DER0012779MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: October 21, 1953. Advertised on December 6, 1956

GERMAN PATENT OFFICE

PATENT APPLICATION

CLASS 12 ο GROUP 19 03 INTERNAT. CLASS C 07c; d

R 12779 IVb / 12 ο

Marian Frances Fegley, Morft Clare, and Newman Mayer Bortnick, Oreland, Pa. (V. St. A.)

have been named as inventors

Rohm & Haas Company, Philadelphia, Pa. (V. St. A.)

Representative: Dr.-Ing. H. Ruschke, Berlin-Friedenau, and Dipl.-Ing. K. Grentzenberg, Munich 13, Ainmillerstr. 26 patent attorneys

Process for the preparation of N, N'-disubstituted 1,4-diaminobutadienes (1,3)

The priority of registration in the V. St. v. Occupied America of October 23, 1952

The invention relates to a method for transferring from i, 4-Diaminobutinen- (2) into the isomeric i, 4-Diaminobutadiene- (i, 3).

Attempts, 1, 4-Bisaminqbutine- (2) on thermal Ways to isomerize have been unsuccessful, and butadienes have failed to be established. Surprisingly, however, it was found that bisaminobutine is simple can be isomerized in the way, if to you with an alkali metal as a catalyst in heated liquid phase. All kinds of bisaminobutines, including those that have substituents Containing one or both of the terminal carbon atoms of butyne can in this way smoothly in liquid phase are isomerized.

According to the invention a process for the preparation of N, N'-disubstituted diaminobutadienes-i, 3 of the formula

-C = CHCH = C-N

R ² '

, R ^fi

Re.

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R 12779 IVb / 12 ο

in which R ¹ , R ^2, R ⁵ and R ⁶ , each for themselves, monovalent hydrocarbon groups or R ¹ and R ²

,, AND ₁ RaUnCl R ^{6 taken} together are divalent, optionally 'by oxygen or sulfur

■ 5 - interrupted. Carbon chains which form a heterocyclic ring with the nitrogen, and R ³ and R ⁴ denote hydrogen or monovalent hydrocarbon groups, claimed in which an N, N'-disubstituted i, 4-diaminobutyne- (2)

ίο the formula

R ¹

R ² '

R ⁵

R ⁸

R ⁴

wherein R ¹ , R ² , R3, R ⁴ , R5 and R ^{6 have} the above meaning, in the liquid phase between ο and

250 ⁰ with metallic sodium, metallic lithium or a sodium hydrocarbon in

/. Presence of an inert organic solvent is treated with isomerization.

In the aforementioned formulas, R ¹ , R ² , R ⁵ and R ^ß , each for itself, alkyl, - alkenyl, aryl, aralkyl or cycloalkyl groups and R ³ and R ^{4 can be} hydrogen or the aforementioned monovalent hydrocarbon groups mean.

In the process according to the invention for the isomerization of 1,4-diaminobutynes (2) to 1,4-D1-aminobutadienes (1,3), the butyne is treated with one of the alkali metal catalysts defined below at about ο to 250 ⁰ , preferably between 20 and 150 ⁰ treated. The reaction is carried out in the presence of an inert organic solvent such as gasoline, benzene, toluene, xylene, dioxane, isopropyl ether. From the reaction mixture

■ the solvent is then deposited. the butadiene compound formed is usually distilled under reduced pressure. Some butadiene compounds can be separated by crystallization.

Metallic sodium or metallic lithium in finely divided form or sodium hydrocarbons, such as sodium alkyl, aralkyl, aryl or alkenyl, are used with good success as catalysts. Sodium amide also converts diaminobutine into diaminobutadienes; but to a large extent it causes the formation of dimeric products. Dispersions of metallic potassium mainly catalyze the formation of dimeric products, although to a certain extent aminobutadienes are also formed here. Are particularly preferred ¹ Natriumallyl, -amyl, -Cyclo- hexyl, benzyl, phenyl, furyl. The alkali metals are best used in the form of dispersions, in gasoline, toluene, xylene, dioxane or another inert solvent. Sodium dispersions are particularly easy to produce.

But even with good dispersions, the rate of isomerization drops rapidly as the substituent groups in the diaminobutins increase. A satisfactory speed: however, in the case of this ^; ■ '''-Λ' bonds are reached if a small amount of a low molecular weight diaminobutine is first taken up in the dispersion. Bis (dimethylamino) butyne- (2) is most useful for this purpose. The sodium hydrocarbons are soluble in the butyne compounds with higher molecular weight substituents and are very effective isomerization catalysts for such aminobutines with a considerable molecular size.

The diaminobutyne to be isomerized and the catalyst are expediently in molar ratios from 5: ι to 100: 1 to be used. The best The proportions are between 20: 1 and 50: 1. The catalyst may be progressing from time to time Reaction added.

The isomerization reaction can in many cases be initiated at room temperature slow addition of a diaminobutine to the dispersion "of; Sodium or lithium in a solvent can often cause the reaction without external." Heating can be started. However, since an induction period must be expected, can set in a pretty violent reaction. It is better to set the catalyst dispersion to 40 to 90 ° to heat and then add the diarninobutin to this. The reaction is then calm.

The diaminobutines are known to be prepared by condensing 2 moles each of a secondary amine and an aldehyde and 1 mole of acetylene in the presence of a heavy metal from group L or II of the Periodic Table. To promote condensation, copper and its salts, e.g. B. Cuprochlqrid, copper acetate or copper formate, proven to be effective. Temperatures of up to 120 ° can be used. will. Details of the process are described in U.S. Patent 2,273,141. Although this process is primarily aimed at the production of propargylamines, molar ratios for the production of the butynes can be found. Furthermore, in a manner not claimed here, a propargylamine composed of a secondary amine, an aldehyde and acetylene can first be used. getting produced. The monoamine thus obtained is reacted with an aldehyde, which can be the same as that used first or a different one, and also with a secondary, amine, which also corresponds to that in the first. Level used to match or from this. can be different. In this way, symmetrical or asymmetrical diaminobutines can be obtained. As secondary amines, dialkylamines, e.g. B. dimethylamine, diethylamine, dipropylamine, dibutylamine, diamylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, methyl ^1- butylamine, methyloctylamine, methylidononylamine, methyldodecylamine, can be used. The total number of carbon atoms in the groups R ¹ and R ² or R ⁵ and R ⁶ should expediently not exceed 18. These groups can also be cycloaliphatic, as in Dieyclohexylatnin, Dicyclopentylatnin or Cyclohexylmethylatnin,

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R 12779 IVb / 12 ο

or aralkyl groups, such as in dibenzylamine or N-methyl-N-benzylamine, or unsaturated aliphatic hydrocarbon groups such as the allyl, methallyl, crotyl or undecenyl group, or aryl groups such as the phenyl, alkylphenyl or naphthyl group. The secondary amine can also be a heterocyclic amine. In this case, Ri and R ² or Rs and R ⁶ together form a divalent carbon chain, e.g. B.

-CH ₂ -CH ₂ OCH ₂ CH ₂ -

-CH ₂ CH ₂ SCH ₂ CH ₂ -,
- CH ₂ CH ₂ CH ₂ CH ₉ - or
-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -,

as they are in morpholine, thiamorpholine, pyrrolidine or piperidine or in similar heterocyclic amines. When formaldehyde has been used as the aldehyde, R ³ and R ^{4 are} hydrogen. In the case of other aldehydes, these groups correspond to hydrocarbon groups. Such aldehydes are acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, heptaldehyde, nonylaldehyde, dodecylaldehyde, benzaldehyde, alkylbenzaldehyde, tetrahydrobenzaldehyde, hexahydrobenzaldehyde, /? - phenylpropionaldehyde, 2-ethyl-3-ρropylacrol. ^{The groups R 3} and R ^{4 provided} by the aldehydes should preferably not contain more than 11 carbon atoms in each group.

Diaminobutines to be reacted according to the invention are, for example, 1,4-bis- (dimethylamino) -butyn- (2), r, 4-bis- (diethylamino) -butyn- (2), 1,4-bis- (din - butylamino) - butyne - (2), 1,4-bis - (N - methyl-N-octylamino) - butyne- (2), 1,4-Dimorpholino-butyne- (2), 1,4-Dipiperidino-butyne- (2), 1,4-Dipyrrolidino-butyne- (2), i-dimethylamino-4-morpholinobutyn- (2), i-Dimethylamino-4-piperidino-butyne- (2), 1,4-bis- (diallylamino) -butyne- (2), 1,4-bis- (N-methyl-N-phenylamino) -butyne- (2 ), 1, 4-bis (dicyclohexy 1 amino) - butyne - (2), 1 - methyl - 1 - morpholino-4-dimeth: ylamino-butyne- (2), T, 4-Diisopropyl-1,4-bis (dimethylamine, o) -butyn- (2), 1-phenyl- i-morpholino-4-dimethylamino-butyne- (2), 1, 4-diphenyl-i, 4-bis (dimethylamino) butyne - (2), 1,4-bis (dimethylamino) -i, 4-di- (2,4,4-trimethylpentyl) -butyn- (2), 1,4-bis- (diethylamino) -i, 4-diisopropyl-butyn- (2).

Details of the isomerization of diamino

butynes to diaminobutadienes are brought in the following examples. The parts are Parts by weight.

Example ι

A funnel with a stirrer, drip, condenser and thermometer equipped reaction vessel was charged with 121 parts of gasoline and 4.5 parts of sodium dispersion in toluene and heated in an oil bath at 63 ^0th Then 1,4-bis- (di-

. methylamino) butyne- (2) was added. After adding 342 parts of this butyne, the reaction mixture was refluxed for 2 hours. The solvents were then separated off and the product distilled. The following fractions were obtained: At .100 to 1090/20 mm 145 parts with a refractive index of 1.5475, 96% of which consisted of pure 1,4-bis (dimethylamino) -butadiene- (1.3); at ii2 ° / 2y mm 57 parts with a refractive index of 1.547, which contained 95 to 96 ⁰ Zo of the same substance; at 53 to 59%, i to 0.13 mm, 108.5 parts of a product with the refractive index 1.5475 which, on the basis of analysis, contained 95.7%> of the same butadiene compound; and at 63 to 73 ° / i, i to 0.65 mm 15 parts with the refractive index 1.5492 and a content of 97.2% of the same butadiene compound. These four fractions combined gave a conversion of 89%. The distillates contained 3.2% unconverted 1,4-bis (dimethylamino) butyne- (2). . .

This butadiene compound can be used as a corrosion inhibitor and stabilizer.

The above procedure can be successfully applied to diaminobutines, the. N-Sub, contain substituents with 1 to 4 carbon atoms. With increasing N-substituents the decreases Reaction speed noticeably. With even larger hydrocarbon substituents, the Speed too slow for practical purposes. That apparently depends on the decreasing rate Solubility of the catalyst decreases with increasing molecular size of the reactant. It however, it has been found that the isomerization reaction occurs at a practically acceptable rate proceeds with a favorable degree of conversion if the sodium dispersion in 1,4-bis (dimethylamino) -butyne- (2) added and this mixture with substituted by higher molecular weight radicals Diaminobutinen · was added. A cheap speed and a good one. Conversion will too with a sodium alkyl or a sodium aryl receive.

Example 2

In accordance with the above, a reaction vessel equipped as above was charged with 50 parts of gasoline and 4 parts of a 50% sodium dispersion in xylene. This charge was ^{warmed to above 40 0} and 14 parts of 1,4-bis (dimethylamino) butyne- (2) were slowly added. Then a total of 136 parts of 6, 9-bis- (dimethylamino) -2, 2, 4, 11, 13, 13-hexamethyl-tetra, -no decin- (7) were slowly added. The temperature of the reaction mixture was maintained at 60 to 70 ^° C. during the 40 minutes required for the addition of the reactant. It was then increased to 70 to 80 degrees for about 2.5 hours. The solvent was then distilled off. At 68 to i32 ° / 2.8 to 5 mm a fraction of 10 parts was removed, which consisted of 1,4-bis (dimethylamino) butadiene (i, 3). At 187 to 192 ⁰ / 4.4 to 3.2 mm, 131 parts were obtained which, on the general basis of the analysis, were 98% pure substance of the formula

(CH ₃ ) ₂ N - C = CH- CH = CN (CH ₃ ) ,,
C ₈ H ₁₇ C ₈ H ₁₇

609 710/364

R 12779 IVb / 12 ο

in which the C ₈ H ₁₇ groups are 2, 4, 4, trimethylpentyl groups. This product has an index of refraction nf 1.4986.

Example 3

The reaction vessel was charged with 163 parts of dioxane and 112 parts of 1,4-dimorpholino-butyne- (2). This mixture was stirred and heated until the butyne dissolved. After cooling to about 30 ⁰ 10 parts of a 50 ^fl / o sodium dispersion in.Dioxan were added. Es'setzte a · an exothermic reaction in which the temperature of the mixture rose to 54 ^0th The reaction vessel was then placed in an 86 ° oil bath. The temperature of the reaction mixture rose to 93 °. The mixture was stirred for 20 hours at 83 ^0th Most of the dioxane was driven off under reduced pressure. The residue was taken up in toluene, treated with decolorizing charcoal and nitrated while hot. A solid separated out from the filtrate. Based on the analysis, it was identified as 1,4-dimorpholino-butadiene- (i, 3). Additional amounts of crystal were deposited. They melted at 138.5 to 139.5 ⁰

Other butynes containing heterocyclic amino substituents can be reacted in the same way will. This gives 1,4-dipiperidinobutyn- (2) i, 4-dipiperidino'-butadiene- (i, 3) and from i, 4 ~ dithiamorpholino-butyne- (2) 1,4-dithiamorpholino-butadiene- (i, 3).

Example 4

A reaction vessel equipped with a stirrer, a dropping funnel and a condenser carrying a drying tube was charged with about 5 parts of a 40% sodium dispersion in toluene and 40 parts of gasoline. The stirred ^{mixture, heated to 70 0} , was slowly added to a total of 40 parts of i, 4-dipyrrolidino-butyne- (2). Heating the reaction mixture added. When the addition had ended, the mixture was stirred and kept in an oil bath at 100 ° for 1 hour. The reaction mixture was fractionally distilled. At ii5 ° / o.35 mm and ii8 ° / 0.9 mm, i, 4-dipyrrolidino-butadiene- (i, 3) was obtained. Its refractive index at 20 ⁰ was 1.5988.

It should be pointed out that the corresponding butadiene compounds can also be obtained from mixed aminobutines can be prepared in which only one amino group is heterocyclic.

Example 5

To a mixture of 40 parts of gasoline and 0.65 parts of lithium metal cut into small pieces, 102 parts of 1,4-bis (dimethylamino) butyne- (2) were slowly added. At first the temperature rose. The vessel was then heated 1 hour in oil bath at 6o ° and 1.5 hours at 95 ^0th At 47 ° / <ι mm and 56 to 10 ° l <C 1 mm, fractions were removed, of which the first 93 ° A> pure 1,4-bis (dimethylamino) -butadiene- (i, 3) and the second contained the same substance in a purity of 95%. The conversion was 70%.

Example 6

1,4-Bis- (dibutylamino) -butyne- (2) was in xylene solution treated with a sodium dispersion in xylene as in Example 2. The product was at distilled i42 ° / o, 35 mm. Analysis showed that it contained 9.1% nitrogen (theoretical 9.07%); its refractive index was 1.5020 at 20 ° .i Based on the ultraviolet analysis, the distillate consisted of 92% pure 1,4-bis- (dibutylamino) -butadiene- (i, 3). ■

Example 7A

By treating 1,4-bis (diethylamino) butyne- (2) with a sodium dispersion. according to Example ι was 1,4-bis (diethylamino) -butadiene- (i, 3) receive. This product distilled at 64 ° / 0.25 mm and had an index of refraction of 1.5155.

Example 7 B ₈ _

From i, 4-B1S- (dimethylamino) -I, 4-diisopropylbutyne- (2) was according to the method described in Example 2 1, 4 ~ bis (dimethylamino) -i, 4-diisopropyl-butadiene- (i, 3) manufactured. This product distilled at 68 to 75 ° / 0.2 mm and had the refractive index 1.4948.

The starting butin was prepared from dimethylamine, isobutyraldehyde and acetylene with cuprous chloride as a catalyst. It distilled at 67 to 7O ° / o, 3 mm, and had a refractive index of 1.4550 at 20 ^0th

Example 8

From morpholine, acetaldehyde and acetylene, according to the US Pat. No. 2,273,141 described procedure,

, CH ₂ CH ₂

CH ₂ CH ₂

, N-CHC = CH

CH,

manufactured. This acetylene derivative was then mixed with formaldehyde and dimethylamine in the presence from cuprochloride to 4 - morpholine -1 -dimethylamino-pentine- (2) implemented, which boiled at 112 to ii4 ° / i mm and the refractive index 1.4828 had.

This Pentinverbindung was treated in naphtha solution with a sodium dispersion in toluene in a ratio of ng per gram mole of sodium at 74 ⁰ 2.7 hours. The butadiene compound obtained in the no to II5 ° / o, 3 mm boiled and showed a refractive index of 1.5625 at 20 ⁰ has the structural formula

, CH ₂ CH ₂

CHoCHn

ά Δ

= CHN (CH ₃ ) ₂ .

CH,

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R 12779 IVb / 12 ο

A. analogous product was obtained from i-morpholino-I - phenyl - 4 - dimethylamine »- butyne - (2) produced. The butadiene compound obtained boils at 150 to 160 ° / o.5 mm and has the structural formula

0:

, CHoCHn ν

CHnCHo

: N-C = CHCH = CHN (CH ₃ ) ₂

Example 9

To ι, 4-bis- (dimethylamino) -butyn- (2) given sodium dispersion was with a xylene solution of I, 4-bis- (dimethylamino) -1, 4-diphenyl-butyn- (2) [from dimethylamine, benzaldehyde and Acetylene] mixed. The reaction mixture was heated for 2 hours at 70 ^0th The product obtained was 1,4-bis (dimethylamino) -1, 4-diphenyl-butadiene- (1, 3). It distills at 169-174%, 15mm; be, refractive index Avar 1.593. The product crystallized on standing.

Example 10

Following the procedure of H ans ley (Ind. Eng. Chem., 43, p 1759 [1951] sore phenylsodium in toluene. To 5 parts of phenyl sodium in 20 parts of toluene and 30 parts of gasoline, which were heated to 55 ^0, were 100 parts of 1,4-bis- (dimethylamino) -butyn- (2) were added over the course of 50 minutes An exothermic reaction set in, which is controlled by the reflux of the gasoline.

would. When the addition was complete, the mixture was refluxed for ι hour and then distilled. After separation of the solvent was under reduced pressure 1, 4-bis (dimethylamino) -butadiene- (1, 3) obtained in 85% conversion.

Some of the starting product was recovered. The yield, based on the starting product, was 94%.

Example 11

Benzyl sodium in toluene was prepared using the Hansley method above. 10 parts of the benzyl sodium in 20 parts of toluene and 30 parts of gasoline were mixed and 3,6-bis- (dimethylaimino) -2, 7-dimethyl-octyne- (4) were added over the course of 30 minutes, the temperature being 60 to 90 ^{0 was} held. The reaction mixture was refluxed for 2 hours and then distilled. In 65% conversion, 3,6-bis (dimethylamino) -2,7-dimethyloctadiene- (3,5) was obtained.

Sodium phenyl, -benzyl, -allyl, -amyl can be used with success when bis- (amino) -butine with larger molecules can be used as starting materials.

In the treatment of 1, 4-bis (dimethylamino) -butin- (2) with potassium in toluene under heating at 115 ⁰ iV2Stündigem products were obtained from which fractions were distilled off. The first fraction taken at 45 to 48 ° / <1 mm contained 19% 1,4-bis (dimethylamino) butadiene (i, 3) on the basis of the ultraviolet absorption analysis. The conversion to the diaminobutadiene was 18.5%. At the same time, dimeric products were formed in 11% conversion in the above reaction time.

When using \ ^r on sodium as a catalyst were 65 ^fl / o in dimeric products and i2 ° / o in bis (dimethyla.mino) -butadien- (i, 3) converted.

The diaminobutadienes are very reactive chemical intermediates. You react with Alcohols and mercaptans with the formation of new substances that are called insecticides, fungicides or Wetting agents can be used. They react with hydrogen cyanide to form dinitriles which in turn polyamines, amides, acids, salts and esters can be produced. they react with some vinylidene compounds additively to form new cyclic products.

The diaminobutadienes ¹ can be transaminated into other diaminobutadienes. It is most expedient to start from a diamino'-butad'iene which is derived from a volatile secondary amine, e.g. B. dimethylamine or diethylamine, derives and introduces a secondary amino group substituted by higher molecular weight carbon hydrogen groups.

The process also gives 1,4-diaminobutadiene- (i, 3), which are asymmetrical in construction. All new compounds of the invention are as Intermediate products are particularly valuable. The compounds., Whose amino nitrogen is in heterocyclic Wrestling has some unusual properties. They have greater stability than that simple diaminobutadienes and provide derivatives that are also very stable. In particular, they are Butadienes with heterocyclic rings are not sensitive to acids.

Claims (3)

PATENT CLAIMS: i. Process for the preparation of N, N'-disubstituted 1, 4-diaminobutadienes (i, 3) of the formula R ² ' ^X ; N - C = CHCH == C - N R ³ .R ⁵ R ⁸ in which R ¹ , R ² , R ⁵ and R ^{6 are} each monovalent hydrocarbon groups or R ¹ and R ² and R ⁵ and R ^{G taken} together are divalent carbon chains, optionally interrupted by oxygen or sulfur, which form a heterocyclic ring with the nitrogen atom , and R ³ and R ^{4 are} hydrogen or monovalent hydrocarbon groups, characterized in that one 609 710/364 R 12779 IVb 112 ο N, N'-disubstituted
the formula ι, 4-diaminobutyne- (2) n — CHC = CCh- R ⁶ R ² R ³ R ⁴ in which R ¹ , R ² , R ³ , R *, R ⁵ and R ^{6 have} the above meaning, treated in the liquid phase with metallic sodium, lithium or a sodium hydrocarbon at ο to 250 ⁰ in the presence of an inert organic solvent with isomerization. 2. The method according to claim 1, characterized in that those starting materials are used, in which R ¹ and R ² and R ⁵ and R ^{6 are} the divalent carbon chains .. - CH ₂ CH ₂ O CH ₂ CH ₂ -, -CH ₂ CH ₂ S CH ₂ GH ₂ -, or-CH ₂ CH ₂ CH ₂ CHgCH _2; - represent. 3. The method according to any one of the preceding claims, characterized in that the isomerization
to be led. between .20 and 150 ⁰ through Documents considered: French Patent No. 880,372.