DOCSLIB.ORG

Process for Producing Laurolactam Verfahren Zur Herstellung Von Laurolactam Procédé De Production De Laurolactame

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Process for Producing Laurolactam Verfahren Zur Herstellung Von Laurolactam Procédé De Production De Laurolactame (19) TZZ _T (11) EP 2 292 599 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C07D 201/04 (2006.01) C07D 225/02 (2006.01) 06.01.2016 Bulletin 2016/01 C07B 61/00 (2006.01) (21) Application number: 09750568.9 (86) International application number: PCT/JP2009/059197 (22) Date of filing: 19.05.2009 (87) International publication number: WO 2009/142206 (26.11.2009 Gazette 2009/48) (54) PROCESS FOR PRODUCING LAUROLACTAM VERFAHREN ZUR HERSTELLUNG VON LAUROLACTAM PROCÉDÉ DE PRODUCTION DE LAUROLACTAME (84) Designated Contracting States: • YASUMATSU, Ryouta AT BE BG CH CY CZ DE DK EE ES FI FR GB GR Ube-shi HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL Yamaguchi 755-8633 (JP) PT RO SE SI SK TR • KAWAI, Joji Ube-shi (30) Priority: 20.05.2008 JP 2008131425 Yamaguchi 755-8633 (JP) 20.10.2008 JP 2008269262 (74) Representative: Cabinet Plasseraud (43) Date of publication of application: 52, rue de la Victoire 09.03.2011 Bulletin 2011/10 75440 Paris Cedex 09 (FR) (73) Proprietor: Ube Industries, Ltd. (56) References cited: Ube-shi, Yamaguchi 755-8633 (JP) WO-A1-2007/125002 WO-A1-2008/096873 WO-A1-2009/069522 JP-A- 2001 342 174 (72) Inventors: JP-A- 2006 219 470 • KUGIMOTO, Junichi Ube-shi • FURUYA YOSHIRO ET AL: "CYANURIC Yamaguchi 755-8633 (JP) CHLORIDE AS A MILD AND ACTIVE BECKMANN • II, Nobuhiro REARRANGEMENT CATALYST", JOURNAL OF Ube-shi THE AMERICAN CHEMICAL SOCIETY, Yamaguchi 755-8633 (JP) AMERICAN CHEMICAL SOCIETY, • DOI, Takashi WASHINGTON, DC; US, vol. 127, 1 January 2005 Ube-shi (2005-01-01), pages 11240-11241, XP002441494, Yamaguchi 755-8633 (JP) ISSN: 0002-7863, DOI: 10.1021/JA053441X & • FUJITSU, Satoru FURUYA YOSHIRO ET AL: "SUPPORTING Ube-shi INFORMATION: CYANURIC CHLORIDE AS A Yamaguchi 755-8633 (JP) MILD AND ACTIVE BECKMANN • GOTOU, Tadashi REARRANGEMENT CATALYST", JOURNAL OF Ube-shi THE AMERICAN CHEMICAL SOCIETY, Yamaguchi 755-8633 (JP) AMERICAN CHEMICAL SOCIETY, • SHIMOMURA, Hideo WASHINGTON, DC; US, vol. 127, 1 January 2005 Ube-shi (2005-01-01), page S1-S6, XP002441494, ISSN: Yamaguchi 755-8633 (JP) 0002-7863, DOI: 10.1021/JA053441X Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 2 292 599 B1 Printed by Jouve, 75001 PARIS (FR) (Cont. next page) EP 2 292 599 B1 • RUSSELL R: "One-Pot Synthesis Aids Scale-Up and Data Collection", PHARMACEUTICAL TECHNOLOGY, ADVANSTAR COMMUNICATIONS,INC, US, no. Nov, 1 November 2003 (2003-11-01), page 17,22, XP002433225, ISSN: 1543-2521 2 EP 2 292 599 B1 Description Technical Field 5 [0001] The present invention relates to an industrially useful process for producing laurolactam from cyclododecanone oxime. Background Art 10 [0002] A common industrial process for producing an amide compound involves Beckmann rearrangement of a cor- responding oxime compound. For example, ε-caprolactam which is industrially useful is produced by Beckmann rear- rangement of cyclohexanone oxime. Rearrangement catalysts used are generally concentrated sulfuric acid and oleum. Since these strong acids must be used in the stoichiometric amounts or more, they form a large amount of ammonium sulfate as a byproduct during neutralization. Although laurolactam, which is a starting material for Nylon 12, is also 15 produced in a similar manner, the process is more complex because cyclododecanone oxime as an intermediate product has a high melting point. In producing ε-caprolactam, both cyclohexanone oxime and ε-caprolactam have relatively low melting points, so that oxime formation or rearrangement reaction can be conducted in a solvent-free system, but production of laurolactam requires a reaction solvent. This reaction solvent must be able to substantially dissolve cy- clododecanone oxime and be inert to concentrated sulfuric acid or oleum, and therefore the selection of the solvent is 20 considerably restricted. [0003] The following references have described a known process for industrially producing laurolactam from cyclodo- decanone and an aqueous solution of hydroxylamine. [0004] Patent Reference 1 has described the following process. Cyclododecanone is converted into an oxime using isopropylcyclohexane as a solvent, and after separating layers, a resulting solution of cyclododecanone oxime in iso- 25 propylcyclohexane is slowly added to concentrated sulfuric acid at a low temperature to prepare a solution of a cyclodo- decanone oxime sulfate adduct in sulfuric acid. After separating and recovering isopropylcyclohexane, the residual solution of cyclododecanone oxime sulfate adduct in sulfuric acid is heated to carry out Beckmann rearrangement of the oxime. After the rearrangement reaction, water is added to the system to dilute sulfuric acid and from the mixture, the laurolactam produced is extracted with an organic solvent. Here, the extraction solvent may be isopropylcyclohexane 30 or cyclododecanone. The extraction solvent is recovered by distillation from the resulting extraction solution and then laurolactam in the residue is purified by distillation. [0005] This process does not generate ammonium sulfate as a byproduct in the rearrangement reaction step, but requires enormously large facilities and energy for treating a large amount of waste diluted sulfuric acid. Furthermore, since cyclododecanone reacts with concentrated sulfuric acid to form a byproduct, the oxime-forming reaction must be 35 completed for eliminating residual cyclododecanone, but due to hydrophobicity of isopropylcyclohexane, a mass transfer rate is low in an oil-water interface, leading to a longer oxime-forming reaction. As a whole, the process involves many steps of separation, recovery and recycling of solvents and, therefore, requires considerably large equipment expenses and energy. [0006] Patent Reference 2 has described the following process. A mixture of cyclododecanone and cyclohexanone 40 is blended with an aqueous solution of hydroxylamine to produce oximes. Cyclohexanone oxime produced has a low melting point and is a good solvent for cyclododecanone oxime, so that the reaction can be conducted at 100 °C or lower and at an ambient pressure. Furthermore, cyclohexanone oxime is adequately hydrophilic for the oxime-forming reaction to quickly proceed, and the mixture is transferred to the rearrangement step without residual cyclohexanone or cyclodo- decanone. A rearrangement catalyst used is concentrated sulfuric acid or oleum. Whereas laurolactam produced has 45 a high melting point, it is highly soluble in caprolactam having a low melting point which is simultaneously produced. Therefore the reaction can be carried out even at a temperature of 100 °C or lower. The resulting rearrangement reaction solution is neutralized with ammonia water and then extracted with an organic solvent. Caprolactam can be dissolved in water to some extent, but is extracted into an organic solvent due to salting-out effect of ammonium sulfate formed by neutralization. Next, a large amount of water is added to the solution containing extracted laurolactam and caprolactam, 50 and caprolactam is extracted into the aqueous phase. From the separated organic phase, the organic solvent is recovered and laurolactam is purified by distillation. On the other hand, the aqueous phase is concentrated and after removing impurities, caprolactam is purified. [0007] This process is excellent in that laurolactam and caprolactam can be produced together. However, as a process for producing laurolactam, it has the following problems; (1) separation and purification of caprolactam requires large 55 amounts of equipment expenses, resulting in low investment efficiency and the process involves operations of low energy efficiency such as concentration of an aqueous solution of caprolactam; (2) there is a restriction to a production ratio of laurolactam/caprolactam; and (3) caprolactam is a low-value-added product in comparison with laurolactam and an use efficiency of hydroxylamine is low. 3 EP 2 292 599 B1 [0008] Patent Reference 3 has described Beckmann rearrangement of an oxime compound in a polar solvent, wherein a rearrangement catalyst used is an aromatic compound (1)containing, as an aromatic-ring member, at least one carbon atom having a leaving group, (2)containing at least three aromatic-ring members, which are either or both of heteroatoms or/and carbon atoms having an electron- withdrawing group, and (3)wherein two of the heteroatoms and/or carbon atoms 5 having an electron-withdrawing group are at the ortho- or para-position to the carbon atom having an electron-withdrawing group. Non-Patent Reference 1 has described in detail a rearrangement reaction using the rearrangement catalyst disclosed in Patent Reference 3. Focusing attention on a low yield of rearrangement when a non-polar solvent is used in Non-Patent Reference 1, Patent Reference 4, 5 and 6 have improved the yield and thus extended the range of solvents which can be used, to non-polar solvents. Generally, a non-polar solvent is more thermally and chemically stable, has 10 a lower boiling point and has a smaller evaporative latent heat than a polar solvent, and thus, can be easily recovered and recycled, while it little dissolves a polar organic material or an inorganic material. [0009] We have selected trichlorotriazine among the catalysts disclosed in Patent Reference 3, and have investigated its reaction with cyclododecanone oxime. [0010] Patent Reference 3 and Non-Patent Reference 1 have explained a mechanism of the catalytic action of trichlo- 15 rotriazine (R3-Cl wherein R3 represents dichlorotriazinyl) in Beckmann rearrangement of a ketoxime (R 1-C(-R2)=N-OH wherein R1 and R2 represent alkyl or these may together form cycloalkane) as follows. [0011] First, hydrogen chloride is eliminated from trichlorotriazine and the ketoxime to form R 1-C(-R2)=N-O-R3 (ether).
Load more

Recommended publications
  • (12) Patent Application Publication (10) Pub. No.: US 2013/0157779 A1 Kim Et Al
    US 2013 O157779 A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2013/0157779 A1 Kim et al. (43) Pub. Date: Jun. 20, 2013 (54) GOLF BALL COMPOSITION cover layer. The outer cover layer and/or one or more inter mediate layers includes a blend of a)2 to 60 wt % (based on (75) Inventors: Hyun J. Kim, Carlsbad, CA (US); Hong the total weight of the blend composition) of a cyclic olefin G. Jeon, Carlsbad, CA (US) polymer which includes a norbornene-based monomer hav (73) Assignee: Taylor Made Golf Company, Inc. ing the general formula: (21) Appl. No.: 13/330,453 (22) Filed: Dec. 19, 2011 Publication Classification (51) Int. Cl. A63B 37/00 (2006.01) A63B 37/2 (2006.01) R18 R19, R2 A63B 37/08 (2006.01) R20 A63B 37/02 (2006.01) A63B 37/06 (2006.01) (52) U.S. Cl. where R' to R' independently representahydrogenatom, a USPC ........... 473/373; 473/378; 473/385; 473/372; halogenatom or a hydrocarbon group and mis from 0 to about 473/376; 473/377 3; and b) about 40 to about 98 wt % (based on the total weight of the blend composition) of one or more additional polymer (57) ABSTRACT components. The blend composition has a melt flow index This invention pertains to a golf ball which includes a core, (MFI) from 1 to 80 g/10 min., a material hardness of 30 to 90 optionally one or more intermediate layers; and an outer Shore D, and a flex modulus of 10 to 120 kpsi.
    [Show full text]
  • Synthesis of Functionalized Polyamide 6 by Anionic Ring-Opening Polymerization Deniz Tunc
    Synthesis of functionalized polyamide 6 by anionic ring-opening polymerization Deniz Tunc To cite this version: Deniz Tunc. Synthesis of functionalized polyamide 6 by anionic ring-opening polymerization. Poly- mers. Université de Bordeaux; Université de Liège, 2014. English. NNT : 2014BORD0178. tel- 01281327 HAL Id: tel-01281327 https://tel.archives-ouvertes.fr/tel-01281327 Submitted on 2 Mar 2016 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Logo Université de cotutelle THÈSE PRÉSENTÉE POUR OBTENIR LE GRADE DE DOCTEUR DE L’UNIVERSITÉ DE BORDEAUX ET DE L’UNIVERSITÉ DE LIEGE ÉCOLE DOCTORALEDE SCIENCES CHIMIQUES (Université de Bordeaux) ÉCOLE DOCTORALE DE CHIMIE (Université de Liège) SPÉCIALITÉ POLYMERES Par Deniz TUNC Synthesis of functionalized polyamide 6 by anionic ring-opening polymerization Sous la direction de Stéphane CARLOTTI et Philippe LECOMTE Soutenue le 30 octobre 2014 Membres du jury: M. PERUCH, Frédéric Directeur de recherche, Université de Bordeaux Président M. HOOGENBOOM, Richard Professeur, Ghent University Rapporteur M. MONTEIL, Vincent Chargé de recherche, Université Claude Bernard Rapporteur M. YAGCI, Yusuf Professeur, Istanbul Technical University Examinateur M. AMEDURI, Bruno Directeur de recherche, Institut Charles Gerhardt Examinateur M. SERVANT, Laurent Professeur, Université de Bordeaux Invité Preamble This PhD had been performed within the framework of the IDS FunMat joint doctoral programme.
    [Show full text]
  • 172 Subpart C—Substances for Use As Components
    § 175.210 21 CFR Ch. I (4–1–13 Edition) not to exceed 0.05 percent by weight of Rubber hydrochloride. the finished pressure-sensitive adhe- Rubber (natural latex solids or crepe, sive. smoked or unsmoked). (8) 2-Hydroxy-1-[4-(2-hydroxyethoxy) Terpene resins (a- and b-pinene), homopolymers, copolymers, and conden- phenyl]-2-methyl-1-propanone (CAS sates with phenol, formaldehyde, cou- Reg. No. 106797–53–9) as a photoinitiator marone, and/or indene. at a level not to exceed 5 percent by Tetrasodium ethylenediaminetetraacetate. weight of the pressure-sensitive adhe- Tri(mixed mono- and dinonylphenyl) sive. phosphite (which may contain not more than 1 percent by weight of (9) Butanedioic acid, sulfo-1,4-di-(C9- triisopropanolamine). C11 alkyl) ester, ammonium salt (also known as butanedioic acid sulfo-1, 4- (c) Acrylonitrile copolymers identi- diisodecyl ester, ammonium salt [CAS fied in this section shall comply with Reg. No. 144093–88–9]) as a surface ac- the provisions of § 180.22 of this chap- tive agent at a level not to exceed 3.0 ter. percent by weight of the finished pres- sure-sensitive adhesive. [42 FR 14534, Mar. 15, 1977, as amended at 42 FR 15674, Mar. 22, 1977; 48 FR 15617, Apr. 12, (b) Pressure-sensitive adhesives pre- 1983; 63 FR 3464, Jan. 23, 1998; 63 FR 51528, pared from one or a mixture of two or Sept. 28, 1998; 64 FR 48291, Sept. 3, 1999] more of the substances listed in this paragraph may be used as the food-con- Subpart C—Substances for Use as tact surface of labels and/or tapes ap- plied to raw fruit and raw vegetables.
    [Show full text]
  • Tepzz¥ Z89 7A T
    (19) TZZ¥ Z _T (11) EP 3 208 927 A1 (12) EUROPEAN PATENT APPLICATION published in accordance with Art. 153(4) EPC (43) Date of publication: (51) Int Cl.: 23.08.2017 Bulletin 2017/34 H02M 7/12 (2006.01) C07C 251/44 (2006.01) H01L 33/00 (2010.01) C07B 61/00 (2006.01) (2006.01) (2006.01) (21) Application number: 15849932.7 C07D 201/04 C07D 223/10 C07D 225/02 (2006.01) (22) Date of filing: 18.09.2015 (86) International application number: PCT/JP2015/076613 (87) International publication number: WO 2016/059942 (21.04.2016 Gazette 2016/16) (84) Designated Contracting States: • TAKAHASHI, Toru AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Otsu-shi GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO Shiga 520-8558 (JP) PL PT RO RS SE SI SK SM TR • ITO, Hiroyasu Designated Extension States: Nagoya-shi BA ME Aichi 4558502 (JP) Designated Validation States: • SUGAWARA, Kazuki MA Tokai-shi Aichi 476-8567 (JP) (30) Priority: 15.10.2014 JP 2014210567 (74) Representative: Hoefer & Partner Patentanwälte (71) Applicant: Toray Industries, Inc. mbB Tokyo 103-8666 (JP) Pilgersheimer Straße 20 81543 München (DE) (72) Inventors: • OHNO, Fumikatsu Otsu-shi Shiga 5208558 (JP) (54) THREE-PHASE AC/DC CONVERSION DEVICE, PHOTOCHEMICAL REACTION DEVICE AND METHOD USING SAME, AND METHOD FOR PRODUCING LACTAM (57) Provided are a three-phase AC/DC converter means outputs the pulse width modulation signals based disposed between a three-phase AC power supply and on a power supply voltage phase and an output voltage a light emitting diode group, the converter comprising: a between the DC buses, a photochemical reaction device three-phase full bridge circuit in which pairs of switching and a photochemical reaction method using the device, elements are connected in parallel between DC buses and a method for producing lactam using the photochem- for the three phases of the three-phase AC power supply; ical reaction method.
    [Show full text]
  • Certified Reference Materials for Food Packaging Specific Migration Tests: Development, Validation and Modelling
    Certified reference materials for food packaging specific migration tests: development, validation and modelling Niels H. Stoffers Promotor Prof. dr. ir. M.A.J.S. van Boekel Hoogleraar Productontwerpen en Kwaliteitskunde, Wageningen Universiteit. Co-promotoren Dr. ir. M. Dekker Universitair Hoofddocent bij de leerstoelgroep Productontwerpen en Kwaliteitskunde, Wageningen Universiteit Dr. ir. J.P.H. Linssen Universitair docent bij de leerstoelgroep Productontwerpen en Kwaliteitskunde, Wageningen Universiteit Samenstelling promotiecommissie Prof. dr. ir. A.G.J. Voragen (Wageningen Universiteit) Prof. dr. ir. R.M. Boom (Wageningen Universiteit) Prof. dr. ir. G. van Straten (Wageningen Universiteit) Dr. R. Franz (Fraunhofer Institut IVV, Freising, Duitsland) Dit onderzoek is uitgevoerd binnen de onderzoekschool VLAG Certified reference materials for food packaging specific migration tests: development, validation and modelling Niels H. Stoffers Proefschrift ter verkrijging van de graad van doctor op gezag van de rector magnificus van Wageningen Universiteit, Prof. dr. ir. L. Speelman in het openbaar te verdedigen op dinsdag 18 januari 2005 des namiddags te half twee in de Aula ISBN: 90-8504-136-8 Abstract Stoffers, N.H. (2004). Certified reference materials for food packaging specific migration tests: development, validation and modelling. PhD thesis, Wageningen University, The Netherlands. This thesis compiles several research topics during a feasibility study for the certification of 6 reference materials for specific migration testing of food packaging materials. The overall results of the certification exercise, covering results for 3 certification parameters (initial concentration of migrants, specific migration value and diffusion coefficient) from 4 participating laboratories were evaluated. The development and validation of analytical methods for the nylon 12 monomer laurolactam was described.
    [Show full text]
  • Reactivity Features of Cyclododecanone
    Reviews and Accounts ARKIVOC 2011 (i) 429-495 Reactivity features of cyclododecanone Hanafi H. Zoorob, Mohamed S. Elsherbini, and Wafaa S. Hamama* Chemistry Department, Faculty of Science, Mansoura University, El-Gomhoria Street, 35516 Mansoura, Egypt E-mail: [email protected] Abstract Cyclododecanone is a highly important synthetic intermediate for macrocyclic systems. This review is the sole and comprehensive one that covers the different aspects of cyclododecanone chemistry over the period from 1950 to 2010. Keywords: Cyclododecanone, muscone, fragrances, macrocylic ketones, ring enlargement and heterocycles Table of Contents 1. Introduction 2. Synthesis of Cyclododecanone 3. Chemistry of Cyclododecanone 3.1. Halogenation 3.2. Oxidation 3.3. Alkylation 3.4. Mannich reaction 3.5. Ring enlargement 3.5.1. Macrocyclic ketones and esters 3.5.2. Macrocyclic lactames and lactones 3.5.3. Macrocyclic Acetylenes 3.6. Ring contraction 3.7. Construction of spiro and fused heterocyclic systems 3.7.1. Spiro heterocyclic systems 3.7.2. Fused heterocyclic systems 3.8. Photochemistry 3.9. Miscellaneous reactions 4. Conformational Characteristics of Cyclododecanone 5. Conclusion Page 429 ©ARKAT-USA, Inc. Reviews and Accounts ARKIVOC 2011 (i) 429-495 6. Appendix: Abbreviations and Acronyms 7. References 1. Introduction Cyclododecanone 1 is a commercially available ketone, and important synthetic intermediate in the synthesis of natural products containing macrocyclic ring systems such as the anticancer rosphellin 2,1 the potent microglial activation modulators tocopherol fatty alcohols (TFAs) 3,2 cytotoxic sponge alkaloids motuporamine A 4, motuporamine B 5,3 ingenes 6 and 7,4,5 (Scheme 1). N RO O H3CO (CH2)n O O OH NH R=H,Me,Ac Cl n=11to15 Cyclododecanone roseophilin TFAs 1 23 H N N N H2N N N 2 H H Motuporamine A Motuporamine B 4 5 O O O O O O 6a 6b 7 Scheme 1 Cyclododecanone is also an important intermediate for synthesis of natural muscone 8 and macrocyclic fragrances of musk like odor e.g.
    [Show full text]
  • THE EFFECTS of SEVERAL PAPER CHARACTERISTICS and APPLICATION METHODS on the SUBLIMATION RATE of CYCLODODECANE by Kelli A. Piot
    THE EFFECTS OF SEVERAL PAPER CHARACTERISTICS AND APPLICATION METHODS ON THE SUBLIMATION RATE OF CYCLODODECANE by Kelli A. Piotrowski A thesis submitted to the Department of Art In conformity with the requirements for the degree of Master of Art Conservation Queen’s University Kingston, Ontario, Canada (September, 2013) Copyright © Kelli Piotrowski, 2013 ABSTRACT Cyclododecane (CDD) is a waxy, solid cyclic hydrocarbon (C12H24) that sublimes at room temperature and possesses strong hydrophobicity. In paper conservation CDD is used principally as a temporary fixative of water-soluble media during aqueous treatments. Hydrophobicity, ease of reversibility, low toxicity, and absence of residues are reasons often cited for its use over alternative materials although the latter two claims continue to be debated in the literature. The sublimation rate has important implications for treatment planning as well as health and safety considerations given the dearth of reliable information on its toxicity and exposure limits. This study examined how the rate of sublimation is affected by fiber type, sizing, and surface finish as well as delivery in the molten phase and as a saturated solution in low boiling petroleum ether. The effect of warming the paper prior to application was also evaluated. Sublimation was monitored using gravimetric analysis after which samples were tested for residues with gas chromatography-flame ionization detection (GC-FID) to confirm complete sublimation. Water absorbency tests were conducted to determine whether this property is fully reestablished. Results suggested that the sublimation rate of CDD is affected minimally by all of the paper characteristics and application methods examined in this study. The main factors influencing the rate appear to be the thickness and mass of the CDD over a given surface area as well as temperature and ventilation.
    [Show full text]
  • (12) United States Patent (10) Patent No.: US 6,649,757 B2 Kuroda Et Al
    USOO6649757B2 (12) United States Patent (10) Patent No.: US 6,649,757 B2 Kuroda et al. (45) Date of Patent: Nov. 18, 2003 (54) PROCESS FOR PRODUCING FOREIGN PATENT DOCUMENTS LAUROLACTAM FROM CYCLODODECANONE CH 532 OS3 A 12/1972 EP O 487 090 A 5/1992 (75) Inventors: Nobuyuki Kuroda, Ube (JP); Joji EP O 785 188 A 7/1997 Kawai, Ube (JP); Hideo Shimomura, JP B43 12153 5/1968 Ube (JP) JP B48 10475 4/1973 (73) Assignee: Ube Industries, Ltd., Ube (JP) OTHER PUBLICATIONS * ) Notice: Subject to anyy disclaimer, the term of this patent is extended or adjusted under 35 Ritz, J. et al., “Caprolactam” Ullmann's Encyclopedia of U.S.C. 154(b) by 0 days. Industrial Chemistry. Cancer Chemotherapy to Ceramic Colorants, Weinheim, VCH Verlag, DE, vol. 15, 1986, pp. (21) Appl. No.: 10/345,548 31-50, XP002909167. (22) Filed: Jan. 16, 2003 (65) Prior Publication Data Primary Examiner Bruck Kifle US 2003/0139596 A1 Jul. 24, 2003 (74) Attorney, Agent, or Firm- Piper Rudnick LLP (30) Foreign Application Priority Data (57) ABSTRACT Jan. 16, 2002 (JP) ....................................... 2002-007549 Laurolactam having high quality is produced by reacting Feb. 28, 2002 (JP) ...... ... 2002-053903 cyclododecanone with a hydroxylamine Salt of a mineral Feb. 28, 2002 (JP) ...... ... 2002-053931 Mar. 29, 2002 (JP) ...... 2002-095O24 acid, and converting the resultant cyclododecanoneoxime to Jul. 18, 2002 (JP) r 2002-209935 laurolactam through the Beckmann rearrangement reaction, wherein a content of each of oxygen atom-containing C2 (51) Int. Cl. .............................................. C07D 225/02 organic compounds, for example, cyclododecenone or (52) U.S.
    [Show full text]
  • 162 Part 175—Indirect Food Addi
    § 174.6 21 CFR Ch. I (4–1–19 Edition) (c) The existence in this subchapter B Subpart B—Substances for Use Only as of a regulation prescribing safe condi- Components of Adhesives tions for the use of a substance as an Sec. article or component of articles that 175.105 Adhesives. contact food shall not be construed as 175.125 Pressure-sensitive adhesives. implying that such substance may be safely used as a direct additive in food. Subpart C—Substances for Use as (d) Substances that under conditions Components of Coatings of good manufacturing practice may be 175.210 Acrylate ester copolymer coating. safely used as components of articles 175.230 Hot-melt strippable food coatings. that contact food include the fol- 175.250 Paraffin (synthetic). lowing, subject to any prescribed limi- 175.260 Partial phosphoric acid esters of pol- yester resins. tations: 175.270 Poly(vinyl fluoride) resins. (1) Substances generally recognized 175.300 Resinous and polymeric coatings. as safe in or on food. 175.320 Resinous and polymeric coatings for (2) Substances generally recognized polyolefin films. as safe for their intended use in food 175.350 Vinyl acetate/crotonic acid copoly- mer. packaging. 175.360 Vinylidene chloride copolymer coat- (3) Substances used in accordance ings for nylon film. with a prior sanction or approval. 175.365 Vinylidene chloride copolymer coat- (4) Substances permitted for use by ings for polycarbonate film. 175.380 Xylene-formaldehyde resins con- regulations in this part and parts 175, densed with 4,4′-isopropylidenediphenol- 176, 177, 178 and § 179.45 of this chapter.
    [Show full text]
  • United States Patent Office Patented Feb
    3,792,045 United States Patent Office Patented Feb. 12, 1974 1. 2 fore the production of pure lactam, especially of unsubsti 3,792,045 tuted lactams having 6-12 carbon atoms in the ring, and PROCESS FOR THE PURIFICATION OF LACTAMS in particular caprolactam, from extract lactam or another Ruthild Henn, Domat-Ems, Grisons, and Dirk Deiters, raw lactam by combined treatment of distillation under Hans-Joachim Schultze, and Clau Berthers. 9hrs reduced pressure and crystalline extraction of the lactam Grisons,Forschting Switzerland, und Patentverwertung, assignors to Zurich, Invent Switzerland AG fur with an aliphatic or cycloaliphatic hydrocarbon having No Drawing. Filed Dec. 22, 1971, Ser. No. 211,102 5-10 carbon atoms, particularly with cyclohexane or pe troleum ether. It is of no significance whether the raw Claims priority, applicatiwitzerland, Jan. 6, 1971, lactam is first distilled and then extracted in the crystalline Int, C. C07d 41/06 O state, or vice versa. The purification effect is unexpectedly U.S. C. 260-239.3 A 14 Claims equally good and the selection of the sequence of opera tions need only be suited to technical requirements. The process may advantageously be carried out continuously. ABSTRACT OF THE DISCLOSURE This simple combination of two purification stages has A process characterized in that raw caprolactam is sub 15 the following advantages over existing purification proc jected, in either sequence, to a crystal extraction with an eSSeS aliphatic or cycloaliphatic hydrocarbon having 5-10 car It avoids complicated multi-stage distillation and recti bon atoms and to distillation under reduced pressure. fication plant, requires no additional physical purification treatment, e.g.
    [Show full text]
  • Staging Category Base Rate Article Description HTS Heading
    HTS Heading/Article Subheading description Base Rate Staging Category I. CHEMICAL ELEMENTS 2801 Fluorine, chlorine, bromine and iodine: 28011000 -Chlorine Free E 28012000 -Iodine Free E 280130 -Fluorine; bromine: 28013010 --Fluorine 3.7% A 28013020 --Bromine 5.5% A 28020000 Sulfur, sublimed or precipitated; colloidal sulfur Free E Carbon (carbon blacks and other forms of carbon not 28030000 elsewhere specified or included) Free E 2804 Hydrogen, rare gases and other nonmetals: 28041000 -Hydrogen 3.7% A -Rare gases: 28042100 --Argon 3.7% A 28042900 --Other 3.7% A 28043000 -Nitrogen 3.7% A 28044000 -Oxygen 3.7% A 28045000 -Boron; tellurium Free E -Silicon: --Containing by weight not less than 99.99 percent of 28046100 silicon Free E 280469 --Other: ---Containing by weight less than 99.99 percent but not 28046910 less than 99 percent of silicon 5.3% B 28046950 ---Other 5.5% B 28047000 -Phosphorus Free E 28048000 -Arsenic Free E 28049000 -Selenium Free E Alkali or alkaline-earth metals; rare-earth metals, scandium and yttrium, whether or not intermixed or 2805 interalloyed; mercury: -Alkali metals: 28051100 --Sodium 5.3% B 28051900 --Other 5.5% B -Alkaline-earth metals: 28052100 --Calcium 3% A 280522 --Strontium and barium: 28052210 ---Strontium 3.7% A 28052220 ---Barium Free E -Rare-earth metals, scandium and yttrium, whether or 28053000 not intermixed or interalloyed 5% A 28054000 -Mercury 1.7% A II. INORGANIC ACIDS AND INORGANIC OXYGEN COMPOUNDS OF NONMETALS Hydrogen chloride (Hydrochloric acid); chlorosulfuric 2806 acid: 28061000 -Hydrogen
    [Show full text]
  • United States Patent Oihce Patented June 22, 1971 1 2 of the Components of the Mixture in ?Nely Divided Form
    3,586,068 United States Patent Oihce Patented June 22, 1971 1 2 of the components of the mixture in ?nely divided form. 3,586,668 The mixture thus prepared may either be tabletted or PROCESS FOR THE PRODUCTION OF LACTAMS Otto Immel, Krefeld-Urdingen, and Hans - Helmut pelletised. Alternatively, it may even be made into a paste Schwarz and Hermann Schuell, Krefeld, Germany, as with water or an organic liquid, for example a polyhydric signors to Farbenfabriken Bayer Aktiengesellschaft, alcohol, and the resulting paste dried. It is also possible, Leverkusen, Germany for example, to stir carbon black into a solution of boric No Drawing. Filed Feb. 23, 1968, Ser. No. 707,423 acid and to dry the resulting mixture by conventional Claims priority, applicatisoln7ggrmany, Mar. 3, 1967, methods. This may be followed by calcination, optionally in vacuo, at a temperature of from 400 to 800° C. The Int. Cl. c0’7d 41/06 10 US. Cl. 260-2395 9 Claims ratio of boric acid to carbon may be from 1:2 to 9:1, although particularly good results are obtained by rear rangement of the oximes in the presence of a catalyst in ABSTRACT OF THE DISCLOSURE which the ratio of boric acid to carbon is from 5:4 to 8:2. With one part by weight of catalyst, it is possible to re The invention relates to a process for the production of arrange 6 to 12 parts by weight of oxime. Thereafter, it lactams by catalytic rearrangement of ketoximes in the is advisable to regenerate the catalyst by heating it at a gaseous phase, using as a catalyst system a mixture of temperature from 500 to 800° C.
    [Show full text]