Dimethyl-1,1’-ferrocene dicarboxylate

At this column temperature many of the compounds listed in Table 163 are separated. When a single component sample is handled, the column temperature should be 10 to 20°C lower than the indicated column temperature, (for example, ferrocene, ferrocenemercury chloride, iodoferrocene) or higher than the indicated temperature (namely 1,1 -diacetylferrocene, dimethyl 1,1 -ferrocene dicarboxylate, phenyl-ferrocene) but when the sample contains several ferrocenes the column temperature should be selected in order to optimize the separation. 

During the synthesis of 1,1 ferrocene dimethanol from ferrocene, the starting material, ferrocene and the intermediates, 1,1 -diacetyl-ferrocene and dimethyl 1,1 -ferrocene dicarboxylate all occur in the product, and chromatograms of this mixture are shown in Figure 234. 

It also was found that the direction of the photobiocatalytic switch of the nitrospiropyran-FAD-reconstituted enzyme is controlled by the electrical properties of the electron transfer mediator. With ferrocene dicarboxylic acid as a diffusional electron transfer mediator, the enzyme in the nitrospiropyran-FAD state (10a) was found to correspond to the OFF state bio-catalyst, while the protonated nitromerocyanine state of the enzyme (10b) exhibits ON behavior. In the presence of the protonated 1-[1-(dimethyl-amino )ethyl]ferrocene, the direction of the photobioelectrocatalytic switch is reversed. The nitrospiropyran-enzyme state (10a) is activated toward the electrocatalyzed ox idation of glucose, while the protonated nitromerocyanine enzyme state (10b) is switched OFF, and is inactive for the electrochemical oxidation of glucose. This control of the photoswitch direction of the photoisomerizable reconstituted enzyme was attributed to electrostatic interactions between the diffusional electron mediator and the photoisomefizable unit... 

Ferrocene-1,l -dicarboxylic acid [1293-87-4] IV 274.1, m >250°(dec), >300°. Orange-yellow crystals from AcOH. Sublimes above 230°. Monometh ester m 147-149° [Dokl Acad Nauk USSSR 115, 518 1957]. Dimethyl ester m 114-115° [JACS 74, 3458 1958]. Diacid chloride m 92-93° from pet ether. [Dokl Acad Nauk USSSR 120 1267 1958 127 333 7959]. 

SAFETY PROFILE Poison by inhalation and ingestion. A corrosive eye, skin, and mucous membrane irritant. Potentially explosive reaction with water evolves hydrogen chloride and phosphine, which then ignites. Explosive reaction with 2,6-dimethylpyridine N-oxide, dimethyl sulfoxide, ferrocene-1,1 -dicarboxylic acid, pyridine N-oxide (above 60°C), sodium -L heat. Violent reaction or ignition with BI3, carbon disulfide, 2,5-dimethyl pyrrole + dimethyl formamide, organic matter, zinc powder. Reacts with water or steam to produce heat and toxic and corrosive fumes. Incompatible with carbon disulfide, N,N-dimethyl-formamide, 2,5-dimethylpyrrole, 2,6-dimethylpyridine N-oxide, dimethylsulfoxide, ferrocene-1,1-dicarboxylic acid, water, zinc. When heated to decomposition it emits highly toxic fumes of Cl" and POx. 

PHOSPHORUS CHLORIDE (10025-87-3) Fumes in moist air. Contact with water, steam, or alcohols produces hydrochloric acid, phosphoric acid, and phosphine gas, which is pyrophoric, with possible ignition or explosion (may be a delayed reaction). Contact with air produces corrosive fumes. Violent reaction with carbon disulfide, 2,6-dimethylpyridine-iV-oxide, dimethyl sulfoxide, ferrocene l,l -dicarboxylic acid, pyridine, zinc powder. Reacts, possibly violently, with acids, alkali metals, alkalis, combustible materials, dimethyl for-mamide, organic matter, zinc powder. Incompatible with acetic anhydride, yV,V-dimethyl formamide, 2,5-dimethylpyrrole, sodium. Rapid corrosion of steel and most metals, except lead, occurs in the presence of moisture. 

---