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United States Patent (19) (11) 3,886,211 Keenan (45) May 27, 1975

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United States Patent (19) (11) 3,886,211 Keenan (45) May 27, 1975 United States Patent (19) (11) 3,886,211 Keenan (45) May 27, 1975 54). CARBOXYLIC ACID HYDRAZIDE 57) ABSTRACT DERVATIVES Hydrazides containing, as a characterising feature, the 75) Inventor: John Francis Edmund Keenan, grouping having the formula: Cheadle Hulme, England (73) Assignee: Ciba-Geigy Corporation, Ardsley, R - CO.NH.N - C N.Y. (22 Filed: Mar. 5, 1970 (21) Appl. No.: 16,971 wherein R is alkyl, aryl or the group Related U.S. Application Data R 63 Continuation-in-part of Ser. No. 881,282, Dec. 1, t 1969, abandoned. c = N.NH (corn - 30 Foreign Application Priority Data R2 Dec. 10, 1968 United Kingdom............... 58503/68 wherein R is hydrogen or alkyl, R is alkyl or the 52 U.S. Cl..... 260/561 H; 252/5.5 A, 260/347.3; group -CH=N.NHCOR or R and R, together are cy 260/404.5; 260/482 R; 260/500.5; 260/554; cloalkyl or 5-nitrofuryl, R is alkylene, or a vinylene or 26O1558 H phenylene residue and n is 0 or 1; and synthetic lubri (51) Int. Cl........................................... C07 c 103/30 cant compositions comprising hydrazides having the 58 Field of Search...................... 260/404.5, 561 H formula: R 56 References Cited UNITED STATES PATENTS 2,355,911 8/1944 Graenacher ................. 2601404.5 X R2 3,182,039 5/1965 Remy............... ..., 260/561 H X 3441,606 4/1969 Moore et al........................ 260/56 wherein R is amino, alkyl, aryl or one of the group 3,547,646 12/1970 Hori et al........................ 260/56 H ings 3,564.048 2/1971 Fletcher et al...................... 260/.514 FOREIGN PATENTS OR APPLICATIONS R 1 R 1 1,247,320 7/1957 France............................. 260/404.5 1,085,028 6/1954 France............................ 2601561 H D C = N.N- De s N. NHCO - OTHER PUBLICATIONS R 2 R 2 Hiroshi, Chem. Abstracts, 72:4264 lb. Bellasio, Chem. Abstracts, 69: 10392t. CA: 7 :60967 u. R N CA: 70:1 49 6. r 1. c - N.NHCo.R R2 Primary Examiner-Lewis Gotts Assistant Examiner-Ethel G. Love wherein R, R, R and n are as defined above. Attorney, Agent, or Firn-Wenderoth, Lind & Ponack 5 Claims, No Drawings 3,886,211 1. 2 CARBOXYLIC ACID HYDRAZIDE DERIVATIVES If R is an alkylene residue having from 1 to 12 car bon atoms, it is advantageously of straight-chain and This application is a continuation-in-part of applica may be, for instance, methylene, ethylene, n tion Ser. No. 881,282, filed Dec. 1, 1969, now aban propylene, n-butylene, n-amylene, n-hexylene, n doned. heptylene, n-octylene, n-decylene or n-dodecylene. The present invention relates to new chemical com Examples of preferred compounds of formula I in pounds and in particular to new hydrazides and to com clude, therefore, acetic acid cyclohexylidene hydra positions comprising said hydrazides. zide, n-heptanoic acid cyclohexylidenehydrazide, fur According to the present invention, there is provided maric acid di-(cyclohexylidene hydrazide), fumaric a carboxylic acid O acid di-(2-n-butylcyclohexylidene hydrazide), glyoxal R di-(heptanoic hydrazide), malonic acid di (cyclohexylidene hydrazide), succinic acid di 1. (cyclohexylidene hydrazide), adipic acid di R-CO. NH.N = C (cyclopentylidene hydrazide), adipic acid di N 15 (cyclohexylidene hydrazide), sebacic acid di R2 (cyclohexylidene hydrazide), sebacic acid di wherein R is an alkyl group having from 1 to 12 carbon (isopropylidene hydrazide), sebacic acid di atoms or an aryl group which is either unsubstituted or (heptylidene hydrazide) dodecane-l, 2-dioic acid di hydroxysubstituted; or R represents a group having the (cyclohexylidene hydrazide), terephthalic acid di formula:- (cyclohexylidene hydrazide), N:N' di-(cyclohexylidene carbohydrazide), oxalic acid di-(4-n-carbobutoxybut R 1 2-ylidene hydrazide), and adipic acid di-(4-n- N carbobutoxybut-2-ylidene hydrazide), and adipic acid di-(2-octylidene hydrazide). I 25 The present invention also provides a process in R2 which a hydrazide of formula I is produced, which com prises contacting a hydrazide having the formula: wherein R is hydrogen or an alkyl group having from 1 to 12 carbon atoms which may be substituted by a R.CO.NH.NH carboxylic acid ester group, R is an alkyl group having 30 from 1 to 12 carbon atoms which may be substituted wherein R is as hereinbefore defined, with a compound with a carboxylic acid ester group or represents the having the formula: group -CH = N.NH COR wherein R has its previous significance, or R and Rare linked to form a cycloal 35 kyl residue having 5 or 6 carbon atoms which is unsub stituted or substituted with an alkyl group having from 1 to 6 carbon atoms, or to form a 5-nitrofuryl group, R W is an alkylene residue having from 1 to 12 carbon atoms, a vinylene residue, or a phenylene residue, and 40 n is 0 or . If R is an alkyl group having from 1 to 12 carbon wherein R and R are as defined under formula . atoms, the group may be of straight- or branched The process of the present invention may be conve chain, for instance a methyl, ethyl, n-propyl, n-butyl, niently effected by contacting the carbonyl compound iso-butyl, tertiary-butyl, n-amyl, iso-amyl, n-hepty, n 45 of formula IV, which is normally a liquid, with a stirred octyl, iso-octyl, n-nonyl, n-decyl, n-undecyl or n suspension or solution of the hydrazide compound of dodecyl group, but is preferably of from 1 to 6 carbon formula III, in a solvent inert under the reaction condi atoms and is more preferably methyl or n-hexyl. tions. If a homogenous reaction mixture is obtained in As an alternative, R may be an aryl group optionally the cold, no heating is usually necessary to effect reac hydroxy-substituted, a preferred example of such a 50 tion. However, if a homogeneous reation mixture is not group being an unsubstituted phenyl group. obtained in the cold, it is normally desirable to heat the If R is hydrogen, R is advantageously an alkyl group mixture until all, or substantially all of the undissolved having from 1 to 6 carbon atoms especially a methyl or material has gone into solution. n-hexyl group. The use of a reaction solvent is not essential however If R and Rare each alkyl radicals having from 1 to 55 and, if desired, the reaction may be performed in the 12 carbon atoms, they may be, for example, a methyl, absence of an extraneous solvent, in which case it is ethyl, n-propyl, n-butyl, iso-butyl, tertiaryr-butyl, n normally advantageous to employ an amount of the liq amyl, iso-amyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, n uid compound of formula IV in excess of the stoichio nonyl, n-decyl, n-undecyl or n-dodecyl group, but are metric proportion required in the reaction. In the pre preferably of from 1 to 6 carbon atoms and most pref. 60 ferred instance in which a reaction solvent is used, the erably are each a methyl group. respective proportions of the compounds of formula II The groups R and R* may also be joined together to and IV employed in the reaction are desirably substan form a cyclopentyl or cyclohexyl residue, each prefera tially the stoichiometric proportions required to pro bly unsubstituted but optionally substituted with one or duce the compound of formula I. more alkyl groups having from 1 to 6 carbon atoms, es 65 The reaction is normally advantageously continued pecially an n-butyl group. Alternatively, R and R may until the reaction mixture becomes homogeneous or be linked to form a 5-nitrofuryl residue. substantially homogeneous. In most instances, a reac 3,886,211 3 4 tion period of from 10 minutes to 5 hours is sufficient Synthetic carboxylic acid esters which are suitable as to ensure the completion of the reaction. components of the compositions of the present inven When the reaction period is over, the desired product tion include, di-esters of a dibasic acid and a monohy of formula I is normally precipitated from solution and dric alcohol, for example, dioctyl sebacate or dinonyl may consequently be isolated by filtration. If desired, adipate, tri-esters of trimethylol propane and mono the product of formula I may be purified, for example, basic acids or mixtures of such acids, for instance, tri by recrystallisation from a suitable solvent. methylol propane tripelargonate, trimethylol propane The process of the present invention may be effected tricaprylate or mixtures thereof, tetraesters of penta using the hydrazide of formula III prepared previously erythritol and monobasic acids or mixtures thereof, for or prepared in situ. The hydrazide of formula III for use O example, pentaerythritol tetracaprylate, pentaerythri in the process of the present invention may be conve tol tetraheptanoate or mixtures thereof, acid end niently obtained by reacting an alkyl ester of the car stopped complex esters derived from monobasic acids, boxylic acid having the formula:- dibasic acids and polyhydric alcohols, for instance, a complex ester derived from trimethylol propane, ca R-COH 5 prylic acid and sebacic acid, alcohol end-stopped com W plex esters derived from monohydric alcohols, dibasic wherein R has its previous significance, with hydrozine acids and polyhydric alcohols, for instance, a complex hydrate. ester derived from iso-octanol, sebacic acid and an al There is also provided, according to the present in kylene glycol such as ethylene glycol, or mixtures of vention, a composition comprising a synthetic carbox 20 such esters. ylic ester lubricant and, as a metal corrosion inhibitor, If R is an alkyl group having from 1 to 12 carbon a compound having the formula: atoms the group may be of straight- or branched-chain, for instance a methyl, ethyl, n-propyl.
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