Bis hydroxymethyl malonate

DIETHYL BIS(HYDROXYMETHYL)MALONATE (Malonic acid, bis(hydroxymethyl)-, diethyl ester)... 

Diethyl bis (hydroxymethyl) malonate is a useful intermediate for preparing substituted malonic esters. 

Fluorenylamine, 40,5 Formaldehyde, reaction with diethyl malonate to form diethyl bis-(hydroxymethyl)malonate, 40,27 Formamide, condensation with 4,4-dimethoxy-2-butanone to give 4-methylpyrimidine, 43, 77 Formic acid, and hydrogen peroxide, with indcne, 41, 53... 

Ethyl a-(bromomethyl)acrylate Acrylic acid, 2-(bromomethyl)-, ethyl ester (8) 2-Propenoic acid, 2-(bromomethyl)-, ethyl (9) (17435-72-2) Diethyl bis(hydroxymethyl)malonate Malonic acid, bis(hydroxymethyl)-, diethyl ester (8) (20605-01-0)... 

Diethyl bis(hydroxymethyl)malonate was prepared up to an 8.0-mol scale by the method of Block.2 After suction filtration to remove the drying agent, the dried diethyl ether extracts were concentrated directly on a Biichi rotary evaporator at aspirator vacuum using a bath temperature of 50°C concentration was continued for ca. 2 hr after removal of the ether. The crude, oily diethyl bis(hydroxymethyl)malonate, obtained in 94—96% yield, solidified on standing and was suitable for use without further purification. The malonate can be stored at room temperature with no special precautions. 

The checkers ran this reaction on a 20% scale [starting with 88 g (0.4 mol) of diethyl bis(hydroxymethyl)malonate]. At this scale, yields between 63 and 75% were realized. 

With diethyl malonate. Two different products are obtainable in moderate yield by reaction of malonic ester with formalin. With a 1 2 ratio of aldehyde to ester and diethylamine as catalyst, the product is the tetraester (1), an intermediate in one synthesis of glutaric acid. With a 2 1 ratio and potassium bicarbonate as catalyst, the product is the crystalline solid diethyl bis(hydroxymethyl)malonate (2). ... 

Diethyl malonate, reaction with formaldehyde to form diethyl bis-(hydroxymethyl)malonate, 40, 27... 

Klaas therefore reasoned analogously that pentaerythritol (LVII) should produce bis(hydroxymethyl)malonic acid (LVIII) and, ultimately, 3-hy-... 

Aryl-5,5-bis(oxazolin-2-yl)-l,3-dioxanes 169 have been easily prepared in three steps from diethyl bis(hydroxymethyl)malonate, amino alcohols, and aromatic aldehydes. They have been used for the copper-catalyzed asymmetric cyclopropanation of styrene with ethyl diazoacetate in up to 99% ee for the trawx-cyclopropane (maximum transicis ratio = 77/23) <05TA1415>. The same reaction performed on 2,5-dimethyl-2,4-hexadiene with tert-butyl diazoacetate in the presence of copper catalysts bearing ligand 170, prepared from arylglycines, exhibited remarkable enhancement of the rrawx-selectivity (transicis ratio = 87/13), with 96% ee for the trans product <05JOC3292>. 

Guzaev and Lonnberg [221] have proposed an original diethyl 2,2-bis(hydroxymethyl)malonate anchor (Figure 19.11) on LCAA-CPG (up to 60 xmolg 1) that is cleavable under basic conditions via a retroaldol reaction followed by P-elimination. Formation of the 3 -phosphate takes about 20 min in concentrated ammonia and progressively longer under milder conditions 3h in 0.05 M potassium carbonate in methanol and 10 h in 50% ethanolic ethylenedi-... 

Materials. Terephthaldicarboxaldehyde (Aldrich), diethyl bis(hydroxymethyl) malonate (Aldrich), p-toluenesulfonic acid (Aldrich), potassium hydroxide (85 wt%, Fisher), pyridine (Fisher), glutaric dialdehyde (50wt% aqueous solution, Aldrich), ethylene glycol divinyl ether (Aldrich), ethyl glycolate (Aldrich), isophthalic dicarboxaldehyde (Lancaster), propionaldehyde (Eastman Chemical), isovaleraldehyde (Aldrich), 2-ethyl-2-oxazoline (Acros), ammonia (7M in methanol, Acros), l-methoxy-4-(methylthio)benzene (Aldrich), silver... 

---