JPS59108731A - Novel phenols and composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

The present invention relates to new phenols, processes for their production and their use as stabilizers and corrosion inhibitors. Regarding phenols with similar structure to goldite, see Japanese Patent Application Laid-open No. 5
No. 7-203030. According to the present invention, the following formula (1): (wherein p is 1.2 or 3, and q is 0.1 or 2, provided that p+ct≦3; R is the following formula; and when p is 2 or 3, each group R
may be the same or different, and 2-4- or j
It exists in the halo position; n is an integer from 2 to 30;
is 1 or 2; Q is the following group; l) -COO
R' or -CONR'R': [In the above formula, R' is
Hydrogen atom; optionally separated by 1 to 5 oxygen atoms, and optionally a group -OR'(R' is a C3 to C+Z cycloalkyl group, a linear or branched C5 to C1° alkenyl group, optionally - or C6-C+o aryl group substituted with 01-C4 alkyl group or C7
A straight-chain or branched alkyl group having 1 to 20 carbon atoms substituted with an aralkyl group of ~CI3; a divalent straight-chain or branched alkylene group having 2 to 20 carbon atoms;
Straight-chain or branched alkenyl group having 3 to 20 carbon atoms; 7-chloroalkyl group having 3 to 12 carbon atoms; optionally substituted with a C, to C4 alkyl group having 6 to 1 carbon atoms
0 aryl group; aralkyl group having 7 to 13 carbon atoms;
Contains oxygen atoms, optionally 1 or 200, ~C4
a 5- or 6-membered heterocyclic group substituted with a straight-chain or branched alkyl group of is a methyl group substituted with a 5- or 6-membered heterocyclic group, but if k is 2, the two carbon atoms to which the group -COOR' is bonded are not adjacent to each other. R5 is a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms; It may also form a 5- or 6-membered heterocyclic group substituted with a C4 alkyl group. ] II) -〇X: [In the above formula, X is t or COR', where R5
has the above meaning, R7 is a hydrogen atom; number of carbon atoms is 1 to
20 straight or branched alkyl groups; 3 to 3 carbon atoms
20 linear or branched alkeni/l/X; C
A 3-C+Z cycloalkyl group, a C7-CI3 aralkyl group; or a C6-Coo aryl group optionally substituted with - or 2-01-C4 alkyl groups. ] ++:)-NR"R9: [In the above formula, R8 is a hydrogen atom or a straight or branched alkyl group having 1 to 4 carbon atoms; R9 is a hydrogen atom,
a straight-chain or branched alkyl group having 1 to 4 carbon atoms, or an anru group of the formula -COR7 (R7 has the meaning given above): or R8 and R9 together with the nitrogen atom to which they are respectively bonded; , depending on the case - or two zeros
All 5- or 6-membered ring groups substituted with 1 to C4 alkyl 8 are formed. ]IV) -PO(ORIo)[0
), R'': [In the above formula, X is O or 1; when X is 1, R10 and R'' may be the same or yellow,
each a hydrogen atom or a straight-chain or branched alkyl group of 1 to 2 o carbon atoms, or R'' and R'' are combined with each other and optionally substituted with - or two C1-C20 alkyl groups; -C3 alkylene chain may be formed; when X is O, R'. is a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms, and R'' is a C3 to C3 direct alkyl group.] V) CN, hao)fy atom, N02: and Vl) -COR12: [In the above formula, R'' is a hydrogen atom, a straight chain or branched alkyl group having 1 to 20 carbon atoms, or a lodene atom. ]; R2 and W may be the same or different and are each a straight chain or branched alkyl group having 1 to 5 carbon atoms; when Q is -CO, *, R2 or R3 is selected from Either one is optionally a group -co! Is it replaced by r (
each group R4 is independent), or R2 or R3
is bonded to the group cfit(2n, , -, and the group -(Co
may form a C3-C12 cycloalkylene group substituted with tR')kl (wherein rt4 and k have the above meanings); Q is a group -COR'', R2 or R3 is bonded to the group CnH2n41- and optionally the group -COR
"f-substituted C3-C+Z cycloalkylene group may be formed; however, 1. JilFQ is a group -co
2t < * is a divalent straight chain or branched alkylene group with 1 to 2 carbon atoms); p and k
are both 1, and the compound is represented by the following formula 1a: (wherein R'' is a divalent straight or branched alkylene group having 2 to 2 o carbon atoms); the group Q is a group - CONR'R'(R' is carbon,
is a divalent straight chain or branched alkylene group having 2 to 20 atoms, and R5 has the above meaning), 9
and kl are both 1, and the compound 2) is represented by the following formula: (wherein, R41 is a divalent straight or branched alkyl group having 2 to 2 carbon atoms); R1 is a straight chain of 01 to CI2, 1 is a branched alkyl group, and C? ~C0 aralkyl group, haloke 1 atom, -C
Fs, -8t(, -8R+3, -C02H, -C0z
R", -COR", -C0CaHa, -C0NH?
, -CN, -5OsH, -SO2NH2, -PO
(OF()t, -PO(OR”)21j: -NO!
(Kokote, Rld C+ ~C4) is a straight chain or branched alkyl group); when q is 2, the group R
1 may be the same or different; when q is 1, R1 in 2■ is represented by the following formula ■ or ■: [wherein R and R1 have the above meanings; r is 01 or 2; , S is 0 or 1, provided that r+S≦2; Mid direct bond, -C(R14)(R")-. -3-, -8-3-, -3O-, -8Ow -, -CruS CH2-1-O-, -CHtOCH2- or -NR
"-" (herein, "R" and "R" may be the same or different, and each represents a hydrogen atom, or a straight or branched alkyl group having 1 to 20 carbon atoms separated by 1 to 3 sulfur atoms) , an aryl group having 6 to 10 carbon atoms, or the carbon atom to which R'4 and R1I' are bonded, -
or forms a 5- or 6-membered ring which may be further substituted with two C1-C8 alkyl groups, and R'' is a wood surface atom, a straight chain or 7- or branched alkyl group having 1 to 12 carbon atoms. or a phenyl group)] However, in 7, the compound of formula (1) has only one group of formula (I) or (2), and this group (2) or (2) is a group. - Exists at the 2-94- or 6-position with respect to H? p is 1, R1 is a C2-CI2 alkyl group, R2 and W
is a C0 to C6 alkyl group, k is 1, and Q is -Co01r
(R' is a hydrogen atom, and when q has the abovementioned meaning, n is other than 2) and salts thereof with organic or inorganic acids and bases are provided. When the group R1 is a C4-C12 linear or branched alkyl group, the group 7 is, for example, a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 5ec -butyl-q, isobutyl group, 1-butyl group, t-amyl group, ], , 1, 3, 3-tetramethylbutyl group, n-denyl group or n-dobutyl group. When the group J or R3 is a C1-C5 14-chain or branched alkyl group, the group is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a n-butyl group, a 5ac-butyl group, group, n-pentyl group or neopentyl group, optionally separated by 1 to 5 oxygen atoms.
When it is a 1 to C26 straight or branched alkyl group, the group is, for example, a methyl group, an ethyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, a 2-n-propoquinethyl group, a 2-n-propoquinethyl group, -n-butquinethyl group, n-pentyl group, n-hexyl group, n-hebutyl group, ■-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, n-eicosyl group, group -(C! HA O)2 CH3, group -(C2'H40
)s CHs , the group -(C2H40)4CH8) or the group -(ctpbO)5CH3. When R1, R6 or R1 is a C3-CtO linear or branched alkenyl group, the group is, for example, 2-
propenyl group, 2-n-butenyl-Jli, 2-methyl-2-7'robenyl group, 2-n-takutenyl group, 2-n
=hexenyl group, 2 + 4 n-hexazoenyl 2@
, □. -1-, 2 resins.・′-1-0i. It may also be a cenyl group. When the group R4, R6 or R7 is a C3-C1 noacroalkyl group, the group is, for example, a cyclopropyl group,
It may be a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclodecyl group, an adamantyl group, or a cyclooctyl group. Group R', R1'
Or when R7 is an aralkyl group of 0r-C, s,
The group may be, for example, an innor group, a phenylethyl group, a tanzhydryl group or a naphthylmethyl group. When R4, R6 or R7 is a C6-CIO aryl group optionally substituted with a-C4 straight or branched alkyl group, the group is a phenyl group, tolyl group, quinryl group, cumyl group. (cumenyl group), butylphenyl group or naphthyl group.0° group Q is -C00R
', when R4 is an oxygen atom or a 5 or 6 heterocyclic group optionally substituted with one or two linear or branched C1-C4 alkyl groups, the group R4 is For example, it may be a 3-tetrahydrofuranyl group, a 4-tetrahydropyranyl group, or a 2,6-nomethyl-4-tetrahydropyranyl group. When the group W is a methyl group substituted with a 5- or 6-membered heterocyclic group containing an oxygen atom and optionally substituted with - or two linear or branched 01-C4 alkyl groups, the group teeth,
For example, it may be a furfuryl group, a tetrahydrofurfuryl group or a 2-tetrahydropyranyl group. If the group R8, RO or RIB is a C2-C4 straight-chain or branched alkyl group, it can be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-
-butyl group or 5ec-butyl group. The radicals R4 and R5, and the radicals R6 and R9, together with the nitrogen atom to which they are bonded, form a 5- or 6-membered heterocycle optionally substituted with - or two 01-C4 alkyl groups. If so, the ring may be, for example, pyrrolidine, biverison, morpholine or 2,5-dimethylmorpholine. Group R', R71R10,R1' I R12,R1
', R' or R16 is a Cl-C20 linear or branched alkyl group, these groups may be the same or different; for example, methyl group, ethyl, etc., n-
Propyl group, isopropyl group, n-butyl group, 5ea-
Butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-
It may be a nonyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, n-eicosyl group, or the like. The groups R" and R" are bonded to optionally - or more C7 to CtO alkyl groups 1! exchanged C2
Or, if a C3 methylene chain is formed, the chain is, for example, -CT(2CFI2-1(JTs-CH2
-CH2-1-CH2CT((CH3)-1-CH
(CtFTq)-1-CT(zC)i (C20H4
1)-1-CH(CHs)CH(CH3)-1-CH(
CH3) C(CH3)2-1- C(CH3)2-〇(CHs)t-, -CHtCHz-C(CHs)t-
1 or -CH(CHSCf(2CH(Ct et al))-. The groups R14 and R15, together with the carbon atom to which they are attached, form a 5- or 6-membered ring substituted by If the group R4Q or R41 is a carbon atom In the case of a divalent linear or branched alkylene group having a number of 2 to 20, the group is, for example, -CH2CFI2-1- (CT(Js
-1-(C1■2)4-1- (CH2)+-1-(
CHJa-1-(mount C), -1-(low-1-(CH2
)+. -, - (CI also), 2-1-<C horse), Ji, -
(CH2)+6-1- (CH2)+g-1-(CH2
)20-1-CT(2CH(CH3)-1-C)h
C(CH,), -1-CHCHsCHCf (s- or -
〇(CT-+8)2c (may be CH312-. When the group Q and R1 are halogen atoms, the atom is a fluorine atom, chlorine atom, bromine atom or iodine atom. The group R1!) - In the case of a location atom, the atom may be a chlorine atom or a bromine atom. Specific examples of salts include salts with metals, alkaline earth metals, and amines;
In the case of R8R'', salts with organic or inorganic acids such as hydrochloric acid, sulfuric acid, Il+-)luene-sulfonic acid and oxalic acid may be mentioned. As one preferred embodiment, the following formula V: [In the above formula, R1, p and q have the above-mentioned meanings, and Ro
is a group represented by the following formula: % formula %() (wherein n, +R'+R', R' and R5 have the above-mentioned meanings) ] Examples of the compounds of the present invention include the compounds of the present invention. More preferred compounds of formula V are those where k=1;
Particularly preferred are compounds in which Ro is a group of formula IIa; particularly preferred are compounds in which R'' and R3 are CH3 and R1 is a C1-C6 straight-chain or branched alkyl group; most preferred A compound in which n = 3. Other preferred compounds of the invention are compounds in which p is 1 and qn t
k + R' + u2* Compounds of formula 1 in which R' and Q have the meanings given above. In this embodiment, more preferred compounds are those in which k is 1; particularly preferred are compounds in which R2 and R' are carbon atoms and R1 is a linear or branched alkyl group of C, -C. Yes; most preferably a compound in which n is 3 to 10. Particularly preferred are those compounds of formula V that do not contain a group of formula (1) or (2). Specific examples of the compound of formula 1 are described below, but the compound is not particularly limited to the following: 5-(2-hydroxyphenyl)-5-methyl
4-human "loquinphenyl)-5-methylhexanoic acid and its sodium salt, methyl 5-(2-hydroxyphenyl)-5-methylhexanoate 5-(4-hydroxyphenyl)-5-methylhexanoate 5, -(4-hydroxyphenyl)-5-methylhexanoate n-hexyl s-(4-hydroxyphenyl)-5-methylhexanoate 2-ethylhexyl 5-(4-hydroxyphenyl)-5-methylhexanoate eicosyl 5-(4-hydroxyphenyl)-5-methylhexanoate - (4-hydroxyphenyl)-5-methylhexanoate 2-butoxyethyl 5-('4-hydroxyphenyl)-5-methylhexanoate 2-cyclohexyloxyethyl 5-(4-hydroxyphenyl)- 5-Methylhexanoic acid 2-allyloxyethyl 5-(4-hydroxyphenyl)-5-methylhexanoic acid 2-phenoxyethyl 5-(4-hydroxyphenyl)-5-methylhexanoic acid 2-(4-methylphenoxy) Ethyl 5-(4-
Undecenyl 5-(4-hydroxyphenyl)-5-methylhexanoate 2-Benzyloxyethyl 5-(4-hydroxyphenyl)-5-methylhexanoate Allyl 5-(4-hydroxyphenyl)-5-methylhexanoate Cyclohexyl 5-(4-hydroxyphenyl)-5-methylhexanoate 5-(4-hydroxyphenyl)-5-methylhexane 1-phenyl 5-(4-hydroxyphenyl)-5-methylhexanoate 4-methylphenyl 5- (4- Hydroquine fubenlucu Benzyl 5-methylhexanoate 5-(4-hydroxyphenyl)-5-methylhexanoate tetrahydrofurfuryl 5-(4-hydroxyphenyl)-5-methylhexanoate furfuryl 2shi5- (4 -hydroxyphenyl)-5-methylhexanoic acid 4-tetrahydropyranyl 5-(4-hydroquinphenyl) -5-methylhexanamide N-methyl-5-(4-hydroxyphenyl) = 5-methylhexanamide N- n-butyl-5-(4-hydroxyphenyl-5-
Methylhexanamide N,N-dimethyl-5-(4-hydroquinphenyl)-
5-Methylhexanamide N,N-diethyl-5-(4-hydroxyphenyl)-
5-Methylhexanamide N, N-di-n-butyl-5-(4-hydroquinphenyl-5-methylhexanamide N -n-eicosyl-5-(4-hydroxyphenyl)-5-methylhexanamide N -7!J-ru 5-(4-hydroquinphenyl)-5-
Methylhexanamide N-cyclohexyl-5-(4-hydroxyphenyl)
-5-Methylhexanamide ψ N-yne true 5- (4-hydroxyphenyl)-
5-Methylhexanamide N-phenyl-5-(4-hydroxyphenyl) = 5-
Methylhexanamide N-(5-(4-hydroxyphenyl)-5-methylhexanoyl 3-morpholine 5- (4-hydroxy-3-methylphenyl)-5-
Methylhexanoate 5-(4-hydroxy-3-methylphenyl)-5-
Allyl methylhexanoate 5-(4-hydroquine-3-methylphenyl)-5-cyclohexylhexanoate 5-(2-hydroxy-5-methylphenyl)-5-
Methylhexanoate 5-(2-hydroxy-5-methylphenyl)-5-methylhexanoate 5-(2-hydroxy-3.5-dimethylphenyl)-
5-Methylhexanoate 5- (2-hydroxy-3,5-dimethylphenyl)
Methyl-5-methylhexanoate sL (4-hydroxy-3,5-zomethylphenyl)
= Methyl 5-methylhexanoate 5- (5-ethyl-2-hydroquinphenyl)-5-
Methylhexanoate 5-(5-ethyl-2-hydroxyphenyl) = Methyl 5-methylhexanoate 5-(3-ethyl-4-hydroxyphenyl)-5-methylhexanoate 5-(3,5-diethyl -4-hydroxyphenyl)
-5-methylhexanoate methyl 5-(5-n-decyl-2-hydroxyphenyl)-5
-Methylhexanoate 5-(2-hydroquine-5-isopropylphenyl)-
5-Methylhexanoate 5-(2-hydroxy-5-isopropylphenyl)- Methyl 5-methylhexanoate 5-(4-hydroxy-3-isopropylphenyl)-
Methyl 5-methylhexanoate 5-(2-hydroxy-3,5-diisopropylphenyl)-5-methylhexanoate 5-(4-hydroxy-3,5-diisozolopylph, =c=ru)-5 -Methylhexanoate 5- (3-5eq-butyl-4
-hydroxyphenyl)-5-methylhexanoate 5-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-methylhexanoate 5-(3-j-
Butyl-4-hydroxy-5-methylphenyl)-5-
Methyl methylhexanoate 5-(3-1 mil-4-hydroquinphenyl)-5-methylhexanoate 5-(3-cumyl-4-hydroxy-5-methylphenyl)-5-methylhexanoate 5- (3-t-butyl-2-hydroquine-5-isopropylphenyl)-
Methyl 5-methylhexanoate 5- (3,5-not-butyl-2-hydroxyphenyl)-5-methylhexanoate #5- (3,5
-di-t-butyl-4-hydroxypheni)v)-5-
Methylhexanoate 5-[2-hydroxy-5-(
1,1,3,3-tetramethylbutyl)phenyl yo5
-Methylhexanoate 5-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-methylhexanoate 5- (3-t-butyl-2-hydroxy-5-methylphenyl)-5 -Methylhexanoyl chloride 1,6-hexanediol and 5-(3-t-butyl-4
-hydroxy-5-methylphenyl)-5-methylhexanoic acid diester with 1,6-hexanediol and 5-(a-t-butyl-4
-Diester with 1,6-hexanediol and 5-(3,5-di-t-butyl-4-hydroxyphenyl)-5-methylhexanoic acid diester with 1.1.3.3-tetramethylbutylamine and 5-(3
-t-butyl-2-hydroxy-5-methylphenyl)
Amide of -5-methylhexanoic acid Amide of n-dodecylamine and 5-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-methylhexanoic acid Amide of 1,6-soaminohexane 5-(3-t-butyl-2
-Diamide with 5-hydroxy-5-methylphenyl)-5-methylhexanoic acid 5-(5-chloro-2-hydroxyphenyl)-'5-
Methylhexanoate 5-(3-chloro-2-hydroxy7ethyl)-5-
Methyl methylhexanoate 5-(3-dichloro-4-hydroxyphenyl)-5-methylhexanoate 5-(3,5-dichloro-4-hydroxyphenyl)-5-methylhexanoate 2+4''' His(5-methoxycal is nyl-2-methyl-2-pentyl) phenol 2.6'-4''s(5-methoxycarbonyl-2-methyl-2-pentyl)phenol 2,6-bis(methoxycal? Niru-2-methyl-2
-pentyl)-4-methylphenol2.4.6-)lis(5-carboxy-2-methyl-2-pentyl)phenol2.4.6-)lis(5-methquine carbinyl-2-
methyl-2-pentyl)phenol 2.4-bis(5-carboxy-2-methyl-2-pentyl)phenol 2.6-bis(5-carboxy-2-methyl-2-inchyl)-4-methylphenol 2-( 8-n-butoxy-2,6-dimethyl-2-
octyl)-4-(5-methoxycarvinyl-2-methyl-2-pentyllaphenol) Carbinyl-2.2.4-trimethyl-4-hebutyl)phenol 5-(4-hydroxyphenyl)-2-methquinal?
Methyl 2-carboxy-5-5-methylhexanoate
-(2-hydroxy-5-methylamine/I/) -5
-Methylhexanoic acid 5- (2-hydroxy-5-methyl7
Methylhexanoate 5-methyl-5-(2-hydroxyphenyl)dimethyl azelaate 5-methyl-5-(4-hydroxyphenyl)dimethyl azelaate 7-(4-hydroxyphenyl) -3,7-nomethyl-1- Octatool 7-(2-hydroxy-5-methylphenyl)-3,7
-Nomethyl-1-octatool 1-n-butoxy-7-(4-hydroxy-3,5-)
; If thylenyl) -3,7-dimethyloctane 1-
Acetoxy-7-(4-hydroxyphenyl)-3,7
-dimethyloctane 1-eikotyloxy-7-(4-hydroxyphenyl) -3,7-dimethyloctane 1-crotonoyluoquine-7-(4-hydroquinphenyl) -3,7-dimethyloctane 1 -Cyclohexanecarbunyloxy-
7-(4-hydroxyphenyl) -3,7-dimethyloctane-1-phenylacetoquine-7-(4-hydroquinphenyl) -3,7-dimethyloctane-1-pentyloxy-7-(4-hydroxyphenyl )-3,7-
・Dimethyloctane 1-(4-methylindiyloxy)-7-(4-hydroxyphenyl) -3,7-dimethyloctane 6-(2-hydroxyphenyl-6-methyl-2-methylamine hebutane 6-( 2-Hydroxyphenyl)-6-methyl-2-dimethylaminohebutane 2-n-ethylamino-6-(4-hydroxyphenyl)-6-methylhebutane 2-n-butylamino-6-(2-hydroxy phenyl)-6-methylhebutane 2-di-n-butylamino-6-(2-hydroxyphenyl)-6-methylhebutane 6-('2-hydroxyphenyl)-6-methyl-2-
Morpholinohebutane 2-amino-6-(2-hydroxyphenyl)-6-methylhebutane and its hydrochloride 2-ami/-6=(4-hydroxyphenyl)-6-methylhebutane and its hydrochloride 2- Acetamide-6-(2-hydroxyphenyl)-
6-Methylhebutane 2-acetamido-6-(4-hydroxyphenyl)-
6-Methylhebutane 2-eicosanamide-6-(4-hydroxyphenyl)-6-methylhebutane 2-crotonamide-6-(4-hydroxyphenyl)
-6-Methylhebutane 2-cyclohexylcardenyamide-6-(4-hydroquinfer)-6-methylhebutane 2-inzamide-6-(4-hydroxyphenylene/L/) to -6-methyl Dimethylbutane 3-(2-hydroxyphenyl)-3-methylbutanephosphonate 3-(4-hydroquinophenyl)-3-methylbutanephosphonatedimethylthanephosphonate 3-(2-hydroquine-5-methylphenyl) -3-methylbutanephosphonate (4-hydroxy-3,5-dimethylphenyl)
-Dimethyl 3-methylbutanephosphonate 3-(4-hydroquine-3,5-noisozolopylphenyl) -Dimethyl 3-methylbutanephosphonate 7-(4-hydroxyphenyl) -3,7-cystyloctanephosphonic acid Diethyl 2-ethoxycarbonyl-5-(2-hydroquinophenyl)-5-methylhexanephosphonate Diethyl 2-ethoxycarbonyl-5-(4-hydroxyphenyl)-5-methylhexanephosphonate 3-(2-hydro quinphenyl)-3-methylbutanephosphonic acid 3-(2-hydroquine-5-methylphenyl)-3-methylbutanephonufonic acid 3-(2-hydroxyphenyl)-3-methylbutanemethylphosnic acid and Its sodium salt 3-(4-hydroxyphenyl)-3-methylbutylphosphonic acid didodezyl 2-(3-(4-hydroxyphenyl)-3-thylbutyl)-2-okine-1.3.2- ・dioxa Phosphorane 1-bromo-7-(4-hydroxyphenyl) = 3.7
- Dimethyloctane 7-(2-hydroxyphenyl) -3,7-dimethyl-1-nitrooctane 7-(4-hydroxyphenyl) -3,7--/Methyl-1-nitrooctane 1-acetoquine-3- (4-hydroxyphenyl-3-
Methylbutane 6- (2-hydroxyphenyl)-6-methyl-2-
He-sitanone 6-(4-hydroxyphenyl)-6-methyl-2-hegetanonecis-[4-acetyl-1-(4-hydroxyphenyl)]-]1-methylZchlorhexanetrans-4-acetyl- 1-(4-hydroxyphenyl))-1-methylcyclohexane 1-cyano-4-(2-hydroxyphenyl)-4-methylpentane 1-17/-4-(4-hydroginphenyl)-4-methylpenta / Nsu [4-cyano-1-(4-hydroxyphenyl)
)-1-Methylcyclohexane trans-[4-cyano-1-(4-hydroquinphenyl))-1-methaneclohexane 2-cya/-5-(
Ethyl 4-hydroxyphenyl)-5-methylhexanoate) (1-(4-hydroxyphenyl)-4L
methoxycardenyl]-1-methylcyclohexanetrans(1-(4-hydroquinphenyl)-4-methoxycardenyl)-1-methylcyclohexanecis-(1-(2-hydroxyphenyl)-4-I toxical? ]-1-methylcyclohexanedine [:1-(2-hydroxyphenyl)-4-methoxycaly+e=]-1-methylcyclohexanesu[1-(4-hydroxyphenyl)-cis-3,
4-dimethoxycarnyl]-1-methylcyclohexanetrans-c-1-(4-hydroxyphenyl)-cis-3,4-dimethoxycarnyl]-1-methylcyclohexanecis-(1-(2-hydroxyphenyl) -5-methyl7enyl)
-4-methoxycarvinyl-1-methylcyclohexanetrans-[:1-(2-hydroxy-5-methyl7x
=l)-4-methoxycaryl'l]-1-methylcyclohexanecis-(1-(4-hydroxy-3,5-diisopropylphenyl)-4-methoxy/carvinyl)-1-methylcyclohexanetrans-[ 1-, (4-hydroxy-3,5-diisopropylphenyl)-4-methquinecarbonyl]-1-
Methylcyclohexane trans-(1-(4-hydroxy-3,5-diisopropylphenyl)-4-carboxy)-1-methylcyclohexane trans-(1-(3,5-di-t-butyl-4-hydroxyphenyl) )-4-methoxycarvinyl-1-methylcyclohexane 1,6-hexanediol and 4-methyl-trans-4
-(3I5-di-t-butyl-4-hydroxyphenyl)cyclohexane-1-caldenate diester 5=(5-carboxy-2-methyl-2-pentyl)-
2-hydroxybenzoic acid 2-hydroxy-5-(5-methoxycarbunyl-2-
Methyl-2-pentyl)benzoate methyl 3,5-bis(
5-carboxy-2-methyl-2-pentyl)-2-hydroxybenzoic acid 2-hydroxy-3,5-bis(5
-Methoxycarbonyl-2-methyl-2-4thyl)benzoate 5-(6-amino-2-methyl-2-heptyl)-2-
Hydroquine benzoate 5-(6-amino-2-methyl-2-heptyl)~2-
Hydroquine benzoate methyl 2-hydroxy-5-(2-methyl-4-phosphono-2
-butyl)2-hydroxy-5-(2-methyl-4-tumethylphosphono-2-butyl)benzoate methyl 4-hydroxy-3
-(5-methoxycarbinyl-2-methyl-2-pentyl)methylbenzoate 2-humanoxy-5-(5-methoxycarbinyl-2-methyl-2-pentyl)acetophenone 2-hydroquine-3-( 5-methoxycarvinyl-
2-methyl-2-pentyl]acetophenone 4-hydroxy-3-(5-methoxyrudenyl=2-methyl-2
-pentyl)acetophenone 2-hydroquine-5-(5
-methoxycarbunyl-2-methyl-2-pentyl)benzophenone 2-hydroxy-3-(5-methoxycarzenyl-2-methyl-2-pentyl)benzophenone 4
-Hydroxy-3-(5-methoxycarbonyl-2-methyl-2-pentyl)benzophenone 2-aneano 4-
(5-Methoxycarbonyl-2-methyl-2-pentyl)phenol 4-/ano-2-(5-methoxycarbonyl-2-methyl-2--+!!Ntimethyphenol 2-hydroxy-
5-(5-Methoxycarbonyl-2-methyl-2-pentyl)henzamide 4-humanoxy-3-(s-methoxycarbonyl-2-methyl-2-Allltin)benzamide 4-(5-methoxycal Δ- diru-2-methyl-
2-hentyl)-2-(methylthio)phenol 2-
(5-methoxyalyl-2-methyl-2-pentyl)-4-(methylthiolaphenol 4- (5-methoxycaryl-2-methyl-2-methyl-2-pentyl)-2-)
Lifluoromethylphenol 2-hydroxy-5-(5-methoxycardenyl=2-
Methyl-2--(l-methyl)benzenesulfone-2-hydroxy-5-(5-methoxycarvinyl-2-methyl-
2-pentyl]benzenesulfonamide 2-hydroxy-5-(5-methoxycarbunyl-2-
Methyl-2-pentyl)benzenephosphonic acid 2-hydroxy-5-(5-methquine carbunyl-2-
diethyl 4-(5-methoxycarvinyl-2-methyl-2-pentyl)-2-ditrophenolbis[2-hydroxy-5-(5-methoxyrudenyl-2-pentyl)phenylphosphonate] 2-methyl-2-pentyl]-3-methylphenyl]
Methane bis[2-hydroquine-3-(5-methoxycardinyl-2-methyl-2-pentyl)-5-methylphenylcomethane bis[4-hydroxy-5-(5-methoxycarginyl-2-methyl-2 --!Methyl)-3-methylphenylcomethane 2.2-bis[4-hydroquine-5-(5-methoxycarbonyl-2-methyl-2--'!!ntyl)-3-methyphenyl]furonoyant 1-Bis[2-hydroxy-5-(5-methoxycarbunyl-2-methyl-2-pentyl)-3-methylphenylconclohexane bis[2-hydroxy-5-(5-methoxycarbunyl-2- Methyl-2-pentyl]-3-methylphenyl]
Sulfide bis[2-hydroxy-5-(5-methoxycarbonyl-2-methyl-2-methyl)-3-methylphenyl]
Disulfide bis[2-hydroxy-3-(5-methoxycarbonyl-2-methyl-2-pentyl)-5'-:)tylphenyl]sulfoquindo bis[2-hydroxy-5-(5-methoxycarvinyl-2-methyl) -2--!Methyl)-3-methylphenyl]sulfonebis[2-hydroxy-3-(5-methoxycarbunyl-2-methyl-2-4thyl)-3-methylpennol]
Sulfide bis[4-hydroquine-5-(5-methoxycarbonyl-2-methyl-2-'''2thimethy-3-methylphenyl)ether bis[2-hydroxy-5-(5-methoxycarbonyl-2-methyl-2 -pentyl)-3-methy,I+/insol]ether 4.4'-dihydroxy-5,5'-(5-methoxycarbunyl-2-methyl-2-pentyl) -3,3'-
Dimethyldiphenylamine The present invention provides a method for producing a compound represented by formula (1).
say a phrase This method for producing a compound of formula (1) is carried out by using the following formula: is 2-1 for the hydroxyl group
The phenol represented by the following formula: (in which R2, R3, Q, n and k It is possible to introduce a group represented by (having the above-mentioned meaning) by reacting it with a functional alkylating agent (2). The alkylation process is
It is suitably carried out within a temperature range of 20-170'G, preferably 100-150°C. The catalyst is a Brønsted acid (
Br5nsted acid), active earth or metal salts. Preferred Brønsted acids for this purpose are inorganic mineral acids such as hydrochloric acid, sulfuric acid, perchloric acid and orthophosphoric acid, although they may also be organic or inorganic acids or their partial salts; Sulfone ip - Alkyl, aryl or alkaryl substituted inorganic acids such as toluenesulfonic acid and methanesulfonic acid; organic acids such as dichloroacetic acid, trichloroacetic acid and trifluoroacetic acid. Active earths suitable for alkylation include Fulmo
nt) 237 (trade name) and Full Cut (Fulc
at) 22 (trade name), aluminum phenoxide is the preferred metal salt. Preferred catalysts are active earths. The reaction may be carried out in the presence or absence of a solvent; suitable solvents include hydrocarbons such as benzene, cyclohexane and heptane. Other solvents include methanol/sulfuric acid and water/sulfuric acid, where the solvent acts as a catalyst. It may be produced from the compound of formula (1) by reacting with a compounding agent.More specifically, when obtaining the compound of formula (1) in which p is 1 and q is 0.1 or 2, the compound of formula (1) 0.1 to 1 mole of compound
1.0 moles of alkylating agent ■ are used; when p is 2 and q is O or 1, at least 2 moles of alkylating agent ■ are used per mole of compound of formula ■; R1 is S
is 0 or 1 and r is 0 or 1, in which case 4 moles or less of the alkylating agent ■ are used per 1 mole of the compound ■0.Alternatively, even if the R groups are the same, Compounds of formula (1), where p is 2 or 3, which may be different, are sequentially reacted with compounds of formula (1), where p is 1 or 2, using at least 1 mole of alkylating agent per mole of the compound. It may also be produced by introducing an R group (3). Alternatively, p is 1 or 2, q is 1 or 2, and R1 is C4
-Q is an alkyl group, the compound of formula I is prepared by alkylating the compound of formula I with at least 1 mole of α to C8 olefin or alcohol in the presence of an acid catalyst, where q is 0 or 1 and p may be prepared from compounds of formula 1 where is 1 or 2. A compound of formula (2) containing a group of formula (1) or (2) as defined above is a compound of formula (2) in which q is 0 and p is 1 or 2.
The compound may be produced by a well-known method such as condensation with a reagent capable of introducing a bonding group M. Specific examples of phenols ■ are listed below. Phenol, 0-cresol, m-cresol, p-cresol, 2.6-xylenol, 2.4-xylenol, 2-ethylphenol, 4-ethylphenol, 2
．． 6-ethylphenol, 2-isopropylphenol, 4-isopropylphenol, 2,6-diitupropylphenol, 2-5ec-butylphenol, 4-
Bec-butylphenol, 2+6--) -5ee-
Butylphenol, 4-t-butylphenol, 4-(
1,1,3,3-tetramethylbutyl)phenol, 4
-n-decylphenol, 2-chlorophenol, 4-
Chlorophenol, 2.6--)Chlorophenol, 2
-10 Rho 4-71 tylphenol, salicylic acid, methyl salicylate, 4-hydroxybenzoic acid, p-hydroquine methyl benzoate, 2-hydroxyacetophenone, 2
-Hydroxybutyrophenone, 4-hydroxyacetophenone, 2-hydroxybenzophenone, 4-hydroxyRnzophenone, 2-cyanophenol, 4-cyanophenol 1.2-hydroxyinzamide, 4-hydroxybenzamide, 2-methylmercaptophenol, 4- (methylthio)phenol, 4-(n-butylthio)phenol, 2-trifluoromethylphenol,
4-trifluoromethylphenol, 2-hydroxy 4
hydroquine inzenesulfonic acid, 4-hydroxybenzenesulfonic acid, 2-hydroquine benzenesulfonamide, 4-hydroquine inzenesulfonamide, 2-hydroquine inzenephosphonic acid, 4-hydroxybenzenesulfonic acid, 2-
Diethyl hydroxyphenylphosphonate, diethyl 4-hydroxyphenylphosphonate, 2-ditrophenol, 4-nitrophenol, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxy-3,3'-dimethyldiphenylmethane, 2 .2-di(4-hydroxyphenyl)furopane, [2,2-(4゜4'-dihydroxydiphenyl)propane J, 1゜1-di(4-hydroxyphenyl)cyclohexane, (1,1-(4, 4'
-dihydroxyphenyl)cyclohexane), 4.4'
-dihydroxydiphenylamine, 4,4'-dihydroxydiphenyl ether. Functional alkylating agent that is reacted with phenol■
is eliminated during the alkylation reaction process. to be transformed or transposed. It has a reactive center such as an olefin group or a hydroxyl group. Specific examples of olefins suitable for alkylating the compound represented by formula (1) are listed below. 5-Methyl-5-hexenoic acid, methyl 5-methyl-4-hexenoate, methyl 5-methyl-5-hexenoate, 5-
Ethyl methyl-5-hexenoate. 5-Methyl-5-hexene 111n-hexyl. n-hexadecyl, 5-methyl-5-hexenoate, 5,7.7-)methyl riftyl-4-octenoate, 1
, 7-Simethoxycarbonyl-4-methyl-3-hegetene, 1-acetoxy-3-methyl-3-butene, citronellol, lutronellyl acetate 1In-butyl ether, citronel acid, methyl citronelate, citronellyl nitrile, l-7''como-3,t-dimethyl-6-octene, 3,7-dimethyl-1-nitro-6-
Octene, diethyl 3.7-cymethyl-6-octene-1-phosphonate, methyl 2-methoxycarbonyl-5-methyl-4-hexenoate, 2-ethoxycarbonyl-5
-Ethyl methyl-4-hexenoate, diethyl 2-ethoxycarbonyl-5-methyl-4-hexene-2-phosphonate, ethyl 2-cyano-5-methyl-4-hexenoate, dimethyl brenylphosphonate, brenyl Diethyl phosphonate, 1-cyano-4-methyl-4-pentene, 6-
Methyl-6-hebuten-2-one, 2-amino-6-mether-5-hebutene and its hydrochloride, 2-amino-6-
Methyl-6-heptene and its hydrochloride, 2-acedoamide-6-mether-5-heptene, 2-7cetoide-6
-mether-6-hextene, 4-methoxycarbonyl-1
-Methyl-1-cyclohexene, 4-cyano-1-methyl-1-cyclohexene, 4-acetel-1-methyl-
1-7 Chlohexene. Specific examples of suitable functional hydroxyl compounds for the functional alkylation of compounds of formula vI are listed below. 2-Avino-6-hydroxy-6-meteheptane and its hydrochloride, 2-acetamido-2-hydroxy-6-
Metelhebutane, 11-amino-2,2,12-1rimether-1-tridecanol and the primary formula: Alkyl group + Y2 and Y4 are each independently a C□-C8 alkyl group; Y6 and Y6 are each independently a hydrogen atom or a C□-C4 alkyl group) A compound selected from Banoundecanols. The 11-aminoxidecanol slope, together with its industrial method of preparation, is described in detail in DE 28 31 299. Examples of suitable olefins for alkylating compounds of formula I where q is 0 or 1 and p is 1 or 2 include inbutylene and diimbutylene, where q is 0 or 1 and p Specific examples of alcohols suitable for alkylating compounds of formula I where is 1 or 2 include t-butanol and 1.1.3°3-tetramethyl-
1-butanol is mentioned. Any functional derivative of the compound of formula I can be converted into other different functional derivatives. For example, when Q is an acid group -CO□H, the acid group is esterified with a monohydric alcohol R'OH. The corresponding ester -C02R' or may be esterified with a dihydric alcohol R" (OH) 2 to form the corresponding ester (-CO2)2R40. If Q is an ester group -CO□ If R4, the ester group is transesterified to form another group R or R4.
0(z or has an ester group -C02R
' is treated with an amine R4R5 (H4 and R5 have the meanings given above) and converted to an amide-C0NR'R' or a cyamine R'HN-R'' -NHR
'(R's are each independent as described above). Compounds of formula I are useful as stabilizers and antioxidants in polymers, oils or photographic systems and as corrosion inhibitors. Compounds of formula I are useful as photographic quality intermediates. The present invention also provides a composition comprising a base and a compound of formula I as a stabilizer as defined above. , when the base is an aqueous medium in contact with metals, especially ferrous metals, and in this case, the compound of formula 1 has the function of preventing corrosion of the metal by the aqueous medium. The preferred condition is that the base material system is easy to oxidatively decompose,
In the case of organic compounds such as polymeric substances, oils or photographic systems, the compound of formula 1 functions as an antioxidant and optionally as a thermal antioxidant. The invention will be explained in more detail by the following examples. In the examples, 1 part and 1 are parts by weight and 11j!, respectively. The pressure is given in hibbar (mb). Example 1 (a) 94 parts of phenol, 14.2 parts of methyl 5-methyl-5-hexenoate and Fulmont
237 (trade name) was stirred at 110° C. for 20 hours. The catalyst was then filtered off from the partially cooled reaction mixture and the filtrate was distilled. After recovering 82 parts of phenol, methyl 5-(4-hydroxyphenyl)-5-methylhexanoate was obtained. This compound is... (0,49
1aHP) At 167-72°C, it has a primary salmon composition (@. CH Actual value: 71.01 8.60 Calculated value (C, H2oOa): 71.16 8.53 (
b) Implementation? 5.0 parts of methyl 5-(4-hydroxyphenyl)-5-methylhexanoate, 5.0 parts of sodium hydroxide and 50 parts of water were refluxed for 3 hours. Acidification of the homogeneous i#It with 36% hydrochloric acid gave an oil that solidified upon cooling. This solid was collected by filtration and recrystallized from petroleum ether at 40 to 60°C at 0°C to obtain 5-(4-hy)xyphenyl)-5-methylhexanoic acid. , 94~
Primary mold composition at 6°C (having 28.5 parts of -1-Meg-L-1-cyclohexene BB and 5.0 parts of Normont 237 (trade name) were incinerated and treated in the same manner as in Example 1.]-(]4-Hydroxyphenyl-4- Consisting of cis and trans isomers of methoxycarbonyl-1-methylcyclohexane, 4(0
, 3 carp ILP) was fractionally crystallized from both-stimulated ether at 167-94°C. Crystallization of the initial product from methanol and water yielded the trans isomer. This isomer is rn, p. It has a 5th order l1 composition (@) at 120~2℃. OH Actual value: 72,59 8.03 Calculated value (C engineering, R2゜03): 72.!15 8.12
Further crystalline product was obtained by concentrating the ether-containing mother liquor from which the initial product crystals were precipitated. When this was recrystallized from methanol and water, the cis isomer was obtained. 1 of this isomer at 1 U m, p, 128-30°C
The following N needle composition (has effect. CH Actual d] 11 I Direct Near 2.01
7.91 calculated value (C151 (2003):
72.55 s,t The esters of Examples 3 to 20, further illustrated in the following table, were obtained by the method described in Example 1. Example 21 (a) 12.5 parts of methyl 5-(2-hydroxy-5-methylphenyl)-5-methylhexanoate prepared as described in Example 10. 14.2 parts of methyl 5-methyl-5-hexenoate and p-
Toluenesulfonic acid], heated on an Oifl steam bath for 8 days. The reaction mixture was diluted with ether, washed with 2N sodium hydroxide solution, and evaporated. The remaining oil is distilled and heated to 200°C. ,4(0,
3 Simple HP) When the fractions are separated, 2.6-bi, 1. (5-
methoxycarbonyl-2-methyl-2-pentyl)-4
-Methylphenolka? I was beaten. This compound is 40
When recrystallized from petroleum ether at ~60°C, b,, (
0,3fi) (ri) 206~10℃, m, p, 55
At ~7°C, it has a first-order composition (has a function. CH Actual value: 70.25 9.01 Calculated value (,C23H3,O,): 7 o-389,24
(b) 2.6-bis(2-methoxycarbonyl-2-M'thyl-2-pentyl)-4-methylphenol of Example 21a was hydrolyzed with a potassium hydroxide water bath solution to give 2.
Recrystallization of the salmon ether from petroleum ether at 40-60°C gave the corresponding diacid with m, p, 138-40°C. CH Actual value: 's9.3s 9.13 Calculated value (C2□H3□0.): 69.20 8.8
5 Example 22 2,4-bis(5-methoxycarbonyl-2) of Example 8
-methyl-2-pentyl)phenol 3, 7.8 parts, 5
28.4 parts of -methyl-5-hexenoic acid and 3.0 parts of 1)-toluenesulfonic acid were heated on a steam bath for 48 hours. Proceed according to Example 21a. When distilled, 10% of 2,4-bis diester was mixed in. , 3 (0,23 parrot HP) 2°4 of 230-42°C
．． 6-) Lis(5-methoxycarbonyl-2-methyl-
2-pentyl)? ? Enol was obtained. Triester containing impurities is treated with potassium hydroxide.
D When hydrolyzed and recrystallized from water, it becomes pure 2゜4.6-)
Lis(5-carboxy-2-methyl-2-pentyl)phenol was obtained. This compound has m, p, 156-6
It has a first-order weight composition (%) at 0°C. CR actual value: 67.61 8.89 total T1-
Value (C27H4207): 67-76 s, s
4 Fire Alms 1J23 (a) 94 ftB of phenol, 35.4 parts of dimethyl brenylphosphonate and Flumont 237 (trade name) 5
．． 0 parts was stirred at 125°C for 15 hours. The reaction mixture was filtered, excess phenol was distilled off under reduced pressure, and the remaining oil was purified with ether with a boiling point range of 40-60°C.
of petroleum ether. When stored at 0<0>C, this bath Al75=dimethyl 3-(4-hydroxyphenyl)-3-methylbutanephosphonate was obtained. This compound has a primary type needle composition (@2) at m, p, 98-101°C. CHP actual value: 57.41 7.83 11
．． 38 calculated value (C□3■ (2□0.P): 57.
56 7.75 11.07(b) 3.0 parts of dimethyl 3-(4-hydroxyphenyl)-3-methylbutanephosphonate from Example 23a and 30 parts of 48% hydrobromic acid on a steam bath for 1 hour. The mixture was heated and then volatiles were removed at 80° C. under reduced pressure. When the remaining solid is recrystallized from water,
3-(4-hydroxyphenyl)-3-methylbutanephosphonic acid was obtained. This compound has rn, p, 192~
At 5°C, it has the following N cycle composition (a). . CHP actual value: 54.01 7.06 12
．． 52 calculated value (C11H□704P): 54°3
26゜99 12.34 Example 24 Phenol 94iA, 26 parts of diethyl 2-ethoxycarbonyl-5-methyl-4-hexene-2-phosphonate and 5.0 parts of fulmone) 237 (trade name) were added to 110'
C: The mixture was stirred for 24 hours, and then 6 iJ of the mixture was filtered. After removing excess phenol, 0.13mb (0,101
When the residue is short-circuit distilled with 1EffHP), 5-
(2-and 4-hydroxyphenyl)-2-ethoxy'/
A mixture of carbonyl-phonic acids was imbued. This compound has the following weight 1 set 5y. (H). C HP Real 6111 I Nao
: 60.14 8.16 7.73 Calculated value (C2.H3606P) : 60.15 8
．． 27 7.51 After injecting 10 parts of this mixture once into a column of 300 parts of glue force, previously inactivated with hexane containing 6% ethanol. Separation was performed using high performance liquid chromatography (H.P.L.C.). Ortho-substituted isomer pt = phantom, 5 Obtained by elution with 5-bar ethanol-containing hexane. When recrystallized at 0°C from petroleum ether at 40-60°C containing an ether with j>tg, m. p. The temperature was 78-80°C. Next.
The para-substituted isomer is obtained from dichloromethane solvent. When recrystallized from petroleum ether at 40-60°C containing 2 mackerel ether, m.p. p. The temperature was 86-9°C. Diethyl 2-ethoxycarbonyl-5-methyl-4-hexene-2-phosphonate used in this reaction was. Obtained by the following method. Dissolve 4.8 parts of IJum in 200 parts of absolute ethanol. 50 parts of diethyl 1-ethoxycarbonyletherphosphonate was added to this bath solution. Add 2 to this stirred reaction mixture.
31.3 parts of -bromo-2-methyl-3-butene were added dropwise at room temperature over a period of 1 hour. After the addition was complete, stirring was continued at room temperature for 1 hour and then at 60° C. for 2 hours. After cooling, filter the sodium bromide from the reaction mixture. reactor[
' was concentrated under reduced pressure to remove ethanol. Remove the remaining oil with ether. Wash the ether solution with water. Distilled away. Fractional distillation of the residue yielded diethyl 1-ethoxycarbonyl-4-methyl-3-penten-1-phosphonate. This compound h bo,3(0.23f1
1. Hri) at 126 to 34°C, and has the following N dispersion composition (1). C HP actual value: 54.87 9.17
9.84 Calculated value (C□4H270.P): 55.
(18 8.85 9.83 Example 25 2,6-xylenol 24.4 parts, 98 sulfuric acid 98 parts,
18 parts of water and 17.8 parts of dimethyl brenylphosphonate were stirred at room temperature for 4 days and then poured into 1000 parts of water. The separated oil was extracted with ether, and the ether solution was poured into water.
Washed sequentially with N potassium carbonate and water. After distilling off the ether.
Distilling the remaining oil. b, 4 (0.3 mHP) 2 0 3- at 0-5°C
(4-human o'f"/-3.5-dimethylphenyl)-
3#f Luptan phosphonate dimedel was obtained. When this compound is recrystallized from ether-containing petroleum ether with a boiling point range of 40-60°C, m.p. p. At 89-91℃. A crystalline product having the following weight composition (low weight composition) was obtained. HP actual value: 59. sls. 6710.3
4 Calculated value (C□, H, 50, P): 59.98
8.39 10.31 Example 26 (a) 35.6 parts of 2.6-diimbrobylphenol was used in place of 2.6-xylenol. When the same operation as in Example 25 was carried out, dimethyl 3-(4-hydroxy-3.5-diimpropylphenyl)-3-meterphthanephosphonate was obtained. This compound is. , a (0.231BHP) 1 8 0 ~
204℃, m. p. At 81-3°C. The following M1 composition (@contained. HP actual value: 64.22 9.29 9
．． 00 calculated value (C1-, 304P): 64.02
9.27 8.70(b) Example 26a-3-
(4-hydroxy-3,5-diinpropylphenyl)
-3-1 Dimethyl methylbutanephosphonate Example 23b
Hydrolysis according to the procedure provided gave 3-(4-hi)"0x-3.5-diinpropyl-7enyl)-3-methylbutanephosphonic acid. This compound had a small boiling point range of 40 When recrystallized from carbon tetrachloride containing petroleum ether at ~60°C, cod CHP with m, p, and 179~82°C Actual value: 59.Fl8 8.55
B-86 calculated value (C,, H2,04P"H2O): 5
8.95 8.95 g, 95 Example 2. 12.8 parts of 6-dichlorophenol, 5-methyl-
14.2 parts of methyl 5-hexenoate, 130 parts of 98% sulfuric acid and 24 parts of methanol were heated and stirred on a steam bath for 24 hours, and then the reaction mixture was treated in the same manner as in Example 125. Distillation yielded methyl Fl-(3,5-dichloro-4-hydroxyphenyl)-5-methylhexanoate. This compound is bo,, (0,38uHP)'140
~60°C, m, p, 101 ~ 3°C, first-order 1-day composition (
It had @. CHC1 Actual value: 55.18 6.04 2
3.07 Calculated value (C engineering,) 11. (J, 0.): 5
5.09 5.94 23.24 Examples 28 to 43 further illustrating the method of alkylating phenols are listed in the following table. Example 34b 3,7-dimether-1-nitro-6-octene V used in the preparation of the alkylated phenol of Example 34a; [
, 13.3 parts of anhydrous phloroglu-7nol and 1 part of urea were added to 200 parts of dimethylformamide prepared as follows.
3.3 parts of sodium nitrite and 12.0 parts of sodium nitrite were stirred, while maintaining the temperature below 25°C. Citronellyl bromide 2], 9 parts were added dropwise. After the addition was completed, stirring was continued for an additional 48 hours.Then, the reaction mixture was poured into water, and the separated organic phase was extracted with ether.
The extract was washed with water and evaporated. When the residual liquid is fractionally distilled,
bl, (1211iHP) 1.4.8 parts of 7tronellol below 10°C, followed by bl, (12uH
y) At 130-2°C the following mold needle composition (3,7 with @
8.2 parts of -dimether-1-nitro-6-octene were obtained. CI (N Actual value: 64.47 10.F17 7.
32i1 calculated value (C, oH□, NO2'): 64.83
10.30 7.56 Example 44 In 35.0 parts of methyl 5-(4-hydroxy-3-methylphenyl)-5-methylhexanoate of Example 9, 2.0 parts of 98% sulfuric acid, and 200 parts of toluene. Then, inbutylene was passed through the mixture for 2 hours at 75°C. Toluene solution? After washing with 1l-10 hydroxide) and subsequent water washing, the toluene was removed. Distillation of the residue gave methyl 5-t3-t-buna-4-hydroxy-5-methylphenyl)-5-merhexanoate. This compound is. 63(0
, 23 Visit By) 16s to 72°C with a primary composition (@) CH Actual value: 74.71 10.08 Calculated value (C19H3003): 74.47 9
．． 87 Example 45 5-(2
-Hydroxy-5-inglobylphenyl)-5-methylhexanoic acid was used in the same manner as in Example 44. Methyl 3-t-butyl-2-hydroxy-5-impropylphenyl)-5-methylhexanoate was obtained. This compound has the following revised composition (@. CH actual value: 75.58 10.31 subtraction value (C21H3403): 75.41 10.25
Example 5-(2-hydroxy-5-methylphenyl)-5-methylhexane dissolved methyl 50 g (l, imbutylene 30B
+1. p-) 2.0 M of luenesulfonic acid and 160 parts of cyclohexane were sealed in an autoclave and heated at 100°C.
I pushed it for 24 hours. Take out the reaction mixture and add 1
After washing with 0% sodium hydroxide and then water, the residual oil obtained by distillation was mixed with 500 parts of silica and 4
Petroleum ether at 0 to 60°C was supported on a column prepared from a medium and subjected to column chromatography. Elution with petroleum ether containing 5% ether gave pure menal 5-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-methylhexanoate. This one-hi compound Vj, bo,, 3 (0,101 m) 1
y) 142-50℃-c, rnottft group bZ
(%) 'r, there is. C) 1 Actual 11111 value: 74.94 9.9
1it calculation value (C,, H3oO3): 74. '47
9.87 After alkaline hydrolysis, the above ester is recrystallized from petroleum ether with a boiling point of 40-60°C to give 5
-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-methylhexanoic acid was obtained. Co(7) compound has m, p, 11 composition (@) of first order at 99-101'C. C'H Real value: 73.35 9.85 Subtraction value (C18H2803): 73.93 9.6
5 Example 47 5-(3,5-di-t- Methyl butyl-4-hydroxyphenyl)-5-methylhexanoate Total v1 points When recrystallized from petroleum ether at 40-60°C, m, p. The temperature was 71-2°C. This compound has the following composition ((2
). c H Actual value: 75.96 10.64 Calculated value (C2°H3603): 75.81 10.41
Example 48 Starting from methyl 5-<5-t-butyl-2-hydroxyphenyl)-5-methylhexanoate from Example 17 and imbutylene. ,, (0,531EHri) 152
Producing methyl 5-(3,5-di-t-butyl-2-hydroxyphenyl)-5-methylhexanoate at ~8°C,
It was refined according to the method of Example 46. CH Actual value: 75.78 10.47 Calculated value (C2□H3603): 75.81 10.41
Example 49 In a bath solution of 20 M of cis- and trans-4-methoxycarbonyl-1-(p-hydroxyphenyl)-1-methyl-cyclohexane of Example 2, 2.0 parts of '98% sulfuric acid and 50 parts of benzene. , butylene was passed through the mixture at 70° C. for 3 hours. At the end of the conduction, the cooled bath liquid was diluted with ether, washed with 1 sodium bicarbonate and evaporated. The remaining oil was then diluted with petroleum ether having a boiling point of 40-60°C. cis-[4-methoxycarbonyl-1 as the second product
-(3,5-di-t-butyl-4-hydroxyphenyl)3-1-methylcyclohexane crystals were obtained. This compound has a primary composition (m, p, 152-5°C) (
%il. CH Actual value:, 76.79 10.07 Calculated value (C,, H360,): 76.62 10.0
7 m, p as second products from the mother liquor of the above crystalline product. A crystalline product with a temperature of 92-5°C was obtained. This crystalline product was recrystallized from methanol to obtain pure trans-[4-methoxycarbonyl-1-(3,5-di-t-butyl-4-hydroxyphenyl))-1-methylcyclohexane. This compound is m, p. It has a first-order 1-density composition ((6) at 95 to 7°C. c H Actual value: 76.90 10.02 Calculated value (C23H3,0,): 76.62 l O
,07Example 5゜)7ns(4-methoxycarbonyl-1-(3,5-
(di-L-butyl-4-hydroxyphenyl), 1-1-
27.0 parts of methylcyclohexane. 1.6-hexanediol 4.4 parts and 13mb
(10aHP) Stirred for 724 hours. After adding 2.0 parts of glacial acetic acid, the reaction mixture was diluted with ether, washed with water,
Distilled away. The remaining solid was recrystallized from methanol. 4-Methyl-trans-4 of 1.6-hexanediol
-(3,5-di-t-butyl-4-hydroxyphenyl)cyclohexane-1-carboxylic acid diester was obtained. This compound has a primary superposition composition (@f6: m, p, 120-2°C.
77.80 9.84 Calculated value (
C. H,80,): 77.47 10.1
4 Examples 51 to 53, further illustrating esters similarly prepared according to the procedure of Example 50, are listed in the following table. Example 5-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-methylhexanoic acid2. 25 parts of toluene mixed with Om and 2.0 parts of thionyl chloride were left at room temperature for 2 hours. Then, toluene and other volatiles were added to
It was removed at room temperature under a pressure of 16 mb (1211 Hj'). Then 10 parts of 1.1.3.3-tetramethylbutylamine were added to the residue and the mixture was heated on a steam bath for 3 hours. After diluting the reaction mixture with ether, the ether solution was washed successively with dilute hydrochloric acid, water, dilute sodium hydroxide, and water. When the ether is distilled off and recrystallized from petroleum ether with a boiling point of 60-80°C, 1.1.3.3-tetramethylmethylamine and S-<3-t-butyl-2-hydroxy-5-methylphenyl) are obtained. Abad with -5-methylhexanoic acid was obtained. This compound is m, p. It has a primary chemical composition (a) at 110-2°C. CHN actual value: 77.30 11.24
3.40 Calculated value (C26H, 6No□): 77
．． 37 11,24 3.47 Example 55 5-(3-t-butyl-2-hydroquine- of Example 46)
9.0 parts of 5-methylphenyl)-9-methylhexanoic acid and 30.0 parts of n-dodesolamine were stirred at 175°C for 24 hours. When excess dodenorabane is distilled off, n-
An amide of dodecylamine and 5-(3-t-phthyl-2-hydroxy-5-methylphenyl)-5-methylhexanoic acid was obtained. This compound is bo, s(0,23
MHP) 246℃. m, p, has a primary IT composition (@) at 43-5°C. CHN Actual value Near 8°64 11,84 2.9
3 calculated value (C3°H, N02): 78.43 11
．． 54 3.05 Example 5-(3-t-butyl-2-hydroxy-
5-methylphenyl)-5-methylhexanoic acid 14.6
72.9 parts of 81X and hexametelenedia were heated at 150℃.
It was heated for 24 hours. When the solid obtained by cooling is recrystallized from toluene, 1,6-diabanohexane and 5-
Thiagod with (3-t-butyl-2-hydroxy-5-methylphenyl)-5-methylhexanoic acid was obtained. This compound has a first-order mass at m, p, 139 to 42°C.

[
# Composition (head) I1 c, CHN ν36 River I Nao
: 76.17 10.08 4.1
9t'[)[(C42H, 8N204):
75.9] 10.23 4.24 Example 57 5.0 parts of R-(3-t-butyl-2-human quin-5-15F ruphenyl)-5-nor-1r-ruhexanoic acid of Example 46 and 20 parts of aniline was refluxed for 20 hours and then poured into the excess vinegar. The separated oil was extracted with ether, then washed with 2N hydrochloric acid, bicarbonate, IJ solution, and water. Distilling off the ether gave a brown solid. This was then subjected to N'BM from 100 parts of silica and a petroleum ether solvent with a boiling point of 40-60°C and passed through nine columns. When eluted with the above bath containing 10% ether and recrystallized from petroleum ether with a boiling point of 40-60°C containing two ethers, m, p, N of 122-4°C are obtained.
-71Nyl-5-methyl-5(3-t-butyl-2-hydroxy-5-methylphenyl)hexanamide was obtained. CHN actual value: 78.06 9.09 3.
50 calculated value (C2, H33NO,): 78.43
9.05 3.81 Example 58 30.4 parts of methyl salicylate, 28.4 parts of methyl 5-methyl-5-hexenoate, 130 parts of 98% sulfuric acid and 24 parts of methanol were stirred at room temperature for 4 days. The reaction mixture was treated as described in Example 25,
When distilled * b63 (0,23 追Hy) 150~2
2-Hydroxy-5-(5-methoxycarbonyl-
Methyl 2-methyl-2-pentyl)benzoate: H Actual value: 65.27 7.65 Calculated value (C□, H2, OS): 65.29 7.53 and bo,, (0,081EIHj') 220℃ 2
-Hydroxy-3,5-bis(5-methoxycarbonyl-2-methyl-2-pentyl)methylbenzoate: CH Actual value: 65.75 8.28 Calculated value (C24H3607): 66.03 8.3
1 was obtained. When the above ester li k is hydrolyzed with alkali, m, p
. 5-(5-carboxy-2-methyl-2
-pentyl)-2-hydroxybenzoic acid and m, p,
3.5-bis(5-carboquine-2-methyl-2-pentyl)-2-human 0-oxybenzoic acid was obtained at 161-3°C. Methyl 5-(6-amino-2-methyl-2-hebutyl)-2-human oxybenzoate (i-) can be obtained in the same manner as in Example 58. C).CM N Actual value: 67.93 9.10 4.
90 calculated value (C16H25No.): 68.79
9.02 5.015-(6-A1)-2-methyl-
2-hegtyl)-2-hydroxybenzoic acid, m, p, 1
82-5°C: CHN Actual value: 64.58 8.97
5.00 Calculated value (C15H2, No, ・) 120G
63.58 8,89 4.942-Hydroxy-5-
Methyl (2-methyl-4-dimethylphosphono-2-butyl)benzoate, bo, □ (0,081JLHF)
1 7 5 ℃: CHP Actual value: 54.20 7.3o 9
．． 08 calculated value (C,, H230, P): 54.5
4 7.02 9.382-Hydroxy-5-(2-methyl-4-phosphono-2-butyl)benzoic acid, m, p,
125-35℃ 2C1-LP Actual value: 49.07 6.25 11
．． 97 calculated value (C□2H□, 0.P): 50.0
0 5.95 10.744-hydroxy-3-(5-
Methyl methoxycarbonyl-2-methyl-2-pentyl)benzoate. m, p, 80~2℃: CH Actual value: 6F+, 45 7.68 subtraction value (C□6n22og): 65-2 q
7.53 Example 59 tR stirring of 19.0 parts of water, 98% tffl [90.5 parts and 0.2 parts of sodium dodecylbenzenesulfonate @
i&ni. 25.0 parts of methyl 5-(4-hydroquino-3-methylphenyl)-5-methylhexanoate from Example I+l19 and 1.0 part of petroleum ether of 80-100"C were added. The temperature of the stirred mixture was increased to 80"C. Then, 4.4 parts of 40% formaldehyde was added dropwise every hour. After the addition was completed, the temperature was raised to 80"C for another 2 hours.
After the mixture was heated, 100 parts of water was added. The organic phase was extracted with ether, the extract was washed with bicarbonate, water and evaporated. When the residue is short-circuit distilled, bo,, (
5-(0,53 HP) 150"C (open temperature)
Methyl 4-hydroxy-3-methylphenyl)-5-methylhexanoate 11. . Department, followed by that. ,y (0,53fυ4Hy)
250℃ (open temperature)
-(5-Me)oxycarbonyl-2-methyl-2-pentyl)-3-methylphenylcomethane was obtained. C) I ・ Real 6411 Sen: 72.55 8
．． 69th revision value (C31H,,06): 72.63
8.65 Example 5-5 of Example 10 according to the method described in Example Row 59
From methyl (2-hydroxy-5-methylphenyl)-5-methylhexanoate, b. 7 (0,053 words HP)
Bis[2-hydroxy-3-(5-methoxycarbonyl-2-methyl-2-pentyl)-5-methylphenylcomethane] of 284"C was obtained. CH 1 value: 72.75 8.30 Calculated value (C3□H4606): 72.63 8
．． 12.2 parts of 2.6-dimeterphenol, 5.3 parts of citronellyl@n-butyl ether and 1 part of 70% perchloric acid
．． 30 parts of methylene chloride mixed with 0 parts was left at room temperature for 3 days. After pouring the mixture into water, it was extracted with ether, and the ether solution 1 [sodium carbonate solution, then washed with water and distilled off, the remaining oil was distilled, b.
8 (0,6 excitation Hy) 1-n as both parts of 168-76℃
-Butoxy-7-(4-hydroxy-3,5-dimethyl7:r-:ru)-3,7-dimethyloctane was obtained, CH Actual value: 79.05 11.52 Calculated value εC2□H3802) : 78.99 ] 1.
45 Example 62 4-(5-methquinecarbonyl-2-nonal-2-pentyl)phenol 10.3J Citronellyl n-butyl ether 4.2 parts and 70% Mo, A chlorine Mt 0.5
25 parts of methylene chloride were left at room temperature for 4 days. Treated according to Example 61. When distilled, bo, 8 (0,6 mHy) 22 s ~ 3
2-(8-n-butoxy-2,6-dimeteru2) at 6°C
-octyl)-4-(5-methoxycarbonyl-2-methyl-2-pentyl)phenol was obtained. , CH Actual value: 75.02 11.08 Calculation (1i (028H4804): 74.95
10.78 Example 63 2.3 parts of 4-1-decylphenol, 5-methyl-5-
1.4 iF' of methyl hexenoate, 0.25 parts of 70% perchloric acid and 10 parts of methylene chloride were left at room temperature for 12 days. When processed and distilled according to chestnut processing method 61, b
o, 8 (0,6 g, Hj) 5-(5-
Methyl n-decyl-2-hydroxyphenyl)-5-methylhexanoate was obtained. H Actual value: 76.66 10.80 Calculated value (C24H4003): 76-5510-7 s
Example 64 2-methyl-4-(F
, -meth)-'f-dicarbonyl-2-nonal-2-pentyl)phenol 5.013 α-methylstyrene 2
4 parts of 70% overheated acid: 0.5 parts of acrylic acid were reacted and treated as described in Example 61. It is distilled as an oil. ,, (0,53#,)LP) 210
5-(3-hydroxy-5-methylphenyl)-5-methylhexane at ~4°C was added to (JJ). This compound has the following weight composition (CH real 6111 value) : 78.22 8.75 Calculated value (C24H3□03) : 78°78 8.8
9 Fire Enri 65 2-Hydroquinoacetophenone 2762 BIS and methyl 5-methyl-5-hexenoate 14.2 i1+ were mixed with W.
;4 Added to the prepared bath solution. After stirring the reaction mixture at room temperature for 3 days, it was poured into water and the organic phase was extracted with ether. The ether extract was washed with sodium bicarbonate and water and then evaporated. The residue was distilled to give 2-hydroxy-3-(
5-methoxycarbonyl-2-nonal-2-pentyl)
A mixture of acetophenone and 2-hydroxy-5-(5-methoxycarbonyl-2-methyl-2-pentyl)acetophenone was obtained. CH Actual value: 69.31 8.19 Calculated value (C, 61-12□0.): 69.04 7.
97 Example 66 Art f! except that 2-hydroxybenzenephenone 19.8131st was used instead of 2-hydroxyacetophenone. /l, 165 was repeated. The period is 5 days. By distillation b, 7 (0,5311 mHy) 1
A fraction of 98-204°C was obtained. Both components are 2-hydroxy-3-(5-methoxycarbonyl-2-methyl-
2-pentyl)benzophenone and 2-hydroxy-5
-(5-methoxycarbonyl-2-methyl-2-pentyl)benzophenone.
CH Actual value: 74.00 7.32 Calculated value (C2□H2,04): 74.09 7.11
Example 67 Methyl 5-(4-hydroxy-3-methylphenyl)-5-methylhexanoate obtained as described in Example 9, allyl alcohol in the presence of p-toluenesulfone catalyst. transesterified with b,7(0,53
aHP) 5-(4-hydroxy-3-
Allyl (methylphenyl)5-methylhexanoate was obtained. CH Minoru 6 River I Nao:
73.69 8.66 Calculated value (C engineering, H2403): 73.88 8.75 Example 68 According to the method of Example 67, cyclohexanol and 5-(
From methyl 4-hydroxy-3-methylphenyl)-5-methylhexanoate, b,, (0,681H))2
Cyclohexyl 5-(4-hydroxy-3-methylphenyl)-5-methylhexanoate was obtained at 00-4°C. CH Actual fi+'￥: 75.03 9.41
Calculated value (C2, H3oO3): 75.43 9.
Example 50 In a stirred suspension of 100 parts of anhydrous tetrahydrofuran mixed with 2.0 parts of lithium aluminum hydride, 5.3 parts of 2-acedoabado-6-(4-hydroxyphenyl)-6-metehbutane were dissolved. 50 parts of anhydrous tetrahydrofuran were added. After the addition is complete, the reaction mixture is heated for an additional 21f at room temperature. The mixture was stirred and then ethyl acetate was added to decompose excess lithium aluminum hydride. The mixture was then poured into water and the solids were filtered off. Extract the aqueous phase and solids with ether, ether! ? [Washed with all water and evaporated. The remaining oil was heated to an open temperature of 190°C. Short-circuit rotary distillation at 0.7 mb (0,531 mHy) gave 2-N-ethelagono-6-(4-hydroxyphenyl)-6-methylheptane as a colorless oil. HN actual value: 76.78 11. ．． 26 5
．． 50 Calculated value (C,, H2, NO): 77.06
10.91 5.62 Example 70 10.0 parts of thionyl chloride was added to 75 parts of toluene in which 1000 parts of 5-(4-hydroxyphenyl)-5-methylhexanoic acid was clouded. The mixture was gradually warmed to 50° C. to remove all suspended acid in mM and then left overnight at room temperature. Then remove toluene and other volatile components under reduced pressure. It was removed at room temperature, and the residual liquid was treated with 75 parts of an ammonia water bath solution of 0.88 (P/1 tll). The 41 phase was extracted with ether and the ether solution was washed with dilute #A acid followed by water and evaporated. The residue was taken out with diluted sodium hydroxide, and the liquid was treated with solid carbonic acid (dry ice).
Recrystallization from ether-colored methanol gave 5-(4-hydroquinphenyl)-5-methylhexanamide with rn, p, 137-9°C. C) I N Actual value: 70.48 8.57 6.
03 words 1 Calculation (C□3H,,NO,):
70.56 8,65 6.33 Meijin t I N Kuri 71 Methyl 5-(4-hydroxyphenyl)-s-metahexanoate 5.0 @I and 750 parts of n-butyl aba were sealed in a glass tube. and heated at 200°C for 24 hours. After cooling the reaction, the excess butylamine was removed under reduced pressure; the remaining oil was subjected to short-circuit rotary distillation at 0.7 mb (0,53 min Hy). N-n-phthyl-5-(4-hydroxyphenyl)
-15-methyl-xanabad was obtained. HN Fruit 11 value: 73.47 9.99 4
．． 82 calculated value (C17H27No,): 73.61
9.81 5.05 Example 72 Example 71 was repeated using 50 parts of diethylamine in place of the n-phytylamine. Heating time is 48 hours. N,N-diethyl-5-(4-hydroxyphenyl)-5-methylhexanamide was obtained from this reaction product. This compound has the following switch composition (9)). RN actual measurement value: 73.43 9.95 4.・
62 calculated value (C□7H,,NO,): 73.61
9,81 5.05 Corrosion inhibitory effect in active compounds of formula 1. The following composition: 20P, C,SO2・2H2015P,
MgSO4・7H204,6y, NaHCO
s 7.71! , CaCl2・6H2045, //
Colon 1701) Aerated bath liquid bottle test using standard corrosive water consisting of distilled water (Aer
ated 5solution Bottle Te5t
) was proven using the following method. A 5 cm x 2.5 mm piece of mild steel was cleaned with pumice, immersed in hydrochloric acid for 1 minute, then washed, dried, and weighed. Compound of formula I 0. The IP was dissolved in 100 sI/ of standard corrosive water. The concentration was 100 ppm. The steel pieces were suspended in the solution and the whole was stored in a thermostatically controlled bottle at 40°C. During storage, air was passed into the solution at a rate of 500 parts/m2, but the air passage was blocked by a piece of steel. Water loss due to evaporation is caused by the water being removed by a leveling device (c
It is replenished by being supplied as distilled water from the instant head apparatus. After 48 hours, take out the steel piece, clean it with pumice, and place it in one layer.
It was immersed for 1 minute in hydrochloric acid to which iL% of hexane was added, then washed, dried, and weighed again. A slight decrease of 1 yen occurred. Blank test, i.e. any
Continuous low iron tests were each carried out by immersing mild steel specimens in test water in the absence of potential corrosion inhibitors. The corrosion rate is expressed as weight loss t/square decimeter/day (m, d, d,) in mP, but for convenience, the unity is expressed as the linear equation: The obtained results are shown in the first
It was posted on the table. TABLE 1 Mild Steel Corrosion Prevention of Compounds of Formula I in Standard Corrosion Water The results of Table 1 indicate that compounds of Formula I have effective moderate F+ corrosion inhibiting properties. The corrosion resistance of the cutting water bath liquid composition of the present invention was determined by the Japan Petroleum Association test by 1%.
(the In5 position of Petrole
It was evaluated by the method below, which is a modification of um'l'est) 287. In the test, enough TEA was added to a 1% aqueous corrosion inhibitor solution to adjust the pH value to 9. Furthermore, this Iwa frg was diluted 2.4, 8, and 16 times, and each liquid resistance was brought into contact with a piece of chime iron according to the IP287 test procedure. The test was conducted using ion-exchanged water. Visual evaluation of the condition of the gold strips after being immersed is based on the first-order standard. No rust O ≦5% T (slight) ≦10 rust area (in Mc) ≦10% rust area S (strong) The results obtained are shown in Table 2, and this is due to the This clearly shows the effectiveness of the compound. Example 81 The thermal oxidation prevention of the active f-hybrid compound of formula I dissolved in temperature-controlled oil was evaluated according to 1 Petroleum Institute Test 229. Test oil, water and a copper catalyst coil were placed in a glass container and placed in a cylinder equipped with a pressure gauge. Pressure inside the cylinder with oxygen is 90 psi (6.3 Kf/
d) Pressurized to 150°C, placed in a heated oil bath, and rotated at 1100 rpm in the axial direction at an angle of 30 from the horizontal plane.
I rotated it. The onset time (in minutes) at which the test oil begins to react with the supplied oxygen is measured. End...f is indicated by a constant decrease in pressure. , The results listed in Table 3 show how the compound of formula 1 is prepared using rotary vacuum oil (Rotary Vacuum QiC).
RVO) and reduce the production of acidic by-products when compared to RVO in the absence of such additives.

Claims (1)

[Claims] (1) The following formula: (wherein p is 1.2 or 3, and q is 0°1 or 2, provided that p+q≦3; R is the following formula ■ : 2 is a group represented by ', and when p is 2 or 3, each group R
may be the same or different. is present at the 2-94- or 6-position; n is an integer from 2 to 30; is 1 or 2; Q is the following group; 1) -C00E' or -〇〇NR4R11 : [In the above formula, R4 is an elementary atom; optionally separated by 1 to 5 oxygen atoms, and optionally a group ~OR'(R' is C9
~C+Z 7-chloroalkyl group, linear or branched 03~(40 alkenyl group, optionally substituted with - or 200, ~C4 alkyl group)
aryl group or C1-C83 aralkyl group)
A straight chain or branched alkyl group having 1 to 20 carbon atoms substituted with; a divalent straight chain or branched alkylene group having 2 to 20 carbon atoms; a straight chain or branched chain having 3 to 20 carbon atoms; Alkenyl group; cycloalkyl group having 3 to 12 carbon atoms; aryl group having 6 to 10 carbon atoms, optionally substituted with a C1 to C4 alkyl group: carbon, aralkyl group having 7 to 13 atoms; oxygen atom a 5- or 6-membered heterocyclic group containing an oxygen atom, optionally substituted with a - or two C, -C linear or branched alkyl group; or containing an oxygen atom, optionally a C or two C, -C
, 5 substituted with a straight or branched alkyl group of
or a methyl group substituted with a 6-membered heterocyclic group, provided that when k is 2, the two carbon atoms to which the group -COOR' is bonded are not adjacent to each other; R5 is a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms, while W and R5, together with the nitrogen atom to which they are respectively bonded, optionally contain - or two C1 to C4 atoms. It may form a 5- or 6-membered heterocyclic group substituted with an alkyl group. [II)
-OX: [In the above formula,
0 straight or branched alkyl group; 3 to 2 carbon atoms
0 linear or branched alkenyl group; C5-C12 cycloalkyl group, C1-CI3 aralkyl group; or C6-C0° aryl group optionally substituted with - or two 01-C4 alkyl groups. It is. ]Il+
) -NR8R': [, in the above formula, R8 is a hydrogen atom or a straight chain or branched alkyl group having 1 to 4 carbon atoms; R9 is a hydrogen atom, a straight chain or branched chain having 1 to 4 carbon atoms; alkyl group,
or is an acyl group of the formula -COR7 (R7 has the meaning given above); or R6 and R9, together with the nitrogen atom to which they are respectively bonded, are optionally - or an alkyl group of 2001 to 2001 to C4 forms a 5- or 6-membered ring group substituted with ]IV) -PO(OR”)C
o), R: [In the above formula, X is 0 or 1; when X is 1, R'' and R'' may be the same or different, and each a chain or branched alkyl group, or R'' and R11 are bonded to each other, optionally - or two Q'' = Ct
o may form a C1-C9 alkylene chain substituted with an alkyl group; when x is O, R'' is a hydrogen atom or a straight or branched alkyl group having 1 to 20 carbon atoms; and R'' is a C, -C, straight chain alkyl group. [V) CN1 halodane atom, No, : and vl) -COR'': [In the above formula, R'' is a hydrogen atom, a straight or branched alkyl group having 1 to 20 carbon atoms, or a halogen atom. ] and R3 may be the same or different and are each a straight chain or branched alkyl group having 1 to 5 carbon atoms; when Q is -COt R',
Either R2 or R3 is optionally a group=C02?
: Substituted (each group R4 is independent),
Alternatively, R'' or R3 may be bonded to the group CnH2n+t- to form a C3-CI2 cycloalkylene group substituted with the group -(COx R')kt (the groups R4 are each independent). (wherein R4 and k have the meanings given above); when Q is the group -COR''',
R2 or R8 may be combined with the group CnH2n+, -2 to form a C5-CI2 cycloalkylene group optionally substituted with the group -COR''; however, the group Q
is a group -co2a' (R4 is a divalent straight chain or branched alkylene group having 1 to 2 carbon atoms),
p and k are both 1, and the compound is represented by the following formula Ia: (wherein R'' is a divalent straight or branched alkylene group having 2 to 2 o carbon atoms); Based on
CONR' RII (R' ha carbon JiK-7-number 2~2
0 divalent straight or branched alkylene group, R
5 has the meaning given above), p and k are both 1, and the compound of formula 1 has the following formula 1b= (wherein 'R'' is a divalent straight compound having 2 to 20 carbon atoms), then p and k are both 1, and the compound of formula 1 is a chain or branched alkyl group); R1 is a C1-CIρ straight-chain or branched alkyl group;
C7-co aralkyl group, nologne atom, -CFs
, -8H, -sR'3, -Cozy, -CO! R”
, -coR'3, -CoCoHa, -CoNH,
, -CN, -8O8H1-8OzNHt, -PO(
OH)t , -PO(OR")z' or -Not (where R" is a straight-chain or branched alkyl group of CI-C4); when q is 2, the group R1 is May be the same or different; when q is 1, R1 in the formula ■ is the following formula ■ or ■: rod (N) (IV) [wherein R and R' have the above meanings; r is 0.1 or 2, and S is 0 or 1, provided that r0g≦2; M is a direct bond, -c (g')[has]l1l)-
, -8-, -HdoS-, -8O-1-8O2-1-C
1-I2SCH2-, -0-, -CH,QC几- or-
N R16- (here, RI4 and R1'' may be the same or different, each a hydrogen atom, optionally 1
A linear or branched alkyl group having 1 to 20 carbon atoms separated by ~3 sulfur atoms, an aryl group having 6 to 10 carbon atoms, or RI4 and R1'' are the carbon atoms to which they are bonded. together with - or 200, to form a 5- or 6-membered ring which may be further substituted with a C6 alkyl group; R16 is a hydrogen atom, and has 1 to 1 carbon atoms
2 straight or branched alkyl group or phenyl group). ] However, the compound of formula 1 has only one group of formula (■) or (■), and this group (■ or
is present at the 2-14- or 6-position with respect to the group -OH; p is 1, R1 is an alkyl group of C1 to C11, R2 and R
3 is an alkyl group of 01 to C6, k is 1, and Q is -C0OR
'(R' is a hydrogen atom, and when q has the above meaning, n is other than 2) and their salts with organic or inorganic acids and bases. (2) The following formula V: [wherein R1, p and q are defined as described in claim 1: Ro is the following formula: (wherein, R'' + R' + R', R '+ n and k are groups represented by ? defined as described in claim 1] Compound 0 according to claim 1 (3) where k is 1; A compound of formula 1 according to claim 2. (4) t is of the following formula; (wherein R1, R8, R4 and n are
3. A compound of formula V according to claim 3, which is a group of the formula (5) R'' and R3 are each a methyl group, and k
5. A compound of formula V according to claim 4, wherein is a straight-chain or branched C1-C6 alkyl group. (6) A compound of formula (2) according to claim 2, wherein n is 3. (7) p is 1, q, n, k, R, R
', R'. The compound of claim 1, wherein R3 and Q are defined as defined in claim 1. (8) A compound of formula (1) according to claim 7, wherein k is 1. (9i R' and R3 are each a methyl group, R
9. A compound of formula 1 according to claim 8, wherein ' is a C7-C3 straight or branched alkyl group. (A compound of formula I according to claim 1, in which IG n is 3 to 10. 0]) A patent that does not contain a group of formula ■ or ■ defined as described in claim 1 Compound of formula V according to claim 2 0 (+2' Composition consisting of a compound of formula I as defined in claim 1 as agent and stabilizer 0 03 Base The composition according to claim 12, wherein the metal is an aqueous point in contact with the metal. 1 (14) The composition according to claim 13, wherein the metal is an order metal. (151--The composition of claim 12, wherein the base is an organic substance susceptible to oxidative decomposition.