Method of producing substituted ureas

专利摘要:
The invention relates to heterocyclic compounds and, in particular, to the preparation of substituted urea of the formula (R 1 O) (R 2 O) CH-CH (OR 3 ) -N (A) -C (O) -N (A 1 ) - CH (OR 3 ) CH (OR 1 ) (OR 2 ), where R 1 and R 2 - C 1 - C 4 -alkyl R 3 - H, C 1 - C 4 -alkyl A and A 1 - each H or together form an ethylene radical, which can be used as a finishing agent for cellulosic fibers. The preparation is carried out by the reaction of disubstituted ethanal (R 1 O) (R 2 O) CHCHO, where R 1 and R 2 have the indicated values with urea ANH-CO-NH-A 1 followed by reaction with alcohol R-CH 2 -OH, where C 1 - C 3 -alkyl or hydrogen. 1 tab.
公开号:SU1609447A3
申请号:SU884355522
申请日:1988-04-01
公开日:1990-11-23
发明作者:Вильхельм Дидье；Желабер Антонио；Бланк Ален
申请人:Сосьете Франсэз Хехст (Фирма)；
IPC主号:

专利说明:

cl
with
This invention relates to a process for the preparation of new substituted ureas of the general formula KiOx ORii.
. OR, and about AI OR,
where RI and R2 is C1-C4-alkyl;
Rs-hydrogen. C 1 -C 4 alkyl;
A and Ai each means a hydrogen atom or together form an ethylene radical, which can be used as a finishing agent for cellulose fibers. ..
The aim of the invention is to develop a process for the production of substituted ureas, which, compared with the known compounds, impart a higher crushability to cellulose fibers.
PR and MER 1. 1,3-Bis- (2,2-dimethoxy-1-hydroxyethyl) -urea.
With stirring, 24 g, (0.4 mol) of urea is dissolved in 96 g of an 81% methanol solution of dimethoxyethanol, i.e. 0.8 mol.
The resulting solution is then adjusted to pH 8 by adding a few drops of 2N. Atri hydroxide solution, then it is heated with stirring for 2 hours at 50 ° C. Thereafter, methanol is distilled off, then the oily residue is treated with a mixture of methanol and diethyl ether. The resulting product is crystallized, sucked off, then dried under vacuum to constant weight at CO. ° C.
Thus, 65% of 1,3-bis- (2,2-dimethoxy-1-hydroxyethyl) urea is obtained in the form of colorless prisms, melting at 90-110 ° C.
ABOUT
o you
Jiw
4 VI

SA)
Calculated. %: C, 40.29; H 7.51; N 10 44-041.75.
C9H20N207 (supposedly, 27)
Found,%; C 40.8; H 7.8; N 10.6.
Physical analyzes. This product, subjected to high pressure chromatography on a POLYGOSIL C 18 column with a water-methanol 96.5-3.5 mixture, was yielded two expected diastereoisomers; the first isomer has a retention time of 244 s, and the second is 635 s (1 cm / min).
The two diastereoisomers thus isolated have the following H-NMR spectra in deuterated dimethyl sulfoxide (DMSO de). ppm;
1st isomer 2nd isome
MN {d, 2H, 4 Hz) 6,666
OH (d, 2H, 6 Hz) 5,
N-CH-0 (M, 2H) 5.025.02
CH (OCHN) 2 (d.2N1 3.9 Hz) 4.13 4.14
OSSN (s, ZN) 3,343,34
OSSN (s, ZN) 3,313,31
PRI mme R 2. 1,3-Bis- (2,2-dibutoxy-1-hydroxyethyl) -imidazolidin-2-one.
Under stirring at 40 ° C, 860 mg (10 mmol) of ethylene urea (imidazolidin-2-one) and 2.7-6 g (20 mmol) of dibutoxyethanal are dissolved in 4 g of acetone. The resulting solution is then adjusted to a slightly alkaline pH value by adding a few drops of 2N sodium hydroxide solution, then it is heated under stirring for 30 minutes at 30 ° C and concentrated under vacuum; The residual oil is then purified by chromatography on silica gel with zylation with ethyl acetate. Thus, two fractions were isolated; the first one contains the product s, 6, and the second one contains the product with Rf 0.45.
After removal of the depletion solvent, both products are isolated in the form of an oil, which correspond to the two expected diastereoisomers 1,3-bis- (2,2-dibutoxy-1-hydroxyethyl) -imidazolidin-2-one, Yield 95%,
Physical analyzes, H-NMR, 200 MHz (DMSO de), ppm,
1st isomer 2nd isomer
v)


5.82
5.06 4.40
5.79 5.06 4.36
3.6-3.23 3.6-2.23 1.57-1.25 1.53-1.24
0.92-0.83 0.92-0.82
CO de), ppm;

2nd isomer C 0 158.7
0
CH
-about
101.5
5 10
15
20
25
30 5 0
five
0
five
NHCHOH75.0
0-CH2-66.3
0-CH2-65,5
N-CH2-37.2
-CH2-31.5
-CH2-18,8
-СНз13,7
N-CHOH74,9
0-CH2-66.3
0-CH2-65,1
N-CH2-37.2
-CH2-31.5
-CH2-18,8
-СНз13,7
Example 3. 1,3-Bis- (1,2,2-tributoxy-methyl) -imidazolidin-2-one.
Under stirring at 40 ° C, 860 mg (10 mmol) of ethylene urea and 3.765 g (20 mmol) of dibutoxyethanal are dissolved in 4 g of acetone. The resulting solution is then adjusted to slightly alkaline pH by adding a few drops of 2N sodium hydroxide solution, then it is heated with stirring for 30 minutes at 30 ° C and concentrated under vacuum. The residual oil is dissolved in 16 g of n-butanol, the resulting solution is acidified with a few drops of 50% aqueous sulfuric acid and then left to stir for 2 hours at room temperature before pouring it into 100 g of water. Decanted, then the aqueous phase is washed three times with 50 g of hexane, the combined organic phases are washed with 1N. sodium hydroxide solution, then with water until the neutral reaction of the wash water, and finally dried over anhydrous calcium chloride, filtered and concentrated to dryness under vacuum. The crude residual oil is then purified by chromatography on silica gel eluting with ethyl acetate. Thus, 3.43 g (6 mmol) of 1,3-bis- (1., 2,2-tributoxyethyl) -imidazolidin-2-one are obtained in the form of a colorless oil, soluble in hexane and diisopropyl ether. Yield 60%.
This product is a mixture of two expected diastereoisomers.
Physical analyzes. n-NMR, СРС1з (deuterated chloroform), ppm:
1st isomer 2nd isomer
N-CH-0 {fl, 2H) 5.16 (1-5.9 Hz) 5.15 (1-5 BHz)
CH (OC4H9) 2 (d. 2H) 4.52 (I-5.9 Hz) 4.51 (1-5 6 Hz) OCH2iSN2 (m, 16H) 3.63-341
CH2 (m, 24H) 1.61-129
SNZ (m, 12H) 0.95-0.86
.YAMR. СДС1з, ppm;
1st isomer 2nd isomer
, O160,42160,35
-CH (OC4H9) 2 100.8100.9.
N-CH-OC Hg 81,781,8
OCH268.1-68.0-67.1-67.0
65.5 and 65.4 N-CH237,737.9
CH231.9-31.8-31.5-19.3
SNS13,8
EXAMPLE 4 1,3-Bis- (2,2-diethoxy-1-oxyethyl) -imidazolidin-2-one.
With stirring and at a slightly alkaline pH-value, 45 g (0.34 mo / 1b) diethoxyethanol and 14.6 g (0.17 mol) of ethylene-urea are heated for 1 hour at 65 ± 5 ° C.
After cooling, the desired product crystallizes spontaneously. It is recrystallized from diisopropyl ether and in this way 50.6 g (0.114 mmol) of 1,3-bic- (2,2-diethoxy-1-oxyethyl) -imidazolidin-2-ona are obtained in the form of colorless crystals with m. square 105 ° C. The yield is 85% of theoretical.
Calculated,%: C, 51.41; H 8.63; N 8.0 O 31.96. ,
Ci5H3oN207 (mol.v.350.4) Found;%; C, 51.3; H 8.7; N 8.0. This product, analyzed by thin layer chromatography on silica gel, eluted with a mixture of dichloromethane and methanol 95; 5, reveals the presence of two products having respectively Rf 0.16 and Rf 0.21. After separation by preparative HPLC, these two products have the following NMR spectra.
H-NMRDMO, d6, ppm;
1st isomer 2nd isomer
OH (d. 2H, I- 6.0 Hz) 5,865.81
N-CH-O (T, 2H, 1-6.0 Hz) 5.04504
CH (OC2H5) 2 (D, 2H. 1-6.0 Hz) 4.414.41
-CH2- (m, 12H) 3.69-3.25
- CH3 (m, 12H) 1.17-1.05
- C-JMPDMCOd6, ppm;
1st isomer 2nd isomer C 0159,4156,6
-CH101.4101.2
N-CH-075,174,9
OCH262,262,2
OCH261,461.0
N-CH237,137,1
SNS15,315,3
The product is not described in the literature.
PRI me R 5. 1,3-Bis- (2,2-dimethoxy-1.- hydroxyethyl) -imidazolidin-2-one.
With stirring for 1 h, the solution formed from 292.5 g (2 mol) of dimethoxyethanal in the form of a 53% aqueous solution, 86 g (2 mol) of ethyleneurea and a sufficient amount of 2N is heated at 50 ° C. sodium hydroxide solution to achieve a pH of 8. Then, the resulting solution is concentrated under vacuum. The desired product crystallizes spontaneously. After treatment with diethyl ether and drying under a vacuum of constant weight, 5 262 g of crystallized (0.89 mol) 1,3-bis (2,2-dimethoxy-1-hydroxyethyl) -imidazolidin-2-o having a mp. 127 ± 3 ° C. Yield 89%. Calculated,%; C, 44.89; H 7.54; N 9.52; About 10 38.05.
CiiH22N207 (mol. H.294.31). Found,%: C 44.8; H 7.7; N 9.6. C-NMR, DMSO da, ppm; C 0159.2
15-СН (ОСНз) 2103.1
N-CH-074,5
0-CH354.2
0-CH353,6
N-CH236,7
0 Product not described in literature.
EXAMPLE 6 1,3-Bis- (1,2,2-trimethoxy-methyl) -imidazolidin-2-one.
During 90 minutes at 50 ° C and with stirring, a solution of 40.8 g is heated 5. (0.125 mol) of 1,3-dimethoi-1-hydroxyethyl) -imidazolidin-2-one in 85 g of methanol and a sufficient amount of 25% aqueous sulfuric acid for pH 4.
The resulting solution is then cooled to room temperature, neutralized to pH 7 with sodium bicarbonate and concentrated to dryness with vacuum. The resulting crystalline product is recrystallized by heating and cooling from 5 diisopropyl ether.
Thus, 36.3 g (0.2125 mol) of crystallized 1,3-bis- (1,2,2-trimethoxyethyl) -imidazolidin-2-one having mp. 66 ± 3 ° C. Yield 90% | I
0Calculated,%; C 48.4; H 8.13; N 8, B9; ABOUT
34.74.
C1ZN2bM207 (mol.v.322.4)
Found,%; C 48.3; H 8.2; N 8.7.
PRI me R 7. 1,3-Bis- (2,2-dimethoxy-1-5 hydroxyethyl) -4,5-dioxy-imidazolidin-2-one.
Under stirring at 50 ° C, 29.5 g (0.25 mol) of the trans-isomer of 4,5-dioximidazolidin-2-one is dissolved in 104 g of d11-methoxyethanal in the form of an aqueous 50% 0 solution, or 0 , 5 mol, then the resulting solution is adjusted to pH 8-9 by adding a few drops of 2N. sodium hydroxide solution. This solution is then heated for 1 h at 50 ° C and with stirring, 5 then it is concentrated under vacuum.
The residual oil obtained is purified by chromatography on silica gel eluted with a mixture of dichloromethane and methanol. Thus, 40.7 g (0.125
mol) 1,3-bis- (2,2-dimethoxy-1-hydroxyethyl) - 4,5-dioxy-imidazolidin-2-one in the form of a colorless oil, the H and C NMR spectra of which are consistent with the proposed structure.
Calculated,%: C40.49; H 6.79; N 8.59; About 44.13.
CiiH22N209 (mol.326.3)
Found,%: C 39.8; H 6.9; N 8.4.
EXAMPLE 8. A padded 100% cotton fabric, boiled and bleached, weighing about 130 g / m, squeezed 75%, in a water bath containing 0.4354 mol / l of substituted urea according to the invention, 12 g / l of hexahydrate magnesium chloride, 2.1 g / acetic acid, 2 g / l of ethoxylated 10 mol of nonylphenol ethylene oxide.
Then the fabric is dried at 120 ° C, after which it is subjected to heat treatment at 180 ° C for 35 s in a laboratory spreading machine (frame).
Then, on the samples of the treated fabric, the incompatibility is determined according to the AATSS Mg 66-1972 method on such samples as they are, and on the samples subjected to three gentle washes at 60 ° C (the crushability is expressed by the sum of the angles obtained after base direction and weft direction), tensile strength (R expressed in daN, base direction plus weft direction, according to AFNOR G07 001 and residual formaldehyde content (Tfr) on fabric by the AATCC method 112-1982,
The results are shown in the table.
As can be seen from the table, the compounds obtained according to the proposed method improve the incorrigibility of the treated fabric.
Phromu l and 3 obre e H and a method for producing substituted ureas of the general formula
/ CH-CH-N-C-N-CH-CHC RoOI. I П I I ODo
OHS A 0 AI OR3
where RI and R2 is C1-C4-alkyl;
Ra is hydrogen, C1-C4-alkyl;
AI and AI - each means a hydrogen atom or together form an ethylene radical ;. characterized in that disubstituted ethanal of the general formula
Rto
sssn
where RI and R2 have the indicated meanings, they are reacted with urea of the general formula
ANH-CO-NH-AI,
the resulting product of the general formula
P . l CH-CH-N-C-N-CH-CH
OR, OR2
{I 11 OH A O AI OH
where Ri, R2, A, Ai have the indicated meanings, isolate or, if necessary, etherify the alcohol of the general formula
R-CH20H, where R is Ci-C3-alkyl or hydrogen.

权利要求:
Claims (1)
[1]
Fo rmu l and z o brie n e i Method of obtaining substituted ureas of general formula
CH-CH-K-C--sn-I. I And 1 |
0¾ A ABOUT {OP3
where Ρι and Pr ~ C1 – C4-alkyl;
Рз - hydrogen, С-gС-alkyl;
15 A and Αι - each means a hydrogen atom or together form an ethylene radical, characterized in that the disubstituted ethanal of the general formula
20
ΚιΟ
R ₇ Basic
where Ρι and Pr have the indicated meanings, are reacted with urea of the general formula
ΑΝΗ <Ο-ΝΗ-Αι,
the resulting product of the general formula
thirty
ΚιΟ
/ ΟΡι
CH-CH-L1-C-C-CH-CH <<
I. I and II · ^x 0P ₂ OH A O Αι OH
where Ρι, Pr, A, Αι have the indicated values, 35 are singled out or if necessary
etherifying with an alcohol of the general formula P-CH2OH,
where P is C- | -C3 alkyl or hydrogen.
I Finishing Agent Distribution angles after crushing on fabric, hail. Ρί TTg ppm what kindthere is after three washes On untreated fabric . 174 174 98.4 Not found On the fabric treated with the product of example 5 273 248.5 ' 63.1 _II_ On the fabric treated with the product of example 6 271 248 50.5 Fabric treated with the reaction product of dimethyldihydroxyethylene urea with a polyol (comparative compound) 261 261 50 110

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引用文献:

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US3487088A|1967-04-14|1969-12-30|American Cyanamid Co|Process for preparing 1,3-dimethylol-4,5-dihydroxy-2-imidazolidinone|

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FR2554447B1|1983-11-08|1987-02-13|Hoechst France|PROCESS FOR MANUFACTURING IMIDAZOLIDINIC STRUCTURE CYCLIC UREA AND ITS APPLICATION IN PARTICULAR IN THE MANUFACTURE OF TEXTILE FINISHES|GB9101690D0|1991-01-25|1991-03-06|Bp Chem Int Ltd|Process|

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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FR8704629A|FR2613361B1|1987-04-02|1987-04-02|SUBSTITUTED UREAS, THEIR PREPARATION PROCESS AND THEIR APPLICATION IN PARTICULAR IN THE ENNOBLISSEMENT OF CELLULOSIC FIBERS|

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