CA1067085A - Stabilizers for vinyl chloride polymers and copolymers - Google Patents

Abstract

The subject of the invention is new stabilizers for polymers and copolymers of vinyl chloride, characterized in that they correspond to the general form: in which, R1 and R2, which are identical or different, each represent an alkyl radical, linear or branched and comprising from 1 to 12 carbon atoms, a cyclohexyl radical, an alkyloxy radical, linear or branched and comprising from 1 to 12 carbon atoms, a benzyloxy radical, a hydroxy radical, where R1 and R2 together represent a radical alkylenedioxy comprising from 1 to 3 carbon atoms, R3 represents hydrogen, a methyl or methoxy radical, it being understood that: a) at least one of the substituents R1 and R2 does not represent an alkyl radical; b) the substituents R1 and R2 do not simultaneously represent hydroxy radicals when R3 represents hydrogen or the methyl radical; etc) the substituents R1 and R2 do not simultaneously represent alkyloxy radicals when R3 represents the methoxy radical. These stabilizers are particularly useful for the preparation of food packaging, because they meet in particular the "migration criterion of the stabilizer in the contents of the packaging".

Description

1 ~ 6708S
The present invention relates in one way general to stabilizers of polymers and copolymers of vinyl chloride, and more particularly ~ derivatives of 2-phenyl indole as new stabilizers for poly-vinyl chloride mothers and copolymers.
The present invention also relates to ~, as as new industrial products, ~ new derivatives of 2-phenyl indole.
The present invention finally relates to methods for preparing these stabilizers of polymers and copolymers ~ res vinyl chloride.
The compounds according to the invention are derivatives, di-or trisubstituted, 2-phenyl indole and have the formula following general:
Rl ~ 3 H

in which, Rl and R2, which are identical or different, each represents an alkyl radical, linear or r ~ mified and comprising from 1 to 12 carbon atoms, a cyclohexyl radical, an alkyloxy radical, linear or branched and comprising from 1 to 12 carbon atoms, a ben ~ yloxy radical, a hydroxy radical, or Rl and R2 together represent an alkylenedioxy radical comprising from 1 to 3 carbon atoms, R3 represents hydro-gene, a methyl or methoxy radical, it being understood that a) one at least of the substituents R1 and R2 does not represent simulta-particularly hydroxy radicals when R3 does not represent a radical alkyl, b) the substituents R1 and R2 do not represent simultaneously alkyloxy radicals when R3 represents hydrogen or the methyl radical, and c) the substituents Rl and R2 do not represent : -.
do not feel alkyl oxyl radicals simultaneously when R3 represents - the methoxy radical.

.. __. . ..

70 ~ 35 The compounds according to the i ~ ventiorl can, of my ma ~ lie ~ e general be prepared according to the Fischer method, making - r.cagir a cler.ive su ~ stitUe of acetoplleno1le ~ rél ~ on ~ allt.-1 la following general formula ~

'' ;,?

CH ~

dan ~ which Rl, R2, R3 take the same values as in the ~ general formula I, with phenylhydrazine to obtain a de-: ~ substituted rivet of phenylhydrazone of acetophenone corresponding ~ the ~ general formula:

~ 3 -YH-N = ~

in which Rl, R2 and R3 take the same values as above sus, and by cyclizing the compound of formula III either by means of a dehydrating agent such as, for example, sul ~ uric acid, a-polyphosphoric acid or zinc chloride, either by thermolysis, po ~ r obtain a substituted derivative of 2-phenyl indole corresponding the general formula Io hes compounds according to the invention can also 8tre - prepared according to the Blschler method, by reacting a derivative v substituted for acetophenone corresponding to the general formula:

O
'' R ~ -C-CH2X
R2 ~ IV

-2-,.

~) 67,085 in which Rl, R2 and R3 have the same values as in the general formula I and X represents a halogen ~ preferably : bromine or chlorine, with llaniline to obtain a derivative 8ub8 2-phenyl indole compound corresponding to the general formula I.
The compounds of general formula: -in which at least one of the substituents R1, ~ 2 and R3 represents has an alkyloxy radical, linear or branched and comprising 1 ~ 12 carbon atoms, can be prepared by reacting the corresponding hydroxylated derivative of formula I, said derivative having ~ tee prepared by one of the two general methods above ~
~ with an alkyl halide, linear or branched and comprising .. of 1 ~ 12 carbon atoms, in the presence of sodium methylate ......... and, optionally, N, N-dimethylformam ~ de.
~ es compounds of general formula:
-.

; H
in which at least one of the substituents Rl and R2 represents a hydroxy radical, can be prepared by demethylation of.s corresponding methoxylated derivatives of formula I which have been -. prepared by one of the two general methods above, at using aluminum chloride or pyridine hydrochloride, possibly in the presence of benz ~ ne.

~ es compounds of general formula II are known or can be prepared by methods known per se.
~ es compounds of ~ general formula IV are either known compounds, either can be prepared by reacting the appropriate compound of formula II has ~ a halog ~ ne, preferably Refer to bromine or chlorine.
~ es compounds-according to the invention have proven to be good stabilizers for vinyl chloride polymers and copolymers ~
such as, for example, polyvinyl chloride, chloride polyvinyl-polyvinyl acetate, polyvinyl chloride polyvinylidene chloride. They turned out to be particularly ~ ants for the stabilization of polymers and copolymers intended ~ ~ be shaped by molding-extrusion, extrusion ~
sou ~ lage and calendering, mainly, but not exclusively, intended for the manufacture of food packaging, such as bottles for the packaging of wine, oil,.
vinegar and mineral waters.
~ ~ es compounds according to the invention below are ~ new compounds and ~ claimed as in-: 20 new manufacturers:
Dihydroxy-2 ', 4' phenyl-2 indole (compound 1) Methoxy-3 'hydroxy-4' ph ~ nyl-2 indole (compound 2) Dimethoxy-3 ', 5' phenyl-2 indole (compound 3) Hydroxy-2 'methoxy-4' phenyl-2 indole (¢ omitted 4) : Hbdroxy-2 'methyl-4' phenyl-2 indole (compound 5) ~ ethyl-2 'hydroxy-4' phenyl-2 indole (compound 6) 2-methoxy-4-methyl-2-phenyl indole (compound 7) Methyl-3'-methoxy-4 'phenyl-2 indole (compound 8) ~ imethoxy-2 ', 4' phenyl-2 indole (compound 9) 2-methyl-4-methoxy-2-phenyl indole (compound 10) Methoxy-2 'methyl-5' phenyl-2 indole (compound 11) Methyl1-3 'hydroxy-4' phenyl-2 indole (compound 12) Hydroxy-3 'methoxy-4' phenyl-2 indole (compound 13) Dodecyl- ~ '4-methoxy' 2-phenyl indole (compound 14) Isopropyl-3 'methoxy-4' phenyl-2 indole (compound 15) Cyclohexyl-3 'methoxy-4' phenyl-2 indole (compound 16) Dimethyl-3 '~ 5' methoxy-4 'phenyl-2 indole (compound 17) Dim ~ thyl- ~ ', 5' ethoxy-41 phenyl-2 indole (compound 18) Dodecyl-3 'bydroxY-4' phenyl-2 indole (compound 19) I sopropyl-3 'hydroxy-4' pheny1-2 indole (compound 20) - Cyclohexyl-3'hydroxy-4'phenén-2 indole (compound 21) Dimethyl-3 ', 5-hydroxy-4'phenyl-2 indole (compound 22) Methoxy-3'ethoxy-4'phenyl-2 indole (compound 23) M ~ thoxy-3'dodecyloxy-4'phenyl-2 indole (compound 24) ~ - ~ Methoxy-3'butyloxy-4'phenyl-2 indole (compound 25) Methoxy- ~ 'propyloxy-4' phenyl-2 indole (compound 26) : Methoxy-3'isopropyloxy-4'phenyl-2 indole (compound 27) Diethoxy-3 ', 4'phenyl-2 indole (compound 28) Benzyloxy-3'-methoxy-4'phenyl-2 indole (compound 29) Methyl-3'dodecyloxy-4'phenyl-2 indole ~ compound 30) Methoxy-3'benzyloxy-4'phenyl-2 indole (compound 31) Methyl-3'-benzyloxy-4'phenyl-2 indole (compound 32) ~ ethylenedioxy-3 ', 4'-phenyl-2 indole (compound 33) Ethylenedioxy-3 ', 4'phenyl-2 indole (compound 34) ; M ~ thy1-3'ethoxy-4'phenyl-2 indole (compound 35) Furthermore the compounds of ~ ormule I below are already known and are claimed as new stabilizers polym ~ res and copolymers of vinyl chloride.
Dimethoxy-3 ', 4'phenyl-2 indole (compound 36) Trimethoxy-3 ', 4', 5'phenyl-2 indole (compound 37) Hydroxy-2'methyl-5'phenyl-2 indole (compound 38) ~ ihydroxy-3 ', 4'phenyl-2 indole (compound 39) We know that vinyl resins tend to degrade with heat, and that it is essential to introduce ~ 067 () 8`5 in these masses of synthetic materials of stabilizing agents, in order to delay thermal degradation, and therefore the colo-ration.
Among the organic stabilizers used in this effect, 2-phenyl indole has been found to be particularly interesting, in because of its stabilizing power and its low toxicity. he is also widely used ~ the industrial scale for stabilize vinyl polymers and copolymers, in particular link those that go into the composition of food packaging shut up.
~ however, good stabilizing power is not the only quality required for a substance used for sta-polymerization of polymers. ~ The following features have also of great importance:
~ i _ heat resistance of the stabilized material - - tendency to sticking of stabilized material - held ~ extrusion of stabilized material - - held in the sou ~ fla ~ e of the stabilized material - sublimation of the stabilizing substance - heat resistance of the stabilizing substance ~
Finally, in the particular case of food packaging the substance selected as a stabilizer should not only Lement have a low ~ toxicity, it must also respond ~ favorably to the following criterion:
- ~ igration of the stabilizer in the contents of the package.
- ~ es compounds according to the invention have been found, for one or more of the above characteristics, greater than 2-phenyl indole.
In particular, the compound pre ~ ered according to the invention, namely 3-hydroxy-4'-phenyl-2 indole (compound 2), has found to be superior in all respects to 2-phenyl indole.
~ The toxicity of the compounds according to the invention has been de-completed in the first place and the satisfactory results obtained allowed the continuation of the study.
A) Study of acute toxicity We studied the acute toxicity of the compounds included in the table below by determining the dose of provo-~ as for 50% of deaths in the treated animals (D ~ 50 ~.
: ~ a determination is ~ aite by oral administration of a gummy suspension of the compounds retained in batches of minus 10 mice.
- ~ 10 ~ he following results were obtained:

~ IL50 (mg / kg) Sympt ~ mes ~ o ~ ;:
: 2> 2000 none . 3> 2000 none . 14> 3000 none > 3000 none 2-phenyl indole> 3000 none The dose was also determined by the same method maximum killing no animals (D ~ o) The following results were obtained:
, . . . . .
Compounds DLo (mg / kg) Toxic symptoms . . . _ ..... _ ... ~ 3000 none . 23> 500 none : ~ 30. __> 3000 nevertheless ~.

~ 067085 Compounds ¦ D ~ o (mg / kg) Toxic symptoms . . .
. 27 ~ 3000 nil.
29 ~ 500 n ~ ant 31> 500 none 33> ~ 000. nil : 34 ~ 3000 none 39 ~ 500 n ~ ant _ . ~ ~
~ ~) Study of the thermal stability of the stabilized material .
~ e stabilizing power of compounds according to the invention ; has been the subject of two studies:
: a) Study of static thermal stability b) Study of dynamic thermal stability These studies were conducted on the following 5 formulas of vinyl polymers (compounds):
ormule 1 Constituents Parts by weight Polyvinyl chloride resin 100 Anti-shock resin 9 Epoxidized soybean hulle 2 Hydroxy ~ 12 st ~ 0.2 calcium spleen SL 2016 0.1 Stabilizer 0.3 ; Formula 2 Constituents - Parts by Weight.
PolyYinyle100 chloride resin Anti-shock resin 9 : 30 Epoxidized soybean oil 2 Chelating 1832 ~ ~ 0.25 : ' . ~.

. ~.
Slution ~ 10% 2-ethyl potassium potassium hexanoate 0.025 0.5 stearyl pure alcohol Trihydroxy-12 glycerine stearate. 0.5 0.2 Glycerol Irimontanate Oalcium montanate 0.1 : `- SL
~ T 2016 0.1 Stabilizer 0.3 ~ ormule 3 Constituents Parts by weight Depol chloride resin ~ vinyl 100 Anti-shock resin 12 Epoxidized soybean oil ¦ 3 Chelating 1832 i 0.25 10% potassium solution of ethyl-2 potassium hexanoate 0.025 0.2 calcium-zinc stearate St ~ calcium arate "0.2 ~ rihydroxy-12 st ~ glycerine arate Glycerol trimontanate. 0.3 Acrylic resin 0.5 Stabilizer 0 ~ 3 ormule 4 Constituents Parts by Weight Polyvinyl chloride resin 90 Vinyl chloride-chloride copolymer vinylidene 10 Anti-shock resin 7 Acrylic resin 2 Epoxidized soybean oil 0.5 ~ 2-hényl-3-phenyl-1,2-epoxy propane 0,6 Organostatic stabilizer 0.5 . _9_ .

1 ~) 67085 0.2 calcium gearate Hydrogen rapeseed oil ~ eo, 5 ~ methyl ihydroxystearate 0.2 Micronized silica 0.2 Antioxidant 0.1 Stabilizer 0.3 Formula 5 Constituents Parts by weight Polyvinyl chloride resin 100 Anti-shock resin 12 80ja epoxidized oil 3 Trih ~ droxy-12 glycerin stearate Glycerol trimontanate ~ 0.3 Acrylic resin I 0.5 Stabilizer ~ l 1 In the ~ ormules above, the following ingredients represent:
2016: solution of 2-ethyl hexanoate of zinc in a mixture of aromatic hydrocarbons boiling from 158 to 184C.
. ... .
Chelating agent 1832: diphenyldecyl phosphite: 67 parts by weight ~
10% zinc octoate in diisophthalate butyl: ~
33 parts in weight.
a) Study of static thermal stability : ~ dif ~ erent compounds selected for these tests have ~ mixed head and underwent calendering in a cy- blender heated linders carried ~ a temperature of 160C.
~ es ~ rigid eyelets obtained by this treatment are then subject ~ stays in an oven, at temperatures taken between 180C and 215C, until beginning of carbonization.
For this treatment, a rotary drum oven is used.
ti ~, ventilated and thermostatically controlled.

~ o6qos5 .

In the examples below, we compare the evolution , - .......................................... ..
of a sheet containing the stabilizer ~ test, to the range of degradation of a leaf obtained under the same conditions, but contains ~ 2-phenyl indole as stabilizer.
This comparison can be done using two methods:
1) The colors of the samples to be studied, taken from the oven ~ regular time intervals are compared ~ a - ~ standard color scale, called GARINER color scale, and are expressed in ~ unction of the reference figures of the-so-called GARD ~ ER scale.
~ es measurements are made in a comparator with é- -- GARDNER color scale, containing 18 ~ colored glass isters and allowing to observe by transparency, simultaneously and in a restricted field of vision, the product sample to be ter and the reference filters. he : Dan8 some cases, the shades of the samples are very far from those of the GAR scale ~ NER and the measurements are then difficult or even impossible.
The following results were obtained:
~ The compound of formula 2 was used for this test.
Thickness of the test specimen at time 0: 0.9 mm ~ ,,! Thickness of the test specimen at time 0: 1 mm q test temperature: 210C
.. ~. . . _ ................... ._ S ~ ABI ~ ISANTS: TIME IN MINUTES
; : 0: 3: 6: 9: 12: 15: 18: 21:
Phény1-2indole: 1: 1: 2: 3: 4: 7: 9: ~ 18:
Compos ~ 2: 1: 1: 2: 3: 4: 6: 9: 11:

:.:
Compound 2 has a sta ~ ilisant power clearly su-lower ~ that of 2-phenyl indole, since the control test tube is calcined after 21 minutes, while the test specimen --i1--10670 ~ 35 only has a coloration of 11 GARDNER after the same interval of time.
Methoxy-3'h ~ droxy-4 'phen ~ l-2 indole ~ e compound of ~ ormule 1 has this ~ been used ~
Thickness of the test piece at time 0: 0.8 mm Thickness of the test specimen at time 0: 0.9 mm ~ test temperature: 210C

: STABI ~ ISANTS: ~ EMPS IN MINU ~ ES
: o: 3: 6: 9: 12; 15; 18;
Pn ~ nyl-2 indole. : 1: 2: 3: 4: 9: 12: 13:
, Dial 2 ~ 5: 2: 5: 9: 11:

With this compound Nl, compound 2 is also revealed ; ~ higher than 2-phenyl indole.
Methox ~ - ~ 'benz! Yloxy-4' phenyl-2 indole ~ e compound of ~ ormule 1 was used Thickness of witness specimen at time 0: 0 ~ 9 mm Thickness of the test specimen at time 0: 0 ~ 9 mm Test temperature: 185C
`.:. ..................., S ~ A ~ I ~ ISANTS: ~ EMPS IN MID ~ U ~ ES
, '.' : 0: 6: 12: 18: 24: 30: 36: 4 ~: 48: 54: 60:
: ~ 2-phenyl indole: 1: 2: 4: 9: 11: 15: 15: 16: 16: 18: burned:
Compound 31: 1: 1: 2: 6: 9: 10: 11: 11: 15: 15: burnt.
'. ;
2) Cn also used a simpli ~ iée ~ faster method 39 than the previous one and however leading to valid results.
A reference range has been established ~ using heat treated polyvinyl chloride samples, -12_ 1 ~) 67085 whose coloring has been determined once and for all in GARDNER units, according to the previous method.
This gives a GARDNER leaf subscale polyvinyl chloride directly comparable to the samples lons ~ test, without using the colorimeter.
The following results were obtained:
M ~ thoxy-3-hydroxy-4 '~ 2-hényl indole ~ e compound of formula 3 was used Test temperature: 210C
lQ _ _ : S ~ ABI ~ ISANTS T $ MPS IN MINUTES
: O: 10: 20: 30: 40 s50: 55 60:
: `
. ~
2-phenyl indole: 1: 1.5: 2: <3: 3 s ~ 3: 3.5: ~ 4:
. ,, ~.
`Compound 2: <1: 1 1.5: 2: 2.5: <3: 3: <4:

; ~ The stability bands are quite far apart, for their coloration, of the GARD ~ ER scale and the intensity of the color is therefore difficult to appreciate. We can however find that in this case also compound 2 is a stabilizer superior to indole phenyl-2 ~
Methox ~ -3'h ~ droxy-4 'phen, yl-2 indole ~ e compound of ~ ormule 4 was used Test temperature: 185C
_,. . . _ S ~ ABI ~ ISANTS: ~ EMPS IN MINU ~ ES
`: O: 10: 20: 30: -Phenyl-2 indole: 1: 1: ~ 2: 2:
Composed? : << 1 <l 1 ~ 2:.
. -.
. - ''' ~ the superiority of compound 2 is remarkable at times 0, 10 and 20 minu'es ~ mainly regarding. the co-loration imparted to the ~ reO copolymer Dimethoxy-3 ~, 5 ~ phenyl-2 indole ~ e compound of ~ ormule 1 was used Temperature of the test: 210C

: S ~ ABI ~ ISAN ~ S: TIME IN MINUTES
:; 0; 3; 6; 9; 12; 15;
-, ,, __ ~ ,,, _ __ ~
: 2-phenyl indole: 1: 2: ~: 8 ~ 13:

: Compound ~: 1: 1: 2: 3: 8 ~

. . . _.
At 15 minutes, the test specimen has edges br ~ les, unlike the test specimen.
From the 9th minute, compound 3 is clearly superior to . laughs at 2-phenyl indole.
ydroxy-39 4-methoxy ~ 2-phenyl indole ; ~ 20 The compound of formula 1 was used Test temperature: 210C

... .
- S ~ ABI ~ ISANTS: ~ EMPS IN MINUTES
: 0: 3: 6: 9: 12: 15: 18 . _,. . . .
2-phenyl indole: 1: 1: 2: 5: 9: 13: burnt Compound 13: 1: 1: 1: 4: 7: lO .: br ~ lé

... . . _.
~ e oomomé 13 is clearly superior to 2-phenyl indole

3 ~ the results shown in the table below have been obtained with the compound of formula 1 and ~ a temperature of 210C.

"
~ ~ 06708S

. _. ... . .
: STABI ~ ISAN ~ S: ~ EMPS E ~ MINU ~ ES
-:: 0: 3: 6: 9: 12: 15: 18:
______________________________________________________________ 14: 1: 1: 2: 5: 8: 10: 16 : 2-phenyl indole: 1: 1: 2: 9 ~ 13: br ~
________________________________________________________________ : 1: 1: 2: 4: 11: 13: burn : Phenyl-2 indole: 1: 1: 3: 10: 12: 13: brQlé

16: 1: 1: 2: 3: 9: 13: burned : 2-phenyl indole: 1: 1: 3: 4: 12: 14: burned _______________________________________ _________________________ 17: 1: 1: 1: 3: ll 6: 8: 12 : Phenyl-2 indole: 1: 1: 1: 4 ~ 10: 12: br ~ lé
__________________________________________. _________, ________ 18: 1: 1: 2: ~: 10: 11: 13 .: 2-Phenyl indole: 1: 1: 2: 8: 9: 10: brQlé

, ..,. . ------_____ __ 2019: 1: 1: 3: 6: 6: 11: 16 : 1: 1: 3: 6: 10: 11: burn : 2-phenyl indole: 1: 1: 2.;: 9: 11: 13: brQlé
_________________________________________________________________ :. 23: 1: 1: 2: 2: 3: 9: burned : Phény1-2 indole `1: 1: 3: 10: 12: 13: burned _____________ _______________________________________________ ~ ____ 24: 1: 1: 1: 4: 10: 13: burned 29 ~ 4:10: 13: burned : 2-phenyl indole: 1: 1: 3: 6: 14: 14: ~ r ~ lé
__________________________________________________._______________ :: 0: 3: 6: 9: 12: 15: 18 .

: 25; 1: 1: 2: 3: 9: 12: burned 28 ~ 2 2: 10: 13: brl ~ lé
: Phenyl-2 indole ~ 3: 4: 12: 14: br ~ lé
__________________________________________________ ~ ____________ : 26 ~ 2: 3: 4: 10 :. 27: 1: 1: 1: 3: 4: 9: 13 : Ph ~ nyl-2 indole: 1: 1: 1: 4: 10: 12: br ~ lé
_______________ ________________________________________________ : ~ 0: 1: 1: 3: 5: 6: 13: burned : 32: 1: 1: 4: 4: 11: 1 ~: burned : 2-phenyl indole: 1: 1: 3: 5: 6: 13: burned ----------_____________ . : 21: 1: 1: 2: 3: 8: 12: 14 .-: 35: 1: 1: 2 5: 5: 11: 12 : 2-phenyl indole ~ 2: 8: 9: 10: br ~ lé

: 33: 1: 1: 2: 5: 11: 13: burnt : 34: 1: 1: 2: 5: 10: 13: burn : Phenyl-2 indole: 1: 1: 3: 11: 1 ~: 14: br ~ lé
______ ____________________________ ___________________________ 36: 1: 1: 2: 3: 7: 8:
: 2-phenyl indole: 1: 1: 2: 3: 9: 11:
_______ ________________________ _________________ __ _ : ~ 7: 1; 1: 2: 2: 8: 10: 12 : 2-Phenyl indole: 1: 2: 3: 4: 11: 12: burned b) _ Study of dynamic thermal stability ~ dynamic thermal stability has been studied for 3-methoxy-4-hydroxy-2-phenyl indole (compound 2), compara-2-phenyl indole.
3. For the sake of clarity of the results, we have numbered rotated as follows the different compound formulas subject to tests.
- No. 609: compound of formula 3 with 2-phenyl indole as stabilizing.
- no 676: compound of ~ ormule 3 with compound 2 as stabilizing.
- no 633: compound of formula 5 with 2-phenyl indole as stabilizing.
- no 674: - compound of ~ ormule 5 with compound 2 as sta-biliary.
~ es tests were carried out on a plastograph working at a temperature of 190C, at a speed of ~ otation of 60 revolutions per minute and with a load of 30 g of material gelled ~ e.
Two curves are drawn:
-1 decomposition curve giving the value of the resistive torque both in m.kg versus time.
From this curve, we obtain ~ them important results:
. the minimum resistive torque and the decomposition time.
-1 curve giving the self-heating time as a function of the temperature, this self-heating time is characterized by the moment when the temperature of the material exceeds that of the ~ en ~
belt thermostatically controlled at 190C.
~ the results obtained ~ from the two curves are grouped in the table below:

.
COMPOUNDS
'~. . ', ~.
Measures: 609: 676: 633: 674 . ________________________________________ ________________________ Resistant torque: 1.1: 1.1: 0.96: 0.95: ~
minimum in m ~ kg:
_____________________ __ _______________________________________ ~ 0 67 0 8 5 ... _. ..
COMPOUNDS

, _ : ~ decompo- emps, : sition in min. : 23 ~ 5 23 43 ~ 544.5:
________________________________________________________________ : Auto-é time:
- heating in min. : 6 8 9 22.5:
., 4 .-- _ I
If the results are comparable with regard to the minimum resistive torque and the decomposition time, there is no e ~ t not the same for the self-heating time which is clear-higher for resins stabilized with the compound 2.
c) Study of the bonding of the stabilized material ~ es tests are done on a mixer ~ cylinders of type already used for the study of static thermal stability t ~ that.
~ compounds n 609 and 676 have been selected for this trial.
~ e compound is introduced into the mixer, the oylindres are ~ a fixed temperature of 210C, and it is subject alternating work and rest periods ~ lasting 3 minutes ~.
After 19 minutes, compound No. 676 does not stick, the opposite of compound n 609.
~ has superiority of compound 2 over phenyl-2 indole elst therefore also checked with regard to the tendency to colla-ge deæ compoundsO
D) Study of the resistance to extrusion of stabilized material ~ 'extrusion is carried out on an extruder fitted with a Vi8 45 mm in diameter, with compounds n 609 and 6760 On notes that compound No. 676 undergoes perfect extrusion, this ~ ui is not the case of compound n 609.
The superiority of compound 2 over phenyl-2 indole is therefore also checked with regard to the holding - at the extrusion of the compound.
E) Study of the breath resistance of the stabilized material ~ 'blowing test was carried out on a mold bottle-shaped with compounds n 633, 674, 609, 676.
~ the operating conditions observed made it possible to 10- find that the bottles obtained with compound n ~ 633 have a fairly strong yellow color ~ On the other hand, with compound n 674, bottles are obtained whose coloring is much less sustained.
Likewise, the bottles obtained with the compound n 676 are very clear, much more transparent and less yellow than the ~ bottles obtained with compound No. 609.
In this trial, the superiority of compound 2 is also total with respect to 2-phenyl indole.
~) Study of the sublimation of the compounds according to the invention ; 20 ~ We know that 2-phenyl indole has the disadvantage deny sublimating during its handling in the pulp state crooked, during compound formation and extrusion of it.
This relatively large sublimation is a drawback major because, apart from the significant losses of stabilizer, it is at the origin of a pollution of the atmosphere of the workshops in which operations take place.
~ tends to sublimate 3-hydroxy-4-methoxy phenyl-2 indole (compound 2) was compared to that of phenyl-2 indole.
~ he principle of the experimented method is the following:

10670 ~ 35 A sample of the test product is introduced into a tube.
~ test and immersed in a heating bath ~ thermostatically controlled under reduced pressure.
; ~ We recover ~ re on a mobile cold wall, thermostatically controlled, the fra ~ tion of sublimated product and, after a certain period, the collected product is weighed, The result is expressed as a percentage (by weight) of product collected in relation to the intake of test.
Observed results can only have value 10 relative to compare two products tested in the even my conditions.
Operating conditions (chosen arbitrarily) 120C hot wall temperature cold wall temperature 13C
pre8sion 15 ~ orr duration 150 minutes test portion 150 mg ~ es percentages of products sublimated under these conditions ; are as follows:
~ 2-phenyl indole; 26.9%
3-methoxy-4-hydroxy-2-phenyl indole: 1.2 The ability to sublimate the product tested compared to to 2-phenyl indole can be quantified, by calculating the ratio from the quantity of sublimated product to the quantity of 2-phenyl dole sublimated under the same conditions. We obtain:
3-methoxy-4-hydroxy-2-phenyl indole: 4.5%
~ 'interest of this compound compared to 2-phenyl indole ~
is well demonstrated, since it has a tendency to sublimation 20 times less than that of 2-phenyl indole.
G) Thermal Sta ility of the Compounds According to the Invention :.:
~ es thermal stabilities of compound 2 and phenyl-2 indole were compared by differential thermal analysis and ,., ..........;
. . ... ..... . .

`~ ~ 067085 psr thermogravimetric analysis.
a) Differential thermal analysis The differential thermal analysis diagrams have - ~ tee determined by study of samples of 2 mg of product placed in a leak-proof container, the temperature rise being 2C / minute and the sensitivity of 4 mcal / sec.
The diagrams were successively obtained with the 2-phenyl indole (i) and with compound 2 (ii ~
They lead to the following conclusions:
(i) 2-phenyl indole sublimates from 140C and especially from from 185-190C (point of ~ usion).
There is no water departure ~ 100C. ~ e beginning of decomposition seems to be around 210-220Co It is very difficult to set the temperature for `~ o precision composition of the $ ait that we cannot separate the eifet of thermolysis from that of subli-mation.
(ii) there is no water departure - we notice a ~ wear at 160C
and a start of decomposition at 235-240C, then a se-of exothermic waves.
b) Anal, yse thermo ~ ravimetric ~ 'thermogravimetric analysis ~ ique gave rise to 2 series of tests e ~ carried out under air and under gas in ~ rte (argon), in order ~ eliminate any possible oxygen aotion. ~ es ob ~ results held were identical.
The temperature variation was 80C / hour.
~ The thermograms have been drawn in air with respect 2-phenyl indole (i) and compound 2 (ii) They lead to the following conclusions:
(i) The onset of weight loss begins around 190-195C. he is both ~ sublimation and ~ a beginning of composition. In the case of experimentation under air, i. '' --2i--i `10 ~ 7085 indeed, at ~ 210C, a yellow residue proving is obtained this decomposition. Although the sample was not maintained at the temperature of 210C ~ we can predict that ~ a prolonged stay ~ this temperature, at least in the presence air, must lead to a significant degradation of said sample.
(ii) ~ e beginning of weight loss is around 235-240C, this which corresponds to the beginning of the decomposition.
~ - ~ the results of the thermogravimetric analysis overlap the results of the di ~ erential thermal analysis, showing the superiority mani ~ este of compound 2 vis-~ -vis of phenyl-2 indole regarding their heat stability.
This factor is very important because the preparation of the compound and its implementation require ~ frequently temperatures-erasures ~ ariant from 180 ~ 220a, lasting several minutes in certain cases.
H) Extractability of the stabilizer ~ es products according to the invention being capable of 8tre used as stabilizers for polymers used in the composition sition of food packaging, it was necessary, despite their ~ low toxicity, study the ~ ur extractability by different sol-vants simulating food.
This study was conducted under the conditions imposed ~ - by the "~ ood and ~ rug Administration" (U ~ S ~ Ao) ~ The solvents used are: water, aqueous ethanol 50/50, 3% aqueous acetic acid, heptane.
~ es extractions were carried out in bottles semi-rigid, prepared from compounds 609 and 676 and with the following dimensions:
diameter: 62 mm height: 170 mm capacity: 375 ml weight: 28g `~ 67085 ~ e ratio of the volume of the extraction solvent to the plastic surface subject to e8t neighbor extraction 1 per 100 ml of solvent, taking into account the characteristics geometric bottles.
~ E ~;
- temperature: 49C
- heating mode ~ age: thermostatically controlled study for non-solvents flammable (water and acetic acid) thermostatically controlled bain-marie for flammable solvents (alcohol and heptane).
- extraction time: the extraction times were voluntary considerably higher than those which would have made it possible to reach stable limit values. The exact extraction times are indicated below the results obtained.
The amount of stabilizer extracted was determined by a colorimetric assay with p-dimethylaminobenzaldehyde, according to the method described in A ~ alytical Chemistry 36, 425-26 (1964).
A blank test was carried out with a compound of same formula as compounds n 609 and 676, but not containing no stabilizer. A null result has been obtained. ~ or - the results are collated in the table below. ~ when dosed stabilizer tities are expressed in ~ g per liter of extraction solvent, or what comes to the same mame per 1000 cm2 of on ~ ace extracted.

. . _ : COMPOUND

: Solvents n 609 N 676 _________________________ _________________________________________.
: Water: 40 (6 days) <3 (10 days) ________________________________________________________________ __ __ : Aqueous solution of acid ~ acéti ~ eu 3%. ~ 3 (20 ~ days) <3 ~ 20 days ~:
: ______._ ~ .____ _______: _____, ___, ___________ ___ ____ __________ Ethanol has ~ 50 ~ 50 ~ 100 (9 days) ___ <10 ~ _iours ~ _ _____ : Heptane: 875 (48 hours) 175 (48 hours) A ~ -23_ .,.
Other tests have also been carried out with the Compound of formula 1 containing the stabilizers below:

: S ~ ABI ~ ISANTS SOLVENTS
:: 14: 19: 24: 30 : water: c3 <3 ~ 3 <3 (10 days): (10 ~ bear) :( 10 days): (10 days) : Aqueous solution ; acetic acid: <3 <3 <3 <3 ~ 3%: (20 days); (20 days) :( 20 days): (20 days) .
: Aqueous ethanol: ~ 10 <10 <10 <10 50/50: (9 days) :( 9 days) :( 9 days); (9 days) : Heptane: 175 175 175 175 (48 hours): (48 hours) :( 48 hours) (48 hours .
. , According to these results the compounds 2, 14, 19, 24 and 30 are much less extractable than 2-phenyl indole by water, aqueous ethanol and heptane.
In the case of dilute acetic acid, the amounts are close, but it is difficult to draw x clu ~ ion because these quantities are below the sensitivity threshold of the dosing method.
With regard to water, it is proven that the Compound 2 is clearly superior to 2-phenyl indole, since its extrac-tibillity is at least 10 times lower. This finding is important, because it is linked to the problem of conditioning ~
mineral waters and their possible pollution by packaging in stabilized polymer.
The stabilizers according to the invention are introduced into -24_ thermoplastic materials ~ 0.1% ~ 1% by weight.
~ es The following examples illustrate, in a non limiting, the processes for preparing the compounds according to the ~ ention:

Process for the preparation of hydroxy-2 'methoxy-4' phen ~ l-2 indole a) Pre ~ aration of the ~ hénylh ~ drazone of the h ~ dro ~ -2 methox ~ -4 ___ ______________ __ _ _______________ ___ _________ __ acetophenone _____ ______ To a benzene solution containing 166 g (1 mole) of 2-hydroxy-4-methoxy acetophenone, 94 g (1 mole) of phenylhydrazine and a catalytic amount of acetic anhydride.
Chau ~ fe the mixture at reflux for one hour, then eliminate the soil ~ ant by evaporation.
~ e raw product obtained is used as is dansll ~ tape next.
Using the same method, but using the pro-suitable starting materials, the following compounds were prepared:
- phenylhydrazone of 2-hydroxy-5-methyl acetophenone 2-methyl-4-methoxy-acetophenone phenylhydrazone 2-hydroxy-4-methylphenylhydrazone acetophenone 3-methyl-4-methoxy-acetophenone phenylhydrazone 2,4-dimethoxyphenylhydrazone acetophenone 3-dodecyl-4-methoxy-acetophenone phenylhydrazone 3-isopropylphenylhydrazone-4-methoxy acetophenone 3-cyclohexyl-4-methoxy-acetophenone phenylhydrazone 3,5-dimethyl-4-methoxy-acetophenone phenylhydrazone dimethyl phenylhydrazone ~ 4, 5-ethoxy-acetophen ~ one b) Preparation of h ~ droxy-2 'methoxy-4' ~ hén ~ 1-2 indole ___ _____________ ____ __________ ____ ___ __________ 450 g of polyphosphoric acid are prepared by mixing 1 part of orthophosphoric acid to a part of anhydride phosphoric and the mixture is brought to ~ a temperature : '..

1 ~ 67085 between 140C and 1 ~ 0C. 230 g (1 mole) of 2-hydroxy-4-methoxy-acetophenone phenylhydrazone and the same temperature is maintained for one hour. We pour The reaction medium in one liter of water and the precipitate which is formed is taken up in ether. ~ the ethereal phase is washed water until neutral, then dried.
After purification of the solution with activated carbon and evaporation of the ether, a green oil is obtained which crises tallises to give the raw product.
After recrystallization from benzene, 60 are obtained.
g of hydroxy-2 'methoxy-4' phenyl-2 indole, melting at 195C.
Yield: 25%
By an identical method, but using the pro-suitable starting materials, the compounds below were obtained ~
Compound Melting Point 2-hydroxy-5-methyl-2-phenyl indole 178C
2-hydroxy-4-methyl-2-phenyl indole 191C
3-methyl-4-methoxy-2-phenyl indole 210C
.
. ~ dimethoxy-2 ', 4' phenyl-2 indole 143C
~ EMPLE 2 PREPARATION PROCEDURE FOR 2-Methyl 2-methox ~ -4 '2-phenyl indole `~ e methyl-2 'methoxy-4' phenyl-2 indole is prepared by cyclization of phenylhydrazone from 2-methyl-4-methoxy-ao tophenone in polyphosphoric acid, according to the operating mode roof of Example 1, but operating at a temperature of ~ iron 110-120C. ~ e product obtained is recrystallized from ethanol and gives 95 g of 2-methyl-4-methoxy-2-phenyl-indole, ~ waving at 131C.
Yield: 40%

Process for E ~ separation of 3-dodecyl-4-methoxy-2-phenyl-indole 50 g of polyphosphoric acid are prepared by mixing part of orthophosphoric acid ~ part of anhydride phosphoric and the mixture is brought to a temperature of 100C.
-We slowly add 40.8 g (0.1 mole) of the phenylhydrazone 3-dodecyl-4-methoxy acetophenone, prepared as in Example 1, and the reaction medium is maintained ~ in ~ iron 100-110C for one hour. After re ~ cooling ~ 80C the mixture is poured in ice water and the indolic precipitate that forms is filtered and washed with water until neutral, dried and then washed hexane.
After recrystallization from ethanol, under the atmosphere nitrogen, 9 g of dodecyl-3 'methoxy-4' phenyl-2 indole are collected, melting at 111C.
Yield: 2 ~%
By an identical method, but using the pro-suitable starting materials, the compounds below were obtained:
~ omitted Melting Point Isopropyl- ~ '4-methoxy' 2-phenyl indole 160C
. (~ enzyme pUlS ethanol) Cyclohexy1-3 '4-methoxy-2-phenyl indole 176C
(~ enzyme) Dimethyl-3 '5' methoxy-2 phenyl-indole 175C
(Ethanol then acetone) Dimethyl1-3 ', 5' 4-ethoxy-2-phenyl indole 134C
(column chromatography silica with benzene as eluent) Process for the preparation of methoxy-3 'hydroxy-4' Phe-n-yl-2 indole a) Pré_aration of Ehénylh ~ drazone of metho ~ y-3 hydrox ~ -4 ___ ______________ ___ __ ___________________ ____ ____ __ acetoP-eno ~ e _____ ______ . A mixture comprising 8.3 g (0.05 mole) of 3-methoxy 4-hydroxy acetophenone, 5.4 g (0.05 mole) phenylhydrazine, 20 ml ethanol and a drop of acetic acid e ~ t heated ~ reflux in a double boiler for 6 hours, then is kept for one night ~ a temperature of about 5C ~ ~ e precipitate formed is wrung, washed with a minimum of benzene and dried under vacuum ~
ambient temperature. Gn obtains 10.5 g of phenyl hydrazone 3-methoxy-4-hydroxy acetophenone, melting at 131C.
Yield: 82 ~ o b) Pre ~ aration of methox ~ -3 '~ drox ~ -4' ~ 2-hényl indole 40 g of orthophosphoric acid are poured onto 7.68 g ~ 10 (0.0 ~ mole) of phenylhydrazone of 3-methoxy-4-hydroxy - tophenone, then the mixture is heated to ~ 130C for one hour and finally at 180C for 10 minutes O After 30 minutes of rest at room temperature, the reaction medium is taken up by 200 ml of water and the aqueous suspension is used up several times with methylene chloride. The organic phases are brought together, washed with water and dried over magnesium sulfate anhydrous, then it is ~ iltered on an alumina column.
After ~ s dry evaporation of the solution, we obtain 5.1 g of crude product. After two recrystallizations in the toluene, 4.8 g of 3-methoxy-4-hydroxy-2-phenyl are collected indole, melting at 165 ~.
Yield: 67.3%

Process for the preparation of ~ 4 '2-ethenyl indole a) Pre ~ aration of the ~ hén ~ lh drazone of dimethox ~ -3 ~ 4 acetoPhenone _ _ ______________ __ __ ______________________ __ _______ ______ A mixture comprising 60 g (0.3 mole) of 3,4-dimethoxy to ketophenone, 33 ml of phenylhydrazine, 100 ml of ethanol at 1.5 ml of acetic acid is heated to reflux under a nitrogen atmosphere for 10 hours. The alcohol is then evaporated in an evaporator rotary and the residue obtained is recrystallized from toluene 56.8 g of crystals are obtained which are added to the 28.2 g of product.

- recovered by concentration of the mother liquors. We have in total 85 g of phenylhydrazbne of 3,4-dimethoxy acetophenone, used raw sand ~
.y, By following the same method, but starting from the products suitable starting materials, the following compounds were obtained:
3,5-dimethoxyphenylhydrazone acetophenone 3,4,5 trimethoxy phenylhydrazone acetophenone b) Preparation of dimethoxy-3 ', 4' phenyl-2 indole ________ Qn adds ~ 450 g of polyphosphoric acid, prepared as ~ Example 1, 67.5 g (0925 mole) of phenylhydrazone 3,4-dimethoxy acetophenone, the temperature being maintained ~ about 170-185C and the addition being done with stirring - canic. ~ -~ 'addition completed, the temperature is maintained at 180C for 10 minutes. After 10 minutes of temperate rest room temperature, the mixture is taken up in 1 liter of water and stirred until the oily phase disappears. After cooling up to room temperature, the aqueous suspension is exhausted seated in several times ~ ether. ~ the ethereal phase is washed at water, dried over anhydrous sodium sulfate, then filtered through neutral alumina column to give, after recrystallization in tolu ~ ne, 22 g of dimethoxy-3 ', 4' phenyl-2 indole, ~ ondant at 188C
Yield: 35 ~ 0 Using the same method, but using the pro-suitable starting materials, the following compounds were prepared:
Compound Melting Point .
dimethoxy-3 ', 5' phenyl-2 indole 124C
trimethoxy-3 ', 4', 5 'phenyl-2 indole 206C
EXE ~ PLE 6 .4 Process for the preparation of hydroxyl ~ -3 '4-methoxy-2-phenyl indole , .

6 ~ 0 8 5 :: ~ a) Pre ~ aration of the ~ hén ~ lhydrazone de la hydro ~ y- ~ 'métho ~ -4' ___ ______________ __ __ ________ - ______ ___ _________ ___ aceto ~ hénone ---- ______ - After having introduced into 500 cm3 of benz ~ ne 60 g (0 ~ 36 mole) 3-hydroxy-4-methoxy acetophenone, 20 g (0.2 mole) of phenylhydrazine and 5 cm3 of acetic anhydride, heated to reflux with stirring for one hour. ha benzene solution -is then concentrated by evaporation under reduced pressure and the phenylhydrazone of 3-hydroxy-4-methoxy acetophenone obtained ~ The raw state is directly engaged in the next step.
b) Preparation of 3-hydroxy-4-methoxy-2-phenyl-indole ----_______ 20 g (0.12 mol) of the phenyl-hydrazone of 3-hydroxy-4-methoxy acetophenone ~ 100 g of acid polyphosphoric acid, prepared by mixing 60 parts of phos-phoric and 40 parts of phosphoric anhydride, ~ at temperature medium is maintained at 110C for 30 minutes after the ~ in of addition. We then pour the mixture into ice water and extracting the indole derivative with ether. The ethereal phase is washed, dried pUi9 concentrated under reduced pressure. The pro-raw product obtained is recrystallized from a toluene-ethanol mixture - (80/20) to give 14.3 g of hydroxy-3 'methoxy-4' phenyl-2 indole.
P. ~. : 217C
Yield: 50%

Process for the preparation of dihydrox ~ -2 ', 4' 2-phenyl indole A.) Pre ~ aration of the ~ hénylh ~ drazone of the dih ~ dro3 ~ -2 4 aceto ~ hénone ___ ______________ __ __ ________________ ___ __L_______ ______ A mixture containing 15.2 g (0.1 mole) of 2,4-dihydroxy acetophenone 50 ml ethanol, 10 ml phenylhydrazine and 3 drops acetic acid is heated ~ reflux for 2 hours then left in an ice bath for 30 minutes. ~ es crystals obtained are wrung and washed with 100 ml of hexane. We get 21 g of -3o-'1067085 brown crystals ~ melting at 159 ~ C.
b) Preparation of the dihydrox ~ -2 ', 4' phenyl-2 indole ___ ______________ ____ ___ ___ __ __________ 12.2 g (0.05 mole) of the phenylhydrazone are added.
dihydroxy-2 ~ 4 acetophenone ~ 60 g of orthophosphoric acid, the reaction medium being maintained at 130C for one hour, then at 180C for 10 minutes. ~ e mixture is then poured under stirring in one liter of ice water and is extracted with a-ethyl acetate. ~ the organic phase is washed with 100 ml of water, dried and the solvent is removed by evaporation. We get a brown residue which is chromatographed on a column of gel of silica, with an ethyl acetate-ether mixture (10/90) as eluting. After removal of the solvent and recrystallization from - ~!
a toluene-methanol mixture, 4.6 g of 2 ', 4' dihydroxy are obtained 2-phenyl indole, melting at 188C.
Yield: 40%.

Process for the preparation of methoxy-3 'h ~ droxy-4' phen ~ yl-2 indole ~ 32.5 g is added (0.35 mole ~ of aniline brought to the 20 g (0.1 mol) bullion of GJ-chloro-methoxy-3 hydroxy-4 aceto-phenone, adding in 15 minutes. The temperature of the the reaction medium is then maintained at 180C for 20 minutes nutes. ~ e mixture is then poured into an aqueous solution di-hydrochloric acid and extract the indole derivative at llétherO ~ ethereal phase is washed, dried and concentrated under reduced pressure. ~ e crude product is refilled with toluene and wrung out. After recrystallization from a toluene-ethanol mixture (80/20) 4.8 g of methoxy-3 'hydroxy-4' pheny ~ -2 in dole, melting ~ 165C.
Yield: 20 ~ o ~
- 3 By an identical method, but using the product appropriate starting point, the compound below was prepared:

- -31-;

~ 067C ~ 85 Compound Melting Point - Isopropyl-3 'methoxy-4' phenyl-2 indole 160C
(ethanol) Process for the preparation of dimethoxy-3'L4 'phenyl-2 indole A mixture containing 372 g (4 moles) of aniline and 215 g (1 mole) of ~ -chloro-dimethoxy-3,4 acetophenone is hot ~ fairy reflux for an hour. After cooling of the medium reaction around 50C, it is poured into ice water addi-with 50 cm3 of concentrated hydrochloric acid.
It is extracted with chloroform and the organic phase is washed ~ water, dried and concentrated under reduced pressure. ~ e crude product obtained is recrystallized from ethanol and re ~
picks 100 g of dimethoxy-3 '~ 4' phenyl-2 indole, melting at 190C-192C.
; Yield: 40%.

Process for ~ repair of methox ~ -2 'meth ~ lS' 2-phenyl indole To a solution of 223 g (1 mole) of hydroxy-2 'is added 5 'methyl-2-phenyl indole ~ prepared as in Example 1, in 1200 ml of N, N-dimethylformamide, 65 g (1.2 mole) of methylate ~ odium, at a temperature of 90C. We then add, drop- ~ -drop, 170 g tl, 2 moles) of methyl iodide and, when the dition is finished ~ the mixture is heated to 100C for 3 hour 8. The mixture is allowed to cool and the crude product is precipitated by addition of water. ~ e precipitate is taken up in ether, washed and dried ~.
After evaporation of the ether, the product is purified chromatography on a silica column, with benzene as eluting. 150 g of 2-methoxy-5-methyl-2-phenyl-2 are collected.
dole, melting at 119C.
Yield: 59%.

~ 0 6 70 8 S
E ~ 'MP ~ E 11 Process for the preparation of 2-methoxy-4-methyl-2-hényl-indole To a solution of 223 g (1 mole) of hydroxy-2 'is added 4-methyl-2-phenyl indole, prepared as in Example 1, in 1200 ml of N, N-dimethylformamide, 54 g (1 mole) of methylate sodium then 170 g (1.2 mole) methyl iodide, the medium reaction being at a temperature of 25U ~. ~ 'addition complete ~
shake for 2 hours. The crude product is precipitated by addition of water and recrystallized from benzene. We re-collects 166 g of 2-methoxy-4-methyl-2-phenyl-indole, fondant at 125C.
Yield: 70%.

Process for the preparation of 3-methoxy-4-ethoxy-2-phenyl indole To a mixture of 50 ml of N, N-dimethylfor-mamide and 1.23 g (0.022 mole) potassium hydroxide 4.8 g (0.02 mole) 3-methoxy-4-hydroxy-2-phenyl-indole, prepared as ~ Example 4 above, the reaction medium being heated a temperature of 50C. We then introduce in 10 minutes

4.68 g (0.03 mole) of ethyl iodide and then heated to 60C
during two hours. After re ~ stiffening, pour the medium reaction in water and extracted with ether. ~ a phase ethereal and washed with water until neutral, dried and concentrated under reduced pressure.
After recrystallization from toluene, it is collected 3.06 g of 3-methoxy-4 'ethoxy-2' phenyl-2 indole, melting at 177C.
Yield: 60%.

Process for the preparation of metodoxy-3 'dodé ~ loxy-4' phenyl-2 indole Is added in 15 minutes ~ a mixture of 120 ml of N, N-dimethylformamide and 6.75 (0.125 mol) of methyl methoxide sodium 23.9 g (0.1 mol) of 3-methoxy-4-hydroxy-2-phenyl-indole, ~ `~ 06708 ~

pr ~ ready co ~ me ~ e ~ example 8 above, and we stir the melan ~ e for 15 minutes before introducing in 15 minutes 25.6 g (0.1 mole) of chloro-l dodecane. We then carry the reaction medium-nel ~ a temperature of 130C and we main ~ ient llagitation to this temperature for 3 hours. After cooling, we pour the reaction medium into water and the precipitate formed is filtered and washed with water until ~ neutral.
After two successive recrystallizations in llétha ~
nol 20 g of methoxy-3 'dodecyloxy-4' phenyl-2 are collected indole, ionating ~ 104C.
Yield; 50%.
By an identical method, but using the products of appropriate starting points, the following compounds were prepared:
Compounds llPoint of ~ usion 3-methoxy-4-butyloxy-2-phenyl indole 140C
~ (ethanol) 3-methoxy-4-propyloxy-2-phenyl indole 138C
(etha ~ ol then acetone) 3-methoxy-4-isopropyloxy-2-phenyl indole 139C
J '' (ethanol then acetone) diethoxy-3'4 'phenyl-2 indole 163C
(benzene then ethanol) benzyloxy-3 'methoxy-4' phenyl-2 indole174C
(ethanol) methyl-3 'dodecyloxy-4' phenyl-2 indole112C
(hexane) 3-methyl-4-benzyloxy-2-phenyl indole184C
(ethanol then acetone) 3-methoxy-4-benzyloxy-2-phenyl indole157C
(toluene) methylenedioxy-3 ', 4' phenyl-2 indole191C
(methanol) '~ 067085 ethyl ~ nedioxy-3 ', 4' phenyl-2 indole 190C
- ~ methanol) 3-methyl-4-ethoxy-2-phenyl indole167C
(ethanol-acetone 80/20) ExFMp ~ EA-l4 Process for pre ~ aration of methyl-2 'hydroxy-4' phenyl-2 indole A solution containing 1800 ml of benzene, 237g (1 mole) 2-methyl-4-methoxy-2-phenyl indole, prepared as in Example-ple 2, 300 g (2.25 moles) of aluminum chloride is heated ~ reflux for 2 hours. After cooling, we extract the ether and the ethereal phase is then washed until neutral, then dried over anhydrous sodium sulfate. ~ e product obtained after evaporation of the ether is recrystallized from benzene.
Qn collects 167 g of 2-methyl-4-hydroxy-2-phenyl indole, melting . ~ i at 106C.
Yield ~ 75%.
By an analogous method, but using the pro-appropriate starting materials, the following compounds have been prepared:
Compound Melting Point methyl-3 'hydroxy-4' phenyl-2 indole 222C
(recrystallization in ethanol / water 95-5) n-dodecyl-3 'hydroxy-4' indole-2 phenyl 115C
- (benzene) isopropyl-3 'hydr ~ xy-4' phenyl-2 indole 195C
(benzene) dihydroxy-3 ', 4' phenyl-2 indole 236C
(methanol) cyclohexyl -3 'hydroxy-4' phenyl-2 indole 161C
3o (benzene / heptane) dimethyl-3 ', 5' hydroxy-4 'phenyl-2 indole254 C
~ ethanol)

Claims (10)

The embodiments of the invention about which an exclusive right of property or privilege is claimed are defined as follows: 1. Stabilizers of polymers and copolymers of vinyl chloride, characterized in that they respond to the general formula:
I

in which, R1 and R2, which are identical or different, each represents an alkyl radical, linear or branched and comprising from 1 to 12 carbon atoms, a cyclohexyl radical, an alkyloxy radical, linear or branched and comprising of 1 with 12 carbon atoms, a benzyloxy radical, a hydroxy radical, where R1 and R2 together represent an alkylenedioxy radical comprising from 1 to 3 carbon atoms, R3 represents the hydrogen-ne, a methyl or methoxy radical, it being understood that:
a) at least one of the substituents R1 and R2 does not not represent an alkyl radical;

b) the substituents R1 and R2 do not represent simultaneously hydroxy radicals when R3 represents hydrogen or methyl radical; and c) the substituents R1 and R2 do not represent simultaneously alkyloxy radicals when R3 represents the methoxy radical. 2. Methoxy-3 'hydroxy-4' phenyl-2 indole. 3. Process for the preparation of poly- stabilizers mothers and copolymers of vinyl chloride, of general formula:

I

in which R1 and R2, which are identical or different, each represents an alkyl radical, linear or branched and comprising from 1 to 12 carbon atoms, a cyclohexyl radical, an alkyloxy radical, linear or branched and comprising from 1 to 12 carbon atoms, a benzyloxy radical, a hydroxy radical, where R1 and R2 together represent an alkylenedioxy radical comprising from 1 to 3 carbon atoms, R3 represents hydrogen, a methyl or methoxy radical, it being understood that:
a) at least one of the substituents R1 and R2 does not represent not have an alkyl radical;

b) the substituents R1 and R2 do not represent simultaneously hydroxy radicals when R3 represents hydrogen or methyl radical; and c) the substituents R1 and R2 do not represent simultaneously alkyloxy radicals when R3 represents the methoxy radical, characterized in that one reacts a acetophenone derivative of general formula:

in which R1, R2 and R3 take the same values as pre-cédemment and X represents a hydrogen atom or an atom halogen with a compound of general formula:

in which Z represents a group - NHNH2 or a group -ment -NH2, it being understood that:
- when X represents a hydrogen atom, Z
represents the group -NHNH2, the phenylhydrazone of aceta-phenone then obtained being cyclized either by dehydration, either by thermolysis, to obtain the desired product, and - when X represents a halogen atom, Z
represents the group -NH2. 4. Preparation process according to claim 3, characterized in that an acetophenone derivative is reacted corresponding to the general formula:

in which R1, R2 and R3 take the same values as in formula I, with phenulhydrazine, phenulhydrazone the acetophenone obtained being cyclized either by means of an agent desiccant either by thermolysis to obtain the desired compound of formula I. 5. Preparation process according to claim 4 characterized in that the cyclization is carried out by means polyphosphoric acid. 6. Preparation process according to claim 4 characterized in that the cyclization is carried out by means sulfuric acid. 7. Preparation process according to claim 3 characterized in that a derivative of acetophen is reacted none of general formula:

in which R1, R2 and R3 take the same values as in formula I, X representing a halogen, with aniline to obtain the desired compound of formula I. 8. Preparation process according to claim 7 characterized in that X represents a chlorine atom or bromine. 9. Polymers and copolymers of vinyl chloride characterized in that they contain at least one stabilizer according to claim 1. 10. Polymers and copolymers according to claim 9 characterized in that the stabilizer is introduced correctly from 0.1% to 1% by weight.