• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    New method for the preparation of N-aryl-N'(mono- or disubstituted)-urea derivatives having the general formula (I), (FORMULA) wherein aryl is an optionally substituted phenyl group, and R<s1>s and R<s2>s each stand for an optionally substituted alkyl, cycloalkyl, alkoxy or phenyl group, or R<s1>s and R<s2>s may form, together with the adjacent nitrogen atom, a nitrogen-containing heterocyclic group which may contain a further hetero atom, or one of R<s1>s and R<s2>s may also stand for hydrogen, with the proviso that if one of R<s1>s and R<s2>s is an optionally substituted phenyl group, the other may represent only hydrogen atom or an optionally substituted alkyl or alkoxy group, by reacting a carbamate of the general formula (II) with an amine of the general formula (III), R<s1>sR<s2>sN-CO-X (II) Aryle-NH<u2>u (III) or a carbamate of the general formula (IV) with an amine of the general formula (V), Aryle-NH-CO-X (IV) R<s1>sR<s2>sNH (V) wherein R<s1>s, R<s2>s and aryl are as defined above and X is a lower alkoxy, phenoxy or substituted phenoxy group, in the presence of a tertiary amine catalyst. According to the invention a tertiary alkylamine containing altogether at least 6 carbon atoms and minimum one alkyl chain with at least 4 carbon atoms or a mixture of such tertiary alkylamines is applied as catalyst.
    公开号:SU1246891A3
    申请号:SU813336817
    申请日:1981-09-24
    公开日:1986-07-23
    发明作者:Терек Шандор；Верешази Лайош；Галамбош Петер；Дароци Иван；Ерменьи Золтан
    申请人:Реанал Финомведьсердьяр (Инопредприятие)；
    IPC主号:
    专利说明:

    112
    The invention relates to an improved method for the preparation of N- (mono- or disubstituted) -N aryl-uric compounds;
    ApHJi-NH-CO-N lJ k.
    . 1 С - apkilna
    where Aryl is unsubstituted or substituted by Hbrii with one or more halogen atoms, nitro, C — C-alkyl-D t, C alkoxy-trP1-halogen-C, groupe and phenyl f
    R, Rj are independently of each other - alkyl,.-Alkoxy group or substituted by one or more halogen atoms or phenyl nitrogroup, or one of R. and R - hydrogen, and R i is a pyridylmethyl group, and Kj ™ is hydrogenoxy.
    and.; gi R., and R form together with the nitrogen atom a new ring morfol.
    These compounds can be used as precursors in the smtsez of biologically active substances.
    11, the purpose of the invention is to
    PR n m er 1. Preparation of N- (4-nitrophenyl) (3-pyridylmethyl) -ureas, 4j22 g {0.02 mol) (A-nitrofeyl) -carbamate, 1.80 g (O5 0167) 3-aminomethylpyridine and 3.18 G (O j 0173 mol1) tributylamine is dissolved in 25 ml of dry toluoot and the mixture is kept at the boiling point for 5 hours. The precipitated product O1 is filtered 2 times, washed with acetone, using: cd1) 1 × 10 ml of the latter, and then dried. As a result, 4.33 g (85–1%) of M (-4-nitrophenyl) - H - (3-pyridmetmet) - urea, the melting point of which is 22.2-224 ° C (a specially prepared sample has a melting point of 223 225 C),
    The described reaction is repeated with the difference that 1.72 g (0.01775 mol) of triethylamine is used as a catalyst. The desired product begins to settle only 4 hours after the start of the boiling of the reaction mixture. The reaction mixture is maintained at the boiling point for 36 hours, after which the precipitated product is filtered off, the product is filtered and washed 2 times with acetone, using each
    68912
    10 ml times. As a result, 3j3 g (64.9%) of M - (4-nitrophe NILE) -N - (3 pyrcidylmethyl) -ureas with a melting point of 222-224 C are obtained.
    5 Example 2. Preparation of N- (4-nitrophenyl) -N - (3-pyridylmethyut) -mochines 196ji3 g (1 mol) me- tip of K- (4-nitrophenyl) -carbamate, 108z14 g (1 mol) 3 aminomethylpyridine and
    0 106.7 g (0.15 col.) S, C-di; atil-n-to-decipamine is dissolved in 3 liters of xylene. The reaction mixture is heated at the boiling point under reflux, npj-gchem traces of water are removed from
    5 mixtures together with the resulting alcohol; using Dean-Stark nozzles. 15--20 minutes after the start of heating, the final product was precipitated from the reaction mixture. Blend on
     M is heated at the boiling point for 4 hours, after which the suspension is filtered at a temperature of 100-110 ° C. Collector, the product is washed on the filter 2 times with heated xylene, using k: already, 100 ml of the last , then with a small amount of acetone, after which the product is dried under vacuum; As a result, 218.6 g (80.3%) of M- (4-nitrophenyl) -K- (3-pyri30 dilmetip) -urea is obtained; melting point 221-223 WITH,
    EXAMPLE 3 Preparation of N- (4-n-itro4-enyl) -N - (3-pyridylmethyl) -urea. The method is carried out according to anajc; With example 2, but as KaTaj H3aTOpa, Or5 mol NjN diethut-H hexadecylamine is used. As a result, 240y 67 g (88, 4%) N- (4-11Itrofepil) S- (3-pyridylmethyl) -Mo4C cheviky, melting point 222 224 C.
    Example 4, Preparation of N- (4-nitrophenip) -H - (3-pyridylmethyl) -mogup. Mixture J consisting of 5 ,, 88 g
    / 15 (0.03 mol-l) methyl-M- (4-nitro-1enyl) -carbamate, 2/70 g (Os025 mol) nomethylpyridine 5 9.6 ml of genamine CS 302 E (mixture N, N-diesel c10- e, alkylamines, product firm; hoechst
    50 AG and 50 ml of xylene 5 are placed in a flask equipped with a Vigrex and Nasa column, Dean-Stark column, and the mixture is heated at its boiling point for 2 hours. During this time, 6 ml of a mixture of water is distilled methyl alcohol and xylene. The reaction mixture is then filtered hot, the crystalline final product is washed 2 times with heated xylene, each time using 5 ml of the latter, and then with a small amount of acetone, after which the product is dried. As a result, 6.0 g (88.2%) of N- (4-nitrophenyl) -K - (3-pyridylmethyl) urea are obtained, the melting point of which is 223-2254.
    Example 5. Obtaining N- (4-nitrophenyl) -Y - (3-pyridylmethyl) -urea. 11.77 g (0.06 mol) of methyl-K- (4-nitro1 |) enyl) carbamate, 5.4 g (0.05 mol) of 3-aminopyridine, 18.7 g (0.065 mol) of genome SH 302 D (mixture K, C-dcmethyl-C a-alkylamines, product of Hoechst AG) and 200 ml of toluene are placed in the device described in Example 4 and the mixture is heated at boiling point for 4 hours. During this time, 15 ml of the mixture is collected in the packing water, methyl alcohol and toluene. The precipitated solid is filtered off, washed 2 times with heated toluene, using 10 ml of the latter each time, then the filtrate is combined with the washing solution and the resulting mixture is used to repeat the indicated reaction. The mother liquor is recycled 10 times. The results of the individual cycles are presented in table 1.
    Table 1
    five
     O 15 20 5 o
    five
    0
    five
    0
    PRI me R 6. Getting N, N - bis- (4-nitrofe.nil) -urea. 9.81 g (50 mmol) of methyl 7-K- (4-nitrophenyl) -carbamate, 6.9 g (50 mmol) of 4-nitroaniline, 140 ml of xylene and 11.8 g (approximately 50 mmol) of genamine CS 302 D (a mixture of Ы, К-dimethyl C, d. „- alkynamines) is placed in a flask equipped with a reflux condenser, after which the mixture is heated at boiling point. The final yellow crystalline product appears in the reaction mixture already on the third minute of heating, and the amount of crystalline precipitate quickly increases. After the thick and orange colored suspension of crystals is heated at a boiling point for 0.5 h, it is filtered under vacuum in a hot state. The product collected on the filter is washed 2 times with hot xylene, using each time 20 ml of the latter, and then with acetone, after which the product is dried in vacuum. As a result, 12.78 g (85.2%) of K, S-bis- (D-nitrophenyl) -urea are obtained. According to the data of chromatography in a layer of sorbent, when a mixture of n-hexane and acetone in the ratio of 3: 1 is used as a solvent, the product is a homogeneous substance. According to chromatography, the product is identical to a specially prepared sample.
    Example 7. Obtaining N.N - bis- (4-nitrophenshko) urea. The method is carried out by analogy with that described in Example 6, but with the difference that a distillation column is connected to the flask, the mixture being kept in a light boiling state, and methyl alcohol is constantly removed from the mixture. After reacting for 2 hours, the product is filtered off, 50 mmol of methyl jH- (4-nitrophenyl) carbamate and 50 mmol of 4-nitroaniline are added to the filtrate, and the reaction is repeated. The results obtained in four successively carried out cycles are presented in table 2.
    Table 2
    Continuation of table 2
    3 13j58 90.5 A 14.75 98.3
    Note: According to the melting point, the quality of the product cannot be characterized accurately enough, since immediately after melting the compound begins to sublimate.
    Example 8 Preparation of N- (4-Chlorophenyl) -carbamoylmorpholine A mixture of 9j28 g (50 mmol) methyl-K- (4-chlorophen-11n) -carb 1ata5 4.36 g (50 mmol) of morpholine, 100 ml of xylene and 10.6 g (50 mmol) of K, M-dimethyltetra Heat gently at the boiling point of the reaction mixture for 6 hours. By distillation, methyl graph is continuously removed from the reaction mixture. After that, the heating is stopped, the mixture is cooled and the slug is nodded overnight, the precipitated crystallization product is filtered off and dried, the result is 9.1 g (75.6%) of N- (4-chlorophenyl) -carbamoylmorpholine 5 the melting point of which is 196 - 200 С (specially prepared sample has a melting point of 196-200 ° С) „
    Example 9. Preparation of N- (4-chlorophenyl N-3,4-dichlorophenyl) urea. A mixture of 4j61 g (25 mmol) methyl-L- (4-chlorophenyl) -carbate, 4.07 g (25 mmol) of Ze4-dichloraniline, 100 ml of toluene and 4.7 g (25 mmol) of N, N-dime- tildodecylamine is introduced into the reaction by analogy with that described in Example 8, and the reaction is carried out for 20 hours, after which the mixture is allowed to cool. As a result of separation from the mixture, 4.60 g (58.4%) M- (4- chloro-HHJi) -N - (3,4-dichlorophenyl) urea as a crystalline substance.
    Example 10. Preparation of N- (dichlorophenl) -carbamoi. Pmorpholine.
    0
    A mixture consisting of 5.50 g (25 mmol) methyl-N- (3, 4-dichlorophenyl) carbamate, 2.18 g (25 mmol) of morpholine, 100 ml of xylene and 4.7 g (25 mmol) M, K-dimethyldodecylamine J is introduced into the interaction by analogy with that described in Example 8, and the reaction is carried out for 12 hours. The crystalline substance that precipitated upon cooling is filtered off, 25 mmol methyl-N is added to the f-s. - (3, 4-dichlorophenyl) carbamate and 25 mmol of morpholine J, after which the reaction was repeated. After the first reaction, 5.0 g (72.7%) of N- (3,4-dichlorophenyl) -carbamoylmorpholine 5 is obtained, while after the second reaction, 6.35 g (92.3%) of the same compound is obtained. Both fractions have temperature
    0
    0
    S
    0
    five
    melting at 152-155 ° C (a specially prepared sample melts at 157-158 ° C).
    The above reaction is repeated in such a way that 25 mmol of triethylamine is added to the mixture instead of N, N-dimethyldrdecylamine. The result is 3.05 g (44.3%) of the final product after reaction for 24 hours.
    Example 11 Preparation of N- (3,4-dichlorophenyl) -gc -methyl K -butylbenches, See: All 5 consisting of 5.50 g (25 mol) methyl-N- (354-dichlorophenyl) -carbamate 2, 18 g (25 mmol) of N-butylmethylamine 4; 7 g (25 mmol) of N5N-dimetidodecylamine and 100 ml of light gasoline are introduced into the reaction by analogy with that described in example B, and the interaction is carried out for 3 h. The precipitated solid is filtered off, 2.18 g (25 mmol) of K-butylmethylamine and 25 mmol of methyl N- (3 p of 4-di x.phenyl) carbamate p are added to the fcter and then rea. re-run. After the first reaction, g (53-8%) N (3p 4-dichlorophenyl) -K-methyl-N-butylurea is obtained, while after the second reaction, 5.05 g (73J4%) of the same compound is isolated. Both fractions have a melting point of 108-111 ° C (a specially prepared sample has a melting point of 11 6-1 1 7 s).
    Example 12. Preparation of N- (3,4-Dichlorophenyl) -N-methyl-N-butyl urea. The tutorial is implemented by analogy with oiTMcajSHbiM in example 1-1, but in ka712
    100 ml of xylene are used as the solvent. The course of the reaction is controlled by chromatography in a layer of sorbent. When the reaction proceeds by approximately 90% according to chromatography, the mixture is evaporated in vacuo. The result is a viscous, yellowish residue that dissolves well in such organic solutions.
    scavengers such as acetone and
    methyl ethyl ketone, and which can be used in the preparation of a herbicidal solution for spraying.
    Example 13. Preparation of N- (4-chlorophenyl) -N, S -dimethylurea. A mixture consisting of 12.8 g (0.1 mol of 4-chloroaniline, 10.3 g (0.1 mol) of methyl-N, N-dimethylcarbamata, 20 ml of dimethylhexadecylamine and 100 ml of high-boiling petroleum fraction ether (boiling point in the range of 160-180 ° C), introduced into the reaction by analogy with that described in example 12 When, according to chromatography data, the reaction proceeds by about 90%, the reaction is stopped. As a result, a solution of K- (4-chlorophenyl) - dimethyl urea (monuron), which can be directly used in the preparation of a herbicidal preparation such as spray liquid Vani or impregnated granular preparation. I
    Limer 14. Preparation of N- (4-chlorofensh1) -M, K -dimethylurea. 4.64 g (0.025 mol) of methyl-N- (4-chlorophenyl) -carbamate and 21.3 ml of LA 302 D genamine (a mixture of H, H-dimethyl-C, 2.-alkylamines, products from HöchstAG mix in a 100 ml flask which is equipped with a distillation column. The mixture is heated to 150-160 ° C and dimethylamine gas is added. At the final stage of the reaction, the reaction mixture is heated above 160 ° C in order to remove methyl alcohol.
    The resulting solution, colored yellowish-brown, is allowed to cool, after which a white solid is filtered off. The filter cake is washed 3 times with n-hexane, using 10 ml of the latter each time, and then dried. The filtrate is combined with the washing solution and the resulting mixture is applied in
    eight
    These cycles as the reaction medium. In the next cycle, 4.64 g of the specified carbamate is introduced into the reaction medium, after which the mixture is heated while feeding dimethylamine gas. First, n-hexane is distilled off, which is used in the pre-cycle as a washing agent, then it is collected separately and reused as a washing agent.
    The combined mother liquor and wash solution are refined 10 times. The results obtained in separate cycles are presented in Table 3.
    Table 3
    20
    five
    The average
    about (
    J
    78.07
    Note. According to the literature, the melting point of N- (4-chlorophenyl) -N, N-dimethylurea (monuron) is 174-175 C.
    Example 15. Preparation of N-phenyl-N, N-dimethylurea. The method is carried out by analogy with that described in Example 14, but 3.78 g are used as the starting material.
    9
    (0.025 mol) metip-K-f8Nilcarbamate and the mixture is heated at HO-180 ° C for IjS h. The combined mother liquor and industrial solution are recycled 8 times. The results obtained in separate cycles are presented in Table 4.
    Table 4
    124689110
    Approximately 90% of the reaction is complete. As a result, a solution of N- (3, 4 - dich. Porphylen-K-marks of C-N-methyl1 of ureas (linuron) is obtained. The resulting solution can easily be diluted with common organic solvents such as acetone or methyl ethyl keogN; and then it can directly be used to obtain herbicide compositions S, for example, j, the capacity for specimen shann or nponHTaHHof-o of a granulated hydro drug.
    Example 17, Mix 3 ,, 7 8 g (Oj, 025 mol). methyl complex
    15 N-phenylcarbamic acid ester and 21.3 ml of LA 302 D genamine (mixture H5A D1-methyl C ,, .- alkylamiovi J manufactured by Höcht AG) are heated in a flask with a volume of 100 ml, equipped with
    20 with a distilling nozzle, the dimethylamine gas being blown through the mixture. During the longest part of the reaction time, the temperature is maintained at -.
    are at 140-160 GS and
    Note, According to the literature data, the melting point of N-f-Hi-ra-N 5N di1 1et1urea (phenuron) is 133-134 s,
    Example 16 “Preparation of N (3 ,; dichlorophenyl) N ° -methoxy-M-m: methyl. 5.5 g (0.025 col) methyl M- (354 dsporpheneschd) ™ carbamate is dissolved in 23 ml (approximately mol) of LA 302 D genamine (mixture of NjN-dime-TSH1-C-alkylamino) during heating and heating; -y maintained at 200 ° Cj, after which 2.3 g (0.0375 mol) of methoxymethylamine gas are passed through the mixture for approximately 3.4. The reaction is monitored by chromatography in the adsorbent layer; control by measuring the temperature of the vapors above the mixture. When the degree of transformation reaches
    0 with a distilling nozzle, and dimethylamine gas is blown through the mixture. But during the longest part of the reaction time, the temperature is maintained -.
    0

    are at 140-160 GS and
    only in
    .
    the end
    allow up to, until the distillate (methanol) is volatilized. The whole reaction time is about 1.5 hours,
    The solution is cooled; the final product is precipitated in crystalline form; the filter is washed three times with 10 ml of n-hexane; then the filtrate 5, combined with the washing liquid, is dried in the next reaction, used again as a medium, and again, 3, 78 N of methyl N-ester are added again. phenylcarbamic acid and, along with the introduction of dg-pchetylamine, repeat this reaction. When heated, the n-hexaH used for proms is first subjected to re-distillation; which is separately captured and reused for washing the following final product.
    The reaction is carried out using the same recipe; the ionic mixture is repeated 8 times. The results obtained are summarized in Table 5.
    Table 5
    Final product
    Continuation of table.5
    The melting point of N-phenyl-N |, N -dimethylurea (phenurone) is 133-134 ° C according to literature data.
    Example 18. Obtaining N- (3j4 dichlorophenyl) -N-methoxy N-methylurea (linuron). 5.5 g (0.025 mol) of N- (3,4-dichlorophenyl) -carbamic acid methyl ester with stirring and heating are dissolved in 23 ml (about 0.075 mol) of the amine LA 302 D (mixture of dimethyl-C ,,., - Alkylamine, manufactured by Hoechst AG) and through the gas supply pipe, only 2.3 g (0.0375 mol of methoxymethylamine) is blown through the mixture for about 3 hours, while the temperature is maintained at about 200 C. For the course of the reaction is followed, firstly, on the basis of the temperature of the steam, secondly, due to the layer-by-layer chromatography. When about 90% of the reaction ends, it stops A conversion of N- (3,4-dichlorophenyl) -N-marks of CH-N-methyl urea is obtained, which can be easily diluted further with organic solvents, for example, acetone or methylethylene ketone and used in this form my to obtain herbicidal preparations, for example, spray solutions or impregnated granules
    Example 19. Preparation of N- (3-chloro-4-methyl-phenyl) -N, N-dimethyl-urea (chlorotoluron). Mixture
    4.99 g (25 mol). Methyl-N- (3-chlorometh-10-phenyl) -carbamate, 6.74 g (25 mmol) of Armin DM16D (N, N-AiiMeTimreKcaflemm- amine of technical quality, manufactured by AkEO Chemie Stalia Spa) and 25 ml of Xtol are converted as described in npiCT epe 14, with dt methyl amine for 5 following one after another reactions. The results obtained are summarized in table 6.
    Table 6
    Final product
    thirty
    The melting point of chlorotoluron is according to the special literature 147-148 Cs
    Example 20 “Preparation of N- (4 isopropyl phenyl) -N, N-di ethnyl moieties (isoproturon), a mixture of 14.50 g (75 mmol) of metpl-N- (4 isopropyl-phenone) urea 6, 04 g (25 mmol) of the DM14D catalyst catalyst (N, K-dimethyltetradecyl-apt of technical quality, Akzo Chemie Stalia Spa manufacturer) and 25 ml of lacquer gasoline are maintained at a constant supply of dimepsamine gaseous gas, as in Example 14, at 140-150 ° C. After one hour of conversion, the heating and gas flow is stopped. When the mixture is cooled, it begins with the cooling of the final product. The product is filtered at room temperature,. washed with 2 times 20 ml of lacquer gasoline, then with hexane and dried. 7.60 g (49.13 / 0 of N- (4-isopropyl phenyl) -b, N -dpmethylurea, point
    13I
    melting at 153-155 ° C (according to literature data 155-156 ° C).
    Example 21, Preparation of N- (3-trifluoromethyl-phenyl) -N, N-dimethyl-, chevine (fl ometronone), Acts as in Example 17, but takes 12j1 g (75 mmol) 3- as the starting material trifluormeth1-ans1nna. Obtain 11 pO g (63.2%) of N- (3-trifluoromethyl-phenyl) -N 5K -dimethylurea5 melting point 159-162, (according to literature data 163-16455 С)
    Example 22. Getting A / (3 - chloro - 4 - methoxy - fe Editor R. Tsitsika
    Compiled by S. Paul Kova
    Tehred J. Popovi Proofreader L. Pilipenko
    Order 4029/59 Circulation 379Subscription
    VNIIPI USSR State Committee
    for inventions and open. tiy, 113035, -Moscow, Zh-35, Raushsk na6,, d. 4/5
    Production and printing company, Uzhgorod, st. Project, 4
    A689114
    NIL) - A /, l / - dimethyl - urea (methoxuron).
    The operation is carried out as in Example 17, but 5 G (3 g, 75 g (75 mmol) of 3-chloro-4-methoxy-aniline is taken as the starting material. 14.10 g (82.3%) of No.- (3- -chloro-4-methoxy-phenyl) -N ,, N - dimetschl yuchevin = a melting point of 123-125 ° C (according to literature data 126-10).
    The proposed method makes it possible to obtain the claimed compounds in a simpler way with a good yield, which was previously unknown.
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING N- (MOHO- OR DISPLACED) -YARYL UREA DERIVATIVES of the general formula!
    Aryl-HH-S0-M / X 1 R !
    where Aryl is unsubstituted or substituted by one or more halogen atoms of nitro, C ^ -C ^ -alkyl, -C, alkoxy-trihalo-C ^ ~ C 4 -alkyl group of phenyl;
    R 4 , R is, independently of one another, a C-C alkyl, C 4 -C 4 alkoxy group or substituted with one or more halogen atoms or a phenyl nitro group, or one of R ( and R, is hydrogen, or R ( is pyridylmethyl group , a R 2 hydrogen, or R, and And 2 form together with the nitrogen atom a morpholine ring by the interaction of the carbamate of the general formula II
    Aryl-NH-CO-X, where Aryl has the indicated values ^ X is a lower alkoxy group, is reacted with an amine of the general formula III
    P, R 2 NH where R ^ and Rj have the indicated meanings in an organic solvent at the boiling point of the reaction medium in the presence of a trialkylamine catalyst, characterized in that, in order to simplify the process, a tertiary alkylamine of the general formula IV is used as a catalyst, where R } and R 4 is lower alkyl;
    Rf is C 4 -C 1 ~ alkyl, provided that a total of at least 6 carbon atoms are contained, and one alkyl radical contains at least 4 carbon atoms, or a mixture of tertiary alkyl amines of the general formula IV, in an amount of 0.51 mol per 1 mol of the reaction component.
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    同族专利:
    公开号 | 公开日
    GB2080808A|1982-02-10|
    WO1981002156A1|1981-08-06|
    BR8106184A|1981-11-24|
    CH649078A5|1985-04-30|
    US4410697A|1983-10-18|
    GB2080808B|1984-01-04|
    引用文献:
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    US3161676A|1962-05-21|1964-12-15|Berkeley Chemical Corp|Preparation of substituted alkyl ureas|
    CH473537A|1966-12-22|1969-06-15|Geigy Ag J R|Herbicidal agent|
    IT1037577B|1975-04-23|1979-11-20|Snam Progetti|PROCEDURE FOR THE TRANSESTERIFICATION OF ESTERS OF THIOCARBAMIC ACIDS|US5003106A|1983-07-19|1991-03-26|American Cyanamid Company|Antiatherosclerotic ureas and thioureas|
    US4889589A|1986-06-26|1989-12-26|United Technologies Corporation|Gaseous removal of ceramic coatings|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    HU15880A|HU185613B|1980-01-25|1980-01-25|Process for preparing n-acyl-n'-/mono- or disubstituted/-carbamides|
    HU15780A|HU184715B|1980-01-25|1980-01-25|Process for the preparation of n-bracket-4-nitro-phenyl-bracket closed-n-comma above-bracket-3-pyridyl-methyl-bracket closed-urea|
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