US3322804A - Aliphatic polyether substituted ferrocene - Google Patents

Description

3,322,804 Patented May 30, 1967 United States Patent Oflice 3,322,804 Hr ALIPHATIC POLYETHER SUBSTITUTED FERROCENE Roy L. Pruett, Charleston, W. Va., assignor to Union Carbide Corporation, a corporation of New York 5 No Drawing. Filed June 11, 1963, Ser. No. 286,947

6 Claims. (Cl. 260-439) C This invention relates to a novel-aliphatic polyether substituted ferrocene. 10 Ferrocene is an art term for the compound bis(cyclo- H H5 pentadienyl)iron. This compound has evoked considerable interest resulting in the manufacture of a variety of derivatives. This invention relates to a derivative of ferrocene l1 H' jQ Which possesses significant and singular properties in a 0 v C C specialized field of use. X It has been found that ferrocene has significant vola- G I C tility and because of this it has found favor as a burning C :OCHzOHzOOHzCHaCH: rate accelerator of solid propellant rocket fuels. However, i I the total dispersibility of ferrocene in the propellant matrix is typically less than desirable. Modifications of ferrocene H5 H4 by afiixing substituent groups on a cyclopentadienyl radical thereof, e.g., acyloxy, keto and simple mono-ether, achieve only moderate improvements in the oompounds H -H- dispersibility in the propellant matrix. c g 0 C This invention relates to ferrocene derivatives which possess substantially improved dispersibility in a solid pro- 0 pellant matrix and are excellent burning-rate accelerators. gmogmcmoomcmcmcm The ferrocene derivatives of this invention are characterized as a methylcycyopentadienyl cyclopentadienyl iron compound having an aliphatic polyether radical bonded H4 H5 by an oxygen to carbon bond to the methyl group. The aliphatic polyether radical may be termed an alkoxy- GT alkoxy or cycloalkoxyalkoxy group and an alkoxypoly- I Be alkyleneoxy or cycloalkoxypolyalkyleneoxy group at- C tached to the methyl group. These compounds may be characterized by the formula: 0 C

CHzOCHzCHz O CHzCHCHzCHgCHz OH: (I) H4 H5 49 OHrCHa.

C- }O 0---0 v i t n (i o o o 0 1 OG X H -FG-H ,-H-H,

O O CH1[O omcHmcmmoRl R C C 50 omoonzomcmoomon zcmom wherein at least one of the Rs is hydrogen and not more than one of the Rs is an alkyl group, typically of from 1 to 18 carbon atoms, and preferably of from 1 to 8 car- H4 H, bon atoms; R is an alkyl group of from 1 to 18 carbon atoms and preferably from 1 to 12 carbon atoms, or a H cycloalkyl group of from 4 to 8 carbon atoms preferably of from 5 to 8 carbon atoms; n is an integer of from 0 to C 0 C aobut 2; and m is an integer of from about 1 to 6. Specific illustrations of aliphatic polyetheric substituted ferrocene encompassed within the above formula, include, 9310 01110320320310 CHZCHB as examples, l 7

a H5 H4 H6 (l u at n C Q X 0 0 0 0 0 o X c ioomcno omomomom CHzOCHzCHzOCH:

044; 04-0 :1 'l l' l C C C CH2OCHCH2OCH2CH3 H4 H5 C C (1+0 1" it ir ll C C C C C C CH QCEHCHOCHQ CH (5H2 l l l l C4) CHzCHzO CHzCHgO CH3 H4 C44 ii ii CHQO CH CH O CHzCHaO CHzCHzCHzCHa I Ha C l c C l C o o '0 ,ocH'zoHocHmHocmcHa' Y CH3 cm 1 1 044 C-i-C ll li it ll 0 c o c C :0 CHzCHaO CHzCHzO CHzCHaO CHgCHgO CHaCHa 1 CHQO CHzCHzO CHzCHqCHaCHnC CHzC CHzHgCHgCHzCHz CHzO CH2CHO CHzCHzCHzCHzCHgCHzCHzCHzCHnCHG CHzCHzCHzCHzCHzCHzCHzCHs H, H: Hg

0 0 o-o-o omocmomoomomoo CH1 and the like. Many other specific compounds encompassed by Formula I are readily apparent and are included as part of this invention.

The above ferrocenyl compounds are advantageously obtained by the reaction of an alkali metal (e. g., Na, K, or Li) alcoholate of an ether alcohol, such as those of the formula mo omoHmcmmo R1 wherein R, R m and n are as described previously, with the methiodide or ethobromide of (dimethylarninomethyl)ferrocene, i.e.,

The iodine and bromide are described by Nesmeyanov et al., Iz-vestiya Akademii Nauk SSSR, Otdelenie Khimicheskikh Nauk No. 3, pages 554-555 (March 1960).

Specific aliphatic ether alcohols encompassed by Formula II include, e.g., the mono-methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, 2-ethylhcxyl, n-octyl, n-nonyl, n-undecyl, n-octadecyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, etc., ethers of ethylene glycol, di-, tri-, tetra-, penta-, heXa-ethylene glycol, 1,2- and 1,3propylene glycol, 1,2-, 1,3- and 1,4-butylene glycol, di, t1'i-, tetra-, penta-, hexa-1,2-, 1,3-, and 1,4-butylene glycol,

1,2-, 1,3-, 1,4-penty1ene glycol, 1,2-, 1,3-, 1,4-hexylene glycol 1,2-dodecylene glycol, 1,2-octadecylene glycol, 1,4- docosylene glycol, and the like.

The reaction may be elfected by simple admixture of the reactants at a temperature sufiicient to evolve amine from the reaction mixture. Typically the temperature of reaction is above 25 C., usually at least 50 C., up to 200 C. Preferably, the reaction temperature is between about 70 C. and 125 C. The alkali metal alcoholate of the ether alcohol is typically provided in at least a stoichiometric amount, i.e., at least one mole of the alcoholate per mole of the methiodide or ethobromide of (dimethylaminomethyl)ferrocene. In some instances, it may be desirable to employ an amount of alcohol, as alcoholate, up to twice the stoichiometric requirements.

The desired ferrocenyl product may be separated by dissolution of the reaction product mixture in an inert solvent, such as benzene, followed by Water and/or dilute acid washing. Upon drying, the desired product may be obtained by conventional distillation.

The following examples are supplied in order to more specifically explain the invention and are not intended to be construed as limitations on this invention.

Example I A solution of 4.5 grams of sodium in 250 milliliters of monobutyl ether of diethylene glycol is placed in a reaction flask equipped with a stirrer thermometer and reflux condenser. 72 grams of methiodide of (dimethylaminomethyDferrocene (also called ferrocenylmethyltrimethylammonium iodide) is added to the flask and the resulting mixture is heated. At 100 C. trimethylamine is noted to be evolved. The temperature of the mixture is held at 100 to 110 C. for two hours. During this time the ferrocene salt is dissolved to give a deep red solution. The solution is cooled, diluted with 300 milliliters of benzene, and washed once with Water, once with dilute hydrochloric acid and twice with water. After drying over anhydrous potassium carbonate, the product is distilled. There is obtained 47 grams of the butyl ether of ferrocenylmethyloxyethyloxyethanol distilling 01f at 120 C. at 5 microns pressure.

Example II Operating according to the procedure cited in Example I, the methiodide of (dimethylaminomethyl)ferrocene is reacted with the anhydrous sodium salt of the monoethyl ether of diethylene glycol to provide good yields of the ethyl ether of ferrocenylrnethyloxyethyloxyethanol.

Example 111 Operating according to the procedure cited in Example I, the methiodide of (dimethylaminomethyl)ferrocene is reacted with the anhydrous sodium salt of the monoethyl ether of ethylene glycol to provide good yields of the ethyl ether of ferrocenylmethyloxyethanol.

Though the above relates to a plurality of specific details, such are not intended to be considered as limitations on this invention unless they appear in the claims.

I claim:

1. Methylcyclopentadienyl cyclopentadienyl iron compound having a radical bonded to the methyl group from the class consisting of alkoxyalkoxy, cycloalkoxyalkoxy, alkoxypolyalkyleneoxy and cycloalkoxypolyalkyleneoxy.

2. A ferrocene compound having the formula:

wherein at least one of the Rs is hydrogen and not more than one of the Rs is an alkyl group; R is a member from the groups consisting of alkyl and cycloalkyl; n is an integer of from 0 to about 2; and m is an integer of from about 1 to 6.

3. The monobutyl ether of ferrocenylmethyloxyethyloxyethanol.

4. The monoethyl ether of ferrocenylmethyloxyethyloxyethanol.

5. The monoethyl ether of ferrocenylmethyloxyethanol.

6. A process for making methylcyclopentadienyl cyclopentadienyl iron compound having an acyclic aliphatic polyether radical from the class consisting of alkoxyalkoxy, cycloalkoxyalkoxy, alkoxypolyalkyleneoxy and cycloalkoxypolyalkyleneoxy, bonded by an oxygen to carbon bond to the methyl group which comprises reacting an alkali metal alcoholate of an ether alcohol corresponding to said aliphatic polyether radical with a compound from the class consisting of the methiodide and ethobromide of (dimethylarninomethyl)ferrocene.

vol. 22, No. 4, May

UNITED STATES PATENT ()FEICE CERTIFICATE OF CORRECTION Patent No 3 ,322 ,804 May 30 1967 Roy L. Pruett It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3, lines 67 to 75, the formula should appear as shown below instead of as in the patent:

C C C C H OCH CH OCH CH OCH CH CH CH CH CH CH CH3 Signed and sealed this 9th day of January 1968 Attest:

Edward M. Fletcher, J1. EDWARD J. BRENNER Attesting Officer Commissioner of Patents

Claims (1)

1. METHYLCYCLOPENTADIENYL CYCLOPENTADIENYL IRON COMPOUND HAVING A RADICAL BONDED TO THE METHYL GROUP FROM THE CLASS CONSISTING OF ALKOXYALKOXY, CYCLOALKOXYALKOXY, ALKOXYPOLYALKYLENEOXY AND CYCLOALKOXYPOLYALKYLENEOXY.