Atlanta College of Art Chemistry Organic Syntheses Questions read the documents given. Please read the paper given to you and answer the questions that fol

Atlanta College of Art Chemistry Organic Syntheses Questions read the documents given. Please read the paper given to you and answer the questions that follow.This is an open book assignment and you have a week to complete it.You can use the internet, any books you want, feel free to use any resources you need. A Publication
of Reliable Methods
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DOI:10.15227/orgsyn.036.0050
Organic Syntheses, Coll. Vol. 4, p.576 (1963); Vol. 36, p.50 (1956).
p-METHOXYPHENYLACETONITRILE
[Acetonitrile, p-methoxyphenyl-]
Submitted by Kurt Rorig, J. Derland Johnston, Robert W. Hamilton, and Thomas J. Telinski1.
Checked by William S. Johnson, Stanley Seltzer, and Peter Yates.
1. Procedure
In a 1-l. flask fitted with a paddle-blade stirrer are placed 138 g. (1 mole) of anisyl alcohol (Note 1)
and 248 ml. of concentrated hydrochloric acid. After stirring vigorously for 15 minutes the contents of
the flask are transferred to a separatory funnel. The lower layer (anisyl chloride) is separated, dried over
20 g. of granular calcium chloride for about 30 minutes, and filtered to remove the drying agent.
In a 2-l. three-necked round-bottomed flask, fitted with an efficient sealed stirrer and a reflux
condenser capped by a drying tube, are placed the dried anisyl chloride (Note 2) and (Note 3), 73.6 g.
(1.5 moles) of finely powdered sodium cyanide, 10 g. of sodium iodide, and 500 ml. of dry acetone
(Note 4). The heterogeneous reaction mixture is heated under reflux with vigorous stirring for 16–20
hours, then cooled and filtered with suction. The solid on the filter is washed with 200 ml. of acetone
and discarded (Note 5). The combined filtrates are distilled to remove the acetone. The residual oil is
taken up in 300 ml. of benzene and washed with three 100-ml. portions of hot water. The benzene
solution is dried over anhydrous sodium sulfate for about 15 minutes, and the solvent is removed by
distillation at the reduced pressure of the water aspirator (Note 6). The residual pmethoxyphenylacetonitrile is purified by distillation under reduced pressure through an 8-in. Vigreux
column; b.p. 94–97°/0.3 mm.; nD25 1.5285–1.5291. The yield is 109–119 g., or 74–81% based on anisyl
alcohol (Note 7) and (Note 8).
2. Notes
1. Givaudan-Delawanna (330 W. 42nd Street, New York 18, N. Y.) “Anisic Alcohol” of 97% minimum
purity was used.
2. The crude anisyl chloride is unstable. It should be used the same day it is made.
3. This step should be performed in a well-ventilated hood.
4. The acetone is dried over about one-quarter its volume of granular calcium chloride for one day. The
dried acetone is then filtered and distilled.
5. This residue should be discarded with due regard for the unused sodium cyanide it contains.
6. The undistilled p-methoxyphenylacetonitrile weighs 125–139 g. (85–95%) and has a refractive index
close to that of the distilled product. It can be used for many purposes, such as condensation with
aromatic aldehydes to yield ?-p-methoxyphenylcinnamonitriles, without further purification.
7. The submitters have carried out this preparation on five times the scale described here with
comparable yields.
8. This method is particularly applicable to the more reactive benzyl halides which are easily
hydrolyzed in the aqueous media usually employed for the metathetical reaction with alkali cyanides.
For example, anisyl chloride treated with sodium cyanide in aqueous dioxane gives, as a by-product, 5–
10% of anisyl alcohol as determined by infrared analysis. The use of anhydrous acetone not only
prevents hydrolysis to the alcohol but also decreases the formation of isonitriles. This method was also
applied successfully by the submitters to the preparation of p-chlorophenylacetonitrile in 74% yield.
3. Discussion
This method is an adaptation of that of Dengel.2 p-Methoxyphenylacetonitrile can also be prepared
by the metathetical reaction of anisyl chloride with alkali cyanides in a variety of aqueous solvent
mixtures;3,4,5,6,7,8,9,10,11 by the nitration of phenylacetonitrile, followed by reduction, diazotization,
hydrolysis, and methylation;12,13 by the reduction of ?-benzoxy-p-methoxyphenylacetonitrile (prepared
from anisaldehyde, sodium cyanide, and benzoyl chloride);14 by the reaction of acetic anhydride with
the oxime of p-methoxyphenylpyruvic acid;15 and through the condensation of p-methoxybenzaldehyde
with rhodanine.16
References and Notes
1. G. D. Searle and Company, Chicago 80, Illinois.
2. Dengel, German pat. application (DBP, Anm. K2355, March 30, 1950; Knoll-A.G.) as reported
by Müller, Methoden der Organischen Chemie (Houben-Weyl), Vol. 8, p. 294, Georg Thieme
Verlag, Stuttgart, 1952.
3. Shriner and Hull, J. Org. Chem., 10, 230 (1945).
4. Métayer, Ann. chim. Paris, [12] 4, 210 (1949).
5. Van Heyningen, J. Am. Chem. Soc., 74, 4862 (1952).
6. Dankova, Evdokimova, Stepanov, and Preobrazhenskii, Zhur. Obshchei Khim., 18, 1724 (1948)
[C. A., 43, 2606 (1949)].
7. Lapiné, Bull. soc. chim. France, [5] 6, 390 (1939).
8. Lee, Ziering, Berger, and Heineman, Jubilee Vol. Emil Barell, 1946, 280 [C. A., 41, 6252
(1947)].
9. Livshits, Bazilevskaya, Bainova, Dobrovinskaya, and Preobrazhenskii, Zhur. Obshchei Khim.,
17, 1675 (1947) [C. A., 42, 2606 (1948)].
10. Cagniant, Ann. chim. (Paris), 7, 442 (1952).
11. Burckhalter, Jackson, Sam, and Meyer, J. Am. Chem. Soc., 76, 4112 (1954).
12. Pschorr, Wolfes, and Buckow, Ber., 33, 171 (1900).
13. Silverman and Bogert, J. Org. Chem., 11, 43 (1946).
14. Campbell and McKail, J. Chem. Soc., 1948, 1255; Wawzonek and Fredrickson, J. Electrochem.
Soc., 106, 325 (1959).
15. Baker and Eastwood, J. Chem. Soc., 1929, 2902; Seshadri and Varadarajan, Proc. Indian Acad.
Sci., 37A, 145 (1953).
16. Yoder, Cheng, and Burroughs, Proc. Iowa Acad. Sci., 61, 271 (1954) [C. A., 49, 13236 (1955)].
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
oxime of p-methoxyphenylpyruvic acid
calcium chloride (10043-52-4)
hydrochloric acid (7647-01-0)
Benzene (71-43-2)
acetic anhydride (108-24-7)
sodium cyanide (143-33-9)
sodium sulfate (7757-82-6)
acetone (67-64-1)
benzoyl chloride (98-88-4)
phenylacetonitrile (140-29-4)
Anisic Alcohol (90-05-1)
sodium iodide (7681-82-5)
dioxane (5703-46-8)
Rhodanine (141-84-4)
p-chlorophenylacetonitrile (140-53-4)
anisyl alcohol (150-76-5)
anisyl chloride (623-12-1)
anisaldehyde,
p-methoxybenzaldehyde (123-11-5)
p-Methoxyphenylacetonitrile,
Acetonitrile, p-methoxyphenyl- (104-47-2)
?-benzoxy-p-methoxyphenylacetonitrile
Copyright © 1921-2005, Organic Syntheses, Inc. All Rights Reserved
Paper assignment – worth 10 % of grade (NOT 25 % as the final would have been)
Please read the paper given to you and answer the questions that follow.
This is an open book assignment and you have a week to complete it. You can use the internet, any
books you want, feel free to use any resources you need.
Take a picture of your answers and send it to me.
Total points: 120 (20 bonus points)
1. Is the first reaction SN1 or SN2? Explain. (35 points)
2. Would p-Tolyl alcohol (you can look up this structure if in doubt) react faster or slower in the
first reaction?
Briefly explain. (35 points)
3. What is the purpose of NaI in the second step (second reaction)? (30 points)
4. BONUS QUESTION 1 – 10 points:
The paper briefly mentions an alternative route starting with phenylacetonitrile (see the
discussion for the mechanism details). Write the reaction scheme.
BONUS QUESTION 2 – 10 points:
Maybe using Wikipedia answer the question: – what was the world event that led to the
founding of the Organic Synthesis Journal?
Paper assignment – worth 10 % of grade (NOT 25 % as the final would have been)

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