2- Fluoro-1,3,5-trinitrobenzene

From 1, 1.4,10,10-tctrafluoro-9(10//)-anthrone (5 %) and l,4-difluoro-9,10-anthraquinonc arc obtained as byproducts, 2-Fluoro-1,3.5-trinitrobenzene (picryl fluoride. 4) has been synthesized from pyridinium picrate (3) by the use of diethylaminosulfur trifluoride (DAST), ... 

ESTERS N-Bromosuccinimide. 2-Fluoro-1,3,5-trinitrobenzene. Iron carbonyl. Ozone. Silver(I) trifluoroacetate. 2,4,6-Ttiphenylpyrylium tetrafluoroborate. 

Synthesis.—Af-Phenylamides can be prepared from carboxylic acids by first esteri-fying the acid with 2-fluoro-1,3,5-trinitrobenzene followed by displacement of the ester group with aniline.This mild method is successful for a good range of acids, giving consistently high yields of the amide. A direct, high-yield conversion of esters into AW-disubstituted amides is by reaction with dimethylaluminium amides, which similarly convert lactones into hydroxyamides. ... 

Picryl Fluoride. See Fluoro-2,4,6-Trinitrobenzene in Vol 6, F137-L. This compd has been evaluated at PicArsn as an expl. The parameters are presented in the following limited distribution Refs 1) H J. Jackson et al, A Comparative Evaluation of Selected Fluoroexplosives , PATR 3941 (1970) 2) L. Avrami et al, Effects of... 

The reaction of l-fluoro-2,4,6-trinitrobenzene and 2,4-dimethoxyaniline, in cyclohexane, shows a negative activation enthalpy274 (—SOkJmoU1), in agreement with a desolvative association mechanism in which the nucleophile competes with the solvent in associating with the substrate in an equilibrium preceding the substitution process. 

Taking into account, for instance, the slight differences in K observed for l-fluoro-2,4,6-trinitrobenzene and 1 -chloro-2,4,6-trinitrobenzene in Table 13, it is difficult to explain such a difference in K /K. Nevertheless, a H/D isotopic effect of 1.5 could be easily explained... 

Fluoro Derivatives of Symmetrical Trinitrobenzene , TechRept 2682, FREL, Picatinny Arsenal, Project TB3—0115B, Item D, Proj 5, A04-10-006, April I960... 

Summary DATBA is prepared from trifluorotrinitrobenzene in a three step process beginning with the preparation of 5-fluoro-l,3-diamino-2,4,6-trinitrobenzene (during this first step, the by-product TATB will be produced, which can be saved). After which, the 5-fluoro-l,3-diamino-2,4,6-trinitrobenzene is then converted into 5-Cyano-l,3-diamino-2,4,6-trinitrobenzene by the reaction with cynotrimethylsilane and nitromethane. The 5-Cyano-l,3-diamino-2,4,6-trinitrobenzene is then converted into 5-Carboxy-l,3-diamino-2,4,6-trinitrobenzene by the reaction with sulfuric acid. The reaction mixture is then treated with ice, and the desired product of 5-Carboxy-l,3-diamino-2,4,6-trinitrobenzene is filtered-off, washed with water, and then dried. Commercial Industrial note For related, or similar information, see Application No. 596,123, April 2, 1984, by The United States Navy, to Michael Chaykovsky, Columbia, MD, Horst G. Adolph, Silver Spring, MD. Part or parts of this laboratory process may be protected by international, and/or commercial/industrial processes. Before using this process to legally manufacture the mentioned explosive, with intent to sell, consult any protected commercial or industrial processes related to, similar to, or additional to, the process discussed in this procedure. This process may be used to legally prepare the mentioned explosive for laboratory, educational, or research purposes. 

Prepare a mixture by adding 10.44 grams of 5-fluoro-l,3-diamino-2,4,6-trinitrobenzene (prepared in step 1), and 9.92 grams cyanotrimethylsilane into 200 milliliters of nitromethane. Afterwards, reflux the mixture at 100 Celsius for two hours. After refluxing the mixture for 2 hours, remove the heat source, and allow the mixture to cool to room temperature. Then filter the reaction mixture to remove any insoluble impurities. After which, recrystallize the crude product from the nitromethane, and then vacuum dry or air-dry the product. Then recrystallize the dry product from 200 milliliters of acetonitrile. After recrystallization, vacuum dry or air-dry the product. The yield of 5-cyano-l,3-diamino-2,4,6-trinitrobenzene will be 8.8 grams as orange-brown crystals with a melting point of 212 Celsius (with decomposes). 

The example shown in Figure 5.11 is a fluorinated solid explosive called PF. PF is l-fluoro-2,4,6-trinitrobenzene (picryl fluoride). The elemental formula is... 

Although the compound possesses very good explosive properties an application could not be found for it owing to the difficulty of making it, A new laboratory method was given by Olah and tin 112] of nitrating m-dinitro-benzene to s> m-trinitrobenzene with nitronium tetraHuoroborate in fluoro-sulphuric acid solution. A short description of the method is given below. 

Nitronium tetraHuoroborate and m dinitrobenzene were added to fluoro-sulphuric acid and cooled in a dry ice/acetone bath. The temperature was gradually raised to ISO C. After three hours of heating the reaction mixture was poured on to crushed ice. The nitro product was extracted with dichloro-methane, washed with sodium hydrogen carbonate solution and dried over magnesium sulphate. The yield of sym-trinitrobenzene was 61.6% with 5% unreacted m-dinitrobenzene. 

Esterification. Acids can be esterified at 25° and in yields of 85-95% by Ircutmcnt with 2-fluoro-l, 3,5-trinitrobenzene (1 equivalent), DMAP (2 equivalents), mid an alcohol in acetonitrile lor 2 24 hours. The method is successful with... 

Thioesters.—Mixed anhydrides prepared from 2,4,6-trichlorobenzyl chloride and a carboxylic acid react with various thiols in the presence of 4-dimethyl-aminopyridine to give thioesters in 78—86% isolated yield.Somewhat less impressive yields were obtained in a few of the cases studied when l-fluoro-2,4,6-trinitrobenzene was used to couple the acid and the thiol.Treatment of 1-acylimidazoles with thiols in the presence of a catalytic amount of Mg(OEt)2 furnishes thioesters in good yields. Diphenyl-2-oxo-3-oxazolinylphosphonate brings about effective reaction between acids and thiols. Thiolacetates are efficiently prepared using the reaction of an alcohol with triphenylphosphine and di-isopropyl azodicarboxylate in the presence of thiolacetic acid/ A synthesis of some amino-acid derivatives containing the thioester functional group is achieved by the reaction of a vinyloxyborane with a Schiffs base (Scheme 56). ... 

Arylation with l-fluoro-2,4-dinitrobenzene (Sanger s reagent FDNB) and trinitrobenzene sulfonic acid was outlined in Section 1.2.4.2.2. FDNB also reacts with cysteine, histidine and tyrosine. 

Subsequent to the 1982 compilation of Lounila and Jokisaari [237], a large number of studies report chemical shift anisotropies for various nuclei in liquid crystalline solvents. Representative examples include ACTh in dichloromethylphosphine [243], methylisothiocyanide [244], and norborna-diene [141] A(Tc in chloro- and bromoform [245], bis(trimethylsilyl)diacetylene [246], and pyridine, pyrazine, pyridazine, and pyrimidine [247] ACTh and ACq in butyne [248], fluoro- [245,249], bromo- [245], and iodomethane [244, 245, 250], ethylene [251], methylisocyanide [252], dimethyl-mercury [253], benzene [250, 254, 255], 1,3,5-trichloro- [99, 256], 1,3,5-tribromo-[244], and 1,3,5-trinitrobenzene [244] Afluoro-methane [249] Aa in dimethylmercury [253] AcTsein carbon diselenide [258] AcTje in tellurophene [259] and AOxe [260]. 

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