2,2,4,4-Tetramethyl-1,3-cyclobutanediol

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2,2,4,4-Tetramethyl-1,3-cyclobutanediol
CBDO.png
cis- (left) and trans-2,2,4,4-Tetramethyl-1,3-cyclobutanediol (right)
(E)-CBDO-3D-balls.png
(Z)-CBDO-3D-balls.png
Names
IUPAC name
2,2,4,4-Tetramethylcyclobutane-1,3-diol
Other names
1,1,3,3-Tetramethyl-2,4-cyclobutanediol
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.019.219 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/C8H16O2/c1-7(2)5(9)8(3,4)6(7)10/h5-6,9-10H,1-4H3 Yes check.svgY
    Key: FQXGHZNSUOHCLO-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C8H16O2/c1-7(2)5(9)8(3,4)6(7)10/h5-6,9-10H,1-4H3
    Key: FQXGHZNSUOHCLO-UHFFFAOYAA
  • OC1C(C)(C)C(O)C1(C)C
Properties
C8H16O2
Molar mass 144.214 g·mol−1
AppearanceCrystalline white solid (powder)
Melting point 126 to 134 °C (259 to 273 °F; 399 to 407 K)
Boiling point 210 to 215 °C (410 to 419 °F; 483 to 488 K)
Hazards
Flash point 51 °C (124 °F; 324 K)
Safety data sheet (SDS)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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2,2,4,4-Tetramethyl-1,3-cyclobutanediol (CBDO) is an aliphatic diol. This diol is produced as a mixture of cis- and trans-isomers, depending on the relative stereochemistry of the hydroxyl groups. It is used as a monomer for the synthesis of polymeric materials, usually as an alternative to bisphenol A (BPA). CBDO is used in the production of tritan copolyester which is used as a BPA-free replacement for polycarbonate.

Contents

Replacement for BPA

The controversies associated with BPA in large quantities are ultimately related to its endocrine disrupting abilities. [1] Like BPA, CBDO is a diol with a structure suitable for making polyesters. CBDO’s C4 ring is sufficiently rigid to prevent the two OH groups from forming cyclic structures. Unlike BPA, there is no current evidence of carcinogenic or toxic effects from CBDO-based consumer products. There are, however, few studies on the toxicology of CBDO for both long term and short term effects.

CBDO has potential advantages relative to BPA as a building block for production of polyesters. CBDO is very stable thermally and mechanically. Polyesters prepared from CBDO are rigid materials, but the combination of CBDO with flexible diols results in materials with high impact resistance, low color, thermal stability, good photooxidative stability and transparency. [2] As an added bonus, CBDO-derived polymers have high ductility. [3] The thermal and mechanical properties of CBDO-derived polyesters are often superior to conventional polyesters. [2]

Preparation

Synthesis of CBDO involves pyrolysis of isobutyric anhydride followed by hydrogenation of the resulting 2,2,4,4-tetramethylcyclobutanedione. [4] This synthesis resembles the method used to produce CBDO today. The first step involves conversion of the isobutyric acid or its anhydride into the ketene. This ketene then dimerizes to form a four-membered ring with two ketone groups.

The product ring is hydrogenated to give a diol. The last step commonly involves catalytic hydrogenation with ruthenium, nickel, or rhodium catalysts. Hydrogenation of the diketone ring results in both cis and trans isomers. [3] [5] A simplified scheme for the production of CBDO is presented below.

CBDO Reaction Scheme.png

Structure and properties

The C4 ring of the cis isomer of CBDO is non-planar. For simple non-planar cyclobutanes, dihedral angles range from 19 to 31°. CBDO’s cis isomer crystallizes as two conformers with an average dihedral angle of 17.5° in the solid state. [6] However, the trans isomer has a dihedral angle of 0°. [7]

Polyesterification

The current economic method for the production of polyesters is direct esterification of dicarboxylic acids with diols. This condensation polymerization adds monomeric units to a chain. Individual chains react with one another through carboxyl and hydroxyl terminal groups. Finally, transesterification occurs within the chain. [8] Although CBDO is most often used in polyesters, mixed copolycarbonates of CBDO and a series of bisphenols have also been synthesized. The differing reactivities of the cis and trans isomers have not been studied in depth.

Related Research Articles

<span class="mw-page-title-main">Petrochemical</span> Chemical product derived from petroleum

Petrochemicals are the chemical products obtained from petroleum by refining. Some chemical compounds made from petroleum are also obtained from other fossil fuels, such as coal or natural gas, or renewable sources such as maize, palm fruit or sugar cane.

<span class="mw-page-title-main">Diels–Alder reaction</span> Chemical reaction

In organic chemistry, the Diels–Alder reaction is a chemical reaction between a conjugated diene and a substituted alkene, commonly termed the dienophile, to form a substituted cyclohexene derivative. It is the prototypical example of a pericyclic reaction with a concerted mechanism. More specifically, it is classified as a thermally-allowed [4+2] cycloaddition with Woodward–Hoffmann symbol [π4s + π2s]. It was first described by Otto Diels and Kurt Alder in 1928. For the discovery of this reaction, they were awarded the Nobel Prize in Chemistry in 1950. Through the simultaneous construction of two new carbon–carbon bonds, the Diels–Alder reaction provides a reliable way to form six-membered rings with good control over the regio- and stereochemical outcomes. Consequently, it has served as a powerful and widely applied tool for the introduction of chemical complexity in the synthesis of natural products and new materials. The underlying concept has also been applied to π-systems involving heteroatoms, such as carbonyls and imines, which furnish the corresponding heterocycles; this variant is known as the hetero-Diels–Alder reaction. The reaction has also been generalized to other ring sizes, although none of these generalizations have matched the formation of six-membered rings in terms of scope or versatility. Because of the negative values of ΔH° and ΔS° for a typical Diels–Alder reaction, the microscopic reverse of a Diels–Alder reaction becomes favorable at high temperatures, although this is of synthetic importance for only a limited range of Diels-Alder adducts, generally with some special structural features; this reverse reaction is known as the retro-Diels–Alder reaction.

<span class="mw-page-title-main">Epoxy</span> Type of material

Epoxy is the family of basic components or cured end products of epoxy resins. Epoxy resins, also known as polyepoxides, are a class of reactive prepolymers and polymers which contain epoxide groups. The epoxide functional group is also collectively called epoxy. The IUPAC name for an epoxide group is an oxirane.

<span class="mw-page-title-main">Epoxide</span> Organic compounds with a carbon-carbon-oxygen ring

In organic chemistry, an epoxide is a cyclic ether, where the ether forms a three-atom ring: two atoms of carbon and one atom of oxygen. This triangular structure has substantial ring strain, making epoxides highly reactive, more so than other ethers. They are produced on a large scale for many applications. In general, low molecular weight epoxides are colourless and nonpolar, and often volatile.

<span class="mw-page-title-main">Butadiene</span> Chemical compound

1,3-Butadiene is the organic compound with the formula CH2=CH-CH=CH2. It is a colorless gas that is easily condensed to a liquid. It is important industrially as a precursor to synthetic rubber. The molecule can be viewed as the union of two vinyl groups. It is the simplest conjugated diene.

A diol is a chemical compound containing two hydroxyl groups. An aliphatic diol is also called a glycol. This pairing of functional groups is pervasive, and many subcategories have been identified.

<span class="mw-page-title-main">Bisphenol A</span> Chemical compound used in plastics manufacturing

Bisphenol A (BPA) is a chemical compound primarily used in the manufacturing of various plastics. It is a colourless solid which is soluble in most common organic solvents, but has very poor solubility in water. BPA is produced on an industrial scale by the condensation reaction of phenol and acetone. Global production in 2022 was estimated to be in the region of 10 million tonnes.

<span class="mw-page-title-main">Azobenzene</span> Two phenyl rings linked by a N═N double bond

Azobenzene is a photoswitchable chemical compound composed of two phenyl rings linked by a N=N double bond. It is the simplest example of an aryl azo compound. The term 'azobenzene' or simply 'azo' is often used to refer to a wide class of similar compounds. These azo compounds are considered as derivatives of diazene (diimide), and are sometimes referred to as 'diazenes'. The diazenes absorb light strongly and are common dyes. Different classes of azo dyes exist, most notably the ones substituted with heteroaryl rings.

In organic chemistry, an electrocyclic reaction is a type of pericyclic rearrangement where the net result is one pi bond being converted into one sigma bond or vice versa. These reactions are usually categorized by the following criteria:

<span class="mw-page-title-main">Cyclohexane conformation</span> Structures of cyclohexane

Cyclohexane conformations are any of several three-dimensional shapes adopted by molecules of cyclohexane. Because many compounds feature structurally similar six-membered rings, the structure and dynamics of cyclohexane are important prototypes of a wide range of compounds.

<span class="mw-page-title-main">Dicyclopentadiene</span> Chemical compound

Dicyclopentadiene, abbreviated DCPD, is a chemical compound with formula C10H12. At room temperature, it is a white brittle wax, although lower purity samples can be straw coloured liquids. The pure material smells somewhat of soy wax or camphor, with less pure samples possessing a stronger acrid odor. Its energy density is 10,975 Wh/l. Dicyclopentadiene is a co-produced in large quantities in the steam cracking of naphtha and gas oils to ethylene. The major use is in resins, particularly, unsaturated polyester resins. It is also used in inks, adhesives, and paints.

<span class="mw-page-title-main">Isosorbide</span> Chemical compound

Isosorbide is a bicyclic chemical compound from the group of diols and the oxygen-containing heterocycles, containing two fused furan rings. The starting material for isosorbide is D-sorbitol, which is obtained by catalytic hydrogenation of D-glucose, which is in turn produced by hydrolysis of starch. Isosorbide is discussed as a plant-based platform chemical from which biodegradable derivatives of various functionality can be obtained.

<span class="mw-page-title-main">Polyester</span> Category of polymers, in which the monomers are joined together by ester links

Polyester is a category of polymers that contain the ester functional group in every repeat unit of their main chain. As a specific material, it most commonly refers to a type called polyethylene terephthalate (PET). Polyesters include naturally occurring chemicals, such as in plants and insects, as well as synthetics such as polybutyrate. Natural polyesters and a few synthetic ones are biodegradable, but most synthetic polyesters are not. Synthetic polyesters are used extensively in clothing.

1,2-Dichloroethene, commonly called 1,2-dichloroethylene or 1,2-DCE, is the name for a pair of organochlorine compounds with the molecular formula C2H2Cl2. They are both colorless liquids with a sweet odor. It can exist as either of two geometric isomers, cis-1,2-dichloroethene or trans-1,2-dichloroethene, but is often used as a mixture of the two. They have modest solubility in water. These compounds have some applications as a degreasing solvent. In contrast to most cis-trans compounds, the Z isomer (cis) is more stable than the E isomer (trans) by 0.4 kcal/mol.

<span class="mw-page-title-main">Ladderane</span>

In chemistry, a ladderane is an organic molecule containing two or more fused cyclobutane rings. The name arises from the resemblance of a series of fused cyclobutane rings to a ladder. Numerous synthetic approaches have been developed for the synthesis of ladderane compounds of various lengths. The mechanisms often involve [2 + 2] photocycloadditions, a useful reaction for creating strained 4-membered rings. Naturally occurring ladderanes have been identified as major components of the anammoxosome membrane of the anammox bacteria, phylum Planctomycetota.

<i>trans</i>-Cyclooctene Chemical compound

trans-Cyclooctene is a cyclic hydrocarbon with the formula [–(CH2)6CH=CH–], where the two C–C single bonds adjacent to the double bond are on opposite sides of the latter's plane. It is a colorless liquid with a disagreeable odor.

<span class="mw-page-title-main">Cyclohexanedimethanol</span> Chemical compound

Cyclohexanedimethanol (CHDM) is a mixture of isomeric organic compounds with formula C6H10(CH2OH)2. It is a colorless low-melting solid used in the production of polyester resins. Commercial samples consist of a mixture of cis and trans isomers. It is a di-substituted derivative of cyclohexane and is classified as a diol, meaning that it has two OH functional groups. Commercial CHDM typically has a cis/trans ratio of 30:70.

<span class="mw-page-title-main">Tritan copolyester</span> Brand of copolymer

Tritan" is a copolymer offered by the Eastman Chemical Company since 2007 is a transparent plastic intended to replace polycarbonate, because of health concerns about Bisphenol A (BPA). Tritan is a copolymer made from three monomers: dimethyl terephthalate (DMT), cyclohexanedimethanol (CHDM), and 2,2,4,4-tetramethyl-1,3-cyclobutanediol (CBDO). Tritan (PCTG) is made without using any BPA.

<span class="mw-page-title-main">2,2,4,4-Tetramethylcyclobutanedione</span> Chemical compound

2,2,4,4-Tetramethylcyclobutanedione is the organic compound with the formula (CH3)4C4O2. The compound is a diketone of cyclobutane, bearing four methyl groups. It is a white solid that is used as a precursor to diverse industrial products.

The methods for sequence analysis of synthetic polymers differ from the sequence analysis of biopolymers. Synthetic polymers are produced by chain-growth or step-growth polymerization and show thereby polydispersity, whereas biopolymers are synthesized by complex template-based mechanisms and are sequence-defined and monodisperse. Synthetic polymers are a mixture of macromolecules of different length and sequence and are analysed via statistical measures.

References

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  2. 1 2 Hoppens, Nathan C.; Hudnall, Todd W.; Foster, Adam; Booth, Chad J. (2004-07-15). "Aliphatic–aromatic copolyesters derived from 2,2,4,4-tetramethyl-1,3-cyclobutanediol". Journal of Polymer Science Part A: Polymer Chemistry. 42 (14): 3473–3478. doi:10.1002/pola.20197. ISSN   0887-624X.
  3. 1 2 Kelsey, Donald R.; Scardino, Betty M.; Grebowicz, Janusz S.; Chuah, Hoe H. (2000-08-01). "High Impact, Amorphous Terephthalate Copolyesters of Rigid 2,2,4,4-Tetramethyl-1,3-cyclobutanediol with Flexible Diols". Macromolecules. 33 (16): 5810–5818. Bibcode:2000MaMol..33.5810K. doi:10.1021/ma000223+. ISSN   0024-9297.
  4. Wedeking, E.; Weisswange, W. (March 1906). "Ueber die Synthese eines Diketons der Cyclobutanreihe". Berichte der Deutschen Chemischen Gesellschaft. 39 (2): 1631–1646. doi:10.1002/cber.19060390287. ISSN   0365-9496.
  5. W. Theilheimer "1,3-Cyclobutanediols from 1,3-cyclobutandiones" Synthetic Methods of Organic Chemistry, 1962, Volume 16, pp. 29.
  6. Shirrell, C. D.; Williams, D. E. (1976-06-01). "The crystal and molecular structure of cis -2,2,4,4-tetramethyl-1,3-cyclobutanediol". Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry. 32 (6): 1867–1870. Bibcode:1976AcCrB..32.1867S. doi:10.1107/S0567740876006559. ISSN   0567-7408.
  7. Margulis, T. N. (1969). "Planar cyclobutanes: structure of 2,2,4,4-tetramethyl-cyclobutane-trans-1,3-diol". Journal of the Chemical Society D: Chemical Communications (5): 215–216. doi:10.1039/c29690000215. ISSN   0577-6171.
  8. Köpnick, Horst; Schmidt, Manfred; Brügging, Wilhelm; Rüter, Jörn; Kaminsky, Walter. "Polyesters". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.a21_227. ISBN   978-3527306732.