935-79-5

Basic information

• Product Name: cis-1,2,3,6-Tetrahydrophthalic anhydride
• Synonyms: 1,3-isobenzofurandion,3a,4,7,7a-tetrahydro-,cis-;3-Isobenzofurandione,3a,4,7,7a-tetrahydro-,cis-1;4,7,7a-tetrahydro-3-isobenzofurandioncis-3a;cis-3a,4,7,7a-Tetrahydro-1,3-isobenzofurandione;CIS-THPA;CIS-DELTA4-TETRAHYDROPHTHALIC ANHYDRIDE;CIS-4-TETRAHYDROPHTHALIC ANHYDRIDE;CIS-4-CYCLOHEXEN-1,2-DIMETHANOIC ANHYDRIDE
• CAS NO: 935-79-5
• Molecular Formula: C₈H₈O₃
• Molecular Weight: 152.15
• EINECS: 213-308-7
• Product Categories: Diels-Alder Adducts
• Mol File: 935-79-5.mol

Chemical Properties

• Melting Point: 98 °C
• Boiling Point: 234.6°C (rough estimate)
• Flash Point: 156 °C
• Appearance: white flakes
• Density: 1.2143 (rough estimate)
• Vapor Density: 5.2 (vs air)
• Vapor Pressure: <0.01 mm Hg ( 20 °C)
• Refractive Index: 1.4447 (estimate)
• Storage Temp.: under inert gas (nitrogen or Argon) at 2-8°C
• Solubility: soluble in Toluene,Benzene
• Water Solubility: REACTS
• Sensitive: Moisture Sensitive
• BRN: 82341
• CAS DataBase Reference: cis-1,2,3,6-Tetrahydrophthalic anhydride(CAS DataBase Reference)
• NIST Chemistry Reference: cis-1,2,3,6-Tetrahydrophthalic anhydride(935-79-5)
• EPA Substance Registry System: cis-1,2,3,6-Tetrahydrophthalic anhydride(935-79-5)

Safety Data

• Hazard Codes: Xn
• Statements: 41-42/43-52/53
• Safety Statements: 22-24-26-37/39-61-52/53-42/43-41
• RIDADR: UN 2698 8/PG 3
• WGK Germany: 3
• RTECS: GW5775000
• TSCA: Yes
• HazardClass: 8
• PackingGroup: III
• Hazardous Substances Data: 935-79-5(Hazardous Substances Data)

Usage

Uses

Used in Coatings Industry:
cis-1,2,3,6-Tetrahydrophthalic anhydride is used as an anhydride hardener for enhancing the properties of coatings, providing improved thermal stability and chemical resistance.
Used in Epoxy Resin Curing Agents Industry:
THPA serves as a curing agent for epoxides, which is crucial for the cross-linking process in the production of epoxy resins, leading to enhanced mechanical properties and durability.
Used in Polyester Resins Industry:
cis-1,2,3,6-Tetrahydrophthalic anhydride is used as a chemical modifier in the modification of polyester resins, improving their thermal stability and performance characteristics.
Used in Adhesives Industry:
THPA is employed as a hardener in adhesive formulations, contributing to the bonding strength and resistance to environmental factors.
Used in Plasticizers Industry:
cis-1,2,3,6-Tetrahydrophthalic anhydride is used as a chemical intermediate for light-colored alkyds, which are essential for the production of plasticizers.
Used in Pesticides Industry:
THPA is utilized as a chemical intermediate in the synthesis of various pesticides, contributing to the development of effective and environmentally friendly products.
Used in Chemical Modifiers for Polystyrene Industry:
cis-1,2,3,6-Tetrahydrophthalic anhydride is used as a chemical modifier in the modification of polystyrene via Friedel-Crafts acylation, enhancing the thermal stability of the polymer.
Used in Synthesis of cis-Tetrahydroisoindole-1,3-Dione Derivatives and Cyclic Diimides:
THPA is employed as a reactant in the synthesis of cis-tetrahydroisoindole-1,3-dione derivatives and cyclic diimides, which have potential applications in various chemical and pharmaceutical processes.

Preparation

A flask containing 500 ml of dry benzene and 196 gm (2 moles) of maleic anhydride is heated with a pan of hot water while butadiene is introduced rapidly (0.6-0.8 liter/min) from a commercial cylinder. The solution is stirred rapidly and the heating is stopped after 3-5 min when the temperature reaches 50°C. In 15-25 min the reaction causes the temperature of the solution to reach 70-75°C. The absorption of the rapid stream of butadiene is nearly complete in 30-40 min. The addition of butadiene is continued at a slower rate for a total of 2\ hr. The solution is poured into a 1-liter beaker which is covered and kept at 0-5°C overnight. The product is collected on a large Buchner funnel and washed with 250 ml of b.p. 35-60°C petroleum ether. A second crop is obtained by diluting the filtrate with an additional 250 ml of petroleum ether. Both crops are dried to constant weight in an oven at 70-80°C to yield 281.5-294.5 gm (96- 97%, m.p. 99-102°C). Recrystallization from ligroin or ether raises the melting point to 103-104°C.

Synthesis Reference(s)

Journal of the American Chemical Society, 64, p. 802, 1942 DOI: 10.1021/ja01256a018

InChI:InChI=1/C8H8O3/c9-7-5-3-1-2-4-6(5)8(10)11-7/h1,3,5-6H,2,4H2

Upstream product

• 85-43-8 trans-4-Cylohexene-1,2-dicarboxylic anhydride 
• 88-98-2 trans-cyclohex-4-ene-1,2-dicarboxylic acid 
• 108-31-6 maleic anhydride 
• 106-99-0 buta-1,3-diene 
• 77-79-2 3-Sulfolene 
• 17673-68-6 dimethyl trans-cyclohex-4-ene-1,2-dicarboxylate 
• 4841-84-3 dimethyl cis-1,2,3,6-tetrahydrophthalate 
• 18668-68-3 4-bromo-buta-1,2-diene 

Downstream Products

• 355830-81-8 (1SR,6RS)-6-(pyrrolidine-1-carbonyl)cyclohex-3-enecarboxylic acid 
• 73825-63-5 2-(3-morpholino-propyl)-(3ar,7ac)-3a,4,7,7a-tetrahydro-isoindole-1,3-dione 
• 19692-02-5 (+/-)-cis-6-thiazol-2-ylcarbamoyl-cyclohex-3-enecarboxylic acid 
• 73839-58-4 2-[3-(4-methyl-piperazino)-propyl]-(3ar,7ac)-3a,4,7,7a-tetrahydro-isoindole-1,3-dione 
• 4841-84-3 dimethyl cis-1,2,3,6-tetrahydrophthalate 
• 93603-11-3 1-methyl hydrogen 1,2-cis-1,2-cyclohex-4-ene dicarboxylate 
• 75005-76-4 (+/-)-cis-cyclohex-4-ene-1,2-dicarboxylic acid monopropyl ester 
• 21577-85-5 (+/-)-cis-cyclohex-4-ene-1,2-dicarboxylic acid monoheptadecyl ester 
• 20141-48-4 cis-6-(ethoxycarbonyl)cyclohex-3-ene-1-carboxylic acid 
• 94259-70-8 Tetrahydrophthalsaeure-dipentylester 
• 96374-43-5 cis-cyclohex-4-ene-1,2-dicarboxylic acid bis-decyl ester 
• 100720-23-8 (+/-)-cis-6-[bis-(2-cyano-ethyl)-carbamoyl]-cyclohex-3-enecarboxylic acid 
• 28915-98-2 2-ethyl-3a,4,7,7a-tetrahydroisoindole-1,3-dione 
• 351982-48-4 (+/-)-cis-6-phenethylcarbamoyl-cyclohex-3-enecarboxylic acid 

Relevant articles and documents

cis-1,2,3,6-Tetrahydrophthalic anhydride at 173 K

The title compound, C8H8O1, (I), crystallizes with two nearly identical molecules in the asymmetric unit. Each molecule has a boat conformation and non-crystallographic mirror symmetry. The structure was determined in connection with a study of the possible chemical decomposition of the compound in different solvents and in contact with the atmosphere. A similar boat conformation was found in five of six structures retrieved from the Cambridge Structural Database which contain (I) as a moiety. The present structure exhibits nearly the same packing motif as the recently found monoclinic polymorph.

Novel 1,2,3-triazole compounds: Synthesis, In vitro xanthine oxidase inhibitory activity, and molecular docking studies

In this study, novel 1,2,3-triazole compounds containing carbasugar frameworks (5 and 6) were synthesized by the copper-catalyzed azide-alkyne cycloaddition reactions and their in vitro inhibition effects on the enzyme xanthine oxidase were investigated. All of the synthesized compounds were characterized by spectroscopic methods. According to the enzyme inhibition results, compounds 5 (IC50 = 0.586 ± 0.017 μM) and 6 (IC50 = 0.751 ± 0.021 μM) showed stronger inhibition effects than allopurinol (IC50 = 1.143 ± 0.019 μM), which is a standard drug used for inhibition of xanthine oxidase. The binding modes of the 1,2,3-triazole compounds (5 and 6) with the active site of xanthine oxidase were explained based on molecular docking studies. The molecular docking studies showed that the aromatic structure, π-π interactions and hydrophobic interactions play a major role in xanthine oxidase inhibition for compounds 5 and 6.

An anomalous addition of chlorosulfonyl isocyanate to a carbonyl group: The synthesis of ((3aS,7aR,E)-2-ethyl-3-oxo-2,3,3a,4,7,7a-hexahydro-1H-isoindol-1-ylidene)sulfamoyl chloride

In this study, we developed a new addition reaction of chlorosulfonyl isocyanate (CSI), starting from 2-ethyl-3a,4,7,7a-tetrahydro-1H-isoindole-1,3(2H)-dione. The addition reaction of CSI with 2-ethyl-3a,4,7,7a-tetrahydro-1H-isoindole-1,3(2H)-dione resulted in the formation of ylidenesulfamoyl chloride, whose exact configuration was determined by X-ray crystal analysis. We explain the mechanism of product formation supported by theoretical calculations.

Access to amphiphilic cis-configurated polyamide-3 using alcohols as initiators

The synthesis of polyamide-3 from 4a,5,8,8a-tetrahydro-1H-benzo[d][1,3]oxazine-2,4-dione (β-NCA, 1) using methanol, dye (Disperse Red 13), and poly(ethylene glycol) as initiator is described. The ring-opening polymerization under release of CO2 produces polyamides-3 with definite terminal groups, high purity, and relatively narrow dispersity. This route was used for preparation of block copolymers from as an example.

Tandem Diels-Alder/cross-coupling reactions of generated in situ organoindium reagents in a one-pot process

[Chemical equation presented] Tandem Diels-Alder/ cross-coupling reactions with organoindium reagents generated in situ from 1-bromo-2,3-butadiene and indium were developed in a one-pot process. [4 + 2] Cycloaddition reactions using organoindium reagents and subsequent Pd-catalyzed cross-coupling reactions provided the rapid synthesis of six-membered carbocycles starting from 1-bromo-2,3-butadiene.

Synthesis of diazacrown compounds with polyfunctional cyclohexane fragments

A convenient synthetic method was developed for new diazacrown compounds that contained at polyether cavity polyfunctional cyclohexene or cyclohexane fragments of definite configuration. The synthetic procedure consists in fusion in toluene of equimolar quantities of anhydrides of 4-cyclohexene and 4,5-trans-dibromocyclohexane-cis-1,2-dicarboxylic acids with hydroxy-substituted diazacrown ether. The crown compounds synthesized under complexing conditions with AgBF4 undergo disproportionation yielding bis-crown compounds.

Improved synthesis of both enantiomers of trans-cyclohex-4-ene-1,2- dicarboxylic acid

A facile synthesis of both enantiomers of trans-cyclohex-4-ene-1,2- dicarboxylic acid on a multigram scale, that starts from inexpensive, commercially available compounds, is described.

Diastereoselective cis to trans desymmetrization of dimethyl succinates

Meso-succinates, readily available by Diels-Alder cycloaddition of dimethyl maleate or maleic anhydride followed by esterification, can be isomerized quantitatively from the cis to the trans isomers in the presence of lithium alkoxides. The reaction performed with enantiopure chiral lithium alkoxides yields diastereomeric trans-succinates in good yield and selectivity.

Preparations and Crystal Structures of the 2-Oxides of Some Octahydro-3,2,1-benzoxathiazines and Octahydro-2H-3,1,2-benzoxazaphosphorines

The cis- and trans-fused 1-benzyl-1,4,4a,5,6,7,8,8a-octahydro-3,2,1-benzoxathiazine 2-oxides and cis- and trans-fused 1-benzyl-2-phenyl-1,4,4a,5,6,7,8,8a-octahydro-2H-3,1,2-benzoxazaphosphorine 2-oxides have been prepared from the cis- and trans-2-benzylaminocyclohexanemethanols and their structures have been determined by n.m.r. and crystallographic methods.

STEREOCHEMICAL STUDIES 83. SATURATED HETEROCYCLES 76. PREPARATION AND CONFORMATIONAL STUDY OF PARTIALLY SATURATED 3,1-BENZOXAZINES, 3,1-BENZOXAZIN-2-ONES AND 3,1-BENZOXAZINE-2-THIONES

The cis- and trans-2-amino-4-cyclohexene-1-carboxylic acids 1 and 3 react with imidates to give the condensed-skeleton, bicyclic cis- and trans-pyrimidin-4-ones 8 and 9.The amino acids 1 and 3 were reduced to the cis- and trans-1,3-aminoalcohols 6 and 7, which were cyclized by means of imidates to the bicyclic tetrahydro-4H-3,1-benzoxazines 10 and 11, or were converted, via the corresponding carbamates 14 and 15 into the tetrahydro-4H-3,1-benzoxazin-2(1H)-ones 16 and 17.The 2-thioxo analogues 18 and 19 were prepared by cyclization of the dithiocarbamates obtained from the aminoalcohols 6 and 7 by treatment with carbon disulphide.The trans-aminoalcohol 7 and its saturated analogue reacted with p-chlorobenzaldehyde to furnish the hexahydro 13 and octahydro-4H-3,1-benzoxazine 13a, respectively. 1H and 13C NMR studies showed that, similarly to the earlier-investigated analogues containing oxygen or unsubstituted nitrogen at position 1, the synthesized cis isomers 8, 10, 16 and 18 occurred as the preferred conformer in the heterocyclic twist inverse form of N-inside type (quasiaxal C6-N bond) (B).In the trans isomers containing a saturated C-2 atom (13 and 13a), H-2 and H-6 are in cis relative positions.