexing agents and flocculants, penetration auxiliaries for use in wood preservation, corrosion inhibitors, and immobilization agents of proteins and enzymes.
专利号:WO-2022148752-A9 优先权日:2021-01-08 标 题 :Photochromic dyes and polymeric matrix for an efficient dimming film 发明人:KARIPIDOU ZOI; KNORR NIKOLAUS; HENNIG DIANA; ROSSELLI SILVIA; ONO HIDEKI; TAKANASHI HIDEHIKO; HERON MARK; EDGAR ROSS 权利人:SONY GROUP CORP; SONY EUROPE BV 摘要:The present disclosure relates to a photochromic molecule and uses of said molecule. The present disclosure further relates to a method of preparing a film comprising said molecule. The present disclosure also relates to a film prepared using said molecule and a device comprising said molecule. Furthermore, the present disclosure relates to a method for synthesis of said molecule. The photochromic molecules are represented by the following formulas: (1), (2), (3), (4), wherein Ar1, Ar2, Ar3, Ar4, Ar5, Ar6, Ar7, and Ar8 are, at each occurrence, independently selected from the group consisting of formula (I).
专利号:US-9056887-B2 优先权日:2011-07-26 标 题 :Minor groove binder phosphoramidites and methods of use 发明人:VOROBIEV ALEXEI; LUKHTANOV EUGENY A 权利人:VOROBIEV ALEXEI; LUKHTANOV EUGENY A; ELITECH HOLDING BV 摘要:Minor groove binder phosphoramidites having the formula M-L-PA, wherein M is a minor groove binder comprising a protected heteroaromatic amine, L is a linker, and PA is a phosphoramidite group, have been synthesized. Preferred methods of synthesis include synthesizing a minor groove binder intermediate containing a transiently protected hydroxyl group, protecting heteroaromatic amines of the corresponding minor groove binder intermediate as carbamate intermediates, reacting the carbamate intermediate to remove the transient protecting group to yield carbamate-protected minor groove binder agent as an intermediate with a free hydroxyl group, and converting the intermediate with a free hydroxyl group to the desired minor groove binder phosphoramidite. These minor groove binder phosphoramidites are useful in the preparation of oligonucleotide conjugates, particularly those for use as probes and primers. In preferred methods, an oligonucleotide sequence is synthesized using nucleoside phosphoramidites and the minor groove binder phosphoramidite is incorporated into the oligonucleotide sequence to form a protected oligonucleotide-minor groove binder conjugate. Then, deprotection produces the oligonucleotide-minor groove binder.
专利号:WO-2025039354-A1 优先权日:2023-08-23 标 题:Intermediate compound of oxcarbazepine and preparation method therefor 发明人:ZHAO JIANHONG; LI YONGGANG; XU YINGZHOU; ZHENG CHENGHAO 权利人:ZHEJIANG JIUZHOU PHARM CO LTD; ZHEJIANG RAYBOW PHARMACEUTICAL CO LTD 摘要:The present invention relates to the field of pharmaceutical synthesis, and specifically relates to a method for preparing a key intermediate of oxcarbazepine. Specifically, a compound represented by formula A is prepared from a compound represented by formula 4 under the action of a ring-opening reagent and selectively under the action of an esterification reagent, a protective reagent, a hydrolysis reagent and a chlorination reagent; a compound represented by formula 10 is prepared from the compound represented by formula A by means of a ring-closing reaction; and finally oxcarbazepine is prepared from the compound represented by formula 10. The route of the present invention achieves a relatively high conversion rate, and is more advantageous in the aspect of cost control. The reaction formulas are shown in formula (I), wherein R3 is OR1 or R2; R1 is hydrogen, a C1-C6 alkyl or substituted alkyl, or Na, K or Li; R2 is Cl or -OCOR5; R5 is a C1-C6 alkyl or substituted alkyl, an aryl, a substituted aryl, a phenyl, a benzyl or a substituted benzyl; and R4 is a C1-C6 alkyl, a substituted alkyl, an aryl, a substituted aryl, a benzyl or a substituted benzyl.
参考标题:Sequential 1,3-N- To C- And 1,3-C- To C-Migration Of Sulfonyl Groups Through The Synthesis Of 1,4-Diazepines From The Aza-[5 + 2] Cycloaddition Of Indoloazomethine Ylides 作者:Namrim Heo,Ilyong Jung,Dae Kyum Kim,Sang Hoon Han,Kooyeon Lee,Phil Ho Lee |发布日期:2020.8.21 摘要:Sequential 1,3-N- To C- And 1,3-C- To C-Migration Of Sulfonyl Groups Through The Synthesis Of 1,4-Diazepines From An Operationally Simple Thermal Aza-[5 + 2] Cycloaddition Reaction Of Indoloazomethine Ylides With Dialkyl Acetylenedicarboxylates Under Mild Conditions, Leading To The Formation Of C-Sulfonylated 1,4-Diazepines.
合成参考文献
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