DE1928370A1 - Process for the production of long-chain, polyfunctional compounds - Google Patents

Description

PATENT LAWYERS
, DR.W.SCHALK DIPL.-ING. P.'WIRTH · DIFL.-I NC. C. DAN NEN BERG

DR ₁ V ₁ SCHMIED-KOWARZiK DR. P. WEINHOLD '928370

6 FRANKFURT AM MAIN
OR. ESCHENHEIMER STR. SO

Fc Montecatini Edison Sp «, A _o

Foro Buonaparte, 31
Hailand / Italy

Process for the production of long-chain, polyfunctional compounds

The present invention relates to a new method of manufacture long-chain polyfunctional compounds used in the field of Resins, especially polyester resins, for paints and for plasticizers for plastic masses of the PVC type are of particular importance.

According to the process of the invention, a free carbon radical, R ", with an olefin (conjugated to an electron acceptor group Y) R'-GH = CH-Y and with a conjugated diene GH ₂ = CR ¹¹ -CR ¹ " = CH ₂ according to the following general scheme implemented?

2R ° + 2 R'-CH = CH-Y + 2 CH ₂ = CR ¹¹ -CR ¹ "= CH ₂ _J ^

R-CH - CH-CH ₉ -C = C-CH ₇ -CH ₉ -C = C = CHo-CH-CH-R (I)

R ¹ YR "R ^I!. « R "R ^I1! YR «It says

R for a carbon radical ,, and
R ¹ PR "and R" ¹ each denote hydrogen or an alkyl group _e

In the olefins R ¹ -CH = CH = Y 'is the double bond with an electron acceptor group Y of the type -CN', -NO ₂₈ , -SU ₂ = R ¹¹¹ O = COOH _S = CONH ₂₉ '-COOR ¹ " ^1,. -CO-R "» (where R "" stands for © ine AlIgrlgzTAppa with up to 7 carbon atoms) etc. ₀ conjugated o

BAD ORIOINAL

The olefin has 2-10 carbon atoms. The conjugated alkadiene, CH ₂ = CR "-GR ¹ " = CH ₂ has 4-12 carbon atoms and has free, indpositions. The radical R * is a free carbon radical; it can optionally be an (aliphatic, cycloaliphatic, aromatic etc.) hydrocarbon radical which is bound to an electron donor group.

The temperature for carrying out the process is between -3 ° C. and +30 C, preferably between -15 C. and +15 C. One works at atmospheric or optionally under autogenous pressure. Appropriately in Ab-. "Essence of oxygen worked, which does not inhibit the reaction, however is consumed to the extent that it is present, especially from the solvent depending on the particular solvent used = 'While thus the effect of oxygen in water is at its minimum, it will in Methanol quite noticeable.

If R ¹ , R "and R ¹ " each represent hydrogen, the derivative (II) is obtained:

(2) 2R * +2 CH ₂ = CH-Y + 2 CH ₂ = CH-CH = CH ₂ - ^

R-CH ₂ -CH-CH ₂ -CH = CH-CH ₂ -CH ₂ -CH = CH-CH ₂ -CH-Ch ₂ -R (II)

YY
where Y has the meaning given above »

The novel process is of particular practical interest when the radial R * comes from a source .billige _s such as "Industrierohmaterialien ₉ as ketones, 'alcohols' hydrocarbons

0098 23/1959

BAD ÖRlGttiÄL AS

A cheap source of free carbon radicals are the peroxides of ketones, such as 1-hydroxy-cyclohexyl hydroperoxide (the one made from cyclohexanone and hydrogen peroxide or is easily obtainable by self-oxidation of the cyclohexanol).

In the presence of ferrous sulfate with acrylonitrile and butadiene, this compound forms a dinitrile of a tetraarboxylic acid with 26 carbon atoms in 90% yield according to the following scheme:
KO 0OH

(3) f% ^{+ Fe} - >

HOOC- (CH,) .- CH, * + FeOH

2 HOOC- (CH ₂ ) ^ - CH ₂ * + 2 CH ₂ = CH-CH = CH ₂ + 2 CH ₂ = CH-CN ->

HOOC- (CH ₂ ) ₆ -ch-ch ₂ - <: h = ch-ch ₂ ch ₂ -ch = ch-ch ₂ -ch-Cch ₂ ) ₆ = ccoh (in)

- CN 'CM

8,17-Dicyantetracos-10,14-diene-1,2-di-acid

The product (HI) is of small amounts of the branched isomer from the 1,2- and 1,4-dimerization of the allylic radical accompanied;

HOOC- (CH ₂ ) ₆ -CH-CH ₂ -CH-CH ₂ -CH = CH-CH ₂ -CH ^ (CH ₂ ) ₆ -COOH (IV)

CN CH = CH ₂ , CS

10-vinyl-8,15-dicyano-docos-12-en-1,22-diacid

These products are also valuable as they are hydrogenated into the appropriate To convert amino acids. Using methyl acrylate instead of acrylonitrile gives the corresponding derivative with two ester groups instead of the nitrile groups; with the vinyl methyl ketone, on the other hand, is obtained the corresponding diketone.

00982 3/19 5 9 BAD ORIGINAL ^

The use of acyclic ketones as a source of free carbon radicals R * enables bifunctional products to be achieved; so you get e.g. from Methyl ethyl ketone peroxide (which forms the ethyl radical according to (5)), Butadiene and acrylonitrile, the dinitrile (V), a valuable intermediate for dicarboxylic acids and diaraine.

HO 0OH ■

(5) CE ₃ -C-CH ₉ -CH- + Fe -> CH ^ COOH + CHo-CH ₉ * + FeOH

CH - (CH ₂ ) ₂ -CH-CH ₂ -CH = CH-CH ₂ -CH ₂ -CH = CH-CH ₂ -CH- (CH ₂ ) ₂ -CH ₃ (V)

cn approx

Kexadaca-6, 10-diene-4,13-dicarlxmitril

2, ll-DipiOpyldodeca-4 ', 8-diene-l, 12-dinitrile

Another way of obtaining free carbon radicals R "from Ketones consists of the adutiai of N-chloramines and the manufacture of oxyaziridines; the corresponding one is obtained from cyclohexanone and N-chloroethylamine Oxyaziridine, which by decomposition with ferrous salt gives an alkyl radical:

(6) ^ ₁ r ^

[J ^ [j ^N N-CH ₃

0
[J + Cl-NH-CH ₃ - ^> - [j ^N NC

(7) ^ O

Γ ρ N-CH ₃ + Fe """, + H _£ 0

* + SeOE ⁺ *

In the presence of acrylonitrile and butadiene, the product (VI) is obtained, which corresponds to the general formula (II) in which R = CHo-1; iiCÜ- (üH ₂ ) - and Y = -CH, ie the products are analogous to those obtained from cyclohexanone peroxide with the difference that they contain an amide function instead of a carboxylic function.

009823/1959
BADJ0RIGINAL -

The general character of the procedure is further enhanced by the possibility proved to use a different source of the carbon radical R *, i.e. the hydroxyl radical (derived from hydrogen peroxide and ferrous sulfate), the Dissolve hydrogen atoms from C-H bonds and free carbon radicals can deliver:

(8) H ₂ O ₂ 13+ Fe ⁺ *> HO * + FeOH ⁺ *

(9) RH + OH> R * + H ₂ O

Thus, with alkanols such as methanol and ethanol, the CH ₉ OH and CH_CHOH radicals are formed and products of the general formula II are obtained in which R - depending on whether iyfethanol or ethanol was used - - CH ₉ OH or CH ₃ --CH (OH) - means. .

The redox system for the formation of the radical R * is formed by an organic oxidizing agent and an inorganic reducing agent. The organic oxidizing agent is a hydroperoxide, a peroxide, a perester, an alcohol + H ₂ O ₉ , an alcohol + persulfate, etc. The inorganic reducing agent is a salt of a polyvalent transition metal, the metal

.i _{a m} t _m t ι ι ι ι ι ρ

Provides ions in the low valence state, such as Cu, Co, Fe, Cr, V and Ti ⁺ " ¹ " ¹ *.

For 1 mole of oxidizing agent (reference substance), 1 mole of reducing agent is used. With a theoretical yield, 1 mole of R * radical can be obtained. The olefin of the formula R ¹ -CH = GH-I and the alkadene of the formula CH ₂ = CR ¹¹ -CR " ¹ = CH ₉ are used in amounts of 1-k mol, the molar ratio of olefin to diene being between 1-Λ can vary up to 4: 1.

00982 3 / 195S

BAD ORJQINAL

The implementation of the method according to the invention is simple and exists in the treatment of monoolefin and alkadiene in an aqueous or methanolic solution with the redox system, the free carbon radical forms. Other solvents such as acetone or ethyl alcohol can be used, but with less success.

When the reaction is carried out in water, the main product becomes minor Amounts of telomeres accompanied by the higher. feed solubility of

The alkene has more than one alkene unit per alkadiene in comparison to the diene unit included. In any case, it is to alleviate this disadvantage

expedient to work in water with a ratio of alkene to alkadiene which is always less than 1; the process is preferably carried out with monoolefin / diene ratios between 1: 1 to ΙΆ. The excess diene can easily be recovered by distillation and then recycled.

The following examples illustrate the method according to the invention, without limiting it.

The following summary is provided to simplify the description of the examples of the compounds obtained given:

General formula:

(II) R-CH ₂ -CH-CH ₂ -CH = CH-CH ₂ -CH ₂ -CH = CH-Ch ₂ -CH-GH ₂ -R YY

009823/1959

BATH ORIGINAL

link R R. (in) HOQC- (CH) -
* · J (ν) CH ~ -CH ₉ -. (VI) CH ₃ -NHGO- (CH ₂ ) ₅ - (VII) CH ₃ OOC- (CH ₂ ) - (ix) H00C- (CH ₂ ) ₅ - (χ) CH ₃ OOC- (CH ₂ ) .- (XI . HDOC- (CH ₂ ) - (XII) . CH ₃ OOC- (CH ₂ ) ₅ - (XIII) CH ₃ ^ CH ₂ - (XIV) HO-CH ₂ - (XV) CH - CH-

-1

- ^r J; i -CU -CIi -CN

-COUCH, -CUuOH ₃

*O

-CO-CH. -Chi -CN -CN

OH

Each of these compounds became more asymmetrical due to the presence of two Centers obtained as a mixture of two stereoisomers

Example 1

10 g of a 3% aqueous H ₂ O solution were added to 20 g of cyclohexanone with constant stirring. After the heat development ceased,

Methanol and 5 ecm
I50 ecm / conc. Sulfuric acid added. To this solution, cooled to -5 ° C., 16 g of butadiene and 8 g of acrylonitrile were added. Then, with constant stirring and under a nitrogen atmosphere, an aqueous solution of 10 g of heptahydrated ferrous sulfate in 50 ml of 10% sulfuric acid was added dropwise. When the addition was complete, the mixture was diluted with water and brought to room temperature. The excess butadiene was then distilled off and recovered. The mixture was then extracted with ether and the ethereal solution was precipitated with an aqueous 10% strength KaOH solution. After evaporation of the ether, the excess cyclohexanone was distilled off; thus obtained 10 g of neutral product (VII) while

009823/1959

by acidifying the alkaline solution, 10.2 g of acidic product (111) received.

The two products differ in that the first is the methyl ester while the second is the free acid which can be converted to the same ester by treatment with diazomethane.

The ester (VII) distilled at 235-240 ° C. / l Torr as a very thick Gl; according to analysis by thin-layer chromatography, it consisted of 2 main components, L · which corresponded to the two stereoisomers, and of other, minor,

components corresponding to the branched isomers. It didn't become quantitative Separation of the two. Isomers carried out. Through belt analysis, IR spectrography, gnawing nuclear magnetic resonance spectrography and mass spectrography structure III was determined in the presence of small amounts of its esterified isomer IV in the esterified mixture.

Elemental analysis:

Calc .: C 71.15 jS H 9.38 tf N 5.93 £

Found: C £ 70.93 H £ 9.22 N $ 5.88

The IR spectrum showed bands at 2120 cm ~ (-GN group), 1740 () C = 0 "'Group of the ester), 970 (CH-CH-trans), 920 (narrow band of the double

-GH = CH ₂ bond due to the branched isomers). The nuclear magnetic resonance spectrum in CCL, internal reference value IMS (tetramethylsilane)

showed bands at 5.3-5.7 ppm (olefinic hydrogens), 3.6 ppm (ester methyl groups), 2.3-2.15 ppm (CH and CH in qC-position with respect to -COOH, double bonds and -CN) and 1.3 ppm (CH ₂ residues). The cash spectrum showed a molecular weight of 472 for the ester and a molecular weight of 290 (corresponding to the molecular weight less of the CHoOOC-CCH ₂ Jg-CH (CN) fraction) and 236 (corresponding to half the molecule) for the two fractions.

00982 3/1959 BAD ORlQlNAi.

3 eis ρ ie 1

Example 1 was repeated "wherein a molar ratio of hydrogen peroxide / cyclohexanone / acrylonitrile / butadiene of 1: 2: 5 and ₉ used 15I was carried out in a methanol solution; d _'e h is the ferrous sulphate, dissolved in methanol, added to the methanol solution of the other components For the same products, however, were obtained as in Example I. ₈ in unterschfedlichen ratios; the sster yield was increased to $ 60 while the acid yield decreased to $ 40, Example 3

Example 1 was repeated, but with 14.5 instead of acrylonitrile g of methyl acrylate were used. This gave 8.5 g of acidic product (IX) and 12.4 g of ester '(X), which distills at 240-245 ° C ^ 1 Torr as a very thick oil. In this case too, the structure of the mixture of isomeric esters (stereoisomers and branched isomers) was determined by elemental analysis, IR spectrography, nuclear magnetic resonance spectrography and mass spectrography determined; the latter analysis revealed the molecular size and the order in which the various units that are part of the molecule are linked together »

Example 4

10 g of an aqueous hydrogen peroxide solution (34 % ± g) became 20 g. Cyclohexanone was added and the mixture was then dissolved in 60 ecm of methanol, the 5 ecm of conc. Containing sulfuric acid, dissolved. The solution thus obtained was in a nitrogen atmosphere and under stirring, at the same time, cooled to -10 ⁰ C. to 4 ⁰ C, in a mixture of 7 g of methyl vinyl ketone, 16.2 g of butadiene and 40 g of ferrous sulfate in heptahydratisiertem I50 ecm Added dropwise methanol. After the addition had ended, excess butadiene and methanol were distilled off, and the whole was then taken up in water and extracted with ether, using a sodium hydroxide solution such as

009823/1959

- ίο -

above the acid product was separated from the ester. 8.3 g of acid (XI) and 7 g of ester (XII) were thus obtained which, according to elemental analysis and spectroscopy, had the same composition as in the preceding examples, with the difference that they had groups instead of Ϊ -GOGH. Example 5

10 g of oxyaziridine (obtained from cyclohexanone and S-chloromethylamine) were under a nitrogen atmosphere at a temperature between -10 G. and -5 ° C. with stirring in a solution of 16 g of butadiene, 10 g of acrylonitrile and 23 g L · heptahydratisiertem ferrous sulfate in 100 cc of methanol einget-Auchter, "excess butadiene and methanol were distilled off, taken up in water, and 8.1 g of product were then incubated with Ether extracted that itself. partially solidified; ' crystallized after being taken up in ethyl acetate

a solid product with a F. of 102 C. The melting point changed not by subsequent recrystallizations, and according to thin layer chromatography the product was a single derivative »According to elemental analysis, determination of molecular weight and IR, nuclear magnetic resonance and mass spectrography, the isomer had the structure (¥ 1).

. Elemental analysis:

"Calculated: C $ 71.45 H $ 9.85 N 11.90 i
found: C 71-6 £ H 9.62 % N 11.9 ^ $

The mass spectrum showed a molecular weight of 470 (theory = ¹ Y] Qi) with two main peaks at 236 (half mass) and 289 (corresponding to the _{molecule reduced by CH 3} -NHCO- (CH ₂ ) £ * £ H (CN) -) .

The IR spectrum showed bands at 965 cnT (-CH = CH-trans), 2250 cm "(-GN) and 1650 cra ~ (amidic CO) ...

009823/1 95-9

BAD QpQINALj \} hB.

The part which was soluble in ethyl acetate and showed itself as a viscous product had the same analytical properties as the crystallized product, but the spectral analysis _{showed the presence of the branched isomer (-CK = CH 9} group).
Example 6

In a mixture of 10.8 g of butadiene, 5 »3 g of acrylonitrile, Ik g heptahydratisiertem ferrous sulfate, 100 cc water and 50 g of urea (for preventing consolidation of the water), at a temperature between -8 and -5 ° C. c . 6.3 g of oxaziridine were added dropwise. When the addition had ended, the mixture was brought to room temperature, the excess butadiene was recovered and the separated oil was decanted. Thus there was obtained 11.2 g of a product νiskosen _s according to elemental analysis a low content of carbon and hydrogen and a higher content of nitrogen than it had been calculated for (VI) \ _s iar. The mass spectrum showed in addition to the molecular ion ^ 70, which corresponds to the molecular weight of (VI)) a molecular ion 523 "which corresponds to a telomeric (VIII) rat of a further acrylonitrile unit (^ 70 + 53)"

Example 7

Example 1 was made using i & hyläthylketon instead of cyclohexanone repeated. This gave 6.7 g of dinitrile, which at 155-160 ° C./l Torr distilled; from the analytical and spectrographic data, the dinitrile turned out to be a derivative (XIII) with small amounts of the branched isomers. In this case, too, there was no separation of the isomers.

Example 8 ^:

Into a solution of 8 g of acrylonitrile and 16.2 g of butadiene in 250 cc of methanol two solutions of each of 6 g of hydrogen peroxide in cc of water and 5 were added simultaneously under stirring and cooling to -10 ⁰ C. until ^ ⁰ C. under a nitrogen atmosphere $ g of heptahydrated ferrous sulfate in 1 * K) ecm of a 5-pi.gQn

009823 / 1959- 6AD ORiQJNAU "'-" *

Sulfuric acid solution added. When the addition was complete, the mixture became brought to room temperature, excess butadiene and methanol were added distilled off and the residue extracted with ether.

Thus obtaining 10 g of a product "that distilled at 230-24Q ⁰ C./4 Torr. The analytical data showed it to be a mixture of isomers of two molecules of methanol, two molecules of acrylonitrile, and two molecules of butadiene. In particular, the mass spectrum showed the order in which the various units are bound; it corresponded to structure XIV. Small bands of the -CH = CH ₂ group indicated the presence of the stereoisomers corresponding to the branched isomers as by-products. Example 9 ^:

In a mixture of 8 g of acrylonitrile, butadiene l6,2 g, 4-1 g heptahydratisiertem ferrous sulfate, 50 cc water and 250 cc of ethanol was added with stirring in a nitrogen atmosphere and with cooling to -12 ⁰ C. to -8 ° C. 4.5 g of hydrogen peroxide were added dropwise to 80 ecm of water. After further work as in Example 8, 4 g of product (XV) were obtained with the same properties as the product obtained with methanol, but with two CHo-CHGH groups

instead of CH ₉ OH.

009823 / 19E9 BAD ORIGINAL

Claims (1)

- 13 - ■ Patent claims /l.A Process for the production of long-chain, "polyfunctional compounds the general formula: R-GH - CH-CH ₀ -G = C-CH ₀ -CH ₉ -C = C-CH ₉ -CH-CH-R 1 1 ⁴ I ι ^{ά c} 1 1 ^c - 1 I Ri. Y R "R <" R "R '" Y Ri in which R stands for a carbon radical, R ', R- "and R ¹¹¹ each mean hydrogen or alkyl and Y stands for a slectron acceptor group, characterized in that one takes place at a temperature between -3O ⁰ C. and +30 ⁰ C, a free carbon radical R 'in solution with a monoolefin of the formula R ^! -CH = CH-i with 2-10 carbon atoms and with a conjugated alkadiene of the formula CH ₂ = CR "-CR" ¹ = CH ₂ with 4--12 2.- The method according to claim 1, characterized in that the electron acceptor group Y -CN, -COOH, -NO ₂ , -SO ₂ ^ R "", CONH ₂ , -COOR "" or -CO-R "" is where R ¹ " ^{1 is} alkyl. 3, - Method according to claim 1 and 2, characterized in that the free Carbon radical R "is formed by a redox system from an oxidizing organic compound and an inorganic reducing salt. 4. - Method according to claim 3 _f, characterized in that the oxidizing organic compound is a hydroperoxide, a peroxide, a perester, an alcohol + H ₂ O ₂ , an alcohol + ■ persulfate or an oxyaziridine. 5.- The method according to claim 3 ». Characterized in that the reducing inorganic salt is a salt of a polyvalent transition metal, the Cu ⁺ , Co ⁺ *, Fe ⁺ *. Cr ⁺⁴ ", V ⁺ * or Ti" ^r yields, 9823/1959 - Ik - 6.- The method according to claim 1 to 5i, characterized in that per mole of the oxidizing organic compound 1 mol of inorganic, reducing salt, 1-Λ mol of monoolefin and 1- ^ mol of alkadiene can be used. 7 · - Method according to claim 1 to 6, characterized in that one preferably works in solution in methanol, water or in methanol / water. 8.- Method according to claim. 1 to?> characterized in that at a temperature preferably between -15 ° C and -15 C and at atmospheric Pressure works. 9.- The new compounds according to the formulas (III), (V), ^ T), (VII), (IX), (X), (XI), (XII), (XIII), (XIV) and (XV) in the table. , The patent attorney: 009823/1959