DE1087594C2 - Process for the production of new nitrogen-containing epoxy compounds - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

PATENT 1 087

ON REPORTING DAY:

NOTICE
THE REGISTRATION
AND ISSUE OF
EDITORIAL:

ISSUE OF
PATENT LETTERING:

DBP 1087594 kl. 12 ο 25

INTERNAT. KL. C 07 d APRIL 1, 1959

AUGUST 25, 1960

MARCH 16, 1961

DIVERS FROM

EDITORIAL

(C 18705 IVb / 12o)

The invention relates to the production of new nitrogen-containing epoxy compounds of the general formula

R ₂ R ₁ / / R ₈ CH \ X κ; St. n- 1 _/ R ₃ ' \ /
C. V ^ iI ₂ ■ vr / Y " C. /
C.
/ \ \ /
C. , -! - N- C. \ - CH, R ₆ Ri ' \, \ /
-C \ /
C.
/ \ / \ /
C.
/ \ /

Method of manufacture
new nitrogenous epoxy compounds

Patented for:

CIBA Aktiengesellschaft, Basel (Switzerland)

Claimed priority:
Switzerland from April 2 and July 23, 1958

15 Dr. Hans Batzer, Ariesheim,

and Dt. Erwin Nikles, Basel (Switzerland),

have been named as inventors

ao

R ₇ '

R ₄ '

R ₆

wherein R ₁ , R ₁ ', R ₂ , R ₂ ', R ₃ , R ₃ ', R ₄ , R ₄ ', R ₅ , R ₅ ', R ₆ , R ₆ ', R ₇ , R ₇ ', R ₈ , R ₈ ', R ₉ and R ₉ ' stand for monovalent substituents such as halogen atoms or aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon radicals, in particular for lower alkyl radicals with 1 to 4 carbon atoms, or for hydrogen atoms, where R ₁ and R ₅ or R ₁ 'and R ₅ ' together can also mean a divalent substituent, such as a methylene group, X and Y mean acyl, carbalkoxy, carbaryloxy, carbaminyl, cyano or sulfonyl radicals, Z stands for a divalent organic A radical which can be interrupted by functional groups or by heteroatoms such as nitrogen, oxygen or sulfur atoms, in particular an alkylene or phenylene radical, m is an integer not exceeding 2 and η is a small integer.

The new compounds of the general formula I are obtained according to the invention by adding compounds the general formula

R ₂

R ₁

R ₃

CH ₉ -N-

- (Z ^ ₁ -N-

n-l CH ₉

R ₁ 'R ₂ '

R ₃ '

R. '

R ₇

R ₇ '

wherein R ₁ , R ₁ ', R ₂ , R ₂ ', R ₃ , R ₃ ', R ₄ , R ₄ ', R ₅ , R ₅ ', R ₆ , R ₆ ', R ₇ , R ₇ ', R ₈ , R ₈ ', R ₉ , R ₉ ', X, Y, Z, m and η have the meaning given above, treated in a manner known per se with epoxidizing agents such as peracetic acid or perbenzoic acid.

The starting compounds of the general for-

109 533/363

mel II can in turn be obtained by adding secondary amines of the general formula R ₂ R ₁ R ₁ 'R ₂ '

R ₀

CH ₂ -N-

- (Z) _n ^ ₁ -N-CH ₉

R ₈ '

C C

R ₇

wherein R ₁ , R ₁ ', R ₂ , R ₂ ', R ₃ , R ₃ ', R ₄ , R ₄ ', R ₅ , R ₅ ', R ₆ , R ₆ ', R ₇ , R ₇ ', R ₈ , R ₈ ', R ₉ , R ₉ ', Z, m and η have the meaning given in the general formula I, treated with agents which have an acyl, carbalkoxy, carbaryloxy, carbaminyl, cyano or Ability to introduce sulfonyl radical.

For example, mono- and dicarboxylic acids and their functional ones are used to introduce the acyl radical Derivatives, such as acid halides and especially acid anhydrides, are possible.

The acyl radical introduced in this way can be one of the formula

R ₇ '

—C:

where A _{1 is} an optionally substituted aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon radical or a heterocyclic radical; He can also, for example, the formula

c — A ₂ - c:

OH

O

correspond, where A _{1 has} the same meaning as

R ₂

R _B '

20th

25th

in the acyl radical of the formula

-CA ₁

■ II ο

To introduce the carbaminyl radical, one can start, for example, from urea or from an N-substituted urea, with a radical of the formula _{being split off from NH 3}

A,
- C - NC

O ^

is introduced, where A ₃ and A ₄ can stand for hydrogen atoms or aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radicals.

The introduction of the cyano radical - C = N can, for example, with a halogen cyanide, such as cyanogen bromide, respectively.

A sulfonyl radical can be introduced, for example, by means of chlorosulfonic acid or halosulfuric acid esters or sulfonic acids or their functional derivatives, such as sulfonic acid halides. the Sulphonyl radical can, for example, of the formula

correspond, where A ₂ denotes an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radical which is optionally interrupted by functional groups or heteroatoms.

A carbalkoxy or carbaryloxy radical can be introduced, for example, by means of haloformic acid esters respectively. The carbalkoxy or carbaryloxy radical can, for example, have the formula

f \ A

VY X \ |

correspond, in which A _{1 has} the same meaning as in the acyl radical of the formula

Il ο

and p is an integer of 1 or 2.

The secondary amines of the general formula III can be obtained by various methods.

One can in this way lead to secondary monoamines of the formula

R ₁ 'R ₂ '

R ₉ R ₉ '

. \ CH ₂ -NH-CH ₂ C

R ₈ R ₈ '

R ₄

R ₇

R /

R ₅

R ₆

R ₆ '

arrive by adding compounds of the general or formula

R ₂ R ₁

R ₃ C

^R e

-CH = N-CH ₉

R ₁ 'R ₂ ' CC

^R 8

CC

R ₁ CR ₇

R ₈ '

R ₇ '

R ₆ '

R ₅ '

-r / ^ Tj means, or their formation components one

⁵⁶ 15 Hydrogenation under conditions which do not

wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R _{9 represent} the above saturation of the C = C double bond in the cyclohexene

have given meaning and B _{cause a monovalent r} j _n g, subjects.

Remainder of the formulas By suitable choice of the starting components

O can be built symmetrically or asymmetrically

./*_λτ r " CH = NH CH = N OH ²⁰ gray compounds of the general formula IV

'\' ~~ will hold.

NH,

R ₂ R ₁

s / \ • C C-

Symmetrical compounds of the formula R ₁ R ₂

R ₃

CH ₉ -NH-CH ₉

C C

/ \ / R ₄ C

R ₈

R ₇

C C

R ₇ CR ₄

are obtained, for example, when imines, common formula V hydrogenated or when one of one

N ll

Oximes, acid amides or, in particular, nitriles of the general

R ₂ R ₁

Schiff's base of the general formula

CH = N-CH ₉

R ₄

C C

R5 R ₆

R ₈

R ₇

R ₉ c R ₃

R ₈

C C

R ₇ CR ₄

goes out. Such Schiff bases are in turn directly linked to the general formula VII for example accessible by condensation of 2 moles of formula VI get by a mixture of

Mole of the compound of general formula VIII and about 1 mole of ammonia hydrogenating conditions subject.

The Schiff bases can also be obtained by adding 1 mol of an amine of the general formula

R ₂ R ₁

60

of an aldehyde of the general formula R ₂ R ₁

R \ ^χ C C-

C C

R ₈

R ₇

VIII

* C

C C

R ₉

CH ₂ NH ₂

with 1 mol of ammonia under reducing conditions. You can do this without isolating the intermediate preserved Schiff base of the general

R ₄

C C

R5 R ₆

R ₈

R ₇

7 8

with 1 mole of an aldehyde of the general formula VIII The secondary ones are particularly easily accessible

implements. Amines of the general formula

CH,

CH,

CH

CH-CH ₂ -NH-CH ₂ -CH

CH

CH CH-R

CH ₂

R'-CH CH

\ /
CH,

wherein R and R 'represent a hydrogen atom or a starting from ammonia and 6-methyl-zl ³ -tetra-

stand lower alkyl. 15 hydrobenzaldehyde, are produced, with the

For the production of bis (/ l ³ -tetrahydrobenzyl) - the last-mentioned compound again conveniently

amine can be obtained from ^{I 3} tetrahydrobenzonitrile- addition of crotonaldehyde to butadiene-

go, which is convenient by the addition of acrylic Hch. The bis-

acid nitrile can be produced on butadiene. (1,5-endomethylene-zl ³ -tetrahydrobenzyl-) amine.

The bis- (6-methyl-, d ³ -tetrahydrobenzyl) -amine can, 20 to secondary diamines of the general formula

R,

Ri '
R ₉ '\'

CH, - NH-Z-NH-CH ₅

R ₈

c c

R ₄ CR ₇

R ₅ Re

is obtained by adding compounds of the general formula

R ₂ R ₁

</ R ₉

R _a '

C C

/ \ / \ R ₇ 'CR ₄ '

R ₁ 'R ₂ '

R ₅ '

CH = N-Z-N = CH

R ₈

C C

/ \ / \ R ₁ CR ₇

/ \. R ₅ R ₆

or compounds of the general formula

R ₂ R ₁

₃ ^X c ^/ R ₉

C C

R ₇ 'CR ₄ '

CH ₉ -N = Z = N-CH,

R ₁ 'R ₂ '

R ₉ 'c R ₃ '

—C C

R ₇

C C

R ₇ 'CR ₄ '

R5

wherein R ₁ , R ₁ ', R ₂ , R ₂ ', R ₃ , R ₃ ', R ₄ , R ₄ ', R ₅ , R ₅ ', R ₆ , denents a hydrogenation which does not have any saturation R ₆ ', R ₇ , R ₇ ', R ₈ , R ₈ ', R ₉ and R ₉ 'and Z have the meanings given above for the C =C double bonds in the cyclohexene ring, or the formation of which acts, is subject.

The Schiff bases of the general formula XII can be obtained by condensation of 2 moles of an aldehyde of the general formula VIII with 1 mole of a diprimary di- or polyamine, such as ethylenediamine, propylenediamine, hexamethylenediamine, Diethylenetriamine, triethylenetetramine, tetraethylene pentamine, diaminocyclohexane, phenylenediamine, Benzidine, ρ, ρ'-diaminodiphenylmethane and ρ, ρ'-diaminodiphenyl sulfide, sulfone or oxide.

The Schiff bases of the general formula XIII are accessible by condensation of 2 moles of one Amine of the general formula IX with 1 mole of a dialdehyde, such as glyoxal, malealdehyde, succinaldehyde, Phthalaldehyde and terephthalaldehyde.

When using polyamines with more than two primary amine groups, such as 1,2,3-triaminopropane or triaminobenzene, or polyaldehydes with more than two aldehyde groups, Schiff bases or amines of the general formula XI obtained therefrom by hydrogenation with more than two cyclohexene radicals bonded to secondary amine nitrogen atoms, ie the radical Z in this case is represented by further radicals of the formula
9

C ^R 3

R ₁

-ISTH-CH ₂ C

R ₈

CC

R ₇ CR ₄

R ₆ R ₈

substituted.

The hydrogenation of the compounds of the general formulas V, XII or XIII can be carried out according to the customary Reduction methods take place, which a hydrogenation of

-C = N, —C = N- or -

-Groups

NH,

without simultaneous hydrogenation of the C =C double bond allow in the cyclohexene nucleus.

Such methods are, for example, reduction with sodium in an alcoholic medium and reduction with lithium aluminum hydride.

For certain compounds, such as cyclohexenenitrile, the catalytic hydrogenation in Presence of catalysts such as Raney nickel or copper chromite.

The epoxidation of the C = C double bonds according to the invention in the cyclohexene rings is carried out by customary methods, for. B. with the help of peracetic acid or perbenzoic acid.

The novel epoxy compounds of general formula I obtainable according to the invention react with the usual hardeners for epoxy compounds. By adding such hardeners, they can therefore be crosslinked or cured in the same way as other polyfunctional epoxy compounds or epoxy resins. Basic or, in particular, acidic compounds are suitable as hardeners of this type. For example, amines or amides, such as aliphatic and aromatic, primary, secondary and tertiary amines, e.g. B. mono-, di and tributylamines, p-phenylenediamine, ethylenediamine, Ν, Ν-diethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraäthylenpentamin, trimethylamine, diethylamine, triethanolamine, Mannich bases, piperidine, piperazine, guanidine, phenyldin, guanidine, such as diphenylduanidine Dicyandiamide, aniline-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins, polymers of aminostyrenes, polyamides, e.g. B. those from aliphatic polyamines and di- or trimerized, unsaturated fatty acids, isocyanates, isothiocyanates; polyhydric phenols, e.g. B. resorcinol, hydroquinone, quinone, phenolaldehyde resins, oil-modified phenolaldehyde resins, reaction products of aluminum alcoholates or phenolates with tautomeric compounds of the acetoacetic ester type, Friedel-Crafts catalysts, e.g. B. AlCl ₃ , SbCl ₅ , SnCl ₄ , FeCl ₃ , ZnCl ₂ , BF ₃ and their complexes with organic compounds; Phosphoric acid. Polybasic carboxylic acids and their anhydrides are preferably used as hardeners, for example phthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, hexachloroendomethylenetetrahydrophthalic anhydride or mixtures thereof; Maleic or succinic anhydride, optionally together with accelerators such as tertiary amines.

The term "hardening" as used here means the transformation of the foregoing epoxidized compounds to form insoluble and infusible resins.

The new epoxy compounds or their mixtures with hardeners can be in fillers, plasticizers and coloring substances are added to any phase. As a stretching and fillers can, for example, asphalt, biturns, glass fibers, mica, quartz powder, cellulose, Kaolin, finely divided silica (»AEROSIL«) or metal powder can be used.

The epoxy compound fertilizers produced according to the invention or their mixtures with hardeners can be in the unfilled or filled state as well as in solution or emulsion as textile auxiliaries, laminating resins, varnishes, paints, dipping resins, casting resins, molding compounds, Spreading, filling and leveling compounds and adhesives or for the production of such agents serve.

In the following examples, parts are parts by weight, percentages are percentages by weight, and the Temperatures are given in degrees Celsius.

For the production of the starting material, protection is not given in the context of the present invention claimed.

example 1
a) bis (/ l ³ -tetrahydrobenzyl) -amine

922 parts of z) ^3- tetrahydrobenzonitrile are stirred in a stirred autoclave at 131 to 132 ^P and 140 atm. Hydrogenated initial pressure in the presence of 40 parts of copper chromite. After taking up 398 800 parts by volume

Hydrogen (normal conditions) the reduction is interrupted. The catalyst is filtered off and the filtrate is distilled. In addition to a ^{forerun containing z) 3} -tetrahydrobenzylamine, 580 parts of bis - ^ - tetrahydrobenzyl) amine are distilled at 162 to 164 ° / 14 mm Hg. n ² S = 1.5059.

109 533/363

b) A solution of 229 parts of zi ³ -tetrahydrobenzylamine in 750 parts by volume of benzene is mixed with 227 parts of zf ³ -tetrahydrobenzaldehyde in 750 parts by volume of benzene, with immediate heating and separation of water. The mixture is heated to the boil and dehydrated in a circulation distillation apparatus as described in the article by H. Batzer and co-workers in "Makromolekulare Chemie", Vol. 7, 1951, pp. 84 and 85. The solvent is evaporated and the residue is distilled in vacuo at 11 mm Hg. 382 parts (92% of theory) Schiff base distill at 147 °.

51.0 parts of the Schiff base described above are dissolved in 188 parts of absolute alcohol and a total of 23.3 parts of sodium in pieces, from 3 to 4 g, are added over the course of 30 minutes. The mixture is then refluxed until the sodium has completely dissolved. The again cooled mass is poured onto 500 parts of ice water. The separated oil is separated off, treated with 160 parts by volume of 2N sulfuric acid and distilled with steam until 2000 parts of water have condensed. The distillate is discarded. The mixture is made alkaline with strong sodium hydroxide solution and extracted with ether. After drying over sodium sulfate, the extract is evaporated and distilled at 11 mm Hg. At 152 ° to 157 °, 42.8 parts (84% of theory) of bis-zi ³ -tetrahydrobenzyl) amine distill.

c) 54 parts of z ( ^3- tetrahydrobenzaldehyde are dissolved in 170 parts by volume of methanol, and 7.7 parts of ammonium chloride in 25 parts of water and 26 parts by volume of 25% ammonia are added, the mixture heating up and a precipitate being formed, in the presence of 13 parts Raney nickel is hydrogenated at 56 to 65 ° and 70 to 120 atmospheres of hydrogen until the theoretically required amount is taken up. The catalyst is filtered off. After the solvent has been driven off, the residue is taken up in 500 parts by volume of ether and twice 200 parts by volume of 2 η The acidic aqueous solutions are combined, made alkaline with concentrated sodium hydroxide solution and extracted with twice 250 parts by volume of ether. The ethereal extract is dried over sodium sulfate, evaporated and distilled at 14 mm Hg. At 60 to 70 ° 19 parts of I ³ -Tetrahydrobenzylamine (35% of theory) and at 141 to 156 ° 24 parts of bis (zl ³ -tetrahydrobenzyl) amine (47%).

d) N, N-bis (tetrahydrobenzyl) formamide

102.5 parts of bis (z) ³ -tetrahydrobenzyl) amine are boiled with 300 parts by volume of benzene and 55 parts of 85% formic acid in a circulating distillation apparatus charged with sodium sulfate until the distillate runs clear. The solvent and the excess formic acid are evaporated in a water jet vacuum and the residue is distilled at 0.2 mm Hg. 106 parts (91% of theory) of N, N-bis (z) ³ -tetrahydrobenzyl) formamide with a boiling point of 141 ° are obtained. M ² o ° = 1.5218.

Analysis: C ₁₅ H ₂₃ ON

Calculated ... C = 77.20, H = 9.94%;
found ... C = 77.10, H = 9.94%.

e) N, N - bis (3,4 - epoxyhexahydrobenzyl) formamide

93 parts of bis (zJ ³ -tetrahydrobenzyl) formamide are dissolved in 400 parts by volume of benzene. After 20 parts of anhydrous sodium acetate have been added, 180 parts of 42% strength peracetic acid are added dropwise over the course of 31 minutes. The temperature is kept at 29 ° by external cooling. After a further 30 minutes at 29 °, 94% of theory of peracetic acid has been consumed. The lower, aqueous phase is separated off and the benzene is washed three times with 200 parts of water, 200 parts of 2 η soda and 50 parts of monosodium phosphate solution. The aqueous parts are extracted with twice 300 parts of benzene. The combined extracts

ίο are dried over sodium sulfate and then evaporated. After drying in a high vacuum at 60 to 70 °, 89 parts of epoxy are obtained. The product, that is a mixture of several stereoisomeric compounds' is, crystallizes after standing for some time.

Epoxy content: 6.8 equivalents per kg (90% of theory).

B e i s ρ i e 1 2

a) N, N-bis (zl ³ -tetrahydrobenzyl) acetamide

To 102.5 parts of bis (zl ³ -tetrahydrobenzyl) amine, 75 parts of acetic anhydride are added dropwise with stirring. The mixture heats up to 150 °. After 30 minutes at 140 °, the acetic acid formed and the excess acetic anhydride are distilled off in a water jet vacuum. On distillation, the residue gives 117.9 parts (95% of theory) of bis (zl ³ -tetrahydrobenzyl) acetamide with a boiling point of 134 to 136 ° / 0.05 mm Hg.

Analysis: C ₁₆ H ₂₃ ON

Calculated ... C = 77.68, H = 10.19%;
found ... C = 77.56, H = 10.19%.

e) N, N-bis (3,4-epoxyhexahydrobenzyl) acetamide

102 parts of bis (zf ³ -tetrahydrobenzyl) amine are mixed with 400 parts by volume of benzene. 51 parts of acetic anhydride are then added dropwise over 14 minutes while stirring and cooling with ice. The temperature rises to 25 °. After adding 30 parts of anhydrous sodium acetate, 230 parts of 42% strength peracetic acid are added in portions over 40 minutes with stirring. The temperature is kept at 29 ° by cooling with ice. The cooling is then removed and the reaction is allowed to react again for 38 minutes at 29 °. After this time 90% of the theory of peracetic acid has been consumed. The aqueous layer is separated off and the benzene is washed three times with 500 parts by volume of water, 400 parts by volume of 2 η soda and 50 parts by volume of monosodium phosphate. The aqueous parts are extracted with 500 parts by volume of benzene. When evaporated, the extracts together give 95 parts of a viscous resin which contains 6.33 epoxy equivalents per kg (89% of theory).

Example 3
a) N, N-bis (zl ³ -tetrahydrobenzyl) -p-toluene-sulfonamide

To the mixture of 205 parts of bis (zl ³ -tetrahydrobenzyl) amine in 300 parts by volume of ethylene chloride and 500 parts by volume of 2η sodium hydroxide solution, the solution of 191 parts of p-toluenesulfonic acid chloride in 500 parts by volume of ethylene chloride is added dropwise with thorough stirring.

The temperature is kept at 10 ° by cooling with ice. After 2 hours at room temperature, the Separated aqueous layer and extracted with 200 parts by volume of ethylene chloride. The extracts are made with Washed twice 100 parts of 0.5N sodium hydroxide solution, dried over sodium sulfate and evaporated in vacuo. 358.2 parts (99.7% of theory) are obtained

N, N - bis - (A ³ - tetrahydrobenzyl) - ρ - toluenesulfonamide, melting point 87 to 89.5 °.

After three crystallizations from methanol, a preparation with a melting point of 95 ° to 96 ° is obtained.

Analysis: C ₂₁ H ₂₉ O ₂ NS

Calculated. . . C = 70.16, H = 8.13, S = 8.92%;
found ... C = 70.14, H = 8.40, S = 8.84%.

e) N, N-bis (3,4-epoxyhexahydrobenzyl) -p-toluenesulfonamide

358 parts of p-toluenesulfonamide are dissolved in 1500 parts by volume of ethylene chloride and mixed with 50 parts of anhydrous sodium acetate. 450 parts of 42% strength peracetic acid are added dropwise at 30 ° with stirring and ice cooling over 45 minutes. The "mixture is kept for a further 75 minutes through occasional cooling at 30 °. After this time are 97 ° / o of theory of peracetic acid consumed. The solution is extracted with three times 500 parts by volume of water and twice with 200 parts by volume of 2 η-Soda, dried over sodium sulfate dried and then evaporated to give 375 parts of crystallized epoxy. The product has an epoxy content of 4.72 epoxy equivalents per kg (92.3% of theory).

A preparation is crystallized three times from methanol for analysis. Melting point 131 to 132 °.

C ₂₁ H ₂₉ O ₄ NS

Calculated ... C = 64.42, H = 7.46, O = 16.35%;
found ... C = 64.67, H = 7.66, O = 16.02%.

Example 4
, a) N, N-bis (zl ^s -tetrahydrobenzyl) urethane

102.5 parts of bis (4 ³ -tetrahydrobenzyl) amine are dissolved in 400 parts by volume of ethylene chloride, and 250 parts by volume of 2 η soda are added. With thorough stirring and cooling, 56 parts of ethyl chloroformate are added dropwise at 5 ° to 7 ° in 30 minutes. The mixture is then allowed to warm to room temperature with stirring. The ethylene chloride is separated, and the aqueous layer having a _pH value of 6 is extracted with 250 parts by volume of ethylene chloride. The extracts are combined, dried over sodium sulfate and evaporated. On distillation, the residue gives 119.5 parts (86% of theory) of N, N-bis ( ^{I 3} -tetrahydrobenzyl) urethane with a boiling point of 131 ° to 136 ° (0.02 mm Hg). w ² _D ° = 1.5006.

Analysis: C ₁₇ H ₂₇ O ₂ N

Calculated ... C = 73.60, H = 9.81, N = 5.05%;
found ... C = 73.6, H = 9.7, N = 5.2%.

e) N, N-bis (3,4-epoxy-hexahydrobenzyl) urethane

108 parts of N, N-bis (z4 ³ -tetrahydrobenzyl) urethane are dissolved in 500 parts by volume of benzene, and 20 parts of sodium acetate are added. 200 parts of 42% strength peracetic acid are then added dropwise at 30 ° over the course of 30 minutes, with cooling and stirring, and the mixture is kept at 30 ° for a further 2 hours. After this time, 97% of theory of peracetic acid has been consumed.

The benzene solution is diluted three times with 150 parts of ice water and twice with 150 parts by volume Washed soda solution. The aqueous parts are extracted with 250 parts by volume of benzene. the combined extracts are dried over sodium sulfate and evaporated. You get a water-clear Resin with an epoxy content of 5.67 equivalents per kg (87.7% of theory).

Example 5 a) N, N-bis - (^ - tetrahydrobenzyl) cyanamide

102.5 parts of bis (ziMetrahydrobenzyl) amine become dissolved in 400 parts by volume of ethylene chloride and covered with 250 parts by volume of 2N soda solution. Under

With good stirring and cooling, 54 parts of cyanogen bromide, dissolved in 200 parts by volume of ethylene chloride, are added dropwise at −2 to + 2 ° in 15 minutes. The mixture is then warmed to room temperature with constant stirring. The aqueous layer now shows a _pH value of. 6

The ethylene chloride is separated off and the water is extracted with 200 parts by volume of ethylene chloride. The extracts are combined, dried over sodium sulfate, evaporated and distilled. At 144 to 148 ° / 0.04 mm Hg, 97.3 parts (85% of theory) of N, N -bis- (A ^s - tetrahydrobenzyl) -cyanamide are transferred. n ² § = 1.5157.

Analysis: C ₁₅ H ₂₂ N ₂

Calculated. .. C = 78.21, H = 9.63, N = 12.16%; found ... C = 78.07, H = 9.83, N = 11.91%.

e) N, N - bis (A ³ - epoxyhexahydrobenzyl) cyanamide

85.0 parts of bis (d ³ -tetrahydrobenzyl) cyanamide are dissolved in 300 parts by volume of benzene. After 20 parts of sodium acetate have been added, 190 parts of 42% strength peracetic acid are added in portions over 33 minutes, while cooling and stirring at 30 °. After a further 60 minutes at 30 ° to 28 °, 96% of theory of peracetic acid has been consumed. The benzene is washed three times with 100 parts by volume of water and twice with 100 parts by volume of soda solution. The aqueous parts are extracted with 250 parts by volume of benzene. The combined extracts give, on evaporation, 77.0 parts (80% of theory) of a water-clear resin with an epoxy content of 6.76 equivalents per kg (88.6% of theory).

Example 6

b) Di-Schiff base from zl ³ -tetrahydrobenzaldehyde and ethylenediamine

31 parts of ethylenediamine are mixed in 200 parts by volume of benzene with 118 parts of 93% strength zf ³ -tetrahydrobenzaldehyde. The mixture immediately excretes water. It is heated to the boil and drained in a circulating distillation apparatus. The solution is evaporated and the residue is distilled in a high vacuum. At 117 to 126 ° and 0.01 mm Hg, 107 parts (88% of theory) of Di-Schiff base are obtained. n% ° = 1.5177.

Analysis: C ₁₆ H ₂₄ N ₂

Calculated ... C = 78.63, H = 9.90, N = 11.46%; found ... C = 78.84, H = 10.19, N = 11.14%.

c) N, N'-bis (zl ³ -tetrahydrobenzyl) ethylenediamine

122 parts of the Di-Schiff base described above are dissolved in 800 parts of absolute alcohol and a total of 92 parts of sodium are added in portions, causing the mixture to boil. Against At the end of the reaction, a further 100 parts of alcohol are added and until the solution is complete of sodium boiled. After cooling, 1750 parts of water are added, the separated oil

separated off and the aqueous parts extracted twice with 250 parts by volume of benzene. The extract will combined with the oil, dried over sodium sulfate and evaporated.

When the residue is distilled in a high vacuum (0.05 to 0.08 mm Hg), 102 parts (82% of theory) of N, N'-bis (zl ³ -tetrahydrobenzyl) ethylenediamine with a boiling point of 132 ° to 142 ° are obtained. n% ° = 4.5092.

Analysis: C ₁₆ H ₂₈ N ₂

Calculated ... C = 77.36, H = 11.36, N = 11.28 "/ ¹ O;
found ... C = 77.46, H = 11.26, N = 11.40%.

d) N, N '- diacetyl - Ν, Ν' - bis - (A ³ - tetrahydrobenzyl) ethylenediamine

99 parts of N, N'-bis (zl ³ -tetrahydrobenzyl) ethylenediamine are mixed with 90 parts of acetic anhydride with cooling. After the acetic acid formed has been driven off in a water jet vacuum, the residue is distilled in a high vacuum. At about 200 ° (0.07 mm Hg), 102 parts of an extremely viscous liquid pass over, which slowly crystallizes on standing for a long time.

Analysis: C ₂₀ H ₃₂ O ₂ N ₂

Calculated. . . N = 8.43 <> / o;
found . . . N = 8.53%.

e) N, N'-diacetyl-N, N'-bis (3,4-epoxyhexahydrobenzyl) ethylenediamine

33 parts of the product described above are dissolved in 200 parts by volume of benzene. Be at about 20 ° 840 parts by volume of benzene peracetic acid solution containing 19 parts of peracetic acid were added dropwise. the Mixture is slowly warmed up to 27 ° and after 7 hours with twice 200 parts by volume ice-cold 1 η soda and then washed with 200 parts by volume of saturated sodium chloride solution. After drying over Sodium sulfate, the solvent is evaporated.

The epoxy resin obtained (25 parts) can be recrystallized from carbon tetrachloride with cooling will. Melting point 128 to 129 °.

Example 7

b) Di-Schiff base from z ( ^3- tetrahydrobenzaldehyde and hexamethylenediamine

58 parts of hexamethylenediamine are mixed in 200 parts by volume of benzene with 118 parts of 93% zl ^{3 -tetrahydrobenzaldehyde.} The separated water is removed in a circulation distillation apparatus. After the solvent has been driven off, the residue is distilled at 154-159 ° (0.05 mm Hg). Yield: 144 parts (96% of theory). n% ° = 1.5074.

Analysis: C ₂₀ H ₃₂ N ₂

Calculated ... C = 79.94, H = 10.74, N = 9.32%;
found ... C = 79.55, H = 10.82, N = 9.48%.

c) N, N'-bis (zl ³ -tetrahydrobenzyl) -hexamethylenediamine

525 parts of the Schiff base described above are mixed with 3800 parts by volume of absolute alcohol. To this, 325 parts of metallic sodium are gradually added in pieces of about 4 g with stirring, the mixture heating to the boil. Towards the end of the reaction, the mixture is refluxed until the sodium has completely dissolved. After cooling, 4000 parts of water are added, the separated oil is separated off and the aqueous part is extracted twice with 500 parts by volume of benzene. The extract is combined with the oil and drained in a circulating distillation apparatus. The benzene is now evaporated and the remaining residue is distilled, 440 parts of the N, N'-bis (zl ³ -tetrahydrobenzyl) -hexamethylene diamine being obtained at 150 to 160 ° (0.05 mm Hg). w | ° = 1.5032.

Analysis: C ₂₀ H ₃₆ N ₂

Calculated ... C = 78.88, Ή = 11.92, N = 9.20%;
found ... C = 78.55, H = 11.90, N = 9.27%.

e) N, N'-diacetyl-N, N'-bis (3,4-epoxyhexahydrobenzyl) -hexamethylenediamine

430 parts of N, N'-bis (tetrahydrobenzyl) hexamethylenediamine are dissolved in 2000 parts by volume of benzene. To this, 289 parts of acetic anhydride are added dropwise, the temperature being reduced to 15 to by cooling with ice 38 ° is held. Then 60 parts of anhydrous sodium acetate are added and the Over the course of 42 minutes, 600 parts of 42% strength peracetic acid were added in portions. The temperature will kept at 30 ° by cooling. After a further 2 hours at 32 °, the benzene with three times 500 parts by volume of water, three times 500 parts by volume of 2N soda solution and finally with 50 parts by volume Washed 1 m-monosodium phosphate solution. The aqueous parts are mixed with 750 parts by volume of benzene extracted. The extracts are combined, dried over sodium sulfate and evaporated. You get 478 parts of product containing 4.26 epoxy equivalents per kg (89.5% of theory).

Example 8

c) N, N'-bis (./ | ³ -tetrahydrobenzyl) -hexamethylene diurethane

61 parts of Ν, Ν '- bis (A ³ - tetrahydrobenzyl) hexamethylenediamine are dissolved in 200 parts by volume of ethylene chloride and covered with 250 parts by volume of 2N sodium carbonate solution. With thorough stirring, 50 parts of ethyl chloroformate are added dropwise at 0 ° to 10 °, a precipitate being formed. After the mixture has been stirred for a further hour after the addition of the chloroformic acid ester has ended, it becomes 1000 parts by volume. Ethyl acetate is added and the aqueous layer is separated off. The solution is washed with 100 parts each of 2η-soda and saturated sodium chloride solution, dried over sodium sulfate and evaporated. 66 parts of Ν, Ν'-bis (A ³ - tetrahydrobenzyl) hexamethylene diurethane are obtained from the residue by distillation at about 200 ° (0.04 mm Hg).

Analysis: C ₂₆ H ₄₄ O ₄ N ₂

Calculated ... C = 69.60, H = 9.89, N = 6.24%;
found ... C = 69.1, H = 9.8, N = 6.5%.

*

e) N, N'-bis (3,4-epoxyhexahydrobenzyl) -hexamethylene diurethane

57.5 parts of Ν, Ν '- bis (A ³ - tetrahydrobenzyl) hexamethylene diurethane are dissolved in 300 parts by volume of benzene. With stirring and cooling in the presence of 5 parts of sodium acetate, 60 parts of 42% strength peracetic acid are added over the course of 13 minutes, and the mixture is left to react for a further hour at 30 °. After this time, 81% of the theory of peracetic acid has

organic phase

needs. The organic phase is mixed with 100 parts by volume of ice water three times and 100 parts twice washed diluted soda solution. The aqueous parts are extracted with 250 parts by volume of benzene. The. combined extracts after drying and evaporation yield 54.2 parts of diepoxide with a Epoxy content of 3.85 epoxy equivalents per kg.

Example 9

b) Di-Schiff base from zf ³ -tetrahydrobenzaldehyde

and p-phenylenediamine

108 parts of p-phenylenediamine are mixed in 500 parts by volume of benzene with 238 parts of 93% <d ⁸ -tetrahydrobenzaldehyde and dehydrated in a circulation distillation apparatus. The benzene is then distilled off and the residue is distilled at 0.03 mm Hg and about 200 °. Yield: 241 parts (82% of theory). The product solidifies when it cools.

c) N-N'-bis (J ³ -tetrahydrobenzyl) -p-phenylenediamine

73 parts of the Di-Schiff base described above are dissolved in 500 parts by volume of absolute alcohol. 46 parts of sodium are gradually introduced into the solution. Then another 200 parts by volume of absolute alcohol are added and the mixture is boiled until the sodium has completely dissolved. During the reaction, the product separates out in the form of droplets. After cooling, 500 parts by volume of benzene and 2000 parts of water are added. The aqueous layer is separated. The organic phase is evaporated and the residue is distilled at 0.05 mm Hg and about 200 °, 56 parts of immediately crystallizing N, N'-bis- (zJ ³ -tetrahydrobenzyl) -p-phenylenediamine being obtained. The product can be crystallized from cyclohexane. Melting point 96 °.

Analysis: C ₂₀ H ₂₈ N ₂

Calculated ... C = 81.03, H = 9.52, N = 9.45%;
found ... C = 81.19, H = 9.62, N = 9.27 Vo.

a, e) N.N'-diacetyl- ^ N'-bis-CS ^ -epoxyhexahydrobenzyl) -p-phenylenediamine

50.3 parts of N, N'-bis (tetrahydrobenzyl) -p-phenylenediamine are dissolved in 300 parts by volume of benzene. Then 35.0 parts of acetic anhydride are added and the mixture is boiled for 15 minutes. Man cools to 30 °, 10 parts of sodium acetate are added and the epoxidation is carried out for 40 minutes at 30 to 35 ° 75 parts of 42% peracetic acid. The product is worked up as described in the preceding examples. 63.4 parts of crystallized product with an epoxide content of 3.36 equivalents are obtained per kg.

Example 10
d) N, N-bis (zl ³ -tetrahydrobenzyl) -stearic acid amide

For a well-stirred mixture of 102.5 parts of N ₇ N-bis (^ l ³ -tetrahydrobenzyl) amine in 400 parts by volume of ethylene chloride and 53 parts of anhydrous soda, dissolved in 400 parts by volume of water, at 7 to 13 °

ίο 152 parts of stearic acid chloride added dropwise in 27 minutes. The mixture is stirred for a further 3 hours at room temperature. The aqueous phase shows a _pH value of 7. The lower phase (ethylene chloride) is separated, washed twice with 200 parts by volume of 2N nitric acid and 100 parts by volume of 2N-potassium bicarbonate solution, dried over sodium sulfate and evaporated. The product (236 parts, 100% of theory) partially crystallizes.

e) N, N-bis (3,4-epoxy-hexahydrobenzyl) -stearic acid amide

100 parts of N, N-bis (zl ³ -tetrahydrobenzyl) stearic acid amide are dissolved in 500 parts by volume of benzene. Furthermore, 11 parts of anhydrous sodium acetate are added with stirring and 110 parts of 42% peracetic acid are added in portions over 10 minutes at 30 °. After a further 85 minutes at 28 to 33 °, the aqueous layer is separated off. The benzene phase is washed with water and 2N soda until the acids are completely removed. The solution will be over. Sodium sulfate * dried and evaporated. 103 parts of crystallized product with a content of 3.25 epoxy equivalents per kg are obtained.

The advantageous properties of the compounds produced according to the invention are based on the following Comparison test.

Solvent resistance

In 20 parts of bis (3,4-epoxyhexahydrobenzyl) acetamide, 0.50 parts of the boron trifluoride-ethylamine complex compound are dissolved at about 100 °. The mixture is poured into tin molds (4X1X1 cm) and heated to 150 °. Gelation occurs after 60 minutes. The mixture is then cured at 150 ° for a further 40 hours.
B. In the same way, castings are made from 6,6'-dimethyl - 3,4 - epoxyhexahydrobenzyl - 3 ', 4'-epoxy hexahydrobenzoate. The mixture gels after 6 minutes.

The castings obtained are placed in solvent. The castings obtained after B begin to swell rapidly (increase in weight) and then disintegrate (decrease in weight), while those according to A The castings obtained are unchanged and show no surface damage. The following table shows the increase or decrease in the cast body

Pour
body solvent Original
Weight 32 minutes Weight according to 2 ³ Ii hours 18 hours after. mg 3353 83 minutes 3353 3355 A. chloroform 3353 3949 *) - 3353 3676 720 B. the same 3881 3904 3640 3640 A. acetone 3640 3896 4003 B. the same 3879 4968 A. Dimethylformamide 4968 3366 *) B. the same 3290

*) Surface strongly attacked.

109 533/363

Claims (3)

19 20 Claims: 1. Process for the production of new nitrogen-containing epoxy compounds der.allgemen formula JtV ₂ Xv ₁ JCV ₁ Xv ₂ C C -CH ₉ -N- C C CR ₇ - (Z) _n ^ ₁ - N- re — 1 CH ₅ , c R ₃ ' -C C C C R ₇ 'C wherein R ₁ , R ₁ ', R ₂ , R ₂ ', R ₃ , R ₃ ', R ₄ , R ₄ ', R ₅ , R ₅ ', R ₆ , R ₆ ', R ₇ , R ₇ ', R ₈ , R ₈ ', R ₉ , R ₉ ' represent monovalent substituents such as halogen atoms or aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon radicals, in particular lower alkyl radicals with 1 to 4 carbon atoms or hydrogen atoms, where R ₁ and R ₅ or R ₁ 'and R ₅ ' together can also mean a divalent substituent, such as a methylene group, X and Y acyl, carbalkoxy, carb VR ₉ ^x CC CH ₂ -N- aryloxy, carbaminyl, cyano or sulfonyl radicals, Z stands for a divalent organic radical which can be interrupted by functional groups or by heteroatoms such as nitrogen, oxygen or sulfur atoms, in particular an alkylene or phenylene radical, m an integer with a value of at most 2 and η a small integer, characterized in that compounds of the general formula R ₁ 'R ₂ ' - (Z) _n ^ ₁ -NR _n ' CH ₂ R ₃ ' R ₇ R ₇ ' R ₈ Re' wherein R ₁ , R ₁ ', R ₂ , R ₂ ', R ₃ , R ₃ ', R ₄ , R ₄ ', R ₅ , R ₅ ', R ₆ , R ₆ ', R ₇ , R ₇ ', R ₈ , R ₈ ', R ₉ , R ₉ ', X, Y, Z, m and η have the meaning given above, treated in a manner known per se with epoxidizing agents such as peracetic acid or perbenzoic acid. R ₂ R ₁ 2. The method according to claim 1, characterized in that compounds of the general formula 45 R ₉ R, CH ₂ -N-CH ₂ C C / \ / \
R ₄ CR ₇ / \
R ₈ Re C C R ₇ CR ₄ wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and X have the 6o compounds of the general formula given in claim 1, such as CH ₂ ( CH 'CH-CH ₂ -N-CH ₈ -CH IX H, CH CH CH-R \ /
CH, R'-CH CH \ /
CH ₂ wherein X has the meaning given above and R and R 'represent a hydrogen atom or a lower alkyl radical, preferably the compounds of the formulas or.
CH / ^CH \. / ^H \ CH CH-CH ₂ -N-CH ₂ -CH CH C = O H CH CH ₂ CH, CH CH ₂ \ /
CH, 22nd CH-CH ₂ -NH-CH ₂ -CH CH C = CH ₃ CH ₂ CH \ / CH ₂ CH ₂ CH ₂ R ₂ R, ~ ^ ₂ v, ^ ₂ Qjj treated with epoxidizing agents. 3. The method according to claim 1, characterized in that compounds of the general formula R ₁ R ₂ C C CR ₇ Rs R ₆ R ₈ c c R ₇ CR ₄ R ₆ R ₅ wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , X, Y are like compounds of the general formula and Z have the meaning given above, CH CH, CH CH-CH ₂ -NH-Z-NH-CH ₂ -Ch X Y CH CH CH-R CH ₂ wherein X, Y and Z have the meaning given above and R and R 'represent a hydrogen CH ₂ R '- CH CH CH ₂ atom or a lower alkyl radical, preferably the compound of the formula CH ₅ CH CH-CH ₂ -N -CH ₂ -CH _a -N-CH _a -CH C = O C = O CH ₃ CH ₃ CH CH CH ₂ \ / CH ₂ treated with epoxidizing agents. CH ₂ CH CH ₂ © 009 5S8 / 431 8.60 (109 533/363 3. 1)