Methyl glycolate

Nippon Shokubai in Japan has announced the development of a gold cata- 

A 50 tonne per annum pilot plant was commissioned and there are plans to build a larger scale plant in about three years time. The proprietary catalyst contains highly dispersed gold supported on a metal oxide such as 

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IE) Obtaining [3-l6-Methoxy-2-Naphthylj]2,2-Dimethyi Pentanoic Acid 2.5 g of the previous ester are saponified by means of 15 cc of soda lye and 25 cc of methyl glycol. 

It is worth pointing out that the stereochemistry of intermediate 147 at C-9 and C-10 is inconsequential since both positions will eventually bear trigonal carbonyl groups in the final product. The synthetic problem is thus significantly simplified by virtue of the fact that any or all C9-C10 diol stereoisomers could be utilized. A particularly attractive means for the construction of the C9-C10 bond and the requisite C8-C10 functionality in 147 is revealed by the disconnection shown in Scheme 41. It was anticipated that the venerable intermolecular aldol reaction could be relied upon to accomplish the union of aldehyde 150 and methyl glycolate (151) through a bond between carbons 9 and 10. 

Propanediol (1,2-Propylene glycol, 1,2-Dihydroxy propane, Methyl glycol). CH3.CHOH.CH2OH mw 76.09 colorl, viscous, stable, hygr liq bp 187.3°, d 1.0381g/cc at 20/20° RI 1.4293 at 27° fl pt (open cup) 210°F autoignition temp 780°F. Misc with w, ales, and many org solvents in all proportions. Can be prepd by hydration of propylene oxide. On nitration it yields the exp] 1,2-Propanediol Dinitrate (see below)... 

As early as 1904, 1,2-Propanediol Dinitrate was proposed (Ref 3) as an additive to lower the freezing temp of NG, but its practical application on a large scale was hindered by lack of the raw material, propane-1,2-diol. It is only recently that the synthesis of glycol from ethylene led to the development of a method for producing methyl glycol from propylene via cnioro-hydrin. Even so, propylene-1,2-glycol is somewhat more expensive than glycols derived from ethylene (Ref 9)... 

The pyrimido[6,l-F][l,4]oxazine-6,8-diones 164 (Y = O) and pyrimido[6,l-c][l,4]thiazine-6,8-diones 164 (Y = S) were synthesized by treating 6-chloromethyl-uracil with methyl glycolate 162 (Y = O) or methyl thioglycolate 162 (Y = S), respectively, and reacting the resulting 163 with DMF-dimethyl acetal (Scheme 20) <2004W02004/014354>. 

In addition to the successful hydrogenation of the two fluorinated esters, this report describes the hydrogenation of dimethyl oxalate. Using the reactive anionic ruthenium catalyst, a 70% conversion to methyl glycolate could be achieved (TON = 235 TOF 12 h-1) (Scheme 15.19, Table 15.14, final entry). 

Pressure [bar] Catalyst concentration [mmol L-1] Temperature [°q Methyl glycolate [%] Ethylene glycol [%]... 

Scheme 15.20 Two-stage hydrogenation of esters giving ethylene glycol (EG), without decomposition products. MG = methyl glycolate.

Methyl glycol acetate, see Methyl cellosolve acetate... 

Synonyms Ethylene glycol monomethyl ether acetate EGMEA 2-MEA methyl cellosolve acetate methyl glycol acetate... 

Reactions of methyl formate with paraformaldehyde yields methyl glycolate (Equation 17). 

Methyl glycolate can be used to prepare a variety of fine chemicals exhibited in Figure 7. 

HOCHjCONHCH CHjOH mw 119.12, crystals, mp 72.5-73.5°. May be prepd by treating methyl glycolate with monoethanolamine A colorless oil was obtained when 2g of the compound were dissolved in 10ml of white nitric acid and then heated at 50-60° for one-half hour and poured oh ice. This oil was not further investigated, but it might have been a liquid explosive, suitable as a plasticizer for NC etc Refs 1) Beil, not found 2) R. Adams C.S. Marvel, OSRD No 86 (1941), pp 12 36-37 3) CA not found thru 1971... 

N, Nf-E tby leriedi glycolamide% HO.CH2.CO.NH.CH2.CH2.NH.CO.CH2OH mw 167.17 crysts, mp 141°, It can be prepd by slowly adding 17.5g of 68.8% aq ethylene-diamine to 36g of methyl glycolate. After addn, die so In is partly evaporated by heating under reduced pressure on a water bath and then cooled. The resulting crysts are separated and purified by recrystallization from 95% ethanol (Ref 2)... 

The duPont Co in 1940 put in operation a unique plant at Belle, West Virginia, in which glycol was manufd by hydrogenation of methyl-glycolate, the raw materials (or which included its own high pressure synthesis products formaldehyde and methanol... 

Methyl glycol dinitrate (propylene-1,2-glycol dinitrate or 1,2-propanediol dinitrate) is an oily liquid, boiling at 92°C at 10 mm Hg. Its spedfic gravity is 1.368 (at 20°Q. The liquid does not freeze at a temperature of —20°C. It is more volatile thfcn the isomeric propylene-1,3-glycol dinitrate. 

In physical properties and explosive parameters methyl glycol dinitrate resembles its isomer. The heat of detonation as 1110 kcal/kg (water as vapour). The expansion produced in the lead block with water tamping is 540 cm3 [4j. 

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