DE1518698C - Process for the preparation of disubstituted alkyl ureas - Google Patents
Process for the preparation of disubstituted alkyl ureasInfo
- Publication number
- DE1518698C DE1518698C DE1518698C DE 1518698 C DE1518698 C DE 1518698C DE 1518698 C DE1518698 C DE 1518698C
- Authority
- DE
- Germany
- Prior art keywords
- preparation
- water
- reaction
- disubstituted alkyl
- alkyl ureas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- -1 disubstituted alkyl ureas Chemical compound 0.000 title claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 7
- 235000013877 carbamide Nutrition 0.000 title claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 150000001350 alkyl halides Chemical class 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 7
- GKKCIDNWFBPDBW-UHFFFAOYSA-M Potassium cyanate Chemical compound [K]OC#N GKKCIDNWFBPDBW-UHFFFAOYSA-M 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N [N-]=C=O Chemical compound [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 229920002396 Polyurea Polymers 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- YQKDMDVDMWPYTF-UHFFFAOYSA-N 1,3-di(tetradecyl)urea Chemical compound CCCCCCCCCCCCCCNC(=O)NCCCCCCCCCCCCCC YQKDMDVDMWPYTF-UHFFFAOYSA-N 0.000 description 1
- YLOGJPLTYYDQCN-UHFFFAOYSA-N 1,3-didodecylurea Chemical compound CCCCCCCCCCCCNC(=O)NCCCCCCCCCCCC YLOGJPLTYYDQCN-UHFFFAOYSA-N 0.000 description 1
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 1
- KOFZTCSTGIWCQG-UHFFFAOYSA-N 1-bromotetradecane Chemical compound CCCCCCCCCCCCCCBr KOFZTCSTGIWCQG-UHFFFAOYSA-N 0.000 description 1
- ZTEHOZMYMCEYRM-UHFFFAOYSA-N 1-chlorodecane Chemical compound CCCCCCCCCCCl ZTEHOZMYMCEYRM-UHFFFAOYSA-N 0.000 description 1
- CLWAXFZCVYJLLM-UHFFFAOYSA-N 1-chlorohexadecane Chemical compound CCCCCCCCCCCCCCCCCl CLWAXFZCVYJLLM-UHFFFAOYSA-N 0.000 description 1
- 238000001321 HNCO Methods 0.000 description 1
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M Sodium cyanate Chemical compound [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N isocyanate Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
- 210000004885 white matter Anatomy 0.000 description 1
Description
Aliphatische disubstituierte Harnstoffe sind bekannte Verbindungen. Man kann sie durch Umsetzung von Isocyanaten mit Wasser (I) oder Aminen (II) herstellen. Weitere Darstellungsmethoden für disubstituierte Harnstoffe sind die Umsetzung von Harnstoff mit Monoalkylaminen (III) und von Monoalkylaminen mit Phosgen (IV).Aliphatic disubstituted ureas are known compounds. You can do it by implementing it of isocyanates with water (I) or amines (II). Other methods of representation for disubstituted people Urea is the reaction of urea with monoalkylamines (III) and of monoalkylamines with phosgene (IV).
2R —NCO2R -NCO
R — NCO + NH2 · RR - NCO + NH 2 · R
2R-NH2+ NH2-CO-NH2
4 RNH2 + COCl2 2R-NH 2 + NH 2 -CO-NH 2
4 RNH 2 + COCl 2
-CO,-CO,
[R · NH · CO — O · CO · NH . R]
R —NH-CO-NH-R
R-NH-CO-NH-R[R • NH • CO - O • CO • NH. R]
R -NH-CO-NH-R
R-NH-CO-NH-R
R-NH-CO-NH-RR-NH-CO-NH-R
R — HN · CO · NH · R + 2RNH2ClR - HN • CO • NH • R + 2RNH 2 Cl
II
III
IVII
III
IV
Aus Kaliumcyanat mit Dialkylaminen in wäßriger Lösung erhält man asymmetrische Dialkylharastoffe (V) [I].Asymmetric dialkyl resins are obtained from potassium cyanate with dialkylamines in aqueous solution (V) [I].
RRNH + HNCO -> H2N · CO · NRR VRRNH + HNCO -> H 2 N • CO • NRR V
Allen Verfahren gemeinsam ist die Verwendung von Aminen als Ausgangsprodukte oder wie im Falle des Isocyanats (I) als Zwischenprodukt.Common to all processes is the use of amines as starting materials or as in the case of the Isocyanate (I) as an intermediate.
Diese Amine sind jedoch nur durch einen Mehrstufenprozeß aus Kohlenwasserstoffen zugänglich und meistens dann auch nur in ungenügender Reinheit.However, these amines are only accessible from hydrocarbons through a multistage process mostly then only in insufficient purity.
Zweck der Erfindung ist es, aliphatische disubstituierte Harnstoffe darzustellen, die als Zusätze von Waschmittelkompositionen, Weichmacher und Plastinkatoren Bedeutung haben.The purpose of the invention is to prepare aliphatic disubstituted ureas that are used as additives of Detergent compositions, plasticizers and plasticizers are important.
Der Erfindung liegt die Aufgabe zugrunde, die bisher zur Synthese dieser Verbindungsklasse verwandten . aliphatischen Amine durch leichter zugängliche Rohstoffe zu ersetzen, insbesondere Reaktionsbedingungen aufzufinden, die den Einsatz von AlKylhalogeniden ermöglichen. The invention is based on the object so far related to the synthesis of this class of compounds. aliphatic amines through more accessible raw materials to replace, in particular to find reaction conditions that allow the use of AlKylhalogeniden.
Es wurde nun gefunden, daß sich Alkylhalogenide und Alkalicyanate ftf Dimethylformamid als Lösungsmittel bei Reaktionstemperaturen von 60 bis 1600C in Gegenwart von Wasser zu aliphatischen disubstituierten Harnstoffen in guten Ausbeuten umsetzen lassen.It has now been found that alkyl halides and Alkalicyanate ftf dimethylformamide as solvent at reaction temperatures from 60 to 160 0 C in the presence of water can be implemented to aliphatic disubstituted ureas in good yields.
Der Reaktionsverlauf ist folgendermaßen formulierbar: The course of the reaction can be formulated as follows:
a) R—Hal + KNCOa) R-Hal + KNCO
b) 2[R-NCO]+ H2Ob) 2 [R-NCO] + H 2 O
ao mit unterschiedlicher Kettenlänge und durch Verwendung von Alkylhalogeniden mit Doppelbindungen lassenr sich die Eigenschaften und damit die Einsatzmöglichkeiten der Produkte weitgehend variieren. Weiterhin lassen sich durch Umsetzung von α,ω-Di-ao with different chain lengths and through use of alkyl halides with double bonds, the properties and thus the possible uses of products vary widely. Furthermore, by converting α, ω-di-
a5 halogeniden Polyharnstoffe darstellen.a5 represent halide polyureas.
Das erfindungsgemäße Verfahren wird an folgenden Beispielen erläutert:The method according to the invention is illustrated by the following examples:
[R- NCO] + K — Hai R-NH-CO-NH-R[R-NCO] + K - Hai R-NH-CO-NH-R
+ COa + CO a
Das in der Reaktion a) intermediär entstehende Alkylisocyanat ist zwar bisher nicht isolierbar, aber nachweisbar. An Hand des in der Reaktion b) entstehenden Kohlendioxids ist der Ablauf quantitativ verfolgbar.The alkyl isocyanate formed as an intermediate in reaction a) has not yet been isolatable, but verifiable. The process is quantitative based on the carbon dioxide formed in reaction b) trackable.
Verwendet man größere Wassermengen, wird das Alkaliisocyanat hydrolysiert,If larger amounts of water are used, the alkali isocyanate is hydrolyzed,
KNCO + 2H1O -» KHCO8 + NH3 KNCO + 2H 1 O - »KHCO 8 + NH 3
und Ammoniak reagiert mit dem intermediär gebildeten Alkaliisocyanat zum Monoalkylharnstoff;and ammonia reacts with the intermediate formed Alkali isocyanate to monoalkylurea;
[R - NCO] + NH3 -> R · NH · CO · NH11 [R - NCO] + NH 3 -> R • NH • CO • NH 11
Durch Variation der Kettenlänge der Alkylhalogenide, durch Eiinsatz von AlkylhalogenidgemischenBy varying the chain length of the alkyl halides, by using mixtures of alkyl halides
Zu einer Mischung von 62,3 g Dodecylbromid In 125 ml Dimethylformamid gibt man 22,5 g Kaliumcyanat, versetzt mit 9 ml Wasser und erhitzt langsam auf 13O0C. Man beläßt 1 Stunde bei dieser Temperatur.To a mixture of 62.3 g of dodecyl bromide In 125 ml of dimethylformamide is added 22.5 g of potassium cyanate, mixed with 9 ml water and slowly heated to 13O 0 C. The mixture is left for 1 hour at this temperature.
Nach Abkühlen gießt man das gesamte Reaktionsgemisch in Wasser, erhitzt auf etwa 800C und läßt abkühlen. Dadurch scheidet sich der Di-dodecyl-harnstoff als obere Schicht ab und kann nach dem Abkühlen abgetrennt werden. Man erhält 55 g (88 % der Theorie) Alkylharnstoff vom Schmelzpunkt 97 bis 10O0C. Nach einmaligem Umkristallisieren zeigt der N,N'-Di-dodecyl-harnstoff einen Schmelzpunkt von 1050C. 'After cooling, the entire reaction mixture is poured into water, heated to about 80 ° C. and allowed to cool. As a result, the di-dodecyl urea separates out as an upper layer and can be separated after cooling. This gives 55 g (88% of theory) alkyl urea of melting point 97 to 10O 0 C. After one recrystallization of the N shows, N'-di-dodecyl-urea having a melting point of 105 0 C. '
B e i s ρ i e 1 2B e i s ρ i e 1 2
145 g Octädecylchlorid, gelöst in 250 ml Dimethylformamid und 9 ml Wasser, werden nach Zusatz von 45 g' Kaliumcyanat unter Rühren im Paraffinbad 2Vj Stunden auf 1300C erhitzt. Die Aufarbeitung erfolgt wie im Beispiel 1. Man erhält 135 g (96%) Ν,Ν'-Di-octadecyl-harnstoff von} Schmelzpunkt 100 bis 1020C. . ■■ '145 g Octädecylchlorid dissolved in 250 ml of dimethylformamide and 9 ml of water, after addition of 45 g 'of potassium cyanate with stirring in paraffin 2Vj hours at 130 0 C heated. Working up is effected as in Example 1 to give 135 g (96%) Ν, Ν'-di-octadecyl-urea} of melting point 100 to 102 0 C.. ■■ '
.·..·■;■· B ei sp i el 3. · .. · ■; ■ · Example 3
7Og Tetradecylbromid, 125 ml Dimethylsulfoxid, 4Vi ml Wasser und 25 g Natriumcyanat werden bei einer Reaktionstemperatur von 800C und einer Reaktionszeit von 2 Stunden analog Beispiel 1 umgesetzt. Man erhält 30 g (53%) N,N'-Di-tetradecyl-harnstoff vom Schmelzpunkt 97 bis 1010C.7Og tetradecyl bromide, 125 ml of dimethyl sulfoxide, 4vi ml of water and 25 g of sodium cyanate are at a reaction temperature of 80 0 C and a reaction time of 2 hours as in Example 1 implemented. 30 g (53%) of N, N'-di-tetradecyl urea with a melting point of 97 to 101 ° C. are obtained.
Bei sp iel 4At game 4
29 g Hexadecylchlorid, 22 g Decylchlorid, 22,5 g Kaliumcyanat, 150 ml Dimethylformamid und 15 ml Wasser werden bei einer Temperatur von 1100C 1 Stunde gerührt. Verfahren und Aufarbeitung analog Beispiel 1 und 2. Man erhält 50 g (100%) eines29 g hexadecyl chloride, 22 g of decyl chloride, 22.5 g of potassium cyanate, 150 ml dimethylformamide and 15 ml of water are stirred for 1 hour at a temperature of 110 0 C. Process and work-up analogous to Examples 1 and 2. 50 g (100%) of one are obtained
Ν,Ν'-Bis-alkylharnstoff-Gemisches mit gallertartigen Eigenschaften.Ν, Ν'-bis-alkylurea mixture with gelatinous Properties.
■■ ■■.■··-■■ ■■. ■ ·· -
122 g Hexamethylendibromid, 250 ml Dimethylformamid,
9 ml Wasser und 45 g Kaliumcyanat werden bei einer Temperatur von 13O0C 27a Stunden gerührt.
Verfahren und Aufarbeitung analog Beispiel 1 und 2. Man erhält 40 g (56%) N.N'-Hexamethylenpolyharnstoff.
Die feste weiße Substanz zeigt
Schmelzintervall von 163 bis über 20O0C*122 g hexamethylene, 250 ml of dimethylformamide, 9 ml of water and 45 g of potassium cyanate are stirred for 27 hours at a temperature of 13O 0 C. The process and work-up are analogous to Examples 1 and 2. 40 g (56%) of N.N'-hexamethylene polyurea are obtained. The solid white matter shows
Melting range from 163 to over 20O 0 C *
Claims (1)
Family
ID=
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE1518698C (en) | Process for the preparation of disubstituted alkyl ureas | |
DE1123662B (en) | Process for the preparation of alkylbenzene diisocyanates | |
CH307541A (en) | Process for the preparation of a tropic acid N- (B-picolyl) -N-alkenyl amide. | |
DE1518698B (en) | Process for the preparation of disubstituted alkyl ureas | |
DE1745660A1 (en) | Process for the preparation of monomeric imidazoline derivatives | |
AT313298B (en) | Process for the production of new pyrrolidine-N-carboxylic acid haloanilides | |
DE929191C (en) | Process for the production of aminocarboxylic acids | |
DE866647C (en) | Process for the production of secondary 1,3-alkenediamines | |
CH434232A (en) | Process for the preparation of organic intermediates and compounds containing urea groups | |
DE2206167C3 (en) | Production of herbicidally active 3- (halophenyl) -1,1-dialkylureas | |
DE866193C (en) | Process for the preparation of carboxylic acid amides substituted in the amide group | |
DE1518698A1 (en) | Process for the preparation of aliphatic disubstituted ureas | |
DE929192C (en) | Process for the preparation of aliphatic aminocarboxamides which are acylated or sulfonylated on the nitrogen atom | |
DE1593487C3 (en) | Process for making triuret | |
CH357400A (en) | Process for the preparation of 2-oxo-hexahydropyrimidines | |
DE860636C (en) | Process for the production of acrylic azide | |
AT239253B (en) | Process for the production of new bis (chloromethyl) carbamic acid chloride | |
DE939928C (en) | Process for the production of carbamyl chloride | |
DE543108C (en) | Process for the production of urea or products containing urea | |
DE875523C (en) | Process for the preparation of pentamethylene diamines mono- or asymmetrically disubstituted on nitrogen | |
DE842345C (en) | Process for the preparation of heterocyclic nitrogen compounds | |
DE1081887B (en) | Process for the preparation of N- (1, 2, 3, 4-tetrahydro-2-naphthyl) ureas | |
CH175675A (en) | Process for the production of a new nitrogenous basic product. | |
DE522058C (en) | Process for the preparation of Senfoelen | |
DE678194C (en) | Process for the preparation of compounds of mercaptothiazoles |