The synthesis of PYX

[megalomania]

I have compiled this bit of information as the latest addition to my website. I have detailed the lab synthesis of the high explosive PYX from the available literature sources. I present here as a preview until I put the finishing touches and upload it to my site.

Mp 360 C
Den 1.77 g/mL
Vdet 7448 m/s
C17H7N11O16

2,6-Bis(picrylamino)-3,5-dinitropyridine, more frequently referred as PYX, is an insensitive high explosive with similar properties and usefulness as RDX or HMX. The explosive performance is less than that of RDX, but PYX finds uses in high temperature applications since it can withstand a considerable amount of heat. PYX is typically used for blasting in oil mining.

In a small beaker, prepare a solution of 100 mL of water and 10.9 g of 2,6-diaminopyridine. In a 1000-mL round-bottom Florence flask, prepare a solution of 400 g of isopropyl alcohol (100%) and 55 g of picryl chloride. Stir well to dissolve some of the chloride and then add 8.4 g of magnesium carbonate. Heat both the beaker and the flask to 28 C while stirring. Continue stirring until the picryl chloride completely dissolves in the alcohol and the diaminopyridine is mixed with the water. Configure the flask for reflux with addition and add the water-diaminopyridine mix to the flask of alcohol solution slowly over a 30 minute period while maintaining a gentle reflux. The addition will generate some CO2 waste, so control the addition accordingly to regulate the reaction. After the addition, continue refluxing for about 5 hours. At the end of the refluxing period, pour the hot solution over a filter to collect the crystals of the intermediate compound 2,6-bis(picrylamino)pyridine. Wash this compound several times with small portions of water. Yield is about 96%.

Add 825 parts by weight of 98% nitric acid to a 1000-mL round-bottom Florence flask. Slowly add 100 parts by weight of wet 2,6-bis(picrylamino)pyridine as prepared above to the flask at such a rate as to keep the acid between 0 C and 30 C. Having an ice water bath handy may help if the temperature rises too much. After the addition, set the flask up for reflux and heat the flask to the reflux temperature of the nitric acid (about 76 C) while stirring. Continue to reflux the flask for about 5 hours. Afterwards, discontinue cooling the reflux condenser and heat the flask (about 84 C) to distill off about 20% of the nitric acid. Allow the acid mix to cool to about 27 C and the solid product to settle. Decant off as much acid as possible and vacuum filter the remaining contents to collect the solid product. An acid resistant filter paper is advised, or the acid can be diluted with a large quantity of water before pouring on the filter paper. Wash the obtained product of PYX several times with water to remove all traces of acid. The wet product is placed in an oven and heated at 38 C until a constant weight is obtained. Yield is about 80 based on the mass of the intermediate.

Optionally, PYX of increased sensitivity can be prepared. As PYX is rather difficult to detonate reliably, it is sometimes advantageous to make it more sensitive. Into a small beaker add 1 part by weight (for example 50 g) of PYX prepared above to 5 parts by weight of DMSO (about 250 mL). Heat the beaker to 80-85 C while stirring until all of the PYX dissolves. Slowly pour the hot solution into another beaker containing 100 parts by weight (4 L) of acetone. It is important to add the solution to the acetone, not the acetone to the solution. Stir the mixture slightly to mix it. Quickly add 40 parts by weight (2 L) of cold water to the solution to precipitate the PYX. Collect the crystals by filtration and wash them with 20 parts (1 L) of acetone. Allow to dry at reduced pressure. This process alters the crystal structure of PYX to obtain a more sensitive form.

[IPN]

Sounds highly interesting!!

Is there a known synthesis for diaminopyridine?
Also where did this information come?

[megalomania]

I thought I wrote this a few days ago, but I guess I didn’t post it. Anyway, the sources I used for this synth were US patents 3,678061; 4,855,436; and 4,564,405. Also European patent 104,717. There are 2 recent Chinese journal articles detailing the synth of PYX, but being in Chinese I did not use them.

I looked up the synthesis of 2,6-diaminopyridine today. I didn’t really find anything that stands out in the recent literature, although there are a bunch. I found three references to older material that probably has the good stuff. The journals should arrive in a couple of weeks (if they are available), so I will post the details then. One is probably in French, the other in Russian, and the third should be in English as it’s from the Journal of Organic Chemistry.

Here are the recent references that are supposed to contain a synthesis of 2,6-diaminopyridine:


Bibliographic Information

Compound comprising supramolecular complexes of glutarimide-containing polymers with aminopyridines and their preparation. Loontjens, Jacobus Antonius; Clauswitz, Kai Uwe. (DSM N.V., Neth.). Eur. Pat. Appl. (2001), 11 pp. CODEN: EPXXDW EP 1136506 A1 20010926 Designated States R: AT, BE, CH, DE, DK, ES, FR, GB, GR, IT, LI, LU, NL, SE, MC, PT, IE, SI, LT, LV, FI, RO. Patent written in English. Application: EP 2000-201062 20000323. CAN 135:273657 AN 2001:709753 CAPLUS (Copyright 2003 ACS on SciFinder (R)

Patent Family Information

Patent No. Kind Date Application No. Date
EP 1136506 A1 20010926 EP 2000-201062 20000323
R: AT, BE, CH, DE, DK, ES, FR, GB, GR, IT, LI, LU, NL, SE, MC, PT, IE, SI, LT, LV, FI, RO
WO 2001070829 A2 20010927 WO 2001-NL224 20010319
WO 2001070829 A3 20020307
W: AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, BZ, CA, CH, CN, CO, CR, CU, CZ, DE, DK, DM, DZ, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW, AM, AZ, BY, KG, KZ, MD, RU, TJ, TM
RW: GH, GM, KE, LS, MW, MZ, SD, SL, SZ, TZ, UG, ZW, AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE, TR, BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG

Priority Application
EP 2000-201062 A 20000323


Abstract

The compd. comprises a supramol. complex of an aminopyridine (e.g., melamine) and glutarimide-contg. polymer with low acid level prepd. by cyclization of a copolymer of (meth)acrylate and (meth)acrylamide or a (meth)acrylamide homopolymer (e.g., methacrylamide-Bu methacrylate copolymer) in the presence of an acid (e.g., ZnCl2). The compd. having little bubble formation during processing is used in engineering plastics for high temp. applications.

Bibliographic Information

Analysis of aminopyridines and diaminopyridines by capillary electrophoresis. Sabbah, S.; Abu-Khurmah, M.; Oelschlager, H.; Scriba, G. K. E. School of Pharmacy, Department of Pharmaceutical Chemistry, University of Jena, Jena, Germany. Chromatographia (2001), 53(9/10), 559-562. CODEN: CHRGB7 ISSN: 0009-5893. Journal written in English. CAN 135:207714 AN 2001:506086 CAPLUS (Copyright 2003 ACS on SciFinder (R)

Abstract

A capillary electrophoresis method was developed for the sepn. of aminopyridines and diaminopyridines. The influence of the buffer pH and type of buffer was studied. Optimum sepn. conditions were 100 mM sodium acetate buffer, pH 5.15, and an applied voltage of 20 kV using a capillary of 50 cm effective length. In addn. to use of the migration times the compds. could be identified by their UV spectra when using a DAD detector. The assay was applied to the anal. of 3,4-diaminopyridine.

Bibliographic Information

Centipede polymers grafted with hydrogenated block copolymers and polyalkylenes and gels thereof. Wang, Xiaorong; Matsuse, Takahiro; Foltz, Victor J.; Mashita, Naruhiko; Hall, James E.; Toyosawa, Shinichi; Takeichi, Hideo. (Bridgestone Corporation, Japan). Eur. Pat. Appl. (1999), 16 pp. CODEN: EPXXDW EP 955329 A1 19991110 Designated States R: AT, BE, CH, DE, DK, ES, FR, GB, GR, IT, LI, LU, NL, SE, MC, PT, IE, SI, LT, LV, FI, RO. Patent written in English. Application: EP 99-107308 19990419. Priority: US 98-73617 19980506. CAN 131:337863 AN 1999:722767 CAPLUS (Copyright 2003 ACS on SciFinder (R)

Patent Family Information

Patent No. Kind Date Application No. Date
EP 955329 A1 19991110 EP 1999-107308 19990419
R: AT, BE, CH, DE, DK, ES, FR, GB, GR, IT, LI, LU, NL, SE, MC, PT, IE, SI, LT, LV, FI, RO
US 6054532 A 20000425 US 1998-73617 19980506
JP 11343320 A2 19991214 JP 1999-120365 19990427

Priority Application
US 1998-73617 19980506


Abstract

The present invention teaches a method for enabling the formation of a high damping, soft polymer gel. The method includes: reacting a alkenylbenzene-maleimide copolymer with a maleated polyalkylene and a maleated hydrogenated block copolymer and an alkyl diamine grafting agent under substantially dry conditions sufficient to form a hydrogenated block copolymer-polyalkylene grafted poly(alkenyl benzene-co-maleimide) polymer product, and dispersing this product with an extender oil sufficient to form the gel.

Bibliographic Information

Acid-catalyzed N-debenzylation of (benzylamino)pyridines. Kowalski, P.; Majka, Z.; Kowalska, T. Institute of Organic Chemistry and Technology, Cracow University of Technology, Krakow, Pol. Chemistry of Heterocyclic Compounds (New York)(Translation of Khimiya Geterotsiklicheskikh Soedinenii) (1998), 34(6), 740-741. CODEN: CHCCAL ISSN: 0009-3122. Journal written in English. CAN 130:209581 AN 1999:83141 CAPLUS (Copyright 2003 ACS on SciFinder (R)

Abstract

Several 2- and 4-(benzylamino)pyridines, 2,6-bis(benzylamino)pyridine, and 2-(benzylamino)quinoline underwent N-debenzylation in 95% H2SO4. Yields were 73-85%. The reaction failed with 3-(benzylamino)pyridine.

Bibliographic Information

Synthesis of phenazopyridine hydrochloride. Yin, Xiumei; Quan, Zheshan; Li, Yuanchun; Zhao, Liming; He, Wenfeng. College of Pharmacy, Yanbian University, Yanji, Peop. Rep. China. Yanbian Daxue Xuebao, Ziran Kexueban (1998), 24(3), 71-72. CODEN: YXZKE8 ISSN: 1004-4353. Journal written in Chinese. CAN 130:52306 AN 1998:734337 CAPLUS (Copyright 2003 ACS on SciFinder (R)

Abstract

Reaction of pyridine with NaNH2 in N,N-dimethylaniline gave 78.9% 2,6-diaminopyridine, coupling reaction of which with benzenediazonium chloride in aq. HCl gave 76% the title compd.

Bibliographic Information

Preparation of pyridine-2,6-diamines from 3-hydroxyglutaronitrile and amines. Reichwein, Adrianus Maria; Sikkema, Doetze Jakob. (Akzo Nobel N.V., Neth.; Reichwein, Adrianus, Maria; Sikkema, Doetze Jakob). PCT Int. Appl. (1996), 15 pp. CODEN: PIXXD2 WO 9636607 A1 19961121 Designated States W: CA, CN, JP, KR, MX, US. Designated States RW: AT, BE, CH, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE. Patent written in English. Application: WO 96-EP1730 19960424. Priority: NL 95-1000360 19950515. CAN 126:47117 AN 1997:26461 CAPLUS (Copyright 2003 ACS on SciFinder (R)

Patent Family Information

Patent No. Kind Date Application No. Date
WO 9636607 A1 19961121 WO 1996-EP1730 19960424
W: CA, CN, JP, KR, MX, US
RW: AT, BE, CH, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE
NL 1000360 C2 19961118 NL 1995-1000360 19950515
EP 825985 A1 19980304 EP 1996-914986 19960424
EP 825985 B1 19990526
R: AT, BE, CH, DE, DK, ES, FR, GB, GR, IT, LI, LU, NL, SE, MC, PT, IE, FI
JP 11505535 T2 19990521 JP 1996-534494 19960424
AT 180472 E 19990615 AT 1996-914986 19960424
ES 2132921 T3 19990816 ES 1996-914986 19960424
TW 385305 B 20000321 TW 1996-85105328 19960503
IN 180700 A 19980307 IN 1996-MA743 19960506
US 5939553 A 19990817 US 1997-952788 19971113

Priority Application
NL 1995-1000360 A 19950515
WO 1996-EP1730 W 19960424


Abstract

Pyridine-2,6-diamines having ³1 primary amino group were prepd. by reaction of 3-hydroxyglutaronitrile (I) with NH3 (donors), or primary or secondary amines. In the case of a primary or secondary amine, no hydrogen halide catalyst is used. Thus, I, NH3, and CuCl in MeOH were heated at 150° in an autoclave for 3 h to give >95% 2,6-diaminopyridine.

Bibliographic Information

Polymer scale preventive agent and its use. Shimizu, Toshihide; Watanabe, Mikio. (Shin-Etsu Chemical Co., Ltd., Japan). Eur. Pat. Appl. (1994), 25 pp. CODEN: EPXXDW EP 614915 A1 19940914 Designated States R: ES, FR, NL, PT. Patent written in English. Application: EP 94-103808 19940311. Priority: JP 93-77633 19930311; JP 93-77635 19930311; JP 93-77636 19930311; JP 93-136459 19930514; JP 93-136460 19930514; JP 93-181887 19930628. CAN 122:266334 AN 1995:538236 CAPLUS (Copyright 2003 ACS on SciFinder (R)

Patent Family Information

Patent No. Kind Date Application No. Date
EP 614915 A1 19940914 EP 1994-103808 19940311
EP 614915 B1 19980624
R: ES, FR, NL, PT
JP 07010904 A2 19950113 JP 1993-181887 19930628
JP 2727402 B2 19980311
JP 06316601 A2 19941115 JP 1993-347555 19931224
JP 3276498 B2 20020422
JP 06316603 A2 19941115 JP 1993-347557 19931224
JP 06316604 A2 19941115 JP 1993-347558 19931224
JP 07025913 A2 19950127 JP 1993-347560 19931224
JP 3251411 B2 20020128
JP 07025914 A2 19950127 JP 1993-347561 19931224
JP 3251412 B2 20020128
US 5420214 A 19950530 US 1994-208947 19940311

Priority Application
JP 1993-77633 A 19930311
JP 1993-77635 A 19930311
JP 1993-77636 A 19930311
JP 1993-136459 A 19930514
JP 1993-136460 A 19930514
JP 1993-181887 A 19930628


Abstract

A polymer scale preventive agent, for use in polymn. of a monomer having an ethylenically unsatd. double bond, comprises an alk. soln. contg. a condensation product of (A) a heterocyclic compd. having at least two amino groups and (B) a quinone. This agent is used by forming a coating on the inner wall, etc., of a polymn. vessel. A MeOH soln. of 40 g 2,6-diaminopyridine (I) and 60 g a-naphthoquinone was heated at 65° for 10 h to give a condensation product, which was combined 1:1:1 with gelatin and colloidal SiO2, and the combination was incorporated at 0.3 wt.% in 30% aq. MeOH and adjusted to pH 10.0 with NaOH to give a coating material. Manuf. of PVC in a vessel coated with this material gave polymer with 16 fish eyes per 100 cm2 in a plasticized extruded sheet and resulted in no scale on the portion of the polymn. vessel in contact with the liq. phase and 6 g/m2 scale at the gas-liq. interface, compared with 37 fish eyes, 22 g/m2, and 90 g/m2 when I was used in place of the condensate.

Bibliographic Information

Triplex formation by an oligodeoxyribonucleotide containing N4-(6-aminopyridinyl)-2'-deoxycytidine. Huang, Chin Yi; Miller, Paul S. Sch. Hyg. Public Health, Johns Hopkins Univ., Baltimore, MD, USA. Journal of the American Chemical Society (1993), 115(22), 10456-7. CODEN: JACSAT ISSN: 0002-7863. Journal written in English. CAN 119:271603 AN 1993:671603 CAPLUS (Copyright 2003 ACS on SciFinder (R)

Abstract

An oligodeoxyribonucleotide, d-C'TTC'TTTTTTTQTTTT, where C' is 5-methyl-2'-deoxycytidine and Q is N4-(6-aminopyridinyl)-2'-deoxycytidine forms stable triplexes with the duplex oligonucleotide d-GAAGAAAAAAXAAAA/d-TTTTYTTTTTTCTTC where X-Y are G-C, A-T, C-G or T-A as detd. by UV melting curves and CD spectroscopy. The third strand melting temp. of triplexes formed with A-G or C-G contg. duplexes are approx. 12-14° higher than those of the T-A or G-C contg. duplexes. Triplex formation in the former cases may involve Q-A-T and Q-C-G triads in which the imino tautomer of Q contacts both bases of the base pair and forms three hydrogen bonds with A-T or two hydrogen bonds with C-G. Proton NMR and UV spectra of Q suggests that this nucleoside can exist in the imino tautomeric form. The results suggest that Q and similar base analogs might be used to extend the types of duplex sequences recognized by third strand oligo-pyrimidines.

Bibliographic Information

Structural and thermal studies of the chloro complexes of cobalt, nickel and copper with 2,6-diaminopyridine and an assessment of their suitability as anti-static additives for polyethylene. Allan, J. R.; Gardner, A. R.; McCloy, B.; Smith, W. E. Dep. Appl. Chem. Phys. Stud., Napier Univ., Edinburgh, UK. Thermochimica Acta (1992), 208 125-31. CODEN: THACAS ISSN: 0040-6031. Journal written in English. CAN 118:72450 AN 1993:72450 CAPLUS (Copyright 2003 ACS on SciFinder (R)

Abstract

The prepn. and some properties of Co2LCl4 (L = 2,6-diaminopyridine), NiLCl2, and CuL2Cl2 are described. Spectral, magnetic and soly. studies indicate that the cobalt and Ni complexes have polymeric octahedral structures, whereas the Cu complex has a tetragonal structure. The thermal behavior of these complexes was studied by TG and DTA. The thermal decompn. studies show that the compds. decomp. with loss of org. ligand and halogen to give the metal oxide. The complexes were studied as possible antistatic additives, but are less effective than the com. compds. However, there is evidence that they may produce longer lasting antistatic properties.

Bibliographic Information

Process for the preparation of substituted maleimides. Adda, Michel; Eidelman, Chaim; Shorr, Leonard. (Bromine Compounds Ltd., Israel). Eur. Pat. Appl. (1992), 16 pp. CODEN: EPXXDW EP 499959 A1 19920826 Designated States R: BE, ES, FR, GB, NL. Patent written in English. Application: EP 92-102323 19920212. Priority: IL 91-97267 19910218. CAN 117:251235 AN 1992:651235 CAPLUS (Copyright 2003 ACS on SciFinder (R)

Patent Family Information

Patent No. Kind Date Application No. Date
EP 499959 A1 19920826 EP 1992-102323 19920212
R: BE, ES, FR, GB, NL
IL 97267 A1 19950124 IL 1991-97267 19910218
US 5306828 A 19940426 US 1992-835198 19920213
JP 05065269 A2 19930319 JP 1992-29244 19920217

Priority Application
IL 1991-97267 19910218


Abstract

A process for the prepn. of maleimides comprises the treatment of an amine with maleic anhydride to effect imidization of the resulting amic acid in a mixed polar/aprotic solvent in the presence of an acid catalyst; removal of a substantial portion of the apolar solvent results in the pptn. of the product. This pptn. process yields products of com. acceptable purity. Mixt. of aniline (149 g) in toluene (200 mL) was added to maleic anhydride (173 g) in DMF (43 mL) and toluene (2.5 L total). The mixt. was heated to 100° and 28 mL water and 2 L toluene were removed by distn.; thus N-phenylmaleimide was obtained in 60% yield and 99.7% pure.

Bibliographic Information

Oxidative hair composition containing diaminopyridine derivatives. Tamura, Tadashi; Kiyomine, Akira; Tanaka, Michio; Nishizawa, Yoshiinori; Tagami, Hidetoshi; Ogawa, Masahiko; Yoshihara, Toru; Muraoka, Tsutomua; Kawase, Jiro. (Kao Corp., Japan). Eur. Pat. Appl. (1991), 18 pp. CODEN: EPXXDW EP 441263 A1 19910814 Designated States R: AT, CH, DE, FR, GB, LI, NL. Patent written in English. Application: EP 91-101374 19910201. Priority: JP 90-28829 19900208; JP 90-412660 19901221; JP 90-412661 19901221. CAN 115:214517 AN 1991:614517 CAPLUS (Copyright 2003 ACS on SciFinder (R)

Patent Family Information

Patent No. Kind Date Application No. Date
EP 441263 A1 19910814 EP 91-101374 19910201
R: AT, CH, DE, FR, GB, LI, NL

Priority Application
JP 90-28829
JP 90-412660
JP 90-412661


Abstract

A hair dye compn. contains a developing substance and, as a coupling substance, a 3,5-diaminopyridine deriv. (I; R1 = alkoxy, [OCH2C(R2R3)]nR4; R2, R3 = H, hydroxyalkyl, R4 = OH, alkoxy, hydroxyalkyl, n = 1-4) or salts thereof. 3-(3,5-Diamino-2-pyridyloxy)-2-hydroxypropanol (II) (prepn. given) was reduced under H over 5% Pd/C and purified over silica gel before HCl gas was bubbled into the soln. to ppt. the II-dihydrochloride (III). 0.01 Mol of p-phenylenediamine and 0.01 mol of III were added to 100 g of a base contg. oleic acid 10, oleic acid diethanolamine 8, oleyl alc. 2, polyoxyethylene octyldodecyl ether 10, EtOH 15, propylene glycol 10, NH4Cl 3, 25% ammonia 7, and water 35%. The mixt. was adjusted to pH 9.5 to produce a dye compn.

Bibliographic Information

Nonlinear polyphosphazenes containing Schiff-base moieties and their manufacture and curing. Maruyama, Isao; Fujiwara, Hiroshi; Ito, Zenji; Shigematsu, Hitoshi. (Maruzen Petrochemical Co., Ltd., Japan). Jpn. Kokai Tokkyo Koho (1990), 36 pp. CODEN: JKXXAF JP 02024325 A2 19900126 Heisei. Patent written in Japanese. Application: JP 88-174410 19880713. CAN 113:60133 AN 1990:460133 CAPLUS (Copyright 2003 ACS on SciFinder (R)

Patent Family Information

Patent No. Kind Date Application No. Date
JP 02024325 A2 19900126 JP 1988-174410 19880713
US 4988791 A 19910129 US 1989-379930 19890711

Priority Application
JP 1988-174410 19880713


Abstract

The title polymers, exhibiting £20% wt. loss at 400°, having glass temp. ³120°, and giving cured products with good heat, water, and corrosion resistance (no data), are prepd. by the condensation of a primary di- or polyamine with cyclic phosphazenes [P(R2):N]n (n = 3, 4; R = OC6H4CHO, OPh, halogenated or alkylated PhO, N-arom. azomethynephenoxy, fluoroalkoxy; ³2 R = OC6H4CHO). A soln. of hexakis(4-formylphenoxy)cyclotriphosphazene in dioxane was mixed with p-phenylenediamine, cast on glass, dried, and heated 1 h at 225° to give a transparent flexible film having glass temp. 235°.

Bibliographic Information

Investigation of the process of polyimide formation from benzophenonetetracarboxylic diester complexes with various diamines. 3. Investigation of thermal imidization by a dielectric method. Borisova, T. I.; Nikonorova, N. A.; Artem'eva, N. N.; Smirnova, E. A.; Kukarkin, E. N.; Kudryavtsev, V. V.; Koton, M. M. Inst. Vysoko Mol. Soedin, Leningrad, USSR. Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya (1990), (3), 534-9. CODEN: IASKA6 ISSN: 0002-3353. Journal written in Russian. CAN 113:41370 AN 1990:441370 CAPLUS (Copyright 2003 ACS on SciFinder (R)

Abstract

Dielec. spectra for complexes of benzophenonetetracarboxylic acid di-Me ester (I) with diaminodiphenylmethane (II), hexamethylenediamine (III), and diaminopyridine (IV) exhibited loss peaks which were assocd. with thermal imidization based on H-bonded and/or ionic complexes. The I-II complex existed in both the H-bonded and ionic forms, whereas the I-III complex was only in the ionic form. A mechanism of polyimide formation from such I complexes is discussed. I-IV formed dimeric complexes with ionic and H bonds, with imidization occurring only through the H-bonded complex. The thermal imidization of I-III complex, in contrast to the other complexes, was completed at <220°.

Bibliographic Information

Binuclear palladium(II) and platinum(II) chelates with tetradentate Schiff bases derived from benzoylacetone and aromatic diamines. Singh, D. P.; Singh, Kiran, Mrs. Dep. Chem., Reg. Eng. Coll., Kurukshetra, India. Journal of the Institution of Chemists (India) (1988), 60(3), 76-8. CODEN: JOICA7 ISSN: 0020-3254. Journal written in English. CAN 109:243039 AN 1988:643039 CAPLUS (Copyright 2003 ACS on SciFinder (R)

Abstract

m-C6H4(NH2)2 or 2,6-diaminopyridine condensed with PhC(O)CH2C(O)Me to give tetradentate Schiff bases (H2L), which with PdCl2 or PtCl2 gave (ML)2 (M = Pd, Pt), which were characterized by IR and electronic spectra. These data and the diamagnetism of the complexes confirm square planar geometry. The phenylenediamine or diaminopyridine moieties are bridges in the dimeric structures. The ligands coordinate through the 4 azomethine N and enolic O atoms.

Bibliographic Information

Polyimide foam and polyimide laminate. Lee, Raymond; Ferro, Gregory A.; Okey, David W. (IMI-Tech Corp., USA). Eur. Pat. Appl. (1986), 30 pp. CODEN: EPXXDW EP 189983 A2 19860806 Designated States R: CH, DE, FR, GB, IT, LI, NL, SE. Patent written in English. Application: EP 86-300210 19860114. Priority: US 85-696007 19850129; US 85-754774 19850715. CAN 105:192500 AN 1986:592500 CAPLUS (Copyright 2003 ACS on SciFinder (R)

Patent Family Information

Patent No. Kind Date Application No. Date
EP 189983 A2 19860806 EP 1986-300210 19860114
EP 189983 A3 19880504
EP 189983 B1 19910403
R: CH, DE, FR, GB, IT, LI, NL, SE
US 4576862 A 19860318 US 1985-754774 19850715

Priority Application
US 1985-696007 19850129
US 1985-754774 19850715


Abstract

Polyimide foams are prepd. from prepolymers formed from an org. tetracarboxylic acid, anhydride, or ester deriv., an arom. diamine H2NZNH2 (Z = C5-12 arom. group), and an org. liq. diamine contg. ³50% conjugated dienes, and have a heat-formed vapor-impermeable skin on one surface. The laminate comprises a polyimide film adhered to the skin by a fire-resistant, heat-activated adhesive. The polyimide foams are useful in aircraft cabins, space vehicles, and land and sea transport equipment. Thus, 1 mol benzophenone tetracarboxylic acid dianhydride was refluxed with 240 mL MeOH and 24 mLH2O at 67-72° to form the Me ester which was refluxed with 0.654 g amine-terminated acrylonitrile-butadiene copolymer, 32.70 g 26 diaminopyridine, and 138.45 g p,p'-methylenedianiline. The mixt. was cooled to 60°, treated with a surfactant, dried, pulverized, sifted, foamed by exposure to microwave energy (1.4-100 kW) for 6-200 min., and cured at 232-300° for 30-200 min. A Kapton polyimide film (0.001-in thick) having on the 1 side a coating of a heat-activated adhesive and on the other Teflon FEP 54A fluorocarbon and a teflon-coated glass sheet, was laminated with a 1.25-in thick of the closed cell polyimide foam to form a flexible abrasion- and fire-resistant laminate having H2O wafer transmission rate 0.34 perm-in.

Bibliographic Information

Improved Chichibabin amination of pyridine derivatives. (Reilly Tar and Chemical Corp., USA). Jpn. Kokai Tokkyo Koho (1983), 18 pp. CODEN: JKXXAF JP 58208266 A2 19831203 Showa. Patent written in Japanese. Application: JP 83-62056 19830408. Priority: US 82-366598 19820408; US 83-478138 19830323. CAN 100:120901 AN 1984:120901 CAPLUS (Copyright 2003 ACS on SciFinder (R)

Patent Family Information

Patent No. Kind Date Application No. Date
JP 58208266 A2 19831203 JP 1983-62056 19830408
JP 04050304 B4 19920813
US 4386209 A 19830531 US 1982-366598 19820408

Priority Application
US 1982-366598 19820408
US 1983-478138 19830323


Abstract

Twenty-two pyridine derivs. were aminated by NaNH2 in aq. solvents in an improved Chichibabin reaction during which the pressure over the reaction mixt. was >50 psi and the partial pressure of the added NH3 was >5 psi. Thus, NH3(l) was added to 29.9 g Na over Fe(NO3)3×6H2O to give 1.3 mol NaNH2, NH3(l) evapd., xylene contg. oleic acid added, followed by 1.0 mol 3-picoline, NH3 (g) introduced at 30 psig and N at 60 psig, and the mixt. heated at 145-152° to give 72.4 g aminomethylpyridine isomers I and II (3.92:1).



Bibliographic Information

Chichibabin reaction. McGill, Charles K.; Sutor, James J. (Reilly Tar and Chemical Corp., USA). U.S. (1983), 10 pp. CODEN: USXXAM US 4386209 A 19830531 Patent written in English. Application: US 82-366598 19820408. CAN 100:6343 AN 1984:6343 CAPLUS (Copyright 2003 ACS on SciFinder (R)

Patent Family Information

Patent No. Kind Date Application No. Date
US 4386209 A 19830531 US 1982-366598 19820408
EP 98684 A2 19840118 EP 1983-301960 19830407
EP 98684 A3 19841017
EP 98684 B1 19910116
R: BE, CH, DE, FR, GB, IT, LI, NL
CA 1255675 A1 19890613 CA 1983-425407 19830407
JP 58208266 A2 19831203 JP 1983-62056 19830408
JP 04050304 B4 19920813
US 5003069 A 19910326 US 1989-386025 19890726

Priority Application
US 1982-366598 19820408
US 1983-478138 19830323
US 1985-727593 19850426
US 1986-942034 19861215
US 1988-168638 19880304


Abstract

Chichibabin amination of pyridines with NaNH2 was carried out at a pressure of ³50 psi in the gas phase in the presence of sufficient NH3 to give a NH3 partial pressure of ³5 psi in the gas phase. Aminopyridines could be added as catalysts. Thus 1 mol 3-picoline was treated with NaNH2 in the presence of 0.1 mL oleic acid and 0.05 mol of a 2.9:1 mixt. of 2-amino-5-methylpyridine with 2-amino-3-methylpyridine, pressurized to 30 psig with NH3 and to 220 psig with N. The product was 84.7 g of a 3.69:1 mixt. of 2-amino-5-methylpyridine with 2-amino-3-methylpyridine.

Bibliographic Information

Low-temperature elastomeric polyamides containing perfluorinated polyether building blocks. Caporiccio, Gerardo; Strepparola, Ezio; Bargigia, Gianangelo; Novaira, Giuseppe; Peveri, Glauco. Montefluos Cent. Ric. Sviluppo, Milan, Italy. Makromolekulare Chemie (1983), 184(5), 935-47. CODEN: MACEAK ISSN: 0025-116X. Journal written in English. CAN 99:23778 AN 1983:423778 CAPLUS (Copyright 2003 ACS on SciFinder (R)

Abstract

Reductive cleavage of derivs. from tetrafluoroethylene photooxidn. resulted in perfluorinated polyethers with a,w-carboxylic ester groups [RO2CCF2O(CF2O)m(C2F4O)nCF2CO2R (R = alkyl, aryl)]. Their condensation with suitable aliph. and arom. diamines gave a new class of elastomers, crosslinkable by org. peroxides. A good balance of low temp. elasticity, resistance to solvents, and thermal stability was particularly found for arom. polyamides.

Bibliographic Information

Platinum(II) complexes containing amine ligands. Haghighi, S.; McAuliffe, C. A.; Hill, W. E.; Kohl, H. H.; Friedman, M. E. Inst. Sci. Technol., Univ. Manchester, Manchester, UK. Inorganica Chimica Acta (1980), 43(1), 113-19. CODEN: ICHAA3 ISSN: 0020-1693. Journal written in English. CAN 94:40633 AN 1981:40633 CAPLUS (Copyright 2003 ACS on SciFinder (R)

Abstract

PtQ2X2.nH2O (Q = 2-aminopyridine; X = Cl or I; and n = 1 or 2) in which Q is coordinated through the heterocyclic N atom were prepd. Pt3L2X6.6H2O (L = 3,4-diaminopyridine, X = Cl, I), Pt2L'3Cl3OH (L' = 2,3-diaminopyridine), Pt3L''4I5OH (L'' = L or 2,6-diaminopyridine (L''')), and [PtL'''3Cl4].4H2O which contain both ring N and NH2 groups coordinated to the metal were prepd. PtZX2 (Z = o- and p-phenylenediamine; X = Cl, I) were prepd. in which the amine groups are coordinated.

Bibliographic Information

Rearrangements of N-mono- and N,N'-disubstituted 2,6-diaminopyridines in the presence of aluminum chloride. Czuba, Wladyslaw; Kowalski, Piotr. Inst. Org. Chem. Technol., Polytech. Univ., Krakow, Pol. Polish Journal of Chemistry (1979), 53(2), 507-11. CODEN: PJCHDQ ISSN: 0137-5083. Journal written in English. CAN 91:56787 AN 1979:456787 CAPLUS (Copyright 2003 ACS on SciFinder (R)

Abstract

Thermal rearrangement of piperidinediamine I (R = 2-pyridylmethyl) in the presence of AlCl3 gave II in addn. to the mono- and didealkylated derivs. of I. I (R = 6-methyl-2-pyridylmethyl) underwent only dealkylation and no rearrangement. Similar reaction of I (R = CH2Ph) gave III (R = CH2Ph) and 2,6-pyridinediamine (IV), whereas I (R = CH2C6H4OMe-4) gave the corresponding II, III and IV. V (R = CH2Ph) similarly gave III (R = CH2Ph) and IV, whereas V (R = 2-pyridylmethyl) did not react.



Bibliographic Information

Hofmann-Martius reaction in pyridine series. Czuba, Wladyslaw; Kowalski, Piotr. Inst. Org. Chem. Technol., Polytech. Univ. Krakow, Krakow, Pol. Polish Journal of Chemistry (1978), 52(7-8), 1403-9. CODEN: PJCHDQ ISSN: 0137-5083. Journal written in English. CAN 90:22766 AN 1979:22766 CAPLUS (Copyright 2003 ACS on SciFinder (R)

Abstract

Heating pyridineamines I (R = 2-pyridylmethyl, 6-methyl-2-pyridylmethyl, 4-MeOC6H4CH2, benzyl) at 220-30° gave some of II, III, IV and 2,6-diaminopyridine (V). E.g., I (R = benzyl) gave 41.5% II, 20.1% III and 2.3% V. The reactivity of I decreased in the stated order of R.



Bibliographic Information

Aminopyridines. Enomoto, Saburo. (Sumitomo Chemical Co., Ltd., Japan; Koei Chemical Co., Ltd.). Jpn. Kokai Tokkyo Koho (1978), 2 pp. CODEN: JKXXAF JP 53053662 19780516 Showa. Patent written in Japanese. Application: JP 76-128511 19761025. CAN 89:197341 AN 1978:597341 CAPLUS (Copyright 2003 ACS on SciFinder (R)

Patent Family Information

Patent No. Kind Date Application No. Date
JP 53053662 A2 19780516 JP 1976-128511 19761025
JP 59053910 B4 19841227

Priority Application
JP 1976-128511 19761025


Abstract

Aminopyridines were prepd. by treating chloropyridines which contain at least one Cl in the 2- or 6-position of the pyridine nucleus, with NH3 in the presence of metallic Cu or Al. Thus, a mixt. of 2-chloropyridine 100, Cu powder 15, and 28% aq. NH3 250 g was autoclaved at 200° for 2.5 h, and the aq. layer extd. with benzene to give 87.7% 2-aminopyridine.

Bibliographic Information

2-Substituted adenosine-5'-carboxylates in the treatment of anginal pain. Prasad, Raj N.; Stein, Herman Hal; Tietje, Karin R. (Abbott Laboratories, USA). U.S. (1976), 5 pp. Division of U.S. 3,903,073. CODEN: USXXAM US 3992531 19761116 Patent written in English. Application: US 74-505703 19740913. CAN 86:106989 AN 1977:106989 CAPLUS (Copyright 2003 ACS on SciFinder (R)

Patent Family Information

Patent No. Kind Date Application No. Date
US 3992531 A 19761116 US 1974-505703 19740913
US 3903073 A 19750902 US 1973-428516 19731226
AU 7475800 A1 19760527 AU 1974-75800 19741127
CA 1028695 A1 19780328 CA 1974-215600 19741210
NL 7416203 A 19750630 NL 1974-16203 19741212
SE 7416191 A 19750627 SE 1974-16191 19741220
SE 413895 C 19801016
JP 50096595 A2 19750731 JP 1974-145848 19741220
DK 7406796 A 19750908 DK 1974-6796 19741223
GB 1472910 A 19770511 GB 1974-55637 19741223
FR 2271837 A1 19751219 FR 1974-42896 19741226

Priority Application
US 1973-428516 19731226


Abstract

The title compds. [I (R = NH2, NHAc, OH; R1 = H, Et; R2R3 = H2 Me2C)], useful in treating cardiovascular disorders and as anti-anginal agents (no data), were prepd. The reaction of 2,6-diaminopurine with Ac2O and HgCl2 and subsequent reaction with triacetyl-D-ribofuranosyl chloride gave adenosine pentaacetate (II). Treatment of II with MeOH-NH3 (g) followed by reaction with Me2CO and oxidn. with KMnO4 gave I (R = NHAc; R1 = H; R2R3 = Me2C) (III). Cleavage of the Me2C moiety of III followed by reaction with SOCl2 in EtOH gave I (R = NH2, R1 = Et, R2 = R3 = H) (IV), which, when reacted with NaNO2 in HOAc-H2O, gave IV (R = OH).



Bibliographic Information

Chichibabin reaction in aminopyridines, azaindoles, and azaindolines. Pozharskii, A. F.; Kuz'menko, V. V.; Azimov, V. A.; Yakhontov, L. N. Rostov. Gos. Univ., Rostov-on-Don, USSR. Khimiya Geterotsiklicheskikh Soedinenii (1973), (9), 1232-9. CODEN: KGSSAQ ISSN: 0132-6244. Journal written in Russian. CAN 80:3412 AN 1974:3412 CAPLUS (Copyright 2003 ACS on SciFinder (R)

Abstract

Amination of 4-(dimethylamino)pyridine with NaNH2 in cymene at 160-5° gave 30% 2-amino-4-(dimethylamino)-pyridine. Analogously, 3-(dimethylamino)pyridine gave 62% 2-amino-3-(dimethylamino)pyridine, but 2-(dimethylamino)pyridine gave only 50% 2,6-diaminopyridine. Heating the 5-azaindole I 2 hr with NaNH2 in cymene yielded 51% the pyridine II. Analogously attempted aminations of the azaindole III and azaindolines IV (R = Ph, H) yielded only starting material.

Bibliographic Information

Acylated nitrogen-containing dispersant polymers. (Lubrizol Corp.). Fr. (1966), 12 pp. CODEN: FRXXAK FR 1457520 19661104 Patent written in French. Application: FR 19650831. CAN 67:4685 AN 1967:404685 CAPLUS (Copyright 2003 ACS on SciFinder (R)

Patent Family Information

Patent No. Kind Date Application No. Date
FR 1457520 19661104 FR 19650831
CA 964637 CA



Abstract

A copolymer of a succinic, succinimidoyl, or succininoyloxy compd. with an aliphatic C³50 hydrocarbon or essentially hydrocarbon substituent and a N compd. in which the N is directly attached to a succinic radical which may have as a substituent a hydrocarbon group, an amino group with ³3 C atoms between successive N atoms and ³11 successive aliphatic C atoms in the group, a hydroxyalkylamino, hydroxyhydrocarbon, alkoxyhydrocarbon, amino, carbamoyl, guanyl, or acylimidoyl group is an effective dispersant, esp. when a dialkyldithiophosphate of a Group II metal, esp. Zn or Ba, is also present. Thus, polyisobutylene of mol. wt. 5000 was chlorinated to 10% by wt. Cl content, and mixed with succinic anhydride to produce a reaction product with an acid no. of 24. An equiv. mixt. of this product and tetratrimethylenepentamine was heated to 70-145° for 45 min. and then blown with N for 4 hrs. at 160-80° to remove all H2O, after which the product was collected. The prepn. of other copolymers of the invention by similar means is described. The prepn. of Zn and Ba alkyl, aryl, and alkylaryl thiophosphates by conventional means is also described. A lubricating oil contg. 2% by wt. of I and 0.01% of P as Zn dioctyldithiophosphate is described, with similar formulations contg. Ba and (or) Ca sulfonates and (or) phenates, with no performance data.

[IPN]

Thanks for the info, that’s really helpful!
But as I don't have time to make diaminopyridine I ordered 100g of it :p
The next step is to chlorinate benzene to trichlorobenzene and then nitrate that :rolleyes:
Lot of work but that PYX sounds too interesting to just pass by!

Does anyone have any tips for the chlorination of benzene to trichlorobenzene?

[IPN]

Ok, just received 100g of 2,6-diaminopyridine. It looks like pieces of gravel :p
And I guess that making trichlorobenzene from benzene won't be so easy.. So I'm getting that too from 'elsewhere'

Then SWIM has to nitrate the TCB to picryl chloride and THEN it's time to make the PYX :D

[vulture]

Making TCB from benzene is a pain in the ass, as any added chlorine atom will severely decrease the addition speed of another chlorine atom.

I'm not sure, but IIRC the same thing goes for NO2 decreasing Cl addition and vice versa.

[cutefix]

I think that is one reason that TATB synthesis from symmetrical trichlorobenzene was gradually abandoned and replaced with the alternative: Aside from the fact that the by product ammonium chloride is difficult to remove completely from the fine TATB crystals

As this raw material TCB is difficult (and expensive)to synthesize and there is not much use for it anyway
Currently the manufacture of TATB is being improved
It ranges from the
Vicarious neucleuphilic substitution
http://www-cms.llnl.gov/s-t/vns_tatb.html
to the use of these method recently using phloroglucinol as the raw material
http://www.dtic.mil/ndia/2003insensitive/sanderson.pdf

[Hystrix]

About symm-TCB. It can be prepared from aniline and not from benzene (cause chlorine activates ortho- and para- positions). The first stage is chlorination of aniline which gives 2,4,6-trichloroaniline (TCA). The second stage is diazotization of TCA with NaNO2/H2SO4 in anhydrous ethanol (where EtOH is not only solvent but also it gives hydrogen for substituting diazo group).

By the way, I have a doubt that TATB will be useless in amounts which can be prepared at home. It is too insensitive, how heavy booster will it require? And what minimum charge of TATB can be detonated?

[IPN]

Luckily I didn’t place an order for the TCB as picryl chloride is made from chlorobenzene. :o

Title: Picryl Chloride
CAS Registry number: [88-88-0]
CAS name(s): 2-Chloro-1,3,5-trinitrobenzene
Molecular formula: C6H2ClN3O6
Molecular weight: 247.55
Percent Composition: C 29.11%, H 0.81%, Cl 14.32%, N 16.97%, O 38.78%.
Properties: Almost white needles. Insol in water; freely sol in benzene, hot chloroform, boiling alcohol, slightly in ether or petr ether.
Density: d 1.797
Melting Point: 83degrees

That info is from the merck index.

[KABOOOM [pyrojustforfun]]

if you can order such chemicals so easy you probably can order phosphorous oxychloride as well. I think picric acid can be made into CTNB by action of POCl3 on it.