|Publication number||US3171857 A|
|Publication date||Mar 2, 1965|
|Filing date||Sep 25, 1961|
|Priority date||Sep 27, 1960|
|Publication number||US 3171857 A, US 3171857A, US-A-3171857, US3171857 A, US3171857A|
|Inventors||Benzing Erhard P|
|Original Assignee||Monsanto Co|
|Export Citation||BiBTeX, EndNote, RefMan|
|Non-Patent Citations (1), Referenced by (1), Classifications (12)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent 3,171,857 HYDRAZODICARBOXYLIC ACIDDIHYDRAZIDES Erhard P. Benzing, St. Louis, Mo., assignor to Monsanto Company, a corporation of Delaware No Drawing. Filed Sept. 25, 1961, Ser. No. 140,265 Claims priority, application Switzerland, Sept. 27, 1960, 10,918/ 60 5 Claims. (Cl. 260554) It has been found that hydrazodicarboxylic aciddihydrazides which have been unknown until now are obtained by reaction of a hydrazodicarboxylic acid diester with hydrazine or a substituted hydrazine.
The hydrazidation proceeds according to the following equation:
In this formula R has the significance usual in such esters and R, R and R are hydrogen atoms or hydrocarbon radicals.
When substituted hydrazines of the formula HNRINRIIRIII are used as reactants in the process of the invention, the R, R" and R radicals are hydrogen or hydrocarbon radicals, except of course one must be a hydrocarbon radical to fit the definition of substituted hydrazine. Usually it is preferred that R, R and R be hydrocarbon radicals of not more than 18 carbon atoms, more preferably not more than 8 carbon atoms. Illustrative of substituted hydrazines usable in the process of the invention are the following: Methyl hydrazine, t-butyl hydrazine, n-dodecyl hydrazine, cyclohexyl hydrazine, benzyl hydrazine, phenyl hydrazine, p-tolyl hydrazine, [3- naphthyl hydrazine, N,N'-diinethyl hydrazine, N,N-diphenyl hydrazine, N,N,N'-trimethyl hydrazine, N-phenyl- N-methyl hydrazine, etc.
The hydrazodicarboxylic acid esters serving as starting material can be prepared in known manner from hydrazine and chloroformic acid esters. In principle, all esters available can be used in this reaction. However, the hydrazidation does not occur equally easily with all esters, as is shown in the following table:
But, these yields which for comparison purposes were obtained with hydrazine by using the working method described in Example 1 do not represent the maximum that can be obtained. Esters wherein R is an araliphatic or cycloaliphatic radical, e.g. the benzyl radical or the cyclohexyl radical, can also be used. Usually it is preferred that R contain not more than 18 carbon atoms, and more preferably not more than 8 carbon atoms. In general, the methyl ester owing to its price and technical availability is preferred in carrying out the invention.
The reaction of an optional hydrazodicarboxylic acid diester is best eilected by heating a mixture of hydrazine and ester for some time at higher temperature. Using hydrazine or aliphatically substituted hydrazines, the reaction is complete at about 100 C. in most cases after 3040 minutes. However, the hydrazidation also occurs at room temperature when the reaction mixture is left standing for a prolonged time. The less basic aromatical- 1y substituted hydrazines need more prolonged reaction time and possibly a higher reaction temperature. The
3,171,857 Patented Mar. 2, 1965 process of invention can be carried out with or without a solvent. The lower aliphatic alcohols are especially suitable as solvents. A lower aliphatic alcohol is one having from 1 to 6 carbon atoms. In general, the same or similar working methods are applicable as with the amidation of carboxylic acids by using esters thereof.
To supplement the compound of the invention of the examples the following compounds are named as illustrative of compounds of the invention: hydrazodicarboxylic acid bis-(trimethyl-hydrazide), hydrazodicarboxylic acid bis-(tribenzylhydrazide), hydrazodicarboxylic acid bis (tricyclohexylhydrazide), hydrazodicarboxylic acid bis-(tri-n-dodecylhydrazide), hydrazodicarboxylic acid bis-(N-phenyl-N-methyl-N-ethyl-hydrazide), etc.
The hydrazodicarboxylic acid-dihydrazides of the invention are useful as reducing agents. They also have similar uses to hydrazine. Unlike hydrazine the compounds of the invention are solid and more stable. They are useful as solid rocket propellants, since on oxidation large volumes of nitrogen as well as water are formed.
Hydrazodicarboxylic acid-dihydrazides are valuable intermediates. The compound obtained with hydrazine reacts with ketones and aldehydes in the same way as semicarbazide, thereby two molecules of the carbonyl compound can be condensed with one molecule of hydrazodicarboxylic acid-dihydrazide. Derivatives of acetone, ben zaldehyde, isobutyraldehyde, etc., are formed very easily and practically quantitatively on mixing the reactants in warm water. The novel compounds, as long as they contain a replaceable hydrogen atom, can be reacted with carboxylic acid chlorides or anhydrides in the normal manner, thus obtaining, the corresponding mono, di or even polyacylderivative. With for example two equivalents of benzenesulfonyl chloride, one obtains the symmetrical dibenzenesulfonylderivative.
Example 1 7.5 g. of hydrazodicarboxylic acid-dimethylester (0.05 mole) and 10 g. of hydrazine hydrate (0.2 mole) are heated at C. for /2 hour. Crystals separate on cooling and standing for some time. These are filtered off, washed with water and methyl alcohol and dried. Recrystallization from hot water gives pure hydrazodicarboxylic acid-dihydrazide.
Yield 70%; MP. 203205 C.
Analysis.C H N O I Percent C calcd., 16.22; found, 16.34 Percent H calcd., 5.44; found, 5.41 Percent N calcd., 56.74; found, 56.72
Example 2 60.8 g. of hydrazine hydrate (1.2 moles) are dissolved in m1. of ethyl alcohol. 81.6 g. of hydrazodicarboxylic acid-diphenylester (0.3 mole) are slowly added with stirring. The reaction mixture is subsequently refluxed for /2 hour, then cooled and the precipitated crystals filtered 01f.
Yield 40.4 g. (=91% of the theory); M.P. 203-2o5 c.
Hydrazodicarboxylic acid-dihydrazide is insoluble in most common solvents but soluble in hot water. The aqueous solution is weakly alkaline (pH 7-8). Two baseequivalents can be titrated with perchloric acid in acetic acid solution. The aqueous solution displays strong reducing properties.
Example 3 To a 10% solution of hydrazide in warm water a corresponding amount of acetone is added. Crystallization begins at once. The reaction mixture is kept at 50 C. for 15 minutes, then cooled and filtered.
Yield 95%. Recrystallization from acetonitrile, M.P. 234-235 C.
3 Analysis.C H N O (228.3)
Percent C calcd., 42.09; found, 42.16 Percent H calcd., 7.07; found, 7.31 Percent N ca1cd., 36.82; found, 36.97
Example 4 Isobutyraldehyde is used instead of acetone and one then proceeds as in Example 3.
Yield (crude) 100%. Recrystallization from DMF/ water, M.P. 199200 C.
AlZalySl S.'C10H20N 02 Percent C calcd., 46.82; found, 46.91
Percent H calcd., 7.87; found, 7.98 Percent N calcd., 32.79; found, 32.61
Example 5 Benzaldehyde is used instead of acetone and one then proceeds as in Example 3.
Yield 52.4% from pyridine/water. from DMF, M.P. 234-235 C.
Analysis.C H N O (324.3)
Percent N calcd., 25.91; found, 25.23.
Example 6 0.88 g. of sodium hydroxide (0.022 mole) and 1.48 g. of hydrazodicarboxylic acid-dihydrazide (0.01 mole) are successively dissolved in 10 ml. of water. Then, 2.56 g. of benzenesulfonylchloride (0.02 mole) are added and the mixture is shaken vigorously. The reaction is started by immersing the flask briefly in hot water; it then proceeds exothermally. After minutes shaking it is left standing for 3 hours. The crystals are filtered off and washed with water. Recrystallization from 50% ethyl alcohol.
Yield 0.65 g. (:15% of the theory); MP. 234236 C.
Analysis.C H N O S (428.5):
Percent C calcd., 39.25; found, 39.14 Percent H calcd., 3.76; found, 3.98 Percent N calcd., 19.62; found, 19.41 Percent S calcd., 14.97; found, 14.88
This compound of the invention has the structure @somrmno ONHNHC ONHNHS o@ and it kills nematodes at concentrations as low as 10 p.p.m. If, in Example 6, instead of benzenesulfonylchloride, an equimolar amount of p-toluene-sulfonylchloride, 2,4-
Recrystallization SO2NHNHO ONHNHC ONHNHSO )n )n wherein Y is a halogen atom, preferably chlorine, or a methyl group, and n is an integer from 010 5 inclusive. Y, if there is more than one Y on a phenyl radical, can be a mixture of halogens and methyl groups.
What is claimed is: 1. A compound of the formula SOzNHNHC ONHNHC ONHNHSO )n (Y)n wherein Y is selected from the class consisting of halogen atoms and the methyl radical, and n is an integer from 0 to 5, inclusive.
@sozmmno ONHNHC ONHNHS o 3. A compound of the formula R (R' C=NNHCONHNHCONHN=C (R' R wherein R is alkyl having not more than 8 carbon atoms and R is selected from the class consisting of hydrogen atoms and the methyl radical.
4. (CH C=NNHCONHNHCONHN=C(CH (CH CHCH=NNHCONHNHCONHN =CHCH(CH References Cited in the file of this patent Stolle: Chem. Berichte, volume 43 (1910), pages 2468-70.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 ,l7l, 857 March 2, 1965 Erhard P: Benzing It is hereby certified that error appears in the above numbered paten't reqiiring correction and that the sa id Letters Patent should read as corrected, below Column 4, line 33, beginning with "3 a A compound of" strike out all to and including "=CHCH(CH in line 43, same column 4; in the heading to the printed specification, line 8, for "5 Claims read 2 Claims H i Signed and sealed this 24th day of August 19 650 (SEAL) Attest:
-ERNEST W. SWIDER EDWARD J. BRENNER -All.0sting Officer Commissioner of Patents UNITED STATES PATENT OFFICE I CERTIFICATE F fifl REQTEQN Patent No. 5,171,857
March 2, 1965 Erhard Pa Benzin It is hereby certified that error appears the above numbered patent reqiiring correction and that the sa id Letters Patent should read as oorrectedbelow.
line 33, beginning with "5.; strike out all to and including "=CHCH(CH column 4; in the headin for "5 Claims." read A compound of" J in line 43, same g to the printed specification, ,line- 8,
Z Claimsc Signed and sealed this 24th day of August 1965- e (SEAL) Attest:
ERNEST W. SWIDER Ailcsting Officer EDWARD J. BRENNER Commissioner of Patents
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US4358611 *||Jan 9, 1978||Nov 9, 1982||Shell Oil Company||Preparation of 2-phenylsemicarbazides|
|U.S. Classification||564/35, 252/188.1, 149/36, 252/188.26|
|International Classification||C06B47/08, A01N47/28, A01N47/34, C06B47/00|
|Cooperative Classification||A01N47/34, C06B47/08|
|European Classification||A01N47/34, C06B47/08|