JPH072756A - Cyclopentadience derivative - Google Patents

Abstract

PURPOSE: To obtain a cyclopentadiene derivatives effective as a dispersing agent of lubicating oil or fuel.

CONSTITUTION: The compounds of formula I {R¹ and R² are each H or taken together to form C-C single bond; R⁴ to R⁶ are each H, optionally substituted 1-20C alkyl or optionally substituted phenyl; R⁷ is -CH₂-NHR⁸ or -NHR⁸ [R⁸ is substituted alkyl or -COX (X is substituted alkoxy)]; R⁶ and R⁷ are taken together to form CO-NR⁸-CO, CH₂-NR⁸-CO or CH₂-NR⁸-CH₂; α is 1 to 6; R³ is substituted alkyl, substituted alkenyl, formula II, formula III or D-Y [(m) is 0 to 25; (n) is 1 to 20; R⁹ is H, methyl or ethyl; D is a group derived from 20-500C saturated or unsaturated hydrocarbon; Y is formula IV (X' is 0 to 5; R³' is alkyl or alkynyl; R⁷' is R⁷, CHO, COOH or taken together with R⁶ to form a group formed by together R⁶ and R⁷ and CO-O-CO)]}, e.g. compounds of formula V are provided. The compounds of formula I are used as a dispersing agent and most favorably mixed by 0.5 to 5weight% in a lubicant oil composition or by 0.01 to 0.5weight% in a fuel composition.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a cyclopentadiene derivative, a method for producing them, a lubricating composition containing them,
It concerns fuel compositions and additive concentrates, their use as dispersants, and novel intermediates.

[0002]

2. Description of the Related Art U.S. Pat. No. 3,311,634
formula:

[0003]

[Chemical 13]

[Wherein Y is

[0005]

[Chemical 14]

7-Y—N—R ₃ —, which is a group selected from the group consisting of, and the 7-carbon of norbornene (norbornane) is further substituted with hydroxyl.
Disclosed is (R ₄ -5-norbornene) -2,3-dicarboximide and the corresponding norbornane.

Although the group "R ₄ " is not shown in any of the above formulas, in the first column, lines 40-45, R ₃ substituents other than hydrogen are attached to the nitrogen of the imide by a carbon-nitrogen single bond. Attached, and the R ₄ substituent is said to be attached to one or more available carbons on the ring nucleus, if other than hydrogen.

R ₁ and R ₂ can be the same or different, substituted or unsubstituted carbocyclic groups. R ₁ and R ₂ may also be heterocyclic groups containing 4 to 5 carbon atoms with an oxygen, nitrogen or sulfur bond therebetween. R ₂ may also be a saturated or unsaturated, substituted or unsubstituted, aliphatic group containing 1 to 7 carbon atoms.

R ₃ is hydrogen, lower alkyl, carbamoyl or hydroxy lower alkyl group, a heterocyclic group containing 4 to 5 carbon atoms with oxygen, nitrogen or sulfur bonded therebetween, or aralkyl, aralkenyl. , Aryl, substituted arylcarbonyl lower alkyl, amino lower alkyl, or lower alkylamino lower alkyl groups.

R ₄ can be one or more substituents as defined for R ₁ , R ₂ and R ₃ , including hydrogen. R ₄ may also be a lower alkenyl, lower alkynyl, cycloalkyl or cycloalkyl lower alkyl group, optionally substituted with a nitro, amino or hydroxyl group or a hydrogen atom. In the second column, lines 25-28, "the amino and hydroxyl substituents may be attached to a lower hydrocarbon group (represented by R ₄ ) or may be attached directly to the ring. , Ie R ₄ ″. R ₄ is norbornene (norbornane)
It may be oxygen, an epoxy group, attached to the 5th and 6th positions of the nucleus by a single bond, respectively.

In the above patents there are examples where one R ₄ group is present, eg Examples XLVIII and LI, but in each case the R ₄ group is either an epoxy or a hydroxyl group. Further, the only Y groups exemplified include those containing at most a total of 14 carbon atoms, such as the Examples
It is an o-methyldiphenylmethylene group in XXXII.

The compounds of the above formula are 2-R ₃ -3a, 4, which are therapeutically active compounds effective in the treatment of peptic ulcers.
7,7a- tetrahydro -4,7- (Y) R ₄ - isoindoline, corresponding 3a, 4,5,6,7,7a-hexahydro compound, N- oxides and their acid addition salts and quaternary ammonium It is said to be useful as an intermediate in the production of compounds. The above compounds (intermediates) in which R ₁ and / or R ₂ are aromatic and Y is R ₁ , R ₂ -methylene functional group are said to be useful as UV absorbers, while some Compound (intermediate) is CNS
It is said to have suppressive or anti-inflammatory activity.

US Pat. No. 3,320,267 discloses 7-
_{R 1, R 2 -Y-2} -R 3 -3-R 4 - norbornene, discloses corresponding norbornane, and salts thereof.
Y for R ₁ and R ₂ is a saturated or unsaturated aliphatic group containing 2 to 7 carbon atoms, one of which is a norbornene optionally substituted with a hydroxy or epoxy group. / It constitutes the 7th carbon atom of the norbornane nucleus.

R ₁ and R ₂ can be the same or different, substituted or unsubstituted aromatic lower carbocyclic aryl groups. R ₁ and R ₂ may also be substituted or unsubstituted lower alkyl groups or heterocyclic groups containing 4 to 5 carbon atoms with an oxygen, nitrogen or sulfur bond therebetween.

The only Y groups responsible for R ₁ and R ₂ which are exemplified contain at most a total of 16 carbon atoms as in Example XLIV.

R ₃ is hydrogen or carboxamide,
It can be a substituted carboxamide, amino, aminomethyl, substituted aminomethyl, carboxyl, esterified carboxyl, or hydroxymethyl group.

Although there is no definition of R ₄ itself in the above patent specification, R ₄ is a substituted or unsubstituted lower hydrocarbon group (from the _4th to 6th lines of the second column and the 54th and 55th lines). Obviously, it may represent a carboxyl group or an esterified carboxyl group.

From the 63rd line in the first column to the 1st in the second column
By line 8, a compound of the above formula and the corresponding norbornane may be further substituted at any available position in the ring nucleus with R ₁ ,
Substituted by one or more optional substituents defined for R ₂ , R ₃ and R ₄ or a lower alkynyl, cycloalkyl, cycloalkyl lower alkyl, or amino group, formula 7-R ₁ , R _2- Y-2-R ₃ -5- compounds and the corresponding norbornane [R ₅ here represents a substituent further contained in the ring] norbornene -R ₅ -3-R ₄ have been shown to be capable of generating a There is. From Example LIV, R ₅ may represent an oxygen atom bonded to the 5th and 6th positions of the norbornene (norbornane) nucleus by a single bond, respectively, ie R
It seems that ₅ is an epoxy group. There are no other examples where the R ₅ substituent is present.

Compounds of the above formula, especially those where the R ₃ and R ₄ substituents are a carboxamide and a carboxyl group, respectively, are 7-R ₁ , R ₂ -Y-N-R ₃ -5-norbornene-
Said to be useful as intermediates in the preparation of R ₄ -2,3-dicarboximide and the corresponding norbornanes, these compounds are further therapeutically active compounds effective in the treatment of peptic ulcers, 2-R ₃ -3a, 4,7,
7a- tetrahydro _{-4,7- (R 1, R 2 -Y} ) -R 4
-Isoindoline, the corresponding 3a, 4, 5, 6, 7, 7a
Useful as an intermediate in the production of hexahydro compounds, N-oxides and acid addition salts thereof, and quaternary ammonium compounds.

US Pat. No. 3,641,108 has the general formula:

[0021]

[Chemical 15]

[Wherein R is hydrogen or alkyl,
Z is a 1,3-cyclopentylene or 1,3-cyclopent-4-enylene group which has no substituents other than lower alkyl, and has 5 or less, preferably 1 or less substituents, if any. A]] propargyl ester is disclosed. The term lower alkyl means a straight or branched chain alkyl of up to about 4 carbons, such as methyl, ethyl, isopropyl, tert-butyl, etc., with methyl being preferred.

Propargyl ester is a bactericide.
icides and fungicides).

Surprisingly, it has been found that certain cyclopentadiene derivatives have effective dispersibility.

[0025]

According to the present invention, the general formula (I):

[0026]

[Chemical 16]

[In the formula, R ¹ and R ² each represent a hydrogen atom or, together, represent a carbon-carbon single bond; R ⁴ and R ⁵ are each independently a hydrogen atom, or optionally substituted. R ⁶ represents an optionally substituted C ₁ -C ₂₀ alkyl or phenyl group; R ⁶ represents a hydrogen atom, or an optionally substituted C ₁ -C ₂₀ alkyl or phenyl group, and R ⁷ represents a group —CH. _2- NHR ⁸ {wherein R ⁸ represents an optionally substituted alkyl group or a group --COX (wherein X represents an optionally substituted alkoxy group)} or --NHR ⁸ (wherein R ⁸ is the above Is as defined); or, R ⁶ and R ⁷ are taken together to form the group:

[0028]

[Chemical 17]

Wherein R ⁸ is as defined above; x is 1-6, preferably 1-4; each R ³
Are independently optionally substituted alkyl or alkenyl groups or formulas:

[0030]

[Chemical 18]

"In the formula, m is in the range of 0 to 25, n is in the range of 1 to 20, each R ⁹ independently represents a hydrogen atom or a methyl or ethyl group, and D is 20 to 500.
Derived from a saturated hydrocarbon containing 4 carbon atoms, Y is of formula (IV):

[0032]

[Chemical 19]

{Wherein R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ are as defined above; x'is 0 to 5; R ³ '
Is R ³ other than a group of formula (II), (IIIA) or (IIIB)
R ⁷ ′ represents a group R ⁷ or a group —CHO or —COOH as defined above, or R ⁶ and R ⁷ ′ together form a group:

[0034]

[Chemical 20]

(Wherein R ⁸ is as defined above), which represents the group
³ is provided that, at the same time, up to 3 R ³ groups can each contain more than 40 carbon atoms, and that all R ³ groups together contain more than 20 carbon atoms, Containing up to 550 carbon atoms in total]. That is, if one R ³ group contains more than 40 carbon atoms, then no more than 2 other R ³ groups may individually be 4
Contains more than zero carbon atoms.

In the present specification, unless otherwise specified, the alkyl moiety in the alkyl or alkenyl group or the alkoxy or haloalkyl group may be linear or branched.

In the above formula (I), R ¹ and R ² together preferably represent a carbon-carbon single bond.

R ⁴ and R ⁵ each independently represent a hydrogen atom, or an optionally substituted C ₁ -C ₂₀ alkyl or phenyl group. Examples of suitable substituents are halogen atoms and, in the case of phenyl groups, additionally C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy and C _1-
C ₆ haloalkyl group.

Preferably, R ⁴ and R ⁵ are each independently a hydrogen atom, a C ₁ -C ₁₂ alkyl group, or a C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy and C ₁ -C ₃ haloalkyl group. Represents a phenyl group optionally substituted with one or more substituents selected from

More preferably, R ⁴ and R ⁵ are each independently hydrogen atom, C ₁ -C ₆ alkyl, especially methyl group, or one or two selected from methyl and methoxy groups.
Represents a phenyl group optionally substituted with one substituent.

Most preferably, R ⁴ and R ⁵ both represent a hydrogen atom.

R ⁶ may represent a hydrogen atom or a C ₁ -C ₂₀ alkyl or phenyl group, each of which may be optionally substituted. Examples of suitable substituents include R
Those mentioned above for ⁴ and R ⁵ are mentioned.

Preferably, R ⁶ is a hydrogen atom, C ₁ -C ₁₂
Alkyl group, or a C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy and C ₁ -C ₃ 1 or more substituent a phenyl group optionally substituted with a group selected from haloalkyl group.

More preferably, R ⁶ is a hydrogen atom, C _1-
C ₆ alkyl, especially methyl, or represents one or two substituents optionally substituted phenyl group with a group selected from methyl and methoxy groups.

Most preferably R ⁶ represents a hydrogen atom.

R ⁷ is a group —CH ₂ NHR ⁸ [wherein R ⁸ is
May represent an optionally substituted alkyl group or the group --COX, where X represents an optionally substituted alkoxy group, or --NHR ⁸ where R ⁸ is as defined above. .

When X represents an optionally substituted alkoxy group, it is an unsubstituted C _{1 to} C ₂₀ , preferably C ₁₂
To C ₁₅ alkoxy groups, or substituted alkoxy groups such as pentaerythritol-derived moieties or polyalkylene glycol-derived moieties such as the formula R ¹⁰ —O— (C
H ₂ CH ₂ O) _p − [where p is 3 to 9 and R ¹⁰ is C ₉
To C ₁₅ alkyl group] or the formula HO- (CH ₂
CH ₂ O) _q - [wherein q is 4 to 14] may be a group of. Two groups X together are a bridging group, for example a group:

[0048]

[Chemical 21]

Alternatively, the formula --O-(CH ₂ CH ₂ O) _q-
[Wherein q is as defined above].

The groups --NHR ⁸ and --NR ⁸ contain one or more nitrogen atoms, eg 1 to 8 nitrogen atoms and optionally one or more oxygen atoms, eg 1 to 200 oxygen atoms. Derived from primary amines.

For example, primary amines are branched or unbranched saturated aliphatic C ₁ containing one or two nitrogen atoms.
To C ₁₈ , preferably C _{1 to} C ₁₀ amines such as methylamine, ethylamine, propylamine, butylamine,
It can be sec-butylamine, 1,2-diaminoethane, ethanolamine, and 3-dimethylamino-1-propylamine. The primary amine has the general formula (V):

[0052]

[Chemical formula 22]

[In the formula, A is —NH or —O—,
Each R ¹¹ independently represents a hydrogen atom or a methyl group, r is in the range of 1 to 3, and s is 1 when A is —NH.
In the range of ~ 8, and 1 to 200 when A is -O-.
In the range].

Particularly preferred compounds of formula (V) are those in which A is-
NH, r is 1, each R ¹¹ represents a hydrogen atom, and s is in the range of 1 to 5; or A is —O—
And r is 1, each R ¹¹ represents a methyl group, and s is in the range of 4 to 40.

The primary amines may also be of the formula (VI):

[0056]

[Chemical formula 23]

[In the formula, R ¹² represents a hydrogen atom or an ethyl group, but when R ¹² represents a hydrogen atom, t, u and v
Is in the range of 1 to 100, and when R ¹² represents an ethyl group, each of t, u and v is in the range of 1 to 10].

The two radicals R ⁸ together are a bridging group, for example of the formula (V '):

[0059]

[Chemical formula 24]

A group of the formula (A, R ¹¹ , r and s are as defined above), or a group of formula (VI ′):

[0061]

[Chemical 25]

[Wherein R ¹² , t, u and v are as defined above] and three groups R ^{8 taken} together are of formula (VI ″):

[0063]

[Chemical formula 26]

[Wherein R ¹² , t, u and v are as defined above].

R ⁶ and R ⁷ together form a group:

[0066]

[Chemical 27]

Of these, the first group of these is particularly preferred.

In formula (I), each of R ⁴ , R ⁵ and R ⁶ represents a hydrogen atom, R ⁷ represents a group —CH ₂ NHR ⁸ or each of R ⁴ and R ⁵ represents a hydrogen atom. Represent, R
⁶ and R ^{7 taken} together form a group:

[0069]

[Chemical 28]

It is preferred to represent wherein R ⁸ is as defined above.

Each radical R ³ can contain a total of up to 550, preferably up to 400, more preferably up to 300, in particular up to 250 carbon atoms, provided that at the same time up to 3 R 3 are present. Each of the ^three groups can contain more than 40 carbon atoms and the total number of groups R ³ is 20
More than 3 carbon atoms are included, for example up to 300, preferably up to 150 carbon atoms.

R ³ is, for example, C _{1 to} C ₄₀ , preferably C ₁
To C ₃₆ , more preferably C _{1 to} C ₂₀ , especially C _{7 to} C ₁₈ alkyl group, or (number average molecular weight (M _n ) 280 to 70).
(Corresponding to 00) 20 to 500, preferably 50 to 4
00 pieces (M _n 700~5600), in particular carbon atoms of 50 to 200 _{(M n 700~2800), C 2} ~C 6
A polyalkenyl group derived from an olefin monomer,
Preferably it can be a polyisobutenyl group, any given R ³ groups, one or more, preferably optionally substituted with one or two substituents.

Examples of suitable substituents are halogen atoms (eg chlorine atom), nitro, hydroxyl, cycloalkyl, alkoxy, haloalkoxy, amino, alkylamino, dialkylamino, formyl, alkoxycarbonyl, carboxyl, alkanoyl, alkylthio. , Alkylsulfinyl, alkylsulfonyl, carbamoyl, alkylamide, aryl, alkaryl,
Heterocycles and polyoxyalkylene groups are included. If any of the aforementioned substituents contain an alkyl or alkylene moiety, it may be straight-chain or branched and contain up to 12, preferably up to 6, especially up to 4 carbon atoms. 3 to 8 cycloalkyl groups, preferably 3
It may contain up to 6 carbon atoms. The aryl group may be any aromatic group, especially a phenyl or naphthyl group. An alkaryl group is an aryl group substituted with one or more, preferably one or two alkyl groups. The heterocyclic group is
A saturated or unsaturated ring system containing at least one heteroatom selected from oxygen, nitrogen and sulfur, such as C _5-
It may be a C ₇ ring system, but 5 and 6 membered rings are particularly preferred,
Examples include the tetrahydrofuranyl, furanyl, piperidinyl, pyridinyl, tetrahydrothiophenyl or thiophenyl (thienyl) groups.

R ³ is represented by the above formulas (II) and (III
It may be a group of A) or (IIIB), but is preferably a group of formula (II) or (IIIB). In the formula (IIIB), D is preferably 20 to 400, more preferably 3
5 to 300, most preferably from 50 to 200 carbon atoms, C ₂ -C ₆ unsaturated hydrocarbon which is a polyalkene is prepared from olefin monomers, are derived from, for example polyisobutene.

X'in the above formula (IV) is preferably 0, 1
Or 2, and more preferably 0 or 1.

In formula (IV), R ⁶ and R ⁷ 'are taken together to form the group:

[0077]

[Chemical 29]

Preferably, R ⁸ is as defined above.

Particularly preferred compounds of formula (I) are those in which x is 1
Wherein R ₃ is a C ₅₀ -C ₂₀₀ polyalkenyl group or a group of formula (IIIB), wherein D is derived from an unsaturated hydrocarbon and x ′ in formula (IV) is 0. X is 2, one R ³ represents a C ₅₀ -C ₂₀₀ polyalkenyl group, and the other R ³ represents a group of formula (II) (where x ′ in formula (IV)). Is 1 and R ³ 'represents a C ₅₀ -C ₂₀₀ polyalkenyl group); or x is 3
4 and each R ³ independently represents a C ₇ -C ₁₈ alkyl group.

It is understood that the compounds of formula (I) may exist in different geometric isomers. The invention therefore includes both the individual isomers and mixtures of such isomers.

The present invention further provides a process for the preparation of a compound of formula (I) as defined above, which comprises the general formula (VII):

[0082]

[Chemical 30]

[Wherein, x, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are as defined above, provided that the group R ³ is of the formula (I
I), (IIIA) or (IIIB) is represented by the formula (I
R ⁷ ′ in V) represents a group —CHO or —COOH, or R ⁶ and R ⁷ ′ together form a group:

[0084]

[Chemical 31]

R ⁷ ″ is a group —CHO or —C
Represents OOH, or R ⁶ and R ⁷ ″ together represent the group:

[0086]

[Chemical 32]

A compound of the formula (VIII): BH (VIII) [wherein, when R ⁷ ″ represents a —COOH group, B represents a group X as described above, and R ⁷ taken together "is or R ⁶ and R ⁷ represents a -CHO group" group:

[0088]

[Chemical 33]

When B is represented, B is a group --NH as described above.
Representing R ⁸ ] and, if necessary or desired, the product thus obtained is selectively hydrogenated to give a carbonyl (C═O) or imine (C
= N) provides a method of reducing unsaturation.

The compounds of formulas (VII) and (VIII) are conveniently reacted under reflux conditions in the presence of a solvent.
Suitable solvents include aromatic hydrocarbon solvents such as toluene and xylene, and chlorohydrocarbons such as dichloromethane.

If desired, the compound of formula (VII) and the compound of formula (V
The reaction product of the compound of III) is prepared in a conventional manner, for example in J
error March by Advanced Or
ganic Chemistry, Reaction
s, Mechanismsand Structr
e, 3rd edition, published by Wiley-Interscience, pp 1093-1100.

The compound of formula (VIII) is a known compound, and can also be produced by a method similar to a known method.

For example, B is a group X (where X is C ₁₂ -C ₁₅
An alkoxy group) or formula R ¹⁰ -O- (CH ₂ C
H ₂ O) _p - (compound of formula (VIII) is wherein p and R ¹⁰ are as defined above) is, the Royal
It is commercially available under the trademark "DOBANOL" from an affiliated company of the Dutch / Shell Group.

A compound of formula (VIII) in which B is a group --NHR ⁸ , eg 3-dimethylamino-1-propylamine, and A is --NH, eg diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine. Certain compounds of formula (V) above have t
he Aldrich Chemical Compa
ny Ltd. , (UK); A
The compound of the formula (V) and the compound of the formula (VI) in which is oxygen is a compound of the Texaco Chemical
Company, Bellaire, Texas, U.S.A.
S. A. Is commercially available from.

The compound of formula (VII) is a novel intermediate. Accordingly, the invention further provides a compound of formula (VII) above.

The compound of formula (VII) is conveniently represented by the general formula (IX):

[0097]

[Chemical 34]

[Wherein, x is as defined above, and each R is
³ ″ is independently an optionally substituted alkyl or alkenyl group as defined for R ³ , or a formula:

[0099]

[Chemical 35]

{Where m, n, R ⁹ and D are as defined above, and Y'is of formula (X):

[0101]

[Chemical 36]

(Wherein x ′ and R ³ ′ are as defined above)}, and each group R ³ ″
At the same time up to 3 radicals R ³ ″ can each contain more than 40 carbon atoms and all radicals R ³ ″
Containing a total of up to 550 carbon atoms, with the proviso that it contains more than 20 carbon atoms in total], a compound of the general formula (XI):

[0103]

[Chemical 37]

Reacting with a compound of the formula: wherein R ⁴ , R ⁵ , R ⁶ and R ⁷ ″ are as defined above, and if desired,
The product thus obtained is used, for example, in Jerry Ma
rch by Advanced Organic C
chemistry, Reactions, Mecha
nims and Structre, 3rd edition, Wi
ley-Interscience Publishing, pp 745
It can be prepared by a method comprising hydrogenating and reducing carbon-carbon double bond (C = C) unsaturation as described at 750.

The selective hydrogenation reaction to reduce the C = C unsaturation is conveniently carried out by known methods, such as using palladium on charcoal catalyst.

The compounds of formulas (IX) and (XI) are known compounds and can be prepared by methods similar to known methods.

That is, the compound of formula (IX) is conveniently cyclopentadiene or dicyclopentadiene as described in US Pat. Nos. 4,721,823 and 5,012,023.
As stated in the issue,

[0108]

[Chemical 38]

[Wherein m, n, R ³ ′, R ⁹ and D are as defined above, and L represents a leaving group such as a halogen atom or a hydroxyl group] and at least one selected from the group consisting of It can be produced by reacting with the compound of.

When a compound of formula (IX) is prepared using a reactant containing two leaving groups L, it is possible to form complex structures containing three or more cyclopentadiene rings linked together. Such a structure is expected to react with a compound of formula (XI) as well as a compound of formula (IX) and the product thus obtained likewise has the same formula as the compound of formula (VII). It is expected to react with compounds of formula (VIII) to form analogs of compounds of formula (I). In fact, it was observed that a small amount of very high molecular weight material was formed (as revealed by gel permeation chromatography analysis). It is presumed that such a high molecular weight substance exhibits the same excellent dispersibility as the compound of the formula (I).

Particularly preferred compounds of formula (XI) are maleic anhydride and acrolein.

The compounds of formula (I) above can be used as dispersants in lubricating oils. Therefore, the present invention further provides a major quantity (5
0% by weight or more) and a small amount, i.e. preferably 0.1 to 10% by weight, especially 0.5 to 5% by weight of the total composition
There is provided a lubricating oil composition comprising, by weight, a compound of formula (I) above.

Suitable lubricating oils are natural, mineral or synthetic lubricating oils.

Natural lubricating oils include animal and vegetable oils, such as castor oil. Mineral oils are derived from crude oils, coals or shale oils and consist of clay-acids, solvents or lubricating oil fractions which have undergone certain treatments such as hydrotreatment. Synthetic lubricating oils include synthetic polymers of hydrocarbons, modified alkylene oxide polymers, and ester lubricating oils, which are known in the art. These lubricating oils are preferably crankcase lubricating oils for spark ignition and compression ignition engines, although
Also included are ulic lubricants), metalworking fluids and automatic transmission fluids.

The lubricant base oil component of the composition of the present invention is, for example, the Royal Dutch / Shell Gro.
Trade name "HVI" or "XH" by up affiliates
It is preferably a mineral oil-based lubricating oil or a mixture of mineral oil-based lubricating oils such as those sold under the trade name VI "™.

The viscosity of the lubricating base oil present in the compositions of this invention can vary over a wide range, but generally ranges from 3 to 35 at 100 ° C.
mm ² / s.

The lubricating oil composition of the present invention comprises various other additives known in the art such as viscosity index improvers (eg linear or star polymers of dienes such as isoprene or butadiene or such dienes). And optionally substituted styrene). Suitably such a copolymer is a block copolymer,
It is preferably hydrogenated to the extent that it will saturate most of the olefinic unsaturation. Other suitable additives include those based on block copolymers or dispersible V.I. I. Improvers, extreme pressure / antiwear additives such as zinc or sodium dithiophosphate,
Ashless dispersants, such as polyolefin-substituted succinimides (such as those described in GB 2 231 873), antioxidants, friction modifiers, or metal-containing detergents such as phenates, sulfonates, alkyl salicylates or naphthenates ( All detergents may be overbased).

The compounds of formula (I) above can also be used as dispersants in fuels. Therefore, the present invention further provides a major quantity (5
0% by weight or more) and a small amount, that is, preferably 0.01 to 2% by weight, particularly 0.01 to 2% by weight, based on the total composition
There is also provided a fuel composition comprising 0.5% by weight of a compound of formula (I) above.

Suitable fuels include hydrocarbon-based fuels that substantially boil within the gasoline boiling range of 30-230 ° C. Such base fuel may include a mixture of saturated olefinic hydrocarbons and aromatic hydrocarbons. They may be derived from straight run gasoline, synthetic aromatic hydrocarbon mixtures, pyrolysis or catalytic cracked hydrocarbon feedstocks, hydrocracked petroleum cuts, or catalytic reformed hydrocarbons.

The fuel composition of the present invention comprises various other additives known in the art such as lead compounds as antiknock agents; phenolic materials (eg 2,6-di-t).
ert-butylphenol) or phenylenediamine (eg N, N'-di-sec-butyl-p-phenylenediamine);antioxidants;dyes; metal deactivators; polyester-based ethoxylated alkylphenol formaldehyde resins, such as defoamers. (Dehazer);
For example, a polyhydric alcohol ester of a succinic acid derivative having an unsubstituted or substituted aliphatic hydrocarbon group having 20 to 500 carbon atoms on at least one α carbon atom (for example, the polyisobutylene group has a number average molecular weight of 950). Corrosion inhibitors such as polyisobutylene-substituted succinic acid pentaerythritol diesters); anti-knock agents other than lead compounds such as methylcyclopentadienyl-manganese tricarbonyl or ortho-azidophenol; anti-knock aids such as benzoylacetone; Polyether (eg C ₁₂ -C ₁₅ alkyl substituted propylene glycol (the Royal Dutch / She
"SA sold by an affiliated company of ll group
P 949 "))," HVI "or" XHVI "base oil, or, C ₂ -C ₆ derived from monomers polyolefins (e.g. 20-175, polyisobutylene) in such carriers, especially carbon atoms 35 to 150 It may contain a liquid.

The lubricating oil composition and fuel composition of the present invention are
It may be prepared by individually adding one or more compounds of formula (I) above to a lubricating oil or fuel. Conveniently, the additive concentrate is mixed with a lubricating oil or fuel. Such concentrates generally consist of an inert carrier liquid and one or more additives in concentrated form. The present invention therefore also provides an additive concentrate comprising an inert carrier liquid and 10 to 80% by weight, based on the total concentrate, of a compound of formula (I) above.

Suitable inert carrier liquids are hydrocarbons and
Mixtures of carbohydrates with alcohols or ethers such as methanol, ethanol, propanol, 2-butoxyethanol or methyl tert-butyl ether. For example, the carrier liquid may be an aromatic hydrocarbon solvent such as toluene, xylene, a mixture thereof, or a mixture of toluene or xylene and an alcohol. Alternatively, the carrier liquid may be the Royal Dutch / Shel
l "HVI" or "XH" from an affiliate of Group
Mineral oil base oils such as those sold as VI "™,
For example, "HVI 60" base oil may be used.

The invention further provides the use of the compounds of formula (I) above as dispersants.

The invention will be further understood by the following examples.

[0125]

EXAMPLES Example 1 (i) Preparation of multiple alkylated cyclopentadiene
Call method) (the Royal Dutch / Shell Gr)
C ₉ -C ₁₁ alcohols average relative molecular weight as measured by the associated companies are sold under the trademark "Dobanol 91" from) the gas phase chromatography oup is 160 ± 3 (424g, 2.65mol mixture deoxygenated) And powdered potassium hydroxide (87%) in a reaction vessel equipped with a dean and stark trap.
(10.3 g, 0.16 mol) and dicyclopentadiene (6.6 g, 0.05 mol) and heated to 180 ° C. As soon as water began to accumulate in the Dean and Stark trap, the reaction mixture was charged with additional dicyclopentadiene (28.4 g, 0.215 mol).
I added it little by little over time. The temperature of the reaction mixture is about 24
Gradually increased to 0 ° C and maintained at this temperature until no more water was produced. Once cooled, the reaction mixture was diluted with hexane (500 ml), washed until the pH was neutral (8 x 500 ml), then dried over magnesium sulfate. Then, hexane was removed under reduced pressure to obtain a crude product (430 g). Thin film forming evaporator (wipe)
The crude product was purified using a d film evaporator) to remove unreacted alcohol and yield 241
This gives g of the desired product, a multiply alkylated cyclopentadiene, which after step (ii) below is ¹³ C.
When measured by nuclear magnetic resonance spectroscopy (NMR),
It contained an average of 3.4 C _{9 to} C ₁₁ alkyl substituents.

(Ii) Multiple alkylated cyclopentadiene
Preparation of succinic anhydride derivative of ## STR00003 ## The multiple alkylated cyclopentadiene (11.4 g, 20 mmol) obtained in the above (i) and maleic anhydride (3
g, 30 mmol) was dissolved in toluene (200 ml), and the mixture was heated under reflux for 2 hours under a nitrogen blanket. The reaction mixture was cooled, then toluene was removed under reduced pressure to give a residue. Petroleum spirit / diethyl ether mixture (95: 5 v / v) on silica as eluent
The residue was purified by flash chromatography using to give the desired product as a pale yellow oil, a succinic anhydride derivative of multiple alkylated cyclopentadiene (7.4
g) was obtained. Infrared spectrum analysis of this product is 1
Peaks (V _max ) were shown at 855 cm ^-1 (m) and 1778 cm ^-1 (vs).

(Iii) Preparation of bisimide adduct R ¹ and R ² together represent a carbon-carbon single bond,
x is 3.4, each R ³ is C ₉ -C ₁₁ alkyl,
R ⁴ and R ⁵ are each hydrogen, and R ⁶ and R ⁷ are taken together,

[0128]

[Chemical Formula 39]

And two groups R ⁸ together form a bridging group — (CH ₂ ) ₂ —NH— (CH ₂ ) ₂ —NH— (C
H _{2) 2} - has a form compounds of formula (I), i.e.

[0130]

[Chemical 40]

Was produced.

A succinic anhydride derivative (15 g, prepared as described in (ii) above, was added to toluene (200 ml).
0.025 mol) and triethylenetetramine (1.8
3g, 0.0125mol) containing Dean
Reflux for 2 hours while removing water using an and Stark trap. Toluene was then removed under reduced pressure and the remaining residue was purified by flash chromatography on silica using a dichloromethane / methanol mixture (95: 5 v / v) as eluent to give the desired pale yellow oil. The product, bisimide (15 g), was obtained. Infrared spectrum analysis of this product is 1765c
V _max was shown at m ^-1 (m) and 1698 cm ^-1 (s).

Example 2 (i) Hydrogenated anhydrous multiple alkylated cyclopentadiene
A solution containing succinic anhydride derivative which was produced in during manufacture heptane succinic acid derivative (250 ml) Example 1 (ii), was placed in an autoclave together with 5% palladium on charcoal (1 g) as a hydrogenation catalyst. The autoclave was pressurized with hydrogen (6 MPa) and the contents of the autoclave were stirred for 2 days. The contents of the autoclave were then filtered through "Hyflo" (TM) filter aid to remove the catalyst and heptane was removed from the resulting filtrate under reduced pressure to give a yellow oily product (4g).
Was obtained (as determined by ¹³ C NMR, 15%
Was the starting material and 85% was the hydrogenated succinic anhydride derivative).

(Ii) Preparation of bisimide adduct R ¹ and R ² are each hydrogen, x is 3.4, and each R is
³ is C ₉ -C ₁₁ alkyl, R ⁴ and R ⁵ are each hydrogen, and R ⁶ and R ⁷ are taken together,

[0135]

[Chemical 41]

And two groups R ⁸ together form a bridging group — (CH ₂ ) ₂ —NH— (CH ₂ ) ₂ —NH— (C
H _{2) 2} - has a form compounds of formula (I), i.e.

[0137]

[Chemical 42]

Was produced.

The product (12 g, 20 mmol) prepared as described in (i) above in toluene (300 ml).
And triethylenetetramine (1.4g, 9.5mmo
The solution containing l) was refluxed for 2 hours while removing water using a Dean and Stark trap. The toluene was then removed under reduced pressure and the remaining residue was purified by flash chromatography on silica using a dichloromethane / methanol mixture (95: 5 v / v) as eluent to give the desired pale yellow oil. Product,
Bisimide (7.2 g) was obtained. Infrared spectrum analysis of this product showed 1768 cm ^-1 (m) and 1702c
V _max is shown in m ⁻¹ (s).

Example 3 (i) Preparation of multiply alkylated cyclopentadiene (interphase)
Transfer method) 1-bromooctadecane (500 g, 1.5 mol),
Cyclopentadiene (20 g, 0.3 mol) and aqueous potassium hydroxide solution (50%) (400 ml, 6.0 mo)
1) in the presence of [methyltrialkyl (C ₈ -C ₁₀ ) ammonium chloride] (a phase transfer catalyst sold under the trademark “Adogen 464”), first at 70 ° C. for 0.5 hours and then at 90 ° C. Heated for 2 hours. The reaction mixture was cooled, diluted with toluene (400 ml) and washed with water (5
00 ml) and filtered through "Celite" filter agent. The filtrate was dried over magnesium sulfate and the toluene was removed under reduced pressure to give 440 g of the desired product, alkylated cyclopentadiene. The product was measured by ¹³ C NMR after step (ii) below,
It contained an average of 3.8 C ₁₈ alkylating substituents.

(Ii) Multiple alkylated cyclopentadiene
Preparation of succinic anhydride derivative of ## STR00003 ## The polyalkylated cyclopentadiene (100 g, 0.1 mol) obtained in the above (i) and maleic anhydride
g, 0.11 mol) was dissolved in toluene (300 ml), and the mixture was heated under reflux for 1 hour under a nitrogen blanket. The reaction mixture was cooled, then toluene was removed under reduced pressure,
A residue was obtained. The residue was applied onto silica as eluent Petroleum spirit / diethyl ether mixture (90:
Purified by flash chromatography using 10 v / v) to give the desired product as a pale yellow solid, a succinic anhydride derivative of multiple alkylated cyclopentadiene (5
0 g) was obtained. Infrared spectrum analysis of this product
V at 1850 cm ^-1 (m) and 1780 cm ^-1 (s)
showed _max .

(Iii) Preparation of monoimide adduct R ¹ and R ² together represent a carbon-carbon single bond,
x is 3.8, each R ³ is C ₁₈ alkyl, R ⁴ and R ⁵ are each hydrogen, and R ⁶ and R ⁷ are taken together,

[0143]

[Chemical 43]

And R ⁸ is-(CH ₂ ) ₂ --NH--
_{(CH 2) 2 -NH- (CH} 2) 2 -NH 2 in which formula (I)
A compound of

[0145]

[Chemical 44]

Was produced.

The succinic anhydride derivative (15 g, 15 mmol) obtained in (ii) above in xylene (300 ml).
And triethylenetetramine (22g, 0.15mol)
The solution containing and was refluxed for 2 hours while removing water using a Dean and Stark trap. The xylene was then removed under reduced pressure and the remaining residue was dissolved in petroleum spirit (300 ml) and washed with a methanol / water mixture (90:10 v / v) (2 × 1).
00 ml). The solution is then dehydrated with magnesium sulfate,
Filtration and removal of petroleum spirit under reduced pressure gave the desired product as a pale yellow oil, monoimide (15.4 g). Infrared spectrum analysis of this product is 1770
It showed V _max in cm ^-1 (m) and 1700cm ^-1 (s).

Examples 4-26 Compounds of the invention detailed in Tables I and II below were prepared by methods analogous to those described in Examples 1-3.
The following symbols are used in the table: DAP: 3-dimethylamino-1-propylamine; DETA: diethylenetriamine; TETA: triethylenetetramine; TEPA: tetraethylenepentamine; PEHA: pentaethylenehexamine; D400: "Jeffamine D400" polyoxyalkylene amine (a compound of the above formula (V) in which A is -O-, r is 1, each R ¹¹ represents a methyl group, and s is 4-5); D2000 : "Jeffamine D2000" polyoxyalkylene amine (a compound of the above formula (V) in which A is -O-, r is 1, each R ¹¹ represents a methyl group, and s is 33).

[0149]

[Table 1]

[0150]

[Table 2]

Example 27 (i) Acroley of multiple alkylated cyclopentadiene
Preparation of the benzene derivative Into a stirred solution of multiple alkylated cyclopentadiene having an average of 3.4 C ₉ -C ₁₁ alkyl substituents obtained in Example 1 (i) above in toluene (300 ml) was added acrolein (10 g). , 0.14 mol) was added. The reaction mixture was refluxed for 1 hour, cooled and then the toluene was removed under reduced pressure to give a residue. The residue was purified by flash chromatography on silica using as eluent a petroleum spirit / diethyl ether mixture (90:10 v / v) to give the desired product as a pale yellow oil, a multiply alkylated cyclohexyl. An acrolein derivative of pentadiene (15 g) was obtained. Infrared spectrum analysis of this product showed a V _max at 1718 cm ^-1 (s).

(Ii) Preparation of the bisimine adduct The acrolein derivative prepared as described in (i) above in dry dichloromethane (100 ml) (20 g, 0.
(033 mol) and magnesium sulfate to a solution containing triethylenetetramine (2.4 g, 0.166 mol).
Was added. The reaction mixture was stirred at ambient temperature (20 ° C.) for 1 hour and the reaction process was monitored by infrared spectroscopy. The magnesium sulphate was then filtered off and the dichloromethane was removed under reduced pressure to give a crude product containing the desired bisimine adduct.

(Iii) Hydrogenation of the bisimine adduct R ¹ and R ² together represent a carbon-carbon single bond,
x is 3.4, each R ³ is C ₉ -C ₁₁ alkyl,
R ⁴ , R ⁵ and R ⁶ are each hydrogen, and R ⁷ is —CH ₂ —N.
HR ⁸ and the two groups R ⁸ together form a bridging group — (C
_{H 2) 2 -NH- (CH 2} ) 2 -NH- (CH 2) 2 - has a form compounds of formula (I), i.e.

[0154]

[Chemical formula 45]

Was produced.

The crude product obtained in (ii) above was dissolved in dry tetrahydrofuran and the resulting solution was cooled to -30 ° C. To selectively hydrogenate the bond of the imine (C = N) in the bisimine adduct, lithium aluminum hydride (1.6 g, 0.04 mol) was added to the solution after cooling, and the reaction mixture was stirred at room temperature for 2 hours. Stir for hours. The reaction mixture was then cooled to 0 ° C. and water was added slowly to it. The reaction mixture was filtered to remove solids, then tetrahydrofuran was removed under reduced pressure to give a residue. The residue was purified by flash chromatography on silica using a methanol / dichloromethane mixture (10:90 v / v) as eluent to give the desired product bisamine compound (15 g) as a yellow oil.

Example 28 (i) Mono-polyisobutylene substituted cyclopentadiene
Preparation of Monochlorinated polyisobutylene (PIB) (M _n 950) (50 g, 0.05 mo) in toluene (50 ml)
l), cyclopentadiene (13 g, 0.2 mol),
50% potassium hydroxide aqueous solution (54 g), and "Ado
A solution containing gen 464 "phase transfer catalyst (1 g) was placed in a reaction vessel and stirred for 10 minutes at 5 ° C. The reaction mixture was stirred at 80 ° C. for 2 hours, then cooled to ambient temperature (20 ° C.) and added to petro. Diluted with sodium spirit (600 ml), washed the solution with water (5 x 200 ml), dried over magnesium sulphate and concentrated under reduced pressure to give crude product mono-PIB.
Substituted cyclopentadiene (52 g) was obtained.

(Ii) Mono-PIB-substituted cyclopentadiene
Preparation of succinic anhydride derivative of ## STR00003 ## The crude product (52 g) obtained in the above (i) was dissolved in toluene (200 ml), and maleic anhydride (10
g, 0.1 mol) was added. The reaction mixture was then heated at reflux under a nitrogen blanket for 1 hour. Let it cool down,
The reaction mixture was concentrated under reduced pressure and the resulting residue was purified by flash chromatography on silica using dichloromethane / petroleum spirit mixture (50:50 v / v) as eluent, pale yellow. An oily desired product was obtained, a succinic anhydride derivative of monoPIB-substituted cyclopentadiene (14.5 g).

(Iii) Preparation of bisimide adduct R ¹ and R ² together represent a carbon-carbon single bond,
x is 1, R ³ is a polyisobutenyl chain, R ⁴ and R ⁵ are each hydrogen, and R ⁶ and R ⁷ are taken together,

[0160]

[Chemical formula 46]

And two groups R ⁸ together form a bridging group-(CH ₂ ) ₂ --NH-(CH ₂ ) ₂ --NH-(C
H _{2) 2} - has a form compounds of formula (I), i.e.

[0162]

[Chemical 47]

Was produced.

A succinic anhydride derivative (27 g, prepared as described in (ii) above, was added to toluene (200 ml).
0.0022 mol) and triethylenetetramine (1.
6 g, 0.0011 mol) with Dean
Reflux for 1 hour with removal of water using an and Stark trap. The toluene was then removed under reduced pressure and the remaining residue was purified by flash chromatography on silica using a dichloromethane / methanol mixture (95: 5 v / v) as eluent to give the desired product as a yellow oil. A bisimide (28 g) was obtained.

Example 29 In this example, substantially the same procedure as described in Example 28 was repeated, except that in step (i) M _n 1800 PIB was used and in step (iii) Pentaethylene hexamine (0.45 g.0.0
0195 mol) was used. The bisimide product of a brown viscous liquid, i.e. R ¹ and R ² together represent a carbon-carbon single bond, x is 1, R ³ is a polyisobutenyl chain and R ⁴ and R ⁵ are each hydrogen. And R ⁶ and R ⁷
Together,

[0166]

[Chemical 48]

A compound of formula (I) in which _two radicals R ⁸ together form a bridging radical — (CH ₂ ) ₂ — [NH— (CH ₂ ) ₂ —] ₄ ,

[0168]

[Chemical 49]

There was obtained (8.9 g).

Example 30 (i) Preparation of Bridged Alkylated Cyclopentadiene Cyclopentadiene (1
4 g, 0.22 mol), monochlorinated polyisobutylene (PIB) (M _n 1378) (200 g, 0.2 mo)
1), α, α′-dichloroxylene (17.5 g, 0.
1 mol) and an “Adogen 464” phase transfer catalyst (5 g) were added to an ice-cooled mixture containing ice-cooled 50% aqueous potassium hydroxide solution (100 g) with stirring. The reaction mixture was stirred first at ambient temperature (20 ° C.) for 15 minutes and then at 80 ° C. for 2 hours. Once cooled, dilute the reaction mixture with petroleum spirit (800 ml),
Wash with water until pH is neutral (5 x 300 ml),
It was dehydrated with magnesium sulfate. Concentrate under reduced pressure to give the crude product xylyl bridged mono-PIB-substituted cyclopentadiene (2
20 g) was obtained.

(Ii) Bridged alkylated cyclopentadiene
Preparation of succinic anhydride derivative of ## STR00003 ## The crude product obtained in (i) above (220 g, 0.2 mol) and maleic anhydride (19 g, 0.2 mol) were dissolved in toluene (800 ml) and then under a nitrogen blanket. The mixture was heated to reflux for 1 hour. After cooling the reaction mixture, toluene was removed under reduced pressure to give a residue. The residue was purified by flash chromatography on silica using first petroleum spirit, then dichloromethane as eluent to give the desired product as a brown oil, a succinic anhydride derivative of the xylyl bridged mono-PIB-substituted cyclopentadiene (220 g). Got Infrared spectrum analysis of this product was 1861 cm ^-1 (m) and 17
V _max was shown at 83 cm ^-1 (vs).

(Iii) Preparation of Imide R ¹ and R ² together represent a carbon-carbon single bond,
R ⁴ and R ⁵ are each hydrogen, and R ⁶ and R ⁷ are taken together,

[0173]

[Chemical 50]

And the group R ⁸ is a bridging group — (CH ₂ ) ₂ —
_{[NH- (CH 2) 2 -} ] is ₃ -NH _2, x is 2, one R ³ is polyisobutenyl chain, the other R ³
In the formula (IV), x ′ is 1, R ³ ′ is a polyisobutenyl chain, and R ⁶ and R ⁷ ′ are combined,

[0175]

[Chemical 51]

A compound of formula (I) wherein R ¹ , R ² , R ⁴ , R ⁵ and R ⁸ are groups of formula (II) as defined above,

[0177]

[Chemical 52]

Was prepared.

The succinic anhydride derivative (20 g, 0.0143 m) obtained in the above (ii) was added to toluene (300 ml).
ol) and tetraethylenepentamine (1.35 g, 0.
(009 mol) with Dean and S
1.5 while removing water using the tark trap
Reflux for hours. The toluene was then removed under reduced pressure and the remaining residue was eluted on silica first with dichloromethane and then with a dichloromethane / methanol mixture (90:
Purified by flash chromatography using 10 v / v) to give the desired product imide (2
1 g) was obtained. Infrared spectrum analysis of this product is 1
V _{max at} 770 cm ^-1 (m) and 1702 cm ^-1 (s)
showed that.

Examples 31-39 By repeating the steps of Example 30 in the variations shown in Table III below, another compound of formula (I) was prepared. The following symbols are used in Table III.

CPD: cyclopentadiene; DCX: α, α'-dichloroxylene; PIB: polyisobutylene; MALA: maleic anhydride; TETA: triethylenetetramine; TEPA: tetraethylenepentamine; PEHA: pentaethylenehexamine; HEPA: Higher ethylene polyamine (substantially a mixture of tetraethylene pentamine, pentaethylene hexamine and hexaethylene heptamine in a molar ratio of 1: 2: 1).

[0182]

[Table 3]

Example 40 (i) Preparation of cross-linked cyclopentadiene In toluene (250 ml), cyclopentadiene (2
0 g, 0.3 mol), dichlorinated polyisobutylene (P
IB) (M _n 1800) (138 g, 0.076 mo
l), and "Adogen 464" phase transfer catalyst (1
To an ice-cooled mixed solution containing g), ice-cooled 50% aqueous potassium hydroxide solution (200 ml) was added. First, mix the reaction mixture with 5
The mixture was stirred at 0 ° C for 10 minutes and then at 80 ° C for 2 hours. Once cooled, the reaction mixture is mixed with petroleum spirit (5
(00 ml), washed with water until pH neutral (5 x 200 ml) and dried over magnesium sulfate. Concentration under reduced pressure gave the crude product PIB-bridged cyclopentadiene (100 g).

(Ii) Anhydrous bridged cyclopentadiene
Production of Cucic Acid Derivative The crude product (100 g) obtained in (i) above and maleic anhydride (10 g, 0.1 mol) were mixed with toluene (200 g).
ml) and then heated at reflux under a nitrogen blanket for 1 hour. After cooling the reaction mixture, toluene was removed under reduced pressure to give a residue. The residue was dissolved in petroleum spirit (1000 ml) and the solution was purified by centrifugation in a centrifuge at 2500 rpm for 30 minutes. Then, the supernatant liquid was absorbed and concentrated under reduced pressure to obtain a desired product as a clear brown oil, a succinic anhydride derivative of PIB-bridged cyclopentadiene (100 g). Infrared spectrum analysis of this product is 1783 cm
V _max was shown at ⁻¹ (s) and 1853 cm ⁻¹ (m).

(Iii) Preparation of Imide R ¹ and R ² together represent a carbon-carbon single bond,
R ⁴ and R ⁵ are each hydrogen, and R ⁶ and R ⁷ are taken together,

[0186]

[Chemical 53]

And R ⁸ is — (CH ₂ ) ₂ — [NH—
(CH _{2) 2} -] is ₃ -NH _2, x is 1, R
³ , D is derived from polyisobutylene (M _n 1800), x ′ in the formula (IV) is 0, R ⁶ and R ⁷ ′
Together,

[0188]

[Chemical 54]

A compound of formula (I) wherein R ¹ , R ² , R ⁴ , R ⁵ and R ⁸ are groups of formula (IIIB) as defined above, ie

[0190]

[Chemical 55]

Was prepared.

The succinic anhydride derivative (20 g, 0.0143 m) obtained in (ii) above was added to toluene (250 ml).
ol) and tetraethylenepentamine (1.35 g, 0.
(009 mol) with Dean and S
Reflux for 2 hours while removing water using a tark trap. The toluene was then removed under reduced pressure and the remaining residue was first eluted on silica with dichloromethane as eluent,
Then dichloromethane / methanol mixture (90:10)
Purified by flash chromatography using (v / v) to give the desired product imide (21) as a brown oil.
g) was obtained. Infrared spectrum analysis of this product is 17
70cm ^-1 (m) and 1702cm ^-1 to (vs) V _max
showed that.

Example 41 (i) Carbon black dispersibility test (CBDT) (Br
itish Rail Publication BR
669: 1984) SAE 15W40 with a commercial package of zinc dialkyldithiophosphate, overbased alkyl calcium salicylate, and a VI improver.
A sample of Middle East lubricating oil was used in Example 1,
Modifications were made by incorporating the imide products of 2, 7, 13, 14, 24-26, 38 and 39 to give oils containing these products at an active ingredient concentration of 1% by weight. Then add 3% by weight of carbon black to each oil and add Ubbelohd
Increase in kinematic viscosity at 60 ° C using viscometer (%)
Was measured. The smaller the value, the better the efficacy. Since the absolute values obtained depend on the effective surface area of the carbon black used, it is necessary to carry out a series of comparative tests with the same carbon black sample. The test was conducted with "Flamruss" (trademark) or "C" as carbon black.
Performed using any of the abot Carbon Elftex 460 "™.

(Ii) Fluorine rubber seal compatibility test (FS
CT) The imide products of Examples 1, 2, 7, 13, 14, 24-26, 38 and 39 were incorporated into lubricating oils to a concentration of the active ingredient of 1.5% by weight, and DIN 53504, especially Dai 53504.
Compatibility with fluororubber sealing materials was tested according to the method of mler Benz Specification DB 6615. The decrease (%) in tensile strength (TS) and elongation at break (EB) was evaluated. Since the test results depend on the particular seal material used, a series of comparative tests should be performed with seals from the same batch throughout. The smaller the value, the better the efficacy.

The results of the above tests are given in Table IV below.

[0196]

[Table 4]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication location C07C 225/20 243/20 C07D 209/72 9284-4C 209/74 9284-4C 209/76 9284- 4C C10M 133/06 133/46 9159-4H // C10L 1/22 Z 6958-4H C10N 30:04 (72) Inventor Robert William Siyot Kent M E 10 1 P Wai, Sitting Bone, Gatsby Road 89

Claims (12)

[Claims] 1. A compound represented by the general formula (I): [In the formula, R ¹ and R ² each represent a hydrogen atom or, together, represent a carbon-carbon single bond; R ⁴ and R ⁵ are each independently a hydrogen atom or optionally substituted. Represents an optionally substituted C ₁ -C ₂₀ alkyl or phenyl group; R ⁶ represents a hydrogen atom, or an optionally substituted C ₁ -C ₂₀ alkyl or phenyl group,
R ⁷ represents a group —CH ₂ —NHR ⁸ {wherein R ⁸ represents an optionally substituted alkyl group or a group —COX (where X represents an optionally substituted alkoxy group)} or —NH
Represents R ⁸ (wherein R ⁸ is as defined above);
Alternatively, R ⁶ and R ⁷ together form a group: (Wherein R ⁸ is as defined above); x is 1-6; each R ³ is independently an optionally substituted alkyl or alkenyl group or a formula: “In the formula, m is in the range of 0 to 25, n is in the range of 1 to 20, each R ⁹ independently represents a hydrogen atom or a methyl or ethyl group, and D is 20 to 500 carbon atoms. Derived from a saturated or unsaturated hydrocarbon containing, Y is of formula (IV): {Wherein R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ are as defined above; x ′ is 0 to 5; R ³ ′ is the formula (II),
As defined for R ³ other than groups (IIIA) or (IIIB); R ⁷ 'represents group R ^{7 as} defined above or group --CHO or --COOH, or R ⁶
And R ⁷ 'are taken together to form the group: (Wherein R ⁸ is as defined above)}, and each group R ³ is at the same time more than 40 groups of up to ³ R ³ groups each. A total of 550, provided that they can contain carbon atoms and that all groups R ³ together contain more than 20 carbon atoms.
Containing up to 4 carbon atoms]. 2. A compound according to claim 1, wherein R ¹ and R ² together represent a carbon-carbon single bond. 3. Each R ³ is independently a C ₁ -C ₄₀ alkyl group, C
₅₀ -C ₂₀₀ polyalkenyl group or claim 1 claim 1 or 2 represents a group of formula (II) or (IIIB) according to,
The compound according to. 4. x is 1, R ³ is a C ₅₀ -C ₂₀₀ polyalkenyl group, or D is derived from an unsaturated hydrocarbon and x ′ in the formula (IV) is 0. Certain formula (IIIB)
Represents any of the groups described above; x is 2 and one R
³ represents a C _{50 to} C ₂₀₀ polyalkenyl group, and the other R ³
In the formula (IV), x ′ is 1 and R ³ ′ is C _{50 to} C _200.
Or it represents a group of formula (II) representing the polyalkenyl group; or, x is from a 3-4 A compound according to claim 3 in which each R ³ represents a C ₇ -C ₁₈ alkyl group independently. 5. R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom and R ⁷ represents a group —CH ₂ NHR ⁸ or R ⁴
And R ⁵ each represent a hydrogen atom, and R ⁶ and R ⁷ together represent the group: The compound according to any one of claims 1 to 4, which represents: wherein R ⁸ is as defined in claim 1. 6. —NHR ⁸ or —NR ⁸ is represented by the general formula (V): [In the formula, A is —NH or —O—, each R ¹¹ independently represents a hydrogen atom or a methyl group, r is in the range of 1 to 3, and s is when A is —NH. In the range of 1 to 8 and in the range of 1 to 200 when A is —O—] or two radicals R ^{8 taken} together have the general formula (V '): [In the formula, A, R ¹¹ , r and s are as defined above]
The compound according to any one of claims 1 to 5, which is a crosslinking group of 7. A process for producing a compound of formula (I) according to any one of claims 1 to 6, which comprises the formula (VI)
I): [In the formula, x, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are as defined in claim 1, provided that the group R ³ is the formula (II),
When it represents a group of (IIIA) or (IIIB), it has the formula (IV)
The group R ⁷ 'in the group represents a group -CHO or -COOH, or R ⁶ and R ⁷ ' are taken together to form a group: R ⁷ ″ represents —CHO or —COOH, or R ⁶ and R ⁷ ″ together represent the group: Of the general formula (VIII): B—H (VIII) [wherein, when R ⁷ ″ represents a —COOH group, B represents the group X as described above and R ⁷ ″ represents Represents a CHO group or is a group in which R ⁶ and R ⁷ ″ are taken together: B represents a group represented by the group —NHR ⁸ as described above] and, if necessary or desired, the product thus obtained is selectively hydrogenated to give a carbonyl group (C═O). ) Or imine (C = N) unsaturation. 8. An intermediate compound of formula (VII) according to claim 7. 9. A lubricating oil composition comprising a major amount of lubricating oil and a minor amount of a compound of formula (I) according to any one of claims 1-6. 10. A fuel composition comprising a major amount of fuel and a minor amount of a compound of formula (I) according to any one of claims 1-6. 11. An additive concentrate comprising an inert carrier liquid and 10 to 80% by weight, based on the total concentrate, of a compound of formula (I) according to any one of claims 1 to 6. . 12. Use of a compound of formula (I) according to any one of claims 1 to 6 as a dispersant.