1111-97-3Relevant articles and documents
Six- and eightfold palladium-catalyzed gross-coupling reactions of hexa- and octabromoarenes
Stulgies, Balder,Prinz, Peter,Magull, Joerg,Rauch, Karsten,Meindl, Kathrin,Ruehl, Stephan,De Meijere, Armin
, p. 308 - 320 (2005)
Palladium-catalyzed sixfold coupling of hexabromobenzene (20) with a variety of alkenylboronates and alkenylstannanes provided hexaalkenylbenzenes 1 in up to 73% and 16 to 41% yields, respectively. In some cases pentaalkenylbenzenes 21 were isolated as the main products (up to 75%). Some functionally substituted hexaalkenylbenzene derivatives containing oxygen or sulfur atoms in each of their six arms have also been prepared (16 to 24% yield). The sixfold coupling of the less sterically encumbered 2, 3, 6, 7, 10, 11-hexabromotriphenylene (24) gave the desired hexakis(3,3-dimethyl-1-butenyl) triphenylene (25) in 93% yield. The first successful cross-coupling reaction of octabromonaphthalene (26) gave octakis-(3,3-dimethyl-1-butenyl)naphthalene (27) in 21% yield. Crystal structure analyses disclose that, depending on the nature of the substituents, the six arms are positioned either all on the same side of the central benzene ring as in 1a and 1i, making them nicely cup-shaped molecules, or alternatingly above and below the central plane las in 1h and 23. In 27, the four arms at C-1, 4, 6, 7 are down, while the others are up, or vice versa. Upon catalytic hydrogenation, 1a yielded 89% of hexakis(tert-butylethyl)benzene (23). Some efficient accesses to alkynes with sterically demanding substituents are also described. Elimination of phosphoric acid from the enol phosphate derived from the corresponding methyl ketones gave 1-ethynyladamantane (3b, 62% yield), 1-ethynyl-1-methylcyclohexane (3c, 85%) and 3,3-dimethylpentyne (3e, 65%). 1-(Trimethylsilyl)ethynylcyclopropane (7) was used to prepare 1-ethynyl-1-methylcyclopropane (3d) (two steps, 64% overall yield). The functionally substituted alkynes 3 f-h were synthesized in multistep sequences starting from the propargyl chloride 11, which was prepared in high yields from the dimethylpropargyl alcohol 10 (94%). The alkenylstannanes 19 were prepared by hydrostannation of the corresponding alkynes in moderate to high yields (42-97%), and the alkenylboronates 2 and 4 by hydroboration with catecholborane (27-96% yield) or pinacolborane (26-69% yield).
Poutsma
, p. 2925 (1969)
VISCOSOL, A C-3' PRENYLATED FLAVONOID FROM DODONAEA VISCOSA
Sachdev, Kusum,Kulshreshtha, Dinesh K.
, p. 1967 - 1970 (1986)
The structure of viscosol, a new prenylated flavonoid isolated from the aerial parts of Dodonaea viscosa, was established on the basis of spectral studies as well as by the conversion of the flavonol penduletin into permethyl viscosol.
Asymmetric epoxidation of chromenes mediated by iminium salts: Synthesis of mollugin and (3S,4R)-trans-3,4-dihydroxy-3,4-dihydromollugin
Bulman Page, Philip C.,Chan, Yohan,Noor Armylisas, Abu Hassan,Alahmdi, Mohammed
, p. 8406 - 8416 (2016)
Organocatalytic asymmetric epoxidation of chromenes mediated by iminium salt catalysts under non-aqueous conditions provided ees as high as 99%. Contrastingly, reaction under aqueous conditions can form the corresponding diol products with ees as high as 71%. The process has been used for the synthesis of the East African medicinal plant metabolite (3S,4R)-trans-3,4-dihydroxy-3,4-dihydromollugin.
Enantioselective epoxidation of dihydroquinolines by using iminium salt organocatalysts
Page, Philip C. Bulman,Day, David P.,Chan, Yohan
, p. 8029 - 8034 (2014)
The first examples of asymmetric epoxidation of dihydroquinoline substrates using iminium salt organocatalysts are reported. The 3,4-epoxytetrahydroquinoline products are obtained in good yields and with moderate to good enantioselectivities.
Natural product-inspired rational design, synthesis and biological evaluation of 2,3-dihydropyrano[2,3-f]chromen-4(8H)-one based hybrids as potential mitochondrial apoptosis inducers
Sakthivel, Palaniappan,Ilangovan, Andivelu,Kaushik, Mahabir Prasad
, p. 302 - 318 (2016)
Synthesis of novel pyranochromanone amide hybrids, by combining pyranochromanone pharmacophore and privileged scaffolds such as 2-amino-1,3,4-thiadiaole/2-aminothiazole/aminopyridine/aminonaphthalene and anti-cancer evaluation of a series led us to discover a series of new chemical entities (NCEs) showing broad spectrum of anti-cancer activity against three different human cancer cell lines (MCF-7, A549 and HeLa), at IC50values ranging from 14.3 to 97.8?μM. Among them, some compounds such as 15b, 15d, 20a and 20b displayed excellent activity against breast cancer cell line MCF-7. Detailed biological studies such as AO/EB dual staining, Hoechst 33342 staining, FACS analysis of mitochondrial membrane potential (Δψm) using JC-1 dye and DNA fragmentation confirmed the apoptosis induced by the hybrids. Gene expression studies by Real time RT-PCR has shown that these compounds are efficient regulator of anti-apoptotic gene Bcl-2. Western blot analysis also revealed that these compounds persuade apoptosis through intrinsic pathway by up-regulating the pro-apoptotic protein Bax and down-regulating the anti-apoptotic protein Bcl-2. Molecular docking studies reveal that compounds 15b and 20b binds efficiently with Bcl-2 promoter G-quadruplex.
Process for preparing 3-chloro-3-methylbutyne by usingsophthalic acid acylating chlorination byproduct hydrogen chloride gas
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Paragraph 0022-0027, (2021/05/12)
The invention discloses a production process for preparing 3-chloro-3-methylbutyne by using an isophthalic acid acylating chlorination byproduct hydrogen chloride gas, which basically comprises the following steps: putting quantitative trichloromethyl benzene, isophthalic acid and a catalyst into an acylation reaction kettle, and simultaneously putting hydrochloric acid with a certain concentration, a catalyst and 3-methyl butyn-3-ol into a chlorination kettle; slowly raising the temperature of the acylation kettle to the reaction temperature, controlling the temperature of the chlorination kettle to be within a specified temperature range, and slowly dropwise adding the rest trichloromethyl benzene after the temperature of the acylation kettle is stable; subjecting the acylation byproduct hydrogen chloride gas to washing and impurity removal by a hydrochloric acid tower and deep cooling and water removal, and then introducing the treated hydrogen chloride gas into the chlorination kettle for chlorination of 3-methyl butyn-3-ol to prepare 3-chloro-3-methylbutyne, and returning deep cooling condensate to a hydrochloric acid washing tower; and after hydrochloric acid in the hydrochloric acid washing tower is recycled for a certain batch, conducting suction filtration, tap water washing and drying to obtain a small amount of byproduct benzoic acid.
Synthesis and biological evaluation of 2,2-dimethylbenzopyran derivatives as potent neuroprotection agents
Du, Fangyu,Zhou, Qifan,Fu, Xiaoxiao,Shi, Yajie,Chen, Yuanguang,Fang, Wuhong,Yang, Jingyu,Chen, Guoliang
, p. 2498 - 2508 (2019/02/01)
The development of novel neuroprotection agents is of great significance for the treatment of ischemic stroke. In this study, a series of compounds comprising 2,2-dimethylbenzopyran groups and cinnamic acid groups have been synthesized. Preferential combination principles and bioisostere that improved the neuroprotective effect of the compounds were identified for this series via biological activity assay in vitro. Meanwhile, a functional reversal group of the acrylamide amide resulted in the most active compounds. Among them, BN-07 significantly improved the morphology of neurons and obviously increased cell survival rate of primary neurons induced by oxygen glucose deprivation (OGD), superior to clinically used anti-ischemic stroke drug edaravone (Eda). Overall, our findings may provide an alternative strategy for the design of novel anti-ischemic stroke agents with more potency than Eda.
Preparation method for propyzamide
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Paragraph 0007-0008; 0036-0040; 0054; 0058, (2018/05/01)
The invention discloses a preparation method for propyzamide. The preparation method comprises the following steps: preparing 3-chloro-3-methylbutyne through a chlorination reaction; then preparing 3-amino-3-methylbutyne through an aminolysis reaction; and then carrying out an amidation reaction so as to prepare high-purity propyzamide. The optimal preparation method for propyzamide is screened out through a large number of experiments; the preparation method is reasonable in the whole process design and simple and efficient in process operation; in particular, optimal reaction conditions arescreened out, optimal raw material composition is determined for the chlorination reaction in the step 1, the aminolysis reaction in the step 2 and the amidation reaction in the step 3, and the proportions of reaction raw materials, reaction temperature, reaction time and the like are optimized, so reaction yield can be greatly increased (wherein the yield can reach 93% or more), side reactions can be reduced, reaction rate can be increased, and production cost can be greatly lowered; so the preparation method has good application prospects.
