Antoncho (Official Hive Translator)
09-22-01 20:43
No 216197
      A completely OTC ;) acetic anhydride synthesis  Bookmark   

These syntheses were brought to us by most outstanding Garin (of http://www.voy.com/12987/, who dug up somewhere a really good farmaceutical syntheses book published in 1915, scanned it and uploaded it at http://chembook.narod.ru in DejaVu format (BTW - really superior to PDF's, as far as the size goes).
Their main advantage is that these synths eliminate need for Br2, which is an expensive and truly vile substance. Instead  Na acetate and sulfur/chlorine or sulfur monochloride are used, both of which can bee easily made from OTC chemicals - S2Cl2 synthesis is described elsewhere on the Hive by Catastrophe.
Antoncho will see what other useful synths he can find in that book and will post them here soon.



Mix quickly and thoroughly 205-215 g of pulverized fine NaOAc and 10g dry sulfur powder, the mixtr is quickly transferred to a wide-mouth 1 liter RBF and wetted w/25 ml acetic anhydride
(a number of substitutes for it is possible - S2Cl2 is surely the 1st coming to mind). Into the flask through the rubber cork extend 1) a wide tube for chlorine in-flow 2) a hand stirrer, which is hermetized w/an aid of a piece of rubber tubing greased w/vaseline and 3) an out-leading tube for xcess Cl2 release. The flask is immersed in an ice-bath. Chlorine is initially passed in very carefully, w/often stirring or shaking, over the passage of time the rxn gets hotter and more and more liquid, so the stirrer may bee after some time rotated w/a motor. Chlorine stream should bee regulated so that almost all of it is absorbed. When the rxn mixtr stops heating and Cl2 is no longer taken up, the rxn contents are distilled in vacuo at oil bath temp ~150-180 C (???), then redistilled at ordinary pressure, collecting the fraction boiling between 132 and 142 C.
Yield ~90%



And another one:




2CH3COONa + S2Cl2 ---> (CH3COO)2S2 + 2 NaCl (at cold)
2 (CH3COO)2S2 ---> 2(CH3CO)2O +3S + SO2

Prepare 100g freshly fused NaOAc and 65g S2Cl2. A small quantity of NaOAc is placed in a thin-walled glass cooled in an ice bath. To this is added some sulfur chloride, the mixtr is vigorously stirred w/a wooden spatula, not allowing the temp to rise. Then some NaOAc is added again, and the process is repeated several times until all is mixed in. The semi-liquid mass is transferred into a 1 liter RBF. The previous operation is repeated 4 times, so that 400g NaOAc and 260 g S2Cl2 total are taken into work. The RBF is then equipped w/a reflux condenser and gently heated on a water bath to ~80-85 C. As soon as the rxn starts, the heating is removed, and in case the rxn gets too vigorous it's cooled w/cold water. After 20-30 min SO2 evolution ceases and the mxtr is heated for 10 more min's on a boiling water bath.
The rxn product is then distilled off under vacuum, then fractionally re-distilled at ordinary pressure, collecting the fraction boiling between 132-142 C.
For further purification it's ditilled with 2-3% KMnO4 or K2Cr2O7 for breakage of sulfurous contaminants (test for their presence: 1 ml of the distillate upon neutralization w/pure NH3 mustn't give a dark precipitate on treatment w/Pb(AcO)2)
The yield is ~90% based on S2Cl2


Antoncho
 
 
 
 
    lunatic_asylum
(Newbee)
09-22-01 22:56
No 216217
      Re: A completely OTC ;) acetic anhydride synthesis  Bookmark   

I have heard that phosphorus pentoxyde is sometimes used in making anhydrides.
What about mixing GAA and enough phosphorus pentoxyde, reflux and distil of the acetic anhydride?
 
 
 
 
    foxy2
(Distinctive Doe)
10-29-01 20:37
No 229993
      Acetyl Chloride/Acid chloride production!  Bookmark   

Antoncho
This post is sweet, it opens lots of doors. Along with this info.
Post 208025 (Antoncho: "Preparation of S2Cl2", Novel Discourse)  Courtesy of Antoncho smile
All summarized here, thanks to Rhodium laugh
../rhodium/chemistry /anhydrides.html

I had this idea a while ago, guess my instincts are correct.
Post 208435 (foxy2: "Re: Vilsmeier mechanism: the alternatives to POCl3", Chemistry Discourse)
Wonder if it works with oxylic acid?? Hmmm

Well here it is.

Organocarbonyl chlorides from sulfur monochloride.     Takada, Yoshiyuki; Matsuda, Toshio; Inoue, Goro. 
(Asahi Chemical Industry Co., Ltd.).   Japan.  (1968),
JP  43012123  19680522   
Patent  written in Japanese.  

Abstract
Some carboxylic acid chlorides are prepd. from the corresponding acids and S2Cl2 (I) under catalytic action of Fe(AcO)3 (II), Fe2(C2O4)3 (III), Fe(NO3)3 (IV), or ferric benzoate (V) in 1/100 to 5/100 mole range.  Thus, 16.6 g. terephthalic acid, 135 g. I, and 0.19 g. II are stirred and refluxed 5 hrs. at 125-30 to give 19.8 g. terephthaloyl chloride, b13 140-2.  Similarly are prepd. isophthaloyl, benzoyl, acetyl, and caproyl chlorides by use of II, III, IV, or V catalysts.


Here are more details

Synthesis of acid chlorides by the reaction of carboxylic acids with sulfur monochloride.  III.    
Matsuda, Toshio; Yokota, Kazuaki; Takata, Yoshiyuki.    Fac. Eng.,  Hokkaido Univ.,  Sapporo,  Japan.  
Hokkaido Daigaku Kogakubu Kenkyu Hokoku  (1978),  87  151-4.   Journal  written in Japanese.

Abstract
Recycling S, produced in the reaction of carboxylic acids with sulfur monochloride in the presence of iron salt catalyst, was attempted by the introduction of Cl2 into the reaction mixt.  Acid chlorides, such as benzoyl, p-nitrobenzoyl, terephthaloyl, isophthaloyl, acetyl, propionyl, butyryl, and adipoyl chlorides, were obtained with no contamination by S in the 70-96% yields.


Synthesis of acid chlorides by the reaction of carboxylic acids with sulfur monochloride.  IV.  Direct synthesis of acid chlorides from carboxylic acids, chlorine and sulfur.
Matsuda, Toshio; Yokota, Kazuaki; Takata, Yoshiyuki.    Fac. Eng.,  Hokkaido Univ.,  Sapporo,  Japan.   
Hokkaido Daigaku Kogakubu Kenkyu Hokoku  (1979),   (95),  87-90. 
CODEN: HDKKAA  Journal  written in Japanese.   

Abstract
Acid chlorides were prepd. by reaction of 2 mol carboxylic acids with 1 mol S and 2 mol Cl over Fe(OAc)3 catalysts.  By this method, benzoic, p-nitrobenzoic, iso- and terephthalic, acetic, propionic and n-butyric acid chlorides were obtained in high yields. 

Synthesis of acid chlorides by reaction of carboxylic acids with sulfur chloride.  I.  Reaction of carboxylic acids with sulfur monocloride using iodine as catalyst.    
Takata, Yoshiyuki; Matsuda, Toshio; Okasaka, Hotuma.    Hokkaido Univ.,  Sapporo,  Japan.    Kogyo Kagaku Zasshi  (1969),  72(11),  2502-3.  CODEN: KGKZA7  Journal  written in Japanese.   

Abstract
A mixt. of 0.1 mole BzOH, 0.3 millimole iodine, and 0.2 mole S2Cl2 was refluxed 5 hr at 150 to give 93% BzCl.  Similarly prepd. were RC6H4COCl (R and % yield given):  o-Me, 65; m-Me, 83; p-Me, 87; o-NO2, - (decompd. on distn.); m-NO2, 88; p-NO2, 65; o-Cl, 82; m-Cl, 20; p-Cl, 90.  Aromatic dicarboxylic acids and fatty acids gave no acid chlorides.


II.  Synthesis of acid chlorides by the reaction of carboxylic acids with sulfur monochloride in the presence of an iron-salt catalyst.
Matsuda, Toshio; Naruse, Shoichi; Hayashi, Ikuo; Takata, Yoshiyuki.    Fac. Eng.,  Hokkaido Univ.,  Sapporo,  Japan.    Nippon Kagaku Kaishi  (1974),   (1),  198-200.  CODEN: NKAKB8  Journal  written in Japanese.   

Abstract
Sulfur monochloride and carboxylic acids react in the presence of catalysts [e.g. FeCl2, FeSO4, Fe, Fe(OAc)3] to give the corresponding acid chlorides.  Aromatic mono- and dicarboxylic acids (isophthalic and terephthalic acids, with exception of phthalic acid) and lower fatty acids produced acid chlorides in good yields.  Adipic acid, aliph. dicarboxylic acid, produced small quantity of acid chloride in the presence of Fe(OAc)3 only, but in the presence of Fe(OAc)3 and pyridine the yield of acid chloride rose to about 50%. 


Manufacture of high-purity sulfur monochloride.    
Sato, Makoto; Kajiwara, Juji; Sakai, Masanobu.  (Sumitomo Seika Kk, Japan).    Jpn. Kokai Tokkyo Koho  (1995),     4 pp. 
JP  07118004  A2  19950509  Heisei.  
Patent  written in Japanese.  

Abstract
The process comprises quant. reacting Cl with S by reacting S dissolved in S2Cl2 with the stoichiometric amt. of Cl, or reacting S dissolved in S2Cl2 with Cl while monitoring the reaction mixt. to detect the end of the reaction.  Both processes are carried out in the presence of a Lewis acid and/or metals.  High-purity S2Cl2 is manufd. in high yields.

The lewis acids used appear to be FeCl3 and Nickel chlorides.  Actually I think you can just add a bit of iron of nickel powder to the S2Cl2 and you get the catalyst.


   

There are some very good uses for acetyl chloride that I will post soon. 

Do Your Part To Win The War
 
 
 
 
    Antoncho
(Official Hive Translator)
10-29-01 21:27
No 230004
      Re: Acetyl Chloride/Acid chloride production!  Bookmark   

Appetitious!

Actually i do remember hearing smwhere a mention that this process is suitable for producing monochloroacetic acid! I think they said .. wait a minute.. here - they said when passing Cl2 into sulfur-containing AcOH ClCH2COOH was obtained w/a quite small AcOCl%, but at RT the main product was AcOCl.

Also - DO NOT MAKE S2Cl2 AS SWIA STATED IN HIS POST - use Catastrophe's variation instead (see same thread).

Antoncho
 
 
 
 
    joyman
(Stranger)
10-30-01 17:51
No 230520
      Re: Acetyl Chloride/Acid chloride production!  Bookmark   

for acid chlorides with sulphur monochloride i saw this lurking at Rhodiums -

../rhodium/chemistry /phenylacetone.html
Propionyl chloride was prepared not only by the usual methods with phosphorus bichloride or phosphorus pentachloride, but also by the chlorination of propionic acid in the cold with sulfur monochloride present.

To 540 g of propionic acid, 245 g of sulfur monochloride was added and chlorine was passed through the mixture while it was stirred for 15 hours. The chlorination proved to be incomplete at this point, since 150 g of unchanged propionic acid was recovered. There  was also considerable sulfur monochloride, which was removed from the propionyl chloride by treatment with hydrogen sulfide. The  propionyl chloride obtained amounted to 250 g. This product functioned as satisfactorily in the subsequent preparation of propiophenone as that prepared by the phosphorus halide methods
[1] JACS 44, 1751-1752 (1922)


Also for the prep of pcl3 for gaa -> acetyl chloride found this in a newsgroup -

Phosphorous trichloride is prepared by scraping the red phosphorous from the "striker" on book matches, boiling the powder with 50% alcohol and collecting the crude red phosphorus as an insoluable residue.  It is then placed in reflux with dry chlorine until all the phosphorous is gone into solution.  Phosphorous trichloride is a clear, fuming liquid.  Protect from moisture!

also -

Theres something called the Hell-Volhard-Zelinsky halogenation which i think uses phosphorus in situ and then passes in br or cl gas. The first stage of this results in the OH of the carboxyllic being attack after which the halogen gets shuffled around. If this process could be arrested at the first reaction then it might be an interesting way to make acetyl/propionyl chloride using only a small ammount of phosphorus and without having to first prep the pcl3. 
 
 
 
 
    cilliersb
(Hive Bee)
10-31-01 13:12
No 230875
      Re: Acetyl Chloride/Acid chloride production!  Bookmark   

on ../rhodium/chemistry /anhydrides.html

At the bottom of the page there is a procedure for making AA while producing SCl2 in situ. I mentions adding AA during the reaction. Should this not be GAA and not AA?
 
 
 
 
    Rhodium
(Chief Bee)
10-31-01 17:03
No 230923
      Re: Acetyl Chloride/Acid chloride production!  Bookmark   

Actually, the reaction uses some AA to make more AA.
 
 
 
 
    cilliersb
(Hive Bee)
11-01-01 08:29
No 231465
      Re: Acetyl Chloride/Acid chloride production!  Bookmark   

I know that this may lower yields, but can a pre run be done with GAA instead to produce a little AA that can be used in a larger scale AA production.

I'll try this and report back.
 
 
 
 
    Bozakium
(Hive Bee)
11-01-01 08:37
No 231467
      Re: Acetyl Chloride/Acid chloride production!  Bookmark   

One can never have enough pathways on one's pallette.
What does hot sulfur chloride smell like? It would probably make a good air freshener for the Bozak lab!
 I chill with roadkill, cadaverine dream..
 
 
 
 
 
    cilliersb
(Hive Bee)
11-01-01 08:57
No 231472
      Re: Acetyl Chloride/Acid chloride production!  Bookmark   

Prolly something similar to an egg fart, or maybe the adams family attick. HeHesmilelaugh
 
 
 
 
    Rhodium
(Chief Bee)
11-01-01 14:37
No 231550
      Re: Acetyl Chloride/Acid chloride production!  Bookmark   

Yes, a low-yield pre-run with GAA can probably be performed.
 
 
 
 
    foxy2
(Distinctive Doe)
05-20-02 08:05
No 311175
      Acid Chloride Synthesis
(Rated as: excellent)
 Bookmark   

A mild and efficient procedure for the preparation of acid chlorides from carboxylic acids.    
Jang, Doo Ok; Park, Doo Jin; Kim, Joonggon.   
Tetrahedron Letters  (1999),  40(29),  5323-5326.

Abstract
Various carboxylic acids are converted into the corresponding acid chlorides by treatment with trichloroacetonitrile and triphenylphosphine in methylene chloride at room temp.  Aryl acids show higher reactivity than alkyl acids under the conditions.

Typical Experimental Procedure:
To a mixture of benzoic acid (122 mg, 1.0 mmol) and trichloroacetonitrile (288 mg, 2.0 mmol) in CH2Cl2 (1 mL) under argon was added Ph3P (524 mg, 2.0 mmol) in CH2Cl2 (1 mL) dropwise at room temperature.  The reaction mixture was stirred for 40 min (TLC showed the dissappearance of benzoic acid).  The reaction mixture was then treated with cyclohexylamine (99 mg, 1.0 mmol) followed by triethylamine (0.42 mL, 3mmol).  The reaction mixture was allowed to react for 30 min.  The mixture washed with water.  Organic layer dried over MgSO4.  Column chromatography on silica gel (hexanes/EtOAc, 2:1) to give N-cyclohexylbenzamide (197 mg, 97 %).


Table 1 - Results in various solvents, procedure as above
------------------------------------------------------------------------------------------
Solvent         Yeild
----------------------------------------------------------------------------------------------------
CHCl2             97%
CHCl2 (0C)        95%
toluene           92%
THF               94%
CH3CN             99%
EtOAc             89%
Et2O              77%
--------------------------------------------------------------------------------------------------
An attempt to use carbon tetrachloride as the chlorine source failed, 0% yeild.


Table 2 - Results with other acids
-------------------------------------------------------------------------------------------------------
Acid          reaction time(h)a    yeild
---------------------------------------------------------------------------------------------------------
p-bromo benzoic        2      90%
p-methoxy benzoic      2      90%
p-(t)-butyl benzoic    1      95%
p-nitro benzoic        2      80%
acetylsalicylic        2      70%
trans-Cinnamic         2      83%
2-octenoic             4      79%

(the following used 4 equivalents each CCl3CN and PPh3, instead of 2)
n-octanoic             4      80%
2-bromoisovaleric      2       76%
-----------------------------------------------------------------------------------------------------------
a - time required for dissappearance of benzoic acid on TLC



A rapid, mild and acid-free procedure for the preparation of acyl chlorides including formyl chloride.    
Villeneuve, G. B.; Chan, T. H.   
Tetrahedron Lett.  (1997),  38(37),  6489-6492.

Abstract
Carboxylic acids are converted by hexachloroacetone and triphenylphosphine at -78 C in methylene chloride to the corresponding acyl chlorides.  Formic acid can be used to generate formyl chloride at -78 C in order to perform formylation under very mild conditions.

Experimental

N-benzylbenzamide: To a mixture of benzoic acid (122 mg, 1.0 mmol) and hexachloroacetone (132 mg, 0.5 mmol) in CH2Cl2 (2 mL) was stirred under argon and cooled to -78C.  Ph3P (262 mg, 1 mmol) in CH2Cl2 (1 mL) was added dropwise and the mixture stirred for 20 min.  The acylchloride solution was then treated with a solution of benzylamine (107 mg, 1 mmol) in CH2Cl2 (1 mL) dropwise followed by truethylamine (101 mg, 1 mmol) in CH2Cl2 (1 mL).  This was allowed to reach room temperature and the solvent removed under vacuum.  The residue was suspended in 20% EtOAc in hexane (4 ml) and silica gel added to obtain a pasta.(Their cookin smile).  Purified by column chromatography with same solvent. 
Yeild 187 mg, 95%.

N-4-methylphenylformamide:  Procedure same as above except reagents were formic acid 100% (92 mg, 2 mmol), hexachloroacetone (264 mg, 1 mmol), Ph3P (524 mg, 2 mmol), p-methylanaline (107 mg, 1 mmol) and TEA (202 mg, 2 mmol).
Yeild 119 mg, 88%.



Use of oxalyl chloride and bromide for producing acid chlorides, acid bromides or acid anhydrides. III.
Adams, Roger; Ulich, L. H.   
J. Am. Chem. Soc.  (1920),  42  599-611.

Abstract
cf. C. A. 12, 587.  Aromatic or aliphatic acids warmed with 2.5 mols. (COCl)2 (A) are converted quickly and practically quant. into the corresponding acid chlorides, even in C6H6 as solvent. p-HOC6H4CO2H gives a complex condensation product.  Certain NO2 derivs. of BzOH yield double anhydrides of 2 mols. of the aromatic acid and 1 of (CO2H)2, even after refluxing several hrs. with excess of A.  Instead of the acid, the Na salt can be added gradually to 1-1.5 mols. of A in C6H6; in fact, this method of prepg. acid chlorides appears to be more general than that from the free acids and is generally preferable, as a smaller excess of A is required.  Those NO2 acids which give double anhydrides, as mentioned above, yield the chlorides exclusively when used in the form of their Na salts.  Acid chlorides are also readily formed from the anhydrides and A alone or in C6H6 refluxed a few hrs. 

The method of prepn. of aromatic acid anhydrides by the action of 1 mol.  A on 2 mols. of the acid in C6H6 described in the earlier paper is apparently general.  Again certain NO2 derivs. of BzOH behave peculiarly, giving double anhydrides of (CO2H)2 which, when melted, decomp. into the simple anhydrides.  With aliphatic acids the yields are not so good; in most cases some of the acid is unchanged and the chloride is obtained as a by-product.  In prepg. anhydrides also, the Na salt of the acid, suspended in C6H6, may be used instead of the free acid; in the case of aliphatic compds., this is the better method.  The mechanism of these reactions can be represented as follows: RCO2H + A --> (RCO2CO)2 + 2HCl; (RCO2CO)2 --> (RCO)2O + CO2 + CO; (RCO)2O + A --> 2RCOCl + CO2 + CO.  In the case of the Na salts, the chlorides and simple anhydrides are possibly formed directly, without passing through the double anhydride stage.  In the 2 cases tried (As2O2. and CrO3) the inorg. acid chlorides were obtained by refluxing the oxides with a slight excess of A.

A also proved to be an excellent reagent for producing the Beckmann rearrangement in ketoximes. (COBr)2 acts like A.  The following compds. were prepd. by the methods given above (the figures represent the % yields): Chlorides: valeryl 95, hydrocinnamyl 98, benzoyl 98, o-bromobenzoyl 93, p-bromobenzoyl 94, lauryl 99, salicylyl 98, chloroacetyl 80, phenylacetyl 74. p-Nitrobenzoic oxalic anhydride, yellowish crystals, m. 169-70, decompg. into (p-O2NC6H4CO)2O, immediately decompd. by C5H5N. 2,4,6-Trinitrobenzoic oxalic anhydride, slightly yellowish crystals, m. 228-30, decompg. into C6H3(NO2)3 (not (O2N)3C6H2CO2H), and is decompd. by Na2CO3, into (O2N)3C6H2CO2Na.  Anhydrides: From the free acids: butyric 56, phenylacetic 46, cinnamic 76.  From the Na salts: benzoic, m- and p-nitrobenzoic, o-chlorobenzoic (the yields with aromatic compds. are 75-90%), chloroacetic 54, butyric 79, valeric 92, lauric 80.  AsCl3 and CrCl3 were obtained in 95 and 80% yield, resp.  BzNHPh, MeOC6H4CONHPh and p-MeC6H4CONHPh were obtained in over 90% yield by warming Ph2C:NOH, Ph(MeOC6H4)C:NOH and Ph(MeC6H4)C:NOH, resp., for 10 min. in Et2O with 0.75 mol. A.  Bromides (from the Na salts; yield, generally over 90%): benzoyl; o-chlorobenzoyl, b37 143-5; m-isomer, b40 143-7; p-isomer, b27 141.3; o-bromobenzoyl, b18 166-8; p-isomer, b18 135-7; p-iodobenzoyl, crystals from CCl4, m. 54-5, becomes very dark in 2 days, even in sealed tubes; o-methylbenzoyl, b37 133-6; m-isomer, b52 136-7; p-isomer, b42 145-9; p-methoxybenzoyl, b27 183-6; m-nitrobenzoyl, yellowish crystals from CCl4, m. 42-3, b18 165-7, p-isomer, yellow crystals from CCl4, m. 63-4; 3,5-dinitrobenzoyl, yellow crystals from CCl4, m. 59-60; cinnamyl, yellow crystals, m. 47-8, b40 180-4; phenylacetyl, b50 150-5.  These bromides can be obtained also, although not with as good yields nor in as pure state, with PBr5. 


Experimental:
Action of Oxalyl Chloride on Organic Acids-Preparation of Acid Chlorides.
The general procedure by which acid chlorides are produced from acids by means of oxalyl chloride is as follows: In a round-bottom flask, the neck of which is ground to fit the bottom of a reflux condenser, is placed one mole of the organic acid and 2 to 2.5 moles of oxalyl chloride. In some cases, an evolution of gas starts immediately, indicating that the reaction is taking place; in other cases slight warming is necessary before gases are evolved. After once starting, the reaction proceeds spontaneously for 15-20 min. or sometimes even longer. After this period of time a small flame is again applied and the mixture refluxed for about 2 hours. The reaction mixture is then distilled under atmospheric pressure till the excess of oxalyl chloride is collected and then generally under diminished pressure (preferably in a flask such as is described by Noyes1 without the separatory funnel attached, however) to obtain the acid chloride. By this method the series of acid chlorides which are given in the table below were produced:

---------------------------------------------------------------------------------------------------------------
Acid / Acid wt. / wt. oxalyl Cl / Acid Cl wt. / Yeild %                 
---------------------------------------------------------------------------------------------------------------
n-Valeric. ..........     25    77    28    95
Hydrocinniamic....... 35    60    38    98
Benzoic..............      25    60    28    98
o-Bromobenzoic....... 25    40    25    93
p-Bromobenzoic....... 10    13    10    94
Lauric...............       25    40    27    99
Salicylic ...........    15    28    16.5  98
Monochloroacetic .... 25    80    24    80
Phenylacetic. ....... 35    70    30    74
---------------------------------------------------------------------------------------------------------------

It is noticeable that only in 2 cases, namely monochloroacetic acid and phenylacetic acid, do the yields drop below 90%. Monochloroacetic acid forms an anhydride with extreme ease in the presence of almost any sort of dehydrating agent and small amounts were isolated in the above reaction. Phenylacetyl chloride is not very stable and extremely reactive, giving certain amounts of tarry material, probably condensation products between several molecules. The yields, however, in both cases, are very much better than are obtained with other acid chloride reagents with the possible exception of thionyl chloride.

The preparation of these acid chlorides can be carried out if desired in benzene as a solvent (about 50 cc. of benzene being used for a 25 g. portion of acid); thus, both benzoic and monochloroacetic acids gave satisfactory results under these conditions. In the case of salicylic acid, because of the instability of the acid chloride, the preparation of this latter compound was not attempted except with benzene as a solvent, and after the reaction had taken place the benzene and excess of oxalyl chloride were removed by distilling off under diminished pressure at room temperature. The action of oxalyl chloride upon p-hydroxybenzoic acid was carried out but complex condensation products were obtained and no acid chloride was produced.

When excess of oxalyl chloride reacts with m-nitro, p-nitro-, 3,5-dinitro-, and 2,4,6-trinitrobenzoic acids, the acid at first goes into solution and in the course of a few minutes a solid separates. After refluxing for 2 hours the reaction mixture is treated directly with benzene, the solid filtered, washed with dil. sodium carbonate solution (except in the case of the trinitrobenzoic acid), dried and washed with hot benzene. The benzene filtrates from the original reaction mixture are evaporated and a small amount of solid material is always obtained, This is unchanged acid. Of the 4 nitro compounds produced, the double anhydride of m-nitrobenzoic acid2 and 3,5-dinitrobenzoic acid have already been described in previous communication and the decomposition points here agree with those previously obtained. The double anhydrides of oxalic and p-nitrobenzoic acid as well as of 2,4,6-trinitrobenzoic acid, however, are new.


Action of Oxalyl Chloride on the Sodium Salts of Organic Acids - Preparation of Acid Chlorides.
The general procedure by which acid chlorides are produced from the sodium salts of acids and oxalyl chloride is as follows. A round-botton flask is used which has 2 openings; the one is a neck ground to fit a reflux condenser and the second is a side tube(1.5 cm in diameter and 2.5 cm long). This second side tube is cork-stoppered and is used for the addition of solid sodium salt. In the flask with the reflux condenser attached is placed 1.2 to 1.5 moles of oxalyl
chloride dissolved in benzene (20 cc. of benzene is used when about 10 g of oxalyl chloride is needed). One mole of the dry sodium salt of the acid is now added in small portions through the side arm. Upon each addition, gases are evolved. After all of the sodium salt has been added,
the mixture is refluxed for 2 hours with occasional stirring to be certain that the reaction is completed. At the end of this time the sodium chloride and any traces of unchanged sodium salt of the organic acid are filtered off, The filtrate is distilled and after recovering the benzene, the acid chloride, if solid, is crystallized or if a liquid, vacuum distilled, In this way yields of: acid chloride varying from 75% to over 90% are easily produced. In the experiments carried out to test the method only small
amounts (10 to 20 grams) of the sodium salts of the acid were used and consequently the loss involved in a distillation or crystallization was proportionately large. It is probable that if 100 gram lots of acid chloride
should be made, the yields would be consistently over 90%. The compounds are practically pure as obtained directly from the benzene, but in the experiments described the products were either recrystallized or once distilled. By this method, the following acid chlorides were made: cinnamyl, phenylacetyl, benzoyl; and the following substituted benzoyl
chlorides: p-chloro-, o-bromo-, p-bromo-, p-methoxy-, m-nitro-, p-nitro-, and 3,5-dinitro-. The constants agreed in every case with those appearing in the literature.


Action of Oxalyl Chloride on Organic Acid - Preparation of Organic Acid Anhydrides.
The general procedure by which acid chlorides are produced from acid anhydrides by means of oxalyl chloride is as follows. In a round-bottom flask of the type used for the production of acid chlorides from organic acids and oxalyl chloride, is placed one mole of the organic acid anhydride and 1.5 to 2.5 moles of oxalyl chloride. The mixtnre is gently refluxed for 2 hours. Evolution of gas takes place, as the reaction proceeds. At the end of the heating, the reaction mixture is distilled to free it from the excess of oxalyl chloride and the acid chloride which is thus obtained is purified by crystallization or distillation under atmospheric pressure or diminished pressure. By this general process, acetic, monochloroacetic, benzoic, m-nitro- and 3,5-dinitro-benzoic acid anhydrides were converted into the corresponding acid chlorides, and yields of 80-95% obtained.


Action of Oxalyl Chloride on Organic Acids - Preparation of Organic Acid Anhydrides.
The general procedure by which acid anhydrides are produced from acids and oxalyl chloride is as follows. A benzene solution or suspension is made of 2 moles of aromatic acid (100 cc. of benzene for 25 g. of organic acid) and one mole of oxalyl chloride is gradually run in. The mixture is refluxed for 2 hours and then the benzene distilled off. The yields of aromatic acid anhydrides by this
method are very good, but in the aliphatic series they seldom amount to more than 50% to 70%. As by-products in these latter reactions are obtained free acid and acid chloride. The particular compounds which were studied were n-butyric acid (56% yield), phenylacetic acid (46% yield)
and cinnamic acid (76% yield). If these same reactions with the acids are carried out without benzene as a solvent, the yields are about the same as indicated.


Action of Oxalyl Chloride on the Salts of Organic Acids - Preparation of Organic Acid Anhydrides.
The general procedure is to suspend 2 moles of the powdered, dry sodium salt of the acid in benzene (50 cc. of benzene for 25 g. of sodium salt) and then to allow 1 to 1.2 moles of oxalyl chloride to run in. The reaction takes place rapidly and after 2 hours refluxing, is complete. The sodium chloride is filtered off and the anhydrides are obtained by evaporation of the benzene. With some of the aromatic acids, the anhydrides are only slightly soluble in benzene and
consequently must be recovered from the mixture with sodium chloride by treatment with dilute sodium carbonate. The aromatic acid anhydrides as obtained from the benzene are washed with dil. sodium carbonate solution, dried and recrystallized while the aliphatic acid anhydrides are purified by distiliation with a good fractionating column. In the aromatic series, the yields are very good, amounting to 75% to 90%. In the aliphatic series, however, some acid chloride is produced although in smaller amounts than when anhydrides are made from the free acids and oxalyl chloride. The sodium salts of the following acids were converted to anhydrides as just described : benzoic, m- and p -nitrobenzoic, o-chlorobenzoic, monochloroacetic (54% yield), n-butyric (79% yield), n-valeric (91% yield), lauric (80% yield). The physical constants werc not different from thosc already given in the literature.


Action of Oxalyl Chloride on Certain Aromatic Ketoximes-Preparation of Substituted Acid Amides.
Benzophenone oxime, anisyl-phenyl ketoxime and phenyl-p-tolyl ketoxime are treated in the following way:
One mole of the ketoxime is dissolved in a small amount of absolute ether. To the solution is added slowly 3/4 of a mole of oxalyl chloride. The mixture is kept warm for 10 minutes, during which time acid amide separates. At the end of this period half oh the ether is evaporated, the mixture cooled and the solid acid amide filtered. The yields of benzanilide, anisanilide and p-toluic anilide amount to over 90%.


Action of Oxalyl Chloride on Inorganic Acids - Preparation of Inorganic Acid Chlorides.
In a gask similar to the one used in the previous experiments are placed arsenic trioxide (one mole) and excess of oxalyl chloride (2 moles). The reaction mixture is refluxed gently for 5 hours, during which time the oxide qradually goes into solution. The reaction mixture is then distilled, a small excess of oxalyl chloride collected first and then the arsenic trichloride, b.p. 130. The yield amounts to about 95%.
In the same way dry chromium trioxide (one mole) and oxalyl chloride (2 moles) upon refluxing for 5 hours gives an 80% yield of chromyl chloride, b.p. 114-116 at 748 mm.


Action of Oxalyl Bromide on the Sodium Salts of Organic Acids - Preparation of Acid Bromides.
The general procedure by which acid bromides are produced from the sodium salts of the acids is exactly analogous to the method used for the preparation of acid chlorides from the sodium salts of organic acids and oxalyl chloride. The products are worked up in exactly the same way. The yields of acid bromides are in general over 90%. The following table contains a list of the bromides thus prepared with their constants and chemical analyses.


Other Reactions with Oxalyl Bromide.
In order to determine whether oxalyl bromide might be used in place of oxalyl chloride for the production of acid anhydrides, benzoic acid, o- and p-chloro- and p-bromo-
benzoic acids were treated in benzene in the proportion of 2 moles of acid to one mole of oxalyl bromide. The directions followed were exactly analogous to those used with oxalyl chloride and in every case very good yields of the corresponding anhydrides were produced.
In order to show that excess of oxalyl bromide on the organic acids will yield acid bromides in the same way that oxalyl chloride yields acid chlorides, n-butyric acid (one mole) was refluxed with an excess of oxalyl bromide (2 moles) as described under the reaction between organic acids and oxalyl chloride. After the evolution of gas stopped, the reaction mixture was refluxed for 2 hours and then distilled in the usual way.  The bromide was produced in good yields.


The Action of Phosphorus Pentabromide upon Aromatic Acids and the Salts of Aromatic Acids.
One mole of phosphorus pentabromide is suspended in benzene and one mole of organic acid is added. The mixture is refluxed for 1 to 2 hours, at the end of which time the reaction is complete. Upon distillation under diminished pressure, phosphorus oxybromide comes over first and then the acid bromide. In this way benzoic and o-chlorobenzoic acids were converted to the acid bromides. The yields amounted to about 50%. The constants were the same as those already mentioned.
If the phosphorais pentabromide is suspended in benzene (50 cc. of benzene to 25 g. of acid) and the dry sodium salt or the acid is added gradually, a rapid reaction takes place and after refluxing a short time is complete. The sodium bromide is filtered off and the benzene filtrate distilled, first under atmospheric pressure to remove the benzene, then under diminished pressure to remove the phosphorus oxybromide and finally the acid bromide. The yields of pure product amount to 60-75%. By this method benzoic acid and its o- and p-bromo-, o- and m-methyl-, m-nitro-, 3,5-dinitro derivatives were converted in to the corresponding acid bromides.


Summary
1. Organic acids when treated with 2 moles of oxalyl chloride alone or in benzene as a solvent are converted almost quantitatively into acid chlorides.
2. The sodium salts of organic acids when added to 1.2-1.5 moles of oxalyl chloride in benzene are converted almost quantitatively into acid chlorides.
3. Certain nitro derivatives of benzoic acid when treated as in (1) are converted into double anhydrides of oxalic acid and the aromatic acid; when treated as in (2) are converted into acid chlorides as is the case with other acids.
4. Organic acid anhydrides when treated with oxalyl chloride are converted almost quantitatively into acid chlorides.
5. Certain inorganic oxides are readily converted by oxalyl chloride into the corresponding acid chlorides.
6. Aromatic organic acids (2 moles) when treated in benzene solution with oxalyl chloride (one mole) are converted almost quantitatively into acid anhydrides. Aliphatic organic acids under the same treatment are converted to acid anhydrides only to the extent of 50-70%, some unchanged acid and acid chloride being by-products.
7 . The sodium salts of aromatic organic acids (2 moles) when suspended in benzene and treated with oxalyl chloride (one mole) are converted almost quantitatively into acid anyhydrides. In the aliphatic series, the yields of acid anhydride are not so good as in the aromatic series,
but much better than are obtained by the action of oxalyl chloride on the free organic acid.
8. Certain nitro derivatives of benzoic acid when treated as in (6) are converted into double anhydrides of oxalic acid and aromatic acid; when treated as in (7) are converted into acid anhydrides as is the case with other acids.
9. The Beckmann rearrangement in ketoximes is readily produced by the action of oxalyl chloride.
10. If organic acids or the salts of organic acids are treated with oxalyl bromide under the same conditions as in (1), organic acid bromides are produced. Several new aromatic acid bromides are described.
11. Organic acids are converted into their anhydrides by oxalyl bromide when treated as described in (6).

Reference
{1} J. Am. Chem. Soc. 39, 2718 (1917).
{2} J. Am. Chem. Soc. 40, 424 (1918).
 
 
 
 
    Mountain_Girl
(Hive Bee)
05-20-02 12:01
No 311238
      Innnerrresting  Bookmark   

The prep of acid chlorides using oxalyl chloride is quite interesting in particular. Unfortunately, afaik in order to synth oxalyl chloride (from oxalic acid) you would need a chlorination agent like SOCl2, PCl5, etc. If you already have such reagents then you may as well just use them to make your acid chloride directly (or make AA via the acid chloride of GAA). Perhaps someone has an alternative route to oxalyl chloride ?
 
 
 
 
    foxy2
(Distinctive Doe)
05-20-02 15:05
No 311282
      Interesting!
(Rated as: excellent)
 Bookmark   

Chlorides and anhydrides of aliphatic acids.    
Patent GB344116
Abstract
Chlorides and anhydrides of aliphatic acids are produced by reacting with sulphuryl chloride (or sulphur dioxide and chloride) on dry alkaline-earth salts of the acids in presence of a solid inert diluent such as sand, with or without a solvent, and at a low temperature. The solid diluent may be a substance capable of neutralizing the inorganic acids liberated, such as a phosphate silicate or a single or double carbonate of calcium, magnesium, barium or the like. If the alkaline-earth salt of the organic acid is moist, calcium oxide may be added, and the sulphuryl chloride may contain free chlorine or thionyl chloride. In an example, sand and calcium carbonate are mixed with the calcium salt of the aliphatic acid and the mixture treated with sulphuryl chloride or its constituents in a closed vessel provided with a stirrer and cooling-jacket, the chloride or anhydride being then distilled off at ordinary or reduced pressure respectively; in this process a small quantity of calcium oxide and an acidyl chloride or anhydride produced in a preceding operation may be added. The process may be applied to the production of separate aliphatic acids from mixtures of their calcium salts, as the mixed anhydrides can be separated by fractional distillation more easily than can the acids, the anhydrides being then hydrolyzed to produce the acids.


Acetic anhydride.   
(E. B. Badger & Sons Co.) (1929)    
Patent GB333991 
Abstract
Anhyd.NaOAc, S chloride or sulfuryl chloride and Cl are fed to a batch reaction chamber surrounded by a cooling jacket and the temp. is preferably maintained slightly below 10.  Various details of app. and procedure are described. 

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