Acetic acid yield

In the case of 4-(chloromethyl)-2-phenylthiazole, chloration in acetic acid yields only theproductsubstitutedat the 5-position ofthethiazolering(247). 

Reaction of benzamhde (C6H5NHCC6H5) with chlorine in acetic acid yields a mixture of two monochloro denvatives formed by electrophilic aromatic substitution Suggest reasonable structures for these two isomers... 

The important chemical properties of acetyl chloride, CH COCl, were described ia the 1850s (10). Acetyl chloride was prepared by distilling a mixture of anhydrous sodium acetate [127-09-3J, C2H202Na, and phosphorous oxychloride [10025-87-3] POCl, and used it to interact with acetic acid yielding acetic anhydride. Acetyl chloride s violent reaction with water has been used to model Hquid-phase reactions. 

Nitroso compounds are formed selectively via the oxidation of a primary aromatic amine with Caro s acid [7722-86-3] (H2SO ) or Oxone (Du Pont trademark) monopersulfate compound (2KHSO KHSO K SO aniline black [13007-86-8] is obtained if the oxidation is carried out with salts of persulfiiric acid (31). Oxidation of aromatic amines to nitro compounds can be carried out with peroxytrifluoroacetic acid (32). Hydrogen peroxide with acetonitrile converts aniline in a methanol solution to azoxybenzene [495-48-7] (33), perborate in glacial acetic acid yields azobenzene [103-33-3] (34). 

Trityl Ethers. Treatment of sucrose with four molar equivalents of chlorotriphenylmethyl chloride (trityl chloride) in pyridine gives, after acetylation and chromatography, 6,1, 6 -tri-O-tritylsucrose [35674-14-7] and 6,6 -di-O-tritylsucrose [35674-15-8] in 50 and 30% yield, respectively (16). Conventional acetylation of 6,1, 6 -tri-O-tritylsucrose, followed by detritylation and concomitant C-4 to C-6 acetyl migration using aqueous acetic acid, yields a pentaacetate, which on chlorination using thionyl chloride in pyridine and deacetylation produces 4,l, 6 -trichloro-4,l, 6 -trideoxygalactosucrose [56038-13-2] (sucralose), alow calorie sweetener (17). 

When activating substituents are present in the benzenoid ring, substitution usually becomes more facile and occurs in accordance with predictions based on simple valence bond theory. When activating substituents are present in the heterocyclic ring the situation varies depending upon reaction conditions thus, nitration of 2(177)-quinoxalinone in acetic acid yields 7-nitro-2(177)-quinoxalinone (21) whereas nitration with mixed acid yields the 6-nitro derivative (22). The difference in products probably reflects a difference in the species being nitrated neutral 2(177)-quinoxalinone in acetic acid and the diprotonated species (23) in mixed acids. 

As might be expected from a consideration of electronic effects, an amino substituent activates pyrazines, quinoxalines and phenazines to electrophilic attack, usually at positions ortho and para to the amino group thus, bromination of 2-aminopyrazine with bromine in acetic acid yields 2-amino-3,5-dibromopyrazine (Scheme 29). 

Thermal conversion of diazirines to linear diazo compounds was postulated occasionally and proved by indirect methods. The existence of a diazo compound isomeric to diazirine (197) was proved spectroscopically on short thermolysis in DMSO (76JA6416). An intermediate diazoalkane was trapped by reaction with acetic acid, yielding the ester (198) (77JCS(P2)1214). 

Degree of substitution Acetyl content (%—COCH3) Acetic acid yield (%) Solubility Uses... 

This, on reduction with zinc dust and acetic acid, yielded the corresponding oxime, which was further reduced by sodium amalgam to -3 4 5-trimethoxyphenylethylamine, CgHjj(OMe)3. CH. CH. NHg, and this proved to be identical with mezcaline (I). Like the latter, it behaves on analysis as if it contained the grouping —NHMe but this had already been disproved by Heffter. Interest in the remarkable physiological properties attributed to mezcaline has led to many syntheses of this alkaloid and of its isomerides and analogues. ... 

Stryehnine-9-acetic acid yields a typical yellow benzylidene derivative, m.p. 285-8°, but dihydrostryehnine-9-aeetie acid forms a colourless compound, isolated as the perchlorate, C3(,H3(,04N2, H2O, HCIO4, m.p. 205-225° (dec.), which may be an isobenzylidene derivative, though it gives a transient blue colour with sulphuric acid and potassium diehromate. 

This on heating with nialonic and acetic acids yielded 4-carbethoxy-3 5-dimethoxyben zylidenemalonic acid,... 

The bromination of 5,8-dimethoxyquinoxaline in methanol gives a mixture of 6-bromo and 6,7-dibromo compounds/ Treatment of 2-methylquinoxaline with bromine in acetic acid yields a mixture of 27% of 2 bromomethyl- and 37% of 2-dibromomethyl-quinoxaline." Thus in the absence of powerfully activating groups, side-chain rather than nuclear substitution takes place. 

Costol is a diolefinic bicyclic sesquiterpene alcohol, which, on oxidation by chromio acid in acetic acid yields an aldehyde, CjgH jO, which jrields a semi-carbazone, melting at 217° to 218°. This aldehyde, which U triolefinic has the following characters —... 

The production of acetic acid from n-butene mixture is a vapor-phase catalytic process. The oxidation reaction occurs at approximately 270°C over a titanium vanadate catalyst. A 70% acetic acid yield has been reported. The major by-products are carbon oxides (25%) and maleic anhydride (3%) ... 

The reaction conditions are approximately 100-120°C and 15-25 atmospheres. The oxidation step is noncatalytic and occurs at approximately 200°C and 60 atmospheres. An acetic acid yield of 58% could he obtained. By-products are formic acid (6%), higher boiling compounds (3%), and carbon oxides (28%). Figure 9-1 shows the Bayer AG two-step process for producing acetic acid from n-butenes. ... 

Ketene further reacts with one mole acetic acid, yielding acetic anhydride ... 

Michler s base, N,N,N, N -tetramethyl-4,4 -diaminodiphenyl-methane) in 10 ml glacial acetic acid (yields a greenish solution) and make up to 100 ml with 80% 2-propanol. 

In contrast to the behavior of 3-hexyne in trifluoroacetic acid, addition of HCl in acetic acid yields essentially rra s-3-chloro-3-hexene (48%) and 3-hexanone (52%) as products, with less than 1% of the cis chloride (31,42,43). The 3-hexanone has been shown to arise from an intermediate vinyl acetate. The kinetics are complicated, but they seem to be of first order in substrate and second order in HCl. Added tetramethylammonium chloride increases the rate of product formation and changes the product composition to >95% trans-3-chloro-3-hexene and <5% 3-hexanone. A termolecular electrophilic addition via an intermediate such as 14 has been proposed (31,42) to account for these data. 

The five-coordinate iridium complexes may be protonated by glacial acetic acid, yielding [Ir(PPh3)2(CNR)3H] + the structure of this complex is determined by PMR measurements to be (XXIX). However, in the analogous HCl reaction [Ir(PPh3)2(CNR)2Cl2] is obtained. The reaction of [Ir(PPh3)2(CNR)3] with methanol also proved quite out of the ordinary. 

The cobaltous acetate reduction of tert-butyl hydroperoxide in acetic acid yields mainly ter/-butanol and oxygen the metal ion stays in the +2 oxidation state because of the reactivity of Co(III) towards hydroperoxides (p. 378) °. The rate law is... 

Elder leaves combined with alum or chrome as a mordant dyes fabric green. When the leaves are mixed with alum and salt, a lilac color emerges. Adding elder leaves to copper and acetic acid yields a... 

Treatment of atropine (26) with trichloroethyl chloroformate leads to the formation of a mixture of compounds 194 and 195, which when treated with zinc dust in acetic acid yields noratropine (21) (103) (Scheme 18). Similarly, the... 

Dihydropyrrole a-ketoester 423 when reacted with 2,2,2-trichloroethyl carbazate in refluxing xylene underwent smooth cycloaddition to afford cycloadduct 48 in 86% yield. Reaction of 423 with thiosemicarbazide in acetic acid yielded a product mixture to give the tetracycle 48. Its benzyloxycarbonyl group was cleaved by reaction with HBr to give crystalline 424 <2002JOG7880> (Scheme 94). 

Reaction of yohimbine (74) with cyanogen bromide in ethanol-chloroform afforded an isomeric mixture of (3/ )- and (3S)-ethoxy-3,4-secocyanamide derivative (562 and 563, respectively) (277, 278). It was found that the relative amounts of 562 and 563 depend on the molar ratio of ethanol to the substrate applied during the reaction. Stereospecific ring closures of 562 and 563 with hot acetic acid yielded yohimbine and pseudoyohimbine (88), respectively. 

Reaction of /cr/-butyl 1-hydrazinecarboxylates with triphosgene and ethyl 2-pyrrolidinecarboxylate, followed by removal of the BOC-protecting group with gaseous hydrogen chloride in anhydrous acetic acid, yielded hexahydro-pyrrolo[l,2-rf][l,2,4]triazin-l,4-dione 79 (Scheme 9) <2003SC1011>. 

As shown in Scheme 16, the A-oxidations of 112 can yield 4-oxides 113 and/or 5-oxides 114 can be formed. In some special cases (e.g., if R3 = Br), formation of exclusively 114 was experienced. The reverse transformation was also carried out reduction of the A-oxides (113, 114) by triethylphosphite or Zn/acetic acid yielded the deoxy compound 112. 

One of the issues of the industrial process design is related to the heat released by this reaction. A temperature rise will decrease the acetic acid yield, not only because the equilibrium constant becomes lower (the reaction is exothermic see section 2.9) but also because it will reduce the enzyme activity. It is therefore important to keep the reaction temperature within a certain range, for instance, by using a heat exchanger. However, to design this device we need to know the reaction enthalpy under the experimental conditions, and this quantity cannot be easily found in the chemical literature. 

---