DE2327717A1 - PIPERIDINE DERIVATIVE AND PROCESS FOR ITS PRODUCTION - Google Patents

Description

PATENT LAWYERS

BRA. O. ΌΓΓΓΜΛΝΝ κ. ία. scriirrF ¹ im. A. ν. FÜKISR Dipl. Inc. P. STRfCIIL υπ. U. SCIIÜBEL-HOPF rjii'i.-iN-o. Ό. 32nHINGIIAXJS

D-S MUNICH 9α MARIAHICPPLATZ 2 S:

POSTAL ADDRESS ID-S MUNICH 95 POST BOX Ü5 0180

(OSIl) 4-83 TELEGR. AUROUAKCPAT MUNICH TELEX'fJ-23 505 AtJRO

SAiJICYO COMPANY LIMITED

30th quay 1973 2327717 ■ 014-10452 Sl / Rt

Piperidine derivative and process for its

Manufacturing

Priority: May 31, 1972, No. 54059/1972, Japan

The invention relates to a new piperidine derivative and a method to establish this connection.

The invention provides a new piperidine derivative, 1,3,8-Tria3a-7,7,9,9-tetramethyl-spiro £ 4.5] decan-2 _r 4-dithione, the v.ärd represented by the following SOrmel:

CH ₃ CH ₃

309881/1 198

The invention also relates to a method of manufacture of the piperidine derivative of the above formula I.

The compound according to the invention of Porsel I is a previous one new substance not yet described in the literature, which are suitable as an intermediate for the synthesis of piperidine spiro-hydantoin derivatives is what highly effective stabilizers for synthetic polymers such as olefin, diene and styrene polymers, for example polyethylene,! polypropylene and polystyrene, for polyacetals, for example "polyoxymethylene, for Polyesters, for example polyethylene texephthalate, for polyamides, for example nylon-6, polyurethanes and the like against degradation by exposure to light and heat. To illustrate, it should be stated that Ä? .A according to the invention Piperidine derivative I, for example, according to the reaction scheme shown below by reaction with halides of following ^ Formula III into the piperidine spirohydantoin derivatives the following formula II can be converted.

R- (X) n (TII)

(I)

(Π)

In the above formulas II and III η means a whole Numbers from 1 to 4 and inclusive

When η denotes 1, R stands for an alieny group, the given one; if substituted with halogen, cii: ^ Aikiny! group, the £>: -

• 3 09881/1198

is optionally substituted by phenyl, an aralkyl group which is optionally substituted by halogen atoms, alkyl groups with 1 to 4 carbon atoms or halomethyl groups, a hydroxyalkyl group, alkoxyalkyl group, an alkenyl oxyalkyl group, an aryloxyalkyl group, an alkylthioalkyl group, an acyloxyalkyl group, an epoxyalky group, an IT -alkyl-substituted aminoalkyl group _; an alkoxycarborylalkyl group, an aryloxycarbonylalkyl group, an aliphatic acyl group, an alkoxyearbony group, a phosphine group which is phenoxy or alkoxy substituted or a phosphinyl group which is phenoxy or alkoxy substituted; if η is 2, for an alkylene group with 4 to 18 carbon atoms, a dialkylene ether group, an aralkylene group, a bis (acyloxyalkylene) group or an alkylene bis (oxycarbonylalkyl) group,

when η 3 means for a £ ris (acyloxyalkylene) group, a Alkane-tris (oxycarbonylalkyl) group or a group of the formula ■

- 0- (CH ₂ ) _p -)

in which ρ denotes an integer from 1 to 8 inclusive and the numbers equal to ρ can be the same or different, and

when η denotes 4, denotes an ietrakis (acyloxyalkylene) group
and X represents a halogen atom.

When carrying out the process described above by way of example for the preparation of the piperidine-spiro-hydantoin derivative II, the reaction can be carried out by adding a stoichiometric amount of the halide R- (X) _n to the starting compound I, which may be in water or a suitable organic solvent is dissolved or suspended, - for example in benzene, toluene, xylene, dimethylformamide and the like.,

309881/1198

ORIGINAL INSPECTED

2327V17

and the resulting mixture either left to stand at room temperature or heated to reflux.

Representative examples of suitable piperidine-ßpiro-hydantoin derivatives II are the following compounds:

1. 3-Allyl-1,3,8-triaza-7,7,9,9-tetramethyl-spiro 4. ^ 1 decane-2,4-dithione

2. 1,3,8-Iriaza-7,7,9,9-tetramethyl-3- (Z-dimethylaminoethy-1) ~ spiro J4.5J decane-2,4-dithione

3. 1,3 »8-Triasa-7» 7,9,9-tetramethyl-3-diphenoxyphosphinospiro Γ4.5Ι decane-2,4-dithione

4. 1,3,8-Iriaza ~ 7,7,9,9-tetramethyl-3-dipbenoxyphoaphiny1-spiro [4.5] decane-2 ₅ 4-ditbione

5. 2,2 ', 2 "-Tris (1,3,8-triaza-7,7,9,9-tetramethyl-2,4-ditbioxospiro (4.5} -3-decyl) triethyl phosphite

6. Tetrakis [j- (1,3,8-triaza-7,7,9,9-tetramethy1-2,4-dithioxospiro ^ .5j -3-decyl-ethyl-pyrolyilitate.

The piperidine-spiro-hydantoin derivatives which can be used as stabilizers II can be performed by any of the various standard procedures commonly used in the art added to the synthetic polymers. The stabilizer can be incorporated into the synthetic polymers at any stage prior to the manufacture of molded articles from the polymers will. For example, the stabilizer can be in the form a dry powder can be mixed with the synthetic polymer or it can be a suspension or emulsion of the Stabilizer can be mixed with a solution, suspension or emulsion of the synthetic polymer.

The amount of piperidine spirohydantoin derivative admixed with the synthetic polymer II can, depending on the type, the properties and the special purpose of the to stabilizing synthetic Pol2 / meren within further Cot,;, - zen fluctuate. In general, the Piperiöin-spiro-hydaiixc--

30 9 88 1/1198.

ORIGINAL INSPECTED

2327 '· '17

inderiv.ate of the formula II in an amount in the range from 0.01 to 5.0% by weight, based on the amount of the synthetic polymer, added. However, the practical range is varied depending on the kind of synthetic polymer and is 0.01 to 2.0 wt .- $, preferably 0.02 to 1.0 wt .- ^ for polyolefins, 0.01 to 1, 0 wt. ~ $, Preferably 0.02 to 0.5 GeY /. ~ 5 £ for polyvinyl chloride and polyvinylidene chloride and 0.01 to 5 »0 wt .- ^, preferably 0.02 to 2.0 Gev, ^r .- £ 5 for polyurethanes and polyamides.

The stabilizer II can be used alone or in combination with other known antioxidants, ultraviolet absorbers, fillers, pigments and the like. Examples of antioxidants that can be used include 2,6-di-tert-butyl-p-cresol, 4,4'-thio-bis (3-methyl-6-tert-butylphenol), 4,4 ^l- butylidene-bis (3-methyl-6-tert-butylphenol), tris (2-methyl-4-hydroxy-5-tert-butyl-phenyl) butane, tetrakis "[_β- (3,5-di- lert. - butyl-4-hj> -droxyph € myl) propoxymethyl | methane, triphenyl phosphite, dilauryl thiodipropionate and the like.

Examples of suitable ultraviolet absorbers include 4-tert-butylphenyl salicylate, 2-hydroxy-4-octoxybenzophenone, 2- (2 ^f -hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole , Methyl-OC-cyano-β-methyl-β- (p-methoxyphenyl) acrylate5 the Ni-II salt of 2.2 ^l -thiobis (4-tert-butylphenolate) -n-butylamine and the like. If the additives listed above are used, they can usually be embedded in a synthetic polymer composition in a ratio of about 0.5 to 3-0 to 1, based on the piperldine-spiro-hydantoin derivative II. If desired, 2 or more of the piperidine-spirohydantoin derivatives of the formula II can also be used in a satisfactory manner according to the invention.

Some of the piperidine-spiro-hydantoin derivatives listed above II 'are compared to their stabilizing effect: r

3 0 9 8 8 1/119 8.
ORIGINAL INSPECTED

- 6 - 23z7 ^{r <} ! 7

light-induced and thermal degradation of synthetic polymers checked. An example of this test is shown below described in more detail.

Try sb egph training

Mixtures of 100 parts of polypropylene (Boblen JHK-G Mitsui Toatsu Chemicals Ine ;, Japan), which after two Recrystallization from monochlorobenzene was used, and respectively 0.25 parts of the stabilizer compounds given in Table 1 were prepared. The resulting mixtures were mixed and melted, and the melted mixtures were cast into sheets 0.5 mm thick under heat and pressure. It a stabilizer-free control film was also made. The films were at 45 ° C in the "Standard Fade-Lieter Type PA-1 "from Toyo Tika Instruments Inc., Japan (a modification of the Atlas Fade-O-Meter type PDA-R, which has the requirements set out in § 3.8 of Japanese Industrial Standard L-1044 met, exposed to ultraviolet radiation. The time it takes for each film to become brittle is given in Table 1.

Table 1

Stabilizer Ver
binding Time to
brittleness (hours) 1 750 .2 480 4th 760 "5 320 without 60

309881/1 198
ORIGINAL

The above information relates to the Piperidinspirö-hydäntoinderivate II, which can be prepared from the compounds of the invention. More information about these connections are found in German patent application P 22 33 122.2. . '

The invention also relates to a method for production from 1.3 »8-Tria2a-7> 7.9» 9-tetrainethyl-spirο | 4 · 5 | decan ~ 2,4 ~ dithione, which is characterized in that 4-amino-4-cyano-2,2,6,6-tetramethylpiperidine Reacts with carbon disulfide and sulfur,

In carrying out the inventive method, the reaction can be advantageously carried out by contacting the piperidine derivative used as starting material is dissolved in a suitable solvent _s will be given as in alcohols, for example methanol, ethanol and the like, carbon disulfide and sulfur to the resulting solution and then the reaction is carried out at a temperature in the range from room temperature to about 50 ^° C. The time required for the reaction can be varied widely depending on the reaction temperature used, but the reaction is usually complete in "about 1 to 10 hours.

After the reaction has ended, the desired product can be added recovered and purified using a common method. According to an exemplary embodiment, the desired product after completion of the reaction precipitated in situ as a crystalline mass and the mass is recovered by filtration, after which the pure product is obtained by recrystallization from a suitable alcohol, for example methanol.

^x For a better understanding of the invention, the following examples are given.

309881/119 8

ORiQlNAL INSPECTED

2211 ": M

Example l

To a solution of 9.0 g of 4-amino-4-cyano-2,2,6,6-tetraiuethyl piperidine in 70 ml of ethanol were added 6 g of carbon disulfide and 0.2 g of sulfur, and the resulting mixture was allowed to stand at room temperature. Stirred for 6 hours. Then the precipitated in situ crystalline mass was recovered by filtration and recrystallized from ethanol, 1,3, ß-Triaza-7,7,9 $ 9-tetramethyl-spiro J4. 5j ~ decane 2,4-dithione having a melting point above 260 ⁰ C was obtained.

Analysis for · 'C ₁ ^^ N ^ Sg -

Calculated: C, 51.35 % \ H, 7.44 Ji; ^, 16.33 % found: 'C, 51.25 f \ H, 7.36 #; N, $ 16.21,

IR spectrum (Nujöl trituration): | ./^ _H 3360, 3270 cm

Comparative example

5-allyl-1,3, e-triaza-7,7 _< 9,9-tetra methyl-spiro _i C4.5I decan-. 2,4-dithione

50 ml of dimethylformamide were added to a mixture of 14.8 g of the potassium salt of 1,3,8-triaza-7,7,9,9-tetramethyl-spiro 4,5-decane-2,4-dithione and 7 g of allyl bromide the mixture obtained was ^{heated to 70 to 80 °} C. for 5 hours. After the completion of the reaction, the reaction mixture was concentrated and the residue was dissolved in benzene. The benzene solution was concentrated and the precipitated crystalline substance was recrystallized from aqueous ethanol, the desired product being obtained as crystals with a melting point of 182 to 183 ^° C.

3 0 9 8 8 1/119 8
ORiQfMAL fNSPECTEEl ·

2327-17

Analysis for ^c i4 ^H 23 ^N 3 ^S 2 ^:

■ Calculated: $ 0.56.55 \ H, £ 7.80; N, H, 13 g; $ 8.21.52

found: C, 56.43 & i H, 7.72 ^; N, 14.22 j6; S, 21.40 ^

IR spectrum (Nujol friction); ^^ 5300. cm ", ^ _ q 1640 cm".

309881/1198

ORIGINAL INSPECTED ^;

Claims (2)

DA-10452 PATENT CLAIMS 1. 1,3,8-Triaza-7,7,9,9-tetramethyl-spiroj4 -5j decane-2,4-dithione. 2. Process for the preparation of 1,3,8-triaza-7,7,9,9-tetramethyl-spiro U.51 decane-2,4-dithione, marked thereby net that 4-amino-4-cyano-2,2,6,6-tetramethylpiperidine with Carbon disulfide and sulfur is implemented. 303881/1198