1111-97-3

Usage

Uses

Used in Chemical Synthesis:
3-Chloro-3-methyl-1-butyne is used as a propargyl chloride to alkylate methanol, ethanol, ammonia, and amines, resulting in the formation of propargylic ethers and amines. This application is crucial in the synthesis of various organic compounds and intermediates.
Used in Pharmaceutical Industry:
In the pharmaceutical industry, 3-chloro-3-methyl-1-butyne is utilized in the preparation of a series of benzo[b]pyrano[2,3-i]xanthen-6-ones and benzo[b]pyrano[3,2-h]xanthen-7-ones, which are important compounds with potential therapeutic applications.
Used in Organic Chemistry Research:
3-Chloro-3-methyl-1-butyne is also used in the synthesis of 6-hydroxy-3,3-dimethyl-3H,7H-benzo[a]pyrano[3,2-h]xanthen-7-one, 5-hydroxy-2,2-dimethyl-2H,6H-benzo[a]pyrano[2,3-i]xanthen-6-one, and 3,3-dimethyl-3Hbenzofuro[3,2-f][1]-benzopyran. These compounds are valuable for research in organic chemistry and may have potential applications in various fields, including materials science and pharmaceuticals.

InChI:InChI=1/C5H7Cl/c1-4-5(2,3)6/h1H,2-3H3

Upstream product

• 115-19-5 2-methyl-but-3-yn-2-ol 
• 598-23-2 3-methyl-but-1-yne 
• 36566-81-1 dimethylethynylmethyl hydroperoxide 
• 108176-11-0 1-chloro-3,3-dimethylcyclopropene 
• 7647-01-0 hydrogenchloride 
• 78-80-8 2-methylbut-1-en-3-yne 
• 21678-37-5 N,N,2-trimethylpropionamide 
• 26189-59-3 1-chloro-1-(dimethylamino)-2-methyl-1-propene 

Downstream Products

• 7223-44-1 1-(1,1-dimethyl-2-propynyl)-pyrrolidine 
• 113895-25-3 methyl 2,4,4-trimethyl-5-methylene-4,5-dihydro-3-furoate 
• 100053-51-8 5-methoxy-2,4,4,5-tetramethyl-4,5-dihydro-furan-3-carboxylic acid methyl ester 
• 52148-91-1 methyl 5-methyl-2,4-hexadienoate 
• 64236-30-2 2-Methyl-6-(2-methyl-propenyl)-4-oxo-cyclohex-2-enecarboxylic acid methyl ester 
• 13994-57-5 3-methoxy-3-methylbut-1-yne 
• 7740-69-4 3-ethoxy-3-methyl-but-1-yne 
• 78-80-8 2-methylbut-1-en-3-yne 
• 30504-61-1 ((2-methylbut-3-yn-2-yl)oxy)benzene 
• 21079-27-6 diethyl 2-(1,1-dimethyl-2-propynyl)malonate 
• 918-82-1 3,3-dimethyl-1-pentyne 
• 1604-29-1 1,1-dimethyl-2-propynyl acetate 
• 64236-30-2 (+/-)-2-methyl-6t-(2-methyl-propenyl)-4-oxo-cyclohex-2-ene-r-carboxylic acid methyl ester 
• 598-25-4 Dimethylallene 

Relevant academic research and scientific papers

Six- and eightfold palladium-catalyzed gross-coupling reactions of hexa- and octabromoarenes

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).

VISCOSOL, A C-3' PRENYLATED FLAVONOID FROM DODONAEA VISCOSA

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.

SYP-5, a novel HIF-1 inhibitor, suppresses tumor cells invasion and angiogenesis

Hypoxia-inducible factor-1 (HIF-1) plays an essential role in carcinogenesis. The overexpression of HIF-1 induced by hypoxia is closely associated with metastasis, poor prognosis and high mortality. In this study, a novel HIF-1 inhibitor SYP-5 was first observed by the luciferase reporter assay. Western blots results showed SYP-5 inhibited hypoxia-induced upregulation of HIF-1. Moreover, the proteins of vascular endothelial growth factor (VEGF) and matrix metalloproteinases (MMP)-2 that are targets of HIF-1, were down-regulated by SYP-5. Furthermore, in the tube formation assay, SYP-5 suppressed angiogenesis induced by hypoxia and VEGF in vitro. Additionally, using Transwell and RTCA assays, we found that SYP-5 also retarded the Hep3B and Bcap37 cells migration and invasion induced by hypoxia and FBS. Last, we also detected the upstream pathways related to HIF-1 and found both PI3K/AKT and MAPK/ERK were involved in the SYP-5 mediated invasive inhibition of Bcap37 cells. These results indicates that SYP-5 inhibits tumor cell migration and invasion, as well as tumor angiogenesis, which are mediated by suppressing PI3K/AKT- and MAPK/ERK-dependent HIF-1 pathway. It suggests that SYP-5 might be a potential HIF-1 inhibitor as an anticancer agent.

Asymmetric epoxidation of chromenes mediated by iminium salts: Synthesis of mollugin and (3S,4R)-trans-3,4-dihydroxy-3,4-dihydromollugin

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.

Comparative reactivity of hydroxyketones and their derivatives in the reactions with N,S-nucleophiles

The reactions of thiosemicarbazide (TSC), thiocarbohydrazide, and hydrazine thiocarbamate with oxyketones, haloketones, and derivatives of acetylenic alcohols were studied. Thiadiazines bearing exocyclic thio and hydrazo groups were synthesized. Acetylenic alcohols react with TSC to give the corresponding thiazolidines. The reactions of halo derivatives of acetylenic alcohols with TSC are complicated by side reactions.

Enantioselective epoxidation of dihydroquinolines by using iminium salt organocatalysts

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

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.

Calix[n] arenes mediated phase-transfer catalytic synthesis of purine derivatives

A new route was designed to achieve the synthesis of purine derivatives under phase-transfer catalysis conditions using calix[n]arenes TACnA (n = 4, 6, and 8) as phase-transfer catalyst for the first time in this particular type of synthesis. The compounds were synthesized in excellent yields (70%-80%) and the structures were established on the basis of consistent IR, 1H NMR, FAB-Mass, and elemental analyses data. Their purity has been ascertained by chromatographic resolution using acetonitrile, methanol, and water (50:30:20, v/v) as eluenting system. Moreover, the kinetics of the reaction was studied and it was found to obey first-order kinetics. Effect of various parameters, namely, temperature, amount of catalyst, stirring speed, and so on was also investigated.

Process for preparing 3-chloro-3-methylbutyne by usingsophthalic acid acylating chlorination byproduct hydrogen chloride gas

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.

A mild method for the replacement of a hydroxyl group by halogen: 3. the dichotomous behavior of α-haloenamines towards allylic and propargylic alcohols

A study of the deoxyhalogenation of allylic and propargylic alcohols with tetramethyl-α-halo-enamines is reported. Primary allylic and primary and secondary propargylic alcohols gave the corresponding halides in high yields. Secondary allylic and propargylic alcohols yielded the corresponding secondary halides but the reaction also produced some rearranged primary halides (I > Br > Cl). The reactions with tertiary allylic and tertiary propargylic alcohols gave several products and was therefore of little synthetic value. However, the addition of triethylamine to the reaction mixture or the use of lithium alkoxide instead of alcohol brought about a major change of the course of the reaction which led to amides carrying an allyl or an allenyl group at C2. This was shown to result from a Claisen-Eschenmoser rearrangement of an intermediate α-allyloxy- or propargyloxy-enamine.