Amination with ammonia

Naphthalenediol. 1,5-Dihydroxynaphthalene or Asurol is a colorless material which darkens on exposure to air. It is manufactured by the fusion of disodium 1,5-naphthalenedisulfonate with sodium hydroxide at ca 320°C in high yield. 1,5-Naphthalenediol is an important coupling component, giving ortho-a2o dyes which form complexes with chromium. The metallised dyes produce fast black shades on wool. 1,5-Naphthalenediol can be aminated with ammonia under pressure to 1,5-naphthalenediamine. 

Butanol and isobutyl alcohol are aminated with ammonia over alumina at 300—350°C to give the corresponding mono-, di-, and tributylainines. 

Amination with ammonia over zeolite catalysts at 350-400°C to give methylamine (and some dimethylamine) ""... 

Fischer polypeptide synthesis org chem A synthesis of peptides in which a-amino acids or those peptides with a free amino group react with acid halides of a-haloacids, followed by amination with ammonia. fish-ar pal-e pep,tTd. sin tha sas ) Fischer projection orgchem) A method for representing the spatial arrangement of groups around chiral carbon atoms the four bonds to the chiral carbon are represented by a cross, with the assumption that the horizontal bonds project toward the viewer and the vertical bonds away from the viewer fish-ar pra.jek-shon) Fischer s salt See cobalt potassium nitrite. fish-3rz solt)... 

Scheme 9.19 Asymmetric allylic amination with ammonia as nucleophile.

Although there have been few new developments in the period since 1993, halogenopyrazines 42 have been convenient precursors for a variety of pyrazine derivatives. For example, the halogenopyrazines 42 are cyanated by palladium-catalyzed cross-coupling with alkali cyanide or by treatment with copper cyanide in refluxing picoline, to yield cyanopyrazines 48. Alkoxypyrazines 49 are produced by treatment with alkoxide-alcohol, and aminopyrazines 50 are prepared by amination with ammonia or appropriate amines. The nucleophilic substitution of chloropyrazine with sodium alkoxide, phenoxide, alkyl- or arylthiolate is efficiently effected under focused microwave irradiation <2002T887>. 

Tanabe et al. (142, 143) find that silica-titania is highly acidic and has high catalytic activity for phenol amination with ammonia and for double-bond isomerization in butenes. Its acidity determined by n-butylamine titration varies with pretreating temperature and catalyst composition. The highest acidity per unit weight of catalyst was obtained when Ti02-Si02 (1 1 molar ratio) was heated at 500°C. 

Chlorosilane and chloromethylsilane both give the tris(silyl)amine with ammonia, while the disilazane is the only silicon-nitrogen product formed from chlorotrimethylsilane. Increasing the size of the silicon substituents impedes deamination, so both aminosilane and disilazane result and the amount of the latter increases on prolonged heating. 

LP mordenite doped with platinum is the catalyst used in the Shell Hysomer process for alkane hydroisomerization this can be linked to the Isosiv separation process whereby -/n-alkanes are separated on LTA zeolite. This link is the basis of the joint Shell/UOP Total Isomerization Process (TIP). Similar catalysts have been employed to hydrocrack (i.e. dewax) diesel fuels. There have also been reports of commercial use of mordenite to catalyze methanol amination with ammonia, to produce dimethylamine. 

The more reactive 2-chloro-3-fluoropyridine (89) is aminated readily by piperazine in boiling -butanol to give —60% of 90 (83JMC16%). The presence of a polar cyano group allows the 2-chloro-3-cyanopyridine (72) to be aminated already at I00°C by methylamine to 2-methylamino-3-cyanopyridine (91) in 63% yield (85SC10I3). An additional 6-chloro group, as in 92, leads, upon amination with ammonia to a mixture of the corresponding amino compounds 93 and 94. With the weakly basic aniline in the... 

Synthetic approaches that have been developed or extended in the review period and have the potential for general use include radical alkoxycarbonylation to give 4-alkoxycarbonylpyridazines (Section 6.01.5.6) preparation of 4(5)-aminopyridazines by direct amination with ammonia or amide ions followed by oxidation (Section 6.01.5.4.3) C—C bond formation by palladium catalyzed coupling reactions of pyridazine O-triflates (Section 6.01.7.12.2) and halopyridazines (Section... 

Leuckart-like reactions have been noted for the co-phosphinoylalkanals 304 and related compounds In these reactions, and also for those with analogous ketones the carbonyl reactant is subjected to reductive amination with ammonia (as ammonium acetate) or amines and NaBH3CN in MeOH at pH 7-7.5 the process is very sensitive to steric hindrance and probably proceeds via an enaminophonate intermediate. The sequence is illustrated (Scheme 38) by a direct synthesis of racemic phosphinothricin, but the involvement of the optically active 1,2-azaphospholidine 118 led to an optically active product ". ... 

The preparation of fluazinam is shown in Scheme 11.10. The key intermediate that is used to produce fluazifop-butyl, 2-chloro-5-trifluoromethylpyridine (4) (see Scheme 11.1), is used as a starting material for the synthesis of fluazinam as well. Further chlorination of pyridine 4 with chlorine gas in the presence of a catalyst such as acetic acid followed by amination with ammonia gives aminopyridine 34. The synthesis of fluazinam is completed by nucleophilic reaction of 34 with 2,4-dichloro-3,5 -dinitrobenzotrifluoride. 

Methanol can be esteriiied using a mixture of sulfuric and nitric acid, converted to methyl chloride with hydrogen chloride and to methyl amines with ammonia. Alkali metals are dissolved by methanol with alkali methylates fcam-ing if this reaction takes place in the presence of CO, methyl formiate occurs. One of the most important reaction occurring in the presence of carbonyl catalysts is CO being taken up by methanol producing acetic acid. 

Subsequently, direct amination with ammonia (NH3/MeOH) using BOP in the presence of DBU in DMF produced the target compounds for anticancer activity evaluation (13CC1275). 

The nitrogen of the basic amino acids lysine, histidine and arginine is not derived from wort amino acids but possibly from ammonium ions. In these cases intracellular oxoglutarate is aminated with ammonia to produce glutamate for biosynthesis. The imino acid proline is synthesized, without... 

This is particularly the case for the amine cations when we are comparing secondary and tertiary amines with ammonia or a primary amine. 

In 2008, the Beller group extended the method to the iV-alkylation of aryl amines with secondary amines and tertiary amines (Eq. 74) [215]. In the same year, they further applied the method to the A -alkylation of tert-alkylamines with aliphatic amines [216]. In 2011, the Beller group also reported the synthesis of primary amines by the reaction of secondary and tertiary amines with ammonia catalyzed by Shov catalyst (Eq. 75) [217]. 

Ye X, Plessow PN, Hofmann P (2014) Alcohol amination with ammonia catalyzed by an acridine-based ruthenium pincer complex a mechanistic study. J Am Chem Soc 136(16) 5923-5929... 

Formyl-pinane can be isolated from the aldehyde mixture as pure compound in moderate yield by distillation with a column of 20 trays [70a]. In turn, the aldehyde was converted into the primary amine by reductive amination with ammonia. The chiral amine has been utilized, for example, for the optical resolution of racemic pantolactone. Alternatively, aldol condensation of the formed aldehydes with ketones and subsequent hydrogenation give alcohols that might have a broad scope of potential applications in perfumes, soaps, and shampoos [73]. 

One can dso make use of the directing effect of the 3-bromine to chlorosulfonate directly in the 2 position (3-bromotiiiophene 35). Amination with ammonia give the free sulfonamide, while rm-butyl amine treatment gives a protected sulfonamide that can be used for the cross coupling reaction and nucleophilic displacements already described for the other isomers. The bromide 36 can also be used to direct transmetalation to the 3 position for the introduction of a variety of electrophiles. 

RCM of an iron complex containing an N heteroatom. The complex [CpFe(aniline) [PF6 ] 42 may be obtained by direct ligand exchange from aniline, but die yields is low (10%). An alternative method is die syndiesis from [CpFe(chlorobenzene) [PF6T by amination with ammonia in dichloromethane. 

High-level CCSD(T) calculations for the mechanism of double-hydrogen transfer (DHT) in the reduction of ketones to alcohols or of borate esters and imines to amines with ammonia borane suggest a concerted process which starts with the DHT forming alcohol and NH2BH2, followed by alcoholysis of NH2BH2 to form the first B-0 bond. 

ALTAM A process for making caprolactam from butadiene and carbon monoxide. Developed by DSM in the late 1990s and subsequently improved by Shell Chemicals, which contributed catalyst know-how. In the first two steps of the process, butadiene undergoes two hydroformylations with carbon monoxide, followed by reductive amination with ammonia and then cyclization to caprolactam. First commercialization was expected in Taiwan. A joint venture with Chiyoda Corporation, to further develop and commercialize the process, was announced in 2002. 

Ammonia and amines are photochemically reactive species acting as a base, a reductant, and a nucleophile. Therefore, the photochemical reactions may make direct amination with ammonia and amines possible to provide more convenient and powerful synthetic method among many synthetic methodologies. 

As can be seen from Table 2, when polymers are modified, the porous structure parameters do not substantially change. Only if aminated with ammonia, S value increases due, perhaps, to additional crosslinking of the skeleton. 

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