933-52-8

Usage

Uses

Used in Life Science Research:
TETRAMETHYL-1,3-CYCLOBUTANEDIONE is used as a chemical for life science research, where it can be employed in the development and study of new compounds and their potential applications in biological systems.
Used in Chemical Synthesis:
TETRAMETHYL-1,3-CYCLOBUTANEDIONE is used as a chemical intermediate in the synthesis of other chemical compounds. Its unique structure allows it to be a valuable building block in the creation of a wide range of molecules.
Used in Organic Chemistry:
TETRAMETHYL-1,3-CYCLOBUTANEDIONE is used in organic chemistry as a reagent or intermediate in various organic reactions. Its cyclobutane ring and methyl groups can participate in a variety of chemical transformations, making it a useful component in the synthesis of complex organic molecules.

Synthesis Reference(s)

Canadian Journal of Chemistry, 50, p. 3923, 1972 DOI: 10.1139/v72-619

Purification Methods

Crystallise the dione from *C6H6 and dry it in vacuo over P2O5 in an Abderhalden pistol. [Beilstein 7 III 3234, 7 IV 2004.]

InChI:InChI=1/C8H12O2/c1-7(2)5(9)8(3,4)6(7)10/h1-4H3

Upstream product

• 598-26-5 dimethylketene 
• 121-44-8 triethylamine 
• 79-30-1 isobutyryl chloride 
• 10181-59-6 2,2,4,4-tetramethyl-3-thioxocyclobutanone 
• 13994-57-5 3-methoxy-3-methylbut-1-yne 
• 694-59-7 pyridine N-oxide 
• 73876-87-6 2-methyl-1-(trimethylsilyl)prop-1-enyl triflate 
• 917-95-3 t-butylnitrite 
• 861356-33-4 3,3,7,7,10,10-hexamethyl-[1,5]dioxecane-2,4,6,8,10-pentaone 
• 109-92-2 ethyl vinyl ether 
• 931-89-5 (E)-cyclooctene 
• 15848-07-4 thiobenzophenone S-oxide 
• 23604-61-7 1,1,3,3-tetramethyl-8-thia-5,6-diazaspiro[3.4]oct-5-en-2-one 
• 39257-42-6 2,2,4,4-tetramethyl-3-thioxocyclobutanone S-oxide 

Downstream Products

• 16424-58-1 5-hydroxy-2,4,4,5-tetramethyl-hexan-3-one 
• 67-64-1 acetone 
• 565-80-0 2,4-dimethylpentan-3-one 
• 119-61-9 benzophenone 
• 16424-64-9 2,2,4-Trimethyl-1-(2',4',6'-trimethylphenyl)pentane-1,3-dione 
• 598-26-5 dimethylketene 
• 76-84-6 triphenylmethyl alcohol 
• 4406-41-1 N-phenylisobutyramide 
• 1192-14-9 2,2-dimethylcyclobutanone 
• 32674-76-3 2,2,4-Trimethyl-4-(methyl-phenoxy-phosphinoyl)-3-oxo-pentanoic acid methyl ester 
• 32687-25-5 Dimethyl-phosphoramidous acid 1-(1-dimethylcarbamoyl-1-methyl-ethyl)-2-methyl-propenyl ester phenyl ester 
• 103570-79-2 3,3,5-trimethyl-1-(triphenyl-λ⁵-phosphanylidene)-hexane-2,4-dione 
• 90205-22-4 2,2,4-Trimethyl-3-oxo-valeramid 
• 4298-75-3 2,2,4,4-tetramethylcyclobutanone 

Relevant academic research and scientific papers

Episulfidation of trans-Cyclooctene with an 1,2,4-Oxadithiolane

The dipolar cycloaddition of thiobenzophenone S-oxide (1) and 2,2,4,4-tetramethyl-3-thioxocyclobutanone (2) generates the labile 1,2,4-oxadithiolane I, which in the presence of trans-cyclooctene (3) affords trans-episulfide (9). In this direct sulfur tran

Unexpected products from the reaction of 2,2,4,4-tetramethylcyclobutane- 1,3-dione with the Makosza reagent

Reaction of 2,2,4,4-tetramethylcyclobutane-1,3-dione (2) under phase- transfer-catalysis (PTC) conditions (CHCl3/aqueous NaOH) yielded a complex mixture of unexpected products (Scheme 2). From the organic phase, three ring-enlarged products 7-9 with a cyclopentane-1,3-dione (cf- 7 and 9) or a cyclopentenone skeleton (cf. 8) were isolated in low yield. After acidification of the aqueous phase, the oily residue was treated with CH2N2, and methyl 3-oxopentanoate 12 and dimethyl 2-hydroxybutanedioate 13 were obtained in almost equal amounts. The structures of 8 and 9 were established by X-ray crystal-structure analysis (Fig.). Mechanisms for the formation of the products, initiated by nucleophilic attack of trichloromethanide ion and opening of the cyclobutane ring, are proposed in Schemes 3 and 4.

Preparation method of 2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol

The invention discloses a preparation method of 2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol, which comprises the following steps: dissolving isobutyryl chloride in a first organic solvent, adding triethylamine and zinc powder while stirring, heating to reflux, reacting, cooling, filtering, washing, and carrying out reduced pressure distillation to obtain a distillation substrate; and dissolving the distillation substrate in a second organic solvent, cooling, filtering, introducing hydrogen under the action of a catalyst, and carrying out a reaction to obtain the product. According to the method, on the basis of the process of the BASF company, after triethylamine hydrochloride is formed by triethylamine serving as an acid-binding agent, triethylamine is released from the triethylamine hydrochloride by using proper metal, so that the triethylamine serving as the acid-binding agent can be recycled, and the triethylamine only plays a role of a bridge in a system; through continuous exchange and circulation of a small amount of triethylamine, the reaction is carried out until the reaction is complete.

Tetramethylcyclobutanedione and tetramethylcyclobutane diol Method for manufacturing the same

The invention provides tetramethylcyclobutanedione and tetramethylcyclobutane diol, and a manufacturing method thereof. The present invention provides the following method. 2, 2, 4, 4 - Tetramethylcyclobutane -1, 3 - diketones can be easily produced by carrying out the dimerization reaction of the dimethylketene in a solvent suitable for the actual production (reaction time) by easily treating and general low boiling solvent in the production process. The dimerization reaction of the dimethyl ketene can be accelerated, and the time required for solvent removal can be shortened as compared with the high-boiling solvent. Compared with the prior art, the manufacturing can be performed in a short time.

The fluoride anion-catalyzed sulfurization of thioketones with elemental sulfur leading to sulfur-rich heterocycles: First sulfurization of thiochalcones ?

Fluoride anion was demonstrated as a superior activator of elemental sulfur (S8) to perform sulfurization of thioketones leading to diverse sulfur-rich heterocycles. Due to solubility problems, reactions must be carried out either in THF using tetrabutylammonium fluoride (TBAF) or in DMF using cesium fluoride (CsF), respectively. The reactive sulfurizing reagents are in situ generated, nucleophilic fluoropolysulfide anions FS(8?x)?, which react with the C=S bond according to the carbophilic addition mode. Dithiiranes formed thereby, existing in an equilibrium with the ring-opened form (diradicals/zwitterions) are key-intermediates, which undergo either a step-wise dimerization to afford 1,2,4,5-tetrathianes or an intramolecular insertion, leading in the case of thioxo derivatives of 2,2,4,4-tetramethylcyclobutane-1,3-dione to ring enlarged products. In reactions catalyzed by TBAF, water bounded to fluoride anion via H-bridges and forming thereby its stable hydrates is involved in secondary reactions leading, e.g., in the case of 2,2,4,4-tetramethyl-3-thioxocyclobutanone to the formation of some unexpected products such as the ring enlarged dithiolactone and ring-opened dithiocarboxylate. In contrast to thioketones, the fluoride anion catalyzed sulfurization of their α,β-unsaturated analogues, i.e., thiochalcones is slow and inefficient. However, an alternative protocol with triphenylphosphine (PPh3) applied as a catalyst, offers an attractive approach to the synthesis of 3H-1,2-dithioles via 1,5-dipolar electrocyclization of the in situ-generated α,β-unsaturated thiocabonyl S-sulfides. All reactions occur under mild conditions and can be considered as attractive methods for the preparation of sulfur rich heterocycles with diverse ring-size.

PROCESS FOR PREPARING 2,2,4,4-TETRAMETHYL-1,3-CYCLOBUTANEDIOL

The present invention refers to 2, 2, 4, 4 - tetramethyl - 1, 3 - cyclohexanedimethanol bhutan d this year a number bath method disclosure as follows. the method (A) meta acrylic acid (methacrylic acid, MAA) removed from the raw material (B) use as an intermediate in the mote [lik [lik] it buys [...] (isobutyric acid, IBA), 2, 2, 4, 4 - tetramethyl - 1, 3 - cyclohexanedimethanol [...] (C) dimethyl ketene (dimethyl Ketene, DMK) and (D) (2, 2, 4, 4 a-tetramethyl-a 1, 3 non-cyclobutanedione, CBDK) via a final material sequentially (E) 2, 2, 4, 4 - tetramethyl bhutan d this year cycle - 1, 3 - (2, 2, 4, 4 a-tetramethyl-a 1, 3 non-cyclobutanediol, CBDO) bath a number comprise substrate. According to the present invention number bath step optimization and a green protective environmental 2, 2, 4, 4 - tetramethyl - 1, 3 - cyclohexanedimethanol bhutan d this year through mirror number is encoded number bath method is highly lipophilic ball number. (by machine translation)

PROCESS FOR PREPARING 2,2,4,4-TETRAMETHYL-1,3-CYCLOBUTANEDIOL

Disclosed is a method for preparing 2,2,4,4-tetramethyl-1,3-cyclobutanediol, which prepares (E) 2,2,4,4-tetramethyl-1,3-cyclobutanediol (CBDO) which is a final material by sequentially going through (A) methacrylic acid (MAA) as a raw material, and (B) isobutyric acid (IBA), (C) isobutyric anhydride (IBAN), and (D) 2,2,4,4-tetramethyl-1,3-cyclobutanedione (CBDK) as an intermediate. According to the present invention, the method for preparing 2,2,4,4-tetramethyl-1,3-cyclobutanediol which is economical and eco-friendly by optimizing preparation steps and maximizing the efficiency is provided.COPYRIGHT KIPO 2019

Method for synthesis of 2, 2, 4, 4-tetramethyl-1, 3-cyclobutanedione

The invention belongs to the technical field of organic compound preparation and discloses a preparation method of 2, 2, 4, 4-tetramethyl-1, 3-cyclobutanedione. The preparation method comprises that isobutyric acid or isobutyric anhydride undergoes a cracking reaction according to a volume ratio of isobutyric acid or isobutyric anhydride to inert gas of 1: 10 to 1: 5 in a fixed bed pyrolysis reactor to produce dimethyl ketene and the dimethyl ketene directly undergoes a polymerization reaction in the solution in the same polymerization reactor to produce 2, 2, 4, 4-tetramethyl-1, 3-cyclobutanedione. The method optimizes a 2, 2, 4, 4-tetramethyl-1, 3-cyclobutanedione preparation process, realizes direct polymerization of cracking products, reduces a device investment, is free of a washing tower or an absorbing tower and prevents consumption of a lot of an absorption liquid and a loss of energy. Through above characteristics, compared with the existing competitive industrial methods, the method provided by the invention has better flexibility.

Photochemical formation and reactivities of substituted oxathiiranes in low-temperature argon matrices

Thiocarbonyl S-oxides (sulfines) derived from aliphatic and cycloaliphatic thioketones were irradiated in argon matrices at 10 K, and the resulting oxathiiranes were identified by comparison of computed and experimental IR spectra. Upon photolysis at 10 K, depending on the substitution pattern, the oxathiiranes underwent either H-shift reactions or regioselective ring enlargements to form the corresponding thioesters. After warming of the matrix material to 38-40 K, the oxathiiranes underwent fast desulfurization to yield the corresponding ketones. Density functional theory (DFT) computations at the B3LYP/6-311+G(3df,3pd) level suggest that the desulfurizations of oxathiiranes occurred as bimolecular processes with activation enthalpies near 0 kcal mol-1.

Polyester from dimethylketene and acetaldehyde: Direct copolymerization and β-lactone ring-opening polymerization

Two ways to obtain aliphatic polyesters (PEs) from dimethylketene and acetaldehyde were investigated. On the one hand, a direct anionic copolymerization was carried out in toluene at -60 °C. The resulting polymer was mainly composed of PE units. On the other hand, a two-step process involving the synthesis of 3,3,4-trimethyl-2-oxetanone by [2+2] cycloaddition, followed by its ring-opening polymerization, with various initiators and solvents, led to the expected PE. Molecular weights up to 9000 g mol -1 (measured by nuclear magnetic resonance (NMR)), with narrow polydispersity around 1.2, were obtained. These polymers were found stable up to 274 °C under nitrogen and a broad and complex endothermic peak attributed to crystallinity was observed near 139 °C by differential scanning calorimetry (DSC). The crystallinity, measured by X-ray diffraction, was close to 0.45.