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Absorption spectra and dispersion curves have been obtained for dichloro-, dibromo- and diiodomethane in the liquid phase between 500 and 20 cm−1 using interferometric and Fourier spectroscopic techniques. The refractive index data extend existing information on these molecules to include all infrared active fundamental modes. Dispersion curves have also been obtained for deuterated dichloro- and dibromomethane, in the liquid phase, between 5000 and 450 cm−1. The refractive indices have been used to calculate absolute band intensities, dipole moment derivatives and vibrational polarizations.

A method for measuring the surface energy of solids and for resolving the surface energy into contributions from dispersion and dipole-hydrogen bonding forces has been developed. It is based on the measurement of contact angles with water and methylene iodide. Good agreement has been obtained with the more laborious γc method. Evidence for a finite value of liquid-solid interfacial tension at zero contact angle is presented. The method is especially applicable to the surface characterization of polymers.

The homogeneous solution of iodomethylzinc iodide produced by reaction of equimolar quantities of ethylzinc iodide and diiodomethane in tetrahydrofuran was used to prepare Me 3 SnCH 2 I, Me 2 Sn(CH 2 I) 2 and Hg(CH 2 I) 2 in good yield; this procedure is much superior to that using the reagent prepared from the reaction of diiodomethane with zinc/copper couple. The reaction of ethylzinc iodide with CH 3 CHI 2 , Me 3 SiCHI 2 and Me 3 SnCHI 2 in THF gave good yields of CH 3 CHIZnI, Me 3 SiCHIZnI and Me 3 SnCHIZnI, respectively. These reagents were used to prepare, generally in high yield, the following compounds: Me 3 SnCHICH 3 , Hg(CHICH 3 ) 2 , Me 3 SiCHISnMe 3 , Hg(CHISiMe 3 ) 2 and (Me 3 Sn) 2 CHI. The Hg(CHISiMe 3 ) 2 /Ph 2 Hg reagent pair was found to transfer Me 3 SiCH to cyclohexene and cyclooctene, but the silylcyclopropane product yields were quite low.

A method was developed for the almost quantitative conversion of unsaturated esters (from monoenes to tetraenes) to cyclopropanes using diiodomethane and a highly active zinc-copper couple. These derivatives are sufficiently volatile for GLC analysis andcis andtrans isomers can be distinguished by this technique. Equivalent chain lengths of the cyclopropane derivatives were measured on polar and nonpolar phases. The mass spectra of the monocyclopropane compounds are very similar to those of the parent unsaturated esters. Those of dicyclopropanes, however, are quite distinctive so that the original structure of the ester can be deduced. Polycyclopropanes give complex spectra which are difficult to interpret in terms of the position of the original double bonds.

Unsymmetrisch disubstituierte Thioharnstoffe konnen mit Dijodmethan unter geeigneten Bedingungen zu 1,3-Thiazetidinen reagieren. Wahrend „gewohnliche Thioharnstoffe”, wenn uberhaupt, nur sehr langsam und in geringen Ausbeuten reagieren, fuhrt die Umsetzung von (4-Chinazolyl)thioharnstoffen 1, die eine starke intramolekulare Wasserstoffbruckenbindung ausbilden, in kurzer Zeit und mit guten Ausbeuten zu den entsprechenden Thiazetidinen 4. Der Bildungsmechanismus wird diskutiert. Tautomerism of Heterocyclic Compounds, III1). — 1,3-Thiazetidines from Thioureas with an Intramolecular Hydrogen Bond Unsymmetrically disubstituted thioureas are capable of reacting under suitable conditions with diiodomethane to give 1,3-thiazetidines. Normal thioureas′′ react, if at all, only very slowly and in small yields, whereas (4-quinazolyl)thioureas 1, which have an intramolecular hydrogen bond, react within a short time and with good yields to the thiazetidines 4. The mechanism of formation is discussed.

Reactions of ClCH 2 I with the sodium salts Na[M(CO) 3 C 5 H 5 ] (M = Mo and W) in tetrahydrofuran at room temperature give fairly good yields of the corresponding chloromethyl derivatives ClCH 2 M(CO) 3 C 5 H 5 (M = Mo and W). A similar reaction of ClCH 2 I with the more nucleophilic Na[Fe(CO) 2 C 5 H 5 ] gives a rather low yield of the corresponding chloromethyl derivative ClCH 2 Fe(CO) 2 C 5 H 5 . Reactions of diiodomethane with the sodium salts Na[M(CO) 3 C 5 H 5 ] (M = Mo and W) in tetrahydrofuran at room temperature give the very unstable iodomethyl derivatives ICH 2 M(CO) 3 C 5 H 5 (M = Mo and W). Reactions of ClCH 2 CH 2 I with metal carbonyl anions do not give any isolable 2-chloroethyl transition metal derivatives.

An experimental study has been made of the gaseous drag torque on an isolated sphere rotating at high Mach numbers. The sphere was suspended electromagnetically and spun by induction. The drag torque has been measured through the transition régime from continuum to free molecule flow at Mach numbers (based on equatorial speed) of up to about five. These high Mach numbers were achieved in heavy vapours (diiodomethane, germanium tetrabromide and stannic bromide) with sonic speed as little as a quarter of that in air. To measure the pressure in the vapour a second (smaller) rotating sphere was used as a pressure gauge. The results agree well with those previously obtained and show an unexpected Mach number dependence in the transition régime.

Methylene bridges having an average length n ranging from 1.04 to 1.21 were introduced into cellulose by reaction with dibromomethane or with dichloromethane under strongly alkaline conditions. Similarly, bis(bromomethyl)ether or bis(chloromethyl)ether gave n values ranging from 2.25 to 2.72. Repeated treatments with dibromomethane gave formaldehyde contents leveling off at 17 to 18%, or a D.S. of about 2.

Absorption spectra and dispersion curves have been obtained for dichloro-, dibromo- and diiodomethane in the liquid phase between 500 and 20 cm−1 using interferometric and Fourier spectroscopic techniques. The refractive index data extend existing information on these molecules to include all infrared active fundamental modes. Dispersion curves have also been obtained for deuterated dichloro- and dibromomethane, in the liquid phase, between 5000 and 450 cm−1. The refractive indices have been used to calculate absolute band intensities, dipole moment derivatives and vibrational polarizations.

Highly flexible model red cells were molded of acrylamide gel and suspended in a mixture of castor oil and diiodomethane to produce a neutrally buoyant fluid suspension in which the particles behaved mechanically very much like living erythrocytes. The various suspensions were permitted to flow down long cylindrical tubes while measurements of flow rate and pressure drop were made for various concentrations. The fluid suspensions were found to exhibit non-Newtonian viscous behavior which agrees very well with that of whole blood under comparable conditions. The fluid suspensions also exhibited a yield stress below which particle motion ceases. The yield stress was found to depend strongly on particle concentration, as is the case for whole blood.

Raman displacements, semiquantitative relative intensities, quantitative depolarization factors, and wave numbers for the infrared bands in the region 400–3800 cm−1 have been obtained for liquid CH2I2. A normal coordinate treatment was carried out, and a reasonable set of potential constants was determined, using the most general quadratic potential energy function. Assignments were made for all observed Raman and infrared bands. The heat content, free energy, entropy, and heat capacity at constant pressure were calculated for 12 temperatures from 100° to 1000°K.