Adipic acid dimethyl ester

Figure 12.12 THM GC/MS curves of a Winsor Newton lemon alkyd paint (a) and of an alkyd sample taken from Fontana s work Concetto spaziale (1961) (b). Peak assignments 1, 1,3 dimethoxy 2 propanol 2, 1,2,3 trimethoxy propane 3, 3 methoxy 1,2 propandiol 4, 4 chloro benzenamine 5, 3 methoxy 2,2 bis(methoxymethyl) 1 propanol 6, 3 chloro N methyl benzenamine 7, 3 methoxy 2 methoxymethyl 1 propanol 8, 4 chloro N methyl benzenamine 9, phthalic anhydride 10, 3 chloro 4 methoxy benzenamine 11, suberic acid dimethyl ester 12, dimethyl phthalate 13, azelaic acid dimethyl ester 14, sebacic acid dimethyl ester 15, palmitic acid methyl ester 16, oleic acid methyl ester 17, stearic acid methyl ester 18, 12 hydroxy stearic acid methyl ester 19, 12 methoxy stearic acid methyl ester 20, styrene 21, 2 (2 methoxyethoxy) ethanol 22, 1,1 oxybis(2 methoxy ethane) 23, benzoic acid methyl ester 24, adipic acid dimethyl ester 25, hexadecenoic acid methyl ester 26, dihydroisopimaric acid methyl ester 27, dehydroabietic acid methyl ester 28, 4 epidehydroabietol...

One process that capitalizes on butadiene, synthesis gas, and methanol as raw materials is BASF s two-step hydrocarbonylation route to adipic acid(3-7). The butadiene in the C4 cut from an olefin plant steam cracker is transformed by a two-stage carbonylation with carbon monoxide and methanol into adipic acid dimethyl ester. Hydrolysis converts the diester into adipic acid. BASF is now engineering a 130 million pound per year commercial plant based on this technology(8,9). Technology drawbacks include a requirement for severe pressure (>4500 psig) in the first cobalt catalyzed carbonylation step and dimethyl adipate separation from branched diester isomers formed in the second carbonylation step. 

Dimethyl hexanedioate Adipic acid, dimethyl ester (8) Hexanedioic acid, dimethyl ester (9) (627-93-0)... 

ADIPIC ACID, DIMETHYL ESTER (627-93-0) CgH,404 Combustible liquid. Forms explosive mixture with air [explosion limits in air (vol %) 0.8 to 8.1 flash point 225°F/107°C cc autoignition temp 680°F/360°C Fire Rating 1]. Incompatible with strong acids and caustic solution (both... 

ADIPIC ACID, DIMETHYL ESTER (627-93-0) Combustible liquid (flash point 225°F/ I07 C cc). Incompatible with strong acids, nitrates, oxidizers. 

Beilstein Handbook Reference) Adipic acid, dimethyl ester AI3-00668 BRN 1707443 DBE 6 Dimethyl adipate Dimethyl hexanedioate 1,8-Dimethylhexanedioate Dimethyladipate EINECS 211-020-6 Hexanedioic acid, dimethyl ester HSDB 5021 Methyl adipate NSC 11213. Used as a solvent and plasticizer. Liquid mp = 10.3° bpi3 = 115° d = 1.0600 insoluble in H2O, soluble in EtOH, Et20, CCI4, AcOH. DuPont Morflex UCB SA. 

Adipic acid bis (2-ethylhexyl) ester. See Dioctyl adipate Adipic acid, diallqrl (C7-C9) ester. See Di (C7-9 alkyl) adipate Adipic acid, diisobutyl ester. See Diisobutyl adipate Adipic acid dimethyl ester. See Dimethyl adipate AEP. SeeAminoethylpiperazine Agalmatolite. See Pyrophyllite... 

CAS 627-93-0 EINECS/EEINCS 211-020-6 Synonyms Adipic acid dimethyl ester Dimethyl hexanedioate Hexanedioic acid, dimethyl ester Methyl adipate Classification Dicarboxylic acid ester Definition Diester of methyl alcohol and adipic acid Empirical CsH Oj Formula CH302C(CH2)4C02CH,... 

Adipic acid dimethyl ester. See Dimethyl adipate... 

Amidation. Heating of the diammonium salt or reaction of the dimethyl ester with concentrated ammonium hydroxide gives adipamide [628-94-4] mp 228°C, which is relatively insoluble in cold water. Substituted amides are readily formed when amines are used. The most industrially significant reaction of adipic acid is its reaction with diamines, specifically 1,6-hexanediamine. A water-soluble polymeric salt is formed initially upon mixing solutions of the two materials then hea ting with removal of water produces the polyamide, nylon-6,6. This reaction has been studied extensively, and the hterature contains hundreds of references to it and to polyamide product properties (31). 

Reduction. Hydrogenation of dimethyl adipate over Raney-promoted copper chromite at 200°C and 10 MPa produces 1,6-hexanediol [629-11-8], an important chemical intermediate (32). Promoted cobalt catalysts (33) and nickel catalysts (34) are examples of other patented processes for this reaction. An eadier process, which is no longer in use, for the manufacture of the 1,6-hexanediamine from adipic acid involved hydrogenation of the acid (as its ester) to the diol, followed by ammonolysis to the diamine (35). 

Seb cic Acid. Sebacic acid [111-20-6] C QH gO, is an important intermediate in the manufacture of polyamide resins (see Polyamides). It has an estimated demand worldwide of approximately 20,000 t/yr. The alkaline hydrolysis of castor oil (qv), which historically has shown some wide fluctuations in price, is the conventional method of preparation. Because of these price fluctuations, there have been years of considerable interest in an electrochemical route to sebacic acid based on adipic acid [124-04-9] (qv) as the starting material. The electrochemical step involves the Kolbn-type or Brown-Walker reaction where anodic coupling of the monomethyl ester of adipic acid forms dimethyl sebacate [106-79-6]. The three steps in the reaction sequence from adipic acid to sebacic acid are as follows ... 

The dimethyl ester of adipic acid, rather than adipic acid, was used as a transesterification substrate. Reaction rate studies had shown that the transesterification would be much faster than the esterification reaction. It was considered that the rate of attack on the oxazolidine ring by methanol would be slower than the rate of attack by water and that the ring opening would not be catalysed by the enzyme, whereas the rate of the transesterification would be increased significantly, particularly at the low temperature of the enzymatic esterification. 

A solution of borane in tetrahydrofuran reduces esters at room temperature only slowly [977]. Under such conditions free carboxylic groups of acids are reduced preferentially monoethyl ester of adipic acid treated with 1 mol of borane in tetrahydrofuran at — 18° to 25° gave 88% yield of ethyl 6-hydroxy-hexanoate [977]. Borane-dimethyl sulfide in tetrahydrofuran was used for... 

In Japan the need for new technology was answered by the development of an electrolytic route to sebacic acid(33). The Kolbe type electrolytic process developed by Asahi involves dimerization of adipic acid half methyl ester salt to give dimethyl sebacate(34). The dimerization proceeds in 92% yield with 90% selectivity based on the adipate half ester. The main drawbacks of this process are the cost of energy utilized by the electrolytic process and the cost of adipic acid. A Chem Systems report indicates a small advantage for the Asahi electrolytic process with ample room for new technology development(35). 

Copper or silver can be used to condense /3-iodo-propionic acid to adipic acid, and also for condensing a-brom-propionic ester to dimethyl succinic ester... 

Electrolysis of a methanol solution of methyl oxalate with ethylene under pressure yielded 70-90% of the dimethyl esters of succinic, adipic, suberic, and sebacic acids. Decrease in the ethylene pressure or increase of the current density led to a decrease in the higher esters in the product mixture [241]. The influence of mechanism and kinetic data on yields and selectivities in addition reactions of anodically generated radicals to olefins has been calculated and predictions have been tested in preparative electrolyses [244]. 

Asahi Chemical is said to have been using the Kolbe synthesis for the production of sebacic acid for 20 years now. The electrolysis itself is one of three chemical steps (Scheme 7). In the first step, the monoester of adipic acid is produced. This is anodically dimerized to dimethyl sebacate. This ester is hydrolyzed to give crude sebacic acid. 

In the second step, the concentration of pyridine as ligand must be low because it has an inhibitory effect on the hydroalkoxycarbonylation. In situ isomerization to the 4-pentenoic acid ester is a prerequisite for the subsequent carbonylation which provides dimethyl adipate. To ensure internal double-bond rearrangement, the temperature of the reaction is increased to 160-200 °C to give dimethyl adipate with 80 % selectivity. After hydrolysis of the ester, adipic acid is obtained with an overall selectivity of about 70% [1]. So far, this process has been performed on pilot-plant scale. 

Synthesized from dimethyl ester of adipic acid, DMA Synthesized from adipic acid, AA... 

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