US2500110A - Bispyridyl compounds containing a silicon atom and process of preparation - Google Patents

Description

Patented Mar. 7, 1950 UNITED STATES PATENT OFFICE BISPYRIDYL COMPOUNDS CONTAINING A SILICON ATOM AND PROCESS OF PREP- ARATION Charles F. H. Allen and Donald M. Burness, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application June 12, 1948,

7 Serial No. 32,734

compounds in which the linkage between carbon and silicon is interrupted by oxygen, sensitize photographic silver halide emulsions (whether spectrally sensitized or not) and have the added advantage of not diffusing appreciably from the emulsions into the film support upon which the emulsions are usually coated.

It is, accordingly, an object of our invention to provide a new class of chemical compounds and a process for preparing them. Another object of our invention is to provide a new class of chemical compounds which are useful in increasing the speed and sensitivity of photographic silver halide emulsions. Still another object is to provide a new class of chemical compounds useful in increasing the speed and sensitivity of photographic silver halide emulsions which do not diffuse from the emulsions into the film support upon which the emulsions are usually coated. A still further object is to provide photographic silver halide emulsions (whether spectrally sensitized or not) sensitized with a new class of chemical compounds, and to a process for preparing such emulsions. Other objects will become apparent from a consideration of the following description.

According to the process of our invention, we prepare our new compounds byv interacting an alcohol containing as a substituent, a heterocyclic nucleus of the pyridine series, and an organic dihalosilane. ried out in the presence of a tertiary organic amine.

The alcohols containing, as a substituent, a heterocyclic nucleus of the pyridine series, which are useful inpracticing our invention, can advantageously be represented by the general formula:

--zrf on -on)i..= -(on,)..-on wherein Z represents the non-metallic atoms 12 Claims. (01. 260-290) The process is advantageously carnecessary to complete a heterocyclic nucleus of the Pyridine series, d represents a positive integer from 1 to 2, and m represents a positive integer from 2 to 3. Typical alcohols include, for example, fi- (Z-pyridyl) -ethanol, 7- (2-pyridyl) propanol, 18- (4-methylpyridyl-2) -ethanol, .18- (6- methylpyridyl-2) -ethanol, p-(5-ethylpyridy1-2) ethanol, fl- (4-pyridyl) -ethanol, '7- (4-pyridyl) propanol, fl-(3-ethyl pyridyl-4)-ethanol, etc. In addition to containing alkyl substituents such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, etc. (i. e., an allryl group of the formula CnH2n+1 wherein n is a positive integer from 1 to 4), the pyridine nucleus can have substituted thereon such groups as C1, Br--, ChaO-,

The organic dihalosilanes useful in practicing our invention can advantageously be represented by the general formula:

X -SPXT wherein R and R1 each represents a member selected from the group consisting of an alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, etc. (i. e., an alkyl group of the formula CnHiln+1 wherein n is a positive integer from 1 to 4) and a mononuclear aryl group of the benzene series, e. g., phenyl (CsHs), 0-, mand p-tolyl (CHaCaH4-), o-, mand p-chlorophenyl (C1CsH4-). o-, mand p-bromophenyl (BrC6I-I4), etc. and X1 represents a halogen atom, such as a chlorine atom or a bromine atom.

. Typical silanes include, for example, dibromodimethylsilane, dichlorodimethylsilane, dichlorodiethylsilane, dichlorodi-n-propylsilane, dichlorodiphenylsilane, dibromodiphenylsilane, di-(pbromophenyl) dichlorosilane, dichlorodi (ptclyl) -silane, dichloroethylpropylsilane, dichloroethylisobutylsilane, dichloroethylphenylsilane, dichloro-p-bromophenylphenylsilane, etc.

The process of our invention can advantageously be carried out in the presence of an organic amine, such as a tertiary organic amine. Typical tertiary organic amines include, for example, the trialkyl amines, such as triethyl amine, tri-n-propylamine, trilsopropylamine, trl-nbutylamine, triisobutylamine, the tertiary aromatic amines, such as N,N-dimethylaniline, N,N- diethylaniline, N,N-dipropylaniline, etc., and the tertiary heterocyclic amines, such as pyridine,

quinoline, isoquinoline, a-picoline, p-picoline,

2,500,110 4 be carried out in a solvent which does not react the above formula represents a bromide ion or an with any of the materials present in the .rciodide ion can convenientlybe prepared by interaction mixture. Typical solvents include the diacting a quaternary salt of our bis-pyridyl comaikyl ethers, such as diethyl ether, diisopropyl pounds, suchasthe d-methyl-p-toluenesulionate, ether, etc., the halogenated hydrocarbons, such 5 with potassium bromide and potassium iodide,reas chloroform, carbon tetrachloride, ethylene dispectively. Compounds where X represents a chloride, etc., 1,4-dioxane, the normally liquid perchlorate '(ClOr) ion can advantageously be hydrocarbons, such as n-heptane, benzene, prepared by interacting a quaternary salt of our toluene, o-, mand p-xylenes, etc. The tembls-pyridyl compounds, such as the dimetho-pperature at which our process can be carried out tcluenesulfonate, with sodium perchlorate. Comvaries and is generally a function of the repounds where Xrepresents a chloride ion or a thiactants emp oye W av found that ocyano (SCN-) ion can conveniently be obtained peratures of from to 40 C. are usually suillby interacting a quaternary salt where X reprecien f r h rp 0! r inve n, h h sents an iodide ion with a methanol suspension of lower or higher temperatures can be used, if de- 15 silver chloride or silver thiocyanate, respectively. sired. Other methods of preparing our new quaternary ammonium compounds can be used, if desired, The process or our invention can conveniently Such methods are commonly employed and are be illustrated by the following general equation: well known to those skilled in the art. For exa -z sf-icn- -cn)-,==ccm).-0-%l-ocm)..-C"=== oa-on le R1 wherein R, R1- Z, d and m have definitions desigample, compounds where X represents a halide nated above. The hydrogen halide HXi which is ion can be prepared by heating our new free bases formed during the reaction readily combines with with the appropriate alkyl halide in a sealed tube.

the tertiary organic amine to form a salt which The following examples will serve to illustrate can be filtered oil from the reaction mixture. further the manner whereby we practice our in- Our new bis-pyridyl compounds, which are obvention.

tained as free bases in the reaction illustrated above, can be further treated to obtain their qua- Example WOW] ternary salts. For example, when the free base is heated with an alkyl ester of p-toluenesulfonic acid, a quaternary ammonium compound is readily formed. Other quaternary ammonium can compounds can be readily prepared by heating 40 the free bases with a compound containing an acidic anion. Another method for preparing q a y ammonium compounds of our new 35.1 parts by weight of 7-(2-pyrldyl)-propanol bases comprises heating one of the alkyl sulfuric (B. P. 134 to 139 C./11 mm.) were dissolved in or sulfonic acid ester addition salts of our new 250 parts by weight of anhydrous diethyl ether, bases with an inorganic salt (1. e., by double deand 30 parts by weight of triethylamine added.

composition). The quaternary addition com- While this solution was vigorously stirred, a secpounds which are readily obtainable from our 0nd solution of 20 parts by weight of redistilled new bases can be represented by the general fortechnical dichlorodiethylsiiane in anhydrous dimula: ethyl ether was added dropwise. After the addia z fl z RI I-1 :(CH--CH) =;b-(CHQ-OBlo-(CHI)||6= ZCH*CH)d-l wherein R, R1, Z, d and m have the definitions destion was complete, the mixture was stirred for an ignated above, and R2 represents an alkyl group. additional hour at room temperature (20-25 C.) such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and then filtered. The ethereal filtrate was isobutyl, sec-n-butyl, amyl, etc. (i. e., an alkyl washed thoroughly with water, dried, and alter group of the formula Cam's-+1 wherein n repreremoval of the ether, the residue was fractionally sents a positive integer from 1 to 5), and X repdistilled under a vacuum. There were thus obresents an anion (or acid radical), such as halide tained 33 parts by weight of dlethyl-di-[y-(Z- (e. g., C1-, Br-, 1-), perchlorate 0104-), thiopyridyD-propoxy] silane distilling at 194 to 198' cyano (SCN'), alkylsulfate (e. g., CHJSOA"), ben- C./1.5 mm. The analysis of this compound zenesulfonate (Cal-158020), p-toluenesulfonate 05 was as follows:

(p-CHaCeH4SO2O-), etc. Typical esters which can be reacted directly by heating with our new bases to ive useful quaternary salts include diemulated Found methylsulfate, diethylsulfate, methylbenzenesul- C 67 0 6m fonate, ethyl benzenesulfonate, n-propyl benzene- 70 a. s14 as sulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, n-propyl p-toluenesulfonate, n-butyl p-toluenesulfonate, isobutyl p-toluenesulfowhen an ethereal solution of 0.256 mol of hate, sec-n-butyl p-toluenesulfonate, n-amyl p- 7-(4-pyridyl)-propano1 was reacted with an toluenesulfonate, etc. Compounds wherein X in 76 ethereal solution of 0.127 mol of dichlorodiethylsilane in the presence or trlethylamine in exactly the same manner as described in Example I, diethyLdi-[y- (4-pyridyl) -propoxyl silane boiling at 210 to 216 C./1.5 mm. was obtained. The

formula of this compound can berepresented as:

- 01H: CHrCHrCHt-O-AiOCKr-CHt-CH The analysis of this compound was as follows:

Calculated Found Example Il.Diethyl-di- [p- (Z-pyridul) -etho:ul

silane filtrate was washed thoroughly with water, dried and, after distilling off the ether from the solution, the residue was fractionally distilled. There were thus obtained 28.6 parts by weight of diethyl-di-[p-(2-pyridyl)-ethoxy] silane as a pale yellow liquid distilling at 158 to 162 C./1 mm. The analysis of this compound gave the following results:

Calculated Found When an ethereal solution of 0.256 mol of B-(l-pyridyl) -ethanol was reacted with an ethereal solution of 0.127 mol of dichlorodiethylsilane in the presence of triethylamine in exactly the same manner as described in Example II, diethyldi-ifi-(i-pyridyl) -ethoxy] silane distilling at 199 to 204 C./3mm-. was obtained. The formula of this compound can be represented as:

j can VCHr-CIIrO-A The analysis of this compound gave the following results:

CHx-C HrCHz-O- Si-O-CHrC HrCH Calculated Found When an ethereal solution of 0.256 mol of p- (5- ethylpyridyl-2) -ethanol is reacted with an ethereal solution or 0.127 mol of dibromodimethylsilane in the presence of quinoline in exactly the same manner as described in Example IIJdi-[p- (5-ethylpyridyl-2-ethoxyl dimethylsilane represented by the formula;

can be obtained. In like manner, when an ethereal solution of 0.256 mol of ,8-(3-ethylpyridyl-4)-ethanol is reacted with an ethereal solution of 0.127 mol of dichloroethylisobutylsilane in the presence or dimethylaniline, di te- (3-ethylpyridyl-4)-ethoxy] ethylisobutylsilane represented by the formula:

CrHi

can be obtained.

Example III.Dieth1 Z di ['y -(2 pyridyD- propoxz l silane dimetho-p toluenesulfonate CQHI I N .2 p-CliiaCoHrS 0:0-

4.8 parts by weight of methyl p-toluenesulfonate were added to 3.6 parts by weight of the diethyl-di-[Y-(2-pyridyl) -propoxy] silane obtained in Example I, and the mixture was heated at to C. on an oil bath for one hour.. The excess methyl p-toluenesulfonate which was used was removed by extraction with warm benzene, all traces of which were removed under reduced pressure. A quantitative yield (7.3 parts by weight) of diethyl-di-[7-(2-pyridyl) -propoxy] silane dimetho-p-toluenesulfonate was obtained.

It was found to be soluble in water, ethyl alcohol or hot acetone, but insoluble in hydrocarbon solvents, such as benzene, etc.

When 4.8 parts by weight of methyl p-toluenesulfonate were added to 3.6 parts by weight of the diethyl-di-[y-(i-pyridyl) -propoxy] silane obtained in Example I, dieth'yl-di-[y-(-pyridyl)- propoxy] silane dimetho-p-t0luenesulfonate, which exhibited solubility properties similar to those of the product obtained in Example III, was obtained. When either of these dimetho-ptoluenesulfonates are warmed with a methanol solution of potassium iodide, the corresponding dimeth iodides are readily formed. When these dimeth iodides are warmed with a methanol solution of silver thiocyanate (Ag SCN), the

corresponding dimetho thiocyanates are formed with ease.

Example IV.-Diethyl-di-[fi-(Z-pvridyl)ethorill silane dimetho-p-toluenesulfonate 4.8 parts by weight of methyl p-toluenesuiiohate were added to 3.3 parts by weight of the diethyldi- {3- (Z-pyridyl) -ethoxyl silane obtained in Example II, and the mixture was heated on a steam bath for one hour. The excess methyl p-toluenesulfonate which was used was removed by extraction with warm benzene, all traces of which were removed by warming the residue under a vacuum. An almost quantitative yield (6.5 parts by weight) of diethyl-di- [/3- (Z-pyridyl) ethoxy] silane dimetho p-toluenesulfonate was thus obtained. It was found to be soluble in water, ethyl alcohol or warm acetone, but insoluble in hydrocarbon solvents, such as benzene.

When 4.8 parts by weight of methyl p-toluenesulionate were added to 3.3 parts by weight of diethyl-di-[fi-Ol pyridyl) ethoxy] silane obtained in Example II, and the mixture warmed on a steam bath for one hour, diethyl-di-[p- (4-pyridyD-ethoxy] silane dimetho p-toluenesulfonate, which exhibited solubility properties similar to those of the products obtained in Examples III and IV, was obtained. When either of these dimetho p-toluenesulfonates are warmed with a methanol solution of sodium perchlorate, the corresponding dimetho perchlorates are readily formed.

Similarly, when 0.01 mol of di-[B-(3-ethylpyridyi-4)-ethoxy] ethylisobutylsilane is warmed with 0.0275 mol of diethylsulfate, and the excess diethylsulfate removed as described above, di- [fi-(B-ethylpyridyl 4) ethoxy] ethylisobutylsilane diethyl sulfate represented by the formula:

can be obtained.

Example V.-Diphenyl-di- [{3- (Z-pyridyl-ethoxy] silane 31.5 parts by weight of [3-(2-pyridy1) -ethanol were dissolved in 250 parts by weight of anhydrous diethyl ether, and parts by weight of triethylamine added. While this solution was vigorously stirred, a second solution of 32.1 parts by weight of redistilled technical dichiorodiphenyisilane in anhydrous diethyl ether was added dropwise. After the addition was complete, the mixture was stirred for an additional hour at room temperature (20-25 C.) and then filtered. The ethereal filtrate was washed thoroughly with water, dried, and after removal of the ether, the residue was iractionaliy distilled under a vacuum. There was thus obtained, dlphenyl-di-[fi-(2-pyridyl) -ethoxyl 51- lane as a yellow oil distilling at 221 C./1 mm. This oil darkened on standing.

When a molecularly equivalent amount of dichlorodi-(p-tolyi) silane is reacted with 542- pyridyl) -ethanol in accordance with the process described above, di-[fl-(Z-pyridyD-ethoxyl di- (p-tolyl) silane represented by the formula:

is formed.

Example VI.Diphem/l-di- [p-(Z-puridyl) ethomy] silane dimetho-p-toluenesulfonate 4.8 parts by weight 0! methyl p-toluenesulfonate were added to 4.3 parts by weight of the diphenyl-di- B- (Z-pyridyl) -ethoxy] silane obtained in Example V, and the mixture was heated on a steam bath at IOU- C. for one hour. The excess methyl p-toluenesulionaie was removed by dissolvin the reaction mixture in water and extracting with benzene. The last traces of methyl p-toluenesultonate were removed by warming the aqueous solution in a vacuum, and the water was then removed under reduced pressure. There remained an almost quantitative yield of diphenyl-di-[fi-(Z- pyridyD-ethoxy] silane dimetho-p-toluenesulfonate as an amber oil. It was soluble in water, alcohol, and acetone, but insoluble in benzene. When this dimetho-p-toluenesultonate is reacted with a methanol solution of potassium bromide, the quaternary salt, diphenyl-di-[,B-(Z-pyridyl)- ethoxy] silane dimethobromide is readily formed. Similarly, by reacting this dimetho-p-toluenesulfonate with a methanol solution of potassium iodide, diphenyl-di- [,3- (Z-pyridyl) -ethoxy] silane dimethiodide is formed.

Operating in a similar manner, other bis -or methyl alcohol.

pyridyl compounds, as well as their quaternary ammonium salts, can be prepared by reacting alkanols substituted by a pyridyl nucleus with other organic dihalogenosilanes in the presence of a tertiary organic amine. For example, when fi-(4-methylpyridyl-2)-ethanol is reacted with dichlorodipropylsilane in the presence of triethylamine, di- [,8- (4-methylpyridyl-2) -ethoxyl dipropylsilane represented by the formula:

can be obtained. when propyl benzenesulfonate is warmed with this base, the dipropo benzenesulfonate addition salt is readily formed.

In accordance with our invention, the polyammonium salts of our bis-pyridyl compounds can be incorporated in photographic silver halide emulsions in any suitable form, e. g., .in the form of a solution in a suitable solvent, such as water The olyammonium salts should be thoroughly incorporated in the emulsion. Since the introduction of halide anions into photographic silver halide emulsions alters the halide concentration in the emulsion, and compensating changes in the emulsion may be desirable, if such poly-ammonium salts are employed, we generally prefer to employ polyammonium salts containing anions other than halides. Perchlorates and p-toluenesulfonates have been found to be especially useful.

In the case of spectrally sensitized emulsions,

the polyammonium salts of our bis-pyridyl compounds can be incorporated in the emulsion before, simultaneously with or afterthe sensitizing dye, although in some cases it may be advantageous to incorporate the sensitizing dye before incorporating the polyammonium salt. The methods of incorporating sensitizing dyes in emulsions are, of course, well known to those skilled in the art. Ordinarily, it is advantageous to employ a solution of the sensitizing dye in a suitable solvent, e. g., methyl alcohol; ethyl alcohol or acetone can be employed in cases where the solubility of the sensitizing dye in methyl alcohol is very low. Sensitizing dyes are ordinarily incorporated in the washed, finished emulsions, and, in accordance with our invention, the polyammonium salts are advantageously also incorporated in the washed, finished emulsions. However, the polyammonium salts can be added to the emulsion during the preparation thereof, i. e., during the precipitation, the first digestion or the second digestion (ripening). After preparing the emulsions in the presence of the polyammonium salts, the sensitizing dyes can be incorporated in the so-prepared emulsions.

The quantity of the polyammonium salt which is most advantageously employed varies with the nature of the polyammonium salt and with the nature of the emulsion. In most instances,

a satisfactory concentration was found to be between about 20 mg. and 200 mg. of th polyammonium salt per gram-mole of silver halide in the emulsion, although greater or smaller concentrations could be employed. We have found, however, that too large quantities of the polyammonium salts are advantageously avoided, since excesses tend to produce fogin the emulsions.

Th upper range of concentration for any particular one of our polyammonium salts in any particular type of emulsioncan be determined by employing a series of concentrations of the polyammonium salt separately in several batches of the same emulsion, and determining the sensitivity of the several emulsions before and'after incorporation of our polyammonium salt or salts. This method of determining the optimum concentration may be carried out in any conventional manner. Briefly, the method we would employ would comprise coating the aforementioned emulsions in suitable thickness onto glass plates and then testing the resultant photos graphic plates in a wedge spectograph and a sensitometer, whereby the spectral sensitivity and speed of the emulsion on th plate may be determined.

When employing spectrally sensitized emulsions, the spectral sensitizers are advantageously employed in about their optimum concentration, which, for most purposes may be considered as lying between about 3 mg. and 20 mg, of spectral sensitizer per liter of emulsion containing about 0.25 mole of silver halide, although it is to be understood that these values are merely set forth for purposes 0! illustration and the concentrations above or below the aforementioned concentrations can be employed. With fine-grain emulsions (which includes many of the ordinarily employed silver chloride emulsions), the ratio of the sensitizing dye to the concentration of the silver halide in the emulsion may advantageously be larger than in the coarser-grained emulsions, where smaller amounts of sensitizing dye will, in many instances, give satisfactory or optimum sensitization. The optimum concentration, as discussed herein, of a sensitizing dye, namely the concentration at which the apparently greater sensitivity occurs, can also be determined in any conventional manner known to those skilled in the art by measuring the sensitivity of a series of emulsions containing different concentrations of the sensitizing material.

We wish to point out, however, that when our polyammonium salts are incorporated into a spectrally sensitizedemuision (as contrasted to an unsensitized emulsion), it is desirable that the sensitizing dye be compatible with our polyammonium salt.

For this reason, as spectral sensitizers (sensitizing dyes), we would employ only those which are substantially non-acidic. As non-acidic sensitizing dyes, we include all the known neutral and basic sensitizing dyes, and it is to be understood that our invention is not restricted in this respect. Examples of some of the non-acidic sensitizing dyes are the sensitizing cyanine dyes (see, for example. United States Patents 1 846,300; 1,846,301; 1,846,302; 1,846,303 and 1,846,304, each dated February 28, 1932; United States Patent 1,861,836, dated June 7, 1932; United States Patent 1,939,201, dated December 12, 1933; United States Patent 1,942,854, dated January 9, 1934; United States Patent 1,957,869, dated May 8, 1934; United States Patent 1,962,124, dated June 12, 1934; United States Patent 1,969,446, dated August 7, 1934; United States Patent 1,973,462, dated September 11, 1934 United States Patent 1,990,507, dated February 12, 1935; United States Patent 2,094,580, dated October 5, 1937; United States Patent 2,112,140, dated March 22, 1938, and French Patent 757,813, published January 5, 1934), the sensitizing merocyanine ,dyes (see United States Patent 2,078,233, dated April 27, 1937; United States Patent 2,089,729, dated August 10, 1937; United States Patent 2,153,169, whereinRand R1 each represents an alkyl group dated April 4, 1939; and United ,States Patents of the formula CnHZn-H wherein n is a positive 2,177,401, 2,177,402, and 2,177,403, dated October integer from 1 to 4.

1939), the sensitizing ya ine dyes see 4. A bis-pyridyl compound selected from those United States Patent 2,166,736, dated July 18, represented by the general formula;

1939) and the sensitizing hemioxonol dyes (see United States Patent 2,165,339, dated July 11,

1939, and French Patent 841,632, published May f 24, 1939). N/ H:)- l Hi)-- \N It is consequently apparent from the foregoing l0 n, that our polyammonium salts may be incorpo- X x R: J rated in emulsions containing a large variety of wherein R and R1 each represents an alkyl group diflerent sensitizing dyes. of the formula CnHZn-H. wherein n is a positive S already Pointed out, 1 p o ess s subject integer from 1 to 4, R2 represents an alkyl group to considerable variation, particularly as respects of the formula CnHin-l-l wherein n is a positive the method of addition of our polyammonium integer from 1 to 5, mrepresents a positive integer salts, the type of photographic material treated from 2 to 3 and X represents an anion. (spectrally sensitized or not) and the nature of 5. A bis-pyridyl compound selected from those the material and amounts added. Our invention represented by the general formula: is useful for all types of optically sensitized emulsions, especially unsensitized emulsions of R relatively low iodide content. 1

What we claim and desire secured by Letters r 0-GH,-CH, \N Patent of the United States is: v R

1. A bis-pyridyl compound selected from those RI X X n: represented by the two general formulas: wherein R and R1 each represents an kyl gr up z R ,,.z N1:-(-CH-- mai iboHnr-o-si-mom).-6 on flh-lfq and R! z II R,

ti' lcfl cmd-i bom)..-o-si -oonl)rdwln-cmi-i" x 1 \X wherein Z represents the non-metallic atoms of the formula CnHZvH-l wherein n is a positive necessary to complete a heterocyclic nucleus of int r from 1 to 4. R2 repres ts an a yl up the pyridine series, R and R1 each represents 3, 0f the formula CnHZrH-l wherein Tl 1S 8. positive member selected from the group consisting of an 40 integer from t0 and X represents an anion.

alkyl group of the formula CnH2n+1 wherein n A bis-pyridyl compound represented by the is a positive integer from 1 to 4, and a monoformula: nuclear aryl group of the benzene series, R2 represents an alkyl group of the formula CnH27i+1 I wherein n is a positive integer from 1 to 5, m represents a positive integer from 2 to 3, d rep- N/ CHFCHFO QX OCH' CH a resents a positive integer from 1 to 2, and X rep- 1 resents an anion. 7. A bis-pyridyl compound represented by the 2. A bis-pyridyl compound selected from those a! represented by the general formula:

C311 6 g N/ om-cHr-oHr-og-o-om-oHr-OH= CHrCHg-0--Bl0CH2-CH: :m N 1 N 8. A bis-pyridyl compound represented by the formula:

01H! Ii-I CHr-CH:-()Ai-;IOCH:CHr fi -2p=CBiClH|SO:O' (13H; 2 (EH1 wherein R and R1 each represents an alkyl group of the formula CnH2n+1 wherein n is a positive integer from 1 to 4.

9. A process for preparing a bis-pyridyl compound selected from those represented by the general formula:

n z z l= on--oml ,=oom),..-o-sl -oon, .,-6= on-orl)l ,==N

3. A bis-pyridyl compound selected from those wherein Z represents the non-metallic atoms represented by the general formula: necessary to complete a heterocyclic nucleus of the pyridine series,'R and R1 each represents a R member selected from the group consisting of an all: 1 rou of the N, CHECHPCHPO QI O CH, CHPCHP\ y g p formula CnH2n+i wherein n is a positive integer from 1 to 4 and a mononuclear i aryl group of the benzene series, d represents a positive integer from 1 to 2, and m represents a positive integer from 2 to 3, comprising reacting a compound selected from thou represented by the general formula:

R Xr-Al-Xl wherein R and R1 each represents a member selected from the group consisting of an alkyl group of the formula Cums-+1 wherein n is a positive integer from 1 to 4 and a mononuclear aryl group of the benzene series and Xi represents a halogen atom in the presence of a tertiary organic amine.

10. A process for preparing a bis-pyridyl compound selected from those represented by the general formula:

wherein R and R1 each represents an alkyl group of the formula CnHmH-i wherein n is a positive integer from 1 to 4 and m is a positive integer from 2 to 3, comprising reacting a compound selected from those represented by the general formula:

(CHQrOH wherein m represents a positive integer from 2 to 3, with a silaneselected from those represented by the formula:

wherein R and R1 each represents an alkyl group of the formula CnH2n+1 wherein n is a positive integer from 1 to 4 and X1 represents a halogen atom in the presence of a tertiary organic amine.

11. A process for preparing a bis-pyridyl com.- pound selected from those represented by the general formula:

wherein R. and R1 each represents an alkyl group of the formula CnH2n+1 wherein n is a positive integer from 1 to 4 and m is a positive integer from 2 to 3, comprising reacting a compound selected from those represented by the general formula:

wherein m represents a positive integer from 2 to 3, with a silane selected from those represented by the formula:

wherein R and R1 each represents an alkyl group of the formula CnH2n+1 wherein n is a positive integer from 1 to 4, in the presence of a trialkyl amine.

12. A process for preparing a bis-pyridyl compound selected from those represented by the general formula:

wherein R and R1 each represents an alkyl group of the formula CnH2n+i wherein n is a positive integer from 1 to 4 and m is a positive integer from 2 to 3, comprising reacting a compound selected from those represented by the general formula:

I cunt-mu wherein m represents a positive integer from 2 to 3, with a silane represented by the formula:

in the presence of a trialkyl amine.

CHARLES F. H. ALLEN. DONALD M. BURNESS.

No references cited.

Certificate of Correction 1 Patent No. 2,500,110 March 7, 1950 CHARLES F. H. ALLEN ET AL.

It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows:

Column 6, line 12, for -2-ethoxy] read -2) ethoxy] Example III, for that portion of the formula reading column 7, Example IV, second formula thereof, for that portion reading Ha Ha Example V, in the formula, for CH GH, read 0H,--OH,; column 8, lines 38 to 40, inclusive, for

column 12, line 60, for that portion of the formula reading .2p==CH; read .2p-C'H,

and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the casein the Patent Office.

Signed and sealed this 4th day of July, A. I). 1950.

THOMAS F. MURPHY,

Assistant C'omrm'aaioner of Patents.

Claims (1)

1. A BIS-PYRIDYL COMPOUND SELECTED FROM THOSE REPRESENTED BY THE TWO GENERAL FORMULAS: