3-Methyl-adipic

Extension by three carbon atoms is possible with methyl glutarate [183], by the isoprene unit with ethyl 3-methyl adipate [184], by four carbon atoms with methyl adipate [143], by five carbon atoms with methyl pimelate [185] and by six carbon atoms with methyl suberate [186]. A series of branched -fluorocarboxylic acids were prepared by cross-coupling with oo-fluorocarboxylic acids [187]. For further examples see Tables 6, 7. 

Recently Blumstein and coworkers reported on the thermotropic properties of a series of main chain copolyesters with different azoxybenzene mesogenic units and flexible spacers consisting of varying ratios of (-I-) 3-methyl adipic acid and 1,12-dodecanedioic acid. Melting temperature of the copolyesters showed minimum values for either the 50/50 compositions or the 25/75 combination of the two spacer components, depending on the nature of the mesogenic units. However, Tj tended to decrease linearly with the content of the 1,12-dodecanedioic acid unit, except in one case. They also observed that the cholesteric pitch of the copolyesters seemed to increase as the concentration of the achiral unit, dodecanedioic acid, increased. Similar observations were reported earlier by Strzelecki s group... 

Complex with distinct discotic shapes can also be obtained by hydrogen bonds between different (complementary) molecules (Fig. 5.1b). For example, supramolecular chiral LC assemblies can be obtained by hydrogen bonding clipping association (Fig. 5.9) [65]. 3-Methyl adipic acid (MeAdip) acting as a chiral clip is... 

Kohn [23] Tyrosine Desamino tyrosine Succinic acid, glutaric acid, diglycolic acid, adipic acid, 3-methyl adipic acid, suberic acid, dioxaoctanedioic acid, or sebacic acid Methanol, ethanol, isopropanol, butanol, isobutanol, sec-butanol, hexanol, octanol, dodecyl, or phenol... 

It is interesting to observe that cholesteric copolyesters synthesized from i+,U -dihydroxyazoxybenzene and mixtures of (+) -3-methyl-adipic acid and dodecanedioic acid do not orient. Systematic variations with molecular weight and careful analysis in certain homologous series should give information on the influence of the intrinsic flexibility of the chains, the apparent viscosity of the melt and certain basic microscopic processes such as entanglement effects on the tendency for macromole cular chains to become aligned when placed in a magnetic field. 

Scheme 13.28. The conversion of (+)-citronellal to (+)- 3-methyl adipic acid and (+)-methyl-succinic acids. After Tiemann, E Schmidt, R. Chem. Ber., 1895,28, 2137 and von Braun, X Jostes, F. Chem. Ber., 1926,59,1091,1444.

Table 9. The transition temperatures and phase assignments of diesters derived from the chiral 3-methyl adipic acid and 4-hydroxybenzylidene-4 -alkoxyanilines.

A more recent continuation of this theme using (i )-3-methyladipic acid, was the systematic study of dimeric or twin structures which are capable of forming highly twisted helical structures [102-105]. These examples, differ from the previously mentioned Z7/5-azomethines in that they employ 2-pyrimidinylpheny] (116 and 117) and phenyl core units (118) they were made simply by esterification of (/ )-3-methyl-adipic acid with the appropriately substituted phenol using dicyclohexylcarbodiimide (DCC) and the catalyst 4-iV,iV-dimethyl-aminopyridine (DMAP). The structures and phase transitions of members of these two classes are given in structures 116 to 118. 

In this chapter chiral thermotropic semisynthetic and synthetic polymers are included. They will be treated in separate sections focused on cellulose and polypeptide systems and on polyesters containing (-h)-(/ )-3-methyl-adipic acid as the chiral moiety. Mixtures of achiral condensation polymers with optically active low molar mass compounds will be also briefly discussed. 

METHOXY-n-VALERIC-TMS-l 2-METHYL-ACETOACETIC-EO-TMS-l (PK 1) 2-METHYL-ACETOACETIC-EO-TMS-l (PK 2) 3 METHYL ADIPIC-TMS-2... 

Table 5. Yield of methyl decanoate in the cross-coupling of methyl adipate and hexanoate [146]...

The electrolysis of methyl adipate in the presence of butadiene has received considerable attention, because it makes long chain diacids easily accessible. A total yield of 96% diester has been claimed for this reaction (Table 8, No. 7). 

The addition of various Kolbe radicals generated from acetic acid, monochloro-acetic acid, trichloroacetic acid, oxalic acid, methyl adipate and methyl glutarate to acceptors such as ethylene, propylene, fluoroolefins and dimethyl maleate is reported in ref. [213]. Also the influence of reaction conditions (current density, olefin-type, olefin concentration) on the product yield and product ratios is individually discussed therein. The mechanism of the addition to ethylene is deduced from the results of adsorption and rotating ring disc studies. The findings demonstrate that the Kolbe radicals react in the surface layer with adsorbed ethylene [229]. In the oxidation of acetate in the presence of 1-octene at platinum and graphite anodes, products that originate from intermediate radicals and cations are observed [230]. 

Menispermum palmatum L. Pulegone, pinenes, limonene, lauric acid, myristic acid, palmitic acid, beta-methyl-adipic acid, phenol, cresols, eugenal.100 For uterine tumors, uterine fibroids, indurations of the uterus. 

Methyl adipate, MeOH Butadiene Dimethyl 6,10-hexadecadiene-l,16-di- 263)... 

The synthetic potentiality of the Kolbe dimerization has been well documented for a variety of symmetrical target molecules. For example, the dimerization of acids (XII and XIII) is the key step of the pentacyclosqualene [55] and o -onocerin [56] syntheses. A large-scale production of sebasic acid has been realized by the Kolbe dimerization of methyl adipate half-ester [57]. 

A solution of SS g (0.27 mol) of methyl azelate in 350 mL methanol, neutralized to the extent of 6% with KOH in methanol, is electrolyzed in a flow-through cell (Figure 1) at 35-40 °C at a cell voltage of 40 V between a platinum anode (area = 17 cm ) and a steel cathode at a current density of 200 mA cm" until 1.2 F m" were consumed. The methanol is then evaporated, and the residue is dissolved in 500 mL ether and extracted with a saturated aqueous NaHCOs solution (3 x 100 mL) and subsequently washed with water. After drying (MgS04) and removal of the ether, fractionated distillation affords at b.p. 107-113 °C/0.02 Torr, 34.14 g (80%) dimethyl hexadecanedioate." For the preparation of dimethyl decane-dioate from methyl adipate see ref. 114. 

Crossed coupling has also been applied to the extension of the carbon chain in fatty acids. Extension by two carbon atoms is achieved with succinate half esters,whereby separation problems can be simplified by using the benzyl half ester.Expansion by the propane unit has been accomplished with methyl glutarate, ° by the isoprene unit with ethyl 3-methyladipate, by four carbons with methyl adipate, by the pentane unit with methyl pimelate, and by six carbon atoms with methyl suberate. 

The addition of the 5-pentanoate radical from methyl adipate to butadiene has been intensively investigated, because in this way long chain l,n-diacids are easily accessible a total yield of 96% has been claimed for this reaction (Table 8, entry 7). Different Kolbe radicals from acetic acid, monochloroacetic acid, trichloroacetic acid, oxalic acid, methyl adipate and methyl glutarate have been added to ethylene, propylene, fluoroalkenes and dimethyl maleate. In this detailed study the influence of current density, alkene type and alkene concentration on the product yields and product ratios have been discussed. 

Bis(3,4-Epoxy-6-methyl cyclohexyl methyl) adipate 0.47 928 to 1885 cps in 5 days... 

In the second step, the olefmic ester is sent to another reactor with a new quantity of carbon monoxide and methanol. The operation takes place at high temperature, 185°C, hut at lower pressure (3. IQ6 Pa absolute). Methyl adipate is formed with a molar yield of 75 per cent Methyl glutarate and methyl ethyl succinate are also formed. After purification by distillation, the methyl adipate is hydrolysed to adipic acid. 

METHYL ADIPATE (627-93-0) Combustible liquid (flash point 225°F/107°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. 

Chem. Descrip. Methyl glutarate (59-67%), methyl succinate (20-28%), methyl adipate (9-17%)... 

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,... 

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